Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
O Pollution reduction
gas - converting harmful gases to non-harmful ones
liquid - de-pollution, de-odder, de-colour etc
solid - landfill, factory wastes
C
C
B P
B P
s 0
0
1
des
ads
k
k
B =
0
P B k / k
P k / k
des ads
des ads
0
) ( 1
) (
+
=
case I
A
CH4003 Lecture Notes 13 (Erzeng Xue)
22
Adsorption On Solid Surface
O The Langmuir adsorption isotherm (contd)
O Case II - single molecule adsorbed dissociatively on one site
A-B(g) +M(surface site) D A-M-B
the rate of A-B adsorption r
ads
=k
ads
(1
)(1
)P
AB
=k
ads
(1 )
2
P
AB
the rate of A-B desorption r
des
=k
des
=k
des
2
at equilibrium r
ads
= r
des
k
ads
(1 )
2
P
AB
= k
des
2
rearrange it for
Let.
Catalysis & Catalysts
case II
A B
B A
=
1/2
0
1/2
0
) ( 1
) (
AB
AB s
P B
P B
C
C
+
= =
des
ads
k
k
B =
0
) ( 1
) (
AB des ads
AB des ads
P k / k
P k / k
+
=
CH4003 Lecture Notes 13 (Erzeng Xue)
23
O The Langmuir adsorption isotherm (contd)
O Case III - two molecules adsorbed on two sites
A(g) +B(g) +2M(surface site) D A-M + B-M
the rate of A adsorption r
ads,A
= k
ads,A
(1
) P
A
the rate of B adsorption r
ads,B
= k
ads,B
(1
) P
B
the rate of A desorption r
des,A
= k
des,A
at equilibrium r
ads ,A
= r
des ,A
and r
ads ,B
= r
des ,B
k
ads,A
(1
)P
A
=k
des,A
and k
ads,B
(1
)P
B
=k
des,B
rearrange it for
where are adsorption coefficients of A & B.
Adsorption On Solid Surface
Catalysis & Catalysts
B , des
B , ads
B ,
A , des
A , ads
A ,
k
k
B
k
k
B = =
0 0
and
B B , A A ,
B B , B , s
B
B B , A A ,
A A , A , s
A
P B P B
P B
C
C
P B P B
P B
C
C
0 0
0
0 0
0
1
1 + +
= =
+ +
= =
case III
A B
CH4003 Lecture Notes 13 (Erzeng Xue)
24
O The Langmuir adsorption isotherm (contd)
Adsorption On Solid Surface
Catalysis & Catalysts
B , des
B , ads
B ,
A , des
A , ads
A ,
k
k
B
k
k
B = =
0 0
and
B B , A A ,
B B , B , s
B
B B , A A ,
A A , A , s
A
P B P B
P B
C
C
P B P B
P B
C
C
0 0
0
0 0
0
1
1
+ +
= =
+ +
= =
Adsorption
Strong k
ads
>> k
des
k
ads
>> k
des
B
0
>>1 B
0
>>1
Weak k
ads
<< k
des
k
ads
<< k
des
B
0
<<1 B
0
<<1
1/2
0
1/2
0
) ( 1
) (
AB
AB s
P B
P B
C
C
+
= =
des
ads
k
k
B =
0
case II
A B
= =
+
C
C
B P
B P
s 0
0
1
des
ads
k
k
B =
0
case I
A
1 =
C
C
s
1 =
C
C
s
P B
C
C
s
0
= =
1/2
0
) ( P B
C
C
s
= =
Adsorption
A, B both strong
A strong, B weak
A weak, B weak
B B , A A ,
B B , B , s
B
B B , A A ,
A A , A , s
A
P B P B
P B
C
C
P B P B
P B
C
C
0 0
0
0 0
0
+
= =
+
= =
B B , B , s B
A A , A , s A
P B C / C
P B C / C
0
0
= =
= =
A
B
A , B , B , s B
A , s A
P
P
B / B C / C
C / C
) (
1
0 0
= =
=
case III
A B
CH4003 Lecture Notes 13 (Erzeng Xue)
25
OLangmuir adsorption isotherm
case I
case II
Case III
Adsorption On Solid Surface
Catalysis & Catalysts
Langmuir adsorption isotherm established a logic picture of adsorption process
It fits many adsorption systems but not at all
The assumptions made by Langmuir do not hold in all situation, that causing error
Solid surface is heterogeneous thus the heat of adsorption is not a constant at different
Physisorption of gas molecules on a solid surface can be more than one layer
B B , A A ,
B B , B , s
B
B B , A A ,
A A , A , s
A
P B P B
P B
C
C
P B P B
P B
C
C
0 0
0
0 0
0
1
1
+ +
= =
+ +
= =
1/2
0
1/2
0
) ( 1
) (
AB
AB s
P B
P B
C
C
+
= =
= =
+
C
C
B P
B P
s 0
0
1
large B
0
(strong adsorp.)
small B
0
(weak adsorp.)
moderate B
0
Pressure
A
m
o
u
n
t
a
d
s
o
r
b
e
d
mono-layer
1 =
C
C
s
P B
C
C
s
0
= =
Strong adsorption k
ads
>> k
des
Weak adsorption k
ads
<< k
des
CH4003 Lecture Notes 14 (Erzeng Xue)
26
O Five types of physisorption isotherms are found over all solids
O Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are not
O Type II for non-porous materials
O Type III porous materials with cohesive force between adsorbate
molecules greater than the adhesive force between adsorbate
molecules and adsorbent
O Type IV staged adsorption (first monolayer then build up of additional
layers)
O Type V porous materials with cohesive force between adsorbate
molecules and adsorbent being greater than that between
adsorbate molecules
Adsorption On Solid Surface
Catalysis & Catalysts
I
II
III
IV
V
relative pres. P/P
0
1.0
a
m
o
u
n
t
a
d
s
o
r
b
e
d
CH4003 Lecture Notes 14 (Erzeng Xue)
27
O Other adsorption isotherms
Many other isotherms are proposed in order to explain the observations
O The Temkin (or Slygin-Frumkin) isotherm
O Assuming the adsorption enthalpy H decreases linearly with surface coverage
From ads-des equilibrium, ads. rate des. rate
r
ads
=k
ads
(1-)P r
des
=k
des
where Q
s
is the heat of adsorption. When Q
s
is a linear function of
i
. Q
s
=Q
0
-iS (Q
0
is a
constant, i is the number and S represents the surface site),
the overall coverage
When b
1
P >>1 and b
1
Pexp(-i/RT) <<1, we have =c
1
ln(c
2
P), where c
1
& c
2
are constants
Valid for some adsorption systems.
Adsorption On Solid Surface
Catalysis & Catalysts
1
1
1
1
0
0
P e b
P e b
P B
P B
RT / Q
RT / Q
s
s
s
+
=
+
=
H
o
f
a
d
s
Langmuir
Temkin
( )
|
|
.
|
\
|
+
+
=
+
= =
RT
i
RT / Q
RT / Q
s
exp P
P
i
RT
dS
P e b
P e b
dS
s
s
1
1
1
0
1
1
1
0
b 1
b 1
ln
(1
[
CH4003 Lecture Notes 14 (Erzeng Xue)
28
O The Freundlich isotherm
O assuming logarithmic change of adsorption enthalpy H with surface coverage
From ads-des equilibrium, ads. rate des. rate
r
ads
=k
ads
(1-)P r
des
=k
des
where Q
i
is the heat of adsorption which is a function of
i
. If there are N
i
types of surface
sites, each can be expressed as N
i
=aexp(-Q/Q
0
) (a and Q
0
are constants), corresponding to a
fractional coverage
i
,
the overall coverage
the solution for this integration expression at small is:
ln=(RT/Q
0
)lnP+constant, or
as is the Freundlich equation normally written, where c
1
=constant, 1/c
2
=RT/Q
0
Freundlich isotherm fits, not all, but many adsorption systems.
Adsorption On Solid Surface
Catalysis & Catalysts
+
= =
0
0
1 1
0
0
e
e )] (1 [
dQ a
dQ a P e b / P e b
N
N
Q/Q
Q/Q RT / Q RT / Q
i
i
i
i i
1
1
1
1
0
0
P e b
P e b
P B
P B
RT / Q
RT / Q
i
i
i
+
=
+
=
H
o
f
a
d
s
Langmuir
Freundlich
2
1
1
C /
p c =
CH4003 Lecture Notes 14 (Erzeng Xue)
29
O BET (Brunauer-Emmett-Teller) isotherm
O Many physical adsorption isotherms were found, such as the types II and III, that the
adsorption does not complete the first layer (monolayer) before it continues to stack
on the subsequent layer (thus the S-shape of types II and III isotherms)
O Basic assumptions
the same assumptions as that of Langmuir but allow multi-layer adsorption
the heat of ads. of additional layer equals to the latent heat of condensation
based on the rate of adsorption=the rate of desorption for each layer of ads.
the following BET equation was derived
Where P - equilibrium pressure
P
0
- saturate vapour pressure of the adsorbed gas at the temperature
P/P
0
is called relative pressure
V - volume of adsorbed gas per kg adsorbent
V
m
-volume of monolayer adsorbed gas per kg adsorbent
c - constant associated with adsorption heat and condensation heat
Note: for many adsorption systems c=exp[(H
1
-H
L
)/RT], where H
1
is adsorption heat of 1st layer &
H
L
is liquefaction heat, so that the adsorption heat can be determined from constant c.
Adsorption On Solid Surface
Catalysis & Catalysts
) (
1 1
1
0
0
0
P / P
cV
c
cV ) P / P ( V
P / P
m m
+ =
+ =
P P
V P P
/
( / )
0
0
1
P/P
0
P P
V P P
/
( / )
0
0
1
A A N A
V
V
s m m m
m
T P
= =
,
. 6022 10
23
V
m
- volume of monolayer adsorbed gas molecules calculated from the plot, L
V
T,P
- molar volume of the adsorbed gas, L/mol
A
m
- cross-section area of a single gas molecule, m
2
CH4003 Lecture Notes 14 (Erzeng Xue)
32
O Summary of adsorption isotherms
Name Isotherm equation Application Note
Langmuir
Temkin =c
1
ln(c
2
P)
Freundlich
BET
Adsorption On Solid Surface
Catalysis & Catalysts
) (
1 1
1
0
0
0
P / P
cV
c
cV ) P / P ( V
P / P
m m
+ =
= =
+
C
C
B P
B P
s 0
0
1
2
1
1
C /
p c =
Chemisorption and
physisorption
Chemisorption
Chemisorption and
physisorption
Multilayer physisorption
Useful in analysis of
reaction mechanism
Chemisorption
Easy to fit adsorption
data
Useful in surface area
determination
CH4003 Lecture Notes 14 (Erzeng Xue)
33
OLangmuir-Hinshelwood mechanism
O This mechanism deals with the surface-catalysed reaction in which
that 2 or more reactants adsorb on surface without dissociation
A(g) +B(g) D A(ads) +B(ads) " P (the desorption of P is not r.d.s.)
O The rate of reaction r
i
=k[A][B]=k
A
B
From Langmuir adsorption isotherm (the case III) we know
O We then have
When both A & B are weakly adsorbed (B
0,A
P
A
<<1, B
0,B
P
B
<<1),
2nd order reaction
When A is strongly adsorbed (B
0,A
P
A
>>1) & B weakly adsorbed (B
0,B
P
B
<<1 <<B
0,A
P
A
)
1st order w.r.t. B
Mechanism of Surface Catalysed Reaction
Catalysis & Catalysts
+ +
=
+ +
=
B B , A A ,
B B ,
B
B B , A A ,
A A ,
A
P B P B
P B
P B P B
P B
0 0
0
0 0
0
1
1
B B , A A ,
B A B , A ,
B B , A A ,
B B ,
B B , A A ,
A A ,
i
P B P B
P P B kB
P B P B
P B
P B P B
P B
k r
0 0
0 0
0 0
0
0 0
0
1 1 1 + +
=
|
|
.
|
\
|
+ +
|
|
.
|
\
|
+ +
=
B A B A B , A , i
P P ' k P P B kB r = =
0 0
B B B ,
A A ,
B A B , A ,
i
P ' ' k P kB
P B
P P B kB
r = = =
0
0
0 0
A B
+ "
P
CH4003 Lecture Notes 15 (Erzeng Xue)
34
OEley-Rideal mechanism
O This mechanism deals with the surface-catalysed reaction in which
that one reactant, A, adsorb on surface without dissociation and
other reactant, B, approaching from gas to react with A
A(g) D A(ads) P (the desorption of P is not r.d.s.)
O The rate of reaction r
i
=k[A][B]=k
A
P
B
From Langmuir adsorption isotherm (the case I) we know
O We then have
When both A is weakly adsorbed or the partial pressure of A is very low (B
0,A
P
A
<<1),
2nd order reaction
When A is strongly adsorbed or the partial pressure of A is very high (B
0,A
P
A
>>1)
1st order w.r.t. B
Mechanism of Surface Catalysed Reaction
Catalysis & Catalysts
A A ,
A A ,
A
P B
P B
0
0
1+
=
A A ,
B A A ,
B
A A ,
A A ,
i
P B
P P kB
P
P B
P B
k r
0
0
0
0
1 1 +
=
|
|
.
|
\
|
+
=
B A B A A , i
P P ' k P P kB r = =
0
B
A A ,
B A A ,
i
kP
P B
P P kB
r = =
0
0
A
"
P
B
+B(g)
CH4003 Lecture Notes 15 (Erzeng Xue)
35
O Mechanism of surface-catalysed reaction with dissociative adsorption
O The mechanism of the surface-catalysed reaction in which one
reactant, AD, dissociatively adsorbed on one surface site
AD(g) D A(ads) +D(ads) P
(the des. of P is not r.d.s.)
O The rate of reaction r
i
=k[A][B]=k
AD
P
B
From Langmuir adsorption isotherm (the case I) we know
O We then have
When both AD is weakly adsorbed or the partial pressure of AD is very low (B
0,AD
P
AD
<<1),
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 (B
0,A
P
A
>>1)
1st order w.r.t. B
Mechanism of Surface Catalysed Reaction
Catalysis & Catalysts
( )
( )
2 1
0
2 1
0
1
/
AD AD ,
/
AD AD ,
AD
P B
P B
+
=
( )
( )
( )
( )
2 1
0
2 1
0
2 1
0
2 1
0
1 1
/
AD AD ,
B
/
AD AD ,
B /
AD AD ,
/
AD AD ,
i
P B
P P B k
P
P B
P B
k r
+
=
+
=
( )
B
/
AD B
/
AD AD , i
P P ' k P P B k r
2 1 2 1
0
= =
( )
( )
B /
AD AD ,
B
/
AD AD ,
i
kP
P B
P P B k
r = =
2 1
0
2 1
0
+B(g)
"
P
B
A B
CH4003 Lecture Notes 15 (Erzeng Xue)
36
O Mechanisms of surface-catalysed rxns involving dissociative adsorption
O In a similar way one can derive mechanisms of other surface-catalysed reactions,
in which
dissociatively adsorbed one reactant, AD, (on one surface site) reacts with
another associatively adsorbed reactant B on a separate surface site
dissociatively adsorbed one reactant, AD, (on one surface site) reacts with
another dissociatively adsorbed reactant BC on a separate site
O The use of these mechanism equations
O Determining which mechanism applies by fitting experimental data to each.
O Helping in analysing complex reaction network
O Providing a guideline for catalyst development (formulation, structure,).
O Designing / running experiments under extreme conditions for a better control
O
Mechanism of Surface Catalysed Reaction
Catalysis & Catalysts
CH4003 Lecture Notes 15 (Erzeng Xue)
37
O Bulk and surface
O The composition & structure of a solid in bulk and on surface
can differ due to
Surface contamination
Bombardment by foreign molecules when exposed to an environment
Surface enrichment
Some elements or compounds tend to be enriched (driving by thermodynamic
properties of the bulk and surface component) on surface than in bulk
Deliberately made different in order for solid to have specific properties
Coating (conductivity, hardness, corrosion-resistant etc)
Doping the surface of solid with specific active components in order perform certain
function such as catalysis
O To processes that occur on surfaces, such as corrosion, solid sensors and
catalysts, the composition and structure of (usually number of layers of)
surface are of critical importance
Solids and Solid Surface
Catalysis & Catalysts
CH4003 Lecture Notes 15 (Erzeng Xue)
38
OMorphology of a solid and its surface
O A solid, so as its surface, can be well-structured crystalline (e.g. diamond C,
carbon nano-tubes, NaCl, sugar etc) or amorphous (non-crystallised, e.g.
glass)
O Mixture of different crystalline of the same substance can co-exist on
surface (e.g. monoclinic, tetragonal, cubic ZrO
2
)
O Well-structured crystalline and amorphous can co-exist on surface
O Both well-structured crystalline and amorphous are capable of being used
adsorbent and/or catalyst
O
Solids and Solid Surface
Catalysis & Catalysts
CH4003 Lecture Notes 15 (Erzeng Xue)
39
ODefects and dislocation on surface crystalline structure
O A perfect crystal can be made in a controlled way
O Surface defects
terrace
step
kink
adatom / vacancy
O Dislocation
screw dislocation
O Defects and dislocation can be desirable for certain catalytic reactions
as these may provide the required surface geometry for molecules to be
adsorbed, beside the fact that these sites are generally highly energised.
Solids and Solid Surface
Catalysis & Catalysts
Terrace Step
CH4003 Lecture Notes 15 (Erzeng Xue)
40
OPore sizes
O micro pores d
p
<20-50 nm
O meso-pores 20nm <d
p
<200nm
O macro pores d
p
>200 nm
O Pores can be uniform (e.g. polymers) or non-uniform (most metal oxides)
OPore size distribution
O Typical curves to characterise pore size:
Cumulative curve
Frequency curve
O Uniform size distribution (a) &
non-uniform size distribution (b)
Pores of Porous Solids
Catalysis & Catalysts
b
d
a
dw
dd
d
wt
b
a
wt
d
Cumulative curve Frequency curve
CH4003 Lecture Notes 15 (Erzeng Xue)
41
O Many reactions proceed via chain reaction
O polymerisation
O explosion
O
O Elementary reaction steps in chain reactions
1. Initiation step - creation of chain carriers (radicals, ions, neutrons etc, which are capable of
propagating a chain) by vigorous collisions, photon absorption
R R (the dot here signifies the radical carrying unpaired electron)
2. Propagation step - attacking reactant molecules to generate new chain carriers
R + M R + M
3. Termination step - two chain carriers combining resulting in the end of chain growth
R + M R-M
There are also other reactions occur during chain reaction:
Retardation step - chain carriers attacking product molecules breaking them to reactant
R + R-M R + M (leading to net reducing of the product formation rate)
Inhibition step - chain carriers being destroyed by reacting with wall or foreign matter
R + W R-W (leading to net reducing of the number of chain carriers)
Chain Reactions - Process
Complex Reactions
E
CH4003 Lecture Notes 16 (Erzeng Xue)
42
O Rate law of chain reaction
Example: overall reaction H
2
(g) +Br
2
(g) 2HBr(g) observed:
elem step rate law
a. Initiation: Br
2
2Br r
a
=k
a
[Br
2
]
b. Propagation: Br + H
2
HBr + H r
b
=k
b
[Br][H
2
]
H + Br
2
HBr + Br r
b
=k
b
[H][Br
2
]
c. Termination: Br + Br Br
2
r
c
=k
c
[Br][Br]=k
c
[Br]
2
H + H H
2
(practically less important therefore neglected)
H + Br HBr (practically less important therefore neglected)
d. Retard
n
(obsvd.) H + HBr H
2
+ Br r
d
=k
d
[H][HBr]
HBr net rate: r
HBr
= r
b
+ r
b
- r
d
or d[HBr]/dt=k
b
[Br][H
2
]+k
b
[H][Br
2
]-k
d
[H][HBr]
Apply s.s.a. r
H
= r
b
- r
b
- r
d
or d[H]/dt=k
b
[Br][H
2
]- k
b
[H][Br
2
]-k
d
[H][HBr]=0
r
Br
= 2r
a
-r
b
+r
b
-2r
c
+r
d
or d[Br]/dt=2k
a
[Br
2
]-k
b
[Br][H
2
]+k
b
[H][Br
2
]-2 k
c
[Br]
2
+k
d
[H][HBr]=0
solve the above eqns we have
Chain Reactions - Rate Law
Complex Reactions
[HBr] ] [Br
] ][Br [H [HBr]
2
3/2
2 2
' k
k
dt
d
+
=
( )
( )[HBr] ] [Br
] ][Br [H 2 [HBr]
2
3/2
2 2
1/2
b d
c a b
' k / k
k / k k
dt
d
+
=
CH4003 Lecture Notes 16 (Erzeng Xue)
43
O Monomer - the individual molecule unit in a polymer
O Type I polymerisation - Chain polymerisation
O An activated monomer attacks another monomer, links to it, then likes another
monomer, so on, leading the chain growth eventually to polymer.
rate law
Initiation: I
x
xR (usually r.d.s.) r
i
=k
i
[I]
R + M M
1
(fast)
Propagation: M + M
1
(MM
1
) M
2
(fast)
M + M
2
(MM
2
) M
3
(fast)
M + M
n-1
(MM
n-1
) M
n
r
p
=k
p
[M][M] (r
i
is the r.d.s.)
Termination: M
n
+ M
m
(M
n
M
m
) M
m+n
r
t
=k
t
[M]
2
Apply s.s.a. to [M] formed
The rate of propagation
or the rate of M consumption
or the rate of chain growth
Chain Reactions - Polymerisation
Complex Reactions
[I]
] [M
i
k x
dt
d
=
initiator chain-carrier
2 1
2
2
[I]
] [M 0 ] [M 2 [I] 2
] [M
/
t
i
t i p i
k
k x
k - k x r r x
dt
d
|
|
.
|
\
|
= = = =
[M] [I]
2
[M]
i.e. ] [M][M
[M]
1/2
2 1/
t
i
p p p
k
k x
k
dt
d
k r
dt
d
|
|
.
|
\
|
= = =
is the yield of I
x
to xR
CH4003 Lecture Notes 16 (Erzeng Xue)
44
O Type II polymerisation - Stepwise polymerisation
A specific section of molecule A reacts with a specific section of molecule B forming chain
(a-A-a) +(b-B-b) {a -A-(ab)-B-b}
H
2
N(CH
2
)
6
NH
2
+ HOOC(CH
2
)
4
COOH H
2
N(CH
2
)
6
NHOC(CH
2
)
4
COOH + H
2
O (1)
H-HN(CH
2
)
6
NHOC(CH
2
)
4
CO-OH
H-[HN(CH
2
)
6
NHOC(CH
2
)
4
CO]
n
-OH (n)
Note: If a small molecule is dropped as a result of reaction, like a H
2
O dropped in rxn (1), this type of
reaction is called condensation reaction. Protein molecules are formed in this way.
O The rate law for the overall reaction of this type is the same as its elementary step
involving one H- containing unit & one -OH containing unit, which is the 2
nd
order
the conversion of B (-OH containing substance) at time t is
Chain Reactions - Polymerisation
Complex Reactions
0
0 2
[A] 1
[A]
[A] or [A] [A][-OH]
[A]
kt
k k
dt
d
+
= = =
0
0
0
0
[A] 1
[A]
[A]
[A] [A]
kt
kt
X
B
+
=
=
CH4003 Lecture Notes 16 (Erzeng Xue)
45
O Type I Explosion: Chain-branching explosion
Chain-branching - During propagation step of a chain reaction one attack by a
chain carrier can produce more than one new chain carriers
Chain-branching explosion
When chain-branching occurs the number carriers increases exponentially
the rate of reaction may cascade into explosion
Example: 2H
2
(g) + O
2
(g) 2H
2
O(g)
Initiation: H
2
+ O
2
O
2
H + H
Propagation: H
2
+ O
2
H OH + H
2
O (non-branching)
H
2
+ OH H + H
2
O (non-branching)
O
2
+ H O + OH (branching)
O + H
2
OH + H (branching)
Chain Reactions - Explosion
Complex Reactions
Lead to explosion
CH4003 Lecture Notes 16 (Erzeng Xue)
46
OType 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
O Must be exothermic reaction
O Must be in a confined space and within short time
H T r H T r H
O A combination of chain-branching reaction with heat accumulation can occur
simultaneously
Explosion Reactions
Complex Reactions
CH4003 Lecture Notes 16 (Erzeng Xue)
47
O Photochemical reaction
The reaction that is initiated by the absorption of light (photons)
O 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)
O 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,
O The number of reactant molecules that react as a result of each photon absorbed is call
overall quantum yield,
E.g. HI + hv H + I primary quantum yield =2 (one H and one I)
H + HI H
2
+ I
2I I
2
overall quantum yield =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. =10
4
The quantum yield of a photochemical reaction depends on the wavelength of light used
Photochemical Reactions
Complex Reactions
CH4003 Lecture Notes 16 (Erzeng Xue)
48
O Wave-length selectivity of photochemical reaction
O 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
O Isotope separation (photochemical reaction Application)
Different isotope species - different mass - different frequencies required to match
their vibration-rotational energys
e.g. I
36
Cl + I
37
Cl I
36
Cl + I
37
Cl* (only
37
Cl molecules are excited)
C
6
H
5
Br + I
37
Cl* C
6
H
5
37
Cl + IBr
O 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.
e.g. Hg + H
2
Hg* + H
2
(Hg is, but H
2
is not excited by 254nm light)
Hg* + H
2
Hg + 2H* & Hg* + H
2
HgH + H*
H* HCO HCHO + H*
2HCO HCHO + CO
Photochemical Reactions
Complex Reactions
508 nm light
254 nm light
CO H
2
CH4003 Lecture Notes 16 (Erzeng Xue)
49
O 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
O What to be discussed
O Theoretical background of spectroscopy
O Types of spectroscopy and their working principles in brief
O Major components of common spectroscopic instruments
O Applications in Chemistry related areas and some examples
Introduction to Spectroscopy
Spectroscopy
CH4003 Lecture Notes 17 (Erzeng Xue)
50
O Electromagnetic radiation (e.m.r.)
O Electromagnetic radiation is a form of energy
O 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
O Characteristics of wave
O Frequency, v - number of oscillations per unit time, unit: hertz (Hz) - cycle per second
O velocity, c - the speed of propagation, for e.m.r c=2.9979 x 10
8
ms
-1
(in vacuum)
O wave-length, - the distance between adjacent crests of the wave
wave number, v, - the number of waves per unit distance v =
-1
O The energy carried by an e.m.r. or a photon is directly proportional to the
frequency, i.e. where h is Plancks constant h=6.626x10
-34
J s
Electromagnetic Radiation
Introductory to Spectroscopy
c ' v
c
v = =
c ' hv
hc
hv E = = =
cm
Frequency
v
Hz
Energy
kcal/mol
Electron
vole eV
Type of
radiation
Type of
spectroscopy
Type of
quantum
transition
9.4x10
7
4.1x10
6
3.3x10
10
3.0x10
-11
10
21
9.4x10
5
4.1x10
4
3.3x10
8
3.0x10
-9
10
19
9.4x10
3
4.1x10
2
3.3x10
6
3.0x10
-7
10
17
9.4x10
1
4.1x10
0
3.3x10
4
3.0x10
-5
10
15
9.4x10
-1
4.1x10
-2
3.3x10
2
3.0x10
-3
10
13
9.4x10
-3
4.1x10
-4
3.3x10
0
3.0x10
-1
10
11
9.4x10
-5
4.1x10
-6
3.3x10
-2
3.0x10
1
10
9
9.4x10
-7
4.1x10
-8
3.3x10
-4
3.0x10
3
10
7
Gamma
ray
X-ray
Ultra Violet
Visible
Microwave
Radio
X-ray
absorption
emission
Nuclear
Gamma ray
emission
Electronic
(outer shell)
Molecular
rotation
Molecular
vibration
Nuclear magnetic
resonance
Microwave
absorption
UV absorption
IR absorption
Raman
Vac
UV
Vis
Electronic
(inner shell)
Introductory to Spectroscopy
CH4003 Lecture Notes 17 (Erzeng Xue)
56
1. A laser emits light with a frequency of 4.69x10
14
s
-1
. (h =6.63 x 10
-34
J s)
A) What is the energy of one photon of the radiation from this laser?
B) If the laser emits 1.3x10
-2
J during a pulse, how many photons are emitted during the pulse?
Ans: A) E
photon
=h = 6.63 x 10
-34
J s x 4.69x10
14
s
-1
=3.11 x 10
-19
J
B) No. of photons =(1.3x10
-2
J )/(3.11 x 10
-19
J ) =4.2x10
16
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
-34
J s)
Ans: E
photon
=h =hc/ =(6.63 x 10
-34
J s x 3 x 10
8
ms
-1
)/650x10
-9
m =3.06x10
-19
J
3: Compare the energies of photons emitted by two radio stations, operating at 92 MHz
(FM) and 1500 kHz (MW)?
Ans: E
photon
=h
92 MHz =92 x 10
6
Hz (s
-1
) =>
E =(6.63 x 10
-34
J s) x (92 x 10
6
s
-1
) =6.1 x 10
-26
J
1500 kHz =1500 x 10
3
Hz (s
-1
)
E =(6.63 x 10
-34
J s) x (1500 x 10
3
s
-1
) =9.9 x 10
-28
J
Examples
.
Introductory to Spectroscopy
CH4003 Lecture Notes 17 (Erzeng Xue)
57
O Shell structure & energy level of atoms
O In an atom there are a number of shells and
of subshells where e
-
s can be found
O The energy level of each shell & subshell
are different and quantised
The e
-
s in the shell closest to the nuclei has
the lowest energy. The higher shell number
is, the higher energy it is
The exact energy level of each shell and
subshell varies with substance
O Ground state and excited state of e
-
s
O Under normal situation an e
-
stays at the
lowest possible shell - the e
-
is said to be at
its ground state
O Upon absorbing energy (excited), an e
-
can
change its orbital to a higher one - we say
the e
-
is at is excited state.
Atomic Spectra
Introductory to Spectroscopy
n =1
n =2
n =3,
etc.
energy
E
ground
state
Excited
state
E
n
e
r
g
y
n=1
n=2
n=3
n=4
1s
2s
2p
3s
3p
4s
3d
4p
4d
4f
CH4003 Lecture Notes 18 (Erzeng Xue)
58
O Electron excitation
O The excitation can occur at different degrees
low E tends to excite the outmost e
-
s first
when excited with a high E (photon of high v)
an e
-
can jump more than one levels
even higher E can tear inner e
-
s away from
nuclei
O An e
-
at its excited state is not stable and
tends to return its ground state
O If an e
-
jumped more than one energy levels
because of absorption of a high E, the
process of the e
-
returning to its ground state
may take several steps, - i.e. to the nearest
low energy level first then down to next
Atomic Spectra
E
n
e
r
g
y
n=1
n=2
n=3
n=4
1s
2s
2p
3s
3p
4s
3d
4p
4d
4f
n =1
n =2
n =3,
etc.
energy
E
Introductory to Spectroscopy
CH4003 Lecture Notes 18 (Erzeng Xue)
59
O Atomic spectra
OThe level and quantities of energy supplied
to excite e
-
s can be measured & studied in
terms of the frequency and the intensity of
an e.m.r. - the absorption spectroscopy
OThe 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
OThe level & quantities of energy absorbed
or emitted (v & intensity of e.m.r.) are
specific for a substance
OAtomic spectra are mostly in UV (sometime
in visible) regions
Atomic Spectra
E
n
e
r
g
y
n=1
n=2
n=3
n=4
1s
2s
2p
3s
3p
4s
3d
4p
4d
4f
n =1
n =2
n =3,
etc.
energy
E
Introductory to Spectroscopy
CH4003 Lecture Notes 18 (Erzeng Xue)
60
O Motion & energy of molecules
O Molecules are vibrating and rotating all the time,
two main vibration modes being
stretching - change in bond length (higher v)
bending - change in bond angle (lower v)
(other possible complex types of stretching &
bending are: scissoring / rocking / twisting
O Molecules are normally at their ground state (S
0
)
S (Singlet) - two e-s spin in pair E
T (Triplet) - two e-s spin parallel J
O Upon exciting molecules can change to high E
states (S
1
, S
2,
T
1
etc.), which are associated with
specific levels of energy
O The change from high E states to low ones can
be stimulated by absorbing a photon; the
change from low to high E states may result in
photon emission
Molecular Spectra
Spectroscopy
S
0
T
1
S
2
S
1
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
CH4003 Lecture Notes 18 (Erzeng Xue)
61
O Excitation of a molecule
O The energy levels of a molecule at
each state / sub-state are quantised
O To excite a molecule from its ground
state (S
0
) to a higher E state (S
1
, S
2,
T
1
etc.), the exact amount of energy equal
to the difference between the two
states has to be absorbed. (Process A)
i.e. to excite a molecule from S
0,v1
to S
2,v2
,
e.m.r with wavenumber v must be used
O The values of energy levels vary with
the (molecule of) substance.
O Molecular absorption spectra are the
measure of the amount of e.m.r., at a
specific wavenumber, absorbed by a
substance.
Molecular Spectra
Spectroscopy
1 0 2 2 v , v ,
S S
E E ' hcv =
v
1
v
2
v
3
v
4
S
0
T
1
S
2
S
1
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
absorption
A
A
CH4003 Lecture Notes 18 (Erzeng Xue)
62
O Energy change of excited molecules
An excited molecules can lose its excess
energy via several processes
O Process B - Releasing E as heat when changing
from a sub-state to the parental state occurs
within the same state
O The remaining energy can be release by one of
following Processes (C, D & E)
O Process C - Transfer its remaining E to other
chemical species by collision
O Process D - Emitting photons when falling back
to the ground state - Fluorescence
O Process E
1
- Undergoing internal transition
within the same mode of the excited state
O Process E
2
- Undergoing intersystem crossing
to a triplet sublevel of the excited state
O Process F - Radiating E from triplet to ground
state (triplet quenching) - Phosphorescence
Molecular Spectra
Spectroscopy
S
0
T
1
S
2
S
1
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
I nter- system
crossing
I nternal
transition
B
B
E
1
E
2
C
F
A
B
Fluorescence
D
Fluorescence
J ablonsky diagram
CH4003 Lecture Notes 18 (Erzeng Xue)
63
O Two types of molecular emission spectra
O Fluorescence
In the case fluorescence the energy emitted can be the
same or smaller (if heat is released before radiation) than
the corresponding molecular absorption spectra.
e.g. adsorption in UV region - emission in UV or visible
region (the wavelength of visible region is longer than that
of UV thus less energy)
Fluorescence can also occur in atomic adsorption spectra
Fluorescence emission is generally short-lived (e.g. s)
O Phosphorescence
Phosphorescence generally takes much longer to
complete (called metastable) than fluorescence because
of the transition from triplet state to ground state involves
altering the e
-
s spin. If the emission is in visible light
region, the light of excited material fades away gradually
Molecular Spectra
Spectroscopy
S
0
S
2
v
1
v
2
v
3
v
4
v
1
v
2
v
3
v
4
B
A
phosphor-
enscence
D
Fluore-
scence
T
1
v
1
v
2
v
3
v
4
F
CH4003 Lecture Notes 18 (Erzeng Xue)
64
O Comparison of atomic and molecular spectra
O Quantum mechanics is the basis of atomic & molecular spectra
O The transitional, rotational and vibrational modes of motion of objects of atomic /
molecular level are well-explained.
Atomic Spectra & Molecular Spectra
Introductory to Spectroscopy
Atomic spectra Molecular spectra
Adsorption spectra Yes Yes
Emission spectra Yes Yes
Energy required for excitation high low
Change of energy level related to change of e
-
s orbital change of vibration states
Spectral region UV mainly visible
Relative complexity of spectra simple complex
CH4003 Lecture Notes 18 (Erzeng Xue)
65
O Observations
When a light of intensity I
0
goes through a liquid of concentration C & layer thickness b
O The emergent light, I, has less intensity than the incident light I
0
scattering, reflection
absorption by liquid
O 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)
UV & Visible Spectrophotometry
Spectroscopy Application
Incident light, I
0
(UV or visible)
Emergent light, I
C
b
ultraviolet visible infra-red
200 - 400 400 - 800 800 - 15
nm nm nm nm nm m
CH4003 Lecture Notes 19 (Erzeng Xue)
66
O Theory of light absorption
Quantitative observation
O The thicker the cuvette
- more diminishing of light in intensity
O Higher concentration the liquid
- the less the emergent light intensity
These observations are summarised by Beers Law:
Successive increments in the number of identical absorbing molecules in the path of a beam
of monochromatic radiation absorb equal fraction of the radiation power travel through them
Thus
UV & Visible Spectrophotometry
Spectroscopy Application
Incident light
I
0
Emergent light
I
C
b
I ' k
dx Ncs
dI
=
2
I
0
dx
b
x
s
s
I
number of
molecules
N-Avogadro number
light
absorbed
fraction
of light
acdx dx Ncs ' k
I
dI
= =
2
acb
I
I
dx ac
I
dI
b
b I
I
b
= =
0
0
ln
0
A abc
I
I
=
0
log
Absorbance
CH4003 Lecture Notes 19 (Erzeng Xue)
67
O Terms, units and symbols for use with Beers Law
Name alternative name symbol definition unit
Path length - b (or l) - cm
Liquid concentration - c - mol / L
Transmittance Transmission T I / I
0
-
Percent transmittance- T% 100x I / I
0
%
Absorbance Optical density, A log(I / I
0
) -
extinction
Absorptivity Extinction coeff., a (or , k) A/(bc) [bc]
-1
absorbance index
Molar absorptivity Molar extinction coeff., a A/(bc)
molar absorbancy index [or a
M
AM/(bc) ] M-molar weight
c -gram/L
UV & Visible Spectrophotometry
Spectroscopy Application
CH4003 Lecture Notes 19 (Erzeng Xue)
68
O Use of Beers Law
- Beers law can be applied to the absorption of UV, visible, infra-red & microwave
l The limitations of the Beers Law
O Effect of solvent - Solvents may absorb light to a various extent,
e.g. the following solvents absorb more than 50% of the UV light going through them
180-195nm sulphuric acid (96%), water, acetonitrile
200-210nm cyclopentane, n-hexane, glycerol, methanol, ethanol
210-220nm n-butyl alcohol, isopropyl alcohol, cyclohexane, ethyl ether
245-260nm chloroform, ethyl acetate, methyl formate
265-275nm carbon tetrachloride, dimethyl sulphoxide/formamide, acetic acid
280-290nm benzene, toluene, m-xylene
300-400nm pyridine, acetone, carbon disulphide
O Effect of temperature
Varying temperature may cause change of concentration of a solute because of
thermal expansion of solution
changing of equilibrium composition if solution is in equilibrium
UV & Visible Spectrophotometry
Spectroscopy Application
CH4003 Lecture Notes 19 (Erzeng Xue)
69
O What occur to a molecule when absorbing UV-visible photon?
O A UV-visible photon (ca. 200-700nm) promotes a bonding or non-bonding
electron into antibonding orbital - the so called electronic transition
Bonding e
-
s appear in & molecular
orbitals; non-bonding in n
Antibonding orbitals correspond to the
bonding ones
e
-
s transition can occur between various
states; in general, the energy of e
-
s
transition increases in the following order:
(n*) < (n*) < ( *) < ( *)
O Molecules which can be analysed by UV-visible absorption
O Chromophores
functional groups each of which absorbs a characteristic UV or visible radiation.
UV & Visible Spectrophotometry
Spectroscopy Application
*
*
n
Antibonding
Antibonding
non-bonding
Bonding
E
n
e
r
g
y
*
n
*
n
E
0
)=hv
2
O Laser uses the stimulated emission process to amplify the light intensity
As in the stimulated emission process, one incident photon (P
1
) will bring about the
emission of an additional photon (P
2
), which in turn can yield 4 photons, then 8
photons, and so on.
CH4003 Lecture Notes 21 (Erzeng Xue)
84
O The conditions must be satisfied in order to sustain such a chain reaction:
O Population Inversion (PI), a situation that there are more atoms in a certain excited
state than in the ground state
PI can be achieved by a variety means (electrical, optical, chemical or mechanical), e.g., one
may obtain PI by irradiating the system of atoms by an enormously intense light beam or, if the
system of atoms is a gas, by passing an electric current through the gas.
O 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.
O 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.
Laser - Formation & Conditions
Spectroscopy Application
CH4003 Lecture Notes 21 (Erzeng Xue)
85
Laser - Functional Elements
Spectroscopy Application
Energy pumping
mechanism
Energy
input
Lasing medium
High
reflectance
mirror
Partially
transmitting
mirror
Output
coupler
Feedback mechanism
CH4003 Lecture Notes 21 (Erzeng Xue)
86
Laser Action
Spectroscopy Application
Lasing medium
at ground state
Population
inversion
Start of stimulated
emission
Stimulated emission
building up
Laser in
full operation
Pump energy
Pump energy
Pump energy
Pump energy
CH4003 Lecture Notes 21 (Erzeng Xue)
87
Types of Lasers
O There are many different types of lasers
O The lasing medium can be gas, liquid or solid (insulator or semiconductor)
O Some lasers produce continuous light beam and some give pulsed light beam
O 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 type Physical form of lasing medium Wave length (nm)
Helium neon laser Gas 633
Carbon dioxide laser Gas 10600 (far-infrared)
Argon laser Gas 488, 513, 361 (UV), 364 (UV)
Nitrogen laser Gas 337 (UV)
Dye laser Liquid Tunable: 570-650
Ruby laser Solid 694
Nd:Yag laser Solid 1064 (infrared)
Diode laser Semiconductor 630-680
CH4003 Lecture Notes 21 (Erzeng Xue)
88
Laser - Applications
O Laser can be applied in many areas
O Commerce
Compact disk, laser printer, copiers, optical disk drives, bar code scanner, optical
communications, laser shows, holograms, laser pointers
O Industry
Measurements (range, distance), alignment, material processing (cutting, drilling,
welding, annealing, photolithography, etc.), non-destructive testing, sealing
O Medicine
Surgery (eyes, dentistry, dermatology, general), diagnostics, ophthalmology,
oncology
O Research
Spectroscopy, nuclear fusion, atom cooling, interferometry, photochemistry, study
of fast processes
O Military
Ranging, navigation, simulation, weapons, guidance, blinding
Spectroscopy Application
CH4003 Lecture Notes 21 (Erzeng Xue)