Based on the foundations of thermodynamics and the equilibrium conditions for the coexistence of two phases in a magnetic Ising-like system, we show, first, that there is a critical point where the isothermal susceptibility diverges and the specific heat may remain finite, and second, that near the critical point the entropy of the system, and therefore all free energies, do obey scaling. Although we limit ourselves to such a system, we elaborate about the possibilities of finding universality, as well as the precise values of the critical exponents using thermodynamics only.
We describe a new approach to the understanding of the thermodynamic properties of a physical system near a critical point. The critical point is characterized by the peculiar dependence of various quantities on the size of the system, rather than by the mathematical singularities which appear in an infinite system. We indicate a very general method of obtaining scaling laws for the critical behavior of any thermodynamic system by considering its thermodynamic fluctuations. As an example, a new scaling law is obtained for the susceptibility at a gas-liquid critical point.
Thermodynamic functions in the vicinity of an ordinary critical point are expected to obey asymptotic scaling laws as $t=\frac{(T\ensuremath{-}{T}_{c})}{{T}_{c}}$ and the ordering field,
h, approach zero. However, the optimal scaling variables are the nonlinear scaling fields, ${g}_{t}=t+{b}_{t}{h}^{2}+{c}_{t}{t}^{2}+\ensuremath{\cdots}$ and ${g}_{h}=h(1+{c}_{h}t+\ensuremath{\cdots})$. The nonlinearities yield correction factors to the leading power-law (and scaling) variation of thermodynamic quantities,
L, of the form ($1+{a}_{L}t+{b}_{L}{t}^{2}+\ensuremath{\cdots}$), etc., where the correction amplitudes
aL,bL,…, are uniquely determined by the nonlinear scaling-field coefficients. It follows that "analytic" corrections to, e.g., the susceptibility, are directly related to those for the free energy and magnetization (in zero field). The term
bth2 also generates nonanalytic contributions such as an additive, energylike term, varying as ${|t|}^{1\ensuremath{-}\ensuremath{\alpha}}$ in the zero-field susceptibility, and factors like ($1+{c}_{L}{|h|}^{2\ensuremath{-}\frac{1}{\ensuremath{\Delta}}}$) on the critical isotherm,
t=0. Irrelevant scaling fields yield further, in general distinct, nonanalytic corrections, and cause shifts in
Tc and various amplitudes although "universal" ratios remain constant.
There are two independent critical exponents that describe the behavior of systems near their critical point. However, at the critical point only the exponent η, which describes the decay of the correlation function, is usually discussed. We emphasize that there is a second independent exponent η′ that describes the decay of the fourth-order correlation function. The exponent η′ is related to the exponents determining the behavior of thermodynamic functions near criticality via a fluctuation-response equation for the specific heat. We also discuss a scaling law for η′.