The evolution of an isotachophoresis (ITP) system in acidic or basic p
H ranges can be quite different from that predicted by the existing th
eory. It was found theoretically and proved experimentally that the co
ntribution of hydrogen or hydroxyl ion to conductivity of solution and
/or its net charge changes the behavior of the ITP system, creating in
the terminating electrolyte an additional zone close to the initial i
nterfaces between electrolytes (leader and terminator). One boundary o
f the zone, being either sharp or dispersed, moves toward the leader;
the other is always sharp and stationary and coincides with initial el
ectrolytes' discontinuity. The latter can be registered in the presenc
e of electroosmotic flow which delivers it to the detection point. In
order to describe the dynamics of the ITP system at pH extremes an alg
orithm of analytical solution was developed, based on the revised Kohl
rausch theory. Its predictions coincide well with computer simulations
and experimental data. The results presented can help in a correct an
alysis of ITP data and explain some confusing phenomena which were con
sidered to be artifacts.