1024 A. ŠARI] ET AL. The FT-IR spectra were recorded using a Perkin-Elmer spectrometer 2000 model. The IRDM (Infrared Data Manager) program, obtained by Perkin-Elmer, was used to process <strong>the</strong> recorded spectra. Mössbauer spectra were recorded using standard equipment and a 57Co source. Ma<strong>the</strong>matical dec<strong>on</strong>voluti<strong>on</strong>s <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>the</strong> recorded spectra were performed using a standard procedure. X-ray powder diffracti<strong>on</strong> measurements were performed using <strong>the</strong> Philips diffractometer MPD 1880 model (Cu-K radiati<strong>on</strong>, graphite m<strong>on</strong>ochromator and proporti<strong>on</strong>al counter). The size and shape <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>the</strong> particles were m<strong>on</strong>itored by transmissi<strong>on</strong> electr<strong>on</strong> microscopy (Opt<strong>on</strong> EM-10 model). Before <strong>the</strong> transmissi<strong>on</strong> electr<strong>on</strong> microscopic observati<strong>on</strong>, <strong>the</strong> powders were dispersed in doubly distilled water by ultras<strong>on</strong>ic waves and <strong>the</strong>n a drop <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>the</strong> dispersi<strong>on</strong> was placed <strong>on</strong> a copper grid, previously covered by a polymer film. RESULTS AND DISCUSSION FT-IR Spectroscopy The present work shows high potentials <str<strong>on</strong>g>of</str<strong>on</strong>g> FT-IR spectroscopy in m<strong>on</strong>itoring phase changes in <strong>the</strong> ir<strong>on</strong> oxide precipitates. This is illustrated by <strong>the</strong> FT-IR spectra shown in Figures 1 to 6. Figures 1 and 2 show <strong>the</strong> FT-IR spectra <str<strong>on</strong>g>of</str<strong>on</strong>g> samples C1 to C10, prepared by varying <strong>the</strong> c<strong>on</strong>centrati<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>FeCl3</strong> , and at an initial c<strong>on</strong>centrati<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> 0.025 M urotropin. After 24 hours <str<strong>on</strong>g>of</str<strong>on</strong>g> aging <strong>the</strong> precipitati<strong>on</strong> system, prepared <strong>from</strong> 0.005 M <strong>FeCl3</strong> soluti<strong>on</strong>, a mixture <str<strong>on</strong>g>of</str<strong>on</strong>g> -Fe2O3 and -FeOOH was observed. The IR bands at 563 and 464 cm –1 are due to <strong>the</strong> presence <str<strong>on</strong>g>of</str<strong>on</strong>g> -Fe2O3 , whereas <strong>the</strong> bands at 896 and 799 cm –1 are typical <str<strong>on</strong>g>of</str<strong>on</strong>g> -FeOOH. At a c<strong>on</strong>centrati<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> 0.02 M <strong>FeCl3</strong> , <strong>the</strong> -FeOOH phase appeared in sample C3, as c<strong>on</strong>cluded <strong>on</strong> <strong>the</strong> basis <str<strong>on</strong>g>of</str<strong>on</strong>g> a new and str<strong>on</strong>g IR band at 694 cm –1 . The origin <str<strong>on</strong>g>of</str<strong>on</strong>g> IR bands corresp<strong>on</strong>ding to -FeOOH, -FeOOH and -Fe2O3 will not be discussed here because adequate assignati<strong>on</strong>s <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>the</strong>se IR bands were presented in earlier papers. 18,21–23 At c<strong>on</strong>centrati<strong>on</strong>s <str<strong>on</strong>g>of</str<strong>on</strong>g> 0.05 and 0.3 M <strong>FeCl3</strong> , <strong>the</strong> presence <str<strong>on</strong>g>of</str<strong>on</strong>g> -FeOOH, as a single phase in samples C4 and C5, is observed. These phase changes in <strong>the</strong> precipitates were associated with <strong>the</strong> pH change in <strong>the</strong> mo<strong>the</strong>r liquor <strong>from</strong> 7.61 to 0.78. After 7 days <str<strong>on</strong>g>of</str<strong>on</strong>g> aging <strong>the</strong> precipitati<strong>on</strong> systems C6 to C10, <strong>the</strong> main change was observed in <strong>the</strong> FT- IR spectrum <str<strong>on</strong>g>of</str<strong>on</strong>g> sample C8, precipitated <strong>from</strong> 0.02 M <strong>FeCl3</strong> . The fracti<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>the</strong> -FeOOH phase (IR bands at 896 and 800 cm –1 ) significantly increased, whereas <strong>the</strong> -FeOOH phase was absent. The pH <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>the</strong> mo<strong>the</strong>r liquor decreased <strong>from</strong> 5.55 to 5.29. This shows that <strong>the</strong> fracti<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> -FeOOH, formed at <strong>the</strong> beginning <str<strong>on</strong>g>of</str<strong>on</strong>g> <strong>the</strong> precipitati<strong>on</strong> process, dissolved after 7 days.
PRECIPITATION OF IRON OXIDES 1025 Figure 1. FT-IR spectra <str<strong>on</strong>g>of</str<strong>on</strong>g> samples C1-C5, recorded at room temperature. Figure 2. FT-IR spectra <str<strong>on</strong>g>of</str<strong>on</strong>g> samples C6-C10, recorded at room temperature.