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====Van der Waals- Gleichung in reduzierten Variablen (dimensionslos):==== :<math>\begin{align} & \tilde{v}=\frac{v}{{{v}_{c}}} \\ & \tilde{p}=\frac{p}{{{p}_{c}}} \\ & \tilde{t}=\frac{T}{{{T}_{c}}} \\ & \Rightarrow \left( \tilde{p}+\frac{3}{{{{\tilde{v}}}^{2}}} \right)\left( \tilde{v}-\frac{1}{3} \right)=\frac{8}{3}\tilde{t} \\ \end{align}</math> bzw. :<math>\tilde{p}{{\tilde{v}}^{3}}-{{\tilde{v}}^{2}}\frac{1}{3}\left( 8\tilde{t}+\tilde{p} \right)+3\tilde{v}-1=0</math> Kritischer Punkt folgt dann für die Lösung mit <math>\tilde{v}=\tilde{p}=\tilde{t}=1</math> . '''Allgemein '''auf der Stabilitätsgrenze: :<math>\begin{align} & {{\kappa }_{T}}=-\frac{1}{v}{{\left( \frac{\partial v}{\partial p} \right)}_{T}}\tilde{\ }\frac{1}{{{\left( \frac{\partial p}{\partial v} \right)}_{T}}}=\infty \\ & \alpha =\frac{1}{v}{{\left( \frac{\partial v}{\partial T} \right)}_{p}}=-\frac{{{\left( \frac{\partial p}{\partial T} \right)}_{v}}}{v{{\left( \frac{\partial p}{\partial v} \right)}_{T}}}=\infty \\ & {{c}_{p}}={{c}_{v}}+T{{\left( \frac{\partial p}{\partial T} \right)}_{v}}{{\left( \frac{\partial v}{\partial T} \right)}_{p}}=\infty \\ & {{\left( \frac{\partial v}{\partial T} \right)}_{p}}\to \infty \\ \end{align}</math> Dabei wurde verwendet, dass ganz allgemein gilt für: :<math>z(x,y):dz={{\left( \frac{\partial z}{\partial x} \right)}_{y}}dx+{{\left( \frac{\partial z}{\partial y} \right)}_{x}}dy</math> falls diese Funktion nun konstant ist: :<math>\begin{align} & z(x,y)=const. \\ & \Rightarrow dz=0={{\left( \frac{\partial z}{\partial x} \right)}_{y}}dx+{{\left( \frac{\partial z}{\partial y} \right)}_{x}}dy \\ & \Rightarrow {{\left( \frac{\partial z}{\partial x} \right)}_{y}}dx=-{{\left( \frac{\partial z}{\partial y} \right)}_{x}}dy\Rightarrow {{\left( \frac{\partial y}{\partial x} \right)}_{z}}=-\frac{{{\left( \frac{\partial z}{\partial x} \right)}_{y}}}{{{\left( \frac{\partial z}{\partial y} \right)}_{x}}} \\ \end{align}</math> '''Bemerkung''' Das singuläre kritische verhalten kann durch '''kritische Exponenten ''' beschrieben werden: :<math>\begin{align} & {{c}_{v}}\tilde{\ }{{{\hat{t}}}^{-\alpha }} \\ & \Delta \rho \tilde{\ }{{{\hat{t}}}^{\beta }} \\ & {{\kappa }_{T}}\tilde{\ }{{{\hat{t}}}^{-\gamma }} \\ & \hat{p}\tilde{\ }\Delta {{\rho }^{\delta }} \\ & \hat{t}:=\tilde{t}-1 \\ & \hat{p}:=\tilde{p}-1 \\ & \hat{v}:=\tilde{v}-1 \\ & \Delta \rho :={{\rho }^{fl\ddot{u}ssig}}-{{\rho }^{gas}} \\ \end{align}</math> '''Nach dem Fluktuations- / Dissipationstheorem (§ 1.3, S. 27)''' gilt: :<math>\left\langle {{\left( \Delta M \right)}^{2}} \right\rangle =-\frac{\partial \left\langle M \right\rangle }{\partial \lambda }</math> also für das Druckensemble <math>M=V,\lambda =\frac{p}{kT}</math> :<math>\left\langle {{\left( \Delta V \right)}^{2}} \right\rangle =-kT{{\left( \frac{\partial V}{\partial p} \right)}_{T}}=kTV{{\kappa }_{T}}\to \infty </math> Das heißt: Die Volumen- und Dichteschwankungen divergieren am kritischen Punkt! * man spricht von kritischer Opaleszenz! * (stark wachsende Lichtstreuung wegen der Schwankung des optischen Brechungsindex infolge der Dichteschwankungen) '''Verletzung der Stabilitätsbedingung → Phasenübergang!!'''
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