Lab Test Book CHT

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). The so-called catalytic damage is a problem of pretreatment 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.
Holes caused by catalytic damaging
The presence of iron on fabric or in industrial waters can be proven rather easily.
`eq=oK=_bfqif`e=dj_e=
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.
CH2OH
Undamaged cellulose Cellulose CH2OH OH

O O O
OH OH
Qualitative proof of hydro- or oxycellulose

Damaged cellulose forms hydro-and oxycellulose at the damaged parts and this can be proven by simple means. Independently from the reason for the damaging, that means by acid or oxidation agents, a mixture of hydro- and oxycellulose is formed. By means of the following reactions of evidence it is indeterminate whether the damaging was caused by oxidation agents or acids.
OH
O
CH2OH
OH OH
Hydrocellulose
CH2OH OH O OH C OH H OH CH2OH OH O C H OH
O
CH2OH
OH
OH
Oxycellulose
CH2OH CHOH OH COOH O CH O HC CH2OH CHOH COOH
O
OH CH2OH
OH
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 in an ammoniacal silver nitrat e solution. C
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

The basic dye methylene blue strongly dyes oxycellulose very much because of the carboxylic groups and the depth of the dyeing corresponds to the degree of the damage.
To note: Merzerised CO reacts like damaged CO. Caution is advised.
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 swelling test (immaturity control by swelling test)

Undamaged CO fibre pieces treated with caustic soda show a phenomena which looks like mushrooms at the fibre ends under the microscope. However considerably chemically damaged CO fibre do not show such characteristic phenomena. Because of this it is possible to distinguish chemically damaged fibres from mechanically damaged ones.
To note: The swelling reaction can be done successfully only on CO fibres. Mercerised CO reacts in the same way as damaged CO. Caution is advised.
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. 26050.
Residual oils and fats on the fabric often coming from preperations can have disturbing effects during dyeing e.g. resist effects. The evidence of fats or oils can be provided by a fat dye Ceres red 7B.
Fabric free of oil or fat
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 at a liquor ratio of 1:60 for 5 - 10 minutes. C Then wash off cold for approx. 1 min, dry and fix the dye at 150 for 3 min. C The fats which are on the fabric are dyed in an intense red shade.
Methods of evidence
Production of Ceres red stock solution Ceres red 7B CHT-DISPERGATOR SMS 0.4 g/l 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
Variations in the degree of caustification and mercerisation lead to differences of dyeability and colour depth. The following test helps to recognize such differences. If a fibre sample is treated in a solution with both direct dyes of Tubantin red 8BL conc. and Tubantin green BL highly concentrated (BEZEMA AG), mercerised materials are dyed from grey to green. This is because of the affinity differences of dyes, depending on the degree of caustification and mercerisation, and the materials which have not been treated with lye become red. 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 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.
Differences of degree of caustification and mercerisation

Smt 3l%n ocr 0.si dhe v o i li uo olt u o Sn ha om re t N 3 0
not caustified
N2 [g] ax52% a- /k p.2=5 C g r 44) l O o(. cetn[g 3 ono /l] 0 ntis cr a 0 100 At s p e c stye-ecr lihrnyw ggislole l eh a liq u id
g/l NaOH 100 %
Dy)[g3 1 e(2 /c] 2 n0 m 2 s i t Siiyaa oltiwt0 lbntr2 u e C uitd ne lim
150 g/l NaOH 100 %
Sfrtlia C ax5 trcatn[] p.a ys r 1 t si o o o Ro anHax) en lke-lur.3 a a(veo c l pap1 t i i
200 g/l NaOH 100 %
Dead CO
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. C.I. Direct red 81
120 110 100 90 Temperature [ C]
Liquor ratio 1:40
45 min at 98 C
TUBANTIN conc.
green
BL
highly
80 70 60 50 40 30 20 10 0 0 10 20 30 40 Time [min] 50 60
C.I. Direct green 26
add fabric at boiling temp.
take out after 15 and 30 min and add 2.5 % NaCl (normal salt
0.8 % TUBANTIN red 8BL conc. 3.2 % TUBANTIN greenBL hightly conc.
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 TEGEWA-drop test: see
The textile absorption or hydrophilic effect is mostly analyzed by the following two methods: TEGEWA-drop test Capillary rise method
TEGEWA-drop test a method for a rapid determination of textile absorption 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.
Methods of evidence
TEGEWA-drop test brief description

The test material is put into the tension device and a drop of aqueous patent blue of 0.2 % is applied. 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 woven fabric e.g. on irregularly distributed residual deposits of size, warp waxes etc.
Alternative for Patentblau V ERKA Typ S 4030

Ringe Kuhlmann GmbH & Co KG Hamburg, Germany
Good pretreatment
Bad pretreatment
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 liquor surface.
30 mm
C
Variation 2 Wait until the liquid level is at a height of 10 mm (mark B) and take time until mark C at 20 mm is obtained.
20 mm 10 mm
B A
Methods of evidence
See further details TEGEWA-violet scale:
to
The degree of desize the TEGEWA-violetblue scale

Because there is a relation between the colour intensity of the iodine starch complex and the residual starch content on the fabric, the colour reaction of starch and free iodine is applied to judge in a semi-quantitative way the residual size content or better the residual content of starch after the pretreatment. Procedure
The Violet Scale, a criterion for assessing the desizing degree of starch-sized fabrics Textil praxis international (1981), 1331-1332, 1349-1350 12
Remark A complete description of the evidence of sizes is at disposal in a separate CHT brochure
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 cold water for a short time and then dapped off with a starch free filter paper and compared immediately with the TEGEWAviolet 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 readymade solutions (e. g. Fixanal or Titrisol) are applied at a concentration of c(I2) = 0.05 mol/l (= 0.1 N). Of this solution 50 ml are taken and filled up to a litre with distilled water. The solution itself can be made as follows: 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.
Remark Because of the volatility of the iodine, iodine solutions should always be kept in a brown flask closed with a ground-in stopper.
Methods of evidence
pH value on the fabric

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. With Morapex extraction. The sample is extracted with hot distilled water at the Morapex and then the pH measured as well in the extract. Dropping of a pH-indicator directly on the sample.
Morapex A (Habotex)
pH-Indicator (Merck) pH 3.5
pH-value determination description
with
pH-indicator
brief
pH 6.5
The easiest method is the pH-determination by dropping a pHindicator (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 pHindicator is dropped on. Then it is compared with the colour scale.
Determination of the conductivity

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 be determined.
Conducting meter
high conductivity (180 S/cm) Print side
low conductivity (20 S/cm) Print side
Procedure 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 filtering, measurement of the conductivity of the extract by means of a conducting meter. The measuring value is given in S/cm or mS/cm.
Back side
Back side
Methods of evidence
Evidence of non ionic residual surfactants

Precipitations of a reactive dye with a non ionic surfact
Some reactive dyes (mostly turquoise types) react sensitively in 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 non ionic surfactant
Concentration in % on weight of fabric (LR 1:20)
The material to test is extracted at a liquor ratio of 1:20 with cold distilled water at 5 for 5 minutes (e.g. in beaker). C It is important that the temperature of the water is approx. 5 C; because it guarantees that the non ionic surfactants are from the fabric to the water phase extract Concentration removed 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 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 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
0.10
0.05
0.20
0.10
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.
10
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.
11
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, microscopical analysis or dissolution in acids, alkali, organic solvents. 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.
Fibre Odour
Burning test Dry distillation
Remark In case of fibre mixtures caution is advised. Mixed pH values might turn up and the identification becomes difficult. Preliminary tests should be burning test and dry distillation.
Natural and man-made fibres
Burning test Burning, residue burns down fast, white grey ashes
Dry distillation pH-value
Vegetable fibres like cotton, linen, hemp, viscose Animal fibres, like wool, silk
of burnt paper of burnt hair
pH 5-6 pH 9-10
burns slowly, white grey ashes burns fast, burnt-out particles with Acetate fibres sour, like acid subsequent white grey ashes melts and burns, sweetish and sooting only in flame, Polyester fibres stinging glassy, ropy melt, black enamel pearl goes on melting and slightly of burning without sooting, Polyamide fibres burnt hair glassy yellow to brown, ropy melt
pH 2-3
pH 3-4
pH 10-11
12
Fibre Odour
Burning test Burning, residue melts and burns, then soots, black and brittle melting residue melts and goes on burning, without sooting, black, hard and brown metling residue melts and goes on burning without sooting, light brown and brittle melting residue melts but does not burn, white smoke, yellowish melt
Dry distillation pH-value
Polyacrylonitrilefibres
sweetish
pH 10-11
Polyurethanes
malodorous
pH 10-11
Polyethylene fibres
like burning candle
pH 5-6
Polypropylenefibres
like burning candle
pH 6-7
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 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.
Man-made fibres
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.
Polyamide 6.6 Polypropylene
Polyacrylonitrile Dissolving behaviour
Polyurethane
Acetone Dimethylformamide Dioxane o-Dichlorobenzene Phenol 40% Xylol Formic acid (98%) Pure acetic acid Hydochloric acid conc. Sulphuric acid conc. KOH 40%
u u u q u s u u u u s
r u s u s u u u u s
s s s s u s u r u u s
s r s s u s u r u u s
s r s r r s s s s u v
s r s s q s s s s u s
r s r r s r q v u v
s q s r q r s s s q q
s q q r q r q q q q q
u cold soluble r soluble at boiling temperature s insoluble q insoluble, but changes during boiling v 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).
14
Polyethylene
Polyamide 6
Triacetate
Polyester
Acetate
As simple examples can be mentioned

Vegetable fibre: odour of burnt paper Animal fibre: Odour of burnt hair Not mercerised: typical corkscrew like twists of the fibre; kidney shaped cross-section Mercerised: smooth fibre, round cross-section Ripe cotton fibre: red dyeing Unripe cotton fibre green dyeing Cotton: typical cork-screw like twists of the fibre Regenerated cellulosic fibre: smooth fibre Different longitudinal section pictures of the fibres Wool: dissolves during boiling in NaOH of 5%, typical scales layer Wild silk: dissolves only partly even if boilt for a longer time Pure silk: dissolves during boiling in HCl conc. (after approx. 60 sec.) Wild silk: dissolves only after boiling for a longer time
Different procedures of analysis
Vegetable fibres Animal fibres
Burning test Dyeing test
Mercerised not mercerised cotton
Microscopical analysis Red-/green test
Ripe and unripe cotton Cotton regenerated cellulosic fibres Cotton Bast fibre Wool Silk
Red-/green test Microscopical analysis Dyeing method Microscopical analysis Dissolving tests microscopical analysis dyeing method
Pure silk (bombyxs mori) and wild (e.g. Tussahsilk) silk
Dissolving tests
15
Hydrogen peroxide
Hydrogen peroxide
Chemical formula: Molar mass: H2O2 34.02 g/mol
Properties of commercially available H2O2solutions

Short name
[% by weight] [Vol.-%]
W 30 30 111 300 334 14. Jan 1.114
W 35 35 132 350 396 16. Mai 1.132
W 50 50 199 500 598 23. Mai 1.195

+
W 60 60 249 600 745 28. Feb 1.241
Aktive oxygen Peroxides have -O-O- groups, of which an oxygen atom can easily be separated as active oxygen . (For calulation see below)
H2O2 -concentrations
[g H 2 O 2 /kg] [g H 2 O 2 /l]
Active oxygen content Density (20) Acid content
[% by weight] [g/cm ]
3
0.5 - 5 mmol H /l
Storage life and storing of hydrogen peroxide

Decomposition of H2O2 H2O2 (liq.) H2O (liq) + O 2 (g.) H = -98.31 kJ/mol
In presence of catalytic substances hydrogen peroxide easily decomposes in an exothermal reaction to water and oxygen. Stability of hydrogen peroxide is influenced by:
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 the reacti on speed C, 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).
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
34.0146 g/mol
H2O
18.0152 g/mol
+
+
O2
31.9988 g/mol
Example 1 How much active oxygen in g/kg does a H2O2-solution of 50% contain ? Active oxygen = 50 4.704 = 235g/kg = 23.5%
Out of 34.0146g H2O2 100 % result from 31.9988g = 15.9994g of so-called active oxygen. The conversion factor of % by weight of H2O2-solution in active oxygen is the following:
Active oxygen [g/kg sol.] = % by weight H2O 2 sol. 15.9994 10 34.0146 = % by weight H2O 2 solution 4,704
Example 2 How much active oxygen does a bleaching bath with 10ml/l H2O2 50% (density 20 = 1,132 g/cm3) contain? 10 ml H2O2 50% contain 10 1.132 = 11.32 g H2O2 50% or 11.32g H2O2 50% /1000ml
= 2.7 g/l 1000 Aktive oxygen content = 2.7 g/l x= 4.704 50 11,32
In bleaching baths normally the total content of hydrogen peroxide is determined and not the active oxygen content.
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.
17
Hydrogen peroxide
Permanganometric determination of H2O2

Reaction of H2O2 with KMnO4 5 H2O2 + 2 2 Mn MnO42+ +6H + 5 O2 + 8 H2O
+
Titration with potassium manganate in sulphuric acid solution is often running from colourless to slightly pink.
The equivalent mass ratios result from the reaction equation or equivalent numbers of potassium permanganate and hydrogen peroxide. Equivalent number z Hydrogen peroxide Potassium permanganate The equivalent ratios result from: n(eq) (KMnO4) = n(eq) (H2O2)
n (KMnO4 ) z (KMnO4 ) = n (H 2 O2 ) z(H 2O2 ) = n (KMnO4 ) = m (H 2 O2 ) z (H 2 O2 ) M (H 2 O2 ) z (KMnO4 ) m (H 2O2 ) z (H 2O2 ) M (H 2O2 )
Molar mass 34.0146 g/mol 158.034 g/mol
2 5
Normally a solution of 0.02 mol/l (= 0.1 N) KMnO4 is applied. Then the following equation is valid:
0.02 mol KMnO4 = m (H2O2 ) = m (H2O2 ) 2 34.0146 g/mol 5
0.02 mol KMnO4 34.0146 g/mol 5 2 m (H2O2 ) =1.7007 g
According to this 1 ml of a solution of 0.02 mol/l (= 0.1 N) KMnO4exactly 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%.
18
Hydrogen peroxide
Procedure of titration An aliquot part is taken, normally 1 to 10 ml of the bleaching bath and given into an Erlenmeyer flask containing approx. 10 ml of a sulphuric acid (20%). The titration is carried out immediately with the potassium permanganate solution to a faint pink colour.
Remark: In the annex, there is a very much simplified variation of the titration instruction.
Calculation The variables applied for calculation are the following ones: Consumption in ml of a KMnO4 solution at a concentration of x mol/l. Concentration of the applied potassium permanganate solution, normally 0.02 mol/l = 0.1 N ml of taken quantity of bleaching liquor Density of hydrogen peroxide solutions
(H2O2 35%ig = 1.132; H2O2 50% = 1.195)
V x mol/l KMnO4 F 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 solution is applied.
1 ml 0.02 mol/l KMnO4 = 0.0017g H2O2 100%
Calculation of H2O2-concentration in g/l:

g/l H2O 2 x % = = x mol/l KMnO 4 5 34.0146 V 100 2 F W
Example For titration of F = 10ml bleaching liquor with 0.02mol/l KMnO4-solution (= 0.1 N) are used V = 8.5ml KMnO4solution. How much of H2O2 50% (W=50) in g/l does the bleaching liquor contain ?
g/l H 2 O 2 50% = 0.02 8503.65 8,5 10 50
x mol/l KMnO 4 8503.65 V F W
g/l H2O2 50% = 2,89g/l
19
Hydrogen peroxide
Example For titration of F = 10ml of bleaching liquor with 0.02 mol/l KMnO4-solution (= 0.1 N) V = 8.5 ml KMnO4-solution are consumed. How much H2O2 50% in ml/l (W=50, =1.195) does the bleaching liquor contain?
ml/l H 2 O 2 50% = 0.02 8503.65 8,5 10 50 1.195
Calculation of H2O2-concentration in ml/l:

ml/l H2O 2 x % = x mol/l KMnO 4 5 34,0146 V 100 2 F W
=
x mol/l KMnO 4 8503,65 V F W
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 concentration of x mol/l. Concentration of the applied potassium permanganate solution, normally 0.02 mol/l = 0.1 N Mass of taken sample in grammes Density of hydrogen peroxide solution
(H2O2 35% = 1.132; H2O2 50% = 1.195)
V x mol/l KMnO4 M W
% by weight of hydrogen peroxide solution
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.
Calculation of the H2O2-concentration in g/kg:

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

x mol/l KMnO 4 5 34.0146 V 100 ml/lkg H2O 2 x % = 2 M W
=
Example After impregnation a samplehaving a mass of 2.8 g is taken. For titration with 0.02mol/l KMnO4-solution (= 0,1 N) V = 8,5ml KMnO4solution is consumed. How much H2O2 50%(W=50) ml/kg are on the fabric ?
ml/kg H2O 2 50%ig = 0.02 8503.65 8.5 2.8 50 1.195
x mol/l KMnO 4 8503.65 V M W
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.
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 [Ti aq] + H2O2 2+ [Ti(O2) aq] + H2O yellow to orange
2+
The determination method is based on a colour change during the reaction of hydrogen peroxide with titanylchloride (TiOCl2). Depending on the concentration of hydrogen peroxide there is a yellow to a deeply orange red dyeing. 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 of hydrogen peroxide in aqueous solutions.
Determination in aqueous solutions colour scale L

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 of hydrogen peroxide directly on the fabric
Determination directly on the fabric colour scale T

2 3 drops of titanylchloride solution are spotted onto the 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.
22
Hydrogen peroxide
23
Hydrogen peroxide
Semi-quantitative determination of the hydrogen peroxide content with Merck-test sticks

Application for aqueous solutions 1. 2. 3. Take test sticks and close the tube again. Dip test stick for 1 sec into the test solution so that the reactive zone is completely wet. 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 Mercktest stick container scale.
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

The quantitative determination of the three alkalis in the bath are carried out by acidimetrical titration with salt or sulphuric 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.
Remark: In the annex there is a very much simplified version of the tiitration instruction.
Titration An aliquot part, usually 1 to 10 ml, of the liquor is given into an Erlenmeyer flask containing some distilled water. It is titrated with the acid solution up to the colour change of the indicator.
Common indicators
Colour change
Indicator
of to red colourless orange ret yellow ret
Phenol phthalein
Calculation The parameter of calculation are the following: Consumption in ml of acid-solution. Normally 0.1 mol/l (= 0.1 N) hydrochloric acid or 0.05 mol/l (= 0.1 N) sulphuric acid ml of taken liquor quantity. Factor for the conversion on caustic soda, soda or ammonia 1 ml 1 ml 1 ml = = = 4.0 mg caustic soda (NaOH) 5.3 mg soda (Na2CO3) 1.7 mg ammoniac (NH3)
Methyl orange Methyl red
Valid for hydrochloric acid of 0.1 mol/l (= 0,1 N) or sulphuric acid of 0.05 mol/l (= 0,1 N)e.
25
Alkali
Example F = 10 ml are taken of a bleaching liquor and titrated with hydrochloric acid of 0.1 mol/l with phenol phthalein as indicator. The consumption of the acid is: 11.2 ml. Which content of caustic soda (f = 4) in the liquor ?
g/l NaOH100% = 4 11,2 10
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 found as follows.
Alkali in g/l:
g/l Alkali = f V F
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 hydrochloric acid of 0.1 mol/l (= 0,1 N) or sulphuric acid of 0.05 mol/l (= 0.1 N) taken quantity of liquor in ml . Density of caustic lye
(NaOH 50%ig = 1.53)
V
Example For titration of F = 10ml of bleaching liquor of 0.1 mol/l of hydrochloric acid (= 0.1 N) V = 11.2 ml hydrochloric acid solution is used. How much caustic lye of 50% in g/l (W=50) does the bleaching liquor contain ? 4112100 . g/l g/l NaOH % = 50 10 50 NaOH 50% = 9 g/l
F W
% by weight of caustic lye
Caustic lye in g/l:

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

ml/l NaOH x % = 4 V 100 F W
ml/l NaOH 50%ig = 5,9 ml/l
26
Sodium hypochlorite (chlorine bleaching lye)
Sodium hypochlorite (Chlorine

bleaching lye)
Chemical formula: Molar mass: NaOCl 74.5 g/mol
Properties of common chlorine bleaching lye

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

The most important reactions for bleaching with sodium hypochlorite are the following:
Hydrolysis Release of bleaching agent Maximal HOCl-development Formation of free chlorine Active chlorine
NaOCl + H2O NaOH + HOCl HOCl HCl + [O] NaOCl + HCl NaCl + HOCl HOCl + HCl H2O + Cl2
Summarized in a diagram the pH-dependance of the composition of sodium hypochlorite bleaching liquors is as follows:
100 Cl2 80 Concentration [%] 60
b est r ang e f o r b l eachi ng p r o c ess
HOCl OCl-
40 20
0 0 1 2 3 4 5 6 7 8 pH-value 9 10 11 12 13 14
The best pH range for bleaching is between 9 and 12.
27
Active chlorine
Active chlorine HOCl + HCl H2O + Cl2
Although chlorine does not have any bleaching effect, active chlorine is defined as the quantity of chlorine which is released 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 2 HOCl + 4 I + 2 H 2 I2 + 2 Cl + 2 H2O
+
Out of an acid potassium iodide solution (KI) sodium hypochlorite separates an equivalent quantity of iodine (I) to the quantity of chlorine (Cl2), and it can be titrated with sodium thiosulphate solution (Na2S2O3).
The equivalence mass ratios result of the reaction equation or the equivalence numbers of sodium thiosulphate and of chlorine (Cl2). Equivalence Molar mass number z Chlorine Sodium thiosulphate 2 1 70.906 g/mol 158.10 g/mol
Back titration of iodine with sodium thiosulphate 2 S2O32- + I2 2 I- + S4O62-
The equivalence ratios are the following: n(eq) (Na2S2O3) = n(eq) (Cl2)
n (Na2 S2O3 ) z (Na2 S2 O3 ) = n (Cl 2 ) z(Cl 2 ) = n (Na2 S2 O3 ) = m (Cl 2 ) z (Cl 2 ) M (Cl 2 ) z (Na2 S2 O3 ) m (Cl 2 ) z (Cl 2 ) M (Cl 2 )
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.
28
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 concentration of 0.1 mol/l (= 0.1 N). ml of taken quantity of bleaching liquor
1ml 0.1mol/l Na2S2O3 = 0.00355g active chlorine
V F
1ml of 0.1mol/l Na2S2O3 = 0.00355g active chlorine
Example
Calculation of active chlorine content in g/l:

g/l Active chlorine = 0.00355 V 1000 F
For titration of F = 10ml bleaching liquor with 0.1 mol/l (= 0.1 N) sodium thiosulphate solution are consumed V = 6,8 ml Na2S2O3 solution. How much active chlorine in g/l does the bleaching bath contain ?
g/l Active chlorine = 0.00355 6.8 1000 10
g/l Aktive chlorine = 2.41 g/l
29
Dechlorination
Dechlorination has two purposes: 1. 2.
Formation of chloramines
Protein compound
Elimination of the active chlorine from the fabric, because it would damage the fibres during drying and storing. Separation of chloramines (chlorine protein compounds).
R-NH2 + NaOCl R-NHCl + NaOH

Chloramine
Vegetable fibres are composed of protein compounds of the protoplasma and form so-called chloramines in contact with chlorine bleach lye. Chloramines tend to form hypochlorite in an humid atmosphere, and this has a fibre damaging effect during storing. In addition to that chloramines separate hydrochloric acid during the drying process and this might cause fibre damage as well.
Decomposition of chloramines in a humid atmosphere R-NHCl + H2O
Dechlorination agent
Dechlorination can be done with reducing agents or with hydrogen peroxide: Dechlorination agent
Sodium thiosulphate 4 HOCl + S2O32- + H2O 2 SO42- + 6 H+ + 4 ClSodium hydrogen sulphite HOCl + HSO3- HSO4- + H+ + ClSodium dithionite 3 HOCl + S2O42- + H2O 2+ 2 SO4 + 5 H + 3 Cl
Theoretically necessary quantity for the destruction of 1g/l of active chlorine

4 x HOCl = 2 x 35.5g active chlorine = 158.1g sodium thiosulphate
Sodium thiosulphate (Antichlorine) Sodium hydrogen sulphite (Bisulphite) Sodium dithionite (Hydrosulphite)
1g/l active chlorine = 0.55g/l sodium thiosulphate

1 x HOCl = 35.5g active chlorine = 104.06g sodium hydrogen sulphite
1g/l active chlorine = 2.9g/l sodium hydrogene sulphite

3 x HOCl = 1.5 x 35.5g active chlorine = 158.1g sodium hydrogen sulphite
1g/l active chlorine = 1.5g/l sodium hydrogen sulphite

1 x HOCl = 35.5g active chlorine = 34.02g hydrogen peroxide
Hydrogen peroxide HOCl + H2O2 Cl- + H2O + H+ + O2
Hydrogen peroxide
1g/l active chlorine = 0.48g/lH2O2 100% = 1.21ml/l H2O2 35% = 0.8ml/l H2O2 50%
30
Determination of active chlorine content commercially available chlorine bleach lyes
in
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 lye per liter. Usually 20 50 ml/l. Consumption in ml of Na2S2O3- solution with a concentration of 0.1 mol/l (= 0.1 N). ml of taken quantity of diluted chlorine bleach lye for titration.
Example
KV
V F
Calculation of active chlorine content in g/l:

g/l Active chlorine = 0.00355 V 1000 1000 F KV
KV = 20 ml commercially available chlorine bleach lye was diluted on a liter. Of this diluted solution F = 10 ml were 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.
g/l Active chlorine = 0.00355 8.5 1000 1000 10 20
g/l Active chlorine = 150 g/l
31
Sodium chlorite
Sodium chlorite
Chemical formula: Molar mass: NaClO2 90.5 g/mol
Properties of commercially available sodium chlorite

Sodium chlorite Short name NaClO2 concentrations Aspect Density (
20)
30 vol.% solution
N 30
[g/kg] [g/l]
approx. 245 (= 24.5 %) 300 slightly greenish-yellow clear liquid
[g/cm ]
1 22 unlimited
Solubility in water at 20 C Start of crystallisation Reaction

[ C]
approx. -15 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 Release of bleaching agent
NaClO2 + H2O NaOH + HClO2 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

32
Sodium chlorite
Summarized in a diagram the pH dependance of the composition of sodium chlorite bleach liquors is as follows:
100 HClO2 80 Concentration [%] ClO2
b est r ang e f or b leachi ng p r o cess
ClO2-
60
40
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 content is obtained by iodometric titration. Sodium chlorite separates from an acid potassium iodide solution (KI) a quantity of iodine (I) equivalent to the sodium chlorite (NaClO2), which can be titrated with sodium thiosulphate solution (Na2S2O3).
The equivalence mass relations result from the reaction equation or equivalence numbers of sodium thiosulphate and sodium chlorite.
Transformation of sodium chlorite with iodide ClO2- + 4 I- + 4 H+ 2 I2 + Cl- + 2 H2O Back titration of iodine with sodium thiosulphate 2 S2O32- + I2 2 I- + S4O62-
Equivalence number Sodium chlorite Sodium thiosulphate 4 1
Molar mass 90.5 g/mol 158.10 g/mol
33
Sodium chlorite
The equivalence ratios result from: n(eq) (Na2S2O3) = n(eq) (NaClO2)

n (Na2 S2O3 ) z (Na2 S2O3 ) = n (NaClO2 ) z(NaClO2 ) = n (Na2 S2O3 ) = m (NaClO2 ) z (NaClO2 ) M (NaClO2 ) z (Na2 S2O3 ) m (NaClO2 ) z (NaClO2 ) M (NaClO2 )
Usually a solution of 0.1 mol/l (= 0.1 N) Na2S2O3 is applied. The following equation is valid:
0,1 mol Na2 S2 O3 = m (NaClO2 ) 4 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) Na2S2O3solution 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.
34
Sodium chlorite
Calculation The calculation parameters are the following: Consumption in a Na2S2O3- solution with a concentration of 0.1 mol/l (= 0.1 N). Taken quantity of bleach liquor in ml Density of sodium chlorite solution
NaClO2 24.5% (30 Vol.%, N 30) = 1.22
V F W
% by weight of sodium chlorite solution

1ml 0.1mol/l Na2S2O3 = 0.00226g NaClO2 100 %
1ml of a 0.1mol/l Na2S2O3 = 0.00226g NaClO2 100 %
Calculation of sodium chlorite content in g/l:

g/l NaClO 2 100% = 0.00226 V 1000 100 F W
Example For titration of F = 10ml of bleach liquor with 0.1 mol/l (= 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 ?
g/l NaClO 100% = 2 0.00226 4.2 1000 100 10 100
Usually sodium chlorite solutions are applied (mostly 24.5 %, 30 Vol.%, N 30).
g/l NaClO2 100% = 0.95g/l
Calculation of sodium chlorite content in ml/l:

ml/l NaClO 2 100% = 0,00226 V 1000 100 F W
Example For titration of F = 10ml of bleach liquor with 0.1 mol/l (= 0.1N) sodium hiosulphate solution V = 5.0ml Na2S2O3 solution is consumed. How much sodium chlorite 24.5% ml/l (W=24.5, =1.22) does the bleach liquor contain ?
ml/l NaClO 2 24,5% = 0.00226 5.0 1000 100 10 24 .5 1.22
ml/l NaClO2 24.5% = 3.78ml/l
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.
Reducing agent Sodium hydrogen sulphite

ClO2 + 2 HSO3 + 2 SO4 + 2 H + Cl
-
Theoretically necessary quantity to destruct 1g/l sodium chlorite 100%

1 x 90.5g NaClO2 = 2 x 104.06g NaHSO3
Sodium hydrogen sulphite (Bisulphite)
1g/l NaClO2 100% = 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- 2 SO4- + Cl--
Sodium sulphite
1g/l NaClO2 100% = 2.8g/l sodium sulphite = 5.6 g/l sodiumsulphite heptahydrate
36
Persulphates
Persulphates
Properties of persulphates
Name Chemical formula Molar mass Active oxygen content (minimum) 10 C Solubility, g/100 g aqueous solution at 20 C 30 C
[g/mol]
Ammonium Potassium Sodium persulphate persulphate persulphate (NH4)2S2O8 228,2 6,9 49 54 59 K2S2O8 270,3 5,8 3,0 5,5 8,8 Na2S2O8 238,2 6,5 46 54 58
[%]
[g/100g]
[g/100g] [g/100g]
Persulphates slowly decompose particularly at higher temperatures.
in
aqueous
solution,
Decomposition of persulphate S2O82- + H2O 2 SO42- + 2 H+ + O 2
For this reason solutions of persulphates are stable only to a limited degree. A higher bath temperature than 40 should be C 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.
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. 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.
2.
Procedure 1. Fabrication of iron (II) (II) salt solution

Ammonium iron(II)sulphate = Mohrs salt (NH4)2Fe(SO4)2 6 H2O
A suitable iron (II) salt for the titration of persulphates is the ammonium iron (II) sulphate, which is known under the name of Mohrs salt. 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 ammonium iron (II) sulphate solution (= blank sample) should be determined again before every titration.
The iron (II) of the fabricated ammonium iron (II) sulphate solution is slowly oxidated to iron (III) by oxygen from the air. For this reason the actual content of iron (II) has to be determined before the titration is done. 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.
38
Persulphates
The consumption of potassium permanganate solution is recorded (VB). It serves for the calculation of the persulphate content.
VB = consumption of potassium permanganate solution in case of a titration of 20 ml ammonium 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 of sulphuric acid of 10 % and the content of hydrogen peroxide is determined with potassium permanganate (see also chapter 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.
Titration of hydrogen peroxide with a solution of 0.2 mol/l (= 0.1 N) KMnO4.
4. Determination of the content of persulphate 20 ml of the ammonium iron (II) sulphate solution are added to the completely titrated sample. At any rate the same quantity of ammonium iron (II) sulphate solution has to be added as for the 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).
VP = Consumption of potassium permanganate solution out of the titration of the before completely titrated liquor sample.
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 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 0.02mol/l = 0,1 N) in titration of completely titrated bath samples. Concentration of the applied potassium permanganate solution. Normally 0.02 mol/l = 0.1 N Conversion factor for sodium-, potassium or ammonium persulphate. 1 ml 1 ml 1 ml = = = 11.910 mg sodium persulphate 13.515 mg potassium persulphate 13.515 mg ammonium persulphate
VB
VP
x mol/l KMnO4
Example In a cold bleach bath the content of sodium persulphate is to be determined. 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. F = 10 ml of the cold bleach bath was taken and first the content of hydrogen peroxide was determined with a solution 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 ammonium iron (II) sulphate solution and titrated with 0.02 mol/l KMnO4-solution (= 0.1 N) up to the colour shade change to light pink. A consumption of KMnO4 of VP = 13.7 ml was recorded. The content of sodium persulphate is calculated as follows:
g/l Na - persulphat e = (20.4 - 13.7) 0.02 11.910 0.02 10
for a solution of 0.02 mol/l of KMnO4
Calculation of the H2O2-concentration:

The determination and calculation of the hydrogen peroxide concentration is done as described in the chapter about HYDROGEN PEROXIDE.
Calculation of the persulphate concentration:

The following calculation formula is such that it can be calculated with every concentration of potassium permanganate solution. Only the concentration in mol/l should be known. Independently from the applied potassium permanganate solution for the conversion on sodium-, potasium or ammonium persulphate the factors f have to be taken out of the above given table.
g/l Na-persulphate = 8 g/l
g/l Persulphat = e
(VB - VP ) xmol/lKMnO f 4 0.02 F
40
Silicates
Silicates
Properties of commercially available sodium silicates
Name Sodium silicate 37/40 Density (20) Density in Be Silicium oxide SiO2 Sodium oxide Na2O Mole ratio (SiO2 : Na2O) Weight ratio (SiO2 : Na2O) Viscosity at 20 C
[mPa s] [g/cm 3 ]
Sodium silicate 40/42 1,38 - 1,40 40 - 42 28 - 30 8,5 - 9,3 3,2 - 3,4 3,1 - 3,3 100 - 240
1,34 - 1,38 37 - 40 26,5 - 28,5 8-9 3,3 - 3,5 3,2 - 3,4 50 - 150
[ Be]
[%]
[%]
Properties of commercially available metasilicates

Name Nametasilicate anhydrous Na2SiO3
[g/mol]
Na-metasilicate Na-metasilicate 5-hydrate 9-hydrate Na2SiO35 H2O 230 28.0 - 29.4 28.1 - 29.5 56.5 - 58.5 Na2SiO39 H2O 302 21.8 - 23.8 21.7 - 23.7 44 - 47
Chemical formula Molar mass Silicium oxide SiO2 Sodium oxide Na2O Dry substance
140 46.2 - 47.6 50.4 - 51.8 96.5 - 99.5
[%]
[%]
[%]
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.
41
Hardness of water
Silicate precipitations with hardening substances (schematically)

Ca ONa O Si O OH O Si O O Ca ONa O Si O OH O Si O O Mg OH Si O O O Si O OH ONa Si O O Ca ONa Si O ONa ONa Si O O Ca OH Si O O ONa Si O O OH Si O ONa O Si O O Mg O Si O O Mg ONa Si O O Mg O Si O ONa
Silicates have a very high sequestering power on heavy metals and thus have an anticatalytic effect Silicates hydrolyze at high temperatures and can form insoluble silicic acid. Silicates form insoluble compounds with alkaline earths and can cause sediments on fibres and machine parts. Silicates have a high buffering power.
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
61.979 g/mol
+
+
H2O
18.0152 g/mol
2 NaOH
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 The data of density and content of sodium oxide are the average values of above given tables. It is possible that the values differ from the applied sodium silicate. Therefore the data should better be taken from the specifications.
Content of sodium oxide (Na2O)

(37/40 = 8.5%; 40/42 = 8.9%)
Density of sodium silicate

(37/40 = 1.36; 40/42 = 1.39)
Applied quantity of silicate of soda in ml/l (in case of metasilicates in g/l)
Example How much NaOH g.kg does sodium silicate 37/40 contain? The Na2O-content of this silicate of soda is indicated with 8-9 % in the table (medium value 8.5 %). NaOH 100% = 12.904 8.5 = 110g/kg = 11 %
Calculation of NaOH-concentration in g/kg:

Corresponding to the sodium oxide indications (Na2O) of above given table the sodium hydroxide content of the silicates can be calculated as follows.
NaOH 100% [g/kg ] = 79,98 10 W 61.979
= 12.904 W
42
Silicates
Calculation of NaOH-concentration in g/l:

In bleach liquors sodium silicate is normally applied in ml/l. The sodium hydroxide content (NaOH) out of sodium of silicate in such a bleaching bath is calculated as follows:
NaOH 100% [g/l ] = 79.98 W V 61.979 1000 12.904 W V 1000
Example In a bleach liquor V=10ml sodium silicate 37/40 (=1.36, W=8.5) is applied. How much NaOH 100 % in g/l does the bath contain ?
NaOH 100% [g/l ] = 12,904 8,5 10 136 , 1000
NaOH 100% = 1.49 g/l
For metasilicates it is not possible to indicate density because it is a solid substance. Therefore the calculation formula for metasilicates is the follwing:
NaOH 100% [g/l ] = 79.98 W V 61.979 1000 12.904 W V 1000
43
Hardness of water
Hardness of water
Hardness classification Total hardness dH 0-7 7-14 14-21 > 21 Description
Hardness of industrial waters can have a considerable influence on pretreatment and dyeing results. High hardness for example can cause: Deposits of hardening substances on machines or textiles. Precipitations of dyes which are sensitive to hardness in the dyeing liquor.
soft medium hard very hard
Total hardness (GH) Total concentration of all dissolved calciumand magnesium ions. Carbonate hardness (KH) = Cand Mg-hydrogen carbonates. During boiling insoluble Ca- or Mg-carbonate is formed:
Ca(HCO3)2 CaCO3 + H2O + CO2
For this reason a regular control of the hardness of the industrial water can be very helpful so that possible reasons for defects can be recognized early and eliminated. On thebasis of the total hardness of water it is differentiated between carbonate hardness (former temporary hardness) and permanent hardness. The carbonate hardness forms insoluble Ca- or Mg-carbonates during boiling and therefore causes deposits whereas the permanent hardness remains in solution even at a higher temperature.
Permanent hardness = Caand 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 The solution becomes more or le ss red C. 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:

V F x mol/l EDTA
Consumption in ml of EDTA-solution at a concentration of x mol/l. Taken quantity of water sample in ml Concentration of applied EDTA-solution, usually 0.01 mol/l.
44
Hardness of water
EDTA always forms with metal ions a 1:1 complex. 1 mol EDTA binds 1 mol of a metal ion, e.g. calcium. Table: = 0.4008 mg = 0.5608 mg = 1.00 mg Ca CaO CaCO3
O C O
EDTA-complex
O O O C O Ca2+ N CH2 O C O CH2 N CH2 CH2 CH2 C CH2
1 ml of 0.01 mol/l EDTA-solution corresponds to 0.01 mmol metal
= 0.24305 mg Mg = 0.4030 mg MgO = 0.8431 mg MgCO3
Calculation of content of hardening substances in mmol/l:

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

According to definition: 1 = 10 mg/l CaO dH
= 7.19 mg/l MgO
Example For the titration of F = 100ml of a water sample 0.01 mol/l EDTA-solution V = 13ml EDTAsolution is consumed. How much dH has the water ?
dH = 0,01mol/l EDTA 13 5.608 1000 100
x mol/l EDTA V 5.608 1000 dH = F
= 7.3 dH dH
45
Hardness of water
Conversion factors for common units of water hardness

mmol/l Alkaline earth ions English hardness French hardness German hardness Russian hardness ppm as CaCO3
Definition of different hardness data

1 1 German hardness French hardness 10 mg/l CaO 10 mg/l CaCO3 10 mg/0,7 l CaCO3 14.29 mg/l CaCO4
mmol/l alkaline earth ions English hardness
7,02
10
5,6
40
100
0,14
1,429
0,7999
5,714
14,29
English hardness
1 French hardness German hardness Russian hardness ppm as CaCO3
0,1
0,7
0,5599
10
1
1 American hardness (USA) 1 mg/l CaCO3
0,18
1,25
1,786
7,144
17,85
0,025
0,175
0,25
0,14
2,5
0,01
0,07
0,1
0,06
0,4
46
Average polymerisation degree and fluidity
Average degree of polymerisation (DP-value)

The cellulose molecule is a polysaccharide composed of -1.4 linked glucose units. The so-called polymerisation degree gives evidence of the number of chain elements (glucose units). E.g. if there is chemical damage in bleaching, the long chain 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.
CH2OH O OH OH O OH O CH2OH OH O CH2OH O OH OH n/3
n = degree of polymerisation
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 Difficulties can be caused by resin finished, reactive dyed or mercerized fabrics depending on the procedure because sometimes the fibre material is not completely dissoved in the solvent and measuring becomes impossible.
The fibre material is dissolved in a solvent according to all procedures (in case of the nitrate procedure after a preceding nitration) and the running time of the solution is measured by means of a capillary as well as the running time of the pure solvent as reference. The fibre material applied for the DP value determination 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.
47
Calculations
DP-values of different fibres Substrate
Natural fibres: Cotton, flax, Ramie Regenerated cellulose: Copper procedure Viscose procedure Acetate procedure
DP - value
2000 3000
According to Staudinger the following formula is valid for the DP-value:

DP = 0 1 1 C km
400 500 250 400 200 300
: 0: c: Km:
Runnning time of solution in sec. Running time of solvent in sec Cellulose concentration in g/l 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:
2000 2000 log + 1 Pt Ptx s= 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
s-factor
0.010.20 0.210.30 0.310.50 0.510.75 > 0.75
dam aging factor 1,2 3600 DP-value before damaging 1,0 0,8 0,6 0,4 0,2 0,0
judgment
very good undamaged good, very gentle bleaching sufficient slightly damaged very much damaged
3200 2800 2400 2000 1600 800
1200
1600
2000
2400
2800
3200
3600
DP-value after dam aging
48
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 fluidity is the reciprocal value of the dynamic viscosity.
Judgement of fluidity
Fluidity
2 2.1-3.5 3.6-5.0 5.1-8.0 > 8.0
Judgement
undamaged good, very gentle bleach sufficient slightly damaged very damaged
Calculations
The fluidity formula is:
F= C' k t t
C' =
C: k: t: :
Constant of viscosimeter Factor of correction Run-out time of solvent Density of solvent
There is the following relation between DP-value and fluidity:

74,35 + F DP = 2032 log 573 F
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 Fluidity 12 14 16 18 20
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 20 1,000 1,005 1,010 1,015 1,020 1,025 1,030 1,035 1,040 1,045 1,050 0,0 0,7 1,4 2,1 2,7 3,4 4,1 4,7 5,4 6,0 6,7 Be
Sulphuric acid Hydochloric acid

% w/w 0,261 0,985 1,731 2,485 3,242 4,000 4,746 5,493 6,237 6,956 7,704 g/l 2,609 9,904 17,483 25,223 33,068 41,000 48,884 56,852 64,865 72,690 80,892 % w/w 0,360 1,360 2,360 3,370 4,390 5,410 6,430 7,460 8,490 9,510 10,520 g/l 3,600 13,670 23,840 34,210 44,780 55,450 66,230 77,210 88,300 99,380 110,460
Nitric acid
% w/w 0,333 1,255 2,164 3,073 3,982 4,883 5,783 6,661 7,530 8,398 9,259 g/l 3,330 12,610 21,860 31,190 40,620 50,050 59,570 68,940 78,310 87,760 97,220
Caustic lye
% w/w 0,159 0,602 1,045 1,490 1,937 2,384 2,839 3,289 3,735 4,199 4,655 g/l 1,590 6,050 10,550 15,120 19,760 24,440 29,240 34,040 38,840 43,880 48,880
Caustic potash
% w/w 0,197 0,743 1,295 1,839 2,380 2,931 3,480 4,030 4,580 5,121 5,660 g/l 1,970 7,470 13,080 18,670 24,280 30,040 35,840 41,710 47,630 53,510 59,430
1,055 1,060 1,065 1,070 1,075 1,080 1,085 1,090 1,095 1,100
7,4 8,0 8,7 9,4 10,0 10,6 11,2 11,9 12,4 13,0
8,415 9,129 9,843 10,510 11,260 11,960 12,660 13,360 14,040 14,730
88,778 96,767 104,828 112,460 121,040 129,170 137,360 145,620 153,740 162,030
11,520 12,510 13,500 14,490 15,480 16,470 17,450 18,430 19,410 20,390
121,540 132,610 143,780 155,040 166,410 177,880 189,330 200,890 212,540 224,290
10,120 10,970 11,810 12,650 13,480 14,310 15,130 15,950 16,760 17,580
106,770 116,280 125,780 135,360 144,910 154,550 164,160 173,860 183,520 193,380
5,107 5,562 6,017 6,471 6,928 7,378 7,827 8,283 8,734 9,189
53,880 58,960 64,080 69,240 74,480 79,680 84,920 90,280 95,640 101,080
6,200 6,740 7,280 7,820 8,360 8,890 9,429 9,960 10,489 11,030
65,410 71,440 77,530 83,670 89,870 96,010 102,310 108,560 114,860 121,330
1,105 1,110 1,115 1,120 1,125 1,130 1,135 1,140 1,145 1,150
13,6 14,2 19,3 15,4 16,0 16,5 17,1 17,7 18,3 18,8
15,410 16,080 16,760 17,430 18,090 18,760 19,420 20,080 20,730 21,380
170,280 178,490 186,870 195,220 203,510 211,990 220,420 228,910 237,360 245,870
21,360 22,330 23,290 24,250 25,220 26,200 27,180 28,180 29,170 30,140
236,030 247,860 259,680 271,600 283,720 296,060 308,490 321,250 334,000 346,610
18,390 19,190 20,000 20,790 21,590 22,380 23,160 23,940 24,710 25,480
203,210 213,010 223,000 232,850 242,890 252,890 262,870 272,920 282,930 293,020
9,643 10,097 10,554 11,007 11,463 11,919 12,344 12,825 13,279 13,729
106,560 112,080 117,680 123,280 128,960 134,680 140,100 146,200 152,040 157,880
11,560 12,080 12,610 13,140 13,660 14,190 14,706 15,220 15,741 16,260
127,740 134,090 140,600 147,170 153,670 160,350 166,910 173,510 180,230 186,990
50
Annex Density and concentration of sulphuric acid, hydrochloric acid, nitric acid, caustic lye and caustic potas
Density 20 1,155 1,160 1,165 1,170 1,175 1,180 1,185 1,190 1,195 1,200
Be
Sulphuric acid Hydrochloric aicid

% w/w g/l 254,450 262,970 271,550 280,210 288,810 297,480 306,200 314,990 323,850 332,640 % w/w 31,140 32,140 33,161 34,180 35,200 36,230 37,270 38,320 39,370 g/l 359,670 372,820 386,320 399,910 413,600 427,510 441,650 456,010 470,470 -
Nitric acid
% w/w 26,240 27,000 27,761 28,510 29,250 30,000 30,740 31,470 32,210 32,948 g/l 303,070 313,200 323,410 333,570 343,690 354,000 364,270 374,490 384,910 395,380
Caustic lye
% w/w 14,182 14,634 15,090 15,538 15,990 16,441 16,891 17,345 17,797 18,253 g/l 163,800 169,760 175,800 181,800 187,880 194,000 200,160 206,400 212,680 219,040
Caustic potash
% w/w 16,780 17,290 17,810 18,320 18,840 19,350 19,860 20,370 20,879 21,380 g/l 193,810 200,560 207,490 214,340 221,370 228,330 235,340 242,400 249,510 256,560
19,3 19,8 20,3 20,9 21,4 22,0 22,5 23,1 23,5 24,0
22,030 22,670 23,309 23,950 24,580 25,210 25,840 26,470 27,100 27,720
1,205 1,210 1,215 1,220 1,225 1,230 1,235 1,240 1,245 1,250
24,5 25,0 25,5 26,0 26,4 26,9 27,4 27,9 28,4 28,8
28,330 28,950 29,570 30,180 30,790 31,400 32,010 32,610 33,220 33,820
341,380 350,290 359,280 368,200 377,180 386,220 395,320 404,360 413,590 422,750
33,680 34,410 35,160 35,930 36,700 37,480 38,250 39,020 39,800 40,580
405,840 416,360 427,200 438,350 449,580 461,000 472,390 483,850 495,510 507,250
18,709 19,160 19,615 20,072 20,526 20,979 21,438 21,897 22,355 22,813
225,440 231,840 238,320 244,880 251,440 258,040 264,760 271,520 278,320 285,160
21,880 22,380 22,880 23,380 23,869 24,370 24,860 25,360 25,850 26,340
263,650 270,800 277,990 285,240 292,400 299,750 307,020 314,460 321,830 329,250
1,255 1,260 1,265 1,270 1,275 1,280 1,285 1,290 1,295 1,300
29,3 29,7 30,2 3,6 31,1 31,5 32,0 32,4 32,8 33,3
34,420 35,010 35,600 36,190 36,780 37,360 37,950 38,530 39,100 39,680
431,970 441,130 450,340 459,610 468,940 478,210 487,660 497,040 506,340 515,840
41,360 42,140 42,920 43,700 44,480 45,270 46,060 46,850 47,630 48,420
519,070 530,960 542,940 554,990 567,120 579,460 591,870 604,370 616,810 629,460
23,273 23,730 24,190 24,643 25,098 25,556 26,014 26,478 26,941 27,403
292,080 299,000 306,000 312,960 320,000 327,120 334,280 341,560 348,880 356,240
26,830 27,320 27,800 28,290 28,770 29,250 29,731 30,210 30,680 31,150
336,720 344,230 351,670 359,280 366,820 374,400 382,040 389,710 397,300 404,950
51
Density 20 1,305 1,310 1,315 1,320 1,325 1,330 1,335 1,340 1,345 1,350
Be
Sulphuric acid Hydrochloric acid

% w/w g/l 525,260 534,740 544,280 553,740 563,260 572,830 582,330 591,880 601,480 611,010 % w/w g/l -
Nitric acid
% w/w 49,210 50,000 50,850 51,710 52,560 53,410 54,270 55,130 56,040 56,950 g/l 642,190 655,000 668,680 682,570 696,420 710,350 724,500 738,740 753,740 768,830
Caustic lye
% w/w 27,868 28,330 28,794 29,261 29,727 30,195 30,652 31,134 31,613 32,089 g/l 363,680 371,120 378,640 386,240 393,880 401,600 409,200 417,200 425,200 433,200
Caustic potash
% w/w 31,620 32,090 32,560 33,030 33,500 33,970 34,430 34,900 35,360 35,820 g/l 412,640 420,380 428,170 436,000 443,880 451,800 459,640 467,660 475,590 483,570
33,7 34,2 34,6 35,0 35,4 35,8 36,2 36,6 37,0 37,4
40,250 40,820 41,390 41,950 42,510 43,070 43,620 44,170 44,720 45,260
1,355 1,360 1,365 1,370 1,375 1,380 1,385 1,390 1,395 1,400
37,8 38,2 38,6 39,0 39,4 39,8 40,1 40,5 40,8 41,2
45,800 46,330 46,860 47,390 47,920 48,450 48,970 49,480 49,990 50,500
620,590 630,090 639,640 649,240 658,900 668,610 678,230 687,770 697,360 707,000
57,870 58,780 59,689 60,670 61,689 62,700 63,721 64,740 65,840 66,970
784,140 799,410 814,760 831,180 848,230 865,260 882,530 899,890 918,470 937,580
32,561 33,059 33,553 34,015 34,502 35,014 35,495 36,000 36,502 37,000
441,200 449,600 458,000 466,000 474,400 483,200 491,600 500,400 509,200 518,000
36,280 36,735 37,190 37,650 38,105 38,560 39,010 39,460 39,920 40,370
491,590 499,600 507,640 515,810 523,950 532,130 540,290 548,490 556,890 565,180
1,405 1,410 1,415 1,420 1,425 1,430 1,435 1,440 1,445 1,450
41,6 42,0 42,3 42,7 43,1 43,4 43,8 44,1 44,4 44,8
50,967 51,520 51,984 52,510 53,010 53,500 54,000 54,490 54,970 55,450
716,090 726,430 735,580 745,640 755,390 765,050 774,900 784,660 794,320 804,030
68,100 69,230 70,390 71,630 72,860 74,090 75,351 76,710 78,070 79,430
956,810 976,140 996,020 1017,150 1038,250 1059,490 1081,280 1104,620 1128,110 1151,740
37,495 37,986 38,473 38,986 39,495 40,000 40,502 41,028 41,550 42,069
526,800 535,600 544,400 553,600 562,800 572,000 581,200 590,800 600,400 610,000
40,820 41,260 41,710 42,155 42,600 43,040 43,479 43,920 44,360 44,790
573,520 581,770 590,200 598,600 607,050 615,470 623,930 632,450 641,000 649,460
52
Density 20 1,455 1,460 1,465 1,470 1,475 1,480 1,485 1,490 1,495 1,500
Be

% w/w g/l 813,780 823,590 833,440 843,440 853,140 862,990 872,880 882,680 892,520 902,550 % w/w g/l -
Nitric acid
% w/w 80,880 82,390 83,911 85,500 87,289 89,070 91,130 93,490 95,460 96,730 g/l 1176,800 1202,890 1229,290 1256,850 1287,520 1318,240 1353,280 1393,000 1427,120 1450,950
Caustic lye
% w/w 42,584 43,123 43,631 44,163 44,692 45,216 45,737 46,255 46,796 47,333 g/l 619,600 629,600 639,200 649,200 659,200 669,200 679,200 689,200 699,600 710,000
Caustic potash
% w/w 45,230 45,660 46,094 43,469 46,960 47,390 47,820 48,250 48,674 49,100 g/l 658,100 666,640 675,280 638,990 692,660 701,370 710,130 718,930 727,680 736,500
45,1 45,4 45,8 46,1 46,4 46,8 47,1 47,4 47,8 48,1
55,930 56,410 56,890 57,377 57,840 58,310 58,780 59,240 59,700 60,170
1,505 1,510 1,515 1,520 1,525 1,530 1,535 1,540 1,545 1,550
48,4 48,7 49,0 49,4 49,7 50,0 50,3 50,6 50,9 51,2
60,620 61,080 61,540 62,000 62,450 62,910 63,360 63,810 64,260 64,710
912,330 922,310 932,330 942,400 952,360 962,520 972,580 982,670 992,810 1003,010
97,990 99,260
1474,750 1498,830 -
47,841 48,371 48,898 49,421 49,967 50,484
720,000 730,400 740,800 751,200 762,000 772,400 -
49,530 49,950 50,380 50,800 51,220 51,640
745,430 754,250 763,260 772,160 781,100 790,090 -
1,555 1,560 1,565 1,570 1,575 1,580 1,585 1,590 1,595 1,600
51,5 51,8 52,1 52,4 52,7 53,0 53,3 53,6 53,9 54,1
65,150 65,590 66,030 66,470 66,910 67,350 67,790 68,230 68,660 69,090
1013,090 1023,200 1033,370 1043,580 1053,840 1064,130 1074,470 1084,860 1095,120 1105,440
53
Density 20 1,605 1,610 1,615 1,620 1,625 1,630 1,635 1,640 1,645 1,650
Be

% w/w g/l 1115,960 1126,360 1136,800 1147,280 1157,810 1168,220 1178,670 1189,330 1200,030 1210,610 % w/w g/l -
Nitric acid
% w/w g/l -
Caustic lye
% w/w g/l -
Caustic potash
% w/w g/l -
54,4 54,7 55,0 55,2 55,5 55,8 56,0 56,3 56,6 56,9
69,530 69,960 70,390 70,820 71,250 71,670 72,090 72,520 72,950 73,370
1,655 1,660 1,665 1,670 1,675 1,680 1,685 1,690 1,695 1,700
57,9 57,1 57,4 57,7 58,2 58,4 58,7 58,9 59,2 59,5
73,800 74,220 74,640 75,070 75,490 75,920 76,340 76,770 77,200 77,630
1221,390 1232,050 1242,750 1253,670 1264,450 1275,460 1286,330 1297,410 1308,540 1319,710
1,705 1,710 1,715 1,720 1,725 1,730 1,735 1,740 1,745 1,750
59,7 60,0 60,2 60,4 60,6 60,9 61,1 61,4 61,6 61,8
78,060 78,490 78,930 79,370 79,810 80,250 80,700 81,160 81,620 82,090
1330,920 1342,180 1353,650 1365,160 1376,720 1388,330 1400,150 1412,180 1424,270 1436,580
54
Density 20 1,755 1,760 1,765 1,770 1,775 1,780 1,785 1,790 1,795 1,800
Be

% w/w g/l 1449,110 1461,860 1475,110 1488,220 1501,830 1515,850 1530,460 1545,670 1561,470 1578,420 % w/w g/l -
Nitric acid
% w/w g/l -
Caustic lye
% w/w g/l -
Caustic potash
% w/w g/l -
62,1 62,3 62,5 62,8 63,0 63,2 63,5 63,7 64,0 64,2
82,570 83,060 83,576 84,080 84,610 85,160 85,740 86,350 86,990 87,690
1,805 1,810 1,815 1,820 1,821 1,822 1,823 1,824 1,825 1,826 1,827 1,828 1,829 1,830 1,840
64,4 64,6 64,8 65,0 65,0 65,1 65,1 65,2 65,2 65,3 65,3 65,4 65,4 65,4 65,9
88,430 89,230 90,120 91,110 91,334 91,560 91,780 92,000 92,250 92,510 92,825 93,030 93,361 93,640 95,598
1596,160 1615,060 1635,680 1658,200 1663,190 1668,220 1673,150 1678,080 1683,560 1689,230 1695,910 1700,590 1707,570 1713,610 1759,000
55
Annex Brief instruction Titration of hydrogen peroxide
Brief instruction - Titration of hydrogen peroxide

Remark Calculation is only valid for a 0.02 mol/l (= 0.1N) potassium permanganate solution.
An aliquot part is taken out, usually 1 to 10 ml, of the bleaching bath and given into an Erlenmeyer flask containing approx. 10 ml of a sulphuric acid of 20%. Titration is done immediately with a potassium permanganate solution of 0.02 mol/l (= 0./1 N) 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 For titration of 2 ml bleach liquor with solution of 0.02mol/l KMnO4 (= 0.1 N) 8.7ml of KMnO4-solution are consumed. How much H2O2 of 50% in ml/l does the bleaching liquor contain ? The factor for 2 ml of bleaching liquor and of H2O2 50% is 1.423 (see table). ml/l H2O2 50% = 8.7 1.423 = 12.4 ml/l
Sample of H2O2 100% bleach liquor in g/l

1 ml 2 ml 5 ml 10 ml
H2O2 50% in g/l in ml/l
H2O2 35% in g/l in ml/l
1,701 0,850 0,340 0,170
3,401 1,701 0,680 0,340
2,846 1,423 0,569 0,285
4,859 2,430 0,972 0,486
4,293 2,146 0,859 0,429
ml/l H2O2 x-% = consumption of KMnO4-solution factor
56
Annex Brief instruction Titration of caustic lye
Brief instruction - Titration of caustic soda

Remark The calculation is only valid for a hydrochloric acid of 0:1 mol/l (= 0.1N) or a sulphuric acid solution of 0.05 mol/l (= 0.1 N)
An aliquot part, usually 1 to 10 ml of the bath are taken and given into an Erlenmeyer flask containing some distilled water. Titration is done with 0.1 mol/l hydrochloric acid or 0.05 mol/l sulphuric acid (both of 0.1 N) up to the colour shade change of the indicator phenol phthaleine of red to colourless.
Calculation
Valid for a hydrochloric acid of 0.1 mol/l or sulphuric acid of 0.05 mol/l (both 0.1 N) Factor for Faktor for Factor for
Example 1 For titration of 2ml of bleach liquor with 0.1mol/l HCl-solution Lsung (= 0.1 N) 9.3ml of HClsolution are consumed. How much NaOH 100% in g/l does the bleach liquor contain ? The factor for a sample of 2 ml bleach liquor and NaOH 100% is 2 (see table). g/l NaOH 100% = 9:3 2 = 18.6 g/l
Sample of bath
1 ml
NaOH 100 % in g/l
NaOH 50 % in g/l in ml/l
NaOH 38 Be in g/l in ml/l
4,000 2,000 0,800 0,400
8,000 4,000 1,600 0,800
5,229 2,614 1,046 0,523
12,099 6,050 2,420 1,210
8,896 4,448 1,779 0,890
2 ml
5 ml 10 ml
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 HClsolution 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
57
Annex Brief instruction Titration of hydrogen peroxide
CHT R. BEITLICH GmbH Bismarckstrae 102 D 72072 Tbingen Germany Fon + 49 (0) 7071 154 0 Fax +49 (0) 7071 154 290 www.cht.com info@cht.com
58

Lab Test Book CHT

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Lab methods for judgement of pretreatment

Identification of fibre materials.....................................................12 Hydrogen peroxide ........................................................................16

Sodium hypochlorite (chlorine bleach lye) .................................27

Average polymerisation degree (DP-value) ................................ 47 Fluidity F......................................................................................... 49 Annex.............................................................................................. 50

Chemical damage of cellulosic fibres

Qualitative proof of iron

Undamaged cellulose Cellulose CH2OH OH

Qualitative proof of hydro- or oxycellulose

Qualitative proof of hydrocellulose with silver nitrate

Qualitative evidence of oxycellulose with methylene blue

To note: Merzerised CO reacts like damaged CO. Caution is advised.

Qualitative evidence of damaged CO by swelling test (immaturity control by swelling test)

Evidence of fats and oils on the fabric

Fabric free of oil or fat

Differences of degree of caustification and mercerisation

g/l NaOH 100 %

Dy)[g3 1 e(2 /c] 2 n0 m 2 s i t Siiyaa oltiwt0 lbntr2 u e C uitd ne lim

150 g/l NaOH 100 %

Sfrtlia C ax5 trcatn[] p.a ys r 1 t si o o o Ro anHax) en lke-lur.3 a a(veo c l pap1 t i i

200 g/l NaOH 100 %

Liquor ratio 1:40

C.I. Direct green 26

add fabric at boiling temp.

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

Then dewater the sample and air dry it.

TEGEWA-drop test brief description

Alternative for Patentblau V ERKA Typ S 4030

Capillary rise procedure brief description

Variation 1 (DIN 53924)

See further details TEGEWA-violet scale:

The degree of desize the TEGEWA-violetblue scale

pH value on the fabric

pH-Indicator (Merck) pH 3.5

pH-value determination description

Determination of the conductivity

high conductivity (180 S/cm) Print side

low conductivity (20 S/cm) Print side

Evidence of non ionic residual surfactants

Solution B: A barium chloride solution of 20 % in distilled water

Identiification of fibre materials

Identification of fibre materials

Natural and man-made fibres

Dry distillation pH-value

of burnt paper of burnt hair

Identification of fibre materials

Dry distillation pH-value

like burning candle

like burning candle

Identiification of fibre materials

Analysis of natural fibres

Identification of fibre materials

As simple examples can be mentioned

Different procedures of analysis

Vegetable fibres Animal fibres

Burning test Dyeing test

Mercerised not mercerised cotton

Microscopical analysis Red-/green test

Pure silk (bombyxs mori) and wild (e.g. Tussahsilk) silk

Properties of commercially available H2O2solutions

W 30 30 111 300 334 14. Jan 1.114

W 35 35 132 350 396 16. Mai 1.132

W 50 50 199 500 598 23. Mai 1.195

W 60 60 249 600 745 28. Feb 1.241