Methods of Thermal Analysis€¦ · Fire is the general analysator of matter. ... manner as can be...
Transcript of Methods of Thermal Analysis€¦ · Fire is the general analysator of matter. ... manner as can be...
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Methods of Thermal Analysis
Michael Feist
Berlin Humboldt University, Institute of Chemistry
1. Conventional Thermal Analysis
2. Simultaneous Thermal Analysis
3. Hyphenated techniques in Thermal Analysis (EGA)
4. PulseTA® and catalysis
5. Determination of other thermal properties
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1. Conventional Thermal Analysis
History
Cooling curves
The phase rule
Measuring principles of DTA and DSC
Information content
Sample carriers
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Aristoteles (384-322 B.C.)
Fire is the general analysator of matter.
Robert Boyle „The Sceptical Chemist“ (1661):
No, it is not, because it is destructive.
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Thermal analysis: T = f(t)
∆T = f(t or T)Following the change of a physical property of asubstance subjected to a controlled heating programdepending on time or temperature.
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Joseph Black (1728-1799)
Latent heat
Antoine L. Lavoisier (1743-1794)
Mass balance of chemical reactions
Henri-Louis LeChatelier (1850-1936)
Pt - PtRh10 thermocouple for measuring T (1887)
William C. Roberts-Austen (1843-1902)
Differential measuring setup with inert reference (1899)
Josiah Willard Gibbs (1839-1903)
The phase rule F = K - P +1 (for p=const)
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In many cases, the temperature-depending change of properties characterize a substance in the same unequivocal manner as can be done by its formula or its structure.
K. Heide (1982)
The subject investigated: A phase or a phase mixture
Changing temperature changes the phase state which yields
Information about purity
state diagrams
material constants
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ThermogravimetryTG
Mass
DifferentialScanning Calorimetry
DSC
DifferentialThermal Analysis
DTA
TemperatureHeat flow
Thermosonimetry
Thermooptical AnalysisTOA
ThermomechanicalAnalysis
TMA
ThermodilatometryTD
Other parameterse.g. length
Thermal Analysis
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Classical thermal analysis -
Heating and cooling curves of one-component systems
T T
t t
m.p.
melting solidification
F=1
F=0
F=1
second phase appears
F = K - P + 2 - E E = 1 for p=const
F = K - P + 1
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Differential measuring setup - Generation of the DTA signal
Asymmetricsignal shape
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The information contained in the DTA signal
h = u + pvdh = du + pdv + vdp
du = dq - pdvdq = du + pdv
dh = dq + vdpvdp = 0
dh = dqP
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DTA sample holders
Pt or Al2O3crucibles (baker)
Metal block with symmetric holes
Pt or Al2O3 crucibles with „crucible shoes“ as thermocouples
Rapidly ∆T=0 :High resolution
„Slower“ :High sensitivity
Minimal sample mass
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Heating of the environment(oven) - sample and measuring system follow passively; Sample and refence areconnected via a gold band which sets ∆T=0
Variable heat flow from separate heaters to maintain ∆T=0
Difference in heating power is the measuring signal
Differential Scanning Calorimetry
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2. Simultaneous Thermal Analysis
Heating and cooling (CsFeF4 ·2 H2O)
Repeated heating runs (NaClO4 · H2O)
Gas changes (Coal)
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TG
DTG
DTA
2mg
0,4mg/min
4µV
T
-10,76 %
81107
597
606659
676
687
636
638 595
594
100 300 500 700 700 600T / °C
heating cooling
CsFeF4 · 2 H2O
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301
54
55150
308
307
303
303305144
4,33%
7,91%
TG
DTA
DTA
TG
n(H2O)
1
0,5
0
1st + 2nd heatingin N2
1st coolingin N2
2 hrs isothermallyin moist air
T
endo
T
TG
NaClO4 · H2O
T / °C
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TG-Analysis of coal with changing atmosphere
One TA run -
Four parameterscharacterizinga natural product
Ottaway (1981)
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S
SS
O OO
O
O
O
O NN+
N–
N+N
–N
NN+
N– hν, ∆
- 3 N2
S
SS
O OO
O
O
O
O N
N
N
Explosive decompositionof a Tris-azide at 130°C15 mg sample
C24H15S3O7N9 25,55% N
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3. Hyphenated Techniques in Thermal Analysis (EGA)
Gas flow in thermobalances
Pressure reduction and unfalsified gas transfer
Coupling systems in TA-MS
Examples
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Speed and Flow ⇒ delay in detection ?
Flow profile ⇒ laminar, turbulent ?Distribution of evolved gases inpurge gas stream
Flow direction ⇒ influence of convectionControlled convection in verticalTG systems (chimney effect)
Temperature gradients
Position of transfer line connection
Gas flow in thermobalances -The influence of transport conditions
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Pressure reduction
103 mbar → 10-5 mbar
Condensation and secondary reactionsUnfalsified gas transferDifferent viscosity - Demixing
Attribution to a chemical processPyrolysis or Evaporation ?
Fragmentation in MS or sample behavior ?
Three main problems for TA-MS coupling devices
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OrificeValve
Throttle
Pump
Capillary
AdapterMS
Capillary Coupled System 2400°C
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MS analysator
Overflow
Orifice 2
Orifice 1
Cooling Trap Orifice Coupling System
1500°C
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MS analysator
Orifice 2 Skimmer
Orifice 1
Skimmer Coupling System
Overflow
1500°C
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NETZSCHSTA 409 C Skimmer®
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Amorphous ZrO2 · n H2O → ZrO2 (tetragonal)
-40
-20
0
20
40
DTA /uV
75
80
85
90
95
100
TG /%
100 200 300 400 500 600 700Temperature /°C
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
Ionenstrom *10-9 /Am18 H2O
m44 CO2
m17 OH
TG
DTG
DTA
-4.89
-8.77-0.97
426
↑ Exo
Dehydratation,Dehydroxylation
Squeezing out of residualH2O and CO2 moleculesduring the crystallization
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0
0.2
0.4
0.6
0.8
1.0
Ionenstrom *10 -9 /A
50 100 150 200 250Temperatur /°C
60.0
65.0
70.0
75.0
80.0
85.0
90.0
95.0
100.0
TG /%
m18
m28
Santos D2O Bohne(in Ar / 20%O2)
m44
m19
TG
196 °C
196 °C
214 °C
Simulation of the roasting of coffee beans
Corundum platecrucible, Pt netArgon / 20% O2
m/z 18 (H2O+) m/z 28 (CO+, N2+)
m/z 19 (HDO+) m/z 44 (CO2+, ... )
m/z 20 (D2O+, Ar++)
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m/z 28 (12CO+, 14N2+)
m/z 29 (13CO+, 14N15N+)
i28 : i29 = 16 : 1
65
70
75
80
85
90
95
100
TG /%
50 100 150 200 250Temperatur /°C
0
1.0
2.0
3.0
4.0
5.0
[4]Ionenstrom *10 -10 /A
m28
m29 (x10)
Santos D2O Bohne(in Ar / 20%O2)
m44TG
196 °C
215 °C
• No discrimination between CO and N2• Bean bursts due to water pressure
• Decarboxylation at higher temperature
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m/z 68 (C3H4N2+, ... )
m/z 80 (C6H4N2+, ... )
m/z 109 (coff)
m/z 194 (coffM+)
• MAILLARD products together with CO2• Three roasting stages
• Coffeine partially evaporates
0
0.5
1.0
1.5
Ionenstrom *10 -12 /A
50 100 150 200 250Temperatur /°C
60.0
65.0
70.0
75.0
80.0
85.0
90.0
95.0
100.0
TG /%
Santos D2O Bohne(in Ar / 20%O2)
m80
m68
m109
m194
TG
196 °C
214 °C
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4. Pulse Thermal Analysis® and Catalysis
Quantitative evaluation of MS or FT-IR signals
Taylor made redox catalysts
Applications
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Maciejewski et al. (1997)
PulseTA® with aNETZSCHSTA 409 C Skimmer®
Injection of known voluminaof one or two gases
Quantitative evaluation ofMS and FT-IR signals
Appropriate m/z⇒ chemical composition
TG ⇒ sorption phenomena
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Calibration of MS signals for PulseTA® Maciejewski et al. (1997)
1. On line
2 NaHCO3 → Na2CO3 + CO2 + H2O
2 PdO → Pd + O2
2. Off line
Injectionof a known gas volume into the purge gas
SeparateTA run of a suitable calibration substance
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Taylor made catalysts with PulseTA® (1)
Maciejewski et al. (1997)
Reduction of CuO
by H2 pulses at 450°C
Oxidation of Pd/ZrO2by O2 pulses at 100°C
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Taylor made catalysts with PulseTA® (2)
Maciejewski et al. (1997)
Reduction of PdO/ZrO2by CH4 pulses
and its subsequent
re-oxidation
by O2 pulses at 500°C
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Mass change of H-ZSM-5 zeolite after pulses of 1 ml NH3 at 200°C
Chemisorption and Physisorption studied by PulseTA®
Eigenmann et al. (2000)
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The HTB structure of β-CrF3 (hexagonal tungsten bronze)
De Pape et al. (1987)
• (CrF6) octahedra
• Hexagonal channels
• Hosting of small molecules
(NH4)3CrF6β-CrF3 · n NH3
β-CrF3 Menz & Bentrup (1992)
β-CrF3 · m H2O · n NH3
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PulseTA Calibration of m19with NaHF2 · n H2O
m/z 20 HF+ H218O+ Ar++
m/z 19 F+
NaHF2 · n H2O → NaF + HF + n H2O
(1) Determination of mH2O by PTA after calibration of m/z 18 with NaHCO3
(2) Calculation of mHF using the residue mass
msample = mNaF + mHF + mH2O (3) Calibration factor:
= 1,21mg
0,236 10 As6⋅ − = 5,127 ⋅ 106 mg/As
F HF( ) = mHF calA cal
( )( )m19
100 200 300 400
0,0
0,5
1,00,12 H2O
=0,149 mgA sAm18=0,188 10
-6
A sAm19=0,236 10-6
I.C.
10-9 [
A ]
T [ °C]
70
80
90
100
in N2
NaF + HF + 0,12H2O
Ton112
endo
.0,12 H2ONaHF2
30,07%
DTA
TG
∆m/m
[%]
m20m19
m18
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100 200 300 400 500 600 700
0
1
2
3
I.C. [
10 -9
A]
T [ °C]
92
94
96
98
100
0,05 H2O .
DTG
endo
599
Te 593
. 0,06 NH3β-CrF3
0,27mg
1,25mg
0.40mgDTA
TG
∆m/m
[%]
1,22mg
0,10mg0,21mg
151917
18
5x
in Ar • Water release in threetemperature ranges
• Slight endothermal shiftdue to pyrohydrolysis
• β-CrF3 structure collapsesat 593°C ⇒ NH3 loss
• Major part of NH3 lost onlybetween 589 and 604°C
Quantitative descriptionof all details of the thermalbehavior of a fluoride beingsensitive to hydrolysis
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1. Transformation of unwanted CFC's
Chlorofluorocarbon (CFC) ⇒ Hydrofluorocarbon (HFC)
Substitution of refrigerants Recycling of refrigerators
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Hydrodechlorination Removal of Cl from C-Clby use of H2 Replacing Cl with H
Dehydrochlorination Elimination of HCl
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1,1 Dichlorotetrafluoroethane , CF3-CCl2F (CFC-114a)
Nomenclature: 1 1 4 aC-1 H+1 F (Cl = rest)
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The HTB structure of β-AlF3 (hexagonal tungsten bronze)
De Pape et al. (1987)
• (AlF6) octahedra
• Hexagonal channels
• Strong LEWIS acid sites
• Hosting of small molecules
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Catalytic hydrodechlorination of CFC-114a -
via stepwise or carbene mechanism
CF3-CCl2F + n H2
CF3-CH2FHFC-134a
CF3-CH3HFC-143a
CF3-CHClFHCFC-124
CF3-CF:
- 2 HCl
- HCl- HF
- HCl
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CF3-CCl2F R114a
CF3-CHClF R124
CF3-CH2F R134a
CF3-CH3 R143a
Fragment
31 (52) 31 (49) 31 (18) 31 (12) CF+
- - 33 (100) 33 (8) CH2F+
- - 34 (100) 34 (8) CHDF+
35 (18) 35 (8) 35 (100) 35 (8) CD2F+ , 35Cl+
- 51 (52) 51 (20) 51 (3) CHF2+
- 52 (52) 52 (20) - CDF2+
- - - 65 (40) CH3CF2+
- 67 (100) - 67 (40) CHClF+, CHD2CF2+
68 (8) 68 (100) - - CDClF+ , C37ClF+
69 (40) 69 (27) 69 (72) 69 (100) CF3+
83 (5) - 83 (65) 83 (2) CF3CH2+
85 (57) 85 (1) 85 (65) - CF3CD2+ , CClF2+
101 (80) 101 (40) 101 (1) - CCl2F+ , CF3CHF+
- 102 (40) 102 (1) - CF3CDF+, CF3CH2F+
135 (100) - - - CF3CClF+
Discrimination
of HFC‘s
via
characteristic
mass numbers
Why D2 used ?
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Why D2 used ? (2)
to distinguish the main reaction (DCl) from side reactions (HCl)
m/z 39 (D37Cl+)
(1) Reaction of the freon with Al-OH groupsCF3-CCl2F + 4 OH- → CO2 + CO + 4 F- + 2 HCl + H2O
(2) Reaction of D2 with neighboured surfacial Al-OH groups
D• … HO D• … DO Pd Al → Pd Al + H D
Side reactions :
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Main steps of a PulseTA experimentcharacterizing a Pd/β-AlF3 catalyst
1. Thermal pretreatment in N2 at 300°C
2. Cooling down to 25°C
3. CFC pulse at 25°CMS : m/z in SIM modeTG : Chemi- / Physisorption ?
4. D2 pulse at 25°CTG: Chemisorption: activated D...D
5. Heating in N2 with 10K/min up to 270°C withPulses of CFC and/or D2
MS : Products ?
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0 20 40 60 80
Ion
curr
ent /
A
m102 (x5)
m18
m33 (x1000)
Time / min
92
94
96
98
100
T
TG
m101
0
100
200
300
∆m/%
1E-9
T/°C
m34 (x1000)
m39 (x1000)
ß-AlF3/Pd + R114a 5E-11
• Freon pulses only
• m101 (CCl2F+) = CFC-114a
• No educt consumption
• No product formation
• Temporary buoyancy effects (freon density)
• No adsorption
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• Freon and D2 pulsedsimultaneously
• First educt pulse:chemisorption of D2
• Physisorption of productsat higher T
• Water as byproduct
0 20 40 60 80
E-10
T/°C
Time / min
Ion
curr
ent /
A
ß-AlF3/Pd + R114a / D2
m102 (x5)
m33 (x10)
m34
92
94
96
98
100
E-9
TG0,24%
∆m/%
(x10)m18
m101
0
100
200
300
m39 (x0.5)
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0 20 40 60 80
ß-AlF3/Pd + R114a / D2
Time / min
Ion
curr
ent /
A
E-11m68(x0.1)
m65(x0.5)
92
94
96
98
100
T/°C∆m/%
m20(x0.1)
m4
TG
0
100
200
300
T
0.06mg
5E-10
0 20 40 60 800 20 40 60 80
m52(x0.5)
0 20 40 60 80
• m4 (D2+): educt consumption
• m20 (HF+): byproduct
• m65 (CH3CF+): formation ofhydrogenated products
• m52 (CDF2+): bothHCFC-124 and HFC-134a
⇓m102 (CF3CDF+, CF3CH2F+)remains const and low
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Catalytic hydrodechlorination of CFC-114a -
via stepwise or carbene mechanism
CF3-CCl2F + n H2
CF3-CH2FHFC-134a
CF3-CH3HFC-143a
CF3-CHClFHCFC-124
CF3-CF:
- 2 HCl
- HCl- HF
- HCl
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0 20 40 60 80
R143a
Time / min
ß-AlF3/Pd + R134a / D2
DFm21
m65
92
96
100
2E-9
0.06mg
R134am33
TG
0
100
200
300
400T/°C
5E-12
∆m/%
0 20 40 60 80
Pulsing the intermediateHFC-134a
• m33 (CH2F+): no consumptn.
• m21 (DF+): no reaction
• m65 (CH3CF+): no formationof HFC-143a
⇓No direct transformationof HFC-134a into 143a -
Confirms the carbene mechanism.
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5. Other thermal properties
Heat capacity
Thermal diffusivity
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3 step procedure fordetermination of Cpby DSC :Heat flow rate of1. Empty crucibles2. Calibr. substance R3. Sample S
Höhne, Hemminger, Flammersheim (1996)
β⋅−=−==∆ )(d
dd
d- RSRRSSRSSR CCtTC
tTCΦΦΦ
β - average heating rate(different heating ratesof sample and reference)
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Thermal diffusivity - The Laser Flash Method (1)
ρλ
pctT =
∂∂
q = - λ grad THeat flow
Thermal diffusivity
T = T(x,y,z)λ - thermal conductivity
cp - heat capacityρ - density
Temperatureresponse
Sample diskLaser flash
T = f(t)
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Thermal diffusivity - The Laser Flash Method (2)
The t1/2 method
2/1
21388.0
tda ⋅=
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Thermal diffusivity - The Laser Flash Method (3)