Tom Walker's wife is depicted as a termagant, selfish woman who loves confrontation and continually argues with her husband. After learning about the deal Old Scratch offered her husband, Tom's wife demands that he accept the offer and attempts to bully him into making a decision. When Tom refuses to accept the devil's offer, his wife takes matters into her own hands and meets up with Old Scratch in the swamp. She fearlessly approaches the devil and tries to make a deal with him, which he refuses. When Tom's wife returns home, she gathers her valuable possessions and returns to the swamp, never to be heard from again. Tom eventually searches for his wife and only ends up finding her checkered apron, which holds the remains of her heart and liver.
One could argue that Tom's wife's two main sins were her greed and temper. My guess is that...
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Tom's wife argued with the devil, who ended up chopping her into pieces and taking her soul. Symbolically, the heart represents love, faith, and emotion, while the liver represents purity, which corresponds to its function. The devil may have left the heart and liver behind because those two organs are typically associated with love, faith, and purity, which are positive traits he detests.
Mrs Walker is described as being just as miserly as Tom, and spends most of her time attempting to cheat and deceive him. She has no obvious job, nor does she appear to have any hobbies, interests, pastimes or friends. This casts her as a somewhat one-dimensional personification of greed, although that may simply be a choice to suit the author's purpose.
Classifying sins is a fairly subjective task, but if we were to go by the famous "seven deadly sins", then her two greatest sins are greed and wrath. While we could easily make a case for her exhibiting lust and envy as well, greed is what inspires her to try to make a deal with Scratch on her own, and it is her wrath (uncontrolled anger) that gets her killed; she doesn't control her temper well enough to realize that picking a physical fight with the embodiment of evil is probably a bad idea.
The question of whether Mrs. Walker deserved this fate is uncertain. Does anyone deserved be killed by the Devil, and have their heart and liver tied up in an apron? It might be better to ask if her fate is surprising, considering the way she lived her life.
Symbolically, the heart and liver have many and mixed meanings, and the exact one intended here is not explicitly stated, if in fact there was any intended meaning as opposed to Irving just attempting to shock his audience. The heart symbolizes emotion, the life force, and love, while the symbolism of the liver is somewhat more obscure, but is often tied to similar qualities, and its functional role in the body is purification. We might interpret that Scratch left these items behind either because they were offensive to him, being associated with love and purity.
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