ENSTA Paristech IIT Bombay

Adsorption of PEG at air/water interface

Projet de recherche (PRE)

MATHILDE CHANCEREL
PROMOTION 2016

Tuteur ENSTA : Jean BOISSON Tuteur Organisme : Rochish THAOKAR

Professor Professor

Mention de Confidentialité

This document is not confidential

May 11th - July 17th 2015

Confidentiality

This report is non confidential.

Mumbai, July 2015

Mathilde CHANCEREL

1
Abstract

A study of the adsorption of a polyether compund, PEG-400, at air/water interface is

reported. Adsorption has been observed through measurements of the water surface ten-
sion with time at the interface, using both Wilhelmy plate and pendant drop methods. The
experiments have been conducted during one hour for two concentrations. As expected
with the Ward and Tordai equation, a decrease of the water surface tension has been
observed. Different values for surface tension have been obtained with the two methods.
A short time analysis has been conducted to see if the experiments fit the adsorption
isotherms, proposed by Henry and Langmuir. It has been found, that for these results,
Wilhelmy plate matches more the theory than pendant drop method.

Keywords

Adsorption, Diffusion, Surface tension, the Ward and Tordai equation, Air-water in-
terface, Adsorption isotherms, PEG400, PEG600000.

3
Acknowledgements

This internship I had in the Chemical Department of IIT Bombay was a great chance
for learning and discovering the background of research. I consider myself as a very lucky
individual as I was provided with an opportunity to be part of it.
I would like to thank all the people who helped me conducting this project during
these two months in IIT. First of all, I express my deepest gratitude to my guide , Professor
Rochish Thaokar, who took time out to hear, guide and keep me in the correct path when
I was facing difficulties with my project work. I also would like to thank Subhankar Roy,
who helped me conducting my experiments and trying to understand when they did not
work.
I perceive this project as a real opportunity because I discovered the research work
and could have extended my knowledge to others areas I had not studied until now.

Sincerely,
Mathilde Chancerel

5
Contents

Confidentiality 1

Abstract 3

Acknowledgements 5

Glossary 13

1 Introduction 15

2 Background of surface tension 17

2.1 What is surface tension ? . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.1 In terms of energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.2 In terms of force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2 How to measure surface tension ? . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.1 The pendant drop method . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.2 The Wilhelmy plate method . . . . . . . . . . . . . . . . . . . . . . . 20

3 Kinetics of surfactant adsorption 23

3.1 Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.2 Theoretical background of adsorption . . . . . . . . . . . . . . . . . . . . . 24
3.2.1 Phenomena of diffusion . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.2.2 The Ward-Tordai equation . . . . . . . . . . . . . . . . . . . . . . . . 25
3.2.3 Model adsorption isotherms . . . . . . . . . . . . . . . . . . . . . . . 25
3.2.4 Solving the Ward and Tordai equation . . . . . . . . . . . . . . . . . 26

4 Experimental study of adsorption 29

4.1 Evolution of the surface tension with time . . . . . . . . . . . . . . . . . . . 29
4.1.1 Using pendant drop method . . . . . . . . . . . . . . . . . . . . . . . 29
4.1.2 Using Wilhelmy plate method . . . . . . . . . . . . . . . . . . . . . . 30
4.1.3 Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.2 Analysis of the results for short times . . . . . . . . . . . . . . . . . . . . . 33
4.2.1 For Henry adsorption isotherm . . . . . . . . . . . . . . . . . . . . . 33
4.2.2 For Langmuir adsorption isotherm . . . . . . . . . . . . . . . . . . . 35
4.3 Influence of a higher concentrated compund . . . . . . . . . . . . . . . . . 36
4.4 System composed of both PEG-400 and PEG-600000 . . . . . . . . . . . . . 38

7
CONTENTS

5 Numerical study of adsorption 41

5.1 Getting closer to the experiments . . . . . . . . . . . . . . . . . . . . . . . . 41
5.2 Influence of concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.3 Influence of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

6 Conclusion 47

Appendices 49

A The Young-Laplace equation 51

B Solving the Ward and Tordai equation 53

Bibliography 55

8
List of Figures

1.1 Classification of surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . 15

2.1 Separation of an interface . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.2 Movable side of a frame . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Pendant drop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.4 Drop of a liquid suspended from a needle . . . . . . . . . . . . . . . . . . . 19
2.5 Diagram of the Wilhelmy plate method . . . . . . . . . . . . . . . . . . . . 20
2.6 Experimental set up of the Wilhelmy plate method . . . . . . . . . . . . . . 20

3.1 Without adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

3.2 Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.3 Studied system and parameters . . . . . . . . . . . . . . . . . . . . . . . . 24

4.1 Chemical structure of PEG . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

4.2 Evolution of surface tension for two concentrations using pendant drop
method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.3 Evolution of surface tension for two concentrations using Wilhelmy plate
method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.4 Evolution of surface tension for C = 1000 ppm . . . . . . . . . . . . . . . . 32
4.5 Evolution of surface tension for C = 3000 ppm . . . . . . . . . . . . . . . . 32
4.6 ln(σ0 − σ) versus ln (t ) for C = 3000 ppm . . . . . . . . . . . . . . . . . . . . 33
4.7 ln(σ0 − σ) versus ln (t ) for C = 1000 ppm . . . . . . . . . . . . . . . . . . . . 34
4.8 Evolution of D versus time for Wilhelmy plate and pendant drop method for
C = 1000ppm and C = 3000 ppm . . . . . . . . . . . . . . . . . . . . . . . 34
4.9 ln(σ0 − σ) versus t for C = 1000 ppm . . . . . . . . . . . . . . . . . . . . . . 35
4.10 ln(σ0 − σ) versus t for C = 3000 ppm . . . . . . . . . . . . . . . . . . . . . . 36
4.11 Surface tension versus t for C = 1000ppm for PEG-400 and PEG-600000
using Wilhemy plate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.12 Surface tension versus t for C = 1000ppm for PEG-400 and PEG-600000
using pendant drop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.13 Surface tension versus t for a system composed of 2.10−6 mol of PEG-400
and PEG-600000 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

5.1 Comparison of numerical and experimental solutions for KL = 103 m 3 /mol 42

5.2 Comparison of numerical and experimental solutions for KL = 103 m 3 /mol
and σ0 = 47 mN/m . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

9
LIST OF FIGURES

5.3 Numerical simulations for different values of KL . . . . . . . . . . . . . . . 43

5.4 Numerical simulations for different concentrations . . . . . . . . . . . . . . 44
3
5.5 Numerical simulations 2.5 and 5 mol/m for t = 100000 s . . . . . . . . . 44
5.6 Influence of temperature on surface tension . . . . . . . . . . . . . . . . . 45

A.1 Drop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

10
List of Tables

3.1 Model adsorption isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . 26

4.1 Values of σ0 for different concentrations . . . . . . . . . . . . . . . . . . . . 31

4.2 Equations of ln(σ0 − σ ) versus ln (t ) . . . . . . . . . . . . . . . . . . . . . . 33
4.3 Values of η for C = 1000ppm and C = 3000ppm . . . . . . . . . . . . . . . 36
4.4 Surface tension for C = 1000 ppm . . . . . . . . . . . . . . . . . . . . . . . 37

5.1 σ0 - σ2700 for experiment and simulation . . . . . . . . . . . . . . . . . . . 45

11
Glossary

term description
σ surface tension in N/m
σ0 initial surface tension in N/m
Γ surfactant concentration area at the interface in mol/m 2
Γ0 initial surface excess in mol/m 2
Γ∞ surface excess in mol/m 2
D diffusion coefficient in m 2 /s
CB initial bulk concentration in mol/m 3
CS concentration at the interface in mol/m 3
c bulk concentration in mol/m 3
KH the Henry constant in m
KL the Langmuir constant in m 3 /mol
KV the Volmer constant in m 3 /mol
T absolut temperature in K
r radius of curvature of a spherical interface in m
kB the Boltzmann constant in m 2 .kg.s−2 .K −1
NA the Avogadro number in mol −1
ppm part per million : 1 ppm = 1 mg/L
PEG polyethylene glycol

13
Chapter 1
Introduction

A dsorption can be defined as a surface-based process in which gas or liquid molecules

settle down on solid/liquid, liquid/liquid or gas/liquid interfaces. This process
creates a film of the absorbate on the surface of the absorbant.
Even if adsorption is a natural process, it can be the basis for some processes, such as
the separation of chemical components. For example, nowadays, adsorption is widely
used in industrial applications such as activated charcoal, capturing and using waste
heat to provide cold water for air conditionning, synthetic resins and water purification.
It seems that knowing the whole process of adsorption is essential for progress in these
technologies.

The adsorption of PEG (polyethylene glycol) at air/water interface has been studied in
this project work through measurements of the water surface tension σ, which is modified
with the presence of surfactants into the solution. Surfactants are organic compounds
that are amphiphilic, meaning they contain both hydrophobic groups (their tails) and
hydrophilic groups (their heads). Therefore, a surfactant contains both water-insoluble
and water-soluble component.
Most commonly, surfactants are classified according to polar head group. Non-ionic
surfactants do not have charge groups in their head. On the contrary, ionic surfactants
can be anionic (negative charge) or cationic (positive charge).

Figure 1.1: Classification of surfactants

When coupled to hydrophobic molecules, PEG produces non-ionic surfactants.

15
 This study, as indicated in its title, investigates the adsorption of PEG at air/water
interface. After a review of previous research on surface tension and the methods used to
measure it, this report establishes the theoretical background of adsorption. An experi-
mental study was then made to understand the theory and the phenomena of adsorption.
Finally, a draft of a numerical simulation has been conducted to try to compare experi-
mental and theoretical data.
Chapter 2
Background of surface tension

T his chapter explains what surface tension is. It is necessary to know and under-

tension.
stand this physical property because adsorption is physically seen through surface

First of all, the theoretical background of surface tension is explained. Then, two
methods used to measure the surface tension (Pendant drop and Wilhelmy plate) are
presented.

2.1 What is surface tension ?

Let us begin with the following definition of surface tension : it is the elastic tendency of
liquids which makes them acquire the least surface area possible. There are two different
ways of understanding this phenomena : one using an energetic approach, and the other
focusing on a force approach. Both method are explained in the following sections.

2.1.1 In terms of energy

The following example, shown in Figure (2.1), is considered.

Figure 2.1: Separation of an interface

To create a separation at the interface of a liquid, energy must be given, to makes it

possible. This energy can be measured in term of work during the change in the area.
Now, one can write the following relation between surface tension σ and work W :

W = 2σA (2.1)

17
 The factor of 2 is here because the liquid has 2 sides.
Surface tension can then be seen as the ratio of the change in energy of the liquid and
the change in the surface area of the liquid. It can be expressed in J/m 2 .

2.1.2 In terms of force

A rectangle frame with three unmovable sides and one movable side, and a liquid
stretched into a thin film on this frame, is considered.

Figure 2.2: Movable side of a frame

When the fourth side is moved, a force F is created to stop the movable side. F is
proportional to the length L of the frame.
One can easily write the following equation :

F = 2Lσ (2.2)

As indicated above, the factor of 2 is here because the liquid has 2 sides, each of which
contributes equally to the force.
Surface tension can be interpreted as the force by length unit, required to stop a
movable frame where a liquid is stretched.

2.2 How to measure surface tension ?

Surface tension can be measured by using many different methods such as the pen-
dant drop method, the Wilhelmy plate method, the maximum bubble pressure method
etc ...
Here, two methods only are presented, which have been used during this project work
: pendant drop and Wilhelmy plate.

2.2.1 The pendant drop method

In this method, a pendant drop of a liquid is suspended from the end of a tube
by surface tension. An increased pressure is produced inside the drop as a result of
the interfacial tension between the inner and outer phase. The correlation between the
pressure difference ∆p, the radius of curvature r and the interfacial tension is described
by the Young-Laplace equation (see Appendix A for the demonstration of this equation) :
 Figure 2.3: Pendant drop

2σ
∆p = (2.3)
r
The pendant drop is deformed under the effect of gravity, as a hydrostatic pressure
which affects the main radius of curvature r is produced inside the drop due to the weight.

For these experiments, the software Windrop is used. The experimental setup is showed
behind :

Figure 2.4: Drop of a liquid suspended from a needle

The drop of the studied liquid is suspended from a needle. With this needle, the
volume of the drop can be controlled by the user. Then, with a camera recording the
movements of the drop, the software is able to measure the volume of it and to calculate
surface tension using the Young-Laplace equation. However, this method did not give
accurate results because many measures and not a unique one are given, because σ is
calculated for each picture the camera has recorded. Besides, the volume of the drop
keeps changing with time, which may falsify the results. Besides, many factors such as
ambient noise, wind and movements, can influence the results of the measurement.
2.2.2 The Wilhelmy plate method

This method uses the relation between the surface tension of a liquid, the contact
angle between a liquid and a solid, which in this case in a plate, and the force acting
vertically on this plate.
When a vertically suspended plate touches a liquid surface or interface, the force F,
which correlates with the surface tensionσ and with the contact angle Θ according to the
following equation, acts on this plate :

F
σ= (2.4)
L cos Θ

Figure 2.5: Diagram of the Wilhelmy plate method

Platinum is chosen as the plate material as it is chemically inert and easy to clean,
and because it can be optimally wetted in account of its very high surface free energy and
therefore generally forms a contact angle Θ of 0◦ with liquids. The surface tension σ can
be calculated directly from the measured force.

The experimental set up of this method is shown below :

Figure 2.6: Experimental set up of the Wilhelmy plate

method
 The platinum plate needs to be burned before each measure to withdraw all the impu-
rities which can influence the result. The container, which can be seen in Figure (2.6)
is confined into a box to limit the impact of outer factors. The software Balance 3S can
be programmed to take measures automatically : the plate goes down into the liquid and
then moves up at each time interval as required by the user.
Chapter 3
Kinetics of surfactant adsorption

K inetics of surfactant adsorption have been addressed by experimental and theoret-

ical studies since the 1940s. The aim of this chapter is to present what has been
studied over the past years and to establish the pioneering equation of Ward and Tordai
(1946).

3.1 Experimental setup

A beaker filled with water and a surfactant is considered. The study consists in
measuring the evolution of surface tension at the air/water interface, knowing the initial
concentration of surfactant CB .

During the experiments, a phenomena has been observed : adsorption. It can be

described by some characteristics : this process is spontaneous and can occur at all
surfaces, it is accompanied by a decrease in the free energy of the system. Some factors
can affect adsorption such as the nature of the adsorbent and the adsorbate, and the
temperature. This will be proved in the following section.

Figure 3.1: Without adsorption Figure 3.2: Adsorption

Adsorption can be easily described as followed. A solution of uniform concentration

CB of surfactant with a plane surface between the solution and the air is considered. At
the initial time, the concentration of the solute at the interface is the same as the bulk.

23
Then, molecules go to the surface : it is diffusion. As a consequence, the surfactant
concentration in number per unit area ΓS , will rise until reaching equilibrium. The
process is shown in Figures (3.1) and (3.2).

3.2 Theoretical background of adsorption

As explained above, adsorption appears with diffusion.The fact that molecules go to

the interface implies that a concentration gradient is being considered. Consequently,
the concentration at the interface CS changes with time. Besides, CS can be related to
ΓS , through the adsorption equilibrium relationship (see section 3.2.3). However, Γ is not
accessible with experiments, only the surface tension σ can be measured. This section
explains how σ and Γ can be related.

3.2.1 Phenomena of diffusion

Diffusion is ruled by Fick’s second law. In this project, this equation is considered in
one dimension :
∂c ∂2 c
=D (3.1)
∂t ∂2 x
where D is the diffusion coefficient in m 2 /s and c the bulk concentration.

Figure 3.3: Studied system and parameters





 c(x=0,t) = CS

The boundary conditions of this problem can be written as followed :  c(x=∞,t) = CB




 c(x=0,t=∞) = CB

where CS is the concentration at the interface and CB the initial bulk concentration.

This equation can be solved using an unidimensional parameter η = √x .

Dt
Then, one can obtain :

∂c CB − CS −η 2
= √ e 4 (3.2)
∂η π
 c is obtained when integrating equation (3.2) :

Z √x
CB − CS Dt −u 2
c (x, t ) = √ e 4 du + CS (3.3)
π 0

3.2.2 The Ward-Tordai equation

ΓS has been introduced as the surfactant concentration in number per unit area at
the interface (mol/m 2 ). Now, by a dimensional analysis, one can write :

∂ΓS

∂c 
=D  . (3.4)
∂t ∂x x =0
Using (3.3) and derivating it, one can obtain the following equation for ΓS :

r t
√
Z
D CS (τ )
ΓS (t ) − Γ0 = (2CB t − √ dτ ) (3.5)
π 0 t−τ
This equation is known as the Ward and Tordai equation (1946) [1]: it is one of the
pioneering equation for surfactant adsorption. The first term is the contribution from the
bulk concentration. The second is the contribution from the interface itself.
The Ward and Tordai equation is unsuitable to describe the experimental results
(measurements of the surface tension σ) since its contains two unknown functions : Γ
and CS .

For short times t → 0, one can write the following equation :

r
Dt
ΓS (t ) − Γ0 = 2CB (3.6)
π
If adsorption is considered to be a fast process, the diffusion time τD and the surface
excess Γ∞ can be related with equation (3.7) :

π Γ∞
τD = ( )2 (3.7)
D 2CB

3.2.3 Model adsorption isotherms

The Ward and Tordai equation can be solved when an adsorption isotherm is consid-
ered : it is a relation which connects CS and σ. Langmuir (1917) was the first scientist to
develop such a theory : before, adsorption was only studied as a thermodynamic phenom-
ena and not as a kinetics process. Others scientists such as Volmer and Henry addressed
the same problem and developed their own adsorption isotherm.
The surface equation of state, which links σ and Γ is then obtained using Gibbs
adsorption isotherm for surfactants :

dσ = −kB T Γ ln(CS ) (3.8)

 The results previously evoked are presented in Table (3.1) [2].

Type of isotherm Surfactant adsorption isotherm Surface equation of state : σ0 - σ

Γ
Henry KH CS = Γ S σ0 − σ = kB TNA ΓS
∞
ΓS Γ
Langmuir KL CS = Γ −Γ σ0 − σ = kB TNA Γ∞ ln( Γ −Γ∞
)
∞ S ∞ S
ΓS ΓS ΓS
Volmer KV CS = Γ −Γ exp( Γ∞ −ΓS ) σ0 − σ = kB TNA Γ∞ Γ −Γ
S ∞ ∞ S

Table 3.1: Model adsorption isotherms

It is important to notice that the results presented in Table (3.1) are valid for non-
ionic surfactants only. Indeed, if the adsorption process is diffusion controlled, there
is local equilibrium between the surface adsorption and the subsurface concentration.
The relation between both is given by the adsorption isotherms previously presented. If
the adsorption process is not diffusion controlled, the equation of Ward and Tordai still
applies but the condition of local equilibrium between surface and subsurface is to be
replaced by a kinetic equation. This is the case for ionic surfactants : the kinetics of the
system includes, apart from the diffusive transport of molecules and their adsorption at
the interface, the formation of an electric double layer due to the electrostatic interactions.

Considering a non-ionic surfactant and short times, the surface equation of state for
Henry isotherm can be approximated as followed (with Γ0 =0) :
r
Dt
σ0 − σ = 2CB kB TNA (3.9)
π
Considering Langmuir adsorption isotherm, the surface equation of state becomes :

Γ∞
σ0 − σ = kB TNA Γ∞ ln( q ) (3.10)
Γ∞ − 2CB Dt
π

3.2.4 Solving the Ward and Tordai equation

Using Henry adsorption isotherm, equation (3.5) becomes :

Γ S (τ )
r t
√
Z
D
ΓS (t ) − Γ0 = (2CB t − √ dτ ) (3.11)
πt 0 KH Γ∞ t − τ
(3.11) is a Volterra equation of the second type. An analytical solution can’t be calcu-
lated. The way to solve the Ward and Tordai equation is to use a numerical resolution,
based on the trapezian method. The aim of this project work was not to set up the code to
solve this equation, this is the C++ code, Diffusion-controlled adsorption rate and DST cal-
culator, written by Xueliang Bruce Li and Paul Stevenson of the University of New Castle,
Australia has been used [3]. A part of this code can be found in Appendix B.

This code takes into account all the parameters previously evoked in this chapter :
the bulk concentration CB , the saturation surface excess Γ∞ , the temperature T and
the diffusion coefficient D. It also enables us to choose between the different adsorption
isotherms (Langmuir, Volmer or Henry) and the experimental method used to measure
surface tension (Wilhelmy plate or pendant drop). If the method chosen is pendant drop,
the radius r of the spherical interface is also needed.
Chapter 4
Experimental study of adsorption

I n this chapter, the adsorption of PEG-400 from water into air/water interface is stud-
ied. PEG-400, also known as polyethylene glycol, is a polyether compound with
many applications from industrial manufacturing to medicine. The chemical formula for
PEG is C2n H4n +2 On +1 . The numbers that are often included in the name of PEGs indicate
their average molecular weights. For example, a PEG with n = 9 would have an average
molecular weight of approximatively 400 daltons (1 dalton = 1 g/mol) : it is PEG-400. So,
MPEG400 = 400 g/mol. Figure (4.1) shows the chemical structure of PEG in the general
case.

Figure 4.1: Chemical structure of PEG

As explained in Chapter 3, adsorption can be monitored experimentally by measuring

the surface tension. This is what has been done in this project for two concentrations
: 1000 ppm and 3000 ppm (ppm meaning part per million : 1 ppm = 1 mg/L). The two
methods presented previously (pendant drop and Wilhelmy plate) have been used.

4.1 Evolution of the surface tension with time

4.1.1 Using pendant drop method

The results for C = 1000 ppm and C = 3000 ppm with pendant drop method are given
in Figure (4.2).

With time, surface tension decreases as the PEG gets adsorbed at the air/water interface
at a finite rate. This follows the theory of adsorption explained in Chapter 3. Using Henry
adsorption isotherm, one can write : σ0 − σ = kB TNA ΓS .

29
 Figure 4.2: Evolution of surface tension for two concentrations using
pendant drop method

ΓS is the surfactant concentration in number per unit area at the interface. Surfactant
molecules go to the surface by diffusion : as a consequence, there are more and more
molecules at the interface as time goes through. So, σ0 − σ is expected to increase which
means that σ should reduce with time.

4.1.2 Using Wilhelmy plate method

The experimental results for the PEG-400 concentrations, 1000 and 3000 ppm are
given in Figure (4.3).

Figure 4.3: Evolution of surface tension for two concentrations using

Wilhelmy plate method

The same results observed in section (4.1.1) are shown here : the surface tension σ
reduces with time. However, contrary to pendant drop, the decrease of σ doesn’t seem to
be linear.

4.1.3 Analysis

Figures (4.2) and (4.3) show that the surface tension decreases with time. However,
when analyzing it more precisely, some differences can be pointed out.

The first thing that can be noticed is that σ0 is lower than the water surface tension
(σwater = 71 mN/m). This is due to a first diffusion step in the adsorption kinetics which is
too fast to be detected by the plate technique. However, for Wilhelmy plate, the first value
is very small (48-50 mN/m) which is quite surprising, even when taking into account
this first step. Besides, at first sight, one may think that σ0 should be related to the
concentration : the less concentrated the solution is the closer to water surface tension
σ0 should be : PEG-400 should not interact so much with water. Experiments were
conducted using Wilhelmy plate method with different concentrations of PEG-400 to see
if this qualitative theory can be reliable. The results are presented in Table (4.1).

Concentration (mol/L) σ0 (mN/m)

25.10−4 46,527
75.10−4 50,674
10−3 50,854
2.10−2 48,280
10−1 47,408
1 44,246

Table 4.1: Values of σ0 for different concentrations

The results seem to be following very well that σ0 reduces when the concentration
increases, except for C = 1000 ppm and C = 3000 ppm. This exception can be explained
by the fact that between the making of the solution and the first measurement, there is a
period of time. Indeed, the experimental set up has to be made : the platinum plate needs
to be burned, and the software has to be settled up. During this, PEG-400 interacts with
water and surface tension decreases.

Figures (4.4) and (4.5) represent the evolution of surface tension for C = 1000 ppm and
C = 3000 ppm respectively.
In both cases, the decrease of the surface tension is very slow : in one hour, σ reduces
of 2 mN/m. It occurs that, after end of the experiments, Wilhelmy plate method seem
to give more accurate than pendant drop. Indeed, as we have introduced the system
in Chapter 2, the container is placed in a box, which doesn’t interact with the outer
environment. On the contrary, pendant drop depends on the lab environment : the
volume of the drop keeps changing all the time because of evaporation, and the drop
can move from top to bottom when there is too much activity in the surroundings, which
modifies surface tension. Moreover, the software Windrop might not be reliable.
 Figure 4.4: Evolution of surface tension for C = 1000 ppm

Figure 4.5: Evolution of surface tension for C = 3000 ppm

Besides, the evolution of σ for Wilhelmy is the same for both cases whereas for pendant
drop, the shape of the graph is different for the two concentrations. However, with these
results, it is not possible to affirm or not if the experiments are following quantitatively
the theory of adsorption presented in Chapter 3.
4.2 Analysis of the results for short times

In this section, short times are analyzing to see if the experimental results are following
the theory of adsorption. Besides, the difference σ0 − σ is studied, to get rid of the
surprising value of the initial surface tension. Two isotherms are being considered :
Henry and Langmuir.

4.2.1 For Henry adsorption isotherm

For short times, one can write, when taking the neperian logarithm of equation (3.7) :
r
D 1
ln(σ0 − σ ) = ln(2CB kB TNA )+ ln(t ) (4.1)
π 2
If the experiments are following Henry adsorption isotherm, ln(σ0 − σ ) should evolve
1
like 2
ln(t ).

ln (σ0 − σ ) versus ln (t ) is plotted for C = 1000 ppm and C = 3000 ppm in Figures (4.6)
1
and (4.7) respectively. 2
ln (t ) is also added to compare the experimental data and theory.

Figure 4.6: ln(σ0 − σ) versus ln (t ) for C = 3000 ppm

A linear regression was made for both experiments to obtain a linear equation for
ln(σ0 − σ ). The results are presented in Table (4.2).

Concentration Pendant drop Wilhelmy plate

1000 ppm ln (σ0 − σ ) = 1, 59 ln(t ) − 11, 86 ln (σ0 − σ ) = 0, 69 ln(t ) − 11, 86
3000 ppm ln(σ0 − σ ) = 0, 95 ln(t ) − 6, 95 ln(σ0 − σ ) = 0, 69 ln(t ) − 4, 82

Table 4.2: Equations of ln(σ0 − σ ) versus ln (t )

 Figure 4.7: ln(σ0 − σ) versus ln (t ) for C = 1000 ppm

Graphically and with the linear regression, it is easy to see that the Wilhelmy results
are more accurate than the pendant drop ones : the slope of the graph is closer to theory.
D can be easily calculated with the following equation :

π σ0 − σ
D= ( )2 (4.2)
t 2CB kB TNA
Figure (4.8) shows the values of D with time, calculated with equation (4.2) for pendant
drop and Wilhelmy plate.

Figure 4.8: Evolution of D versus time for Wilhelmy plate and

pendant drop method for C = 1000ppm and C = 3000 ppm
 Figure 4.9: ln(σ0 − σ) versus t for C = 1000 ppm

For Wilhelmy plate method, D keeps approximatively the same value with time (except
at the beginning), for both concentrations. However, a difference can be seen between
the two methods : D is 10 times greater for pendant drop than for Wilhelmy, and keeps
increasing during all the experiment. D is not plotted for C = 3000 ppm using pendant
drop because the values of D are 100 times greater than for Wilhelmy.
These results are questioning the accuracy of pendant drop method. Besides, these
values are surprising : D is expected to be contained between 10−8 and 10−10 m 2 /s, which
is not the case here. The calculations were made many times, but the results have not
been explained yet, and the mystery remains unsolved.

4.2.2 For Langmuir adsorption isotherm

Γ∞
For short times, surface tension follows this equation : σ0 −σ = kB TNA Γ∞ ln( √ ).
Γ∞ −2CB Dtπ
Taking the neperian logarithm, one can write :

1
ln(σ0 − σ ) = ln(kB TNA Γ∞ ) + ln(ln( √ )) (4.3)
1−η t
q
with η = Γ B
2C D
π
.
∞

As opposite to Henry adsorption isotherm, Γ∞ intervenes into the term which depends
upon time.
1√
Figures (4.9) and (4.10) represent ln(σ0 − σ ) and ln(ln( )) versus t for η = 10−5 .
1 −η t

Qualitatively, the results when using Wilhelmy plate method seem to have a similar
1√ 1√
shape than ln(ln( )). η was varied to see if the shape of ln(ln( )) changes a lot,
1−η t 1−η t
 1√
but it is not. A logarithmic regression was made to obtain the equation of ln(ln( ))
1−η t
versus ln (t ). It appears that, when varying η with Matlab, the slope of pendant drop
equation for both concentrations (see Table (4.2)), could not be reached.
η was then modified until the same slope of the logarithmic equation has been obtained
for the experimental results of Wilhelmy plate and the theoretical values.

The final values of η are given in Table (4.3).

Figure 4.10: ln(σ0 − σ) versus t for C = 3000 ppm

Concentration η (s−1/2 )
1000 ppm 0,0137751212
3000 ppm 0,014350899

Table 4.3: Values of η for C = 1000ppm and C = 3000ppm

4.3 Influence of a higher concentrated compund

In this section, PEG-600000 is studied instead of PEG-400. PEG-600000 is also

known as PEO (polyethylene oxide) because its molecular mass is above 20 000 g/mol (in
that case M = 600 000 g/mol). The experiments were made using both pendant drop and
Wilhelmy plate methods. The results are presented in Tables (4.4) and (4.5).
For both methods, surface tension seems to be decreasing at the beginning but then
increases. At first sight, because pendant drop was first used, the results seemed to
be not accurate. However, after using Wilhelmy plate method, the values are following
the same evolution than with pendant drop. This might mean that adsorption does not
 Time (min) Pendant drop Wilhelmy plate
0 48,41 56,239
5 48,38 56,213
10 47,79 56,061
20 48,48 55,761
25 48,26 55,686
30 48,125 55,639
40 48,21 55,522
50 47,88 55,688
60 47,53 55,828

Table 4.4: Surface tension for C = 1000 ppm

appear immediately because the process is very slow : the molecular mass of PEG-600000
is so high that diffusion hasn’t had enough time to establish. An other solution which can
explain these weird results is that PEG-600000 hasn’t had time to solubilize enough into
water when the experiments were made. The values might have been different if a longer
period of time has been allowing before taken the measurements. However, because time
was running out, this hypothesis could not have been verified. Besides, these results
are not good enough to do a short time analysis and then try to compare them with a
numerical simulation (see Chapter 5).

Figures (4.11) and (4.12) represent surface tension for C = 1000ppm using Wilhelmy
plate and pendant drop for PEG-400 and PEG-600000.

Figure 4.11: Surface tension versus t for C = 1000ppm for PEG-400 and
PEG-600000 using Wilhemy plate
 Figure 4.12: Surface tension versus t for C = 1000ppm for PEG-400 and
PEG-600000 using pendant drop

4.4 System composed of both PEG-400 and PEG-600000

In this section, the studied system is composed of water and half PEG-400, half PEG-
600000. The amount of PEG introduced into water is 2.10−6 mol for each compound,
which represents 1.2 g of PEG-600000 and 0.71 µL of PEG-400.

Figure 4.13: Surface tension versus t for a system composed of 2.10−6

mol of PEG-400 and PEG-600000
 When preparing the solution, it appears that PEG-600000 does not solubilize imme-
diately into water : some particles stay into the solution until being completely absorb.
This process lasted almost one hour before measurements started. Surface tension was
measured using Wilhelmy plate and lasted 105 minutes. The results are plotted in Figure
(4.13).
For this experiment, the results seem to be quite similar to the ones presented in
section (4.3) (use of PEG-600000 only) : surface tension decreases but not continuously
with time. The final value is lower than the first one but the shape of the graph is
not uniform like for PEG-400. One hypothesis can be made : for the same amount
of compound between PEG-400 and PEG-600000, the latter predominates. This might
have been expected when conducting the experiment : the amount of PEG-600000 added
into the solution was very important as compared to the one added of PEG-400. This
was shown when preparing the solution : PEG-400 solubilizes immediately into water
whereas PEG-600000 had to be added little by little to help the compound being absorb
by water. The amount of PEG-600000 was so important that one hour had to be waited
before the experiment started.
Chapter 5
Numerical study of adsorption

T
B).
he aim of this chapter is to understand adsorption with numerical values, obtained
using the C++ code written by Xueliang Bruce Li and Paul Stevenson (see Appendix

As presented in Chapter 3, this code solves numerically the Ward and Tordai equa-
tion. Langmuir adsorption isotherm is being considered because, as explained in the last
chapter, the experimental results match more this isotherm than Henry’s one.

The equation becomes in that case :

Γ(τ )
r t
√
Z
D
Γ(t ) − Γ0 = (2CB t − √ dτ ) (5.1)
πt 0 KL (Γ∞ − Γ(τ )) t − τ

The parameters taken into account are Γ∞ , T , CB , D, KL and the surface tension of
the solvent (here σwater ). However, for the system PEG-400/water, Γ∞ and KL remain
unknown.
To solve this problem, the results of Chapter 4 are being considered :

- D will be taken equal to 10−17 m 2 /s (see section 4.2.1).

- η will be taken equal

q to 1,4.10−2 s−1/2 . This leads to Γ∞ = 6, 2.10−7 mol/m 2 using
relation η = Γ B Dπ .
2C
∞

The concentration considered to obtain these results is CB = 1000 ppm (25.10−1

molm 3 ). The next section explains how to find KL .

5.1 Getting closer to the experiments

The first numerical simulation was made with σwater = 72 mN/m and KL = 1.103
m 3 /mol. The experimental and numerical results for CB = 1000 ppm are plotted in Figure
(5.1).

Some differences can be pointed out between the experimental and numerical solutions.
First of all, σ0 is not the same : for the simulation, it starts from 72 mN/m (i.e σwater )
whereas experimentally, it is 46,5 mN/m. This might mean that the simulation does not

41
 Figure 5.1: Comparison of numerical and experimental solutions for KL
= 103 m 3 /mol

take into account the first diffusion step in the adsorption kinetics supposed previously.
On the contrary, if this hypothesis is wrong, this indicated that the experimental measures
are not accurate. Besides, one can add that the shape of the graph seems to be different
for simulation and experiment (but this KL is a random data).

A closer look was made to see the difference between the two shapes. For the simulation,
σ0 has been taken equal to 47 mN/m to match the experiment as closely as possible. The
new simulation is plotted in Figure (5.2).

Figure 5.2: Comparison of numerical and experimental solutions for KL

= 103 m 3 /mol and σ0 = 47 mN/m
 KL was then varying to find the value which matches the experiment as closely as
possible. Figure (5.3) shows the numerical simulations for different values of KL .

Figure 5.3: Numerical simulations for different values of KL

It seems that the closest value for KL , which corresponds to the experiment, is con-
tained between 4 and 4.5 m 3 /mol. However, it is important to notice that these are
hypothetical results. Indeed, all the parameters settled up are based upon the experi-
mental results presented in Chapter 4. D was calculated assuming that σ follows Henry
adsorption isotherm for short times. On the contrary, Γ∞ was obtained using Langmuir
isotherm. The value of D has been kept because the diffusion coefficient is supposed to be
related to the compound (here diffusion of PEG-400 into water) and not the concentration
or adsorption isotherm studied. Besides, D was calculated equal to 10−17 m 2 /, which is
relatively small : usually D is expected to be contained between 10−8 and 10−10 m 2 /s.
This all numerical work is based on assumptions which might have been verified with
empirical experiments if the project work had been longer.

5.2 Influence of concentration

In this section, the values calculated and presented previously are considered :
- D = 10−17 m 2 /s
- Γ∞ = 6,2.10−7 mol/m 2
- KL = 4,5 m 3 /mol
- T = 300 K

Figure (5.4) shows the numerical simulation for different concentrations : C1 = 5.10−1
mol/m 3 (1000 ppm), C2 = 2,5.10−1 mol/m 3 (3000 ppm), C3 = 1.10−3 mol/m 3 , and C4 =
10 mol/m 3 .

Figure 5.4: Numerical simulations for different concentrations

The numerical results show that the more concentrated the solution is, the faster
surface tension decreases. Besides, for higher concentrations, diffusion time (time when
σ∞ is reached) is shorter than for smaller ones. However, Figure (5.4) does not show if
σ∞ is the same for all the concentrations. A new simulation has been made for C1 = 5
mol/m 3 and C2 = 2.5 mol/m 3 for longer times.

Figure 5.5: Numerical simulations 2.5 and 5 mol/m 3 for t = 100000 s

Figure (5.5) shows the results for the previous simulation : σ∞ will not be the same for
all concentrations. This could have been expected because ΓS (which is related to σ with
adsorption isotherms) depends on CB (see equation (5.1)).
 This study can be related to the experimental ones in calculating the difference σ0 -
σ2700 to see if the two studies evolves similarly. The results are given in Table (5.1).

Method C = 1000 ppm C = 3000 ppm

Simulation 1.657 mN/m 4.953 mN/m
Experiment 1.691 mN/m 1.835 mN/m

Table 5.1: σ0 - σ2700 for experiment and simulation

The results seem to be very close for C = 1000 ppm. However, the simulation and the
experiment does not match for C = 3000 ppm.

It is important to point out that all this numerical study has been made with hy-
potheses. Indeed, to obtain the values of D and η both Henry and Langmuir adsorption
isotherms were supposed to be verified (which actually is not accurate). Besides, an other
hypothesis has been made for Γ∞ . Here, only one value of q
Γ∞ is considered for different
concentrations. However, the following equation η = Γ shows that Γ∞ is related
2CB D
π
∞
to the concentration. Different values of η have been calculated in section (4.2.2) which
must lead to different Γ∞ for 1000 and 3000 ppm. Nevertheless, not enough experiments
using different concentrations had been made to obtain all these values. The numerical
graph might had looked differently if the study had been conducted with the real values.

5.3 Influence of temperature

For these simulations, C = 1000 ppm is considered. The parameters calculated previ-
ously are used : just the temperature T is modified to see its influence upon the evolution
of surface tension.

Figure 5.6: Influence of temperature on surface tension

Figure (5.6) represents surface tension for T = 273, 300 and 350 K. It shows that the
higher the temperature is, the faster the decline of σ is. However, this simulation can’t
be verified experimentally because the experiments were conducted for T = 300 K only.
Chapter 6
Conclusion

H ow does adsorption manifest itself into a solution of water and PEG ? This is what
has been studied during this project work through conducting measurements of
water surface tension. This phenomena was first explained theoretically to understand
the closer link between surface tension and adsorption. With this theoretical background,
the results of the experiments could have been understood. However, obscure points,
such as the differences in the initial water surface tension when using Wilhelmy plate
and pendant drop method or the surprising value of D, still remain. Finally, a numerical
test has been conducted to compare simulated and experimental results. Nevertheless,
not enough experiments had been made to obtain all the missing parameters which make
the simulation run. Therefore, the numerical results presented in this report are not
accurate.

This internship makes me realize how difficult the research work can be. I have been
facing many difficulties when conducting this project, some of which remain unsolved.
Besides, I also have noticed that chemistry is not always experimental : a long research
work has to be done to understand the setting up, especially when the results are not
the ones expected. I wish my internship had been longer so I could have tried solving
the unexpected results and the experimental issues I have been through. However, this
project was very instructive and I learnt a lot.

47
Appendices

49
Appendix A
The Young-Laplace equation

This appendix shows how the Young-Laplace equation can be obtained mathemati-
cally. Let us consider a liquid bubble of radius r, shown in Figure (A.1). The pressure
inside and outside the drop is P(z) and P0 respectively.

Figure A.1: Drop

Now, lets consider that the size of the bubble expands from r to r + dr. The work W
necessary for the expansion is

W = (P (z ) − PC )dV = 4∆Pπr 2 dr (A.1)

As a manifestation of increase of radius, the surface energy of the bubble increases.

Consequent to this, the energy of interaction E changes by dE :

dE = σdA = 8πσrdr (A.2)

Now, one can obtain the following equation, known as the Young-Laplace equation :

2σ
∆P = (A.3)
r

51
Appendix B
Solving the Ward and Tordai equation

In this appendix, a part of the code of Xueliang Bruce Li and Paul Stevenson [2] to
solve the Ward and Tordai equation is presented.

Diffusion-controlled adsorption rate and DST calculator

"This code is written by Xueliang Bruce Li and Paul Stevenson of the University of
Newcastle, Australia. If using this code for publication, please cite our contribution. Any
questions please contact us: paul.stevenson@newcastle.edu.au "
This code is provided as is for educational and indicative purposes only. The authors
do not accept liability for, and make no claims regarding the accuracy or applicability of
calculations or formulae contained herein. The user may only use information provided in
this code at their own risk which is provided without either express or implied guarantee."
system("PAUSE");
"Adsorption onto a planar interface is calculated using the equation of Ward and
Tordai (Ward AFH, Tordai L 1946 Time-dependence of boundary tensions of solutions:
The role of of diffusion in time effects, J Chem Phys 14, 453-461. Adsorption onto a
convex interface is calculated using the equation of Lin et al. (Lin et al. 1990 Diffusion-
controlled surfactant adsorption studied by pendant drop digitization, AIChE Journal 36,
1785-1795.) The forms of the adsorption isotherm adopted are those given in section 2.3
of: Eastoe J, Dalton JS 2000 Dynamic surface tension and adsorption mechanisms of
surfactants at the air-water interface, Adv Colloid Int Sci 84, 103-144."
char option;
"Would you like to use the advanced mode (the advanced mode allows you to change
settings of the numerical routine such as the tolerance and maximum number of itera-
tions)? Use this mode only if the default settings does not produce satisfactory results.
(Y/N)";
if (option== ’Y’ || option== ’y’)
"Please enter the tolerance you want to use (default: 1e-30) : "
"Please enter the maximum iteration you want to use (default: 100) : "
"Now you will be asked to give values of the model parameters. Please use the units
suggested and the scientific notation, e.g., type 1e-6 for 0.000 001"

53
 system("PAUSE");
"Please enter the thermodynamic (absolute) temperature (K)"
"Please enter the surface tension of the solvent (N/m) : ";
"Please enter the bulk concentration (mol/m 3 ) : ";
"Please enter the molecular diffusivity (m/s2 ) : ";
"Please enter the value of n (-) : ";
"Please enter the total time of simulation (s) : ";
"Please enter the time increment (s) : ";
"Please specify the shape of the interface, type 0 (number zero) for a convex spherical
interface or 1 (number one) for a planar interface: ";
"Please specify the adsorption isotherm,"
" 1 for Henry’s Law isotherm"
" 2 for the Langmuir isotherm"
" 3 for the Frumkin isotherm"
" 4 for the Freundlich isotherm"
" 5 for the Volmer isotherm"
"Please check the values you have entered. Restart the program if any mistakes."
system("PAUSE");
Bibliography

[1] A. Ward and L. Tordai, J. Chem. Phys., vol. 14, pp. 14–453, 1946.

[2] D. Ruthven, Principles of adsorption and adsorption processes. Wiley-Blackwell, 1984.

[3] X. Li, R. Shaw, G. M. Evans, and P. Stevenson, “A simple numerical solution to the
ward–tordai equation for the adsorption of non-ionic surfactants,” Computers and
Chemical engineering, vol. 34, no. 2, pp. 146–153, February 2010.

55