Computersthem. Engng,Vol. 17, No. 12, pp. 1157-1165. 1993 0098- I354/93 86.00 + 0.

00
Rinted in Great Britain Pergamon Press Ltd

A PHYSICO-CHEMICAL METHOD TO CALCULATE

TIME-DEPENDENT REACTION MIXTURES

I’. KOUICKARI
Kemira, Inc., P.O. Box 368, President St Ext., Savannah, GA 31402, U.S.A.

(Received 4 June 1992;finnl revision received IO May 1993; received for publicarion 3 June 1993)

Abstract-A method is proposed to calculate multicomponent chemical reaction mixtures as a series of

sequential, time-dependent thermochemical states. The procedure is based on the two general principles
of physical chemistry, viz., decreasing Gibbs-energy for a natural process and the exponential Arrhenius
rate law for the overall reaction kinetics. The calculation is performed in repeated sequences for a closed
system element with known heat transfer to its surroundings. The temperature of each sequential reactor
element is determined by a Gibbs-energy minimization routine (SOLGASMIX) connected to the closed
system enthalpy balance iteration. The extent of overall reaction is limited by the Arrhenius kinetics, while
the possible side reactions may reach equikbrium. The mass balance relations forming the subsidiary
constraintsof the Lagrange method are modified to facilitate the Gibbs-energy minimization for the
intermediate “reactor states”. The well-known reaction of titanium (IV) chloride oxidation to titanium
dioxide with such side reactions as chlorine dissociation and oxychloride formation is given as a
calculational example.

1. INTRODUCTION where wa now has negative values for the above

A simple method is presented by which a series of species denoted by A.

chemical compositions may be calculated for a multi- In a small time interval dt the reaction takes place
component chemical reaction. The compositions are to the extent &:
received each in a given intermediate temperature and 0 = Iwe &B, (3)
pressure. The method examines the combination of
the Arrhenius overall reaction rate and the minimiz- where de/dt is the reaction rate. The thermodynamic
ation of Gibbs energy for the reaction mixture in each conditions for a natural process and equilibrium are:
discrete calculational step. As a result, a time-depen-
~w~J+, & /dt (: 0 (natural process), (4)
dent series of intermediate “states” with known
chemical composition, temperature and pressure is cw,~, = 0 (equilibrium) (5)
obtained, the cakulation thus modelling the route of
where pg is the chemical potential of species B and the
a “natural process”. With known reactor geometries
affinity of the reaction is -&v,p,, .
as well as heat and mass transfer rates the method
If a system of any number of phases is considered
becomes a practical tool in reactor design.
at constant T and P (temperature and pressure), the
conditions are given in terms of the system’s Gibbs
2. THEORY energy (e):

The general chemical reaction is presented symbol- de = & dn,, -z 0 (natural process)
ically as follows:
(T, P constant), (6)

Cw,A -+ZwsB (1) de = GB dn, = 0 (equilibrium)

meaning that wA moles of A and the like react
together to give ws moles of B and the like. Following
the notation of Guggenheim (1977), symbols A and
B specify both the chemical species i and the phase a
in which they are present. Equation (1) can be
modified by collecting both the reactants and the
products on the right:
O=Zw,B (2)
(T, P constant). (7)
The mole numbers and the extent of reaction are here
related by the equality dn, = wg dE, or, more gener-
ally in a multireaction system with N reactions:
cl+, = c wBda,, (i = 1, 2, _ . , N).
i
Following Levine (1978), the reaction rate in terms
of unit volume V is r = (l/ V)(ds/dt) and can be

1157
I158
expressed with an experimental
coefficient k and the reactant
([AI, VI . . .):
r = k[A]"[B]b . . * [M]”
r = F(k, [Al, [S], . . . , [MI)
where s = Q + b + . - . + m is the order of the reac-
tion, and k is the temperature-dependent reaction rate
coefficient commonly following the Arrhenius
equation:
In k = In u - g/T.
Where u and #I are parameters defining the frequency
factor and reaction activation energy, respectively.
In the case of a single reaction, for which the
reaction rate is known, the time-dependence of
chemical change is given by (8). The reaction should
then proceed to equilibrium along (4) and (5). For a
change in a multi-phase system, (6) and (7) are valid.
In the calculation model presented in the following
it is assumed that equations (6). . . (8) are sequen-
tially valid in the reactive system. The overall reaction
rate is assumed to follow equation (8) during succes-
sive, short time periods of At. The reaction is then
suppressed, or “frozen” at constant T and P, to check
the corresponding minimum of the Gibbs energy of
the system by equation (7). For each intermediate
“state”, a calculational minimum following equation
(7) is received. After repeating the calculation to a
stage, where no more reaction takes place (de sz 0) a
series of intermediate “states” and the final (stable)
equilibrium state have been reached.
For each intermediate “state”, there is a corre-
sponding time value, derived from equation (8). This
then gives a simulated, time dependent reaction route
for the “natural process” obeying equations (4)
and (6).
3. HEAT BALANCE CONDITION OF THE REACTOR
ELEMENT
The temperature of the closed system reactor
element is discussed here in terms of an exothermic
multicomponent reaction, for which the actual model
has been developed.
The oxidation of a gaseous metal chloride is
usually an exothermic reaction taking place at high
temperatures above 900°C. The rapid dissociation of
the chlorine [Cl,(g)]-molecule, however, strongly
affects the temperature of the reaction mixture and
thus the reaction rate. The other salient factor is, of
course, heat exchange with the surroundings. Any
P. KOUKKARI
reaction rate calculation model of the reaction channel should thus
concentrations include the effect of both.
For titanium tetrachloride (TiCI,), the reactions
are:
(f-9
TiCl,(g) + 02(g)+Ti02(c) + 2C12(g), (i)
Cl,(g)+2Cl(g). (ii)
(9)
The enthalpy of the reaction for the overall oxidation
reaction is - 177 kJ/mol and for the chlorine dis-
sociation +250 M/m01 (lOOO°C).
The rate equation for reaction (i) was recently
given by Pratsinis er al. (1990):
(10) -d[TiCl,]/dt = (k + k’[0,]‘/3[TiCl,], (11)
where k and k’ are given in the usual Arrhenius form:
k = ,f - e(-GIR~
with numerical values of the frequency factors A, A’
and the activation energy E. known by experiments.
The time-course of the overall reaction (i) may thus
be derived. However, a simultaneous solution for the
extent of reaction (ii) would be necessary to end with
a correct enthalpy of the chemical change. Other
possible side reactions for the TiCl,-O,-system are
discussed, e.g. by Pratsinis et al. (1990), and have
been experimentally recorded by Karlemo et al.
(1992). Connected with the heat exchange of the
system and surroundings there then would be enough
data to reach a time-dependent temperature profile
for the reaction channel.
To combine both of these effects, it has been
assumed that the side reactions may reach equi-
librium and hence thermodynamic rules be applied to
these and the reactor heat exchange. Using this
assumption in pace with the gradual extent of the
overall reaction enables one to calculate a series of
thermochemical “states” along the time axis of the
reaction.
When calculating these intermediate “states”, it
remains to determine the temperature and pressure
for each step. A practical simplification is to consider
a constant pressure system. The enthalpy change in a
closed system 2 with reaction is thus:
dHZ = C, dT + c wiHi de (P constant) (12)
where C, = heat capacity of the system and Hi de-
notes the partial molar enthalpy of species i (Haase,
1969).
As the heat flow is dQ/dt = dH’/dt, when no work
is done on the system, this becomes:
C,dT/dt =dQ/dt -xwiHi&fdt. (13)
 Time-dependentreactionmixtures I159

Thus the temperture of the closed, reactive system is
controlled by the heat flow and the heat evolved by
the reaction. For the adiabatic case dQ = 0 and the
reaction endo/exothermicity reflects directly the tem-
perature of the system.
Tbe adiabatic approach often leads to approxi-
mations with certain limited practical values. Results
from the adiabatic calculation are illustrated in
Fig. 1. The curves give the reaction rate pattern with
different Arrhenius parameters, as received from
equation (11) in an adiabatic reaction channel for the
stoichiometric reactant mixture.
The heat transfer rate is obtained by either calcu-
lation or measurement, e.g. for a tubular flow reactor
it is often possible to reach the measured Q-values.
The closed system may then be treated as a steadily
moving reactive element, proceeding through the
known reactor tube. Combining a rate pattern for the
tubular flow, known reactor geometry and dQ/dt-
values based on measured or calculated heat flows, a
more realistic picture of the reaction history may be
obtained.
to reach the system composition for the intermediate
reactor “states”.
Solgasmix was originally developed by Eriksson
(1971). The search of the Gibbs energy minimum is
realized in terms of the mole numbers of the system
components, which satisfy the overall mass balance
constraints of the closed system. Lagrange’s method
is used with the mass balance relations as subsidiary
constraints. Here, for simplicity, a system consisting
of an ideal gas phase and a number of pure, con-
densed phases is considered. The system Gibbs energy
is then given in terms of substance mole numbers and
chemical potentials:
The mass balance constraints for the system are:
In (14-15) Gz is again the system Gibbs energy and
pi the partial molar Gibbs energy of a substance, the
rest of the notation is as explained below:

4. MASS BALANCE CONDITIONS FOR THE GIBBS

ENERGY MIMMIZATION
Multicomponent equilibria as a rule are calculated
by extremization methods (Hillert, 1981). One of the
most widespread of these is the well-known Solgas-
mix, which involves the minimization of the Gibbs
free energy at constant temperature and pressure
(OTT, 1992; Sippola et al., 1992). The true equi-
librium composition of a multicomponent system is
received. For the present method, a modification of
the Solgasmix mass balance relations was examined
nf = mole number of a substance in phase q.
au= number of atoms of the ith element in a
molecule of the ith substance (element of
stoichiometrical matrix in Solgasmix),
b,= the number of moles of the ith element,
I = total number of elements,
m, s = number of substances present at gas phase and
the condensed phases, respectively.
The search of the minimum of the Gibbs energy is
then subject to the mass balance relations as sub-
sidiary conditions. Using 5% as undetermined multi-

0.6

Reaction
rate,
mol/(l*s)
0.4 -

0.3 -

0.2 -

0.1

0
0 0.00!5 0.01 0.015 0.02 0.025 0.03

time, set

Fig. I. TiCI, oxidation kinetics. Adiabatic reaction rates.

1160 P. KOUKKARI

I
I
I hit:
SGM-INP

I
?
4 -& , p,*t
r
z

ul
I

K
I

R
0
IMRES
U
T
I
N Call . SGMTEMP:
E SGMTEMP ___ T, X, (q)ro

Define
Options

-
Fig. 2. Flowchart of the program RATEMIX.

pliers of the Lagrange method, the function becomes 6L/&, = 6, - C afnf - C a$nf = 0. (19)
(Eriksson, 1971):
As is mathematically plausible, additional constraints
may be taken into account in the minimization
procedure. This has been done, e.g. by Gupta et al.
(1991) to achieve a more effective algorithm for
+ixj b,--~a@z~-_aa;n; =L(n,x). (16)
( > simultaneous computation of the stability of phases
and the isothermal-isobaric multiphase equilibrium
The minimization of L(n,n) gives, equivalently, the
for reacting systems.
minimum of w/RT and thus the equilibrium number
To calculate a temperature-dependent series of
of moles of each substance at constant T and P. The
suppressed (or “frozen”) equilibria by Solgasmix a
derivation gives:
modification of the mass balance is needed.
The stoichiometrical input matrix of Solgasmix,
6L/6n$ = pf JRT - i njafj = 0, (17) describing the thermodynamical system to be calcu-
lated, may also involve chemical substances as “com-
BL/6n; = p;/RT - f: nja; = 0,
ponents of the system” (Eriksson, 1975; Forssberg
(18)
et al., 1986). These are then introduced to the matrix
 Time-dependentreaction mixtures 1161

T/Tmax

0.04
time, seconds
Fig. 3. TiCl, oxidation. Extent of reaction and T/T_,.

as columns in addition to or to replace the elements. here to introduce the reactive substance to the
The stoichiometric coefficients of the replenished matrix in the form of an inert component of the
matrix must be given correctly to match the overall system, which only gets consumed in pace of the
mass balance. The same approach has been utilized overall reaction rate.

0.05

KP, or

0.03

CPGI)l 2
CP(CW

0.01

0
0 0.5 1
Extent of overall reaction [E(TD)] by calculation
Fig. 4. TiCI, oxidation. Calculated Cl,-dissociation compared to equilibrium constant.
1162
2
Change
InTandS
1( E
-1- T/l-l
Extent of reaction (thermodynamic)
Fig. 5. Intermediate “reactor states”. Relative entropy change in the series of closed systems.
The “inactive reactant” always has to have the
actual reactive component present as a substance
counterpart among the rows of the matrix. During a
minimization step the former is “frozen” and does
not attend the reaction. In the subsequent calculation
the inactive reactant is then discretely transformed to
its reactive counterpart, which, obeying thermodyn-
amics, reacts during the minimization sequences to
give the respective products. Throughout the pro-
cedure, the inert “component of the system’* and the
corresponding reactive component have the same
thermophysical properties to match the calculation’s
energy balance.
Supposing that it is possible to add an inactive
reactant to either or both phases g and c, a modified
mass balance is received:
&)nl;+&‘,n+bf 0’=1,2,...1*)
m*=m+r8,
s* = s + r=,
rcc here denoting the number of reactants introduced
as additional “components of the system” in phases
g or c, respectively, and b* indicating the number of
moles of each “element” in the new system. As the
reactants are added to the system in the form of
inactive (inert) “elements”, the number of elements
P. KOUKKARI
.......... . . . . ........................................... ......... ...... .& ..____._.__
I
(I*) in the extended matrix of the suppressed system
becomes:
I* = I + rE -I- rc. (23)
The mass balance relation (20) is similar to the
relation (15). Thus, with analogous Lagrange ex-
pressions as those of (16-19) the minimization pro-
cedure remains formally untouched. The minimum is
reached either at the zero differential (dGa = 0) or as
an extreme value at the region boundary (Vaisala,
1971).
The additional condition to be fulfilled in the
calculation is the overall mass balance:
(25)
(20)
where mto, is the total mass and Mj the atomic or
molecular mass of the jth component of the system.
The total mass of the suppressed and the original
system of course must always be equal. From (24)
(21)
and (25) the mass-balance condition is then:
(22)
f: (bf - bj)M, = 0,
where bj = 0 when C <cj < I+.
This condition must be balanced between the mini-
mization sequencies of the calculation. In short, when
the inactive reactant becomes consumed, the corre-
sponding reactive substance must be increased in the
 Time-dependentreactionmixtures
Solgasmix input. This can be done by using a finite
difference related to the time increment AI and deter-
mined solely by the rate-determining kinetic
equation(s). The inactive reactant is thus consumed in
pace with the rate equation, and the suppressed
minima of the system Gibbs energy are received for
such intermediate “states’*, for which only part of the
reactant is allowed to react.
When the calculation proceeds to such a time
value, where no reaction exists any more, 6,*-+0 for
j > 1. At the final equilibrium state no inactive reac-
tant should be left and from (24) and (25) it follows:
b, = bf (j = 1,2, ___I; at equilibrium). (27)
The mass balance relations of (15) and (20), then
become equivalent for the real equilibrium position
Thus, due to the flexibility of the Solgasmix stoi-
chiometrical approach, it is viable to restrict the
“consumption” of reactive species in different phases
without affecting the mathematical form of the mini-
mization procedure. In case of a single reactant, for
which the reactant rate law is known, the system
modification is particularly simple (14 = l), and facili-
tates a yielding simulation of the effect of side
reactions and heat losses on the reaction history.
5. CALCULATION PROCEDURE
The computer algorithm (RATEMIX), is based on
the Arrhenius power law kinetics, known mass and
heat transfer estimates and on an iterative thermo-
dynamic routine, which searches the Gibbs energy
minimum of a closed system. It is assumed that
equations (6). . . (8) are sequentially valid in the
reactive system. The flowsheet of the routine is shown
in Fig. 2.
The TiCl,-O,(-TiO,)-system consists of some
18-20 substances, the thermodynamic data of which
is firstly compiled as Solgasmix-input. The reaction
starts at a given pressure and temperature. The
reactants (TiCl,, 0,) are typically present in their
stoichiometric ratio or with some percentage of excess
oxygen.
The overall reaction rate is assumed to follow
equation (8) [or, in this case, equation (ll)] during
successive, short time periods of At. This is done by
the subroutine RATE. For each instant of time ti, a
corresponding extent of reaction ci is received.
RATE is followed by an optional subroutine RE-
ACTOR, which is used to calculate the heat flow in
terms of measured Q-values or by known heat trans-
fer coefficients and the possible spatial co-ordinates
(Lj) in terms of the flow pattern and reactor
geometry.
1163
In the subroutine SGMTEMP the Gibbs energy of
the reactive system is then minimized, utilizing the
flexibility of Solgasmix’s stoichiometrical approach
as described above. The reactive system is “frozen” in
pace with the extent of the TiCl,-overall reaction (hi,
constant T and P). while the corresponding minimum
of the Gibbs energy of the suppressed system is cal-
culated. Before the itermediate “state” is accepted,
however, the heat balance given by equation (13) is
checked by an iterative temperature routine com-
bined to Solgasmix (Niemela and Koukkari, 1989).
The intermediate data is collected into a logbook
file (subroutine IMRES in Fig. 2 with X denoting any
quantity from SGMTEMP). After repeating the
sequential calculation to a stage where no more
reaction takes place (dE % 0) a series of intermediate
“frozen equilibria” and the final (stable) equilibrium
state have been reached. This may, yet, change with
temperature while heat removal goes on.
For each intermediate “state”, there is a corre-
sponding time value, derived from equation (8). This
then gives a simulated, time dependent reaction route
for the “natural process” obeying equations (4)
and (6).
6. CALCULATION RESULTS AND DISCUSSION
The computation of the “time-dependent inter-
mediate states” is, of course, subdued to some mod-
elling agreements. Those used with the above
calculational example are discussed here shortly.
The intermediate states as combined represent the
supposed virtual reaction route. The properties of
these “states” are unambiguous once the modifying
constraints on the mass balance relations have been
set. However, they are dependent on the choice of
these relations, as well as on the kinetic rate
equation(s) and the heat balance. The suppression
technique applied thus designates the modelling
agreements. The choice of constraints may yet be
verified against measured or thermodynamic data.
To reach an intermediate “state”, which would be
in pace with the overall kinetic reaction rate, the
amount of reactants must be sufficient for each
intermediate minimization. The procedure provides
that L,3 (6,)rD, which is the necessary condition. Thus
cir the extent of reaction received by the Arrhenius
rate equation in subroutine RATE, reaches unity
before (ci)rD , the thermodynamically allowed extent
of the overall reaction from subroutine SGMTEMP.
This is illustrated in Fig. 3. The latter then becomes
completed obeying strict thermodynamic rules when
heat is removed from the system. For further treat-
ment of the intermediate results, (ti)rD is consequently
the more interesting quantity.
1164 P. KOUKKAM
The search of the Gibbs energy minimum con-
dition is free for any side reactions, to which no
kinetic constraint is set. As the thermodynamic mini-
mization routine now involves the enthalpy balance
of the closed system, the side reactions become
accounted in the heat balance. In the case of TiCl,-
oxidation, the endothermic dissociation of chlorine
strongly affects the temperature of each intermediate
volume element and thus the subsequent overall
temperature profile (and reaction rate) received for
the reactor. In Fig. 3, curve 1 describes part of such
a T-profile, the squares indicating calculated inter-
mediate “states”.
The heat capacity of the system is controlled either
by using an inert substance as the suppressing
“dummy” component or by defining the inactive
reactant in the input matrix of Solgasmix. During the
calculation steps the inert substance must be replaced
with the actual reactive component in their heat
capacity ratio. The inactive reactant technique is yet
more general, e.g. in this example directly giving the
correct (ideal) gas volume for the intermediate reac-
tor elements.
The assumed instantaneous dissociation of chlor-
ine should yield, in the stoichiometric “RATEMIX”
system, a temperature-dependent dissociation degree
comparable to that of pure chlorine gas. This is
presented in Fig. 4 in terms of a calculated pressure
ratio [p(Cl(g))]‘/[p(Cl,(g))] from the intermediate
“states” and the tabulated thermodynamic equi-
librium constant (K,) for chlorine in the correspond-
ing temperatures (Barin et al., 1977; Roine, 1988).
The curves differ to some extent at higher tempera-
tures. In the “RATEMIX’‘-system, higher partial
pressures of different gaseous oxychlorides are found
at this temperature range. When (ci)rD~lr the K,-
ratio limits to zero following the overall reaction (i).
In this example, the side reactions were assumed to
be “fast”, that is, they take place within each finite
difference period At. If their reaction rates were to be
taken into account (and known by experiment), a
similar procedure as in the case of the overall reaction
could be applied. However, more complex systems
should deserve increasing attention towards the
physico-chemical significance of the calculated
results.
In the case of a thermally insulated system, the
Gibbs energy continuously decreases towards the
actual minimum value (equilibrium), which is finally
received as the result of calculation. For the closed
system, the heat balance rules any state function. In
Fig. 5, the relative change of entropy is shown for a
series of successive intermediate “states”, each calcu-
lated as a closed system with known heat flow to the
surroundings. The system experiences an exothermic
reaction and a simultaneous heat flow to the low-
temperature surroundings. The corresponding en-
tropy change within the system is positive while the
reaction exotherm exceeds the heat loss, and then,
with proportionally increased cooling, becomes the
(negative) isothermal entropy of the overall reaction.
The “RATEMIX”-method combines the exper-
imental overall reaction kinetics to the supposed
“frozen equilibria” of a reactor process. Given the
overall Arrhenius power law reaction rate, the sol-
ution does not imply any specific reaction mechan-
ism. The general kinetic mechanism, if known, would
result with the time course of the reaction (Alberty,
1991). Yet the calculation of intermediate “states” as
described above, also provides time-dependent ther-
mochemical information in such a form that may be
experimentally verified. This information includes the
temperature-, enthalpy- and composition profiles
for a steady-state reactor, which, of course, are of
practical importance.
AcknowledPements-To Kemira Ov (Academy of Industry).
to Dr S. Liikkonen and Dr J. Rasiai at Helsinki Univers&
of Technology, Laboratory of Physical and ElectroChem-
istly.
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 Time-dependent reaction mixtures 1165

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