Determinton of the viscosity average

molecular weight of polyvinyl alcohol

graphically.
Tuhin Subhra Haldar
1111055

Molecular Weight Determinaton
Molecular weight determinaton is a fundamental characterizaton technique, which can be
experimentally obtained by measuring the iscosity, !omatc "ressure and light sca#ering
measurements of the soluton containing the dissolved polymer. iscosity and !omatc pressure are
called $olligatve propertes because they are systematcally dependent on the number of polymer
molecules in the soluton. %n instrument &nown as iscometer is used to determine the viscosity of
any liquid, and the equaton governing the dynamics inside the viscometer apparatus is given by'
()*
(
g
8V
)
t=ct
, .............+,-
Where,
. * /adius of the tube through which liquid 0ows,
g * %cceleraton due to gravity,
1 * Density of the solvent,
t * 2ime ta&en by the liquid to 0ow through the tube.
2erms present in the brac&ets can be expressed as another constant )c), which are the characteristcs
of any viscometer tube. 2hey can be determined by calibratng the viscometer with pure water.
(
sp
*()3(
4
5(
4
()3(
4
* 6ractonal change in viscosites,
(
4
* iscosity of solvent, i.e. pure water,
(
sp
* !peci7c iscosity,
%nother

useful quantty is intrinsic viscosity which is sometmes referred to as !taudinger index.
8(9*lim
$m:4
+(
sp
5$
m
-*+;4</
=
-5=m
2he limit of in7nite diluton +$
m
:4- is required to de7ne a viscosity property that is intrinsic to the
solute +in the given solvent-, that is independent of the concentraton. 2his approach eliminates
problems caused by the fact that the bul& propertes of the polymer soluton vary with
concentraton.
,f a linear chain polymer is constructed of > monomer units lin&ed together such that each lin& is
rotatonally 0exible, the radius of gyraton is predicted to be proportonal to the square root of the
number of lin&s in the chain, thus / ? +>-
;5@.
. !o the relaton for intrinsic viscosity with molecular
weight is given by,
8(9*AM
;5@
2he above equaton relates intrinsic viscosity to the desired molecular weight of the polymer. But,
many polymer solutons deviate from this equaton because of the nature of the soluton and the
eCects brought about by solvent associaton. 2hus, a more general relatonship is provided by Mark-
Houwink equaton, as shown below'
8()9*AM
a
here, )A) and )a) are polymer, solvent and temperature dependent parameters to be veri7ed
experimentally. 2herefore, the viscosity average molecular weight +M
4
- of the solute can be
expressed as'
M
v
*+8()95A-
;5a
where the parameter )a) is referred to as ))phobicity)) of the interacton between polymer and solvent
molecules.
$hemicals /equired '
"olyvinyl alcohol stoc& soluton+4.44Dg5ml-
Water
%pparatus /equired:
iscometer
!topwatch
Bea&ers
6unnel
"ipe#e and bulb
olumetric 6las&
"rocedure'
@Eml of D4F, G4F, H4F and @4F concentraton soluton were prepared from the stoc&
soluton.
2he viscometer was clamped and pure water was 7lled. Ising a pipe#e bulb, the liquid was
pushed above the 7ducial and then allowed to 0ow through the capillary.
2he tme required for the liquid to 0ow through the capillary was noted and the procedure
was repeated thrice.
>ow the mixture was drained and D4F polyvinyl alcohol soluton was 7lled in it.
2he tme of 0ow was noted as above, ta&ing three readings and the whole procedure was
repeated for three other concentratons.
D%2% %>%JK!,!
2o determine the !peci7c iscosity +()
sp
- we 7rst need to experimentally 7nd the value of constant )c).
2his can be easily done by caliberaton of the viscometer by pure water.
DL2L/M,>%2,M> M6 )$)
2he solvent in the diluton of the polyvinyl alcohol was water, whose intrinsic values are already
&nown,
iscosity of water +(
4
- * 4.DG@
Density of water ta&en +1
w
- * 4.NNO4OE
%verage tme ta&en for pure water to 0ow through the viscometer was obtained to be ;4O.;H
seconds.
"uPng the above values in Lquaton +,-, we get
4.4DG= * $ Q 4.NNO4OE Q ;4O.;O
*R $ * 4.44D4D units
$alculaton of ,ntrinsic viscosity '
Density of "MS soluton * ;.=g5ml
$oncentraton of the !toc& !oluton * 4.44D g5ml
$oncentraton +F- 2ime, t +sec- Mean 2ime +sec- () * $ Q 1 Q t (T
sp
*()3(
4
5(
4
@4 ;;N
;@4 ;;N ;.@@D=;D 4.H@HNG@
;;N
H4 ;H4
;H; ;H4 ;.HHE4D4 4.GOGH@O
;H4
G4 ;E@
;E= ;E@ ;.EGDNHH 4.D@4;@4
;E@
D4 ;ON
;OD ;OD ;.D=O=;G ;.;=;HEO
;OD
Plotng data points:
Fig.1 Plot % concentraton vs '
sp
,ntrinsic viscosity () * ,ntercept of the graph * 4.@HG@O
%L/%UL MMJL$IJ%/ M%!! $%J$IJ%2,M> '
Ising the value of intrinsic viscosity of "olyvinyl alcohol and already &nown set of values of )A) and
)a), determinaton of the Molecular weight of the polymer is performed.
A a

'
K

M
v
=
gm5mole
4.444@ 4.OG EO4=.=;
4.=4 4.E4 @@H4.ND
4.;H 4.G4 NNO.OD
2he values of viscosity average molecular weight obtained from the last two parameters are very
small. Sence they can be neglected.
2hus the value of viscosity average molecular mass is @NDH.GD g5mol.
/L!IJ2 '
2he viscosity of polyvinyl alcohol was calculated using Mswald viscometer and the value of
viscosity average molecular mass found out experimentally is @NDH.GD g5mol.