Electrochemical doping of bundles of unopened nanotubes with bisulfate ions (acceptor) and Lithium ions (donor) has been studied using coulometry and Raman spectroscopy. The interstitial channels between the tubes in the "rope lattice" or bundles provide a new graphitic environment for intercalation. Using concentrated (18 M) sulfuric acid, a spontaneous charge-transfer reaction is observed prior to the application of the electrochemical driving force, in sharp contrast to previous studies in graphite-H2SO4 system. Using Raman scattering, we were able to separate the spontaneous and electrochemical contributions to the overall charge transfer between the intercalant and the rope lattice.