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The document provides a comprehensive profile of Titanium Dioxide (TiO2), focusing on its rutile phase, crystallographic structure, and thermodynamic properties. Key properties include a tetragonal crystal system, a density of 4.23 g/cm³, and a melting point of 2116 K. Additionally, it discusses photocatalytic behavior, phase stability parameters, and quantum yield equations relevant to its applications.

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0% found this document useful (0 votes)
3 views3 pages

Some Stuff

The document provides a comprehensive profile of Titanium Dioxide (TiO2), focusing on its rutile phase, crystallographic structure, and thermodynamic properties. Key properties include a tetragonal crystal system, a density of 4.23 g/cm³, and a melting point of 2116 K. Additionally, it discusses photocatalytic behavior, phase stability parameters, and quantum yield equations relevant to its applications.

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Comprehensive Physical & Thermodynamic Property Profile: Titanium

Dioxide ($\text{TiO}_2$)
●​ [Registry_ID: CAS 13463-67-7]
●​ [Systematic_Name: Titanium(IV) Oxide]
●​ [Polymorph_Focus: Rutile Phase]
●​ [Classification: Transition Metal Oxide]

Crystallographic & Structural Specifications


●​ Crystal System: Tetragonal
●​ Space Group: $P4_2/mnm$ (No. 136)
●​ Lattice Parameters (at 298 K):
○​ $a = b = 0.4594\text{ nm}$
○​ $c = 0.2959\text{ nm}$
●​ Coordination Geometry: Octahedral ($\text{Ti}$ surrounded by 6 $\text{O}$ atoms;
$\text{O}$coordinated to 3 $\text{Ti}$ atoms)
●​ Refractive Index (Rutile): 2.61 (Ordinary ray), 2.90 (Extraordinary ray)

Thermodynamic & Mechanical Property Matrix


Parameter / Standard Value High-Temp Critical Variance (σ)
Property Value Limit
(1500 K)

Density ($\rho$) $4.23\text{ $4.08\text{ Melting $\pm$ $0.02\text{


g/cm}^3$ g/cm}^3$ Point g/cm}^3$
:
2116
K

Molar Heat $55.06\text{ $74.20\text{ Decompositi $\pm$ $0.15\text{


Capacity J/(mol}\cd J/(mol}\cd on: J/(mol}\cd
($C_p$) ot\text{K)} ot\text{K)} >300 ot\text{K)}
$ $ 0K $
Thermal $11.8\text{ $3.2\text{ Phase $\pm$ $0.4\text{
Conductiv W/(m}\cd W/(m}\cd Trans W/(m}\cd
ity ot\text{K)} ot\text{K)} ition: ot\text{K)}
$ $ 1184 $
K

Band Gap $3.06\text{ eV}$ $2.75\text{ eV}$ Metal $\pm$ $0.05\text{


(Direct) Trans eV}$
ition:
N/A

Bulk Modulus $211\text{ GPa}$ $178\text{ GPa}$ Fracture $\pm$ $5\text{


($K$) Point GPa}$
:
Varia
ble

Dielectric 170 230 Breakdown: $\pm$ 8.0


Constant >15
($\epsilon MV/
_\parallel$ m
)

X-Ray Diffraction (XRD) Powder Pattern Peak Indexing


Plaintext

●​ 2-Theta (deg) Intensity (%) h k l d-spacing (Å)


●​ 27.44 100.0 1 1 0 3.247
●​ 36.08 50.2 1 0 1 2.487
●​ 41.22 23.1 2 0 0 2.188
●​ 54.32 58.4 2 1 1 1.687
●​ 56.64 18.6 2 2 0 1.623
●​ 62.74 11.2 0 0 2 1.480
●​ 69.01 14.9 3 0 1 1.360

Quantum Yield and Photo-Kinetics Equations


The rate of photocatalytic hydroxyl radical ($\cdot\text{OH}$) generation via electron-hole pair
separation upon ultraviolet excitation ($\lambda \le 400\text{ nm}$) is calculated using the
steady-state approximation for charge carriers:

$$\frac{d[\cdot\text{OH}]}{dt} = \frac{\Phi \cdot I_{abs} \cdot k_t [H_2O]}{k_r (n_e \cdot p_h) +
k_t [H_2O]}$$

Where:

●​ $\Phi$ represents the primary quantum yield of initial charge separation.


●​ $I_{abs}$ represents the volumetric rate of photon absorption
($\text{einsteins/s}\cdot\text{dm}^3$).
●​ $k_t$ and $k_r$ represent the pseudo-first-order surface trapping rate constant and
second-order electron-hole recombination rate constant, respectively.
●​ $n_e$ and $p_h$ represent the local spatial densities of photo-induced conduction band
electrons and valence band holes.

When $k_r (n_e \cdot p_h) \gg k_t [H_2O]$, the radiative and non-radiative recombination
pathways dominate, driving the effective photon utilization efficiency down to less than 1.5%.

Phase Stability Parameters


●​ Anatase to Rutile Transition Temperature: 873 K to 1184 K (Highly dependent on
dopant concentration and grain size)
●​ Standard Enthalpy of Formation ($\Delta H_f^\circ$): $-944.7\text{ kJ/mol}$
●​ Standard Gibbs Free Energy ($\Delta G_f^\circ$): $-889.4\text{ kJ/mol}$
●​ Standard Entropy ($S^\circ$): $50.3\text{ J/(mol}\cdot\text{K)}$
●​

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