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Chemical km'etics
Chemical kin'etics is' the study of reaction rates and reaction mecham'sms. The reaction rate is defm'ed
as the change in the concentration of the reactants or products as a function of time. The reaction mechanis'm is' a sequence of steps by which the overall change is' accomplished. For a hypothetical reaction
aA+bBch+dD
(1)
the reaction rate, r, can be m'dependently expressed 111' terms of the rate of disappearance of the reactants
or the rate of appearance of the products
1A[A]
1A[B] _ 1A[C]
r-_________
a At
b At
6 At
_ _1A[D]
d
At
(2)
The rate law expresses the reaction rate as a function of concentration at a particular temperature. The
rate law has the form:
r = kIAllBl"
(3)
where k 15' the rate constant charactens'tic of the reaction at a given temperature. The rate constant does
not change as the reaction proceeds, so long as the temperature is' held constant. The exponents x and y
are the reaction orders, also characteristic of the reaction, regardless of temperature. The overall reaction
order is the sum of the reaction orders found 1n' the rate law. All of "156 rate law parameters are experimentally determined.
The kin'etics of the reaction between persulfate, 31032 and iodide, 1 ions Will be studied
expenm'entally.
520.1 (aq) + 21' (aq) ~> 2503 (aq) + 12(aq)
(4)
r = kl5202a llllv
(5)
In this' experiment, the method of initial rates is' used to determine the reaction orders a: and y. This'
method relies on deterrrumn"g how the rru'hal rate of reaction varies with a particular uutial reactant concentration, provided that all other reactant concentration's are held constant. Consider the kin'etic data in' Table
1.
E___________Table
3: Samle kin'etic data for method of uu"tial rates
[r]. .. [M
________mmal__mmL_Run
Initial rate, M/s [520821. .. [M
1
r;
0.04
0.02
2
3
r;
r3
0.04
008
0.01
0.02
Consider runs 1 and 2. Both runs wrll' have the same form of rate law, only different in the reaction rates
and reactant concentrations. Hence, takm'g the ratio of the rates:
r1 _ k(0.04)(0.02)
r2 ' k(_0.04)=(0.01)v
(6)
Note how the [$2032_]uu-~al, and the In terms will cancel out. Therefore.-
= log
y
104%)
(7)
(8)
where R 15' the gas constant, 8.314 I K1 11101, and A is the Arrhenius constant. Note that Ed and A
are parameters characteristic of the reaction and its mechanism, independent of temperature and concentration. To obtam these parameters, rate constants are obtained at different temperatures. Then, In k is'
plotted as a lmear function of 1 /T. The resultm'g slope and intercept will give the desired parameters.
In this experiment, the rate of 1; formation will be measured to describe the rate of the reaction. The I;
formed from the origm'al reaction is reduced back to I by 82032 ions. When all the $203 ' is used up,
free 1; starts to form m solution. By measurm'g the tim'e taken for the known amount of 1; during that
time can be calculated.
CHEMICALS
Amount
Risk phrases
Ian35
Immmm:m
U1
l328
Chemical
APPARATUS
Alcohol thermometer
Hotplate
Safety phrases
PROCEDURE
Solution Preparatwn'
QWPPN?
Table 3.1.
Beaker A
0.2 M Kl
0.2 M KCl, ml.
10.0
0.0
5.0
5.0
2.5
7.5
5.0
5.0
5.0
5.0
3. Cool beakers A and B of run 2 (set 3) m' an ice bath. Once the temperature has already reached aroun
5C (0C-10C), pour the contents of beaker A mto beaker B and start timing the reaction. Stop the
Ma after a blue solution is observed.
10
DATA TREATMENT
Prepare the followm'g graphs:
1. 1n rate versus 1n[3308"] for runs 2,4, and 5 (constant [11) with the slope of the he equal to the rate
order of 8203
2. ln rate versus ln[l] for runs 1, 2, and 3 (constant [520821) with the slope of the lin'e equal to the rate
order of I
3. In R versns l/T for sets 1, 2, and 3 of mn 2 with the slope multiplied with R equal to the activation
energy
CALCULATIONS
Deterrrun'e the:
1. rate for each setup (M/s) by usmg the concentration of $2032 smce it acts as the lxm'itm'g reactant
2.
3.
4.
5.
0 Proposed mechanism 2:
1(n-q)+5,02
1H"
80) equilibrium
[1...520313(0")
_
_
_ _mgl I
2M, + 2303)
[1. . 3,0313, + 1) '
- Proposed mechanis'm 3:
_
2__n_w,al .
1(aq) + 32030) ~93]?
3
. 92081010
0 Proposed mechanism 4:
2_
1 I,(M, + 250W,
2101"" ) + 320;) '
6. How do your results compare to previously done studies? If your results are signicantly different,
explam how the differences could have occurred.
11
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