Experimental methods for determination of vapor/sublimation pressures
There is no single experimental technique capable of measuring VP in the
whole pressure range of interest
- from fragmets of pascal for many solids and also for many liquids near the triple point temperature
- to hudreds of kilopascals or even several megapascals near the critical temperature
The following sources describe respective techniques in detail:
1. Ambrose,
D., Vapor pressure. In Experimental
Thermodynamics of Non-reacting Systems, Le Neindre, B.; Vodar, B., Eds. Butterworths:
London, 1975; pp 607-656.
I.
Introduction
II. Static Measurements
III.
The Isoteniscope and Related Methods
IV.
Static Measurements at Elevated Temperatures and Pressures
V.
The Critical Point
VI.
Effect of the Presence of Mercury
VII.
Vapor Pressures of Liquefied Gases
VIII.
Effect of Thermal Transpiration
IX. Comparative
Static Measurements
X.
Static Measurements at Very Low Pressures
XI. Use
of Radioactive Tracers
XII.
Ebulliometric Measurements
XIII.
Ebulliometric Measurements at Pressures below 2 kPa
XIV. Method
of Ramsay and Young
XV.
Dynamic Measurements without a Buffer Gas
XVI.
The Quasi-static Method
XVII. Measurement
of the Force Exerted by the Vapor
XVIII. Evaporation
Methods for Low Pressures
XIX. Gas-saturation
Method
XX.
Differential Thermal Analysis
XXI. Gas
Chromatography
XXII. Mass
Spectrometry
XXIII. Vapor
Pressures of Mixtures
2. Carson, A. S., The measurement of
vapor pressure. In Thermochemistry and
Its Applications to Chem./Biochem. Systems, Ribeiro da Silva, M. A. V., Ed.
D.Riedel Publ. Comp.: 1984; pp 127-41.
Manometric
Transpiration
Ebulliometric
Vibrating fibre
Thermistor
Knudsen effusion
3. Delle Site, A., The vapor pressure of environmentally
significant organic chemicals: A review of methods and data at ambient
temperature. J. Phys. Chem. Ref. Data 1997, 26, 157-193.
2.
Experimental methods
2.1. Direct
experimental methods
2.1.1.
Manometric methods
2.1.2.
Boiling point at reduced pressures
2.1.3.
Effusion
2.1 .4. Gas saturation
2.1.5.
Partition coefficient
2.1.6. Other
methods
2.2.
Indirect experimental methods
2.2.1.
Relative volatilization rate
2.2.2.
Chromatographic methods
4. Verevkin, S. P., Chapter 2. Phase Changes in Pure Component Systems: Liquids and Gases
In Measurement of the Thermodynamic Properties
of Multiple Phases, Weir, R. D.; de Loos, T. W., Eds.
Elsevier: Amsterdam,
2005; pp 5-30.
2.1 Static Measurements
2.2 Ebulliometry
2.3 Knudsen Effusion Methods for Vapour Pressure Measurement
2.3.1 Conventional Mass-Loss Technique
2.3.2 Torsion-Effusion Method
2.3.3 Simultaneous Torsion and Mass-Loss Effusion Techniques
2.3.4 Isothermal Knudsen Effusion Method in Thermogravimetric-Type Apparatus
2.3.5 Non-Isothermal Knudsen Effusion Method in TG-Type Apparatus
2.3.6 Mass-Loss Knudsen Technique with a Quartz Crystal Microbalance
2.3.7 Mass-Loss Knudsen Technique by Heat-Conducting Calorimetry
2.3.8 Mass-Loss Knudsen Technique with a Mass Spectrometry Method
2.3.9 Knudsen Cell with Differential Scanning Calorimetry
2.4 Langmuir Effusion Methods for Vapour Pressure Measurement
2.5 The Transpiration Method
2.6 Chromatographic Methods
2.6.1 Headspace Analysis
2.6.2 GC-Correlations with Retention Times and Vapour Pressures of Reference
Compounds
2.6.3 GC-Correlations with Net Retention Times
2.7 Calorimetric Measurements of the Enthalpy of Vaporization
2.7.1 Adiabatic Calorimeters
2.7.2 Drop Calorimetry Method
2.7.3 Differential Calorimetry
5. Verevkin, S. P.; Zaitsau, D. H.;
Schick, C.; Heym, F., Chapter 1 Development of Direct and Indirect Methods for the Determination of Vaporization Enthalpies of Extremely Low-Volatile Compounds.
In Handbook
of Therm. Anal. and Calorimetry, Vol. 6, Vyazovkin, S.; Koga, N.; Schick,
C., Eds.
Elsevier: Amsterdam, 2018; Vol. 6, pp 1-46.
1.2 KINETIC
METHODS OF THERMAL ANALYSIS (VAPORIZATION) OF LOW-VOLATILE COMPOUNDS
1.3
TEMPERATURE PROGRAMED DESORPTION COMBINED WITH LOSMS
1.4 THERMOGRAVIMETRIC METHODS FOR THE DETERMINATION OF VAPOR PRESSURES AND
THERMAL
STABILITY OF HIGH BOILING SUBSTANCES
1.5 ABSOLUTE
VAPOR PRESSURES OF EXTREMELY LOW-VOLATILE COMPOUNDS FROM FSC
1.6
DIFFERENTIAL SCANNING CALORIMETRY (DSC)
1.7 STATIC
VAPOR PRESSURE MEASUREMENTS
1.8 CALVET
VAPORIZATION DROP MICROCALORIMETRY
1.9 TRANSPIRATION METHOD
1.10 UV
SPECTROSCOPY FOR VAPORIZATION STUDIES OF LOW-VOLATILE COMPOUNDS
1.11
CORRELATION GAS CHROMATOGRAPHY
1.12 HOW TO
ADJUST VAPORIZATION ENTHALPY VALUES TO THE REFERENCE TEMPERATURE
298.15 K PROPERLY?
1.13 INDIRECT DETERMINATION OF MOLAR ENTHALPIES OF VAPORIZATION OF ILs FROM
CALORIMETRIC
RESULTS
6. Zaitsau,
D. H.; Paulechka, E., CHAPTER 15 Experimental Determination of Vapor Pressures.
In Gibbs Energy and Helmholtz Energy:
Liquids, Solutions and Vapours, The Royal Society of Chemistry: 2022; pp
425-448
1 Static Method
1.1 Manometric Setups
1.2 Static
Technique with Determination of the Gas-phase Concentration
2 Boiling Point
Techniques
2.1 Ebulliometry
2.2
Quasi-static Methods
3 Dynamic
Methods
3.1 Transpiration Technique
3.2 Thermogravimetric Analysis
(TGA)
3.3 Fast Scanning Calorimetry
(FSC)
4 Kinetic
Methods
7. Bilde, M.; Barsanti, K.; Booth, M.; Cappa, C. D.; Donahue, N.
M.; Emanuelsson, E. U.; McFiggans, G.; Krieger, U. K.; Marcolli, C.; Topping,
D.; Ziemann, P.; Barley, M.; Clegg, S.; Dennis-Smither, B.; Hallquist, M.;
Hallquist, Å. M.; Khlystov, A.; Kulmala, M.; Mogensen, D.; Percival, C. J.;
Pope, F.; Reid, J. P.; Ribeiro da Silva, M. A. V.; Rosenoern, T.; Salo, K.;
Soonsin, V. P.; Yli-Juuti, T.; Prisle, N. L.; Pagels, J.; Rarey, J.; Zardini,
A. A.; Riipinen, I., Saturation Vapor Pressures and Transition Enthalpies of
Low-Volatility Organic Molecules of Atmospheric Relevance: From Dicarboxylic
Acids to Complex Mixtures. Chemical
Reviews 2015, 115, 4115-4156.
Most methods in this review are not covered by book chapters and reviews above:
3. Experimental Methods
3.1. Knudsen-Cell-Based Methods
3.1.1. Knudsen Mass Loss Methods
3.1.2. Knudsen Effusion Mass Spectrometry
3.2. Single-Particle Methods
3.2.1. Electrodynamic Balance
3.2.2. Optical Tweezers
3.3. Particle Size Distribution Methods
3.3.1. Flow Tube Tandem Differential MobilityAnalyzer
3.3.2. Volatility Tandem Differential MobilityAnalyzer
3.3.3. Integrated Volume Method
3.4. Thermal Desorption Methods
3.4.1. Thermal Desorption Particle Beam Mass Spectrometry
3.4.2. Temperature-Programmed Desorption Proton Transfer Chemical Ionization Mass Spectrometry
3.4.3. Atmospheric Solids Analysis Probe Mass Spectrometry