SIST-TP CEN/TR 17365:2019
(Main)Method for the determination of C3A in the clinker from cement analysis
Method for the determination of C3A in the clinker from cement analysis
This document describes the analytical procedures used to determine the content of C3A in the clinker starting from a chemical analysis on cement. The method can be applied to CEM type I and IV for the determination of the requirement of C3A, as defined on EN 197-1.
This document describes two methods, traditional wet and XRF analysis (EN 196-2), which can be considered to be equivalent, in the scope of this CEN/TR 17365, for the determination of Al2O3, Fe2O3 and SO3.
The same methods are described in EN 196-2, but for the scope of this document, the X-ray fluorescence (XRF) is the preferred method to be used for the determination of Al2O3, Fe2O3 and SO3.
Verfahren für die Bestimmung des C3A-Gehalts im Klinker aus der Zementanalyse
Metoda za ugotavljanje C3A v klinkerju na podlagi analize cementa
Ta dokument opisuje analitske postopke, ki se uporabljajo za določanje vsebnosti C3A v klinkerju, začenši s kemijsko analizo cementa. Metodo je mogoče uporabiti za CEM tipa I in IV za določanje potrebe po C3A, kot je opredeljeno v standardu EN 197-1.
Ta dokument opisuje dve metodi, tradicionalno mokro analizo in analizo XRF (EN 196-2), ki ju je v smislu tega standarda CEN/TR 17365 mogoče šteti za enakovredni pri določanju Al2O3, Fe2O3 in SO3.
Isti metodi sta opisani v standardu EN 196-2, toda za področje uporabe tega dokumenta je za določanje Al2O3, Fe2O3 in SO3 najprimernejša rentgenska fluorescenca (XRF).
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
SIST-TP CEN/TR 17365:2019
01-oktober-2019
Metoda za ugotavljanje C3A v klinkerju na podlagi analize cementa
Method for the determination of C3A in the clinker from cement analysis
Verfahren für die Bestimmung des C3A-Gehalts im Klinker aus der Zementanalyse
Ta slovenski standard je istoveten z: CEN/TR 17365:2019
ICS:
91.100.10 Cement. Mavec. Apno. Malta Cement. Gypsum. Lime.
Mortar
SIST-TP CEN/TR 17365:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST-TP CEN/TR 17365:2019
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SIST-TP CEN/TR 17365:2019
CEN/TR 17365
TECHNICAL REPORT
RAPPORT TECHNIQUE
May 2019
TECHNISCHER BERICHT
ICS 91.100.10
English Version
Method for the determination of C3A in the clinker from
cement analysis
Verfahren für die Bestimmung des C3A-Gehalts im
Klinker aus der Zementanalyse
This Technical Report was approved by CEN on 12 May 2019. It has been drawn up by the Technical Committee CEN/TC 51.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 17365:2019 E
worldwide for CEN national Members.
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CEN/TR 17365:2019 (E)
Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 4
4 Principle of the method . 4
5 Expression of masses, volumes, factors and results. 5
6 Ignitions . 5
7 Determination of constant mass . 5
8 Preparation of a test sample of cement . 6
9 Reagents . 6
10 Apparatus . 8
11 Determination of BCR residue on cement . 10
12 Decomposition of the test sample for CEM I and IV type cements . 11
13 Decomposition of the BCR residue and precipitation of silica in the residue . 12
14 Chemical analysis of the filtrate obtained from treatment of the test sample and of
the filtrate obtained from treatment of the BCR residue . 13
15 Determination of Sulfur trioxide (SO ) . 14
3
16 Volumetric determination of carbon dioxide (CO ) in the cement test sample . 14
2
17 Chemical analysis by X-ray fluorescence . 17
18 Calculation and expression of results . 17
19 Repeatability and reproducibility . 18
Bibliography . 19
2
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CEN/TR 17365:2019 (E)
European foreword
This document (CEN/TR 17365:2019) has been prepared by Technical Committee CEN/TC 51 “Cement
and building limes”, the secretariat of which is held by NBN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
3
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CEN/TR 17365:2019 (E)
1 Scope
This document describes the analytical procedures used to determine the content of C A in the clinker
3
starting from a chemical analysis on cement. The method can be applied to CEM type I and IV for the
determination of the requirement of C A, as defined on EN 197-1.
3
This document describes two methods, traditional wet and XRF analysis (EN 196-2), which can be
considered to be equivalent, in the scope of this CEN/TR 17365, for the determination of Al O , Fe O
2 3 2 3
and SO .
3
The same methods are described in EN 196-2, but for the scope of this document, the X-ray fluorescence
(XRF) is the preferred method to be used for the determination of Al O , Fe O and SO .
2 3 2 3 3
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
EN 196-2, Method of testing cement — Part 2: Chemical analysis of cement
EN 196-7, Methods of testing cement — Part 7: Methods of taking and preparing samples of cement
ISO 385, Laboratory glassware — Burettes
ISO 835, Laboratory glassware — Graduated pipettes
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
4 Principle of the method
The principle of the method is based on the calculation of the amounts of Al O and Fe O that may be
2 3 2 3
occurring in the clinker by the chemical analysis of cement corrected for the oxide fraction resulting
from materials other than clinker.
Once Al O and Fe O values are obtained, the amount of C A in the clinker is calculated according to
2 3 2 3 3
Bogue.
The following assumptions should be made to determine the Al O and Fe O amounts in the clinker:
2 3 2 3
a) Any sulfate occurring in the cement is ascribable to CaSO ⦁2H O; all determined CO is CaCO .
2
4 2 3
Moreover, the Al O and Fe O input from minor additional constituents and calcium sulfate is
2 3 2 3
assumed to be zero.
b) The residue from the base-complexing agent treatment (BCR) is constituted by pozzolanic
materials only (natural pozzolana, siliceous fly ash and microsilica) and the dissolution is selective
and complete.
4
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Based on the above assumptions and on the calculated quantities of CaSO ⦁2H O and CaCO Al O
4 2 3, 2 3
and Fe O percentages in the clinker can be calculated by subtracting the oxide fraction in the cement
2 3
and the BCR, corrected for the amount of gypsum and pozzolanic materials (see Figure 1).
Figure 1 — General outline of the analytical procedures and the chemical substances to be
determined
5 Expression of masses, volumes, factors and results
Express masses in grams to the nearest 0,000 1 g and volumes from burettes in millilitres to the nearest
0,05 ml.
Express the factors of solutions, given by the mean of three measurements, to three decimal places.
Express the results, where a single test result has been obtained, as a percentage generally to two
decimal places.
Express the results, where two test results have been obtained, as the mean of the results, as a
percentage generally to two decimal places.
The results of all individual tests shall be recorded.
6 Ignitions
Carry out ignitions as follows.
Place the filter paper and its contents into a crucible which has been previously ignited and tared. Dry it,
then incinerate slowly in an oxidising atmosphere in order to avoid immediate flaming, while ensuring
complete combustion. Ignite the crucible and its contents at the stated temperature, then allow to cool
to the laboratory temperature in a desiccator. Weigh the crucible and its contents.
7 Determination of constant mass
Determine constant mass by making successive 15 min ignitions followed each time by cooling and then
weighing. Constant mass is reached when the difference between two successive weighings is less than
0,000 5 g.
5
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8 Preparation of a test sample of cement
Before chemical analysis, treat the laboratory sample, taken in accordance with EN 196-7, as follows to
obtain a homogeneous test sample.
Take approximately 100 g of the laboratory sample by means of a sample divider or by quartering.
Sieve this portion on a 90 μm sieve until the residue remains constant. Remove metallic iron from the
material retained on the sieve by means of a magnet (see Note). Then grind the iron-free fraction of the
retained material so that it completely passes the 90 μm sieve. Transfer the sample to a clean dry
container with an airtight closure and shake vigorously to mix it thoroughly.
Carry out all operations as quickly as possible to ensure that the test sample is exposed to ambient air
only for the minimum time.
NOTE Where the analysis is one of a series subject to statistical control and the level of the metallic iron
content has been shown to be insignificant in relation to the chemical properties to be determined then it is not
necessary to remove metallic iron.
9 Reagents
Use only reagents of analytical quality. References to water mean distilled or de-ionized water having
an electrical conductivity ≤ 0,5 mS/m.
Unless otherwise stated percent means percent by mass.
Unless otherwise stated the concentrated liquid reagents used in this document have the following
3
densities (ρ) (in g/cm at 20 °C):
hydrochloric acid 1,18 to 1,19 perchloric acid 1,60 to 1,67
acetic acid 1,05 to 1,06 ammonium hydroxide 0,88 to 0,91
The degree of dilution is always given as a volumetric sum, for example: dilute hydrochloric acid 1 + 2
means that 1 volume of concentrated hydrochloric acid is to be mixed with 2 volumes of water.
9.1 Triethanolamine (TEA): [N(CH CH OH) ] (d = 1,12 g/cm3).
2 2 3
9.2 EDTA - dihydrated disodium salt of ethylenediaminetetra-acetic acid.
9.3 0,025M EDTA solution
In a litre flask, dissolve 9,306 0 g of EDTA, previously dried in an oven at a temperature of 80 ± 2°C for
4 d, add distilled water up to the calibration mark and blend.
9.4 Diethylamine (DEA): [(C H )2NH].
2 5
9.5 Ethanol 95°: [C H OH].
2 5
9.6 Anhydrous sodium carbonate (Na CO ).
2 3
9.7 Perchloric acid, (HClO ).
4
9.8 Acetic acid, glacial (CH3COOH)
9.9 Hydrochloric acid, (HCl)
6
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9.10 Hydrochloric acid 12 % (HCl)
Dilute 100 ml of concentrated HCl (9.9) with 250 ml of distilled water.
9.11 Hydrochloric acid, dilute (1 + 1)
9.12 Hydrochloric acid, dilute (1 + 100)
9.13 Acetic anhydride (CH COOCH )
3 3
9.14 Sulfo-5-salicylic acid dehydrate
9.15 Sulphosalicylic acid indicator:
Dissolve 5 g of sulphosalicylic acid dihydrate (9.14) in 100 ml of H2O.
9.16 Anhydrous sodium acetate (CH COONa).
3
9.17 Acetic buffer solution at pH 4,7-4,8
On a magnetic stirrer, dissolve 82,0 g of CH3COONa (9.16), 57 ml of glacial acetic acid (9.8) in 1000 ml
of distilled water, blend and store in a plastic spray bottle.
9.18 Ammonium chloride (NH Cl).
4
9.19 Ammonium hydroxide (NH OH)
4
9.20 buffer solution, ammoniacal
Dissolve 540,0 g of ammonium chloride (NH Cl) (9.18) and 6,00 ml of 25 % concentrate
4
ammonium hydroxide (9.19) in 4 l of distilled water.
9.21 Potassium hydroxide (KOH),
9.22 Potassium hydroxide solution 4N,
Dissolve 250,0 g of potassium hydroxide (KOH) (9.21) in 900 ml of distilled water.
9.23 Methylthymol blue complexone indicator
9.24 Methyl orange indicator
9.25 Potassium Nitrate (KNO )
3
9.26 Methylthymol blue mix complexone indicator
Mix and grind together 0,15 g of Methylthymol blue (9.23), 0,0165 g of methylorange and 15 g of dried
KNO3.
9.27 Hydrous copper sulfate (CuSO •5H O)
4 2
9.28 Copper complexonate solution
In a 250 ml volumetric flask, dissolve 2,0 g of CuSO4⦁5H2O (9.27) and fill to the calibration mark.
Pipette 10,0 ml of this solution into 400 ml beaker and dilute with 200 ml of distilled water.
7
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Adjust the pH to 10,2 with the ammoniacal buffer solution (9.20), add a spatula-tip of murexide
indicator (9.24), then titrate with a 0,025M solution of EDTA until the colour changes from green to
violet: let n be number of millilitres of EDTA used. Take exactly 100 ml of the copper solution, add 10 ml
of 0,025M EDTA and blend thoroughly the copper complexonate solution thus obtained.
9.29 PAN indicator solution [1(-pyridine) - 2 naphthol] 0,1 % in ethanol at 95 °.
9.30 Murexide indicator
Prepare by grinding (1,0 ± 0,1) g of murexide (ammonium purpurate, C8H4N5O6.NH4) with (100 ± 1) g
of sodium chloride (NaCl).
9.31 Copperchloride (Cu Cl ).
2 2
9.32 Copper chloride (CuCl •H O)
2 2
9.33 Reagent for determination of carbon dioxide
Dissolve 1,50 g of cuprous chloride and 2,50 g of copper chloride in 350 ml of 12 % hydrochloric acid
(9.10).
10 Apparatus
10.1 Balance(s), capable of weighing to an accuracy of ± 0,000 5 g.
10.2 Laboratory oven(s), capable of being set at (150 ± 5) °C.
10.3 Electric furnace or Bunsen burner for temperatures up to 950 °C
10.4 Electromagnetic stirrer
10.5 Membrane filters, preferably made from polycarbonate, 47 mm or 90 mm in diameter, with
maximum pore size of 1μ.
10.6 Vacuum filtration device
10.7 Vacuum pump, for vacuum filtration at negative pressures of approximately 700 mmHg.
10.8 Silica gel desiccator, with indicator.
10.9 Rod with rubber tip, to facilitate removal of any particles that stick to the sides of the apparatus.
3
10.10 Platinum crucibles, 10 to 20 cm capacity, with lids
10.11 Hot plate (or sand bath) capable of being set to temperatures up to 350°C.
10.12 Sand bath set to a temperature of 105 ± 5°C (or bain-marie).
10.13 Dietrich-Frühling apparatus (Figure 2)
Comprised of a fixed burette 1 with class A graduation, containing 12 % HCl (connected at the bottom
via flexible acid-resistant tubing 2 to a reservoir 3 held in a vertically sliding clamp. The top of the
graduated burette is connected via flexible acid-resistant tubing 4 to a flask 5 with a bored stopper 6
forming an airtight seal (use preferably a flask with ground rim and a silicone rubber stopper).
8
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At this same end, the burette 1 is also connected to the external atmosphere by way of a vacuum tap 7.
When assembling a new apparatus, when changing the manometric liquid or when the manometric
liquid has remained in contact with the external atmosphere for more than 3 h with the apparatus
inactive, it will be necessary to recondition the apparatus.
In this case, using any carbonate, perform a series of 3 to 4 CO releases at 70 % to 100 % of the
2
capacity of the graduated burette, with a pause of at least 2 min between each release.
On completion of the series of CO releases, both for the conditioning and for the measurements, close
2
the three points of possible contact with the external atmosphere at 6, 7 and 11, balance approximately
the levels in 1 and 3 and maintain the apparatus in this condition while not in use.
Key
1 Fixed burette 7 Vacuum tap
2 Flexible tubing 8 Thermometer
3 Reservoir 9 Magnetic stirrer
4 Flexible pipe 10 Water bath
5 Flask 11 Stopper for apparatus when not in use
6 Stopper with bore
Figure 2 — Dietrich-Frühling apparatus
9
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10.14 Thermometers, with accuracy of 0,1 °C for measuring the ambient temperature and the
temperature of the water bath in the range of 20 °C to 30 °C.
10.15 Barometer, with an accuracy of at least 0,5 mmHg
10.16 Class A volumetric glassware, according to ISO 385 or ISO 835.
11 Determination of BCR residue on cement
11.1 Procedure
In a tall graduated 1 000 ml beaker, put a suitable magnetic stirrer and approximately 700 ml of water.
Working under a fume hood, add to the water and dissolve, stirring the mixture continuously, the
following reagents in the order given:
— 4,65 g of EDTA (9.2);
— 12,5 ml of TEA (9.1);
— 8,7 ml of DEA (9.4).
Once the substances are dissolved, stop magnetic stirring and dilute with water to bring the level up to
the 800 ml (lower meniscus).
Place the beaker on the magnetic stirrer at approximately 300 rpm. Add to ±0,000 5 g,
(0,500 0 ± 0,000 5) g of the test sample gradually in 30 s to 40 s, cover the beaker, start timing the
treatment, and control the temperature of the solution at (20 ± 2) °C.
After 5 min, stop stirring and break up any lumps using a glass rod with a flat end. Remove the rod and
wash
...
SLOVENSKI STANDARD
kSIST-TP FprCEN/TR 17365:2019
01-marec-2019
Metoda za ugotavljanje C3A v klinkerju na podlagi analize cementa
Method for the determination of C3A in the clinker from cement analysis
Verfahren für die Bestimmung des C3A-Gehalts im Klinker aus der Zementanalyse
Ta slovenski standard je istoveten z: FprCEN/TR 17365
ICS:
91.100.10 Cement. Mavec. Apno. Malta Cement. Gypsum. Lime.
Mortar
kSIST-TP FprCEN/TR 17365:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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kSIST-TP FprCEN/TR 17365:2019
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kSIST-TP FprCEN/TR 17365:2019
FINAL DRAFT
TECHNICAL REPORT
FprCEN/TR 17365
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
January 2019
ICS 91.100.10
English Version
Method for the determination of C3A in the clinker from
cement analysis
Verfahren für die Bestimmung des C3A-Gehalts im
Klinker aus der Zementanalyse
This draft Technical Report is submitted to CEN members for Vote. It has been drawn up by the Technical Committee CEN/TC 51.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.
Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are
aware and to provide supporting documentation.
Warning : This document is not a Technical Report. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a Technical Report.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprCEN/TR 17365:2019 E
worldwide for CEN national Members.
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FprCEN/TR 17365:2019 (E)
Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 4
4 Principle of the method . 4
5 Expression of masses, volumes, factors and results. 5
6 Ignitions . 5
7 Determination of constant mass . 5
8 Preparation of a test sample of cement . 6
9 Reagents . 6
10 Apparatus . 8
11 Determination of BCR residue on cement . 11
12 Decomposition of the test sample for CEM I and IV type cements . 12
13 Decomposition of the BCR residue and precipitation of silica in the residue . 13
14 Chemical analysis of the filtrate obtained from treatment of the test sample and of
the filtrate obtained from treatment of the BCR residue . 14
15 Determination of Sulfur trioxide (SO ) . 15
3
16 Volumetric determination of carbon dioxide (CO ) in the cement test sample. 15
2
17 Chemical analysis by X-ray fluorescence . 18
18 Calculation and expression of results . 18
19 Repeatability and reproducibility . 19
Bibliography . 20
2
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European foreword
This document (FprCEN/TR 17365:2019) has been prepared by Technical Committee CEN/TC 51
“Cement and building limes”, the secretariat of which is held by NBN.
This document is currently submitted to the Vote on TR.
3
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FprCEN/TR 17365:2019 (E)
1 Scope
This document describes the analytical procedures used to determine the content of C A in the clinker
3
starting from a chemical analysis on cement. The method can be applied to CEM type I and IV for the
determination of the requirement of C A, as defined on EN 197-1.
3
This document describes two methods, traditional wet and XRF analysis (EN 196-2), which can be
considered to be equivalent, in the scope of this CEN/TR 17365, for the determination of Al O , Fe O
2 3 2 3
and SO .
3
The same methods are described in EN 196-2, but for the scope of this document, the X-ray fluorescence
(XRF) is the preferred method to be used for the determination of Al O , Fe O and SO .
2 3 2 3 3
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
EN 196-2, Method of testing cement — Part 2: Chemical analysis of cement
EN 196-7, Methods of testing cement — Part 7: Methods of taking and preparing samples of cement
ISO 385, Laboratory glassware — Burettes
ISO 835, Laboratory glassware — Graduated pipettes
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
4 Principle of the method
The principle of the method is based on the calculation of the amounts of Al O and Fe O that may be
2 3 2 3
occurring in the clinker by the chemical analysis of cement corrected for the oxide fraction resulting
from materials other than clinker.
Once Al O and Fe O values are obtained, the amount of C A in the clinker is calculated according to
2 3 2 3 3
Bogue.
The following assumptions should be made to determine the Al O and Fe O amounts in the clinker:
2 3 2 3
a) Any sulfate occurring in the cement is ascribable to CaSO ⦁2H O; all determined CO is CaCO .
4 2 2 3
Moreover, the Al O and Fe O input from minor additional constituents and calcium sulfate is
2 3 2 3
assumed to be zero;
b) The residue from the base-complexing agent treatment (BCR) is constituted by pozzolanic
materials only (natural pozzolana, siliceous fly ash and microsilica) and the dissolution is selective
and complete.
4
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Based on the above assumptions and on the calculated quantities of CaSO ⦁2H O and CaCO Al O and
4 2 3, 2 3
Fe O percentages in the clinker can be calculated by subtracting the oxide fraction in the cement and
2 3
the BCR, corrected for the amount of gypsum and pozzolanic materials (see Figure 1).
Figure 1 — General outline of the analytical procedures and the chemical substances to be
determined
5 Expression of masses, volumes, factors and results
Express masses in grams to the nearest 0,0001 g and volumes from burettes in millilitres to the nearest
0,05 ml.
Express the factors of solutions, given by the mean of three measurements, to three decimal places.
Express the results, where a single test result has been obtained, as a percentage generally to two
decimal places.
Express the results, where two test results have been obtained, as the mean of the results, as a
percentage generally to two decimal places.
The results of all individual tests shall be recorded.
6 Ignitions
Carry out ignitions as follows.
Place the filter paper and its contents into a crucible which has been previously ignited and tared. Dry it,
then incinerate slowly in an oxidising atmosphere in order to avoid immediate flaming, while ensuring
complete combustion. Ignite the crucible and its contents at the stated temperature then allow to cool
to the laboratory temperature in a desiccator. Weigh the crucible and its contents.
7 Determination of constant mass
Determine constant mass by making successive 15 min ignitions followed each time by cooling and then
weighing. Constant mass is reached when the difference between two successive weighings is less than
0,0005 g.
5
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8 Preparation of a test sample of cement
Before chemical analysis, treat the laboratory sample, taken in accordance with EN 196-7, as follows to
obtain a homogeneous test sample.
Take approximately 100 g of the laboratory sample by means of a sample divider or by quartering.
Sieve this portion on a 90 μm sieve until the residue remains constant. Remove metallic iron from the
material retained on the sieve by means of a magnet (see Note). Then grind the iron-free fraction of the
retained material so that it completely passes the 90 μm sieve. Transfer the sample to a clean dry
container with an airtight closure and shake vigorously to mix it thoroughly.
Carry out all operations as quickly as possible to ensure that the test sample is exposed to ambient air
only for the minimum time.
NOTE Where the analysis is one of a series subject to statistical control and the level of the metallic iron
content has been shown to be insignificant in relation to the chemical properties to be determined then it is not
necessary to remove metallic iron.
9 Reagents
Use only reagents of analytical quality. References to water mean distilled or de-ionized water having
an electrical conductivity ≤ 0,5 mS/m.
Unless otherwise stated percent means percent by mass.
Unless otherwise stated the concentrated liquid reagents used in this document have the following
3
densities (ρ) (in g/cm at 20 °C):
hydrochloric acid 1,18 to 1,19 perchloric acid 1,60 to 1,67
acetic acid 1,05 to 1,06 ammonium hydroxide 0,88 to 0,91
The degree of dilution is always given as a volumetric sum, for example: dilute hydrochloric acid 1 + 2
means that 1 volume of concentrated hydrochloric acid is to be mixed with 2 volumes of water.
9.1 Triethanolamine (TEA): [N(CH CH OH) ] (d = 1,12 g/cm3).
2 2 3
9.2 EDTA - dihydrated disodium salt of ethylenediaminetetra-acetic acid.
9.3 0,025M EDTA solution
In a litre flask, dissolve 9,3060 g of EDTA, previously dried in an oven at a temperature of 80 ± 2°C
for 4 days, add distilled water up to the calibration mark and blend.
9.4 Diethylamine (DEA): [(C H )2NH].
2 5
9.5 Ethanol 95°: [C H OH].
2 5
9.6 Anhydrous sodium carbonate (Na CO ).
2 3
9.7 Perchloric acid, (HClO ).
4
9.8 Acetic acid, glacial (CH3COOH)
9.9 Hydrochloric acid, (HCl)
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9.10 Hydrochloric acid 12 % (HCl)
Dilute 100 ml of concentrated HCl (9.9) with 250 ml of distilled water.
9.11 Hydrochloric acid, dilute (1 + 1)
9.12 Hydrochloric acid, dilute (1 + 100)
9.13 Acetic anhydride (CH COOCH )
3 3
9.14 Sulfo-5-salicylic acid dehydrate
9.15 Sulphosalicylic acid indicator:
Dissolve 5 g of sulphosalicylic acid dihydrate (9.14) in 100 ml of H O.
2
9.16 Anhydrous sodium acetate (CH COONa).
3
9.17 Acetic buffer solution at pH 4,7-4,8
On a magnetic stirrer, dissolve 82,0 g of CH COONa (9.16), 57 ml of glacial acetic acid (9.8) in
3
1000 ml of distilled water, blend and store in a plastic spray bottle.
9.18 Ammonium chloride (NH Cl).
4
9.19 Ammonium hydroxide (NH OH)
4
9.20 buffer solution, ammoniacal
Dissolve 540,0 g of ammonium chloride (NH Cl) (9.18) and 6,00 ml of 25 % concentrate
4
ammonium hydroxide (9.19) in 4 l of distilled water.
9.21 Potassium hydroxide (KOH),
9.22 Potassium hydroxide solution 4N,
Dissolve 250,0 g of potassium hydroxide (KOH) (9.21) in 900 ml of distilled water.
9.23 Methylthymol blue complexone indicator
9.24 Methyl orange indicator
9.25 Potassium Nitrate (KNO )
3
9.26 Methylthymol blue mix complexone indicator
Mix and grind together 0,15 g of Methylthymol blue (9.23), 0,0165 g of methylorange and 15 g of
dried KNO .
3
9.27 Hydrous copper sulfate (CuSO •5H O)
4 2
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9.28 Copper complexonate solution
In a 250 ml volumetric flask, dissolve 2,0 g of CuSO ⦁5H O (9.27) and fill to the calibration mark.
4 2
Pipette 10,0 ml of this solution into 400 ml beaker and dilute with 200 ml of distilled water.
Adjust the pH to 10,2 with the ammoniacal buffer solution (9.20), add a spatula-tip of murexide
indicator (9.24), then titrate with a 0,025M solution of EDTA until the colour changes from green to
violet: let n be number of millilitres of EDTA used. Take exactly 100 ml of the copper solution, add
n.10 ml of 0.025M EDTA and blend thoroughly the copper complexonate solution thus obtained.
9.29 PAN indicator solution [1(-pyridine) - 2 naphthol] 0,1 % in ethanol at 95 °.
9.30 Murexide indicator
Prepare by grinding (1,0 ± 0,1) g of murexide (ammonium purpurate, C H N O .NH ) with
8 4 5 6 4
(100 ± 1) g of sodium chloride (NaCl).
9.31 Copperchloride (Cu Cl ).
2 2
9.32 Copper chloride (CuCl •H O)
2 2
9.33 Reagent for determination of carbon dioxide
Dissolve 1,50 g of cuprous chloride and 2,50 g of copper chloride in 350 ml of 12 % hydrochloric
acid (9.10).
10 Apparatus
10.1 Balance(s), capable of weighing to an accuracy of ± 0,0005 g.
10.2 Laboratory oven(s), capable of being set at (150 ± 5) °C.
10.3 Electric furnace or Bunsen burner for temperatures up to 950 °C
10.4 Electromagnetic stirrer
10.5 Membrane filters, preferably made from polycarbonate, 47 mm or 90 mm in diameter, with
maximum pore size of 1μ.
10.6 Vacuum filtration device
10.7 Vacuum pump, for vacuum filtration at negative pressures of approximately 700 mmHg.
10.8 Silica gel desiccator, with indicator.
10.9 Rod with rubber tip, to facilitate removal of any particles that stick to the sides of the apparatus.
3
10.10 Platinum crucibles, 10 to 20 cm capacity, with lids
10.11 Hot plate (or sand bath) capable of being set to temperatures up to 350°C.
10.12 Sand bath set to a temperature of 105 ± 5°C (or bain-marie).
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10.13 Dietrich-Frühling apparatus (Figure 2)
Comprised of a fixed burette 1 with class A graduation, containing 12 % HCl (11.1.24 connected at
the bottom via flexible acid-resistant tubing 2 to a reservoir 3 held in a vertically sliding clamp. The
top of the graduated burette is connected via flexible acid-resistant tubing 4 to a flask 5 with a
bored stopper 6 forming an airtight seal (use preferably a flask with ground rim and a silicone
rubber stopper).
At this same end, the burette 1 is also connected to the external atmosphere by way of a vacuum
tap 7.
When assembling a new apparatus, when changing the manometric liquid or when the manometric
liquid has remained in contact with the external atmosphere for more than 3h with the apparatus
inactive, it will be necessary to recondition the apparatus.
In this case, using any carbonate, perform a series of 3-4 CO releases at 70 to 100 % of the capacity
2
of the graduated burette, with a pause of at least 2 min between each release.
On completion of the series of CO releases, both for the conditioning and for the measurements,
2
close the three points of possible contact with the external atmosphere at 6, 7 and 11, balance
approximately the levels in 1 and 3 and maintain the apparatus in this condition while not in use.
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Key
1 Fixed burette
2 Flexible tubing
3 Reservoir
4 Flexible pipe
5 Flask
6 Stopper with bore
7 Vacuum tap
8 Thermometer
9 Magnetic stirrer
10 Water bath
11 Stopper for apparatus when not in use
Figure 2 — Dietrich-Frühling apparatus
10.14 Thermometers, with accuracy of 0,1 °C for measuring the ambient temperature and the
temperature of the water bath in the range of 20 to 30 °C.
10.15 Barometer, with an accuracy of at least 0,5 mmHg
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10.16 Class A volumetric glassware, according to ISO 385 or ISO 835.
11 Determination of BCR residue on cement
11.1 Procedure
In a tall graduated1000 ml beaker, put a suitable magnetic stirrer and approximately 700 ml of water.
Working under a fume hood, add to the water and dissolve, stirring the mixture continuously, the
following reagents in the order given:
— 4,65 g of EDTA (9.2);
— 12,5 ml of TEA (9.1);
— 8,7 ml of DEA (9.4).
Once the substances are dissolved, stop magnetic stirring and dilute with water to bring the level up to
the 800 ml (lower meniscus).
Place the beaker on the magnetic stirrer at approximately 300 rpm. Add to ± 0,0005 g,
(0,5000 ± 0,0005) g of
...
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