CEMENT and CONCRETE RESEARCH. Vol. 23, pp. 603-608, 1993. Printed in the USA.

0008-8846/93. $6.00+00. Copyright © 1993 Pergamon Press Ltd.

QUANTITATIVE DETERMINATION OF TRIETHANOLAMINE I N CEMENTS

V . T . Y ~ l m a z , N. M e n e k a n d M. O d a b a s o ~ l u
Ondokuz Mayls University, Chemistry Department
55139, Kurupelit, Samsun-TURKEY

(Communicated by P.L.Dan)
(Received May 29, 1992)

ABSTRACT
A new analysis method for the quantitative d e t e r m i n a t i o n of
t r i e t h a n o l a m i n e (TEA) in the aqueous phase of cements was
developed. TEA was converted into the TEA-Fe 3+ complex by
t r e a t i n g it with IM NaOH and 10% Fe 3+ solutions. This
m e t h o d was based on the determination of the TEA-Fe 3+
complex by polarographic techniques. The TEA content in the
aqueous phase of the tricalcium a l u m i n a t e - g y p s u m system was
analysed using the analysis method and the amount of TEA
adsorbed was found to be ~ l . 5 m g per g of the solid phase.

Introduction

T r i e t h a n o l a m i n e (TEA) is used as a grinding aid in cement

p r o d u c t i o n and as a raw material in many cement admixtures (1,2).
In w a t e r r e d u c i n g - a c c e l e r a t i n g types of admixtures, TEA is
employed to reduce the excessive retardation effect of the water
r e d u c i n g agent and generally preferred to calcium chloride owing
to the potential corrosive effect of the chloride ion on embedded
metals in concrete.

The m e c h a n i s m of the action of TEA in cement h y d r a t i o n is not

completely understood. For example, R a m a c h a n d r a n (3-5) showed that
TEA alone acted as a retarder in the h y d r a t i o n of the silicate
phases and as an accelerator in the h y d r a t i o n of the aluminate
phases as its addition rate was higher than 0.1% by weight of
cement. Pauri, et al.(6) found the similar findings for tricalcium
silicate. However, Dusmuradov and Kantsepolskii (7) observed that
the addition of TEA (0.1-1.0%) accelerated the setting time of
h i g h - a l i t e cements while retarding the setting time of sulphate-
resistant cements. It was also reported that at an addition rate
of 0.02%, T E A acted as an accelerator, at 0.25% as a m i l d set
retarder, at 0.5% as a severe retarder, at 1.0% as a very strong
a c c e l e r a t o r in the hydration of Portland cement (8).

603
604 V.T. Yilmaz et al. Vol. 23, No. 3

From the results given in the literature, it is not yet clear

whether TEA is an accelerator or a retarder. It is p o s s i b l e that
TEA may act as either an accelerator or a retarder, d e p e n d i n g on
the chemical composition of cement and the amount of TEA added. In
order to assess the actual role of TEA in cement hydration, it
would be very useful to analyse the aqueous phase of cements for
TEA. The present analysis methods for TEA, established by
M c C a l l - M a n n o n e (9) and Connolly-Hime (i0), include several
treatments such as acidification, evaporation to dryness and
solvent extraction etc., and only provide qualitative information.

It is long known that TEA has the ability to chelate certain

metallic ions in h ~ h l y alkaline m e d i u m (pH > 12), one of which is
the ferric ion (FeJT). The proposed m e c h a n i s m for the complexation
of the ferric ion by TEA is illustrated in Fig.l (ii). In light of
this information, we developed a new analytical m e t h o d based on
the m e a s u r e m e n t of the concentration of the TEA-Fe 3+ complex by
using p o l a r o g r a p h i c techniques. This paper describes the
experimental details of the analysis method and its application to
the T E A - 3 C a O . A I 2 0 3 - C a S O 4 . 2 H 2 0 - H 2 0 system.

o~C~'~CH2

3+
HOCHgCH2\ 20H-
Fe + HOCHzCH
2-N !6 CH2
CH2
HOCH2CH2
/ H~)-j/
I
OH

FIG. 1
Chelation of the ferric ion by TEA after Chaberek and Martell (ii)

Experimental

Solutions
a) A stock solution of TEA was p r e p a r e d by d i s s o l v i n g ig of
TEA (Merck, extra pure) in a liter of distilled water.
b) 86.35g of N H 4 F e ( S O 4 ) 2 . 1 2 H 2 0 (BDH, >98%) was dissolved in a
liter of distilled water. This solution contains 10g of Fe 3+ per
liter.
c) IM NaOH solution (40g NaOH/I).

Procedure
In order to prepare standard TEA-Fe 3+ complex solutions, 0 to
1.5ml of the stock solution of TEA were t r a n s f e r r e d to 100ml
volumetric flasks. 15ml of IM NaOH and 5ml of the Fe 3+ stock
solution, respectively, were added into each v o l u m e t r i c flask.
The solutions were brought to the m a r k by adding d i s t i l l e d water
Vol. 23, No. 3 TEA. QUANTITATIVEDETERMINATION, POLAROGRAPHY 605

and shaken for about 2 min. These solutions were then filtered off
to remove the precipitation product, Fe(OH) 10ml of each
solution was placed in the polarographic cell ~nd deaerated with
nitrogen gas for 4 min. The polarograms of these solutions were
obtained by a EG & G PARC M O D E L 384 B POLAROGRAPHIC A N A L Y S E R using
the differential pulse polarographic mode of the instrument. An
inert atmosphere (N2) was maintained over the solutions during
measurements. The setting parameters were as follows: pulse
height, 20mV; drop time, is; scan increment, 4V; potential -0.6 to
-I.2V.

A p p l i c a t i o n of the analysis method

To provide an example of application of the method, the
adsorption of TEA by the 3CaO.AI203-CaSO4.2H20 (70%+30%) mixture
was studied, lg of this mixture was shaken with 5ml of water
containing 5mg TEA for 5 min. After predetermined hydration times,
the excess aqueous phase was filtered off and lml of the aqueous
phase was used to prepare 100ml test solutions as explained above.

Results and Discussion

Fig. 2 shows a typical

36 differential pulse polarogram
obtained from a 15 ppm TEA-Fe 3+
complex solution. Reduction of
Fe 3~ of the complex by elemental
mercury produced this type of
polarogram which is quite
suitable for the analysis of this
complex, because TEA alone does
30 not give any polarogram. In fact,
polarographic measurements are
normally carried out using
<
supporting electrolytes (12). In
t- this study, initially a
recommended supporting
I--.4
electrolyte consisting of 0.2M
NaOH and 0.3M TEA solutions was
24 used. However, it was observed
that the filtrates obtained from
the preparation of TEA-Fe 3+
complexes were found to be much
more convenient to use for this
purpose, without needing an extra
supporting electrolyte. The pH of
the filtrates after the
precipitation of Fe(OH)3 was
found to be approximately pH 13.
-0.6 -0.8 -1.0 -1.2 The potential m a x i m u m (Emax) of
E,V the peak was -0.81+0.05V.

FIG. 2
Typical current-potential curve Fig.3 shows the r e l a t i o n s h ~
for a 15 ppm TEA-Fe 3+ complex between TEA and Fe ~T
concentrations in the highly
alkaline aqueous phase. After forming the TEA-Fe 3+ complex using
different amounts of TEA, the solutions were analysed for Fe 3+.
 606 V.T. Yilmaz et al. Vol. 23, No. 3

I t is clearly shown that there is a linear relationship between

TEA and Fe 3+ concentrations in the aqueous phase. The
relationship is very close to the theoretical calculations (149g
TEA-56g Fe 3+ ). TEA in the alkaline solution strongly chelates
the ferric ion and the amount of the TEA-Fe 3+ complex linearly
increases with increasing TEA content in the aqueous phase.
Therefore, the polarogram produced by the TEA-Fe 3+ complex can be
used for the direct analysis of TEA.

5 F 10
| y= -0.095 + 0.392x
y=-0.247+ 0.615x
r = 0.999
r= 0.999
4-
E
Q_
Q.

c"
.o 3 - ~6
_D
o
~n
.c_
+ 2 -

1 - 2

I/ l L I I/ i I L
4 8 12 0 5 10 15
TEA in solution, ppm TEA concentrotion, pprn
FIG. 3 FIG. 4
Fe 3+ concentrations against Typical calibration curve
TEA concentrations in the obtained by p o l a r o g r a p h y
highly alkaline solution

A typical calibration curve obtained in this study is shown

in Fig. 4. The p o l a r o g r a m of the TEA-Fe 3+ complex was considered
as a peak and the peak height of the complex was directly
proportional to the TEA concentration; increasing departures from
linearity were observed beyond 20 ppm TEA. The calibration curve
indicates that it is possible to analyse TEA concentrations as low
as 1 ppm.

The a p p l i c a t i o n of this method is illustrated in Fig. 5,

showing a plot of the initial TEA concentration (5mg) against that
remaining in solution. An immediate drop in the TEA content of
solutions occured due to adsorption by the initially formed
h y d r a t i o n products (ettringite) of the t r i c a l c i u m a l u m i n a t e - g y p s u m
mixture. The adsorption reached a saturation level after 30 min of
h y d r a t i o n and remained almost unchanged at longer times. The
adsorbed amount of TEA was found to be ca.l.5mg TEA per g of the
 Vol. 23, No. 3 ~ QUANTITATIVED ~ A T I O N , POLAROGRAI:qlY 607

C
. m
0--8 O O FXG. 5
TEA concentrations in the
LU 3 - aqueous phase of C3A +
I-- CaSO4.2H20 mixtures
O.
(W/S=5, initial TEA= 5mg)
E
2 I I I
0 60 120 180
Hydration time, rain
solid mixture. The adsorbed amount of TEA on ettringite, reported
by Pauri, et al.(6), was 40mg TEA per g of the solid. They used a
U V m e t h o d to determine the TEA content in the aqueous phase,
altough they did not give any experimental detail for the analysis
method. However, we observed that TEA alone as well as its complex
with the ferric ion does not produce UV spectra. In fact, TEA is a
weak base (kb=5.89x10-7) and most of TEA in the aqueous phase is
in the m o l e c u l a r state. The positively charged hydrated cement
surfaces will preferentially adsorb the anionic m o l e c u l e s such as
superplasticizers. The adsorbed amount of superplasticizers by
ettringite or by Portland cement was reported to be in the range
of 5 to 15mg superplasticizer per g of the solid phase (13,14).
Therefore, it is unlikely that ettringite adsorbs TEA at high
amounts as reported by Pauri, et al. (6). The results of the
present study show that the adsorbed amount of TEA by the
t r i c a l c i u m a l u m i n a t e - g y p s u m mixture is very small and is in
agreement with theoretical expectations.

The ferric ion in the TEA-Fe 3+ complex may be determined by

other analysis methods for the Fe 3+ and thus TEA content in
solution may be determined indirectly. All solutions obtained from
the different stages of this study were also analysed using an
atomic absorption spectrometer and the calculated TEA
concentrations were found to be in very good agreement with those
obtained by the new analysis method.

Conclusions

A superior analytical method now exists to analyse the TEA

content in cements. TEA in solution is converted into the TEA-Fe 3+
complex by adding IM NaOH and 10% Fe 3+ solutions. This complex can
be analysed by using polarographic techniques. The polarograms
produced by the complex are very suitable for the quantitative
d e t e r m i n a t i o n of TEA. Application of the analysis method shows
that TEA is adsorbed by the initial hydration products of the
t r i c a l c i u m a l u m i n a t e - g y p s u m mixture. The adsorbed amount of TEA is
l. Smg per gram of the solid.
608 V.T. Yflm~ et -1. Vol. 23, No. 3

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