MSE 854

Characterization of Materials
Dr. Sofia Javed
sofia.javed@scme.nust.edu.pk
Office: 306
12th Sept. 2017
Course Content
Characterization of Materials
Energy dispersive and wavelength dispersive analysis, Quantitative
and Qualitative analysis, XRF
Structural Characterization, X Ray diffraction patterns
Spectroscopic techniques:
UV/Vis Spectroscopy
FTIR Spectroscopy,
NMR Spectroscopy
Raman Spectroscopy
Mass Spectrometry,
X-Ray Photoelectron Spectroscopy
Auger Spectroscopy and Gamma Ray Spectroscopy (just Introduction)
Thermal analysis; Differential Calorimetry, Thermal Gravimetric
analysis,
Atomic Force Microscopy
 Recommended Books
MATERIALS CHARACTERIZATION Introduction to Microscopic and
Spectroscopic Methods by Yang Leng (eBook will be provided).
ENCYCLOPEDIA OF MATERIALS CHARACTERIZATION by C. Richard
Brundle Charles A. Evans, Jr. Shaun Wilson (eBook will be provided)
Fundamentals of Molecular Spectroscopy by Banwell & McCash
(Available at SCME Library)
Handouts
Grading and Assessment

Quiz: 4-5 (unannounced) 10%

Assignment: 2 10%
OHTs: 2 30%
End Semester Exam: 1 50%
 MSE-854
Characterization of Materials
Part 1: Spectroscopic Techniques
Instructor: Dr. Sofia Javed
12-09-17
o Introduction to spectroscopy
o UV/Vis Spectroscopy
o FTIR Spectroscopy,
o Raman Spectroscopy,
o NMR Spectroscopy,
o Mass Spectrometry,
o X-Ray Photoelectron Spectroscopy,
o Auger Spectroscopy and Gamma Ray Spectroscopy
THE ELECTROMAGNETIC SPECTRUM
SPECTROSCOPY
Atoms and molecules interact with electromagnetic
radiation (EMR) in a wide variety of ways.
Atoms and molecules may absorb and/or emit EMR.
Absorption of EMR stimulates different types of motion in
atoms and/or molecules.
The patterns of absorption (wavelengths absorbed and to
what extent) and/or emission (wavelengths emitted and
their respective intensities) are called spectra.
The field of spectroscopy is concerned with the
interpretation of spectra in terms of atomic and
molecular structure (and environment).
 The entire electromagnetic spectrum is used for characterization!

Frequency, n in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

Energy (kcal/mol)
> 300 300-30 300-30 ~10-4 ~10-6

g-rays X-rays UV IR Microwave Radio

nuclear core electronic molecular molecular Nuclear Magnetic
excitation electron excitation vibration rotation Resonance NMR
(PET) excitation (p to p*) 104 J/mol 100J/mol (MRI), ESR
109-1011 (X-ray 100kJ/mol 0.001-10 J/mol
J/gram atom cryst.)
10MJ/mol

Visible
PET: Positron Emission Tomography
 Molecular Motions
Three ways molecules can change
to emit or absorb E-M radiation.

change electron arrangement

(e.g., electron in the outermost orbital of the oxygen
atom moves to lower or higher energy state)

change rotational state to a

lower/higher energy mode

change vibrational state to a lower

or higher energy mode
 Ultraviolet and Visible Spectroscopy

Violet: 400 - 420 nm

Indigo: 420 - 440 nm
Blue: 440 - 490 nm
Green: 490 - 570 nm
Yellow: 570 - 585 nm
Orange: 585 - 620 nm
Red: 620 - 780 nm
Electronic Excitation by UV/Vis Spectroscopy :
UV: valance Radio waves:
X-ray: IR: molecular
electronic Nuclear spin states
core electron vibrations
excitation (in a magnetic field)
excitation
UV/Vis Spectroscopy
Ultraviolet radiation stimulates electronic transitions (and
molecular vibrations).
Absorption spectroscopy from 160 nm to 780 nm
Measurement absorption or transmittance
Identification of inorganic and organic species.
The transitions that occur upon absorption of UV/Vis
radiation are among the electronic energy levels.
It is also called Electronic spectroscopy
Transmission and Color

The human eye sees the complementary color to that which is

absorbed
Absorbance and Complementary Colors
UV-Visible Spectroscopy 430nm
662nm
 Molecular energy levels
The electronic energy levels of simple molecules are widely
separated and usually only the absorption of a high energy photon,
i.e. one of very short wavelength, can excite a molecule from one
level to another.
In complex molecules the energy levels are more closely spaced
and photons of near ultraviolet and visible light can effect the
transition. These substances, therefore, will absorb light in some
areas of the near ultraviolet and visible regions.
Idealized Molecular Spectrum
In addition, when molecules are closely packed together they
exert influences on each other which slightly disturb the
already numerous, and almost infinite energy levels and blur
the sharp spectral lines into bands.
These effects can be seen in the spectra of benzene as a vapor
and in solution. In the vapor, the transitions between the
vibration levels are visible as bands superimposed on the main
electronic transition bands.
 Types of transitions occurring in UV/vis region
The energy supplied by the light will promote electrons from their ground
state orbitals to higher energy, excited state orbitals or antibonding orbitals.
Potentially, three types of ground state orbitals may be involved:
Sigma () bonding molecular orbital
Pi () bonding molecular orbital
Nonbonding atomic orbital (n)
Two types of antibonding orbitals may be involved in the transition:
* (sigma star) orbital
* (pi star) orbital
Note: there is no such thing as an n* antibonding orbital as the n electrons do
not form bond
UV-Visible Spectroscopy

Electronic transitions
Molecular Orbital Theory
Examples of transitions and resulting max
UV-Visible Spectroscopy

Electronic Transitions in
Formaldehyde
Types of transitions occurring in UV/vis region (contd.)

d-d Transitions
3d and 4d 1st and 2nd transitions series
Partially occupied d orbitals
Transitions from lower to higher energy levels
C C

p p
hv
= hv
=hc/l
p p

p p
Example: ethylene absorbs at longer wavelengths:
lmax = 165 nm = 10,000
C O

p p
n hv
n

p p

n p
The n to pi* transition is at even lower wavelengths but is not as strong as
pi to pi* transitions. It is said to be forbidden.
Example:
Acetone: n lmax = 188 nm ; = 1860
np lmax = 279 nm ; = 15
C C 135 nm

pp 165 nm
C C

H
C O n 183 nm weak

C O pp 150 nm
n 188 nm
np 279 nm weak

180 nm

C O
A

279 nm

l
Spectra
Effect of Conjugation on UV/Vis spectra
Conjugated systems:

C C

LUMO

HOMO

Preferred transition is between Highest Occupied Molecular Orbital

(HOMO) and Lowest Unoccupied Molecular Orbital (LUMO).
Note: Additional conjugation (double bonds) lowers the HOMO-LUMO energy
gap:
Example:
1,3 butadiene: lmax = 217 nm ; = 21,000
1,3,5-hexatriene lmax = 258 nm ; = 35,000
Shift in UV/Vis spectra

Terminology for Absorption Shifts

Nature of Shift Descriptive Term

To Longer Wavelength Bathochromic

To Shorter Wavelength Hypsochromic

To Greater Absorbance Hyperchromic

To Lower Absorbance Hypochromic

Chromophore Example Excitation lmax, nm Solvent

p __> p
C=C Ethene 171 15,000 hexane
*

C@C 1-Hexyne p __> p* 180 10,000 hexane

n __> p* 290 15 hexane

C=O Ethanal __> p*
p 180 10,000 hexane

ethano
n __> p* 275 17 l
N=O Nitromethane __> p*
p 200 5,000 ethano
l

Methyl
C-X X=Br n __> * 205 200 hexane
bromide
X=I n __> * 255 360 hexane
Methyl Iodide
 Taking spectrum
cuvette
slit
source
detector

Good plots have a range of absorbances from 0.010 to 1.000

Absorbances over 1.000 are not that valid and should be avoided
Instrumentation

Fixed wavelength instruments

Scanning instruments
Diode Array Instruments
Fixed Wavelength Instrument

LED serve as source

Pseudo-monochromatic light source
No monochrometer necessary/ wavelength selection
occurs by turning on the appropriate LED
4 LEDs to choose from
sample

beam of light

LEDs photodyode
 Scanning Instrument

Scanning Instrument
monochromator

Tungsten slit
Filament (vis)

Photomultiplier
slit tube
cuvette

Deuterium lamp
Filament (UV)
 Diode array Instrument

mirror
Diode array detector
328 individual detectors
Tungsten
Filament (vis)

slit
slit

cuvette
Deuterium lamp
Filament (UV)

monochromator
Comparison
Scanning instrument
High spectral resolution, l/l
Long data acquisition time (several minutes)
Low throughput
Diode array
Fast acquisition time (a couple of seconds), compatible with on-line
separations
High throughput (no slits)
Low resolution (2 nm)
Conventional Spectrophotometer

Schematic of a conventional single-beam spectrophotometer

UV-Visible Instrumentation

Light source
Tungsten lamp (350-2500 nm)
Deuterium (200-400 nm)
Xenon Arc lamps (200-1000 nm)
Sample containers
Cuvettes
Plastic
Glass
Quartz
Cell Types I

Open-topped rectangular standard cell (a)

and apertured cell (b) for limited sample volume
Cell Types II

Micro cell (a) for very small volumes and flow-through cell (b)
for automated applications
Transmission Characteristics of Cell
Materials

Note that all materials exhibit at least approximately 10% loss in

transmittance at all wavelengths
Applications of UV/Vis Spectroscopy
Measurement of Concentration of Solutions: Beer Lambert Law
Transmittance and Concentration
The Bouguer-Lambert Law
For a light absorbing medium, the light intensity falls exponentially with
sample depth.

T I / I 0 e ConstPathlength
Transmittance and Path Length: Beers Law
For a light absorbing medium, the light intensity falls exponentially with
increasing sample concentration.

Concentration

T I / I 0 e ConstConcentration
 The Beer-Bouguer-Lambert Law

The negative logarithm of T is called

the absorbance (A) and this is directly
proportional to sample depth (called
pathlength, l) and sample
concentration (c). The equation is
called the Beer-Bouguer-Lambert law.

is called the molar

absorption coefficient
and has units of dm3
mol-1 cm-1
A log T logI / I 0 logI 0 / I l c
Finding concentration using UV/vis
spectra
Prepare standards of known concentration
Measure absorbance at lmax
Plot A vs. concentration
Obtain slope
Use slope (and intercept) to determine the concentration of the analyte in the
unknown
Finding concentration using UV/vis
spectra
Absorbance at 540 nm
1.2

0.8

0.4

1 2 3 4
Concentration (g/l) glucose

Avoid very high or low absorbencies when drawing a

standard curve. The best results are obtained with 0.1 < A
< 1. Plot the Absorbance vs. Concentration to get a
straight line
 Every instrument has a useful range for a
particular analyte.
Often, you must determine that range
experimentally.
This is done by making a dilution series of the
known solution.
These dilutions are used to make a working
curve.
Make a dilution series of a known quantity
of analyte and measure the Absorbance.
Plot concentrations v. Absorbance.
What concentration do you think the
unknown sample is?
In this graph, values above A=1.0 are not linear. If we
use readings above A=1.0, graph isnt accurate.
Measurement of Reaction Rates

Rate studies involve the measurement of the

change in concentration of a participant in the
reaction as a function of time.
The reaction commonly used in clinical assays for
disease diagnosis is the reduction of nicotinamide
adenine dinucleotide (NAD) to NADH2.
The absorbance is monitored at the NADH2 peak at
340nm the reading will increase as the reaction
progresses towards NADH2.
Calculating Band Gap of Semiconductors
Metal ion transitions

Degenerate
D-orbitals D-orbitals
of naked Co of hydrated Co2+

Octahedral Configuration
HPLC-UV

HPLC
Pump

6-port HPLC
Mobile Sample column
valve
phase loop
UV
detector
syringe

Solvent
waste