We test the recently developed macroscopic approach to modeling chemistry in DSMC [Lilliley & Macrossan, Physics of Fluids, 16(6), 2054-2066 (2004)], by simulating the flow of rarefied dissociating nitrogen over a blunt cylinder. In this macroscopic method, chemical reactions are decoupled from the collision routine. Molecules are chosen to undergo dissociation at each time step, after the collisions are calculated. The required number of reaction events is calculated from macroscopic reaction rate expressions with macroscopic information taken from the time-averaged cell properties. One advantage of this method is that "state-of-the-art" macroscopic information about reaction rates can be used directly in DSMC in the same way as in continuum codes. Hybrid Navier-Stokes/DSMC codes can therefore easily use the same chemical models in both rarefied and continuum flow regions. Here we show that the macroscopic method can capture dissociation-vibration (DV) coupling, which is an important effect in vibrationally cold blunt body flows because it results in increased surface heat fluxes. We use the macroscopic method with Park's two-temperature rate model, often used in continuum studies, to capture DV coupling in DSMC. This produces a flowfield in reasonable agreement with that calculated using the conventional collision-based threshold line dissociation model.