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Here, it is convenient to carry out a clock reaction involving the product I2. ... and we know the general rate law for the iodine-clock reaction:.
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Chemical Kinetics: The Iodine-Clock Reaction:
S 2 O 82 − (aq) + 2 I− (aq) → I (^2) (aq) + 2 SO 42 − (aq)
To measure the rate of this reaction we must measure the rate of concentration change of one of the reactants or products. Here, it is convenient to carry out a clock reaction involving the product I 2. To do this, you will include (to the reacting S 2 O 82 −^ and I−) i ) a small (but accurately known) amount of sodium thiosulfate, Na 2 S 2 O 3 , and ii) some starch indicator. The added Na 2 S 2 O 3 does not interfere with the rate of above reaction, but it does consume the I (^2) as soon as it is formed (see below):
2 S 2 O 32 − (aq) + I 2 (aq) → S 4 O 62 − (aq) + 2 I− (aq)
This reaction is much faster than the previous, so the conversion of I 2 back to I−^ is essentially instantaneous. In a typical experiment, known concentrations of S 2 O 8 2-^ and I−^ are mixed with a small amount of S 2 O 3 2-^ and starch. As reaction the first proceeds, S 2 O 8 2-^ and I−^ react to produce I 2 , but nothing appears to be happening because the second reaction is consuming the I 2 as quickly as it is formed. The important moment is when the S 2 O 3 2-^ runs out, for then the I 2 is no longer consumed (see the second reaction), and the dark blue starch−I 2 complex forms. The stoichiometry of the second reaction indicates that one I 2 molecule must have been generated for every 2 ions of S 2 O 32 −^ initially present in the solution.
[I 2 ] generated(from first reaction) = [I 2 ] consumed(in second reaction) = {1/2[S 2 O 3 2-] initially present}
Note that the change in concentration of I 2 (before the blue complex forms) is fixed by
amount of S 2 O 3 2-^ included in the initial reaction mixture.
rate
d I dt
t
− [ 2 ] [^2 3 ]
Where t = time for blue color to appear.
In this experiment you will:
A. Determine Rate Law and Rate Constant {k is constant at constant temperature} B. Vary temperature and estimate EA {Using the Arrhenius Equation} A. Determining the rate constant (k) and the rate law for the iodine-clock reaction:
We know [S 2 O 8 2-^ ] and [I-], because we know initial volume and concentration of each solution and the final volume for each solution, (Remember M 1 V 1 =M 2 V 2 )
e.g for [S 2 O 8 2-^ ] in trial 1: [S 2 O 8 2-^ ] = (0.100 M)(0.00100L)/(0.0100L) = 0.0100 M
and we know the general rate law for the iodine-clock reaction: rate = k [S 2 O 8 2-^ ]α^ [I -^ ]β
So we will:
rate d I dt
t
− [ ]
2 2 3
a. If temperature is constant, k is constant. If [I -^ ] is constant, log[I-^ ] is constant
log(rate) = αlog[S 2 O 8 2-^ ] + C (Where C = log(k) + βlog[I-]) y = m x + b
For trials 1 -5, you should plot log(rate) vs αlog[S 2 O 8 2-^ ] slope (rounded to the nearest integer) = α
y = 1.1704x - 3. R 2 = 0.
B. Varying the temperature, measure rate of reaction, calculate k and estimate E (^) A
Arrhenius Equation: ln k ( )
= a A
k = rate constant E (^) A = activation energy T = temperature (°K) R = Ideal Gas Constant (8.314 J•mol-1^ •°K -1^ ) A = reaction specific constant
For trials 8, 11 - 14 you should plot ln(k) vs 1/T
slope = -E (^) A /R
In this example : -E (^) A = (R)(-6227.7 °K) E (^) A = (8.314 J•mol -1^ •°K -1^ )( 6227.7 °K) E (^) A = 51777 J/mol or 51.777 kJ/mol
ln k vs 1/T
y = -6227.7x + 15. R^2 = 0.
-7.
-6.
-5.
-4.
-3.
0.0031 0.0032 0.0033 0.0034 0.0035 0.0036 0. 1 / T