JTC

John M Turner
JT Consultant Services
28 Wing Road, Linslade, Leighton Buzzard
Bedfordshire, LU7 2NJ United Kingdom

Mobile: +44 (0) 7710 668302 Email: jtc@jtconsult.co.uk

Web site: www.jtconsult.co.uk

Issue 5  JT Consultant Services 2015

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ALKALI CONTENT IN CEMENT

Contents

Health and Safety 3

Hazard Warning

References 4
Introduction and principle
Application
Preparation of apparatus 5
General requirements 6
Preparation of stock solutions
Test procedures 7
Reference method 8
Alternative method 12
Apparatus 15
Chemicals
Technical note T005-02 – Trouble shooting Flame Photometer ignition
Protocol P05-060A Determination of alkali metals in cement

Disclaimer

 This document has been produced taking into account the published test method (s)
and accepted good practice.

 JT Consultant Services can accept no responsibility for any test results and their
subsequent use in any design, control or other such activity obtained when using this
document.

 The application of the data obtained to the design process is outside the scope of this
document.

 Users are advised to consult the latest standard in force at the time of use.

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Health and Safety

 The method may involve the use of hazardous materials, operations and apparatus.

 It is the responsibility of management and the users of this document to ensure

that appropriate health and safety practices are adopted and to comply with current
local health and safety regulations in force.

Hazard Warning

 Solvents/chemicals may be hazardous to health and are subject to occupational

exposure limits as detailed in statutory national and/or local regulations. Exposure
levels are related to both handling procedures and ventilation precision.

 Adequate training should be given to staff in the use of these substances.

 When cement is mixed with water, alkali is released. Take precautions to avoid
dry cement entering the eyes, mouth and nose whilst mixing concrete. Prevent
skin contact with wet cement or concrete by wearing suitable clothing.

 If cement or concrete enters the eye, immediately wash it out thoroughly with
clean water and seek medical treatment without delay. Wash wet concrete off the
skin immediately.

 The exhaust gases from the chimney of the Flame Photometer are very hot. No
obstruction should be placed above the instrument and it should be located such
that accidental contact with the chimney or its exhaust is unlikely.

 The fuel gases used in the Flame Photometer are inflammable and a potential fire
hazard. Gas cylinders should be stored and used in accordance with the supplier’s
instructions.

 During the ignition sequence there is a possibility that a small quantity of fuel may
escape from the Flame Photometer. This is essentially harmless although it may
smell slightly.

 If the smell persists the instrument should immediately be shut down and the
source of leakage determined and rectified before further use.

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References

 EN 196-2 Methods of testing cement; chemical analysis of cement

 EN 196-7 Methods of taking and preparing samples of cement
 Flame Photometer PFP7 operators manual by Jenway Ltd
 Technical note T005-02 – Trouble shooting Flame Photometer ignition by Jenway Ltd
 Protocol P05-060A Determination of alkali metals in cement by Jenway Ltd

Introduction

 Oxides of sodium and potassium, Na2O and K2O, referred to as the alkalis may react
with some aggregates, the products of the reaction causing disintegration of concrete.
They also may affect the rate of gain in the strength of cement.

Principle

 A butane, propane or acetylene flame is used to excite the alkali metals to emit their
characteristic spectrum in the visible range. The emission is proportional to the alkali
content at low concentrations.

 When using a flame photometer difficulty is experienced when lime (calcium) is

present in appreciable amounts of more than a few percent. This is due to the calcium
emitting radiation, which passes through the sodium filter to a measurable extent.

 This error must be taken into account or it can, in the case of cements, cause errors of
up to 100% in the reported sodium content.

 The influence of large quantities of calcium in the sample on the sodium

determination is suppressed by means of phosphoric acid. The influence of
phosphoric acid on the potassium emission from the calibration solutions is
suppressed by adding calcium to the calibration solutions. An alternative method of
suppressing this influence is by the addition of aluminium to the sample.

Application
 Specifications for cement will often limit the alkali content and standard tests have
been developed for factory production control and compliance testing.

 Where a new supplier of cement is used for the first time, it may be appropriate to
perform checks on the supplier’s specified values of alkali content until such time as
confidence in the source of supply is reached.

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Apparatus
 Prior to testing all apparatus should be cleaned, assembled and tested for compliance.

 It is absolutely imperative that the test procedures described in the manufacturer’s

manual are followed if valid test results are to be obtained.

Schematic representation of the PFP7

Reagents

 Only reagents of analytical (AR) quality shall be used. Unless otherwise stated the
concentrated liquid reagents shall have the following densities (ρ) in g/cm3 at 20 OC.

 Hydrochloric acid – 1.18 to 1.19

 Phosphoric acid – 1.71 to 1.75
 Nitric acid – 1.40 to 1.42

 The degree of dilution is given as a volumetric sum, e.g. dilute hydrochloric acid 1+2
means that 1 volume of concentrated hydrochloric acid is to be mixed with 2 volumes
of water.

 Use distilled or de-ionised water having an electrical conductivity < 0.5 mS/m.

 Failure to observe these requirements will lead to erroneous test results.

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General requirements

Number of tests

 The number of tests for each determination of each chemical property shall be two.

Expression of mass, volume, factors and results

 Express mass to the nearest 0.0001 g and volume to the nearest 0.05 ml.

 Express solution factors, given by the mean of 3 measurements, to 3 decimal places.

 Express the mean of the 2 test results as a percentage to 2 decimal places. Individual
test results shall also be recorded to 2 decimal places.

 If the 2 test results differ by more than twice the standard deviation of repeatability,
repeat the test and take the mean of the 2 closest test results.

Preparation of stock solutions

Alkali stock solution for definitive method

 Weigh 0.5660 + 0.0005 g of sodium chloride and 0.4750 + 0.0005 g of potassium

chloride and place in a 600 ml beaker. Add about 150 ml of water and allow the salts
to dissolve.

 Transfer the solution quantitatively, rinsing the beaker with water, to a 1000 ml
volumetric flask and make up to the mark with water mixing thoroughly.

 The solution contains 0.300 g each of sodium oxide Na2O and potassium oxide K2O.

Acid stock solution (HCl/H3PO4) for definitive method

 Place about 500 ml of water in a 1000 ml volumetric flask; add 50 ml of concentrated

hydrochloric acid and 50 ml of concentrated phosphoric acid.

 Allow to cool then make up to the mark with water mixing thoroughly.

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Calcium stock solution

 Place 11.25 + 0.01 g of calcium carbonate in a 600 ml beaker; add 100 ml of water
and dissolve the calcium carbonate by cautiously adding 25 ml of concentrated
hydrochloric acid.

 After the reaction is complete, bring slowly to boiling in order to expel the dissolved
carbon dioxide then allow to cool.

 Transfer the solution, rinsing the beaker with water, into a 1000 ml volumetric flask
and make up to the mark with water mixing thoroughly.

Alkali stock solution for alternative method

 Dissolve 0.2542 + 0.0005 g of sodium chloride and 0.1907 + 0.0005 g of potassium

chloride in water in a 1000 ml volumetric flask and make up to the mark with water.

TEST PROCEDURES

Determination of alkali – EN 196-2

PROCEDURAL STAGES

PREPARE APPARATUS PREPARE CALIBRATION

AND TEST SAMPLES SOLUTIONS

TEST BLANK CONSTRUCT

CALIBRATION SOLUTIONS CALIBRATION CURVES

TEST CEMENT EVALUATE AND

SAMPLES REPORT RESULTS

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Reference method

Preparation of cement samples

 Obtain about 100 g of the laboratory sample by riffling or quartering and sieve this
portion on a 150 mic or 125 mic sieve until the residue remains constant.

 Remove metallic iron from the material retained on the sieve using a magnet then
grind the iron-free fraction of the retained material so that it completely passes the
sieve.

 Transfer all the material passing the sieve to a clean dry container

 Before preparing the sample for chemical analysis, shake the container vigorously to
mix it thoroughly.

Preparation of calibration solutions and curves

 Whenever a new batch of reagent is used, determine the alkali content by means of
this method.

 If the alkali content of a reagent exceeds 0.01%, either replace the batch with a new
one, which shall be verified in the same way, or prepare new calibration solutions.

 Prepare the calibration solutions using the volumes of alkali, acid and stock solutions
listed in the table below.

Calibration Alkali stock Acid stock Calcium stock Na2O and K2O
solution solution (ml) solution (ml) solution (ml) concentrations (mg/l)
S1 - 100 100 0.0
S2 5 100 100 1.5
S3 10 100 100 3.0
S4 20 100 100 6.0
S5 30 100 100 9.0
S6 40 100 100 12.0
S7 50 100 100 15.0

 Make up the volumes of S1 to S7 to 1000 ml with water and mix thoroughly then
store in polyethylene bottles.

 Spray the blank solution (S1) into the flame photometer and set the indicator to zero.

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 Spray solution (S7) into the flame photometer and set the indicator to maximum
intensity.

 Spray the other solutions (S2 to S6) in the order of increasing concentrations into the
flame photometer. Measure the intensities for Na2O at 589 nm and for K2O at 768 nm.

 Construct curves of the measured intensities against the corresponding concentrations

of Na2O and K2O in the calibration solutions.

Dissolution of the test portion

Cement with an insoluble residue < 3%

 Weigh 0.5000 + 0.0005 g of cement into a 250 ml beaker making a slurry by adding
50 ml of water then add 50 ml of hydrochloric acid 1+19.

 Warm the mixture until the cement has decomposed crushing any lumps with a glass
rod and allow the suspension to cool to ambient temperature.

 Transfer the contents of the beaker, rinsing the beaker with water, into a 500 ml
volumetric flask.

 Add 50 ml of phosphoric acid 1+19, make up to the mark with water mixing
thoroughly.

 Filter, without washing, sufficient solution through a medium, ashless filter paper that
has been pre-washed with hot water into a clean, dry beaker before spraying the
solution into the flame photometer.

Cement with an insoluble residue > 3%

Hazard Warning

 Vapours from nitric acid, perchloric acid and hydrofluoric acid are hazardous.
Perform the following evaporation procedures in a fume cabinet.

 Wear eye protection and suitable rubber or plastics gloves when handling or agitating
these acids or their mixtures.

 Perchloric acid vapours form explosive mixtures with organic materials. Take special
precautionary measures, e.g. the use of a fume cupboard that has been flushed with
water and a general ban on the use of organic substances in the same fume cabinet.

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 Weigh 0.5000 + 0.0005 g of cement into a platinum dish and add 15 ml of nitric acid.
Heat the mixture and evaporate to dryness.

 Disperse the residue from evaporation in 15 ml of water, add 5 ml of perchloric acid

and then 25 ml of hydrofluoric acid.

 Prevent overheating by frequent agitation with a stirrer resistant to hydrofluoric acid,

e.g. a platinum rod.
 Add 10 ml of water and 50 ml of hydrochloric acid 1+19 to the residue from
evaporation; heat until dissolved then allow to cool to room temperature.

 Transfer the contents of the platinum dish, rinsing with water, into a 500 ml
volumetric flask.

 Add 50 ml of phosphoric acid 1+19 to the solution and make up to the mark with
water mixing thoroughly.

 Filter, without washing, sufficient solution through a medium, ashless filter paper that
has been pre-washed with hot water into a clean, dry beaker before spraying the
solution into the flame photometer.

 Spray the sample solution into the flame of the flame photometer measuring the
intensity of the sodium line at 589 nm and the potassium line at 768 nm.

Calculations

 Obtain the sodium oxide or potassium oxide concentration in the solution respectively
by means of a linear interpolation from the intensities and associated concentrations
of the calibration solutions used.

 Use the calibration curves to obtain the sodium oxide and potassium oxide
concentrations of the solution in mg/l or use the intensities and associated
concentrations of the calibration solutions with the next higher and the next lower
intensity for the calculation as follows:

 Calculate the sodium oxide concentration, CNa2O from:

CNa2O = CBn + (CBh – CBn) x (INa2O – IBn) / (IBh – IBn)

 Calculate the potassium oxide concentration, CK2O from:

CK2O = CBn + (CBh – CBn) x (IK2O – IBn) / (IBh – IBn)

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Where
CBn is the concentration of the sodium or potassium oxide in the calibration
solution having a lower concentration than the sample solution in mg/l

CBh is the concentration of the sodium or potassium oxide in the calibration

solution having a higher concentration than the sample solution in mg/l

IBn is the intensity of the calibration solution having a lower concentration than
the sample solution.

IBh is the intensity of the calibration solution having a lower concentration than
the sample solution.

Sodium and potassium oxide content

 Calculate the sodium and potassium oxide content in % from:-

Na2O = 0.1 x CNa2O

K2O = 0.1 x CK2O

Where
CNa2O is the sodium oxide concentration of the sample solution in mg/l

CK2O is the potassium oxide concentration of the sample solution in mg/l

Sodium oxide equivalent

 Calculate the sodium oxide equivalent content in % by converting the potassium

oxide content to the equivalent sodium oxide content and adding the measured sodium
oxide content from:-

Sodium oxide equivalent = Na2O + 0.658K2O

Note
The sodium oxide equivalent is sometimes referred to as the acid soluble alkali content to
differentiate from determinations carried out using other extraction methods, e.g. water
soluble alkali content.

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Alternative method

Preparation of calibration solutions and curves

 Whenever a new batch of reagent is used, determine the alkali content by means of
this method.

 If the alkali content of a reagent exceeds 0.01%, either replace the batch with a new
one, which shall be verified in the same way, or prepare new calibration solutions.

 In the case of cements with an insoluble residue < 3%, evaporate 20 ml of

hydrochloric acid 1+9 to dryness, and, in the case of cements with an insoluble
residue > 3%, evaporate 15 ml of hydrofluoric acid and 5 ml of sulphuric acid to
dryness for the purpose of preparing calibration solutions.

 In both cases dissolve the residue from evaporation with 2 ml of hydrochloric acid
1+9 and 3 ml of water.

 Transfer the solution to a 100 ml volumetric flask and add 10 ml of buffer solution
(dissolve 50 g of caesium chloride and 250 g of aluminium nitrate in water and make
up to 1000 ml with water).

 Add the quantities of the alkali stock solution to the volumetric flasks in the table
below then make up to the mark with water.

Volumetric flasks 1 2 3 4 5 6 7
Stock solution (ml) 0 1 3 5 10 20 30

 For an original test portion of 0.2000 g, the values measured for flasks 1 to 7
correspond to the Na2O and K2O contents shown in the table below.

Volumetric flasks 1 2 3 4 5 6 7
Na2O content (%) 0 0.07 0.20 0.34 0.67 1.35 2.02
K2O content (%) 0 0.06 0.18 0.30 0.60 1.20 1.81

 Spray the blank solution 1, into the flame photometer and set the indicator to zero.

 Spray the other solutions (2 to 7) in the order of increasing concentrations into the
flame photometer. Measure the intensities for Na2O at 589 nm and for K2O at 768 nm.

 Construct curves of the measured intensities against the corresponding concentrations

of Na2O and K2O in the calibration solutions.

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Cement with an insoluble residue < 3%

 Weigh 0.2000 + 0.0005 g of cement into a 250 ml beaker making a slurry by adding
3 ml of water then add 20 ml of hydrochloric acid 1+9 and evaporate to dryness.

 Add hot water and 2 ml of hydrochloric acid 1+9 to the residue and filter through a
medium, ashless filter paper that has been pre-washed with hot water into a 100 ml
volumetric flask containing 10 ml of buffer solution.

 Spray the sample solution into the flame of the flame photometer measuring the
intensity of the sodium line at 589 nm and the potassium line at 768 nm.

Cement with an insoluble residue > 3%

Hazard Warning

 Vapours from sulfuric acid and hydrofluoric acid are hazardous. Perform the
following evaporation procedures in a fume cabinet.

 Wear eye protection and suitable rubber or plastics gloves when handling or agitating
these acids or their mixtures.

 Weigh 0.2000 + 0.0005 g of cement into a platinum dish making a slurry by adding
3 ml of water and evaporate after adding 5 ml of sulfuric acid and 20 ml of
hydrofluoric acid.

 Evaporate to dryness under a heating lamp then mix the residue with hot water and
2 ml of hydrochloric acid 1+9 and filter through a medium, ashless filter paper that
has been pre-washed with hot water into a 100 ml volumetric flask containing 10 ml
of buffer solution.

 Spray the sample solution into the flame of the flame photometer measuring the
intensity of the sodium line at 589 nm and the potassium line at 768 nm.

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Calculations

 Obtain the sodium oxide or potassium oxide concentration in the solution respectively
by means of a linear interpolation from the intensities and associated concentrations
of the calibration solutions used.

 The scale values read off in conjunction with the calibration curves give the contents
of Na2O and K2O in percent respectively.

Sodium and potassium oxide content

 Calculate the sodium and potassium oxide content as a percentage for an original test
portion of 0.2000 g by dividing each value obtained, in percent by the actual mass of
the test portion and multiplying by 0.2.

Sodium oxide equivalent

 Calculate the sodium oxide equivalent content in % by converting the potassium
oxide content to the equivalent sodium oxide content and adding the measured sodium
oxide content from:-

Sodium oxide equivalent = Na2O + 0.658K2O

Note
The sodium oxide equivalent is sometimes referred to as the acid soluble alkali content to
differentiate from determinations carried out using other extraction methods, e.g. water
soluble alkali content.

Report

 Report that the test was carried out in accordance with BS 196-2
 name of the testing organisation and date of test;
 sample identification reference or number and location;
 unavoidable variations from specified procedure, with reasons;
 The test procedure used.
 The sodium and potassium content.
 The sodium oxide equivalent.

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Apparatus

 A Flame Photometer with a compressor and gas supply.

 250 ml and 600 ml beakers
 100 ml, 500 ml and 1000 ml volumetric flasks
 Glass stirring rods
 Hotplate, thermostatically controlled
 Heating lamp
 Platinum dishes
 Analytical balance readable to 1 mg
 Polyethylene storage bottles
 Magnet
 Platinum stirrer
 Filter funnel
 Pipettes and burettes
 Medium filter paper, ashless

Chemicals

 Concentrated nitric acid HNO3

 Concentrated perchloric acid HClO4
 Concentrated hydrofluoric acid (>40%) HF
 Concentrated sulfuric acid (>98%) H2SO4

 For the alkali stock solution (both methods)

 Sodium chloride NaCl dried to constant mass at 110 + 5 OC
 Potassium chloride KCl dried to constant mass at 110 + 5 OC

 For the acid stock solution (HCl/H3PO4)

 Concentrated hydrochloric acid HCl
 Concentrated phosphoric acid H3PO4

 For the calcium stock solution

 Calcium carbonate CaCO3 of purity > 99.9% dried to constant mass at 200 + 10 OC
 Concentrated hydrochloric acid HCl

 For the buffer solution

 Caesium chloride CsCl
 Aluminium nitrate Al(NO3)3.9H2O

The above solutions can be obtained made up ready for use

Note

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Notes

Quality assurance requirements specify that the equipment used shall be recorded and be
within its valid calibration period.

All apparatus should be clean, in good condition and comply with the dimensions specified.

Where a dimension or other specified requirement has a tolerance applied, this should be
checked regularly for compliance and a record maintained.

Where a dimension is specified with manufacturing tolerances or limits, it shall be an

essential dimension. Dimensions stated without tolerances are given for guidance.

Where mass is specified, the manufacturing tolerance shall be within + 1 % of the specified
mass unless otherwise stated.

Working tolerances apply to apparatus after being subjected to wear in use, and shall not
exceed twice the manufacturing tolerance unless other requirements are specified

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