Intrinsic viscosity Lab:

Determination of Chain Linkage in Poly Vinyl

Alcohol
Daniel Gonzalez
Partner: Jenny Jiou
Physical Measurements
Goux
Spring 2016
ABSTRACT:
Two solutions of 1% and .5% poly vinyl alcohol (PVOH) in water, one un-
cleaved and the other cleaved with KIO4, were prepared and analyzed with an
Ostwald viscometer. The flow times were compared to water as a standard
with the apparatus constant (B) calculated to be 3.3x10-7+/- 1.5x10-9 (cm2s-2)
and the coefficients of viscosity of the cleaved and un-cleaved 1% and .5%
solutions were determined to be 2.4x10-4 , 1.5x10-4 and 1.2x10-4, 1.1x10-4
(g/cm s) respectively. The calculated viscosity coefficients were used to
calculate the relative viscosities and then after dividing by the concentration,
the reduced and inherent viscosities of the cleaved and un-cleaved PVOH
were calculated. The intrinsic viscosities of the 1% and .5% PVOH solutions
were then graphically determined to be .8834+/-.029 and .3444+/-.01 (dL/g)
respectively. Using the Mark Houwink Sakurada method, the molecular
weights of viscosity MMv was calculated for cleaved and un-cleaved PVOH to be
64,524.08 +/-719.9 and 18,588.2+/-164.09 (g/mol) respectively. Using the
conversion method outlined by Shoemaker, MMn was calculated for cleaved
and un-cleaved PVOH to be 34,139.72 +/-380.89 and 9,835.03+/-86.82
(g/mol)respectively. Two values were calculated using MMn and MMv being .
00337 and .00318 respectively and collectively corresponding to an average
of 1 out of every 306 linkages being a head to head linkage.

INTODUCTION:
Poly vinyl alcohol is a nontoxic, water soluble polymer frequently used in the
food industry as a thickening agent and with a wide range of other
applications ranging form high school slime lab experiments, to foundations
for membranes used in tissue engineering labs. Poly vinyl alcohol is a macro
molecule formed of multiple repeating vinyl alcohol groups joined by a
carbon-carbon bond formed by spitting the double bond on the vinyl group.

Figure 1. Vinyl Alcohol

 Figure 2.
When vinyl alcohol polymerizes as shown in figure 2. there are two possible
orientation in which it can do so, head to tail, or the less common head to
head linkage. Because the head to head linkages is a vicinal diol, this group
is susceptible to cleavage by KIO4 and will result in smaller chains.
k E a

k =(S) e (1)
RT

The above equation relates the two rate constants k and k that correspond
to a head to tail and a head to head linkage respectively. (S) is the steric
constant that determines if the polymer is sterically hindered to the point of
affecting the linkages and Ea= Ea-Ea such that this term should be positive
given Ea is much larger (and thus more energetically unfavorable).
In order to know anything useful about a polymer, it is critical to first
estimate the size of the polymer. Intuitively for linear polymers, the longer
the polymer, the greater the mass, and if in solution, the more viscous the
solution. Viscosity itself can be defined in multiple ways however the most
applicable way to think of it is the resistance to shear force in a fluid, or
rather a frictional force in the fluid itself. More viscose fluids will be thicker
and act more like jellies while a less viscose fluid is easy to pour and will be
more like water. In this experiment the longer the PVOH chains are will
directly result in a greater viscosity coefficient ().

=B (t) (2)

The above equation relates the viscosity coefficient and density to the
Apparatus constant B (of the ostwald viscometer) and flow time t in seconds.
 Using Known values for the density of water and the viscosity coefficient of
water, the time water takes to flow through the viscometer can be measured
and B can be calculated by rearranging equation 2 to be in the form of:

B= t (3)

Once B is solved for, any solutions with known densities can be run through
the viscometer and can be calculated. Once is calculated for the
solutions, the following terms can be derived using and o , the viscosity
coefficient of water.

Relative Viscosity:

r = o (4)

Specific Viscosity:
o
sp = o =( r -1) (5)

Reduced Viscosity:
red = sp/c (6)
with c being the concentration in g/cm3

Inherent Viscosity:
ln ( r )
inh = c (7)

Intrinsic viscosity:
sp ln ( r )
lim lim
[] = c0 c = c0 c (8)

This can be solved for graphically by graphing reduced viscosity and inherent
viscosity against concentration together and linearly approximating to where
concentration is equal to zero.
For non branching polymers, an approximation for the molecular weight
comes from the Mark Houwink Sakurada equation which relates intrinsic
viscosity to molecular mass by two correction coefficients K and .
 []=K[M] (9)
Where K and are predetermined constants for the material at a given
temperature. For Poly vinyl alcohol this equation can be re-written with
substituted K and values as the equation bellow:
M=7.6x104[]1.32 (10)
Where M will be MMv which is the molecular mass from the viscosity averaged
mass.
According to Shoemaker, this mass is different than the number average
mass ( MMn) which can be thought of as the average of different polymer chain
lengths together.
For rigid polymers that act as perfect rods, the true mass will lie closer to MMn
compared to polymers that can ball up and coil which will have a mass closer
to MMv. the ratio between these two values is anywhere between 1 and 2, 1
meaning they are the same and 2 being completely different. For polyvinyl
alcohol the molecule is mostly linear, but can coil to some extent. According
to Shoemaker the relationship between the two is defined as follows:

MM v
1.89 = MMn (11)

Thus, by determining [] graphically for both cleaved and un cleaved PVOH,

MMv can be calculated for both solutions (with the cleaved being denoted as
MMv. ) which can then be used to calculate MMn and MMn.
Knowing the masses of cleaved and un cleaved PVOH, assuming KIO 4 only
cleaves at head to head linkages, one can calculate which is the proportion
of head to head linkages to regular head to tail linkages using the following
two equations:
1 1
= 44( MM ' n M
n
(12)

1 1
= 83( MM ' v M
v
(13)

METHODS:
Preparation of solutions PVOH
All methods were carried out at the University of Texas at Dallas Berkner
Hall under the guidance of Dr. Warren Goux. 4 solutions of PVOH 1%,.5% and
1% cleaved and .5% cleaved were made from a stock of 4% PVOH in water
provided by Sigma Aldrich. One solution was created by taking 50ml of stock
and diluting to the mark of a 100ml volumetric flask with DiH2O resulting in a
2% solution. 50ml of the 2% solution was pipetted to another 100 ml
volumetric flask and diluted to the mark resulting in a 1% PVOH solution. Two
of these 1% solutions were prepared but one had .25g KIO4 added before
being filled to the mark. This was the 1% cleaved solution and was used to
make the .5% cleaved solution. The .5% cleaved and un- cleaved solutions
were prepared by taking 50ml form the respective 1% solutions and diluting
to the mark in a 100ml volumetric flask.

Preparation of apparatus:

Figure 3 Set up of Apparatus [1]

Running of experiment:
The Viscometer was cleaned with acetone and thoroughly dried before each
use. The first 3 runs was performed with pure deionized water at 25 degrees
Celsius. A small sample of each of the prepared solutions were stored in
disposable reaction vials and stored submerged in the water bath at 25 C.
The sample to be analyzed was pipetted into the bulb of the viscometer and
suction using the bulb of a large pipetter was used to draw up the solution to
mark a on figure 3. Thesuction was ceased and the time it took for the
solution to fall to mark B was recorded.

RESULTS:
Table 1

water (g/cm) (g/cm s) T (s) B (cm2s-2)

0.99709 8.91E-05 267.53 3.3E-07
269.61 3.31E-07
269.6 3.3E-07
Average 268.91 3.3E-07
SD 1.49E-09

Table 2

PVOH 1% (g/cm) T (s) (g/cm s)

1.19 609.95 0.00024
1.19 610.1 0.00024
1.19 587.5 0.000231
Average 5.10E-06 0.000237
SD 5.10708E-
06

Table 3

PVOH .5% (g/cm) T (s) (g/cm s)

1.19 378 0.000148
1.19 379 0.000149
1.19 380 0.000149
Average 0.000149
SD 3.927E-07

Table 4
 PVOH 1%
cleaved (g/cm) T (s) (g/cm s)
1.19 303 0.000119
1.19 302.92 0.000119
1.19 307 0.000121
Average 0.00012
9.16105E-
SD 07

Table 5
PVOH .5%
cleaved (g/cm) T (s) (g/cm s)
1.19 269.89 0.000106
1.19 270 0.000106
1.19 270 0.000106
Average 0.00011
2.49398E-
SD 08

Graph 1.

Intrinsic Viscosity of Uncleaved PVOH

160
140
f(x) = 4443.87x + 86.26
120
R = 1
100 n sp/c

80 Linear (n sp/c)
reduced and inherent viscosities f(x) = - 700.54x + 90.42
R = 1 ln(n/no)/c
60
Linear (ln(n/no)/c)
40
20
0

Concentraiton( g/ml)

Graph 2.
 Intrinsic Viscosity of Cleaved PVOH
50

40

f(x) nsp/c
30 f(x) =
= -- 545.03x
763.52x +
+ 35.17
33.76
R =
R = 11 Linear (nsp/c)
reduced and inherent viscosities
20 ln(n/no)/c
Linear (ln(n/no)/c)
10

concentration g/ml

Table 6.
PVOH Averag SD r sp red inh Avera SD
3
e (cm / (cm3/ ge
g) g) []
(g/cm (cm3/g
s) )
1% .0024 5.11E- 2.66 1.656 139.4 82.08 88.33 2.931
6 6 9
.5% . 3.93E- 1.67 .671 112.7 86.25
00015 7 1
1% .0012 9.16E- 1.34 .341 28.69 24.69 34.44 .956
cleaved 7 1
. . 2.49E- 1.19 .189 31.93 29.23
5%cleav 00011 8
ed

Table 7.
 MMv MMv MMn MMn n v Average

PVOH 18588.2 64524.0 9835.03 34139.7 .00318 .00337 .00326
+/- 8 +/- 2
164.09 +/- 86.82 +/-
719.9 380.89

Regression Analysis Un-Cleaved PVOH

SUMMARY OUTPUT nsp/c uncleaved

Regression Statistics
Multiple R 1
R Square 1
Adjusted R
Square 65535
Standard Error 0
Observations 2

ANOVA
Significanc
df SS MS F eF
349.563240 349.563 #NUM
Regression 1 5 2 ! #NUM!
Residual 0 0 65535
349.563240
Total 1 5

Coefficie Standard P- Upper Lower Upper

nts Error t Stat value Lower 95% 95% 95.0% 95.0%
#NUM
Intercept 86.264 0 65535 ! 86.264 86.264 86.264 86.264
#NUM 4443.86
X Variable 1 4443.866 0 65535 ! 4443.866 6 4443.866 4443.866

SUMMARY OUTPUT ln(/o)/c uncleaved

Regression Statistics
Multiple R 1
R Square 1
Adjusted R
Square 65535
Standard Error 0
Observations 2
ANOVA
Significan
df SS MS F ce F
8.6869622 8.68696 #NUM
Regression 1 93 2 ! #NUM!
Residual 0 0 65535
8.6869622
Total 1 93

Coefficie Standard P- Lower Upper Lower

nts Error t Stat value 95% 95% 95.0% Upper 95.0%
90.4169 #NUM 90.4169
Intercept 1 0 65535 ! 90.41691 1 90.41691 90.41691
#NUM -
X Variable 1 -700.538 0 65535 ! -700.538 700.538 -700.538 -700.538

Regression Analysis Cleaved PVOH

SUMMARY OUTPUT nsp/c cleaved

Regression Statistics
Multiple R 1
R Square 1
Adjusted R
Square 65535
Standard Error 0
Observations 2

ANOVA
Significan
Df SS MS F ce F
Regression 1 5.2582002 5.2582 #NUM! #NUM!
Residual 0 0 65535
Total 1 5.2582002

Coefficie Standard Lower Upper Lower Upper

nts Error t Stat P-value 95% 95% 95.0% 95.0%
Intercept 35.171 0 65535 #NUM! 35.171 35.171 35.171 35.171
-
X Variable 1 -545.025 0 65535 #NUM! -545.025 545.025 -545.025 -545.025

SUMMARY OUTPUT ln(n/no)/c cleaved

Regression Statistics
Multiple R 1
R Square 1
Adjusted R
Square 65535
Standard Error 0
Observations 2

ANOVA
Significan
df SS MS F ce F
10.319
Regression 1 10.319088 09 #NUM! #NUM!
Residual 0 0 65535
Total 1 10.319088

Coefficie Standard Lower Upper Lower Upper

nts Error t Stat P-value 95% 95% 95.0% 95.0%
33.7648 33.7648
Intercept 1 0 65535 #NUM! 33.76481 1 33.76481 33.76481
-
X Variable 1 -763.517 0 65535 #NUM! -763.517 763.517 -763.517 -763.517

Sample Calculations:
1) calculate B from the time average of water runs given o of water to be .
8909E-5 and density to be .99709g/cm3 at 25 C.

B= t

1 1
0.00008909 g c m s
B= g -7 2 -2
0.99709 3
(268.91 ) s = 3.3x10 cm s
cm

2)Calculate for 1%, .5% 1% cleaved and .5% cleaved PVOH solutions using
B value from step 1 and using 1.19 g/cm3 for the density of PHOH (example
calculation is only for 1% and .5% PVOH)
= B t
1%= 3.3x10-7 (cm2s-2 )587.5 (s) 1.19 (g/cm3)= .0024 (g/cm s)
.5%= 3.3x10-7 (cm2s-2 )379 (s) 1.19 (g/cm3)= .00015 (g/cm s)

3) Calculate relative viscosity, specific viscosity reduced viscosity and

inherent viscosity of 1% and .5% PVOH

Relative Viscosity:

r = o

.0024 .00015
1% r = .8909E-5 =2.66 .5%r = .8909E-5 = 1.67

Specific Viscosity:
o
sp = o =( r -1)

1%sp=(2.66-1)=1.66
.5%sp=(1.67-1)=.67

Reduced Viscosity:
red = sp/c
C ) in this case 1.19g/ml is density. In 1% solution that means 1ml PVOH in
100ml solution or 1.19g in 100ml so 1% c=.0119 and .5% c=.00595
1%red=1.66/.0119=139.46 (cm-3/g)
.5%red=.67/.0119=112.71(cm-3/g)

Inherent Viscosity:
ln ( r )
inh = c

ln ( 2.66)
1%inh = .0119 = 82.0805 (cm-3/g)

ln ( 1.67)
-3
.5%inh = .00595 = 86.2487 (cm /g)

4) Determine the Inherent Viscosity by Graphing the following Data to obtain

graph 1. And run linear regression for both trend lines to approximate the
intercept value.
Table 8
C (independent) red (dependent 1) inh (dependent 2)
g/cm3
.00595 112.71 86.2487
 .0119 139.46 82.0805

Intercept Values: 86.264 and 90.4169

Take average and SD for Error
[] of PVOH= 88.337 (cm-3/g) +/- 2.931 (cm-3/g)
5) Calculate Mass
M=7.6x104[]1.32
Convert [] to dL/g by multiplying by .01
M=7.6x104[.88337]1.32
MMv=64524.08 +/- 719.9
Do steps 1-5 for 1% and .5% un-cleaved to obtain:
MMv=18588.2 +/- 164.09
6) Calculate MMn and MMn
MM v
1.89 = MMn

64524.08
1.89 = MMn

MMn=34139.72+/-380
MMn=9835.03+/-86.82
7) Calculate
1 1
= 44( 9835.03 34139.72 = .00318

or
1 1
= 83( MM ' v M
v =.00326

The average value is .00322

This corresponds to 1/310 monomers being a head to head linkage.
DISCUSSION:
Over all the experiment was successful in the sense that the solutions were
made, data was obtained and the graphs when plotted resulted in
reasonable appearing values. As far as literature values go, the mass of poly
vinyl alcohol has been reported form ranges of 10,000 to 300,000 g/mol. An
accurate estimate of the molecular mass for a 1% or 5% solution of poly
vinyl alcohol in water was not able to be determined as many factors such as
different solvents, temperatures, and different experiments entirely have
been performed with similar experiments to this one resulting in very high
amounts of error. One such experiment performed by a student of Colorado
University resulted in an error of 93%[6] . The relative viscosities tabulated in
table 6 seems reasonable as the clearly smaller .5% PVOH solutions indeed
have lower values and lower relative viscosity values that of the
corresponding 1% solutions.
According to finding by Misra, an intrinsic viscosity for PVOH was determined
to be around .25 Dl/g in a 6M solution at 30 C which is very small
compared to the values of .88 Dl/g that was obtained in a 1% solution of
PVOH. Interestingly enough despite the discrepancies in , it was found that
the over all calculated masses were 64.524.08+/- 719.9 using the viscosity
average mass and 34139.72+/-380.89 using the number average mass. Both
of these values fall into an acceptable rang for what is expected for PVOH,
despite such glaring differences in the viscosity coefficients and one value
does not seem better than another without a reliable literature value to base
the comparison off of. Intuitively, PVOH is a fairly linear molecule rather than
a highly coiled polymer so it would be reasonable to assume the MMn value to
be more accurate.
According to the handbook of Fiber Chemistry, it should be expected to have
1 to 2 head to head linkages for every 100 monomer units of PVOH. These
findings are much larger than what was calculated as it was determined that
delta was around 1 in every 306 monomers, being far fewer than expected.
One consideration though is that the 1-2/100 value was taken at 20C while
this particular experiment was carried out at 25C. Despite this fact, it should
then be expected to have a larger percentage of head to head linkages as
there is more energy to allow for k to proceed with head to head additions.
It would be expected though that an over estimation in the mass would
result in a lower than expected delta value meaning the true issue could lay
in an intrinsic viscosity that is too large.
The sources of error for this experiment could have risen from the fact that
the times recorded from the water runs were particularly close to those
values recorded for the .5% PVOH. This could mean that the value for B was
calculated correctly, but with inaccurate values resulting in a systematic
error through every calculation of . The times could have been off due to a
multitude of reasons, such as impure water, a dirty viscometer, systematic
incorrect readings of the viscometer, or simply a very catastrophic error in
preparation of the solutions. Perhaps more PVOH was in our solutions than
expected yielding in viscosity coefficients that are much larger than
expected. However if the B value from the water run was too large, every
viscosity coefficient will systematically be too large as B is directly
proportional to .
In conclusion using an Ostwald Viscometer to determine polymer mass and
head to head linkages of poly vinyl alcohol does not seem to be a very
precise way to approximate the true values. Multiple sources yielded very
different results as well as very different methods of calculations and with
the heavy reliance on non mechanical or spectroscopic methods the
possibility for error seems very high.

REFFERENCES:
1. Shoemaker, Garland, Nibler, "Experiments in Physical Chemistry, 8th ed."
McGraw-Hill Publishing Company, Toronto (2009)
2. P.J. Flory and F.S. Leutner, J. Polym. Sci. 3, 880 (1948); 5, 267 (1950).
3. Stokes, R.H., and Mills, R., "Viscosity of Electrolytes and Related Properties,"
Permagon Press, London.
4. Kline, Gordon M., ed., "Analytical Chemistry of Polymers, Part II," Interscience
Publishers, New York (1962).
5. Jellinek, H.H.G., "Degradation of Vinyl Polymers," Academic Press Inc., New York
(1955).
6. http://chem.colorado.edu/chem4581_91/images/stories/ExampleLabReportb.pdf

7. G. S. Misra, P. K. Mukherjee Colloid and Polymer Science February

1980, Volume 258, Issue 2, pp 152-155

APPENDIX: