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916 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 31, NO.

7
For example, the latent heat of vaporization can be calcu- published. The information developed in this investigation
lated from the vapor pressure equation and the saturated will therefore become generally available in a form readily
liquid and vapor densities. The same quantity can be ob- usable for engineering work.
tained by calculation of the heat content of the saturated
vapor by means of the equation of state, the heat capacity Aclrnowledgment
of the gas a t constant pressure of one atmosphere, and the
heat capacity of the liquid. If this is done, the agreement The authors wish to acknowledge the assistance of W. H.
between the two sets of heats of vaporization will be a measure Markwood, Jr., and W. J. Smith in performing some of the
of the over-all consistency of the experimental work. Figure experimental work-the former for measurements of the
8 shows the change of this quantity with temperature calcu- heat capacity of the liquids and both for some measurements
lated by the two largely independent methods. The solid of the heat capacity of the vapors. They also wish to ac-
lines represent the heat of vaporization calculated from the knowledge the assistance of F. B. Downing, of the Jackson
Clausius-Clapeyron equation; the dotted lines show the same Laboratory, E. I. du Pont de Nemours & Company, Inc.,
calculation from the heat capacity measurements of both the whose advice and criticisms were available during the entire
liquid and vapor as well as the equation of state. The agree- prosecution of this work.
ment is found to be good, considering that all the errors which
may have entered into the work would tend to accumulate Literature Cited
in this one property. (1) Beattie, J. A., and Bridgeman, 0. C.,
J. Am. Chem. SOC.,50,
The mutual agreement of the physical and thermal prop- 3133-8 (1928).
erties, together with consideration of the normal behavior of ( 2 ) Bichowsky, F. R., and Gilkey, W. K., IND. E m . CHEM..23,366-7
(1931).
these compounds, as shown by the linearity of the rectilinear (3) Buffington, R. M., and Fleischer, J., Ibid., 23, 1290-2 (1931).
diameter, the Trouton constants, and the independent checks (4) Buffington, R. M., and Gilkey, W. K., Ibid., 23, 254-6 (1931).
of the methods on materials whose properties are accurately (6) Buffington, R. M., and Gilkey, W. K., Ibid., 23, 1292-4 (1931).
known, leads to the conclusion that the information de- (6) Cope, J. Q., Lewis, W. K., and Weber, J. C., Ibid., 23, 887-92
(1931).
veloped in this study is of a reasonably high degree of a?- (7) Gilkey, W.K.,Gerard, F. W., and Bixler, M. E., Ibid., 23,364-6
curacy. It appears to be sufficiently complete to more than (1931).
justify use of the data for all normal engineering needs. (8) Midgley, T.,Jr., and Henne, A. L., Ibid., 22,542-5 (1930).
It is expected that detaiied and complete reports of this PRBSZNTZD before t h e Division of Industrial and Engineering Chemistry at
work will appear in the journals of this society and that com- t h e 96th Meeting of t h e American Chemical Society, Milwaukee, WIR.
plete thermodynamic tables for these compounds will be Contribution No. 1 from Kinetic Chemicals, Inc.

Relation between Catalvtic J

*Activityand Size of Particle


E. W. THIELE
Standard Oil Company (Indiana), Whiting, Ind.

A FEW heterogeqeous catalysts (for example, the plati-


num wires used in the oxidation of ammonia) consist of
dense, massive metal. In other cases the catalyst
exists in the form of a sol. More commonly, however, the
tend to become proportional to the external surface of the
grains (or lumps). There appears to be little or no published
information on this point. Rideal and Taylor (4) assume
that a reduction in grain size will regularly be accompanied
catalyst is in the form of more or less porous grains, ranging by an increase in catalyst activity per unit weight of catalyst.
from powder size to good-sized pills, often artificially made. Since the size of the catalyst grains is a practical matter of
I n general, it appears to be tacitly assumed by workers in some importance, it seemed worth while to treat the matter
this field that the reacting fluid penetrates to the pores in the mathematically, with a view to determining the factors that
interior of the grains and maintains substantially a constant will be of importance and to developing a means of predicting
composition throughout all the pores of a single grain, which the effect of varying grain size on activity. Although a number
is the same as the composition of the bulk of the fluid bathing of simplifying assumptions were necessary, the results ob-
the grain at the time. It was actually demonstrated in tained seem to give a correct idea of the influence of various
certain cases (1, 2) that further subdivision of the grains pro- factors, although it was not found possible to determine the
duced no change in the catalytic activity. behavior of catalysts in this respect independently of experi-
Qualitatively, however, it is evident that the size of the ment.
grains cannot be indefinitely increased without ultimately The treatment is also applicable to cases like the water-gas
reaching a point a t which the reaction will produce products reaction where a gas reacts with a porous solid. In this case,
in the interior of the grain faster than diffusion can carry them however, the porosity changes with time, so that some addi-
away. The reaction will then tend to be confined to the outer tional factors are introduced, and the results apply only
layers of the grain, the interior being relatively inactive. As during a short period or where there is a countercurrent flow
the grain size is further increased, the catalytic activity will of fluid and solid. The modifications introduced in this case
JULY, 1939 INDUSTRIAL AND ENGINEERING CHEMISTRY 917

(where the solid is used u p in the reaction)


are not further discussed in the present
work.

Results of Calculations
Details of the calculations are given in a
subsequent section, but the results will be
presented here. The quantity to be deter-
mined is the ratio of the reaction rate with a
given grain size to the reaction rate that
would be observed if the composition of the
fluid throughout the interior of the grain were
the same as in the fluid surrounding the grain;
in other words, it is desired to determine the
reaction rate as a fraction of the rate that
would be observed with the same amount of
catalyst divided into infinitely small grains.
If the reaction is kinetically of the first
order, the ratio in question depends on the
dimensionless modulus, 2, - d ( c / k r ) ,

where xa some linear dimension fixing the grain


=
size (for example, the radius of the -Mol Fraction = 0.4
equivalent sphere) -Mo/ f r a c t / o n = O J
IC = coefficient of diffusion of the reactants
through the fluid
T = average area of pore cross section
per unit length of perimeter of pore
cross section (hydraulic radius of
pores)
c = activity of the pore surface
FIGURE
1

A mathematical treatment, based on rea- CASE11. First-order reaction, no change in volume, catalyst
sonable assumptions, indicates that below a in spherical grains; z =, radius of the grains.
CASE111. Second-order reaction, no change in volume, cata-
certain grain size the activity of a porous lyst in flat plates.
catalyst is proportional to the amount pres- CASEIV. First-orderareaction, catalyst in flat plates, reac-
tion accompanied by a change in volume. In this case the mole
ent. If the grain size is increased much fraction of the reacting substances in the body of the fluid greatly
above this value, the activity will depend affects the results. Several cases have been worked out:
a. Reaction doubles the volume; mole per cent of reactant
on the total external surface of the grains. in the fluid 100 per cent.
The dividing region between these two b. Reaction doubles the volume; mole fraction 40 per cent.
c. Reaction halves the volume; mole fraction 100 per cent.
conditions is determined (for a first-order d. Reaction halves the volume; mole fraction 50 per cent.
reaction) by a dimensionless quantity
x s d m , where x, is the radius of the The first three cases are shown in the upper part of Figure 1;
grains, c is the activity of unit internal case IV is shown in the lower part. All the curves have sub-
stantially the same trend. For values of the modulus much
surface of the pores, r is the hydraulic ra- smaller than unity, the relative reaction rate is nearly un-
dius of the pores, and k is the diffusion co- affected by changes in the modulus (which would arise, other
efficient. If consistent units are used, things being equal, from a change in the catalyst grain size xJ.
the transition values of the modulus do not For values of the modulus much greater than unity, the rela-
differ greatly from unity. tive reaction rate falls off inversely as the modulus and is
therefore proportional to the external surface.
Although numerous other cases might arise, most of which
would not be amenable to mathematical treatment, the curves
It may happen that in addition to a system of larger pores, for the cases studied are so similar that in all cases the results
the catalyst has a finer system of a smaller order of magnitude. would probably be substantially similar to those shown.
In this case r refers to the larger system only, and c is the Unfortunately the quantities c and r are not directly de-
activity based on the surface of the larger pores. terminable, so that it will not be possible t o compute in ad-
vance the effect of grain size in any given case. However,
If the reaction is second order, the modulus is z 8 d m - , for any given reaction under given conditions of temperature
where ye is the concentration of the reactant in the body of and pressure with a given catalyst, there will be a certain
the fluid. This quantity is also dimensionless; for a second- grain size below which the catalyst volume will tend to con-
order reaction, c has different units from those for a first-order trol the rate of reaction, and above which the catalyst external
reaction. The following cases have been considered : surface will tend to control. A knowledge of this size, which
should be determinable experimentally, will help in determin-
CASE I. First-order reaction not accompanied by a change in
volume, catalyst in flat plates; z = one half the thickness of the 8 ing the optimum size of catalyst for any given process and
plates. fuinish additional insight into the character of the catalyst.
918 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 31, NO. 7

Since wide variations in the quantities making up the modulus In the following sections, various cases are treated which are
may be expected, it seems likely that in a great many cases manageable mathematically and which give an insight into
this critical size will be outside the practical range of sizes. the relations involved.
One important consequence of the discussion relates to the
, effect of temperature. A rise in temperature will greatly in- Derivations for Case I
crease e. Suppose the modulus is large and let c increase The conditions are a single pore (or flat plate of catalyst),
fourfold; then the modulus will double and the relative rate no change in volume on reaction, and first-order reaction.
of reaction will be halved, so that the increase in observed Figure 2 shows a section of catalyst bathed in fluid on both
reaction rate will be only twofold instead of fourfold. If, sides, and a single pore through the catalyst. The reacting
therefore, the catalyst grain size is such that the reaction rate substance is assumed to be converted into another (or others)
is proportional to the external surface, then the activation without substantial change in volume. This may arise in a
energy of the reaction will appear to be abnormally low. gaseous fluid, because the number of moles on the two sides
However, the same thing might happen when the modulus is of the equation is the same, or because the reactant is diluted
small, if a small (second-order) pore system exists in which with a large amount of inert gas. Liquids will in general not
most of the reaction takes place. This point has been con-
sidered by Schwab and Zorn ( 5 ) .
It is also obvious that where successive reactions occur,
large values of the modulus will tend to give a different prod-
uct composition from those for small values, for a given
amount of the primary reaction; but a quantitative treat-
I ccYta/yst
I

ment of this case is quite difficult.


A derivation of the equations on which the curves are based
follows.

General Assumptions
The fluid may be either liquid or gas but not a mixture of
the two. Attention is fixed on an individual portion of
catalyst, bathed in a fluid of constant composition (this is
substantially the case where a flow process is used).
Heat effects are not considered. The temperature is as-
sumed to be uniform throughout the grain, but not necessarily FIGURE2
throughout the catalyst bed.
The greater part of the surface available for reaction is change greatly in volume on reacting. Since the back re-
assumed to be on the walls of the pores in the catalyst. The action is assumed negligible, products may be present, but
actual external surface is assumed to be negligible in com- only the concentration of the reacting substance is important.
parison. I t is obvious that there may be all degrees between It is assumed that it reacts a t a rate proportional to the con-
smooth platinum or nickel and a very porous material; in centration of one constituent; if there are other reactants,
general, however, the above requirement is realized. their concentration does not affect the rate.
Diffusion through a surface film is very fast compared to It is evident that the results obtained will be applicable to
diffusion into the grain interior. This is usually a safe as- catalysts in the form of flat plates, which will contain many
sumption since surface films are normally very thin. Lau- pores similar to that shown.
pichler (3) finds this to be the case for the catalyzed water- In the following nomenclature the dimensions of the quanti-
gas reaction. In the case of the combustion of coke (6) this ties are given for illustration, but any other consistent units
is not the case, but most catalytic reactions are much slower. may be used:
The pores in the catalyst grain are interconnecting, and
the diffusion of reacting gases and products takes place Let z = distance from center line of catalyst, measured along the
pore, em.
through these pores and not through the solid catalyst. za = distance from center to surface of catalyst, measured
It is not necessary to make any hypothesis as to whether along the pore, cm.
the reaction actually occurs on the walls of the pores. In ?/ = concentration of reactant in the fluid in the pore at point
2, moles/cc.
addition to the network of pores of the largest size, the walls ya = concentration of reactant in the body of the fluid at the
of the pores may exhibit a much finer network of cracks, catalyst surface, moles/cc.
within which most of the reaction actually occurs. It is c = rate of reaction, in moles per see. per sq. cm. of catalyst
necessary to consider only the largest type of pore and to pore surface, per mole per cc. of reactant Concentration,
specify the rate of reaction per unit area of wall of these cm./sec.
k = coefficient of diffusion of reactant in moles per sq. em.
pores, even though the reaction occurs mainly within pores of per sec., per mole per cc. of concentration, per om. of
the second or third order. length, sq. cm./sec.
The pores of the first order need not be straight or round, r = area of pore cross section per unit length of perimeter of
pore cross section, em.
but it is assumed that the ratio of the periphery to the area of a = a r e a p o r e cross section, sq. cm.
all cross sections is constant for each pore and the same from h = d(c/kr)
pore to pore. This amounts to assuming an average value
for this quantity. I t is to be expected that the pores will not Consider an infinitesimal section of the pore of thickness
be very much longer than the shortest dimension of the grains. dz (Figure 2). The concentration of the reactant decreases
This is not assumed; it is assumed, however, that the length toward the center of the pore. Since conditions are sta-
of the pores is proportional to this dimension. tionary, the amount of reactant diffusing to the left through
There is no draft or mass flow through the catalyst grains, the right boundary of the section is greater than the amount
all transfer being by diffusion, or resulting from a change in similarly diffusing through the left boundary by the amount
volume during reaction. of reactant disappearing by reaction on the walls of the pore
The reverse reaction is negligible in rate. section.
JULY, 1939 INDUSTRIAL AND ENGINEERING CHEMISTRY 919

The amount passing through any section by diffusion is


ka dy/dx. The difference between the amounts passing the
and
ka, (2) 6 =
1
ka,hya (tanh (hx,) hx,
‘ two sections is: The whole area of the pore walls is equal to
kad ( d y l d x ) (1)
The area of the walls of the section of pore is adx/r. The
amount of reaction on this surface is:
and the whole reaction per unit time when y = y8 throughout
acydxlr (2)
the grain will be ca,ysxs/3r. The ratio of the actual reaction
Equating the two quantities: to this will be
d / d x (dy/dx) = c y / k r
d2yldx2 = c y / k r = h2y ”(
hx,
1
tanh (hx,)
- )’hx8
.4t the center of the pore the flow by diffusion must be zero which is the formula used for the curve for case 11,Figure 1.
by symmetry. Therefore d y / d x = 0 when x = 0. Also
y = y8 when x = 2,. With these conditions the solution of Derivations for Case I11
the above differential equation is:
The reaction is second order; otherwise the conditions are
cosh (hx)
Y Ys ( e hehx
r , + e-hz,
+ ) = cash (hxs)
the same as in case I. The nomenclature will be as in case I.
There may be only a single reactant or two reactants present
The total amount converted by one half pore in unit time in stoichiometrical proportions. The symbols y and y, refer
is equal to the amount diffusing into one entrance of the pore to the concentration of the single reactant or of the stoichio-
in that time, or ka (dylclx),. This can be computed to be metrical mixture. The symbol c is defined as the rate of
kahy, tanh (hx,). The same result can be obtained by con- reaction, in moles per second per sq. cm. of catalyst pore sur-
sidering that the amount of reaction per unit area a t any point face per (mole per e ~ . of) ~reactant concentration, (3111.4 per
in the pore is equal to cy, so that the total in the half pore is: mole second.
The derivation is similar to case I, and the differential
equation is:
ydx
d2y/dx2 = h2y2

It is evident that if there were no effect of pore size, y In this case i t is desirable to state the limits somewhat dif-
would equal ys throughout the pore, and the total reaction ferently-namely, that d y / d x = 0 when x = 0, and that y =
per half pore in unit time would be acy,x,/r. When the yo when x = 0. The integration of the equation will give y p
actual rate of reaction is divided by this, the result is as a function of x,. From the above equation:
tanh (hx,)/hx, dyldx = h 4- (3)
which is the formula used for the curve for case I (Figure 1). The integral of this equation with the limits stated above is
Derivations for Case I1
the following: Sf7hen yJy0 is less than 1 + 4%
Conditions are the same as in case I except that the grains
are spherical.
The nomenclature for this case will be the same as for case
I, except that a in this case will be the area of the cross section
of all the pores a t distance z from the center, and therefore
variable. As the center is approached, the number of pores
(all having the same value of r ) will decrease in proportion to
the area of the shell of radius x.
In place of Equation. 1 we must write: xsh fi =
kd (a d y l d x ) = k ( d y l d x ) da + kad ( d y l d x )
But a = 4 m x 2 and da = 8wnxdx = 2a dx/x,where n is the
fraction of surface occupied by pores. Hence:
-
2ka d y dx + kad (
(&) 2)= acydx/r
X (5)
where F is the elliptic integral of the first kind, and K is the
complete elliptic integral of the first kind.
As before whtn x = 0, d y / d x = 0; and when x = x,, In determining the total amount of reaction, it is convenient
y = ya, The solution of this equation is: to start with Equation 3, noting that the total reaction
xs
” 2 (e..
ehx
8
- e-hx
- e-hza)
ysxs sinh (hx)
= z sinh

As in case I the amount of reaction is ka,(dy/dx),, where


(hxJ equals Ly xa cay2dx

half pore (ca/rh)


. This gives for the total reaction in the
4%4- The amount of reaction
for constant composition throughout the pore is cayszxs/r, and
a, is the whole pore area on the external surface of the spheri- the ratio of these quantities is:
cal grain. Bv.‘
- (21:Es) 164 ; - (31
hxa
[1 (6)
920 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 31, NO. 7
Expressions 4, 5, and 6 involve the quantity ys/yo. The
curve for case I11 in Figure 1 was determined by assuming
simple. It is convenient to put q = In - + 1) so that
(7
various values for y,/yo, and computing values of x , h G
from expressions 4 or 5. Then from these values and the
corresponding values of ya/y0, expression 6 was computed.
I n Figure 1, h x , f i is used as modulus. Since the quantity l / ( e g - e--q - q +
qo) becomes in-
finite for q = qo, use is made of the fact that for values of q
Derivations for Case IV near qo, the equation becomes nearly equal to
Reaction products differ in volume from reactants, It is
evident that there will be mass flow into the pores if the re-
action is accompanied by contraction and out of the pores if
it is accompanied by expansion: which may be integrated analytically.
Let t = total number of moles per cc. in the fluid
m = additional volumes of material formed for each volume
-
The total amount of reaction will be my?: t ( %).a

of the rate-controlling reactant that reacts


w = rate of mass flow outward at point x per unit area of
pore, cc./sq. cm./sec. (this is variable and may be
negative)
The other symbols are the same as for case I. Hence the total amount of reaction in unit time is
I n Figure 2 the net moles of the rate-controlling reactant
passing to the left past any section are equal to the amount kat (-J-)~
dq As in case I the total reaction in unit time, with
brought in by diffusion less the amount pushed out by the constant composition throughout the pore, would be acyexe/r.
mass flow resulting from increase in volume. This is ka dy/dx The ratio required is therefore (after substitution from
- wya/t. But the total amount of mass flow to the right is Equation 7)
equal to the amount of reactant passing to the left, multiplied
b y m. Hence:
m (ka d y l d x - wya/t) = wa This quantity depends on y,/t, which is the mole fraction of
Solving this equation, the rate-controlling constituent in the body of the fluid. It
also depends on m. Hence there will be a separate line for
‘w = ““(L) each value of each of these quantities.
dx m y + t The curves (Figure 1) show the values for the cases m = 1,
and the net moles of reacting substance passing any section y,/t = 1; m = 1,y,/t = 0.4; m = - l / ~ , y J t = 1; a n d m =
equal (by substitution) : --l/Z, y./t = 0.5. The curve for case 1, which is equivalent
to m = 0, is also shown. As y 8 / t decreases, the curves ap-
--
kat d y
my + tax
proach that for case I, as would be expected from physical
considerations.
Considering as before a differential section of the pore, and In computing the curves, m is fixed. Then various values
equating material left in the section to material reacting on of yo/t are assumed, and by graphical integration of Equation
the walls, 7 a relation between q (and therefore y / t ) and hx is obtained.
For given values of hx8 and corresponding values of q. and
y J t the required ratio is computed from Equation 8.
Literature Cited
(1) Cawley and King, Dept. Sci. Ind. Research (Brit.), Fuel Research
Paper 45 (1937).
The limits are as in case 111. This gives: (2) Juliard, Bull. S O C . chim. Belg., 46,587 (1938).
(3) Laupichler, IND. ENO.CHEM.,30,583 (1938).
(4) Rideal and Taylor, “Catalysis in Theory and Practice”, 1st ed.,
1919.
(5) Schwab and Zorn, 2. physik. Chem., 32B,197 (1936).
(6) Walker, Lewis, and McAdams, “Principles of Chemical Engi-
neering”, 1st ed., p. 200 (1923).
It does not appear feasible to integrate this equation in PRESENTED before the Division of Petroleum Chemistry at the. 96th Meeting
terms of known functions, but graphical integration is fairly of the Amerioan Chemiaal Society, Milwaukee, Wis.

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