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Polymer Physics

M. Rubinstein, Ralph H. Colby

Chapter 1

Introduction - all with Video Answers

Educators


Chapter Questions

02:09

Problem 1

Consider a 'true macromolecule' - a chunk of polybutadiene network of mass 100 g . How many monomers all covalently bonded together does it contain if the molar mass of a monomer is $M_{\text {mon }}=54 \mathrm{~g} \mathrm{~mol}^{-1}$ ? What is the molar mass of this macromolecule?

Arpit Gupta
Arpit Gupta
Numerade Educator
02:50

Problem 2

If two different monomers A and B prefer to react with each other than react with their own kind, explain how you would synthesize the following copolymers:
(i) alternating copolymer
(ii) diblock copolymer
(iii) triblock copolymer

Ameer Said
Ameer Said
Numerade Educator
01:08

Problem 3

Consider a dense globule of polyethylene with molar mass $M=10^6 \mathrm{~g} \mathrm{~mol}^{-1}$ in a non-solvent. What is the radius of the globule if the density inside the globule is $\rho=0.784 \mathrm{~g} \mathrm{~cm}^{-3}$ ?

Stephen Ho
Stephen Ho
Numerade Educator
03:25

Problem 4

Consider an ideal polyethylene chain with molar mass $M=10^6 \mathrm{~g} \mathrm{~mol}^{-1}$. Its mean-square end-to-end distance is given by

$$
\left\langle R^2\right\rangle=C b^2 N
$$

where the monomer length is $b=2.5 \dot{\AA}$ and the coefficient $C=5.5$. Estimate its root-mean-square end-to-end distance $\sqrt{\left\langle R^2\right\rangle}$ if the molar mass of the monomer is $M_{\text {mon }}=28 \mathrm{~g} \mathrm{~mol}^{-1}$.

Ameer Said
Ameer Said
Numerade Educator
01:14

Problem 5

What is the maximum length

$$
R_{\max }=b N
$$

of a polyethylene chain with molar mass $M=10^6 \mathrm{~g} \mathrm{~mol}^{-1}$ and monomer length $b=2.5 \dot{\mathrm{~A}}$ ?

Manik Pulyani
Manik Pulyani
Numerade Educator

Problem 6

Calculate the fractal dimension of the Koch curve in Fig. 1.27 with the center third of each segment replaced by three sides of a square (instead of two sides of a triangle as discussed in Section 1.4).

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04:39

Problem 7

Determine the fractal dimension of a Sierpinski carpet (see Fig. 1.28), constructed by dividing solid squares into $3 \times 3$ arrays and removing their centers.

Lucas Gagne
Lucas Gagne
Numerade Educator
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Problem 8

Calculate the fractal dimension of a Menger sponge (see Fig. 1.29), a threedimensional version of the Sierpinski carpet. A solid cube is divided into $3 \times 3 \times 3$ cubes and the body-center cube along with the six face-center cubes are removed. The same procedure is repeated for each of the remaining 20 cubes, etc.

Victor Salazar
Victor Salazar
Numerade Educator
01:14

Problem 9

A polymer in a melt is in its ideal state, which is a fractal with fractal dimension $\mathcal{D}=2$. Consider two such chains, a longer one with degree of polymerization $N_1=1000$ and a shorter one with degree of polymerization $N_2=250$. What is the ratio of their sizes $R_1 / R_2$ ?

Manik Pulyani
Manik Pulyani
Numerade Educator
01:14

Problem 10

A linear polymer in a good solvent is a fractal with fractal dimension $\mathcal{D} \cong 1.7$. What fraction of a chain has size (average distance between its two end monomers) equal to half of the average distance between two ends of the whole chain?

Manik Pulyani
Manik Pulyani
Numerade Educator

Problem 11

An ideal randomly branched polymer is a fractal object with fractal dimension $\mathcal{D}=4$. In Chapter 6 , we will learn how this polymer can fit into three-dimensional space. What is the ratio of molar masses $M_1 / M_2$ of two ideal randomly branched polymers if the ratio of their sizes is $R_1 / R_2=3$ ?

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04:27

Problem 12

In Chapter 3, we will learn that a linear polymer confined to an air-water interface is a fractal object with fractal dimension $\mathcal{D}=4 / 3$. What is the ratio of sizes $R_1 / R_2$ of two linear polymers at the air-water interface it the ratio of their molar masses is $M_1 / M_2=16$ ?

Sana Riaz
Sana Riaz
Numerade Educator

Problem 13

Give additional examples of: (i) regular fractals; (ii) fractals in nature.

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00:36

Problem 14

The density of a 1,4 -polybutadiene melt at 298 K is $\rho=0.895 \mathrm{~g} \mathrm{~cm}^{-3}$. What is the monomer volume $v_{\text {mon, }}$ if the mass of the monomer is $M_{\text {mon }}=54 \mathrm{~g} \mathrm{~mol}^{-1}$ ?

Ronald Prasad
Ronald Prasad
Numerade Educator

Problem 15

Consider a polystyrene solution with concentration $c=\lg \mathrm{L}^{-1}$ in a solvent with density $\rho=0.9 \mathrm{~g} \mathrm{~cm}^{-3}$. Estimate the volume of a polystyrene monomer in this solution if the density of bulk polystyrene is $\rho=1 \mathrm{~g} \mathrm{~cm}^{-3}$ and the mass of the monomer is $M_{\text {mon }}=104 \mathrm{gmol}^{-1}$. What is the volume fraction of polystyrene in this solution?

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06:39

Problem 16

What is the volume fraction of $1 \mathrm{mg} \mathrm{mL}^{-1}$ poly(vinyl chloride) in solution if the volume of each monomer is $v_{\text {mon }}=75 \AA^3$ and the molar mass of each monomer is $M_{\text {mon }}=62 \mathrm{~g} \mathrm{~mol}^{-1}$ ?

Yongyao Zhou
Yongyao Zhou
Numerade Educator

Problem 17

Calculate the overlap volume fraction $\phi^*$ of a polymer with degree of polymerization $N=10^4$ and monomer volume $v_{\text {mon }}=100 \AA^3$, if its pervaded volume is a sphere with radius $200 \dot{\mathrm{~A}}$.

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Problem 18

Consider a solution of rod polymers with degree of polymerization $N=100$ and end-to-end distance $L=N b$ with monomer length $b=5.5 \AA$ and monomer mass $M_{\text {mon }}=75 \mathrm{gmol}^{-1}$.
(i) What is the pervaded volume of this polymer?
(ii) Is a solution with concentration $10^{-3} \mathrm{~g} \mathrm{~cm}^{-3}$ dilute or semidilute?

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Problem 19

Consider a polymer solution with degree of polymerization $N=500$, volume fraction $\phi=10^{-2}$, monomer volume $v_{\text {mon }}=90 \hat{\mathrm{~A}}^3$ and pervaded volume $10^4 \mathrm{~nm}^3$. What is the overlap parameter $P$ of this solution?

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Problem 20

Consider a 10 mL solution obtained by mixing 20 mg of dry polymer with solvent. The bulk density of the dry polymer is $\rho=0.8 \mathrm{~g} \mathrm{~cm}^{-3}$. What is the volume fraction of polymer in this solution? Assume no change of volume upon mixing.

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Problem 21

A polymer with molar mass $M=10^5 \mathrm{~g} \mathrm{~mol}^{-1}$ is at overlap in a solution with concentration $c^*=1.67 \times 10^{-2} \mathrm{~g} \mathrm{~cm}^{-3}$. What is the pervaded volume $V$ of each polymer chain?

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01:14

Problem 22

Estimate the overlap parameter $P$ for polymers with fractal dimension $D$ in the melt $(\phi=1)$ if the degree of polymerization is $N$. Estimate the overlap parameter for an ideal chain (with $D=2$ ) in a melt with $N=10^4$ monomer segments.

Manik Pulyani
Manik Pulyani
Numerade Educator
00:36

Problem 23

Consider five textbooks from the polymer bookshelf; by P. J. Flory consisting of 672 pages, by P. G. de Gennes consisting of 324 pages, by M. Doi and S. F. Edwards consisting of 391 pages, by A. Yu. Grosberg and A. R. Khokhlov consisting of 350 pages and by J. des Cloizeaux and G. Jannink consisting of 896 pages.
(i) What is the number-average number of pages per textbook?
(ii) What is the weight-average number of pages per textbook?
(iii) What is the polydispersity index?

Mishal Gul
Mishal Gul
Numerade Educator
03:58

Problem 24

Science Fiction: Three Planets.
(i) On the planet Demos, all major decisions are made by votes of all inhabitants. All votes are counted with equal weight. What kind of average decision is achieved on the planet Demos?
(ii) On the planet Fatos all major decisions are also made by votes of all inhabitants. Votes on Fatos are counted proportional to the weight of the corresponding inhabitant. What kind of average decision is achieved by this weighted voting on the planet Fatos?
(iii) On the planet Thinos all major decisions are also made by votes of all inhabitants. Votes on Thinos are counted inversely proportional to the weight of the corresponding inhabitant. What kind of average decision is achieved by this weighted voting on the planet Thinos?

Jennifer Stoner
Jennifer Stoner
Numerade Educator
11:05

Problem 25

Consider a system consisting of one elephant with mass $M_1=10^4 \mathrm{~kg}$ and nine mosquitoes riding on its back with mass $M_2=0.1 \mathrm{~g}$ each.
(i) Calculate the number-average molar mass $M_n$ of this system.
(ii) Calculate the weight-average molar mass $M_{\mathrm{w}}$ of this system.
(iii) Calculate the polydispersity index of this system.
(iv) Which average is appropriate for calculating the damage to your Land Rover in a collision with this system?

Susan Hallstrom
Susan Hallstrom
Numerade Educator
01:47

Problem 26

Consider the following distribution of polymer chains:

10 chains with degree of polymerization 100
100 chains with degree of polymerization 1000
10 chains with degree of polymerization 10000
(i) Calculate the number-average degree of polymerization $N_{\mathrm{n}}$ of this distribution.
(ii) What is the weight-average degree of polymerization $N_w$ of this distribution?
(iii) What is the polydispersity index of this distribution?

Crystal Wang
Crystal Wang
Numerade Educator
02:26

Problem 27

Consider a blend obtained by mixing 1 g of a polymer with molar mass $M_{\mathrm{A}}=1 \times 10^5 \mathrm{~g} \mathrm{~mol}^{-1}$ and 2 g of the same type of polymer with molar mass $M_{\mathrm{B}}=2 \times 10^5 \mathrm{~g} \mathrm{~mol}^{-1}$.
(i) Calculate the number-average molar mass $M_{\mathrm{n}}$ of this blend.
(ii) What is the weight-average molar mass $M_w$ of this blend?
(iii) What is the polydispersity index of this polymer blend?

Kratika Bhadauria
Kratika Bhadauria
Numerade Educator
02:26

Problem 28

A protein sample consists of $80 \%$ by weight material with $M=$ $5 \times 10^4 \mathrm{~g} \mathrm{~mol}^{-1}$ and $20 \%$ by weight of dimer with molar mass $10^5 \mathrm{~g} \mathrm{~mol}^{-1}$. Calculate $M_{\mathrm{n}}, M_{\mathrm{w}}$, and polydispersity index.

Kratika Bhadauria
Kratika Bhadauria
Numerade Educator
01:02

Problem 29

(i) Is it possible for a number fraction $n_N$ of a chain of $N$ monomers to be larger than the weight fraction $w_N$ of this species? What can you state about the molar mass $M_N$ of this species?
(ii) Is it possible for a number fraction $n_N$ of a chain of $N$ monomers in a polydisperse sample to be equal to its weight fraction $w_N$ ? What can you state about the molar mass $M_N$ of this species?

Narayan Hari
Narayan Hari
Numerade Educator
02:26

Problem 30

The number fraction (or mole fraction) of a protein with molar mass $M_{\mathrm{A}}=10^5 \mathrm{gmol}^{-1}$ in an unknown mixture of different protein species is $n_{\mathrm{A}}=0.1$. The weight fraction of this protein in the same mixture is $w_{\mathrm{A}}=0.2$.
(i) What is the number-average molar mass $M_n$ of the mixture?
(ii) What is the weight-average molar mass $M_w$ of this mixture?

Kratika Bhadauria
Kratika Bhadauria
Numerade Educator

Problem 31

Show that the $k$-moment of the number fraction distribution $n_N$ is related to the $(k-1)$-moment of the weight fraction distribution $w_N$ [derive Eq. (1.54)].

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01:20

Problem 32

Consider the condensation polymerization of aminocaproic acid to make nylon 6:

$$
n \mathrm{H}_2 \mathrm{~N}\left(\mathrm{CH}_2\right)_5 \mathrm{COOH} \rightarrow\left[\left(\mathrm{CH}_2\right)_5 \mathrm{CONH}\right]_n+n \mathrm{H}_2 \mathrm{O}
$$

(i) What is the number-average molar mass $M_n$ at the extent of reaction $p=0.99 ?$
(ii) What is the weight-average molar mass $M_{\mathrm{w}}$ and polydispersity index at the same extent of reaction $p=0.99$ ?

Kratika Bhadauria
Kratika Bhadauria
Numerade Educator

Problem 33

At what extent of reaction $p$ is the polydispersity index of a linear condensation polymerization sample equal to $M_{\mathrm{w}} / M_{\mathrm{n}}=1.5$ ?

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01:02

Problem 34

Prove that the weight-average molar mass is never smaller than the number-average molar mass and therefore the polydispersity index is never less than unity:

$$
\frac{M_{\mathrm{w}}}{M_{\mathrm{n}}} \geq 1
$$

Narayan Hari
Narayan Hari
Numerade Educator

Problem 35

Calculate the degree of polymerization $N_{\max }(p)$ corresponding to the maximum of the most-probable weight fraction $w^{\prime}(p)$ [Eq. (1.53)] at the extent of reaction $p$. Is this value $N_{\max }(p)$ better approximated for small ( $1-p$ ) by the number-average $N_{\mathrm{n}}$ or by the weight-average $N_{\mathrm{w}}$ degree of polymerization? Hint: Expand the logarithm for small $(1-p)$.

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Problem 36

Consider condensation polymerization of $f$-arm stars. Each star molecule contains one multifunctional monomer $\mathrm{B}_f$ and $N-1$ bifunctional monomers AB with condensation reaction possible only between unreacted A and B groups. Arms of the star are polydisperse with each of $f$ arms containing between 0 and $N-1$ monomers AB.
(i) Demonstrate that the number fraction distribution function of N -mers is

$$
n_N(p)=\frac{(N+f-2)!}{(f-1)!(N-1)!} p^{N-1}(1-p)^f
$$

where $N$ is the total degree of polymerization of all arms of the star.
(ii) Show that the number-average degree of polymerization is

$$
N_{\mathrm{n}}=\frac{(f-1) p+1}{1-p}
$$

(iii) Calculate the weight-average degree of polymerization and show that as extent of reaction $p \rightarrow 1$, the polydispersity index decreases with the number of arms as

$$
\frac{N_{\mathrm{w}}}{N_{\mathrm{n}}} \cong 1+\frac{1}{f}
$$

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Problem 37

Addition polymerization
(i) Calculate the weight-fraction distribution function $w_N$ for addition polymerization without termination from the Poisson number fraction distribution function $n_N$ [Eq. (1.67)] using

$$
w_N=\frac{N n_N}{\sum_{N=1}^x N n_N}
$$

(ii) Prove that the number-average degree of polymerization of the Poisson distribution is $N_{\mathrm{n}}$.
(iii) Calculate the weight-average degree of polymerization $N_{\mathrm{w}}$ and polydispersity index for addition polymerization without termination. Does $N_{\mathrm{w}} / N_{\mathrm{n}}$ increase or decrease as the reaction proceeds?
(iv) The number-average degree of polymerization of an addition polymerization sample is $N_n=100$. What is the polydispersity index of this sample?

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Problem 38

Prove that the Shultz distribution $w_N\left[\mathrm{Eq}\right.$. (1.70)] has a maximum at $N=N_{\mathrm{n}}$ for any value of $s>0$.

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Problem 39

List the necessary conditions for formation of a narrow molar mass distribution in addition polymerization.

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02:51

Problem 40

The osmotic pressure of a polymer solution at temperature $T=23^{\circ} \mathrm{C}$ was measured at several concentrations and is reported in the table below.
$$
\begin{array}{llllll}
\hline c\left(\mathrm{gcm}^{-3}\right) & 2 \times 10^{-3} & 4 \times 10^{-3} & 6 \times 10^{-3} & 8 \times 10^{-3} & 10^{-2} \\
\Pi\left(\mathrm{dyncm}^{-2}\right) & 508 & 1.04 \times 10^3 & 1.58 \times 10^3 & 2.15 \times 10^3 & 2.74 \times 10^3 \\
\hline
\end{array}
$$
Determine the number-average molar mass $M_{\mathrm{b}}$ of the polymer and the second virial coefficient of the solution $A_2$.

Narayan Hari
Narayan Hari
Numerade Educator

Problem 41

Light scattering measurements at scattering angle $\theta=3^{\circ}$ were performed on a dilute polymer solution using a laser with a wavelength $\lambda=5500 \AA$. The refractive index of the solvent is $n_0=1.4$ and the refractive index increment of the solution is $\mathrm{d} n / \mathrm{d} c=0.1 \mathrm{~cm}^3 \mathrm{~g}^{-1}$. The following data for the Rayleigh ratio were obtained:
$$
\begin{array}{llllll}
\hline c\left(\mathrm{~g} \mathrm{~cm}^{-3}\right) & 5 \times 10^{-4} & 10^{-3} & 1.5 \times 10^{-3} & 2 \times 10^{-3} & 2.5 \times 10^{-3} \\
R_\theta\left(\mathrm{cm}^{-1}\right) & 4.9 \times 10^{-4} & 8.4 \times 10^{-4} & 1.1 \times 10^{-3} & 1.3 \times 10^{-3} & 1.5 \times 10^{-3} \\
\hline
\end{array}
$$
(i) What is the value of the optical constant $K$ if one can assume that in dilute solutions $n \cong n_0$ ?
(ii) Plot $K c / R_\theta$ as a function of the concentration $c$ and determine the weight-average molar mass $M_w$ and the second virial coefficient $A_2$.

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Problem 42

Modern light scattering uses a polarized laser, but since much of the older literature used unpolarized light sources, it is useful to understand them. Unpolarized light can be represented as a combination of a vertically and horizontally polarized waves-the first one with electric field oscillating along the vertical $x$ axis and the second one-along the horizontal $y$ axis. The intensities of these two parts of the incident light are $I_x=I_y=I_i / 2$. The intensity per unit scattering volume of the vertically potarized scattered wave is $\bar{I}_{\text {polar }} / 2$.
(i) Show that the intensity at scattering angle $\theta$, per unit scattering volume of the horizontally polarized scattered wave, is $\left(\bar{I}_{\mathrm{polar}} / 2\right) \cos ^2 \theta$.
(ii) Show that the intensity of the scattered light per unit scattering volume using an unpolarized light source valid for any radial position of the detector with scattering angle $\theta$ is

$$
I_{\text {unpolar }}=\frac{2 \pi^2 n^2}{\lambda^4 r^2}\left(1+\cos ^2 \theta\right)\left(\frac{\mathrm{d} n}{\mathrm{~d} c}\right)^2 \frac{c M}{\mathcal{N}_{\mathrm{Av}}} I_{\mathrm{i}}
$$

(iii) Demonstrate that the Rayleigh ratio from an unpolarized light source [Eq. (1.87)] is equal to

$$
\begin{aligned}
R_\theta^{\text {unpolar }} & \equiv \frac{\bar{I}_{\text {unpolar }} r^2}{I_i}=\frac{2 \pi^2 n^2}{\lambda^4}\left(\frac{\mathrm{~d} n}{\mathrm{~d} c}\right)^2 \frac{c M}{\mathcal{N}_{\mathrm{Av}}}\left(1+\cos ^2 \theta\right) \\
& =K c M \frac{1+\cos ^2 \theta}{2}
\end{aligned}
$$

where $K$ is the optical ratio defined in Eq. (1.89).

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04:14

Problem 43

The intensity of the incident beam decreases due to scattering following Beer's Law:

$$
I_{\mathrm{i}}(z)=I_0 \exp \left[-\tau\left(z-z_0\right)\right]
$$

where $\tau$ is the turbidity of the sample and $z-z_0$ is the length of the path of the incident beam between the entry into the sample $z_0$ (with intensity $I_0$ at $z_0$ ) and the point with coordinate $z$. Turbidity can be obtained from the Rayleigh ratio by integrating the radiated energy over all scattering directions. Using the Rayleigh ratio for an unpolarized light source [Eq. (1.109)], show that the turbidity is

$$
\tau=\frac{8 \pi}{3} K c M
$$

Nicole Wood
Nicole Wood
Numerade Educator
01:29

Problem 44

Size exclusion chromatography

A fraction of a polystyrene sample elutes in tetrahydrofuran at $25^{\circ} \mathrm{C}$ at 48 mL . Estimate the molar mass of this fraction using the universal calibration for this set of columns presented in Fig. 1.26 and the Mark-Houwink coefficients listed in Table 1.4.

Kratika Bhadauria
Kratika Bhadauria
Numerade Educator

Problem 45

Determine the moment of the molar mass distribution measured by intrinsic viscosity of a polydisperse sample.

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