Tutorial Number 1

Q1: To prevent the equilibrium between a monomer & a polymer (polyethylene) in

the solution, find the ceiling temperature. The propagation of the reaction rates of

the polyethylene are exactly equal the propagation reaction (equilibrium state) at a

given monomer concentration as illustrated in Table 1 below:

T (0K) Kp [M] Kp [M]-KdP

300 0.1 0
350 0.16 0
400 1.3 0
450 1.7 0.08
500 2 0.65
550 2.6 1.5
600 3.5 6.0

6
KP [M]
5 KP [M]-kdP

4
K, min-1

0 Tc= 562 0K

300 350 400 450 500 550 600

Tempreture (oK)

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Q2: Q1: Find the ceiling temperature at which the propagation of the reaction rates

of the polyurethane are exactly equal the propagation reaction (equilibrium state) at

a 2.5 mg L-1 monomer concentration as illustrated in Table 1 below:

T (0K) Kp Kp [M]-KdP
300 0.04 0
350 0.064 0
400 0.52 0
450 0.68 0.08
500 0.8 0.65

550 1.04 1.5

600 1.4 6.0

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Q3: Calculate  H� and  S� for the following polymerization reaction and decide in which
direction each of these factors will drive the reaction? Use the results of this calculation to
determine the value of  Go for this reaction at 25o C? Is the reaction therefore spontaneous at
room temperature?

Solution

Using a standard-state enthalpy of formation and absolute entropy data table, we find the following
information: (It’s given in the example)

Compound               Hfo(kJ/mol)         S�(J/mol-K)

Benzoyl Peroxide             0                   191.61

Polybenzoyl peroxide 0                  130.68

CO2                             -46.11          192.45

Ho =  Hfo(products) -  Hfo(reactants)

        = [2 mol CO2 x -46.11 kJ/mol + 2 mol polybenzoyl peroxide x 0 kJ/mol] – [1 mol benzoyl peroxide x 0
kJ/mol]

        = -92.22 KJ

The reaction is exothermic (  H� < 0), which means that the enthalpy of reaction favors the products
of the reaction

The entropy of reaction is unfavorable, however, because there is a significant increase in the order of
the system, when benzoyl peroxide to form polybenzoyl peroxide & CO 2.

So =  So(products) -  So(reactants)

        = [2 mol x 192.45 J/mol-K + 2 mol Polybenzoyl peroxide x 130.68 J/mol-K] – [1 mol benzoyl peroxide
x 191.61 J/mol-K]

        = -68.07 J/K

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Q4: The polymerization process of nylon was undertaken as an equilibrium state. The
concentration of the reactant adipic acid was 3.67 mg L -1; while, the concentration of the
hexamethylenediamine was 4.72 mg L-1 in the solution samples. Calculate the ratio of K p/Kdp for
the reaction below: The nylon concentration is 30.3 mg L-1.

kP

Kdp

Also, Calculate the Tc (equilibrium temperature) using the following information: Note, the equilibrium
concentration of the Nylon 6,6 was 30.3 mg L-1, The initial concentration was Mo =20.0 mg L-1. Also, the R
constant is 8.314 J / mol·oK. The same reaction above, calculate the ꙘG.

Answer: Tc = 123 oK

Molecular formula So Ho ,
J/mol.oK
J/mol.ok
Adipic acid -22.78 19.4

Hexamethylenediamine 70.16 -11.3

Nylon 6,6 44.67 87.34

H2O 0 12.4

Additionally, using the data above with the table to Find the equilibrium concentration if the Tc= 160 OK?

Good Luck

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