INFRARED SPECTROSCOPIC EXAMINATION OF THE INTERACTION OF UREA WITH THE NATURALLY-OCCURRING ZEOLITE CLINOPTILOLITE

Infrared spectroscopy has shown for the first time that the naturally occurring zeolite clinoptilolite can absorb urea, (NH2)2CO, under ambient conditions from either aqueous or ethanolic solutions. The two strongest NH stretching bands at 3441 and 3344 cm-1 in pure, solid urea shift to higher frequency (about 3504 and 3401 cm-1) after absorption. Two of the four urea bands in the 1800-1300 cm-1 range (at 1683 and 1467 cm-1) undergo marked downward shifts to about 1670 and 1445 cm-1. The other two bands show little change in frequency. The strong band at 1602 cm-1, however, diminishes in intensity to little more than an ill-defined shoulder on the 1626-cm-1 peak. When clinoptilolite is heated to 450 °C and then treated with molten urea (ca. 140 °C) for several minutes, and finally washed twice with ethanol to remove excess unreacted urea, further changes become apparent in the spectrum of the urea-treated clinoptilolite. The two NH stretching bands broaden without significant change in frequency. Two new bands appear in the midfrequency range at 1777 (weak) and 1719 (medium strong) cm-1. Of the four original midfrequency peaks, the one at 1602 cm-1 is now absent. Two others (1627 and 1440 cm-1) exhibit little change, while the fourth has broadened and shifted down to 1663 cm-1, where it appears as a shoulder on the band at 1627 cm-1. Both treatments clearly induce interaction between urea and the zeolite which seems to result in significant modifications in the nature of the hydrogen bonding of the substrate. © 1991.