Calculation · Vol. V

Crystal growth.

Kinetics · Thermodynamics
6 models · MathJax
01

Classical nucleation rate

Energy barrier of the critical cluster and nucleus radius in classical nucleation theory.

Nucleation rate $J$ (per volume, per time):

$$J = A\,\exp\!\Big(-\frac{\Delta G^*}{k_B T}\Big)$$

with the homogeneous nucleation barrier

$$\Delta G^* = \frac{16\pi\,\sigma^3}{3(\Delta G_v)^2}$$

where $\sigma$ is the surface tension and $\Delta G_v \approx \tfrac{R T}{V_m}\ln S$ for a supersaturation ratio $S$. Critical radius: $r_c = \tfrac{2\sigma}{\Delta G_v}$.

Inputs 5 parameters
ENTER · run
02

Growth rate — diffusion vs. surface

Two limiting regimes for linear crystal growth.

For supersaturation ratio $S$:

$$G_{\text{diff}} = k_d\,(S - 1), \qquad G_{\text{surf}} = k_r\,(S - 1)$$

$k_d$ reflects mass transport ($D/\delta$) and $k_r$ the surface attachment rate.

Inputs 3 parameters
ENTER · run
03

Avrami equation (JMAK)

Crystallization kinetics — transformed fraction and mean size.

$$Y(t) = 1 - \exp\!\big[-K\,t^n\big]$$

$Y$ is the crystallised fraction at time $t$, $n$ the Avrami exponent, $K$ the rate constant. Optional fields estimate the mean crystal diameter assuming spherical crystals.

Inputs · required 3 + 5 optional
Optional · mean size
ENTER · run
04

Supersaturation ratio

$S = C / C^*$ — ratio of actual concentration to equilibrium solubility.

Inputs 2 parameters
ENTER · run
05

van't Hoff equation

Temperature dependence of solubility, assuming constant $\Delta H_{\text{sol}}$.

$$\ln\frac{C_2}{C_1} = -\frac{\Delta H_{\text{sol}}}{R}\Big(\frac{1}{T_2} - \frac{1}{T_1}\Big)$$

$R = 8{,}314\ \text{J/(mol·K)}$. ΔH > 0 corresponds to endothermic dissolution (solubility increases with $T$).

Inputs 4 parameters
ENTER · run
06

Dimensionless numbers

Reynolds, Péclet and Richardson — characterise the flow regime.

  • Re — inertial vs. viscous forces: $\text{Re} = \rho v L / \mu$.
  • Pe — advection vs. diffusion: $\text{Pe} = v L / D$.
  • Ri — buoyancy vs. shear: $\text{Ri} = g \, (\Delta\rho/\rho) \, L / v^2$.

If $\rho_2$ is left blank or equal to $\rho_1$, Ri treats $\Delta\rho = 0$.

Inputs 7 parameters (2 optional)
ENTER · run
07

Flow regime (Navier–Stokes)

Simplified forms dominating fluid dynamics in crystallisation.

The Navier–Stokes equation for incompressible flow with gravity:

$$\rho\Big(\frac{\partial \mathbf{v}}{\partial t} + (\mathbf{v}\cdot\nabla)\mathbf{v}\Big) = -\nabla p + \mu\,\nabla^2 \mathbf{v} + \rho\,\mathbf{g}$$
Low Re

Viscosity-dominated

Inertia is negligible — Stokes (creeping) flow: $-\nabla p + \mu\nabla^2\mathbf{v} + \rho\mathbf{g} \approx 0$. Flow is laminar and reversible.
High Re

Inertia-dominated

The viscous term is small — Euler flow: $\rho(\mathbf{v}\cdot\nabla)\mathbf{v} \approx -\nabla p + \rho\mathbf{g}$. Can become turbulent at very high Re.
High Ri

Buoyancy-dominated

Density differences govern the flow — natural convection, possibly stratified. Low Ri → buoyancy can be ignored (forced convection).
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