Modeling Chemical Reactivity at the Interfaces of Emulsions: Effects of Partitioning and Temperature
<p>(<b>Left</b>) Basic illustration of an oil-in-water emulsion droplet. The diameter of the droplet may range from tens of nanometers to micrometers, and the volume of the interfacial region is only a small fraction of the total volume of the droplet. (<b>Right</b>) Optical microscope photograph of an O/W emulsion stabilized with Tween 20 and conceptual division of the domains with different solvent properties.</p> "> Figure 2
<p>TEM microphotographs (15,000×) of stained (uranyl acetate) of 1:9 (<span class="html-italic">vol</span>:<span class="html-italic">vol</span>) fish oil-in-water nanoemulsions prepared with different amounts of surfactant. (<b>Left</b>) Φ<sub>I</sub> = V<sub>surf</sub>/V<sub>emulsion</sub> = 0.0047, (<b>right</b>), Φ<sub>I</sub> = 0.0378. Reproduced from ref. [<a href="#B34-molecules-26-04703" class="html-bibr">34</a>].</p> "> Figure 3
<p>Changes in <span class="html-italic">k</span><sub>obs</sub> as a function of log(<span class="html-italic">k</span><sub>chem</sub>) for a bimolecular reaction in aqueous solution, according to Equation (4). Figures extracted from ref. [<a href="#B48-molecules-26-04703" class="html-bibr">48</a>].</p> "> Figure 4
<p>Variations of <span class="html-italic">k</span><sub>obs</sub> with Φ<sub>I</sub> for methyl caffeate in 4:6 (squares) and 1:9 (circles) olive oil emulsions. The solid lines are the theoretical curves obtained by fitting the experimental data to Equations (16) and (17). Adapted from ref. [<a href="#B96-molecules-26-04703" class="html-bibr">96</a>].</p> "> Figure 5
<p>Illustrative examples of the variations of <span class="html-italic">k</span><sub>obs</sub> with Φ<sub>I</sub> for the reaction between 16-ArN<sub>2</sub><sup>+</sup> with gallic acid (<b>A</b>) and with lauryl gallate (<b>B</b>) in 1:9 fish oil-in-water emulsions at T = 25 °C. The solid lines are the theoretical curves obtained by fitting the experimental data to Equations (16) and (18) (<b>A</b>) and (17) and (19) (<b>B</b>). Adapted from ref. [<a href="#B98-molecules-26-04703" class="html-bibr">98</a>].</p> "> Figure 6
<p>Variations of 1/<span class="html-italic">k</span><sub>obs</sub> with Φ<sub>I</sub> in 1:9 (blue) and 1:4 (red) <span class="html-italic">v</span>:<span class="html-italic">v</span> octane-in-water emulsions for the reaction of 16-ArN<sub>2</sub><sup>+</sup> with octyl (<b>A</b>) and lauryl (<b>B</b>) gallate. Extracted from ref. [<a href="#B99-molecules-26-04703" class="html-bibr">99</a>].</p> "> Figure 7
<p>Changes in <span class="html-italic">k</span><sub>obs</sub> upon increasing Φ<sub>I</sub> for the reaction between 16-ArN<sub>2</sub><sup>+</sup> and TBHQ in (<b>A</b>) CTAB emulsions and (<b>B</b>) in SDS emulsions. Figure extracted from ref. [<a href="#B87-molecules-26-04703" class="html-bibr">87</a>].</p> "> Figure 8
<p>Effects of increasing temperature (°C) on the reaction of caffeic acid with 16-ArN<sub>2</sub><sup>+</sup> in 1:9 (O:W) corn oil-in-water emulsions stabilized with Tween 20. The solid lines were obtained by fitting the variations of <span class="html-italic">k</span><sub>obs</sub> (<b>A</b>) and 1/<span class="html-italic">k</span><sub>obs</sub> (<b>B</b>) with Φ<sub>I</sub> to Equations (12)–(15). Reprinted from ref. [<a href="#B63-molecules-26-04703" class="html-bibr">63</a>].</p> "> Figure 9
<p>Variations in ln <span class="html-italic">k</span><sub>I</sub> and ln(<span class="html-italic">hk</span><sub>I</sub>/<span class="html-italic">k</span><sub>B</sub>T) as a function of 1/T (Kelvin) for the reaction of propyl (PG), octyl (OG), and lauryl (LG) gallates with 16-ArN<sub>2</sub><sup>+</sup> in the interfacial region of 1:9 (O/W) corn oil emulsions. Figure extracted from ref. [<a href="#B59-molecules-26-04703" class="html-bibr">59</a>].</p> "> Scheme 1
<p>Formation of emulsions after mixing oil, an aqueous solution, and the appropriate surfactant with some agitation. Addition of surfactants is needed to stabilize kinetically the droplets.</p> "> Scheme 2
<p>Chemical structures of some common surfactants employed to stabilize kinetically emulsions.</p> "> Scheme 3
<p>Main destabilization mechanisms of emulsions. Adapted from ref. [<a href="#B36-molecules-26-04703" class="html-bibr">36</a>].</p> "> Scheme 4
<p>(<b>A</b>) Illustrative representation of the formation of different products from two reactants in equilibrium with one another, such as stereoisomers, constitutional isomers, conformational isomers, etc., showing the rate constants involved. (<b>B</b>) Illustrative representation of a bimolecular reaction taking place in an emulsion where the reactants (<b>A</b>,<b>B</b>) can distribute and react simultaneously in the three regions.</p> "> Scheme 5
<p>Structures of the chemical probe 16-ArN<sub>2</sub><sup>+</sup> and of some reactive antioxidants.</p> "> Scheme 6
<p>Dissection of a small portion of a non-ionic emulsion showing the oil (O), interfacial (I), and aqueous (W) regions. Because of the special molecular characteristics of the chemical probe, the reaction between 16-ArN<sub>2</sub><sup>+</sup> and the antioxidant takes place exclusively in the interfacial region of the emulsion. Φ indicates the volume fraction of a region, <span class="html-italic">P</span> is the partition constant, and <span class="html-italic">k</span><sub>I</sub> is the rate constant for the reaction between the chemical probe 16-ArN<sub>2</sub><sup>+</sup> and the antioxidant. The chemical structures of the surfactants Tween 20 and Span 80 are also shown.</p> "> Scheme 7
<p>Distribution of a hydrophilic (oil insoluble) AO (<b>left</b>) and a hydrophobic (water-insoluble) antioxidant (<b>right</b>) in emulsions. <math display="inline"><semantics> <mrow> <msubsup> <mi>P</mi> <mi mathvariant="normal">W</mi> <mi mathvariant="normal">I</mi> </msubsup> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msubsup> <mi>P</mi> <mi mathvariant="normal">O</mi> <mi mathvariant="normal">I</mi> </msubsup> </mrow> </semantics></math> are the partition constants of the AO between the aqueous and interfacial and the oil and interfacial regions, respectively, and <span class="html-italic">k</span><sub>I</sub> is the interfacial rate constant for the reaction between 16-ArN<sub>2</sub><sup>+</sup> and AO.</p> "> Scheme 8
<p>Limiting case where both reactants do not partition and are located in the interfacial region of a non-ionic emulsion.</p> "> Scheme 9
<p>Outlines of the application of the pseudophase model to ionic emulsions illustrating: (<b>A</b>) the Donnan equilibrium in CTAB emulsions and (<b>B</b>) the ion exchange in SDS emulsions. TBHQ stands <span class="html-italic">t</span>-butylhydroquinone. Reproduced from ref. [<a href="#B87-molecules-26-04703" class="html-bibr">87</a>].</p> ">
Abstract
:1. Introduction
2. Emulsions: Classification, Physical Stabilization, and Main Properties
3. Dynamic Aspects of Emulsions and Mass Transfer
3.1. Kinetics of Chemical Reactions at Interfaces: Diffusive vs. Reactive Systems
3.2. Modeling Chemical Reactivity at the Interfaces of Emulsions
4. Main Equations Derived from the Application of the Pseudophase Model Emulsions
4.1. Reactions in Non-Ionic Emulsions
4.1.1. Reactions Where the Antioxidant Partitions between the Three Regions
4.1.2. Reactions Where the Antioxidant Partitions between Two Regions
4.1.3. Reactions Taking Place Exclusively at the Interfacial Region
4.2. Reactions in Ionic Emulsions
5. Effects of Temperature on the Kinetics in Emulsions: Interfacial Activation Parameters
6. Conclusions and Perspective
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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HLB Range | Application |
---|---|
<3 | Surface films |
3–6 | Water-in-oil emulsions |
7–9 | Wetting agents |
8–15 | Oil-in-water emulsions |
13–15 | Detergents |
15–18 | Solubilizers |
Ea (kJ mol−1) | kchem (dm3 mol−1 s−1) |
---|---|
~0 | ~1010 |
<25 | 109–1010 |
50 | 105 |
100 | 10−4 |
>200 | <10−22 |
AO | Emulsion | Intercept | 102 kI (M−1 s−1) |
---|---|---|---|
OG | 1:1 | 5 ± 5 | 1.0 ± 0.1 |
OG | 1:4 | 2 ± 2 | 1.1 ± 0.2 |
LG | 1:1 | 1 ± 1 | 1.2 ± 0.1 |
LG | 1:4 | −2 ± 2 | 1.4 ± 0.3 |
CA | TOC | PG | OG | LG | |
---|---|---|---|---|---|
T (°C) | 102 kI (M−1 s−1) | 102 kI (M−1 s−1) | 102 kI (M−1 s−1) | 102 kI (M−1 s−1) | 102 kI (M−1 s−1) |
15 | 0.97 ± 0.01 | --- | 4.5 ± 0.1 | 12.9 ± 0.1 | 9.3 ± 0.2 |
20 | 2.15 ± 0.04 | 9.2 ± 0.5 | 11 ±0.1 | 20 ± 1 | 18 ± 1 |
25 | 3.03 ± 0.02 | 16.8 ± 0.5 | 16 ± 0.5 | 33 ± 1 | 29 ± 1 |
30 | 6.64 ± 0.03 | 21 ± 0.4 | 37 ± 4 | 48 ± 3 | 61 ± 4 |
35 | 12.1 ± 0.05 | 37.6 ±0.6 | 91 ± 2 | 75 ± 5 | 105 ± 10 |
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Costa, M.; Paiva-Martins, F.; Losada-Barreiro, S.; Bravo-Díaz, C. Modeling Chemical Reactivity at the Interfaces of Emulsions: Effects of Partitioning and Temperature. Molecules 2021, 26, 4703. https://doi.org/10.3390/molecules26154703
Costa M, Paiva-Martins F, Losada-Barreiro S, Bravo-Díaz C. Modeling Chemical Reactivity at the Interfaces of Emulsions: Effects of Partitioning and Temperature. Molecules. 2021; 26(15):4703. https://doi.org/10.3390/molecules26154703
Chicago/Turabian StyleCosta, Marlene, Fátima Paiva-Martins, Sonia Losada-Barreiro, and Carlos Bravo-Díaz. 2021. "Modeling Chemical Reactivity at the Interfaces of Emulsions: Effects of Partitioning and Temperature" Molecules 26, no. 15: 4703. https://doi.org/10.3390/molecules26154703