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‎input/kinetics/libraries/phenolic_pyrolysis/dictionary.txt‎

Lines changed: 65 additions & 128 deletions
Original file line numberDiff line numberDiff line change
@@ -937,136 +937,73 @@ multiplicity 2
937937
41 H u0 p0 c0 {1,S}
938938
42 H u0 p0 c0 {2,S}
939939

940-
C9H11O
941-
multiplicity 2
942-
1 O u0 p2 c0 {8,S} {21,S}
943-
2 C u1 p0 c0 {5,S} {11,S} {12,S}
944-
3 C u0 p0 c0 {7,S} {13,S} {14,S} {15,S}
945-
4 C u0 p0 c0 {6,S} {16,S} {17,S} {18,S}
946-
5 C u0 p0 c0 {2,S} {6,B} {8,B}
947-
6 C u0 p0 c0 {4,S} {5,B} {10,B}
948-
7 C u0 p0 c0 {3,S} {8,B} {9,B}
949-
8 C u0 p0 c0 {1,S} {5,B} {7,B}
950-
9 C u0 p0 c0 {7,B} {10,B} {19,S}
951-
10 C u0 p0 c0 {6,B} {9,B} {20,S}
952-
11 H u0 p0 c0 {2,S}
953-
12 H u0 p0 c0 {2,S}
954-
13 H u0 p0 c0 {3,S}
955-
14 H u0 p0 c0 {3,S}
956-
15 H u0 p0 c0 {3,S}
957-
16 H u0 p0 c0 {4,S}
958-
17 H u0 p0 c0 {4,S}
959-
18 H u0 p0 c0 {4,S}
960-
19 H u0 p0 c0 {9,S}
961-
20 H u0 p0 c0 {10,S}
962-
21 H u0 p0 c0 {1,S}
963-
964-
C18H21O2
965-
multiplicity 2
966-
1 O u0 p2 c0 {16,S} {40,S}
967-
2 O u0 p2 c0 {15,S} {41,S}
968-
3 C u1 p0 c0 {11,S} {21,S} {22,S}
969-
4 C u0 p0 c0 {5,S} {9,S} {23,S} {24,S}
970-
5 C u0 p0 c0 {4,S} {12,S} {25,S} {26,S}
971-
6 C u0 p0 c0 {10,S} {27,S} {28,S} {29,S}
972-
7 C u0 p0 c0 {13,S} {30,S} {31,S} {32,S}
973-
8 C u0 p0 c0 {14,S} {33,S} {34,S} {35,S}
974-
9 C u0 p0 c0 {4,S} {14,B} {15,B}
975-
10 C u0 p0 c0 {6,S} {13,B} {16,B}
976-
11 C u0 p0 c0 {3,S} {15,B} {19,B}
977-
12 C u0 p0 c0 {5,S} {16,B} {20,B}
978-
13 C u0 p0 c0 {7,S} {10,B} {17,B}
979-
14 C u0 p0 c0 {8,S} {9,B} {18,B}
980-
15 C u0 p0 c0 {2,S} {9,B} {11,B}
981-
16 C u0 p0 c0 {1,S} {10,B} {12,B}
982-
17 C u0 p0 c0 {13,B} {20,B} {36,S}
983-
18 C u0 p0 c0 {14,B} {19,B} {38,S}
984-
19 C u0 p0 c0 {11,B} {18,B} {39,S}
985-
20 C u0 p0 c0 {12,B} {17,B} {37,S}
940+
char_mature17
941+
1 O u0 p2 c0 {13,S} {33,S}
942+
2 C u0 p0 c0 {6,S} {7,S} {18,S} {19,S}
943+
3 C u0 p0 c0 {10,S} {20,S} {21,S} {22,S}
944+
4 C u0 p0 c0 {9,S} {23,S} {24,S} {25,S}
945+
5 C u0 p0 c0 {8,S} {26,S} {27,S} {28,S}
946+
6 C u0 p0 c0 {2,S} {12,D} {14,S}
947+
7 C u0 p0 c0 {2,S} {11,D} {15,S}
948+
8 C u0 p0 c0 {5,S} {11,S} {13,D}
949+
9 C u0 p0 c0 {4,S} {13,S} {15,D}
950+
10 C u0 p0 c0 {3,S} {14,D} {16,S}
951+
11 C u0 p0 c0 {7,D} {8,S} {12,S}
952+
12 C u0 p0 c0 {6,D} {11,S} {17,S}
953+
13 C u0 p0 c0 {1,S} {8,D} {9,S}
954+
14 C u0 p0 c0 {6,S} {10,D} {31,S}
955+
15 C u0 p0 c0 {7,S} {9,D} {32,S}
956+
16 C u0 p0 c0 {10,S} {17,D} {29,S}
957+
17 C u0 p0 c0 {12,S} {16,D} {30,S}
958+
18 H u0 p0 c0 {2,S}
959+
19 H u0 p0 c0 {2,S}
960+
20 H u0 p0 c0 {3,S}
986961
21 H u0 p0 c0 {3,S}
987962
22 H u0 p0 c0 {3,S}
988963
23 H u0 p0 c0 {4,S}
989964
24 H u0 p0 c0 {4,S}
990-
25 H u0 p0 c0 {5,S}
965+
25 H u0 p0 c0 {4,S}
991966
26 H u0 p0 c0 {5,S}
992-
27 H u0 p0 c0 {6,S}
993-
28 H u0 p0 c0 {6,S}
994-
29 H u0 p0 c0 {6,S}
995-
30 H u0 p0 c0 {7,S}
996-
31 H u0 p0 c0 {7,S}
997-
32 H u0 p0 c0 {7,S}
998-
33 H u0 p0 c0 {8,S}
999-
34 H u0 p0 c0 {8,S}
1000-
35 H u0 p0 c0 {8,S}
1001-
36 H u0 p0 c0 {17,S}
1002-
37 H u0 p0 c0 {20,S}
1003-
38 H u0 p0 c0 {18,S}
1004-
39 H u0 p0 c0 {19,S}
1005-
40 H u0 p0 c0 {1,S}
1006-
41 H u0 p0 c0 {2,S}
1007-
1008-
1009-
novolak_trimer
1010-
1 O u0 p2 c0 {24,S} {60,S}
1011-
2 O u0 p2 c0 {22,S} {61,S}
1012-
3 O u0 p2 c0 {23,S} {62,S}
1013-
4 C u0 p0 c0 {5,S} {16,S} {31,S} {32,S}
1014-
5 C u0 p0 c0 {4,S} {13,S} {33,S} {34,S}
1015-
6 C u0 p0 c0 {7,S} {14,S} {35,S} {36,S}
1016-
7 C u0 p0 c0 {6,S} {17,S} {37,S} {38,S}
1017-
8 C u0 p0 c0 {15,S} {39,S} {40,S} {41,S}
1018-
9 C u0 p0 c0 {18,S} {42,S} {43,S} {44,S}
1019-
10 C u0 p0 c0 {19,S} {45,S} {46,S} {47,S}
1020-
11 C u0 p0 c0 {21,S} {48,S} {49,S} {53,S}
1021-
12 C u0 p0 c0 {20,S} {50,S} {51,S} {52,S}
1022-
13 C u0 p0 c0 {5,S} {20,B} {23,B}
1023-
14 C u0 p0 c0 {6,S} {19,B} {22,B}
1024-
15 C u0 p0 c0 {8,S} {18,B} {24,B}
1025-
16 C u0 p0 c0 {4,S} {22,B} {27,B}
1026-
17 C u0 p0 c0 {7,S} {24,B} {30,B}
1027-
18 C u0 p0 c0 {9,S} {15,B} {25,B}
1028-
19 C u0 p0 c0 {10,S} {14,B} {26,B}
1029-
20 C u0 p0 c0 {12,S} {13,B} {28,B}
1030-
21 C u0 p0 c0 {11,S} {23,B} {29,B}
1031-
22 C u0 p0 c0 {2,S} {14,B} {16,B}
1032-
23 C u0 p0 c0 {3,S} {13,B} {21,B}
1033-
24 C u0 p0 c0 {1,S} {15,B} {17,B}
1034-
25 C u0 p0 c0 {18,B} {30,B} {54,S}
1035-
26 C u0 p0 c0 {19,B} {27,B} {56,S}
1036-
27 C u0 p0 c0 {16,B} {26,B} {57,S}
1037-
28 C u0 p0 c0 {20,B} {29,B} {58,S}
1038-
29 C u0 p0 c0 {21,B} {28,B} {59,S}
1039-
30 C u0 p0 c0 {17,B} {25,B} {55,S}
1040-
31 H u0 p0 c0 {4,S}
1041-
32 H u0 p0 c0 {4,S}
1042-
33 H u0 p0 c0 {5,S}
1043-
34 H u0 p0 c0 {5,S}
1044-
35 H u0 p0 c0 {6,S}
1045-
36 H u0 p0 c0 {6,S}
1046-
37 H u0 p0 c0 {7,S}
1047-
38 H u0 p0 c0 {7,S}
1048-
39 H u0 p0 c0 {8,S}
1049-
40 H u0 p0 c0 {8,S}
1050-
41 H u0 p0 c0 {8,S}
1051-
42 H u0 p0 c0 {9,S}
1052-
43 H u0 p0 c0 {9,S}
1053-
44 H u0 p0 c0 {9,S}
1054-
45 H u0 p0 c0 {10,S}
1055-
46 H u0 p0 c0 {10,S}
1056-
47 H u0 p0 c0 {10,S}
1057-
48 H u0 p0 c0 {11,S}
1058-
49 H u0 p0 c0 {11,S}
1059-
50 H u0 p0 c0 {12,S}
1060-
51 H u0 p0 c0 {12,S}
1061-
52 H u0 p0 c0 {12,S}
1062-
53 H u0 p0 c0 {11,S}
1063-
54 H u0 p0 c0 {25,S}
1064-
55 H u0 p0 c0 {30,S}
1065-
56 H u0 p0 c0 {26,S}
1066-
57 H u0 p0 c0 {27,S}
1067-
58 H u0 p0 c0 {28,S}
1068-
59 H u0 p0 c0 {29,S}
1069-
60 H u0 p0 c0 {1,S}
1070-
61 H u0 p0 c0 {2,S}
1071-
62 H u0 p0 c0 {3,S}
1072-
967+
27 H u0 p0 c0 {5,S}
968+
28 H u0 p0 c0 {5,S}
969+
29 H u0 p0 c0 {16,S}
970+
30 H u0 p0 c0 {17,S}
971+
31 H u0 p0 c0 {14,S}
972+
32 H u0 p0 c0 {15,S}
973+
33 H u0 p0 c0 {1,S}
974+
975+
char_mature19
976+
1 O u0 p2 c0 {12,S} {34,S}
977+
2 C u0 p0 c0 {5,S} {6,S} {19,S} {20,S}
978+
3 C u0 p0 c0 {8,S} {21,S} {22,S} {23,S}
979+
4 C u0 p0 c0 {7,S} {24,S} {25,S} {26,S}
980+
5 C u0 p0 c0 {2,S} {10,D} {14,S}
981+
6 C u0 p0 c0 {2,S} {9,D} {13,S}
982+
7 C u0 p0 c0 {4,S} {9,S} {12,D}
983+
8 C u0 p0 c0 {3,S} {12,S} {13,D}
984+
9 C u0 p0 c0 {6,D} {7,S} {10,S}
985+
10 C u0 p0 c0 {5,D} {9,S} {16,S}
986+
11 C u0 p0 c0 {14,D} {15,S} {17,S}
987+
12 C u0 p0 c0 {1,S} {7,D} {8,S}
988+
13 C u0 p0 c0 {6,S} {8,D} {31,S}
989+
14 C u0 p0 c0 {5,S} {11,D} {30,S}
990+
15 C u0 p0 c0 {11,S} {16,D} {28,S}
991+
16 C u0 p0 c0 {10,S} {15,D} {29,S}
992+
17 C u0 p0 c0 {11,S} {18,D} {27,S}
993+
18 C u0 p0 c0 {17,D} {32,S} {33,S}
994+
19 H u0 p0 c0 {2,S}
995+
20 H u0 p0 c0 {2,S}
996+
21 H u0 p0 c0 {3,S}
997+
22 H u0 p0 c0 {3,S}
998+
23 H u0 p0 c0 {3,S}
999+
24 H u0 p0 c0 {4,S}
1000+
25 H u0 p0 c0 {4,S}
1001+
26 H u0 p0 c0 {4,S}
1002+
27 H u0 p0 c0 {17,S}
1003+
28 H u0 p0 c0 {15,S}
1004+
29 H u0 p0 c0 {16,S}
1005+
30 H u0 p0 c0 {14,S}
1006+
31 H u0 p0 c0 {13,S}
1007+
32 H u0 p0 c0 {18,S}
1008+
33 H u0 p0 c0 {18,S}
1009+
34 H u0 p0 c0 {1,S}

‎input/kinetics/libraries/phenolic_pyrolysis/reactions.py‎

Lines changed: 47 additions & 25 deletions
Original file line numberDiff line numberDiff line change
@@ -367,33 +367,16 @@
367367
# ==============================================================================
368368

369369
# ------------------------------------------------------------------------------
370-
# Stage I — facile initiation (physical trimer bridge homolysis; sets DTG peak)
370+
# Stage I — facile initiation: applied at the SPLICE step, not seeded.
371+
# The physical bridge homolysis (proxy -> C9H11O + C18H21O2) is degenerate under
372+
# kineticsFamilies=['polymers'] -- RMG cannot generate sinks for the benzyl
373+
# products, which then consume all proxy and short-circuit the cascade (residue
374+
# 100% C18H21O2, char chemistry inactive). The lumped initiation
375+
# (proxy => trimer_rad33 + H, Ea=62.9, the C-C-homolysis rate) is injected in
376+
# splice_yaml.py instead -- it directly produces the propagating radical that has
377+
# the seeded beta-scission sink. See ~/runs/RMG/poly_101/v9_report.md.
371378
# ------------------------------------------------------------------------------
372379

373-
entry(
374-
index = 15,
375-
label = "novolak_trimer <=> C9H11O + C18H21O2",
376-
degeneracy = 1,
377-
kinetics = Arrhenius(
378-
A = (1.995e15, 's^-1'),
379-
n = 0.0,
380-
Ea = (62.9, 'kcal/mol'),
381-
T0 = (1, 'K'),
382-
),
383-
shortDesc = u"R15: novolak trimer ethano-bridge central C-C homolysis (initiation)",
384-
longDesc = u"""
385-
Provenance: Direct (model compound), via the bibenzyl analog of seed entry 1
386-
(PhCH2-CH2Ph central C-C BDE 62.9 kcal/mol, A=10^15.3 s^-1). Homolysis of one
387-
trimer ethano bridge yields a C9 benzyl radical (C9H11O) and a C18 benzyl-type
388-
radical (C18H21O2). This is the *physical* facile initiation that replaces the
389-
v8 stand-in (proxy -> trimer_rad33 + H): the peak is initiation-limited and an
390-
Ea=62.9 initiation lowers the DTG peak from ~704 to ~510 C (handoff peak
391-
diagnosis). RMG is expected to propagate via H-abstraction (benzyl + trimer ->
392-
closed + trimer_rad33/38/44), feeding the seeded beta-scissions (entries 12-14).
393-
Uncertainty factor: x3.
394-
""",
395-
)
396-
397380
# ------------------------------------------------------------------------------
398381
# Stage III — char formation (dehydrogenative cross-linking of aryl radicals)
399382
# ------------------------------------------------------------------------------
@@ -530,3 +513,42 @@
530513
Uncertainty factor: x10.
531514
""",
532515
)
516+
517+
# ------------------------------------------------------------------------------
518+
# Stage III — char maturation / carbonization (v10, 2026-05-27)
519+
# ------------------------------------------------------------------------------
520+
# The v9 char (char_C17/char_C19) was terminal -> the TGA was flat above the main
521+
# peak. Real novolak char keeps losing mass at high T (Zone III: dehydrogenation,
522+
# decarbonylation, ring-fusion -> H2, CO, CH4). These two lumped maturation steps
523+
# give the second high-T DTG peak (~660-720 C) and pull the residue toward the
524+
# literature 55+/-5 wt%. The matured lumps (char_mature17/_19) are more-condensed
525+
# fused aromatics. Rate = the seed's own phenol decarbonylation (R9: A=1e12,
526+
# Ea=60.8); the 2nd-peak position + extent EMERGE from it. See v9_report.md / v10.
527+
528+
entry(
529+
index = 25,
530+
label = "char_C17 <=> char_mature17 + CO + H2",
531+
degeneracy = 1,
532+
kinetics = Arrhenius(A = (1.0e12, 's^-1'), n = 0.0, Ea = (60.8, 'kcal/mol'), T0 = (1, 'K')),
533+
shortDesc = u"R25: Zone-III char maturation (decarbonylation + dehydrogenation), C17",
534+
longDesc = u"""
535+
Provenance: Analogy (seed R9, phenol -> CO + cpd: A=1e12, Ea=60.8 kcal/mol).
536+
Lumped high-T carbonization of the C17 char: a phenolic ring decarbonylates
537+
(-> CO) and the structure dehydrogenatively fuses (-> H2), leaving a more-
538+
condensed aromatic lump (char_mature17, C16H16O). Gives the second high-T DTG
539+
peak the v9 terminal-char model lacked. Uncertainty factor: x10.
540+
""",
541+
)
542+
543+
entry(
544+
index = 26,
545+
label = "char_C19 <=> char_mature19 + CO + CH4",
546+
degeneracy = 1,
547+
kinetics = Arrhenius(A = (1.0e12, 's^-1'), n = 0.0, Ea = (60.8, 'kcal/mol'), T0 = (1, 'K')),
548+
shortDesc = u"R26: Zone-III char maturation (decarbonylation + demethanation), C19",
549+
longDesc = u"""
550+
Provenance: Analogy (seed R9). As R25 for the C19 char; releases CO + CH4
551+
(both classic Zone-III novolak gases) leaving char_mature19 (C17H16O).
552+
Uncertainty factor: x10.
553+
""",
554+
)

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