View metadata, citation and similar papers at core.ac.

uk
brought to you by CORE

provided by ethesis@nitr

EFFECT OF DIFFERENT
ADDITIVES ON CLOUD POINT OF
NON IONIC SURFACTANT

A Thesis submitted to the

National Institute of Technology, Rourkela
In partial fulfilment of the requirements
of
Bachelor of Technology (Chemical Engineering)
By Dhananjay
Singh Roll No.
107CH028

Under the guidance of

Dr. Santanu Paria

DEPARTMENT OF CHEMICAL ENGINEERING

NATIONAL INSTITUTE OF TECHNOLOGY, ROURKELA
ODISHA -769 008, INDIA
2011
 NATIONAL INSTITUTE OF TECHNOLOGY,
ROURKELA

CERTIFICATE

This is to certify that the thesis entitled “Effect of Different Additives on

Cloud Point of Non Ionic Surfactant”, submitted by Dhananjay Singh for the
requirements of bachelor’s degree in Chemical Engineering Department of
National Institute of Technology, Rourkela is an original work to the best of my
knowledge, done under my supervision and guidance.

Date-12/06/11
Dr. Santanu Paria
Department of Chemical Engineering
National Institute of Technology,
Rourkela - 769008
 ACKNOWLEDGEMENT

In the pursuit of this academic endeavour, I feel I have been singularly

fortunate. I should fail in my duty if I do not record my profound sense of
indebtedness and heartfelt gratitude to my supervisor Dr. Santanu Paria who
inspired and guided me in the pursuance of this work.

I want to acknowledge the support and encouragement of Mr Nihar Ranjan

Biswal, Mr Rajib Ghosh Chaudhuri, and Mr K. J Rao in the lab work.

I owe a depth of gratitude to Prof. K.C. Biswal, H.O.D. of Chemical

Engineering department, National Institute of Technology, Rourkela, and all
other fa culties for all the facilities provided during the course of my tenure.

Date-12/06/11 Dhananjay Singh

 CONTENTS

Title Page No.

ABSTRACT i
List of Figures ii
List of Tables iv

1 INTRODUCTION 1
1.1 Surfactants 2
1.1.1 Anionic Surfactants 2
1.1.2Cationic Surfactants 2
1.2.3 Non-Ionic Surfactants 3
1.2.3.1 Types of Non-ionic Surfactants 3
1.2.3 Zwitterionic Surfactant 4
1.3 Cloud Point 3
1.4 Turbidity 5
1.5 Objective 5
2 LITERATURE REVIEW 6
2.1 Single Surfactant 7
2.2 Mixed Surfactants 8
2.3 Effect of Electrolyte 10
3 EXPERIMENTAL WORK 19
3.1. Materials 20
3.2. Methods 20
4 RESULT AND DISCUSSION 23
4.1 Cloud Point of Surfactant 24
4.2 Effect of Concentration 25
4.3 Effect of Mixed Surfactant 26
4.3.1 Mixing of TX-100 with CTAB 27
4.3.2 Mixing of TX-100 with SDS 29
4.3.3 Comparison of CTAB and SDS 29
4.4 Effect of Additives on Non- Ionic Surfactant 32
4.4.1 Effect of Na2SO4 on TX-100 32
 4.4.2 Effect of CaCl2 on TX-100 33
4.4.3 Effect of NaCl on TX-100 34
4.4.4 Comparison of Additives 36
5 CONCLUSION 38
REFERENCES 39
 ABSTRACT

Determination of cloud point of non-ionic surfactants have wide applications as it is the

temperature where the mixture starts to phase separate and the two phases appear, thus

becoming cloudy. Non-ionic surfactants find suitable applications for recovery of membrane

components under mild non-denaturing condition. Knowing the cloud point helps us to

determine the storage stability since storing formulations at temperatures significantly higher

than the cloud point may result in phase separation and instability. Generally, non-ionic

surfactants show optimal effectiveness when used near or below their cloud point.

In this present work, effects of different additives on cloud point of non-ionic surfactants

have been studied. Triton X-100 (TX-100) has been used as the non-ionic surfactant and

observations have been done subsequently for different concentration of TX-100 by taking

various additives like NaCl, Na2SO4, CaCl2 and corresponding temperature were noted down.

Other than non-ionic surfactants, experiments were conducted for both cationic as well as

anionic surfactants. Based upon the result, graphs were plotted which comply well with the

theoretical study.

Keywords: cloud point, non-ionic surfactants.

i
 List of Figures

Page
Figure No. Title
No.
Fig. 2.1 Cloud point of aqueous solutions of Triton X-100 as a function of its 7
concentration.

Fig. 2.2 The effect of the addition of CTAB on the cloud point of 0.1% () and 8
1% () solutions of TX-100.

Fig. 2.3 The effect of hydrocarbon chain length of ionic surfactant homologs on 9
the cloud point of 1%. Solution of TX-100 .,SCS; ,SDS; ,CTAB;
,DTAB.

Fig. 2.4 Relation between cloud point of 1 wt% aqueous solutions of NPE8, 10
NPE10, NPE12, and concentration of additives: oleic acid, PEG 400, PEG
1000, and PEG 4000.

Fig. 2.5 Effects of nonionic additives on the cloud point of poloxamine 908 at 1 11
% (w/v).

Fig. 2.6 Cloud point shift values ∆ of 2.0% Triton X-100 solutions as a function 12
of the molality of added electrolytes.

Fig. 2.7 Cloud point shift values ∆ of 1.0% Brij 76 solutions as a function of the 13
molality of added electrolytes.

Fig. 2.8 The effect of the alcohols on the cloud point of 2 wt % NPEx solutions. 14
Fig. 2.9 Cloud point (CP) of a 1 % solution of Triton X-100 as a function of the 15
molar concentration of added sodium alkyl sulfates: C8H17OSO3Na (O),
C12H25OSO3Na (X), and C14H29OSO3Na (●).

Fig. 2.10 The effect pf cryptand 222 (∆) and NaCl (▲) on the cloud point (CP) of 15
a 1 % solution of Triton X-100 and the cloud point data for Triton X-
100- sodium octyl sulfate (SOS) mixtures without ( X ) and with
cryptand 222 (O) and NaCl (●). The molar ratios of cryptand 222/SOS
and NaCl/SOS were 1:1.

ii
Fig . 2.11 The effect of cryptand 222 ( X ) on the cloud point (CP) of C8E4-sodium 16
octyl sulfate (SOS) mixtures (●). The molar ratio of cryptand 222/SOS
was 1:1.

Fig. 2.12 Cloud point of 10 % Triton X-100 solution in the presence of methanol, 16
ethanol, propanol, butanol, and butoxyethanol (BE) of different
concentrations.

Fig. 2.13 Cloud point of 10 % Triton X-100 solution in the presence of hexanol, 17
heptanol, octanol and decanol of different concentrations.

Fig. 3.1 Plate Heater. 21

Fig. 3.2 Turbidity Meter. 22
Fig. 4.1 Change in turbidity with temperature from 20 Mm solution using TX- 24
100.

Fig. 4.2 Cloud point of aqueous solutions of Triton X-100 as a function of its 25
concentration.

Fig. 4.3 Cloud point of TX-100 in the presence of CTAB. 27

Fig. 4.4 Cloud point of TX-100 in the presence of SDS 28
Fig. 4.5 Comparison between cloud points for the mixture of CTAB with TX-100 29
and SDS with TX-100.
Fig. 4.6 Cloud point of TX-100 with different concentration of Na2SO4 31
Fig. 4.7 Turbidity for 10mM of TX -100 mixed with different concentration of 32
Na2SO4

Fig. 4.8 Turbidity for 20mM of TX -100 mixed with different concentration of 32
Na2SO4

Fig. 4.9 Turbidity for 30mM of TX -100 mixed with different concentration of 33
Na2SO4

Fig. 4.10 Cloud point of TX-100 with different concentration of CaCl2 34

Fig. 4.11 Cloud point of TX-100 with different concentration of NaCl 35
Fig. 4.12 Comparison of cloud point for mixtures of different additives with TX- 36
100

3
 List of Tables

Table No. Title Page

No.
The list of different non-ionic surfactant groups depending on the
Table 1.1
3
head groups. (Salager, 2002)
Table 2.1 Previous Studies using various additives and surfactants. 18

Linear equation for cloud point of TX-100 in the presence of

Table 4.1
27
CTAB
Table 4.2 Linear equation for cloud point of TX-100 in the presence of SDS 28

Comparison between the linear equations for cloud point of the

Table 4.3
29
mixture of CTAB with TX-100 and SDS with TX-100

Linear equations for cloud point of TX-100 with different

Table 4.4
31
concentration of Na2SO4.

Linear equations for cloud point of TX-100 with different

Table 4.5
35
concentration of NaCl.

Comparisons among the linear equations for cloud point of mixture

Table 4.6 3
of different additives with TX-100

4
 CHAPTER 1

INTRODUCTION

1
.

Introduction

1.1 Surfactants

Surfactants are compounds that lower the surface tension of a liquid, the interfacial

tension between two liquids, or that between a liquid and a solid. There is a broad

range of different surfactant types, each having unique properties and characteristics.

Depending on the type of the charge of the head, a surfactant belongs to the anionic ,

cationic, non-ionic or amphoteric/zwitterionic family.

1.1.1Anionic Surfactants

In solution, the head is negatively charged. The anionic surfactants have the advantage

of being high and stable foaming agents; however, they do have the disadvantage of being

sensitive to minerals and the presence of minerals in water (water hardness) or pH

changes. They include alkylbenzenesulfonates (detergents), (fatty acid) soaps, lauryl

sulfate (foaming agent), di-alkyl sulfosuccinate (wetting agent), lignosulfonates

(dispersants).

1.1.2 Cationic Surfactants

In solution, The head is a positive charge on the head. A very large proportion of this

class consists of nitrogen compounds such as fatty amine salts and quaternary

ammoniums, with one or several long chain compounds, which are derived from

natural fatty acids. Common examples of cationic surfactants are Benzalkonium

chloride, Benzethonium chloride, Bronidox, Cetrimonium bromide, Cetrimonium

chloride, Lauryl methyl gluceth-10 hydroxypropyl dimonium chloride,

Tetramethylammonium hydroxide and Dimethyldioctadecylammonium chloride.

2
1.1.3 Non-Ionic Surfactants

Nonionic surfactant is a different class of surfactant that about 45% of the total

surfactant production worldwide. This type of surfactants does not have any net

positive or negative charges on their head groups. They do not ionize in aqueous

solution, because their hydrophilic group is of a non-dissociable type, such as alcohol,

phenol, ether, ester, or amide. A large proportion of these non-ionic surfactants are

made hydrophilic by the presence of a polyethylene glycol chain, obtained by the

polycondensation of ethylene oxide. They are called polyethoxylated non-ionic.

Depending on the head group this surfactant can be classified in different groups. The

percentage of different group non-ionic surfactant those are more important for the

industrial applications are given in the table 1.1.

1.1.3.1 Types of Non-ionic Surfactants

Table 1.1. The list of different non-ionic surfactant groups depending on the head

groups. (Salager, 2002)

Surfactant Type % Total

Ethoxylated Linear Alcohols 40
Ethoxylated Alkyl Phenols 15
Fatty Acid Esters 20
Amine and Amide Derivatives 10
Alkylpolyglucosides ---
Ethleneoxide/Propyleneoxide Copolymers ---
Polyalcolols and ethoxylated polyalcohols ---
Thiols (mercaptans) and derivates ---

3
 Some common non-ionic surfactants are Triton X-100, TX-165, cetomacrogol

1000, poloxamer, cetyl alcohol, stearyl alcohol, lauryl glucoside, octylglucoside,

cocamide DEA, nonoxynols and sorbitantristearate.

1.2.3 Zwitterionic Surfactants

When a single surfactant molecule exhibit both anionic and cationic dissociations it is

called amphoteric or zwitterionic. This is the case of synthetic products like betaines

or sulfobetaines and natural substances such as aminoacids and phospholipids.

1.3 Cloud Point

The cloud point of a fluid is the temperature at which dissolved solids are no longer

completely soluble, precipitating as a second phase giving the fluid a cloudy

appearance.

The cloud point is an important criterion for determining the storage stability

of surfactants. Cloud points are characteristic properties of nonionic surfactants.

Anionic surfactants are more water-soluble than nonionic surfactants due to the

presence of negatively charged head, and typically exhibits higher cloud points. The

presence of other components in the formulation of surfactant can affect the cloud

point of the mixture.

4
1.4 Turbidity

Turbidity is the cloudiness or haziness of a fluid caused by individual particles or

suspended solids in a solution or mixture. The turbidity measurement acts as a key

characteristic for water quality.

1.5 Objective
To determine the effects of additives on the cloud point of non-ionic surfactants.

Following are some of the applications of cloud point determination

 The cloud point of petroleum products and biodiesel fuels is an index of the

lowest temperature of their utility for certain applications. Wax crystals of

sufficient quantity can plug filters used in some fuel systems.

 Petroleum blending operations require a precise measurement of the cloud

point.

 For low-foam applications, the cloud point of the product should be just below

the use temperature.

 Cloud point extraction is used for determination of pyrene in natural water.

 For determining of the Nickel and zinc through the cloud point pre-

concentration.

 For finding out the lead from the water samples by using cloud point

extraction flow injection-atomic absorption.

 For pre-concentration of fulve and bumic acids by using cloud point extraction

technique.

5
 CHAPTER 2

LITERATURE REVIEW

6
Literature Review

2.1 Single Surfactant

This study report and investigations on the effect of organic additives on the cloud

point of Triton X-100 . The cloud point of Non ionic surfactants is useful as compare

to other because it application emulsifier .as a detergent and in pharmaceutical

formulation. The cloud point depends upon on the TX-100 solutions range 1-10%

have been measured. The estimates cloud point of TX-100 Solutions over this

concentration range is shown on the graph (Alauddin et al.2009).

Fig. 2.1: Cloud point of aqueous solutions of Triton X-100 as a function of its
concentration(Alauddin, et al.2009).

7
2.2 Mixed Surfactants

Fig.2.2 The effect of the addition of CTAB on the cloud point of 0.1% () and 1%

()solutions of TX-100 (Gu, et al.1989).

Fig 2.2: Shows the results of addition of small amounts of CTAB into two different

concentration (.1 and 1%) of solution of TX-100 .Fig.:2.3 shows the effect of

hydrocarbon chain length of sodium alkyl sulfates on the cloud point of anionic-

nonionic mixed solution as well as that of alkyltrimethyl ammonium bromides on the

cloud point of cationic-nonionic mixed solutions in the presence of small amount of

-5 -4 -3
ionic surfactant. The concentrations of the ionic surfactants of 10 and 10 mole dm

will correspond to a maximum of about one ionic surfactant molecule per micelle of

TX-100 in 0.1 and 1% solutions, respectively. CMC and the aggregation number of

-4 -3
TX-100 used in the calculation were 3.2 x 10 mole dm and 150 respectively (Gu, et

al.1989).

8
Fig. 2.3. The effect of hydrocarbon chain length of ionic surfactant homologs on the

cloud point of 1%. Solution of TX-100 .,SCS;,SDS;,CTAB;,DTAB (Gu, et

al.1989).

It can be see that concentration of the ionic surfactants was far below the

concentration of TX-100 and far below the CMC of the ionic surfactant used .Thus it

was safe to assume that the surface active cations as well as surface active anions

were present either as monomers or as mixed micelles with TX-100 and that there

were no pure ionic surfactant micelles. The rise in the cloud point was due to the

formation of mixed micelles which changed the nature of the micelle surface by a

small amount of ionic surfactant (Gu, et al.1989).

9
2.3 Effect of Electrolyte

Fig. 2.4: Relation between cloud point of 1 wt% aqueous solutions of NPE8, NPE10,

NPE12, and concentration of additives: oleic acid, PEG 400, PEG 1000, and

PEG4000(Marszall, 1997).

Fig. 2.4 depicts the effects of oleic acid and various other additives on the cloud

points of NPEx, (x = 8, 10, and 12) aqueous solutions. Oleic acid depresses the cloud

points significantly. This result is satisfactory, according to comparisons with other

research studies. Therefore, Oleic acid can be considered to decrease the effective

HLB value of the surfactants since there was decrease in the cloud point recorded

(Marszall, 1997).

Fig. 2.5 indicates the effect of various electrolytes on the cloud point of the non-ionic

surfactant poloxamine 908. The research study was carried out with electrolytes

10
methanol, ethanol, n-propanol, i-propanol and glycerol, and propylene glycol. It was

concluded that the monoalcohols, ethanol, methanol and iso propanol had effective

effects on boosting the cloud point. However, it was also evident that n-propanol and

glycerol were only slightly effective. The results obtained clearly stated that the cloud

point of surfactants can be modified using various electrolytes (George, et al.1999).

Fig. 2.5: Effects of nonionic additives on the cloud point of poloxamine 908 at 1 %

(w/v) (George, et al.1999).

11
Fig. 2.6: Cloud point shift values ∆ of 2.0% Triton X-100 solutions as a function of
the molality of added electrolytes (Scott, et al.1986).

Various studies on the shift in cloud point was done on Triton X-100 using sulfuric

acid, silver nitrate, ammonium bromide, ammonium chloride, Zn(NO3)2 and

(NH4)2SO4. The cloud point shift was plotted as a function of molality of the

electrolytes in Fig. 2.6. The studies led to the conclusion that the sulfuric acid and

silver nitrate had great cloud point boosting abilities on triton X-100 (Scott, et

al.1986).

12
Fig. 2.7: Cloud point shift values ∆ of 1.0% Brij 76 solutions as a function of the
molality of added electrolytes(Scott, et al.1986).

Similar studies were carried out with Brij 76 and it was concluded that sulfuric acid

provided to be the best cloud point booster. However, even small concentrations of

Na2SO4 decreased the cloud point by large values. Fig. 2.7, depicts the same results as

a function of molality of the electrolytes (Scott, et al.1986).

13
Fig. 2.8: The effect of the alcohols on the cloud point of 2 wt % NPEx solutions

(Marszall,1977).

The effects of various alcohols on the cloud point of NPEx solutions were studied.

The results obtained from the research have been plotted in Fig. 2.8. The values

indicate that alcohols act as agents to increase the cloud point of the NPEx solutions

(Marszall, 1977).

14
Fig. 2.9: Cloud point (CP) of a 1 % solution of Triton X-100 as a function of the
molar concentration of added sodium alkyl sulfates: C8H17OSO3Na (O),
C12H25OSO3Na ( X ), and C14H29OSO3Na (●)(Marszall, 1989).

Fig. 2.10: The effect pf cryptand 222 (∆) and NaCl (▲) on the cloud point (CP) of a
1% solution of Triton X-100 and the cloud point data for Triton X-100- sodium octyl
sulfate (SOS) mixtures without ( X ) and with cryptand 222 (O) and NaCl (●). The
molar ratios of cryptand 222/SOS and NaCl/SOS were 1:1(Marszall, 1989).

15
Fig . 2.11: The effect of cryptand 222 ( X ) on the cloud point (CP) of C8E4-sodium
octyl sulfate (SOS) mixtures (●). The molar ratio of cryptand 222/SOS was
1:1(Marszall, 1989).

Fig. 2.9, 2.10 and 2.11 denotes the various studies carried out on the cloud point

variation using electrolyte systems on single and mixed surfactant systems (Marszall,

1989).

Fig. 2.12: Cloud point of 10 % Triton X-100 solution in the presence of methanol,

ethanol, propanol, butanol, and butoxyethanol (BE) of different concentrations

(Alauddin, et al.2009).

16
Fig. 2.13: Cloud point of 10 % Triton X-100 solution in the presence of hexanol,

heptanol, octanol and decanol of different concentrations (Alauddin, et al.2009).

Fig. 2.12 and 2.13 depict the various results obtained on studies done on the cloud

point of Triton X-100. In these studies, The cloud point was then varied using

different concentration of organic alcohols. The various results obtained from these

experiments have been plotted in Fig. 2.12 and Fig. 2.13(Alauddin, et al.2009).

17
Table 2.1 denotes the various surfactants and additives that have been used for studies

by various researchers.

Table 2.1: Previous Studies using various additives and surfactants.

Sl. No. Surfactants Used Additive Used

3
1 TX-100 Toxic Eosin Dye
4
2 Poloxamine 908 Polyglycols
4
3 Poloxamine 908 Alcohols and Polyalcohols
4
4 Poloxamine 908 Saccharides
4
5 Poloxamine 908 Phospholipids
5
6 Octoxynol 9 Primidone
5
7 Octoxynol 9 Prednisone
6
8 Triton X-100 NaBr
6
9 Triton X-100 Na2SO4
7
10 Triton X-100 Urea
7
11 Triton X-100 Methylurea
7
12 Triton X-100 Acetamide

18
 CHAPTER 3

EXPERIMENTAL WORK

19
Experimental Work

3.1 Materials
The surfactants used were Triton X-100 (molecular weight 617gm/mole from Loba

Chemie, India). CTAB (Cetyl trimethyl ammonium bromide) (molecular weight

364.46gm/mole from Loba Chemie, India). SDS (Sodium dodecyl sulphate)

(molecular weight 288.38gm/mole from Loba Chemie, India).

Electrolyte used were NaCl (molecular weight58.44 from Rankem, India). Na2SO4

(molecular weight124.02gm/mole from Rankem, India). CaCl2 (molecular

weight147.02gm/mole from Rankem , India) . No further surfactants or electrolytes

was adopted for cloud point.

3.2. Methods
For determining cloud point, plate heater provided with a test tube is used. Initially a

50 ml stock solution is prepared containing 100 millimoles of TX-100. From the

prepared stock solution, solution of different concentration are made ranging from 10

millimoles to 30 millimoles . For each concentration, the cloud point is determined

with help of plate heater. Beaker filled with water is placed on the plate heater. After

the setup is arranged, test tube containing the prepared solution is placed and heating

is started. Controlled heating is done, starting from the room temperature at a rate of
0
0.3 C/min till the required cloud point temperature is obtained. Cloud point

temperature of surfactant solutions was determined by the visual examination of the

abrupt change in the appearance of the surfactant solutions as it occurs during the

heating of the sample solutions.

20
Fig.3.1: Plate Heater.

As well as for turbidity, the solution is put in the hole with clean of the test tube. No

water should be there outside the test tube otherwise the instrument will be damaged.

Digital temperature readings are also noted.

21
Fig. 3.2: Turbidity Meter.

After the temperature exceeds the cloud point, the solution should be cool down

below the cloud point temperature and then it was heated again to check the

reproducibility of the measurements. This procedure was repeated at least 2 times.

22
 CHAPTER 4

RESULT AND DISCUSSION

23
Result and Discussion

4.1 Cloud Point of Surfactant

When the temperature increases gradually the turbidity value of the solution also

increases. But at a certain temperature the cloudy appearance signifies the cloud point,

and its corresponding turbidity is also very high (as shown in the Fig.).

The experiment was carried out with only a single concentration of the solution

initially. Later various concentration of the same solution was tested for its cloud

point. The results of various concentration of TX-100 were found out experimentally,

and Fig. 4.1 depicts the results of one such experiment.

160

140

120
Turbidity in NTU

100

80

60

40

20

0
37 42 48 51 53 56 60 62 63 65 66.5
Temperature in C
ͦ

Fig. 4.1: Change in turbidity with temperature from 20 Mm solution using TX-100.

24
4.2 Effect of Concentration

The cloud point of TX-100 of different concentrations was determined by the

experiments. The cloud point obtained from this experimental procedure was plotted

in Fig. 4.2 . The cloud point is plotted as a function of concentration of TX-100. From

Fig. 4.2 it can be determined that there is an increasing trend in the cloud point values

with an increase in the concentration of the TX-100 concentration. The least value of

cloud point for 10mM TX-100 is around 66 °C, and maximum being around 68.5 °C

for 40 mM TX-100.

69

68.5

68
Temperature in C

67.5
ͦ

67

66.5

66

65.5

65

64.5
10 15 20 25 30 35 40
TX-100 in mM

Fig. 4.2: Cloud point of aqueous solutions of Triton X-100 as a function of its
concentration.

25
4.3 Effect of Mixed Surfactant
4.3.1 Mixing of TX-100 with CTAB

Mixing of surfactants induces a synergistic effect on the cloud point which may

depend on the specific type of surfactants that have been used for the experiment. In

this case the surfactants used are TX-100 and CTAB.

As it can be clearly detected, there has been a sharp increase in the cloud point

values of the 10 mM TX-100 solution when mixed with CTAB. From Fig. 4.3 it can

be noticed that the cloud point of 10 mM TX-100 is 66 °C. But when 10 mM TX-100

solution is mixed with CTAB, the cloud point tends to increase in values for

increasing values of CTAB concentration. For 0.5 mM of CTAB mixed with TX-100,

the mixture has a cloud point of 70 °C. The same trend of increase in cloud point is

spotted for an increase in the CTAB concentration.

However, the cloud point of the mixture for fixed CTAB concentration and

varying TX-100 yields that, 10 mM concentration of TX-100 has the highest effect

compared to 20 mM and 30 mM. Hence mixing CTAB with TX-100 has greater

effect at lower concentrations of TX-100 than higher concentrations.

26
 100

95 10 mM

90 20 mM
Temperature in C
ͦ

85 30 mM

80

75

70

65

60
0 0.1 0.2 0.3 0.4 0.5 0.6
CTAB in mM

Fig. 4.3: Cloud point of TX-100 in the presence of CTAB.

Table 4.1. Linear equation for cloud point of TX-100 in the presence of CTAB
2
TX-100 Concentration (mM) Equation R

10 Y = 65x + 65.167 0.953

20 Y = 42.5x + 63.083 0.9819

30 Y = 16.25x + 65.292 0.9119

4.3.2 Mixing of TX-100 with SDS

Mixing of different surfactants has tremendous effects on the cloud point of the

mixture. But since all the effects are due to the microscopic interaction of molecules

present chemically in the mixture.

In this case TX-100 was mixed with SDS and its effect on cloud point was studied.

From Fig. 4.4 and Fig. 4.4 it is evident that the cloud point of TX-100 solution is

increased when mixed with SDS than its pure form. However, on increasing the

27
concentration of the SDS that is being mixed, the cloud point of the solution tends to

increase. But when a fixed value of SDS concentration is compared for a varying

concentration of TX-100, it can be Fig.d that the lower the concentration there is

better interaction of the system and hence better cloud point boosting characteristics.

Thus from Fig. 4.4 it can be clearly noted that for a given SDS concentration highest

cloud point is for the least value of TX-100 ( here 10 mM TX-100).

97 SDS
TX-100-10 mM
92
TX-100-20 mM
Temperature in ͦC

87 TX-100-30 mM

82

77

72

67
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
SDS in mM

Fig. 4.4: Cloud point of TX-100 in the presence of SDS.

Table 4.2. Linear equation for cloud point of TX-100 in the presence of SDS.
2
TX-100 Concentration (mM) Equation R

10 Y = 46.5x + 67.65 0.9856

20 Y = 27.25x + 66.975 0.9955

30 Y = 16.75x + 67.425 0.9987

28
4.3.3 Comparison of CTAB and SDS
CTAB and SDS have very good effect of increasing the cloud point of TX-100

solutions. But both these surfactants have greater effect on the cloud point when TX-

100 is present in lower concentrations and its effect keeps decreasing as concentration

of the TX-100 increases. But comparing for a given TX-100 concentration and same

mixing surfactant concentration (either CTAB or SDS) it can be noted that the cloud

point of CTAB and TX-100 solution is higher than SDS mixtures. But this valid only

when the concentration of TX-100 is very low, but for higher concentration of 30 mM

TX-100 and 0.5 mM of mixing agent (CTAB and SDS), the effect of SDS as a cloud

point booster is better than CTAB.

120

110

100
Temperature in C
ͦ

90

80 SDS

70 CTAB

60
0.1 0.3 0.5
Ionic Surfactant in mM

Fig. 4.5: Comparison between cloud points for the mixture of CTAB with TX-100

and SDS with TX-100.

29
Table 4.3. Comparison between the linear equations for cloud point of the mixture of
CTAB with TX-100 and SDS with TX-100
2
Surfactant Concentration (mM) Equation R

CTAB Y = 13x + 58.667 0.953

SDS Y = 10.5x + 61 0.9932

4.4 Effect of Additives on Non- Ionic Surfactant

4.4.1 Effect of Na2SO4 on TX-100

Na2SO4 when mixed with TX-100 decreases the cloud point of the solution. It can be

noted from the Fig. 4.6 that for a constant TX-100 concentration, increasing the

Na2SO4 concentration, decreases the cloud point of the TX-100 solution. But when

focused on a single Na2SO4 concentration it can be determined that the effect of

decreasing the cloud point is strongly felt at higher concentrations of TX-100. In this

case, the cloud point of 30 mM TX-100 and 100 mM Na2SO4 is 57 °C but for 10 mM

TX-100 and 100 mM Na2SO4 the cloud point is 58 °C. Hence there is a greater

activity of depressing the cloud point using Na2SO4 at higher concentrations of TX-

100.

30
 66
65 10
64
15
63
Temperature in ͦC

62 20

61 30
60
59
58
57
56
0 20 40 60 80 100
Concentration of Na2SO4

Fig. 4.6: Cloud point of TX-100 with different concentration of Na2SO4.

Table 4.4. Linear equations for cloud point of TX-100 with different concentration of
Na2SO4.
2
TX-100 Concentration (mM) Equation R

10 Y= -0.0793x + 65.665 0.9774

15 Y= -0.0669x + 64.596 0.996

20 Y= -0.0647x + 64.365 0.9914

30 Y= -0.0669x + 63.596 0.996

As discussed previously, the cloud point and turbidity are interconnected. The cloud

point is marked by a sharp change in the turbidity values and cloudy appearance.

For the effect of Na2SO4 on the cloud point of TX-100, its turbidity has also been

studied and plotted in Fig. 4.7. The turbidity results too help to conclude that the

cloud point has been achieved at lower temperatures for high concentrations of

Na2SO4. At high concentrations of Na2SO4 it can be seen that the cloud point of TX-

31
100 are reduced. This implies that the turbidity has increased rapidly at lower

temperatures to form cloud point. This is evident from Fig. 4.7 that for 100 mM

Na2SO4 and 10 mM TX-100, there is a steeper change in turbidity compared to other

concentrations, implying a greater change in turbidity at a lower temperature.

120
10mM
100 25mM
50mM
Turbidity in NTU

80
100mM
60

40

20

0
30 40 50 60 70
Temperature in ͦC

Fig. 4.7: Turbidity for 10mM of TX -100 mixed with different concentration of

Na2SO4

180
160 10mM

140 25mM

120 50mM
Turbidity in NTU

100 100mM

80
60
40
20
0
30 35 40 45 50 55 60 65 70
Temperature in C
ͦ

Fig. 4.8: Turbidity for 20mM of TX -100 mixed with different concentration of

Na2SO4

32
 250

10mM

200 25mM

50mM
Turbidity in NTU

150 100mM

100

50

0
30 35 40 45 50 55 60 65 70
Temperature in C
ͦ

Fig. 4.9: Turbidity for 30mM of TX -100 mixed with different concentration of

Na2SO4

Figs 4.7, 4.8, 4.9. show a similar pattern for a varying concentration of Na2SO4.

However, as the concentration of TX-100 increases the curve gets steeper at lower

temperature. This implies that the cloud point is being formed at a lower temperature

for higher concentration of TX-100 that is mixed with Na2SO4.

4.4.2 Effect of CaCl2 on TX-100

Fig. 4.10 denotes the effect of CaCl2 on the cloud point of different concentration of

TX-100. It can be noted that the cloud point depressing property of CaCl2 can be

effectively determined at lower concentrations of TX-100. For a fixed TX-100

concentration there is a decreasing trend of cloud point, for an increasing

concentration of CaCl2. But on comparing cloud point values at fixed CaCl2

concentration of 100 mM, it was observed that for 30 mM TX-100 solution had

maximum cloud point depression. Hence it may be recognized that CaCl2 serves as an

33
efficient cloud point depressing agent when used in high concentration along with

high concentrations of TX-100.

67

66
Temperature in ͦC

65

64

63 10

15
62
20
61
30
60
0 20 40 60 80 100
Concentration of CaCl2

Fig. 4.10: Cloud point of TX-100 with different concentration of CaCl2.

4.4.3 Effect of NaCl on TX-100

When NaCl was used as an additive for cloud point variation there was a cloud point

depression observed. The values obtained experimentally were plotted and Fig. 4.11

was obtained. From Fig. 4.11 it can be noted that the cloud point of TX-100 (at fixed

concentration) is drastically decreased for an increase in NaCl concentration.

However for a fixed concentration of NaCl, the least cloud point can be noted for the

highest concentration of TX-100. This implies that the NaCl acts as a good cloud

point depressant for high concentration of TX-100.

34
 67

66

65
Temperature in C
ͦ

64
10
63
15
62
20
61
30

60
0 20 40 60 80 100

Concentration of NaCl

Fig. 4.11: Cloud point of TX-100 with different concentration of NaCl.

Table 4.5. Linear equations for cloud point of TX-100 with different concentration of
NaCl.
2
TX-100 Concentration (mM) Equation R

10 Y= -0.0292x + 66.6 0.9356

15 Y= -0.0388x + 66.546 0.9705

20 Y= -0.0273x + 65.263 0.9948

30 Y= -0.0446x + 65.687 0.9577

35
4.4.4 Comparison of Additives

In general, all the additives used in our study have a cloud point depressant role. But

our study gives us a general idea about the effect of various additives on the cloud

point of TX-100. From these experiments we are able to come to a comparison that

100 mM Na2SO4 and 30 mM TX-100 has the maximum cloud point depression with a

value of 57 °C. However corresponding 100 mM CaCl2 and NaCl values are 61 °C.

Hence Na2SO4 may be considered as a better cloud point depressing agent than CaCl2

and NaCl.

66
65
64
63
Temperature in C
ͦ

62
61
Na2SO4
60
59 CaCl2
58
NaCl
57
56
0 20 40 60 80 100
Concentration of additives in mM

Fig. 4.12: Comparison of cloud point for mixtures of different additives with TX-100

Table 4.6. Comparisons among the linear equations for cloud point of mixture of
different additives with TX-100
2
TX-100 Concentration (mM) Equation R

NaCl Y = -0.0446x + 65.687 0.9577

CaCl2 Y = -0.0373x + 64.602 0.9739

Na2SO4 Y = -0.0669x + 63.596 0.996

36
 CHAPTER 5

CONCLUSION

37
Conclusion

It is observed that cloud point increases with increase in Triton X-100 concentration.

For a fixed Triton X-100 concentration, the cloud point increase as the concentration

of ionic surfactant increases.

For a fixed concentration of ionic surfactant, the cloud point decreases with increase

in concentration of triton X-100. So an increase in concentration of TX-100 reduces

the probability of SDS and CTAB at the surfaces which reduces the cloud point.

For CTAB solution cloud point temperature is higher as compare to SDS.

For a fixed Triton X-100 concentration, the cloud point decreases as the concentration

of additives increases.

For a fixed concentration of additives, the cloud point negligibly decreases as the

concentration of TX-100 increases.

For Na2So4 solution, decrease in cloud point temperature is more as compared to

CaCl2 and NaCl.

38
REFERENCES
1. Scott, H.; Royce, A. Effect of inorganic additives of solution of non-ionic

surfactant. Colloids Surf. 19 (1986) 399-418.

2. Salager, J. L. Surfactants types and uses. Version 2, Universidad De Los

Andes, Merida-Venezuela, 2002.

3. Purkait, K. M.; Banrjee, S.; Mewara, S.; Dasgupta, S.; De, S. Cloud point

extraction of toxic eosin dye using Triton X-100 as nonionic surfactants.

Water Res. 39 (2005) 3885–3890.

4. Na, G. C; Yuan, B. O.; Steven, H. J. Jr.; Weekley, B. S.; Rajgopalan, N.

Cloud point of nonionic surfactants: Modulation of with pharmaceutical

excipients. Pharm. Res. 16 (1999) 562-568.

5. Scott, H., Royce, E. A.; Han, K. S. Effect of inorganic additives on solutions

of non-ionic surfactants. J. Colloid Interface Sci. 98 (1984) 196-201.

6. Gu, T.; Qin, S.; Ma, C. The effect of electrolytes on the cloud point of the

mixed solutions of ionic and nonionic surfactants. J. Colloid Interface Sci.

127 (1989) 586-588.

7. Han, K. S.; Lee, M. S.; Schott, H. The effect of protein denaturants on the

cloud point of non-ionic surfactant. J. Colloid Interface Sci. 196 (1988) 393-

396.

8. Alauddin, M.; Parvin, T.; Begum, T. Effect of organic additives on the cloud

point of triton x-100 micelles. J. Appl. Sci. 9, 12 (2009) 2301-2306.

9. Marszall, L. Cloud point and emulsion inversion in the presence of additives.

J. Colloid Interface Sci. 59 (1977) 376-377.

39
10. Na, G. C; Yuan, B. O.; Steven, H. J. Jr.; Weekley, B. S.; Rajgopalan, N.

Cloud point of nonionic surfactants: Modulation of with pharmaceutical

excipients. Pharm. Res. 16 (1999) 562-568.

11. Marszall, L. The effect of alcohols on the hydrophile-lipophile balance of

nonionic surfactants. J. Colloid Interface Sci. 60 (1977) 570-573.

12. Marszall, L. Effect of counter ion complexation by a macro-cyclic ligand on

the cloud point mixed anionic-nonionic surfactant solutions. Colloids Surf.

35 (1989) 1-6.

40