Applications: Free Radical Initiators Thermal Initiators: Decomposition Rate and Half-Life (continued) Table I: Decompositon Rates and 10-Hour Half-life Temperatures of Common Thermal Initiator (arranged alphabetically by initiator) Aldrich Cat. No. Initiator 44,146-5 tert-Amyl peroxybenzoate 11,816-8 4,4-Azobis(4-cyanovaleric acid) 38,021-0 1,1'-Azobis (cyclohexanecarbonitrile) 44,109-0 2,2-Azobisisobutyronitrile (AIBN) 17,998-1 Benzoyl peroxide² 44,169-4 2,2-Bis(tert-butylperoxy)butane 38,814-9 1,1-Bis(tert-butylperoxy)cyclohexane 38,809-2 2,5-Bis(tert-butylperoxy)-2,5- 32,953-3 44,171-6 38,808-4 41,666-5 tert-Butyl hydroperoxide dimethylhexane 2,5-Bis(tert-Butylperoxy)- 2,5-dimethyl-3-hexyne Bis(1-(tert-butylperoxy)-1- methylethyl)benzene 1,1-Bis(tert-butylperoxy)-3,3,5- trimethylcyclohexane 38,807-6 tert-Butyl peracetate 16,852-1 tert-Butyl peroxide 15,904-2 tert-Butyl peroxybenzoate 44,147-3 tert-Butylperoxy isopropyl carbonate 24,750-2 Cumene hydroperoxide 28,908-6 Cyclohexanone peroxide 32,954-1 Dicumyl peroxide 29,078-5 Lauroyl peroxide 44,182-1 2,4- Pentanedione peroxide 26,933-6 Peracetic acid 21,622-4 Potassium persulfate³ Solvent Acetone Water Water Toluene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Water 0.1M NaOH T(°C) 70 69 80 80 95 102 50 70 100 60 78 100 93 115 145 130 160 170 183 85 100 130 80 100 130 100 130 115 145 40 60 85 80 50 60 80 90 k(s.¹) 4.6 x 10 1.9 x 10 9.0 x 105 6.5 x 104 5.4 x 105 1.3 x 104 2.2 x 10 3.2 x 10 1.5 X 10 2.0 x 10 2.3 x 10 5.0 x 104 1.9 x 10 1.1 x 10 4.7 x 10+ 3 x 107 6.6 x 10 2.0 x 105 3.1 x 10 1.2 x 104 1.5 x 10 5.7 x 104 7.8 x 10 8.8 x 10 3.0 x 105 1.1 x 10-5 3.5 x 104 4.0 x 10 6.6 x 10€ 4.9 x 10 9.2 x 10° 3.8 x 10 6.9 x 10-5 9.5 x 107 3.2 x 10 9.2 x 10 3.5 x 10+ 10h Half-life °C (Solvent) 99 (benzene) 69 (water) 88 (toluene) 65 (toluene) 70 (benzene) 100 (benzene) 120 (benzene) 125 (benzene) 115 (benzene) 85 (dibutyl phthalate) 170 (benzene) 100 (benzene) 125 (benzene) 103 (benzene) 98 (aliphatic hydrocarbons) 135 (toluene) 90 (benzene) 115 (benzene) 65 (benzene) 125 (triethyl phosphate) 135 (toluene) 60 (H₂O) 70 (0.1M NaOH) ¹"Polymer Handbook", Eds. Brandrup, J; Immergut, E.H.; Grulke, E.A., 4th Edition, John Wiley, New York, 1999, II/2-69; Aldrich Catalog No. 241,247-3 ²Amines can significantly increase the decomposition rates of peroxides, e.g., addition of N,N-dimethyl aniline to benzoyl peroxide causes the latter decompose rapidly at room temperature. ³Persulfate decomposition is pH dependent. • Polymer Products from Aldrich
Applications: Free Radical Initiators Thermal Initiators: Decomposition Rate and Half-Life (continued) Table I: Decompositon Rates and 10-Hour Half-life Temperatures of Common Thermal Initiator (arranged alphabetically by initiator) Aldrich Cat. No. Initiator 44,146-5 tert-Amyl peroxybenzoate 11,816-8 4,4-Azobis(4-cyanovaleric acid) 38,021-0 1,1'-Azobis (cyclohexanecarbonitrile) 44,109-0 2,2-Azobisisobutyronitrile (AIBN) 17,998-1 Benzoyl peroxide² 44,169-4 2,2-Bis(tert-butylperoxy)butane 38,814-9 1,1-Bis(tert-butylperoxy)cyclohexane 38,809-2 2,5-Bis(tert-butylperoxy)-2,5- 32,953-3 44,171-6 38,808-4 41,666-5 tert-Butyl hydroperoxide dimethylhexane 2,5-Bis(tert-Butylperoxy)- 2,5-dimethyl-3-hexyne Bis(1-(tert-butylperoxy)-1- methylethyl)benzene 1,1-Bis(tert-butylperoxy)-3,3,5- trimethylcyclohexane 38,807-6 tert-Butyl peracetate 16,852-1 tert-Butyl peroxide 15,904-2 tert-Butyl peroxybenzoate 44,147-3 tert-Butylperoxy isopropyl carbonate 24,750-2 Cumene hydroperoxide 28,908-6 Cyclohexanone peroxide 32,954-1 Dicumyl peroxide 29,078-5 Lauroyl peroxide 44,182-1 2,4- Pentanedione peroxide 26,933-6 Peracetic acid 21,622-4 Potassium persulfate³ Solvent Acetone Water Water Toluene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Benzene Water 0.1M NaOH T(°C) 70 69 80 80 95 102 50 70 100 60 78 100 93 115 145 130 160 170 183 85 100 130 80 100 130 100 130 115 145 40 60 85 80 50 60 80 90 k(s.¹) 4.6 x 10 1.9 x 10 9.0 x 105 6.5 x 104 5.4 x 105 1.3 x 104 2.2 x 10 3.2 x 10 1.5 X 10 2.0 x 10 2.3 x 10 5.0 x 104 1.9 x 10 1.1 x 10 4.7 x 10+ 3 x 107 6.6 x 10 2.0 x 105 3.1 x 10 1.2 x 104 1.5 x 10 5.7 x 104 7.8 x 10 8.8 x 10 3.0 x 105 1.1 x 10-5 3.5 x 104 4.0 x 10 6.6 x 10€ 4.9 x 10 9.2 x 10° 3.8 x 10 6.9 x 10-5 9.5 x 107 3.2 x 10 9.2 x 10 3.5 x 10+ 10h Half-life °C (Solvent) 99 (benzene) 69 (water) 88 (toluene) 65 (toluene) 70 (benzene) 100 (benzene) 120 (benzene) 125 (benzene) 115 (benzene) 85 (dibutyl phthalate) 170 (benzene) 100 (benzene) 125 (benzene) 103 (benzene) 98 (aliphatic hydrocarbons) 135 (toluene) 90 (benzene) 115 (benzene) 65 (benzene) 125 (triethyl phosphate) 135 (toluene) 60 (H₂O) 70 (0.1M NaOH) ¹"Polymer Handbook", Eds. Brandrup, J; Immergut, E.H.; Grulke, E.A., 4th Edition, John Wiley, New York, 1999, II/2-69; Aldrich Catalog No. 241,247-3 ²Amines can significantly increase the decomposition rates of peroxides, e.g., addition of N,N-dimethyl aniline to benzoyl peroxide causes the latter decompose rapidly at room temperature. ³Persulfate decomposition is pH dependent. • Polymer Products from Aldrich
Introduction to Chemical Engineering Thermodynamics
8th Edition
ISBN:9781259696527
Author:J.M. Smith Termodinamica en ingenieria quimica, Hendrick C Van Ness, Michael Abbott, Mark Swihart
Publisher:J.M. Smith Termodinamica en ingenieria quimica, Hendrick C Van Ness, Michael Abbott, Mark Swihart
Chapter1: Introduction
Section: Chapter Questions
Problem 1.1P
Related questions
Question
Use the data provided for tert-Butyl hydroperoxide, AIBN, and Potassium persulfate.
Using an Arrhenius fit, what is the activation energy of decomposition for these initiators?
Transcribed Image Text:4
Applications: Free Radical Initiators
Thermal Initiators: Decomposition Rate and Half-Life (continued)
Table 1: Decompositon Rates and 10-Hour Half-life Temperatures of Common Thermal Initiators
(arranged alphabetically by initiator)
Aldrich
Cat. No.
Initiator
44,146-5
tert-Amyl peroxybenzoate
11,816-8 4,4-Azobis(4-cyanovaleric acid)
38,021-0 1,1'-Azobis(cyclohexanecarbonitrile)
44,109-0 2,2¹-Azobisisobutyronitrile (AIBN)
17,998-1 Benzoyl peroxide²
44,169-4 2,2-Bis(tert-butylperoxy)butane
38,814-9 1,1-Bis(tert-butylperoxy)cyclohexane
38,809-2 2,5-Bis(tert-butylperoxy)-2,5-
32,953-3
44,171-6
38,808-4
41,666-5 tert-Butyl hydroperoxide
dimethylhexane
2,5-Bis(tert-Butylperoxy)-
2,5-dimethyl-3-hexyne
Bis(1-(tert-butylperoxy)-1-
methylethyl)benzene
1,1-Bis(tert-butylperoxy)-3,3,5-
trimethylcyclohexane
38,807-6 tert-Butyl peracetate
16,852-1 tert-Butyl peroxide
15,904-2 tert-Butyl peroxybenzoate
44,147-3 tert-Butylperoxy isopropyl carbonate
24,750-2 Cumene hydroperoxide
28,908-6 Cyclohexanone peroxide
32,954-1 Dicumyl peroxide
29,078-5 Lauroyl peroxide
44,182-1 2,4- Pentanedione peroxide
26,933-6 Peracetic acid
21,622-4 Potassium persulfate³
Solvent
Acetone
Water
Water
Toluene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Water
0.1M NaOH
T(°C)
70
69
80
80
95
102
50
70
100
60
78
100
93
115
145
130
160
170
183
85
100
130
80
100
130
100
130
115
145
40
60
85
80
50
60
80
90
k (s.¹)
4.6 x 10-5
1.9 x 10-5
9.0 x 10-5
6.5 x 10-5
5.4 x 10-5
1.3 x 10+
2.2 x 10⁰
3.2 x 10-5
1.5 X 10-³
2.0 x 10-6
2.3 x 10-5
5.0 x 10*
1.9 x 10-5
1.1 x 10-5
4.7 x 10+
3 x 10-7
6.6 x 10-6
2.0 x 10-5
3.1 x 10-5
1.2 x 10⁰
1.5 x 10-5
5.7 x 10+
7.8 x 10-⁹
8.8 x 10-7
3.0 x 10-5
1.1 x 10-5
3.5 x 10-
4.0 x 10
6.6 x 10€
4.9 x 10
9.2 x 10€
3.8 x 10+
6.9 x 10
9.5 x 10-7
3.2 x 10-6
9.2 x 10-5
3.5 x 104
10h Half-life °C (Solvent)
99 (benzene)
69 (water)
88 (toluene)
65 (toluene)
70 (benzene)
100 (benzene)
120 (benzene)
125 (benzene)
115 (benzene)
85 (dibutyl phthalate)
170 (benzene)
100 (benzene)
125 (benzene)
103 (benzene)
98 (aliphatic hydrocarbons)
135 (toluene)
90 (benzene)
115 (benzene)
65 (benzene)
125 (triethyl phosphate)
135 (toluene)
60 (H₂O)
70 (0.1M NaOH)
¹"Polymer Handbook", Eds. Brandrup, J; Immergut, E.H.; Grulke, E.A., 4th Edition, John Wiley, New York, 1999, II/2-69; Aldrich Catalog No. 241,247-3.
²Amines can significantly increase the decomposition rates of peroxides, e.g., addition of N,N-dimethyl aniline to benzoyl peroxide causes the latter to
decompose rapidly at room temperature.
*Persulfate decomposition is pH dependent.
• Polymer Products from Aldrich
Transcribed Image Text:A
ALDRICH
Applications: Free Radical Initiators.
Thermal Initiators: Decomposition Rate and Half-Life
ww
Ideally, a thermal free radical initiator should be relatively
stable at room temperature but should decompose rapidly
enough at the polymer-processing temperature to ensure a
practical reaction rate. In addition to temperature, the
decomposition rate (k) of the initiator will depend on the
solvent/monomer system used. The confining effect of
solvent molecules (the cage effect) causes secondary
"wastage" reactions including recombination of radicals to
regenerate the initiator. The cage effect becomes more
significant as viscosity increases.
The most important indicator of activity of an initiator is its
half-life (t2). It is the time required to reduce the original
initator content of a solution by 50%, at a given
temperature.
Fig 1: Relationship of Half Life (t) to Decomposition Rate (k.).
L=85d
20d
200d
1y-
2y-
k x 10⁰
8.5d-
10d-
20d
40d
60d-
x 10
20h
24h
40h
60h
120h-
x 10°
120m-
200m -
5h-
10h
x 10
12m
20m-
30m-
40m
80m
Assuming first order decomposition kinetics, which is tru
for most free radical organic initiators, the half-life (₁/2)
related to the initiator decomposition rate (k) as follows
t₁/2 = In2/k
Table I lists the decomposition rate (k) data¹ for sever
commonly used free radical initiators, at specific temper
tures and solvents. To further assist you in your selection
a thermal initiator, the temperature corresponding to a
hour half-life in a specific solvent is also shown. Fig.
relates the initiator decomposition rate (k.) in s¹ to th
half-life for a broad range of k, values, including those four
in Table I.
x 10
How to read the chart:
See circled example: Half lives are to
the left of each vertical line.
A half life of 200s has a rate constant
of 3.4 x 10-³
70s
80s
120s
200s
10m -
x 10¹
7s
10s
20s
30s-
40s-
Key:
y = years
d = days
h = hours
x 10°
0.75s-
m = minutes
s
seconds
1s
3s
5s
x 10'
0.07s
0.12s
0.25s-
0.35s
0.5s
x 10°
10 =
9
8
7
6
5
4
3
2
This chart is reprinted with permission from Wiley Interscience
1
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