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Intrinsic Viscosity: Chain Linkage in

Polyvinyl Alcohol
Bea Lorraine S Acosta
Department of Chemistry
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro, Philippines

Abstract The experiment aimed to calculate the intrinsic where Rh is the hydrodynamic volume. The hydrodynamic
viscosity of PVOH solutions at different concentrations, volume is related in some way to the physical size of the
which was then used to determine the molecular weights of chain, given by the mean square radius of gyration as
both cleaved and uncleaved PVOH solutions using Flory
and Leutner method. Prior to calculation of intrins ic (Eq 2)
viscosity, the viscosity of the solutions was first calculated
and this was used to calculate for s pecific viscosity. where is the hydrodynamic coil expansion factor. (1)
Specific viscosity is the fractional increase in the viscosity
over that of the pure solvent caused by the addition of a Intrinsic viscosity, [], is defined as the ratio of the specific
polymer. The intrinsic viscosity was determined by viscosity to the weight concentration of solute, c, in the limit
plotting specific viscosity over concentration as a function of zero concentration:
of concentration and extrapolating at zero concentration.
The intrinsic viscosity of uncleaved and cleaved PVOH
[ ] ( ) ( ) (Eq 3)
solution was found to be 0.9434 and 0.0195 100mL g -1 ,
respectively. Using Flory and Leutner method, the average
viscosity molecular weight (M v) of both uncleaved and c is usually expressed in grams of solvent per 100 mL of
cleaved solutions were found to be 7.03710 4 and 420.4 g solution yielding [] with units of 100 g/cm3 . [] can be found
mol -1 , respectively. Moreover, the fraction of reverse by plotting either vs. c or vs. c and extrapolating to
linkages () was also calculated. The obtained delta was
zero concentration (the y-intercept of the best-fit line). (2)
found to be 0.1967; the inverse of this value is 5.086. This
implies that after cleaving the PVOH, 1 reverse link in
every 5 monomer units is formed; this large value signified
that the formation of head-to-head linkages was more II. EXPERIMENT AL SECT ION
favored during the polymerization process.

Keywords- Intrinsic Viscosity, Specific Viscosity, Polymer, The viscometer was thoroughly cleaned with chromic
Flory & Leutner Method acid cleaning solution and rinsed copiously with water, and
dried with acetone and air. The viscometer was immersed in a
water bath at 25C to equilibrate. The viscometer was
calibrated with distilled water.
I. INT RODUCT ION
Preparation of Stock Solution. A stock solution of the
polymer was prepared by weighing out accurately 4.0 to 4.5 g
The viscosity of even dilute polymer solutions is usually far
of dry polymer. It was slowly added with stirring to about 200
larger than just the viscosity of the background solvent, due to
mL of hot distilled water in a beaker. The powder was sifted
the large differences in size between the polymer and solvent
onto the surface and stirred gently to prevent bubbles and/or
molecules. In the non-free draining limit, we consider the
foam. When the entire polymer has dissolved, it was cooled
polymer chain to move as an equivalent impermeable particle
and then transferred carefully and quantitatively into a 250-
with an associated hydrodynamic volume that produces the
mL volumetric flask. The flask was filled with distilled water
same drag as the polymer chain. The friction coefficient is
up to the mark and was slowly inverted a few times to miss the
given by Stokes law as
contents.
(Eq 1)
Preparation of Uncleaved Solution. From the stock
solution, 50 mL was pipetted into 100-mL volumetric flask,
and diluted to the mark with distilled water, observing
precautions to prevent foaming. where and 0 are the viscosity of the solution and the
solvent, respectively. The calculated specific viscosities sp
Preparation of Cleaved Solution. To cleave the were 0.2798 and 0.2631.
polymer, 50 mL of the stock solution was pipetted to a 250-
mL flask; added with 25 mL distilled water and 0.25 g of solid The specific viscosity is dependent on the amount of
KIO4 . The flask was heated to about 70C and the solution PVOH in the solutions. However, it is more desirable to obtain
was stirred until all the salt was dissolved. The flask was then a viscosity independent to the concentration of PVOH
placed in a water bath and stirred until the solution was at solution. This is done by defining the viscosity of the solution
25C. The solution was transferred to a 100-mL volumetric at infinite dilution as shown in Eq 3. The intrinsic viscosity []
flask and diluted to mark with distilled water. was obtained by plotting vs. c or vs. c and

A second concentration of each material was extrapolating it to . The calculated intrinsic viscosity []
prepared by transferring 50 mL of the initial solution into a of the uncleaved PVOH solution was 0.9434100 mL g -1 .
100-mL volumetric flask and diluted to the mark with distilled Table 1 shows the summary of results while Figure 1 shows
water. All solutions were placed in water bath to equilibrate. the graph for the uncleaved solution. In Figure 1, the blue
graph represents vs. c while the red graph represents
The viscosities of the polymer solutions were vs. c; the value of the intrinsic viscosity [] is the value of the
measured using the viscometer. In between uses, it was y-intercept, where .
thoroughly rinsed with distilled water to remove the polymer,
and then dried with acetone and air. Table 1. Summary of obtained results for the uncleaved
PVOH solution.
c sp []
(g/100 mL) (g/cm3) (cP)
III. RESULT S AND DISCUSSION
0.8192 0.9980 1.144 0.2798
In this experiment, a stock solution of polyvinyl 0.4096 0.9980 1.129 0.2631 0.9434
alcohol (PVOH) was prepared and then used to produce
cleaved and uncleaved polymers. The intrinsic viscosities of
the cleaved and uncleaved PVOH solution was calculated, and
then used to calculate for the molecular weight of the
polymers.

Prior to viscosity measurements of the PVOH


solutions, the viscometer was calibrated to obtain its apparatus
constant B; water was used as the reference liquid. The
following equation (Eq 4) was used

(Eq 4)

where is the viscosity coefficient, cP, and is the density,


g/cm3 , of the reference liquid. The calculated value of B was
0.02909.

The first part of the experiment is the determination


of intrinsic viscosity of the uncleaved PVOH solution. Two Figure 1.The extrapolated graphs for the uncleaved PVOH
concentrations of this solution were prepared; 0.8192 and solution.
0.4096 g/100 mL. Using Eq 4, the calculated viscosity, ,
were 1.144 and 1.129 cP, respectively. This property is The second part of the experiment involves cleaving
dependent on the molecular properties of PVOH such as the PVOH with KIO4 . From the structure of PVOH, it can be
molecular size, molecular shape, and structure. Since it is in inferred that ts monomer unit can link to other monomer unit
solution form, it is dependent on the PVOH concentration, in a head-to-tail and head-to-head manner. The frequency of
molecular weight, and structure. The specific viscosity sp of head-to-head linkage depends on the relative rates of the head-
PVOH was calculated using the equation below (Eq 5). to-tail growth-step reaction and the head-to-head growth step
reaction.
(Eq 5)
The addition of KIO4 at 70C to the PVOH solution molecular weight known as the viscosity average molecular
causes the cleavage of 1,2-glycol linkages, which will then weight .
produce smaller chains. The size of the smaller chains depends
on the number of head-to-head linkages in the PVOH. Two kinds of averages are not equal but can be
related using the following expression (Eq 7):
In a similar manner with the first part of the
experiment, the viscosity, specific viscosity, and intrinsic

(Eq 7)
viscosity of the cleaved PVOH were calculated to be 1.160
and 0.9637 cP, 0.2975 and 0.0784, and 0.0195 100 mL g -1 .
The equation above is specific to the polydisperse PVOH.
Table 2. Summary of obtained results for the cleaved PVOH Rearranging Eq 7, was calculated to be 3.723104 and
solution. 222.4 g mol-1 for the uncleaved and cleaved PVOH,
c sp [] respectively.
(g/100 mL) (g/cm3) (cP)
By comparing the values of viscosities and average
0.8192 1.0978 1.160 0.2975 molecular weights of both uncleaved and uncleaved PVOH
0.4096 0.9980 0.9637 0.0784 0.0195 solution, it is concluded that the cleavage caused a decrease in
value of the said parameters.

The fraction of head-to-head linkages in the PVOH


was calculated using the obtained values of viscosities and
molecular weights of the uncleaved and cleaved polymer. The
fraction was calculated using the following equation (Eq 8)

(Eq 8)

where M n and Mn are the average molecular weights of the


uncleaved and cleaved polymer, and M 0 is the molar mass of
the monomer which is 44.0 g mol-1 . Substituting the previous
value to Eq 8 and combining it with Eq 7 gives an expression
that makes use of the viscosity average molecular weight M v
to calculate for directly (Eq 9).

( ) (Eq 9)
Figure 2.The extrapolated graphs for the cleaved PVOH
solution.
The obtained value of delta was 0.1966; the inverse
of this value is the ratio of head-to-head linkages for a number
In the molecular level, PVOH contains many single
bonds which make rotations in the structure pos sible. The of monomer units of PVOH, in this case that value is 5.086. In
the PVOH there is 1 head-to-head link in every 5 monomer
configuration around successive carbon atoms are independent
units. This large value signifies that the formation of head -to-
and unrelated, thus the two parts of PVOH chain are more
than a few carbon atoms apart are unrelated in terms of head linkages was more favored during the polymerization
process.
direction in space. Thus PVOH chain tends to adapt a tight,
ball-like form in solution.

Moreover, Flory and Leutner recognized correlation IV. ERROR ANALYSIS


between the molecular weight and the intrinsic viscosity for
PVOH in aqueous solution at 25C as shown in the equation
below (Eq 6): The obtained results were not guaranteed to be fully
[ ] (Eq 6) accurate due to inevitable instrumental and experimental
errors encountered during the experiment. Instrumental errors
The was calculated to be 7.037104 and 420.4 g mol-1 for include the use of uncalibrated apparatus such as the
volumetric flasks, pipettes, and burets, which contributes to
the uncleaved and cleaved PVOH, respectively. This value is
the uncertainty in calculating for the concentrations of
an average of molecular weights of molecules since PVOH is
solutions especially since concentration of solutions plays a
a polydisperse polymer; it is due to the dependence of
vital role in calculating for the viscosities. Another factor is
viscosity on both size and mass thus it produces is own
the non-uniformity of the temperature of water bath since it
affects the viscosity of the solutions. Experimental error due to 2. Uncleaved Solutions
the limitations of the experimenter includes inaccurate a. 1 st uncleaved solution
measurement of time at the appearance of the blue color in the c = 0.8192 g (100 mL)-1
reaction mixtures, which affected the calculation of the rate of = 0.9980 g cm-3
reaction.
Table B1. Data for the 1st uncleaved PVOH solution
(1/c)(ln
time (s) (cP) sp (ln /n 0 ) sp / c /n 0 )
V. CONCLUSION
39.95 1.160 0.2978 0.2607 0.3635 0.3182
Using Flory and Leutner method M v was calculated 40.32 1.171 0.3098 0.2699 0.3782 0.3294
to be 3.723104 and 222.4 g mol-1 for the uncleaved and 38.71 1.124 0.2575 0.2291 0.3143 0.2797
cleaved PVOH, respectively. This was obtained by calculating
the intrinsic viscosity for both uncleaved and cleaved solution 39.30 1.141 0.2767 0.2442 0.3377 0.2982
by plotting specific viscosity as a function of concentration. 38.70 1.124 0.2572 0.2289 0.3139 0.2794
The intrinsic viscosity of the uncleaved and cleaved PVOH
39.40 1.144 0.2798 0.3415 0.3010
was 0.9434 and 0.0195 100mL g -1 , respectively. The
obtained values for the cleaved PVOH proved the dependence
of viscosity to molar mass. The fraction of reverse linkages
b. 2 nd uncleaved solution
was calculated to be 0.1966; the inverse of this value, 5.086,
means that there is 1 reverse link in every 5 monomer units. c = 0.4096 g (100 mL)-1
= 0.9980 g cm-3

Table B2. Data for the 2nd uncleaved PVOH solution.


REFERENCES
(ln (1/c)(ln
time (s) (cP) sp /n 0 ) sp / c /n 0 )
(1) Viscosity of Polymer Solutions. Retrieved September 29,
39.15 1.137 0.2718 0.2404 0.6635 0.5870
2017 from
https://www.eng.yale.edu/polymers/docs/classes/polyphys/lect 39.59 1.149 0.2861 0.2516 0.6984 0.6143
ure_notes/5/handout5_wsu2.html 38.62 1.121 0.2546 0.2268 0.6215 0.5537
(2) Intrinsic Vsicsity: Chain Linkage in Polyvinyl Alcohol. 38.25 1.110 0.2426 0.2172 0.5922 0.5302
Retrieved September 29, 2017 from 38.81 1.127 0.2607 0.2317 0.6366 0.5657
http://www.chem.mun.ca/courseinfo/c3303/labs/exp_a.pdf
38.88 1.129 0.2631 0.6424 0.5702

[] = 0.9434
M v = 7.034104 g mol-1
APPENDICES M n = 3.723104 g mol-1

A. COLLECTED DATA
3. Cleaved Solutions
1. Viscometer a. 1 st cleaved solution
0 = 0.8937 cP c = 0.8192 g (100 mL)-1
= 0.9970 g cm-3 = 1.0978 g cm-3
B = 0.02909
Table B1. Data for the 1st cleaved solution.
Table A1. Data for calibration of viscometer. (1/c)(ln
time (s) (cP) sp (ln /n 0 ) sp / c /n 0 )
time (s) B
35.33 1.128 0.2625 0.2331 0.3204 0.2845
30.97 0.02894
37.37 1.193 0.3354 0.2892 0.4094 0.3530
31.08 0.02884
36.34 1.161 0.2986 0.2613 0.3644 0.3189
30.41 0.02948
36.99 1.181 0.3218 0.2790 0.3928 0.3406
30.82 0.02909
35.52 1.134 0.2693 0.2384 0.3287 0.2911
36.31 1.160 0.2975 0.3631 0.3176
b. 2 nd cleaved solution 5) Mn
c = 0.8192 g (100 mL)-1

= 0.9980 g cm-3

Table B2. Data for the 2nd cleaved solution.

(ln (1/c)(ln
time (s) (cP) sp /n 0 ) sp / c /n 0 )
6) Reverse linkages fraction,
34.45 1.0001 0.1191 0.1125 0.2908 0.2747
( )
33.23 0.9647 0.0795 0.0765 0.1940 0.1867
34.05 0.9885 0.1061 0.1009 0.2591 0.2462 ( )
32.80 0.9522 0.0655 0.0635 0.1599 0.1549
32.80 0.9522 0.0655 0.0635 0.1599 0.1549
32.56 0.9453 0.0577 0.0561 0.1409 0.1370
32.48 0.9430 0.0551 0.0536 0.1346 0.1310
33.20 0.9637 0.0784 0.1913 0.1836

[] = 0.0195
M v = 420.4 g mol-1
M n = 222.4 g mol-1

Note: All values in yellow are average values.

B. SAMPLE CALCULATIONS

1) Viscometer constant, B

2) Viscosity of solutions,

3) Specific viscosity, sp

4) Viscosity average molecular weight, M v


[ ]