STKL 2313

Kuliah 6
Pencirian Mangkin Heterogenous
1. Sifat Fizikal Mangkin (Luas permukaan,
isipadu liang dll)
2. Sifat Kimia Mangkin (Permukaan dan
pukal)
3. Komposisi Kimia Mangkin
4. Marfologi Mangkin



1.Sifat Fizikal Mangkin
(Luas permukaan, isipadu liang dll)

Volumetric Adsorption
Measurement
N
2
(77.3 K) or
Ar, He, CH
4
, CO
2
, Kr
adsorbate
adsorbent
pressure
gauge
P
V
1
V
2
high vacuum

230810

BET Model
reality model
u
5

u
4

u
3

u
2

u
1

u
0

( ) ... 3 2 1
2 1 0 m ad
+ u + u + u = = u

n n
i
1 - n n 1 - n
1
0
n n 1 - n
1
0 1 0
1
0
1 1
1
0
0
u = u = u u = u
u = u = u u = u

p K p
k
k
k p k
p K p
k
k
k p k
d
a n
d
n
a
d
a
d a
1
st
layer

n
th
layer
For every layer
Langmuir model

Assume
RT
H
RT
H
RT
H
K K K
K K
cond n
ads
e e
e
0 , n 0 , n n
0 , 1 1
A

~ =
=
( )
|
|
.
|

\
|
+
|
|
.
|

\
|

=
0
0
0
m
ad
1 1 1
p
p
C
p
p
p
p
C
n
n
RT
H H
C
cond ads
e
A A
= with
BET (Brunauer, Emmett, Teller)
Method
Modification of Langmuir isotherm
Both monolayer and multilayer adsorption
Layers of adsorbed molecules divided in:
First layer with heat of adsorption AH
ad,1

Second and subsequent layers with H
ad,2
= AH
cond


BET isotherm:

BET equation does not fit entire adsorption
isotherm
different mechanisms play a role at low and at high p

( )
0
m m
0
ad
1 1
p
p
C n
C
C n p p n
p

+ =

|
.
|

\
| A A
=
RT
H H
C
cond ad
exp
Surface Area & Monolayer
Capacity
S = n
m
A
m
N
monolayer
capacity (mol/g)
specific surface area
(m
2
/g)
area occupied by one
molecule (m
2
/molecule)
Avogadros number
(molecules/mol)
BET model: S
BET

t model:
S
t

Contoh pengiraan
V
m
=100cm
3
N
2
/gm sampel
Avo Number=6.023x10
-23
N
2
= 14 Angstrom

S
a
=.
Adsorption Isotherms
III
n
a
d

p / p
0
VI
n
a
d

p / p
0
V
n
a
d

p / p
0
I
n
a
d

p / p
0
p / p
II
n
a
d

0
B
IV
n
a
d

p / p
0
B
Types I,II, and IV most materials
Type III uncommon
Type V rare
Type IV highly uniform surface
Langmuir Adsorption Isotherm
(Type I)
Assumptions:
homogeneous surface
(all adsorption sites energetically identical)
monolayer adsorption (so no multilayer adsorption)
no interaction between adsorbed molecules
p K
p K
n n n
m m ad
+
= u =
1
I
n
a
d

p / p
0
Type II and IV Isotherms
Multilayer adsorption (starting at B)
Common for pore-free materials
Similar to II at low p
Pore condensation at high p
p / p
II
n
a
d

0
B
IV
n
a
d

p / p
0
B
Type III and V Isotherms
III
n
a
d

p / p
0
V
n
a
d

p / p
0
Strong cohesion force between
adsorbed molecules, e.g. when water
adsorbs on hydrophobic activated
carbon
Similar to III at low p
Pore condensation at high p
Adsorption Isotherms
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1
Adsorption
Desorption
2. Jerapan Kimia
Catalyst
s
Typical Preparation
Supports alumina, silica, carbon, zeolites,

Metal source salt or complex

Metal deposition incipient, wetness, wash-coat, chemical vapor
deposition, sputerring,

Calcination (optional) decompose salt or complex to metal
oxide. Often
considered necessary to fix the metal to the support surface.

Activation convert from salt, complex, or oxide to active phase

Catalysts
Pt on Alumina Characterization
Platinum oxide on alumina

Disperson preparation efficiency

Metal surface area number of active sites

Crystallite size

. Thus is a small fraction of the desired
information
Typical ( chemisorption )
characterization
Calcine (optional) remove residual chlorine and
remove water from the support

Degas (optional) water from the support prevent
steaming

Activation reduce in hydrogen to convert platinum
oxides to platinum metal

Inert purge remove (chemi) sorbed hydrogen from
the activated Pt surface

Reaction selectively react probes with active
surface to minimize stray adsorption example H
2

O
2
H
2
titration
Diverse Pt on alumina
Considerations ..
CO chemisorption stoichiometry one Pt per
CO molecule
H
2
chemisorption stoichiometry two Pt per H
2

molecule
Spillover excess sorbed molecules


Volume of active gas
injected from a syringe
Example volume injected
using 10% active gas
Volume of active gas dosed
from a loop
Example volume dosed
using 10% active gas
Calculating Volume
Chemisorbed
Example CO Chemisorption On
0.5 wt % Pt Alumina
240810

% Metal Dispersion
Example - % Dispersion of
0.5 wt % Pt on Alumina
Active Metal Surface Area
(per gram of sample)
Example Active Metal Surface
Area (per gram of sample ) 0.5 wt
% Pt on Alumina
Example Active Metal Surface Area
(per gram of metal) of 0.5wt % Pt on alumina
Average Crystallite Size
Example - Average Crystallite Size
of 0.5 wt % Pt on Alumina
CO Adsorption on Platinum
Total and Weak Isotherms
Extrapolation to Determine
Strong Chemisorption
Difference Method to Determine
Strong Chemisorption
3.Komposisi Kimia Mangkin
Menentukan komposisi mangkin yang diterima sebelum
digunakan atau menganalisis komposisi unsur pada
mangkin yang telah disediakan.

Contoh:

1% Pt/Al
2
O
3
(m/m): menentukan terdapat 1% Pt
terdapat pada mangkin.
Komposisi Unsur Sesuatu Mangkin Boleh
Ditentukan menggunakan beberapa teknik yang
lazim seperti:
i. Spektroskopi Serapan Atom (AAS)
a. Sampel dilarutkan, ukur serapan
menggunakan AAS. (Jelaskan Konsep)
ii. Spektrometer Gandingan Aruhan (ICP)
a. Sampel dilarutkan, ukur intensiti pancaran
unsur yang teruja menggunakan ICP.
(jelaskan)
300810

iii. Spektrometer Sinar-x Pendarflur (XRF)
a. Sampel mangkin (pepejal) + Asid Borik,
press membentuk kepingan, analisis
menggunakan teknik XRF.
b. Baik untuk unsur yang mempunyai nombor
atom tinggi.
X-ray-1
X-ray-2
iv. Spektroskopi Fotoelektron
Sinar-X (XPS)


Surface Analysis - Techniques Available
photons
ions
electrons
EMISSION
TRANSMISSION
Interaction
with material
EXCITATION
Properties and reactivity of the surface will depend on:
bonding geometry of molecules to the surface
physical topography
chemical composition
chemical structure
atomic structure
electronic state


No one technique can provide all these
pieces of information. However, to
solve a specific problem it is seldom
necessary to use every technique
available.
X-ray Photoelectron
Spectrometer
Applications:
To determine the
chemical states of
sample surface,
qualitatively and
quantitatively
Measures x-ray photoelectrons
X-ray
Source
Detect Binding Energy
of Photoelectrons
Sample
Quality of catalyst can
be defined by studying
the chemical state of
the its surface.
X-ray Photoelectron Spectrometer
Multi-technique XPS
Applications:
To determine the chemical states of
sample surface, qualitatively and
quantitatively.
Chemical states mapping at 3m
resolution.
Auger Emission, Secondary Ion Mass
Spectr
The Photoelectron Process
X-rays in
photoelectrons out
Sample Surface Layer
binding energy (eV) = photon energy - kinetic energy - work function
BE (eV) = hv - KE - |
|
E
v


E
f

KE
BE
valence
band
core
levels
photon
010910

X-ray Photoelectron
Spectrometer
Xray
Photoelectron
Spectrometer
(XPS)
X-ray
Source
Detect Binding Energy
of Photoelectrons
Sample
Auger
Electron
Spectrometer
(AES)
Secondary
Ion Mass
Spectrometer
(SIMS)
Electron
Flood
Detect Auger electrons
Sample
Ions Bombard
Detect Secondary Ions
Sample
The Photoelectron Spectrum
Inelastically scattered photoelectrons
Both photoemission and Auger peaks
observed in a spectrum.
Peaks are superimposed on a rising
background, due to inelastically
scattered photoelectrons.
Cu 2p
O KLL Auger
O 1s
N 1s
C 1s
Cu LMM
Auger
Cu 3p
Cu 3s
Cl 2p
Inelastically scattered photoelectrons contribute to
the spectral background
Ultra Spectrometer
Spectral Mode
Standard input lens
Electrons dispersed
between inner and
outer hemisphere,
using standard
spectrometer
Common detector
plane