METHOD A15 (a)

THE DETERMINATION OF THE CEMENT OR LIME CONTENT OF

STABILIZED MATERIALS BY MEANS OF THE ETHYLENE DIAMINE
TETRA ACETATE (EDTA) TEST

1. SCOPE

This method covers the determination of the proportion by mass of the lime or cement in a
stabilized material. This is done by extracting the calcium from the raw material, from the
stabilizing agent and from the stabilized material with hydrochloric acid and titrating with
EDTA.

From the results obtained the proportion of stabilizing agent in the stabilized material can be
calculated.

2. APPARATUS

2.1 A riffler with 25,0 mm openings.

2.2 The following test sieves (recommended diameter 200 mm): 19,0 mm, 13,2 mm, 2,36 mm and
0,425 mm with pan and lid.

2.3 A suitable laboratory crusher.

2.4 A suitable mechanical pulverizer, capable of pulverizing the sample to pass the 0,425 mm sieve.

2.5 A balance to weigh up to 100 kg, accurate to 0,001 g.

2.6 A balance to weigh up to 5 kg, accurate to 2 g.

2.7 A drying oven, thermostatically controlled and capable of maintaining a temperature of 105 to
110ºC.

2.8 Heating apparatus such as hotplates or Bunsen burners.

2.9 A 25 ml pipette (at least Class B, accurate at 20ºC).

2.10 A 50 ml burette with stand (at least Class B, accurate at 20ºC).

2.11 250, 500 and 1 000 ml volumetric flasks (at least Class B, accurate at 20ºC).

2.12 250 ml Erlenmeyer flasks.

2.13 500 ml breakers.

2.14 A wash bottle.

2.15 Filter funnels.

Standard Test Methods – Method A15(a) 1

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2.16 Filter paper (Whatman 541 or 41 or similar).

2.17 A fume cupboard (optional).

2.18 Cover glasses for the beakers.

2.19 Glass stirring rods with rubber tips.

2.20 A 50 ml measuring cylinder.

2.21 A dropping bottle.

Reagents

2.22 Nitric acid, concentrated (CP).

2.23 Hydrogen peroxide 100 vol.

2.24 1:1 hydrochloric acid solution (equal volumes of concentrated hydrochloric acid (CP) and
distilled water).

2.25 1:1 ammonia solution (equal volumes of concentrated ammonia (CP) and distilled water.

2.26 10 per cent sodium hydroxide solution (dissolve 10 g of sodium hydroxide (CP) in 100 ml of
distilled water).

2.27 2 per cent ammonium chloride solution (dissolve 20 g of ammonium chloride (CP) in 1 000 ml
of distilled water).

2.28 Nile blue ‘A’ indicator (dissolve 0,05 g of Nile blue ‘A’ in 1 000 ml of ethyl alcohol).

2.29 Calcein indicator (mix 0,2 g of calcein in 20 g of finely ground sodium chloride).

2.30 0,05 M EDTA solution (dissolve 18,612 g of EDTA (CP) disodium salt M 372,24) in distilled
water and make up to 1 000 ml). This solution should be stored in a plastic container as the
metal iron from the glass may decrease the titre of the EDTA.

2.31 Red litmus paper.

3. METHOD

3.1 Preparation of test sample

By means of the riffler quarter out a representative laboratory sample of the size given below. If
the sample contains aggregate retained on the 13,2 mm sieve, it should be crushed to pass the
13,2 mm sieve. The loss of fines and dust should be kept to an absolute minimum. For the sake
of convenience it is suggested that the raw soil and the stabilizing agent be tested
simultaneously.

Type of material Approximate mas of

Standard Test Methods – Method A15(a) 2
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 laboratory sample
Coarsely graded material (more than 20 % retained
on the 19,0 mm sieve) 6 kg
………………………………
Medium graded material (less than 20 % retained
on the 19,0 mm and less than 80 % passing the
2,36mm 2,5 kg
sieve………………………………………..
Finely graded material (more than 80 % passing
the 2,36 mm sieve) 250 g
……………………………………...

Dry the laboratory sample to constant mass at a temperature of 105 to 110 ºC. Pulverize the
dried sample to pass a 0, 425 mm sieve and mix thoroughly. Quarter out and weigh accurately,
approximately 10 g and transfer to a 500 ml glass beaker. In the case of lime or cement the
sample should be approximately 1 g.

3.2 Dissolving the test sample

It is recommended that 3 to 4 ml of hydrogen peroxide per gram of sample be added to peroxide

organic matter that may be present. Slight heating is suggested to accelerate the reaction. Wait
until all surface froth has disappeared, and then add about 10 ml of distilled water to prevent
gelling which may occur when hydrochloric acid is added.

Add about 10 ml of 1:1 hydrochloric acid per gram of sample (25 ml in the case of lime or
cement) and then add a few drops of concentrated nitric acid to oxidize any iron that may be
present and boil gently for about 5 minutes (not longer, as prolonged boiling may cause the
forming of a gel which will impede the subsequent filtration). Add the 1:1 ammonia solution
until the red litmus paper turns blue. An excess of ammonia must be avoided. A brown
precipitate will probably be formed owing to the presence of iron, aluminium, etc. (see 5.1).
Boil the solution gently for one minute (not mor as the precipitate may become slimy).

Filter the hot solution into a 500 ml volumetric flask. In order to reduce filtration time, first wet
the filter paper with hot 2 per cent ammonium chloride. Transfer the contents of the beaker
quantitatively into the funnel and wash the beaker and the residue on the filter at least four times
with hot 2 per cent ammonium chloride. Allow the filtrate to coll to room temperature and make
up to the mark with distilled water.

This is called the master solution.

3.3 Titration for calcium

By means of a pipette, transfer 25 ml of the master solution to an Erlenmeyer flask and add two
to three drops of Nile blue ‘A’ indicator. Add 10 per cent sodium hydroxide solution until the
blue colour changes to pink. Add 1 ml in excess. In samples with a high calcium content a
white precipitate of calcium hydroxide may form but during titration this will normally
disappear. This may be expedited by agitating the flask vigorously. If the precipitate still
remains, take another 25 ml of the master solution but add 50 ml of distilled water before adding
the sodium hydroxide solution.

Add approximately 10 mg of the prepared calcein insicator and titrate with the 0,05 M EDTA
solution until the green fluorescent colour disappears and a non-fluorescent pink colour
develops. If this pink colour remains for longer than 15 seconds the end point has been reached.
Record the quantity of EDTA used.
Standard Test Methods – Method A15(a) 3
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 A duplicate titration is recommended.

4. CALCULATIONS

4.1 Calculations of percentage of CaO in sample

Molecular mass of CaO = 56 g

1 litre1 M EDTA = 56 g CaO

1 litre 0,1 M EDTA = 5,6 g CaO

1 litre 0,05 M EDTA = 2,8 g CaO

1 ml 0,05 M EDTA = 0,0028 g CaO

% CaO in sample =

= (E1 x 0,0028) Vms x 100

Vp Ms

Where

E1 = volume of EDTA used for titration in 3.3 (ml)

Vms = volume of master solution prepared (ml)

Vp = volume of master solution used for titration (ml)

Ms = mass of test sample (g)

4.2 Calculation of percentage of lime or cement in sample

% lime or cement sample

= Cm – Cs
Ca – Cm x 100

Where

Ca = % CaO in cement or lime

Cm = % CaO in mixture

Cs = % CaO in raw material

Report the percentage of stabilizer to the nearest 0,1 per cent.

5. NOTES

5.1 If there is a large precipitate, calcium may be coprecipitated and it would be advisable to
redisolve the residue obtained during filtration by washing it back into the original beaker and

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 repeating the process as described under 3.2, but using 50 ml of the 1:1 hydrochloric acid.

5.2 When two stabilizing agents (e.g. cement plus slagment) have been used and it is required to
determine the proportion of each of these in the mixture, it will be necessary to determine the
MgO content in addition to the CaO content. The master solutions prepared for determining the
CaO can be used for this purpose as well. The following additional reagents are required:

5.2.1 Buffer solution (dissolve 34 g of ammonium chloride (CP) in 285 ml of ammonia. When
dissolved, make up to 500 ml in a volumetric flask with distilled water).

5.2.2 Eriochrome Black ‘T’ indicator (mix 0,05 g of Eriochrome Black ‘T’ indicator with 100 g of
finely ground sodium chloride).

5.2.3 Titrate as follows for CaO + MgO:

Pippette 25 ml of the master solution into an Erlenmeyer flask and add 10 ml of the buffer
solution. Heat the flask with contents to approximately 70 ºC (avoid boiling as this will cause
the ammonia in the buffer solution to evaporate which in turn will impede the colour change
during titration). Add approximately 10 mg of Eriochrome Black ‘T’ indicator and titrate with
0.05 M EDTA until the dark colour changes to dark blue. Record the quantity of EDTA used.

A duplicate titration is again recommended.

5.2.4 The percentage of MgO in the sample is calculated as follows:

Molecular mass of MgO = 40,30

1ml 0,05 M EDTA = 0,002015 g MgO

% MgO =

[0,002015 (E2 – E1)] Vms x 100

Vp Ms

Where

E1 = volume of EDTA used for the titration in 3.3 (ml)

E2 = volume of EDTA used for this titration (ml)

Calculate the percentage of stabilizing agents in stabilized material (e.g. cement and slagment)
as follows:

% cement =

(Mm – Ms) (Cb – Cs) – (Cm – Cs) (Mb – Ms)

(Cb – Cs) (Ma – Ms) – (Ca – Cs) (Mb – Ms) x 100

where

Ca = % CaO in cement

Cb = % CaO in slagment
Cs = % CaO in raw material

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 Cm = % CaO in mixture

Ma = % MgO in cement

Mb = % MgO in slagment

Ms = % MgO in raw material

Mm = % MgO in mixture.

% slagment =

(Cm – Cs) (Ma –Ms) - (Ca – Cs) (Mm - Ms)

(Cb – Cs) (Ma –Ms) - (Ca – Cs) (Mb - Ms) x 100

% cement + slagment = the sum

of the values obtained above.

The content may also be calculated from the following formula:

% cement + slagment =

(Cm – Cs) (Ma – Mb) - (Mm - Ms) (Ca – Cs)

(Cb – Cs) (Ma –Ms) - (Ca – Cs) (Mb - Ms) x 100

5.3 It is not possible to caary out accurate determinations of stabilizer content in cases where the Ca
(and Mg) content of the raw soil varies, as in the case of calcretes, for example.

REFERENCES

BS 1924 - 1967
ASTM Designation 2901 - 1970
Road Note 28 (R.R.L. England)

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