We report millimeter line observations of CO, (CO)-C-13, SiO, SiC2, CN
, HCN, HNC, HCO+, CS, and HC3N to study the chemistry in planetary neb
ulae (PNe) with massive envelopes of molecular gas. The sample observe
d consists of representative objects at different stages of developmen
t in order to investigate evolutionary effects: the proto-PNe CRL 2688
and CRL 618, the young PN NGC 7027, and the evolved PNe NGC 6720 (the
Ring), M4-9, NGC 6781, and NGC 7293 (the Helix). The observations con
firm that the chemical composition of the molecular gas in PNe is radi
cally different from that in interstellar clouds and the circumstellar
envelopes of Asymptotic Giant Branch (AGE) stars. There are also clea
r trends in the chemical evolution of the envelopes. As a star evolves
beyond the AGE, through the proto-PN and PN phases, the abundances of
SiO, SiC2, CS, and HC3N decrease, and they are not detected in the PN
e, while the abundances of CN, HNC, and HCO+ increase dramatically. On
ce a PN has formed, the observed abundances in the molecular clumps of
the envelope remain relatively constant, although HNC is anomalously
underabundant in NGC 7027. In the evolved PNe, CN is about an order of
magnitude more abundant than HCN, HNC, and HCO+, and the average abun
dance ratios are CN/HCN = 9, HNC/HCN = 0.5, and HCO+/HCN = 0.5. These
ratios are, respectively, one, two, and three orders of magnitude high
er than in the prototypical AGE envelope IRC+10216. The C-12/C-13 rati
os are approximate to 10-25, within the large range found in AGE envel
opes. The chemical evolution of the envelopes likely occurs through th
e development of photon-dominated regions produced by the ultraviolet
radiation field of the central star. The observations also provide imp
ortant information on the physical conditions in the molecular gas. Mu
lti-line observations of CN, CO, and HCO+ show that the clumps which f
orm the envelopes of the evolved PNe maintain remarkably high gas dens
ities (similar to few x 10(5) Cm-3) and low temperatures (similar to 2
5 K). These values are consistent with the idea that the clumps are in
rough pressure equilibrium with the more diffuse, ionized gas and can
last for a significant part of the nebular lifetime, providing the en
vironment needed for the survival of the molecules. Thus the clumping
of the gas in these PNe is an essential aspect of both their physical
and chemical evolution.