STUDIES ON INTERFACIAL PROPERTIES OF

NATURAL SURFACTANTS AND ITS

APPLICATIONS

Under the esteemed guidance of

Prof. Santanu Paria.

Presented by
Nihar Ranjan Biswal

National Institute of Technology, Rourkela - 769008

Orissa. India
 Outline
Introduction
Origin of the problem.
Environmental need.
Background.
Objectives of the study.
Plan of work and methodology.
Work done.
1. Adsorption Studies.
2. Wetting properties.
Conclusions & Further Work.

2
Introduction
Surface-Active Agent or Surfactant

Surfactant represents a heterogeneous and long-chain molecule containing both hydrophilic

(water-loving) and hydrophobic (water fearing) moieties.

Hydrophilic (Head) Hydrophilic (Tail)

CMC (critical micelle concentration)

3
 Outline

Introduction

Origin of the problem.

Environmental need.
Background.
Objectives of the study.
Plan of work and methodology.
Work done.
1. Adsorption Studies.
2. Wetting properties.
Conclusions & Further Work.

4
 Origin of the problem.

More and more use of surfactants due to its wide range of applicability (detergency, wetting, flotation,
colloidal stability, emulsions, pharmaceutical, cosmetics products, remediation processes).
Synthetic surfactants are not easily biodegradable.
Creates environmental problem.

5
Origin of the problem
Production of the different types of surfactants used in the USA,
Japan and western Europe pa.

6
 Origin of the problem.
Surfactant consumption in the USA, Japan and western Europe pa.

7
The US-EPA report shows that developed countries like USA, 2-3 % are
using surfactant enhanced remediation technology for removal of
contaminants in laboratories only.
But when it will come to a field huge amount of surfactant will needed
and after application it will go to the environment.

8
 Origin of the problem.

But after the application domestic waste-water containing soaps and detergent solutions are thrown to
the environment can also lead to groundwater contamination if added to the soil matrix without any
treatment.

9
Table from US-EPA
 Origin of the problem.

Most of the surfactants used in different application are synthetic surfactants, manufactured by
synthetic chemical route. Depending on the structure of the surfactants, mostly synthetic surfactants
are not biodegradable and create a large numbers of environmental problems.

Breakdown products are more toxic to aquatic organisms than the APE/LAS themselves

Decrease of hormone oestrogen endocrine disruptors may be responsible for a decreasing male sperm
count, testicular and breast cancer.
On zooplankton effect is their sex determination and development.

11
 Outline

Introduction
Origin of the problem.

Environmental need
Background.
Objectives of the study.
Plan of work and methodology.
Work done.
1. Adsorption Studies.
2. Wetting properties.
Conclusions & Further Work.

12
Environmental Need

1) Cost effective,
2) Lower toxicity,
3) Higher biodegradatibiliy,
4) Better environmental compatibility,
5) Higher foaming,
6) Higher selectivity for metal ions and organic compounds,
7) More tolerant to pH, salt and temperature variation, and
8) The ability to be synthesized from renewable sources.

13
 Outline
Introduction
Origin of the problem.
Environmental need.

Background.
Objectives of the study.
Plan of work and methodology.
Work done.
1. Adsorption Studies.
2. Wetting properties.
Conclusions & Further Work.

14
Environmentally Friendly Surfactants

Synthetic
Food grade synthetic surfactants (Sugar based,)
Natural
Bio-surfactants
Plant
Background.

Bio-surfactants
Bio-surfactants are amphiphilic biological compounds synthesized by extracellularly or as a part of
the cell membrane by variety of yeast, bacteria and filamentous fungi.

The hydrophobic part fatty acids, and the hydrophilic portion a carbohydrate, amino acid, cyclic
peptide, phosphate, carboxylic acid or alcohol.

Types

Low molecular mass molecules with lower surface and interfacial tension (e.g. rhamnolipid and
sophorolipids).
High molecular mass polymers which bind tightly to surfaces (e.g. Emulsan, and Liposan).

16
 Literature Review on Bio-surfactant
Surfactant Types of System Reference Country
study

Rhamnolipid Adsorption Soil. 1. Noordman et al., Environ. Sci. USA

Metal oxides, Technol. 2000, 34, 832-838.
Clay minerals 2. Torrens et al., Environ. Sci. Technol.
1998, 32, 776-781.
3. Ochoa-Loza et al., Chemosphere, 66,
(9), 1634-1642.

Rhamnolipid Solubilization Hexadecane. 1. Mulligan et al., Engineering Geology.,

Pentachloro- 2001, 60, 371380. Canada
phenol (PCP) 2. Thangamani and Shreve, Environ. Sci. Thailand
Crude oil, Technol., 1994, 28 (12), 1993-2000. Japan
3. Pornsunthorntawee et al., Biochemical India
Engineering Journal., 2008, 42, 172
179.
4. Bordoloi and Konwar, Colloids and
Surfaces B: Biointerfaces, 2008, 63 73 17

82.
Literature Review on Bio-surfactant

Surfactant Types of study System Reference Country

Rhamnolipid Removal of Arsenic, 1. Wang and Mulligan, Process Canada

Metal Zinc, Biochemistry., xxx (2008) xxx Turkey
Heavy Metals. xxx.
2. Asc1 et al., Desalination 2008, 223
361365.

Rhamnolipid Wetting Glass, 1. Ozdemir and Malayoglu., Colloids Turkey

Polyethylene and surfaces B: Biointerfaces,
Terephthalate 2004, 39, 1-7.

18
Bio-surfactant

The preparation of bio-surfactants is not a very easy process and it is difficult to

produce huge amount of bio-surfactant to replace synthetic one. At the same time it may not
be cost effective as compared to synthetic surfactants where requirement is high.

19
 Plant surfactants

Reetha Shikakai Acacia

Saponins: soap-like foams with water, occurring primarily in the plant kingdom.

Chemically, saponins as a group include compounds that are glycosylated steroids, triterpenoids,
and steroid alkaloids.

They consist of nonpolar aglycones coupled with one or more monosaccharide moieties.

1. Reetha (Sapindus Mukorossi)

2. Shikakai (Acacia concinna)
3. Acacia (Acacia auriculiformis)

20
 Literature Review on Plant-surfactant
Surfactant Types of study System Reference Country

Acacia Extraction, - 1. Mahato et al., Tetrahedron, 1992, India

auriculi- Isolation 48, (32), 6717-6728.
formis and 2. Mahato et al., Tetrahedron, 1992, India
Structural 48, (32), 6717-6728.
Elucidation 3. Garai and Mahato, India
Phytochemistry, 1997, 44, (1), 137-
Acacia 140.
concinna 4. Gafur et al., Chem. Pharm. Bull., Japan
1997, 45, (4) 620-625.
5. Tezuka et al., J. Nat. Prod. 2000, Japan
63, 1658-1664.

Sapindus Micellar Aqueous 1. Balkrishnan et al., Tenside Surf. India

Mukorossi Characteriza- medium Det. 2006, 43, (5), 262-268.
ion 2. Majhi et al., Langmuir, 1999, 15, 21

6624-6630.
 Literature Review on Plant-surfactant
Surfactant Types of study System Reference Country

Sapindus Solubilization Naphthalene, 1. Rao and Paria., J. Phys. Chem. B India

Mukorossi Hexachloro- XXXX, xxx, 000. Louisiana
benzene. 2. Roy et al., Environ. Sci. Technol.
Cruid oil 1997, 31, 670-675.
3. Balkrishnan et al., Tenside Surf.
Det. 2006, 43, (5), 262-268.

Quillaja Removal of Metal Cd, Pb, Cu, Ni 1. Chen et al., Process Biochemistry, China
saponin. 2008, 43, 488498.
Tea 2. Yuan et al., Colloids and Surfaces
saponin A: Physicochem. Eng. Aspects, Taiwan
2008, 317, 256261.

22
 Outline

Introduction
Origin of the problem.
Environmental need.
Background.

Objectives of the study.

Plan of work and methodology.
Work done.
1. Adsorption Studies.
2. Wetting properties.
Conclusions & Further Work.

23
Objectives of the study.

1. To study the adsorption kinetics and isotherm of plant surfactants on

hydrophobic as well as hydrophilic surfaces and its comparison with
synthetics surfactants.
2. To evaluate the Wettability of hydrophobic and hydrophilic surfaces by
plant and synthetic surfactants.
3. To find out the micellar solubilization efficiency of PAHs by three plant
surfactants Reetha, Shikakai and Acacia and its comparison with synthetic
surfactants.
4. Mixed micellar behavior of three plant surfactants Reetha, Shikakai and
Acacia along with synthetic surfactants.
24
 Outline
Introduction
Origin of the problem.
Environmental need.
Background.
Objectives of the study.

Plan of work and methodology.

Work done.
1. Adsorption Studies.
2. Wetting properties.
Conclusions & Further Work.

25
 ROAD MAP FOR RESEARCH WORK FOR THREE YEARS DURATION

Activity Time period

Jan, 08 to July, 08 to Jan, 09 July, 09 Jan, 10 to July, 10 Remark
June, 08 Dec, 08 to June, 09 to Dec, 09 June, 10 to Dec, 10

Course work and literature completed

survey

Course work and completed

development of procedure for
experiments.
Study of adsorption kinetics Under
and Isotherm. process

Its application Under

1.Wetting. process
2.Solubilization.
3.Mixed micellar behavior.

Results Analysis. Under

process
Thesis Writing.

26
Methodology

Extraction (Plant),
Characterization

Surfactant Analysis

Characterization of
adsorbent
Methodology
Kinetics and Adsorption
Isotherm

Wetting properties

Removal study

27
Start the journey

28
 Outline

Introduction
Origin of the problem.
Environmental need.
Background.
Objectives of the study.
Plan of work and methodology.

Work done.
1. Adsorption Studies.
2. Wetting properties.
Conclusions & Further Work.

29
Extraction and Characterization of Plant surfactants

Plant surfactant

Extraction Characterization

Surface tension Conductance

1. Reetha (Sapindus Mukorossi)

2. Shikakai (Acacia concinna) 30
3. Acacia (Acacia auriculiformis)
Acacia auriculiformis

Mol mass-1765.
31
Reetha (Sapindus Mukorossi)

R=
Mol. mass = 966.
32
Shikakai (Acacia concinna)

Mol. mass =

33
 Adsorption
Kinetics

Teflon/PTFE Isotherm
Hydrophobic
Surface
Effect of
Electrolyte
Adsorption

Kinetics
Hydrophilic
Surface Kaolin,
Sand

Isotherm 34
Contact Angle/Wetting Triton X-
100

Reetha
Hydrophilic
Glass
Shikakai

Acacia
Wetting
Triton X-
100

Reetha
Hydrophobic
Teflon/PTFE
Shikakai

Acacia 35
Adsorption of Synthetic surfactants on PTFE surface

1. Kinetics
2. Isotherm
3. Effect of electrolyte

36
 Adsorption process

Adsorption of surfactants at the solid-water interface is strongly influenced by the

The nature of the structural group on the solid surface.
The molecular structure of the surfactant going to be adsorb.
The environment of the aqueous phase.

Together all these factors determine the mechanism by means of which adsorption occurs, the
efficiency and effectiveness adsorption.

37
 Adsorption process

There are nos. of mechanisms by which adsorption may takes place

Ion pairing and ion exchange.
Hydrogen bonding .
Hydrophobic bonding.
Adsorption by dispersion force.

38
 Adsorption process

Mainly there are two types of forces acting between two charged particles in an electrolyte solution.
Electrostatic double layer interaction.
Vander Waal's force of attraction.
Depending upon the relative magnitude of these two interactions, the net interaction may be repulsive
or attractive.

39
Kinetics of adsorption of different synthetic and Plant surfactants on
PTFE powder solid surface.

Graph-1 Graph-2

40
Adsorption isotherm of TX-100 surfactant on PTFE surface.

The adsorption isotherms for Nonionic/mono-ionic surfactant on PTFE surface are mainly of
Langmuir type. They appear to show the surface saturation in the vicinity of CMC and orientation of
the surfactant perpendicular to the surface and mainly due to the dispersion forces.
41
Adsorption isotherm of CPBr and SDBS surfactant on PTFE surface

In many cases the adsorption isotherm shows inflection that is due to

change in orientation.
42
Adsorption isotherm of CPBr and SDBS surfactant on PTFE surface

The adsorption initially may be parallel to the solid surface, slightly tilted or L-shaped with the
hydrophobic group close to the surface and hydrophilic group towards the aqueous phase.

As we will goes on increasing the surfactant concentration the orientation of the surfactant molecule
from more and more perpendicular.

43
 Effect of Electrolyte

Neutral electrolyte addition increases both the efficiency of adsorption by decreasing the repulsion
between the similarly charged adsorbed ion and oncoming ion as well as the effectiveness of
adsorption probably by decreasing the electrical repulsion between the similarly charged adsorbed
ions permitting closer packing.

Cations have great effect on anions adsorption and vice versa.

44
Effect of Electrolyte
Effect of electrolyte NaCl on CMC and amount of adsorption
0.1 mM CpBr + NaCl

0.05 mM SDBS + NaCl

 Effect of Electrolyte

The depression of the CMC of these cases is mainly due to the decrease in the thickness of the ionic
atmosphere surrounding the ionic head groups in the presence of the additional electrolyte and the
consequent decreased electrical repulsion between them in the micelle.
Effect of Electrolyte
Effect of electrolyte Na2SO4 on CMC and amount of adsorption
0.1 mM CpBr + Na2SO4

0.05 mM SDBS + Na2SO4

 Effect of Electrolyte

The stern layer potential for SDBS and CPBr decreases with the concentration of added salt. The natures
of counter ions affect the electrostatic potential as well as the mobility.
Effect of Electrolyte
Effect of electrolyte CaCl2 on CMC and amount of adsorption
0.1 mM CpBr + CaCl2

0.05 mM SDBS + CaCl2

Contact Angle/Wetting

50
Conclusions.

It will be a better substitute to utilize plant derived saponin instead of synthetic surfactants and bio-
surfactants produce by microorganism, which have the following advantages: is cost effective, lower
toxicity, higher biodegradatibiliy, better environmental compatibility, higher foaming, higher
selectivity for metal ions and organic compounds, more tolerant to pH, salt and temperature
variation, and the ability to be synthesized from renewable sources.

51
 Further Work

1. Micellar solubilization of PAHs by three plant surfacts Reetha (Sapindus

Mukorossi), Shikakai (Acacia concinna), and Acacia (Acacia auriculiformis)
and its comparission with synthetic surfactants will be done .
2. Mixed micellar behavior of three plant surfactants Reetha (Sapindus
Mukorossi), Shikakai (Acacia concinna), and Acacia (Acacia auriculiformis)
along with synthetic surfactants will be investigated.

52
 References
Abrlola, L. M., Dekker, T. J., Pennell, K. D., Surfactant-Enhanced Solubilization of
Residual Dodecane in Soil Columns. 2. Mathematical Modeling. Environ. Sci. Technol. 1993,
27, 2341-2351.
As1 Y., Nurbas M, A1kel, Y. S., Removal of zinc ions from a soil component Na- feldspar by a
rhamnolipid bio-surfactant. Desalination 2008, 223 361 365.
Balkrisnan, S., Varughese, S., Deshpande, A.P., Micellar characterisation of saponin from
Sapindus Mukorossi. Tenside Surf. Det. 2006, 43, (5), 262-268.
Bordoloi, N.K. Konwar, B.K., Microbial surfactant-enhanced mineral oil recovery
under laboratory conditions. Colloids and Surfaces B: Biointerfaces, 2008, 63 73 82.
Chen, W. J., Hsiao, L.C., Chen, K. K. Y., Metal desorption from copper (II)/nickel (II)-
spiked kaolin as a soil component using plant-derived saponin bio- surfactant. Process
Biochemistry, 2008, 43, 488498.
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bio-surfactants. Advances in colloid and interface science, 2007, 134-135, 24- 34.
Gafur, M. A., Obata, T., Kichi, F., Tsuda, Y., Acacia concinna saponin I. Structure of
prosapogenols, concinnosides A-F, isolation from the alkaline hydrilysate of highly polar 53
saponin fraction. Chem. Pharm. Bull., 1997, 45, (4) 620- 625.
 References

Garai, S., Mahato, S. B., Isolation and structure elucidation of three terpenoid saponin from acacia
auriculiformis. Phytochemistry, 1997, 44, (1), 137-140.
Mahato, S. B., Pal, B. C., Nandy, A. K., Structure elucidation of two acylated triterpenoid
bisglycosides from acacia auriculiformis Cunn. Tetrahedron, 1992, 48, (32), 6717- 6728.
Majhi, P. R., Mukherjee, K., Moulik, S. P., Sen, S., Sahu, N. P., Solution properties of a saponin
(acaciaside) in the presence of triton x-100 and igepal. Langmuir, 1999, 15, 6624- 6630.
Mulligan, C. N., Eftekhari F., Remediation with surfactant foam of PCP- contaminated soil.
Engineering Geology, 2003, 70, 269279.
Noordman, W. H., Brusseaubu,M. L., Janssen, D B., Adsorption of a multicomponent rhamnolipid
surfactant to soil. Environ. Sci. Technol. 2000, 34, 832- 838.
Ozdemir, G., Malayoglu, U., Wetting characteristics of aqueous rhamnolipids solution. Colloids and
surfaces B: Biointerfaces, 2004, 39, 1-7.
Pornsunthorntawee,O., Arttaweeporn, N., Paisanjit,S., Somboonthanate, P., Abe, M.,
Rujiravanit, R., Chavadej, S., isolation and comparison of bio-surfactants produced by
Bacillus subtilis PT2 and Pseudomonas aeruginosa SP4 for microbial surfactant- enhanced oil
54
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 References

Rosen, M. J. surfactant and interfacial phenomena, 2 nd edition, Jhon wiley & Sons, New York, 1989, p-
240.
Roy, D., Kommalpati, R. R., Manava, S.S., Valasaraja, K. T., Constant, W. D., Soil washing
potential of a natural surfactant. Environ. Sci. Technol. 1997, 31, 670- 675.
Tezuka, Y., Honda, K., Banskota, A. H., Thet, M. M., Kadota, S., Kinmoonosides A-C, three new
cytotoxic saponins from the fruits of acacia concinna, a medicinal plant collected in
myanmar. J. Nat. Prod. 2000, 63, 1658-1664.
Torrens J. l., Herman D. C., and Maier R. M. M., Bio-surfactant (Rhamnolipid) sorption and the
impact on rhamnolipid-facilitated removal of cadmium from various soils under saturated
flow conditions, Environ. Sci. Technol. 1998, 32, 776-781.
Wang, S., Mulligan, C. N., Rhamnolipid bio-surfactant-enhanced soil flushing for the removal
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Yuan, X. Z., Meng, Y.T., Zeng, G.M., Fang, Y. Y., Shi, J.G., Evaluation of tea-derived
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and Surfaces A. 2008, 317, 256261.
Any Queries ?
56