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0.3 to 0.2 when Filons (3) method is used for data reduction. The authors are grateful to the National Science Foundation
At normalized frequency contents above 0.2 to 0.3, pulse for support of this work.
testing results are in excellent agreement with those obtained
by direct frequency forcing and mathematical model solution. Nomenclature
Excessive experimental pulse time, due to pulse tailing, was
the major cause of the inability to extend the dynamic fre- G = mass velocity of air, lb./(hr.)(sq. ft.)
h = convective conductance, B.t.u./(hr.) (sq. ft.) ( F.)
quency range using pulse testing techniques. MR = magnitude ratio
Pulsing temperature limits the high frequency results obtain- R = tube radius, ft.
able because the thermal capacity of the physical system r = variable radius, ft.
results in energy storage and therefore excessive pulse tailing or s = humid heat capacity, B.t.u./(lb.)( F.)
time duration. t = dynamic temperature, F.
T, = time duration of pulse, sec.
For a given pulse shape, the normalized frequency content u = local velocity, ft./hr.
does not appear to be affected by pulse amplitude or pulse i(w) = frequency content
strength. S(w), = normalized frequency content
For pulses of long time duration, the time duration rather x = axial distance, ft.
than rise or decay times was found to be the best criterion for
X = total wetted section length, ft.
predicting the relative normalized frequency content of the GREEKLETTERS
pulses. CY = thermal diffusivity, sq. ft./hr.
6 = time, hr.
Further Work p = density, lb./cu. ft.
4 = phase shift, deg.
Although many investigators have done an excellent job in w = frequency, rad./sec. or cycles/hr.
advancing the methodology of pulse testing to its present state,
there is still a need for further refinement and improvement. literature Cited
Although the method appears to be adequate for the dynamic
(1) Bruley, D. F., Prados, J. W., A.Z.Ch.E. J. 10, No. 5, 612
analysis of most physical systems, difficulties might be encoun- (1964).
tered in special cases such as the one discussed. (2) Clements, W.C., Jr., Schnelle, K. B., Jr., IND.ENG.CHEM.
Further studies on in-plant pulse-generating techniques along PROCESS DESIGN DEVELOP. 2,94 (1963).
(3) Filon, L. G.N., Proc. Roy. SOC.Edinburg 49, 38-47 (1928-29).
with studies concerning pulse types (one-sided, two-sided, (4) Hougen, J. O., Experiences and Experiment with Process Dy-
multiple, etc.) and their characteristics with respect to nor- namics, Chem. Eng. Progr. Mono. 60, No. 4 (1964).
(5) Middleton, R. C., Pulse Circuit Technology, pp. 11-13,
malized frequency content could be helpful in the practical Bobbs-Merrill, New York, 1964.
application of pulse-testing techniques. Also there is a need
for review April 4, 1966
RECEIVED
for further study of existing data reduction schemes with the ACCEPTED January 9, 1967
intent of improving present methods or developing new ones.
59th National Meeting, American Institute of Chemical Engineers,
Studies of the above nature are at present in progress a t Columbus, Ohio, May 1966. Study carried out under NSF
Clemson University. Contract GP-3027.
UMEROUS kinetic studies of alcohol-acid esterifications desirable high yield. A number of conclusions developed from
are cited in the literature. Goldschmidt (6) developed previous studies:
a n equation which related the rate constant to the initial Organic acid-alcohol esterification is catalyzed by a strong
reactant acid concentration, ester concentration, catalyst mineral acid.
concentration, protonated alcohol concentration, and time. The rate constant is a function of catalyst concentration,
He tested the equation for a number of esterification reactions temperature, and alcohol-acid molar ratio.
The equilibrium constant is strongly influenced by the al-
a t 25 C. and found it successful in obtaining the rate constant. cohol-acid molar ratio, weakly influenced by temperature,
Smith (74, 75) confirmed Goldschmidts equation for normal and not influenced by the catalyst concentration.
aliphatic acids in methanol catalyzed by hydrochloric acid The reaction is second-order with respect to the organic acid
over the range 20 to 50 C. I n these and other studies concentration.
(7, 8, 9, 73, 76, 77, ZO), either sealed glass ampoules or a I n previous experiments involving equimolar cyclohexanol
ground-glass-stoppered flask was used as the reactor. The and acetic acid, this author found the rate constant to be a
studies were also similar in that the alcohol was always in function of the initial reactant concentration as well as tem-
excess, and the organic acid concentration was initially con- perature and catalyst concentration, and the reaction to be
stant. A high alcohol-to-acid ratio was found to result in a third order. T h e present work involved the study of the
esterification of equimolar cyclohexanol and acetic acid cata- 68.8' C. a t 20 mm. of mercury, and the refractive index was
lyzed by sulfuric acid with dioxane as the diluent. Reactions 1.44070 at 20' C. Density us. temperature data were corre-
lated in the 20' to 80' C. range by the empirical equation:
were carried out in a stirred batch reactor. The main objec-
tive was to develop an empirical equation which would relate Density (grams per ml.) = 0.9893 - 0.000966 T (" C.)
the forward reaction rate constant to initial reactant concen-
tration, catalyst concentration, and temperature. Range of Commercial 1,4-dioxane was purified and dried ( I ) , but
these variables was 1.25 to 5.00M, 0.0930 to 0.1245M, and the resulting dioxane was more impure than the original. The
104'F. (40' C.) to 176' F. (80' C.),respectively. dioxane was finally purified by drying it over Drierite, passing
it through activated alumina, and then distilling it. T h e
T h e reverse reaction, cyclohexyl acetate and water forming purified dioxane boiled at 95.2' C. at 622 mm. of mercury, and
cyclohexanol and acetic acid, was also studied. did not react with calcium hydride. It was stored over cal-
cium hydride in pint bottles which were flushed with nitrogen
Experimental Work and sealed with paraffin.
Commercial carbonate-free, 1 N sodium hydroxide solution
Apparatus a n d Equipment. A 300-ml., 3-necked, round- was used to titrate for the acetic and sulfuric acids in water
bottomed, glass boiling flask was constructed for use as the with phenolphthalein as the indicator.
reactor. The center neck was 7 34/45, and the two side Procedure. PREPARATION OF REACTANT SOLUTIONS FOR
necks were both 7 24/40, angled to avoid contact with the FORWARD RUNS. The densities of cyclohexanol and acetic
mercury-seal stirrer in the center neck. acid were determined by weighing 100 ml. of the reagent in a
The temperature bath was a MagniWhirl visibility j a r bath, volumetric flask immediately preceding the preparation of the
Model MW 1152, manufactured by the Blue M Electric Co. solution. Appropriate amounts of the acid and alcohol were
It was an on-off controlled bath with a room temperature to put in a 1- or 2-liter volumetric flask and diluted with dry
100' C. temperature range. Commercial mineral oil was the dioxane. After the solution reached room temperature, the
heat transfer medium. solution was diluted to the volumetric mark and thoroughly
Saybolt viscosity thermometers with 0.2' F. increments were mixed. The solution was then poured in 160-ml. amounts
used in the reactor. An all-glass, 1-cc. syringe calibrated in into '/*-pint bottles which were stored a t -20' C. Each
0.01-cc. increments was used to inject the catalyst into the bottle was labeled as to initial reactant concentration, and each
reactor. Equipment used for analytical work included 1-ml. contained enough solution for one experimental run. Prepara-
transfer pipets with 0.006-ml. tolerance, 250-ml. Erlenmeyer tion was done in this manner to ensure that the initial reactant
flasks, a 5-ml. buret inscribed with 0.01-ml. increments, and concentration for each run was identical.
a Voland and Sons analytical balance. PREPARATION OF REACTOR. After each run was completed,
Materials a n d Reagents. Eastman EK-703 cyclohexanol the apparatus was disassembled, cleaned with Alconox, washed
was used with no further purification. Infrared spectral data with acetone, and dried with air to remove any possible catalyst.
indicated that the cyclohexanol contained less than 1.O% The equipment was then assembled.
water. The boiling range was 136.8-37.2' F. at 10 mm. of INTRODUCTION OF REACTANTS INTO REACTOR.The bath
mercury. was heated to the desired temperature, and a reactant bottle
Baker and Adamson 20% fuming sulfuric acid was mixed was taken from the freezer and allowed to warm to room tem-
with B and A sulfuric acid (assay 95.5 to 96.5%), and the perature. One milliliter of the solution was titrated with
concentration was adjusted by titration to yield about 50 ml. standard base, and the value was recorded as CaoTa, the initial
of 1 0 0 ~ osulfuric acid. This catalyst was stored in a 50-ml. concentration of acid at room temperature. Pipetted into the
ground-glass volumetric flask. reactor were 150 ml. of the reactant solution; the reactor was
Cyclohexyl acetate was extracted from the reaction products sealed, and the stirring was begun. When the solution
and purified in the following manner. One liter of the reaction reached the desired temperature, another 1-mi. sample was
products was put in a 2-liter boiling flask. T o this were added withdrawn and titrated. This value was recorded as Caor,
50 ml. of commercial glacial acetic acid, 150 ml. of distilled the initial acid concentration a t the operating temperature.
benzene, and 1 ml. of concentrated sulfuric acid. The solution INJECTION OF CATALYST INTO REACTOR.An appropriate
was refluxed until all of the water had been collected out of a amount of catalyst was drawn into the syringe. The syringe
moisture test receiver, then washed in a separatory funnel with was weighed before and after injection, and the difference in
tap water, which was slightly basic, to remove the dioxane, weight was recorded as "grams of HzS04," the grams of
unreacted acetic acid, and sulfuric acid. Cyclohexyl acetate catalyst. The catalyst was injected into the reactor and a
is insoluble in water, so as much as 5 liters of tap water were stopwatch was started. A 1-ml. sample was taken with a pipet
used. T h e solution was then washed with 1 liter of distilled after 0.5 minute (0.0083 hour) and thereafter a t convenient
water. Benzene was added to the washed solution, and the intervals. Each sample was immediately titrated in 150 ml.
solution was refluxed as before until all the water from the of distilled water in a 250-ml. Erlenmeyer flask with standard
washing step was collected. Then the temperature was base and phenolphthalein. The amount of base necessary
allowed to rise to about 140' C. by taking off benzene. The to neutralize the acids was measured to 0.005 ml. and recorded
resulting solution of approximately 98% ester-2% benzene as "ml. of NaOH." Generally 20 to 30 samples were titrated
was vacuum-distilled at room temperature and 5 mm. of before equilibrium was attained.
mercury until all the benzene was removed. Then the tem- PROCEDURE FOR REVERSE RUNS. The procedure for re-
perature was raised and the ester collected. The first and last verse runs duplicated the previous procedure, except that each
5yo was discarded, even though the refractive index remained reactant solution of ester, water, and dioxane was mixed
constant over the entire distillation. The boiling point was separately.
Caoro
TIME (HR)
where 4 = concentration of catalyst (moles per liter, M ) Figure 1. Relation between reactant concentration and
calculated from grams of catalyst added time for runs at 2.5M initial reactant concentration
caor Forward reaction
-= alcohol-dioxane volume correction from room to
Cao~o operating temperature
y = ml. of N a O H necessary to neutralize a 1-ml. raised to the reaction order with respect to each product
sample divided by the concentration of reactants raised to the reaction
N a O H = normality of base order with respect to each reactant.
- *LN-
- 03 C*r
CAO,
/
1.4 - - 0.2
-0.1
I I
2.0 3.0 410 5100
TIME (HR)
l/CUT2 = 2 k f ( t ) +z (5)
where I is the constant of integration. If this is the governing Goldschmidts equation (6) is applicable only to a second-
equation, the graph of l/CaTz should yield a straight line with a order reaction or one in which the alcohol is in excess.
slope of 2kf. Reaction Rate Constant Equation. T h e following ex-
It was assumed in Equation 4 that the concentration of the plains how the various relationships among the variables,
alcohol equaled the concentration of the acid. There was a initial reactant concentration, catalyst concentration, and
reaction, however, between the alcohol and the catalyst which temperature were combined to obtain an equation which
depleted the alcohol by an amount #. Since the reaction of could be used to predict the reaction rate constant.
catalyst and alcohol was complete in less than 10 minutes for all T h e rate expression for many reactions can be written as
runs, $ was considered to be a constant. For this assumption a function of temperature times a function of composition, or:
the defining third-order differential equation becomes:
r = f(temperature) . g(composition)
- (dCaT/dt) = k f C a T 2(Car - #) (6)
where f(temperature) equals the rate constant, k . If an
Equation 4 may be written in finite difference form: Arrhenius-type dependency is assumed, then :
- (A t)/CaT3 = k f (7) k = k, exp [ - E / R ( I / T - l/T,)] (70) (9)
Equation 6 may be rewritten in the same manner:
If the graph of -In k f us. 1/T abs. yields a straight line, then
- (A CaT/A t)/CaTz ( C U T - #) = kf (8) the slope of that line equals E/R. Figure 3 is that graph at
When the rate constant, k f , was calculated from Equations 7 constant catalyst concentration and various values of initial
and 8 by means of original data, the range of per cent devia- reactant concentration. I t was found that E/R was a function
tion of Equation 8 from Equation 7 was 0.4 to 7.270, the
of initial concentration, but not catalyst concentration. Figure
majority of the runs having a deviation of about 3y0. After 4, a plot of E/R us. CaoTo,was assumed to yield a straight
consideration of the error involved, the stability of the solu- line. This line had the equation: E/R = 9860 +
788 CaoT,.
tion, and the relative ease of calculation, the rate constant was A base temperature of 618 R. (158 F.) was chosen, and the
calculated by means of Equation 5 by the graphical method. exponential term was written:
Only the values of Car in the range 20 to 80% reaction were
exp[-E/R(l/T - l/T,)] =
used to construct the graph of 1/CaT2us. time. The slope was
then calculated to be 2 k f . exp[(9860 + 788 Caoro) (0.0016181 - 1 / T ) ] (10)
Theoretically, the same type of analysis could have been
C was then defined as grams of H2S04 per gram of cyclo-
used to determine the governing equation for the reverse
hexanol times 100. Figure 5 is a plot of kf/C us. CaoT, a t the
reaction. I t was found experimentally, however, that even a n
base temperature and constant catalyst concentration. The
ester-water concentration of 2.5M was heterogeneous upon
equation of the straight line obtained was
addition of the catalyst. Because samples could not be taken,
the reverse rate constant, k,, could not be calculated for the k f = C (0.0425 - 0.0034 C a o T o ) (11)
majority of possible combinations of variables. Other aspects
of the reverse reaction are discussed later. Given the volume of 0.1 5 liter, the weight of the cyclohexanol
;
0.175
O.I5O; I I
I /)__, I I
/I
62
I
+
k, = [0.01152 0.0815(grams of catalyst)] X
0.150 - -
(0.2829/CaoT, 0.02263) . exp [(9860 4- 788 CaoT,) X
0.125 (0.0016181 - 1/T)] (14)
k, At the base concentration and base temperature, Equation 14
should become only a function of catalyst concentration.
0.075
The exponential term becomes exp (0) at the base tempera-
0.050 ture. A value of 2.5Mwas substituted into the second term of
/@ 1 1 I I
Equation 14,and the term was calculated to be 0.09053. The
0 .0250,0 first term of Equation 14 was divided by 0.09053to obtain the
0.025i0 0.5 1.0 1.5 2.0 2.5
GRAMS Has04 +
term: 0.1272 0.900 (grams of catalyst). Equation 14 for
k , did not contain a volume term; therefore (gram of catalyst)
Figure 6. Relation between rate constant and catalyst was converted to moles per liter, 9, given the volume 0.15
weight at 2.5M and 158' F. +
liter. The term thus became equal to (0.1272 13.24084).
Therefore the equation for the prediction of the reaction rate
constant became
was calculated to be 15.024CaoT,. Therefore, Equation 11
could be simplified to:
k, = (0.1272+ 13.24084) [0*282g
- - 0.022631 x
CaOTo
k, = grams of HzSOa (E
- 0g
.02263)
COOTO
(12) exp [(9860 + 788 Caoro) (0.0016181- 1/T)] (15)
Calculated and experimental rate constants, per cent devia-
An initial reactant concentration of 2.5Mwas chosen as the tions, and data leading to the results are tabulated in Table 11.
base concentration. The rate constant was found to be a Equilibrium constants of the forward and reverse runs and the
function of catalyst concentration at constant initial reactant results of the steps leading to their calculation are tabulated in
concentration and constant temperature. Figure 6 is a plot of Table 111.
k, us. grams of catalyst a t 2.5Mand 158' F. The equation for
the straight line through the points was Interpretation of Results
k, = 0.01152 + 0.0815 . (grams of catalyst) (13) Activation Energy. The activation energy was calculated
from a plot of -In k, us. 1/T' abs. At an initial reactant con-
Equation 13 was substituted for grams of H2SOa in Equation centration of 2.5M; 0.25,0.75,and 1.00 ml. of catalyst gave
12,and the result was multiplied by Equation 10 to yield values of E / R equal to 11,800', 11,830', and 11,800' abs.,
i
constant for the reverse reaction. However, an ester and water
'Ob6 concentration of 2.5M or greater was heterogeneous after the
catalyst was added. Figure 7 is a graph of Cur us. time for runs
36 to 40, each at an initial reactant concentration of 2.5M.
The only variable in these runs was temperature. The first
point on each graph was taken as close as possible to the time
when the reaction mixture became homogeneous. Reverse
rate constants could not be calculated for these runs, but the
runs were useful in determining the effect of temperature on the
RUN TF equilibrium constant.
36
37
104
122 1 Solutions at an ester-water concentration of 1.25M with
either 0.25 or 0.75 ml. of catalyst per 150 ml. of solution were
0.400 38
39
40
140
158
176 1 homogeneous throughout the reaction. These were the only
two combinations of variables covered in this study that gave
0.300
0.200
1 homogeneous solutions at all times. I t was determined from
Figure 8, a plot off(&) us. time, where Cer is the ester concen-
tration, that the reverse reaction was third order. Rate
0.100
constants were calculated by the graphical method discussed
I I I I I I earlier and are tabulated in Table 11.
o.ooo~,o 10.0 20.0 30.0 40.0 50.0 55.0
Reactions in Dimethyl Sulfoxide. The discussion thus far
TIME (HRI
has pertained to reactions carried out in 1,4-dioxane. Esteri-
Figure 7. Acetic acid concentration vs. time for a series of fication reaction rates should increase as the polarity of the
temperatures at 2.5M and 0.75 ml. of catalyst per 150 ml. solvent is lowered and so dioxane was chosen because of its low
Reverse reaction polarity ( p = 0.3 Debye above 30' C.) (3) and low dielectric
constant [ E = 2.252 - 0.00717'(' C.)] (79). T o examine
the effect of solvent polarity on the rate constant three runs
were carried out in dimethyl sulfoxide with a dipole moment
of 3.96 D (5) and a dielectric constant of [e = 48.5 - 0.075T
(' C.)] (4). Runs were also made in dioxane with the same
initial reactant concentration, catalyst concentration, and tem-
perature (Table IV).
The esterification in dimethyl sulfoxide was third order
over-all. Therefore, the units on the rate constant in both
solvents are (liter)2 (moles) -* (hr.) -l.
At 122' F. (50' C.), the highest temperature for which the
dielectric constant of dioxane is applicable, the ratio eDMBO/
0.800 ~ D I O X is 20.65. The ratio, P D J T ~ O / ~ D I Ois~ 13.2. Although
these two ratios are within 25% of the ratio of the rate con-
stants, there exists no theoretical justification for this.
1.100
/
I . 500 0 42
Conclusions
1.300
The esterification reaction was first order with respect to
cyclohexanol and second order with respect to acetic acid.
The reverse reaction was third order.
0.900
Esterification reaction rate constants can be predicted within
5y0 by an empirical equation.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0
The rate constant was a function of initial reactant concen-
TIME (HR)
tration, catalyst concentration, and temperature.
Figure 8. Relation between initial reactant concentration The activation energy was not a function of catalyst concen-
and time tration, but was a function of initial reactant concentration.
Reverse reactions The equilibrium constant was at most weakly influenced by
temperature and not influenced by catalyst concentration.
I t could not be determined from the experimental data if the
equilibrium constant was influenced by initial reactant concen-
tration.
Table IV. Reactions of 2.5M Cyclohexanol and Acetic Acid
in Dimethyl Sulfoxide
Acknowledgment
The authors express their appreciation for financial aid
140 0.75 0.0710 0.0041 17.30 received from a National Aeronautics and Space Administra-
158 1 .oo 0.1555 0.0090 17.29
176 1.oo 0.2475 0,0144 17.15 tion graduate fellowship (D.J.M.) granted to the Colorado
School of Mines.
The performance of an ejector in single-phase (air-air) and two-phase (air-liquid) systems has been studied
with air as the motive fluid, and air and various liquids as the entrained fluid. Data for air-air system have
been analyzed, using energy and momentum equations; the values of mass entrained calculated from the
theoretical expression agreed with experimental results only in the limited range of small area ratios. Corre-
lations based on the method of dimensional analysis have been developed for both air-air and air-liquid
systems relating the mass ratio of entrained fluid to motive fluid in terms of Reynolds number of motive
fluid, geometry of the ejector, and the physical properties of the fluid system.
HE mechanism of jet flow has largely been exploited in to problems of great complexity. Apart from the importance
Tejectors or jet pumps in which the momentum and kinetic of fluid physical properties and solid particle characteristics,
energy of a high velocity fluid stream are used to entrain and there are interrelated problems such as solubility, holdup, and
pump a second fluid stream. Ejectors with steam o r com- slip. Hence, it is considered logical to carry out this investiga-
pressed air as the motive fluid have found application in indus- tion on momentum transfer in stages-first, using a single-
trial operations for the creation of vacuum, exhausting corro- phase system, where the motive and entrained fluids are gases,
sive fumes, pneumatic conveyor feeding, etc. Its incorpora- then a two-phase system where the motive fluid is gas and the
tion especially in slurry-type chemical reactors holds consider- entrained fluid is liquid, and finally a three-phase system where
able promise. By this technique the kinetic energy of the the motive fluid is gas and the entrained fluid is solid-liquid
reactant motive gas can be utilized to maintain the solid catalyst slurry. Studies carried out in single-phase systems with air
particles in suspension, cause intense mixing between gas and as the motive and entrained fluid in the motive pressure range
fluid, and circulate the catalyst slurry through an external side of 25 to 100 p.s.i.g. have been reported (8).
tube, thereby obviating the difficulties normally encountered This paper presents studies carried out in a single-phase
in conventional mechanically stirred reactors. Satisfactory (air-air) system in the low motive pressure range and in two-
operation of such a type of reactor employing an ejector as a phase (air-liquid) systems.
pump for hydrocarbon synthesis has been reported ( 9 ) .
The present investigation on the momentum transfer in Single-phase (Air-Air) System
ejectors has been carried out to obtain necessary data and The many analyses (7,4-7, 76, 78) that have been attempted
correlation, with the ultimate object of designing and in- in the design of ejectors, notably those of Keenan, Neumann,
corporating ejectors in slurry-type chemical reactors and allied and Lustwerk (5, 6), Kastner and Spooner ( 4 ) , Smith (76),
process operations. and Van der Lingen (78), have all been made using the
In a multiphase system consisting of gas, liquid, and solid a equations of continuity, momentum, energy, and state. Most
large number of variables are involved which usually give rise of them deal with constant area and constant pressure mixing.
Nearly all the experimental investigations reported in the
literature on the performance of ejectors relate to relatively
high motive pressure, the only exception being the work of
Present address, Indian Institute of Technology, Madras,
India. Kastner and Spooner.