Density is customarily defined as the amount of mass contained in a unit volume of fluid. Density is the single-most important property of a fluid, once we realize that most other properties can be obtained or related to density. Both specific volume and density — which are inversely proportionally related to each other — tell us the story of how far apart the molecules in a fluid are from each other. For liquids, density is high — which translates to a very high molecular concentration and short intermolecular distances. For gases, density is low — which translates to low molecular concentrations large intermolecular distances.

The question then is: Given this, how can we obtain this all-important property called density? This takes us back to Equations of State (EOS). Since very early times, there have been correlations for the estimation of density of the liquids (oil, condensates) and gases/vapors (dry gases, wet gases). In modern times, equations of state (EOS) are a natural way of obtaining densities. The density of the fluid ‘f’ is calculated using its compressibility factor (Z_{f}) as predicted by an appropriate equation of state. From the real gas law, the density can be expressed as:

where: MW_{f} is the molecular weight of fluid ‘f’. Expression (18.2) is used for both the gas and liquid density. In either case, the proper value for MW_{f} (either MW_{g} or MW_{l}) and Z_{f} (either Z_{g} or Z_{o}) has to be used. This takes us back to the discussion of equations of state. From Equation (18.2) it is clear that all that we need is the Z-factor.

The all-important parameter to calculate density is the Z-factor, both for the liquid and vapor phases. The relation between liquid behavior and Z-factor is not obvious, because Z-factor has been traditionally defined for gases. However, we can get “Z” for liquids. “Z” is, indeed, a measure of departure from the ideal gas behavior. Fair enough, for defining “Z” for liquids, we still measure the departure of liquid behavior from ideal gas behavior. A “liquid state” is a tremendous departure from ideal-gas conditions, and as such, “Z” for a liquid is always very far from unity. Typical values of “Z” for liquids are small.

Equations of State have proven very reliable for the estimation of vapor densities, but they do not do as good a job for liquid densities. There is actually a debate among different authors about the reliability of Z-factor estimations for liquids using EOS. In fact, people still believe the EOS are not reliable for liquid density predictions and that we should use correlations instead. However, Peng-Robinson EOS provides fair estimates for vapor and liquid densities as long as we are dealing with natural gas and condensate systems.

Empirical correlations for Z-factor for natural gases were developed before the advent of digital computers. Although their use is in decline, they can still be used for fast estimates of the Z-factor. The most popular of such correlations include those of Hall-Yarboroug and Dranchuk-Abou-Kassem.

Chart look-up is another means of determining Z-factor of natural gas mixtures. These methods are invariably based on some type of corresponding states development. According to the theory of corresponding states, substances at corresponding states will exhibit the same behavior (and hence the same Z-factor). The chart of Standing and Katz is the most commonly used Z-factor chart for natural gas mixtures.

Methods of direct calculation using corresponding states have also been developed, ranging from correlations of chart values to sophisticated equation sets based on theoretical developments.

However, the use of equations of state to determine Z-factors has grown in popularity as computing capabilities have improved. Equations of state represent the most complex method of calculating Z-factor, but also the most accurate. A variety of equations of state have been developed to describe gas mixtures, ranging from the ideal EOS (which yields only one root for the vapor and poor predictions at high pressures and low temperatures), cubic EOS (which yields up to three roots, including one for the liquid phase), and more advanced EOS such as BWR and AGA8.

### References:

Hall K., and Yarborough, L. (1973), “A New Equation of State for Z-factor Calculations”, Oil and Gas Journal, June 1973, pp. 82-92.

Dranchuk, P. and Abou-Kassem, J. (1975), “Calculation of Z-factors for Natural Gases Using Equations-of-State”, JCPT, July-September 1975, p. 34-36.

Standing, M. and Katz, D. (1942), “Density of Natural Gases”, Trans. AIME, v. 146, pp. 140-149.