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Ɋɢɫ. 3.15. Ƚɢɛɪɢɞɧɵɟ ɨɪɛɢɬɚɥɢ (
ɢ ɝɟɨɦɟɬɪɢɱɟɫɤɚɹ ɤɨɧɮɢɝɭɪɚɰɢɹ ɦɨɥɟɤɭɥɵ PCl
sp3d)
5
ȼ ɦɨɥɟɤɭɥɟ PCl
ɟɫɬɶ ɞɜɚ ɬɢɩɚ ɜɚɥɟɧɬɧɵɯ ɭɝɥɨɜ Cl – P – Cl: 120° ɜ ɩɥɨɫɤɨ-
5
ɫɬɢ ɬɪɺɯ ɚɬɨɦɨɜ ɯɥɨɪɚ ɢ 90° ɩɟɪɩɟɧɞɢɤɭɥɹɪɧɨ ɷɬɨɣ ɩɥɨɫɤɨɫɬɢ.
ɉɪɢɦɟɪɧɵɣ ɬɟɫɬ 5 (ɏɢɦɢɱɟɫɤɚɹ ɫɜɹɡɶ)
1. Cɨɝɥɚɫɧɨ ɦɟɬɨɞɭ ȼɋ, ɤɨɜɚɥɟɧɬɧɚɹ ɫɜɹɡɶ ɯɚɪɚɤɬɟɪɢɡɭɟɬɫɹ:
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. ɇɟɧɚɫɵɳɚɟɦɨɫɬɶɸ ɢ ɧɟɧɚɩɪɚɜɥɟɧɧɨɫɬɶɸ.
ȼɚɪɢɚɧɬ 2. ɇɚɫɵɳɚɟɦɨɫɬɶɸ ɢ ɧɟɧɚɩɪɚɜɥɟɧɧɨɫɬɶɸ.
ȼɚɪɢɚɧɬ 3. ɇɟɧɚɫɵɳɚɟɦɨɫɬɶɸ ɢ ɧɚɩɪɚɜɥɟɧɧɨɫɬɶɸ.
ȼɚɪɢɚɧɬ 4. ɇɚɫɵɳɚɟɦɨɫɬɶɸ ɢ ɧɚɩɪɚɜɥɟɧɧɨɫɬɶɸ.
ȼɚɪɢɚɧɬ 5. Ⱦɟɥɨɤɚɥɢɡɚɰɢɟɣ ɷɥɟɤɬɪɨɧɨɜ ɜ ɦɨɥɟɤɭɥɟ.
2. Ʉɚɤɨɜɚ ɦɚɤɫɢɦɚɥɶɧɚɹ ɜɚɥɟɧɬɧɨɫɬɶ, ɤɨɬɨɪɭɸ ɦɨɠɟɬ ɩɪɨɹɜɥɹɬɶ ɜ ɫɨ-
ɟɞɢɧɟɧɢɹɯ ɭɝɥɟɪɨɞ?
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 1.
ȼɚɪɢɚɧɬ 2. 4.
ȼɚɪɢɚɧɬ 3. 2.
ȼɚɪɢɚɧɬ 4. 5.
ȼɚɪɢɚɧɬ 5. 3.
3. Ʉɚɤɨɜɚ ɦɚɤɫɢɦɚɥɶɧɚɹ ɜɚɥɟɧɬɧɨɫɬɶ, ɤɨɬɨɪɭɸ ɦɨɠɟɬ ɩɪɨɹɜɥɹɬɶ ɜ ɫɨ-
ɟɞɢɧɟɧɢɹɯ ɦɚɪɝɚɧɟɰ?
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 5.
ȼɚɪɢɚɧɬ 2. 3.
ȼɚɪɢɚɧɬ 3. 2.
ȼɚɪɢɚɧɬ 4. 7.
ȼɚɪɢɚɧɬ 5. 4.
61
4. ɍɤɚɡɚɬɶ ɤɪɚɬɧɨɫɬɶ ɯɢɦɢɱɟɫɤɨɣ ɫɜɹɡɢ ɜ ɦɨɥɟɤɭɥɟ N
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 1.
.
2
ȼɚɪɢɚɧɬ 2. 3.
ȼɚɪɢɚɧɬ 3. 2.
ȼɚɪɢɚɧɬ 4. 1,5.
ȼɚɪɢɚɧɬ 5. 4.
5. ɍɤɚɡɚɬɶ, ɫɤɨɥɶɤɨ V- ɢ S-ɫɜɹɡɟɣ ɜ ɦɨɥɟɤɭɥɟ O
.
2
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 2
ȼɚɪɢɚɧɬ 2. 2
ȼɚɪɢɚɧɬ 3. 1
ȼɚɪɢɚɧɬ 4. 1
ȼɚɪɢɚɧɬ 5. 2
6. ɍɤɚɡɚɬɶ, ɫɤɨɥɶɤɨ V- ɢ S-ɫɜɹɡɟɣ ɜ ɦɨɥɟɤɭɥɟ N
V
-ɫɜɹɡɢ.
S
-ɫɜɹɡɢ.
V
-ɫɜɹɡɶ ɢ 2 S-ɫɜɹɡɢ.
V
-ɫɜɹɡɶ ɢ 1 S-ɫɜɹɡɶ.
V
-ɫɜɹɡɢ ɢ 1 S-ɫɜɹɡɶ.
.
2
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 3 V-ɫɜɹɡɢ.
ȼɚɪɢɚɧɬ 2. 1 V-ɫɜɹɡɶ ɢ 2 S-ɫɜɹɡɢ.
ȼɚɪɢɚɧɬ 3. 2 V-ɫɜɹɡɢ ɢ 1 S-ɫɜɹɡɶ.
ȼɚɪɢɚɧɬ 4. 3 S-ɫɜɹɡɢ.
ȼɚɪɢɚɧɬ 5. 1 V-ɫɜɹɡɶ ɢ 1 S-ɫɜɹɡɶ.
7. ɍɤɚɡɚɬɶ, ɫɤɨɥɶɤɨ V- ɢ S-ɫɜɹɡɟɣ ɜ ɦɨɥɟɤɭɥɟ NF
.
3
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 3 S-ɫɜɹɡɢ.
ȼɚɪɢɚɧɬ 2. 1 V-ɫɜɹɡɶ ɢ 2 S-ɫɜɹɡɢ.
ȼɚɪɢɚɧɬ 3. 2 V-ɫɜɹɡɢ ɢ 1 S-ɫɜɹɡɶ.
ȼɚɪɢɚɧɬ 4. 1 V-ɫɜɹɡɶ ɢ 1 S-ɫɜɹɡɶ.
ȼɚɪɢɚɧɬ 5. 3 V-ɫɜɹɡɢ.
8. ɍɤɚɡɚɬɶ ɬɢɩ ɝɢɛɪɢɞɢɡɚɰɢɢ ɰɟɧɬɪɚɥɶɧɨɝɨ ɚɬɨɦɚ ɜ ɦɨɥɟɤɭɥɟ SiF
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1.
ȼɚɪɢɚɧɬ 2.
ȼɚɪɢɚɧɬ 3. sp3.
ȼɚɪɢɚɧɬ 4. sp2.
ȼɚɪɢɚɧɬ 5. sp
sp.
sp3d.
3d 2
.
9. ɍɤɚɡɚɬɶ ɬɢɩ ɝɢɛɪɢɞɢɡɚɰɢɢ ɰɟɧɬɪɚɥɶɧɨɝɨ ɚɬɨɦɚ ɜ ɦɨɥɟɤɭɥɟ CO
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1.
ȼɚɪɢɚɧɬ 2.
ȼɚɪɢɚɧɬ 3. sp3.
ȼɚɪɢɚɧɬ 4. sp2.
ȼɚɪɢɚɧɬ 5. sp
sp.
sp3d.
3d2
.
.
4
.
2
62
10. Ʉɚɤɨɜɚ ɝɟɨɦɟɬɪɢɱɟɫɤɚɹ ɤɨɧɮɢɝɭɪɚɰɢɹ ɦɨɥɟɤɭɥɵ AlF
ɭ
r
r
a
a
?
3
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. Ɍɟɬɪɚɷɞɪɢɱɟɫɤɚɹ.
ȼɚɪɢɚɧɬ 2. ɉɢɪɚɦɢɞɚɥɶɧɚɹ.
ȼɚɪɢɚɧɬ 3. Ɍɪɟɭɝɨɥɶɧɚɹ.
ȼɚɪɢɚɧɬ 4. Ʌɢɧɟɣɧɚɹ.
ȼɚɪɢɚɧɬ 5. Ɍɪɢɝɨɧɚɥɶɧɚɹ ɛɢɩɢɪɚɦɢɞɚ.
11. Ʉɚɤɨɜɚ ɝɟɨɦɟɬɪɢɱɟɫɤɚɹ ɤɨɧɮɢɝɭɪɚɰɢɹ ɦɨɥɟɤɭɥɵ NH
?
3
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. ɉɪɹɦɨɭɝɨɥɶɧɚɹ.
ȼɚɪɢɚɧɬ 2. ɉɢɪɚɦɢɞɚɥɶɧɚɹ.
ȼɚɪɢɚɧɬ 3. Ɍɪɟɭɝɨɥɶɧɚɹ.
ȼɚɪɢɚɧɬ 4. Ʌɢɧɟɣɧɚɹ.
ȼɚɪɢɚɧɬ 5. Ɍɪɢɝɨɧɚɥɶɧɚɹ ɛɢɩɢɪɚɦɢɞɚ.
Ɂɚɞɚɱɢ
3.1–3.14. ɉɨ ɦɟɬɨɞɭ ɜɚɥɟɧɬɧɵɯ ɫɜɹɡɟɣ ɩɨɤɚɡɚɬɶ ɫɬɪɨɟɧɢɟ ɞɚɧɧɨɣ ɦɨɥɟɤɭɥɵ.
Ɉɩɪɟɞɟɥɢɬɶ ɬɢɩ ɝɢɛɪɢɞɢɡɚɰɢɢ ɜɚɥɟɧɬɧɵɯ ɨɪɛɢɬɚɥɟɣ ɰɟɧɬɪɚɥɶɧɨɝɨ ɚɬɨɦɚ, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɭɸ ɫɬɪɭɤɬɭɪɭ ɦɨɥɟɤɭɥɵ ɢ ɤɨɥɢɱɟɫɬɜɨ
ı- ɢ ʌ-ɫɜɹɡɟɣ.
ʋ Ɇɨɥɟɤ
3.1 AlCl
3.2 BeI
3.3 CCl
3.4 AlI
3.5 BB
3.6 CS
3.7 GaCl
ɥɚ ʋ Ɇɨɥɟɤɭɥɚ
3.8 MgCl
3
3.9 SiF
2
3.10 PbCl
4
3.11 SnCl
3
3.12 GaB
3
3.13 CaCl
2
3.14 CH2Cl
3
2
4
4
4
3
2
2
3.15–3.28. ɉɨɤɚɡɚɬɶ ɨɛɪɚɡɨɜɚɧɢɟ ɦɨɥɟɤɭɥɵ ɩɨ Ɇȼɋ. Ɉɩɪɟɞɟɥɢɬɶ ɤɨɥɢɱɟɫɬɜɨ
ı- ɢ ʌ-ɫɜɹɡɟɣ. ɂɡɨɛɪɚɡɢɬɶ ɩɟɪɟɤɪɵɜɚɧɢɟ ɚɬɨɦɧɵɯ ɨɪɛɢɬɚɥɟɣ.
ʋ Ɇɨɥɟɤɭɥɚ ʋ Ɇɨɥɟɤɭɥɚ
3.15 S
3.16 Si
3.17 P
3.18 C
3.19 As
3.20 Ge
3.21 Se
2
2
2
2
2
2
2
3.22 Sn
3.23 B
3.24 Al
3.25 Li
3.26 N
3.27 G
3.28 Cl
2
2
2
2
2
2
2
63
ȽɅȺȼȺ 4. ɗɅȿɆȿɇɌɕ ɏɂɆɂɑȿɋɄɈɃ ɌȿɊɆɈȾɂɇȺɆɂɄɂ
ɏɢɦɢɱɟɫɤɚɹ ɬɟɪɦɨɞɢɧɚɦɢɤɚ
ɢɡɭɱɚɟɬ ɩɪɟɜɪɚɳɟɧɢɹ ɯɢɦɢɱɟɫɤɨɣ ɷɧɟɪɝɢɢ ɜ
ɬɟɩɥɨɬɭ, ɪɚɛɨɬɭ ɢ ɞɪɭɝɢɟ ɮɨɪɦɵ ɷɧɟɪɝɢɢ. Ɉɛɴɟɤɬɚɦɢ ɢɫɫɥɟɞɨɜɚɧɢɹ ɯɢɦɢɱɟɫɤɨɣ
ɬɟɪɦɨɞɢɧɚɦɢɤɢ ɹɜɥɹɸɬɫɹ ɬɟɩɥɨɜɵɟ ɛɚɥɚɧɫɵ ɮɢɡɢɤɨ-ɯɢɦɢɱɟɫɤɢɯ ɩɪɨɰɟɫɫɨɜ, ɮɚɡɨɜɵɟ ɢ ɯɢɦɢɱɟɫɤɢɟ ɪɚɜɧɨɜɟɫɢɹ, ɫɜɨɣɫɬɜɚ ɜɟɳɟɫɬɜ ɜ ɪɚɫɬɜɨɪɚɯ.
4.1. Ɍɟɩɥɨɜɵɟ ɷɮɮɟɤɬɵ ɯɢɦɢɱɟɫɤɢɯ ɪɟɚɤɰɢɣ
ɉɟɪɜɵɣ ɡɚɤɨɧ ɬɟɪɦɨɞɢɧɚɦɢɤɢ. Ʉɨɥɢɱɟɫɬɜɟɧɧɨɟ ɫɨɨɬɧɨɲɟɧɢɟ ɦɟɠɞɭ ɢɡ-
ɦɟɧɟɧɢɟɦ ɜɧɭɬɪɟɧɧɟɣ ɷɧɟɪɝɢɢ, ɬɟɩɥɨɬɨɣ ɢ ɪɚɛɨɬɨɣ ɭɫɬɚɧɚɜɥɢɜɚɟɬ
ɩɟɪɜɵɣ ɡɚɤɨɧ
ɬɟɪɦɨɞɢɧɚɦɢɤɢ.
ɉɭɫɬɶ ɤ ɡɚɤɪɵɬɨɣ ɫɢɫɬɟɦɟ ɩɨɞɜɟɞɟɧɨ ɤɨɥɢɱɟɫɬɜɨ ɬɟɩɥɨɬɵ Q. ɗɬɚ ɬɟɩɥɨɬɚ
ɢɞɟɬ ɜ ɨɛɳɟɦ ɫɥɭɱɚɟ ɧɚ ɭɜɟɥɢɱɟɧɢɟ ɜɧɭɬɪɟɧɧɟɣ ɷɧɟɪɝɢɢ
ɫɬɟɦɨɣ ɪɚɛɨɬɵ
W:
U ɢ ɧɚ ɫɨɜɟɪɲɟɧɢɟ ɫɢ-
Q = 'U + W. (4.1)
Ⱦɥɹ ɛɟɫɤɨɧɟɱɧɨ ɦɚɥɵɯ ɷɥɟɦɟɧɬɚɪɧɵɯ ɩɪɨɰɟɫɫɨɜ ɭɪɚɜɧɟɧɢɟ (4.1) ɩɪɢɧɢɦɚ-
ɟɬ ɜɢɞ:
G
ɢɥɢ G
ɝɞɟ
pdV – ɷɥɟɦɟɧɬɚɪɧɚɹ ɪɚɛɨɬɚ, ɫɨɜɟɪɲɚɟɦɚɹ ɫɢɫɬɟɦɨɣ ɩɪɨɬɢɜ ɜɧɟɲɧɟɝɨ ɞɚɜ-
Q = dU + GW (4.2)
Q = dU + pdV + GW´, (4.3)
ɥɟɧɢɹ (ɪɚɛɨɬɚ ɪɚɫɲɢɪɟɧɢɹ);
G
W´ – ɫɭɦɦɚ ɜɫɟɯ ɨɫɬɚɥɶɧɵɯ ɜɢɞɨɜ ɷɥɟɦɟɧɬɚɪɧɵɯ ɪɚɛɨɬ (ɷɥɟɤɬɪɢɱɟɫɤɚɹ,
ɦɚɝɧɢɬɧɚɹ ɢ ɬ. ɩ.).
ɍɪɚɜɧɟɧɢɹ (4.1)–(4.3) ɹɜɥɹɟɬɫɹ ɦɚɬɟɦɚɬɢɱɟɫɤɢɦɢ ɜɵɪɚɠɟɧɢɹɦɢ
ɤɨɧɚ ɬɟɪɦɨɞɢɧɚɦɢɤɢ.
ɉɟɪɜɵɣ ɡɚɤɨɧ ɬɟɪɦɨɞɢɧɚɦɢɤɢ ɹɜɥɹɟɬɫɹ ɱɚɫɬɧɵɦ ɫɥɭɱɚɟɦ
ɩɟɪɜɨɝɨ ɡɚ-
ɡɚɤɨɧɚ ɫɨɯɪɚɧɟɧɢɹ ɷɧɟɪɝɢɢ ɩɪɢɦɟɧɢɬɟɥɶɧɨ ɤ ɦɚɤɪɨɫɤɨɩɢɱɟɫɤɢɦ ɫɢɫɬɟɦɚɦ.
Ɉɱɟɧɶ ɱɚɫɬɨ ɩɪɢ ɩɪɨɬɟɤɚɧɢɢ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢɯ ɩɪɨɰɟɫɫɨɜ ɟɞɢɧɫɬɜɟɧɧɨɣ
ɪɚɛɨɬɨɣ ɹɜɥɹɟɬɫɹ ɪɚɛɨɬɚ ɪɚɫɲɢɪɟɧɢɹ. ɉɪɢ ɷɬɨɦ ɭɪɚɜɧɟɧɢɟ (4.3) ɩɪɢɧɢɦɚɟɬ ɜɢɞ:
G
Q = dU + pdV. (4.4)
ɗɧɬɚɥɶɩɢɹ. ȼ ɬɟɪɦɨɞɢɧɚɦɢɤɟ ɩɪɢ ɪɚɫɫɦɨɬɪɟɧɢɢ ɦɧɨɝɢɯ ɩɪɨɰɟɫɫɨɜ ɧɚɪɹɞɭ
ɫ ɜɧɭɬɪɟɧɧɟɣ ɷɧɟɪɝɢɟɣ ɲɢɪɨɤɨ ɢɫɩɨɥɶɡɭɟɬɫɹ ɮɭɧɤɰɢɹ:
H = U + pV,
ɤɨɬɨɪɚɹ ɧɚɡɵɜɚɟɬɫɹ ɷɧɬɚɥɶɩװɹ. ɗɧɬɚɥɶɩɢɹ – ɷɬɨ ɮɭɧɤɰɢɹ ɫɨɫɬɨɹɧɢɹ ɫɢɫɬɟɦɵ.
Ɇɨɠɧɨ ɩɨɤɚɡɚɬɶ, ɱɬɨ ɜ
ɢɡɨɯɨɪɧɨɦ ɩɪɨɰɟɫɫɟ (V = const) ɬɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɪɚ-
ɜɟɧ ɢɡɦɟɧɟɧɢɸ ɜɧɭɬɪɟɧɧɟɣ ɷɧɟɪɝɢɢ ɫɢɫɬɟɦɵ:
Q
Ɍɚɤɠɟ ɦɨɠɧɨ ɩɨɤɚɡɚɬɶ, ɱɬɨ ɜ
= U1 – U2 = 'U. (4.5)
V
ɢɡɨɛɚɪɧɨɦ ɩɪɨɰɟɫɫɟ (p = const) ɬɟɩɥɨɜɨɣ ɷɮ-
ɮɟɤɬ ɪɚɜɟɧ ɢɡɦɟɧɟɧɢɸ ɷɧɬɚɥɶɩɢɢ ɫɢɫɬɟɦɵ:
Q
= H2 – H1 = 'H. (4.6)
p
64
Ɍɟɪɦɨɯɢɦɢɹ. Ɋɚɡɞɟɥ ɯɢɦɢɱɟɫɤɨɣ ɬɟɪɦɨɞɢɧɚɦɢɤɢ, ɩɨɫɜɹɳɟɧɧɵɣ ɢɫɫɥɟɞɨ-
ɜɚɧɢɹɦ ɬɟɩɥɨɜɵɯ ɷɮɮɟɤɬɨɜ ɯɢɦɢɱɟɫɤɢɯ ɪɟɚɤɰɢɣ, ɬɟɩɥɨɬ ɮɚɡɨɜɵɯ ɩɟɪɟɯɨɞɨɜ,
ɬɟɩɥɨɬ ɪɚɫɬɜɨɪɟɧɢɹ ɜɟɳɟɫɬɜ, ɪɚɡɛɚɜɥɟɧɢɹ ɪɚɫɬɜɨɪɨɜ ɢ ɬ. ɩ., ɧɚɡɵɜɚɟɬɫɹ
.
ɯɢɦɢɟɣ
ɬɟɩɥɨɜɵɦ ɷɮɮɟɤɬɨɦ ɯɢɦɢɱɟɫɤɨɣ ɪɟɚɤɰɢɢ ɩɨɧɢɦɚɸɬ ɤɨɥɢɱɟɫɬɜɨ ɬɟɩ-
ɉɨɞ
ɬɟɪɦɨ-
ɥɨɬɵ, ɤɨɬɨɪɨɟ ɜɵɞɟɥɹɟɬɫɹ ɢɥɢ ɩɨɝɥɨɳɚɟɬɫɹ ɩɪɢ ɭɫɥɨɜɢɹɯ:
1. ɉɪɨɰɟɫɫ ɩɪɨɬɟɤɚɟɬ ɧɟɨɛɪɚɬɢɦɨ ɩɪɢ
p = const ɢɥɢ V = const;
2. ȼ ɫɢɫɬɟɦɟ ɧɟ ɫɨɜɟɪɲɚɟɬɫɹ ɧɢɤɚɤɢɯ ɜɢɞɨɜ ɪɚɛɨɬ, ɤɪɨɦɟ ɪɚɛɨɬɵ ɪɚɫɲɢɪɟ-
ɧɢɹ ɫɢɫɬɟɦɵ (
W c = 0);
3. ɉɪɨɞɭɤɬɵ ɪɟɚɤɰɢɢ ɢɦɟɸɬ ɬɭ ɠɟ ɬɟɦɩɟɪɚɬɭɪɭ, ɱɬɨ ɢ ɢɫɯɨɞɧɵɟ ɜɟɳɟɫɬɜɚ
(
T
= T2).
1
ɋɥɟɞɫɬɜɢɟɦ ɢɡ ɩɟɪɜɨɝɨ ɡɚɤɨɧɚ ɬɟɪɦɨɞɢɧɚɦɢɤɢ ɩɪɢɦɟɧɢɬɟɥɶɧɨ ɤ ɯɢɦɢɱɟ-
ɫɤɢɦ ɩɪɨɰɟɫɫɚɦ ɹɜɥɹɟɬɫɹ
ɡɚɤɨɧ Ƚɟɫɫɚ (1840 ɝ.), ɤɨɬɨɪɵɣ ɮɨɪɦɭɥɢɪɭɟɬɫɹ ɫɥɟɞɭ-
ɸɳɢɦ ɨɛɪɚɡɨɦ:
ɬɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɪɟɚɤɰɢɢ ɧɟ ɡɚɜɢɫɢɬ ɨɬ ɩɭɬɢ ɩɪɨɰɟɫɫɚ (ɩɪɨɦɟɠɭɬɨɱɧɵɯ
ɫɬɚɞɢɣ), ɚ ɨɩɪɟɞɟɥɹɟɬɫɹ ɬɨɥɶɤɨ ɧɚɱɚɥɶɧɵɦ ɢ ɤɨɧɟɱɧɵɦ ɫɨɫɬɨɹɧɢɹɦɢ ɫɢɫɬɟɦɵ
(ɬɨ ɟɫɬɶ ɫɨɫɬɨɹɧɢɟɦ ɢɫɯɨɞɧɵɯ ɜɟɳɟɫɬɜ ɢ ɩɪɨɞɭɤɬɨɜ ɪɟɚɤɰɢɢ).
Ɍɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɯɢɦɢɱɟɫɤɨɣ ɪɟɚɤɰɢɢ ɩɪɢ ɩɨɫɬɨɹɧɧɨɦ ɞɚɜɥɟɧɢɢ ɪɚɜɟɧ ɢɡɦɟɧɟɧɢɸ ɷɧɬɚɥɶɩɢɢ ɫɢɫɬɟɦɵ, ɤɨɬɨɪɭɸ ɧɚɡɵɜɚɸɬ ɷɧɬɚɥɶɩɢɟɣ ɯɢɦɢɱɟɫɤɨɣ ɪɟɚɤɰɢɢ '
H.
r
Ɍɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɫɱɢɬɚɸɬ ɩɨɥɨɠɢɬɟɥɶɧɵɦ ɞɥɹ
ɫɨɜ ('
H > 0, ɬɟɩɥɨɬɚ ɩɨɝɥɨɳɚɟɬɫɹ) ɢ ɨɬɪɢɰɚɬɟɥɶɧɵɦ ɞɥɹ ɷɤɡɨɬɟɪɦɢɱɟɫɤɢɯ ɩɪɨ-
ɰɟɫɫɨɜ ('
H < 0, ɬɟɩɥɨɬɚ ɜɵɞɟɥɹɟɬɫɹ).
ɷɧɞɨɬɟɪɦɢɱɟɫɤɢɯ ɩɪɨɰɟɫ-
ȼ ɬɟɪɦɨɯɢɦɢɢ ɩɪɢ ɧɚɩɢɫɚɧɢɢ ɯɢɦɢɱɟɫɤɨɝɨ ɭɪɚɜɧɟɧɢɹ ɩɪɢɧɹɬɨ ɜɤɥɸɱɚɬɶ
ɜ ɧɟɝɨ ɬɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɪɟɚɤɰɢɢ.
ɋɬɟɯɢɨɦɟɬɪɢɱɟɫɤɨɟ ɭɪɚɜɧɟɧɢɟ ɪɟɚɤɰɢɢ, ɡɚɩɢɫɚɧɧɨɟ ɫ ɭɤɚɡɚɧɢɟɦ ɚɝɪɟɝɚɬɧɵɯ ɫɨɫɬɨɹɧɢɣ ɢɫɯɨɞɧɵɯ ɜɟɳɟɫɬɜ ɢ ɩɪɨɞɭɤɬɨɜ ɢ ɬɟɩɥɨɜɨɝɨ ɷɮɮɟɤɬɚ, ɧɚɡɵɜɚɟɬɫɹ
ɬɟɪɦɨɯɢɦɢɱɟɫɤɢɦ.
Ɍɟɪɦɨɯɢɦɢɱɟɫɤɢɦɢ ɭɪɚɜɧɟɧɢɹɦɢ, ɟɫɥɢ ɬɟɩɥɨɜɵɟ ɷɮɮɟɤɬɵ ɩɪɢɜɨɞɹɬɫɹ ɩɪɢ
ɨɞɧɢɯ ɢ ɬɟɯ ɠɟ ɜɧɟɲɧɢɯ ɭɫɥɨɜɢɹɯ, ɦɨɠɧɨ ɨɩɟɪɢɪɨɜɚɬɶ ɬɨɱɧɨ ɬɚɤ ɠɟ, ɤɚɤ ɫ ɚɥɝɟɛɪɚɢɱɟɫɤɢɦɢ. ȼ ɱɚɫɬɧɨɫɬɢ, ɢɯ ɦɨɠɧɨ ɫɤɥɚɞɵɜɚɬɶ, ɜɵɱɢɬɚɬɶ ɨɞɧɨ ɢɡ ɞɪɭɝɨɝɨ ɢ ɬ. ɩ.
ɗɬɨ ɫɜɨɣɫɬɜɨ ɬɟɪɦɨɯɢɦɢɱɟɫɤɢɯ ɭɪɚɜɧɟɧɢɣ ɜɵɬɟɤɚɟɬ ɢɡ ɡɚɤɨɧɚ Ƚɟɫɫɚ.
ɋɨɩɨɫɬɚɜɥɟɧɢɟ ɬɟɩɥɨɜɵɯ ɷɮɮɟɤɬɨɜ ɢ ɩɪɨɜɟɞɟɧɢɟ ɬɟɪɦɨɯɢɦɢɱɟɫɤɢɯ ɪɚɫɱɟ-
ɩɪɢɜɟɥɨ ɤ ɧɟɨɛɯɨɞɢɦɨɫɬɢ ɜɜɟɞɟɧɢɹ ɩɨɧɹɬɢɣ ɫɬɚɧɞɚɪɬɧɨɝɨ ɫɨɫɬɨɹɧɢɹ ɜɟ-
ɬɨɜ
ɳɟɫɬɜɚ
ɥɟɧɢɢ
ɢ ɫɬɚɧɞɚɪɬɧɨɝɨ ɬɟɩɥɨɜɨɝɨ ɷɮɮɟɤɬɚ.
ɉɨɞ ɫɬɚɧɞɚɪɬɧɵɦ ɬɟɩɥɨɜɵɦ ɷɮɮɟɤɬɨɦ ɩɨɧɢɦɚɸɬ ɟɝɨ ɜɟɥɢɱɢɧɭ ɩɪɢ ɞɚɜ-
0
p
= 105 ɉɚ (1 ɛɚɪ) ɢ ɬɟɦɩɟɪɚɬɭɪɟ Ɍ. Ɍɚɤ ɤɚɤ ɜ ɧɚɫɬɨɹɳɟɟ ɜɪɟɦɹ ɬɟɪɦɨɯɢ-
ɦɢɱɟɫɤɢɟ ɢɫɫɥɟɞɨɜɚɧɢɹ ɱɚɳɟ ɜɫɟɝɨ ɩɪɢɜɨɞɹɬ ɩɪɢ 25 °ɋ, ɬɨ ɜ ɫɩɪɚɜɨɱɧɵɯ ɬɚɛɥɢɰɚɯ ɬɟɩɥɨɜɵɟ ɷɮɮɟɤɬɵ ɪɟɚɤɰɢɢ ɩɪɢɜɨɞɹɬ ɩɪɢ
ɥɨɜɨɣ ɷɮɮɟɤɬ ɪɟɚɤɰɢɢ ɩɪɢ 298,15 K ɩɪɢɧɹɬɨ ɡɚɩɢɫɵɜɚɬɶ ɜ ɜɢɞɟ '
Ɂɚ
ɫɬɚɧɞɚɪɬɧɨɟ ɫɨɫɬɨɹɧɢɟ ɱɢɫɬɨɝɨ ɠɢɞɤɨɝɨ ɢɥɢ ɬɜɟɪɞɨɝɨ ɜɟɳɟɫɬɜɚ ɩɪɢ-
Ɍ = 298,15 K. ɋɬɚɧɞɚɪɬɧɵɣ ɬɟɩ-
0
H
.
r
298
ɧɢɦɚɟɬɫɹ ɟɝɨ ɧɚɢɛɨɥɟɟ ɭɫɬɨɣɱɢɜɨɟ ɮɢɡɢɱɟɫɤɨɟ ɫɨɫɬɨɹɧɢɟ ɩɪɢ ɞɚɧɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɢ ɧɨɪɦɚɥɶɧɨɦ ɚɬɦɨɫɮɟɪɧɨɦ ɞɚɜɥɟɧɢɢ. ȼ ɤɚɱɟɫɬɜɟ ɫɬɚɧɞɚɪɬɧɨɝɨ ɫɨɫɬɨɹɧɢɹ
ɞɥɹ ɝɚɡɚ ɩɪɢɧɹɬɨ ɝɢɩɨɬɟɬɢɱɟɫɤɨɟ ɫɨɫɬɨɹɧɢɟ, ɩɪɢ ɤɨɬɨɪɨɦ ɝɚɡ, ɧɚɯɨɞɹɫɶ ɩɪɢ ɞɚɜ-
65
5
T
G
T
G
ɥɟɧɢɢ 10
ɉɚ, ɩɨɞɱɢɧɹɟɬɫɹ ɡɚɤɨɧɚɦ ɢɞɟɚɥɶɧɵɯ ɝɚɡɨɜ, ɚ ɟɝɨ ɷɧɬɚɥɶɩɢɹ ɪɚɜɧɚ ɷɧ-
ɬɚɥɶɩɢɢ ɪɟɚɥɶɧɨɝɨ ɝɚɡɚ.
ɋɥɟɞɫɬɜɢɟ ɢɡ ɡɚɤɨɧɚ Ƚɟɫɫɚ. Ɍɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɪɟɚɤɰɢɢ ɪɚɜɟɧ ɪɚɡɧɨɫɬɢ
ɦɟɠɞɭ ɫɭɦɦɨɣ ɷɧɬɚɥɶɩɢɣ ɨɛɪɚɡɨɜɚɧɢɹ ɩɪɨɞɭɤɬɨɜ ɪɟɚɤɰɢɢ ɢ ɫɭɦɦɨɣ ɷɧɬɚɥɶɩɢɣ
ɨɛɪɚɡɨɜɚɧɢɹ ɢɫɯɨɞɧɵɯ ɜɟɳɟɫɬɜ.
ɉɨɞ ɷɧɬɚɥɶɩɢɟɣ ɨɛɪɚɡɨɜɚɧɢɹ ɜɟɳɟɫɬɜɚ ɩɨɧɢɦɚɸɬ ɬɨ ɤɨɥɢɱɟɫɬɜɨ ɬɟɩɥɨɬɵ,
ɤɨɬɨɪɨɟ ɜɵɞɟɥɹɟɬɫɹ ɢɥɢ ɩɨɝɥɨɳɚɟɬɫɹ ɩɪɢ ɨɛɪɚɡɨɜɚɧɢɢ ɨɞɧɨɝɨ ɦɨɥɹ
i-ɝɨ ɜɟɳɟ-
ɫɬɜɚ ɢɡ ɩɪɨɫɬɵɯ ɜɟɳɟɫɬɜ, ɜɡɹɬɵɯ ɜ ɭɫɬɨɣɱɢɜɨɦ ɫɨɫɬɨɹɧɢɢ ɩɪɢ ɪɚɫɫɦɚɬɪɢɜɚɟɦɵɯ
ɭɫɥɨɜɢɹɯ (
ɪ, Ɍ).
ɗɧɬɚɥɶɩɢɢ ɨɛɪɚɡɨɜɚɧɢɹ ɜɟɳɟɫɬɜ ɩɪɢ ɫɬɚɧɞɚɪɬɧɵɯ ɭɫɥɨɜɢɹɯ ɩɪɢɧɹɬɨ ɨɛɨɡɧɚɱɚɬɶ '
0
H
. ɋɬɚɧɞɚɪɬɧɵɟ ɬɟɩɥɨɬɵ (ɷɧɬɚɥɶɩɢɢ) ɨɛɪɚɡɨɜɚɧɢɹ ɫɨɟɞɢɧɟɧɢɣ ɫɭɳɟ-
f
298
ɫɬɜɟɧɧɨ ɡɚɜɢɫɹɬ ɤɚɤ ɨɬ ɫɨɫɬɨɹɧɢɹ ɜɟɳɟɫɬɜɚ, ɬɚɤ ɢ ɨɬ ɟɝɨ ɩɪɢɪɨɞɵ. ɇɚɩɪɢɦɟɪ, ɞɥɹ
ɪɨɦɛɢɱɟɫɤɨɣ ɫɟɪɵ '
0
H
(S
f
298
) = 0, ɞɥɹ ɦɨɧɨɤɥɢɧɧɨɣ ɫɟɪɵ '
(ɪɨɦɛ.)
= 0,3 ɤȾɠ/ɦɨɥɶ, ɞɥɹ ɝɚɡɨɨɛɪɚɡɧɨɣ ɫɟɪɵ '
Ⱦɥɹ ɭɫɥɨɜɧɨɣ ɯɢɦɢɱɟɫɤɨɣ ɪɟɚɤɰɢɢ:
0
H
(S
f
298
= 129,1 ɤȾɠ/ɦɨɥɶ).
(ɝ))
0
H
(S
f
298
(ɦɨɧɨɤɥ)
) =
Q1 A1 + Q2 A2 = Q3 A3 + Q4 A4
ɫɬɚɧɞɚɪɬɧɨɟ ɢɡɦɟɧɟɧɢɟ ɷɧɬɚɥɶɩɢɢ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ
Ɍ = 298 K ɦɨɠɧɨ ɪɚɫɫɱɢɬɚɬɶ
ɩɨ ɮɨɪɦɭɥɟ:
0
'
H
= Q3 '
r
298
H
f
0
(A3) +Q4 '
298
H
f
0
(A4) – Q1 '
298
H
f
0
(A1) – Q2 '
298
0
H
(A2).
f
298
4.2. ɇɚɩɪɚɜɥɟɧɢɟ ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨɝɨ ɩɪɨɬɟɤɚɧɢɹ ɯɢɦɢɱɟɫɤɢɯ ɪɟɚɤɰɢɣ
ɇɚ ɨɫɧɨɜɚɧɢɢ ɩɟɪɜɨɝɨ ɡɚɤɨɧɚ ɬɟɪɦɨɞɢɧɚɦɢɤɢ ɧɟɥɶɡɹ ɫɞɟɥɚɬɶ ɤɚɤɢɯ-ɥɢɛɨ
ɜɵɜɨɞɨɜ ɨ ɧɚɩɪɚɜɥɟɧɢɢ ɩɪɨɰɟɫɫɚ ɢ ɨ ɫɨɫɬɨɹɧɢɢ ɪɚɜɧɨɜɟɫɢɹ. Ⱦɥɹ ɜɵɹɫɧɟɧɢɹ
ɷɬɢɯ ɜɨɩɪɨɫɨɜ ɢɫɩɨɥɶɡɭɟɬɫɹ ɜɬɨɪɨɣ ɡɚɤɨɧ ɬɟɪɦɨɞɢɧɚɦɢɤɢ. Ⱥɧɚɥɢɬɢɱɟɫɤɢɦ ɜɵɪɚɠɟɧɢɟɦ
ɜɬɨɪɨɝɨ ɡɚɤɨɧɚ ɬɟɪɦɨɞɢɧɚɦɢɤɢ ɹɜɥɹɟɬɫɹ ɭɪɚɜɧɟɧɢɟ:
Q
ɨɛɪ
(4.7)
dS
ɞɥɹ ɥɸɛɨɝɨ ɨɛɪɚɬɢɦɨɝɨ ɩɪɨɰɟɫɫɚ. Ɏɭɧɤɰɢɹ
S ɧɚɡɵɜɚɟɬɫɹ ɷɧɬɪɨɩɢɟɣ. Ⱦɥɹ ɧɟɨɛ-
ɪɚɬɢɦɨɝɨ ɩɪɨɰɟɫɫɚ ɪɚɜɟɧɫɬɜɨ (4.7) ɩɪɟɜɪɚɳɚɟɬɫɹ ɜ ɧɟɪɚɜɟɧɫɬɜɨ:
Q
.
!
dS
ɋɨɝɥɚɫɧɨ ɭɪɚɜɧɟɧɢɸ (4.7) ɪɚɡɦɟɪɧɨɫɬɶ ɷɧɬɪɨɩɢɢ [Ⱦɠ/(ɦɨɥɶ K)].
Ⱦɥɹ ɢɡɨɥɢɪɨɜɚɧɧɵɯ ɫɢɫɬɟɦ ɜɟɪɧɨ ɫɥɟɞɭɸɳɟɟ ɭɬɜɟɪɠɞɟɧɢɟ:
ɜ ɢɡɨɥɢɪɨɜɚɧɧɨɣ ɫɢɫɬɟɦɟ ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨ ɩɪɨɬɟɤɚɸɬ ɬɨɥɶɤɨ ɬɟ ɩɪɨɰɟɫ-
' S
!
ɫɵ, ɤɨɬɨɪɵɟ ɫɨɩɪɨɜɨɠɞɚɸɬɫɹ ɭɜɟɥɢɱɟɧɢɟɦ ɷɧɬɪɨɩɢɢ (
0).
ɉɪɢ ɪɚɜɧɨɜɟɫɢɢ 'S = 0.
ȼ 1911 ɝ. Ɇ. ɉɥɚɧɤ ɫɮɨɪɦɭɥɢɪɨɜɚɥ ɩɨɫɬɭɥɚɬ:
ɚɥɶɧɨɝɨ ɢɞɟɚɥɶɧɨɝɨ ɤɪɢɫɬɚɥɥɚ ɩɪɢ ɚɛɫɨɥɸɬɧɨɦ ɧɭɥɟ ɪɚɜɧɚ ɧɭɥɸ S
ɷɧɬɪɨɩɢɹ ɥɸɛɨɝɨ ɢɧɞɢɜɢɞɭ-
(0 K) = 0 .
ɗɬɨ ɩɨɥɨɠɟɧɢɟ ɧɟ ɨɬɧɨɫɢɬɫɹ ɤ ɫɬɟɤɥɚɦ, ɪɚɫɬɜɨɪɚɦ, ɞɟɮɟɤɬɧɵɦ ɤɪɢɫɬɚɥɥɚɦ,
ɧɨ ɢ ɞɥɹ ɧɢɯ ɷɧɬɪɨɩɢɹ ɩɪɢ 0 K ɨɛɵɱɧɨ ɨɱɟɧɶ ɦɚɥɚ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɡɚ ɬɨɱɤɭ ɨɬ-
66
ɫɱɟɬɚ ɦɨɠɧɨ ɩɪɢɧɹɬɶ S 0 (0 K) = 0. ɉɨɫɬɭɥɚɬ ɉɥɚɧɤɚ ɫɱɢɬɚɟɬɫɹ ɬɪɟɬɶɢɦ ɡɚɤɨ-
ɧɨɦ ɬɟɪɦɨɞɢɧɚɦɢɤɢ.
Ɍɪɟɬɢɣ ɡɚɤɨɧ ɬɟɪɦɨɞɢɧɚɦɢɤɢ ɩɨɡɜɨɥɹɟɬ ɜɵɱɢɫɥɢɬɶ ɬɚɤ ɧɚɡɵɜɚɟɦɵɟ ɚɛɫɨ-
ɥɸɬɧɵɟ ɡɧɚɱɟɧɢɹ ɷɧɬɪɨɩɢɢ ɞɥɹ ɥɸɛɨɝɨ ɜɟɳɟɫɬɜɚ ɜ ɥɸɛɨɦ ɚɝɪɟɝɚɬɧɨɦ ɫɨɫɬɨɹɧɢɢ, ɟɫɥɢ ɢɡɜɟɫɬɧɵ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɡɧɚɱɟɧɢɹ ɬɟɩɥɨɟɦɤɨɫɬɟɣ ɨɬ 0 K ɞɨ ɞɚɧɧɨɣ ɬɟɦɩɟɪɚɬɭɪɵ
Ⱦɥɹ ɯɢɦɢɱɟɫɤɨɣ ɪɟɚɤɰɢɢ: Q
ɩɪɢ
Ɍ = 298 K ɦɨɠɧɨ ɪɚɫɫɱɢɬɚɬɶ ɩɨ ɮɨɪɦɭɥɟ:
'
r
Ɍ, ɚ ɬɚɤɠɟ ɬɟɩɥɨɬɵ ɮɚɡɨɜɵɯ ɩɟɪɟɯɨɞɨɜ.
+ Q2 A2 = Q3 A3 + Q4 A
1 A1
0
S
298
= Q
3
0
S
(A3) + Q
298
4
S
0
298
(A4) – Q
ɢɡɦɟɧɟɧɢɟ ɷɧɬɪɨɩɢɢ
4
0
S
(A1) – Q
1
298
0
S
(A2).
2
298
ɗɧɟɪɝɢɹ Ƚɢɛɛɫɚ. ɇɚɩɪɚɜɥɟɧɢɟ ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨɝɨ ɩɪɨɬɟɤɚɧɢɹ ɩɪɨɰɟɫ-
ɫɨɜ ɜ ɡɚɤɪɵɬɵɯ ɫɢɫɬɟɦɚɯ
. ȼ ɬɟɪɦɨɞɢɧɚɦɢɤɟ ɜɚɠɧɨɟ ɡɧɚɱɟɧɢɟ ɢɦɟɟɬ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɚɹ ɮɭɧɤɰɢɹ, ɤɨɬɨɪɚɹ ɧɚɡɵɜɚɟɬɫɹ ɷɧɟɪɝɢɹ Ƚɢɛɛɫɚ. Ɉɧɚ ɨɩɪɟɞɟɥɹɟɬɫɹ
ɫɥɟɞɭɸɳɢɦ ɨɛɪɚɡɨɦ:
G = U – TS + pV = H – TS.
Ɇɨɠɧɨ ɩɨɤɚɡɚɬɶ, ɱɬɨ ɭɛɵɥɶ ɮɭɧɤɰɢɢ G ɯɚɪɚɤɬɟɪɢɡɭɟɬ ɦɚɤɫɢɦɚɥɶɧɭɸ ɩɨ-
ɥɟɡɧɭɸ ɪɚɛɨɬɭ, ɤɨɬɨɪɭɸ ɦɨɠɧɨ ɩɨɥɭɱɢɬɶ ɩɪɢ ɩɨɫɬɨɹɧɧɵɯ ɬɟɦɩɟɪɚɬɭɪɟ ɢ ɞɚɜɥɟɧɢɢ.
ȼ ɬɟɪɦɨɞɢɧɚɦɢɤɟ ɭɫɬɚɧɚɜɥɢɜɚɟɬɫɹ ɫɥɟɞɭɸɳɢɣ ɤɪɢɬɟɪɢɣ ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨ-
ɝɨ ɩɪɨɬɟɤɚɧɢɹ ɩɪɨɰɟɫɫɨɜ ɜ ɡɚɤɪɵɬɵɯ ɫɢɫɬɟɦɚɯ.
ȼ ɡɚɤɪɵɬɵɯ ɫɢɫɬɟɦɚɯ ɩɪɢ ɩɨɫɬɨɹɧɧɵɯ ɬɟɦɩɟɪɚɬɭɪɟ ɢ ɞɚɜɥɟɧɢɢ ɫɚɦɨɩɪɨɢɡ-
ɜɨɥɶɧɨ ɩɪɨɬɟɤɚɸɬ ɩɪɨɰɟɫɫɵ, ɫɨɩɪɨɜɨɠɞɚɸɳɢɟɫɹ ɭɦɟɧɶɲɟɧɢɟɦ ɷɧɟɪɝɢɢ Ƚɢɛɛɫɚ:
dG
< 0 (ǻG
p, T
p, T
< 0).
ȿɫɥɢ ɧɚ ɫɢɫɬɟɦɭ ɧɟ ɞɟɣɫɬɜɭɸɬ ɜɧɟɲɧɢɟ ɫɢɥɵ:
dG
= 0 (ǻG
p, T
p, T
= 0).
ɗɬɨ ɨɡɧɚɱɚɟɬ, ɱɬɨ ɫɢɫɬɟɦɚ ɧɚɯɨɞɢɬɫɹ ɜ ɪɚɜɧɨɜɟɫɢɢ.
Ɋɚɫɱɟɬ '
G
ɜ ɯɢɦɢɱɟɫɤɢɯ ɪɟɚɤɰɢɹɯ ɦɨɠɧɨ ɨɫɭɳɟɫɬɜɢɬɶ ɩɨ ɭɪɚɜɧɟɧɢɸ ɞɥɹ
p,T
ɫɬɚɧɞɚɪɬɧɵɯ ɭɫɥɨɜɢɣ:
'
G
r
0
= 'r H
0
– T '
S 0. (4.8)
r
ȼ ɷɬɨɦ ɫɥɭɱɚɟ ɜ ɪɚɫɱɟɬɚɯ ɦɨɠɧɨ ɢɫɩɨɥɶɡɨɜɚɬɶ ɫɬɚɧɞɚɪɬɧɵɟ ɢɡɦɟɧɟɧɢɹ ɷɧ-
ɬɚɥɶɩɢɢ ɢ ɷɧɬɪɨɩɢɢ ɪɟɚɤɰɢɢ.
ɉɪɢɦɟɪɵ ɪɟɲɟɧɢɹ ɡɚɞɚɱ
ɉɪɢɦɟɪ 4.1. Ⱥɰɟɬɢɥɟɧ ɲɢɪɨɤɨ ɩɪɢɦɟɧɹɸɬ ɞɥɹ ɫɜɚɪɤɢ ɢ ɪɟɡɤɢ ɦɟɬɚɥɥɨɜ.
Ɋɚɫɫɱɢɬɚɬɶ ɬɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɫɝɨɪɚɧɢɹ 20 ɥ (ɧ. ɭ.) ɚɰɟɬɢɥɟɧɚ ɩɪɢ ɩɨɫɬɨɹɧɧɨɦ
ɞɚɜɥɟɧɢɢ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ
Ɍ = 298 Ʉ.
Ɋɟɲɟɧɢɟ. Ɂɚɩɢɲɟɦ ɭɪɚɜɧɟɧɢɟ ɝɨɪɟɧɢɹ ɚɰɟɬɢɥɟɧɚ:
C
2H2 (ɝ)
+ 2,5O
2 (ɝ)
= 2CO
2 (ɝ)
+ H2O
(ɠ)
.
67
ɋɩɪɚɜɨɱɧɵɟ ɞɚɧɧɵɟ:
f
ȼɟɳɟɫɬɜɨ C
0
'
H
, ɤȾɠ/ɦɨɥɶ
298
O
2H2 (ɝ)
226 0 –393 –286
CO
2 (ɝ)
H
2 (ɝ)
ɉɪɨɜɨɞɢɦ ɪɚɫɱɟɬ ɞɥɹ ɫɝɨɪɚɧɢɹ 1 ɦɨɥɹ ɚɰɟɬɢɥɟɧɚ ɩɨ ɮɨɪɦɭɥɟ:
0
'
H
= 2'
r
298
H
f
0
(CO2) + '
298
H
f
0
(H2O) – '
298
0
H
f
298
(C2H2) – 2,5 '
H
f
Ɋɟɡɭɥɶɬɚɬ ɜɵɱɢɫɥɟɧɢɣ:
0
'
H
= 2 ā (–393) + (–286) – 226 – 2,5 ā 0 = - 1298 ɤȾɠ/ɦɨɥɶ.
r
298
ȼɵɱɢɫɥɹɟɦ ɤɨɥɢɱɟɫɬɜɨ ɜɟɳɟɫɬɜɚ ɚɰɟɬɢɥɟɧɚ:
(C H ) 0,89 ɦɨɥɶ.
n
22
V
V
M
20 ɥ
22,4 ɥ/ɦɨɥɶ
ȼɵɱɢɫɥɹɟɦ ɤɨɥɢɱɟɫɬɜɨ ɬɟɩɥɨɬɵ, ɜɵɞɟɥɹɸɳɟɣɫɹ ɩɪɢ ɫɝɨɪɚɧɢɢ 20 ɥ (ɧ. ɭ.)
ɚɰɟɬɢɥɟɧɚ:
0
'
H
r
x
= n (C2H2) Â '
0
H
= 0,89 ɦɨɥɶ Â (–1298) ɤȾɠ/ɦɨɥɶ = –1158,9 ɤȾɠ.
r
298
ɉɪɢɦɟɪ 4.2. ɉɨ ɬɟɪɦɨɯɢɦɢɱɟɫɤɨɦɭ ɭɪɚɜɧɟɧɢɸ ɪɚɫɫɱɢɬɚɬɶ ɫɬɚɧɞɚɪɬɧɭɸ
ɷɧɬɚɥɶɩɢɸ ɨɛɪɚɡɨɜɚɧɢɹ ɩɪɨɞɭɤɬɚ ɪɟɚɤɰɢɢ:
2Fe
3O4(ɬ)
+ 9SO
2(ɝ)
+ 5O
= 3Fe2(SO4)
2(ɝ)
3(ɬ)
0
,
H
' = 2845,7 ɤȾɠ.
298
r
Ɋɟɲɟɧɢɟ. ɉɨ ɩɟɪɜɨɦɭ ɫɥɟɞɫɬɜɢɸ ɢɡ ɡɚɤɨɧɚ Ƚɟɫɫɚ ɫɬɚɧɞɚɪɬɧɚɹ ɷɧɬɚɥɶɩɢɹ
ɞɚɧɧɨɣ ɪɟɚɤɰɢɢ:
0
H
'
= 3'
r
298
ɋɥɟɞɨɜɚɬɟɥɶɧɨ, ɫɬɚɧɞɚɪɬɧɚɹ ɷɧɬɚɥɶɩɢɹ ɨɛɪɚɡɨɜɚɧɢɹ Fe
'
+ 5'
0
H
f
298
H
f
0
H
(Fe2(SO4)3) =
f
298
(O2) =
0
(Fe2(SO4)3) 2'
298
1
('
1
3
3
[2845,7 + 2(1117,1) + 9(296,9) + 50] = 2584 ɤȾɠ/ɦɨɥɶ.
0
H
(Fe3O4) 9'
f
298
0
H
+ 2'
r
298
0
H
f
298
(Fe3O4) + 9'
0
H
f
298
(SO2) 5'
(SO4)
2
3(ɬ)
0
H
(SO2) +
f
298
f
:
ɉɪɢɦɟɪ 4.3. ȼɵɱɢɫɥɢɬɶ ɫɬɚɧɞɚɪɬɧɭɸ ɷɧɬɚɥɶɩɢɸ ɫɝɨɪɚɧɢɹ ɚɰɟɬɢɥɟɧɚ C
0
(C H )
ɩɨ ɟɝɨ ɫɬɚɧɞɚɪɬɧɨɣ ɷɧɬɚɥɶɩɢɢ ɨɛɪɚɡɨɜɚɧɢɹ
Ɋɚɫɫɱɢɬɚɬɶ ɫɬɚɧɞɚɪɬɧɵɣ ɬɟɩɥɨɜɨɣ ɷɮɮɟɤɬ ɫɝɨɪɚɧɢɹ 7,33 ɥ C
ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 17 qC ɢ
p = 98,6 ɤɉɚ) ɩɪɢ ɩɨɫɬɨɹɧɧɨɦ ɞɚɜɥɟɧɢɢ.
H'
f
298 2 2
= 226,8 ɤȾɠ/ɦɨɥɶ.
(ɨɛɴɺɦ ɢɡɦɟɪɟɧ
2H2
Ɋɟɲɟɧɢɟ. Ɂɚɩɢɲɟɦ ɭɪɚɜɧɟɧɢɟ ɪɟɚɤɰɢɢ ɫɝɨɪɚɧɢɹ ɨɞɧɨɝɨ ɦɨɥɹ ɚɰɟɬɢɥɟɧɚ:
C
2H2(ɝ)
+ 2,5O
= 2CO
2(ɝ)
2(ɝ)
+ H2O
(ɠ)
.
ɋɨɝɥɚɫɧɨ ɫɥɟɞɫɬɜɢɸ ɢɡ ɡɚɤɨɧɚ Ƚɟɫɫɚ ɢ ɨɩɪɟɞɟɥɟɧɢɸ ɫɬɚɧɞɚɪɬɧɨɣ ɷɧɬɚɥɶ-
ɩɢɢ ɫɝɨɪɚɧɢɹ ɜɟɳɟɫɬɜɚ ɦɨɠɟɦ ɡɚɩɢɫɚɬɶ:
0
'
H
= '
r
298
0
'
H
= '
r
298
0
H
(C2H2) = 2'
c
298
0
H
– '
0
H
c
298
(C2H2) – 2,5 '
f
298
(C2H2) = 2Â(393,5) + (285,8) 226,8 2,50 =
= 1299,6 ɤȾɠ/ɦɨɥɶ C
H
f
0
(CO2) + '
298
H
f
0
298
2H2
(O2).
.
H
f
68
0
298
(H2O) –
2O(ɠ)
0
298
H
(O2).
0
298
(O2).
2H2
Ⱦɥɹ ɜɵɱɢɫɥɟɧɢɹ ɤɨɥɢɱɟɫɬɜɚ ɜɟɳɟɫɬɜɚ ɚɰɟɬɢɥɟɧɚ ɩɪɢɜɟɞɺɦ ɨɛɴɺɦ ɝɚɡɚ
p
ɤ ɧɨɪɦɚɥɶɧɵɦ ɭɫɥɨɜɢɹɦ (
= 101,3 ɤɉɚ, T0 = 273K) ɩɨ ɨɛɴɟɞɢɧɺɧɧɨɦɭ ɝɚɡɨɜɨɦɭ
0
ɡɚɤɨɧɭ:
pV
pV
00
TT
0
pVT
V
|
0
0
101,3 (273 17)
pT
0
98,6 7,33 273
;
6, 72 ɥ.
ɍɱɢɬɵɜɚɹ, ɱɬɨ 1 ɦɨɥɶ ɝɚɡɚ ɩɪɢ ɧɨɪɦɚɥɶɧɵɯ ɭɫɥɨɜɢɹɯ ɩɨ ɡɚɤɨɧɭ Ⱥɜɨɝɚɞɪɨ
ɡɚɧɢɦɚɟɬ ɨɛɴɟɦ 22,4 ɥ, ɨɩɪɟɞɟɥɢɦ:
V
nV
CH
22
CH
22
M
6, 72
22,4
0,3 ɦɨɥɶ.
Ɉɬɫɸɞɚ ɩɨɥɭɱɚɟɦ:
QHn ' |
pr
0
298 2 2
1299,6 0,3 389,9 ɤȾɠ.(C H )
ɉɪɢɦɟɪ 4.4. Ɋɚɫɫɱɢɬɚɬɶ ɫɬɚɧɞɚɪɬɧɭɸ ɷɧɟɪɝɢɸ Ƚɢɛɛɫɚ ɞɥɹ ɪɟɚɤɰɢɢ ɪɚɡɥɨ-
ɠɟɧɢɹ ɩɟɪɯɥɨɪɚɬɚ ɤɚɥɢɹ:
KClO
4 (ɬ)
= KCl
+ 2O
(ɬ)
2 (ɝ)
.
Ɋɟɲɟɧɢɟ:
0
'
H
= '
r
298
0
H
'
'
'
'
'
= (–437) + 2 0 – (–427) = –10 ɤȾɠ;
r
298
0
S
= S
r
298
0
S
= 83 + 2205 – 151 = 342 Ⱦɠ/Ʉ;
r
298
0
G
= '
r
298
0
G
= –10000 Ⱦɠ – 298 Ʉ342 Ⱦɠ/Ʉ = –111916 Ⱦɠ | –112 ɤȾɠ.
r
298
Ʉɨɝɞɚ ɢɡɦɟɧɟɧɢɟ ɷɧɬɚɥɶɩɢɢ ɨɬɪɢɰɚɬɟɥɶɧɨ ('
ɩɨɥɨɠɢɬɟɥɶɧɨ ('
ɧɟɧɢɸ (5.8) ɜɫɟɝɞɚ ɨɬɪɢɰɚɬɟɥɶɧɨ ('
0
H
(KCl) + 2 '
f
298
0
(KCl) + 2
298
0
H
r
298
S ! 0), ɬɨ ɢɡɦɟɧɟɧɢɟ ɷɧɟɪɝɢɢ Ƚɢɛɛɫɚ ɪɟɚɤɰɢɢ, ɫɨɝɥɚɫɧɨ ɭɪɚɜ-
r
– T '
S
S
r
0
H
(O2) – '
f
298
0
298
0
298
(O2) – S
0
298
G 0) ɩɪɢ ɥɸɛɵɯ ɬɟɦɩɟɪɚɬɭɪɚɯ. Ɍɚɤɢɟ ɪɟ-
r
0
H
(KClO4);
f
298
(KClO4);
H 0), ɚ ɢɡɦɟɧɟɧɢɟ ɷɧɬɪɨɩɢɢ
r
ɚɤɰɢɢ ɜɫɟɝɞɚ ɦɨɝɭɬ ɩɪɨɬɟɤɚɬɶ ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨ ɜ ɩɪɹɦɨɦ ɧɚɩɪɚɜɥɟɧɢɢ (ɫɥɟɜɚ
ɧɚɩɪɚɜɨ).
ɉɪɢɦɟɪ 4.5. Ɋɚɫɫɱɢɬɚɬɶ ɫɬɚɧɞɚɪɬɧɭɸ ɷɧɟɪɝɢɸ Ƚɢɛɛɫɚ ɞɥɹ ɪɟɚɤɰɢɢ ɪɚɡɥɨ-
ɠɟɧɢɹ ɯɥɨɪɨɜɨɞɨɪɨɞɚ ɧɚ ɩɪɨɫɬɵɟ ɜɟɳɟɫɬɜɚ:
2HCl
(ɝ)
= H
2 (ɝ)
+ Cl
2 (ɝ)
.
Ɋɟɲɟɧɢɟ.
0
'
H
= '
r
298
0
H
'
'
'
'
'
= 0 + 0 – 2 (–92) = 184 ɤȾɠ;
r
298
0
S
= S
r
298
0
S
= 131 + 223 – 2 187 = –20 Ⱦɠ/Ʉ;
r
298
0
G
= '
r
298
0
G
= 184000 Ⱦɠ – 298 Ʉ(–20) Ⱦɠ/Ʉ = 189960 Ⱦɠ | 190 ɤȾɠ.
r
298
H
f
0
298
H
r
0
(H2) + '
298
(H2) + S
0
– T '
298
H
f
0
(Cl2) – 2 S
298
0
S
r
298
0
298
(Cl2) – 2'
0
(HCl);
298
0
H
(HCl);
f
298
69
Ʉɨɝɞɚ ɢɡɦɟɧɟɧɢɟ ɷɧɬɚɥɶɩɢɢ ɩɨɥɨɠɢɬɟɥɶɧɨ ('
f
S
ɩɢɢ ɨɬɪɢɰɚɬɟɥɶɧɨ ('
S 0), ɬɨ ɢɡɦɟɧɟɧɢɟ ɷɧɟɪɝɢɢ Ƚɢɛɛɫɚ ɪɟɚɤɰɢɢ, ɫɨɝɥɚɫɧɨ
r
ɭɪɚɜɧɟɧɢɸ (5.8) ɜɫɟɝɞɚ ɩɨɥɨɠɢɬɟɥɶɧɨ ('
G ! 0) ɩɪɢ ɥɸɛɵɯ ɬɟɦɩɟɪɚɬɭɪɚɯ. Ɍɚ-
r
H ! 0), ɚ ɢɡɦɟɧɟɧɢɟ ɷɧɬɪɨ-
r
ɤɢɟ ɪɟɚɤɰɢɢ ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨ ɜ ɩɪɹɦɨɦ ɧɚɩɪɚɜɥɟɧɢɢ ɧɟ ɢɞɭɬ, ɚ ɫɚɦɨ ɩɪɨɢɡɜɨɥɶɧɨ ɩɪɨɬɟɤɚɟɬ ɨɛɪɚɬɧɚɹ ɪɟɚɤɰɢɹ (ɫɩɪɚɜɚ ɧɚɥɟɜɨ).
ɉɪɢɦɟɪ 4.6. ȼ ɤɨɧɜɟɪɬɟɪɚɯ ɜɵɯɥɨɩɧɵɯ ɝɚɡɨɜ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɝɟɬɟɪɨɝɟɧɧɨ-
ɝɨ ɤɚɬɚɥɢɡɚɬɨɪɚ ɩɪɨɬɟɤɚɟɬ ɪɟɚɤɰɢɹ:
2CO
+ 2NO
(ɝ)
= 2CO
(ɝ)
2 (ɝ)
+ N2
.
(ɝ)
Ɉɩɪɟɞɟɥɢɬɶ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɭɸ ɜɨɡɦɨɠɧɨɫɬɶ ɩɪɨɬɟɤɚɧɢɹ ɞɚɧɧɨɣ ɪɟɚɤɰɢɢ ɩɪɢ
ɫɬɚɧɞɚɪɬɧɵɯ ɭɫɥɨɜɢɹɯ (
Ɍ = 298 K).
Ɋɟɲɟɧɢɟ. ɋɩɪɚɜɨɱɧɵɟ ɞɚɧɧɵɟ:
ȼɟɳɟɫɬɜɨ CO
0
'
H
, ɤȾɠ/ɦɨɥɶ
298
0
, Ⱦɠ/(ɦɨɥɶÂK) 198 211 214 192
298
NO
(ɝ)
–110 91 –393 0
CO
(ɝ)
2 (ɝ)
N
2 (ɝ)
Ɋɚɫɱɺɬ ɫɬɚɧɞɚɪɬɧɨɣ ɷɧɬɚɥɶɩɢɢ ɪɟɚɤɰɢɢ ɩɪɨɜɨɞɢɦ ɩɨ ɮɨɪɦɭɥɟ:
0
H
'
= 2'
r
298
H
f
0
(CO2) + '
298
H
f
0
(N2) – 2 '
298
H
f
0
(CO) – 2 '
298
0
H
(NO).
f
298
Ɋɟɡɭɥɶɬɚɬ ɜɵɱɢɫɥɟɧɢɣ:
0
'
H
= 2 ā (–393) + 0 – 2 ā (–110) – 2 ā 91 = –748 ɤȾɠ.
r
298
Ⱦɚɧɧɚɹ ɪɟɚɤɰɢɹ ɹɜɥɹɟɬɫɹ ɷɤɡɨɬɟɪɦɢɱɟɫɤɨɣ.
Ɋɚɫɱɺɬ ɫɬɚɧɞɚɪɬɧɨɣ ɷɧɬɪɨɩɢɢ ɪɟɚɤɰɢɢ ɩɪɨɜɨɞɢɦ ɩɨ ɮɨɪɦɭɥɟ:
0
'
S
r
298
= 2S
0
(CO2) + S
298
0
(N2) – 2S
298
0
(CO) – 2S
298
0
298
(NO).
Ɋɟɡɭɥɶɬɚɬ ɜɵɱɢɫɥɟɧɢɣ:
0
S
'
'
'
ɂɡɦɟɧɟɧɢɹ ɷɧɬɚɥɶɩɢɢ ɢ ɷɧɬɪɨɩɢɢ ɨɬɪɢɰɚɬɟɥɶɧɵ ('
= 2 ā 214 + 192 – 2 ā 198 – 2 ā 211 = –192 Ⱦɠ/K.
r
298
0
G
= '
r
298
0
G
= –748000 Ⱦɠ – 298 K(–192) Ⱦɠ/K = –690784 Ⱦɠ | –690,8 ɤȾɠ.
r
298
0
H
– T '
r
298
0
S
r
298
H 0, 'r S 0). ȼ ɷɬɨɦ
r
ɫɥɭɱɚɟ ɧɚɩɪɚɜɥɟɧɢɟ ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨɝɨ ɩɪɨɰɟɫɫɚ ɨɩɪɟɞɟɥɹɟɬɫɹ ɬɟɦɩɟɪɚɬɭɪɨɣ.
ɉɪɢ ɧɢɡɤɢɯ ɬɟɦɩɟɪɚɬɭɪɚɯ, ɤɨɝɞɚ |'
ɪɟɚɤɰɢɹ. ɉɪɢ ɜɵɫɨɤɢɯ ɬɟɦɩɟɪɚɬɭɪɚɯ, ɤɨɝɞɚ |'
ɢɞɺɬ ɨɛɪɚɬɧɚɹ ɪɟɚɤɰɢɹ. ɉɪɢ ɜɵɩɨɥɧɟɧɢɢ ɭɫɥɨɜɢɹ '
T'r S, ɢ ɪɚɜɧɨɜɟɪɨɹɬɧɵ ɨɛɚ ɧɚɩɪɚɜɥɟɧɢɹ ɪɟɚɤɰɢɢ.
=
H| ! |T'r S|, ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨ ɢɞɺɬ ɩɪɹɦɚɹ
r
H| | T'r S|, ɫɚɦɨɩɪɨɢɡɜɨɥɶɧɨ
r
G = 0 ɜɟɪɧɨ ɪɚɜɟɧɫɬɜɨ 'r H =
r
Ɍɟɦɩɟɪɚɬɭɪɚ, ɩɪɢ ɤɨɬɨɪɨɣ ɪɚɜɧɨɜɟɪɨɹɬɧɵ ɨɛɚ ɧɚɩɪɚɜɥɟɧɢɹ ɪɟɚɤɰɢɢ, ɩɪɢ-
ɛɥɢɠɟɧɧɨ ɪɚɜɧɚ:
0
H
'
r
T
|
'
r
748000
298
0
S
298
192
3896 K.
70
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