This thesis is made as it is submitted as a sum of published papers by the candidate. Aluminium hydroxides including gibbsite, boehmite and diaspore, are the major components, while iron hydroxides/oxides and kaolinite are the major impurities in bauxite. The dehydroxylation pathways during thermal activation of bauxite have been debated for decades. Phase transformation during thermal activation or calcination of bauxite to achieve high yields of alumina has been an important goal for the refining industry. This study deals with natural and synthetic aluminium and iron hydroxides using vibrational spectroscopy in conjunction with X-ray diffraction and electron microscopy, followed by the characterisation of the phase transformation in activated bauxite. In the Raman spectra, gibbsite shows four bands at 3617, 3522, 3433 and 3364 cm-1, and bayerite shows seven bands at 3664, 3652, 3552, 3542, 3450, 3438 and 3420 cm-1 in the hydroxyl stretching region. Five bands at 3445, 3363, 3226, 3119 and 2936 cm-1 for diaspore and four at 3371, 3220, 3085 and 2989 cm-1 for boehmite are present. The far infrared spectrum of boehmite resembles that of diaspore in the 300-400 cm-1 region. Boehmite has two characteristic bands at 366 and 323 cm-1 while diaspore has five at 354, 331, 250, 199 and 158 cm-1. The far infrared spectrum of gibbsite resembles that of bayerite in the 230-300 cm-1 region. Gibbsite shows three characteristic bands at 371, 279 and 246 cm-1 whereas bayerite shows six at 383, 345, 326, 296, 252 and 62 cm-1. The far infrared spectra are in-harmony with the FT-Raman spectra, allowing the study and differentiation of the stretching of AlO4 units to characterize these four alumina phases. The surface properties of kaolinite and gibbsite are studied using Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS). The FTIR-PAS spectra of kaolinite are recorded at mirror velocities of 0.05, 0.1, and 0.2 cm s-1, and compared to the gibbsite spectra recorded at mirror velocity of 0.2 cm s-1. It is found that the hydroxyl surface spectra are a function of depth. For the FTIR spectroscopy of thermal dehydroxylation of goethite to form hematite, the intensity of hydroxyl stretching and bending vibrations decreased with the extent of dehydroxylation of goethite. Infrared absorption bands clearly show the phase transformation between goethite and hematite, in particular the migration of excess hydroxyl units from goethite to hematite. Data from the band component analysis of FT-IR spectra indicate that the hydroxyl units mainly affect the a- plane in goethite and the equivalent c- plane in hematite. A larger amount of non-stoichiometric hydroxyl unit is found to be associated with a higher aluminium substitution. A shift to a higher wavenumber of bending and hydroxyl stretching vibrations is attributed to the effects of aluminium substitution associated with non-stoichiometric hydroxyl units on the a-b plane relative to the b-c plane of goethite. The dehydroxylation pathways of both the aluminium hydroxides and the impurities are intensively studied. Gibbsite completely decomposed at 250 °C, followed by boehmite and kaolinite at 500 °C. No phase transformations were observed for hematite, anatase, rutile or quartz up to 800 °C. Small amounts of gibbsite transformed to boehmite but the majority transformed to chi (χ) alumina, a disordered transition alumina phase, after dehydroxylation at 250 °C. The dehydroxylation pathways of crystalline gibbsite follow the orders: (a) gibbsite (&lt250 °C) to boehmite (250-450 °C) to gamma alumina (γ) (500-800 °C); or (b) gibbsite (&lt250 °C) to chi alumina (χ) (250-800 °C) to chi (χ) + kappa alumina (κ) (700-800 °C). Boehmite completely altered to gamma alumina (γ), while kaolinite altered to metakaolinite at 500 °C. The vibrational spectroscopy including FT-IR and FT-Raman, is a rapid, accurate and non-destructive technique in characterising both single and mixed mineral phases. In particular, the vibrational spectroscopy has shown its advantages over other techniques in terms of its sensitivity to hydroxyl groups. Future work on the simulation of bauxite dehydroxylation with emphasis on the studies of transition aluminas is proposed. The application of the advanced technique synchrotron x-ray spectroscopy, in addition to those techniques used in the present study, is recommended.