Massive binary systems are important laboratories in which to probe the properties of massive stars and stellar physics in general. In this context, we analysed optical spectroscopy and photometry of the eccentric short-period early-type binary HD 152218 in the young open cluster NGC 6231. We reconstructed the spectra of the individual stars using a separating code. The individual spectra were then compared with synthetic spectra obtained with the CMFGEN model atmosphere code. We furthermore analysed the light curve of the binary and used it to constrain the orbital inclination and to derive absolute masses of 19.8 +/- 1.5 and 15.0 +/- 1.1 solar masses. Combining radial velocity measurements from over 60 years, we show that the system displays apsidal motion at a rate of (2.04^{+.23}_{-.24}) degree/year. Solving the Clairaut-Radau equation, we used stellar evolution models, obtained with the CLES code, to compute the internal structure constants and to evaluate the theoretically predicted rate of apsidal motion as a function of stellar age and primary mass. In this way, we determine an age of 5.8 +/- 0.6 Myr for HD 152218, which is towards the higher end of, but compatible with, the range of ages of the massive star population of NGC 6231 as determined from isochrone fitting.
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