EXAMPLES OF CHETAH METHOD APPLICATIONS

Apply the Chetah Method to the following substances:

1) 2-Nitroaniline

2) 2,3-Epoxy-1- propanol

Note:
for the calculation of 𝛥𝛥𝐻𝐻𝐹𝐹° = ∑𝛥𝛥𝐻𝐻𝐹𝐹,𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 with the method of the contributing groups,
it is necessary to add a corrective contribution for three-membered rings, as shown in
the following table:
 2-Nitroaniline

I° CRITERIUM (the maximum decomposition heat)

1
𝐶𝐶6 𝐻𝐻6 𝑂𝑂2 𝑁𝑁2 → 2𝐻𝐻2 𝑂𝑂 + 𝐶𝐶𝐻𝐻4 + 5,5𝐶𝐶 + 𝑁𝑁2
2
°
1 °
°
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 = 2∆𝐻𝐻𝐹𝐹,𝐻𝐻 2 𝑂𝑂
+ ∆𝐻𝐻° °
+ 5,5∆𝐻𝐻𝐹𝐹,𝐶𝐶 °
+ ∆𝐻𝐻𝐹𝐹,𝑁𝑁 − ∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚
2 𝐹𝐹,𝐶𝐶𝐻𝐻4 2

°
∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚 : the method of the contributing groups
° °
∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚 = � ∆ 𝐻𝐻𝐹𝐹,𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔

GROUPS ∆𝑯𝑯°𝑭𝑭,𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈 (Kcal/mol)

NH2 -1.19
NO2 -5.97
C 5.57*2 (carbon bonded to substituents)
CH 3.30*4
TOT = 17.18 Kcal/mol

°
∆𝐻𝐻𝐹𝐹,𝐻𝐻2 𝑂𝑂
= −58 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
°
∆𝐻𝐻𝐹𝐹,𝐶𝐶𝐻𝐻4
= −18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
1
°
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 = 2 ∙ (−58) + ∙ (−18) − 17.18 = −142.18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
2
°
∆𝐻𝐻𝑅𝑅,298𝐾𝐾
𝑄𝑄𝑀𝑀𝑀𝑀𝑀𝑀 =
𝑃𝑃𝑃𝑃
𝑔𝑔
𝑃𝑃𝑃𝑃 = 6 ∙ 12 + 6 + 2 ∙ 16 + 2 ∙ 14 = 138 �𝑚𝑚𝑚𝑚𝑚𝑚

−142.18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
𝑄𝑄𝑀𝑀𝑀𝑀𝑀𝑀 = 𝑔𝑔 = −1.03 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑔𝑔
138 �𝑚𝑚𝑚𝑚𝑚𝑚

High hazard, points 3

 II° CRITERIUM (complete combustion heat)

𝐶𝐶6 𝐻𝐻6 𝑂𝑂2 𝑁𝑁2 + 6.5𝑂𝑂2 → 6𝐶𝐶𝑂𝑂2 + 3𝐻𝐻2 𝑂𝑂 + 𝑁𝑁2

° ° ° °
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 = ∆𝐻𝐻𝐹𝐹,𝐶𝐶𝑂𝑂2
∙ 6 + ∆𝐻𝐻𝐹𝐹,𝐻𝐻2 𝑂𝑂
∙ 3 − ∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚 = 6 ∙ (−95) + 3 ∙ (−58) − 17.18
= −761.18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚

°
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 −761.18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
𝑄𝑄𝐶𝐶 = = 𝑔𝑔 = −5.51 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑔𝑔
𝑃𝑃𝑃𝑃 138 �𝑚𝑚𝑚𝑚𝑚𝑚

𝑄𝑄𝐶𝐶 − 𝑄𝑄𝑀𝑀𝑀𝑀𝑀𝑀 = −5.51 − (−1.03) = −4.48 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑔𝑔

Medium hazard, points 2

 III° CRITERIUM (oxygen index)
𝐶𝐶𝑥𝑥 𝐻𝐻𝑦𝑦 𝑂𝑂𝑧𝑧
𝑦𝑦 16 16
𝐼𝐼𝑂𝑂2 = �𝑧𝑧 − − 2𝑥𝑥� ∙ ∙ 100 = (2 − 3 − 12) ∙ ∙ 100 = −150.72
2 𝑃𝑃𝑃𝑃 138
Medium hazard, points 2

IV° CRITERIUM (practical rule)

2
𝑃𝑃𝑃𝑃 138
𝐼𝐼4 = 10 ∙ 𝑄𝑄𝑀𝑀𝑀𝑀𝑀𝑀 ∙ = 10 ∙ (−1.03)2 ∙ = 91.5
𝑛𝑛. 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 16
Medium hazard, points 2

The sum of the points is: 3 + 2 + 2 + 2 = 9 > 7, this substance can be dangerous!
 2,3-Epoxy-1-propanol

I° CRITERIUM
1 5
𝐶𝐶6 𝐻𝐻6 𝑂𝑂2 → 2𝐻𝐻2 𝑂𝑂 + 𝐶𝐶𝐻𝐻4 + 𝐶𝐶
2 2
° °
1 ° °
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 = 2 ∙ ∆𝐻𝐻𝐹𝐹,𝐻𝐻 𝑂𝑂 + ∆𝐻𝐻𝐹𝐹,𝐶𝐶𝐻𝐻 − ∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚
2
2 4

°
∆𝐻𝐻𝐹𝐹,𝐻𝐻2 𝑂𝑂
= −58 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
°
∆𝐻𝐻𝐹𝐹,𝐶𝐶𝐻𝐻4
= −18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
°
∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚 : the method of the contributing groups

GROUPS ∆𝑯𝑯°𝑭𝑭,𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈 (Kcal/mol)

CH -1.09
CH2 -4.926
OH -41.9
O -27.2
corrective contribution for
24.22
three-membered rings
°
∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚 = −1.09 + 2 ∙ (−4.926) − 41.9 − 27.2 + 24.22 = −55.82 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚

°
1
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 = 2 ∙ (−58) + ∙ (−18) − (−55.82) = −69.18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾
2
𝑔𝑔
𝑃𝑃𝑃𝑃 = 3 ∙ (12) + 6 + 2 ∙ (16) = 74 �𝑚𝑚𝑚𝑚𝑚𝑚
°
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 −69.18
𝑄𝑄𝑀𝑀𝑀𝑀𝑀𝑀 = = = −0.93 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑔𝑔
𝑃𝑃𝑃𝑃 74
High hazard, points 3
 II° CRITERIUM
7
𝐶𝐶3 𝐻𝐻6 𝑂𝑂2 + 𝑂𝑂2 → 3𝐶𝐶𝑂𝑂2 + 3𝐻𝐻2 𝑂𝑂
2
° ° ° °
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 = 3 ∙ ∆𝐻𝐻𝐹𝐹,𝐶𝐶𝑂𝑂2
+ 3 ∙ ∆𝐻𝐻𝐹𝐹,𝐻𝐻2 𝑂𝑂
− ∆𝐻𝐻𝐹𝐹,𝑚𝑚𝑚𝑚𝑚𝑚
= 3 ∙ (−95) + 3 ∙ (−58) − (−55.82) = −403.18 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑚𝑚𝑚𝑚𝑚𝑚
°
∆𝐻𝐻𝑅𝑅,298𝐾𝐾 −403.18
𝑄𝑄𝐶𝐶 = = = −5.4 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑔𝑔
𝑃𝑃𝑃𝑃 74
𝑄𝑄𝐶𝐶 − 𝑄𝑄𝑀𝑀𝑀𝑀𝑀𝑀 = −5.4 − (−0.93) = −4.51 𝐾𝐾𝐾𝐾𝐾𝐾𝐾𝐾�𝑔𝑔

Medium hazard, points 2

III° CRITERIUM
𝐶𝐶𝑥𝑥 𝐻𝐻𝑦𝑦 𝑂𝑂𝑧𝑧
𝑦𝑦 16 16
𝐼𝐼𝑂𝑂2 = �𝑧𝑧 − − 2𝑥𝑥� ∙ ∙ 100 = (2 − 3 − 6) ∙ ∙ 100 = −151.35
2 𝑃𝑃𝑃𝑃 74
Medium hazard, points 2
 IV° CRITERIUM

2
𝑃𝑃𝑃𝑃 74
𝐼𝐼4 = 10 ∙ 𝑄𝑄𝑀𝑀𝑀𝑀𝑀𝑀 ∙ = 10 ∙ (−0.93)2 ∙ = 58.18
𝑛𝑛. 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 11
Medium hazard

The sum of the points is: 3 + 2 + 2 + 2 = 9 > 7, this substance can be dangerous!