A pressure and flow calculation technique can be used in a distributed process network simulation system that uses the sequential solving method to perform better or faster simulations of a process flow, especially with respect to process junction nodes at which flow either converges or diverges. The pressure and flow variable determination technique uses a grouped node identification technique that identifies a local set of nodes for each junction node of the process network to use when solving for the pressure at the junction node, a grouped node iteration technique that uses the grouped set of nodes at each junction node to perform iterative pressure calculations at the junction node, and a flow-based pressure calibration technique at each junction node to enable the system to perform highly accurate pressure and flow variable determination at each junction node in real-time.