Cellulose 7: 263–286, 2000.

c 2000 Kluwer Academic Publishers. Printed in the Netherlands.

Alkaline hydrogen peroxide bleaching of cellulose

ROBERT E. BROOKS and SAMUEL B. MOORE∗

Burlington Chemical Company, Inc., P.O. Box 111, 615 Huffman Mill Road, Burlington,
NC 27215

Received 16 February 2000; accepted 20 June 2000

Abstract. A closed system bleaching apparatus was designed to determine the kinetics and
effects of various factors on alkaline hydrogen peroxide bleaching of textile cellulose fabrics.
It was confirmed that perhydroxyl anion is the primary bleaching moiety in alkaline hydrogen
peroxide systems. The use of the apparatus in the measurement of fabric color, waste oxygen,
and the subsequent calculation of hydroxyl ion, and molecular hydrogen peroxide confirmed
that pH and titration of ‘free’ hydrogen peroxide in alkaline bleaching systems are not good
indicators of bleaching mechanism. The role of the cellulose itself in the chemical bleach-
ing system was determined. The rate of bleaching on cotton fabric was shown to be a first
order reaction in concentration of perhydroxyl anion at 60 and 90 ◦ C. An activation energy
of 17 kcal/mole was estimated. Decomposition of H2 O2 into waste oxygen was found to be
second order kinetics.

Key words: bleaching, cellulose, hydrogen peroxide

Introduction

The bleaching of cellulose by alkaline hydrogen peroxide is an established

industrial process. This does not mean however, that the mechanism of al-
kaline peroxide bleaching of cellulose is well elucidated. A review of the
pertinent literature indicates continued disagreement on both the mechan-
ism of bleaching and the appropriate techniques to measure the chemical
changes in aqueous alkaline peroxide solutions in contact with bleachable cel-
lulose (Simon and Drelich, 1946; Evans and Uri, 1949; Duke and Haas, 1961;
Goodman and Wilson, 1962; Koubek et al., 1963; Taher and Cates,1975;
Steinmiller and Cates, 1976; Isbell et al., 1981; Galbacs and Gangi, 1983;
Evans and Upton, 1985; Dannacher and Schlenker, 1996; Spiro and Griffith,
1997; Thompson et al., 1993, 1994, 1999; Milne, 1998).
Textile, paper, and the domestic and commerical laundry industries are
all interested in producing the highest bleaching effects on cellulose without
damaging the cellulose polymer. To achieve this ‘holy grail’ of bleaching

∗ Author for correspondence.

264

requires the ability to precisely measure many chemical parameters of al-

kaline peroxide solutions in contact with cellulose.

Goals

In order to clearly define the chemistry and action of alkaline bleaching, the
following measurements are necessary:
• Amount of oxygen (O2 ) released during bleaching,
• Bleach bath pH,
• Hydrogen peroxide and sodium hydroxide concentrations during bleach-
ing,
• Fabric ‘whiteness’ i.e., bleaching effectiveness,
• Temperature.
These measurements required the fabrication of a gas tight bleaching sys-
tem and ‘real time’ measurements during the bleaching cycle. From these
measurements, calculation of the following factors is necessary to model the
bleaching process:
• kinetics of fabric bleaching (whiteness over time)
• kinetics of the decomposition of alkaline H2 O2 into oxygen
• Perhydroxyl anion, hydroxylanion, and undissociated H2 O2 concentra-
tions
The research described in this paper discusses some relevant literature
on bleaching with alkaline H2 O2 . It describes the apparatus and techniques
developed to measure the factors discussed above, and the calculations ne-
cessary to determine the species involved in bleaching performance. In the
conclusions it lays the groundwork for further investigations into the effect-
iveness of auxiliary chemicals in textile bleaching.

Literature review

Bleaching of cellulose with H2 O2 has been extensively studied, but problems

remain in quantification of the bleaching species versus whiteness of fabrics.
As a general consensus, the perhydroxyl anion is proposed as the primary
species responsible for bleaching and is a product of the reaction between
H2 O2 and NaOH in aqueous solution. However, debate continues on the roles
played in bleaching by free radicals, nascent oxygen, or some other form of
oxygen.
Taher and Cates (1975a) proposed a mechanism where the hydroxyl radi-
cal OH· and the perhydroxyl radical OH2 · forms a chain reaction, which
 265

results in the decomposition of H2 O2 into oxygen and water. Bleaching oc-

curs when the fabric reacts with these radicals and thereby acts in a chain
termination role. Steinmiller and Cates (1976a) later examined the effect of
different fabric treatments and were able to demonstrate the presence of free
radicals by initiating the polymerization of methyl methacrylate in a bleach
bath, but the existence of ‘free radicals’ alone does not confirm their role in
bleaching.
Dannacher and Schlenker (1996a) rejected the role of the perhydroxyl
anion in bleaching because of a belief that there is an optimum pH beyond
which bleaching decreases. But these authors also point out that this has not
been substantiated experimentally. This pH dependence of H2 O2 bleaching
suggests that the perhydroxyl anion is not the active bleaching agent. They
−
purposed instead that the active oxygen is the superoxide radical Ȯ2 , formed
in an alkaline medium from the perhydroxyl radical. The relationship they
use to estimate the concentration of this radical is not clearly defined but has
a lot of similarity to that used by Duke and Haas (1961a) to measure the
decomposition of H2 O2 .
Spiro and Griffith (1997a) claim that there is no need to involve any other
oxidizing species other than HO− 2 and H2 O2 . The extensive investigations
by Thompson et al., (1993), (1994) and (1999a) were concerned with the
bleaching of certain dyes by H2 O2 in aqueous solution and did not include
fabric. The need to include fabric in any study of textile bleaching was clearly
demonstrated by Simon and Drelich, (1946a).
In many of the references, measurements of H2 O2 concentration are made,
but many without cotton fabric being present. In actual textile and paper
bleaching production situations, the perhydroxyl anion is not measured but in-
stead total H2 O2 available is determined by titration under acidic conditions.
pH and total alkalinity are also measured during the course of bleaching, but
this data is not used to calculate perhydroxyl anion concentrations, which
must be determined to define bleaching efficiency.
Our belief is that the perhydroxyl anion formation is the key to textile
bleaching and that the degree of whiteness obtained is directly related to
the concentration of perhydroxyl anion in the bleaching solutions. There are
two competing reactions of H2 O2 in the bleaching bath: first, there is the
reaction with colored bodies on the fabric to give bleached fabric and second,
decomposition to form oxygen. An enclosed apparatus was developed that
can measure the release of gaseous oxygen and the whiteness of bleached
fabrics. The design of the apparatus and its operation are described in the
experimental section.
266

Experimental

Calculations of perhydroxyl anion in alkaline H2 O2 bleach solutions were

performed and measurements were made of the effects on bleaching perform-
ance on cotton, cellulose based textile fabrics.
Hydrogen peroxide was provided by Solvay Interox as Ultra Pure 31% and
was diluted with deionized water for use as a stock solution of about 0.7 M.
This stock solution was then standardized against potassium permanganate
just before each use and diluted accordingly.
Sodium hydroxide was reagent grade, certified 0.5 or 1.0 N and was di-
luted and used as needed. Aliquots of each of the above stock solutions were
taken by use of a Rainin2 automatic pipette, which could be adjusted, from 0
to 10 ml in 0.1 ml increments.
De-ionized water was used in all dilutions and great care was used to
prevent contamination by trace metal ions.
To insure complete wetting and to aid in the removal of entrapped air, a
nonionic wetting agent, Neodol 25–20, (Shell Chemical, USA) was added
from a stock solution at a level of 0.10% in each bleach run. This surfactant
is a primary alcohol (C12 –C18 ) with 20 moles of ethylene oxide per mole of
alcohol.

Fabric

Desized but unbleached, 100% cotton fabric was used to measure the rate of
bleaching. This fabric was obtained from Test Fabrics, Inc., West Pittson, PA,
as Style 428-U, Army Carded Sateen. The fabric as received had a uniform
light tan color. Each bleaching experiment used a piece cut 2 inches by 4
inches and weighed on average 1.21–1.22 g. Analysis of this fabric gave 0.2%
total ash content and indicated the following concentration of metals in mg/kg
as seen in Table 1.

Apparatus

All bleaching experiments were conducted in an 125 ml Erlenmeyer flask

placed in a constant temperature bath controlled to ±0.5 ◦ C. Stirring during
bleaching was provided by a magnetic stir bar in the flask placed over a sub-
mersible variable speed magnetic stirrer. An overhead glass column provided
an outside addition funnel connected though a stopcock to a tube dipping to
below the surface of the liquid in the bleach bath for peroxide addition after
assembly and reaching temperature. This column also had a stopcock to a vent
 267
Table 1. Fabric analysis metal concentrations

Element mg/kg

Ca 528.0
Mg 166.0
Al 24.0
Fe 12.0
Mn 1.6
Zn 1.3
Cu 0.5

tube, which could be opened to allow the peroxide addition at atmospheric

pressure. At the top of the column was a pressure transducer to detect the
oxygen pressure generated. The output voltage was converted directly to mm
Hg by a DP25-S Strain Gage Meter from Omega Engineering, Inc., Stamford,
CT. The total overhead volume was kept to a minimum and was calibrated for
each flask for the purpose of calculating the moles of oxygen produced. The
overhead temperature was monitored during each run. Figure 1 illustrates this
apparatus.

Conditions

The conditions for each experiment were set as follows unless otherwise
stated: total volume of bleach bath 120 ml; one piece of fabric 2 inches by
4 inches; temperature of the bath 90 ◦ C; time of measurement of oxygen
pressure every 2 min for 12 min; time of fabric bleach 12 min; time of equi-
libration at temperature before the addition of H2 O2 30 min.

Procedure

Each flask was charged with de-ionized water, nonionic surfactant and the
required amount of NaOH. A sample of loosely rolled fabric was then added
to the flask. The flask was placed in the water bath and an overhead condenser
was attached to the flask. The flask was brought to temperature and allowed to
equilibrate to remove any air trapped in the fabric. After 30 min the flask was
moved and connected to the overhead column through a spherical glass joint
(without silicone grease). A Teflon O-Ring sealed this joint and was held in
place by a locking clamp. The required amount of H2 O2 was added with the
268

Figure 1. Experimental bleaching apparatus.

vent tube open. Immediately all stopcocks were closed and the timer was star-
ted. Oxygen pressure was measured every 2 min for a total of 12 min. After
12 min, the fabric was removed and rinsed thoroughly in running cold water.
The fabric was air dried over night and the K/S (whiteness) value measured.

pH measurement

The pH was not measured continuously throughout the procedure because of

the constraints of the procedure and equipment. The bleach bath was cooled
in an ice water bath immediately after termination of the 12 min bleach cycles
and the pH measured at 25 ◦ C. This final pH is slightly different than the start-
ing pH because a small amount of H2 O2 , a weak acid, was used for bleaching
and oxygen production.
 269

K/S measurement

All cotton samples were dried at ambient conditions for 12 h prior to reflect-
ance measurements. The reflectance of the fabric was read on a Spectraflash
SF-600 reflectometer by Datacolor International with the readings converted
by the instrument to the Kubelka and Munk K/S value. An ‘unbleached’
and a ‘complete bleach’ fabric sample were included in each set of experi-
mental bleached samples as standards. The ‘unbleached’ sample was fabric
treated 120 min at bleaching temperature in a bath of 0.1% Neodol and 0.10 M
NaOH. The ‘complete bleach’ sample was treated the same as above with
0.10 M H2 O2 . For a quantitative measure of ‘color matter’ the following
equations were used:
 
K
Ao = = ‘Unbleached’ Fabric
S o
 
K
A∞ = = ‘Complete Bleach’ Fabric
S ∞
 
K
As = = ‘Experimental Sample’ Fabric
S s

Ct , the ‘color’ remaining in a bleached sample after time, t, is equal to:

 
As − A∞
Ct = (1)
Ao − A∞

Oxygen measurement

Immediately after the H2 O2 was added to the bleaching apparatus at temperat-

ure, the pressure was recorded every 2 min for a total of 12 min. This pressure
represents the total pressure in the apparatus, which is composed of air, water
vapor, and oxygen generated in the decomposition of the peroxide. A plot
of the logarithm of the pressure versus time is linear after the initial up-set
conditions. Extrapolation back to zero time gives the logarithm of the pres-
sure correction, log (Po ), which is converted, back to Po . This is background
pressure and corrects for air, water vapor, etc. and is subtracted from every
total pressure reading to give an estimate of the partial pressure of oxygen
produced by the decomposition of H2 O2 to form gaseous oxygen. While an
estimate of the oxygen partial pressure is used, it is the rate of change that we
270

use to calculate the rate constant (k) and would be independent of a constant
error in the absolute partial pressure.
The partial pressure of oxygen is converted to moles of oxygen by use of
the ideal gas laws and apparatus over-head volume and temperature. Moles
of oxygen are multiplied by two to give moles of H2 O2 used for oxygen
production by the stoichometry of the Equation (2)

2H2 O2 −→ 2H2 O + O2 . (2)

This defines the quantity of H2 O2 used to produce oxygen and is subtracted

from the initial concentration of H2 O2 , Ao , to give At , the concentration of
hydrogen peroxide left at each time, t. Finally the reciprocal of this H2 O2 con-
centration is tabulated for each measurement time. The integrated expression
of the second order kinetic rate equation is:
1 1
− = ko t. (3)
At Ao
Plotting 1/At versus time gives straight line with a slope of Ko , the observed
rate constant. The overall rate constant, k1 , is calculated using the following
equation (see derivation in the oxygen kinetic section)
ko
k1 = . (4)
Keq [OH− ]
As a matter of experimental practice, reaction times are kept as short as pos-
sible to produce an initial rate where reactants and pH remain effectively
constant.

Bleach kinetics

If bleaching were dependent upon the concentration of the perhydroxyl anion,

then the equations for bleaching cotton fabrics would be represented by:

OH− + H2 O2  HO−
2 + H2 O. (5)

Followed by the rate controlling step

C + HO−
2  Bleached fabric. (6)

Where the symbol C is intended to represent the reaction component of the

coloring matter in the fabric. The mechanism of bleaching as depicted in
Equation (6) is not well understood. Some of the chromophoric bodies oxid-
ized during the bleaching process are undoubtedly conjugated double bonds.
 271

The mechanism of oxidation proceeds to alcohol formation via an inter-

mediate epoxide as suggested by Milne (1998a).
The rate equation for the bleaching process in Equation (6) may be
described as follows:
dC
− = koverall [HO−
2 ][C]. (7)
dt
If the bleach experiment is conducted under conditions where a large excess
of peroxide and caustic are maintained over the amount of ‘color’, then the
kinetics will be pseudo first-order in terms of ‘color’ removal. Let
kobs = koverall [HO−
2 ], (8)
Then
dC
= −kobs [C], (9)
dt
which integrates to
 
Ct
ln = kobs t, (10)
Co
where kobs is the specific rate constant for the particular concentration of
peroxide and caustic being used. Then a plot of the experimental observed
kobs versus the perhydroxyl anion concentrate should be linear with the slope
equal to the overall rate constant, koverall , as given in Equation (8).

Oxygen kinetics

The decomposition of hydrogen peroxide may proceed by both a chain and

a non-chain process as observed by Isbell et al., (1981a). The chain reaction
is thought to be started by radicals mainly generated by metal ions such as
iron and copper (Koubek et al., 1963a; Galbacs and Gangi 1983a; Thompson
et al., 1993, 1994, 1999b). We used every precaution to avoid the introduction
of such ions, and no chelating agents were used.
In the absence of metal ions, a non-chain process occurs when one mole
of H2 O2 and one mole of perhydroxyl anion form an intermediate complex,
which decomposes to molecular oxygen. The formation of this intermediate
is the rate-controlling step. This is the mechanism suggested by Duke and
Haas (1961b) and later by Goodman et al. (1962a).
In alkaline solutions this can be represented by a series of reactions:
keq
OH− + H2 O2  HO−
2 + H2 O, (11)
272
k1
H2 O2 + HO− −
2  HO + H2 O + O2 , (12)
K2

kion
H2 O2 H+ + HO−
2. (13)

From reaction Equation (11), the equilibrium constant can be calculated:

[HO−
2] Kion
Keq = − = , (14)
HO [H2 O2 ] Kw
where
Kw = [OH− ][H+ ] and, (15)

[H+ ][HO− 2]
Kion = , (16)
[H2 O2 ]
for the rate controlling reaction Equation (12), the rate equation is calculated
by
dO2
= +K1 [H2 O2 ][HO−
2 ]. (17)
dt
The stoichiometry of the overall equation is obtained by adding Equation (11)
and (12)
2H2 O2 → 2H2 O + O2 (18)
and thus
dH2 O2 dO2
= −2 . (19)
dt dt
The factor of minus two (−2) is accounted experimentally when we calculate
the moles of H2 O2 used, from the oxygen pressure,
 
dH2 O2 dO2
cal. = . (20)
dt dt
Substitution of Equation (20) into Equation (17) gives the rate equation in
terms of hydrogen peroxide.
dH2 O2
= k1 [H2 O2 ][HO−
2 ]. (21)
dt
Substituting perhydroxyl anion (HO−
2 ) from Equation (14), this becomes

dH2 O2
= k1 [H2 O2 ]2 [HO− ]Keq . (22)
dt
 273

At a fixed starting concentration of NaOH and H2 O2 , the concentration of

[OH− ] is determined completely by the equilibrium constant and is therefore
fixed. Let
ko = k1 Keq [OH− ].
Substituting and separating variables Equation (22) becomes
dH2 O2
= ko dt. (23)
[H2 O2 ]2
This is now a second-order equation in H2 O2 and may be integrated to give
1 1
− = ko t. (24)
[H2 O2 ]t [H2 O2 ]o
A plot of 1/[H2 O2 ]t versus t is linear with a slope equal to ko . Rearrangement
of the equation ko = k1 Keq [OH− ], from above, gives the overall rate constant
k1 .
ko
k1 = . (25)
keq [OH− ]
To determine the change in rate as a function of pH, [OH− ] = Kw /[H+ ] is
substituted into Equation (25) and recall that,
 
HO− Kion
Keq = −
2
=
[HO ][H2 O2 ] Kw
from Equation (14). This gives
Kion
ko = k1 × . (26)
[H+ ]
Taking the logarithm of both sides of the equation and rearranging gives
log K1 = log k0 − log Kion − pH. (27)
Therefore, the rate of oxygen produced should be a linear function of the pH.

Perhydroxyl anion calculation

It is necessary that the ionization constant, Kion , for H2 O2 be calculated at the

temperature at which the bleaching is to be carried out. The ionization rate
constant Kion is available in the literature for 25 ◦ C but must be calculated for
the experimental temperature.
kion
H2 O2 H+ + HO−
2 (28)
274

[H+ ][HO− 2]
Kion = . (29)
[H2 O2 ]
Using the values given by Evans and Uri (1949a):
Kion = 2.24 × 10−12 @25 ◦ C,
with a heat of reaction equal to +8.2 kcal/mol. This allows for the utilization
of the van’t Hoff equation for the calculation of the Kion at temperatures other
than 25 ◦ C. Assuming the heat of reaction does not change much over the
temperature range.
 
1H T2 − T1
Log K2 − Log K1 = , (30)
4.576 T2 × T1
where
1H = Heat of reaction (cal),

T = absolute temperature(◦ K).

Using this relationship the following ionizations constants were calculated:

Temperature Ionization constant

35 ◦ C 3.51 × 10−12
60 ◦ C 9.49 × 10−12
90 ◦ C 2.66 × 10−11

Dividing this ionization constant by the ionization constant for water, Kw =

[H+ ][OH− ], we obtain the equilibrium constant for the reaction:
keq
OH− + H2 O2 HO− 2 + H2 O (31)
 
HO− Kion
Keq = −
2
= . (32)
[HO ][H2 O2 ] Kw
This resulted in the following equilibrium constants:

Temperature Keq Kw

35 ◦ C 168 2.09 × 10−14

60 ◦ C 99 9.61 × 10−14
90 ◦ C 62 4.30 × 10−13
 275

where Kw is value as given in the Handbook of Chemistry and Physics, 66th

Edn, page D-164.
Evans and Uri (1949a) also expected that the second dissociation of H2 O2
to be extremely small due to the high endothermicity that they estimated,
∼100 kcal for this step. Therefore, we did not include the reaction:

HO− + −
2  H + O2 , (33)

with the above equilibrium constants, the concentration of perhydroxyl anion

may now be calculated from the starting NaOH and H2 O2 concentrations.
Let
N = Starting NaOH concentration in moles/l
H = Starting H2 O2 concentration in moles/l
X = [HO− −
2 ] formed and is also equal to [OH ] reacted.

Then by charge balance

[HO− − + +
2 ] + [OH ] = [Na ] + [H ]. (34)

However, at pH above 10, [H+ ] approaches zero, and upon rearrangement

Equation (34) becomes

[OH− ] = N − X. (35)

By H2 O2 balance

H = [HO−
2 ] + [H2 O2 ], (36)

which gives

[H2 O2 ] = H − X. (37)

Where [H2 O2 ] is undissociated hydrogen peroxide left at equilibrium. Then

[HO−
2] X
Keq = − = , (38)
[OH ][H2 O2 ] (N − X)(H − X)
solving for X gives
√
−R − R2 − 4NH
X= , (39)
2
where
 
1
R −N − H − , (40)
Keq
276

from the value of X = [HO−

2]

[H2 O2 ] = H − X by Equation (37)

and

[OH− ] = N − X by Equation (35).

From the value of [OH− ]

Kw
[H+ ] =
[OH− ]

and

pH = log[OH− ] − log Kw ,

where Kw must be for the same temperature as that at which the pH is meas-
ured. Because of the large difference in Kw at various temperatures, this can
be significant. For this reason and because of the importance of pH in the
discussion of the kinetic of bleaching, we calculated the pH at both ambient
and at bleach temperature.
The importance of calculating the perhydroxyl anion concentration can
be illustrated by the following examples. Because of the interaction of the
hydroxyl ion and H2 O2 , a weak acid, different solutions where either OH
or H2 O2 may be in excess might have the same pH and yet have a 10-fold
difference in perhydroxyl anion concentration. For example:

Starting Calculated
NaOH H2 O2 [HO−
2] [H2 O2 ] [OH− ] pH@60 ◦ C pH@25 ◦ C

0.075 0.010 0.0087 0.0013 0.0663 11.84 12.83

0.150 0.100 0.0864 0.0136 0.0636 11.82 12.80

Conversely, two solutions may give the same approximate concentration

of perhydroxyl anion and have a different pH.

Starting Calculated
NaOH H2 O2 [HO−
2] [H2 O2 ] [OH− ] pH@60 ◦ C pH@25 ◦ C

0.050 0.080 0.0399 0.0401 0.0101 11.02 12.00

0.075 0.050 0.0391 0.0109 0.0359 11.57 12.56
 277

This data clearly demonstrates why plotting reaction rates versus pH can-
not describe bleaching results. The more preferred correlation is between the
specific rate constant and perhydroxyl anion concentration. pH alone does
not adequately define the concentration of various ionic forms of hydrogen
peroxide and hydroxide ions present. This is addressed in the performed
experiments.
Some past investigations have used buffers to maintain a constant pH to
avoid this issue. If the purpose is to study the effects of various species on
bleaching, then these reactants must be analyzed or calculated by the use of
equilibrium constants. The use of a buffer will prevent this calculation of the
perhydroxyl anion.

Fabric bleaching results

Bleaching experiments were made varying the concentration of NaOH and

H2 O2 [one at a time]. Table 2 demonstrates no correlation between bleach
rate and the concentration of these reactants.The specific rates constant for
bleaching was plotted against the pH to try to verify the work of (Dannacher
and Schlenker, 1996b). This is shown in Figure 2. There seems to be no direct
correlation between pH and the reaction rate, particularly at higher pH where
we are most interested.
The results from the experiments listed in Table 2 demonstrates the need
to know the concentrations of the three species, hydroxyl, perhydroxyl, and
undissociated H2 O2 . Titration for H2 O2 under acidic conditions, as is usually
performed, in bleaching is of no help since this does not reveal the concen-
tration of the species present under alkaline conditions of bleaching. Using
the procedure given earlier, the concentrations of each of these species was
calculated from the starting concentrations of NaOH and H2 O2 . Also calcu-
lated was the pH the solution would have at 90 ◦ C. These results are given in
Table 3. The calculated concentration of perhydroxyl anion [HO− 2 ] is plotted
against the specific rate constants, in Figure 3. The data and calculations
from the bleach experiments show the linear relationship expected from the
mechanism proposed in the kinetics section of this paper. The slope of the
graph is equal to the overall rate constant, koverall, as given in Equation (10).

koverall = 27.2 × 10−3 l/mol s@90 ◦ C.

To get an estimate of the effect of temperature, a limited number of bleach

runs were made at 60 ◦ C. These results are in Table 4.
Again, the specific rate constant for bleaching was plotted against the
pH to look for direct correlation. As shown in Figure 4, there is a general
278
Table 2. rates at 90 ◦ C; rates in l/mol s using Keq = 61.78@90 ◦ C

Run # Start NaOH Start H2 O2 25 ◦ C pH 25 ◦ C pH Bleach -kx

measured calculated 1000

15 0.025 0.037 11.34 12.02 1.093

16 0.025 0.044 11.30 11.96 0.815
17 0.025 0.052 11.22 11.90 0.907
18 0.025 0.059 11.13 11.85 0.870
19 0.006 0.044 10.40 11.26 0.491
20 0.013 0.044 10.83 11.60 0.691
21 0.019 0.044 11.10 11.80 0.927
22 0.025 0.044 11.32 11.96 0.918
23 0.031 0.044 11.49 12.09 0.966
24 0.038 0.044 11.64 12.19 1.046
25 0.044 0.044 11.80 11.93 0.957
26 0.050 0.044 11.94 12.37 1.041
27 0.063 0.044 11.94 12.52 1.104
28 0.075 0.044 12.10 12.63 1.095
29 0.088 0.044 12.20 12.73 1.082
30 0.100 0.044 12.33 12.81 1.255
31 0.050 0.044 11.80 12.37 1.071
32 0.025 0.059 11.07 11.85 1.043
41 0.100 0.059 12.16 12.74 1.856
42 0.100 0.074 12.12 12.66 1.895
43 0.100 0.089 12.06 12.58 2.098
44 0.100 0.103 12.00 12.50 2.273
45 0.075 0.059 11.96 12.54 1.625
46 0.075 0.074 11.88 12.45 1.733
47 0.075 0.089 11.76 12.36 1.975
48 0.075 0.103 11.65 12.28 2.060
Table 2 shows the starting concentration, together with the measured final pH
and the specific rate constants kobs . Also in Table 2 is shown the calculated
value the pH of the starting mix would have if cooled to 25 ◦ C.

increase in the rate as the pH increases. However, at pH values above 11.5,

data is scattered and it would be difficult to draw any conclusions. When these
same rates are plotted against the corresponding calculated concentrations of
perhydroxyl anion as in Figure 5, a linear relationship is revealed. The slope
of this line gives the overall rate constant for bleaching at 60 ◦ C.

koverall = 5.5 × 10−3 l/mol s@60 ◦ C.

 279

Figure 2. Bleach rate (90 ◦ C).

Finally the Arrhenius equation was used to estimate the activation energy, Ea ,
from the overall rate constant at 60 ◦ C and 90 ◦ C.

Ea = 17 kcal/mole.

This is close to the values of 16.4 and 16.7 kcal/mole given by (Thompson
et al., 1993, 1994, 1999c) for the bleaching of Alizarin and Crocetin by H2 O2 .
These authors suggest that the mechanism of the bleach reaction is similar and
involves formation of an epoxide.

Oxygen results

It is difficult to study the rate of alkaline decomposition of H2 O2 to oxygen

because the reaction is so sensitive to adventitious catalysis. Many materials
can act as catalysts, both homogeneous and heterogeneous. Even the nature
of the reaction vessel and atmospheric carbon dioxide are reported to increase
the ‘spontaneous’ decomposition of peroxide. Perhaps the most unavoidable
is the purity of the alkali used. Literature values for the uncatalysed decom-
position of at H2 O2 35 ◦ C vary with the degree of purification from 7.4×10−4
l/mole s to 3.7 × 10−8 l/mole s (1985a).
The object of this investigation was not to determine the absolute rate for
the spontaneous decomposition H2 O2 but to find the order of reaction with
respect to H2 O2 and perhydroxyl anion and the dependency of the rate upon
pH under the same conditions as the bleach experiments.
280
Table 3. Rates at 90 ◦ C; rates are in liter/moles s using Keq = 61.78@90 ◦ C

Run # Bleach kx Calculated Calculated Calculated Calculated pH

1000 [HO−2] [H2 O2 ] [OH−] @ 90 ◦ C

15 1.093 0.145 0.022 0.011 10.390

16 0.815 0.159 0.028 0.009 10.330
17 0.907 0.017 0.035 0.008 10.270
18 0.870 0.018 0.041 0.007 10.220
19 0.491 0.005 0.040 0.002 9.630
20 0.691 0.009 0.036 0.004 9.970
21 0.927 0.013 0.032 0.006 10.170
22 0.918 0.159 0.029 0.009 10.320
23 0.966 0.019 0.025 0.012 10.450
24 1.046 0.022 0.023 0.016 10.560
25 0.957 0.024 0.020 0.015 10.660
26 1.041 0.026 0.018 0.024 10.740
27 1.104 0.030 0.014 0.033 10.890
28 1.095 0.032 0.012 0.043 11.000
29 1.082 0.034 0.010 0.054 11.100
30 1.255 0.035 0.009 0.065 11.180
31 1.071 0.026 0.180 0.024 10.740
32 1.043 0.018 0.041 0.007 10.220
41 1.856 0.046 0.014 0.054 11.100
42 1.895 0.055 0.019 0.046 11.020
43 2.098 0.062 0.027 0.038 10.950
44 2.273 0.068 0.035 0.032 10.870
45 1.625 0.040 0.019 0.035 10.910
46 1.733 0.047 0.027 0.028 10.810
47 1.975 0.052 0.037 0.023 10.730
48 2.060 0.056 0.047 0.019 10.650

Table 2 shows the specific rate contant, kobs , and calculated values.

The experimental oxygen data generated during bleaching could be

modeled on the basis of the equation for the second order rate constant, ko , as
developed in the section on oxygen kinetics. Table 5 gives this rate constant,
ko , together with the overall rate constant, k1 , and the measured final pH at
25 ◦ C.
The derived Equation (27) predicts that the logarithm of the overall rate
constant, k1 , should be a linear function of the pH. Figure 6 shows a plot of
Log k1 versus pH. This graph gives a reasonable linear fit considering the
experimental difficulties in keeping out spurious catalytic decomposition.
 281

Figure 3. K/S bleach rate (90 ◦ C).

Table 4. Results for bleach study at 60 ◦ C; all concentrations are in moles/l rate constant is
in l/mole s

Second Start Start Calculated Calculated Calculated Measured Bleach kx

set run NaOH H2 O2 [HO−2 ] [H 2 O 2 ] [OH−] pH @ 60 ◦ C 1000

1 0.015 0.050 0.012 0.038 0.003 10.770 0.583

2 0.020 0.050 0.016 0.035 0.005 11.030 0.664
3 0.030 0.050 0.022 0.028 0.008 10.330 0.653
4 0.050 0.050 0.032 0.018 0.018 11.820 0.687
5 0.080 0.050 0.040 0.010 0.040 12.220 0.846
6 0.080 0.080 0.056 0.024 0.024 12.020 1.154
7 0.100 0.080 0.063 0.017 0.037 12.220 0.955
8 0.100 0.100 0.730 0.027 0.027 12.090 1.000
9 0.120 0.100 0.080 0.020 0.040 12.280 1.035
10 0.150 0.100 0.086 0.014 0.064 12.460 0.886
11 0.170 0.100 0.089 0.011 0.081 12.580 0.942
12 0.200 0.110 0.100 0.010 0.100 12.640 1.191

Note that in general the specific rate constant, ko shows some increase
with pH, but does not pass through a maximum and decrease as has been
reported by some (Duke and Haas, 1961c). Our findings are more like those
of Thompson et al. (1993, 1994, 1999d) who found the rate continued to
increase even at pH above 12.
282

Figure 4. K/S bleach rate (60 ◦ C).

Figure 5. K/S bleach rate (60 ◦ C).

To understand the contribution made by the fabric, a series of experiments

were made at 90 ◦ C. with no fabric in the peroxide bath. This data is presented
in Table 6 and a plot of the logarithm of the overall rate constant, Log k1 ,
versus pH is shown in Figure 7. Again a linear relationship is shown to sup-
port the mechanism purposed in the section on oxygen kinetics. Comparing
the rate constants at 90 ◦ C with and without fabric is made difficult by the
fact that while the starting range of alkali concentration was the same, the
 283
Table 5. Rates at 90 ◦ C; rates are in l/moles s using Keq = 61.78 @ 90 ◦ c sorted by pH

Run # Start Start Measured ko × 1000 k1 × 1000 Log k1

NaOH H2 O2 pH

19 0.0063 0.0444 10.40 1.57 14.12 −1.85020

20 0.0128 0.0444 10.83 1.86 7.53 −2.12340
18 0.0250 0.0589 11.13 2.12 0.84 −2.31580
17 0.0250 0.0517 11.22 1.61 3.26 −2.48710
16 0.0250 0.0444 11.30 2.27 4.04 −2.39390
22 0.0250 0.0444 11.32 4.04 7.19 −2.14350
15 0.0250 0.0367 11.34 2.85 4.39 −2.35720
24 0.0375 0.0444 11.64 3.14 3.24 −2.48980
48 0.0750 0.1032 11.65 3.13 2.65 −2.57630
47 0.0750 0.0885 11.76 1.96 1.38 −2.86030
25 0.0438 0.0444 11.80 2.56 2.86 −2.88000
31 0.0500 0.0443 11.80 1.93 1.32 −2.54400
45 0.0750 0.0588 11.88 2.39 1.11 −2.95400
46 0.0750 0.074 11.88 2.51 1.45 −2.83990
26 0.0500 0.0444 11.94 3.37 2.31 −2.87400
27 0.0630 0.0441 11.94 2.75 1.34 −2.63610
44 0.1000 0.1032 12.00 3.07 1.57 −2.80480
43 0.1000 0.0885 12.06 2.86 1.22 −2.91430
28 0.0750 0.0441 12.10 2.77 1.04 −2.98180
42 0.1000 0.0739 12.12 2.76 0.98 −3.00800
41 0.1000 0.0592 12.16 3.42 1.02 −2.99240
29 0.0880 0.0441 12.20 3.43 1.03 −2.98880

pH is higher with no fabric in the bath. We do not have an explanation for

this fabric effect. However, there are two experiments that have the same pH
of 12.2, (No. 29 with fabric and No. 58 without fabric). Comparing these
two runs, we find an oxygen decomposition rate of 1.03 with fabric and 6.81
without. This indicates that the cotton fabric used in these bleaching trials act
as a stabilizer for the peroxide. This supports the findings of Taher and Cates
(1975b).

Conclusion

We have demonstrated an apparatus that is capable of independently measur-

ing the oxygen produced and the color removed from a piece of fabric in a
284

Figure 6. Oxygen rate (90 ◦ C).

Table 6. Rate constants 90 ◦ C – No fabric sorted by pH

Run # pH k1 × 1000 Log (k1 × 1000)

58 12.22 6.81 −2.1671

57 12.28 7.23 −2.1408
56 12.31 6.4 −2.1940
51 12.57 3.35 −2.4743
59 12.61 3.53 −2.4522
50 12.66 2.32 −2.6344
55 12.73 2.18 −2.6607
54 12.75 2.18 −2.6614
53 12.78 2.56 −2.5925
52 12.83 1.98 −2.7042

bleach bath. In addition, procedures were developed that allow the calculation
of the concentrations of the perhydroxyl ion, hydroxyl ion and undissociated
H2 O2 from the starting levels of NaOH and H2 O2 .
The rate of bleaching of cotton fabric was shown to be a first-order reac-
tion in concentration of perhydroxyl ion as calculated by this procedure. First-
order kinetics was shown at both 60 ◦ C and 90 ◦ C with estimated activation
energy of 17 kcal/mole.
 285

Figure 7. Oxygen rate; no fabric (90 ◦ C).

The rate at which H2 O2 decomposes into oxygen was found to be second-

order kinetics. A mechanism involving the reaction of undissociated H2 O2
and perhydroxyl ion was developed. The kinetics of this reaction was suppor-
ted by the linear relationship of the overall rate constant and the pH of the
bath.

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