**7. References**


Mass transfers occurring within different kinds of emulsions, simple, mixed and multiple, have been described in this chapter. Almost of the examples given are dealing with mass transfer occurring at ambient temperature between phases of different composition. Focus has been made about the results obtained by submitting time to time an emulsion sample to a cooling and heating cycle during which freezing and melting of the phases concerned by the mass transfer are registered through the energies involved in the liquid – solid transition thanks to a differential scanning calorimeter. The amount of the transferred mass is deduced either from the freezing or melting of the pure material droplets A or from the calibration curve that gives the freezing temperature of the droplets made of A+B, versus the composition. This DSC technique appears to be suitable to study this kind of phenomenon as far it permits to follow the transfer and furthermore to get the kinetic of the transfer. Doing so a model of the transfer can be set up and the mechanisms involved can be described. It appears that the mechanism to be considered is a solution – diffusion transfer facilated by micelles that entrapped the compound to be transferred. Therefore a control release can be set up through the formulation of the emulsion. Another type of mass transfer has been described that induces solid ripening as the result of the mass transfer. The case of hydrate formation has been given as an example. The mass transfer due to the diffusion of a material in the oil phase of a W/O emulsion, induces the formation of a solid compound, namely an hydrate, when this compound chemically reacts with water of the dispersed water. Here as well, the DSC technique appears to be suitable but due to overlapping of transitions dealing with water and hydrate a complementary technique is needed. That shows the limit of the DSC technique that needs net liquid-solid transitions and a reduced overlapping of the transitions. To conclude these studies show the great advantage to use emulsions for having mass transfer in a rather short time due to the total high surface area of exchange and the presence of micelles. Therefore, these systems can be considered to set up separation processes, the emulsions being seen as liquid membranes systems or as mini reactors for getting chemical reactions between compounds. Nevertheless a control of the formulation of the emulsions in order to get kinetically stable emulsions at least during the process

Ariyaprakai, S. & Dungan, S. R. (2010). Influence of surfactant structure on the

Avendano-Gomez, J.; Grossiord, J.L. & Clausse, D. (2000). Composition ripening in o/w

Avendaño-Gomez, J. (2002).Etude par calorimétrie du mûrissement de composition dans

Doctorat de l'Université de Technologie de Compiègne, France

contribution of micelles to Ostwald ripening in oil-in-water emulsions. *Journal of Colloid and Interface Science*, Vol. 343, No. 1, (March 2010) pp. 102-108 ISSN

emulsions. *Entropie*, Vol. 36, No. 224-25, (September 1999) pp. 110-116 ISSN 0013-

une émulsion mixte H1-H2/eau et une émulsion multiple H1/eau/H2. Thèse de

**6. Conclusion** 

involved is needed.

0021-9797

9084

**7. References** 


Mass Transfers Within Emulsions Studied by

Oxford, UK

9797

Differential Scanning Calorimetry (DSC) - Application to Composition Ripening and Solid Ripening 775

Garti, N. & Lutz, R. (2004). Recent progress in double emulsion, In: *Emulsions: Structure* 

Geiger, S.; Tokgoz, S.; Fructus, A.; Jager-Lezer, N.; Seiller, M.; Lacombe, C. & Grossiord, J. L.

Grossiord, J. L.; Seiller, M. & Silva-Cunha, A. (1998). Obtaining multiple emulsions, In :

Hasan, M. A.; Selim, Y. T. & Mohamed, K. M. (2006). Removal of chromium from aqueous

Jakobsen, T.; Sjöblom, J. & Ruoff, P. (1996). Kinetics of gas hydrate formation in W/O-

*and Engineering Aspects*, Vol. 112, No. 1, (July 1996) pp. 73-84 ISSN 0927-7757 Jiao, J. & Burgess, D. J. (2003). Ostwald ripening of water-in-hydrocarbon emulsions. *Journal* 

Kaghazchi, T.; Kargari, A.; Yegani, R. & Zare, A. (2006). Emulsion liquid membrane

Kharrat, M. & Dalmazzone, D. (2003). Experimental determination of stability conditions of

Koh, C. A.; Westacott, R.E.; Zhang, W.; Hirachand, K.; Creek, J. L. & Soper, A. K. (2002).

Krishna, R.; Goswami, A. N. & Sharma, A. (1987). Effect of emulsion breakage on selectivity

*Journal of Membrane Science*, Vol. 34, No. 2, (1987) pp. 141-154 ISSN 0376-7388 Kumbasar, R. A. (2009). Extraction and concentration study of cadmium from zinc plant

*Desalination*, Vol. 190, No.1-3, (April 2006) pp. 161-171 ISSN 0011-9164 Kentish, S. E. & Stevens, G. W. (2001). Innovations in separation technology for the recycling

(October 2001) pp. 149-159 ISSN 1385-8947

(March 2002) pp. 143-151 ISSN 0378-3812

(September 2003) pp. 1489-1505 ISSN 0021-9614

Grossiord, pp. 57-80, Edition de santé. ISBN 2-86411-119-5, Paris, France. Hai, M. & Magdassi, S. (2004). Investigation on the release of fluorescent markers from

No. 1-2, (March 1998) pp. 99-107 ISSN 0168-3659

Vol. 96, No. 3-18, (May 2004) pp. 393-402 ISSN 0168-3659

168, No. 2-3, (September 2009) pp. 1537-1541 ISSN 0304-3894

*Stability and Interactions*, D. N. Petsev, pp. (557-667), Elsevier. ISBN 0-12-088499-2,

(1998). Kinetics of swelling–breakdown of a W/O/W multiple emulsion: possible mechanisms for the lipophilic surfactant effect. *Journal of Controlled Release*,Vol. 52,

Multiple emulsions : structure, properties and applications, M. Seiller, J. L.

w/o/w emulsions by fluorescence-activated cell sorter. *Journal of Controlled Release*,

waste solution using liquid emulsion membrane. *Journal of Hazardous Materials*, Vol.

emulsions the model system trichlorofluoromethane/water/non-ionic surfactant studied by means of dielectric spectroscopy. *Colloids and Surfaces A: Physicochemical* 

*of Colloid and Interface Science*, Vol. 264, No. 2, (August 2003) pp. 509-516 ISSN 0021-

pertraction of L-lysine from dilute aqueous solutions by D2EHPA mobile carrier.

and re-use of liquid waste streams. *Chemical Engineering Journal*, Vol. 84, No. 2,

methane hydrate in aqueous calcium chloride solutions using high pressure differential scanning calorimetry. *Journal of Chemical Thermodynamics*, Vol. 35, No. 9,

Mechanisms of gas formation and inhibition . *Fluid Phase Equilibria*, Vol. 194-197,

in the separation of hydrocarbon mixtures using aqueous surfactant membranes.

leach solutions by emulsion liquid membrane using trioctylamine as extractant. *Hydrometallurgy*,Vol. 95, No.3-4, (February 2009) pp. 290-296 ISSN 0304-386X


Colinart, P.; Delepine, S.; Trouve, G. & Renon, H. (1984). Water transfer in emulsified liquid

Dalmazzone, D.; Kharrat, M.; Lachet, V.; Fouconnier, B. & Clausse, D. (2002). DSC and PVT

Dalmazzone, D.; Hamed, N. & Dalmazzone, D. (2009). DSC measurements and modelling of

*Engineering Science*, Vol. 64, No. 9, (May 2009) pp. 2020-2026 ISSN 0009-2509 Davies, S. R.; Hester, K. C.; Lachance, J. W.; Koh, C. A. & Sloan, E. D. (2009). Studies of

Drelich, A.; Gomez, F.; Grossiord, J. L.; Clausse, D. & Pezron, I. (2011). to be published. Elwell, M.W.; Roberts, R.F. & Coupland, J.N. (2004). Effect of homogenization and surfactant

Fouconnier, B.; Legrand, V.; Komunjer, L.; Clausse, D.; Bergfoldt, L. & Sjöblom, J. (1999).

Fouconnier, B.; Manissol, Y.; Dalmazzone, D. & Clausse, D. (2002). Study of

Fouconnier, B.; Komunjer, L.; Ollivon, M.; Lesieur, P.; Keller, G. & Clausse, D. (2006). Study

Frasca, S.; Couvreur, P.; Seiller, M.; Pareau, D.; Lacour, B.; Stambouli, M. & Grossiord, J. L.

*Pharmaceutics*, Vol. 380, No.1-2, (October 2009) pp 142-146 ISSN 0378-5173 Grossiord, J. L. & Stambouli, M. (2007). Potentialities of W/O/W Multiple Emulsions in

Garti, N. & Kovacs, A. (1991). Facilitated emulsion liquid membrane separation of complex

No. 3, (May 2004) pp. 413-418 ISSN 0268-005X

187 ISSN 0376-7388

493-505 ISSN 1418-2874

Compiègne, France

pp. 105-108 ISSN 0340-255X

2002) pp. 72-77 ISSN 0013-9084

Hoboken, USA

239-246 ISSN 0376-7388

(December 2006) pp. 76-82 ISSN 0378-3812

membrane process. *Journal of membrane Science*, Vol. 20, No. (August 1984) pp. 167-

measurements of methane and trichlorofluoromethane hydrate dissociation equilibria in highly concentrated calcium chloride solutions and water-in-oil emulsions. *Journal of thermal Analysis and Calorimetry*, Vol. 70, (February 2002) pp.

the kinetics of methane hydrate formation in water-in-oil emulsion. *Chemical* 

hydrate nucleation with high pressure differential scanning calorimetry. *Chemical Engineering Science*, Vol. 64, No. 2, (January 2009) pp. 370-375 ISSN 0009-2509 Drelich, A. (2009). Emulsions formulées avec des particules de silice : caractérisation,

stabilité, transfert de matière. Thèse de Doctorat de l'Université de Technologie de

type on the exchange of oil between emulsion droplets. *Food Hydrocolloids,* Vol. 18,

Formation of trichlorofluoromethane hydrate in w/o emulsions studied by differential scanning calorimetry*. Progress in colloid & polymer science*, vol. 112,

trichlorofluoromethane hydrate formation in W/O emulsions : dissociation energy and equilibrium with salt + water solutions. *Entropie*, Vol. 38 No. 239-240, (August

of CCl3F hydrate formation and dissociation in W/O emulsion by differential scanning calorimetry and X-ray diffraction. *Fluid Phase Equilibria*, Vol. 250, No. 1-2,

(2009). Paraquat detoxication with multiple emulsions. *International Journal of* 

Drug Delivery and Detoxification, In: *Multiple Emulsion: Technology and Applications,*  A. Aserin, pp. (209-234), John Wiley and Sons Inc. ISBN 978-0-470-17093-9,

hydrocarbon mixtures. *Journal of Membrane Science*, Vol. 56, No. 3, (March 1991) pp.


Mass Transfers Within Emulsions Studied by

pp. 582-588 ISSN 0304-3894

Amsterdam, The Netherlands

2001) pp. 45-53 ISSN 0168-3659

ISSN 0376-7388

*Proceeding ACAT*, Vol. 23

(January 2005) pp. 63-72 ISSN 0378-5173

Differential Scanning Calorimetry (DSC) - Application to Composition Ripening and Solid Ripening 777

Mortaheb, H. R.; Aminia, M. H.; Sadeghiana, F.; Mokhtarania, B. & Daneshyara, H. (2008).

Muschiolik, G.; (2007). Multiple emulsions for food use. *Current Opinion in Colloid* & *Interface* 

Muguet, V.; Seiller, M.; Barratt, G.; Ozer, O.; Marty, J. P. & Grossiord, J. L. (2001).

Ng, Y. S.; Jayakumar, N. S. & Hashim, M. A. (2010). Performance evaluation of organic

Noble, R. D. & Stern, A. A. (1995). Membrane separation technology: Principle and

Tedajo, G. M.; Seiller, M.; Prognon, P. & Grossiord, J. L. (2001). pH compartmented W/O/W

Tedajo, G. M. et al. (2005). Release of antiseptics from the aqueous compartments of a

Venkatesan, S. & Meera Sheriffa Begum, K.M. (2009). Emulsion liquid membrane pertraction

*Engineering Journal*, Vol. 148, No. 2-3, (May 2009) pp. 254-262 ISSN 1385-8947 Yan, J. & Pal, R. (2001). Osmotic swelling behavior of globules of W/O/W emulsion liquid

Yan, J. & Pal, R. (2004). Effects of aqueous-phase acidity and salinity on isotonic swelling of

Potier, L.; Raynal, S.; Seiller, M.; Grossiord, J.L. & Clausse, D. (1992). Study state transitions

Potier, L. (1993). Etude par calorimétrie des changements d'état dans une émulsion multiple

Raynal, S.; Potier, L.; Garcia, S. & Clausse, D. (1992). Etude par analyse Enthalpique

Sacca, L.; Drelich, A.; Gomez, F.; Pezron, I. & Clausse, D. (2008). Composition Ripening in

*Science and Technology*, Vol. 29, N° 7, (2008) pp. 948-952 ISSN 0193-2691

*Science,* Vol. 16, No. 1, (February 2011) pp. 41-60 ISSN 1359-0294

de Doctorat de l'Université de Technologie de Compiègne, France

Vol. 204, No. 1, (July 1992) pp. 145-155 ISSN 0040-6031

*Science,* Vol. 12, (August 2007) pp. 213-220 ISSN 1359-0294

184, No.1-3, (December 2010) pp. 255-260 ISSN 0304-3894

70, No. 1-2 (January 2001) pp. 37-49 ISSN 0168-3659

Study on a new surfactant for removal of phenol from wastewater by emulsion liquid membrane. *Journal of Hazardous Materials*, Vol. 160, No. 2-3, (December 2008)

Formulation of shear rate sensitive multiple emulsions. *Journal of control release*, Vol.

emulsion liquid membrane on phenol removal. *Journal of Hazardous Materials*, Vol.

application, In: , R. D. Noble & A. A. Stern, Elsevier Science ISBN 044481633X,

multiple emulsion: a diffusion study. *Journal of control release*, Vol. 75, No. 1-2 (July

W/O/W multiple emulsion. *International Journal of Pharmaceutics*, Vol. 288, No. 1, 6

of benzimidazole using a room temperature ionic liquid (RTIL) carrier. *Chemical* 

membranes. *Journal of Membrane Science*, Vol. 190, No.1, (August 2001) pp. 79-91

W/O/W emulsion liquid membranes under agitation conditions. *Journal of Membrane Science*, Vol. 244, No.1-2, (November 2004) pp. 193-203 ISSN 0376-7388 Pal, R. (2011). Rheology of simple multiple emulsions. *Current Opinion in Colloid* & *Interface* 

within multiple W/O/W emulsions using calorimetry (DSC). *Thermochimica Acta*,

E/H/E : Application aus transferts de solvant entre deux phases aqueuses. Thèse

Différentielle de la surfusion et de la sursaturation de solutions aqueuses d'urée.

Mixed Water-in-oil Emulsions Stabilized with Solids Particles. *Journal of Dispersion* 


Lachance, J. W.; Dendy Sloan, E. & Koh C. A. (2008). Effect of hydrate formation/

Laugel, C.; Rafidison, P.; Potard, G.; Aguadisch, L. & Baillet, A. (2000). Modulated release of

Le Parlouër, P.; Dalmazzone, C.; Herzhaft, B.; Rousseau, L. & Mathonat, C. (2004).

Lutz, R.; Aserin, A.; Wicker, L. & Garti, N. (2009). Release of electrolytes from W/O/W

Mandal, A. B.; Gupta, S. & Moulik S. P. (1985). Characterization of Tween-20 and Tween-80

McClements, D. J.; Dungan, S. R.; German, J. B. & Kinsella, J. E. (1992). Oil exchange

McClements, D. J.; Dungan, S. R.; German, J. B. & Kinsella, J. E. (1993b). Factors which affect

McClements, D. J. & Dungan, S. R. (1993c). Factors that affect the rate of oil exchange

Mishra, B. & Pandit, J. R. (1989). Prolonged release of pentazocine from multiple O/W/O

*Hydrocolloids*, Vol. 6, No. 5 (November 1992) pp. 415-422 ISSN 0268-005X McClements, D. J.; Dungan, S. R.; German, J. B. & Kinsella, J. E. (1993a). Evidence of Oil

Vol. 160, No.1, (January 1998) pp. 109-117 ISSN 0378-5173

Li, N. N. (1968). Membrane separation process. US Patent 3 410 794

24A, No. 8, pp. 670-674 (1985) ISSN 0376-4710

97, No. 28 (July 1993) pp. 7304-7308 ISSN 0022-3654

ISSN 0168-3659

pp. 178-185 ISSN 0927-7765

1388–6150

0021-9797

ISSN 0927-7757

(1989) ISSN: 0363-9045

dissociation on emulsion stability using DSC and visual techniques. *Chemical Engineering Science*, Vol. 63, No. 15, (August 2008) pp. 3942-3947 ISSN 0009-2509 Laugel, C.; Baillet, A.; Youenang Piemi, M. P.; Marty, J. P. & Ferrier, D. (1998). Oil–water–oil

multiple emulsion for prolonged delivery of hydrocortisone after topical application: comparison with simple emulsion. *International Journal of Pharmaceutics*,

triterpenic compounds from a O/W/O multiple emulsion formulated with dimethicones: infrared spectrophotometric and differential calorimetric approaches. *Journal of Controlled Release*, Vol. 63, No.1-2, (January 2000) pp. 7-17

Characterisation of gas hydrate formation using a new high-pressure micro-DSC. *Journal of Thermal Analysis and Calorimetry*, Vol. 78, No. 1, (2004) pp. 165–172 ISSN

double emulsions stabilized by a soluble complex of modified pectin and whey protein isolate. *Colloids and Surfaces B: Biointerfaces*, Vol. 74, No. 1, (November 2009)

micelles in aqueous medium from transport studies. *Indian Journal of chemistry*, Vol.

between oil-in-water emulsion droplets stabilised with a non-ionic surfactant. *Food* 

Exchange between Oil-in-Water Emulsion Droplets Stabilized by Milk Proteins. *Journal of Colloid and Interface Science,* Vol. 156, No. 2 (March 1993) pp. 425-429 ISSN

oil exchange between oil-in-water emulsion droplets stabilized by whey protein isolate: protein concentration, droplet size and ethanol. *Colloids and Surfaces A: Physicochemical and Engineering Aspects,* Vol. 81, No. 13 (December 1993) pp. 203-210

between oil-in-water emulsion droplets stabilized by a non-ionic surfactant: droplet size, surfactant concentration, and ionic strength. *Journal of Physical Chemistry*, Vol.

emulsions. *Drug Development Industrial Pharmacy,* Vol. 15, No. 8, pp. 1217-1230


**34** 

*Iran* 

**Mass Transfer -** 

Behnam Khoshandam

*Semnan University* 

**The Skeleton of Purification Processes** 

The purification or generally separation processes play a major role in a chemical, petrochemical, oil and gas industry. After producing a synthetic material usually a purifying section should be designed. The purification processes contain broad units of absorption/ desorption, distillation, liquid-liquid extraction, leaching, humidification/dehumidification, drying, adsorption/desorption, evaporation, membrane and crystallization. Processing design of these units is one of duties of chemical engineers and for this reason literatures related to purification are taught to chemical engineers as different courses on unit

The basic rules of mass transfer are as skeleton of different separation or purification processes. Concentration gradient of one or more constituents in a media can force the molecules to transfer in different directions based on Fick's first law of diffusion. Creating a convection form in flow of molecules using different ways in industrial units helps the molecules transportation and in other word the purification rate. Of course to this scenario addition of other phases also should be considered. Addition of a phase or an excess media to the first media produces the problem of passing molecules from the interface between phases and answer to the question of how much molecules are able to pass the interface dam. Therefore in this stage phase equilibrium coming from thermodynamics can help us to answer the question. Using different equilibrium data in handbooks helps us to construct

On the other hand, different contact processes of crosscurrent, countercurrent and cocurrent of different phases create operating line or operating curve that can show the conditions of flows pass next to each other in mass exchanger equipment. Stagewise and differential types of contact are two usual forms of phase contact in mass exchanger equipments. The equipments used these forms of contacts are tray and packed towers and number of theoretical trays and the height of packed beds are two processing parameters that need to

Many good literatures have been published on separation processes. Different units have been studied in a valuable book under the title "Mass Transfer Operations" (Treybal, 1955) and added others as well, (McCabe et al., 1956), (Pavlov et al., 1979), (Henley et al., 1981), (Hines & Maddox, 1985), (Khoury, 1995) and (Geankoplis, 2003). The analysis of different separation processes was carried out from the same point of view. The processes were

**1. Introduction** 

operations and separation processes.

be calculated in separation processes.

the equilibrium curves.

