THEORY OF CALORIMETRY

Hot Topics in Thermal Analysis and Calorimetry

Volume 2
Series Editor:
Judit Simon, Budapest University of Technology and Economics, Hungary

The titles published in this series are listed at the end of this volume.
Theory of Calorimetry
by

Wojciech Zielenkiewicz
Institute of Physical Chemistry,
Polish Academy of Sciences, Warsaw, Poland

and

Eugeniusz Margas
Institute of Physical Chemistry,
Polish Academy of Sciences, Warsaw, Poland

KLUWER ACADEMIC PUBLISHERS

NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW
eBook ISBN: 0-306-48418-8
Print ISBN: 1-4020-0797-3

©2004 Kluwer Academic Publishers

New York, Boston, Dordrecht, London, Moscow

Print ©2002 Kluwer Academic Publishers

Dordrecht

All rights reserved

No part of this eBook may be reproduced or transmitted in any form or by any means, electronic,
mechanical, recording, or otherwise, without written consent from the Publisher

Created in the United States of America

Visit Kluwer Online at: http://kluweronline.com

and Kluwer's eBookstore at: http://ebooks.kluweronline.com
 Contents

Preface ix

Chapter 1
The calorimeter as an object with a heat source 1
1.1. The Fourier law and the Fourier-Kirchhoff equation 2
1.2. Heat transfer. Conduction, convection and radiation 10
1.3. General integral of the Fourier equation. Cooling and heating processes 14
1.4. Heat balance equation of a simple body. The Newton law of cooling 20
1.5. The heat balance equations for a rod and sphere 26
1.6. General heat balance equation of a calorimetric system 33

Chapter 2
Calorimeters as dynamic objects 37
2.1. Types of dynamic objects 39
2.2. Laplace transformation 41
2.3. Dynamic time-resolved characteristics 47
2.4. Pulse response 55
2.5. Frequential characteristics 58
2.6. Calculations of spectrum transmittance 61
2.7. Methods of determination of dynamic parameters 66
2.7.1. Determination of time constant 66
2.7.2. Least squares method 74
2.7.3. Modulating functions method 76
2.7.4. Rational function method of transmittance approximation 79
2.7.5. Determination of parameters of spectrum transmittance 81
vi CONTENTS

Chapter 3
Classification of calorimeters. Methods of determination
of heat effects 85
3.1. Classification of calorimeters 85
3.2. Methods of determination of heat effects 97
3.2.1. General description of methods of determination of heat ef-
fects 97
3.2.2. Comparative method of measurements 101
3.2.3. Adiabatic method and its application in adiabatic and scan-
ning adiabatic calorimetry 103
3.2.4. Multidomains method 104
3.2.5. Finite elements method 109
3.2.6. Dynamic method 111
3.2.7. Flux method 114
3.2.8. Modulating method 114
3.2.9. Steady-state method 116
3.2.10. Method of corrected temperature rise 119
3.2.11. Numerical and analog methods of determination
of thermokinetics 123
3.2.11.1 Harmonic analysis method 123
3.2.11.2. Method of dynamic optimization 124
3.2.11.3. Thermal curve interpretation method 125
3.2.11.4. Method of state variables 127
3.2.11.5. Method of transmittance decomposition 128
3.2.11.6. Inverse filter method 129
3.2.11.7. Evaluation of methods of determination of total heat effects
and thermokinetics 131
3.3. Linearity and principle of superposition 136

Chapter 4
Dynamic properties of calorimeters 139
4.1. Equations of dynamics 139
4.2. Dynamic properties of two and three-domain calorimeters with
cascading structure 143
4.2.1. Equations of dynamics. System of two domains in series 143
4.2.2. Equations of dynamics. Three domains in series 148
4.2.3. Applications of equations of dynamics of cascading systems 151
CONTENTS vii

4.3. Dynamic properties of calorimeters with concentric configuration 154

4.3.1. Dependence of dynamic properties of two-domain calorimeter
with concentric configuration on location of heat sources and
temperature sensors 155
4.3.2. Dependence between temperature and heat effect as a function
of location of heat source and temperature sensor 165
4.3.3. Apparent heat capacity 168
4.3.4. Energy equivalent of calorimetric system 171

Final remarks 177

References 179
 Preface

Calorimetry is one of the oldest areas of physical chemistry. The date

on which calorimetry came into being may be taken as 13 June 1783, the
day on which Lavoisier and Laplace presented a contribution entitled
,,Memoire de la Chaleur“ at a session of the Academie Française.
Throughout the existence of calorimetry, many new methods have been
developed and the measuring techniques have been improved. At pre-
sent, numerous laboratories worldwide continue to focus attention on the
development and applications of calorimetry, and a number of compa-
nies specialize in the production of calorimeters.
The calorimeter is an instrument that allows heat effects in it to be
determined by directly measurement of temperature. Accordingly, to
determine a heat effect, it is necessary to establish the relationship be-
tween the heat effect generated and the quantity measured in the calo-
rimeter. It is this relationship that unambiguously determines the
mathematical model of the calorimeter. Depending on the type of calo-
rimeter applied, the accuracy required, and the conditions of heat and
mass transfer that prevail in the device, the relationship between the
measured and generated quantities can assume different mathematical
forms.
Various methods are used to construct the mathematical model of a
calorimeter. The theory of calorimetry presented below is based on the
assumption of the calorimeter as an object with a heat source, and as a
dynamic object with well-defined parameters. A consequence of this
assumption is that the calorimeter is described in terms of the relation-
ships and notions applied in heat transfer theory and control theory.
With the aim of a description and analysis of the courses of heat effects,
the method of analogy is applied, so as to interrelate the thermal and the
x PREFACE

dynamic properties of the calorimeter. As the basis on which the thermal

properties of calorimeters will be considered, the general heat balance
equations are formulated and the calorimeter is taken as a system of
linear first-order inertial objects.
The dynamic properties of calorimeters are defined as those corre-
sponding to proportional, integrating and inertial objects. Attention is
concentrated on calorimeters as inertial objects. In view of the fact that
the general mathematical equations describing the properties of inertial
objects contain both integrating and proportional terms, a calorimeter
with only proportional or integrating properties is treated as a particular
case of an inertial object.
The thermal and dynamic properties that are distinguished are used
as a basis for the classification of calorimeters. The methods applied to
determine the total heat effects and thermokinetics are presented. For
analysis of the courses of heat effects, the equation of dynamics is for-
mulated. This equation is demonstrated to be of value for an analysis of
various thermal transformations occurring in calorimeters.
The considerations presented can prove to be of great use in studies
intended to enhance the accuracy and reproducibility of calorimetric
measurements, and in connection with methods utilized to observe heat
effects in thermal analysis.