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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 m the formatlon of carbamate and that the reactlon of DEA (but not of MEA) LScatalysed by
bases

The absorption of CO, by solutions of alkanolammes IS remam m solution The reaction and analysis have to be
an operation of such mdustrlal Importance that the performed qmckly because the carbamate IS SubJect to
kmetlcs of the reactions between CO, and these ammes hydrolysis This IS more marked m the case of DEA, and
are of considerable interest I shaIl confine myself to a calculated correction had to be apphed with consequent
aqueous solutions of monoethanolamme (MEA) and doubts as to their accuracy Depletion of the reagents by
dlethanolamme (DEA), with a glance at trlethanolamme preferential reaction near the Interface was probably
(TEA), although other ethanolammes and other solvents negligible and had been the subJect of some m-
are sometimes used Only the forward reaction ~111 be vestlgatlons by Jensen et al [4] The mltlal concen-
considered here, although the reverse reactlon IS equally trations of amme and NaOH. the amount of CO2 ab-
important sorbed (mol/l) and the percentage of the CO2 absorbed
In the recent chemical engtneermg literature It has which was not precipitated as carbonate were recorded
been usual to write the reaction as The rate of formation of carbamate was assumed to be
L[COt] [Am1 and km was calculated from
COz + RzNH + RzNCOOH (1)
% non-carbonate = k,[Am]
R2NCOOH + RzNH + RzNCOO- + RzNHz+ (2) (3)
% carbonate k&OH-1
the first step being bimolecular, second-order and rate
The results have been recalculated using the value of
determining, while the second step was supposed to take
kOH given by Pmsent et al [5]
place mstantaneously The carbamlc acrd can be regar-
ded as fairly strong, with pK, (7, and the zwitterion
log,okoH = 13 65 - 2895/T (4)
R&HCOO- IS msufficlently stable to be formed In ap-
preciable concentration, these supposltlons are borne out (TK) and the mean values of the concentrations of
tn the case of (H2NCOO- + NH4) by the electrical amine and OH- between the begmnmg and end of the
conductrvlty measurements of Faurholt [ 11 which showed reaction calculated by means of the stolchlometnc rela-
that the equivalent conductlvlty of ammomum carbamate tions
1s not much less than that of ammomum chloride
However, recent rapid-mixing mvestlgatlons by Hlklta CO1 + Am + OH-+ AmCOO- + Hz0 (5)
et al [2] show that while the reaction of CO, with MEA
1s first-order, that with DEA IS second-order m the CO_r+ 20H- + CO1- + Hz0 (6)
concentration of amine (m the amme concentration
ranges 0 0152-O 177 and 0 174-O 719 M respectively, be- The resultmg value of k,, for MEA at 18C 1s 4065 -+ 5%
tween temperatures of about 6C and 40C) l/mols (based on 3 experiments with [OH-] and [MEA]
Reference to earlier pubhcatlons shows that the both uutlally at 0 1 and 0 2 M), compared with 3934
kmetlcs of the reactions between CO1 and ammes m interpolated from the results of Hlkita et al [2] There 15
general and MEA and DEA tn particular are more com- possibly a slight dependence of k,, on [OH-], but dou-
plicated than had prevrously been assumed by chemical bling the latter only Increased the former by 7-8% The
engineers The results to be consldered are results for DEA were discarded in favour of those
(a) Jensen et al [3]-MEA and DEA The rates were below
determined by the competltrve method, 10% CO* in air (b) JargensonE6]-DEA Slmdar experiments at OC,
was bubbled through solutions contaming amtne and carried out more rapidly, thus reducing the error due to
NaOH (each at 0 1 and 0 2 M) at 18C The soluttons hydrolysis The concentrations of amine and OH- were
were then analysed by adding BaC12 and filtering-off the permutated at the levels 0 1. 0 2 and 0 3 M Jtirgenson
barium carbonate preclpltated, the carbamate (and any Interpreted the results as follows
aIkyl carbonate formed from the hydroxyl groups of the (I) a second-order reaction of CO, with DEA to form
ammes-assumed m [3] to be of neghglble amount) carbamate ,

443
444 P V DANCKWERTS

(II) a reactlon system fitted the kmetlcs to the expresslon

C-OH+OH-=C-O-+HzO (7) R/[C021[Aml = a~ + 01 [OHI (12)

C-0-+COt-+C-OCO*- (8) The reactlon was defimtely catalysed by OH- but he was
unable to determine whether or not there was a third
where (8) 1s the rate-determmmg step Thus (If the frac-
term, a2[Am], mdlcatmg catalysis by the amme He con-
tlon of the -OH groups lomsed were small) the rate of
sidered the mechmsm to be the formation of a zwltterlon
formation of alkyl carbonate would be proportional to
followed by the removal of a proton by a base B
[C021[DEAI[OH-I, giving

% non-carbonate = [Am](ao + a,[OH-]) COz + RzNH 2*_1 R&HCOz- (13)


(9)
% carbonate kcw[OH-1
R&HC02- + BLB- R2NC02- + BH (14)
However, a glance 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 the second step being rate-determmmg The base may be
of confirmation 0 86, mcluston of a term a2[DEA] gives water (+H20), leading to the term a0 or OH- (+H20),
leading to the term aI One might expect a third term
R = [C02][DEA](692 + 3380[OH-] + 1056[DEA]) a*[Am] correspondmg to specdic catalysis by the amme
(10) (+ AmH)
There IS a close analogy between the formation of
with a coefficient of confirmation 0 93 (R bemg the rate carbamates by CO, and the formatlon of substituted
of reaction of amme, mol/l s) ureas by cyamc acrd
Jergensen also carried out a set of experiments m
which CO* reacted with NaOH solutions contammg /NR2
OCNH + RzNH+ 0C,NH2 (15)
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 Jensen[8] pomts out that the rate constants (for an
last experiment did not agree well with that predicted assumed simple second-order reaction) for CO* are m
from the results of the first two, no doubt because of a general about 12 times those for cyamc acid Williams
mlsmterpretatlon of the kmetlcs as suggested above and Jencks[9] have investigated reactlon (15) thoroughly
Companng (10) with an extrapolation of Hlkltas They show that the reactlon of weakly-basic ammes IS
results (m which the concentration of OH- formed by subject to general acid-base catalysis, with a term such
the hydrolysis of DEA was small enough for the second as &Am], but that strong bases (hke MEA) react ac-
term m (10) to be Ignored) to WC by cordmg to simple second-order kmetlcs The results are
consistent with a mechanism analogous to (13) and (14)
log,dR/[C02][DEA]) = I2 41-2775/T (11) above, but It IS concluded that in the case of strong bases
the proton-removal step (14) IS so fast that the forward
we find R/[CO-rl[Amls- rate constant, k,, in (13) becomes controlhng
In general, then, It seems reasonable to suppose that
[DEA] = 0 174 M Hlklta 31 the mechamsm of formation of carbamates IS as shown
m (13) and (14) If [Z] IS the concentration of zwltterlon
(10) 876
(at quasi-steady state) then
[DEAI = 0 7 19 M Hiklta 126
R = kI[C021[Aml - kr[Zl = [Z]XkeIBl (17)
(10) 1451
the term Zke[B] mdlcatmg the contrlbutlon of the
There IS a gross discrepancy m the rates and (10) IS far
various bases present to the rate of removal of protons
from leadmg to values which are second-order m [DEA],
Thus
because of the dominance of the term 692 Even d this
term were Ignored, (10) would yield a thud-order rate kl
constant R/[CO,][DEA]* with a value of 1056 i*/mol%, (17)
[CO*:Am] = k-
comapred to the value 176 from (11) This 6-fold dls- l+Y%&
crepancy remains mexphcable
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* R = kI[C02][Am] (18)


with a number of ammes (not alkanolammes) with CO* at
varying pH, using a sophisticated (but apparently not Almost every zwltterlon IS deprotonated before it can
very accurate) version of the competitive method He revert to CO2 + amme, and the rate-controlhng step IS the
The reactIon of CO2 with ethanolammes 445

formation of the zwltterlon which IS not subject to great interest to find out whether this IS the case as DEA
catalysis Conversely, d the second term 1s + 1 we get 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
R/[COdAml =& CkdBl
comphcated by the fact that amme added to car-
bonate/bicarbonate solution reacts m part to form car-
This reaction scheme seems to fit all the phenomena bamate
Trial shows that Jergensens results[6] with DEA can
only be fitted to (17) d the second term m the denomma- The formatron of alkyl carbonate
tor dommates, leading to (10) The term 692 could be It IS generally assumed that rn the reactlon of COZ with
attributed to deprotonation by water MEA and DEA the rate of formatlon of alkyl carbonate
If we consider solely the results of HIklta et al with can be ignored compared to the formatton of carbamate
MEA and DEA we can explain them by assuming that Since J@rgensens[6] attempt to determine the relative
k_, IS very much larger for DEA than for MEA-that is, rates m the case of MEA does not seem to be valid one
the zwittenon IS much less stable This could plausibly may turn to the reactlon of CO* with TEA, which forms
be attributed to seterrc effects. the -C2H20H chains may no carbamate One might assume that the rate of reactton
be enlarged by hydrogen-bonding to water molecules of the alkyl group (Jargensen asserts that not more than
(there does not seem to be a slmdar difference m one alkyl group m any molecule of TEA IS carbonated) in
behavlour between mono- and dlethylamme) The DEA 1s of the same order as m TEA Three sets of
difference m stability of the zwltterlons may be parallel determmatlons of the rate of reactlon of TEA with CO*
by the difference m stability of the carbamates[lO] The are avadable Jorgensen and Faurholt [ 1 l] and
eqmhbrium constant J@rgensen[6] measured the rate by the competltlve
method at 0C and 18C respectively (the barmm alkyl
tAmlCCOzl carbonate IS soluble m water) In each set the concen-
[H][AmC02-] tration of OH- was kept constant while that of TEA was
varied, so It IS not possible to verify that the reactlon IS
IS (at 20aC) 5 8 x lo4 for MEA and 3 8 x 10 for DEA first-order with respect to [OH-] as assumed by the
Sterlc effects may also lead to ka bemg smaller for DEA authors, who tool the mecharusm to be (7). (8), the latter
than for MEA, because It IS more difficult for the bemg the rate-determmmg step, leading to
nitrogen atom to reach and remove the proton
Moreover, the lower basic strength (by a factor of 0 26) R = k[CO>][TEA][OH-] (20)
of DEA IS likely to have a Brgnsted effect on the
magmtude of ka, which may be expected to vary as a Another posnbdity, which would be kmetlcally mdls-
fractional power of this ratlo tmgulshable, IS that the oxygen atom of the alkyl group
Thus It 1s assumed that catalysts by the amme attacks the carbon atom of CO+ and that OH- removes a
dominates m the case of DEA and that (19) becomes 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,
R= p [CO,][DEA]*
found rates of reactton which were much larger than
could be accounted for by (20) m view of the low values
when CO2 reacts with a solution contammg only DEA of the pH m solutions contammg no NaOH (the pK, for
Possibly, If the concentration of DEA were much greater TEA IS 8 22 at OC) The concentrations of TEA in
than 07 M (concentrations up to 3 M may be used m Hlkltas experiments ranged from 0 335 to 1 06 M and the
practice) the second term m the denommator of (17) reaction was found to be first-order wtth respect to both
might become comparable with unity, or even less, and amme and CO2
the order of reaction with respect to DEA might become Using Htkltas results, one finds the ratio of the rates
less than 2 (slmdarly at concentrations of MEA less than or reaction of TEA to that of MEA to be 1% at 0C and
0 015 M the reaction might tend to a higher order than 2% at lOOC, whde the ratio for TEA to DEA IS almost
unity m [MEA]) independent of temperature, being 6% when IDEA1 =
It may be supposed that the term 3380 [OH-] m (10) IS 0 174 M and 1% when [DEA] = 0 719 M Under practical
at least m part due to the catalysis of the formatlon of condltlons It IS probably Justdiabie to Ignore the for-
carbamate by OH- and not solely to the formahon of mation of alkyl carbonate from MEA and DEA m rela-
alkyl carbonate as assumed by J@rgensen[6] A more tion to the formatlon of carbamate m determmmg the
Important conslderatlon, from the mdustrlal pomt of total rate of reactlon and hence of absorption
view, 1s that MEA and DEA are often mlxed with This dlscusslon does nothmg to reconcde the rate-
potassium carbonate solution (up to 3 M orlgmal car- constants determmed by Hlklta et al [2] with those
bonate) as absorbents for CO+ Carbonate ion, which IS a deduced from rates of CO2 absorption This topic will be
stronger base than MEA or DEA (pK, at 20C 10 38, duscussed separately
9 81 and 9 22 respectively) and which IS less hable to
sterlc hindrance, might be expected to catalyse the car- Acknowledgemenis-I am grateful for suggestlons from Dr I
bamatatlon reactlon m the case of DEA It would be of Flemmg and Dr A Kirby
446 P V DANCKWERTS

REFERENCES
[6] Jdrgensen E , Actu Chem Stand 1956 10 1612
[I] Faurholt C , J Chrm Phys 1925 22 1 [7] Caplow M , J Am Chem Sot 1%8 90 6795
[2] I-I&lta H , Asal S , Islukawa H and Honda M , Chem [8] Jensen M B , Acta Chem Stand 1959 13 289
Engng / 1977 13 7 [9] Wdhams A W and Jencks W P , J Chem Sot Perktn II
[3] Jensen M 3 , Jflrgensen E and Faurholt C , Acfa Chem 1974 1753, 1760
Stand 1954 8 1137 [lo] Danckwerts P V and Sharma M M , The Chemrcal
[4] Jensen A, Jensen M B and Faurholt C , Acta Chem Engzneer Ott 1966 CE 244
Stand 1954 8 1129 [II] Jdrgensen E and Faurholt C Acta Chem Stand 1954 8
[5] Pmsent B R W , Pearson L and Roughton F J W , Tram 1141
Faraday Sot 1956 52 1512

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