This study of the N2O4-NO2 equilibrium allows the student to measure several thermodynamic quantities on a gas phase equilibrium and provides extensive laboratory experience in physical chemistry.
Within the frame of the scheme shown in IV, this conclusion is of course only valid if theinterconversions shown occur in the excited state. It is also perhaps interesting to note that the observed interconversion between 1 and 2 may also be rationalized through the initial excited state generation of 7 and 8 depicted in Scheme IV followed by electronic deactivation of these species and subsequent thermal, symmetry-controlled, closure to 2 and 1, respectively. Nonetheless, we tend to favor the mechanistic interpretation of Scheme IV owing to the obvious inability of the "thermal" process to readily accommodate the substantial photostationary predominance of the cis isomer irrespective of N substituent.
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