Equilibrium distributions of key components of spearmint oil in sub/supercritical carbon dioxide

Effects of temperature (at 35, 45 or 55°C) and pressure (10–110 atm) on the relative distribution coefficients of the twelve key components of spearmint oil (essential oil ofMentha cardiaca; Scotch spearmint) at equilibrium in dense CO₂ were investigated under conditions ranging from subcritical to supercritical regions. Effects of vapor pressure, molecular weight and polarity of the key components on their equilibrium distributions in sub/supercritical CO₂ are discussed. At 35°C, all key components of spearmint oil are equally soluble in dense CO₂ within the 12–102 atm pressure region. At 45 and 55°C, the key components are equally soluble for pressures greater than about 60 atm. However, around either 45°C/27 atm or 55°C/35 atm conditions, the relative distribution coefficients of all monoterpene hydrocarbons and of isomenthone (an oxygenated monoterpene) exhibit maxima, which are due to significantly higher vapor pressures of these components and significantly lower solvating power of the dense-gas solvent at these particular temperatures and pressures. Vapor-pressure effects, coupled with the decrease in solvating power, dominate the effects of polarity and molecular mass of the key components. Deterpenation of spearmint oil with dense CO₂ is possible around either 45°C/27 atm or 55°C/35 atm, where the monoterpene hydrocarbons tend to concentrate in the CO₂-rich phase.