I

OBJECTIVES
KINIETICS EXPERIMENT
To study the rate of reactions.
To determine reaction orders.
To determine the rate law for a chemical system.
INTRODUCTION
One of the methods used in studying chemical reactions is to measure the change in reactant
concentration over a given period of time. This change in concentation with respect to a time unit
(seconds, minutes, hours, etc.) is called the rate of a chemical reaction. This rate of change depends
on the concenffation of the reacting species; the temperature of the reaction system; and an energy
factor called the activation energy. The study of reaction rates and the factors which affect rates of
reactions is called Kinetics.
In kinetics a complete description of a reaction system starts with the writing of a general rate
expression. The following example serves to illustrate how this is done.
Given a reaction:
A + B ------->
General rate expression is:
Rare
=
k[A]m
[B]"
where "k" is a constant, called the rate constant, and "m" and "n" are called reaction orders. The
brackets (
t I )
are interpreted as molarity units or the number of moles per liter of reactant A and B.
The general rate expression tells us that the Rate of any reaction depends on the values of; (1) the
rate constant;
(2) the concentration of reactants; (3) the reaction orders.
One of the major objectives of Kinetics is the experimental determination of the values of the
reaction orders to obtain a Rate Law. For example, if experiments indicate the the value of "m" is I
and the value of "n" is 0, the rate expression above can be re-written as:
Rate
=
k[A]t
(note:
[B]o
drops out as any number raised to the zero power is "1" and will not affect the value of
Rate in the equation)
This rate expression now tells us that the rate of the reaction is directly proportional to the
concenffation of
[A]
and it is called a First Order reaction. Once it has been determined that it is a
first order reaction, the first order rate equation can be used to predict concentrations of reactant "A"
at any time value.
If, on the other hand, experiments indicate that the value of "m" is 2 and that of "n" is 0, the
following rate expression can be written:
Rate
=
k[e1z
and the reaction is said to be a Second Order reaction and the rate law above tells us that the rate of
the reaction will depend on the square of the concentration of "A".
If both "m" and "n" are determined to be equal to 1, the rate expression for the system becomes:
Rate
--
klAlt
[B]t
and the reaction system is said to be first order with respect to "A" and "B" and Second Order
Overall (overall order is the sum of "m" and "n").
The values of "m" and "n" must be determined experimentally as they cannot be predicted
by the stoichiometry (the coefficients of the balanced equation) of thd reaction. The valu'es of the
reaction orders need not be whole numbers although they are often rounded offto the nearest whole
numbers to make the calculations simpler.
THE REACTION TO BF STUDIED
The system
you
will be working with is a rather complex reaction involving three separate steps as
illusfated below:
STEP 1
2IO3- +
iodate
ions
2 SO3-2
sulfite
ions
iodide sulfite
ions ions
An excess of iodate ions is allowed to react with sulfite ions to produce iodide ions in solution.
When all of the sulfite ions (the limiting reagent) is consumed, the iodate reacts further with the
iodide ions in the presence of acid (H+) producing iodine molecules as described in step 2:
STEP 2
IOa- + 5I-+6H+ ------------->
the iodine molecules p-roduced can be detected by the_addition of starch as they form a complex
which exhibits a dark blue color as described in step 3.
STEP 3
starch + Iz ------------->
The rate of this reaction can be determined by measuring the time it takes for the blue color to
_appar. ,Although
the reaction is a complex one, it can be studied rather easily because of the "rate-
limiting"
ltep
concept in Kinetics. According to this concept, the slowest stei in any multi-step
reaction determines the overall rate of the reaction. The slow step in this reaCtion has been found to
pe Step 1 and Steps 2 and 3 can be assumed to occur instantaneously as soon as all of the sulfite
ions are consumed.
Hence, the rate expression for this reaction is that expression which describes the slowest
step.
Rate
=
k
[iodate]m [sulfite]n
MEASUREMENT OF TIIE RATE OF REACTION
In this experiment the rate of the reaction will be based on how long it takes for the blue
color of the starch-iodine complex to appear. We will assume that when the blue color appears, all
of the sulfite ions will have been consumed. The rate of the reaction will be expressed as the
change in sulfite concenfration with time or:
Rate
=
Alsulfitel
=
time
M
seconds
PROCEDURE
You will be provided with two stock solutions, A and B. Solution A contains 0.020 M iodate ions
and solution B contains 0.010 M sulfite ions along with some acid and starch. In preparing your
reaction systems always add water first followed by solution B and then add solution A.
Use pipets to measure out the water and solutions A and B. Use a 50 Erlenmeyer flask as
your reaction vessel. After each trial simply rinse out the flask with tap water. The volumes of
solution you are to use are those found below in the sample data.
As temperature changes affect reaction rates, you will want to minimize contact with the
solutions; after adding all solutions, grasp the top of the flask with your fingertips, swirl it gently
and quickly, and place the flask on the lab bench. Swirl the mixture intermittently until a color
change occurs. Time each reaction to the nearest second. Run each reaction system several times
to obtain an average time value. Record the temperature of the room for each reaction.
SAMPLE DATA
Determination of the Rate of Reaction
To determine the reaction order with respect to iodate ions and sulfite ions, you will have to measure
the rate of several reaction systems. In this example, the original solutions are 0.020 M iodate and
0.010 M sulfite.
system I 0.50 mL iodate 0.50 mL sulfite 4.00 mL water
system 2 1.00 mL iodate 0.50 mL sulfite 3.50 mL water
system 3 0.50 mL iodate 1.00 mL sulfite 3.50 mL water
The first two systems are designed to determine the effect of increasing iodate concentrations while
maintaining sulfite concentration const?nt. Then, a comparison of the rates of system 3 and system
1 determines the effect of increasing sulfite concenffation while maintaining constant iodate
concenfration.
The following represents sample data obtained at20.0 C.
trial I ttal2 fial 3 trial4 average
system 1 103 s 100 s 105 s 104 s 103 s
system2 55s 58s 54s 53s 55s
system3 42s 46s 44s 43s 44s
The rates for systems 1 and2 are determined by dividing the average time for color appearance into
the starting colcentration of the sulfite ion. The sulfite concenfration is calculated by ionsidering
the dilution of the solution and using Mt Vt
=MZYz.
M2
=
MtVt
Y2
=
(0.50
mL)
(0.010
M)
5.00 mL
=
0.0010 M
Rateofslstem 1
=
0.0010M/ 103 s
=
9.7 xl0-5IWs
Rateofslstem2
=
0.0010M1 55s
=
1.8x 10-3M/s
Since the amount of sulfite ions was doubled in system 3, the sulfite ion concentration must be
doubled in determining the rate of system 3:
Rateofsystem3
=
0.0020lNl/44s
=
4.5x10-5Nrys
I
Deterrnination of Reaction Orders
\*
The reaction order with respect of iodate ions is determined in the following way. Note that the
dilution calculations for the solutions have been done and are not shown.
Rate.system2
=
kliodatel*Isulfite.ln
Rate, system 1 kliodate]*[su1fite1n
1.8x10-s
=
k[0.0020M1-10.001-0Mln
9.7 x t0_a k
[0.0010M]m [0.0010M]n
simplify by canceling out "k". We can also cancel the (0.0010M)n term because regardless of the
value of "n", the result of the division will be 1.
Hence,
l.g
=
(2.0),r,
solving by use of logs,
log 1.9
=
m(log2.0)
solve for m,
m
=
log 1.9
=
0.93
log2.0
This would be the reaction order with respect to the iodate ions. It can be rounded to 1, indicating
that it is first order with respect to iodate
The reaction order with respect to the sulfite ion can be determined by comparing the rates of
system 3 with that of system 1.
rate.system3
=
kfiodatelo'e3lsulfiteln
rate, system I kliodatslo.l:[su1fite]n
4.5x10rM/s
=
kl0.00lMl0.e3l0.0020Mln
9.7 x 10-6 tWs kt0.001M10.e3[0.0010M]n
4.6
=
(1)
o.rl
12;
n
( Note that (t)
0.e3
=
I
)
Using logs to solve,
log4.6= nlog(2)
n=log4.6=2.2
log2
This is second order with respect to sulfite.
The reaction is therefore lst order (to the nearest whole number) in iodate ion concenffation and
2nd order with respect to sulfite ions. The overall order is therefore 3.
Rate
=
k[iodate]l
[sulfite]2
Determination
of Rate Constants
Once the reaction orders have been determined, the rate constants can be calculated by
solving for "k" for each reaction system. For system 1:
k1
=
Rate. system 1
liodatslo.ra lsulfitslz.z
k1
=
9.7 x 10-6 M/s
(0.00 1 0M)0.e3 (0.001
0w1z.z
k1
=
2.4x104 M-2s-l
Note: To find what (0.0010)0'r: it
"O,ral
to, take tltg log of the expression which gives,
0.93 ln(0.0010)
=
-6.4 to two significant figures. Then-find the adtilog (inverse
log; to'fina wnat
the number is. The antilog or inverse log of -6.4
=
r.6 x l0-3 to two sig figs.
Using this approach the " k" values for the system 2 and 3 are calculated, and both came out to be
2.3 x l}a M-2s-1, to 2 significant figures. The "k" value is then reported as the averageof all three
"k's".
The units M-2s-l are characteristic of a third order reaction.
il
1r
DATA SHEE NAME
trial 1
tr:ral2
seconds sulfite M
seconds iodate
trial 3
_seconds Average time
_sec
trtal4
_seconds Rate, System l_M/s
System 2 1.00 mL of 0.010 M iodate; 0.50 mL of 0.010M sulfitQ and 3.50 mL warer
i!
t1
ti
i
System 1 0.50 ni[, of 0.010 M iodate, 0.50 mL of 0.010M sulfitg and 4.00 mL of water
!
I
M
trial I
tnal2
trial 3
_seconds sulfite
_seconds iodate
-M
M
\
Ytal4
_seconds Rate, System 2
_M/s
System 3 0.50 mL of 0.010 M iodatel 1.00 mL of 0.010M sulfite;and 3.50 mL water
il
trial 1
_seconds sulfite M
_seconds Average time
_sec
seconds iodate
-M
seconds Average time
_sec
seconds Rate, System 3
_M/s
tnal2
frial3
trial 4
Calculation of orders of reaction:
Determination of "m"
Determination of "n"
Calculation of rate constants:
Rate Constant 1
Rate Constant 2
Rate Constant 3
Average Rate Constant
Rate Law
,
I
\!,
Prelab Assignment
.
Try the following as a check to see if you understand what was presented above.
1. If 200. mL of a 12M HCI solution were diluted to a final volume of 600. mL, what is its final
concenfation?
(ans. 4.0 M)
2. If 500. mL of water were added to 100. mL of a18 M solution, what is the final concenffation of
this diluted solution?
(ans. 3.0 M)
3. How much water must be added to 600. mL of an 18 M solution to decrease its concenkation to
3.0 M?
\-
(ans. 3000 mL or 3.0liters)
4.If 250. mL of a 0.25 M solution is dilut*, doncentration of 0.10 M what must have been the
final volume of this solution?
(ans. 625 mL)
5. In the above problem (#4) how much water must have been added to starting solution? (ans. 375
mL)