Exercise 8 o Does not obey Newton’s law

VISCOSITY OF PURE LIQUIDS AND SOLUTIONS o Viscosity dependent on shear

Postlab Notes o e.g. blood
Viscosity,
 Resistance of a liquid to flow Factors affecting Viscosity
 Unit: SI 1. Temperature
2. Pressure
CGS 3. Composition

Types of Fluid Hagen-Poiseuille Equation

1. Newtonian fluid
o Exhibits laminar flow (i.e. uninterrupted flow)
o Viscosity constant at constant temperature and independent of
viscosity gradient
2. Non-Newtonian fluid
o Exhibits turbulent flow
o Viscosity dependent on shear force (i.e. movement by sliding
from one part to another)

Newton’s Law of Viscosity for Laminar Flow Poiseuille Law

 Visualized as a fluid being stratified into layers of planes of molecules
wherein one plate is stationary and the other is moving parallel to it at
Where: and (A and B are capillary dimensions)
a certain velocity
 The moving plate drags a layer of liquid along transferring momentum
to it so this layer of fluid drags another layer along transferring
momentum to it and so on
 Due to frictional losses, the speed of each layer is a little slower than
the layer above it
 Each layer exerts frictional resistive force on the other which gives rise
to viscosity
(Modified) Eyring’s Theory
Types of Fluid Flow  Theory of Absolute Reaction Rates
1. Laminar flow - relates viscosity to temperature
o Exhibited by Newtonian fluids
o Uninterrupted flow of liquid
o Flow is constant at each region
2. Turbulent flow
o Not in smooth layers; movement in different directions

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 2. Cannon-Fenske viscometers
o Has two bulbs ; allows the quantitative assessment of the effect
of shear stress on the viscosity of the solution
o Lower reservoir is directly below the upper reservoir ⟶ this
condition has been shown to give the minimum changes in
 Assuming enthalpy change for flow, , and entropy of activation, , pressure head resulting in the vertical alignment of the
to be independent of temperature viscometer
3. Ubbelohde viscometer
Plot: vs. o Constructed such that the pressure head of the suspended
Slope: liquid at the capillary outlet is independent of the liquid
y-int: originally introduced to the viscometer
o Used for very viscous solutions (e.g. polymers)
Methods of Determining Viscosity o Not calibrated because no constant is needed
1. Falling Ball method/Rising Bubble o Reverse Flow viscometers – for highly colored solutions
2. Capillary Flow method
3. Rotational method Experimental Procedure
4. Timed-fall of Piston method 1. Calibration of viscometer
5. Pressure drop thru Friction tube
6. Torque Viscometer
Plot: vs.
7. On-line process viscometer
8. Ultrasonic probe

Types of Viscometer Used for Capillary Flow Method

Slope:

y-int:
2. Determination of viscosities of pure liquids and solutions
a. Effect of increasing mole fraction
1) Calibration constants A and B

1. Ostwald viscometer Plot: vs.

o Dependent on the volume used since pressure area head will
vary with different solutions
o Has one bulb, thus the liquid is connected to the main reservoir
and affecting pressure

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 Slope: Relationship is usually a curve
Association Homo > hetero
y-int: Dissociation Homo < hetero

2) Calculation of ρsolution o Stronger IMFA (between solute and solvent particles) in a

liquid will hinder flow resulting to a higher value of
o e.g. acetone and water
o Several conditions to be met for accurate
measurement:
1) Flow characteristics of the liquid → Newtonian fluid
3) Calculation of ƞ at each mole fraction
(exhibits laminar flow)
2) Liquid must be pure and free from any impurity (may
clog capillary tube)
3) Temperature constancy → changes with
temperature
4) Pressure constancy

b. Effect of temperature
1) Calculation of ƞ at each temperature
Effect of increasing mole fraction on viscosity is
dependent on the type of binary solution and the IMFA present
between the solute and the solvent particles.

Case 1:
Solute-solute or

>
Solute-solvent
Solvent-solvent
interactions
interaction 2) Calculation of for each temperature
(heterogeneous)
(homogeneous) Modified Eyring’s equation:

(solute does not interact with the solvent, no dissolution)

Case 2:
Solute-solute or

<
Solute-solvent 3) Determination of and
Solvent-solvent
interactions
interaction
(heterogeneous) Plot: vs.
(homogeneous)

Slope:

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 y-int:

At higher temperature, there is higher kinetic energy that

disrupts IMFA between solute and solvent particles thereby
resulting to a decrease in .
* for NaCMC
3. Viscosity of NaCMC polymer
5) Molecular radius, r
 use of Ubbelohde viscometer
 Flow times of different polymer solutions were measured as
well as the flow time of the pure solvent (
 Polymers
o high molecular weight substances
o viscosity measurements give information on the size
and shape of the polymer molecule
1) Calculation of ƞsp 6) Root-mean-square end-to-end,
- derived from Kirkwood-Riseman equation

2) [ƞ]
 [ƞ] from ƞred
Plot: vs.

y-int:

 [ƞ] from ƞinh

Plot: vs. Derived Viscosity Functions
Relative Viscosity:
y-int:

3) Molecular weight,
Specific Viscosity:

Reduced Viscosity:

Inherent Viscosity:

4) Molecular size, s
Intrinsic viscosity:

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Mark-Houwink Equation


Well-coiled (tightly
coiled)
Rigidly extended
polymer
 and can also be determined experimentally

Effect of Polymer Concentration on Viscosity

 ↑ [NaCMC], ↑
More polymer chains, stronger attraction

 ↑ [NaCl], ↓ “salting out”

o At low [NaCl], solvation effect increases causing uncoiling of
polymer. Thus, increase in molecular attractions between NaCMC
and water molecules.
o Competing interactions between NaCMC-NaCl and NaCMC-water
o Uncoiled polymer molecules has more area for interaction (unlike
the coiled polymer molecules) thus higher viscosity

Solvation of Polymer
GOOD solvent BAD solvent
hetero > homo hetero < homo
Uncoiled polymer Coiled polymer

energy not needed energy is needed to form solution

Increase in Decrease in
*Therefore, the better solvent is 0.001 M NaCl than 0.100 M NaCl

Possible Sources of Error

1. Temperature fluctuation
2. Drainage errors
3. Vertical alignment
4. Timing
5. Changes in sample composition
6. Assumption that flow is laminar
Notes from PLJA©2014

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