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Empirical formulae are presented for calculating vapor-liquid equilibria (VLE) in the CO 2 -H 2 O system at 10 temperatures between 110 and 350 °C. At each temperature, separate functions are used to represent the bubble- and dew-point boundary curves that: originate at the saturation vapor pressure of water (P sat;  H₂O ) at X CO₂  = 0; diverge with increasing pressure up to ~P(X max  CO₂ ) where ∂P/∂X CO₂  = +∞ along the dew-point curve; then converge with increasing pressure above P(X max  CO₂ ). At temperatures below 265 °C and pressures &gt; P(X max  CO₂ ), the compositions of coexisting liquid and vapor [X CO₂  L(V)  and X CO₂  V(L) ] do not converge completely with increasing pressure due to the absence of critical behavior. Thus, relatively simple functions suffice to accurately represent VLE at those temperatures. In contrast, at T &gt; 265 °C, X CO₂  L(V)  and X CO₂  L(V)  converge rapidly as P approaches P c  (the critical pressure in the CO 2 -H 2 O system at a given temperature between 265 and 374 °C and P ≤ 215 MPa). For those temperatures, therefore, more complex VLE formulae are required to achieve close representation of phase relations. For dew-point equations, this includes adding an exponential “correction term” to ensure that ∂P/∂X CO₂  = 0 at the critical points indicated by corresponding bubble-point functions.

The CO 2 –H 2 O system: IV. Empirical, isothermal equations for representing vapor-liquid equilibria at 110–350 °C, P ≤ 150 MPa