TECHNIQUES FOR CHEMICAL ANALYSIS TPX Techniques

TECHNIQUES FOR
CATALYTIC STUDIES
B. Viswanathan
National Centre for Catalysis Research
Indian Institute of Technology Madras
NCCR 1
A pictorial representation of generating the possible techniques in terms of
input and out put probes
29th October 2008 NCCR 2
Representation of the techniques based on Electrons in – electron, ion, neutral and
photon out LEED: Low Energy Electron Diffraction; HEED: High Energy Electron
diffraction; RHHED: Reflected High Energy Electron Diffraction; ILEED: Ineleastic
Low Energy Electron Diffraction; AES: Auger Electron Spectroscopy; EELS:
Electron Energy Loss Spectroscopy; EIID: Electron Induced Ion Desorption;
SEPSMS: Electron Probe Surface Mass Spectrometry; EID: Electron Induced
Desorption; SDMM: Surface Desorption Molecular Microscope; CIS: Characteristic
Isochromat Spectroscopy; APS: Appearance Potential Spectroscopy.
Schematic representation of the techniques that can be generated from Photon- in
photon, neutral, electron or ion-out methodology. XPS: X ray Photoelectron
Spectrroscopy; ESCA: Electrons Spectroscopy for Chemical Analysis
Schematic representation of the techniques that can be generated from Ions-in ion-,
neutral-, electron- or photon-out methodology. ISS: Ion Scattering Spectroscopy,
SIMS: Secondary Ion Mass Spectrometry, INS: Ion Neutralization Spectroscopy, PIX:
Proton Induced X ray emission
Partial listing of the surface Analytic Techniques with the appropriate acronym.
Acronym Technique
AEAPS Auger Electron Appearance Potential Spectroscopy
AES Auger Electron Spectroscopy
AFM Atomic Force Microscopy
APECS Auger Photoelectron Coincidence Spectroscopy
APFIM Atom Probe Field Ion Microscopy
APS Appearance Potential Spectroscopy
ARPES Angle Resolved Photoelectron Spectroscopy
ARUPS Angle Resolved Ultraviolet Photoelectron Spectroscopy
ATR Attenuated Total Reflection
BEEM Ballistic Electron Emission Microscopy
BIS Bremsstrahlung Isochromat Spectroscopy
CFM Chemical Force Microscopy
CHA Concentric Hemispherical Analyzer
CMA Cylindrical Mirror Analyzer
CPD Contact Potential Difference
CVD Chemical Vapour Deposition
DAFS
29th October 2008Diffraction Anomalous Fine Structure
NCCR 6
DAPS Disappearance Potential Spectroscopy
EDX Energy Dispersive X-ray Analysis
EELS Electron Energy Loss Spectroscopy
Electron induced luminescence
Ellipsometry
EMS Electron Momentum Spectroscopy

EPMA Electron Probe Micro-Analysis
ESDMS Electron Stimulated Desorption Mass Spectrometry
ESCA Electron Spectroscopy for Chemical Analysis
ESD Electron Stimulated Desorption
ESDIAD Electron Stimulated Desorption Ion Angle Distributions
EXAFS Extended X-ray Absorption Fine Structure
FEM Field Emission Microscopy
FIM Field Ion Microscopy
FTIR Fourier Transform Infra Red
FTRA-IR Fourier Transform Reflectance-Absorbtion Infra Red
HAS Helium Atom Scattering
HDA Hemispherical Deflection Analyser
HEIS High Energy Ion Scattering
HREELS High Resolution Electron Energy
29th October 2008 Loss Spectroscopy
NCCR 7
IETS Inelastic electron tunnelling spectroscopy
ILS Ionisation Loss Spectroscopy
INS Ion Neutralisation Spectroscopy
IPES Inverse Photoemission Spectroscopy
IRAS Infra-Red Absorption Spectroscopy
Ion Excited Auger Electron Spectroscopy
ISS Ion Scattering Spectroscopy
LEED Low Energy Electron Diffraction
LEEM Low Energy Electron Microscopy
LEIS Low Energy Ion Scattering
LFM Lateral Force Microscopy
MBE Molecular Beam Epitaxy
MBS Molecular Beam Scattering
MCXD Magnetic Circular X-ray Dichroism
MEIS Medium Energy Ion Scattering
MFM Magnetic Force Microscopy
MIES Metastable Impact Electron Spectroscopy
MIR Multiple Internal Reflection
MOCVD Metal Organic Chemical Vapour Deposition
MOKE Magneto-Optic Kerr Effect
NEOM Near Field Optical Microscopy
MIR Multiple Internal Reflection
MOCVD Metal Organic Chemical Vapour Deposition
MOKE Magneto-Optic Kerr Effect
NEOM Near Field Optical Microscopy
NIXSW Normal Incidence X-ray Standing Wave
NEXAFS Near-Edge X-ray Absorption Fine Structure
NSOM Near Field Scanning Optical Microscopy
PAES Positron annihilation Auger Electron Spectroscopy
PECVD Plasma Enhanced Chemical Vapour Deposition
PEEM Photo Emission Electron Microscopy
PhD Photoelectron Diffraction
Photon Excited Auger Electron Spectroscopy
PIXE Proton Induced X-ray Emission
Raman Spectroscopy
PSD Photon Stimulated Desorption
RAIRS Reflection Absorbtion Infra-Red Spectroscopy
RAS Reflectance Anisotropy Spectroscopy
RBS Rutherford Back Scattering
RDS Reflectance Difference Spectroscopy
REFLEXAFS Reflection Extended X-ray Absorption Fine Structure
RFA29th October 2008
Retarding Field Analyser NCCR 9
RHEED Reflection High Energy Electron Diffraction
SERS Surface Enhanced Raman Scattering
SEXAFS Surface Extended X-ray Absorption Spectroscopy
SHG Second Harmonic Generation
SH-MOKE Second Harmonic Magneto-Optic Kerr Effect
SIMS Secondary Ion Mass Spectrometry
SKS Scanning Kinetic Spectroscopy
SMOKE Surface Magneto-Optic Kerr Effect
SNMS Sputtered Neutral Mass Spectrometry
SNOM Scanning Near Field Optical Microscopy
SPIPES Spin Polarised Inverse Photoemission Spectroscopy
SPEELS Spin Polarised Electron Energy Loss Spectroscopy
SPLEED Spin Polarised Low Energy Electron Diffraction
SPM Scanning Probe Microscopy
SPR Surface Plasmon Resonance
SPURS Spin Polarised Ultraviolet Photoelectron Spectroscopy
SPXPS Spin Polarised X-ray Photoelectron Spectroscopy
STM Scanning Tunnelling Microscopy
SXAPS Soft X-ray Appearance Potential Spectroscopy
SXRD Surface X-ray Diffraction
Synchrotron Radiation Photoelectron Spectroscopy
TDS29th October 2008
Thermal Desorption Spectroscopy NCCR 10
TEAS Thermal Energy Atom Scattering
TIRF Total Internal Reflectance Fluorescence
TPD Temperature Programmed Desorption
TPO Temperature Programmed Oxidation
TPRS Temperature Programmed Reaction Spectroscopy
TPS Temperature Programmed sulphidation
TXRF Total Reflection X-ray Fluorescence
UHV Ultra High Vacuum
UPS Ultraviolet Photoemission Spectroscopy
XANES X-ray Absorption Near-Edge Structure
XAES X-ray Induced Auger Electron Spectroscopy
XPD X-ray Photoelectron Diffraction
XPS X-ray Photoemission Spectroscopy
XRR X-ray Reflectometry
XSW X-ray Standing Wave

What is Thermal Analysis?
Thermal Analysis refers to a number of methods that measure change
in any property of a system with respect to temperature, when it is
subjected to a controlled temperature variation.

THERMAL ANALYSIS TECHENIQUES
Thermo gravimetric analysis (TGA)- Monitoring the change of

weight as a function of temperature.
Differential Thermal analysis (DTA)-Change in thermal energy as

a function of temperature. (exo- or endothermic).
Differential scanning calorimetry (DSC)- Change in heat as a

function of temperature.
4. Thermomechanical analysis (TMA)- Change of dimensions.
There are other techniques such as Electrothermal analysis,

Thermoacoustimetry and so on
Principle behind various TA methods
TGA-DTG
The first derivative of TG (rate of weight change) as a function of
temperature is called DTG, i.e., the rate of weight change (dW/dt) as a
function of temperature. This facilitates clear pinpointing of maximum
weight change.

DTA: In this technique the difference in temp. (T) between the sample
and an inert reference material is measured as a function of temperature.
Exotherm T > 0 Exo

Endotherm T < 0
Endo
DSC: In DSC instead of allowing a temperature difference to be
developed, heat/energy is supplied to maintain same temperature of the
sample and reference.

EGA : It is nothing but the analysis of volatile products released on
heating, analyzed generally through a QMS or IR. (called as hyphenated
Multiple thermal techniques
It is useful to examine the behaviour of a sample by more than
one thermal method while heating the sample in a programmed
way.
TG and DTA- Simultaneous
TG and EGA-Coupled technique (TG-MS, TG-IR).
TG-DTG (no extra cost involved)
Cost effectiveness
is also one
consideration to use
simultaneous Fig1.3a
thermal
measurement.

Applications of thermal methods
1. Determination of thermal constants,

Heat of fusion, specific heat , freezing point and melting point.
The MP of pure metals (Au, Pb, Sn etc) is often used for calibration of DTA/DSC.
The area under a melting endotherm is proportional to the latent heat of fusion of
the sample.
2. Phase changes and phase equilibria

Solid to liquid phase change or liquid to gaseous state.
3. Structural changes
Solid-solid transitions where a change in crystal structure occurs, it could be exo-or
endothermic.
4. Thermal stability
One can monitor the thermal stability of an oxide, particularly stability of a porous
material.

Applications of thermal methods contd
5. Thermal decompositions
 Decomposition of a polymer.
 Decomposition of template or an occluded material
from a zeolite. Thermal decomposition of copper
sulphate (CuSO45H2O).
CuSO4.5H2O  CuSO4.3H2O + 2H2O
CuSO4.3H2O  CuSO4.H2O + 2H2O
CuSO4.H2O  CuSO4 + H2O
6. Characterization of materials.
 Determination of glass transition temperature.
 Analysis of Portland cement versus high alumina
cement.
Applications of thermal methods contd
Quantitative analysis (TGA)
Plaster contains gypsum (CaSO42H2O), lime Ca(OH)2 and chalk
CaCO3.
Fig 1.4m

Thermo gravimetric analysis-
Instrumentation
It is is a thermo balance
consisting of
(a) High precision balance,
(b) A furnace for achieving high
temperatures, e.g.., 1500 oC
(c) A temperature programmer,
(d) Data acquisition system.
(e) Auxiliary equipment to
provide inert atmosphere
A – beam F – Magnet
B – Sample cup G – control amplifier
C –Counter weight H – Tare calculator
D – Lamp and photodiode I – Amplifier
E – Coil J – Data station
Cross Section of TGA (Horizontal)
Reactive and
Cooling protective gas inlets
Balance
Balance: :1g,5g;1µ,0.1µg
1g,5g;1µ,0.1µg
GAS FLOW
Gas
Vacuum and
outlet
purge gas tubing
stopcock
Vacuum connection and purge gas inlet

Requirements of a TG balance:
1. A thermo balance should provide accurate weight of the
sample as a function of temperature. (capacity upto 1g,
typical sample in mg). Its reproducibility should be very high
and also highly sensitive.
2. It should operate over a wide temperature range, say from RT
to 1000/1500 oC.
3. The design of thermo balance should be such that sample
container is always located within a uniform hot zone inside
the furnace.
4. The sample container should be such that it does not react
with the sample at any given temperature.
5. The balance should not be subject to radiation or convection
effects arising from the proximity of the furnace.
6. It will be advantageous if thermo balance can be coupled to a
GC or IR or to QMS.
Types of Balances
Null point balance:
As weight change occurs, the balance beam starts to deviate from its
normal position, a sensor detects the deviation and triggers the
restoring force to bring the balance beam back to the null position. The
restoring force is directly proportional to the weight change.
Deflection balance:
When balance arm is deflected by a change in weight, the relative
illumination of photocells from light source changes due to the
movement of shutter attached to the balance beam, resulting in flow
of compensating current through one of the pair of photocells.
The current produced is proportional to the change in sample

weight and after amplification is passed to the coil thus restoring it
to its original position. There are two types of deflection balances,
(i) Beam type and (ii) Cantilever type.

Furnace:
(i) Furnace is the heart of a thermal analysis instrument. It should
give very good uniform heating zone.
(ii) Uniform heating zone can be achieved, if the mass of furnace
is high, but it is difficult to heat or cool such furnaces quickly.
Low mass furnaces are faster to heat or cool, but it is difficult
to attain linear rise in the temperature.
(iii) The heating coil should not get affected by the liberated gases
during heating of the samples.
Temperature measurement:
Usually chromel/alumel (~1000 oC) or Pt/Rh thermocouples
(>1000 oC) are used. They must be chemically inert even at
high temperatures and their location with respect to the
sample is critical.

Sources of error in Thermogravimetry
1. Buoyancy effect of sample container
It is nothing but apparent gain in weight when an empty, thermally
inert crucible is heated. It has three components;
(i) decreased buoyancy of atmosphere around the sample at higher
temperatures;
(ii) the increased convection effect; and (iii) the possible effect of
heat from the furnace on the balance itself.
Modern instruments take care of these factors. A blank run with
an empty crucible is always preferable.
Archimedes principle : any object, when wholly or partially
immersed in a fluid, is buoyed up by a force equal to the
weight of the fluid displaced by the object
The density of gases decreases with increasing temperature :
e.g. Air : 25°C 1.29 mg/ml
225°C 0.62 mg/ml
425°C 0.41 mg/ml
Sources of Error in Thermogravimetry
2. Furnace and temperature effects
Heat from the furnace may cause convection.
Magnetic and inductive interaction between certain samples and
winding of the furnace.
Thermocouple calibration
3. Other effects
Turbulence in the gas flow.
Temperature measurement effects.
Placement of the thermocouple.
Quantity of sample used for analysis.
Packing of the sample
Container materials. Mostly Pt, Alumina crucibles are used.
Gas flow to evacuate the decomposition products.

Applications of TGA
Decomposition of calcium oxalate
Step-I
CaC2O4.H2O  CaC2O4 + H2O
MW 146 128 18
Step-II
CaC2O4  CaCo3 + CO
MW 128 100 28
Step-III
CaCo3  CaO + CO2
MW 100 56 44

Applications of TGA in Quantitative analysis
Ca, Sr and Ba are

precipitated as monohydrated
oxalates.
In the first step, H2O is
removed from all the three
oxalates, while in the second
carbonates are formed by
losing CO. The third step,
stable oxides are formed by
losing CO2.

Factors affecting TGA curves
can
Experimental conditions
alter the onset as well as
the end of decomposition.
Shape/sharpness of curves
change with heating rate.
Experimental conditions
should be known for
comparison of curves from
different sources.
Change of atmosphere
influences the decomposition.
Oxidation takes place in air,
while decomposition takes
place in its absence.

GAS FLOW RATES
• High flow purge rates ? Not recommended, specially for
vertical TGA balances due to more turbulence) :
• Better controlled atmosphere (inert) specially at higher

temperatures
• Typical purge gas flow rate for small furnace : 60

ml/min for a vertical TGA , but can be increased up to
500 ml/min ( even 1000 ml/min ) in case of horizontal
models, to rapidly purge the furnace without the use of
vacuum.

DTA and DSC
DTA: Gives information on heat change by measuring
difference in temp. between sample and reference.
DSC: Temperature of sample as well as reference is
maintained same by supply of required heat to the
sample/reference depending on exo- or endothermic
change.
Peak areas:
DTA: peak area (A) =  K. H.m
m- mass of sample, H- heat of reaction and K –constant
which depends upon sample geometry as well as thermal
conductivity. K varies with the temperature, hence instrument
has to be calibrated at each temperature.
DSC: Peak area can be calculated similar way as in DTA,
however K is electrical conversion factor which does not
change with temp for well designed equipment.
Types of DTA, DSC analysis systems

Applications of DTA
DTA of Sulphur
113 oC peak-
Rhombic to monoclinic
124 OC peak-
Melting point
179 OC peak-
Transition among three
forms of liquid ’S’.
446 OC peak-
Boiling point of sulphur

Combined TGA-DTA

CeAlO3 formation-TG-DTA study
0.00 (c)
Derivative Weight (mg/min)
-0.02
-0.04
CeAlO3 CA-prec
CeAlO3 CP-prec
CeAlO3 HD-prec
-0.06
100 (b) CeAlO3 CA-prec
98
CeAlO3 CP-prec
-0.08 DTG 96
CeAlO3 HD-prec
94
-0.10 92
90
Weight %
-0.12
88 TGA
86
200 400 600 800 1000
84
o
Temperature ( C) 82
80
(a) CeAlO3 CA-prec
Heat Flow (mW),Endo down/Exo up
10
78
CeAlO3 CP-prec
76
0 CeAlO3 HD-prec
74
72
-10
200 400 600 800 1000
o
-20 Temperature ( C)
-30
-40 DTA
-50
-60
200 400 600 800 1000

o
Temperature ( C)
Hyphenated systems
TGA-MS
TG Analyzer Purge Capillary Gas Analyzer

Purge
gas +
gas
Balance Furnace products Heater Quadrupole Pump
TGA-FT IR
Transfer
TG Analyzer Purge Gas Analyzer
Purge Line
gas +
gas Gas
Balance Furnace products Heater Interferometer
Cell

Coupled techniques
29th October 2008

TG-DTG-DTA-MS of Calcium Oxalate
NCCR 42
Coupled techniques

Typical DSC-Trace

DSC
When H for reaction > 0
the sample is heated.
When H for reaction < 0
the reference is heated.
When the sample is heated
the rate of heat flow is
proportional to CP,

DSC of Liquid Crystal

Polymorphism of Sulfapyridine

Calibration procedures in DSC/DTA
Accurate temp of the peak is very important as it is a
kind of finger print for a particular system, hence the
temperature has to be calibrated.
DSC is used for quantitative enthalpy estimations, hence
it has to be calibrated for this.
International Committee for Thermal Analysis has
certified a number of materials for the purpose of
temperature calibration.
The sample temperature data can then be compared with
the data obtained on other instruments.

Transition Temperature Data of Reference Materials
Reference DSC/DTA mean values, oC

material
Onset temp Peak temp
KNO3 128 135
In 154 159
Sn 230 237
KClO4 299 309
Ag2SO4 424 433
K2SO4 582 588
K2CrO4 655 673
BaCO3 808 819
Sr CO3 928 938
Enthalpy calibration reference materials
Element or Melting Point Enthalpy of
compound (oC) fusion (J g-1)
Naphthalene 80.3 149.0
Benzoic acid 122.4 148.0
Indium 1 56.6 28.5
Tin 231.9 60.7
Lead 327.5 22.6
Zinc 419.5 113.0
Aluminium 660.2 396.0
Silver 690.8 105.0
Gold 1063.0 62.8
Suggestions for Reading
1. Methods of Thermal Analysis - Applications from
Inorganic Chemistry, Organic Chemistry, Polymer
Chemistry and Technology by Dr. Hermann Utschick
(108 pages).
2. Thermal Methods
From Series: Analytical Chemistry by Open Learning
Authors: James W. Dodd, Kenneth H. Tonge, Brian R.
Currell.
1. Principles of Instrumental Analysis,
Douglas A. Skoog.

Temperature Programmed Methods for
Characterization of Materials

T P Methods in catalysis-Its importance
 Investigation of surface structures is important for optimum design

of catalysts.
Interaction of reactants with the catalyst surface is an important
step in heterogeneous catalysis.
 Temperature at which species are desorbed from a surface is
indicative of the strength of the surface bond.
 Neither strong chemisorption nor very weak chemisorption is
helpful.
Steps in a heterogeneous catalytic reaction
Transport of reactants to surface of the catalyst.

Chemisorption of reactant.
Surface reactions involving chemisorbed species.
Product generation and liberation from catalyst
Removal (diffusion) of products from the surface

How a TP experiment is carried out?
 Probe molecules are adsorbed at lower temperatures and their
desorption/reaction with increased temperature is monitored to
characterize surface properties of a catalyst and also properties
of an adsorbent.
 Alternately a carrier gas containing the desired species is used

and the reaction is carried out by increasing the temperature.
There are many variants

Of these experiments
based on the information
one looking for

Temperature Programmed Methods-Classification
Thermo analytical Analytical Instrumentation

technique
Change of Dimension Dilatometry
Change in weight Thermogravimetry
Change in energy DTA, DSC
Evolved gas analysis Temperature programmed

desorption
Gas evolved after TPR, TPO and temperature
chemical reaction programmed (surface) reaction
Usually the analysis is qualitative describing peak maxima,
(position of peaks) and the number of peaks. However, total
consumption of reactant as well as under each component can
be October
29th obtained.
2008 NCCR 55
Temperature Programmed Techniques-classification
There are three principal processes that are studied as a function of
temperature: 1) Desorption, 2) Reduction and 3) Oxidation.
TPD- Temperature Programmed Desorption
A solid material after cleansing its surface is exposed to
adsorbate gas under well-defined conditions (at various
pressures and temperatures) and then heated under inert
conditions in a programmed way to desorb it.
TPR- Temperature Programmed Reduction OR
Temperature Programmed Reaction.
Surface of a solid is cleansed in oxidizing atmosphere and
subsequently heated linearly in a programmed way under the
flow of dilute stream of reducing gas (H2/CO in Ar). The rate of
redn. is monitored by following the change of its concentration
at the outlet. This experiment permits determination of total
H2/CO consumed, thereby degree of reduction and average
oxidation state can be calculated.
Temperature Programmed Desorption
Developed by Cvetanovic and

Amenomiya (Adv Catal 1967, 17, 103)
The gas stream contains
desorbed molecules, monitored by
TCD.
The TCD signal is proportional to
quantity of molecules desorbed
while thermal energy required in
terms of temperature is monitored
by a thermocouple.
Quantities desorbed under
different Tmax provide information TPD chromatogram of H2 desorbing
on the number, strength and
from Pt supported on alumina
heterogeneity of the adsorption
(Reproduced from Paul A Webb’s article)
sites .
Experimental requirements
Set up for TP experiments mainly consist of four components
1. System for introduction of reactant/probe molecule:
Sampling valves, gases and gas mixtures, mass flow controllers.
1. A programmable furnace and reactor assembly:
Furnace should be suitable for rapid heating and cooling, temp
raise has be linear. It should have uniform heating zone. Reactor
should be made of quartz preferably.
3. Detector and data acquisition system:
Mostly TCD detectors are employed, TCD with quadrupole
mass spectrometer is a preferred option. Micro GC also can help
in distinguishing various components in the desorbed gas stream.
TGA balance also can be used for monitoring weight changes
during the heating of sample. Data system should be capable of
fast sampling and display of evoluted species with respect to
time and temperature.
Experimental Set up for TPD/TPR/TPO
High TCD
sensitivity.
Volume between
reactor outlet and
TCD should be
low.
Using MFC is
better.
Cold trap for TPR.
Lower H2
concentration in
gas for achieving
differential
conditions.
Temperature Programmed Reduction
Described first by Robertson et al ( J. Catal 1975, 37, 424)
MO (s) + H2 (g)  M (s) + H2O
Starting temp is below

reduction temperature.
As the temperature is increased
reduction takes place in steps.
Each reduction peak corresponds
to a different oxide and the
area under each peak is
proportional to its concentration.
Hence, one can obtain
information on number of Temperature programmed reduction
reducible species as well as their of Fe2O3 by hydrogen.
activation energies. (Reproduced from Paul A Webb’s article)
Standardization of TPR
AgO + H2 → Ag + H2O
Theoretical H2 consumption
is 96.7 cc at STP.

dn/dt – rate of reduction

- degree of reduction
Rate of reduction is definitely related to rate of H2
consumption and hence can be determined as a
function of time.
The parameters that determine the

position of the maximum rate and
shape of the H2 consumption peaks
are:
(i) The heating rate  (oC/sec or K/sec),
(ii) Amount of reducible species no( mole),
(iii) Flow rate F (cc/sec) of reducing mix gas,
(iv) concentration co( mole/cc) of H2 in the gas
mixture.
(i) The heating rate  (oC/sec or K/sec),
(ii) Amount of reducible species no( mole),
(iii) Flow rate F (cc/sec) of reducing mix gas,
(iv) concentration co( mole/cc) of H2 in the gas
mixture.
Monti and Baiker defined a characteristic number K which relates the
above parameters that facilitate selection of proper exp values.
K = no/(F x co)
For heating rates between 6-20 oC/min

K between 55s to 140s is optimum for obtaining good profiles.
K < 55s, the sensitivity is too low.
K> 140s, the amount of H2 consumed is too large.
For bringing heating rate  also into consideration, Malet and
Caballero proposed a characteristic number P = (nox ) / (F x co)
Condition for optimum reduction profile in this case is that P  20 K
Kinetics and mechanism of reduction
Nucleation model
Oxygen is removed,
rearrangement takes
place in the lattice of
oxide sphere, after
which reduction.
progresses rapidly
Critical time
Typee of red solids

Contracting sphere model
1. Bulk reducible
species
2. Supported reducible
species
3. Solid solutions
containing reducible
species
Kinetics and mechanism of Reduction
(a) Bulk reducible compounds:

Bulk reducible compounds such as oxides can be interpreted in
terms of either nucleation or contracting sphere model. It is
nucleation controlled, if the rate of reduction is limited by the slow
formation of first nuclei. After a critical amount of oxygen is
removed, the lattice rearranges forming a metal nuclei. Reaction
interface will move into bulk oxide either by inward diff of H2 or
by outward diff of oxygen ions.
In contracting sphere model the rate of reduction is assumed to be
proportional to the specific surface area So of the bulk reducible
compound. Based on this an equation was derived that relate actual
state of reduction
d/dT = (So x ko/)x(1-)2/3 exp(-E/RT)
Based on this, the shape of TPR profile will be different for nucleation and
contracting sphere mechanisms.
Kinetics and mechanism of Reduction
(b) Supported reducible species:

If supported oxides are present as 3-dimensional islands, they
reduce similar to bulk reduction. If they are homogeneously
distributed, interaction will impact its reduction mechanism and
kinetics. Homogeneously dispersed species may reduce into
metals or clusters, which may migrate and form small particles.
These may contribute to spill over leading to auto-catalytic
reduction.
(C)Solid solutions (metals in zeolites or oxide matrices)
Reducible species are homogeneously distributed. Reduction is
similar to contracting sphere model initially. However, the
reaction interface area ‘S’ of catalyst particle does not change
during reduction process and is equal to spe. surface area.
Hence, the reduction rate continuously decrease due to depletion
of reducible species.
The energy equation for TPR is G = Go + RT (log PH2O/PH2)
Where G is free energy, PH2O/PH2 are partial pressures.

The above equation produces –ve results for a number of oxides.
However, reduction proceeds even when Go is positive because
PH2O is removed continuously.
Even when PH2O is low at elevated pressures, RT (log PH2O/PH2)
may become sufficiently –ve to cancel a +ve G0.
Reduction of oxides differ when they are in bulk and when they
are supported.
The interaction of the support with metal alters its reduction
behaviour. Higher the interaction, more difficult to reduce.
TPR of mixed Copper and Manganese oxides
Important parameters
Heating rate
H2 concentration
Flow rate
Content of reducible
species

Dependence of TPR curves on experimental parameters
A. Heating rate
B. H2 concentration
C. Flow rate
D. Content of
reducible species

TPR of bulk oxides- Cu2O, CuO and CuO:ZnO oxides
TPR results suggest that CuO reduces
to the metal in a one-step process:
CuO + H2  Cuo + H2O
67 : 33
480K
TPR of CuO:ZnO of various ratios

Temperature Programmed Reduction-Supported metal oxides
V2O5 supported on TiO2

In addition, reduction strongly depends on dispersion and
interaction with the support. NCCR
29th October 2008 71
T P R of Supported metal precursors
62 K
85 K
TPR of (A) unsupported and SiO2 supported Cu

(B) unsupported and SiO2 supported Ni
It29thwas shown that metal supportNCCR
October 2008
interaction Al2O3> SiO2 > TiO2 72
TPR- Effect of preparation and salt used
TPR of 0.5%Pt/SiO2 TPR profiles of pure Pt salts

A. Impregnation of H2PtCl6
B. Ion exchange with Pt(NH3)4(OH)2
TPR of Bimetallic systems
An additive may influence

activation energy of reduction
In case of Pt-Re system,

hydrated state facilitated
mobility of Re2O7 thus giving
single red peak. If the sample
is calcined at >773K, only
single peak is obtained.
In normal case, it is difficult to
reduce Sn. But, in case of Pt-
A. 3 wt%Cu/SiO2 Sn on alumina, Sn could be
B. 5 wt% Ru/SiO2 reduced.
C. (3%Cu+5%Ru)/SiO2
TPR of promoted metal catalysts
Noble metal catalysts are often

promoted.
RhVO4 phase can be formed when
RhCl3 and NH4VO3 precursors are
impregnated on silica followed by
calcination at 900 oC.
Since, no reduction was observed
below 500 K, Rh2O3 must have
reacted with VOx to form ternary
oxide precursor RhVO4. This was
proved with other techniques. As a
result, well dispersed Rh was A. Rh2O3/SiO2
formed. B. V2O5/SiO2
29th October 2008 NCCR C. (RhVO4+V2O5)/SiO2 75
TPR of metals in zeolites
Mn+ + n/2 H2 Mo + nH+
Cations at different sites in a zeolite have different
electrochemical potentials, hence reducibility differs.
Cations in small pores are difficult to reduce as they
are stabilized by high –ve charge density.
29th October 2008 TPR of (A) Pd/NaY NCCR

(B) Pd/MgY 76
TPR of Nitrides
A Quadruple mass spec aids monitoring of

species released during the TPR process.
The passivated catalyst has atleast one

monolayer of oxygen on the surface.
Water and ammonia were evolved during

TPR experiment, while consuming H2.
TPR of Molybdenum nitride

prepared through Temp Prog
reaction
29th of2008
October MoO3 with NH3 NCCR 77
TPO- Temperature Programmed Oxidation
As the name suggests, a sample, which is in reduced state is

oxidized in dilute (2% O2 in He) oxygen stream while heating it
in a programmed way.
It is mostly performed after TPR.
Difficult to attain total oxidation as diffusion prevents oxidation of
bulk species.
Oxygen consumption can be measured, which can be used for
finding surface oxidizable species. When carried out in succession
with TPR, it provides information on redox properties of the sample.

Temperature Programmed oxidation
During calcination of Pd(NH3)42+-NaY

Nitrogen is evolved while oxygen is
consumed which is monitored by QMS.
This technique is more useful to find

surface oxidation and reduction properties
of metal oxide based catalysts.
TPO of Pd(NH3)42+-NaY
Summary of TPR and TPO
TPR is a useful technique to determine the reducibility of sample
and to find the amount of H2 consumed.
Using H2 consumed one can calculate mean oxidation state .
Kinetic parameters can also be estimated and it can be

determined whether the species is reduced in one step or in
multisteps.
Active phase to support interactions can be followed and also the
influence of pretreatment.
Nature of precursor species, role of additives and influence of
one phase on the reduction of other phase can be investigated.
Red-ox behaviour of oxides can be investigated with cyclic TPR-
TPO experiments.
Experimental Set up for TPD/TPR/TPO

Methods of introducing the probe gas/vapour
Treating with gas in

continuous mode.
Pulsing/dosing the required

quantities

TPD
Determining the quantity and strength of the acid sites on
catalysts like silica-alumina, zeolites, mixed oxides is crucial
to understand and predict performance.
For some of acid catalyzed reactions, the rate of reaction
linearly related to acid sites.
There are three types of probe molecules for TPD: NH3, non-
reactive vapors and reactive vapors.
Advantages and disadvantages of NH3 as a probe
 Its molecular size facilitates penetration into all pores in a solid
 However, large molecules can not access all the sites available,
hence it over estimates the quantity of acidity.
 It is highly basic, hence titrates even weak acid sites.
 Strongly polar adsorbed NH3 also capable of adsorbing additional
NH3 from gas phase.
TPD of Amines
Large non-reactive amines such as pyridine and t-butyl amine

are alternative to NH3.
They titrate only the strong and moderate acid sites.
Though pyridine chemisorption studies by IR spectroscopy is
most appropriate, lack of extinction coefficient data complicates.
Most commonly used are propyl amines.
It reacts and decompose to propylene and ammonia over B-acid
sites.
NH2
+ NH3

Temperature programmed desorption of NH3
 H2, CO on metals
 Basic compounds on solids with acid sites
 Acidic compounds for solids with basic sites
Plots are deconvoluted to derive
WEAK and STRONG acidity
H-Beta
6
4
Desorption
0
100 200 300 400 500 600
Temperature(o C)
Acidity distribution in H-beta and dealuminated samples
Sample Si/A Weak Strong

118 H-Beta l acidity acidity
D-Beta 34 (meq/g (meq/g
116 D-Beta 46 ) )
D-Beta 175
114 H-Beta 15 0.55 0.66
Desorption
112 H-Deal 1 34 0.21 0.30

110 H-Deal 2 46 0.09 0.30
108 H-Deal 3 175 - -
100 200 300 400 500 600
Temperature(oC)

Ammonia TPD of various zeolites
NH3 TPD of various zeolite structures NH3 TPD of HY zeolites with various
SiO2/Al2O3

Ammonia TPD of metal substituted MFI zeolites
Al-MFI

NH3 TPD of ZSM-5 zeolites after and before modification
Acidity
Catalyst Tmax (K) (mmoles of NH3)
weak strong
HZ-40 473, 594 0.43 0.34
HZ-100 471, 621 0.34 0.31
HZ-250 459, 601 0.18 0.29
HZ250 CLD 446, 582 0.12 0.19
HZ250 CLD-LE 455, 577 0.14 0.11

TPD of Ammonia for zeolite acidity-Effect of heating
rate
There are clearly two types of acid sites giving

two Tmax
Heating rate shift the Tmax
Identification of desorption peaks

Acidity Vs Al content
Relationship between number of acid sites

and Al content in the framework

TPD of pyridine for zeolite acidity
Pyridine adsorption was done at different temperatures

Quantity of weakly adsorbed pyridine is affected, while it hardly
affected strongly sorbed pyridine.
TPD of IPA for zeolite acidity
NH2
+ NH3
Temp <300 oC, TPD gives only IP

Above 300 oC IP produces both NH3 and propylene
There is a lag in NH3 desorption because of re-adsorption.
Hence,
29th Octoberpropylene
2008 desorbed is good .
to be used to calculate the acidity94
NCCR
TPD of Dimethylpyridines
Appl Cat A: 194-95 (2000) 253-63

TPD of Dimethylpyridines
Appl Cat A: 194-95 (2000) 253-63

Shape Index
• The ratio of a/b corresponding to the
HWFM
• (a/b) = 1 symmetric denotes Gaussian
distribution
• (a/b) not equal to 1 indicates certain
features of the reaction taking place in
DTA
• Skewing is important
Significance of shape index
• Shape index = 1 what does it mean
• Homogeneous nature of the substance
• Uniform heat distribution
• Temperature uniformity
• Ideal situation

Significance of Shape Index
• Shape index not equal to 1
• Less than one fast process followed by
slow process
• Greater than 1 denotes slow process
followed by a slow process

Universality of Shape index
• Is this applicable for all thermal methods
• Or only for differential methods
• Or only programmed methods
• Or even to isothermal methods

Leading Edge
• Can the skew in the trace can be thought
of the leading edge parameters
• Leading edge what is its significance
• Is there alternate significance for the
shape index or leading edge

Isothermal data
• Alpha versus t data
• This type of data are already available with
you ( kindly refer to the kinetic project
given to you)

Alpha time plots
how they have to be treated

Table 1. Thermal Analysis Techniques.
Abbr. Name Characteristic factor monitored
DTA, Differential thermal analysis Temperature difference between

DSC Differential scanning calorimetry sample and reference
TG Thermogravimetry Weight of sample
DTG Differential thermogravimetry Rate of weight changes
TMA Thermomechanical analysis, Specific volume of solid sample

Dilatometry
TMA Thermomagnetic analysis Magnetic susceptibility
DMC Differential microcalorimetry Enthalpy difference between

sample and reference
TPx Temperature-programmed reaction Gas composition at the reactor
(x =Reduction, Oxidation, outlet
Desorption, Sulphidation or Surface
Reaction
Thermal methods are employed for the study
Decomposition
oxidation
reduction
solid state reactions and so on for
Materials of quality
Thermal stability and
Chemical processes /transformations.

It is appropriate to quote Flynn at this stage. He
said “ the unfortunate fact is that, since in thermal
analysis, properties of the system are measured
as a function of (both) time and temperature, all
thermo-analytical results are potentially kinetic
data, and many people ill grounded on kinetics
( like the present author) feel obliged to perform a
kinetic analysis of them”

Kinetic triplet
• Activation energy
• Pre-exponential factor
• g(α) or f (α)
• Kinetic data derived from thermal methods are always considered

with some skepticism – why is this so?
• The kinetic triplets do not have a physical meaning but can help in
predicting the rate of the processes for conditions when the
collection of experimental data is impossible.
• The kinetic parameters do not have a physical meaning and can be
used to help in elucidating the solid state reaction mechanisms
• Truth is in between.

Kinetic data from thermal methods
• Ambiguity inescapably accompanies interpretation of kinetic data obtained in

thermal methods.
• May be short comings from computation methods or experimental shortcomings.
• Experiments are often done either isothermal or under iso-conversions or under

suitable heating rates all these are unable to provide the details of all that take place
under thermal methods.
• The reactions are not normally not simple stoichiometric like dehydration
decomposition – a single set of kinetic triplet can describe a simple reaction at the
most or if the mechanism is independent of temperature and the progress of the
reaction.
• Finally non-isothermal kinetics is obliged to give the same results as isothermal

kinetics. There are enough support for both for and against.

Table 2. Types of information obtainable from TPx techniques.
TPD, Temperature-programmed desorption

· Characterization of adsorptive properties of materials
· Characterization of surface acidity
· Temperature range of adsorbate release, temperatures of rate maxima
· Total desorbed amount, adsorption capacity, metal surface area and dispersion
· Surface energetic heterogeneity, binding states and energies of adsorbed molecules
· Mechanism and kinetics of adsorption and desorption
TPR, Temperature-programmed reduction

· Characterization of redox properties of materials, .fingerprint. of sample
· Temperature range of consumption of reducing agent, temperatures of rate maxima
· Total consumption of reducing agent, valence states of metal atoms in zeolites and metal oxides
· Interaction between metal oxide and support
· Indication of alloy formation in bimetallic catalysts
· Mechanism and kinetics of reduction
TPO, Temperature-programmed oxidation

· Characterization of redox properties of metaand metal oxides
· Characterization of coke species in deactivated catalysts
· Total coke content in deactivated catalysts
· Mechanism and kinetics of oxidation reactions

Kinetic analysis of data generated by
thermal methods
Various options
(i) Model based
(ii) parameter based
(iii) geometry based
(iv) experimental variables based
and so on………..
Why do we question the kinetic analysis of thermal
methods?
In contrast to the conventional homogeneous

kinetics, there is no conception of a simple reaction
in the solid-state reaction kinetics. The geometric-
probabilistic phenomenology currently in use is not
adequate for describing the interplay between the
chemical mechanism and the observed kinetic
behaviour. Hence it is necessary to question the use
of the mode and formulations employed for
homogeneous reactions when they are applied to
solid state
29th October 2008 reactions. NCCR 119
Arrhenius Equation why?
• Since temperature is the main variable and
temperature and time are related by the heating
rate these data are suited for kinetic analysis.
• The basic equation in kinetics relating

temperature and rate constant is the Arrhenius
equation and hence we wish to seek in this
presentation the appropriateness of employing
this equation for the analysis of kinetic data from
data obtained from thermal methods.

The applicability of Arrhenius equation
for homogeneous molecular level
reactions is well known and has been
established beyond doubt since these
systems obey the Maxwell-Boltzmann
distribution. However the energy
distributions in solids are not the same
However alternate functions like
relating ln k with T or relating ln k
with ln T in addition to ln k versus 1/T
have been proposed but these
equations are “theoretically sterile”
since the constants of the se proposed
equations do not lead to any deeper
understanding of the steps of chemical
reaction.
The kinetic reaction mechanism can be determined from the
Arrhenius equation
K = A exp ( - Ea/RT)
Ea is the activation energy and R is the universal gas constant,

A is the pre-exponential factor; T is the absolute temperature
and k is the reaction rate constant.
The above equation upon log transformation can be rewritten

as
Ln k = ln A - Ea/RT
The activation energy can be determined from the slope of the

plot of ln k verses 1/T. and the intercept would yield the value
of29th
pre-exponential
October 2008 factor. NCCR 123
TWO CONSTANTS OF ARRHENIUS EQUATION
The use of Arrhenius equation gives rise to

values for two important parameters namely
the value of activation energy (Ea) and the
pre-exponential factor (k0). Both have great
significance in treating kinetic data of
chemical reactions in general. They also
relate to two basic thermodynamic
parameters namely ΔH and ΔS but for the
formation of the activated species
In the terminology of homogeneous kinetics, the activation
energy Ea is usually identified as the energy barrier ( or
threshold) that must be surmounted to enable the
occurrence of the bond redistribution steps required to
convert the reactants into products. The pre-exponential
term A provides a measure of the frequency of occurrence
of the reaction situation usually envisaged as incorporating
the vibration frequency in the reaction coordinate.

This normally implies that the fractional reaction g (α) = kt is linear.
Polanyi-Wigner model probably assumes such a relationship for solid
state decompositions as well
The equation (dx/dt) = (2νE/RT)x0 exp (-E/RT)
This equation is based on for linear rate of advance of the interface.

This has been modified for geometry in deriving rate equations.
The vibration frequency ν is expected to be or the order of 1013 s-1
Experimental or derived values of A have been compared with this
expected value.
Reactions are normal when A is one or two orders less than 10 13 and
E is in the range of enthalpy of dissociation.
Reactions are abnormal when both A and E are different from the
critical values.
The thermodynamics of the activation process ((ΔS ± and
ΔH±) for an irreversible reaction is given by Eyring type of
equation
The equation
(dx/dt) = (k B T/h) xo exp (ΔS ±/ R) exp (-ΔH±/RT)
The so called normal values of ν is calculated on the
assumption that the entropy of activation (ΔS± ) is zero.
For abnormal reactions the value of (ΔS± ) is of the order
or 200 to 500 JK -1mol -1. It is possible to derive the transition state
terminology using the concept of partition functions Q ± and Q. Values of Q ±/Q can be
less than or equal to or greater than 1. However mechanistic differences are only postulates.
The introduction of T dependence on A also has not improved the situation. Concept of
discrete activated state itself is not clear. Immobility of species in solid state different from
homogeneous reactions. Multi-step process electronic or phonon activation, thermal
gradient and other parameters.
Data from A.K.Galwey, Thermochimica Acta, 242 (1994) 259-264
Fig The frequency of occurrence of Arrhenius pre-exponential values, expressed as
lgA/s-1) in steps of equal increment. Note that there is no preference towards the
normal expected value of A = Approx 10 13 s-1
Data from A.K.Galwey, Thermochimica Acta, 242 (1994) 259-264
Table 2. Kinetic parameters of thermal decomposition for
explosives. The relevant equation is
ln (β/Tp2) = ln (AR/T) –Ea/RTp

pentaerythritol tetranitrate (PETN),

RDX, hexanitrostilbene or 2,2′,4,4′,6,6′-hexanitrostilbene (HNS) and
HMX are investigated
Table experimental data of alpha –temperature curves for the decomposition of
calcium carbonate in vaccum at different heating rates, 18,2,5,3,5,5,0,6.2,10.0 K
min -1 [Data reproduced from Thermochimical Acta 355(2000)125-143

Table experimental data of alpha –time isothermal data for the decomposition of
calcium carbonate in vacuum at different temperatures, 550,540,530,520,515) [Data
reproduced from Thermochimical Acta 355(2000)125-143

Table experimental data of alpha –temperature curves for the decomposition of
calcium carbonate in vaccum at different heating rates, 18,2,5,3,5,5,0,6.2,10.0 K
min-1 [Data reproduced from Thermochimical Acta 355(2000)125-143

Table experimental data of alpha –time isothermal data for the decomposition of
calcium carbonate in nitrogen at different temperatures, 773,750,740,732,719,710
and 700 0 C) [Data reproduced from Thermochimical Acta 355(2000)125-143

Graphical presentation of the Arrhenius parameters for the
decomposition of CaCO3 in nitrogen [data from
Thermochimica Acta 355(2000) 145-154.]

Graphical presentation of the Arrhenius parameters for the
decomposition of CaCO3 in vaccum [data from
thermochimica Acta 355(2000) 145-154.]

Multi step nature of solid State Reactions
Interface advance or proportional to surface area –

deviation due to local reactivity
local decrease of E or strain
or formation of defect
the interface R/P or R/inert gas or vacuum
or topo-tactic reactions or R/I/P intervening phase of melt or R/R
(mod)/I/P
In this context it is possible that Polanyi-Wigner treatment is

applicable averaging effect
Energy in te form phonons ( vibrations internal or other wise)
may be similar to the homogeneous phase reactions.
Fig. Suggested Band structure across the reaction zone
(Reproduced from A.K.Galwey abd B.E.Brown Thermochimical Acta 386(2002)91-98.

Azide excitation
29th and activation energy arecomparable
October 2008 NCCR 140
Energy Distributions
Fermi Dirac distribution when Ee is far exceeds

Ef then it reduces to a Maxwell-Boltzmann
distribution.
If phonon energy obeys Bose Einstein statistics

even then at higher energies that is hω »2πkBT
then the expression is similar to M –B
distribution fucntion.
Distribution of Activation Energies
1.Compensation between ln(A) being linear

function of E
2.A single common value of A and a continuous

distribution of activation energies
3.A single value of E and a continuous distribution

of Pre-exponential factors.

Kinetics under different experimental conditions –
some cautions
• Main reasons for studying • Activation parameters
the kinetics of thermal should be stated with
decompositions. specifying the kinetic
• Product quality triplet. At least like under
• Thermal stability vacuum etc.
• Chemical processes in • Single heating rate data
the transformation should be avoided
• Kinetic triplet-isothermal, • Model filling multi heating
poly thermal atmosphere rate data under the triplet
• Iso-conversional methods
(ozawa, Friedmann) are
sensitive to experimental
noise.

Some questions but not complete list
• What is the significance of the values of A when

they differ from the conventional expected value
of 1013 s-1?
• The value of the activation energy is not in the
range of conventional bond breaking and bond
formation. If the value were to differ considerably
what does it signify?
• When the values of A is far different very low or
very high how are they to be accounted?

The mechanism of reaction in solid state may be different
from that occurring in homogeneous systems, where
movement and collision are envisaged as initiating steps of
the reaction. In solids, the species are immobilized and
hence this type of collisions may not be the initiator of the
reaction.
The reactions ( at least some of the reactions in solid state)

may be due to bond activation through electronic energy or
through phonon activation.

If softening and melting were to precede the solid state reaction, then
one can visualize the reaction sequence as in homogeneous medium.
The variation of E with α the extent of reaction, (smooth or abrupt)
denotes the nature of consecutive steps involved in solid state
reactions.
If the solid state reaction proceeds by the development and growth of
a reaction interface, then the local strain, imperfections, the
crystalline phases of the reactants and products all will contribute to
the acceleration or deceleration of reaction rates as well as for the
change of Ea with α. It is not yet clear how the various forms of the
intervening phase, like a molten product, a defect crystalline phase or
reorganizations in react ( like removal of water) could provide a
chemical environment where the conventional Polanyi-Wigner
treatment will be as much applicable as in homogeneous phase.
In terms of energy transfer, the species in the interracial zone is more ordered in
homogeneous liquid medium, but less ordered as compared to the fully crystalline
phase. The in-between crystalline phases (interface region) may provide additional
allowed energy levein the forbidden regions of energy bands in the solid. The
electronic energy levethough normally follow Fermi-Dirac statistics, can
approximate to Maxwell-Boltzmann distribution under the temperature conditions
employed for the solid state reaction. If this situation prevaithen one can justify the
use of Arrhenius equation for evaluating Ea and pre-exponential factor.
If on the other hand phonons are the mode of activation, then one can expect the
Bose-Einstein statistics will approximate to Maxwell-Boltzmann distribution for the
conditions prevailing under reaction conditions and hence the use of Arrhenius
equation can still be justified.
Though the summary of the arguments given justify the use of Arrhenius type of
relationship to evaluate the kinetic parameters ( Ea and ln A) it has not provided
any explanation for the variation of Ea and ln A. These variations are considered
in terms of compensation between Ea and ln A, or by the variation of one ( Ea o

The linear relationship between Ea and ln A is termed as
compensation effect in the literature. The observance of this effect is
usually identified by the inherent ‘heterogeneity’ of the surface and
hence the changes in reactivity of these sites. However, a simple
linear variation between Ea and ln A for sites of varying reactivity is
not expected unless one has to invoke additional internal
reorganizations which can give rise to smooth variation in both Ea
and ln A.
It must be remarked that these solid state reactions were to involve an
intermediate vapourization and condensation steps, then it is probable
that one can still invoke Arrhenius type of equation for evaluating Ea
and ln A. However not all solid state reactions do proceed by
evaporation of reactant and condensation of the product.

It is appropriate to re-quote Flynn at this stage. He said “
the unfortunate fact is that, since in thermal analysis,
properties of the system are measured as a function of
(both) time and temperature, all thermo-analytical results
are potentially kinetic data, and many people ill grounded
on kinetics ( like the present author) feel obliged to
perform a kinetic analysis of them”

Even if one were to admit inexperience in treating kinetic data from thermal
analysis, the physical significance of the kinetic parameters derived from the
analysis is not clear yet. Secondly, it is yet to resolved, why the same experimental
data can be fitted to various mode simultaneously? Do they reflect on the
closeness of the models, or the inadequacy of the treatment of data based on the
mode chosen. The widely practiced method of extracting Arrhenius parameters
from thermal analysis experiments involves ‘force fitting’ of experimental data to
simple reaction order kinetic models. The ‘force fit’ may not be suitable for the
analysis of data of thermal analysis, outside the applicable range of variables and
hence can be of limited utility for drawing mechanistic detail of the reaction. It
should be remarked that the concept of kinetic order of the reaction has to assume
a new significance in the case of solid state reactions.
Even for simple decomposition reactions, the available mode cannot

appropriately take into account like sintering before decomposition, simultaneous
existence of polymorphic transition.
It should be recognized that the mode so far proposed, are oversimplified and
envisages one nucleation site per particle. There can be multiple and different
types of nucleation simultaneously and their growth may be a complex function
which cannot be treated in terms of simple geometrical considerations.
The direct observation of the texture and morphology of the substances have
to be coupled with the kinetic fit of the data for developing a model and draw
29th Octoberdeductions
meaningful 2008 NCCRand growth.
regarding nucleation 150
The values of the activation energy for solid state reactions can be rationalized only
in some simple restricted conditions. For example for two systems if g(α) and A
were to be equal then, the magnitude of Ea can be used to postulate on the
reaction kinetics. However, even in these cases , if Ea were to vary with α , the
fraction of the reaction, then it denotes changes in reactivity as a result of extent of
reaction and the complex nature of the reaction.
There is overwhelming tendency to compare Ea values obtained for isothermal and
non-isothermal experimental conditions. Even though time and temperature are
mathematically related by the heating rate (β = dT/dt), it is not clear how the
species of the system will respond to the bimodal variation. Whether the changes
observed will be an arithmetic sum or product of the variations observed with each
of these variables. It appears that it is neither of these two mathematical functions.
In conclusion, one can state that if carefully used and complemented with other
techniques, the analysis of solid state kinetics can provide indications on the
reaction mechanism and may yield information on reactivity which can be exploited
for synthetic strategies.

In essence, even though the thermal data is
normally kinetic in nature, the interpretation of the
data within the premises of kinetics requires
caution. Discussing reactions on the basis of one
of the kinetic triplet is not advisable. Even when
the kinetic triplet is employed it is necessary to
define them in the context of the experimentation .

Table 1. Thermal Analysis Techniques.
Abbr. Name Characteristic factor monitored
DTA, Differential thermal analysis Temperature difference between

DSC Differential scanning calorimetry sample and reference
TG Thermogravimetry Weight of sample
DTG Differential thermogravimetry Rate of weight changes
TMA Thermomechanical analysis, Specific volume of solid sample

Dilatometry
TMA Thermomagnetic analysis Magnetic susceptibility
DMC Differential microcalorimetry Enthalpy difference between

sample and reference
TPx Temperature-programmed reaction Gas composition at the reactor
(x =Reduction, Oxidation, outlet
Desorption, Sulphidation or Surface
Reaction
Table 2. Types of information obtainable from TPx techniques.
TPD, Temperature-programmed desorption
· Characterisation of adsorptive properties of materials

· Characterisation of surface acidity
· Temperature range of adsorbate release, temperatures of rate maxima
· Total desorbed amount, adsorption capacity, metal surface area and dispersion
· Surface energetic heterogeneity, binding states and energies of adsorbed molecules
· Mechanism and kinetics of adsorption and desorption
TPR, Temperature-programmed reduction

· Characterisation of redox properties of materials, .fingerprint. of sample
· Temperature range of consumption of reducing agent, temperatures of rate maxima
· Total consumption of reducing agent, valence states of metal atoms in zeolites and metal oxides
· Interaction between metal oxide and support
· Indication of alloy formation in bimetallic catalysts
· Mechanism and kinetics of reduction
TPO, Temperature-programmed oxidation
· Characterisation of redox properties of metals and metal oxides

· Characterisation of coke species in deactivated catalysts
· Total coke content in deactivated catalysts
· 29th October 2008
Mechanism NCCR
and kinetics of oxidation reactions 166
Table. 3.3 Typical experimental conditions
employed in TPX experiments
TPD TPR TPO
Gas He or N2 or Ar 5%H2/N2 5%O2/N2
composition
Flow rate 15-60 15-30 30-90

ml/min
Heating Rate 10-60 4-60 10-60
K/min
Detecting TCD or MS TCD TCD or MS
system
Temperature-Programmed Techniques
There are a range of techniques for studying surface reactions and molecular
adsorption on surfaces which utilise temperature-programming to
discriminate between processes with different activation parameters. Of these,
the most useful for single crystal studies is :

Temperature Programmed Desorption (TPD)
When the technique is applied to a system in which the adsorption process is,
at least in part, irreversible and T-programming leads to surface reactions,
then this technique is often known as :

Temperature Programmed Reaction Spectroscopy (TPRS)
However, there is no substantive difference between TPRS and TPD.
The basic experiment is very simple, involving
Adsorption of one or more molecular species onto the sample surface at low
temperature (frequently 300 K, but sometimes sub-ambient).
Heating of the sample in a controlled manner (preferably so as to give a linear
temperature ramp) whilst monitoring the evolution of species from the
surface back into the gas phase.
The basic experiment is very simple, involving
Adsorption of one or more molecular species onto the sample surface

at low temperature (frequently 300 K, but sometimes sub-ambient).
Heating of the sample in a controlled manner (preferably so as to

give a linear temperature ramp) whilst monitoring the evolution of
species from the surface back into the gas phase.

In modern implementations of the technique the detector of choice is a small,
quadrupole mass spectrometer (QMS) and the whole process is carried out under
computer control with quasi-simultaneous monitoring of a large number of
possible products.

The data obtained from such an experiment consists of the intensity variation of
each recorded mass fragment as a function of time / temperature. In the case of a
simple reversible adsorption process it may only be necessary to record one
signal - that attributable to the molecular ion of the adsorbate concerned.

The graph below shows data from a TPD experiment following adsorption of CO
onto a Pd(111) crystal at 300 K.

Since mass spectrometric detection is used the sensitivity of the technique is

good with attainable detection limits below 0.1% of a monolayer of adsorbate

The following points are worth noting :
The area under a peak is proportional to the amount originally
adsorbed, i.e. proportional to the surface coverage.
The kinetics of desorption (obtained from the peak profile and the
coverage dependence of the desorption characteristics) give
information on the state of aggregation of the adsorbed species e.g.
molecular v's dissociative.
The position of the peak (the peak temperature) is related to the
enthalpy of adsorption, i.e. to the strength of binding to the surface.
One implication of the last point, is that if there is more than one
binding state for a molecule on a surface (and these have
significantly different adsorption enthalpies) then this will give rise
to multiple peaks in the TPD spectrum.

The graph below shows data from a TPD experiment following
adsorption of oxygen on Pt(111) at 80 K.

Which peak correspond

s to the state which is m
ore weakly adsorbed
29th October 2008 ?
NCCR 173
The peak at ca. 140 K corresponds to desorption of the more weakly bound state.
Rationale
The more weakly bound

state has the lower
activation energy for

desorption and will
therefore undergo
desorption at a lower
temperature.
The two peaks correspond
to the presence of both
molecularly and atomically
(i.e. dissociatively)
adsorbed oxygen on the
surface.
The molecular species is
the more weakly adsorbed.

Theory of TPD
As discussed in Section 2.6, the rate of desorption of a surface species will in
general be given by an expression of the form :
Rdes =  . Nx exp ( - Eades / R T ) [1]
Rdes - desorption rate ( = -dN/dt )

where
x - kinetic order of desorption (typically 0,1

or 2)
Eades - activation energy for desorption
In a temperature programmed desorption experiment in which the temperature is increased linearly

with time from some initial temperature To , then :
T = To + .t and dT = .dt [2]
The intensity of the desorption signal, I(T) , is proportional to the rate at which the surface
concentration of adsorbed species is decreasing. This is obtained by combining [1] and [2] to give

combining [1] and [2] to give
[3]
This problem may also be considered in a rather simplistic graphical way -the key to
this is to recognise that the expression for the desorption signal given in the above
equation is basically a product of a coverage term ( N x - where N depends on T ) and
an exponential term (involving both Ea and T ).
Initially, at low temperatures Ea >> RT and the exponential term is vanishingly small.
However, as the temperature is increased this term begins to increase very rapidly
when the value of RT approaches that of the activation energy, Ea .

29th October 2008 NCCR

176
By contrast, the pre-exponential term is dependent upon the
coverage, N(T), at the temperature concerned - this term will remain
at the initial value until the desorption rate becomes of significance
as a result of the increasing exponential term. Thereafter, it will
decrease ever more rapidly until the coverage is reduced to zero.
The shaded area is an approximate representation of the product of
these two functions, and hence also an approximate representation
for the desorption signal itself - whilst this illustration may be
overly simplistic it does clearly show why the desorption process
gives rise to a well-defined desorption peak.
If you wish to see exactly how the various factors such as the
kinetic order and initial coverage influence the desorption profile
then try out the
Interactive Demonstration of Temperature Programmed Desorption
; we will however continue to look at one particular case in a little
more detail.
CASE I (Molecular adsorption) - in this case the desorption kinetics will
usually be first order (i.e. x = 1 )
The maximum desorption signal in the I(T) trace will occur when ( dI / dT ) =
0,
i.e. when

Hence , remembering that the surface coverage changes with temperature
i.e. N = N(T),


where we have substituted Ea for Eades purely for clarity of presentation.
Substituting for dN/dT from eqtn.[3] then gives

The solution is given by setting the expression in square brackets to be equal to
zero , i.e.

where we have now defined the temperature at which the desorption maximum
occurs to be T = Tp (the peak temperature ).

Unfortunately, this equation cannot be re-arranged to make Tp the
subject (i.e. to give a simple expression of the form Tp = .....), but
we can note that :
as Eades (the activation energy for desorption) increases, then so Tp
(the peak temperature) increases.
the peak temperature is not dependent upon, and consequently does
not change with, the initial coverage, Nt=0 .
the shape of the desorption peak will tend to be asymmetric, with
the signal decreasing rapidly after the desorption maximum.


Temperature Programmed Reaction Spectroscopy
In TPRS a number of desorption products will normally be detected in any
one experiment - this is where mass spectrometric detection and multiple ion
monitoring really becomes essential.
A good example of TPRS results are those obtained from dosing formic acid
( HCOOH ) onto a copper surface.


The spectra contain two regions of interest - the first at around room temperature
where there is desorption of hydrogen (m/z = 2) alone, and the second between
400 & 500 K where there are coincident desorption peaks attributable to hydrogen
and carbon dioxide (m/z = 44).
The lower temperature hydrogen peak is at about the same temperature at which
hydrogen atoms recombine and desorb as molecular hydrogen from a hydrogen-
dosed Cu(110) surface i.e. the kinetics of its evolution into the gas phase are those
of the normal recombinative desorption process. By contrast, the higher
temperature hydrogen peak is observed well above the normal hydrogen
desorption temperature - its appearance must be governed by the kinetics of
decomposition of another surface species. The carbon dioxide peak must also be
decomposition limited since on clean Cu(110) carbon dioxide itself is only weakly
physisorbed at very low temperatures.
More generally, you should note that coincident desorption of two species at
temperatures well above their normal desorption temperatures is characteristic of
the decomposition of a more complex surface species.

Recombination and
desorption of this hydrogen
(at ca. 280 K)

H(ads) + H(ads)  H2 (g)
leaves only the formate
species on the surface.
The formate species is
stable to relatively high
temperatures but
eventually decomposes
yielding the observed
coincident desorption of
hydrogen and carbon
dioxide.
The hydrogen trace thus contains examples of both a desorption limited peak (at
ca. 280 K) and a decomposition limited peak (at ca. 440-470 K)
TEMPERATURE-
PROGRAMMED TECHNIQUES
RECENT TRENDS AND
FURTURE PROSPECTS

INFLUENCE OF PARTICLE SIZE
Calculated TPD curve for desorption from
A bed of catalyst. The sample is assumed
To be made up of spherical particles, with
Half of the mass with particles with a dia of
100 µm and the other half with a dia of 10
µm
Temperature
VACUUM VS CARRIER GAS
• NH3 ON HSZM-5 : DIFFERENCE COULD
BE150 K
• METHANOL AND ACETONE FROM
HZSM-5:
– BOTH DESORB LARGELY INTACT IN
VACUUM
– BUT REACT TO GIVE A RANGE OF
HYDROCARBON PRODUCTS USING A
CARRIER GAS
DESIGN EXPERIMENTS TO TAKE ADVANTAGE
OF THE OPTIONS AVAILABLE
1. TEMPERATURE RAMP AND HOLD-UP

IN SAMPLE CHARACTERIZATION
1. INTRODUCTION OF A GAS, INERT OR REACTIVE AT
DESIRED TIME AND TEMPERATURE
EXAMPLE:
COKING OF A ZEOILTE CATALYST USING AN OLEFIN (1-PENTENE)
A HYDROCARBON (N-HEPTANE) OR AN AROMATIC (ETHYLBENZENE)
STUDY:
A) COKE PRECURSORS;
B) SMALL COKE PRECURSORS;
C) LARGE COKE PRECURSORS;
D) HARD COKE
E) TOTAL COKE
B. Wang and G. Manos, J. Catal., 250 (2007) 121

MULTIPULSE AND DESORPTION
EXPERIMENTS
• CERTAIN NUMBER OF PULSES (50-100) IN AN INERT
(He) FLOW AT CERTAIN TEMPERATURE
• TEMP.RAMP TO FOLLOW DESORPTION OF THE
SURFACE BOUND SPECIES FORMED DURING THE
PULSES
• EXAMPLE: Fe-ZSM-5 and N2O Interaction
Formation of monoatomic surface oxygen species (α-
oxygen), extremely high reactivity for the oxidation of CO,
H2 and hydrocarbons including benzene and CH4, even at
room temperature.
Ref: The Interaction of N2O with ZSM-5-type Zeolites:

A Transient, multipulse investigation
A. Ates and A. Reirsmann,
29th October 2008 NCCR
J. Catal., 235 (2005) 164
189
MULTIPULSE AND DESORPTION
EXPERIMENTS

ACID-BASE PROPERTIES
• BOTH ACID AND BASE SITES ON THE CATALYST
SURFACE ARE IMPORTANT
• MANY OXIDES, MIXED OXIDES HAVE ACID-BASE
PAIRS ON THE SURFACE TUNED TO EFFECT AN
INITIAL ADSORPTION OF THE SUBSTRATES
• EQUAL EMPHASIS SHOULD BE GIVEN FOR THE
CHARACTERIZATION OF THE BASIC SITES
• TPD OF NH3 AND TPD OF CO2
• CORRELATION OF CATALYTIC ACTIVITY WITH
ACIDITY AS WELL AS BASICITY
Ref: Direct synthesis of dimethyl carbonate from methanol
and carbon dioxide
Kyung
29th October 2008 Won La et al J. Mol.Catal.A.,
NCCR 269 (2007) 41 193
CORRELATION OF CATALYTIC ACTIVITY WITH ACIDITY
AS WELL AS BASICITY

IRMS-TPD OF AMMONIA: DIRECT AND
INDIVIDUAL MEASUREMENT OF BRØNSTED
ACIDITY IN ZEOLITES
• IT IS IMPOSSIBLE TO DIFFERENTIATE BETWEEN BRONSTED AND
LEWIS ACID SITES WITH NH3 TPD, WHICH DOES NOT PROVIDE
INFORMATION ABOUT THE ACID SITES AT MOLECULAR LEVEL.
• IR OF ADSORBED PYRIDINE MUST BE MEASURED.
• GLASS VACUUM SYSTEM WITH IR AND MS SPECTROMETERS.
• MEASURED ∆H (ENTHALPY CHANGE OF NH3 ADSORPTION) AS A
PARAMETER OF STRENGTH WAS CORRELATED WITH THE IR BAND
POSITIONOF OH, THE LOWER THE WAVE NUMBER OF OH BAND
POSITION, THE STRONGER THE ∆H.
• A LINEAR CORRELATION BETWEEN ∆H WITH BAND POSITION OF
OH LOCATED IN 12- AND 10-MEMBER RINGS OF ZEOLITES.
• DETECTION OF 4 KINDS OF OH IN Y-ZEOLITE, THEIR POSITIONS AND
ACID SITE STRENGTH WERE STUDIED.
• MEASURED TOF (OCTANE CRACKING) RELATED STRONGLY WITH
THE ∆H OF THE BRONSTED SITES.
Ref: M. Niwa, K. Suzuki et al., J.Phys.Chem.B, 109 (2005)18749;

J. Phys.Chem.C.,111(2007) 894;
29th October 2008 J. Catal., 250 (2007)151.
NCCR 195
J. Catal., 85 (1984) 362.
SURFACE AREA OF
MONOLAYER OXIDES
• TITANIA ON SILICA: TITANIA IS A
STRONGER LWEWIS ACID
• ADSORPTION OF 2-PROPANOL WHICH
DEHDRATES CONSIDERABLY AT
LOWER TEMPERATURE FOR TITANIA:
TPD WITH MS (m/e = 41, propene) at
200C for titania and > 450C for silica
• TITANIA SURFAE AREA: 1.8 X 1018
molecules of 2-propanol per m2
Determination of Brönsted acid
sites
• Isorpropyl amine on HZSM-5: takes up a
H+ and decompose to give propene and
NH3
• Combined TG and TPD (mass spec)
• Desorption of propene and NH3 around
575-650K
• This reaction is insensitive to Lewis sites

NOx STORAGE AND
DECOMPOSITION

BASICITY, CO2-PHILICITY AND
STRENGTH
• DIFFERENCE BETWEEN
MgO, γ-alumina, and meso alumina from
• TPD of CO2(Vacuum system with QMS)
• Pre-evacuation of CO2 at RT for 30 min
 CO2 –philicity: MgO>>γ-Al2O3>mesoAl2O3
• Pre-evacuation of CO2 at 673K for 5 min
 Strong basic sites: meso Al2O3> γ-Al2O3
 Knoevenagel reaction in ScCO2 medium: the activity
increases in the order: MgO << γ-Al2O3
< mesoAl2O3
Ref: Elucidation of basic properties of mesoporous alumina

29thT. Seki
October and M. Onaka, J.Mol.Catal.A.,
2008 NCCR 263 (2007) 115 203
BASICITY, CO2-PHILICITY AND
STRENGTH

• Introduction of transition metal cations results in
the formation of active sites responsible for the
formation single step, double exchange between
gas pahse oxygen and lattice oxygen.
• The activity for facilitating single step, double
exchange between gas phase 18O2 and lattice
oxygen(16O) and activity for oxydehydrogenation
of ethane to ethylene decrease in the same
order, Co-H-ZSM-5 > Cu-Na-ZSM-5 > V-ZSM-5
>Nb-ZSM-5 > Na-ZSM-5 ~H-ZSM-5~Cu-ZSM-5
Y.F. Chang,
29th October G.A. Somorjai and H.
2008 Heinemann, J. Catal., 154 (1995)205
NCCR 24
A Highly Sensitive Detection Method for
Temperature Programmed Oxidation of Coke Deposits:
Methanation of CO2 in the Presence of 02
29th October
S. C.2008
FUNG NCCR
AND C. A. QUERINI, J. Catal., 138 (1992) 240 206
Temperature Programmed Oxidation of Coke
Deposits

HIGH PRESSURE TPR OF
SULFIDED CATALYSTS
• A NEW GENERATION OF EQUIPMENT
WORKING UNDER CONDITIONS
APPROACHING THOSE USED IN REALITY
• BASIC HYDRODYNAMIC CONSIDERATIONS
EMPLOYED FOR CORRECTING THE SIGNAL
FROM THE VARIATIONS OF THE RESIDENCE
TIME DISTRIBUTION OF THE MOELCULESS
IN THE REACTOR
• WHEN RAW SIGNALS ARE SUITABLY
CORRECTED, THE HYDROGEN PRESSURE
DOES NOT INFLUENCE THE TPR PATTERNS
HIGH PRESSURE TPR

TPR CORRECTIONS FOR HIGH
PRESSURE CONDITIONS

KINETIC MODELS FOR POROUS
CATALYSTS
• Desorption can never be described by simple first order
or second order kinetics;
• Rate constant be coverage dependent;
• Partial pressure is not directly related to the intrinsic
desorption rate;
• Ads-Des in equilibrium or quasi equilibrium
• Diffusion limits the desorption process;
• Under flow or vac. conditions, readsorption cannot be
neglected;
• Peak max in the TPD curve could be shifted by hundreds
of degrees due to readsorption, coupled with diffusion,
even when the sample is placed in ultra high vacuum
KINETIC MODELS (CONTINUED)
• Simultaneous desorption, adsorption and diffusion from a
catalyst pellet: CSTR or PFR model?
• Desorption model using six dimensionless groups of
measuable experimental variables (Demmin and Gorte);
• Desorption is in the diffusion-limited regime; Internal
diffusion is much slower than desorption or readsorption.
• A complete heterogeneous TPD simulation model;
• It is possible to adjust experimental conditions and
properties to collect experimental TPD data undisguised
by intraparticle diffusion limitations, and apply a pseudo-
homogeneous model in kinetic analysis.
Ref: R.J. Gorte, Catal. Today, 28 (1996) 405

TECHNIQUES FOR CHEMICAL ANALYSIS TPX Techniques

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TECHNIQUES FOR CHEMICAL ANALYSIS TPX Techniques

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TECHNIQUES FOR

EMS Electron Momentum Spectroscopy

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Thermo gravimetric analysis (TGA)- Monitoring the change of

Differential Thermal analysis (DTA)-Change in thermal energy as

Differential scanning calorimetry (DSC)- Change in heat as a

4. Thermomechanical analysis (TMA)- Change of dimensions.

There are other techniques such as Electrothermal analysis,

Exotherm T > 0 Exo

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1. Determination of thermal constants,

2. Phase changes and phase equilibria

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Vacuum connection and purge gas inlet

The current produced is proportional to the change in sample

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Ca, Sr and Ba are

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• Better controlled atmosphere (inert) specially at higher

• Typical purge gas flow rate for small furnace : 60

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200 400 600 800 1000

TG Analyzer Purge Capillary Gas Analyzer

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Reference DSC/DTA mean values, oC

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 Investigation of surface structures is important for optimum design

Transport of reactants to surface of the catalyst.

29th October 2008 NCCR 53

 Alternately a carrier gas containing the desired species is used

There are many variants

29th October 2008 NCCR 54

Thermo analytical Analytical Instrumentation

Change in weight Thermogravimetry

Change in energy DTA, DSC

Evolved gas analysis Temperature programmed

Developed by Cvetanovic and

Cold trap for TPR.

Starting temp is below

29th October 2008 NCCR 61

dn/dt – rate of reduction

The parameters that determine the

For heating rates between 6-20 oC/min

Typee of red solids

(a) Bulk reducible compounds:

(b) Supported reducible species: