CEMENTand CONCRETERESEARCH.Vol. 22, pp. 112-120,1992. Printedin the USA.

0008-8846/92 $5.00+.00. Copyright© 1991 PergamonPress plc.

REACTION KINETICS OF PORTLAND CEMENT MORTARS

HYDRATED AT DIFFERENT TEMPERATURES

Knut O. Kjellsen
Swedish Cement and Concrete Research Institute
S-100 44 Stockholm, Sweden

Rachel J. Detwiler
Department of Civil Engineering
University of Toronto
Toronto, Ontario M5S 1A4, Canada

(Communicatedby H.F.W.Taylor)
(ReceivedJuly 29, 1991)

ABSTRACT
This work is a portion of a larger study of the microstructure and properties of concrete
cured at temperatures of 5 ° to 50°C, a range chosen to reflect temperatures encountered in
field curing. This paper discusses the overall hydration reaction kinetics of a 0.5
water/cement ratio portland cement mortar at ages up to 91 days. The results are correlated
with microstructural observations of companion cement paste specimens. The apparent
activation energy is found to be 11.2 kcal/mol for degrees of hydration between 20 and 30%,
indicating that at this stage the rate of reaction is controlled by a chemical process. Beyond
about 30% hydration the apparent activation energy gradually decreases.

Introduction
This work is a portion of a larger study of the effects of curing temperature on the developing
microstmcture and properties of portland cement paste, mortar, and concrete. Because concrete in the field
is not cured under ideal conditions of either time or temperature, it is important to understand how the
resulting properties may deviate from those produced using the standard laboratory cure. This paper
discusses the overall reaction kinetics of portland cement mortars cured at temperatures ranging from 5°
to 50°C. The effects of curing temperature on the microstructure and pore structure of cement paste, the
strength and strength development of mortar, and the chloride permeability of concrete are discussed in
separate papers.
Several factors influence the rate of hydration. Among the most important are the fineness and
composition of the cement, the water/cement ratio and the curing temperature. Kondo and Ueda [ 1] state
that the rate and mechanisms of hydration are controlled more directly by the concentration and the
constitution of the liquid phase at various sites, nucleation and crystal growth in the liquid or in hydrates,
the pore structure and the ease of mass transfer in the product. Brown et al. [2] state that the hydration
reaction involves processes in series, such as dissolution, nucleation and growth. The overall kinetics of
the reaction are determined by the rate of the slowest step. The rate and mechanism of hydration vary
with the progress of the reaction. According to Kondo and Ueda the rate of hydration of cement

112
Vol. 22, No. 1 REACTIONKINETICS,TEMPERATURE,HYDRATION 113

components is generally determined by mass transfer through the product layer formed around the reactant
particles except at early stages in the hydration, when the rate is controlled by a mechanism other than
diffusion, generally a chemical process.
Brunauer et al. [3] examined cement paste of very low porosity. They found that diffusion becomes the
rate controlling step after about 30% hydration. Teoreanu and Muntean [4] report that the hydration of
C3S and C2S is controlled by a surface chemical reaction in the early period of hydration and by the
diffusion of reactants through the layers of hydration products in later stages.
The dependence of the rate of hydration on temperature is frequently expressed as an apparent activation
energy. Diffusion is considered to be relatively independent of temperature.
Diffusivity may obey the Arrhenius equation, although presumably with a relatively low activation energy.
As the diffusivity decreases with increasing degree of hydration, the apparent activation energy may
decrease accordingly.
Brown et al. [5] state that the activation energy of a chemically controlled process is generally above 10
kcal/mol, while that of a diffusion controlled process is generally not greater than 5 kcal/mol. Large
variations in estimated activation energies have been reported. Some of these variations may be due to
differences in the methods used for rate determination and the subsequent calculations. Brunauer and
Greenburg [6] point out that large variations in reported rates of hydration, even of pure compounds, are
caused by differences in the methods of preparation of C3S and C2S. The nature of the raw materials
used, the temperature of burning, the rate of cooling and, in the case of beta-C2S, the nature and amount
of stabilizer used can all affect the rate of hydration. Kondo and Ueda state that the activation energy is
sometimes estimated as more than 10 kcal/mol even when the hydration of cement is controlled by
diffusion. According to them this seems to depend on the effect of the increase in porosity with increased
curing temperature.
Fujii and Kondo [7] examined the kinetics of C3S paste at temperatures between 5 ° and 50 ° C for
hydration times up to 100 hours. They hypothesized a diffusion controlled reaction stage when the surface
of C3S had become entirely covered with C-S-H. They calculated the activation energy as 5 kcal/mol.
The same authors [8] report an activation energy of 11.7 kcal/mol with beta-C2S paste at an early stage
of hydration. Kondo and Daimon [9] report activation energies in the acceleration period of C3S hydration
of 13 to 37 kcal/mol. Thus they conclude that the rate of hydration in the acceleration period is probably
controlled by a chemical reaction. Brunauer and Kantro [10] report that the temperature dependence of
beta-C2S hydration is normal (i.e., positive) up to about 70% hydration. The hydration of C3S has a
positive temperature dependence only up to about 35% hydration. They propose that in the early stages
of hydration, when the reaction of both C2S and C3S have normal temperature coefficients, the rate-
determining step is a chemical reaction. Later, the small temperature coefficients indicate diffusion
control. Because C2S is far less reactive than C3S, a thicker gel coating must build up on it before
diffusion begins to limit hydration. Copeland and Kantro [11] report activation energies of 9.8 kcal/mol
and 6.3 kcal/mol at 60 and 70% hydration, respectively, for alite paste. According to these authors the
significant decrease in the apparent activation energy from 60 to 70% hydration indicates that the
hydration process is becoming more and more diffusion controlled.
Experimental
The 0.50 water/cement mortar mixes were made from distilled water and an ordinary portland cement, the
properties of which are given in Table 1. The sand used was a standardized ISO-12679 sand, and the
cement/sand ratio was 0.289. All curing took place at constant temperature: 5 °, 12.5 °, 20 °, 35 °, or 50°C.
In each case the mixing temperature was held as close as possible to the intended curing temperature,
except for the 50°C mixes. In this case the mixing and casting temperature was held at approximately
35°C in order to prevent them from stiffening too quickly. The mortar was cast in 20 mm cube molds
and consolidated by vibration. The molds were covered with brass plates, sealed with silicone sealant and
placed in water baths at the intended curing temperature about 30 minutes after the start of mixing. The
specimens intended for prolonged curing were demolded at approximately 30% hydration, sealed in plastic
and returned to their curing tanks.
 ~.~(0.287) 5oC
0.8 (0.315)20oc
Mean value (0.201)20oc (o.136)
~ Standard deviation (s.lO)
(0.265)35°C
0.7
(0.276)12o5°C

0.6
c- ./ / • / /
o
r~
L
"O 0.5
/ ./ /" ,F /~/ /
I , / / /

"6
0,4 /
0J
l_ /
o~
ID
,g
t~ / /
/
0.3 / /

0.2 , /
/ //
• /

0.1

I I I I I I 1 2 3 7 14 28 91
2 4 6 8 10 14 I I I I I I I

Hydration Time, hoursl, daysl

,<
?-
FIG. 1
Degree of hydration vs. hydration time for Z
9
various isothermal curing temperatures
Vol. 22, No. 1 REACTIONKINETICS,TEMPERATUR~HYDRATION 115

TABLE 1
Characteristics of Norwegian P30 cement

Si02 20.55%
A1203 4.78%
Fe203 2.88%
Ca0 64.31%
Mg0 1.67%
SO 3 2.98%
Insoluble residue 0.55%
K20 0.84%
Na20 0.59%
Total alkali 1.14%
Free Ca0 1.54%
Fineness (Blaine) 395 m2/kg
Specific weight 3130 kg/m 3
C2S 13.0%
C3S 60.9%
C3A 7.8%
C4AF 8.8%

The mortar cubes were tested in uniaxial compression, as reported in references [12] and [13]. Specimen
fragments were immediately immersed in acetone to prevent further hydration. These fragments were used
to determine the amount of nonevaporable water. All mixes were replicated three times in order to
increase the confidence level of batch-to-batch uniformity. With each mix, the nonevaporable water
content was determined from three parallel specimens at each testing time.
The nonevaporable water content has been used as a means of estimating the degree of hydration. The
ratio of the amount of nonevaporable water to the degree of hydration was taken as 0.25. A variance
analysis of the measured nonevaporable water content and backscattered electron image analysis of the
unhydrated cement remaining in companion cement paste specimens [13] showed that 0.25 is a reasonable
value for this cement. The variance analysis indicated that within this range of temperatures the relation
between nonevaporable water content and degree of hydration is independent of temperature. The
nonevaporable water content per gram of cement was calculated by accounting for the ignition loss of the
sand and unlaydrated cement according to Bellander [14].
Results and Discussion
Fig. 1 shows the experimental results. At early ages the effect of temperature on the rate of hydration is
marked, while at later ages it becomes less significant. There is even a tendency of the curves to cross,
indicating that the ultimate degree of hydration will be somewhat higher for the lower temperatures.
Verbeck and Helmuth [15] believed that dense zones of hydration products would form around the
hydrating grains at higher temperatures, and that these hydration "shells" would limit or even prevent
diffusion of ions, thereby reducing the ultimate degree of hydration. Backscattered electron images of
mature pastes [16, 17] confirm the existence of the "shells", which are distinguishable in cement pastes
hydrated at 20°C and are denser when formed at higher temperatures. There is some microstructural
evidence [17] that even at 30% hydration the "shells" can act as barriers against the diffusion of sulfate
ions.
The rate of a homogeneous reaction is in general a function of the temperature and the composition of the
phase of reaction, and can be written as

r = f(temperature, composition) (1)

116 K.O. Kjellsen and R.J. Detwiler Vol. 22, No. l

If experiments are performed at several different constant temperatures, it is generally found that the
dependence on concentration or composition exhibited in the rate equation is unchanged but that the value
of the rate constant r is strongly dependent on temperature. Equation (1) can then be written as

r = fl(temperature), f2(composition) (2)

According to Copeland and Kantro [ 18], the relationship between the rate of reaction and the composition
of the system in heterogeneous reactions such as cement hydration is of such complexity that it is
extremely difficult, or impossible, to obtain a rate constant. In such cases it is frequently assumed that
the rate is proportional to an unknown function of the composition. An "apparent activation energy" can
be obtained by determining the rate as a function of temperature at an arbitrarily chosen composition. The
degree of hydration has been used as a measure of the composition of the system in question.
An analytical approach has been undertaken to obtain apparent activation energies of the hydration data.
Table 2 gives the algorithm. Details of the procedure are given in [13]. The results of the analysis are
depicted in the Arrhenius plot of Fig. 2. Numerical values of the apparent activation energies were
obtained by linear regression analysis. The results are shown in Fig. 3.

TABLE 2
Algorithm for Calculating Apparent
Activation Energies of Hydration Data

A. Functional representation of the hydration data for

each isothermal curing regime
B. Calculation of the derivative of the hydration
functions of A at fixed degrees of hydration.
C. Construction of Arrhenius plots and calculation of
apparent activation energies at these degrees of
hydration.

The apparent activation energy is approximately 11.2 kcal/mol between 20 and 30% hydration and is
relatively stable in this interval. This value indicates that the rate of the overall reaction is controlled by
a chemical reaction at degrees of hydration up to about 30%. After this point the apparent activation
energy decreases gradually. The Arrhenius plot is approximately linear to about 60% hydration. Beyond
this point the linearity becomes poor.
If the apparent activation energy is the same for all degrees of hydration (concentrations or compositions),
there is probably a single mechanism for the reaction, according to Copeland and Kantro [18]. If the
apparent activiation energy is not constant, then either the fundamental assumptions are not valid (i.e. the
composition and temperature variables in Equation (1) are not separable mathematically) or the mechanism
depends on composition. Copeland and Kantro attribute the change in activation energy to a change in
the mechanism, since it is generally anticipated that cement hydration is increasingly governed by diffusion
processes. Since the activation energy of a diffusion process should be smaller than that of a chemical
process, a decrease in the apparent activation energy with hydration would be expected. The overall
apparent activation energy decreases steadily, perhaps partly because of the increasing diffusion resistance
of the hydration shells. In addition, the different minerals may have different rate controlling mechanisms
at the same overall hydration levels. For example, C3S hydration will presumably be diffusion controlled
at an earlier stage than C2S hydration. In addition, the broad particle size distribution and the
polymineralic composition of most grains contributes to an overlap of rate controlling mechanisms.
Vol. 22, No. 1 REACTION KINETICS, TEMPERATURE, HYDRATION 117

-2.0

-3.0

-4.0

"O -5.0
i-
"0
f-
-6.0 ~ b" °. 6

-7.0

e. e ~ ~ e

-8.0
• % 0 ~ 0

O-- •

I I I I !
150)-I 135) -I 120)-I (12.5)-I 1.5)-I
(Temperature, °C)-I

FIG. 2
Arrhenius plot of the calculated hydration data.

We found [16,17] that hydration temperature strongly influences the distribution of hydration products
throughout the cement paste matrix at degrees of hydration above about 30%. This implies that the
restriction on ionic movement and the general conditions for hydration will probably vary with temperature
for a given degree of hydration. The validity of the separation made in Equation (2) may be questionable
at more advanced stages of hydration.
In the early stages of hydration, rims form on the surfaces of the cement grains. Dissolved species pass
through, increasing the liquid-filled space between the unhydrated cement core and the outward-thickening
rim. They then nucleate in the bulk solution. From the SEM study in [17] this appears to be the general
mode of hydration up to about 30% hydration regardless of temperature for specimens hydrated at
temperatures between 5 ° and 50°C. A change in the hydration mechanism is then obviously occurring,
the change being more significant and the "threshold degree of hydration" lower the higher the
temperature. Up to about the threshold, the reaction proceeds mainly through-solution at both 5 ° and
118 K.O. Kjellsen and R.J. Detwiler Vol. 22, No. 1

12.0

E
10.0 _

U
..Y

O3
l_
¢J
\
8.0
E
LJJ

6.0

.<

f,..
ro 4.0
o.

2.0

I I I I I 1
0.2 0.3 0.4 0.5 0.6 0.7
D e g r e e of H y d r a t i o n

FIG. 3
Apparent activation energy vs. degree of hydration.

50°C. This implies that hydration is essentially a reaction with processes in series. The favored through-
solution mechanism may be due to the relatively high diffusivity of the hydration rims at this stage. As
the hydration proceeds a topocbemical reaction will be increasingly favored and much more so the higher
the temperature. This is apparent from the SEM study.

The shift from the through-solution mechanism will probably occur at lower hydration levels the higher
the temperature. This implies that the reaction changes from being essentially a series reaction to parallel
reactions; that is, through-solution and topochemical reactions now proceed concurrently. The rate of
reaction involving a succession of steps as the series reaction is generally controlled by the slowest step.
According to Bezjak [19], in parallel reactions the overall rate of reaction will be a complex function of
the individual rate-determining steps. Levenspiel [20] states that if the various parallel paths are
independent of each other, the overall rate will simply be the sum of the individual rates of each parallel
path. This implies that a change in the hydration mechanism from essentially through-solution to
simultaneous topochemical and through-solution processes does not necessarily entail a noticeable change
in the apparent activation energy. Thus the inhomogeneous distribution of C-S-H as formed at higher
temperatures may not be a result of regular diffusion control. However, when the intra-shen gaps
eventually fill up with hydrates it is likely that further hydration becomes diffusion controlled. Since the
hydration shells formed at higher temperatures presumably have a very low diffusivity, the rate of reaction
will be substantially reduced. These conditions may explain the formation of the dense hydration shells
Vol. 22, No. 1 REACTIONKINETICS.TEMPERATURE,HYDRATION 119

at higher temperatures and higher degrees of hydration, as observed in [16] and [17], and the tendency
of the hydration curves to cross at later ages as seen in Fig. 1.
Conclusions
1. The apparent activation energy for this portland cement mortar is calculated as 11.2 kcal/mol for
degrees of hydration between 20 and 30% (as indicated by the amount of nonevaporable water). This
value suggests that the rate of hydration is controlled by a chemical process at this stage. Beyond 30%
hydration the apparent activation energy gradually decreases.
2. Microstructural observations of companion cement paste specimens show that as hydration proceeds
the hydration products tend to form "shells" around the cement grains. The higher the temperature the
denser the "shells" relative to the surrounding hydration products in the bulk paste. The formation of the
shells is a result of increasingly favored topochemical or local through-solution reactions. However, the
change in hydration mechanisms does not seem to cause any differences in the apparent activation energy,
which for a given degree of hydration remains independent of temperature up to about 60% hydration.
3. Since the hydration temperature strongly influences the microstructure at a given degree of hydration
beyond about 30%, the separation of the composition and temperature functions in the fundamental rate
equation (Equations (1) and (2)) may not be correct.
4. For isothermal curing the higher the temperature, the lower the degree of hydration at which
topochemical reactions displace through-solution reactions as the favored mode of further hydration.
Acknowledgements
We would like to express our appreciation for the support provided by the Division of Building Materials
at the Norwegian Institute of Technology, where the laboratory work for this paper was performed. We
would also like to thank the Royal Norwegian Council for Scientific and Industrial Research (NTNF),
Aker Entrepren(6r A/S, BEA Consult A/S, Scancem Chemical A/S, Rescon A/S, Norcem Betong A/S,
Norcem A/S and Norges Betongindustriforbund for their financial support. The second author gratefully
acknowledges the postdoctoral fellowship given by NTNF.
References
1. Kondo, R. and Ueda, S. "Kinetics and Mechanisms of the Hydration of Cements," Proceedings of
the 5th International Congress on the Chemistry of Cement, Tokyo, 1968.
2. Brown, P.W.; Pommersheim, J.M. and Frohnsdorff, G. "Kinetic Modeling of Hydration Processes,"
Cements Research Progress, American Ceramic Society, 1983.
3. Brunauer, S.; Yudenfreund, M.; Odler, I. and Skalny, J. "Hardened Portland Cement Pastes of Low
Porosity VI. Mechanism of the Hydration Process," Cement and Concrete Research, vol. 3, no. 2, 1973.
4. Teoreanu, I. and Muntean, M. 'Whe Kinetics of the Hydration Process of the Silicate Constituents of
Portland Cement Clinker, Under the Influence of Electrolytes," Silicates Industriels, no. 2, 1974.
5. Brown, P.W.; Pommersheim, J. and Frohnsdorff, G. "A Kinetic Model for the Hydration of Tricalcium
Silicate," Cement and Concrete Research, vol. 15, no. 1, 1985.
6. Brunauer, S. and Greenburg, S.A. 'q'he Hydration of Tricalcium Silicate at Room Temperature,"
Proceedings of the 4th International Congress on the Chemistry of Cement, vol. 3, Washington, D.C.,
1960.
7. Fujii, K. and Kondo, W. "Kinetics of the Hydration of Tricalcium Silicate," Journal of the American
Ceramic Society, vol. 57, no. 11, 1974.
8. Fujii, K. and Kondo, W. "Rate and Mechanism of Hydration of Beta-Dicalcium Silicate," Journal
of the American Ceramic Society, vol. 62, no. 3-4, 1979.
9. Kondo, R. and Daimon, M. "Early Hydration of Tricalcium Silicate: A Solid Reaction with Induction
and Acceleration Periods," Journal of the American Ceramic Society, vol. 52, no. 9, 1969.
120 K.O. Kjellsenand R.J. Detwiler Vol. 22, No. 1

10. Brunauer, S. and Kantro, D.L. "The Hydration of Tricalcium Silicate and Beta-Dicalcium Silicate
from 5 ° to 50°C, '' The Chemistry of Cements, Academic Press, 1964.
11. Copeland, L.E. and Kantro, D.L. "Hydration of Portland Cement," Proceedings of the 5th
International Congress on the Chemistry of Cement, Tokyo, 1968.
12. KjeUsen, K.O. and Detwiler, R.J. "Later Age Strength Prediction by a Modified Maturity Model,"
to be submitted to ACI Materials Journal.
13. Kjellsen, K.O. Physical and Mathematical Modelling of Hydration and Hardening of Portland
Cement Concrete as a Function of Time and Curing Temperature, Dr. Ing. Dissertation 1990:76, Division
of Building Materials, Norwegian Institute of Technology, Trondbeim, December 1990.
14. BeUander, U. "Accelererad prOvning av betongs h~Ufasthet. Best/~mning av hydratationsgrad,"
Swedish Cement and Concrete Research Institute report no. Fo 7312/P5, Stocldaolm 1973.
15. Verbeck, G.J. and Helmuth, R.H. "Structures and Physical Properties of Cement Pastes,"
Proceedings of the 5th International Congress on the Chemistry of Cement, Tokyo, 1968.
16. Kjellsen, K.O.; Detwiler, R.J. and Gj~rv, O.E. "Backscattemd Electron Imaging of Cement Pastes
Hydrated at Different Temperatures," Cement and Concrete Research, vol. 20, no. 2, 1990, pp. 308-311.
17. Kjellsen, K.O.; Detwiler, R.J. and GjCrv, O.E. "Development of Microstructure in Plain Cement
Pastes Hydrated at Different Temperatures," Cement and Concrete Research, vol. 21, no. 1, 1991, pp.
179-189.
18. Copeland, L.E. and Kantro., D.L. "Chemistry of Hydration of Portland Cement at Ordinary
Temperature," The Chemistry of Cements, Academic Press, 1964.
19. Bezjak, A. "A New Approach to Mathematical Modeling of Nucleation and Growth in Kinetic
Analysis of Cement Hydration," Advances in Cement Manufacture and Use, Engineering Foundation
Conference, Missouri, 1988.
20. Levenspiel, O. Chemical Reaction Engineering, Wiley, 1972.