An example of an amine containing drug is Procaine which contains 2 amine groups.When HCl is added to procaine I think the tertiary amine is protonated as it has more electrons and the benzene amine is delocalised by resonance with the ring so is less available for proton bonding but how can I distinguish between the protonated tertiary amine(NH+) and the protonated primary amine(NH3+) in a HNMR or CNMR spectra for procaine?

Are there any other distinguishable chemical shifts or splitting patterns in hnmr or cnmr spectra for NH+ or NH3+ protons(or carbons attched to them)? Does the Cl- have any impact? Very limited knowledge of nmr so detailed explanations please!