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Bleaching systems in domestic laundry detergents:

a review
Cite this: RSC Adv., 2015, 5, 65365
Giulia O. Bianchetti,a Carolyn L. Devlin*b and Kenneth R. Seddonb

Received 25th March 2015
Accepted 21st July 2015
DOI: 10.1039/c5ra05328e
www.rsc.org/advances
Laundry detergent is an indispensable commodity which is used by consumers worldwide. The global
market for laundry detergents is in the region of $60.9 billion (2012, based on retail value), of which $11.7
billion comes from Western Europe. Non-chlorine bleach was incorporated in a detergent for the first
time just over a century ago and it remains an important component of detergents, particularly powder
detergents. Detergent development is mainly carried out in industrial laboratories and, as a result,
relatively few papers have been published in this area. The aim of this review is to compile this
information, along with that contained in the patent literature and other sources, to give future
researchers a more comprehensive overview of this important topic. Specifically, oxygen-based
bleaching systems have been examined, with focus on their development through the years. Current
research targets as described by the available literature are also discussed, such as the development of
better bleaching species, alternative bleach systems, and steps to incorporate a bleaching system in
liquid laundry detergents (a key development which continues to elude researchers).

detergent’ contained in the title or abstract of patents led.3

1 Introduction
This review will give the reader an introduction to the world of
the common household laundry detergent, with emphasis on
the bleaching action of detergents, and including the history
and development of detergent bleaches, as well as outlining
current research targets in this area, as described in the litera-
ture. Laundry detergent is an indispensable commodity which
is used by consumers worldwide. The global market for laundry
detergents is in the region of $60.9 billion† (2012, based on
retail value), of which $11.7 billion comes from Western
Europe.1
There is very little information in the primary literature
about this topic, as the majority of the work is carried out in
industrial laboratories and revealed to the wider scientic
community mainly through patent applications and the occa-
sional book or conference proceedings. From 2005 to 2014, a
Web of Science search reveals just 153 articles for the topic
‘laundry detergent’;2 although on further examination, many of
these articles relate to toxicity and exposure studies rather than
new developments. However, a quick search of the patent
literature tells a different story. For the same period, http://
www.espacenet.com gives over 1700 results for ‘laundry
a
Procter & Gamble Services Company NV/SA, 1853 Strombeek Bever, Belgium. E-mail:
Bianchetti.g@pg.com
b
QUILL Research Centre, School of Chemistry and Chemical Engineering, The Queen's
University of Belfast, Belfast, Northern Ireland, UK, BT9 5AG. E-mail: cdevlin25@qub.
ac.uk; k.seddon@qub.ac.uk
† In all instances in this paper, billion is used to represent the more precise term,
milliard (1000 million, 109).
This correlates to over 170 patent applications per year, which
indicates a strong industrial interest.
To avoid any ambiguity in this work, it is necessary to clarify
some terms here. Firstly, it is important to establish what is
meant by ‘detergent’. Oen the word detergent is used to
describe surfactants, or any material which has ‘detergency’ or
‘surface-active’ properties. However, here, the word detergent
will be used solely to describe a formulation, of which surfac-
tants are the main, but not the sole, active component: ‘a
detergent is a formulation comprising essential constituents
(surface-active agents) and subsidiary constituents (builders,
boosters, llers and auxiliaries)’.4
Secondly, and specically, this review will discuss laundry
detergents for domestic use. Laundry detergents for use outside
the home (e.g. in hospitals, restaurants, and hotels) are classi-
ed separately as industrial and institutional (I&I) detergents.
The groups are distinguished because there are considerable
differences between them. For example, in the average house-
hold, a single laundry detergent may be used to wash several
types of fabric, of different colours, both lightly and heavily
soiled, at different temperatures. However, a commercial
laundry will typically encounter a specic wash load e.g. in a
hotel, the wash load typically consists of lightly soiled towels
and linens, which have predictable soils arising from make-up,
cosmetics and body oils.5 As a result, the washing programme
can be tailored to suit those specic stains and fabrics.
Commercial laundry machines oen have multi-compartment
dispensers, which can automatically introduce separate deter-
gent components into the wash, as needed.5 This means that

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instead of using a fully-formed single detergent product, the
detergent components can be purchased and added separately.
The composition of the detergent is also adapted to suit
conditions: as commercial laundries oen use soened water,
this reduces the need for hard metal complexing agents,5 and
commercial detergents still contain phosphate builders (up to
40%), as their use has not been restricted for industrial and
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institutional use as it has for domestic detergents.6 The market
for industrial and institutional laundry detergents is not as
large as that for domestic laundry detergents, but it is still
signicant: A.I.S.E., the International Association of Soaps,
Detergents and Maintenance Products (or Association Inter-
nationale de la Savonnerie, de la Détergence et des Produits
d'Entretien), estimates that the European (EU 28, plus Norway
and Switzerland) market for laundry products for industrial and
institutional uses was V658 million in 2013.7
It has already been stated that this paper will focus on those
domestic laundry detergents containing bleach. To avoid any
ambiguity in this work, it is necessary to establish that by
bleach we mean non-chlorine bleach. The best known chlorine
bleach is probably sodium hypochlorite, which is sold as a
stand-alone product. To date – given its reactivity – it cannot be
incorporated into detergents. This review focusses on non-
chlorine bleaches that can be incorporated in detergents.
Bleach is an active component in numerous cleaning products,
including detergents for laundry and dish care, laundry addi-
tives, and products for hard surface cleaning. Laundry additives
are products which are used by consumers, in combination
with detergents, as detergent boosters. Standard domestic
powder laundry detergents contain bleach. This is typically
listed in the ingredients section under the title ‘oxygen-based
bleaching agents’ (Fig. 1).
Oxygen-based bleaching agents refer to hydrogen peroxide
and related compounds, and differentiate from those bleaches
based on chlorine. Chlorine bleaches are used in hard surface
cleaners as well as some laundry additives for whites. The main
functions of a bleach system are to provide whiter garments
(through dingy removal), and to remove stains, either alone or
in combination with a surfactant system. In most cases, bleach
systems work through oxidation mechanisms; however, there
are some commercially available products which use reducing
agents, such as thiourea dioxide, C(]NH)(NH2)S(]O)OH.
These are typically powder products, and for specic purposes
such as targeting dye bleeding in the wash, or for whites reju-
venation (e.g. lingerie whiteners from Dylon8).
Fig. 1 Standard domestic detergent ingredients, as described on a
typical product packet.
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Fig. 2 Bleich-Soda19 from 1878 (left) and the first Persil20 package in
1907 (right).
In Europe, bleach has been a component of laundry deter-
gent since the earliest days of detergents. Laundry detergent
itself is a relatively new product, having existed for little over a
century. Predating detergents, there was soap (which, in its
basic form, is simply the sodium or potassium salt of a fatty
acid).9 Numerous references to soap have been uncovered
dating back over four thousand years from the Babylonians ca.
2800 BC,10 to the Sumerians ca. 2200 BC,11 the Ancient Egyptians
ca. 1500 BC,12 and the Phœnicians ca. 600 BC.13,14 Throughout
the millennia and these varied civilisations, the essential recipe
for soap remained the same; a crude mixture prepared by
boiling together vegetable and/or animal fats with alkaline salts;
potash (potassium carbonate) or soda ash (sodium carbonate).
The alkaline salts were usually sourced from burning wood/
trees.15 This process continued right up until the 18th century,
and hard soap prepared in this way was employed for various
uses including personal hygiene, laundry and medicinal
purposes.
In the 19th century, soap powders and akes became avail-
able; however, these products were mostly pulverised soap,
sometimes mixed with soda ash, and therefore, under our
earlier denition, were not detergents. Additives began to
appear which improved performance. These were used along-
side, or sometimes incorporated into, the soap products. For
example, in 1878, the German manufacturer Henkel released a
product known as Bleich-Soda (bleaching soda, Fig. 2), which
contained sodium carbonate (soda) and sodium silicate (water
glass), to the German market.16 When used with soap, this
prevented the build-up of water-insoluble soap residues; a
problem which arose in areas of hard water.17 Sales of Bleich-
Soda soared in the succeeding years, highlighting a demand for
multi-component laundry systems.16 Despite the name, Bleich-
Soda didn't actually contain bleach. The rst detergent to
contain bleach was Persil‡ (Fig. 2), which was released by
Henkel in 1907; also in Germany.18 Persil's main ingredients
were soap (which at that time was still based on animal/vege-
table fats), sodium carbonate, sodium silicate and hydrogen
‡ The Persil trade name is now used on compositions owned in some countries by
Henkel and others by Unilever.
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peroxide (in the form of sodium perborate). The name Persil
stemmed from the two active ingredients: ‘per’ from perborate,
and ‘sil’ from silicate. At the time of its release, Persil was
described as the rst ‘self-acting detergent’18 because, with the
inclusion of sodium perborate, it signicantly decreased the
workload of doing laundry by hand. Clothes no longer needed
to be scrubbed by hand or hung outside for prolonged periods
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to be bleached by the sun. The demand for Persil grew.
2 Oxygen-based bleaching agent:
hydrogen peroxide
As already stated, the bleach-active ingredient in Persil was
sodium perborate, which is a type of compound known as a
persalt or solid hydrogen peroxide carrier. Persalts release
hydrogen peroxide when they come into contact with water.
Hydrogen peroxide (H2O2) was rst discovered in 1818 by Louis-
Jacques Thenard.21 Pure hydrogen peroxide is a pale blue,
viscous liquid, but hydrogen peroxide is typically sold either as a
persalt or an aqueous solution (up to 70% w/v as more
concentrated solutions are hazardous).22 It is extremely impor-
tant to understand the hazards associated with hydrogen
peroxide. In all forms, hydrogen peroxide is thermodynamically
unstable and undergoes a disproportionation reaction, evolving
oxygen and generating heat, eqn (1) and (2).21
H2O2(g) / H2O(g) + ½O2(g); DH ¼ 105.8 kJ mol1
H2O2(l) / H2O(l) + ½O2(g); DH ¼ 98.3 kJ mol1
Hydrogen peroxide is kinetically stable in the absence of
catalysts or other accelerating factors (e.g. light, heat), and strict
storage conditions (typically involving radical scavengers, the
minimisation of transition metal ion sources, and an acidic pH)
can minimise decomposition. However, even low levels of
decomposition generate oxygen, which can pressurise sealed
equipment and create ‘oxygen enrichment’ in the headspace of
the container.21 The decomposition rate increases with
temperature at a rate of 2.3 times per 10  C.21 While hydrogen
peroxide solutions are non-ammable (at all concentrations),
the powerful oxidising properties of hydrogen peroxide, coupled
with the evolution of heat and oxygen on decomposition, makes
hydrogen peroxide a very efficient re initiator. Mixtures made
at high hydrogen peroxide concentration can surpass TNT in
terms of explosive power, and approach nitroglycerine with
regard to shock sensitivity (Table 1).
Table 1Comparison of explosive powers and shock sensitivities of
some materials21
Substance Explosive power Sensitivity (kg cm)
Nitroglycerine 52 2–5
85% w/w H2O2/glycerol 46 10–15
70% w/w H2O2/polyethylene 30 22
Picric acid 32 75
Trinitrotoluene (TNT) 30 150
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Fig. 3 Left: Sodium perborate tetrahydrate; Right: structure of the
anion (hydrogen atoms not shown), generated from the crystal
structure determined by Hansson.24
As a result, storage conditions are critical to avoid the risk of
explosion for concentrated hydrogen peroxide, both in liquid
and solid forms. Solid sources of hydrogen peroxide proved
more suitable for inclusion in detergent products, as solid soap
forms were used for laundry purposes, ca. 1900. Pure hydrogen
peroxide has an active oxygen content of 47%. In detergent
chemistry, the term active oxygen refers to peroxy compounds,
which contain the (–O–O–) linkage, in which one of the oxygen
atoms is active. The active oxygen content of a compound is the
atomic mass of active oxygen divided by the molecular mass of
the compound, and is usually expressed as a percentage:22
100  no: of active oxygen atoms  16
Active oxygen % ¼
molecular weight of compound
When sodium perborate was rst included in detergents, it
was used in the form known as sodium perborate tetrahydrate. A
(1)
second grade, known as sodium perborate monohydrate, became
(2) available later. The two grades differ by the number of waters of
crystallisation present. However, both names are misleading as
they are not directly related to the composition, due to an inac-
curate initial understanding of the structures.23 When the tetra-
hydrate was rst prepared, its structure was reported as
NaBO3$4H2O. However, in 1961, the crystal structure was deter-
mined by Hansson,24 and shown to be the disodium salt of the
1,4-diboratetroxane dianion [Na2B2(O2)2(OH)4$6H2O] (Fig. 3).
This was later conrmed by Carrondo and Skapski in 1978.25
The IUPAC name is sodium tetrahydroxo-di-m-peroxodibor-
ate(III) hexahydrate, however the commercial product is still
referred to as sodium perborate tetrahydrate and its molecular
structure is almost always reported as NaBO3$4H2O, with an
associated molecular mass of 154.23§ Sodium perborate tetra-
hydrate has an active oxygen content of ca. 10%.26
Sodium perborate monohydrate was later prepared by
dehydration of the tetrahydrate form. The nomenclature of the
monohydrate is also inaccurate, and is based on the structure
incorrectly being described historically as NaBO3$H2O. The
crystal structure of the monohydrate has not been determined;
however, it is believed to contain the same cyclic structure as the
tetrahydrate (Fig. 3), and does not have any water of crystal-
lisation. The monohydrate has a faster dissolution prole
compared to the tetrahydrate, and also has a higher active
oxygen concentration (ca. 16%). These advantages increased the
use of the monohydrate over the tetrahydrate.
§ For example, see Sigma Aldrich, sodium perborate tetrahydrate (product
number 244120).
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Both forms of sodium perborate are stable and can be
introduced to the wash with the detergent. On coming into
contact with water, sodium perborate hydrolyses to form
hydrogen peroxide and sodium borate, eqn (3).
[(HO)2B(mO2)2B(OH)2]2 + 4H2O / 2[B(OH)4] + 2H2O2 (3)
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In the 1990s, a second persalt, sodium percarbonate, began
to replace sodium perborate in laundry detergents. There have
been some reports that this was due to concerns over the eco-
toxicity of boron products.26,27 However, a HERA (Human &
Environmental Risk Assessment) investigation in 2002
concluded that there is no risk to humans or the environment
from the use of perborates in detergents.28 Sodium percar-
bonate (2Na2CO3$3H2O2) is an adduct of sodium carbonate and
hydrogen peroxide.23 Again, the nomenclature is inaccurate as,
unlike sodium perborate, sodium percarbonate contains no
peroxocarbonate bonds (C–O–O–C).29 In sodium percarbonate,
the hydrogen peroxide is hydrogen bonded to the carbonate
ions and held loosely bound in a crystal lattice.30 This makes it
inherently less stable than the perborate. The active oxygen
content is >13%.26 Sodium percarbonate releases hydrogen
peroxide in water at least as quickly as sodium perborate
monohydrate, which is advantageous, but requires more
protection in granular form to improve its stability than sodium
perborate.31 Stabilising coatings (e.g. sodium silicate, sodium
sulfate32) are used to decrease decomposition rates and allow
safe bulk handling. Particularly for liquid detergent formula-
tions containing hydrogen peroxide, in order to prevent its
decomposition according to eqn (2), extra measures must be
taken to minimise the presence of transition metal ions
through the careful selection of ingredients, and the use of
radical scavengers and chelants (such as 2-({2-[bis(carboxy-
methyl)amino]ethyl}(carboxymethyl)amino)acetic acid, H4edta,
─ trivially called EDTA i.e. ethylenediaminetetraacetic acid ─
and various polyphosphonates).33 Other measures include
maintaining an acidic pH (ideally pH 2–5) and avoiding expo-
sure to heat (the Arrhenius dependence of the disproportion-
ation reaction has already been mentioned) and UV radiation
(typically through the use of opaque plastic bottles). In addition
to the above measures to prevent the decomposition of
hydrogen peroxide, care must also be taken to ensure that the
other detergent components are stable in the presence of
hydrogen peroxide. For example, ingredients that are easily
oxidizable (e.g. dyes) will not be stable in the presence of
hydrogen peroxide.33
3 Regional variations in washing
conditions
Detergents do not include the same components (in terms of
types and concentrations) in all regions. One of the reasons for
this is that, across the world, a wide range of differing laundry
wash conditions exist (Table 2). In the First World, washing
machines are commonplace, but there are many areas of the
world, such as parts of Asia and Africa, where laundry washing
is still carried out by hand.34 Where washing machines are
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available, the types of machine vary; from the drum type that is
common in the UK and Europe, to the top loading agitator used
in America. In Japan, pulsator washing machines, which use a
rotating ribbed disk to move the laundry in the wash, are
common.17 Washing conditions also differ: for example, in the
UK, washing is typically carried out in heated water, but in
Japan, washing is carried out at the ambient temperature of tap
water. Generally, laundry is carried out at an alkaline pH (8.0–
10.5). Table 2 contains a summary of the different wash
conditions in Europe, the USA, and Japan.
As a result of these varying conditions, innovations in
laundry detergent might require to be adapted for each region.
All components must be soluble and active at the temperature
of the wash. Short wash times in particular require components
which are readily soluble and have high activity in order to give
effective cleaning in the short time allowed.
This has inuenced the development of bleaches. When
Persil was introduced in 1907, laundry washes in Europe were
typically carried out at 95  C (‘at the boil’), and sodium perbo-
rate was an efficient stain remover. However, in the USA,
washing conditions were milder with lower wash temperatures
(40–60  C) and shorter wash times (10–20 min compared to 45–
60 min).35 Under these conditions, sodium perborate was inef-
fective.35,36 Instead, sodium hypochlorite solution became the
traditional bleaching agent. The use of sodium hypochlorite for
the bleaching of cloth was rst developed by Berthollet in the
1780s,37 and was quickly adopted on both sides of the Atlantic
for the industrial bleaching of cotton, among other uses. In the
1910s and 1920s, dilute sodium hypochlorite solutions (5.25%)
were developed and launched in the USA for use in household
laundry applications.22 By the 1930s, these products were
available nationwide.22,35 Due to compatibility issues with other
detergent components (such as uorescent dyes and enzymes),
sodium hypochlorite solutions were sold as a separate product
and added separately to the wash process. In the 1950s, prod-
ucts containing dry sources of hypochlorite were introduced,
but these disappeared by the late 1960s, most likely due to lower
efficiency than their liquid counterparts and fabric damage
claims.22 Chlorine-based bleaches were also dominant in Japan.
Following the development of sodium perborate monohydrate
and activated bleach systems (see Section 5), oxygen-based
bleaching products appeared on the American market in the
1980s,31 and became popular in Japan in the 1990s.38
4 Changing wash conditions
A major and continuing trend in washing conditions in Europe
is the lowering of wash temperatures. This began in the 1970s,
and was driven by the need to increase energy efficiency and the
increased use of temperature-sensitive synthetic bres and dyes
in clothing.31,39,40 Hydrogen peroxide (and the persalts which
release hydrogen peroxide) cleaning is temperature dependent.
Depending on the hydrogen peroxide concentration in the wash
and the wash conditions (e.g. wash duration, pretreatment), it is
possible to see benets on bleachable stains even at 30  C.
However, higher temperatures lead to better results and best
cleaning is expected at $60  C.17 It is known that the bleaching
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Table 2 Generalised washing conditions
Europe
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Washing machine
type
Cold water (internal heater),
horizontal axis, ‘Li & Drop’
horizontal axis, centre post or “Li & Drop”
agitation
Main wash volume Front load, 15 l
Temperature 20–90  C
Main wash time 20–90 min
Water hardness 12–25 gpg
Detergent 6000–11 000 ppm
concentrationa
a
Variations are due to differences in machine time and/or use of liquid vs. powder detergent.
rate of hydrogen peroxide has an Arrhenius temperature
dependence,39 therefore, the poor rate of hydrogen peroxide
bleaching observed at low temperatures is a kinetic phenom-
enon, so given more time or a higher concentration of hydrogen
peroxide, good bleaching results should be obtainable at low
temperatures. However, this slow rate of bleaching is not
acceptable under domestic laundry conditions, and adding
more persalts to the detergent formulation to compensate for
this slow rate of bleaching cannot be pursued for monetary and
formulation space considerations.31 Partly for this reason,
laundry additives are available, as these are used in combina-
tion with detergents and increase the overall concentration of
hydrogen peroxide in the wash. A complementary approach is to
nd more active bleaching species which can be formulated
directly into detergents.
While sodium hypochlorite bleaches were cheaper and more
effective at lower temperatures, thanks to faster kinetics and a
higher redox potential, associated colour and fabric damage,
strong odours, and compatibility issues with other detergent
ingredients prevented their broader usage in detergency. As
oxygen bleaches were safer to use on colours and fabrics, and
were more compatible with detergent ingredients such as
uorescent dyes,35 it was desirable to retain oxygen bleaches but
to nd methods to improve their efficiency at lower tempera-
tures. Thus began the development of bleach activation.
5 The history of bleach activation
The earliest reference to bleach activation dates back to the
1920s, when two patents (both Stoddard and Kokatnur)
emerged regarding the use of mixtures of compounds for
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USA/Canada Japan
High efficient top and
front load hot & cold water ll, vertical &
Front load top load, cold water,
vertical axis, spinning disc
agitation
in bottom of tub, swirling action
64 l top load, 30 l high efficiency top load, Top load: 45 l, front load: 30 l
18 l high efficiency front load
10–45  C 5–25  C
12 min 6–12 min
6–12 gpg 2–4 gpg
790–2800 ppm 300–1000 ppm
bleaching foodstuffs.41,42 These patents claimed that fatty acid
peroxides derived from oils (such as coconut) could act as
bleaching agents, and could also ‘act as activators’ for other
organic peroxides (such as benzoyl peroxide), increasing the
overall bleaching efficiency of those peroxides. In particular,
higher fatty acids as the ‘soap-forming fatty acids’ were found to
work best. Three decades later, organic nitriles (1956) and
aliphatic carboxylic acid amides, e.g. RC(O)NR0 R00 , (1957) were
discovered to give improved bleaching at lower temperatures
(60–70  C) when used with sodium perborate.43,44 The bleaching
performance attained at this temperature was as good as could
be achieved at 95–100  C using perborate alone. It was proposed
that the amide ‘activators’ were able to increase the amount of
oxygen liberated by the perborate. This was determined from
studies which measured the peroxide content under varying
conditions, as demonstrated in Fig. 4.
Three wash solutions were prepared as described in Fig. 4.
The peroxide content of each bath was measured periodically,
via titration with potassium manganate(VII) solution. Further
experiments showed increased bleaching in the system of Bath
C compared to Bath B, so a decrease in peroxide content
appeared to correlate with improved bleaching. By looking at
these results, it is understandable why one would assume that
the action of adding methanamide (formamide) to the wash
solution increases the activity of hydrogen peroxide, i.e. the
methanamide is ‘activating’ hydrogen peroxide. It appears that
more peroxide is used up when methanamide is present. In
1959, Unilever revealed that acyl organoamides, e.g. R0 C(O)
NHR00 , also had an ‘activating effect’ on the bleach activity of
inorganic persalts.45 The proposed mechanism suggested that
the persalt releases hydrogen peroxide, which then reacts with
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Fig. 5 Current commercial activators.

are compounds which contain the functional group –O–OH, e.g.

RC(O)O2H or RC(NH)O2H.
However, it wasn't until 1990, when experiments showed the
presence of peroxyethanoic acid formed in a solution of sodium
perborate and the activator TAED, that the occurrence of per-
hydrolysis was proven for the rst time.56 Only the perhydroxyl
Fig. 4 Example, described in a Degussa patent,43 of three bleaching
anion, and not the hydrogen peroxide molecule, reacts with the
systems tested.
activator, as the rate of peroxyethanoic acid formation was
observed to increase with increasing alkalinity, as a conse-
quence of the equilibrium shown in eqn (4).57
the amide forming a new bleaching species which is more active
than hydrogen peroxide, although no suggestions were made
H2O2 # H+ + [HO2], pKa 11.64 (4)
regarding the nature of this species. This new bleach was found
to be efficient at temperatures 50–60  C. Further work In aqueous solutions, the hydroxide ion is also present, but
continued into similar and alternative compounds which could owing to the greater nucleophilicity of the perhydroxyl anion, it
‘activate’ hydrogen peroxide at lower temperatures. Compounds will react preferentially. The perhydroxyl anion has been shown
which complied became known as bleach activators. Examples to be more reactive than the hydroxide ion with a range of
include: carboxylic esters (Unilever, 1956–1958);46,47 N-diacetyl- substrates (Table 3).58
amines (Koninklijke Industrieele, 1959);48 polyacetyl methylene At pH 10–11, the perhydrolysis reaction occurs independent
diamines, e.g. R0 (COCH3)NCH2N(COCH3)2 (British Celanese, of temperature, and is complete within a few minutes at 25  C.32
1963);49 acyloxybenzene sulfonates, e.g. RCO2(C6H4)SO3M Higher oxidation potentials have been measured for peroxy
(Procter & Gamble, 1983);50 4-sulfophenylalkylcarbonates, e.g. acids compared to hydrogen peroxide – a property which may
ROCO2(C6H4)SO3M (Akzo NV, 1986).51 explain their greater bleaching power.22
Activated bleach systems were far superior to simple persalt
systems and, from the 1970s, ‘activating’ compounds began to
be produced on a commercial scale and included in detergent
formulations. The rst bleach activator to be incorporated in a
detergent product was tetraacetylglycoluril, TAGU (Cid, Henkel,
1972).52 TAGU was expensive to manufacture and is not
completely biodegradable, which limited its use.53 Despite the
large number of bleach activators that have been investigated Fig. 6 The perhydrolysis reaction, where X is a leaving group.
and patented, only a few are commercially relevant, even today.
Currently, there are four main activators which are used in
commercial products across the globe (Fig. 5): TAED (Europe), Table 3 Relative nucleophilicities of [HO2] and [HO] anions58
NOBS (America and Asia), LOBS (Asia) and DOBA (Asia),
although 98% of the market value is accounted for by the rst Substrate kperhydroxide/khydroxide
two.54 These activators will be discussed in more detail in PhCN 66 000
Section 7.3. 2,4-(NO2)C6H3Cl 300
From the early studies, it was theorised that the ‘activator’ DADHTa 250
compound was reacting with hydrogen peroxide in solution via 4-(NO2)2C6H4 145
the perhydrolysis reaction (Fig. 6), forming a peroxy acid, which 4-NO2C6H4OAc 77
PhCH2Br 34
then either acted as a bleach, or formed another bleaching
a
species through a decomposition mechanism.36,55 Peroxy acids DADHT (diacetyl dioxohexahydrotriazine) is a bleach activator.

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6 Preformed peroxy acids
An obvious question which emerges from the above method-
ology is that as peroxy acids are the bleaching species, would it
be more efficient to add peroxy acids directly to the wash as part
of the detergent formulation? This would remove the need to
add a source of hydrogen peroxide, saving space and reducing
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waste. Preformed peroxy acids would also avoid the extra mass
associated with the leaving group of a bleach activator, e.g. as
shown in Fig. 7, less than 50% of the mass of the bleach acti-
vator forms the peroxy acid in each case. The leaving group,
which plays no part in bleaching, makes up the rest.
A further benet of preformed peroxy acids is the avoidance
of some of the wasteful reactions associated with bleach acti-
vator methods, such as loss of hydrogen peroxide through
reaction with the enzyme catalase or metal ions, and hydrolysis
of the activator; all of which reduce the efficiency of peroxy acid
generation and bleach efficiency.39 A further advantage is the
immediate availability of the peroxy acids in the wash.59 The
above advantages have not gone unnoticed, and several inves-
tigations into suitable peroxy acids have occurred. However, in
practise, there are many technical challenges encountered in
the use of preformed peroxy acids, including thermal insta-
bility, product compatibility, and cost, which have limited their
use. Peroxycarboxylic acids with an active oxygen content > 7%
are thermodynamically unstable and can explode under
thermal or mechanical stress (derivative of their structural
similarities with hydrogen peroxide, Section 2).26 As a result, low
molecular mass peroxy acids must be avoided due to their
hazardous nature, but high molecular weight compounds are
less mass-effective. Peroxycarboxylic acids are also typically
unstable, both isolated and in solution, and particularly in an
alkaline environment, which is typical for detergent composi-
tions: the short shelf-life prevents their use.60 For example, in
1960, peroxybenzoic acid was investigated and shown to have
poor stability: reportedly 10% decomposition per week occurred
at room temperature, even when it was maintained in ‘an iso-
lated state’.61 Despite being far superior to perborate with
respect to bleaching activity, insufficient stability prevented
commercialisation. Later studies demonstrated that substitu-
tion on the benzene ring improved the stability: depending on
the form of substitution, the decomposition rate could be
decreased to as little as 0.1% per week.61 However, derivatives of
peroxybenzoic acid were found to have undesirable side-effects,
including damage to fabrics, colours and uorescent whitening
Fig. 7 Mass distribution in bleach activators NOBS (left) and TAED
(right) where the blue areas denote leaving groups.
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agents, which ultimately prevented their use in laundry
detergents.62
Various efforts have been made to increase the stability of
peroxycarboxylic acids through the formation of ‘inclusion
complexes’, for example, with urea.60 However, the stability was
still diminished in the presence of alkaline compounds.
Several other peroxy acids were investigated, including
magnesium bis(monoperoxyphthalate) hexahydrate (Mg-MPP,
see Fig. 8), which was released commercially by Interox.62 Mg-
MPP contains 5.5% active oxygen and is safe to handle.
However, it has a limited bleaching ability due to a high
hydrophilic/lipophilic balance (dened in Section 7.1), and dye
damage potential limited its use in laundry products. 1,12-
Diperoxydodecanoic acid (DPDDA, Fig. 8) was found to be
effective as a bleaching agent on both hydrophilic and hydro-
phobic stains due to its hydrotropic nature.62 However, poor
stability in alkaline detergent formulations, and potential
runaway exothermic reactions, resulted in handling problems
and high cost, leading to limited commercialisation, despite
considerable research to overcome these issues.39,62
The incorporation of a polar functional group such as an
amido or imido linkage into an alkyl peroxycarboxylic acid was
found to increase the thermal stability of the peroxy acid. One
successful example of this is 6-(phthalimido)peroxyhexanoic
acid (PAP, Fig. 8), which is a white, odourless powder.63
Hydrogen bonding results in innite chains of molecules in the
solid state, and provides stability.64 Even in the pure state, PAP
is not explosive, and is highly volume-effective: >95% active
matter. Optimum bleach activity is achieved at 20–50  C and pH
7–10, which correlates well with current washing conditions.
PAP is only sparingly water-soluble (0.2 g l1 at 20  C, pH 4.5),
allowing stable aqueous dispersions to be prepared in an acidic
pH range.26 The solubility of PAP improves with increasing pH
and temperature: at pH 10 and 20  C, 80% of PAP dissolves
within 5 min, so it functions under typical alkaline washing
conditions.26 Under alkaline conditions, the phthalimido ring
may open irreversibly. The ring-opened peroxy acid is consid-
erably less bleach active due to the negative charge on the ring.
At pH 9.2 and 40  C, the half-life of PAP is 20 min.26 Numerous
patents have emerged using PAP in recent years, indicating that
there is still a high interest in this peroxy acid.65,66
Fig. 8 Preformed peroxy acids Mg-MPP, PAP and DPDDA.
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Overall, the issues highlighted above, including the ther-
modynamic instability of peroxy acids, focussed research into
developing bleach activators which form the peroxy acid in situ
in the wash. When bleach activators are used, a source of
hydrogen peroxide must also be included in the formulation.
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7 Bleach activators
7.1 Design strategies
Activators can be considered as being composed of two parts:
the peroxy acid precursor and the leaving group.26 Activators are
modied by altering these parts. The peroxy acid precursor
affects the bleaching properties of the peroxy acid: determining
activity, selectivity, hydrophilic/lipophilic balance, and oxida-
tion potential. The leaving group inuences the solubility,
perhydrolysis rate, and storage stability of the activator.26 In an
earlier article by Grime and Clauss (1990), the authors laid out a
number of design strategies which occurred following the
development of the rst activators.62 These included:
 increasing the rate of perhydrolysis by using more facile
leaving groups,
 increasing the reactivity of the peroxy acid through
increased oxidation potential,
 increasing the efficiency of surface bleaching over solution
bleaching through increased surface activity of the resultant
peroxy acid, and
 improving the bleaching of more hydrophobic stains and
soils by reducing the hydrophilic/lipophilic balance (HLB) of
the resultant peroxy acid.
The HLB is a theory which states that the hydrophilic/lipo-
philic character of a peroxy acid determines what type of stains
the peroxy acid will bleach most efficiently.62,67 The balance is
related to surface activity measurements, and plays an impor-
tant part in the design strategy of activators.67 Peroxy acid types
are differentiated by surface activity measurements, which are
calculated using critical micelle concentrations (CMCs) and
HPLC retention times.
7.2 Performance of peroxy acids
Very few papers have emerged which examine the performance
of peroxy acids, or the relationship between performance and
structure. In 1988, Bolsman et al. published a study examining
the relationship between peroxy acid structure and bleaching
performance for a range of 13 mono- and diperoxycarboxylic
acids.36 In this study, both aliphatic and aromatic peroxy-
carboxylic acid compounds of various chain-lengths and
degrees of branching were tested, under a range of conditions.
The quantities of bleaching species added were based on the
assumption that each diperoxy acid provides two active
oxygens, while monoperoxy acids provide one. However, other
sources have shown this is not the case56,58 (also, see Section
7.3.1). This assumption gives rise to error, in differences which
are already very small. Therefore, the results from the mono-
and diperoxy acid bleaching tests described in this paper
should not be directly compared. For a series of straight-chain
aliphatic peroxy acids, increasing the chain length through
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C10–C12–C14–C16 appeared to have a slightly negative impact
on performance. This effect is in agreement with other sources
which have claimed optimal stain removal for chain lengths
C8–C9.39
In Bolsman's study, the highest level of stain removal was
achieved by 4-tert-butylperoxybenzoic acid, which, as already
described in Section 6, is in agreement with other studies
which have shown that peroxybenzoic acids are very good
bleaches. This was succeeded by peroxydecanoic acid, the
results of which were comparable to the TAED/perborate
system. The study also tested the bleaching performance of a
number of peroxy acids on bleaching a water-soluble dye in
solution. The authors concluded that the results from this
study would suggest that bleaching performance improves on
increasing the chain length of the peroxy acid in the order C12
> C14 > C10 > C16. For the diperoxy acids, the rate appeared to
be C16 > C12. This suggested to the authors that micellar
interactions strongly affected the rate. However, while this
work may give an indication of likely trends, the studies are too
limited in scope to draw any real conclusions. It is unclear from
the text if any of the experiments were repeated, or are
reproducible.
In 1997, Reinhardt and Löffler published a study of nitrile
activators, which generate peroxyimidic acids.68 This study was
more extensive, with reportedly seventy different nitriles tested,
although limited information is given on the structures of the
majority of these compounds. Most of the compounds tested
were found to have insufficient bleach activity, in part due to
their poor solubility in water. Aromatic compounds were found
to be more active, and the addition of electron-withdrawing
groups onto the aromatic ring was found to increase bleach
activity further, in some cases. The effects of adding an amino
group, and the effects of adding a spacer between the nitrile and
the amino functionality, were also examined: a nitrogen adja-
cent to the nitrile group increased bleach activity, whereas even
the presence of a methylene spacer group reportedly decreased
bleach activity by 80%. Many of the nitriles tested (particularly
cyanamide and its derivatives) were found to be highly aggres-
sive towards dyes and fabrics, making them unsuitable for use
in laundry detergents. The usefulness of this study is limited by
the lack of structure information.
While these are interesting studies, and few of their kind
have been published, bleaching is complex, and viable bleach-
ing agents cannot be identied by simple tests involving a
single stain or dye. We have already mentioned, for example,
that hydrophilic bleaches are more efficient at removing
hydrophilic stains and vice versa. The important point to
acknowledge here is that a bleach which is efficient at removing
a certain type of stain, will not necessarily remove other stains
efficiently. For use in laundry detergent, a bleaching agent that
has a wide scope of activity is required for effective removal of
the range of stains encountered in the wash. Ultimately, this
shows that it is not possible to make accurate sweeping judge-
ments based on simple systems. Another point, which was
highlighted by Bolsman's study, is that the efficiency of any
peroxy acid changes for different systems e.g. solution bleach-
ing vs. fabric bleaching. Ultimately, while solution studies are a
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Fig. 9 The pH effect on the bleach performance of peroxyethanoic
acid (generated from TAED) with various stains, where C is tea, , is
red wine, : is grass and - is ketchup.26 Delta remission is calculated
by measuring the reflection of a fabric before and after a washing test
and expressing the difference as a % relative to a white standard.
Reproduced from ref. 26 with permission from Taylor and Francis
Group LLC Books.
useful tool for quickly testing bleach activity, as laundry
washing deals mostly with stains on clothes, fabric washing
trials are required to give substantial information on the
viability/activity of any bleach system. Reinhardt has published
several articles on this subject.69,70 These studies have shown
that bleach activity depends strongly on the washing condi-
tions, the bleach-active species, the type of stain, and the type of
fabric on which the stain is present. For example, even using the
same peroxy acid, each stain has a different optimal pH for
bleaching (Fig. 9).
Stain removal is not specic just to the conditions, but to the
conditions for each bleaching agent. Each stain has different
optimal conditions for each bleach. For example, tea is best
removed at pH 10–11 using a catalyst, but at pH 7–8 using the
peroxy acid PAP (see Fig. 10).
These examples show that stain removal is dependent on the
stain, the bleaching agent, and the bleaching conditions. This
must be held in consideration when judging the reliability of
any bleaching test. As shown by the examples of peroxybenzoic
acids and cyanamides, increased bleach activity does not
necessarily preclude to an improved system, as dye and fabric
damage over repeated washing trials must be examined.
Fig. 10 Optimum conditions for various systems to bleach tea stains.
Reproduced from ref. 26 with permission from Taylor and Francis
Group LLC Books.
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7.3 Current activators
It has already been stated that there are currently four bleach
activators of relevance on the world market (see Fig. 5). These
activators are considered the standard in bleach activation.
They are not the most reactive activators that have been devel-
oped, but are acceptable as a compromise between activity and
damaging effects. More reactive activators have been developed
and patented (e.g. cyanamide salts71), but oen an increase in
reactivity leads to an increase in dye and fabric damage, which
becomes apparent aer a few washes and is unacceptable. As
new activators are developed, their performance is compared
against these standards.69,70 These activators will now be
considered in greater detail.
7.3.1 TAED. Tetraacetylethylenediamine (TAED, Fig. 5), a
crystalline amide, is a hydrophilic bleach activator and has been
used in commercial products since 1978 (Skip, Unilever).52
TAED is the main activator used in European detergents62 and
has an estimated annual consumption of 75 kt.26 TAED was rst
prepared by Franchimont et al. in 1911,72 although numerous
patents have emerged on different methods to synthesise TAED
and related compounds.73–75 In aqueous alkaline solution, the
perhydroxyl anion reacts with TAED to form tri-
acetylethylenediamine (TriAED) and diacetylethylenediamine
(DAED) consecutively, and releases (roughly) two equivalents of
peroxyethanoic acid (Fig. 11). TAED, TriAED and DAED are all
completely biodegradable and substantially removed during
wastewater treatment.76
Theoretically, the perhydrolysis of TAED could yield four
moles of peroxyethanoic acid per mole of TAED, as there are
four acyl groups present. However, a molecule of TAED can only
provide a maximum of two equivalents of peroxyethanoic acid
due to the substantial increase in the conjugate acid pKa of the
leaving group going from an amide (pKa ¼ 17) to an amine
(pKa ¼ 35).22 Therefore, TAED can only deliver a maximum of
two equivalents of peroxyethanoic acid. However, due to a
competing reaction of TAED with hydroxide anions (saponi-
cation), two equivalents is not quite achieved, and various
values have been measured e.g. 1.5 mol (ref. 56) or 1.7 mol.58
TAED is not the only activator developed capable of delivering
more than one equivalent of peroxy acid per molecule of acti-
vator, but it is the only current, commercially used bleach
activator to do this. TAED crystals have excellent storage
stability, which can be further increased by granulation with
suitable storage aids.77 The benets of TAED are lost at
temperatures >60  C due to the activity of the persalt at higher
Fig. 11 The perhydrolysis of TAED.
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Fig. 13 Tide with Bleach: the first detergent to contain the bleach
activator NOBS.

Fig. 14 The perhydrolysis of NOBS.

methods have been patented for the synthesis of NOBS.81–84 Its

structure is designed to have a degree of hydrophobicity, for
easier approach of the bleach to oily soils at the fabric surface.79
This is achieved by an optimal chain length in the C8–C10
range.85 When attacked by the perhydroxyl anion, NOBS forms
the peroxy acid peroxynonanoic acid and releases the leaving
group 4-hydroxybenzene sulfonate, which (as its sodium salt) is
an inert by-product (Fig. 14).
Fig. 12 (a) A comparison of the bleaching performance of sodium In the wash, peroxynonanoic acid, once formed, can react
perborate and sodium perborate/TAED as a function of temperature. with another NOBS molecule forming a diacyl peroxide (DAP);
Reproduced from ref. 17 with permission from Wiley-VCH. (b) The
bleaching performance of the preformed peroxyethanoic acid versus
in this case, dinonanoyl peroxide (see Fig. 15). Despite many
TAED and sodium percarbonate (which generates peroxyethanoic acid reports that dinonanoyl peroxide is not an active bleaching
in situ). SPC is sodium percarbonate. Reproduced from ref. 26 with agent,31,55 it has been shown to have some bleaching activity
permission from Taylor and Francis Group LLC Books. and, importantly, it acts on different stains (particularly,
tomato-based) to peroxynonanoic acid.32,86 As a result, the
formation of a small amount of DAP is benecial, but too much
temperatures, combined with the thermal instability of
is considered a waste of NOBS. DAP formation can be controlled
peroxyethanoic acid (Fig. 12(a)).53
by manipulating the persalt to NOBS ratio and the wash pH.
From Fig. 12(b), at lower temperatures, the activity of the
High persalt ratios and high pH favour low DAP formation, as
TAED/sodium percarbonate system is comparable to peroxy-
perhydroxyl anion formation is favoured and the excess of
ethanoic acid, with a slight decrease in rate due to the delay
NOBS is minimised.79 If excess persalt is not used, the yield of
incurred from dissolution and perhydrolysis. However, above 60
 peroxynonanoic acid falls dramatically.55 Ratios of persalt/NOBS
C, the TAED/sodium percarbonate system activity is increased
of at least 3 : 1 are recommended.79 Such high excesses of per-
due to the large stain-removing effect from the excess persalt,
salt are not necessary in cases where the activator is not an ester,
which is active at higher temperatures. The activity of peroxy-
e.g. TAED, and does not form diacyl peroxides.31 Persalt/TAED
ethanoic acid falls at temperatures >60  C due to thermal
ratios of 1.5 : 1 to 3 : 1 are optimal.71
instability.
NOBS can hydrolyse to sodium nonanoate and sodium
7.3.2 NOBS{. Sodium nonanoyloxybenzene sulfonate
4-hydroxybenzene sulfonate in alkaline solution.32 Bruice et al.
(NOBS, see Fig. 5) is a hydrophobic bleach activator that was
calculated the rate constants of the alkaline hydrolysis of
developed by Procter & Gamble in 1983,78 and introduced in
sodium 4-decanoyloxybenzene sulfonate, in the presence or
1988 in Tide with Bleach (Fig. 13).79 FutureFuel (owned by
absence of surfactants, and found that the rate of hydrolysis
Eastman) currently produce NOBS for Procter & Gamble, which
is readily biodegradable by European standards.80 Numerous

{ The abbreviation NOBS refers to nonanoyloxybenzene sulfonate; the presence of

sodium is assumed. Occasionally, the abbreviation SNOBS is used to include the
sodium, but this is rare. Fig. 15 The formation of dinonanoyl peroxide.

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On reaction with the perhydroxyl anion, DOBA produces per-

oxydecanoic acid.

7.4 New activators

Fig. 16 IsoNOBS, sodium 3,5,5-trimethylhexanoyloxybenzene
sulfonate.
As already stated, TAED was rst included in a commercial
product in 1973, and NOBS in 1988. These remain the standard
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bleach activators in commercial products, demonstrating their

efficiency, but also highlighting that no better replacements
decreased in the presence of surfactants.87 Substituents on the
have been found, despite considerable research. From patents
phenyl ring were also found to inuence the rate.
led regarding the development of new bleach activators, one
Reportedly, under certain conditions, NOBS can produce
major trend which has emerged is to produce variations on the
unpleasant odours in the wash liquor.88 This unwanted ‘blea-
NOBS theme.51,79,95 This is dealt with very well in the paper by
chy’ odour cannot be masked by perfume spray. It was found
Grime,79 who highlighted a number of these efforts. One
that branching in the alkyl chain stopped the occurrence of
example has already been discussed, being the development of
unwanted odours.62,88 Sodium 3,5,5-trimethylhexanoyloxy-
branched isomers of NOBS (see Section 7.3.2). Alternative
benzene sulfonate (IsoNOBS, see Fig. 16) is one example that
strands also involve using a carbonate ester moiety rather than a
was developed. It is claimed that the branched isomers provide
carboxylate, Fig. 17(b).96 Alkanoyloxyethanoate compounds
effective bleaching at temperatures around 60  C, although no
were also patented. These contain the same hydrophobic chain
direct performance comparison is made between IsoNOBS and
and phenol sulfonate leaving group as NOBS, but also contain
NOBS in the mentioned patent. However, later sources report
the glycolate function, adding an extra perhydrolysis point,
that the branched IsoNOBS is less active under typical wash
Fig. 17(c).97 Depending on the pH, up to three different peroxy
conditions.53
acids can be produced from one activator. In theory, this would
7.3.3 LOBS. Sodium lauroyloxybenzene sulfonate (LOBS,
provide bleach activity over a wider pH range and broaden the
Fig. 5) is a higher homologue of NOBS, and is more hydrophobic
spectrum of stains bleached. However, the composition of the
and less water-soluble than NOBS.26 LOBS was reported in the
bleaches formed is highly dependent on the reaction condi-
same Procter & Gamble patent as NOBS,78 which included all
tions, leading to varied performance.79 Another line of investi-
compounds of this type with an alkyl chain ranging from 5–13
gation involved replacing the alkyl chain of NOBS with a
carbon atoms, and a variety of leaving groups. LOBS is most
quaternary ammonium functionality, Fig. 17(d).98 These are
commonly used in Japan.38 In the wash, the perhydroxyl anion
reported to be very effective bleaches, likely due to the adsorp-
reacts with LOBS to form peroxydodecanoic acid. Due to the
tion of the cationic moiety to the anionic fabric surface in the
added hydrophobicity of the long alkyl chain, peroxydodecanoic
alkaline wash solution.62
acid is able to remove highly lipophilic stains.26 LOBS was the
Decreasing wash temperatures and shorter wash cycles are
rst bleach activator to be incorporated into a liquid detergent
driving the development of more active bleach activators. Acti-
product (see Section 12) and has been shown to have a higher
vators which generate peroxybenzoic acids, such as benzoyloxy-
antibacterial effect at lower concentrations than TAED, which
benzene sulfonate (BOBS) or benzoyl caprolactam (BCL), have
may lead to an increased importance of this activator in future
been prepared.26 Peroxybenzoic acid has a higher oxidation
as washing conditions change.89
potential due to the electron-withdrawing effect of the aromatic
7.3.4 DOBA. Another class of activators has 4-hydroxy-
ring.62 BOBS, while having an improved soil-bleaching perfor-
benzoic acid as the leaving group, an example of which is
mance, causes more damage to dyes and uorescent whitening
4-decanoyloxybenzoic acid (DOBA, see Fig. 5). Like LOBS, DOBA
agents.62
is also used in Japan.38 A number of patents give preparative
Several nitrile species, which release peroxyimidic acids (e.g.
routes to DOBA.90,91 At neutral or slightly acidic pH, DOBA is
RC(NH)OOH) on perhydrolysis, have been investigated.69,71 As
virtually insoluble in water, which allows storage-stable
bleach activators, nitriles are very volume-effective, as they have
aqueous dispersions and slurries to be prepared.26 Under
no leaving group and so are not carrying extra mass (and,
alkaline washing conditions, DOBA dissolves quickly and
equally, no extra waste). However, many have been found to be
generates peroxydecanoic acid. Again, due to the long hydro-
very aggressive towards dyes and fabrics. A number of liquid
phobic chain, DOBA works primarily on hydrophobic stains,
activators have been developed, including 4-morpholinocarbo-
like curry and ketchup92 (in accordance with the hydrophilic/
nitrile (MOR) and acetyl caprolactam (ACL). Liquid activators
lipophilic balance) and is bleach-active at 30–60  C. The long
chain also shows increased antibacterial effects compared with
TAED.93 The sodium salt of DOBA has a higher melting point
and greater solubility compared with the acid. However, the
acid is more easily isolated and can be obtained in higher yields
in synthesis. If the acid is spray-dried, producing a ne powder,
the solubility and rate of perhydrolysis are comparable with the Fig. 17 Representations of bleach activators with similar structure to
sodium salt, so there is no advantage to using the sodium salt.94 NOBS, where R is an alkyl chain and L is the leaving group 4-
C6H4SO3Na.

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are preferred in industrial applications as they can easily be
dosed via pumps, and dissolve more quickly in the bleaching
bath than solid activators.26
7.5 Mixtures of activators
Several patents have emerged claiming improved performance
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using mixtures of bleach activators.67,99,100 These methods
involve adding two activators separately, or forming co-granules
of two activators.94 A further development is the investigation of
bleach activators that can give two peroxy acids from one
molecule: one hydrophobic and one hydrophilic.71 Examples
include asymmetrically substituted polyesters or imides, and a
number of patents have been led in this area.97,101,102 These new
activators are claimed to have superior bleaching ability over
the prior art. Theoretically, the latter approach is advantageous
compared to a mixed activator system, where two or more
activators are added, requiring more space and creating more
waste. The commercial viability of these activators is not dis-
cussed in publicly available sources.
8 Advantages of an activated bleach
system
Croud identied a number of advantages of an activated
bleaching system.53 Firstly, an activated system allows bleaching
to occur at lower temperatures, which is more energy efficient,
better for the environment, and maintains clothes longer. The
activated system also provides low temperature sanitisation:
peroxy acids reduce the level of microorganisms present, min-
imising the spread of disease and infections. According to the
UK Department of Health, a wash temperature of 71  C for three
minutes, or 65  C for ten minutes, is required for effective
thermal disinfection of hospital laundry. The TAED/perborate
system was shown to give the same level of kill at 40  C as can be
achieved by thermal disinfection at 71  C. Activated systems
also attack microbes and inhibit bacterial growth. This has a
number of follow up benets: inhibition of odours caused by a
high microbial loading on fabric (the musty smell of damp
laundry); inhibition of fabric damage caused by microorgan-
isms; inhibition of microbially-induced washing machine
corrosion (some bacteria liberate ammonia which erodes
aluminium).53 Activated oxygen systems are also advantageous
when compared with chlorine-based bleaches, as these are
incompatible with many additives in the detergent formulation,
such as optical brighteners and enzymes, both of which are
oxidised by chlorine bleach, but are affected to a much lesser
extent by oxygen bleaching systems.
9 Requirements for new bleach
activators
At the end of the 1990s, Milne31 and Croud53 independently
suggested a number of requirements for effective new bleach
activators. In order to be commercially viable, new bleach acti-
vators must:
(a) be compatible with other detergent ingredients,
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(b) be active under current wash conditions,
(c) be cost effective,
(d) be colour and fabric safe,
(e) have low toxicity and acceptable environmental effects,
(f) exhibit sufficient chemical and physical stability,
(g) exhibit sufficient resistance to product separation,
(h) be æsthetically acceptable,
(i) be easily processed, and
(j) have no adverse effects on washing machine parts.
Some requirements are set at a chemical level (b, c, d, e, j),
while in other cases, additives or processing techniques can be
used to improve suitability (a, f, g, h). Points (e) and (j) apply to
both the activator and its perhydrolysis/decomposition prod-
ucts. Most of these points are self-explanatory and further
details can be found in the references listed.31,53
10 Mechanism of bleaching
Bleaching is a decolourisation, or whitening, process. In
laundry systems, the purpose of the bleach is to remove stains
from fabrics and also, to a lesser extent, to remove any dyes in
solution which have leaked from laundry items in order to
prevent their transfer onto other fabrics in the wash.
Bleaching is essentially oxidation chemistry. As stated in
Section 1, reductive bleaches do exist, but are not commonly
used in laundry applications.22 This is partly due to the
discovery that many chromophores commonly found in laundry
stains, when bleached reductively, become colourless, but later
the colour returns as a result of air oxidation.17
Stains can come from a variety of sources – spilled food and
beverages, mud, dust, grass, as well as biological soils. The
colours of stains and dyes encountered in the laundry normally
arise from conjugated p-bonded chromophores, due to their
extended conjugation which allows them to absorb light in the
visible region. Bleaches remove a coloured stain by altering the
stain chromophore so that it is no longer coloured. This action
may also break up the stain molecule into smaller, more soluble
pieces, which can then be removed by surfactants/wash liquor,
or simply make the stain less apparent on the fabric.
An oxidising bleaching agent works by: (1) destroying one or
more of the double bonds in the conjugated chain, (2) cleaving
the conjugated chain, or (3) oxidising one of the other moieties
in the conjugated chain.22 As stain chromophores are large
structures with long stretches of conjugation, they have
multiple points of attack. Peroxy species can break up conju-
gation by a number of different routes:22
(i) addition of an oxygen across a double bond to give an
epoxide
(ii) oxidation of aldehydes to acids
(iii) oxidation of sulfur compounds to sulfoxides and
sulfones
(iv) oxidation of nitrogen compounds to amine oxides,
hydroxylamine, or nitro compounds
(v) oxidation of a-diketone compounds to anhydrides
(vi) oxidation of ketones to esters.
If any of these actions occur, they will lead to a decrease in
the level of conjugation and an associated increase in the energy
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Fig. 18 (A) Bleaching by the perhydroxyl anion, and (B) bleaching by
the peroxy acid anion through nucleophilic attack on an alkene group.
gap between the ground and excited states, so that the molecule
then absorbs light in the ultraviolet region and no colour is
produced.
Bleaching reactions with hydrogen peroxide or peroxy acids
follow a second-order rate law (rst-order with respect to both
the substrate and the active ion concentration).103 This indicates
that both reactants are involved in the rate-determining step.
Bleaching by perhydroxyl anions or peroxy acid anions is
believed to proceed via nucleophilic attack on electrophilic
centres (e.g. alkene groups), as shown in Fig. 18.31 The mecha-
nism of bleaching by hydrogen peroxide/perhydroxyl anion or
peroxy acid/peroxy acid anion has been detailed elsewhere31,39
and so it will not be covered in further detail here.
The above is a simplication of the laundry process. Typi-
cally, for stains which are present on the fabric surface, the
bleach must rst be absorbed into the subsurface of the bres
or diffuse into the interior of the bres to reach the stain.
However, other stain components can make this difficult. For
example, lycopene is a carotenoid pigment that is present in
many red foods such as tomatoes. In a spaghetti sauce stain, for
example, the lycopene is dissolved in oil, which can provide
some protection against hydrophilic bleaches as it is more
difficult for the bleach to approach the chromophore. As a
result, stain removal is a synergistic process between the bleach
and other components of the formulation, such as surfactants,
which work together in the wash e.g. the surfactant removes the
oily compounds, allowing the bleach to approach the stain.
Some wash conditions are particularly relevant for effective
bleaching, and it is important to be aware of these. For example,
a high pH (10–11) is required to accelerate the perhydrolysis
step and generate enough peroxy acid for effective bleaching. In
a further complexity, optimum bleaching performance by a
peroxy acid occurs at a slightly lower pH, typically 8.5–9.5.26 In
practice, in the domestic wash, this is usually obtained by
releasing an organic acid (e.g. a polycarboxylic acid such as
citric acid) from a coated particle.104 The reaction is triggered
either by temperature (e.g. if the coating material is wax, it will
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melt during the heating phase), or by the time-delayed disso-
lution of a fatty acid via a neutralisation step.26
11 Bleach catalysts: an alternative
chemistry
A disadvantage of the bleach activator approach is that activa-
tors must be added in stoichiometric quantities. A much more
efficient system would be based on catalysts, which could also
provide reduced space, mass and ultimate waste advantages
too. A number of investigations have been carried out in this
area, which can be divided into two parts: metal catalysts and
organic catalysts. In some instances, organic bleach catalysts
are referred to as bleach boosters.105 However, this could be a
misleading term, as it is also used in other instances to mean
any bleaching solution used for pretreating laundry or laundry
additive containing bleach.106,107
Metal bleach catalysts had a brief start in detergents with the
introduction of Persil Power by Unilever in 1994. The product
was also released in the Netherlands, where it was called Omo
Power, and in France, where it was called Skip Power.108 The
catalyst was a binuclear manganese complex with the ligand
1,4,7-trimethyl-1,4,7-triazocyclonoane (Mn-TMTACN, Fig. 19),
and was dubbed ‘the accelerator’.108 At 40  C, only one
hundredth of the dose (0.05 wt% of formulation) was required
for as good a bleaching performance as the standard TAED
system (5 wt% of formulation).109
However, almost immediately following its release, the
product came under scrutiny amid reports that unacceptable
dye and fabric damage occurred aer several washes. Both
Procter & Gamble and Henkel ordered independent washing
tests. A Henkel-commissioned study found that damage
occurred aer just 12 washes using Omo Power.108 The product
was reformulated to contain 80% less catalyst. Further market
tests followed and the reformulated powder was found to still
cause unacceptable damage to fabrics.110 Persil Power was
replaced with New Generation Persil, minus the manganese
catalyst.111 Persil Power was withdrawn from the market in
1995.112 The catalyst was later used in automatic dishwashing
detergents, where the colour and bre damage effects were not
as relevant.113 Further studies on the Mn-TMTACN catalyst have
shown that bre damage appears to be dye-mediated, as in one
study, the bres of un-dyed fabrics were not as damaged as
those of dyed fabrics,109 leading to the suggestion that metal
catalysts are more suited for purposes such as the bleaching of
raw cotton.113
Fig. 19 Mn-TMTACN, a bleach catalyst.
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Since this unsuccessful rst launch, work has continued to
look for more suitable catalysts, and a number of metal bleach
catalysts have been put forward as ‘safe’, such as complexes
with iron(III)-tetraamido macrocyclic ligands (Fe(III)-TAML),114
and terpyridine–manganese complexes.115 Catalytic bleaches
are an intriguing eld due to their many potential advantages,
including low dosage and less space occupied in the formula-
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tion. The lower mass required allows catalysts to be more
expensive than their counterpart activators. However, to be
suitable for use in laundry detergents, bleach catalysts must
meet a number of criteria, many of which are the same as for
bleach activators.
They must:
(a) be active:
(i) at low temperature (<30  C)
(ii) in an aqueous medium
(iii) at an alkaline pH,
(b) be compatible with other detergent components,
(c) be sufficiently stable (processing, storage, time),
(d) have low reactivity to catalyse the decomposition of
hydrogen peroxide,
(e) have ligands which are sufficiently robust to oxidation,
(f) have selective stain removal over dye and fabric damage,
(g) be environmentally acceptable,
(h) be cost effective, and
(i) have no adverse effects on washing machine parts.
Overall, research has focussed on catalysts based on iron or
manganese complexes.116 A number of technical challenges
exist for this methodology: for example, many catalysts have a
relatively low thermodynamic complex stability under alkaline
conditions, resulting in a fast decomposition to manganese(IV)
oxide or iron(III) oxide, and thus are unsuitable.116 Furthermore,
many ligands are not stable to oxidation, which limits the type
of catalysts which could be used. It has been estimated that 98%
of ligands used in iron and manganese complexes described in
the literature would be unsuitable for laundry processes due to
low intrinsic activity or insufficient stability.116 Studies have
been carried out to nd and/or design oxidation-resistant
ligands,117,118 and a number of potentially suitable ligand types
are now known, such as halogenated porphyrins, phthalocya-
nines, and tetraamido macrocyclic ligands.117 Another disad-
vantage of bleach catalysts is that the metal can be abstracted
from the ligand, and oxidised to form an insoluble residue
which can deposit on fabrics.119
In the 1980s, novel organic catalytic oxidising agents
appeared in the literature. In 1988, Davis et al. oxidised
aliphatic and aromatic suldes to sulfoxides using novel N-
sulfonyloxaziridine generated from potassium peroxy-
monosulfate and a sulfonimine (e.g. RSO2N]R0 ).120 The sulfo-
nimine was then regenerated, rendering the process catalytic.
The reaction was carried out in a biphasic toluene/water solu-
tion. The compounds were found to be highly selective: they did
not react with carbonyl groups, alcohols or alkynes, and would
only epoxidise alkenes at temperatures >60  C. In the same year,
Hanquet et al. presented oxaziridinium salts as oxygen transfer
agents.121 The oxaziridinium salt reacted with a variety of
compounds with ethene groups to form epoxides in high yields.
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The reactions were carried out in organic solvents. In both of
these publications, the chemistry is presented merely as a
synthetic tool. A breakthrough came when this chemistry was
applied to stain removal and adopted for use in completely
aqueous systems. In 1991, Lever Brothers presented sulfoni-
mines as bleach catalysts,122 and in 1993, quaternary imine
salts123 and quaternary oxaziridinium salts124 followed. Quater-
nary imine salts were later found to produce unacceptable
colour damage,125 and dihydroisoquinolinium catalysts were
found to undergo decomposition reducing their efficiency.105
Quaternary imine zwitterions, which generate quaternary oxa-
ziridinium compounds in situ in the wash, were later presented
as colour-safe alternatives. These molecules can also be
described as organic bleach boosters.125 A source of peracid
must also be included in the detergent formulation in order to
generate the oxaziridinium salt.
It is clear from the above examples that it is one thing to nd
catalysts that are efficient oxidisers of typical laundry stains, but
it is quite another to nd catalysts that also have acceptable dye
and fabric damage proles and are both environmentally
acceptable and cost effective. Extensive studies carried out on a
variety of catalysts and bleaching systems have shown that each
individual bleach system has its own characteristic colour and
fabric damage prole, which cannot be predicted.54 Due to the
risk involved, extensive testing is required before any new
system can be included in a commercial product. Bleaches
affect individual dyes differently and considerations must be
made for the most commonly used dyes, which are likely to have
the most noticeable effect in the market if affected.
12 Challenge of using bleach
activators in liquid detergents
In recent decades, the detergent product line has expanded to
include liquid detergents and single-dose detergents (both
liquid/gel and solid forms). In the USA, liquid detergents have
held a strong market share for some time.40 In Europe, while
liquid detergents have been available since 1981, they have been
slower to take on a signicant market share.17,126 Single-dose
detergents were rst introduced into the UK in 2000, and by
2011 had captured a 16% share of the UK detergent market by
value.127 It has been predicted that this will increase to 22% by
2016.127
When liquid detergents were rst introduced in Europe,
some reported that they were less effective than powder deter-
gents.40 This is understandable because, in Europe, most
powder detergents contain a built-in bleach system; however,
most liquid detergents do not, due to the difficulties associated
with incorporating a bleaching agent in a liquid detergent. In
the USA, historically, the bleach (sodium hypochlorite) was
added separately to the wash, in addition to the main detergent,
regardless of the form of the main detergent.40 As a result, there
is no reduction in efficiency observed by moving from a powder
to a liquid detergent.
It has already been stated that it is possible to have storage-
stable hydrogen peroxide solutions if appropriate measures are
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taken (Section 2). However, forming storage-stable solutions of
bleach activators has proven a challenge, as they tend to
decompose rapidly in solution. Even more elusive is a storage-
stable liquid detergent which includes bleach activators. These
issues are well-recognised and many, many attempts have been
made to develop stable systems (for examples, see the patent by
Croud et al.128 and the references listed therein). Most of these
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methods use deionised water (to avoid metals) or non-aqueous
solvents (particularly alcohols), groups of sequestering agents,
free radical scavengers, and/or solutions with an acidic pH to
enhance stability. Another method investigated involves form-
ing a ‘shell layer’ over a peroxy acid to protect it from the
surrounding solution.129 However, it was found that the
protective layer can dissolve or degrade over time, giving a
limited shelf-life, and shell layers based on waxes proved
problematic as relatively high temperatures are required to melt
the wax to release the peroxy acid, and oen insoluble residues
are le behind.65 Another patent describes the formation of an
aqueous suspension using water-insoluble peroxy acids,
specically detailing a liquid composition using the preformed
peroxy acid DPDDA (Fig. 8).130 Even though a fatty acid and a
secondary alkyl sulfonate were included, and the solution was
maintained at a low pH (preferably 2–5), the resulting solutions
were not sufficiently storage-stable for commercial use.65 Again,
this patent refers to the formation of a liquid peroxide product
and not an all-inclusive detergent formulation.
Many of the methods describe the use of an acidic solution
to increase the acidity of the peroxide-containing liquid
product. From a performance perspective, an acidic wash pH
leads to inefficient bleaching, and alkaline solutions are more
suitable. In order to form a compromise, research was under-
taken to develop laundry detergent compositions in which the
formulation is stored at an acidic pH, and the product contains
a ‘pH jump system’, which creates an alkaline environment in
the wash, allowing effective cleaning to occur.26 In one example,
the peroxy acid is water-insoluble and maintained as a
suspension. The pH jump system involves a polyol, which
complexes with borate in the concentrated product, forming an
acidic solution. On dilution, the borate ion is released from the
polyol, causing an increase in pH.131
PAP (see Section 6) suffers from the same disadvantages with
regard to shelf-life as the bleach activators. It has been reported
that PAP undergoes a steady loss of activity in a liquid
medium.65 However, Solvay currently has a number of aqueous
PAP suspensions available commercially under the brand name
EURECO™. Several concentrations are available, e.g. EURECO
LX5 (5% PAP) and EURECO LX17 (17% PAP),132 and the use of
these products in combination with detergents has been
described by other sources.133 It has been reported that PAP, like
many other peroxy acids, can react with polyvinyl alcohol lms,
weakening or completely destroying the lm.65 This could limit
the use of PAP in liquitab products. However, a recent patent
(2012)65 has claimed storage-stable (and polyvinyl alcohol
stable) aqueous PAP suspensions formed using concentrated
sugar solutions. The quantity of PAP included is 20–40% (of
which 60–70% is active PAP, as the commercial solid contains
stabilisers). In one example, 97% of active PAP remained in the
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suspension aer 12 weeks at room temperature. No degradation
of a polyvinyl alcohol lm was observed over the same time
period.
In 1996, a liquid laundry bleach additive containing the
bleach activator LOBS (Wide Haiter, Kao Corp134) was released
onto the market in Japan.89 This was the rst liquid product in
the world which contained a bleach activator. The anionic
activator was dissolved with a cationic surfactant in a non-ionic
micelle to suppress decomposition by hydrolysis and perhy-
drolysis in the liquid, allowing stable formulations to be
prepared.38 In 2001, a compact version was released,38 demon-
strating the success of the earlier product. However, the bleach
system still undergoes signicant decomposition as reports
have detailed a 20% loss of activity aer thirty days.89 Once
again, this product is a liquid bleach solution, which can be
used as a laundry additive, and is not a complete detergent
formulation.
Multi-chamber systems provide the opportunity to combine
incompatible ingredients in one product. For example, in 2011,
Procter & Gamble led a patent detailing a multi-compartment
pouch, containing a solid bleach in one section, and liquid
detergent composition in a second section.135 Retaining the
bleach in a solid form could avoid issues with activator/peroxy
acid stability in solution.
13 Recent advances
More recent patents continue to show innovation work in the
area of organic bleach boosters, as well as more focus on
formulation; for example several patents from P&G have
emerged regarding the production of co-granules or co-parti-
cles, which are particles consisting of hydrogen peroxide and a
bleach activator bound together.136,137 One of the ideas behind
co-particles is to locate the persalt and the bleach activator in
close proximity, whereby the perhydrolysis reaction will occur
more readily in the wash, and the amount of hydrogen peroxide
lost through reaction with catalase or metal ions is reduced. The
aim is to increase the efficiency of the bleaching system by
reducing the excess of persalt required (as currently, typically 3–
5 times molar excess of persalt is added).
Several patents have emerged which detail bleach catalysts
that can react with atmospheric oxygen for the removal of
stains.138,139 Unilever patented a catalyst capable of using
dioxygen from the air as early as 1999, but the intended use
appeared to be in combination with an oxygen source in the
formulation.119 Later, patents emerged where the omission of
peroxygen bleaching agents was intended,138 and detailed the
use of these catalysts in aqueous solutions.139 Currently, this
technology appears to be limited to specic stain removers, but
ideally this chemistry could be applied to a complete detergent
formulation, the advantages of which are obvious. While
hydrogen peroxide is a benign bleaching agent, persalts can
assume up to 20% of a typical detergent formulation. The
removal of these compounds would decrease the mass and
space occupied by detergents and open up opportunities for the
further compaction of detergents.
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Given the current environment of convenience (e.g.,
compaction) and energy saving (e.g., low temperature wash),
combined with the capital investment required for stoichio-
metric chemistry, we expect bleach innovation to continue in
the area of nding a suitable bleach catalyst (see Section 11)
which can withstand the scrutiny of repeated washing trials.
Another area which has already been discussed is the drive to
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incorporate oxygen-based bleaching agents in liquid detergents
(Section 12). While efforts have been made in this area, an ideal
solution has not yet been found.
14 Conclusions
This review has described the development of oxygen-based
bleaching systems as used in domestic laundry detergents. As it
should have become clear to the reader, developing new
bleaching systems and stably formulating them into detergents
poses several challenges. Innovation in this eld is still possible
and of interest.
All the new bleaching systems developed through the years
are being exploited mainly in powder detergents (see Table 4).
As far as liquids are concerned, there has been some success in
the use of hydrogen peroxide or LOBS/hydrogen peroxide, yet
only for liquid laundry additives, not in fully formulated
detergents.
There is still a desire in the eld to nd new or improved
systems which are more active at lower temperatures, as the
drive for energy efficiency continues. The areas of incorporating
bleaching systems in liquid detergents, and the development of
bleach catalysts are continuing areas of research, with the aims
to satisfy consumer demand and, ideally, lead to the further
compaction of detergents. As the majority of this work is carried
out in industrial laboratories, previously very little information
on detergent developments has been shared in the journal
literature. We trust this review will shed some much needed
light on this fascinating, and challenging, chemistry.
15 Glossary
Bleach: general term to indicate oxidative chemistry used in
detergency. Bleaches can be chlorine based (e.g., hypochlorite)
or oxygen based (e.g., hydrogen peroxide). It can be used also to
indicate reductive chemistry (e.g., thiourea dioxide). Typically
the latter are called reducing bleaches.
Bleach activator: a compound which reacts with hydrogen
peroxide to form a peroxy acid.
Table 4 Summary of current bleach systems used in powder
detergents
Bleaching systems US Europe Asia
NOBS/percarbonate 3 3
TAED/percarbonate 3
DOBA 3
LOBS 3 washing machine images in Table 2; Panasonic for the Japan
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Bleaching: a decolourisation or whitening process that can
occur in solution or on a surface.
Detergent: a formulation comprising essential constituents
(surface-active agents) and subsidiary constituents (builders,
boosters, llers and auxiliaries) that is used for cleaning.
Fluorescent whitening agent: a substance that is added to
detergents to make fabrics appear whiter and some colours
appear brighter. Fluorescent whitening agents are absorbed
onto fabrics where they act by converting invisible UV light to
visible blue light.
Gpg: ‘grains per gallon’; a unit of water-hardness.
Industrial and institutional detergents: (I&I detergents) refers to
those detergents used outside the home e.g. in hospitals,
schools, hotels etc.
Laundry additive: a product used in combination with a deter-
gent for improved stain removal.
Optical brightener: see uorescent whitening agent.
Oxidative bleach: a compound that releases chloride, hydrogen
peroxide or singlet oxygen during the wash, or is a peroxide of
an organic acid.
Oxygen bleach: a bleach containing peroxygen compounds e.g.
hydrogen peroxide.
Perhydrolysis reaction: the reaction between the perhydroxyl
anion and a bleach activator to form a peroxy acid.
Peroxide: a compound containing an oxygen–oxygen single
bond or the peroxide anion [O–O]2.
Peroxy acid: (also known as peracid) is a compound which
contains the functional group ‘–O–OH’
Persalt: a solid hydrogen peroxide carrier.
Pretreatment: in order to remove larger stains and soils, fabrics
are oen subjected to a stain-removing process such as soaking,
or use of a laundry additive/stain remover before being placed
in the washing machine. These processes are known as
pretreatments.
Saponication: hydrolysis of an ester under basic conditions to
form an alcohol and the salt of a carboxylic acid.
Soap: sodium or potassium salts of fatty acids.
Stain: a discolouration produced by absorption of or contact
with foreign matter; usually, one that penetrates below the
surface and is not easily removable.140
Surfactant: a contraction of ‘surface-active agent’, is a substance
which lowers the surface tension of the medium in which it is
dissolved, and/or the interfacial tension with other phases, and,
accordingly, is positively adsorbed at the liquid/vapour and/or
at other interfaces.141
Acknowledgements
The authors would like to thank a number of sources who
shared or provided information and images which were used in
this review. These include: Euromonitor for allowing us to use
the market data provided in the abstract and introduction;
Henkel for providing the images in Fig. 2; Procter & Gamble for
providing the information included in Table 2 and Fig. 13;
Whirlpool for use of the USA/Canada and Western Europe
washing machine image in Table 2 and help on the information
This journal is © The Royal Society of Chemistry 2015

Review
shared in the table; Taylor and Francis US for use of Fig. 9, 10
and 12(B) conveyed through Copyright Clearance Center, Inc.;
and Wiley VCH for use of Fig. 12(A).
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