Chemistry IIE Experiment 13 Page 1 of 5

EXPERIMENT 13 REACTIONS IN NON-IDEAL SOLUTION - THE EFFECT OF IONIC STRENGTH ON THE RATE OF THE REACTION 2I- + S2O8= I2 + 2SO4= IN AQUEOUS SOLUTION AT 25C (A PRIMARY SALT EFFECT)
In this experiment the impact that increasing ionic strength has on the rate of the above reaction is explored. The experimental results are also compared to the theoretical expectation as defined by the Debye-Hckel limiting law.

Reference
P.W. Atkins, Physical Chemistry 6th. ed. pp. 249-253 & 836-837 (1998)

Introduction & Theory

[ ]

(1)

In an ideal system, the reactants are randomly located and are extremely dilute (i.e at an infinite distance from each other). Thus ideally there are no interactive forces acting upon each member of the system. In the above reaction, however, both reactants and the activated complex (i.e the complex formed between the reactants prior to the formation of products, written as (I-...S2O8=)) are charged. Therefore, charge-charge interactions will exist in this system, introducing one deviation from ideality. Question: What other interactions contribute to non-ideality? When the rate and rate constant are defined in terms of concentrations as in (1), the effects of non-ideality appear in the rate-constant, k. This is formalized in the Brnsted equation (Atkins 5th ed. p. 949):
k = k0 y I yS O =
2 8

y
2O8 =

(2) are the

where k0 is the rate constant for an ideal solution; yI- & yS

concentration-scale activity coefficients for the reactants; and y is the concentration-scale activity coefficient of the activated complex (I-...S2O8=).

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Since both reactants and the activated complex are charged, the major non-ideality effect arises from charge-charge interactions. For dilute solutions (with total ionic strength I < 0.01), the effects of charge-charge interactions are given to a reasonable approximation by the Debye-Hckel limiting law (Atkins 5th ed pp. 321-323, 949). For an ion i of charge zi: log yi ~ 0.509 zi2 I1/2 (in water at 25C) where the ionic strength, I, is defined by: I= 1 m z2 2 i i i (4) (3)

= 1molkg-1) where mi is the molality of the ion (mo Note: In calculating ionic strength, all ions must be included in the calculation whether they are involved in the reaction or not. In this experiment, we can replace molality by molarity of ions in the solution when calculating I. Why? Substitution of (3) into (2), noting that z = 3, gives the Brnsted-La Mer equation: log k = log k0 + 2.04 I1/2 (5)

That is, for the conditions of the Debye-Hckel limiting law, a plot of the log of the rate constant for the reaction versus the square root of the ionic strength of the solution should yield a straight line with a slope of 2.04 and an intercept of logk0. To test this theory, the reaction rate will be monitored while varying the ionic strengths by adding magnesium sulphate, a substance that will increase the ionic strength of the solution without being directly involved in the reaction at all. One way of monitoring the reaction rate is to measure how long it takes for a pre-determined amount (C) of product (I2) to be formed. This is not always possible to measure directly, as time elapsed while taking an accurate measure of C for I2 would result in missing the actual t of the reaction that produced it. (For example, [I2] can be measured via titration, but by the time the end point was reached and C determined, the reaction would have proceeded further).

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Therefore C of I2 is determined indirectly: 2I- + S2O82- I2 + 2SO42It is known that thiosulphate reacts very quickly with I2: 2S2O32- + I2 S4O62- + 2IReaction 2. Reaction 1.

Therefore if a known constant amount of thiosulphate is added to the reaction mixture, we can measure how long it takes for Reaction 1 to produce sufficient iodine to react with and consume the known amount of thiosulphate added. The complete consumption of thiosulphate can be detected by adding starch to the system, which also reacts with iodine to form a bright blue starch-iodine indicator complex. Therefore, after all the added thiosulphate has been consumed by iodine, an excess of iodine will be produced by Reaction 1 and be released into solution. This excess iodine will then be available to react with the added starch, resulting in a bright blue colour. So, the time taken for the appearance of a bright blue colour in the solution, t = the time taken to produce C amount of iodine = 1/2[S2O32-] initially added. So, the initial rate (vinitial) can be determined by measuring the time, t, for the reaction to go to a small extent, C. vinitial = C t (6)

provided C is small. The initial rate is measured at different ionic strengths, obtained by adding MgSO4. If each experiment is carried to the same extent (i.e. C kept constant) Equation 6 becomes: logvinitial = constant logt The initial concentrations of reactants are kept constant so, from (7) and (1), logk = constant logt (8) (7)

Remember: The small, constant extent-of-reaction (C) is set by adding a small, constant amount of thiosulphate. This reacts very rapidly with I2. So, the I2 formed in Reaction (1) does not appear in solution but is consumed by the thiosulphate. When the thiosulphate is consumed, free iodine appears and is manifest in the blue colour of the starch-iodine complex. So: C = [I2]formed by Reaction 1 = 1/2[S2O3 ]added initially
=

(9)

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Reagents supplied
A. B. C. D. E. 0.2M KI solution; 0.1M sodium thiosulphate (Na2S2O3); Potassium peroxydisulphate, solid (K2S2O8), (potassium persulphate); Starch solution; 2.0M MgSO4 solution.

Preparation of stock solutions

Wash the weighed amount of potassium peroxydisulphate into the same flask, add sufficient deionised water to dissolve the salt, dissolve it, top up to the 500cm3 mark and store the flask in a 25C thermostatted water bath. REDUCTANT SOLUTION a) The reductant I-: Pipette 100cm3 of standard KI into a 500cm3 volumetric flask.

b) S2O32-: This sets C. Pipette 1cm3 of standard 0.1M thiosulphate solution into the same 500cm3 volumetric flask, make up to the mark with deionised water and place in the 25C thermostatted water bath.

Experimental
1. Into separate 250cm3 conical flasks add: 1) 50cm3 of the REDUCTANT solution and 2) 50cm3 of the OXIDANT solution plus 5cm3 water (i.e. as a control for zero additional ionic strength, or added MgSO4). Place both solutions in the 25C thermostatted water bath until thermal equilibrium is reached (approximately 10 minutes). Start the reaction by quickly pouring the REDUCTANT into the flask containing the OXIDANT solution and water. 2. Start timing as soon as the pour is finished. Immediately shake vigorously, pour the resultant solution back into the empty flask and replace it in the thermostatted water bath.

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3. Watch the flask continuously. Record the time taken for the blue colour of the starchiodine complex to first appear. This is t. If you miss this, then repeat the experiment. 4. Record log t and calculate I1/2 using Equation 4. (Remember to include all ions present, including the spectator ions). Note, in this experiment molar concentration can be used instead of molality. Question: Why can we replace molality with molarity in calculating the ionic strength of the reacting solution in this experiment? 5. Repeat the experiment, replacing the 5cm3 of water added to the OXIDANT solution by 5cm3 of MgSO4 solutions of successively increasing concentrations (see below): Question: Do you expect t to increase, decrease or remain the same? 5a. Fill one burette with deionised water and another with the standard 2.0M MgSO4 solution. 5b. Prepare the two reactant solutions as above BUT instead of adding 5cm3 of water to the OXIDANT solution, add in successive experiments: 1cm3 2M MgSO4 2cm3 2M MgSO4 3cm3 2M MgSO4 4cm3 2M MgSO4 5cm3 2M MgSO4 Repeat a run if you miss the first appearance of the iodine-starch complex. If time permits, add a few intermediate MgSO4 concentrations to the experiment. & & & & 4cm3 water 3cm3 water 2cm3 water 1cm3 water

Results
Plot log(t) against (a) I and (b) I1/2. Questions: What does (a) indicate about the reaction? Explain your conclusion. Looking at (b), does the reaction follow the Debye-Huckel limiting law? Provide an explanation for your findings.

Report
Your report should contain the 2 graphs as well as all calculations and answers to questions. Your report should follow the format given in the Semester 2 Introduction (see Typical outline for a scientific report, page iv and the Sample extended report on your CD-ROM) as well as following the guidelines for referencing (Semester 2 Introduction, page iii).