Unit 1

Preview of previous class

Bleaching

Topics covered
Hypochlorite bleach
Introduction
Mechanism

Peroxide bleach
Introduction
Mechanism

Bleaching with Hypochlorites

Hypochlorite bleaching (OCl-) is the oldest
industrial method of bleaching cotton.
Until 1940 most cotton fabrics were bleached
with NaOCl today only 10 % of the cotton.
It is however the main stay of home laundry
bleaching products.
Their use is declining because of anti-chlorine
lobby and environmental pressures.

Sodium hypochlorite (NaOCl) Bleaching:

Sodium hypochlorite is the strongest oxidative
bleach - used in textile processing.
NaOCl is a highly unstable compound at normal
conditions of temperature and pH. It doesnt exist
as solid form.
Prior to bleaching with hypochlorite, it is
necessary to thoroughly scour fabrics to remove
fats, waxes and pectin impurities. These impurities
will deplete the available hypochlorite, reducing its
effectiveness for whitening fabric.
Product strength of hypochlorites is generally
expressed as the available chlorine content.

Commercial NaOCl will have 12 to 15 %

active chlorine. Household bleach is 5 %
active
chlorine.
Bleaching
Mechanism:
NaOCl is the salt of a moderately strong
base (OCl-) and a weak acid (HOCl).
NaOCl solution is strongly alkaline (pH ~
11.55) and the free caustic present in the
solution acts as a stabilizer.
Stability of sodium hypochlorite solution is
also improved by storing it in a dark room
below 30 C.
NaOCl + H2O Na+ + OCl - (hypochlorous ion)
OCl - + H2O HOCl + OH

effect on bleaching with hypochlorite.

Addition of caustic favors the formation of
OCl- ion.
Na2CO3 is used to buffer the
bleach bath to pH 9 - 10.
At pH > 10,
little to no bleaching takes place.
When acid is added, the HOCl
concentration increases.
pH 5 - 8.5,
HOCl is the major species present very rapid
bleaching takes place, but rapid degradation
of fiber.
When the pH drops below 5, chlorine
gas is liberated and the solution has no
bleaching effectiveness at all.

are interrelated.
Concentration is also
interrelated with time and temperature.
1 hr at 40
C is satisfactory for effective bleaching.
Effect of Metals
Copper and iron catalyze the
oxidation of cellulose by sodium hypochlorite
degrading the fiber.
. Stainless steel equipment is
required and care must be taken that the water
supply be free of metal ions and rust from pipes.
Antichlor
Fabrics bleached with hypochlorite

 It cannot be used on wool,

polyamides (nylon), acrylics. These fibers will
yellow from the formation of chloramides.
Bleaching with hypochlorite is
performed in batch equipment. It is not used in
continuous operations because chlorine is liberated
into the atmosphere.
Typical Batch Procedure:
NaOCl - 2.5% active bleach
Na2CO3 - 1.0% pH buffer (5 g/l)
Bleach Cycle:
Run 1 hr at 40 C
Drop bath, rinse

Bleaching with Hydrogen Peroxide (H2O2)

H2O2 was discovered in 1818.
By 1940, about 65% and to-day about 90 95 % of all cotton and cotton/synthetic blends
are bleached with H2O2.
It is available commercially as 35, 50 and 70
% solutions.
It is a corrosive, oxidizing agent which may
cause combustion when allowed to dry out on
oxidizable organic matter.
H2O2 is an irritant to the skin and mucous
membranes and dangerous to the eyes.
H2O2 - Ecologically acceptable

Bleaching Mechanism:
H2O2 is a weak acid and ionizes in water to
form:
H2O2+H2OH+ + HOO- (active bleaching agent)
HOO- (unstable) OH + O* (active or nascent
oxygen)
O* + X X-O, X- oxidizable substance
H2O2 decomposition is catalyzed by metal ions
e.g. Cu++, Fe+ + ...undesired rxn: no bleaching
effect and causes fiber damage
Effect
pH 2O + 1/2O2
H2of
O2H
pH has a profound effect on
bleaching with hydrogen peroxide..
H2O2 is an extremely weak acid.

ions.
pH = 10.2-10.7 ( with
NaOH) is optimum.

pH >11, rapid generation of perhydroxyl ion.

pH
11.8 all H2O2 is converted to HOO- and rxn is
out of control.
Effect of Time and Temperature
Stabilized H2O2
does not decompose at high temperature
therefore faster and better bleaching occurs
at 95 to 100 C ideal for continuous
operations.
Temp - rate of bleaching but solution

 Batch
process = 2-4% H2O2
In the
continuous process =1-2%
H2O2 Very high concentration may
damage the fiber.
Effect of time
The time
depends
Auxiliaries for Bleaching
With
H2O2

on temp, class of fiber and equipment used for

bleaching.
1. Stabilizers

temp. of bleaching bath time of bleaching

To control the decomposition of H2O2.

It provide buffering action to control the pH
and to complex with trace metals which catalyze
the degradation of the fibers.
Major types are Sodium silicate, organic
compounds and phosphates

provide alkalinity
Na2CO3, Na3PO4,etc.

eg:NaOH,

Sequestering agent:
organic stabilizers or separate
Uses: Sodium hexa meta phosphate
eg:EDTA,
H2O2 is the
bleach most widely used for cellulosic
Wetting
agent
fibers [cotton, flax, linen, jute etc.) and well as
wool, silk,tonylon
andwetting
acrylics.
provide
and detergency
Unlike hypochlorites, peroxide bleaching
does not require a full scour.
Residual fats, oils, waxes and pectines do not
reduce the bleaching effectiveness of
H2O2.Impurities help in stabilization.

 Since it ultimately decomposes to oxygen

and water, it doesnt create effluent
problems.

Advantages of H2O2

Universal bleaching for Cotton, Rayon, Wool

and
Silkwater is required with peroxide
Less
Itneed
can be
on
bleaching and there is no
for used
souring
continuous
equipment.
after
bleaching.

Peroxide bleached goods are more

Permanentthan
Whiteness
absorbent
hypochlorite bleached
goods.