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In the novel 'The Picture of Dorian Gray' by Oscar Wilde, Gray locks away a portrait of his in the attic for 18 years and over that time the picture degrades to an almost unrecognisable version of its former self. The novel explains this as the fulfilment of a wish by Gray to have the portrait age instead of himself but I have been wondering recently, are there be any natural reasons that could explain this transformation if a painting is locked away for a large period of time?

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    $\begingroup$ Good thing you didn't ask about the other prominent usage of chemistry in the novel. $\endgroup$ – Ivan Neretin Jun 14 '17 at 19:12
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Preface: So far, I do not know the novel you refer to, and assume the portrait is a classical oil painting.

Such a painting consists of several layers of products applied. Similar to a wall in your living room, the canvas is prepared to accomodate the pigments dispersed in linseed oil, what in other fields of application would be called a "primer". Then there are multiple layers of the painting itself, topped by the varnish. To mention a few of the potential issues,

  • Pigments may change their colour upon exposure to air. Pigments like lead white turned over time black, for example.

  • Pigments may interact with the oil, forming complexes, of different mechanical and complexation strength:

enter image description here

(source)

  • Components may migrate across the picture and locally, and reactions may occur. The formation of soaps of lead and zinc are the most prominently known ones, for example based on palmitic, stearic, or azelaic acid. These processes may alter colors, even rendering them transparent enough to recognise the support of the paint, and they may eventually protrude the surface of the paintings as shown from a topview:

enter image description here

(source, p. 14)

or cross section:

enter image description here

(source)

These may not simply be "washed off" as a normal cleansing would do, as water and humidity in general amplify the problem. If left untreated, the painting however will age and degrade.

Further reading may be found, for example, here, here, here, here/here.

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