A MATHEMATICAL

MODEL FOR EQUILIBRIUM

SOLUBTLITY OF HYDROGEN
SULFIDE AND
CARBON DIOXIDE IN AQUEOUS
ALKANOLAMINE
SOLUTIONS
R. D. DESHMUKH* and A. E. MATHER
Department of Chemical Engineering. University of Alberta, Edmonton, Alberta, Canada T6G 2G6
(Received 3 April 1979: accepted 26 June W80)

Abstract-A thermodynamic model is proposed for the solubility of the acid gases (H,S and CO,) in alkanolamine
solutions. The model is based on the extended Debye-Hiickel theory of electrolyte solutions. Predicted partial
messures of the acid gases over monoethanolamine solutiom are in good agreement with experimental data over
;he temperature rangeZ-INPC.
PiTItODUCTlON

Aqueous alkanolamine sotutions are widely used for the

removal of the acid gases (H2S and CO*) from natural
gas, synthesis gas and refinery gas streams. Processes
utilizing alkanolamine solutions are usually classed as
chemical processes because of the reaction of the acid
gases with the weak bases formed by alkanofamines in
aqueous solution. These processes have the advantage of
being able to reduce the concentration
of HzS and CO,
to tow levels, even if the gas stream is at a low total
pressure. The characteristics
of chemical gas treating
processes
have been discussed
by Richardson
and
OConnell [l]. For the rational design of separation processes, a knowledge of the equilibrium sotubility of the
HZS and CO, in the alkanolamine solution is necessary.
While solubility data for a number of atkanolamines have
been published, the range of temperatures,
partial pressures and concentration
of atkanolamine is so great that
a method of correlation of the solubility data is desirable
for extrapolation and interpolation.
SOLUBILITY MODEL

The first attempt to correlate the solubility data for a

COJethanolaminelwater
systems was made by Mason
and Dodge[2]; although the method was not described, it
apparently was a curve-fitting approach. At that time the
reactions between alkanolamines and carbon dioxide had
not been studied. Van Krevelen et a!.[31 developed a
method for the prediction of the partial pressures of HzS
and NH, over aqueous solutions. They use pseudoequilibrium
constants
which do not contain activity
coefficients
and relate these pseudo-equilibrium
constants to the ionic strength of the solution. This study
was successful in representing the ammonia-rich region,
but was not useful for the complete range of concentrations. Danckwerts and McNeil141 used this approach
to predict the equilibrium partial pressure of carbon
dioxide over carbonated
amine solutions. The central
feature of this model is the use of pseudo-equilibrium
constants and their dependence
on ionic strength. The
most serious limitation of this model is that the ionic
*Author to whom correspondence should be

addressed.

strength alone is insufficient to determine the concentration dependence of the pseudo-equilibrium

constants.
Kent and Eisenberg[5] have recently used a modification
of this method to correlate equilibrium solubilities in the
C02/HzS/aminelH20
system. They tried to correlate the
sotubility data using published equilibrium
constants
without any dependence on ionic strength. It was found
that the predicted values deviated significantly from the
experimental
values. Instead of using ionic characterization factors for the dependence
of the pseudoequilibrium constants on ionic strength, they accepted
the values of all but two pseudo-equilibrium
constants
and treated these two as variables to be found by fitting
experimental data.
Atwood d a1.[6] proposed
a method for the catculation of equilibria in the HtS/amine/HZO system. The
central feature of this model is the use of a mean ionic
activity coefficient. The activity coefficients of all ionic
species are assumed to be equal. This assumption is good
at low ionic strengths or if only one cation and one anion
are present in significant amounts. However,
this is
generally
not the case for the COJHzS/alkanolamine/Hz0
system.
This model was utilized by
Klyamer and Kolesnikova[7]
for the COz/amine/H,O
system and was generalized by Klyamer et ai. [S] to make
it applicable to the C02/HzS/amine/H20
system. If the
activity coefficients in the Klyamer et al. model are set
equal to unity, the model is algebraically equivalent to
the Kent and Eisenberg
model. Comparisons
of both
models with experimental data obtained ifi recent years
have been made in papers
by Lee et n1.[9, to].
Differences between the predicted partial pressures and
the experimental
values often were as high as 100%. It
appears that an improved model is necessary for quantitative calculation of the partial pressures of the acid
gases over alkanolamine solutions.
The thermodynamic
framework is based on two types
of equilibria: dissociation of electrolytes in the aqueous
solution and the vapor-liquid equilibrium of the acid gas
species. The dissociation is expressed by the dissociation
equilibrium constant:
K = na,pi

(1)

356

R. D.

and the vapor-liquid

is given by:

equilibrium

DESHMUKHand

for the acid gas species

&YiP = ~$PQHi.
For the solvent,
given by:

water,

(2)

the vapor-liquid

equilibrium

is

MATHER

acidgas equilibria as only a small fraction of the reactants is

used up in these reactions. The alkanolamines have two
active groups, viz. -NH2 and -OH. On account of this
bifunctional nature of alkanolamines, the following reactions are possible:
RI-OH + OH- = RI-O- + Hz0

&Y,P

= y;z, fu.

(3

The activities of the electrolyte species are defined so

that the activity coefficients
approach
unity in an
infinitely dilute solution. The reference state is that of a
hypothetical ideal solution of unit molality. On the other
hand, the activity coefficient of the solvent approaches
unity as the mole fraction of water approaches
unity.
The reference state is that of pure water at the system
pressure and temperature. Equations (lH3) describe the
conditions
for equilibrium in an aqueous solution in
contact with its vapor. To use these equations to predict
the equilibrium composition, information about Q and y
for atl the components present in the system, as well as
the Henrys constants and equilibrium components
are
required.
The main reactions
occuring in the CO#I&alkanolamine/H20
system are as follows:
Ionization of water:
HZ0 = H + OH-.
Dissociation

A. E.

of hydrogen

(4)

R,-O-

= R&-COO-.

These reactions are excluded from consideration because

the amount of products is negligibly small (Jensen ef
&.[I 11). Astarita et ~I.[121 report that these reactions
take place only in a basic solution where pH is II or
greater; these reactions can be neglected as the pH of
even a slightly carbonated solution is less than IO.
The chemical reactions 4-10 are accompanied
by the
vapor-liquid equilibria of the volatile species.
Free amine may also be present in the vapor phase.
Under the conditions of interest, the vapor pressures of
the amines are very small and we can assume that the
amine is present only in the liquid phase. The thermodynamic framework enables us to write the equilibrium relations among the reacting species. These equations are as follows:
K, = y(H)y(OH-)m(H+)m(OH-)/a,

(11)

KW = r(H)y(HS-)m~H)m(HS-)/y(H~S)mlH2S)
K,,

sulfide:

+COi

(12)

= y(H*)y(HCOj-)m(H)m
(HC03-Mr(C02)m(C~,)a,

H&Z = H + HS-.
Dissociation

(5)

Ki = r(RRNH,)y(OH-)m(RRNH*)m

of carbon dioxide:

(OH-)lr(RRNH)m(RRNH)a,

Hz0 + CO2 = H + HCO,-.

(6)

of alkanolamine:

Kzc = y(H)rtS-)m(H)m(S)ly(HS-)m(HS-)

I$0 + RRNH = RRNH2+ + OH-.

Formation

(8)

= H(CWy(CWm(C9)

(19

MWGY(H2S)P

= H(H&)y(H&m(H&

(19)

of bicarbonate
HCO,-

4uYwp = (P!u)pa,.
(9)

ion:
= H + CO,-.

(10)

In these equations RRNH is the chemical formula of the

alkanolamine. Tertiary amines (TEA and MDEA) lack the
extra hydrogen atom and do not form carbamates
by
reaction 8. In addition to the reactions 4-10, other reactions
maytakeplaceinthesolution.Theaminesreactwithcarbon
dioxide to form heterocyclic compounds. The amines may
react with impurities in the sour gas such as carbonyl sulfide
andcarbondisulfide.Thesereactionshavelittleeffectonthe

(17)

W02MC02P

of bisulfide ion:
HS- = H + S-.

Dissociation

(16)

(CO,-)lr(HCO~-)m(HC09)
+ H.

(15)

KY = rW)r(C03-)m(H)m

of carbamate:

RRNH + CO* = RRNCOODissociation

(7)

(14)

KA = y(H+)y(RRNCOO-)m(H+)m(RRNCOO-)ly

(RRNH)y(COZ)m(RRNH)m(COZ)
Dissociation

(13)

(20)

In this work the activity of the water, a,, has been set
equal to its mole fraction, since in most instances the
liquid phase is predominantly water. As well as the effect
of pressure on the fugacity of pure liquid water has been
neglected.
Equations
(llH20)
describe
the thermodynamic
equilibrium
in the COz1H2S/aminelFL0
system.
The following balance equations for the reacting species can be formed:
Electroneutrality:

m(H) + m(RRNHz)
+ m(HC03-)

= m(OH-) + m(HS-)

+ m(RRNCOO-)+

2m(S)+

2m(C%).
(21)

357

A mathematicalmodel for equilibriumsolubility

Mass balances:
tnA = m(RRNH) + m(RRNH2)

+ m(RRNCOO-)
(22)

+ m(C03)
+ m(RRNCOO-)

(23)

= m(H2S) + m(HS-) + m(S).

124)

mAa(COZ) = m(CO3 + m(HCOa-)

m&H&

The fugacity coefficients, & were calculated using the

PeneRobinson[28]
equation
of state. The activity
coefficients take into account interactions between solute
species in the liquid phase. In this work, the extended
Debye-Hiickel
expression given by Guggenheim[29] has
been used to obtain yk:

Here mA is the concentration of the alkanolamine which

is determined by titration (also called the stoichiometric
concentration)
and n(C0,)
and a(HzS) are the mole
ratios in the liquid phase (carbon to nitrogen and sulfur to
nitrogen). These ratios are the usual experimental values
which are obtained in solubility experiments.
The equilibrium constants and Henrys constants needed
for predictionof theequilibriumcomposition
were obtained
from the literature where possible. The references are given
in Table 1. It should be noted that the most reliable
measurements
of the dissociation
constants of the alkanolamines
are those of Bates and coworkers.
They
report acidic dissociation constants, KbL. These are related
to the basic dissociation constant, Ki,usedhere by the
equation:

The first term expresses

the Debye-Hiickel
law and
represents
the electrostatic
forces. The second term
takes into account short-range Van der Waals forces.
The quantity A is related to the dielectric constant of the
solvent and b, may be considered a constant. Edwards et
a/.[301 used eqn (26) in their model for correlation of the
equilibria in dilute solutions of NH1, COZ, HzS, SO2 and
HCN in water. The interaction parameters in eqn (26),
show
a weak dependence
on ionic strength
AJ
(Scatchard[31])
and temperature
(Edwards et al. [30]).
The interaction
parameters
for all pairs of species
present in the mixture must be known to estimate
activity coeficients.
Edwards et al. [30] used a procedure
described by Bromley[32] to estimate some of the interaction parameters.
This procedure
cannot be applied
system since the
Ki= KJKbh(25) directly to the C021H2S/amine/H20
parameters needed (entropies of the ions and salting-out
coefficients) have not been determined for all the species
Values of Kbh for DEA and TEA have also been
present in this system. In the next section the method
reported[l7,
181, but only over the temperature
range
used to estimate these interaction parameters
will be
b5oC.
described. Pitzer[33] has proposed
a more accurate
Equilibrium
constants
for carbamate
formation
in
expression
than the extended Debye-Hiickel
equation
MEA and DEA solutions are available only at 18C.
for activity coefficients and this equation was used by
Jensen ef nL[ll] used the Bjerrum expression to calEdwards et al.[34] in extending their previous work to
culate the equilibrium constant. McNeil[f9] studied the
more concentrated
solutions.
Beutier and Renon [35J
same reaction, but used a different method to anafyse his
have also used Pitzers expression to calculate the equilresults. For moderate degrees of carbonation,
the caribria
in the
NHnlC02/H20,
NH3/H2S/H20
and
bamate is the main product of the reaction and it is
NH,/S02/HZ0
systems.
Even though the reactions
unfortunate that this key reaction has received so little
occuring in these systems have been well-studied, Beuattention from researchers.
Table I. Source of dissociation constants
Variable
%
RlC
RlY
KiWEA)

Temperature

K2Y

RC02

H-S

Henrys constants

Range

Reference

O0

- 150 %

olofeson

00

- 250

Rao

25O

- 250

"c

Read

O0

KAWW
K2C

and

25O
00

and

Bates

I ac

Jensen

- 150 %

uyukov

Oc

Hepler

and

O0

- 350

- 330

DC

"c

b3]

p4)

Warned

Pinching

et

al.

et

al.

US]

(111
[203

Scholes
Strafelda

c21
@ 2I
I?31

and

Cuta and
Ryzhenko
O0

Kepler

b5]

- 50 *c

- 300

and

wiabe and Gaddy

Zel'venskii
Ellb

P 2;

Lee

@7]

and

Mather

R. D.

358

DESHMUKH and

tier and Renon had to make several assumptions about

the interaction
parameters
to render the expression
manageable. It appears that Pitzers expression is too
complicated for use in aIkanolamine solutions given the
present knowledge regarding the reactions occurring in
the solution.
MGTHODOF

!ZOLUTlON

The mathematical problem is to solve eqns (11)-(24).

Twelve species exist: HsS, CO*, RRNH, HS,
S,
HCOI-, COa, RRNHz+, RRNCOO-, H, OH-, H20.
Hence there are twenty-three
unknowns (mi and ri) for
all species and the mole fraction water. To solve for the
unknowns,
there are twenty-three
independent
equations: seven chemical equilibria, three mass balances,
electroneutrality,
the use of eqn (26) for the eleven
activity coefficients and the vapor-liquid equilibria. The
problem is one of solving a system of non-linear algebraic equations. Browns method [36,37] was chosen
for this purpose. It is an efficient procedure which is
baaed on a partial pivoting technique, The successive
substitution nature of Browns method is analogous to
Gaussian elimination in linear systems of equations. To
obtain fast convergence with Browns method, the variables and the functions are normalized so that they are
all of the same order of magnitude. The molalities and
the partial pressures in the C0JH2S/amine/Hz0
system
range over several orders of magnitude. To normalize the
variables, the equations were formulated
in terms of
their logarithms. The functions were normalized so that
the convergence criteria could be expressed as If(x)1-CE
where c is a small positive constant. For example, eqn
(I I) was normalized by writing it as:
f, = 1 - y(H+)y(OH-)m(H+)m(OH-)IK~,.

(27)

The remaining equations were normalized in the same

manner. A FORTRAN program for the calculation of the
equilibrium compositions
was written, The sequence of
calculations is as follows:
(1) The temperature, concentration
of the ,amine. and
either the acid gas partial pressure or the acid gas mole
ratios in the liquid are specified.
(2) The equilibrium constants, the Henrys constants,
the dielectric constant of water, and the binary-interaction parameters are calculated.
(3) A preliminary solution is calculated by setting all
activity coefficients and fugacity coefficients equal to
unity.
(4) The preliminary estimate is refined using Browns
method for the solution of the system of non-linear
equations.
(5) The equilibrium composition
is determined
from
the converged solution.
In the COJH2S/alkanolamine/Hz0
systems, the direct
prediction of the equilibrium composition is not possible
since some of the equilibrium constants and the specific
interaction parameters are unavailable. These parameters
can be obtained by least squares fitting of experimental
data.
&,I be the array of the interaction
I-etB=[/%.B*.....

A. E.

MATHER

parameters and E = [e,, ez, . __, eM] be the array of the

errors in predictions.
We wish to find the interaction
parameters
B* that minimize
s = IEI. When s is
minimum,
a$afii=O,

i=1,2

,...,

44.

The N equations can, in principle, be solved for the N

unknown Bs, However, such a procedure is not feasible
because of the excessive computational effort involved.
To simplify the calculations, the following assumptions
may be made.
(1) The-interaction
parameters for the species which
are present
in very small concentrations
can be
neglected.
(2) The effect of the Bs on the errors in prediction is
assumed to be additive.
When a certain chemical species is present in a very
small concentration,
it has little effect on the equilibria.
The concentration
of that species may be neglected from
the balance equations. A reduced set of equations can be
solved in terms of a smaller set of variables. For example, if S is present in a very small amount, its concentration can be ignored from the charge balance and the
sulfur balance equations.
The equations
(except the
equilibrium relation for the dissociation of the bisulfide
ion) can he solved for the variables (excluding S-).
Secondly, the term &jmf in the extended Debye-Htickel
theory may be neglected if nt, is small.
The additivity assumption implies that the total deviation in predictions may be expressed as a sum of the
individual deviations
due to each of the interaction
parameters.
Let p be the predictions
using B=
[0, 0,L. _,03 and let P be the measured values. Therefore,
I? = P - p is the total error. The effect of the interaction
parameters can be found by setting jth parameter to a
small number, say A& Let the new predictions
be
P(A&). This means that setting the jth parameter to A/3,
has caused a deviation of [P(A&) -m in the predictions.
If 6s are small, this deviation is proportional
to the
magnitude of /3; i.e.
PO3j)- FIIS, = D%W,) - PllW,

W/3,)-PO = (~~/MVD(WI) - PI.

Define C, = [P(A&) - P]/A& Since the total deviation
the sum of the individual deviations,
CT = c

is

B,C,.

This can be written as

CT =X.B
where X = [C,, C2,. . . , C,]. We wish to find B so that CT
is the best estimate of &, i.e. we wish to minimize the
squared error q = IJ!? - CT\*.
q =

(EO-CTy(E?-cCT).

A mathematical model for equilibrium solubilily

Substituting CT = X . B and expanding

349

loo00

q = E%? - BXP - EOXB+ BXXB

aq/a& = - 2IXEY
+ 2IXXB.

loo0

When q is minimum, aq/la& = 0.

:. XXB = Xti

I
B
g

loo

B = (XX)-X@.
c
LL

All arrays required in this method can be calculated by

using the computer program described above. The
method can be extended to determine the equilibrium
constants outside their range of measurement. Define
K = K. exp 6 The exponential function is used to ensure
that K is always positive. Given an initial estimate of K,
f can be determined by the least squares fitting as
described above.
AP?LICATtON TO MONOETHANOLAMINE (MEA) !XUlTIONS

The application of the model to MEA solutions is

hampered by the lack of information regarding the
specific interaction parameters for monoethanolammonium ions and carbamate ions. As well the equilibrium
constant for carbamate formation is available only at
WC and the equilibrium constant for the dissociation of
MEA is known only between
0 and 50C. In the
COJHtS/MEA/HtO
system, the only species which are
present in significant concentrations are the free amine
and the monoethanolammonium,
carbamate. bicarbonate
and bisulfide ions. This means that the interaction
parameters for the other species (CO,, H& OH-, H+,
S and CO,) will have little effect on the observed
equilibria. However, at very high loadings, the concentration of the free CO2 and free HIS are also high. The
important interaction
parameters
are /3(RNHTRNHz).
/3(RNHrRNHCOO-),
B(RNHrHCO,-),
@(RNHr
HS-), /3(RNHz-RNHCOC-),
@(RNH,+-HCO,-)
and
p(RNH*-HS-)
where R = -CH,CH,OH.
The first of
these can be determined from the correlation of Atwood
et a1.[6]. It should be noted that there are no mixture
parameters
in the list. The parameters for the
COJMEA/H20
system and the H2S/MEA/Hz0
system
are
sufficient
to predict
the
equilibria
in the
C0,1H2S/MEA/H,0
system and hence the parameters
may be determined from data for the three component
systems.
The partial pressures
of HZS over 2.5 N and 5.0 N
MEA solutions at 25, 40. 60. BO, loo and 120% have
been reported by Lee et al.[38]. These data were used to
determine
/3(RNHrHS--).
fi(RNH2+-HS-)
and the
equilibrium constant for the dissociation of MEA at
IOWC. Figures 1 and 2 show the comparison between the
predictions and the experimental data. The agreement is
good for both 2.5 N and S.ON MEA solutions at all
temperatures.
Thepartialprersuresof
COzover 1.0 N,2.5 N.3.75 Nand
5.0 NMEAsolutionsat
25,#,W,W.
1Wand 120C have
been measured by Lee et al. [lo]. The equilibrium constant
for carbamate formation at WY!, as well as the fi(RNH,

t
2
(I)

10

1.0

0.1

0.2

0.1

0.6

0.8

1.0

1.4

a.*

Mole Ratlo in Liquid. H~.s/MEA

Fig.

10000

I.

Solubility of HIS in 2.5 N MEA solutions.

t

,.;t

0.2

( ,

01

Ratio

, ,

0.8

06

Mole

10

in Liquid,

1.2

1.4

H&MEA

Fig. 2. Solubility of H# in 5.0 N MEA solutions.

Table 2. Specific interaction parametersfor MEA
kg/mole
B(RNtlt- HS-)
~CRNH,+
B(RNHt

w-1

URNH*

HCO,-)
Rt4~~00-)

0.0375

0.005

liCO,-)

B(RNH*+-

BIRN~+

RNHCOO-)

0.0245

0.0375

0.063
0.006

R. D. DE-SHMUKH
and A. E. MATHER

3&l

HCO,-1, fi(RNHz+-HCOs-),
fi(RNH,RNHCOO-)
and
,9(RNH,-RNHCOO-)
were determined from these data.
The interaction parameters which were obtained from the
dataon the three-component
systems are presented in Table
I. Figures 3 and 4compare some of the predictions with the
experimental
data. The agreement is good at all temperatures and normalities. The agreement shown on Figs.
14sameasureofthegoodnessof
fitofthemodel,sincethe
parameters were obtained from the experimental data.
The partial pressures of mixtures of CO1 and H2S over

MEA solutions at 40 and 1OCPChave been measured by

Lee et al.[9] in 2.5.N solution and by Lee ef al.[39] in
5.0 N solution. The parameters obtained above were used
to predict the equilibria for the mixtures of CO, and H2S
in the MEA solutions. Figure 5 illustrates the effect of
CO, on the solubility of H2S in the 2.5 N MEA solution
at lWC, while Fig. 6 shows the reverse. Similar plots for
the 5.0 N solution at 100C are presented in Figs. 7 and 8.
On the whole, the agreement of predicted partial pressures with experimental values is much better than that
10000~

wooo

lax,

B
f

100

F
g

10

1.0

0.1

0.2

0.4

0.6

0.8

1.0

1.2

Fig. 3. Solubility of C& in 2.5 N MEA

1.4

0.2

0.4

MOle

Mole Rail0 in Liquid, U&/MEA

solutions.

0 6

0.8

Ratio in Liquid,

1.0

1.2

1.4

H.$VMEA

Fig. 5. Effect of CO2 on the solubifily of H,S in 2.5 N MEA

solutions at 100C.
1OOW

loo00

1WO
1000

s
f

2
-r
f

d
g

i!

0.

z
h
N

100

100

h
N
8

10

10

1.0

1 .o

0.10

0.1
0

0.2

0.4

0.8

I.0

12

Mole Ratio In Liquid. C02/~~~

Fig. 4. Solubility of CO, in 5.0 N MEA solutions.

1.1

02

0.4

0 6

0.8

1.0

1.2

1.4

Mole Ratio in Liquid. CO&IEA

Fig. 6. Effect of H2S on the solubiIity of CO, in 2.5 N MEA

solutions at 100C.

A mathematical model for equilibrium solubility

0.2

0.4
Mole

Fig.

Q.6
Ratio

0.8

in Liquid.

1.0

I.*

1.1
Mole

H@/MEA

7. Effect of CO, on the solubility of HIS in MN MEA

F&

8.

solutions at IOLPC.

of models proposed previously. Generally, the predictions tend to bracket the experimental
data. At hiih
loadings, the agreement is poorer and the predicted partial pressures are lower than the experimental
values.
This suggests that interaction parameters such as p(COr
HS-) and /3(H&HCO,-)
become important at these
conditions.
Directions for improvement
of this model
include the use of parameters involving COz and H,S. To
determine
these parameters.
equilibrium data for the
C0JH2S/Hz0
system
would
be needed.
Reliable
experimental data for the carbamate formation equilibria
would also be helpful to predict sotubilities over wide
ranges of temperature.
Ackmwledgemenf-This
work was supported
Research Council of Canada.

361

by the National

X
Y

Ratio

in Liquid.

COzlMEA

Effect of HzS on the solubifity of COr in S.ON MEA

solutions at IOOV.
vector of deviations
mole fraction in vapor phase
charge on an ion

Greek svmbols
mole ratio in the liquid phase, moljmol
specific interaction coefficient in extended
Hiickel equation
activity coefficient
a small perturbation
a small tolerance
stoichiometric
coefficient
product
summation
fugacity coefficient

Debye-

Subscripts
NOTATION

:
B

C
E
Ii

I
I

K
m
P
P
:
B
X

activity
constant in Debye-Hiickel
equation
vector of /3s
vector of deviations in predictions
vector of errors in predictions
Henrys cpastant, kg Pa mol-
ionic strength = 0.5 Z miz?, mol kg-
identity vector
equilibrium constant
molality, mol/kg solvent
pressure, partial pressure, kPa
vector of partial pressures
squared error
gas constant, J mol- K-
squared error
temperature, K
mole fraction in liquid phase

bh
i
i
A
w
IC
2C
1Y
2 I

acidic dissociation of amine

component i
dissociation of amine
carbamate formation
water
ionization of hydrogen sulfide
dissociation of bisulfide ion
ionization of carbon dioxide
dissociation of bicarbonate ion

Superscripts
0 reference state
0 base case, fi = 0
REFERENCES

[t] Richardson 1. M. J. and OConnell J. P., Ind. Engng Chem.

Pmt. Lks. Lkv. 1975 14 467.
[21 Mason J. W. and Dodge B. F., Tmns. A.I.ChE. 193632 27.

R. D. DESHMUKHand A. E. MATHER

362

[31 Van Ktevelen D. W., Hoftijzer P. J. and Huntjens F. J.,

Rec. True. Chim. 1949 68 191.
[4] Danckwerts
P. V. and McNeil1 K. M.. Trans. Inst. Chem.
Engng I%7 45 T32.
Proc. 1977655(Z)
[51 Kent R. L. and Eisenberg B., IJydrocarbon
87
-.

161 Atwood K., Arnold M. R. and Kindrick R. C., Ind. Engng

Chem. 1957 49 1439.
171 Klyamer S. D. and Kolesnikova T. L., Zhur. Hz. Khim. 1972
46 1056.

I81 Klyamer S. D., Kolesnikova T. L. and Rodin Yu. A., Gazov.

Pmm. 1973 lB(2) 44.
[91 Lee J. I., Otto F. D. and Mather A. E., Can. J. Chem. Engng
1976 54 214.
1101 Lee J. I., Otto F. D. and Mather A. E., J. Appl. Chem.
Biotechnol. 1976 26 541.
IIf1 Jensen M. B., Jorgensen E. and Faurholt C., Acta Chem.
&and. 1954 8 1141.
1121 Astarita G.. Marrucci G. and Gioia F., Chem. Engng Sci.
1964 19 95.
[I31 Olofsson G. and Hepler L. G., J. Solufion Chem. 1975 4 127.
[I41 Rao S. R. and Healer L. G.. HvdrometaNurnv 1977 2 293.
il5j Read A. J., /. So&ion Chetk j975 4 53.
-_
I161 Bates R. G. and Pinching G. D., J. Res. NBS 1951 46 349.
[17] Bower V. E., Robinson R. A. and Bates R. G., J. Res. NBS
I%2 66A 71.
[I81 Bates R. G. and Allen G. F.. /. Res. NBS 1960 64A 343.
1191 McNeil K. M., Ph.D. Dissertation,
Cambridge University

1965.
1201 Kryukov P. A., Starostina
L. 1.. Tarasenko
Primanchuk M. P., Geokhimiyu 1974 (7) 1003.

S. Ya. and

[211 Harned H. S. and Scholes S. R., 1. Am. Chem. Sot. 1941 63

1706.
1221 Cuta F. and Strafelda F.. Chem. Listv 1954 48 1308.
i23j Ryzhenko B. N., Geakhikiyn 1963 (i) 137.
1241 Wiebe R. and Gaddy V. L.. 1. Am. Chem. Sot. 1939 61 315.
[25] Zelvenskii Ya. D., _f. Chem. Ind. (USSR) 1937 14 1250.
1261 Ellis A. J.. Am. 1. Sci. 1959 257 217.
1271 Lee J. 1. and Mather A. E.. Ber. Eltnsenges. Phys. Chem.
1977 RI 1020.
1281 ien8 D. and Robinson D. B., Ind. Engng Chem. Fund/s t976
15 59.
1291 Guggenheim E. A., Phil. &fag. 1935 19 588.
1301 Edwards T. I., Newman J. and Prausnitz J. M., A.1.Ch.E.J.
1975 21 248.
[31] Scatchard G., Chem. Rev. 1936 19 309.
[32] Bromley L. A., J. Chem. Thermodyn. 1972 4 669.
[331 Pitzer K. S., L Phys. Chem. 1973 77 268.
[341 Edwards T. J., Maurer G., Newman J. and Prausnitz, J. M.,
A.LC7t.E. J. 1978 24 966.
1351 Beutier D. and Renon H., fnd. Engng Chem.Proc. Des. &u.
19x3 17 220.
t361 Brown K. M., SIAM J. Numer. Anal. 1%9 6 560.
[37l Brown K. M. Numerical Solution of Nonlinear Algebraic
Equations (Edited by Byrne G. D. and Hall C. A.), p. ,281.
Academic Press, New York 1973.
t38l Lee J. I., Otto F. D. and Mather A. E.. 1. Chem. Engng Data
1976 21 207.

t39l Lee J. I., Otto F. D. and Mather A. E.. 1. Chem. Engng

157520

161.

Duta