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The first time Darnay is arrested, it is because he has been accused of conducting secret business between France and England for at least five years; in other words, he is accused of being a spy.
The second time he is arrested, he is on his way to Paris; Darnay is captured, imprisoned, charged with being an aristocratic emigrant. Now he must suffer the justice of the revolution.
The second time Darnay is arrested for being an emigrant he is imprisoned only briefly. Dr. Manette uses he influence to free Darnay. Yet almost immediately upon being released he is arrested again based on charges from the DeFarges and "one other." This final arrest sets in motion the exchange between Carton and Darnay that leads to the novel's climax.
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