Heat capacity anomaly in the vicinity of the tricritical and upper critical points

The anomalous behavior of the isochoric heat capacity of a mixture of methane, pentane and heptane is studied experimentally in the vicinity of the liquid-vapor critical point in the cases when (a) the critical temperature T _c approaches the tricritical point T _TCP and (b) the critical temperature approaches the upper critical end point T _U . It is shown that in all cases, the singular part of the heat capacity of the mixture has the form C_sing=A¦τ¦^?α, where τ=(T ? T _c )/T _c and α≈0.11. When T _c →T _U , amplitude A of the heat capacity anomaly is found to be approximately constant. At the same time, the amplitude of the anomaly tends to zero in the vicinity of the tricritical point: A∝¦τ_c¦^ε, where τ_c=(T _c ? T _TCP )/T _TCP and ε=1.6?1.7. The inevitable vanishing of this mode of the heat capacity anomaly leads to a negative value of the critical index \(\tilde \alpha\) characterizing the heat capacity anomaly at the tricritical point, while the tricritical point theory and the isomorphism hypothesis predict \(\tilde \alpha = 0.5\).