A classial method to determine the hydration degree of Portland Cement is the chemical bound water or non evaporable water describes by Powers in 1949. You can found it in the PCA bookstore
So many ways could be used to determine the degree of hydration. However the best is using the Thermal gravimetric analysis. Sometimes certain compounds may not be determined so, there is always the need to corroborate TGA results with some form of spectroscopic studies such as solid state MAS NMR and FTIR. In other cases, shrinkage studies (total and autogeneous) have been used to analyse the extent of hydration
It is not clear what you mean by "determine the hydration of cement", you can use isothermal calorimetry test to measure the heat of hydration, you can also use other techniques such as computed tomography or SEM to see changes during hydration, it should be clear what aspect of hydration you want to focus on it.