Abstract: Freezing and melting techniques are described for separating 1,3-butadiene from a mixture of four-carbon compounds by fractional freezing of the liquid mixture and by fractional melting thereof. It has been discovered that when a frozen four-carbon mixture (BB) containing about 36% 1,3-butadiene (BD) is initially frozen, the first frozen fraction of up to about 30% of the mixture is enriched about 80% over the feed sample while the filtrate is decreased in BD about 36%. A second fractional crystallization of the melt and of the filtrate shows continued enrichment and impoverishment as to BD content, respectively. It has also been discovered that when a solidly frozen BB mixture is slowly thawed and the melt is progressively removed, the melt becomes markedly enriched in BD. A continuous fractional crystallization process that uses these discoveries for producing BD at purities greater than 99% is described.