Separation and Purication Technology 75 (2010) 17

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Separation and Purication Technology

journal homepage: www.elsevier.com/locate/seppur

Kinetics of reactive absorption of carbon dioxide with solutions of

1,6-hexamethylenediamine in polar protic solvents
Srikanta Dinda 1 , Vaibhav V. Goud , Anand V. Patwardhan 2 , Narayan C. Pradhan
Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721302, India

a r t i c l e

i n f o

Article history:
Received 27 January 2010
Received in revised form 1 July 2010
Accepted 2 July 2010
Keywords:
Kinetics
Reactive absorption
Carbon dioxide
HMDA
Methanol

a b s t r a c t
Reactive absorption of carbon dioxide with solutions of 1,6-hexamethylenediamine (HMDA) in methanol
and water was studied in stirred cell and model stirred contactor at 303 1 K. The volumetric rate of
absorption of pure CO2 , at atmospheric pressure, was measured using a soap-lm meter of appropriate
size. Carbon dioxide partial pressure was varied from 0.41 to 0.96 atm and concentration of liquid phase
reactant HMDA was varied from 0.5 to 3.0 kmol m3 . The specic absorption rates were analysed using
mass transfer with chemical reaction theory. The reaction order was found to be 0.85 with respect to CO2
and HMDA each in water as solvent. The intrinsic kinetic rate constants (km,n ) at 303 1 K were found to be
in the range of (1.11.5) 102 (kmol m3 )0.7 s1 . In the case methanol as solvent, the reaction appeared
to be the instantaneous reaction regime. These data are expected to be useful for the design and scale up
of carbon dioxide absorbers in the process development for carbamates/isocyanates synthesis.
2010 Elsevier B.V. All rights reserved.

1. Introduction
The reactive absorption of carbon dioxide (CO2 ) with 1,6hexamethylenediamine (HMDA) dissolved in methanol and water
was studied. Industrially, aqueous solutions of alkanolamines and
various types of amine blends are widely used in gas purication
processes for the absorption of acid gases such as CO2 , hydrogen
sulde, and carbonyl sulphide, etc. [1,2]. Particularly, the removal
of CO2 from the gas produced by burning fossil fuel has been of great
interest owing to the global warming caused by the increase in the
concentration of CO2 in the atmosphere. Recently, the potential of
CO2 as a source of carbonyl (in place of phosgene) in the synthesis of high value industrial chemicals and intermediates, such as
carbamates, isocyanates, and urethanes is being evaluated extensively. The traditional manufacturing route for organic isocyanates
is by reaction of an amine with phosgene (COCl2 ), the intermediate of this reaction is converted to the corresponding isocyanate
in the presence of a nonaqueous aprotic solvent [38]. There is a
large number of recent publications [921] in which phosgene have
been replaced by a benign substitute. Use of carbon dioxide as a
reagent in place of phosgene has the potential for cheaper, greener,

Corresponding author. Present address: Department of Chemical Engineering, Indian Institute of Technology, Guwahati 781039, Assam, India Tel.: +91 361
2582272; fax: +91 361 2582291.
E-mail address: vvgoud15@yahoo.com (V.V. Goud).
1
Present address: Reliance Industries Limited, Jamnagar 361142, India.
2
Present address: Department of Chemical Engineering, Institute of Chemical
Technology, Nathalal Parekh Marg, Matunga (East), Mumbai 400019, India.
1383-5866/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2010.07.002

inherently safer, and more selective route to produce carbamates,

isocyanates, and polyurethanes. However, the commercial utilisation of the process requires systematic kinetic study. In addition,
the information available in the literature on the kinetics of reactive absorption of CO2 with solution of diamines in polar solvents
is not very comprehensive. It is, however, apparent that these reactions are fast and mass transfer may be accompanied by chemical
reaction in the diffusion lm. It was, therefore, thought desirable
to study the kinetics of reactive absorption of CO2 with solutions of
HMDA in methanol and water.
1.1. Previous studies
Recently, Aresta et al. [3] have reported the kinetics and mechanism of the homogeneous reaction of some organic amines
with dimethyl carbonate (DMC) in the presence of dissolved CO2 .
Second-order kinetics was used in the analysis. Caplow [22] has
studied the homogeneous uncatalysed and hydroxide-catalysed
reactions of some secondary amines with CO2 . Second-order kinetics was observed. Crooks and Donnellan [23,24] have reported
the formation of N,N-dialkylcarbamate from diethanolamine
and CO2 in anhydrous ethanol. The rate of formation of N,Ndialkylcarbamate from diethanolamine and CO2 in anhydrous
ethanol was found to depend on the square of the amine concentration. The rate and activation data are consistent with the
Danckwerts mechanism [25,26] in which a zwitterion intermediate is present at very low concentration and reacts with a second
molecule of amine at the diffusion-controlled limit to give a nal
salt in the rate-determining step. Ali et al. [27] have reported the

S. Dinda et al. / Separation and Purication Technology 75 (2010) 17

Nomenclature
A
AR
aB
cAo
cAi
cBo
cBi
DA
DB
fhyp. liq 2
fgas 2
km
km,n
kL
l
m, n
pA
R
RA
T

v2
x2
z

solute gas component (CO2 )

analytical reagent
surface area per unit volume (m1 )
liquid phase reactant (HMDA)
concentration of A in bulk liquid phase (kmol m3 )
concentration of A at gasliquid interface
(kmol m3 )
bulk concentration of B in liquid phase (kmol m3 )
concentration of B at gasliquid interface
(kmol m3 )
diffusivity of A in liquid phase (m2 s1 )
diffusivity of B in liquid phase (m2 s1 )
fugacity of hypothetical liquid 2, for Eq. (1) (kPa )
fugacity of gas 2, for Eq. (1) (kPa )
pseudo m-order rate constant, km = km,n cBo n or
km = km,n cBi n
intrinsic kinetic rate constants dened in Eq. (3)
((kmol m3 )1(m+n) s1 )
physical liquid side mass transfer coefcient of the
solute gas (m s1 )
liquid hold-up
order with respect to solute gas A and liquid-phase
reactant B, respectively
partial pressure of A in gas phase (atm)
universal gas constant
specic absorption rate of solute gas (kmol m2 s1 )
temperature (K)
molar liquid volume of the solute (m3 kmol1 )
mole fraction of the solute gas in the liquid phase
stoichiometric factor for chemical reaction
expressed by Eq. (3)

Alvarez-Fuster et al. [29] and Sada et al. [30]. Alvarez-Fuster et al.

[29] found that the reaction order with respect to cyclohexylamine
in ethanediol to be 1. Sada et al. [30] studied the heterogeneous kinetics of reactive absorption of CO2 with mono- and
diethanolamine in solvents such as methanol, ethanol, 2-propanol,
and water, using a stirred tank absorber with a plane gasliquid
interface at 303 K. The reaction was found to be rst order with
respect to CO2 for every solvent. The order of reaction with respect
to ethanolamine was found to be 1 only for an aqueous solution of
monoethanolamine; for the other solutions, the order ranged from
1.4 to 2, depending on the solvent species. Very recently, Dinda et
al. [31] have studied the kinetics of reactive absorption of CO2 with
solutions of aniline in nonaqueous aprotic solvents, namely, acetonitrile, methyl ethyl ketone, toluene, and m-xylene. The reaction
was found to be rst order with respect to CO2 for all the solvents
studied. The order of reaction with respect to HMDA was found to
be 0.5 in acetonitrile, 1 in methyl ethyl ketone, 2 in toluene, and
2.5 in m-xylene.
From the foregoing discussion, it is clear that very limited data
are available on the kinetics of reactive absorption of CO2 with
solutions of simple aliphatic diamines in aqueous or nonaqueous
solvents. These data will be essential for the potential utilisation of
CO2 in the commercial production of many commercially important carbamates/isocyantes. This work was, therefore, undertaken
to study the kinetics of reactive absorption of CO2 with solutions
of HMDA (as a model aliphatic diamine) in methanol and water.
It is expected that the data obtained for HMDA will be useful for
many more commercially important aromatic and aliphatic monoand di-amines, which are used in the industrial manufacture of
carbamates and isocyanates.
2. Experimental details and materials
2.1. Stirred cell

Greek symbols
1 , 2
Hildebrand solubility parameter of solvent and
solute gas respectively (MPa1/2 )

relative dielectric constant of solvent


viscosity of the components (kg m1 s1 )
1
volume fraction of the solvent

homogeneous kinetics of reaction of some primary amines with

CO2 in ethanol solution, using the stopped ow technique. The
highest conversion to carbamate ion was detected with hexamine.
The results favour the zwitterion intermediate mechanism proposed by Danckwerts [25,26]. The reaction order was found to
increase (ranging from 1 to 2) with the basicity of the amine. Very
recently, Masuda et al. [28] have studied the solvent dependence of
the carbamic acid formation from -(1-naphthyl) alkyl-amines and
dissolved CO2 , in a variety of solvents such as dimethyl sulphoxide
(DMSO), dimethyl formamide (DMF), pyridine, dioxane, acetonitrile, benzene, water, 2-propanol, methanol, and water. Bubbling
of CO2 through solutions of naphthyl alkyl amines in DMSO, DMF
or pyridine (protophilic, highly dipolar, aprotic solvent) resulted
in complete conversion of the amines to the corresponding carbamic acids. In dioxane (protophilic, dipolar, aprotic solvent), the
carbamic acid and a small amount of the ammonium carbamates
were formed. By contrast, in (protophobic, dipolar, aprotic solvent),
in benzene or water (polar, aprotic solvent), or in 2-propanol or
methanol (dipolar, amphiprotic solvent), ammonium carbamates
were formed, although the ammonium bicarbonates/carbonates
were competitively formed in methanol.
Most of the reactive absorptions of CO2 studies have been
conducted in aqueous media except in recent research work by

Pure CO2 was stored in a balloon at atmospheric pressure. Experiments were carried out in a 64 mm, i.d. glass stirred cell. The design
of the stirred cell was similar to that used by Patwardhan and
Sharma [32]. A glass stirrer with four blades, which was set just
into the liquid, was used. The gas phase in the stirred cell was also
agitated using a cruciform stirrer. The stirrer speed was varied from
45 to 102 rev/min. The effective interfacial area was 31.2 104 m2 .
A known amount of a solution was taken, and the volumetric rate
of absorption of pure CO2 , stored in a balloon at essentially atmospheric pressure, was noted, using a soap-lm meter of appropriate
size. Prior to the measurement of the volumetric rate of absorption,
the stirred cell was purged with pure CO2 for a sufcient time. The
purging was stopped, and the unit was connected to a balloon containing pure CO2 at essentially atmospheric pressure. After about
100 s, the volumetric rate of uptake of CO2 was noted.
2.2. Stirred contactor with a at gasliquid interface
This type of contactor, which has independent stirrers for gas
and liquid phases and where the interface is kept at and no gas
dispersion is allowed, was employed to study the effect of CO2 partial pressure on the specic rate of CO2 absorption with HMDA
solutions in different solvents. The design features of this contactor
were akin to those employed by Patwardhan and Sharma [32], and
Yadav and Sharma [33]. This model stirred contactor was operated
at a gas-side stirrer speed of about 1200 rev/min and liquid-side
stirrer speed of 110 rev/min. The mode of operation of contactor
was semicontinuous. Experiments were conducted at 303 1 K and
essentially at atmospheric pressure by employing mixtures of CO2
and nitrogen. The specic rates of absorption were calculated on

S. Dinda et al. / Separation and Purication Technology 75 (2010) 17

Fig. 1. Variation in predicted solubility of CO2 in HMDA solutions of methanol and

water at 303 K.

the basis of chemical analysis of carbamate formed in the liquid

phase.
2.3. Materials
HMDA was procured from Alfa Aesar (Lancaster). Synthesis
grade methanol was obtained from Merck Limited. CO2 cylinder
containing AR grade CO2 was obtained from BOC (Special Gases)
Limited, Mumbai. Nitrogen gas cylinder was obtained from a reputable rm.
3. Physicochemical data


exp

3.3. Physical mass transfer coefcient

Values of the physical mass transfer coefcient, kL , are needed to
check the conditions for different controlling regimes [37,38] and
to predict the reaction rate parameters. The kL values at different
speeds of stirring in the stirred cell were determined by absorbing
pure CO2 in deionised water. The kL values at different speeds of
stirring in the model stirred contactor were obtained from earlier
work by Yadav [33] conducted on a model stirred contactor with
identical conguration. The values of kL of HMDA solutions were
estimated from Eq. (2):

v2 (1 2 )2 12

RT

water /solution

(2)

4. Theory

The equilibrium mole fraction (x2 ) of CO2 in pure methanol

and water was determined experimentally by measuring the dissolved CO2 concentration in CO2 -saturated solutions of methanol
and water at 303 1 K. The experimentally measured values for
methanol and water compared well with those reported in the literature [34,35]. From that measured equilibrium mole fraction value,
we predicted the solubility parameter for pure methanol and water
using regular solution theory [36], using Eq. (1):
fhyp,liq2
1
=
x2
fgas2

Fig. 2. Variation in predicted diffusivity of CO2 in HMDA solutions of methanol and

water at 303 K.

kL,solution = kL,water

3.1. Solubility of CO2 in solutions of HMDA in methanol and water

The following chemical reaction was considered for the analysis

of experimental results:
km,n

A(dissolved gas) + zB(liquid-phase reactant) product

(3)

The theory of mass transfer accompanied by irreversible and

reversible reactions of general order, and the methods of discerning the controlling mechanism has been discussed in detail by
Doraiswamy and Sharma [37]. Please see the Appendix A for rele-

(1)

The equilibrium mole fraction (x2 ) of CO2 in the mixtures of HMDA

in methanol and water was predicted using Eq. (1). The CO2 solubility (cAi ) values for the mixtures of HMDA in methanol and water
were calculated from predicted mole fraction solubility value and
are shown in Fig. 1. As the concentration of HMDA increases the
solubility of CO2 decreases in both the solvents.
3.2. Diffusivity of CO2 in solutions of HMDA in methanol and
water
The values of diffusivity of CO2 in methanol, water and in the
mixtures of HMDA in methanol and water were predicted using
the Wilke-Chang correlation. Please refer to Fig. 2. The diffusivity of CO2 decreases with HMDA concentration due to an increase
of viscosity. The variation of estimated combined physicochemi1/2
cal property (cAi DA ) of CO2 in the liquid medium with different
HMDA concentrations is shown in Fig. 3.

1/2

1/2

Fig. 3. Estimated variation of cAi DA / cAi DA

methanol and water at 303 K.


cBo =0

with HMDA concentration in

S. Dinda et al. / Separation and Purication Technology 75 (2010) 17

vant equations. When the rate of reaction between the dissolved A

and B is very much slower, than the rate of transfer of A into the B
phase then the chemical absorption process lies within a very slow
reaction regime and the absorption rate of A is given by Eq. (A1). The
condition to be satised for the very slow reaction regime is given
by Eq. (A2). For slow reaction regime, the rate of reaction between A
and B is faster than the rate at which A is transferred to the B phase
and the rate is controlled by the transfer of A into the B phase.
When the concentration of dissolved A in the bulk B phase is negligible, then the specic reaction rate can be given by Eq. (A3). The
conditions to be satised for the slow reaction regime, if the bulk
concentration of A in liquid phase is negligible, are given by Eqs.
(A4) and (A5). When the diffusion of A and the reaction between
dissolved gas A and reactant B occurs simultaneously and if the A
is entirely consumed by B within the lm, then the absorption process belongs to the fast-reaction regime and the absorption rate can
be given by Eq. (A6) and the conditions to be satised is given by
Eq. (A7). When the reaction between solute A and reactant B is so
fast that the solute gas and the reactant B cannot coexist, then the
absorption process belongs to instantaneous reaction regime and
at a certain distance from the interface, a reaction plane is formed.
The rate of mass transfer in this case will be governed by the rate at
which dissolved gas and the liquid reactant are supplied to the reaction plane. The rate expression for instantaneous reaction regime
is given by Eq. (A8). The condition to be satised for instantaneous
reaction regime is given by Eq. (A9).
5. Results and discussion
Most of the experiments were conducted in the stirred cell.
However, the solubility of CO2 in solutions of HMDA in both the
solvents used is not very small (1.06 101 kmol m3 in pure
methanol, 2.96 102 kmol m3 in water); hence, it is expected
that the gas-side resistance may be present when CO2 is absorbed
from mixtures of CO2 and nitrogen. Therefore, to nd out the order
of reaction with respect to CO2 , some experiments were conducted
in the model stirred contactor as well, wherein the gas-side resistance was eliminated by stirring the gas-phase independently at
a very high stirring speed of about 1200 rev/min. In the present
study, CO2 mole percentage in the mixture of N2 and CO2 was tried
to keep at least above 50% to neglect the gas phase mass transfer resistant at a stirring speed of 1200 rev/min. However, with a
lower mole percentage of CO2 , the gas-side resistance can also be
eliminated at a very high stirring speed. The major problem associated with high stirring speed is uctuation of at liquid surface.
For amine-methanol system (which belongs to the instantaneous
reaction regime), kinetics is practically independent on CO2 partial pressure and if gas-phase resistance is properly eliminated
then kinetics will not be change even if the CO2 partial pressure
is varied from of 0.20.96 atm instead of 0.420.96 atm. Therefore,
to eliminate the gas-phase resistance and to avoid the uctuation
of gasliquid at interface at a high stirring speed, CO2 pressure
was varied from 0.42 to 0.96 atm keeping the total pressure of one
atmosphere.

Fig. 4. Variation of specic absorption rate of CO2 with partial pressure of CO2 at
1.50 kmol m3 HMDA concentration, in methanol and water, at 303 1 K (liquid
phase stirring speed = 110 rev/min, stirred contactor).

The variation of the specic absorption rate of pure CO2 with

stirring speed in the stirred cell, under atmospheric pressure and
at 303 1 K, in different concentration of methanolic HMDA solutions are shown in Fig. 5. The concentration of HMDA solutions was
varied from 0.5 to 3.0 M. The specic rate was found to be dependent on the hydrodynamic factors in the range of stirring speed
from 45 to 102 rev/min, for the studied HMDA concentrations.
In Table 1, it can be seen that the specic absorption rate at
303 K increased as the concentration of HMDA increased from 0.5
to 3.0 M at a constant stirring speed of 102 rev/min but the rate
of increment is not linear. This is due to the reduction of solubility of CO2 , and reduction of diffusivity of dissolved gas with the
increase of HMDA concentrations. To nd out the controlling mechanism and the regime of reaction, we have calculated the values of
RA /(kL cAi ) and (cBo /z.cAi )(DB /DA )0.5 . These values are tabulated in
Table 1. From the foregoing analysis, when HMDA concentration is
less than/equal to 2.5 M, the reactive absorption of CO2 in methanolic HMDA appears to be an instantaneous reaction regime, where
the reaction between dissolved CO2 and HMDA is potentially so fast
that the solute gas and the reactant cannot coexist. At a certain distance from the interface, a reaction plane is formed. The rate of mass
transfer in this case will be governed by the rate at which dissolved
gas and the liquid reactant are supplied to the reaction plane. However, at higher HMDA concentrations, the reaction shifted towards
the intermediate between fast and instantaneous reaction regime.

5.1. Absorption of CO2 with solution of HMDA in methanol

The inuence of CO2 partial pressure on the specic rate of
absorption was investigated at constant HMDA concentration of
1.5 kmol m3 in the model stirred contactor, where the partial pressure of CO2 was varied from 0.41 to 0.81 atm at the gasliquid
interface at 303 K (Fig. 4). It was found in Fig. 4 that m, namely
the order of reaction with respect to solute gas A (CO2 ), is 0.1,
which means the specic rate of absorption is almost independent
on partial pressure of solute gas A (CO2 ).

Fig. 5. Variation of specic absorption rate of CO2 with stirring speed at different
HMDA concentrations in methanol (stirred cell) at 303 1 K.

S. Dinda et al. / Separation and Purication Technology 75 (2010) 17

Table 1
Calculated values of {RA /(kL .cAi )} and {(cBo DB0.5 )/(zcAi DA0.5 )} for the absorption of CO2 with HMDA dissolved in methanol at 303 K.
Contactor

Stirring speed (rev/min)

pA a (atm)

cBo (kmol m3 )

RA 106 (kmol m2 s1 )

RA /(kL cAi )

Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred contactor
Stirred contactor
Stirred contactor
Stirred contactor

102
102
102
102
102
102
110
110
110
110

0.80
0.81
0.81
0.82
0.83
0.83
0.81
0.66
0.512
0.412

0.5
1.0
1.5
2.0
2.5
3.0
1.5
1.5
1.5
1.5

32.2
36.4
39.3
41.5
43.1
44.3
35.1
34.4
33.5
32.7

9.17
14.4
20.2
26.5
33.9
41.2
22.6
27.2
34.25
41.57

cBo D0.5
B

zcAi D0.5
A

3.49
8.27
14.3
21.6
30.3
40.1
14.3
17.5
22.66
28.18

values are corrected for the vapour pressure of methanol.

Table 2
Calculated values of {RA /(kL cAi )} and {(cBo DB0.5 )/(zcAi DA0.5 )} for the absorption of CO2 with HMDA dissolved in water at 303 K.
Contactor

Stirring speed (rev/min)

pA a (atm)

cBo (kmol m3 )

RA 106 (kmol m2 s1 )

RA /(kL cAi )

Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred contactor
Stirred contactor
Stirred contactor
Stirred contactor

102
102
102
102
102
102
110
110
110
110

0.96
0.96
0.96
0.96
0.96
0.96
0.96
0.81
0.66
0.56

0.5
1.0
1.5
2.0
2.5
3.0
1.5
1.5
1.5
1.5

6.90
8.76
9.77
10.4
10.9
11.2
9.29
8.17
6.79
5.90

7.85
12.9
17.4
21.7
25.6
29.0
20.7
21.6
22.0
22.6

cBo D0.5
B

zcAi D0.5
A

11.9
26.0
41.0
56.3
71.3
85.7
41.0
48.6
59.7
70.4

values are corrected for the vapour pressure of water.

5.2. Absorption of CO2 with solution of HMDA in water

The specic rate of absorption in the model stirred contactor was
found to be proportional to the partial pressure of CO2 , which was
varied from 0.56 to 0.96 atm, at the gasliquid interface at constant
HMDA concentration of 1.5 kmol m3 at 303 K (Fig. 4). It was found
from this graph that m, namely the order of reaction with respect
to solute gas A (CO2 ), is 0.85.
Fig. 6 shows the variation of the specic absorption rate of pure
CO2 with stirring speed, in the stirred cell at 303 K with different
concentration of HMDA solutions. The specic rate appeared to be
dependent on the hydrodynamic factors in the range of stirring
speeds from 45 to 102 rev/min, for the studied HMDA concentration
range. However, for higher HMDA concentration the specic rate
was less dependent on the hydrodynamic factors.

The specic rate of absorption of CO2 at 303 K in aqueous

solution of HMDA in stirred cell at a constant stirring speed of
102 rev/min is tabulated in Table 2. It can be seen that the RA
increases with the increase of HMDA concentration but the increment is very small at high concentration of HMDA. This is due to
the reduction of solubility of CO2 , and reduction of diffusivity of
dissolved gas with the increase of HMDA concentrations.
To nd out the regime of reaction, we have calculated the value
of RA /(kL cAi ) and (cBo /z.cAi )(DB /DA )0.5 . The values are tabulated in
Table 2. From the foregoing analysis, the absorption of CO2 with
HMDA dissolved in water, therefore, appears to conform to the
intermediate regime between very fast and fast reactions regime,
where the concentration of B (HMDA) in the liquid lm will be
substantially lower than that in the bulk.
Here again, instead of plotting ln(RA ) versus ln(cBi ), we have
plotted ln(km ) (km was obtained considering intermediate regime
between instantaneous and fast reactions regime) versus ln(cBi ) in
Fig. 7, owing to our observation that both cAi and liquid viscosity
(and hence DA ) changes with a change in cBi . It was found from this
graph that n, namely the order of reaction with respect to liquid
phase reactant B (HMDA), is 0.85. Table 3 gives the pertinent details.
The average value of the intrinsic kinetic rate constant (k0.85,0.85 ), at
303 1 K, was estimated at 1.38 102 (kmol m3 )0.7 s1 in stirred
cell.

5.3. Effect of solvent on reaction regime

Fig. 6. Variation of specic absorption rate of CO2 with stirring speed at different
HMDA concentrations in water (stirred cell) 303 1 K.

The regime of reaction and the reaction kinetics of an organic

reaction in a solvent generally reect the solvent effects. For observing the effect of solvent on the reaction regime and reaction rate
constants, various physical properties such as Hildebrand solubility parameter 1 and the relative dielectric constant of the solvent
has been proposed [31]. The Hildebrand solubility parameter is the
total van der Waals force, and is a numerical value that indicates the
relative solvency behavior of a specic solvent. It is derived from the

S. Dinda et al. / Separation and Purication Technology 75 (2010) 17

Table 3
Absorption of CO2 with HMDA dissolved in water at 303 1 K.
Contactor

cBo (kmol m3 )

pA a (atm)

cBi (kmol m3 )

K0.85,0.85 102 ((kmol m3 )0.7 s1 )

Remarks

Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred cell
Stirred contactor
Stirred contactor
Stirred contactor
Stirred contactor

0.5
1.0
1.5
2.0
2.5
3.0
1.5
1.5
1.5
1.5

0.96
0.96
0.96
0.96
0.96
0.96
0.96
0.81
0.66
0.56

0.23
0.55
0.91
1.27
1.65
2.03
0.79
0.87
0.98
1.05

1.43
1.33
1.35
1.40
1.41
1.40
1.50
1.39
1.16
1.10

Between instantaneous and fast reaction regime

Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime
Between instantaneous and fast reaction regime

Values are corrected for the vapour pressure of water.

water respectively. The reaction order with respect to HMDA was

found to be 0.85 in the case of water, as solvents. The average
intrinsic kinetic rate constant (km,n ) at 303 1 K was found to be
1.38 102 (kmol m3 )0.7 s1 for amine water system in stirred
cell. These ndings will have a direct bearing on the design
and scale up of absorber in the process development for carbamates/isocyanates. In addition, there appears to be a correlation
between the intrinsic kinetic rate constant and the polarity of the
solvent employed.
Acknowledgement
Srikanta Dinda (Institute Research Fellow) gratefully acknowledges the award of Senior Research Fellowship granted to him by
the Indian Institute of Technology Kharagpur.
Appendix A.
Fig. 7. Variation of ln km with
speed = 102 rev/min, stirred cell).

ln(cBi )

in

water,

at

303 1 K

(stirring

RA a = lkm,n (cAi )m (cBo )n

(A1)

kL (cAi )  lkm,n (cAi ) (cBo )

Table 4
Values of solubility parameters, relative dielectric constants, for methanol and
water.
Properties

Methanol

Water

1 , at 298 K, MPa1/2
, at 298 K
Reaction regime

29.7
33.0
Reaction belongs to
instantaneous reaction
regime

48.0
88.0
Reaction belongs to
fast reaction regime

cohesive energy density of the solvent. In the present study, it can

be seen in Table 4, as the solubility parameter 1 and the relative
dielectric constant of the solvent increases the reaction regime
is shifted towards the fast reaction regime from the instantaneous
reaction regime.

RA = kL (cAi )

(A3)

kL (cAi )  lkm,n (cAi ) (cBo )

(A4)

(2/m + 1)DA km,n (cAi )m1 (cBo )

kL

RA =

 2
m+1

3 < M 1/2 

DA km (cAi )m+1
cBo
zcAi

RA = kL cAi 1 +
M 1/2 >>

6. Conclusions
The absorption of CO2 with solutions of HMDA in methanol,
within the HMDA concentration range between 0.5 and
3.0 kmol m3 , was found to conform to the instantaneous reactions
regime, where the reaction between dissolved CO2 and HMDA
is potentially so fast that the solute gas and the reactant cannot
coexist. At a certain distance from the interface, a reaction plane
is formed. The absorption of CO2 with solutions of HMDA in
water, was found to conform to the intermediate regime between
instantaneous and fast reactions regime, where the concentration
of B (HMDA) in the liquid lm will be substantially lower than
that in the bulk. The reaction was found to be almost zero order
and of the order of 0.85 with respect to CO2 in methanol and

(A2)

cBo
zcAi

D
1/2
B

DA

cBo DB
.
z.cAi DA
B

= M 1/2  1

(A5)

1/2
(A6)

(A7)

D
1/2
DA


n 1/2

(A8)

(A9)

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