RSY,
In general, pressure vessels can be subject to a variety of loading conditions. When you enter a value for internal pressure, that value along with other data will be used to determine the total pressure that will be used in the design equations.
If you enter in a value of external pressure, this value will be used to determine the external MAWP and required thickness.
Please note that the design for these cases is mutually exclusive (for the most part).
In conclusion, there is nothing to keep you from doing this if the vessel does not have an internal pressure design consideration.
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Scott MayeuxCADWorx & Analysis Solutions
Intergraph Process, Power, & Marine