CEMENT and CONCRETE RESEARCH, Vol. 20, pp. 739-745, 1990. Printed in the USA.

0008-8846/90. $3.00+00. Copyright (c) 1990 Pergamon Press plc.

THE EFFECT OF CHLORJDE ION SOURCE ON THE FREE CHLORIDE ION

PERCENTAGES IN OPC MORTARS

M.J. A1-Hussaini*, C.M. Sangha*, B.A. Plunkett#, P.J. Walden*

* School of Civil Engineering, # Department of Chemistry
Portsmouth Polytechnic
Portsmouth
England
(Communicated by C.D. Pomeroy)
(Received Feb. 13; in final form March 14, 1990)

ABSTRACT
The effect of incorporating varying percentages of sodium chloride
(NaCI) and calcium chloride (CaC12) in ordinary Portland cement
(OPC) mortar mixes on the free chloride ion content was investigated.
After curing for 28 days with different levels of chloride ions, mixes
were tested to assess the percentages of chlorides that remain in the
pore solutions and those that are chemically bound by the cement
hydration products. It was found that a considerable amount of
chloride remains in a free form and that NaCI produces higher
percentages of free chloride ions than CaCI2 at all concenm'ations up to
2% (C1- ion by mass of cement). NaC1 was also found to produce
lower pH than CaCI2. Thus NaCI will present a greater threat in terms
of corrosion of reinforcement than CaCI2.

Introduction

For many years calcium chloride had been used as an admixture in

concrete for its desirable effect of reducing the initial and final setting times,
facilitating early strength development and reducing the risks of frost attack.
Sodium chloride on the other hand produces rather erratic changes in the setting
times and is therefore rarely used as an admixture. The economics of transporting
land-based aggregates has forced the use of sea-dredged aggregates (with their
high NaC1 content) in concrete manufacture in many parts of the U.K. Ingress of
NaC1 into concrete structures in a marine environment, and into bridge decks
from deicing salts, is causing concern regarding its effect on the corrosion of the
embedded reinforcement.

Chlorides in concrete are usually present either bound with the hydration products
of cement (with the C-S-H gel) ,or found in free state within the pore solution. At
present, the chloride levels in concrete (1) are specified in terms of total chloride
mn content. However, the risk to corrosion of reinforcement is posed by the free

739
740 M.J. AI-Hussaini, et al. Vol. 20, No. 5

chlorides. Although it is the C1- ion that primarily constitutes the danger in
corrosion, it is possible that the free chloride levels may be affected by the cation
type (2). There is little information in literature regarding this point. It is
therefore the aim of this study to investigate the effect of the associated cation on
the ability of the cement to bind the salt and to determine the percentages of these
chlorides that remain in a free water soluble state.

Materials

Ordinary Portland cement, supplied by Blue Circle Swanscombe, was

used in making the mortars. Its chemical composition is shown in Table 1.

TABLE 1.

Composition of Ordinary Portland Cement

Oxides (% of cement by mass)

SiO 2 AI203 Fe20 3 CaO MgO SO 3 LiO K20 Na20

21.8 5.0 0.3 65.2 0.4 2.8 1.6 0.1 0.05

Cement Compounds from Bogue's Equations (% of cement)

C3S C2S C3A C4AF

57.7 19.1 12.7 0.90

Sand used in mortars was 1.18 mm maximum size land based flint, oven
dried at 105oC for 24 hours. It was found to contain negligible amounts of
chloride. The total water/cement ratio was 0.5 and the aggregate/cement ratio
was 4. Since the sand used was oven-dry, and the water absorption for saturated
surface-dry condition was found to be 1.5% , the free water/cement ratio for the
mortars was effectively 0.,1-4.
Chloride ions were introduced into the mixes by dissolving Analar grade
calcium chloride and sodium chloride salts in distilled water, to make up solutions
that would produce equivalent chloride ion concentration levels of 0 to 2% by
mass of cement for both salts.

Sample Preparation Technique

Each mortar sample was produced by mixing 50 g cement and 200 g oven-dry
sand with 100 ml of the chloride solution, and casting the mix into small stainless
Vol. 20, No. 5 CHLORIDE SOURCE, FREE CHLORIDE 741

steel moulds. The samples were compacted by hand and covered with polythene
film to avoid any moisture loss. All samples were stripped from the moulds after
24 hours and left to cure in small airtight plastic bags at 20oC.

After 28 days, the samples were crushed down to small lumps of

approximately 5 mm nominal size. A tungsten carbide shatter box was used for
three minutes to grind down the samples to a fine mesh. Final grinding was done
using a mortar and pestle until the whole of the sample passed a 150 micron
sieve. Samples were stored in airtight plastic bags over silica gel until tested.

Chloride Extraction Technique

Samples containing 3 g of cement were weighed to the nearest 0.01 g and

used for determining both the free and total chloride ion contents. The free, water
soluble chlorides were extracted by dispersing the powdered sample in 100 ml of
distilled water at 20oC, stirring for approximately 1 minute, then standing for 24
hours.
An alternative method of extracting the free chloride was also used for
mortars containing 0, 0.1, 0.2, 0.3, and 0.4% chloride ion (w.r.t. cement). This
involved extracting the free chloride ions using water at 45oC, stirring for the first
5 minutes and leaving the solution standing for 60 minutes with the temperature
maintained at 45oC. This temperature was found, by Ar3'a et al (3), to be that at
which all the free chlorides go into the solution from a mortar mix containing 1%
total chloride. Above this temperature the release of bound chlorides into
solution occurs.

Total chlorides were extracted using a mixture of 10 mi of concentrated

nitric acid and 40 ml of warm distilled water and heating the extract to near
boiling. A further 50 ml of distilled water was added and the extract kept warm
for 15 minutes on a hotplate. All extracts were filtered using a fast grade 42
Whatman filter paper and made up to 250 ml with distilled water.
The pH of each of the extracts was measured using an E.I.L. pH meter
and glass electrode. The percentage of chloride ions w.r.t, cement was determined
by the Volhard indicator method of titration. This method which is described in
B.S.1881 (4), involves adding a measured excess of standard silver nitrate
(AgNO3) solution and titrating against standard potassium thiocyanate (KCNS)
solution. Ammonium ferric sulphate is used as indicator. Silver nitrate solution
was standardized using Analar grade sodium chloride dried at 105oC for 4 hours.

Results and Discussion

The results obtained are given in Table 2 and displayed graphically in

Figures 1 and 2. Results are an average of three extractions carried out on each
sample. Figures 1 and 2 show that both of the methods for free chloride ion
extraction exhibit a similar trend and clearly highlight the importance of the
cation.
742 M.J. Al-Hussaini, et al. Vol. 20, N o 5

TABLE '~ Z.,o

Percentage of the total chloride present in the pore solution

Equivalent Present Results Ramachandran Arya

CI- % of (Fig.2) (5) (3)
cement CaC12 NaCI CaCI2 NaCI
V
I 0.5 44 % 50 % 17 % 27 %
1.0 55 % 60 % 30 % 57 %

!r 2.0 63% 70% 35% 81%

10~t- lgtlt -

SK~-

tat-

~ICE-

.,~t-

~t-

I~-

OPC. i
J

; i ! i i i
i I i r l i i i i !
(L~ 0,10 0.~ 0.~ 0.40 0d~ g.4 0,8 1.2 1,8 7,0

" CI- ion" % a d d e d (w.r.t. c e m e n t ; " CI- ion" % a d d e d (w.r.t. cement)

x NaCI + CaCI 2 x NaC1 + CaCI 2

F I G 1. F I G 2.
(1 hour extraction at 45oc) (24 hours extraction at 20oc)
F I G U R E S 1 & 2.

FREE C H L O R I D E IONS
(AS A P E R C E N T A G E OF THE TOTAL C H L O R I D E CONTENT)

For the 1 hour, 4 5 o c extraction method (Figure 1) and chloride ion

dosages of 0.1% to 0.4%, NaC1 tends to produce over twice the amount of water
soluble chlorides than does CaC12. Extractions at 20oC for 24 hours for the same
range of chloride additions, show that the water soluble chlorides from NaC1 are
30% higher than those of CaC12 (Figure 2).
Vol. 20, No. 5 CHLORIDE SOURCE, FREE CHLORIDE 743

Comparison of the two extraction methods shows that 1 hour extractions

at 45oC give free chloride percentages that are slightly lower for CaC12 and
higher for NaCI than those achieved by the 24 hours at 20oC method. Hence, the
1 hour at 45oC method tends to exaggerate the relative effect of the two cations
on the free chloride levels.
Figure 2 shows the variation of free chloride ion levels as a percentage of
the total chloride content at different dosages. The percentage of NaC1 present in
a water soluble form rises steadily with an increase in dosage, up to 70% at 2%
addition (by mass of cement). A similar increase in the case of CaC12 is observed
across the range up to 62% at 2%.

For comparison Table 2 also presents results reported by Arya et al (3) for
0.5 w/c ratio OPC pastes containing NaC1 and by Ramachandran et al (5) for
cement pastes containing CaC12 and a water/cement ratio of 1. It should be noted
that in Arya's work the pore solutions were extracted from the pastes by pressure.
The present results compare favorably with those of Arya et al (3) in the
case of NaC1 additions of 1%. At 0.5% their results are lower than the present
reported and slightly higher at 2.0% additions. Ramachandran's (5) much lower
results for CaC12 may be due to the rather high w/c ratio. His method of
extraction is not known, and hence it is difficult to assess the significance of the
discrepancy.

Q.24

0.22.

0.20.

0.18 •
:t
0.70-
0.18 •

0.10-
Q.14 •

0.12 •

&10 •
0.40-

0.~-
0.06.
0.20-
0.04.

0.10 -

O.O0 i 1 1 i i i i : i i i l i i i i ~ i
0.10 O.20 Q.30 0.40 0.D 0.4 0.~ 1.2 1.e 2-O

" CI- ion" % added (w.r.t. cement) " CI" ion" % added (w.r.t. cement)
.-: NaCI + CaCI 2 x NaC1 + CaCI 2

FIG .3 FIG.4
(1 h o u r e x t r a c t i o n at 4 5 o C ) (24 h o u r s e x t r a c t i o n at 2 0 o C )

FIGURES 3 & 4
CHLORIDE ION P E R C E N T A G E ( b y m a s s of cement )
B O U N D BY OPC MORTAR.
744 M.J. AI-Hussaini, et al. V o I 20, No. 5

Kawamura et al (6) reported similar results to those of Ramachandran in

the case of CaCI2 addition. For NaCI however, the free chlorides were 51, 85 and
121% at 0.5, 1.0 and 2.0% chloride additions respectively. (Their data related to
cement pastes with a water/cement ratio of 0.475 cured for 35 days). These
percentages would appear to be questionable in the light of present work and that
of others.

Berman (7) digested powdered samples containing CaCI2 in boiling water

and allowed them to stand at room temperature for 48 hours before filtering. He
found the water soluble chloride percentage to be 78% and 76% of the total at
1.84% and 0.88% addition ( by mass of dry cement )respectively. It is to be
expected that extractions at high temperatures would release a considerable
amount of bound chlorides and this would explain the high percentages reported.
Figures 3 and 4 show the chloride ion levels bound by the cement hydration
products at 28 days. For both NaC1 and CaC12 the percentage of bound chlorides
increases almost directly with the rise in chloride content. Above 1% and up to
2% chloride ion addition the increase occurs at a slightly lower rate. It is
apparent that the ability of the cement to bind NaC1 in stable compounds
decreases at dosages above 1% C1- ion by mass of cement. Within the range of
chloride levels generally specified for reinforced concrete by standards (1),
approximately 40% of the chloride ions remain in a free state.

The free chloride extracts (20oC for 24 hours) were used to assess the
effect of the cation on the pH of mortar at different chloride additions. Figure 5

12-q0,

12.4¢.

12JO.

IZ.20 '

12.10.

12.100.

11.KI,

11.B0.

11,70 •

lt.lO •

1t~0 •

11.40 '

11J10 •

1 ~..20 -

~1.10 •

11.00 ; ~ J t i i ! i i
OJO0 ~.4¢ 8~0 1.20 1.1R

" C1- i o n " % a d d e d (w.r.t. c e r n e m )

r: NaC1 + CaCI 2

FIG.5
EFFECT OF CHLORIDE ION SOURCE ON THE pH OF OPC
MORTARS.
Vol. 20, No. 5 CHLORIDE SOURCE, FREE CHLORIDE 745

indicates an average difference of approximately 0.2 pH in the extracts of mortars

containing CaCI2 and NaC1. The change of the solution pH with an increase in
chloride ion concentration is small. Figure 5 shows that the pH of solutions
containing NaC1 are about 0.1 to 0.2 units lower than those with CaCI2. Although
this difference appears to be small, it is consistent at all chloride levels up to 2 %.

Conclusions

1. NaCI produces significantly higher levels of free chloride ions than CaCI2 at
all chloride levels up to 2% by mass of cement.

2. The free chloride ion content as a percentage of the total chloride increases
with increasing chloride dosage.

3. The pH of OPC mortar appears to be lower in mixes containing NaC1 than

those containing equal levels of CaC12.

4. The present method of specifying chloride limits in reinforced concrete (1)

does not take into account the marked dependance of the free chloride ion
on both total chloride level and associated cation type.

References

1. British Standard Institute, "Structural Use of Concrete", B.S. 8110, Part 1,

1985.
2. Imre Biczok, "Concrete Corrosion Concrete Protection", Akademiai Kiado,
Budapest, 1964.
3. C. Arya, N.R. Buenfeld and J.B. Newman, Cement and
Concrete Research, 17, p907, 1987.
4. British Standard Institute, "Methods of Testing Concrete", B.S. 1881 :Part 6 :
1971.
5. V.S. Ramachandran, R.C. Steeley and G.M. Polomark, Materiaux et const. ,
17, p285, 1984.
6. M. Kawamura, O.A. Kayyali and M.V. Haque, Cement and
Concrete Research, 18, p763, 1988.
7. H.A. Berman, Journal of Materials, JMLSA, 7 (3), p330,1972.