Abstract
$TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.
n-propanol 용매내에서 titanium n-propoxide($Ti(O^nPr)_4$)의 가수분해반응에 의하여 $TiO_2$ 미분말을 합성하였고, 가수분해속도를 자외선 분광법에 의하여 측정하였다. 분말합성은 water/alkoxide의 농도비가 약 300정도에서 실시하였으며, 물농도, 반응온도, 반응시간 및 반응용액의 산 염기효과에 의한 합성조건을 조사하였다. 반응은 $Ti(O^nPr)_4$의 농도에 비하여 물농도를 과량으로 하여 유사일차반응으로 진행시켰고, 반응속도상수를 Guggenheim method로 계산하였다. 또한 물의 동위원소효과($D_2O$)를 측정하여 반응에 관여하는 물분자의 촉매성을 확인하였다. 실험결과 중성 및 염기성 용액 조건에서 $TiO_2$미분말이 합성되었고, 미세구조 관찰로부터 $TiO_2$입자는 직경 $0.4-0.7{\mu}m$ 정도의 구형입자로 확인되었으며, 물의 농도와 반응온도가 증가할수록, 반응시간이 감소할수록 입자크기는 작아지는 경향을 보였다. 물의 동위원소효과로부터, 물분자는 nucleophilic catalysis로 작용하고 있으며, 반응속도로부터 전이상태에 참여하는 n-value와 열역학적 파라미터를 계산한 결과, $Ti(O^nPr)_4$의 가수분해반응은 이분자 반응인 associative $S_N2$ mechanism으로 진행하는 것으로 추정되었다.
