Effect of water on the formamide-intercalation of kaolinite.
The molecular structures of low defect kaolinite completely intercalated with formamide and formamide-water mixtures have been determined using a combination of X-ray diffraction, thermoanalytical techniques, DRIFT and Raman spectroscopy. Expansion of the kaolinite to 10.09 A was observed with subtle differences whether the kaolinite was expanded with formamide or formamide-water mixtures. Thermal analysis showed that greater amounts of formamide could be intercalated into the kaolinite in the presence of water. New infrared bands were observed for the formamide intercalated kaolinites at 3648, 3630 and 3606 cm(-1). These bands are attributed to the hydroxyl stretching frequencies of the inner surface hydroxyls hydrogen bonded to formamide with water, formamide and interlamellar water. Bands were observed at similar positions in the Raman spectrum. At liquid nitrogen temperature, the 3630 cm(-1) Raman band separated into two bands at 3633 and 3625 cm(-1). DRIFT spectra showed the hydroxyl deformation mode at 905 cm(-1). Changes in the molecular structure of the formamide are observed through both the NH stretching vibrations and the amide 1 and 2 bands. Upon intercalation of kaolinite with formamide, bands are observed at 3460, 3344, 3248 and 3167 cm(-1) attributed to the NH stretching vibration of the NH involved with hydrogen bonded to the oxygens of the kaolinite siloxane surface. In the DRIFT spectra of the formamide intercalated kaolinites bands are observed at 1700 and 1671 cm(-1) and are attributed to the amide 1 and amide 2 vibrations.
Frost
R L
RL
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, Brisbane, Australia. r.frost@qut.edu.au
Kristof
J
J
Horvath
E
E
Kloprogge
J T
JT
D000577:Amides / Q000737:chemistry; D004055:Differential Thermal Analysis; D005559:Formamides / Q000737:chemistry*; D007616:Kaolin / Q000737:chemistry*; D008968:Molecular Conformation; D013055:Spectrophotometry, Infrared / Q000379:methods*; D013059:Spectrum Analysis, Raman / Q000379:methods; D014867:Water / Q000737:chemistry*; D014961:X-Ray Diffraction / Q000379:methods
D000577:Amides; D005559:Formamides; D014867:Water; D007616:Kaolin