EP1474667A1 - Ensemble permettant de mesurer des quantites de chaleur en mesurant simultanement les cinetiques d'evaporation et/ou de condensation de quantites minimales de liquide, afin de determiner des parametres thermodynamiques - Google Patents

Ensemble permettant de mesurer des quantites de chaleur en mesurant simultanement les cinetiques d'evaporation et/ou de condensation de quantites minimales de liquide, afin de determiner des parametres thermodynamiques

Info

Publication number
EP1474667A1
EP1474667A1 EP03739433A EP03739433A EP1474667A1 EP 1474667 A1 EP1474667 A1 EP 1474667A1 EP 03739433 A EP03739433 A EP 03739433A EP 03739433 A EP03739433 A EP 03739433A EP 1474667 A1 EP1474667 A1 EP 1474667A1
Authority
EP
European Patent Office
Prior art keywords
liquid
arrangement according
measuring
measuring chamber
smallest amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03739433A
Other languages
German (de)
English (en)
Inventor
Peter MÜHLIG
Thomas Klupsch
Rolf Hilgenfeld
Hans-Jürgen KIEL
Axel Walter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xtalconcepts GmbH
Original Assignee
IMB Institut fur Molekulare Biotechnologie eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IMB Institut fur Molekulare Biotechnologie eV filed Critical IMB Institut fur Molekulare Biotechnologie eV
Publication of EP1474667A1 publication Critical patent/EP1474667A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K17/00—Measuring quantity of heat
    • G01K17/006—Microcalorimeters, e.g. using silicon microstructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
    • G01N25/4846—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a motionless, e.g. solid sample

Definitions

  • thermodynamic parameters for measuring quantities of heat while simultaneously measuring the evaporation and / or condensation kinetics of the smallest quantities of liquid for determining thermodynamic parameters
  • the invention relates to an arrangement for measuring amounts of heat while simultaneously measuring the evaporation and / or condensation kinetics of the smallest amounts of liquid for determining thermodynamic parameters according to the preamble of the claims.
  • the quantities of heat can be taken up from very small samples, which mainly consist of liquid, during the evaporation and / or the condensation.
  • the arrangement according to the invention is used primarily for the simultaneous measurement of specific heat of vaporization and vapor pressure of solutions near room temperature. If there is a chemical equilibrium in the liquid and the evaporation and / or condensation process is associated with a shift in the chemical equilibrium, the arrangement also serves to measure the specific chemical heat of reaction.
  • the device On composite systems, consisting of a solution in contact with a solid (crystalline) phase of the solute, the device also serves to measure the concentration of the saturated solution and the specific heat of solution.
  • the smallest amount of liquid can also be a gel-like substance that binds the solvent.
  • the arrangement is intended for measurements on solutions in which the vapor pressure of the solvent does not exceed that of saturated water vapor and the vapor pressure of the solute over the solution is negligibly small compared to that of the solvent.
  • the resulting characteristic time determines the time constant that the calorimeter must have at least in order to to determine the total amount of heat released.
  • the still reliably detectable power is approximately 0.1 ⁇ W; it drops to approx. 10 nW at a time constant of 30 s.
  • the invention is based on the object of small thermal outputs in the nW range which during the evaporation and / or condensation of a part of the liquid of the sample over a period of preferably 1000 s of the sample of the order of magnitude 1 ⁇ l itself or given, as well as to determine small differences in heat outputs compared to a reference measurement of the same order of magnitude. Since the thermal output to be measured also depends on the rate of evaporation and / or condensation, the desired arrangement according to the invention should also enable measurement of the evaporation and / or condensation kinetics of the smallest liquid samples, these measurements simultaneously determining the vapor pressure of the liquid or small differences of the vapor pressure compared to a reference sample.
  • a sample is introduced into a measuring chamber in which the temperature and vapor pressure of the solvent (relative air or gas humidity) are kept constant.
  • the spontaneous loss of mass of the sample and the spontaneous lowering of the temperature on the sample surface compared to the temperature in the measuring chamber are measured as a function of time.
  • the arrangement is basically constructed in such a way that the sample is in thermal contact exclusively with the gas in the measuring chamber and a substance transition on the sample surface can only take place with the gas in the measuring chamber.
  • the surface temperature of the sample becomes pyrometric, i.e. H. measured without contact.
  • the evaluation of all data is computer-supported in a subordinate periphery.
  • the sample itself represents the working substance of a calorimeter, which is preferably operated under the condition of quasi-steady-state heat exchange with the surroundings, the heat output released or absorbed by the sample being calculated from the time course of the temperature measured on the sample surface.
  • the arrangement is particularly intended to carry out measurements on small samples in the event that the amount of heat to be detected is released very slowly. With a sample mass of approx. 1 mg, a resolution of the thermal output in the order of 10 nW should be achievable with a time constant in the order of 1000 s.
  • the arrangement according to the invention serves in particular to determine thermodynamic variables that can be derived therefrom, such as the excess contribution of the chemical potential or the enthalpy of the solvent, the interaction of the dissolved substance with the solvent or the interaction of the molecules of the Characterize solvents with each other.
  • thermodynamic variables such as the excess contribution of the chemical potential or the enthalpy of the solvent, the interaction of the dissolved substance with the solvent or the interaction of the molecules of the Characterize solvents with each other.
  • the arrangement also serves for the direct determination of parts of the phase diagram.
  • the device according to the invention should meet with regard to its performance parameters and its structural details the requirements which are required for measurements on aqueous solutions of biological macromolecular compounds, e.g. Proteins, including
  • the arrangement according to the invention is intended to enable thermodynamic measurements in a time-economical manner, so that it can be used for routine characterization (comparable to differential thermal analysis in inorganic systems) in all investigations of the crystal growth of proteins.
  • two independent measurements are carried out simultaneously on the sample to be examined (aqueous solution). During the entire measurement period, the mass loss of the sample due to a constant evaporation of the solvent due to the environmental conditions to be selected is recorded.
  • a calorimetric measurement of the heat of vaporization per unit of time is carried out during the entire measurement period, the working substance of the calorimeter arrangement, which represents the arrangement, being represented by the sample to be examined itself.
  • This calorimetric measurement is implemented in a non-invasive way in that the surface temperature of the sample is determined pyrometrically and continuously recorded with the help of at least one thermal sensor.
  • the sample to be examined (aqueous solution) is located in the arrangement according to the invention in an airtight sealed measuring chamber, in which the temperature and relative air humidity can be set precisely and are kept constant during the entire measuring period, and temperature gradients and convection are largely avoided.
  • the arrangement is such that the sample has thermal contact with its surroundings practically only via its free interface to the surrounding gas space and a substance transition from the sample to its surroundings can practically only take place via this free interface.
  • An elliptical concave mirror and a radiation receiver are located inside the measuring chamber for pyrometric measurement of the surface temperature of the sample.
  • the invention can, for example, be designed such that the sample is present as a hanging drop at the tip of a fine, vertically aligned capillary.
  • the geometry of the capillary is chosen so that the hanging drop is as large as possible Diameter, based on the outer diameter of the capillary, is formed in a coaxial alignment with the capillary (capillary with a wall thickness that decreases in a wedge shape towards the tip, for example, produced by grinding. Outside or inside diameter of the capillary at the tip about 80 ⁇ m or 50 ⁇ m) ,
  • the surface of the capillary in its mouth area is passivated (e.g.
  • the drop mass is determined using a measuring microscope, which leads from the outside into the measuring chamber and is arranged in such a way that the drop is in its object plane and allows the geometric parameters of the drop to be measured.
  • the capillary can be formed as the tip of a measuring pipette that can be filled and operated from the outside, which can simultaneously serve as a reservoir for the sample liquid and for thermal equilibration of the sample before the start of the measurement.
  • the arrangement according to the invention can, for. B.
  • the sample to be examined is in an upwardly open cup-shaped container inside the measuring chamber, so that only the upper meniscus of the liquid has contact with the measuring chamber volume.
  • the container must consist of a very difficult to wet, inert material with extremely low thermal conductivity and have typical internal dimensions of a maximum of 4 mm in diameter and 1 mm in height.
  • the sample mass is determined by weighing.
  • the container is connected to a weighing pan of a precision balance with electromagnetic force compensation and a measuring accuracy of approx. 0.1 ⁇ g which leads into the measuring chamber, whereby the mass of the liquid in the container can be registered continuously.
  • a pipette that leads from the outside through the wall into the measuring chamber and can be operated from the outside is attached in such a way that it can be used to fill a defined amount of sample liquid into the well-shaped container.
  • this pipette serves as a reservoir and for thermal equilibration the solution to be examined.
  • this measuring pipette can have such a large outlet opening that a small single crystal (typical dimension a few hundred ⁇ m) into the solution with the solution to be examined provided for receiving the solution can be introduced.
  • the measuring chamber wall can contain a feedthrough for a measuring microscope (eg endoscope), which is arranged in such a way that the liquid meniscus in the cup-shaped container and possibly a single crystal located therein can be observed.
  • a measuring microscope eg endoscope
  • the measuring arrangement includes a peripheral for data acquisition and evaluation as well as for control.
  • the temporal recording of the geometry parameters of the hanging drop via the measuring microscope is preferably carried out by means of a downstream image processing.
  • the vapor pressure of the solvent (e.g. water) in the measuring chamber is determined at a great distance from the sample by the relative air humidity in the measuring chamber and is usually lower than the equilibrium vapor pressure of the solvent over the solution, which is directly above the liquid meniscus.
  • the sample is introduced into the measuring chamber as soon as the temperature of the sample liquid in the pipette has adjusted to the temperature in the measuring chamber (temperature differences of up to 1 degree C are permissible).
  • the evaporation of the solvent begins by directional diffusion from the free interface of the sample into the measuring chamber volume.
  • the evaporation rate of the solvent is determined from the measured change in the mass of the sample over time, and the equilibrium vapor pressure of the solvent is determined therefrom.
  • the temperature of the sample lowers compared to the temperature in the measuring chamber (at a great distance from the drop) until the heat of evaporation (evaporation enthalpy of the solvent) and the drop due to heat conduction from the gas space of the measuring chamber are reduced supplied heat output almost balanced and a quasi-steady temperature difference arises.
  • the evaporation enthalpy of the solvent is determined from the pyrometrically measured time-dependent difference of the temperatures on the sample surface on the one hand and in the measuring chamber on the other hand and by using the measured time-dependent evaporation rate of the sample.
  • the continuous evaporation of the solvent during the measurement results in a constant increase in the concentration of the solution and thus a constant change (generally a decrease) in the vapor pressure of the solvent as long as the dissolved components do not crystallize.
  • a constant change generally a decrease
  • the enthalpy of evaporation of the solvent also depends on the time.
  • the excess of the molecular enthalpy of the solvent in the solution is determined as the target variable from the characteristic deviations, based on the constant enthalpy of evaporation of the pure solvent. If the relative air humidity in the measuring chamber is set so that the vapor pressure of the solvent in the measuring chamber is lower than that above the saturated solution, an initially undersaturated solution shows an increase in the concentration over time as a result of the delayed nucleation kinetics of the crystalline phase , If a small single crystal of the solute of the above-mentioned typical dimensions is introduced into the undersaturated solution of known concentration at a suitable point in time, its dimensions are first reduced by dissolution until crystal growth takes place with the transition to the region of the supersaturated solution.
  • the mass of the crystal introduced is so small that the additional increase in the concentration of the solution caused by its dissolution remains negligible.
  • the dimensions of the introduced crystal recorded in time and determined the saturation concentration (point in the phase diagram) from the time of the transition from dissolution to growth.
  • the transition from dissolution to growth is registered as a significant kink in the pyrometric temperature measurement, since a change in the heat of solution used and released takes place.
  • the molecular enthalpy of solution follows from the data of the pyrometric temperature measurement, from which the temperature dependence of the saturation concentration (curve in the phase diagram) can be determined ,
  • All versions of the arrangement according to the invention can be expanded such that a plurality of smallest amounts of liquid are arranged in the same way in a common measuring chamber in such a way that the surface temperature and the evaporation or
  • Condensation kinetics can be measured. If there is a sample among these smallest amounts of liquid, the heat of vaporization and vapor pressure of which are known, the measurement data of the other samples can be related to this known sample, so that those measurement errors which are based on an inaccurate determination of Temperature and vapor pressure in the measuring chamber at a great distance from the smallest amounts of liquid are caused.
  • the time-dependent temperature difference ⁇ 7 to the surroundings measured on the working substance is a measure of the thermal output N (t) emitted or absorbed by the sample, provided quasi-steady-state conditions are met, ie when
  • N (t) changes so slowly in time that the course of N (t) at earlier times than the measuring time t only increases as a small correction
  • ⁇ ⁇ N (t) l (dN (t) / dt) ⁇ ⁇ l ⁇ 0 3 s.
  • the theoretical resolving power of the arrangement when measuring N (t) is limited by two fundamental influencing factors: the noise of the thermal sensor together with the downstream electronics and the accuracy of the determination of the evaporation rate.
  • a highly sensitive thermal sensor with a maximum spectral sensitivity in the wavelength range of the maximum of the radiation of the black body at room temperature, ie in the spectral range around 10 ⁇ m or above, is used for the pyrometric temperature measurement. This ensures that the surface temperature of the hanging drop is largely independent of the special composition of the aqueous solution.
  • a commercial thermal sensor that does not require cooling is suitable for this. Its time constant is approximately 60 ms.
  • the dynamic range of this thermal sensor is> 10 5 .
  • the detection sensitivity of the thermal sensor was determined in practical operation with a device working on a hanging drop to 170 ⁇ V / K.
  • a noise-related measurement error of ⁇ 0.5 ⁇ V of the registered voltage values results, corresponding to a measurement error of the registered temperature of ⁇ 3-10 -3 K per individual measurement.
  • the temperature data are adapted to the ideal theoretical course over characteristic time intervals of length ⁇ .
  • FIG. 1 shows a first arrangement according to the invention, in which the sample is present as a hanging drop
  • FIG. 2 shows a second arrangement according to the invention, in which the sample liquid is in a nappy-shaped container
  • FIG. 3 shows a third arrangement according to the invention with direct measurement of the heat radiation.
  • Fig. 1 is a gas-tight measuring chamber 10 with a geometric axis XX by holding means 11 in two parts 101 and 102 divided, of which the upper part 102 can be placed on the lower part 101 after the preparations for the measurement have been carried out.
  • the holding means 11, which are designed as a structure or an intermediate floor with a central opening 111, are intended for holding an elliptical mirror 12 which fills the central opening 111 or is at least located therein and whose optical axis OO preferably coincides with the geometric axis XX.
  • the diameter of the drop 14 should be ⁇ 2 mm and the amount of sample liquid contained in it should be ⁇ 4 ⁇ l.
  • the drop 14 hangs freely and under the effect of gravity, vertically on a capillary 15, the diameter of which is ⁇ 300 ⁇ m, which is connected to a micropipette 17 via a (flexible) pipe or hose connection 16.
  • a measurement beam path 18, which is located essentially in the measurement chamber part 101 and which serves as optical elements, a light source 181, a beam splitter 182, a filter 183 and a lens 184 and an optical sensor 185 (for example a CCD camera) is used for the simultaneous determination of the drop diameter ) contains.
  • the drop 14 is illuminated by the light source 181 via the beam splitter 182 and the lens 184.
  • the measuring beam path 18 reflected and scattered at the drop 14 passes through the lens 184 and the beam splitter 182 to the sensor 185 and generates an image of the drop 14 there.
  • the optical filter 183 arranged in the measuring beam path 18 removes all interfering radiation which influences the thermal equilibrium of the drop 14 and its surroundings.
  • a cooling / heating system 19 which is controlled by a computer 21 using a temperature sensor 20, is used to maintain or regulate the temperature in the measuring chamber 10.
  • a moisture sensor 22 and a moisture sensor or dryer 23 are provided, which are also controlled by the computer 21.
  • the measurement data of the surface temperature from the thermal sensor 24 and the drop diameter, which changes over time, is recorded by sensor 185 and stored and evaluated in computer 21.
  • a measurement is carried out on a reference system which, apart from the same composition, contains no protein.
  • This reference measurement simplifies the task of determining the contributions to the measurement data that are directly related to the protein content of the solution.
  • all measurements are ended as soon as the drop volume has reached half the initial value or the concentration of the dissolved substances has reached twice the initial value. It takes 1620 s for the actual measurement and 2900 s for the reference measurement.
  • thermodynamic data which are determined by the protein content, can be determined from the time course of the measured values compared to those of the reference system.
  • L / kT 0.3% ⁇ the
  • both the measured values listed in the table and the corresponding difference amounts to the Reference measurements significantly higher than the noise-related measurement errors derived above.
  • the smallness of the measurement errors caused by noise is very important, for example, if, under the conditions of very slow droplet kinetics (temporal changes in the droplet radius ⁇ 10 ⁇ m / s), small differences (in the range of 1%) to corresponding reference measurements must be reliably determined.
  • FIG. 2 shows a measuring chamber 25 in which an upper part 251, which forms a hollow body, preferably a hollow cylinder, can be closed airtight by a base 252.
  • a rod-shaped holder 261 of a bowl 262 of an ultra-microbalance (precision scale) 26 is guided through the bottom 252, on which there is a cup or bowl 264 with a sample liquid 265, the capacity of which is 810 ⁇ l, directly or via a support 263 the well 264 is thermally insulated from its base.
  • the ultra-microbalance 26 is used to determine the sample mass; on the basis of the compensation principle, it keeps the vertical position of the meniscus of the liquid 265 constant due to its rigid coupling to the weighing pan 262 via the carrier 263.
  • the sample liquid 265 is located in the focal point (focal spot) FI or in the vicinity of an elliptical mirror 12 which is attached to the ceiling of the upper part 251 and in whose other focal point (focal spot) F2 and its immediate vicinity a thermal sensor 24 is arranged.
  • a temperature sensor 20 in the measuring chamber 25 with a heating / cooling system 19 and a humidity sensor 22 a humidification / drying system 23.
  • Both the systems like the Ultarini microbalance 26, are connected to a computer 21, which stores the measured values of the heating / cooling system 19 and the humidification / drying system 23 and controls both systems.
  • the measuring microscope 28 which in the exemplary embodiment can be an endoscope, changes in a crystal introduced into the sample liquid 265 with the manipulator 27 and in the dissolved substance can be observed.
  • the arrangement shown in FIG. 2 can also be used to measure the temporal changes in the sample volume and the temperature, and the vapor pressure and the specific heat of vaporization of the solvent of the substance and further thermodynamic parameters can be determined therefrom by means of the software contained in the computer 21.
  • the bottom has a central opening 253 and carries a moisture transmitter or dryer off-center. 23.
  • the holder 261 of a weighing pan 262, which is part of an ultra-microbalance 26, projects through the opening 253.
  • a carrier 263 of a small bowl 264 with a sample liquid 265 is arranged on the weighing pan 262.
  • the bowl 264 has the properties of a gray IR emitter.
  • the hollow cylinder 251 has two openings 254 and 255 for the insertion of an endoscope 28 and a manipulator 27; both can be moved in these openings 254, 255 in the direction of double arrows 30 and 29, respectively.
  • a cooling and heating system 19 in the form of a spiral attached to the cylinder side walls, a temperature sensor 20, a moisture sensor 22 and a thermal sensor 24 are all arranged in the hollow cylinder 251, all of which are connected to a computer 21 for control purposes.
  • the thermal sensor 24 is thermally insulated and decoupled, taking into account its maximum opening ratio, as close as possible to the carrier 263, in the present case approx. 1 mm below the carrier 263.
  • the distance between the thermal sensor 24 and the well 264 remains constant when the mass of the sample liquid 265 changes due to the compensation principle of the Ulframware balance 26.
  • the cooling and heating system 19 is controlled by the computer 21 in accordance with the temperature uptake of the transmitter 20 in order to maintain or regulate the temperature in the measuring chamber 25.
  • the moisturizer or dryer 23 is controlled by the computer 21 in accordance with the measured values of the transmitter 22 given to the computer 21 in order to maintain a constant gas moisture in the measuring chamber 25.
  • the measured values of the thermal sensor 24 and the balance 26 are likewise forwarded to the computer 21 and processed there for the generation, setting or display of heat quantities, vapor pressure, evaporation ring kinetics or thermodynamic parameters.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Investigating Or Analyzing Materials Using Thermal Means (AREA)

Abstract

L'invention concerne un ensemble permettant de mesurer des quantités de chaleur en mesurant simultanément les cinétiques d'évaporation et/ou de condensation de quantités minimales de liquide, afin de déterminer des paramètres thermodynamiques. La présente invention doit permettre de déterminer les faibles puissances thermiques, qui sont absorbées ou débitées par l'échantillon, ainsi que les petites différences en matière de puissances thermiques par rapport à une mesure de référence du même ordre de grandeur. A cet effet, une quantité minimale de liquide est située à l'intérieur d'une chambre de mesure à température et humidité atmosphérique constantes. Au moins un capteur de température permet une mesure répétée du rayonnement thermique émanant de cette quantité minimale de liquide. Un moyen de mesure sert également à déterminer un changement de quantité minimale de liquide en fonction du temps. De plus, un ordinateur, associé à ladite chambre de mesure, permet l'enregistrement, l'affichage, l'évaluation et/ou le traitement ultérieur des valeurs de mesure.
EP03739433A 2002-02-12 2003-02-11 Ensemble permettant de mesurer des quantites de chaleur en mesurant simultanement les cinetiques d'evaporation et/ou de condensation de quantites minimales de liquide, afin de determiner des parametres thermodynamiques Withdrawn EP1474667A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10206546 2002-02-12
DE10206546 2002-02-12
PCT/DE2003/000432 WO2003069292A1 (fr) 2002-02-12 2003-02-11 Ensemble permettant de mesurer des quantites de chaleur en mesurant simultanement les cinetiques d'evaporation et/ou de condensation de quantites minimales de liquide, afin de determiner des parametres thermodynamiques

Publications (1)

Publication Number Publication Date
EP1474667A1 true EP1474667A1 (fr) 2004-11-10

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EP03739433A Withdrawn EP1474667A1 (fr) 2002-02-12 2003-02-11 Ensemble permettant de mesurer des quantites de chaleur en mesurant simultanement les cinetiques d'evaporation et/ou de condensation de quantites minimales de liquide, afin de determiner des parametres thermodynamiques

Country Status (8)

Country Link
US (1) US7137734B2 (fr)
EP (1) EP1474667A1 (fr)
JP (1) JP2005517919A (fr)
CN (1) CN1630812A (fr)
AU (1) AU2003210143A1 (fr)
CA (1) CA2475793A1 (fr)
DE (2) DE10306077B4 (fr)
WO (1) WO2003069292A1 (fr)

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DE10306077A1 (de) 2003-08-28
DE10390520D2 (de) 2005-01-13
DE10306077B4 (de) 2007-04-26
JP2005517919A (ja) 2005-06-16
CA2475793A1 (fr) 2003-08-21
CN1630812A (zh) 2005-06-22
US7137734B2 (en) 2006-11-21
WO2003069292A1 (fr) 2003-08-21
US20050141587A1 (en) 2005-06-30
AU2003210143A1 (en) 2003-09-04

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