Liquid-Liquid Interfaces

By:

Ashoordin Ashoormaram

Capstone Project 2011-2012 Academic Year

Abstract
A scientific issue of significance to society is the separation of different chemical species. Real life examples occur in mining processes where by-products need to be filtered out; treatment of nuclear waste, and environmental cleanup for the removal of toxic metals. The separation processes take place at the oil-water interface. Since our current understanding of the physics of the interface is limited, my research is focusing on this area. I am studying the effect of Er 3+ ions on the ordering of extractant molecules at the interface between an organic solution of Dodecane / DHDP and an aqueous solution of ErBr3 / HBr with
pH 2.5 . I am testing the hypothesis whether formation of a monolayer at the interface between

two phases would allow us to understand better the ion-extractant interaction. A typical graph of interfacial tension versus temperature for such an interface consists of two parts: (1) A linear relationship between interfacial tension and temperature; as the temperature increases the surface tension correspondingly increases linearly; (2) A plateau region characterized by slight changes in the surface tension. The distinction between these two regions is a sudden change in the slope of the plot at some particular temperature named transition temperature. It is basically a temperature at which the interaction forces between surfactant molecules are broken as the interface undergoes an increase in the temperature passing from an ordered phase to a disordered phase. Thermodynamically, the high positive slope below the transition shows that the entropy of molecules at the interface is highly less than the entropy of the same molecules in the bulk phase. In other words, transition is between a highly ordered and a slightly disordered interface. Also, there is an offset between the plots for different concentrations of ErBr3 accompanied by a shift in the transition temperature which is an indication of Er 3+ ions being absorbed into interface.

Introduction
For many practical reasons, an understanding of the properties of aqueous solutions at interfaces is very important. Some reactions take place only at an interface. Membranes and the electrodes of an electrochemical cell are some obvious examples. A scientific issue of significance to society is the separation of different chemical species. Real life examples occur in mining processes where by-products need to be filtered out; treatment of nuclear waste, which is associated with separation of radionuclides; and environmental cleanup for the removal of toxic metals. The separation processes take place at the interface of two liquids, typically oil and water. The target species is in the water phase, along with many other chemical species. An organic molecule, called an extractant, is placed into the oil phase. The extractant will journey to the interface, where it grabs hold of the target species, and drags it into the oil phase. In this way, the target species is separated from other chemicals in the water phase and can then be further processed. Improving this process involves an understanding of the chemical interactions of the target species, the extractant and the oil and water phases. Much of this understanding relies upon chemistry. However, an important part of this process is the interaction that takes place at the interface. Our current understanding of the physics governing the interface is inadequate1 and my research focuses on this area. My efforts go toward developing a model system to probe the interaction of metal ions with extractants. Currently, I am working with Professor Schlossman of UIC, whose research group has shown that the interaction of ions with extractants does not result in a buildup of the ionextractant complex at the interface.2

Questions, Problems and Objectives

I am investigating the role of multivalent (multiple charge) ions on molecular ordering at liquidliquid interfaces. The electric field near multivalent ions is much larger than near monovalent ions. Although this higher field is believed to have a significant effect on the nearby ordering of other ions and molecules, it is not well understood and is a topic of current research. The specific question that I am asking is: What is the effect of Er3+ ions on the ordering of extractant molecules at the interface between a bulk oil phase (Dodecane) and bulk water? I am testing the hypothesis whether formation of a monolayer at the interface between two phases would allow us to understand better the ion-extractant interaction. My faculty mentors research group is studying the role of electrostatic interactions at soft interfaces. My studies contribute to this field of research by their investigation of the role of multivalent ions in molecular ordering at interfaces. Finding an appropriate surfactant that has a similar chemical interaction with the ion as the extractant in a stable layer at the interface is important because it will allow us to study the structure of this ion-surfactant complex with x-ray scattering. This information will then allow us to understand the ion-extractant interaction and, as a result, we will have more practical methods in separation processes in industry. For this purpose, we are looking for the formation of a stable monolayer or bilayer formed at the interface between two phases namely, the lower aqueous solution of ErBr3 / HBr and the upper organic solution of DHDP / Dodecane . It is assumed that the formation of this layer is implied through a considerable decrease in the slope of interfacial tension versus temperature graph below the transition temperature as the sample cools down in its first cycle. In other words, any decrease in the slope, in cooling stage of each cycle of measurements, is an indication of the Er3+ ions being absorbed into the interface. It is believed that this absorption happens via DHDP

surfactants at the interface at the time during which the sample is beyond the transition temperature in the first cycle because the interface has a less ordered structure in the plateau region. According to this hypothesis, then, the time that the sample is stayed beyond the transition temperature is of crucial importance as it characterizes the chance being given to the Er3+ ions to be absorbed into the interface. So, to show this is the case, we need to have a control over this time period by changing it on our will. However, before modifying the Python program associated with the tension measurements, we had no control over the amount of time that the sample is stayed beyond the transition temperature. For this purpose, we chose to do the extreme case in which the sample was heated up beyond the transition temperature for about a complete day, giving more chance to the Er3+ ions leaving the lower phase and, hence, changing its composition causing a shallower surface tension versus temperature plot below the transition temperature.

Physics and Chemistry of Interfaces

An interface between two immiscible liquids is an inhomogeneous6 environment. The molecular environment at the interface is different than in the bulk.12A liquid-liquid interface is not an infinitesimal sharp boundary in the direction of its normal, but rather, it has a certain thickness.5In other words, the density profile ( z ) normal to the surface will exhibit a behavior similar to Fig. 1 adapted from Ref. [6]. The orientation of the molecules at the interfaces also affects the thickness of an interface.8

Figure 1: A schematic illustration of the interface between two immiscible liquids, showing the total density variation. The dotted line is the intrinsic step function prole, and the solid line is the result of the capillary broadening.

Surface tension and surface potential are the only macroscopic properties exhibiting some information about separation of different chemical species mentioned earlier. However, standing alone, these techniques lack the ability to provide a detailed understanding at the microscopic level.(Benjamin, 2). This is why X-ray reflectivity has been employed as a complementary technique. However, in this paper I try to address the macroscopic understanding of the interfaces through utilizing the most relevant thermodynamic property of the interface, namely surface tension, and draw a conclusion (if possible at all) about the structural ordering at microscopic level. Physical Interpretation of Surface Tension It is energetically favorable for molecules to be surrounded by other molecules. They attract each other through different electrostatic interactions such as van Der Waals and hydrogen bonding. However, at the boundary surface of a liquid, molecules are partially enclosed by other molecules and, hence, the number of neighboring molecules is less than that of in the bulk. This is energetically unfavorable.5In order to bring molecules from the bulk to the surface, work has to be done. The energy required for bringing molecules from the bulk to the surface for creating new surface area is called surface tension, labeled with the typical range of 20-80 mN/m for most liquids.5Since is a direct indication of the magnitude of intermolecular forces, it is an important property of a liquid.12Thus, the Statistical mechanical expression for the surface tension adapted from Ref. [6], is

dW 1 1 f ( i, j ) R ( i, j ) , with = x, y , z = Vzz (Vxx + Vyy ) , whereV = dA A 2 i< j

(1)

, where f ( i, j ) and R ( i, j ) are the th component of the total force and the distance between molecules i and j , respectively.

Thermodynamic Definitions of Surface Tension In order to have a concrete picture regarding the nature of interfaces and their corresponding tensions, we can make use of thermodynamics. 1. The surface tension is the increase in the Helmholtz free energy of the system per increase in surface area at constant temperature, the total volume, the volume of phase and the total numbers of all components3:

( F A )

T ,V ,V , Ni

2. The surface tension is the increase in the Gibbs free energy per increase in surface area at constant temperature, pressure and the total numbers of all components3:

( G A )

T , P , Ni

3. The most relevant concept is the excess interfacial entropy, which is the negative derivative of the tension with temperature at constant pressure and surface area.3-5

s ( T ) P , A

(2)

For the majority of pure liquids, the surface tension decreases with increasing temperature. The entropy on the surface is thus increased, which implies that the molecules at the surface are less ordered than in the bulk liquid.5However, as we will see later on, this is not the case in water-oil interfaces. Interfacial tension is directly6 related to the interface thickness and density profiles of the two liquids. Using Gibbs adsorption equation ( / ln c )T = RT , one can indirectly obtain a microscopic interpretation of the interface structure.6Here, c is the molar concentration, is the surface excess concentration, R is the gas constant and, T is the temperature. Surface tension measurement is one of the first techniques developed to study adsorption thermodynamic and kinetics. (Benjamin, 20). According to this equation, adsorption at the interface is accompanied by a decrease in surface tension.

Sperline & Freiser (6) have used situIR spectroscopy in order to study the adsorption of cetylpyridinium chloride at the water-hydrocarbon interface, and they measured the extraction kinetics of aqueous metal ions into the organic phase. Surfactants Soluble amphiphiles, also known as surfactants, dominate much of the interfacial phenomena. The name is a contraction of the phrase surface active agent.5The term amphiphiles indicates that one part of the molecule favors a particular solvent while the other favors another solvent and the two solvents are immiscible. In most cases, one solvent is water and the water-loving part is called hydrophilic. The other part that likes oily environment or air is hydrophobic. The hydrophobic part consists of a long, straight alkyl chain CH 3 ( CH 2 )n

C 1

, nC = 8 20 . For special

applications the hydrocarbons might be fluorinated to some extent.5 According to Butt, Craf and Kappl, Surfactants are divided into four groups: Anionic surfactants have a hydrophilic group carrying a negative charge. Cationic surfactants carry a positive charge in their hydrophilic part. Nonionic surfactants are not charged. The hydrophilic head derives its water solubility from highly polar groups such as polyethylene oxide or sugars. Amphoteric surfactants bear both positive and negative charges so that the net charge is zero. The Role of Extractants at the Water/Oil Interfaces Ion transfer through the interface is a key point in describing processes that take place at the interface. Most of the extractants are insoluble in water and display surface activity at the wateroil interface upon adsorption from the organic phase. The adsorption process at the interface is part of the general process of ion transfer through the interface. So, as Popov argues, there must be a correlation between the extraction and adsorption characteristics in water-oil systems.11

Capillary Wave Theory

Capillary wave theory yields a direct relation between the interfacial width and interfacial tension as mentioned in Ref. [6]:
12

2 =

kT 1 + 2 2lc 2 b 2 ln 4 1 + 2 2lc 2 A

(3)

2 , where lc = 2 g m1 1 m2 2 is capillary length, A = L is the surface area of the interface,

mi , i = 1, 2 are the molecular masses of the two liquids, g is the Earths gravity and, b is the
liquid bulk correlation length (which is a measure of the range over which fluctuations in one region of liquid are correlated with those in another region. In other words, two points separated by a distance larger than the correlation length will have relatively independent fluctuations) 7.

= z) The density profile is also given by (

(1 2 )( 1 + 2 ) (1 2 )( 1 2 ) erf ( z

2 2

(4)

Equation 4 describes a smooth change in the total density from the value 1 (for z 0 ) to the value 2 (for z 0 ) as shown in Figure 1.

Scattering Theory
The first approximation of the scattering theory in X-ray surface measurement of specular reflectivity from a flat surface, as mentioned earlier, is a rapid jump in the electron density across the interface. The expression given for the reflectivity for this model is known as the Fresnel reflectivity, RF ( Qz ) ( Qc 2Qz )4 . Contrary to the Fresnel reflectivity, the Parratt approach to an arbitrarily shaped profile requires numerical computation, and is valid only for very small angles of incidence. The Master Formula, R ( Qz ) = M 21 M 22 ( Qc 2Qz )
2 4

dz

( z) z

exp ( iQz z ) ,

is an analytic expression in order to explain the reflectivity for non-grazing angles of incidence for an arbitrary profile of a flat surface.8 In the case of a monotonic variation through the interface described by the macroscopically

z) averaged electron density profile ( =

( 2 ) (1 + erf z

2 along the surface normal,

z , the prediction from the Master Formula is that the reflectivity for a flat surface would fall
exponentially as the wave vector Qz = ( 4 ) sin i increases with incident angle i :

R ( i ) RF (= i ) exp ( Qz 2 2 2 ) .8 (See Fig. 2 adapted from Ref. [10]).

Figure 2: X-ray scattering geometry from a water-oil interface. X-ray reflectivity is measured with equal incident and reflection

angles namely, = . The wave-vector transfer for reflectivity, Qz is normal to the interface, showing that reflectivity analyses structure normal to the interface. Off-specular diffuse scattering is measured by fixing and scanning , leading to a nonzero inplane component of the wave-vector transfer and a sensitivity to in-plane structure.

For other types of interfacial profiles, R ( i ) RF ( i ) is proportional to the absolute square of the effective surface structure factor , eff ( Qz ) =
1
+

dz

( z) z

exp ( iQz z ) , that can be achieved

using either the numerical Parratt method or the analytical Master Formula.8 However, as a result of thermal fluctuations, liquid surfaces are not flat. As mentioned by Schlossman (8), the Born approximation is the link between the reflectivity from surfaces obtained by either the Fresnel expression or the Master Formula for flat surfaces and thermally

rough surfaces. There is a distinction between eff ( Qz ) and the intrinsic surface structure factor,
( Qz ) 1
+

dz

z h ( rxy ) z

|h( r )=0 exp ( iQz z ) , which arises from the intrinsic electron density xy

profile ( z ) excluding the effects of thermal fluctuations. In the case of a flat interface between two bulk phases with different electron densities, the factor of is replaced by = j= 0 j= , where j =0 and j=
J +1 J +1

refer to the electron densities of the bulk phases.8Using Born

approximation, the following expression for the differential cross-section can be formulated:
4 2 d Af ( Qc 2 ) ( Qz ) H Qxy , Qz , where 2 4 d Qz 1 1 = = iQxy rxy H Qxy , Qz d 2 rxy exp Qz 2 h 2 ( 0 ) h ( rxy ) h ( 0 ) exp iQxy rxy d 2 rxy H ( rxy , Qz ) exp 2 2 4 4

that is valid both on and off the specular condition. As seen from the above formulae, the Born approximation differs from either the Parratt or Master Formula in that eff ( Qz ) is replaced by
2

the product of ( Qz ) and a term that accounts for the thermal capillary fluctuations.8
2

As Schlossman argues, in the absence of gravitational effects, the primary problem for scattering from liquid surfaces is that the angular dependence of d d exhibits an algebraic singularity at the specular condition and the specular reflectivity is calculated by integration of this algebraic singularity over the experimental resolution. However, the major failing of the Born approximation is that both the incident and scattered angles must be sufficiently far away from the grazing incidence condition that refraction effects associated with the finite x-ray index of refraction can be neglected.8 The Distorted Wave Approximation (DWA) is developed to overcome this limitation. Surface inhomogeneities of the liquids can be either thermally induced or in-plane. The latter have length scales anywhere from the atomic up to the macroscopic. If these inhomogeneities are random

they will cause diffuse off-specular scattering in addition to the scattering from thermal capillary waves. On the other hand, if the inhomogeneities are periodic they will produce interference peaks.8 Interfacial Tension, Molecular Ordering and Phase Behavior of Water-Oil Interfaces A typical graph of interfacial tension versus temperature for an interface made between an organic solution of Dodecane-DHDP and an aqueous solution of ErBr3-HBr with pH of about 2.5 is made up of two parts: the first part is a linear relationship between interfacial tension and temperature; as the temperature increases the surface tension correspondingly increases linearly. The second part is a more subtle relationship characterized by slight changes in the surface tension with temperature. This region is regarded as a plateau region. The distinction between these two different regions is a sudden decrease in the slope of the plot at some particular temperature named transition temperature. (See Fig. 3).

Surface Tension (mN/m)

Linear

Plataue

Transition Temperature

Temperature (C)

Figure 3. A typical temperature dependence of interfacial tension of the Dodecane-Erbium (III) Bromide interface

As seen from the plot and based on formula 2 mentioned earlier, the higher positive slope below the transition shows that the excess entropy is highly negative; the entropy of molecules at the

interface is highly less than the entropy of the same molecules in the bulk phase. Similarly, beyond the transition temperature, the excess interfacial entropy is slightly negative, showing that the interfacial molecules still have smaller entropy than in the bulk, even though now the difference is much less than before. This qualitative analysis shows that the transition is between a highly ordered (such as liquid state) and a slightly disordered (such as gas state) interface. (See Fig. 4 adapted from Ref. [16]). Quantitative analysis demonstrates that the low temperature phase is an ordered layer of surfactants at the interface.2

Figure 4: The difference between an ordered (left-hand) and a disordered (right-hand) interface in terms of the way surfactants
are packed together to form a stable monolayer at the oil-water interfaces.

Using the Born approximation, under the assumption that X-rays reflected from the solid and gas domains interfere coherently, for domains of diameter at most equal to 10 m ,13 the normalized reflectivity can be written as
2 2 R= RF c (T ) A1 + (1 c (T ) ) A2 exp Qz

(5)

where A1 represents the reflection from domains of thickness d , A2 represents the reflection from the regions between the domains, is a temperature-dependent interfacial roughness due to capillary waves and the coverage c (T ) is the fraction of interface occupied by the solid domains. For the case of fluorinated monolayers at the water-hexane interfaces,13 at temperatures well below the phase transition, the monolayer cover the entire interface. In this case, c (T ) 1 , and the expression (5) reduces to a single layer model with a homogenous monolayer of surfactant packed in between bulk water and hexane solution. Tikhonov, Li and Schlossman observed a sharp change in coverage at transition temperature correlating very well with the location of kink in the interfacial tension for the case of FC10OH and FC12OH .

Using SALR potential model14

, r , v (r ) = exp z1 ( r 1) r + A exp z2 ( r 1) r, r > .

, the phase behavior of a system of particles is schematically shown in Fig. 5 adapted from Ref. [14]. This phase diagram is a result of competing between an interparticle attraction whose strength is controlled by a parameter > 0 and a repulsion whose strength is controlled by a parameter A > 0 based on the assumption z1 > z2 . Thus, surfactants at water-oil interfaces display a phase structure consisting of homogenous and inhomogeneous phases encompassing solid, liquid and, gas monolayer regions.10The transition temperature of a water-oil interface is one in which a drastic change in the molecular ordering and phase behavior of surfactants occur. It is basically a temperature at which the interaction forces between surfactant molecules are broken as the interface undergoes an increase in the temperature passing from an ordered phase to a disordered
Figure 5: A schematic representation of a full
phase diagram based on SALR potential model

phase. It is shown10 that the fluorocarbon alkanols with rigid rod tails form ordered solid phases and the hydrocarbon alkanols with flexible tails form disordered liquid phases even though both form solid phases at the water-vapor interface. Whether the interface is a monolayer or a multilayer depends,10 on molecular length of both the alkane solvent and the alkanol surfactants. Also it is shown15 that at the water-vapor interface, n alkanols and n alkanoic acids of adequate tail length form monolayer phases containing ordered tails but, at the water-hexane interfaces, due to the hydrogen bonding interactions in surfactant monolayers, the molecular ordering is different; they form monolayer phases with disordered tails. In the same reference, it

is proved that a small variation in the headgroup structure results in a considerable change from disordered to ordered tailgroups. Sometimes, the adsorption of amphiphilic molecules at the surface of a liquid is so strong that a monolayer is formed. If the amphiphiles do not dissolve in water, they form insoluble monolayers like phospholipids.5On the other hand, introducing a solute to a pure liquid, will lower the surface tension and, hence by the Gibbs equation, the solute must be adsorbed at the interface. This adsorption amounts to formation of a monolayer of solute on the surface.3Monolayers show ordered phases similar to three-dimensional systems and their structural molecular ordering is investigated by X-ray reflectivity; X-ray reflectivity determines the film thickness and electron density distribution normal to the water surface. The surface tension reduces with surfactant concentration and with the increase in the surfactant tail. A large effort had been put2 to establish the fact that for a water/Dodecane interface, the surface tension decreases with an increase in the concentration of the surfactant. (See Fig. 6 adapted from Ref. [2]) This could be explained by the fact that any increase in the surfactant will result in a denser interface formed by the surfactant in which the polar heads of the DHDP establish new and stronger hydrogen bondings with the polar water molecules compensating the loss of neighboring contacts at the interface minimizing the Gibbs free energy of the surface. In other words, surface molecules have more available neighbors to bind with.

Figure 6: Interfacial tension measurements for water/Dodecane systems using Wilhelmy Plate method at
different concentrations of DHDP surfactant. As seen above, the excess interfacial entropy changes slightly in different directions of heating/cooling procedures and the number of the cycle.

Methodology
I am using interfacial tension measurements to determine if the surfactant/extractant forms a stable single layer of molecules at the interface between two phases. Interfacial tension is proportional to the integrated density profile across the interface and is sensitive to the net effect of all molecules that adsorb to the interface. X-ray reflectivity can measure the density profile on the Angstrom length scale. These techniques characterize the molecular ordering at the interface. They are used to characterize this ordering both with and without Er3+ ions. As part of my project, I am developing a model system to probe the interaction of metal ions with extractants between two phases. I am in search of a surfactant that has a similar chemical interaction with the ion as the extractant, but will exist in a stable layer at the interface. For this purpose, I am studying the variation of interfacial tension with temperature at different concentrations of the

ErBr3 being used in the lower aqueous solution. Comparing these profiles with the images
obtained through X-ray reflectivity methods will justify our hypothesis mentioned earlier. Experimental methods for measuring surface tension involve the contact of three phases, usually glass, air and the liquid being studied. This implies that we must understand the properties of three interfaces namely, the liquid/gas, the liquid/solid and, the solid/gas. However, as mentioned by Fawcett,12 the interface is usually curved because in such simple system the cohesion forces in the liquid are not necessarily the same as adhesion forces between the glass and the liquid. Moreover, since curved interfaces have complicated properties compared with the flat surfaces, we have to establish a flat interface in order to measure its surface tension. For this purpose, we use a Mylar strip in contact with the glass containing the sample at a level where the interface will be formed. In other words, the macroscopic boundary line between two phases must be leveled with the bottom line of the Mylar strip supported by a stainless steel strip from inside.

The presence of the Mylar strip will prevent the formation of curved boundary along the glass by reducing the adhesion forces between the liquid and the walls, providing a flat interface. The Wilhelmy-plate method is applied in order to measure the surface tension. (See Fig. 7 adapted from Ref. [9]). This technique uses a thin filter plate that is weighed before and after being placed in contact with the interface. The difference in weight, as measured by a sensitive electronic balance, is proportional to the interfacial tension namely, F = 2 L where L is the length of the plate. It is important that the plate is wetted by the liquid and, also close to the three-phase contact line the liquid surface is oriented almost vertically (provided that contact angle is 0o ). Otherwise, this method is simple and no correction factors are needed provided that plates are clean by preventing contamination in air.5

Figure 7: A schematic Demonstration of Wilhelmy Method

The organic solution of our sample is made up of anionic surfactant solute named dihexadecyl phosphate, (also known as DHDP), with the chemical formula dissolved in a liquid alkane hydrocarbon solvent of the paraffin series named Dodecane, (also known as dihexyl, bihexyl or, adakane 12), with the chemical formula CH3(CH2)10CH3. And, the aqueous solution of our sample is made up of Erbium (III) Bromide dissolved in the acidic solution of HBr with a pH of about 2.5.

First of all, the organic and aqueous solutions are made separately. The organic solution is heated up to 550 600 C using a hotplate. The hot solution must remain at that temperature for at least one hour until it is needed later on. Then two stainless steel and Mylar strips which are already cleaned are put together: the latter on top of the former. They are bent in a circle configuration and then placed inside a small cleaned dish letting them slowly expand getting in direct contact with the walls of the dish. Using a reference level, the bottom line of the outer Mylar strip must be leveled; it is where the interface between two phases will form. However, in order to have a better look at the interface at any time, it is important that the stainless steel strip be raised for about half a centimeter above the bottom line of the Mylar strip. Then, the dish is put inside the system mounted on top of a leverage surrounded by the thermostat. A clean small stir bar is placed inside the dish along with the cleaned filter plate hanging on a sensitive microbalance. Using a pipette, we transfer the aqueous solution first into the dish until it reaches about two millimeters above the bottom line of the Mylar. We turn on the stir bar at an intermediate rate and then turn the heater on using the Lake Shore connected to the thermostat covering the system. The setpoint temperature should be about 280 C in order to pre heat the aqueous solution before adding the organic solution on top of it. It is worthwhile to mention that during the whole process of heating the aqueous solution, the filter plate must be immersed wholly into the water phase with the voltmeter connected to the microbalance turned on. This makes the filter plate completely wet before being ready for any later measurements. The system will reach equilibrium in about an hour and then we turn off the stir bar motor so that to give some time (about half an hour) giving the impurities inside the aqueous solution some chance to be collected on the surface.

From now on, the procedures must be followed as fast and careful as possible for reasons mentioned later on. We aspirate the surface of the aqueous solution using an aspirator with a cleaned pipette so that the surface of the solution is leveled exactly with the bottom line of the Mylar strip. As soon as the temperature of the beaker containing the flask of organic solution reaches to some temperature about 300 C , we turn on the stir bar motor again and, we add the organic solution on top of the aqueous solution using another cleaned pipette in the amount of

( 65 75) mL . Then, we cover the dish with the provided parts and the thermostat together in
order to cover the whole system minimizing any possible loss of heat transferred to the dish containing two phases. We put two temperature probes in place: one in the upper part of the thermostat which controls the temperature of the system namely, channel A and the other inside the solution through a hole provided on the upper part of the thermostat namely, channel B to read the actual temperature of the system inside the dish. Then, quickly and carefully, we set the temperature to 280 C and wait for the system to reach thermal equilibrium in about an hour. Now, it is the time to explain the reason of being fast and careful in the last paragraph in preparing the sample for interfacial tension measurements. One of the drawbacks of this procedure is that for some, yet unknown, reasons precipitation of the crystalline DHDP constituent of the organic solution occurs at the interface especially at low temperatures. The existences of these precipitations affect the interfacial tension and will cause a lot of ambiguities about the actual meaning of the data. Since we usually heat up the sample starting with 280 C , this temperature is of great importance because it is the minimum temperature that the sample will be exposed to and hence very prone to precipitation. The time during which the heater is turned off, the temperature of the aqueous solution is going down and the final equilibrium temperature of the system after adding the organic solution will be lowered, probably helping the

precipitation takes place on the interface. This is why it is crucial to minimize the time the heater is turned off by doing the last procedures as fast as possible and, more importantly, to check the interface at about equilibrium temperature just before running the experiment; if there is any precipitation present on it, the measurement will have no meaning and the sample must be disregarded. This actually happened in some cases and I had to prepare new samples for interfacial tension measurements. For interfacial tension measurements, for both time and temperature scaling, a program is written in Python in which all measurements are taken automatically as the temperature of the sample is changed over time. Before any measurements, the software must be connected to both instruments namely, the Lake Shore Temperature Controller and the Voltmeter Weight Controller. Once the program is ready, we can enter the size of the filter plate and the channel corresponding to the actual temperature of the sample inside the dish namely, channel B. After reaching equilibrium, we take the filter plate out of the aqueous solution and we adjust it such that it is just above the interface before being drawn into it. Then, we measure the reference voltage which is needed for measuring the reference weight of the plate by pressing the first measure button of the opened window on the left. Then, we bring the plate slowly down such that it just grabs the interface. At this point we press the second measure button of the opened window on the right to read the instantaneous interfacial tension. Using the surface tension vs. time feature of the program, we can monitor the tolerance of the surface tension values at equilibrium temperature in order to set the sample settings of the software. After being satisfied with the tolerance of the surface tension values at thermal equilibrium, we basically are ready to run the Surface Tension vs. Temperature experiment by pressing the Start button of the last part of the opened window.

Notes: 1. Contamination is the main source of error for the measurement procedures. So, it is of great importance to follow the procedures in a very systematic and clean manner. Before using any laboratory accessories or parts including, but not limited to, flasks, dishes, pipettes, filter plates, stir bars, strips, and temperature probes, we must be sure that they are already cleaned according to the Cleaning Protocol of Laboratory Glassware. 2. The stir bar motor must be working constantly during the whole process which may take up to 4 days in each run. And, whenever the temperature is changed by an increment of 10 C , it is recommended to check the interface making sure of the cleanness of the interface regularly.

Measurements and Results

The appendix figures (8 through 25) provide the whole set of our interfacial-tension measurements. They display the variation of interfacial tension with temperature at different concentrations of the ErBr3 as well as initial conditions namely, the initial temperatures of the two phases just before mixing. The aqueous phase of the samples that I used contained HBr / ErBr3 with three different concentrations of ErBr3 but, a fixed value for the DHDP concentration of the organic solution which was chosen to be (1.07 0.03) 104 M . As seen from Figs. 8 through 25, Instead of having a falling region after the transition temperature, we encountered a slightly rising region, considered basically a plateau; For the cases where we used stainless steel and Mylar strips, (1) the excess interfacial entropies of the systems before transition temperatures were slightly different; there were consistent shifts in the location of the transition temperatures; And, the plots were not smooth

enough to be used for any possible explanation for the behavior of the system in different conditions. These all led us to our first hypothesis that during the first heating of the sample, new impurities are introduced somehow to the system which manipulates the interactions between the constituents of the interface by changing the composition of the system thereafter. By removing the stainless steel strip from the procedures, and conducting the measurements using only Mylar strip, we eliminated the inconsistency. Plots became smooth with only slight shifts in the transition temperature and the linear slope of the plots; For the cases where we used only Mylar strip, we observed the following trends: 1. The slope of the plot above the transition temperature, with or without ErBr3 , no matter in what stage of the cycle, was constant; (See Figs. 17-19, 22-25). 2. In the absence of ErBr3 in the lower phase, the system is reproducible; all three stages: first heating, first cooling, and second heating have almost identical plots. (See Fig. 22). 3. When there is ErBr3 in the lower phase, aside from the first heating stage which has the lowest slope, all other stages have small difference in appearance. (See Figs. 17-19, 2225). 4. Introducing ErBr3 to the lower phase causes a decrease in the interfacial tension and an increase in the transition temperature of the interface; (See Figs. 22-25).

5. For systems containing ErBr3 in the lower phase, the first heating stage of the first cycle
has smaller slope than the same systems without ErBr3 . However, in the first cooling stage, the difference is almost vanished. Interestingly enough, in the second heating stage, the trend is reversed; the slope is slightly larger than the same systems without ErBr3 . (See Figs. 22-25).

Note:
Two important features of each plot are the slope of the linear region below transition temperature and the location of transition temperature itself. These two parameters are found using best linear fit feature of M.S. Excel. Each plot is modeled as two straight lines with different slopes and y-intersections. The line with the higher slope and smaller y-intersection corresponds to the linear region of the plot below transition, and the line with lower slope and larger y-intersection corresponds to the plateau region. The x-component of the intersection point of the two modeled lines will represent the transition temperature. The uncertainties of the two features which are included in each plot for different (heating/cooling) stages are found using the following tricks: I. Linear slope: the points below transition region that are best described as being followed by a single line are chosen. Then, the best linear fit is found using all of them; the slope of this line will be the mean value of the actual slope. However, by changing the number of the points being considered, which is at least equal to three, we found the minimum and the maximum value of the slope. Of course, one of these extreme has maximum distance from the mean value. The difference between the mean value and that extremum is the uncertainty of the measurement. II. Transition temperature: always is chosen somewhere in the range (0.2-0.5) C based on the sharpness of the transition region. The smoothest transition will have the largest uncertainty, e.g. 0.5C and the sharpest transition will have the smallest uncertainty, e.g. 0.2C. Thus, this uncertainty is qualitatively extracted by the amount of deviation between the modeled straight lines and the actual plot; the closer the modeled lines to the actual behavior of the system are, the less uncertainty of the transition temperature is.

Conclusion
Since, interfacial tension is the most relevant thermodynamic property of the interface, Interfacial tension vs. temperature plots are valuable means for studying the thermodynamics of the oil/water interfaces. Even though, it is a direct indication of the magnitude of intermolecular forces, but surfaces-tension measurements, alone, cannot determine the structural ordering at microscopic level. This is why x-ray reflectivity has been employed as a complementary technique to study the structure of the ion-surfactant complex at oil/water interfaces. However, here, the most relevant concept used to study the macroscopic characteristics of oil/water interfaces is the excess interfacial entropy, which is the negative derivative of the tension with temperature at constant pressure and surface area. For majority of pure liquids, the surface tension decreases with increasing temperature. The entropy on the surface is thus increased, which implies that the molecules at the surface are less ordered than in the bulk liquid. However, this is not the case in the interfaces under study. Here, the highly positive slope below the transition temperature indicates that the excess interfacial entropy is highly negative; the entropy of molecules at the interface is much smaller than the entropy of the same molecules in the bulk phase. Similarly, the slowly increasing plateau region above the transition temperature, indicates that the excess interfacial entropy is still negative, indicating that the interfacial molecules have slightly smaller entropy than in the bulk. In other words, the interface is always more ordered than the two bulks. But, the drastic change in the slope at the transition temperature indicates that two regions behave differently. The qualitative analysis shows that the transition is between an ordered low-temperature phase and a disordered high-temperature phase at the interface.

Secondly, the plots of any individual system are almost identical above the transition temperature for different (heating/cooling) stages independent of the presence of Er ions in the aqueous solution. In other words, once the system is above the transition temperature, the variations in the structural order of the interface are very small. Thirdly, in the absence of Er , the plots of different (heating/cooling) stages of any individual system are almost identical even for the lower-temperature phase. In other words, when there is no Er in the lower phase, the excess interfacial entropy, more or less, remains unchanged as the system undergoes a transition in any (heating/cooling) stage of measurements. However, as Er
3+ 3+ 3+ 3+

is added to lower phase, the linear region of the plot for any system is

considerably varied for different (heating/cooling) stages of measurements. More precisely, once the system undergoes a transition in the first (heating) stage, the composition of the interface changes in such a way as to decrease the excess interfacial entropy. A promising explanation for this decrease in the entropy is that, depending on the initial concentration of Er
3+

ions in the

aqueous solution, at least some have been transferred to the oil phase once the system is above the transition temperature for many hours in the first heating stage. And, this mechanism requires a positive adsorption of Er
3+

ions at the interface while the sample is below the transition

temperature. Based on Gibbs adsorption equation ( / ln c )T = RT , one can measure the excess interfacial concentration of Er by measuring interfacial tension versus natural logarithm of the concentration of Er at constant temperature. Since we had used only two different concentrations, it is implausible to extract a complete analysis. Introducing Er to aqueous solution causes a decrease in the interfacial tension and an increase in the transition temperature of the system. This could be explained only by the fact that more
3+ 3+ 3+

Er ions are present at the interface surrounding the interfacial DHDP molecules. And, the increase in the transition temperature is understood through the fact that ionic interactions between Er
3+

3+

and OOH head of the DHDP surfactants need more thermal energy to be broken
3+

than the previous interactions in the absence of Er . Finally, in the presence of Er , the slope of the linear region of the plots has the smallest value for the first heating stage of an individual sample. In other words, the ionic interactions mentioned earlier are so strong that once some portion of Er
3+ 3+

ions are transferred to oil phase,

successive (heating/cooling) stages are unable to bring these ions back to the lower phase; once the first transition occurs, it is impossible to bring the Er
3+

ions back to the lower phase under

3+

normal conditions. All this phenomena together could explain why for systems containing Er , (1) The first heating stage has smaller slope than the same systems without Er ; (2) The first cooling stage has more or less the same slope; and, (3) The second heating stage has slightly larger slope. Put it all together, these three observations indicate that once the system undergoes the transition corresponding to the first heating stage, the molecular structure of the interface along with both bulk phases changes irreversibly; the heating stage of the first cycle is not reproducible. ______________________________________________________________________________
3+

References
1. Danesi, P. R., & Chiarizia, R., (1980). The Kinetics of Metal Solvent Extraction. Crit. Rev. Anal. Chem., 10, 1-126. 2. W. Bu, M. Mitrinovic, G. Luo, L. Soderholm, M. L. Schlossman, unpublished work. 3. Adamson, A. W. & Gast, A. P. (1997). Physical chemistry of surfaces. New York: John Wiley & Sons, Inc.

4. Als-Nielsen, J & McMorrow, D. (2011). Elements of Modern X-ray Physics. (2nd Edition). London: John Wiley & Sons, Inc. 5. Butt, Hans-Jrgen, Karlheinz Graf, and Michael Kappl.Physics and Chemistry of Interfaces. Weinheim: WILEY-VCH Verlag GmbH & Co. KGaA, 2003. Print. 6. Benjamin, Ilan. Molecular Structure and Dynamics at Liquid-Liquid In. Annual Review of Physical Chemistry. 48. (1997): 407-51. Web. 15 Feb. 2012. <http://www.annualreviews.org/doi/pdf/10.1146/annurev.physchem.48.1.407>. 7. R. Parwani, Rajesh. Correlation Function. National University of Singapore, 03 Jan 2002. Web. 25 Feb 2012. <http://staff.science.nus.edu.sg/~parwani/c1/node52.html>. 8. Pershan, Peter S., and Mark L. Schlossman. Liquid Surfaces and Interfaces: Synchrotron Xray Methods. Cambridge University Press, 2012. 9. Rulison, Christopher. Plate Method. Rings are for Fingers - Plates are for Surface Tension. Augustine Scientific, America's premier contract analytical testing and consulting laboratory for surface and interface science, Jun 2004. Web. 28 Feb 2012. <http://www.kruss.de/en/newsletter/newsletter-archives/2004/issue06/application/application01.html?type=98&cHash=ba43108154dee631e3f749aadac248e2>. 10. Schlossman, Mark L., and Alexey M. Tikhonov. Molecular Ordering and Phase Behavior of Surfactants at Water-Oil Interfaces as Probed by X-Ray Surface Scattering. Annual Review of Physical Chemistry. 59. (2008): 153-77. Web. 4 Mar. 2012. <http://www.annualreviews.org/doi/abs/10.1146/annurev.physchem.59.032607.093822>. 11. Popov, Alexander N. The Interface Structure and Electrochemical Processes at the Boundary Between Two Immiscible Liquids. Berlin, Heidelberg, New York, London, Paris, Tokyo: Springer-Verlag, 1987. 179. 12. Fawcett, W. Ronald. Liquids, Solutions, and Interfaces: From Classical Macroscopic Descriptions to Modern Microscopic Details. Oxford, New York: Oxford University Press, Inc., 2004. 383-443. Print. 13. Tikhonov, Aleksey M., Ming Li, and Mark L. Schlossman. Phase Transition Behavior of Fluorinated Monolayers at the Water-Hexane Interface. Journal of Physical Chemistry B. 105.34 (2001): n. page. Print. 14. Archer, Andrew J., and Nigel B. Wilding. "Phase behavior of a fluid with competing

attractive and repulsive interactions." Physical Review E: statistical, nonlinear, and soft matter Physics. 76.031501 (2007): n. page. Print. <http://pre.aps.org/abstract/PRE/v76/i3/e031501>. 15. Tikhonov, Aleksey M., Harshit Patel, Shekhar Garde, and Mark L. Schlossman. Tail Ordering Due to Headgroup Hydrogen Bonding Interactions in Surfactant Monolayers at the WaterOil Interface. Journal of Physical Chemistry B. 110. (2006): 1909319096. Web. 12 Mar. 2012. <http://pubs.acs.org/doi/abs/10.1021/jp064120q>. 16. Snyder, Kendra. United States, New York. Office of Science of the U.S. Department of Energy (DOE).Expanding the Degrees of Surface Freezing: Molecular ordering phenomenon found at interface between complex liquids and solids. Upton: Brookhaven National Laboratory, 2011. Web. <http://www.bnl.gov/bnlweb/pubaf/pr/PR_display.asp?prID=1256>.

APPENDIX A

Interfacial Tension vs. Temperature Plots

Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 41 1)o C

o

ErBr3 = ( 3.0 0.1) 107 M , pH = 2.5 At ( 21 1) C

Control Settings: Temperature Tolerance = 0.005(o C ) Tension Tolerance = 0.03(mN / m) Wait Time = 10 min .

Figure 8

41

Surface Tension (mN/m)

40.6 40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 Increasing Slope=0.730.08 (mN/mC) Transition Temperature=(32.30.5) (C) Decreasing Slope=0.840.05 (mN/mC) Transition Temperature=(31.00.4) (C) Decreasing Slope=0.720.05 (mN/mC) Transition Temperature=(31.80.4) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2) Decreasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

Temperature (C)
Control Settings: Temperature Tolerance = 0.005(o C ) Tension Tolerance = 0.02(mN / m) Wait Time = 20 min .

Figure 9
41.2 41 40.8 40.6 40.4 40.2 40 39.8 39.6 39.4 39.2 39 38.8 38.6 38.4 38.2 38 37.8 37.6 37.4

Surface Tension (mN/m)

Increasing Slope=0.820.03 (mN/mC) Transition Temperature=(31.10.3) (C) Decreasing Slope=0.820.14 (mN/mC) Transition Temperature=(30.00.4) (C) Increasing Slope=0.720.10 (mN/mC) Transition Temperature=(30.30.5) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

Temperature (C)

Concentration and Temperature of the phases DHDP = (1.07 0.03) 104 M At ( 36 1)o C ErBr3 = ( 3.0 0.1) 107 M , pH = 2.5 At ( 21 1)o C
Control Settings: Temperature Tolerance = 0.005(o C ) Tension Tolerance = 0.03(mN / m) Wait Time = 10 min .

Figure 10
40.4 40.2 40 39.8 39.6 39.4 39.2 39 38.8 38.6 38.4 38.2 38 37.8 37.6 37.4 37.2 37 36.8

Surface Tension (mN/m)

Increasing Slope=0.82 (mN/mC) Transition Temperature=(31.00.3) (C) Decreasing Slope=0.64 (mN/mC) Transition Temperature=(29.60.5) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

Temperature (C)

Figure 11
42.4 42.2 42 41.8 41.6 41.4 41.2 41 40.8 40.6 40.4 40.2 40 39.8 39.6 39.4 39.2 39 38.8 38.6 38.4 38.2 38 37.8 37.6 37.4

Surface Tension (mN/m)

Increasing Slope=0.90 (mN/mC) Transition Temperature=(32.30.5) (C) Decreasing Slope=0.80 (mN/mC) Transition Temperature=(30.70.5) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

Temperature (C)

Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 36 1) C
o

ErBr3 = (1.0 0.1) 107 M , pH = 2.5 At ( 21 1)o C

Control Settings: Temperature Tolerance = 0.005(o C ) Tension Tolerance = 0.03(mN / m) Wait Time = 10 min . Figure 12
42.2 41.8 41.4 41 40.6 40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 37 36.6 36.2 35.8

Surface Tension (mN/m)

Increasing Slope=0.75 (mN/mC) Transition Temperature=(34.50.5) (C) Decreasing Slope=0.81 (mN/mC) Transition Temperature=(34.30.5) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

Temperature (C)
Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 36 1) C

o
o ErBr = 5.0 107 M , pH = 2.5 At ( 21 1) C 3

Control Settings: Temperature Tolerance = 0.005(o C ) Tension Tolerance = 0.02(mN / m) Wait Time = 20 min .

Figure 13
41.4 41 40.6 40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 37 36.6 36.2 35.8 35.4

Surface Tension (mN/m)

Increasing Slope=0.75 (mN/mC) Transition Temperature=(34.50.5) (C) Decreasing Slope=0.81 (mN/mC) Transition Temperature=(33.30.5) (C) Increasing Temperature (1) Decreasing Temperature (1)

27

28

29

30

31

32

33

34

35

36

37

38

Temperature (C)

Control Settings: Temperature Tolerance = 0.005(o C ) Tension Tolerance = 0.03(mN / m)

Wait Time = 10 min . Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 30 1) C
o

o ErBr3 = ( 5.0 0.1) 107 M , pH = 2.5 At ( 28 1) C

Figure 14
40.6

Surface Tension (mN/m)

40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 37 36.6 36.2 Increasing Slope=0.74 (mN/mC) Transition Temperature=(32.30.2) (C) Decreasing Slope=0.86 (mN/mC) Transition Temperature=(31.00.5) (C) Increasing Temperature Decreasing Temperature

27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48

Temperature (C)

Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 33 1)o C o ErBr3 = ( 5.0 0.1) 107 M , pH = 2.5 At ( 28 1) C
Figure 15
40.4 40 39.6 39.2 38.8 38.4 38 37.6 37.2 36.8 36.4 36 35.6 35.2 34.8 34.4 34

Surface Tension (mN/m)

Increasing Slope=0.81 (mN/mC) Transition Temperature=(34.20.3) (C) Decreasing Slope=0.81 (mN/mC) Transition Temperature=(32.70.5) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)

Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 29 1) C
o

o ErBr3 = ( 5.0 0.1) 107 M , pH = 2.5 At ( 28 1) C

Figure 16
41 40.6 40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 37 36.6 36.2 35.8 35.4 35 34.6 34.2 Increasing Slope=0.860.01 (mN/mC) Transition Temperature=(34.20.1) (C) Decreasing Slope=0.850.03 (mN/mC) Transition Temperature=(32.00.5) (C) Increasing Slope=0.770.05 (mN/mC) Transition Temperature=(32.70.5) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

Surface Tension (mN/m)

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)

Figure 17: Only Mylar

42.2 41.8 41.4 41 Interfacial Tension (mN/m) 40.6 40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 37 Increasing Slope = 0.630.02 (mN/mC) Transition Temperature = (31.60.4) (C) Decreasing Slope = 0.870.03 (mN/mC) Transition Temperature = (31.70.4) (C) Increasing Slope = 0.820.03 (mN/mC) Transition Temperature = (32.00.4) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)

Figure 18 (Only Mylar)

42.2 41.8

Interfacial Tension (mN/m)

41.4 41 40.6 40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 37 Increasing Slope = 0.710.01 (mN/mC) Transition Temperature = (31.80.3) (C) Decreasing Slope = 0.850.01 (mN/mC) Transition Temperature = (31.30.3) (C) Increasing Slope = 0.790.03 (mN/mC) Transition Temperature = (31.70.3) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)

Figure 19 (Only Mylar)

42.2

Surface Temsion (mN/m)

41.8 41.4 41 40.6 40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 Increasing Slope = 0.720.02 (mN/mC) Transition Temperature = (31.70.3) (C) Decreasing Slope = 0.930.05 (mN/mC) Transition Temperature = (31.00.3) (C) Increasing Slope = 0.750.03 (mN/mC) Transition Temperature = (31.80.3) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)

Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 31 1) C
o

ErBr3 = 0M + HBr ( pH = 2.67) , At ( 28 1)o C

Figure 20
41.2 40.8 40.4 40 39.6 39.2 38.8 38.4 38 37.6 37.2 36.8 36.4 36 35.6 35.2

Surface Tension (mN/m)

Increasing Slope=0.60.2 (mN/mC) Transition Temperature=(33.90.3) (C) Decreasing Slope=0.940.03 (mN/mC) Transition Temperature=(32.60.5) (C) Increasing Slope=0.880.02 (mN/mC) Transition Temperature=(32.60.5) (C) Increasing Temperature (1) Decreasing Temperature (1)

27

28

29

30

31

32

33

34

35 36 37 38 Temperature (C)

39

40

41

42

43

44

45

Concentration and Temperature of the phases

DHDP = (1.07 0.03) 104 M At ( 28 1) C
o o ErBr3 = 0M + HBr ( pH = 2.5) , At ( 28 1) C

Figure 21

40.2 39.8 39.4 39 38.6 38.2 37.8 37.4 37 36.6 36.2 35.8 35.4 35 34.6 34.2

Surface Tension (mN/m)

Increasing Slope=0.870.07 (mN/mC) Transition Temperature=(33.80.3) (C) Decreasing Slope=0.790.03 (mN/mC) Transition Temperature=(31.60.5) (C) Increasing Slope=0.730.03 (mN/mC) Transition Temperature=(32.40.5) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)

Figure 22 (Only Mylar)

42.4 42

Surface Tension (mN/m)

41.6 41.2 40.8 40.4 40 39.6 39.2 38.8 38.4 38 Increasing Slope = 0.720.01 (mN/mC) Transition Temperature = (30.90.2) (C) Decreasing Slope = 0.800.04 (mN/mC) Transition Temperature = (30.90.2) (C) Increasing Slope = 0.710.04 (mN/mC) Transition Temperature = (31.50.2) (C) Increasing Temperature (1) Decreasing Temperature (1) Increasing Temperature (2)

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)

Figure 23: Only Mylar

First Heating Stage of First Cycle

42.4 42

Interfacial Tension (mN/m)

41.6 41.2 40.8 40.4 40 39.6 39.2 38.8 38.4 38 Linear Slope =0.72 0.01 (mN/mC) Transition Temperature = (30.90.2) (C) Linear Slope =0.630.02 (mN/mC) Transition Temperature = (31.60.4) (C) No ErBr3 5.0*10^(-7) M ErBr3

27

28

29

30

31

32

33

34

35 36 37 38 Temperature (C)

39

40

41

42

43

44

45

Figure 24: Only Mylar

42.4 42 41.6 41.2 40.8 40.4 40 39.6 39.2 38.8 38.4 38 37.6 37.2 36.8

First Cooling Stage of First Cycle

Interfacial Tension (mN/m)

Linear Slope =0.870.03 (mN/mC) Transition Temperature = (31.70.4) (C) Linear Slope=0.80 0.04 (mN/mC) Transition Temperature = (30.90.2) (C) 5.0*10^(-7) M ErBr3 No ErBr3

27

28

29

30

31

32

33

34

35 36 37 38 Temperature (C)

39

40

41

42

43

44

45

Figure 25: Only Mylar

Second Heating Stage of Second Cycle

42.4 42 41.6 41.2 40.8 40.4 40 39.6 39.2 38.8 38.4 38 37.6 37.2 36.8

Interfacial Tension (mN/m)

Linear Slope =0.710.04 (mN/mC) Transition Temperature = (31.50.4) (C) Linear Slope =0.820.03 (mN/mC) Transition Temperature = (32.00.4) (C) No ErBr3 5*10^(-7) M ErBr3

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

Temperature (C)