J
II

'1' f
‘15:

)l

>
|
l

H
‘
II

I

If}
1
' HI

1
L
I

ll z

| 1‘
I
.
l

l
L

‘l
,t

I:

l
‘||
\
p
\
‘ |

4 I.
I”

I

r”
H

,J

 

SOME KINETiC STUDiES ON
THE CATALYTEC HYDROGENATIGN 53F
MCDN'O-ALKYLEENZEHES
AT LOW AND HIGH #‘RESSURE WQTH
PLAYINUM OKEUE

Thesis for the Degree of M. 3.
MICHIGAN STATE COLLEGE
Lean Ciporin

1951

.1“:
"a." g
L .g ' -" ~—

‘L’

 

 

f.
v? ww- mw— fr

,. £1 A .1 '. M‘ no «lie- ~ .fib-gi’w

3*

1'

LIB? A R Y

i
. 1 o (\
r: IA 3“»). r. y‘ w“
4 ;p11..' -!. 4 L. . .4

}

Vin: ' *.-2....'.;...~.-.*::.:1

.
J

I

‘_ .
‘!
‘ " "W‘wi‘ “5".» u w- v; uni».

 

'1

' ""’ "El-3".»

n.— f")
LIIA‘V ’(I!"” \;‘l A,<_.

 

“hm-“fl—“w

 

‘I

 

[ii E5

 

 

 

 

30E YIR'uTIC STYTDI 1:3 (7-?! TH“: CATALYTIC H‘IW‘ZO¢T?*F'ATI(W 0F
’vf‘fiO-ALYYLBFSY'ZTVB AT LOW Am HIC- PRS‘EST’R'E WITH
PYATIR‘T"! CXID'FS

By

Loon Cipodn

A THESIS

Submitted to the Rohool of fluctuate Studies of Michigan
mt. 0011050 or Agriuultmn and Applied So! me.
in partial fulfillmt of the requirement!“
for the dog?" of

RA??? 3'3 0? SCI EM? '5

Dopartment of Chad-try

1961

AC? T702”, :11 X3? ’37?

The writer with“ to apt-no nu
deepest gratitude to Doctor Robert D-
Sclmuts for hi. 0mm .1 sad manna.
during the prognu of this tort.

Intttttttt
attic...“
titttt
O...

a:

c

()Q (‘1‘; 3 I)
"xvii! \Ji‘i‘) i: .x

JIM};

Kane 1 Leon C! {to flu

30ml mm: 15, 192.13 121 Rev York City

Acaiemio Career:
33mm: High School of Sciatica, 33w York City, 11342-48
Few York Univmlty, Fm: York City. 1946-49
Vichigzm Stat. College, Fast Lanaing. 1969-51

Dear-m field:

B. A. $3” York ”altar-ity 1949

com an: »

a?

«onus-r

1H?RDDflCTXGRQOO00.0.0.0.00....fittooobOlOOOiOOOIOCOOO
HISTORY.003.0.0...no.toOoouooouooaooo.¢o.00....coo-O
mm'zIHMALOOQOODOIOOODOtODOOOOOOOIOOIOOIOOOOOOOOO .

BCIqutloooo:ocan...cocoa-ooooo.-aooooo¢0u¢tooo

LO" Pruauro mmmtiOMOtoouooscotoocotooooc
High hunt. Hydrogenation»..."Hanna”

H
00

CALCULATIWB MD RsBYTHS...""unnunu"a..." 13

DISC?E§IO§OOOOOOOOOOOOIOOO0.0.QOCOIIIOOOOOOOOOODOOOO 17
svzfl‘fAthoooonnoooocoooocctooOQOIQOOOOOQOOOOOOO&OOQO 23
LITE-{“1733}?! cnmcooououooooooooonoooooooOoCccocoocot "
APQ}EDIXOOC00....$0.00..00.000000000000000.OOOQOOOOO 23

FJdNfiflt‘.“ T3b1...’ootuccoo-oouooarQUQCooouoc‘ :6
Hydrogmttan Gtho.o.anaoooooccontact-coo. 52

131’}?le OH

INT RODYCTI 0H

Thor. being no recordcd ayatomtio count-hon oi" the hydrogmtim
of the benzene melons at 10! um! high prusuro. the purpolo of this
war): III to uh ouch a study. In. probln 1m awn-chad with tho bo-
1101' that a quantitative W11”: of velocity col-taut. and 1mm
margin of tcti'ntim at a soda 0! mpmml. at bath high an! III
pron-urea. would gin can insight into the anemia: cf «Myth
hydrogmtion of 11:0th compounds.

1h. comma- chum run a homologous nrioc of minimum.-
The «hat and no ghoul techie acid Ind the «Wt m Ann'-
phtllmn nu. catalyst. Fydmgumtim tor. carried out at two airtim-
n! tutti-L1 pros-nun. Ono notion at radian m conducted at In
innit! prmuro 0! approximately four ntmphor- 1nd the “her In
«mot-a at upmmeay dghty nun-phon- mun: pram".

-1-

519703?

HIST 031'

'rho fir-h renamed catalytic hydrogmation of on organic compound
took place in 1563 when mm: (1) formed methylainlne by poaeing the
vapor or hydrooyanio eoid, nixed with hydrogu. our platinum black.
'rhe scatter-ea instance: of catalytic hydrogenation of organic nob.
mace- ia flu following three decade- are of minor importance.

In 1891, hydrogoation begun to be recognised ea on. of the major
method- of chemical technique. u the remit: of the ablative re-
eearohee of aabafier and hie "acetates. Thin work ie deeoribed in em-
deneed form in :12} Cetalyee enui‘hiwie Organique (I) and 1e seatially
ballad on the discovery of the rmrimblo activity of nickel ae a wan-
mutation catalyst. The procure of passing; the vapor or an matunte
and hydrogoo our nickel to know as tho moo of Sahetier and
sandal-coo. The grant value of Sohati er'e rueorohoa wae the demon-
tioa that almost any vaporieeblo organic ownpound capable of reduction
could be manhun- hydmgmated in the vapor phaee. give: appro-
priate taper-Liza" condition: and a euitable catalyst.

A eeoond omen. developed in 1903. involved the reunion of hy-
drogm at ene to five otnaephoru pressure with a solution in which
the oaeelyet. and Ivdrogm were agitated. Thie method heome particu-
larly ueeful with the development of colloidal platinum. platinum
black (2), and platinum oxide or Adam' «mm (3).

A third prooeae. introduced by Iputiefr in 1904. involved tho re-

action of hydrogen at high teapot-amt“ amour prams-ca of 100 to 300

atmopheree in a heavy etul reaction voeeel with the coupon! in the
liquid phaee (4).

Fee eyetmtio etudioa of the effect of twdrogeo oreeeoro on w-
Grog-nation at eolid catalytie eurfaoee were conducted preview to the
atodiee at Are-tron; and Hilditoh (5). ‘1'th eon-km fund that the
velocity of lvdrogooetioo 1e directly proportional to the hydrogen
prmre in tho abeenoe of autos-hing fautore. Among thue futon
m be included elow-aotixo; pennant catalyet poison. preforntial
adeorbtion of gum imitiee at the catalyet eurfaoe, and the prun-
moe or a amount! containing a fimotioml group not moeptihle to
hydrogmatioo but havim: an affinity for tho eaten-t aorta”. It to
factor: such ae thoeo that explain the imtanoee in which earlier
worker! have tom ourva mggeetive of other than Hour hydrogen-
time ounce.

The nee of platinum oaide no a oatalyet hr the hydmgmtiu of
the boom moleue at low preeeore and moderate tmoratnree an in
rather gluon]. one by 1928. At this time. Adam and Vial-shall (6)
etudiod the hydrogenation of a harbor of phml enbetitutod wounds
in a qualitative manner. Their rmlte indict-Ltd inoroaeed airfioolty
or hydrogenation with ioorooeing molecular complexity. Enter: a. Smith
anti oomrkon (7), (a). (9) ado a montitotive etudy. in 1945. of
tho offeot of etmoture on the hydrogenation of the benzene moleue
with Adam catalyst at low pronoun. They ehowod that, under the In-
perinatal oooiitiom employed. the auto of hydrogomtion wae that
order with respect to the hydrogen pressure. zero order with roepeot

to the hydrogen aooeptor. and directly proportional to the amount of
oetelyet med. Their reenlte eohetentiatod the feet that the hydro-
gemtioo rate decreased with imrming molecular oorqalemity.

In 1947, Better and Remote (10). in tho tint recorded one of
Adam oatalyat by the lpatiei'f high pro-euro method. hydrogenated eer-
enl benaonoid commode. They demonstrated that tho twdmgmtioa
folio-red neutially the some kinotioe an at low pronoun, although the

tin of hydrogmation was comma-ably loos.

PEP} 7'21 W11? :‘:‘AL

The reagente need in e etndy of the kinetice of e reaction eaten
lyeed by phtimm amide met neceeurlly be of high purity became of
the poieonim effecte of mu «senate or foreign materiel-e ‘l’he
chmdoah need in thie work were:

G‘Leclel eeetie ecm
Cyclohezue

mleio mid

Platinum aide «hint
Haney nickel catalyet
Rename

Toluene

Ethylbmeene
Ieopropflbemene
tert-Butylbmem
m1}: meme

zhlele ecld. Pfenetlehl c. P. grade. m reoryetellied twine rm
hat teeter. ‘Phe melting: point e! the reoxyetellteed materiel m 130-
131' c.

The pletimee aide catalyst need me obtained free tee Cour...
One betah new precured tun the America Pletim Herb. Yhe ether
pletinmn aide emple need in thie inveetigetion \ne prepered tron
Chlemphtinie e016 by the netted of Adam. Veal-hen, end Shrine!- (11).
In e 600 ml. teeter. 20 gum or emmintely 1&3? ehlempletime eeid.
10 m1. enter, end 40 grew at eodhm nitrate were placed. The better
wee eupported on 1 wire eereen end the mixture me «repeated to dryneee
ever e and Bums! flame with etirrlng. The twenture use thm mined
end mum took piece. erter whioh the temperature In gmdueuy rend

te the sexism: heat eutput of the Baum tie-m. When the vigorou-

erolotion of nitric uidoo Ind ceased. oe indicated by the dieoppearanoo
of brown colored mm. the mixture m digested at mime heat for on
additional 30 aim-tee. After olloeiog the digested noee to cool to room
temperature. it we treated with 200 ml. water to diooolvo the ooluble
oodiun ealto. The insoluble bm platinum aside me filtered and dried
in an are: at 108’ c. for eight house. A eooond «pantity er the plati-
mn aide ontolyot no promrod according to the procedure doeoribod
above. The total yield of platimm aide obtained in the" too prepara-
tim omntd to 7 grow.

The Buoy nickel ootolyot one prepared from a nickel-olundmze allow.
procured from the Central Soionti fie Company, by the method or Poolio
1nd Adldne (12 ). In a two-necked three-liter {look equipped with a
otirrer and thomonotor. 129 gram or loditm ludromido and am .1. of
utter tore placed. the {look no imorood in cold running water and
100 gram of the alloy were added in wall portion to the ropidly etirred
«lotion. The coupon-emu nu mintoinod at 50° c. mar the addition
or the olloy no complete, the eueponeion one digoeted for one hour on a
uter- beth at 50’ C. The mepmion of nickel catelyet no mhod by
decantaticn with water about treaty time to two all alkali and water
eolnblo eolte. The rooulting finely divided nickel woe tnoeferrod to a
250 Ill. centrifuge tube and nehod three time by etirring oith 952‘!
ethonol centrifuging: after each addition of alcohol. The om procedure
we followed with aboolute ethanol to rte-eve the loot of the Inter 1m

the cotalyot. The product one than otorod under abooluto ethanol.

.6.-

.l:ull)|\ll\l I’ll): I,\ ll ‘ ll}

Bonemo, ethylbonoene. ieopropylbmeoo. and m—butylbemone
were obtained ae the boot grade mote-n chemical“ All of the above
mono-albumen. except ioopropylbeueno could be need for kinetic
otudiod otter fractionation in a 60 on... 15 m. bore colon: poked oith
1/8 inch glue holioee. The ioopropylbemene had to be refluxed am
annoy nickel for 24 More and then refrectiocoted. In all «no.
middle cute were need in the hydmgantiono. Telnmq‘reagocd: grade, to
purified by extracting; one liter three timeo with BO :1. portion! or
concentrated oulfurio ooid accordlg to the method of flat (13). The
air-acted toluene one than nehed Idth eater, refined for 84 houro
o'er oodimo rollover! by reflux for an additional :4 been ova Mq
nickel. followed by fractiomtion in the colon ddoribod obo'ro.

'rho o-anylbmae one outbound by following isortoo'e modifica-
tion of the darts-Finis motion. (14).

K p 8 . r ' m z 2 ‘02 T18
\ 4' mac zitflaCHaCl e NI y?

0, Heel e 1/5 III

A mopene ion or 400 gram of eodime eend we prepared by heating; eodion
metal in one liter of toluene ooutoined in o three-liter. three-mocked
flank. oqzippod with a Herohberg etirror end themomoter. The eodiun
and no formed by Vigormo etirriug of the medium with tolumo at 100°
C. After the eand one formed, the oueponeion of eodiun in toluene ole
stirred and cooled to 70-75" c. and no gram of 3.13mi chloride were
added over o pried of too homo. Ptirring who continued too bonro

-7.

ether the addition of the elkyl halide use completed. The fiction
mixture m then attracted with other, the amber removed on I stun
beth, end the product (nonmetal 1n the calm previemly deeorlbede
The {notion of adwlbemme cemented dietuled at 201-208” c. at
etmeephodo preeaure. The yield an 107 gram or 16:51 or the thwetleel
Md on the n-butyl chloridoe
Cyclehexene, Eeetm practical grade. end glaciel eodfle eeid.
Bekor'e 6.9. grade, were found miteble for use after dietilhtlone
The upedmtul boiling palate. corrected to 760 m. by noon-
ef' Trenton'e Rule and the Gleueiueamepqrren equation. a well u the
reported boiling pollute (15) of fine liquid new: used in male at!

are recorded in fetal. Ie

 

 

 

1181.2 1
Compound Corrected BePe Recorded 8. P.

Roman 80 80
Toluene 110 111
81:11be one one 13 4 136
Ieopmyylbmene 151 152
herb-Butylb emcee 185 169
n—melbemme 203 205
Ioetic eeid 118 ll

Cyclohemene 83 E3

go: Pressure Hydrogenation
The six mn‘lkylbenzmee hydrogenated were benzene, toluene. ethyl-

hence. leopropylbmme. tort-butylbmme, and rewlbmeuee hot:

.6.

00mm! m hydrogenated at four di’Tereut temperature“ unholy;
35°. 45°. 55“. end 65° c.

A etenderd l’err lee preeeure epperetue ue need for theee hydre-
genehionee The eeeonpenying, preeenre gouge wee gndueted in ponede per
equere inch from which the preemre readinge were eetiuted to the ear--
eei: hath ef I made The rotation fluk, or heevy ulled Pyrc glen.
me filled Iihh e directly ineerted thermometer end e heeting Jeekeh
eoeizrelled by e veriee. The tmmtnre control dun-in e Magnetic:
eu minteined eonetent with e verietion of 1: 0.5" c.

The volume er hydrogu void of the eppretne we determined by hy-
drogemting en ecetie eoid eolution of neleie eeid (Tehle l. Aegean).
Meaning e quantitetive hydmgmetion of the olefinio double head end
vein; the ideel gee he, the hydroga void In oelonleted to be 4.35
literee The nine for the void eee reehecked by hydrogeneeing eyele-
heereue end egein oelenleted to be 4.35 litere (Teble 1. Appendix).

ash elicylhmene imimgenehion we carried out employing e nix-
here of eppreuinetely Oe05 uncle of the empeund he he hydrogeneted.
0e! gree of pletinm oxide oetelyeh. end 10 ml. of gleciel eeeeie eoid
eelvat et en initiel mama: pruenre of 64.3 ponede per equere ieohe
i'he precednre need during eech hydrogenation eee ee follow. The re-
eehion fleet oonteining the neeenred enentitiee of hydrogen eeoeptor,
eetelyeh, end eelveui: wee reetened to the epperetne whet-expat it we
fluehed out three tin. with ivdrogene The fleet we the: heeted to

the appropriate twenhure end edjueted to the duired inihiel hydroga

09-

preeenre. When thie we completed eheking one eterted end et the end

of definite time intervele oorreepending prueure rudiuge were tek-Ie
At the outset of the vex-k. eone difficulty one mounterd beoenee

of unexpected devietiom tron lineer hydrogen-tine ourne (Tehlee 3. 4,

end 6, Appendix). the difficulty eee found to be owned by the nee of

tee lerze en meant of gleoiel eeetie eoid eolvmt, 50 ll. Apperutly.

not the rete of hydrogenation but the rete of diffueion through the eel-

vent one being mount-ed. When the quentity of eelvent eee rodnoed to

lo ale. {he upected firet order corre- vere obteined. The recorde of

eubeequent low preeeure hydrogenation ere enmerieei in Tehlee 6.29

( Appendix ).

flhfi Preeeure hydrofiemtiong

The standard Perr high preeeure epgeretue we need for the hydro-
gehetiom. All the mm were made Iith e boat o! 60 ml. void end e 20
file glue liner. The eooompemring preemre gouge nee gnduetod in 10
We per equere inch unite end me read ee ouch. The tnporetnre no
controlled by the etenderd etteohed heater end no moored by e thermo-
couple etteohnmte The tempereture during e hydrogenation wee nin-
teined oomtert iith e verietion of 2 1° c.

The volume or hydrogm void of the epperetue eee determined by hr-
drogeneting: en eoetie eoid eolntion of eyelohexene (Tobie 30, Appendix).
homing quentitetive hydrogenetion of the olefinie double bond end
ueing the ideel gee lee, the hydrogen void one oelonleted to be 65 111.

Each elhylb eneene lordrogeneti on m oerrled out on e nixture of

eppmimtely 0.025 mole of midi-egg: eoceptor. 5 cc. of gleodel eoetio

.10-

ecid,'end 0.1 gram of pletinum oxide et en initiel hydrogen preeeure
of 1200 pounde per equre inch. The: the retio of melee of hydroga
eeoeptor to 5mm of oetelyet wee epproutimetely 0.25. the eene retie
ee in the lee preemre hydrogenetieme

the procedure used during eeoh twdrogenetion no ee follow. The
liner eonteining the metered enounte of Mdmgm eoewtor. «but.
and oetelyet wee pleoed in the boat which one emlod end etteohed to
the eheher. The bomb me then heated to the desired tempereture et
which time the initiel Mrogm preeeure wee edjneted to 1200 pounde
per equere inch. Sinking; one eterted end oorreeponding reedinge of
time and prueure were token no in the nor): on lee preeeure hydrogen-
tiom. The date on these hydrogenation et three differmt taper-eta"-
for eeeh compound ere mmrieed in Teblee 31-48 (Appendix).

It ehonld be noted here thet different hetohee of eetelyet ere
need for the low end high preemre hydrogeheti one. The pletinun oxide
procured from the Amerioee Pletimn Wen-he no need for the lee preeeure
rune end the propend platinum oxide for the high preemre me Sine.
the eotivity of eeperete betohee of oetelyet differs. it would hove been
prefereble to me only one utelyet batch. However, on ie indioeted by
Tehle II. the epperent eotivetim energiee of the melhylheneenee.
end prominently of any hydrogen eoooptor. very with the portionler oete-
lyet need. Teble II lmlioetee elee thet the relative epprmt ectivetioe
Clergy veluee of the monoolkylbeneenee. ieee. the poeition of one eon-

poond in the eeriee in the order of inoreeeing epperent ectivetim

eel 1-

margin. do nab chenge. Therefore. by comparing the ectivetion aer-

giee of one or more ”We hydmgemted over two different ample-
or cetflyeh. e11 value: are referred to e eingle utelyeb hatch.

TABLE II

APPAREIT Acrnmxw 3mm CAL/”0L!

 

~ . - ‘-_.s—.~—.-- nae-o. -- v-w" —y~q—u a..-» 1. ---—e.- .—.. v~~Ior “~-

 

 

Compcund Get. A Cet. D
Rivlbeneene 4900‘ 2700°
toluene 3600b 1800‘

e mete in Tehlee 14.17 (Appendix)
b ' I U 1%” I
o " " " 49-51 '
d ' ' ' 52-54 '

-12 o

CALCUULTIOE'} A???) RESULTS

CALCTUAT I CHE M70 P. $3138

It hee been damnetratod in this end other (7). ('8), (9) etudiee
that the ivdrogemtion of benem derivatives over platinum oxide in
ghoiel acetio eoid eolvent‘ ie firet order with reepoot to the hydrogen
preeeure. eero order with reapect to the consultation of the hydrogen
eoeeptor, end directly proportionel to the emuut er oetelyet need. It
hate the been ohm that in the kinetio study of heterogeneous metim.
the rate oomtmte depend on the volume of the gum eyetn need (16).
Therefore. the rete of the motion for e givm mount of oetelyet on

be «proceed by the equatia

”42513-3
15" 7

ehieh. when integrated end converted from mturel logrithm to logarithm

PM

on the heee ten. given

log P; 33 kt .
YE” T553"!
where k is the velocity content. t is the time, ‘9' ie the hydrogen void.
Pg: ie the initial hydrogm preeeure, end F132 ie the hydrogai pressure
at time. t.

Thus to oeloulete the veluoe or k, the elopee of the linee obtained
by plotting log gig/PB: Against t were mltiplied by 2.3m. These eon-
stunt-e, determined from different emanate of mtelyet met then he re-

ferred to one graze of mtelyet in order that ell veluoe say he compenble.

-13-

All the velocity comtante determined in this moor are recorded in

Table III.

in Figural 1-14.

TABLE III

The plate used to oeloulate those rote contents ere ehom

W
I: I: 103 It 80 113mg

 

k x 103 et 4 eta

 

 

Comggund 35° 45° 55° “M‘659 379__ 55° ‘30° _11
Toluene 74.0' 98.8 109 130 8.06 11.4” 13.7
Ethylbeneene 30.4' 102 125 151 10.7 12.3c 13.5
Ieopropylbeneene 59.3 74.0 63.2 115 7.13 9.02 10.1
Butylbemeoe 41.4 57.5 74.9 94.0 5.55 6.69':' 1.33
Mwlbmlme 60.5 67.9 81.0 9P.6 1.58 8.44 10.2
Toluene‘ 59.56! “ea 70e°° In -- n- .-
Ethylbenxene‘ 31.0 105 .. 157’ .. .- .-

e Compound wee hydrogenated with some «lately-t need et

80 atmosphere.

b At 31° c.

e At 40° c.

d 11% ea“ c.

0 At 57° Ce

1 At 63° 0.

g Velnee ere corrected to eemple of cutelyet used e1:

4 etaoepheree

fiinoe the rate oomtente for etch coapouod. It both high end low

pronun- wore determined at ewerel teapemturee, en epperdl: eatin-

ticm energy can be calculated from the Arrhenius equation

.14.-

k I [19"3/3
where T3 in the apparent acti‘zetion energy, T is the absolute tempomture.
R in the me constant. and A in the Arrhenius frequmcy rector. ‘I’hie
equation my eieo be ropreaewted to
log; k I - M 4 10:; A

Thus, a plot. of 10;; in venous 1/!) should rooult in a straight line whee.
elooe when mitipiiod by 2.303 I: in the epmrmt activetion energy.
Thoee plate are ohm in Figures 2 and II, for low and high prmeure.
reepoctively. Coco the apparent activation may he been determined.
the frequency rector. A, can be obteined by reeubetitution in the
Arrhmiue equation.

' The nluee ohm for both the apparent eotivetion energiee end tn.
treqneewy rectore vere oheokod by «hunting than by the method of
evongee (17) and ere found to be quite eoourete. the mean deviation

being; lees than 3:33 in e11 canoe. 'fhoae value- ere listed in Tobie I7.

.15.

TfiB‘LF‘. IV

 

 

 

W A J“ , ' _ W
461112110: pheree 80 Atmo- phere:
C 3 e ' Le A 5‘ Col Lo A
OW m 5 775T: 6

 

Bea: me 280’.) 0.99 7000 2 .93
Toluene 86300 1.43 E400 3.61
mayhem one 4-900 3.41 3909 0.23
Ieepropylhmme 4200 1.74 5600 1.92
t-Butylbens one 5800 2.74 5500 1.59
n-mel'oem one 5600 1.29 4900 1.25
roium" moo .. .. ..

11:11wa each 2800 .- .. ..

e Veluee corrected to the eeme betch of utelyet
need et 4 otmoegheree

h Hydrogenated over the use batch of oetelyet
need et 80 etmoepheree

-16-

«cur-5“

 

Qfi

‘04-51 “901

1.9
FIG. :1:

Low PRESSURE
m ARRREMUS Fug-S-

 

”235 300

3D: 3w) 3M5
Ufi‘fillo3

VJ

IDDD’O

BENZEME

TOLUENE
ETfiweaaNzENg
isoPRDMLBENzENE
TERY-BUTYLBENLENE
NSAMALBbNZENE

 

”310 azg’

v *1”?-

 

 

   

\ o BEN‘LENE
2. O TOLUENE
3 A ETMLBEN‘LENE
4 A ISOPRQPVLBEHLENE
5 c3 TERV‘BUTXLEENIENE
G I N-MNLBEN'LENE
|
10
mo\
2-6
Loo
r
0 0
CD 1+
7: \
l
+ 90 6
I" .
‘ o

 

FIGfl

HIGH PRESSURE
ARRH EN 105 PLOTS

  
   

 
      

 

 

DISCWISI CW

DI§C33310fl

An interesting obsemtion my he needs using the epperut active-b
tion mergiee sheen in Table II. The results obteined in this investi-
getion indiute that the epgerent eotivetion energies of the comrade
studied Very with the pertiouhr staple of platinum oxide catalyst need.
end thet these eerietioos out be or e countable magnitude. The theo-
retieel besie behind this obserretion depends on the feet thet the
energy or eotivetion e! e surface eeteiysed relation my be eoepesed of
eererei factors. If to new with Hiasheleood (18) thet the veto
determining step in e sot-hoe reeotieo is e eimlteneeus reactin on
and desorption I'm the eurfeoe. the: the eigeitude of 3 I111 11mm! on
the energ or reecti on end the energ or desorption. both sorreee de-
pendent rectors. Adsorption based on the ective outer theory of e oete-
ly‘tio surface propoeed by B. 3. Taylor (19) end «tended by A. A.
filendin (20) mid account for the dung“; ulna of B Iith differut
utelyst emploe. The nrietion would be due to the difference in eotive
center speak; in different outeiyst staples.

Herertheieee, there ere may int-med in the literehxre were ex-
perimtere empere emrerrt energies of eotivetioe without referring
the vulnee to e single ottelyet hatch. In oddition. there hes been I
tendency to regard individoei nines e! epperut eotivetion duel-glee es
eoourete in the obsolete some. As reeeotiy so 1940. Smith end veri-
eether (21) suggest. on the besis of such eheelute nines. tint in the

following reaction path for the hydrogeuetioo of lemme. the first

-17.

etep ie. rete determining. Date. on the heats of hydrogemtion e‘how

©L©k©k©

thet the energy or reaction for thie step is 6600 aloriee per mole
tree with it reno— thet the clergy of eotivetiou of benzene comet
be leee then thie nine. oetelytieelly or otherwise. Smith end Heri-
Iether then indioete hoe variably ole-e their veloee for 3 ere to
5m oeloriee per mole. Yet, the nine determined in the preeat eerk
for the eppermt energy of activation of benzene ivdrogenetion with e
different oetelyet emple ie 2800 calorie: per mole.

turning to e cone Mention of Table III, it ie eeen tint the
velocity oonetente tear-cue by e rector of ten eha: the hydrogen pree-
enre ie nieed than four to eighty etmepheree initiel preeeure. Thie
deereue ie in eocoraanoe with the Mm-Polanvi transition etete treet-
meat of the effect of pro-sure on reaction velocity (28 )e They derive
the eqnetiu

1%}: a (v1... ‘72)

there 71 ie the volume of reacteme in eohtion end VT ie volume of the
tnmition etete complex. fluey indicate that in e taction of the type
A e 3 -—?A3. of which hydrogenetioo is en eutemple. VT ie much closer
to the nine of 17,. the volume of the produote. then it ie to Y1.

therefore, the ehove reletion my be mdifled to give

dink _(V1-V)
T" "5"";

eel

.16-

Since the deneity ie inversely proportion“ to the volume. deneitiee

my be eubetituted it the ebove equation to give

diet (and)
‘13“ 33:34

A. an be em from Tobie v. the difference in omitiee (:3) gm. e
negative velue tor e11 the reactions studied, thue Validating the a-
perimentel decree" in velocity eonetent with inoreeeing preeem-e.
Quantitative egrment ie not to be expectei. eince the reletion ie en

epproximti on.

 

 

 

 

TABLE V

W ~_:*r::

Roeotent end Product :11 d, ‘1'41
8 on: ene-Cycloheuzene .879 .779 «100
Toluene-fiethyloyolohenne .E C 6 .769 0.097
mhylhmme-Ettvlqoiohmoe .867 .798 «079
i n-Propylbem ene-i-Propyloyolohexe no .9. 62 .790 v.0?!
t-Butylh ene ene—t-Butyloyol ohmne .8 67 .8 18 0.064
“when: me-leoyoloheme e 8 58 .802 «056

The verietion ef eppermt eotivetion energiee et four etveoepheree
preeeure with the etmeimre of the enqbeuxene eppoere to be releted to
the moieouler complexity of the compound. The decreeee of the rete
content with eeleouler complexity bee been noted by ewes-e1 wrkere (6).(7)

who. in general, eeoribe thie «home in rote to eterio rectore. The
epperent ectivetien new: eould be expected to be e better criterion
of the influence of etmoture upon roeetivity thee ie the 'e'elooitgv eon-
etent. The epoereot eotivetion new when dotemined in thie earl:
eho' thet eterio hotel-e oennot oompletely expleio the mletive ntee
or ivdrogmeti on of the homologoue eeriee. For «an?! e, ethylbemeae
he: e moh higher ems-rent eotivetion energy than g—ewlbmooe. iee-
propylbeeeeoe he I lower open-eat ectivetiou user-51 thee ethylhemeuee
Theee hate cannot he reconciled by eterio effect fine. A better «-
pleoetion on be mde on the huie of electronic efieote. elthoogh ieo—
pmgylbemme romaine ee e dieorepenoy.

The dipole moment being e measure or the electronic mture of e
molecule, ehmld ehoe e reletionehip to the eotivetioe energy. if
electronic effecte ere regarded to influencing "notion rote. Bethen

end 'fs‘eteoo (24) have proposed the exoroeeion
3: BC + 135 (A e 43a”)

for functional group reaction of eubetitnted beneeueo. “to ie the
ectivetion Clergy or the unouhetituted molecule. 3 ie that of the out-
etitutod melanin/xx ie the dipole moment in Dobye unite, end the con-
etoote ere dependmt upon the iniividuel series etudieci. Applying the
apt-onion to the date oz" thin work, relative opmroot activation
enorgioe have been calculated one! ere compared to the experimental

mluee in Teble VI.

TABLE VI

 

Couponnd ' Womeut (251 uptl. Cele.
Baum 0.00 D 2800 2800
Toluene 0.37 D 3600 3600
Ethylhmene 0.58 D 4900 (F00
Iaoprom'lbenzene 0.65 D 4200 61-300
avg-91113511139213 one 0.70 D ERGO 5900
g-Awlbemme 0.4 D 3600 mm

 

The agreement between the experimeutal and calculated veluee ie good
with the one exception mentioned before, ieoprepylbmme. Ho «-
plemtion one be ednnoed for the epperent eotivetian energy of the
letter oompmnd on the beeie of the present work or an eny infer-tin
enileble in the literature.

next. the ohengee in eotivetion energy with inereeee in preeenre
ere to be oomidered. Theee veluee et 80 eteeepheree ere eo rende- in
their reletioe to one enether thet they eppeer to be impeble of ur-
plenetion. In order that the reletionehip between the high end lee
preeem'e veluee any be better eeen. they ere lieted in Table VII ee
ntiee for the velocity eomtente end frequency teetere end ee differ»

mee- ror the eppreut ectiveti on energies.

.21..

TABLE VII

 

 

 

 

 

 

 

W: ._ :===ele
CW 1: sac/u e 55" c. Eeo- 54 A BO/A e
Bmue 0.156 . £200 85.1
Toluene 0.163 . 4800 161.
Ethylbemme 0.152 - 1000 0.0295
Ieopropylbenene 0.163 - 1400 1.32
magnum». 0.123 . 300 0.0703
g-Awlbeneme 0.153 - 1300 0.912

 

The only eonolueion that can be preeently deem ie thet e eemider-eble

change is produced in the eppermt eetivetion energiee by the eimple

expedient of nieing the initiel preeeure. Finelly. the dete in

‘rehle III indioetee thet the order of one of hydrogeeetion of the leane-

eltylhemene ee deter-name! by the rete eenetent ie eeemtiell: the em

et both high end low initiel Weir-egg preeeure.

-1-

2-

1.

3.

4.

STITQA RY

Rate conetente. epherent energies of ectivetion. end Arrheniue
frequmcy rectore heve been determined for the oatelytio 1min»
genetion of bemene end some of its mno-elkyl homlege we:-

platinum oxide.

It he been ehm thet the epperm'h ectivetien meta of the re-

eotion veriee with the perticuler eetelyet ample need.

he aplemtion of the effect of molecular etm-cture upon hydro-

genetion he been mee

The decreeee of velocity content with inereeeing prcmre he
been eoeounrted for on the buie of the ehenge in volume hetee.

reeotente end produote in chenieel reeetiene.

LIT 3'5; T7733 CIT I)

LIT "57;! T33R32 CI? 5;?)

(l) 9&1”. Ann. m. 200 (1PM).

(2) Tmmletion by Reid. Cetelfeie in Organic ChenietryJ Yen fiesta-and
Co.. New York. 152:. ‘

 

(3) Adamo, Veorheee. end Shriner, Ormnio 9 ntheeee. Collective Vol. I.
p. 452, John fllw end Sone. flew 50745. 15.32.

(4) I peti eff,
ancni

Cetel tie Reectigee et High Bruegel-es end Tagger-atone,
Qfi. Li“70?k. 193E. ——

 

   

(5) Ismetrong end Hilditoh. Pros. Key. 300. .199}... 249 (1921).

(G) [idem end *‘arehell, J. fin. Chen. Soc. 22, 1970 (1928).

(7) Smith, Aldormn, end Hedig, J. An. Chen. See. £1, 1'72 (1945).
(a) Smith end Peiinohmp. 3m... 276 (1945).

(9) Smith end Pennokemp. 33g... 279 (1945).

(10) Baker end fidmote. J. Am. Chem. Soc. E2, 1250 (1947).

(ll) Aden, Voorheee. end Shriner, Orr: nio By ntheeee, Collective Vol. I.
p. 452, John Wiley end Sane, our or . .2.

(12) Pevlio end Adkins. J. Am. Chem. See. 51. 1471. (1946).

(13) Fieeer, moorinente in Organic Chewing, Kath end 00.. New York,
1953. 9. 5E.

 

(14) Horton. J. An. Chen. See. $9, 1429, (1958 ).

(15) Lego. 'Eiendbooig of Chemiet ." Handbook Publiehere. Senduekq,
unmet. 1

(16) Fuel): end Smith. J. Am. Chem. Soc. 22, 3743 (1040).

(l?) Fieniele, 'E’ethnticel Preparation for Maysicol Chemistry,” "0an-
mn. my York, 1928. 92>. 235-237.

(18).:‘iineheleood. 'Kinetioe o! Chemieel Chenge." Detox-d University Preee.
New York, 1940, p. 187.

(19) Taylor, J. We. Chem. 32, 145, (1926).

.2 4..

(20) Belendln. Ante Physicochim (7.7.3.9..8.) fig. 92 (1947).
(21) Emith end ”eriwether, J. Am. Chem. fine. 11, 413, (1949.).
(22) Wane and Polanyi. 'E’mns. For. 906. E3. 1537 (1955).

(23) Q3310”. ”Physical Comteote of Etrdrocerbovn,” Reinhold, ”em York,
1940.

(24) :fa’chen end flatten, J. Chem. Soc. 1033, 893.

(25) Baker and Graves. J. Chen. Soc. 1339, 1144.

a I.
an". .3-

AP? QIZUX

HYDROC 3&1? I 0?? T131 ‘53

l‘eble l

 

 

thieie Acid Lon Preeenre
0.0473 uolee 0.0595 5e 900'
166 ml. eeetie eeid Po
Time Win.) Tenn. (°C.) Preee. (P.S.I.) Log «F-
0 83 60 .0000
16 32 58 .0141
31 33 81 .0220
68 83 5‘! .0220
100 33 56 .0298
135 33 66 .0298
165 33 56 .0290

 

 

 

 

 

 

_ Cyclohatene Low Prueure
0.1428 nelee 0e). 80 Pro:
25 n1. eoetie eoid P.
Time Win.) Twp. (“0.) Preee. (P.8.I.) Log '5.
0 an 64.4 4-
l 28 00.4 ..
17 23 33.7 .-
20 28 02.0 one
Tehle 8
Benzene ' Low Preeeure
36 n1. eoetio ecid '
Tine Win.) Tenn. (00.) Preee. 0.3.1.) Leg $9.
0 35 64.4 .0000
6 86 63.0 .0090
10 86 82.1 .0164
86 34 60.6 .0268
40 84 60.8 .0290
57 55 60.1 e0293

 

.26-

Teble 0

 

 

 

 

 

 

 

Benene Lew Preeeure
0.0686 melee 0.1213 g. we2
85 ml. eoetie eoid Po
’1” (mine) I”. (03.) Pf... (P.3010) M r
0 38 64.4 .0000
5 36 63.0 .0000
10 86 81.8 .0190
18 80 00.8 .0280
20 84 59.0 .0346
18 36 68.6 .0410
88 34 ".7 .0465
56 35 57.0 .0387
Tehle 5
Ethylbeneene Le! Preeeure
0.0492 melee 0.2037 fie PTO.
50 n1. eeetie eoid Po
Time (mu...) Temp. (°c.) Pr... (10.34.) Le; ,-
0 20 64.0 .0000
10 28 03.1 .0086
10 87 62.! .0154
80 28 61.8 .0100
00 20 60.5 .0261

 

47..

2.51.10

 

 

 

 

 

 

 

3mm Lee Prawn
0.0550 melee 0.1973 g. 3"1'0a
10 n1 eoetie ecid
nu. me.) me. ( c.) Preee. (9.9.1.) Log 33.;
0 85 64.4 .0000
6 85 62.7 .0116
ll 35 61.0 .0208
16 86 60.3 .0286
20 85 59.1 .0314
30 35 56.5 .0565
87 36 55.0 .0682
05 38 53.4 .0813
50 35 53.4 .0813
Teble 7
4; _* eéi===
Beneene Lee Preeenre
10 n0. eoetie eeid
Tl“. (mile) T‘Pe (030) Pf-"e (55301.) L98 .2;

0 46 64.0 .0000
13 48 60.4 .028!
15 44 59.5 .0048
82 48 57.7 .0477
87 46 58.0 .0813
38 45 65.1 .0671
87 65 53.8 .07?0
43 45 83.1 .0028
45 46 53.1 .0328

 

~00-

 

 

 

 

 

0 .05 55 ”I .I

10 m1. tactic told

3mm Low Prmuro
0.0557 molt: 0.2065 g. Prq:
10 ml. tactic acid Po
Tim Fan.) ramp. (00.) Pro... (P.3.I.) Log ,-
0 55 64.4 .0000
10 65 60.9 .0245
15 55 50.1 .0370
20 65 57.8 .0504
23* 54 54.0 .0759
35 55 02.5 .0888
‘1 53 53.3 .0896
fatal-g 9
8mm Lav Pr. aur-

0.2088 s. ”0‘

 

rm. (mm) Twp. 0°C.) Frau. (353.1.) has £3

0 as 65.2‘ .0000
a as 88.3 .0133
10 64 61.3 .0363
15 cs 59.: .041.
as as 55.4 .0112
30 65 53.2 00985
as 61 52.8 .0910

hblo 10

 

 

 

 

 

1011191). Low Prouuro
0.0554 moles 0.2095 5. PM:
10 m1. acetic ucid Po
mm. (”3111.) rm. (0c.) Pro... (32.1.) Log 15"
0 35 64.5 .0000
10 85 62.8 .0158
15 55 61.0 .0249
20 35 60.0 .0310
35 55 66.5 .0542
45 55 55.0 .0689
55 55 63.3 .0824
64 34 52.1 .0927
66 33 52.1 .0927
11151. 11
1‘01qu Low Prawn
10 m1. acetic mid P.
T1" (31111.) Temp. (00.) PP... (PQSQIQ) Log ‘5-
0 45 64.4 .0003
5 45 62.0 .0095
10 45 61.5 .0199
15 44 60.3 .0290
52 45 55.? .0628
40 45 03.6 .0799
4.5 45 52.3 .0905
47 43 62.1 .0910

 

40-

Tablo 12

 

 

 

rah: an. Lav Pro: auto
0.0564 moles 0.1988 g. 9702
10 m1. acetic acid
T110. (513.) 7m. (60.) 1"... (1303.10) Lot :3
O 55 64.4 .0000
5 56 62.7 .0107
10 65 61.3 .0212
1 53 09.8 .0626
25 55 68.7 .0554
40 55 62.6 .08?1
49 53 51.8 .0938
Tabl. 13

._ -.. «.— . .uflu. --— ._- -.¢-~.-n-—.....~ “”0”“an

 

 

Toluene Lo- Pnuuro
0.0530 Hole. 0.2021 3. P10,
10 ml. 45.010 tcid ,3
21-. (’fin.) romp. (°c.) 9r... (9.3.1.) Lop; 'F"
0 65 64.4 .0000
8 65 62.6 .0120
15 65 59.0 .0378
20 66 58.7 .0546
30 84 53.4 .0810
40 65 51.5 .0966
43 64 51.8 .0980

o8!-

Tabla 14

 

 

 

 

 

 

Ethylbansuno Low Pressure
c.0459 mu. 0.2067 5. Pro:
10 m1. lactic Icid Pb
Tim (3am) “Imp. (°C.) Pram. 0.5.1.) Log ~5-
0 35 64.8 .0000
5 55 63.5 .0078
15 35 60.8 .0245
20 55 59.6 .0330
30 35 57.4 .0496
55 35 65.0 .0573
40 55 55.4 .0648
45 35 54.5 .0719
80 35 53.7 .0788
36 33 58.6 .0792
$3131. 15
$tv1hmuno Low Pressure
0.0473 solo. 0.2073 3. H02
10 n1. hectic ncia P
Tim mu.) Tap. (°c.) Pr... (9.3.1.) Log .52
0 45 64.4 .0000
6 45 63.0 .0096
15 45 59.7 .0528
20 45 58.5 .0428
30 45 55.5 .0641
35 ‘5 54.8 .0734
38 45 53.6 .0792
40 48 53.3 .0821

v. w—V

Tablc 18

 

 

 

 

 

Ethylbmmc Lav Prat-arc
0.0530 m1.- 0.2054 5. no,
10 ml. acetic acid Po
T1“. (Film) rm. (Oct) PP... (Pug-I.) 103 F-
0 55 “a0 .0000
5 55 63.5 .0128
10 56 60.6 .0257
20 55 57.0 .0537
15 55 55.3 .0653
80 56 53.5 .0799
35 85 52.4 90090
36 52 52.8 .0899
f‘bl. 17 o
whibmam Low Pr-mro
0.0478 m1.- 002110 3. no!
10 m1. acetic acid Po
Tim (”13.) Twp. (0a.) Pf”. {903010) Log r
0 85 64.4 .0000
8 65 61.5 .0199
10 65 59.5 00338
15 65 57.: 00500
20 65 55.2 .0663
25 65 53.1 .0881
31 61 52.9 .0857

-33-

Tahla 18

to: Praaaura
0.20“ {a ”0g

ioPropbeaamc
0.0427 "1.
10 ml. acctic acid

 

 

 

 

 

um. Mn.) rap. (°C.) Frau. (P.3J.) Log ;9-
0 88 64.4 .0000
8 38 65.4 .0065

15 35 61.0 .0183
26 84 60.0 .0308
86 35 58.8 .0488
43 35 57.2 .0613
03 88 55.7 .0626
80 38 55.1 .0614
66 a 64.6 .0112
Tabla 19
t-Prcpylbmaua . Lav Prcaaura
000064 ”I“ 001975 5- ”Ga
10 ml. acatic acid - Po

1113. Olin.) Tap. (06.) PP... (PaSQIO) “g 1F-
0 45 64.4 .0000
5 45 63.2 .0073

10 44 62.1 .0149
20 45 60.2 .0290
81 44 57.9 .0467
41 46 56.0 .0600
50 45 64.8 .0697
68 45 53.7 .0788
63 48 63.4 .0810

 

~34-

Tabla 20

l-Pnogylbcncaaa

10 E1. ‘c‘bt. ‘01‘

Low Pracmra

 

 

 

 

 

Tim 000.) rap. (°C.) Prawn. (P.3.I.) Log ;3
0 55 64.4 .0000
5 55 63.1 .0032
16 54 60.4 .02‘5
20 55 59.5 .0538
85 58 56.2 .0584
45 55 54.1 .0748
50 55 5343 .0821
55 52 53.8 .0821
Tabla 81
1-Prcpylbauaua Low Precaura
0.0405 1-qu 0.3000 g. 1mI
10 m1. accflc acid
um (3am) Imp. (°c.) Praaa. 0.3.1.) Log 15,3
0 63 64.4 .0000
5 64 62.6 .0112
80 65 57.7 .0469
27 65 85.8 .0641
88 65 03.6 .0792
36 65 83.6 .0793

~35.

Tabla 22

 

 

t-Butylbanzwa

19 0.1. acetic acid

Low Pressure
0.1952?! fig P7503

 

 

 

 

 

 

Tim (41“) Twp. (°C.) Press. (P.3J.) Lag; g?-
0 35 64.4 .0030
5 55 63.5 .0052

15 55 62 .4 .0133
25 55 81.3 .0212
85 55 60.2 .0090
46 38 59.0 .0376
Tabla 23
Wylbcmma Low Praaaura
10 m1. acabic acid

Tim (0121.) Temp. (00.) Pm... (9.0.1.) Log {,2
0 46 64A .0000
5 44 63.4 .0070

10 45 62.5 .0128
15 45 61.6 .0170
25 45 60.1 .0290
36 45 58.0 .0422
45 45 57.3 .0504
56 45 66.2 .0588
60 45 65.6 .0637
~50-

Tablc 24

.‘_‘

 

t—Butylb mama Law Pruaura
OaOQVS H010. 0.3000 8a P302
10 111. .0’310 ‘dd
Tim (”111.) T659. (00.) Fran. (P.3d.) Log E9.

0 65 65.8 .0000
5 54 84.6 .0030
10 55 83.3 .0166
20 55 61.2 .0314
30 55 59.1 .0461
41 55 57.1 .0607
50 55 55.6 .0720
60 65 54.6 .0821

h. #1

Table 25

 

fi-autylbcncanc
0a0531 ”100

Law Pramaura
0.2040 5. P102
10 m1. acetic acid

 

Tina Win.) Tap. (°c.) Praaa. (P.S.I.) Log g...

0 85 64.4 .0000

5 64 62.9 .0099
15 55 60.2 a0?”
20 65 5f! .7 .0398
40 6-5 54.! .0748
50 ea 52 .0 .0888
55 62 52 .5 .0888

 

93 7-

Tabla 26

 

v—r a. —fi

 

 

 

 

 

48-

n-A’vlbamono Law Prawn-o
0.0490 1|qu 0.1997 5. Pro:
10 31. tenth acid
11‘. (Mn) Tflpo (°C.) PPQOQ (PCRQIQ) ‘08 $9.
0 .55 54.9 .0000
5 36 33.9 .0070
10 35 63.0 .0128
15 35 62.1 .0188
25 as 60.4 .0310
43 35 67.4 .0631
50 35 56.3 .0611
62 35 84.5 .0768
Table 27

:14..wa mam Low Prawn

0.0483 solos 0.2012 5. H03
10 131. wide mm P

Thu ('flu.) Tap. (“0.) Prat. (P.$.I.) Log .99.

O 45 64.4 .0000
5 45 83.3 .0078
10 45 62.3 .0145
15 45 61.3 .0216
:5 45 59.4 .0650
55 45 57.6 .0480
45 45 65.9 .001).
55 45 84.5 .0719
65 45 53.3 .0821

Tab}. 28

 

yr—vw

nquylhanIIno

Low Pressure

 

 

 

 

 

10 m1. acetic acid .
TIM (”13.) Temp. (0C0) F’PGUO (453.5010) L05 ;2
0 65 65.6 .0300
5 54 64.2 .0086
10 65 63.0 .0166
‘80 55 60.3 .0333
30 55 58.2 .0512
45 55 65.2 .0741
53 55 54.1 .0826
55 68 64.1 .0828
Table 29
.7 A M
34:71}:me Lav Prawn
10 m1. tactic acid P
Time (11111.) rap. («3.) Pro". 09.3.1.) Log 15?-

O 65 64.4. .0000
5 54 6300‘ .0994
10 65 61.5 .0200
20 £36 68.5 .0410
30 65 56.1 00593
40 £5 53.? .0785
42 63 53.4 .0010
44 63 63.3 .0814

 

-3 3..

‘rablo 30

 

 

 

 

 

 

Cyclohuono High Pronuro
0.0621 M10. 001 g. ”02
4 m1. cookie acid po
’13. (man) Twp. (96.) PP“. (ngglo) Log T
0 30 1200 .0000
6 80 1110 .0838
10 30 1.050 .05"
20 30 910 .1202
38 30 850 .1498
55 30 810 .1703
76 30 810 .1708
Table 31
Baum. High Pram"-
0.0288 .01» 0.1096 3. Pro,
8 ml. ”duo acid Po
Tin. ($113.) Tap. (°C.) Prat. (KS-1.) L98 ,—
O 87 1200 .0000
8 87 1140 .0216
6 I? 1090 .0414
10 81' 1030 .0660
15 37 960 .0969
20 31 890 .1800
25 86 830 .1600
30 38 780 .18?!
88 38 700 .2345
‘6 88 670 .2531
‘7 3!! 870 .2631

 

.40-

rm. 8:

 

 

 

 

 

Benson. High Pmmru
5 31. not“: told Po
1'13. (151110) 7.9. (°C.) Pf“.. (’g3.1.) Log ,-
0 65 1200 .0000
3 56 1120 .0294
0 56 1070 .0492
10 55 930 .0881
16- 55 890 .1300
20 55 880 .1600
25 55 m .1929
85 53 600 .“70
88 M 680 .1670
Table 53
Emma High Prawn
000353 ”I“ 0.1018 s. ”0.
8 :1. “one told Po
1'1!» Win.) Tap. (00.) Pun. 0.8.1.) has $-
0 11 1200 .0000
4 11 1070 .0496
8 1’0 980 .0881
11 69 920 .1186
15 89 860 .1453
20 70 730 .1873
25 69 710 .8279
28 69 700 .3345

~41-

Table 84

 

 

 

 

 

 

Toluene mgh Pro-sun
moses moles 0.1010 5. mol
6 n1. Ioohlo cold Po
11m. ($5111.) Imp. (°c.) Freon. 9.8.1.) Log 3"
0 39 1200 .0000
3 39 1150 .0179'
6 39 1109 0037‘
12 30 1010 .0763
16 33 958 00993
24 58 B70 .1399
30 38 800 .1761
37 37 700 .3101
‘5 5? 670 .2533
65 37 680 .2601
Tnblo 35
mm # L * * ' 4* * “* _ * v {M
101mm. High Prmuro
0.0261 ”10. 0.1009 go no:
3 n1. usable acid 1’0
1'1?” ($4113.) Yup. (0C0) PP... (P.8J.) L08 F—
O 55 1200 .0000
8 55 1130 a025,
3 58 1070 ‘0493
10 54 990 .0835
15 55 920 .1156
25 58 770 01929
30 55 710 .2279
33 50 690 .2403
38 54 690 .3608

v _, ‘ __‘,_

~42.

lelo 86

 

 

 

 

 

 

W L 7 m
2011mm: High Prnluri
5 n1. tactic acid ‘P
111“. (1011.) 113?. (0C9) Prau. (13.3.1.1 1-05 F94
0 7'0 1200 .0300
3 70 1100 0037.4:
6 89 1030 ' .0863
19 38 950 .1014
15 71 870 .1396
35 71 720 .2222
28 70 700‘ .3338
80 89 700 .3358
Tnblo 87
muons». High Pram"
0.0249 ulna 0.1091 g. 1"1‘0a
5 E1. £0¢1° .014 P0
T1.“ (who) Tarp. (060) Prus- (Pogolo) 1’03 r
0 41 1200 .0000
8 ‘1 1130 .0261
B ‘0 1070 .0498
m 40 1000 .0192
15 40 920 .1153
20 39 850 .1498
35 $9 790 .1810
80 39 750 .8039
33 39 730 .2159
85 59 720 .2223
58 39 720 .3223

Tahla 38

Efihylbansoni

High Freeware

5 n1. acotio acid

 

 

 

 

 

T1319 (‘31!) Twp. 0°C.) Prma. (P.§.Io) Log g2
0 55 1200 .0000
3 55 1130 .0257
6 55 1063 .053

10 55 930 .0278
18 56 890 .1300
20 55 81-0 .1706
25 55 740 .2098
81 65 720 .2219
36 65 720 .2219
Tabla 39
3:11:11me High Present.
0.0246 mules 0.1055 5. Pro:
5 ml. acetic acid

11m, (’13.) Twp. (00.) Prafiit (P.9J.) L03 ?
O 69 1200 .0000
3 69 1110 .0338
6 71 1040 .0618

10 71 950 .1011
15 Y2 860 .1448
20 7'1 780 .1875
25 70 720 .2219
37 70 710 .2276

 

~44-

Table 40

A— A..— -_‘

 

 

 

 

 

i-Pmpylbmtmo High Pram-arc
0.0225 mlea 0.1009 3. W02
5 n1. acetic acid
T1130 (333.1.) 7311?. (00.) 3151.13,. (PCSOII) Log £2
0 37 1200 .0090
5 37 1140 ‘0220
10 37 1080 .0457
16 37 1020 .0708
20 37 _ 930 .0685
30 35 913 01202
40 38 54’) .1553
‘7 33 319 01709
51 38 790 .1816
55 08 780 .1878
Table 41
1~Pmpjlbamm I’iath Frassmro
0.0240 moles 0.1002 5. P202
6 a)... neat“ acid
Tim (mm) ”Panza. (0m) mm. (33.1.) to; £3

0 55 1200 .0000
3 85 1140 .0216
O 54 1059 .0635
15 56 980 .OI‘BI
26 56 6:70 .1399
38 55 FOO .1751
47 54 720 .2219
49 64 720 .2210

.45-

Tablo 42

 

- . fl“. ”.“m q-u-n-v-o‘ww m.- v—QW w—Q-WMofiaaN-anwmnmn-...>.~.-.-.as.

 

 

 

 

1-Pmpy1bcmmc High Pram"
000343 W10. 0.1%6 80 m0:
5 :11. «one told P.
fla- Mn.) rump. (’0.) Frau. 0.5.1.) Log r
0 71 1200 .0000
4 11 1100 .0374
10 10 1000 .079!
18 69 m .10”
IO 71 880 .1840
26 70 010 .1105
30 09 780 .18”
85 70 740 .3098
Table 43
tcfiwhylbmao High Frame
0 m1. auntie mid
71m (any) Tm. (03.) PT... (P’s-Io) Log g!
0 87 1200 .0000
5 57 1140 “115
10 37 1100 .0370
20 87 1010 .0660
30 03 060 .0960
01 43 890 .1800
50 4: MO .1050
61 ‘0 810 .1708
66 40 j 800 .1761

Tablo’40
W

 

 

 

 

 

t—Bueylbc-xuno High Priflluf.
0.023: mole. 0.1073 g. FTC:
‘ In]... COWi. ‘01d P.
1'13. (filo) flip. (00.) Pr... (P3010) Log F-
0 55 1200 .0000
8 06 1150 .0110
11 B4 1060 .0535
18 53 1030 .0660
24 57 960 .1014
30 80 010 .1202
38 55 860 .1452
48 56 810 .1700
55 55 76° .1937
80 54 750 .2039
0; 54 150 .2039
Table 46
t-Butylbom an. High Pro-inf.
0.0281 mole: . 0.1050 5. Pro:
6 an. taltic .016
Tim ($111.) Tap. (°C.) Pun. (P.8J.) Log $3
0 70 ' 1200 .0000
3 70 1150 .0170
8 f 70 1090 .0418
15 69 1030 .0533
16 11 960 .0960
35 89 900 .1248
45 70 860 .1490
56 69 800 .1761
85 70 160 .1987
73 11 740 .2098
77 11 740 .2090

 

«47-

Tablo 46

 

=a========================E:

n-Amylb «zone

5 :1. acetic um

_

{1gb Pressure
051070 $9 FTC:

 

 

 

 

 

11m. (”10.) Temp. (00.) Frau. (0.3.1.) Log $3
0 37 1200 .0000
4 3? 1140 .0216
9 3? 101730 .0457
15 36 1010 .0758
32 36‘: 040 .1068
SO 37 560 .1453
35 3? £20 .1652
45 35 700 .1072
40 87 780 .1818

mm 47
n-Awlbmeno High Fracture
0.0224 m1» 0.1072 5. H03

5 n1. acetic laid Po

Tim. (310.) rap. (0C0) Prat. (P08 .1.) Log T
0 56 1200 .0000
3 55 1140 .0216
1 66 1090 .0410
10 55 1050 .0577
10 57 950 .1014
28 55 070 .1399
32 64 800 .1761
37 55 770 .1929
40 55 770 .1920

 

~48-

1.1310 48

 

 

 

 

 

 

ndwwmmo mfih Pram?-
o.oeso m1.- 0.0993 5. mug
5 I11. 0.001310 “id
11!» ($1121.) Temp. (°C.) Press. 0.0.1.) has €9-
0 70 1200 .0000
3 10 1130 .0251
6 10 1000 .0051
10 71 1020 .0708
15 11 950 .1010
20 70 B90 .1300
85 00 830 .1605
36 70 150 .2030
41 69 140 .8101
mu. 49
W _ * W
1491qu Law Mauro
0.0015 mola- OJOS? 5. P10,
10 31. «this “1d
’15. (35111.) Tm. (OCQ) 1”... (9.3.1.) L“ g
0 ‘ 09 64.4 .0000
5 30 63.! .0083
10 89 63.3 .0154
20 30 m.5 .0018
30 39 59.2 .0310
I10 39 51.1 .0481
66 30 65.1 .0650
60 39 55.3 .0666

~43-

Tabla 50

 

iiii

 

 

 

 

 

~50—

1'o1uono Lou Prcuuro
000550 ”I“ 002075 5. Pro:
10 n1 . “this “id
11- (‘tfind Twp. (°C.) Frau. (9.8.1.) 10; 3°
0 45 64.4 .0000
6 «H ($3.2 .0088
10 ‘6 62.1 .0158
20 46 60.3 .0280
80 45 58 .5 .0414
4 6 45 06.1 .0606
56 05 54.4 .0736
66 05 03.0 .OESO
15 45 51.6 .0959
83 43 51.3 .0985
Table 51
101mm Lat Pronto
0.0601 119100 0.2010 5. no:
10 :11. watts told
11:. (M30) ram (00.) Pr... ( ”.3 01 0) 108 g.
0 58 64.4 .0000
5 51 83.0 .0005
10 80 62.0 .0152
20 50 60.1 .02 90
81 81 80 .0 .0453
40 51 56.4 .0611
50 51 64.4 .0126
63 65 52 o: 008 99
68 85 02 .3 .00 99

Tublo 52

    

.-~ . .fiw... boo- --»pu-- "u‘~-modm.—

 

 

 

 

 

 

Rum/15mm. La: Pram?-
000403 m1. 002006 E. ”02
10 1111. acetic acid Po
T1" (15.11.) gm. (06.) 91‘... (9.0.1.) 105 r
0 35 64.4 .0000
5 30 55.3 .0013
10 55 62.5 .0141
20 35 53.9 .0322
40 35 55.3 .0056
60 32 54.5 .0726
Table 53
WW
7051171514130!” Lou Pram"
0.0413 m1” 0.2151 g. PM.
10 :11. mo Po
1'10. (“13.) Twp. (96.) Pr... (PQSOIQ) 1“ r
0 45 64.4 .0000
5 46 62.8 .0112
10 40 61.1 .0224
20 45 51.9 .0461
30 44 55.4 ‘ .0652
42 44‘ 52.5 .0810
52 40 52.6 ' .08 "
1451. 54
Emhylbmma Low Prawn \ \
0.0541 m1“ 0.2005 g. ”02
10 :11. mo 9
Tim (3011.) reap. (°C.) PHI-h (05.1.) "’3 "a:
0 63 04.4 .0000
5 63 02.: .0150
10 63 50.1 .0350
20 63 55.1 .0650
51 64 52.4 .0596

~51-

HYDROCTMATIOE 6311 no

 

 

 

 

/
. I)! 6/
I ’ _,
‘ / V f
; I , 5
i I} {I /
8 k f/ If x f
/ v /
f v
r" f
1/ If ° ’/ ' O Afic
£365) f, 55 / 4 1': .~ 4.;
/ If /
7 P , ,1" f
I‘ 71 lb
I/ 17/ I,
‘1
F' if / /
8 f ,
u —
E / fl
‘0 l
X
5
m
5 _
O
I
4 ..
0 I;
0
3 _ O, 'I
. .
" FIG. I
2" " BENZENE
RATE CURVES
I"
\ ..
l l .1 l 1 i

MINUTES

 

 

 

 

 

 

 

<3
9_
8—
7..
6-
r
O o
63
§ 4
~.5'
U
x
5
N
4—
C)
3--
FK32
2' TOLUENE
RATE. CURVES
H"
10 20 30 4O 50 60

MINUTES

 

 

 

x d/°d 90 1

O I

//
/

 

//

/ /

// /

l0 20

FIG, 3

ET HYLBENZEV‘E
RATE CURVES

l I l L
30 4O 5O 60

MINUTES

 

 

'1 q- .5«

 

 

 

9 _
a - /O
O
O
7 _.
O
0
065° 55° 45° 35°
0
6 - O
O
5 " O
O /
O
O
4 _'
O
... O
3 /O
0 FIG. 4
2 ~ ISOPROPYLBENZENE
0 RATE CURVES
0/
'h 8
! 1 e l I 1
IO 20 30 4O 50 60

MINUTES

 

 

 

d/od 901

30' X

 

I I l
'0 20 30
MINUTES

 

 

FIG. 5

T-BUTYLBENZENE
RATE CURVES

 

 

 

 

 

 

9 .—
8 _ /é
7 I. O
65
O
r-
05 " O
o
-o
o\ O
1:
S — O
x
N
4.—
O
O
O
A r
FIG. 6
2- Q N-AMYLBENZENE
RATE cURVES
O
O .
O
I“ W
l l l l l 1
IO 20 30 40 50

MINUTES

60

 

 

 

(LC,

1%

ll

’10

I8

I'L

IO

 

70°

55°
37°
0 /
O
O
O
/ /O
<3 <3
FIG—.7

BENZEN E RATE CURV ES,

Htén PRESSURE

 

10 30 ‘30

MIN UT’Tg

 

 

 

 

26

22

.501 x A/oA 0°"?

 

O
O
O
OO
0/
O

 

TOLUENE RATE QURV ES.

H \G H PRESSURE

FIG.$

 

20

30
rJNUTES

4O

50

 

 

F‘-

 

 

“LOT >< tiled 90 ’7

1%

'23.

9.0

 

FIG. 9
7: TH‘I LBEN‘EENE RATE
CURVES

HI 0. H PRESSURE

 

2.0

 

 

11

 

'10
55°

 

I1 0 w ‘
r I Cr; IO
ISCWNRfiTAHABEfVLngT
£C\ IAwa&i iCAJfKQEIS
R O O ( ‘
L H.187I’L I " I
6
OO
/
IO 1.0 3C) «4:0 5.0

MINUTES

 

 

 

101 ‘X é/QCI 991

27.

10

 

 

HG, II
TERT ”BU'T‘ILBENz‘cI-Ié
I\/DQTE. CURVEg

we I‘I PR 5: :éRE’

 

lo

30
MINUTES

4+0 50 e. O

 

 

 

 

p
O

6'5 00

‘4':

‘OI x (J/Ocl 50“
co 5 3

63

J:

 

FIG. I“).
N- AM \I EBENIENE
RATE CORVES

H IG H PRESSuRE

 

ID 10 30 “+0 5’0

MINUTES

 

 

 

(it/“1 {)0'1

10’ X

A:

 

OO

 

FIG. I3
TOLUENE RATE CURVES

AT LOW PRESSURE WITII
SAME CATAL‘IST A:
usEt? AT HIGII PRESSURE

 

ID

10

'30
MINuTES

00 5'0 60

 

 

 

 

 

630'
‘I O
I?”
8
350
7
O
O
6
r
O
Q 5
*0
O
Q 0
x
,. ‘I
o
r’
O 0 FIG. I“I‘
3 E‘I‘HILBEMALENE RATE CURVES
AT JUN PRESSURE W ITH
O SAME CRTAL‘IST AS USED
1 AT HIGH PRESSuRE
O
x o
0
IO 10 3c +0 50 so

MINUTES

 

 

 

I'll. I III