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The 'blue bottle' reaction


BY COLIN BAKER | 1 NOVEMBER 2006

A colour change experiment for investigating reaction kinetics

Methylene blue is an aromatic compound that produces a blue solution when dissolved in water. It
is a redox indicator and relies on electron transfer rather than changes in hydrogen ion
concentration to change colour. A redox indicator undergoes a de nite colour change at a
speci c electrode potential.

A number of features of the 'blue bottle' reaction makes it ideal to use for investigating reaction
kinetics - it is very quick, the chemicals are relatively cheap and safe, and the measurements are
straightforward. In this demonstration, a stoppered ask is half- lled with a colourless solution. On
shaking, the solution turns blue, and on standing, the solution returns to colourless. This cyclic
colour change can be repeated by successive shaking and standing.

The 'blue bottle' reaction1

Glucose (an aldohexose) in an alkaline solution is slowly oxidised by oxygen, forming gluconic
acid:

CH2OH-(CHOH)4-CHO + O2 CH2OH-(CHOH)4-CO2H

In the presence of sodium hydroxide, gluconic acid is converted to sodium gluconate. Methylene
blue speeds up the reaction by acting as an oxygen transfer agent. As glucose is oxidised by the
dissolved oxygen, methylene blue itself is reduced, forming the colourless methylene white, and
the blue colour of the solution disappears.

Kit

6 g sodium hydroxide, NaOH;


10 g glucose, C6H12O6;
300 cm3 distilled water;
0.2 per cent methylene blue indicator solution; Source: Colin Baker
one-litre conical ask;
rubber stopper for ask.

Procedure

Put the water in the ask, add and dissolve the sodium hydroxide. Add the glucose when the
sodium hydroxide has dissolved. When all the glucose has dissolved, add ve drops of the
indicator solution and swirl. Allow to stand and the blue colour in the ask slowly disappears
forming a colourless solution. If the ask is shaken a few times, then the blue colour is restored.
This cycle of colour change can be repeated many times over a period of 45 minutes.

Safety

Sodium hydroxide is corrosive, contact with the eyes can cause serious, long-term damage.
Signi cant heat is released when sodium hydroxide dissolves in water.

Special tips

Several variations on this demonstration are possible, one of which allows students to see the
e ect of concentration on the rate of reaction.

Half ll two one-litre conical asks with distilled water. Put 2.5 g of glucose into one ask (A) and 5
g of glucose into the other (B). Dissolve 2.5 g of sodium hydroxide in ask A and 5 g of sodium
hydroxide in B. Add 1 cm3 of 0.2 per cent solution of methylene blue into each ask, stopper both
asks and shake to dissolve the indicator. Set aside the asks and observe as the blue colour
gradually disappears at a di erent rate in each ask.
The ask with the higher concentration takes about half the time for the colour to disappear, using
up the dissolved oxygen twice as fast. You should point out to students that, having gone
colourless, a blue zone remains close to the surface of the solution. This is a result of oxygen
di using from the air space within the ask into the solution.

Teaching goals

This experiment could be used to determine the kinetics of the reaction and thus the mechanism.

The reaction is rst order with respect to the hydroxide ion, methylene blue and glucose but zero-
order with respect to oxygen. The rate law can be found by measuring how long it takes for a
solution of known concentration to go colourless.

The activation energy can be calculated using a normal Arrhenius plot - natural logarithm of the
decolouration time (lnt) against the reciprocal of absolute temperature (1/T). Campbell2 explains
this can be done because the rate of the slow step is independent of the oxygen concentration,
and thus the time, t, which is required for the total oxygen to disappear, is directly related to the
rate constant, k. A straight line is obtained from the plot of lnt against 1/T. The rate law for the
reaction is:3

Rate = k[Dox][CH][OH-]

where Dox is the oxidised (blue) form of methylene blue and CH is the carbohydrate, glucose. A
simple mechanism for the reaction is:

CH + OH- C- + H2O

O2 + D Dox (Fast)

Dox + C- D + X- (Slow)

where D is the reduced (colourless) form of methylene blue and X- represents the oxidation
products from glucose (arabinoic, formic, oxalic and erythronic acids). The enthalpy of the
reaction has been reported as 23 kJ mol-1.
References

1. Chemistry demonstrations illustrated and explained on the Delights of Chemistry website.


2. J. A. Campbell, J. Chem. Educ., 1963, 40, 578.
3. A. G. Cook, R. M. Tolliver and J. E. Williams, J. Chem. Educ., 1994, 71, 160.