12. Danish Environmental Protection Agency, Brominated name retardants, Substance now analysts and
4.3 計算結果および考秦
4.3.2 臭素系ダイオキシン類の生成に関する熱力学的検討
AHfO = 43.437 X ‑ 9.784 y I 96.060
AGfO = 35.036 X‑4.438 y+ 17.880
S0 ‑39.104 X+28.675 y+414.624
(R2 ‑ 0.988)
(R2 ‑ 0.979)
(R2 ‑ 0.999)
cp(298K)‑ 16･816X+15･765y+ 181･594 (R2‑0･9998)
(4.14)
(4.15)
(4.16)
(4.17)
I‑tOuJ･fV1.DV
160 140 120 100 80 60 40 20
0
‑20
‑40
‑60
‑80
300 500 700 900 1100 1300 1500
r/K
図4.13 臭化および塩化によるDDから2,3,7,8lTeBCDDs‑の反応の自由エネルギー変化
次に､ PCDDsおよびPBDDsの優先安定領域を臭素一塩素ポテンシャル線図を用いて考察する｡
2,3,7,8‑TeCDDから2,3,7,8‑TeBCDDs ‑の臭化反応は以下のように表される.
2/m TeCDD + Br2(g) ‑ 2/m BrmCl(4̲m)DD + Cl2(g), (m=1,2,3,4)
AG/ =‑RTlnK=‑RTln
PB2,1冒,(. ̲ 〜 PD Pc/2
P;13;D PB,,
ここで､ AGroは反応の自由エネルギー変化､ Rは気体定数､ pは分圧(atm)を表す｡図4･14に反応式(4･19) に関して､臭素一塩素ポテンシャル線図を示す.ポテンシャル線図の計算では､便宜上､ 2,3,7,8‑TeCDD および2,3,7,8‑TeBCDDの分圧を1と仮定し､温度は598Kである.図中には､同時に種々のPfBJPHCl 分圧比に対する臭素一塩素ポテンシャル線も示している｡反応式は以下のように表される｡
2IiCl(g) + Br2(g) ‑ 2HB4g) + C12(g) (4121)
AGo･ ‑ ‑RT.nK ‑ ‑RTlnR '4･22'
図4.14より､臭素化のためには､臭素ポテンシャルが塩素ポテンシャルに比べて7桁ほど高い必要が
あることがわかる｡しかし､ 2,3,7,8‑TeBDDの優先安定領域においてさえも､ HBrのHClに対する比率
はそれほど高くなく､両者は同程度であることがわかる｡この理由は､ HBrはHClに比べて､相当に熱
力学的に不安定であるためである｡
標準生成自由エネルギー(AGP)からは臭素化ダイオキシンは塩素化ダイオキシン【4,181に比べて不安 定であり､優先生成のためには相当に高い臭素ポテンシャルが必要であることがわかる｡しかし､図4.14 より､ HBrとHClの分圧が同程度ならば､十分に臭素ポテンシャル高くなることがわかる｡これは非常 に単純化した計算結果であるため詳細な議論は難しいが､条件によっては臭素化ダイオキシンの優先生 成が熱力学的に可能であることを示唆している｡
Sakaiら【19】は､難燃プラスチック試料の燃焼排ガス中のPBDD/FsおよびPCDD/Fsを分析している｡
例えば､投入サンプル中の塩素濃度が1.66 massO^'0､臭素濃度が3.2 mass%の場合､冷却後排ガス中の PBDD/FsとpcDD/Fsの含有割合はほぼ同等であることを報告している｡実際のプロセスでは非平衡状 態で反応が進行しているため直接的には言及できないが､臭素化ダイオキシンが､塩素化ダイオキシン に比べて熱力学的に相当に不安定であるにも関わらず､分解されずに排ガス中に同程度存在している理 由の一つとしては､図4.14の臭素一塩素ポテンシャル図に示したように､臭素ポテンシャルが塩素ポテ ンシャルよりも相当に高いガス雰囲気となっていることが考えられる0
1.0× 105
0.8× 105
0.6× 105
0.4× 105
0.2× 105
0
0 0.5× 10‑2 1.0× 10･2 1.5× 10‑2 2.0× 10‑2 2.5× 10‑2
PcJ2仲a
図4.14 TeBCDDsに関する臭素一塩素ポテンシャル線図
以下の表4.2から表4.5にPBDDs､ PBDFs､ PBCDDsおよびPBCDDFsの熱力学データ､比熱cp､標 準生成エントロピーAHfO､エントロピーSo､標準生成自由エネルギー△GfOの計算結果一覧をそれぞれ示
している｡
表4.2密度汎関数法によるPBDDsの熱力学データの計算結果(298･15K〜1500K)
AHfO(29 8 K) AGfO(29 8K)
So(29 8K)
compotmds kJ･morl kJ･mo1‑I J･mo1‑1･K‑I=AT3+B T2+c T+D
J･mol l･K IAXIO7 BX104 cxlO D
DD ‑59.28 56.2 409･9 1 1679 ･6･6 10 79.9 450.6 1.67 1 ‑6.544 73.7 452.5 1.672 ･6.542 106.4 491.2 1.667 ‑6.489
′
100.5 49 1.7 1.663 ‑6.472 i 05.6 491.4 1.662 ‑6.477 1 04.0 491.9 1.663 ‑6.477 98.4 492.7 1.664 16.476 98.7 492. 1 1.665 ‑6.477 105.4 492.0 1.663 =6.477 1 00.7 49 1.3 1.667 ‑6.484 92.7 493. 1 1.665 ‑6.475 92.9 492.5 1.666 ‑6.477 136.8 528.8 1.663 ‑6.43 I 134.0 532.6 1.667 16.417 131.5 531.6 1.660 ‑6.423 126.0 53 1.1 1.662 ‑6.425 125.8 533. 1 1.661 16.422 1 32.3 532.2 1.660 ‑6.423 125.4 534.3 1.655 ‑6.406 120. 1 533.0 1.657 ‑6.407 120.0 534.3 1.657 ‑6.406 1 26.5 534.4 1.655 ‑6.406 131.5 534.1 1.655 ‑6.409 124.9 533.9 1.656 ‑6.409 120.2 532.8 1.661 ‑6.419 173.7 568.4 1.659 ‑6.381 162.2 570.0 1.656 ‑6.367 156.6 570.6 1.657 ‑6.368 156.6 571.2 1.657 ‑6.368 162.7 571.5 1,656 16.368 160.5 573.6 1.649 ‑6.350 154.2 573.7 1.652 ‑6.354 154.3 572.8 1.652 ‑6.353 160.4 574.3 1.649 16.350 159.5 569.3 1.657 ‑6.371 153.6 572.5 1.652 ‑6.352
9.596 49.10 9.400 ‑26.92 9.388 ‑25.86 9.212 ‑4.55 9.191 ‑3.6$
9.206 14.87 9.204 ‑4.63 9.194 ‑3.70 9.195 ‑3.75 9.204 ‑4.63 9.201 ‑3.78 9.184 12.85 9.187 ‑2.98 9.023 1 7.82 9.014 17.62 9.018 17.57 9.011 18.39 9.008 18.54 9.017 17.64 S.996 18.58 8.989 19.3 I 8.986 19.49 8.995 18.67 9.008 17.55 9.000 18.37 8.998 1 9.26 8.847 39.34
8.829 40.04 8.822 40.84 8.82 1 40.93 8.830 39.95 8.&18 39.80 8.815 40.48 8.813 40.53 8.818 39.i6 S.835 39.63 S.810 40.77 1 ̲MoBDD ‑26.5
2̲MoBDD l32.2
1 ,2‑DiBDD 8.7 1 ,3‑DiBDD 3.0 I ,4‑DiBDD 8.0 1 ,6‑DiBDD 6.6
1 ,7‑DiBDD 1.3 1 ,S‑DiBDD I.4
1 ,9‑DiBDD 8.0 2,3‑DiBDD 3. 1 2,7‑DiBDD ‑4.4 2,8‑DiBDD ‑4･4 1 ,2,3‑TrBDD 47･ 1 1 ,2,4‑TrBDD 45 ･4 1 ,2,6‑TrBDD 42 ･6 1 ,2,7‑TrBDD 37･0 1 ,2,省一TrBDD 3 7･4 1 ,2,9‑TrBDD 43 ･7 1 ,3 ,6‑TrBDD 3 7･4
1,3,7‑TrBDD 3 1.7 1 ,3,8‑TrBDD 3 I.9 1 ,3,9‑TrBDD 38.5 1 ,4,6‑TrBDD 43.4 1 ,4,71TrBDD 36.8 2,3 ,6lTrBDD 3 7 14 2,3,7‑TrBDD 3 1 ･7 I ,2,3,4‑TeBDD 92 ･6 1 ,2,3,6‑TeBDD 8 1 ･6 I,2,3,7‑TeBDD 76. 1 1 ,2,3,8‑TeBDD 76.3 1 ,2,3,9lTeBDD 82･5 1 ,2,4,6‑TeBDD 80･9 I ,2,4,7‑TeBDD 74･7 1 ,2,4,8‑TeBDD 74.5
1,2,4,9‑TeBDD 8 1 ･0
1 ,2,6,7‑TeBDD 7i･6
表4.2 (続き)
AHfO(298K) AGfO(298K) So(298K)
Compounds
kJ･morl kJ･mo1‑I J･mo1‑1･K‑I
cD=A Te+B TZ+c T+D
J･mol 1･K 1AXIO7 BX104 cxlO D
1 ,2,6,8‑TeBDD l ,2,6,9‑TeBDD l ,2,7,8‑TeBDD l ,2,7,9‑TeBDD l ,2,8,9‑TeBDD l ,3 ,6,81TeBDD l ,3,6,9‑TeBDD l ,3,7,8‑TeBDD l ,3 ,7,9lTeBDD l ,4,6,9‑TeBDD l ,4,7,8‑TeBDD 2,3 ,7,8‑TeBDD 1 ,2,3,4,6‑PeBDD 1 ,2,3,4,7･PeBDD I ,2,3 ,6,71PeBDD 1 ,2,3 ,6,8‑PeBDD 1 ,2,3 ,6,9‑PeBDD 1 ,2,3,7,8‑PeBDD 1 ,2,3,7,9‑PeBDD 1 ,2,3 ,8,9‑PeBDD 1 ,2,4,6,7‑PeBDD I ,2,4,6,8‑PeBDD 1 ,2,4,6,9‑PeBDD 1 ,2,4,7,S‑PeBDD 1 ,2,4,7,9‑PeBDD 1 ,2,4,8,9‑PeBDD 1 ,2,3,4,6,7‑HxBDD 1 ,2,3,4,6,81HxBDD 1 ,2,3 ,4,6,9‑HxBDD 1 ,2,3 ,4,7,8‑HxBDD I ,2,3,6,7,S‑HxBDD I ,2,3,6,7,9‑HxBDD
736676465253. 220290203606549. 440224｣｣808
737973747968746869約73級128̲ 22m̲ 13m̲ 1 31 14̲ 19̲ 1 7̲ 12̲=̲ 121 ‑ 7̲ 64̲60̲65̲ 59朋̲ 57̲ 57̲ 581 561 56204204m 0ノ 4 4 0 7 3 00 5 5 5 ∠U 4 5 4 1 1 1 1 1 1 1
8 q/ 3 00 0 4 0 0 5 0 5 5 0 00 2 0ノ 3 3 00 00 2 cc 3 2 0 0 2 00 00 0 7 00 4 5 5 4 0 0ノ 2 0ノ 8 qノ 00 00 9 8 00 8 00 00 00 2 2 2 2 2 2 2 2 1 1 ′0 5 0ノ 1 1 1 1 つ一 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2
3 572.2 1.65 1 ‑6.356 2 570.2 1.657 ‑6.369 5 572.5 1.652 ‑6.354 1 570.9 1.656 ‑6.369 S ′ 575.0 1.648 ‑6.337 6 575.0 1.648 ‑6.341 3 573.2 1.652 ‑6.350 8.8 574.6 1.648 ‑6.338 9.3 575.3 1.647 ‑6.344 4 572.7 1.652 ‑6.355 8.5 571.3 1.657 ‑6.364 4 609.1 1.652 ‑6.317 .3 609.4 1.654 ‑6.3 18
2 532.8 1.661 ‑6.419 5 608.4 1.653 ‑6.3 15
3 609.6 1.649 16.30 1 4 611.8 1.648 ‑6.301
5 608.3 1.653 ‑6.3 13
2 613. 1 1.648 ‑6.296
7 611.2 1.653 ‑6.315
0 614.1 1.647 ‑6.299 7 6 1 6.2 1.643 ‑6.283
0 613.3 1.641 ‑6.285 5 6 1 0.4 1.648 ‑6.300
4 613.7 1.643 ‑6.284 8 61 1.8 1.647 ‑6.299
6 648.9 1.649 ‑6.264 9 651.9 1.645 ‑6.249 8 649.6 1.642 ‑6.246 9 646.2 1.65 1 ‑6.267 1 647.5 1.650 ‑6.26 I
1 65 1.4 1.644 ‑6.246
8.824 39.60 8.825 40.43 8.812 40.73 8.832 39.83 8.790 41.69 8.805 40.48 8.801 41.54 8.791 41.64 8.818 39.36 8.815 40.44 8.813 41.35 8.655 61.46 8.646 62.39 8.998 19.26 8.646 62.14 8.627 62.97 8.636 62.08 8.638 62.77 8.621 63.3 1 8.646 62.14 8.635 61.93 8.615 62.90 8.627 61.68 8.63 1 62.44 8.618 62.62 8.636 61.87 8.470 83.68 8.450 84.56 8.459 83.45 8.466 84.21 8.460 84.46 8.45 1 84.20
表4.3密度汎関数法によるPBDFsの熱力学データの計算結果(298.15K〜1500K)
AGfO(298K) So(298K)
Compounds
kJ･mo1‑1 kJ･morl J･mol l･K l
‑ATJ+B TC+c T+D
J･mol■】･K 1
AXIO7 BX104 cxlO D DF
1 ‑MoBDF 2‑MoBDF 3‑MoBDF
4‑Moも DF 1 ,2‑DiBDF 1 ,3‑DiBDF 1 ,4‑DiBDF 1 ,6‑DiBDF 1 ,7‑DiBDF 1 ,S‑DiBDF 1 ,9‑DiBDF 2,3‑DiBDF 2,4‑DiBDF 2,6‑DiBDF 2,7‑DiBDF 2,8‑DiBDF 3,4‑DiBDF 3 ,6‑DiBDF 3 ,7‑DiBDF 4,6‑DiBDF 1 ,2,3‑TrBDF 1 ,2,4‑1YBDF
1 ,2,6‑TrBDF
1 ,2,7‑TrBDF 1 ,2,8‑TrBDF 1 ,2,9‑TrBDF 1 ,3,4‑TrBDF1 ,3,6‑TrBDF
1 ,3,7‑TrBDF 1 ,3,8‑TrBDF1 ,3 ,9‑TrBDF
1 ,4,6‑TrBDF 1 ,4,7‑TrBDF I ,4,8‑TrBDF 1 ,4,9‑TrBDF 1 ,6,7‑TrBDF 1 ,6,8‑TrBDF 1 ,7,8‑TrBDF21 .4 2 0 0･ 3 2 6 0 6 3 7 9 6 0 0 4 2 9 7 5 2 2 6 ｣ 9 ｣ 9 9 4 0 3‑: 8 4 0 4 5･
55.768 1.8 1.86.m to51 09to8to2t o3̲331 1 61 14̲ 1 310古畑̲ 1 91 12to7̲ 1 8̲ 50146̲43朋1381 72棚̲ 37̲321 33̲ 61̲43̲36̲ 37湖̲4 t t 37̲ od α 4 4 9 7 0 5 3 7 00 ′0 2 0ノ 7 2 2 4 7 2 3 7 3 0 5 5 ′0 2 4 00 9 4 q′ 3 3 3 00 3 6 4 ′0 ∠U ∠U ′b OO 8 00 8 7 7 0 9 00 8 00 8 0ノ 00 00 9 1 1 1 0 0 4 1 0 0ノ q′ 2 0 0 0 3 0 0 0
1 1 1 1 1 1 1 1 1 1 1 2 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 1 1 2 2 2 2 2 2 2 2 2 382.2 1.600 ‑6.331 9.254 ‑58.33 9 421.5 1.597 ‑6.281 9.075 ‑36.81 9 424.3 1.593 ‑6.263 9.045 ‑34.98 8 424.1 1.595 16.268 9.052 ‑35.18
′
9 423.5 1.590 ‑6.261 9.056 ‑36.22 3 461.1 1.594 ‑6.227 8.887 114.40 5 463.2 1.59l ‑6.213 8.869 113.58 3 462.2 1.586 ‑6.207 8.878 114.96 6 462.6 1.588 16.210 8.879 ‑14.81 9 463.6 1.593 ‑'6.220 8.874 113.62 7 463.0 1.592 ‑6.216 8.872 ‑13.73 2 472.9 1.603 ‑6.257 8.919 ‑15.40 2 463.5 1.591 16.211 8.862 ‑12.82 4 465.2 1.583 ‑6.191 8.847 ‑12.86 8 465.0 1.584 ‑6.194 8.851 ‑13.06 6 465.9 1.589 ‑6.203 8.846 ‑ll.93 9 466.1 1.588 ‑6.197 8.840 ‑ll.65 7 462.7 1.587 ‑6.206 8.869 ‑13.94 6 465.5 1.586 ‑6.198 8.854 113.09 5 465.3 1.591 ‑6.209 8.854 112.27 6 464.2 1.582 ‑6.193 8.863 114.37 9 499.8 1.592 ‑6. 1 77 8.703 8.04 4 501.7 1.582 ‑6.150 8.687 7.59
.6 502.2 1.584 ‑6.155 8.690 7.64 .0 502.7 1.589 ‑6.165 8.686 8.66 .9 502.5 1.589 16.163 8.685 8.72 .6 477.1 1.604 ‑6.125 8.742 ‑I.43
.2 501.1 1.581 ‑6.149 8.690 7.22 4.3 504.1 1.582 ‑6.146 8.676 8.23 5 505.1 1.587 ‑6.154 8.670 9.48 9.2 505.0 1.586 ‑6.151 8.667 9.57 4.6 514.6 1.610 ‑6.225 8.734 8.51 6 503.7 1.577 ‑6.137 8.682 7.07 4 503.6 1.583 ‑6. 149 8.680 8.04 8 504.3 1.581 ‑6.142 8.672 8.37 0 509.0 1.592 ‑6.183 8.722 6.42 6 501.6 1.584 16.156 8.692 7.39 9 504.1 1.581 ‑6.143 8.672 8.43 1 502.4 1.590 ‑6.169 8.692 8.40
表4.3 (続き)
AHfO(29SK) AGfO(298K) So(298K)
C ompounds
kJ.mo1‑1 kJ･mo1‑1 J･mol'1･K‑1
=ATJ+B T2+c T+D
J･morl･K‑IAXIO7 BXIO4 cxlO D
2,3 ,4‑TrBDF
2,3 ,6‑TrBDF
2,3,7‑TrBDF 2,3 ,8‑TrBDF2,4,6‑TrBDF
2,4,7‑TrBDF2,4,8‑TrBDF
2,6,7‑TrBDF 3 ,4,6‑TrBDF 3,4,7‑TrBDF I ,2,3,4･TeBDF I ,2,3,6‑TeBDF I ,2,3,7‑TeBDF 1 ,2,3,8‑TeBDF I ,2,3,9‑TeBDF 1 ,2,4,6‑TeBDF I ,2,4,7‑TeBDF I ,2,4,8‑TeBDF 1 ,2,4,9‑TeBDF I ,2,6,7‑TeBDF 1 ,2,6,8‑TeBDF 1 ,2,6,9‑TeBDF I ,2,7,8‑TeBDF 1 ,2,7,9‑TeBDF I ,2,8,9‑TeBDF 1 ,3 ,4,6‑TeBDF I ,3,4,71TeBDF I ,3 ,4,i‑TeBDF I ,3,4,9‑TeBDF I ,3,6,7lTeBDF 1 ,3,6,8‑TeBDF 1 ,3 ,6,9‑TeBDF′b540035000577475‑320035703370004000‑0ノ5203394 574944叫48424247524692.弘77.78.は弧74.74.帆77.73.07.75.0 ll '79.7 473.03.7 1楓97.69.92.77.73.04.73.臥
1 1 1 I 1 1 1 l 1 11 ･1 1 1 1 2 1 1 1 2 1 1 2 1 2 2 1 1 1 2 1 1 1 1 1 1 1 2 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 22 1 1 1 1 0 0 1 1‑1 5 4 3 3 7 3 3 3 7 3 3 7 3 ′0 00 3 3 3 5 2 2 5 2 4 3 3 5 3 34 5 0 ‑ '4 8 cc 3 9 3 2 2 6 7 8 00 2 2 4 6 L 2 3 7 L 7 L L 9 9 5 3 7 7 5 0 8 2 9 8 9 5 ｣ ･ 5 3 2 1 3 0 2 2 5 4 2 9 ｣ 4 7 8 9 0 0 ｣ 0 5 5 8 5 5 4 0 2 9 4 0 . 1 501.8 1.584 ‑6.151 504.3 1.582 ‑6.144 505.3 1.587 ‑6.152 504.8 1.586 ‑6.150 506.2 1.575 ‑6.125 506.9 1.5$0 ‑6.132 506.9 1.578 16.127 504.5 1.582 ‑6.142 503.3 1.579 ‑6.141 504.3 1.583 こ6.147 538.0 I.585 ‑6.116 541.3 1.583 ‑6.109 541.6 1.588 ‑6.118 541.1 1.587 ‑6.115 515.0 1.603 ‑6.168 543.0 1.573 ‑6.08 1 543.4 1.578 ‑6.090 543.2 1.577 ‑6.08$
517.3 1.592 ‑6.137 540.5 1.582 ‑6.105 543.5 1.578 ‑6.091 517.4 1.593 ‑6.141 541.5 1.587 ‑6.114 5 17.5 1.598 ‑6.149 515.5 1.606 ‑6.178 543.0 1.572 ‑6.079 542.7 1.578 16.091 542.9 1.577 16.088 548.4 1.587 ‑6. 126 543.7 1.578 ‑6.09 1 545.3 1.576 ‑6.081 551.5 1.586 ‑6.118
8.679 8.69 等.669 9.03 8.664 10.17 8.662 10.15 8.656 8.98 8.650 10.05 8.644 10.27 8.666 9.22 8.679 7.83 i.671 9.01 8.521 29.35 8.508 30.03 8.504 31.02 8.503 30.99 8.561 20.83 8.492 29.53 8.489 30.60 8.4i7 30.60 8.542 20.45 8.509 29.62 8.487 30.74 8.544 20.44 8.505 30.76 8.539 21.58 8.570 20.62 8.492 29.34 8.493 30.21 8.489 30.36 8.535 28.59 8.489 30.61 S.473 31.43 8.520 29.48
表4.3 (続き)
AHfO(29 8K) AGfO(298K) So(298K)
Compounds
kJ･morI kJ･morl J･morl･K‑I
‑A TJ+B T2+c T+D J･mol 1･K l
AX107 BX104 cxlO D 5 249.8 542.4 1.576 ‑6.086 8.488 30.45 8 243.9 543.3 1.580 16.093 8.482 31.65 3 244.2 543.6 1.579 ‑6.089 8.477 31.87 7 241.7 543.2 1.580 ‑6.093 8.486 31.21
′
0 237.1 546.4 1.577 ‑6.079 8.464 32.44 5 239.3 544.0 1.584 16.100 8.479 32.44 6 239.9 545.5 1,572 ‑6.071 8.470 31.26 6 235,3 547.8 1.568 ‑6.055 8.447 32.37 8 245.2 542.1 1.576 ‑6.089 8.495 29.95 1 277.7 579.3 1.580 ‑'6.057 8.334 51.16 8 271.2 579.8 1.581 ‑6.058 8.323 52.41 5 271.8 579.9 1.580 ‑6.055 8.320 52.52 7 314.0 553.2 1.596 16.110 8.382 42.07 4 267.8 580.0 1.580 ‑6.056 8.324 52.ll 1 263.6 582.8 1.577 ‑6.043 8.304 53.17 8 305.5 555.3 1.593 ‑6.096 8.366 42.63 0 265.2 580.4 1.5$6 ‑6.067 S.322 53.17 9 299.5 555.7 1.598 ‑6.105 8.361 43.81 3 313.2 554.4 1.606 ‑6.133 8.389 43.05 6 264.4 581.7 1.571 ‑6.031 8.311 51.62 260.5 584.2 1.567 ‑6.016 8.290 52.57 302.3 557.1 1.581 ･6.065 8.347 42.25 261.3 581.9 1.575 ‑6.039 8.306 52.66 295.5 557.8 1.586 16.074 8.341 43.49 309.1 556.1 1.595 ‑6.103 8.371 42.59 267.1 580.1 1.579 ‑6.051 8.319 52.28 299.9 555.7 1.588 ‑6.085 8.359 42.45 263.1 581.6 1.569 ‑6.028 8.311 51.40 258.7 584.3 1.566 ‑6.015 8.290 52.47 286.4 592.0 1.576 ‑6.053 8.339 50.35 260.0 582.0 1.575 ‑6.038 8.307 52.44 280.6 589.7 1.581 ‑6.062 8.335 51.50 261.0 582.1 1.577 ‑6.042 8.305 53.01 266.5 581.7 1.571 ‑6.032 8.310 51.75 276.0 582.0 1.573 ‑6.035 8.305 52.63 271.5 584.1 1.570 ‑6.020 8.283 53.76 273.1 582.6 1.578 ‑6.041 8.298 53.84 303.6 618.1 1.574 ‑5.997 8.145 73.40 299.6 620.2 1.571 ‑5.986 8.127 74.35
2,3 ,4,6‑TeBDF 2,3 ,4,7‑TeBDF 2,3 ,4,8‑TeBDF 2,3 ,6,7‑TeBDF 2,3 ,6,8‑TeBDF 2,3 ,7,8‑TeBDF 2,4,6,7‑TeBDF 2,4,6,8‑TeBDF 3 ,4,6,7lTeBDF 1 ,2,3 ,4,6‑PeBDF 1 ,2,3 ,4,7‑PeBDF 1 ,2,3,4,S‑PeBDF 1 ,2,3 ,4,9‑PeBDF 1 ,2,3 ,6,7‑PeBDF 1 ,2,3,6,S‑PeBDF I ,2,3 ,6,9‑PeBDF 1 ,2,3,7,8‑PeBDF 1 ,2,3 ,7,9‑PeBDF 1,2,3,8,9‑PeBDF 1 ,2,4,6,7‑PeBDF
191
185 186 183 180 181 182 178 186
227 220221 255 217
214247 215 241 255 214
1 ,2,4,6,8‑PeBDF 2 1 1.4 1 ,2,4,6,9‑PeBDF 245. 1 1 ,2,4,7,8‑PeBDF 2 1 1.6 1 ,2,4,7,9‑PeBDF 23 8.6 I ,2,4,i,9‑PeBDF 25 I.6 1 ,2,6,7,8‑PeBDF 2 1 6.8 1 ,2,6,7,9‑PeBDF 242.3 I ,3,4,6,7‑PeBDF 2 1 3.2 1 ,3,4,6,8‑PeBDF 209.6 1 ,3 ,4,6,9‑PeBDF 239.7 1 ,3,4,7,S‑PeBDF 2 10.2 1 ,3,4,7,9‑PeBDF 233.2 1 ,3,6,7,8‑PeBDF 2 1 1.3 1 ,4,6,7,8lPeBDF 2 1 6.7 2,3 ,4,6,7‑PeBDF 226.2 2,3,4,6,8‑PeBDF 222.4 2,3,4,7,8lPeBDF 223.5 1 ,2,3,4,6,7‑HxBDF 26 1.4 1 ,2,3,4,6,8‑HxBDF 257.9
表4.3 (続き)
AHfO(298K) AGfO(298K) SD(298K)
C ompounds
kJ･morl kJ･morI J･morl･K‑I
‑Ate+B TJ+c T+D J･mo1‑1･K‑I
AXIO7 BX104 cxlO D
1 ,2,3,4,6,9‑HxBDF 1 ,2,3 ,4,7,i‑HxBDF 1 ,2,3 ,4,7,9‑HxBDF 1 ,2,3 ,4,8,9‑HxBDF I ,2,3 ,6,7,8‑HxBDF 1 ,2,3 ,6,7,9‑HxBDF 1 ,2,3,6,8,9‑HxBDF 1 ,2,3 ,7,8,9‑HxBDF I ,2,4,6,7,8lHxBDF 1 ,2,4,6,7,9‑HxBDF l ,2,4,6,8,9‑HxBDF l ,3 ,4,6,7,S‑HxBDF 1 ,3 ,4,6,7,9‑HxBDF 2,3 ,4,6,7,8‑HxBDF I ,2,3 ,4,6,7,S‑HpBDF 1 ,2,3 ,4,6,7,9‑HpBDF I ,2,3 ,4,6,i,9‑HpBDF 1 ,2,3 ,4,7,8,9‑HpBDF 1 ,2,3,4,6,7,8,9‑OBDF
7 5 0 6 3 2 9 5 00 7 . 1 2 4 2 5 4 3 9 00 2 00 ′0 0ノ 7 3 2 ′0 4 0 0 3 5 人V 1 OO 8 0 ′b 9 5 00 9 5 00 9 0ノ 5 00 9 5 7 ′0 0 2 3 4 00
2 2 2 2 2 2 2 2 2 2 2 2 2 2 3 3 3 3 3 0ノ l qノ 0ノ ー 9 0ノ 0ノ 2 0ノ q′ 2 つJ 2 5 3 3 3 ′02 00 4 2 00 4 4 2 0 5 5 0 0 0 /0 1 2 0 8 5 ′0 5 5 ′0 5 5 5 ′b 5 5 /b ′b /b /0 ′b ′0 ′0 /b
′ 5 ′b 5 ′b 4 /0 3 3 4 7 0 00 qノ 7 5 0ノ ′0 00 5 2 0 5 9 9 2 2 ∠U ∠U 9 9 4 tJ 7 5 0ノ 9 2 0 4 0 3 4 0ノ 3 4 4 9 2 3 9 1 0 3 ′0 7 00 2
3 3 3 3 2 3 3 3 2 3 3 2 3 3 3 3 3 3 4 8 1.586 ‑6.039 8.189 63.80
8 1.578 ‑6.006 8.140 74.52 0 1.590 ‑6.046 8.181 65.09 .2 1.600 ‑6.076 8.213 64.21 6 1.579 ‑6.006 8.140 74.49 0 1.588 ‑6.041 8.182 64.64 2 1.595 ‑6.059 8.193 64.83 9 1.607 ‑6.090 8.212 65.32 3 1.568 ‑5.980 8.126 73.97 4 1.577 ‑'6.011 8.164 64.18 7 1.5i3 ‑6.027 8.175 64.32 3 1.567 ‑5.977 8.125 73.83 5 1.572 ‑5.998 8.156 72.26 6 1.572 ‑5.984 8.118 75.25 7 1.572 ‑5.949 7.962 95.82 4 1.581 15.983 8.004 85.81 2 1.5$8 ‑6.002 8.016 86.00 2 1.601 ‑6.035 8.038 86.35 4 1.594 ‑5.978 7.861 107.50
aChirico et al., 1990 [20]
表4･4 密度汎関数法によるPBCDDsの熱力学データの計算結果(298.15K〜1500K)
AHfO(298K) AGfO(298K) So(298K)kJ･mol 1 kJ･morl J･mo1‑1･K‑1 c
28･ 0149424463519260719274081533620410063604230046009
.5945.5346T7.55‑5 546‑43505 1536 160535 8626573726460738 1帥7265747465糾73657 17 1625860糾7 17 1625 77 1 ･乃787 1 ･707S
l l l l I I l l l l I l I I I l l l l l一l l l I I l l l l一t I l 】 l l l‑l
C ompound
DD 1‑Br1‑2‑Cll‑DD
I ‑BrJ‑3{11‑DD
1‑Br14‑Cll‑DD I ‑Br1‑6‑Cll‑DD 1 ‑Br1‑7‑Cll‑DD 1 ‑Br1‑8‑Cll‑DDトBr1‑9‑Cll‑DD 2‑Brl‑トCII･DD
2‑Br1‑3‑Cll‑DD 2lBr1‑4‑Cll‑DD 2‑8r1‑6‑Cl I ‑DD 2‑Br1‑7‑Cll･DD 2‑Br1‑8‑Cll‑DD 2‑Br1‑9‑Cl 1‑DD 1 ‑8r1 ‑2,3‑C12‑DD 1 ‑Br1 ‑2,4‑Cl2‑DD
1 ‑Br] ‑2,6{12‑DD
1 ‑Br1 ‑2,7lCI2‑DDトBr1 ‑2,8‑C12‑DD
I ‑Br1 ‑2,9‑C12‑DD 1 ‑Br1 ‑3 ,4‑C12‑DD 1 ‑Br1 ‑3,6‑C12‑DD l ‑Br1 ‑3 ,7‑C12‑DD 1 ‑Brl l3,8‑C12‑DD
I ‑Br1 ‑3 ,9‑C12‑DD
I ‑Br14,6‑Cl2‑DDトBr1 ‑4,7‑C12‑DD
1 ‑Brl 4,8‑Cl2‑DD
I ‑Br1 ‑4,9‑C12‑DD
1 ‑Br1‑6,7‑C12‑DD 1 ‑Br] i,i‑Cl2‑DDトBr1 ‑6,9‑C12‑DD
1 ‑Br1 ‑7,S‑C12‑DD I ‑Brl ‑7,9‑C12･DD
トBr1‑8,9‑C12‑DD
2‑Br1‑1 ,3‑C12‑DD 2‑Br1 ‑ 1 ,4‑Cl2‑DD 2‑Br1‑1 ,6‑C12‑DD 2‑Br1‑1 ,7‑Cl2‑DD
2‑Brll1 ,8{121DD
2lBr7‑ 1 ,9‑C12lDD 2‑Br1 ‑3,4‑Cl2‑DD 2‑Br1‑3 ,6‑C12‑DD 2‑Br1 ‑3 ,7‑C12‑DD 2‑Br1 ‑3,8‑C12‑DD 2‑Br1 ‑3 ,9‑C12‑DD 2‑Br14,6‑C12･DD 2‑Br1 ‑4.7‑ClrDDcp, J･mo1‑1･K‑I ATa+BT2+cT+D AxlO7
409.9 1.679 479.3 1.682 481.8 1.679 482.1 1.676 481.5 1.677 480.9 1.681 480.9 1.681 480.3 1.678 480.2 1.679 480.3 1.682 482.0 1.676 481.9 1.678 480.5 1.682 ' 481.0 1.682 481.9 1.678 5082 1.691 510.3 1.685 510.8 1.689 509.7 1.693 510.5 1.693 509.5 1.690 5 10.6 1.684 512.6 1.685 511.9 1.689 511.5 1.689 5日.9 1.686 510.4 1.683 511.7 1.686 511.2 1.686 5112 1.682 5 10.7 1.686 511.5 1.685 511.7 1.681 509.8 1.689 512.2 1.685 509.9 1.687 508.2 1.690 509.5 1.682 510.5 1.686 510.4 1.690 510.7 1.690 509.9 1.687 507.7 1.689 510.1 1.689 510.6 1.692 510.4 1.692 508.7 1.689 512.5 1.683 511.7 1,6i7
BxlO4 cxl0
‑6.6 10 9.596
‑6.539 9.270
‑6.526 9.25 I
‑6.520 9.252
‑6.523 9.254 J.532 9.256 J.532 9.257 16.526 9.257
‑6.529 9.259
‑6.534 9.258
‑6.5 16 9.240
‑6.522 9.245 16.533 9.250 J.532 9.249
‑6.523 9.245 16.528 9.134 16.510 9.118
‑6.519 9.123 i.529 9. 128 J.529 9.127
‑6.523 9.128
‑6.507 9.117
‑6.506 9. 107 i.515 9.109
‑6.516 9.Ill i.509 9.109
‑6.502 9.110
‑6.510 9.111
‑6.510 9.112 16.500 9. 109
‑6.513 9.120 i.505 9.106 i.496 9. 1 04 i.519 9.120 i.506 9. 106
‑6.517 9.124
‑6.523 9. 128 16.500 9.108 i.511 9.116
‑6.521 9.119
‑6.520 9.118
‑6.513 9.119
‑6.521 9.127 i.517 9.117 i.525 9.118 i.524 9.117 i.519 9.119
‑i.499 9.098
‑6.506 9.099 2896292｣19754485465〜57403$98962166108140233509082
667435658097007cc40332525530LIO2305448625540587657
5656655666555555554455433454455454455554456433443 l l I l l l 7 I I T.I '.I I.‑..I
4666666666555541 3131 31 31 31 31 31 4‑414141 314131 31 3141 31 314̲31 31 31 31 4̲41 31 31414141 3̲4t
….9｡6㌶諾2 I 06‑65‑〝鵬5 ‑36‑55‑ 04 1 〝讐‑｡完‑‑‑ I‑ ‑㍍‑600‑9‑6｡篭7‑3 ‑完4｡諾0‑̲ ｡票04芸9‑諾表4.4 (続き)
AHfO(298K) AGfO(298K) So(298K)
kJ･mo1‑I kJ･mo1‑I J･morl･K‑I c
cp, J･mo1‑1･K‑I
‑ATa+BT2+cT+D
AxlO7 BxlO4
C ompound
2‑Br1 4.8‑C1,‑DD 2‑Br1 ‑4,9‑C12‑DD 2‑Br1 ‑6,7‑C12‑DD 2‑Br1 ‑6,S‑C12‑DD 2‑Br1 ‑6,9‑Cl2‑DD
2‑Br1‑7,8{lTDD 2‑Brl17,9{12‑DD
2‑Br1‑8,9‑C12‑DD 1 ‑Br1‑2,3 ,4‑ClrDD1 ‑Br1‑2,3 ,7{13‑DD
トBr1‑2,3 ,9‑ClrDD
I ‑Br1 ‑2,4,6‑C13‑DD
1 ‑Br1 ‑2,4,S一C13‑DD
1 ‑Br1‑2,6,7{13lDD J
1 ‑Br1‑2,6,9｣C13‑DD
I ‑Brl･2,7,S⊥ClrDD
I ‑Br1‑2,8,9{lrDD 1 ‑Br1 ‑3 ,4,8ClrDD
1 ‑Br1‑3 ,4,9‑C13‑DD 1 ‑Br1‑3 ,6,8‑C13‑DD 1 ‑Br1‑3,7,9lCl3‑DD I ‑Br1‑4,6,7‑C13‑DD 1 ‑Br1‑4,7,8J:13‑DDトBr1‑6,7,8‑C13‑DD
1 ‑Br) i,7,9‑C13‑DD 21Br1‑I ,3,4lClrDD 2‑Br1‑ 1 ,3,6‑C13‑DD 2‑Br1‑1 ,3,S‑C13‑DD
2‑Br1‑ I ,4,6{13‑DD
2‑Br1 ‑ 1 ,4,7‑ClrDD 2‑Br1‑ 1 ,4,9‑C13‑DD21Br1‑ I ,6,8{13‑DD
2‑Br1‑,I ,7,8‑C13‑DD 2‑Br1‑1 ,8,9‑ClrDD 2‑Br1‑3,4,7‑C13‑DD 2‑Br1 ‑3 ,4,9‑C13‑DD 2‑Br1 ‑3 ,6,7‑C13‑DD 2‑Brl ‑3 ,6,9‑ClrDD 2‑Br1‑3,,8,9‑ClrDD
2‑Br1 ‑4,6,8‑CIつ‑DD
2‑Brl ‑4,7,8{13lDD
2‑Br1‑4,8,9‑C131DD 2‑Br1 ‑6,7,8‑ClrDD2‑Br1 ‑6,番,9‑C13‑DD
‑79.0 36.7 5 12.8 1.686 ‑6.506
‑71.6 44.4 5 12.1 1.683 ‑6.497 169.5 46.5 5 I 1.9 1.688 ‑6.514
‑78.7 37.3 51 1.9 1.686 ‑6.504
‑72.1 43.7 5 12.6 1.674 ‑6.470
‑76.7 39.5 ′ 511.3 1.690 ‑6.517 178.5 37.5 51 I.7 1.686 ‑6.505
‑69.2 47.2 5 10.5 1.688 ‑6.514
‑63.1 59.5 536.6 1.698 ･6.514
･85.9 36.0 538.5 1.702 ‑6.520
‑77.2 44.6 539.1 1.699 ‑6.512
‑80.6 40.8 540.2 1.692 16.492
‑89.2 32.1 540.7 1.696 一 一6.501
‑81.4 40.2 539.7 1.699 ‑6.51 1
‑82.7 38.5 541.1 1.693 ‑6.495
‑88.3 33.6 538.5 1.702 ‑6.518
‑79.9 42.2 538.1 1.700 ‑6.515
‑87.8 33.4 54 I.0 1.695 ‑6.498
‑79.4 41.7 541.4 1.691 ‑6.489
‑97.7 22.9 542.9 1.693 ･6.489
‑96.8 24.2 54 1.8 1.694 ‑6.49 1
‑8 1.0 40.3 540.6 1.692 ‑6.493
‑89.3 3 1.9 540.9 1.695 ‑6.497
‑76.5 45. 1 539.6 1.695 ‑6.502
‑78.8 42.4 540.7 1.689 ‑6.4$2
‑62.6 59.3 538.6 1.696 ‑6.506
‑78.2 43.9 53i.2 1.697 ‑6.505
･85.5 36.3 539.1 1.701 ‑6.515
‑79.1 42.1 541.0 1.689 ‑6.480
‑87.6 33.5 541.3 1.693 ‑6.490
‑79.0 42.2 540.9 1.702 ‑6.522
‑88.6 32.5 54 1.5 1.694 16.493
‑86.5 35.1 539.6 1.699 16.508
̲77.9 43.4 540.8 1.697 ‑6.505
‑$3.9 37.9 539.0 1.700 ‑6.512
‑76.7 45.1 538.9 1.695 ‑6.501
‑86.5 35.3 539.0 1.699 ‑6.5 10
‑89. 1 32.2 540.6 1.693 ‑6.49 1
‑86.4 35.4 538.9 1.699 16.509
‑94.8 26.4 540.9 1.692 ･6.484
‑94.0 27.0 54 1.9 1.695 ‑6.494 187.0 34.1 541.5 1.693 ･6.489
‑82.1 39.5 539.5 1.697 ‑6.505
‑85.3 35.5 542. 1 1.690 ‑6.482
表4.4 (続き)
Compound
l ‑Br1 ‑2.3.8.9‑ClrDD l ‑Br) ‑2,4,6,8lCl4‑DD
l ‑Br] ‑2,4,7,8{l4‑DD
l ‑Br1 ‑2,4,8,9‑C14‑DDl ‑Br1 ‑2,6,7,9{14‑DD
l ‑Br1 ‑2,7,8,9‑C14‑DDl ‑Br1 ‑3 ,4,6,8{14‑DD l ‑Br1 ‑3,4,7,8{l4lDD
l ‑Br1 ‑3 ,4,8,9‑C14‑DD I ‑Brt l3 ,6,7,9lCI4lDD l ‑Br1 ‑3 ,7,S,9‑C14‑DD l ‑Br1 4,6,7,9‑C14‑DD l ‑Br1 ‑4,7,S,9‑ClrDD l ‑Brl i,7,8,9‑C14‑DD2‑Br】 ‑ 1 ,3 ,4,7‑C14‑DD
2‑Br1 ‑ 1 ,3 ,4,9･C14‑DD 2‑Br1‑1 ,3,6,7‑C14‑DD 2‑Br1‑ 1 ,3,6,9‑Cl4‑DD 2‑Br1‑ 1 ,3,7,8‑C14‑DD 2‑Br1 ‑ I ,4,6,7‑Cl4lDD 2‑Br1 ‑ 1 ,4,6,9‑C14‑DD 2‑Br1 ‑ 1 ,4,7,9‑C14‑DD 2‑Br1 ‑ 1 ,6,7,8･C141DD 2‑Br1 ‑ I ,6,S,9‑C14‑DD
2‑Brr3,4,6,8{14‑DD
2‑Br1‑3 ,4,7,8‑Cl4‑DD 2‑Br1‑3 ,4,S,9‑Cl4‑DD2‑Br) ‑3,6,7,8{14‑DD
2‑Brl ‑3 ,7,8,9‑Ch‑DD 2‑Br1‑4,6,7,i‑C141DD 2‑Br14,6,8,9lCl4‑DD 2lBr1 ‑6,7,i,9‑C14‑DD1 ‑Brr2,3 ,4,6,8{151DD
1 ‑Br1‑2,3,4,7,8‑ClrDD 1 ‑Br1‑2,3 ,4,S,9‑C15‑DD 1 ‑Br1‑2,3 ,6,7,8‑ClrDDトBr1 ‑2,3 ,6,7,9‑C15‑DD 1 ‑Br1‑2,3,7,等,9‑CI〜‑DD
1 ‑Br1 ‑2,4,6,7,9‑C15‑DD I ‑Brl l2,4,7,8,9lCl5‑DD
トBr1‑3 ,4,6,7,8‑ClrDD トBr1‑3,4,6,S,9‑C15‑DD
1 ‑Br1‑3,6,7,8,9{15‑DD
1 ‑Br14,6,7,8,9‑C15‑DD 2‑Br1‑ 1 ,3 ,4,6,7‑C15‑DD 2‑Br1‑ 1 ,3,4,6,9‑C15‑DD 2lBrll 1 ,3,4,7,i‑Cl5‑DD2‑Br1‑ I.3.6.7.名‑ClrDD
AHfO(298K) AGfO(298K) So(298K) kJ.morl kJ･mor I J･mo1‑ I ･K‑ I
Cp, J･mo1‑1･K･t ATa+BT2+cT+D
AxlO7 BxlO4 ー92.4
‑104.6
‑103.9
‑95.7
‑95.8
‑92.2
‑103.0
‑102.5
‑94.5
‑103.1
‑99.9
‑95.2
‑93.2
‑79.2
‑89.3
‑80.7
‑93.3
‑94.4
‑100.3
‑94.2
‑95.3
･102.8 191.8
‑93.7
‑99.5
‑98.9
‑92.0
‑98.6
‑98.7
‑97.7
‑101.0
‑85.7
‑104.7
‑104.0
‑96.1
‑105.3
‑107.6
‑104.3
‑109.6
‑107.5
‑105.9
‑108.1
‑103.1
‑95.3
‑95.6
‑96.7
‑103.7
‑105.0
792724944942924419051964036356317088415582631316709098090091987888701080988$791OC8666860771896866676766767767666666677767666666769999990990999999555555555555555555555555555555555555556556555555
7685gtt81191893SO374｣18417309359131620326619730284
41200434136037cc63272035270048cc85178674814628675$7322333223223343433233233223222242232222222233322 1.709 ‑6.504 8.862 1.700 ‑6.474 8.828 1.705 16.49 1 8.845 1.702 ‑6.484 8.844 I.701 ‑6.481 8.841 1.708 ‑6.503 8.860 1.699 ‑6.473 8.829 1.704 ‑6.487 8.843 1.70 1 ‑6.482 8.843 1.697 ‑6.467 8.824 I.705 16.49 1 8.845 1.694 ‑6.46 1 8.824 1.70 1̀ .6.483 8.843 1.700 ‑6.484 8.853 1.707 ‑6.500 8.857 I.703 16.489 8.852 1.707 ‑6.499 8.i55 1.702 ‑6.483 8.84 I 1.710 ‑6.505 8.856 1.699 ‑6.474 8.833 1.693 ･6.456 8.816 1.697 ‑6.465 8.819 1.705 ‑6.492 8.850 1.698 ‑6.472 8.83 I 1.704 ‑6.487 8.839 1.709 ‑6.50 1 8.852 1.706 ‑6.494 8.85 1 1.708 16.499 8.850 1.708 ‑6.499 8.852 1.703 ‑6.483 8.835 1.695 ‑6.458 8.il2 1.703 ‑6.486 8.847 1.713 ‑6.480 8.716 1.718 16.496 8.732 1.716 16.491 8.732 1.717 ‑6.493 8.727 1.71 1 ‑6.472 8.708 1.71 8 ‑6.495 8.730 1.704 ‑6.453 8.692 1.712 ‑6.476 8.712 1.710 ‑6.473 S.712 1.703 ‑6.450 8.690 1.710 ‑6.472 8.710 1.707 ‑6.465 8.710 1.7 14 ‑6.484 8.725 1.707 ‑6.465 8.705 1.717 ‑6.490 8.725 1.7 1 6 ‑6.489 8.72260454739‑759863094540716939530733071251069860413
2495622743884742488936592959838549526094273cc9434
535453535353545353545353535253535353535354545353545353535354545373727273737373737373737272737373
表4.4 (続き)
AHfO(298K) AGfO(298K) So(298K) kJ･morl kJ.mo1‑I J･mol‑I ･K‑I
cp, J･mol‑l･K‑1
‑ATa+BT2+cT+D
AxlO7 BxlO4 1.710 ‑6.468 1.717 ‑6.492 1.708 ‑6.465 1.716 ‑6.487 1.715 ･6.485 1.714 ‑6.483 1.707 ‑6.462 1.725 ･6.482 1.725 ‑6.481 1.723 ‑6.477 1.716 ‑6.455 1.724 ‑6.477 1.723 ･ ‑6.475 1.723 ‑6.474 I.72 1 16.469 1.730 ‑6.464 1.729 ‑6.458 I.678 ‑6.482 1.670 ‑6.454 1.673 ‑6.466 1.67 1 ･6.460 1.675 ‑6.47 1 1.669 ‑6.45 1 1.672 ‑6.463 1.677 ‑6.474 1.671 ‑6.454 1.676 ‑6.470 1.6$5 ･6.469 1.678 ‑6.437 1.673 ‑6.430 1.683 ‑6.458 1.678 ‑6.438 1.684 ‑6.455 1.684 ‑6.460 1.687 ‑6.466 1.686 ‑6.463 1.683 ‑6.456 1.686 ‑6.464 1.684 ‑6.460 1.687 ‑6.467 1.696 ‑6.463 1.698 ‑6.464 I.686 ‑6.429 1.692 ‑6.452
Compound
2‑Brll 1 3.6.8.9{IrDD
21Br1‑ 1 ,3 ,7,8,9‑C15‑DD 2‑Br1‑ 1 ,4,7,S,9‑C15‑DD 2‑Br1‑3 ,4,6,7,8‑C15‑DD2‑Br1‑3 ,4,7,i,9{151DD
2‑Brr3 ,6,7,8,9lC15‑DD 2‑Brl 4,6,7,8,9‑ClrDD 1 ‑Br1‑2,3 ,4,6,7,8‑C16lDD1 ‑Br1‑2,3 ,4,7,8,9{16‑DD 1 ‑Br1‑2,3,6,7,8,9{16‑DD
1 ‑Br1‑3 ,4,6,7,等,9‑ClrDD
2‑Br1‑ I ,3,4,6,7,8‑Cl6･DD
2lBr1‑1 ,3,4,7,8,9{161DD 2‑Br1‑ I ,3,6,7,8,9{16‑DD
2‑Br1‑3 ,4,6,7,8,9lC16‑DD 1 ‑Br1 ‑2,3 ,4,6,7,8,9‑ClrDD 2‑Br1‑ 1 ,3,4,6,7,S,9‑ClrDDl ,2‑BrT3‑Cll ‑DD l ,3‑Br2‑9‑Cl 1‑DD l ,4‑Br2‑7‑Cll‑DD
l ,6‑Br2‑3{11‑DD
l ,7‑Br2J‑Cll‑DD l ,8lBri‑6‑Cl I‑DD l ,9‑Br2‑3‑Cll‑DD 2,3 ‑Br2‑7‑Cl 1‑DD 2,7‑Br24‑Cl 1‑DD 2,8‑Br2‑3‑Cll‑DD l ,2‑Br2‑3 ,4‑C12‑DD l ,3‑Br2‑7,9‑ClrDD l ,4lBr2‑6,9{lTDD l ,6‑Br2‑2,8lCl2‑DDl ,7‑Br2‑3,9‑CI…‑DD
l ,8‑Br2‑3 ,7{I2‑DD l ,9‑8r2‑2,7‑C12‑DD 2,3‑Br2‑ I ,8‑Cl2‑DD 2,3‑Br2‑7,8‑C12‑DD 2,7‑Br2‑3 ,4‑C12‑DD 2,7‑Br2‑3 ,S‑C12‑DD 2,8‑Br2‑ 1 ,7･C12‑DD 2,8‑Br2‑3,7‑C12‑DD 1 ,2‑Br2‑3 ,4,7‑ClrDD 1 ,2‑Br2‑3 ,7,8‑C13‑DD 1 ,2‑Br2‑6,7,9‑ClrDD I ,3‑Br2‑2,4,6‑C13‑DD
26912575880643135｣726824982242839214099024661467386767685447345644923313302173203L 1 O90999780各70202999999922222222551222222222455555554544477877888005555555666666666655555555555555555555555555555555
075376854543202004$2321028867316314893000884149080 5006080000091112346623654790769166257096954057cc933 222323333323333339008880087789677AV677686767670066676
‑106.9
‑103.7
‑105.6
‑102.3 1103.6
･101.8
‑101.0
‑107.2
‑107.5
･107.4
‑107.9
‑107.0
‑106.8
‑106.8
‑105.3
‑109.2
･108.5
‑6.4
‑16.0
‑19.7
‑18.7
‑16.2
‑17.0
‑17.7
‑24.S
‑22.3
･22.0
‑ll.1
‑40.6
‑28.2
‑36.0
‑40.5
･41.2
‑35.1
‑32.0
‑40.2
‑27.6 138.9
‑31.9
‑39.1
‑37.8
‑48.6
‑42.2
‑28.1
表4.4 (続き)
Compound
l.7‑Br,12.3.8‑ClrDD l ,7‑Br2‑2,4,9‑C13‑DD l ,7‑Br2‑3 ,4,8‑ClrDD l ,8‑Br2‑2,3 ,7‑ClrDD
l ,8lBr2‑3,4,6‑ClrDD l ,8lBr2‑6,7,9lCl3‑DD l ,9lBr212,4,71CIrDD
2,3‑Br2‑ 1 ,7,8‑C13‑DD 2,3‑Br2‑6,7,8‑ClrDD 2,7lBr2‑ 1 ,3,8‑Cl3‑DD 2,7･Br2‑3 ,4,8‑ClrDD 2,8‑Br2‑ 1 ,3,7‑C13‑DD2,8‑Br213 ,4,71Cl3‑DD
l ,2‑Br2‑3,4,7,8‑C14‑DD1 ,2や213,6,7,8‑C14lDD
l ,2‑Br2‑3,7,8,9‑C14‑DD l ,3‑Br212,4,7,81Cl4‑DD l ,3‑Br2‑2,6,7,8lCI4‑DD l ,3lBr2‑2,7,8,9IC14‑DD
l ,31Br2‑4,7,8,9lCレDD
l ,4･Br2‑2,3 ,7,8‑C14‑DD
l ,4‑Br2‑6,7,8,9‑C14･DD
l ,6lBr2‑2,3 ,7,8lCl4‑DD l ,6‑Br2‑2,4,7,9‑Cl4･DDl ,7‑Br2‑2,3 ,4,8lCl4‑DD l ,7‑Br2‑2,3 ,6,8‑Cl4‑DD l ,7lBr2‑2,3 ,8,9‑Cl4‑DD l ,7‑Br2‑3 ,4,S,9‑C14‑DD l ,8‑Br2‑2,3 ,4,7‑C14‑DD l ,8‑Br2‑2,3 ,6,7‑C14･DD l ,S‑Br2‑2,3,7,9‑C14‑DD l ,8‑Br2‑2,4,7,9‑CIA‑DD l ,9‑Br2‑2,3 ,7,8‑C14‑DD l ,9‑Br2‑2,4,6,8‑C14‑DD
2,3‑Br2‑ I ,4,7,81Cl4‑DD 2,3 ‑Br2‑ 1 ,6,7,8‑C14‑DD 2,3‑Br2‑ 1 ,7,8,9‑C14‑DD 2,3‑Br2‑6,7,8,9‑C14･DD 2,7‑Br2‑ 1 ,3 ,4,8‑C14‑DD2,7‑Br2‑ 1 ,3 ,6,S‑C14‑DD
2,7‑Br2‑ 1 ,3 ,8,9‑Cl4‑DD 2,7･Br2‑3 ,4,S,9‑C14‑DD2,8‑Br2‑ 1 ,3 ,4,7‑C14‑DD 2,8‑Br2‑ 1 ,3,6,71Cl4‑DD 2,8‑Br2‑ 1 ,3 ,7,9‑C141DD
2,S‑Br2‑3 ,4,6,7‑C14‑DD 1 ,2lBr2‑3 ,4,6,7,8IC15‑DD l ,2lBr2‑3 ,6,7,8,9‑C15‑DDl.3̲Br,‑2.4.7.8.9‑CIち‑DD
AHfO(298K) AGfO(29iK) So(298K)
kJ･mo1‑1 kJ･morl J,mo1‑1･K‑I
cp, J･mo1‑1･K‑1
‑ATa+BT2+cT+D
BxlO4 cxlO
D一棚器洲舶洲紺船脚船舶諾oSsg豊洲棚御霊認諾棚謂即諾器W棚㌶棚諾m棚諾棚抑槻棚
60007609483036026971369608032570651441589OC t5069760 7L18271$6888cc766657869606679667760566565576655456 78cc70078777777000000000010000000001000000000000333 5555555555555666666666666666666666666666666666666 60CC20′4568738‑55439623736466269306233690CO6693208$2
6 764646 76 58 76 1666 86 7696769666 5666 76 76名666 77 66 76069666 8666 9676 764666 06 76 76 870696 76969696 8朗7 16 86 86 0470037706162144420152524408294626964291500790537
霊霊宝霊霊霊霊5｡宗5 5｡霊宝霊霊5 諾5 15〝宗5 霊霊霊霊霊霊諾
l l l ‑ l l l l l l l 一一 l ‑ I l l l
Ax107
1.697 ‑6.462 8.808 1.685 ‑6.423 8.771 I.689 ‑6.439 8.788 1.697 ‑6.46 1 8.805 1.683 ‑6.41 9 8.769 1.689 ‑6.445 8.804 1.687 ‑6.432 8.782 1.696 ‑6.456 8.799 1.694 ‑6,452 8.799 1.696 ‑6.457 8.800 1.695 ‑6.454 8.799 I.696 ‑6.457 8.800 1.694 ‑6.452 8.796 1.706 ‑6.453 8.680 1.704 ‑6.448 8.675 1.705 ‑6.450 8.677 1.706 16.453 8.680 1.704 ‑6.446 8.673 1.704 ‑6.446 8.673 1.696 ‑6.424 8.657 1.707 ‑6.460 8.690 1.693 ‑6.420 S.661 I.707 ‑6.456 8.684 1.694 16.419 8.651 1.704 ‑6.446 8.675 1.706 ‑6.452 8.679 1.704 ‑6.448 8.675 I.697 ‑6.425 等.657 1.704 ‑6.448 8.677 1.704 16.446 8.674 1.706 ‑6.453 8.678 1.699 ‑6.432 8.66 1 1.706 ‑6.455 8.682 1.693 ‑6.4 1 5 8.647 1.704 ‑6.448 8.674 1.702 ‑6.44 1 8.667 1.703 ･6.444 8.670 1.699 ‑6.434 8.665 1.702 ‑6.44 1 8.668 1.705 ‑6.44$ 8.673 1.704 ‑6.447 8.673 1.70 1 ‑6.437 8.665 1.703 ‑6.443 8.670 I.703 ‑6.444 8.670 1.705 ‑6.450 8.675 1.702 ‑6.442 8.670 1.713 ‑6.439 S.549 1.71 1 ‑6.433 8.543 1.712 16.438 8.547
表4.4 (続き)
AHfO(298K) AGfO(298K) SD(29SK)
kJ･morl kJ･morl J･mo1‑I.K'l c
cp, J･morl･K‑I
‑ATa+BT2+cT+D
AxlO7 BxlO4 635.8 1.709 ‑6.428 636.2 1.7 14 ‑6.445 635.6 1.714 ‑6.443 634.8 1.713 ‑6.439 635.3 1.712 ‑6.436 635.8 1.712 ‑6.438 636.0 1.712 ‑6.436 635.9 1.713 ‑6.441 633.7 1.709 J.427 634.3 1.71 1 ‑6.433 635.3 1.71 1 ‑6.433 665.4 1.720 ‑6.427 663.9 1.719. ‑6.424 664.0 1.716 ‑6.414 663.2 1.718 16.419 557.9 1.672 ‑6.424 560.8 1.672 ‑6.42 1 561.4 1.671 ‑6.414 565.4 1.659 ‑6.385 561.0 1.672 ‑6.415 588.0 1.683 ‑6.413 591.8 1.669 ‑6.374 588.6 1.680 ‑6.406 588.8 1.682 ‑6.410 589.7 1.679 ‑6.401 5i9.1 1.681 16.407 616.5 1.690 ‑6.398 623.4 1.676 ‑6.360 622. 1 1.678 ‑6.364 6 1 5.7 1.692 ‑6.405 6 1 7.9 1.693 ‑6.409 618.7 1.689 16.396 645.3 1.699 16.392 644.9 1.70 1 ‑6.399 645.8 1.700 ‑6.396 644.8 1.700 ‑6.396 646.2 1.700 16.394 645.1 1.698 J.389 675.8 1.704 ‑6.373 673.7 1.706 ‑6.381 675.3 1.708 ‑6.386 674.4 1.706 ‑6.310 675.5 1.706 ‑6.378 676.5 1.704 ‑6.372
C ompound
1.3‑Br7‑2.6.7,8.9‑Clで･DD
I ,4‑Br2‑2,3,6,7,8･C15‑DD 1 ,6‑Br2‑2,3 ,4,7,8‑C15‑DD
1 ,7‑Brr2,3 ,4,6,8‑ClrDD 1 ,7‑Br2‑2,3 ,6,S,9‑C15‑DD
1 ,8‑Br2‑2,3 ,4,7,9‑C15‑DD 1 ,8‑Br2‑2,3 ,6,7,9‑C15‑DD1 ,9‑Br2‑2,3,4,7,かClrDD
2,3‑Br2‑ 1 ,6,7,8,9‑C15‑DD 2,7‑Brr 1 ,3,4,6,8‑C15‑DD 2,8‑Br21 1 ,3 ,4,7,9‑C15‑DD 1 ,4lBr2‑2,3,6,7,8,9‑C16･DD I ,7‑Br2‑2,3,4,6,8,9‑Ck‑DD 2,3‑Br2‑ 1 ,4,6,7,8,9‑C16rDD 2,8‑Br2‑ 1 ,3,4,6,7,9‑C16‑DD
l ,2,3̲‑Br34‑Cll ‑DD l ,2,6‑Br317‑Cll‑DD l ,3 ,7‑Br3‑2‑Cl 1‑DD
l ,4,6‑Br3‑9{11‑DD
2,3 ,7‑Br3‑8‑Cll‑DD l ,2,3‑Br3‑7,8‑C12‑DD l ,2 ,4‑ Br3‑6, 9‑Cl2‑DD l ,3 ,71Br312,4‑C12‑DDl ,3 ,7‑Br3‑2,‰C12‑DD
2,3 ,7‑Br3‑8,9‑C12‑DD
2,3,かBr3‑ 1 ,7‑C12‑DD
1 ,2,3‑Br3‑6,7,8‑C13‑DD 1 ,2,4‑Br316,7,9‑C13‑DD I ,2,6lBr3‑4,8,9lC13‑DD 1 ,3,7‑Br3‑2,4,S‑ClrDD I ,3,7‑Bra‑2,6,8‑C13‑DD 2,3,7‑Br3‑ 1 ,6,8lC13‑DD 1 ,2,3‑Br3‑4,6,7,8‑C14‑DD 1 ,2,4‑Br3‑3 ,7,8,9lC14‑DD 1 ,2,7‑Brr3 ,4,6,S‑C14‑DD 1 ,3 ,7‑Br3‑2,4,6,8‑C14‑DD 1 ,3 ,8‑Br3‑2,4,7,9‑C14‑DD
2,3,7‑Bra‑ 1 ,4,6,8{lrDD
1 ,2,3‑Br3‑4,6,7,S,9‑CI〜‑DD
1 ,2,41Br3‑3,6,7,8,9lC15‑DD
1 ,2,かBr3‑3 ,4,7,8,9‑C15‑DD 1 ,2,7‑Br3‑3 ,4,6,等,9‑C15‑DD
1 ,3 ,7‑Br3‑2,4,6,i,9‑C15‑DD 2,3 ,7‑Br3‑ 1 ,4,6,S,9‑C15‑DD
o8096446363. ‑‑88･ 82975672972‑600C89930C‑357620702680C6
7 1686969696969687 1707｡72737273.̲351 19̲ 1 81 1 8108t o41 0St 1 9t o71081 07t o5toOt o It o8t o61 05106107to7̲ 09to81 08t o9t 1 0̲ 10川川mt 52̲45147̲48̲
0103565339805･ 7･ 99210. 57, 0. 63400｣6. 6303. 63650163378154906
535555545454545 5535353575656.5540.252526̲ 44.̲ 0̲ 9&9.7..0ユー23.2.し.3rjq'･T faaT;i;‑57.3T65596 1656
[ l l l l I l l J I l I l l
表4.4 (続き)
C ompound
l.2.3.4‑Br4‑7.8‑ClrDD l ,2,4,7‑Br4‑3,8‑C12‑DD
l ,2,6,7‑Br4‑3 ,8‑C12‑DD
1 ,3,7,9‑Br412,8‑C12‑DD 1 ,4,6,9‑Br4‑2,7‑C12‑DD2,3 ,7,S‑Br〟‑ I ,6‑C12‑DD
1 ,2,3 ,41Br4‑6,7,8‑Cl3･DD l ,2,4,8‑Br4‑3 ,7,9‑ClrDD 1 ,2,6,7‑Br4･3,4,8‑C13‑DD 1 ,3 ,6,8‑Br4‑2,4,7‑ClrDD 1 ,4,6,9‑Br4‑2,3,7‑C13‑DD 2,3 ,7,S‑Br4‑ 1 ,4,6‑ClrDD
1 ,2,3 ,4‑Br4‑6,7,等,9‑C14‑DD
1 ,2,4,7‑Br4‑3,6,S,9‑C14̀DD 1 ,2,6,7‑Br4･3 ,4,8,9‑C14‑DD 1 ,3 ,6,8‑Br4‑2,4,7,9‑Ch‑DD
I ,4,6,9‑Br412,3 ,7,8lCl4‑DD
2,3,7,8lBr4‑ 1 ,4,6,9‑Cl4･DDl ,2,3 ,4,7‑BrrS‑Cl 1‑DD l ,2,3,6,7‑BrrS‑Cl I ‑DD l ,2,3 ,7,8‑Br5‑6‑Cl 1‑DD l ,2,4,6,9‑Br5‑7‑Cl 1‑DD l ,2,4,7,8‑Br5‑3lC11‑DD 1 ,2,3,4,6‑Br5‑7,8‑C12‑DD 1 ,2,3,6,7‑Br5‑4,8･C12‑DD 1 ,2,3 ,7,8‑Br5‑6,9‑C12‑DD 1 ,2,4,6,8lBr5‑3,7‑Cl2‑DD
I ,2,4,6,9‑Br5‑3 ,7‑CI…‑DD
1 ,2,4,7,9‑Br5‑3 ,S‑C12‑DD 1 ,2,3 ,4,6‑Br5‑7,8,9‑ClrDD 1 ,2,3 ,7,81Br5‑4,6,9‑C13‑DD 1 ,2,3,8,9‑Br514,6,7‑C13‑DD
1 ,2,4,6,省一Br5‑3 ,7,9‑C13･DD
1 ,2,4,6,9‑Br513 ,7,8‑ClrDD I ,2,4,8,9‑Br5‑3 ,6,7‑Cl3lDD 1 ,2,3,4,6,7lBr6･8‑Cl l‑DD I ,2,3 ,4,6,9lBr6‑7‑CI I‑DD 1 ,2,3,4,7,8‑Br616lCI I ‑DD 1 ,2,3,6,7,8‑Br614lCl 1‑DD 1 ,2,4,6,8,9･Br6‑3‑Cll‑DD I ,2,3 ,4,6,7lBr618,9‑Cl2‑DD 1 ,2,3,4,6,9‑Br6‑7,8‑Cl2‑DD
1 ,2,3 ,4,7,8‑Br6‑6,9‑Cl2‑DD
1 ,2,3 ,6,7,8‑Br614,9‑C12‑DD 1 ,2,4,6,7,9‑Br6‑3 ,8‑C12‑DD 1 ,2,3,4,6,7,8‑Br7‑9‑Cll‑DD 1 ,2,3 ,4,6,7,9‑BrTi‑Cll‑DD aKolesov et al., 1998 [8]cp, J･morl･K‑I
‑ATa+BT2+cT+D
BxlO4AHfO(298K) AGfO(298K) So(298K)
kJ･mo1‑1 kJ･morl J･morl･KlI
626.5 1.680 ‑6.364 627.7 1.680 ‑6.366 625.8 1.681 ‑6.367 627.1 1.678 ‑6.357 632.3 1.668 ‑6.334 627.4 1.675 ‑6.348 656.0 1.686 ‑6.349 656.0 1.689 ‑6.355 654.7 1.689 16.356 656.5 1.687 ‑6.350 660.6 1.683 ‑6.343 655.1 1.684 ‑6.345 685.1 1.692 I 16.331 687.9 1.694 ‑6.338 684. 1 1.696 ‑6.345 685.0 1.696 ‑6.343 686.3 1.698 ‑6.353 684.6 1.692 ‑6.328 637.7 1.665 ‑6.315 638.9 1.665 ‑6.312 637.3 1.663 ‑6.306 646.3 1.653 ‑6.282 638.2 1.665 ‑6.3 15 666.9 1.675 ‑6.309 665.0 1.675 ‑6.308 664.8 1.67 1 ‑6.297 666.6 1.675 ‑6.309 670.4 1.669 ･6.295 667.4 1.674 ‑6.308 695. 1 1.682 ‑6.296 694. 1 1.680 ‑6.289 696.2 1.68 1 ‑6.294 697.2 1.683 ‑6.30 1 698.2 1.685 ‑6.307 696.4 1.683 ‑6.30 1 676.7 1.66 1 ‑6.263 680.2 1.655 16.244 678.7 1.659 16.256 675.4 1.660 ‑6.257 681.1 1.654 ･6.243 704.7 1.669 ‑6.252 707.3 1.670 ‑6.257 708.7 1.667 ‑6.245 705.0 1.668 ‑6.249 706.4 1.67 1 ‑6.261 715.4 1.655 ‑6.204 721.8 1.656 ‑6.209 51.1 142.7
54.$ 146.0 51.2 143.0 56.4 147.9 50.0 139.8 54.9 1 46.2′
47.6 144.3 49.5 146.2 48.8 145.9 52.1 148.6 48.3 143.6 51.4 148.4 45.4 147.4 47.5 14S.6 46.3 148.6 48.5 1 50.4 46.7 148.2 47.9 150.0 105.8 183.4 104.6 181.9 106.5 184.2 103.2 17S.2 108.6 186.0 99.6 1 82.5 100.6 1 84.0 102.4 185.8 103.1 186.0 100.1 181.9 102.9 185.6 97.3 185.6 99.1 187.7 97.9 185.9 99.2 186.8 98.3 185.7 98.4 1 86.3 151.5 220.7 151.1 219.3 153.8 222.5 154.1 223.7 153.2 221.1 149.2 224.0 149.2 223.2 1 50.0 223.6 150.1 224.8 149.9 224.2 201.1 262.I 200.8 259.8
49
表4.5 密度汎関数法によるPBCDFsの熱力学データの計算結果(29S.15K〜1500K)
cp, J･morl･K‑1‑ATa+BT2+cT+D
≒曇二三三圭幸二‡幸!::Z(:I;読?rit,空室圭曇(,こ.;二,. I:;I.!･;57.:,:.(.,莞芋,1EJ::I.::小皿
BxlO4
‑6.331
‑6.28 1
‑6.252
‑6.257
‑6.277
‑6.304
‑6.266
‑6.242
･6.257
‑6.259
‑6.265
‑6.247
‑6.238
‑6.277
‑6.266
‑6.229
‑6.278
‑6.272
‑6.272
‑6.233
.6.264
‑6.229
‑6.235
‑6.230
‑6.255
‑6.236
‑6.826
‑6.248
‑6.228 i.258
‑6.244
‑6.247
‑6.238
‑6.225
‑6.250
‑6.254
‑6.276
‑6.225
‑6.267
‑6.265 16.248
‑6.24S
‑6.272
‑6.245 AHfO(29SK) AGfO(29SK) So(298K)
compound kJ･mo1‑1 kJ･mo1‑I J･mol･l･K‑I
26714065′04420ノ35373070ノl6960′000007225395419360ノ75542702 201227244344392268LI25333460231423279̲416908002L t2
娼45454545裾454545454545454748484848胡48胡4848胡4848胡484848胡48網棚4850505 15 15 15 15052505 15 15 15 15 15
24 4 51 0 00ノ 61 7 27 4 5 11 9 7 00 7 310ノ 00 4 01 4 4 1 3300 ∠U2 900qノ ー 30 2 7 2 93 3 007 4 2 5 /0 2 6 0 2 0ノ 7 つ一〇ノ 3 00 0 0 5 7 7 5 5 4 0 5 4 7 0 9 4 3 cc 0 4 7 5 7 0 4 7 2 4 0 5 00 3 4 4 00 4 4 4 4 3 ′0 5 4 4 4 3 4 5 3 1 2 5 5 2 3 2 2 2 2 3 2 4 4 4 2 3 2 3 3 tJ 3 1 1 4 0 3 2 4 4 2 ‑ 1 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ‑ 1 1
260291003020593490346792234469524702. 4. 65. 027759058.
55575553457g625名52535 15 86344̲ 9335 8583042333 13 13 1363 15 152463 53929443640371 5̲ 84 14.4022473925柑̲ 42524̲
DF IBr1‑2CllDF IBrlJCllDF IBr1‑6CllDF IBr1‑7CllDF
1 Brト9CllDF 2Br1‑3CllDF 2Brト6Cl lDF 2Brl‑‡CllDF
3BrトlCllDF
3Br1‑7CllDF4Brト2Cl 1 DF 4Br1 ‑6Cll DF 1 Br1 ‑23C12DF IBr1 ‑37C12DF 1 Brl l46C12DF 1 Br 1 ‑49C12DF
I Brト69CuDF
IBr1‑78C12DF 2Brト14C12DF2Br1 ‑37C12DF 2Br 1 ‑48C12DF 2Br1 ‑49C12DF 2Br 1 ‑69C12DF 2Br 1 ‑78C12DF 3Br1‑ 16C12DF 3Br1‑19CI2DF
3 Brト24C12DF 3Br1 ‑46C12DF 3Br1 ‑78C12DF 4Br1‑13C12DF
4Brト27C12DF
4Br 1 ‑36C12DF 4Br 1 ‑69C12DF 4Br 1 ‑7SC12DF I Brト234C13DF IBr1 ‑237C13DF I Br1 ‑246C13DF IBr1 ‑349C13DF I Br1 ‑37SC13DF 1 Brト469C13DF 1 Br1 ‑678C13DF IBr1‑689C13DF 2Br1 ‑134C13DF表4.5 (続き)
Compound
2Br 1 469C13DF 2Br 1 ‑678C13 DF 2Br1 ‑689C13DF 3Br1‑126C13DF 3Br1‑128C13DF 3Br1‑147C13DF 3Br1‑168C13DF 3Br1‑248C13DF 3Br 1 ‑269C13DF
3Brト278C13DF
3Br1467C13DF 3Br 1 ‑7$9C13DF 4Br1‑123C13DF 4Br1‑ 126C13DF 4Br1 ‑23 7C13 DF 4Br1 ‑3 79C13DF 4Brll678C13DF 1 Br 1 ‑2346C14DF IBr1‑234SC14DF IBr1 ‑237SC14DF 1 Br1 ‑2469C14DF IBrl l2678C14DF I Br1 ‑34$9C14DF 1 Br1 ‑3679C14DF IBr1 ‑6789C14DF 2Br1 ‑1347C14DF 2Br1 ‑I 349C14DF 2Br1 ‑1 37SC14DF 2Br1 ‑1469C14DF 2Br 1 ‑3478C14DF 2Br1 ‑3678C14DF 2Brト3 789C14DF 2Br1 ‑6789C14DF 3Br1 ‑1248C14DF 3Br1 ‑127SC14DF 3Br1‑1469C14DF 3Brト1 679C14DF 3 Brト2478C14DF3Brト267SC14DF
3Br1 ‑2789C14DF 3Br 1 4689C14DF 4Br1‑1239C14DF 4Brト1 26‡C14DF 4Br1 ‑ 1 379C14DF 4Br1‑1 679C14DF 4Br I ‑23 78CI4DF 4Br 1 ‑26$9C14DF 4Br1 ‑3678C14DF 4Br 1 ‑6789C14DF 1 Brト23469C15DFcp, J･mo1‑1･K‑]
=ATa+BTa+cT+D
BxlO4‑6.203
‑6.23 1
‑6.220
‑6.246
‑6.264
̲6.230
‑6.226
‑6.244
̲6.236
‑6.26 1
‑6.222
‑6.257
･6.253
‑6.222
‑6.253
‑6.245
‑6.228
‑6.235
‑6.252
‑6.274
‑6.258
‑6.250
‑6.272
‑6.25 1
̲6.282
‑6.244
‑6.284
‑6.265
‑6.240
‑6.237
‑6.237
･6.257
‑6.182
̲6.243
‑6.263
‑6.227
‑6.238
‑6.243
‑6.238
‑6.260
‑6.208
̲6.293
‑6.212
‑6.255
‑6.23 1
‑6.249
‑6.208
‑6.229
‑6.222
‑6.27 I
州一昔即豊胸.99豊霊深窓測器㈲側豊霊脚側価脱脳愉悦榔脳霊雌脚霊意思器深淵胸
AHfO(298K) AGfO(298K) So(298K) kJ･mol･ 1 kJ･mo1‑ 1 J･mo1‑I ･K‑1
64000082‑55000034920ノ4305′0つJO900000‑400′b79002′b7′07′025′000530350
̲4.̲2.̲2.t 0.t 0.1 2.̲4.I 1.̲2.1 1.1 1.t 1.OSt I.t 1.̲ 1.1 1.38粥矧5538494547粥433947404039.39.粥3945453940394 14342444540424039叫
55 5 5 5 ′つ 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 415622712519549374009′07300′00ノ92003408441′03513005310340
17′b′b O2 443000000′120ノ225/b Oノ010ノOO′06815′b O 170′004′b 0 O /b I∠U′0420ノ/b4 12122102 1122322032 1021 つJ I4 14 0311121122 11111 4 01210124 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
51
90506. 00. 7. 1175. t t40. 2, 167, 72. 5215, 2各. 7,2. 65, 2. 63･2･ 09. 767･ 52｣･ 24. 2･ 545
̲ 2281 72720̲ 36.241 4̲ 9282 1392223川3 3̲ 79.0.295.29̲ 646日433.2=;5.̲ 6̲ 25.231 79;5.5.42.21 3239..21 42 12
表4.5 (続き)
AHfO(298K) AGfO(298K) So(298K) kJ･morl kJ.mo1‑ I J･mor ) ･Kl 1
cp, J･mo1‑1･K‑1
ATa+BT2+cT+D
AxlO7 BxlO4 1.679 ‑6.335 1.655 ‑6.264 I.668 ‑6.306 1.641 ‑6.224 1.651 ‑6.25S 1.649 ‑6.24 1 1.650 ‑6.244 1.675 ‑6.322 1.649 ‑6.245 1.640 ‑6.216 1.647 ‑6.237 1.646 ‑6.233 1.636 ‑6.203 1.649 ‑6.243 1.648 ‑6.240 1.674 ‑6.320 1.639 ‑6.215 1.642 ‑6.223 I.649 ‑6,243 I.646 ‑6.235 1.638 J.213 1.651 ‑6.251 1.652 ‑6.256 1.642 ‑6.226 1.651 ‑6.25$
1.644 ‑6.229 1.651 ‑6.250 1.64 1 ‑6.224 1.655 ‑6.230 1.683 ‑6.3 16 1.682 ‑6.3 1 1 1.670 ‑6.276 1.652 ‑6.219 1.679 ‑6.299 1.678 ‑6.298 1.650 ‑6.2日 1.653 ‑6.222 1.679 ‑6.301 1.677 ‑6.295 I.652 ‑6.218 1.655 ‑6.229 1.681 ‑6.308 1.667 ‑6.269 1.654 ‑6.224
･J;.I:i. (.こ完㌍≡! :; i:..禦[;C. :(, '註二二叫霊㌍.;こ,:!J.!:1{'Mm2'烹C;f:て÷禦:,:I,｣いニ):L=誌ドニ‥二･.二､二::'1. '聖二;二f二･f.二:…
州4‑44‑24‑74034‑名4｡54｡84‑04 1 3諾4｡｡3 ‑44084054‑83 ‑83‑.40840 13 ‑94‑04‑74004‑ 74｡｡㌶慧3 ‑73‑7諾34 1荒34｡3 ‑ 8崇3 ‑43‑2277㌫2｡9諾憲7‑3
C8.8.臥8.8.8.8.8.臥8.8.臥8.8.8.8.臥8.臥8.8.8.8.8.8.8.8.8.8.臥oioa.臥8.8.8.8･臥8･8･臥8 ･臥8･8･8･臥8･8 ･S･8･8
Compound
1 Br1 ‑23789C15DF 1 Br1 ‑24689C15DF 1 Br1 ‑267$9C15DF 1 Br1 ‑34679C15DF 1 Brl 467$9C15DF 2Br1‑1 347SC15DF 2Brll 1 367SCI5DF 2Brト137$9C15DF
2Br1‑14689C15DF 2Brl l34678C15DF 2Br 1 ‑347$9C15DF 2Brl l36789C15DF 2Br1 46789C15DF 3Br1 ‑12478C15DF 3Br1 ‑1267SC15DF 3Brト1 27$9C15DF 3Br1 ‑14679C15DF 3Br 1 ‑24678C15DF 3Br 1 ‑24789C15DF 3Br 1 ‑26789C15DF 3Br146789C15DF 4Br1‑ 12378C15DF 4Br1 ‑ 12689C15DF
4Brト13679C15DF
4Br1 ‑ 16789C15DF 4Br1 ‑23678CI5DF 4Br 1 ‑237$9C15DF 4Br 1 ‑367$9C15DF 1 Br1 ‑234678C16DF 1 Br1 ‑2347$9C16DF IBrl l236789C16DF I Br 1 ‑246789C16DF 2Br1‑1 34678C16DF 2Br1 ‑1 347$9C16DF 2Br1 ‑1 367$9C16DF 2Br1 ‑346789C16DF 3Br1 ‑124678C16DF 3Br1 ‑ 1247$9C16DF 3Br1 ‑126789C16DF 3Br 1 ‑246789C16DF 4Br1 ‑123678C16DF4Brト1237$9C16DF
4Br1 ‑1267$9C16DF 4Br 1 ‑236789C16DF38. 52I･133. 1, 70. 92027. 415. 2. 27. 7,23,4さ. 95･ 2350oOJ518690C25563633492 26̲ 8329.29.2.3261 95.7012. 127&3..3.04..2̲ 96.272..32.. 1 12 12 ll 8.82 12 1.6.名2022.7.820̲ 8.p1 7̲ 71 4̲ 692別988
‑ l 一
28457,‑.ーー640318357762‑989990508799COCC527738‑14255092333 443 550.̲ 7.360名073326̲ 5.鵬1 0㈹㈹08.34.̲ 6.̲ 3.07.t 0.け0725̲ 4.3 5̲ 3.06.1 304叫舶400732330907.32.34.07.07.32.30.074633433 1.7362.臥6
1 1 1 1 1 1 1 1 1 1 1 1一.1 1一1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 700793977445965t 0 CO OO236473996729537992506156429983450252477770988978CC4OO7QO87034甚775‑026976690669969ー03L‑945454545757朗56575 856565656565657575656565656粥5 75 7565656595 75 7575960605959606 15959606059596460糾49494849
表4.5 (続き)
Compound
14Br2‑3Cll DF 1 4Br2‑6Cl l DF 1 6Br2‑4CllDF 16Br2‑8Cll DF 1 7Br212C11DF 17Br2･9CllDF 1 8Br2‑3Cll DF 1 8Br217CllDF 19Br2‑2CllDF 19Br2‑4Cll DF 23Br2‑7Cll DF 23Br2‑9Cl 1 DF
24Br2‑9CH DF
26Br2‑3Cl I DF 27Br2‑4Cl 1 DF 28Br2‑3Cl lDF 34Br2‑6Cl 1 DF 36Br2‑ I Cll DF 37Br2‑2Cll DF 46Br2‑1 CllDF 1 2Br2‑3 7C12DF 1 2Br2‑67C12DF 1 3Br2‑24C12DF 1 3Br2‑79C12DF1 4Br2‑28C12DF 1 4Br2‑69C12DF
I 6Br2･38C12DF 1 6Br2‑49C12DF 1 7Br2‑26C12DF1 7Br2‑34C12DF 1 8Br2‑27C12DF
1 SBr2‑79C12DF1 9Br2‑28C12DF I 9Br2‑3 7C12DF 23Br2‑47C12DF
23Br2‑78C12DF 24Br2‑37C12DF 24Br2‑68C12DF 2 6Br2 ‑3 9C 12DF 26Br2‑7SC12DF27Br2‑ 1 9C12DF
27Br2‑3 8C12DF2SBr2‑3 7C12DF
2SBr246C12DF 34Br2‑ 1 9C12DF 3 4Br2‑79C 12DF 36Br2‑ 1 8C12DF3 6Br2‑24C 12DF
37Br2‑ I 6C12DF 37Br2‑28C12DF46Br2128C12DF 46Br2‑3 7C12DF
AHfO(298K) AGfO(298K) So(298K) kJ･morl kJ.morl J･mo1‑1･K‑I
cp, J･mol･1･K‑1
=ATa+BT2+cT+D
Bx lO4 cx̲lQ
｡tE州. I:]=: I. ,.:i･芸!:, ;:;州, I: I.,.:仰:. I:I(,i:こ.7', I:;:〔幸二烹:,,二=rZ.,,:.,.I::!･.'1..･.I.. :) :H?,:I;:EJ二..:i I:,:;:.:'..).: Ll, 'ZfJ1 ‑:Jt::,二, i:if. ,rJJ'::;二.T.. I...'iil:'jl･ '1:iL.;Z :S.,..こ'+.I::ml;I,;
̲601066176977024cc6456197643007cc7493371927581995707407
̲23327326932446424439078183702074222253272364242325L 9999999969999999999912122222222293222222222222222222 4444444444444444444455555555555545555555555555555555 780724983086576829606394029325003203368000440402205612
289156656277557085013764180800239023003236799479523915 7666685609666767767755765747555806656556755574475556 11tttttI21111111111111111111111121111111111111ttItIt
53
1.597 16.202 8.747 1.591 ‑6.1$5 8.733 1.591 ‑6.183 8.730 1.599 ‑6.201 8.738 1.606 ‑6.220 8.747 1.61 1 ‑6.238 8.765 I.603 ‑6.208 8.732 1.605 ‑6.218 8.748 1.621 ‑6.271 8.803 1.607 ‑6.23 1 8.772 I.604 ‑6.2 10 8.729 1.604 ‑6.212 8.735 1.596 ｣6.18$ 8.718 1.598 ‑6.197 8.729 1.593 ‑6.178 8.699 1.601 ‑6.201 8.720 1.593 ‑6.186 8.727 1.596 ‑6.191 8.721 1.603 ‑6.208 8.726 1.592 ‑6.2$3 8.728 1.62 1 ‑6.228 8.629 1.610 ‑6.199 8.613 1.612 16.208 8.627 1.62 1 ‑6.226 8.623 1.61 1 ‑6.200 8.6日 1.609 ‑6.201 8.621 1.610 ‑6.194 8.600 1.6 10 ‑6.203 8.623 1.61 1 ‑6.202 8.614 1.605 16.181 8.592 1.618 ‑6.218 8.622 1.63 1 ‑6.262 8.66$
1.640 ‑6.290 8.693 1.624 16.236 8.638 1.610 ‑6.193 8.594 1.616 16.206 8.599 1.612 ‑6.199 S.603 1.599 ‑6.157 8.560 1.609 ‑6.191 8.597 1.609 ‑6.191 8.595 1.624 ‑6.236 8.632 I.6 1 6 ‑6.208 8.602 1.615 ‑6.205 8.598 1.595 ‑6.144 8.543 1.616 ‑6.219 8.631 1.610 ‑6.193 8.598 1.607 ‑6.183 8.582 1.604 16. 1 82 8.597 1.606 ‑6.179 8.5$2 1.617 ‑6.21 1 8.605 1.603 ‑6.172 8.579 1.608 ‑6.194 8.610