Experimental Determination of

Monoethanolamine Protonation Constant and

Its Temperature Dependency
Sholeh Ma’mun, Kamariah, Sukirman, Desi Kurniawan, Eleonora Amelia, Vitro Rahmat and Deasy R. Alwani
Department of Chemical Engineering, Faculty of Industrial Technology, Islamic University of Indonesia, Yogyakarta 55501,
Indonesia, [email protected]*

Abstract: Carbon dioxide as one of the major contributors to the global warming problem is produced in large
quantities by many important industries and its emission seems to rise from year to year. Amine-based absorption
is one of the methods to capture CO2 from its sources. As a reactive system, mass transfer and chemical reaction
take place simultaneously. In a vapor-liquid equilibrium model for the CO2-amine-water system, some
parameters e.g. mass transfer coefficients and chemical equilibrium constants need to be known. However, some
parameters could be determined experimentally and the rests could be regressed from the model. The protonation
constant (pKa), as one of the model parameters, could then be measured experimentally. The purpose of this
study is to measure the pKa of monoethanolamine (MEA) at a range of temperatures from 303 to 330 K by a
potentiometric titration method. The experimental data obtained were in a good agreement with the literature
data. The pKa data from this work together with those from the literature were then correlated in an empirical
correlation to be easily used for future research.

Keywords: Carbon dioxide, Absorption, Monoethanolamine, Protonation constant, Potentiometric titration

1. INTRODUCTION 26.3 Gt of CO2 was emitted globally and reached 32 Gt in 2010

Carbon dioxide (CO2) is known as one of the major [4]. Necessary efforts to reduce the CO2 emission are, therefore,
contributors to the global warming problem. Carbon dioxide is required. Absorption is one of the methods to capture CO2 from
produced in large quantities from coal-fired power plants, steel its emission sources.
production, petrochemical manufacturing, cement production, A commercial absorbent for CO2 removal requires both a
and natural gas purification as well as the exhaust gas from the high net cyclic capacity and high reaction rate for CO2, as well
transportation sectors. as high chemical stability. In addition, other criteria that need to
In the past decades, CO2 removal from flue gas streams be considered are, according to [5], base strength (pKa),
started as a potentially economic source of CO2, mainly for molecular weight per NH functionality, slope of equilibrium
enhanced oil recovery (EOR) operations. Moreover, CO2 was curve, heat of absorption, viscosity, nature of degradation
also produced for other industrial applications such as products, nitrosamine formation potential, cost and availability,
carbonation of brine, welding as an inert gas, food and beverage and HSE (Health, Safety, and Environment). Research on
carbonation, dry ice, urea production, and soda ash industry [1, solvent development has been conducted to meet those criteria
2]. However, environmental concerns, such as the global by testing alkanolamines and their blends, sodium carbonate
climate change, are now focused as one of the most important solutions, chilled ammonia, and amino acid salts [3, 6-13].
and challenging environmental issues facing the world Aqueous solutions of alkanolamines are the most commonly
community, and drive an intensive research on CO2 capture and used as chemical absorbents for the CO2, such as CO2 removal
sequestration [3]. from natural gas, from refinery and synthesis gas streams.
The CO2 emission seems to rise from year to year. In 2005, Among them, aqueous monoethanolamine (H2NCH2CH2OH,
MEA) as a primary amine has been used extensively for this
*email address of author to whom correspondence should be addressed purpose. It has several advantages over other commercial
1 Sriwijaya International Conference on Engineering, Science and Technology (SICEST) 2016
alkanolamines, such as high reactivity, low solvent cost, low ions, so that the protonation constant (Ka) can be expressed as
molecular weight and, thus, high absorbing capacity on a mass follows
basis and reasonable thermal stability and thermal degradation
H + A-
rate. However, MEA has some drawbacks such as high Ka = total
H+ (10)
enthalpy of reaction with CO2 leading to higher regeneration HA left
energy consumption in desorber, formation of a stable Equation (10) indicates that the Ka value of the weak acid HA
carbamate and also formation of degradation products with approximately is equal to the concentration of H+ ions or, in
COS or oxygen bearing gases, inability to remove mercaptans, other words, the pKa equals the pH of the solution.
vaporization losses because of relatively high vapor pressure, The temperature dependency of the protonation constant (Ka)
more corrosive than many other alkanolamines and, thus, needs can, according to [19], be expressed in the form
corrosion inhibitors at higher concentrations [14-17].
The objective of this study is to evaluate the protonation B
ln K a A C ln T DT ET 2 (11)
constant (pKa) of MEA at a range of temperatures from 303 to T
333 K using a potentiometric titration method. where T is the temperature in K, while A, B, C, D and E are the
coefficients that can be determined from the regression method
which gives the Sum of the Squared Errors (SSE) minimum.
2. THEORY The minimization of errors will produce linear systems
Carbon dioxide capture using amine-based absorption is mathematically expressed as
categorized as a chemical absorption process where mass 1
ln K a nA B C ln T D T E T2 (12)
transfer and chemical reaction occur simultaneously. A series of T
physical and chemical reaction equilibria for the CO2-amine- ln K a 1 1 ln T
H2O system can, according to [18], be written as follows: A B C D E T (13)
T T T2 T
CO2 g CO2 l (1) ln T 2
ln K a ln T A ln T B C ln T
+ T (14)
2H 2 O H 3 O + OH (2)
D T ln T E T 2 ln T
CO2 l + 2H2 O HCO3 + H3O+ (3)
T ln K a A T B C T ln T
HCO3 + H 2 O CO3= + H 3O + (4) 2 3
(15)
D T E T
AmH + + H 2 O Am + H 3O + (5)
T 2 ln K a A T2 B T C T 2 ln T
Am + CO2 l + H2 O AmCOO + H3O +
(6) (16)
D T3 E T4
+
HAmCOO + H 2 O AmCOO + H 3 O + (7) where n is the number of data. From (12) to (16), it is obtained
where g, l, and Am refer to gas, liquid, and amine molecule. a set of linear equations. Some method can be applied to solve
From (1) to (7), the chemical equilibrium constants as a the linear equation systems, e.g. the Gauss elimination method
function of the activity coefficients i and mole fraction xi can [20]. This solution method will be used in this work.
be formulated as follows
v v
Kj ai
ij
x
i i
ij
j 1, 2,...,R (8) 3. MATERIALS AND METHOD
i i
where vij is the stoichiometric coefficient for component i in A. Materials
reaction j and R is the number of chemical reactions. The materials used in this work consist of
The equilibrium constant in (5) is the protonation constant monoethanoalmine (MEA) obtained from Sigma-Aldrich with
(pKa) of amine in which its value can be experimentally purity of min. 98%, sulfuric acid (H2SO4) from Merck with
measured. purity of 96.0%, and distilled water. Moreover, MEA received
The protonation constant, also known as the acid from the manufacturer was directly used without further
dissociation constant, can be calculated from the reaction of a purification.
weak acid and a strong base where Ka value is equal to the B. Apparatus and Procedure
concentration of H+ ions in the solution. This occurs when the Figure 1 shows the experimental setup consisting of a 300-
total volume of titrant added is equal to half of the equivalence mL jacketed reactor, a pH meter (Lutron PH-201 with pH
volume (Ve) required. electrode PE-03 and accuracy up to 0.01), a TFA® digital
Let a weak acid HA react with a strong base BOH in thermometer with accuracy up to 0.1°C, a memmert water bath,
solution an OHAUS® digital balance with readability up to 0.0001 g, a
HA + BOH BA + H2 O (9) magnetic stirrer, and a 5-mL syringe.
in which the remaining weak acid HA and the salt formed BA A certain amount of MEA min. 98%, about 0.5 g, was
dissociate in the solution. Since HA is a weak acid with small added into a beaker glass containing about 50 mL of distilled
Ka value, the amount of HA in the solution is, therefore, water. The solution was then stirred some time to make it
assumed to be constant. The number of A ions in the solution homogeneous. A certain amount of titrant, i.e. 0.1 M H2SO4
are mostly from BA dissociation, i.e. A ions from HA solution, in a syringe was added into the beaker glass. The
dissociation is negligible. In this condition, the weak acid HA reaction taken place was exothermic, so that the solution
concentration in the solution is equal to the concentration of A temperature was slightly increase. It took some time until the
temperature and pH of the solution stable. The addition of 0.1
2
M H2SO4 from the syringe was repeated until the equivalence agree with the literature data, except at 333 K, where the ln K a
point is reached. When the titration was about the equivalence from this study is a bit lower compared to [26]. Even though
point, the titrant must be added with a very small amount to the vapor pressure of MEA at 333 K is very low (P o = 0.66 kPa
ensure that the pH did not change much, so that the equivalence [28]); the evaporation loss during titration might slightly reduce
point was not exceeded. the amount of MEA in the solution, thereby slightly affecting
the measurement result.
0
6

-1

-2
4 TI pH 5
-3

(pH)/(V)
-4
7 8
-5

-6

-7
1
-8
0 10 20 30 40 50 60 70 80 90 100
3 VH2SO4 0.1M, mL

Fig 2. Titration curve of MEA at 303K (Ve = the volume

2
of titrant at the equivalence point)

Fig 1. Experimental setup for pKa measurements (1:

jacketed reactor, 2: magnetic stirrer, 3: stirrer, 4: 12
thermometer, 5: pH meter, 6: syringe, 7: heating
medium inlet, 8: heating medium outlet) 10
pKa = pH
0.5Ve = 22.50 mL
8
4. RESULTS AND DISCUSSION
pH

The pKa measurements of MEA were conducted at a range 6

of temperatures from 303 to 333 K using the potentiometric
titration method with 0.1 M H2SO4 solution as the titrant. 4

As seen in Fig. 1, the titrant was discretely added. The Ve = 45.01 mL

2
amount of titrant added was calculated from the syringe weight
difference. The titration was terminated after the solution
0
reached pH about 2.0, i.e. excess H2SO4. This is to ensure that 0 10 20 30 40 50 60 70 80 90 100
all MEA molecules have reacted with H2SO4. VH2SO4 0.1M, mL
From the titration curve obtained, the pKa value can then be
Fig 3. Titration slope (pH/V) of MEA at 303K
determined graphically. Figure 2 shows the titration curve for
Run 1 in which the equivalence point was reached when the
titrant volume (Ve) added was about 45 mL. It was quite 0
challenging to determine the precise equivalence point directly
-1
from the curve. Another step is therefore required, i.e.
determination of pH slope (pH/V) for every single point, as -2
seen in Fig. 3. The equivalence point is reached when the slope
-3
(pH/V) gives minimum value. However, the precise
(pH)/(V)

equivalence point cannot still be read from the figure; therefore -4

enlarging the figure scale around the equivalence point is -5
required. It can be seen from Fig. 4 that the equivalence volume
(Ve) for Run 1 is 45.006 mL. -6

Furthermore, the pKa value occurs when the titrant volume -7

equals half of the equivalence volume. At this point, pKa is -8
equal to pH. It can be seen from Fig. 2 that pK a is 9.41. Similar 44.97 44.98 44.99 45.00 45.01 45.02 45.03
procedure was applied to the other data and the results are then VH2SO4 0,1M, mL
summarized in Table 1.
Fig 4. Titration slope (pH/V) around the equivalence
The pKa values of MEA obtained from this work are then
point at 303K
compared to those from the literatures as given di Table 2 and
Fig. 5. It can be seen from Fig. 5 that the results, in general,

3
 TABLE 1. pKa VALUES AT DIFFERENT linear regression method, the protonation constant Ka can then
TEMPERATURE be correlated as a function of temperature in an empirical
Run T, K Number of data pKa pKa-avg equation form as follows:
1 303 79 9.41 9.43 4.36 10 4
ln K a 164.40 25.50ln T
2 303 85 9.44 T (17)
1.37 10 8 T 3.11 10 5 T 2
3 313 76 9.18 9.14
4 313 86 9.10 Equation (17) could be useful to determine the protonation
constant with its temperature dependency for future work.
5 323 89 8.88 8.90
6 323 82 8.91
5. CONCLUSION
7 333 87 8.68 8.67
The protonation constant (pKa) measurements of MEA were
8 333 85 8.66
conducted at a range of temperatures from 303 to 330 K by a
potentiometric titration method to complement the existing data
TABLE 2. COMPARISON OF EXPERIMENTAL DATA in the literature. The experimental pKa data obtained in this
WITH LITERATURE work, in general, agree well with the results published in the
literature. The pKa data from this work together with those from
-ln Ka
T, the literature were then correlated in an empirical form to easily
[21] [22] [23] [24] [25] [26] [27] This
K be used for future research.
work

273 23.73
ACKNOWLEDGMENT
278 23.33
The authors acknowledge the Islamic University of
283 22.95 Indonesia for the financial support through the Department of
288 22.57 22.57 22.25 Chemical Engineering Research Grant 2016.
293 22.21 22.08

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