The acentric factor was put forward as a means of representing the non-sphericity and

polarity of many compounds. The original Equation of State PV=nRT was based on a
model of hard spheres which behaved in a classical and predictable fashion. The vast
majority of compounds are, unfortunately, far from ideal and far from spherical. The
acentric factor provides a number which can be used in the equation of state to match
predicted PT behaviour with reality.

To quote the authors in !olecular Thermodynamics of "luid-Phase Equilibria by #
Prausnit$ and %. &. 'ichtenthaler.
"Acentric Factors are arbitrary and chosen for convenience"

There was originally an empirical basis for the value of the acentric value. (ased on the
observed deviation of some fluids from that predicted for simple fluids, Pit$er proposed
an e)perimental method for determining the acentric factor.