VARIAN

INSTRUMENTS
AT WORK
ATOMIC ABSORPTION
Chemical Analysis of Portland
Cement by Atomic Absorption
Spectroscopy
Number AA-18
December 1981
Roger M. Januszke and Graham J. Glover,
Materials and Research Laboratories,
Highways Department, Adelaide, Australia.
Summary
A relatively rapid and accurate atomic absorption
procedure is described for the determination of seven
oxides, Ca, Si, Al, Fe, Mg, Na and K, in Portland
cement. The method employs only simple fusion and
dilution techniques and allows all seven elements to
be determined from one fusion. NBS standards were
employed for calibration of the instrument to minimize
the matrix effects. The precision and accuracy is
sufficient for quality assurance purposes and compares
well with wet analysis carried out according to
Australian Standards. The time required for analysis
of a single sample is approximately six hours and this
would be decreased if more samples had to be tested.
Introduction
The chemical analysis of cement is carried out in
order to check if the supplied product conforms to
Specification requirements. For routine check of the
cement chemical composition, the application of
UV-Vis spectroscopy is adequate (1). In the case of
dispute with the supplier, time-consuming methods
based on classical wet analysis (2) must be employed.
The application of atomic absorption spectroscopy
(AAS) for the analysis of cement has been reported by
a number of workers (3-8). There are a number of
dissolution procedures for silicate materials, and efforts
were directed into evaluating which of the methods is
most suitable for subsequent analysis. A number
of fluxing agents were evaluated, such as lithium
metaborate (9), lithium tetraborate (5) lithium tetraborate
with lithium carbonate (10,11), lithium carbonate
with boric acid (3), and sodium hydroxide (12).
Further work was directed into the selection of
optimum conditions for each element in the
concentration ranges (percentage of their oxides)
indicated below:
Ca as CaO 60-66
Si as SiO
2
18.5-24
Al as Al
2
O
3
0-7
Fe as Fe
2
O
3
0-4.5
Mg as MgO 0-4
Na as Na
2
O 0-0.7
K as K
2
O 0-0.7
The standard solutions for calibration were prepared
from NBS standard cement samples and thus matrix
effects were decreased to a minimum.
Experimental
Apparatus and Reagents
A Varian Model AA-775 double-beam atomic
absorption spectrophotometer with background
corrector, microprocessor control and digital display
was used in this study. Instrumental parameters are
listed in Table 1.
Lanthanum/cesium solution.
A 5% lanthanum/0.5% cesium solution in 1.5 M
hydrochloric acid was prepared by moistening 29.32 g
of lanthanum oxide (L.R.) and 3.17g cesium chloride
(A.R.) with distilled water and adding slowly 67.5 mL of
concentrated hydrochloric acid (A.R.), before dilution
with distilled water to 500 mL.
Reference samples.
National Bureau of Standards cement samples and
Cement and Concrete Association co-ordination
samples of cement.
Lithium metaborate - spectro flux grade 100A supplied
by Johnson-Matthey Chemicals.
Procedure
Weigh 1.50 g of lithium metaborate into a 30 mL
platinum crucible and mix well with 0.5000 0.0001 g
of cement. For the blank no cement is added to the
crucible. Place the crucible in the mouth of the muffle
furnace and heat at 1050C for 15 minutes. Take out
the crucible at 5 minute intervals and swirl contents
gently to ensure melt is homogeneous and that
complete solution is achieved. Remove from the
furnace and gently swirl. Cool for 30 seconds.
Place the platinum crucible in a polypropylene beaker
containing 10 mL of concentrated hydrochloric acid
made up to approximately 130 mL with boiling distilled
water Place on a magnetic stirrer and stir until
completely dissolved (10-20 minutes).
Solution 1. Wash contents of beaker into a 250 mL
volumetric flask through a funnel, rinsing beaker,
crucible and stirrer with distilled water. Add 25 mL of
lanthanum/cesium solution and make up to the mark
with distilled water.
Solution 2. Take a 10 mL aliquot of Solution 1 and
place in a 100 mL volumetric flask. To this add 10 mL of
lanthanum/cesium solution and make up to the mark
with distilled water.
Solution 3. Take a 10 mL aliquot of Solution 2 and
place in a 100 mL volumetric flask. To this add 10 mL of
lanthanum/cesium solution and make up to the mark
with distilled water.
A fresh fusion blank solution should be prepared each
time a new batch of lithium metaborate is used.
Select three to four reference cement samples that will
bracket the expected concentrations of the elements
in the unknown sample.
SiO
2
and CaO are determined in the absorbance
mode. Al
2
O
3
, MgO, Na
2
O and K
2
O are determined in
the concentration mode. However, each time a new
set of standards is prepared a check must be made on
the standards in the absorbance mode.
Acknowledgement
The authors thank Mr. F. Krebbekx for his assistance
during the experimental section of this work and the
Commissioner of Highways for permission to publish
this paper.
References
1. Australian Standard 1378/72 - Method for the
Spectrophotometric Analysis of Cement.
2. Australian Standard 2350.2/80 - Chemical
Composition of Portland Cement.
3. S.H. Omang, Anal. Chim. Acta 46, 225 (1969).
4. J.T. Roos and W.J. Price; Analyst 94, 89 (1969).
5. L.R. Butler and K. Kroger, Cement Technology 2,
81 (1971).
6. G. Legrand, J. Louvrier, N. Musikas and
I.A. Voinovitch, Analusis 2, 9 (1973).
7. R.F. Crow and J.D. Connolly, J. Testing and
Evaluation 1, 382 (1973).
8. C. Falinower, Analusis 4, 227 (1976).
9. C.O. Ingamells, Anal. Chim. Acta 52, 323 (1970).
10. H. Kodama, J.E. Brydon and B.C. Stone,
Geochim. Cosmochim. Acta 31, 649 (1967).
11. K. Govindaraju, Appl. Spectrosc. 20, 302 (1966).
12. Analytical Methods for Flame Spectroscopy
by Varian Techtron Pty. Limited, Australia (1978).
13. J.H. Medlin, N.H. Suhrand J.B. Bodkin,
At. Absorpt. Newsl. 8, 25 (1969).
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Table 1
Instrumental Parameters for Varian AA-775
Parameters calcium silicon aluminium iron magnesium sodium potassium
Wavelength (nm). 422.7 251.6 309.3 248.3 285.2 589.0 766.5
S.B.W. (nm) 0.5 0.2 0.5 0.2 0.5 0.5 1.0
Lamp current (mA) 3.5 20.0 5.0 5.0 3.5 5.0 5.0
Burner height (mm) 10.0 7.0 7.0 7.0 7.0 7.0 7.0
Flame Type (a,b) A-A N-A N-A A-A A-A A-A A-A
Oxidant/Fuel Scale
Units(g)
Oxidant (L/min)
Fuel (L/min)
50/15 50/100 50/95 50/15 50/10 50/15 50/15
10.0 9.3 9.3 10.0 10.0 10.0 10.0
1.7 5.0 4.8 1.7 1.3 1.7 1.7
Integration time
(seconds) 10.0
Background Corrector off
Solution 3
Element concentration
(g/mL) 8.5-9.2
(NBS Stds)
Nebulizer uptake
3 mL/min
5.0 5.0 5.0 5.0 5.0 5.0
on on on on off off
1 1 2 3 2 2
172-217 32-67 2-6 0.1-0.5 0.1-1.0 0.1-10
(a) A-A Air-Acetylene
( b) N- A Nitrous Oxide-Acetylene
Automatic Gas Control
3
( g)
Table 2
Evaluation of Fusion Techniques
Fluxing Agent Lithium Lithium tetraborate Sodium hydroxide Lithium carbonate Lithium
tetraborate lithium carbonate boric acid mixture metaborate
mixture
Flux/sample ratio 5:1
(0.500 g cement)
4.5:1 4:1, 10:1 5:1 2:1, 3:1, 4:1
Fusion conditions
muffle furnace C 1000
Meker burner -
Fusion action Slow
Action on Nil
platinum crucible
1000, 1200 -
- Below red heat
Fast with evolution Fast
of carbon dioxide
sputtering
Nil Slight
- 1050
Below red heat
-
Slow with evolution Fast
of carbon dioxide-
incomplete
Slight Nil
Sample Silicon dioxide Silicon dioxide
dissolution not taken up not taken up
Total dissolution
for 10:1 flux
sample
Total dissolution
for 3:1 & 4:1 flux
ratios
Comments Considered Improvement over (i) Not applicable Unsatisfactory Best available
unsatisfactory lithium tetraborate for sodium Unable to obtain fusion method
but unsatisfactory determinations proper melt providing procedure
followed correctly.
(ii) 10:1 ratio
tended to clog
nebulizer
Table 3
AAS Results of Reference Standards
CaO Si O
2
Al
2
O
3
Fe
2
O
3
MgO Na
2
O K
2
O
NBS Value Certified 64.5 21.8 3.7 4.2 1.0 0.64 0.17
633 Value found (AAS) 64.5 0 21.9 0.14 3.8 0.07 4.2 0 1.0 0 0.63 0.007 0.13 0.03
NBS Certified 59.8 18.4 6.2 2.61 1.2 0.05 0.45
635 (AAS) 59.7 0.14 18.3 0 6.2 0 2.6 0 1.2 0 0.04 0.03 0.41 0.03
NBS Certified 63.5 23.2 3.0 1.61 3.9 0.11 0.59
636 (AAS) 63.4 0.14 23.1 0.14 3.0 0.07 1.6 0 4.0 0.07 0.07 0.01 0.57 0.06
WET 63.5 23.1 3.4 1.6 4.6
NBS Certified 65.0 21.0 4.97 3.71 0.42 0.55 0.04
1016 (AAS) 64.6 0.35 20.9 0.21 4.9 0.07 3.7 0 0.4 0 0.55 0.07 0.03 0.04
Cement & 27 Reported 64.7 20.5 5.9 4.3 0.8 0.51 0.29
Concrete (AAS) 63.9 0.07 20.2 0 5.8 0.07 4.3 0 0.8 0.07 0.42 0.05 0.24 0.007
Assocn WET 64.3 20.4 6.1 4.3 1.4
Co-ordin-
ation
Test 28 Reported 64.5 21.2 4.9 4.0 1.7 0.14 0.66
Number (AAS) 64.70.6 21.1 0 4.9 0.07 4.0 0.07 1.8 0.07 0.11 0.05 0.66 0.07
WET 64.3 21.1 5.0 4.0 1.6
The AAS analyses are the
average of two determinations
carried out on separate fusions
by two analysts.
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