(5) Heerden, C. van, Conference on Fluidization Technology, Soc.

Chem. Ind. (London), June 1952.

(6) Heerden, C. van, Nobel, A. P. P., and Krevelen, D. W. van,
Chem. Eng. Sci., 1, 51 (1951).

(7) Heerden, C. van, Nobel, A. P. P., and Krevelen, D. W. van,

(8)
(9)

(10)
(11)

General Discussion on Heat Transfer, Inst. Mech. Engrs.

(London) and Am. Soc. Meoh. Engrs. (1951).
Jolley, L. J., Fuel, 28, 114 (1949).
Leva, M., General Discussion on Heat Transfer, Inst. Mech.
Engrs. (London), and Am. Soc. Mech. Engrs. (1951).
Leva, M., and Grummer, M., Chem. Eng. Progr., 48,307 (1952).
Leva, M., Grummer, M., and Weintraub, M., Ibid., 45, 563
(1949).

(12) Levenspiel, O., and Walton, J. S.,Chem. Eng. News, 27, 1999
(1949).
(13) Logwinuk, K., thesis, Cae Institute of Technology, 1948.
(14) Mickley, H. S., and Trilling, C. A,, IXD.EKG.CHEM.,41, 1135
(1949).
(15) Philips Tech. Ret., 11, 91 (1949).
(16) Vreedenberg, H . A , , Conference on Fluidization Technology,
Soc. Chem. Ind. (London), June 1952.
(17) Vreedenberg, H. h., General Discussion on Heat Transfer,
Inst. Mech. Engrs. (London) and Am. Soc. Mech. Engrs.
(1951).
RECEIVED
f o r review January 3, 1953.

ACCEPTEDMarch 30, 1953.

Autothermic Processes
Properties and Reactor Design
C. VAN HEERDEN
STAATSMIJNEN IN LIMBURG, GELEEN, THE NETHERLANDS

1 n autothermic processes t h e temperature level a t which the reaction proceeds is maintained

by t h e heat of reaction alone, It is shown in this paperthat these processesare characterized
by a simple diagram consisting of two curves which give the production and the consumption of heat as functions of some reference temperature. From this diagram t h e typical
need of a n ignition by external heating being t h e
properties of autothermic reactions-the
most peculiar o n e - c a n easily be understood. This type of diagram i s indispensable for
t h e calculation of industrial converters i n which autothermic processes are carried out.
As a n illustration of t h e principles involved, the temperature and t h e concentration distributions i n a n ammonia synthesis converter are calculated.

HEN the temperature level a t which an exothermic chemi-

cal reaction proceeds is above room temperature, this level

is often maintained by the heat of reaction alone. The combustion of fuels belongs to this group of autothermic processes. Besides, it is common practice in chemical industry to make a conversion proceed autothermically if possible, in order t o avoid expensive heating by external means. Well-known examples are
the Haber-Bosch ammonia synthesis and the shift-reaction of
carbon monoxide with steam.
I n these processes a steady state must be established a t which
the heat consumption is balanced by the heat production. As
the rate of reaction generally varies very rapidly with temperature, the fractional conversion will change from near zero to near
unity within a relatively small temperature region. However,
the heat consumed-which mainly consists of the sensible heat of
the reaction products leaving the system and of the heat losses to
the surroundings-will change approximately linearly with temperature. From the general behavior of heat consumption and
heat production, the peculiar properties of autothermic properties can be easily understood. The most characteristic feature is
the necessity of an ignition by external heating before a steady
state a t which the reaction processes can be established.
r h e principles discussed in this paper are generally applicable
t o all autothermic processes and are applied to a practical example, the ammonia synthesis column.
GENERAL D I A G R A M

OF A U T O T H E R M I C PROCESSES

The simplest diagram of an autothermic process is shown in

Figure 1. It is assumed that the reaction proceeds isothermally
a t a temperature, T,, that the reaction products leave the reactor
a t the same temperature, T,, and that the reactants enter a t a
temperature, To, normally room temperature. For the moment,
it is assumed that t,he reaction also proceeds adiabatically, so t h a t
the heat consumed consists solely of the sensible heat of the

1242

reaction product. To simplify the discussion, all heat quantities

will be expressed per gram mole of a suitably chosen reaction
component.
At a given residence time of the reactants in the reactor, the
heat, QI,produced by the reaction will depend on the reaction
temperature in a way schematically represented by curve a in
Figure 2.
Starting a t low temperatures the reaction will a t first be so slow
that Q, is practically zero. ilt a certain temperature level the
reaction rate starts rising rapidly with temperature; as a result,
the heat produced will arrive a t a constant maximum value within
a relatively small temperature interval. When the value of Qr
remains constant the conversion is complete.
The heat consumption is given by the relation
&E

c(T,

- To)

where c is the heat capacity of the reaction products per gram

mole of one of the reaction components. If it is assumed that c
is independent of temperature and of the degree of conversion,
Qcis represented by a straight line, b, which intersects the temperature axis a t Ti.
At points of intersection 0, I , and S of curves a and b the production and consumption of heat are e,qual. A t point I this
equilibrium is unstable. With a small rise in temperature the
heat production increases more rapidly than the heat consumption and the temperaturewill continue to rise untila stableequilibrium a t ASis reached. In the opposite case of a small temperature drop a t I the temperature will continue to fall until it reaches
the value Toa t 0. Point I corresponds to a state of ignition and
Ti is the ignition temperature. The equilibrium a t 0 correspond
with the stable nonreacting state before ignition, while at the
temperature T , the stationary reacting state is established after
ignition by external heating t o temperature T,.
Of course it is possible for curves a and b to have no points of

INDUSTRIAL A N D ENGINEERING CHEMISTRY

Vol. 4.5, No. 6

intersection other than 0 (b' in Figure 2). This will occur when
the reaction is too slow or the heat of reaction too small. In that
case autothermic reaction is not possible.
One important property of autothermic reactions can be deduced from Figure 2. Because of the characteristic S-shape of
the heat production curve, the stationary state, S, will lie in the
region of almost complete conversion. This conclusion is in full
agreement with practical experience. For instance, when burning solid fuels the oxygen content of the exit gases is always very
low, and in flames either the fuel or the oxygen is completely consumed, even a t the
limits of flammability.
Stability of Autoreactants

thermic
Practical Reactions.
examples
of autothermic processes are normally
much more complicated than the

7
1Reo;;or

} -

Figure 1.
Simple Diagram
Autotherm io Processes

of

schematic approach
outlined.
Nevertheless, it is possible to draw some general conclusions from the diagram of Figure 2 about the way in which the stable state, represented by S, is effected by a variation in operating conditions,
The most important variable in this respect is the feed rate of
the reactants, If the feed rate is increased, the fractional conversion a t any value of the reaction temperature will decrease.
This means that curve a will shift to the right, while the constant value, approached a t high temperature, will remain the same
(see Figure 3). I n the absence of heat losses to the surroundings,
the slope of the straight line is independent of the feed rate. Thus,
a t a continued increase of the feed rate, curve a will ultimately
arrive at position a'. A t a still further increase a stable equilibrium no longer exists and the reaction cuts out.

and b" and a t a further decrease of the feed rate, the reaction will
be quenched.
Thus it can be understood t h a t for any autothermic process
there exist an upper and a lower limit for the feed rate. Beyond
these limits the reaction cannot proceed autothermically. Because of the rapid change of reaction rate with temperature, these
limits are generally very wide apart, while in the whole region
between these limits the conversion will be almost complete.
A typical example of quenching due to a too low value of the
feed rate is the extinction of a stove when the air is throttled
down too much. The blowoff limit of flames is an example of the
upper limit of feed rate.
Dilution of the reactants with-some inert component has an
effect similar to the reduction of the feed rate. If it is remembered that all heat quantities in Figures 2 and 3 are taken per
gram mole of one of the reactants, it is clear that the slope of the
heat consumption line increases proportionally with the degree of
dilution.
If it is assumed that the reaction is of the first order, the acurve will not change for a given value of the residence time.
Thus it follows that there is an upper limit of dilution above which
the reaction is quenched. Examples of this phenomenon are the
limits of flammability of a mixture of air and, say, methane.
Here too, the conversion between the limits is almost completein poor flames the conversion of the methane fuel, in rich flames
that of the oxygen.
f

//

Tr

Figure 3.

Figure 2. Schematic Diagram of Heat Production

and Heat Consumption as Functions of Reaction
Tern peratu re

Consequently, there exists an upper limit for the feed rate of

autothermic processes above which the reaction is blown out.
If, on the other hand, the feed rate is reduced, curve a shifts to
the left and the conclusion might be drawn that a t a sufficiently
low feed rate every exothermic reaction can be carried out autothermically. Here, however, heat losses t o the surroundings
must be taken into account and a t very low values of the feed
rate these losses will outweigh the sensible heat of the reaction
products. In this region the slope of the straight line will increase and, because of the rapid change of reaction rate with temperature, this effect will ultimately outweigh the shift of curve a
to the left. The curves will finally arrive a t the positions a"
June 1953

Influence of Variation i n Feed Rate

Recovery of Heat. I n the preceding sections it was pointed

out that the main heat consumption is the sensible heat of the
reaction p,roducts leaving the reactor at the reaction temperature. It is possible to recover an important part of this heat by
heat exchange between the hot outlet and the cold inlet.
It can easily be shown that the amount of heat recovered in any
type of heat exchanger is approximately proportional to the temperature difference between flows entering the heat exchanger.
Thus, the application of a heat exchanger between inlet and outlet
of an autothermic process corresponds to a decrease in the slope
of the straight line, b, in the diagrams. Heat recovery may be
applied t o carry out a process autothermically, if this is impossible
without recovery of heat, and to heighten the stationary reaction
temperature, T,.
To carry out exothermic catalytic processes autothermically,
recovery of heat is very often necessary. The ammonia synthesis and t h e shift-reaction of carbon monoxide with steam belong
to this group. An example, where preheating of the feed with the
outlet gases is only applied to heighten the reaction temperature,
is the blast furnace.
Reactions Limited by Equilibrium Conditions. For reactions
in which a t the temperatures involved the chemical equilibrium

INDUSTRIAL AND ENGINETRING CHEMISTRY

1243

between reactants and reaction products limits the degree of

conversion attainable, the a-curve in the diagram will have a
different shape. As autothermic reactions are always exothermic,
at increasing temperature the equilibrium composition will shift
t o the side of the reactants. Consequently, a t high temperatures,
where the conversion is almost complete, the production of heat
will decrease and the a-curve will be of the shape shown in Figure 4.
Point S, corresponding to the stationary reaction state, lies on
the falling part of the curve and a reduction of the slope of the
heat consumption line, b, not only increases the reaction tempera-

@?\.g
~~

.O n

55
:g
CL"

c
0

7z

L
TO

Figure 4.

which means that the heat content of the outlet gases above the
inlet tempkrature equals the heat of reaction produced in the
column. This is approximately equivalent to the statement that
the temperature difference between inlet and outlet gases is proportional to the fractional conversion.
To facilitate the calculations, the following assumptions are
made:
1. There is no temperature difference between the catalyst
granules and the interstitial gas.
2. The temperature in the catalyst bed is constant in any
cross section of the converter.
3. As a consequence of the second assumption, the rate of
heat exchange between the ascending and descending currents of
gas is represented by an over-all heat transfer coefficient, U ,
which is constant throughout the converter. In the following
calculations this rate of heat exchange will be expressed in terms
C
of the height of transfer unit, H = 7 ,where C is the feed rate
Ila
expressed as heat capacity per unit time and a is the total heat
exchanging surface per unit of length of the converter.
4. The heat capacity of the gas is independent of temperature
and conversion; the temperature rise, 7, of the reacting gas
corresponding to the adiabatic formation of 1% of ammonia is
constant and equals 15" C.
5. The reaction velocity satisfies the well-known relation of
Temkin ( 2 ) .

Schematic Diagram of Reaction Limited

by Equilibrium Conditions

ture but also decreases the reaction yield. Thus, for those processes where this slope can be varied-for instance, by a variation
of the degree of heat exchange between outlet and inlet-it is
advantageous to choose the conditions such that the slope of b is
as great as possible (b' in Figure 4). Under these conditions, at
the limit of stability the conversion will reach its maximum.
This important point will be discussed more fully in the next section, which deals with the calculation of ammonia synthesis
converters.

catalyst bed
heat

tubes

exchanger

PRACTICAL APPLICATION

Calculation of Ammonia Synthesis Converter. The general

principles of the preceding sections may be applied to the calculation of the temperature and concentration distribution in an
ammonia synthesis converter. The main purpose of this practical example is to illustrate how the properties of this much
more complicated system can be completely understood from a
modified diagram like Figure 2 , and how the use of such a diagram is indispensable in technical calculations.
To simplify this calculation, it is based on the most simple construction of a synthesis converter, consisting of a cylindrical
catalyst vessel with a large number of countercurrent heat exchanger tubes inside (see Figure 5 ) . The cold nitrogen-hydrogen
mixture enters the column a t the bottom, Aon~supward through
the heat exchanger tubes and downward through the catalyst
bed, and leaves a t the bottom. The degree of heat exchange can
be varied by by-passing the upn-ard flow in the heat exchanger
tubes through a central tube of large diameter.
With some modifications the following calculation method can
also be applied to more complicated constructions, including the
use of a separate heat exchanger and the application of cold gas
injection somewhere in the top of the column.
The characteristic temperature distribution in a converter of
the type shown in Figure 5 is given in Figure 6. Following the
path of the gas stream, the temperature rises gradually inside the
heat exchanger tubes. I n the upper part of the catalyst bed
vihere the heat of reaction exceeds the heat removed by the cooling tubes, the temperature rises and passes through a maximum
value.
I n the lower part of the converter the reaction rate decreases
gradually, so that the bottom section mainly Serves as a heat exchanger. The process as a whole is assumed to be adiabatic,

1244

inlet
Figure 5.

Ammonia Synthesis Converter

The original relation of Temkin reads:

where I< is the equilibrium constant and IC the temperature-dependent rate constant. After some modifications, substituting
a nitrogen to hydrogen ratio of 1 to 3 and the temperature dependency of k , this relation can be written as:
dz

2.4 X 1012
= F(2,

T)=

+ z)(l

P-3/*(1

INDUSTRIAL AND ENGINEERING CHEMISTRY

20,000
-_
_ X

- z)'&

Vol. 45, No. 6

This relation was used in the numerical calculations in this paper,

where v is the linear gas velocity in the empty vessel and P is the
total pressure.
6. N o heat is lost t o the surroundings.
7. The numerical data are as follows:
12
Height of converter, L, meters
Diameter of converter, meters
0.7
Pressure, atmospheres
300
1to3
N Zto Hz ratio
%
1.5
Inlet "3,
50
Inlet temperature, O C.
Linear gas velocity in empty vessel, meters per
second
0.16
3
Height of transfer unit (H), meters
The value of the height of the transfer unit, H,was estimated
by a rough calculation, using literature data on heat transfer rate
in packed columns. The value of 3 meters must be considered
as the minimum value obtained if the column is operated a t its
maximum heat exchanging capacity. By-passing of the heat exr

of maximum reaction rate, T,, the temperature, To.lwhere the

reaction rate is 0.1 times the maximum rate, and

T,,O C.

0.02
0.05
0.10
0.15
0.20

950
760
650
590
540

T,,

c.

To.l,O C.

840
680
580
530
490

-L

Distance from top, x

Figure 6. Temperature Distribution in Synthesis Converter with Internal Heat Exchange

T , for

500
420
370
340
320

Mole
Fraction/M.
1.6
0.23
0 048
0 017
0.007

In the last column the maximum reaction rate a t T , is given,

Because of the complexity, of the function F ( z , Tz) an analytical solution of the Differential Equations 1, 2, and 3 is impossible. A numerical stepwise integration is the usual line of attack for this kind of problem.
However, besides the Differential Equations 1, 2, and 3, the
solution must satisfy the following boundary conditions (see
Figure 6):

Tl = To when x =

\Y

- at

dx

some values of z :

T2 = T I when x = 0

Outlet

dz

(4)
(5)

When solving such a problem by the method of stepwise integration, one starts a t one end of the column with given values of T I ,
TB,and z and integrates step by step until the other end is reached.
For the present problem this procedure is not possible, as the two
boundary conditions (Equations 4 and 5) are given a t different
ends of the column. Thus for x = L,z or Tz is unknown. For
2 = 0, temperature Tt ( T I = T 2 )a t the top of the column is unknown.
This difficulty was solved in the following way: Starting from
an arbitrary value of the top temperature, T t , at x = 0, the stepwise integration was carried out until x = L. It is clear that this
arbitrary choice will not lead t o the correct value TOof T I (2)at
x = L. The integration is repeated for a number of different
values of T,,and in this way the temperature difference between
the ends of the heat exchanger tubes, T 2 T I ( L ) = 9,as found
by stepwise integration, is calculated as a function of Tt.
The relation found is represented by curve a in Figure 7 and
the general shape of the curve can be understood easily.

changing tubes increases the value of the height of the transfer

unit. The results of these calculations will prove that the values
used are reasonable.
Starting from the above assumptions, the
concentration and temperature distribution
1000.
must satisfy the following differential equations:
800.

9 6oo.
I

I
400.

(3)

F(z, T z ) is a modified formulation of the re200.

action velocity, obtained from the original rate
equation of Temkin. After substitution of the
given conditions, F was calculated as a function
of T2 for a number of z values and plotted as a
set of curves with z as the parameter. The nuFigure 7.
mericalvaluesneeded ware found by interpolation.
For any value of z there is some corresponding temperature, T,,a t which the gas mixture
is in chemical equilibrium. Far below this equilibrium temperature the reaction rate increases rapidly with the temperature.
Approaching T , the function, F , passes through a maximum to
' 'become zero at T , and negative above T,.
The following tabulation, prepared for orientation purposes,
gives values of the equilibrium temperature, T,,the temperature

June 1953

Tt P U

Relation between 9 and Tt for Varying Height of Transfer

Unit

Because a t low values of Tt the reaction is slow, the temperature

difference, TZ T I ,remains small, and according to Equation 1
the total change, 9, in T1 during the integration will also be small.
For Tt = T,, the equilibrium temperature for the inlet gas, the
reaction rate is zero and T2 and T I are constant throughout the
integration. For a nitrogen t o hydrogen ratio of 1 to 3 and an

INDUSTRIAL AND ENGINEERING CHEMISTRY

1245

inlet percentage of 1.5% of ammonia, the equilibrium temperature equals 1080' C. Thus, in all calculated curves like t h a t in
Figure 7, 0 is zero for Tg = 1080" C. In the region between low
temperature where the reaction rate is practically zero and the
equilibrium temperature where the reaction rate becomes zero
again, the 0, Tt curves will show a maximum. For those points of
the $-curve which satisfy the condition 0 = Tt - Tothe corresponding solutions satisfy the boundary condition of Equation 5 .
This means t h a t curve a in Figure 7 must be intersected by
straight line b. The diagram of Figure 7 is then equivalent to t h e
diagram of Figure 4. Point of intersection 0 corresponds with
the nonreacting state, 1 with the state of ignition, and S with the
steady reaction state.

9 M ~

stability is reached and at still higher values autothermic reaction

is no longer possible. The temperature and concentration distributions a t H = 7.5 meters are given in Figure 9, and from a
comparison with Figure 8 it is clear t h a t it is much better to operate the converter a t the limit of stability. The temperature
level is then much lower and the outlet ammonia concentration
higher. The decrease in stability is demonstrated by the fact
t h a t the region PQ,where the reaction rate has a negative temperature coefficient, is much smaller in Figure 9 than in Figure 8.
These results are in complete agreement with practical experience. In practice, synthesis converters are always operated in
such a way t h a t some reference temperature-e.g., the temperature at the top of the column-is kept as low as possible, continuously taking care t h a t the reaction does not cut out.
The influence of a decreasing activity of the catalyst is illustrated in Figure 10. Here the a-curves are given for different
values of the catalyst activity, accounted for in activity coefficient, f, by which the reaction rate-F(z, T2)in Equation 3-is
multiplied. The curves in Figure 10 correspond with f = I, 0.5,
0.25, and 0.15 and were calculated with H = 3 meters. At this
value of H the limit of stability is reached for f = 0.15-that is,
for a catalyst activity about seven times lower than the original
900

700

OJ
0

Distonce from top (n-)

Figure 8. Temperature and Concentration

Distribution Corresponding w i t h Stationary
State, S, i n Figure 7
Reaction rate has negative temperature coefficient
between P and Q
Equilibrlum temperature T. corresponds with
local ammonia cAnceAtration, z

If 0 is multiplied by the heat capacity of the feed the equivalence between the diagram of Figure 7 and Figure 4 becomes more
direct. Yet the a-curve in Figure 7 does not correspond with the
heat of reaction, as it does in Figure 4, but with the heat transferred from the reaction space to the heat exchanging tubes.
Generally, it can be said that any specified problem will have its
own diagram, depending on the way in which the integration of
the differential equations is carried out. Such a diagram will
always consist of a n a-curve, giving some heat quantity determined by the reaction rate function and a b-curve, giving some
heat quantity determined by the boundary conditions, both as
functions of some reference temperature.
In Figure 8 the complete temperature and concentration distribution is given corresponding to the steady state, S, in Figure 7.
Moreover, the variation of the equilibrium temperature throughout the converter is given. From this figure it is clear that the
converter owes its stability to the fact t h a t for an important part
the reaction proceeds in the direct vicinity of chemical equilibrium, where (between points P and &) the reaction rate has a
negative temperature coefficient.
The complete calculation was repeated for higher values of the
H.T.U.-that is, for lower values of the heat exchanging capacity
of the converter. The resulting a-curves for H
6 and 7.5
meters are also given in Figure 7. 4 t H = 7.5 meters the limit of

1246

01
0

4
6
8
1
Distance from top (m)

Figure 9. Temperature and Concentration

Distribution Corresponding w i t h Stationary
State a t L i m i t of Stability, S', i n Figure 7
Reaction rate has negative temperature coefficient
between P and Q
Equilibrium temperature, Te, corresponds w i t h
local ammonia concentration, z

value. Comparing the limit of stability a t f = 1 with t h a t a t J

= 0.15, it was found that the top temperature increases from 400'
to 570" C., the H.T.U. value decreases from 7.5 meters to 3
meters, and the exit ammonia concentration decreases from 21.5
to 12%. These results are also in agreement with practice,
where because of the decreasing catalyst activity, the heat exchange capacity must be enlarged gradually. This is accompanied by a continual rise of the temperature level and a decrease
in the degree of conversion.
Finally, the results obtained with different catalyst activities
can be used aB an orientation about the influence of a change in
the feed rate. If it is assumed, t h a t the H.T.V. is independent of
the gas velocity (because H =

c;

-,Ua C

INDUSTRIAL AND ENGINEERING CHEMISTRY

V , and U

d.8,

this aa-

Vol. 45, No. 6

sumption is approximately correct), it can be deduced from the

Differential Equations 1, 2, and 3 t h a t an increase in feed rate is
equivalent with a proportional decrease in catalyst activity.

fixed beds. A paper on this subject will be published in the near

future, the contents of which may be found in the thesis of van
Loon (1).
NOMENCLATURE

1000.

= heat exchanging surface per unit of

= feed rate expressed as heat capacity

= activity coefficient, dimensionless

length of column

f7 I

per unit of time

800

""I

c
Ua

= height of transfer unit (H.T.U.), m.

= eauilibrium constant of the reaction

\\\

1 N~ + 3 H* + N H ~

2
reaction rate constant
height of column, m.
total pressure, atm.
quantity of heat produced, respectively, consumed per gram mole
of one of the reactants
Tt 1%)
U = over-all heat transfer coefficient
Figure 10. Relation between 6 and Tt for Different Values of Catalyst
5
= distance from the top of the colActivity
umn, m.
= linear gas velocity in empty catalyst
u
vessel, m./sec.
z
= mole fraction of ammonia, dimensionless
Thus the four curves of Figure 10 also apply by approximation to
0 16
= F(z, T ) = modified reaction rate function, m.-l
the conditions f = 1 and v = - meters per second. Again in
f
T = temperature, O C.
agreement with practice, it follows that a n increase in the gas
To = inlet temperature of reactants
velocity necessitates a n increase in the heat exchanging capacity
TI = temperature in heat exchanger tubes
T z = temperature in catalyst bed
and, consequently, operation at a higher temperature level.
T I = equilibrium temperature
T , = temperature of maximum reaction rate
CONCLUSION
To.r = temperature (<T,) where the reaction rate = 0.1 X
maximum rate
The elaborate calculations on the ammonia synthesis converT , = temperature of isothermal reactor
ters have proved t h a t the special features of this autothermic
T , = temperature of isothermal reactor at the steady
reaction state
process can be understood completely from the diagrams given in
Tt = temperature at the top of the column
Figures 7 and 10. Moreover, it is clear t h a t for practical calculaTi = ignition temperature
tions of this k i d these diagrams are indispensable. T h a t the
T
= temperature rise of synthesis gas at the adiabatic
results of these calculations are also in quantitative agreement
formation of 1% of NH, ( T = 15' C.)
iy
= temperature difference between top of the column
with practice is only a confirmation of the reliability of the reacand gas inlet
tion velocity relation of Temkin and of the correctness of the
H.T.U. values used.
LITERATURE C I T E D
It is remarkable that the elementary considerations given in
(1) Loon, W. van, dissertation, Delft, 1952.
this paper, which are essential for a right understanding of all
(2) Temkin, M., and Pyzhev, Y., Acta Physicochim. U.R.S.S., 12,
autothermic processes, have not been presented before.
327 (1940).
Another very important application of the principles involved
can be found in the combustion and gasification of solid fuels in
ACCEPTED
March 30, 1953.
RECEIVED
for review January 3, 1953.
k

=
L =
P =
QP,,=

Kinetics of Gas-liquid Reactions

Simultaneous Absorption and Chemical Reaction
R O B E R T H. P E R R Y

AND

R O B E R T L. P I O F O R D

UNIVERSITY O F DELAWARE, NEWARK, DEL.

N ORDER to,build gas absorbers of the smallest possible size

to accomplish a given separation, i t is advantageous to use as
a solvent a material which has a small equilibrium back-pressure
of solute. This, of course, increases the driving force and hence
the rate of mass transfer through the gas phase. One way in
which this lowered equilibrium partial pressure is often obtained
is by using a solvent which reacts with the solute material, destroying i t chemically when i t enters the liquid. One of the most
common industrial examples of this is the absorption of carbon
dioxide by ethanolamine solutions.
June 1953

It is possible t o choose as the reacting component in the 901vent a material whose speed of reaction with the solute is so
rapid t h a t the chemical solvent is completely depleted a t the
gas-liquid interface. I n this case, the mass transfer is increased
in a manner different from the gas-phase effect mentioned above.
While pure physical absorption occurs in the liquid near the interface as usual, the liquid-phase resistance is decreased, owing t o
the increased concentration gradient a s a result of the rapid liquidphase reaction.
Finally, it is often most advantageous to employ a reversible

INDUSTRIAL AND ENGINEERING CHEMISTRY

1247