Isotope Effect on Dissociation Probabilities in the Mass Spectra of Chloroform and Chloroform-d

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The mass spectra of the isotopic molecules CHCl3 and CDCl3 have been determined, using electron energies of 50 v and 70 v. It was found that the probability of dissociation of the C–H bond is approximately three times that for the dissociation of the C—D bond. The relative probability of dissociating H+Cl and D+Cl is the same as the relative probability of obtaining HCl+ and DCl+ ions, namely, about 1.6. Equal probability was observed for the dissociation of H+2Cl and D+2Cl. The probability of removing chlorine atoms is only slightly affected by the deuterium substitution.