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Lab methods for judgement of

pretreatment
Our department for applied technique is always at your service for further information and advice.

Our technical advice and recommendations given verbally, in writing or by trials are believed to be correct. They are neither binding
with regard to possible rights of third parties nor do they exempt you from your task of examining the suitability of our products for the
intended use. We cannot accept any responsibility for application and processing methods which are beyond our control.

If producers or sources of different chemicals are mentioned for evidence reaction tests, it is done without evaluation. It is impossible
to take into account all chemical producers in such an infomation brochure.
Methods of evidence........................................................................1
Chemical damaging of cellulosic fibres ................................................... 1
Qualitative evidence for iron.................................................................... 2
Qualitative evidence for hydro- or oxycellulose....................................... 2
Qualitative evidence of hydrocellulose with silver nitrate ........................ 2
Qualitative evidence of oxycellulose with methylene blue....................... 3
Qualitative evidence of damaged cotton by swelling test (immaturity
control by swelling test)........................................................................... 3
Evidence of fats and oils on the fabric .................................................... 4
Red-green test ........................................................................................ 5
Determination of absorbency .................................................................. 6
The degree of desize – the TEGEWA-violet scale.................................. 8
pH- value on the fabric ............................................................................ 9
Conductivity test...................................................................................... 9
Evidence of non ionic residual surfactants............................................ 10
Identification of fibre materials.....................................................12

Hydrogen peroxide ........................................................................16


Properties of commercially available H2O2-solutions ............................ 16
Storage and storage life of hydrogen peroxide ..................................... 16
Stoichiometrical calculation of the active content in H2O2-solutions ..... 17
Analysis of H2O2-content in bleaching baths......................................... 17
Analysis of H2O2-content on fabric ........................................................ 20
Semi-quantitative analysis of hydrogen peroxide content with titanyl
chloride.................................................................................................. 22
Semi-quantitative analysis of hydrogen peroxide content with
Merck-test rods ..................................................................................... 24
Alkali................................................................................................25
Analysis of alkali-content in liquors ..................................................... 25
Sodium hypochlorite (chlorine bleach lye) .................................27
Properties of commercially available chlorine bleach lye ....................................27
Reactions of sodium hypochlorite .......................................................................27
Active chlorine ....................................................................................................28
Analysis of active chlorine content in sodium hypochlorite bleaching liquors ......28
Dechlorination.....................................................................................................30

Sodium chlorite..............................................................................32
Properties of commercially available sodium chlorite..........................................32
Reactions of sodium chlorite...............................................................................32
Analysis of sodium chlorite content in bleaching baths .......................................33
Destruction of residual chlorite............................................................................36
Persulphates .................................................................................. 37
Properties of persulphates ................................................................................. 37
Analysis of persulphate content in addition to hydrogen peroxide in bleaching
baths.................................................................................................................. 37

Silicates .......................................................................................... 41
Properties of commercially available silicates of sodium .................................... 41
Properties of commercially available metasilicates ............................................ 41
Other properties of silicate of soda..................................................................... 41

Water hardness.............................................................................. 44
Analysis of water hardness (total hardness)....................................................... 46
Conversion factors in common units for water hardness .................................... 47

Average polymerisation degree (DP-value) ................................ 47

Fluidity F......................................................................................... 49

Annex.............................................................................................. 50
Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic
soda and caustic potash solution ....................................................................... 50
Brief instruction - titration of hydrogen peroxide ................................................. 56
Brief instruction - titration of caustic lye.............................................................. 57
Methods of evidence

Methods of evidence
Pretreatment exerts a strong influence on all following
processes, like dyeing, printing etc. Mistakes made in
pretreatment can hardly be corrected or even not at all in later
processes. The following simple test methods help to
determine mistakes prior to processing or to obtain the
chemical evidence for them so that damaging effects can be
avoided.

Chemical damage of cellulosic fibres


Cellulosic fibres can be chemically damaged by different
influences, such as

• catalytic damage during hydrogen peroxide bleach caused


by heavy metal contamination.
• damage by contamination of fabric with concentrated
acids, mostly mineral acids like hydrochloric or sulphuric
acid.
• damage by insufficiently stabilized hydrogen peroxide
bleach.

Such damages become visible by holes or by a general


reduction of tear strength or the DP value (average polymerisation
degree).
Holes caused by catalytic
The so-called catalytic damage is a problem of pretreatment damaging
which quite often occurs. It is caused by the presence of heavy
metals, which have a catalyzing effect in peroxide bleach and
promote a spontaneous peroxide decomposition and finally
fibre damage.

In addition to copper and manganese, there is mostly iron or


rust in pretreatment coming from the greige goods itself or
introduced onto the fabric e.g. by the following reasons

• Metal abrasion during storage or transport of fabric.


• Rusty pipelines or machines parts in the pretreatment
plant.
• Contamination of the industrial water with heavy metals.

The presence of iron on fabric or in industrial waters can be


proven rather easily.

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Methods of evidence

Qualitative proof of iron


Ammonium thiocyanate (NH4SCN) forms a very red complex
with iron.

This proof can be obtained directly on the fabric or as well as in


aqueous solutions.

Procedure

The fabric sample is treated with a solution of 1-2 spatula tops


of ammonium thiocyanate (NH4SCN) in approx. 10-15 ml
hydrochloric acid of 10%. A very red iron thiocyanate complex
is formed if there is iron.

Undamaged cellulose
CH2OHCellulose
OH CH2OH
Qualitative proof of hydro- or oxycellulose
O O
O OH
OH
O
O OH
Damaged cellulose forms hydro-and oxycellulose at the
OH CH2OH OH
damaged parts and this can be proven by simple means.
Hydrocellulose Independently from the reason for the damaging, that means
CH2OH OH CH2OH
OH O
OH
OH O by acid or oxidation agents, a mixture of hydro- and
C C
OH H
O
O OH H
oxycellulose is formed. By means of the following reactions of
OH CH2OH OH
evidence it is indeterminate whether the damaging was caused
Oxycellulose by oxidation agents or acids.
CH2OH O O CH2OH

CHOH CH HC CHOH

COOH COOH
OH O OH
O
OH CH2OH OH

Qualitative proof of hydrocellulose with


silver nitrate
The hydrocellulose with the reducing effect separates
elementary silver from a silver nitrate solution, and this
becomes visible at the damaged parts by a yellow brown to
black dyeing.

Procedure

The degreased sample free of size and finish is treated for


some minutes at 80°C in an ammoniacal silver nitrat e solution.
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2
Methods of evidence

Then it is rinsed with distilled water and with diluted ammonia


solution.

Production of the ammoniacal silver nitrate solution

A solution of 10 g silvernitrate in 100 ml water is mixed carefully


with a ammonia solution of 10 % until the white sediment which
had been formed is dissolved again.

Qualitative evidence of oxycellulose with


methylene blue To note:

The basic dye methylene blue strongly dyes oxycellulose very Merzerised CO reacts like
damaged CO. Caution is
much because of the carboxylic groups and the depth of the advised.
dyeing corresponds to the degree of the damage.

Procedure

The degreased sample which is free of size or finishing is dyed


in a hot and aqueous methylene blue solution of 0.1% at 60 °C
for 5 min. Then it is washed with boiling distilled water until
there is no dye left.

Qualitative evidence of damaged CO by To note:


swelling test (immaturity control by swelling test) The swelling reaction can
be done successfully only
Undamaged CO fibre pieces treated with caustic soda show a on CO fibres.
phenomena which looks like mushrooms at the fibre ends
Mercerised CO reacts in
under the microscope. However considerably chemically the same way as damaged
damaged CO fibre do not show such characteristic CO. Caution is advised.
phenomena.

Because of this it is possible to distinguish chemically damaged


fibres from mechanically damaged ones.

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Methods of evidence

Undamaged CO
Procedure

Fibres are taken from damaged and undamaged parts of a


sample. Th cotton fibres are cut vertically to the fibre direction
in pieces of 2 to 3 mm with some sharp-edged scissors or a
razorblade. They are put on an object holder, covered with a
cover glass, and caustic soda of 10 to 15% is added from the
side by means of glass capillary.
Damaged CO
The fibres are compared under the microscope by transmitted
light and magnified as large as possible.

At the undamaged CO there are phenomena looking like


mushrooms at the fibre ends.

Chemically damaged CO does not show such "mushroom"


phenomena, or only to a small degree.

Evidence of fats and oils on the fabric


Ceres red 7B corresponds
to Color Index Number C.I. Residual oils and fats on the fabric often coming from
26050.
preperations can have disturbing effects during dyeing e.g.
resist effects.
Fabric free of oil or fat
The evidence of fats or oils can be provided by a fat dye Ceres
red 7B.

Procedure

Fabric with oil stripes The Ceres red stock solution is diluted with water at a ratio of
1:9 just before the application. This dilution is the utility
solution.

The fabric which is to be analyzed is treated with the utility


solution at 60 °C at a liquor ratio of 1:60 for 5 - 10 minutes.
Then wash off cold for approx. 1 min, dry and fix the dye at
150 °C for 3 min.

The fats which are on the fabric are dyed in an intense red
shade.

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Methods of evidence

Production of Ceres red stock solution

Ceres red 7B 0.4 g/l


CHT-DISPERGATOR SMS 1.0 g/l

The dye and the dispersant are ground in a plate and pasted
with cold soft water. The solution is filled up with soft water at
1 l.

With time, the Ceres red dye precipitates to the bottom of the
container. Therefore the solution has to be shaken or stirred
before it is applied.

Red-green test

Analysis of effects of caustification and


mercerisation of CO and CV and of ripe and unripe
CO Differences of degree of
caustification and mercerisation
Variations in the degree of caustification and mercerisation
S
o
d
iu
mchrite 3
lo 0vol.%
solution
lead to differences of dyeability and colour depth. The following not caustified
S
h
ortn
am
e N
30
test helps to recognize such differences.
2- a
NaC lO [g/kg] pro
x.245(=24.5%
)
co
n
cen
tratio
ns[g/l] 300
If a fibre sample is treated in a solution with both direct dyes of 100 g/l NaOH 100 %
slightlygreenish-yelow
clear
Tubantin red 8BL conc. and Tubantin green BL highly A
sp
ect
liquid
concentrated (BEZEMA AG), mercerised materials are dyed D
en 3
sity(20)[g/cm
] 1
22
from grey to green. This is because of the affinity differences of 150 g/l NaOH 100 %
S
o
lu
b
ilityinw
aterat20
unlim
ited
dyes, depending on the degree of caustification and C°
mercerisation, and the materials which have not been treated
S
tarto
fcrystalisatio
nC
[]° a
prox.-15
with lye become red. 200 g/l NaOH 100 %
R
eactio
n alkaline(pH
-valueaprox.13)

The red-green-test can be applied to differentiate between ripe


and unripe CO. The ripe fibres are dyed red in the test and the Dead CO
unripe green.

Dead CO fibres are dyed much less or not at all. They can be
recognized as well by their neppy agglomerations in the fibre
texture.

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Methods of evidence

Procedure

The CO sample is wet-out well with boiling distilled water and


then treated with the following dyeing recipe:
TUBANTIN red 8BL conz. 120
Liquor ratio 1:40
110
C.I. Direct red 81 45 min at 98 °C
100
90
TUBANTIN green BL highly Temperature [°C]
80
conc.
70 add fabric at take out after 15 and 30 min
boiling temp. and add 2.5 % NaCl (normal
C.I. Direct green 26 60
salt
50
40
30
20 0.8 % TUBANTIN red 8BL conc.
10 3.2 % TUBANTIN greenBL hightly conc.
0
0 10 20 30 40 50 60
Time [min]

After dyeing rinsing is carried out as follows (liquor ratio 1:40):

- 2 times rinse cold


- 1 time rinse for 30 s with boiling water
- 2 times rinse cold

Then dewater the sample and air dry it.

Analysis of absorbency
For more details see
TEGEWA-drop test: The textile absorption or hydrophilic effect is mostly analyzed
by the following two methods:
„TEGEWA-drop test – a method for
a rapid determination of textile
absorption“ • TEGEWA-drop test
• Capillary rise method
„Melliand Textilberichte 68 (1987),
581-583

The TEGEWA-drop test is usually applied for the rapid


determination of the absorbency. In case of small differences of
absorbency and if the best possible absorbency is necessary
for the further transformation of the textile, the more
complicated capillary rise method is advantageous.

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Methods of evidence

TEGEWA-drop test – brief description Alternative for Patentblau V


ERKA Typ S 4030
The test material is put into the tension device and a drop of Ringe Kuhlmann GmbH & Co KG
aqueous patent blue of 0.2 % is applied. Hamburg, Germany
As soon as the drop touches the test material, time is
measured. As soon as the shiny surface of the drop is no
longer visible, time measuring is stopped.

Evaluation criteria are the following:

• sinking time of the drop


• spread diameter of drop.
• picture of flowing. Jagged borders of the drop can indicate Good Bad
pretreatment pretreatment
woven fabric e.g. on irregularly distributed residual
deposits of size, warp waxes etc.

Capillary rise procedure – brief description


There are different variations of the capillary rise procedure,
and the two most important are mentioned in the following.

Strips of approx. 3 x 25 cm in warp and weft direction (or in


longitudinal or transversal direction) are taken out and hung in
water colorated with dye (e.g. solution V of patent blue 0.2 %).

Variation 1 (DIN 53924)


40 mm
As soon as the sample is immersed in the liquid, the capillary
rise is taken in mm after 10, 30 and 60 s from mark A at the 30 mm
liquor surface.
C 20 mm

B 10 mm
Variation 2

Wait until the liquid level is at a height of 10 mm (mark B) and A


take time until mark C at 20 mm is obtained.

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Methods of evidence

The degree of desize – the TEGEWA-violet-


See further details to
TEGEWA-violet scale: blue scale
„The Violet Scale, a criterion for
assessing the desizing degree of Because there is a relation between the colour intensity of the
starch-sized fabrics“ iodine starch complex and the residual starch content on the
Textil praxis international 12
fabric, the colour reaction of starch and free iodine is applied to
(1981), 1331-1332, 1349-1350 judge in a semi-quantitative way the residual size content or
better the residual content of starch after the pretreatment.

Procedure

Remark A fabric sample of approx. 4 x 4 cm is laid for one minute into a


iodine solution at a concentration c = 0.005 mol/l, rinsed with
A complete description of the
evidence of sizes is at cold water for a short time and then dapped off with a starch
disposal in a separate CHT free filter paper and compared immediately with the TEGEWA-
brochure violet scale.

Evaluation

9= completely
goo
desized

good good

average bad

The mark 9 on the scale indicates a complete starch


elimination, and mark 1 an insufficient one.

Fabrication of the iodine solution

To produce the 0.005 mol/l iodine solution preferably ready-


made solutions (e. g. Fixanal or Titrisol) are applied at a
concentration of c(I2) = 0.05 mol/l (= 0.1 N). Of this solution
Remark
50 ml are taken and filled up to a litre with distilled water.
Because of the volatility of
the iodine, iodine solutions
should always be kept in a
brown flask closed with a
The solution itself can be made as follows:
ground-in stopper.
10 g potassium iodide are dissolved in 100 ml of water, 0.65 g
of iodide are added and agitated until complete dissolution.
Then filling up with distilled water up to 1 l.

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Methods of evidence

pH value on the fabric Morapex A (Habotex)

The pH value on the fabric is determined by the following


method:

• According to DIN EN 1413. The sample is extraced in cold


distilled water for 2 h at a liquor ratio of 1:50 and then the
pH is measured in the extract. pH-Indicator
• With Morapex extraction. The sample is extracted with hot (Merck)
distilled water at the Morapex and then the pH measured
as well in the extract. pH 3.5

• Dropping of a pH-indicator directly on the sample.

pH-value determination with pH-indicator – brief


description pH 6.5

The easiest method is the pH-determination by dropping a pH-


indicator (e.g. of Merck) directly on the sample. This procedure
does not give absolutely reliable results, but at least a rough
estimation about the pH on the fabric.
pH 8
The sample is moistened with distilled water, and then the pH-
indicator is dropped on. Then it is compared with the colour
scale.

Conducting
Determination of the conductivity meter

The electrolyte content (residual alkali, neutralisation salts and


others) of a pretreated material has an important influence on
the print result of a pigment printing. A high electrolyte
concentration leads, for example, to a decrease of the printing
paste viscosity, and therefore to an increasing and thus
unwanted penetration of the print. A measure for the electrolyte
content of a fabric is the electrical conductivity which can easily
high low
be determined.
conductivity conductivity
(180 µS/cm) (20 µS/cm)

Procedure Print side Print side

4.00 – 10.00 g of the test fabric are weighted in a round-bottom


flask of 250 ml, distilled water is added at a liquor ratio of 1:20,
and the solution is boiled for 1 h by reflux. After cooling and Back side Back side
filtering, measurement of the conductivity of the extract by
means of a conducting meter.

The measuring value is given in µS/cm or mS/cm.


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Methods of evidence

Evidence of non ionic residual surfactants


Precipitations of a reactive dye Some reactive dyes (mostly turquoise types) react sensitively in
with a non ionic surfact the presence of non ionic surfactants which had been
unsufficiently eliminated from pretreatment.

If non ionic residual surfactants are suspected to be the reason


for a problem, their presence can be proven in the extract after
extraction of the fabric in cold water according to the so-called
Draggendorff-reaction.

Procedure
Example
series of concentrations of a The material to test is extracted at a liquor ratio of 1:20 with
non ionic surfactant cold distilled water at 5°C for 5 minutes (e.g. in beaker).
It is important that the temperature of the water is approx. 5 °C;
Concentration in
% on weight of
because it guarantees that the non ionic surfactants are
fabric Concentration removed from the fabric to the water phase extract
(LR 1:20) in g/l quantitatively.

0.0 0.0 10 ml of the extract are prepared in a test tube. Then 2 ml of


Draggendorff-reagent are given to the extract, and the test tube
is agitated. The orange deposit is absorbed through stainless
steel filter, and the filter paper is dried.

0.04 0.02
Judgement

The intensity of the desposit is a measure for the concentration


0.10 0.05 of the present non ionic surfactant. Depending on the chemical
base of a surfactant precipitations of different intensity can
result, and therefore a series of concentrations of the applied
surfactants should be produced for comparative purposes and
0.20 0.10 to allow a semi-quantitative result by this.

10 ml of every different surfactant solution is mixed with the


reagent and filtered.
0.30 0.15

Fabrication of the Draggendorff-reagent

The ready-made Draggendorff reagent can be applied only for


a limited time, and therefore it is best to produce two different
stock solutions (A and B), which are mixed just before their
application.

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Methods of evidence

Solution A:

1.7 g of bismuth nitrate are dissolved in 20 ml of pure acetic


acid. After addition of 80 ml of water, a solution of 40 g of
potassium iodide, 100 ml of distilled water and 200 ml pure
acetic acid are filled up to 1000 ml in a graduated flask.

Solution B:

A barium chloride solution of 20 % in distilled water

Ready-made reagent:

Mix 2 volume parts of solution A with 1 volume part of


solution B.

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Identiification of fibre materials

Identification of fibre materials


For a quantitative analysis of the fibre materials on natural or
synthetic basis and their mixtures there are instructions of
analysis at disposal in the technical literature.

To identify the individual fibres there are different qualitative


rapid methods like burning test, dry distillation, dyeing reaction,
Remark microscopical analysis or dissolution in acids, alkali, organic
solvents.
In case of fibre mixtures
caution is advised. Mixed pH
values might turn up and the Burning test and dry distillation
identification becomes difficult.
Preliminary tests should be
burning test and dry distillation.
For the burning test the fibre which is to be analyzed is held
into the flame, and the criteria of burning, fume, odour and
residue are judged.
In the dry distillation the fibres are heated in a dry test tube,
and the vapours are tested on their pH value by means of a
moistened pH paper.

Natural and man-made fibres Dry


Fibre Burning test
distillation
Odour Burning, residue pH-value
Burning test
Dry distillation Vegetable fibres
of burnt burns down fast, white
like cotton, linen, pH 5-6
paper grey ashes
hemp, viscose
Animal fibres, burns slowly, white grey
of burnt hair pH 9-10
like wool, silk ashes
burns fast, burnt-out
particles with
Acetate fibres sour, like acid pH 2-3
subsequent white grey
ashes
melts and burns,
sweetish and sooting only in flame,
Polyester fibres pH 3-4
stinging glassy, ropy melt, black
enamel pearl
goes on melting and
slightly of burning without sooting,
Polyamide fibres pH 10-11
burnt hair glassy yellow to brown,
ropy melt

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12
Identification of fibre materials

Dry
Fibre Burning test
distillation
Burning,
Odour pH-value
residue

melts and burns, then


Polyacrylonitrile-
sweetish soots, black and pH 10-11
fibres
brittle melting residue
melts and goes on
burning, without
Polyurethanes malodorous sooting, black, hard pH 10-11
and brown metling
residue
melts and goes on
burning without
Polyethylene like burning
sooting, light brown pH 5-6
fibres candle
and brittle melting
residue
melts but does not
Polypropylene- like burning
burn, white smoke, pH 6-7
fibres candle
yellowish melt

Dyeing method

The dyeing method with special dye reagents can be applied


without any problems, and allows a good to rough evaluation
depending on the material which is to be analyzed e.g. fabric
out of one fibre kind, mixed articles of singular or uniform fibres.
This does not work on dyed material, and therefore coloured
fabric has to be stripped before testing. The dyeing method
serves only as a preliminary test because it can be applied only
under certain conditions on stripped or pretreated fabric.

Special fibre material reagents for the analysis of fibre


materials are offered under the name of „Neocarmin“ by the
company FESAGO Chemische Fabrik Dr. Gossler, 69207
Sandhausen. The producer supplies colour scales for
identification together with the reagents.

Analysis of man-made fibres

For a uniform fibre mixture, dyeing reactions or burning tests Man-made fibres
are not sufficient to identify singular components. A
classification is possible only by a process of separation with
different dissolving tests with organic or inorganic chemicals.

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13
Identiification of fibre materials

The following dissolving behaviour in different solvents


describes only the qualitative analysis. There are further
methods in technical literature for the quantitative
determination.

Dissolving behaviour

Polyamide 6.6

Polypropylene
Polyacrylonitrile

Polyurethane

Polyethylene
Polyamide 6
Triacetate

Polyester
Acetate
Acetone ❑ ■ ■ ■ ■ ■ ■ ■
Dimethylformamide ❑ ❍ ■ ❍ ❍ ❍ ❍ ● ●
Dioxane ❑ ❑ ■ ■ ■ ■ ■ ■ ●
o-Dichlorobenzene ● ■ ■ ■ ❍ ■ ❍ ❍ ❍
Phenol 40% ❑ ❑ ❑ ❑ ❍ ● ❍ ● ●
Xylol ■ ■ ■ ■ ■ ■ ■ ❍ ❍

Formic acid (98%) ❑ ❑ ❑ ❑ ■ ■ ❍ ■ ●


Pure acetic acid ❑ ❑ ❍ ❍ ■ ■ ● ■ ●
Hydochloric acid conc. ❑ ❑ ❑ ❑ ■ ■ ▲ ■ ●
Sulphuric acid conc. ❑ ❑ ❑ ❑ ❑ ❑ ❑ ● ●
KOH 40% ■ ■ ■ ■ ▲ ■ ▲ ● ●

❑ cold soluble
❍ soluble at boiling temperature
■ insoluble
● insoluble, but changes during boiling
▲ swells and decomposes during boiling
partly soluble during boiling

Natural fibres Analysis of natural fibres

A rapid analysis of singular cellulose fibres e.g. cotton, viscose


or protein fibres like wool and silk cannot be taken for granted,
especially not if it is a uniform fibre mixture. Dyeing reactions
and a microscopical analysis mostly can give an indication, but
for singular determinations sometimes complicated wet
chemical analyses have to be carried out (see technical
literature).

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Identification of fibre materials

As simple examples can be mentioned Different


procedures of analysis
Vegetable fibre: odour of burnt
Vegetable fibres Burning test paper
Animal fibres Dyeing test Animal fibre: Odour of burnt
hair
Not mercerised: typical cork-
Microscopical screw like twists of the fibre;
Mercerised
analysis kidney shaped cross-section
not mercerised cotton
Red-/green test Mercerised: smooth fibre,
round cross-section
Ripe cotton fibre: red dyeing
Ripe and unripe cotton Red-/green test Unripe cotton fibre green
dyeing
Cotton: typical cork-screw like
Cotton Microscopical
twists of the fibre
regenerated cellulosic analysis
Regenerated cellulosic fibre:
fibres Dyeing method
smooth fibre
Cotton Microscopical Different longitudinal section
Bast fibre analysis pictures of the fibres
Wool: dissolves during boiling
Dissolving tests
in NaOH of 5%, typical scales
Wool microscopical
layer
Silk analysis
Wild silk: dissolves only partly
dyeing method
even if boilt for a longer time
Pure silk: dissolves during
Pure silk (bombyxs mori) boiling in HCl conc. (after
and wild (e.g. Tussahsilk) Dissolving tests approx. 60 sec.)
silk Wild silk: dissolves only after
boiling for a longer time

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15
Hydrogen peroxide

Hydrogen peroxide
Chemical formula: H2O2
Molar mass: 34.02 g/mol

Properties of commercially available H2O2-


solutions
Short name W 30 W 35 W 50 W 60

[% by weight] 30 35 50 60

[Vol.-%] 111 132 199 249


H2O2 -concentrations
Aktive oxygen [g H 2 O 2 /kg] 300 350 500 600

Peroxides have -O-O- groups, [g H 2 O 2 /l] 334 396 598 745


of which an oxygen atom can
easily be separated as „active Active oxygen content [% by weight] 14. Jan 16. Mai 23. Mai 28. Feb
oxygen“ . ρ20)
Density (ρ [g/cm ]
3
1.114 1.132 1.195 1.241
(For calulation see below)
+
Acid content 0.5 - 5 mmol H /l

Storage life and storing of hydrogen


peroxide
Decomposition of H2O2 In presence of catalytic substances hydrogen peroxide easily
decomposes in an exothermal reaction to water and oxygen.
H2O2 (liq.) → H2O (liq) + ½ O 2 (g.) Stability of hydrogen peroxide is influenced by:
∆H = -98.31 kJ/mol
• Heavy metals
(Iron, copper and manganese even in smallest concentrations
reduce very much the hydrogen peroxide stability).
• pH-value
(The best pH value is between 3.5 and 4.5)
• The concentration of hydrogen peroxide
(The higher the H2O2-concentration is, the more decomposition
tends to diminish).
• Temperature
(At a higher temperature of about 10 °C, the reacti on speed
• increases at a factor of 2.2).
• Influence of light
(Hydrogen peroxide should be stored in containers which are
impervious to light).
• Other soilings
(Soiling of any kind reduces substantially the stability of hydrogen
peroxide).

`eq=oK=_bfqif`e=dj_e=

16
Hydrogen peroxide

For the above mentioned reasons hydrogen peroxide should be


protected from light and stored in its original containers or
special tanks.

Stoichiometric calculation of active oxygen


content in H2O2-solutions
For the determination of the active oxygen content the
bimolecular decomposition reaction of hydrogen peroxide is
taken as basis:

H2O2 → H2O + ½ O2
Example 1

34.0146 g/mol → 18.0152 g/mol + ½ · 31.9988 g/mol How much active oxygen in
g/kg does a H2O2-solution of
50% contain ?
Out of 34.0146g H2O2 100 % result from ½ · 31.9988g =
Active oxygen = 50 · 4.704 =
15.9994g of so-called active oxygen. 235g/kg = 23.5%

The conversion factor of % by weight of H2O2-solution in active


oxygen is the following: Example 2

How much active oxygen does


% by weight H2O 2 − sol. ⋅ 15.9994 ⋅ 10
Active oxygen [g/kg sol.] = a bleaching bath with 10ml/l
34.0146 H2O2 50% (density ρ20 = 1,132
g/cm3) contain?

= % by weight H2O 2 − solution ⋅ 4,704


10 ml H2O2 50% contain
10 ⋅ 1.132 = 11.32 g H2O2 50%
In bleaching baths normally the total content of hydrogen or 11.32g H2O2 50% /1000ml
peroxide is determined and not the active oxygen content. 4.704 ⋅ 50 ⋅ 11,32
x= = 2.7 g/l
1000
Aktive oxygen content = 2.7 g/l

Determination of H2O2-content in bleaching


baths
The hydrogen peroxide content can be determined by titration
with potassium permanganate (permanganometrically) or with
iodine (iodometrically). Titration with potassium permanganate
certainly is the most often used method, and therefore it is the
only procedure which is mentioned here.

`eq=oK=_bfqif`e=dj_e=

17
Hydrogen peroxide

Permanganometric determination of H2O2

Reaction of H2O2 with KMnO4 Titration with potassium manganate in sulphuric acid solution is
often running from colourless to slightly pink.
5 H2O2 + 2MnO4- +6H → +

+ 5 O2 ↑ + 8 H2O
2+
2 Mn
The equivalent mass ratios result from the reaction equation or
equivalent numbers of potassium permanganate and hydrogen
peroxide.

Equivalent
Molar mass
number z

Hydrogen peroxide 2 34.0146 g/mol

Potassium
5 158.034 g/mol
permanganate

The equivalent ratios result from:

n(eq) (KMnO4) = n(eq) (H2O2)

m (H 2O2 ) ⋅ z (H 2O2 )
n (KMnO4 ) ⋅ z (KMnO4 ) = n (H 2 O2 ) ⋅ z(H 2O2 ) =
M (H 2O2 )
m (H 2 O2 ) ⋅ z (H 2 O2 )
n (KMnO4 ) =
M (H 2 O2 ) ⋅ z (KMnO4 )

Normally a solution of 0.02 mol/l (= 0.1 N) KMnO4 is applied.

Then the following equation is valid:

m (H2O2 ) ⋅ 2
0.02 mol KMnO4 =
34.0146 g/mol ⋅ 5
0.02 mol KMnO4 ⋅ 34.0146 g/mol ⋅ 5
m (H2O2 ) =
2
m (H2O2 ) =1.7007 g

According to this 1 ml of a solution of 0.02 mol/l (= 0.1 N) KMnO4-


exactly corresponds to 0.0017 g H2O2 100 %.

Normally a solution of 0.1 N (= 0,02 mol/l) potassium


permanganate is applied for titration. However special solutions
can be applied as well, e.g. for the AATCC test 102 a solution
of 0.588 N or for Europe a solution of 0.23 N. The main reason
for these special solutions is a direct relation between
consumption of potassium permanganate and the hydrogen
peroxide concentration. The consumption of a 0.23 N
potassium permanganate solution in case of a sample of 10 ml
just gives the content of ml/l H2O2 35%.

`eq=oK=_bfqif`e=dj_e=

18
Hydrogen peroxide

Procedure of titration Remark:

In the annex, there is a very


An aliquot part is taken, normally 1 to 10 ml of the bleaching much simplified variation of the
bath and given into an Erlenmeyer flask containing approx. titration instruction.
10 ml of a sulphuric acid (20%). The titration is carried out
immediately with the potassium permanganate solution to a
faint pink colour.

Calculation

The variables applied for calculation are the following ones:

Consumption in ml of a KMnO4 solution at a


V
concentration of x mol/l.
Concentration of the applied potassium
x mol/l
permanganate solution, normally 0.02 mol/l =
KMnO4
0.1 N
F ml of taken quantity of bleaching liquor

Density of hydrogen peroxide solutions


ρ (H2O2 35%ig = 1.132; H2O2 50% = 1.195)

W % by weight of hydrogen peroxide solution

The following calculation formula are such that calculation can


be done with every concentration of potassium permanganate
solution and every concentration of hydrogen peroxide.

Normally a 0.02 mol/l = 0.1 N of potassium permanganate 1 ml 0.02 mol/l KMnO4


=
solution is applied. 0.0017g H2O2 100%

Calculation of H2O2-concentration in g/l: Example

x mol/l KMnO 4 ⋅ 5 ⋅ 34.0146 ⋅ V ⋅ 100 For titration of F = 10ml


g/l H2O 2 x − % = bleaching liquor with 0.02mol/l
2 ⋅ F ⋅ W KMnO4-solution (= 0.1 N) are
x mol/l KMnO 4 ⋅ 8503.65 ⋅ V used V = 8.5ml KMnO4-
= solution. How much of H2O2
F ⋅ W 50% (W=50) in g/l does the
bleaching liquor contain ?
0.02 ⋅ 8503.65 ⋅ 8,5
g/l H 2 O 2 50% =
10 ⋅ 50
g/l H2O2 50% = 2,89g/l

`eq=oK=_bfqif`e=dj_e=

19
Hydrogen peroxide

Example Calculation of H2O2-concentration in ml/l:


For titration of F = 10ml of
x mol/l KMnO 4 ⋅ 5 ⋅ 34,0146 ⋅ V ⋅ 100
bleaching liquor with 0.02 mol/l ml/l H2O 2 x − % =
KMnO4-solution (= 0.1 N) 2 ⋅ F ⋅ W ⋅ ρ
V = 8.5 ml KMnO4-solution are
consumed. How much H2O2
50% in ml/l (W=50, ρ=1.195) x mol/l KMnO 4 ⋅ 8503,65 ⋅ V
=
does the bleaching liquor F ⋅ W ⋅ ρ
contain?

0.02 ⋅ 8503.65 ⋅ 8,5


ml/l H 2 O 2 50% =
10 ⋅ 50 ⋅ 1.195
ml/l H2O2 50% = 2,42 ml/l Determination of H2O2-content on the fabric
To verify the application of chemicals during impregnation
processes the hydrogen peroxide content can be determined
directly on the fabric in a quantitative way.

Procedure

A piece of approx. 2-3 g is cut out of the fabric after


impregnation and given immediately into an Erlenmeyer flask
containing approx. 100 ml of an sulphuric acid of 20%. With the
potassium permanganate solution titration is done up to first
persisting violet dyeing.

Then the sample is taken out of the flask, rinsed briefly with
water, dried and weighted.

Calculation

The parameters of calculation are the following:

Consumption in ml of KMnO4-solution with a


V
concentration of x mol/l.
Concentration of the applied potassium
x mol/l
permanganate solution, normally 0.02 mol/l =
KMnO4
0.1 N
M Mass of taken sample in grammes

Density of hydrogen peroxide solution


ρ (H2O2 35% = 1.132; H2O2 50% = 1.195)

W % by weight of hydrogen peroxide solution

`eq=oK=_bfqif`e=dj_e=

20
Hydrogen peroxide

The following calculation formula are such that calculation can


be done at every concentration of potassium permanganate
solution and every concentration of hydrogen peroxide.

Normally a 0.02 mol/l = 0.1 N potassium permanganate


solution is applied.

Example
Calculation of the H2O2-concentration in g/kg:
After impregnation a sample
having a mass of 2.8 g is taken.
x mol/l KMnO 4 ⋅ 5 ⋅ 34.0146 ⋅ V ⋅ 100
g/kg H2O 2 x − % = For titration with 0.02mol/l
2 ⋅ M ⋅ W KMnO4-solution (= 0,1 N)
V = 8.5ml KMnO4-solution are
consumed. How much H2O2
x mol/l KMnO 4 ⋅ 8503.65 ⋅ V 50% (W=50) in g/kg are on the
= fabric ?
M ⋅ W
0.02 ⋅ 8503.65 ⋅ 8.5
g/kg H2O2 50%ig =
2 .8 ⋅ 5 0
g/kg H2O2 50% = 10.3 g/kg

Calculation of H2O2-concentration in ml/kg:


Example

After impregnation a
x mol/l KMnO 4 ⋅ 5 ⋅ 34.0146 ⋅ V ⋅ 100 samplehaving a mass of 2.8 g is
ml/lkg H2O 2 x − % = taken. For titration with
2 ⋅M ⋅ W ⋅ ρ 0.02mol/l KMnO4-solution
(= 0,1 N) V = 8,5ml KMnO4-
solution is consumed. How
x mol/l KMnO 4 ⋅ 8503.65 ⋅ V
= much H2O2 50%(W=50) ml/kg
M ⋅ W ⋅ ρ are on the fabric ?

0.02 ⋅ 8503.65 ⋅ 8.5


ml/kg H2O 2 50%ig =
2.8 ⋅ 50 ⋅ 1.195
ml/kg H2O2 50% = 8.6 ml/kg

Reagents
Potassium permanganate solution

To produce the potassium permanganate solution preferably


ready-made solutions are applied. If the solution is produced, it
is done as follows:

For a 0.02 mol/l KMnO4-solution 3.1607 g of solid potassium


permanganate are weighted and dissolved in distilled water.
After complete dissolution of the potassium permanganate,
filling up with distilled water up to the marking in a 1 l graduated
flask.
`eq=oK=_bfqif`e=dj_e=

21
Hydrogen peroxide

Semi-quantitative determination of the


hydrogen peroxide content with
titanylchloride
For hydrogen peroxide a semi quantitative determination can
be done in a bath sample or directly on the fabric with
titanylchloride. Particularly in case of cold dwelling procedures
or steaming processes (before the washing off) the fabric can
be determined very rapidly on its residual peroxide content and
the recipe can be modified accordingly in case of need.
Reaction of H2O2 with
titanylchloride The determination method is based on a colour change during
the reaction of hydrogen peroxide with titanylchloride (TiOCl2).
[Ti ⋅ aq]
2+
+ H2O2 Depending on the concentration of hydrogen peroxide there is
→ [Ti(O2) ⋅ aq]
2+
+ H2O a yellow to a deeply orange red dyeing.
yellow to orange

Depending on the determination of the hydrogen peroxide


content on the fabric or in a solution, there are two colour
scales at disposal.

Colour scale L Determination in aqueous solutions – colour scale L


Determination of hydrogen
peroxide in aqueous solutions.
0.5 ml of the test solution are mixed on a white droplet plate
with 1 drop of titanylchloride solution. After approx. 1 min the
colour shade is compared with the colour scale.

The content of hydrogen peroxide is given in ml/l.

Colour scale T Determination directly on the fabric – colour scale T


Determination of hydrogen 2 – 3 drops of titanylchloride solution are spotted onto the
peroxide directly on the fabric
textile and the reagent is left to act for 20 – 30 s. The colour
shade is compared with the colour scale.

The content of hydrogen peroxide is given in ml/kg.


If there is not any yellow colouration, there is hardly any
hydrogen peroxide.

Fabrication of the titanylchloride solution

10 ml of titan(IV)chloride is slowly dropped in 20 ml


hydrochloric acid conc. and stirred. The reaction should be
done under an extractor hood because of the very strong
exothermic reaction and the development of hydrogen chloride
(fumes).
After having produced the mix, the solution is heated up to
boiling and after 1 min 800 ml of diluted hydrochloric acid (1
part of conc. hydrochloric acid and two parts of water). After
cooling off, the solution is ready for use.
`eq=oK=_bfqif`e=dj_e=

22
Hydrogen peroxide

`eq=oK=_bfqif`e=dj_e=

23
Hydrogen peroxide

Semi-quantitative determination of the


hydrogen peroxide content with
Merck-test sticks

Application for aqueous solutions

1. Take test sticks and close the tube again.


2. Dip test stick for 1 sec into the test solution so that the
reactive zone is completely wet.
3. Take out test stick and shake off excess liquid and
compare the reactive zone after 15 sec with the colour
scale.

Depending on the blue dyeing of the stick, a value of


0 – 25 mg/l hydrogen peroxide is read off from the Merck-
test stick container scale.

`eq=oK=_bfqif`e=dj_e=

24
Alkali

Alkali
In pretreatment the following alkali are used:

• Caustic soda (NaOH), solid or in solution


• Soda (sodium carbonate, Na2CO3)
• Ammonia solution
• Silicates or silicate of soda

Determination of alkali content in liquors Remark:

In the annex there is a very


The quantitative determination of the three alkalis in the bath much simplified version of the
are carried out by acidimetrical titration with salt or sulphuric tiitration instruction.
acid (mostly 0.1 N). The end point of the titration is indicated by
a suitable acid-base indicator like e.g. phenol phthalein,
methylorange or by a colour change.

Titration
Common indicators

An aliquot part, usually 1 to 10 ml, of the liquor is given into an


Colour change
Erlenmeyer flask containing some distilled water. It is titrated Indicator
of → to
with the acid solution up to the colour change of the indicator.
Phenol red →
phthalein colourless
Methyl orange orange → ret
Calculation
Methyl red yellow → ret
The parameter of calculation are the following:

Consumption in ml of acid-solution. Normally


V 0.1 mol/l (= 0.1 N) hydrochloric acid or 0.05
mol/l (= 0.1 N) sulphuric acid

F ml of taken liquor quantity.


Factor for the conversion on caustic soda, soda
or ammonia

1 ml = 4.0 mg caustic soda (NaOH)


f 1 ml = 5.3 mg soda (Na2CO3)
1 ml = 1.7 mg ammoniac (NH3)

Valid for hydrochloric acid of 0.1 mol/l (= 0,1 N)


or sulphuric acid of 0.05 mol/l (= 0,1 N)e.

`eq=oK=_bfqif`e=dj_e=

25
Alkali

Example
For a 0.1 mol/l (= 0,1 N) hydrochloric acid or 0.05 mol/l (= 0,1
N) sulphuric acid, the concentrations of different alkalis are
F = 10 ml are taken of a found as follows.
bleaching liquor and titrated
with hydrochloric acid of 0.1
mol/l with phenol phthalein as
indicator. The consumption of Alkali in g/l:
the acid is: 11.2 ml. Which
content of caustic soda (f = 4)
f ⋅V
in the liquor ? g/l Alkali =
F
4 ⋅ 11,2
g/l NaOH100% =
10
g/l NaOH 100% = 4.5 g/l
Particularly in continuous processes caustic lye is applied
instead of solid caustic soda. In such cases it is useful to get
the caustic lye content in g/l or ml/l. It is necessary to take
account of the density and the concentration of the applied
caustic lye for the calculation.

The parameters of calculation are the following:

Consumption in ml of acid solution. Usually


V hydrochloric acid of 0.1 mol/l (= 0,1 N) or
sulphuric acid of 0.05 mol/l (= 0.1 N)
Example
F taken quantity of liquor in ml .
For titration of F = 10ml of
Density of caustic lye
bleaching liquor of 0.1 mol/l of ρ (NaOH 50%ig = 1.53)
hydrochloric acid (= 0.1 N) V =
11.2 ml hydrochloric acid
solution is used. How much W % by weight of caustic lye
caustic lye of 50% in g/l
(W=50) does the bleaching
liquor contain ?
4⋅11.2⋅100
g/l NaOH50% = g/l Caustic lye in g/l:
10 ⋅ 50
NaOH 50% = 9 g/l
4 ⋅V ⋅100
g/l NaOH x − % =
F ⋅ W
Example

For titration of F = 10ml


Caustic lye in ml/l:
bleaching liquor 0.1 mol/l
hydrochloric acid (= 0.1 N) V = 4 ⋅V ⋅100
ml/l NaOH x − % =
11.2 ml hydrochloric acid F ⋅ W⋅ ρ
solution is used. How much
caustic of 50% lye in g/l
(W=50, ρ=1.53) does the
bleaching liquor contain ?
4 ⋅11.2 ⋅100
ml/l NaOH 50 % =
10 ⋅ 50 ⋅1.53
ml/l NaOH 50%ig = 5,9 ml/l

`eq=oK=_bfqif`e=dj_e=

26
Sodium hypochlorite (chlorine bleaching lye)

Sodium hypochlorite (Chlorine


bleaching lye)

Chemical formula: NaOCl


Molar mass: 74.5 g/mol

Properties of common chlorine


bleaching lye
„Active chlorine“ is the
% by quantity of chlorine which is
Content of active chlorine of weight 12.5
released during acidification of
commercially available chlorine approx. sodium hypochlorite with
bleach g/l
150 hydrochloric acid (see below)

Reactions of sodium hypochlorite


The most important reactions for bleaching with sodium
hypochlorite are the following:
Hydrolysis NaOCl + H2O → NaOH + HOCl

Release of bleaching agent HOCl → HCl + [O]

Maximal HOCl-development NaOCl + HCl → NaCl + HOCl


Formation of free chlorine
„Active chlorine“ HOCl + HCl → H2O + Cl2

Summarized in a diagram the pH-dependance of the


composition of sodium hypochlorite bleaching liquors is as
follows:

100
Cl2 HOCl
OCl-
80
Concentration [%]

60
b est r ang e f o r
b l eachi ng
40 p r o c ess

20

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH-value

The best pH range for bleaching is between 9 and 12. `eq=oK=_bfqif`e=dj_e=

27
Sodium hypochlorite (chlorine bleaching lye)

Active chlorine

Active chlorine Although chlorine does not have any bleaching effect, active
chlorine is defined as the quantity of chlorine which is released
HOCl + HCl → H2O + Cl2 during acidification of sodium hypochlorite with hydrochloric
acid.

Determination of active chlorine content in


sodium hypochlorite bleaching baths
The quantitative determination of the content of active chlorine
is done by a iodometric titration.
Transformation of sodium
hypochlorit e with iodide Out of an acid potassium iodide solution (KI) sodium
hypochlorite separates an equivalent quantity of iodine (I) to the
2 HOCl + 4 I + 2 H →
- +
-
2 I2 + 2 Cl + 2 H2O quantity of chlorine (Cl2), and it can be titrated with sodium
thiosulphate solution (Na2S2O3).
Back titration of iodine with
sodium thiosulphate The equivalence mass ratios result of the reaction equation or the
equivalence numbers of sodium thiosulphate and of chlorine (Cl2).
2 S2O32- + I2 → 2 I- + S4O62-
Equivalence
Molar mass
number z

Chlorine 2 70.906 g/mol

Sodium thiosulphate 1 158.10 g/mol

The equivalence ratios are the following:

n(eq) (Na2S2O3) = n(eq) (Cl2)

m (Cl 2 ) ⋅ z (Cl 2 )
n (Na2 S2O3 ) ⋅ z (Na2 S2 O3 ) = n (Cl 2 ) ⋅ z(Cl 2 ) =
M (Cl 2 )
m (Cl 2 ) ⋅ z (Cl 2 )
n (Na2 S2 O3 ) =
M (Cl 2 ) ⋅ z (Na2 S2 O3 )

Normally a 0.1 mol/l (= 0.1 N) Na2S2O3-solution is applied.


The calculation ist:
m (Cl 2 ) ⋅ 2
0.1 mol Na2 S2O3 =
70.906 g/mol ⋅ 1
0.1 mol Na2 S2O3 ⋅ 70.906 g/mol ⋅ 1
m (Cl 2 ) =
2
m (Cl 2 ) = 3.545 g
That means that 1 ml of a 0.1 mol/l (= 0,1 N) Na2S2O3-solution
corresponds to exactly 3.545 mg Cl2 or active chlorine.

`eq=oK=_bfqif`e=dj_e=

28
Sodium hypochlorite (chlorine bleaching lye)

Procedure of Titration

An aliquot part, usually 1 to 10ml, is taken from the bleaching


liquor and given into an Erlenmeyer flask containing some
distilled water and approx. 10ml potassium iodide solution
(approx. of 10%).

Then approx. 20ml of a sulphuric acid solution of 20% are


added.

The transformation which takes place of sodium hypochlorite


with potassium iodide to iodine is recognisable by a stronger
brown colouration of the solution.

With a sodium thiosulphate solution of 0.1 ml/l (= 0.1 N)


titration is done until a weak brown colouration is obtained.

After addition of 5 ml of a starch solution (approx a solution of


1 % of some soluble starch) the titration solution gets a strong
blue dyeing. Titration is continued with sodium thiosulphate
solution until the titration solution becomes colourless.

Calculation

The parameter of calculation are the following:

Consumption in ml of a Na2S2O3-solution with a


V
concentration of 0.1 mol/l (= 0.1 N).

F ml of taken quantity of bleaching liquor

1ml 0.1mol/l Na2S2O3


=
1ml of 0.1mol/l Na2S2O3 = 0.00355g active chlorine 0.00355g active chlorine

Example
Calculation of active chlorine content in g/l: For titration of F = 10ml
bleaching liquor with 0.1 mol/l
0.00355 ⋅ V ⋅ 1000 (= 0.1 N) sodium thiosulphate
g/l Active chlorine = solution are consumed V = 6,8
F ml Na2S2O3 solution. How
much active chlorine in g/l does
the bleaching bath contain ?

0.00355 ⋅ 6.8 ⋅ 1000


g/l Active chlorine =
10
g/l Aktive chlorine = 2.41 g/l

`eq=oK=_bfqif`e=dj_e=

29
Sodium hypochlorite (chlorine bleaching lye)

Dechlorination
Dechlorination has two purposes:

1. Elimination of the active chlorine from the fabric, because it


would damage the fibres during drying and storing.

2. Separation of chloramines (chlorine protein compounds).

Formation of chloramines Vegetable fibres are composed of protein compounds of the


protoplasma and form so-called chloramines in contact with
Protein compound
R-NH2 + NaOCl chlorine bleach lye.
→ R-NHCl + NaOH
Chloramine Chloramines tend to form hypochlorite in an humid
atmosphere, and this has a fibre damaging effect during
storing.

Decomposition of In addition to that chloramines separate hydrochloric acid


chloramines in a humid
during the drying process and this might cause fibre damage as
atmosphere
well.
R-NHCl + H2O

Dechlorination agent

Dechlorination can be done with reducing agents or with


hydrogen peroxide:

Theoretically necessary quantity for


Dechlorination
the destruction of 1g/l of active
agent
chlorine
4 x HOCl = 2 x 35.5g active chlorine = 158.1g sodium
Sodium thiosulphate thiosulphate
4 HOCl + S2O32- + H2O →
Sodium thiosulphate
(Antichlorine) 1g/l active chlorine = 0.55g/l sodium
2 SO42- + 6 H+ + 4 Cl-
thiosulphate
1 x HOCl = ½ 35.5g active chlorine = 104.06g
Sodium hydrogen sulphite Sodium hydrogen sodium hydrogen sulphite
HOCl + HSO3- → sulphite
HSO4- + H+ + Cl- (Bisulphite) 1g/l active chlorine = 2.9g/l sodium
hydrogene sulphite
3 x HOCl = 1.5 x 35.5g active chlorine = 158.1g sodium
Sodium dithionite hydrogen sulphite
3 HOCl + S2O42- + H2O → Sodium dithionite
2- + -
2 SO4 + 5 H + 3 Cl (Hydrosulphite) 1g/l active chlorine = 1.5g/l sodium hydrogen
sulphite
1 x HOCl = ½ 35.5g active chlorine = 34.02g hydrogen
peroxide
Hydrogen peroxide
HOCl + H2O2 → Hydrogen peroxide 1g/l active chlorine = 0.48g/lH2O2 100%
Cl- + H2O + H+ + O2
= 1.21ml/l H2O2 35%
= 0.8ml/l H2O2 50%

`eq=oK=_bfqif`e=dj_e=

30
Sodium hypochlorite (chlorine bleaching lye)

Determination of active chlorine content in


commercially available chlorine bleach lyes

In commercially available chlorine bleaching lyes the active


chlorine content usually is at 140 – 160 g/l. To test the content
of active chlorine, the concentrated chlorine bleaching lye is
diluted before the titration.

Titration is done with the same method as for the diluted


bleaching bath.

A dilution of 20 – 50 ml concentrated chlorine bleach lye per


liter with distilled water is advised.

Calculation

The parameters of calculation are the following:

Dilution of KV ml concentrated chlorine bleach


KV
lye per liter. Usually 20 – 50 ml/l.

Consumption in ml of Na2S2O3- solution with a


V
concentration of 0.1 mol/l (= 0.1 N).

ml of taken quantity of diluted chlorine bleach


F
lye for titration.

Example
Calculation of active chlorine content in g/l: KV = 20 ml commercially
available chlorine bleach lye
0.00355 ⋅ V ⋅ 1000 ⋅ 1000 was diluted on a liter. Of this
g/l Active chlorine = diluted solution F = 10 ml were
F ⋅ KV taken out and titrated with 0.1
mol/l (= 0.1 N) Na2S2O3
solution. A consumption of V =
8.5 ml Na2S2O3 solution was
found. How much active
chlorine in g/l does the
concentrated bleaching lye
contain.

0.00355 ⋅ 8.5 ⋅ 1000 ⋅ 1000


g/l Active chlorine =
10 ⋅ 20

g/l Active chlorine = 150 g/l

`eq=oK=_bfqif`e=dj_e=

31
Sodium chlorite

Sodium chlorite
Chemical formula: NaClO2
Molar mass: 90.5 g/mol

Properties of commercially available sodium


chlorite
Sodium chlorite 30 vol.% solution
Short name N 30

NaClO2 - [g/kg] approx. 245 (= 24.5 %)


concentrations [g/l] 300
slightly greenish-yellow clear
Aspect
liquid
Density ( 20) [g/cm ]
3
1 22
Solubility in water at 20
unlimited
°C

Start of crystallisation [°C] approx. -15

Reaction alkaline (pH-value approx.13)

Reactions of sodium chlorite


The most important reactions for bleaching with sodium chlorite
are the following.

Alkaline sodium chlorite solutions are very stable at room


temperature. In an acid medium, however, sodium chlorite
solutions are rapidly decomposed.

Hydrolysis NaClO2 + H2O → NaOH + HClO2

Release of bleaching agent HClO2 → HCl + 2 [O]

Decomposition of bleaching
agent in an acid solution 5 HClO2 → 4 ClO2 + HCl + 2 H2O
Formation of chlorine dioxide

3 HClO2 → 2 HClO3 + HCl

`eq=oK=_bfqif`e=dj_e=

32
Sodium chlorite

Summarized in a diagram the pH dependance of the


composition of sodium chlorite bleach liquors is as follows:

100
HClO2
ClO2-
80
Concentration [%]

ClO2
60
b est r ang e
f or
40 b leachi ng
p r o cess

20

0
0 1 2 3 4 5 6 7 8 9 10 11 12
pH-value

Determination of sodium chlorite content in


bleach liquors
The quantitative determination of the content of sodium chlorite Transformation of sodium
content is obtained by iodometric titration. chlorite with iodide

ClO2- + 4 I- + 4 H+ →
Sodium chlorite separates from an acid potassium iodide 2 I2 + Cl- + 2 H2O
solution (KI) a quantity of iodine (I) equivalent to the sodium
chlorite (NaClO2), which can be titrated with sodium Back titration of iodine with
sodium thiosulphate
thiosulphate solution (Na2S2O3).
2 S2O32- + I2 → 2 I- + S4O62-
The equivalence mass relations result from the reaction equation or
equivalence numbers of sodium thiosulphate and sodium chlorite.

Equivalence
Molar mass
number

Sodium chlorite 4 90.5 g/mol

Sodium thiosulphate 1 158.10 g/mol

`eq=oK=_bfqif`e=dj_e=

33
Sodium chlorite

The equivalence ratios result from:

n(eq) (Na2S2O3) = n(eq) (NaClO2)

m (NaClO2 ) ⋅ z (NaClO2 )
n (Na2 S2O3 ) ⋅ z (Na2 S2O3 ) = n (NaClO2 ) ⋅ z(NaClO2 ) =
M (NaClO2 )
m (NaClO2 ) ⋅ z (NaClO2 )
n (Na2 S2O3 ) =
M (NaClO2 ) ⋅ z (Na2 S2O3 )

Usually a solution of 0.1 mol/l (= 0.1 N) Na2S2O3 is applied.

The following equation is valid:

m (NaClO2 ) ⋅ 4
0,1 mol Na2 S2 O3 =
90,5 g/mol ⋅ 1
0,1 mol Na2 S2 O3 ⋅ 90,5 g/mol ⋅ 1
m (NaClO2 ) =
4
m (NaClO2 ) = 2,2625 g

That means that 1 ml of a solution of 0.1 mol/l (= 0.1 N) Na2S2O3-


solution exactly corresponds to 0.00226g NaClO2 100%.

Procedure of titration

An aliquot part is taken, normally 1 to 10ml of the bleaching


liquor and given into an Erlenmeyer flask containing some
distilled water and approx. 10ml of potassium iodide solution
(approx. 10%).

Then approx. 20ml of a sulphuric acid solution of 20% are


added.

The transformation of sodium hypochlorite with potassium


iodide to iodine becomes visible by a strong brown colouration
of the solution.

With a sodium thiosulphate solution of 0.1 ml/l (= 0.1 N) a


titration is done until a slightly brown titration is obtained.

After addition of 5 ml of a starch solution (approx. solution of 1


% of a soluble starch) the titration solution gets a strong blue
colouration. Titration with a sodium thiosulphate solution is
continued until the titration solution becomes colourless.

`eq=oK=_bfqif`e=dj_e=

34
Sodium chlorite

Calculation

The calculation parameters are the following:

Consumption in a Na2S2O3- solution with a


V
concentration of 0.1 mol/l (= 0.1 N).

F Taken quantity of bleach liquor in ml


Density of sodium chlorite solution
ρ
NaClO2 24.5% (30 Vol.%, N 30) = 1.22
W % by weight of sodium chlorite solution

1ml 0.1mol/l Na2S2O3


1ml of a 0.1mol/l Na2S2O3 = 0.00226g NaClO2 100 % =
0.00226g NaClO2 100 %

Calculation of sodium chlorite content in g/l: Example

0.00226 ⋅ V ⋅ 1000 ⋅ 100 For titration of F = 10ml of


g/l NaClO 2 100% = bleach liquor with 0.1 mol/l (=
F ⋅ W 0.1N) sodium thiosulphate
solution V = 4.2ml Na2S2O3
solution is consumed. How
much sodium chlorite 100% in
g/l does the bleach liquor
contain ?
0.00226 ⋅ 4.2 ⋅ 1000 ⋅ 100
g/l NaClO 100% =
2 10 ⋅ 100
Usually sodium chlorite solutions are applied (mostly 24.5 %,
g/l NaClO2 100% = 0.95g/l
30 Vol.%, N 30).

Calculation of sodium chlorite content in ml/l: Example

For titration of F = 10ml of


bleach liquor with 0.1 mol/l (=
0,00226 ⋅ V ⋅ 1000 ⋅ 100 0.1N) sodium hiosulphate
ml/l NaClO 2 100% = solution V = 5.0ml Na2S2O3
F ⋅ W ⋅ ρ solution is consumed. How
much sodium chlorite 24.5%
ml/l (W=24.5, ρ=1.22) does the
bleach liquor contain ?

0.00226 ⋅ 5.0 ⋅ 1000 ⋅ 100


ml/l NaClO 24,5% =
2 10 ⋅ 24 .5 ⋅ 1.22

ml/l NaClO2 24.5% = 3.78ml/l

`eq=oK=_bfqif`e=dj_e=

35
Sodium chlorite

Destruction of residual chlorite


The destruction of residual chlorite is obtained in particular with
the reducing agents sodium hydrogen sulphite (bisulphite) and
sodiumsulphite. In contrast to the situation in sodium
hypochlorite bleach, hydrogen peroxide and sodium
thiosulphate are less suitable for this purpose.

Before the reducing agents are added, the bleach liquor should
be neutralized to avoid smell because of the formation of
sulphure dioxide (SO2) from the reducing agent.

Theoretically necessary quantity to


Reducing agent destruct
1g/l sodium chlorite 100%
Sodium hydrogen
1 x 90.5g NaClO2 = 2 x 104.06g NaHSO3
sulphite Sodium hydrogen
ClO2 + 2 HSO3 →
- -
sulphite 1g/l NaClO2 100%
- + -
2 SO4 + 2 H + Cl (Bisulphite) = 2.3g/l sodium hydrogen sulphite
1 x 90.5g NaClO2 = 2 x 126.04g Na2SO3
= 2 x 252.14g Na2SO3 7 H2O
Sodium sulphite
ClO2- + 2 SO32- → 1g/l NaClO2 100%
2 SO4- + Cl--
Sodium sulphite
= 2.8g/l sodium sulphite
= 5.6 g/l sodiumsulphite
heptahydrate

`eq=oK=_bfqif`e=dj_e=

36
Persulphates

Persulphates
Properties of persulphates
Ammonium Potassium Sodium
Name
persulphate persulphate persulphate

Chemical formula (NH4)2S2O8 K2S2O8 Na2S2O8

Molar mass [g/mol] 228,2 270,3 238,2

Active oxygen content


[%] 6,9 5,8 6,5
(minimum)

10 °C [g/100g] 49 3,0 46
Solubility,
g/100 g aqueous 20 °C [g/100g] 54 5,5 54
solution at
30 °C [g/100g] 59 8,8 58

Persulphates slowly decompose in aqueous solution,


particularly at higher temperatures. Decomposition of persulphate

S2O82- + H2O
For this reason solutions of persulphates are stable only to a → 2 SO42- + 2 H+ + ½ O 2
limited degree. A higher bath temperature than 40 °C should be
absolutely avoided.

Evidence of persulphate content in addition


to hydrogen peroxide content in bleaching
liquors
In cold bleaches, persulphate is added in additon to hydrogen
peroxide. On the contrary to hydrogen peroxide a direct titration
of persulphate with potassium permanganate is not possible,
because persulphates do practically not react with
permanganate because of their rather high oxidation potential
at room temperature.

However the determination of the persulphate content is


possible by an indirect titration.

In the following the determination of hydrogen peroxide and


persulphate in bleaching liquors will be described.

`eq=oK=_bfqif`e=dj_e=

37
Persulphates

Principle of titration

Titration of hydrogen peroxide and persulpate is done in the


same bath sample as follows:

1. A liquor sample is taken and first the content of hydrogen


peroxide is titrated as usually with potassium
permanganate. Because persulphate does not react with
permanganate under these conditons, in this completely
titrated sample there is only pure persulphate. Complete
titration is absolutely necessary to destroy the hydrogen
peroxide.

2. A defined iron (II) salt solution is added to the completely


titrated sample. A part of the iron (II) is oxidated by
persulphate to iron(III). The iron(II) which was not oxidated
is back titrated with potassium permanganate, and the
content of persulphate is calculated.

Procedure

1. Fabrication of iron (II) (II) salt solution


Ammonium iron(II)sulphate A suitable iron (II) salt for the titration of persulphates is the
=
Mohr’s salt ammonium iron (II) sulphate, which is known under the name of
Mohr’s salt.
(NH4)2Fe(SO4)2 ⋅ 6 H2O
Approx. 40 g of ammonium iron (II) sulphate are dissolved by
vigourously shaking and with addition 100 ml of sulphuric acid
2+
of 10 % to one litre. The solution contains approx. 5.7 g/l Fe .

2. Determination of the content of iron (II) in the blank


sample

The content of iron (II) in the The iron (II) of the fabricated ammonium iron (II) sulphate
ammonium iron (II) sulphate solution is slowly oxidated to iron (III) by oxygen from the air.
solution (= blank sample) For this reason the actual content of iron (II) has to be
should be determined again determined before the titration is done.
before every titration.

20 ml of the ammonium iron (II) sulphate solution are mixed


with approx. 20 ml of sulphuric acid of 10 % and with a
potassium permanganate solution (normally 0.02 mol/l = 0.1 N),
which is applied for all further titrations, and tritrated until the
colour shade change to light pink is obtained.

`eq=oK=_bfqif`e=dj_e=

38
Persulphates

The consumption of potassium permanganate solution is VB = consumption of potassium


permanganate solution in case
recorded (VB). It serves for the calculation of the persulphate of a titration of 20 ml ammonium
content. iron II sulphate solution (= blank
sample).

3. Determination of the content of hydrogen peroxide in the


bleaching bath

A liquor sample is taken, usually 5 – 10 ml with approx. 20 ml Titration of hydrogen peroxide


of sulphuric acid of 10 % and the content of hydrogen peroxide with a solution of 0.2 mol/l
is determined with potassium permanganate (see also chapter (= 0.1 N) KMnO4.
HYDROGEN PEROXIDE).

In cold bleaching liquors the content of hydrogen peroxide is


normally rather high. For this reason it is advised to apply a
KMnO4 solution of 0.2 mol/l (= 1 N) instead of the usual 0.02
ml/l (= 0.1 N), so that the consumption is not too high. For the
titration of persulpate a solution of KMnO4 of 0.02 mol/l (=
0.1 N) should be applied.

The completely titrated sample is applied for further


titration.

4. Determination of the content of persulphate

20 ml of the ammonium iron (II) sulphate solution are added to VP = Consumption of potassium
the completely titrated sample. At any rate the same quantity of permanganate solution out of the
ammonium iron (II) sulphate solution has to be added as for the titration of the before completely
titrated liquor sample.
blank value determination.

Then titration is done with the potassium permanganate


solution which served for the determination of the content of
iron (II) in the ammonium iron (II) sulphate solution (= blank
sample), until the colour shade change to ligh pink is obtained
(VP).

`eq=oK=_bfqif`e=dj_e=

39
Persulphates

Calculation

The parameters for the calculation are the following:

F ml taken quantity of bleaching liquor.


Consumption of potassium permanganate
solution with a concentration of x mol/l (usually
VB
0.02 mol/l = 0.1 N) in titration of the ammonium
iron (II) sulphate solution in the blank sample.
Consumption of potassium permanganate
solution with a concentration of x mol/l (usually
VP
0.02mol/l = 0,1 N) in titration of completely
titrated bath samples.
Concentration of the applied potassium
x mol/l
permanganate solution. Normally 0.02 mol/l =
KMnO4
0.1 N
Conversion factor for sodium-, potassium or
ammonium persulphate.
Example
f 1 ml = 11.910 mg sodium persulphate
In a cold bleach bath the 1 ml = 13.515 mg potassium persulphate
content of sodium persulphate
is to be determined.
1 ml = 13.515 mg ammonium persulphate
for a solution of 0.02 mol/l of KMnO4
Titration of 20 ml ammonium
iron (II) sulphate solution (=
blank vat) gave a consumption
of 0.02 mol/l KMnO4- solution
(= 0.1 N) of VB = 20.4 ml. Calculation of the H2O2-concentration:
F = 10 ml of the cold bleach
bath was taken and first the
The determination and calculation of the hydrogen peroxide
content of hydrogen peroxide concentration is done as described in the chapter about
was determined with a solution HYDROGEN PEROXIDE.
of 0.2 mol/l (= 1 N) KMnO4 .
The liquor sample which had
been completely tritrated in this
way was then mixed with 20 ml Calculation of the persulphate concentration:
ammonium iron (II) sulphate
solution and titrated with
0.02 mol/l KMnO4-solution (= The following calculation formula is such that it can be
0.1 N) up to the colour shade calculated with every concentration of potassium
change to light pink. A permanganate solution. Only the concentration in mol/l should
consumption of KMnO4 of VP = be known. Independently from the applied potassium
13.7 ml was recorded.
permanganate solution for the conversion on sodium-,
The content of sodium potasium or ammonium persulphate the factors f have to be
persulphate is calculated as taken out of the above given table.
follows:
(20.4 - 13.7) ⋅ 0.02 ⋅ 11.910
g/l Na - persulphat e =
0.02 ⋅ 10 (VB - VP ) ⋅ xmol/lKMnO4 ⋅ f
e=
g/l Persulphat
g/l Na-persulphate = 8 g/l
0.02 ⋅ F

`eq=oK=_bfqif`e=dj_e=

40
Silicates

Silicates
Properties of commercially available
sodium silicates
Name Sodium silicate Sodium silicate
37/40 40/42

ρ20)
Density (ρ [g/cm 3 ] 1,34 - 1,38 1,38 - 1,40

Density in °Be [°Be] 37 - 40 40 - 42

Silicium oxide SiO2 [%] 26,5 - 28,5 28 - 30

Sodium oxide Na2O [%] 8-9 8,5 - 9,3

Mole ratio
3,3 - 3,5 3,2 - 3,4
(SiO2 : Na2O)
Weight ratio (SiO2 :
3,2 - 3,4 3,1 - 3,3
Na2O)

Viscosity at 20°C [mPa ⋅ s] 50 - 150 100 - 240

Properties of commercially available


metasilicates
Na-
Na-metasilicate Na-metasilicate
Name metasilicate
5-hydrate 9-hydrate
anhydrous

Chemical formula Na2SiO3 Na2SiO3⋅5 H2O Na2SiO3⋅9 H2O

Molar mass [g/mol] 140 230 302

Silicium oxide SiO2 [%] 46.2 - 47.6 28.0 - 29.4 21.8 - 23.8

Sodium oxide Na2O [%] 50.4 - 51.8 28.1 - 29.5 21.7 - 23.7

Dry substance [%] 96.5 - 99.5 56.5 - 58.5 44 - 47

Other properties of silicate of soda


• In combination with magnesium compounds (e.g. Epsom
salt) there is a good stabilizing effect in the hydrogen
peroxide bleach.
• Silicates increase the soil suspending property of washing
baths. `eq=oK=_bfqif`e=dj_e=

41
Hardness of water

Silicate precipitations with • Silicates have a very high sequestering power on heavy
hardening substances metals and thus have an anticatalytic effect
(schematically)
Ca Mg • Silicates hydrolyze at high temperatures and can form
ONa O O ONa ONa OH O O

O Si O Si O Si O Si O Si O Si O Si O Si O
insoluble silicic acid.
OH O OH O O ONa O ONa
• Silicates form insoluble compounds with alkaline earths
Ca Ca Mg

ONa O OH ONa ONa OH O ONa


and can cause sediments on fibres and machine parts.
O Si O Si O Si O Si O Si O Si O Si O Si O
• Silicates have a high buffering power.
OH O O ONa O O O O

Mg Ca Mg

Ca-silicate deposits on
cotton fibres
Alkali content of silicates

For the calculation of the alkali content (caustic lye) of silicates


the following decomposition reaction is taken as a basis:

Na2O + H2O → 2 NaOH

61.979 g/mol + 18.0152 g/mol → 2 ⋅ 39.99 g/mol

2 ⋅ 39.99 g = 79.98 g of sodium hydroxide (NaOH) are formed


of 61.979g Na2O.

The parameter of calculation are the following:

Remark
Content of sodium oxide (Na2O)
W
The data of density and content (37/40 = 8.5%; 40/42 = 8.9%)
of sodium oxide are the
average values of above given
tables. It is possible that the Density of sodium silicate
values differ from the applied ρ (37/40 = 1.36; 40/42 = 1.39)
sodium silicate. Therefore the
data should better be taken
from the specifications. Applied quantity of silicate of soda in ml/l
V
(in case of metasilicates in g/l)

Example Calculation of NaOH-concentration in g/kg:


How much NaOH g.kg does
sodium silicate 37/40 contain? Corresponding to the sodium oxide indications (Na2O) of above
The Na2O-content of this given table the sodium hydroxide content of the silicates can be
silicate of soda is indicated with calculated as follows.
8-9 % in the table (medium
79,98 ⋅ 10
value 8.5 %). NaOH 100% [g/kg ] = ⋅W
61.979
NaOH 100% = 12.904 · 8.5
= 110g/kg = 11 %
= 12.904 ⋅ W

`eq=oK=_bfqif`e=dj_e=

42
Silicates

Calculation of NaOH-concentration in g/l:


In bleach liquors sodium silicate is normally applied in ml/l. The Example
sodium hydroxide content (NaOH) out of sodium of silicate in
In a bleach liquor V=10ml
such a bleaching bath is calculated as follows:
sodium silicate 37/40 (ρ=1.36,
W=8.5) is applied. How much
79.98 ⋅ W ⋅ V ⋅ ρ NaOH 100 % in g/l does the
NaOH 100% [g/l ] =
61.979 ⋅ 1000 bath contain ?
12,904 ⋅ 8,5 ⋅10 ⋅ 1,36
NaOH 100% [g/l ] =
1000

12.904 ⋅ W ⋅ V ⋅ ρ
= NaOH 100% = 1.49 g/l
1000

For metasilicates it is not possible to indicate density because


it is a solid substance. Therefore the calculation formula for
metasilicates is the follwing:

79.98 ⋅ W ⋅ V
NaOH 100% [g/l ] =
61.979 ⋅ 1000

12.904 ⋅ W ⋅ V
=
1000

`eq=oK=_bfqif`e=dj_e=

43
Hardness of water

Hardness of water
Hardness classification
Hardness of industrial waters can have a considerable
Total hardness Description influence on pretreatment and dyeing results. High hardness
° dH
for example can cause:
0-7 soft
7-14 medium • Deposits of hardening substances on machines or textiles.
14-21 hard • Precipitations of dyes which are sensitive to hardness in
> 21 very hard
the dyeing liquor.

Total hardness (GH)


For this reason a regular control of the hardness of the
Total concentration of all industrial water can be very helpful so that possible reasons for
dissolved calcium- and defects can be recognized early and eliminated.
magnesium ions.

Carbonate hardness (KH) =


On thebasis of the total hardness of water it is differentiated
Ca- nd Mg-hydrogen between carbonate hardness (former temporary hardness) and
carbonates. During boiling permanent hardness. The carbonate hardness forms insoluble
insoluble Ca- or Mg-carbonate Ca- or Mg-carbonates during boiling and therefore causes
is formed:
deposits whereas the permanent hardness remains in solution
Ca(HCO3)2 → CaCO3 + H2O + CO2 even at a higher temperature.
Permanent hardness = Ca-
and Mg-chlorides, sulphates,
nitrate and others Determination of water hardness (total
hardness)
Ca- and Mg-ions can be determined in ammoniacal solution
complexometrically with EDTA (ethylene diamine tetraacetate) and
with Eriochrom black T (or indicator buffer tablet) as indicator.

Procedure of titration

100 ml are taken of the water sample and an indicator-buffer


tablet is dissolved in it. 2 ml ammonia 25 % are added and
heated up at 40 °C. The solution becomes more or le ss red
depending on the water hardness. Then titration is carried out
immediately with 0.1 mol/l EDTA-solution from red to green.

Calculation

The parameters of calculation are the following:

Consumption in ml of EDTA-solution at a
V
concentration of x mol/l.
F Taken quantity of water sample in ml
x mol/l Concentration of applied EDTA-solution, usually
EDTA 0.01 mol/l.
`eq=oK=_bfqif`e=dj_e=

44
Hardness of water

EDTA always forms with metal ions a 1:1 complex. 1 mol EDTA EDTA-complex
binds 1 mol of a metal ion, e.g. calcium. O

O C
Table:
O
CH2
C CH2
= 0.4008 mg Ca O N
1 ml of 0.01 mol/l EDTA-solution = 0.5608 mg CaO CH2
Ca2+
= 1.00 mg CaCO3 CH2
O N
corresponds to
C CH2
= 0.24305 mg Mg CH2
O
0.01 mmol metal = 0.4030 mg MgO O C
= 0.8431 mg MgCO3 O

Calculation of content of hardening substances Example


in mmol/l: For the titration of F = 100ml of
a water sample with 0.01 mol/l
x mol/l EDTA ⋅ V ⋅1000 EDTA-solution V = 13ml EDTA-
mmol/l = solution is consumed. How
F much mmol/l of hardness does
water contain ?
With this formula the content of CaCO3 can be exactly 0.01mol/l EDTA ⋅ 13 ⋅1000
mmol/l =
100
calculated in mg/l.
mmol/l hardness = 1.3 mmol/l

Calculation of content of hardening substances Example

in °dH: For the titration of F = 100ml of


a water sample 0.01 mol/l
EDTA-solution V = 13ml EDTA-
solution is consumed. How
According to definition: 1 °dH = 10 mg/l CaO = 7.19 mg/l MgO much °dH has the water ?

0,01mol/l EDTA ⋅13 ⋅ 5.608 ⋅ 1000


°dH =
100
x mol/l EDTA ⋅ V ⋅ 5.608 ⋅ 1000
°dH = °dH = 7.3 °dH
F

`eq=oK=_bfqif`e=dj_e=

45
Hardness of water

Conversion factors for common units of


water hardness
mmol/l Alkaline English French German Russian ppm as
earth ions hardness hardness hardness hardness CaCO3
Definition of different
hardness data mmol/l alkaline
1 1 7,02 10 5,6 40 100
German earth ions
1° 10 mg/l CaO
hardness
French English
1° 10 mg/l CaCO3 1° 0,14 1 1,429 0,7999 5,714 14,29
hardness hardness

10 mg/0,7 l CaCO3
English 1 ° French hardness 0,1 0,7 1 0,5599 4 10

hardness
14.29 mg/l CaCO4
German
1° 0,18 1,25 1,786 1 7,144 17,85
American hardness
1 1 mg/l CaCO3
hardness (USA)
Russian
1° 0,025 0,175 0,25 0,14 1 2,5
hardness

ppm as
1 0,01 0,07 0,1 0,06 0,4 1
CaCO3

`eq=oK=_bfqif`e=dj_e=

46
Average polymerisation degree and fluidity

Average degree of polymerisation


(DP-value)
The cellulose molecule is a polysaccharide composed of β-1.4 CH2OH
O
OH CH2OH
O
O OH
linked glucose units. The so-called polymerisation degree gives OH
O
O OH

evidence of the number of chain elements (glucose units). OH CH2OH OH n/3

n = degree of
E.g. if there is chemical damage in bleaching, the long chain polymerisation
molecule is separated into smaller fragments. The
polymerisation degree decreases. If the cellulose is completely
dissolved in a solvent, the viscosity of the solution is higher at a
higher polymerisation degree, because there are more of the
bigger molecules and vice versa. Due to this the polymerisation
degree of a cellulose fibre can be determined by a viscosity
measurement.

The average polymerisation degree only reflects the extent of a


chemical damage, and can be used to distinguish between
chemical and mechanic damage. This is different from the
determination of the tear strength e.g. , the average
polymerisation degree is completely independent from the
structure of the fabric and thus much more specific.

Measuring method
There are four procedures for the viscosimetric determination
of the polymerisation degree of cellulose fibres and cellulose
material with the difference in solvents.

• Cuoxam procedure
• The cupriethylene diamine procedure
• EWNN - procedure
• Nitrate procedure Remark

The fibre material is dissolved in a solvent according to all Difficulties can be caused by
resin finished, reactive dyed
procedures (in case of the nitrate procedure after a preceding or mercerized fabrics
nitration) and the running time of the solution is measured by depending on the procedure
means of a capillary as well as the running time of the pure because sometimes the fibre
solvent as reference. material is not completely
dissoved in the solvent and
measuring becomes
The fibre material applied for the DP value determination impossible.
should be free of sizes, finishs etc.

The methods for the determination of the average


polymerisation degree are all very difficult, and a lot of
experience and accuracy is needed, so that the measurements
should be carried out only in well equipped laboratories.
`eq=oK=_bfqif`e=dj_e=

47
Average polymerisation degree and fluidity

Calculations
DP-values of different fibres According to Staudinger the following formula is valid for the
DP-value:
Substrate DP - value

Natural fibres: η − η0 1 1
Cotton, flax, Ramie 2000 – 3000 DP = ⋅ ⋅
η C km
Regenerated
cellulose:
Copper procedure 400 – 500 η: Runnning time of solution in sec.
Viscose procedure 250 – 400
200 – 300 η0: Running time of solvent in sec
Acetate procedure
c: Cellulose concentration in g/l
Km: Constant of solvent

There is a decrease of the polymerisation degree in case of


every damage, and its amount on the other hand gives
conclusion on degree of the damage. According to O. Eisenhut
the functioning of polymerisation degree - decrease = fibre
damage is defined as damage factor by the following formula:

æ 2000 2000 ö
log ç − + 1÷
s= è Ptx Pt ø
log 2
Pt: DP – value of cellulose before the chemical treatment
Ptx: DP – value of cellulose after the chemical treatment
2000: DP – value of CO as point of reference

The relation of the DP value before and after the damaging and
the damaging factor is shown in the following graph.

Judgment of damaging degree


dam aging factor
s-factor judgment 1,2 1,0 0,8 0,6 0,4 0,2 0,0
3600
DP-value before damaging

0.01–0.20 very good – undamaged


0.21–0.30 good, very gentle 3200
bleaching
0.31–0.50 sufficient 2800
0.51–0.75 slightly damaged
> 0.75 very much damaged
2400

2000

1600
800 1200 1600 2000 2400 2800 3200 3600

DP-value after dam aging

`eq=oK=_bfqif`e=dj_e=

48
Average polymerisation degree and fluidity

Fluidity F
In different countries not the DP-value but the fluidity number is
given. The basis of the measuring procedure to determine the
fluidity number is like the principle of the DP-determination, that
means the determination of viscosities. Strictly speaking the Judgement of fluidity
fluidity is the reciprocal value of the dynamic viscosity.
Fluidity Judgement

Calculations ≤2
2.1-3.5
undamaged
good, very gentle
bleach
The fluidity formula is: 3.6-5.0 sufficient
5.1-8.0 slightly damaged
> 8.0 very damaged
C' C
F= C' =
k ρ
t −
t

C: Constant of viscosimeter
k: Factor of correction
t: Run-out time of solvent
ρ: Density of solvent

There is the following relation between DP-value and fluidity:

æ 74,35 + F ö
DP = 2032 ⋅ ç log ÷ − 573
è F ø

Illustrated in a diagram:

Relation between DP value and fluidity


3400

3000

2600
DP-value

2200

1800

1400

1000

600
0 2 4 6 8 10 12 14 16 18 20

Fluidity

`eq=oK=_bfqif`e=dj_e=

49
Annex – Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic lye and caustic potash

Annex
Density and concentration of sulphuric acid,
hydrochloric acid, nitric acid, caustic lye
and caustic potash solution

Density °Be Sulphuric acid Hydochloric acid Nitric acid Caustic lye Caustic potash

ρ20 % w/w g/l % w/w g/l % w/w g/l % w/w g/l % w/w g/l

1,000 0,0 0,261 2,609 0,360 3,600 0,333 3,330 0,159 1,590 0,197 1,970
1,005 0,7 0,985 9,904 1,360 13,670 1,255 12,610 0,602 6,050 0,743 7,470
1,010 1,4 1,731 17,483 2,360 23,840 2,164 21,860 1,045 10,550 1,295 13,080
1,015 2,1 2,485 25,223 3,370 34,210 3,073 31,190 1,490 15,120 1,839 18,670
1,020 2,7 3,242 33,068 4,390 44,780 3,982 40,620 1,937 19,760 2,380 24,280
1,025 3,4 4,000 41,000 5,410 55,450 4,883 50,050 2,384 24,440 2,931 30,040
1,030 4,1 4,746 48,884 6,430 66,230 5,783 59,570 2,839 29,240 3,480 35,840
1,035 4,7 5,493 56,852 7,460 77,210 6,661 68,940 3,289 34,040 4,030 41,710
1,040 5,4 6,237 64,865 8,490 88,300 7,530 78,310 3,735 38,840 4,580 47,630
1,045 6,0 6,956 72,690 9,510 99,380 8,398 87,760 4,199 43,880 5,121 53,510
1,050 6,7 7,704 80,892 10,520 110,460 9,259 97,220 4,655 48,880 5,660 59,430

1,055 7,4 8,415 88,778 11,520 121,540 10,120 106,770 5,107 53,880 6,200 65,410
1,060 8,0 9,129 96,767 12,510 132,610 10,970 116,280 5,562 58,960 6,740 71,440
1,065 8,7 9,843 104,828 13,500 143,780 11,810 125,780 6,017 64,080 7,280 77,530
1,070 9,4 10,510 112,460 14,490 155,040 12,650 135,360 6,471 69,240 7,820 83,670
1,075 10,0 11,260 121,040 15,480 166,410 13,480 144,910 6,928 74,480 8,360 89,870
1,080 10,6 11,960 129,170 16,470 177,880 14,310 154,550 7,378 79,680 8,890 96,010
1,085 11,2 12,660 137,360 17,450 189,330 15,130 164,160 7,827 84,920 9,429 102,310
1,090 11,9 13,360 145,620 18,430 200,890 15,950 173,860 8,283 90,280 9,960 108,560
1,095 12,4 14,040 153,740 19,410 212,540 16,760 183,520 8,734 95,640 10,489 114,860
1,100 13,0 14,730 162,030 20,390 224,290 17,580 193,380 9,189 101,080 11,030 121,330

1,105 13,6 15,410 170,280 21,360 236,030 18,390 203,210 9,643 106,560 11,560 127,740
1,110 14,2 16,080 178,490 22,330 247,860 19,190 213,010 10,097 112,080 12,080 134,090
1,115 19,3 16,760 186,870 23,290 259,680 20,000 223,000 10,554 117,680 12,610 140,600
1,120 15,4 17,430 195,220 24,250 271,600 20,790 232,850 11,007 123,280 13,140 147,170
1,125 16,0 18,090 203,510 25,220 283,720 21,590 242,890 11,463 128,960 13,660 153,670
1,130 16,5 18,760 211,990 26,200 296,060 22,380 252,890 11,919 134,680 14,190 160,350
1,135 17,1 19,420 220,420 27,180 308,490 23,160 262,870 12,344 140,100 14,706 166,910
1,140 17,7 20,080 228,910 28,180 321,250 23,940 272,920 12,825 146,200 15,220 173,510
1,145 18,3 20,730 237,360 29,170 334,000 24,710 282,930 13,279 152,040 15,741 180,230
1,150 18,8 21,380 245,870 30,140 346,610 25,480 293,020 13,729 157,880 16,260 186,990

`eq=oK=_bfqif`e=dj_e=

50
Annex – Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic lye and caustic potas

Density °Be Sulphuric acid Hydrochloric aicid Nitric acid Caustic lye Caustic potash

ρ20 % w/w g/l % w/w g/l % w/w g/l % w/w g/l % w/w g/l

1,155 19,3 22,030 254,450 31,140 359,670 26,240 303,070 14,182 163,800 16,780 193,810
1,160 19,8 22,670 262,970 32,140 372,820 27,000 313,200 14,634 169,760 17,290 200,560
1,165 20,3 23,309 271,550 33,161 386,320 27,761 323,410 15,090 175,800 17,810 207,490
1,170 20,9 23,950 280,210 34,180 399,910 28,510 333,570 15,538 181,800 18,320 214,340
1,175 21,4 24,580 288,810 35,200 413,600 29,250 343,690 15,990 187,880 18,840 221,370
1,180 22,0 25,210 297,480 36,230 427,510 30,000 354,000 16,441 194,000 19,350 228,330
1,185 22,5 25,840 306,200 37,270 441,650 30,740 364,270 16,891 200,160 19,860 235,340
1,190 23,1 26,470 314,990 38,320 456,010 31,470 374,490 17,345 206,400 20,370 242,400
1,195 23,5 27,100 323,850 39,370 470,470 32,210 384,910 17,797 212,680 20,879 249,510
1,200 24,0 27,720 332,640 - 32,948 395,380 18,253 219,040 21,380 256,560

1,205 24,5 28,330 341,380 - 33,680 405,840 18,709 225,440 21,880 263,650
1,210 25,0 28,950 350,290 - 34,410 416,360 19,160 231,840 22,380 270,800
1,215 25,5 29,570 359,280 - 35,160 427,200 19,615 238,320 22,880 277,990
1,220 26,0 30,180 368,200 - 35,930 438,350 20,072 244,880 23,380 285,240
1,225 26,4 30,790 377,180 - 36,700 449,580 20,526 251,440 23,869 292,400
1,230 26,9 31,400 386,220 - 37,480 461,000 20,979 258,040 24,370 299,750
1,235 27,4 32,010 395,320 - 38,250 472,390 21,438 264,760 24,860 307,020
1,240 27,9 32,610 404,360 - 39,020 483,850 21,897 271,520 25,360 314,460
1,245 28,4 33,220 413,590 - 39,800 495,510 22,355 278,320 25,850 321,830
1,250 28,8 33,820 422,750 - 40,580 507,250 22,813 285,160 26,340 329,250

1,255 29,3 34,420 431,970 - 41,360 519,070 23,273 292,080 26,830 336,720
1,260 29,7 35,010 441,130 - 42,140 530,960 23,730 299,000 27,320 344,230
1,265 30,2 35,600 450,340 - 42,920 542,940 24,190 306,000 27,800 351,670
1,270 3,6 36,190 459,610 - 43,700 554,990 24,643 312,960 28,290 359,280
1,275 31,1 36,780 468,940 - 44,480 567,120 25,098 320,000 28,770 366,820
1,280 31,5 37,360 478,210 - 45,270 579,460 25,556 327,120 29,250 374,400
1,285 32,0 37,950 487,660 - 46,060 591,870 26,014 334,280 29,731 382,040
1,290 32,4 38,530 497,040 - 46,850 604,370 26,478 341,560 30,210 389,710
1,295 32,8 39,100 506,340 - 47,630 616,810 26,941 348,880 30,680 397,300
1,300 33,3 39,680 515,840 - 48,420 629,460 27,403 356,240 31,150 404,950

`eq=oK=_bfqif`e=dj_e=

51
Annex – Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic lye and caustic potash

Density °Be Sulphuric acid Hydrochloric acid Nitric acid Caustic lye Caustic potash

ρ20 % w/w g/l % w/w g/l % w/w g/l % w/w g/l % w/w g/l

1,305 33,7 40,250 525,260 - 49,210 642,190 27,868 363,680 31,620 412,640
1,310 34,2 40,820 534,740 - 50,000 655,000 28,330 371,120 32,090 420,380
1,315 34,6 41,390 544,280 - 50,850 668,680 28,794 378,640 32,560 428,170
1,320 35,0 41,950 553,740 - 51,710 682,570 29,261 386,240 33,030 436,000
1,325 35,4 42,510 563,260 - 52,560 696,420 29,727 393,880 33,500 443,880
1,330 35,8 43,070 572,830 - 53,410 710,350 30,195 401,600 33,970 451,800
1,335 36,2 43,620 582,330 - 54,270 724,500 30,652 409,200 34,430 459,640
1,340 36,6 44,170 591,880 - 55,130 738,740 31,134 417,200 34,900 467,660
1,345 37,0 44,720 601,480 - 56,040 753,740 31,613 425,200 35,360 475,590
1,350 37,4 45,260 611,010 - 56,950 768,830 32,089 433,200 35,820 483,570

1,355 37,8 45,800 620,590 - 57,870 784,140 32,561 441,200 36,280 491,590
1,360 38,2 46,330 630,090 - 58,780 799,410 33,059 449,600 36,735 499,600
1,365 38,6 46,860 639,640 - 59,689 814,760 33,553 458,000 37,190 507,640
1,370 39,0 47,390 649,240 - 60,670 831,180 34,015 466,000 37,650 515,810
1,375 39,4 47,920 658,900 - 61,689 848,230 34,502 474,400 38,105 523,950
1,380 39,8 48,450 668,610 - 62,700 865,260 35,014 483,200 38,560 532,130
1,385 40,1 48,970 678,230 - 63,721 882,530 35,495 491,600 39,010 540,290
1,390 40,5 49,480 687,770 - 64,740 899,890 36,000 500,400 39,460 548,490
1,395 40,8 49,990 697,360 - 65,840 918,470 36,502 509,200 39,920 556,890
1,400 41,2 50,500 707,000 - 66,970 937,580 37,000 518,000 40,370 565,180

1,405 41,6 50,967 716,090 - 68,100 956,810 37,495 526,800 40,820 573,520
1,410 42,0 51,520 726,430 - 69,230 976,140 37,986 535,600 41,260 581,770
1,415 42,3 51,984 735,580 - 70,390 996,020 38,473 544,400 41,710 590,200
1,420 42,7 52,510 745,640 - 71,630 1017,150 38,986 553,600 42,155 598,600
1,425 43,1 53,010 755,390 - 72,860 1038,250 39,495 562,800 42,600 607,050
1,430 43,4 53,500 765,050 - 74,090 1059,490 40,000 572,000 43,040 615,470
1,435 43,8 54,000 774,900 - 75,351 1081,280 40,502 581,200 43,479 623,930
1,440 44,1 54,490 784,660 - 76,710 1104,620 41,028 590,800 43,920 632,450
1,445 44,4 54,970 794,320 - 78,070 1128,110 41,550 600,400 44,360 641,000
1,450 44,8 55,450 804,030 - 79,430 1151,740 42,069 610,000 44,790 649,460

`eq=oK=_bfqif`e=dj_e=

52
Annex – Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic lye and caustic potas

Density °Be Sulphuric acid Hydrochloric acid Nitric acid Caustic lye Caustic potash

ρ20 % w/w g/l % w/w g/l % w/w g/l % w/w g/l % w/w g/l

1,455 45,1 55,930 813,780 - 80,880 1176,800 42,584 619,600 45,230 658,100
1,460 45,4 56,410 823,590 - 82,390 1202,890 43,123 629,600 45,660 666,640
1,465 45,8 56,890 833,440 - 83,911 1229,290 43,631 639,200 46,094 675,280
1,470 46,1 57,377 843,440 - 85,500 1256,850 44,163 649,200 43,469 638,990
1,475 46,4 57,840 853,140 - 87,289 1287,520 44,692 659,200 46,960 692,660
1,480 46,8 58,310 862,990 - 89,070 1318,240 45,216 669,200 47,390 701,370
1,485 47,1 58,780 872,880 - 91,130 1353,280 45,737 679,200 47,820 710,130
1,490 47,4 59,240 882,680 - 93,490 1393,000 46,255 689,200 48,250 718,930
1,495 47,8 59,700 892,520 - 95,460 1427,120 46,796 699,600 48,674 727,680
1,500 48,1 60,170 902,550 - 96,730 1450,950 47,333 710,000 49,100 736,500

1,505 48,4 60,620 912,330 - 97,990 1474,750 47,841 720,000 49,530 745,430
1,510 48,7 61,080 922,310 - 99,260 1498,830 48,371 730,400 49,950 754,250
1,515 49,0 61,540 932,330 - - 48,898 740,800 50,380 763,260
1,520 49,4 62,000 942,400 - - 49,421 751,200 50,800 772,160
1,525 49,7 62,450 952,360 - - 49,967 762,000 51,220 781,100
1,530 50,0 62,910 962,520 - - 50,484 772,400 51,640 790,090
1,535 50,3 63,360 972,580 - - - -
1,540 50,6 63,810 982,670 - - - -
1,545 50,9 64,260 992,810 - - - -
1,550 51,2 64,710 1003,010 - - - -

1,555 51,5 65,150 1013,090 - - - -


1,560 51,8 65,590 1023,200 - - - -
1,565 52,1 66,030 1033,370 - - - -
1,570 52,4 66,470 1043,580 - - - -
1,575 52,7 66,910 1053,840 - - - -
1,580 53,0 67,350 1064,130 - - - -
1,585 53,3 67,790 1074,470 - - - -
1,590 53,6 68,230 1084,860 - - - -
1,595 53,9 68,660 1095,120 - - - -
1,600 54,1 69,090 1105,440 - - - -

`eq=oK=_bfqif`e=dj_e=

53
Annex – Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic lye and caustic potash

Density °Be Sulphuric acid Hydrochloric acid Nitric acid Caustic lye Caustic potash

ρ20 % w/w g/l % w/w g/l % w/w g/l % w/w g/l % w/w g/l

1,605 54,4 69,530 1115,960 - - - -


1,610 54,7 69,960 1126,360 - - - -
1,615 55,0 70,390 1136,800 - - - -
1,620 55,2 70,820 1147,280 - - - -
1,625 55,5 71,250 1157,810 - - - -
1,630 55,8 71,670 1168,220 - - - -
1,635 56,0 72,090 1178,670 - - - -
1,640 56,3 72,520 1189,330 - - - -
1,645 56,6 72,950 1200,030 - - - -
1,650 56,9 73,370 1210,610 - - - -

1,655 57,9 73,800 1221,390 - - - -


1,660 57,1 74,220 1232,050 - - - -
1,665 57,4 74,640 1242,750 - - - -
1,670 57,7 75,070 1253,670 - - - -
1,675 58,2 75,490 1264,450 - - - -
1,680 58,4 75,920 1275,460 - - - -
1,685 58,7 76,340 1286,330 - - - -
1,690 58,9 76,770 1297,410 - - - -
1,695 59,2 77,200 1308,540 - - - -
1,700 59,5 77,630 1319,710 - - - -

1,705 59,7 78,060 1330,920 - - - -


1,710 60,0 78,490 1342,180 - - - -
1,715 60,2 78,930 1353,650 - - - -
1,720 60,4 79,370 1365,160 - - - -
1,725 60,6 79,810 1376,720 - - - -
1,730 60,9 80,250 1388,330 - - - -
1,735 61,1 80,700 1400,150 - - - -
1,740 61,4 81,160 1412,180 - - - -
1,745 61,6 81,620 1424,270 - - - -
1,750 61,8 82,090 1436,580 - - - -

`eq=oK=_bfqif`e=dj_e=

54
Annex – Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic lye and caustic potas

Density °Be Sulphuric acid Hydrochloric acid Nitric acid Caustic lye Caustic potash

ρ20 % w/w g/l % w/w g/l % w/w g/l % w/w g/l % w/w g/l

1,755 62,1 82,570 1449,110 - - - -


1,760 62,3 83,060 1461,860 - - - -
1,765 62,5 83,576 1475,110 - - - -
1,770 62,8 84,080 1488,220 - - - -
1,775 63,0 84,610 1501,830 - - - -
1,780 63,2 85,160 1515,850 - - - -
1,785 63,5 85,740 1530,460 - - - -
1,790 63,7 86,350 1545,670 - - - -
1,795 64,0 86,990 1561,470 - - - -
1,800 64,2 87,690 1578,420 - - - -

1,805 64,4 88,430 1596,160 - - - -


1,810 64,6 89,230 1615,060 - - - -
1,815 64,8 90,120 1635,680 - - - -
1,820 65,0 91,110 1658,200 - - - -
1,821 65,0 91,334 1663,190 - - - -
1,822 65,1 91,560 1668,220 - - - -
1,823 65,1 91,780 1673,150 - - - -
1,824 65,2 92,000 1678,080 - - - -
1,825 65,2 92,250 1683,560 - - - -
1,826 65,3 92,510 1689,230 - - - -
1,827 65,3 92,825 1695,910 - - - -
1,828 65,4 93,030 1700,590 - - - -
1,829 65,4 93,361 1707,570 - - - -
1,830 65,4 93,640 1713,610 - - - -
1,840 65,9 95,598 1759,000 - - - -

`eq=oK=_bfqif`e=dj_e=

55
Annex – Brief instruction Titration of hydrogen peroxide

Brief instruction - Titration of hydrogen


peroxide

Procedure of titration

Remark An aliquot part is taken out, usually 1 to 10 ml, of the bleaching


bath and given into an Erlenmeyer flask containing approx.
Calculation is only valid for a 10 ml of a sulphuric acid of 20%. Titration is done immediately
0.02 mol/l (= 0.1N) potassium with a potassium permanganate solution of 0.02 mol/l (= 0./1 N)
permanganate solution.
on a first persisting pink-violet colouration.

Calculation
Valid for a potassium permanganate solution of 0.02 mol/l (= 0.1 N)

Factor for Factor for Factor for


Example Sample of H2O2 100% H2O2 50% H2O2 35%
bleach liquor
For titration of 2 ml bleach in g/l in g/l in ml/l in g/l in ml/l
liquor with solution of 0.02mol/l
KMnO4 (= 0.1 N) 8.7ml of 1 ml 1,701 3,401 2,846 4,859 4,293
KMnO4-solution are consumed.
2 ml 0,850 1,701 1,423 2,430 2,146
How much H2O2 of 50% in ml/l
does the bleaching liquor 5 ml 0,340 0,680 0,569 0,972 0,859
contain ?
10 ml 0,170 0,340 0,285 0,486 0,429
The factor for 2 ml of bleaching
liquor and of H2O2 50% is 1.423
(see table).
ml/l H2O2 x-% = consumption of KMnO4-solution ·factor
ml/l H2O2 50% = 8.7 · 1.423
= 12.4 ml/l

`eq=oK=_bfqif`e=dj_e=

56
Annex – Brief instruction Titration of caustic lye

Brief instruction - Titration of caustic soda

Procedure of titration Remark

An aliquot part, usually 1 to 10 ml of the bath are taken and The calculation is only valid for
given into an Erlenmeyer flask containing some distilled water. a hydrochloric acid of 0:1 mol/l
Titration is done with 0.1 mol/l hydrochloric acid or 0.05 mol/l (= 0.1N) – or a sulphuric acid
solution of 0.05 mol/l (= 0.1 N)
sulphuric acid (both of 0.1 N) up to the colour shade change of
the indicator phenol phthaleine of red to colourless.
Example 1

Calculation For titration of 2ml of bleach


liquor with 0.1mol/l HCl-solution
Valid for a hydrochloric acid of 0.1 mol/l or sulphuric acid of 0.05 mol/l (both 0.1 N) Lösung (= 0.1 N) 9.3ml of HCl-
solution are consumed. How
Factor for Faktor for Factor for much NaOH 100% in g/l does
Sample of the bleach liquor contain ?
NaOH 100 % NaOH 50 % NaOH 38 °Be
bath
in g/l in g/l in ml/l in g/l in ml/l The factor for a sample of 2 ml
bleach liquor and NaOH 100%
1 ml 4,000 8,000 5,229 12,099 8,896 is 2 (see table).

2 ml 2,000 4,000 2,614 6,050 4,448 g/l NaOH 100% = 9:3 · 2


= 18.6 g/l
5 ml 0,800 1,600 1,046 2,420 1,779
10 ml 0,400 0,800 0,523 1,210 0,890

Example 2
ml/l or g/l of NaOH x-% = consumption acid solution · factor For titration of 2ml bleach liquor
with HCl solution of 0.1mol/l
HCl (= 0,1 N) 9.3 ml HCl-
solution are consumed. How
much NaOH 50% in ml/l does
the bleach liquor contain ?

The factor for a sample of 2 ml


of bleaching liquor and NaOH
of 50% is 2.615 (see table).

ml/l NaOH 50% = 9.3 · 2.614


= 24.3 ml/l

`eq=oK=_bfqif`e=dj_e=

57
Annex – Brief instruction Titration of hydrogen peroxide

CHT R. BEITLICH GmbH


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D – 72072 Tübingen
Germany
Fon + 49 (0) 7071 – 154 –0
Fax +49 (0) 7071 – 154 – 290
www.cht.com
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58