Calorimetric study of alternating copolymer of bicyclo[2,2,1]-hepta-2,5-diene and carbon monoxide in the range from T → 0 to 510 K

Abstract

By adiabatic vacuum and dynamic calorimetry, the temperature dependence of heat capacity for alternating copolymer of bicyclo[2,2,1]-hepta-2,5-diene and carbon monoxide has been determined over the 6–510 K range with an uncertainty of 0.2–0.5% between 6 and 350 K and 0.5–1.5% from 330 to 510 K. In the above temperature ranges, the physical transformations of the copolymer have been detected and their thermodynamic characteristics have been estimated. In a calorimeter with a static bomb and an isothermal shield, the energy of combustion of the copolymer has been measured at 298.15 K. Based on the experimental data, the thermodynamic functions of the copolymer, namely, the heat capacity C p ∘ ( T ) , enthalpy H°( T) − H°(0), entropy S°( T) − S°(0) and Gibbs function G°( T) − H°(0) have been determined for the range from T → 0 to 400 K. The enthalpy of combustion Δ c H° and the thermodynamic parameters Δ f H°, Δ f S°, Δ f G° and ln K f ∘ of reaction of formation of the copolymer from simple substances at T = 298.15 K and p = 0.1 MPa have been calculated. The data cited in the present work and literature data were used to calculate the thermodynamic characteristics of the alternating copolymerization in bulk of bicyclo[2,2,1]-hepta-2,5-diene and CO in the 0–340 K range at standard pressure as well as to compare them with the thermodynamic characteristics of the synthesis of isomeric polyketone.