ETHIOPIAN ES 1176-2:2005

ES 4050
STANDARD

First edition
2005-03-12

Methods of testing cement

Part 2. Chemical analysis of cement

ICS: 91.100.10

Descriptors:

Reference number
Price based on 63 pages. ES 1176-2 :2005
ES 1176-2:2005

Foreword

This Ethiopian Standard has been prepared under the direction of Civil Engineering, Building and Construction
Materials Technical Committee and published by the Quality and Standards Authority of Ethiopia (QSAE)

In preparing this Ethiopian Standard reference has been made to the following:

European Standard EN 196 –2: 2005 Chemical analysis of cement

Acknowledgement is made fo r the use of information from the above publication.

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 ES 1176-2 :2005

Contents
Page

Foreword ii
Content iii

1 Scope 1
2 Normative refe rences 1
3 General requirements for testing 1
4. Reagents 2
5. Apparatus 12
6. Preparation of a cement sample 13
7 Determination of loss on ignition 13
8 Gravimetric determination of sulfate 14
9. Determination of residue insoluble in
hydrochloric acid and Sodium carbonate 15
10. Determination of residue insoluble in
hydrochloric acid and potassium hydroxide 16
11 Determination of sulfide 17
12 Photometric determination of manganese 18
13. Determination of main constituents 19
Annex A (informative) 30
Annex B (informative) 31
Annex C (informative) 34
Annex D (informative) 36

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ETHIOPIAN STANDARD ES 1176-2:2005

Methods of testing cement part 2. Chemical analysis of cement

1 Scope
This Ethiopian Standard describes the procedures for the chemical analysis of cement. The Ethiopian Standard
describes the reference procedures and, in certain cases, an alternative method which can be considered as giving
equivalent results. If other methods are used it is necessary to show that they give results equivalent to those given
by the reference methods. In the case of a dispute, only the reference procedures are used.

This standard applies to cements, and also to their constituent materials such as clinker and blastfurnace slag.
Standard specifications state which methods are to be used.

2 Normative references

The following Ethiopian Standards contain provisions, which, through reference to this text, constitute provisions of
this Ethiopian Standards. At the time of publication, the editions indicated were valid. All standards are subject to
revision, and parties to agreements based on this Ethiopian Standards are encouraged to investigate the possibility
of applying the most recent editions of the Ethiopian Standards indicated below. Registers of currently valid
standards are maintained in the Quality and Standards Authority of Ethiopia.

ES 4926-7, Methods of testing cement — Methods of taking and preparing samples of cement.

ES ISO 3534:2003, Statistics — Vocabulary and symbols.

3 General requirements for testing

3.1 Number of tests

The number of tests for the various determinations (clauses7 to13) is fixed at two (see also 3.3).
3.2 Repeatability and reproducibility

The standard deviation of repeatability gives the closeness of agreement between successive results obtained with
the same method on identical material tested under the same conditions (same operator, same apparatus, same
laboratory and short time interval) 1)

The standard deviation of reproducibility gives the closeness of agreement between individual results obtained with
the same method on identical material but tested under different conditions (different operators, different apparatus,
different laboratories and/or different times).
2)
The standard deviations of repeatability and reproducibility are expressed in absolute % .

3.3 Expression of masses, volumes, factors and results

Express masses in grams to the nearest 0,0001g and volumes from the burette in millilitres to the nearest 0,05ml.

Express the factors of solutions, given by the mean of three determinations, to hree
t decimal places. Express the
results of the tests, given by the mean of two determinations, as a percentage, generally to two decimal places. If
the difference between two determinations is more than twice the repeatability standard deviation, repeat ht e test
and take the mean of the two closest values.

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ES 1176-2:2005

3.4 Ignitions

Carry out the ignitions as follows. Place the filter paper and its contents into a crucible which has been previously
ignited and tared. Dry it, then incinerate it slowly in an oxidizing atmosphere, without flaming while ensuring
complete combustion. Then ignite at the stated temperature. Allow the crucible and its contents to cool to the
laboratory temperature in a desiccator. Weigh the crucible and its contents.

3.5 Determination of constant mass

Determine constant mass by making successive15min ignitions followed each time by cooling and then weighing.
Constant mass is reached when the difference between two successive weighings is less than 0,0005g.

3.6 Check for absence of chloride ions (silver nitrate test)

After generally five to six washes of a precipitate, rinse the base of the filter stem with a few drops of water. Wash
the filter and its contents with several millilitres of water and collect this in a test tube. Add several drops of silver
nitrate solution (4.33).

Check the absence of turbidity or precipitate in the solution. If present, continue washing while carrying out periodic
checks until the silver nitrate test is negative.

4 Reagents

4.0 General requirements

Use only reagents of analytical quality and distilled water, or water of equal purity, during the analysis.

Unless otherwise stated % means % by mass. The concentrated liquid reagents used in this Ethiopian Standard
3 0
have the following densities (ρ) (in g/cm at 20 C):

hydrochloric acid 1,18 to 1,19

hydrofluoric acid 1,13

nitric acid 1,40 to 1,42

sulfuric acid 1,84

phosphoric acid 1,71 to 1,75

acetic acid 1,05 to 1,06

ammonium hydroxide 0,88 to 0,91

triethanolamine 1,12

The degree of dilution is always given as a volumetric sum, for example: hydrochloric acid 1 + 2 means that
1volume of concentrated hydrochloric acid is to be mixed with 2 volumes of water.

4.1 Concentrated hydrochloric acid (HCl).

4.2 Dilute hydrochloric acid 1 + 1.

4.3 Dilute hydrochloric acid 1 + 2.

4.4 Dilute hydrochloric acid 1 + 3.

4.5 Dilute hydrochloric acid 1 + 9.

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4.6 Dilute hydrochloric acid 1 + 11.

4.7 Dilute hydrochloric acid 1 + 19.

4.8 Dilute hydrochloric acid 1 + 99.

4.9 Dilute hydrochloric acid of pH 1,60. Add five or six drops of concentrated hydrochloric acid to 2 l
water. Control the pH value by means of a pH-meter. Store the solution in a polyethylene flask.

4.10 Concentrated hydrofluoric acid (HF).

4.11 Dilute hydrofluoric acid 1 + 3.

4.12 Nitric acid (HNO 3).

4.13 Concentrated sulfuric acid (H 2 SO).

4.14 Dilute sulfuric acid 1 + 1.

4.15 Phosphoric acid (H 3 PO 4).

4.16 Boric acid (H 3 BO 3).

4.17 Acetic acid (CH 3 COOH).

4.18 Amino-acetic acid (NH 2 CH 2 COOH).

4.19 Metallic chromium in powder form (Cr).

4.20 Concentrated ammonium hydroxide (NH 4 OH.).

4.21 Dilute ammonium hydroxide 1 + 1 .

4.22 Dilute ammonium hydroxide 1 + 10.

4.23 Dilute ammonium hydroxide 1 + 16.

4.24 Sodium hydroxide (NaOH).

4.25 Sodium hydroxide solution 4 mol /l. Dissolve160g of sodium hydroxide in water and make up to
1000ml. Store in a polyethylene flask.

4.26 Sodium hydroxide solution 2mol/l. Dissolve 80g of sodium hydroxide in water and make up to
1000ml. Store in a polyethylene flask.

4.27 Ammonium chloride (NH 4Cl).

4.28 Tin (II) chloride (SnCl 2 2H2O).

4.29 Potassium periodate (KIO4 ).

4.30 Sodium peroxide in powder form (Na 2O2).

4.31 Mixture of sodium carbonate and sodium chloride. Mix 7g of sodium carbonate (anhydrous Na2
CO3) with 1g sodium chloride (NaCl).

4.32 Barium chloride solution. Dissolve120g of barium chloride (BaCl 2 2H 2O) in water and make up to
1000ml.

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ES 1176-2:2005

4.33 Silver nitrate solution. Dissolve 5g of silver nitrate (AgNO3) in water, add10ml of concentrated nitric
acid (HNO3 ) and make up to 1000ml with water.

4.34 Sodium carbonate solution. Dissolve 50g of sodium carbonate (anhydrous Na2 CO 3 ) in water and
make up to 1000ml.

4.35 Potassium hydroxide solution. Dissolve250g of potassium hydroxide (KOH) in water and make up
to 1000ml.

4.36 Ammoniacal zinc sulfate solution. Dissolve50g of zinc sulfate (ZnSO 4 7H 2O) in150ml water and
add 350ml of concentrated ammonium hydroxide (NH4OH). Leave to stand for at least24h and filter.

4.37 Lead acetate solution. Dissolve approximately 0,2g of lead acetate Pb (CH 3 COO)2 .3H 2 O in
water and make up to100ml.

4.38 Starch solution. To 1g of starch (water soluble), add 1g of potassium iodide (KI), dissolve in water
and make up to100ml.

4.39 Polyethylene oxide solution. Dissolve 0,25g of polyethylene oxide –CH 2–CH 2 –O–) n of average
molecular mass 200000 to 600000, in100ml water while stirring vigorously.

This solution is stable for approximately two weeks.

4.40 Boric acid solution, saturated. Dissolve approximately 50g of boric acid (H 3BO3) in water and make
up to 1000ml.

4.41 Citric acid solution. Dissolve10g of citric acid (C 6H 8O 7 .H 2O) in water and make up to100ml.

4.42 Ammonium molybdate solution. Dissolve10g of ammonium molybdate (NH4)6Mo 7O24 .4H2O in
water and make up to100ml.

Store the solution in a polyethylene flask. This keeps for approximately one week.

4.43 Copper sulfate solution. In a 50ml volumetric flask dissolve 0,45g of copper sulfate (CuSO4 .5H2O)
in water and make up to the mark.

4.44 Ammonium acetate solution. Dissolve 250g of ammonium acetate (CH 3COONH4 ) in water and
make up to 1000ml.

4.45 Triethanolamine N(CH 2CH 2OH)3 solution 1 + 4.

4.46 Reducing solution. Dissolve successively in water 0,15 g of 1-amino-2-hydroxy naphthalene-4-

sulfonic acid (C10H 9NO4S), 0,7g of sodium sulfite (anhydrous Na 2SO3) and 9,0g of sodium metabisulfite
(Na 2S2O5 ) and make up to 100 ml.

This solution will keep for a maximum of one week.

4.47 Buffer solution of pH 1,40. Dissolve 7,505 g of amino-acetic acid(NH2CH 2COOH) and 5,850g of
sodium chloride (NaCl) in water and make up to 1000ml. Dilute300ml of this solution to 1000ml with
dilute hydrochloric acid1 + 99.

4.48 Standard potassium iodate solution containing approximately 0,0166 mol/l3). Dissolve
successively, in freshly boiled and cooled water in a 1000ml volumetric flask, (3,6 ± 0,1) g of potassium
iodate (KIO 3 , dried at 120 0C), two tablets of sodium hydroxide (NaOH) and 25g of potassium iodide (KI).
Make up to the mark with freshly boiled and cooled water. The factor F of this solution is calculated from
the following formula:

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 ES 1176-2:2005

m1
F= (1)
3,5668

where m 1 is the mass of the portion of potassium iodate, in grams.

4.49 Sodium thiosulfate solution approximately 0,1mol/l 3)

4.49.1 Preparation

Dissolve24,82g of sodium thiosulfate (Na 2S 2O 3 .5H 2O) in water and make up to 1000ml. Before each test series,
determine the factor f of this solution as described in 4.49.2

4.49.2 Standardization

4.49.2.1 This standardization is carried out preferably in relation to the standard potassium iodate solution (4.48).

For this standardization, pipette20ml of the standard potassium iodate solution into a 500ml conical flask and dilute
with approximately150ml of water. Acidify with25ml of hydrochloric acid1 + 1 and titrate with the approximately
0,1mol/l sodium thiosulfate solution to a pale yellow colour.

Then add 2ml of the starch solution (4.38) and continue the titration until the colour changes from blue to
colourless.

The factor f of this solution is calculated from the formula:

20 x0 ,01667 x 214 ,01 xF F (2)

f = = 20 x
3,5668 V1 V1

where:

F is the factor of the standard potassium iodate solution (4.48);

V1 is the volume of the approximately 0,1 mol/l sodium thiosulfate solution used for the titration, in milliliters

3,5668 is the mass of potassium iodate corresponding to a solution with exactly 0,01667 mol/l of potassium iodate,
in grams;

214,01 is the molecular mass of KIO3

4.49.2.2 The standardization may also be carried out in relation to a known quality of potassium iodate.

For this standardization, place in a500ml conical flask (0,07± 0,005)g (m 2 ) of potassium iodate and dissolve in
approximately 150ml of water. Add about 1g of potassium iodide, acidify with25ml of hydrochloric acid 1 + 1 and
titrate with the approximately 0,1mol/l sodium thiosulfate solution until a pale yellow colour is obtained. Then add
2ml of the starch solution (4.38) and titrate until the colour changes from blue to colourless.

The factor f of this solution is calculated from the formula:

1000 x m2 m
f = = 280 ,3634 x 2 (3 )
3,5668 xV2 V2

where:

m 2 is the mass of the portion of potassium iodate, in grams;

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ES 1176-2:2005

V2 is the volume of the approximately 0,1 mol/l sodium thiosulfate solution used for the titration, in milliliters

3,5668 is the mass of potassium iodate, in grams corresponding to a solution with exactly 0,01667 mol/l of
potassium iodate.

4.50 Standard manganese ion solution

4.50.1 Anhydrous manganese sulfate

Dry some hydrated manganese sulfate (MnSO4. x H2O) to constant mass at a temperature of (250 ± 10) °C. The
composition of the product obtained corresponds to the formula MnSO4.

4.50.2 Preparation

Into a 1000ml volumetric flask, weigh approximately2,75g of anhydrous manganese sulfate (m 3 ); dissolve in water
2
and make up to the mark. The content G of manganese (II) ions of this solution, expressed in milligrams of Mn +
/ml, is calculated from the formula:

m3
G= (4)
2,7485

where:

m3 is the mass of the portion of anhydrous manganese sulfate, in grams.

4.50.3 Construction of the calibration graph

Into each of two volumetric flasks, respectively 500ml (No.1) and 1000ml (No.2), pipette20ml of the standard
manganese ion solution. Make up to the mark with water. Into each of three volumetric flasks, respectively 200ml
(No.3),500ml (No.4) and 1000ml (No.5) pipette100ml of the solution from flask No.2 and make up to the mark with
water.

Take100ml of each solution from flasks 1 to 5 and pipette each portion into a 400ml beaker. Add 20ml of
concentrated nitric acid, 1,5g of potassium periodate (4.29) and10ml of phosphoric acid (4.15), heat to boiling and
boil gently for30min.

Cool to20°C and transfer the contents of each beaker to a200ml volumetric flask. Cool the flasks and their contents
to20°C and make up to the mark with water. Measure the optical density of the solutions using a photometer (5.9)
at a wavelength of around 525nm, against water (use one or more cells (5.10) of appropriate sizes). Record the
optical density values to three decimal places. For each cell optical length plot a separate graph of the optical
densities of these standard solutions E 1 to E 5 as a function of the corresponding manganese concentrations in
milligrams of Mn per 200ml. The corresponding manganese concentrations are given in Table 1. They can be used
as given if the content G obtained in accordance with 4.50.2 has the value1,0000. Otherwise, multiply the
manganese concentrations in table 1 by G.

Table 1 — Concentrations of manganese standard solutions

Standard solution E1 E2 E3 E4 E5

Concentration of manganese in mg 4,0 2,0 1,0 0,4 0,2

of Mn per 200 ml

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 ES 1176-2:2005

4.51 Standard silica solution

4.51.1 Silica (SiO 2 ), of purity >99,9% after ignition

4.51.2 Sodium carbonate, anhydrous (Na2C O3 )

4.51.3 Basic solution

Weigh 0,2000g of silica, freshly ignited at (1175 ± 25) °C, in a platinum crucible already containing2,0g of sodium
carbonate.

Heat the mixture and fuse it at a bright-red heat for at least15min. After cooling to room temperature, place the
fused solid in a polyethylene beaker and dissolve it in water, then transfer the solution quantitatively to a200ml
volumetric flask and make up to the mark with water.

Store the solution in a polyethylene bottle.1ml of solution contains 1mg of SiO2 .

4.51.4 Standard solution

Pipette 5ml of the basic solution into a 250ml volumetric flask and make up to the mark with water. Store the
solution in a polyethylene bottle.1ml of the solution contains 0,02mg silica. This solution will keep for a maximum of
one week.

4.51.5 Compensating solutions

Prepare the compensating solutions according to the procedure adopted for the silica content (13.3 to13.5) by
dissolving the amounts of the reagents given in Table 2 in water and making up to500ml.

4.51.6 Construction of the calibration curve

Add from a burette the volumes of the silica calibration solution given in Table 3 into100ml polyethylene beakers
each containing a magnetic stirrer bar. Add20ml of the compensating solution by pipette and make up to40ml with
water from a burette. The volumes required for this are also given in Table 3. While stirring with a magnetic stirrer,
add15drops of hydrofluoric acid1 + 3. Stir for at least 1min. Then pipette15ml of the boric acid solution (4.40) into
the solution.

Table 2. Composition of the compensation solutions for a volume of 500ml

Precipitation by Precipitation by Decomposition

polyethylene oxide double evaporation by HCL and
(13.3) (13.4) NH4Cl (13.5)
HCl conc. ml 70 75 15
H2SO4 1+1 ml 1 1 -
HNO3 conc. ml - - 1
Polyethylene oxide solution ml 5 - -
NH4Cl g - - 1
Na2C O3 g 1.75 1.75 1.75
NaCl g 0.25 0.25 0.25
Na2O 2 g 3 3 -

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ES 1176-2:2005

Table 3. Composition of the silica calibration solutions and their silica content
Serial No. Blank 1 2 3 4 5 6 7 8

Standard SiO2 0 2 4 5 6 8 10 15 20
solution (ml)

Water (ml) 20 18 16 15 14 12 10 5 0

Silica content (mg 0 0.04 0.08 0.10 0.12 0.16 0.20 0.30 0.40
SiO2/100ml)

Adjust the pH of the solution to (1,15 ± 0,05) by adding, drop by drop, either the sodium hydroxide solution (4.25),
or hydrochloric acid1 + 2. Carry out this operation with the aid of a pH meter calibrated using a buffer (4.47) with a
neighbouring pH value (e.g.1,40).

Pipette 5ml of the ammonium molybdate solution( 4.42) into the solution (time0). Adjust the pH of this solution
to1,60by adding, drop by drop, either the sodium hydroxide solution (4.25) or hydrochloric acid1 + 2. Transfer the
solution to a100ml volumetric flask rinsing with dilute hydrochloric acid of pH =1,60 (4.9). After20min, pipette 5ml of
the citric acid solution (4.41) into the volumetric flask, stir and leave to stand for 5min.

Then pipette 2ml of the reducing solution (4.46) into the volumetric flask. Make up to the mark with dilute
hydrochloric acid pH = 1,60 (4.9) and mix thoroughly. Exactly 30min after introducing the ammonium molybdate
(time0 + 30), measure the optical density with a photometer (5.9) using a cell of 1cm optical length against the
blank solution prepared in the same way, using the wavelength of maximum extinction near815nm. Construct a
graph giving the measured optical densities as function of the corresponding silica contents given in Table 3.

The blank solution used in constructing the calibration curve may be used as the blank solution here. The
calibration curve enables the silica content in mg SiO 2 /100ml to be determined.

4.52 Standard calcium ion solution, approximately 0,01mol/l

4.52.1 Calcium carbonate (CaCO 3 ), dried at200ºC of purity >99,9 %.

4.52.2 Standard solution

Weigh approximately 1g of calcium carbonate and place it in a400ml beaker with approximately100ml of water.
Cover the beaker with a watch glass and carefully introduce approximately10ml of hydrochloric acid1 + 2. After the
reaction is completed, bring to boiling in order to expel the dissolved carbon dioxide. Cool and make up to 1000ml
in a volumetric flask.

4.53 EDTA solution, approximately0, 03mol/l

4.53.1 Dihydrated disodium salt of ethylenediaminetetra-acetic acid (EDTA)

4.53.2 Preparation

Dissolve11,17g of EDTA in water and make up to 1000ml. Store in a polyethylene bottle.

4.53.3 Standardization

Pipette 50ml of the standard calcium ion solution (4.52) into a beaker suitable for the measuring apparatus (5.11).
Then dilute with water to a volume suitable for the operation of the apparatus. Using a pH meter, adjust the pH of
this solution to12, 5with the sodium hydroxide solution or solutions (4.25 and4.26).

Determine the end-point using one of the following two methods.

a) Photometric determination of the end-point (reference method)

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 ES 1176-2:2005

Add about0, 1g of murexide (4.57) or of mixed indicator (4.63). Place the beaker in the apparatus (5.11) set
at620nm when using murexide or at520nm when using the mixed indicator and, while stirring continuously, titrate
with0, 03mol/l EDTA solution. In the vicinity of the indicator colour change, construct a diagram giving the optical
density values as a function of the volume of EDTA added. The volume V 3 used is determined from the
intersection of the line of greatest slope near the colour change and the line of almost constant optical density after
the colour change.

The factor f D of this solution is calculated from the formula:

50 x m4 m
fD = = 16 ,65 x 4 (5)
100 ,09 x 0,03 x V3 V3

where

m4 is the mass of the portion of calcium carbonate taken to prepare the standard calcium ion solution (4.52), in
grams;

V3 is the volume of the EDTA solution used for the titration, in milliliters.

b) Visual determination of the end-point (alternative method)

Add about 0,1g of the calcon indicator (4.59). Stir and titrate with 0,03mol/l EDTA solution until the colour changes
from pink to blue, and one drop in excess does not further increase the intensity of the blue colour. The volume V 3
is used to calculate the standardization factor fD using the formula (5).

4.54 Copper complexonate solution

Pipette25ml of the copper sulfate solution (4.43) into a400ml beaker and add from a burette an equivalent volume
of the 0,03mol/l EDTA solution(4.53). The required volume of EDTA solution is calculated as follows. Pipette10ml
of the copper sulfate solution (4.4 3) into a600ml beaker. Dilute to approximately200ml with water and add10ml of
concentrated ammonium hydroxide and about0,1g of murexide indicator (4.57). Titrate with the0,03mol/l EDTA
solution (4.53) until the colour changes from pink to violet. If V 4 is the volume used, the volume V 5 of the0,03mol/l
EDTA solution to be added to25ml of the copper sulfate solution to obtain copper complexonate is:

V5=2,5V4

4.55 EGTA solution, approximately0,03mol/l

4.55.1 Ethylenebis (oxyethylenenitrilo) tetra-acetic acid (EGTA ).

4.55.2 Preparation

Weigh approximately11,4g of EGTA into a600ml beaker and add about400ml of water and10ml of the sodium
hydroxide solution (4.2 6). Heat the mixture until the EGTA is completely dissolved. Allow to cool to room
temperature. Using a pH meter, adjust the pH value of the solution to7, by adding, drop by drop, dilute hydrochloric
acid 1 + 2. Transfer the solution quantitatively to a 1000ml volumetric flask and make up to the mark with water.
Store the solution in a polyethylene bottle.

4.55.3 Standardization

Pipette50ml of the standard calcium ion solution(4.52) into a beaker suitable for the measuring apparatus (5.1 1).
Then dilute with water to a volume suitable for the correct operation of the apparatus. Add25ml of the
triethanolamine 1 + 4 solution (4.4 5). Using a pH meter, adjust the pH of this solution to12,5with the sodium
hydroxide solution or solutions (4.25 and 4.26). Add about0,1g of murexide (4.57) or of calcein indicator (4.5 8).
Place the beaker in the apparatus(5.11) set at620nm when using murexide or at520nm when using calcein and,
while stirring the solution, titrate using the0,03mol/l EGTA solution. In the vicinity of the indicator colour change,

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ES 1176-2:2005

construct a diagram giving the optical density values as a function of the volume of EGTA added. The volume V 6
used is determined from the intersection of the line of greatest slope near the colour change and the line of almost
constant optical density after the colour change.

The factor fG is calculated from the formula:

50 x m5 m
fG = = 16 ,65 X 5 (7)
100 ,09 x 0,03 x V6 V6

where:

m 5 is the mass of the portion of calcium carbonate taken to prepare the standard calcium ion solution (4.52), in
grams;

V 6 is the volume of EGTA solution used to titrate 50ml of the standard calcium ion solution (4,52), in milliliters

4.56 DCTA solution, approximately 0,01mol/l

4.56.1 Cyclohex-1,2-ylenedinitrilotetra-acetic monohydrate (DCTA)

4.56.2 Preparation

Weigh3,64g of DCTA into a600ml beaker and add about400ml of water and10ml of sodium hydroxide solution
(4.26). Heat the mixture until the DCTA is completely dissolved. Allow to cool to room temperature. Using a pH
meter, adjust the pH value of the solution to 7by adding dilute hydrochloric acid1 + 2, drop by drop. Transfer the
solution quantitatively to a 1000ml volumetric flask and make up to the mark with water. Store this solution in a
polyethylene bottle.

4.56.3 Standardization

Pipette50ml of the standard calcium ion solution(4.52) into a beaker appropriate for the measuring apparatus
(5.11). Then dilute with water to a volume suitable for the correct operation of the apparatus.

Using a pH meter, adjust the pH of this solution to10,5with concentrated ammonium hydroxide. Add
approximately0,1g of murexide (4.57) or of calcein indicator (4.58). Place the beaker in the apparatus (5.11) set
at620nm when using murexide or at520nm when using calcein and, stirring the solution, titrate with the DCTA
solution. In the vicinity of the colour change of the indicator, construct a diagram of the optical density values as a
function of the volume of DCTA added. The volume V 7 used is determined by the intersection of the line of
greatest slope near the colour change and the line of almost constant optical density after the colour change. The
factor f c is calculated from the formula:

50 x m6 m
fc = 49 ,955 x 6 (8 )
100 ,09 x 0,01 XV 7 V7

where

m 6 is the mass of the portion of calcium carbonate taken for preparing the standard calcium ion solution (4.52), in
grams;

V 7 is the volume of DCTA solution used for the titration, in milliliters

4.57 Murexide indicator

Grind 1g of murexide (ammonium purpurate) with100g of sodium chloride (NaCl).

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4.58 Calcein indicator

4.58.1 Calcein

Bis [(bis (carboxymethyl)-amino-methyl] – 2’, 7’-fluorescein.

4.58.2 Preparation

Grind 1g of calcein with99g of potassium nitrate (KNO 3 ).

4.59 Calcon indicator

4.59.1 Calcon

Sodium 2-hydroxy-4-(2-hydroxy-1-naphthylazo) naphthalene-1-sulfonate.

4.59.2 Preparation

Grind 1g of calcon with100g of anhydrous sodium sulfate (Na2SO4).

4.60 Sulfosalicylic acid indicator (sulfo-5-salicylic acid dihydrate)

4.61 PAN indicator

4.61.1 PAN

1-(2-pyridylazo)-2-naphthol.

4.61.2 Preparation

3
Dissolve0,1g of PAN in100ml ethanol (C2 H5 OH, ρ =0,79g/cm ).

4.62 Methylthymol blue indicator

4.62.1 Methylthymol blue

Sodium salt of 3’, 3’’-bis- [bis (carboxy-methyl)-aminomethyl]- thymolsulfonphthalein.

4.62.2 Preparation

Grind 1g of methylthymol blue with100g of potassium nitrate (KNO3).

4.63 Mixed calcein and methylthymol blue indicator

Grind 0,2g of calcein and 0,1g of methylthymol blue with100g of potassium nitrate (KNO3 ).

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5 Apparatus

5.1 Balance(s), capable of weighing to the nearest 0,0001g.

5.2 Porcelain and/or platinum crucible(s), 20ml to25ml capacity, fitted with a lid.

5.3 Fire proof ceramic support(s), for preventing overheating of the crucible. It shall be in thermal
equilibrium with the furnace at the moment the crucible is introduced.

5.4 Porcelain evaporating dish, of approximately200ml.

5.5 Electric furnace(s), naturally ventilated, capable of being set at the following
temperatures:500°C,925 °C,975 °C and 1175 °C.

5.6 Desiccator(s), containing anhydrous magnesium perchlorate (Mg(ClO4)2 ).

5.7 Bulb condenser.

5.8 Apparatus for determining sulfides. A typical apparatus is shown in Figure 1.

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 ES 1176-2:2005

A Woolf bottle may be added for controlling the flow of gas.

The connecting tubes shall be made of a material free from sulfur (polyvinyl chloride, olyethylene, etc.).

5.9 Photometer(s), for measu ring the optical density of a solution in the vicinity of525nm and 815nm.

5.10 Cells, for the photometer.

5.11 Apparatus, for measuring the optical density at520nm and at620nm of a solution contained in a
titration beaker, while stirring the solution with a magnetic stirrer.

5.12 Magnetic stirre r, with PTFE covered bar.

5.13 Evaporation apparatu s, controlled at(105 ± 3) °C.

5.14 Sand bath or hot plate, controlled at approximately 400°C.

5.15 Filter papers. The filter papers used shall be ashless.

NOTE Filter papers with a mean pore diameter of around 24m are called fine, those with a mean pore diameter of around7 4m
are called medium and those with a mean pore diameter of around204m are called coarse.

5.16 Volumetric glassware. The volumetric glassware shall be of analytical accuracy, i.e. class A as
defined in the ISO standards on laboratory glassware .

6 Preparation of a cement sample

Before chemical analysis, the laboratory sample taken in accordance with ES 4926-7 is treated to give a sample for
testing. Take approximately100g of the sample by means of a sample divider or by quartering. Sieve this portion on
a150 µm or125 µ0m sieve until no more passes through. Remove with a magnet all the metallic iron from the
material retained on the sieve. Then grind the iron-free fraction of the retained material so that it completely passes
the150 µm or 125µm sieve. Transfer the sample to a clean dry flask with an airtight closure and shake vigorously to
mix it thoroughly. The preceding operations are to be carried out as quickly as possible so that the sample is
exposed to ambient air for the minimum time.

NOTE. The sample is presented for analysis as marketed. If it contains particles of metallic iron, such as those that may be
introduced accidentally during grinding, the complete separation of these iron particles is carried out by means of a magnetic
stirrer in a suspension, for example in cyclohexane.

7 Determination of loss on ignition

7.1 Principle

The loss on ignition is determined in an oxidizing atmosphere (air). By igniting in air at (975 ± 25) °C the carbon
dioxide and water are driven off and any oxidizable elements present are oxidized. A correction for the influence of
this oxidation on the loss on ignition is described.

7.2 Procedure

Weigh (1 ± 0,05) g of cement (m 7) into a crucible which has been previously ignited and tared. Place the covered
crucible in the electric furnace (5.5 ) controlled at (975 ± 25) °C. After heating for 5min, remove the lid and leave the
crucible in the furnace for a further 10min. cool the crucible to room temperature in the desiccator. Weigh.
Determine constant mass in accordance with 3.5.

NOTE For cement containing sulfides, a more precise determination of the loss on ignition can be obtained by determining the
sulfate contents before and after ignition. The corrections applicable to these cements are given in 7.4.

13
ES 1176-2:2005

7.3 Expression of results

The observed loss on ignition is calculated in percent from the formula:

m7 x m8
Observed loss on ignition= X 100 (9)
m7

Where

m 7 is the mass f the test portion, in grams;

m 7 is the mass of the ignited test portion, in grams.

7.4 Errors and corrections

Errors are caused either by the presence of carbon or by oxidation of sulfides of any remaining metallic iron, of
bivalent iron and of bivalent manganese. The error resulting from the presence of these different elements may be
corrected for, but only the correction due to oxidation of sulfides is to be applied, the others usually being
2–
considered to be negligible. In this case, the correction due to sulfide is 1,996 × S and:

the corrected loss on ignition

= Observed loss on ignition + (1,996 × S 2– )

where S 2– and the losses on ignition are expressed in percent.

For determination of sulfate present before and after ignition the relation is:

SO3 (final) - SO 3 (initial) = SO3 resulting from the oxidation of sulfides i.e. a correction of: 0.8 X (SO 3 from oxidation
of sulfide) = oxygen taken up and corrected loss on ignition = observed loss on ignition+ oxygen taken up where all
the values are expressed in percent. Any corrections applied shall be indicated in the test report. In the case of
dispute, only the correction due to oxidation of sulfide shall be applied.

7.5 Repeatability and reproducibility

The standard deviation for repeatability is 0,04%. The standard deviation for reproducibility is 0,08%.

8 Gravimetric determination of sulfate

8.1 Principle

Sulfate ions, dissolved by decomposing cement with hydrochloric acid, are precipitated at a pH between1 and 1,5
by a solution of barium chloride. The precipitation is carried out at boiling point:
2– 2+
SO4 + Ba = BaSO 4

The determination is then completed gravimetrically and expressed as SO3.

8.2 Procedure

To (1 ± 0,05) g of cement (m 9), placed in a 250ml beaker, add 90ml of cold water. While stirring the mixture
vigorously, add10ml of concentrated hydrochloric acid. Heat the solution gently and crush the sample with the
flattened end of a glass stirring rod until decomposition of the cement is complete. Allow the solution to digest
for15min at a temperature just below boiling. Filter the residue through a medium filter paper into a400ml beaker.
Wash thoroughly with hot water. Check for the disappearance of Cl – ions by the silver nitrate test (3.6). Adjust the
volume to about250ml; if necessary, adjust the pH of the solution to between1 and1, 5 with hydrochloric acid 1 + 11

14
 ES 1176-2:2005

or ammonium hydroxide 1 + 16. Bring to the boil and boil for 5min. Check that the solution is clear; if not, start the
test again using a new portion. While stirring vigorously the solution maintained at boiling point, add drop by
drop10ml of the barium chloride solution (4.32) heated to just below boiling. Continue the boiling for15min so that
the precipitate is properly formed. Allow the solution to stand for 12h to24h below boiling temperature but above60
°C, taking care to avoid concentration by evaporation.

Filter the precipitate through fine filter paper and wash thoroughly with boiling water until free from Cl – ions, tested
by the silver nitrate test (3.6). Ignite at (925 ± 25) °C (3.4) then check for constant mass (3.5). In general, an
ignition period of15min is sufficient for obtaining constant mass.

8.3 Expression of results

The sulfate content, expressed as SO 3 , is calculated in percent from the formula:

m10 x 0,343 x 100 m

SO3 = = 34 ,3 x 10 ( 10 )
m9 m9

where:

m 9 is the mass of the test portion, in grams;

m 10 is the mass of barium sulfate, in grams

8.4 Repeatability and reproducibility

The standard deviation for repeatability is 0,07%. The standard deviation for reproducibility is 0,08%.

9 Determination of residue insoluble in hydrochloric acid and sodium carbonate

9.1 Principle

This is a conventional method in which the insoluble residue in cements is obtained by treatment with a dilute
hydrochloric acid solution so as to avoid as far as possible the precipitation of soluble silica. The residue from this
treatment is treated with a boiling solution of sodium carbonate in order to re-dissolve traces of silica which may
have been precipitated. The residue is determined gravimetrically after ignition.

9.2 Procedure

To (1 ± 0.05) g of cement (m 11), placed in a 250ml beaker, add90ml of water and, while stirring the mixture
vigorously, add10ml of concentrated hydrochloric acid.

Heat the solution gently and crush the sample with the flattened end of a glass stirring rod until decomposition of
the cement is complete. Allow the solution to digest for15min at a temperature just below boiling.

Filter the residue through a medium filter paper and wash thoroughly with almost boiling water. Transfer the filter
paper and its contents back to the reaction beaker and add100ml of the sodium carbonate solution (4.34). Boil
for15min. Filter on a medium filter paper and wash with almost boiling water, then four times with hot hydrochloric
acid 1+ 19 until pH < 2 is obtained and finally at least ten times with almost boiling water until free from Cl– ions,
tested by the silver nitrate test (3.6).

Ignite at (975 ± 25) °C (3.4) then checks for constant mass (3.5). In general, an ignition period of30min is sufficient
for obtaining constant mass.

NOTE If a cloudy filtrate is observed, filter again on a fine filter paper, wash thoroughly with hot water and combine the two
residues on their filter papers to ignite them. If in spite of this operation the filtrate remains cloudy, its effect on the insoluble
residue may be neglected.

15
ES 1176-2:2005

9.3 Expression of results

The insoluble residue is calculated in percent from the formula:

m12
Insoluble residue= x 100
m11

where:

m 11 is the mass of the test portion, in grams;

m 12 is the mass of the ignited insoluble residue, in grams.

9.4 Repeatability and reproducibility

The standard deviation for repeatability is 0,04 %. The standard deviation for reproducibility is 0,06 %.

10 Determination of residue insoluble in hydrochloric acid and potassium hydroxide

10.1 Principle

This is a conventional method in which the insoluble residue in cements is obtained by treating with a hydrochloric
acid solution. The residue from this treatment is then treated with a boiling solution of potassium hydroxide. The
residue is determined gravimetrically after ignition.

10.2 Procedure

To (1 + 0.05) g of cement (m 13), placed in a porcelain dish (5.4), add25ml of cold water and disperse using a
glass stirring rod. Add40ml of concentrated hydrochloric acid. Heat the solution gently and crush the sample with
the flattened end of a glass stirring rod until decomposition of the cement is complete. Evaporate to dryness on a
water bath. Repeat the operation twice more with20ml concentrated hydrochloric acid. Treat the residue from the
last evaporation with100ml of dilute hydrochloric acid 1 + 3. Re-heat, filter through a medium filter paper and wash
with almost boiling water at least ten times until free from Cl – ions, tested by the silver nitrate test (3.6).

Transfer the filter and its contents to a 250ml conical flask fitted with a bulb condenser and add100ml of the
potassium hydroxide solution (4.35). Leave to stand for16h at room temperature and then boil the solution under
reflux for 4 h.

Filter on a medium filter paper and wash with water then with100ml of hydrochloric acid 1 + 9 and finally with
almost boiling water until free from Cl – ions, tested by the silver nitrate test (3.6).

Ignite at (975 ± 25) °C (3.4) then check for constant mass (3.5). In general, an ignition period of30min is sufficient
for obtaining constant mass.

10.2.1 Expression of results

The insoluble residue is calculated in percent from the formula:

m14
Insoluble residue = x 100 (12)
m13

where

16
 ES 1176-2:2005

m 13 is the mass of the test portion, in grams;

m 14 is the mass of the ignited insoluble residue, in grams.

10.3 Repeatability and reproducibility

The standard deviation for repeatability is 0,15 %. The standard deviation for reproducibility is 0,18 %.

11 Determination of sulfide

11.1 Principle

The sample is decomposed by hydrochloric acid under reducing conditions. The sulfides are transformed into
hydrogen sulfide, which is carried over by a gaseous stream into an ammoniacal solution of zinc sulfate. The
precipitated zinc sulfide is determined by iodometry.

11.2 Procedure
Use the apparatus described in 5.8.Place (1 ± 0,05)g of the cement (m 15 ) 4) in a 250ml stoppered round bottom
flask with a ground glass joint. Add about2,5g of tin II chloride (4.28) and0,1g of chromium (4.19)5) . Disperse
in50ml of water. Fix the flask to the ground neck of the separating funnel and connect to the condenser the glass
outlet tube which dips into the beaker containing15ml of ammoniacal zinc sulfate solution (4.36) and285ml of water.
Connect the gas supply (air, nitrogen or argon) and adjust the flow to about10ml per min. Stop the flow of gas.
Release50ml of hydrochloric acid 1 + 1 from the separating funnel ensuring that a small quantity of acid remains
in the separating funnel to prevent leakage. Reconnect the gas supply, heat the contents of the flask to boiling and
boil for10min. Disconnect the outlet tube which will serve as a stirrer during the titration. Cool the receiver to20 °C,
add exactly10ml of potassium iodate solution approximately0, 0166mol/l (4.48) and25ml concentrated hydrochloric
acid. Titrate with sodium thiosulfate solution (4.49) until pale yellow. Then add 2ml of starch solution (4.38) and
titrate until the colour changes from blue to colourless.

11.3 Expression of results

The sulfide content is calculated in percent from the formula:

2- (V8 x F ) − (V9 x f ) x 1,603 x 100

S =
1000 Xm15

(V8 x F ) − (V9 x f )
= 0,1603 X ( 13 )
m15

Where

V8 is the volume of potassium iodate solution, in milliliters;

F is the factor of the potassium i odate solution as in 4.48

V9 is the volume of the sodium thiosulfate solution used for the titration, in milliliters;

f is the factor of the sodium thiosulfate solution as in 4.49

m 15 is the mass of the test portion, in grams, as in 11.2

17
ES 1176-2:2005

11.4 Repeatability and reproducibility

The standard deviation for repeatability is 0,02%. The standard deviation for reproducibility is 0,04 %.

12 Photometric determination of manganese

12.1 Principle
–
The manganese present is oxidized to MnO 4 by means of potassium periodate. The optical density of the violet
3+
solution is measured at525nm. The Fe ions are complexed with phosphoric acid which also assists the formation
of MnO4 and stabilizes the colour of the solution.

12.2 Procedure

According to the manganese content expected 6), weigh 0,1g to1, 0g of cement into a250ml beaker. Disperse in
about75ml of water. Stir, add cautiously15ml of concentrated nitric acid and boil until free from any hydrogen
sulphide (H2S) present and all the cement is decomposed.

Filter through a medium filter paper into a 400ml beaker. Wash the residue with hot water until the volume of the
filtrate is120ml. To this filtrate, add10ml of phosphoric acid (4.1 5), mix and add1.5g of potassium periodate (4.2 9).
Heat to boiling until the characteristic pink colour of permanganate appears. If it does not appear, reduce the acidity
by adding a few drops of concentrated ammonium hydroxide. Once the colour has appeared, continue boiling
gently for30min. Cool and transfer the contents of the beaker to a 200ml volumetric lask. f Cool to20°C and make
up to the mark with water. Using a photometer, measure the optical density of the solution against water at a
wavelength of approximately525nm (5.9 and5.10). Record the optical density value to three decimal places. The
optical density read from the calibration graph corresponding to the cell used gives the concentration of
manganese, C, in milligrams of Mn per200ml. Record the manganese concentration, C, to three decimal places.

12.3 Expression of results

The manganese content is calculated in percent from the formula:

C x 100 C
Mn = = 0,1 x ( 14 )
1000 x m16 m16

where

C is the manganese concentration of the solution in mg/200 ml;

m 16 is the mass of the test portion, in grams, as in 12.2

The manganese content may be converted into MnO or Mn2O3 by means of the following formulae:

MnO = 1,2912 X Mn (in %) ( 15 )

Mn2O 3 = 1,4368 X Mn (in %) ( 16 )

12.4 Repeatability and reproducibility

The standard deviation for repeatability is 0,003%. The standard deviation for reproducibility is0,03 %.

18
 ES 1176-2:2005

13 Determination of main constituents

13.1 Principle
The analysis is carried out after the sample is completely dissolved. The cement is decomposed by sintering with
sodium peroxide or by treatment with hydrochloric acid in the presence of ammonium chloride. In the first case,
after dissolution of the sintered solid in hydrochloric acid, the major part of the silica is precipitated either by
hydrochloric acid with coagulation by polyethylene oxide or by double evaporation; in the second case, the major
part of the silica is separated by the treatment. The impure silica precipitated is treated with hydrofluoric acid and
sulphuric acid to volatilize silica; the residue, treated with a mixture of sodium carbonate and sodium chloride, is
dissolved in hydrochloric acid and added to the silica filtrate.

In the case of the treatment with hydrochloric acid in the presence of ammonium chloride, if the residue obtained
after volatilization of impure silica by means of hydrofluoric acid and sulfuric acid is greater than0,5 %, the method
is not applicable. The cement shall in this case be decomposed by sodium peroxide. In the final solution made up
to500ml, the silica in solution is determined by photometric determination, and iron (III) oxide, aluminium oxide,
calcium oxide and magnesium oxide are determined by complexometric methods. The schematic diagram of the
chemical analysis is shown in Figure 2.

The scheme given in Figure 2 results, as far as the determination of silica is concerned, in the same values for total
silica whichever path is chosen.

13.2 Decomposition with sodium peroxide

Weigh (1 ± 0,05) g of cement (m 17 ) and 2 g of sodium peroxide (4.3 0) into a platinum crucible (5.2); mix thoroughly
with a spatula. Brush back into the mixture any particles adhering to the spatula. Cover the mixture with 1g of
sodium peroxide. Carefully preheat the covered crucible for about 2min at the opening of the furnace (5.5) before
placing it on its support (5.3) in the heated zone controlled at a uniform temperature of (500 ± 10) °C.

After30min, remove the crucible from the furnace and allow it to cool to room temperature. The sintered mass
should not stick to the sides of the crucible. If it does, then repeat the decomposition at a temperature 10 °C lower
than was first used.

Transfer the sintered mass to a 400ml beaker and rinse the crucible with150ml cold water.

Cover the beaker with a watch glass and heat until the solid is completely dissolved. Then add cautiously50ml of
concentrated hydrochloric acid. The solution obtained shall be perfectly clear. If not, reject it and repeat the
decomposition by peroxide at a temperature increased by 10°C or for double the time in the furnace. Add to the
solution 1ml of sulfuric acid1 + 1. Bring the solution to the boil and boil for30min. This solution is ready for use for
the precipitation of silica in accordance with 13.3 or 13.4.

13.3 Precipitation and determination of silica—Polyethylene oxide method (reference method)

13.3.1 Procedure

Evaporate to dryness the solution prepared as described in 13.2. Allow the beaker to cool. Treat the residue with
5ml of water and10ml of concentrated hydrochloric acid. While stirring, add some ashless filter paper pulp to the
mixture and then 5ml of the polyethylene oxide solution (4.39) ensuring that the precipitate and the polyethylene
oxide are thoroughly mixed, especially the precipitate adhering to the sides of the beaker. Stir the mixture
thoroughly then add10ml of water, stirring briefly and leave to stand for 5min. Then filter through a medium filter
paper into a 500ml volumetric flask and rinse with hot hydrochloric acid 1 + 19. Remove any precipitate adhering to
the sides of the beaker using a rubber scraper. Wash the filter and precipitate at least five times with hot
hydrochloric acid1 + 19, then rinse with hot water, ensuring that the residue in the filter is broken up thoroughly
during washing, until free from Cl – ions, tested by the silver nitrate test(3.6). Collect the washings in the
same500ml volumetric flask. Ignite the filter and the precipitate in a platinum crucible (1 175 + 25) °C (3.4). Check
for constant mass (3.5). In general, an ignition period of60min is sufficient for obtaining constant mass (m 18 ).
Volatilize the decomposed residue as in 13.6. Add the decomposed residue (13.7) to the filtrate and washings in
the500ml volumetric flask. The combined solution is used for the colorimetric determination of silica remaining in
solution (13.8) and also for the complexometric determinations of iron (III) oxide (13.10), aluminium oxide (13.1 1),
calcium oxide (13.12 or 13.14) and magnesium oxide (13.13 or 13.15).

19
ES 1176-2:2005

13.3.2 Expression of results

The impure silica content is calculated in percent from the formula:

m18
Im pure SiO2 = x 100 ( 17 )
m17

20
 ES 1176-2:2005

where

M17 is the mass of the e test portion as in 13.2, in grams;

m 18 is the mass determined in accordance with 13.3.1, in grams.

13.4 Precipitation and determination of silica— Double evaporation method

(alternative method)
13.4.1 Procedure

Evaporate to dryness the solution prepared as described in 13.2 on evaporation apparatus controlled at (105 ±
3)°C (5.13). Moisten with several drops of concentrated hydrochloric acid. Leave for 1h at this temperature. After
cooling to room temperature, treat the residue with10ml of concentrated hydrochloric acid. After a few minutes
dilute with50ml of water, bring to the boil and filter the hot solution through a medium filter paper into a500ml
volumetric flask. Wash the filter and the residue three times with hot water. Evaporate the filtrate and washings in
the same way, treat with10ml of concentrated hydrochloric acid and dilute with50ml of water. Boil, then pass
through the same filter into a 500ml volumetric flask. Wash the filter and the residue with hot water until free from Cl
– ions, tested by the silver nitrate test( 3.6). Collect the washings in the same500ml volumetric flask. Ignite the filter
and precipitate in a platinum crucible at (1 175 ± 25) °C (3.4). Check for constant mass (3.5). In general, an ignition
period of 60min is sufficient for obtaining constant mass. Volatilize the decomposed residue as described in 13.6.
Add the decomposed residue (13.7) to the filtrate and washings in the500ml volumetric flask. The combined
solutions are used for the colorimetric determination of silica remaining in solution (13.8) and for the
complexometric determinations of iron (III) oxide (13.10), aluminium oxide (13.1 1), calcium oxide (13.12 or 13.1 4)
and magnesium oxide (13.13 or13.1 5).

13.4.2 Expression of results

The impure silica content is calculated in percent from the formula:

m19
Im pure SiO2 = x 100 ( 18 )
m17

where

m17 is the mass of the test portion as in 13.2, in grams;

m19 is the mass determined in accordance with 13.4.1, in grams.

13.5 Decomposition with hydrochloric acid and ammonium chloride and precipitation of silica
(alternative method).
13.5.1 Procedure

Weigh (1 ± 0,05)g of cement (m 20 ) and place in a100ml beaker. Add about 1g of ammonium chloride (4.27) and
mix thoroughly with a glass stirring rod. Cover the beaker with a watch glass and cautiously add10ml of
concentrated hydrochloric acid taking care to let the acid run down the side of the beaker. When effervescence has
stopped, add10drops of nitric acid and stir with a glass stirring rod.

Place the beaker and its watch glass on a boiling water bath and leave for30min. Filter through a coarse filter paper
into a500ml volumetric flask: transfer the gelatinous precipitate to the filter as completely as possible without
dilution, and allow the solution to drain through the filter. Remove all precipitate adhering to the beaker by using a
rubber scraper.

Rinse the beaker and precipitate with hot hydrochloric acid1 + 99. Then wash the precipitate and filter12times with
small amounts of hot water until free from Cl – ions, tested by the silver nitrate test (3.6). Collect the washings in

21
ES 1176-2:2005

the same500ml volumetric flask. This is used, together with the decomposed residue treated as described in 13.7
for the photometric determination of silica in solution in accordance with 13.8. Ignite the filter and the precipitate in
a platinum crucible at (1 175 ± 25) °C (3.4). Check for constant mass (3.5). In general, an ignition period of60min is
sufficient for obtaining constant mass. Volatize the decomposed residues as described in13.6.

13.5.2 Expression of results

The impure silica is calculated in percent from the formula:

m21
Im pure SiO2 = x 100 (19)
m 20

where:

m 20 is the mass of the test portion as in 13.5.1, in grams;

m 21 is the mass determined in accordance with 13.5.1, in grams.

13.6 Determination of pure silica

13.6.1 Procedure

Moisten the residue obtained in accordance with13.3.1 (m 18 ) or13.4.1 (m 19 ) or 13.5.1 (m 21 ) with about0,5ml
to 1ml of water, add approximately10ml of hydrofluoric acid then two drops of sulfuric acid. Evaporate in a fume
cupboard over a sand bath or hot plate (5.14), then continue to heat until free from white sulfuric acid fumes. Ignite
the crucible with the evaporation residue in an electric furnace (1 175 ± 25) °C (5.5) for10min, leave to cool to room
temperature in a desiccator and weigh (m 22). The evaporation residue is decomposed as described in 13.7. If the
residue obtained by this method exceeds0, 5%, the analysis shall be restarted and decomposition with sodium
peroxide used (13.2).

13.6.2 Expression of results

The pure silica content is calculated in percent from the formula:

m24 − m22
Pure SiO2 = x 100 (20)
m 23

m 22 is the mass determined in accordance with 13.6.1, in grams;

m 23 is the mass of the test portion as in 13.2 (m17) or 13.5.1 (m20), in grams;

m 24 is the mass determined in accordance with 13.3.1 (m18), 13.4.1 (m19) or 13.5.1 (m21), in grams.

13.7 Decomposition of the evaporation residue

To the evaporation residue, obtained in accordance with 13.6.1, add 2g of the sodium carbonate and sodium
chloride mixture (4.31) and fuse to a bright red heat using a gas burner. Swirl the melt frequently until the residue is
completely dissolved. Check visually that no part of the residue remains at the base of the crucible. Allow the
crucible and its contents to cool, transfer to a250ml beaker, add about100ml water and acidify with a few milliliters
of concentrated hydrochloric acid.

When the decomposed mass is completely dissolved, remove the platinum crucible from the solution and rinse it
with water. The solution shall be perfectly clear. If not, filter through a medium filter paper, wash, burn off the paper,

22
 ES 1176-2:2005

ignite and then repeat the decomposition as above. Transfer the solution to the 500ml volumetric flask containing
the filtrate and washings from the precipitation of silica in accordance with 13.3.1 or 13.4.1 or 13.5.1. Fill the flask
up to the mark with water. After stirring, this solution is ready for use.

It is used in the photometric determination of the silica remaining in solution (13.8) and also in the complexometric
determinations of iron (III) oxide (13.10), aluminium oxide (13.1 1), calcium oxide (13.12 or 13.14) and magnesium
oxide (13.13 or13.15).

13.8 Determination of soluble silica

13.8.1 Procedure

Pipette 20ml of the solution prepared in accordance with 13.7 from the500ml volumetric flask into a polyethylene
beaker already containing a magnetic stirrer bar and add20ml water. While stirring with the magnetic stirrer,
add15drops of hydrofluoric acid1 + 3. Stir again for at least 1min. Then pipette15ml of the boric acid solution (4.4 0).
Adjust the pH of the solution to (1,15 ± 0,05) by adding, drop by drop, sodium hydroxide (4.25) or hydrochloric
acid1 + 2, using a pH meter calibrated with a buffer solution of similar pH value (e.g.1,40, see 4.47). Add from a
pipette 5ml of the ammonium molybdate solution (4.42) to the solution (time0). Adjust the pH of the solution to1,60
by adding, drop by drop, the sodium hydroxide solution(4.25) or hydrochloric acid1 + 2. Transfer the solution to
a100ml volumetric flask and rinse the beaker with hydrochloric acid of pH1, 60 (4.9). After20min, add from a pipette
5ml of the citric acid solution (4.4 1), stir and leave to stand for 5min. Then add from a pipette 2ml of the reducing
solution (4.46). Make up to volume with dilute hydrochloric acid of pH1, 60and mix. At time0 + 30min measure the
optical density with the photometer (5.9) against a blank solution prepared in a similar way and using the same
wavelength of a cell of the same optical length as used for the construction of the calibration graph(4.50.3). The
silica concentration in mg SiO2 /100ml is read from the calibration graph.

13.8.2 Expression of results

The soluble silica content is calculated in percent from the formula:

500 x m 25 x 100
Solub le SiO2 =
20 x 1000 x m23

m25
= 2,5 x ( 21 )
m23

m 23 is the mass of the test portion as in 13.2 (m 17) or 13.5.1 (m 20), in grams;

m 25 is the silica content of the solution in accordance with 13.8.1 in mg SIO 2/100 ml.

where

13.9 Total silica

13.9.1 Expression of results

The total silica content is equal to the sum of the pure silica content (13.6) and the soluble silica content (13.8).

13.9.2 Repeatability and reproducibility

The standard deviation for repeatability is 0,10 %. The standard deviation for reproducibility is 0,25 %.

23
ES 1176-2:2005

13.10 Determination of iron (III) oxide

13.10.1 Procedure

Pipette100ml of the solution prepared in accordance with 13.7 from the 500ml volumetric flask into a beaker
compatible with the measuring apparatus (5.11). Then make up with water to a volume suitable for the correct
operation of the equipment. Add 0,5 g amino-acetic acid (4.18) and 0,3 g to 0,4 g of Sulfosalicylic acid indicator
(4.60). Using a pH meter, adjust the pH of this solution to (1,5 ± 0,1) with the ammonium hydroxide 1 + 1 (4.21) and
1 + 10 (4.22). Heat to (47,5 ± 2,5) °C. Place the beaker in the apparatus (5.1 1) set at 520 nm and, while stirring the
solution, titrate with 0,03 mol/l EDTA solution (4.53). In the vicinity of the indicator colour change, construct a
diagram of the optical density values as a function of the volume of EDTA added. The volume V 10 used is
determined from the intersection of the line of greatest slope in the region of the colour change and the line of
almost constant optical density after the colour change.

During the titration, the temperature of the solution shall not exceed 50 °C. Otherwise the determination shall be
repeated. This titrated solution is retained for the determination of aluminium oxide content in accordance with
13.11.1. The presence of titanium oxide (TiO 2) can disturb the determination of iron oxide (Fe2O 3) in the presence
of peroxide and the latter shall be completely decomposed.

NOTE. The presence of titanium affects the speed of the titration of iron by EDTA. This cause of error can be overcome by
proceeding slowly, for example with the help of an automatic burette. It is equally possible to mask the titanium by adding 2ml of
sulfuric acid1 + 1 to the solution before titration.

13.10.2 Expression of results

The iron (III) oxide content is calculated in percent from the formula:

0,03 x 159 ,692 x 500 x V10 X f D

Fe 2 O3 = x 100
2 x 1000 x 100 x m23

V10 x FD
= 1,1977 x ( 22 )
m23

where

V10 is the volume of 0,03 mol/1 EDTA solution used for the titration, in milliliters;

fD is the factor of the 0,03 mol/1 EDTA solution defined in 4.53;

m 23 is the mass of the test portion as in 12.2 (m17) or 13.5.1 (m 20), in grams.

13.10.3 Repeatability and reproducibility

The standard deviation for repeatability is 0,08%. The standard deviation for reproducibility is 0,15 %.

13.11 Determination of aluminium oxide

13.11.1 Procedure

Cool the solution retained from 13.10.1 to room temperature. Then add 5ml of acetic acid (4.1 7) then, drop by drop,
the ammonium acetate solution(4.44) so as to obtain a pH of (3,05 ± 0,05). This zone shall be strictly adhered to
and controlled by means of a pH meter. Under no circumstances is a pH of 3,1 to be exceeded. Bring to the boil,
add three drops of the copper complexonate solution(4.54) and 10 drops of PAN indicator (4.61). During the
titration, the solution shall be kept gently boiling (work in a fume cupboard). Titrate with the 0,03 mol/l EDTA

24
 ES 1176-2:2005

solution (4.5 3) until the colour changes from violet-pink to pale yellow. When the pink colour reappears, add the
0,03 mol/l EDTA drop by drop until the yellow colour persists for at least 1min.

13.11.2 Expression of results

The aluminium oxide content is calculated in percent from the formula:

0 ,03 x 101,961 x 500 x V11 x FD

Al 2 O3 = x 100 ( 23 )
2 x 1000 x 100 x m 23

V11 XFD
= 0 ,7647 X
m23

where

v11 is the volume of 0,03 mol/l EDTA solution used for the titration, in milliliters;

fD is the factor of the 0,03 mol/l EDTA solution defined in 4.53.3;

m 23 is the mass of the test portion as in 13.2 (m17) or 13.5.1 (m20), in grams.

13.11.3 Repeatability and reproducibility

The standard deviation for repeatability is 0,10 %. The standard deviation for reproducibility is 0,25 %.
13.12 Determination of calcium oxide by EGTA (reference method)
13.12.1 Procedure

Pipette25ml of the solution prepared in accordance with 13.7 from the500ml volumetric flask into a beaker
compatible with the measuring apparatus(5.11) and make up to the same volume as in 4.55.3 with water and then
add25ml of the triethanolamine solution 1 + 4 (4.45). Adjust the pH of this solution to 12,5 (using a pH meter) with a
sodium hydroxide solution (4.25). Add about 0,1 g of murexide (4.57) or calcein indicator (4.58). Place the beaker
in the apparatus (5.1 1) set at 520 nm when using calcein or at 620 nm when using murexide and, while stirring,
titrate with the 0,03 mol/l EGTA solution (4.55). In the vicinity of the colour change, construct a diagram of the
readings from the measuring apparatus as a function of the volume of EGTA added. The volume V 12 used is
determined from the intersection of the line of greatest slope in the region of the colour change and the line of
almost constant optical density after the colour change.

13.12.2 Expression of results

The calcium oxide content is calculated in percent from the formula:

0,03 x 56 ,08 x 500 x V12 x f G

CaO = X 100
1000 x 25 x m23

V12 x FG
= 3,3648 x ( 24 )
m23

25
ES 1176-2:2005

where

V12 is the volume of 0,03 mol/l EGTA solution used for titration, in milliliters;

fG is the factor of the 0,03 mol/l EGTA solution defined in 4.55.3;

m 23 is the mass of the test portion as in 13.2 (m 17) or 13.5.1 (m 20), in grams.

NOTE Strontium oxide is determined and expressed as calcium oxide.

13.12.3 Repeatability and reproducibility

The standard deviation for repeatability is 0,18 %. The standard deviation for reproducibility is 0,37%.

13.13 Determination of magnesium oxide by DCTA (reference method)

13.13.1 Procedure

Pipette50ml of the solution prepared in accordance with 13.7 from the500ml volumetric flask into a beaker
compatible with the measuring apparatus(5.11), add50ml of triethanolamine solution 1 + 4 (4.45) and a volume V
13 of the EGTA solution. The volume V 13 required is calculated in millilitres from the formula:

V13=2 V12 +1,5 (25 )

where

V12 is the volume of the EGTA solution used for titration in accordance with 13.12.1, in milliliters;

V13 is the volume of the EGTA solution, in milliliters.

After addition of the calculated volume of EGTA solution, dilute with water to a volume suitable for the correct
operation of the apparatus. Using a pH meter, adjust the pH of this solution to 10,5 with concentrated ammonium
hydroxide. Add about 0,1g of methylthymol blue indicator (4.62).

Place the beaker in the apparatus (5.11) set at 620 nm and, while stirring the solution, titrate with the0,01 mol/l
DCTA solution (4.56). In the vicinity of the colour change of the indicator, plot a graph of the optical density values
as a function of the volume of DCTA added. The volume V 14 used is determined from the intersection of the line
of

greatest slope in the region of the colour change and the line of almost constant optical density after the colour
change.

13.13.2 Expression of results

The magnesium oxide content is calculated in percent from the formula:

0,01 x 40 ,311 x 500 x V14 f c

MgO = 100
1000 x 50 Xm 23

V14 X f c
= 0 ,4031 x ( 26 )
m 23

26
 ES 1176-2:2005

where

V14 is the volume of 0,01 mol/l DCTA solution used for the titration, in milliliters;

fc is the factor of the 0,01 mol/l solution defined as 4.56.3;

m 23 is the mass of the test portion as in 13.2 (m 17) or 13.5.1 (m 20), in grams.

13.13.3 Repeatability and reproducibility

The standard deviation for repeatability is 0,15 %. The standard deviation for reproducibility is 0,15%.

13.14 Determination of calcium oxide by EDTA (alternative method)

13.14.1 Restriction on the method

This method shall be preceded by the determination of manganese content (see clause 12 and also 13.15.1).

13.14.2 Procedure

Pipette50ml of the solution prepared in accordance with 13.7 from the500ml volumetric flask into a beaker
compatible with the measuring apparatus (5.11). Then dilute with water to a volume suitable for the correct
operation of the equipment. Add50ml of the triethanolamine solution1 + 4 (4.45). Using a pH meter, adjust the pH
of this solution to12,5 with the sodium hydroxide solution (4.25). Add about 0,1g of murexide (4.57) or calcein
indicator (4.58). Place the beaker in the apparatus (5.11) set at 620 nm when using murexide or at 520 nm when
using calcein and, while stirring the solution, titrate with the 0,03mol/l EDTA solution (4.53). In the vicinity of the
colour change of the indicator, plot a graph of the optical density values as a function of the volume of EDTA
added. The volume V 15 used is determined from the intersection of the line of greatest slope in the region of the
colour change and the line of almost constant optical density after the colour change.

13.14.3 Expression of results

The calcium oxide content is calculated in percent from the formula:

0,03 x 56,08 x 500 x V15 x f D

CaO = x 100
1000 x 50 Xm23

V15 Xf D
= = 1,6824 x ( 27 )
m23

where

V15 is the volume of 0,03 mol/l EDTA solution used for the titration, in milliliters;

fD is the factor of the 0,03 mol/l EDTA solution defined in 4.53.3,

m 23 is the mass of the test portion as in 13.2 (m 17) or 13.5.1 (m 20), in grams.

NOTE. Strontium oxide is determined and expressed as calcium oxide.

27
ES 1176-2:2005

13.14.4 Repeatability and reproducibility

The standard deviation for repeatability is 0,15 %. The standard deviation for reproducibility is 0,43 %

13.15 Determination of magnesium oxide by EDTA (alternative method)

13.15.1 Restriction on the method

For the rare particular instances where cements have a manganese oxide (Mn 2 O 3 ) content greater than 0,5 %,
the method of determination of magnesium oxide by DCTA (13.13) is applicable. Indeed in this case, the alternative
method gives high results, or it requires a preliminary separation of hydroxides by precipitation.

13.15.2 Procedure

Pipette50ml of the solution prepared in accordance with 13.7 from the500ml volumetric flask into a beaker
compatible with the measuring apparatu s(5.11). Then dilute with water to a volume suitable for the correct
operation of the equipment. Add50ml of the triethanolamine solution 1 + 4 (4.45).

Using a pH meter, adjust the pH of this solution to10,5 with dilute ammonium hydroxide1 + 1. Using a burette, add
the volume V 15 of EDTA required for the titration of calcium oxide previously determined in 13.14.2. Then add
about 0,1g of methylthymol blue indicator (4.62). Place the beaker in the apparatus (5.1 1) set at 620nm and, while
stirring the solution, titrate with the 0,03 mol/l EDTA solution (4.53). In the vicinity of the colour change of the
indicator, plot a graph of the optical density values as a function of the volume of EDTA added. The volume V 16
used is determined from the intersection of the line of greatest slope in the region of the colour change and the line
of almost constant optical density after the colour change.

13.15.3 Expression of results

The magnesium oxide content is calculated in percent from the formula:

0,03 x 40 ,311 x 500 x (V16 − V15 ) f D

MgO = x 100
1000 x 50 Xm 23

(V16 − V15 )
= 1,2093 x ( 28 )
m 23

where

V15 is the volume of EDTA required for the determination of calcium oxide determined in 13.14.2, in milliliters;

V16 is the volume of EDTA required for the determination of calcium oxide and magnesium oxide defined in
13.15.2, in milliliters;

fD is the factor of the 0,03 mol/l EDTA solution defined in 4.53.3;

m 23 is the mass of the test portion as in 13.2 (m17) or 13.5.1 (m20), in grams.

13.15.4 Repeatability and reproducibility

The standard deviation for repeatability is 0,21 %. The standard deviation for reproducibility is 0,25 %.

13.16 Comments on the visual observation of the titrations for the determinations of calcium oxide and magnesium
oxide

28
 ES 1176-2:2005

The methods described in 13.12, 13.13, 13.14 and 13.15 use a photometric determination of the end-points.

It is possible to make visual observations of the titrations but with less precision. The indicators often used for this
purpose are as follows:

a) For the determination of calcium oxide by EGTA: mixed indicator: calcein and methylthymol blue (4.63)
(colour change from pale green to pink). This indicator is suitable also for the photometric determination.

b) For the determination of magnesium oxide by DCTA: methylthymol blue (4.62) (colour change from blue to
grey).

c) For the determination of calcium oxide by EDTA: calcon (4.5 9) (colour change from pink to blue).

d) For the determination of magnesium oxide by EDTA:

a dispersion of 1 g of phthalein purple in 100 g of solid NaCl (colour change from violet to pale pink).

29
ES 1176-2:2005

Annex A
(informative)
Determination of total sulfur

A.1 Procedure
To 1.000g of cement add 25ml of saturated bromine water and while stirring vigorously add 5ml of hydrochloric
acid saturated with bromine. If necessary, heat the solution and break up the cement with the flattened end of a
glass rod until decomposition is complete. Dilute the solution to150ml and heat it to boiling point until all the
bromine has been driven off. Then follow the procedures from the second paragraph of 8.2.

A.2 Calculation

Calculate the sulfur content, S, as a percentage from the formula:

S = W × 13.73

where

W is the mass of barium sulfate (in g).

30
 ES 1176-2:2005

Annex B (informative) Determination of minor constituents

(TiO2 and P2O5 ) and free lime

B.1 Colorimetry

An approximate determination can be made by visual comparison with a colorimetric scale corresponding to known
quantities of the constituent to be determined.

A more precise determination can be made absorptiometrically. Two kinds of spectrophotometric apparatus are in
common use: that employing a prism or grating monochromator capable of selecting a wavelength band of about
1nm, and that using an optical filter of the ordinary or the interference type, allowing the passage of a band of 5nm
to 20nm. The narrower the wave band the more accurately does the additivity law apply to the optical densities
measured.

B.2 Colorimetric determination of titanium

B.2.1 Reagents

B.2.1.1 Ammonium nitrate. Dissolve 20g of ammonium nitrate in 1 l of water and just neutralize to methyl red with
ammonia solution.

B.2.1.2 Hydrogen peroxide. 6 % (20 volumes).

B. 2.1.3 Standard titanium stock solution. Boil for15min a mixture of 4.435g of potassium titanium oxalate dihydrate
with 8g of ammonium sulfate and50ml of sulfuric acid. Cool, dilute with water to 1 1 and mix. One ml contains
1.0mg TiO 2

B. 2.1.4 Standard titanium working solution. Dilute the stock solution ten times to give a solution of which 1ml
contains 0.10mg TiO2.

B.2.2 Procedure

Dilute the filtrate, including the dissolved hydrofluoric acid residue, from a silica separation(13.5.1) to500ml. Take
a50ml aliquot (equivalent to 0.1 g of cement), heat to boiling and neutralize with dilute ammonia solution (1 + 1),
using methyl red indicator. Filter the precipitated hydroxides on a rapid filter paper 8) and wash with hot ammonium
nitrate solution until the washings are chloride-free. Transfer the precipitate to the original beaker, first with water
and then with30ml of hot dilute sulfuric acid (1 +4), taking care to dissolve all the precipitate. Filter if necessary to
remove paper fibres. Cool and transfer to a100ml volumetric flask, add 5ml of hydrogen peroxide, dilute to100ml
and mix the contents. Allow 5min for full colour development before measuring the optical density.

B.2.3 Measurement

The colour can be measured by visual comparison or instrumentally, using a spectrophotometer. With the
monochromator-type instrument, operate at410nm; with the filter-type instrument, use a blue filter of which the
wavelength band is as near as possible to 410nm 9). Prepare a range of standards containing known amounts of
titanium. Each standard should contain30ml of sulfuric acid (1 + 4) and 5ml of hydrogen peroxide in 100ml.
construct a standard curve giving the opti cal density as a function of concentration. Refer the optical density
obtained for the sample solution to this curve and calculate the percentage TiO 2 content.

31
ES 1176-2:2005

B.3 Colorimetric determination of phosphorus

B.3.1 Reagents

B.3.1.1 Ammonium vanado molybdate (AVM).

Dissolve 1g of ammonium vanadate in300ml of water, preferably with the help of mechanical stirring. After
complete solution, add slowly 140ml of nitric acid then400ml of10 % ammonium molybdate solution. Make up the
mixture to 1 l with water.

B. 3.1.2 Standard phosphate solution. Dissolve exactly 0.186g of dry diammonium phosphate in water and dilute to
1 l. One ml contains 0.1mg P2O5.

B.3.1.3 Sodium fluoride solution. Dissolve 20g of sodium fluoride in 1 l of water.

B.3.2 Procedure

Dilute the filtrate, including the dissolved hydrofluoric acid residue, from a silica separation(13.5.1) to500ml. Place
a50ml aliquot (equivalent to 0.1 g of cement) in a100ml volumetric flask, add15ml of AVM reagent(NB.3.1.1) and
allow to stand. (If the iron content of the cement exceeds 3 % Fe 2 O 3 add 5ml of sodium fluoride solution after 20
min). Dilute to100ml and mix. Measure the optical density30min after adding the AVM solution.

B.3.3 Measurement

The colour can be measured by visual comparison or instrumentally, using a spectrophotometer. With the
monochromator-type instrument, operate at 426 nm; with the filter-type instrument, use a filter of which the
wavelength band is as near as possible to 426 nm 10) .

Prepare a range of standards containing known amounts of phosphorus and the same amounts of reagents as the
sample. Construct a standard curve giving the optical density as a function of concentration. Refer the optical
density obtained for the sample solution to this curve and calculate the percentage P 2 O 5 content.

B.4 Estimation of free lime (calcium oxide plus calcium hydroxide)

B.4.1 Special reagents

B.4.1.1 Mixed indicato r. Dissolve 0.05g of methyl red in about40ml of absolute ethyl alcohol, and0.05g of
bromocresol green in about40ml of ethyl alcohol. Mix both solutions and make up to100ml with ethyl alcohol.

B.4.1.2 Absolute ethyl alcohol. This liquid readily absorbs moisture from the atmosphere. It should be kept in tightly
stoppered bottles fitted with an airtight cap, and opened only for the lapse of time necessary for manipulations.

B.4.1.3 Glycol. (1: 2 ethane diol). Ensure that this reagent is pure and anhydrous. It absorbs atmospheric moisture
and should be treated in the same way as absolute alcohol. Ensure that the glycol does not contain more than
0.5% of water.

NOTE Water content in absolute alcohol and glycol can be determined by titration by the Karl Fischer method. Add to each litre
of glycol 5ml of mixed indicator (NB.4.1.1) and adjust if necessary by the addition of alcoholic potassium hydroxide to a green
colour.

32
 ES 1176-2:2005

B.4.1.4 Hydrochloric acid. (0.1 N).

B.4.1.5 Calcium oxide standard. Ignite about 0.20g of calcium carbonate in a weighed platinum crucible at 1000 °C
in an electric furnace. Verify the complete removal of carbon dioxide by re-weighing and record the mass of calcium
oxide.

B.4.2 Procedure

Weigh a 1000g sample into a dry conical200ml flask, add 1g to 2g of dry sand 11) . and about0.5g of dry filter
paper or pulp. Mix thoroughly. Add 40ml of glycol, stopper the flask. Shake or stir vigorously. Place the flask
for30min in a water bath at 65°C to70 °C and shake manually every 5min. Continuous mechanical agitation is
even better.

Filter the mixture under suction through a dry filter of suitable porosity to provide a clear filtrate. Unless the filtration
is rapid it may be necessary to keep the mouth of the sintered glass filter protected by an apparatus which will
remove moisture and carbon

dioxide from incoming air (for instance a close fitting rubber cover connected to guard tubes containing soda-lime
and magnesium perchlorate). Wash with three separate10ml portions of absolute alcohol or hot glycol, carefully
rinsing the conical flask, then remove the filtration flask and titrate with 0.1N hydrochloric acid until the colour
changes (colour changes through brown to orange).

B.4.3 Standardization

Transfer the weighed calcium oxide obtained in B.4.1.5 to a dry conical flask, add40ml of glycol, agitate and heat
as in B.4.2. The lime should dissolve without residue. Nevertheless, filter and titrate as in B.4.2.

B.4.4 Calculation

Calculate the free lime content, Ca , as a percentage from the formula:

100 w
Ca = t X
ts

where

w is the mass of standard calcium oxide (in g);

ts is the volume of hydrochloric acid used in NB.4.3 (in ml);

t is the volume of hydrochloric acid used in NB.4.2 (in ml).

33
ES 1176-2:2005

Annex C (informative)
Determination of propylene glycol
content

C.1 Principle

The cement is extracted with industrial methylated spirits containing decanol as an internal standard. After
centrifuging, the clear solution is analysed by gas liquid chromatography.

C.2 Reagents

C.2.1 Industrial methylated spirits.

C.2.2 Decanol solution (250mg/l). Weigh 0.250g of decan-l-ol and dilute to 1000ml in a volumetric flask with the
industrial methylated spirits.

C.2.3 Propylene glycol solution (500m g/l). Weigh0.100g of propane-1,2-diol and dilute to200ml in a volumetric flask
with the industrial methylated spirits.

C.3 Apparatus

C.3.1 Electric centrifuge 12) , complying with BS 4402, capable of whirling two or more filled centrifuge tubes at a
2
speed controlled to give an acceleration of 7000m/s at the tips of the tubes calculated from the formula:

2 –6
acceleration = 11 n r × 10

where

n is the rate of rotation (r/min);

r is the radial distance to the inside of the tips of the tubes when rotating (mm).

C.3.2 15ml glass vials (with caps), suitable for use with NC.3.1.

C.3.3 Graduated pipettes(10ml and1 ml).

C.3.4 Gas liquid chromatograph equipped with flame ionization detector.

C.4 Method

Weigh1.000g of the sample and place into a glass vial. Pipette into the vial 4.0ml of industrial methylated spirits
and 1.0ml of the decanol solution.

34
 ES 1176-2:2005

2
Place the cap on the vial and shake vigorously for 1min. Centrifuge at an acceleration of 7000 m/s for 5min.
Decant the clear liquid into a clean vial. Inject 1.0µl into the chromatograph using the following operational
conditions.

a) Column 10 % polyethylene glycol (molecular weight 20 000) on diatomite Grade C, acid-

washed150µm to125µm, length 1.5 m, internal diameter 4mm.

b) Carrier gas Nitrogen, flow rate 40ml/min.

c) Column temperature 150 °C.

d) Recorder chart speed 10mm/min.

The chromatograms of the calibration solutions (see NC.5) give peaks due to propylene glycol and decanol at
approximately 7min and14min respectively after the sample is injected. If propylene glycol is present in the sample
then the chromatogram obtained from the sample containing the internal standard will give peaks with similar
retention times. Measure these peak areas either manually or using an integrator. Calculate the ratio:

areaforpropyleneglycol
areafordecanol

Read off the proportion of propylene glycol in the cement from the calibration graph, prepared as in NC.5 and
report it as a percentage to the nearest0.01 %.

C.5 Preparation of calibration graph

Transfer by means of a pipette0.5ml, 1.0ml, 2.0ml, 3.0ml, 4.0ml and5.0ml aliquots of the propylene glycol solution
each into one of six glass vials. Add to each vial1.0ml of the decanol solution and mix thoroughly.

Analyse each mixture on the chrom atograph as in NC.4. Plot a graph of the ratio of the peak areas against
percentage of propylene glycol in 1g of cement. (The above aliquots are equivalent to 0.025%, 0.05%, 0.10%,
0.15%, 0.20% and 0.25% propylene glycol in cement respectively.)

C.6 Normative reference

BS 4402:1982, Specification for safety requirements for laboratory centrifuges.

35
ES 1176-2:2005

Annex D (informative)
Method of analysis of cements by X-ray
fluorescence spectrometry
D.1 General
The method is intended for the determination of the major oxide contents of Portland cement, conforming to
BS12:1991 (see note), within the following compositional ranges.

Oxide %

SiO 2 18 – 24

Al 2 O 3 2.6 – 8

Fe 2 O 3 1.5 – 7

CaO 61 – 69

MgO 0.5 – 4

SO 3 0.2 – 4

K 2O 0.2 – 1.0

It is not considered appropriate to apply this method to the determination of Na 2 O content in view of the
inadequate precision at present obtainable by X-ray fluorescence (XRF) spectrometry using fused beads at the
levels normally present in cements.

NOTE Whilst the method was originally developed for cements conforming to the 1978 and 1989 editions of BS12, the
calibration range has been extended to allow for minor constituents of up to 5%. It is therefore believed that the method and
precision values will be valid for Portland cement conforming to BS 12:1991.

D.2 Principle

The cement is fused with a mixture of lithium tetraborate and lanthanum oxide. The resultant melt is cast to form a
glass bead suitable for introduction into an X-ray fluorescence spectrometer. The intensities of the fluorescent X-
rays of the required elements are measured and the chemical composition of the cement is determined by
reference to previously established calibrations. These have been selected to cover narrow compositional ranges
so that, together with the use of lanthanum oxide as a heavy absorber, matrix effects are minimized. A monitoring
scheme is incorporated to compensate for any short-term instrumental drift and thus to avoid the need for full re-
calibration with every batch of test samples. The frequency of full re-calibration for each particular instrument is
determined by the analyst. An on-going check on the accuracy of the method is made by incorporating beads made
with a certified reference cement with each batch of test samples.

36
 ES 1176-2:2005

D.3 Symbols

I Intensity for an element

IM Intensity for an element from the single monitor bead

IH Intensity for an element from the high monitor bead

IL Intensity for an element from the low monitor bead

m Slope of a calibration line in concentration per unit intensity

k 1,m 1 Intercept (concentration at zero intensity) and slope (concentration per unit intensity ratio)
for an element when using the single monitor method

k 2, m 2 Intercept (concentration at zero intensity) and slope (concentration per unit intensity) for an
element when using the high/low monitors.

C Concentration of an oxide in the calibration standards calculated using a calibration line

CH,CL Concentration of an oxide in the high and low monitors calculated using a calibration line at

the time of calibration

C Actual concentration of an oxide in a standard bead, calculated from the masses given in
D.5

C Average concentration of an oxide in the14 calibration standards, calculated from the

masses given in D.5

C K2O Concentration of K 2 O in the unknowns calculated using the calibration line for K 2 O (as

used in D.11.3)

C’ CaO Apparent concentration of CaO

C ’ CaO Apparent concentration of CaO calculated using the calibration line for CaO, prior to

applying the a-correction for K 2 O

CaO Calculated concentration CaO after applying the !-correction for K2O

s Influence coefficient of potassium on calcium

K Figure of merit

S Calibration standard deviation

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ES 1176-2:2005

D.4 Sample preparation (see D.7)

Remove a100g subsample from the original laboratory sample by repeated riffling, or by use of a rotating sampler,
or by spreading the material in a thin layer and taking about50evenly spaced spoonfuls.

Separate the subsample into coarse and fine fractions by passing through a150 4m sieve. Remove with a magnet
any iron from the material retained on the sieve and then grind the remainder so that it passes the1504m sieve.

Transfer both fractions to a clean, dry, 200ml bottle with an air-tight closure and thoroughly mix by tumbling, rolling
and shaking for at least2 min, (test portion).

D.5 Reagents

D.5.1 Lithium tetraborate flux (purity not less than 99.99%). Ignite the lithium tetraborate at (600 ± 25) °C for a
minimum of 2h and allow to cool over a suitable desiccant immediately prior to weighing.

D.5.2 Lanthanum oxide (purity not less than 99.9%). Sieve the lanthanum oxide to pass a1504m sieve, ignite at
(1000 ± 25)°C for a minimum of 1h and allow to cool over a suitable desiccant immediately prior to weighing.

NOTE See ND.8.1 e) for action to be taken after changing the batch of either of the flux components.

D.5.3 Chemicals for synthetic calibration standards. Ignite the high quality purity chemicals at the temperature and
for the time specified in Table ND.1 and allow to cool over a suitable desiccant immediately prior to weighing. It is
necessary for the silicon dioxide and calcium carbonate to have purities of not less than99.99 %, the aluminium,
iron and magnesium oxides to have purities of not less than99.95 %, and the remaining reagents to be of analytical
reagent quality or better.

Table D.1 — Ignition conditions for pure standards

Temp. 0C Time h

Silicon dioxide (SiO 2 ) 1200 1

Aluminium oxide (Al 2 O 3 ) 1200 1

Iron oxide (Fe 2 O 3 ) 700 1

Calcium carbonate (CaCO 3 ) 220 2

Magnesium oxide (MgO) 1200 1

Calcium sulfate (CaSO 4 .2H 2 O) 500 1

Potassium carbonate (K 2 CO 3 ) 220 2

D.6 Apparatus

D.6.1 General. Vessels used for the fusion of samples with the flux and for casting the beads, made from a
platinum alloy which is not wetted by the melt.

NOTE Platinum 95 %/ gold 5 % is suitable.

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 ES 1176-2:2005

D.6.2 Fusion dishes, of sufficient capacity to hold the quantity of unfused sample and flux required by the size of
the casting mould.

NOTE A fusion dish of50ml capacity is generally suitable.

D.6.3 Casting moulds, designed to give a circular bead of a diameter within the range 35mm to 40mm and of
thickness to exceed the critical depth for the element lines used in analysis, with sides set at a suitable angle to the
vertical, to ensure that the beads are readily released. The moulds are frequently polished and examined for
flatness, unless the top surface is used as inND.8.2, and reforming is carried out if there is any noticeable bowing.
Carry out calibration and analysis using the same pattern and size of casting mould throughout.

NOTE It is usually necessary, especially when using moulds of small size, to place the mould on a heat reservoir, e.g. a small
piece of refractory material, so that the bead does not crack as a result of rapid cooling. D.6.4 Fusion mould. An alternative
method is fusion in a dish followed by casting into a mould, for which a combined vessel functioning both as a fusion dish and a
casting mould (see Figure ND.1) may be used. It is necessary for the capacity of the dish to be sufficient to hold the unfused
sample and flux required to fill the mould part of the vessel when fused. The mould part of the vessel has the same
specifications as given in D.6.3. However, where such combined vessels are used, only the top surface of the bead is suitable
for measurement (seeD.8.2).

D.7 Preparation of beads

D.7.1 Number of tests

Carry out all determinations on test samples and calibration standards on duplicate beads.

D.7.2 Loss on ignition

Determine the loss on ignition, L, of the test portion using the method described in clause 7 and calculate the result
to two decimal places. Calculate, to four decimal places, the mass of sample in grams, W L , required to give
1.0000g of ignited sample using the equation:

39
ES 1176-2:2005

100
WL =
100 − L
Alternatively, take approximately 1.5g, carry out a test for loss on ignition in accordance with clause7 and use the
ignited sample for bead preparation.

D.7.3 Weighing

Weigh (9.000 ± 0.001) g of the freshly ignited lithium tetraborate flux, (1.000 ± 0.001) g of the freshly ignited
lanthanum oxide and either (W L ± 0.0001)g of the test portion or (1.0000± 0.0001)g of freshly ignited test portion,
into a glass container. Stopper the container and mix thoroughly.

NOTE It is not necessary to stopper the container completely after weighing the two flux components. In practice a small
amount of moisture, picked up by the flux, aids the mixing and the transfer to the fusion dish.

D.7.4 Fusion

Transfer the mixture as completely as possible to the fusion dish.

NOTE If desired,1.01ml of1 % aqueous lithium iodide may be added to aid bead release.

Place the fusion dish in the furnace at (1100± 20)°C. After 5 min remove the dish, swirl the melt and return it to the
furnace. Place the casting mould (with the refractory reservoir if used, see note to ND.6.3) in the furnace.

After a total fusion time of10min (± 10s) remove the casting mould and reservoir, swift the melt and pour into the
mould as quickly as possible. Cover with a beaker and allow to cool. Remove the bead from the casting mould; if
this is not easily achieved, tapping the casting mould gently onto a firm warm surface will normally release it.
Inspect the bead surface to be analysed for blemishes and if these are present reject the bead. Alternative
techniques for bead preparation may be used providing the following criteria are satisfied:

a) the same preparation technique is applied consistently;

b) the melts produced are homogeneous;

c) there is no measurable loss of any component from the sample during fusion;

d) any loss of flux during fusion is reproducible;

e) the process does not contaminate the sample;

f) beads produced are free from blemishes on the analytical surface.

D.8 Measurement

D.8.1 Instrument requirements

Owing to the inherent differences in commercial XRF instruments it is not possible to specify conditions precisely;
in consequence the requirements for the instrument to meet the needs of the analysis are as follows.

a) The instrument is used and maintained in accordance with the limitations imposed by the manufacturer.

b) The detector is used within its linear response region.

c) The X-ray line, crystals, collimators, detectors, use of off-peak backgrounds and pulse height analysis are
chosen to avoid line overlap wherever possible.

d) The differential detection limit, D, for each element is given by the equation

40
 ES 1176-2:2005

D = 4m √ N EL

where

m1 m
m= or m = 2 according to the monitor method used (see ND.9);
NM t

where

NM is the total number of counts on the single monitor;

t is the counting time (in s);

NEL is the total number of counts at the mean element concentration.

NOTE For elements where there is no bead containing the mean concentration (SiO 2 , CaO, SO 3 ) N EL is obtained by linear
interpolation from the two beads on either side of that concentration.

With the instrumental parameters used, it is necessary for the instrument to satisfy the maximum allowable
differential detection limits given in Table ND.2. However, operators should strive for the lowest differential
detection limits obtainable within practical counting times. It is necessary that the chosen counting time as
determined in this clause is used for all measurements.

e) In order to maintain the ongoing accuracy of the method, a bead prepared with the same batch of flux and
lanthanum oxide as each batch of test portions, but using a certified reference cement, is presented to the
instrument with that batch of test samples. It is necessary that the determined value for each element lies
within ± D/2 [see item d)] of the certified value. If this is not the case after repeated measurements,
undertake recalibration for that element. If a calibration change has occurred immediately after the use of
a new batch of flux component, prepare new calibration standards.

Table D.2 — Maximum allowable differential detection limits

Oxide Maximum allowable differential detection limit

%

SiO 2 0.30

Al 2 O 3 0.15

Fe 2 O 3 0.05

CaO 0.25

MgO 0.20

SO 3 0.10

K2O 0.05

41
ES 1176-2:2005

D.8.2 Presentation of the bead

Place the bead in the instrument such that the bottom (flat) surface is presented to the X-ray beam for analysis.
The suitability of this method using the top (convex) surface of beads has not been verified, but providing it can be
demonstrated that the precision is not inferior, then its use is permitted. In this case additional requirements for the
specifications of the casting and fusion moulds are as follows.

There is an adequate horizontal rim to the casting mould or, in the case of fusion moulds, interposed between the
top of the mould and the sides of the dish. The mass of melt is sufficient to fill the mould (or mould section in the
case of fusion moulds) and give a reproducible convex top surface.

D.8.3 Measurement of intensities

Measure and record, for the appropriate counting time [see D.8.1 d)], the intensities of the seven elements in either
the single monitor bead (I M ) or the high and low monitor beads (I H and I L ); (see D.9.2 or D.9.3). Then measure
and record, for the same counting time, the intensities (I) of the same elements in a maximum of two test sample
beads. Repeat this cycle until the batch of test samples is complete.

D.9 Compensation for instrumental drift

D.9.1 General

This may be achieved by one of two methods, using either a single monitor bead or a pair of high and low monitor
beads. Ignition of reagents to use is not necessary in the preparation of monitor beads.

D.9.2 Single monitor method

Prepare a bead using the masses of oxides, carbonate, sulfate and flux specified in Table ND.3 and following the
procedure given in D.7.3 and D.7.4.

Table D.3 — Mass of ingredients to be used for single monitor bead

Ingredient Mass g
SiO2 0.2
Al 2O 3 0.1
Fe 2O 3 0.1
CaCO3 1.0
MgO 0.1
K 2CO3 0.1
CaSO4 0.1
La2O 3 1.0
Flux 8.9

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 ES 1176-2:2005

D.9.3 High and low monitors method

Prepare beads using the masses of oxides, carbonate, sulfate and flux specified in Table ND.4 and following the
procedure given in D.7.3 and D.7.4.

Table D.4 — Mass of ingredients to be used for “high and low” monitor beads

Ingredient High (g) Low (g)

SiO2 0.3 0.1

Al 2O 3 0.1 Nil

Fe 2O 3 0.1 Nil

CaCO3 1.2 1.0

MgO 0.1 Nil

K 2CO3 0.1 Nil

CaSO4 0.1 Nil

La2O 3 1.0 1.0

Flux 8.5 9.3

D.10 Calibration

D.10.1 Preparation of standards

Prepare a series of seven beads in duplicate using the masses given in Table ND.5 and following the procedure
given in D.7.3 and D.7.4. The composition of these beads corresponds to cements with the compositions given in
Table ND.6.

D.10.2 Measurement

Using the cycle of monitor (single or high and low) and two test samples as in D.8.3 measure and record, for the
appropriate counting time [see D.8.1 e)], the intensities of the seven elements in the14calibration standards
(duplicate beads 1to7 of Table ND.6). The values are designated I and I M (or I H and I L ) as appropriate. a)
Single monitor method. Using a linear regression procedure, determine for each element, except calcium
(seeD.10.3), the slope, m 1 , and intercept, k 1 , of the calibration line of actual concentration, C, (taken from Table
ND.6) against I/I M . Determine the calculated value for each element in the calibration standards from the formula:

C = k 1 + (m 1 × I/I M )

43
ES 1176-2:2005

b) High and low monitors method. Using a linear regression procedure, determine for each element, except calcium
(see D.10.3), the slope, m 2 , and intercept, k 2 , of the calibration line of actual concentration, C, (taken from Table
ND.6) against I. Then determine the calculated concentration, and , of the high and low monitors from intensities I
H and I L using the formulae:

CH= k 2 + (m 2 × I H ) and

CL= k 2 + (m 2 × I L ) respectively.

Determine the calculated value for each element in the calibration standards from the formula:

 (C H - C L )X(I H - I) 
C=CH-  
 (I H - I L ) 

Table D.5 Calibration standards: mass of ingredients required for e ach fusion

Ingredient Bead number

1 2 3 4 5 6 7
g g g g g g g

SiO2 0.2400 0.1950 0.2040 0.2230 0.1800 0.1870 0.2140

Al 2O 3 0.0720 0.0810 0.0260 0.0540 0.0450 0.0630 0.0360

Fe 2O 3 0.0150 0.0610 0.0680 0.0420 0.0530 0.0230 0.0340

CaCO3 1.0422 1.0912 1.0960 1.1487 1.1354 1.1886 1.1992

MgO 0.0110 0.0170 0.0400 0.0260 0.0220 0.0320 0.0050

K 2CO3 0.0147 0.0059 0.0029 0.0117 0.0088 0.0176 —

CaSO 4 0.0680 0.0306 0.0459 0.0034 0.0578 0.0170 0.0391

La2O 3 1.000 1.000 1.000 1.000 1.000 1.000 1.000

9.000
Li2B4O7 9.000 9.000 9.000 9.000 9.000 9.000

44
 ES 1176-2:2005

Table D.6 — Composition of calibration standards

Oxide Bead number

1 2 3 4 5 6 7 Mean
% % % % % % %

SiO2 24.0 19.5 20.4 22.3 18.0 18.7 21.4 20.6

Al 2O 3 7.2 8.1 2.6 5.4 4.5 6.3 3.6 5.4

Fe 2O 3 1.5 6.1 6.8 4.2 5.3 2.3 3.4 4.2

CaO 61.2 62.4 63.3 64.5 66.0 67.3 68.8 64.8

MgO 1.1 1.7 4.0 2.6 2.2 3.2 0.5 2.2

SO3 4.0 1.8 2.7 0.2 3.4 1.0 2.3 2.2

K 2O 1.0 0.4 0.2 0.8 0.6 1.2 0.0 0.6

D.10.3 Influence of potassium on calcium

To calibrate for calcium it is necessary to know the influence coefficient (!) of potassium on calcium. This is defined
by the equation:

CCaO = C' CaO (1 + aC K2 O ).

NOTE This equation is based on an alpha coefficient expressed in terms of per cent concentration units. Where ! has been
calculated from intensity or other units, an appropriate conversion is required. Hence, for calcium, utilize in D.10.2 a) or D.10.2
b) the calibration lines of apparent concentration, calculated from:

CCaO
C 'CaO =
1 + aCK2 O

The value of !, which will be specific for a particular set of instrumental parameters, may be obtained by one of the
following means:

a) from a published theoretical paper;

b) calculated using appropriate computer software;

c) determined using the following method. Prepare two beads in duplicate using the masses given in Table
ND.7 and following the procedure given in D.7.3 and D.7.4.

Measure the intensities for calcium on each bead using identical measuring conditions to those used in the main
calibration, and calculate ! for potassium on calcium using the formula:

45
ES 1176-2:2005

I1 − I 2
a+
10XI 2

where

I1 is the intensity for calcium inbead 1;

I2 is the intensity for calcium in bead 2

Table D.7 — Composition of beads for determination of a -correction

Ingredient Bead 1 Bead 2

Mass g Equivalent oxide Mass g Equivalent oxide

% %

SiO 2 0.3500 35 0.2500 25

CaCO 3 1.1600 65 1.1600 65

K 2 CO 3 0 0 0.1467 10

La 2 O 3 1.000 — 1.000 —

9.000
Li 2 B 4 O 7 9.000 — —

D.10.4 Examination of calibration data

Examine the data to determine whether linear calibration has been obtained (for calcium after applying the !
correction), with K values not exceeding 0.05,

S
where K=
C

S=
∑ (C − C ) 2

(n − 2 )

n is the number of standards (7 duplicate beads, i.e. 14).

If higher K values are obtained, examine the calibration data for outliers and, if necessary, re-make the standards.

C − K 
NOTE If C differs from by more than 2.6  b  , where
 

46
 ES 1176-2:2005

k = k 1 or k 2 and b = I M /m 1 or 1/m 2 as appropriate, then the measurement may be considered to be an outlier

rated at the 1% significance level and excluded.

If difficulty is still encountered in achieving these requirements, check the sensitivity for that element [see D.8.1d)].

D.11 Measurement of test samples

D.11.1 Single monitor method

Calculate the oxide content of the test sample for all elements except calcium using the equation: % oxide (as-
received basis)

100 − loss 
= [ K1 + m1I / IM ] X 
 100 

D.11.2 High and low monitors method

Calculate the oxide content of the test sample for all the elements except calcium using the equation:

% oxide (as-received, basis)

 (CH − CL )( IH − I )  100 − loss 

= CH −  X  100 
 ( IH − IL )   

D.11.3 Calculation of calcium oxide content

Calculate:

a) an apparent calcium oxide content of the test sample

( C’CaO ) and the potassium oxide content of the test sample

(CK2O) using the equation in D.10.2 a)or D.10.2 b) as appropriate;

b) the corrected calcium oxide content using the equations:

100 − loss
CcaO= C’CaO (1+aCK 2O) and % CaO in the test sample =C caO X (as - received basis)
100

D.12 Precision

D.12.1 The precision values for SiO 2 and CaO are given in Table ND.8.

47
ES 1176-2:2005

Table D.8 — Precision values for SiO2 and CaO

13.16 Range r1 r2 R
Oxide
% % %
%

SIO2 19.9 to 23.4 0.17 0.28 0.49

CaO 64.2 to 66.4 0.27 0.46 0.63

D.12.2 The precision value at a particular level of concentration of Al 2 O 3 , Fe 2 O 3 , MgO, K 2 O and SO3 is
calculated as:

r 1 (or r 2 or R) % = b √c

where

b is the multiplier from table ND.9;

c is the level of concentration in %.

Table D.9 — Multipliers for precision values for Al 2 O 3 , Fe 2 O 3 , MgO, K 2 O and SO 3

Oxide Range r1 r2 R
% % % %

Al 2 O 3 3.1 to 6.7 0.050 0.065 0.099

Fe 2 O 3 2.3 to 5.0 0.029 0.038 0.077

MgO 0.9 to 2.7 0.094 0.097 0.143

K 2O 0.2 to 1.0 0.018 0.025 0.101

SO 3 1.4 to 3.7 0.035 0.077 0.151

D.12.3 The precision information given here was obtained from an experiment carried out in the period1986
to1988, involving12 laboratories. The experiment was designed, and the data analysed, by following the principles
set out in BS5497-1. Seven cements were used with the compositions shown in Table ND.10. Approximately 5kg
of each of these cements was homogenised and one100g sample of each sent to each participant. The participants
were required to calibrate their instruments by the procedure described in the method, make two beads from each
sample, then do two analyses on each bed one or two weeks apart.

D.12.4 Each of the values r 1 , r 2 and R is a value which should be exceeded on only 1in20occasions by the
difference between two test results:

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 ES 1176-2:2005

r 1 should be used when the two results are obtained from repeat runs on the same bead (and obtained by the
same operator, using the same equipment);

r 2 should be used when the two results are obtained from different beads made from the same cement sample
(and obtained by the same operator, us ing the same equipment);

R should be used when the two results are obtained by different operators, using different equipment, analysing
different beads made from the same cement sample. The precision values were first calculated for each cement
separately. For SiO 2 and CaO the ranges of concentrations in the seven cements were numerically small, so
values of r 1 , r 2 and R were calculated as averages over the seven cements.

These values are given in Table ND.8. For the other oxides the precision values varied with the level of
concentration of the oxides, so equations of the form given in D.12.2 are used to provide a concise summary of the
results.

Table D.10. Composition of cements used in precision experiment

SiO 2 Al 2 O 3 Fe 2O 3 CaO MgO SO 3 K 2O
Cem Type
%
ent % % % % % %

XP1 21.0 4.9 2.8 64.2 1.60 3.7 1.04

14 RHPC1)

XP2 OPC1) 19.9 5.5 3.3 64.7 2.70 2.6 0.48

1)
XP3 OPC 20.1 6.7 2.3 65.2 1.18 3.1 0.60

1)
XP4 OPC 20.7 5.1 2.9 64.8 2.33 2.6 0.76

2)
XP5 CPA55 23.4 3.1 2.5 66.3 1.17 1.9 0.21

XP6 Ground 21.4 6.1 2.5 66.4 0.96 1.4 0.62

clinker

3)
XP7 SRPC 22.3 3.4 5.0 65.0 0.89 2.2 0.70

1) Conforming to BS 12.
2) Conforming to F P 15-301 (identical with DD ENV 197-1).
3) Conforming to BS 4027.

D.12.5 The data obtained in the precision experiment were examined for outliers and stragglers using the methods
described in BS5497-1. All the data for one laboratory were excluded from the calculation of the CaO precision
values, all the data from another laboratory were excluded from the calculation of the SO 3 precision values, and all

49
ES 1176-2:2005

the data from two laboratories were excluded from the calculation of the K 2 O precision values. Some other data
were also excluded.

D.13 Equivalence of X-ray fluorescence spectrometry method

Table ND.11 and able ND.12 offer supportive evidence for the equivalence of the method to the reference methods
as required by clause1. The precision figures are compared to those obtained from the co-operative XRF CERILH
exercise (1986/7). Table ND.12 shows comparisons to wet analysis figures for two of the samples from the
precision experiment.

Table D.11 — Comparison of precision values for CERILH inter laboratory test sample (XP5)
oxide r1 R

BSI Panel % CERILH % BSI Panel % CERILH %

SiO 2 0.17 0.25 0.60 0.56

Al 2 O 3 0.09 0.11 0.23 0.25

Fe 2 O 3 0.04 0.06 0.11 0.18

CaO 0.27 0.31 0.74 0.74

MgO 0.10 0.08 0.13 0.19

SO 3 0.04 0.06 0.21 0.20

Table D.12 — Accuracy checks against wet analysis figures

Oxide Sample XP6 Sample XP5

BSI (XRF) Blue Circle (wet) BSI (XRF) % CERILH (Wet) %

% %

SiO 2 21.40 21.38 23.40 23.24

Al 2 O 3 6.10 5.97 3.10 3.22

Fe 2 O 3 2.50 2.56 2.50 2.55

CaO 66.40 66.39 66.30 66.60

MgO 0.96 0.97 1.17 1.16

SO 3 1.40 1.44 1.90 1.79

K 2O 0.62 0.60 0.21 0.21

D.14 Reporting

Calculate the average of the results from duplicate beads and report SiO2 and CaO to one decimal place and the
other oxides to two decimal places.

50
 ES 1176-2:2005

D.15 Informative references

BS 12:1991, Specification for Portland cement.

ES 4027:1991, Specification for sulfate-resisting Portland cement.

ES 5497, Precision of test methods.

ES 5497 Guide for the determination of

Part 1:1987, repeatability and reproducibility for a standard test method by interlaboratory tests.

DD ENV 197-1:1994, Cement. Composition, specifications and conformity criteria Part1: Common cements.

51
ES 1176-2:2005

Annex
(informative)
Methylene blue test

E.1 Object

The object of the present standard is a description of the method for the determination of the blue value of the fine
fraction of a sand.. It also describes a rapid method of checking the conformity of a sand with a specified blue
value.

E.2 Field of application

The present standard is applicable to sands of natural or artificial origin, for use in building and public works.

E.3 Purpose of the test

This test permits the measurement of the capacity of the fine particles of a sand to adsorb methylene blue.

Since methylene blue is adsorbed preferentially by clays, organic substances and iron hydroxides, this capacity
takes account of the total surface activity of these elements.

The blue value of the fines is the quantity of methylene blue adsorbed by100g of fines.

E.4 Principle of the test

The test consists of measuring, by titration, the adsorption capacity of the material.

Aliquots of methylene blue solution are injected successively into the water bath containing the test sample. The
adsorption of the blue is checked after each addition by making a stain on a filter paper (stain test, see E.7.2.1).

For a simple conformity check, the specified quantity of blue is injected at one time.

52
 ES 1176-2:2005

E.5 Apparatus

E.5.1 Specific apparatus

14.1.1 Burette
3 3
Capacity: 100cm or 50 cm
3 3
graduation 0.1cm or 0.2cm
2
Filter paper: analytical, ash-less (<0.010); weight: 95 g/m

thickness: 0.20mm, filtration rate:75;

retention: 8µm.

Glass rod: length 300mm; diameter 8 mm.

Blade stirrer, rotating between 400 min-1 and 700 min-1.

500 ml beaker (glass or plastics) of diameter about 100 mm.

E.5.2 Apparatus for general use

Balance, the capacity of which is compatible with the mass of the test sample and is accurate to within about 1%.

Stopclock or stopwatch.

Sampling equipment 15) .

E.5.3 Materials

Methylene blue solution of medicinal quality at(10 ± 0.1)g/l.

Demineralized or distilled water.

E.6 Calculation of the sample size Knowing the contents of moisture, w, and of fines, f, (see
standard F P 18-597+ + ) calculate the mass of the test sample, to the nearest1 g, including the
water content, by the formula :

(w + 100 )
Mh= f
f

where

f’ represents the quantity of fines, in g, which it is desirable to have in the test sample (about 30g).

53
ES 1176-2:2005

E.7 Test method

E.7.1 Dispersing the test sample

Place the test sample into a 500ml beaker with 200cm3 of demineralized or distilled water. Stir for one minute at700
–1
min , then continuously at 400 min –1 during the whole duration of the test using the stirrer, the blades being
situated at 1cm above the bottom of the beaker.

E.7.2 Determination by titration of the quantity of blue adsorbed.

E.7.2.1 Description of the stain test

Following each injection of blue (see E.7.2.2), this test consists of using the glass rod to pick up a drop of
suspension which is deposited on the filter paper. The stain which is formed comprises a central deposit of
material, tinted by a generally strong blue colour, surrounded by a colourless wet zone.

The drop taken shall be such that the diameter of the deposit is between 8mm and12mm.

The test is considered to be positive if, in the wet zone, a light blue halo appears around the central deposit. It is
considered to be negative if the halo is colourless.

E.7.2.2 Titration

Using the burette, add 5cm 3 of blue solution to the beaker, this addition being followed by the stain test on the filter
paper.

Proceed in this way until the test becomes positive. At this stage, allow the adsorption of the blue to take place,
while carrying out tests every minute without adding anything.

If the light blue halo disappears from the stain before the fifth minute, proceed with new unit additions of blue,
which are:
3 3
5cm as before, if the volume of the blue solution already added is more than or equal to 30cm , or
3 3
2cm if this volume is less than 30cm .

Follow each addition by tests carried out every minute. Repeat these operations until the test remains positive for
five consecutive minutes; the titration is then considered finished.

NOTE Clean the apparatus as soon as the tests are finished, the blue deposits being easily removed when they are fresh. The
apparatus can easily be cleaned with water. If detergents are used, then a final thorough rinse in water is necessary.

E.8 Expression of results

The blue value of the fines expressed in grams of blue for100g of fines is given by the formula:

V
VB =
f

where

3
V is the final volume of solution added (in cm ).

54
 ES 1176-2:2005

E.9 Conformity control in relation to a given specification

The specification is expressed as blue value for 100g of fines; let this value be s.

The volume of the blue solution to be added at one time is therefore:

V´ = f´ · s

The stain test is carried out after stirring for 8min. If it is positive, the sand conforms to the specification; if it is
negative, then add a volume of blue solution equal to:

f .s
10
If the test is still negative after 5min, carry out the titration in accordance with NE.7.2; if the test is positive, the sand
conforms to the specification.

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ES 1176-2:2005

Annex F
(informative)
Determination of total organic carbon

F.1 Introduction
It describes a reference method and two alternative procedures which have been shown to give similar results for
the total organic carbon content in naturally occurring limestone.

F.2 Scope and field of application

The following procedures are suitable for the determination of the total organic carbon content (TOC) in naturally
occurring limestone which si intended to be used for the production of fillerized cements. Procedure1 shall be taken
as the reference method. Alternatively the procedures 2 and 3 may be used. All three procedures have been
proved by comparative tests to give similar results for the determination of TOC content without statistically
apparent deviations of the mean values.

The three procedures only differ in equipment, cost and in analysis time. The reference method 1 requires the least
expensive apparatus but takes the longest time. The alternative method 2 is moderate in equipment expense and
needs less operation time. The alternative method 3 requires a comparatively expensive, automatic apparatus
which can be used advantageously for analyzing many samples within a short time, once ht e decarbonation stage
has been completed.

F.3 General requirements

In general all procedures consist of the following stages:

decarbonation of the original limestone sample; purification of the carrier gas; oxidation of the organic carbon
matter; drying of the CO2 produced by oxidation; measurement of the CO2 content.

The different steps may be performed by various techniques provided they give the same result. The number of
determinations shall be at least two. The result shall be expressed as the mean of the single determinations.
Depending on the size of the raw material a sample of at least 1kg up to10 kg shall be taken, crushed, reduced and
ground to form a representative laboratory sample for analysis. The laboratory sample should pass the90 µm ISO
sieve.

F.4 Wet oxidation method (reference method)

F.4.1 Principle

The carbon dioxide in the limestone is first removed by the use of phosphoric acid. The remaining organic carbon is
then oxidized to carbon dioxide with a strong oxidizing reagent mixture. The liberated carbon dioxide is absorbed
on an inorganic carrier impregnated with sodium hydroxide in a U-tube. The increase in weight is directly
proportional to the carbon content in the sample.

F.4.2 Apparatus

The apparatus for TOC determination is illustrated in Figure F.1. A small vacuum pump or an aspirator is used to
generate reduced pressure in the apparatus. The U-tube (8) is filled to approximately two thirds of its volume with
the absorbent for carbon dioxide and with magnesium perchlorate. The U-tube is then inserted into the apparatus
as shown in Figure F.1 drawing through it about 4 l of carrier gas. At this time the apparatus should be checked for

56
 ES 1176-2:2005

leaks by turning off the drying tower tap whilst keeping the small vacuum pump or the aspirator trap fully open. If
leaks are absent, the gas flow through the bubble counter (9) stops completely. After this, check that the taps of the
U-tube (8) are turned off, transfer it to a desiccator for10 min, wipe it with a clean cloth and weigh to the
nearest0.0 001g. Reassemble the apparatus as shown in Figure F.1.

F.4.3 Reagents

Use only reagents of analytical quality and distilled water or water of equal purity for analysis. The densities of
concentrated liquid reagents are expressed in g/cm3. The degree of dilution is expressed as a volumetric sum (i.e.
nitric acid1 + 9 means that1 volume of concentrated nitric acid has to be mixed with 9volumes of water).

Phosphoric acid, H 3 PO 4 , ρ = 1.71 to 1.75

Sulfuric acid, H 2 SO 4, ρ= 1.84

Nitric acid, HNO 3, ρ = 1.40 to 1.42

Nitric acid, dilute, 1 + 9

Hydrogen peroxide, H 2 O 2, ρ = 1.11

Hydrogen peroxide, dilute, 1 + 9

Phosphorus pentoxide, P 2 O 5

Potassium dichromate, K 2 Cr 2 O 7

Potassium iodate, KIO 3

Chromium trioxide, CrO 3

Ammonium hydroxide, NH 4 OH, ρ = 0.91

Lead chromate, PbCrO 4

Zinc wool, Zn

Oxidizing mixture. To85ml sulfuric acid in a250ml beaker add, in order, 15ml phosphoric acid,20g phosphorus
pentoxide,15g potassium dichromate, and 1g potassium iodate. Heat the mixture carefully to about170 °C and
keep for 5min at this temperature with occasional stirring with a thermometer. After cooling, store the mixture in a
stoppered bottle.

Chromic acid. Dissolve 5g of chromium trioxide in10ml of water. Add sulfuric acid with stirring, until the chromium
trioxide, which initially precipitates, is just redissolved. Silver gauze, Ag. Wash the silver gauze with ammonium
hydroxide, nitric acid 1 + 9 and hydrogen peroxide. Rinse the gauze with water between each washing.

Magnesium perchlorate. Mg (ClO 4) 2 with a particle size between0.6mm and1.2 mm. Absorbent for carbon dioxide.
NaOH on an inert inorganic carrier.

Carrier gas. Air (carbon dioxide free), alternatively the use of oxygen, nitrogen or argon is possible.

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ES 1176-2:2005

F.4.4 Procedure
Weigh 1g of the limestone sample to the nearest0.0001g. Transfer to the 150ml round bottom flask (4), add 2ml of
water and 30ml phosphoric acid. Heat the mixture and boil gently to expel the carbon dioxide. Cool the mixture and
connect the flask to the apparatus. Substitute for the U-tube (8) a glass tube and pass 2 l of carrier gas through the
apparatus, to clear the system of any carbon dioxide. Fit the weighed U-tube again to the apparatus and check
once more for leaks. Open the taps of the U-tube. Add approximately 30ml of oxidizing mixture to the flask through
the inlet tube (3) by lifting the glass rod stopper. At this stage the flow rate of the carrier gas should be producing
about 2bubbles per second (9). Heat the sample mixture in the round bottom flask gently to boiling and keep at
boiling for 4min. Then remove the heater and whilst cooling pass approximately 3 l of carrier gas through the
system. Close the taps of the U-tube. Transfer it to a desiccator, cool for 30min, wipe with a clean cloth and weigh
to the nearest0.0001g.

F.4.5 Calculation

Calculate the carbon content as a percentage by mass using the formula:

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 ES 1176-2:2005

mu 2 − mu1
C= X 27 .29
m

where

m u1 is the mass of the U -tube before absorption of carbon dioxide (in g);

m u2 is the mass of the U -tube after absorption of carbon dioxide (in g);

m is the mass of the sample (in g).

Express the result to two decimal places.

F.5 Furnace oxidation method (alternative method 1)

F.5.1 Principle

The carbon dioxide in the limestone is driven off by the use of hydrochloric acid in a PTFE dish. The insoluble
residue is transferred to a platinum boat. The remaining organic carbon is oxidized in an oxygen atmosphere at
900°C and the liberated carbon dioxide is absorbed on an inorganic carrier impregnated with sodium hydroxide in a
U-tube. The increase in weight is directly proportional to the carbon in the sample (2).

F.5.2 Apparatus

The apparatus for the determination of carbon is shown in Figure F.2.

The PTFE dish has a diameter of approximately 8cm and a height of approximately 3cm. The dimensions of the
platinum boat are 5.0cm × 0.8cm × 0.8cm.

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ES 1176-2:2005

F.5.3 Reagents

Use only reagents of analytical quality and distilled water or water of equal purity during the analysis. The density of
concentrated liquid reagents is expressed in g/cm 3 Oxidation catalyst. Ignited silver permanganate with a
composition of approximately AgMnO2.

Silver gauze, Ag

Lead chromate, PbCrO 4

Platinum on quartz wool as carrier

Oxygen, O2

Hydrochloric acid, HCl, ρ = 1.19

Magnesium perchlorate. Mg (ClO4)2 with a particle size of 0.6 mm to 1.2 mm. Absorbent for carbon dioxide. NaOH
on an inert inorganic carrier.

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 ES 1176-2:2005

F.5.4 Procedure

F.5.4.1 Filling the quartz tube

Close the left-hand side outlet of the quartz tube in Figure F.2 with a 1 cm quartz wool plug. While holding the
quartz tube in a vertical position, fill it with 6cm of the oxidation catalyst (Ox), 6cm silver gauze (Ag), and 6.5cm
lead chromate (Bc). Compact the catalyst and the lead chromate by slight vibration while filling the tube. Compact
the silver gauze with a glass rod.

Fix the three layers in place with a plug of platinum on quartz wool 18) . Position the tube in the long furnace (6) as
shown in Figure F.2. Heat the long furnace to (500 ± 20)°C, while passing oxygen through the tube. The flow rate
of the oxygen should be at least 7ml/min. After 30min the equipment is ready for the carbon determination. The
catalyst filling in the tube is sufficient for about 15 carbon determinations, after which it has to be renewed.

F.5.4.2 Analysis

Weigh (0.4 ± 0.1) g of the limestone sample to the nearest 0.0001g in a PTFE dish. Moisten the weighed test
sample with 1or 2drops of water and then add slowly10ml of hydrochloric acid. At the end of the first intensive
reaction heat the dish on a hot plate with a furnace temperature of (140± 10)°C. Heat the sample to complete
dryness. Break up the residue and remove it from the wall of the bowl with a PTFE rod, while still on the hot plate.
Transfer the dried residue completely into a platinum boat, which is immediately introduced into the right-hand side
inlet of the quartz tube (3), whilst oxygen is still passing through the tube at a flow rate of at least 7 ml/min. Close
the inlet with a rubber stopper. Move the short furnace (4) into position, and heat to (900 ± 25) °C maintaining this
temperature for15min. Then switch it off, but pass oxygen through the tube for another20min. After that close the
taps of the U-tube (8). Remove the U-tube, cool in a desiccator, and weigh it to the nearest0.0001 g.

F.5.5 Calculation

Calculate the carbon content using the formula (1) (see F.4.5 ). Express the result to two decimal places.

F.6 Automatic determination method (alternative method 2)

F.6.1 Principle

The carbon dioxide in the limestone is driven off by the use of hydrochloric acid. The carbon content of the residue
is oxidized with oxygen in a high frequency furnace in the presence of an accelerator at approximately 1500 °C.
The resulting gas mixture which consists of oxygen, carbon dioxide, carbon monoxide, sulfur dioxide and water is
treated with manganese dioxide to absorb sulfur dioxide. The carbon monoxide is oxidized by copper oxide to give
carbon dioxide. The water is absorbed by magnesium perchlorate. The carbon dioxide is first absorbed on a
molecular sieve, then liberated again, and quantitatively determined by a thermal conductivity meter (10).

F.6.2 Apparatus

The apparatus for the automatic determination of carbon is illustrated in a flow sheet in Figure F.3. After thirty
determinations the dust filter (4) and the water traps (7) and (9) have to be changed. At the same time the
combustion tube in the furnace (3) has to be cleaned. The SO 2 absorbent (5) has to be changed every 500
analyses. The CO 2 and water traps (1) and (2) have to be changed once a month and the catalyst (6) once a year.

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ES 1176-2:2005

F.6.3 Reagents

Use only reagents of analytical quality and distilled water or water of equal purity for analysis. The densities of
3
concentrated liquid reagents are expressed in g/cm . The degree of dilution is expressed as a volumetric sum.

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 ES 1176-2:2005

Hydrochloric acid, HCl, ρ = 1.19

Hydrochloric acid, dilute,1 + 5

Sodium hydroxide, NaOH

Sodium hydroxide solution.

Dissolve40g sodium hydroxide in 1000ml water

Absorbent for carbon dioxide. NaOH on an inert anhydrous inorganic carrier

Absorbent for water. Mg(ClO4)2 with a particle size of 0.6mm to1.2mm Absorbent for sulfur dioxide. MnO 2 with a

Particle size of 0.6mm to1.2mm

Catalyst. CuO with a particle size of 0.6mm to1.2mm

Iron accelerator. Fe, free of carbon

Copper accelerator. Cu, free of carbon

Calibration reagent. Metal, for example iron,

with known carbon content

F.6.4 Procedure

F.6.4.1 Calibration

First, several blank determinations are performed to obtain a low and stable reading of the thermal conductivity cell.
The apparatus will keep this reading as the blank. Next, several different weights of the calibration reagent are
analyzed and the readings are stored in the calculator of the apparatus to give a straight calibration line. This
calibration line is used to calculate the result.

F.6.4.2 Determination

Weigh in a100ml beaker0.4g of the limestone sample to the nearest0.0001g. Wet the sample with 2 drops of water.
Add gently 10ml of hydrochloric acid (1 + 5). Swirl the sample and leave it to stand for approximately 16h
(overnight) covered with a watch glass. Heat the mixture to (75± 5) °C until the dolomitic parts of the sample are
dissolved completely and CO 2 is no longer evolved.

Neutralize the excess of hydrochloric acid with sodium hydroxide solution 19). After neutralization leave the beaker
to stand until the residue has settled. Decant the supernatant liquid without loss of the residue. Filter the remaining
liquid and the residue by suction through the special crucible used with the high frequency furnace. After washing
the residue with water dry the crucible and the residue in an oven at (105 ± 5) °C. Add iron and copper accelerators
to the crucible, place it in the holder of the high frequency furnace and start the apparatus. The apparatus stops
automatically and the meter gives a reading which corresponds to the percentage of carbon present in the sample.

F.6.5 Calculation

Report the TOC content as a percentage by mass. Express the result to two decimal places.

F.7 Precision of test results

The standard deviation of repeatability (with one exception) was found to be less than0.07 % by mass and was
independent of the method used and the amount of carbon present. Similar results were obtained in different
laboratories during comparison tests for the standard deviation of reproducibility.

63