In the Laboratory
Determination of Free Lime in Clinker and Cement
by Iodometry
An Undergraduate Experiment in Redox Titrimetry
Oi-Wah Lau,* Shiu-Fai Luk, Nina L. N. Cheng, and Hoi-Yin Woo
Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong
The need to cover many new topics in the undergraduate
curriculum has required a reduction in the amount of volu-
metric analysis in the syllabus. There is also a strong view
that the curriculum should include practical applications.
Hence, ideally each experiment should cover several laboratory
skills, statistical data analysis, and preferably some practical
application. This paper describes an experiment to determine
the free lime in cement and clinker (a granular substance
formed as a result of burning raw materials at 1400 °C in
the cement kiln), which involves the skills of extraction,
filtration, redox and acid–base titrations, and statistical data
analysis. Thus, it is a suitable experiment for the undergraduate
analytical chemistry laboratory course. Besides, it demonstrates
how classical wet chemistry can be used in industry and pro-
vides a chance for students to learn about cement processing.
The determination of free lime (CaO) (an unwanted
component of cement) in clinker (ca. 1.5%) and cement
(0.5–1.5%) is essential at a cement plant for controlling the
quality of cement. High free lime contents render cement
unsound (1) and reduce its strength (2). The methods
commonly used for the determination of free lime are based
on the organic solvent extraction of free lime followed by
titration with acid (3, 4 ) or EDTA (5). American Society
for Testing and Materials recommends titration with an
alcoholic solution of perchloric acid after ethyl acetoacetate–
isobutanol extraction, using thymol blue as indicator (4). The
British Standard (BS) method involves titration with hydro-
chloric acid using methyl red and bromocresol green as indi-
cators after extraction with ethylene glycol (3) at 65–70 °C
for about 30 min. The extraction time for the BS method is
considered long for on-line determination and it is difficult
to detect the end point for subsequent titration, especially
for less experienced workers.
In this paper, a simple, inexpensive, and rapid iodom-
etry method for the determination of free lime in clinker and
cement is developed, which is suitable to be adopted as an
undergraduate experiment to illustrate the principles of volu-
metric analysis and is also recommended for use in cement
manufacturing for quality control purposes. The method is
based on the BS method (3) and the well-known application
of iodometry to determine the acid content of solutions (6 ).
The results found by this iodometry method were compared
with those obtained using the BS method. The iodometry
method was superior to the BS method in having a shorter
extraction time, more easily detectable and sharper end point,
JChemEd.chem.wisc.edu • Vol. 78 No. 12 December 2001 • Journal of Chemical Education
W
higher sensitivity, better precision, a smaller sample size, and
a smaller requirement of ethylene glycol.
Experimental Method
Free Lime Determination by Iodometry Method
Twenty milliliters of ethylene glycol (analytical reagent
grade) are placed in an Erlenmeyer flask, which is then
stoppered with a rubber stopper and heated in a water bath
at 70 °C until thermal equilibrium is attained. About 0.5 g
of the sample is accurately weighed and transferred to the
Erlenmeyer flask. The flask is stoppered again and shaken
mechanically and continuously in a water bath for 15 min.
The mixture is then filtered rapidly by vacuum filtration
through a Whatman No. 42 filter paper supported on a Büch-
ner funnel. The Erlenmeyer flask and the residue on the filter
paper are washed with several portions (with a total volume
of 15 mL) of pure ethanol.
An aliquot (3.00 mL for sample containing <1 % free
lime) of 0.10 M standard hydrochloric acid is added to the
filtrate in the suction flask. This is followed by the addition
of 50 mL of 0.005 M potassium iodate solution and 0.5 g of
solid potassium iodide. The liberated iodine is titrated with
0.005 M standard sodium thiosulfate solution with constant
stirring until the mixture turns pale yellow. Then 5 mL of
0.2% w/v starch solution is added and the titration is con-
tinued until the solution changes from blue to colorless.
The free lime content is calculated using the equation
free lime (%) = 2.804(Va Ma – V t Mt)/m × 100
where Va is the volume (in mL) of hydrochloric acid added
initially, Ma is the molarity of HCl, Vt is volume (in mL) of
thiosulfate solution used for the titration of the liberated io-
dine, Mt is the molarity of thiosulfate; and m is the mass of
the sample (in g).
British Standard Method
About 1.000 g of sample is accurately weighed and trans-
ferred to a dry Erlenmeyer flask containing 1 g of dry sand
and 0.5 g of dry filter paper. Then 40 mL of ethylene glycol
is added and the flask is stoppered. The mixture is mechani-
cally shaken continuously for 30 min in a water bath at 70 °C
and then filtered rapidly by vacuum filtration through a
Whatman No. 42 filter paper supported on a Büchner funnel.
The Erlenmeyer flask is rinsed and the residue on the filter
1671
 In the Laboratory
paper is washed with three 10-mL portions of pure ethanol.
The filtrate in the suction flask is titrated with 0.1 M stan-
dard hydrochloric acid using a mixture of methyl red and bro-
mocresol green as indicator until the color changes to orange.
The free lime content is then calculated using the equation
free lime (%) = 2.8MaVa/m × 100
where Va is the volume (mL) of hydrochloric acid used, Ma
is the molarity of HCl, and m is the mass (in g) of the sample.
Hazards
Ethylene glycol is harmful if swallowed. Pure ethanol
is highly flammable. Skin contact with potassium iodide
and potassium iodate should be avoided.
Results and Discussion
The principle of the iodometry method is that after
extraction, a known amount with slightly excess of standard
hydrochloric acid is added to react completely with the free
CaO in the sample. The excess acid is then allowed to react
with excess iodate and iodide to yield iodine rapidly and
quantitatively. The amount of iodine is proportional to the
amount of unreacted acid. Once the amount of iodine gen-
erated is determined, the quantity of acid consumed by the
free lime can be easily worked out and the free lime in the
sample can be calculated. The iodometry method has a very
sharp end point and hence is good for the titration of dilute
solution of strong acids.
The time for the extraction of free lime by ethylene
glycol can be reduced by raising the extraction temperature,
and extraction times of 5–10 min at temperatures 80–100 °C
have been reported to be adequate for the determination (7 ).
In preliminary experiments at 80–90 °C, the rubber stopper
was easily expelled from the Erlenmeyer flask and water was
found to condense at the mouth of the flask, causing hydrolysis
of silicates and yielding high free lime values. Therefore, the
extraction was conducted at 70 °C and the solvent was pre-
heated to 70 °C before the sample was added. More than
90% of the free lime was extracted within 5 min, and 10–15
min was adequate to extract it quantitatively. Therefore a
total extraction time of 15 min was chosen.
Table 1. Determination of Free Lime in
Clinker and Cement
Sample % Free Lime Found a (% RSD)a
Type No. Iodometry Method BS Method
Clinker 1 0.37 (2.7) 0.39 (3.0)
2 1.19 (0.8) 1.15 (4.2)
3 1.21 (0.2) 1.15 (2.1)
4 2.06 (0.4) 1.99 (3.2)
Cement 1 0.38 (2.5) 0.40 (3.9)
2 0.65 (0.9) 0.64 (2.6)
3 0.78 (1.3) 0.75 (2.9)
4 0.79 (1.0) 0.77 (1.2)
5 0.88 (1.1) 0.88 (1.8)
6 1.36 (0.6) 1.37 (1.0)
aResults are the mean of 3 determinations except those
for cement sample no. 2, which are the mean of 6 deter-
minations.
1672 Journal of Chemical Education • Vol. 78 No. 12 December 2001 • JChemEd.chem.wisc.edu
A recovery test with the iodometry method was per-
formed on a cement sample. The mean recovery of three
analyses for an added pure and known quantity of CaO was
96%, which can be considered as good. The precision of the
iodometry method was checked by calculating the relative
standard deviation for six determinations of free lime in a
cement sample (having 0.65% of free lime), and the result
was 0.9%. A number of cement and clinker samples were
analyzed by two undergraduate students using both the BS
method and the iodometry method; the results are summa-
rized in Table 1, which shows that there is a good agreement
between the two methods. The relative standard deviations
for the determinations shown in Table 1 also indicate that
the precision using the iodometry method is slightly better
than that using the BS method.
As a laboratory experiment for undergraduates, each
student is asked to determine the free lime in a cement
sample three times by both methods. Students then assess
the precision by calculating the relative standard deviation
of each method and apply the F test (8) to show if there is any
significant difference in precision between the two methods.
With reference to Table 1, making use of the standard deviation
and average values of cement sample number 6, the calculated
t value (8) was 1.08, which is less than the theoretical t value of
2.776 at the 95% confidence level for four degrees of freedom.
This shows that there is no significant difference between the
two methods. Students can also assess the accuracy and pre-
cision of their own work by comparing their individual data
with the mean and relative standard deviation for results com-
piled from results of the whole group of students analyzing
the same cement sample.
If different cement (or clinker) samples are available, the
experiment can be run so that another statistical method, the
paired t-test (9), can be used. In this approach, students are
given different cement (or clinker) samples to be analyzed as
above. The t test can be used to assess the accuracy of the
method; students can then pool their results and apply the
paired t-test to show whether there is a significant difference
between the two methods. This enables the students to
discuss the difference between these two statistical methods
for method validation.
The iodometry method has several advantages over the
BS method (3) or EDTA method (5). While calcium origi-
nating from gypsum interferes with the complexometric
determination of free lime (10), calcium has no effect on the
iodometry method. Compared with the BS method, it gives
a much sharper and more easily detected end point and needs
a shorter extraction time. The sample size is reduced to 0.5 g
in the iodometry method so that less sample is consumed
for each analysis. Further, less ethylene glycol is used so that
the running cost can be cut down using the iodometry
method. The reagents are readily available, and standard
solutions can be conveniently prepared using the iodometry
method, whereas the BS method employs CaO as the standard,
and CaO needs to be prepared by igniting calcium carbonate
in a platinum crucible at 1000 °C
The student laboratory report should include a brief de-
scription of the cement manufacturing process, a discussion
on the advantages of the iodometry method over the BS
method, and the ways of improving the sensitivity of the
method.

Conclusion
A simple, rapid, and accurate method has been developed
for the determination of free lime in clinker and cement. Free
lime is first extracted with nonaqueous ethylene glycol at
70 °C for 15 min. The suspension is filtered and allowed to
react with a known excess of hydrochloric acid. The excess
acid is determined by iodometry. The method is better than
the classical BS method for the determination in terms of
speed, sensitivity, and precision. This method was developed
with the help of two undergraduate chemistry majors. It is
an excellent addition to the undergraduate analytical experi-
ments currently available. Students use a variety of techniques
(nonaqueous extraction, filtration, and iodometry) in a single
experiment. This experiment also gives students unique op-
portunities for data collection and analysis, and to become
acquainted with the cement industry.
W
Supplemental Material
Additional background information is available in this
issue of JCE Online.
JChemEd.chem.wisc.edu • Vol. 78 No. 12 December 2001 • Journal of Chemical Education
In the Laboratory
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3. BS EN 196-2, British Standards Institution: London, 1995.
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