1. Chemistry of Oscillating Color- Changing Reactions Andrew Aspaas and Levi Stanley Augustana College Advanced Inorganic Chemistry December 1, 2000

2. Contents Introduction History Mechanisms –Briggs-Rauscher Reaction –Belousov-Zhabotinsky Reaction Demonstrations References

3. Introduction The Briggs-Rauscher and the Belousov- Zhabotinsky (BZ) reactions are two of the most commonly demonstrated oscillating reactions. The demonstrations are not difficult to put together, but the chemistry behind the color changes is often neglected.

4. Introduction Briggs-Rauscher reaction - colorless liquids are mixed to form an amber solution which turns a blue-black color, and cycles between the two colors. BZ reaction - the reaction mixture cycles through steps of green, blue, purple, and red colors.

5. The Chemists Behind the Reactions B.P. Belousov - Russian Chemist –1950s - attempting to simulate Krebs cycle –Discovered his reaction oscillated – Submitted manuscript to a journal, rejected on the grounds that "it's impossible" – Conventional opinion of the time - all reactions should go to thermodynamic equilibrium smoothly

6. The Chemists Behind the Reactions Belousov was so offended by this rejection that he decided to leave science forever! Biochemistry professor S.E. Schnoll took an interest in Belousov's reaction Under Schnoll, A.M. Zhabotinsky investigated the mechanism and spatial distribution patterns of the reaction

7. The Chemists Behind the Reactions W.C. Bray and H. Leibhafsky, U.C. Berkeley –Described first homogeneous isothermal chemical oscillator in 1921, ignored by scientific journals for many years T.S. Briggs and W.C. Rauscher - Galileo High School in San Francisco –Investigated Bray reaction at U.C. Berkeley –Combined parts of the Bray reaction with parts of the BZ reaction to form their BR reaction

8. Briggs-Rauscher Reaction 3 solutions are mixed: –A: 4.0M H 2 O 2 –B: 0.20M KIO 3 and 0.077M H 2 SO 4 –C: 0.15M malonic acid and 0.020M MnSO 4 –Spiked with 1% starch solution

9. Briggs-Rauscher Reaction Non-radical reduction of iodate to hypoiodous acid: If there is an abundance of I - ions: –IO 3 - + I - + 2H +  HIO 2 + HOI(1) –HIO 2 + I - + H +  2 HOI(2) –HOI + H 2 O 2  I - + O 2 +H + + H 2 O(3) The net result of which is: –IO 3 - + 2 H 2 O 2 + H +  HOI + 2 O 2 +2 H 2 O(4) Hypoiodous acid reacts with malonic acid: –HOI + CH 2 (CO 2 H) 2  ICH(CO 2 H) 2 + H 2 O(5) As HOI is used up in rxn 5, the I - concentration from rxn 3 decreases, and rxns 1 and 2 slow greatly

10. Briggs-Rauscher Reaction When I - concentration is low, the radical reduction of iodate takes over, but has the same end result of the non- radical reduction –IO 3 - + HIO 2 + H +  2 IO 2 + H 2 O(6) –IO 2 + Mn 2+ + H 2 O  HIO 2 + Mn(OH) 2+ (7) Since more HIO 2 is produced than consumed, the rate of the above steps increases as they occur, and therefore much more HOI is formed from rxn 8: –2 HIO 2  IO 3 - + HOI + H + (8) Mn is oxidized in rxn 7,providing a means for the reduction of IO 2 to HIO 2, and Mn is reduced in rxn 9: –Mn(OH) 2+ + H 2 O 2  Mn 2+ + H 2 O + HOO(9) –2 HOO  H 2 O 2 + O 2 (10)

11. Briggs-Rauscher Reaction The HOI produced in the radical process reacts with malonic acid, as in rxn 5 of the non-radical process. But the production of HOI from the radical process is faster than its rxn with malonic acid, and an excess of HOI builds up This excess HOI reacts with H 2 O 2 as in rxn 3 to produce I - The buildup of I - shuts off the radical process and returns the system to the slow, nonradical process we saw first

12. Briggs-Rauscher Reaction Where does the color change come from? –The reaction of HOI and malonic acid is actually a sequence: –I - + HOI + H +  I 2 + H 2 O(11) –I 2 + CH 2 (CO 2 H) 2  ICH(CO 2 H) 2 + H + + I - (12) The amber color is the I 2 produced in rxn 11 –[HOI] > [I - ] from radical process The dark blue color is from an I 3 - complex with starch –When [I - ] > [HOI] from rxn 3 with H 2 O 2 –Causes slower non-radical process to take over –Color fades as I 2 is consumed by rxn 12 –Cycle repeats once radical process starts again

13. Briggs-Rauscher Reaction A summation of this complicated process is diagrammed below:

14. B-Z Reaction 3 Solutions are combined –A: 0.23M KBrO 3 –B: 0.31M malonic acid and 0.059M KBr –C: 0.019M cerium(IV) ammonium nitrate and 2.7M H 2 SO 4 –Spiked with ferroin solution 1,10-phenanthroline, ferrous sulfate

15. B-Z Reaction Belousov originally used citric acid instead of malonic acid It was later found that a number of different carboxylic acids could be used Also, manganese ions could be used instead of cerium ions This overall rxn is cerium-catalyzed oxidation of malonic acid by bromate ions in dilute sulfuric acid

16. B-Z Reaction The overall rxn is represented by this eqn: –3 CH 2 (CO 2 H) 2 + 4 BrO 3 -  4 Br - + 9 CO 2 + 6 H 2 O(1) –But, this equation does not account for the color changes seen in the reaction, the catalytic effect of cerium, or the role of bromide ions Again, the mechanism involves 2 different processes –Process A: ions and 2-electron transfers –Process B: radicals and 1-electron transfers Concentration of Br - ions determines which process is dominant. –Process A: High Br - concentration –Process B: Low Br - concentration

17. B-Z Reaction Process A net reaction: –BrO 3 - + 5 Br - + 6 H +  3 Br 2 + 3 H 2 O(2) –This is a reduction of bromate ions by bromide ions in 2 electron transfers –This occurs when solutions A and B are mixed This process occurs through these three steps: –BrO 3 - + Br - +2 H +  HBrO 2 + HOBr(3) –HBrO 2 + Br - + H +  2 HOBr(4) –HOBr +Br - +H +  Br 2 + H 2 O(5)

18. B-Z Reaction Malonic acid exists mainly in the diacid form but slowly enolizes.. The bromine reacts with the enol form of malonic acid: –Br 2 + CH 2 (CO 2 H) 2  BrCH(CO 2 H) 2 + Br - + H + (6) These reactions together reduce the concentration of Br - in the solution

19. B-Z Reaction Once process A has consumed most of the Br -, process B takes over The overall reaction of process B is represented by: –2 BrO 3 - + 12 H + + 10 Ce 3+  Br 2 + 6 H 2 O 10 Ce 4+ (7) This process is composed the following rxns: –BrO 3 - + HBrO 2 + H +  2 BrO 2 + H 2 O(8) –BrO 2 + Ce 3+ + H +  HBrO 2 + Ce 4+ (9) –2 HBrO 2  HOBr + BrO 3 - + H + (10) –2 HOBr  HBrO 2 + Br - + H + (11) –HOBr + Br - + H +  Br 2 + H 2 O (12)

20. B-Z Reaction The net result of eqn 8 + 2 (eqn 9) is: –2 Ce 3+ + BrO 3 - + HBrO 2 + 3 H +  2 Ce 4+ + H 2 O + 2HBrO 2 (13) This sequence produces HBrO 2 autocatalytically Autocatalysis is an essential feature of this reaction, but does not continue until the reactants are depleted, because there is a 2nd-order destruction of HBrO 2 (rxn 10) Rxns 11 and 12 represent the disproportionation of hyperbromous acid (HOBr) to bromous acid (HBrO 2 ) and Br 2

21. B-Z Reaction Ce 4+ and Br 2 oxidize malonic acid to form bromide ions Once this concentration of Br - becomes high enough, process A is reactivated

22. B-Z Reaction Ferroin provides two of the colors seen in this reaction –As [Ce(IV)] increases, it oxidizes the iron in ferroin from iron(II) (red) to iron(III) (blue) Cerium(III) is colorless, and Ce (IV) is yellow –The combination of Ce(IV) and Fe(III) make the green color The oscillating concentrations and oxidation states of Fe and Ce account for the color changes

23. References "B.P. Belousov: The Way To Discovery," Available: [online] 11/28/2000 http://www.musc.edu/~alievr/belous.html Shakhashiri, B.Z (1985), Chemical Demonstrations, 2: 232-261. Winfree, A.T. (1984), "The Prehistory of the Belousov-Zhabotinsky Oscillator," Journal of Chemical Education, 61: 661-663.