The mechanism of detection of chemical vapors in air by an ionization chamber supplied by DC and AC voltage has been described. The theoretical explanation is based on numerical solutions of the differential equations of the cylindrical ionization chamber. The current of the ionization chamber operating in the AC regime has two components: aconductive component, caused by the ions drifts, and acapacitive component, caused by the distortion of the electric field. The ionization chamber operating in the DC regime has only the first component; hence the AC supplied chamber has larger response than the DC supplied chamber.