Her Spanish-language Wikipedia article, with a link to this image, is here. She backed the Habsburgs in the War of the Spanish Succession and died in prison as a result. She married a member of the de Guevara family. Is it possible a member of that family was born in Argentina, helped the Castro revolution in Cuba, and died in Bolivia? Her genealogical sketch is here.
From Wikimedia; spots throughout the image, but especially in the top fifth and the bottom tenth, were removed with Photoshop.Also posted to the Iberian Style in the Louis XIII and XIV Eras Album here.