Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

The influence of the halogen size in the volatility and melting of methyl p-halobenzoic esters and of their parent acids

Almeida, A. R. R. P.[Ana R.R.P.], Monte, M. J. S.[Manuel J. S.]
J. Chem. Thermodyn. 2013, 57, 160-168
ABSTRACT
The vapour pressures of the condensed phases of the methyl esters of p-halobenzoic acids were measured over wide temperature ranges. The results enabled the determination of the standard molar entropies and enthalpies of sublimation and of vapourisation, at T = 298.15 K, of these four compounds. The temperatures and molar enthalpies of fusion were determined using differential scanning calorimetry and were compared with the values derived from the vapour pressure measurements. Temperature and enthalpy of fusion of p-chlorobenzoic acid were also measured using DSC. The enthalpies of the intermolecular hydrogen bonds O H O formed in the crystals of the parent halobenzoic acids were calculated. From the available results for these compounds and from the ones determined in this work, several correlations involving thermodynamic properties of sublimation and fusion as well as the volume of the halogen substituent were derived.
Compounds
# Formula Name
1 C8H7ClO2 methyl 4-chlorobenzoate
2 C8H7IO2 methyl p-iodobenzoate
3 C8H7FO2 methyl p-fluorobenzoate
4 C8H7BrO2 methyl 4-bromobenzoate
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 1
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 1
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Vapor or sublimation pressure, kPa ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Gas
  • Closed cell (Static) method
  • 19
  • POMD
  • 1
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • Closed cell (Static) method
  • 27
  • POMD
  • 2
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Vapor or sublimation pressure, kPa ; Crystal
  • Crystal
  • Liquid
  • Gas
  • DSC
  • 1
  • POMD
  • 2
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 2
  • Vapor or sublimation pressure, kPa ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Gas
  • Closed cell (Static) method
  • 30
  • POMD
  • 2
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • Closed cell (Static) method
  • 12
  • POMD
  • 3
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 3
  • Vapor or sublimation pressure, kPa ; Crystal
  • Crystal
  • Liquid
  • Gas
  • DSC
  • 1
  • POMD
  • 3
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 3
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • Closed cell (Static) method
  • 42
  • POMD
  • 4
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 4
  • Vapor or sublimation pressure, kPa ; Crystal
  • Crystal
  • Liquid
  • Gas
  • DSC
  • 1
  • POMD
  • 4
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 4
  • Vapor or sublimation pressure, kPa ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Gas
  • Closed cell (Static) method
  • 29
  • POMD
  • 4
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • Closed cell (Static) method
  • 13