Surfactant S

Center for Miljø og Luftveje
Surfactants
Their abilities and important

physico-chemical properties
DET STRATEGISKE
MILJØFORSKNINGS-
PROGRAM
Surfactants

Rapport fra Center for Miljø og Luftveje
Charlotte Pilemand, EnPro ApS
Arbejdsmiljøinstituttet
København 2002
DET STRATEGISKE
MILJØFORSKNINGS-
PROGRAM
EnPro ApS
Surfactants

Charlotte Pilemand, EnPro ApS
ISBN: 87-7904-108-6
København 2002
Tryk: DTKommunikation A/S
Arbejdsmiljøinstituttet
Lersø Parkallé 105
2100 København Ø
Tel.: 39 16 52 00
Fax: 39 16 52 01
www.ami.dk
e-mail: ami@ami.dk
Preface
In 1998 the Danish Environmental Research Programme for 1998-2001 "Environmental

and health damaging compounds" established a multidisciplinary research centre “the
Environment and the Lung” (in Danish “Center for Miljø og Luftveje). The overall
objective of the Centre is to provide a scientific knowledge base for decision making,
aiming at reduction of exposure to environmental pollutants being a substantial health
risk to the population.
The research activities of the Centre have focus on the three high priority types of
exposure:
• Traffic emission
• None-infectious microorganisms and biologically active components thereof
• Plasticizers and detergents
In this report data on structure, HLB-values (HLB=hydrophilic Lipophilic Balance),

surface tension, critical micelle concentration (CMC) and cloud point for detergents are
collected from the literature, raw material suppliers and relevant industries. The aim is
to systematize these data and make them available for research partners, industries and
authorities. The results can also be used to evaluate the need for measurement of
missing data and technical properties for specific detergents in connection with
industrial applications.
On behalf of the Centre for the Environment and the Lung
Otto Melchior Poulsen

Centre leader, M.Sc., Dr. Vet. Sci.
3
Table of contents
Summary 7
1. Introduction 8
2. Surfactants 9
2.1 Surfactants in general 9
2.1.1 Anionic surfactants 11
2.1.2 Non-ionic surfactants 12
2.1.3 Cationic surfactants 13
3. Important surfactant abilities 15
3.1 Emulsification and solubility 16
3.2 Wetting 17
3.3 Dispersing 19
3.4 Foaming 19
3.5 Detergency 20
4. Important properties of surfactant solutions 22
4.1 Critical micelle concentration 22
4.2 Krafft point 23
4.3 Cloud point 24
4.4 HLB-number 24
4.5 Phase inversion temperature 26
4.6 Surface tension 26
5. Comments 27
6. References 28
Appendix A 29
5
Summary
Surfactants are described in general terms by discussion of chemical structure, types and
abilities. The four different main types of surfactants: anionic, cationic, non-ionic and
amphoteric surfactants are shortly presented and examples of compounds belonging to each
type are listed.
The most important technical abilities of surfactants and surfactant solutions like
emulsification, solubility, wetting, dispersing, foaming and detergency are discussed and
these abilities are related to relevant physico-chemical properties. The most important
physico-chemical properties are described as well as their usefulness from a technical point
of view when working with formulations containing surfactants.
Appendix A lists properties commonly available for some selected non-ionic and
anionic surfactants (ethoxylated alcohols and alkyl sulphates respectively).
7
1. Introduction
Surface-active agents, surfactants, are used in almost any household product and personal
care product as well as in nearly every industrial process. Contact with products containing
surfactants is therefore inevitable. This literature study concerning surfactants in general
has been performed as a part of the centre “Environment and the Lung". The Centre is
mainly concerned with biological and physiological aspects of plasticisers and surfactants,
but this part of the work concerns surfactants from a technical and formulation viewpoint.
The different industries using surfactants in their formulation are from time to time
faced with the need for substitution of one surfactant with another, often due to
environmental consideration. Substitution work can be very difficult and time consuming.
Besides finding a proper alternative to the original surfactant it might be necessary to
reformulate the product to retain its optimal abilities. First step in the substitution work is to
select some alternative surfactants to test in the formulation. The more proper alternatives
that can be selected from the beginning the less trial and error work needs to be performed
later on.
Fundamental for the choice of alternative surfactants is the knowledge of the physico-
chemical properties that determine the surfactant abilities. The more the physico-chemical
properties of the alternatives resembles the properties of the original surfactant the more
likely that the alternative surfactants might work in the formulation. Another thing that
could make the substitution work less laborious is development of models that can predict
how surfactants behave in solutions.
This report gives a general description of surfactants, their chemical structure, the
existing main types and the important abilities such compounds posses. It is discussed what
physico-chemical properties that is important for surfactants from a technical point of view
and therefore useful to know if substitution is the issue.
The physico-chemical properties pointed out in the academic literature as being
important from a technical viewpoint differs to some extent from the data that is actually
available for commercial surfactants and therefore often used in practical formulation
techniques. This can be observed by comparing the properties described in the report with
the data given in appendix A, which are data commonly available for some selected
commercial surfactants. The kind of data that is important in practical formulation
techniques furthermore differs from application to application.
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2. Surfactants
Surfactants are chemicals, which show ability to adsorb at surfaces. They are therefore
classified as surface-active compounds or surface-active agents. The surfaces (interfaces),
at which they adsorb, can either be between two liquids, between liquid and gas (air) or
between solids and liquids1,2. The short term for surface-active agents is surfactants, but
they are also often called amphiphiles.
Despite that surfactants often are present in very small amounts in solutions (detergents,
cleaning agents and microemulsions being an exception) they greatly affect the overall
properties of the system because of their ability to adsorb at surfaces 1,2. Surfactants are
therefore sometimes referred to as effect chemicals and instead of using the general term
surfactants, many surface-active compounds are named after the specific effect they show
in solutions, for instance dispersing agents, foaming agents, wetting agents, emulsifiers
etc3.
The characteristic properties of solutions containing surfactants, such as
detergency, wetting, emulsification, dispersion, and foaming, all depend on the
tendency of surfactants to accumulate at the interfaces between the solution and the
adjacent gaseous, liquid and solid phases4.
2.1 Surfactants in general
Surfactants, are compounds that have an amphiphilic nature, as their molecular structure
contains parts with different polarity, a hydrophobic (non-polar) part and a hydrophilic
(polar) part. See figure 2.1. The hydrophobic part is commonly a hydrocarbon
(branched or linear) which may contain aromatic structures. This part of the surfactant
is soluble in oils (non-polar solvents) but is not very soluble in water and other polar
solvents.
The hydrophilic part on the other hand has a great affinity to water but is not very
compatible with non-polar solvents. The hydrophilic part is an ionic or strongly polar
group (for instance ethylene oxide) 1,2,5.
hydrophobic hydrophilic
tail head-group
non-polar part polar part
Figure 2.1 Schematic surfactant molecule
9
The hydrophobic part of the surfactants is often referred to as the hydrocarbon tail, whereas
the polar part is referred to as the head-group5. Even though called the head-group the
hydrophilic part is not necessarily placed at the end of the hydrocarbon chain. More than
one hydrophilic or hydrophobic group can be present in a surfactant molecule2,22.
A surfactant molecule is not fully compatible with either a non-polar or polar medium.
There is always a conflict between the affinity of the head-group and the tail and this is
giving surfactants their unique properties5. Relative sizes and shapes of the hydrophobic
and hydrophilic parts play an important role for the physical properties of surfactants. For
instance an anionic surfactant having a straight hydrocarbon chain as the hydrophobic part
will show maximum surfactant properties in aqueous solutions when the hydrophobic chain
contains 10 to 18 carbon atoms. More than one hydrophilic group in the surfactant
increases the solubility and allows a higher number of carbon atoms in the hydrophobic tail
before optimum surfactant properties are reached1,2.
The majority of surfactants contain hydrophobic groups with 10 to 16 carbon atoms in
the chain. Straight chain surfactants usually show better biodegradability compared to
surfactants with branched or cyclic chains1,2. Investigations of branched ethoxylated
surfactants have though shown that the biodegradability is very dependent on where the
branching is situated as well as the length of the site chain. By proper branching as good or
almost as good biodegradability can be obtained for ethoxylated branched surfactants as for
straight chain ethoxylated surfactants. That combined with a lower toxicity could make
certain types of branched ethoxylated surfactants interesting alternatives to straight chain
ethoxylated surfactants6.
Surfactants are classified according to the nature of their head-group. Four main types
of surfactants exist: anionic, cationic, non-ionic and amphoteric surfactants. The ionic
surfactants carry a net charge located on the head-group, whereas the non-ionics are
neutral, but have polar head-groups e.g. ethylene oxide (EO)1,2,5. Amphoteric surfactants
can be either anionic or cationic depending on the alkalinity of the solution. See figure
2.2.
Anionic and cationic surfactants are generally not compatible. Non-ionic and
amphoteric surfactants are compatible with each other and with anionics and cationics.
Anionic and non-ionic surfactants account for more than 80 % of the consumed
surfactants.
Anionic
Cationic
Amphoteric
Non-ionic
Figure 2.2 The four different main types of surfactants.
10
2.1.1 Anionic surfactants
Anionics are manufactured and used in large volume because they are used in almost every
type of detergent and cleaning agent. Anionic surfactants consisting of a linear chain with
the polar group situated at the end show optimal detergency with a chain length in the
range of C12-C161. Good foaming is also observed for this chain length. C12-C16 surfactants
are water soluble, but the solubility improves further if the chain length is decreased.
Anionic surfactants attract the positive charge of other large molecules, leaving a
negative charge on the surface, causing excellent wetting in aqueous systems7. Optimal
wetting is usually observed for surfactants containing C12 chains.
Of the anionic surfactants utilised in the industrial sector as well as in the
household and personal care sector soap, sulphonates and sulphates are especially
important. Apart from soap the most important mass produced products are linear
alkylbenzene sulphonates, alkyl sulphates and alkyl ether sulphates2.
The most common counter-ions (cations) used in these surfactants are sodium,
potassium, calcium, ammonium, isopropylamine, monoethanolamine, diethanolamine and
triethanol amine1.
Examples of anionic surfactants:
• Carboxylates (soaps)
• Sulphates:
Alkyl Sulphates
Alkyl Ether Sulphates
• Sulphonates:
Linear Alkyl Benzene Sulphonates (LAS)
Alkyl Sulphonates
Ester Sulphonates
• Sulphosuccinates and Sulphosuccinamtes
• Isethionates and Taurates
• Phosphates
• Sarcosinates
The solubility of soap declines with increasing chain length. The alkali salts of fatty
acids with less than 10 carbon atoms do not show the characteristic properties of soaps.
The surface-active properties become apparent only with longer hydrocarbon chains,
with an optimum of 12-18 atoms2.
The properties of alkyl sulphates are mainly determined by the chain length and the
degree of branching. They are generally very foam intensive and wash effective
surfactants and they possess high interfacial activity. The solubility decreases with
increasing chain length while the hardness sensitivity increases2. Surfactants with
relatively short chains are therefore preferred.
Ether sulphates exhibit synergistic effects in combination with other surfactants,
e.g. regarding the foaming power and the oil dispersing ability. These effects are
especially utilised in the field of dishwashing and cleaning agents. Combinations of the
ether sulphates with alkylbenzene sulphonates or alkanol amides are particularly
notable here2.
Ester sulphonates of short chain alcohols (e.g. methyl ester sulphonates) have good
detergency properties. However, if the hydrophilic sulphonate group is located in the
11
centre of the molecule (e.g. in ester sulphonates of long chain alcohols) the detergent
properties decrease but the products are then good wetting agents2.
2.1.2 Non-ionic surfactants

Non-ionic surfactants do not have a charged group as implied by the name. The hydrophilic
group is provided by a water-soluble group, which does not ionise. The most common
water-soluble groups used are the hydroxy group, (-OH), and the ethylene oxide group (–
OCH2CH2-). Especially surfactants containing ethylene oxide groups are widely used and
this is why the class of non-ionic surfactants more or less has become synonymous with
ethylene oxide (EO) based surfactants (ethoxylated surfactants)8.
Alkoxylated non-ionic surfactants are surfactants containing ethylene oxide (EO) or
higher alkylene oxides (e.g. propylene or butylene oxides). Alkoxylated non-ionic
surfactants are compatible with all other surfactant types and do often form mixed micelles
with these. Non-ionics show excellent stability in a very large number of aqueous
formulations1.
The presence of several hydroxy or EO groups increases the solubility of a surfactant
molecule, meaning that the length of the hydrocarbon chain can be increased. If a non-ionic
surfactant just contains one hydrophilic group the hydrocarbon chain can only contain 6-8
carbon atoms before the surfactant molecule becomes insoluble in water1.
Examples of ethoxylated non-ionic surfactants:
• Alcohol Ethoxylates
• Alcohol Alkoxylates
• Alkyl Phenol Ethoxylates
• Fatty Acid Ethoxylates
• Ethylene Oxide/Propylene Oxide copolymers
• Alkanol amides
• Fatty Amine Ethoxylates
Examples of multihydroxy non-ionic surfactants:
• Glycol Esters
• Glycerol Esters
• Polyglycerol Esters
• Alkyl Polyglucosides
• Sorbitan Esters and Sorbitan Ester Ethoxylates
• Sucrose Esters
In the past alkyl phenol ethoxylates have extensively been used as non-ionic surfactants
in detergents and cleaning compounds. Octyl, nonyl, dodecyl phenol ethoxylates having
the greatest commercial importance. Especially nonyl phenol ethoxylates have found
extensive use over many years. They have been employed in simple formulation
through more complex emulsion based systems9.
Alkyl phenol ethoxylates will increasingly be substituted by alternative surfactants
with better environmental properties10. Their replacement is not straightforward and no
single replacement type has been identified. However, it has been demonstrated that in
many cases, nonylphenol ethoxylate based systems may be satisfactory replaced with
12
those based on alcohol ethoxylates. Substitution requires a degree of reformulation
effort, particularly when the surfactant is the primary emulsifier for a hydrocarbon
solvent9. It has furthermore been shown that alkyl phenol ethoxylates in some cases,
e.g. in paint, can be substituted with fatty amide ethoxylates23.
Fatty acid ethoxylates are applied as emulsifiers in pharmaceuticals, cosmetics and
food industry, as wetting agents in the manufacture of fibres and paints, as plasticisers
in the plastic industry2, and are used in cleaning agents.
Alkanol amides are utilised as foam stabilisers and thickening agents. Due to good
antistatic and anticorrosion properties, and the capability to increase the emulsifying
properties of many anionic and other non-ionic surfactants, alkonol amides do find
utilisation in detergents and cleaning compounds, in the textile industry and for many
technical application purposes2.
EO/PO block polymers are used as mild, skin compatible emulsifiers, as thickeners
in cosmetic and pharmaceutical industry, and as additives in plastics and paints2.
Increasing the molecular weight and increasing the EO content the water solubility
improves. Products with low molecular weight and low EO content have the best
wetting properties2.
Sorbitan esters belong to the group of non-ionic surfactants without EO groups
(but they can contain such groups). Sorbitan esters find use in the cosmetic, food and
pharmaceutical industry. They further find use in the fibre industry, in the manufacture
of pesticide and herbicide emulsions, dyestuff pigment pastes, cutting and lubricating
oils and in explosives2.
Alkyl polyglucosides have during the last years become the most used non-ethoxylated
non-ionic surfactants due to their easy biodegradability and good surfactant abilities. They
are used in detergents, in dishwashing agents, in cleaning agents and as emulsifiers.
Furthermore they find use in cosmetics and food2.
2.1.3 Cationic surfactants

Most cationic surfactants have hydrophilic groups, which are based on a nitrogen atom
carrying the positive charge, few exceptions are based on phosphor and sulphur atoms.
Most solid surfaces are negatively charged and the surface properties can therefore be
modified by using cationic surfactants, as they carry a positive charge1.
Examples of cationic surfactants:
• Quaternary Ammonium Salts

• Imidazolinium Salts
• (Ethoxylated Fatty Amines)
The simple salts of long-chain tertiary amines, obtained by neutralisation of the amines
with organic or inorganic acids are rarely used in detergents and cleaning agents. Their
main application is in textile treatments and occasionally as rinse fabric softener2.
Quarternary ammonium salts, containing C12-C14 alkyl groups are primarily
utilised as antimicrobial active substances2,22.
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Amphoteric surfactants
Amphoteric surfactants are characterised by a molecular structure containing two
different hydrophilic groups, one with anionic and one with cationic character. Most
amphoteric surfactants are able to behave in acidic media like cationic surfactants and
in alkaline media like anionics. The betaines are an exception, as they cannot be forced
to assume anionic behaviour through an increase in pH-value2. The most common
anionic group is the acid group, -COOH, whereas the most common cationic group is the
amino group, -NH21.
Amphoteric surfactants have an isoelectric point where both ionic groups show equal
ionisation (a Zwitterion). At this point the surfactants generally show minimum surfactant
properties1.
Examples of amphoteric surfactants:
• N-alkyl Aminopropionates
• N-alkyl Iminopropionates
• N-alkyl Betaines
• N-alkyl Glycinates
• Alkyl Imidazolin products
Amophoteric surfactants show excellent compatibility with other types of surfactants and
mixed micelles are frequently formed. This often improves the overall surfactant properties
of a solution, why amphoteric surfactants can be used for stabilising unstable systems based
on other surfactant types22. The amphoterics are excellent wetting agents in high electrolyte
concentrations. They do also show some biocidal effect1. The amphoteric surfactants are
relatively expensive products compared to anionic surfactants2.
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3. Important surfactant abilities
The characteristics vary from surfactant to surfactant. Some surfactants are good wetting
agents, some are good dispersing agents, and some are good emulsifiers and so forth.
This depends on the surfactants but also on the formulation in which the surfactants are
used. Three basic concepts explain the majority of observed phenomena in surfactant
solutions.
These are solubility, adsorption of surfactants at surfaces (interfaces) and the
formation of micelles in solution. These phenomena make surfactants different from
other chemical compounds1.
The major characteristic of surfactants is that surfactant molecules are present at
higher concentration at the surface than in the bulk of the liquid. This phenomenon is
known as adsorption and occurs at liquid/solid interfaces, liquid/liquid interfaces and at
air/liquid surfaces. Many chemicals produce foams and wet surfaces, but are not
considered as surfactants as they do not adsorb at surfaces1.
Surfactants accumulate at the interface between polar and non-polar regions. This is
due to energetic reasons, where surfactant molecules always tend to reduce the contact
between the hydrocarbon tail and water2. In an aqueous solution of a surfactant there is an
excess concentration at the surface where the surfactant can orientate their hydrophobic tail
away from the polar water phase towards the air. If hydrophobic surfaces are present in the
solution the surfactant molecules will adsorb to these surfaces with the hydrophobic tail
pointing towards the hydrophobic surface1,5. If the relative strength of hydrophobic and
hydrophilic effects changes, the water-solubility of the surfactant changes1.
The adsorption of a surfactant at an air/water surface will result in physical changes of
the solution. The more surfactant presents at the surface, up to complete coverage of the
surface, the more pronounced the change1. The solution will show a decrease in surface
tension as long as surfactant molecules can be adsorbed at the surface. When a monolayer
of surfactants is formed at the surface, the surface tension has reached its minimum and
will no longer decrease. If more surfactant molecules are present in the solution they will
begin to aggregate and form micelles. When saturation of the surface occurs, the solution
has reached the so-called critical micelle concentration (CMC)1. Surfactant solutions are
essentially at its optimum for many applications, e.g. wetting, when they reach the critical
micelle concentration1. To obtain optimum abilities in a practical surfactant solution it is
often necessary to have surfactants in amounts that exceeds CMC considerably as the
surface areas often are expanded during application22.
There is a similar effect when a surfactant is present in a system of two liquids, which
do not mix. Here the surfactant adsorbs at the interface and reduces the interfacial tension1.
The ability of the surfactant to adsorb at surfaces and to form micelles in solution,
determine the properties of the surfactant2. It is adsorption at surfaces that gives the
surface-active effects of foaming, wetting, emulsification, dispersion and detergency,
whereas the micellar properties give the surfactant solution its bulk properties such as
viscosity and solubilisation, but the micellar properties are necessary in emulsification and
detergency as well1.
Adsorption and hence surface-active properties are high in a surfactant solution when
solubility is poor. Practical formulations are usually a compromise between surface-active
properties and solubility1.
15
Surfactants show abnormal solubility characteristics compared to most other organic
chemical compounds. The solubility of most non-surfactants will increase with increasing
temperature1. The solubility of ionic surfactants on the other hand do only show a slow
increase up to a certain temperature, the Krafft temperature or the Krafft point, after which
there is a rapid increase in solubility with practically no further increase in temperature. At
the Krafft temperature the critical micelle concentration (CMC) of the surfactant solution is
reached. Below the Krafft temperature no micelles are formed and the solubility is limited.
Above the Krafft point micelles are formed and therefore solubility is increased
extensively1.
The solubility behaviour of alkoxylated non-ionics appears to be quite different from
that of ionic surfactants, as the solubility of alkoxylated non-ionic surfactants decreases
dramatically above a certain temperature known as the cloud point1. Krafft points for
alkoxylated non-ionics are in most cases hypothetical because they will exist below the
freezing point of water. Alkoxylated non-ionics containing large hydrobic groups can
though have a Krafft point above 0ºC1,24.
The Krafft point and CMC of a surfactant gives practical information about the
conditions under which a surfactant operates. The relationship between Krafft point and
CMC and the chemical structure of surfactants is therefore of considerable interest and
knowing these properties can help in the choice of a particular surfactant for a particular
formulation1. Krafft point and CMC are usually not available for commercial surfactants
why these properties still most are of academic interest. CMC can be of interest in many
formulations, but not in detergents and cleaning agents22.
3.1 Emulsification and solubility
One of the widest applications of surfactants is to solubilise or to disperse water insoluble

substances in water. This application area tends to become greater and greater due to the
fact that many organic solvents are totally or partly being substituted by water-based
systems.
When water insoluble compounds are added to an aqueous solution of surfactants one
of following situations can be observed:
• An oil in water emulsion (O/W emulsion) is formed. The system consists of two
liquid phases where the oil (a non-polar compound) is present as immiscible
droplets in the water phase. The system is unstable and will separate on standing.
• An oil in water microemulsion is formed. The oil is dispersed or dissolved in the
water phase. A very stable solution is formed which does not separate on standing.
• A water in oil emulsion (W/O emulsion) is formed. Two liquid phases are present.
Water is present as immiscible droplets in the oil phase. The system is unstable and
will separate on standing.
• A water in oil microemulsion is formed. Water is dispersed or dissolved in the oil
phase. A very stable solution is formed which does not separate on standing.
• Solubilisation of non-polar compounds in the aqueous solution with surfactant. The
non-polar compounds dissolve in the polar phase and a stable system is obtained,
which does not separate on standing (a true solubilisation).
The emulsions are formed because of the ability of the surfactants to adsorb on the
interface. The hydrophobic part of the surfactant molecule is located in the oil phase
16
whereas the hydrophilic part is located in the aqueous phase. Water-soluble surfactants are
most efficient for W/O emulsions whereas water-insoluble surfactants are most efficient for
O/W emulsions1.
The physico-chemical properties of surfactant solutions change due to the formation
of surfactant aggregates (micelles). Surfactant solutions above CMC can solubilise (or
emulsify) otherwise insoluble organic materials by incorporating it into the interior of the
micelles. The bigger the micelles present in a surfactant solution the more water-
insoluble compounds can be solubilised, but the less stable does the system also
become. The longer the carbon chain in a surfactant molecule the better a solubilisation
of water-insoluble compounds is usually obtained.
The location of the solubilised molecules in the micelle will depend upon the
chemical nature of the organic compound and the surfactant. Hydrocarbons will be
associated with the core of the micelles, while slightly polar compounds can be found in
the outer regions1.
In practise it is found that a mixture of surfactants with differing solubility properties
will produce emulsions with enhanced stability1. As solubilisation of a compound is
dependent on the size and number of micelles present in the solution a true
solubilisation can therefore only be obtained if the surfactant concentration is in excess
of the material being solubilised1.
For a non-ionic surfactant solution an increase in temperature can bring about a phase
inversion from O/W to W/O due to the non-ionic alkoxylated surfactants becoming less
water-soluble as the temperature increases. The temperature at which the inversion takes
place is known as the phase inversion temperature (PIT)1.
One way of characterising the efficiency of a surfactant as emulsifier is the
Hydrophilic-Lipophilic Balance, HLB. This method was developed by Griffin in 1949 and
has been proved very successful with alkoxylated non-ionic surfactants but less successful
with ionic surfactant1. High HLB-numbers indicate water-soluble surfactants, whereas low
HLB-numbers indicate water-insoluble surfactants1. The HLB numbers of surfactants
depend on the oil type as well as the solution temperature12.
Properties as critical micelle concentration (CMC), the hydrophilic-lipophilic balance
(HLB), The Krafft point, the cloud point and the phase inversion temperature (PIT) are
important parameters for the emulsification and solubilisation abilities of surfactant
solutions. Although both the HLB number and the PIT concept are empirical they can be
very useful1. However, in practice a considerable amount of trial and error work is still
needed, as there can be many different mixtures of surfactants, which will possess a single
HLB number or PIT1. From the viewpoint of a formulator cloud point is the most important
property when choosing surfactants for most common application as this property is more
well-defined than HLB numbers and offers greater flexibility22.
3.2 Wetting
When a drop of water is placed on a surface it can either spread over the surface, which
means it wets the surfaces, or it can form a stable drop, which means that it does not wet
the surface1.
17
The final shape of the drop depends on the relative magnitude of the molecular forces that
exist within the liquid (cohesive forces) and the forces between the liquid and solid
(adhesive forces). The index of this effect is the contact angle, which is a measure of the
degree to which a solid substance is wetted by a liquid1,5.
In general it is found that liquids with low surface tension easily wet most solid
surfaces, giving a zero contact angle. The molecular adhesion between solid and liquid is
greater than the cohesive forces between the molecules of the liquid. Liquids with a high
surface tension mostly give a finite contact angle and here the cohesive forces become
dominant13.
Although wetting is often described in terms of the spreading coefficient and Young´s
equation, such mathematical relations are true only at equilibrium1. In most practical
applications of wetting the process is only in one direction and it is then the kinetics of the
wetting process, which is more important1. Furthermore only few surfaces are smooth why
there usually also are considerable capillary effects1.
Reduction in surface tension of water by adding a surfactant can make a non-wetting
solution into a wetting solution on particular substances. The ability to wet depends upon
the surface tension of the solution and the critical surface tension (CST) of the solid. The
CST is the surface tension of a liquid, which exactly will form a contact angle of zero with
the solid, i.e. the liquid spreads over the solid1.
An important concept is the rate at which the surface tension decreases. In order to
spread, the surface of the liquid must expand. A new surface is then formed and the
surface tension increases unless the surfactant is immediately adsorbed at the new
surface at the same concentration as at the original surface. Surfactant molecules will
diffuse from the interior back to the surface in order to lower the surface tension. Thus
if diffusion is slow the rate of wetting is poor1. The faster a surfactant molecule diffuses
to freshly formed surfaces in the solution the better (faster) the wetting. This is why
small surfactant molecules in general give better wetting than large molecules, as small
molecules diffuse faster through a solution1.
The optimum wetting characteristics are shown at hydrophobic chain lengths shorter
than for foaming or detergency, and are usually found in the region of C9-C12, but there
are exceptions1. Additional polar groups usually results in a loss of wetting power1.
Particularly anionic surfactants are used as wetting agents in many applications, but
non-ionic surfactants are good wetting agents as well11.
If the temperature is increased in a system the wetting power is reduced as the
solubility of the solution improves (adsorption is thereby reduced and a poorer lowering
of surface tension is obtained). Alkoxylated non-ionics are an exception1.
Ethoxylated non-ionic surfactants will pass through a minimum of wetting
performance as the EO content increases. The minimum is where the cloud point is just
above the test temperature1.
If addition of an electrolyte causes a further reduction in surface tension the wetting
is improved. Co-surfactants can also be added to improve wetting abilities of anionics.
Furthermore pH can play a role if weak basic and or acidic groups are present1.
Irregular shaped surfactant molecules are often very good wetting agents, since
micelle formation is not favoured, owing to steric considerations, this permits relatively
high concentrations of non-associated surfactant molecules and hence a greater
lowering of surface/interfacial tension11.
Properties such as surface tension, contact angles and CMC have importance for the
wetting abilities of surfactant solutions. The diffusion rate of surfactant molecules in the
solution is also important.
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3.3 Dispersing
Surfactants are used in suspensions to prevent other particles present from aggregating as
they can reduce the interfacial energy between solid and liquid interfaces. This favours the
formation of new surfaces between the solid particles and the solutions instead of
aggregation of particles. When adsorbed on the surface of the solid particles the surfactants
produce an electrostatic barrier to prevent re-aggregation of the particles. A dispersion of
particles in solution will be stable if any attractive forces can be counteracted by repulsive
forces between the particles. The adsorption of surfactants on the solid causes the solid to
acquire a charge, which repel similarly charged particles by increasing the electrostatic
force1. The type of surfactant that will give efficient dispersing properties will depend upon
the nature of the solid particles1.
The majority of solid surfaces are negatively charged, this means that anionic
surfactants commonly are the most effective stabilisers of suspensions. However, steric
effects can also act in stabilising hydrophobic particles1. Surfactants that stabilise solid
suspensions are in general large whereas surfactants with good wetting properties in
general are small1.
On hydrophilic surface the adsorption of ionic surfactants can be high. On hydrophobic
surfaces the adsorption of ionic surfactants is extremely low, but can be increased by
adding electrolytes on hydrophobic surfaces. Non-ionic surfactants are adsorbed in
considerably higher amounts than ionic surfactants on hydrophobic surfaces.
An increase in temperature will decrease the adsorption of ionic surfactants while that
of alkoxylated surfactants is increased due to the product becoming more hydrophobic1.
3.4 Foaming
Most surfactants give rise to foam, which can be desirable or undesirable depending upon
the application. Whether much foam, little foam or no foam is needed, the formulator
wishes to control the level of foam and to know which outside factors can affect the foam.
Only few guidelines exist in solving problems of foaming and defoaming, and most
practical problems are still solved empirically1.
As a general rule, foam is not generated in a pure liquid phase and a surfactant that
strongly adsorbs at the air interface is necessary in order to produce foam in aqueous
solutions1. Foam consists of a thermodynamically unstable two-phase system of gas
bubbles in liquid. The formation of foam from a bulk liquid involves the expansion of the
surface area. As surface tension is the work involved in creating a new system, the amount
of new area formed (i.e. the foam) will be greater the lower the surface tension. Thus
reduction of surface tension by the surfactant is the primary requirement of foam
formation1.
In all applications foam is practically simultaneously being generated and collapsing.
The observed foam performance of the surfactant is the net effect of this1. At a certain
critical thickness, the film of the bubbles collapses, and the foam bubbles burst. The
stability of the film will depend upon a number of factors such as type of surfactant,
concentration of surfactant, temperature, presence of electrolytes and the presence of other
organic materials1.
19
The foam volume formed increases with an increase in the concentration of surfactant up to
CMC. Above CMC the amount of foam is relatively constant. There is no similar rule with
respect to the stability of the foam1.
Some empirical generalisations can be made relating chemical structure to foam
performance. There are however distinct differences between concentrations at or close to
CMC and those considerably in excess of the CMC1.
Ionic surfactants usually produce more foam and more stable foam than non-ionics.
Alkyl poly glucosides are an exception as they are very foam intensive. Surfactants with
straight hydrocarbon chains show better foaming than those with branched chains and the
foam amount goes through a maximum when the chain length is increased in a homologous
series.
The effect of temperature on foaming ability will be similar to the temperature effect on
solubility where ionic surfactant will show better foaming with increased temperature,
while non-ionics will either show a decrease or go through a maximum in foam production
with increasing temperature. Polar surfactants, which lower the critical micelle
concentration for another surfactant, can improve stability of the foam1.
The easiest way to control foam is by choosing a suitable surfactant. However, in many
practical applications there will be limitations on the choice of surfactant with respect to its
foaming ability. The primary reason for using a surfactant, e.g. detergency, may give higher
foaming products than wanted, the ideal surfactant may be very costly or the interaction
with other components may change the foam performance. Therefore there can be a need to
control the foam by adding a foam control agent. Such foam control agents are called
antifoamers or defoamers. The two terms are not synonymous, as an antifoamer will
prevent foam from being produced, whereas a defoamer will collapse produced foam1.
Surface tension is an important parameter for the foaming ability of surfactants.
3.5 Detergency
Detergency is removal of soil from a substrate immersed in a medium, generally

through the application of a mechanical force in the presence of a chemical substance,
which may lower the adhesion of the soil to the substrate. The process is completed
when the soil is maintained in suspension so it can be rinsed away14.
In practise detergency involves essentially four processes: wetting the soiled
substrate, removal of soil from the substrate, suspension of the soil and prevention of its
re-deposition. Thus detergency involves the surface-active processes of wetting,
adsorption, emulsification/solubilisation and dispersion, all of which have already been
described1.
The wetting of the substrate is a similar process to that already discussed under
wetting, but is complicated by the fact that additional compounds are present (the soil).
If the aqueous solution shows a greater tendency to wet the surface than the oily soil
does, then the aqueous solution will replace the soil that will be released from the solid
surface1.
Detergents and cleaning agents, which are formulated products used to remove soil
from surfaces, are the most important applications of surfactants, and detergents do
therefore account for the bulk of surfactant usage11.
Detergents are often very complex products that contain several other compounds
than surfactants, such as builders, foam control agents, silicates to prevent corrosion,
anti-re-deposition agents such as copolymers, homopolymers and carboxymethyl
20
cellulose, colourants, perfume and softeners, all of which can effect the properties of the
surfactants. As detergents are very complex formulation it can be misleading to try to
judge the performance of a surfactant in a formulated detergent on data obtained in the
absence of builders and other additives1. Many different detergent formulations exist
because there is a very wide variety of soils, media and substrates1.
The presence of polyvalent cations, mainly calcium, in hard water has a severe
effect on detergency because the adsorption of such cations onto negatively charged
substrates (most fabrics are negatively charged when wetted with water) and onto soil
can reduce electrostatic repulsion and increase re-deposition of the soil. Furthermore,
calcium salts of anionic surfactants tend to be insoluble in water, and thus they
precipitate and become ineffective. Builders, phosphates, zeolites, copolymers and
EDTA can eliminate or reduce the effect of hard water by sequestration or precipitation
of polyvalent cations1.
A detergent must possess good wetting characteristics, in order to come into proper
contact with the surface that has to be cleaned. It needs to be able to remove or help to
remove the dirt from the surface into the bulk of the liquid, and it needs to solubilise or to
disperse the removed dirt and thereby prevent it from re-depositing on the surface11. The
best wetting agent is not necessarily the best detergent. The choice of surfactant therefore
involves a compromise between a small hydrocarbon chain for rapid diffusion (good
wetting) and a longer hydrocarbon chain for better dirt removal and dispersion
characteristics11.
Therefore detergents usually contain more than one surfactant and often many
surfactants are used in combination to create a cleaning agent with the right balance of
detergency, foaming, wetting, emulsifying, solubilising and dispersing properties,
where each surfactant contributes with its own special abilities to the cleaning
formulation.
Non-ionics seem to perform better above their cloud point as the maximum
detergency of ethoxylated non-ionics usually is observed 15-30°C above the cloud
point, where particles of surfactant rich phases are present1. This optimum temperature
is often more or less identical with the phase inversion temperature (PIT) of non-ionic
surfactants/oil/water systems1.
Years of empirical experience have shown that optimum detergency often is
obtained by using mixtures of anionics and non-ionics. The addition of non-ionics to
anionics will lower the CMC and PIT 1.
21
4. Important properties of surfactant solutions
Surfactants are added to formulations due to that one or more of the surfactant abilities
described in the previous chapter are wanted in the product. To get an indication
beforehand, whether a surfactant can be expected to give the wanted effects in the
formulation, it is important to know certain properties of the surfactant in solution.
Properties such as critical micelle concentration (CMC), the Krafft point, the cloud
point, surface tension, hydrophilic-lipophilic balance (HLB) and phase inversion
temperature (PIT) can be of importance, depending on the effects that are wanted from
the surfactant.
4.1 Critical micelle concentration
The critical micelle concentration (CMC) of a surfactant indicates the point at which
monolayer adsorption of surfactant molecules at the surface is complete and the surface-
active properties are at an optimum1. As the concentration of surfactant increases the
interface becomes packed with surfactant until a complete monolayer is formed. Further
addition of surfactant molecules causes them to aggregate into micelles. When the CMC is
reached in a surfactant solution the solubility is increased. Since micelles themselves are
not surface–active, the surface tension remains approximately constant beyond the CMC11.
The actual shape and structure of micelles depends on the temperature, the type of
surfactants and its concentration, other ions present in the solution and other water-soluble
compounds present, e.g. alcohols. The structure and shape can change as micelles are
dynamic entities1. The formed micelles can for instance be lamellar, cylindrical or
spherical1.
The number of surfactant molecules in a micelle is known as the aggregation number.
Non-ionic surfactants generally have higher aggregation numbers than anionics and
cationics. The aggregation number of non-ionics is temperature dependent, while this is not
the case for anionics and cationics. Furthermore, non-ionic surfactants form micelles at
much lower concentrations than ionic surfactants1.
The CMC is dependent on the chemical structure of the surfactant. From experimental
test it has been shown that for a homologous series of surfactants with the structure
CH3(CH2)nX, (with the same hydrophilic group X), the following is in general valid. The
CMC decreases as n increases and the CMC is at a minimum when X is situated at the end
of the molecule. If X = (EO)m, CMC decreases as the number of ethylene oxide groups, m,
decreases1.
The CMC is affected by factors such as relative size of hydrophobic and hydrophilic
parts in the molecule, the counter-ions, presence of electrolytes, pH and temperature1.
Aqueous solutions of surfactants invariably contain electrolytes (e.g. calcium ions from
hard water). The CMC decreases significantly when electrolytes are added to ionic
surfactant solutions while addition of electrolytes to non-ionic or amphoteric surfactant
solutions does not affect their CMC to the same extent1.
There is a considerable interest in the CMC property as this in practise represents the
lowest surfactant concentration needed to get maximum benefit if surfactant abilities based
on surface-activity are needed (e.g. wetting and foaming)1. For many applications it is
22
though difficult to use this property as the surface area is not constant. Often the surface
area will expand, when the surfactant formulation is used in practice. If improved solubility
of a solution is wanted the surfactant concentration needs to be above the CMC.
4.2 Krafft point
Surfactants forming micelles exhibit unusual solubility behaviour as their solubilities show
a rapid increase above a certain temperature, known as the Krafft point or Krafft
temperature. This solubility behaviour is mostly observed for ionic surfactants as only few
non-ionic surfactants posses a real Krafft point1,24. The explanation of this behaviour arises
from the fact that non-associated surfactants have a limited solubility, whereas micelles are
able to solubilise non-polar materials. Below the Krafft point temperature the surfactant
molecules are non-associates and the solubility power of the solution is low. When the
temperature is raised, the solubility increases very slowly until the Krafft point is reached.
As the Krafft point also is the temperature where the surfactant solution reaches its CMC,
micelles are formed and a large increase in solubility is therefore observed11. Thus it is
desirable to make a formulation above the Krafft temperature if complete solubility is
required1.
The Krafft point depends on a complex three phase equilibrium and depends largely on
the counter ion of the surfactant1. The chain length of the hydrophobe and the presence of
electrolytes does also influence the Krafft point of ionic surfactants1. The addition of
electrolytes increases the Krafft point at CMC1.
Surfactants with a high Krafft temperature have ionic head groups or have compact highly
polar head-groups and long straight alkyl chains. Lower Krafft point temperature can be
obtained with branched alkyl chains or bulkier hydrophobic groups (e.g. two alkyl chains)1.
If a surfactant solution needs to show surface-activity based abilities, such as wetting,

the solution should be used below or near its Krafft point, whereas if solubility is the
wanted ability the solution need to be used at temperatures above the Krafft point.
23
4.3 Cloud point
Non-ionic surfactants in aqueous solution show a miscibility gab with an upper critical
temperature. When heating a non-ionic aqueous solution a separation into two phases
occurs at a certain temperature as the surfactant “drops out of” the solution. This
temperature is called the cloud point, as this mixture becomes cloudy when the
separation process starts1.
The cloud point of non-ionics arises because the solubility of the polyethylene
oxide entity is due to hydrogen bonding. If the ability of compounds to solubilise
depends on hydrogen bonding in aqueous solutions, they are commonly found to exhibit
an inverse temperature/solubility relationship1.
The cloud point increases with increasing EO content in non-ionic surfactants. The
cloud point of alkoxylated alcohols decreases if the hydrophobicity of the surfactants is
increasesd1. The surface activity of the surfactant solution is highest just below the
cloud point15.
Cloud point temperatures are an excellent means of characterising many of the
non-ionic surfactants. In fairly diluted solutions (0.1-5%) the cloud point is independent
of concentration and is a characteristic of a particular surfactant1.
For laundry and cleaning applications optimal cleaning generally occurs at
temperatures above the cloud point15.
4.4 HLB number
The hydrophilic - lipophilic balance system (HLB) is one of the most common methods
to correlate surfactant structure with their effectiveness as emulsifiers1. The system
consists of an arbitrary scale to which HLB numbers are experimentally determined and
assigned18. The HLB numbers of surfactants depend on the oil type and the solution
temperature12. The value of the HLB number indicates how the surfactant will behave in
a solution. The method works very well for alkoxylated non-ionic surfactants but is less
successful with ionic surfactants1.
An empirical scale from 1-20 was established for non-ionic emulsifiers as it was
proposed to calculate the HLB number from the chemical structure of alkoxylated
surfactants in the following way1:
HLB = % of molar hydrophilic group dived by 5
The maximum HLB number was therefore 20 and represented a product composed
entirely of ethylene oxide with no hydrophobic group, whereas a HLB number equal to
zero represented a complete water-insoluble product with no ethylene oxide groups1.
The scale was later extended when HLB numbers were introduced for ionic surfactants
as well2.
An indication of an approximate HLB number can be obtained by adding a small
quantity of surfactant to water and shake the mixture. The appearance of the resulting
solution gives an indication of the value of the HLB number. The connection between
HLB number and the appearance of the mixture is shown in table 4.11. The higher the
HLB number the more hydrophilic the surfactant1,2,19.
24
Appearance on adding
HLB no. Emulsion type
surfactant to water
1-4 Insoluble W/O
4-7 Poor dispersion (unstable) W/O
7-9 Stable opaque dispersion -
10-13 Hazy solution O/W
≥ 13 Clear solution O/W
Table 4.1 Indication of an approximate HLB numbers based on the appearance of a mixture of
1
a small quantity of surfactant and water .
Hydrophilic surfactants are used for solubilisation and detergency whereas lipophilic
surfactants are used to couple water-soluble material into non-aqueous oil-based
systems16. Roughly it can be said that surfactants with HLB numbers less than 8
preferentially work as emulsifiers for W/O emulsions, while those surfactants with HLB
numbers higher than 10 preferentially yield O/W emulsions.
A more detailed connection between the value of the HLB number and the function
of the surfactant can be seen in table 4.2.
HLB no. Surfactant application
1-3 Antifoaming agents
3-6 W/O emulsifiers
7-9 Wetting agents
8-18 O/W emulsifiers
12-16 Detergents
15-18 Solubilisers
Table 4.2 Connection between the HLB-number and the function expected from the surfactant
17,18
in aqueous solution .
A number of different methods exist for calculating HLB numbers from chemical
composition and/or other physico-chemical data of the surfactant 20. HLB numbers can
also be determined experimentally11.
In commercial emulsion formulation, HLB numbers can be used as an initial guide
to choose some emulsifiers before the testing work starts in the laboratory. By choosing
surfactants with HLB-values appropriate for emulsifying any given oil/water system the
trial and error testing can be reduced, and optimum performance can usually be
obtained faster11,16. The application of the HLB system is though limited by the fact that
the emulsion type is frequently also affected by numerous other parameters, e.g. the
25
water/oil ratio, the temperature, and the viscosity2. With increasing temperature the
emulsifying agent becomes less hydrophilic which means its HLB number decreases11.
Often a blend of emulsifiers produces a more stable emulsion than the use of a
single emulsifier with the correct HLB. Since HLB numbers are additive, the HLB
number of a blend can be calculated18.
To determine the required HLB number for a mixture the individual HLB numbers
for each emulsifying agent is multiplied by its weight percent in the oil phase. The sum
of these values gives the approximate total HLB number19. One single HLB-number can
therefore be obtained with many different surfactant mixtures.
4.5 Phase inversion temperature
An alternative method for characterising emulsifying agents is the phase inversion

temperature (PIT). At this temperature the emulsion changes from an O/W to a W/O
emulsion1,11. Temperature has a big effect on emulsion systems made with non-ionic
(alkoxylated) surfactants, as the non-ionic surfactant becomes less water-soluble when the
temperature increases. The emulsion then becomes less stable and at a certain temperature
it changes from O/W to W/O1. The PIT of a given system should be higher than the
proposed storage temperature for an O/W emulsion and lower for a W/O emulsion11.
The PIT is usually 10 to 30°C higher than the cloud point of the emulsion. For
detergents optimum detergency is usually obtained in the neighbourhood of this
temperature.1 Although both the HLB and PIT concepts are empirical they are useful in
practice1.
4.6 Surface tension
Surface tension is a measure of the wetting ability of a compound and is a very important
parameter for surfactants. Surface tension is defined as the work required to increase the
area of a surface isothermally and reversibly by unit amount11. The phenomenon of surface
tension (interfacial tension) can be explained in terms of the short-range forces of attraction
that exist between molecules in a liquid. The molecules which are located in the bulk of a
liquid are, on average, subjected to equal forces of attraction in all directions, whereas those
located at a liquid-air interface experience unbalanced attractive forces resulting in a net
inward pull.
As many molecules as possible will leave the liquid surface for the interior of the bulk.
The surface will therefore tend to contract spontaneously. This is the reason why droplets
of liquid and bubbles of gas tend to attain a spherical shape11.
There is no fundamental distinction between the terms surface and interface, although it
is customary to describe the boundary between two phases of which one is gaseous as a
surface and the boundary between two non-gaseous phases as interfaces11.
26
5. Comments
When formulating or reformulating a product containing surfactants it is important to

clarify which abilities are wanted from the surfactant/product. If more than one ability is
wanted (e.g. both wetting and detergency) it is often unlikely that it can be obtained
with only one surfactant why several different surfactants are needed.
In a substitution process the most straightforward way to find alternative
surfactants is to compare the physico-chemical properties of the original surfactant or
surfactant mixture with those of the alternatives. The more the properties resembles
each other the more likely it is that the alternatives will work in the formulation. It is
therefore essential in a substitution process to know as many of those physico-chemical
properties described here as possible. That improves the chances of choosing proper
alternatives for further testing in the formulation. The better the initial choice of
alternative surfactants the less trial and error work is probably needed in the laboratory.
The physico-chemical properties emphasized in the academic literature as being
important from a technical viewpoint differ to some extent from the data that is actually
available to the practical formulators. Krafft point and CMC are rarely available for
commercial surfactants, whereas properties as cloud point and HLB numbers often are
available, especially for non-ionic surfactants. The reason for this is according to the
surfactant industry that the data mainly used in practical substitution situations are cloud
point, wettability, concentration (density), structure, colour, and pH21.
In appendix A tables with commonly available data for commercial non-ionic and
anionic surfactants are shown. Some examples of data from the open academic literature
are given as well.
The difference between the more academic point of view and the practical/industrial
point of view is probably due to that the skill of formulating systems containing surfactants
since its early beginning has been based on experiences and a lot of trial and error work.
This does not mean that the industry on longer terms could not benefit from using/knowing
more of the properties described in this report.
One of the really big obstacles is that physico-chemical properties available in the open
literature cannot be used in practical formulation work, as most academic studies of
surfactants are based on purified products. Commercially available surfactants are not
pure substances, but mixtures of homologous substances with different chain length due
to the fact that the raw materials is a mixture of compounds, for instance fatty acids with
different chain lengths1,2,3. Alkoxylated non-ionic surfactants are furthermore a mixture of
substances with different alkoxylation degree. Conclusions based on pure surfactants may
therefore not be applicable to commercial mixtures1.
Besides getting an indication of whether a surfactant can be expected to work in the
formulation or not by using the physico-chemical properties it is very important to
determine the toxicity and biodegradability of the alternatives. To get any
environmental benefit from a substitution the alternatives of course need to be less toxic
and/or more biodegradable than the original surfactant. From a commercial point of
view it is furthermore very important that the reformulated product retains its
characteristic after the substitution without any appreciable raise in price.
27
6. References
1. Porter, M.R.; ”The Handbook of Surfactants” ; 2. Edition, Chapman & Hall, 1994.
2. Falbe, J. ; ”Surfactants in Consumers Products”; 1987.
3. "Additives - An Introduction", Journal of Coating Technology, vol. 68, no 857, p.78-85,
1996.
4. Schick M.J.; "Nonionic Surfactants: Physical Chemistry"; Surfactants Science Series 23,
Dekker, NY, 1987.
5. Landgren, M.; ”Thermodynamic Modelling of Ionic Surfactant Systems”, A doctoral
dissertation, Lund University, 1990.
6. Kaluza U & Taeger K.; "Influence of Chemical Structure on the Ecotoxicological
Properties of Alkanol Ethoxylates", Tenside, Surfactants, Detergents, vol. 33, no.1, 1996.
7. Learch R.H.; " The printing Ink Manual"; Fourth Edition, 1988.
8. Hellsten M.; "Industrial Applications of Nonionic Surfactants", Industrial Applications of
Surfactants I, Royal Society of Chemistry, Special publication no. 39, p. 179-194, 1987.
9. Bognolo G., John G.R. & Evans J.G.; "Surfactants in the Environment - Some Recent
Developments", Industrial Applications of Surfactants III (Editor Karsa D.R.), Royal
Society of Chemistry, Special publication no. 107, p. 23-28, 1992.
10. Turner A. H & Houston, "The Market for Industrial Surfactants in the 1990s - An
Overview", Industrial Applications of Surfactants III (Editor Karsa D.R.), Royal Society of
Chemistry, Special publication no. 107, p. 3-19, 1992.
11. Duncan S.; “Introduction to Colloid and Surface Chemistry”; Third Edition, Butterworths,
1983.
12. Shinoda, K & Friberg, S.; “Emulsions and solubilization”; John Wiley & Sons, 1986.
13. Jaycock M.J. & Parfitt G.D; “Chemistry of Interfaces”; Ellis Horwood Limited, 1981.
14. Cutler, W. G. & Cavis, R.C.; "Detergency. Theory and test methods", Surfactant Science
Series, vol 5, Dekker, 1981.
15. www.huntsman.com/products/chemicals/pch8f004.htm 16-08-99.
16. www.surfactants.com/HLBsystem.html 07-05-99
17. www.tigerchem.com/surf.html 29-07-99
18. www.paddocklabs.com/secundum/secart41.htm 12-08-99
19. www.icisurfactant.com/HLBsystem.html 16-08-99
20. Lindman M. "Surfactants in Solution", vol. 3, Plenum Press, 1984.
21. Reckweg Anders, BASF – personal communication 21st January 2000.
22. Reckweg Anders, BASF – personal communication 25th April 2000.
23. Österberg E., Akzo Nobel; “Tensider – Miljøvenlige overfladeaktive stoffer”,
Presentation at the Danish Varnish and Paint Chemist Association (DLFF) meeting on
Tuesday the 21st September, 1999.
24. Schott H.; "Effect of electrolytes and protein denaturants on nonionic surfactants";
Tenside Surfactant Detergent, vol. 33, no. 6, p. 457-463, 1996.
28
Appendix A
29
Data for selected surfactants
Here are some examples of available properties for some selected surfactants. The data are mainly collected from surfactant suppliers, but a few
data from the open academic literature are given as well.
Table A.1 lists the names of presented surfactants together with synonyms and CAS numbers. Table A.2 to A.6 concern non-ionic surfactants
whereas table A.7 to A.9 presents data for anionic surfactant.
Table A.2 to A.4 list data available for commercial non-ionic surfactants. The data are kindly supplied by BASF and concern different
ethoxylated alcohols.
Table A.5 and A.6 list data for C12, C13 and C15 alcohol ethoxylates obtained from the open academic literature2.
Table A.7 and A.9 list data for commercial available anionic surfactants, alkyl sulphates and an alkyl ether sulphate respectively. The data are
kindly supplied by Albright & Wilson.
Table A.8 presents properties available in the open academic literature for sodium lauryl sulphate.
Table A.10 presents a few biodegradability data from the open academic literature.
1
Table A.1 Name, type, synonyms and cas numbers for the surfactants described in table A.2 to table A.9 . Be aware of that the lists of synonyms and cas
numbers are not complete.
Surfactant Type Synonyms CAS numbers

Ammonium dodecyl sulphate 2235-54-3
Ammonium lauryl
Anionic, alkyl sulphate Dodecyl ammonium sulphate 68081-69-9
sulphate
Sulfuric acid monododecyl ester, ammonium salt 90583-12-3
Lauryl sodium sulphate
Sodium monododecyl sulphate
Sodium dodecyl sulphate 151-21-3
Sodium lauryl sulphate Anionic, alkyl sulphate Dodecyl sodium sulphate 68585-47-7
Monododecyl sodium sulphate 68955-19-1
Dodecyl sodium sulphate
Sulfuric acid monododecyl ester, sodium salt
Triethanolammonium lauryl sulphate
Trolamine lauryl sulphate
139-96-8
TEA lauryl sulphate Anionic, alkyl sulphate Trietahnolamine lauryl sulphate
68908-44-1
Sulfuric acid monododecyl ester compound with
2,2´,2´´-nitrilotris[ethano] (1:1)
Sodium laureth sulphate
1335-72-4
Sodium lauryl ethoxy sulphate
3088-31-1
Sodium lauryl diethoxy sulphate
9004-82-4
Sodium lauryl ether Sodium lauryl triethoxy sulphate
Anionic, alkyl ether sulphate 13150-00-0
sulphate Sodium POE lauryl sulphate
15826-16-1
PEG(1-4) lauryl ether sulphate, sodium salt
68585-34-2
Poly(oxy-1,2-ethanediyl), α-sulpho-ω-(dodecyloxy)-
68891-38-3
,sodium salt
3055-93-4; 3055-94-5; 3055-95-6;
Laureth-x
3055-96-7; 3055-97-8; 3055-98-5;
PEG-x lauryl ether
Ethoxylated C12 alcohol Non-ionic, ethoxylated alcohol 3055-99-0; 3056-00-6; 4536-30-5;
POE(x) lauryl ether
5274-68-0; 6540-99-4; 9002-92-0;
68131-39-5; 68439-50-9
Trideceth-x
4403-12-7
Ethoxylated C13 alcohol Non-ionic, ethoxylated alcohol PEG-x tridecyl ether
24938-91-8
POE-x tridecyl ether
Ethoxylated C12-C14
Non-ionic, ethoxylated alcohol 68439-50-9
alcohol
Ethoxylated C13-C15
Non-ionic, ethoxylated alcohol 64425-86-1
alcohol
Ethoxylated iso-C13 Ethoxylated branched tridecyl alcohol 9043-30-5
Non-ionic, ethoxylated alcohol
alcohol Polyoxyethylene isotridecyl ether 69011-36-5
Table A.2 Data commonly available for selected commercial nonionic surfactants, C12-C14 alcohol ethoxylats
Alcohol ethoxylates
Physico-chemical properties C12-C14 ethoxylate C12-C14 ethoxylate C12-C14 ethoxylate
Property Method Reference Property Method Reference Property Method Reference

RO(CH2CH2O)x RO(CH2CH2O)x RO(CH2CH2O)x
Structure – formula 4 4 4
H H H
aliphatic, aliphatic, aliphatic,
Chain type 4 4 4
R=C12-C14 R=C12-C14 R=C12-C14
Surfactant type non-ionic 4 non-ionic 4 non-ionic 4
Ethoxylation degree approx. 3 4 approx. 4 4 approx. 7 4
MW average (g/mol) approx. 320 4 approx. 370 4 approx. 500 4
Concentration (%) approx. 100 4 approx. 100 4 approx. 100 4
Density at 23ºC (g/cm3) approx. 0.92 4 approx. 0.94 4 approx. 0.98 4
Solubility (10 % solution in water) 23ºC no 4 no 4 yes 4
Solubility ( 10 % in 5 % NaCl solution)
no 4 no 4 yes 4
23ºC
DIN DIN DIN
Surface tension (mN/M) at 20ºC, 1g/l H20 approx. 27 4 approx. 27 4 approx. 28 4
53914 53914 53914
Wetting ability at 23ºC, 2 g soda/l H2O, 0.5 DIN DIN DIN
> 300 4 approx. 40 4 approx. 90 4
g surfactant /l (S) 53901 53901 53901
Wetting ability at 23ºC, 2 g soda/l H2O,1 g DIN DIN DIN
approx. 100 4 approx. 30 4 approx. 40 4
surfactant /l (S) 53901 53901 53901
Wetting ability at 23ºC, 2 g soda/l H2O,2 g DIN DIN DIN
surfactant /l (S) 53901 53901 5390
Table A.2 Continued.
Alcohol ethoxylates

Solidification point (ºC) <5 4 <5 4 approx. 13 4
Brookfield Brookfield Brookfield
Viscosity at 23ºC (mPa * s) approx. 35 4 approx. 50 4 approx. 150 4
, 60 rmp , 60 rmp , 60 rmp
DIN DIN DIN
Foam power (cm3) approx. 20 4 approx. 50 4 approx. 440 4
53902-1 53902-1 53902-1
Hydroxy number (mg KOH/g) approx. 174 4 approx. 153 4 approx. 112 4
HLB approx. 8 4 approx. 9 4 approx. 12 4
pH (5 % surfactant in water) approx. 7 4 approx. 7 4 approx. 7 4
Cloud point - 1 g surfactant in
approx. 56 4
100 g water (ºC)
Cloud point - 5 g surfactant in 25
g of 25 % butoxyethanol solution Approx. 53 4 approx. 62 4 approx. 79 4
(ºC)
Colour colourless 4 colourless 4 colourless 4
Table A.3 Data commonly available for selected commercial nonionic surfactants, C13-C15 alcohol ethoxylats
Alcohol ethoxylates

H H H
Chain type 5 5 5
R=C13-C15 R=C13-C15 R=C13-C15
Flash point (ºC) approx. 130 DIN 51376 5 approx. 140 DIN 51376 5 approx. 150 DIN 51376 5
Solubility (10 % in water) 23ºC no 5 no 5 (yes) 5
Solubility ( 10 % in 5 % NaCl
no 5 no 5 (yes) 5
solution) 23ºC
Surface tension at 20ºC, 1g
approx. 28 DIN 53914 5 approx. 28 DIN 53914 5 approx. 28 DIN 53914 5
surfactant /l H20 (mN/M)
Wetting ability at 23ºC, 2 g
soda /l H2O, 0.5 g surfactant > 300 DIN 53901 5 > 300 DIN 53901 5 approx. 200 DIN 53901 5
g/l (S)
> 300 DIN 53901 5 > 300 DIN 53901 5 approx. 100 DIN 53901 5
soda/l H2O,1 g surfactant/l (S)
> 300 DIN 53901 5 approx.100 DIN 53901 5 approx. 40 DIN 53901 5
Solidification point (ºC) <5 5 <5 5 <5 5
Brookfield, Brookfield, Brookfield,
Viscosity at 23ºC (mPa * s) approx. 40 5 approx. 50 5 approx. 80 5
60 rmp 60 rmp 60 rmp
DIN DIN DIN
53902-1 53902-1 53902-1
Alcohol ethoxylates

HLB approx. 8 5 approx. 9 5 approx. 10 5
approx.62
25 g of 25 % butoxyethanol approx. 45 DIN 53917 5 approx. 57 DIN 53917 5 DIN 53917 5
solution
Colour colourless 7
R phrases 36/38, 50 7 36/38, 50 5 36/38, 50 5
Acute toxicity -
> 2000 7
LD50/oral/rat (mg/kg)
OECD 301B /
Biodegradability ( % in 28 ISO 9439/
> 70 7
days) EEC 84/445
C.5
Algea toxicity –
0.1 - 1 7
EC50 (72 h) (mg/l)
ISO 9439,
Bacteria toxicity (mg/l) > 10000 pseudomonas 7
putida
Daphnie toxicity –
0.1 - 1 7
EC50 (48 h) (mg/l)
Brochydanio
Fish tox. - LC50 (96 h) (mg/l) 1-10 7
rerio
Alcohol ethoxylates

Structure - formula 5 5 5
H H H
Chain type 5 5 5
R=C13-C15 R=C13-C15 R=C13-C15
approx. 0.96 approx 0.98
Density at 23ºC (g/cm3) approx. 0.98 5 5 5
(60ºC) (60ºC)
Flash point (ºC) approx. 190 DIN 51376 5 approx. 200 DIN 51376 5 approx. 200 DIN 51376 5
Solubility (water) 23ºC yes 5 yes 5 yes 5
Solubility (5 % NaCl solution)
(yes) 5 yes 5 yes 5
23ºC
Surface tension at 20ºC, 1 g
surfactant/l H20 (mN/M)
soda /l H2O, 0.5 g surfactant/l approx. 90 DIN 53901 5 approx. 90 DIN 53901 5 approx. 120 DIN 53901 5
(S)
Solidification point (ºC) approx. 15 5 approx. 18 5 approx. 20 5
Brookfield, approx. 30 Brookfield, Approx. 40 Brookfield,
Viscosity at 23ºC (mPa * s) approx.100 5 5 5
60 rmp (60ºC) 60 rmp (60ºC) 60 rmp
DIN DIN DIN
53902-1 53902-1 53902-1
Alcohol ethoxylates

HLB approx. 12 5 approx. 12.5 5 approx. 13.5 5
Cloud point - 1 g surfactant
in 100 g water (ºC)
Colour Colourless 8
R phrases 22, 36/38, 50 8 22, 36/38, 50 5 22, 36/38, 50 5
S phrases 61 8
Acute toxicity –
> 2000 8
OECD
Biodegradability ( % in 28
> 70 (in 27 days) 301A/ 8
days)
ISO 7827
Algea toxicity –
0.1 - 1 8
EC50 (72 h) (mg/l)
Bacteria toxicity (mg/l) > 1000 Warburg 8
0.1 - 1 8
EC50 (48 h) (mg/l)
0.3 8
NOEC (21 d) (mg/l)
Fish toxicity – Brachydanio
1-10 8
LC50 (96 h) (mg/l) rerio
COD-value (mg O2/g) 2430 8
Alcohol ethoxylates
Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate
Property Method Reference Property Method Reference

RO(CH2CH2O)x RO(CH2CH2O)
Structure - formula 5 5
H xH
aliphatic, aliphatic,
Chain type 5 5
R=C13-C15 R=C13-C15
Surfactant type non-ionic 5 non-ionic 5
Ethoxylation degree approx. 11 5 approx. 30 5
MW average (g/mol) approx. 690 5 approx. 1530 5
Concentration (%) approx. 100 5 approx. 100 5
Density at 60ºC (g/cm3) approx. 0.99 5 approx. 1.03 5
Flash point (ºC) approx. 220 DIN 51376 5 approx. 250 DIN 51376 5
Solubility (10 % in water) 23ºC yes 5 yes 5
Solubility (10 % in 5 % NaCl
yes 5 yes 5
solution) 23ºC
approx. 31 DIN 53914 5 approx. 40 DIN 53914 5
surfactant/l H20(mN/M)
soda approx. 130 DIN 53901 5 > 300 DIN 53901 5
/l H2O, 0.5 g surfactant/l (S)
approx. 60 DIN 53901 5 > 300 DIN 53901 5
approx. 30 DIN 53901 5 > 300 DIN 53901 5
Alcohol ethoxylates
Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate

Solidification point (ºC) approx. 20 5 approx. 35 5
Brookfield, Brookfield,
Viscosity at 60ºC (mPa * s) approx.30 5 approx. 60 5
60 rmp 60 rmp
DIN 53902- DIN 53902-
Foam power (cm3) approx. 400 5 approx. 360 5
1 1
Hydroxy number (mg KOH/g) approx. 80 5 approx. 37 5
HLB approx. 14 5 approx. 17 5
pH (5 % surfactant in water) approx. 7 5 approx. 7 5
approx. 86 DIN 53917 5
Colour Colourless 5 Colourless 5
R phrases 22, 36/38 9
Acute toxicity-
2450 9
Algea toxicity –
1-10 9
EC50 (72 h) (mg/l)
Bacteria (mg/l) > 1000 Warburg 9
1-10 9
EC50 (48 h) (mg/l)
Fish toxicity – Brachydanio
1-10 9
LC50 (96 h) (mg/l) rerio
Table A.4 Data commonly available for selected commercial nonionic surfactants, iso-C13 alcohol ethoxylates
Alcohol ethoxylates
Physico-chemical properties iso-C13 ethoxylate iso-C13 ethoxylate iso-C13 ethoxylate

H H H
branched branched branched
Chain type aliphatic, R= iso 6 aliphatic, R= iso 6 aliphatic, R= iso 6
C13 C13 C13
MW average (g/mol) approx.340 6 approx. 430 6 approx. 500 6
Flash point (ºC) > 100 DIN 51376 6 > 100 DIN 51376 6 > 100 DIN 51376 6
Solubility (10 % in water) 23ºC no 6 No 6 no 6
Solubility (10 % in 5 % NaCl
no 6 No 6 no 6
solution) 23ºC
soda /l H2O, 0.5 g surfactant/l > 300 DIN 53901 6 approx. 80 DIN 53901 6 approx. 60 DIN 53901 6
(S)
> 300 DIN 53901 6 approx. 50 DIN 53901 6 approx. 20 DIN 53901 6
Alcohol ethoxylates
Physico-chemical properties iso-C13 ethoxylate iso-C13 ethoxylate Iso-C13 ethoxylate

Solidification point (ºC) <5 6 <5 6 approx. 5 6
Brookfield, Brookfield, 60 Brookfield,
Viscosity at 23ºC (mPa * s) approx.50 6 approx. 70 6 approx. 100 6
60 rmp rmp 60 rmp
DIN 53902- DIN
Foam power (cm3) approx. 10 6 approx. 50 DIN 53902-1 6 approx. 120 6
1 53902-1
Hydroxy number (mg
KOH/g)
HLB approx. 9 6 approx. 10.5 6 approx. 12 6
in 25 g of 25 % approx. 40 DIN 53917 6 approx. 62 DIN 53917 6 approx. 70 DIN 53917 6
butoxyethanol solution (ºC)
Colour colourless 10 colourless 11
R phrases 36/38 10 36/38 11
Acute toxicity –
>2000 10 > 2000 11
OECD OECD 301E/
Biodegradability
75 screening 10 > 70 EEC 84/449 11
( % in 28 days)
test C.3
Algea toxicity –
1-10 11
EC50 (72 h) (mg/l)
1-10 11
EC50 (48 h) (mg/l)
Fish toxicity – Leuciscus Leuciscus
1-10 10 1-10 11
LC50 (96 h) (mg/l) idus idus
COD-value (mg O2/g) 2595 10 2438 11
Alcohol ethoxylates
Physico-chemical properties iso-C13 ethoxylate iso-C13 ethoxylate

RO(CH2CH2O)x
Structure - formula 6 RO(CH2CH2O)xH 6
H
branched
branched aliphatic,
Chain type aliphatic, R= iso 6 6
R= iso C13
C13
MW average (g/mol) approx. 600 6 approx.750 6
approx. 0.99
Density at 23ºC (g/cm3) approx.1.01 6 6
(60 ºC)
Flash point (ºC) > 100 DIN 51376 6 > 100 DIN 51376 6
Solubility (10 % in water) 23ºC yes 6 Yes 6
Solubility ( 10 % in 5 % NaCl
yes 6 Yes 6
solution) 23ºC
soda /l H2O, 0.5 g surfactant/l approx. 70 DIN 53901 6 approx. 120 DIN 53901 6
(s)
Alcohol ethoxylates
Physico-chemical properties iso-C13 ethoxylate Iso-C13 ethoxylate

Solidification point (ºC) approx. 10 6 approx. 20 6
Brookfield, approx. 40
Viscosity at 23ºC (mPa * s) approx. 150 6 Brookfield, 60 rmp 6
60 rmp (60ºC)
DIN 53902-
Foam power (cm3) approx. 550 6 approx. 600 DIN 53902-1 6
1
Hydroxy number (mg KOH/g) approx. 99 6 approx. 75 6
HLB approx. 13 6 approx. 14.5 6
pH (5 % surfactant in water) approx. 7 6 approx. 7 6
25 g of 25 % butoxyethanol approx. 80 DIN 53917 6 approx. 88 DIN 53917 6
solution (ºC)
Colour colourless 12
R phrases 22, 36/38 12
Acute toxicity –
approx. 1080 12
OECD
Biodegradability
90-100% 301A/ 12
( % in 28 days)
ISO 7827
Algea toxicity –
1-10 12
EC50 (72 h) (mg/l)
1-10 12
EC50 (48 h) (mg/l)
Fish toxicity – Leuciscus
1-10 12
LC50 (96 h) (mg/l) idus
Table A.5 Data from the open academic literature for alcohol ethoxylates. A: Concentration not specified. Presumably pure matter.
Alcohol ethoxylates
Physico-chemical
C12 ethoxylate C12 ethoxylate C12 ethoxylate
properties
Property Reference Property Reference Property Reference
RO(CH2CH2O)x
Structure – formula 2 RO(CH2CH2O)xH 2 RO(CH2CH2O)xH 2
H
Chain type aliphatic, R=C12 2 aliphatic, R=C12 2 Aliphatic, R=C12 2
Surfactant type non-ionic 2 non-ionic 2 Non-ionic 2
Ethoxylation degree 3 2 4 2 7 2
A A A
Concentration (%) approx. 100 2 approx. 100 2 Approx. 100 2
Mp (ºC) 17.6 2 20.5 2
Bp (ºC) 234 at 16 mbar 2 152 at 0.013 mbar 2 214 at 0.013 mbar 2
50
Density, d4 (g/cm3) 0.908 2 0.928 2 0.967 2
50
Refractive Index. Nd 1.4391 2 1.441 2 1.4460 2
10-11 ( in heptane) ;
30 ( in hexadecane);
PIT (ºC) 2
37 ( in
hexadecane/squalane)
CMC (mmol/l) – 25ºC 0.046 - 0.064 2 0.08 (23ºC) 2
Delta H micellisation
5.9 2 8.8 2 12.5 2
(KJ/mol) - 25ºC
Delta G micellisation
-24.4 2 -23.9 2 -23.3 to -22.6 2
(KJ/mol) - at 25ºC
Delta S micellisation (J/
102 2 110 2 120 - 201 2
(mol *K)) - at 25ºC
Table A.6 Data from the open academic literature for nonionic surfactants - alcohol ethoxylates.
A: Concentration not specified. Presumably pure matter.
Physico-chemical properties C13 ethoxylates C15 ethoxylates
Property Reference Property Reference
Structure – formula RO(CH2CH2O)xH 2 RO(CH2CH2O)xH 2

Chain type aliphatic, R=C13 2 Aliphatic, R=C15 2
Ethoxylation degree 8 2 8 2
A A
Surface tension (mN/M) at
34.9 2 34.3 2
25ºC
CMC (mmol/l) – 25ºC 0.027 – 0.112 2 0.0035 2
Aggregation number at 25ºC 171 2
Delta H micellisation (KJ/mol)
13.7 2 11.4 2
- 25ºC
Delta G micellisation
-38.7 2 -41.1 2
(KJ/mol) - at 25ºC
Delta S micellisation (J/ (mol
167 2 176 2
*K)) - at 25ºC
Table A.7 Data commonly available for selected commercial anionic surfactants, alkyl sulphates.
Alkyl sulphates
Physico-chemical
Ammonium lauryl sulphate Sodium lauryl sulphate TEA lauryl sulphate
properties
Cas no. (generic)# 68081-96-9 14 68585-47-7 16 68908-44-1 18

EINECS no. 268 364 5 14 271 557 7 16 272 675 1 18
CH3(CH2)n-O-SO3
CH3(CH2)n-O-SO3 NH4 CH3(CH2)n-O-SO3 Na
Structure – formula 15 17 NH(CH2-CH2OH)3 19
n = 9-15 n = 9-15
n = 9-15
Chain type Aliphatic Aliphatic aliphatic
Surfactant type Anionic anionic anionic
MW average (g/mol) 291 15 296 17 423 19
Aqueous solution -
27 ± 0.5 14 29 ± 0.5 16 40.5 ± 0.5 18
concentration (%)
Apperearance at 25ºC clear to hazy liquid 14 liquid 16 clear to hazy liquid 18
Colour pale yellow 14 yellow 16 yellow 18
Odour faint, characteristic 14 faint, characteristic 16 faint, characteristic 18
Unsulphated matter (%) max. 2.0 14 max. 1.0 16 max. 1.5 18
Unreacted matter (%) ammonium sulphate : max. 1.0 14 sodium sulphate: max. 1.0 16 sulphate ion: max. 1.0 18
Unreacted matter (%) ammonium chloride: max. 0.3 14 sodium chloride: max. 0.2 16 chloride ion: max. 0.2 18
Mp (ºC) < - 10 15 15 – 25 17
Bp (ºC) approx. 100 15 > 100 17 approx. 100 19
Alkyl sulphates
Physico-chemical
Ammonium lauryl sulphate Sodium lauryl sulphate TEA lauryl sulphate
properties
Cas no. (generic)# 68081-96-9 14 68585-47-7 16 68908-44-1 18

EINECS no. 268 364 5 14 271 557 7 16 272 675 1 18
CH3(CH2)n-O-SO3
CH3(CH2)n-O-SO3 NH4 CH3(CH2)n-O-SO3 Na
Structure - formula 15 17 NH(CH2-CH2OH)3 19
N = 9-15 N = 9-15
N = 9-15
Density at 20ºC (g/cm3) 1.02 14 1.05 17 1.08 19
Solubility (water) soluble at 20ºC 15 fully miscible at 20ºC 17 fully miscible at 20ºC 19
pH 6.5 ± 0.5 14 9.0 ± 0.5 16 7.0 ± 0.5 18
Viscosity at 20ºC (mPa*s) approx. 5000 14 < 100 (25ºC) 17 approx. 100 19
R phrases R36/38 15 R36/38 17 R36/38 19
S phrases S26 15 S26 17 S26 19
B: Pure surfactant
Table A.8 Data from the open academic literature for an anionic surfactant – sodium lauryl sulphate.
Physico-chemical properties Sodium lauryl sulphate
Property Method Reference
Structure – formula C12H25SO4Na

Chain type aliphatic
Surfactant type anionic
MW average (g/mol) 288.377 3
A
Concentration (%) approx. 100 2
Mp (ºC) 204-207 3
Solubility (water) < 1 g/l H2O 3
C,D
Krafft point in water (ºC) 8 - 16 Solubility 2
C: Several data points exist at this temperature – see original literature
D: Data points exist at other temperatures or by other methods – see original literature
Physico-chemical properties Sodium lauryl sulphate
Property Method Reference

C,D
CMC (mmol/l) – 25ºC 7.4 - 8.27 electrical conductivity 2
CMC (mmol/l) - 35ºC 8.38 electrical conductivity 2
CMC (mmol/l) - 0.1 mol NaCl/l - D Dye solubilisation,
1.46 2
25ºC Electrical conductivity
CMC (mmol/l) - 0.2 mol NaCl/l – D
0.92 Light scattering 2
25ºC
C,D
aggregation no. At cmc - 25ºC 64.4 Light scattering 2
aggregation no. At cmc, 0.1 mol C,D
88-101 Light scattering 2
NaCl/l - 25ºC
aggregation no. At cmc, 0.2 mol C,D
90-97 Light scattering 2
NaCl/l - 25ºC
micelle radius (10 e-9 m) at cmc D
1.91 Density 2
at 25ºC
2.53 Light scattering 2
and 0.1 mol NaCl/l at 25ºC
2.47-2.55 Light scattering 2
and 0.2 mol NaCl/l at 25ºC
Diffusion coefficient (10 e-6
D
cm2/s)at cmc - 0.1 mol NaCl/l - 25 0.96 Light scattering 2
ºC
Diffusion coefficient (10 e-6
D
cm2/s)at cmc - 0.2 mol NaCl/l - 25 0.95-0.98 Light scattering 2
ºC
Delta H micellisation (KJ/mol) - 25 C,D
ºC -2.13 to 2.2 Calorimetry 2
Delta H micellisation (KJ/mol) - 35 C,D
ºC -7.45 to - 4.78 Calorimetry 2
Delta Cp micellisation ( J/(mol K) ) D
-516 Calorimetry 2
– 25ºC
C: Several data points exist at this temperature – see original literature
D: Data points exist at other temperatures or by other methods – see original literature
Table A.9 Data commonly available for a commercial anionic surfactant, An alkyl ether sulphates.
Alkyl ether sulphate

Physico-chemical properties Sodium lauryl ether sulphate
Property Reference
Cas no. (generic)# 68585-34-2 20
Surfactant type anionic 20
Concentration 70.0 ± 1.0 20
Ethoxylation degree 2 20
Density at 20ºC (g/cm3) 1.10 20
Viscosity at 30ºC (mPa * s) 20
Unsulphated matter (%) max. 3.5 20
Sodium sulphate (%) max. 1.5 20
Sodium chloride (%) max. 0.3 20
PH 8.0 ± 1.0 20
B: Pure surfactant
Table A.10 Biodegradability data from the open academic literature13.
C13-C15 ethoxylates C13-C15 ethoxylates alkyl sulphates alkyl ether sylphates
Ethoxylation degree approx. 5 approx. 7

Aerob biodegradable yes yes yes yes
Anaerob biodegradable yes yes yes yes
EC/LC 50 (mg/l) 0.01 – 1 0.75 – 2 0.58 – 1.3 0.4 – 2.5
Potential bio
yes (no) no no
acummulative
Reference list
1. Ash Michael & Irene; “Handbook of industrial surfactants”, vol. 1 & 2, Gower, 1997.
2. Van Os N.M., Haak J.R. & Rupert L.A.M.; " Physico-chemical properties of selected anionics, cationics and non-ionic surfactants"; Elsevier, 1993
3. www.chemfinder.com
4. Lutensol AN marken, Tecnische Information, TI/ES 1145 d, October 1994, BASF
5. Lutensol AO marken, Tecnische Information, TI/ES 1070 d, July1995, BASF
6. Lutensol TO marken, Tecnische Information, TI/ES 1029 d, February 1997, BASF
7. MSDS - Lutensol AO3, 27 July 1997, BASF
8. MSDS - Lutensol AO7, 9 December 1999, BASF
9. MSDS - Lutensol AO11, 30 November 1996, BASF
10. MSDS - Lutensol TO3, 4 July 1997, BASF
11. MSDS - Lutensol TO5, 29 October 1996, BASF
12. MSDS - Lutensol TO8 4 July 1997, BASF
13. Madsen T., VKI; "Miljøvurdering af colour vaskemidler", Teknik & Miljø nr. 10, 1999
14. EMPICOL AL 30/T; Technical information, TD0031, 16 January 1995; Albright & Wilson
15. MSDS - EMPICOL AL 30/T; 28 April 1998; Albright & Wilson
16. EMPICOL LX 28; Technical information, TD0058, 16 January 1995; Albright & Wilson
17. MSDS - EMPICOL LX 28; 22 July 1998; Albright & Wilson
18. EMPICOL TL 40/T; Technical information, TD0067, 16 January 1995; Albright & Wilson
19. MSDS - EMPICOL TL 40/T; 28 April 1998; Albright & Wilson
20. EMPICOL ESB 70; Technical information, TD0049 , 16 January 1995; Albright & Wilson
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Center for Miljø og Luftveje

Their abilities and important

Their abilities and important

Rapport fra Center for Miljø og Luftveje

Charlotte Pilemand, EnPro ApS

Their abilities and important

Charlotte Pilemand, EnPro ApS

In 1998 the Danish Environmental Research Programme for 1998-2001 "Environmental

In this report data on structure, HLB-values (HLB=hydrophilic Lipophilic Balance),

On behalf of the Centre for the Environment and the Lung

Otto Melchior Poulsen

2.1 Surfactants in general

non-polar part polar part

Figure 2.1 Schematic surfactant molecule

Figure 2.2 The four different main types of surfactants.

Examples of anionic surfactants:

2.1.2 Non-ionic surfactants

Examples of ethoxylated non-ionic surfactants:

Examples of multihydroxy non-ionic surfactants:

2.1.3 Cationic surfactants

Examples of cationic surfactants:

• Quaternary Ammonium Salts

Examples of amphoteric surfactants:

3.1 Emulsification and solubility

One of the widest applications of surfactants is to solubilise or to disperse water insoluble

Detergency is removal of soil from a substrate immersed in a medium, generally

4.1 Critical micelle concentration

4.2 Krafft point

If a surfactant solution needs to show surface-activity based abilities, such as wetting,

4.4 HLB number

HLB = % of molar hydrophilic group dived by 5

4-7 Poor dispersion (unstable) W/O

7-9 Stable opaque dispersion -

10-13 Hazy solution O/W

≥ 13 Clear solution O/W

HLB no. Surfactant application

1-3 Antifoaming agents

3-6 W/O emulsifiers

7-9 Wetting agents

8-18 O/W emulsifiers

4.5 Phase inversion temperature

An alternative method for characterising emulsifying agents is the phase inversion

4.6 Surface tension

When formulating or reformulating a product containing surfactants it is important to

Surfactant Type Synonyms CAS numbers

Property Method Reference Property Method Reference Property Method Reference

Physico-chemical properties C12-C14 ethoxylate C12-C14 ethoxylate C12-C14 ethoxylate

Property Method Reference Property Method Reference Property Method Reference

Ethoxylation degree approx. 3 4 approx. 4 4 approx. 7 4

Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate C13-C15 ethoxylate

Property Method Reference Property Method Reference Property Method Reference

Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate C13-C15 ethoxylate

Property Method Reference Property Method Reference Property Method Reference

Ethoxylation degree approx. 3 5 approx. 4 5 approx. 5 5

Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate C13-C15 ethoxylate

Property Method Reference Property Method Reference Property Method Reference

Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate C13-C15 ethoxylate

Property Method Reference Property Method Reference Property Method Reference

Ethoxylation degree approx. 7 5 approx. 8 5 approx. 10 5

Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate

Property Method Reference Property Method Reference

Physico-chemical properties C13-C15 ethoxylate C13-C15 ethoxylate

Property Method Reference Property Method Reference