KENYATTA UNIVERBITYOP AGRICULTURE E TECHNOLOGY
MISTRY DEPARTMENT
FSICAL CHEMISTRY LABORATORY
EXPERIMENT NO. 6
ROMINATION OF ACETONE
roduction
ea n een m e a
t ut on
ctloT h etvoveralbl rore tio n
andia cetone is catalyaed by acid,in aqueous
d
BF²+CH₃COCH₃----·CH₃COCH₂Br +HBr
tha purpone of a kinetic atudy on a reaction ts to find evidenca relatad
to the mechanlem of the reaction.“In thie expariaant,the ordar of tha
renctlon with reapect to bromine and acatone ia to be inveatigated.
theory:
The rate equatlei for the above reaction hag the form.
d[Brz!-k-{B[Br₂lb{(cH₃):co]¹
Where a,b and c ate the orders of the reactlon with reapect to the catalyat,
bromine and acetoneraspectively.
it the hydrogen ion concentratton te kept constant in a serles ot axparimaata,
the above equatlon may be written
Where K¹=k[R*]
Moreover,if we keep the concentretlon of acetone in large excess of the
bromine concentration,its concentratlon will remain effectively constant
during the course of the reaction. The rate equation wi¹1 thet further
-k¹¹[Br₂l² [1]
ihare t¹l.·t(cHy)zoy° [2]
ane order In bromlne,b,may then be determined by meaeuring the bromzne
concantratlon at regular intervals during the reaction and fitting,the
date to the approprlate integrated rate equation,In this way,k T
may alao be determined.Note however that,th observed rate constant,
ie a function of the initial acetone consentration. Taking logs of eq.
[2]we get.
1og kll=10g k¹+Clog [(CH)₂co] [3]
Thua tf the expertmant ta fepeated vith different tnttal conegperatlons
of acetone(keeping it in iarge excess over the bromine)and K is
determined each time,then C,the order in acetone and k',the effective
rase constant, may be found from a graph of log k vg.【(ci₃)₂co].
Requirements :
Two 250m1 steppered bottles,thermostat at 25°C,pipettes,stop clock,0.02M
bromine solution IM acetone solution,IM sulphuric acid solution,0.25M potase
lum iodine solution,0.01N sodium thlosulphate solutlon and IM sodiun
bicarbonate
Bolution,
Procedure:
100ml of approximately 0.02M bromlne solution is added to a 250ml stoppered
bottle and to another bottle a mixture of 50ml M.acetone and 50ml M sulphuric
acid is added.The bottles are suspended in the thermostat bath at 25℃
and 15 min,are allowed for the attainment of thermal equlllbrlun. The
acetone solution is then added to the bromine solution with stirring
and the stop clock is started at the same time.At 5 minute.intervals
a
10m1 sample of the reaction mixture is withdrawn and allowed to.run
into a flaak contafntng 10mI of IM sodium bicarbonate solution and about
2m1 of 0.2JM potassium lodide solution. The lodine 1fberated is
titrated
with 0.01N sodium thiosulphate aolution and a graph is plotted of
titre against time.The reaction is followed until it is complete or
for a
maximum of 40 min.
The experiment is repeated using 100 ml of 0.02M bromine solution in
the first bottle each time,but with the other bottle containing;
&. 25ml M acetone,25ml watet,50m1 M sulphuric acid.
b.37.5m1 M acetone,12.5ml water,50ml M sulphuric acid.
Resultg and Dtgcussion:
Plot a graph ot 1og kll against log [acetane]according to equation [3]
t
and thence determine the order in acetone and k'.Pay special
attention to the units of the rate constants.
Suggest further experiments which would enable you to determine the order
in the catalyst and k.
Discuss a possible mechanism for the reaction which agrees with kinetic data
you have obtained.
JOWO KLNYATEA UNIVERSITY OF ACRICULTURE &TECHNOLOG¥
PHYSICAL CHEMISTRY LABORATORY
EXPERIMENT 13
me Effect of Change of Temperature on the
Rate of a Reaction
Introduction;
Hydrogen c nds on from acidifled potassium lodtde at a
rat e wn peroxide
h llberates
on thiodine
e The
i d e c centration of peroxide and hydrolodic acid.1
reaction ca n pe rep resente d by
2HI 2H₂⁰+¹2
If the reaction is carried out in the presence of sodiun thlosulphate,tre
iodine Tormed is converted back to hydrolodic acid as fast as it is
formzd;
1, S +.2n-
end the concentration of the acid therefore remains effectively unchenged.
he reaction will therefore follow pseudo first order kinetics under the se
conditdons.If in addition sane starch indicator solution is added to ihe
reac tion mixture,and only small,measured quantities of thiosulphate at
added at a time,then when all the thiosulphate is used up,the exce3s
lodine produced willl cause a blue colour appear in the solu:icn,
This provldes a convenient method for following the rate of reaction,
heory:
The temperature dependence of the rate constant,X,of a chemical reaction
is given by the Arrhenius equation;
k=A exp(-E/RT)
r ed (1) t
e A a E e con s cal t he i fr quenc or"
re dt a ants. A i l fn cu pona h de
he " ac tiv io n energy Both of hese va l ues are epe n e
studied.R and T are the gas constant and the absolute temperature
respectively. Taking logg of equation(1)gives
(2)
10k 一 +2nA
Differentiation of equatio(2)zives
dn
Which on integrating belween the limits T and Tt gi
20
g
2.00
R
m
Where k and K!are r ce constants corresponding te two differe it
the temperatures T and Tf the ratia K'/K and the temperatures T and T
are known 。 then
E may be calculated.
Requt rements -2
ra.volume hydrogen peroxide,,0.M sodlum thtosulphate,M sPhurie
aeid,solld potasslum lodide,starch indicator solution,10nl pIpettr
sanl burette,25Cml measuring cylinder,ice.themaneter,stoP-Clock,iit …
eonlcal flask,water bath at 359c.
Procedure:
the 10 vol,hydrogen peroxide is diluted ten times with water.Two
ioc,c. portions of this freshly prepared 1 vol.peroxide are pipetted inte
separate test tubes and placed in iced water to prevent decanposiition,
F111 a burette with the thiosulphate solution.Put 800 c.c,of distilled
water into the litre flask,add 40 c.c.of M sulphuric acid and a little
siarch
tsolution, Dissolve 4 g of potassiun lodine ine 'ittle water and add to
the litre flask just before starting the reaction.Rn in 2 c.c.of
sodium thiosulphate from the burette and start the reaction by adding th:
contents of one of the test tubes of hydrogen peroxide,washing it out
with a little watery Start the stop-clock when the peroxide:1s added.W
ien the lodine produced by the reaction is in excess of thiosulphate a blue
colour wlll appearNote the time as soon as you see the colour
starting and inmedlately add a second portion of thiosulphate.()not
stop he
cl ockthe
.Note ti mew hen the bl uecol our re e ar con t n t his 。
t atpa ,and n ee i
ma r n r until about a doze n readings have bee n en Recor h tempe ratu e
of the reaction from time to time and if it varlas( scanaiderably then take
en average value.
Repeat the experiment using the second portion of peroxide,wlth the
reaction vessel imersed in a water bath at 359c.Allow the contents of the
flssk to reach thermal equlllbrlun wlth the water bath before starting the
reaction. Add the thiosulphate in the same succesive quantities as in the
first experiment.
Calculation:
Tabulate the values of thiosulphate added together with the total times
two
t;and tenperatures T and
t;taken for the T',Calculate
solution the ratioo
to turn blue of total
after each timesfort/t'in
addition the
each aase, the mean value of these ratics is equal to the inverse ratio
of the rate constants,i.e,
t = kl (5》
meen k
Discusslon;
Cament on the significance of activation energies for chemical reactions.
Denve eguation(5)trom the rate equatians at the two temgeratures.
—2—
Requfrements
ia~volume hydrogen peroxide,0.1M sodiun thlosulphate,\M sulphuric ad
acid,solid potassfun lodide,starch indioator solution,10ml pipette,[
soml burette,25Cml measuring cylinder,ice,thermcneter,stop-clock,iitre
oalcal flask,water bath at 35°c.
d Procedure;
the 10 vol.hydrogen peroxide is diluted ten times with water.Two
10c,c.portions of this freshly prepared 1 vol.peroxide are pipetted
intc, smparate test tubes and placed in iced water to prevent
decanposiition.
F111 a burette with the thiosulphate solution.Put 800 c.c.of distilled
aLum water into the litre flask,add 40 c.c.of M sulphuric acid and a little siarch
rsolution.Dissolve 4 x of potassium iodine'in e tittle water and add to
the litre flask just before starting the reaction.Run in 2 c,c,of
sodiun thiosulphate from the burette and start the reaction by adding the
contents of one
with a little of the
watert testthe
Start tubes of hydrogen
stop-clock whenperoxide,washing it out
the peroxide:is added.Wren
the lodine produced by the reaction is in excess of thiosulphate a blue
colour wlll appearNote the time as soon as you see the colour starting
and immedlately add a second portion of thiosulphate.(D2 not stop the
clock).Note the time when the blue colour reappear,and continue in this
marner untll about a dozen readings have been taken. Record the
temperatu e
of the reaction from time to time and if it varlous considerably then take
en average value,
Repeat the experiment using the secand portion of peroxide,wlth the
reaction vessel 1mersed in a water bath at 359c,Allow the contents of the
flssk to reach themal equllibriun with the water bath before starting the
reaction.Add the thiosulphate in the same succesive quantities as in the
first experiment.
Calculation:
Tatulate the values of thiosulphate added together with the total times
t:and t:taken for the solution to turn blue after each addition for the
two temperatures T and T',Calculate the ratiohs of total times t/t'in
each oase, The mean valve of these ratics is eaual to the inverse ratio
=kl
of the rate constants,i.e,
(5》
mean k
Discussion ;
Coment on the significance of aotivation energles for chemical reactlons.
Derive equation(5)fram the rate equatians at the two temperatures.
JOHD KENYATTA UNIVERSITY OF AGRICULTURE E TECHNODOCY
CHRITSTRY DEPARTMEN7
PHYSICAL CHEMISTRY LABORATORY EXPERINZNT NO.2
THE ACID CATALYSED BYDROLYSIS OF AN ESTER
Introduceton;
An aster,such as methyl acetate,ie hydrolysed in d1lute molutton
according to the equationt
си,соосв,-Чн,о снсбон сн,он
Aa the water Ia in large axcess during the hydrolyols Its concontration
raaatny effectively constant.Ie ia found that the differentlal rate aquatton
for the apontaneous hydrolyais ia:
а (eseee1 К» (eaeer]
Whare K 。ta the apontaneous rate constant.
In the abeence of actd the aster hydrolyaie Is rather slow,In the prasence
of an acid the rate aquation takee on the form:
(авза ск,чК,Гн,оЧТЭГавєєтТ
Whera k,ta the catalytic rate conatant for the hydroxonfun ton.Tha
atm of Ehie axperiment ta to deteratne both kandkj~ a done by
atudying the variation of astwr concentratlon with tfma during a raaction,
Samplon are withdrawn at knovn times,the roactfon Aa stopped by
cooling. and the aample ts analyaad.
Requiremetng!
Thermostat at 45°℃,250ml and 150m1 contcel tlaake,methyl
acatate,0.IM WaOн soluelon, ucandaed 0.6, 0.3вана 0,15M НC1
вoluttone.5u1plpeeeuo.
50ml pipetta,50ml burette;3 Btop watches.2.Rmd
Procedure:
Taka a dry 250 ml conlcal flask.Pipette 100ml of 0.IM HC1 Anto
it,1ooaely tie a rubber bung and suapend ic In a thermostat at about 45℃.
(Nota
tha exact temparature).Alao guapond in the bath a small atopperad flask
ot uathy1 acataee. Allow 10 mtnutee tor theconeeneuof cha. flaaxuto
reach the thermoatat tempe.ature(Two other conical flaska,contafning
100ml of 0.3N and 0.6M HCI respactively,may convantohtly bu prepared'
In a simllar way at this pelnt,Eacura all flaske are adaquately labelled).
Start the reactlon by plpetting Sml of methyl acatace into the tlask of
0.1sм e1d. Shakewa11andscвrt the stop vaeeh. Iumedlate1y
чteharat
5ml of the solutton and run it Into about 25ml of ice cold watar in a
12Sm. contca1 Elank, In ordez tonrreat rheraвetton. Noee the eAma
ttefaei eBa seXd aв вoonaв ponntble wtth cha MaOH вolutton. Wehdramnnd
tltraee[ turehor nauplea 1n thu same uanner nt tntervala of 15, 30, 50, 7с
100, 130,] 150 mlnucanbfterthostarc ofche raaetlon. Tba runultd=r o1
theraaeeAoa
atxeurа nhou1dba 1eft(ntoppured)_for24 houru_for_ehe_reacttontose
—2—
ьгазчоолатенчузпчуашщолозяеетииидвцатоотэотавоэороВноз
ЕЧнуаощиракорчэтаодртэомячорияскочауаиухоохо,очааиваау
оэиЧёрии оЄГртпочвнчотачзэтзтон
МсхоочэхоартацорооєЧо
рцмоочвомгядпочхрававзвахоогтонжвев
ос
oс *oz*ot бцоаввришва ртпосв Кочтон
иячовчааой таавоз этвХН
д
40,50.65,85 mtnucas and 2a hours.afcar the start of,the.reestione
Calculatlon: BRONT
(eater)·(ko+k(k₃0))[eatex)
k![eater]
шпунокозрАч зивавиоэаю ито
аивзвиоэиэаттхл,ЯЧГоЧвУЧжчГЧжуходочн и
дуазивопоопот r auch condiclonntherasetion
wlil show ise order
ktnetie behavtour
4.e1 g tha
where a "[eater]Antcial
and (a-x)-[ester] cimes
The concentration of acatie acid in the solutlon at any time ia the ra
aqual to the anount of ehter that hag reacted.
оцаЦрив поуаптоворухозркчшпуровXтnитвзата
тваузоро4МРаап
Litre of a sample taken at time t. Where
①| швотлхоёолавтнерии
btomtn
ГнооэчноТ
тизознотоГтонуозтваотаховбхагву- It the
Тчязоззяощ
трпотазосозаптд
ошуаЗРГноорЖноЛ вптвГтонТьвЗ che ab
co che amount of ister ioft afcer cime t 1.a,to'
Дх зивзвноэ Катротва ачу
эзвтпэтчр«вштэ"оа(х—ш)зо вцоваВ зота at each acid
conc&Bcratfon.Craphically teat the dapandance of t on
catalyst(acid)concentration.Prom your graph determine the valugs of
[.д рив "- Ц
М
DLacugalon; нооаоя
ц
1. Diacuss the expertmental errore;are the graphe Iinear withinn the в
р
рьеозпотаэведоцлмоцвлватьмадапокорришваоазовавцало
ватшут sta
ит а
гвцачзодгоагзоваведочатмгаораоавата eater and the
hydroxontum 1on!
2. ваутиалотиттояводпов етатввод)х"потзэчехчацчхозшотнецаоти"з
оэ у воВУлб
втш и чмоххиа
ц in e Ка,КааитшацотиэтиКчанелв
3. иоутавваацаоВитапррашхозвуртав"этаабу ,Would you
expect che reactiol
to becong autocatalytse?
EQUTV
