CHARACTERIZATION OF POLYVINYL ACETATE

by

MOLECULAR WEIGHT DETERMINATION

A Thesis

by

Rosa Elmore Robertson, M.Sc.,

Submitted to the Faculty of Graduate

studies and Research at McGill University,
in partial fulfilment of the requirements
for the degree of Doctor of Philosophy

McGill University
Montreal
Canada April 1944
 ACKNOWLEDGEMENTS

The writer wishes to express his sincere appreciation

to Dr. R. L. Mcintosh for his guidance, encouragement and
assistance throughout thi~ investigation.
Thanks are also due to Dr. W. E. Grummitt who was a
eo-worker during the initial stages of the work.
Acknowledgement is made to the National Research
Council for the grant of a studentship in 1942-43 and a
Fellowship in 1943-44.
 TABLE OF CONTENTS
Page
INTRODUCTION 4

THEORETICAL BACKGROUND 6
EXPERIMENTAL
Xaterials
Polyvinyl Acetate 33
SolTents 34
Solutions 34

Viscosity Measurements
Apparatus 38
Procedure and Calculation 39
Apparatus and Techniques tor Osmotic
Measurements
The Xoditied Carter-Record Cell 41
The Modified Van Campen Cell 4o
Constant Temperature Bath 53
Xembran.es 57
RESULTS
Preliminary Membrane Data 63
Data from Carter-Record Membranes 67
Caustic Treated Membrane Results 69
Viscometrio Results 76
Relative Heterogeneity 82
Rationalization of Inconsistent Osmotic Data 83
DISCUSSION 90
CLAIMS TO ORIGINAL WORK
AND CONTRIBUTIONS TO KNOWLEDGE 106
REFERENCES 107
Ph.D Chemistry

Roslf Elmore Rober.tson, M.sc.

CHARACTERIZ&XION OF POLYVINYL NCETA~E

BY MOLECUL&R ~GH~DETERMINATION

The need for an absolute method to follow the changes

in viscosity shown by polyvinyl acetate in various solvents,
initiated a study of osmotic methods for determining moleo-
ul~r weights of this polymer.
~ Carter-Record type of cell was found less convenient
than a modified form of the Van Campen osmometer. Number
average molecular weights for polyvinyl acetate determined
with the latter did not agree with reasonable predictions
of intrinsic viscosity measurements when Carter-Record type
membranes were used. Reasonable molecular weights were
obtained for Gelva 15,45,150 and 360 with caustic
treated membranes.
A theory for the permeability of membranes is presented
which will account for the observed phenomena. The inconsis-
tencies in Osmotic data obtained with Carter-Record type
membranes are due to real changes in concentration at the
surface of the membrane. Time lags in reaching equilibrium
indicate the presence of adsorption.
A method for estimating the relative heterogeneity
of polymers is presented.
 INTRODUCTION

The rapidly increasing industrial importance of high

polymers requires no emphasis. The need for accurate
characterization of such polymers grows with each new ap-
plication, and the empirical rules of an earlier date no
longer appear adequate.
More than twenty years ago the high viscosity asso-
ciated with solutions of such materials was noted by ex-
perimentalists. Ever increasing attempts have been made
since that time to explore and define such systems by
viscometric measurements, and to relate the effects to
the fundamental structure of the molecules. However,
the interpretation of such data was restricted by its
inherently relative nature. Impetus was therefore given
to the development of the absolute osmotic pressure method
for determining the particle size, and so relating the
properties of the solution to a £undamental characteristic
of the polymer.
A theoretical approach is of recent origin. Flory (1),
Huggins (2)(3)(4), and others (5) expanded the statistical
treatment of Fowler and Rushbrooke (6}, to interpret the
formalized assembly suggested by Meyer {7) as representing
long chain-like molecules dissolved in a solvent consist-
ing of small molecules. Huggins, in a long series of
papers, attempted to show that the expression derived fro.m
 5
such a model permitted the use of classical thermodynamic
relations and gave good agreement with experimental data.
The work described in this thesis grew from a need
to characterize solutions of polyvinyl acetate more completely
than could be done through chemical and viscometric methods.
The inconsistent osmotic results obtained by following the
methods outlined in the literature led to a study of the
theoretical basis for characterizing polymers and a thorough
review of osmotic techniques with particular attention to
the preparation and action of membranes.
 THEORETICAL BACKGROUND

One of the most important problems in defining the

behaviour and characteristics of a given high polymer is
the determination of the average size of the dispersed
particles. The only absolute methods available are direct
osmotic measurements or a determination of the sedimenta-
tion equilibrium {8) using a Svedberg ultracentrifuge. In
certain polymers a determination of the end-group, in the
absence of branching, may give reliable results. However,
the precision of this method is probably inadequate in the
case of very large molecular weights (9). Viscometric
methods were the earliest and remain the most convenient
relative method. The development of optical methods by
Herzog and others (10), and Debye (12) promises to aid
the rapid determination of relative particle size, but as
yet these have not come into general use.
Before discussing the pertinent methods for deter.mining
particle size, it will be profitable to consider the state
of such high polymers when in dilute solution. During the
past ten years, it has generally been assumed that long
chain polymers in dilute solution are dispersed to single
molecules, as opposed to the aggregates commonly associated
with colloidal phenomena. The implications of such an as-
sumption are so important that it will be well to consider
 7
the proof tor its generality.
The classical researches of KcBain, Kruyt. and
Zsigmondy on the size ot colloidal particles led Meyer to
develop a micelle theory (13) to account for the colloidal
behaviour of high polymer solutions. Staudinger (14) had
already provided chemical evidence that in dilute solution
the dispersed particles actually correspond to very long
molecules in the ordinary sense ot the word. The physical
proof was difficult to obtain, but the logic of the conclu-
sion was demonstrated by Kraemer (15). He pointed out that
the intrinsic viscosity, defined as

C7J
~sp • the specific viscosity which is a measure ot
the increase in viscosity que to the suspended
solute and defined mathematically as

where
~s • viscosity of the solution
~~ = viscosity of the pure solvent
~ = concentration in grams per lOO c.c.
was approximately constant (16) for a given polymer when
determined in solvents of a widely different nature.
 8
Sueb a result was unexpected on the basis of previous
experience with colloidal dispersions. Since the intrinsic
viscosity is very sensitive to aggregation and association,
the uniformity of this function as deter.mined in various
solvents, implies that the polymers disperse to the same
degree in eaCh solvent. Using Kraemer's argument, we must
either aasame that the aggregates held together by van der
Waal's forces are of the same average size and immobilize
equal volumes of solvent, or we must adopt the simpler
idea that the unit dealt with in dilute solutions is a
single molecule. This would imply a long chain or group
of atoms held together by hamopolar Chemical covalencies
(17) in such a way that a line representing only covalencies
can be drawn from each individual atom to any other atom ot
the molecule {18). The inference that the remarkable pro-
perties exhibited by suCh molecules were due to the extra-
ordinary size and shape of the individual molecule, was
unavoidable. It is only in very dilute solutions that
such a state exists. In less dilute solutions and in the
solid state (19)(13) secondary valence .f'orces and mutual
interference combine to give exaggerated concentration
deviations, and aggregations to particles of varying sizes
and shapes will occur. Physico-Chemical investigation is
therefore restricted to a study of very dilute solutions,
if we are to avoid secondary effects.
 9

The problem of determining the molecular weight of a

sample is complicated by the inherent heterogeneity of such
materials. This heterogeneity may be classified in three
types:
a) Variation in the arrangement of segments
resulting in head-to-tail, tail-to-tail,
and head-to-head variations throughout
the chain length.
b) Variation in the configuration of chains
such as branching or cross linkages.
c) Variation in the length of the chains 1n
any given sample.
Variations of the first type will not influence the deter-
mination of particle size. Deviations from linearity will
have a marked influence on viscometric deter.minations but
will not alter the absolute osmotic value whiCh depends on
the number of particles present for a known concentration.
Heterogeneity arising from the presence of molecules of
varied chain length is by far the most important type.
Lack of homogeneity in this sense not only complicates the
comparison of average molecular weights obtained by various
methods, but casts doubt on existing values where this
factor has been neglected.
Because of the importance of heterogeneity of chain
length in the determination of molecular weights by any
 10
method, and its controlling influence in the comparison
and interpretation of data, it will be worth while to dis-
cuss this aspect of the general problem in a separate sec-
tion of the theoretical review.
Viscametric measurements are perhaps the most widely
used means for deducing and classifying the characteristics
of solutions. The theoretical basis for suCh classification
was laid in 1906 when Einstein (20) derived the relationship
between the increase in the viscosity of a suspension and
the volume of the dispersed particles. His calculation
dealt with an idealized suspension of rigid spheres at
extremely low concentrations. The spheres are large compared
with the solvent molecules, and are completely wet by them.
The solvent is incompressible and flow rates are so gradual
that turbulence is excluded.
For such a suspension Einstein's viscosity law predicts
that the coefficient of viscosity will increase by a frac-
tion corresponding to 2.5 times the volume fraction of the
suspended spheres. The subsequent experimental verifica-
tion of this law has been reviewed thoroughly by Mark (21).
In the course of these investigations Berl (22}, and
Biltz (23) observed wide variations from the Einstein law
for systems containing starch and cellulose derivatives.
However, no attempt was made to give a quantitative inter-
pretation for such qualitative observations until Staudinger
 ll
published his well-known equation relating the size and
the shape of such molecules to the observed deviations fro.m
assumed ideality (24). He proposed that variations 1n the
viscosity for solutions of the same concentration of fatty
acids and normal paraffins could be related to the molecular
weight of the solute by the simple relation

where
is as previously defined;
is a specific constant;
c is the concentration in monomoles per litre; and
M is the molecular weight or the solute.
His basic assumptions were that such molecules are rod-
shaped; that their effective volume (muCh larger than
their real volume) depends on the chain length and conse-
quently on the molecular weight. This assumption was sup-
ported both by available X-ray (25) and refractive data (26),
and by the concepts derived from surface area measurements
of J.angmuir ( 2!1) and Adams ( 28) •
The Staud1nger equation was quickly confirmed for rod-
like molecules up to 40•50 -- CH2 -- groups. The value
of xm remained constant for any polymerhomologous series
regardless of chain length.
Thus Staudinger was led to apply his rule to the
 12
· determination of molecular weights far beyond the range
where the Km value could be calibrated by the methods avail-
able at that time. Hibbert and Fordyce (29) prepared a
series of polyoxyethylene glycols having unifor.m molecular
weights up to 8,000 and confirmed Staudinger's rule for
molecular weights above 1,000. Staudinger (30) and others
(31) soon showed that in the range between 1,000 and 10,000
the rule gave good agreement with absolute methods tor
straight paraffins, esters, and amines, for cellulose and
cellulose derivatives (16).
At this time the adaptation of classical osmotic methods
to systems using organic solvents gave a ready means for
testing staudinger's rule in the truly high polymer range.
The absolute data obtained by direct osmotic measurements
showed that although the equations gave surprisingly good
agreement in many instances, it was not generally true.
Wide deviations were observed for long flexible molecules
such as the polyvinyl polymers. For these Staudinger and
eo-workers (32) and others (54) found the value of Km to
decrease as the molecular weight in a given species in-
creased. Staudinger insisted that suCh deviations arise
from some specific peculiarity of the polymer such as
branching (32) or from some special characteristics of the
polymer due to its method of preparation.
Mark (33) was the first to suggest that the picture
 13
of a stiff rod-like molecule assumed by Staudinger was a
limiting case and that it was more reasonable to assume a
twisted or kinked configuration. Meyer and Mark {34} and
Kuhn {35) showed that both the theoretical requirements (36)
for a stiff rod-like molecule and experimental evidence led
to results at variance with the Staudinger equation. In
a modification of an earlier treatment Kuhn (37) predicted
that for a more or less coiled chain there will be a pro-
portionality between~ and Jlf where -J has a value be-
tween one-halt and one, probably o.a or 0.9. Staudinger
had empirically set the exponent of ltl as 1. The Staudinger
equation in its modified form was first used by Mark (38)
as

By extending Kuhn's treatment (37) Huggins (39){40)

expressed the interdependence of the structure of the
randomly kinked solute to the specific viscosity and ar-
rived at a limiting equation identical with that of
Staudinger at the limit of infinite dilution

~ 1<. + Kr&r\ M

Flory (41) objected that this treatment did not give as

good agreement as the Kuhn development, but in a recent
 14
paper Huggins claimed that his more general treatment pre-
dicted that ;) , the exponent ot M in the more general form
ot the Staudinger equation, would have a value between 0
and 2. The former would indicate that the molecule had the
shape of a perfect sphere (Einstein's equation), the latter,
a rigid rod. Flory (4l),Houwink (42), Mark and eo-workers
(43)(44) have calculated from experimental data that the
exponent of -::rJ should have a value of about o.s. For the
polyvinyl acetate used in the present work, similar results
have been obtained. A recent paper by Mark and eo-workers
(44) shows that iJ need not be constant for a given chemical
species, say, polystyrene. Like Staudinger they account
for deviation in the more general equation by suggesting
"a different internal arChitecture for the macromolecule".
Further research will be necessary to explain such devia-
tions. For the moment the modified form of the Staudinger
equation is generally considered to be a valid relation
between the intrinsic viscosity and the molecular weight,
where K and V have been determined by comparison with an
absolute method. It applies strictly only to homogeneous
solutions.
An ef:fort to derive :further in:formation from the

viscometric measurements already discussed is of recent

origin. The theory ot viscosity of dilute solutions,
developed by Guth and Gold (55), Shima (45), and Huggina
 15
(39)(40) was based on the assumption that there was no in-
teraction between the small solvent particles and the
randomly kinked chain compound. SuCh an assumption was
certainly too artificial, for the concentration dependency
of the ~ value for a given polymer was found to vary
from one solvent to another, and this dependency could only
be explained as interaction between solute and solvent.
Huggins ( 46) proposed that this interaction, which was a
distinctive property of a given solute-solvent system
might be used to define the nature of the polymer in that
solvent.
Huggins started from first principles using a modified
form of Stoke6' law for computing the frictional force
acting on eaCh submolecule,
I
Force • (p TT '7 k tt.. t.A...
where
/j is the viseosi ty of the solution;
a is the effective diameter of the
submolecule;
u is the velocity of the solvent
molecules in relation to that of
the solute; and
1
k has a magnitude characteristic of
the system under consideration. It
 16
depends on the sizes and shapes;
the cohesional and adhesional pro-
perties of the solvent and solute
submolecules, but is not dependent
on the number of submolecules 1n
the long chain.
By combining this new expression with his earlier deriva-

tions (39)(40) he derived the equation

This equation, in expanded form, is equivalent to the

empirical equations of Schulz and Blaschke ( 47), Baker ( 48),
and many others (49)(50)(51). While the generality or
Huggin's theoretical equation is apparent, the quantitative
,
interpretation of the constant k awaits further exper-
imental data. This constant, k , will be independent of
the chain length and will therefore be the same for hete-
rogeneous samples as for the more homogeneous tractions
obtained from such samples.
The effect of temperature on the viscosity will not
be discussed since the basic aim of this work is to present
methods of distinguishing between poly.mers of different
nature and chain length. A survey of temperature-viscosity
relationships in this field will be found in Mark's
Physical Chemistry of High Poly.mers.
 17
As stated earlier, there are two absolute methods for
determining the particle size of long chain polymers dis-
persed in dilute solution: the sedimentation equilibrium
method using a Svedberg ultracentrifuge and by direct
measurement or the osmotic pressure. Only the latter has
come into general use. The advantages of the ultracentri-
fUge have been stressed by Svedberg (52) and Kraemer (53)
but the very large initial expense effectively prevents
such a method coming into general use. The direct measure-
ment of osmotic pressures has the obvious advantage of re-
quiring relatively simple equipment. It may be pointed
out that other methods for determining the colligative
properties of solutions of small molecules such as the
measurement of vapor pressure lowering, or the Beckmann
methods depending on 1owering of the freezing point or
rise in the boiling point, are inapplicable for molecular
weights above 5,000.
In 1886 van't Hoff published his well-known general-
ization showing the analogy between gases and solutions,
and for the first time applied thermodynamic methods to
the colligative properties of solutions. The experimental
examination of this generalization by Morae and Frazer (56),
Lord Berkley and Hartley (57), and many others,have been
treated too thoroughly in treatises of physical chemistry
to need repetition here. Experimentalists have proven
his limiting law time and again -- but modern thought
considers his kinetic picture of osmotic pressure arising
from 11 the impact of the tlissolved molecules on the semi-
permeable membrane" as false.
Thermodynamics requires that when two phases (58) are
separated by a membrane perfectly permeable to one compo-
nent and quite impermeable to all others, the condition
for equilibrium is that the partial molal free energy of
the component which can pass through the membrane shall be
the same in both phases. There is no condition for the
molecules which cannot pass the membrane. The nature of the
membrane-- its thickness, chemical composition, physical
state, have no effect at equilibrium (59).
The presence of solute on the solution-side of the
membrane reduces the chemical potential of the solvent in
the solution according to the Gibbs-Duhem-Margules relation-
ship and a flow of solvent toward this lower energy level
results. An opposing pressure,P, which will just balance
this potential flow is called the osmotic pressure of the
solution. The thermodynamic consequence of applying a
pressure to the solution is to increase the partial molal
free energy of the solvent according to the familiar equation

dij_ : VI dl2
 19
where vl is the partial molal volume of the solvent.
Writing (Fl)p and (F1 )p 0 as the partial free energy of the
solvent in solution and under pressures of one atmosphere
plus the osmotic pressure (P), and of one atmosphere (P 0 ),
the condition for equilibrium requires:
p

(if) p- (F,}P. =- I V.
r=:
riP ~ RI~a_.
where a1 is the activity of the solvent in the solution.
In very dilute solutions where Raoult's law is applicable,
x1 , the mole fraction may replace a 1 , the activity of the
solvent in the solution, and since

-
and

the above equilibrium condition may be restated as

1t V, = /? T .,_ '!.-

This equation in the limiting ease is equivalent to van•t

Hoff 1 s law.
The usefUlness of this relation in determining the
·molecular weight of the solute is obvious if the van't Hoff
 20
equation is rewritten as

--
where
W2 grams of substance of molecular weight K2 are
dissolved in volume, V;
R is the gas constant in appropriate units;
T is the absolute temperature; and
if is the observed osmotic pressure.
The application of this equation to the deter.mination
of molecular weights of high polymers, however, entails
certain restrictions and modifications. Since M2 is very
large 1f will be very small; the resulting experimental
necessity arises that measurements be carried out on only
moderately dilute solutions, in order that the resulting
osmotic pressure may be determined with requisite accuracy.
Very large deviations from ideality occur even 1n moderately
dilute solutions and as a result the limiting law will no
longer apply. This concentration effect, analogous to that
already discussed in connection with visoosity,suggested
the expansion of the van' t Hoff equation after the fashion
of the Ohnes equation for real gases. Thus where C2 is
the concentration of the solute

1f -
 21
where A, B, and C are characteristic constants. In the
concentration range used in high polymer work, only the
first two terms on the right are needed, and the equation
becomes

IT =
C2
Experimental data (60)(61)(62) support the rectilinear
relationship predicted between T.r and c2 • This is the
. 02
generally accepted relationship used at the present time
for relating osmotic pressure data from non-ideal solutions
to the molecular weight of the solute, since it provides
a ready means for linear extrapolation to the limiting
value of the reduced osmotic pressure 1T
Cz
at Cz = o.
From the classical kinetic point of view, A, the first
coefficient of the power expansion, is directly connected
with the number of particles which move independently in
the solution. As Mark notes (21), A represents the pure gain
in entropy for ideal mixing. Subsequent coefficients will
represent the entropy anomalies and energy terms due to in-
termolecular and intramolecular interaction as a result of
chemical attraction and the unusual shape and size of the
chain-like solute.
Early attempts by Ostwald (63), Schulz (64), and
others (65), to interpret such deviations in terms of
solvation have been superceded by more quantitative
 22
interpretations. The artificial extension of the thermo-
dynamic treatment of systems of small molecules by Kratky
and Musil (66) and Mark {67) gave way in turn to the our-
rent statistical treatment of Eyring and eo-workers {5),
Flory (1}, and Huggins (4).
Meyer and LUhdemann {68) and Boissonnas {69) advanced
the hypothesis that the wide deviations in entropy for
solutions of long Chain molecules (even where AHmix: 0)
were due to the ability of the individual structural units
to move independently. Although this model neglected
obvious restrictions resulting from the physical nature of
a chain of molecules linked by covalencies, it was the one
adopted by Eyring in his statistical treatment (5). suc-
cessive molecules in a chain cannot be interchangeable,
and it is difficult to see how neighboring molecules linked by
valence forces can act quite independently.
In order to overcome such imperfections Meyer (70)
adopted a new model whiCh Flory describes as being a quas~

solid made of cells which may be filled either with a

polymer segment or solvent molecule. Meyer imposed the
restriction that "segments of a given polymer chain must
occupy a continuous sequence of adjacent cells which,
however, may meander thru the lattice". Assuming flexibility
at each chain linkage, there will be many alternative posi-
tions for each succeeding chain molecule and this will
give rise to the unusual entropy associated with solutions
 23
of long chain molecules. Flory (1) and Huggins (2){3)(4}
have carried out statistical analyses for such a system
and derived equivalent equations describing the activity
of long polymers. A comparison between the form of the
osmotic e~ation resulting from the above derivations
(1)
n • RT
VB
and that based on van't Hoff's ideal law ahow them to be
equivalent at infinite dilution where the te~ due to the
non-ideal entropy of mixing disappears. A comparison be-
tween experimental data and the theoretical predictions
of such an equation ~see Curve II Graphs (5-16} ref. (4)]
disclosed that either the original model was in error or
the heat of mixing was not negligible, or both factors were
involved.
Huggins therefore incorporated a secondary heat of
mixing ter.m based on the work of van Laar (71), Hildebrand
(72), and Scatchard (73) for non-ideal solutions of small
molecules [see Curve III Graphs (5•16) ref. (4) ] • The
inclusion of a semi-Eitlpirical heat of mixing term im-
proved the approximation of theoretical predictions to
------·----------------··-···· ·--···~····-· ~--

(l) Tt • osmotic pressure in appropriate units

VB • molal volume of the solvent
T • absolute temperature
NA • mole fraction of solute
NB : volume fractions of solvent
n • the number of elementary units in the long
chain molecule.
 24
experimental data. However, wide deviations were still
found, because the Meyer assembly, as treated by Flory and
Huggins,predicted many physically impossible configurations
(1}.
To take account of these anomalies in entropy result-
ing from over-simplification, Huggins introduced an
empirical constant~ which would be characteristic of a
given solute-solvent system but independent of the molecular
weight of the macromolecule.
This constant corrected the activity equations (1)(4}
both for deviations resulting from ~ ~ix ~ 0 and devia-
tions from predicted entropy values. The activity of the
solvent component when derived by statistical mechanics
became

and the corresponding osmotic expression (in Huggins ter.min-

ology (74) ) became
tt e RT
02 i2 +
where d2 is the density of the solute; and the others are
as previously defined. Since the second term on tbe right
is negligible in quite dilute solutions, this equation
predicts the well known relationship between¥ and c
where the slope will yield~ Huggins has published several
 25
papers (75}(76)(77) supporting the application of this
constant as a defining parameter for high polymer systems.
By its use "the activities of components of a binary
system can be computed quite accurately over a large range
of composition once the value or;n, for the system in
question,is known.n Likewise, Huggins suggests that a
single accurate osmotic pressure determination would be
sufficient to determine the molecular weight of a g1 ven
sample, if the characteristic.}L value for the system
were known. such applications are, however, of secondary
importance since they add nothing new to our knowledge of
such systems.
QUalitatively .)1 "is a measure of the preference of
each molecule (or submolecule) to have like molecules
(or submolecules) rather than units of the other kind for
immediate neignbors". Its value will be specific for a
given system. Its quantitative interpretation is, bow-
ever, complicated and possibly prevented by the fact that
)L combines the heat of mixing with unpredicted entropy
effects; fUnctions which are generally antibatic. Recent
papers by Mark (44)(45) evaluate~! values but limit the
interpretation to qualitative remarks.
The present status Of_)l, like that Of k, from
viscosity data is that while it reflectsthe interaction
of solvent and solute, it has not been given quantitative
 26
significance. The equations already derived for convert-
ing osmotic and viscometric data into molecular weights
have implicitly assumed that the solute was homogeneous
with respect to chain length. This of course is not true,
for polymers whether synthetic or natural are always
composed of chains of varying length usually distributed
in roughly Ry.mmetrical fashion about an average molecular
weight. This inherent heterogeneity not only modifies the
interpretation of molec11lar weight data, but by itself must
be considered a varying characteristic. Unfortunately,
no satisfactory method has been found for determining
this variable. The following discussion will therefore
be limited to the effect of heterogeneity on the molecular
weight equations already derived, and to outline a promising
method for the relative measure of this characteristic.
Flory (92), Ohalmers (93), Dostal and Mark (94) have
shown that a theoretical calculation of the size distribu-
tion is possible if the kinetic mechanism of the polymeri-
zing process is sufficiently understood. SuCh a method
has little practical value, but it does predict that the
process of polymerization will yield a mixture of chains
with few or no extremely short or extremely long molecules
and will approximate symmetrical distribution about a single
maximum analogous to the Gaussian error curve.
The decrease in solubility with increasing chain
 27
length has long formed the experimental basis for deter-
mining the distribution function {95). Data by Schulz {96),
Tuckett and Blease (97), and Wilson (98) confirm the
general shape of the distribution curve. However, the
methods of fractional solubility or precipitation are both
tedious and exacting, and at best the results obtained can
be no more than rough approximations. This latter restric-
tion arises as a result of the similarity in the solubility
properties of molecules of widely different chain length.
At the present time, these difficulties can be avoided, if
an estimate of the relative heterogeneity is sufficient.

Both of the suggested methods (99)( 94) depend upon a com-

parison of osmotic and viscometric data, but this discussion
will be limlted to the more direct method of Kraemer and
Lanaing ( 99).
osmotic measurements are a function of the number of
particles of solute present at a given concentration, and
for a heterogeneous material will yield a number average
molecular weight defined by Kraemer as
i • 00 i = 00
;E._ ni Mi ~ ni Mi
i • 0 i =0
Mnav = 1 • 00
• N
E ni
i • 0

where Mi is the molecular weight of the i-th species; Ni is

the number of the i-th species present; N is the total
number of particles present. For any given concentration
 28
of heterogeneous material, it is clear that the materials
in the lower molecular weight range contribute a larger
number of particles per unit weight of polymer, and there-
fore have a very much larger effect on the osmotic pressure
than the large molecules. On the other hand the intrinsic
viscosity has been shown to depend on the molecular weight
of the dispersed particles. For a heterogeneous mixture
the average intrinsic viscosity will be a function of the
weight traction of the various species present. The small
number of very large molecules at the upper end of the
distribution curve, because of their larger weight contribu-
tion for any given number, will have a disproportionate
influence on the viscosity average molecular weight when
compared to the corresponding numbers at the lower end of
the curve.
To take advantage of the inherent difference between
the average molecular weights, it is first necessary that
they be expressed in terms of a common parameter. Kraemer
and Lansing assumed that replacing the necessarily step-
wise distribution function for real molecules by a function
involving the concept of a continuous variation in the
molecular weights does not introduce appreciable error
into the calculation. Experimental evidence supports the
assumption of a single maximum and the assumption that
the number of extremely short or extremely long molecules
 29

relative to the average is effectively zero. The logarith-

mic number distribution function corresponding to the equa-
tion
dn • N c-y2
ff dy

satisfies the requirements of such a distribution. Here

ln M/Mo
•
~
dn is the number of molecules between y and y + dy
N is the total number of molecules
M0 is the molecular weight of the polymer at the
paint where cJi . is a maximum. Its meaning is
clear from the following graph.

jS is obviously a measure of the non-uniformity. For

a homogeneous material it is zero, while the more non uni-
form the material, the larger the value it will assume. By
incorporating these assumptions with the previous definition
of the number average and replacing the summation with the
appropriate integration the result is that
 30

•
2
-_/
r
00

Mi
2
e-Y dy
iffo

Since
= M0 e Y
"
then
00 A 2
~ M0 e~y-y dy
-2
TT
0

completing the square to take advantage of the relation

-oo
the following equation is derived

For convenience in comparison it will be necessary to

express the average viscosity value in the same tenns. The
intrinsic viscosity for a homogeneous species has been
shown to be given by
 31
In a heterogeneous mixture the contribution of each species
will be proportional to its molecular weight and its weight,
w1 • Beginning with the contribution of the lowest molecular
weight species present (the i-th) the intrinsic viscosity
will result from a summation like

To get the average, divide by the sum of the incremental

weights. The summation of the proportionate contributions
of each species obviously yields the determined intrinsic
viscosity. Hence
or) -i)
.. . .
l"JlAv = L w~: K~· + w,-.,.,
..,....
/( M(·+J
~ u.Jb·

--

By the same substitution used for the number average

molecular weight, Mcintosh (101) has applied Xraemer's
method to derive the following general expression for
the average intrinsic viscosity.
V M-J [{}..±:;:-.:)) ~- ~] !3
l~Jitv :. '' o e
The intrinsic viscosity is a function of the viscosity
average molecular weight and by combining the above
 32

expression with the number average molecular weight

derived from osmotic data,8 2 may be evaluated as follows:
_L AA L({::!:__If}) J.. ] '~
K V f"lo e ,_
'I;-

4- /'f
;r.-'

hence -

or in an equivalent form
I , -a.-

. LjJ ~ J,., K _,. .· .f

--~'r M'YV
The application and usefulness of this equation will be
more conveniently discussed from the specific data obtained
in this investigation. Further discussion on the problem
of heterogeneity will therefore be postponed to a later
section.
 EXPERIMENTAL

Materials

Polzvinyl acetate
The polyvinyl acetate (Gelva) polymers used in this
investigation were commercial products supplied by Shawini-
gan Chemicals, Limited. The polymers are graded on the
basis of the viscosity of a benzene solution at 200 c.,
containing a molecular weight of vinyl acetate per litre.
Such a solution of Gelva 15 has a viscosity of 15 centip6ises
at 200 c. This terminology was retained as a convenient
method of naming the polymers examined. All of these com-
mercial polymers contained small amounts (usually less than
1~} of gel-like material. The following treatment was
therefore adopted as standard for all polymers in order to
remove the insoluble fraction.
A sample large enough for all tests was dissolved in
acetone and filtered through two thicknesses of Kleenex
Tissue and a No. 1 Whatman filter supported on a six inch
Buchner funnel. The clear filtrate was made up to 5 - 6~

concentration with acetone and precipitated by pouring

slowly into distilled water with stirring. The sticky
polymer collected on the stirring rod and was removed at
regular intervals instead of being permitted to accumulate
into a large aggregate. The bulk water was permitted to
 34
drain off, and the wet polymer was then placed in a vacuum
desiccator over ea 01 2 and kept under a vacuum of 5 mm.
overnight. The partially dry, porous mass was sliced
manually into small pieces for further drying. The drying
of the sample was completed under vacuum at room temperature
in two or three days. Heating was avoided at all times
since its effects were unknown. Recent experimental data
(78) show that the polymer will undergo some degradation
at 100° c.
The solvent
The acetone used in osmotic and viscometric work was
either c. P. grade from Standard Chemicals eo., or Marek's
Reagent grade. No difference was observed between the two
grades. The acetone was dried over ea 01 2 and distilled.
It was then either used immediately or stored over Drierite.

Solutions
The precise knowledge of concentrations or polymer
in acetone solutions was important. In both osmotic and
viscometric molecular weight determinations, values at
zero concentration were required, and these were obtained
by extrapolating
~ .
' . the concentration function of the observed
phenomena from the range or finite concentration to an
ideal value at infinite dilution. The accuracy of suCh
extrapolation depended to a large degree on an accurate
 35
knowledge of the concentration.
Two general methods for dete~ining concentrations of
such solutions have been reported. The more satisfactory
was to dissolve a known weight of polyvinyl acetate in the
acetone and make up to any desired concentration by weight.
In the relatively dilute solutions used it is permissible
to assume no change in density when expressing such concen-
tration in te~s of grams per lOO cc. of solution. The
second method depends upon various means tor determining
the concentration of a sample of the solution taken from
the apparatus immediately after the measurement has been
made. Such a method, if accurate, would have two important
advantages for osmotic investigations. It would overcome
the uncertainty about the real concentration in the cell
after indeterminate amounts of adsorption have taken place
on the membrane and at the walls. In addition such a
method would eliminate the wasteful procedures involving
numerous washes -- an important consideration where a
molecular weight determination must be made on a limited
sample.
Determining the concentration by titration of the
acetate groups (79) was tedious, subject to appreciable
error, and did not give more accurate results than could
be obtained by evaporation of the solvent from a weighed
sample of solution.
 36
The direct method of determining the amount or polymer
in a weighed sample of solution by evaporation was not
found satisfactory for the system polyvinyl acetate-acetone.
Errors arising from bydrolysis.adsorption, or other causes
were large enough to cause so muCh scattering of points in
a l i vs. C plot that accurate extrapolation was impossible
c
(see Table I).
For very small concentrations of polymer such as exist
on the solvent side when small quantities of polymer dif-
fuse through the membrane, this direct evaporation method
was the only one available. The values so obtained, while
not precise, are certainly of the right order of magnitude
(within 5 - 10%). Qualitative evidence indicated that a
technique involving platinum weighing bottles would give
satisfactory concentrations by direct evaporation methods.
Since the present osmotic investigation was not carried
out on limited samples no critical examination of this
possibility was made.
 37

TABLE I

ERRORS IN EVAPORATION METHODS

FOR THE SYSTEM ACETONE-POLYVINYL ACETATE

Concentration
by weight Weighing Bottles

gr./100 gr. Soft

soln. Brass Error% Glass Error% Pyrex Error%

0.983 o.9s6 ~ o 31 o. 9 45 - 3.56

• 0.951

0.591 o.soo + o.aa

o.s92

0.408 0.404
0.394

0.335 0.345
0.335
+ 1.5 0.310
0.305
- 8.1

0.256 0.248
0.251 -.2 7
 38
Viscosity Measurements

Apparatus
Viscosities were measured in a modified Ostwald type
viscometer, having sn outflow time of 77 seconds for 2.5
c.cm. of acetone at 20° c. The capillary was 10 ~. long
and had a radius of 0.038 ~. Other dimensions are in-
cluded in Pamphlet No. 188 of the British Engineering
Standards.
The viscometer was mounted on a brass frame which
fitted neatly into grooves in a second frame clamped in
the bath. The supporting system was so arranged that the
viscometer was always in vertical alignment while in the
bath.
A standard mercury thermoregulator-relay system
controlled the temperature at 20 ~ 0.05° c. Under usual
operating conditions no fluctuation was observed on a
ther.mometer graduated in tenths, so that the actual control
during a determination was better than indicated by the
above limits. Accurate temperature control is of particular
importance in specific viscosity measurements since a varia-
tion of as little as 0.01° c. will cause a calculated {81)
variation of 1~ in a specific viscosity determination of
o.os.
 39

Procedure and Calculations

To determine the intrinsic viscosity of a polymer a
series of 4 - 5 solutions varying from 0.1 - 0.8% was made
up by weight in 250 cc. Erlenmeyer flasks. Just before
the determination, the viscometer, which had been soaked in
chrome-sulfuric acid mixture, was thoroughly washed with

distilled water followed by dry acetone. The viscosity

of the acetone used in making up the solutions was then
determined since it is clear that small changes in the
viscosity of the solvent can cause large errors in the
specific viscosity. As a further check, the flow time of
the solvent was generally measured at the end of a series
of determinations.
Because acetone has a high vapor pressure at room
temperature solutions were forced into the viscometer under
slight pressure applied through a drying tube, by replacing
the stopper in the flask with a standard all-glass wash
bottle assembly. The viscometer was rinsed twice with the
solution, and on the third filling the solution level was
adjusted to the graduated line above the lower bulb with a
fine pipette. After the solution had reached temperature
equilibrium, it was forced into the upper bulb and the flow
time determined on a stop-watch. The outflow time was
checked three or four times, and then the viscometer was
refilled with the same solution and the time rechecked.
 40
The average deviation was about 0.1 - 0.2 seconds in a £low
time or lOO seconds and of course the average deviation
from the mean of several determinations was much less. Such
accuracy is none too great since an error of o.os seconds
in the flow time is equivalent to a 1% error in a speci£ic
viscosity of 0.05.
Viscosities were calculated fro.m the flow times by the
formula

where C and cl are constants of the instrument and are

calculated as indicated by Bingham (111) by determining the
flow times for water, benzene, chloroform, and acetone;~
is the density of the solution -- assumed to be the same as
the solvent in such dilute solutions; and t is the time of
flow. The kinetic energy correction term was of the order
of l-3% of the viscosity of the solution. This term shoUld
be as small as is possible, but to decrease it below 1% of
the overall viscosity introduces unnecessarily long times
of flow. The intrinsic viscosity,[)], for any sample was
obtained from a series of such measurements by plotting
the 1n 6/J, against C or 1sP./O against J'.sP. and drawing the
best straight line through the points. The extrapolated
value at zero concentration is the desired intrinsic viscos-
ity. The value of the characteristic constant kl, already
discussed in the theoretical discussion,is given in the
 41
first plot by the limiting slope equal to( kl .. i) [ ~ J 2.
In the second plot the value of k1 is given by the ratio of
the slope to the intercept (at o : o).
Apparatus and Techniques for Osmotic Measurements

The Modified Carter and Record Cell

An osmometer based on the design of Carter and Record
(80) 1 and Gee (81) was first used in this investigation.
The apparent advantages claimed for the stirring device
incorporated in their design coupled with a lack of ex-
perience on the part of the investigators led to the adop-
tion of this design in preference to that of Van Campen
(109). No reliable results were obtained with this cell
in five months of intensive research, except a knowledge
of its inherent weaknesses, and this cell was therefore
replaced by a modified form of the Van Campen oamometer.
The chief causes of trouble in this form of the Carter
and Record cell are included in this section since they
have no bearing on the main discussion.
This osmometer (Fig. 1) consisted of two circular
brass discs, one inch thick, with carefully turned sealing
seats. The membrane is cut large enough to extend beyond
the sealing seats and forms an efficient gasket when the
cell is assembled. In an osmometer such as this, working
on the counter-pressure principle in which an opposing
 42

,..
CD
,p

i
0
UJ

,..
'd

,
.....
0
()

i
.....
J!r:l
CD

,..
CD
,..
,p

(J
'd
ID
.....
'"'
.....
'd
0
~
 43
pressure is applied from a manometer system, a perfectly
rigid membrane is essential to prevent membrane movement
from being superimposed on the flow of liquid through the
membrane. Mechanical aid to such an end is provided through
a perforated membrane support B which has a convex face of
three inches radius on the upper surface. The outer horizon-
tal capillary system consisted of a metal capillary soldered
to the lower solvent chamber and connected through a glass-
to-metal seal with a glass capillary of o.s mm. diameter
and 30 cm. long.
Several types of glass-to-metal seals were tried, but
the most satisfactory was made as follows: a standard taper
10/30 stainless-steel male joint was soldered to the iron
capillary; it was covered with soft solder, then with a
soft silver-tin amalgam; a corresponding glass female
joint was fused to the end of the o.s mm. diameter capillary
and forced down on the metal joint strongly enough to squeeze
some of the mercury out of the amalgam. After standing
overnight, such joints gave uniform satisfaction. Brass
and copper were unduly weakened by the mercury in the amalgam
and so were useless for the inner metal joint.
The upper half-cell contained the solution and provisien
was made to permit the entrance of a stirrer G. This stir-
rer was attached to a soft-iron armature I and phosphor-
bronze spring K, and was actuated by an intermittent current
 44
through the solenoid J. The glass-to-metal seal on this
half-cell at H was made by turning a retaining collar on
the block and packing the annular space between the glass
and the brass with a stiff silver-tin amalgam. A band, 0,
is soldered about the lower half cell to permit the face to
be flooded while a membrane is being replaced and so prevent
the surface of the latter becoming dry. Because of the dif-
ficulty in removing the last traces of oil from the exposed
parts of the cell face, this practise was a constant source
of contamination. The cell was supported in the bath by
three brass rods and connected to the manometer system with
standard taper joints as shown 1n the line diagram (Fig. 1).
The operation of this cell was similar to that of the
dynamic cell described in the next section, due allowance
being made for differences in filling and emptying the cell
of solution and solvent. It is convenient here to point out
the more obvious disadvantages inherent in this form of an
osmometer.
1. The area of the working face of the membrane is
small. This feature tends to give a more rigid membrane
but reduces the speed and accuracy of measurement.
2. The shape of the solution chamber makes complete
drainage impossible and so necessitates excessive rinsing
when changing solutions.
3. Great care must be taken to avoid air bubbles
 45
beneath the membrane. As noted by Gee (81) who used a
similar cell air bubbles occasionally appeared after the
cell was in use -- in spite of utmost care. This neces-
sitated a complete reassembly of the cell with consequent
loss of time while the membrane reached equilibrium and the
zero was checked.
4. This cell did not permit easy access to the sol-
vent side, hence concentrations of polymer in the solvent
could only be determined after the cell had been dismantled.
5. The cell block is open to the bath up to the
sealing seat. Since the whole cell out to the retaining
band must be flooded, this outer border including the well-
like bolt holes must be perfectly clean, otherwise the
solvent will be contaminated. Where an oil bath is used,
this cleaning process is a difficult and tedious problem.

Modified Van Campen Cell

This dynamic cell (Fig. 2) is similar in design to
that of Meyer, Walff and Baissonnas ( 61), and of Montnnna
and Jilk (107). More recently the same fundamental design
has been used by Flory ( 41 ), and FUass and Mead ( 91). Two
brass blacks 4" x 4" x 1" were first turned down sa as to
offset circular planes 3" in diameter as shown in the side
view. Concentric euts 1/16" x 1/16" and joined by a
vertical groove 1/8" x 1/16 11 were then made leaving a
sealing seat 3/8" wide. The supporting ridges on one
 46

J
...
J
a
2
Q •
"'
CD
R
"
~
\J

ll
~
.....
J!q
0
i
~
~
B
!
td

~
....tt-4CD
~ ....
td
~ 0
~ :::!1
 47
half-cell were turned down 1/1000 11 below the level o£ the
sealing seat to make sure that a tight seal was achieved
when the two halves were screwed together. The cellophane
membrane extended to the outer edge of the sealing seat and
was found to act as an efficient gasket. No leaks were
ever found at this joint provided that ordinary care was
observed in tightening the four machine screws. Two glass-
to-metal seals were needed: one joining the vertical glass
connection to the manometer system and the other bearing
the horizontal capillary on the solvent-side of the cell.
Both were made, as already described, by soldering a stain-
less steel standard taper point to the cell and forcing a
standard taper glass joint over it, using a silver-tin
amalgam as a bonding agent. The supporting arm beside the
vertical glass tube {Fig. 2 - Section A-A) eliminated a
frequent source of breakage which existed in earlier models.
Provision for filling both sides o£ the cell and simulta-
neously removing troublesome bubbles was achieved through
a connection in each half-cell with the bottom of the
respective cell faces. This 1/16" hole could be closed by
a screw valve ground to fit a valve seat integral with the
cell block. Pipes, soldered to each block extended above
the oil level and prevented oil from being washed into the
cell; further protection from oil was gained by stoppering
the pipes. The valve stem itself could easily be removed,
 48
when clear of the threads, with a tight fitting cork-borer.
The horizontal arm was a capillary 0.5 mm. in diameter and
30 cm. long. The choice of capillary of uniform bore was
an important step in reducing experimental error. A male
tapered joint on the end of the upright portion of the
capillary provided an easy method Of closure, so preventing
evaporation where observations were made on successive days
on the same solution.
In assembling the cell, the half-cell bearing the
horizontal arm was placed on the edge of the bench with the
cell face upward and the grooves were filled with acetone.
A membrane slightly larger than the sealing seat was placed
over the cell face; a little acetone flowed over it from
a pipette, and while still wet the opposing half-cell was
carefully tightened into place. After several washings
both sides were filled with acetone and allowed to stand
overnight.
After placing a new membrane in the cell the zero point
of the apparatus was determined with pure solvent on both
sides of the membrane. The value - 7.5 cm., for a given
hydrostatic head in the vertical arm, corresponded to the
geometrical requirements of the system plus the surface
tension effect in the horizontal capillary. Variation from
this value usually indicated that traces of oil were present
and repeated washings usually removed this difficulty. If,
 49

as rarely happened, a true zero point could not be obtained,

the membrane was rejected. When the instrument was found
to yield a true zero point, the valve on the side bearing
the vertical arm -- 1 the solution-side' -- was removed
and the solvent replaced by a solution of known concentra-
tion. After rinsing the cell three or four times with this
solution, the valve was replaced and the solution adjusted
in the vertical arm so that it stood in the enlarged por-
tion. The cell was then returned to the bath.
The osmotic pressure corresponding to this solution
was measured by the counter-pressure principle introduced
by Berkley and Hartley (108) and used in modified form by
van Campen (109),BUchner and Samwell (110), and Carter
and Record (89). The system (Fig. 3) consisted of a xylene
manometer attached to the cell and to a 500 cc. surge
volume immersed in the oil bath. Positive and negative
pressures over a wide range could be applied to the solu-
tion side of the osmometer and so either balance any
tendency of the solvent to flow through the membrane to the
solution, or force a small amount of solvent through the
membrane in either direction. The effect of such opposing
pressure, whether larger, smaller, or equal to the osmotic
pressure was shown by the meniscus of the solvent in the
horizontal capillary. A linear relationship between the
rate of movement of the meniscus and excess pressure was
 50

o-·-·-·- ·-·-o
!
.p
•
~
.p
Cd
.p
•
tt)

a e
.....
Pet
~
]
...
Q)
+»

I
==
 51
round (84)(85). This rate could be easily measured with
a telescope having a finely ruled scale in the eye-piece,
and from the corresponding plot, a graphical determination
of the pressure corresponding to zero movement with an ao-
curacy or j t 0.1 cm. The amount or solvent passing
through the membrane in each direction was roughly equal,
and was never great enough either to alter the height of
the vertical arm or materially change the concentration.
At the end of each determination the height of the meniscus
above the cell block was determined by removing the cell
from the bath. The zero correction for the cell was 7.5 cm.
when the meniscus in the vertical arm was 5.0 cm. above
the cell-block. Having obtained a balance point, the cor-
responding osmotic pressure was calculated thus:
Osmotic Pressure a (Value at balance point) ~ 7.5 cm.
1.15
± (heigl1t or vertical arm - 5.0 cm.)
1.1
Typical data for osmotic determinations on three different
solutions with three different membranes is given in Table
II. The lOO% Carter & Record membrane shows the superimposed
effects due to flexibility which disappeared with time.
Readings on the second and third membranes were recorded
5-10 minutes after any given pressure was applied and re-
fleet the convenience obtained by the use of stifr, more
permeable membranes. The quantitative expression of perme-
abilities properly belongs in the section on membranes
 TA.BIE II

TA.l3LE ILLUST.RA.TlNG THE LINEARITY lETIII'EEN RATE AND PRESSUBE

10~ OAHTER AND :RECORD mtBRANE 35% OARTER AND RECORD MEM.IIUNE 10Jb ltORTON MEMBRANE

Pressure(cm.) Rate(div. min.) Pressure{cm.) Rate{div. min.) Pressure(cm.) Rate(div. min.}

·---------------------------------
..... 23.2 + 2·22 25.10 + 6.66) 9.65
-t- 5.95
2.14 6.66)6.62 9.50
2.00} 6.57)
2.01)
- 1.60 - 5 •33 15.30 12·7 4.30
+ 5.1 - 2e16 5.28)
2.10
1.67 17.79 + 3.63 5.3 12.75
1.60 3.60
o.o - 4·05 - 4.41 - 6.72 11e5 15.45
3.33 6.60
2.70
2.66 o.o - 4.34 4re25 7 .a
2.42 4e30
2.16) 4e35
2·22)
26.86 T 7e44
~ 16.5 + 0.7 7.49
0,69 7.39
0.74
0.72
·zero----- 12.2- - - - - MeniscuS- - 5.03 --- zero ---:- 10.0 0'1
N
Menisc~s - 6.35 Zero point- 10.20 Menisc~s - 5.1
"TT 20.9 om. "TT ·- 10.7 - 7.52 - 17.72 U - 2.76
u - o.1a u - 0.45 P - (36.o x lo)-~?
P - (1.5 x lo)-1~ P - (4.5 x 10)~13
 53
and will be considered there.

The Constant T~J2era~:u!:e Ba.th.

Because of the physical characteristics of the osmotic
cells, rate determinations on the movement of the meniscus
in the horizontal capillary are impossible unless the
temperatu~e control is of the order of ~ 4 x lo- 40 c.
This value corresponds to a calculated meniscus movement of
0.02 mm. Experimentally it was found that where variations
exceeding the above occur, rate determinations became in-
accurate.
In order to achieve such efficient temperature control,
a more complicated regulating system was adopted than is
in general usage. The satisfactory results obtained warrant
the inclusion of a detailed description of the system. A
general plan of the controls and heating coils is shown in
Fig. 3. The outer air bath was heated by a grid of No. 40
Nichrome ribbon supported between two stout glass rods in
front of the fan. The heat input was controlled by an
adjustable rheostat, a mercury thermoregulator and a stand-
ard relay assembly. A gradient of 1 ~ 0.1° c. between
the temperature of the air bath and that of the inner oil
bath was found most satisfactory; no observable variations
in temperature were recorded on a sensitive mercury thermo-
meter graduated in tenths.
 Ji 0-. -. ~-

r( ~~J -~ -u--' "! JG

p H
IIIOD.C

Figure 4
Wheatstone Bridge and Electrical Circuit Controlling Thermostat
~
 55
Precise control for the inner bath was secured by the
use of a Wheatstone bridge system (Fig. 4). In accordance
with the suggestions of Eichlberger (103} and Maier (104)
the bridge, W, was made of alternate coils of No. 36 iron
(F), and No. 32 manganin (M) wire; each coil having a
resistance of about 450 ohms. These coils were wound on a
six by four inch rectangle of mica supported by a Bakelite
frame as shown in Fig. 4 1 and protected from accidental
abrasion by a copper screen, P. Since the iron wire has a
relatively large temperature coefficient of resistivity,
and for manganin wire this coefficient is effectively zero,
such a bridge will be in balance at only one temperature.
Any minute change from this temperature will be registered
by a deflection of the galvanometer mirror. To make adjust-
ment over a limited range more convenient a Leeds and
Northrup Variable Resistance Box, B, was incorporated in
one of the arms. The final adjustment of the bridge to
balance at 30° was made on this variable resistance. The
E. M. F. was supplied by a six volt storage battery which
was recharged very simply from the D. c. supply line.
Any change in temperature from that at which the bridge
was balanced caused a current to flow through a sensitive
(1 microvolt/ mm.) D'Arsonval type galvanometer. This
latter was protected by resistances of 10,000 ohms {2)
and 1,000 ohms (3) as indicated. Light reflected from the
 56
galvanometer fell on a 930 General Electric photoelectric
cell, T 1 when the bath was at 30° c. thus actuating the
photoelectric relay, A, which controls the current flow-
ing through the heating element, H. This latter was wound
on a bakelite frame directly in front of the controlling
bridge w. A second photoelectric cell {not shown in the
diagram) was connected in parallel with T and so placed
that it was actuated and so shut off the heat from the
bath, if for any reason the galvanometer light should
overshoot the first cell.
The use of transformer oil as the liquid medium for
the bath had several advantages. Corrosion problems
usually associated with water baths were eliminated. But
more important was the elimination of troublesome lags,
since both the heating element and the controlling bridge
were in direct contact with the oil.
The control obtainable with the system just described
was good, but by incorporating a simple principle sug-
gested by Gouy (105), it was easily improved. A shutter
attached to an arm bearing an armature N was so arranged
that in its normal position it cut off the galvanometer
light from the controlling photoelectric cell, thus permit-
ting heat to flow into the bath during what would be
normally the cooling cycle. The complete heating cycle
was about 40 seconds, but varied from this value if the
 57
air bath was not properly adjusted. Because of the Gouy
interrupter heat flowed into the bath three-quarters of
the above period and hence the heat effective in raising
the temperature of the bath above the average value was,
for a power input of 3 watts, 3/4 x 2/3 x ~ x 60 watt
seconds. Converting this to calories and dividing by the
heat capacity of the bath (12,000 cal./deg.) the calculated
fluctuation was 0.0006° c. Experimental determination of
the mean deviation based upon observed deflections of the
galvanometer light and calibrated against proportionate
deviations through the use of the variable resistance B
and a Beckmann thermometer, confirmed the above calculated
value. Efficient stirring was attained with twin propellor
stirrers.

Membranes
The preparation of suitable membranes is at once the
most difficult and most critical step in osmotic investiga-
tion. such a condition arises partially from the complicated
phenomena which result from interposing a semipermeable
barrier between liquids of different activity and partly
from the mechanical restrictions which define a useful
membrane.
The characteristics of a good membrane are as follows:
1. It must be as nearly semi-permeable as possible.
With samples of polymer that are quite heterogeneous,
 58
particular care must be taken to make certain that the lower
molecular weight material does not pass through the membrane,
if a true number average molecular weight is to be obtained.
2. It must have as high permeability for the solvent
as possible while conforming to res.triction 1.
3. The membrane must have sufficient mechanical
stiffness so that an excess pressure of 10-15 cm. applied
on the manometer system will not displace the meniscus more
than 5-6 cm. in the horizontal capillary.
An elastic membrane not only caused trouble by limiting
the travelling distance in the horizontal capillary, but
had a long lag (Table 2) in assuming an equilibrium position
-- an effect noted by Fuoss {91) in connection with rubber
membranes. These superimposed relaxation effects may nullify
rate determinations for fully one-half hour after a given
pressure has been applied. Moreover Flory {41) claimed
that equilibrium osmotic pressures were more quickly
established where a stiffer membrane was used. Therefore
particular attention was directed throughout this investiga-
tion in search of methods for obtaining membranes having
requisite stiffness. The starting material used for the
preparation of all membranes used was Cellophane No.600 P.~

{not waterproofed) contributed by Canadian Industries,

Limited. Cellophane has been found unsatisfactory for a
few systems (84){85} but has been used successfully by
 59

Carter and Record (80), Flory (41), and in the present

investigation. Its availability and uniform thickness
certainly recommend its use.
The preparation of membranes from such commercial film
falls into three general steps:
{1} the removal of the plasticizers
{2} the adjustment of the permeability
(3) the accomodation of the membrane to organic solvents.
The general method suggested by Carter and Record (89) was
used to obtain membranes having low permeability, while the
caustic treatment, suggested by Morton (90) as a method of
increasing the permeability to water, gave membranes of
high permeability. The method suggested by Flory (41) for
preparing cellophane membranes was in our experience inferior
to the above two methods for the system polyvinylaoetate-
acetone.
In the carter and Record method circles of No. 600 P.T.
Cellophane were first washed free of plasticizers by soak-
ing in warm {35° c.) water for one hour. In accordance
with the suggestion of Carter and Record the membranes were
then soaked in water containing a few drops of ammonium
hydroxide to remove any traces of fatty acids that might be
present and given a final wash in distilled water. McBain
and eo-workers {102),and Carter and Record found that Cello-
phane swells in water to a definite maximum, but is unaf-
fected by organic solvents. By soaking the membrane overnight
 60
in appropriate ethanol-water mixtures, any desired amount
of swelling within a limited range was possible. McBain
and Kistler (112) and this investigation indicate that there
is a qualitative relationship between the amount of swelling
of Cellophane in water and its resulting permeability after
accomodation to organic solvents. Thus by controlling the
initial swelling, any desired permeability in the lower
range was obtained. After a membrane had reached equilibrium
with a given alcohol-water mixture it was washed in a series
of alcohol-water mixtures of increasing alcohol content up
to 99 percent, and allowed to remain in the latter four
hours or more -- usually overnight. The claim (89) that
such treatment completely removes the water from the
membrane was not supported by the findings of this investiga-
tion. These data will be considered later. The membranes
were transferred from the ethanol (99%) to a bath of dry
chloroform, care being taken that the surfaces remained
wet with solvent at all times. This step was purely empiric-
al, but it was found in the early stages of the work that
soaking the membranes for one or two days in chloroform
improved their final performance when placed in the cell.
From the chloroform bath, the membranes were placed in an
acetone bath and after two hours were ready for use. Five
inch desiccators were found most convenient for preparing
and storing membranes. The permeability of such membranes
did not alter with time when stored under dry acetone.
 61
In addition to the empirical chloroform treatment,
other methods for achieving membrane stiffness were briefly
examined:
(1) Treatment with 30~ and 50% sulfuric acid prior to
swelling. These membranes had unpredictable action and were
quite unsatisfactory.
{2) Permitting the prepared membranes to stand in
benzene over sodium. This stiffened the membrane but
affected the permeability adversely.
{3) Placing the membrane in the cell directly from the
final 99~ alcohol treatment and replacing the alcohol in
the membrane with acetone. This method was certainly
promising but will need further investigation.
The well known swelling effect of sodium hydroxide on
cellulose film permitted the preparation of membranes having
higher permeabilities than obtained by the Carter and Record
method. When such permeabilities were required, the Uello-
phane, after having the plasticizers removed, was treated
with a sodium hydroxide solution of a concentration cor-
responding to the desired permeability. Data for membranes
so treated at 20° c. for fifteen minutes will be presented
in the results. Both the time of treatment and the temper-
ature were important if reproducible results were to be
obtained. The technique of washing with dilute hydrochloric
acid and ammonium hydroxide after the caustic treatment
 62

was followed exactly as outlined by Morton {90). The ac-

comodation of these caustic treated membranes to organic
solvents was accomplished by the same method as used for
Carter and Record Membranes and therefore does not need
repetition here. The quantitative expression of membrane
permeabilities has been defined by Bjerrum and Manegold
(116) as

where
D is the cc./c.m.2jsec. for a pressure of 1 cm.
water
~ is the viscosity of the solvent in poises
d is the thickness of the membrane in cm.
P is called the specific permeability of the membrane.
Since the majority of membranes had roughly the same thick-
ness, the rate of movement of the meniscus in the horizon-
tal capillary of the osmometer under unit pressure will
clearly yield a relative value of the permeability. This
relative permeability ( U) was equal to the slope of the
line obtained by plotting rate of meniscus movement against
pressure. In Table II the relative permeabili ties ( U )
for each membrane along with the corresponding specific
permeability, P 1 is given.
 RESULTS

Prelimina!I_M~brane Data
When this investigation was started, the osmotic
deter.minations in non-aqueous solvents carried out by Carter
and Record (89) seemed the most thorough reported in the
literature. The technical difficulties and shortcomings of
their cell became apparent only with experience. These dif-
ficulties, already outlined with the description of the cell,
led to the adoption of a modified form of the Van C~pen

cell. Moreover, these mechanical difficulties, together

with the complexity of the phenomena being studied, served
to conceal two imperfections in the method suggested by
Carter and Record for preparing membranes from Cellophane.
Their method of preparation is based on the question-
able premise that the initial adjustment of permeability by
controlled swelling is irreversible, and further wrongly
suggests that absolute ethanol removes all water from the
membrane, as if this were desirable and necessary. Qualita-
tive observations indicated that a relationship did, indeed,
exist between the degree of swelling and permeability. These
findings are in harmony with the observations of McBain and
Kistler (112), Morton (113), and Table III from this invest-
igation.
However, evidence that the initial adjustment of
permeability is reversible for Carter-Record type me.mbranes,
 64
TABLE III
RELATIONSHIP BETWEEN PERMEABILITY AND THICKNESS
FOR VARIOUS CELLOPHANE MEMBRAJffiS

---
Membrane Permeability Thickness
Relative Specific cm.
(1) ( 2)

35~ Carter and Record 0.53 4.5 x lo- 12 0.0060

4% Caustic 0.90 12.0 X lo-12 0.0075
lO!t Caustic 2.86 36.0 X lo-12 0.0100

(1) For definition, see page 62 of this Thesis.

(2) For definition, see page 62 of this Thesis.

and that the direction to "soak in absolute alcohol four hours

or more, to ensure complete removal of water from the pores"
(89) is misleading, is given in Table IV.
Further, the claim made by Carter and Record (89), and
McBain and Kistler (112) that ethanol completely replaced the
water initially swelling the membrane was not substantiated.
Absolute methanol was substituted for ethanol because of its
known dehydrating effect on cellulose (114), and because the
heat of wetting for methanol on cellulose is very close to
that for water, and very much larger than the corresponding
value for ethanol (115). Forty-eight hours in absolute
methanol reduced fully swollen Carter and Record membranes
to almost immeasurably low (U ~ 0.15} permeability. A
 65
TABLE IV
REVERSIBILITY OF PERMEABILITY IN CARTER-RECORD MEMBRANES
............ ~~·:·

Membrane Time in Relative

99~ Ethanol Permeability

lOO% Carter-Record(l) 4 hours o.ee + o.os

lOO% Carter-Record 10 hours 0.65 + 0.03
lOO% Carter-Record 3 days 0.22 + 0.02

(1) Swollen overnight in lOO% water O% ethanol

similar trend is present in Table IV.

Membranes dehydrated in methanol, however, did not return
to their original thickness. The similarity between the heat
of wetting for methanol and water on cellulose would suggest
proportionate amounts of swelling, and qualitative evidence
for this is seen in the rapid shrinking and wrinkling of
such membranes when removed from methanol. Similar evidence
is given in Table V for strips of Cellophane treated in the
same manner as the membranes themselves. The fact that a
membrane dehydrated with absolute methanol possessed too low
permeability for use, either indicates that a membrane must
have a thickness greater than 1.6 times its original thick-
ness to be sufficiently permeable, or points to the import-
ance of residual water associated with the cellulose. Data
 66
TABLE V
EFFECT OF ABSOLUTE METHANOL ON WATER SWOLLEN CELLOPHANE

Concentration of Ratio of Swollen Ratio of final Thickness

Ethano~~swelling Thickness to after 48 hours in absol-
Solution that of original ute Methanol relative to
Cellophane original

0 2.0 1.6
20 1.85 1.6
35 1.77 1.55
50 1.75 1.65
65 1.70 1.6

given in Table III and Table V indicated that there was some
re1at::ton between degree of swelling and permeability, but
did not seem sufficient to account for the changes in perme-
ability. Cellophane membranes containing residual water
showed high permeability to certain solvents such as ethanol
{112) and acetone, while the same membrane showed very low
permeability towards benzene. These results gave weight to
the argument that the residual water associated with the
membrane was in some way involved in the passage of solvent.
On the basis of these accumulated data, the presence of
small amounts of residual water -- after accommodation to
organic solvents was considered a necessity and 95%
ethanol was used as the final bath in place of absolute
 67
methanol or ethanol. In the early stages of the investiga-
tion the reversibility of permeability unfortunately escaped
attention.

Data from Carter and Record Membranes

Osmotic pressure measurements made with Carter-Record
type membranes in the modified Van Campen osmometer gave a
good rectilinear plot for 1rr/c vs. C in the concentration
range from 1.0 - 7.0 gr./100 gr. of solution for Gelva 360.
Solutions of Gelva 150 and 45 gave values of lnr/c which
were approximately equal and even lower than the correspond-
ing values for Gelva 360. These data are given in Table VI.
It is well to emphasize here that these results were
equilibrium values. No polymer was passing through the
membrane. Nine different Carter-Record type membranes gave
consistent results for any given sample and a rectilinear
plot for 11r/c vs. C over the concentration range examined.
It was therefore concluded at this point that for some un•
known cause, and contrary to thermodynamic reasoning, Carter-
Record type membranes did not give equilibrium values in
accord with reasonable predictions of viscosity data for the
series (Table XII). Such anomalies initiated a critical ex-
amination of the factors influencing the attainment of equil-
ibrium osmotic pressures.
 !!.A.BLE VI
OSMOTIC DETERMIN.ATIONS WITH CARTER-RECORD MEM..BRANES
GELVA 360 GELVA 150

--- -- ---------- - -----

Conc.C 1 l u nl2) u Remarks
1J6 Remarks Cone. 11'
"'16
2.88 0.46 15·40 5·35 1.313 0.58 4.52 3.45

1.95 0.48 9.12 4.67 2.845 0.50 19.60 6 .go

5.61 0.21 10.60 12.60 4.24 0.22 41.80 9.88

3.86 0.29 34.00 8.8 1.40 0.23 5·02 3.58
{~) .0.62 (~) .0.65
3·95 0.26 36.40 9.22 ( C)c.o 3.17 0.25 16.48 5.20 ( C)C:O
3.02 0.66 20.01 6.65 1.87 8 0.23 12.20 6.54

2·51 0.51 15.25 5.94 3.31 0.25 25.45 7.70

1.28 0.62 4.40 3.44 1.76 0.23 7.91 4.50

3.47 0.44 27.60 7.96 1.915 0.50 8.60 4.49

0.942 0.20 2.51 2.67 2oFeb.44.

-1.693 0.22 6.52 3.85 Ge1va
(1) Concentration in g. lOO cc.of sol~tion.
45 en
3·05 0.21 21.21 1.01 (2) Osmotic pres~re in cm. of water. CO

4.12 0.20 37.20 9.05 (~) :0.285

( C)c:o
 69
Caustic Trea~ed Mambrane Results
In order to obtain more permeable membranes that might
more easily achieve what Fuoss calls "dynamic equilibrium"
with the acetone, Cellophane was treated with varying con-
centrations of caustic and then accommodated to organic
solvents. Data for permeabilities of membranes prepared by
this method are given in Table VII. The linearity or the
permeability vs. concentration plot is obvious from Fig. 5.

TABLE VII
PERMEABILITY OF CAUSTIC TREATED CELLOPHANE(l)

~ NaOH Time at 250 c. u d cm.x 103( 2 ) P X 1013( 2 )

2 15 minutes 1.oo 7.5 9.0

4 15 minutes 1.0 9.0 12.0
6 15 minutes 1.12 (14.6) 16.4
8 15 minutes 1.43 14.0 21.0
10 30 minutes 2.72 10.0 36.0

{1) Cellophane Je. 600 P. T.

(2) For definition see page 62 of this Thesis.

Dehydration time for these membranes in 95~ alcohol was not

controlled. The consistency of the results indicates that
the per.meabi1ity is to a controlling degree irreversibly
increased. Residual caustic was easily detected in the ash
>-
1-

illl----------~~-----------t-----------J_________
:J

a:.
Ul
Q.

u
~Id I
Ul
Q.
If)

00 1.25 2.50 3.75 5.00 625 '50 1-- ··:

%NAOH

flgure 5

Bel&ting the concentration of oaustio swelling treatment

-1:1
0
to the !ermeabilit7 of the Membranes
 71
of such membranes. This fact, coupled with the more ef-
ficient screening ability of caustic m~branes compared to
the Carter-Record type for corresponding permeabilities,
points to a phenomenon analogous to the classical "negative
adsorption" suggested to account for the semiper.meability
of copper ferrocyanide membranes toward sugar molecules.
(117). Data for Gelva 15 and 360 on a series of such
caustic membranes are given in Table VIII-A and Table VII~

The extrapolated values obtained from Tr/c vs. C at C•O

(Table IX) were plotted (Fig. 6) against permeability for
both the Carter-Record and caustic membrane series for
Gelva 15 and 360. Gelva 360 values were constant for both
series but thevalues for Gelva 15 showed a definite depend-
ence on permeability. Only with 8 - 10% caustic m~branes

was any polymer definitely found on the solvent side after

a determination. This point was important, for the in-
crease in osmotic pressure for Gelva 15 indicated to the
left of the maximum in Fig. 6 either was a contradiction
of classical thermodynamics, or some factor was present
which was not properly defined. However, the flat maximum
was taken to indicate that the unknown factor had reached
a constant value. Increasing the permeability did not
result in increased osmotic pressures. In addition the
values obtained with these membranes showed the recognized
criteria for equilibrium values in that:
 -
~ T I
4 )~·······- - ,,.r ,.,.. - --- '
--,-- -· -~~-i--__1

,
!
1--
p
! - GELVA 15
3
, -r- ----+~
I

u
z
.
I
0
~2' ( ----~'
_____ _]

t:::

Jr--t-----1--L-
--o . ---~~---------+-------~------_l__j
I -

'""'"'~)
-
I -o
GEL"'' }---...
.
I 'I I l 1-o-
0

20 25
~~
30
_

'>LV 360

35
I
SPECIFIC PERMEABILITY XI0' 3

figure 6

Llmiting Values of (11 0 ) for GelT& 15 and 360 -a

with membranes of Various Permea.b1l1t;r

r
0 & lh Oa.rter-Record type membranes
Oaustic& Caustic treated membranes
 72
TABLE VIII-A

OSMOTIC PRESSURE DATA FOR GELVA 15

Cone. Cone. rr TT/o

gr./100 cc. in so1n u Membrane cm. of
of so1n. -(corrosion) water

3.01 o.o o.85 2!( Caustic 22.39 7.44

1.605 0.95 8.56 5.35
0.792 o.o 1.0 3.48 4.40
(o.o) (3.07)
2.06) 1.0) 4% caustic 15.20) 7.39
2.06) o.o 0.7) 15.25)
1.17 0.96 6.30 5.38
1.17 o.o o.84 6.oo 5.13
o.so o.o o.9o 3.13 5.20
2.78 o.83 23.20 8.35
(o.o) ----- (4.26)
1.695 o.o 1.02 6% Caustic 11.39 6.69
2.323 o.o o.97 17.68 7.61
1.25 o.o 0.96 7.45 5.96
0.824 o.o 1.00 4.6'7 5.6
(O.O) (4.26)
1.00 5 0.047% of 1.40 8% Caustic 4.95 4.94
1.68 polymer 1.23 9.95 5.92
2.375 diffuses
through
1.06 ____
...22.60 9.55
(O.O) ( 4.01)
membrane
2.285 2.'76 10% Caustic 15.30 6.70
1.'7'7 1.5% of 2.6 9.66 5.46
0.951 polymer 2.8 3.62 3.81
2.36 diffuses 2.13 15.65 6.64
2.36) through 2.50 16.60 7.04
(o.o) membrane (2.76)
 73
TABLE VIII-B

OSMOTIC PRESSURE DETERMINATIONS ON GELVA 360

Cone. Cone.
Solvent u :Membrane n

o.o o.88 2% Caustic 14.58

1.06 o.o 0.90
o.o o.7o
(O.O) (?)

1.085 o.o 0.92 4% Caustic

o.o 0.86

o.o 0.87
(O.O) (0.62)

o.o 2.54 10% caustic

trace 1.96 17.65 5.75
o.o 2.42 6.54 3.52
1.42 o.o 2.26 4.10 2.88
(O.O)
 74
(1) they did not permit small molecular weight material
to diffuse through the membrane.
{2) equilibrium values remained constant with time.
(3) results were reproducible within accepted experim-
ental error.
Data for the intermediate members, Gelva 45 and 150, were
therefore obtained (Table VIII-C). No polymer was found to
pass through the caustic membranes and a plot of 1f/c vs C
gave a straight line in the concentration range examined.
The relative values from osmotic determinations for the four
Gelva samples were now in reasonable agreement with the
predictions of corresponding intrinsic viscosity determina-
tions, in contrast to values obtained with Carter-Record
membranes. The values of ( ~>c:o for four polymer samples
and various membranes, together with relative values for
the slope of the 1T/c vs C plots are summarized in Table IX.
The presence of polymer in the solvent accounted for
the decrease in osmotic pressure found with Gelva 15 when
8 - 10% caustic membranes were used. A calculation based
on the difference in the 11/c value (1.50 cm.) and the con-
centration of polymer (1.3% of original) in the solvent led
to a number average molecular weight value of 4800 for the
material diffusing through the_membrane. A similar value
was found with a Flory membrane for the system Gelva 15-
acetone and this value is of the same order as Flory reported
for polyisebutylene (circa-5000). The 10~ caustic membrane
 '15

04.0ri----~
z
0
u
'12
3.0011-- --

2.0

100 2.00 3.00 400

CONCENTR ATION WN<4 .

Daped.eaoe of 01m01i1o Pre11ur t 011. conoeat n.tion

for Solution • of al.J'YiJq 'l Aoetate with C&u1iio !reate4 Ktmbn.nee
 76
TABLE VIII·C
OSMOTIC PRESSURE DATA FOR GELVA 150 and GELVA 45

Gelva Cone. Cone. n

gr./100 cc. in u Membrane cm.. of lT;c
of solution Soln. water

150 0.788 o.o 1.24 8~ caustic 1.92 2.42

l.ll o.o 1.18 3.48 3.14
1.'70 o.o 1.30 6.80 4.00
2.74 o.o 1.15 16.22 5.92
(0.0) ----- (1.24)

45 0.'775 o.o 2.68 10% Caustic 3.18 3.2'7

1.45 o.o 2.46 5.74 5.95
1.684 o.o 2.30 7.76 4.57
1.98 o.o 2.32 9.81 4.95
2.22 o.o 2.10 11.88 5.35
(0.00) .__ .. _..... (l.SS)

bad a permeability more than two and one-half times that of

the Flory membrane indicating a greater screening efficiency
in the former. An alternative explanation will be considered
in the discussion.

Visoometric Results
Reference has already been made to the experimental
 77
TABLE IX
(Tr )
EXTRAPOLATED VALUES FOR( /c)C•o FOR DIFFERENT JIEMBRANES

Gelva Kembrane (tt ) Relative Slope

( /c)Cao
ot Tt/c vs c

15 Carter and Record 0.45 3.16

2% caustic 3.08 1.52
4% caustic) 4,26 1.43
6% Caustic)
8% Caustic 4.01 1.20
10% Caustic 2.76 1.51

45 Carter and Record 0.28 2.08

6% Caustic) 1.88 1.57
10% Caustic)

150 Carter and Record 0.65

6% caustic 1.24

360 carter and Record 2.04

4% Caustic)
6% Caustic) 1.55
 78
methods used in determining intrinsic viscosities, and to
their use for checking relative values of molecular weights
determined osmotically, subject of course to the restric-
tions imposed by heterogeneity. Typical experimental data
are given in full for Gelva 1700 in Table X and in summary
form for the remaining samples in Table XI.

TABLE X

A SERIES OF VISCOSITY MEASUREMENTS ON GELVA 1700

Cone. Flow-time
gr./100 cc. Average Gft ~ 1Jj. k91.1-
c.,
~

0.1475 118.0 0.506 0.015 0.491 1.59 3.14

0.2085 139.1 o.eoo 0.013 0.587 1.900 3.08
0.2955 170.0 0.730 0.010 0.720 2.33 2.86
0.503 299.0 1.284 o.oos 1.230 4.15 2.78
o.eoo 344.0 1.475 o.oo5 1.470 4.75 2.60
Solvent 77.1 0.332 0.023 0.309
co.o) ----- ----- ----- ----- (3.325)

Typical plots of 10Sn~/4fo vs C and~ vs c are shown in

Fig. 7 and Fig. 8. From the slopes of these plots, the
Huggins 1 shape factor, x-., can be calculated as previously
indicated. These values along with corresponding intrinsic
 79
TA.BLE XI
SUMMARY OF VISCOSITY DATA FOR A SERIES OF GELVAS

Ge1va Cone. :Ln~r

gr./100 cc. tJ; c-p
/
Jsp. c

15 0.195 0.356 0.132 .636

0.351 0.388 0.239 .613
0.492 o.431 0.370 .640
o.655 o.47o 0.495 .610
0.767 o.498 0.591 .605
(o.o) ----- .......... - (0.634}
45 0.284 o.417 0.324 0.980
0.357 0.445 0.413 0.964
0.414 0.470 0.490 0.965
0.651 0.577 0.830 0.926
0.955 _____ ...
0.734 1.325 0.884
(O.O) ----- (1.02)
45 0.165 0.363 0.19 1.054
Reaeety1ated 0.422 0.470 0.54 1.024
0.708 0.584 0.915 o.915
0.980
(O.O)
..
,.... ___
0.730 1.39
-----
0.894
(0.0)
145 0.181 0.390 0.280 1.33
0.437 0.528 0.731 1.25
o.716 o.714 1.339 1.185
0.779 0.728 1.384 1.12
(O.O) ----- ----- (1.390)
150 0.133 0.391 0.261 1.74
0.167 0.417 0.345 1.77
0.290 0.508 0.640 1.71
0.393 0.590 0.891 1.62
0.526 0.716 1.295 1.57
0.654 0.832 1.665 1.50
(O.O) -- .. -- ----- (1.87)
360 0.160 0.434 0.400 2.100
0.432 0.711+ 1.305 1.933
0.704 1.073 2.461 1.760
0.872 1.709 3.035 1.600
(0.0) (2.24)
 eo

I'.I.BQ.I'e '
Jlpen4enoe ot T1•ooa1t.f on Conoent~~t1on

tor 8olu:Uona ot PolTriDTl .Acetate

 Gl4~
020.r---.-

v
z
0

~0~~~ I I ::L
f
-n '
I
I
G.4
II
G.l5

1.000 ,250 1.500 1.750 2000

'7

Plgure 8

Dependence ot Viscos1t7 on Concentration (I)

......
f'or Solutions ot Pol.7vil'Jl'l Acetate
 82
viscosities and available number average molecular weights
are given in Table XII.

TABLE XII
VALUES OF INTRINSIC VISCOSITY, k', and
--.;; FOR A SERIES OF GELVAS

Gelva
LtJJ k' ....-;;
15 o.es0 0.31 s.o X 104

45 1.06 0.31 1.36 X 105

45
(Reacetylated) 1.085 0.33 ----------
145 1.39 0.33 ----------
150 1.87 0.34 2.06 X 105
360 2.24 o.3s 4.12 X 105
1700 3.31 0.35 -----------

Relative Heterogeneity
\

According to previous treatment, theory predicts that

a rectilinear log-log plot for Mn vs.[)J should be obtained
provided that the samples have approximately the same degree
of heterogeneity. Since the value orJ is presumed to be
independent of molecular weight for the same kind of molecules,
it may therefore be evaluated from data for heterogeneous
samples subject of course to the above proviso. Samples ot
a different degree of heterogeneity will not lie on the line
 83
as is shown for Gelva 150 in Fig. 9. The straight line
obtained from data on the other three samples has the equa-
tion

or

The value of ~ • o.ss is in good agreement with that cal-

culated by Houwink (42}, from the data of Staudinger and
Warth (32) and the values found by Flory (41} and Mark (43)
(44), for other systems. For any series of Gelvas of compar-
able heterogeneity, values of K and ~ determined from a
log-log plot should give a value of v equal to zero within
the limits of experimental error.
In order to demonstrate the agreement of for dif-
ferent samples and because of known heterogeneity, an
arbitrary value of K was chosen and by its use relative
values of the heterogeneity coefficient rJ were calculated.
These values are given in Table XIII.

Rationalization of Inconsistent Ocmotic Data

With the exception of a material shortening of the time
necessary to establish equilibrium osmotic pressures, caustic
treated membranes gave no evidence to explain the anomalous
results previously obtained with Carter-Record membranes.
 84

TABLE XIII
EVALUATION OF ;<f FROM AN ARBITRARY K
1.53
a • 0.66 Karb =1.96 x lo-4 Karb =
2.11 x 10•6

Gelva 105 ;Sy

No. [~] [ ' ]x 1.53
lo--1 1.53 Mn X 10•4
Karb.

15 0.650 5.15 4.74 6.0 0.62

45 1.06 1.09 4.74 13.6 0.59
150 1.87 2.61 4.74 20.6 o.so
360 2.24 3.44 4.74 41.2 0.61

Whereas with these latter membranes time lags of 6 • 8

hours were found, equilibrium was usually established in
1 - 2 hours with a caustic membrane. In order to prove that
the early inconsistencies were reproducible, and did not
depend on any difference in technique in using the two
types of membranes, deter.minations were made of Gelva 15
using a carter-Record membrane of low permeability ( U. 0.22).
These results {Table XIV) fully confirmed the inconsistencies
found. Certain qualitative observations were made in the
course of the osmotic determinations which suggested a
possible explanation of the apparent inconsistencies.
(1) The permeability of membranes (as indicated by the
slope of the rate-pressure curve) fell off from its value
with pure solvent, by an amount proportional to the
 85
TABLE XIV

OSMOTIC DETERMINATIONS ON GELVA 15

WITH CARTER-RECORD MEMBRANES ( Fe'b. 44)

Cone. n rr;
gr./100 cc.soln. u cm. water c

1.60 0.22 5.55 3.47 low

2.38 0.18 18.20 7.65
17.70 7.44
1.97, 0.19 13.35 6.77
1.25 0.19 4.58 3.65
0.79 2.19 2.77
3.11 0.16 35.20 11.30
1.59 0.24 10.72 6.74
2.41 0.22 13.80 5. 72(?)
(0.0) (0.40)
GE:LVA 360
0.94 0.22 2.49 2.65

concentration of the solution with which it was in contact.

This decrease in permeability was reversible; that is, if
a solution was washed out and bath sides of the cell filled
with pure acetone, the original permeability would be
obtained (see Tables VIII A and B).
(2) Long time lags in reaching equilibrium osmotic
pressures were usually observed for Carter and Record membranes
 1.5 )1---------t------

z
0G.I50
~
C)
0
_j

I.

"

050f.75 0.00 . 0.25 0.50

LOG [~J

:figure 9

Dependence ot Intrinsic V1scosit)r

on Kolecular Weight ot PolyTiiJ71 .Acetate

J
 87
while caustic membranes were characterized by a much shorter
time to equilibrium. It may be mentioned that a long delay
in achieving equilibrium values has been reported by most
authors with the exception of FUoss.
(3) The first determination made with a Carter-Record
membrane was frequently unusually low (See Table XIV# soln
1.60). These experimental observations and the inconsistent
data already presented can be explained if the Carter-Record
membranes are assumed to adsorb appreciable amounts of Gelva
and the caustic membranes little or none. Calculations
indicated that adsorption to the extent of 0.0017 g./cm.
would be sufficient to account for the difference between
the two types of membranes for a one percent solution of
Gelva 15. Preliminary data, (Table XV) from determinations
of equilibrium pressures for successive fillings with the
same solution, support this hypothesis, as do the varia-
tions in permeability of the membranes emphasized above.
Qualitative observations made while compiling the
data in Table XV showed that:
1. With a membrane of low permeability (u • 0.22)
rinsing with solutions of the same concentration did not
disturb the equilibrium, hence presumably did not disturb
the adsorbed layer. With such membranes the equilibrium
osmotic pressure was apparent very shortly after temperature
equilibrium was reached for the second and third filling,
 88
and, further, the equilibrium value for TT;0 in these lat-
ter cases lay above the line accepted as reasonable with
caustic treated membranes.
2. Equilibrium values were not obtained as rapidly with
more permeable Carter-Record type membranes; the adsorbed
layer was probably more easily disturbed and the final
value for ~TT; jc.o was lower than that obtained with less
0
permeable membranes. It· will be noted however that re-
peated washings with the same solution does in every case
increase the (Ttj0 ) value above the well established line
from Table XIV. In addition, where final TT;0 values did
not rise above the caustic line, small amounts or low
molecular weight material were found in the solvent. An-
other fact that will have to be considered in any satisfact-
ory explanation is the intersection of the Carter-Record
and caustic plots or llrj0 vs c at 3 percent.
While it is obvious that many more data will be needed
to define the details of membrane action for this system,
the results presented are considered to be sufficient to
reveal certain fundamental principles which are involved
and which merit a general discussion in relation to data
obtained for similar systems and reported in recent papers.
 TABLE XV

EVIDENCE FOR ADSORPTION OF GELVA :si CAR1!ER AND RECORD l4EM.BRA.NES

,_ --- --- --
Oonc.of
Gelva Cone. u Gelva in Filling n 1T Remarka
solvent 0

360
--
0.94. o.;u o.o 1 2e49 2.65
15 o.ee6 0.21 o.o 1 4.94 5.57 n eq. at once
15 o.eeo 0.21 o.o 2 4.95 5.58 a cell broke

15 1.20 0.65 small 1 5.41 4.50

1.20 0.64 amount 2 5.90 4.90
1.20 0.64 passing 3 5.90 4.90
membrane neq. in
15 o.ssa 0.65 1 1.91 3.52 1 - 2 hr.
0.538 0.65
" 2 2.20 4.08
0.538 0.65 3 2.08 {?)

15 o.8o
o.ao
o.a larger - 1.86p 2.33
'1I eq. in
o.a amt.o:f' 2 2.44 3.06
o.ao o.e low l4nW 3 3.60 4.50 5- 6 hr.
passing
membrane
15 2.22 .a 1.5;16 of polymer 1 15.65 7.05 '"['( eq. in
passing 5 - 6 hr.
15 1.69 1.0 ~ 1 11.4 6.75 Flor,y zrembrane
2 10.0 5.92 overnie;ht
15 1.73 0.62 small l 10.20 5.90 Q)
1.73 0.62 amount 2 10.75 6.21 \0

1.73 0.62 passing 3 10.75 6.21

membram
 DISCUSSION

In the unswollen state, cellophane is composed of

long chain-like molecules arranged to some degree in the
machine direction. Through hydrogen bonding (119) these
chains become interlocked at certain points giving rise to
a three-dimensional network, here and there falling into
crystalline arrangement. One chain may thus be a member of
several crystallites.
X-ray (120) and optical (121) data suggest that these
crystalline regions are not disturbed during swelling, and
therefore act as essential links which prevent dissolution.
In the less highly organized portions of the membrane, the
attraction between the water and the cellulose, during the
swelling process, overcomes the weaker intermolecular
bonding. water is taken up by the cellulose until the
"osmotic forces are balanced by the elastic forces set up
by deformation of the system" (112). A caustic solution is
more powerful than water in competing with intermolecular
hydrogen bonding in the amorphous portions of the membrane
and therefore will cause a larger number of passages to be
opened, hence greater permeability.
It is important to note here that the attractive forces
(119)(122) exhibited by the cellulose seek to be neutral-
ized. Those molecules most capable of satisfying the
 TAB.IE XVI

TIP ICAL DA.TA FOR VAlUOUS OSMO.ME!fERS

:::::::::::::::::::::::::::::::::::::::.:.. . ..
::::::::::::::::::::::::::::::::::~::::::::::::::~::::--:--:::~ ~=- -- ~~

s v_ 1 Time to
Author .Membrane Solute Solvent om. equ1libriam
(approx.)
--
Karae and Fraser(56) copper ferrocyanide augar ftter small 1 2 hour
1.0

Van Oampen( 109} collodion haemoglobin water 20 10 min.

Fuoss and Mead(9l) denitrate polyvi.nyl metb.Jlamyl 5.0 10 min. after

collodion chloride ketone spec 1al pre-
cautions to
overcome
a.dsorbtion
Oarter and Record(80} Cellophane polysac- chloroform 1.6 a hr.without
charide a stirring
1 hr. with
stirring
Flory(41) Cellophane poJ.7iao- cyclahe:xa.ne 3.1 "- a hours
butylene
Modified Van Campen Cellophane polyvin;y-1 acetone 4.5 a hours 15
cell ased in this acetate min. depending
investigation on membrane
treatment,eto.
Table

...
'ID
 92
hydrogen-bonding capacity, such as water and sodium hydrox-
ide, are strongly adsorbed, ethanol less strongly, and
acetone little or none. Where the strongly attracted mole-
cules are removed (Table III, V) the original intermolecular
bonding will be re-established in the amorphous portions of
the membrane and permeability to acetone will accordingly
fall. The permeability of the membrane therefore depends
on the presence of strongly attracted molecules adsorbed in
the unorganized regions.
In the alcohol-water swelling mixtures used by Carter
and Record (89), McBain and Kistler (112), and in this
investigation, water was adsorbed until the activity in
both phases was the same. On soaking in absolute ethanol
there will be a successive replacement first of the free
unbound water in the coarser capillaries (122) followed by
replacement of less tenaciously bound water until equilibrium
is reached. The length of this treatment may be the actual
controlling step in the preparation. Concomitant with the
replacement of water is the re-establishment of inter-chain
bonding and consequent fall in permeability (Table V). The
degree of permeability is clearly dependent on the number
of strongly-attracted residual molecules remaining in the
amorphous portions of the film. It is a corollary there-
fore that these molecules are not disturbed in subsequent
accommodation to unattracted solvents such as acetone or
 93
chloroform.
These views correlate the evidence published by others
and the information obtained in this investigation with the
exception of the data obtained for the low permeability of
benzene. Others (112) have attributed suCh a difference in
permeability to a difference in molecular volume. In view
of the apparent ease with which far larger molecules such
as polymers with molecular weights of 5,000 were found to
diffuse through certain membranes, the possibility that
factors other than molecular volume are involved must be
admitted. However, until further experimental evidence is
available, the writer presents the above as a satisfactory
working hypothesis for the preparation of Cellophane
membranes.
A general theory has been developed to explain the
adjustment of permeability of the membrane to the solvent.
Closely allied is the adjustment of semi-permeability
toward the solute. The inherent heterogeneity of polymers
creates a need for a membrane which is truly semi-permeable,
if true number average molecular weights are to be obtained.
It is well to mention, in this connection, the advantage
of the counter-pressure type of osmometer in determining
the passage of small amounts of low molecular weight
material. In this type of osmometer much larger concentra-
tions could be employed with a proportionate increase in
 94

the absolute amount of diffusing material in the solvent.

This difference was important where the residue from four
grams of solvent was a few tenths of a milligram. That
such small amounts may be significant in heterogeneous
samples is an unfortunate fact, and their presence in the
solvent may be undetected in cells designed to use low
concentrations. Reference has already been made to the
real difference in screening ability of the Carter-Record
membranes and the much more permeable Caustic membranes.
A 10~ caustic membrane was satisfactory for Gelva 150 but
permitted 1.5 - 2% of Gelva 15 to pass. A Carter-Record
membrane with one-fifth or less of the permeability of the
10% Caustic membrane permitted some low molecular weight
material in Gelva 150 to diffuse. In spite of these
specific differences in screening efficiency relative to
permeability, all the evidence found supports the thermo-
dynamic conception that a neutral membrane acts toward
polymers like a screen. The greater screening efficiency
observed for Caustic membranes compared with that of
Carter and Record or Flory type membranes of the same or
lower permeability is remarkable. This feature is of
practical importance in that it permits the use of membranes
of high permeability with less danger from diffusion of low
•
molecular weight material.
On the basis of this general picture of a membrane
 95
made from Cellophane, it is possible to develop a very
reasonable explanation for the inconsistencies in osmotic
pressure data already presented. The data in Table IX
imply that one membrane can give rise to a higher osmotic
pressure than another for the same solution. · This is im-
possible. Therefore either one type of membrane or both
have some effect on the solution which results in differ-
ent equilibrium pressures even though the cell was origin-
ally filled with the same solution. The simplest hypothesis
is that the membrane showing the lowest equilibrium value
actually adsorbs sufficient polymer to change the concentra-
tion by an amount equivalent to the difference in osmotic
pressure. The argument will be presented on the basis of
data from Gelva 15 and afterwards enlarged to include other
Gelvas.
The possibility of such adsorption is favored by the
large membrane surface to volume ratio in the most general
form of the osmometer. Data for several osmometers is
given in Table XVI. (Page 91)
Reference has already been made among the results to
the small amounts of Gelva per square centimeter that need
be adsorbed to account for the observed differences in
osn1otic pressure. More significant than the surface to
volume ratio is the corresponding time to attain equilibrium
pressure. Determinations with Carter and Record membranes
 96
were characterized by a period of 6 - 8 hours during which
osmotic pressure built up from a very low value to equil-
ibrium. Similar effects were observed by Carter and Record
while using the same type of membrane. In their case,
mechanical stirring reduced the time to equilibrium. In
this investigation the slight agitation due to membrane
motion, caused by applying positive and negative pressures,
was observed to hasten the attainment of equilibrium. When
solutions were washed out and replaced with solutions of
the same concentration, equilibrium, contrary to previous
performance, was quickly established. This time, moreover,
the osmotic pressure was higher than previously obtained.
Subsequent fillings were in agreement with the second de-
termination.
Fuoss and Mead (91) suggested that adsorption may take
place both on the walls and on the membrane. The differ-
ences obtained on successive fillings (Table XV) and the
procedure of making deter.minations on successively higher
concentrations (Table XIV) suggests that on the first fil-
ling, some of the weaker solution remained on the walls.
This would tend to lower the total concentration, thus
resulting in slow equilibration. Such an effect would
result in an high osmotic pressure which fell off with
time: an effect contrary to experimental evidence. On
the other hand, the tremendous surface of cellulose (122),
 97
coupled with the known hydrogen-bonding capacity (119),
led to the conclusion that the technique of filling the
cell largely negated any error due to adsorption at the
walls.
If a solution is placed in contact with a membrane
capable of adsorbing polymer, the layer of solution in
close contact with the membrane will be rapidly reduced
in to lower concentration with a corresponding reduction
in osmotic pressure. The time to equilibrium will there-
fore depend on the slow diffusion rates of long polymers
to establish concentration equilibrium tl~oughout the cell.
It is quite reasonable that the small molecules will be
the first to diffuse to the area of lower concentration
and therefore a disproportionate amount of the smaller
molecules will be adsorbed from a heterogeneous mixture,
with a correspondingly larger reduction in osmotic pressure.
On the second and third washing the adsorbed layer is
already established; adsorption is small and equilibrium
is quickly attained. Both the time factor and the higher
equilibrium value support this conclusion. These latter
data also refute any argument based on improper washing.
In the determinations recorded in Table XV the
adsorbed layer appeared to be the most stable with the
least permeable membranes, while with more permeable
membranes equilibrium was not immediately established
 98
after either the second or third wash. The final equilibrium
value was always higher than the original value, but never
reached a value comparable to that obtained with a caustic
membrane or of a Carter-Record membrane of low permeability
( U = 0.22 -- 2nd wash-- Table XV). This was due to a
lack of perfect semi-permeability. Reference has already
been made to the greater screening efficiency of caustic
membranes, and the suggestion that the inconsistencies
observed were caused by the imperfect semi-permeability of
the Carter-Record membranes will be considered. In the
writer's opinion this lack of perfect semi-permeability
displayed by more permeable Carter-Record membranes in no
way interferes with the basic adsorption theory. Rather
the apparent instability of the adsorbed layer shown by
such membranes (which contain more residual water, Table
V) seems to indicate a lowering of the adsorption capacity.
This is reflected in a shorter time to equilibrium on the
first filling (Table XVII).
A summary of data relating membrane treatment, time
lags, and equilibrium values, will serve to coordinate the
general argument. The evidence summarized in Table XVII
indicates that an inverse relationship exists between the
ability of a membrane to adsorb and the extent to which
residual molecules have already satisfied the free valence
forces. Where "negative adsorption" has been proven, such
 ~.BI.l!: XVI I

COORDINATION OF li!Eii1w.NE lEHA.VIO'OR WITH RESIDUAL ADSORPTION

·--_.___
------~
- -----
------~---------.-----------:::::::::::::~:::::::=:::::::::::--:::::;:::::::::::::::::::::::::

Membrane u l!e aidual :Molec u.les ~tme to Equilibrium Evidence for Adsorption
• - - - - - - .. iiiiill
-----------------------
Oarte r-Reoord 0.22 (No small ~) 6 - 8 hours for strong adsorption
polymer in amoUllts lst filling (Table XIV and XV)
solvent eide of b) 2nd and 3rd filling: No fUrther adsorption
with Gelva 15) water almost no time lag on 2nd and 3rd filling.
Oarter-Reoord 0.65 (small more re a idual adsorbed layer more
amoWlts of water because easily disturbed as
polymer diffuse of less ll.,ydra- 5 - 6 hours indicated by appreci-
in solvent with tion (Table able time lags follow-
Gelva 15) IV) ing 2nd and 3rd filling.

Oarter-Record 0.85 (1.5~ of still more time lag after 2nd and
original residual 3rd wash of the order
polymer in water 4- 6 hours of 2 - 3 hours indicat-
solvent for ing that adsorbed l~er
Gelva 15) is easily disturbed.
Oaustio 1.2 (No residual water short if there is adsorption
Membrane polymer in plus NaOH the final i i value
solvent) adsorbed on about l hour indicates that it is
the cellulose small. Time lag ma.y be
due to other causes.
--------------------------------·-------------------------------------------------------------------------------
~
~
 lOO
as the preferential adsorption of water to the exclusion
of sugar by copper ferrocyanide membranes, Morae and
Fraser (56) found equilibrium osmotic pressures were estab-
lished very quickly. The same is true for those deter.mina-
tions (109)(110)(16) where adsorption of the solute was
unlikely. The difference in time to equilibrium found by
Carter and Record when stirring was present or absent sup-
ports the adsorption theory. It is noted that they deter-
mined the concentrations by evaporation of a sample of the
solution taken from the cell after equilibrium had been
established. For this reason their concentrations actually
correspond to the observed osmotic pressures. The general
conclusion from all these data is that where equilibrium
osmotic values are not immediately established, adsorption
is taking place. A series of such deter.minations may yield
a rectilinear plot of rt;0 vs C but the extrapolated value
of (lf/o) C•O will obviously be wrong. The time lags
found by Flory (41) certainly could be partially attributed
to adsorption, though the relative agreement of his series
would indicate that the adsorption effect was small. Fuoss
and Mead (91) assumed adsorption, both to the walls and to
the membrane, but failed to stress the controlling import-
ance of the latter. In view of the data given above, their
technique, while helpfUl, will only be generally valid if
the adsorbed layer is undisturbed on washing. While this
 101
may be true for polyvinyl chloride with denitrated collodion
membranes, the intermediate values in Table XV show that
no general assumption can be made.
The suggestion made by Fuoss and Mead (91) that a
satisfactory membrane is one which is swollen by the solvent
is understandable on the basis of the above hypothesis. The
fact that a membrane is swollen by solvent not only results
in greater permeability, but simultaneously neutralizes the
free valence forces that might lead to adsorption. On this
basis, methanol or ethanol might prove better solvents for
osmotic determinations with Cellophane membranes than
acetone.
Added support for the adsorption theory is obtained
when the results for Gelva 45, 150, and 360 are compared to
those for Gelva 15. From Table IX it is apparent that an
inverse ratio exists between the difference (1T/c>c.o values
assumed to be caused by adsorption and the molecular weight
of the adsorbed particles. Since the membrane may be ex-
pected to adsorb a given weight of polymer, regardless of
the particle size, and since the difference in osmotic pres-
sure depends on the number of particles adsorbed, the in-
verse ratio is exactly the kind of a relationship that might
be expected if adsorption were taking place. However it is
admitted that the change for G@lva 360 is too small to fit
in with such a theory, and can only be explained by assuming
 102
that the experimental error with such large molecules
invalidates the extrapolation at low concentrations.
A second type of inconsistency is present in Fig. 10.
At three percent concentration it would appear that the
adsorption argument reversed itself. Similarly plots of
Gelva 360 for both types of membranes indicate lower
osmotic pressures with caustic membranes than for Carter-
Record membranes, in direct contrast to the data and argu-
ment presented above. Gee (81) and Flory (41) have already
suggested that the slope of a plot of Trfc vs C is a rough
measure of the tendency of solute to solvate. The meaning
attached to this function by Huggins has been thoroughly
discussed in the introduction. While differences in
slope may result from adsorption, it is apparent from the
Gelva 360 data that the solvent-solute relation has been
altered for solutions in contact with caustic-treated
membranes. With the exception of the S% caustic membrane,
the slopes (Table IX) have altered to the same degree for
all caustic membranes. Granted a change has taken place
in the solvent-solute relationship, the intersection of
the Gelva 15 plots and the reversal of plots for Gelva 360
present no difficulty nor anomaly. A similar change was
found by Carter and Record on changing from the first type
of membrane to a caustic-treated type (118). Reference
to the slopes collected in Table IX for plots of TT/c vs C
 102-A

?.:CJ------4--------

u
z
0
~
I=
4C1-------l

301----

100 200 300

~o~.cF_:. ·· RATIOt~ r:.R•JA/IOOCG

l'igure 10

Oemotio Data tor GelYa 15 and S60

with Oarter-ltecord and Oauatio Membrane•

 103
with both types of membranes (Fig. 10) at once reveals
practical difficulties that may limit the quantitative
determination of Huggins' U factor.
The change in permeability of the membranes propor-
tional to the concentration of the solution being measured
is evident in Tables VI, VIII-A, VIII-B, VIII-C, XIV, XV.
Within the experimental error the percentage change is the
same for large molecules as for small ones, for very per-
meable caustie membranes and for impermeable Carter-Record
membranes. This change in permeability was originally
attributed to the impeding effect of an adsorbed layer of
polymer, but the similarity of the change for both types of
membranes did not tally with observed differences in
osmotic data.
A second suggestion was to attribute the change in
permeability to the effect of larger numbers of small
molecules diffusing through the membrane with increasing
concentration. This might be reasonable but for the ex-
perimental fact that the percentage decrease in permeability
with increasing concentrations is approximately the same
where polymer is known to be passing and where no trace
can be found in the solvent after a determination.
The fact that small molecules cann.ot be detected,
however, is not final proof that diffusion through the
membrane is not occurring to a small degree. The 'bra.ss
 104
osmometer tended to corrode in acetone and,after standing
twenty-four hours, to give a residue of 0.6 milligrams for
a 3.8 gram sample of solvent. Because of this residual
value the difficulty in determining small amounts of
polymer (0.0003 gr.) by evaporation of the solvent is
obvious. An alternate method was to pipette the contents
of the solvent side into water. Minute amounts of polymer
in the solvent were thus made visible as a white cloud.
Where osmotic pressure determinations indicated that
polymer was diffusing (right side of maximum Fig. 6) both
of these methods gave positive confirmation. Because of
the disproportionate effect of small amounts of low
molecular weight material on the osmotic pressure (77) the
following question arises. Cannot all of the inconsist-
encies in the osmotic data summarized in Table IX be ex-
plained by the presence or absence of diffUsion of low
molecular weight materials through the membranes? It has
just been shown that very small amounts of polymer cannot
be detected with certainty, and these are the very molecules
that cause the greatest change in (TI/c)c • o on diffusion.
The greater screening efficiency of Caustic membranes is
apparent and these are the membranes with which high

(lT/c>c = o values were obtained. Further evidence in

favor of the "diffusion theory" might be found but in the
writer's opinion such an argument fails because of two
 105
experimental fRets. The first is that with 8 - 10%
Caustic membranes, polymer was easily found on the solvent-
side after a determination, but with both of these membranes
the final (~/c)c • 0 value was higher than when a Carter-
Record membrane was used (Table IX and Fig. 6). With
Carter-Record membranes (Table XIV) and with 4 - 6% Caustic
membranes, (Table VIII) no detectable amounts of polymer
were found in the solvent side. If detectable amounts of
diffused polymer had less effect on the (llfc>c • 0 value
than the change from one membrane to another, it is un-
reasonable to maintain that non-detectable amounts of
polymer will account for the larger observed differences.
Were diffusion the only phenomenon involved the osmotic
pressure would be established at once {as it is where
adsorption is absent, or satisfied) and then fall off as
diffusion occurred. That this does not occur has already
been made clear. The conclusion was therefore reached
that the inconsistencies observed coUld not be explained
on the basis of diffusion.
 CLAIMS TO ORIGINAL WORK
AND CONTRIBUTIONS TO KNOWLEDGE

1. A modified form of the Carter-Record cell was

designed,used, and found wanting.
2. A counter-pressure type osmometer based on the
design or Van Campen was designed, and used successfully
to determine the molecular weights of four polyvinyl
acetate samples.
3. An oil thermostat was built to give control of
0.0008° c., for use with the above osmometers.
4. Membranes prepared from Cellophane, according
to the method outlined by carter and Record led to anomalous
results for the system polyvinyl acetate-acetone.
5. Membranes, which had higher screening efficiency,
more easily controlled permeability and which gave reason-
able osmotic pressure results, were prepared and used.
6. A study Of the characteristics of membranes led
to the development of a general theory to explain the
permeability of cellulose membranes.
7. The importance of adsorption was demonstrated.
This phenomenon is responsible for the time lags in
reaching equilibrium osmotic pressures and for the incon-
sistent osmotic results obtained with the Carter-Record
type membranes for the system polyvinyl acetate-acetone.
 REFERENCES

1. Flory, P. J. , J. Chem. Phys., 2, 660 ( 1941); !Q., 51

(1942)
2. Huggins, M.L., J. Phys. Chem., !§_, 151 (1942)
3. Huggins, M.L., J. Chem. Ph.ys., ~~ 440 {1941)
4. Huggins, M.L., Ann. N. Y. Acad. Sciences, g, 1 (1942)
5. Powel, R.E., Clark, C.R., and Eyring, H., J. Chem.
Phys., ~~ 269 (1941)
6. Fowler, R.H., and Rushbrooke, G.s., Trans. Faraday
Soc., ~~ 1272 (1937)
7. Meyer, K.H., z. physik. Chem. B44:383 (1939); see
Ref. 4, page 3
8. Kraemer, E.O., and Lansing, W.D., J. Am. Chem. Soc.,
E.!' 1369 (1935}
9. Meyer, K.H., and Mark, H., Ber. 61, 1945 (1928); Meyer,
K.H., z. angew. Ghem. 4, 935 (I928); Naturwissen-
schaften, !1 1 255 (1929T
10. Herzog, R.o., Kratky, o., and Petertil, E., Trans.
Faraday Soc., ~~ 60 (1933)
11. Adams, H.E., and Powers, P.o., Ind. Eng. Chem. Anal.
Ed., d£, 711 (1943)

12. Debye, P., Rubber Reports: R. D. C. 6/24/43 -- c. R.

103
13. Staudinger, H., The high polymer chemistry of cellu-
lose and rubber -- Springer -- Berlin -- 1932
14. Staudinger, H., Ber. ~~ 3019 (1926)
15. Kraemer, E.o., Ind. Eng. Chem., Ind. Ed., 30, 1200
{1938)
16. Dobry, A., J. Ghim. phys., 5 2, 1882 (1935); Bul.
soc. chim., 31, 568 {1934) -
17. Pau1ing, L., The Nature of the Chemical Bond, 2nd Ed.,
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 108
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