THEORY OF CALORIMETRY
Hot Topics in Thermal Analysis and Calorimetry
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
Institute of Physical Chemistry,
Polish Academy of Sciences, Warsaw, Poland
Institute of Physical Chemistry,
Polish Academy of Sciences, Warsaw, Poland
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6.7. The Fourier law and the Fourier-Kirchhoff equation 1. Heat transfer. Heat balance equation of a simple body. Cooling and heating processes 1. Modulating functions method 2. convection and radiation 1.2. Calculations of spectrum transmittance 2.7.Contents
The calorimeter as an object with a heat source
1.7. Dynamic time-resolved characteristics 2. The heat balance equations for a rod and sphere 1. Methods of determination of dynamic parameters 126.96.36.199.3.7.4. Types of dynamic objects 2. General heat balance equation of a calorimetric system
Calorimeters as dynamic objects
2. Frequential characteristics 2. Laplace transformation 2.1.7. General integral of the Fourier equation.5. Conduction. The Newton law of cooling
1. Rational function method of transmittance approximation Determination of parameters of spectrum transmittance 2. Pulse response 2.4. Determination of time constant 188.8.131.52.5.1.
.2.1. Least squares method 2.5.
Method of transmittance decomposition 3.
Thermal curve interpretation method 3.2. Dynamic properties of two and three-domain calorimeters with
cascading structure 184.108.40.206
Harmonic analysis method 220.127.116.11. Numerical and analog methods of determination
of thermokinetics 18.104.22.168.11.2.4. Three domains in series 22.214.171.124. Equations of dynamics.6.11.
Methods of determination of heat effects General description of methods of determination of heat ef3.5. Equations of dynamics.
Modulating method 3.
Finite elements method 126.96.36.199. fects 3.
Steady-state method 3. Evaluation of methods of determination of total heat effects
and thermokinetics 3.2.5.
Method of state variables 3.
Classification of calorimeters 188.8.131.52.
Comparative method of measurements 184.108.40.206.2.
Multidomains method 220.127.116.11.7.11. System of two domains in series 4. of heat effects Methods of determination
85 85 97
Inverse filter method 3. Equations of dynamics 4.2.
Method of corrected temperature rise 3.2.2. Applications of equations of dynamics of cascading systems
Classification of calorimeters.1. Linearity and principle of superposition
Dynamic properties of calorimeters
Method of dynamic optimization 3.
Dynamic method 3. Adiabatic method and its application in adiabatic and scan
ning adiabatic calorimetry 3.
Flux method 18.104.22.168.8.
3.4. Dependence between temperature and heat effect as a function of location of heat source and temperature sensor Apparent heat capacity 4.3. Dynamic properties of calorimeters with concentric configuration 22.214.171.124.CONTENTS
vii 154 155 165 168 171 177 179
4. Dependence of dynamic properties of two-domain calorimeter with concentric configuration on location of heat sources and temperature sensors 4. 126.96.36.199. Energy equivalent of calorimetric system
Final remarks References
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to determine a heat effect. the accuracy required. it is necessary to establish the relationship be tween the heat effect generated and the quantity measured in the calo rimeter. The calorimeter is an instrument that allows heat effects in it to be determined by directly measurement of temperature.. The date on which calorimetry came into being may be taken as 13 June 1783. It is this relationship that unambiguously determines the mathematical model of the calorimeter. The theory of calorimetry presented below is based on the assumption of the calorimeter as an object with a heat source. With the aim of a description and analysis of the courses of heat effects. and as a dynamic object with well-defined parameters.Memoire de la Chaleur“ at a session of the Academie Française. Depending on the type of calo rimeter applied. many new methods have been developed and the measuring techniques have been improved. Accordingly. the method of analogy is applied. Various methods are used to construct the mathematical model of a calorimeter. the day on which Lavoisier and Laplace presented a contribution entitled .Preface
Calorimetry is one of the oldest areas of physical chemistry. so as to interrelate the thermal and the
. and the conditions of heat and mass transfer that prevail in the device. 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. Throughout the existence of calorimetry. numerous laboratories worldwide continue to focus attention on the development and applications of calorimetry. At pre sent. the relationship between the measured and generated quantities can assume different mathematical forms. and a number of compa nies specialize in the production of calorimeters.
. This equation is demonstrated to be of value for an analysis of various thermal transformations occurring in calorimeters. Attention is concentrated on calorimeters as inertial objects. The considerations presented can prove to be of great use in studies intended to enhance the accuracy and reproducibility of calorimetric measurements. a calorimeter with only proportional or integrating properties is treated as a particular case of an inertial object. As the basis on which the thermal properties of calorimeters will be considered. the equation of dynamics is for mulated. In view of the fact that the general mathematical equations describing the properties of inertial objects contain both integrating and proportional terms. and in connection with methods utilized to observe heat effects in thermal analysis.x
dynamic properties of the calorimeter. integrating and inertial objects. the general heat balance equations are formulated and the calorimeter is taken as a system of linear first-order inertial objects. The methods applied to determine the total heat effects and thermokinetics are presented. The thermal and dynamic properties that are distinguished are used as a basis for the classification of calorimeters. The dynamic properties of calorimeters are defined as those corre sponding to proportional. For analysis of the courses of heat effects.
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. Particular forms of this equation will be applied to consider problems that form the subject of this book. An understanding of these processes is of importance for a proper interpretation of calorimetric measurements. There is an understandable tendency to attempt to ex press these models in the simplest way. This chapter will present a detailed consideration of this topic.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. which express the dependence of the change in temperature measured directly as a function of the heat effect produced. one has to understand precisely the assumptions made. Selected problems from heat transfer theory are also presented. An analysis of the thermal processes occurring inside the calorimeter. Spe cial attention is paid to a discussion of the processes occurring in a nonstationary heat transfer state.
. To make use of them wisely. In practice. this is achieved by applying simplifications to the original formulas. and those between the calorimeter and its environment. The general heat balance equation is introduced into the considerations.
the absolute gradient values are equal to
where denotes differentiation along an outward-drawn line normal to the surface. Such a surface is called the isothermal surface for temperature T. The value of is an experimentally determined coeffi cient called the thermal conductivity. grad T. is a vector:
At points of an isothermic surface.1) is a function of the coordinates x. The heat flux q. in ing the rate of heat Q transferred through unit surface at point P per unit time dt (Fig.2
1. The gradient of temperature.1):
Quantity T in Eq. isotropic body is mathematically described by the Fourier law :
which assumes proportionality between the heat flux q and the tempera is a vector determin ture gradient grad T. the temperature at this instant is the same. y. (1. expressed in
.1 The Fourier law and the Fourier-Kirchhoff
Heat transfer by conduction in a homogenous. z and time t. At every point upon it. 1. For any time t the value of T determines the scalar temperature field.
and its intensity. The reciprocal of the thermal conductivity of a material is called its thermal resistivity.6]. we will consider the process of heat flow by con duction from a solid body of any shape and volume V located in an environment of temperature [5. Thus. corresponds to the sum of the amount of heat accumulated.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
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. is the essence of the Fou rier law. the amount of heat generated. the general character of which is the basis for analysis of vari ous phenomena of heat considerations. dQ. the variation in may not be large and as a reason able approximation it can be assumed to be constant. and the amount of heat ex changed. expressed by temperature T. The value of for isotropic materials is a scalar.
. If the range of tem perature is limited. When heat is generated in the body. The analysis is performed by use of the heat conduction equation of Fourier-Kirchhoff. two processes can occur: the ac cumulation of heat and heat transfer between the body and its environ ment. Let us derive this equation. its value depending on pressure and temperature changes. To do this. The relation between the heat energy. expressed by the heat flux q.
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. (1.9) and (1. corresponds to
where dS = ndS is a normal vector to a surface element in the external direction. in conformity with Eq. 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.6).4
The heat flux through a surface element dS in time dt. Eq. (1. which states that the surface integral of a vector is equal to the volume integral of the divergence of the vector. (1. to
according to Eq.12) can be written in the form
.11) are taken into account. (1. is equal
When Eqs (1. Eq.5).
20) by dt gives
. expressed in the body of volume V is equal to
The second term on the right-hand side of Eq.12) becomes
Comparison of both sides of Eqs (1. The increase in specific enthalpy is proportional to the increase dT in temperature T:
is the specific heat capacity at constant pressure.13) and (1.16) and (1.17). Eq. the amount of heat can be described for each volume element of the accumulated. (1.14) may be written
With regard to Eqs (1. (1. and p is pressure.18) gives
Equation (1.19) is valid in any element of the body if
Division of both sides of Eq. body as
where dh is the increase in specific enthalpy (due to unit volume). in The increase in enthalpy in
and is the density. (1.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
According to the First Law of Thermodynamics.
(1. Eq.15) and (1.21) can be written in the form
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. z. (1. t) can be expressed by
On introduction of Eqs (1. pressure changes as a function of (x.25) lends to
In a similar way.
Relation (1.33) is called the Fourier equation or the equation of con duction of heat. 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.
the Fourier-Kirchhoff equation (Eq.31) becomes
Equation (1.28) into Eq.e. (1.
Eq.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
Substitution of Eqs (1.27) and (1. When the process takes place under isobaric conditions.22) yields
Equation (1. i.29) is called the Fourier-Kirchhoff equation. which takes place when the changes in temperature T are time-dependent:
. b) A non-stationary (non-steady-state) heat transfer process. z). (1. (1. when g = const.e. i.29)) takes the form
When the velocity vector is equal to zero.y.34) is fulfilled. Let us use the Fourier equation to consider the following processes: a) Stationary (steady-state) heat transfer.
parameter a is often applied:
This is called the thermal diffusivity coefficient.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. For steady-state processes. the temperature changes depend only on the initial dis tribution of temperature. It is usually assumed that the temperature at the beginning of the process is constant. They characterize the heating or cooling proc esses occurring in the thermal by passive body. expressed in Introduction of coefficient a into Eq. it is necessary to de termine the initial and boundary conditions. The boundary conditions prescribe:
When g = 0. (1. The investigation of heat processes for which
is the subject of great numbers of calorimetric determinations. and are constants independent of both pressure and When temperature. the course of the temperature changes does not depend on the initial condi tions. In order to obtain the particular solutions of these equations. 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.
The prescribed distribution of the heat flux or temperature gradient on the surface of S of the body:
3. it is considered that and
are constants. it is convenient to operate with cylindrical coordinates r. x in which the Laplacian has the form
b) Physical parameters such as specific heat density and thermal
conductivity coefficient which characterize the properties of the body
and the environment. where
In the spherical system.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
a) Dimensionless parameters which characterize the shape and dimen sions of the body. In all the problems discussed in this book. These conditions are as follows:
is expressed by
In the case of a cylinder. It is determined that they are constant or a function
of temperature. The defined relation between the temperature and the heat flux on the surface S of the body:
. An example is a homogenous ball with radius R.
c) Surface conditions. The prescribed temperature distribution on the surface S of the body:
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 FourierKirchhoff 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” . 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:
THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
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 heattransfer 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  that even surface irregularities within the range of tens of microns influence the value of the surface heat transfer
coefficient. The variations in thermal resistance between two solid bod ies are the cause of errors in the heat determination. also de The coefficient of surface heat transfer by conduction 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 calorimetric 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 defining the heat ex convection coefficient of surface heat transfer, 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 is the difference in temperature, and is the due to gravity; 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. , free convection occurs in the spherical space is defined by around the calorimeter, and as a result the coefficient the equation
THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
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 radiated through a transparent gas sorptivity. The quantity of heat 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 Introduction of the relation express constant ing the total radiant energy leaving unit surface area:
or, on analogy with Eq. (1.47):
is called the radiation heat transfer coefficient. When the temperature difference
Any assumptions made will not impose any restrictions on the solution. If the value of this fraction is very small. General integral of the Fourier equation. the solution of the Fourier equation will refer to the heating or cooling processes of a thermally passive body. 8]. When heat is generated in the body and the expression of g (x. y.
Cooling and heating processes
Let us consider the temperature changes in a body. on the assumption that the initial conditions are zero. called the heat loss coefficient. the particular solution of the Fourier equation. y. it is assumed that
In the examined case. Accord
. z) = 0. z.
1. 6. The initial condition is defined as
Additionally. In calorimetry.14
is much lower than the temperatures
can be expressed by
where higher–power exponents of ratio are neglected. which is equivalent to the effec tive heat transfer coefficient calculated for the whole surface S. due to the initial temperature difference between the body surface S and the environment [1.3. T(x. it is more common to use coeffi cient G. can be found. then a simplified formula is often valid:
The heat transfer in calorimeters is described in terms of the effective heat transfer coefficient. t) is known. involving the heat transfer of convection. con duction and radiation.
If it is assumed that the physical parameters are constants and the Fourier equation (Eq. (1.e. y. t) can be described as
Substituting the above equations into Eq. T(x. after transformation
and can be written in the form
To solve the differential Eq.63) gives
or. Let the heat transfer between the body and its environment proceed through the surface S according to the boundary condition of third kind. the solution will be the sum of the sepa rately determined solutions. According to this function. z. the Fourier method of separated variables will be used.63). (1. i.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
ing to the superposition rule. (1.
Thus. we obtain the two following differential equations:
Equation (1. both sides must be equivalent to the same constant value. when the initial temperature of the body is higher than the envi ronment temperature. To satisfy Eq.69) is a function only of coordinates (x. let us denote by the value of the sides of Eq. the heating process is characterized by
In order to fulfil this condition. (1. y. whereas the left–hand side is a function only of the independent variable t. instead of one differential equation.69).16
The right–hand side of Eq. z).69). This means that this value should be negative. Thus. when the initial temperature of the body is lower than the envi ronment temperature.73) may be written as
. (1. a cooling process occurs and
The functions in Eq. Since Eq. its solution is also the sum of eigenfunctions:
or.62) is a linear differ ential equation. it can be written in the form
On introduction of the notation
Equation (1.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE and its solution is
which can easily be checked. with regard to Eq.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).
Equation (1.80).80) corresponding to the particular eigenvalues are called eigenfunctions.82) can be written as
. (1. (1. (1.
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 limiting case. These methods are disscused in Chapter 3. excluding the one having in the exponent the smallest value of the constant Equa tion (1. t) is needed. The question of the determination of total heat effects for a multiex ponential temperature course in time was investigated by Hattori et al. The excellent monograph by Camia  is one of the most important works on this field. The expression given by Eq. the monotonously decreases . Whereas the sequence of eigenvalues is an increasing sequence. A number of methods are currently used to determine the heat effects and thermokinetics of short–duration processes.85) was used for the first time in microcalorimetry to describe short–duration heat processes investigated in a Calvet microcalorimeter [10–13]. y. 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.  and Tanaka and Amaya . z. based on the assumption of a multiexponential course of temperature changes. t) changes at any point of the body is the sum of infinite number of exponential functions. it is possible to neglect all the exponential terms.
. y. As a sequence of constants higher accuracy of determination of temperature T (x.18
We see that the course of the temperature T (x. z. This type of description is mostly used in calorimetry and thermal analysis.84) then transforms to an equation equivalent to the mathemati cal expression of Newton’s law. (1.
at constant temperature. Its ends are defined as x = 0 and x = L.3). For the solution of the Fourier equation. that surrounds the calorimeter (Fig.  consider the calorimeter in terms of a onedimensional model of distributed parameters.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
Hattori et al. the heat conductor along which the heat flows has a well-insulated lateral surface. which are solids. Tanaka and Amaya  consider the calorimeter as a concentric and (Fig. These three domains represent the calorimetric vessel. independently of the
. in which heat q heat is generated or adsorbed. the environment is kept at constant temperature. In both of the above papers. The objects distinguished are the calorimetric vessel A. 1. is surrounded Domain by domain Domain is surrounded by domain at constant tem perature. it was shown that. and the heat conductor between the vessel and the shield.2). the following assumptions were made: heat power is generated in the calorimetric vessel at homogenous tem perature and with constant heat capacity. The heat transfer takes place only through the cross-section for x = 0. model of three domains. there exists a heat bridge of the calorimetric vessel with the conductor. the heat conductor B and the medium C. 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 CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
The left–hand side of Eq. (1.88) can be transformed as follows:
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
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, and the temperature on the because the relation between temperature surface is not defined.
If it is assumed that
Equation (1.97) becomes
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.
THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE When
Equation (1.99) becomes
If it is assumed that
Equation (1.102) becomes
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 . 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. Coefficient 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) When these temperatures are is appropriate only when different, Eqs (1.97) and (1.105) can be supplemented by a new parame ter, the coefficient of heterogenity of the temperature field
1. 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. Eq.4).( 1. it would This condition is difficult to be necessary to know the function fulfil. It is assumed that. the relation between heat capacity C. for the ordered state heat transfer. comes after a certain period of time (Fig.97) becomes
In order to solve this non–stationary differential equation.24
Thus. cooling constant and coefficient is expressed as follows:
. The second. heat loss coefficient G. To solve the theory of the problem of ordered state heat transfer . the well-ordered heat transfer period.
5). its value can vary between one and zero. this equation is also used as a mathematical model in determining the P(t) function in instruments with
. The more differs from unity. 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. Only in the case of certain small values of coefficient can it be assumed that a homogenous temperature distribu exists in the examined body. It also indicates that the range tion 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. This coefficient is a function of Biot’s num Coefficient decreases to zero as constant Bi increases ber to infinity. However.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
Coefficient is a dimensionless quantity. 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. the greater is the inequality in the field of temperature. 1.
5. For a body treated as a rod in which the process takes place under isobaric condi tions. while is a time constant. a new mathematical model of the calorimeter was elaborated [8. In the system discussed.26
different values of coefficient It is applied as a mathematical model in conduction microcalorimeters.g. the Fourier-Kirchhoff equation may be written as
. The the physical pa relation between the dimensionless parameter rameters of the system and was elaborated. it would be most convenient to establish a set of parameters (e. For these reasons. without mass exchange. in which heat exchange between the body and environment is extensive and coefficient is significant. Between these parts one can expect the existence of heat resistances and heat bridges. The heat balance equations
for a rod and sphere
A real calorimeter is composed of many parts made from materials with different heat conductivities. 19] based on the assumption that constant tempera tures are ascribed to particular parts of the calorimeter. (1.99). If a maker of a calorimetric system decides to apply the method of determining the heat effect resulting from Eq. A probe to determine such a set of pa rameters was undertaken by Utzig and Zielenkiewicz  for a simple physical model as an approximation of a real calorimetric system.
1. it is very important to verify the accepted model experi mentally. such that the is generated fulfils the conditions calorimeter in which the heat needed to apply this equation. In the parameter the value corresponds to the time interval after which the body temperature changes can be described by one exponential term. temperature gradients can occur a priori. Before defining the general heat balance equation. To describe the heat transfer in such a system. let us consider the particular solutions of the equation of conduction of heat for a rod and sphere.
t) at points gives the following set of equations:
. (1. we have
Consideration of the function T(x.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.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
Consider the above equation for
If we put
116) in Eq. (1. (1.28
If we put
this set of equations becomes
The solutions of the equation set defined by Eq. (1.111) gives
Substitution of Eq.
are the heat transfer coefficients between domains n and n+l. Thus. and do mains n–1 and n. Eq.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
Let the volume of the n-th element be
where F is the cross–sectional area of the rod. (1. Multiplication of both sides of Eq. (1. respectively.118) by gives
is the heat capacity of domain n.120) may finally be writ ten as
. The quantities
denote the heat loss coefficients. whereas
is the heat power generated in domain n.
The same procedure is applied to deduce the equation of heat conduction for a homogenous sphere of radius r. Equa tion (1. respectively. where an isobaric process without mass exchange takes place. t) into a Taylor series in the neglecting terms of higher order than neighborhood of the point the second.30
denote the amounts of heat exchanged between domains n and n+1 and between domains n–1 and n in time interval dt. leads to
gives the set of equations
. The Fourier-Kirchhoff equation written with spherical coordinates be comes
Let us consider the above equation with
The expansion of the function T(r.125) is the desired heat balance equation for a rod considered as a system of domains arranged in a row.
THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
Let us put
and neglect derivatives of higher order than the second:
The solutions of the above set of equations are
the heat exchange between these parts is characterized by heat loss coef ficient G. the second and third terms are the amounts of heat ex changed between this part and the neighboring domains of indicators
CHAPTER 1 From Eqs (1. (1.13 6) by
gives the following differential equation
The heat balance equations for the rod and sphere described as Eqs (1.135) and (1. (1.134).132). domains) are distinguished. each is characterized by a constant heat capacity and homogenous temperature in the total volume.138) are identical in form. They are derived on the basis of the same assumptions: in the examined bodies several elements (parts. (1.128) we have
Multiplication of both sides of Eq. 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.125) and (1.
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 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. but also between any domains characterized by heat capacities and temperatures Each of the separate domains has a uniform temperature throughout its entire volume.6.139) as the basis on which to de rive the generalized heat balance equation of the calorimeter treated as a multidomain (elements. and the heat capacity of domain is constant. the total amount of heat dQ”(t) exchanged between domain j and the remaining domains and the environment is equal to
. General heat balance equation
of a calorimetric system
Let us assume Eqs (1. by assumption. The heat exchange between the body and environment is characterized by the boundary condition of the third kind. a heat source or temperature sensor may be positioned in any of the domains. Let us also assume that the heat transfer in the body can take place not only between the neighboring domains. parts) system of various configurations [19-21]. Temperature gradients appear only in these centers and between the domains and the environment. The amount of heat ex changed between domain j and the environment in time interval dt is equal to
Thus. their heat capacities are. the heat loss coefficient is the propor tionality factor:
The condition is fulfilled. its temperature is a function only of time t.126) and (1. negligibly small.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
n+1 and n–1. Furthermore.
Taking into account Eqs (1. 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).141). Thus:
From Eqs (1.143) and (1.140) and (1. we have
Dividing both sides of the above equation by dt gives
The representation of the calorimeter by mathematical models de scribed by a set of heat balance equations has long traditions. the first term on the right–hand side determines the amount of heat accumulated in domain j. 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.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. Zielenkiewicz et al. For example. The differential equation Eq. the second term the amount of heat exchange between domain j and the environment.148). and the set of these equations is the general heat balance equation of a calorimetric system. To consider the thermal properties of a calorimeter. In 1942 King and Grover  and then Jessup  and Churney et al. In Eq. and the last term the amount of heat exchange between domain j and remaining N–1 do mains. (1.THE CALORIMETER AS AN OBJECT WITH A HEAT SOURCE
v–n.  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. many papers have been published on this field.
is the heat power generated in domain j. 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 general heat balance equation corresponds to the formalization of the general calorimetric model by means of the set of equations with lumped parameters. while Kumpinsky  developed a method or evaluating heat-transfer coeffi cients in a heat flow reaction calorimeter. Socorro and de Rivera  studied microeffects on the continuous-injection TAM microcalorimeter. Since that time. (1. The heat balance equa tion Eq.148) is called the general heat bal ance equation of domain j.
In a corresponding network analog. the thermal resistances and capacities are simulated by electric resistors and capacitors. The thermal-electric analogy was applied by Nico laus  to analyze the problem of reconstruction of the heat flux curve. the differential scanning microcalorimeter of Arndt and Fujita . 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.  used both passive and active analogs to investigate the effect of the holder design on the shape of DTA peaks. which distinguish the domains and the modes of their connection with themselves and the environment. This is based on the similarity of the equations describing heat conduc tion and electric conduction. respectively. Wilburn et al. It is also useful to formulate a suitable system of the balance equations for the bodies (do mains). Rouquerol and Boivinet  presented analogs of electric circuits for the following heat-flux and power com pensation devices: the conventional DTA instrument of Mauras . 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. Ozawa and Kanari  illustrate the discussed heat balance equations for constant heating rate DSC by an equivalent electrical circuit.36
The calorimeter as a system of several domains has often been pre sented by using a method based on thermal-electric analogy [51–53]. and electric capacity and heat capacity. Such a study generally involves both the use of circuit theory and the principle of dimensional similarity. electric resistance and thermal resistance. The thermal–electric analogy method has been used to analyze and represent the operation mode of a number of calorimetric and thermal analysis devices. In construct ing such circuits. The method of analogy is also used in the papers of Claudy et al. The thermal-electric analogy method is useful to represent the ac cepted structures. The increase in the number of its applications is related to the development of analog computer calculation methods. [61–63]. it is considered that there is an equivalence between the quantities: electric current and heat flow. and the Tian-Calvet microcalorimeter . For example. electric voltage difference and temperature difference.
g. When the unchanging relation between the input and output functions is determined. which transforms the input functions into the output functions.e. in calorimetry the output function never reproduces the input function directly. Assuming linearity and applying the superposition rule. The steering theory treats a calorimeter as a dynamic object. it fur nishes an explicit description of the dynamic properties of the calo rimeter. one
. 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. then the dynamic object (calorimeter) is described by a system of n differential equations. Thus. temperature (output signal). 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. If there are many output functions. These equations are treated as the mathemati cal models of calorimeters.
which permits determination of the input function on the basis of a given course of the output function of the calorimeter. The calorimeter is a kind of transducer. Let us describe the input signals by the functions and the output signals by the functions In fact.Chapter 2
Calorimeters as dynamic objects
Calorimeters are physical objects that can be described in different ways. in which the generated heat effects (input signals) are transformed to the quantity measured directly in the calorimeter.
x(s) and y(s) of Eq. the dynamic properties are encoded. The experimental de
. 2. The objects of the
structure shown in Fig. 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 H(s) can be determined only on the basis of ex perimentally determined y(s) and x(s). On analysis of an object described by one input and one output function. It is assumed that the calorimeter can be treated as a linear. (2.3) written in the form
can be visualized by a block diagram (Fig.1 are called open objects in the steering theory. x(s) and y(s) are the Laplace transforms of the output signal x(t) and the input signal y(t).38
may reduce two or n objects to one. The calorimeter is then treated as a “black box” and knowledge of their physical parame ters is neglected.
Let us consider the quantities H(s). we do not lose generality. The transmittance (transfer function) of the object has the form
where s is a complex variable.1). respectively. Equation (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.4). stationary and invariant object. 2. The function is defined as the quo tient of the Laplace transforms of the output and input functions. A convenient method for solving linear equations is to apply the Laplace or Fourier transform. In the transfer function (transmittance). Each of them can be obtained by using the two others: 1. 2.
CALORIMETER AS DYNAMIC OBJECT
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.
2. the following types of dynamic objects can be distinguished [64. and the transmittance H(s) has the form
while the spectrum transmittance
is expressed by Eq. This procedure is convenient to verify the agreement between experimentally de termined and calculated functions x(s).7):
Integrating type. when the input function is proportional to the derivative of the output function:
. This procedure is equivalent to the calibration of the calo rimeter. Types of dynamic objects
Among the open systems. The transform y(s) is evaluated on the basis of previously known H(s) and experimentally determined function x(s). 65]: Proportional type. 3. 4.1. The form of the transmittance depends on the type of the dynamic object. The transform x(s) is determined in the knowledge of the form of the transmittance H(s) and the values of their parameters. when the input function y(t) is proportional to the output function x(t):
where k is the proportionality coefficient. It corresponds to the determination in the domain of the complex variable of the course of the investigated heat effect. (2. Input function y(s) is determined experimentally.
We compare Eq.8).g temperature) has the properties of the proportional object. when the input function is a linear combination of the output function and its derivative:
Let us compare the equations describing the dynamic properties of the distinguished types of objects with suitable heat transfer equations: 1. 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. We compare Eq. The properties of integrating
First-order inertial type. which describes the dynamic properties of an integrating object. (2. with the first term of the left-hand term of Eq. which describes the dynamic properies of a proportional object.11).(1.99). (1.46)]. We compare Eq. (1. 2. which describes the dynamic properties of an inertial object. with the heat balance equation of a simple body [Eq.5). 3. (2. (2. with the Newton heat transfer equation [Eq.99)].
CALORIMETER AS DYNAMIC OBJECT
objects are those of adiabatic calorimeters. It is expressed as a function of time. In this transformation.2. this idealization is well-founded in many cases. the function f(t) of the real variable is changed into the complex function F(s) of the complex variable s. The relation describing the dynamic properties of the object is equivalent to the mathematical model of the calorimeter. inside which the accumula tion of heat occurs. Of course.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. Calorimeters that are inertial objects comprise the most numerous group of calorimeters.14):
and abbreviated as
where while for the existence of the transform F(s) the condition must be fulfilled. frequency or a complex variable domain. (2. The inverse Laplace transformation is defined by Eq. (2. Let us assume that a calorimeter has only the integrating or proportional properties of the object. Its advantages include: 1) The Laplace transforms of simple functions can be deter
. as a certain idealization.
2. Laplace transformation
The Laplace transformation  is the operation of changing one expression into another by integration. The Laplace transform is defined by Eq.
F(s) and are driving forces. Let us apply the Laplace transform to the heat balance equation of a simple body (Eq. called the subsidiary equation of the differential equation. (2. (2. 2) the Laplace transformation is a linear transformation for which superposition holds.99):
On dividing by G and putting
Use of the Laplace transformation for Eq. the simple function f(t) and the transform F(s) representing the function transform pairs are tabulated. T(s) is the response transform of the output function.22).22) is called the subsidiary equation of differential Eq. (1. an ordinary differential equation is reduced to the algebraic equation of the transform. the function of the initial conditions.99). 3) by application of the Laplace transformation. are the transforms of the transient
. (2. (2. The first and third terms on the right-hand side of Eq.21) becomes
Equation (2. Eq. In most cases.19) in the complex domain
After simple rearrangement.42
mined by direct integration or integration by parts. and is the characteristic function of the object. 1.19):
gives the solution for Eq.
If it is assumed that two first-order inertial objects in series are dis tinguished in the calorimeter. When the heat effects are not generated.2). while the output function of the first object is at the same time the input function of the second object (Fig.20) for the other input functions. which is independent of the initial condi tions.CALORIMETER AS DYNAMIC OBJECT
solution. then the calorimeter transmittance H(s) has the form
In the time domain. The second term. Then:
In a similar way. Let us assume that the objects are arranged in series in such a way that the input function of the next iner
. 2. The inverse Laplace transformation defines the function T(t) charac terizing the course of the temperature changes of the calorimeter. and and thus T(t) depends only on the initial temperature difference T(0) between the calorimeter and its environment. (2. represent the transform of the steady-state solution. the Laplace transform can be applied to obtain the solution of Eq. 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.
2.5.3 are characteristic for the open systems and differ from one another only in the number of inertial objects. 2. The dynamic objects are not always arranged in series. is shown in Fig. 2.4. caused by input function forcing corresponding to the unit step function.
A graphical presentation of the output functions for numbers of objects ranging from one to six.1 .
The block diagrams presented in Figs 2. as a result of self-arrangement of the objects and their configurations. while for the calorimeter described by the following set of differential equations:
.3). 2. for the calorimeter described by the differential equation
the resulting block diagram is a in Fig. we must consider the set of differential equations presented by the block diagrams of closed-loop systems. In many cases. For example.44
tial first-order object is the output function of the previous object (Fig.
the transmittance has the form
and we obtain the form of the calorimeter transmittance H(s):
In this case.
When a larger number of inertial objects are distinguished. 2. in the time domain the calorimeter is described by the following set of differential equations:
.CALORIMETER AS DYNAMIC OBJECT
the resulting block diagram is b in Fig. For N objects. the calorimeter transmittance will have a more complicated form.5.
30) takes the form
On application of the Laplace transformation. Determination of the transmittance expressed by Eq.4):
is the transmittance of the analyzed system.37)
. m < N. and N denotes the system rank. (2. we can write
of Eq. (2. (2. (2. (2. If it is assumed that in Eq.46
When the physical parameters of the system are neglected.34) is eqivalent to calculation of the polynomials The equation and
is called the characteristic equation and its roots are the “eigenvalues” or “poles” of transmittance.33) under zero initial conditions can be written in the form Eq. (2. Eq. Eq.35) the polynomial has only single zero values.
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 timeresolved characteristics. With the introduction of
transmittance H(s) becomes
is a constant called the static factor. and the polynomial in this equa tion is expressed by
On substitution of Eqs (2. Thus. 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. In calorimetry. (2.34).38) into Eq. However. the termi nology used for this purpose is different.
. the same input functions are used for their description as in control theory .CALORIMETER AS DYNAMIC OBJECT
are named the “zeros” of transmittance.3.
2.36) and (2.
CHAPTER 2 1. Dirac function) (Fig. The input function described by a short-duration heat pulse of relatively high amplitude.7):
. called in control theory a unit pulse function (impulse function. 2. 2.6). 2. is expressed by
The unit pulse whose surface area is equal to one has a Laplace transform y(s) equal to one. The input function described by a constant heat effect in time corresponds to the unit step function (Fig.
The Laplace transform of the unit step function is 3. The exceptions to the rule are those instruments in the calibration of which the frequency characteris tics are used.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.CALORIMETER AS DYNAMIC OBJECT
The unit step function corresponds to the integral of the unit pulse function with respect to time. 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. The Laplace transform of the rectangular pulse is expressed by
. called the rectangular pulse (Fig. 2.
The Laplace transform of which is
.49): The generation of such a forcing function is used in steering theory as well as in adiabatic and scanning calorimetry. (2.9 and expressed by Eq. 2. Generation of the heat effect of the first-order kinetic reaction is expressed by the exponential function (Fig.50
4. The ramp function has the following Laplace transform:
5. 2. The input function described by a heat effect rising linearly in time is presented in Fig.
while their values are equal to each other with the accuracy of the factor.
. 2. With the inverse transformation. integrating and inertial ob jects for various input functions are collected in Table 2.CALORIMETER AS DYNAMIC OBJECT
6) To evaluate the dynamic properties of calorimeters and calibrate the instruments. 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.11). 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). Output functions x(t) of proportional. and
is the oscillation frequency. those used in modulated scanning calorimetry. the output and input functions have the same shape. e.1. in other words. For proportional objects.
The Laplace transform of the sinusoidal input function is
These periodic heat forcing functions are the basis for some calo rimetric methods. The time-resolved dynamic characteristics presented in Table 2. 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.g.
where A is the amplitude of oscillation.1 show that the shapes of the output functions depend strongly on the type of the dynamic object. we obtain y(t). period input functions have also been used (Fig.
CALORIMETER AS DYNAMIC OBJECT
only the value of the sinusoidal (harmonic) oscillation frequency changes. which is equivalent to the unit step function. production of the ramp forcing function stimulates the response of the object according to the relation For inertial objects. 1.54
For integrating objects. 2. the output function x(s) and the transmittance H(s) is presented graphically by a block diagram (Fig.12)
When the trasmittance is represented by the single symbol H(s). Different values of the function x(t). 2. For an integral object. depending on the values of are responses to the same heat forcing (Fig.1. the values of control the inertial. The object responds to a generated unit pulse with an output signal. the course of the output function is induced by the inertial properties of the object (calorimeter). the course of the output function corresponds to the accumulation process and to the operation of integration. This results from the transmittance form H(s). The courses of the output functions caused by the generation of the sinusoidal input function for proportional. The amplitude of the output function is then inversely proportional to the frequency of the
. for a propor tional object. 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).13). This also means that the value of the time constant determines the course of the output function. damping properties of the object. the sinusoidal input function is transformed by the object to a cosinusoidal function. the character of which is approached more closely for either proportional or integrating objects. it is depicted by the block diagram presented in Fig. which is expressed by the operator 1/(Cs+k) or the operator while the relation between the input function y(s). Simply. 2. the response of the object to the unit step function is a linearly rising function. It is seen that. integrating and inertial firstorder objects are also presented in Table 2.
707 the conversed time constant radians or 45°. the course of the output function is similar to that of the input function y(t). expressing the output function x(t) for the steady state
the factor expresses in terms of f requency the ratio of the output and input function amplitudes. The phase shift is then close to zero and the proper ties of inertial and proportional objects become very similar. when sinusoidal changes have low frequency. It can be obtained by applying the Laplace inverse transformation to the transmittance Eq. When the frequency is related to then the oscillation frequency is 0. The values of the factor and the size of the phase shift characterize the dynamic properties of the iner tial object.4.41):
. the sinusoidal input function is trans formed by the object to an other sinusoidal function that has different phase and amplitude. It is applied for determination of the particular forms of the Laplace transmittance. In the following relation. the shift in the course of x(t) is expressed as radians or –90°. Pulse response
The pulse response function is the output function h(t) caused by the action of the input impulse function (Dirac function). given by the operator or
2. The frequency phase lag is 90° relative to the input function. The shift in the output function course relative to the input function results from the rise in frequency. For inertial objects.CALORIMETER AS DYNAMIC OBJECT
sinusoidal input function. For a frequency close to zero. This is the frequency related to and the phase shift is the transfer function of an inertial object. For infinitely high frequency. (2.
Taking into account Eq. the pulse response is expressed by the derivative of the calorimetric response
. we have
If we take advantage of the theorem of the initial value of the original. (2. The pulse response function is a positive function of real argument t.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. It fulfils the condition given by Eq. the function h(t). (2.56
have the form
from the Cauchy theorem of residues. or b) to the unit step function lasting a sufficiently long time to achieve the stationary state of heat transfer. i. the initial value of the pulse response h(t) on the basis of Eq. In this case.e. (2.57) and integrating.
65) and (2.66) that the values of coefficient and depend not only on the time constants. Since the experimentally obtained response of the sys tem does not fulfil the condition [Eq. the proce dure of numerical derivation influences the accuracy of obtaining the pulse response. 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. 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.60). From Eqs (2. 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
It results from Eqs (2. but also on the zeros of transmittance. we obtain a new course that fulfils the condition needed. (2.CALORIMETER AS DYNAMIC OBJECT
With the measured values of the response respectively
numerical derivation has to be performed in order to obtain discrete values of the pulse response h(t).59) and (2.49)]. Thus. In the second case.
. In the first case.
Fourier transforms are used. frequential char acteristics.13. are determined [8.
2. similarly as time-resolved characteristics.58
In Fig. To obtain the frequency characteristic. 2.5. the pulse response is “flattened”. 67]. Frequential characteristics
To analyze the dynamic properties of calorimeters. the plots of pulse responses of calorimeters of various orders are shown. The Fourier transform which is a complex function of the real variable can be written as follows: or in the form If it is assumed that
where and the transmittance are the real (even) and imaginary (odd) parts of respectively. we can write
. As the order of the system becomes higher. and its maximum value drifts more in time.
78) and (2. The spectrum transmittance of an N-order inertial system has the form
Equation (2.69) leads
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. assuming that In the spectrum transmittance described by Eq. let us distinguish the component transmittances and
It results from Eqs (2.79) that the amplitude of the trans is equal to the product of the amplitudes of particular mittance
. (2. (2.75) is equivalent to Eq.69) we have
is called the amplitude. (2. (2.67).75). Division of Eq.CALORIMETER AS DYNAMIC OBJECT Because
is described by According to Eqs (2. The amplitude-phase characteristic presents the ampli tude changes and the phases of the output function.72) and (2. the coordinates Let us analyze the amplitude-phase characteristics for a few types of spectrum transmittance. (2. the amplitude char acteristics. The dependence of a phase shift in frequency is called the phase characteris tic of the object. the phase the equation
If the magnitude approaches infinity. Thus.60
transmittances.75). The amplitude characteristic is a relation expressing the ratio of the amplitude of the output function to that of the input function.75) and (2. 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 gives the amplitude-phase characteristics. the amplitude by the function
For sufficiently large values of approximated by the equation
. phase characteristics and amplitude-phase characteristics are used. the phase of the transmittance is equal to the sum of the particular transmittances of the phases. then. the value of the limit phase approaches
To analyze the dynamic properties of the object. according to Eq.79). is described According to Eqs (2.80).
14b). In this way.CALORIMETER AS DYNAMIC OBJECT Taking logarithms of both sides of the above equation gives
It results from the above equation that the plot of the amplitude in the asymptotically approaches a straight line coordinate system with direction coefficient equal to –(N – m). Ac cording to the Euler formula:
2. is the temperature response to this heat effect (Fig.85). (2.81)]. The plot of helix shape which passess through the –(N – m) guater of the system in the coordi– nates will be obtained. In order to determine the spectrum transmittance it is neces sary to calculate the integrals on the right-hand side of Eq. the asymptotic plot permits an estimation of the difference between the number of poles and the number of zeros of the transmittance.
where is a heat pulse of constant heat power and time interval u (input step function)(Fig.6. The number of –(N – m) is related with the phase shift [Eq. 2.14a). (2. 2. 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.
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 [Eqs (2.87) and (2.88)] are to be calculated numerically by signal applying a convenient approximation, e.g.
Then, Eqs (2.87) and (2.88) become
CALORIMETER AS DYNAMIC OBJECT
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
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
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
CALORIMETER AS DYNAMIC OBJECT
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 . 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
It results from Eqs (2.96)–(2.99) that the accuracy of the determina depends on the accuracy of the tion of the spectrum transmittance 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.
2. algorithms and listing programs are described in detail in . Equation (2. When we follow this procedure.4. The methods used to determine the dynamic parameters of calorimeters that are inertial objects of order higher than one are also discussed. Different methods are presented for determining the time constant of a calorimeter treated as an inertial object of first order. the dynamic proper ties of a calorimeter can be determined by using the method of Ndomains based on the general heat balance equation [Eq.2. To apply each of the methods presented below.45)] under conditions where the initial temperatures of the calorimeter and isother mal shield are the same. To obtain the most information about the properties of the calorime ter. This method will be presented in Chapter 3. Consider the determination of by applying the input step function [Eq. (2. 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. (1. Several of these methods are similar to those used in steering theory.147)]. different input functions are used. All these numerical methods. 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.66
2.19) can then be written in the form
. 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. These methods have been qualified as useful in calorimetry to identify the dynamic parameters and to study thermokinetics.7.1. a knowledge of the physical properties of the investigated object is not necessary.
2.15.113) and (2.116). the courses of the changes in the calorimeter temperature T in time t are represented by the interval 0K of curve I. II and III shown in Fig. For this period of time. The first term on the right-hand side of Eq. Curves I and II have identical shapes. the course of the to the shield temperature is presented in curve III.CALORIMETER AS DYNAMIC OBJECT
is determined by Eqs (2. but there is a shift in time between them. (2. (2. (2. related to the duration of the heat impulse produced. function T(t) from This is the cooling curve of the calorimeter.115) gives
The function T(t) expressed by Eq. and the second term on the right-hand side of this equation to curve II. (2. (2.116) can be presented graphi cally by using the curves I.
After simple rearrangement.116) is related to curve I. Eqs (2.
The Laplace transform of the function y(t) corresponds to
while after the Laplace transformation Eq.47). The changes in temperature that occur here are only a result of the existing difference in tempera The interval KM of curve III graphically represents the differ tures ence between the values T(t) of the first and second terms on the righthand side of Eq. When t > a.114) can be written in the form
Inverse Laplace transformation of Eq.45) and (2.
Let us use Eq.118) describes the heating process occurring in the calorimeter (curve 0I. Equation (2. (2.68
When the heat generation period is long enough for a new state of thermal equilibrium to be reached. asymptote of the curve at the point relating to
. characterized by Eq.117) when T(0) = 0 is
which corresponds to the first term on the right-hand side of Eq. (2.116).19) can be written in the form
The solution of Eq. 2. (2. (2. (2. Fig.15).119).15). We find the time derivative of the heating curve
From Eq. 2. we have that a tangent to the curve 0K crosses an (Fig.118) to present several procedures for determining the time constant Procedure 1.
. After time T(t) is equal to
After time the temperature becomes and after we have Proceeding in such a way for the time known values of and T(t) of the heating process. The value of the time constant can be determined analytically. Procedure 4.CALORIMETER AS DYNAMIC OBJECT
Procedure 2.117) and (2.15). we have
Thus. 2. the length of the subtangent determined by its point of intersection with the straight line is related to the time constant From Eqs.124) – (2. (2. we can obtain the value of the time constant or its multiplicity. the length of the subtangent is equal to the time constant value Procedure 3.118). The values of T(t) related to time moments and cor respond to
Hence. 2. Eqs (2. At every point of the heating curve characterized by the interval 0K of the curve I (Fig. we have
If we take into account the graphical presentation of the heating curve in (Fig.15).
and the cooling process is expressed by equation
. 2. the time constant is equal to
represents the surface area F1 between the
straight line and the heating curve (Fig. To obtain the time constant can be used. it is assumed that y(t) = 0.70
and after rearrangement we have
the integration method
Hence.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.
The course of T(t) is graphically presented by the cooling curve (curve IV) in Fig. Fig. 2. after time of the cooling proc
. the length of the subtangent at every point of the cooling curve is equal to the time constant (see heating curve. Procedure 2). Procedure 3. one can determine the value of the time constant. (2. In a similar way.16. the value of T(t) can be determined for the time constant multiplic ity. (2. 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. 2. When. 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 2. After time the decrease in T(t) is 36. Procedure 1.CALORIMETER AS DYNAMIC OBJECT
The solution of Eq.135). Knowing temperature and choosing a matching value of T(t). The same as in the case of the heating curve.8% com pared to the initial value This results from Eq.
16b). On calculation of the integral:
Procedure 5.143) 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. (2.136) by Eq. (2.72
CHAPTER 2 and. Taking logarithms of both sides of Eq. 2. after time it becomes
Procedure 4. lnT)
Division of both sides of Eq. the value of T(t) becomes then according to Eq. The time constant for the cooling process can be calculated by an integrating procedure as for the heating process (Fig.135) gives
Equation (2. (2. the plot in the coordinates (t. (2.
a new function of the form
is created and a new plot in the coordinate system can be drawn. for which
This line cuts the axis at the point of the ordinate. (2. 2. The straight line interval (Fig.57)]. The iterative procedure is The second time constant repeated until a plot similar to the plot given in Fig.
. at the begining of the cooling process the relation lnT = f(t) is not linear. the discussed method can be applied to evaluate the higher time constants.CALORIMETER AS DYNAMIC OBJECT
can be drawn. 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 is obtained. 2. Thus
When the dynamic properties of the calorimeter are characterized by more than one constant of time [Eq.17a . as shown in Fig.17b) is extended to the point of intersection with the lnT axis and the first time constant is determined.17b. The following procedure is used. 2. is determined.17a). Next. In this case. as shown in Fig. 2. which forms an angle with the t axis.
In order to use this method. the pulse response is a func tion of time t. This method allows the and the zeros of the transmittance nominator to be time constants obtained by approximation of the pulse response of the calorimeter by the least squares nonlinear curve-fitting procedure described by Marquardt . As a criterion of fitting the and approximated pulse experimentally determined pulse response it is assumed that response
. poles and zeros
where m < N. expansion of this function as a Taylor series in the neighborhood of point is applied:
neglecting the derivatives of higher order. .7.
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.147) can be written in the form As is a nonlinear function of the components. According to these assumptions.2. it is necessary to assume or determine the order of the model number of poles and the number of transmittance zeros. Least squares method
The least squares method for determination of the transmittance pa rameters was proposed by Rodriguez et al. Introducing vector and zeros:
the components of which are poles
we can obtain the values of the parameters only with large error in one iteration. and
In possession of the discrete values of the pulse response.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.154):
we have the following set of equations:
Solving the set of Eqs. (2. assuming the calculated values as initial values and repeat the iterative procedure until we obtain a suitable approximation of the pulse response.
. (2. (2.CALORIMETER AS DYNAMIC OBJECT
Equation (2.152) the following fitting criterion is accepted:
where and is the sampling period. it is necessary to repeat the iteration.150) then becomes
where < 0. From the necessary condition of the minimum of the function expressed by Eq. Thus. T > is the time interval in which the changes in pulse response are measured. instead of Eq.
Multiply ing both sides of Eq..3. N – 1 is also assumed. (2.159). . . k = 0.
Modulating functions method
The modulating functions method was proposed by Ortin et al. These functions have continuous derivatives of desired order. (2.7.. The poles of transmittance are determined on the basis of an ac cepted model in the form of a differential equation.. (2. 2. The order and the smooth ness are connected with the order of differential Eq. .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 Next. This method permits determination of the poles and zeros of transmit tance. N.76
2. As the pulse re sponse h(t) is the finite sum of exponential functions [Eq...159) by and intergrating with respect to time t in the interval yields
leads with respect to the coefficients equations:
to the following set of algebraic
. the time interval in response of the system. 1. and 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..
Eq. only the amplitudes are unknown. which can result in the introduction of large errors. When we have determined the poles of transmittance and know the value of the pulse response h(t) in Eq. (2. taking into account that the time constants The expressions in Eq. These coefficients can be determined by applying the modulating function procedure given above to the pulse response:
we obtain the following set of equations:
. (2.162) (after integrating by parts) can be presented in the form
taking into account the conditions given by Eq. To avoid the calculations of these derivatives. (2. (2.162) contain the derivatives of the pulse response function h(t).CALORIMETER AS DYNAMIC OBJECT
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.160).158).
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
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
is the denominator of the transmittance. By solving the equation the zeros of the transmittance H(s) are obtained. and
is the m–degree polynomial m < N with respect to s.
7. Rational function method
of transmittance approximation
In this method. (2. (2.175) has a similar form as that of the set of Eq. (2. 72. 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. the program algorithm and the listing program are given in . 73]:
where D(s) and L(s) are polynomials of degree m and N(m<N) given by
2. (2. can be simplified to the following form:
The flow diagram of the modulating functions method.162).159) and integrating by parts).177) (taking into account the conditions Eq.CALORIMETER AS DYNAMIC OBJECT
The obtained set of Eq.4. the transmittance H(s) is approximated by a rational function [67.
.185) is a and function of N + m + 1 unknown parameters (n = 0.80
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. after simplification:
. . Function (2. we can write
where is the number of points taken into account in the approximation. (2. The necessary condition of the minimum of function (2. In order to adequately define the criterion Eq. The values are calculated by numerical integration. using Eq. we can assume
or. (2. As the criterion of fitting. having the of the values of the pulse response h(t) and assuming a set of values complex variable s.183). N)..184). the values of variable s must be real.185) with respect to parameters and has the form
and gives the following set of algebraic equations:
or. 1. .
the value of the direction coefficient of the last slope asymptote. or one zero and two poles. As the basis for determination of the transmittance. the transmittance of the compensating system (numeric or analog) [67.CALORIMETER AS DYNAMIC OBJECT
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).7. and the roots of the polynomial D(s) yield the poles of the transmittance. the experimental pulse re sponse of the calorimeter is taken.5. Next. or
. the values of the amplitude (modulus) and the phase of the Fourier transform of the pulse response are calculated.
2. Determination of parameters
of spectrum transmittance
To determine the dynamic parameters of the calorimetric system. From the Bode plot. the transmittance can have one pole. the quotient of which gives the expression approximating to the transmittance H(s). 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. through use of the Fast Fourier Transform (FFT) procedure. If this coefficient is equal to –1. The roots of the polynomial L(s) yield the zeros of transmittance. These values are plotted in a Bode plot. which permits an evaluation of the difference between the number of zeros and the poles of the transmittance is determined.
the transmittance can have two poles.82
two zeros and three poles. for example. that the value of the direction coefficient of the last asymptote is equal to –1. on the basis of the Bode plot (Fig.
Having determined the difference between the number of zeros and poles of the transmittance. or two zeros and four poles. etc. 2. and thus estimate the time constant with he largest value. let us assume. that the value of the direction coefficient is equal to –1. we stop our calculation and assume that our system is the first-order inertial system of transmittance:
In the other case. or one zero and three poles. If this coefficient is equal to –2. according to the relationship In the knowledge of the time constant transmittance we determine a new
and its amplitude and phase and draw their plots. etc. from the relations and it can result that the number of zeros is equal to the number of poles. We assumed ear lier. To illustrate our considerations.18) we can find the point at which the first slope asymptote intercepts the axis. and we
. 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.
etc. we can calculate the second time constant
After calculation of the parameters of the transmittance. we can determine asymptote. In this case. and we have
From the value of the horizontal asymptote. the value of the zero of transmittance is larger than the value of from the slope of the the second pole. Thus. the value of the zero of transmittance is smaller than the value of the second pole. In the first case (Fig. we can write
In the second case.19). as emerges from the previous considera tions. 2. from the slope of the asymptote we can calculate and thus the value of the second time constant is
. Let us assume additionally that the experimental data enable us to de termine only one zero and one pole more. or two poles and two zeros.CALORIMETER AS DYNAMIC OBJECT
have to deal with one pole and one zero.
. If the amplitude plot and the phase plot of the obtained transmittance are similar to the in an appropriate relation that results from the dependence frequency range.84
From the value from the formula
of the horizontal asymptote. we can calculate
and write the form of the transmittance as above. we can assume that the parameters of the transmittance have been determined correctly.
or calorimeter proper) at temperature that is usually in good contact with its contents. Swietoslawski.1. who made their choices on the basis of different criteria. drop calorimeter. Let us first define a “calorimeter” as an instrument devised to deter mine heat. and others. labyrinth flow calorimeter. The contents include the reactant samples and subsidiary accessories necessary to achieve the investigated transformation (e. calo rimetric bomb. in which the studied transformation occurs. container. These devices have been given various names by the authors. high-temperature calo rimeters and high-pressure calorimeters come from the conditions of temperature and pressure under which the measurements are performed. This diversity of the names of calo rimeters justifies an attempt to find features that classify the devices unambiguously. or stopped-flow calorimeter. and 2) the surroundings at temperature
. Junkers.Chapter 3
Classification of calorimeters Methods of determination of heat effects
3. e. heat of evaporation. or to mix the reagents) or to of calibrate the device. we may distinguish: 1) the calorimetric vessel (often called the cell. Bunsen. and others. Calvet. In some cases. to initiate the reaction. Examples here include the calorimeters of Lavoisier. Laplace. the type of process investigated is decisive: calorimeters for heat of mixing. The names of calorimeters often have to contain information about their construction features.g. specific heat measurements. 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.g. Names such as low-temperature calorimeters. In any calorimeter. The name of the device sometimes stems from the name of its creator.
). we can write where is the temperature of the calorimetric vessel and is the shield temperature. As an initial basis for further consid erations.1) by volume V. The classification given here  is based on the assumption that the calorimeter is a dynamic object in which heat is generated.3). Eq. differential and twin calorimeters (see 3.g.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. assuming bound ary conditions of the third kind (Newton’s cooling law). (3. Various classifications of calorimeters have been presented [75–83]. (3. environment or thermostat. Furthermore.4) becomes
. The surroundings form a part of the calorimeter that is functionally distinct from the measuring system. Calorimeters are graded by applying the criteria of the temperature conditions under which the measurement was made.2. we have
where is equal to heat capacity C.2) becomes
With the additional assumptions that mass transport takes place only in the x direction. (3.86
ten called the shield. Taking into account Eq. the Fourier – Kirchhoff equation (Eq. There are single. (3. e. and Eq. and that temperature T and heat power P are functions of the one coordinate x and time t.2. (1. with a defined temperature time dependence . It may also be considered the first thermostat shield of the calorimetric vessel (in some calorimeters there are several shields).
Adiabatic calorimeters.5) describes the heat transfer in calorimeters with mass exchange. to impose the temperature conditions of the calorimetric vessel or of the calorimetric shield or the temperature difference between them. In const. w = 0 and Eq.g. II. calorimeters can be divided into two groups: I. Nonadiabatic calorimeters.5) takes the form:
In the construction of a calorimeter. heat transfer oc curs between the calorimetric vessel and the shield. heat transfer does not occur between the calorimetric vessel and the shield. during the calorimetric measurement. Then. These calorimeters are called open calorimeters. in which the temperature gradient be tween the calorimeter proper and the shield is equal to zero 0). it is possible to provide condi tions which make it possible to carry out an experiment in a desired manner. the following cases of temperature conditions can be dis tinguished:
On the basis of the criteria listed above.. (3. e. Two subgroups of adiabatic calorimeters one can be distinguished:
. calorimeters in which mass exchange does not occur are called closed systems. in which the temperature gradient be tween the calorimeter proper and the shield is different from zero during the calorimetric measurement. this manner. In contrast.CLASSIFICATION OF CALORIMETERS
there are calorimeters with a tempera ture gradient that is stable in time. (3. These equations will then be treated as general mathematical models of the classified calorimeter groups. changes in IIb. The calorimeters in subgroup IIa are nonadiabatic-isothermal. They can be called adiabatic-nonisothermal or simply adia batic.6) for distinguished tem perature conditions. scanning calorimeters).5) will be given only for the types of open or closed calorimeters that are known by the authors. Calorimeters with constant temperature T0(t) (isothermal sur rounding shield). 3. Calorimeters in which the shield temperature time (e.88
They can be called Ia. Particular forms of Eq. Nonisothermal calorimeters involve the following subgroups: IIa.g. In both subgroups IIa and IIb.
Let us determine particular forms of Eq. Calorimeters where the temperature of the shield T0(t) changes in time. The schedule of the presented calorimeters division according to the temperature conditions by Czarnota and Utzig  is shown in Fig. Ib. or with a calorimetric vessel whose temperature changes in time.1. called isoperibol calorimeters. whereas those in subgroup IIb are nonadiabatic nonisothermal. (3. Calorimeters with constant temperature adiabatic-isothermal.
2) room-temperature calorime ters. such as those of Swietoslawski and Dorabialska . like those of Westrum Jr et al. and Prosen and Kilday . 86] and then Swietoslawski . Furukawa et al. Kaji et al. High-pressure adiabatic calorimeters were designed by Goodwin .1 to and the sensitivity of the instrument is A
. and usually called adiabatic calorimeters. When (3. Measurements are performed in the temperature interval from 10 to 100°C. adiabatic calorimeters are used for stud ies of various transformations in a wide temperature range. used to determine the ap parent molar heat capacity and conformational changes of proteins and nucleic acids. Suga and Seki . the shield heating rate can vary from 0.001 K).6) takes the form
Eq. and 3) high-temperature calorimeters. A series of new adiabatic calorimeters was recently designed that allow measurements on very small amounts of substance (< 1 g). and Gmelin and Rodhammer . In measurements performed with the use of adiabatic calorimeters. They are adiabatic-nonisothermal 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. and Zhicheng Tan et al. those of Kubaschewski and Walter . quite large amounts of substances have been applied (even several dozen grams).CLASSIFICATION OF CALORIMETERS
1. from very high temperatures to very low. One of the first scanning adiabatic calorimeters designed in the past was the DASM 1M microcalorimeter . . . Cash et al. Nowadays. . Their dynamic properties are those of integral objects. [87–89].
Calorimeters that are described by Eq. Adiabatic calorimeters were first used by Richards [76. (3.7) are characterized only by heat accumulation. Mention may be made of : 1) low-temperature calorimeters. Rastogiev et al. . Zlotowski .  and others. Takahara et al.g. close to the absolute zero (0. . Matsuo and Suga . e. West and Ginnings . and Sale . among them the calorimeters constructed by Ogata et al.
These conditions can be fulfilled. . Each of these instruments is constructed as the differential system. Eq. Privalov et al. At present. Progress in the development of adiabatic-isothermal calorimeters was made by Tian [114–116]. Dewar (volumetric determination of the air vaporized)  and Jessup (room-temperature operation based on the melting of diphenylether) . Bunsen (pycnometric determination of the volume change of the liquid water-ice system) . in this case it is very difficult or impossible to obtain conditions that correspond to thermodynamic equilibrium . (3. the modern electronic and steering devices applied to generate these effects permit measurements with high accuracy. determinations are made of the changes in the measured quantity that result from the phase transformation. the processes in such adiabatic calorimeters take place under isothermal conditions.. However.V.  and Plotnikov et al. where this type of calorimetry has been developed for almost 40 years. 2. (3. Then: Since and are identical during the measurement. In all of these devices.6) are equal to zero. When and const. when two heat processes of opposite sign and occur: where is the heat power of the process studied and is the compensating heat power.90
new generation of scanning adiabatic calorimeters is represented by the devices designed by S. When and the terms of the left-hand side of Eq.6) becomes
. A good illustration of this is the achievements at Brigham Young University . 119] and the few high-pressure flow calorimeters [120–122] have been constructed there. The best-known  such calorimeters are those of Lavoisier and Laplace (determination of the mass of melted ice) . who utilized the Peltier and Joule effect to compensate the generated heat power. The titration calorimeter [118. 3.
(3. there are instruments that have time and others with time constants of several constants of They have different constructions and find various applications. Wittig and Schilling . Zielenkiewicz and Chajn . 128]. 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. (3. 4.  and Christiansen and Izaat . Pankratiev [127.12) for the open system and Eq. Among them there are:
.13) for the closed system:
It results from Eqs (3.CLASSIFICATION OF CALORIMETERS
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. (3. The parameter that is decisive as concerns their properties is the time constant (or time constants). Closed. nonisothermal-nonadiabatic calorimeters have for a long time been the most widely used class of calorimeters. These are dynamic properties of inertial objects. This class includes the calorimeters of Olhmeyer . 125]. Dzhigit et al. is the compensating heat power generated additionally to carry out the calorimetric measurements under isothermal but nonadiabatic condi tions.6) takes the form of Eq.13) that the calorimeter systems de scribed by these equations are open and closed nonadiabatic nonisothermal (n-n) systems. Hansen et al.12). heat and mass exchange occur simultaneously. (3.12) and (3. Kisielev et al. When and Eq. [124. For the open calorimetric systems de scribed by Eq. In this class of calorimeters. .
.9). This group includes. calorimet ric titration [173–175]. b) Calorimeters with the jacket filled with water or air are mainly used to measure heat effects with a duration of a few minutes. 136]. photochemical reactions . as
. in the accurate instrument of Sunner and Wadsö . calculated by use of the method of corrected temperature rise (§ 3. oxygen [151–153] and fluorine [154–156] calorimetric bombs and calorimeters used to study thermokinetics and the total heat effects of reactions [157– 160]. for example. The well-known Regnault-Phaundler equation is then applied. where the heat exchange between the calorimetric vessel and the isothermal shield is excel lent. Vacuum jackets of special design are used. 164]. investigation of the properties of medica ments .  and and the microcalorimeters of Wedler . like the well-known Calvet microcalorimeter  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.g. such as the well-known Nernst low-temperature calorimeter  or Pierre Curie and Laborde‘s twin calorimeter  used in radiol ogy. etc. the heat of polymerization [138–142]. e. Randzio  for measurement of the heats of chemisorption of gases on thin metal films.2. for in stance. and the precipitation or crystallization of lysozyme . sorption and kinetics of adsorption [168–171]. e) Calorimeters where the heat generated is transferred to the liquid that flows around the outside surface of the calorimetric vessel. c) High-temperature calorimeters such as those of Eckman and Ros sini  or Mathieu et al. The Dewar-type calorimeters have found application in the determination of the average specific heats of organic liquids and their mixtures [135. d) Heat-flow or conduction calorimeters. et al. the metabolism in living organisms [165–167]. the heats of hydration of cements [143–146]. the heat of evaporation . Most of them make use of the thermometric “heat flow meters” in a differential assembly.92
a) Dewar vessel calorimeters in more or less sophisticated form.
Such are the flash calorimeters of Rosencwaig [186. and the photoacoustic calorimeter of Komorowski et al. in the calculation of the heat involved. 179. . Callis et al. f) AC calorimetry. 195]. flow n-n calorimeter are made after a relatively long time
Equation (3. g) A number of “quasi-adiabatic” calorimeters are used in such a way that.CLASSIFICATION OF CALORIMETERS
in the Junkers  and labirynth flow calorimeters [76. Kodama and Woledge  and Berger . 180]. . which is applied intensively for the measurement of heat capacity in the region of phase transitions [181–185].49) as in the
. When and Eq.18) describes the nonisothermal-nonadiabatic system in which changes occur in the shield temperature.17) describes the processes occurring in the flow and stopped-flow calorimeters of Roughton [194.  and Braslawsky et al. Jolicoeur and Desnoyers [191–193]. the transfer of heat between the calorimetric vessel and the surroundings is neglected. The temperature rise is usually linear and described by the ramp function (Eq. 5. There are open nonisothermal-nonadiabatic calorimeters like those of Picker.12) takes the form
Relationship (3. 2. When measurements in an open. (3. 187].6) takes the form for the closed system:
199]. differential thermal analysis.5). (3. This group includes: devices for heating and cooling curve determination (temperature measurement). heat flux differential scanning calo rimetry. They operate via observation of the temperature of the samples caused by the forcing function generated on the shield. In consequence of the same type of inertial properties (of inertial objects) of the devices mentioned. and modulated temperature differential calorimetry.18) in its simplified form can be considered as mathematical model.20) by G yields
The solution of Eq. (3.18) then takes the form
Division of both sides of Eq.21) is
. the course of the output func tion caused by the programmed rise of temperature of the shield is al ways the same (see § 3. hf-DSC (determination of the difference in heat flux between the studied sample and the standard substance to the shield . DTA (meas urement of the temperature difference between the studied sample and the standard substance) [198.94
Calvet scanning microcalorimeter. (3.2. 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. 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. mt-DSC (the tempera ture change of the sample described by the frequency and amplitude of vibration) . There are several thermal analysis devices for which Eq.
i.22) are presented in Fig. the twist of the line is linked to the increase of the heating rate. 3.CLASSIFICATION OF CALORIMETERS
When the calorimeter proper and the shield are initially in thermal are equal to each other. (3.e.
.3(b) shows the temperature change reading determined by differential measurement. For an exothermic reaction. (3. In the case of a Calvet DSC microcalorimeter.2. This is presented in Fig. the course of change in becomes linear. 3. Figure 3. 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. This shows that after a certain period of time following the start of measurement. and the measure equilibrium.22) takes the form
The courses of the changes in and according to Eq. For an endothermic reaction.3(a). and ment is performed until conditions of stationary heat exchange between the calorimeter proper and shield Eq. From this point. thermogram data are usually used for the determination of P(t) and then Q(t). the line appears to be twisted as a result of decrease of the heating rate.
6. The function P(t) is a superposition of at least three heat forcing functions relating to the heat power generated by the studied proc and the heat power gener ess.10). When and Eq. i.6) (similarly as previously) takes the form of Eq. (3. (3. (3. Eq. the compensating heat power ated in the shield in order to keep its temperature in compliance with the programmed changes.6) becomes The authors do not know any examples of calorimeters of this type.
.e.. When and const. 7.
the calibration mode and the methods of measurement and determination of heat effects. General description of methods
of determination of heat effects
Many methods are used to determine heat effects.. etc. Some of them al low the determination of the total heat effect Q studied. Methods of determination of heat effects
3. heat of mixing. 3) nonisothermal-adiabatic. and 4) nonisothermal-nonadiabatic. For the characteristics of these methods.1. 3) the measured quantity and measuring device. the experimental description of the device should also contain information such as: 1) the purpose of the instrument (combus tion. including the ranges of tempera ture and pressure in which measurements can be performed. the general heat balance equation (Eq. heat capacity.2. who distinguished four groups of calorimeters: 1) isothermal-adiabatic. 6) a description of the experi mental procedure used in the calibration and the actual measurements.).148)) has been used :
. 2) isothermal-nonadiabatic. 2) the principles and design of the calorimeter proper. the method of calibration. The mathematical models of calorimeters presented above were ap plied as the basis of methods used to determine heat effects. the accuracy.2. sublimation. while others permit the determination not only of the total heat effects. 5) the operational char acteristics of the calorimetric device. etc. called the thermoki netics or thermogenesis). but also of the course of thermal power P in time t (function P(t). (1.CLASSIFICATION OF CALORIMETERS
The classification of calorimeters presented above conforms with that given in 1930 by Lange and Miszczenko . the sensitivity noise level. 4) the static and dynamic properties of the calorimeter.
A similar procedure is applied in the method of finite elements (§ 3. the calorimeter is treated as a sim ple body of uniform temperature. The left-hand side of Eq.3).4). The heat balance equation (Eq. In the multidomains (N-domains) method (§ 3. (1. it is assumed that only heat accumulates in the calorimeter. The dynamic method is a one of the most frequently used in the determination of total heat effects and thermokinetics.7).148) is equal to zero. A generated heat effect P(t) is then described by the first term on the righthand side of Eq.99)].2. In the dynamic method (§ 3. Several methods are used for nonadiabatic calorimeters.2.148). A model of the calorimeter is expressed
.5).2. (1.2. and their mutual location.10). (1. Eq.6).99)] is also the basis of many methods used to determine total heat effects.148) is then a heat balance equation of a simple body.2. The inertial properties of the calorimeter are neglected.148) is usually reduced to the form of a heat balance equation of a simple body [Eq.8).148) are applied. (1. depending on the number of distinguished domains. (1. the calorimeter is treated as a propor tional object.2.98
In an adiabatic method (§ 3. The steady-state method (§ 3. A group of methods exist which a priori assume that the calorimeter is an inertial object of N order. it is assumed that the accumulation of heat in the calorimeter proper is negligibly small. The detailed form of Eq.2. one of the input forcing functions being a periodic function. (1. In this method.148)) reduced to the heat balance equation of a simple body [Eq. (1.9) 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. often called the Regnault-Phaundler correction. In the modulating method (§ 3. particular forms of Eq. One of the best-known is the method of corrected temperature rise (§ 3. (1. The calorimeter is treated as a proportional object.2. which is treated as an integral object. In the flux method (§ 3.
CLASSIFICATION OF CALORIMETERS
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
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 temperatures 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 and in the time domain t, the solution is the solution is
where H(t) is the matrix of fundamental solutions. If it is assumed that
where is the sampling period and can be rewritten as
is the Dirac function, Eq. (3.31)
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 (§ 188.8.131.52). Eq. (3.31) in the form
represents the mathematical model of the dynamic optimization method (§ 184.108.40.206). Equation (3.26) is the basis of the state variable method (§ 220.127.116.11). Equation (3.33) in the form
represents the mathematical model of the thermal curve interpretation
method (§ 18.104.22.168). Under zero initial conditions, Eq. (3.28) in the form
represents the mathematical model of the method of transmittance de composition (§ 22.214.171.124). Techniques that use analog and numerical correction of the dynamic properties (§ 126.96.36.199) 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
CLASSIFICATION OF CALORIMETERS
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  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”.
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 . 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.
In the second method. as is the electrical power supplied to the calorimeter heater. the calorimeter proper is heated at constant power for a known time interval to attain a certain temperature.2. The second procedure permits study in a precise way of these temperature ranges where interesting phenomena (e.g. The generation of electric energy inside the calorimeter proper does not always lead to a temperature rise. If this assump tion is true. then the three quantities temperature. This cycle can be repeated several times. the temperature will be measured. Adiabatic method and its application in adiabatic and scanning adiabatic calorimetry
The adiabatic method [76.CLASSIFICATION OF CALORIMETERS
. After the power is turned off. Then. 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. after switching-off. It can happen that an isothermal rise of the enthalpy occurs during the studied process.3. unknown phase transitions) are to be observed. 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. two methods are used. the temperature of the calorimeter proper is measured with no power input.” To perform the measurement. “Ide ally. the temperature is measured. the adiabatic shield is always maintained at the temperature of the calorimeter so that there is no temperature differential . the current supply can again be switched in and next. Both of the measurement procedures described above are used in practice. In the first. The calorimeter has the dynamic properties of an integral object. the calorimeter proper and the shield are heated at constant power input throughout the whole period of measurement. Such a procedure is called the intermittent-heating method. called the continuous heating method. We assume that the thermal power generated is used only to heat the studied substance and the other parts of the calorimeter proper. 87–89] is based on the assumption that no heat exchange occurs between the calorimetric vessel and the shield. First. The course of the temperature change with time is meas ured.
it is assumed that is the heat capacity of the calorimetric vessel with the contents.41) describes the “changeable” part of the calorimeter. for various heat capacities there is no need to change the mathematical model of the calls only for the introduction of new data in calorimeter. 210] allows the determi nation of thermokinetics as well as the total heat effects of the process examined.
The multibody (domain) method [67. Equation (3.g.2. The remaining part of the calorimeter described by Eq. is the heat loss coefficient between domains i and the j. 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
. (3. This part is called the “nonchangeable” part of the system. This can also be applied when the heat ca pacities of the calorimetric vessel content changes during the experiment (e. (1.40) corresponds to an “empty” calorimeter. is the heat loss coefficient between domain i and the shield. The mathematical model of the calorimeter is described by the following set of equations:
where N is the number of distinguished domains. such as the number of defined domains. and is the heat power.104
3. The method is based on the general heat balance equation [Eq. the interactions between the domains. The form of the heat balance equations for a given calorimeter de pends on a number of factors. The above form of the set of equations indicates that. in the titration process).4. 209.148)]. a change in the deconvolution program. and the mutual location of the heat source and temperature sensor.
and a heat source and temperature sensor can be located between them.5.4) on the basis of the calorimeter construction allowed the distinction of 19 domains. The propor tionality factors are the corresponding heat loss coefficients. 3. The system of domains is located in a shield of temperature. To elaborate the dynamic model. and the heat capacities of the media are taken to be negligibly small. and to de termine the structure of the model. is presented in Fig. A block diagram of a such system.CLASSIFICATION OF CALORIMETERS
sources. It is accepted that each of the domains has a uniform tempera ture throughout its volume and that its heat capacity is constant. 3.
The distinguished domains are individual parts of the calorimeter. . Tem perature gradients occur only in the media that separate these domains. For example. The amount of heat exchanged between the domains through these media is proportional to the difference between their temperatures. elaborated by Cesari et al. it is necessary to calculate the heat capacities of defined domains and the heat loss coefficients. The calorimeter was divided into upper U and lower B parts. which is treated as the reference temperature. because there is no symmetry of the device in the horizontal plane.
. where are the interaction coefficients between the domains. qualitative analysis of the heat exchange in the BMR calorimeter  (Fig.
This relation was applied when the surface dividing the domains was a plane. 2 – the calorimetric heater R. 13. 9. 4– the shield A of the heaters. the following domains were chosen for the parts of the calorimeter: 1. 11.2. 18– vessel shield support. where is coefficients were calculated from the equation the thermal conductivity. and that the other twin battery has been eliminated. the equation
Starting from the vertical symmetrical axis going through the center of the calorimetric vessel. 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. and is the distance between the centers of the neighboring domains. 19 – the bottom part of the shield. 3. because it does not contribute to the transfer function.15.16– thermocouples. 17–inner thermostat block. It was assumed that the calorimeter is ideally differential. 1 0–t h e cylindrical parts of the vessel shield. 14–thermocouple supports. For a cylindrical surface of heat transfer. 5–8–the block vessel. F is the surface area of heat exchange.
For a system of domains.. where l is the height of the cylinder. The elaboration of the model allows determination of the set of heat balance equations. we obtain
The temperature changes vs.42) for ten in the form
. (3. the temperature is cal culated. The beginning of the procedure is the temperature of the sensor. with the assumption of zero initial conditions for all the temperatures. and and are the radii of the cylindrical surfaces that pass through the centers of the neighbor ing domains. The last equation in the loop calculates the tem perature of the sensor. The procedure of calculating the calorimetric re sponse starts from the heat balance equation of the domain in which the heat source is located. N. Eq.40) and (3. On substituting the derivatives in the set of Eqs (3. Next.43).2. and next the temperatures of the neighboring domains are calcu lated from Eq.. . The temperature changes in these domains are the model responses to a given heat effect.CLASSIFICATION OF CALORIMETERS
was used. for i = 1. (3. . The algorithm of the thermokinetics calculation is very similar to that for thermogram calculations. time are calculated from
When the values of are known.41) by differences. the temperature of the neighboring domain is calculated. There are as many equations as domains distinguished and all calculations are carried out in one calcula tion loop. assuming zero initial temperature for the remain can be writ ing domains.
is used N–1 times to calculate the temperatures of neighboring domains. which is the calculation loop. one calculation loop has as many equations as neighbors. The transmittance (Eq.44). the form
where r is the index of the neighboring domain to the j domain. For example. S is the static amplification factor. In this method.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). The heat exchange between these domains is characterized by heat loss coeffi Coefficients and are the heat loss coefficients between cients domain j and its neighbors and between domain j and the shield. The following loops are related to the number of domains and the configura tion between them. domain j has r neighbors. it is assumed that synchronous knowledge of the
. 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. The finding of the real form of the transmittance is the same as determination of the dynamic properties of the examined calorimetric system.108
Equation (3. respec The calculation loop will then be a set of r equations of tively. 2. up to the last loop for calculating the course of heat power in time. when one domain can have more than two neighbors. For a model of more complicated configurations.
the amount of heat exchanged between the element i and element i+1 is determined by the equation For each element. taking into account the noise-signal ratio [see § 3. the a new model of the system must be worked out. the heat capacity is calculated.2. Next. If any number of time constants of the calorimeter does not satisfy the stability condition. this means that a model useful for the determination of thermokinetics has been elaborated. This method is based on the following assumptions. we can write
. If the result is positive.11. These conditions de mand the admission of the value of a sampling period obtained from the amplitude characteristics of the calorimeter.5. decreasing the number of do mains and calculating new parameters.7]. the model response to a given heat effect is com pared with the experimental response.CLASSIFICATION OF CALORIMETERS
real transmittance form and S and will be suitable for determina tion of the thermokinetics. The optimal sampling period limits the smallest value of the time constants. but only when the optimization and stability conditions of the numerical solution are fulfilled. The maximum order of the new model is limited by the number of time constants which satisfy the sta bility condition. A certain number of elements are distinguished.
3. between which the heat For each ele exchange is characterized by the heat loss coefficients ment. 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.2.
Finite elements method
The finite elements method was proposed and described by Davis and Berger .
and 2) the heat transferred. In order to determine the thermokinetics at moment necessary to know the temperature distribution of all elements and the heat power P at moment t. which causes the temperature increase. In each sampling period the increase in is caused by two effects: 1) the heat generated by the temperature reaction (or pulse). For calculations. The value of the temperature increase is determined on the basis of the thermogram obtained.110
Next. is given by the formula The increase in temperature is calculated on the basis of Eqs (3. if for the first element oftemperature 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 causes the temperature increase Thus. which represents the course of the changes in time of the temperature of the element in which the sensor was placed.48)–(3. Thermokinetics is determined on the basis of deconvolution of the pulse response of the examined system and the measured thermogram. according to the superposi tion principle. the temperature of each element is calculated after time
For example.51). the first nonzero value of the pulse response is taken. which allows transformation of the sensor signal to the signal in the reaction it is vessel. the increase in temperature of the sensor. The magnitude R plays the role of the multiplier. and the increase in temperature is calculated as the difference
. 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.
which characterizes the course of the thermal power change in time. As concerns the explanation of the method principles.CLASSIFICATION OF CALORIMETERS
The value of the increase in temperature is calculated on the ba sis of Eq.53). This assumption enables us to discuss this method by using the procedure proposed by Calvet . Thus.6. time. we use here the heat bal ance equation of a simple body [Eq. (3. As the mathematical model of the calorimeter. 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. This method is very sensitive to the errors in the determination of the value of the pulse response and coefficient R.
3. and c) the total heat effect. (1.
The dynamic method  of measurement is used for the determination of: a) the course of the thermal power change in time. b) the course of the temperature change vs. 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.2. 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). (3.99)].13) is used in the form
or in the form
58) then becomes
Integration of Eq. Accordingly to express T it is convenient to use the quotient with where is the measured magnitude. In practice. and are determined via the calibration procedure. 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. it is characterized by a constant temperature difference. The values of rimetric measurement. where the resistance is a function of temperature.58) and (3. Measurements of the temperature are usually made by using sensors such as a resistance thermometer and thermistor.73) leads to
notes the values of
is equal to the surface area F located between the course of changes in and F are the results of calo time and the time axis t. The calibration consists in generating a rectangular pulse [Eqs (2. (3.59) is equivalent to the amount of heat accumulated in the calorimeter proper.45) and (2. de
. the dynamic equation is used:
The first term on the left-hand side of Eqs (3.112
while to describe the course of the thermal power change in time ex pressed as a function of temperature. G/g. The values of C/g.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.61) is often called the Tian– Calvet equation. Equation (3. and g is the factor of proportionality. where the electromotive force is a function of temperature. or a thermocouple and thermopile. Equation (3.
by means of Eq.104)] and is used to determine the value of the time constant (see § 2. This constant value means that the calorimeter has the lin ear properties of a dynamic object.103) we can de termine the value of C/g:
Besides the determination of the time constant value. it is useful to determine a set of values G/g by generating rectangular pulses with dif ferent amplitudes. (3. (1. When the changes = f(t) are nonlinear during the initial period of the cooling or heating process. The calibration procedure presented here is not the only one used in the dynamic method. very important information is provided by observation of the course of the changes for the calorimeter as a thermally inertial object. A nonlinear course of means that the function is multiexponen tial. 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. we can assume that it occurs in the time period equal to solution of Eq.60) is then
and for Eq. If the generation of the rectangular heat pulse is stopped.CLASSIFICATION OF CALORIMETERS
scribed as and simultaneously by constant value Allowing a small The error. Cooling of the calorimeter then occurs up to the moment when the temperatures of the calorimeter and the shield are the same. (3. This process has been described by Newton‘s cooling law [Eq. then the calorimeter becomes a thermally inertial object. Quite often.1). the value of G/g is defined. it is necessary to analyze whether application of the simple body heat balance equation to the calculations is correct. (1. More precise equations expressing the relation between P(t) and T(t) should then be used.61)
In this way. The literature on this subject
.7. In the knowledge of and G/g.
When excellent heat transfer occurs between the calo rimeter proper and the shield (as in conduction microcalorimeters).2. Under isoperibol conditions. 160].
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. e. it can be assumed that the quantity of heat accumulated is extremely small. Modulating method
The modulating method is based on the measurement of the tempera ture oscillations of a sample heated by oscillating heat power. The first AC calorimetry experiments were performed in 1962 by
contains several modifications of such way of calibration.g.62).
3. Thus. 159.8. This assumption is the basis of the flux method. and its value is determined on the basis of the second term on the left-hand side of Eq.7. this method is called AC calorimetry [213–215]. the course of ob tained from the measurement resembles that of P(t). and in part is transferred to the calo rimetric shield. The amount of heat transferred between the calorimeter proper and the shield is then directly proportional to the temperature difference. (3.61):
while the total heat effect is
which results from Eq. [7. (3.
glass transition. The solution of Eq.49)] generated in the calorimetric shield and 2) the periodic function gener ated in the sample. according to Eqs. the determination of “storage” and “loss” heat capacities [218. two pro cedures are used. e.g. 219]. (2. (2. Reading et al. for “reversing” and kinetic “nonreversing” compo nents . The “reversing” parameter is most readily identified with the heat capacity of the sample. 217] proposed a method in which a DSC is used. as the Modulated DSC of TA Instru
. 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. (2. is
where is the time constant. [216.CLASSIFICATION OF CALORIMETERS
Kraftmacher .55) and (3.
where is the initial temperature. which corresponds to 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. When the periodic function is sinusoidal [Eq. It is a method applied in many instruments.26). In this case. and the melting of polymers. (3. is the temperature amplitude and v is the angular frequency. the response of the calorimeter as a linear system would be a superposition of two input functions: 1) the ramp function [Eq. whereas the nonreversing component in cludes contributions from irreversible processes such as crystallization.68) in the case of steady-state temperature modulation of the sample. who measured the heat capacities of metals in the high-temperature region.53]. For data evaluation.
2. the Alternating DSC  or the ODSC (Seiko Instruments) . Thus. compensating DSC).6) to formulate the basis of the method. Integration of both sides of Eq. the temperature increment in the consid ered time period is
In order to obtain a constant gradient of temperature between the calorimeter proper and its environment. (3. 221].6) with respect to time in the in gives terval
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). the steady-state method is used. and are the temperature oscillations around the average temperature.
CHAPTER 3 of Mettler-Toledo
3. P(t) = 0 (adiabatic-isothermal calorimeters) or P(t)= const.9.116 ments [220. Let us apply Eq. is the compensating heat power. (3. The method is based on the assumption that the following condition is fulfilled: where is the heat power generated during the process examined.
CLASSIFICATION OF CALORIMETERS
The integral of Eq. (3.82) is neglected. 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. (3.
If it is additionally assumed that the amplitude of temperature oscil lations around the average temperature is negligibly small. (3. 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. (3.80) simplifies to the form
For adiabatic-isothermal calorimeters.73) can then be written in the form
When the temperature of the shield can be assumed to be constant: the third term on the left-hand side of Eq. that 0 and the first term on the left-hand side of Eq. (3. we can put
and Eq. it is assumed.77) is
The thermal power is produced by several pulses of Peltier or Joule effects by: a) Application of pulse compensation consisting in the generation of as shown in Fig. and F is frequency. 3. where A is a quantized thermal power pulses pulse amplitude.
. it is assumed that the tempera ture change is proportional to the generated compensation thermal power
c) Use of proportional-integral compensation.
b) Use of proportional compensation.6. is the pulse duration. the proportionality of to and to the integral value of is assumed:
is the integration constant.
The amount of heat generated in the calorimetric vessel corresponding to the temperature can then be expressed as increment
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. 8] is used to de termine the total heat effects in n-n isoperibol calorimeters. As the end of the main period. three periods can be distinguished (Fig. (3. 3. the main period (segment BC).2.CLASSIFICATION OF CALORIMETERS
3. 225.87) can be written in the form
is called the corrected temperature rise. the temperature
.10. Method of corrected temperature rise
The method of corrected temperature rise [224. and the final period (segment CD). During the final period. The method is based on the heat balance equation of a simple body in the form
If we put
Eq. In the calorimetric measurement. The beginning of the main period is the initial moment of the generation of heat by the process studied. the time moment is assumed as the end of the studied process. During the initial period the temperature changes before the examined heat process are measured.7): the initial period (segment AB).
(3. etc.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. 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. we have
. the friction of the stirrer on the calorimetric liquid. the process of evaporation of the calorimetric liquid. In the method. which corresponds to the constant heat effect. 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.120
changes of the calorimeter after the examined heat process are meas ured. involve by secondary process Eq. If we assume that where is the increment of temperature of the calorimetric vessel. it is assumed that.
Thus. the temperature T(t) must be substituted by the term thus. In Eq.87). and can be treated as constant.97). we can approximate them as linear changes in time. respec
By subtraction from Eqs (3. we have
The value of the integral
can be approximated by the expression
.96) and (3. 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. (3. and can be ascribed to the average temperatures tively: and of the initial and final periods.CLASSIFICATION OF CALORIMETERS
and in the final period. we have
Because of the small changes in temperature in these periods of measurement.
(3.98).101) and (3. we obtain Use of Eqs (3.98) gives
On substituting Eqs (3.94). and method involves the assumption that.95). (3. in small time intervals of the main period.101) and (3.99).102) leads to
Substitution of according to Eq. On determining (3.99). temperature T(t) changes linearly.122
where are the values determined during the subsequent read This ings of temperature T(t) in the main period. (3. we can write
or on substituting
by expression (3. we have Similarly.103) into Eq. and the average temperature of the main period is the arithmetic average of the average temperatures from Eq. we obtain
. from Eq. (3. obtained in these small time intervals.
Roth  used the least squares method for approximation of the initial and final periods by straight lines. 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. In prac
tice. 228] pro posed the Simpson rule for calculation of the integral of Eq. various approximations of the course of temperature T(t) are used. (2. Shannon’s theorem is applied. For the determination of an unknown heat effect.CLASSIFICATION OF CALORIMETERS
Harmonic analysis method
In this method. and thus This correction is mostly used in isoperibol calorimetry to calculate the corrected temperature rise Depending on the need for precision of the temperature measure ment.6) has been determined previously. 231] and by van Bokhoven [232.1. first used by Navarro et al.
3.11. a frequency is used which is obtained on the basis of the transfer
. it is assumed that the (§ 2. (3. the convolution recorded in the frequency domain is accepted as the transformation equation [Eq.11.107) for the temperature correction are called the Regnault-Phaundler correction.8)] of the calorimeter. [230.105) and (3.
Numerical and analog methods
of determination of thermokinetics
3.2. White [227. spectrum transmittance Next. The graphicel-numerical methods of calculating the corrected tempera ture rise include the Dickinson method .2. an unknown heat effect is generated and the calorimetric signal is measured. 233]. They assumed the sampling period to be equal to unity. Planimetry at first was used to obtain this integral.
Method of dynamic optimization
In the dynamic optimization method [234–236].11. This method assumes the existence of one input function T(t) and one output function P(t).
and noise is the noise amplitude. we obtain
The task of dynamic optimization consists in selection of the un known thermal power P(t) so that Eq. numerical values
3. The practical frequency basis of the dependence
is determined on the
where = 0.9) is taken as a mathematical model of the calorimeter.
is the value of the spectrum transmittance amplitude for v is the value of the amplitude for the practical frequency. (2. in calorimetric measurements.111) attains a minimum. on substituting the convolution of functions.2. 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. (3. and thus appropriate zero ini tial conditions are assumed. the integral of the square of the difference between these two courses is taken:
or. 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.124
function calculated. As a criterion of accordance be tween the measured temperature change T(t) and the estimated course of temperature x(t). However.
a conjugate gradi ent method is used. the integrals in function (3.3. the re sponse to a heat pulse generated at time moment is In the method [237. which corresponds to the unit pulse generated in the calorimeter at mo ment j.2. and the function therefore becomes a func tion of multivariables: In the search for the minimum of function (3.11. Because of this. are the values of the heat pulse gen erated at moment j.111) are approximated by sums.
3.112). and is the i-th value of the pulse response. 248].
. 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.CLASSIFICATION OF CALORIMETERS
are usually available on the course of the temperature changes T(t) of the calorimeter. 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
where is the sampling period.
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.126
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. because we orthonormalize very similar functions. The ther mal curve interpretation method was proposed by Adamowicz [237– 239]. the co efficients are calculated as
Applying the inverse transformation to transformation (3. (3.
.117)] is difficult. Using the basis of orthonormal functions and curve T.117). Let us transform the set of functions into the set of orthonormal functions –
The condition of orthonormal functions has the form
Orthonormalization of the function [Eq.
Three types of state variables are distinguished: physical variables. 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. canonical variables and phase variables. 244].2. 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.
.124)) written in this way is a system of first-order equations.11. Method of state variables
In the method of state variables [240–242]. is referred to as the state vector. The vector
the components of which are state variables. 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. a certain set of parame ters is distinguished: which characterize the calorimetric system.CLASSIFICATION OF CALORIMETERS
3. . (3. 243. Because of the available calorimetric information.4. These values are referred to as state variables. The method was applied in the fol lowing works [239.
Method of transmittance decomposition
In this method .128
3. in the complex plane.2.11). (2. after dividing (m < N). is described by Eq.41) leads to
or. (3.129).11.5. we have
The expression after the use of Eq. the dependence between the measured calo rimetric signal and the generated heat effect. in the time domain corresponds to the differential equation
The expression after the use of (3. in the time domain corresponds to the convolution function
. Use of Eq. Using Eq. we obtain
R(s) is a polynomial of degree smaller than m (remainder of division).127). (3.128).
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
. the relation between P(t) and T(t) can be expressed according to Eq. when the calorimeter is treated as a object of sec ond order.131). 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. After us ing Eqs (3.
3. (3. 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.2. Inverse filter method
This method [244.13) in the form of the following differential equation:
Using Laplace transformation and replacing the coefficients by the time constants and of the calorimeter: Eq.6. For example.CLASSIFICATION OF CALORIMETERS
where is the inverse Laplace transform of Eq.132).130–3. (2. (3. 246] is based on the assumption that the time con stants of the calorimeter as an inertial object have been determined pre viously. it is necessary to determine first the nominator and denominator of On the the transmittance and next the expressions and basis of we calculate the coefficients and differential equa tion (3.129).
as represented by the rela tionship The practical performance of the inverse filter method is different in different systems [246–257]. Taking into account Eq. and thus that be tween T(t) and P(t). we have
For two correctors. this would lead to the case when the input function corresponds to the output function.136). Another way to achieve the differential correction is numeric correc tion [255–257]. for an inertial object of second order. by which the required function achieved. (3. we have
For an ideal correction.130
determination of the relation between T(s) and P(s). 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. but advantage is always taken of electronic elements active under the form of an operational amplifier and imped is ance divider of the feedback. It consists in the introduction (by the numerical or analog method) of terms providing an inverse function to the terms For an individual corrector. the following equations can be noted:
CLASSIFICATION OF CALORIMETERS
When the time constants and and T(t) are known.2.57)]:
.6) were also developed.4) were elaborated. and thus P(t).3) and the finite elements method (§ 3. it was assumed that the impulse response of the calorimeter is described by an infinite sum of exponential functions [Eq.
3. it is possible values consecutively.1 .2. and the adiabatic method for about 100 years.§ 3. the conduction method) in the past 20–30 years. (2. 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.7. as a basis of consideration the mathematical models used were particular forms of the general heat balance equation.g.2. Improved conditions in calorimetric experiments lead to the creation of more precise mathematical calorimeter models and methods used for the determination of heat effects. There are also new methods (e. as in the multidomains method. to determine the and The numerical differential correction method has also been applied to reproduce the thermokinetics in these calorimetric systems.11. These works extended the applications of the inverse filter method to linear systems with variable coefficients. Numerical methods for the determination of thermokinetics in n-n calorimeters (§ 3. In the multidomains method and in the numerical methods. in accor dance with the detailed solution of Fourier’s heat conduction equation. such as the TAM 2977 titration microcalorimeter produced by Thermometric.2. In many cases [258–262]. 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. the modulating method) or those which have become very important (e. From the methods in which the set of heat balance equations was used. the multidomains method (§ 3.11.g. in which time constant vary in time [258–264].11.2.
harmonic analysis. Three types of measurements were made: 1. in 1978. The dynamic optimization. The values of am plitudes. which corre sponds to 1/300 of the half-period of cooling. and the results of the data reconstruction by dynamic optimization and harmonic analysis in Fig. The purpose was to compare different methods independently proposed to reconstruct thermokinetics from the experimental calorimetric data. These responses concerned normalized series of heat pulses. 3. the time durations of the generated heat effects and the sam pling period were fixed as follows. it was generally approved that the responses of all calorimeters should be distributed to all partici pants of the program. it is neces sary to limit the number of exponential terms (domains).132
Thus.002–0. plots of the series of 7 pulses are given in Fig. 3 or 7 pulses of various durations were generated one after another. It has been proved by the results of a multina tional program  on the evaluation of the new methods of determi nation of thermokinetics.8.003 of the largest constant of the calorimeter. To eliminate the uncertainties caused by the individual features of the various calorimeters in different laboratories. 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). 3. equal to 10. this is due to the compromise between the available information and the possibility of applying it. In fact. in these methods an ideal model for reconstruction of the thermokinetics should be a model of infinite order.7.
. The values of amplitudes were given in relative units. The amplitude equal to 10 was defined as corresponding to the heat power of the pulse of duration equal to 8 sampling periods. generated by the Joule effect in a heater. For exam ple. Generally. The sampling period was taken as 0. 100 and 1000. state variable and numerical correction methods were tested.
CLASSIFICATION OF CALORIMETERS
As a criterion for choosing the optimal sampling period. is of particular importance for the quality of recon struction. (3. 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”.143). 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. but rather decrease of the influence of thermal lags in calorimetric data. after reconstruction. and q corresponds to the number of certain digits in the measurement of the calorimetric signal. It was stated  that “it is clear that the objective is not complete recon struction of thermokinetics (thermogenesis). It appeared that all methods are equally sensitive to noise in the data and that the amplitude of the heat effect under study. it is as sumed that
where denotes the noise-to-signal ratio. The optimisation method shows its advantage especially in the cases when the number of experimental data need not be bigger than 100-150. In order to estimate the values of the sampling period h instead of the approximate values
The results of the investigations indicated that the examined methods reveal considerable progress in the reconstruction of thermokinetics. compared to that of noise in the data. The harmonic analysis. Let us consider the same problem on using amplitude characteristics . amplitude is described by the func tion
and for large values of
can be approximated by Eq. As given in Eq. (3. thus.
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). There also exists a boundary frequency
. 4096. (3. The value of this frequency. In the multidomains method. 12 and N = 1024. e.CLASSIFICATION OF CALORIMETERS
are assumed in Eq. the transmittance is obtained numerically. (3. 11. the values of the constants must be larger than the sampling period with respect to the stability of the numerical solution. using the Fast Fourier Transform. respectively.144):
Raising both sides of Eq. 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.g. In this method. where n = 10.147) to the power 1/m results in
Thus. Another manner of selecting is used when harmonic analysis method is applied. resulting from Shannon’s theorem is a function of the sampling period It is therefore and can be expressed by the relation impossible to use the complete spectrum of the frequency. The discrete measurement of tem perature limits the upper bounds of frequency which can be applied for reconstruction of the thermokinetics. This procedure uses points. 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. this selecting scheme was included in the procedure of determining the particular form of the calorimeter model. 2048. [267–270].
the inverse filter method is used to determine the thermokinetics.3. The comparison of reconstructions of the thermokinetics obtained with the multibody method and with other methods demonstrates the convergence of the results  when the calorimetric system is described by a linear differ ential equation with constant coefficients of the third to sixth order. 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. the linearity of the system has implicitly been assumed. The boundary frequency is the second limitation of the frequency spectrum. 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. When the mathematical model is known. 271] can be expressed by the equations
. use of the flux method is not always suitable. which can be applied in the reconstruction of the thermokinetics for a given calorimetric system. In a calorimeter with a vacuum jacket. the thermokinetics can be determined successfully by means of the dynamic method.
Linearity and principle of superposition
In the review of methods of heat effect determination and thermoki netics. and The high precision of calorimetric measurements today permits a less strict description of the calorimetric system itself. Linearity [8.136
which is related to the measurement noise.
3. In calorimeters whose inertia is very small (conduction calorimeters). 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.
a rectangular pulse or a series of rectangular pulses. To achieve this. Regardless of what method of heat effect determination is applied. the forcing functions acting in the shield influence the calorimeter. To correct the response of the system the linear ity has to be confirmed by the experimental facts.
. Additionally. 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. given earlier (§ 2. for scanning calorimeters. Equation (3. The forcing function in the calorimeter proper is always the heat effect generated as a result of the studied process. tending to achieve the stability of the temperature of the shield. it would be helpful to use the dynamic time-resolved characteristics for the typical input func tion. the best method is to analyze the response of each forc ing input function in the system. if there is a thermally inertial object inside the calorimeter proper. the review of the methods has revealed that there can be forcing functions striving to compensate the generated heat effect of the process.3).142) indicates proportionality for quantitative measurement. The response of the calorimetric system is always a result of super position of some forcing functions acting at the same time. this is a forcing function. it has to be known whether measurements were performed in a linear sys tem. For an isoperibol calorimeter. When we look for the correct answer. (3. However. It is essential to draw a distinction between linear and nonlinear re sponses of the system. periodic heating rate of the sample etc.141) is the basis of the superposi tion principle. and Eq. it is a ramp function.CLASSIFICATION OF CALORIMETERS
where x and y express quantities to be measured and the function ex presses the output signal.
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1.1): the overall coefficient of heat loss. 20]:
The set of differential equations (4. the interaction coefficient and the forcing function. The following notions have been introduced in Eq. we have used particular solutions of the general heat balance equation (1. The overall coefficient of heat loss for each of the domains is de fined as
. (4.Chapter 4
Dynamic properties of calorimeters
4. Equations of dynamics
In our considerations relating to the analysis of the course of heat ef fects that occur in calorimeters. the time constant of the domain.1) is called the general equation of dynamics. the assumptions for which are sufficient to allow the calo rimeter to have different configurations.148):
It is frequently more convenient to apply this equation in the tem perature dimension [8.
This function is defined as
This coefficient characterizes the heat exchange between domain j and the surroundings. 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. 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.149). 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. but also that between domain j and other domains. we have
The function has the dimension of temperature and is propor tional to the heat power evolved. making use of Eq. (1. more exactly. The interaction coefficient is defined as the ratio of the heat loss to the overall coefficient of heat loss coefficient 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. 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 coefficients are defined as
. the notion of the forcing function (taken from con trol theory) was introduced into these considerations.
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). (4. The solution of Eq. and f is the forcing vector Application of the Laplace transformation to Eq. (4.1) can be written in matrix form as follows: 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. (4. The set of differential equations Eq. chosen in such a way that an increment of the tempera in a stationary state is equal to an increment of the forcing ture function Defined in this manner. the coefficients are especially useful in applying the principle of superposition to the system of do mains.DYNAMIC PROPERTIES OF CALORIMETERS
is a determinant whose value depends on the interaction coef is the determinant of the matrix obtained by crossing out
the j-th row and the j-th column of matrix D.9) is where
where is the transfer matrix and its elements are the transmittances which have the form
. The coefficients are dimensionless.
after development into a power series with respect to s. on developing the nominator and the denominator of the transmit tance (4.142
is the determinant of the matrix and
is the is the determinant of
corresponding minor of the matrix
the matrix These determinants. respectively:
Thus. 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.13)] can be written in the form
or.16) into first-degree factors:
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). (4. the transmittance [Eq. When the N-domain method is used to describe the heat effects. with different locations of the heat sources in relation to the temperature sensors. give polynomials of N-th and M-th degree (M < N). determination of the trans
as will be pointed out below. in order to analyze the courses of different heat effects in calorimeters.
Equations of dynamics.2. the general equation of dynamics can be simplified to a few-domain system. 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 The set of heat balance equations of the system is as follows: cient
If we put
.1.DYNAMIC PROPERTIES OF CALORIMETERS
mittance form makes it possible to verify the correctness of the mathe matical model of the calorimeter used in the calculations. characterized by heat capacities and respectively.2. 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. Dynamic properties of two and three-domain calorimeters with cascading structure
4. In many cases.
System of two domains in series
Let us distinguish a system of two domains in series. In such a case.
(4. here is at the same time the input function for domain 2.27).27) gives the solution in the complex domain:
. the initial conditions for Eqs (4.26) and (4.26) and (4. The and the temperature change here is at the same time the input func domain 1 output function tion for domain 2. of domain 2 is measured. the domain 1 output function.19) can be written in the form
Let us consider that the heat power is generated only in domain 1. Equations (4.27)
Application of the Laplace transformation to Eqs (4.26) and (4.23) then become
If we additionally assume that written in the form
Eqs (4.18) and (4. In the general case. Function is the output function of the system.25) can be
As results from Eqs.22) and (4.24) and (4.
29) and (4. 4. respectively.35) becomes:
. Eq.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.31) and (4. (4. 4. The functions G(s) [(Eq.30) can be rewritten as
Simple rearrangement of Eqs (4. the initial conditions being as follows: After simple rearrangement. of eliminating results in
If we put
Eq.32) with the aim.35)] will define the course of T(t) at f(t) = 0.DYNAMIC PROPERTIES OF CALORIMETERS
Equations (4. (4.
The function P(s) provides a basis for defining the function for various functions f(t).1) in which the first and second rectangles represent the dynamic properties of do mains 1 and 2. among
(4. at the initial moment of heat generation. if the initial conditions are zero. each of them over the time period a. This state is char acterized by a temperature higher by than the temperature in the system at the moment t = 0.34) 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
and after an inverse Laplace transformation this gives
If. 2) an input step function of amplitude b and time interval a.40). the time interval between two successive pulses being Z. there is a temperature dif ference between the domains (or domain) and the surroundings. (4. If we assume and with Eq. Let us now define the courses of function in the cases when 1) a unit pulse function. after inverse Laplace transformation Eq. 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. Let us suppose that a heat effect that is constant in time (an input pulse function) is producted in domain 1. and 3) a periodic input function is generated in domain 1. both is to be functions P(s) and G(s) must be determined if the function defined. This function f(t) is defined by rectangular pulses.
the function F(s) is
and Eq. the input function f(t) may be written in the form
For f(t) expressed by Eq. This function is
.34) takes the form
The function corresponding to P(s) in Eq. (4.
are then expressed by
When n rectangular pulses occur in domain 1.DYNAMIC PROPERTIES OF CALORIMETERS
The changes in temperature in time.44). each pulse lasting for a period of time a.47) was deter mined by an inverse Laplace transformation. the interval between two successive pulses being Z. (4. (4.
which at the same time constitutes the input function for domain 2. 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. Function domain 1 output function.f(t) is the input is the function. It may be assigned an arbitrary course. yielding
.2.49). whose output function is For the solution of the above system of differential equations. In Eq.49)-(4. the Laplace transform method was used.51) are assumed to be general differential equations of dynamics describing the courses of the temperature changes in time in the domains considered. Equations of dynamics.2.
Three domains in series
In numerous cases. (4.148
C HAPTER 4
4. The output function of domain 2 constitutes the input function of domain 3. 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).
49)–(4.51) in relation to tion where
is given by the equa
When f(t) = 0. and
a solution of Eqs (4.DYNAMIC PROPERTIES OF CALORIMETERS
The relation between the functions F(s) and P(s) may be represented as in the diagram in Fig. 4.2.
For a forcing function described by Eq.55). the temperature changes are expressed by the equation
. (4. (4.40) and initial condi tions described by Eq.55). we obtain the changes in temperature
For a forcing function f(t) described by Eq. (4.45) and initial conditions described by Eq. (4. (4.150
For a forcing function f(t) described by Eq.55). (4.43) and initial condi tions described by Eq.
3. which is of special importance in measurements of heat effects of short duration. These calculations allow determination of the output function of the system.2. a) The forcing input function f(t) is the input step function gener ated in the calorimetric vessel (in domain 1). 4. The output function of domain 2 is measured (Fig. For the calculations. Domain 2 con sists of the temperature sensor in isolation. For example. This causes differences in the values of the output function. The particular forms of the equations of dynamics for the other input func tions can be obtained in a similar way.DYNAMIC PROPERTIES OF CALORIMETERS
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.
4. Let us assume that the calorimetric vessel contains samples with the same volume. b) The input function is a ramp function. They can be calculated after determination of the particular form of Eq. The input function f(t) of do main 1 is at the same time the output function of domain 2. values characterizing the ramp function and the values of
. Domain 1 is a thermo stat. This selection was made by taking as criterion their application in the analysis of the courses of the heat effects. these equations can be applied as follows: 1) A system of two domains in series. while domain 2 consists of the calorimetric vessel with sample. (4.43). (4.43). 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]. but with differing heat capacities The time constants of domain 2 there fore change.1). The amplitude and generation time of the rectangular pulse and the time constants of domains 1 and 2 are known. one can apply Eq.
In the calorimetric vessel. The input function f(t) is the input step function. the ramp function f(t) is pro duced. 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. The output function of domain 3 is measured. the course of the out put function of the system has to be defined as the result of the operation of several forcing functions. The amplitude and generation time of the rectangular pulse and the time constants of domains 1–3 are known. In the thermostat.
. 4. This can be demonstrated via the following examples. which in turn is the input function of domain 3. To calculate the output function. 3 a) A system composed of a thermostat (domain 1) and a calorime ter (domain 2). and domain 3 is in isolation the temperature sensor located on the outer surface of the inner calorimetric shield.2).152
2) The system consists of three domains in series (Fig. (4. we can apply Eq. heat effect generated. whereas the calorimeter gives the periodic input function
3 b) A system comprising the calorimetric vessel with the sample
(domain 1). the responses of the system to only one forcing function were considered. In many cases. domain 2 is the inner shield of the calorimeter. In the discussed examples.61). The in put function f(t) of domain 1 is at the same time output function of domain 2. the internal shield (domain 2) and the temperature is sensor (domain 3). Domain 1 consists of the calorimetric ves sel filled with the substance studied. while the compensating heat effect expressed by is produced in the internal shield of the calorimeter.
(4. when forcing functions and are produced at the same time. the output function P(s) will be expressed by Eq. 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).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. and the reference substance in the other. The forcing input function is the ramp function generated in the thermostat. 4. The influence of the forcing function on a differential calorimeter is shown
.36) supplemented by the term. the output function is expressed by Eq. for the two-domain system when input functions f(t) and (Fig. (4.3) are produced at the same time.DYNAMIC PROPERTIES OF CALORIMETERS
This leads to the conclusion that.
For the three-domain system. placed in a common shield. Let us assume that this function is at the same time the input function of both calorimeters. The sample is situated in one of them. characterized by the dynamic properties of inertial objects of the first order.
in many cases it is necessary to consider systems having more domains.
4. For the observation of such changes. indicating the dependences of the dynamic properties on the mutual locations of the heat sources and temperature sensors (§ 4.5. that the accuracy of establishing the output function is somewhat sacrificed. The transmittance of the system can then be determined or the system can be approached in terms of a single system with vicarious characteristics.3.3.2). even the identification of these domains may pose considerable difficulties and the direct determi nation of the time constants may be impracticable.1 and § 4. respectively and T(t) is the output function of the differential calorimeter. The application of these characteristics does not mean.154
schematically in Fig.
For this system. both in series and with a concentric configuration. explaining why the calibration of the calorimeter by means of
. where and are the output functions of calorimeters I and II. Dynamic properties of calorimeters
with concentric configuration
Let us discuss the two-domain model with a concentric configura tion. 4. 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. As often as not.3. however. with a high number of domains present in the system.
This is characterized by Eq.3.3.
4.1. 45]. and proving the need for use of the equivalent coefficient (§ 4. 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.DYNAMIC PROPERTIES OF CALORIMETERS
the dynamic method in some cases is accompanied by apparent changes in heat capacity (§ 4.4) instead of the heat capacity value when the method of corrected temperature rise is applied in calculations of heat effects.3).3.18):
and the equation
The time constants
of the distinguished domains 1 and 2
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.74) and (4.18) and (4.72). whereas the thermal inertia of body 2 is influenced by the heat transfer between domains 1 and 2. The interaction coefficients are.73). the overall heat loss coefficients mains 1 and 2 are. we have
With regard to Eqs (4. respectively
From Eqs (4. which are. Eqs (4.7) and (4.68)–(4.75) are called the equations of dynamics of a calorimeter treated as a system of two domains with a
.66) can be written in the form
The differential equations (4. respectively On putting we can write
In order to determine coefficients and are calculated.156
CHAPTER 4 and for the do
In this case.
6. which may be assigned to the equations of dynamics. 4.75) then become
where and are the differences between the initial temperatures of domains 1 and 2.75) referring to the heat balance equation of a simple body.74) and (4. respectively. To obtain the block diagram shown in Fig.
However. con sidered independently of one another.77) become
. It may be noted that the left-hand sides of these equations are similar to the equation of dynamics for a one-domain model. because of the different forms of the right-hand sides of Eqs (4.DYNAMIC PROPERTIES OF CALORIMETERS
concentric configuration [44.74) and (4. the time constants and of the particular do mains thus characterize the first-order inertial properties of each. the Laplace trans formation should be applied. and are the Laplace trans tures forms of the forcing functions and
Eqs (4. and are the Laplace transforms of tempera and respectively. 4.76) and (4.7). Equations (4. 45]. a new quality is obtained: the mutual interaction expressed by and This expression follows from the block diagram (Fig. and that of the temperature of the shield at time = 0.
and the in time are measured. changes in temperature 4.1. (4.7) that the dynamic properties of the system depend on the dy namic properties of the domains and on the interaction between them. the relationships be tween the input function F(s) and output function T(s) are given in Table 4.83) for the distinguished domains 1 and 2. we have
from Eq. (4.3.158
For the transform Eq. let us consider the dependence of the dynamic proper ties of the calorimeter described by Eqs (4.79). A heat power is measured and the changes is temperature in time are measured. (4. Taking into account the form of transmittances given by Eq. A heat power characterized by function is generated. These functions characterize the dynamic properties of the domains that are distin guished in the examined calorimeter. 1. the calorimeter transmittances as functions of trans mittances and [Eq. the transmittances of the calo rimetric system given in Table 4. and the changes in temperature in time are measured. (4. For these cases. The following cases can be distinguished: is generated.
. respectively.80) and the transform
are the transmittances of domains 1 and 2. 3. 2. A heat power characterized by function is generated. 4.83)] of the distinguished domains and interaction coefficient k are given in Table 4.2. It is seen from the block diagram (Fig. In this connection.74) and (4.1 can be written in the form presented in Table 4.75) on the loca tions of the heat sources and temperature sensors in domains 1 and 2. A heat power characterized by forcing function and the changes in temperature in time are measured.
These are the roots of Eq. (4.85).3 can be written in the form given in Table 4.4. de
which satisfy the equation
the transmittances given in Table 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.
.DYNAMIC PROPERTIES OF CALORIMETERS
If we introduce the time constants fined as
of the calorimeter.
4 that depends only on the time constants and of the transmittance calorimeter. which takes into account the tem perature differences between domain 2 and domain 1 in steady-state heat and depend on the time constants transfer.
As a consequence of the different forms of transmittance. transmittances of the distinguished domains as well as on the time constants of the calorimeter. transmittance depends on the constants and but also on the interaction coefficient k. there are different courses of the output function for the same forcing function.
It can be shown from the transmittances collected in Table 4.
the distinguished domains are thermally inert objects.8d and 4. the pulse response of the calo rimetric system at the initial time moment is equal to zero. and are non-negative functions. the shape of the pulse response of the calorimetric system is reminiscent of the response of the calo rimetric system of first order. and 2) the temperature changes of the calorimeter as a thermally inert object. when the heat source and temperature sensor are situated in different domains.8d reveal that. when the heat source and the temperature sensor are situated in the same domain. the pulse responses of the calorimetric system given in Table 4. Thus.8c. their plots are shown in Fig. next in and respectively).8.5 are obtained. it is clear that. Fig ures 4.8a and 4. When the inverse Laplace transformation is applied to the transmit tances given in Table 4.DYNAMIC PROPERTIES OF CALORIMETERS
We can demonstrate this on examples of 1) the pulse response of the calorimeter. the pulse responses depend on the mutual locations of the heat source and temperature sensor.4. 4. and on the parameters of the calorimetric system. and creases to a certain maximum value then decreases to zero. From the shapes of the curves given in Figs 4. which is equivalent to the conditions
Let us also consider the changes in temperature in time of the calo rimeter when there are no heat sources.
91) represent the Laplace transforms of tem and when at least one of the temperatures of the peratures distinguished domains at the initial moment t = 0 is not equal to the en vironment temperature.90) and (4.90) and (4.79) and (4.162
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.80) can be written in the form
The determination of
from these equations leads to
Equations (4.91) gives
. (4. (4. which can be written as When the conditions given by Eq. Application of the inverse Laplace transforma tion to Eqs. Eqs (4.74) are taken into account.
9a and 4.93) are shown in Figs 4. it is seen that domain 1.9b). When the initial temperature of domain 2 is higher by than the envi ronment temperature (Fig. undergoes cool ing. the course of the temperature changes in time being reminiscent in shape of a one-exponential course. 4.
.9a. When the plots of functions (4. 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.84). At time moment temperatures are equal. the domain is heated to the environment temperature.9b. and the course of the temperature changes in time are reminiscent in shape of a one-exponential curve. domain 2 cools to the environment temperature. From the plot in Fig.92) and (4. When
of the calorimeter are given by
the plots of the functions (4. When the initial temperature of domain 1 is smaller by than the environment temperature (Fig. Domain 2. at a temperature higher by than the temperature of the environment. first undergoes heating to temperature by a certain time and then cools to the and environment temperature. 4. 4. whose temperature at the initial moment is equal to the environment temperature.92) and (4.9c).93) are shown in Figs.9c and 4. the temperature of domain 2 cools to by time next returning to the environment temperature.DYNAMIC PROPERTIES OF CALORIMETERS
where the time constants Eq.9d. (4. 4.
and then cools to the environment temperature. If lower than the environment the initial temperature of domain 2 is temperature (Fig. decreases to a certain temperature
. domain 2 heats up to the environment tempera ture. 4. The temperature of domain 1.9d). which at first is equal to the envi and next ronment temperature.164
Domain 1 with an initial temperature equal to the environment tem perature heats up to temperature not reaching the temperature of domain 2. The tempera ture of domain 1 is always lower than the temperature of domain 2.
9e.74) and (4. To re construct the input function on the basis of the form of the output func tion.93) are shown in Figs 4.74) and (4.
4. The examples given above clearly show that the output function is related to the mutual locations of the heat sources and temperature sen sor. When heat power is gen erated only in domain 1.3.76) take the form
. 4. The extremal value of the temperature of domain 1 depends on the value of interaction coefficient k. Eqs (4. we will take the equation of dynamics [Eqs (4. As a basis of consideration. 4.9e and 4. 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.DYNAMIC PROPERTIES OF CALORIMETERS
increases to the environment temperature. but the temperature of domain 1 decreases faster than that of domain 2. it is necessary to know the particular forms of the dynamics equa tion of the two-domain calorimeter with a concentric configuration.9f. but domain 1 does so faster than domain 2. When the initial temperatures are smaller than the environment temperature (Fig. it can be seen that the temperatures of domain 1 and domain 2 decrease in time. 40].75)] expressing the dependence between temperature and heat effect as a function of the locations of the heat source and the tem perature sensor [8.92) and (4. When the initial temperatures of the two domains are equal and dif ferent from the environment temperature: plots of the functions (4.9f). From Fig. both domains heat by up to the environment temperature. The presented equations were defined on the assumption that the form of the input function and the initial conditions are known. the neight of the peak is smaller.74) and (4. As the value of interaction coefficient comes nearer to unity. The course of the temperature changes in domain 1 is remi niscent in shape of a one-exponential course. 30.2.75)].
97)–(4. the elimination of temperature from Eqs (4.166
When heat power is generated only in domain 2.98) furnishes
Division of both sides of this equation by k and taking into account Eq. The temperature is dependent on the function In this case. Eqs (4.102) can be written in the form
. let us consider the following cases: 1.97) and (4.100). (4.74) and (4. (4.75) take the form
Taking into account Eqs (4.84) gives
With the assumption that
because it is necessary to know the derivative of the value we are looking for. This equation cannot be directly applied to determine an unknown heat power. the equation of dynamics has the form
4. by from Eqs.97) and (4.100). which has the form
Analogously.98) and fol eliminating the temperature lowing the above routine.105) connects the changes in temperature of domain 1 with the heat effect generated in the same domain. the de pendences between the heat effect generated in domain 2 and the tem perature changes can be established for the following cases.DYNAMIC PROPERTIES OF CALORIMETERS
. 3. The temperature depends on the function In this case. we can establish the relationship between the of domain 2 and the heat effect generated in temperature changes domain 1.99) and (4. The temperature depends on the function the equation of dynamics has the form
In this case. by taking into account Eqs (4. 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. (4. 2. The temperature depends on the function In this case.
Equation (4.104). it was found that the calculated value treated as heat capacity changes in time. 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 Eq. Changes in the heat capacity of the calorimeter were noted.
4. Particular forms of the equation of dynamics show that.107) has a form similar to that of Eq.3.
Apparent heat capacity
During the calibration of the Calvet microcalorimeter  and the KRM calorimeter .3. such as the apparent change in heat capacity of the calo rimeter with time. Considerations as to the mutual locations of the heat sources and temperature sensors can form the basis of the explanation of several observed facts. corresponding to the number of distinguished domains. (4. it is possible to carry out a meas urement in such a way that the temperature sensor is situated in each domain. (3. when was calculated by using the heat balance equation of a simple body. the temperature sensor should be situated in another domain than the heat source. for the two-domain calo rimeter.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
. In another case. Zielenkiewicz and Tabaka [278–281] showed that correct re sults can be obtained by applying multipoint temperature measurement. 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.
(4. On integration of both sides of Eq.106) in the time interval yields
Comparison of Eqs (4. Integration of both sides of Eq.110) gives
A comparison of Eqs (4.114) gives
3. (4.109) with integrating Eqs (4.104)– (4.111) results in
2.109) and (4. the following cases can be considered: 1. (4. (4.104) in the time interval leads to
Simple rearrangement of Eq. then.107).109) and (4. (4.DYNAMIC PROPERTIES OF CALORIMETERS
. Integration of both sides of Eq.105) in the time interval we have
. in a comparison of Eq.
.2 for a system of two interacting domains.109) and (4.108) in the time interval leads to
On comparing Eqs (4. we find
4.117). (4. 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 effective heat ca pacity is time-invariant in only a few cases.109) and (4. Integration of both sides of Eq. and also the time inter val in which the heat effects are evaluated. when and i = 1.170
By comparison of Eqs (4. the changes in particular temperatures in time and their time derivatives.g.
the calorimeter can be de scribed by one of Eqs (4. (4. in the corrected temperature rise method three periods are dis and tinguished during the experiment: In the initial and final periods.4. it was established [22–24.3. 284] that the calculated heat capacity of the device was not equal to the sum of the heat capacities of the calorimeter parts. the calorimeter is a ther mally inert object. King and Grover  described the calorimetric bomb in terms of a two-domain model with a concentric configuration.DYNAMIC PROPERTIES OF CALORIMETERS
4.116) and (4. 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.119). in the main period. called the energy equivalent of the calorimeter:
where and are the heat capacities of domains 1 and 2.107). depending on the mutual loca tions of the heat sources and temperature sensors.113). in the method of corrected rise the heat capacity C was replaced by a corrected term. (4. leads to
. equal to the smaller of the cooling constants of the calorimeter.3.104)–(4. in the main period. the heat effect is generated in the calorimeter. is the and is heat loss coefficient between domains 1 and 2. As stated pre viously.110). As a result. while integration of these equations in the time interval similarly as for Eqs (4.2. As shown in §4.
Energy equivalent of calorimetric system
When the corrected temperature rise method was applied for the calibration of the calorimetric bomb. Let us analyze [283.
132). we find
. Since the moments and belong in the periods when heat power is not generated:
From Eqs (4.130)–(4. after simple transforma tion and integration. we have
On taking into account Eqs (4.172
and and are the values of the derivatives of the temperatures and with respect to time t at moments and respectively.5).4) and (4.
Eqs (4.123)–(4.123)–(4.DYNAMIC PROPERTIES OF CALORIMETERS
If the temperature changes in the initial and final periods result from the cooling or heating of the calorimeter as a thermally passive object.107) are equal to zero.134) and (4. The solu tions of these equations are
where and are constants.140) are taken into account.136) and (4.138) yield the following equations:
When Eqs (4.137) decreases quickly and we can write
Equations (4.126) can be written in the form
.104)–(4. the right-hand sides of Eqs (4. When the second term of Eqs (4.
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
. the energy equivalent is equal to when the temperature of domain 1 is measured and the heat effect is generated in domain 2. (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.174
Eqs (4. Then.146). taking into account Eq.
but is not the sum of the heat capacities and of the distinguished domains.151)–(4. is equal to
Taking into account the relationships (4. when the temperature is measured in the inner domain.153) that the energy equivalent is the same. (4.157) and Eqs (4. the cali brations and examined heat effects must occur in the same domain be cause The larger root of Eq. (4. (4. equal to the product of the largest time constant of the calo rimetric system and the heat loss coefficient In Eq. (3.154). which corresponds to the time constant of the calorimetric system. If the temperature of the other domains is measured.68)–(4. the location of the temperature sensor is generally fixed.71). 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. we have
It results from Eq.96).DYNAMIC PROPERTIES OF CALORIMETERS
when the temperature of domain 2 is measured and the heat effect is generated in domain 1. the energy equivalent is equal to It can be seen from Eqs (4. the energy equivalent is smaller than in the first three cases. In calorimetric measurements.84).154) that the energy equivalent has the dimension of heat capacity. we obtain
From Eq. When the calo
. while those of the calibrating heat source and the heat source of the examined process can differ. the energy equivalent is equal to when the temperature of domain 2 is measured and the heat effect is generated in domain 2.151)–(4.
When ideal heat exchange occurs 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.
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.
the heat transfer process is stationary (the generated heat effect is compensated). 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. and also those in which this flow of heat is very low. which have been duly pointed out. Of the methods described and
. The considerations presented are based on the general heat balance equation of N-domains. to discuss selected methods of determining thermal effects and ther mokinetics. These give rise to several limita tions. by definition. This makes the calculations very convenient. whether those with a constant or those with a variable temperature of the shield. particular form of this equation. The present theory has been used to develop a classification of calorimeters.Final Remarks
The present theory of calorimetry is a result of the authors’ own work. Calorimeters have been assumed to constitute linear sys tems. 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. This is true for most of the existing calorime ters. but implies a number of simplifying assumptions. Its essential feature is the simultaneous application of the relation ship and notions specific to heat transfer theory and control theory. A majority of the methods used to determine heat effects have been shown to rely on the simplest. and to describe the processes proceeding in calorimeters of various types. This assumption allowed the principle of superposition to be used to analyze several constraints acting simultaneously in and on the calo rimeter. It includes calorimeters in which the flow of heat between the calorimeter proper and its surroundings is quite intense. On the other hand.
and with constant or varying volumes and heat capacities of the samples examined. 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. 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.178
used to determine heat effects and thermokinetics. 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. This is true of the numerous calorimeters produced by the major manufacturers. In such investigations. the method of Ndomains has been given special attention. The method is of particular value when the construction of the calorimeter permits the instrument to be used for various applications. 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. This method may be particu larly useful when the calorimeter constructed is used to study transfor mations of short or long duration. This is of particular concern as regards calorimetric determinations carried out with the recent DSC techniques. 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.
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