UNTT-3 Detercmincutiog of Moleeulout hleight

of polymets

Meleculne hle ight

QUt complex gant moletules hovina
Pelymens
o bnanehuol chuig
tor Chouin
molbeules ane
aue helol fogether
togethen
These Chauys of polymert
of polymt
o fero Hhe bulk quanthy
be oletercmine
moleculcut tueighl of simple caun
The
be chanoR os is does nel
oncl neve
experti menfelly
qnLoueth Ouymone

of poly nnet molo oules, as hemonOmens one

h CoL Se
moeculan meuss net defintte on
heio
hopeofeol
pecmontnt.

depenals s the moeculon

of polymen
The prueperttiet
mass ye polymer
Propenties
Moboulou
Polymert Bright matertiel negigible
l0,000
Po lyehene mechandCel Shonoth

2S, 000 tt become hand Shoney

glousay PloSfic

easiy preciptleukes out

Mli on conveleol
of tHs SoL",
to ibetous
 Moloeulon hleiqhl
Numbeie Avenae
tu lad tueiqbhl nepmosennl och..
acfua
wencoye molo
he no.
Sample
devieleol he arl
by the achual
ttcight ef polyme i
pnosen t
nitmhenfmeltoular

pOug ner fa mple t

n no. of molecules
0 a
Men
let ma ss.
mo leculal
Hhenumbet average

}NNi
Mn Ni

moletules havi.
no. ofpolymert
this
+his Sample N
In have Ma mole
culan tul

meleculart
Cul M)6 N
So 0n. N-Molecules

N
N N N
NI
M M
M Mg My M Mi

AM NgMg NuMy NM NM
N,M

N,M+N,M2+N3Mgt - . NiM
Mn N+N2t Nat t NE

NEM

znlt
 hWeieht AvexageMoleculaut Mass
Lhis methnol He moletlau uoigbhl of eouch moloeulou
spectes Cuhich is ulttpbe( by s confrci butlon to

the dotal moleuulout euteight f oll he pAodu.ct So

ebfaineol ane aololeol do 9et ueetghit auvenane moleuler

tuteigit.
Now fetal ueight o polpmer = NË Mi

letght of macfion-1 NM,

ofnaclton-1 NËMA
hletght naefio) 2Ni Mi

Melecula umètght contretbuhton of haotton-1

NEMxM NiMi
NeMi_xM, - NM
NM

Similaunlu,
The
The meleeulon tig ht confribuhon by the

othert tracfion tuill be NaM NaM

Enli Mi nlamgi
Thus the
the tutegTt CUveraoe mebulon ceeioyht cuhele
N,M
pelym t e Mw NM
ENE M ENi Mi

ENEM
Mw ENi M
ef a polymt
The cneight averncuye uelght
noleeulan
seelimunerdalion
utill be dlelenmined by lightSCotterct noy,
equilibrcium viscoset measnenent dependls on
ounol dlependlt on
he polymer i) given salufion he
tueight
Polymert
 is mou polyelitpenaty
The ratlho of Mw/Mg os

thde
PDT he the polyment is men0 -oispexs
lhen
hWhen
kinds af mon0mens auith
& consist of SLme
e
and stze.
equo tuteigint
have PDT
PDI ,On the
,O0
narturtal polymens
jenertolley
the
th PDI+I
PDI 1 the
he Syn-Hhette polymea
Ovtihert hand ehe-polyape
te be poly~clitpen.
i soid
Censtst-f

Moleculot unelgbht fpolymer

etereminotio of
Metheel
by he viscosty
d dhé uauid uhich
Viscosity is the prrepertthes ertces t'e, when
ottrroctive
intermoleulorr
clepenels iy
ittractve foAceR
tnuROA
te
he nlertmeletulorc

ef lquiod cneases
viseoset
The
The tnlercmelorulart outtroetiveontec neloule uesdh he
meleculourt mass
ü le
We kneuo hot viseesit the pu selvent
f

thot 8 poyme Sol

Hho
thou
sohent ), unol the
Let he thrse viscosidy of pur

visces y of solutton of polymen .

The rolali ve visteset r o to

CLehenei Time to #louw 8 een volume df tautid

to Time to flow f pun Solvent of Sam

volurma.
 Beri gpecei fic viscestty TI
0rc2Dsp
nlow nColuce specitie viscostty *he roufio of speci

yiscosthy to the contenoution df he sol" e inkent

viseosthy ntolutceo ecitic viscosihy p

2 399
oe4tone c concenttofioo dhe solukibn á
2032
ThHS
THS nuoluc eol specifec visceshy reloukeo tuuivh hhoie
viseosify
The nheciend viscost n
C

fo dihuteol polymen sof", whon C-01

1-pt
Li in e Lisp
C

Henl m] kno as mdrensie viseosity

The tnenste viscost [n] ceun be obBauntol ky plotiy

bet" Dsplc n ap/c concenttouion d tpe
a gyrarphh on

SoR

An sple
P

m /mu)
 do
do tha
th
The hirnsre viteosrHy i intedly propnttonsul
molecular tutelgt cof dhe polymed
mothomati taly
The tralauffon eon be epuRO
Sep
km

lepencls on the polyme

lheae k aue centlant
of the solvent sysem.
bel"
oelenmineol by plottire
o qnaph
Ths
Ths co be

n huansec vistosiy vsmeleculan uesah

3
eyc
loheMane
(30'
-Isobuylee (20k)

(an)

Moleeulaiu,

th Velue of x thoun
orlesdpolynen
Fon tecundem
Soluent. gencrclly fo
0.rto fon otven
from
Xles bet" 0.6.to 0.y.
mcuny soP) sygten o
ef polymen by
petertminaien of Moleculovn MoJ

ovol
Osmotie pHRSSLLNOmethio vey acetutale 9r
Senstli've to olefercmine Hhe moleculou masA ofmaco
mo
etules .

> H is useol to clokermine he møhoulou mouy of polyn

oe do folouung noson
 subsfenee have a OSmotte
t iah moleeuloue tuueroht
to
to mok maoJuU
tonvinient
thch
pessene

fropartotfton of seme -petmeouole meorto

v eDLY Ho0n

polmer mole cules.

Lanoen

WPa

solven
Solufio0

Semt- perum@cuble
membrtou

Let us take puuLe solvent oindl o polymed so i a

Centeune as Sheutn u he oliajrtau tuhich oue

Soponoble by o Semi-petmtole membrtoLne

D u to this eSmosis the pos men soen gjeft cl tutel

oLs o rsult the Liagurel levels th the soL sete
tixneoLSes tn s s Umb .

he metase bentnopy of the syglem bs oliluuton

conkercss wittt caunfencolby the thcCa ge in
PHOSSu heoo
A t this peint he chemitoul poleretiol b the saume y boh

the ehoumbens
The pr Syuute oli44encnee inebcateol bs the leels of the
0Smotic phekunt .
2 kimbs ytvies m
 Lef he oSmo lè prosgund f selufiog = n

Mele hactioy of sovent mole thothoy df solenl

X2. mole hoclion ofhe polymen,

Hye osmeRe pnesun

fon egte tlibrniam fthe chonta
SThene concliog emotiem
Osmoie menbran
of Sohent on
bolh slole
pokential
hepnesenleol

Whe : aotiity Codhcient

molat volame o he $ohent
Vdntia)

fort eveuy diuut SN I anol V

volume df purl sohvent

hhene Panftal mo lan

rs X A2

Puting he vole f x, t e O

TV+RT n -) 0
T RTn l1-32)

-RT(,t 5)-
The mole haoflov) of a
pety mex (¥») y ) the SeL
owing conoerthadion c, Con be bleuineol
c/M

cm c
Hon elilue sof" x,, M
Now purtlong he value ef * ) ea"

-RT /.
T RTX
1 )

wlhich i the vitia pAC ron f he ofon

gT1,t +A
A M
RT( cA
M
.) M

pT t Bc +Ba c4...)

lnlhene B, B3 MAa
Vircal
aAL celltosecond
Hhineol
Whet B, B vet hoff e)
and he above ea knouty as

eeeffictent
GSmotie phoune
as OGluced
kn0usn en 33
af his e" ael he guaph
eglect he znd teru-
H ue

Rlc C, give a shaight line

plo Heol y oking Cz0
Dne b ha -plotlin uho
Cuol he shaight
Lne become RT/M
tntenseet of the shoiht
The
 Rle RT /M

So )

Thus fro) he
Thus tnketcept eue Can eosely caltulole
moleeulou maß te) 4.
he Valte of

The no awena ge meleCuln mas Con be maneol

OS mehe peheune he osm9H pulun

becaute
ehr'ch olopenols en the no. af
colligcelte propetdies
molecules afhe polymet ngt on theio ma26

All the molecules make equal Contribufion owanls

uehe khea 4hey aue keqtta) hea
the omotic p
s$unt
he
on Lihht

We know that smotte pounl Congsts

acoli ively of the panfial paiyuutA
of ikont
on the meletules
7h1-
ol euee f polymeni zoton 3

2 , + 7 tA3 t

CRT C2RT 3
M, M M
Lehee C2 C 2t(2t-

'Mpcm ohie
Mosmoie Aveno- mole cbert tvouss f dthe polymll
 t e C RTt GPT+GPT

le
ct G,t Cg PT

Mos mohice

Tetercmination of Meleculan Mauss by ight

Stertenine Methool: o

When a bêum ef ttght posseol thrteugh a colloceloul

soluthon 4 saffers scotferting uehich i lernoutn as
tynololl efteet.

Accortolt'ny to the Rayleigh heony t C moncitomaotic

Light i pusseol thaough a Cohfion havtng pandice
Seze aboul 10 iR& mone han the wawe enqth

hen the nelio f intesihy of Scoctoig

inciclent Light
Ughf (Te)+o dhe tndensehy ef ncident bighf (T»)

nte)-
hlhene : thole o Soutfenire
the
obseRVeR hom the Sample
s t e n c e of
g
Scotteninoj paniCle pen cnit volemetron)
a no. of
of he partttcle
dElectnicoul polctnulTotbt lty

A= lalouve enoyth ofhe Liopht

 tis obserue thot l t e Ught iScotle moue as

compant o neol tight Lecaust Hae lighl i

Rszx kert Shulten utove leno)tth hon the neol lighl

The incident tighi tnchiceo vbrtoting ollpolesi

andhis panticle dhe naolicle light
the pantrcle
ag sounre of Dght
ll ond behaves
t) dinec-hon

The poanticle having neaen vealie vibrain

of vibrtafney

powe.
have mont polartizing
olipoles

The
The polantty f scaterine patfielRo a meaSu
oP Specifrc niho.ctton te, UhocHo pen unit

volume cuhich olependls en nehaefive index

n2+2

n: Rehactive Drclet

Ass uming n 1
, n 293

nefnaofie mdex
Aee oncling to Toylex's Sontes he
corpenhotto
be coulcalorheol hon #s
con
hent Reshaclve melex of pune se lvent
o
he polymo s0 hauine
Refhoclve noler f
Concenhoufio) C.

boh stcles nelecino he ouy

New ee Sqttaning o
dnletc hoving highe pouen

n n+2no

n2- n: 2no
c
pen tuntt volutne
NOW a= no. of Sccutfenina) pcenicle

CNA
Mw
No.
lot: Hvoe ads
molaumass
of aenepe
nlei'ght
Mw

Nou -do

zno(
27N
Mw
toure hane
By naoyleeting

4 Na)
 vezlite o t e"
By puttie he
Sna (14 cos'e)

nEtoldle)iGacoio)
M NA

an*no /14Coste(Mw)
N

C N Mw Mw N
To
To Na

T tt 27 2n0
1ceg MW C
NaX

2xnnl-te)
Luwhuek

X
t
1HDs2

Thi e, toun be delenine tthe moleoule mouy

eou
he polym

Reanncngmnt ep) to make appt'ecoeble

Pnihe co menanauion.
 KC
Ro0
be neyligible.
since q0 t Cos' Can

he solute b
to Einseuo Debye if
Accentcliney he sol n no ligh
disdhiburleol hnough dut,
einitotm ly
Scatervcol by tis solution

oltse do Ae
The conclHton df the solutton #luuchuoutes
(Cnolom brtotunto moticn 00ch xtend Flhuchuatiny
fhichatig

invetslj prepot-dioncul te the smertic pnesULAC T atevelopeol

by diFlenence comendeoetin.

Rop
CTMR
RT

CRT
Ho tcleol Sop

n nc-fenes Jo 6Smplit presgunt Avircial eo-efAtient

RT
l c 4%+ Ai c )
Ke
Pau Mw

kc +2A2 t3Atc
Rap M M
 Forc a oltlufe polyolispense yshe ho aboue oqn

eon e ttonfen a

C
Pap Mw

In
1n genenall cC -2 (B )e
Mw
Cehene 8 : consdernt

hl
ul hon
hen 9raph à ploted i bef" kc/r,0 V
geves a Shrtaiohf tine tue1ve slope lencep

This pecmi he olo-tertminestt on uueight

Mw
awenage moleoulotue1gt Can be Conleuloiteol

GLASS TRANSTTTON TEMPERTURE

AND
TTS TDETERMI NATION
=0= -0=

epenou ng a annengement of polymen molbeulet

the polymoHR Ce Chstellli'ne onol amDnpheus.

hlhenthe Semi-cusfeulltne polymert er amerpheus

polymen on. hcotinoy ehonges trO glou y slocte

to ruubbenp o visco eloushe folte and en huthe
hettng t chounees to viscous #lurde sfoute.

Glassey Sfade A bbeny lo)

Vteo
visco-ela sle la
olymer Shecte
Sdode
 e Hempercotttne be low uhlch p olymen à houtol
honol ouno
Cn

obove at hich t so#4 àtollad gylous -nansion

empencfune
The honel cnol brtiHle &eLhe f polymexu krjout os
o tossycehe ncl he set flextble sheuhe kyoutn as
rLLbbeny t viscoelashe slele

n unthen hecuéina he polymen bec emes highly viscous

thaute and slani #low

The glouss huanstHoempengtut à prepeny amephus

noien f i pely med, uhaut as he cngsalliye nogion
ef the poyme chanat-hen tzeo b melting pomt
Aetorcoling do hermeclinoLunu e glo atn 3t-#on empenakune
ane oloscru'beol a4 tond erolen brangitioy.
The gloss nansron empenoefauce elopenol n athnaedive
fovcces ihe polymen melectde

recHores Aec-line he Glass hansehbg Tempenokuta

he glass tnonstho HempenCeHtt cepenclt on he mohity
of poly mecle chouy
Cuno lexi brl ty

move ecstl hen he gla

h e polymert choug toin
at lowen omp
&eele to be cen veLleolo nubbeni seute
On the othen hano fthe mobibty of polymert Choui
Rehicteol hen he glous ransitog temperodtune
high.

The
Thetec-lont tuthith affee tnm he qla ransilen emp.
QL OLS elloo
TnHercmoleculauc forcoes

poly me
amprg dhe p0l/
-ertmoleeulonHortces me c
choig
h
Strten
henhe polymerthowe hige
veuu ga ransèdtd

Aemp
E Ta o PVc(8o'c) hieyhe thenTaf
inlenmoleculan
) due to Shroren
Polypropy lee -19'c
onces
Chai SHnes
suth as amide canbory
In pMosenee os-H7Yentno gneup
t the polymer Choug. tuthiCh, con
AOoluces he mot y
thoin flexibil't, os a roult tk qloun +rounttio
Ouno

empenaeluut hishea
3 Crossünking
The Cnoss Unks bet" he choui nosrict +the roteution

me-fton as nesult he glous troun&tdton tempexoufug

thcroases.
Geometalc Factens
yeometruc faterns Suchype of Symmetrty f the
back bone t the prosence of olouble bono ana th
moin chou
The polyme tuehich haue Symmehuicol Sfuctune ad Cower
Ty ha
Hhon hose eaith aocymnelricoad uc-kung
ole
yPenelent Gnoup
The pnetente ef penplent 9nnup enn changehe glas

-hansHio0) lempenaufuuo
The pluue noe ot bulky penolont quo up such a benOne nine

Con noshuiet no-leclonoul huccolo leooling o highe oylus

htounsion dempenaluo.
6Pleshiccizeds
Plo&ticizerns ane tow meleculan uueight anol nog- volutile
mactocials cololoo o polyme to ncntale heln ehouu
leui belihy as asult the glast anshon -lonp, Ta
inCnOLLSes.

y Moleculon" nledahelo
he qlog antto)-empencchud clso afecteot b
Hhe moeculou tuueighet of polymerl

lnlh en the moletuloux mas polymon incnco ses the

qlous hun&iten tempenotunt olso menaje.

Accorclg0Fo-Florzy e
pe Mn
etmeen
Tpe is the gluss ncnsMis) femperacfut act mo kiulan
Tolo
uLeigbt f tntinp onolk he Cmpircucal pouametet

Cuthieh reloteed fo the htt voluue instolethe polymer..

 Re latenship Betuteen Gleass hocnsiion empexoeluni
) and mettinq peint
1t is cbset becl hou the tacdon uuhith operl
it oulso affe o
glosstanstyhay empencetuno 7,
melking enpenahantTn

The Vcllue Tmancl T anc Cou be ttert ne loa fegd

Fon symmetnical polymed Tm2

Fon unsymmltltl poumek T,nI:Tg
devicuffon
obsertb many polymeng
But oluue o Some

neu neloHon eseubtsh e t20

To.6.
Thonsthio) and Henjuncment f
Theorttes fGqlou
Cloess TrccmSt-ton Temperaue-

fnelamentel
naittne -
qlouss hounsHon i a
df
The
tushich tnvoves eyeiltbtitunm, dhermeoleyranie
Comple process
ano kinetie factons.

hes base on entnoPy

soThe
The henmglppamie oppxoe
slafeuhile kinette thesup
constclexectb) of qlany
censtlens he nelotaction
f lass nonseliten
assoctaheotidh oL.aus hansiHen.
phenpnenon

uehieh mosd useAl Onal pepaleun

hee volume heouy
The noLnSthon
eplaug qlos
con
 Fnee Voltumeleoy s
FiLee vo litme theouy /toolel exploin by on onel Fexny
his theo r co ns toler the noe volume y of a Subtance

osthe diffenenee beto0e0n- tts spe ci#ic volume Vanol

9peLce octually oCepteol bthe moletule V te

hee volLume V-V

The volume OCeupteol by the moletule t

VoVtdaT
vVolume ef he glouss oat absoluhe zend
tempenottne

C henmal expne Hion co-efHicient t h e glaut

This moolel unthea detine he hee volutme hocthon

F al qeven empeloefuuce 7

ffq1ol IT-T)h o
ree volume Fnacfion at T
Wlhent fa

ofTheumol epansten co--fticien above T

hertmol eupansion cO-ef

frerent below T

Fo mas ambuphous poly mes the hee vo lume

hat/pen
Q qlou nounstHe) kenpEnaul hounol to be coad
vant
0.02j. ru 3a

Onc a babsul
s
 The cemourtp houe polymens tueheeooled ane
up
to become glassy tua hen the zheo volume hondion

atleins his volume

Wiltien lounolel - Fentiy Equadion

WLF Equoehen
hLF ea" ban empertCoue agsociodeof usth

hime, empenpelunt, supenposiHio

he 1allT egn

-C (T-Teg)
Ct (T-Thon)

his en ueod opucolit icoelousthc pnopentie

o polymer al oull dempencetun.e

This mcons hol ou these propenties Con be

THof
mutlteplieel
ate
by at)oy
T

hWhenetT ill be Hime tak Horopnopenty

o ntoch o cettet kovel Hhot the tuwwves tounspond
masto curte
One
ehene T
empencutLML Cunpl nferonce
Hempercritnt Choosen to construCt}e mousten cune

C C a n l empirufco ConsBant adjusteol tort he

SLpercpoSttion poucUme-fer d.
voLlu
The ineartres hlLF e4"

Cat (T-Ther)
leqiet)
C2
loq dT) CT-Thep

1 naph i plet be ipele) Ve T-Tny

ate cc en-ho GlG, em the nesultinoj slope
ano 1/c Fruom the point f tndenseet i pnessune

for glassy motlercictls if e blowe tho the oy lass

doro Manstion
WLF Can only be usedto pHeclict tahad ueill hoppen belobw
the qlass nonsttton. Onee C9
fon lowen
an bterine 7)
empenoutu Can be phedicleol.