J Surfact Deterg (2015) 18:919–922
DOI 10.1007/s11743-015-1699-1
SHORT COMMUNICATION
An Inaccuracy in the Determination of Cocoamidopropyl Betaine
by the Potentiometric Method
Ramin Mostafalu1 • Abbas Banaei1 • Fatemeh Ghorbani1
Received: 10 February 2015 / Accepted: 19 May 2015 / Published online: 3 June 2015
Ó AOCS 2015
Abstract Cocoamidopropyl betaine (CAPB) is one of the
most important amphoteric surfactants frequently used in
cosmetic products, especially shampoos and bath products.
Potentiometric and two-phase active titrations of com-
mercial grade CAPB are not in good agreement. The
findings of this study suggest dimethylaminopropylamine-
betaines interfere with potentiometic titration.
Keywords Zwitterionic surfactant 
Cocamidopropylbetaine  Dimethylaminopropylamine 
Potentiometry  Two-phase titration
Introduction
Cocamidopropyl betaine (CAPB) is a well-known am-
photeric surfactant used in the cosmetic industry. CAPB is
derived from coconut oil and dimethylaminopropylamine
[1]. It is a zwitterionic surfactant consisting of both a
carboxylate anion and a quaternary ammonium cation, as
shown in Fig. 1 [2].
According to toxicological data, CAPB is safe and non-
irritating [3]. It is widely used in cosmetic products,
especially liquid soaps, shampoos and bath products [4],
because of its relative mildness and good conditioning
characteristics compared with other surfactants [5].
The common methods used for qualitative and quantita-
tive analytical control of surfactants are titrimetric,
& Ramin Mostafalu
raminmostafalu@gmail.com
1
Research and Development, Padideh Shimi Jam Co., Bahar 2
St., Ershad 4 St., East Hesabi Blv., Eshtehard Industrial
Town, Karaj, Iran
chromatographic and spectrometric [6, 7]. Active matter of
commercial betaine is determined by potentiometry [8] and
two-phase titration [9]. In general, the active matter as de-
termined by potentiometric and two-phase titration is not in
agreement. In the continuation of our previous research work
[10–12], this article discusses the source of this discrepancy.
Experimental
Materials and Methods
The reagents were purchased from the Merck, Sigma-
Aldrich and Daejung companies and were used without
further purification. The cocamidopropyl betaine (CAPB)
sample was commercially available. Water was double
distilled and purified by a Youngling Aquamax-Ultra water
purifier. The all-purpose titrator 835 Titrando (0.1 mV
resolution) combined with a Metrohm 806 exchange unit
(20-ml burette volume with an outstanding resolution of
20,000 steps per cylinder volume) and controlled by the
Tiamo software was used to perform potentiometric titra-
tions. During the titrations and measurements, the solutions
were magnetically stirred using a 727Ti Stand. The above-
mentioned instruments were purchased from Metrohm,
Switzerland. The potentiometric titrations were performed
by using the following cell assembly:
Ag=AgClðKCl; 3MÞjjtest solutionjjliquid membranej
 ðNaCl; 3MÞAg=AgCl:
Potentiometric Titration
Approximately 0.5 g of the sample was dissolved in 20 ml
of methanol and 30 ml of ethyleneglycol monomethyl
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O the end point was read before the last two drops of SLS.
O The active matter was calculated using Eq. 2.
R N N
H V  N  f  M:W:  2:5
O Active % ¼ ð2Þ
m
Fig. 1 Cocoamidopropyl betaine (CAPB) where V is the SLS intake volume (ml), f is the SLS factor,
ether, and then 0.25 ml of buffer A (buffer A: 8 g of N is the SLS normality, M.W. is the molecular weight of
sodium acetate and 4 g of sodium hydroxide in 200 ml CAPB (358 g/mol), and m is the mass of sample (g).
distilled water) was added to this solution. The resulting
solution was titrated with 0.1 N perchloric acid solution in Preparation of the Mixed Indicator
1,4-dioxane (pH glass electrode and Ag/AgCl reference
electrode). The active matter was determined from Eq. 1. Five grams of dimidium bromide and 25 g of disulfine blue
were weighed and dissolved in H2O–ethanol (50:50) to a
ðV2  V1Þ  N  f  M:W:
Active % ¼ ð1Þ volume of 100 ml. At the end, 25 ml of the solution was
10m diluted with water to a volume of 500 ml.
where V1 is the ml of titrant consumption to reach the first
equivalence point, V2 is the ml of titrant consumption in ml Synthesis of the DMAPA-Betaine
to reach the second equivalence point, f is the perchloric
acid factor, N is the perchloric acid normality, M.W. is the DMAPA-betaine was synthesized by a previously reported
molecular weight of CAPB (358 g/mol), and m is the mass method by Kowalczyk [13] with some modifications.
of the sample (g). DMAPA (0.1 M) was mixed with monochloroacetic acid
(0.1 M) in anhydrous ethanol (20 ml). The mixture was
Two-Phase Titration stirred at 70 °C for 24 h. Then the reaction mixture was
cooled to room temperature, and the pH was adjusted to
About 1 g of CAPB was dissolved in distilled water to a about 5.0 by the addition of NaOH. The solvent was
volume of 250 ml (using a few drops of ethanol to remove evaporated under reduced pressure, and the residue was
the foam). Then 10 ml of the solution was poured into a dried over sodium sulfate and then recrystallized from
glass-stoppered Erlenmeyer flask, and 10 ml of chloro- anhydrous ethanol.
form, 10 ml of mixed indicator and 10 ml of 2 M sulfuric
acid were added. The resulting solution was titrated with
0.004 N sodium lauryl sulfate (SLS) solution until the Result and Discussion
color changed from blue to gray (pink) in the chloroform
phase. The color should be visible. After the appearance of Cocamidopropyl betaine (30 % active) is usually synthe-
pink color, two drops of SLS were added, and the mixture sized using a two-step batch process [14] as shown in
was stirred. If the color intensity increased, the volume of Fig. 2. In the first step a condensation reaction takes place

Fig. 2 Synthesis of Step 1

cocamidopropyl betaine
O O

R O O R
O O

R or O
O + H2N N R N N
H
R OH
or

Step 2
O
O
ONa
R N N + Cl O- + NaCl
H R N N
O H
O

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Fig. 3 Reaction of DMAPA
with sodium monochloroacetate
40
35
30
Active matter content
25 Potenometric traon
Two-phase traon
20
15
10
5
0
0 20 40 60 80
DMAPA-Betaines (wt%)
Fig. 4 Influence of the DMAPA-betaines on the potentiometric and
two-phase titration of CAPB
between the coconut oil or fatty acid and dimethylamino-
propylamine (DMAPA) at about 160 °C. In the second
step, the resultant dimethylaminopropyl cocoamide reacts
with sodium monochloro acetate under alkaline conditions
in aqueous solution.
Unreacted free amines seem to be the most critical im-
purities in cocamidopropyl betaine formulations. The un-
reacted DMAPA from the condensation reaction can react
with sodium monochloroacetate in the second step to
produce betaine-like compounds (DMAPA-betaines) as
shown in Fig. 3. DMAPA-betaines are highly similar to
cocamidopropyl betaine.
To estimate the influence of DMAPA-betaines on the
determination of CAPB activity, model solutions contain-
ing commercial CAPB were analyzed by potentiometric
and two-phase titrations, in the presence of different
amounts of DMAPA-betaines. The results are shown in
Fig. 4. These results indicate that when varying the
weight ratio of a CAPB/DMAPA-betaine mixture con-
taining the same total amount of material (about 30 w.%),
the amount determined by potentiometry is almost con-
stant. Therefore, both CAPB and DMAPA-betaines are
determined by this method. However, this significant in-
terfering effect of DMAPA-betaines on the CAPB deter-
mination is not observed in the two-phase titration method.
Therefore, the results show that the two-phase method is
921
more accurate than the potentiometric method for the de-
termination of amphoteric surfactants in the presence of
other zwitterions.
Conclusion
A significant interfering effect of DMAPA-betaines on the
CAPB determination by the potentiometric method was
observed. The results showed that the two-phase titration
method is more accurate than the potentiometric method
for the determination of amphoteric surfactants in the
presence of other zwitterions.
Acknowledgments We acknowledge Padideh Shimi Jam Co. for
support of this work.
100
References
1. Jacob SE, Amini S (2008) Cocamidopropyl betaine. Dermatitis
19:157–160
2. Foti C, Bonamonte D, Mascolo G, Corcelli A, Lobasso S, Rigano
L, Angelini G (2003) The role of 3-dimethylaminopropylamine
and amidoamine in contact allergy to cocoamidopropylbetaine.
Contact Dermat 48:194–198
3. Armstrong DK, Smith HR, Ross JS, White IR (1999) Sensitiza-
tion to cocamidopropylbetaine: an 8-year review. Contact Dermat
40:335–336
4. Basheva ES, Ganchev DN, Denkov D, Kasuga K, Satoh N, Tsujii
K (2000) Role of betaine as foam booster in the presence of
silicone oil drops. Langmuir 16:1000–1013
5. Fowler JF, Zug KM, Tylor JS, Storrs FJ, Sherertz EA, Sasseville
DA, Rietschel RL, Pratt MD, Mathia CGT, Marks JG, Maibach
HI, Fransway AF, Deleo VA, Belsito DV (2004) Allergy to co-
camidopropyl betaine and amidoamine in North America. Der-
matitis 15:5–6
6. Gheorghe S, Lucaciu I, Grumaz R (2011) Detergents legislative
framework and ecotoxicological testing methodology. J Environ
Prot Ecol 12:1525–1532
7. Yong Q, Gaoyong Z, Baoan K, Yumei Z (2005) Primary aerobic
biodegradation of cationic and amphoteric surfactants. J Surfac-
tants Deterg 8:55–58
8. Gerhards R, Jussofie I, Käseborn D, Keune S, Schulz R (1996)
Modern methods for the analysis of cocoamidopropyl betains.
Tenside Surfactants Deterg 33:8–14
9. Rosen MJ, Zhao F, Murphy DS (1987) Two-phase mixed indi-
cator method for the determination of zwitterionic surfactants.
J Am Oil Chem Soc 64:439–441
10. Mostafalu R, Kaboudin B, Kazemi F, Yokomatsu T (2014) N-ary-
lation of amines: C-N coupling of amines with arylboronic acids
using Fe3O4 magnetic nanoparticles-supported EDTA-Cu(II)
complex in water. RSC Adv 4:49273–49279
11. Kaboudin B, Mostafalu R, Yokomatsu T (2014) Fe3O4
nanoparticle-supported Cu(II)-b-cyclodextrin complex as a
123
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magnetically recoverable and reusable catalyst for the synthesis
of symmetrical biaryls and 1,2,3-triazoles from aryl boronic
acids. Green Chem 15:2266–2274
12. Kaboudin B, Mostafalu R (2012) Triethylphosphate/phosphorus
pentoxide as an efficient reagent for the phosphorylation of
phenols. Phosphorus Sulfur 187:776–780
13. Kowalczyk I (2008) Synthesis, molecular structure and spectral
properties of quaternary ammonium derivatives of 1,1-dimethyl-
1,3-propylenediamine. Molecules 13:379–390
14. Uphues G (1998) Chemistry of amphoteric surfactants. Lipid/Fett
100:490–497
Ramin Mostafalu has a Ph.D. in organic chemistry and has a position
at the R&D department of Padideh Shimi Jam Co. His Ph.D. thesis on
nanotechnology and organic synthesis was co-supervised by Prof.
Babak Kaboudin and Prof. Mohammad Mahdi Najafpour from the
University of IASBS. His principal research interests are in the
synthesis, application and properties of new surfactants. He is also
interested in the investigation of surfactants in nanotechnology.
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J Surfact Deterg (2015) 18:919–922
Currently, his research team is focusong on this field as an emerging
area.
Abbas Banaie has been a researcher in the R&D department at
Padideh Shimi Jam Co. since 2008. His M.Sc. thesis in 2005 at Sistan
and Baluchestan University focused on the synthesis and application
of novel organic compounds containing heterocyclic rings. He is
interested in the synthesis and evaluation of surface active agents in
different applications.
Fatemeh Ghorbani is a research and development expert at Padideh
Shimi Jam Co. where she does research on new products and
improving the quality of products. She received her M.Sc. in organic
chemistry from Shahid Beheshti University in 2007. Before joining
Padideh Shimi Jam Co. in 2011, she worked at Tofigh Darou Co. for
about 4 years in the Department of Chemical Synthesis. She has
worked in research and development on various aspects of surfactant
science and surface chemistry.