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Article history: This paper presents a continuous microuidic calorimeter to measure kinetics and enthalpy of very
Received 10 July 2009 dangerous, highly exothermic chemical reactions. The main idea is to use a microuidic chip, in co-ow
Received in revised form 22 February 2010 or droplet ow, where the microchannel acts as the chemical reactor. A thermopile (Peltier element)
Accepted 24 February 2010
measures the global heat ux dissipated during the chemical reaction. A highly thermal conductive plate
is placed between the thermopile and the reactor to avoid severe temperature gradients and to let most
Keywords:
of the heat ux go through this plate. Because of the microchannel dimensions only a small amount of
Microuidic
products is required.
Thermal and chemical analysis
Flow microcalorimeter 2010 Elsevier B.V. All rights reserved.
Enthalpy
1. Introduction complex design of integrated circuits [35]. Lechner et al. have built
different integrated circuit calorimeters adapted to characterize
The kinetics and the thermodynamics of chemical reactions are enzyme-catalysed reactions [6]. Ross et al. and Arata et al. have
important features for the development and the safety of chemical developed an intrusive method using a uorescent dye to mea-
processes. It is well known that both heat transfer and chemical sure the temperature distribution inside the microchannel [7,8].
kinetics occur during chemical reactions and that one way to con- Another method allows to obtain the temperature eld of all the
trol and to measure those phenomena is by calorimetry. Therefore microuidic chip by the mean of an infrared (IR) camera. Mllmann
the characterization of exothermic chemical reactions is well devel- et al. and Antes et al. have proved the IR camera can be used to
oped in the literature and different types of calorimeters already develop and optimize microsystems [9,10]. The IR thermography
exist [1]. has also been used to estimate the reaction enthalpy of a chemical
The recent development of MEMS (Micro-Electro-Mechanical reaction in microsystem by Hany et al. [11].
Systems) provides a very promising range of new tools to charac- In this context, we have developed a tool which combines the
terize chemical reactions in continuous ow at a small scale. The use of microvolumes, a high thermal sensitivity, a good control of
main advantage of those systems is the small size of the microchan- the reagent mixing and of isothermal conditions.
nels which permits the controlled mixing of the reactants. Indeed, The method applied here measures the global heat ux around
the ow is laminar with low Reynolds number (100). It is also con- the microchannel thanks to a uxmeter located under the standard
venient to use a small amount of products and to be able to easily microuidic chip. The main purpose of this paper is to present this
and quickly test a large number of chemical reaction congurations new microcalorimeter. In the rst part, the experimental device
[2]. Moreover, the high ratio between surface and volume allows to principle is described. An analytical model that describes the ther-
control the heat transfer and to investigate very exothermic reac- mal behaviour is introduced. The importance of thermal properties
tions under safe operation conditions. Nevertheless, measurement of the wafer used for the microuidic chip is discussed. Further-
of the temperature and the heat ux at such a small scale represents more, a thermal calibration (by Joule effect) is performed in order
the main difculty. to verify the features of the microcalorimeter. The second part deals
However to date, several studies address this topic. Most of them with the validation of the microcalorimeter with measurement of
use local temperature microsensors which need specic and quite the enthalpy of a strong acidbase chemical reaction. Such valida-
tion is realised in two ow congurations: co-ow where the two
reactants ow side by side through the microchannel and droplet
Corresponding author. Tel.: +33 556464751; fax: +33 556464790. ow where the reactants are contained inside droplets carried by an
E-mail address: cindyhany@netcourrier.com (C. Hany). inert continuous phase. Then, the conversion rate of this chemical
1385-8947/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2010.02.048
C. Hany et al. / Chemical Engineering Journal 160 (2010) 814822 815
2. Microcalorimeter description
2.1. Microcalorimeter design Fig. 2. Representation of the semi innite thermal problem when a heat ux of 1 W
is imposed.
A differential microcalorimeter has been developed containing
two microuidic chips in two separated chambers (Fig. 1) [12]. One of the baseline on the experiment for several reasons: the mea-
microuidic chip is used for the reference and the other one to carry sured voltage is a differential measurement, the experiment time
out the chemical reaction. Each microuidic chip is placed above a is shorter than 10 h.
thermopile used to measure the heat ux. The reagent ow rates are Then a stainless plate (5) is put below the brass block. This
established with a syringe pump (Nemesys). No uids are injected plate is thermally regulated via a thermostatic ow circulation
in the reference chip which is used as baseline. from Ts = 5 to 90 C. This allows to perform experiments at various
Both microuidic chips are built with a PDMS (PolyDiMethyl- temperatures depending on the uid properties. All parts of the
Siloxane) matrix, containing a negative channel network. This calorimeter are heat shielded by insulating foam (6). Furthermore,
PDMS matrix is glued onto silicon wafer after UVozone activation. the inlet uid is preheated by passing through the brass block via a
Since silicon is a good thermal conductor, the chemical reaction groove allowing to x the tubing. As a result, the chemical reaction
occurs under isothermal conditions in the microchannel. PDMS has begins in the microcalorimeter at the setting temperature (Ts).
been chosen because it is usually employed to realise microuidic
chip, it is easy to use and allows to obtain various channel geome- 2.2. Thermal modeling of the microuidic chip
tries. Moreover, PDMS is good insulator that is necessary in our
device (cf. Section 2.2). However, it is not an inert material and some In order to model the thermal behaviour of the microuidic chip,
interactions can occur with some solvents. The selected substrate a 2D transient thermal problem (Fig. 2) is considered. The system
(thickness 500 m) is made of silicon with a 5 cm diameter. is made of three homogeneous media of different thermal prop-
The microuidic channel is 32 cm long, 250 m wide and erties: medium 1 is the thermopile used as uxmeter, medium
250 m high. The channel is a serpentine channel to optimize the 2 is the wafer of the microuidic chip and medium 3 is the elas-
volume of the chip. tomeric PDMS where the microchannels for chemical reaction are
The voltage is measured with thermopiles (3) by Seebeck effect. imprinted.
The voltage obtained from the reference chamber (1r) is sub- The 2D transient model, described by Eq. (1) allows to calculate
stracted to the voltage from the reaction one (1). Then, by using the temperature eld in the different media of the microuidic chip
the calibration coefcient (cf. Section 2.3) the heat ux produced when a chemical heat ux is generated in the microreactor (Fig. 2).
by the chemical reaction can be determined.
The calorimetric sensitive area is a 50 mm 50 mm square (four 2 Ti 2 Ti 1 Ti i
+ = , i = 1, 2 or 3 and ai = (1)
thermopiles connected in series). The voltage is measured with a x 2 y2 ai t i cp,i
numerical voltmeter (Agilent 34970 A). The temperature (Ts) is set
where i is the subscript of each media, T is the temperature (K),
by a thermostatic ow circulation (5). A computer using LabviewTM
a is the thermal diffusivity (m2 s1 ), is the thermal conductivity
software controls all these steps via a RS232 port.
(W m1 K1 ), is the mass density (kg m3 ) and Cp the heat capacity
In order to minimize perturbations of the baseline caused by
(J kg1 K1 ).
the environmental thermal variations, the thermopiles are placed
First, we assume that the chemical heat ux can be represented
on a brass block (4) of 20 cm 20 cm 2.5 cm used as an isothermal
as a discontinuous function (x, t) along the plate whose value is
reservoir. Due to the high thermal capacity of the bulk, the varia-
zero for x greater than the length b and positive for x between 0 and
tion of the baseline is less than 10 W on 10 h. There is no inuence
b (Eq. (2)).
QH(t) if 0 < x b
(x, t) = (2)
0 if b < x < L
Fig. 3. (a) According to the thermal modelisation the steady state temperature on uxmeter (y = e1 ) can be plotted versus the wafer length for glass and silicon wafer of
500 m thick; thus it is obvious that the local temperature is higher with a glass wafer than with a silicon wafer and (b) the transient heat ux on both thermopile and PDMS
layer is represented by a function of time thanks to the thermal modelisation; thus we can see that most of the heat ux goes through the thermopile, and less than 0.01% of
the heat ux goes through the PDMS.
Fig. 6. Imposed heat ux versus measured tension at Ts = 25 C, the solid line cor- = Hr QCX (5)
responds to the linear regression.
where is the heat ux (W), Hr is the enthalpy (J mol1 ),
Q is
the ow rate (L s1 ), C is the concentration (mol L1 ) and X is the
and this coefcient () is used to deduce the chemical heat ux
conversion rate. Because the reaction is completed, the heat ux
(W).
released by the reaction is directly proportional to the molar ow
As the thermal conductivity and Seebeck coefcient of the
rate. Thus, the reaction must be complete (X = 1) in the microreac-
Peltier depend on temperature, the calibration coefcient should
tor. For this reason, the residence time has to be longer than the
be estimated for each temperature we used (Table 1). The experi-
reaction one. As the plot of the heat ux versus the molar ow rate
mental coefcients are slightly higher than the manufacturer ones
provides a line the reaction is complete in the microuidic chip.
with a proportional coefcient close to 1.25. This difference can be
explained by a different way to estimate this coefcient. However,
3.1.1. Sensitivity of the enthalpy determination
we can observe in Fig. 4 that the evolution of versus temper-
The enthalpy is determined by the use of the microcalorimeter.
ature has the same tendency for both the manufacturer and our
During experiments, the global heat ux produced by the chemical
experimental values.
reaction is measured. As the molar ow rate is known, the reaction
enthalpy can be deduced from Eq. (6).
2.4. Sensitivity
U
Hr = = (6)
The accuracy of the calibration coefcient is estimated by QCX QCX
reproductibility experiments at three different temperatures. The
where Q is the ow rate of the limiting reagent (L s1 ), C is the
calibration coefcient is evaluated 30 times for each tempera-
concentration of the limiting reagent (mol L1 ), Hr is the reac-
ture. The relative error is calculated using the standard deviation
tion enthalpy (J mol1 ), X is the conversion rate, is the calibration
of and Eq. (4).
coefcient (W V1 ) and U is the measured tension (V).
According to Eq. (6), the standard deviation of estimated
u (%) = 100 (4)
enthalpy depends on the ow rate (Q), the numerical voltmeter
where u is the relative error of the calibration coefcient ( (U) and the calibration coefcient (). As the chemical reaction is
(W V1 )), is the standard deviation of the calibration coefcient complete in the microuidic chip, the conversion X is equal to 1.
determined by experiment (W V1 ). Table 2 presents the results The solutions are commercial solutions and the standard error of
obtained for the different temperatures. the concentration is negligible (7 102 %).In order to estimate the
error of each parameter, several experiments are realised.
3. Microcalorimeter testing: results and discussion
- Firstly, the standard error of the injected ow rate is determined
3.1. Reaction enthalpy measurements by a specic experiment. Some uorinated oil is injected by
the syringe pump and the weight of oil is measured as a func-
A promising application of microtechnologies is the use of tion of time. Three different ow rates are tested: 100, 500 and
one phase liquid ow (co-ow) or two-phase liquidliquid ow 1500 L h1 . This experiment is realised 20 times at each ow rate
Table 1
Experimental and manufacturer values of the calibration coefcient: .
Table 2
Results of the standard error of the calibration coefcient for different temperatures.
Temperature ( C) 25 50 80
Average of calibration coefcient (W V1 ) 3.95 3.74 3.98
Standard deviation (W V1 ) 1.103 4.103 5.103
Relative error u (%) 0.025 0.11 0.13
818 C. Hany et al. / Chemical Engineering Journal 160 (2010) 814822
Table 3
Results of the enthalpy sensitivity.
Qtheoretical Qexperimental
usetting = (7)
Qtheoretical
Fig. 8. The measured heat ux is represented versus time for different reagent ow
- Secondly, the accuracy of the measured tension is estimated by rates in co-ow at Ts = 25 C; one point over 500 is drawn.
the experimental error and the reading error (103 mV). We apply
various power by the use of the calibration chip to determine the The diffusion length, which corresponds to the mixing length Xm ,
experimental error. This experiment is performed 30 times for the can be described by Eq. (8).
three different power: 200, 600, and 1000 mW. Thus the exper-
Xm 1 w2 U
imental error is determined. The highest error on the measured = 2Dt = 2D Xm = with
tension is used to calculate the error on the enthalpy estimation. U 8 D
- Finally, the relative error of the calibration coefcient has been wU 1
evaluated previously. Pe = Xm = Pe w (9)
D 8
where is the half width of the diffusion cone (m), D is the diffusion
The results are presented in Table 3. The sum of these results leads coefcient (m2 s1 ), C is the concentration (mol m3 ), U is the ow
to the error on the experimental enthalpy of reaction which is esti- velocity (m s1 ), Xm is the diffusion length (m), t is the time (s), w
mated at 4.7%. is the channel width (m) and Pe is the Peclet number.
We use a microchannel of 250 m width, the ow rate varies
3.1.2. Monophasic ow from 500 to 2500 L h1 thus the mixing length goes from 17 to
We study the acidbase reaction with one liquid phase ow: 90 mm. As the length of the microchannel is 32 cm the reagents are
co-ow. This experiment is performed at Ts = 25 C for several ow fully mixed inside the chip. The acidbase reaction is a fast reaction
rates ranging from 250 to 1250 L h1 . In microuidic device, the thus the reaction is complete inside the chip and the conversion rate
Reynolds number is very low (<1), so the ow is laminar. The is equal to 1.
reagents mixing is realised by diffusion. Measurements performed During experiments, the heat ux produced by the chemical
by an infrared camera allow us to show that the reaction occurs at reaction in the microcalorimeter is recorded as a function of time
the interface between the two reagents (Fig. 7). The interdiffusion at various ow rates, as it is represented in Fig. 8.
area was measured and studied by several investigations and leads Then the heat ux released by the reaction is compared to the
to estimate the mixing time [1517]. molar ow rates. The evolution is linear. By Eq. (5) the slope gives
The solution of Eq. (8) gives the concentration prole of a solute directly the reaction enthalpy (Fig. 9).
which diffuses in a microchannel. The value of the enthalpy we obtained is 54.38 2.78 kJ mol1
with an estimated uncertainty of 5.13%. This value corresponds to
C the value of 55.8 kJ mol1 provided by the literature [18] with a
+ U C = D 2 C (8)
t deviation lower than 3%.
Fig. 7. Infrared image of acidbase reaction co-ow in a microchannel of 250 m Fig. 9. Heat ux versus molar ow rates in co-ow at Ts = 25 C; solid line correspond
width, the white colour corresponds to the highest temperature and the black one to the linear regression and the linear relation allows to determine the reaction
to the coldest temperature. enthalpy.
C. Hany et al. / Chemical Engineering Journal 160 (2010) 814822 819
reaction, which is the same for all oil ow rates. Thus we can assume
that the oil ow rate has no effect on the heat measurement in this
device and the droplet ow can be performed.
Secondly, the total ow rate is varied while the ratio between
the reagents ow rate and the oil ow rate is constant and
equal to 0.5. Then the reaction enthalpy can be estimated
as previously (Fig. 12). The reaction enthalpy is estimated at
55.74 2.86 kJ mol1 . This value is in good agreement with the lit-
erature value of 55.8 kJ mol1 , the deviation is about 0.1% [18]. This
Fig. 10. Droplets formation mechanism in a ow-focusing junction. result is close to the value determined by this microcalorimeter in
co-ow.
Fig. 12. (a) Measured heat ux versus time with constant ratio (reagent ow rate over oil ow rate) in droplets ow at Ts = 25 C; one point over 500 is drawn and (b) heat
ux with constant ratio (reagent ow rate over oil ow rate) versus the reagent molar ow rates in droplets ow at Ts = 25 C; solid line corresponds to the linear regression
and the linear relation allows to determine the reaction enthalpy.
820 C. Hany et al. / Chemical Engineering Journal 160 (2010) 814822
and equal to 0.1 mol L1 . The experiments come out the following
way: the NaOH ow rate is constant and equal to 400 L h1 , then
the HCl ow rate increases until the measured heat ux reaches
a constant value. The reaction occurs in stoichiometric ratio when
the heat ux steady state is reached. Thus, the equivalent ow rate
is determined at the beginning of this steady state. The increase of
the HCl ow rate is done in two different ways: rstly it increases
steadily each 15 min until reaching the steady state (Fig. 15(a));
secondly, as it is shown in Fig. 15(b), the ow rate of HCl increases
continuously each minute.
According to the two sets of experiments, the maximum heat
ux is measured when the HCl ow rate is equal to 800 L h1 .
So the stoechiometry of the chemical reaction is obtained at the
expected value of the NaOH concentration (i.e. 0.2 mol L1 ).
(10)
Fig. 15. Measured heat ux versus time at different ow rates at Ts = 25 C for calorimetric titration of NaOH solution (0.2 mol L1 ) by HCl solution (0.1 mol L1 ): (a) ow rate
of HCl changes each 15 min and (b) ow rate of HCl changes each 60 s.
C. Hany et al. / Chemical Engineering Journal 160 (2010) 814822 821
Fig. 16. Determination of the mixing enthalpy of the esterication reaction in co-ow at Ts = 30 C: (a) measured heat ux versus time at various ow rates and (b) heat ux
versus the reagent molar ow rates, solid line corresponds to the linear regression.
Fig. 17. Determination of the mixing enthalpy of the esterication reaction in droplets at Ts = 30 C: (a) measured heat ux versus time at various ow rates and (b) heat ux
versus the reagent molar ow rates, solid line corresponds to the linear regression.
Firstly, the mixing enthalpy is determined in co-ow, the The plot of the heat ux versus the molar ow rate is linear and
results are presented in Fig. 16. The heat ux measured is neg- allows to determine the global enthalpy (Fig. 18). The estimated
ative (Fig. 16(a)) and increase with the ow rate. Thus the value is Hexo = 54.8 kJ mol1 .
mixing enthalpy is an endothermic phenomenon. According to As the mixing enthalpy (Hendo ) is known, the enthalpy of reac-
the Fig. 16(b), the experimental enthalpy of mixing is 3.98 tion (Hr ) can be determined using Eq. (11).
0.2 kJ mol1 . The deviation of this value compared to the literature
value (Hm = 4.2 kJ mol1 ) is 5.3% which is sufciently good [21]. Hr = Hexo Hendo (11)
The second set of experiment is relative to the measurement
of the mixing enthalpy in droplets. The inert continuous ow in
made of a uorinated oil with a viscosity of 10 mPa s. The results
obtained are shown in Fig. 17. We can also observe that the heat
ux is negative which means that the enthalpy due to the mixing
corresponds to an endothermic phenomenon. The plot of the heat
ux versus the molar ow rate, the mixing enthalpy is estimated
at 4.24 0.22 kJ mol1 that is very close to the literature [21].
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