JOM0 KENXATTA UNIVERSITY OF AGRICULTURE &TECHNOLOG)

CHEMISTRY DEPARTMENT
EXPERIMENT NO,2
PHYSICAL CHEMTSTRX LABORATORY

HE ACID CATALYSED HYDROLYSIS OF AN ESTEF

Introductlon:
An ester,auch as methyl acetate,is hydrolysed in dilute solution according
to the equation:

GH₂CoOcB₃+H₂σ CH₃COOH +CH₃OH

As the water ie in large excess during the hydrolysls its conceneratlon romain:
offectively constant.It is found that the differential rate equatlon for the
apontaneous hydrolysis is:

-d[eater] k。[eater]
dt

Where K 。ls the apontaneous rate constant.

In the absence of acid the ester hydrolyeis is rather
slow. of an acid the rate aquation takes on the form: In the ptasence

- (。+K₁ [H₃O])[aotor]
[eatar]
Whera k,lo the catalytic rate conetant for tho hydroxontum lon.Tha'
aim of this experiment is to determine both,k 。and k dome'by r.
atudying the varlation of ester concentratlon wlth'ttme during
a ronctlon。
8amplen are withdrawn at known tlmea,the raactlon As atopped by cooling,
and the sample 18 analyaed,

Requirametng:

Thermostat at 45°C,250ml and 150ml conlcal flanks,methyl acetate,0.IM

NaOH aolutlon,standard 0.6,0.3 ard 0.15M HCl solutlons,5ml
50m1 pipette,50ml burette;3 Btop watches.2On pipettee,

Procedure:
Take a dry 250 ml conical flask. Pipotte 100ml of 0.1M HC1 into it,1ooaely
a rubber bung and suspend it In at about 45℃.(Note
f exact temparature).Also suspend in a
i thermostat small atoppered flaak
of mothyl acetate.Allow 10 minutes for the contente of the Tldeke to
reach the thermostat temperature(Two other conical flaske,contalning
100mi of 0.3M and 0.6M HC1 respectively,may convenlantly be prepated
in a similar way at this polnt. Ensure all flasks are adequately labelled)。

Start the reaction by 5ml of methyl acetate into the flask of

pipetting 0.15M acid, Shake start the stop watch. Immedlately withdraw
weli and
5ml of the solution and run it into about 25ml of Ice cold watar in a
125m1 conical flask,in order to arrest the reaction.Note the time.Tierate
the acid as soon as posslble with the NaOH solution.Withdraw and titrate
further sanples in the same manner at intervals of 15,30,50,7C.100,130,
150 minutes after the start of the reaction.The remslidar of the reaction
ixture should be left(stoppered)for 24 hours for the reaction to go
 - 2 -

‫ﻉ‬o 8o to eomplacaon ‫ﻉ‬hon a‫ ﻉ‬laaot 'cw p1 营

Aoat eo ba‫ﺩ‬araaaae ue 0‫ ﺩ‬ana 0.s aeta fo ‫ ﺀ‬cho omarmns ua

1s,30,9;69,89;110,120
0.3M and0.6M acid,For
mioutes
the
and 2bHCl,citrattonf
0.3M
hat arceeghould,be
the otatt-o2
Feactton,For the O.6d Hcl,thoy should be made at 0 0,2ton
40,50,65,85 mtnuten and 2a hours.aftar the gtart of the.Feackton
er
Calculation
-[est ]*(ko+k₁[H₃0])[ester]
dt
k[ester]
Where k¹=ko +K₇.[B,0] 。K¹wlll be a conetant at constant hydroxonlum
lon concentt&tion!Uhder such condittons the raactton will ahow 1st
order kinette,behavlour.
f.e ·
"Iog

where a m [ester] initlal

and (a-x)m [ester] time s t

The concentratlon of acetic acid in the solution at any time is aqual

to the anount of ester that has reactad.

lat Too fa the ftnal tlere.in ml.godsum hydrox¹de golutton and "t the
titre of a sample taken at time t。
T le.proportional to [HCl]plus total [CH,COOH]made T.le proportlonal
t8°(Hc1).plua [ca₃coon]at time,t.Therefofe(T 1s praportional
to the amount of deter loft after time t i.e.to°
Plot graphe of(T-T)ve.time.Catculate the velocity conatant xl
at each acid conc&Gtratfon.Graphically test the depandence of kl on
catalyst(acid)concentratlon.From your graph determine the values of
k。and k₁ ·
Discusalon
1.Discugs the experimental errore;are the graphe Iinear with:lnn the
limits of these errors and do your reglts show the reaction to be
first order with respect to both the ester and the hydroxonlum lon?
2.'Suggeet a mechanism for the reaction.(Posstble sources of informatio
ara "Phyeical Chemlstry"by Barrav,and "Physical Organic Chemlatry"
by Hine.)
3.Acetie aeld ia formed during the reaction.Would you expect tha react
to become autocatalytte?
 JONO KENXATTA UNIVERSITY OF AGRICULTURE A TECHNOLOGY

GHEMISTRY DEPARTMENT

PHXSICAL CHEMISTRY LABORATORY EXPERIMENT NO.

BROMINATION OF ACETONF

Introductton:
The reaction betwean bromine and acetone is catalyaed by acid,An aqueous
solution.The overall roactlon 1a

Br2+:GH₃COCH₃ CH₃COCH₂Br +RBr

the purpose af a kinetla study on a raaction Is to find evidence related
to che mechanfsm of the reaction. In this expariment,the ordar.of tae
reactlon with respect to bromine and acatone is to be investigated.

theosyi
The rate equatlen for tha above roaction has the form.

·d[Br₂ ] k、{H]{Br₂ ]b(CH₃);co]

dt

Where a,b and c ate tha ordere of the reactlon wlth reapect to the catalyat,
btomine and acetoneraspectlvely.

If the hydrogen ion concentratlon Ao kapt constanc in a aerles of experimanto,

che above equatfon may be wrftten

Wiere k¹k[aya:
Moreover,if we keep the concentration of acetone in large excess of the
bromine concentratlon,its concentratlon wlll remain effactively constant
during the course of the reactlon.The rate equation wi11 them further
simplify to

d[Br₂]- k¹¹[Br₂] [1]

Wher 1 k(G₃ )₂co] [2]

,;
 —2—
The order in bromtne,b,may .then he deteratned by meahuring che bromine
concentration at regular intervals during the raaction and fitting,the
data to the appropriate Incegratad rate gquation. In this way,k² may
also be determined. Note however that K ,the obeeryed rate gonstant,
ie a functlon of the initial acetona consentration. Taking loge of
[2]wa get.

1og k¹llog k¹+clog【(CH₄),co]

Thus if the experiment ls repeatad with different initial concertrations
of acetone(keeping it in large excess over the bromine)and K is
each time,then C,the order in acetone and k',the determined xace
effective constant,
may be found from a graph of log k' vs.【(CH₃)₂co] ·
w8ma9
: :
Requfrements :
Two 250ml steppered bottlos,thermostat at.25°C;plpettes,stop clock,0.02M
bromine solution IM acetone solution,IM sulphurlc acid aolution,0.25M
potaaelu lodine.salution,0.01N godiun thlosulphate salution and 1M sodium
bicarbonate
solutton
;; x. 文：

Procedure:
100ml of approximately 0.02M bromine solution is added to a 250ml stoppered
bottle and to another bottle a mirture of 50ml M.acetone and 50m1 M suiphuric
acld is added.The bottles are suspended In che chermoetat bath at
25°G and 15 min.are allowed for the atesinment of thermal
equilibrlun.The
acetone solution is then added to the bromine solutlon with atirting
and the stop clock is started at the same time.At 5 minute.intervals
a
10ml
a ont a of the reactlonf Mmlxture
sample s d l is cwlthdrawn
t t and allowed to.run t into
fia a c g 10 I un ar
of 0 M po stsnlu m mlo i e solu ion Tbhie oodnine
e s tlbuetrta dan s abtoiturate2dml.
wlth 0.01N sodium thiogulphate solutlon and a graph is plotted of
tdtre agaimat time:the raaction ie followed until It le conplete ot
for d
maximum of 40 min.
The experiment is repeated using 100 ml of 0.02M bromine solution in the
first bottle each time,but wlth the other bottle contalning";
a.25ml M acetone,25ml water,50ml M sulphurlc acld,
b.37.5ml M acatone,12.5ml water,50ml M sulphuric acid,
,

Rasults and Discusslon:

:
From the grdphs of titre againet time that you have drawn,find the brder
in bromine and also values of k for each experiment.
6aot a gxap or 4og k¹l against log [acetane]according to equatlan {3]
and thence deternine the order in acetone and k'. Pay special attention
to the units of the rate conetaits.
Suggest further experiments which would enable you to determine the order
in the catalyst and k.
DIscuss a posslble mechanism for the reaction which agrees with kinetic date
you have obtained.
 - 2 ·-
Requtrements
10r volume hydrogen peroxide,.0.1M sodlum thiosulphate,\M sulphuric ad
acid,solid potassium iodide,starch indicator solution,10ml plpette,
s0ml burette,250ml measuring cylinder,ice,thermameter,stop-clock,iitre
eonical flask,water bath at 359c.

Procedure :
he 10 vol.hydrogen peroxide is diluted ten times with water. Two
10c,c.portions of this freshly prepared 1 vol.peroxide are:pipetted
separate test tubes and placed in iced water to prevent
Fill a burette with the thiosulphate solution.Put 800 c.c,of dist1lled
water into the litre flask,add 40 c.c.of IM sulphuric acid and a little starch
isolution. Dissolve 4 g of potassium iodine in e rittle water and add to
the litre flask just before starting the reactidn.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 watert Start the stop-clock when the peroxide is added.Wien
the iodine produced by the reaction is in excess of thiosulphate a
colour
and w111 appeart
immediately add aNote the portion
second time as of
soon as you see thenot
thiosulphate.(Dy colour
stop the
clock).Note the time when the blue colour reappear,and continue in this
:marner until about a dozen readings.have been taken.Record the temperatue
of the reaction from time to time and if it varlog considerably then take
an"average value.

Hepeat the experiment using the second portion of peroxide,with the

reaction vessel imersed in a water bath at 35c.Allow the contents of tlre
flask to reach thermal equillbrium with the water bath before starting the
reection.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 tamperatures T and T'.Calculate the ratio of total times t/t'in
each oase.the mean value of these ratics is equal to the inverse ratio
of the rate constants,i,e,
t =k1 (5)

t1 'mean/ k
Discussion
Coment on the stgnificance of activation energies for chemtcal reactions.
nenntton(5)trom the rate equations at the two tengeratures.
JONO KENYATCA UNIVERSITY OF ACRICULTURE &TECHNOLOCY
PHYSICAL,CHEMISTRY LABORATORY

EXPERINENT 13 The Effect of Change of Temperature on the

Rate of a Reaction

Introduction;
Hydrogen peroxide liberates iodine.from acidifled potassium lodtde at a
rate which depends on the concentration of peroxide and hylroiodie acid.Th
reaction can be represented by

H₂O₂
+ 2HI 2H₂⁰+12
If the reaction is carried out in the presence of sodiun thlosulphate,the
iodine fomed is converted back to hydroiodic acid as fast as it is formad:

32
十
28203- S4 言 25~

and the concentration of the acid therefore remains effectively unchenge d.

The reaction will therefore follow pseudo first order kinetics under thse
conditdons. If in addition same starch indicator salution is added to the
reaction mixture,and only small,measured quantities of thlosulphate at
added at a time,then when all the thlosulphate is used up,the excesss
iodine procuced wlll cause a .blue colour appear in the solu:ion.
This providesl a convenient method for following the rate of reaction.

meory:
The temperature dependence of the rate constant,k,of a chemical reaction
is given by the Arrhenius equation;

k=A exp(-E/RT) (1)

Where A and E are constants.A is called the ifrequency factor"and E
the "activation energy".Both of these values are dependent upon the reecti
studied.R and T are the gas constant and the absolute temperature
respectively.Taking loge of equation(1)glves

(2)
ink=F +in A
Differentiation of euatior:(2)gives

Which on integrating heiween the 1imits T amd T'gives

log

Where k and K'are the rite constants correspondimg te two differe

it rf the ratia K'/K and the temperatures T and
T'
then E may be calculated.