As magma cools, minerals crystallize in a sequence determined by equilibrium thermodynamics (Bowen's reaction series). Early-formed crystals are typically denser and sink; liquid becomes progressively enriched in incompatible elements. This process explains compositional variation within individual magma chambers and layered igneous complexes.
You already understand that magma composition controls its viscosity and behavior. Fractional crystallization explains how a single parent magma can produce a whole family of different rock types as it cools — it is the primary engine of magmatic differentiation. The process follows directly from thermodynamics: as temperature drops, the minerals with the highest melting points crystallize first, removing certain elements from the liquid and changing the composition of what remains.
Bowen's reaction series provides the roadmap. On the discontinuous branch, olivine crystallizes first from a basaltic melt, followed by pyroxene, amphibole, and biotite as temperature falls. On the continuous branch, calcium-rich plagioclase crystallizes early and becomes progressively more sodium-rich. The key to differentiation is *separation*: if early-formed crystals remain in contact with the liquid, they react with it and the system stays in equilibrium — no differentiation occurs. But if crystals are physically removed — by settling to the chamber floor under gravity, by being plastered against chamber walls by convection currents, or by filter pressing — the remaining liquid evolves to a new, more silica-rich composition. This is fractional crystallization: the progressive removal of crystalline phases from a cooling melt.
Consider a basaltic magma crystallizing olivine and pyroxene early on. These minerals are rich in magnesium and iron but poor in silica, sodium, and potassium. As they settle out, the remaining liquid becomes depleted in Mg and Fe but enriched in Si, Na, K, and elements that do not fit easily into early-crystallizing mineral structures — the so-called incompatible elements like rubidium, barium, and uranium. Through continued fractionation, an initially basaltic liquid can evolve through intermediate (andesitic) compositions toward silica-rich (rhyolitic or granitic) compositions. This is why a single volcanic system can erupt basalt early in its history and rhyolite later — the magma chamber has been differentiating.
The physical evidence for this process is beautifully preserved in layered igneous intrusions like the Bushveld Complex in South Africa or the Skaergaard intrusion in Greenland. These bodies show rhythmic layers of dense, early-crystallizing minerals (chromite, olivine, pyroxene) alternating with more evolved compositions higher in the sequence — essentially a frozen record of fractional crystallization captured in rock. The equilibrium constant concepts from chemistry apply here: each mineral crystallizes when the melt composition reaches the saturation point for that phase, and the sequence of saturation points defines the crystallization path. Understanding this process is essential for explaining crustal composition and differentiation at the planetary scale, where billions of years of fractional crystallization have progressively concentrated incompatible elements into the continental crust.