Gel volume near the critical point of binary mixture isobutyric acid–water

The volume of a cylindrical polyacrylamide gel was measured when immersed in a binary mixture of isobutyric acid–water at different temperatures and weight fractions of isobutyric acid. Near the upper critical solution temperature of the binary mixture, the curve for gel volume vs. isobutyric acid weight fraction has a shoulder or a peak near the critical weight fraction. On the other hand, in a region away from the critical temperature, the gel volume decreased monotonically with increasing isobutyric acid weight fraction. The cloud point temperature of the binary mixture inside the gel was lower than that outside the gel. Thermodynamic description for the gel in the critical mixture is derived on the basis of the Ising model. By the description, the experimental results are explained consistently. The theoretical analysis shows that the shoulder and the peak appearing in the swelling behavior of the gel are respectively induced by the criticalities of the binary mixture outside and inside the gel. It also shows that the cloud point temperature lowering of the binary mixture inside the gel is attributed to the effective enhancement of the temperature of the binary mixture inside the gel induced by the presence of the gel polymer.