S. K. Syal I a n d S. S.
Kataria 2
Accurate Rapid Analysis of Alkali Contents
in Portland Cement
REFERENCE: Syal, S. K. and Kataria, S. S., "AccurateRapid Analy-
sis of Alkali Contents in Portland Cement," Cement, Concrete, and Ag-
gregates, CCAGDP, Vol. 4, No. 2, Winter 1982, pp. 106-109.
ABSTRACT: Alkali contents of portland cement/clinker significantly
affect the hydration reaction rate and the development of mechanical
strength of cements. An accurate, rapid method has been developed for
the quantitative determination of alkalies sodium oxide and potassium
oxide by use of the flame photometric emission spectroscopic technique.
The procedure is free from errors caused by the presence of calcium
atoms and the mutual disturbance caused by the different ionization be-
havior of sodium and potassium salts in the flame. The determinations
have been performed in a nitric acid medium with use of optimum
amounts of aluminum sulfate and cesium sulfate as the controlling elec-
trolytes. A combination of 2000 ppm of alumina +30 ppm of cesium is
optimum for the analysis of ordinary portland cements and clinkers. In
the procedure a wide range of alkali concentration is covered by the anal-
ysis of solutions for 1 to 10 ppm of sodium oxide and potassium oxide
with the best reproducibility in the range of 4 to 8 ppm. The accuracy of
the determinations is better than 0.01 ppm. The method is suitable for
laboratory analysis as well as for on-line quality control determinations
of alkali content.
KEYWORDS: portland cements, alkalies, flame photometry, hydra-
tion, aluminum sulfate, cesium sulfate
Alkalies play a considerable rote in determining the rate at which
calcium silicates react with water [1-4], which affects significantly
both the hydration reaction rate and the development of mechanical
strength of cements. Kalousek [5] has found that soda brings about
a decrease in calcium oxide/silicate (C/S) ratio of calcium silicate
hydrate. Increased crystallization and morphological change in cal-
cium silicate hydrate gels have often been observed when alkalies are
added to these gels [6, 7]. The rapid release of some of the alkalies
into solutions when portland cement was shaken with water defi-
nitely indicated that alkalies were present partly as sulfates; now it is
also known that Na(CaO)8(AI203) 3 (NC8A3) and K(CaO)23(SiO2)12
(KC23S12), the forms in which the excess alkalies are found to be
present in ordinary portland cement (OPC), hydrate more rapidly
than calcium silicate (C2S) [8]. It has also been reported that the
alkalies can be incorporated into calcium silicate hydrate gels with-
out any changes in X-ray diffraction patterns, scanning electron
microscope (SEM) patterns, and infrared absorption spectra as in
the cases of alumina, ferric oxide, and sulfate [9].
Based on a presentation given at the 1979 Annual Convention of Chem-
ists, India.
1Pool officer, Centre for Rural Development and Appropriate Technol-
ogy, Indian Institute of Technology, New Delhi-110 016, India.
2Executive consultant, Feeders India Consultants, J-12/39, Rajouri Gar-
den, New Delhi, India.
0149-6123/82/0012-0106502.50
106
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absorption spectra as in the cases of alumina, ferric oxide, and sul-
fate [9].
In view of the important role that is played by the alkali contents
in OPC, it is necessary to have an accurate analysis that enables
understanding and assignment of the properties of cements for
quality control purposes. Of all the techniques and procedures tried
throughout the world, the flame photometric method for the deter-
mination of alkalies in cements and ceramics still appears satisfac-
tory [101. The development of the method proposed in this article
has been based on a thorough survey of the available literature and
an actual laboratory comparison of the available standard tech-
niques, namely Indian Standard Methods of Chemical Analysis of
Hydraulic Cement (IS 4032-68) and British Standard Methods of
Testing Cement (BS 4550-70, Part II); also, all known sources of
error were accounted for.
Development of the Proposed Method
The flame photometric technique gave low results for some so-
dium determinations because of ionization effects when acids con-
taining chlorine, such as hydrogen chloride and perchloric acid
were used for the decomposition of the sample [I1]. This effect of
the presence of hydrogen chloride or perchloric acid has been elimi-
nated by the use of sulfuric acid and nitric acid for the decomposi-
tion of the sample.
The high results obtained because of the spectral interference of
calcium on sodium emission have been excluded by the addition of
an aluminum sulfate solution to an aliquot of the main alkali stock
solution [11] as Ca 2+ was complexed by both AI 3+ and 5 0 4 2 - ions.
The quantity of aluminum sulfate added was kept to a m i n i m u m to
avoid contaminating the blanks and to prevent an undesirable in-
crease in the salt content of the solution. There seemed to be no
interference from anions in the flame photometric method. The
method of adding calcium salts to the calibrating alkali solutions
was found to be most unsatisfactory because it is necessary to deter-
mine the calcium concentration in the sample solution and then to
exactly match it, which, as a laboratory technique, is only of theo-
retical value. Even when the exact matching of calcium was done, it
seldom gave the same interference on the sodium emission, because
interference is not a linear function of calcium concentration.
The Indian Standard, British Standard, and International Orga-
nization for Standardization (IS, BS, and ISO) methods were based
on the consideration that there was no discernible interference of
one alkali on another, but Eardley and Reed [11] found that potas-
sium interfered in the determination of sodium because of the ion-
ization equilibria in the flame. Once the temperature of the flame
© 1983 by the American Society for Testing and Materials

was adequate enough to cause the dissociation of the molecules of
alkali salts into atoms, from which the characteristic radiation was
emitted, an equilibrium existed between atoms, ions, and electrons.
Na(atom) ~ Na + + e
K (atom) ~- K + + D e
As the ease of ionization increased in the order of sodium < potas-
sium < rubidium < cesium, it followed that potassium ionized to a
greater extent than sodium and hence produced a greater concen-
tration of electrons. When in a sample solution, such as in cement,
sodium was also present along with potassium, the net effect of their
presence led to the displacement of Na (atom) ~ Na + + e equilib-
rium to the left, thus increasing the concentration of sodium atoms
and, hence, the sodium emission (or the amount of light passing
through the sodium filter). Further, it was unlikely that sodium
would affect the potassium intensity. This interference could be
overcome either by exactly matching the sodium monoxide/potas-
sium oxide content of the standard solutions to that of the sample or
by adding an excess of potassium to ensure maximum light emission
for sodium. Neither of these suggestions was attractive as both
would complicate the determination of the two main alkalies to such
an extent that the method would never be suitable for quality con-
trol and rapid accurate analysis. The novel suggestions of Sanui and
Pace [12] were found to be most suitable and adaptable. They noted
that the apparent low values for potassium and high values for so-
dium when the sodium oxide to potassium oxide ratio is less than 2
could be overcome by the addition of cesium sulfate as an ionization
buffer. During our experimental variations, a combination of 30
ppm of cesium + 2000 ppm of aluminum sulfate has been found to
be the optimum for OPC.
Experimental Reagents
The reagents in the experiment were as follows:
1. Concentrated nitric acid, analytical reagent (AR) grade (spe-
cific gravity 1.42, 14N).
10
g8
-
~6
g
4
IE
2 10
2 ~ 6 8 10
Cone. of Sfondord soln.( pprn )
FIG. 1--Calibration of flame photometer for sodium oxide and potassium oxide analysis.
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SYAL AND KATARIA ON ALKALI CONTENTS 107
2. Nitric acid solution (1:1)--500 mL of concentrated nitric acid,
AR grade, diluted to 1 L with distilled water.
3. Sulfuric acid solution (1:1)--500 mL of concentrated sulfuric
acid diluted to 1 L with distilled water.
4. Aluminum sulfate stock solution (20 000 ppm alumina solu-
tion)--AR grade aluminum metal foil was cleaned by washing with
dilute hydrochloric acid, ethanol, and ether in succession and dried
well. Then, 10.58 g of the aluminum metal was weighed exactly in a
beaker, and the separately prepared solution that contained 40 mL
of sulfuric acid (1:1) + 120 mL of nitric acid (147/) + 50 mL of
double-distilled water was added. The mixture was allowed to react
by occasional heating on a water bath until the metal was fully dis-
solved. When the reaction was slow, a drop of mercury was added to
act as a catalyst. The mixture was heated until the nitrogen dioxide
was completely expelled. The residue was cooled and dissolved in
double-distilled water (DDW) and diluted to 1 L.
5. Cesium sulfate stock solution (300 ppm of cesium)--0.41 g of
cesium sulfate (AR grade) was dissolved to a 1-L solution.
6. Standard alkalies stock solution (100 ppm sodium oxide +
100 ppm potassium oxide)--prepared by dissolving requisite
amounts of sodium chloride and potassium chloride in DDW.
Procedure
The Analytical Instruments Manufacturing Industries, Ltd.,
(AIMIL) Flame Photometer Model C140 was calibrated for 0 to 10
ppm and 0 to 50 ppm by taking sodium chloride and potassium
chloride solutions, both AR grade, and drawing separate calibra-
tion curves (Fig. 1) for both ranges in order to determine the suit-
able workable concentration range. The standard solutions for cali-
bration were prepared as given in Table 1.
About 0.25 g of the cement/clinker sample was accurately
weighed and dissolved in 5 mL of Solution 2 + I0 mL of DDW by
continuous stirring and gentle heating. The mixture of 10 mL of
Solution 4 + 10 mL of Solution 5 was added to it. The contents were
heated, cooled to room temperature, filtered through a Whatmann
#40 filter into a 100-mL measuring flask, given five to six washings
SOl
~,0
30
20
/ h I , 1 ~ I I 1 l
10 20 30 40 50
Cone. of Stnndord soln.(ppm)
108 CEMENT, CONCRETE, AND AGGREGATES

TABLE 1--Standard solutions for calibration of a flame photometer.

Na20/K20 Total
Standard Composition, Solution 2, Solution 4, Solution 5, Solution 6, Volume
Solution ppm mL mL mL mL made, mL

Blank 0/0 5 10 10 0 I00

1 1/1 5 10 10 1 100
2 2/2 5 10 10 2 100
3 3/3 5 10 10 3 100
4 4/4 5 10 10 4 100
5 5/5 5 10 10 5 100
6 6/6 5 10 10 6 100
7 7/7 5 10 10 7 100
8 8/8 5 10 10 8 100
9 9/9 5 10 10 9 100
10 10/10 5 10 I0 10 100
15 15/15 5 10 10 15 100
20 20/20 5 10 10 20 100
25 25/25 5 10 10 25 100
30 30/30 5 10 10 30 100
35 35/35 5 10 10 35 100
40 40/40 5 10 10 40 100
45 45/45 5 10 10 45 100
50 50/50 5 10 10 50 100

TABLE 2--Comparative study by various methods. with warm D D W , and diluted to 100 mL with D D W . F u r t h e r dilu-
tions were made, wherever necessary, to bring the alkali concentra-
Average Analysis, % tions to within 10 p p m of sodium oxide and potassium oxide.
(from statistical data)
Method of Acid The flame photometer was adjusted to give full-scale deflection
Sample Analysis Medium NA20 K20 on a 10-ppm standard solution and zero on a blank solution. Fresh
calibration curves for a 0 to 10 p p m range were drawn for each set,
Japan Cement ISO HCI 0.49 1.01 separately for sodium oxide and potassium oxide, though calibra-
Japan Cement ISO HNO 3 0.46 1.01
tion was mostly reproducible. The sodium oxide and potassium ox-
Japan Cement BS HCI 0.46 0.697
Japan Cement BS HNO 3 0.45 0.73 ide contents of the sample solutions were determined by use of the
Japan Cement IS HCI fluctuating 0.56 calibration curve t h a t was drawn specifically for the same set.
Japan Cement IS HNO 3 0,68 0.65
Japan Cement proposed method HCI 0.436 0.697
Japan Cement proposed method HNO 3 0,434 0.73 Results a n d D i s c u s s i o n
Japan Cement standard values 0.432 0.73
NBS 1014 proposed method HNb 0.210 0,325 The calibration curve for the range 0 to 10 p p m (Fig. 1) was al-
NBS 1014 standard values 0.200 0,320 ways a straight line, while the 0 to 50-ppm range was represented by
NBS 1016 proposed method 0.540 0.040 an arc. So the workable range a d o p t e d was 0 to 10 p p m . The best
NBS 1016 standard values 0.550 0.040
proposed method 0.640 0.160 reproducibility was experimentally attained for the solutions in the
NBS 633 HNO3
NBS 633 standard values 0.640 0.165 range of 4 to 8 p p m of sodium oxide or potassium oxide, or both,
NBS 634 proposed method HNb 0.140 0,435 with an accuracy of + 0 . 0 1 p p m in the m e a s u r e d values.
NBS 634 standard values 0.140 0.430 A comparative study of the IS, ISO, BS, and the proposed meth-
NBS 636 proposed method HNO 3 0.105 0.565
ods was m a d e by the use of Japan Cement and National Bureau of
NBS 636 standard values 0.100 0.570
S t a n d a r d s (NBS) Cements, and the accuracy and reproducibility

TABLE 3--Statistical analytical data on reference cements.

Sample

RC-I RC-II RC-III RC-IV

Constant Factor Na20 K20 Na20 K20 Na20 K20 NA20 K20

1. Average value o.o77~ 0.800 0.226 0.781 0.454 0.474 O.163 0.245
X,%
2. Standard deviation s 6.06 × 10 -3 1.49 × 10 -2 1.269 × 10 2 8.50 × 10 -2 1.204 × 10 -2 1.028 × I0 2 5.75 × 10 -3 6.58 × 10 -3
3. Coefficient of 7.8 1,87 5.61 1.08 2,67 2.18 3.59 2.74
variation. 100S/x
4. Range, R 0.02 0.02 0,02 0.02 0.02 0.02 0.02 0.02

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were checked by use of the NBS cements. The average values de-
rived from the statistical data are given in Table 2.
The reproducibility of the values for OPC/clinker has been found
to be better than +__0.0t5 ppm, by analysis of a set of reference
cements that cover the alkali range 0.10 to 1.00% with reference to
sodium oxide and potassium oxide contents. The statistical data of
the analysis of these samples are given in Table 3.
From the experimental data a clear explanation of the suitability
of the proposed method for alkali analysis in OPC over a wide range
of possible concentrations is seen. All the possible causes of errors
were considered and eliminated in the proposed method. Since the
total experimental time needed for the analysis is very short, it is
quite suitable even for on-line analysis in the cement industry'.
Conclusion
The proposed method of analysis of alkalies by the flame photo-
metric technique, which uses a nitric acid medium in the presence
of 2000 ppm of alumina + 30 ppm of cesium, is quite useful as a
laboratory technique as welt as an on-line quality control technique
in the cement industry and can be considered as a possible standard
method.
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SYAL AND KATARIA ON ALKALI CONTENTS 109
References
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[4] Kryzhanovskaya, I. A., Mirakyan, V. M., and Shokotova, B. G., Tse-
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