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Cement and Concrete Research, Vol. 24, No. 2, pp.

343-352, 1994
Copyright 1994 Elsevier Science Ltd
Pergamon Printed in the USA. All rights reserved
0008-8846/94 $6.00 + .00

RAPID T E C H N I Q U E S F O R D E T E R M I N A T I O N O F F R E E L I M E AND F R E E
M A G N E S I A IN C E M E N T C L I N K E R AND P O R T L A N D I T E IN H Y D R A T E S

P. Arjunan and A. Kumar


Central Glass and Ceramic Research Institute
Jadavpur, Calcutta 700032, India

(Refereed)
(ReceivedMarch22; in finalformSeptember24, 1993)

ABSTRACT
Free lime is estimated by refluxing a sample quantity of ground clinker or cement in an
alcoholic solution of ammonium acetate under gentle boiling. The resultant extract is filtered
and titrated with EDTA to provide free CaO content. The method has been termed the
Ammonium Acetate Method (AAM). The same technique is also applicable to the estimation
of portlandite in hydrated cement. Alcoholic solution prevents cement hydrolysis.

Free MgO is extracted from clinker in the form of a double salt through reaction with
ammonium nitrate. Use of ethanol again prevents hydrolysis of MgO present as solid
solution in cement compounds. The technique has been termed the Ammonium Nitrate
Method (ANM). The developed methods have been compared with existing standard
procedures.

Introduction

The presence of uncombined lime or free lime and free magnesia in cement clinker can lead to
unsoundness in cement materials after hydration through excessive volume change. The content of
free lime in clinker is also an indicator of the efficiency of the clinkerisation process. A variety of
methods have been proposed for the determination of free CaO in clinker and cement based on
extraction methods in aqueous, non-aqueous and acid-solvent media.(1-10) The use of ammonium
salts for the extraction of free lime in cement had also been developed.(11-13) However, no recent
literature is available on the use of ammonium salts to extract free lime from cement. Conventional
techniques for the determination of free lime do not include the use of ammonium salts even though
early studies on cements and the parallel soil systems indicated useful application potential.

A parallel system to free lime in cement clinker exists for the evaluation of exchangeable cations
in soils. A determination of the cation exchange capacity (CEC) of soil/mineral involves the
determination of the total quantity of negative charge per unit weight of the material.(14) The most
common exchangeable cations in soil are Ca 2+, Mg 2+, K +, Na +, NH4+, H +, and the use of
ammonium salts to determine their contents is an age old technique. The use of ammonium
chloride as an exchangeable medium for determination was formulated by Hissink(15) and, later,
Schollenberger (16) proposed the use of ammonium acetate in place of the chloride. Modifications
to the method by Schollenberger were made so as to reduce the possiblity of leaching of calcium
carbonate such as by replacing the aqueous acetate solution with 40 to 80% alcoholic solution of
NH4OAc" (17, 18)
343
344 P. Arjunan and A. Kumar Vol. 24, No. 2

In cement systems there is always a doubt that the leachate will exsolve Ca 2+ from cement
compounds during the extraction process. Lerch and Bogue (19) have indicated that the use of
excess ammonium acetate beyond the end point during titration gives a high value of free lime due
to attack on cement compounds. At the same time, it is well known that this attack can be
countered by using a solvent such as absolute ethanol to reduce the liability of hydrolysis of cement
compounds through a lowered pH. This is the theme on which the current paper has been
developed in an attempt to utilise a purely alcoholic solution to prevent leaching of cement
compounds while extracting free lime from cement clinker/hydrates using ammonium acetate as the
leachant.

Very few analytical techniques have been reported for the determination of calcium hydroxide
in hydrated cement .(4, 5, 20-23) The existing techniques propose the solution of calcium hydroxide
in an organic solvent and the main difficulty, as with all analytical techniques, arises from the
accompanied solution of combined lime. Among the reported techniques, the glycerol-alcohol
method of Lerch and Bogue (20) and the acetoacetic ester-isobutyl alcohol method of Franke (20)
have been widely used to determine the portlandite content of hydrated cement materials.

Methods for the determination of free MgO in cement is not well reported in literature. The one
proposed by Bogue and Taylor (24) is among the only available method thus indicating that it is a
challenging task to evolve methods for the accurate determination of free MgO in cement clinker.
In light of the above, the present work was taken up to evolve a set of methods to determine free
lime, free magnesia and portlandite in cement clinker and hydrates.

Method for the Determination of Free Lime and Calcium Hydroxide

Free lime in cement clinker can be determined through the extraction of this free lime in an
alcoholic solution of ammonium acetate. The method has been termed the Ammonium Acetate
Method (AAM). The first step is to prepare an alcoholic ammonium acetate solution by dissolving
ammonium acetate in absolute ethanol. The second step is to reflux this solution with the cement
sample ground to -75 I~m (200 mesh IS) at gentle boiling temperature for an appropriate time
followed by cooling and filtration.

The basic reaction occuring during refluxing is:

CaO + 2CH3COONH 4 -4 (CH3COO)2Ca + H20 + NH 3 (1)

Water is added to the filtrate and neutralised with dilute hydrochloric acid/sodium hydroxide
solution before titration. NaOH solution (5N) is added along with P and R indicator to the filtrate
and titrated against prestandardized EDTA until the color changes from pink to blue to indicate the
end point and the CaO content is calculated. Portlandite in hydrated cement paste is analysed in a
manner similar to free lime in clinker.

Method for the Determination of Free Magnesia

The method developed for the determination of free magnesia in clinker has been termed the
Ammonium Nitrate Method (ANM). An alcoholic solution of ammonium nitrate is prepared by
dissolving the same in absolute ethanol. As in the case of free lime, finely ground cement sample
is refluxed with the alcoholic solution at gentle boiling temperature followed by cooling and
filtration. Water is added to the filtrate and neutralised with dilute HCI/NaOH. Complexometric
titration with EDTA is conducted in two separate ways:

(a) After addition of pH 10 buffer and mixed indicator, the end point indicated by a color change
from pink to green. This titre value accounts for the total quantity of CaO and MgO.
Vol.24, No. 2 LIME,MgO,CLINKER,PORTLAND1TE,HYDRATES,TECHNIQUES 345

(b) After addition of NaOH (5N) and P and R indicator, the end point indicated by a color change
from pink to blue. The titre value accounts for the CaO content.
A difference between (a) and (b) titre values, after calculation, provides the free MgO content in the
clinker.

Experiments Conducted
Ri~w Materials Used

An ordinary portland cement (OPC-I) analyzing 61.80% CaO and 21.55% SiO 2 was used for
most of the studies. The cement was taken from a regular bag of marketed OPC in India. In
addition, pozzolana admixed portland cement (OPC-POZ), blast furnace slag admixed portland
cement (OPC-BFS), ground granulated blast furnace slag (GGBFS) and pure gypsum were also
used.

Reagents Used

1. Ammonium Acetate (AR) - dried in a desiccator for about 7 days to remove the moisture.
2. Ammonium Nitrate (AR) - dried in a desiccator for about 7 days to remove the moisture.
3. Ethyl alcohol (Absolute) - 99.5% purity.
4. All other reagents used for the experiments were AR/GR

Free Lime Estimation

A series of experments have been conducted to determine the optimum ammonium acetate
concentration required, solvent volume and the duration of refluxing on the CaO content
determined by AAM. Results from this method have been compared to the Bogue (20) and Franke
(20) methods. In the first instance, the solvent volume was fixed at 100 mL and the refluxing time
at 40 minutes, while the acetate concentration was varied from 0.002 to 0.016 N. It should be
mentioned that numerous probe experiments were conducted prior to the control series reported
herein to determine the regimes within for the control experiments.

The second series constituted experiments in which the solvent quantity was optimised.
Experiments were conducted in which the solvent volume was varied between 30 and 100 mL.
The sample weight, refluxing time and acetate concentration were fixed during the experiments. A
third series was designed to optimise the reflux time keeping all other parameters fixed.

Experiments were also conducted on samples in which the CaO content had been enhanced
through external addition of pure CaO, and experimental results compared to the theoretical
predictions. Reverse experiments were also carded out, the free CaO content being reduced
through the addition of a mixture of relatively pure SiO 2 and A1203, and the recovered CaO
compared to the theoretically estimated value. The experimental batches for this part of the study
are listed in Table 1. All experiments were conducted on OPC-I.

Portlandite Estimation

Hydrated pastes of OPC-I were prepared for estimation of portlandite. About 150 g of cement
(OPC-I) was mixed with 60 mL water and vigorously stirred for 5 minutes. Representative
portions of the paste were placed in plastic vials sealed immediately with tight fitting caps, dipped
in molten paraffin wax and stored in an air tight desiccator at room temperature. At specified age
of tests of 3, 7, 14, 21, and 28 days of hydration, the vials were broken away from the samples.
The samples were washed in acetone and crushed to pass through 150 ktm sieve, dried at 100-Z-_5C
for 1 hour and stored as parent sample for further studies. The portlandite estimation by various
techniques described here were conducted from the same dry paste samples.
346 P. Arjunan and A. Kumar Vol. 24. No. 2

Table 1
Theoretical CaO Contents in Batch Compositions
of Modified Ordinary Portland Cement

Sample Weight of CaO SiO2 A1203 CaO


Number cement Added Added Added Estimated
(g) (g) (g) (g) (wt.%)

1 1.0000 0.64*
2 1.0000 0.0010 0.74
3 1.0000 0.0020 0.84
4 1.0000 0.0030 0.94
5 1.0000 0.0040 1.04
6 1.0000 0.0050 1.14
7 1.0000 0.0060 1.24
8 0.8334 0.0833 0.0833 0,52
9 0.6660 0.1670 0.1670 0.44
10 0.5000 0.2500 0.2500 0.34
11 0.3340 0.3330 0.3330 0.24
12 0.1666 0.4167 0.4167 0.14

Solvent Content 100 ml; Ammonium Acetate Concentration 0.004 N; Refluxing Time 40 min.
*: By Experiment in case of sample 1; By calculation with respect to sample 1 in others.

In the AAM procedure, about 0.1 g accurately weighed prepared sample of dry hydrated pastes
was taken in an Erlenmeyer flask. To the flask, 100 mL of 0.12 N ammonium acetate, prepared in
absolute ethyl alcohol, was added and the contents were refluxed for 30 to 40 minutes. After
cooling the flask, the contents were filtered and titrated complexometrically and Ca(OH)2 was
calculated as CaO from the titre value. TGA studies (Shimadzu TGA50) were conducted on the
dry hydrated pastes for portlandite estimation. About 20 mg sample was taken for the experiment.
The heating rate was maintained at 10C/min. up to 80C. The weight loss between about 455
and 485 corresponding to dehydroxylation of Ca(OH) 2 was calculated from digital data and
compared with the value estimated through AAM.
Experiments were also conducted by Franke's method (20)for the determination of Ca(OH)2 as
CaO. A 0.1 g sample was refluxed with 70 mL of 3:20 acetoaceticester and isobutyl alcohol for
about 1 hour. After refluxing, the contents were immediately cooled and filtered. To the filtrate,
10 to 12 drops of Thymol blue indicator were added and titrated against standard perchloric acid.
An experiment was also carried out by the Bogue method (20) on 21 day hydrated sample for the
determination of portlandite in OPC paste.

Free Mamaesia Determination

Free magnesia was determined following the ANM procedure. Since OPC-I did not analyse
for free magnesia, the cement was spiked with pure magnesia. The recovery of free magnesia by
the new method (ANM) was compared with that from the Bogue and Taylor (BT) method. (24)

Results and Discussions

Free Lime Determination

Assuming that the reaction between free calcium oxide and ammonium acetate is as given in
equation (1), the theoretical quantity of the acetate required to react with the free CaO in a 1 g
sample of portland cement with 1 wt.% free lime is 0.0025 moles. At the same time, initial probe
Vol.24, No. 2 LIME,MgO,CLINKER,PORTLANDITE,HYDRATES,TF_~HNIQUES 347

studies showed that the concentration of the acetate solution during reaction controlled the value of
the recoverable free CaO. Experiments to determine this dependence were carried out and the
results are given in Table 2.
Table 2
Effect of Ammonium Acetate Concentration on
the Free Lime Content

Sample Acetate Free Remarks


Weight Concentration Lin~
(g) (N) (%)

0.5 0.002 0.62


1.0 0.004 0.61
1.0 0.008 0.81
1.0 0.016 0.35 Flocculated

It may be stated from Table 2 that when the concentrations were maintained at 0.002 and 0.004
N and the sample sizes were 0.5 and 1.0 g respectively for the same solvent volume of 100 mL
and a reflux time of 40 min., the values obtained for free lime content were alike. Increasing the
concentration to 0.008 N increased the value of free lime content. The theoretical amount of acetate
required for this OPC with 0.64 wt.% free lime is 100 mL. of a 0.002 N solution. Thus it is
possible to extract free CaO without disturbing the CaO in silicates and cement compounds even
with the use of an acetate concentration of at least two or three times the amount theoretically
required as in this particular case keeping all parameters constant. The same solution
concentration, say of 0.004 N in this case and a 100 mL. solvent volume, would permit the
recovery of free CaO up to about 2.5 wt.% by suitably reducing the sample size, at the same time
without affecting the accuracy of the estimation. However, as will be shown later, the system
works with accuracy in a range between half and double the measured value of free CaO obtained
in this particular case.

Effect of Refluxin~ Time on Free Lime Content

In order to determine the rapidity of this method a series of experiments were conducted with
varying refluxing time, while keeping ammonium acetate concentration, sample size, and solvent
volume constant. The refluxing period was varied from 15 minutes to 3 hours. The results are
shown in Figure 1. At 15 minutes, the reaction is incomplete and a low value of free CaO is
obtained compared to that estimated by the Lerch and Bogue method (20) _ hereafter referred to as
the estimated value. At three hours, free lime value was higher than the estimated value. This may
be due to the fact that ammonium acetate extracts some of the CaO from the cement compounds
during this long reflux. However, for the refluxing periods between 30 and 90 minutes, the free
lime value was virtually constant and corresponds to the estimated value.

Effect of Solvent Volume on Free Lime Content

Absolute ethyl alcohol (ethanol) as a solvent medium plays an important role in the estimation
of free lime by AAM. Use of ethanol as a solvent helps to reduce the pH of the system and thereby
prevents the hydrolysis of the cement compounds. Available literature (25) shows that ethanol
forms a Ca-ethoxide intermediate before the formation of Ca-acetate. A series of experiments were
conducted to obtain the optimum solvent volume during refluxing. In this study, the volume of
ethanol was varied from 30 to 100 mL. while keeping theother parameters constant. The results
are given in Figure 2. Low free lime value was obtained for solvent volume of 30 to 40 mL. It
may be stated that at lower solvent volume the concentration of ammonium acetate increases which
is responsible for heavy flocculation of a gelatinous precipitate not permitting complete reaction.
The free CaO content was constant and corresponds to the estimated value for solvent volumes
between 50 and 100 mL.
348 P. Arjurtan and A. Kumar Vol. 24, No. 2

0"80

~0"60

G)
E
~0"40 -

FIG. 1
Q) Influence of refluxing time on
free lime determined in OPC-I
u.
0"20
Acetate Cone. 0'004 N
Solvent Volume I 0 0 mL
Sample Weight I'0 g
O0 i I i I i I
50 I00 150 2OO
Refluxing Time {rains)

Comoarison with Other Standard Methods and Effect of Admixtures

The accuracy of AAM has been compared with two standard methods, viz. the glycerol-ethanol
ASTM method (20) and Franke's acetoacetic ester-iso butyl alcohol method. (20) The results are
given in Table 3. Free CaO contents in OPC-I attained by the three methods reported in Table 3 are
in satisfactory agreement with each other. However, when a second cement, OPC-II, was studied,
AAM yieded the lowest results compared with the other two methods. The data indicates that the
present method compares well with the other two methods in the lower range of free lime content.
Repeat experiments provided free lime values within i-0.01 of the reported values in Table 3.

Grounded Granulated Blast Furnace Slag (GGBFS) does show some leachable CaO both by

0"80

0"60
/ o____---o

EO'40
~
FIG. 2
J Effect of ethanol volume on
free lime determined in OPC-I
L

u. 0 . 2 0 -
Acetate C o n e . 0.004 N
Refluxing Time 4 0 mins.
Sample Weight I-0 g
I , I L I i I I
00 25 50 75 I00 125
Alcohol Volume ( m L )
Vol. 24, No. 2 LIME, MgO. CLINKER, PORTLANDITE,HYDRATES,TECHNIQUES 349

the AAM and Franke methods. Interestingly this CaO is not detectable by the Bogue method due
to heavy flocculation. Again, the AAM provides the lowest free lime in OPC-GGBFS cements
compared to other methods. AAM and Franke methods give lower total free lime compared to the
Bogue method for the OPC-BFS. The free lime content in pozzolana based OPC(OPC-POZ) was
found to be very low by the AAM while none was detected by the Bogue or Franke methods.
Gypsum is expected not to contribute to free CaO estimation in portland cement by the AAM since
only 0.02% CaO is extracted from pure gypsum as reported in Table 3. It shoud be noted that the
CaO extraction from gypsum was carried out in a very concentrated acetate solution of 0.016N.

Table 3
Content of Free Lime Determined by
Standard Techniques (BM and FM) and the Developed Method (AAM)

Cement Sample Acetate Free lime (%)


Sample Weight Conc. AAM BM FM
(g) (N)

OPC-I 1.0 0.004 0.62 0.63 0.68


OPC-II 1.0 0.008 1.71 2.13 2.14
OPC-BFS 1.0 0.004 0.96 1.11 1.07
OPC-POZ 1.0 0.004 0.03 ND ND
GGBFS 1.0 0.008 0.18 NPD 0.12
GYPSUM 1.0 0.016 0.02 NE NE

ND: None Detected; NPD: Not Possible to Detect; NE: Not Estimated; POZ: Pozzolana; GGBFS:
Ground granulated blast furnace slag.

Effc~ of Reduced or Enhanced Free Lime Content in O l ~

The results of a series of experiments (Table 1) conducted on the external addition of cement
constituents (SiO 2 and A1203 ) and pure CaO to OPC-I are given in Figure 3. The figure indicates
that the free lime extracted is equal to the theoretically calculated value from 0.34 to 1.14 wt.% free

1"50 Acetate Conc.


Solvent Volume
0.004N
I 0 0 mL /
/
Sample Weight 1.0 g /

~
Refluxing Time 4 0 rains. /

.~I'00
FIG. 3
m203 + SiO2
added
Experimentally recovered free
lime in OPC samples with
additions of pure CaO or pure '1o
silica and alumina ~0"50
g - ~/~ CaOa d d e d
G)
n," /

00 / = O" I5 0 OPCm I
I" O 0
,

1"50
Estimated Free Lime ( % )
350 P. Arjunan and A. Kumar Vol. 24, No. 2

lime content when all experimental parameters are held constant. The higher value of free lime
content at low sample weight gives further emphasis to the fact mentioned earlier that at higher
ammonium acetate concentration, some of the combined calcium is extracted from the cement
constituents. However, the low value obtained for samples above an estimated free lime content of
1.14 wt.% gives the impression that his method is suitable for low free lime content and requires
suitable modification of experimental parameters for the estimation of relatively high free lime
contents.

Determination of Free Calcium Hydroxide in Hvdrated Cement

The present method (AAM) for the determination of free CaO has been extended to estimate the
free Ca(OH) 2, Portlandite, content in dry hydrated cement pastes. Ammonium acetate
concentration of 0.12 N was used such that the portlandite content can be estimated up to 40 wt.%
as CaO in 100 mL solvent for 0.1 g sample. The results are given in Table 4. The two major
constraints, flocculation due to increase in ammonium acetate concentration and extraction of Ca
from cement compounds due to longer duration of refluxing, observed in free lime determination in
clinker have not been noticed in the determination of portlandite by the present method. However,
both Franke method and the present method show higher portlandite than that estimated through
TGA as seen in Table 4. There is reason to believe that Ca will be leached from cement hydrates
by organic solvents during the refluxing. (6) The low result for the 21 day hydrated sample in the
Bogue method (20) indicates that it requires two or three extractions on the same sample to obtain
the optimum portlandite content. The estimation time for a TGA is 2 hours, for Franke is 1 hour
and 30 mins., for Bogue is 3 hours while the AAM requires 45 minutes. The low values of
portlandite determined in dry hydrated pastes was reconfirmed through repeat experiments which
yielded similar results and may be due to poor reactivity of the marketed OPC-I or due to washing
of the paste with acetone.

Table 4
Estimated Portlandite Content in Dry Hardened OPC-I Pastes
using Standard Techniques and the Developed Method (AAM)

Curing Portlandite Content (wt.%)


Time AAM FM BM TGA
(davs)
3- 9.1 10.0 NE 8.2
7 9.9 11.5 NE 9.2
14 11.2 11.9 NE 9.6
21 12.0 12.3 9.3 10.7
28 12.6 12.8 NE 9.6

NE: Not Estimated; AAM: Ammonium Acetate Method; FM: Franke (20); BM: Bogue (20); TGA:
Thermogravimetry

Determination of Free Magnesia

Free MgO can be determined in cement clinker samples by modifying the method proposed by
Bogue and Taylor. (24) Bogue and Taylor have proposed the use of 60 mL of 5:1 ethanol -
glycerol mixture as the solvent. The free MgO can be extracted with ammonium nitrate after
refluxing for 4 to 5 hours. The extracted MgO is filtered and estimated by titration. The modified
approach in this study (ANM) makes use of ethanol as the solvent. The free MgO is extracted with
ammonium nitrate in ethanol medium by refluxing between 0.5 to 1.0 hour. The method is rapid
and accurate. The proof of the method has been established by physical addition of a known
quantity of MgO to a clinker sample that did not analyse for free MgO. Determination of the MgO
content in this sample was made by the Bogue and Taylor (24) method (BT) and the ANM
technique after this addition of MgO. The results are given in Table 5. As seen from the Table, the
Vol. 24, No. 2 LIMb MgO, CLINKER, PORTLANDITE, HYDRATES, TECHNIQUES 351

results showed a 99.8% efficiency for MgO recovery in the Bogue-Taylor method and a 99.4%
efficiency in the present case which is considered acceptable. The total time for the BT method is
about 135 minutes while it is about 45 minutes for the ANM. The free CaO obtained by this
method is higher than that obtained in the AAM.

Table 5
Free MgO Recovered from Samples of OPC Doped with Magnesia using
the Bogue-Taylor (24) (BT) and the Developed Technique (ANM)

Method Sample MgO Refluxing Recovered Extracted


Used Weight Added Time MgO CaO
(g) (g) (mins) (g) (g)

BT 0.50 0.005 120 0.00499 0.0100


ANM 0.50 0.005 30 0.00497 0.0125

OPC-I was used as the sample and did not analyse for free MgO

Summary
Ammonium acetate reacts with free CaO according to:

CaO + 2CH3COONH4 --->(CH3COO)2Ca + H20 + NH 3

In the developed AAM use of ethanol as a solvent medium helps to reduce the pH of the system
and thereby prevents hydrolysis of the cement compounds. Available literature shows that ethanol
forms a Ca-ethoxide intermediate leading to the formation of Ca-acetate. Ammonium acetate
concentration up to double the amount theoretically requred for reaction can be used without
attacking the cement compounds. The system works well in the lower range of free lime values.
The reaction between free CaO and ammonium acetate is fast and complete within 30 to 40 mins.
The filtration provides a clear solution for titration. The complexometric titration with EDTA is
sensitive, accurate and can be performed with ease. The same technique is also applicable to the
estimation of free Ca(OH) 2 in hydrated cement samples. The basic reaction occuring is same as
that in free lime determination.

Free MgO in portland cement forms a double salt with ammonium nitrate according to the
equation:

MgO + 4NH4NO 3 --->Mg(NO3)2(NH4)2 + 2NH 3 + H20

Use of ethanol prevents hydrolysis of MgO present as solid solution in cement compounds.
Ethanol also enhances the speed of the reaction and avoids disadvantages faced by other solvents in
performing complexometric determination of free MgO. The developed techniques compare well
with existing ones for the determination of free lime, portlandite, and free magnesia. The
techniques are rapid and simple to employ.

Acknowledgements
The authors wish to thank Dr. B.K. Sarkar, Director, GGCRI, for kind permission to publish
this paper. The authors are extremely grateful to Dr. H.S. Maiti, Head Analytical Chemistry
Division, and Dr. G. Banerjee, Head Refractories Division, GGCRI, for their advice and help
during the study.
352 P. Arjunan and A. Kumar Vol. 24, No. 2

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