All fluids flow, some more easily than others.

The property that characterizes a fluid’s resistance

to flow is called viscosity, η (Levine, ). The viscosity of a fluid can be computed with the Hagen-Poiseuille
equation

𝑟 4 𝑡𝜋∆𝑃
𝑉= [8 − 1]
8𝜂𝑙
Where V = volume of liquid

r = tube radius

t = time

ΔP = pressure difference at the tube ends

η = viscosity

The necessary variables can be determined by allowing a known volume of liquid, V, flow
through a capillary tube under the force of gravity and measuring the time of flow. Such can be achieved
with the use of the Ostwald and Cannon-Fenske viscometers.

Both viscometers make use of a tube open at both ends. Assuming that the external pressure at
both ends is the same, we get

Δ𝑃 = 𝜌𝑔ℎ [8 − 2]
Where ρ = density of the liquid

g = acceleration due to gravity

h = height of fluid

Rearranging equation 8-1 and substituting equation 8-2,

𝑟 4 𝑡𝜋𝜌𝑔ℎ
𝜂= [8 − 3]
8𝑉𝑙
We can then define a constant that is characteristic of a viscometer, A.

𝑟 4 𝜋𝑔ℎ
𝐴= [8 − 4]
8𝑉𝑙
Substituting equation 8-4 to equation 8-3,

𝜂 = 𝐴𝜌𝑡 [8 − 5]
However, at the inlet of the capillary, a pressure drop occurs as a result of the necessity of
imparting kinetic energy to the fluid. At the outlet of the capillary, the fluid is carried in a jet stream far
out into the body of fluid beyond the outlet by its kinetic energy. The kinetic energy then dissipates as
heat (rather than as potential energy) (Shoemaker, ). The kinetic energy correction from the inlet and
outlet combined can be labeled as ρB/t, where,
𝜌𝐵 𝜌𝑉
= [8 − 6]
𝑡 𝑡8𝜋𝑙
Integrating the correction factor to equation 8-5 we get
𝜌𝐵
𝜂 = 𝐴𝜌𝑡 − [8 − 7]
𝑡
Both A and B can be determined from the dimensions of the viscometer. However, errors in
measurement and equipment can lead inaccurate values. A and B can be more accurately determined
by measuring ρ and t at known values of η. By linearizing equation 8-7,
𝜂 𝐵
=𝐴− 2 [8 − 8]
𝜌𝑡 𝑡

𝜂
𝜌𝑡
can be plotted against 1/t2 to get the slope, -B, and the y-intercept, A.

The viscous flow of liquids can be observed with respect to its molecular properties. Theories
regarding this were developed and one such theory is the Eyring’s theory which is based on the
transition state theory. Eyring’s equation for viscous flow is
ℎ𝑁𝐴 (∆𝐺̅𝑜 )
𝜂= 𝑒 𝑅𝑇 [8 − 9]
𝑉̅
Where h = Planck’s constant

NA = Avogadro’s number
̅
𝑉 = molar volume
̅
∆𝐺 = standard molar free energy for viscous flow
Getting the natural logarithm of both sides of the equation and rearranging it, we get
𝜂𝑀
∆𝐺̅ = 𝑅𝑇𝑙𝑛 [8 − 10]
ℎ𝑁𝐴 𝜌
Recall the fundamental thermodynamic equation
̅ 𝑜 − 𝑇∆𝑆̅ 𝑜
∆𝐺̅ 𝑜 = ∆𝐻 [8 − 11]
𝑜
̅
Where ∆𝐻 = molar enthalpy change for flow
∆𝑆̅ 𝑜 = molar entropy of activation
Assuming that both the molar enthalpy and the molar entropy are constant within the
̅ against T, we can get the slope, ∆𝑆̅ 𝑜 , and the y-intercept,
temperature range, by plotting ∆𝐺
𝑜
∆𝐻̅ .

The viscosity of polymers can be used to determine its average molecular weight and its
molecular weight. The intrinsic viscosity of polymers are affected by solvents. “Good” solvents
allows a polymer molecule to extend loosely, and a “poor” solvent keeps the polymer molecule
compact.
The derived viscosity functions are:
[insert equation 8-9 to 8-14 from manual]
Where 𝜂 = viscosity of polymer solution

𝜂𝑜 = viscosity of pure solvent

t = flow time for polymer solution

to = flow time for pure solvent

The Mark-Houwink equation relates the intrinsic viscosity and average molecular weight of a
large polymer. The root-mean-square end-to-end distance of a linear molecule was regarded in the
derivation of the Mark-Houwink equation. The equation needs to modified slightly for branched
polymers. The corrections due to bond angles, restriction to free rotation about bonds, and for the finite
volume of the chain segments are already incorporated in the equation.

̅𝑎
[𝜂] = 𝐾𝑀 𝑀𝑎𝑟𝑘 − 𝐻𝑜𝑢𝑤𝑖𝑛𝑘 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 [8 − 19]

Where K = empirical constant

a = empirical constant (function of the geometry of the polymer molecule in

solution)

= varies from 0.5 (well coiled polymer) to 1.7 (rigidly r=extended rod-like
molecule)
̅
𝑀 = (viscosity) average molecular weight
Objectives
This study aims to teach us, the students, how to determine the viscosities of aqueous
solutions (what solutions?) at various concentrations; evaluate thermodynamic properties of
some liquids (what liquids?) using Eyring’s equation; and calculate the molecular weight and
root-mean-square end-to-end length of a polymer at different salt concentrations using Mark-
Houwink’s equation.