THE VISCOSITY OF DILUTE SOLUTIONS OF LONG-CHAIN

MOLECULES. I1bz
MAURICE L. HUGGINS
Kodak Research Laboratories, Rochester, New York
Received July 1, 1988
INTRODUCTION

This paper is a report of an attempt to develop a satisfactory theory,

heretofore lacking, of the viscosity of dilute solutions of long-chain compounds.
For solutions or suspensions of incompressible, spherical particles which
are large in comparison with the molecules of the solvent, Einstein (3, 4)
has derived the relationship

For solutions or suspensions of particles consisting of spheres rigidly

held together t o form a rod-like molecule (the distance between
sphere centers being twice the sphere diameter), Kuhn (15, 16) deduced
the equation

I n the derivation he assumed that the Brownian motion is large in comparison with the velocity gradient in the solution.
For ellipsoidal particles Eisenschitz (5, 6) derived the equation

neglecting the Brownian motion, and

(4)

for very long particles, with a large Brownian motion effect.

Presented a t the Fifteenth Colloid Symposium, held a t Cambridge, Massachusetts, June 9-11, 1938. A preliminary report of this work was presented a t the
Ninety-fourth Meeting of the American Chemical Society, held a t Rochester, Kew
York, September, 1937.
Contribution No. 647 from the Kodak Research Laboratories.
911

912

MAURICE L. HUGGIKS

In these equations,

is the fractional increase in viscosity of the solution over that, of the pure
solvent, c/V- is the volume of solute per unit volume of solution, fi is the
ratio of the length of the rod-like molecule t o the diameter of thespheres
of i\-hich it is composed, and fi is the axial ratio of the ellipsoid.
Enipirically Staudinger (26,27,28) showed that, for yery dilute solutions
of several types of long-chain compounds, the specific viscosity divided by
the concentration in subnioles (Grundmole!) per liter is approximately

.I2
11
10

08
.07

.oa
OS
.04

oa
DZ

0I
0

10

20

15

x)

Fro. 1. Experimental and previous theoretical values of

of parafins i n carbon tetrachloride a t 20C.

35

7.Jc

4011

for dilute solutions

proportional to the number of subwzolecules (Grundniolekule, e.g., CH2

groups in a paraffin chain) in the chain:
9LP =
C

k, n

(5)

This empirical relationship has been much used by Staudinger and others

deducing approximate average molecular weights of high polymers.

The experimental viscosity data of Meyer and van der Wyk (22) and of
Staudinger and Staiger (28) for solutions of normal paraffins are compared
with t h e theoretical values calculated from equations 1, 2, 3, and 4 in
figurc 1. Since, in the writers opinion, the inclusion of an Einstein incomiri

presihilitytern1:rni

(iG)

in equation 2 for rod-like molecules isvery question-

ahle. n curve representing the equation

i; a1.o included in the figure.

VISCOSITY O F SOLUTIONS O F LONG-CHAIN MOLECVLES

913

It is evident that none of the theoretical curves is satisfactory. The

experimental points lie approximately on a straight line, but (from Meyer
and van der Wyks data a t least) not one that passes through the origin.
Aside from this comparison, there is considerable other evidence favoring the supposition that long-chain molecules, such as the paraffis, are
very much kinked in solution, rather than straight. The rigidity of such
kinked molecules is more questionable, although there is considerable
evidence (10, 11, 12, 13, 14, 23, 24, 25; cf., however, 1) for the existence of
potential energy humps of the order of magnitude of 3000 cal. (Le., about
5 times R T ) per mole tending to prevent rotation about each single bond
in a paraffin chain. If so, intermolecular collisions will only very rarely
have sufficient energy to produce rotation over these energy humps, but
rotation through a few degrees will take place much more readily.
In view of the foregoing, a theoretical calculation of the viscosities of
dilute solutions of rigid, randomly kinked chain molecules has been made,

FIG.2. Illustrating the orientation of reference axes, etc.

with some progress in extending the results to non-rigid, kinked chain

molecules. Only an outline of the methods and results will be presented
here; the details will be given in a later paper.
DERIVATION O F A GENERAL EQUATIOK FOR RIGID MOLECULES

We first consider a rigid molecule in dilute solution and, following an

elaboration and extension of Kuhns procedure (15, 16, 17), calculate the
relation between the work done on this molecule by the solution as a
function of the velocity gradient of the solution, the viscosity of the solution, and the coordinates of the atoms in the molecule.
The origin is taken at the center of moments of the molecule, with the
axes so oriented that the surrounding liquid moves in the Z direction with
a velocity, qx, which is proportional to 5 . The atoms are numbered
1, 2, 3 . . . . i.. . . n and their cobrdinates designated as z,,yt! z , (see
figure 2).

914

MAURICE L. HUGGINS

Because of the velocity gradient in the liquid, the molecules rotate

about the Y-axis. We represent the length of the vector from the origin
to the projection of the atom i onto the XZ plane by ri and the angle
measured counterclockwise from the X-axis t o this vector by Oi.
The work expended on atom i in unit time is deduced to be

The work expended on all n atoms, if they all have the same radius a ,
is
c

= 6irvq2aFzr

(8)

where
E X : . ZZ: - ~ r cos2
2 Oi. Zr: sin' Oi
F " = T Zr:

(9)

From this is derived the relationship:

in which N is Avogadro's number and

orientations.
It can be shown that, if

is the average of F,, over all

6nqaq(Zr: cos20; - Zr? sin20:)

kT
is small compared to unity ( k being the Boltzmann constant and T the
absolute temperature) , then

Fa, =

2%

1 2R; sin2 0 ; .2R: cos2 0;

ZR:

12 3. ij

1 (ZR: sin 0: cos 0;)'

-3
2R:

(11)

The angles Oi are constants, being measured relative t o an arbitrary set

of X - and Z-axes rotating with the molecule.
APPLICATION TO RIGID CHAIN MOLECULES

For linear rod-like molecules equation 11 reduces to

-

F,.

t ( n 5- n)

___
144

(12)

VISCOSITY O F SOLUTIONS OF LONG-CHAIN MOLECULES

915

With large n and small concentrations, from equation 10,

qL? =z ?rNa12n2
___

24000

We next consider a rigid, randomly kinked, centrosymmetric chain

molecule. For the average value of R: we make use of a relationship,
derived by Eyring (7) ,

R: = lZBi

(14)

where

B =1

+2

( 5 9 t

9
0

+ 2(-&i - 2

+ 2(-)t3
i - 3
2

+ ... + 2

p (15)

By an extension of Kuhn's (18) statistical methods, it is possible to show

that the average of the square of the distance of the ithatom of the chain
molecule from the straight line joining the origin (at the center of the
molecule) to the end (mth) atom is

Also,

916

YACRICE L. HCGGINS

Making the approximations

Z R sin'
~ 0: .ZR? cos2 O:

ZRZ:

ZR: sin' 0,.212;cos20,

.-.
ZR4

(20)

and performing the summations, we obtain

F,, = 0.0324fiB,Z2a(nZ- 2n

+ I)

(22)

in which is a complicated function of n which approaches unity as n

increases (see figure 4 ) .

By a complicated procedure, involving an analogy with a rod-like

molecule bent in the middle, with all angles of bending equally probable,
for randomly
a factor of 4/5 has been calculated for the conversion of
for ot,herwise similar molecules
kinked centrosymmetric molecules t o
which do not necessarily have centers of symmetry. For this more general
case, then,

zs

= 0.0259fiB,12a(n2- 2n f 1)
VSP
-

4.84 X 10-4NflB,12a(n - 2)
1 - 4.84 X 10-4NpB,12a(n - 2)c

(24)
(25)

For large values of n and small values of c equation 25 reduces to

C

= 4.84 X 10-4NB,12an

(26)

We thus have a theoretical derivation of Staudinger's empirical viscosity

law (26).

VISCOSITY O F SOLUTIONS O F LONG-CHAIN MOLECULES

917

EXTENSION TO NON-RIGID CHAIN MOLECULES

An &tempt has been made to determine the effect of introducing flexibility (resulting from free or restricted rotation about the bonds in the
chain) into the molecular model. The problem is a complicated one, which
will be dealt with in detail a t another time. For the present a few comments will suffice.
In general, the viscosities should be nearly the same for flexible longchain, kinked molecules as if they were rigid. The solvent exerts a stretch2 between 7r and 3 ~ / 2and a coming force for @, between 0 and ~ / and
pression force during the rest of the rotation. Tending to counteract this
is the entropy change, which can be calculated approximately (2, 8, 9, 18,
19, 21). As a net result it can be shown that the qs,/c values, as calculated

FIG. 5

for a rigid molecule, should be multiplied by a flexibility factor, H ,

which varies with

approximately as indicated in figure 5.

In addition, a small constant term should be added to qap/c to allow
for rotation of units other than a t the ends of the chain and a term of the
form const./n to cover rotation of the atoms and groups near the ends.
COMPARISON WITH EXPERIMENTAL DATA

The best experimental data now available for testing these theoretical
results are for solutions of the paraffins (22, 28). We use equation 25 for
rigid, randomly kinked molecules, rough calculations indicating that the
corrections for flexibility would not make much difference in the result.

918

MAURICE L. HUGGINS

In agreement with x-ray and electron diffraction data we take

= 1.54 X 10-Ecm.

(28)

and assume tetrahedral bond angles, hence

B,

= 2

(29)

The effective radius, a, must be of the order of magnitude of

cm.
Certain qualitative considerations suggest that it should approximately
equal the radius of the sphere having the same surface area as the surface,
per unit segment, of the molecule, considered as cylindrical. If this is
assumed we calculate, from the density of liquid paraffins,
a = 1.28 X 10-8cm.

IO

IS

(30)

FIQ.6. Experimental and theoretical values (from equation 25) of vap/c for dilute
solutions of paraffins in carbon tetrachloride at 20C.

Substituting these values for 1, B,, and a in equation 25 and reading @

from figure 4, the values used in plotting the upper curve of figure 6 are
obtained. If the slightly lower value, a = 1.18 X 10-8 cm., is used, the
lower curve is obtained. The agreement is very satisfying, considering
the method of estimating a and other approximations used in the derivation. The slope of the theoretical curve lies between that of the curve
through Meyer and van der Wyk's values and that of the curve through
Staudinger and Staiger's results.
Comparisons with experimental data for other series of compounds will
be made at another time.
THE MC BAIN EXPERIMENTS

McBain and McBain (20) compared the velocities of fall through sucrose
solutions of quartz fibers and quartz spheres of the same weight and volume, showing that the difference in frictional resistance t o movement of
these particles is by no means sufficient to account for the observed high

VISCOSITY O F SOLUTIONS O F LONG-CHAIN MOLECULES

919

viscosities of dilutesolutions of long-chain compounds. They conclude,

therefore, that the chief factor is structural viscosity due to entanglement
and local adherence of molecules and particles, effectively immobilizing
a disproportionate amount of the solvent in comparison with the amount of
the colloid itself.
It should be pointed out that the McBain experiments bear little or no
relation to the problem, since in their experiments the velocity of one side
of the particle relative t o the surrounding liquid is the same as that of the
other side. I n any viscosity determination a velocity gradient is set up.
As is shown in this paper (and has been shown previously by others), it
follows from classical hydrodynamics that because of this velocity gradient
frictional work is done on non-spherical particles by the liquid. This
effect must exist, and the evidence presented here shows that its magnitude is such as to account practically quantitatively for the experimental
data, a t least for dilute solutions of paraffins.
SUMMARY

By an extension of Kuhns hydrodynamical treatment a theoretical

equation has been derived relating the specific viscosity of a solution to the
coordinates and dimensions of the atoms in the solute molecules. Applied
to rod-like molecules this equation leads t o proportionality (with n large)
between qsp/c and n2. Applied to randomly kinked chain molecules, it
leads to proportionality between vlap/cand n, the Staudinger relationship.
Theoretical expressions have been obtained for the proportionality
constant and also for the deviations for small values of n. Using a reasonable value for the effective radius of the CH2 group, without any arbitrary constants whatever, the experimental data for solutions of paraffins
are quantitatively accounted for.
I n conclusion, it is a pleasure to give acknowledgment to Miss Dorothy
Owen, who performed a large part of the necessary calculations during
the preparation of this paper.
REFERENCES
(1) BAR THO LO MI^, E., AND KARWEIL,J.: Z. physik. Chem. B39, 1 (1938).
(2) DOSTAL,H.:Monatsh. 71, 144 (1938).
(3) EINSTEIN,A.: Ann. Physik [4] 17, 549 (1905).
(4) EINSTEIN,A.: Ann. Physik [41 19, 289 (1906).
(5) EISENSCHITZ,
R.: 2. physik. Chem. A168, 78 (1931).
(6) EISENSCHITZ,
R . : 2.physik. Chem. A l a , 133 (1933).
(7) EYRING,H.:Phys. Rev. 39, 746 (1932).
(8) GUTH,E., A N D MARK,H.: Monatsh. 66,93 (1934).
(9) GUTE, E., AND MARK,H.: Z. Elektrochem. 43, 683 (1937).
(IO) HOWARD,J. B.: Phys. Rev. 61, 53 (1937).
(11) KEMP,J. D.,AND PITZER,K. S.: J. Chem. Phys. 4,749 (1936).

920

MAURICE L. HUGGING

(12) KFMP,J. D., AXD PITZER,

K. S.: J. Am. Chem. SOC.69, 276 (1937).
(13) KISTIAKOWSKY,
G. B., AND NAZMI,F.: J. Chem. Phys. 6, 18 (1938).
(14) KISTIAKOWKY,
G. B., AND WILSON,E. B., JR.: J. Am. Chem. SOC.60,494 (1938).
(15) KUHN,W.:Z. physik. Chem. A161, 1 (1932).
(16) KUHN,W.:Z. physik. Chem. A161, 427 (1932).
(17) KUHS, W.:
Kolloid-Z. 62, 269 (1933).
(18) KUHN,W.:
Kolloid-Z. 68, 2 (1934).
(19) KUHX,W.:Kolloid-Z. 76, 258 (1936).
(20) MCBAIN,J. W.,A X D MCBAIK,M. E. L.: J. Am. Chem. Soc. 69, 342 (1937).
(21) MEYER,K. H., . ~ X DFERRI,C.: Helv. Chim. Acta 18, 570 (1935).
(22) MFYER,K. H . , A N D VAN DER WYK, A,: Helv. Chim. Acta 18, 1067 (1935).
K. S.: J. Chem. Phys. 6, 469 (1937).
(23) PITZER,
(21) PITZER,
K. S.: J. Chem. Phys. 6 , 473 (1937).
S. C., A X D ASTON,J. G.: J. Am. Chem. SOC.60, 985 (1938).
(25) SCHUMANN,
(26) STAUDINGER,
H. : Die hochmolekularen organischen Verbindungen. Julius
Springer, Berlin (1932).
(27) S T h V D I N G E R , H.: Helv. Chim. Acta 19, 204 (1936).
(28) STAUDISGER,
H., A S D STAIGER, F.: Ber. 68, 707 (1935).