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I
Houston, TX 77058
A physical chemistry experiment
the formation of phenol and acetone from cumene hydro- H+ + ROOH &ROOH: Equilibrium (5)
k-,A
peroxide is a reaction which is ideally suited for lahoratory
experiments displaying these differences. In addition, the ROOH%+&RO+
k-1
+ HzO Equilibrium (6)
reaction is a good example of an industrially significant pro-
cess. RO+ 3 R , ~ R , , slow (7)
The ~ h e n ofrom
l cumene wrocess. which Droduces over 2.5
billion pounds of phenol pe; year, is typical of modern pet- R ~ R+"H ~ O
%R'OR"OH + H+ Fast (8)
rochemical processes which have been developed over the past n
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: In this mechanism, reactions (4), (51,and (6)are equilibrium
C9H12 0% += CgHs(C3H600H) (2) reactions, reaction (7) is the rate determining step, and reac-
tions (8) and (9) are fast. Under these conditions, the overall
is a dual phase, base catalyzed, autocatalytic, free radical rate expression given below can be obtained. (This is left as
oxidation. T h e formation of phenol and acetone from the a student exercise.)
cumene hydroperoxide:
d[Phenol] - K I A K Z[ROOH][H30+]
--
CsHs(C3HeOOH) = CsHsOH + CaHeO (3) dt ks- (10)
KIB [HzOIZ
is a non-aaueous. acid catalvzed. 1.2-phenvl shift reaction When the svstem is comoletelv anhvdrous. the rate does not
which exhibits bdth negativiandp&iiive catalysis. The ac- become i n f h t e but is governed by the dksociation of the
tivation enerev and the heat of reaction for this last step are sulfuric acid in acetone. The experimental rate data agrees
both easily measured. The experimental rate expression can well with the above rate expression, but this does not unam-
be derived from a proposed mechanism so that this difference biguously establish the reaction mechanism.
between kinetics and thermodynamici can he emphasized. Analytical Procedures
'I'he measurement of the heat reaction for the cleavage re-
Because of decompmition of the hydroperoxide solutions, the exact
action (eqn. (:%)leads to theevaluation of the heat oiformstion concentration of the stock solution must be determinedjust prior to
of cumene hydroperoxide and hence to thecalculation of the the experiments.This determination is done hv a non-aqueous iodine.
heat 01' rearrion ror reaction 121. The heat of reaction for re- ~uplicatedeterminations should be done for accuracy. ~pproaimately
actiun ( 1 1 ran be ohtainrd from standard tablessu that a11 of 0.1 eof the 50-75s cumene hvdroneroxide is weiehed accuratelvinto
the enthalwies for tht. maior reactions are obtained. Additional a 2 j 0 ml Erlenmever flask ebuiobed with a standard taoer ground
details of the process c&be found in article by Armstrong (31,
and Puiado. Salazar. and Beraer ( 4 ) .
The thermodynamic expeAments are essentially calori- heated to the reflux temperature. Ten milliliters of an 80%isopro-
metric studies and can be completed in one period. However, panol-water solution which has been saturated with potassium or
sodium iodide is then added and the solution refluxed for 5 mi". The
because of the number of variables investigated in the kinetics heat is then removed and all traces of iodine washed down the con-
experiment, two periods must he allotted or the work can be denser with isopropanol, and the sample is cooled. Then thesample
divided up among two or more groups. There are five separate is titrated with a 0.025 F sodium thiosulfate solution usine a 50 ml
kinetic reaction sequences, three a t the reflux temperature turette. The end p g h t ipshnrp hut thr rltrarion should"& done
of acetone to measure the effect of hydroperoxide concen- rapidly to minimize air oridatim. The f m t complrw drsappmmrlc~
tration, acid concentration, and water concentration a t a fixed ui rhe rohr should hc used ns the end pcunr. There m m be some
temperature, and two a t lower temperatures to determine the cloudiness due to water which can be remedied by adding more isa-
activation energy of the reaction. If the project is to be a group propanol.
effort, each group should do one high temperature experiment The densities of the solutions, 5%HzSOl in acetone, and the cu-
mene hydroperoxide solution, can be obtained with a pycnometer.
and the two lower temperature runs. At the end of the rotation Because of the large number of analyses required for the kinetics
period, the results of the group effort can he pooled and a final experiment, a spectrophotometric determination of the phenol
report written by each student. This type of project is illus- product is used. A Varian Technitron UV-VIS spectrometer, set at
trative of group~effortswhich are often encountered in in- 284 nm, the peak for the phenolate ion was actually used; but a
dustrial laboratories. 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
Work done in partial fulfilment of the requirements for the degree withdrawn from the reaction vessel at various times and dropped into
of Masters of Science, University of Houston, CLC. Current address: a 20 ml test tube previously filled with 10.0 ml of a 0.1%NaOH solu-
Exxon Research and Development, Baytown, TX. tion. Not only does this caustic produce the phenolate ion but also it
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.