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This episode covers the Franco-Prussian War of 1870-1871. This saw France start a war with the North German Confederation (mostly Prussia) because of a diplomatic slight. The French, to put it mildly, didn't do so well and the war was over in six months with a Prussian victory and the unification of Germany. Importantly for France, the peace saw the annexation of Alsace-Lorraine which would cause problems between the two for decades.
Iron Kingdom by Sir Christopher Clark. Probably the best non-academic single-volume book on Germany (Prussia really). Great for broader context too.