Scribd
Upload
17 views3 pages

Polymerization Kinetics Report

The document discusses the kinetics and thermodynamics of free radical polymerization, detailing the determination of activation energy for two peroxides and the polymerization of methyl methacrylate. It includes calculations for kinetic chain length, polymer formation, and the effects of varying monomer and initiator concentrations. Additionally, it covers styrene polymerization, providing insights into maximum degree of polymerization and the impact of initiator concentration on reaction rate.

Uploaded by

adristephaortega26
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
17 views3 pages

Polymerization Kinetics Report

The document discusses the kinetics and thermodynamics of free radical polymerization, detailing the determination of activation energy for two peroxides and the polymerization of methyl methacrylate. It includes calculations for kinetic chain length, polymer formation, and the effects of varying monomer and initiator concentrations. Additionally, it covers styrene polymerization, providing insights into maximum degree of polymerization and the impact of initiator concentration on reaction rate.

Uploaded by

adristephaortega26
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 3

Free Radical Polymerization Kinetics

and Thermodynamics
1. Determination of Activation Energy (Ed)

Given data:

| Temperature (C) | T (K) | t1/2 (di-t-butyl) [h] | t1/2 (bis(1-hydroxy cyclohexyl)) [h] |
|----------------|-------|------------------------|----------------------------------------|
| 90 | 363 | 800.0 | 9.8 |
| 100 | 373 | 210.0 | 4.5 |
| 110 | 383 | 65.0 | 2.0 |
| 120 | 393 | 20.0 | 1.0 |
| 130 | 403 | 6.5 | 0.5 |

Since it's first-order kinetics:

k_d = ln(2) / t1/2

From the Arrhenius equation:

ln(k_d) = ln(A) - Ed / (RT)

Using linear regression of ln(k_d) vs 1/T:

- di-t-butyl peroxide: Ed ≈ 131.6 kJ/mol


- bis(1-hydroxy cyclohexyl) peroxide: Ed ≈ 91.2 kJ/mol

2. Polymerization of Methyl Methacrylate

Given:
- Volume = 100 L
- Density = 0.94 g/cm³ = 940 g/L
- Molar mass MMA = 100.12 g/mol
- Monomer concentration [M]₀ = 94000 g / 100.12 ≈ 939 mol/L
- Initiator = 10.2 mol in 100 L → [I]₀ = 0.102 mol/L
- f = 0.3
- t1/2 = 50 h = 180,000 s → kd = ln(2) / t1/2 ≈ 3.85 × 10⁻⁶ s⁻¹
- kp = 5.5 L mol⁻¹ s⁻¹
- kt = 25.5 × 10⁶ L mol⁻¹ s⁻¹

(a) Kinetic chain length (v̄):

Ri = 2fk_d[I] = 2(0.3)(3.85×10⁻⁶)(0.102) = 2.35×10⁻⁷ mol L⁻¹ s⁻¹


Rp = kp[M]√(Ri/kt)
v̄ = Rp / Ri = kp[M] / √(Ri * kt)
v̄ ≈ 2887

(b) Polymer formed in 5 h:

Rp ≈ 0.067 mol L⁻¹ s⁻¹


t = 18000 s
Polymer formed = Rp * t = 1206 mol L⁻¹
Total = 120600 mol × 100.12 g/mol ≈ 12.07 kg polymer

3. Effect of Monomer and Initiator Concentration

(a) (i) Increasing [M] by 10x:

Rp ∝ [M][I]¹ᐟ² → 10×[M] ⇒ Rp increases by factor of 10

(ii) Degree of polymerization:

DPn ∝ [M]/√[I] → Increases by factor of 10

(b) Halving [I]:

(i) Rp ∝ √[I] ⇒ Decreases by √2 ≈ 1.41

(ii) DPn ∝ 1/√[I] ⇒ Increases by √2 ≈ 1.41

4. Styrene Polymerization

Given:
- [I] = 6.6 × 10⁻³ mol/L
- Rp = 1.79 × 10⁻³ mol/L·min
- kd = 3.25 × 10⁻⁴ min⁻¹
- Assume f = 0.5
(a) Maximum DPn:

Ri = 2fk_d[I] = 2 × 0.5 × 3.25×10⁻⁴ × 6.6×10⁻³ = 2.145×10⁻⁶ mol L⁻¹ min⁻¹


DPn = Rp / Ri = 1.79×10⁻³ / 2.145×10⁻⁶ ≈ 834

(b) New Rp for [I] = 25×10⁻³ mol/L:

Increase factor = 25 / 6.6 ≈ 3.79 ⇒ √3.79 ≈ 1.95


New Rp = 1.79×10⁻³ × 1.95 = 3.49×10⁻³ mol L⁻¹ min⁻¹

You might also like