CHEMISTRY

Assignment
Home Work DPP

Polymer Chemistry

Syllabus: Basic Introduction – Definition

– Types
– Kinetics of Polymerisation
– Molar mass of polymer
– Why we study the average molar mass
– Different kind of masses
– M n , M  , M z ,M v and properties associated with these
– Methods of determining the molar mass
Polymer/Macromolecules:
A polymer consists of large number of simple monomeric strcutural units which are repeated over

CHEM ACADEMY
and over again to form a giant molecule called a macromolecule. Monomer units are joined with each other
through covalent bonds.
Classification of Polymers:
1. Synthetic Polymer
2. Biological/Natural polymers – proteins, polysaccharides
1. Synthetic Polymers: These are man-made and are of two kind (i) Additon polymer (ii) con-
densation polymer
(i) Addition Polymer : Formed by free radical chain mechanism
Generally formed by reaction between monomers having double bond.
During formation no-loss of simnple molecule e.g.,

Polythene  CH 2  CH 2  n

 CH 2  CH 
PVC  | 
 Cl  n

 CH 2  CH 
Polystyrene  | 
 C 6H 5  n

2. Condensation Polymers: These polymer are formed by the reaction between Difunctional
having two final gp or two reacting side. Monomers units with the elimination of small mol-
ecules like H2O or alcohol.

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 Nylon 6,6, Nylon-6, 10, Polyester, Terelene. These are formed by step growth mechanism.
ZnH 2O
n  NH 2  2   CH 2  6  NH 2   n  HOOC   CH 2  4  COOH   

H H O O
N (CH2) 6 N C (CH 2)4 CH
n
Nylon 6, 6

Homopolymer, Co-polymer and Block Polymer

Homopolymer Co-polymer Block-polymer
These are the polymer having These have two or more different These have two or more different
only one monomer unit as monomers as repeating unit. monomers as the repeating in
repeating unit ABBABABA alternate arrangement
AAAAAAAA AABBAABB

Head to Head Tail to Tail

or Polymer
(α,α) β,β
 
CH2 CH 2  may be asymmetric ;  always symmetric

 /
R
CHEM ACADEMY
   
H H H2
CH 2 C C CH 2 C CH
R R R R



   
H H2 H H2
CH 2 C C C C CH
R R R
Classification : As  -carbon are asymmetric above, also optically active or chiral. It results in
H
H2C C
Polymerchain
R
Optical Isomerism i.e., either monomer units is d or l, the spatial arrangement of ‘R’ depends upon
the manner in which d or l. Configuration are distributed in the molecular chain as the basis of d, l arrange-
ment polymer are classified as
1. Isotactic Polymers : all asymmetric carbon have same different configurations.

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 H H H H H H H
H H H H H H H H

H H R R H H H
R R R R R R R R
2. Atactic Polymers: Having random sequence of different configuration.

H H H H H
H H R H H H

H H H H H
R R H R R R
3. Syndiotactic Polymers: Polymer having regular alternation of different configuration.

H H H H
H R H R H

H H H H
R H R H R
Degree of Polymerization : The degree of polymerisation is the number of monomeric
polymerisation is the number of monomeric units in a polymer. It is represented by ‘P’.
M
P
m
m = molar mass of a monomeric unit

CHEM ACADEMY
P = number of monomeric unit
M = mass of polymer
M
M  pm ; P 
m

Q. CH2 CH 2 CH 2 CH 2 CH 2 CH 2
M = 84
m = 28
84
P 3
28

Why do we Study Average Mass :

A polymer consist of repeating units, chemically bonded in long chains and consists of molecule of
different molecular weight, so its molecular weight is expressed in terms of average molecular weight, e.g.,
when ethylene is taken into polymerisation then polyethylene have different chemical units of
 CH 2  CH 2 n .
n = number of monomer charge, which can change value from 1 to thousands in a sample. So
polymer sample can be assumed as a mixture of molecule of same chemical and different molecular unit.
So standard molecular weight is not a single value, so a polymer sample can therefore be assume as a
mixture of molecule of same chemical structure but of different molecular weight. So the molecular weight
of polymer is here expressed statistically and we determine the average molecular weight.
1. A few polymer like nucleic acid, moleic acid consist of molecule that does not vary, so they

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 have precise molecular weight.
2. All synthetic polymer are polydisperse (means they contain polymers chain of unequal length)
. Mn values are independent of molecular size and highly sensitive to small molecule present in
mixture.
1. Number Average : Number Average molecules value which correspond to chain length
average, called number average molecular weight.
Denoted by Mn
It can be measured using any technique that counts number of molecules or chains, i.e.,
(a) Osmometry – Vapor phase ; Membrane
(b) Depression in freezing point – Cryometry/Cryoscopy
(c) Elevation in b.p. – Ebullometry
(d) End group analysis

   min i Total weight

Mn    
N n  ni Number of maximum unit

M n have direct relationship with number and may also obtained by Rault technique. Most
of thermodynamic properties depends upon/related to number of particles and hence dependent
on M n .

.
CHEM ACADEMY
2. Weight Average: Weight average molecular weight correspond to size of polymer chain con-
tain within it.
This weight average is more dependent on number of long chains as compare to number aver-
age of long chains as compare to number average molecular weight, which depend on number
of each chain
n i m i2
M  as power - 2
n i M i
Hence 2nd moment average
. Bulk properties like viscosity and thickness related to M  .
It is determine by – light scattering photometry. It also describe the heavier chain in a poly-
mer mixture and elasticity.
. However Melt Elasticity is more closely related to third moment called z-average mo-
lecular weights M z

n i m i3
Mz 
n i M i2
The value of Mz can be determined by using either light scattering photometry or using ultra
centriguation i.e., sedimentation.
In heterogeneous sample : (Polydisperse) M z  M   M N

In homogeneous sample – (monodisperse) M z  M   M N as heterogenity  es and homogencity

 es , thre-3-wt. convert to each other..

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 All classical molecular weight technique requires dilute solution generally 0.01 g/ml, tominimize
solute interaction.
. Heterogenity of a polymer sample is generally described by polydispersity index. Polydispersity
index,
M
PDI 
Mn

For homogeneous PDI = 1 monodisperse M n  M 

For heterogenous PDI > 1 polydisperse M n  M 

. Some methods like as light scattering photometry and membrane osomometry are known as
absolute molecular methods, because we may determine the molecular weight of a polydispense
polymere.
. Methods like viscometry are not absolute molecular weight methods because they require
callibration. If we plot a graph between fraction of polymer chain vs mass ‘m’.

Mn
Mu discuss later

M
ni

CHEM ACADEMY M

To know the polymer property we must have a knowledge of both average molecular weight as well
as dispersivity, s polymer are generally poly disperse,

Narrower
Less polydispere

more polydisperse
ni

Methods of Determining the Molecular Weight:

Over all view - General technique for different molecular weights

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 Method Type of Molecular Weight Applicable Weight
Osnometry Number Mn 107  106
Vapour Phenomenon Osnometry Mn 4 × 104
Light Scattery M 0 to 
Electron and X-ray Microscope Mn/M/MZ 102 to 
Centrifugal and Sedimentation M 102 to 

1. Osmometry : It is the most probable technique to measure the Mn. In this technique a semi
permeable membrane is used, through which only solvent molecules are able to pass. The os-
motic pressure of a polymer solution with molar mass of polymer is given by Van’t hoff,
 RT  RT
  BC ;   BC
c M c M
These Methods is Better for Measuring Mn because: Osmotic changes are larger or compare to
other changes like elevation in b.p. dispression f.f. etc.

BC
——
RT

——
CRT

CHEM ACADEMY
C

 RT
  BC
C Mn
 1 BC
 
CRT M n RT
 RT
and also lim 
C 0 C m
The value of slope deepends upon ‘B’ which in twin depends on nature of solvent for good
solvent value of B is large, have P slope and for bad slope B is small.
good solvent

Poor solvent

B=0

B = 0 and  temperature at which polymer of high molecular weight get ppt.

Vapour Phase Osmometry : In this technique solvent and solution are placed in an insulated
chamber, closed to heart source, solvent molecule evaporated more rapidly then polymer molecule a
tempeature difference result, i.e., T , that is related to molarity of polymer, which can be determined if

RT 2M
heat of vaporisation per gram of solvent is known by using following relation T 
H 1000

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 In actual vapour phase osmometry elevation in tempeature is measured by using voltameter and
V K
relation between voltage and molecular weight is C  M  KBC
n

V KB
–—
C

——
Mn

K = Calibrium constant
C = Concentration
V  voltage
B = second virial coefficient
VISCOSITY METHOD
Different Types of Viscosities
Relative Viscosity : = Ratio viscosity of solution to that of solvent.

= n

CHEM ACADEMY 0

Specific Viscosity : Difference between relative viscosity and 1


 1
n0

Specific Viscosity
Reduced Viscosity :
Concentration


1
n0
 Reduced 
C
Intrinsic Viscosity or Limiting Viscosity Number : It is obtained by extrapolation of reduced
viscosity to zero cone.


1
n0
lim   Intrinsic
C0 C

Polymer solution generally consists of higher viscosity than pure solvent.

Intrinsic velocity related to viscosity average molecular weight by relation given by
Kuhn–Mark–Houwink

  K | M |a
a = 0.5 to 1

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K = characterstic constant of polymer solvent temperature
M = Molecular weight
ln  = lnk + alnM

ln a

lnK

ln[M]

Intrinsic velocity is temperature dependent and decreases as tempeature respectively.

LIGHT SCATTERING PHOTOMETRY
Measurement of light scattering is widely used approach for the determination of ‘ M  ’. This
technique is based on optical heterogenity of polymers solution, developed by debye, ace to him the
light is scattered equally and independent of angle of observer tq incoming light.
For large particles intensity of scattered light varies with the angle of observer to incoming light.
These scattered light follow Beers law,
zl
I = I 0e
Scattered Incident l = length

CHEM ACADEMY
Intensity

(z)-is measurement of decrease of incident beam intensity and is called turbidity of solution. The
turbidity is related to molecular weight by relation
HC 1
 1  2BC  CC 2 
Z M P
H = constant
P  scattering factor
B = virial constant
C = constant
For large molecule P  1
For dilute solution, C = small ; C2 = very small

HC
—— 2B
——
Z M

1
—
M

HC 1
 1  2  BC 
z M Pv

HC 1 2BC
 
z M M

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 SOME TERMS AND THEIR FORMULA’S
Contour Length [RC] : Length of polymer chain is measured along its backbone, from atom to
atom R C  Nl . Number of monomer unit = N, l = length of each monomer unit
Contour length is maximum end to end distance of polymer chain.
Root mean square end to end distance of chain

R rms  N1/2l
Mean end to end distance of chain
1/2
 8 
R  N1/2l
 3 
Most probable end to end distance
1/2
2
R mp    N1/2l
3
Radius of Gyration of polymer chain,
1/2
N 1
Rg    l= R rms
6 6

CHEM ACADEMY
Average end to end distance in unit of segment length is equal to
KINETICS OF POLYMORIZATION
N

Let us consider the polymerisation of monomer CH2 = CHX

Initiation : 1st step generate the free radical.

R
1 k
I 
Rate of form of free radical = k1[I] ...... (1)
Propagation : Free radical + monomer form polymeric monomer

R + CH 2 CHX R CH 2 CHX
CH2 CHX H
R CH 2 CH RCH2 C CH2 CH
X X X

R CH 2 CH2
n
X
 
2 k
R  M  RM

Rate of disappearance of monomer = K z [R] M  ..... (2)

d|M|
Radical disapparence of 
dt

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  
k3
Termination : R  R   RR

Rate of decomposition of radical = 2k3|R|2 apply SSA on  R 
Rate of form of R = Rate of decompose of R

K1[I]  2K 3[R  ] 2
 K1
[R]2  I
2K 3
 1/2
 K 
[R]   1   I1/2
 2K 3 
Using in (2)
1/2
dM  K 
  r  K2  1   I1/2  M 
dt  2K 3 
Kinetic chain length (KCL)
1/2
d | M | K  K1   I 1/2 | M |
2 
K.C.L. 
Rate of Product Form
 dt   2K 3 
Rate of Initiation K1  I  K1 | I |

CHEM ACADEMY

K.C.L  K 2 
2K
1
K 
 1 3 I 


1/2
|M|

1. The osmotic pressure (  ) of a polymer sample at different concentrations (c) was measured at
T(K). A plot of (  / c) versus c gave a straight line with slope (m) and intercept (c´). The number
average molecular weight of the polymer is (R = gas constant).
Rt c'
(a) (b) (c) RT (d) mRT
c' RT
2. There are several types of mean molar masses for polymer and they are dependent on experimental
methods like:
(1) Osmometry (2) Light scattering (3) Sedimentation.
Correct relation between mean molar masses and experimental method is:
(a) M n  (3), M w  (2), M z  (1) (b) M n  (2), M w  (3), M z  (1)

(c) M n  (1), M w  (2), M z  (3) (d) M n  (1), M w  (3), M z  (2)

3. During the addition polymerisation, the reaction proceeds via
(a) Step-growth process (b) Free-radical chain reaction
(c) Cascade process (d) Addition reaction

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4. The addition polymerization of M (monomer) involves the following stages:
(I = initiator, R = free radical)
k1 (initiation)
I  R
k2
R  M   RM
RM  M  RM 2 and so on
k
3 R  M  M  R
RM n  M n ' R  n n'

The rate constant for free radical formation is 2 × 10–3 s–1. The initial concentration of initiator is 10–
3
mol dm–3. The overall rate of the reaction is 4 × 10–3 mol dm–3 s–1. Assuming steady state approxi-
mation for free radical, the kinetic chain length is:
(a) 2000 (b) 8 × 109 (c) 20 (d) 200
5. A polymer sample has the following composition.
Number of molecules Molecular weight
10 1000
50 2000
40 4000
The polydispersity index (P.D.I.) of the polymer is
85000 85 850 729
(a) (b) (c) (d)
27 81 729 850

6. CHEM ACADEMY  
The number-average molar mass ( M n ) and weight-average molar mass ( M w ) of a polymer are
obtained respectively by
(a) Osmometry and light scattering measurements
(b) Osmometry and viscosity measurements
(c) Light scattering and sedimentation measurements
(d) Viscosity and light scattering measurements
7. The masses recorded when a substance is weighed 4 times are 15.8, 15.4, 15.6 and 16.0 mg. The
variance (square of the standard deviation) is closest to
(a) 0.02 (b) 0.05 (c) 0.10 (d) 0.20
8. Using standard equation for intrinsic viscosity [  ] = K M aV , for a solution of polymer and any
information from the graph identify viscosity average molar mass ( M ) [given that a = 0.5, K = 5 ×
10–5 L g–1]
0.055
  0 1
.
0 c
0.050
0 c 10
(a) 103 g/mol (b) 104 g/mol (c) 105 g/mol (d) 106 g/mol
9. In radical chain polymerization, the quantity given by the rate of monomer depletion, divided by
the rate of propagating radical formation is called
(a) Kinetic chain length (b) propagation efficiency
(c) propagation rate constant (d) polymerization time

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10. The fraction of groups condensed at time t in any stepwise condensation polymerization (overall
second order) reaction is
1 kt[A]0 1  kt[A]0
(a) 1  kt[A]0 (b) 1  kt[A] (c) 1  kt[A] (d) kt[A]0
0 0

11. A sample experiment revealed that PVC formed in the medium has M n  13 and M w  16 ,

where M n stands for the number average molar mass and M w for the weight average molar
mass. The variance of Mn will then be
(a) 39 (b) 3 (c) 1 (d) 87
12. For a polydispersed macromolecular colloid, osmometry gives
(a) Weight-average molecular weight (b) Number-average molecular weight
(c) Both weight-average and number average molecular weights
(d) Viscosity-average molecular weight
13. The average end-to-end distance of a random coil polymer 106 monomers (in units of segment
length) is
(a) 106 (b) 105 (c) 104 (d) 103

14. The correct expression for the product   M n · M w   [ M n and M w are the number-average and
weight average molar masses, respectively, of a polymer] is

15.
CHEM ACADEMY
(a) N 1i N i Mi (b) N 1i Ni Mi2 (c) N /  N i M i
i i
2
(d) N /  N i Mi

The condensation of a hydroxy acid produces a polyster with the probability of linkage at both ends
being p. The mole fraction of k-merchain formation is
(a) pk (b) p(1 – p)k – 1 (c) pk – 1 (1 – p) (d) pk–1
16. A protein sample consists of an equimolar mixture of ribonuclease (molar mass = 13.7 kg mol–1)
hemoglobin (molar mass = 15.5 kg mol–1) and myoglobin (molar mass = 17.2 kg mol–1). The state-
ment that is true about the weight – average molar mass  M w  , the number – average molar mass

 M  and the poly dispersity index (PDI) for this sample is

n

(a) M w  M n  15.5 kg mol 1 and PDI  1 (b) M w  M n  15.5 kg mol 1 and PDI  1

(c) M w  15.5 kg mol1  M n and PDI  1 (d) M w  15.5 kg mol1  M n and PDI  1
17. Consider the statements
(i) Most thermodynamic properties are dependent of Mn
(ii) For hetrogeneous molecular weight system Mw > Mn > Mz
(iii) Bulk properties like as Viscocity and toughness is closely associated with Mv
The correct statement above are
(i) i (b) ii (c) i, ii (d) i, iii
18. Consider the statements
(i) The ratio Mn / Mw is called the polydispersity index
(ii) Boiling point elevation and end group analysis method may be used to determine the number

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 average molecular weight.
(iii) Polymer never have precise molecular weight they have always average molecular weight.
The correct statements above are
(a) i (b) ii (c) i, ii (d) i, iii
19. Consider the statements
(i) Melt elasticity is more closely related with third moment knwon as z average molecular weight
M
(ii) Kuhn – Mark – Howink – Sakurda equation give a relation between intrinsic viscocity and
molecular weight [M]
(iii) The measurement of light scattering the most widely used approach for determination of M
The correct statements above are
(a) i (b) ii (c) i, ii (d) i, iii
20. The intrinsic viscocity depends upon the molar mass as [] = KMv for a solution of polymer and
any information from the graphy identify the viscocity average molar mass Mv
[Given that a = 0.5 K = 5 × 10–3]
(a) 103 gm /mole (b) 104 gm /mole (c) 105 gm /mole (d) 106 gm /mole
21. Kuhn – Mark – Howink – Sakurda equation is used for the determination of
(a) number – average molar (b) weight – average molar mass
(c) viscosity – average molar mass (d) z – average molar mass
22.
CHEM ACADEMY
For ortho hydrogen the nuclear wavefunction and rotational quanum number respectively are
(a) Antisymmetric and even (b) symmetric and odd
(c) symmetric and even (d) antisymmetric and odd
23. A plot of osmotic pressure against concentration (gL–1) of a polymer is constructed. The slope of the
plot
(a) increases with increase in temperature
(b) increases with increase in molar mass of the polymer
(c) decreaes with decrease in concentration of the polymer
(d) decreses with increase in temperature
24. A common characteristic of conducting polymers, such as polypyrrole and polythiophene, which
make them conduct electricity is
(a) The presence of stereogenic centers of the same configuration
(b) A monodisperse distribution in molecular weight
(c) Conjugation throughout the polymer chain
(d) A very low glass transition temperature.

ANSWER KEY
1. b 2. c 3. b 4. a 5. c 6. a 7. b
8. d 9. a 10. c 11. a 12. b 13. d 14. b
15. c 16. a 17. 18. 19. 20. 21.
22. 23. a 24. c

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