THE

REACTION

OF CO, WITH

ETHANOLAMINES

P V DANCKWERTS
Department of Chemical Engmeermg, Pembroke St, CambrIdge CB2 3RA, England
(Accepted

14 November 1978)

Abstract-Measurements
of the rates of homogeneous reactlon of mono-, dl- and tn-ethanolamme
by various
workers are cntmslly compared Some dlscrepancles remam unexplamed but It seems probable that a zwltterlon IS
the mtermedlate
bases

m the formatlon

of carbamate

and that the reactlon

The absorption of CO, by solutions of alkanolammes

IS
an operation
of such mdustrlal
Importance
that the
kmetlcs of the reactions between CO, and these ammes
are of considerable
interest
I shaIl confine myself to
aqueous
solutions
of monoethanolamme
(MEA)
and
dlethanolamme
(DEA), with a glance at trlethanolamme
(TEA), although other ethanolammes
and other solvents
are sometimes
used Only the forward reaction ~111 be
considered
here, although the reverse reactlon IS equally
important
In the recent chemical
engtneermg
literature It has
been usual to write the reaction as
COz + RzNH + RzNCOOH
R2NCOOH

+ RzNH + RzNCOO-

of DEA (but not of MEA) LScatalysed

by

remam m solution
The reaction and analysis have to be
performed qmckly because the carbamate IS SubJect to
hydrolysis
This IS more marked m the case of DEA, and
a calculated correction had to be apphed with consequent
doubts as to their accuracy
Depletion of the reagents by
preferential
reaction near the Interface was probably
negligible
and had been the subJect
of some
mvestlgatlons
by Jensen
et al [4] The mltlal concentrations of amme and NaOH. the amount of CO2 absorbed (mol/l) and the percentage of the CO2 absorbed
which was not precipitated
as carbonate were recorded
The rate of formation of carbamate was assumed to be
L[COt]
[Am1 and km was calculated from

(1)
+ RzNHz+

% non-carbonate
% carbonate

(2)

the first

step being bimolecular,

second-order
and rate
determining, while the second step was supposed to take
place mstantaneously
The carbamlc acrd can be regarded as fairly strong, with pK, (7,
and the zwitterion

R&HCOOIS msufficlently
stable to be formed In appreciable concentration,
these supposltlons
are borne out
tn the case of (H2NCOO- + NH4)
by the electrical
conductrvlty measurements
of Faurholt [ 11 which showed
that the equivalent conductlvlty
of ammomum carbamate
1s not much less than that of ammomum chloride
However, recent rapid-mixing mvestlgatlons
by Hlklta
et al [2] show that while the reaction of CO, with MEA
1s first-order,
that with DEA IS second-order
m the
concentration
of amine (m the amme concentration
ranges 0 0152-O 177 and 0 174-O 719 M respectively,
between temperatures
of about 6C and 40C)
Reference
to earlier pubhcatlons
shows
that the
kmetlcs
of the reactions
between
CO1 and ammes m
general and MEA and DEA tn particular are more complicated than had prevrously been assumed by chemical
engineers
The results to be consldered are
(a) Jensen et al [3]-MEA
and DEA The rates were
determined by the competltrve
method, 10% CO* in air
was bubbled through solutions
contaming
amtne and
NaOH (each at 0 1 and 0 2 M) at 18C The soluttons
were then analysed by adding BaC12 and filtering-off the
barium carbonate preclpltated,
the carbamate (and any
aIkyl carbonate formed from the hydroxyl groups of the
ammes-assumed
m [3] to be of neghglble
amount)

The

results

have

k,[Am]

(3)

k&OH-1

been recalculated
et al [5]

using the value

of

kOH given by Pmsent

log,okoH = 13 65 - 2895/T

(4)

(TK) and the mean values of the concentrations

of
amine and OH- between the begmnmg and end of the
reaction calculated by means of the stolchlometnc
relations
CO1 + Am + OH-+
CO_r+ 20H-

AmCOO-

+ Hz0

+ CO1- + Hz0

(5)
(6)

The resultmg value of k,, for MEA at 18C 1s 4065 -+ 5%

l/mols (based on 3 experiments
with [OH-] and [MEA]
both uutlally at 0 1 and 0 2 M), compared
with 3934
interpolated from the results of Hlkita et al [2] There 15
possibly a slight dependence
of k,, on [OH-], but doubling the latter only Increased the former by 7-8% The
results for DEA were discarded
in favour of those
below
(b) JargensonE6]-DEA
Slmdar experiments
at OC,
carried out more rapidly, thus reducing the error due to
hydrolysis
The concentrations
of amine and OH- were
permutated
at the levels 0 1. 0 2 and 0 3 M Jtirgenson
Interpreted the results as follows
(I) a second-order
reaction of CO, with DEA to form
carbamate ,
443

444

(II) a reactlon

DANCKWERTS

fitted the kmetlcs

system

C-OH+OH-=C-O-+HzO

(7)

C-0-+COt-+C-OCO*-

(8)

where (8) 1s the rate-determmmg

step Thus (If the fractlon of the -OH groups lomsed were small) the rate of
formation of alkyl carbonate
would be proportional
to
[C021[DEAI[OH-I,
giving
% non-carbonate
% carbonate

= [Am](ao + a,[OH-])

kcw[OH-1

(9)

at the results mdlcates the presence

of a second-order
term m [DEA]
Lmear regresslon
analysis along the lmes of (9) gives a fit with a coefficient
of confirmation
0 86, mcluston of a term a2[DEA] gives
However,

a glance

R = [C02][DEA](692

+ 3380[OH-]

+ 1056[DEA])
(10)

with a coefficient

of confirmation
0 93 (R bemg the rate
of reaction of amme, mol/l s)
Jergensen
also carried out a set of experiments
m
which
CO* reacted
with NaOH
solutions
contammg
dlethylamme
(which forms no alkyl carbonate),
TEA
(which forms no carbamate) and a mixture of NaOH and
the two ammes
The % non-carbonate
observed m the
last experiment
did not agree well with that predicted
from the results of the first two, no doubt because of a
mlsmterpretatlon
of the kmetlcs as suggested above
Companng
(10) with an extrapolation
of Hlkltas
results (m which the concentration
of OH- formed by
the hydrolysis of DEA was small enough for the second
term m (10) to be Ignored) to WC by
log,dR/[C02][DEA])

= I2 41-2775/T

(11)

we find R/[CO-rl[Amls-
[DEA] = 0 174 M Hlklta
(10)

[DEAI = 0 7 19 M Hiklta
(10)
There IS a gross discrepancy
from leadmg to values which

31
876

to the expresslon

R/[C021[Aml

= a~ + 01 [OHI

(12)

The reactlon

was defimtely catalysed by OH- but he was

unable to determine
whether or not there was a third
term, a2[Am], mdlcatmg catalysis by the amme He con-

sidered the mechmsm to be the formation of a zwltterlon

followed by the removal of a proton by a base B
COz + RzNH 2*_1

R&HC02-

+ BLB-

R&HCOz-

(13)

R2NC02- + BH

(14)

The base may be

the second step being rate-determmmg
water (+H20),
leading to the term a0 or OH- (+H20),
leading to the term aI One might expect a third term
a*[Am] correspondmg
to specdic catalysis by the amme
(+ AmH)
There IS a close analogy between
the formation
of
carbamates
by CO, and the formatlon
of substituted
ureas by cyamc acrd

OCNH + RzNH+

/NR2
0C,NH2

(15)

Jensen[8]
pomts out that the rate constants
(for an
assumed simple second-order
reaction) for CO* are m
general about 12 times those for cyamc acid Williams
and Jencks[9] have investigated reactlon (15) thoroughly
They show that the reactlon of weakly-basic
ammes IS
subject to general acid-base catalysis, with a term such
as &Am], but that strong bases (hke MEA) react accordmg to simple second-order
kmetlcs The results are
consistent with a mechanism analogous to (13) and (14)
above, but It IS concluded that in the case of strong bases
the proton-removal
step (14) IS so fast that the forward
rate constant, k,, in (13) becomes controlhng
In general, then, It seems reasonable to suppose that
the mechamsm of formation of carbamates IS as shown
m (13) and (14) If [Z] IS the concentration
of zwltterlon
(at quasi-steady state) then

126
1451

m the rates and (10) IS far

are second-order
m [DEA],

because of the dominance of the term 692 Even d this

term were Ignored, (10) would yield a thud-order
rate
constant R/[CO,][DEA]*
with a value of 1056 i*/mol%,
comapred to the value 176 from (11) This 6-fold dlscrepancy remains mexphcable

R = kI[C021[Aml

- kr[Zl = [Z]XkeIBl

(17)

the term Zke[B] mdlcatmg

the contrlbutlon
of the
various bases present to the rate of removal of protons
Thus
[CO*:Am]

kl
kl+Y%&

(17)

If the second term m the denommator

IS ti I we have
simple second-order
kmetrcs. as m the case of MEA
Caplow[7]
investigated
the rates of reactlon of CO*
with a number of ammes (not alkanolammes)
with CO* at
varying pH, using a sophisticated
(but apparently
not
very accurate) version of the competitive
method He

R = kI[C02][Am]

(18)

Almost every zwltterlon IS deprotonated

before it can
revert to CO2 + amme, and the rate-controlhng
step IS the

The reactIon of CO2 with ethanolammes

formation

catalysis

of

the

which IS not subject to

d the second term 1s + 1 we get

zwltterlon

Conversely,

R/[COdAml

=&

CkdBl

This reaction scheme seems to fit all the phenomena

Trial shows that Jergensens
results[6] with DEA can
only be fitted to (17) d the second term m the denommator dommates,
leading to (10) The term 692 could be
attributed to deprotonation
by water
If we consider solely the results of HIklta et al with
MEA and DEA we can explain them by assuming that
k_, IS very much larger for DEA than for MEA-that
is,
the zwittenon
IS much less stable This could plausibly
be attributed to seterrc effects. the -C2H20H chains may
be enlarged by hydrogen-bonding
to water molecules
(there does not seem to be a slmdar difference
m
behavlour
between
monoand dlethylamme)
The
difference m stability of the zwltterlons may be parallel
by the difference m stability of the carbamates[lO]
The
eqmhbrium constant
tAmlCCOzl

[H][AmC02-]
IS (at 20aC) 5 8 x lo4 for MEA and 3 8 x 10 for DEA
Sterlc effects may also lead to ka bemg smaller for DEA
than for MEA, because
It IS more difficult for the
nitrogen
atom to reach
and remove
the proton
Moreover, the lower basic strength (by a factor of 0 26)
of DEA IS likely to have a Brgnsted
effect on the
magmtude of ka, which may be expected to vary as a
fractional power of this ratlo
Thus It 1s assumed
that catalysts
by the amme
dominates m the case of DEA and that (19) becomes
R= p

[CO,][DEA]*

when CO2 reacts with a solution contammg only DEA

Possibly, If the concentration
of DEA were much greater
than 07 M (concentrations
up to 3 M may be used m
practice) the second term m the denommator
of (17)
might become comparable with unity, or even less, and
the order of reaction with respect to DEA might become
less than 2 (slmdarly at concentrations
of MEA less than
0 015 M the reaction might tend to a higher order than
unity m [MEA])
It may be supposed that the term 3380 [OH-] m (10) IS
at least m part due to the catalysis of the formatlon of
carbamate by OH- and not solely to the formahon of
alkyl carbonate
as assumed by J@rgensen[6]
A more
Important
conslderatlon,
from the mdustrlal
pomt of
view, 1s that MEA and DEA are often mlxed with
potassium
carbonate
solution (up to 3 M orlgmal carbonate) as absorbents for CO+ Carbonate ion, which IS a
stronger base than MEA or DEA (pK, at 20C 10 38,
9 81 and 9 22 respectively)
and which IS less hable to
sterlc hindrance, might be expected to catalyse the carbamatatlon reactlon m the case of DEA It would be of

445

great interest to find out whether this IS the case as DEA

1s though to enhance the rate of absorption by carbonate
solutions more than can be accounted for by an addltlve
effect The analysts of rate measurements
would be
comphcated
by the fact that amme added to carbonate/bicarbonate
solution reacts m part to form carbamate
The formatron of alkyl carbonate

It IS generally assumed that rn the reactlon of COZ with

MEA and DEA the rate of formatlon of alkyl carbonate
can be ignored compared to the formatton of carbamate
Since J@rgensens[6] attempt to determine the relative
rates m the case of MEA does not seem to be valid one
may turn to the reactlon of CO* with TEA, which forms
no carbamate
One might assume that the rate of reactton
of the alkyl group (Jargensen asserts that not more than
one alkyl group m any molecule of TEA IS carbonated) in
DEA 1s of the same order as m TEA Three sets of
determmatlons
of the rate of reactlon of TEA with CO*
Faurholt [ 1 l]
are
avadable
Jorgensen
and
and
J@rgensen[6]
measured
the rate by the competltlve
method at 0C and 18C respectively
(the barmm alkyl
carbonate IS soluble m water) In each set the concentration of OH- was kept constant while that of TEA was
varied, so It IS not possible to verify that the reactlon IS
first-order with respect to [OH-] as assumed by the
authors, who tool the mecharusm to be (7). (8), the latter
bemg the rate-determmmg
step, leading to
R = k[CO>][TEA][OH-]

(20)

Another posnbdity,
which would be kmetlcally mdlstmgulshable, IS that the oxygen atom of the alkyl group
attacks the carbon atom of CO+ and that OH- removes a
proton
The values of R/[C02][Am][OH-]
are found
(after recalculation)
to be 5930 at 0C and 12,730 12/mo125
at 18C Hlklta et al [2], usmg the rapid-mixing method,
found rates of reactton which were much larger than
could be accounted for by (20) m view of the low values
of the pH m solutions contammg no NaOH (the pK, for
TEA IS 8 22 at OC) The concentrations
of TEA in
Hlkltas experiments ranged from 0 335 to 1 06 M and the
reaction was found to be first-order wtth respect to both
amme and CO2
Using Htkltas results, one finds the ratio of the rates
or reaction of TEA to that of MEA to be 1% at 0C and
2% at lOOC, whde the ratio for TEA to DEA IS almost
independent
of temperature,
being 6% when IDEA1 =
0 174 M and 1% when [DEA] = 0 719 M Under practical
condltlons
It IS probably Justdiabie to Ignore the formation of alkyl carbonate from MEA and DEA m relation to the formatlon of carbamate
m determmmg
the
total rate of reactlon and hence of absorption
This dlscusslon
does nothmg to reconcde the rateconstants
determmed
by Hlklta et al [2] with those
deduced from rates of CO2 absorption
This topic will be
duscussed separately
Acknowledgemenis-I
am grateful for suggestlons from Dr I
Flemmg and Dr A Kirby

446

DANCKWERTS

REFERENCES

[I] Faurholt
C , J Chrm Phys 1925 22 1
[2] I-I&lta H , Asal S , Islukawa
H and Honda
M , Chem
Engng / 1977 13 7
E and Faurholt
C , Acfa Chem
[3] Jensen
M 3 , Jflrgensen
Stand
1954 8 1137
[4] Jensen
A, Jensen
M B and Faurholt
C , Acta Chem
Stand
1954 8 1129
[5] Pmsent B R W , Pearson
L and Roughton
F J W , Tram
Faraday Sot 1956 52 1512

[6]
[7]
[8]
[9]
[lo]
[II]

Jdrgensen
E , Actu Chem Stand 1956 10 1612
Caplow M , J Am Chem Sot 1%8 90 6795
Jensen M B , Acta Chem Stand
1959 13 289
Wdhams
A W and Jencks W P , J Chem Sot Perktn II
1974 1753, 1760
Danckwerts
P V and Sharma
M M , The Chemrcal
Engzneer Ott 1966 CE 244
Jdrgensen
E and Faurholt
C Acta Chem Stand
1954 8
1141