Wojciech Zielenkiewicz, Eugeniusz Margas (Auth.) - Theory of Calorimetry-2004

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
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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.
Chapter 1
The calorimeter as an object

with a heat source
A calorimeter can be treated as a physical object with active heat

sources inside it. An analysis of the thermal processes occurring inside
the calorimeter, and those between the calorimeter and its environment,
requires utilization of the laws and relations defined by heat transfer
theory [1–5].
The relations arising from heat transfer theory are applied to design
the mathematical models of calorimeters, which express the dependence
of the change in temperature measured directly as a function of the heat
effect produced. There is an understandable tendency to attempt to ex-
press these models in the simplest way. In practice, this is achieved by
applying simplifications to the original formulas. To make use of them
wisely, one has to understand precisely the assumptions made. This
chapter will present a detailed consideration of this topic.
Selected problems from heat transfer theory are also presented. Spe-
cial attention is paid to a discussion of the processes occurring in a non-
stationary heat transfer state. An understanding of these processes is of
importance for a proper interpretation of calorimetric measurements.
The general heat balance equation is introduced into the considerations.
Particular forms of this equation will be applied to consider problems
that form the subject of this book.
2 CHAPTER 1
1.1 The Fourier law and the Fourier-Kirchhoff

equation
Heat transfer by conduction in a homogenous, isotropic body is

mathematically described by the Fourier law [1]:
which assumes proportionality between the heat flux q and the tempera-
ture gradient grad T. The heat flux q, in is a vector determin-
ing the rate of heat Q transferred through unit surface at point P per
unit time dt (Fig. 1.1):
or
Quantity T in Eq. (1.1) is a function of the coordinates x, y, z and

time t. For any time t the value of T determines the scalar temperature
field. At every point upon it, the temperature at this instant is the same.
Such a surface is called the isothermal surface for temperature T.
The gradient of temperature, grad T, is a vector:
At points of an isothermic surface, the absolute gradient values are equal

to
where denotes differentiation along an outward-drawn line normal

to the surface. The value of is an experimentally determined coeffi-
cient called the thermal conductivity, expressed in
THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE 3
defines the amount of heat conducted through unit area in unit time if a
unit of temperature gradient exists across the plane in which the area is
measured. The value of for isotropic materials is a scalar, its value
depending on pressure and temperature changes. If the range of tem-
perature is limited, the variation in may not be large and as a reason-
able approximation it can be assumed to be constant. The reciprocal of
the thermal conductivity of a material is called its thermal resistivity.
The relation between the heat energy, expressed by the heat flux q,
and its intensity, expressed by temperature T, is the essence of the Fou-
rier law, the general character of which is the basis for analysis of vari-
ous phenomena of heat considerations. The analysis is performed by use
of the heat conduction equation of Fourier-Kirchhoff. Let us derive this
equation. To do this, we will consider the process of heat flow by con-
duction from a solid body of any shape and volume V located in an envi-
ronment of temperature [5,6].
When heat is generated in the body, two processes can occur: the ac-
cumulation of heat and heat transfer between the body and its environ-
ment. Thus, the amount of heat generated, dQ, corresponds to the sum of
the amount of heat accumulated, and the amount of heat ex-
changed,
4 CHAPTER 1
The heat flux through a surface element dS in time dt, in conformity

with Eq. (1.5), corresponds to
where dS = ndS is a normal vector to a surface element in the external

direction, so that the amount of heat transferred through the whole
surface S in time dt is equal to
On application of the Gauss-Ostrogrodsky theorem, which states that

the surface integral of a vector is equal to the volume integral of the
divergence of the vector, Eq. (1.8) becomes
The amount of heat generated in the body by the inner heat

sources of density g (the amount of heat developed by unit volume in
unit time) in element dV of volume V in time dt is equal to
Thus, the heat generated in the total volume V of the body in time dt is
equal to
The amount of heat accumulated, according to Eq. (1.6), is equal

to
When Eqs (1.9) and (1.11) are taken into account, Eq. (1.12) can be
written in the form
According to the First Law of Thermodynamics, the amount of heat

accumulated, can be described for each volume element of the
body as
where dh is the increase in specific enthalpy (due to unit volume), and p

is pressure.
The increase in specific enthalpy is proportional to the increase dT in
temperature T:
where is the specific heat capacity at constant pressure, in

and is the density, expressed in The increase in enthalpy in
the body of volume V is equal to
The second term on the right-hand side of Eq. (1.14) may be written
as
With regard to Eqs (1.16) and (1.17), Eq. (1.12) becomes
Comparison of both sides of Eqs (1.13) and (1.18) gives
Equation (1.19) is valid in any element of the body if
Division of both sides of Eq. (1.20) by dt gives

6 CHAPTER 1
On introduction of Eqs (1.15) and (1.1), Eq. (1.21) can be written in

the form
For a solid body with a distribution of temperature T at time t given

by
we have
Thus, the substantial derivative of temperature takes the form
Introduction of the velocity vector w
into Eq. (1.25) lends to
In a similar way, pressure changes as a function of (x, y, z, t) can be

expressed by
Substitution of Eqs (1.27) and (1.28) into Eq. (1.22) yields
Equation (1.29) is called the Fourier-Kirchhoff equation.

When the process takes place under isobaric conditions, i.e.
the Fourier-Kirchhoff equation (Eq. (1.29)) takes the form
When the velocity vector is equal to zero, i.e.
Eq. (1.31) becomes
Equation (1.33) is called the Fourier equation or the equation of con-

duction of heat.
Let us use the Fourier equation to consider the following processes:
a) Stationary (steady-state) heat transfer, which occurs when the changes
in temperature T are not time-dependent:
and the distribution of temperature is a function only of the Cartesian

coordinates (x,y, z). Relation (1.34) is fulfilled, when g = const,
b) A non-stationary (non-steady-state) heat transfer process, which takes
place when the changes in temperature T are time-dependent:
8 CHAPTER 1
When g = 0, the temperature changes depend only on the initial dis-

tribution of temperature. They characterize the heating or cooling proc-
esses occurring in the thermal by passive body.
The investigation of heat processes for which
is the subject of great numbers of calorimetric determinations.

When and are constants independent of both pressure and
temperature, parameter a is often applied:
This is called the thermal diffusivity coefficient, expressed in

Introduction of coefficient a into Eq. (1.33) gives
where is a Laplace operator:

The Fourier-Kirchhoff differential equation and the equation of con-
duction of heat describe the transfer of heat in general form. In order to
obtain the particular solutions of these equations, it is necessary to de-
termine the initial and boundary conditions.
The initial conditions are be to understood in that the temperature
throughout the body is given arbitrarily at the instant taken as the origin
of the time coordinate t. It is usually assumed that the temperature at the
beginning of the process is constant. For steady-state processes, the
course of the temperature changes does not depend on the initial condi-
tions.
The boundary conditions prescribe:
a) Dimensionless parameters which characterize the shape and dimen-

sions of the body. An example is a homogenous ball with radius R,
where
In the spherical system, is expressed by
In the case of a cylinder, it is convenient to operate with cylindrical

coordinates r, x in which the Laplacian has the form
where
b) Physical parameters such as specific heat density and thermal

conductivity coefficient which characterize the properties of the body
and the environment. It is determined that they are constant or a function
of temperature. In all the problems discussed in this book, it is consid-
ered that and are constants.
c) Surface conditions. These conditions are as follows:
1. The prescribed temperature distribution on the surface S of the
body:
2. The prescribed distribution of the heat flux or temperature gradient

on the surface of S of the body:
3. The defined relation between the temperature and the heat flux on
the surface S of the body:
10 CHAPTER 1
where is the surface heat transfer coefficient (see § 1.2).

Mixed boundary conditions, which are subsequent to the assumption
that particular parts of surface S are characterized by various types of
boundary conditions, can also be used.
d) The form of function g, which describes the inner heat sources.
When the initial and boundary conditions are known, the physical
problem of heat conduction is to find adequate solutions of the Fourier-
Kirchhoff equation or the Fourier equation.
1.2 Heat transfer.

Conduction, convection and radiation
“When different parts of a body are at different temperatures, heat

flows from the hotter to the colder parts. The transfer of heat can take
place in three distinct ways: conduction, in which the heat passes
through the substance of the body itself; convection, in which heat is
transferred by relative motion of portions of the heated body; and radia-
tion, in which heat is transferred directly between distant portions of the
body by electromagnetic radiation” [1].
Heat conduction is a type of transfer of heat in solids and liquids, in-
terpreted as the imparting of kinetic energy resulting from collisions
between disorderly moving molecules. The process occurs without any
macroscopic motions in the body. The conductivity of diamond without
traces of isotope is the highest. The conductivity of a metals is also
high. The lowest conductivity is that of a gas.
Heat transfer by conduction is defined by the Fourier equation (1.1).
The application of Eq. (1.1) in calculations encounters difficulties be-
cause the temperature gradient of the wall must be defined, as well as its
increments around the whole surface S of the body. Accordingly, for
practical reasons the Newton equation is usually applied:
where coefficient is called the surface conductance or the coefficient

of surface heat transfer. It defines the amount of heat transferred in unit
time through unit surface when the existing temperature gradient is
1 deg. For using of the Newton equation, there is no need to introduce
any simplifying assumptions. All the complicated character of the heat-
transfer phenomenon is enclosed in the value of coefficient which
depends on many parameters. When the heat transfer conditions are
described, appropriate attention must be paid to the proper choice of
and the definition of the influence of different factors on its value.
For a description of the heat flow phenomenon on the border of the
body, a differential equation is used:
Equation (1.47) results from the Fourier law [Eq. (1.1)] and the New-
ton equation [Eq. (1.46)], expressed by Eqs (1.48) and (1.49), respec-
tively
by equating the right-hand sides. When the geometry of the considered

system is simple, an exact solution of Eq. (1.47) can easily be deduced.
The value of surface heat transfer coefficient is strongly affected
by the presence of heat bridges and thermal resistances. Imperfect con-
tact between touching surfaces which are at different temperatures
causes a lack of thermal equilibrium inside the free space between them.
The magnitude of the thermal resistance depends on the surface condi-
tions, the number and shape of surface irregularities and the conditions
of heat conduction through the gas present in the space between the
contact points. Temperature variations appear even though the thickness
of the gas layer may be close to the size of the free distance in the gas
molecule. It has been found [6] that even surface irregularities within the
range of tens of microns influence the value of the surface heat transfer
12 CHAPTER 1
coefficient. The variations in thermal resistance between two solid bod-

ies are the cause of errors in the heat determination.
The coefficient of surface heat transfer by conduction also de-
pends on the existence of heat bridges in the system. If a layer of sub-
stance of low heat conductivity isolates two objects, then the heat ex-
change is not intensive. If a third object with heat conductivity higher
than that of an insulating substance joins those two objects, then through
this object (called a “heat bridge”) heat will flow, intensively enhancing
the total heat exchange. Unfortunately, it is often very difficult in calo-
rimetric practice to eliminate the existence of unwanted heat bridges and
thermal resistances. It is crucial to decrease their contribution to the
value of
Heat transfer by convection occurs in liquids and gases where there
is a velocity field caused by extorted fluid motion or by natural fluid
motion caused by a difference in density. The former case involves
forced convection, and the latter case free convection. Combined con-
vection occurs when both forced and free convection are present. The
convection coefficient of surface heat transfer, defining the heat ex-
change in the contact boundary layer between fluid and solid, is deter-
mined. Coefficient is often expressed by equations containing criteria
numbers, such as those of Nusselt (Nu), Prandtl (Pr), Reynolds (Re) and
Grashof(Gr):
The criteria numbers are calculated by use of material constants such as

– thermal conductivity coefficient; a – thermal diffusity coefficient;
and v – kinematic viscosity. In the expressions in (1.50), l is a distinctive
dimension of the body; w is the distinctive velocity; g is the acceleration
due to gravity; is the difference in temperature, and is the
thermal expansivity coefficient.
Coefficient usually depends on the difference in temperature be-
tween the body and its environment. In the microcalorimeter described
by Czarnota et al. [7], free convection occurs in the spherical space
around the calorimeter, and as a result the coefficient is defined by
the equation
A frequent goal in calorimetry is to obtain a constant value of irre-

spective of existing temperature gradients. A more common trend is to
decrease or eliminate the heat transfer by convection. A very effective
way to achieve this is the creation of a vacuum. The contribution of the
heat transfer by convection can also be reduced by increasing the share
of heat conduction in the total heat transfer.
Radiation is the transfer of thermal energy in the form of electro-
magnetic waves; it occurs in processes of emission, reflectivity and ab-
sorptivity. The quantity of heat radiated through a transparent gas
layer from surface at temperature to surface at temperature
completely enclosing the first surface, is
where is a substitute emission coefficient depending on the emission

from a surface, the geometry and the reflectivity, and is a radiation
constant Introduction of the relation express-
ing the total radiant energy leaving unit surface area:
yields
or, on analogy with Eq. (1.47):
where
is called the radiation heat transfer coefficient. When the temperature

difference
14 CHAPTER 1
is much lower than the temperatures and can be expressed by
where higher–power exponents of ratio are neglected. If the value

of this fraction is very small, then a simplified formula is often valid:
The heat transfer in calorimeters is described in terms of the effective

heat transfer coefficient, involving the heat transfer of convection, con-
duction and radiation. In calorimetry, it is more common to use coeffi-
cient G, called the heat loss coefficient, which is equivalent to the effec-
tive heat transfer coefficient calculated for the whole surface S.
1.3. General integral of the Fourier equation.

Cooling and heating processes
Let us consider the temperature changes in a body, due to the initial

temperature difference between the body surface S and the environment
[1, 6, 8]. The initial condition is defined as
Additionally, it is assumed that
In the examined case, the solution of the Fourier equation will refer
to the heating or cooling processes of a thermally passive body. Any
assumptions made will not impose any restrictions on the solution.
When heat is generated in the body and the expression of g (x, y, z, t) is
known, the particular solution of the Fourier equation, can be found, on
the assumption that the initial conditions are zero, T(x, y, z) = 0. Accord-
ing to the superposition rule, the solution will be the sum of the sepa-
rately determined solutions.
Let the heat transfer between the body and its environment proceed
through the surface S according to the boundary condition of third kind,
i.e.
If it is assumed that the physical parameters are constants and

the Fourier equation (Eq. (1.38)) becomes
and can be written in the form
To solve the differential Eq. (1.63), the Fourier method of separated

variables will be used. According to this function, T(x, y, z, t) can be
described as
Then
and
Substituting the above equations into Eq. (1.63) gives
or, after transformation

16 CHAPTER 1
The right–hand side of Eq. (1.69) is a function only of coordinates

(x, y, z), whereas the left–hand side is a function only of the independent
variable t. To satisfy Eq. (1.69), both sides must be equivalent to the
same constant value. This means that this value should be negative.
Thus, when the initial temperature of the body is higher than the envi-
ronment temperature, a cooling process occurs and
whereas, when the initial temperature of the body is lower than the envi-
ronment temperature, the heating process is characterized by
Thus:
In order to fulfil this condition, let us denote by the value of the

sides of Eq. (1.69). Thus, instead of one differential equation, we obtain
the two following differential equations:
Equation (1.73) may be written as

and its solution is
which can easily be checked.

Equation (1.74) may be written in the form
Solving this equation gives a set of values
equivalent to the set of solutions of the function
whereas the compatible function is equal to
The magnitudes are called the eigenvalues of the differential

Eq. (1.65). The functions in Eq. (1.80) corresponding to the particular
eigenvalues are called eigenfunctions. Since Eq. (1.62) is a linear differ-
ential equation, its solution is also the sum of eigenfunctions:
or, with regard to Eq. (1.80), it can be written in the form
On introduction of the notation
Equation (1.82) can be written as

18 CHAPTER 1
or
We see that the course of the temperature T (x, y, z, t) changes at any

point of the body is the sum of infinite number of exponential functions.
Whereas the sequence of eigenvalues is an increasing sequence, the
sequence of constants monotonously decreases [9]. As a
higher accuracy of determination of temperature T (x, y, z, t) is needed, a
greater number of exponential terms must be used for a proper descrip-
tion of the changes in temperature of the body within time. In the limit-
ing case, it is possible to neglect all the exponential terms, excluding the
one having in the exponent the smallest value of the constant Equa-
tion (1.84) then transforms to an equation equivalent to the mathemati-
cal expression of Newton’s law. This type of description is mostly used
in calorimetry and thermal analysis.
The expression given by Eq. (1.85) was used for the first time in mi-
crocalorimetry to describe short–duration heat processes investigated in
a Calvet microcalorimeter [10–13]. The temperature T rise caused by
heat effect was expressed by the following equation:
where the adopted relations made possible the determination of T for an

exponential temperature course of second or third order. The excellent
monograph by Camia [14] is one of the most important works on this
field. A number of methods are currently used to determine the heat
effects and thermokinetics of short–duration processes, based on the
assumption of a multiexponential course of temperature changes. These
methods are disscused in Chapter 3.
The question of the determination of total heat effects for a multiex-
ponential temperature course in time was investigated by Hattori et al.
[15] and Tanaka and Amaya [16].
Hattori et al. [15] consider the calorimeter in terms of a one-

dimensional model of distributed parameters. The objects distinguished
are the calorimetric vessel A, the heat conductor B and the medium C, at
constant temperature, that surrounds the calorimeter (Fig. 1.2). For the
solution of the Fourier equation, the following assumptions were made:
heat power is generated in the calorimetric vessel at homogenous tem-
perature and with constant heat capacity; the heat conductor along which
the heat flows has a well-insulated lateral surface. Its ends are defined as
x = 0 and x = L; there exists a heat bridge of the calorimetric vessel with
the conductor; the environment is kept at constant temperature. The heat
transfer takes place only through the cross-section for x = 0.
Tanaka and Amaya [16] consider the calorimeter as a concentric
model of three domains, and (Fig. 1.3), which are solids.
Domain in which heat q heat is generated or adsorbed, is surrounded
by domain Domain is surrounded by domain at constant tem-
perature. These three domains represent the calorimetric vessel, and the
heat conductor between the vessel and the shield.
In both of the above papers, it was shown that, independently of the
20 CHAPTER 1
number of exponential terms that describe the temperature course in

time, it is possible to calculate the total heat effect determining the sur-
face area between the registrated temperature course in time and the
time axis below the temperature course in time if the measurement starts
from equilibrium conditions and the initial and final temperatures are
equal.
1.4. Heat balance equation of a simple body.

The Newton law of cooling
Linear differential equation of first order called the heat balance

equation of a simple body, has found wide application in calorimetry
and thermal analysis as mathematical models used to elaborate various
methods for the determination of heat effects. It is important to define
the conditions for correct use of this equation, indicating all simplifica-
tions and limitations. They can easily be recognized from the assump-
tion made to transform the Fourier-Kirchhoff equation into the heat bal-
ance equation of a simple body.
Let us consider [1, 6, 8, 17] that the heat transfer process takes place
under isobaric conditions, without mass exchange and that the thermal
parameters of the body are constant. The Fourier-Kirchhoff equation can
then be written as
Integration of both sides of Eq. (1.87) with respect to the volume V

of the body of extremal surface S gives
The left–hand side of Eq. (1.88) can be transformed as follows:
where
is the average temperature of the body of volume V.

The first term on the right–hand side of Eq. (1.88) can be trans-
formed by using the Gauss-Ostrogradsky theorem for the vector gradi-
ent:
where dS is an oriented element of the surface S of the body. Applica-

tion of the average value theory gives
where is the average flux of heat across the surface S of the body.
Application of the boundary condition of the third kind leads to
where is the average temperature of the external surface S of the

body, is the heat transfer coefficient, and is the temperature of
the environment.
The integral of the second term on the right–hand side of Eq. (1.88):
corresponds to the change in the heat power dQ/dt within time t. Thus,
the second term on the left–hand side of Eq. (1.88) can be written in the
form
22 CHAPTER 1
From Eqs (1.89) – (1.95) and Eq. (1.88), and putting
where C is the total heat capacity of the body, we have
Equation (1.97) is accurate, but does not give an explicit solution,

because the relation between temperature and the temperature on the
surface is not defined.
If it is assumed that
Equation (1.97) becomes
or
Equations (1.99) and (1.100) are commonly known as the heat bal-
ance equations of a simple body. From the above considerations, it is
clear that these heat balance equations and the Fourier-Kirchhoff equa-
tion [Eq. (1.87)] are equivalent to each other when:
1. the temperature in the total volume of the body is homogenous
and only a function of time;
2. the temperature on the whole surface is homogenous and only a
function of time;
3. the above temperatures are identically equal to one another at any
moment of time;
4. the heat capacity C and the heat loss coefficient G are constant
and not functions of time and temperature.
When
Equation (1.104) is equivalent to Newton’s law of cooling. The coef-

ficients and of Eqs (1.97) and (1.104) can be characterized as fol-
lows [9]. Coefficient determines the amount of heat transfer by unit
surface in unit time when the temperature difference is equal to 1 deg.
Constant is called the cooling constant and characterizes the rate of
body cooling. This quantity is the reciprocal of the body time constant
It has the same value for any point of the body. Constant does not
depend on the initial temperature field, but depends on the shape and
dimensions of the body, the thermal parameters of the body (e.g. the
thermal diffusivity coefficient) and the conditions of heat transfer. Coef-
ficient is a quantity describing the measure of the ability of the given
body to react to cooling or heating of the environment. The influence of
this environment on the body is characterized by the heat transfer coef-
ficient and/or the heat loss coefficient G.
The dependence between quantities G, C and given by Eq. (1.103)
is appropriate only when When these temperatures are
different, Eqs (1.97) and (1.105) can be supplemented by a new parame-
ter, the coefficient of heterogenity of the temperature field
24 CHAPTER 1
Thus, Eq.( 1.97) becomes
In order to solve this non–stationary differential equation, it would

be necessary to know the function This condition is difficult to
fulfil. To solve the theory of the problem of ordered state heat transfer
[9], two periods of cooling or heating process of the body are specified.
The first period is characterized by a disordered course of temperature

field changes in time. The second, the well-ordered heat transfer period,
comes after a certain period of time (Fig. 1.4). It is assumed that, for the
ordered state heat transfer, the relation between heat capacity C, heat
loss coefficient G, cooling constant and coefficient is expressed as
follows:
Coefficient is a dimensionless quantity; its value can vary between

one and zero. The more differs from unity, the greater is the inequality
in the field of temperature. This coefficient is a function of Biot’s num-
ber Coefficient decreases to zero as constant Bi increases
to infinity. Let us assume that the same body is observed under various
conditions of heat transfer from the body to the environment and that as
a result there are various values of the surface heat transfer coefficient
For the sequence of increasing values of
there is a sequence of increasing values of the constants
According to the discussed theory of the ordered state heat transfer,

together with the increase in the value the reaction of the body be-
comes weaker and the value of the cooling constant drifts towards the
limit value (Fig. 1.5). Only in the case of certain small values of
coefficient can it be assumed that a homogenous temperature distribu-
tion exists in the examined body. It also indicates that the range
where the heat balance equation can be accurately used for determina-
tion of the heat power changes within time (the P(t) function called
thermokinetics) is limited. However, this equation is also used as a
mathematical model in determining the P(t) function in instruments with
26 CHAPTER 1
different values of coefficient It is applied as a mathematical model in

conduction microcalorimeters, in which heat exchange between the
body and environment is extensive and coefficient is significant. For
these reasons, it is very important to verify the accepted model experi-
mentally.
If a maker of a calorimetric system decides to apply the method of
determining the heat effect resulting from Eq. (1.99), it would be most
convenient to establish a set of parameters (e.g. such that the
calorimeter in which the heat is generated fulfils the conditions
needed to apply this equation. A probe to determine such a set of pa-
rameters was undertaken by Utzig and Zielenkiewicz [18] for a simple
physical model as an approximation of a real calorimetric system. The
relation between the dimensionless parameter the physical pa-
rameters of the system and was elaborated. In the parameter the
value corresponds to the time interval after which the body temperature
changes can be described by one exponential term, while is a time
constant.
1.5. The heat balance equations

for a rod and sphere
A real calorimeter is composed of many parts made from materials

with different heat conductivities. Between these parts one can expect
the existence of heat resistances and heat bridges. To describe the heat
transfer in such a system, a new mathematical model of the calorimeter
was elaborated [8, 19] based on the assumption that constant tempera-
tures are ascribed to particular parts of the calorimeter. In the system
discussed, temperature gradients can occur a priori. Before defining the
general heat balance equation, let us consider the particular solutions of
the equation of conduction of heat for a rod and sphere. For a body
treated as a rod in which the process takes place under isobaric condi-
tions, without mass exchange, the Fourier-Kirchhoff equation may be
written as
Consider the above equation for (Fig. 1.6):
If we put
Eq. (1.109) becomes
If we expand the function T(x, t) as a Taylor series in the neighbor-

hood of the point and neglect terms of higher order than the sec-
ond, we have
Consideration of the function T(x, t) at points and

gives the following set of equations:
28 CHAPTER 1
If we put
this set of equations becomes
The solutions of the equation set defined by Eq. (1.115) are
Substitution of Eq. (1.116) in Eq. (1.111) gives

Let the volume of the n-th element be
where F is the cross–sectional area of the rod. Multiplication of both

sides of Eq. (1.118) by gives
where defined by
is the heat capacity of domain n, whereas defined by
is the heat power generated in domain n. The quantities
are the heat transfer coefficients between domains n and n+l, and do-
mains n–1 and n, respectively. The quantities
denote the heat loss coefficients. Thus, Eq. (1.120) may finally be writ-
ten as
30 CHAPTER 1
where
denote the amounts of heat exchanged between domains n and n+1 and
between domains n–1 and n in time interval dt, respectively. Equa-
tion (1.125) is the desired heat balance equation for a rod considered as
a system of domains arranged in a row. The same procedure is applied
to deduce the equation of heat conduction for a homogenous sphere of
radius r, where an isobaric process without mass exchange takes place.
The Fourier-Kirchhoff equation written with spherical coordinates be-
comes
for Let us consider the above equation with
The expansion of the function T(r, t) into a Taylor series in the

neighborhood of the point neglecting terms of higher order than
the second, leads to
Substitution of and gives the set of equations

Let us put
and neglect derivatives of higher order than the second:
The solutions of the above set of equations are

32 CHAPTER 1
From Eqs (1.132), (1.134), (1.135) and (1.128) we have
Multiplication of both sides of Eq. (1.13 6) by where
and putting
gives the following differential equation
The heat balance equations for the rod and sphere described as Eqs
(1.125) and (1.138) are identical in form. They are derived on the basis
of the same assumptions: in the examined bodies several elements
(parts, domains) are distinguished; each is characterized by a constant
heat capacity and homogenous temperature in the total volume;
the heat exchange between these parts is characterized by heat loss coef-
ficient G. The first term on the left–hand side of these equations deter-
mines the amount of accumulated heat in the domain of the body of
indicator n; the second and third terms are the amounts of heat ex-
changed between this part and the neighboring domains of indicators
n+1 and n–1. The heat exchange between the body and environment is
characterized by the boundary condition of the third kind.
1.6. General heat balance equation

of a calorimetric system
Let us assume Eqs (1.126) and (1.139) as the basis on which to de-
rive the generalized heat balance equation of the calorimeter treated as a
multidomain (elements, parts) system of various configurations [19-21].
Let us also assume that the heat transfer in the body can take place not
only between the neighboring domains, but also between any domains
characterized by heat capacities and temperatures
Each of the separate domains has a uniform temperature throughout its
entire volume; its temperature is a function only of time t, and the heat
capacity of domain is constant. The domains are separated by centers
characterized by loss coefficient and the heat exchange between the
domains and between the domains and the environment of temperature
takes place through these centers. Temperature gradients appear only
in these centers and between the domains and the environment; their
heat capacities are, by assumption, negligibly small. Furthermore, a heat
source or temperature sensor may be positioned in any of the domains.
The amount of heat exchanged between domains j and i in the
time interval dt is proportional to the temperature difference of these
domains; the heat loss coefficient is the propor-
tionality factor:
The condition is fulfilled. The amount of heat ex-

changed between domain j and the environment in time interval dt is
equal to
Thus, the total amount of heat dQ”(t) exchanged between domain j

and the remaining domains and the environment is equal to
34 CHAPTER 1
Taking into account Eqs (1.140) and (1.141), we have
The amount of heat dQ´(t) accumulated in domain j is equal to
The amount of heat generated in domain j in time interval dt is

equal to the sum of the heat accumulated in this domain dQ´(t) and the
heat exchanged between this domain and the remaining domains and the
environment dQ´´(t). Thus:
From Eqs (1.143) and (1.144), we have
Dividing both sides of the above equation by dt gives
or
where
v–n,
is the heat power generated in domain j.

In Eq. (1.148), the first term on the right–hand side determines the
amount of heat accumulated in domain j, the second term the amount of
heat exchange between domain j and the environment, and the last term
the amount of heat exchange between domain j and remaining N–1 do-
mains.
The differential equation Eq. (1.148) is called the general heat bal-
ance equation of domain j, and the set of these equations is the general
heat balance equation of a calorimetric system. The heat balance equa-
tion Eq. (1.147) describes in general form the courses of the heat effects
in a calorimeter of any configuration of domains and any localization of
heat sources.
The general heat balance equation corresponds to the formalization
of the general calorimetric model by means of the set of equations with
lumped parameters. To consider the thermal properties of a calorimeter,
the detailed form of this equation has to be derived. It is necessary to
define in it the number and configuration of the distinguished domains
and the centers which separate these domains and where heat transfer
takes place.
The representation of the calorimeter by mathematical models de-
scribed by a set of heat balance equations has long traditions. In 1942
King and Grover [22] and then Jessup [23] and Churney et al. [24] used
this method to explain the fact that the calculated heat capacity of a calo-
rimetric bomb as the sum of the heat capacities of particular parts of the
calorimeter was not equal to the experimentally determined heat capac-
ity of the system. Since that time, many papers have been published on
this field. For example, Zielenkiewicz et al. applied systems of heat
balance equations for two and three distinguished domains [25-48] to
analyze various phenomena occurring in calorimeters with a constant–
temperature external shield; Socorro and de Rivera [49] studied micro-
effects on the continuous-injection TAM microcalorimeter, while
Kumpinsky [50] developed a method or evaluating heat-transfer coeffi-
cients in a heat flow reaction calorimeter.
36 CHAPTER 1
The calorimeter as a system of several domains has often been pre-

sented by using a method based on thermal-electric analogy [51–53].
This is based on the similarity of the equations describing heat conduc-
tion and electric conduction. Such a study generally involves both the
use of circuit theory and the principle of dimensional similarity. In a
corresponding network analog, the thermal resistances and capacities are
simulated by electric resistors and capacitors, respectively. In construct-
ing such circuits, it is considered that there is an equivalence between
the quantities: electric current and heat flow; electric voltage difference
and temperature difference; electric resistance and thermal resistance;
and electric capacity and heat capacity.
The thermal–electric analogy method has been used to analyze and
represent the operation mode of a number of calorimetric and thermal
analysis devices. For example, Rouquerol and Boivinet [54] presented
analogs of electric circuits for the following heat-flux and power com-
pensation devices: the conventional DTA instrument of Mauras [55], the
differential scanning microcalorimeter of Arndt and Fujita [56], and the
Tian-Calvet microcalorimeter [57]. Wilburn et al. [58] used both passive
and active analogs to investigate the effect of the holder design on the
shape of DTA peaks. The thermal-electric analogy was applied by Nico-
laus [59] to analyze the problem of reconstruction of the heat flux curve.
Ozawa and Kanari [60] illustrate the discussed heat balance equations
for constant heating rate DSC by an equivalent electrical circuit. The
method of analogy is also used in the papers of Claudy et al. [61–63].
The thermal-electric analogy method is useful to represent the ac-
cepted structures, which distinguish the domains and the modes of their
connection with themselves and the environment. It is also useful to
formulate a suitable system of the balance equations for the bodies (do-
mains). The increase in the number of its applications is related to the
development of analog computer calculation methods.
It will be demonstrated below that the extended information range
relating to the investigated calorimeter allows analysis of both its ther-
mal and dynamic properties. The use of the method based on the anal-
ogy of the thermal and dynamic properties of the investigated systems is
profitable in this case.
Chapter 2
Calorimeters as dynamic objects
Calorimeters are physical objects that can be described in different

ways. The steering theory treats a calorimeter as a dynamic object, in
which the generated heat effects (input signals) are transformed to the
quantity measured directly in the calorimeter, e.g. temperature (output
signal). Let us describe the input signals by the functions
and the output signals by the functions In fact,
in calorimetry the output function never reproduces the input function
directly. The calorimeter is a kind of transducer, which transforms the
input functions into the output functions. Thus, to reproduce
with the required accuracy on the basis of
the relation between these two types of functions should be determined:
and the procedure should be selected so as to allow the inverse opera-

tion, i.e.
which permits determination of the input function on the basis of a given

course of the output function of the calorimeter. When the unchanging
relation between the input and output functions is determined, it fur-
nishes an explicit description of the dynamic properties of the calo-
rimeter.
A calorimeter is usually regarded as an object that can be described
by one differential equation or a system of linear differential equations
with constant coefficients. These equations are treated as the mathemati-
cal models of calorimeters. If there are many output functions, then the
dynamic object (calorimeter) is described by a system of n differential
equations. Assuming linearity and applying the superposition rule, one
38 CHAPTER 2
may reduce two or n objects to one. On analysis of an object described

by one input and one output function, we do not lose generality.
A convenient method for solving linear equations is to apply the
Laplace or Fourier transform. In the transfer function (transmittance),
the dynamic properties are encoded. The function is defined as the quo-
tient of the Laplace transforms of the output and input functions. The
spectrum transmittance is defined as the quotient of the Fourier trans-
forms of the output and input functions under zero initial conditions.
The transmittance (transfer function) of the object has the form
where s is a complex variable; x(s) and y(s) are the Laplace transforms
of the output signal x(t) and the input signal y(t), respectively.
Equation (2.3) written in the form
can be visualized by a block diagram (Fig. 2.1). The objects of the

structure shown in Fig. 2.1 are called open objects in the steering theory.
Let us consider the quantities H(s), x(s) and y(s) of Eq. (2.4). Each of
them can be obtained by using the two others:
1. The transmittance H(s) can be determined only on the basis of ex-
perimentally determined y(s) and x(s). The calorimeter is then
treated as a “black box” and knowledge of their physical parame-
ters is neglected. It is assumed that the calorimeter can be treated
as a linear, stationary and invariant object.
2. The transmittance H(s) of the calorimeter is based on a mathe-
matical model of the calorimeter with distinguished physical pa-
rameters and mutual relation between them. The experimental de-
CALORIMETER AS DYNAMIC OBJECT 39
mination of the functions y(s) and x(s) is applied for evaluation of

the values of the dynamic and static parameters of the transmit-
tance. This procedure is equivalent to the calibration of the calo-
rimeter.
3. The transform x(s) is determined in the knowledge of the form of
the transmittance H(s) and the values of their parameters. Input
function y(s) is determined experimentally. This procedure is
convenient to verify the agreement between experimentally de-
termined and calculated functions x(s).
4. The transform y(s) is evaluated on the basis of previously known
H(s) and experimentally determined function x(s). It corresponds
to the determination in the domain of the complex variable of the
course of the investigated heat effect.
The form of the transmittance depends on the type of the dynamic
object.
2.1. Types of dynamic objects
Among the open systems, the following types of dynamic objects can
be distinguished [64, 65]:
Proportional type, when the input function y(t) is proportional to the
output function x(t):
where k is the proportionality coefficient, and the transmittance H(s) has

the form
while the spectrum transmittance is expressed by Eq. (2.7):
Integrating type, when the input function is proportional to the

derivative of the output function:
40 CHAPTER 2
while
First-order inertial type, when the input function is a linear

combination of the output function and its derivative:
while
Let us compare the equations describing the dynamic properties of

the distinguished types of objects with suitable heat transfer equations:
1. We compare Eq. (2.5), which describes the dynamic properies of
a proportional object, with the Newton heat transfer equation [Eq.
(1.46)];
2. We compare Eq. (2.8), which describes the dynamic properties of
an integrating object, with the first term of the left-hand term of
Eq.(1.99);
3. We compare Eq. (2.11), which describes the dynamic properties
of an inertial object, with the heat balance equation of a simple
body [Eq. (1.99)].
It can readily be imagined that a calorimeter in which the course of
heat power within time corresponds (with the accuracy of the factor) to
the course of the changes in the output function (e.g temperature) has
the properties of the proportional object. The properties of integrating
objects are those of adiabatic calorimeters, inside which the accumula-

tion of heat occurs.
Calorimeters that are inertial objects comprise the most numerous
group of calorimeters. Let us assume that a calorimeter has only the
integrating or proportional properties of the object, as a certain
idealization. Of course, this idealization is well-founded in many cases.
The relation describing the dynamic properties of the object is
equivalent to the mathematical model of the calorimeter. It is expressed
as a function of time, frequency or a complex variable domain.
2.2. Laplace transformation
The Laplace transformation [66] is the operation of changing one

expression into another by integration. In this transformation, the
function f(t) of the real variable is changed into the complex function
F(s) of the complex variable s. The Laplace transform is defined by Eq.
(2.14):
and abbreviated as
where while for the existence of the transform F(s) the

condition must be fulfilled.
The inverse Laplace transformation is defined by Eq. (2.16):
where C is a contour that outlines all extremes of the function in the

integral formula. This operation is abbreviated as
The Laplace transformation is very convenient to use. Its advantages

include: 1) The Laplace transforms of simple functions can be deter-
42 CHAPTER 2
mined by direct integration or integration by parts. In most cases, the

simple function f(t) and the transform F(s) representing the function
transform pairs are tabulated; 2) the Laplace transformation is a linear
transformation for which superposition holds; 3) by application of the
Laplace transformation, an ordinary differential equation is reduced to
the algebraic equation of the transform, called the subsidiary equation of
the differential equation.
Let us apply the Laplace transform to the heat balance equation of a
simple body (Eq. 1.99):
On dividing by G and putting
we obtain
Use of the Laplace transformation for Eq. (2.19):
gives the solution for Eq. (2.19) in the complex domain
After simple rearrangement, Eq. (2.21) becomes
Equation (2.22) is called the subsidiary equation of differential Eq.

(1.99); T(s) is the response transform of the output function; F(s) and
are driving forces; and is the characteristic function of
the object. The first and third terms on the right-hand side of Eq. (2.22),
the function of the initial conditions, are the transforms of the transient
solution. The second term, which is independent of the initial condi-

tions, represent the transform of the steady-state solution.
The inverse Laplace transformation defines the function T(t) charac-
terizing the course of the temperature changes of the calorimeter. When
the heat effects are not generated, and and thus T(t)
depends only on the initial temperature difference T(0) between the
calorimeter and its environment. Then:
In a similar way, the Laplace transform can be applied to obtain the

solution of Eq. (2.20) for the other input functions.
If it is assumed that two first-order inertial objects in series are dis-
tinguished in the calorimeter, while the output function of the first object
is at the same time the input function of the second object (Fig. 2.2),
then the calorimeter transmittance H(s) has the form
In the time domain, the system is described by the following differ-

ential equations:
Increase of the number of inertial objects causes significant changes

in the course of the output function. Let us assume that the objects are
arranged in series in such a way that the input function of the next iner-
44 CHAPTER 2
tial first-order object is the output function of the previous object (Fig.
2.3).
A graphical presentation of the output functions for numbers of

objects ranging from one to six, caused by input function forcing
corresponding to the unit step function, is shown in Fig. 2.4.
The block diagrams presented in Figs 2.1 - 2.3 are characteristic for
the open systems and differ from one another only in the number of
inertial objects. The dynamic objects are not always arranged in series.
In many cases, as a result of self-arrangement of the objects and their
configurations, we must consider the set of differential equations
presented by the block diagrams of closed-loop systems. For example,
for the calorimeter described by the differential equation
the resulting block diagram is a in Fig. 2.5, while for the calorimeter
described by the following set of differential equations:
where
the resulting block diagram is b in Fig. 2.5.
When a larger number of inertial objects are distinguished, the

calorimeter transmittance will have a more complicated form. For N
objects, the transmittance has the form
and we obtain the form of the calorimeter transmittance H(s):
In this case, in the time domain the calorimeter is described by the

following set of differential equations:
where
46 CHAPTER 2
When the physical parameters of the system are neglected, Eq. (2.30)
takes the form
On application of the Laplace transformation, Eq. (2.33) under zero

initial conditions can be written in the form Eq. (2.4):
where
is the transmittance of the analyzed system; m < N; and N denotes the

system rank.
Determination of the transmittance expressed by Eq. (2.34) is
eqivalent to calculation of the polynomials and
The equation
is called the characteristic equation and its roots are the “eigenvalues”
or “poles” of transmittance. If it is assumed that in Eq. (2.35) the
polynomial has only single zero values, we can write
The roots of Eq. (2.37)

are named the “zeros” of transmittance, and the polynomial in this equa-
tion is expressed by
On substitution of Eqs (2.36) and (2.38) into Eq. (2.34), the

transmittance H(s) can be written in the form
The poles and zeros of transmittance express the inertial properties

of the calorimetric system as a dynamic object. With the introduction of
transmittance H(s) becomes
where
is a constant called the static factor.
2.3. Dynamic time-resolved characteristics
The relation that describes the output function changes in time

caused by the action of the input function is given by the dynamic time-
resolved characteristics. In calorimetry, the same input functions are
used for their description as in control theory [64]. However, the termi-
nology used for this purpose is different. Thus,
48 CHAPTER 2
1. The input function described by a short-duration heat pulse of

relatively high amplitude, called in control theory a unit pulse
function (impulse function, Dirac function) (Fig. 2.6), is
expressed by
The unit pulse whose surface area is equal to one has a Laplace
transform y(s) equal to one.
2. The input function described by a constant heat effect in time
corresponds to the unit step function (Fig. 2.7):
The unit step function corresponds to the integral of the unit pulse
function with respect to time. The Laplace transform of the unit step
function is
3. The input function described by a heat effect that is constant in
time over a determined interval of time corresponds to the input
step function of amplitude b and time interval a, called the
rectangular pulse (Fig. 2.8):
where u(t) is determined by
while u(t–a) is expressed by
This is the shape of the input function that is applied when the cali-
bration of the calorimeter consists in generation of a Joule effect that is
constant in time for a defined duration. The exceptions to the rule are
those instruments in the calibration of which the frequency characteris-
tics are used.
The Laplace transform of the rectangular pulse is expressed by
50 CHAPTER 2
4. The input function described by a heat effect rising linearly in time

is presented in Fig. 2.9 and expressed by Eq. (2.49):
The generation of such a forcing function is used in steering theory

as well as in adiabatic and scanning calorimetry. The ramp function has
the following Laplace transform:
5. Generation of the heat effect of the first-order kinetic reaction is

expressed by the exponential function (Fig. 2.10)
The Laplace transform of which is

6) To evaluate the dynamic properties of calorimeters and calibrate

the instruments, period input functions have also been used (Fig. 2.11).
where A is the amplitude of oscillation, is the oscillation frequency,

and
The Laplace transform of the sinusoidal input function is
These periodic heat forcing functions are the basis for some calo-
rimetric methods, e.g. those used in modulated scanning calorimetry.
Determination of both the transmittance of the investigated object
and the Laplace transform of the input function y(t) furnishes the output
function x(s) = y(s)· H(s). With the inverse transformation, we obtain
y(t). Output functions x(t) of proportional, integrating and inertial ob-
jects for various input functions are collected in Table 2.1.
The time-resolved dynamic characteristics presented in Table 2.1
show that the shapes of the output functions depend strongly on the type
of the dynamic object. For proportional objects, the output and input
functions have the same shape, while their values are equal to each other
with the accuracy of the factor.
This means that in a calorimeter with the dynamic properties of a
proportional object the output function gives direct information on the
course of the output function; in other words, the course of the experi-
mentally determined function T = T(t) corresponds to the course of the
changes in heat power P in time t.
52 CHAPTER 2
54 CHAPTER 2
For integrating objects, the course of the output function corresponds

to the accumulation process and to the operation of integration. The
object responds to a generated unit pulse with an output signal, which is
equivalent to the unit step function; the response of the object to the unit
step function is a linearly rising function; production of the ramp forcing
function stimulates the response of the object according to the relation
For inertial objects, the course of the output function is induced by

the inertial properties of the object (calorimeter). This results from the
transmittance form H(s), which is expressed by the operator 1/(Cs+k) or
the operator while the relation between the input function y(s),
the output function x(s) and the transmittance H(s) is presented
graphically by a block diagram (Fig. 2.12)
When the trasmittance is represented by the single symbol H(s), it is

depicted by the block diagram presented in Fig. 2.1.
The form of the transmittance H(s) indicates that the time constant
is a decisive parameter for characterizing the inertial properties of the
object (calorimeter). This also means that the value of the time constant
determines the course of the output function, the character of which is
approached more closely for either proportional or integrating objects.
Simply, the values of control the inertial, damping properties of the
object. Different values of the function x(t), depending on the values of
are responses to the same heat forcing (Fig. 2.13).
The courses of the output functions caused by the generation of the
sinusoidal input function for proportional, integrating and inertial first-
order objects are also presented in Table 2. 1. It is seen that, for a propor-
tional object, only the value of the sinusoidal (harmonic) oscillation
frequency changes. For an integral object, the sinusoidal input function
is transformed by the object to a cosinusoidal function. The amplitude of
the output function is then inversely proportional to the frequency of the
sinusoidal input function. The frequency phase lag is 90° relative to the
input function. For inertial objects, the sinusoidal input function is trans-
formed by the object to an other sinusoidal function that has different
phase and amplitude. In the following relation, expressing the output
function x(t) for the steady state
where
the factor expresses in terms of frequency the ratio of the

output and input function amplitudes. The values of the factor and the
size of the phase shift characterize the dynamic properties of the iner-
tial object. For a frequency close to zero, when sinusoidal changes have
low frequency, the course of the output function is similar to that of the
input function y(t). The phase shift is then close to zero and the proper-
ties of inertial and proportional objects become very similar. The shift in
the output function course relative to the input function results from the
rise in frequency. For infinitely high frequency, the shift in the course of
x(t) is expressed as radians or –90°. When the frequency is related to
the conversed time constant then the oscillation frequency is 0.707
and the phase shift is radians or 45°. This is the frequency related to
the transfer function of an inertial object, given by the operator
or
2.4. Pulse response
The pulse response function is the output function h(t) caused by the
action of the input impulse function (Dirac function). It is applied for
determination of the particular forms of the Laplace transmittance. It can
be obtained by applying the Laplace inverse transformation to the
transmittance Eq. (2.41):
56 CHAPTER 2
where coefficients have the form
from the Cauchy theorem of residues.

The pulse response function is a positive function of real argument t.
It fulfils the condition given by Eq. (2.43):
Taking into account Eq. (2.57) and integrating, we have
If we take advantage of the theorem of the initial value of the

original, i.e. the function h(t), the initial value of the pulse response h(t)
on the basis of Eq. (2.34) can be given by
The pulse response can be obtained experimentally as the response

of the calorimetric system:
a) to a rectangular heat pulse of short duration (“experimental” Dirac
pulse) expressed as a sequence of discrete values
where and is the sampling period; or

b) to the unit step function lasting a sufficiently long time to achieve
the stationary state of heat transfer. In this case, the pulse response is
expressed by the derivative of the calorimetric response
With the measured values of the response at times and

respectively
numerical derivation has to be performed in order to obtain discrete

values of the pulse response h(t).
In the first case, the accuracy of obtaining the values of the unit pulse
response depends on the degree to which the “experimental” pulse ap-
proximates to the “ideal” Dirac function and on the accuracy of the
measurement of the calorimetric signal. In the second case, the proce-
dure of numerical derivation influences the accuracy of obtaining the
pulse response. Since the experimentally obtained response of the sys-
tem does not fulfil the condition [Eq. (2.49)], it is necessary to calculate
the integral from the course obtained for the calorimetric signal and
divide all the values of the signal by the value of this integral. Thus, we
obtain a new course that fulfils the condition needed.
From Eqs (2.59) and (2.60), the dependences between the amplitudes
and time constants can be obtained:
a) for the first-order system:
b) for the second-order inertial system:
c) for the second-order inertial system whose transmittance contains

one zero
It results from Eqs (2.65) and (2.66) that the values of coefficient
and depend not only on the time constants, but also on the zeros of
transmittance.
58 CHAPTER 2
In Fig. 2.13, the plots of pulse responses of calorimeters of various

orders are shown. As the order of the system becomes higher, the pulse
response is “flattened”, and its maximum value drifts more in time.
2.5. Frequential characteristics
To analyze the dynamic properties of calorimeters, frequential char-

acteristics, similarly as time-resolved characteristics, are determined [8,
67]. To obtain the frequency characteristic, Fourier transforms are used.
The Fourier transform which is a complex function of the real
variable can be written as follows:
or in the form
where and are the real (even) and imaginary (odd) parts of
the transmittance respectively, we can write
Because
from Eq. (2.69) we have
Magnitude is called the amplitude. Division of Eq. (2.69) leads

to
Thus
Magnitude is called the phase and is equal to the argument of

transmittance The phase describes the relative amounts of sine
and cosine at a given frequency.
The spectrum transmittance of an N-order inertial system has
the form
Equation (2.75) is equivalent to Eq. (2.67), assuming that

In the spectrum transmittance described by Eq. (2.75), let us
distinguish the component transmittances and
If
this becomes
and for
It results from Eqs (2.78) and (2.79) that the amplitude of the trans-
mittance is equal to the product of the amplitudes of particular
60 CHAPTER 2
transmittances. Thus, the phase of the transmittance is equal to the sum

of the particular transmittances of the phases.
According to Eqs (2.75) and (2.79), the phase is described by
the equation
If the magnitude approaches infinity, then, according to Eq. (2.80),

the value of the limit phase approaches
To analyze the dynamic properties of the object, the amplitude char-

acteristics, phase characteristics and amplitude-phase characteristics are
used. The amplitude characteristic is a relation expressing the ratio of
the amplitude of the output function to that of the input function. The
dependence of a phase shift in frequency is called the phase characteris-
tic of the object. The amplitude-phase characteristic presents the ampli-
tude changes and the phases of the output function. Two types of plots
are usually used to draw the amplitudes: one in the coordinates
and the other in the coordinates and two types
of plots for the phase: in the coordinates or The plot in
the coordinates gives the amplitude-phase characteristics.
Let us analyze the amplitude-phase characteristics for a few types of
spectrum transmittance.
According to Eqs (2.72) and (2.75), the amplitude is described
by the function
For sufficiently large values of the function can be

approximated by the equation
Taking logarithms of both sides of the above equation gives
It results from the above equation that the plot of the amplitude in the
coordinate system asymptotically approaches a straight line
with direction coefficient equal to –(N – m). In this way, the asymptotic
plot permits an estimation of the difference between the number of poles
and the number of zeros of the transmittance. The plot of helix shape
which passess through the –(N – m) guater of the system in the coordi–
nates will be obtained. The number of –(N – m) is related with
the phase shift [Eq. (2.81)].
2.6. Calculations of spectrum transmittance
The spectrum transmittance can be obtained as the Fourier

transform of the pulse response or as the quotient of the Fourier
transform of the system response to a known heat effect.
where is a heat pulse of constant heat power and time interval u

(input step function)(Fig. 2.14a); is the temperature response to
this heat effect (Fig. 2.14b).
In order to determine the spectrum transmittance it is neces-
sary to calculate the integrals on the right-hand side of Eq. (2.85). Ac-
cording to the Euler formula:
where
62 CHAPTER 2
and are the real (even) and imaginary (odd) parts of the
Fourier transform of the response function, respectively.
The result of the calorimetric measurement is obtained as the number
sequence temperature data [Eq. (2.66)]
at times respectively. Thus, the integrals of the calorimetric

signal [Eqs (2.87) and (2.88)] are to be calculated numerically by
applying a convenient approximation, e.g.
Then, Eqs (2.87) and (2.88) become

Integration and rearrangement of Eqs (2.90) and (2.91) gives
In this way we obtain the real and imaginary parts of

the Fourier transform of the response function to a heat pulse. The
Fourier transform of the input function should also be determined.
Let us determine the transforms for the following input functions: a
step input function, a pulse function, and a periodic (sinusoidal) func-
tion). These functions are often used for spectrum transmittance deter-
mination.
The Fourier transform of the heat pulse can be written in the form
where
are the real and imaginary parts, respectively, of the Fourier transform
of the input pulse.
According to Eqs (2.85), (2.86) and (2.92) – (2.94), we have
64 CHAPTER 2
or
where
When the calorimeter is calibrated by a unit pulse of amplitude

and sufficiently long duration, the spectrum transmittance can be
expressed as
where is the calorimetric response to a unit pulse heat effect. Ap-

plication of the approximation of the calorimetric response given
by Eq. (2.89) yields
and, after integration, the spectrum transmittance obtained can be writ-

ten in the form
where
On the basis of the above method, the algorithm of the calculation of

the Fourier transforms expressed by Eqs (2.85) and (2.100) is calculated
by using the Fast Fourier Transform Method [68].
The Fourier transform of the impulse response h(t) can be obtained
in the case of a sinusoidal input function (Fig. 2.11):
The Fourier transform is equal to
Hence
becomes
where
It results from Eqs (2.96)–(2.99) that the accuracy of the determina-

tion of the spectrum transmittance depends on the accuracy of the
determination of and Errors connected with their determi-
nation are due to the approximation of the thermograms or
and also connected with the accuracy and precision of the measurements
made.
66 CHAPTER 2
2.7. Methods of determination

of dynamic parameters
Selected methods will now be discussed that are used to determine

the dynamic properties of calorimeters as inertial objects. Several of
these methods are similar to those used in steering theory.
Different methods are presented for determining the time constant of
a calorimeter treated as an inertial object of first order. The methods
used to determine the dynamic parameters of calorimeters that are
inertial objects of order higher than one are also discussed. All these
numerical methods, algorithms and listing programs are described in
detail in [67].
To apply each of the methods presented below, a knowledge of the
physical properties of the investigated object is not necessary. These
methods have been qualified as useful in calorimetry to identify the
dynamic parameters and to study thermokinetics.
To obtain the most information about the properties of the calorime-
ter, it is recommended to determine the physical properties of the par-
ticular domains of the calorimeter and quantities characterizing the heat
transfer between the domains themselves and between the domains and
the environment. When we follow this procedure, the dynamic proper-
ties of a calorimeter can be determined by using the method of N-
domains based on the general heat balance equation [Eq. (1.147)]. This
method will be presented in Chapter 3.2.4.
2.7.1. Determination of time constant

The dynamic properties of a calorimeter treated as an inertial object
of first order are characterized unambiguously by the time constant
To evaluate the time constant on the basis of the heat balance equa-
tion of a simple body, different input functions are used. Consider the
determination of by applying the input step function [Eq. (2.45)] under
conditions where the initial temperatures of the calorimeter and isother-
mal shield are the same. Equation (2.19) can then be written in the form
where
is determined by Eqs (2.45) and (2.47).

The Laplace transform of the function y(t) corresponds to
while after the Laplace transformation Eq. (2.111) becomes
After simple rearrangement, Eqs (2.113) and (2.114) can be written

in the form
Inverse Laplace transformation of Eq. (2.115) gives
The function T(t) expressed by Eq. (2.116) can be presented graphi-

cally by using the curves I, II and III shown in Fig. 2.15. The first term
on the right-hand side of Eq. (2.116) is related to curve I, and the second
term on the right-hand side of this equation to curve II. Curves I and II
have identical shapes, but there is a shift in time between them, related
to the duration of the heat impulse produced. For this period of time, the
courses of the changes in the calorimeter temperature T in time t are
represented by the interval 0K of curve I. When t > a, the course of the
function T(t) from to the shield temperature is presented in curve III.
This is the cooling curve of the calorimeter. The changes in temperature
that occur here are only a result of the existing difference in tempera-
tures The interval KM of curve III graphically represents the differ-
ence between the values T(t) of the first and second terms on the right-
hand side of Eq. (2.116).
68 CHAPTER 2
When the heat generation period is long enough for a new state of
thermal equilibrium to be reached, characterized by Eq. (2.19) can be
written in the form
The solution of Eq. (2.117) when T(0) = 0 is
which corresponds to the first term on the right-hand side of Eq.

(2.116). Equation (2.118) describes the heating process occurring in the
calorimeter (curve 0I, Fig. 2.15).
Let us use Eq. (2.118) to present several procedures for determining
the time constant
Procedure 1. We find the time derivative of the heating curve
From Eq. (2.119), we have that a tangent to the curve 0K crosses an

asymptote of the curve at the point relating to (Fig. 2.15).
Procedure 2. At every point of the heating curve characterized by the

interval 0K of the curve I (Fig. 2.15), the length of the subtangent
determined by its point of intersection with the straight line is related
to the time constant From Eqs. (2.117) and (2.118), we have
If we take into account the graphical presentation of the heating

curve in (Fig. 2.15), we have
where
Thus, the length of the subtangent is equal to the time constant

value
Procedure 3. After time T(t) is equal to
After time the temperature becomes and after

time we have Proceeding in such a way for the
known values of and T(t) of the heating process, we can obtain the
value of the time constant or its multiplicity.
Procedure 4. The value of the time constant can be determined

analytically. The values of T(t) related to time moments and cor-
respond to
Hence, Eqs (2.124) – (2.126) become

70 CHAPTER 2
Thus
and after rearrangement we have
Procedure 5. To obtain the time constant the integration method

can be used.
Hence, the time constant is equal to
Integral represents the surface area F1 between the

straight line and the heating curve (Fig. 2.16a).
The changes in temperature T(t) in time, caused only by the initial
temperature difference between the calorimeter and shield, are also used
to determine the time constant In this case, it is assumed that y(t) = 0,
and the cooling process is expressed by equation
The solution of Eq. (2.134) is
The course of T(t) is graphically presented by the cooling curve

(curve IV) in Fig. 2.15.
The procedures used to determine the time constant on the basis of
the cooling curves are not much different from the procedures presented
above.
Procedure 1. The same as in the case of the heating curve; the length
of the subtangent at every point of the cooling curve is equal to the time
constant (see heating curve, Fig. 2.16, Procedure 2).
Procedure 2. After time the decrease in T(t) is 36.8% com-

pared to the initial value This results from Eq. (2.135). In a similar
way, the value of T(t) can be determined for the time constant multiplic-
ity. Knowing temperature and choosing a matching value of T(t), one
can determine the value of the time constant.
Procedure 3. The value of the time constant can be determined ana-

lytically if at least two temperature values of the cooling process defined
as a function of time are known. When, after time of the cooling proc-
72 CHAPTER 2
ess, the value of T(t) becomes and, after time it becomes

then according to Eq. (2.135)
Division of both sides of Eq. (2.136) by Eq. (2.137) gives
Hence
Procedure 4. The time constant for the cooling process can be

calculated by an integrating procedure as for the heating process (Fig.
2.16b). On calculation of the integral:
Hence
Procedure 5. Taking logarithms of both sides of Eq. (2.135) gives
Hence
Equation (2.143) is used for the graphical determination of the time

constant When the experimentally determined T and the t data for the
cooling process have been obtained, the plot in the coordinates (t, lnT)
can be drawn, as shown in Fig. 2.17a [8]. When the dynamic properties
of the calorimeter are characterized by one time constant the relation
lnT = f(t) is expressed by a straight line (Fig 2.17a), which forms an
angle with the t axis, for which
This line cuts the axis at the point of the ordinate. Thus
When the dynamic properties of the calorimeter are characterized by

more than one constant of time [Eq. (2.57)], at the begining of the
cooling process the relation lnT = f(t) is not linear, as shown in Fig.
2.17b. In this case, the discussed method can be applied to evaluate the
higher time constants. The following procedure is used. The straight line
interval (Fig. 2.17b) is extended to the point of intersection with the lnT
axis and the first time constant is determined. Next, a new function of
the form
is created and a new plot in the coordinate system can be drawn.

The second time constant is determined. The iterative procedure is
repeated until a plot similar to the plot given in Fig. 2.17a is obtained.
74 CHAPTER 2
The number of time constants which can be distinguished depends on

the properties of the calorimeter and the accuracy of the determination
of the experimental data.
2.7.2. Least squares method

The least squares method for determination of the transmittance pa-
rameters was proposed by Rodriguez et al. [69]. This method allows the
time constants and the zeros of the transmittance nominator to be
obtained by approximation of the pulse response of the calorimeter by
the least squares nonlinear curve-fitting procedure described by
Marquardt [70].
In order to use this method, it is necessary to assume or determine the
order of the model number of poles and the number of transmittance
zeros. According to these assumptions, the pulse response is a func-
tion of time t, poles and zeros
where m < N. Introducing vector the components of which are poles

and zeros:
Equation (2.147) can be written in the form
As is a nonlinear function of the components, expansion of

this function as a Taylor series in the neighborhood of point is
applied:
neglecting the derivatives of higher order. As a criterion of fitting the

experimentally determined pulse response and approximated pulse
response it is assumed that
Equation (2.150) then becomes
where < 0, T > is the time interval in which the changes in pulse
response are measured, and
In possession of the discrete values of the pulse response, instead of

Eq. (2.152) the following fitting criterion is accepted:
where and is the sampling period. From the

necessary condition of the minimum of the function expressed by Eq.
(2.154):
we have the following set of equations:
Solving the set of Eqs. (2.156) with respect to leads to the poles
and zeros of transmittance according to the equation
Since the linear approximation is applied to the nonlinear function,

we can obtain the values of the parameters only with large error in one
iteration. Thus, it is necessary to repeat the iteration, assuming the
calculated values as initial values and repeat the iterative procedure until
we obtain a suitable approximation of the pulse response.
76 CHAPTER 2
2.7.3. Modulating functions method

The modulating functions method was proposed by Ortin et al. [71].
This method permits determination of the poles and zeros of transmit-
tance. The poles of transmittance are determined on the basis of an ac-
cepted model in the form of a differential equation. As the pulse re-
sponse h(t) is the finite sum of exponential functions [Eq. (2.157)]:
it can be assumed that it satisfies the differential equation with constant

coefficients:
where is k times the derivative with respect to time t of the pulse

response of the system, and Next, the time interval in
which the changes in the pulse response are measured (observed) is
assumed as the basis of the modulating functions which fulfils
the conditions
for i = 1, 2, ... , N; k = 0, 1,..., N – 1 is also assumed. These functions

have continuous derivatives of desired order. The order and the smooth-
ness are connected with the order of differential Eq. (2.159). Multiply-
ing both sides of Eq. (2.159) by and intergrating with respect to
time t in the interval yields
Putting
leads with respect to the coefficients to the following set of algebraic

equations:
The above set of equations can be solved with respect to

From the values of the coefficients from the characteristic
equation
it is possible to determine the eigenvalues (poles) of the transmittance,

taking into account that the time constants
The expressions in Eq. (2.162) contain the derivatives
of the pulse response function h(t). To avoid the calculations of these
derivatives, which can result in the introduction of large errors, Eq.
(2.162) (after integrating by parts) can be presented in the form
taking into account the conditions given by Eq. (2.160).

When we have determined the poles of transmittance and know the
value of the pulse response h(t) in Eq. (2.158), only the amplitudes
are unknown. These coefficients can be determined by applying the
modulating function procedure given above to the pulse response:
On putting
we obtain the following set of equations:

78 CHAPTER 2
The coefficients of the pulse response h(t) can be determined by

solving the above set of algebraic equations after previous calculations
of the coefficients
From the determined time constants and coefficients the
Laplace transform to the pulse response gives
where
is the denominator of the transmittance, and
is the m–degree polynomial m < N with respect to s. By solving the

equation
the zeros of the transmittance H(s) are obtained.

The general form of the equation expressing the relation between the
generated heat power P(t) and the temperature changes T(t) of the
calorimetric system has the form
Multiplying both sides of the above differential equation by the

modulating function and integrating with respect to time t in the
interval leads to the following set of algebraic equations with
respect to coefficients and
where
The obtained set of Eq. (2.175) has a similar form as that of the set of
Eq. (2.162). In the particular case when the calorimeter is calibrated by a
constant heat effect of heat power and duration u smaller than
the relation for coefficients given by Eq. (2.177) (taking into
account the conditions Eq. (2.159) and integrating by parts), can be
simplified to the following form:
The flow diagram of the modulating functions method, the program

algorithm and the listing program are given in [67].
2.7.4. Rational function method

of transmittance approximation
In this method, the transmittance H(s) is approximated by a rational
function [67, 72, 73]:
where D(s) and L(s) are polynomials of degree m and N(m<N) given by
80 CHAPTER 2
The rational function L(s)/D(s) is the approximation expression of

function H(s) if the expansion in the power series with respect to s is
identical with the expansion in the power series of function H(s) to the
degree m +N. As the criterion of fitting, we can assume
or, using Eq. (2.183), we can write
where is the number of points taken into account in the approximation.

The values are calculated by numerical integration, having the
values of the pulse response h(t) and assuming a set of values of the
complex variable s. In order to adequately define the criterion
Eq. (2.184), the values of variable s must be real. Function (2.185) is a
function of N + m + 1 unknown parameters and
(n = 0, 1, ... , N). The necessary condition of the minimum of function
(2.185) with respect to parameters and has the form
and gives the following set of algebraic equations:
or, after simplification:

On solving the above set of equations with respect to parameters

and we can calculate their values as well as the polynomials D(s)
and L(s), the quotient of which gives the expression approximating to
the transmittance H(s). The roots of the polynomial L(s) yield the zeros
of transmittance, and the roots of the polynomial D(s) yield the poles of
the transmittance.
2.7.5. Determination of parameters

of spectrum transmittance
To determine the dynamic parameters of the calorimetric system, the
transmittance of the compensating system (numeric or analog)
[67, 74] should be matched in such a way that the resultant
transmittance corresponds to the non-inertial system and fulfils
the following condition:
where is the spectrum transmittance of the calorimeter. As the

basis for determination of the transmittance, the experimental pulse re-
sponse of the calorimeter is taken. Next, through use of the Fast Fourier
Transform (FFT) procedure, the values of the amplitude (modulus)
and the phase of the Fourier transform of the pulse response are
calculated. These values are plotted in a Bode plot. From the Bode plot,
the value of the direction coefficient of the last slope asymptote, which
permits an evaluation of the difference between the number of zeros and
the poles of the transmittance is determined. If this coefficient is equal
to –1, the transmittance can have one pole, or one zero and two poles, or
82 CHAPTER 2
two zeros and three poles, etc. If this coefficient is equal to –2, the
transmittance can have two poles, or one zero and three poles, or two
zeros and four poles, etc.
To illustrate our considerations, let us assume, for example, that the
value of the direction coefficient of the last asymptote is equal to –1.
Having determined the difference between the number of zeros and

poles of the transmittance, on the basis of the Bode plot (Fig. 2.18) we
can find the point at which the first slope asymptote intercepts
the axis, and thus estimate the time constant with he largest
value, according to the relationship
In the knowledge of the time constant we determine a new

transmittance
and its amplitude and phase and draw their plots. If the plot
of the amplitude and the plot of the phase are similar to the plots of the
relations and for a first-order inertial object in the accepted
frequency range, we stop our calculation and assume that our system is
the first-order inertial system of transmittance:
In the other case, from the relations and it can result that
the number of zeros is equal to the number of poles. We assumed ear-
lier, that the value of the direction coefficient is equal to –1, and we
have to deal with one pole and one zero, or two poles and two zeros, etc.
Let us assume additionally that the experimental data enable us to de-
termine only one zero and one pole more.
In the first case (Fig. 2.19), as emerges from the previous considera-
tions, the value of the zero of transmittance is larger than the value of
the second pole. Thus, we can determine from the slope of the
asymptote, and we have
From the value of the horizontal asymptote, we can calculate the

second time constant
After calculation of the parameters of the transmittance, we can write
In the second case, the value of the zero of transmittance is smaller

than the value of the second pole. In this case, from the slope of the
asymptote we can calculate and thus the value of the second time
constant is
84 CHAPTER 2
From the value of the horizontal asymptote, we can calculate

from the formula
and write the form of the transmittance as above. If the amplitude plot
and the phase plot of the obtained transmittance are similar to the
relation that results from the dependence in an appropriate
frequency range, we can assume that the parameters of the transmittance
have been determined correctly.
Chapter 3
Classification of calorimeters
Methods of determination of heat effects
3.1. Classification of calorimeters
The papers that consider determination of the heat effects that ac-
company physical and chemical processes present a wide spectrum of
types of calorimeters. These devices have been given various names by
the authors, who made their choices on the basis of different criteria.
Names such as low-temperature calorimeters, high-temperature calo-
rimeters and high-pressure calorimeters come from the conditions of
temperature and pressure under which the measurements are performed.
In some cases, the type of process investigated is decisive: calorimeters
for heat of mixing, heat of evaporation, specific heat measurements, and
others. The names of calorimeters often have to contain information
about their construction features, e.g. labyrinth flow calorimeter, calo-
rimetric bomb, drop calorimeter, or stopped-flow calorimeter. The name
of the device sometimes stems from the name of its creator. Examples
here include the calorimeters of Lavoisier, Laplace, Bunsen, Calvet,
Swietoslawski, Junkers, and others. This diversity of the names of calo-
rimeters justifies an attempt to find features that classify the devices
unambiguously.
Let us first define a “calorimeter” as an instrument devised to deter-
mine heat. In any calorimeter, we may distinguish: 1) the calorimetric
vessel (often called the cell, container, or calorimeter proper) at tem-
perature that is usually in good contact with its contents, in which
the studied transformation occurs. The contents include the reactant
samples and subsidiary accessories necessary to achieve the investigated
transformation (e.g. to initiate the reaction, or to mix the reagents) or to
calibrate the device; and 2) the surroundings at temperature of-
86 CHAPTER 3
ten called the shield, environment or thermostat. The surroundings form

a part of the calorimeter that is functionally distinct from the measuring
system, with a defined temperature time dependence [82]. It may also be
considered the first thermostat shield of the calorimetric vessel (in some
calorimeters there are several shields).
There are single, differential and twin calorimeters (see 3.2.2.).
Various classifications of calorimeters have been presented [75–83].
The classification given here [84] is based on the assumption that the
calorimeter is a dynamic object in which heat is generated. Calorimeters
are graded by applying the criteria of the temperature conditions under
which the measurement was made. As an initial basis for further consid-
erations, the Fourier – Kirchhoff equation (Eq. (1.29)) has been used in
the following form:
A set of simplifying assumptions is next introduced to shorten this

form of equation. We assume that the process takes place under isobaric
conditions. On multiplying both sides of Eq. (3.1) by volume V, we have
where is equal to heat capacity C. Furthermore, assuming bound-

ary conditions of the third kind (Newton’s cooling law), we can write
where is the temperature of the calorimetric vessel and is the shield

temperature. Taking into account Eq. (3.3), Eq. (3.2) becomes
With the additional assumptions that mass transport takes place only
in the x direction, and that temperature T and heat power P are functions
of the one coordinate x and time t, e.g. and Eq.
(3.4) becomes
CLASSIFICATION OF CALORIMETERS 87
Equation (3.5) describes the heat transfer in calorimeters with mass

exchange. These calorimeters are called open calorimeters. In contrast,
calorimeters in which mass exchange does not occur are called closed
systems. Then, w = 0 and Eq. (3.5) takes the form:
In the construction of a calorimeter, it is possible to provide condi-

tions which make it possible to carry out an experiment in a desired
manner, e.g. to impose the temperature conditions of the calorimetric
vessel or of the calorimetric shield
const., or the temperature difference between them. In
this manner, the following cases of temperature conditions can be dis-
tinguished:
On the basis of the criteria listed above, calorimeters can be divided

into two groups:
I. Adiabatic calorimeters, in which the temperature gradient be-
tween the calorimeter proper and the shield is equal to zero
0); during the calorimetric measurement, heat transfer does not
occur between the calorimetric vessel and the shield.
II. Nonadiabatic calorimeters, in which the temperature gradient be-
tween the calorimeter proper and the shield is different from zero
during the calorimetric measurement, heat transfer oc-
curs between the calorimetric vessel and the shield.
Two subgroups of adiabatic calorimeters one can be distinguished:
88 CHAPTER 3
Ia. Calorimeters with constant temperature They can be called

adiabatic-isothermal.
Ib. Calorimeters where the temperature of the shield T0(t) changes in
time. They can be called adiabatic-nonisothermal or simply adia-
batic.
Nonisothermal calorimeters involve the following subgroups:
IIa. Calorimeters with constant temperature T0(t) (isothermal sur-
rounding shield), called isoperibol calorimeters.
IIb. Calorimeters in which the shield temperature changes in
time (e.g. scanning calorimeters).
In both subgroups IIa and IIb, there are calorimeters with a tempera-
ture gradient that is stable in time, or with a calorimetric vessel whose
temperature changes in time. The calorimeters in subgroup IIa are non-
adiabatic-isothermal, whereas those in subgroup IIb are nonadiabatic-
nonisothermal.
The schedule of the presented calorimeters division according to the
temperature conditions by Czarnota and Utzig [85] is shown in Fig. 3.1.
Let us determine particular forms of Eq. (3.6) for distinguished tem-

perature conditions. These equations will then be treated as general
mathematical models of the classified calorimeter groups. Particular
forms of Eq. (3.5) will be given only for the types of open or closed
calorimeters that are known by the authors.
1. When and Eq.

(3.6) takes the form
Calorimeters that are described by Eq. (3.7) are characterized only

by heat accumulation. They are adiabatic-nonisothermal calorimeters,
and usually called adiabatic calorimeters. Their functioning rule is based
on the assumption that the temperatures of the calorimetric vessel and
the shield change in the same manner during the measurement. Their
dynamic properties are those of integral objects.
Adiabatic calorimeters were first used by Richards [76, 86] and then
Swietoslawski [76]. Nowadays, adiabatic calorimeters are used for stud-
ies of various transformations in a wide temperature range, from very
high temperatures to very low, close to the absolute zero (0.001 K).
Mention may be made of [83]: 1) low-temperature calorimeters, like
those of Westrum Jr et al. [87–89], Furukawa et al. [90], Suga and Seki
[91], and Gmelin and Rodhammer [92]; 2) room-temperature calorime-
ters, such as those of Swietoslawski and Dorabialska [93], Zlotowski
[94], and Prosen and Kilday [95]; and 3) high-temperature calorimeters,
e.g. those of Kubaschewski and Walter [96], West and Ginnings [97],
Cash et al. [98], and Sale [99]. High-pressure adiabatic calorimeters
were designed by Goodwin [100], Rastogiev et al. [101], Takahara et al.
[102] and others.
In measurements performed with the use of adiabatic calorimeters,
quite large amounts of substances have been applied (even several dozen
grams). A series of new adiabatic calorimeters was recently designed
that allow measurements on very small amounts of substance (< 1 g),
among them the calorimeters constructed by Ogata et al. [103], Matsuo
and Suga [104], Kaji et al. [105], and Zhicheng Tan et al. [106].
One of the first scanning adiabatic calorimeters designed in the past
was the DASM 1M microcalorimeter [107], used to determine the ap-
parent molar heat capacity and conformational changes of proteins and
nucleic acids. Measurements are performed in the temperature interval
from 10 to 100°C, the shield heating rate can vary from 0.1 to
and the sensitivity of the instrument is A
90 CHAPTER 3
new generation of scanning adiabatic calorimeters is represented by the

devices designed by S.V. Privalov et al. [108] and Plotnikov et al. [109].
Each of these instruments is constructed as the differential system.
2. When and the
terms of the left-hand side of Eq. (3.6) are equal to zero. Then:
Since and are identical during the measurement, the proc-

esses in such adiabatic calorimeters take place under isothermal condi-
tions. These conditions can be fulfilled, when two heat processes of
opposite sign and occur:
where is the heat power of the process studied and is the

compensating heat power.
The best-known [83] such calorimeters are those of Lavoisier and
Laplace (determination of the mass of melted ice) [110], Bunsen (pyc-
nometric determination of the volume change of the liquid water-ice
system) [111], Dewar (volumetric determination of the air vaporized)
[112] and Jessup (room-temperature operation based on the melting of
diphenylether) [113]. In all of these devices, determinations are made of
the changes in the measured quantity that result from the phase trans-
formation. However, in this case it is very difficult or impossible to ob-
tain conditions that correspond to thermodynamic equilibrium [76].
Progress in the development of adiabatic-isothermal calorimeters was
made by Tian [114–116], who utilized the Peltier and Joule effect to
compensate the generated heat power. At present, the modern electronic
and steering devices applied to generate these effects permit measure-
ments with high accuracy. A good illustration of this is the achievements
at Brigham Young University [117], where this type of calorimetry has
been developed for almost 40 years. The titration calorimeter [118, 119]
and the few high-pressure flow calorimeters [120–122] have been con-
structed there.
3. When and
const., Eq. (3.6) becomes
Methods for the determination of heat effects in these types of calo-

rimeters are based on the assumption that
where is the heat power generated during the process examined;

is the compensating heat power generated additionally to carry out
the calorimetric measurements under isothermal but nonadiabatic condi-
tions.
This class includes the calorimeters of Olhmeyer [123], Kisielev et
al. [124, 125], Dzhigit et al. [126], Pankratiev [127, 128], Wittig and
Schilling [129], Zielenkiewicz and Chajn [130], Hansen et al. [131] and
Christiansen and Izaat [132].
4. When and Eq. (3.6)
takes the form of Eq. (3.12) for the open system and Eq. (3.13) for the
closed system:
It results from Eqs (3.12) and (3.13) that the calorimeter systems de-
scribed by these equations are open and closed nonadiabatic-
nonisothermal (n-n) systems. For the open calorimetric systems de-
scribed by Eq. (3.12), heat and mass exchange occur simultaneously.
Closed, nonisothermal-nonadiabatic calorimeters have for a long
time been the most widely used class of calorimeters. The heat effect
that is generated in these calorimeters is in part accumulated the in calo-
rimetric vessel and in part exchanged with its surrounding shield. These
are dynamic properties of inertial objects. The parameter that is decisive
as concerns their properties is the time constant (or time constants).
In this class of calorimeters, there are instruments that have time
constants of and others with time constants of several
They have different constructions and find various applications. Among
them there are:
92 CHAPTER 3
a) Dewar vessel calorimeters in more or less sophisticated form, such

as the well-known Nernst low-temperature calorimeter [133] or
Pierre Curie and Laborde‘s twin calorimeter [134] used in radiol-
ogy. The Dewar-type calorimeters have found application in the
determination of the average specific heats of organic liquids and
their mixtures [135, 136], the heat of evaporation [137], the heat
of polymerization [138–142], the heats of hydration of cements
[143–146], etc. Vacuum jackets of special design are used, for in-
stance, in the accurate instrument of Sunner and Wadsö [147],
and the microcalorimeters of Wedler [148], et al. [149] and
Randzio [150] for measurement of the heats of chemisorption of
gases on thin metal films.
b) Calorimeters with the jacket filled with water or air are mainly
used to measure heat effects with a duration of a few minutes,
calculated by use of the method of corrected temperature rise
(§ 3.2.9). The well-known Regnault-Phaundler equation is then
applied. This group includes, for example, oxygen [151–153] and
fluorine [154–156] calorimetric bombs and calorimeters used to
study thermokinetics and the total heat effects of reactions [157–
160].
c) High-temperature calorimeters such as those of Eckman and Ros-
sini [161] or Mathieu et al. [162].
d) Heat-flow or conduction calorimeters, where the heat exchange
between the calorimetric vessel and the isothermal shield is excel-
lent. Most of them make use of the thermometric “heat flow-
meters” in a differential assembly, like the well-known Calvet
microcalorimeter [10] and the others that are characterized by
very high sensitivity (they can even detect signals of and
are applied for various kinds of investigations [163, 164], e.g. the
metabolism in living organisms [165–167], sorption and kinetics
of adsorption [168–171], photochemical reactions [93], calorimet-
ric titration [173–175], investigation of the properties of medica-
ments [176], and the precipitation or crystallization of lysozyme
[177].
e) Calorimeters where the heat generated is transferred to the liquid
that flows around the outside surface of the calorimetric vessel, as
in the Junkers [178] and labirynth flow calorimeters [76, 179,

180].
f) AC calorimetry, which is applied intensively for the measurement
of heat capacity in the region of phase transitions [181–185].
g) A number of “quasi-adiabatic” calorimeters are used in such a way
that, in the calculation of the heat involved, the transfer of heat
between the calorimetric vessel and the surroundings is neglected.
Such are the flash calorimeters of Rosencwaig [186, 187], Callis
et al. [188] and Braslawsky et al. [189], and the photoacoustic
calorimeter of Komorowski et al. [190].
There are open nonisothermal-nonadiabatic calorimeters like those of
Picker, Jolicoeur and Desnoyers [191–193].
When measurements in an open, flow n-n calorimeter are made after
a relatively long time
Equation (3.12) takes the form
Relationship (3.17) describes the processes occurring in the flow and

stopped-flow calorimeters of Roughton [194, 195], Kodama and
Woledge [196] and Berger [197].
5. When and Eq.
(3.6) takes the form for the closed system:
Equation (3.18) describes the nonisothermal-nonadiabatic system in

which changes occur in the shield temperature. The temperature rise is
usually linear and described by the ramp function (Eq. 2.49) as in the
94 CHAPTER 3
Calvet scanning microcalorimeter. There are several thermal analysis

devices for which Eq. (3.18) in its simplified form can be considered as
mathematical model. They operate via observation of the temperature of
the samples caused by the forcing function generated on the shield. This
group includes: devices for heating and cooling curve determination
(temperature measurement); differential thermal analysis, DTA (meas-
urement of the temperature difference between the studied sample and
the standard substance) [198, 199]; heat flux differential scanning calo-
rimetry, hf-DSC (determination of the difference in heat flux between
the studied sample and the standard substance to the shield [200]; and
modulated temperature differential calorimetry, mt-DSC (the tempera-
ture change of the sample described by the frequency and amplitude of
vibration) [116].
Regardless of which measurement method is used, in each of them
the heat effects generated in the sample and in the calorimeter shield are
superimposed. In consequence of the same type of inertial properties (of
inertial objects) of the devices mentioned, the course of the output func-
tion caused by the programmed rise of temperature of the shield is al-
ways the same (see § 3.2.5). Let us confine ourselves to considering
only the changes in temperature that are caused by linear rise of the
shield temperature When the initial temperature of the shield
the temperature of the vessel and the ramp func-
tion is
Equation (3.18) then takes the form
Division of both sides of Eq. (3.20) by G yields
The solution of Eq. (3.21) is

When the calorimeter proper and the shield are initially in thermal
equilibrium, i.e. and are equal to each other, and the measure-
ment is performed until conditions of stationary heat exchange between
the calorimeter proper and shield Eq. (3.22) takes the form
The courses of the changes in and according to Eq. (3.22) are

presented in Fig. 3.2. This shows that after a certain period of time
following the start of measurement, the course of change in
becomes linear. From this point, the difference between and is
equal to and the shift between the temperature curves is equal to the
time constant Such a temperature course is observed when the sample
is a thermally passive object. For an endothermic reaction, the line
appears to be twisted as a result of decrease of the heating rate. For an
exothermic reaction, the twist of the line is linked to the increase of
the heating rate. This is presented in Fig. 3.3(a). Figure 3.3(b) shows the
temperature change reading determined by differential measurement. In
the case of a Calvet DSC microcalorimeter, thermogram data are usually
used for the determination of P(t) and then Q(t).
96 CHAPTER 3
6. When and
const., Eq. (3.6) (similarly as previously) takes the form of Eq. (3.10),
i.e.
The function P(t) is a superposition of at least three heat forcing

functions relating to the heat power generated by the studied proc-
ess, the compensating heat power and the heat power gener-
ated in the shield in order to keep its temperature in compliance with the
programmed changes.
7. When and Eq.
(3.6) becomes
The authors do not know any examples of calorimeters of this type.

The classification of calorimeters presented above conforms with

that given in 1930 by Lange and Miszczenko [1], who distinguished four
groups of calorimeters:
1) isothermal-adiabatic;
2) isothermal-nonadiabatic;
3) nonisothermal-adiabatic; and
4) nonisothermal-nonadiabatic.
Obviously, the experimental description of the device should also
contain information such as: 1) the purpose of the instrument (combus-
tion, heat of mixing, heat capacity, sublimation, etc.); 2) the principles
and design of the calorimeter proper, including the ranges of tempera-
ture and pressure in which measurements can be performed; 3) the
measured quantity and measuring device; 4) the static and dynamic
properties of the calorimeter; the calibration mode and the methods of
measurement and determination of heat effects; 5) the operational char-
acteristics of the calorimetric device, the sensitivity noise level, the
method of calibration, the accuracy, etc.; 6) a description of the experi-
mental procedure used in the calibration and the actual measurements.
The mathematical models of calorimeters presented above were ap-
plied as the basis of methods used to determine heat effects.
3.2. Methods of determination of heat effects
3.2.1. General description of methods

of determination of heat effects
Many methods are used to determine heat effects. Some of them al-
low the determination of the total heat effect Q studied, while others
permit the determination not only of the total heat effects, but also of the
course of thermal power P in time t (function P(t), called the thermoki-
netics or thermogenesis).
For the characteristics of these methods, the general heat balance
equation (Eq. (1.148)) has been used [21]:
98 CHAPTER 3
In an adiabatic method (§ 3.2.3), it is assumed that only heat

accumulates in the calorimeter, which is treated as an integral object. A
generated heat effect P(t) is then described by the first term on the right-
hand side of Eq. (1.148).
Several methods are used for nonadiabatic calorimeters.
In the multidomains (N-domains) method (§ 3.2.4), particular forms
of Eq. (1.148) are applied, depending on the number of distinguished
domains, and their mutual location. A similar procedure is applied in the
method of finite elements (§ 3.2.5).
In the dynamic method (§ 3.2.6), the calorimeter is treated as a sim-
ple body of uniform temperature. The detailed form of Eq. (1.148) is
then a heat balance equation of a simple body. The dynamic method is a
one of the most frequently used in the determination of total heat effects
and thermokinetics.
In the modulating method (§ 3.2.8), Eq. (1.148) is usually reduced to
the form of a heat balance equation of a simple body [Eq. (1.99)], one of
the input forcing functions being a periodic function.
In the flux method (§ 3.2.7), the calorimeter is treated as a propor-
tional object. In this method, it is assumed that the accumulation of heat
in the calorimeter proper is negligibly small.
The steady-state method (§ 3.2.9) is based on the assumption that the
heat power generated in the calorimetric vessel is compensated by addi-
tionally generated heat power of opposite sign. The calorimeter is
treated as a proportional object. The inertial properties of the calorimeter
are neglected. The left-hand side of Eq. (1.148) is equal to zero.
The heat balance equation (Eq. (1.148)) reduced to the heat balance
equation of a simple body [Eq. (1.99)] is also the basis of many methods
used to determine total heat effects. One of the best-known is the
method of corrected temperature rise (§ 3.2.10), often called the Reg-
nault-Phaundler correction.
A group of methods exist which a priori assume that the calorimeter
is an inertial object of N order. A model of the calorimeter is expressed
in the form of a convolution function [42, 43]. The set of linear differen-
tial heat balance equations resulting from Eq. (1.142) is then replaced by
one equation of N order. Let us derive the equations that are the mathe-
matical models of these methods. Equation (1.148) in its matrix form
gives
where is the diagonal matrix whose elements are the heat capacities
of the particular domains; is the matrix whose elements are the heat
loss coefficients; T(t) is a vector whose components are the tempera-
tures of the particular domains; P(t) is a vector whose components are
the heat powers of the distinguished domains; and is the derivative
of the T(t) vector. Laplace transformation of Eq. (1.146) gives
where s is the Laplace operator, is the initial state vector (the initial
temperature condition in the domains), and T(s) and P(s) are the Laplace
transforms of state vector T(t) and P(t), respectively. The solution of Eq.
(3.27) in the complex domain s is
where
is the transfer matrix; in the frequency domain the solution is
and in the time domain t, the solution is
where H(t) is the matrix of fundamental solutions. If it is assumed that

100 CHAPTER 3
where is the sampling period and is the Dirac function, Eq. (3.31)
can be rewritten as
If it is additionally assumed that the heat source is located in one

domain only, and that the temperature is measured in one domain only
and under the zero initial temperature, Eqs (3.30), (3.31) and (3.33) de-
fine the mathematical models for reconstruction of the thermokinetics
P(t). Equation (3.32) written in the form
corresponds to the mathematical model of the harmonic analysis method

(§ 3.2.11.1). Eq. (3.31) in the form
represents the mathematical model of the dynamic optimization method

(§ 3.2.11.2). Equation (3.26) is the basis of the state variable method (§
3.2.11.4). Equation (3.33) in the form
represents the mathematical model of the thermal curve interpretation

method (§ 3.2.11.3). Under zero initial conditions, Eq. (3.28) in the form
where
represents the mathematical model of the method of transmittance de-

composition (§ 3.2.11.5).
Techniques that use analog and numerical correction of the dynamic
properties (§ 3.2.11.6) of the calorimeter compensate the transmittance
zeros and poles and can be also applied to reconstruct the thermokinet-
ics. In agreement with Eq. (3.41), the transmittance has the form
where S is the gain factor.
3.2.2. Comparative method of measurements
Calorimetric determinations are based on the comparative method of

measurements. The International Conferences on Chemistry in Lucerne
in 1936 and in Rome in 1938 accepted the proposal that all physico-
chemical measurements should be divided into two groups, absolute and
comparative [202–205]. The absolute measurements include the deter-
mination of absolute values characterizing a given physicochemical
property of chemical compounds or a mixture. It is necessary to intro-
duce all secondary factors which would change the numerical value
determined by the absolute method. Absolute measurements should be
carried out exclusively by specialists working in bureaus of measures
and standards or in laboratories sufficiently adapted for high-precision
measurements. A comparative method of measurements can be per-
formed when possible to assume certain substances as standards and the
properties of the investigated systems can be compared with the identity
of substances. The main principle of this method is the identity of condi-
tions during the measurements and the system calibration. The achieve-
ment of this condition is difficult on determining the heat power by the
methods when the consideration of the physical parameters of the sys-
tem is abandoned. In these methods it is assumed a priori that the trans-
mittance of the calorimeter during the calibration and measurement are
the same.
The method of comparative measurements is often performed with
use of the differential method of measurement, which is defined [206] as
“a method of measurements in which the measurand is compared with
the quantity of the same kind, of known value only slighty different
from the value of the measurant, and in which the difference between
the two values is measured”.
102 CHAPTER 3
The differential method of measurement is the basis of the use of dif-

ferential calorimeters. It is assumed that such devices are constructed of
two identical calorimeters (I and II) located in a common shield. One of
them contains the sample in which the heat effect is generated; in the
second, the thermally passive object (or standard substance) is located.
The course of the change in temperature of calorimeter I in which the
heat effect is generated is based on the measured temperature difference
between calorimeters I and II.
The conditions of the differential method of measurement are ful-
filled when: a) the static and dynamic properties of the two calorimeters
are identical; and b) the influence on calorimeters I and II of the input
forcing functions generated in the surroundings are the same. This man-
ner of temperature difference measurement allows determination of the
temperature changes caused by the heat power generated in the sample,
and elimination of the influence of other forcing functions. This method
is very often used in isoperibol and scanning calorimetry, in DTA de–
vices and in some cases in adiabatic calorimetry.
From the dynamic properties of differential calorimeters, it is clear
that the disturbances can be eliminated only if the transmittances of
calorimeters I and II are the same. It is very difficult to fulfill this condi-
tion. Hence, for a given differential calorimeter it is useful to determine
an acceptable range of difference of the time constants for which, for a
given disturbance and required accuracy of T(t) measurements, the as-
sumption of a differential character of the calorimetric system is satis-
fied [207]. The application of the dynamic equations discussed in Chap-
ter 4 can be very helpful in this type of investigations.
An other type of calorimeters used is the group of devices called
twin calorimeters. In such calorimetric systems, it is necessary to obtain
equal temperatures of the inner parts of calorimeters I and II in such a
way that in calorimeter II a the heat power has the same magnitude and
course as that in calorimeter I. It is obvious that, for twin calorimetric
systems, similarly as for differential calorimeters, the dynamic proper-
ties of the two calorimeters should be the same.
3.2.3. Adiabatic method and its application

in adiabatic and scanning adiabatic calorimetry
The adiabatic method [76, 87–89] is based on the assumption that no

heat exchange occurs between the calorimetric vessel and the shield.
The calorimeter has the dynamic properties of an integral object. “Ide-
ally, the adiabatic shield is always maintained at the temperature of the
calorimeter so that there is no temperature differential [208].”
To perform the measurement, two methods are used. In the first,
called the continuous heating method, the calorimeter proper and the
shield are heated at constant power input throughout the whole period of
measurement. The course of the temperature change with time is meas-
ured, as is the electrical power supplied to the calorimeter heater. We
assume that the thermal power generated is used only to heat the studied
substance and the other parts of the calorimeter proper. If this assump-
tion is true, then the three quantities temperature, energy rise and tem-
perature rise (caused by the energy rise) are sufficient to define the
measured quantity used to determine the specific heat at temperature T.
The generation of electric energy inside the calorimeter proper does not
always lead to a temperature rise. It can happen that an isothermal rise
of the enthalpy occurs during the studied process.
In the second method, the temperature of the calorimeter proper is
measured with no power input. First, the calorimeter proper is heated at
constant power for a known time interval to attain a certain temperature.
After the power is turned off, the temperature is measured. Then, the
current supply can again be switched in and next, after switching-off,
the temperature will be measured. This cycle can be repeated several
times. Such a procedure is called the intermittent-heating method. Both
of the measurement procedures described above are used in practice.
The first permits control of the temperature of the calorimetric shield in
an easier way and it is certainly more convenient to obtain results in a
full range of measurement. The second procedure permits study in a
precise way of these temperature ranges where interesting phenomena
(e.g. unknown phase transitions) are to be observed.
104 CHAPTER 3
3.2.4. Multidomains method
The multibody (domain) method [67, 209, 210] allows the determi-
nation of thermokinetics as well as the total heat effects of the process
examined. The method is based on the general heat balance equation
[Eq. (1.148)]. The mathematical model of the calorimeter is described
by the following set of equations:
where N is the number of distinguished domains; is the heat loss

coefficient between domains i and the j; is the heat loss coefficient
between domain i and the shield; and is the heat power.
Equation (3.41) describes the “changeable” part of the calorimeter; it
is assumed that is the heat capacity of the calorimetric vessel with
the contents. The remaining part of the calorimeter described by Eq.
(3.40) corresponds to an “empty” calorimeter. This part is called the
“nonchangeable” part of the system.
The above form of the set of equations indicates that, for various heat
capacities there is no need to change the mathematical model of the
calorimeter; a change in calls only for the introduction of new data in
the deconvolution program. This can also be applied when the heat ca-
pacities of the calorimetric vessel content changes during the experiment
(e.g. in the titration process).
The form of the heat balance equations for a given calorimeter de-
pends on a number of factors, such as the number of defined domains,
the interactions between the domains, and the mutual location of the
heat source and temperature sensor. This means that the mathematical
form of the equations is related to the thermal and geometrical parame-
ters of the calorimeter and to the location of the sensors and heat
sources. It is accepted that each of the domains has a uniform tempera-

ture throughout its volume and that its heat capacity is constant. Tem-
perature gradients occur only in the media that separate these domains,
and the heat capacities of the media are taken to be negligibly small. The
amount of heat exchanged between the domains through these media is
proportional to the difference between their temperatures. The propor-
tionality factors are the corresponding heat loss coefficients, and a heat
source and temperature sensor can be located between them. The system
of domains is located in a shield of temperature, which is treated as the
reference temperature.
To elaborate the dynamic model, it is necessary to calculate the heat
capacities of defined domains and the heat loss coefficients, and to de-
termine the structure of the model. For example, qualitative analysis of
the heat exchange in the BMR calorimeter [157] (Fig. 3.4) on the basis
of the calorimeter construction allowed the distinction of 19 domains.
The distinguished domains are individual parts of the calorimeter. A

block diagram of a such system, elaborated by Cesari et al. [211], is
presented in Fig. 3.5, where are the interaction coefficients between
the domains. The calorimeter was divided into upper U and lower B
parts, because there is no symmetry of the device in the horizontal plane.
106 CHAPTER 3
Starting from the vertical symmetrical axis going through the center of
the calorimetric vessel, the following domains were chosen for the parts
of the calorimeter: 1, 2 – the calorimetric heater R; 3, 4– the shield A of
the heaters; 5–8–the block vessel, 9, 10–the cylindrical parts of the
vessel shield; 19 – the bottom part of the shield; 11,2,15,16–
thermocouples; 13, 14–thermocouple supports; 17–inner thermostat
block; 18– vessel shield support. It was assumed that the calorimeter is
ideally differential, and that the other twin battery has been eliminated,
because it does not contribute to the transfer function. The heat capaci-
ties of each of the domains were calculated on the basis of its geometry
and its parameters: the specific heat and density of the domain material;
coefficients were calculated from the equation where is
the thermal conductivity; F is the surface area of heat exchange; and
is the distance between the centers of the neighboring domains. This
relation was applied when the surface dividing the domains was a plane.
For a cylindrical surface of heat transfer, the equation
was used, where l is the height of the cylinder; and and are the radii
of the cylindrical surfaces that pass through the centers of the neighbor-
ing domains.
The elaboration of the model allows determination of the set of heat
balance equations. The procedure of calculating the calorimetric re-
sponse starts from the heat balance equation of the domain in which the
heat source is located, with the assumption of zero initial conditions for
all the temperatures, for i = 1,2, ... , N. On substituting the
derivatives in the set of Eqs (3.40) and (3.41) by differences, we obtain
The temperature changes vs. time are calculated from
When the values of are known, the temperature is cal-

culated, and next the temperatures of the neighboring domains are calcu-
lated from Eq. (3.43). The last equation in the loop calculates the tem-
perature of the sensor. The temperature changes in these domains are the
model responses to a given heat effect. There are as many equations as
domains distinguished and all calculations are carried out in one calcula-
tion loop.
The algorithm of the thermokinetics calculation is very similar to
that for thermogram calculations. The beginning of the procedure is the
temperature of the sensor. Next, the temperature of the neighboring
domain is calculated, assuming zero initial temperature for the remain-
ing domains. For a system of domains, Eq. (3.42) for can be writ-
ten in the form
108 CHAPTER 3
Equation (3.44), which is the calculation loop, is used N–1 times to

calculate the temperatures of neighboring domains. The final calculation
of the heat power gives
where z is the index of the heat source domain, and z – 1 is the index of
the domain next to z.
For a model of more complicated configurations, when one domain
can have more than two neighbors, one calculation loop has as many
equations as neighbors. For example, domain j has r neighbors. The heat
exchange between these domains is characterized by heat loss coeffi-
cients Coefficients and are the heat loss coefficients between
domain j and its neighbors and between domain j and the shield, respec-
tively; The calculation loop will then be a set of r equations of
the form
where r is the index of the neighboring domain to the j domain. The

following loops are related to the number of domains and the configura-
tion between them, up to the last loop for calculating the course of heat
power in time.
The transmittance (Eq. 2.41) of the calorimetric system has the form
where is the root of the transmittance (the root of the numerator

of the transmittance) and is the pole of the transmittance (the
root of the dominator of the transmittance); S is the static amplification
factor. The finding of the real form of the transmittance is the same as
determination of the dynamic properties of the examined calorimetric
system. In this method, it is assumed that synchronous knowledge of the
real transmittance form and S and will be suitable for determina-

tion of the thermokinetics, but only when the optimization and stability
conditions of the numerical solution are fulfilled. These conditions de-
mand the admission of the value of a sampling period obtained from the
amplitude characteristics of the calorimeter, taking into account the
noise-signal ratio [see § 3.2.11.7]. The optimal sampling period limits
the smallest value of the time constants. If any number of time constants
of the calorimeter does not satisfy the stability condition, the a new
model of the system must be worked out, decreasing the number of do-
mains and calculating new parameters. The maximum order of the new
model is limited by the number of time constants which satisfy the sta-
bility condition. Next, the model response to a given heat effect is com-
pared with the experimental response. If the result is positive, this means
that a model useful for the determination of thermokinetics has been
elaborated.
3.2.5. Finite elements method
The finite elements method was proposed and described by Davis

and Berger [212]. This method is based on the following assumptions. A
certain number of elements are distinguished, between which the heat
exchange is characterized by the heat loss coefficients For each ele-
ment, the heat capacity is calculated. It is assumed that temperature
for each of the distinguished element is known at moment t and next
calculated for For each i-th element, the amount of heat
exchanged between the element i and element i+1 is determined by the
equation
For each element, we can write
Thus:
110 CHAPTER 3
Next, the temperature of each element is calculated after time
For example, if for the first element of temperature the heat power
P is generated during time then after time the change in tempera-
ture of this element is
The result of these calculations is the thermogram, which represents

the course of the changes in time of the temperature of the element in
which the sensor was placed.
Thermokinetics is determined on the basis of deconvolution of the
pulse response of the examined system and the measured thermogram.
For calculations, the first nonzero value of the pulse response
is taken. The increase in temperature of the element (in which the
heat effect is generated) is determined on the basis of the equation
where is the increase in temperature of the element in which the

sensor is placed. The magnitude R plays the role of the multiplier, which
allows transformation of the sensor signal to the signal in the reaction
vessel. In order to determine the thermokinetics at moment it is
necessary to know the temperature distribution of all elements and the
heat power P at moment t. In each sampling period the increase in
temperature is caused by two effects: 1) the heat generated by the
reaction (or pulse), which causes the temperature increase; and 2) the
heat transferred, which causes the temperature increase Thus, the
increase in temperature of the sensor, according to the superposi-
tion principle, is given by the formula
The increase in temperature is calculated on the basis of Eqs

(3.48)–(3.51). The value of the temperature increase is determined
on the basis of the thermogram obtained, and the increase in temperature
is calculated as the difference
The value of the increase in temperature is calculated on the ba-

sis of Eq. (3.53). Thus, the temperature of the reaction vessel for
is
The heat power P for is given as
The presented method permits the use of an iterative procedure to de-

termine the values of heat power in sequenced time moments. This
method is very sensitive to the errors in the determination of the value of
the pulse response and coefficient R.
3.2.6. Dynamic method
The dynamic method [10] of measurement is used for the determina-

tion of: a) the course of the thermal power change in time, b) the
course of the temperature change vs. time, which characterizes the
course of the thermal power change in time; and c) the total heat effect.
As the mathematical model of the calorimeter, we use here the heat bal-
ance equation of a simple body [Eq. (1.99)].
As concerns the explanation of the method principles, let us assume
that the calorimeter proper at temperature is surrounded by a shield
at constant temperature while the results of the temperature differ-
ence are expressed by function T(t). This assumption enables
us to discuss this method by using the procedure proposed by Calvet
[10].
To describe the relation between the generated heat effect Q(t) and
the difference T(t) in the calorimeter proper and the shield temperatures,
Eq. (3.13) is used in the form
or in the form
112 CHAPTER 3
while to describe the course of the thermal power change in time ex-
pressed as a function of temperature, the dynamic equation is used:
The first term on the left-hand side of Eqs (3.58) and (3.59) is
equivalent to the amount of heat accumulated in the calorimeter proper,
while the second term on the left-hand side of these equations is equiva-
lent to the amount of heat exchanged between the calorimeter proper
and the shield.
Measurements of the temperature are usually made by using sensors
such as a resistance thermometer and thermistor, where the resistance is
a function of temperature, or a thermocouple and thermopile, where the
electromotive force is a function of temperature. Accordingly to express
T it is convenient to use the quotient with where is the
measured magnitude, and g is the factor of proportionality. Equation
(3.58) then becomes
Integration of Eq. (3.73) leads to
where notes the values of and at times and while
is equal to the surface area F located between the course of changes in

time and the time axis t. The values of and F are the results of calo-
rimetric measurement. The values of C/g, G/g, and are determined via
the calibration procedure. Equation (3.61) is often called the Tian–
Calvet equation.
The calibration consists in generating a rectangular pulse [Eqs (2.45)
and (2.46)] of known heat power inside the calorimetric vessel in a time
long enough for a new state of stationary heat exchange to be achieved.
In practice, it is characterized by a constant temperature difference, de-
scribed as and simultaneously by constant value Allowing a small

error, we can assume that it occurs in the time period equal to The
solution of Eq. (3.60) is then
and for Eq. (3.61)
In this way, the value of G/g is defined. Quite often, it is useful to

determine a set of values G/g by generating rectangular pulses with dif-
ferent amplitudes. It can then be verified if a value of coefficient G/g is
constant in the interesting range of changes in the temperature of the
calorimeter. This constant value means that the calorimeter has the lin-
ear properties of a dynamic object.
If the generation of the rectangular heat pulse is stopped, then the
calorimeter becomes a thermally inertial object. Cooling of the
calorimeter then occurs up to the moment when the temperatures of the
calorimeter and the shield are the same. This process has been described
by Newton‘s cooling law [Eq. (1.104)] and is used to determine the
value of the time constant (see § 2.7.1).
In the knowledge of and G/g, by means of Eq. (1.103) we can de-
termine the value of C/g:
Besides the determination of the time constant value, very important

information is provided by observation of the course of the changes
for the calorimeter as a thermally inertial object. When the changes
= f(t) are nonlinear during the initial period of the cooling or heating
process, it is necessary to analyze whether application of the simple
body heat balance equation to the calculations is correct. A nonlinear
course of means that the function is multiexponen-
tial. More precise equations expressing the relation between P(t) and
T(t) should then be used. The calibration procedure presented here is not
the only one used in the dynamic method. The literature on this subject
114 CHAPTER 3
contains several modifications of such way of calibration, e.g. [7, 159,

160].
3.2.7. Flux method
The dynamic method presented above is based on the assumption

that the heat effect generated in the calorimeter proper in part accumu-
lates in the calorimetric vessel, and in part is transferred to the calo-
rimetric shield. When excellent heat transfer occurs between the calo-
rimeter proper and the shield (as in conduction microcalorimeters), it
can be assumed that the quantity of heat accumulated is extremely small.
This assumption is the basis of the flux method. The amount of heat
transferred between the calorimeter proper and the shield is then directly
proportional to the temperature difference. Thus, the course of ob-
tained from the measurement resembles that of P(t), and its value is
determined on the basis of the second term on the left-hand side of Eq.
(3.61):
while the total heat effect is
which results from Eq. (3.62).
3.2.8. Modulating method
The modulating method is based on the measurement of the tempera-

ture oscillations of a sample heated by oscillating heat power. Under
isoperibol conditions, this method is called AC calorimetry [213–215].
The first AC calorimetry experiments were performed in 1962 by
Kraftmacher [213], who measured the heat capacities of metals in the

high-temperature region.
Reading et al. [216, 217] proposed a method in which a DSC is used.
In this case, the response of the calorimeter as a linear system would be
a superposition of two input functions: 1) the ramp function [Eq. (2.49)]
generated in the calorimetric shield and 2) the periodic function gener-
ated in the sample. When the periodic function is sinusoidal [Eq. (2.53],
where is the initial temperature, is the temperature amplitude and

v is the angular frequency. The solution of Eq. (3.68) in the case of
steady-state temperature modulation of the sample, according to Eqs.
(2.55) and (3.26), is
where is the time constant, which corresponds to and is the

phase angle given by
The resultant signal is then analyzed by using the combination of a

Fourier transform to deconvolute the response of the sample to the un-
derlying ramp from its response to the modulation that can give rise to
an underlying and a cyclic heat capacity. For data evaluation, two pro-
cedures are used, for “reversing” and kinetic “nonreversing” compo-
nents [217], the determination of “storage” and “loss” heat capacities
[218, 219]. The “reversing” parameter is most readily identified with the
heat capacity of the sample, whereas the nonreversing component in-
cludes contributions from irreversible processes such as crystallization,
glass transition, and the melting of polymers.
Temperature-modulated differential scanning calorimetry is a new
analytical technique used to obtain information on the heat capacity in
the range close to the phase transformation. It is a method applied in
many instruments, e.g. as the Modulated DSC of TA Instru-
116 CHAPTER 3
ments [220, 221], the Alternating DSC of Mettler-Toledo

[222] or the ODSC (Seiko Instruments) [223].
3.2.9. Steady-state method
In order to obtain a constant gradient of temperature between the

calorimeter proper and its environment, the steady-state method is used.
The method is based on the assumption that the following condition is
fulfilled:
where is the heat power generated during the process examined;

is the compensating heat power; P(t) = 0 (adiabatic-isothermal
calorimeters) or P(t)= const. (adiabatic-nonisothermal; compensating
DSC).
Let us apply Eq. (3.6) to formulate the basis of the method.
Integration of both sides of Eq. (3.6) with respect to time in the in-
terval gives
or
Let us assume that the temperature can be expressed by two terms:
where is the average temperature of the calorimeter proper (the calo-

rimetric vessel), and are the temperature oscillations around the
average temperature. Thus, the temperature increment in the consid-
ered time period is
The integral of Eq. (3.73) can then be written in the form
or
When the temperature of the shield can be assumed to be constant:
the third term on the left-hand side of Eq. (3.77) is
and Eq. (3.77) becomes
If it is additionally assumed that the amplitude of temperature oscil-

lations around the average temperature is negligibly small, we
can put
and Eq. (3.80) simplifies to the form
For adiabatic-isothermal calorimeters, it is assumed, that

0 and the first term on the left-hand side of Eq. (3.82) is neglected. The
thermal power is used to compensate
For adiabatic-nonisothermal calorimeters when to de-
termine the amount of heat it is necessary to know the time interval
of the process, the average temperature the heat loss coefficient G
and the amount of heat delivered to the calorimeter proper in order
to hold the desired value with minimum oscillations.
118 CHAPTER 3
The thermal power is produced by several pulses of Peltier or

Joule effects by:
a) Application of pulse compensation consisting in the generation of
quantized thermal power pulses as shown in Fig. 3.6, where A is a
pulse amplitude, is the pulse duration, and F is frequency.
b) Use of proportional compensation; it is assumed that the tempera-

ture change is proportional to the generated compensation thermal
power
or
c) Use of proportional-integral compensation; the proportionality of

to and to the integral value of is assumed:
where is the integration constant.

3.2.10. Method of corrected temperature rise
The method of corrected temperature rise [224, 225, 8] is used to de-

termine the total heat effects in n-n isoperibol calorimeters. The method
is based on the heat balance equation of a simple body in the form
If we put
Eq. (3.87) can be written in the form
where
is called the corrected temperature rise. The amount of heat

generated in the calorimetric vessel corresponding to the temperature
increment can then be expressed as
The determination of is the aim of the calorimetric measurement.

The heat capacity C of the calorimeter is determined during the calibra-
tion in which a heat effect of known value is generated.
In the calorimetric measurement, three periods can be distinguished
(Fig. 3.7): the initial period (segment AB); the main period (segment
BC); and the final period (segment CD).
During the initial period the temperature changes before the
examined heat process are measured. The beginning of the main period
is the initial moment of the generation of heat by the process
studied. As the end of the main period, the time moment is assumed as
the end of the studied process. During the final period, the temperature
120 CHAPTER 3
changes of the calorimeter after the examined heat process are meas-
ured.
In the method, it is assumed that, independently of the heat process
studied, during the whole period of measurement a constant heat effect
can be produced in the calorimeter by secondary processes (for example,
the process of evaporation of the calorimetric liquid, the friction of the
stirrer on the calorimetric liquid, etc.). The course of the temperature
changes is then described by
expressing Newton’s law of cooling by magnitudes u corresponding to

the constant heat effect. If we assume that
where is the increment of temperature of the calorimetric vessel,

which corresponds to the constant heat effect, involve by secondary
process Eq. (3.91) can be written in the form
It is assumed that this equation is valid in the initial and the final pe-
riods of measurement. In the initial period, we have
and in the final period, we have
Because of the small changes in temperature in these periods of

measurement, we can approximate them as linear changes in time. Thus,
and can be treated as constant, and can be ascribed to the average
temperatures and of the initial and final periods, respec-
tively:
By subtraction from Eqs (3.96) and (3.97), we can calculate the

value of the cooling constant as
Let us assume that the constant heat effect caused by the secondary
process exists in the main measurement period too. In Eq. (3.87), the
temperature T(t) must be substituted by the term thus, we
have
The value of the integral
can be approximated by the expression

122 CHAPTER 3
where are the values determined during the subsequent read-

ings of temperature T(t) in the main period; and This
method involves the assumption that, in small time intervals of the main
period, temperature T(t) changes linearly, and the average temperature
of the main period is the arithmetic average of the average temperatures
obtained in these small time intervals. On determining from Eq.
(3.94), we have
Similarly, from Eq. (3.95), we obtain
Use of Eqs (3.99), (3.101) and (3.102) leads to
Substitution of according to Eq. (3.98) gives
On substituting Eqs (3.101) and (3.103) into Eq. (3.99), we can write
or on substituting by expression (3.98), we obtain

Equations (3.105) and (3.107) for the temperature correction are

called the Regnault-Phaundler correction. They assumed the sampling
period to be equal to unity, and thus This correction is
mostly used in isoperibol calorimetry to calculate the corrected tempera-
ture rise
Depending on the need for precision of the temperature measure-
ment, various approximations of the course of temperature T(t) are used.
The graphicel-numerical methods of calculating the corrected tempera-
ture rise include the Dickinson method [226]. White [227, 228] pro-
posed the Simpson rule for calculation of the integral of Eq. (3.100).
Roth [229] used the least squares method for approximation of the initial
and final periods by straight lines. Planimetry at first was used to obtain
this integral.
3.2.11. Numerical and analog methods

of determination of thermokinetics
3.2.11.1. Harmonic analysis method

In this method, first used by Navarro et al. [230, 231] and by van
Bokhoven [232, 233], the convolution recorded in the frequency domain
is accepted as the transformation equation [Eq. (2.8)] of the calorimeter.
For the determination of an unknown heat effect, it is assumed that the
spectrum transmittance (§ 2.6) has been determined previously.
Next, an unknown heat effect is generated and the calorimetric
signal is measured. After determination of the spectrum transmit-
tance and the calorimeter response the thermokinetics
is obtained as the inverse Fourier transform
where is the Fourier transform of the response As a criterion

of the possibility of reproduction, Shannon’s theorem is applied. In prac-
tice, a frequency is used which is obtained on the basis of the transfer
124 CHAPTER 3
function calculated. The practical frequency is determined on the

basis of the dependence
where is the value of the spectrum transmittance amplitude for v

= 0, is the value of the amplitude for the practical frequency,
and noise is the noise amplitude.
3.2.11.2. Method of dynamic optimization

In the dynamic optimization method [234–236], Eq. (2.9) is taken as
a mathematical model of the calorimeter, and thus appropriate zero ini-
tial conditions are assumed. This method assumes the existence of one
input function T(t) and one output function P(t). The impulse response
H(t) is determined as a derivative with respect to time of the response of
the calorimetric system to a unit step. As a criterion of accordance be-
tween the measured temperature change T(t) and the estimated course of
temperature x(t), the integral of the square of the difference between
these two courses is taken:
or, on substituting the convolution of functions, we obtain
The task of dynamic optimization consists in selection of the un-

known thermal power P(t) so that Eq. (3.111) attains a minimum. Such a
task can be solved provided that the temperature response T(t) and the
impulse response H(t) of the calorimeter are known in the analytical
form. However, in calorimetric measurements, numerical values
are usually available on the course of the temperature changes

T(t) of the calorimeter. Because of this, the integrals in function (3.111)
are approximated by sums, and the function therefore becomes a func-
tion of multivariables:
In the search for the minimum of function (3.112), a conjugate gradi-

ent method is used.
3.2.11.3. Thermal curve interpretation method
It is known that the response to a Dirac heat pulse of unit ampli-

tude is the pulse response For stationary linear systems, the re-
sponse to a heat pulse generated at time moment is
In the method [237, 248], it is assumed that the heat effect P(t) gen-
erated can be approximated by the function
The thermogram T(t) can then be approximated by the expression
or
where is the sampling period, are the values of the heat pulse gen-
erated at moment j, and is the i-th value of the pulse response,
which corresponds to the unit pulse generated in the calorimeter at mo-
ment j.
126 CHAPTER 3
The aim of the spectrum method is to find the values of coefficients

The scheme of searching for the values of these coefficients can be
shown as follows. Let us transform the set of functions into the set
of orthonormal functions –
The condition of orthonormal functions has the form
where
Orthonormalization of the function [Eq. (3.117)] is difficult, because

we orthonormalize very similar functions.
Using the basis of orthonormal functions and curve T, the co-
efficients are calculated as
Applying the inverse transformation to transformation (3.117), we

obtain the values of coefficients as
The computer realization of this scheme is very simple under the

condition that the orthonormalization does not give problems. The ther-
mal curve interpretation method was proposed by Adamowicz [237–
239].
3.2.11.4. Method of state variables

In the method of state variables [240–242], a certain set of parame-
ters is distinguished:
which characterize the calorimetric system. These values are referred to

as state variables. Three types of state variables are distinguished:
physical variables, canonical variables and phase variables. The vector
the components of which are state variables, is referred to as the state

vector. Thus, the calorimeter transformation equation combines the state
variables with the parameters of the calorimetric system and the thermal
power produced:
The state equation (Eq. (3.124)) written in this way is a system of

first-order equations. Because of the available calorimetric information,
the state variables should be transformed in such a way as to obtain a
relationship between one input function P(t) and one output function.
The relationship between the state variables and the output function has
the following form:
The method of state variables for the determination of thermokinetics

was proposed by Brie et al. [239]. The method was applied in the fol-
lowing works [239, 243, 244].
128 CHAPTER 3
3.2.11.5. Method of transmittance decomposition

In this method [245], the dependence between the measured calo-
rimetric signal and the generated heat effect, in the complex plane, is
described by Eq. (2.11). Use of Eq. (2.41) leads to
or, after dividing (m < N), we obtain
where
R(s) is a polynomial of degree smaller than m (remainder of division).

Using Eq. (3.127), we have
The expression after the use of Eq. (3.128), in the time

domain corresponds to the differential equation
The expression after the use of (3.129), in the time

domain corresponds to the convolution function
where is the inverse Laplace transform of Eq. (3.129). After us-

ing Eqs (3.130–3.132), we obtain the final form of the equation for the
desired heat power:
In order to use the above equation to determine the unknown heat ef-
fect, it is necessary to determine first the nominator and denominator of
the transmittance and next the expressions and On the
basis of we calculate the coefficients and differential equa-
tion (3.131), and on the basis of This enables us to
decrease the number of derivations of m and is very useful when the
difference between the degree of the denominator and the degree of the
nominator of the transmittance is small.
3.2.11.6. Inverse filter method

This method [244, 246] is based on the assumption that the time con-
stants of the calorimeter as an inertial object have been determined pre-
viously. For example, when the calorimeter is treated as a object of sec-
ond order, the relation between P(t) and T(t) can be expressed according
to Eq. (2.13) in the form of the following differential equation:
Using Laplace transformation and replacing the coefficients and

by the time constants and of the calorimeter:
Eq. (3.134) becomes
The purpose of the inverse filter method is the application of a pro-

cedure which allows elimination of the influence of inertia units in the
130 CHAPTER 3
determination of the relation between T(s) and P(s), and thus that be-
tween T(t) and P(t). It consists in the introduction (by the numerical or
analog method) of terms providing an inverse function to the
terms For an individual corrector, we have
For two correctors, we have
For an ideal correction, this would lead to the case when the input
function corresponds to the output function, as represented by the rela-
tionship
The practical performance of the inverse filter method is different in

different systems [246–257], but advantage is always taken of electronic
elements active under the form of an operational amplifier and imped-
ance divider of the feedback, by which the required function is
achieved.
Another way to achieve the differential correction is numeric correc-
tion [255–257]. Taking into account Eq. (3.136), it is intended to calcu-
late numerically the functions corresponding to the terms To
each of these terms there corresponds a linear differential equation of
first order of the form
Thus, for an inertial object of second order, the following equations

can be noted:
When the time constants and and T(t) are known, it is possible
to determine the and values consecutively, and thus P(t).
The numerical differential correction method has also been applied to
reproduce the thermokinetics in these calorimetric systems, in which
time constant vary in time [258–264], such as the TAM 2977 titration
microcalorimeter produced by Thermometric. These works extended the
applications of the inverse filter method to linear systems with variable
coefficients. In many cases [258–262], as in the multidomains method,
as a basis of consideration the mathematical models used were particular
forms of the general heat balance equation.
3.2.11.7. Evaluation of methods of determination

of total heat effects and thermokinetics
The methods discussed above discussion are based on particular
forms of the general heat balance equation. Methods based on the simple
body balance equation or its simplified form have been used in calo-
rimetry for a very long time: the method of corrected temperature rise
for more than 100 years, and the adiabatic method for about 100 years.
There are also new methods (e.g. the modulating method) or those
which have become very important (e.g. the conduction method) in the
past 20–30 years.
Improved conditions in calorimetric experiments lead to the creation
of more precise mathematical calorimeter models and methods used for
the determination of heat effects.
From the methods in which the set of heat balance equations was
used, the multidomains method (§ 3.2.3) and the finite elements method
(§ 3.2.4) were elaborated. Numerical methods for the determination of
thermokinetics in n-n calorimeters (§ 3.2.11.1 - § 3.2.11.6) were also
developed.
In the multidomains method and in the numerical methods, in accor-
dance with the detailed solution of Fourier’s heat conduction equation, it
was assumed that the impulse response of the calorimeter is described
by an infinite sum of exponential functions [Eq. (2.57)]:
132 CHAPTER 3
Thus, in these methods an ideal model for reconstruction of the

thermokinetics should be a model of infinite order. In fact, it is neces-
sary to limit the number of exponential terms (domains). Generally, this
is due to the compromise between the available information and the
possibility of applying it. It has been proved by the results of a multina-
tional program [265] on the evaluation of the new methods of determi-
nation of thermokinetics, in 1978. The purpose was to compare different
methods independently proposed to reconstruct thermokinetics from the
experimental calorimetric data. The dynamic optimization, harmonic
analysis, state variable and numerical correction methods were tested.
To eliminate the uncertainties caused by the individual features of the
various calorimeters in different laboratories, it was generally approved
that the responses of all calorimeters should be distributed to all partici-
pants of the program. These responses concerned normalized series of
heat pulses, generated by the Joule effect in a heater. The values of am-
plitudes, the time durations of the generated heat effects and the sam-
pling period were fixed as follows. The sampling period was taken as
0.002–0.003 of the largest constant of the calorimeter, which corre-
sponds to 1/300 of the half-period of cooling. The values of amplitudes
were given in relative units, equal to 10, 100 and 1000. The amplitude
equal to 10 was defined as corresponding to the heat power of the pulse
of duration equal to 8 sampling periods, for which the maximal tempera-
ture increase was 10 times larger than the amplitude of the measurement
noise (the change in baseline when the thermally inert object is placed in
the calorimeter). Three types of measurements were made: 1, 3 or 7
pulses of various durations were generated one after another. For exam-
ple, plots of the series of 7 pulses are given in Fig. 3.7, and the results of
the data reconstruction by dynamic optimization and harmonic analysis
in Fig. 3.8.
134 CHAPTER 3
The results of the investigations indicated that the examined methods

reveal considerable progress in the reconstruction of thermokinetics. It
was stated [265] that “it is clear that the objective is not complete recon-
struction of thermokinetics (thermogenesis), but rather decrease of the
influence of thermal lags in calorimetric data; thus, after reconstruction,
the residual time constant which appears in the data is ~ 200 times
smaller than the actual order time constant of the instrument used”
and that “the range of application of the presented methods is varied.
The optimisation method shows its advantage especially in the cases
when the number of experimental data need not be bigger than 100-150.
The harmonic analysis, state variable and inverse filtering are not influ-
enced by such a limitation and may be freely applied for the reconstruc-
tion of effects requiring a great number of data points”.
It appeared that all methods are equally sensitive to noise in the data
and that the amplitude of the heat effect under study, compared to that
of noise in the data, is of particular importance for the quality of recon-
struction.
Let us consider the same problem on using amplitude characteristics
[266]. As given in Eq. (3.143), amplitude is described by the func-
tion
and for large values of can be approximated by Eq. (3.144):
As a criterion for choosing the optimal sampling period, it is as-

sumed that
where denotes the noise-to-signal ratio, and q corresponds to the

number of certain digits in the measurement of the calorimetric signal.
In order to estimate the values of the sampling period h instead of
the approximate values
are assumed in Eq. (3.144):
Raising both sides of Eq. (3.147) to the power 1/m results in
Thus, the values of the constants must be larger than the sampling
period with respect to the stability of the numerical solution. In the par-
ticular case when the number of certain digits in the calorimetric me-
surements is equal to the difference between the number of poles and the
number of zeros of the transmitance (q = N – m), the formula for the
optimal sampling period takes the form
A scheme for choosing the optimal signal-to-noise ratio has been the
subject of many papers, e.g. [267–270]. In the multidomains method,
this selecting scheme was included in the procedure of determining the
particular form of the calorimeter model. Another manner of selecting is
used when harmonic analysis method is applied. In this method, the
transmittance is obtained numerically, using the Fast Fourier Transform.
This procedure uses points, where n = 10, 11, 12 and N = 1024,
2048, 4096, respectively. The number of data used for calculations must
cover the whole interval of time from “initial zero” to “final zero” of the
temperature calorimetric response. The discrete measurement of tem-
perature limits the upper bounds of frequency which can be applied for
reconstruction of the thermokinetics. The value of this frequency,
resulting from Shannon’s theorem is a function of the sampling period
and can be expressed by the relation It is therefore
impossible to use the complete spectrum of the frequency. There also
exists a boundary frequency
136 CHAPTER 3
which is related to the measurement noise. The boundary frequency is

the second limitation of the frequency spectrum, which can be applied in
the reconstruction of the thermokinetics for a given calorimetric system,
and
The high precision of calorimetric measurements today permits a less
strict description of the calorimetric system itself. The comparison of
reconstructions of the thermokinetics obtained with the multibody
method and with other methods demonstrates the convergence of the
results [67] when the calorimetric system is described by a linear differ-
ential equation with constant coefficients of the third to sixth order.
A review of the published papers leads to the conclusion that mathe-
matical models which are particular forms of the general heat balance
equation of second or higher order are frequently used in isoperibol and
DSC calorimetry. When the mathematical model is known, the inverse
filter method is used to determine the thermokinetics.
The course of the thermal power change can be determined by using
different calorimeters. The choice of the heat effect determination
method does not depend on the calorimeter type. In a calorimeter with a
vacuum jacket, the thermokinetics can be determined successfully by
means of the dynamic method. In calorimeters whose inertia is very
small (conduction calorimeters), use of the flux method is not always
suitable. Better results in the reconstruction of thermokinetics are ob-
tained from the use of methods where it is assumed that the calorimeter
is an inertial object of first or higher order.
3.3. Linearity and principle of superposition
In the review of methods of heat effect determination and thermoki-

netics, the linearity of the system has implicitly been assumed. Linearity
[8, 271] can be expressed by the equations
where x and y express quantities to be measured and the function ex-

presses the output signal. Equation (3.141) is the basis of the superposi-
tion principle, and Eq. (3.142) indicates proportionality for quantitative
measurement.
Regardless of what method of heat effect determination is applied, it
has to be known whether measurements were performed in a linear sys-
tem.
It is essential to draw a distinction between linear and nonlinear re-
sponses of the system. To correct the response of the system the linear-
ity has to be confirmed by the experimental facts. When we look for the
correct answer, the best method is to analyze the response of each forc-
ing input function in the system. To achieve this, it would be helpful to
use the dynamic time-resolved characteristics for the typical input func-
tion, given earlier (§ 2.3).
The response of the calorimetric system is always a result of super-
position of some forcing functions acting at the same time. The forcing
function in the calorimeter proper is always the heat effect generated as
a result of the studied process. However, the review of the methods has
revealed that there can be forcing functions striving to compensate the
generated heat effect of the process; a rectangular pulse or a series of
rectangular pulses; periodic heating rate of the sample etc. Additionally,
the forcing functions acting in the shield influence the calorimeter. For
an isoperibol calorimeter, this is a forcing function, tending to achieve
the stability of the temperature of the shield; for scanning calorimeters,
it is a ramp function. Analysis of the output functions courses generated
in the shield is quite simple to deal with and usually consists in
considering the course of the system response, if there is a thermally
inertial object inside the calorimeter proper.
Chapter 4
Dynamic properties of calorimeters
4.1. Equations of dynamics
In our considerations relating to the analysis of the course of heat ef-

fects that occur in calorimeters, we have used particular solutions of the
general heat balance equation (1.148):
It is frequently more convenient to apply this equation in the tem-

perature dimension [8, 20]:
The set of differential equations (4.1) is called the general equation

of dynamics, the assumptions for which are sufficient to allow the calo-
rimeter to have different configurations.
The following notions have been introduced in Eq. (4.1): the overall
coefficient of heat loss, the time constant of the domain, the interaction
coefficient and the forcing function.
The overall coefficient of heat loss for each of the domains is de-
fined as
140 CHAPTER 4
This coefficient characterizes the heat exchange between domain j

and the surroundings, but also that between domain j and other domains.
The time constant of domain j is defined as the ratio of heat ca-
pacity and the overall coefficient of heat loss of the domain:
The time constant of domain j is a measure of the thermal inertia

of this domain in the system of domains.
The interaction coefficient is defined as the ratio of the heat loss
coefficient to the overall coefficient of heat loss
This is a measure of the heat interaction of domain i with the domain

j relative to the interactions of the remaining domains and surroundings
with domain j. The interaction coefficients essentially affect the thermal
inertia of the calorimeter and allow us to establish the structure of the
dynamic model of a given calorimeter. If the value of the interaction
coefficient is negligibly small, it may be assumed that there is no
thermal interaction between domains i and j or, more exactly, that the
thermal interaction between domains i and j is small enough to be ig-
nored in comparison with the interactions between domains i and j and
other domains and the surroundings.
Furthermore, the notion of the forcing function (taken from con-
trol theory) was introduced into these considerations. This function is
defined as
or, making use of Eq. (1.149), we have
The function has the dimension of temperature and is propor-

tional to the heat power evolved.
The coefficients are defined as
DYNAMIC PROPERTIES OF CALORIMETERS 141
where is a determinant whose value depends on the interaction coef-

ficient is the determinant of the matrix obtained by crossing out
the j-th row and the j-th column of matrix D. The coefficients are
dimensionless, chosen in such a way that an increment of the tempera-
ture in a stationary state is equal to an increment of the forcing
function Defined in this manner, the coefficients are especially
useful in applying the principle of superposition to the system of do-
mains.
The set of differential equations Eq. (4.1) can be written in matrix
form as follows:
where is the diagonal matrix whose elements are the time constants
is the diagonal matrix whose elements are the coefficients A is
the matrix whose elements are and for is the state
vector, and f is the forcing vector
Application of the Laplace transformation to Eq. (4.8) under zero ini-
tial conditions gives
where T(s) is the Laplace transform of the state vector T(t) and f(s) is
the Laplace transform of the forcing vector f(t). The solution of Eq. (4.9)
is
or
where
is the transfer matrix and its elements are the transmittances

which have the form
142 CHAPTER 4
where is the determinant of the matrix is the

corresponding minor of the matrix and is the determinant of
the matrix These determinants, after development into a power series
with respect to s, give polynomials of N-th and M-th degree (M < N),
respectively:
Thus, the transmittance [Eq. (4.13)] can be written in the form
or, on developing the nominator and the denominator of the transmit-

tance (4.16) into first-degree factors:
where is the static gain, is the root of the nomina-

tor of the transmittance (the zero of the transmittance) and is the
root of the denominator of the transmittance (the pole of the transmit-
tance).
The advantage of the use of the presented transmittance is the ex-
pression of both the input and output functions in temperature dimen-
sions. It can be applied to analyze the courses of the heat effects in calo-
rimeters of different constructions, with different locations of the heat
sources in relation to the temperature sensors. When the N-domain
method is used to describe the heat effects, determination of the trans-
mittance form makes it possible to verify the correctness of the mathe-

matical model of the calorimeter used in the calculations. In such a case,
it is sufficient to compare the values of the calculated and experimen-
tally measured function T (t) as the response to the known heat effect
generated in the calorimeter.
In many cases, the general equation of dynamics can be simplified to
a few-domain system, as will be pointed out below, in order to analyze
the courses of different heat effects in calorimeters.
4.2. Dynamic properties of two and three-domain

calorimeters with cascading structure
4.2.1. Equations of dynamics.

System of two domains in series
Let us distinguish a system of two domains in series, characterized

by heat capacities and respectively. The heat transfer between
these domains is described by the coefficient while that between the
domains and the environment (surroundings) is described by the coeffi-
cient The set of heat balance equations of the system is as follows:
If we put
144 CHAPTER 4
Eqs (4.18) and (4.19) can be written in the form
Let us consider that the heat power is generated only in domain 1,

and the temperature change of domain 2 is measured. The
domain 1 output function here is at the same time the input func-
tion for domain 2. Equations (4.22) and (4.23) then become
If we additionally assume that Eqs (4.24) and (4.25) can be

written in the form
As results from Eqs. (4.26) and (4.27), the domain 1 output function,
here is at the same time the input function for domain 2. Function
is the output function of the system.
In the general case, the initial conditions for Eqs (4.26) and (4.27)
are
Application of the Laplace transformation to Eqs (4.26) and (4.27)

gives the solution in the complex domain:
Equations (4.29) and (4.30) can be rewritten as
Simple rearrangement of Eqs (4.31) and (4.32) with the aim, among
others, of eliminating results in
If we put
Eq. (4.33) reduces to
The function P(s) expresses the effect of the input function F(s) on
This may be represented by a block diagram (Fig. 4.1) in which
the first and second rectangles represent the dynamic properties of do-
mains 1 and 2, respectively.
The function P(s) provides a basis for defining the function for
various functions f(t).
The functions G(s) [(Eq. 4.35)] will define the course of T(t) at f(t) =
0, the initial conditions being as follows:
After simple rearrangement, Eq. (4.35) becomes:

146 CHAPTER 4
and after an inverse Laplace transformation this gives
If, at the initial moment of heat generation, there is a temperature dif-

ference between the domains (or domain) and the surroundings, both
functions P(s) and G(s) must be determined if the function is to be
defined.
Let us now define the courses of function in the cases when 1) a
unit pulse function; 2) an input step function of amplitude b and time
interval a; and 3) a periodic input function is generated in domain 1.
This function f(t) is defined by rectangular pulses, each of them over the
time period a, the time interval between two successive pulses being Z.
Let us suppose that a heat effect that is constant in time (an input
pulse function) is producted in domain 1. In this case:
This forcing function results in a rise in temperature until a new sta-

tionary heat transfer state is established in the system. This state is char-
acterized by a temperature higher by than the temperature in the sys-
tem at the moment t = 0, if the initial conditions are zero.
If we assume and with Eq. (4.40), after inverse Laplace
transformation Eq. (4.34) becomes
If the constant heat effect occurs in domain 1 for a period of time a

and amplitude (unit step function of amplitude the function f(t)
assumes the form
The changes in temperature in time, are then expressed by
When n rectangular pulses occur in domain 1, each pulse lasting for

a period of time a, the interval between two successive pulses being Z,
the input function f(t) may be written in the form
where
For f(t) expressed by Eq. (4.44), the function F(s) is
and Eq. (4.34) takes the form
The function corresponding to P(s) in Eq. (4.47) was deter-

mined by an inverse Laplace transformation. This function is
148 C HAPTER 4
4.2.2. Equations of dynamics.

Three domains in series
In numerous cases, the determination of the output function with a

given accuracy requires that the two-domain cascading system should be
enlarged with an “additional” first-order inertial object (domain).
A cascading system composed of three domains in series can be de-
scribed by the following set of equations of dynamics:
As before, Eqs (4.49)-(4.51) are assumed to be general differential

equations of dynamics describing the courses of the temperature
changes in time in the domains considered. In Eq. (4.49), f(t) is the input
function. It may be assigned an arbitrary course. Function is the
domain 1 output function, which at the same time constitutes the input
function for domain 2. The output function of domain 2 constitutes the
input function of domain 3, whose output function is
For the solution of the above system of differential equations, the
Laplace transform method was used, yielding
where
The relation between the functions F(s) and P(s) may be represented
as in the diagram in Fig. 4.2.
When f(t) = 0, and
a solution of Eqs (4.49)–(4.51) in relation to is given by the equa-

tion
where
150 CHAPTER 4
For a forcing function f(t) described by Eq. (4.40) and initial condi-
tions described by Eq. (4.55), we obtain the changes in temperature
For a forcing function f(t) described by Eq. (4.43) and initial condi-
tions described by Eq. (4.55), we obtain
For a forcing function described by Eq. (4.45) and initial conditions

described by Eq. (4.55), the temperature changes are expressed by
the equation
Forms of the particular equation of dynamics developed for the sys-

tems of two domains and three domains in series are presented only with
selected input functions. This selection was made by taking as criterion
their application in the analysis of the courses of the heat effects. The
particular forms of the equations of dynamics for the other input func-
tions can be obtained in a similar way.
4.2.3. Applications of equations of dynamics

of cascading system
The equations of dynamics of cascading systems have been utilized

in calorimetry for many years [25–35]. For example, these equations can
be applied as follows:
1) A system of two domains in series. The input function f(t) of do-
main 1 is at the same time the output function of domain 2. The
output function of domain 2 is measured (Fig. 4.1).
a) The forcing input function f(t) is the input step function gener-
ated in the calorimetric vessel (in domain 1). Domain 2 con-
sists of the temperature sensor in isolation. The amplitude and
generation time of the rectangular pulse and the time constants
of domains 1 and 2 are known. For the calculations, one can
apply Eq. (4.43). These calculations allow determination of the
output function of the system, which is of special importance
in measurements of heat effects of short duration.
b) The input function is a ramp function. Domain 1 is a thermo-
stat, while domain 2 consists of the calorimetric vessel with
sample. Let us assume that the calorimetric vessel contains
samples with the same volume, but with differing heat capaci-
ties The time constants of domain 2 there-
fore change. This causes differences in the values of the output
function. They can be calculated after determination of the
particular form of Eq. (4.43), values characterizing the ramp
function and the values of
152 CHAPTER 4
2) The system consists of three domains in series (Fig. 4.2). The in-
put function f(t) of domain 1 is at the same time output function of
domain 2, which in turn is the input function of domain 3. The
output function of domain 3 is measured. The input function f(t) is
the input step function. Domain 1 consists of the calorimetric ves-
sel filled with the substance studied, domain 2 is the inner shield
of the calorimeter, and domain 3 is in isolation the temperature
sensor located on the outer surface of the inner calorimetric
shield. The amplitude and generation time of the rectangular pulse
and the time constants of domains 1–3 are known. To calculate
the output function, we can apply Eq. (4.61). The calculations al-
low us to determine the influence of the inertia of the inner shield
and the temperature sensor on the recording of the heat effect
generated in the calorimetric vessel.
In the discussed examples, the responses of the system to only one
forcing function were considered. In many cases, the course of the out-
put function of the system has to be defined as the result of the operation
of several forcing functions. This can be demonstrated via the following
examples.
3 a) A system composed of a thermostat (domain 1) and a calorime-
ter (domain 2). In the thermostat, the ramp function f(t) is pro-
duced, whereas the calorimeter gives the periodic input function
3 b) A system comprising the calorimetric vessel with the sample

(domain 1), the internal shield (domain 2) and the temperature
sensor (domain 3). In the calorimetric vessel, heat effect is
generated, while the compensating heat effect expressed by
is produced in the internal shield of the calorimeter.
This leads to the conclusion that, for the two-domain system when
input functions f(t) and (Fig. 4.3) are produced at the same time,
the output function P(s) will be expressed by Eq. (4.36) supplemented
by the term.
For the three-domain system, when forcing functions and

are produced at the same time, the output function is expressed by
Eq. (4.54) supplemented by the term
This means that in the two cases considered the solution of the equa-
tions of dynamics will be the sum
This procedure results from the application of the superposition rule

to linear systems.
Equations of dynamics are also useful in analysis of the courses of

the heat effects in differential and twin calorimeters.
Let us consider a system composed of two calorimeters (I and II),
characterized by the dynamic properties of inertial objects of the first
order, placed in a common shield. The sample is situated in one of them,
and the reference substance in the other. The forcing input function is
the ramp function generated in the thermostat. Let us assume that this
function is at the same time the input function of both calorimeters. The
influence of the forcing function on a differential calorimeter is shown
154 CHAPTER 4
schematically in Fig. 4.5, where and are the output functions

of calorimeters I and II, respectively and T(t) is the output function of
the differential calorimeter.
For this system, we can determine the changes in the course of the
function T(t) due to the changes in the time constants of both calorime-
ters and therefore the changes caused by the different heat capacities and
heat loss coefficients. For the observation of such changes, in many
cases it is necessary to consider systems having more domains, both in
series and with a concentric configuration. As often as not, with a high
number of domains present in the system, even the identification of
these domains may pose considerable difficulties and the direct determi-
nation of the time constants may be impracticable. The transmittance of
the system can then be determined or the system can be approached in
terms of a single system with vicarious characteristics. The application
of these characteristics does not mean, however, that the accuracy of
establishing the output function is somewhat sacrificed.
4.3. Dynamic properties of calorimeters

with concentric configuration
Let us discuss the two-domain model with a concentric configura-

tion, indicating the dependences of the dynamic properties on the mutual
locations of the heat sources and temperature sensors (§ 4.3.1 and
§ 4.3.2); explaining why the calibration of the calorimeter by means of
the dynamic method in some cases is accompanied by apparent changes

in heat capacity (§ 4.3.3); and proving the need for use of the equivalent
coefficient (§ 4.3.4) instead of the heat capacity value when the method
of corrected temperature rise is applied in calculations of heat effects.
4.3.1. Dependence of dynamic properties of

two-domain calorimeter with concentric
configuration on location of heat sources
and temperature sensors
Let us normalize in the dimension of temperature the isoperibol n-n

calorimeter characterized by a system of two concentric domains shown
in Fig. 4.5 [21, 45].
This is characterized by Eq. (4.18):
and the equation

156 CHAPTER 4
In this case, the overall heat loss coefficients and for the do-
mains 1 and 2 are, respectively
The time constants and of the distinguished domains 1 and 2

are
It may be noted that the thermal inertia of domain 1 is influenced by

the heat transfer between domains 1 and 2 and with the shield, whereas
the thermal inertia of body 2 is influenced by the heat transfer between
domains 1 and 2. The interaction coefficients are, respectively
On putting we can write
In order to determine coefficients and the determinants

are calculated, which are, respectively
With regard to Eqs (4.68)–(4.73), Eqs (4.18) and (4.66) can be written in
the form
The differential equations (4.74) and (4.75) are called the equations
of dynamics of a calorimeter treated as a system of two domains with a
concentric configuration [44, 45]. It may be noted that the left-hand

sides of these equations are similar to the equation of dynamics for a
one-domain model; the time constants and of the particular do-
mains thus characterize the first-order inertial properties of each, con-
sidered independently of one another.
However, because of the different forms of the right-hand sides of

Eqs (4.74) and (4.75) referring to the heat balance equation of a simple
body, a new quality is obtained: the mutual interaction expressed by
and This expression follows from the block diagram
(Fig. 4.7), which may be assigned to the equations of dynamics.
To obtain the block diagram shown in Fig. 4.6, the Laplace trans-
formation should be applied. Equations (4.74) and (4.75) then become
where and are the differences between the initial temperatures

of domains 1 and 2, respectively, and that of the temperature of the
shield at time = 0; and are the Laplace transforms of tempera-
tures and respectively; and are the Laplace trans-
forms of the forcing functions and
When
Eqs (4.76) and (4.77) become

158 CHAPTER 4
For the transform from Eq. (4.80) and the transform from
Eq. (4.79), we have
where
are the transmittances of domains 1 and 2, respectively. These functions

characterize the dynamic properties of the domains that are distin-
guished in the examined calorimeter. It is seen from the block diagram
(Fig. 4.7) that the dynamic properties of the system depend on the dy-
namic properties of the domains and on the interaction between them. In
this connection, let us consider the dependence of the dynamic proper-
ties of the calorimeter described by Eqs (4.74) and (4.75) on the loca-
tions of the heat sources and temperature sensors in domains 1 and 2.
The following cases can be distinguished:
1. A heat power characterized by forcing function is generated,
and the changes in temperature in time are measured.
2. A heat power is measured and the changes is temperature
in time are measured.
3. A heat power characterized by function is generated, and the
changes in temperature in time are measured.
4. A heat power characterized by function is generated, and the
changes in temperature in time are measured.
For these cases, the calorimeter transmittances as functions of trans-
mittances and [Eq. (4.83)] of the distinguished domains and
interaction coefficient k are given in Table 4.1; the relationships be-
tween the input function F(s) and output function T(s) are given in Table
4.2. Taking into account the form of transmittances given by Eq. (4.83)
for the distinguished domains 1 and 2, the transmittances of the calo-
rimetric system given in Table 4.1 can be written in the form presented
in Table 4.3.
If we introduce the time constants and of the calorimeter, de-

fined as
which satisfy the equation
the transmittances given in Table 4.3 can be written in the form given in
Table 4.4. The time constants and determine the inertia of the calo-
rimeter and depend on the time constants of the distinguished domains
and the values of coefficients k. These are the roots of Eq. (4.85).
160 CHAPTER 4
It can be shown from the transmittances collected in Table 4.4 that

transmittance depends only on the time constants and of the
calorimeter; transmittance depends on the constants and but
also on the interaction coefficient k, which takes into account the tem-
perature differences between domain 2 and domain 1 in steady-state heat
transfer; transmittances and depend on the time constants
of the distinguished domains as well as on the time constants of the
calorimeter.
As a consequence of the different forms of transmittance, there are

different courses of the output function for the same forcing function.
We can demonstrate this on examples of 1) the pulse response of the

calorimeter; and 2) the temperature changes of the calorimeter as a
thermally inert object.
When the inverse Laplace transformation is applied to the transmit-
tances given in Table 4.4, the pulse responses of the calorimetric system
given in Table 4.5 are obtained; their plots are shown in Fig. 4.8. Fig-
ures 4.8a and 4.8d reveal that, when the heat source and the temperature
sensor are situated in the same domain, the shape of the pulse response
of the calorimetric system is reminiscent of the response of the calo-
rimetric system of first order. From the shapes of the curves given in
Figs 4.8d and 4.8c, it is clear that, when the heat source and temperature
sensor are situated in different domains, the pulse response of the calo-
rimetric system at the initial time moment is equal to zero, next in-
creases to a certain maximum value and respectively), and
then decreases to zero.
Thus, the pulse responses depend on the mutual locations of the heat
source and temperature sensor, and on the parameters of the calorimetric
system, and are non-negative functions.
Let us also consider the changes in temperature in time of the calo-

rimeter when there are no heat sources; the distinguished domains are
thermally inert objects, which is equivalent to the conditions
162 CHAPTER 4
The temperature changes of the calorimeter are caused only by the

initial differences in temperature of the bodies with respect to the envi-
ronment temperature, which can be written as
When the conditions given by Eq. (4.74) are taken into account, Eqs
(4.79) and (4.80) can be written in the form
The determination of and from these equations leads to
Equations (4.90) and (4.91) represent the Laplace transforms of tem-

peratures and when at least one of the temperatures of the
distinguished domains at the initial moment t = 0 is not equal to the en-
vironment temperature. Application of the inverse Laplace transforma-
tion to Eqs. (4.90) and (4.91) gives
where the time constants and of the calorimeter are given by

Eq. (4.84). When
the plots of the functions (4.92) and (4.93) are shown in Figs. 4.9a and
4.9b.
From the plot in Fig. 4.9a, it is seen that domain 1, at a temperature
higher by than the temperature of the environment, undergoes cool-
ing, the course of the temperature changes in time being reminiscent in
shape of a one-exponential course. Domain 2, whose temperature at the
initial moment is equal to the environment temperature, first undergoes
heating to temperature by a certain time and then cools to the
environment temperature. At time moment temperatures and
are equal. When the initial temperature of domain 1 is smaller by
than the environment temperature (Fig. 4.9b), the domain is heated to
the environment temperature; the temperature of domain 2 cools to
by time next returning to the environment temperature. The
extremum of temperature of domain 2 is accepted as the time moment at
which equalization of the temperatures of the two domains takes place.
When
the plots of functions (4.92) and (4.93) are shown in Figs 4.9c and 4.9d.
When the initial temperature of domain 2 is higher by than the envi-
ronment temperature (Fig. 4.9c), domain 2 cools to the environment
temperature, and the course of the temperature changes in time are
reminiscent in shape of a one-exponential curve.
164 CHAPTER 4
Domain 1 with an initial temperature equal to the environment tem-

perature heats up to temperature not reaching the temperature of
domain 2, and then cools to the environment temperature. The tempera-
ture of domain 1 is always lower than the temperature of domain 2. If
the initial temperature of domain 2 is lower than the environment
temperature (Fig. 4.9d), domain 2 heats up to the environment tempera-
ture. The temperature of domain 1, which at first is equal to the envi-
ronment temperature, decreases to a certain temperature and next
increases to the environment temperature. The extremal value of the

temperature of domain 1 depends on the value of interaction coefficient
k. As the value of interaction coefficient comes nearer to unity, the
neight of the peak is smaller.
When the initial temperatures of the two domains are equal and dif-
ferent from the environment temperature:
plots of the functions (4.92) and (4.93) are shown in Figs 4.9e and 4.9f.
From Fig. 4.9e, it can be seen that the temperatures of domain 1 and
domain 2 decrease in time, but the temperature of domain 1 decreases
faster than that of domain 2. When the initial temperatures are smaller
by than the environment temperature (Fig. 4.9f), both domains heat
up to the environment temperature, but domain 1 does so faster than
domain 2. The course of the temperature changes in domain 1 is remi-
niscent in shape of a one-exponential course.
The examples given above clearly show that the output function is
related to the mutual locations of the heat sources and temperature sen-
sor.
The presented equations were defined on the assumption that the
form of the input function and the initial conditions are known. To re-
construct the input function on the basis of the form of the output func-
tion, it is necessary to know the particular forms of the dynamics equa-
tion of the two-domain calorimeter with a concentric configuration.
4.3.2. Dependence between temperature and heat effect

as a function of location of heat source
and temperature sensor
Let us define particular forms of the equation of dynamics [Eqs

(4.74) and (4.75)] expressing the dependence between temperature and
heat effect as a function of the locations of the heat source and the tem-
perature sensor [8, 30, 40], As a basis of consideration, we will take the
equation of dynamics [Eqs (4.74) and (4.75)]. When heat power is gen-
erated only in domain 1, Eqs (4.74) and (4.76) take the form
166 CHAPTER 4
When heat power is generated only in domain 2, Eqs (4.74) and

(4.75) take the form
Taking into account Eqs (4.97)–(4.100), let us consider the following

cases:
1. The temperature is dependent on the function In this
case, the elimination of temperature from Eqs (4.97) and (4.98)
furnishes
Division of both sides of this equation by k and taking into account

Eq. (4.84) gives
With the assumption that
Eq. (4.102) can be written in the form

Equation (4.105) connects the changes in temperature of domain 1

with the heat effect generated in the same domain. It results from this
equation that the changes in temperature of this domain are determined
by the relation of the heat power and its derivative. This equation cannot
be directly applied to determine an unknown heat power, because it is
necessary to know the derivative of the value we are looking for.
2. The temperature depends on the function In this case, by
eliminating the temperature from Eqs. (4.97) and (4.98) and fol-
lowing the above routine, we can establish the relationship between the
temperature changes of domain 2 and the heat effect generated in
domain 1, which has the form
Analogously, by taking into account Eqs (4.99) and (4.100), the de-
pendences between the heat effect generated in domain 2 and the tem-
perature changes can be established for the following cases.
3. The temperature depends on the function In this case,
the equation of dynamics has the form
4. The temperature depends on the function In this case,

the equation of dynamics has the form
168 CHAPTER 4
Equation (4.107) has a form similar to that of Eq. (4.104). Particular

forms of the equation of dynamics show that, for the two-domain calo-
rimeter, the temperature sensor should be situated in another domain
than the heat source. In another case, it is possible to carry out a meas-
urement in such a way that the temperature sensor is situated in each
domain. Zielenkiewicz and Tabaka [278–281] showed that correct re-
sults can be obtained by applying multipoint temperature measurement,
corresponding to the number of distinguished domains.
Considerations as to the mutual locations of the heat sources and
temperature sensors can form the basis of the explanation of several
observed facts, such as the apparent change in heat capacity of the calo-
rimeter with time.
4.3.3. Apparent heat capacity
During the calibration of the Calvet microcalorimeter [10] and the

KRM calorimeter [282], it was found that the calculated value treated as
heat capacity changes in time.
Changes in the heat capacity of the calorimeter were noted, when
was calculated by using the heat balance equation of a simple body, in
which it is assumed that the heat capacity C depends neither on time t
nor on the geometrical distribution of the heat power source and the
location of the temperature sensor; it is equal to the sum of the heat ca-
pacities of all the parts i of the calorimeter:
On the assumption that the heat capacity C of the system corresponds

to Eq. (3.59) after integration can be written in the form
If we assume that the two-domain model with a concentric configu-

ration is the proper mathematical model for the examined calorimeters
[293], then, in a comparison of Eq. (4.109) with integrating Eqs (4.104)–

(4.107), the following cases can be considered:
1. Integration of both sides of Eq. (4.104) in the time interval
leads to
Simple rearrangement of Eq. (4.110) gives
A comparison of Eqs (4.109) and (4.111) results in

yields
or
Comparison of Eqs (4.109) and (4.114) gives
3. On integration of both sides of Eq. (4.105) in the time interval

we have
170 CHAPTER 4
and
By comparison of Eqs (4.109) and (4.117), we find

leads to
or
On comparing Eqs (4.109) and (4.120), we have
It follows from the above equations that the effective heat capacity
depends on various parameters: the heat capacities of the distin-
guished domains, the heat transfer coefficients between these domains
and the environment, the character of the changes in the heat effects in
time and their derivatives with respect to time, the changes in particular
temperatures in time and their time derivatives, and also the time inter-
val in which the heat effects are evaluated. The effective heat ca-
pacity is time-invariant in only a few cases, e.g. when and i = 1,2
for a system of two interacting domains.
4.3.4. Energy equivalent of calorimetric system
When the corrected temperature rise method was applied for the
calibration of the calorimetric bomb, it was established [22–24, 284] that
the calculated heat capacity of the device was not equal to the sum of the
heat capacities of the calorimeter parts.
King and Grover [22] described the calorimetric bomb in terms of a
two-domain model with a concentric configuration. As a result, in the
method of corrected rise the heat capacity C was replaced by a corrected
term, called the energy equivalent of the calorimeter:
where and are the heat capacities of domains 1 and 2, is the

heat loss coefficient between domains 1 and 2, and is
equal to the smaller of the cooling constants of the calorimeter.
Let us analyze [283, 285] the influence of the mutual locations of the
heat sources and temperature sensors on the value of the energy equiva-
lent for a calorimeter treated as a system of two domains. As stated pre-
viously, in the corrected temperature rise method three periods are dis-
tinguished during the experiment: and
In the initial and final periods, the calorimeter is a ther-
mally inert object; in the main period, the heat effect is generated in the
calorimeter.
As shown in §4.3.2, in the main period, the calorimeter can be de-
scribed by one of Eqs (4.104)–(4.107), depending on the mutual loca-
tions of the heat sources and temperature sensors, while integration of
these equations in the time interval
similarly as for Eqs (4.110), (4.113), (4.116) and (4.119), leads to
172 CHAPTER 4
where
and and are the values of the derivatives

of the temperatures and with respect to time t at moments and
respectively. Since the moments and belong in the periods when
heat power is not generated:
On taking into account Eqs (4.130)–(4.132), after simple transforma-

tion and integration, we find
If the temperature changes in the initial and final periods result from
the cooling or heating of the calorimeter as a thermally passive object,
the right-hand sides of Eqs (4.104)–(4.107) are equal to zero. The solu-
tions of these equations are
where and are constants. When the second

term of Eqs (4.136) and (4.137) decreases quickly and we can write
Equations (4.138) yield the following equations:
For and we have
When Eqs (4.123)–(4.134) and (4.140) are taken into account, Eqs
(4.123)–(4.126) can be written in the form
174 CHAPTER 4
Putting
Eqs (4.141)–(4.144) can finally be written in the form
Let us define the energy equivalent R of the calorimetric system as

the ratio of the generated heat amount Q to the corrected temperature
rise as a function of the mutual location of the heat source
and the temperature sensor. Then, taking into account Eq. (4.146), we
find that
when the temperature of domain 1 is measured and the heat effect
is generated in domain 1, the energy equivalent is equal to



It can be seen from Eqs (4.151)–(4.153) that the energy equivalent is

the same, equal to the product of the largest time constant of the calo-
rimetric system and the heat loss coefficient In Eq. (4.154), the
energy equivalent is smaller than in the first three cases.
In calorimetric measurements, the location of the temperature sensor
is generally fixed, while those of the calibrating heat source and the heat
source of the examined process can differ. If the temperature of the
other domains is measured, it is without difference in that one in which
only the calibrating effect and the heat effect process are situated be-
cause there is equivalence of the heat sources and On the other
hand, when the temperature is measured in the inner domain, the cali-
brations and examined heat effects must occur in the same domain be-
cause
The larger root of Eq. (4.84), which corresponds to the time constant
of the calorimetric system, is equal to
Taking into account the relationships (4.68)–(4.71), we obtain
From Eq. (3.96), we have
It results from Eq. (4.157) and Eqs (4.151)–(4.154) that the energy
equivalent has the dimension of heat capacity, but is not the sum of the
heat capacities and of the distinguished domains. When the calo-
176 C HAPTER 4
rimeter is thermally insulated which corresponds to adiabatic

conditions, the value of the equivalent is equal to the sum of the heat
capacities of the distinguished domains. When ideal heat exchange oc-
curs with the distinguished domain both domains can be
treated as simple domains and the energy equivalent is equal to the sum
of the heat capacities.
Final Remarks
The present theory of calorimetry is a result of the authors’ own

work. Its essential feature is the simultaneous application of the relation-
ship and notions specific to heat transfer theory and control theory. The
present theory has been used to develop a classification of calorimeters,
to discuss selected methods of determining thermal effects and ther-
mokinetics, and to describe the processes proceeding in calorimeters of
various types. Calorimeters have been assumed to constitute linear sys-
tems. This assumption allowed the principle of superposition to be used
to analyze several constraints acting simultaneously in and on the calo-
rimeter.
The present theory of calorimetry is concerned mostly with the in-
struments whose principle of operation is assumed to involve the trans-
fer of heat in the system. This is true for most of the existing calorime-
ters, whether those with a constant or those with a variable temperature
of the shield. It includes calorimeters in which the flow of heat between
the calorimeter proper and its surroundings is quite intense, and also
those in which this flow of heat is very low. On the other hand, the pre-
sent theory is concerned to only a minor degree with calorimeters whose
principle of operation is based on the assumption that there is no heat
transfer (adiabatic calorimeters) or that, by definition, the heat transfer
process is stationary (the generated heat effect is compensated).
The considerations presented are based on the general heat balance
equation of N-domains. A majority of the methods used to determine
heat effects have been shown to rely on the simplest, particular form of
this equation. This makes the calculations very convenient, but implies a
number of simplifying assumptions. These give rise to several limita-
tions, which have been duly pointed out. Of the methods described and
178 FINAL REMARKS
used to determine heat effects and thermokinetics, the method of N-

domains has been given special attention. This method may be particu-
larly useful when the calorimeter constructed is used to study transfor-
mations of short or long duration, and with constant or varying volumes
and heat capacities of the samples examined. This method is advanta-
geous in that it allows the identification of calorimeter parameters by
specifying the “exchangeable” part of the calorimeter as contrasted with
the “nonexchangeable” part; this makes the changes that have to be in-
troduced into the algorithm of calculations when the measuring condi-
tions are modified rather minor ones. The method is of particular value
when the construction of the calorimeter permits the instrument to be
used for various applications. This is true of the numerous calorimeters
produced by the major manufacturers.
The references reviewed illustrate that most investigators have been
looking for ways to enhance the accuracy of measurements by making
use of the conclusions deduced from the analysis of the course of heat
effects proceeding in the calorimeter. This is of particular concern as
regards calorimetric determinations carried out with the recent DSC
techniques. In such investigations, the application of the procedures
described in the book and based on the general equation of dynamics
and on the method of analogy of the thermal and dynamic properties of
the objects, can be of essential assistance.
The numerous illustrative applications of the theory to various prob-
lems in the analysis of heat transfer processes occurring in calorimeters
should encourage investigators to undertake work to improve the theory
of calorimetry still further and to develop more practical applications.
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Hot Topics in Thermal Analysis and Calorimetry
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4.3. Dynamic properties of calorimeters with concentric configuration 154

Final remarks 177

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

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

The calorimeter as an object

A calorimeter can be treated as a physical object with active heat

1.1 The Fourier law and the Fourier-Kirchhoff

Heat transfer by conduction in a homogenous, isotropic body is

Quantity T in Eq. (1.1) is a function of the coordinates x, y, z and

At points of an isothermic surface, the absolute gradient values are equal

where denotes differentiation along an outward-drawn line normal

The heat flux through a surface element dS in time dt, in conformity

where dS = ndS is a normal vector to a surface element in the external

On application of the Gauss-Ostrogrodsky theorem, which states that

The amount of heat generated in the body by the inner heat

The amount of heat accumulated, according to Eq. (1.6), is equal

According to the First Law of Thermodynamics, the amount of heat

where dh is the increase in specific enthalpy (due to unit volume), and p

where is the specific heat capacity at constant pressure, in

With regard to Eqs (1.16) and (1.17), Eq. (1.12) becomes

Comparison of both sides of Eqs (1.13) and (1.18) gives

Equation (1.19) is valid in any element of the body if

Division of both sides of Eq. (1.20) by dt gives

On introduction of Eqs (1.15) and (1.1), Eq. (1.21) can be written in

For a solid body with a distribution of temperature T at time t given

Thus, the substantial derivative of temperature takes the form

Introduction of the velocity vector w

into Eq. (1.25) lends to

In a similar way, pressure changes as a function of (x, y, z, t) can be

Substitution of Eqs (1.27) and (1.28) into Eq. (1.22) yields

Equation (1.29) is called the Fourier-Kirchhoff equation.

the Fourier-Kirchhoff equation (Eq. (1.29)) takes the form

When the velocity vector is equal to zero, i.e.

Eq. (1.31) becomes

Equation (1.33) is called the Fourier equation or the equation of con-

and the distribution of temperature is a function only of the Cartesian

When g = 0, the temperature changes depend only on the initial dis-

is the subject of great numbers of calorimetric determinations.

This is called the thermal diffusivity coefficient, expressed in

where is a Laplace operator:

a) Dimensionless parameters which characterize the shape and dimen-

In the spherical system, is expressed by

In the case of a cylinder, it is convenient to operate with cylindrical

b) Physical parameters such as specific heat density and thermal

2. The prescribed distribution of the heat flux or temperature gradient

where is the surface heat transfer coefficient (see § 1.2).

1.2 Heat transfer.

“When different parts of a body are at different temperatures, heat

where coefficient is called the surface conductance or the coefficient

by equating the right-hand sides. When the geometry of the considered

coefficient. The variations in thermal resistance between two solid bod-

The criteria numbers are calculated by use of material constants such as

A frequent goal in calorimetry is to obtain a constant value of irre-

where is a substitute emission coefficient depending on the emission

or, on analogy with Eq. (1.47):

is called the radiation heat transfer coefficient. When the temperature