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Chemical Formulation: An Overview of Surfactant Based Chemical Preparations Used in Everyday Life
Chemical Formulation: An Overview of Surfactant Based Chemical Preparations Used in Everyday Life
Chemical Formulation: An Overview of Surfactant Based Chemical Preparations Used in Everyday Life
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Chemical Formulation: An Overview of Surfactant Based Chemical Preparations Used in Everyday Life

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Chemical formulation can be traced back to Stone Age times, when hunter-gatherers attached flint arrowheads to shafts using a resin made from birch bark and beeswax. Today, formulated preparations are part of everyday life. Formulations based on surfactants are by far the most prolific, from shampoos and shower gels to emulsion paint and polishes. This book discusses the chemical technology of surfactants and related chemicals, using over forty examples of everyday products. Some basic theory on surface chemistry, molecular interactions and surfactant function is included to aid understanding. Chemical Formulation: An Overview of Surfactant-based Preparations Used in Everyday Life then goes on to look at wider aspects such as surfactant manufacture, raw materials, environment, sustainability, analysis and testing. Throughout, common chemical names are used for formulation chemicals, further aiding the readability of the book. Bridging the gap between theory and application, this book will be invaluable to anyone wishing to broaden their knowledge of applied chemistry, including students on A level, BTEC and technician courses. It will also be of benefit to those new to the formulation industry.
Release dateAug 28, 2003
Chemical Formulation: An Overview of Surfactant Based Chemical Preparations Used in Everyday Life

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    Chemical Formulation - Anthony E Hargreaves


    An Overview of Surfactant-based Preparations Used in

    Everyday Life

    RSC Paperbacks

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    An Overview of Surfactant-based Preparations Used

    in Everyday Life



    ISBN 0-85404-635-6

    EPUB ISBN: 978-1-78801-833-3

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    © The Royal Society of Chemistry 2003

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    My first experience of the chemistry of surfactant-based formulations was when I was working on analysis of solvent blends by Gas Chromatography (GC) back in the early 1980s. In addition to GC work our laboratory would also carry out comparative studies of surfactant formulations like shampoos and related products.

    Instrumental methods such as GC or Infra-red (IR) were out of the question because of the disproportionate amount of preparation required to make the sample, or a part of it, ‘instrument ready’. As such many of these comparative studies were confined to quick and simple tests: pH, conductivity, solids, ash and indicator tests for surfactant type.

    From time to time we would be asked: Can you test this and give an idea of how to make an equivalent? Although cautious of trespassing on someone else’s intellectual property we would often take up the challenge of making and matching formulations based on surfactants. It was an interesting diversion: instead of the analytical approach of breaking down formulations we could go in the opposite direction and build them up.

    It was then that I began to appreciate the difficulty of getting even a basic understanding of what goes into formulations, the amounts used and how each component functions. For a start the raw materials were commercial products with commercial names and often it was a problem knowing what the chemistry was. Although there were many formulations provided by chemical suppliers for us to study there seemed to be few, if any, guidance rules. It was only after a lengthy exercise of studying formulations, basic surfactant chemistry and discussions with surfactant manufacturers that I was able to form a generalised picture of what was going on.

    This book is a summary of the chemistry and technology that was pulled together in the attempts to see more clearly what chemicals go into everyday preparations, how those chemicals function and some related aspects such as environmental effects. Hopefully the book will be of value for those with an interest in household chemicals, others who may wish to consider making such products as a commercial venture and students with an interest in applied chemistry.

    In preparing this book I have used many formulations provided by surfactant manufacturers and to them I wish to express my gratitude. In particular I wish to thank Nick Challoner and Rebecca Webster at Croda Oleochemicals for permission to use their formulations and for the many helpful suggestions to ensure that what is reported is as up-to-date and accurate as possible. I would wish to extend my thanks to Chris Howard at Stepan UK and to Simon Nicholson at Huntsman Surface Sciences for their kind assistance.



    Chapter 1

    Formulation Chemicals

    Chemical Names



    Acids and Bases (Alkalis)



    Chelating Agents, Sequestrants


    The Process of Dissolving

    Ionic Bonds

    Covalent Bonds

    Hydrogen Bonds

    Dipole-Dipole Attractions

    Van der Waals Attractions

    Example 1, Dissolving Sodium Chloride in Water

    Example 2, Dissolving Paraffin Wax in Hexane

    Example 3, Dissolving Sucrose in Water

    Example 4, Dissolving Ethanol in Water

    Example 5, Hydrocarbon Oil and Water

    General Rule


    Aliphatic Hydrocarbons

    Aromatic Hydrocarbons

    Hydrocarbon Blends and Distillates


    Halogenated Hydrocarbons

    Nitrogen Compounds

    Sulfur Compounds

    Choice of Solvent


    Animal Waxes


    Shellac Wax


    Plant Waxes


    Mineral Waxes


    Paraffin Waxes

    Synthetic Waxes

    Polyethylene Glycols (PEGs)





    Corrosion Inhibitors

    Foam Makers and Breakers




    Chapter 2

    Surfactants in Action

    Surface Tension



    Types of Surfactants

    Anionic Surfactants

    Cationic Surfactants

    Non-ionic Surfactants

    Amphoteric Surfactants

    Surfactants, the Future

    Hydrotropes and Viscosity


    Stability of Emulsions

    The HLB System





    Chapter 3




    Sodium Lauryl Ether Sulfate

    Sodium Chloride

    Coconut Diethanolamide

    Coco Amido Propyl Betaine


    Citric Acid

    Quaternary Cationic

    Tetrasodium EDTA

    Formaldehyde, Methyl Paraben and Propyl Paraben


    Machine Dish-wash Powder

    Sodium/Potassium Salts

    EO/PO Surfactant

    Sodium Dichloroisocyanurate

    Convenience Food

    Hydrogenated Vegetable Oil



    Acidity Regulator





    Chapter 4

    Further Formulations

    Personal Care Products

      1  Conditioning Shampoo

      2  Shampoo for Dry Hair

      3  Shampoo for Greasy Hair

      4  Pearlized Shampoo

      5  Conditioning Rinse

      6  Foam Bath

      7  Soluble Bath Fragrance

      8  Shower Gel

      9  Roll-on Antiperspirant

    10  Baby Cleansing Lotion with Lanolin

    11  Baby Cream

    12  Liquid Soap

    13  Toothpaste

    14  Barrier Cream

    15  Cleansing Beauty Milk

    16  Natural Moisture Cream

    17  Insect Repellent Cream

    18  Aerosol Shaving Foam

    Household Products

    Dish-wash Liquids

    19  Dish-wash Liquid 10% Active

    20  Dish-wash Liquid 20% Active

    21  Dish-wash Liquid 30% Active

    22  Air Freshener Gel

    23  Heavy Duty Degreaser

    24  Furniture Polish, Plant Wax

    25  Shoe Cream

    26  Furniture Polish, Siliconized

    27  Metal Polish

    28  Machine Dish-wash Powder

    29  Oven Cleaner

    30  Cream Hard Surface Cleaner

    31  Thick Acid Toilet Cleaner

    32  Carpet Shampoo

    33  Glass Cleaner

    34  Car Shampoo Concentrate

    35  Screenwash

    36  Rust Remover

    37  Thickened Peroxide Bleach

    38  General Hard Surface Cleaner with Pine Oil

    39  Surface Cleaner/Biocide

    40  Hand Gel Kerosene Base

    Blending the Chemicals

    Modifying Formulations


    Quality of Chemicals

    Attempting a Formulation

    Chapter 5

    Environment and Resources

    Manufacture and Resources





    Chelating Agents, Salts, Alkalis


    Environment and Pollution

    Chemical Production

    Formulated Products in Use

    In Perspective

    Chapter 6

    Formulation Analysis

    Basic Methods

      1  Preliminary Examination

      2  Total Solids Content

      3  Ash Determination

      4  Suspended Solids

      5  Dissolved Solids

      6  Emulsions, o/w or w/o

      7  Solvent Extraction

      8  Soxhlet Extraction

      9  Methylene Blue

    10  Dimidium Bromide

    11  Conductivity

    12  pH Determination

    13  Acid/Base Titration

    14  Back Titration

    15  Active Chlorine Titration

    16  Hydrogen Peroxide Titration

    17  Iodine Value

    18  Tests on Ash

    19  Tests on Organics

    20  Distillation, Boiling Point/Range

    21  Dean & Stark

    22  Ammonia Distillation

    23  Kjeldahl Nitrogen

    24  Sequestering (Chelating) Capacity

    25  Karl Fisher

    26  Viscosity

    27  Ross-Miles Foam Test

    28  Drave’s Test

    29  Phase Inversion Temperature

    30  Thin-layer Chromatography

    31  Cloud Point

    32  Saponification Value

    Instrument Methods

    Infra-red (IR) Spectroscopy

    Nuclear Magnetic Resonance (NMR)

    Mass Spectrometry (MS)

    Gas Chromatography (GC)

    Headspace GC

    Pyrolysis GC

    Gas Chromatography–Mass Spectrometry (GC–MS)

    Other Instrument Methods


    Subject Index

    Abbreviations Used


    Chemical formulations go so far back in time that we must turn to the archaeologist for examples. As long ago as Mesolithic times when people were hunter-gatherers they attached worked flint arrow heads to shafts by means of a blend of resin extracted from birch bark and made plastic with beeswax to produce a substance that had the best properties for the job.

    Resin alone, once set, produces a brittle mass but when blended with just the right amount of beeswax it provides not only a strong adhesive but also has sufficient flexibility to withstand the mechanical forces imposed on a weapon such as an arrow.

    Found only in certain limestone deposits flint was scarce and often was brought from far and wide. And so it seems reasonable to assume that a great deal of care went into any experiments of which it formed a part. Quite simply, a lost arrow point demanded a replacement that took a skilled person some time to make and required a fairly large chunk of that valuable material.

    One can imagine that the process would follow the lines: theory, experiment, result, interpretation, new theory, new experiment, new result and so on until performance was optimized. Those stone-age experiments were in fact an early application of plasticizing a polymer -the beeswax was the plasticizer. The product must have been used as a hot melt adhesive which, on cooling, left the flint arrowhead firmly, but flexibly, bonded to its pine shaft.

    The very same principle of plasticizing a polymer is used today to turn rigid uPVC (unplasticized PVC) into pliable PVC. Yes, we use a ten thousand year old discovery to take the ‘u’ out of uPVC. There are other examples from antiquity but the beeswax/resin example is of particular significance in a scientific context as it would have called for a good deal of quantitative experimental work to optimize the properties of the blend.

    Eventually the hunter-gatherer lifestyle gave way to living in settled communities as a result of early agriculture. Now, instead of travelling far and wide to catch animals the task was simplified with much time and effort saved. With the animals in their pens and people living in settled communities two very favourable conditions, the availability of spare time and permanent work space, provided for a basic knowledge of materials to be developed.

    The interest in materials led to the discovery of many chemical reactions that were to mark the onset of materials technology. Thus the foundation was laid for the high temperature chemistry that turns sand and clay into pot. The importance of recognizing essential properties was being learnt: quality of raw materials, proportions to blend together to achieve certain effects, estimation of kiln temperature, rate and duration of firing.

    Later on, other high temperature reaction based processes were discovered, studied and refined to give rise to a new technology based on chemical reduction of a greenish rock to produce bronze. Still later, the iron-age, based on turning brown iron ore into iron developed. Thus, chemical technology was well established in times of antiquity. Much of the chemistry involved was brute force chemical reaction, high temperature stuff.

    In general, chemistry is recognized in its ability to bring about reactions to effect a permanent change from one substance to another; the latter bearing no resemblance to that from which it was made - just like the green rock to bronze referred to above. However, the chemistry involved in making the plasticized resin did not involve chemical reactions to create new substances but was the practice of making chemical mixtures. It is the preparation of mixtures that is the essence of formulation work.

    The properties of mixtures reflect the properties of the substances from which they are made and the mixtures can, by means of simple techniques, be split into their component substances. Often, to the frustration of the chemical formulator, a prepared mixture separates out on its own.

    So, now to consider some simple two-part mixtures; some of these are natural and others are man-made ones:

    Some everyday materials, particularly those that form parts of living systems, go even further and involve combinations of the above types in some incredibly complex mixtures. In the formulations discussed in the following pages the mixtures are relatively simple: solutions, emulsions, suspensions and foams. But just because a mixture is simple in terms of the number of components does not mean it is simple at the molecular level.

    The aim in making formulated preparations is to take readily available substances (man-made or natural) to arrive at a preparation that is tailor-made for a specific task, a task that cannot be effectively carried out by a single substance working on its own. This requires a good deal of applied science and much of that is chemistry. In addition to the technical aspects of putting a preparation together there will also have been a study of many of the other aspects that are essential if a preparation is to be a commercial product.

    Each of the following all have a role to play: formulation recipe, chemicals information, reactivity considerations, blending method, testing and analysis, stability trials (physical/chemical/microbiological) and shelf-life, health and safety, environment resources and waste, quality control, packaging and container interactions, labelling and user instructions and warnings as to adverse effects.

    In all of this there is a big responsibility to ensure the product is fit for its intended purpose. This extends to an awareness of how the chemical blend may interact, physically or chemically, with the materials with which it comes into contact during use.

    For example, a cleaning preparation based on ammonia may well have excellent performance on most surfaces but failure to point out that it should not be used on marble surfaces could turn out to be embarrassing, as could the fact that an acid-based metal brightener when in contact with stainless steel turns the steel black. Of course not all situations can be predicted but what happens to a preparation once it is in the user’s hands is something for consideration.

    There is a tendency to think that once a formulation has been put together and shown to be stable, over a period of days, that it will remain as such ad infinitum. This is almost never the case. It is not unknown for containers with apparently stable, safe and unreactive mixtures in them, even after sitting in a cold storeroom for months or years, to explode due to gassing of the contents or for a natural solvent blend, after being put into a polythene bottle, to ooze out through the polythene and leave a crumpled and collapsed bottle sitting in a sticky pond.

    Chemical preparations are the basis of a whole range of modern materials in the home and at work. By far the largest proportion of these - largest in terms of both tonnage and variety - is formulations that involve surfactants. In fact it was developments in surfactant chemistry that laid the foundation for many of the chemical formulations we see today.

    Surfactants are to be found as important ingredients in shampoos, shower gel, skin creams and ointments, bactericides, surface cleaners, polishes and abrasives, washing powders and liquids, fabric conditioners, engine oil, food and drink, pharmaceuticals, agricultural pesticides, emulsion paints, adhesives, bleach, solvents, toothpastes and mouthwash. The list is endless because it continues to grow.

    Today much of the momentum of that growth comes from our desire to move away from solvent preparations, such as the volatile organic compounds (VOCs) that pollute the atmosphere, towards water-based systems, and that means surfactant-based ones.

    Any chemical preparation must remain as a coherent mixture for a reasonable length of time; it must be stable. A product with poor stability in which the components separate out and which requires an expiry date only two weeks from date of manufacture is not going to go far in terms of customer satisfaction.

    Achieving what at first sight seem to be simple criteria is hardly ever straightforward. For example, a solution of gum acacia is easy to prepare and, to begin with, gives all the impression of being stable. However, a few days later the situation will be very different as it has turned cloudy and clumps of fungal growth adorn its surface.

    What seemed to be a simple task of weighing out, dissolving, straining and bottling is now a bit more involved.

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