Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

Isomerization effect on the heat capacities and phase behavior of oligophenyls isomers series

Rodrigues, A. S. M. C.[Ana Sofia M.C.], Rocha, M. A. A.[Marisa A.A.], Santos, L. M. N. B. F.[Luis M. N. B. F.]
J. Chem. Thermodyn. 2013, 63, 78-83
ABSTRACT
In this work an analysis of the effect of ortho, meta and para isomerization and the number of phenyl rings on the heat capacity and phase behavior of oligophenyls, n(Ph), from 3 up to 5 is presented. The phase behavior from 298.15 K to the melting temperature was analysed by differential scanning calorimetry (DSC) and the temperature, enthalpies and entropies of fusion along the oligophenyls series were determined. With the exception of terphenyl isomers, the meta oligophenyls series show lower melting temperatures and higher entropies of fusion. Heat capacities, at T = 298.15 K, were determined for the ortho and meta quaterphenyl and p-quinquephenyl oligomers by means of high precision drop calorimetry. The heat capacities of the ortho and meta isomers are systematically lower than those of the corresponding para isomers. It was found that the subtle isomerization effect on the heat capacity is partially related to the ring rotation restrictions in their supramolecular structure and increases with the increase of the number of phenyl rings.
Compounds
# Formula Name
1 C18H14 o-terphenyl
2 C18H14 m-terphenyl
3 C18H14 p-terphenyl
4 C24H18 o-quaterphenyl
5 C24H18 metaquaterphenyl
6 C24H18 1,1':4',1'':4'',1'''-quaterphenyl
7 C30H22 o-quinquephenyl
8 C30H22 1,1':3',1'':3'',1'':3'',1''''-quinquephenyl
9 C30H22 1,1':4',1'':4'',1''':4''',1''''-quinquephenyl
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
  • Triple point 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
  • 2
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 3
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 3
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 4
  • Molar heat capacity at constant pressure, J/K/mol ; Crystal
  • Temperature, K; Crystal
  • Pressure, kPa; Crystal
  • Crystal
  • Drop calorimetry
  • 1
  • POMD
  • 4
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 4
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 5
  • Molar heat capacity at constant pressure, J/K/mol ; Crystal
  • Temperature, K; Crystal
  • Pressure, kPa; Crystal
  • Crystal
  • Drop calorimetry
  • 1
  • POMD
  • 5
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 6
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 6
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 7
  • Molar heat capacity at constant pressure, J/K/mol ; Crystal
  • Temperature, K; Crystal
  • Pressure, kPa; Crystal
  • Crystal
  • Drop calorimetry
  • 1
  • POMD
  • 7
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 7
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 8
  • Molar heat capacity at constant pressure, J/K/mol ; Crystal
  • Temperature, K; Crystal
  • Pressure, kPa; Crystal
  • Crystal
  • Drop calorimetry
  • 1
  • POMD
  • 8
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 8
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 9
  • Molar heat capacity at constant pressure, J/K/mol ; Crystal 2
  • Temperature, K; Crystal 2
  • Pressure, kPa; Crystal 2
  • Crystal 2
  • Drop calorimetry
  • 1
  • POMD
  • 9
  • Triple point temperature, K ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 9
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Nematic liquid crystal
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 9
  • Triple point temperature, K ; Nematic liquid crystal
  • Nematic liquid crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 9
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 9
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Nematic liquid crystal
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 9
  • Molar enthalpy of transition or fusion, kJ/mol ; Nematic liquid crystal
  • Nematic liquid crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1