The ability to model and predict the behaviour of high-pressure alcohol and carbon dioxide mixtures is important for industrial purposes. The phase equilibria behaviour of four 8-carbon alcohols in super-critical carbon dioxide are measured to determine the effect of the hydroxyl group position on alcohol solubility. Experimental bubble- and dew point data are generated on a high pressure phase equilibrium cell for the systems 1-octanol, 2-octanol, 3-octanol and 4-octanol in supercritical carbon dioxide between 35 degrees C and 75 degrees C. 1-Octanol is shown to be the least soluble and, at 35 degrees C, exhibits a phase transition pressure 85 bar higher than that of 2-octanol. 1-Octanol also exhibits a temperature inversion near the critical temperature of carbon dioxide in the mixture critical region. 2-Octanol possesses marginally higher phase transition pressures than 3-octanol which, in turn, possesses marginally higher phase transition pressures than 4-octanol. This difference in phase equilibria is believed to result from a difference in polarity. Shifting the hydroxyl group from the first to the second carbon atom causes a large decrease in polarity and increase in solubility. Further movements toward the molecule centre result in progressively smaller polarity reductions and solubility increases, producing phase boundaries that coincide or differ minimally. (C) 2008 Elsevier B.V. All rights reserved.