Intrinsic viscosity

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Intrinsic viscosity \left[ \eta \right] is a measure of a solute's contribution to the viscosity \eta of a solution. It should not be confused with inherent viscosity, which is the ratio of the natural logarithm of the relative viscosity to the mass concentration of the polymer.[1]

Intrinsic viscosity is defined as


\left[ \eta \right] = \lim_{\phi \rightarrow 0} \frac{\eta - \eta_{0}}{\eta_{0}\phi}

where \eta_0 is the viscosity in the absence of the solute and \phi is the volume fraction of the solute in the solution. As defined here, the intrinsic viscosity \left[ \eta \right] is a dimensionless number. When the solute particles are rigid spheres at infinite solution, the intrinsic viscosity equals 
\frac{5}{2}, as shown first by Albert Einstein.

In practical settings, \phi is usually solute mass concentration (c, g/dL), and the units of intrinsic viscosity \left[ \eta \right] are deciliters per gram (dL/g), otherwise known as inverse concentration.

Formulae for rigid spheroids[edit]

Generalizing from spheres to spheroids with an axial semiaxis a (i.e., the semiaxis of revolution) and equatorial semiaxes b, the intrinsic viscosity can be written


\left[ \eta \right] = 
\left( \frac{4}{15} \right) (J + K - L) + 
\left( \frac{2}{3} \right) L + 
\left( \frac{1}{3} \right) M + 
\left( \frac{1}{15} \right)  N

where the constants are defined


M \ \stackrel{\mathrm{def}}{=}\  \frac{1}{a b^{4}} \frac{1}{J_{\alpha}^{\prime}}

K \ \stackrel{\mathrm{def}}{=}\  \frac{M}{2}

J \ \stackrel{\mathrm{def}}{=}\  K \frac{J_{\alpha}^{\prime\prime}}{J_{\beta}^{\prime\prime}}

L \ \stackrel{\mathrm{def}}{=}\  \frac{2}{a b^{2} \left( a^{2} + b^{2} \right)}
\frac{1}{J_{\beta}^{\prime}}

N \ \stackrel{\mathrm{def}}{=}\  \frac{6}{a b^{2}}
\frac{\left( a^{2} - b^{2} \right)}{a^{2} J_{\alpha} + b^{2} J_{\beta}}

The J coefficients are the Jeffery functions


J_{\alpha} = 
\int_{0}^{\infty}  \frac{dx}{\left( x + b^{2} \right) \sqrt{\left( x + a^{2} \right)^{3}}}

J_{\beta} = 
\int_{0}^{\infty}  \frac{dx}{\left( x + b^{2} \right)^{2} \sqrt{\left( x + a^{2} \right)}}

J_{\alpha}^{\prime} = 
\int_{0}^{\infty}  \frac{dx}{\left( x + b^{2} \right)^{3} \sqrt{\left( x + a^{2} \right)}}

J_{\beta}^{\prime} = 
\int_{0}^{\infty}  \frac{dx}{\left( x + b^{2} \right)^{2} \sqrt{\left( x + a^{2} \right)^{3}}}

J_{\alpha}^{\prime\prime} = 
\int_{0}^{\infty}  \frac{x\ dx}{\left( x + b^{2} \right)^{3} \sqrt{\left( x + a^{2} \right)}}

J_{\beta}^{\prime\prime} = 
\int_{0}^{\infty}  \frac{x\ dx}{\left( x + b^{2} \right)^{2} \sqrt{\left( x + a^{2} \right)^{3}}}

General ellipsoidal formulae[edit]

It is possible to generalize the intrinsic viscosity formula from spheroids to arbitrary ellipsoids with semiaxes a, b and c.

Frequency dependence[edit]

The intrinsic viscosity formula may also be generalized to include a frequency dependence.

Applications[edit]

The intrinsic viscosity is very sensitive to the axial ratio of spheroids, especially of prolate spheroids. For example, the intrinsic viscosity can provide rough estimates of the number of subunits in a protein fiber composed of a helical array of proteins such as tubulin. More generally, intrinsic viscosity can be used to assay quaternary structure. In polymer chemistry intrinsic viscosity is related to molar mass through the Mark–Houwink equation. A practical method for the determination of intrinsic viscosity is with a Ubbelohde viscometer.

References[edit]

  1. ^ "Dilute Solution Viscosity of Polymers". 
  • Jeffery GB. (1922) "The Motion of Ellipsoidal Particles Immersed in a Viscous Fluid", Proc. Roy. Soc., A102, 161-179.
  • Simha R. (1940) "The Influence of Brownian Movement on the Viscosity of Solutions", J. Phys. Chem., 44, 25-34.
  • Mehl JW, Oncley JL, Simha R. (1940) "Viscosity and the Shape of Protein Molecules", Science, 92, 132-133.
  • Saito N. (1951) J. Phys. Soc. Japan, 6, 297.
  • Scheraga HA. (1955) "Non-Newtonian Viscosity of Solutions of Ellipsoidal Particles", J. Chem. Phys., 23, 1526-1531.