CEMENT and CONCRETE RESEARCH. Vol. 17, pp. 173-182, 1987. Printed in the USA.

0008-8846/87 $3.00+00. Copyright (c) 1987 Pergamon Journals, Ltd.

EQUILIBRIA OF THE CHEMICAL COMPOSITION OF THE CONCRETE PORE

SOLUTION. PART I: COMPARATIVE ST[rDY OF SYNTHETIC AND
EXTRACTED SOLUTIONS

A. Moragues, A. Macias and C. Andrade

Institute of Construction and Cement
Eduardo Torroja (C.S.I.C.)
Madrid, 28033, Spain

(Refereed)
(Received July 8; in final form, Nov. 13, 1986)

ABSTRACT
A critical review is made on Frattini and Hansen's results on the equi
libria of the different ions present in the aqueous solution of cement
paste after mixing. These values are compared with those obtained from
results of squeezed cement paste specimens drawing the conclusions
that the cement paste solution is oversaturated in Ca(OH)2. just after
mixing but the ions present in it are not in thermodynamlc equilibrium
because the solution is continuously evolving during early ages.

Also the increase in the solubility of the Ca +2 ion because of the pre
sence of SOA = is discussed and attributed to the increase in the ionic
strength of ~he solution.

Introduction

The present controversy on the stability of the corrosion of galvanized re -

bars embedded in concrete have led the authors to a systematic study using
different synthetic solutions which simulate the pore concrete solution. To
carry out this study a saturated solution of Ca(OH) 2 was used as the "mother"
solution and different concentrations of NaOH, KOH, Na2S04, K2SO 4 and CaSO 4
were added (i).

The results on the corrosion behaviour of the galvanized rebars in contact

with these solutions are beingpublished (i) (2). Although the use of such a
solution does not reproduce the real behaviour in concrete (owing to the
variables of physical nature: e.g. resistivity, mobility, discontinuity of
the electrolyte, etc., are not taken into account) this study enables the
identification of the factors which control the corrosion process and sheds
light on the random results previously obtained in other studies (3).

173
174 Vol. 17, No. 2
A. Moragues, et al.

This investigation obliged us to study in depth pore concrete solution's com

position as well as its evolution over time. Since the publication of Fra -
ttini's studies (4) (5) several authors have released interesting results on
the composition of this aqueous phase• Some of these researchers tried to re
produce its composition from synthetic solutions~ among them stands out par-
ticularly the Hansen's report in the Whasington Congress (6). A number of di-
fferent authors have succeeded in extracting this aqueous phase from cement
pastes with high water/cement ration (7) (8) by using filtration or centrifu
gation before the setting of the cement (9). Since Longuet's contribution
(i0) (ll) the pore concrete solution is extracted or squeezed out from harde
ned paste or concrete with the use of a high pressure device (12) (13).
Although it is the composition and evolution of the pore concrete solution
are now more or less understood, some unknown aspects remain with regard to
the interelation with the different species of the equilibrium Ca(OH) 2 -
NaOH - KOH - CaSO..2H^O. Thus, it is commonly stated that during the First
4
steps after mixing, t~e solution is oversaturated in Ca(OH)o. In 1975,
Diamond published (15) an excellent, yet poorly understood ~aper in which
he develops a wax of calculating from Longuet's results the amount of equi-
+L
librium of Ca necessary to accomplish saturation using activities instead
of concentrations. More recently, Rechenberg et al (15) have confronted this
problem attempting to justify the apparent oversaturation as a result of the
presence of S04= which modifies Frattini's curve.
In the first part of this paper the authors present a comparative study of
their results with those of the authors who have prepared synthetic solutions
reproducing the pore concrete solution. The simultaneous presence of Ca(OH) 2
and CaSO 4 which precipitate at high alkaline pH values and which have very
similar ionic product constants, obliges us to consider a conditional one
which will be calculated in part II of the paper taking into account the
ionic strengths. Likewise, the results of other authors who have analized
the aqueous phase of pastes or concrete (with water/cement ratios not over
0,5) are discussed and the real concentration of the different species are
compared to Frattini's equilibrium with and without the presence of S04 =
ions.
Preparation of the synthetic solutions
Frattini (4) reported that his solutions were prepared from anhydrous CaO,
KOH and NaOH in the proportions needed to obtain the different concentrations.
The solutions reported by Hansen (6) were prepared by adding an excess of
CaSO 4 o r Ca(OH) 2 t o s o l u t i o n s o f NaOH o r KOH a t 25~C and 30~C.
Our s o l u t i o n s (1) (2) were prepared using distilled water previously boiled
eliminate dissolved CO_. F i r s t KOH o r NaOH w e r e d i s s o l v e d to obtain the
desired concentration, t h e n 8 g / 1 o f Ca(OH) 2 w e r e a d d e d t o s a t u r a t e the solu
tion I n t h e SO containing solutions, e i t R e r CaSO o r Na SO o r K SO was
• 4 4 2 4 4
added in the proportions shown i n T a b l e I . The t e m p e r a t u r e was m a i n { a i n e d
a t 22 + I~C i n a l l t h e s o l u t i o n s .
Aqueous phase of cement paste or concrete
The r e s e a r c h e r s who h a v e a n a l y z e d t h e a q u e o u s p h a s e o f t h e c e m e n t p a s t e i n
the first minutes after mixing have all used filtration or centrifugation
in the extraction of the solution (8) (9) (16) (17) (18).
We limit our analysis to those authors who have obtained the aqueous phase
by extracting it using pressures applied to hardened paste or concrete speci
mens (i0) (12) (13). The results obtained by the use of this method are at
times critized due to the small amount of water that can be extracted from
Vol. 17, No. 2 175
EQUILIBRIA, PORE SOLUTIONS, THEORY

the pores and because it cannot inform on the real c o m p o s i t i o n of the water
"linked" to the gel. Nevertheless, it is at this point the best approach for
the study of the c o m p o s i t i o n of the pore concrete solution.
Other methods, such us the employed by Delmas (19) in which the h a r d e n e d con
crete is ground and mixed again with water are not c o n s i d e r e d by us to give
accurate results. This m e t h o d makes possible a new hydration and also p r o v ~
kes a dilution and therefore it gives erroneous results.

Analytical methods
The various different methods of analysis employed in either the synthetic
solutions or the aqueous phase (see references (i) (i0) (13) for p r o c e d u r e s
experimental c o n d i t i o n details) extrated were:

- pH m e a s u r e m e n t s - acid titration (HNOq or HCI) with p h e n o l p h t a l e i n or methyl

orange as indicatiors were used (4) (~) (7). In our results, also a c o m b i n e d
glass electrods for pH range 0 - 14 was employed and its accurancy was dis-
cussed (20) c o m p a i r i n g it with the titration method.

- C a l c i u m d e t e r m i n a t i o n s - the most common method r e p o r t e d was the addition

of an excess amount of oxalate in order to p r e c i p i t a t e s calcium oxalate
and afterwards titration of the excess of oxalate by MnO.- g in an acid
medium (4) ours results were o b t a i n e d by the use of compIexone III in a
basic medium (i) using c a l c e y n as an indicator.

- Sodium and P o t a s i u m d e t e r m i n a t i o n s - either flame p h o t o m e t r y (i0) (12) or

athomic a b s o r p t i o n were used.

- Sulfate d e t e r m i n a t i o n s - the traditional method or p r e c i p i t a t i n g SO 4 as

BaSO 4 was employed by all the author reviewed.
Results

Synthetic solutions
The data of Ca ++ as a function of OH given by Frattini (4) at 20~C, Hansen
(6) at 20~ and 30~ and r e p o r t e d by us in Table 1 at 22 + I~C, are p l o t t e d ~n
Figure I Curve A is the well k n o w n "Frattini's curve" of v a r i a t i o n of Ca +z
with the OH- when no SO. = are present. All the results c o n s i d e r e d here fit
4
well with Frattini's results. The only substance which p r e c i p i t a t e s is the
Ca(OH) 2 •
But as R e c h e n b u r g point out in (15), curve B is the modified cur×e w h i c h
+L
results when S04= are taken into account. In this case the (Ca remains
higher for a more extended OH- range due to the p r e c i p i t a t i o n of CaS04,
w h i c h causes the d i s s o l u t i o D of more Ca(OH)~ until OH- is about 0,09 mol/l
+~
(pH 13,05) where the Ca d r a m a t i c a l l y decreases and curve B joins curve
A. for the h i g h e r OH values.

From Table 1 other useful evidence can be deduced: a l t h o u g very high amounts
of Na + and K + were added as Na~SO. (52 g/l) or K ~ S O . ( 8 0 g/l) the pH value of
4
the solution never surpasses the value of pH 13,~. ~his fact explains the
prior o b s e r v a t i o n of real pore concrete solutions early ages when S04= remain
in solution: the h i g h e s t r e p o r t e d pH values achieved (i0) (6) (i) are always
below this limit. The pH value only rises above 13,3 when sulfates disappear
because they are c o m b i n e d with the aluminateso
In figure II the v a r i a t i o n of SO. = as a function of OH- is represented.
4
The trend is similar, but to the contrary of that of curve B of firure I.
176 Vol. 17, No. 2
A. Moragues, et al.

TABLA I
pH C+a 2 a n d values to d i f f e r e n t disolutions studied

KCH/ NaOH CaSO4 K2SO4 Na2SO4 pH Ca 2+ grll

Ca(CH) 2 tool .'1 tool/1 m"ll ~7i ~/i

sat 0,1 - 12,99 0,258

m
sat 0,25 - 13,5~ 0,08
h

sat 0,3 - 13,42 0,058

sat 0,35 - 13,45 0,0?2

sat 0,5 - 13,59 0,053

sat 0,? - m
13,72 0, Oa9

sat - 0,01 12,51 0,722

IIII

sat - 0,05 12,80 0,408

sat - 0,1 m - - m
12,99 0,220

sat - 0,2 13,17 0,112

sat - 0,25 13,30 0,051

sat - 0,3 13,35 0,029

set - 0,5 m
13,5 0,050
.... I

sat - -- 5 m
~ 12,43 I, 132

sat - -- - - 5,22 12,70 0,856

sat -- - - 6,41 - 12,77 0,984

sat - - 5 5,22 12,?1 0,858

sat - -- 5 6,41 12,?? 0,872

sat -- - 5 6,41 5,22 12,72 0,480

I"

sat - - 26,1 12,98 0,624

sat ~ - 52,2 13,06 0,216

sat - - 32,05 13,02 0,644

sat - - 64,1 13,22 O, 288

|

sat I - 13,29 0,211

I
Vol. 17, No. 2 177
EQUILIBRIA, PORE SOLUTIONS, THEORY

0 m
0
3oJ "00 SYNTHETIC
SOLUTIONS

0 o (6)
zs (4)

i . 2 o J -~B
~o
o (I}

o
,0~ 10 o
~o
o
A~ c~ o
, B ~ B B,
o., o.~ o.~ o.~ [o.-] ~o,,,

I I I '~ I
13 13,48 13,7 13,8 pH
FIGURE I
Ca +2 concentration in function OH- concentration solutions

300 SYNTHETIC
SOLUTION

= (6)
0
m 200.
m
0

E
D
0
(n I00- 0

r ~
o.1 o.2 o.~ Lo.-j too,.,

13 13,30 13,48 pH

FIGURE II
Variation of S04= concentration in function of OH- concentration
178 Vol. 17, No. 2
A. Moragues, et al.

Aqueous phase of cement paste

Only w a t e r / c e m e n t ratios equal to o~ below 0,5 are c o n s i d e r e d in this paper.
In figure III the v a r i a t i o n of Ca T~ is again r e p r e s e n t e d in function of OH-
for pastes with w/c ratio of 0,5 and in figure 4, the same variable but for
cement pastes with lower w/c ratios.
The solid lines p l o t t e d are curves A and B obtained from figure I which repre
sent the concentrations of equilibrium. The numeral next to each point deno-
tes the age (seconds, minutes, hours, days or months) of each test.
It is evident from this figure IV, that the values obtained from cement pas-
tes of~normal w/c ratios do not lie on the e q u i l i b r i u m curves. At early ages,
the Ca +z is higher than that of Frattini's theoretical curve and even higher
than concentrations given by sulfate's curve B. Therefore, in the first mo -
- .,, +- --
ments after m i x i n g the solutions seems to be oversa~uratea in Ca . Preci-
pitated Ca(OH) 2 has been identified as well.
As time passes and higher pH values are reached, the points of Ca +2 lie in
a wide range of pH values above and b e n e a t h equilibria's curves. Therefore,
when the points of p e r f e c t equilibrium are achieved they do so only acciden-
tally.

On the other hand, the SO = in cement paste is always below the saturation
4
values drawn by the solutfon e q u i l i b r i u m curve. The d i s p e r s i o n o b s e r v e d in
the c o n c e n t r a t i o n values can be a t t r i b u t e d to the very different amounts
of sulfates p r e s e n t in the cement and the different reaction rates with the
CBA.

CEMENT PASTE
30.
w/c rotio= 0,5
. (1) x (14)
o ~{Ih) ~ v (9) o (13)
- 20. ~k~"-(5h) ,', (iO)
o
E
r--'-I
N
,,(Sh) 3(
÷ '~(1-5 h) X
0
o
I_.._.I
I0.

{4d) 28d
'2ed) ~ ){6m) {7d)
n
t
0,1 0,5 0,5 03 ~OH-Jmol/I

13 13,48 13,7 13,84 pH

FIGURE III
V a r i a t i o n of Ca +2 c o n c e n t r a t i o n in function of c o n c e n t r a t i o n
for pastes made with 0,5 of W/C ratio
Vol. 17, No. 2 179
EQUILIBRIA, PORE SOLUTIONS, THEORY

Discussion
Synthetic solution equilibria
When Ca(OH) 2 is being added to distilled water and the saturation concentra-
tion is achieved, the equilibrium is:
Ca(OH)2~Ca+2 + 2 OH- Ksp = [Ca +2 ] [OH-] 2 = 3,5 x 10 -5 (i)

And when either Na SO or K SO are being added to a saturated solution of

2 4 2 4
Ca(OH)2, the r e a c t l o n which must be considered

Ca(OH) 2 + Na2S04~ ~ CaSO4 + NaOH (2)

redissolving Ca(OH)2 and increasing pH and Ca +2 in solution until the satura-
tion concentration ~f CaSO 4 is achieved and it precipitates in the following
manner:
CaS04~ S04: + Ca+2 Ksp = [Ca+2] ~ S04=]= i0-4 (3)
As the Ca+2 ion i s common i t must accomplish the two e q u i l i b r i a , hence the
two expressions can be equalled. The rssulting expression of S04= in func-
tion of the pH value is:

Ksp Ca(OH) 2

Then, the experimental values given by Hansen (6) an by us in Table i. should

verify this expression. Nevertheless the results of of concentrations of the
different ions do.not
+~
fit with it. In table II ~e show some experimental va-
lues (6) of Ca and SO 4- and those of S04 = calculated from expression
(4)
TABLE 2
Ca 2+ OH- S04 = SO =
experimental experimental experimental calculated from (4)

0,0331 0,0414 0,0123 0,00489

0,0240 0,0502 0,0190 0,0072
0,0183 0,0726 0,0426 0,0150
0,0161 0,0888 0,0722 0,0225
The constants should be valid for any solution saturated in Ca(OH) 2 and CaS04,
but as the electrolyte is a concentrated one, these K values are-not cons--
rant because they are a function of the ionic s t r e n g h ~ of the solution.
Diamond (14) undertook a method for the calculation of ionic strengths to find
an expression which intends to attain an agreement between the experimental
and the calculated results, Diamond concluded that the agreement was only valid
for ionic strengths lower than 0,2 (about pH ~ 13).
Another method we suggest is to work with concentrations calculating an "Appa-
rent" ion product constant in function of the ionic strengths when working only
with concentrations a more complicate expression than (4) is not necessary.
The only precaution which is necessary to take into account is use concentrati-
ons or activities in a coherent manner. The sole of ion concentrations (calcula
ted by titration) or the sole use of activities (calculated from electrode mea~
surements).
After having the apparent ion product constants of CaSO. and Ca(OH)_ it is
4
necessary to calculate a "conditional" one. All these calculations will be
done in part II of this paper.
180 Vol. 17, No. 2
A. Moragues, et al.

w, ~(7')
(30") CEMENT PASTE
norrnol
• (17) w/c: cons.
30[ (3')
v ,~ (I0'1
v (8'1
v (16) w/c=0,27
x (19) w/c :0,35
X= 1120'1
9K
< 20
o
-E k n~u, {lh)

..o

"(2h) (2h) (3h)

t
~
v
V
t
v V~ v ~ d~ ~ 1120'1
0,1 0,3 0,5 O,7 [OH-] mol/I

13 13,48 13,7 13,8 pH

FIGURE IV
Variation of Ca +2 concentration as a function of OH-
concentration for pastes m~G~'~ with W/C ratio lower than 0,5

Cement aqueous phase equilibria

All the conclusions drawn by Diamond in (14) based on Frattini's solution are
theoretically correct, but the expression which he deduces, following the Debye
- HGckel theory, is not accurate enough (as is customany when the electrolyte
is highly concentrated). Therefore Diamond's application of Longuet's values is
equally inaccurate for solutions with ionic strengths higher than 0,2.
Moreover, Diamond only considers the Ca(OH)~ equilibrium when infact SO. = are
4
always present in cement pastes during earls ages. This is the main contribution
of Recherberg and Sprung who have point out the modification which the Ca504
equilibrium introduces in Frattini's curve. Unfortunately these two authors do
not take into account the variation of K values due to the increasing ionic
s
strengths. What's more they make a risky ~ssumption in the consideration of the
two separate equilibria (Ca(OH) 2 and CaSO_). L+2hev~ substract the C ~ ~ correspon-
ding to the CaSO. from the totaI amount o~ Ca in the solution. In our opinion
4
this consideration is incorrect, because when a common ion must accomplish two
different equilibria, it must accomplish them simultaneously and not separately.
The apparently correct deduction they make afterwards has to be seen as a sim-
ple coincidence (figure II in Recherberg's paper (15)).
Another point which Rechenberg and S ~ u n g point out is that the aqueous solu-
tions not really oversaturated in Ca--. However working at~figure III there
is no doubt that the aqueous phase is oversaturated in Ca +L at really ages
after mixing because all points lie above the exprimental curve B. Moreover,
many authors have observed the Ca(OH) 2 to precipitate in such ages which is
Vol. 17, No. 2 181
EQUILIBRIA, PORE SOLUTIONS, THEORY

200-

180.
/ •
V
CEMENT PASTE
(18)
(17)
normal
w/c =cons.
w/c : 0,25
x (19) w/c : 0 , 3 5
160- o (9) w/c=O,5
ii
o (14) w/C=0,5
140 a (10) w/c:O,5
o (3') (8')
x 120 v ~(30")
<
J vv w 130'1
100, • , I =~, v v ~(7') ,
7 (3o)1 ~
f n~'(]
v
h-Sh)
x(lzo )
'm' 80"
/ , v(250')
60" / %o')"
40" o (,56 d)

20 i (,,)(,2o')
I xx ~ (4o')
0
0
~(120') A (Td)
0

I & A A t
0,1 0,3 [o.-] oo, ,
J ! ! :
13 13,.48 13,7 13,84 pH

FIGURE V

Variation of SO. = concentration in function of OH- concentration

4
for pastes made with different W/C ratio

only possible if the saturation concentration has been achieved and surpassed.
In reality when cement is initially mixed with water the hydration reactions
begin and progress quickly and an increasing amount of Ca(O~)p goes into solu-
tion. This constant evolution of solution concentration impedes or even makes
impossible the attainement of a thermodynamic equilibrium. Therefore, there is
no possibility for an equilibrium, at least at erarly ages when the hydration
progresses quickly.
Considering oversaturation however the contrary occurs with the sulfates. A
fixed amount of sulfates exists in the anhydrous cement, which is dissolving
during the early ages but is simultaneously consum ~y its reaction with the
aluminates, This leads to the undersaturated in SO 4 of the solution as figure
V shows.
As time goes and the hydration rate is decreasing, the thermodynamic equili-
brium may be achieved. However at these later ages the OH- has usually evol
red to highe~ values because of the total dzssolutzon
• of Na + and K + and the~e
fore the Ca +L is little enough to be considered negligible.
One final question which remains is the validity of Frattini's test: it does
182 Vol. 17, No. 2
A. Moragues, et al.

mot consider the sulfate's equilibrium. Different criticism has been published
(21) (22) on the accuracy of this test to measure the pozzolanic ability of
different materials. It is not our objetive to go into these types of criti-
cism, but rather to bridge if ~he equilibrium curve (A in figure I) is adequa
te or not. The analysis of Ca +~ and OH- for Frattini's te~t are made at 7, 15
or 28 days after mixing and at these ages usually the SO. have almost totally
4
disappeared from the solution by reaction with the aluminates. Therefore curve
A could be considered as appropiate yet this point requires further experimen-
tal clarification.
Bibliographie
i.- A. Macias, C. Andrade - British Corrosion Journal 18, 82 (1983)
2.- M.T. Blanco, C. Andrade, A. Macias - British Corrosion Journal 19, 41
(1984).
3.- K.W.J. Treadaway, B.L. Brown, R.N. Cox - Corrosion of Reinforcing steel
in concrete, ASTM STP 713, 102 (1980) Tonini and Gaidis Eds.
4.- N. Frattini, Ann, Chim. 39, 41 (1949).
5.- N. Frattini, Ann. Chim. 41, 274 (1951).
6.- W.C. Hansen - Fourth International Symposium on the Chem. of Cement,
Washington (1960) 387.
7.- M.A. Roberts - Rilem Symposium, Brussels (1967).
8.- A.R. Steinberz and N. Welcman, Rev. Mater. 517, 265 (1958).
9.- C.D. Lawrence - Proc. Sympos. Structure Portland Cem. Paste Concr.
Rep. 90, Washington (1966) 387.
lO.-- P. Longuet, L. Burglen and A. Zelwer - Rev. Mater. 676, 35 (1973).
ii.- G. Bellina, M. Hassan and P. Longuet - Fourn@e C.E.R.I.L.H. (1983).
12.- C.L. Page and ~ Vaunesland, Materials and Structures, 16, 19 (1983).
13.- Gh. Abbassi - Rev. Mater., 691, ii (1974).
14.- S. Diamond, Cem. Concr. Res., 5, 607 (1975).
15.- W. Rechenberg and S. Sprung, Cem. Concr. Res. 13, 119 (1983).
16.- K. Takemoto and S. Suzuki, Semento Gijutsu Nempo i0, 32 (1956).
17.- S. Stein - Zement, 19, 240 (1930).
18.- G.L. Kalousek, C.H. Jumper and J.J. Treganing - J. Research NBS 30, 215
(1943).
19,-- P. Delmas, Rev. Mater. 702, 5 (1976).
20.- A. Macias, C. Andrade - Submitted to British Corrosion Journal.
21.- R. Larger - Bull. Larson - Labo. R. at ch. 93, (1978).
22.- R. Luxan and F. Soria - Cem. Concr. Res. 5, 461 (1975).