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Surfactants and Surfactants Titration - Tips and Hints

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Surfactants and Surfactant Titration
Tips and Hints

Cosimo A. De Caro
Mettler-Toledo GmbH, Analytical
Switzerland
Surfactants and Surfactant Titration
Tips and Hints

Cosimo A. De Caro
Mettler-Toledo GmbH, Analytical
Switzerland
Agenda

§  Basics of Surfactants
-  Chemical structure
-  Applications
-  4 types of surfactants
§  Surfactant Titration Reaction
-  Precipitation reaction
-  Neutralization reaction
§  Detection: A Choice of Techniques
-  Colorimetric Two-phase titration
-  Turbidimetric titration
-  Potentiometric titration (aqueous solution)
-  Potentiometric two-phase titration (mixed phases)
§  Tips and Hints
-  Checklist for surfactant titration
§  Summary

3
Surfactants: Basics

Non-polar tail Polar head

(Hydrophobic tail) (Hydrophilic head)

Electrical charge distribution

4
Surfactants: Basics

§  Electrostatic interactions with solvent molecules

Example: Water (H2O)

-
H 2O
+ +
+ + -

-+
+

+
+
-+
5
Tenside: Grundlagen

§  Electrostatic interactions with polar surfaces

Example: Glass (SiO2)
The glass surface is covered with a layer formed by positively charged
surfactants

O O O
Si Si Si Si

6
Surfactants: Basics

§  Electrostatic interactions with polar solvent molecules

-  Formation of aggregates i.e. so-called micelle if the surfactant concentration
is higher than a specific value (critical micelle concentration)

Water

Micelle

7
Surfactants: Basics

Surfactants are classified according to the type and electrical charge of

the hydrophilic group(s) in solution:

§  Anionics Negative charge(s) -

§  Cationics Positive charge(s) +

§  Amphoterics Both electrical charges -,+

§  Nonionics No ions in solutions

8
Anionic and Cationic Surfactants
Anionics
§  Alkyl sulphate (e.g. sodium dodecyl sulphate, SDS)

OSO3- Na+
§  Alkyl ether sulphate
CH3 - (CH2)10 - CH2 - O - (CH2-CH2-O) n - SO3-

Cationics
§  Alkyl pyridinium salts N+ -
(e.g. CPC) Cl

§  Quaternary ammonium salts Cl-

(e.g. Hyamine 1622)
O O N+
9
Amphoteric and Nonionic Surfactants

Amphoterics
§  Amidobetaines CxH2x+1 - CO - NH - (CH2)2 - N+- CH2COO-

§  Alkyl ammonium sulphonates

N+ SO3-

Nonionics
§  Ethoxylated alkyl phenols
O - (CH2-CH2-O)9 - H
(e.g. Nonylphenol 9-mole ethoxylate)

§  Alkyl polyethylene glycols (e.g. Dodecanol 9-mole ethoxylate)

CH3 - (CH2)10 - CH2 - O - (CH2-CH2-O)9 - H

10
Agenda

§  Basics of Surfactants
-  Chemical structure
-  Applications
-  4 types of surfactants
§  Surfactant Titration Reaction
-  Precipitation reaction
-  Neutralization reaction
§  Detection: A Choice of Techniques
-  Colorimetric Two-phase titration
-  Turbidimetric titration
-  Potentiometric titration (aqueous solution)
-  Potentiometric two-phase titration (mixed phases)
§  Tips and Hints
-  Checklist for surfactant titration
§  Summary

11
Surfactant Titration: Anionic/Cationic Surfactants

§  Quantitative analysis based on the formation of

an ion-pair complex between counter-ionic surfactants

- N+
SO3 +

Precipitation

SO3
N

12
Surfactant Titration: Nonionic Surfactants

§  Quantitative analysis based on the formation of

a complex between an activated nonionic surfactant and an appropriate
negatively charged titrant

X+ B-
+ X

Precipitation

13
Surfactant Titration: Amphoteric Surfactants

§  Quantitative analysis based on the precipitation of

an ion-pair complex between a protonated amphoteric surfactant and an
appropriate bulky and negatively charged titrant

N+ -CH2COO-H + B-

§  Quantitative analysis in a non-aqueous solvent

by potentiometric titration of a protonated amphoteric surfactant with
potassium hydroxide

§  Quantitative analysis in a non-aqueous solvent

by potentiometric titration of an amphoteric surfactant with perchloric acid

N+ -CH2COO- + HClO4

14
Agenda

§  Basics of Surfactants
-  Chemical structure
-  Applications
-  4 types of surfactants
§  Surfactant Titration Reaction
-  Precipitation reaction
-  Neutralization reaction
§  Detection: A Choice of Techniques
-  Colorimetric Two-phase titration
-  Turbidimetric titration
-  Potentiometric titration (aqueous solution)
-  Potentiometric two-phase titration (mixed phases)
§  Tips and Hints
-  Checklist for surfactant titration
§  Summary

15
Precipitation reaction: Detection
Surfactant titration: Precipitation reaction
§  Colorimetric two-phase titration
–  Classical standard method: Two-phase titration (Epton titration)
–  Chloroform/water phase
–  Mixed indicator (acid solution of cationic and anionic color indicators)

§  Turbidimetric titration
–  Increase in turbidity during titration
–  Monitoring of the light transmission

§  Potentiometric titration in aqueous solution

–  Monitoring of the potential change with surfactant sensitive electrode

§  Potentiometric titration in an mixed two-phase system

–  Monitoring of the potential change with surfactant sensitive electrode
–  Mixed, two-phase system (organic solvent/water)

16
Standard Method: Two-Phase Titration
Example: Titration of SDS with Hyamine using a DP5 Phototrode™
Principle

H 2O

Mix CHCl3
Separate

t1 t2 Indicator 1
SDS

Add increment Stirring Signal acquisition

EQP

Indicator 2
Hyamine

Before EQP EQP After EQP

17
Automated Two-Phase Titration (2P)

§  Automation of classical two-phase titration

with Titration Excellence Line Instruments

§  Special titration method function

„Titration (2-phase)“ (M434)

18
Automated Two-Phase Titration (2P)

§  Two-phase titration beaker and DP5 PhototrodeTM

19
Automated Two-Phase Titration (2P)
Tips & Hints:

§  When titrating ionic surfactants, do not choose a too large sample size to
avoid foaming during strong stirring.

§  Prepare a sample standard solution and titrate aliquots of it.

§  Add some mL alcohol to the standard solution to avoid foam.

§  High salt concentrations affect the analysis:

the complex is dissolved again, i.e. the colour disappears.

§  Follow exactly the procedure for the preparation of the mixed acid
indicator.

§  During titration, the organic solution can also become turbid;

it strongly depends on the sample.

20
Turbidimetric Titration (DP5)

Principle
§  Colloidal complex between anionic and cationic surfactants
§  Turbidity changes are monitored with a photometric sensor (DP5 Photototrode™)
§  Maximum turbidity at the equivalence point (EQP)

before EQP at EQP after EQP

21
Turbidimetric Titration (DP5)

Example 1: Titer determination of Hyamine with SDS

Further addition of titrant after the

EQP an increase of light
transmission due to

•  Dissolution of the colloidal

precipitate, and

EQP •  Dilution of sample

Example 2: Titer determination of SDS with CPC

EQP
22
Turbidimetric Titration (DP5)
Tips & Hints:

§  Preparation of the photometric sensor DP5 Phototrode™

-  Turn on the DP5 Phototrode™ and wait 15 minutes to achieve a stable

signal.
-  Adjust the mV reading to 1000 mV in deionized water by turning the
knob on top of the DP5 Phototrode™.

§  The precipitate covers the mirror and the stirrer:

-  Clean the DP5 photometric sensor and the stirrer thoroughly after each
sample with water.

§  Avoid formation of a vortex, foaming of sample and inclusion of air bubbles

during stirring.
→ Select a medium to low stirring speed.

23
Potentiometric Titration: Aqueous Solution (DS500)

Principle of a SSE (surfactant sensitive electrode)

Membrane:
•  PVC, softener, ion carrier
•  Potential is formed by interaction between
analyte in the sample and the ion carrier
in the membrane:

Softener
Inner Electrolyte

Ion carrier

PVC
Sample solution

Analyte
24
Potentiometric Titration: Aqueous Solution (DS500)

Tips & Hints:

§  SSE are suitable for the titration of rather low surfactant concentrations
(e.g. 10-4-10-5 M).

§  pH below 2 or above 10 will damage the membrane of the

DS500 surfactant sensitive electrode.

§  Membrane module tips do not last forever.

Depending on the use and maintenance, they usually have a lifetime
between 6 months and max. 1 year.

§  Appropriate cleaning and conditioning (e.g. with a dilute sodium chloride

solution) of the electrode after each sample titration are crucial to achieve
accurate results.

§  Salts affect the profile of the titration curve: high salt concentration ⇒ flat curve

25
Potentiometric Titration: Aqueous Solution (DS500)

Titer determination of Hyamine with SDS

26
 Potentiometric Titration: Two-Phase System (DS800)

§  Resistant against solvents used in two-

phase (2P) surfactant titrations according
to DIN EN standards:
-  DIN EN 14468
-  DIN EN 14469
-  DIN EN 14480
§  Enables quicker and healthier 2P titrations
compared to the classical Epton method
§  Titration in a continuously stirred two-
phase system consisting of water and
MIBK
(Methylisobutylketone, 4-methylpentan-2-
one)
§  Titration of anionic and cationic surfactants
in various sample matrices in the pH range
1-12 MIBK

27
Potentiometric Titration: Two-Phase System (DS800)

Tips & Hints:

§  Titrant: For anionic surfactants: Hyamine 1622

For cationic surfactants: SDS
§  Sensor: DS800-TwoPhase Surfactant sensitive electrode (pH 1-12)
InLab®Reference or DX200 Reference electrode

§  Parameters: DYN (Dynamic titrant add.), EQU (Measure mode: Equil. contr.)
§  Evaluation: Standard
§  Solvent compatibility:
Solvent behavior of DS800 surfactant sensor membrane
Solvent Swelling (weight gain)
MIBK 48 %
CHCl3 600 %
Hexane 2 %
Acetone 93 %
Toluene 48 %
THF dissolution !
Isopropanol OK
28
Agenda

§  Basics of Surfactants
-  Chemical structure
-  Applications
-  4 types of surfactants
§  Surfactant Titration Reaction
-  Precipitation reaction
-  Neutralization reaction
§  Detection: A Choice of Techniques
-  Colorimetric Two-phase titration
-  Turbidimetric titration
-  Potentiometric titration (aqueous solution)
-  Potentiometric two-phase titration (mixed phases)
§  Tips and Hints
-  Checklist for surfactant titration
§  Summary

29
Tips and Hints 1: General Information
Nature of the sample:
•  Raw material or finished product / formulation ?
•  Qualitative (which surfactants?) and quantitative composition (how much?)
•  Additional components: e.g. salts, fragrances, alcohol, water.

Analysis:
•  What is the current analytical procedure used ?
•  If different surfactants are present: Possible interferences ?
•  pH value: Possible interferences ?

Sample preparation:
•  Finished products / formulations:
Ιs a separation step of the components necessary before titration?
•  pH value: Is a pH-adjustment necessary ?
•  Choice of the correct pH value to differentiate between components.

30
Tips and Hints 2: Properties of Surfactants
Surface active behavior
•  Migration and enrichment at e.g. glass-water and water-air interfaces
⇒ Avoid too many dilution steps.
•  Enrichment of cationic surfactants on glass surfaces:
It lowers the concentration of cationic titrants such has Hyamine and CPC.
⇒ Wait before performing the titer determination of a freshly prepared solution.

Foam formation
•  Higher surfactant concentration in foam than in solution.
⇒ Avoid shaking and strong stirring.
⇒ Add few mL ethanol to reduce foam (max. content: 5-10% v/v).

Micelle formation (self-aggregation)

•  Surfactant molecules in micelles are not available for titration. They become
available only after titration of molecules in solution.
⇒ Too fast a titration leads to lower results.
•  Direct surfactant measurements as for metal ions are generally not possible.

31
Tips and Hints 3: Titration Reaction
Precipitation reaction
•  The analyte has to be titrated with a counter-ionic surfactant leading to the
precipitation of a titrant-analyte complex.

Complete precipitation of the titrant-analyte complex

•  Surfactants molecules have non-polar alkyl chains of various lengths:
Chain length > 12 carbon atoms (C12): Complete precipitation
Chain length C8-C12: Partial precipitation
Chain length < C8: Difficult to titrate

Solubility product of the analyte-titrant complex formed

•  It depends on the alkyl chain length: shorter chain ⇒ higher solubility

Endpoint indication
The precipitation reaction leads to
•  a potential change - potentiometric indication
•  a turbidity increase - turbidimetric/photometric indication
•  or to a color change - colorimetric/photometric indication
when indicators are used
32
Tips and Hints 4: Surfactant Titration
Sample size
General rule: avoid too small a sample size (lower content).
Increase sample size when the sample contains
1) Surfactants with additional many hydrophilic groups such as EO-units
2) Surfactants with short alkyl chains and broad chain length distribution

Chemical structure
•  The number of additional polar groups (e.g. ethers) affects the titration results.
•  The presence of nonionic surfactants can affect the analysis of ionic
surfactants

Titration speed
A precipitation reaction requires the appropriate time ⇒ Do not titrate too fast

.
33
Summary
Four different techniques for the titration of surfactants have been
described:

§  Colorimetric Two-Phase Titration DP5 Phototrode™

2P Titration beaker

§  Turbidimetric titration DP5 Phototrode™

§  Potentiometric titration - aqueous phase DS500

§  Potentiometric Two-Phase Titration - mixed phase DS800 TwoPhase

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