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EXPERIMENT 5

INTRINSIC VISCOSITY: CHAIN LINKAGE IN POLYVINYL ALCOHOL


A Laboratory Report in Partial Fulfilment of the Requirements in Chem117 Laboratory

DAGONDON, VANESSA OLGA


CAGAMPAN, JOHN SULUMOR
(Group 1, Cluster 1)
With
Blyth Angela Balgos
Christine Debbie Shanne Angeles
(Group 2, Cluster 1)

Chem117 Laboratory Physical Chemistry II


Section 1

Performed on March 24, 2016


Submitted on May 3, 2016

Mr. Arnold Gaje, RCh


Laboratory Instructor

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ABSTRACT

The abnormal head-to-head chain linkage in polyvinyl alcohol was determined using
intrinsic viscosity measurements. The head-to-head chain linkage was expressed as the
difference between the molecular weight of the cleaved and uncleaved polyvinyl alcohol. The
cleaved polyvinyl alcohol was prepared by treating polyvinyl alcohol with periodic acid which
readily reacts with 1,2 glycols in the polymer which in turn, signifies the occurrence of the headto-head linkages. The molecular weight of the cleaved and uncleaved polyvinyl alcohol was
determined using intrinsic viscosity measurements. The resulting head-to-head chain linkage was
-5.14x10-2 %. The result was considered erroneous because of the lacking of data which thereby
caused false data analysis. Nevertheless, it was found out that as the occurrence of the head-tohead chain linkage depends on the rate constants of the formation of head-to-head and head-totail chain linkages each of which depends on the steric and energy factors. If the activation
energy of the formation of head-to-head chain linkage is much larger compared to that of the
head-to-tail chain linkage the number of head-to-head linkages increases with the polymerization
temperature.

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INTRODUCTION

Viscosity is a fundamental characteristic property of all liquids. When a liquid flows, it


has an internal resistance to flow. Viscosity is a measure of the resistance of flow or shear which
can also be termed as a drag force and is a measure of the frictional properties of fluid. Viscosity
is a function of temperature and pressure, however their effects are different for liquids and gases
(Atkins, 2010).
Polyvinyl Alcohol (PVOH) is a linear polymer of ethanol monomer units:
-Ch2-CHOHUnlike most high molar mass synthetic polymer, PVOH is soluble in water. The structure
of PVOH is determined by the structure of the polyvinyl acetate from which it is prepared by
hydrolysis. In which most of the monomer units are linked in a head-to-tail fashion, but a few are
linked in a head-to-head design.
-CH2-CHX-CH2-CHX-CH2-CHX-CH2(head-to-tail)

X = OH

(head-to-head)

The number of head-to-head linkages within the molecule depends upon the rate constants for
polymerization of PVOH; k and k:
k
R. + M R- M

Normal Reaction

(1)

k
R. + M R- M

Abnormal Reaction

(2)

R. is the growing polymer chain and the arrows give the relative directions of the linking units.
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Since the rate constants depend on the activation energy of each pathway, the ratio of the
rate constants can be expressed as
k eE / RT (E E )/ RT

=e
k e E / RT
b

(3)

And as E < E , the number of head-to-head linkages increases with polymerization temperature.
Each of these head-to-head linkages forms a 1,2-glycol which can be quantitatively cleaved with
Periodate (IO4-). Therefore, a determination of molar mass before and after treatment with
periodate provide an estimate of the fraction of head-to-head linkages in the molecules (Lenz,
1967).
A convenient method for the determination of polymers is via viscosity measurements.
The apparatus to be used in these determinations is the Ostwald viscosimeter. The size of the
capillary is marked '100'.

The viscosity of the solution is given by


=Bt

(4)

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where B is an apparatus constant, r is the liquid density at the measurement temperature, and t is
the time for the meniscus to go from the top fiducial mark (a) to the bottom mark (b). This will
take about 50 s - 60 s for pure water.

It has been shown that the ratio of the volume v of suspended particles in a total fluid volume V
is proportional to the specific viscosity sp; defined as:
sp = ( / 0) 1 v/V

(5)

where h is the viscosity of the solution, and h0 the viscosity of the solvent. Note that h is directly
proportional to t! The ratio of hsp to the solute concentration c (in grams per 100 ml of
solution!!) in the limit of infinite dilution is called the intrinsic viscosity []:

[] = lim sp = lim (1/c ln (/0))


c0 C
c0

(6)

Thus, 1/c . ln( / 0) and sp/c can be plotted vs. concentration and extrapolated to c =
0 to give [].
The problem now is to relate the molar mass to the viscosity. Since these molecules are
longchains with many single bonds about which rotation can take place, parts of the molecule
more than a few atoms apart are essentially randomly oriented and can therefore be treated
statistically. As such it can be shown that the mean distance between the chain ends, which is
also the effective mean diameter d of the molecule, is proportional to the square root of the chain
length (or the molar mass M):
d M1/2

(7)

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The volume of a molecule can be approximated as (vM) = d3 and equation (7) then becomes:
VM M3/2

(8)

Thus, the volume of all the molecules (v) is:


v (cV/M) M3/2= cVM1/2

(9)

From equations (9), (5) and (6) follows


sp
KM = C = []
1/2

(10)

where K is a constant.
These calculations ignore the significant effect of the solvent by assuming that it is a poor
solvent with no solvating effect which would make the molecular size increase; i.e., the statistical
treatment assumes random orientation but in fact an atom in the molecule cannot be in the same
space at the same time as a solvent molecule. Thus equation (10) above must be modified and is
found for PVOH in aqueous solution at 25C to be:

[] = 2.0 . 10-4 (Mv)a.

(11)

where a = 0.76, and Mv has units of g/mol. Equation (11) was derived by Flory and Leutner for
monodisperse samples (i. e., all molecules have the same weight) but also holds for polydisperse
ones (i. e. the sample is made up of molecules with a distribution of molar masses). In the latter
case, the molar mass is Mv, the viscosity average molar mass given by equation (12):

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M 1+a P ( M ) dM

v a = 0

MP ( M ) dM

(12)

where P(M) is the molar mass distribution function. Other experimental methods (i. e.
measurements of osmotic pressure) give number average molar masses

n a=

M 1+a P ( M ) dM
0

MP ( M ) dM

(13)

For monodisperse polymers, M v = M n , but for polydisperse polymers the relationship depends
on "a" and the distribution function P(M). If the chain lengths are random, this function is:

P( M )=

1 M /
e
n

(14)

Along with the aforementioned value of "a" for PVOH of 0.76, it can be shown that

and

n are related as follows:

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v
n = 1.89.

(15)

As previously mentioned, PVOH can be specifically cleaved at "head-to-head" sites, thereby


changing the number average molar mass M n of the uncleaved sample to M n ' of the cleaved
sample. The fraction D of the total monomer units bonded head-to-head is equal to the increase
in number of molecules during cleavage divided by the total number of units present, as number
is inversely proportional to molar mass in each case (Shoemaker, 2009).

1
1/n
n1
=
1/0

(16)

where M0 is the monomer molar mass (= 44 g/mol for PVOH). Therefore (with all molar masses
in g/mol),
1
1/n
n1
)
=44

(17)

and from (15) and (17)

=83(

1 1
)
v1 v

(18)

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METHODOLOGY
Preparation of Solutions
A stock solution of PVOH was prepared before the experiment. To prepare the stock
solution of PVOH a 4.4956 g of dry polymer was weighed into a container. The polymer was
added into a 200 mL hot distilled water slowly with a constant stirring. Then the powder on the
surface was sift and stirred gently as to avoid the formation of bubbles and foams. After the
polymer has dissolved the solution was cooled and transferred into a 250 mL volumetric flask
carefully and quantitatively while letting the solution run down the side of the flask as to avoid
foaming. The solutions was diluted to mark with distilled water and was mix by inverting the
flask slowly.
From the stock solution a cleaved and uncleaved PVOH was prepared. The uncleaved
solution of PVOH with 50.0 mL stock solution pipetted out into a 100 mL volumetric flask. The
solution was diluted to mark with distilled water and mixed slowly and gently as to prevernt
foaming. The flask was then placed in the bath to equilibrate.
The cleaved solution was prepared from the stock solution. A 50 mL stock solution was
pipetted into a 250 mL flask and was added with a 25 mL distilled water and 0.2468g of solid
KIO4. The flask was warmed to about 70 oC and was stirred until all the salt has dissolved. Then
the solution was placed in a thermostat bath with constant stirring until the temperature dropped
to 25 oC. The solution was transferred into a 100 mL volumetric flask and was diluted to mark.
The solution was mixed carefully and was transferred into a bath to equilibrate.
3 sets of solutions with different concentrations was prepared from both the uncleaved
and cleaved solutions. The two solutions prepared served as the initial solutions. The second
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solutions was prepared with a 50 mL of both the initial solutions pipetted into a different 100 mL
volumetric flask and was then diluted to mark with distilled water. A third set of solutions was
prepared by pipetting out 50 mL from the second set of solutions. The solutions was transferred
into a 100 mL volumetric flask and was diluted to mark (the solutions has a concentration equal
to one-quarter of the initial set of solutions).
Calibration of Viscosimeter
The viscosimeter was cleaned thoroughly with cleaning solution, rinsed with distilled
water and dried with acetone and air. The viscosimeter was then immersed into a 25 oC
thermostat bath to equilibrate for 10 minutes. A flask was also equilibrated in a 25 oC bath. The
viscosimeter was then calibrated with water. The viscosimeter was mounted vertically in a
constant-temperature bath as that both the fiducial marks are visible and was below the water
level. The bath was filled with water and the temperature was maintained within 0.1 oC of 27 oC
during the run with the addition of cold water. Since a glass walled thermostat bath wasnt
available. A 1.5 L container of soft drinks (Royal) was used was filled with water that served as
the constant-temperature bath.
Experimentation
To measure the viscosity of the solutions, the efflux time of the solutions were measured.
The viscosimeter was placed invertedly in the solutions as to fill the viscosimeter by drawing the
solutions using the aspirator. Then the viscosimeter was placed in thermostat-bath, returning it to
its normal vertical position. The solutions inside the viscometer were adjusted so that the liquid
only fills the lower bulb. Then the solutions were released from the hold letting the solution flow
through the bulbs. The time needed for the solution to flow from the initial mark up to the second
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mark was recorded as well as the time of flow from the second mark up to the third mark.
Similar procedure was done for the both the cleaved and uncleaved solutions (Shoemaker, 2009).
However due to the insufficient data that was gathered. The required quantities were not
solved using the gathered data. Instead another set of data was used which was taken from the
other group. Thus dry lab was performed.

RESULTS
The following results reflect each of the objectives stated in order to achieve the ultimate
goal of the experiment, to be able to determine the value of , the head-to head attachments, in
the polyvinyl alcohol sample. This value was determined to be -5.14x10-4.
Calibration of the viscosimeter determined the constant apparatus, B, to be 0.001399.
Three solutions of the cleaved and uncleaved polymer were prepared: 1st solution contains 100%
of the stock solution polymer; 2nd contains 50%; and, the 3rd contains 25%. The time of flow of
these solutions were recorded in triplicates. Table 1 summarizes the average of the time of flow
in each of the solutions of cleaved and uncleaved polymer.
Table 1. Average time flow of the solutions of cleaved and uncleaved polymer
Solution

Average time of flow in seconds


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Cleaved Polymer
6.51
5.88
4.62

1
2
3

Uncleaved Polymer
8.60
8.05
7.39

The concentrations of the polymer in grams per 100 mL solution in each solutions of the cleaved
and uncleaved polymer were determined. Table 2 shows the resulting concentration of the
cleaved and uncleaved polymer.

Table 2. Concentration of Polymer (g/100 mL)

Cleaved and Uncleaved Solution

Concentration, c (g/100 mL)

0.6006

0.3003

0.15015

Using the values of the constant apparatus and time of flow, the viscosities ( ) of the uncleaved
and cleaved solutions were determined. Table 2 summarizes the average viscosities obtained in
each solutions of the uncleaved and cleaved polymer.
Table 3. Average viscosities of the solutions of cleaved and uncleaved polymer
Solution

Average viscosity,

Specific viscosity, sp

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(g cm-1 s-1)
Cleaved Polymer

0.009011

0.01985

Uncleaved Polymer

0.01199

0.3461

Cleaved Polymer

0.008202

-0.07932

Uncleaved Polymer

0.01123

0.2605

Cleaved Polymer

0.006445

-0.2766

Uncleaved Polymer

0.01030

0.1566

Plotting sp/c against c and of 1/c ln(/o) against c will yield linear plots having an
intercept which value is equal to the intrinsic viscosity of the polymer, []. Figure 1 shows the
plot of sp/c against c and 1/c ln(/o) against c for the cleaved polymer solutions. Figure 2 shows
the same plot for the uncleaved polymer solutions.
0.5

nsp/c vs c

0
0.1 0.2
-0.5
Linear (nsp/c vs c)

1/concentration (100 m/g)

0.3

0.4

0.5

0.6

0.7

Linear (nsp/c vs c)

-1
-1.5

1/c*n(n/no) vs c

-2
Linear (1/c*n(n/no)
vs c)
-2.5
concentration (g/100mL)

Figure 1. sp/c vs c and 1/c ln(/o) vs c plots for the cleaved polymer solutions.

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0.5
0
0.5
-0.5 0 1
1/concentration (100 m/g)

-1
-1.5
-2

nsp/c vs c
Linear (nsp/c vs c)
Linear (nsp/c vs c)
1/c*n(n/no) vs c
Linear (1/c*n(n/no) vs
c)

-2.5
concentration (g/100mL)

Figure 1. sp/c vs c and 1/c ln(/o) vs c plots for the uncleaved polymer solutions.
Table 4 summarizes the intrinsic viscosities, [] obtained from each of the plots generated in the
cleaved and uncleaved polymer solutions. The average is value of [] is presented as well in the
table.
Table 4. Intrinsic viscosities of the polymer obtained from the two plots
Polymer Solution
Cleaved
Uncleaved

Plots
sp/c vs c
1/c ln(/o) vs c
sp/c vs c
1/c ln(/o) vs c

[ ]
-1.9901
-2.3106
1.1885
1.1067

Average []
2.1507
1.1476

From the value of the intrinsic viscosities, the viscosity average molar mass, M v, and the
number average molar mass, Mn were determined. Finally, these values are then used to
determine the value of , head to head attachments in the polyvinyl polymer. Table 5 shows
the values of Mv and Mn in the cleaved and uncleaved polymer solutions. Table 6 summarizes the

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value of , head to head attachments in the polyvinyl polymer from the two molar masses
determined.
Table 5. Mv and Mn in the cleaved and uncleaved polymer solutions
Polymer Solution
Cleaved
Uncleaved

Mv
208841
91142

Mn
110497
48223

Table 6. , head to head attachments in the polyvinyl polymer from Mv and Mn

Mv
Mn

Value
-0.000514222
-0.000513233

DISCUSSION
The occurrence of the head-to-head arrangements of structural unit in polyvinyl alcohol,
PVOH was determined by taking account the molecular weight decrease of the cleaved PVOH
from the uncleaved PVOH. The head-to-head structure in PVOH indicates the abnormal
arrangement of the substituents that is they are situated on consecutive carbon atoms. PVOH is
prepared from the alcoholysis of polyvinyl acetate. The vinyl acetate normally polymerizes in a
head to tail fashion producing alternating 1,3 acetate and thereby forming 1,3 alcohol by
hydrolysis (Billmayer, 1948). In the abnormal head-to-head arrangement of the substituents to
the growing chain, 1,2 glycols are formed instead of 1,3 glycols. To cleave the PVOH, it was
treated with periodic acid. Periodic acid readily reacts with 1,2 (vicinal) glycols cleaving the
bond between 1o and 2o carbons and forming 2 aldehydes (Figure 1) and does not react with 1,3

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glycols, at all. Thus, treatment of periodic acid decreases the molecular weight of the PVOH due
to the head to head polymerizations.

Figure 1. Reaction of KIO4 with 1,2 glycols (Billmayer, 1948)

The molecular weights of the uncleaved and cleaved PVOH were determined using
intrinsic viscosity measurements. The degradation of PVOH upon treatment of periodic aid was
observed in the decrease of viscosity of the cleaved PVOH compared to the uncleaved PVOH as
shown in Table 3. The specific viscosity is also indicated in Table 3. These values are relevant to
create four linear plots (Figure 1 and 2) each of which has an intercept equal to the intrinsic
viscosity of the cleaved and uncleaved PVOH. A plot of sp/c against c for the cleaved and
uncleaved PVOH is shown to have a positive slope of 3.7097 and a negative slope of -1.0266,
respectively. Moreover, the plot of 1/c ln(/o) against c for the cleaved and uncleaved PVOH is

shown to have a positive slope of 4.3124 and a negative slope of -1.033, respectively. However,
the plot of 1/c ln(/o) against c usually has a negative slope with a smaller magnitude compared
to the plot of sp/c against c (P. J. Dunlop, et. al., 1992). This deviation from the expected result
may signify error. Furthermore, the intercepts of these plots for the cleaved PVOH summarized
in Table 4 show negative values which indicate a negative intrinsic viscosity. This negative
intrinsic viscosity is considered to be erroneous because the value of the molecular weight of the
PVOH cannot be calculated and thereby the change in molecular weights of the cleaved and
uncleaved PVOH which indicates the head-to-head structure in the PVOH cannot be determined.
This erroneous data can be accounted from the calculation of viscosity of each of the solutions in
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the cleaved and uncleaved PVOH because instead of using the density of the solution, the density
of the solvent which is water was used. The density of the solution was no measured due to time
constraints and lack of laboratory resources. However to be able to at least generate some data,
the absolute value of the intrinsic viscosity of the cleaved PVOH solution was obtained to
eliminate the negative sign.

Table 5 shows the resulting molecular weights of the cleaved and uncleaved PVOH
expressed as the viscosity average molar mass, M v, and the number average molar mass, Mn.
Using eq. 17 and 18, the value of , head to head attachments in the polyvinyl polymer was
determined as shown in Table 6. It is showed that the average value of the head to head
attachments, , -5.14x10-2 %. The negative sign signifies that the molecular weight after
degradation is in fact larger than the initial molecular weight of PVOH. This should not be the
case and therefore this result is greatly influenced with the systematic error that was committed
in the calculation of the viscosity.
The study of Flory and Leutner in 1948 yielded results summarized in Table 7. In their
study, they assumed that the 1,2 structures are distributed at random throughout the polymer and
the distribution of the molecular weights obtained are only approximates of the most probable
distribution. They observed a correlation between the temperature the value of head-to-head
attachments in the polymer. As shown in Table 8, as the temperature of polymerization increases
the value of the head-to-head attachments in the polymer also increases. According to their study,
this observation indicates that the 1,2-glycol structures produced in the head-to head attachments
of monomer in PVOH must be formed in the chain - growth process of the vinyl acetate
polymerization (Flory and Leutner, 1948).

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Table 8. Results from the study of Flory and Leutner, 1948

The occurrence of the head-to-head linkages depends on the two rate constants for the
polymerization of PVOH: kp for the normal chain propagation and and kp for the abnormal chain
propagation. (I) of figure 4 shows the free radical addition at the unsubstituted carbon of vinyl
acetate should be favoured by steric and energy factors. However because of the comparatively
low resonance energy of X (-OCOCH3), (II) of figure 4 which denotes the abnormal addition of
substituent may occur (Flory and Leutner, 1948).

Figure. 4 Free Radical Addition in the synthesis of PVOH from PVA (Flory and Leutner, 1948)

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Both of the rate constants depend on the activation energy of each pathway. If the
activation energy of abnormal chain propagation prevails, the number of head-to-head linkages
increases with polymerization temperature. This effect is shown in Table 7.

CONCLUSION
The abnormal head-to-head chain linkage in polyvinyl alcohol was determined using
intrinsic viscosity measurements. The physical properties of polymers including polyvinyl
alcohol depend on the chain length, degree of branching and molecular weight. Polyvinyl alcohol
is a unique polymer because it has a negligible amount of branching and therefore is soluble in
water. Polyvinyl alcohol is usually prepared through the alcoholysis of polyvinyl acetate.
Normal head-to-tail chain linkage forms 1,3-glycols while abnormal head-to-head chain linkage
forms 1,2-glycols. The occurrence of the abnormal head-to-head chain linkage in polyvinyl
alcohol can be determined by treatment of periodic acid that reacts with 1,2-glycols but not with
1,3-glycols. The occurrence of the head-to-head linkage of PVOH can be expressed as the
molecular weight difference between the cleaved and uncleaved PVOH. In the experiment, 3
different concentration of the cleaved and uncleaved polyvinyl alcohol were prepared. To
determine the molecular weights of each of these solutions, the intrinsic viscosity was
determined and thereby the molecular weights, viscosity average molar mass, M v, and the
number average molar mass, Mn and finally the , the head-to-head chain linkage was
determined. However, the data analysis done on the data collected was erroneous because the
density of the solution was not determined which led for the experimenter to use the density of
the solvent. Nonetheless, the data produced the value to be -5.14x10-2 %.

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As the temperature of polymerization increases the value of the head-to-head attachments


in the polymer also increases. The occurrence of the head-to-head linkages depends on the two
rate constants for the polymerization of PVOH: k p for the normal chain propagation and and k p
for the abnormal chain propagation. Both of the rate constants depend on the activation energy of
each pathway. If the activation energy of abnormal chain propagation is larger than the activation
energy of the normal chain propagation, the number of head-to-head linkages increases with
polymerization temperature.

REFERENCES
Atkins, P.; de Paula, J. Physical Chemistry Ninth Edition; Oxford University Press: Great Britain,
2010.
Flory, P. J., Leutner, F. S. Occurrence of Head-to-Head Arrangements of Structural Units in
Polyvinyl Alcohol. Journal of Polymer Science. 1948, 5, 880-890.
Shoemaker, D. P.; et. al. Experiment in Physica1 Chemistry; McGraw-Hill Publishing Company:
Toronto, 2009; pp 318-327.
Dunlop, P. J., Harris, K. R., Young, D. J. Physical Methods of Chemistry, 2nd ed.; WileyInterscience: New York, 1992.
Lenz, R. W. Organic Chemistry of Synthetic High Polymers; Wiley-Interscience: New York,
1967; pp. 261271, 305369.
ACKNWLEDGEMENTS

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We would like to express our deepest gratitude to our laboratory classmates and
especially to our cluster for working with us diligently, to our instructor for guiding us during the
experiment, and to the chemistry department for providing us the materials for the experiment.
CONTRIBUTION OF AUTHORS
Each of the members of the group contributed accordingly in the making of this
laboratory report: Cagampan authored the introduction and material and method sections;
Dagondon, on the other hand, was in charge of the data analysis, the compilation of results,
discussion and also the conclusion; Cagampan wrote the abstract and proof read the overall
report.
APPENDICES
APPENDIX A: TABLES
Table 7. Raw Data
% PVOH

Trials

100

1
2
3
1
2
3
1
2
3

50
25

Time of Flow (s)


Cleaved
Uncleaved
6.46
8.59
6.54
8.58
6.54
8.62
5.85
8.11
5.91
8.04
5.88
8
4.59
7.35
4.63
7.34
4.64
7.47

Table 8. Values for sp/c and 1/c ln(/o) for cleaved and uncleaved PVOH
PVOH

% PVOH

Cleaved PVOH

100
50

nsp/c

1/c*ln(n/no)
0.033045603
-0.264132931

0.032693961
-0.275226346
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Uncleaved PVOH

25
100
50
25

-1.842210318
0.576177405
0.867319241
1.042905818

-2.15660875
0.494795241
0.770754605
0.968672406

APPENDIX B: SAMPLE CALCUATIONS

apparatus constant, B
3
1 1

8.909 10 g cm s
B= =
=0.001399
t (0.99708 g cm3)(6.35 s)

Concentration in g/100 mL of PVOH, c


For 100% PVOH only:
3.003 g PVOH 50 mL
c=

100 mL=0.6006 g /100 mL


250 mL
100 mL

Viscosity, and specific viscosity, sp


For 100% cleaved PVOH trial 1 only:
=Bt=( 0.001399 )( 6.46 s ) ( 0.99708 g cm3 )=0.009011 g cm1 s1
sp =

0.009011 g cm1 s1
1=
1=0.011496342
3
1 1
0
8.909 10 g cm s

sp/c and 1/c ln(/o)


For 100% cleaved PVOH trial 1 only:
sp
0.011496342
=
=0.019141429 g1 100 mL
c 0.60006 g /100 mL

1
ln =
c
0

( )

1
0.60006

g
100 mL

ln

0.009011 g cm1 s1
=0.019032236 g1 100 mL
3
1 1
8.909 10 g cm s

Intrinsic viscosity, [ via Least Square Methods


For the cleaved PVOH sp/c vs c plot only:
[ ] = yintercept =b= y m x

y =

0.0330456030.2641329311.842210318
=0.69109922
3

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x =

0.033045603+ 0.264132931+ 1.842210318


=0.35035
3

m=

S xy
=3.70971991
S xx

[ ] =0.69109922( 3.70971991 )( 0.35035 )=1.990799585

Mv and Mn
For cleaved PVOH only:
M v =7.6 10 4 []1.32=7.6 10 4 [ 2.150684244]1.32 =208840.5243 g /mol
M n=

M v 208840.5243 g/mol
=
=110497.6319 g / mol
1.89
1.89

Mv and Mn
1
1
1
1
Mv =83

=83

=0.000513233
Mv ' Mv
2088404.5243 191142.16204
Mn

)
(
) (
1
1
1
1
=44 (

=44 (

=0.000514222
M ' M )
110497.6319 91142.16204 )
n

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