By L. Ƶechmeister (auth.)
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Additional info for Bibliography of Papers: 1913–1958
101) 4 η + ζ + (Cp,A /Cv,x − 1) λ/Cp,x 3 − (∂ρ/∂x)p,T + kT (∂ρ/∂T )x,p (∂A/∂x)p,T Cp,x 2 D (∂p/∂ρ)x,T ρ0 (∂A/∂x)p,T . 102) September 11, 2009 10:7 42 World Scientific Book - 9in x 6in General-nn Chemistry versus Physics: Chemical Reactions near Critical Points One can readily use the hydrodynamic equation including the chemical term (L0 = 0) and perform the analogous calculations, but this procedure leads to very cumbersome expressions. Therefore, we consider the inﬂuence of a chemical reaction for the simpliﬁed case of a non-compressible liquid (div (v) = 0), neglecting ﬂuctuations of pressure (p = 0) .
In the general case, such a calculation involves a very cumbersome analysis. To avoid this, we consider some special cases. When one neglects the thermal variables, viscous, diﬀusive and chemical modes appear in Eq. 84), × 1+ L = L20 + × ∂A ∂ξ 2 4 3η 2 p,S 4 3η + ζ 2 2 +ζ ∂ρ ∂A L1 /ρ0 Dk 2 + L0 (∂A/∂ξ)ρ,S ρ0 (∂ξ/∂ρ)A,S k + 4ρ0 L1 (∂A/∂ρ)ξ,S + ρ20 ξ,S ∂ξ ∂ρ A,S ∂ρ ∂p . 114) ξ,S Note that the diﬀusive mode appears in Eq. 114) because of the additional phenomenological visco-reactive coeﬃcient L1 introduced in Eqs.
5) where kf and kb are the microscopically determined rate coeﬃcients for the forward and backward reactions, and Ci are the concentrations (fugacities) of the i-th species in an ideal (nonideal) solution. 6) one can rewrite Eq. 7) where A is the aﬃnity of reaction. 2Cl, the rate r is deﬁned as r = For chlorine dissociation, Cl2 2 , and, using µi = µ0i +RT ln Ci , and kf /kb = exp ν i µ0i /RT , kf CCl2 −kb CCl September 11, 2009 10:7 20 World Scientific Book - 9in x 6in General-nn Chemistry versus Physics: Chemical Reactions near Critical Points one gets r = kf CCl2 1 − exp − A RT .