Viscosity

Fluids resist a gradient

Physical Chemistry of flow
 Tries to achieve constant
speed across the sample
This resistance creates
Lecture 3 a force called the
Viscosity and sedimentation viscous drag
  viscosity coefficient
(or just viscosity) dv
Viscosity is measured in Fdrag  A
poise (10-1 kg m-1 s-1) dx

Measurement of viscosity Ostwald viscometer

Need a small-diameter
Measure flow in the tube (capillary)
presence of a Measure time of flow of
gradient of speed a specific volume
through the capillary
Poiseuille’s formula Constant pressure drop
for flow through a across the capillary
cylindrical tube Use Poiseuille’s
subject to a V  r4 equation to calculate
pressure drop  P viscosity
t 8 l Must be calibrated with
a known material 
t  B


Falling-ball viscometer Origins of viscosity

R Liquids
Measure the vt   Short-range attractive intermolecular forces
terminal velocity of t  Hard to model exactly
a ball falling in a  Described empirically
fluid  Viscosity usually decreases with increasing T
Use Stokes Law for Gases
the viscous drag to  Momentum transfer between “fast” and “slow”
molecules
determine viscosity  Simple kinetic theory gives a prediction
n *  v  m
r    0  t
2 2 g
    
mkT
9 R 2  3d 4 N 0
 Predicts an increase with temperature

1
Comparison of temperature- Intermolecular forces –
dependent viscosities Enskøg’s relation
Viscosity of Oxygen

Gas: oxygen Simple kinetic theory

250 Viscosity of Nitrogen at 50 C
200

predicts no particular

 (micropoise)
600

 Increase with 150 500

 (micropoise)
temperature
100
density dependence of 400
300

gas viscosity
50
200
0 100

Inclusion of excluded-
50 100 150 200 250 300 0
T (K) 0 0.005 0.01 0.015 0.02

volume interactions by
Number Density (mole cm -3)

Viscosity of Aniline

Liquid: aniline 0.16

Enskøg gives a density
dependence for the 
Decrease with b  
2

0.12
 b0 
viscosity of a gas   0 1  0.175   0.865 0  
 (poise)

temperature
0.08

0.04
  Vm   Vm  

0
250 300 350 400
T (K)

Including attractive forces –

Sutherland’s equation Viscosity of polymer solutions
Approximate  RM  Viscosity of a solution depends on
T
potential by    3 / 2   Nature of materials in solution
Sutherland   d  1 S  Amount of each material in solution
incorporates T
attractive forces Example: polymers in solution with a small-
Example: oxygen Viscosity of Oxygen
molecule solvent
viscosity as a 250  Einstein’s relation for a solution of solid balls
function of square
  0 1  2.5V 
200
 (micropoise)

150

root of the 100

temperature
50

0
8 10 12 14 16 18
 V is the volume fraction
Square Root of T

Viscosity of polymer solutions Viscosity of polymer solutions

Specific viscosity, sp Example: polystyrene in benzene (from Noggle)
Intercept gives intrinsic viscosity
  0 10 r3
 sp   cm One may calculate the viscosity-average molecular
0 3m weight from [] with the Mark-Houwink equation

Intrinsic viscosity, [] Polystyrene in Benzene

 sp 0.06

   lim c 0.05
cm  0
 sp/cm

m 0.04

Mark-Houwink equation 0.03

 
0.02

 K M
0 5 10 15 20
cm (gm cm -3)

2
 Sedimentation Sedimentation Coefficient
Time (min) r (cm) ln r
Particles settle in a force Data from Tinoco, 16 6.2687 1.836

field based on mass Sauer, and Wang, for a 32 6.3507 1.849

DNA sample 48 6.438 1.862
Measure the settling speed
Plot according to
64 6.5174 1.874

to determine mass equation

80 6.6047 1.888
96 6.6814 1.899
Use centrifugal motion as r
the force ln    St
2

 r0 
r Slope gives S, if the
ln    2 St frequency is known
 r0 
Frequency in rad/sec
unit: Svedberg = 10-13 sec

Sedimentation Coefficient Summary

Used for determining molar mass
Movement of molecules under forces
Example from Reisner, Rowe, and Macindoe, J. Mol. Biol., 32,
587 (1968).  Viscous flow
 Ribosomes
 Sedimentation
 T = 20C
 S = 82.6 Sv Useful in characterizing the material
 D = 1.5210-7 cm2 s-1
 Viscosity coefficient is a material property
 V = 0.61 cm3 g-1
 Sedimentation coefficient, S, depends on
M 
SRT

82.6  1013 s (8.3144349 J K 1mol 1 )( 293K )

molar mass
D (1  V  ) (1.52  1011 m 2 s 1 )(1  (0.61cm 3 g 1 0.99808 g cm 3 ))
1
 3.394  10 kg mol
3