THERMODYNAMICS OF NUCLEATION 1

Thermodynamic Analysis of Nucleation at Low Temperatures

Alex M. Maldonado

Western Michigan University

THERMODYNAMICS OF NUCLEATION 2

Abstract

Pharmaceuticals rely heavily on controlled drug release and their synthesis can be enhanced or

controlled by encapsulating the active drug with SiO2/MgSt core/shell nanoparticles less than 20

nanometers in diameter. Parameters of homogeneous nucleation of the require reactants remains

unknown. Recommendations based on the thermodynamics of homogeneous nucleation can lead

to a desired nucleus size and composition. A temperature infinitesimally under 200 degrees

Celsius with a high degree of saturation would be ideal for small nucleus size. More

experimentation for compound characteristics such as surface energies and molar volume are

needed for precise recommendations and analysis.

Keywords: SiO2/MgSt core/shell nanoparticle; homogenous nucleation; thermodynamics

THERMODYNAMICS OF NUCLEATION 3

Thermodynamic Analysis of Nucleation at Low Temperatures

Problem Statement

Nucleation is an essential step in the formation of core-shell nanoparticles as it is the

process of forming solid particles within an aqueous solution. We will be examining the

mechanism of homogeneous nucleation at low temperatures concerning the synthesis of

SiO2/MgSt core/shell structures.

Task Identified

The homogeneous nucleation of two unique species in a heterogeneous aqueous solution

is a challenge in nanoparticle synthesis. Homogeneous nucleation is rarely observed naturally,

because heterogeneous nucleation has a significantly lower nucleation barrier. The lower

nucleation barrier is due to the lowering of the surface energy cost of forming a nucleus

(Zhigilei, 2016).

The ideal solution would be a single reactor with the capability to control standard

thermodynamic variables to direct the synthesis reaction. The general steps of the synthesis

process would be forming a solution, nucleation, cluster formation, and crystallization. The

nucleation step will be analyzed, discussed, and recommendations will be made to achieve the

ideal reaction.

Parameters Selected

The thermodynamics of homogeneous nucleation can be described by energy

requirements and particle size. Only variables that can be independently controlled or affected to

change particle size will be considered; these variables include temperature of reactor and

concentration of the aqueous solution.

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Background

There are two classifications of nucleation: homogeneous and heterogeneous nucleation.

Homogeneous nucleation is when a second phase spontaneously appears out of a parent phase

(Zhigilei, 2016). For an aqueous solution the phase is solid and phase is liquid.

Heterogeneous nucleation occurs when nucleation and growth initiates on other species already

in the phase which typically are walls of the reaction vessel or impurities in the solution

(Kornfield & Greer, 2016). Any heterogeneous nucleation would incorporate impurities into the

structure and cannot be utilized. Therefore only homogeneous nucleation will be analyzed.

Driving Force of Homogeneous Nucleation

Nucleation is the initial process in the solidification of a

substance. Each phase has a unique function of free

energy which is a function of temperature, pressure, and

composition. A system will spontaneously configure

itself into the phase of lower free energy. The point

Figure 1: Graphical representation of
where free energies of solid and liquids are the same is at G due to supercooling (Zhigilei, 2016).

the melting temperature Tm. At any point where a liquid is cooled below its melting temperature

the system will solidify to decrease the free energy by, = . This difference in

free energy is the ultimate driving force of nucleation (Zhigilei, 2016).

The total free energy is given by (Thanh, Maclean, & Mahiddine, 2014) as

4 ln()
= 4 2 3 (1)
3

Where r is the radius of a spherical particle, is the surface energy of the species, kb is

Boltzmanns constant, T is the temperature, S is the supersaturation of the solution, and v is the

molar volume of the solution. The positive term in the free energy equation is the surface term
THERMODYNAMICS OF NUCLEATION 5

associated with the formation of new interfacial area between phases. The negative term is the

volume term associated with the bulk condensation energy (Zhigilei, 2016).

Critical Parameters of Homogeneous Nucleation

There is a maximum of free energy a nucleus will obtain

when it grows in size. The free energy will always have a

positive surface free energy and a negative crystal energy and

there is a point where the change in Gibbs free energy is zero.

Differentiating equation (1) with respect to r and setting it

equal to zero, ( ) = 0, gives us (Thanh, Maclean, &

Mahiddine, 2014):

4 2
2
= (2) = (3)
3 ln()
Figure 2: Free energy with respect
The critical radius rcrit corresponds to the minimum size a to radius of nucleus (Thanh,
Maclean, & Mahiddine, 2014).
particle must maintain to avoid being dissolved back into the

parent phase. The energy barrier required to reach this size is the critical free energy Gcrit.

There are three thermodynamic regimes when regarding particle size and free energy. When r is

increasing and r < r*, Gr increases and therefore the particle is not thermodynamically stable

and particles dissolve back into the bulk phase. When r = r* and r is still increasing there is still

a positive Gr; however, it starts to decrease but is still thermodynamically unfavorable. Once

the size reaches r0 any further increase in size leads to Gr becoming negative and leads to the

formation of bulk phase transition to the phase (Virkar, 2016).

Approach

In order to produce a stable solid nanoparticle without having it dissolve back into the

solution, but not start solidification, the size of the nucleus needs to stay between r* and r0. If the
THERMODYNAMICS OF NUCLEATION 6

particle size reaches r0 the reactor would being spontaneous solidification and nanoparticle

synthesis would be uncontrollable. Because rcrit is inversely proportional to temperature the

higher temperature would produce a larger particle size. A reaction temperature closer to the

fusion temperature would be ideal for small stable nuclei. The other independent variable that

affects rcrit is degree of supersaturation S which shares the same relationship with rcrit as

temperature, so a higher degree of supersaturation would produce smaller nuclei.

Description

The fusion temperature for Magnesium Stearate (MgSt) is 200 degrees Celsius (Sigma-

Aldrich, 2016). Fusion data for colloidal silica could not be found, but is assumed to be lower

than 200 degrees Celsius. At a temperature lightly below 200 degrees Celsius the MgSt can start

nucleation while the colloidal silica can remain in the liquid phase without having to worry about

solidification. Currently, there is no available data for the surface energies of MgSt or colloidal

silica, so direct calculations cannot be obtained without further experimentation to determine

optimum temperature of reactor. Molar volume v cannot be calculated without knowing the

composition of the solution.

Conclusions

There needs to be additional experimentation to determine the optimal temperature and

concentration for the overall synthesis of SiO2/MgSt core/shell nanoparticles. Once the solution

is made, the temperature should be as close to the fusion temperature of MgSt as possible while

still overcoming the free energy barrier. The degree of supersaturation should be higher to lower

the Gibbs free energy barrier and produce smaller particles.

THERMODYNAMICS OF NUCLEATION 7

References

Kornfield, J., & Greer, J. (2016, April 2016). MS 133. Kinetics of Solid Phase Transformations.

Retrieved December 2016, from Julia R. Green Professor of Materials Science and

Mechanics:

http://jrgreer.caltech.edu/content/teaching/MS133_SP_2016/Lecture_Notes/week5_2.pdf

Sigma-Aldrich. (2016). Magnesium stearate United States Pharmacopedia (USP) Reference

Standard. Retrieved December 2016, from Sigma-Aldrich:

http://www.sigmaaldrich.com/catalog/product/usp/1374340?lang=en&region=US

Thanh, N. T., Maclean, N., & Mahiddine, S. (2014). Mechanisms of Nucleation and Growth of

nanoparticles in Solution. Chemical Reviews, 114, 7610-7630.

doi:dx.doi.org/10.1021/cr400544s

Virkar, A. (2016, January 1). Lecture notes and other materials for MSE 5034 & 6034. Retrieved

December 2016, from The University of Utah Department of Materials Science &

Engineering: http://www.eng.utah.edu/~lzang/mse5034&6034.html

Zhigilei, L. (2016, January). MSE 3050: Thermodynamics and Kinetics of Materials. Retrieved

December 2016, from University of Virginia, Department of Materials Science and

Engineering`: http://www.people.virginia.edu/~lz2n/mse305/
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Figures

Figure 1. At point Tm the chemical potential of a pure substance is equal for the liquid and solid

phase. When the solution is at T* you have a difference in temperature of T. At T* the chemical

potential of the liquid GVL is greater than the chemical potential of the solid GVS; this difference

of Gv is the driving force of the phase transition from liquid to solid (Zhigilei, 2016).

Figure 2. This figure demonstrates the relationship of free energy G to the radius of a nucleus.

The Gv represents the change of free energy due to the increasing volume of the solid phase.

The Gs represents the change of free energy due to new interfacial area between solid and

liquid. The G is the total free energy where Gcrit is the maximum free energy barrier obtained at

the radius rcrit (Thanh, Maclean, & Mahiddine, 2014).