Journal of Thermal Analysis and Calorimetry

, Volume 136, Issue 3, pp 1163–1171 | Cite as

A new accurate calorimetric method for the enthalpy of fusion measurements up to 1000 °C

  • Refat RazoukEmail author
  • Olivier Beaumont
  • Bruno Hay


A new metrological approach is proposed by the Laboratoire National de Metrologie et d’Essais to lower the uncertainty of measurements of enthalpy of fusion from 23 to 1000 °C. It consists, as in our previous works, in putting the studied sample inside a calibration crucible and in performing the heat calibration of the calorimeter by electrical substitution at two temperatures before and after the temperature of fusion of the sample during the same low-rate heating run. The novelty lies in the “electrical compensation” of the endothermic reaction of fusion. The quantification of the electrical energy needed to melt the sample, which can be measured with high accuracy, and the integrated remaining heat flow rate divided by the calibration factor (sensitivity) of the calorimeter at the temperature of fusion, leads to the determination of the enthalpy of fusion of the sample with low uncertainty. This methodology reduces the influence of the uncertainty component associated with the area of the peak of fusion by comparison with the former procedure when no electrical compensation was applied. The relative expanded uncertainty (k = 2) associated with the enthalpy of fusion measurements, performed using this facility and this new procedure, has been assessed to be < 0.2% for tin and indium and to be about 0.3% in the case of silver.


Enthalpy of fusion Calibration Electrical compensation Uncertainty 


  1. 1.
    Della Gatta G, Richardson MJ, Sarge SM, Stølen S. Standards, calibration, and guidelines in microcalorimetry. Part 2. Calibration standards for differential scanning calorimetry (IUPAC Technical Report). Pure Appl Chem. 2006;78:1455–76.CrossRefGoogle Scholar
  2. 2.
    Sarge SM, Höhne G, Hemminger W. Calorimetry: fundamentals, instrumentation and applications. Weinheim: Wiley; 2014.CrossRefGoogle Scholar
  3. 3.
    Razouk R. Mise en place de références métrologiques en enthalpie de fusion entre 23°C et 1000°C. Presses Ac. 2014.Google Scholar
  4. 4.
    Höhne G, Hemminger WF, Flammersheim HJ. Differential scanning calorimetry. Berlin: Springer; 2003.CrossRefGoogle Scholar
  5. 5.
    Sarge SM, Hemminger W, Gmelin E, Höhne GWH, Cammenga HK, Eysel W. Metrologically based procedures for the temperature, heat and heat flow rate calibration of DSC. J Therm Anal. 1997;49:1125–34.CrossRefGoogle Scholar
  6. 6.
    Stølen S, Grønvold F. Critical assessment of the enthalpy of fusion of metals used as enthalpy standards at moderate to high temperatures. Thermochim Acta. 1999;327:1–32.CrossRefGoogle Scholar
  7. 7.
    Haloua F, Hay B, Foulon E. Uncertainty analysis of theoretical methods for adiabatic temperature rise determination in calorimetry. J Therm Anal Calorim. 2013;111:985–94.CrossRefGoogle Scholar
  8. 8.
    Legendre B, Girolamo D, Le Parlouer P, Hay B. Determination of specific heat as function of temperature by drop calorimetry. Rev française métrologie. 2006;1:23–30.Google Scholar
  9. 9.
    Razouk R, Hay B, Himbert M. A new in situ electrical calibration system for high temperature Calvet calorimeters. Rev Sci Instrum. 2013;84:094903.CrossRefGoogle Scholar
  10. 10.
    Razouk R, Hay B, Himbert M. Toward new high temperature reference materials for calorimetry and thermal analysis. In: Filtz J-R, Larquier B, Claudel P, Favreau J-O (eds) EPJ web conference. 2014;77:00019.Google Scholar
  11. 11.
    Razouk R, Hay B, Himbert M. Uncertainty assessment of enthalpy of fusion measurements performed by using an improved Calvet calorimeter. Metrologia. 2015;52:717–29.CrossRefGoogle Scholar
  12. 12.
    van der Plaats G. A theoretical evaluation of a heat-flow differential scanning calorimeter. Thermochim Acta. 1984;72:77–82.CrossRefGoogle Scholar
  13. 13.
    JCGM. 100:2008 Evaluation of measurement data—guide to the expression of uncertainty in measurement; 2008.Google Scholar
  14. 14.
    Razouk R, Hay B, Hameury J, Himbert M. Qualification of a heat-flux calorimeter for accurate measurements of the enthalpy of fusion up to 1000°C. Rev française métrologie. 2015;2:25–32.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Laboratoire National de Metrologie et d’Essais, Laboratoire Commun de Metrologie (LNE-LCM)Scientific and Industrial Metrology CentreParisFrance

Personalised recommendations