See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/306066139

Reaction calorimetry: types, simple theory and application for kinetic study
(overview)

Article · August 2016

CITATIONS READS

0 657

1 author:

Arcady Kossoy
CISP Ltd
40 PUBLICATIONS   305 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Elaboration of experimental methods for study of reaction kinetics View project

Methodology of kinetics-based simulation - theoretical grounds and practical application View project

All content following this page was uploaded by Arcady Kossoy on 12 August 2016.

The user has requested enhancement of the downloaded file.

 CISP Newsletter № 11

Reaction calorimetry:
types, simple theory and application for kinetic study
(overview)

Preface
Reaction calorimetry (RC) became very popular method widely used in chemical engineering for
designing chemical processes, assessment of their reactive hazard, and in some other areas.
Nowadays several types of reaction calorimeters are available each having its own specific features.
Theory and practice of applying reaction calorimetry were considered in numerous articles and
monographs but, as far as we know, neither of these publications contains description of the existing
types of RC in compact form. Therefore we propose this overview believing that it will help in
understanding principles of RC and in choosing the type of instrument most relevant for study of
specific problem.

Contents
1 Introduction ............................................................................................................................ 1
2 Heat-flow RC (HF-RC) ........................................................................................................... 2
2.1 Construction .................................................................................................................. 2
2.2 Mathematical model ...................................................................................................... 2
2.2.1 Mass balance equation ......................................................................................... 2
2.2.2 Energy balance equation ...................................................................................... 3
2.3 True Heat Flow RC ........................................................................................................ 5
3 Heat balance RC (HB-RC) ..................................................................................................... 5
4 Power-Compensation RC (PC-RC) ........................................................................................ 6
5 Interpretation of RC data ........................................................................................................ 7
6 References............................................................................................................................. 7

1 Introduction
Originally reaction calorimeters (hereafter referred to as RC) were designed to allow a reaction to proceed
under conditions that are as close to plant operation conditions as possible. In other words RC was a kind
of large-scale laboratory reactor generating the results that can be easily associated with a full scale
industrial process. The major difference of RC was that in addition to facilities, typical for lab-scale
reactors, such as temperature control, feed of some reagents (modeling the semi-BATCH mode) and
some others RC allowed accurate tracking the thermal phenomena occurring during the reaction
development.
The first RC has been designed for safety analysis of a process, but, as it turned out, it is very useful also
for process development and scale - up; moreover, thanks to the precise temperature control and accurate
measurement of the reaction heat release rate, data obtained by applying RC allowed evaluation of reaction
kinetics. One of the features of RC especially useful for understanding reaction's mechanism and kinetics
evaluation is that RC can easily be coupled with various analytical methods (e.g. chromatography or infra
red spectroscopy) thus providing valuable data on variation of species concentration.
The basis for the calculation of accurate calorimetric data is the balance of the heat and mass flows. In a
very general way the balance can be expressed as
Input = accumulation + output
In terms of mass balance this general equation comes to
Reaction mass at time t = initial mass + sum of all dosing and sampling operations at time t
As far as the energy balance is concerned it can be expressed qualitatively as
sum of rate of heat flow
Rate of heat Rate of heat heat loss
powers of enthalpy vari- rate to/from
accumulation, = generation by + + - - rate,
additional ation due to the jacket,
Wacc reaction, W Wloss
sources, P dosing, Wh Wflow

The more detailed discussion of every term and their math expressions will be given later together with
description of the main types of reaction calorimeters that are available now.

www.cisp.spb.ru; office@cisp.spb.ru
CISP CISP Newsletter # 11

2 Heat-flow RC (HF-RC)
2.1 Construction
HF-RC is the first type of the RC introduced by Mettler and well known as RC-1 [1]. The calorimeter's
vessel is the jacketed reactor equipped with the efficient stirrer so that it can be considered as a well
stirred reactor (Fig. 1). The main output signal is the reacting mixture temperature whereas jacket
temperature is defined by the thermostat. Typically the flow rate of the thermostat media (coolant) is big
enough to provide effective heat exchange with the reactor. Furthermore:
• it prevents significant accumulation of reaction heat in the mixture thus providing small deviation of
mixture temperature from jacket temperature;
• it can be safely assumed that coolant temperature is the same throughout the jacket.
Usually different thermal modes of the RC are
supported - isoperibolic mode (constant jacket
temperature), linear heating, isothermal mode,
when jacket temperature is controlled in such a
way that mixture temperature remains constant.
This type of calorimeter is known as Heat Flow
RC or, in a short form, HF-RC.
The RC can work in a BATCH and semi-BATCH
mode, for this last case the dosing system is
usually added which allows well-controlled feed
of some of the reagents. Other external tools
allow reflux of volatile components, sampling of
a mixture for e.g. chromatographic analysis,
Fig. 1 Scheme of the heat-flow reaction calorimeter. insertion of the transducer of the infra-red
a) jacketed reactor; b) structure of heat transfer
spectrometer, etc.

2.2 Mathematical model

2.2.1 Mass balance equation
In previous section mass balance has been presented schematically in the integral form but the
differential form is much more pertinent for quantitative analysis. The general differential equation of mass
balance is as follows:
dN i
 vdos ( t )  Cidos  vsampl ( t )  Ci ( t )  V ( t )  ν ji r j ; (1)
dt ( j)
Variation rate of Feed rate of Rate of sampling of Rate of change of species i
amount of species i species i species i due to reaction (kinetic term)
where Ni - number of moles of species i;
Cidos - concentration of species i in dosing; Ci ( t ) - current concentration of species i in a mixture;
vdos - volumetric feed rate; vsampl - volumetric sampling rate;
V(t) - current volume of the mixture;

 ji rj - rate of variation of the number of moles of species i due to reaction.

( j)
When deriving this equation we assumed that there is only one inlet to dose mixture of reagents which
can contain one or more species but it can be easily enhanced to take into account several inlets.
The following formulas give the relations that bound species concentrations and mixture volume with
number of moles of species:
1 N
V( t )  
( T ) ( i )
N i M i ; Ci  i ;
V( t )
(2)

where (T) is mixture density, Mi is molecular mass of species i. Kinetic term is defined by the kinetic
model of a reaction. Initial condition that complements equation (1) is:
Ni ( t  0 )  Nio
Integral form of mass balance can be derived from (4):

2
CISP CISP Newsletter # 11

t  t 
M( t )  M( 0 )   Cidos  M i   vdos ( t )  dt    i  sampl
 M v ( t )  Ci ( t )  dt  (3)
(i) 0 (i) 0 
If mass feed rate dmdos/dt and mass sampling rate dmsampl/dt are known then (3) becomes much simpler
t t
dmdos dmsampl
M (t)  M ( 0 )   dt 
dt  dt .
dt
(3a)
0 0
There are two features that should be emphasized.
1. The kinetic term in (1) describes variation of mixture composition but reaction doesn’t affect the mass
balance therefore it has been omitted when deriving the integral form (3).
2. Equations (1) or (3) are equally valid for all the types of RC.

2.2.2 Energy balance equation

The heat flow rate term
The heat flow rate term Wflow is usually assumed to obey the Newton law
W flow  US( T  T j ) , (4)
where U is the overall (or effective) heat transfer coefficient, S denotes the surface of heat exchange.
As a matter of fact U is the complex that can be decomposed to 3 components as shown in Fig. 1b:
1 / U  1 / U r  hw /   1 / U j (5)

where Ur is heat transfer coefficient via boundary layer (film) from mixture to the wall;  is thermal
conductivity of the reactor material; hw denotes wall thickness; Uj is heat transfer coefficient via boundary
layer (film) from the wall to cooling medium.
The main challenge of the HF-RC is that U and S depend on many factors and may change significantly
during the experiment. Let's mention some of the dependencies:
• S may vary in proportion to variation of mixture volume due to
• dosing/sampling;
• variation of mixture density due to change of current composition and thermal expansion;
• production of some gaseous products;
• Ur is function of stirring conditions (rate of agitator rotation, agitator geometry) and mixture viscosity
which varies along the reaction course due to change of mixture composition.
There are some methods that allow estimation of Ur and Uj values form mixture and cooling medium
properties and data about the agitator (see, e.g. [1]), but they are very approximate, there is often not
enough information for such estimates, etc. Therefore the direct determination is usually applied for
getting correct estimates by applying Joule effect-based calibration. For this purpose the RC is equipped
with the calibration heater immersed in the mixture. The essence of the calibration is that the short
rectangular electric pulse with known power Pc is applied to the heater. The heat generated by the heater
causes deviation of mixture temperature T=T(t)-Tj. Assuming that this is the only energy source in the
mixture the effective value of US can be calculated in two ways:
• by obtaining the point (instantaneous) estimate directly from (4):
US  Pc / T , or (6a)
• by obtaining the averaged estimate from the integral form of (4):
t2

US  Pc t / ( T  T j )dt , (6b)
t1
where t is the duration of the calibration pulse, t1 and t2 stand for the time instants when mixture
temperature starts to deviate from stationary value and goes back to this value respectively.
The first method is applicable only when the calibration pulse is long enough for temperature to stabilize.
The second method is more universal because even for short pulses when temperature varies in transient
mode the integral is always proportional to the energy generated by the heater.

3
CISP CISP Newsletter # 11

Several calibrations can be performed during the experiment to take into account the changes of the US. If
a reaction proceeds and calibrations are superimposed on the temperature variation caused by the reaction
then more complex procedure of processing calibration results is used in order to separate reaction impact.

Rate of heat generation by a reaction

Rate of heat generation by a reaction W is defined by the kinetic term W  Q j rj , where Q

j is
( j)
specific heat effect of j stage (it is accepted here that heat effect of an exothermic reaction is positive); rj
is the rate of j stage. Knowledge of this term is important when RC data are used for kinetics evaluation
but the primary aim of the experiment is to get correct estimate of W from the results of measurement.
The sum of powers of the additional sources comprises power of calibration pulses Pc, power generated
by rotation of the agitator Pag, and some others. We will only discuss two items mentioned above.

As it was noted already the calibration pulse causes deviation of mixture temperature. Its power Pc is
known precisely and can easily be taken into account.
The power generated by the agitator Pag is unknown; it depends on rotation speed, it can also depend on
current mixture viscosity which can vary along changing the composition. Let us assume that Pag is
constant. Then after expiring some transient period it will cause certain constant shift of mixture tempera-
ture, therefore it will be eliminated when analyzing data. Therefore Pag won't be included in the energy
balance. (To some extent the effect of Pag is similar to the position of base line in thermal analysis).

Heat accumulation in the reactor

Heat accumulation in the reactor is expressed as Wacc  M( t )c p ( t )dT / dt , where cp is the heat
capacity of the mixture;  represents thermal inertia:   1  ( M r c pr ) / ( Mc p ) ; Mr and cpr are mass
of the reactor and specific heat of its material respectively. Note that heat capacity of the mixture depends
on the current mixture composition and varies in time.
The detailed formula for the rate of enthalpy variation due to feed of reactants at temperature Tdos is:


Wh  vdos Cidos cm pi ( Tdos  T ) , where c pi is molar specific heat of i species; is temperature of
m
(i)
mixture fed. As in the case of mass balance if the mass feed rate is known this formula becomes simpler:
Wh  c p,dos ( Tdos  T )dmdos / dt , where c p,dos is the heat capacity per unit of mass of the mixture
fed.
As far as the heat losses Wloss are concerned they are subject to special calibration but in practice they
are taken into account implicitly when calibration by Joule effect is performed.

Energy balance equation

Now we can compose the energy balance equation. Traditionally it is presented as
dT dmdos
M ( t )  c p( t )   =W+Pc + c p,dos ( Tdos  T )  US( T  T j ) , (7)
dt dt
but for data processing which is aimed at estimation of W the more convenient form is
dT dmdos
W = US( T  T j ) + M ( t )  c p ( t )    Pc  c p,dos ( Tdos  T ) (8)
dt dt
Note that (7) or (8) doesn't include the term related to sampling. It follows from the fact that sampling
affects the total energy of the reactor only via change of mixture mass which is taken into account by the
mass balance equation.
Typical result of RC experiment is depicted in Fig. 2. Three short calibration pulses are shown
schematically. Pc = 12 W and pulse duration is just 3 min so that the temperature response of the RC is
in transient mode.
Dosing is implemented in two rectangular pulses. Temperature of the feed equals to room temperature
therefore it results in lowering mixture temperature in the reactor.

4
CISP CISP Newsletter # 11

Fig. 3 shows contribution of different items of the energy balance equation. Note that all the values are
presented per unit of initial mixture mass.

Fig. 2 Reactor temperature during the semi-BATH
experiment
1 - jacket temperature; 2 - mixture temperature; 3 -
dosing periods; 4 - calibration pulses.
Fig. 3 Contribution of different terms of eq. (8)
1 - W; 2 - W flow, 3 - W h, 4 - Wflow + W h,
5 - Pc, 6 - W acc

2.3 True Heat Flow RC

As it was noted one of the main challenges of heat flow
RC is complex dependency of heat exchange parameters
U and S on various factors such as variation of mixture
volume, mixture viscosity, temperature, cooling medium
flow rate, geometry and rotation speed of the agitator and
some others. Even on-line calibration (calibration during
the experiment) cannot resolve all the problems,
specifically because it is difficult to get precise results of
calibration if calibration pulse is applied when reaction
proceeds and reactor response to the pulse overlaps
temperature variation peak due to reaction heat.
Therefore several methods were proposed for determi-
nation of heat flow from reacting mixture to the jacket that
don't require knowledge of heat transfer parameters.
Fig. 4 Scheme of CPA 202 The original solution to the problem was introduced by
1 - reactor; 2 - thermally insulated reactor walls, 3 - Chemisens [2] which has designed the so-called true
reactor lid; 4 - bath with thermostatic liquid; 5 - heat heat flow RC CPA 202. The calorimetric block is
flow transducer; 6 - Peltier element.
schematically shown in Fig. 4.
The reactor 1 has thermally insulated walls 2 so that almost the whole heat exchange is effected through
the reactor's bottom which is in good thermal contact with the heat flow transducer 5. The transducer is
pre-calibrated, its signal is proportional to the heat flow and doesn't depend on heat transfer coefficient,
therefore there is no need in on-line calibration. Wflow is directly measured during experiment. The Peltier
element 6 is placed under the transducer, it is used for maintaining necessary temperature in the reactor.
To minimize the uncontrolled heat losses the reactor is immersed in the bath with the thermostatic liquid.
o
Its temperature is kept a bit lower that the reactor temperature (the difference is less than 1 C). Thanks
to big mass heat capacity of the liquid the bath provides high stability of thermal mode.
Energy balance for true heat flow RC is presented by the equation
dT dmdos
W = W flow + M ( t )  c p ( t )     c p,dos ( Tdos  T ) (8a)
dt dt
3 Heat balance RC (HB-RC)
Another possible solution is to determine directly the amount of heat carried by the coolant. This type of
instruments is called Heat Balance RC hereafter referred to as HB-RC. If the mass flow rate of the cooling
medium F and its heat capacity cpc are known, and inlet and outlet temperatures of the cooling medium
Tj,in and Tj,out are measured then the heat flow rate to/from the reacting mixture will be expressed as

5
CISP CISP Newsletter # 11

W flow  F  c pc ( T j,out  T j,in ) (9)

and energy balance equation will take the following form:
dT dmdos
W = F  c pc ( T j,out  T j,in ) + M ( t )  c p ( t )    Pc  c p,dos ( Tdos  T ) + Wloss (10)
dt dt
Contrary to the case of heat flow RC heat losses
play very important role in energy balance of the HB-
RC. Wloss comprises heat losses from outer surface
of the jacket and from the reactor's parts that are not
covered by the jacket. In the case of HB-RC Wloss
will depend on the outer (room) temperature, intensi-
ty of natural convection in the air, and other factors.
All this impedes accurate measurement of Wloss
therefore some HB-RCs are equipped with external
thermostats or the double-jacketed reactors are used
to control the heat losses. An example of the RC with
the double-jacketed reactor is SYSTAG Calo 2310
Fig. 4 Scheme of HB-RC Chemisens CPA 102 RC [3] which can work both in HF and HB modes.
1 - reactor; 2 - reactor's jacket; 3 - thermally insulated
reactor's wall; 4 - compartment made from thermal Another example of smart solution is represented by
insulator; 5 - thermostat the ChemiSens CPA 102 calorimeter [2] (see Fig. 4).
The reactor (1) is placed into the thermally insulated compartment (4). The cooling medium temperatures
are measured on the inlet and outlet of the reactor's jacket (2). Then cooling medium goes along the
thermostat (5) which covers the inner surface of the compartment. As thermostat temperature is very
close to jacket temperature the heat losses are minimized.

4 Power-Compensation RC (PC-RC)
Similar to PC-DSC, PC-RC is based on the use of a calibrated heater that maintains necessary reactor
temperature. In the case of an exothermic reaction the appropriate heat removal (heat loss) should be
provided therefore the reactor should be placed in a
thermostat which is kept at temperature somewhat lower than
the required reaction temperature. Typically the difference is
about 20 °C. The semi-BATCH is most appropriate mode for
PC-RC experiments. Initially the reactor is filled with a reagent
or mixture where there is no reaction and the heater elevates
reactant temperature to the set level. When equilibrium is
reached, the heater pumps constant power into the mixture to
compensate heat losses. This is the "base line". When a
reaction begins and reaction heat is generated (exothermic
reaction) or absorbed (endothermic reaction), the control
system reduces or increases the power of the heater by the
same amount as was produced by the reaction to maintain
constant temperature. In such a way PC-RC provides direct
Fig. 5 Scheme of PC-RC with double-jacketed measurement of the rate of enthalpy change of the reacting
reactor mixture.
If to denote Ph as the deviation of the compensation power from the base line, the energy balance takes
simple form
dmdos
W = Ph  c p,dos ( Tdos  T ) (11)
dt
Contrary to (8) and (10) energy balance doesn't contain calibration power Pc and heat accumulation. Pc
is not included because PC-RC doesn't require calibration; the second term equals to 0 because dT/dt=0
(isothermal mode).
There are several commercially available PC-RCs. Examples are HEL group Simular [4] and Syrris Atlas
[5]. In both the cases the double-jacketed reactors are applied (Fig. 5).
Thermostatic liquid which is circulated in the inner jacket provides power compensation. Power of the
heater in the jacket circuit is measured during an experiment.

6
CISP CISP Newsletter # 11

5 Interpretation of RC data
The basis for interpreting RC data is the set of mass and heat balance equations.
As far as the mass balance is concerned it is completely defined by eq. (6) or (6a).
Interpretation of energy data is more complex. As it follows from eq. (8), (8a), (10) or (11) several terms
must be known and taken into account. Though these equations somewhat differ from each other there
are two common terms - energy accumulation and change of the reacting mixture enthalpy due to dosing:
dT dmdos
M ( t )  c p( t )   and c p,dos ( Tdos  T ) (note: in some cases this term can be 0)
dt dt
If data acquisition and processing software of an RC is capable of taking into account these and other
terms then one can expect to get correct estimate of W(t) which is the primary information for proper
understanding of a reaction course in general and for kinetics evaluation in particular. Otherwise all these
corrections should be made when further data analysis is performed.
It is clear therefore that the first question one should ask is what should be expected as the output from
such software.
It should be emphasized that the comprehensive treatment of the measured data is quite complex.
Indeed the self heating rate due to energy accumulation is proportional to mixture heat capacity which
depends on current composition of reacting mixture and properties of species. This information is often
unknown; even measurement of species concentrations doesn't give general solution because in many
cases there is no possibility to measure concentrations of all the species.
If RC data are to be used for kinetics evaluation then there exists the principal solution to this problem.
Kinetics evaluation should be based on the complete model of the reactor which in fact includes the same
equations of mass balance (4) and one of the energy balance equations (8), (8a), (10) or (11) depending
on the type of the RC used. In this case it is enough to retrieve from the experiment the following data:
T(t), Wflow(t), Pc, composition and flow rate of dosing, flow rate of sampling.
Other obligatory information is the set of species properties - molecular mass, density, specific heat.
Apparently such general approach requires use of the appropriate software. CISP designed such kind of
software which meets all the requirements mentioned above. This is the DesK software package [6]
which is supported by the RCPro program [7] for comprehensive processing of PC data. RCPro is useful
despite the availability of data processing options of the instrumental software supplied by the
manufacturers of RC instruments.

6 References
1. Official web site of Mettler toledo: http://www.mt.com/
2. Official web site of Chemisens: http://www.chemisens.se/CMS/
3. Official web site of SYSTAG: http://www.systag.ch/home.html
4. Official web site of HEL Group: http://www.helgroup.com/
5. Official web site of Syrris: http://syrris.com/
6. Official web site of CISP: http://www.cisp.spb.ru/desk-pro
7. Official web site of CISP: http://www.cisp.spb.ru/rcpro

View publication stats