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The kinetics and thermodynamics of the phenol from cumene process: A

physical chemistry experiment

Article  in  Journal of chemical education · June 1980

DOI: 10.1021/ed057p458

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 The Kinetics and Thermodynamics of the
Edward C. M. Chen
and Stephen L. Sjobergl
University of Houston at Clear Lake City
Phenol from Cumene Process
I
Houston, TX 77058
A physical chemistry experiment
The differences between thermodynamics and kinetics are
emphasized in every physical chemistry textbook. However,
these differencesare seldom illustrated in laboratory exper-
iments carried out on the same reaction ( 1 , 2 ) .~ort-unately,
the formation of phenol and acetone from cumene hydro-
peroxide is a reaction which is ideally suited for lahoratory
experiments displaying these differences. In addition, the
reaction is a good example of an industrially significant pro-
cess.
The ~ h e n ofrom
l cumene wrocess. which Droduces over 2.5
billion pounds of phenol pe; year, is typical of modern pet-
rochemical processes which have been developed over the past
thirty years. There are three hasic reactions in the process,
each of which is a verv interesting example
- of a different tvwe
..
of catalysis. T h e a1k;lation reaction:
CaHs + CsHs = CsHs(C3H7) (1)
is an acid catalyzed condensation reaction using a solid or
liquid catalyst. The formation of the hydroperoxide:
C9H12 0% += CgHs(C3H600H) (2)
is a dual phase, base catalyzed, autocatalytic, free radical
oxidation. T h e formation of phenol and acetone from the
cumene hydroperoxide:
CsHs(C3HeOOH) = CsHsOH + CaHeO (3)
is a non-aaueous. acid catalvzed. 1.2-phenvl shift reaction
which exhibits bdth negativiandp&iiive catalysis. The ac-
tivation enerev and the heat of reaction for this last step are
both easily measured. The experimental rate expression can
be derived from a proposed mechanism so that this difference
between kinetics and thermodynamici can he emphasized.
'I'he measurement of the heat reaction for the cleavage re-
action (eqn. (:%)leads to theevaluation of the heat oiformstion
of cumene hydroperoxide and hence to thecalculation of the
heat 01' rearrion ror reaction 121. The heat of reaction for re-
actiun ( 1 1 ran be ohtainrd from standard tablessu that a11 of
the enthalwies for tht. maior reactions are obtained. Additional
details of the process c&be found in article by Armstrong (31,
and Puiado. Salazar. and Beraer ( 4 ) .
The thermodynamic expeAments are essentially calori-
metric studies and can be completed in one period. However,
because of the number of variables investigated in the kinetics
experiment, two periods must he allotted or the work can be
divided up among two or more groups. There are five separate
kinetic reaction sequences, three a t the reflux temperature
of acetone to measure the effect of hydroperoxide concen-
tration, acid concentration, and water concentration a t a fixed
temperature, and two a t lower temperatures to determine the
activation energy of the reaction. If the project is to be a group
effort, each group should do one high temperature experiment
and the two lower temperature runs. At the end of the rotation
period, the results of the group effort can he pooled and a final
report written by each student. This type of project is illus-
trative of group~effortswhich are often encountered in in-
dustrial laboratories.
Work done in partial fulfilment of the requirements for the degree
of Masters of Science, University of Houston, CLC. Current address:
Exxon Research and Development, Baytown, TX.
458 / Journal of Chemical Education
H+ + ~~0& H ~ O + Equilibrium (4)
k-IB
H+ + ROOH &ROOH: Equilibrium (5)
k-,A
ROOH%+&RO+
k-1
+ HzO Equilibrium (6)
RO+ 3 R , ~ R , , slow (7)
R ~ R+"H ~ O
%R'OR"OH + H+ Fast (8)
n
In this mechanism, reactions (4), (51,and (6)are equilibrium
reactions, reaction (7) is the rate determining step, and reac-
tions (8) and (9) are fast. Under these conditions, the overall
rate expression given below can be obtained. (This is left as
a student exercise.)
d[Phenol] - K I A K Z[ROOH][H30+]
--
dt ks- (10)
KIB [HzOIZ
When the svstem is comoletelv anhvdrous. the rate does not
become i n f h t e but is governed by the dksociation of the
sulfuric acid in acetone. The experimental rate data agrees
well with the above rate expression, but this does not unam-
biguously establish the reaction mechanism.
Analytical Procedures
Because of decompmition of the hydroperoxide solutions, the exact
concentration of the stock solution must be determinedjust prior to
the experiments.This determination is done hv a non-aqueous iodine.
~uplicatedeterminations should be done for accuracy. ~pproaimately
0.1 eof the 50-75s cumene hvdroneroxide is weiehed accuratelvinto
a 2 j 0 ml Erlenmever flask ebuiobed with a standard taoer ground
heated to the reflux temperature. Ten milliliters of an 80%isopro-
panol-water solution which has been saturated with potassium or
sodium iodide is then added and the solution refluxed for 5 mi". The
heat is then removed and all traces of iodine washed down the con-
denser with isopropanol, and the sample is cooled. Then thesample
is titrated with a 0.025 F sodium thiosulfate solution usine a 50 ml
turette. The end p g h t ipshnrp hut thr rltrarion should"& done
rapidly to minimize air oridatim. The f m t complrw drsappmmrlc~
ui rhe rohr should hc used ns the end pcunr. There m m be some
cloudiness due to water which can be remedied by adding more isa-
propanol.
The densities of the solutions, 5%HzSOl in acetone, and the cu-
mene hydroperoxide solution, can be obtained with a pycnometer.
Because of the large number of analyses required for the kinetics
experiment, a spectrophotometric determination of the phenol
product is used. A Varian Technitron UV-VIS spectrometer, set at
284 nm, the peak for the phenolate ion was actually used; but a
Spectronic 20 can also be used on the side of the band if the amount
of sample is adjusted. Far our determinations, 0.05 ml samples were
withdrawn from the reaction vessel at various times and dropped into
a 20 ml test tube previously filled with 10.0 ml of a 0.1%NaOH solu-
tion. Not only does this caustic produce the phenolate ion but also it
 immediately quenches the reaction. A 0.20 ml graduated pipette was
used to obtain the samples. Obviously, larger samples could be taken
but would require additional dilutions. Because of the small sample,
special care must he taken to avoid contamination by color bodies.
For this reason, cork stoppers should be avoided. The samples are
poured into the spectrometer cells after being mixed thoroughly. The
reference is a sample taken from the reaction flask before the acid
catalyst is added. The cells and all other glassware should be rinsed
thoroughly with distilled water, acetone, and then dried. As a pre-
caution against a had analysis, duplicate samples should be taken.
Experimental Apparatus
'rhechrmicnls that are nrcded are cumene hvdropen,xide,availahle
from Matheson. Coleman and Bell. rragent grade acetone, nmninally
tr4T water. !A? s u l f u r i ~wld, wdium h\drox~de.p~tassiumiudide.
sodium thiosulfate, and isopropyl alcohol.
For the calorimetric studies, a thermistor bridge and recorder or
an accurate thermometer is required. A stirred insulated beaker was
used successfullyas a calorimeter since the reaction is so rapid. Simple
volumetric glassware for titration and density measurements are
nppded
....-.- ~
to reach infinite nhwrbanw. Alternatively, the infinitr trine value fur
the lower temperaturr runs rau he calculnted from the hich ternper-
ature infin~telime nhkcdrsnce ur ma)' he obtained the fdluwiny week.
In the later case, the samples must be sealed tightly to prevent
evaporation.
While one student is doing a high temperature run, once the low
temperature run is started, the other student can begin the analyses.
Once the high temperature run is completed, the first student can help
with the analvses and olot the data versus time to check for consis-
tency. If a data point is "out of line," then the contingency sample can
be analyzed.
Calculations
The weight percent of the cumene hydroperoxide is calculated
as
ml Thio X F thia X 7.61
wt% ROOH = (11)
wt sample (g)
The heat absorbed hy the calorimeter and solutions is defined as
q and is given by the relationship

For the kinetic studies, besides the spectrometer, a 100 ml3-neck

qbul = c,, AT + (c,. p ."(sol) + c, .p .u(R0OH))AT (12)
distillation flask with ports for thermometer, condenser, and sampling where cpI,, is the heat capacity of the physical system, c,, p, and u
is required for a reactor. A hot water bath is used to heat the mixture (sol) refer to the heat capacity, density, and volume of the sulfuric
t o reflux temperature to prevent "hot spots." The lower temperature acid-acetone solution and e,, p, and "(ROOH) refer to these param-
runs are carried out in 50 ml Erlenmeyer flasks placed in a room eters for the hydroperoxide solution. The last term can he qalculated
temperature or ice bath and mixed with a TeflonQoated stirring bar. from the physical properties of the pure materials and the measured
The temperatures in the samples were measured with thermometers. densities and the experimental heat rise and can be defined as q,,,
For the analysis, a large numher of 20 ml test tubes are needed for t o give upon substitution into eqn. (12)
sample collection. Pipettes needed are as follows: 50 ml, 25 ml, 10m1,
2 ml, graduated 0.2 ml, and a graduated 5.0 ml. Syringes may be used qmta1 = c ,,,,,,A T + q.~, (13)
for the sampling andlor catalyst addition. The volumetric flasks that The heat of reaction, AH, is then given by
are needed are a 100 ml, a 500 ml, and a 1000 ml.
qtota1
(14)
Experimental Procedures AH,= - moles ROOH
The thermodynamic experiments consist of collecting temperature It is obvious that to find the heat ofreaction, the heat capacity of
versus time data for variousamountsof solvents. Earlier, the hydro- the system must he ohtained. The heat capacity e m be done by
peroxide content, the densities of the solutions and a calibration curve plotting qappversus AT and extrapolating to zero. The intercept is
for the thermistor must he established. Also the standard calorimetric qt-I while the slope is the heat capacity of the system.
reaction solution, a 5% solution of H&04 in acetone must he prepared. The heat of formation for the hydroperoxide is obtained from
This preparation is done by takings 200-ml volumetricflask, adding
about 100 ml of acetone, then adding 5 ml of HzSO4 (98%) while AH:, (ROOH) = AH!, (Phenol) + W , (Acetone) - AH,
cooling, and making up to mark with acetone. This solution is best (15)
. .
oreoared hv the instructor , iust before the class since i t is not stahle The heat of combustion of ROOH. the heat of reaction (2) and the
for mure than a day nt n u m temperature. Extreme care must he tnken hydroperoxide oxygen-oxygen bond dissociation energy can be cal-
to moid ptting the acid ruluricm m u m a c t w ~ t hthe hydropennide culated by standard techniques.
stack wlulim 'I'hus the instructor s h d d pour uut ahout 10 mlofrhe Initially, the studentsshould plot the kinetic dateasLn(A- -A,)
solution for each group doing the experiment and keep the supply in versus time. If the water concentration and the acid concentration
another area. nre conitant, and the reaction ir first order in hgdruperuxide eun-
The temperature rise data should he obtained far a t least four so- centration, then this should yield a straight line (see eqn. ~1101.
The
lutions using 1.0 ml of the hydroperoxide solution and varying do1)e of the line wdl he the preudo t m t order rate constant ihr and
amounts of the acid solution. Initially pipette 15ml of theacidsolu- by carryingout the experiment under various water and acid &xs,
tion into the calorimeter, in our ease a 100-ml insulated beaker. The the exponents, a and b, of the expression:
probe or thermometer is then placed in the calorimeter and the
stirring started. When a constant temperature is reached, (almost k = K [Ht]' [HsO] (16)
immediately), record it and add the 1.0 ml of cumene hydroperoxide
can he determined. The empirical rate constant is defined by
from a pipette. Record the temperature every 3 see until the maximum
is reached and then every 10 sec until the temperature drops by sev-
eral degrees. If a thermistor is used, the temperature r-rd is obtained
automatically. Repeat this procedure with 20 ml, 25 ml, 30 ml, and
40 ml of the acid solution. The calorimeter should be cleaned and
rinsed with acetone between each run.
Table 1. Klnetlc Reactlon Conditions
There are three solutions to be prepmed for the kineticstudies, a
0.1% NaOH solution for analysis purposes, a dilute ROOH solution, ROOH H~SOI
10 ml of the standardized concentrated ROOH (--75%setive) made T At sol sol H20
up t o 500 ml, and a 4 % sulfuric acid in acetone solution prepared
. . as Reaction 'C mi" mi ml ml
above.
Table 1summarizes the conditions for the various kinetic erneri-
.~
ments. The three hieh temoerature runs are carried nut in the 160ml
~~~ ~ ~~~~~ ~

llnak. First 50 ml of the stock hydrs,peroxidr rolutim is hrought tu

~~~~

the reflux temperature A sample is xithdmwn and quenched to be

used for a reference. Then the acid is added and the stopwatch started.
At about 25 min, either the second acid addition or the water addition
can be made. While onestudent is doine the hiah temperature run,
the other can be setting up the law temperature r u n s . ~ ~ hice e bath
will provide a temperature of about 5 T in the flask. Time can he
Reactions 1A and 18 are separate runs.
measured with a wrist watch for these runs. The samnles are agitated ,.~~

Remion 28 is a Mtinvatim of2A in which 0.2 ml ol me %SO, soiutim Is added after about
with n Ttflon" covered stirring har. Once enough data points are 20 min.
rollrcr~dtu define thr c u r w , the low temperature snmples may br Resctiwl 38 is a cominuatlon of 3A in which 0.1 ml of water ia added after about 20
healed or ndditwnal acid may be added to decrease thr time required min.

Volume 57, Number 6, June 1980 1 459

Figure 1.TemperaturevwsusTime for 20 mi. 25 mi. 30 ml. and 40 mi of sulfuric
acid solution.

Figure 3. Ln(A. - A3 versus time as a function of hydroperoxide(lA.18)and

ass function of temperature (1.4.5)(See Table 1 for exact cmditions.)

Figure 2.Apparent heat release versus temperature change.

or in the integrated form:

Ln(A, - A3 = k t
Thus Exoeriments 1A and 1B (see Table 1) test the first order rela-
rionahip-, experiments 21\ and 2H esrnhlish thc vnlue d o , and ex. Table 3. Thermodynamic Data
prrimmrqR.4 and RBrital,liih the \,alurot h. tSeeTahle 1 f o r Reac.
tion conditions.)
AH:. 298 -AHcomb mlml
(kcdl (kcail C, Experimental
Once the relationship is established, then the intrinsic rate constant,
Compound mole) mole) callg - O K solution
K, (not to he confused with an equilibrium constant), can he ealeu-
lated and the temperature dependency examined. A plot of LnK Pmpylene 4.879 490.2
versus l i T eives a d o ~ of
e E*IRT and an interce~tof LnA aeeordina Benzene 11.63 782.3
to the kinetic ~ r r h e n Expression.
k Cumene -9.848 1247.3 0.35
K = A erp(-E*lRT) (19) Cumene-OOH - - 0.45 0.9615
Phenol -37.80 732.2 0.50
Typical Results Acetone -59.32 426.8 0.535-0.540
The eumene hydroperoxide content of our sample was determined Sulfuric Acid - - 0.350 0.8163
Imiutionl
to be 51.0%. The experimental temperature nwes are shown in Figure
1, and the data is summarized in Table 2. The heat capacities are
corrected for temperature. The extrapolation data is shown in Figure
2 where the intercept gives a qbhl value of 181.0 cal and a slope of
1.105 cal OC-'. From this the value of -56.11 keal mole-' is obtained Table 4. Heats of Reactlono (kcal-mole-')
using eqn. (4). This value is compared t o literature values of -54.0
and -60.4 kcalmole-' (3.4). With additional thermodynamic data This
taken from standard sources such as Perry and Chilton's "Chemical Experiment Ref (3) Ref (4)
Engineering Handbook" (5) and the "Handbook of Chemistry and
Physics" ( 6 ) .This data and the other calculated thermodynamic -Awl) 23.8
properties are summarized in Tables 3 and 4. -AM(?) 31.26 31.0 27.7
The kinetic data are plotted in Figures 3 and 4. Table 5 gives the -AM31 56.11 54.0 60.4

460 1 Journal of Chemical Education

 Figure 5. Ln K versus reciprocal Temperature for Me formation of phenol h a m
cumene hydroperoxide.

Table 5. Typical Klnetlcs Results OMalned

slope CR- C H+ C H20 Kmin-'
Reaction miK1 molesll lo3 X moles11 moles/l mole11

1A 0.0450 0.025 5.88 0.222 0.377

10 0.0470 0.010 5.88 0.222 0.394
2A 0.0195 0.025 2.74 0.222 0.327
20 0.0405 0.025 5.88 0.222 0.339
t lmin ) 3A 0.0438 0.025 5.88 0.222 0.367
30 0.0205 0.025 5.88 0.332 0.384
Figure 4. Ln(A., - A,) versus time as a function of water (3A. 38). and as a
function of acid (1, 2A, 20). (See Table 1 for the exact conditions.) 4 0.0155 0.023 67.28 0.222 1.14 X lo-'
5 0.0033 0.021 123.34 0.222 1.32 x lo-'
Ef = 19.63 Lullmole
values of the slope, the concentrations of the various species, and the In A = 24.82
intrinsic rate constant K. These were calculated as follows.
sented here. In general, the students obtain a much more re-
alistic " - of the similarity and differences betu,ecn kinetin
erasr,
Thuso = +1
&=
k3*
(=)*
00205
( [ H ~ O I ~=B ) ~
[H2013* 0.222
=
0.0438
and thermodynamics by actually measuring these quantities
on the same reaction,
Acknolwedgment
Thus b = -2 T h e authors are grateful to the University of Houston a t
Clear Lake City for the support of this research. The aid of Dr.
,.- , J. A. Ayala and Dr. B. H. White in running these experiments
A numher id'bnd poinLs can twsrrn in the kinetic plow 'I'hept.~)uld in the Physical Chemistry Laboratories a t the University of
have hwn checked if rontmgenn. cnmplca had hen ohtamed.'l'hc Houston Central Campus is also recognized.
exprrimrntal d a t a agrwswith the rateleu &tamed hum the mcch-
anism. Literature Cited
Figure 5 shows the Arrhenius plot fur the K data. Theslope yields (1) Beftelheim.F. A.,"Experimental PhysicslChemistry..l W. B. Saunders, Philadelphia,
a value of E* = 19.23 keal mole-' and can be compared with avalue Ps., 1971.
of 21.3 kcal mole-' reported by Seubuld and Vaughan (7). (2) Danielr, F.,el al.. '"ExperimentalPhysical Chemistry," MeCraw-Hill, Near York, New
Yurk. 1962.
Conclusions 131 ~ ~ ~ p t ,in~..Modern . ~ .Industry." (EdifocJ.G.Grewry),I.U.P.A.C.,
~ eChemi3tryin
I., m
td n. 196~.I I inr,
This experiment has been carried out in the University of t o P . g ~ ~I,.. K
~ ,. s d l ~ a Ic .H ,..d uerper.l' \' . H ! d m c . r n , m R o e . x . w Y l 5.5. I976
,i, "I~err'.L'tlcrncrl Fn*,npmng Han.1~ k; Mrlir.u.ll,ll. h u Y r i 1963.
Houston Physical Chemistry Laboratories in one form or
another for the past four years. The final form developed last
$C 'IlcndboA ,.l('l.rm 4 r \ .na p h ) ~ ~ ~('n.tn.~al
.,' H Y ~ ~ IPuhl .
P C rhlng I'(. ~lrveland
1970.
year a t the University of Houston a t Clear Lake City is pre- (7) Seubuld, F. H.,and Vaughan, W. E., J Amer Chem. Soc., 75,3794 (1953)

Volume 57, Number 6,June 1980 1 461

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