Thermal Analysis

Terry A. Ring
Chemical Engineering
University of Utah
 Different Techniques
• Thermometric Titration (TT)
– Heat of mixing
• Thermal Mechanical Analysis (TMA)
– Thermal Expansion Coefficient
• Dynamic Mechanical Analysis (DMA)
– Viscoelastic Properties
• Differential Scanning Calorimetric (DSC)
– Heat flow during Transitions
• Thermal Gravimetric Analysis (TGA)
– Weight Loss due to decomposition
– Derivative Thermogravimetric Analysis (DTG)
• Differential Thermal Analysis (DTA)
– Heat of Transitions
• Temperature Programmed Desorption (TPD)
– Temperature at which gas is desorbed from (catalyst) surface
– Emission gas Thermoanalysis (EGT)
 Basic Principle
• Sample is heated at a constant heating
rate
• Sample’s Property Measured
– Wt TGA
– Size TMA
– Heat Flow DSC
– Temp DTA
– Gas evolved TPD
 TGA
• Constant Heating
Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Weight vs Time
– Weight vs Temp.
• Differential This Data
(DTG)
DSC
 DSC
• Constant Heating Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Heat flow to sample minus
Heat flow to reference vs
Time (Temp.)
• Measures heat of
crystallization

Polymer without weight change in this temperature range

 DTA
• Sample and Reference Placed in Heater
• Constant Heating Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Temp of Sample vs Time (or Temp)
– Temp of Reference vs Time (or Temp)
– Reference should be inert, e.g. nothing but latent heat
• Measures
– Heat of crystallization
– Glass Transition Temperature
DTA + DTG
 TMA
• Constant Heating Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Size of Sample vs Time (or Temp.)
• Measures
– Thermal Expansion Coefficient
– Volume change on crystalization or crystal
transformations
– Sintering
– Glass Transitions in Polymers
 TMA

Polymer with glass transition

 DMA
• Constant Heating Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Force vs Time (or Temp.)
– Force delay vs Time (or
Temp.)
– Viscoelastic Properties
• Storage and Loss
Modulus
• Measures
– Glass Transition
Polymer with Glass Transition
– Viscoelastic Properties
 We have TGA - only
• Heating a sample of Calcium oxalate

• Ca(C204)*xH2O  Ca(C204) *H2O + x-1 H2O

• Ca(C204)*H2O Ca(C204) + H2O
• Ca(C204)  CaCO3 + CO
• CaCO3  CaO + CO2
 TGA
• Constant Heating
Rate
– Initial Temp
– Final Temp
– Heating Rate (°C/min)
• Data
– Weight vs Time
– Weight vs Temp.
• Differential This Data
(DTG)
TGA – Ca(C204)*xH2O
Different Heating Rates
 Heating Rate
• Heating Too Fast
– Overlaps Transitions
• Interpretation Problems
• Kinetics of Decomposition
– Sample Size
– Mass Transfer
• Convective Mass Transfer
• Pore Diffusion
– Heat Transfer
• Convective Heat Transfer
• Thermal Conductivity
– Porous solid
Precipitated Zr5O8(SO4)2*15 H2O

This sample was dried fro 48 hrs at 110C before TGA analysis.
What is going on?
 Analysis of Filtrate from
Precipitation
• Precipitation 15 H2O Water Loss Wt. Loss % loss
1 18.0152 1.721573
• 5ZrOCl2 + 2H2SO4 + xH2O  2 36.0304 3.443146
Zr5O8(SO4)2*15 H2O (s) + 10 HCl 3 54.0456 5.164719
4 72.0608 6.886292
5 90.076 8.607865
• Decomposition 6 108.0912 10.32944
7 126.1064 12.05101
• Zr5O8(SO4)2*15 H2O (s)  8 144.1216 13.77258
Zr5O8(SO4)2*14 H2O (s) + H2O (v) 9 162.1368 15.49416
10 180.152 17.21573
11 198.1672 18.9373
• Zr5O8(SO4)2  5 12 216.1824 20.65887
ZrO2 (s) +2 SO2 (v) 13 234.1976 22.38045
14 252.2128 24.10202
15 270.228 25.82359
SO2 1 64.0588 31.9452
2 128.1176 38.0668