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Chemical Industry
ca. $2 bn annual sale of catalysts
ca. $200 bn annual sale of the chemicals that are related products
90% of chemical industry has catalysis-related processes
Catalysts contributes ca. 2% of total investment in a chemical process
1
CH4003 Lecture Notes 11 (Erzeng Xue)
What is Catalysis
Catalysis
Catalysis is an action by catalyst which takes part in a chemical reaction process
and can alter the rate of reactions, and yet itself will return to its original form without
being consumed or destroyed at the end of the reactions
(This is one of many definitions)
2
CH4003 Lecture Notes 11 (Erzeng Xue)
Action of Catalysts
Catalysis action - Reaction kinetics and mechanism
Catalyst action leads to the rate of a reaction to change.
This is realised by changing the course of reaction (compared to non-catalytic reaction)
Forming complex with reactants/products, controlling the rate of elementary steps
in the process. This is evidenced by the facts that
The reaction activation energy is altered uncatalytic
energy
those formed in non-catalytic reaction reactant
The rates of reactions are altered (both
product
desired and undesired ones)
reaction process
Reactions proceed under less demanding conditions
Allow reactions occur under a milder conditions, e.g. at lower temperatures for those heat
sensitive materials
3
CH4003 Lecture Notes 11 (Erzeng Xue)
Action of Catalysts
It is important to remember that the use of catalyst DOES NOT vary DG & Keq
values of the reaction concerned, it merely change the PACE of the process
Whether a reaction can proceed or not and to what extent a reaction can proceed
is solely determined by the reaction thermodynamics, which is governed by the
values of DG & Keq, NOT by the presence of catalysts.
In another word, the reaction thermodynamics provide the driving force for a rxn;
the presence of catalysts changes the way how driving force acts on that process.
Applications of Catalysis
Industrial applications
Almost all chemical industries have one or more steps employing catalysts
Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals
Reducing wastes
Improving selectivity toward desired products - less raw materials required, less unwanted wastes
Replacing harmful/toxic materials with readily available ones
Applications of Catalysis
Environmental applications
Pollution controls in combination with industrial processes
Pre-treatment - reduce the amount waste/change the composition of emissions
Post-treatments - once formed, reduce and convert emissions
Using alternative materials
Pollution reduction
gas - converting harmful gases to non-harmful ones
liquid - de-pollution, de-odder, de-colour etc
solid - landfill, factory wastes
And many more
Other applications
Catalysis and catalysts play one of the key roles in new technology development.
7
CH4003 Lecture Notes 11 (Erzeng Xue)
Research in Catalysis
Research in catalysis involve a multi-discipline approach
Reaction kinetics and mechanism
Reaction paths, intermediate formation & action, interpretation of results obtained under
various conditions, generalising reaction types & schemes, predict catalyst performance
Catalyst development
Material synthesis, structure properties, catalyst stability, compatibility
Analysis techniques
Detection limits in terms of dimension of time & size and under extreme conditions (T, P)
and accuracy of measurements, microscopic techniques, sample preparation techniques
Reaction modelling
Elementary reactions and rates, quantum mechanics/chemistry, physical chemistry
Reactor modelling
Mathematical interpretation and representation, the numerical method, micro-kinetics,
structure and efficiency of heat and mass transfer in relation to reactor design
Catalytic process
Heat and mass transfers, energy balance and efficiency of process
8
CH4003 Lecture Notes 12 (Erzeng Xue)
Solid Catalysts
Catalyst composition
Active phase
Where the reaction occurs (mostly metal/metal oxide)
Promoter
Textual promoter (e.g. Al - Fe for NH3 production)
Electric or Structural modifier
Catalyst
Poison resistant promoters
Support
Support / carrier
Increase mechanical strength
Increase surface area (98% surface area is supplied within the porous structure)
may or may not be catalytically active
13
CH4003 Lecture Notes 12 (Erzeng Xue)
Solid Catalysts
Some common solid support / carrier materials
Alumina Other supports
Inexpensive Active carbon (S.A. up to 1000 m2/g)
Surface area: 1 ~ 700 m2/g Titania (S.A. 10 ~ 50 m2/g)
Acidic Zirconia (S.A. 10 ~ 100 m2/g)
Silica Magnesia (S.A. 10 m2/g)
Inexpensive Lanthana (S.A. 10 m2/g)
Surface area: 100 ~ 800 m2/g Active site
Acidic
Zeolite
mixture of alumina and silica, porous pore
solid
often exchanged metal ion present
shape selective
acidic
14
CH4003 Lecture Notes 12 (Erzeng Xue)
Preparation of catalysts
Precipitation
Drying
To form non-soluble precipitate by desired & firing
reactions at certain pH and temperature precursor add acid/base precipitate filter & wash
solution with pH control or deposit the resulting
Adsorption & ion-exchange precipitation precipitate
Support
Cationic: S-OH+ + C+ SOC+ + H+
adsorbed
Amount
Anionic: S-OH- + A- SA- + OH-
Drying
I-exch. S-Na+ + Ni 2+ D S-Ni 2+ + Na+ Concentration
& firing
Support
Impregnation
Fill the pores of support with a metal salt
solution of sufficient concentration to give Drying
the correct loading. & firing
Soln. of metal Pore saturated
Dry mixing precursor pellets
Physically mixed, grind, and fired
15
CH4003 Lecture Notes 12 (Erzeng Xue)
Solid Catalysts
Preparation of catalysts
Catalysts need to be calcined (fired) in order to decompose the precursor and to
received desired thermal stability. The effects of calcination temperature and time
are shown in the figures on the right. 40
BET S.A.
Commonly used Pre-treatments 75
50
Reduction 25
if elemental metal is the active phase 0 0
0 10
500 600 700 800 900 Time / hours
Sulphidation Temperature C
if a metal sulphide is the active phase
Activation
Some catalysts require certain activation steps in order to receive the best performance.
Even when the oxide itself is the active phase it may be necessary to pre-treat the
catalyst prior to the reaction ActivityInduction period
Normal use
Typical catalyst life span dead
Physisorption Chemisorption
force van de Waal chemcal bond
number of adsorbed layers multi only one layer
adsorption heat low (10-40 kJ/mol) high ( > 40 kJ/mol)
selectivity low high
temperature to occur low high
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CH4003 Lecture Notes 13 (Erzeng Xue)
Surface coverage, q
The solid surface may be completely or partially covered by adsorbed molecules
number of adsorption sites occupied
define q= q = 0~1
number of adsorption sites available
Adsorption heat
Adsorption is usually exothermic (in special cases dissociated adsorption can be
endothermic)
The heat of chemisorption is in the same order of magnitude of reaction heat;
the heat of physisorption is in the same order of magnitude of condensation heat.
18
CH4003 Lecture Notes 13 (Erzeng Xue)
Usually adsorption is only applied for a process dealing with small capacity
The operation is usually batch type and required regeneration of saturated adsorbent
Common adsorbents: molecular sieve, active carbon, silica gel, activated alumina.
Physisorption is an useful technique for determining the surface area, the pore
shape, pore sizes and size distribution of porous solid materials (BET surface area)
19
CH4003 Lecture Notes 13 (Erzeng Xue)
V3>V2
P4>P3
V2>V1
P3>P2
T1 V4>V3
Vol. adsorbed
Vol. adsorbed
T2 >T1 V1
Pressure
P2>P1
T3 >T2
P1
T4 >T3
T5 >T4
k Cs ( B0 PAB )1/2
Let. B0 ads q
k des C 1 ( B0 PAB )1/2
22
CH4003 Lecture Notes 13 (Erzeng Xue)
Cs , A B0 ,A PA Cs ,B B0 ,B PB
rearrange it for q qA qB
C 1 B0 ,A PA B0 ,B PB C 1 B0 ,A PA B0 ,B PB
kads,A k
where B0 ,A and B0 ,B ads,B are adsorption coefficients of A & B.
kdes ,A kdes ,B
23
CH4003 Lecture Notes 13 (Erzeng Xue)
case III
case II Cs , A B0 ,A PA
case I qA
C 1 B0 ,A PA B0 ,B PB
C BP Cs ( B0 PAB )1/2
q s 0 q C B0 ,B PB
C 1 B0 P C 1 ( B0 PAB )1/2 q B s ,B
C 1 B0 ,A PA B0 ,B PB
k ads k ads k k
B0 B0 B0 ,A ads,A and B0 ,B ads,B
k des k des kdes ,A kdes ,B
Adsorption Adsorption qA
Cs , A
B0 ,A PA
A, B both strong C B0 ,A PA B0 ,B PB
Strong kads>> kdes kads>> kdes C B0 ,B PB
q B s ,B
B0>>1 q C s 1 B0>>1 q
Cs
1 C B0 ,A PA B0 ,B PB
C C q A Cs ,A / C 1
Weak kads<< kdes kads<< kdes A strong, B weak PB
q B Cs ,B / C ( B0 ,B / B0 ,A )
Cs C PA
B0<<1 q B0 P B0<<1 q s ( B0 P)1/2 q A Cs ,A / C B0 ,A PA
C C A weak, B weak
q B Cs ,B / C B0 ,B PB 24
CH4003 Lecture Notes 14 (Erzeng Xue)
Amount adsorbed
C 1 ( B0 PAB )1/2
C B0 ,A PA
Case III q A s ,A mono-layer
C 1 B0 ,A PA B0 ,B PB
large B0 (strong adsorp.)
C B0 ,B PB
q B s ,B moderate B0
C 1 B0 ,A PA B0 ,B PB
small B0 (weak adsorp.)
Pressure
DH of ads
Langmuir
B0 P b1eQs / RT P Temkin
q qs
1 B0 P 1 b1eQs / RT P
q
where Qs is the heat of adsorption. When Qs is a linear function of qi. Qs=Q0-iS (Q0 is a
constant, i is the number and S represents the surface site),
1 1 [b1eQs / RT P RT 1 b1P
the overall coverage q q s dS dS ln
1 b P exp(- i
0 (1 b eQs / RT P i RT
0
1 1
When b1P >>1 and b1Pexp(-i/RT) <<1, we have q =c1ln(c2P), where c1 & c2 are constants
DH of ads
rads=kads(1-q)P rdes=kdesq Langmuir
Freundlich
B0 P b1eQi / RT P
q qi
1 B0 P 1 b1eQi / RT P q
where Qi is the heat of adsorption which is a function of qi. If there are Ni types of surface
sites, each can be expressed as Ni=aexp(-Q/Q0) (a and Q0 are constants), corresponding to a
fractional coverage qi, i qi Ni 0 [b1eQ / RT P / (1 b1eQ / RT P)] aeQ/Q0 dQ
the overall coverage q
iN
i 0
ae 0 dQ
Q/Q
30
CH4003 Lecture Notes 14 (Erzeng Xue)
31
CH4003 Lecture Notes 14 (Erzeng Xue)
P / P0 1 c -1
BET ( P / P0 ) Multilayer physisorption Useful in surface area
V ( 1 - P / P0 ) cVm cVm determination
32
CH4003 Lecture Notes 15 (Erzeng Xue)
When both A is weakly adsorbed or the partial pressure of A is very low (B0,APA<<1),
ri kB0 ,A PA PB k' PA PB 2nd order reaction
When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)
kB0 ,A PA PB
ri kPB 1st order w.r.t. B
B0 ,A PA
34
CH4003 Lecture Notes 15 (Erzeng Xue)
We then have ri k
(B0 ,AD PAD
1/ 2
P
k (B0 ,AD PAD PB
1/ 2
When both AD is weakly adsorbed or the partial pressure of AD is very low (B0,ADPAD<<1),
ri k (B0,AD PAD PB k' PAD
1/ 2 1/ 2
PB The reaction orders, 0.5 w.r.t. AD and 1 w.r.t. B
When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)
k (B0 ,AD PAD PB
1/ 2
38
CH4003 Lecture Notes 15 (Erzeng Xue)
39
CH4003 Lecture Notes 15 (Erzeng Xue)
Dd d d
Cumulative curve Frequency curve
40
CH4003 Lecture Notes 16 (Erzeng Xue)
Complex Reactions
Complex Reactions
Complex Reactions
Complex Reactions
d [A] [A]0
-k[A][-OH] -k[A] 2 or [A]
dt 1 kt[A]0
the conversion of B (-OH containing substance) at time t is
[A]0 - [A] kt[A]0
XB
[A]0 1 kt[A]0
44
CH4003 Lecture Notes 16 (Erzeng Xue)
Complex Reactions
Initiation: H2 + O2 O2H + H
45
CH4003 Lecture Notes 16 (Erzeng Xue)
Complex Reactions
Explosion Reactions
Type II Explosion: Thermal explosion
A rapid increase of the rate of exothermic reaction with temperature
Strictly speaking thermal explosion is not caused by multiple production of chain carriers
Must be exothermic reaction
Must be in a confined space and within short time
DH T r DH T r DH
A combination of chain-branching reaction with heat accumulation can occur
simultaneously
46
CH4003 Lecture Notes 16 (Erzeng Xue)
Complex Reactions
Photochemical Reactions
Photochemical reaction
The reaction that is initiated by the absorption of light (photons)
Characterisation of photon absorption - quantum yield
A reactant molecule after absorbing a photon becomes excited. The excitation may lead
to product formation or may be lost (e.g. in form of heat emission)
The number of specific primary products (e.g. a radical, photon-excited molecule, or an ion)
formed by absorption of each photon, is called primary quantum yield,
The number of reactant molecules that react as a result of each photon absorbed is call
overall quantum yield, F
E.g. HI + hv H + I primary quantum yield =2 (one H and one I)
H + HI H2 + I
2I I2 overall quantum yield F =2 (two HI molecules reacted)
Note: Many chain reactions are initiated by photochemical reaction. Because of chain reaction
overall quantum yield can be very large, e.g. F = 104
The quantum yield of a photochemical reaction depends on the wavelength of light used
47
CH4003 Lecture Notes 16 (Erzeng Xue)
Complex Reactions
Photochemical Reactions
Wave-length selectivity of photochemical reaction
A light with a specific wave length may only excite a specific type of molecule
Quantum yield of a photochemical rxn may vary with light (wave-length) used
Isotope separation (photochemical reaction Application)
Different isotope species - different mass - different frequencies required to match
their vibration-rotational energys
508 nm light
e.g. I36Cl + I37Cl I36Cl + I37Cl* (only 37Cl molecules are excited)
C6H5Br + I37Cl* C6H537Cl + IBr
Photosensitisation (photochemical reaction Application)
Reactant molecule A may not be activated in a photochemical reaction because it
does not absorb light, but A may be activated by the presence of another molecule
B which can be excited by absorbing light, then transfer some of its energy to A.
254 nm light
e.g. Hg + H2 Hg* + H2 (Hg is, but H2 is not excited by 254nm light)
Hg* + H2 Hg + 2H* & Hg* + H2 HgH + H*
CO H2
H* HCO HCHO + H*
2HCO HCHO + CO
48
CH4003 Lecture Notes 17 (Erzeng Xue)
Spectroscopy
Introduction to Spectroscopy
What is Spectroscopy
The study of structure and properties of atoms and molecule by means of the spectral
information obtained from the interaction of electromagnetic radiant energy with matter
It is the base on which a main class of instrumental analysis and methods is developed
& widely used in many areas of modern science
What to be discussed
Theoretical background of spectroscopy
Types of spectroscopy and their working principles in brief
Major components of common spectroscopic instruments
Applications in Chemistry related areas and some examples
49
CH4003 Lecture Notes 17 (Erzeng Xue)
Introductory to Spectroscopy
Electromagnetic Radiation
Electromagnetic radiation (e.m.r.)
Electromagnetic radiation is a form of energy
Wave-particle duality of electromagnetic radiation
Wave nature - expressed in term of frequency, wave-length and velocity
Particle nature - expressed in terms of individual photon, discrete packet of energy
when expressing energy carried by a photon, we need to know the its frequency
Characteristics of wave
Frequency, v - number of oscillations per unit time, unit: hertz (Hz) - cycle per second
velocity, c - the speed of propagation, for e.m.r c=2.9979 x 108 ms-1 (in vacuum)
wave-length, l - the distance between adjacent crests of the wave
wave number, v, - the number of waves per unit distance v =l-1
c
v v' c
l
The energy carried by an e.m.r. or a photon is directly proportional to the
frequency, i.e. E hv hc hv' c where h is Plancks constant h=6.626x10-34Js
l
50
CH4003 Lecture Notes 17 (Erzeng Xue)
Introductory to Spectroscopy
Electromagnetic Radiation
Electromagnetic radiation
X-ray, light, infra-red, microwave and radio waves are all e.m.r.s, difference being their
frequency thus the amount of energy they possess
Spectral region of e.m.r.
51
CH4003 Lecture Notes 17 (Erzeng Xue)
Introductory to Spectroscopy
Scattering
reflection scattering refraction
Refraction
52
CH4003 Lecture Notes 17 (Erzeng Xue)
Introductory to Spectroscopy
Spectrum
Spectrum is the display of the energy level of e.m.r. as a function of wave
number of electromagnetic radiation energy
The energy level of e.m.r. is usually expressed in one of these terms
absorbance (e.m.r. being absorbed)
transmission (e.m.r. passed through)
Intensity
The term intensity has the meaning of the radiant power that carried by an e.m. r.
1.0
intensity
0.5
. 0.0
350 400 450
wave length cm-1
53
CH4003 Lecture Notes 17 (Erzeng Xue)
Introductory to Spectroscopy
Spectrum
What an spectrum tells
A peak (it can also be a valley depending on how the spectrum is constructed)
represents the absorption or emission of e.m.r. at that specific wavenumber
The wavenumber at the tip of peak is the most important, especially when a peak is broad
A broad peak may sometimes consist of several peaks partially overlapped each other -
mathematic software (usually supplied) must be used to separate them case of a broad
peak (or a valley) observed
The height of a peak corresponds the amount absorption/emission thus can be used as a
quantitative information (e.g. concentration), a careful calibration is usually required
The ratio in intensity of different peaks does not necessarily means the ratio of the quantity
(e.g. concentration, population of a state etc.)
1.0
intensity
0.5
.
0.0
350 400 450
wave length cm-1
54
CH4003 Lecture Notes 17 (Erzeng Xue)
Introductory to Spectroscopy
Introductory to Spectroscopy
Examples
1. A laser emits light with a frequency of 4.69x1014 s-1. (h = 6.63 x 10-34Js)
A) What is the energy of one photon of the radiation from this laser?
B) If the laser emits 1.3x10-2J during a pulse, how many photons are emitted during the pulse?
Ans: A) Ephoton = hn 6.63 x 10-34Js x 4.69x1014 s-1 = 3.11 x 10-19 J
B) No. of photons = (1.3x10-2J )/(3.11 x 10-19J) = 4.2x1016
2. The brilliant red colours seen in fireworks are due to the emission of red light at a wave
length of 650nm. What is the energy of one photon of this light? (h = 6.63 x 10-34Js)
Ans: Ephoton = hn = hc/l (6.63 x 10-34Js x 3 x 108ms-1)/650x10-9m = 3.06x10-19J
3: Compare the energies of photons emitted by two radio stations, operating at 92 MHz
(FM) and 1500 kHz (MW)?
Ans: Ephoton = hn
92 MHz = 92 x 106 Hz (s-1) =>
E = (6.63 x 10-34 Js) x (92 x 106 s-1) = 6.1 x 10-26J
.
1500 kHz = 1500 x 103 Hz (s-1)
E = (6.63 x 10-34 Js) x (1500 x 103 s-1) = 9.9 x 10-28J
56
CH4003 Lecture Notes 18 (Erzeng Xue)
Introductory to Spectroscopy
Atomic Spectra
Shell structure & energy level of atoms Excited
state
In an atom there are a number of shells and ground
state n=1
of subshells where e-s can be found
n=2
The energy level of each shell & subshell
are different and quantised n = 3,
etc.
The e-s in the shell closest to the nuclei has energy
the lowest energy. The higher shell number DE
is, the higher energy it is
The exact energy level of each shell and
subshell varies with substance 4f
4d
Ground state and excited state of e-s n=4
4p
e-
Under normal situation an stays at the 3d
lowest possible shell - the e- is said to be at 4s
Energy
n=3
its ground state 3p
3s
Upon absorbing energy (excited), an e- can n=2 2p
change its orbital to a higher one - we say 2s
the e- is at is excited state. n=1 1s
57
CH4003 Lecture Notes 18 (Erzeng Xue)
Introductory to Spectroscopy
Atomic Spectra
Electron excitation energy
n=1
DE
The excitation can occur at different degrees n=2
low E tends to excite the outmost e-s first n = 3,
when excited with a high E (photon of high v) etc.
an e- can jump more than one levels
even higher E can tear inner e-s away from
nuclei
Energy
may take several steps, - i.e. to the nearest n=3 3p
low energy level first then down to next 3s
n=2 2p
2s
n=1 1s
58
CH4003 Lecture Notes 18 (Erzeng Xue)
Introductory to Spectroscopy
Atomic Spectra
energy
Atomic spectra n=1
DE
The level and quantities of energy supplied n=2
to excite e-s can be measured & studied in n = 3,
terms of the frequency and the intensity of etc.
an e.m.r. - the absorption spectroscopy
The level and quantities of energy emitted
by excited e-s, as they return to their
ground state, can be measured & studied
by means of the emission spectroscopy
The level & quantities of energy absorbed 4f
4d
or emitted (v & intensity of e.m.r.) are n=4
4p
specific for a substance 3d
4s
Energy
n=3 3p
Atomic spectra are mostly in UV (sometime
3s
in visible) regions n=2 2p
2s
n=1 1s
59
CH4003 Lecture Notes 18 (Erzeng Xue)
Spectroscopy
Molecular Spectra
Motion & energy of molecules
Molecules are vibrating and rotating all the time,
two main vibration modes being
v4
stretching - change in bond length (higher v) v3
v2
bending - change in bond angle (lower v)
v1
(other possible complex types of stretching & v4
bending are: scissoring / rocking / twisting v3
S2 v2
Molecules are normally at their ground state (S0) v1 v4
v3
S (Singlet) - two e-s spin in pair E v2
S1 v1
T (Triplet) - two e-s spin parallel J
Spectroscopy
Molecular Spectra
Excitation of a molecule
The energy levels of a molecule at
v4
each state / sub-state are quantised v3
v2
To excite a molecule from its ground v1
state (S0) to a higher E state (S1, S2, T1 v4
v3
etc.), the exact amount of energy equal S2 v2 v4
to the difference between the two v1 v3
v2
states has to be absorbed. (Process A) v1
S1
i.e. to excite a molecule from S0,v1 to S2,v2,
e.m.r with wavenumber v must be used A
absorption T1
hcv' ES2 ,v 2 - ES0 ,v1
The values of energy levels vary with A
the (molecule of) substance. v4
v3
Molecular absorption spectra are the v2
measure of the amount of e.m.r., at a v1
specific wavenumber, absorbed by a S0
substance.
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CH4003 Lecture Notes 18 (Erzeng Xue)
Spectroscopy
Molecular Spectra
Energy change of excited molecules
Internal Inter- system
An excited molecules can lose its excess v4 crossing
transition
energy via several processes v3
v2
Process B - Releasing E as heat when changing v1
from a sub-state to the parental state occurs B E1 v4
v3
within the same state S2 v2 v4
The remaining energy can be release by one of v1 v3
v2
following Processes (C, D & E) B E2
S1 v1
Process C - Transfer its remaining E to other
chemical species by collision A C D
T1
Process D - Emitting photons when falling back Fluorescence
to the ground state - Fluorescence Fluorescence
F
Process E1 - Undergoing internal transition
v4
within the same mode of the excited state v3
v2
Process E2 - Undergoing intersystem crossing
to a triplet sublevel of the excited state v1
B
Process F - Radiating E from triplet to ground S0
state (triplet quenching) - Phosphorescence Jablonsky diagram
62
CH4003 Lecture Notes 18 (Erzeng Xue)
Spectroscopy
Molecular Spectra
Two types of molecular emission spectra
Fluorescence
v4
In the case fluorescence the energy emitted can be the v3
same or smaller (if heat is released before radiation) than v2 v4
the corresponding molecular absorption spectra. v1 v3
B v2
e.g. adsorption in UV region - emission in UV or visible S2 v1
region (the wavelength of visible region is longer than that
of UV thus less energy) T1
Phosphorescence D F
63
CH4003 Lecture Notes 18 (Erzeng Xue)
Introductory to Spectroscopy
Change of energy level related to change of e-s orbital change of vibration states
Spectroscopy Application
When a light of intensity I0 goes through a liquid of concentration C & layer thickness b
The emergent light, I, has less intensity than the incident light I0
scattering, reflection
absorption by liquid
There are different levels of reduction in light intensity at different wavelength
detect by eye - colour change
detect by instrument
The method used to measure UV & visible light absorption is called spectrophotometry
(colourimetry refers to the measurement of absorption of light in visible region only)
65
CH4003 Lecture Notes 19 (Erzeng Xue)
Spectroscopy Application
Spectroscopy Application
Spectroscopy Application
Spectroscopy Application
n p*
n s*
s s*
pp*
bonding ones
Energy
e-s transition can occur between various n non-bonding
states; in general, the energy of e-s p
transition increases in the following order: Bonding
(np*) < (ns*) < (p p*) < (s s*) s
69
CH4003 Lecture Notes 19 (Erzeng Xue)
Spectroscopy Application
Spectroscopy Application
UV visible
Light source Hydrogen discharge lamp Tungsten-halogen lamp
71
CH4003 Lecture Notes 19 (Erzeng Xue)
Spectroscopy Application
72
CH4003 Lecture Notes 20 (Erzeng Xue)
Spectroscopy Application
IR-Spectroscopy
Atoms in a molecule are constantly in motion
There are two main vibrational modes:
Stretching - (symmetrical/asymmetrical) change in bond length - high frequency
Bending - (scissoring/stretch/rocking/twisting) change in bond angle - low freq.
The same bond in different compounds has a slightly different vibration frequ.
Functional groups have characteristic stretching frequencies.
73
CH4003 Lecture Notes 20 (Erzeng Xue)
Spectroscopy Application
IR-Spectroscopy
IR region
The part of electromagnetic radiation between the visible and microwave regions 0.8
mm to 50 mm (12,500 cm-1-200 cm-1).
Most interested region in Infrared Spectroscopy is between 2.5mm-25 mm
(4,000cm-1-400cm-1), which corresponds to vibrational frequency of molecules
The energy changes thr. infrared radiation absorption is in the range of 8-40 KJ/mol
74
CH4003 Lecture Notes 20 (Erzeng Xue)
Spectroscopy Application
IR-Spectroscopy
Use of Infra-Red spectroscopy
IR spectroscopy can be used to distinguish one compound from another.
No two molecules of different structure will have exactly the same natural
frequency of vibration, each will have a unique infrared absorption spectrum.
A fingerprinting type of IR spectral library can be established to distinguish a
compounds or to detect the presence of certain functional groups in a molecule.
Obtaining structural information about a molecule
Absorption of IR energy by organic compounds will occur in a manner
characteristic of the types of bonds and atoms in the functional groups present in
the compound
Practically, examining each region (wave number) of the IR spectrum allows one
identifying the functional groups that are present and assignment of structure
when combined with molecular formula information.
The known structure information is summarized in the Correlation Chart
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CH4003 Lecture Notes 20 (Erzeng Xue)
Spectroscopy Application
IR Spectrum
Principal Correlation Chart Region freq. (cm-1) what is found there??
O-H 3600 cm-1
XH region 3800 - 2600 OH, NH, CH (sp, sp2, sp3) stretches
N-H 3500 cm-1
triple bond 2400 - 2000 CC, CN, C=C=C stretches
C-H 3000 cm-1
CN 2250 cm-1 double bond 1900 - 1500 C=O, C=N, C=C stretches
CC 2150 cm-1 fingerprint 1500 - 400 many types of absorptions
C=O 1715 cm-1 1400 - 900 C-O, C-N stretches
C=C 1650 cm-1 1500 - 1300 CH in-plane bends, NH bends
C-O 1100 cm-1 1000 - 650 CH out-of-plane (oop) bends
Prism
or
IR Source Lenz Diffraction Slit Sample Recorder
Grating
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CH4003 Lecture Notes 20 (Erzeng Xue)
Spectroscopy Application
Spectroscopy Application
Chopper
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CH4003 Lecture Notes 20 (Erzeng Xue)
Spectroscopy Application
Spectroscopy Application
P0 P
Wavelength Signal Processor
Detector
Selector Readout
90o
Type Method of Atomization Radiation
Source Source
atomic (flame) sample solution aspirated
into a flame sample
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CH4003 Lecture Notes 21 (Erzeng Xue)
Spectroscopy Application
Laser - Characteristics
Laser - is a special type of light sources or light generators. The word
LASER represents Light Amplification by Stimulated Emission of Radiation
Characteristics of light produced by Lasers
Monochromatic (single wavelength)
Coherent (in phase)
Directional (narrow cone of divergence)
Incandescent lamp
Chromatic
Incoherent
The first microwave laser was made in
Non-directional
the microwave region in 1954 by Townes
& Shawlow using ammonia as the lasing
medium.
The first optical laser was constructed Monochromatic light source
by Maiman in 1960, using ruby (Al2O3
doped with a dilute concentration of Cr+3) Coherent
as the lasing medium and a fast Non-directional
discharge flash-lamp to provide the pump
energy.
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CH4003 Lecture Notes 21 (Erzeng Xue)
Spectroscopy Application
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CH4003 Lecture Notes 21 (Erzeng Xue)
Spectroscopy Application
Laser uses the stimulated emission process to amplify the light intensity
As in the stimulated emission process, one incident photon (P1) will bring about the
emission of an additional photon (P2), which in turn can yield 4 photons, then 8
photons, and so on.
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CH4003 Lecture Notes 21 (Erzeng Xue)
Spectroscopy Application
Presence of Metastable state, which is the excited state that the excited e-s can
have a relatively long lifetime (>10-8 second), in order to avoid the spontaneous
emission occurring before the stimulated emission
In most lasers, the atoms/molecules/ions in the lasing medium are not pumped directly to a
metastable state. They are excited to an energy level higher than a metastable state, then
drop down to the metastable state by spontaneous non-radiative de-excitation.
Photon Confinement (PC), the emitted photons must be confined in the system
long enough to stimulate further light emission from other excited atoms
This is achieved by using reflecting mirrors at the ends of the system. One end is made totally
reflecting & the other is slight transparent to allow part of the laser beam to escape.
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CH4003 Lecture Notes 21 (Erzeng Xue)
Spectroscopy Application
Output
Feedback mechanism
coupler
Lasing medium
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CH4003 Lecture Notes 21 (Erzeng Xue)
Spectroscopy Application
Laser Action
Lasing medium
at ground state
Pump energy
Population
inversion
Pump energy
Start of stimulated
emission
Pump energy
Stimulated emission
building up
Pump energy
Laser in
full operation
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CH4003 Lecture Notes 21 (Erzeng Xue)
Spectroscopy Application
Types of Lasers
There are many different types of lasers
The lasing medium can be gas, liquid or solid (insulator or semiconductor)
Some lasers produce continuous light beam and some give pulsed light beam
Most lasers produce light wave with a fixed wave-length, but some can be tuned
to produce light beam of wave-length within a certain range.
Spectroscopy Application
Laser - Applications
Laser can be applied in many areas
Commerce
Compact disk, laser printer, copiers, optical disk drives, bar code scanner, optical
communications, laser shows, holograms, laser pointers
Industry
Measurements (range, distance), alignment, material processing (cutting, drilling,
welding, annealing, photolithography, etc.), non-destructive testing, sealing
Medicine
Surgery (eyes, dentistry, dermatology, general), diagnostics, ophthalmology,
oncology
Research
Spectroscopy, nuclear fusion, atom cooling, interferometry, photochemistry, study of
fast processes
Military
Ranging, navigation, simulation, weapons, guidance, blinding
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