Green vegetables and chlorophyll revisited

"I am an imbecile! I see only half of the picture!"

...is one of my favourite quotes of Agatha Christie's famous detective, Hercule Poirot. After pondering for months about why the broccoli cooking water turns green when using slightly basic and not when the water is slightly acidic the answer was right beneath my nose all the time, and I felt exactly like beloved Hercule (see the posting "Christmas dinner trimmings - a hot potato? Part two").

The trick to cooking wonderfully green vegetables is using a pinch of baking soda (sodium bicarbonate) in the cooking water. Because the water then is slightly basic, the magnesium ion is retained in the chlorophyll, and the colour is a vivid green, see the above mentioned posting. Deliberately using some acid (vinegar) renders the vegetables dull olive green.

What puzzled me was that the cooking water turns green when the vegetables are the most green, whereas the water is completely colourless when the vegetables are dull. How come? For a long time my hypothesis was that the chlorophyll, or some of its derivatives, is extracted to the water when using baking soda, but not when using vinegar.

Earlier this autumn, during a kitchen lab lesson, it suddenly struck me that the chlorophyll (or a chlorophyll derivative) might be there all the time, but that it's invisible in the acidic water, and that seems indeed to be the case. In fact, it retains it's colour, being green in basic water, and colourless in acidic water (see Martin's comment in the Christmas dinner trimming post).

The ultimate test is to look for chlorophyll colour in the acidic water, and the most straightforward experiment was to add some base to the colourless cooking water, and voila: the water took colour! Rendering the solution acidic again by adding some more vinegar resulted in colourless solution, as seen from the video below.

So, this is an example of chemical reversibility: adding one ingredient (i.e. acid/vinegar) you push the situation one way, adding another (baking soda/ammonium chloride, neutralising the acid), you pull it back to towards the starting point.

What might be learned/taught
In my opinion, this adds some chemistry to the kitchen trick of cooking green vegetables with bicarbonate. Also, it provides a meaningful arena for teaching acid/base equilibria and naturally occurring indicators.

Some details
To be honest, in this case it's slightly more complicated than going straight forward and back, and the colour diminishes in going back and forth. Acid and base is added consecutively, whereas the magnesium ions that are responsible for the colour are constantly diluted. Also, adding acid/base introduces other ingredients (acetate/vinegar and sodium/ammonium ions from the base). Thus it's not an entirely pure back and forth situation. I guess, if I'd added magnesium ions together with the baking soda there should might have been a more distinct colour change . One of these days I'll have to do just that.

Finally, the world is usually more complicated than meets the eye. I might very well have missed a point or two somewhere along the way. But anyway; I'm content with this explanation, and the observation of reversibility adds another dimension to using this experiment with students.

Late addition
When chlorophyll (either structure, a or b) reacts with an acid, pheophytin is formed. This is also coloured, but more olive-green or yellowish , depending on whether it's the a or b form. It might very well be these, or derivatives thereof, that are seen in the water solution. There are loads of scientific publications on chlorophyll, of course. A paper of relevance to science education is found in J. Chem. Ed. (This, Valverde, & Vignolle).