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Conductimetric titrations of charge-transfer complexes in solution

✍ Scribed by F. Gutmann; H. Keyzer


Publisher
Elsevier Science
Year
1966
Tongue
English
Weight
821 KB
Volume
11
Category
Article
ISSN
0013-4686

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✦ Synopsis


Al&met-The formation of charge-transfer complexes can be followed by conductimetric titration. Either a donor solution is titrated with a solution of an acceptor, or vice versa, both using the same solvent. A theory is presented requiring the conductivity to pass through a maximum when donor and acceptor are present in the solution in the stoichiometry required for the formation of a chargetransfer complex. Conductimetric titrations yielding conductivity peaks in agreement with the theory are reported for the following corn lexes: chlorpromaxine-iodine in a&o&rile; phthalocyanineiodine in dimethylsulphoxide; an &a ceneiodine in a&o&rile; benxene-chloraml in methanol; and anthracene&loranil in methanol. Dilution of the 1: 1 anthraccne4loranil complex formed in dimethvlsulnhoxide with the inert solvent carbon tetrachloride vielded linear dots between eouivalent Tim&tivi$_and (complex concentration)+, but of reversesloG; the equival&t conductivity bropped creasmg ddutron. The Janx-Danyluk equation IS accurately obeyed, though wrth a "h"p break; thus a solvent interaction involving ionic association is suspected, at least in diithysulphoxide.

R&~~II&-L~ formation de complexes de transfert de charge peut &e suivie par titration conducti-m&rique. On titre une solution du domreur avec une solution de l'accepteur ou inversement. On pr6sente une theorie selon zztp '"t uelle la conductivite passe par un maximum lorsque le donneur et teur sont presents en so ution dans la proportion requise pour la formation d'un complexe de ert de charge. On pr&sente des titrations conductimetriques manifestant, d'accord avec la thdorie, des pits de conductivite pour les complexes suivants: chlorpromazine&de darts l'ac&onitrile; phthalocyanine-iode dans le dimethylsulfoxyde; anthra&n&ode dans l'a&onitrile; ben&nechloranil dans le methanol et anthracen~hloranil dans le m&hanol. En diluant le corn lexe 1: 1 d'anthracene et chloranil forme dans le dimethylsulfoxyde avec le solvant inerte M trach! orure de carbone on observe un comportement lineahe entre la conductivite equivalente et la rachre car&e de la concentration du complexe, mais avec une pente hive&e, la conductivite diminuant avec l'accroissement de dilution. L'equation de Janx et Danlyuk est obeie avec precision, bien qu'avec une coupure nette; ceci permet de supposer une interaction avec le solvant dormant lieu a une association ionique, au moins dans le cas du dii6thylsulfoxyde.


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