高等学校化学学报 ›› 2022, Vol. 43 ›› Issue (2): 20210563.doi: 10.7503/cjcu20210563
邓红日1,2, 曹晓梅3, 王静波1,2(), 李象远1,2
收稿日期:
2021-08-10
出版日期:
2022-02-10
发布日期:
2021-11-23
通讯作者:
王静波
E-mail:wangjingbo@scu.edu.cn
基金资助:
DENG Hongri1,2, CAO Xiaomei3, WANG Jingbo1,2(), LI Xiangyuan1,2
Received:
2021-08-10
Online:
2022-02-10
Published:
2021-11-23
Contact:
WANG Jingbo
E-mail:wangjingbo@scu.edu.cn
Supported by:
摘要:
对2~6个环的多环芳烃的氢提取反应类进行了系统研究, 提取氢原子的不饱和自由基包括丙炔基自由基(C3H3)、 烯丙基自由基(C3H5)、 丁二烯基自由基(nC4H5, iC4H5)、 环戊二烯基自由基(C5H5)以及苯基自由基(C6H5). 采用M06-2X/cc-pVTZ方法得到了多环芳烃的电子结构信息, 利用过渡态理论并结合Eckart隧道校正, 计算了所有反应在500~2500 K范围内的反应速率常数.考察了多环芳烃的大小、 结构对反应速率常数的影响, 对比了不同氢提取自由基及不同氢提取反应类型的速率常数. 结果表明, 多环芳烃的大小对反应速率常数影响不大, 但是多环芳烃的环结构对反应速率常数影响较大. 将不同的氢提取反应类简化为发生在五元环上的C5类和发生在六元环上的C6类两类, 结果表明, C6类的反应活性高于C5类. 研究了nC4H5, iC4H5以及C6H5自由基与多环芳烃的氢提取反应, 它们的氢提取反应活性大小顺序为C6H5>nC4H5>iC4H5. 通过对每类典型反应的速率常数取平均值, 总结出相应类型的速率规则, 可用于构建多环芳烃和碳烟机理.
中图分类号:
TrendMD:
邓红日, 曹晓梅, 王静波, 李象远. 多环芳烃与不饱和自由基氢提取反应类的动力学研究. 高等学校化学学报, 2022, 43(2): 20210563.
DENG Hongri, CAO Xiaomei, WANG Jingbo, LI Xiangyuan. Rate Rules for Hydrogen Abstraction Reactions of Polycyclic Aromatic Hydrocarbons and Unsaturated Radicals. Chem. J. Chinese Universities, 2022, 43(2): 20210563.
Method | ΔE1/(kJ·mol-1) | ΔE-1/(kJ·mol-1) | ΔH298 K/(kJ·mol-1) |
---|---|---|---|
G4MP2 | 42.7 | 38.9 | 3.3 |
CBS?QB3 | 46.9 | 41.8 | 5.0 |
M06?2X/aug?cc?pVTZ | 41.4 | 38.5 | 2.9 |
M06?2X/cc?pVTZ | 41.4 | 37.2 | 4.2 |
Table 1 Comparison of forward and reverse energy barriers(ΔE1 and ΔE-1) at 0 K and reaction enthalpies (ΔH298 K) at 298 K calculated by different methods for the reaction of nC4H5 and naphthalene
Method | ΔE1/(kJ·mol-1) | ΔE-1/(kJ·mol-1) | ΔH298 K/(kJ·mol-1) |
---|---|---|---|
G4MP2 | 42.7 | 38.9 | 3.3 |
CBS?QB3 | 46.9 | 41.8 | 5.0 |
M06?2X/aug?cc?pVTZ | 41.4 | 38.5 | 2.9 |
M06?2X/cc?pVTZ | 41.4 | 37.2 | 4.2 |
Reaction | ΔE1/(kJ·mol-1) | ΔE-1/(kJ·mol-1) | ΔH298 K/(kJ·mol-1) |
---|---|---|---|
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?α | 42.7 | 38.9 | 3.8 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?β | 42.7 | 38.5 | 4.2 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?γ | 44.4 | 40.6 | 3.8 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?δ | 43.5 | 40.6 | 2.9 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?ε | 43.5 | 47.7 | -4.6 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?α | 44.8 | 27.2 | 18.0 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?β | 45.2 | 26.8 | 18.0 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?γ | 46.4 | 28.0 | 17.6 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?δ | 46.0 | 28.9 | 16.3 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?ε | 45.2 | 35.1 | 9.2 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?α | 37.7 | 36.4 | 2.1 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?β | 38.5 | 36.4 | 2.5 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?γ | 38.1 | 36.0 | 2.1 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?δ | 38.1 | 37.2 | 1.3 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?ε | 38.9 | 45.2 | -6.3 |
Table 2 Theoretical predicted forward and reverse barriers and reaction enthalpies for hydrogen abstraction from phenanthrene by nC4H5, iC4H5 and C6H5 radicals
Reaction | ΔE1/(kJ·mol-1) | ΔE-1/(kJ·mol-1) | ΔH298 K/(kJ·mol-1) |
---|---|---|---|
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?α | 42.7 | 38.9 | 3.8 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?β | 42.7 | 38.5 | 4.2 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?γ | 44.4 | 40.6 | 3.8 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?δ | 43.5 | 40.6 | 2.9 |
nC4H5+3cyc?Phen→C4H6+3cyc?Phen?ε | 43.5 | 47.7 | -4.6 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?α | 44.8 | 27.2 | 18.0 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?β | 45.2 | 26.8 | 18.0 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?γ | 46.4 | 28.0 | 17.6 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?δ | 46.0 | 28.9 | 16.3 |
iC4H5+3cyc?Phen→C4H6+3cyc?Phen?ε | 45.2 | 35.1 | 9.2 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?α | 37.7 | 36.4 | 2.1 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?β | 38.5 | 36.4 | 2.5 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?γ | 38.1 | 36.0 | 2.1 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?δ | 38.1 | 37.2 | 1.3 |
C6H5+3cyc?Phen→C6H6+3cyc?Phen?ε | 38.9 | 45.2 | -6.3 |
Reaction class | Radical | Number of aromatic rings | No. | Reaction | ΔE1/(kJ·mol-1) | ΔE-1/(kJ·mol-1) | ΔH298 K/(kJ·mol-1) |
---|---|---|---|---|---|---|---|
C5 class | C3H3 | 3cyc | R1 | 3cyc?Acen→3cyc?Acen?α | 113.8 | 13.0 | 101.3 |
C3H5 | 3cyc | R2 | 3cyc?Acen→3cyc?Acen?α | 128.4 | 12.6 | 117.2 | |
C5H5 | 3cyc | R3 | 3cyc?Acen→3cyc?Acen?α | 145.2 | 5.0 | 140.6 | |
nC4H5 | 3cyc | R4 | 3cyc?Acen→3cyc?Acen?α | 51.0 | 31.8 | 19.2 | |
4cyc | R5 | 4cyc?Acep→4cyc?Acep?α | 51.0 | 32.2 | 18.4 | ||
5cyc | R6 | 5cyc?Cycpy→5cyc?Cycpy?α | 50.2 | 32.6 | 17.2 | ||
6cyc | R7 | 6cyc?Dicpy→6cyc?Dicpy?γ | 50.2 | 33.1 | 17.2 | ||
iC4H5 | 3cyc | R8 | 3cyc?Acen→3cyc?Acen?α | 56.5 | 23.4 | 32.6 | |
4cyc | R9 | 4cyc?Acep→4cyc?Acep?α | 55.6 | 23.0 | 32.2 | ||
5cyc | R10 | 5cyc?Cycpy→5cyc?Cycpy?α | 54.4 | 23.4 | 31.0 | ||
6cyc | R11 | 6cyc?Dicpy→6cyc?Dicpy?γ | 55.6 | 23.4 | 31.0 | ||
C6H5 | 3cyc | R12 | 3cyc?Acen→3cyc?Acen?α | 47.3 | 30.5 | 17.6 | |
4cyc | R13 | 4cyc?Acep→4cyc?Acep?α | 47.3 | 31.4 | 16.7 | ||
5cyc | R14 | 5cyc?Cycpy→5cyc?Cycpy?α | 46.4 | 31.8 | 15.5 | ||
6cyc | R15 | 6cyc?Dicpy→6cyc?Dicpy?γ | 46.4 | 30.5 | 15.5 | ||
C6 class | C3H3 | 2cyc | R16 | 2cyc?Naph→2cyc?Naph?α | 104.2 | 18.4 | 86.2 |
C3H5 | 2cyc | R17 | 2cyc?Naph→2cyc?Naph?α | 120.1 | 19.2 | 102.5 | |
C5H5 | 2cyc | R18 | 2cyc?Naph→2cyc?Naph?α | 131.4 | 6.3 | 125.5 | |
nC4H5 | 2cyc | R19 | 2cyc?Naph→2cyc?Naph?α | 41.4 | 37.2 | 4.2 | |
3cyc | R20 | 3cyc?Anth→3cyc?Anth?β | 42.3 | 38.1 | 4.2 | ||
4cyc | R21 | 4cyc?Tetce→4cyc?Tetce?β | 41.0 | 38.1 | 4.6 | ||
3cyc | R22 | 3cyc?Phen→3cyc?Phen?α | 42.7 | 38.9 | 3.8 | ||
3cyc | R23 | 3cyc?Acen→3cyc?Acen?β | 42.3 | 39.7 | 2.5 | ||
4cyc | R24 | 4cyc?Pyre→4cyc?Pyre?α | 41.8 | 38.5 | 2.5 | ||
4cyc | R25 | 4cyc?Tetph→4cyc?Tetph?α | 41.8 | 45.6 | -3.8 | ||
4cyc | R26 | 4cyc?Acep→4cyc?Acep?δ | 41.8 | 38.5 | 3.3 | ||
5cyc | R27 | 5cyc?Cycpy→5cyc?Cycpy?δ | 41.0 | 38.1 | 4.2 | ||
6cyc | R28 | 6cyc?Dicpy→6cyc?Dicpy?β | 41.4 | 39.7 | 1.7 | ||
iC4H5 | 2cyc | R29 | 2cyc?Naph→2cyc?Naph?α | 44.4 | 26.4 | 18.0 | |
3cyc | R30 | 3cyc?Anth→3cyc?Anth?β | 43.9 | 25.9 | 18.0 | ||
4cyc | R31 | 4cyc?Tetce→4cyc?Tetce?β | 45.6 | 28.0 | 18.0 | ||
3cyc | R32 | 3cyc?Phen→3cyc?Phen?α | 45.6 | 27.6 | 17.6 | ||
3cyc | R33 | 3cyc?Acen→3cyc?Acen?β | 46.9 | 30.1 | 15.9 | ||
4cyc | R34 | 4cyc?Pyre→4cyc?Pyre?α | 45.2 | 27.6 | 15.9 | ||
4cyc | R35 | 4cyc?Tetph→4cyc?Tetph?α | 43.9 | 33.5 | 9.6 | ||
4cyc | R36 | 4cyc?Acep→4cyc?Acep?δ | 45.2 | 27.2 | 17.2 | ||
5cyc | R37 | 5cyc?Cycpy→5cyc?Cycpy?δ | 44.4 | 27.2 | 17.6 | ||
6cyc | R38 | 6cyc?Dicpy→6cyc?Dicpy?β | 45.2 | 29.3 | 15.1 | ||
C6H5 | 2cyc | R39 | 2cyc?Naph→2cyc?Naph?α | 38.1 | 36.4 | 2.5 | |
3cyc | R40 | 3cyc?Anth→3cyc?Anth?β | 38.5 | 36.8 | 2.5 | ||
4cyc | R41 | 4cyc?Tetce→4cyc?Tetce?β | 38.9 | 37.7 | 2.9 | ||
3cyc | R42 | 3cyc?Phen→3cyc?Phen?α | 37.7 | 36.4 | 2.1 | ||
3cyc | R43 | 3cyc?Acen→3cyc?Acen?β | 39.3 | 38.5 | 0.8 | ||
4cyc | R44 | 4cyc?Pyre→4cyc?Pyre?α | 37.7 | 36.4 | 0.8 | ||
4cyc | R45 | 4cyc?Tetph→4cyc?Tetph?α | 37.2 | 43.1 | -5.4 | ||
4cyc | R46 | 4cyc?Acep→4cyc?Acep?δ | 37.7 | 36.0 | 1.7 | ||
5cyc | R47 | 5cyc?Cycpy→5cyc?Cycpy?δ | 36.4 | 35.1 | 2.5 | ||
6cyc | R48 | 6cyc?Dicpy→6cyc?Dicpy?β | 37.7 | 37.7 | 0 |
Table 3 Theoretical predicted forward and reverse barriers and reaction enthalpies for hydrogen abstraction from PAHs by C3H3, C3H5, nC4H5, iC4H5, C5H5, and C6H5 radicals calculated by M06-2X/cc-pVTZ method*
Reaction class | Radical | Number of aromatic rings | No. | Reaction | ΔE1/(kJ·mol-1) | ΔE-1/(kJ·mol-1) | ΔH298 K/(kJ·mol-1) |
---|---|---|---|---|---|---|---|
C5 class | C3H3 | 3cyc | R1 | 3cyc?Acen→3cyc?Acen?α | 113.8 | 13.0 | 101.3 |
C3H5 | 3cyc | R2 | 3cyc?Acen→3cyc?Acen?α | 128.4 | 12.6 | 117.2 | |
C5H5 | 3cyc | R3 | 3cyc?Acen→3cyc?Acen?α | 145.2 | 5.0 | 140.6 | |
nC4H5 | 3cyc | R4 | 3cyc?Acen→3cyc?Acen?α | 51.0 | 31.8 | 19.2 | |
4cyc | R5 | 4cyc?Acep→4cyc?Acep?α | 51.0 | 32.2 | 18.4 | ||
5cyc | R6 | 5cyc?Cycpy→5cyc?Cycpy?α | 50.2 | 32.6 | 17.2 | ||
6cyc | R7 | 6cyc?Dicpy→6cyc?Dicpy?γ | 50.2 | 33.1 | 17.2 | ||
iC4H5 | 3cyc | R8 | 3cyc?Acen→3cyc?Acen?α | 56.5 | 23.4 | 32.6 | |
4cyc | R9 | 4cyc?Acep→4cyc?Acep?α | 55.6 | 23.0 | 32.2 | ||
5cyc | R10 | 5cyc?Cycpy→5cyc?Cycpy?α | 54.4 | 23.4 | 31.0 | ||
6cyc | R11 | 6cyc?Dicpy→6cyc?Dicpy?γ | 55.6 | 23.4 | 31.0 | ||
C6H5 | 3cyc | R12 | 3cyc?Acen→3cyc?Acen?α | 47.3 | 30.5 | 17.6 | |
4cyc | R13 | 4cyc?Acep→4cyc?Acep?α | 47.3 | 31.4 | 16.7 | ||
5cyc | R14 | 5cyc?Cycpy→5cyc?Cycpy?α | 46.4 | 31.8 | 15.5 | ||
6cyc | R15 | 6cyc?Dicpy→6cyc?Dicpy?γ | 46.4 | 30.5 | 15.5 | ||
C6 class | C3H3 | 2cyc | R16 | 2cyc?Naph→2cyc?Naph?α | 104.2 | 18.4 | 86.2 |
C3H5 | 2cyc | R17 | 2cyc?Naph→2cyc?Naph?α | 120.1 | 19.2 | 102.5 | |
C5H5 | 2cyc | R18 | 2cyc?Naph→2cyc?Naph?α | 131.4 | 6.3 | 125.5 | |
nC4H5 | 2cyc | R19 | 2cyc?Naph→2cyc?Naph?α | 41.4 | 37.2 | 4.2 | |
3cyc | R20 | 3cyc?Anth→3cyc?Anth?β | 42.3 | 38.1 | 4.2 | ||
4cyc | R21 | 4cyc?Tetce→4cyc?Tetce?β | 41.0 | 38.1 | 4.6 | ||
3cyc | R22 | 3cyc?Phen→3cyc?Phen?α | 42.7 | 38.9 | 3.8 | ||
3cyc | R23 | 3cyc?Acen→3cyc?Acen?β | 42.3 | 39.7 | 2.5 | ||
4cyc | R24 | 4cyc?Pyre→4cyc?Pyre?α | 41.8 | 38.5 | 2.5 | ||
4cyc | R25 | 4cyc?Tetph→4cyc?Tetph?α | 41.8 | 45.6 | -3.8 | ||
4cyc | R26 | 4cyc?Acep→4cyc?Acep?δ | 41.8 | 38.5 | 3.3 | ||
5cyc | R27 | 5cyc?Cycpy→5cyc?Cycpy?δ | 41.0 | 38.1 | 4.2 | ||
6cyc | R28 | 6cyc?Dicpy→6cyc?Dicpy?β | 41.4 | 39.7 | 1.7 | ||
iC4H5 | 2cyc | R29 | 2cyc?Naph→2cyc?Naph?α | 44.4 | 26.4 | 18.0 | |
3cyc | R30 | 3cyc?Anth→3cyc?Anth?β | 43.9 | 25.9 | 18.0 | ||
4cyc | R31 | 4cyc?Tetce→4cyc?Tetce?β | 45.6 | 28.0 | 18.0 | ||
3cyc | R32 | 3cyc?Phen→3cyc?Phen?α | 45.6 | 27.6 | 17.6 | ||
3cyc | R33 | 3cyc?Acen→3cyc?Acen?β | 46.9 | 30.1 | 15.9 | ||
4cyc | R34 | 4cyc?Pyre→4cyc?Pyre?α | 45.2 | 27.6 | 15.9 | ||
4cyc | R35 | 4cyc?Tetph→4cyc?Tetph?α | 43.9 | 33.5 | 9.6 | ||
4cyc | R36 | 4cyc?Acep→4cyc?Acep?δ | 45.2 | 27.2 | 17.2 | ||
5cyc | R37 | 5cyc?Cycpy→5cyc?Cycpy?δ | 44.4 | 27.2 | 17.6 | ||
6cyc | R38 | 6cyc?Dicpy→6cyc?Dicpy?β | 45.2 | 29.3 | 15.1 | ||
C6H5 | 2cyc | R39 | 2cyc?Naph→2cyc?Naph?α | 38.1 | 36.4 | 2.5 | |
3cyc | R40 | 3cyc?Anth→3cyc?Anth?β | 38.5 | 36.8 | 2.5 | ||
4cyc | R41 | 4cyc?Tetce→4cyc?Tetce?β | 38.9 | 37.7 | 2.9 | ||
3cyc | R42 | 3cyc?Phen→3cyc?Phen?α | 37.7 | 36.4 | 2.1 | ||
3cyc | R43 | 3cyc?Acen→3cyc?Acen?β | 39.3 | 38.5 | 0.8 | ||
4cyc | R44 | 4cyc?Pyre→4cyc?Pyre?α | 37.7 | 36.4 | 0.8 | ||
4cyc | R45 | 4cyc?Tetph→4cyc?Tetph?α | 37.2 | 43.1 | -5.4 | ||
4cyc | R46 | 4cyc?Acep→4cyc?Acep?δ | 37.7 | 36.0 | 1.7 | ||
5cyc | R47 | 5cyc?Cycpy→5cyc?Cycpy?δ | 36.4 | 35.1 | 2.5 | ||
6cyc | R48 | 6cyc?Dicpy→6cyc?Dicpy?β | 37.7 | 37.7 | 0 |
Reaction class | nC4H5 | iC4H5 | C6H5 | |||
---|---|---|---|---|---|---|
AEB | MAD | AEB | MAD | AEB | MAD | |
C5 class | 50.6 | 0.8a | 55.6 | 2.1 | 46.9 | 0.8a |
C6 class | 41.8 | 1.7a | 45.2 | 2.9a | 38.1 | 2.9a |
Difference between C5 and C6 classes | 8.8 | 10.0b | 10.5 | 12.6b | 8.8 | 10.9b |
Table 4 Summary of energy barriers(ΔE1, kJ/mol) belonging to different reaction classes
Reaction class | nC4H5 | iC4H5 | C6H5 | |||
---|---|---|---|---|---|---|
AEB | MAD | AEB | MAD | AEB | MAD | |
C5 class | 50.6 | 0.8a | 55.6 | 2.1 | 46.9 | 0.8a |
C6 class | 41.8 | 1.7a | 45.2 | 2.9a | 38.1 | 2.9a |
Difference between C5 and C6 classes | 8.8 | 10.0b | 10.5 | 12.6b | 8.8 | 10.9b |
Radical | Reaction | Reactant | 500 K | 1000 K | 2500 K | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
krule/ (cm3·mol-1·s-1) | kTST/ (cm3·mol-1·s-1) | f | u | krule/ (cm3·mol-1·s-1) | kTST/ (cm3·mol-1·s-1) | f | u | krule/ (cm3·mol-1·s-1) | kTST/ (cm3·mol-1·s-1) | f | u | |||
nC4H5 | R19 | 2cyc?Naph | 2.31×106 | 1.39×106 | 0.6 | 1.81 | 1.62×109 | 9.47×108 | 0.58 | 1.76 | 5.64×1011 | 3.23×1011 | 0.57 | 1.73 |
R20 | 3cyc?Anth | 2.31×106 | 1.73×106 | 0.75 | 1.62×109 | 1.27×109 | 0.78 | 5.64×1011 | 4.46×1011 | 0.79 | ||||
R21 | 4cyc?Tetce | 2.31×106 | 2.51×106 | 1.09 | 1.62×109 | 1.67×109 | 1.03 | 5.64×1011 | 5.58×1011 | 0.99 | ||||
iC4H5 | R29 | 2cyc?Naph | 2.76×105 | 3.26×105 | 1.18 | 3.50 | 2.62×108 | 3.03×108 | 1.16 | 3.05 | 1.08×1011 | 1.24×1011 | 1.14 | 2.87 |
R30 | 3cyc?Anth | 2.76×105 | 6.44×105 | 2.34 | 2.62×108 | 5.59×108 | 2.14 | 1.08×1011 | 2.19×1011 | 2.02 | ||||
R31 | 4cyc?Tetce | 2.76×105 | 1.84×105 | 0.67 | 2.62×108 | 1.83×108 | 0.70 | 1.08×1011 | 7.62×1010 | 0.70 | ||||
C6H5 | R39 | 2cyc?Naph | 5.88×106 | 2.91×106 | 0.5 | 2.04 | 3.24×109 | 1.62×109 | 0.5 | 1.98 | 1.00×1012 | 4.94×1011 | 0.49 | 1.97 |
R40 | 3cyc?Anth | 5.88×106 | 4.64×106 | 0.79 | 3.24×109 | 2.61×109 | 0.8 | 1.00×1012 | 7.88×1011 | 0.79 | ||||
R41 | 4cyc?Tetce | 5.88×106 | 2.27×106 | 0.39 | 3.24×109 | 1.32×109 | 0.41 | 1.00×1012 | 4.01×1011 | 0.4 |
Table 5 Effect of the size of PAHs on the rate constants of C6 reaction class
Radical | Reaction | Reactant | 500 K | 1000 K | 2500 K | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
krule/ (cm3·mol-1·s-1) | kTST/ (cm3·mol-1·s-1) | f | u | krule/ (cm3·mol-1·s-1) | kTST/ (cm3·mol-1·s-1) | f | u | krule/ (cm3·mol-1·s-1) | kTST/ (cm3·mol-1·s-1) | f | u | |||
nC4H5 | R19 | 2cyc?Naph | 2.31×106 | 1.39×106 | 0.6 | 1.81 | 1.62×109 | 9.47×108 | 0.58 | 1.76 | 5.64×1011 | 3.23×1011 | 0.57 | 1.73 |
R20 | 3cyc?Anth | 2.31×106 | 1.73×106 | 0.75 | 1.62×109 | 1.27×109 | 0.78 | 5.64×1011 | 4.46×1011 | 0.79 | ||||
R21 | 4cyc?Tetce | 2.31×106 | 2.51×106 | 1.09 | 1.62×109 | 1.67×109 | 1.03 | 5.64×1011 | 5.58×1011 | 0.99 | ||||
iC4H5 | R29 | 2cyc?Naph | 2.76×105 | 3.26×105 | 1.18 | 3.50 | 2.62×108 | 3.03×108 | 1.16 | 3.05 | 1.08×1011 | 1.24×1011 | 1.14 | 2.87 |
R30 | 3cyc?Anth | 2.76×105 | 6.44×105 | 2.34 | 2.62×108 | 5.59×108 | 2.14 | 1.08×1011 | 2.19×1011 | 2.02 | ||||
R31 | 4cyc?Tetce | 2.76×105 | 1.84×105 | 0.67 | 2.62×108 | 1.83×108 | 0.70 | 1.08×1011 | 7.62×1010 | 0.70 | ||||
C6H5 | R39 | 2cyc?Naph | 5.88×106 | 2.91×106 | 0.5 | 2.04 | 3.24×109 | 1.62×109 | 0.5 | 1.98 | 1.00×1012 | 4.94×1011 | 0.49 | 1.97 |
R40 | 3cyc?Anth | 5.88×106 | 4.64×106 | 0.79 | 3.24×109 | 2.61×109 | 0.8 | 1.00×1012 | 7.88×1011 | 0.79 | ||||
R41 | 4cyc?Tetce | 5.88×106 | 2.27×106 | 0.39 | 3.24×109 | 1.32×109 | 0.41 | 1.00×1012 | 4.01×1011 | 0.4 |
Radical | Reaction | Structure | 500 K | 1000 K | 2500 K | |||
---|---|---|---|---|---|---|---|---|
kTST/ (cm3·mol-1·s-1) | u | kTST/ (cm3·mol-1·s-1) | u | kTST/ (cm3·mol-1·s-1) | u | |||
nC4H5 | R4 | C5 | 2.07×105 | 19.18 | 4.11×108 | 7.10 | 2.66×1011 | 3.95 |
R6 | C5 | 2.82×105 | 5.20×108 | 3.23×1011 | ||||
R23 | C6 | 3.97×106 | 2.92×109 | 1.05×1012 | ||||
R27 | C6 | 9.42×105 | 6.10×108 | 2.01×1011 | ||||
iC4H5 | R8 | C5 | 3.34×104 | 9.81 | 1.17×108 | 4.04 | 1.06×1011 | 2.35 |
R10 | C5 | 3.14×104 | 8.87×107 | 7.14×1010 | ||||
R33 | C6 | 3.08×105 | 3.58×108 | 1.68×1011 | ||||
R37 | C6 | 2.40×105 | 2.15×108 | 8.63×1010 | ||||
C6H5 | R12 | C5 | 6.43×105 | 18.40 | 1.08×109 | 7.72 | 6.45×1011 | 4.63 |
R14 | C5 | 5.76×105 | 8.56×108 | 4.77×1011 | ||||
R43 | C6 | 1.06×107 | 6.61×109 | 2.21×1012 | ||||
R47 | C6 | 7.87×106 | 4.24×109 | 1.30×1012 |
Table 6 Effect of the structure(five- or six-membered ring) on the rate constants
Radical | Reaction | Structure | 500 K | 1000 K | 2500 K | |||
---|---|---|---|---|---|---|---|---|
kTST/ (cm3·mol-1·s-1) | u | kTST/ (cm3·mol-1·s-1) | u | kTST/ (cm3·mol-1·s-1) | u | |||
nC4H5 | R4 | C5 | 2.07×105 | 19.18 | 4.11×108 | 7.10 | 2.66×1011 | 3.95 |
R6 | C5 | 2.82×105 | 5.20×108 | 3.23×1011 | ||||
R23 | C6 | 3.97×106 | 2.92×109 | 1.05×1012 | ||||
R27 | C6 | 9.42×105 | 6.10×108 | 2.01×1011 | ||||
iC4H5 | R8 | C5 | 3.34×104 | 9.81 | 1.17×108 | 4.04 | 1.06×1011 | 2.35 |
R10 | C5 | 3.14×104 | 8.87×107 | 7.14×1010 | ||||
R33 | C6 | 3.08×105 | 3.58×108 | 1.68×1011 | ||||
R37 | C6 | 2.40×105 | 2.15×108 | 8.63×1010 | ||||
C6H5 | R12 | C5 | 6.43×105 | 18.40 | 1.08×109 | 7.72 | 6.45×1011 | 4.63 |
R14 | C5 | 5.76×105 | 8.56×108 | 4.77×1011 | ||||
R43 | C6 | 1.06×107 | 6.61×109 | 2.21×1012 | ||||
R47 | C6 | 7.87×106 | 4.24×109 | 1.30×1012 |
Hydrogen atom type | PAHS | u | |||||
---|---|---|---|---|---|---|---|
A/(cm3·mol-1·s-1) | n | Ea/(kJ·mol-1) | 500 K | 1000 K | 2500 K | ||
nC4H5 | C5 class | 0.456 | 3.80 | 40.71 | 2.94 | 2.77 | 2.73 |
C6 class | 0.588 | 3.73 | 32.43 | 5.10 | 4.97 | 5.22 | |
iC4H5 | C5 class | 0.111 | 3.81 | 45.52 | 1.43 | 1.64 | 1.78 |
C6 class | 0.118 | 3.74 | 34.73 | 4.32 | 5.09 | 5.64 | |
C6H5 | C5 class | 0.914 | 3.76 | 39.12 | 2.98 | 3.40 | 3.70 |
C6 class | 0.558 | 3.79 | 29.83 | 5.23 | 5.03 | 5.51 |
Table 7 Rate rules for H-abstraction reaction of PAHs by nC4H5, iC4H5, C5H5, and C6H5 radical
Hydrogen atom type | PAHS | u | |||||
---|---|---|---|---|---|---|---|
A/(cm3·mol-1·s-1) | n | Ea/(kJ·mol-1) | 500 K | 1000 K | 2500 K | ||
nC4H5 | C5 class | 0.456 | 3.80 | 40.71 | 2.94 | 2.77 | 2.73 |
C6 class | 0.588 | 3.73 | 32.43 | 5.10 | 4.97 | 5.22 | |
iC4H5 | C5 class | 0.111 | 3.81 | 45.52 | 1.43 | 1.64 | 1.78 |
C6 class | 0.118 | 3.74 | 34.73 | 4.32 | 5.09 | 5.64 | |
C6H5 | C5 class | 0.914 | 3.76 | 39.12 | 2.98 | 3.40 | 3.70 |
C6 class | 0.558 | 3.79 | 29.83 | 5.23 | 5.03 | 5.51 |
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