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Файл:Химия для инженеров в примерах, тестах, задачах. Учебное пособие
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2. ɍɤɚɡɚɬɶ ɩɪɨɰɟɫɫ, ɤɨɬɨɪɵɣ ɧɟ ɩɪɨɬɟɤɚɟɬ ɩɪɢ ɪɚɛɨɬɟ ɷɥɟɦɟɧɬɚ Ⱦɚɧɢɷɥɹ –
əɤɨɛɢ.
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. Ⱦɜɢɠɟɧɢɟ ɚɧɢɨɧɨɜ ɜ ɪɚɫɬɜɨɪɟ ɤ ɰɢɧɤɨɜɨɦɭ ɷɥɟɤɬɪɨɞɭ.
ȼɚɪɢɚɧɬ 2. Zn
ȼɚɪɢɚɧɬ 3. Cu
2e o Zn2+.
2+
+ 2e o Cu.
ȼɚɪɢɚɧɬ 4. Ⱦɜɢɠɟɧɢɟ ɤɚɬɢɨɧɨɜ ɜ ɪɚɫɬɜɨɪɟ ɤ ɦɟɞɧɨɦɭ ɷɥɟɤɬɪɨɞɭ.
ȼɚɪɢɚɧɬ 5. Ⱦɜɢɠɟɧɢɟ ɷɥɟɤɬɪɨɧɨɜ ɜɨ ɜɧɟɲɧɟɣ ɰɟɩɢ ɨɬ ɦɟɞɧɨɣ ɩɥɚɫɬɢɧɵ ɤ
ɰɢɧɤɨɜɨɣ.
3. ɍɤɚɡɚɬɶ ɭɫɥɨɜɧɭɸ ɫɯɟɦɭ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɟɫɥɢ ɩɪɢ ɟɝɨ ɪɚɛɨɬɟ
ɧɚ ɷɥɟɤɬɪɨɞɚɯ ɩɪɨɬɟɤɚɸɬ ɫɥɟɞɭɸɳɢɟ ɩɪɨɰɟɫɫɵ:
2+
+ 2e o Ni; Mn – 2e o Mn2+.
Ni
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. Ni | Ni
ȼɚɪɢɚɧɬ 2. Ni
ȼɚɪɢɚɧɬ 3. Mn | Mn
ȼɚɪɢɚɧɬ 4. Mn
ȼɚɪɢɚɧɬ 5. Mn | Mn
2+
|| Mn2+ | Mn.
2+
| Ni || Mn | Mn2+.
2+
|| Ni2+ | Ni.
2+
| Mn || Ni | Ni2+.
2+
|| Ni | Ni2+.
4. ɉɪɢ ɪɚɛɨɬɟ ɜɨɞɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɩɨɬɟɧɰɢɚɥɨɩɪɟɞɟɥɹɸɳɢɦɢ ɹɜɥɹɸɬ-
ɫɹ ɢɨɧɵ…
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. H
ȼɚɪɢɚɧɬ 2. Pt
ȼɚɪɢɚɧɬ 3. Cu
ȼɚɪɢɚɧɬ 4. H
ȼɚɪɢɚɧɬ 5. H
.
2+
.
2+
.
+
.
2
+
.
5. Ɋɚɫɫɱɢɬɚɬɶ ɷɥɟɤɬɪɨɞɧɵɣ ɩɨɬɟɧɰɢɚɥ ɫɟɪɟɛɪɹɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɩɪɢ T = 298 K
ɜ ɜɨɞɧɨɦ ɪɚɫɬɜɨɪɟ AgNO
, ɤɨɧɰɟɧɬɪɚɰɢɹ ɤɨɬɨɪɨɝɨ ɪɚɜɧɚ 0,01 ɦɨɥɶ/ɥ.
3
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 0,681 ȼ.
ȼɚɪɢɚɧɬ 2. 0,917 ȼ.
ȼɚɪɢɚɧɬ 3. 0,74 ȼ.
ȼɚɪɢɚɧɬ 4. 0,858 ȼ.
ȼɚɪɢɚɧɬ 5. 0,799 ȼ.
6. Ɋɚɫɫɱɢɬɚɬɶ ɩɨɬɟɧɰɢɚɥ ɜɨɞɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ T = 298 K,
ɤɨɧɰɟɧɬɪɚɰɢɹ ɢɨɧɨɜ ɜɨɞɨɪɨɞɚ ɪɚɜɧɚ
C = 10
H
4
ɦɨɥɶ/ɥ.
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 0,236 ȼ.
ȼɚɪɢɚɧɬ 2. 2,36 ȼ.
ȼɚɪɢɚɧɬ 3. (–2,36) ȼ.
ȼɚɪɢɚɧɬ 4. (–0,236) ȼ.
ȼɚɪɢɚɧɬ 5. 0 ȼ.
141
7. ɉɨɥɶɡɭɹɫɶ ɡɧɚɱɟɧɢɹɦɢ ɫɬɚɧɞɚɪɬɧɵɯ ɷɥɟɤɬɪɨɞɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ, ɭɤɚ-
ɡɚɬɶ, ɤɚɤɨɣ ɢɡ ɞɚɧɧɵɯ ɦɟɬɚɥɥɨɜ ɨɛɥɚɞɚɟɬ ɛɨɥɶɲɟɣ ɜɨɫɫɬɚɧɨɜɢɬɟɥɶɧɨɣ ɫɩɨɫɨɛɧɨɫɬɶɸ: Fe, Cu, Mg, Ag, Mn.
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. Fe.
ȼɚɪɢɚɧɬ 2. Mg.
ȼɚɪɢɚɧɬ 3. Ag.
ȼɚɪɢɚɧɬ 4. Mn.
ȼɚɪɢɚɧɬ 5. Cu.
8. ɉɨɥɶɡɭɹɫɶ ɡɧɚɱɟɧɢɹɦɢ ɫɬɚɧɞɚɪɬɧɵɯ ɷɥɟɤɬɪɨɞɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ, ɭɤɚ-
ɡɚɬɶ, ɤɚɤɢɟ ɩɪɨɰɟɫɫɵ ɩɪɨɬɟɤɚɸɬ ɧɚ ɚɧɨɞɟ (Ⱥ) ɢ ɤɚɬɨɞɟ (Ʉ) ɩɪɢ ɪɚɛɨɬɟ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɫɨɫɬɚɜɥɟɧɧɨɝɨ ɢɡ ɫɬɚɧɞɚɪɬɧɵɯ ɦɟɞɧɨɝɨ ɢ ɜɨɞɨɪɨɞɧɨɝɨ
ɷɥɟɤɬɪɨɞɨɜ.
ȼɚɲ ɨɬɜɟɬ.
2+
ȼɚɪɢɚɧɬ 1. Ⱥ: Cu – 2e o Cu
ȼɚɪɢɚɧɬ 2. Ⱥ: ɇ
ȼɚɪɢɚɧɬ 3. Ⱥ: ɇ
ȼɚɪɢɚɧɬ 4. Ⱥ: 2ɇ
ȼɚɪɢɚɧɬ 5. Ⱥ: Cu
– 2e o 2ɇ+; Ʉ: Cu2+ + 2e o Cu.
2
– 2e o 2ɇ+; Ʉ: Cu – 2e o Cu2+.
2
+
+ 2ɟ o ɇ2; Ʉ: Cu – 2e o Cu2+.
2+
+ 2e o Cu; Ʉ: 2ɇ+ + 2ɟ o ɇ2.
; Ʉ: 2ɇ+ + 2ɟ o ɇ2.
9. Ƚɚɥɶɜɚɧɢɱɟɫɤɢɣ ɷɥɟɦɟɧɬ ɫɨɫɬɚɜɥɟɧ ɢɡ ɫɬɚɧɞɚɪɬɧɵɯ ɠɟɥɟɡɧɨɝɨ ɢ ɫɜɢɧɰɨɜɨɝɨ ɷɥɟɤɬɪɨɞɨɜ. ɍɤɚɡɚɬɶ, ɤɚɤɨɣ ɩɪɨɰɟɫɫ ɩɪɨɬɟɤɚɟɬ ɧɚ ɚɧɨɞɟ.
ȼɚɲ ɨɬɜɟɬ.
2+
ȼɚɪɢɚɧɬ 1. Fe
ȼɚɪɢɚɧɬ 2. Pb
ȼɚɪɢɚɧɬ 3. Pb
ȼɚɪɢɚɧɬ 4. Fe 2e o Fe
ȼɚɪɢɚɧɬ 5. Pb
10. Ƚɚɥɶɜɚɧɢɱɟɫɤɢɣ ɷɥɟɦɟɧɬ ɫɨɫɬɚɜɥɟɧ ɢɡ ɫɬɚɧɞɚɪɬɧɵɯ ɷɥɟɤɬɪɨɞɨɜ: ɤɚɞɦɢɟɜɨɝɨ Cd
2+
+ 2e o Fe.
2e o Pb2+.
2+
+ 2e o Pb.
2+
2e o Pb4+.
2+
.
|Cd ɢ ɩɥɚɬɢɧɨɜɨɝɨ Pt2+|Pt. ɍɤɚɡɚɬɶ ɭɪɚɜɧɟɧɢɹ ɚɧɨɞɧɨɝɨ ɢ ɤɚɬɨɞ-
ɧɨɝɨ ɩɪɨɰɟɫɫɨɜ, ɩɪɨɬɟɤɚɸɳɢɯ ɩɪɢ ɪɚɛɨɬɟ ɷɬɨɝɨ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ.
ȼɚɲ ɨɬɜɟɬ.
2+
ȼɚɪɢɚɧɬ 1. Ⱥ: Cd – 2e o Cd
ȼɚɪɢɚɧɬ 2. Ⱥ: Pt – 2e o Pt
ȼɚɪɢɚɧɬ 3. Ⱥ: Pt – 2e o Pt
ȼɚɪɢɚɧɬ 4. Ⱥ: Pt
ȼɚɪɢɚɧɬ 5. Ⱥ: Cd
11. Ɋɚɫɫɱɢɬɚɬɶ ɗȾɋ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɫɨɫɬɚɜɥɟɧɧɨɝɨ ɢɡ ɷɥɟɤ-
2+
ɬɪɨɞɨɜ: Fe
(0,1 Ɇ) | Fe ɢ Ag+ (0,01 Ɇ) | Ag.
2+
+ 2e o Pt; Ʉ: Cd – 2e o Cd2+.
2+
+ 2e o Cd; Ʉ: Pt2+ + 2e o Pt.
; Ʉ: Pt2+ + 2e o Pt.
2+
; Ʉ: Cd2+ + 2e o Cd.
2+
; Ʉ: Cd – 2e o Cd2+.
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 1,21 ȼ.
ȼɚɪɢɚɧɬ 2. (–1,21) ȼ.
ȼɚɪɢɚɧɬ 3. 1,239 ȼ.
142
ȼɚɪɢɚɧɬ 4. 1,151 ȼ.
g
g
ȼɚɪɢɚɧɬ 5. (–1,151) ȼ.
12. Ɋɚɫɫɱɢɬɚɬɶ ɗȾɋ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɫɨɫɬɚɜɥɟɧɧɨɝɨ ɢɡ ɞɜɭɯ ɧɢ-
ɤɟɥɟɜɵɯ ɷɥɟɤɬɪɨɞɨɜ ɩɪɢ ɤɨɧɰɟɧɬɪɚɰɢɹɯ ɢɨɧɨɜ ɧɢɤɟɥɹ Ni
2+
ɜ ɪɚɫɬɜɨɪɚɯ ɷɥɟɤ-
ɬɪɨɥɢɬɨɜ ɪɚɜɧɵɯ:
= 0,1 ɦɨɥɶ/ɥ; ɋ2 = 0,001 ɦɨɥɶ/ɥ.
ɋ
1
ȼɚɲ ɨɬɜɟɬ.
ȼɚɪɢɚɧɬ 1. 0,118 ȼ.
ȼɚɪɢɚɧɬ 2. (–0,118) ȼ.
ȼɚɪɢɚɧɬ 3. 0,059 ȼ.
ȼɚɪɢɚɧɬ 4. (–0, 059) ȼ.
ȼɚɪɢɚɧɬ 5. 0,0295 ȼ.
Ɂɚɞɚɱɢ
9.1–9.12. ɋɨɫɬɚɜɢɬɶ ɫɯɟɦɭ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɧɚ ɷɥɟɤɬɪɨɞɚɯ ɤɨɬɨɪɨɝɨ ɩɪɨɬɟɤɚɸɬ ɭɤɚɡɚɧɧɵɟ ɪɟɚɤɰɢɢ. ɇɚɩɢɫɚɬɶ ɫɭɦɦɚɪɧɨɟ ɭɪɚɜɧɟɧɢɟ ɪɚɛɨɬɵ
ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ.
ɍɪɚɜɧɟɧɢɹ
ʋ
Mg – 2e = Mg
9.1
A
Zn – 2e = Zn
9.2
Co
Cu – 2e =Cu
9.3
Au
Fe – 2e = Fe
9.4
Ni
Cr – 3e = Cr
9.5
Ag
Al – 3e = Al
9.6
Zn
ɩɪɨɰɟɫɫɨɜ
+
+ e = Ag
2+
+ 2e = Co
3+
+ 3e = Au
2+
+ 2e = Ni
+
+ e = Ag
2+
+ 2e = Zn
2+
9.7
2+
9.8
2+
9.9
2+
9.10
3+
9.11
3+
9.12
ʋ
ɍɪɚɜɧɟɧɢɹ
ɩɪɨɰɟɫɫɨɜ
Sn – 2e = Sn
2+
H
+ 2e = Hg
Ti – 3e = Ti
2+
+ 2e = Zn
Zn
Pb – 2e = Pb
3+
+ 3e = Au
Au
Bi – 3e = Bi
2+
+ 2e = Co
Co
Ag – e = Ag
2+
+ 2e = Hg
Hg
Fe – 2e = Fe
2+
+ 2e = Cu
Cu
2+
3+
2+
3+
+
2+
9.13–9.24. Ɂɚɩɢɫɚɬɶ ɭɫɥɨɜɧɭɸ ɫɯɟɦɭ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɫɨɫɬɚɜɥɟɧɧɨɝɨ
ɢɡ ɭɤɚɡɚɧɧɵɯ ɷɥɟɤɬɪɨɞɨɜ. ɇɚɩɢɫɚɬɶ ɭɪɚɜɧɟɧɢɹ ɩɪɨɰɟɫɫɨɜ, ɩɪɨɬɟɤɚɸɳɢɯ ɜ ɚɧɨɞɧɨɦ
ɢ ɤɚɬɨɞɧɨɦ ɩɨɥɭɷɥɟɦɟɧɬɚɯ, ɢ ɭɪɚɜɧɟɧɢɟ ɬɨɤɨɨɛɪɚɡɭɸɳɟɣ (ɫɭɦɦɚɪɧɨɣ) ɪɟɚɤɰɢɢ.
ȼɵɱɢɫɥɢɬɶ ɗȾɋ ɩɪɢ T = 298 K, ɢɫɩɨɥɶɡɭɹ ɫɩɪɚɜɨɱɧɵɟ ɞɚɧɧɵɟ (ɬɚɛɥ. ɉ7).
ʋ ɗɥɟɤɬɪɨɞ 1
9.13 Cr3+|Cr
9.14 Ni2+|Ni
9.15 Sn2+|Sn
Ʉɨɧɰɟɧɬɪɚɰɢɹ
ɢɨɧɨɜ, ɦɨɥɶ/ɥ
01,0
C
3
Cr
1,0
C
2
Ni
01,0
C
2
Sn
ɗɥɟɤɬɪɨɞ 2
Cu
Ag
Ag
2+
+
+
|Cu
|Ag
|Ag
Ʉɨɧɰɟɧɬɪɚɰɢɹ
ɢɨɧɨɜ, ɦɨɥɶ/ɥ
001,0
C
2
Cu
001,0
C
Ag
C
01,0Ag
143
9.16 Fe
|
|
g+|Ag
|
|
|
|
r3+|Cr
2+
|Fe
9.17 Au3+|Au
9.18 Mn2+|Mn
9.19 Pt2+|Pt
9.20 Ti3+|Ti
9.21 V2+|V
9.22 Ag+|Ag
9.23 Zn2+|Zn
9.24 Co2+|Co
1,0
C
2
Fe
001,0
C
3
Au
C
C
2
Pt
C
Ti
C
C
Al
C
C
Co
001,0Mn
0001,0
001,0
3
1,0
2
V
01,0
3
1,0
2
Zn
01,0
2
2+
|Zn
Zn
2+
Co
Cd
Pb
Fe
Sn
Ni
Ag
Mn
2+
2+
2+
2+
2+
2+
|Co
|Cd C
|Pb C
|Fe
|Sn
|Ni C
+
|Ag
|Mn
C
C
C
Zn
Cd
Pb
C
C
Sn
Ni
C
2
2+
2+
= 0,001
2
Fe
2
2+
= 0,001
01,0
0001,0Co
= 0,01
1,0
01,0
01,0Ag
001,0Mn
9.25–9.37. ɋɨɫɬɚɜɢɬɶ ɭɫɥɨɜɧɭɸ ɫɯɟɦɭ ɤɨɧɰɟɧɬɪɚɰɢɨɧɧɨɝɨ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ
ɷɥɟɦɟɧɬɚ, ɧɚɩɢɫɚɬɶ ɭɪɚɜɧɟɧɢɹ ɷɥɟɤɬɪɨɞɧɵɯ ɩɪɨɰɟɫɫɨɜ, ɩɪɨɬɟɤɚɸɳɢɯ ɜ ɞɚɧɧɨɦ
ɝɚɥɶɜɚɧɢɱɟɫɤɨɦ ɷɥɟɦɟɧɬɟ, ɢ ɭɪɚɜɧɟɧɢɟ ɬɨɤɨɨɛɪɚɡɭɸɳɟɣ ɪɟɚɤɰɢɢ. ȼɵɱɢɫɥɢɬɶ
ɗȾɋ ɩɪɢ T = 298 K.
ʋ ɗɥɟɤɬɪɨɞ
Ʉɨɧɰɟɧɬɪɚɰɢɹ
ɢɨɧɨɜ ɜ ɪɚɫɬɜɨɪɚɯ, ɦɨɥɶ/ɥ
ɋ1 ɋ2
9.25 2 3 4
9.26 Cu2+ |Cu 0,001 0,01
9.27 Fe
9.28 Zn
2+
Fe 0,001 0,1
2+
Zn 0,01 0,1
9.29 H+ |Pt, H2 0,001 0,1
9.30 A
9.31 Ti
0,0001 0,1
3+
Ti 0,001 0,01
9.32 Bi3+|Bi 0,001 0,1
9.33 Pb
9.34 Mn
9.35 Sn
9.36 C
2+
Pb 0,0001 1,0
2+
Mn 0,001 0,01
2+
Sn 0,01 0,1
0,001 0,1
9.37 V2+|V 0,0001 0,1
9.38–9.50. ɋɨɫɬɚɜɢɬɶ ɭɫɥɨɜɧɭɸ ɫɯɟɦɭ ɝɚɥɶɜɚɧɢɱɟɫɤɨɝɨ ɷɥɟɦɟɧɬɚ, ɫɨɫɬɚɜ-
ɥɟɧɧɨɝɨ ɢɡ ɭɤɚɡɚɧɧɵɯ ɨɤɢɫɥɢɬɟɥɶɧɨ-ɜɨɫɫɬɚɧɨɜɢɬɟɥɶɧɵɯ ɷɥɟɤɬɪɨɞɨɜ. ɇɚɩɢɫɚɬɶ
ɭɪɚɜɧɟɧɢɹ ɩɪɨɰɟɫɫɨɜ, ɩɪɨɬɟɤɚɸɳɢɯ ɜ ɚɧɨɞɧɨɦ ɢ ɤɚɬɨɞɧɨɦ ɩɨɥɭɷɥɟɦɟɧɬɚɯ, ɢ ɭɪɚɜɧɟɧɢɟ ɬɨɤɨɨɛɪɚɡɭɸɳɟɣ (ɫɭɦɦɚɪɧɨɣ) ɪɟɚɤɰɢɢ. ȼɵɱɢɫɥɢɬɶ ɗȾɋ ɩɪɢ T = 298 K,
ɢɫɩɨɥɶɡɭɹ ɫɩɪɚɜɨɱɧɵɟ ɞɚɧɧɵɟ (ɬɚɛɥ. ɉ7). Ⱦɚɜɥɟɧɢɟ ɝɚɡɨɨɛɪɚɡɧɵɯ ɜɟɳɟɫɬɜ ɪɚɜɧɨ p = 1 ɛɚɪ.
144
ʋ ɗɥɟɤɬɪɨɞ 1
ɭ
9.38 Fe3+, Fe2+|Pt
9.39 V3+, V2+|Pt
9.40 Sn4+, Sn2+| Ɋt
9.41 Ce4+, Ce3+|Pt
9.42 Co3+, Co2+| Pt
9.43 Sn4+, Sn2+| Pt
9.44 Fe3+, Fe2+|Pt
9.45 Cl– |Pt, Cl2
9.46 Ce4+, Ce3+|Pt
9.47 Br2, Br– | Pt
9.48 Fe3+, Fe2+|Pt
9.49 Co3+, Co
2+
| Pt
Ʉɨɧɰɟɧɬɪɚɰɢɹ
ɢɨɧɨɜ ɢ ɦɨɥɟɤɭɥ,
ɦɨɥɶ/ɥ
01,0
C ;
3
Fe
001,0
C
2
Fe
C ;
C ;
C ;
C
C ;
C ;
C ;
C
C ;
C
C ;
C ;
001,0
3
V
1,0
C
2
V
01,0
4
Sn
1,0
C
2
Sn
1,0
4
Ce
001,0
3
Ce
01,0
3
Co
1,0
C
2
Co
01,0
4
Sn
0,1
C
2
Sn
1,0
3
Fe
001,0
2
Fe
1,0
C
Cl
1,0
4
Ce
01,0
3
Ce
C
01,0
Br
2
0,1
C
Br
01,0
3
Fe
1,0
C
2
Fe
01,0
3
Co
1,0
C
2
Co
ɗɥɟɤɬɪɨɞ 2
3+
, Co2+|Pt
Co
+
| Pt, H2
H
, Br– | Pt
Br
2
, I– | Pt
I
2
–
|Pt, Cl2
Cl
3+
Co
, Co2+|Pt
+
H
| Pt, H2
, Br– | Pt
Br
2
4+
, Sn2+| Pt
Sn
+
| Pt, H2
H
+
| Pt, H2
H
, I– | Pt
I
2
Ʉɨɧɰɟɧɬɪɚɰɢɹ
ɢɨɧɨɜ ɢ
ɦɨɥɟɤ
ɥ, ɦɨɥɶ/ɥ
001,0
C ;
3
Co
01,0
C
2
Co
01,0
C
H
C
01,0
Br
2
1,0
C
Br
C ;
001,0
I
2
0001,0
C
I
1,0
C
Cl
C ;
Co
C
C
C
C ;
Sn
C
C
C
C
I
3
2
Co
H
C
Br
2
Br
4
2
Sn
H
H
C
I
2
01,0
1,0
1,0
01,0
1,0
001,0
1,0
0,2
01,0
001,0
0001,0
145
ȽɅȺȼȺ 10. ɗɅȿɄɌɊɈɅɂɁ
M
MkF
ɗɥɟɤɬɪɨɥɢɡɨɦ ɧɚɡɵɜɚɸɬ ɨɤɢɫɥɢɬɟɥɶɧɨ-ɜɨɫɫɬɚɧɨɜɢɬɟɥɶɧɵɟ ɩɪɨɰɟɫɫɵ, ɩɪɨɢɫɯɨɞɹɳɢɟ ɧɚ ɷɥɟɤɬɪɨɞɚɯ ɩɪɢ ɩɪɨɯɨɠɞɟɧɢɢ ɩɨɫɬɨɹɧɧɨɝɨ ɷɥɟɤɬɪɢɱɟɫɤɨɝɨ ɬɨɤɚ
ɱɟɪɟɡ ɪɚɫɬɜɨɪ ɢɥɢ ɪɚɫɩɥɚɜ ɷɥɟɤɬɪɨɥɢɬɚ.
ɉɪɢ ɷɥɟɤɬɪɨɥɢɡɟ ɩɪɨɢɫɯɨɞɢɬ ɩɪɟɜɪɚɳɟɧɢɟ ɷɥɟɤɬɪɢɱɟɫɤɨɣ ɷɧɟɪɝɢɢ ɜ ɯɢɦɢɱɟɫɤɭɸ. ɋɭɦɦɚɪɧɵɣ ɩɪɨɰɟɫɫ ɩɪɢ ɷɥɟɤɬɪɨɥɢɡɟ ɩɪɨɬɢɜɨɩɨɥɨɠɟɧ ɩɨ ɧɚɩɪɚɜɥɟɧɢɸ
ɩɪɨɰɟɫɫɭ, ɩɪɨɬɟɤɚɸɳɟɦɭ ɜ ɝɚɥɶɜɚɧɢɱɟɫɤɨɦ ɷɥɟɦɟɧɬɟ. əɱɟɣɤɚ ɞɥɹ ɷɥɟɤɬɪɨɥɢɡɚ,
ɧɚɡɵɜɚɟɦɚɹ ɷɥɟɤɬɪɨɥɢɡɺɪɨɦ, ɫɨɫɬɨɢɬ ɢɡ ɞɜɭɯ ɷɥɟɤɬɪɨɞɨɜ ɢ ɷɥɟɤɬɪɨɥɢɬɚ
.
ɗɥɟɤɬɪɨɞ, ɧɚ ɤɨɬɨɪɨɦ ɢɞɺɬ ɪɟɚɤɰɢɹ ɜɨɫɫɬɚɧɨɜɥɟɧɢɹ (ɤɚɬɨɞ), ɭ ɷɥɟɤɬɪɨɥɢɡɺɪɚ ɩɨɞɤɥɸɱɺɧ ɤ ɨɬɪɢɰɚɬɟɥɶɧɨɦɭ ɩɨɥɸɫɭ ɜɧɟɲɧɟɝɨ ɩɨɫɬɨɹɧɧɨɝɨ ɢɫɬɨɱɧɢɤɚ ɬɨɤɚ.
ɗɥɟɤɬɪɨɞ, ɧɚ ɤɨɬɨɪɨɦ ɩɪɨɬɟɤɚɟɬ ɪɟɚɤɰɢɹ ɨɤɢɫɥɟɧɢɹ (ɚɧɨɞ), ɩɨɞɤɥɸɱɺɧ ɤ ɩɨɥɨɠɢɬɟɥɶɧɨɦɭ ɩɨɥɸɫɭ ɢɫɬɨɱɧɢɤɚ ɬɨɤɚ.
10.1. Ʉɨɥɢɱɟɫɬɜɟɧɧɵɟ ɡɚɤɨɧɵ ɷɥɟɤɬɪɨɥɢɡɚ
Ⱥɧɝɥɢɣɫɤɢɣ ɭɱɟɧɵɣ Ɇ. Ɏɚɪɚɞɟɣ ɨɬɤɪɵɥ ɡɚɤɨɧɵ (1834 ɝ.), ɨɩɪɟɞɟɥɹɸɳɢɟ
ɡɚɜɢɫɢɦɨɫɬɶ ɦɟɠɞɭ ɤɨɥɢɱɟɫɬɜɨɦ ɩɪɨɲɟɞɲɟɝɨ ɷɥɟɤɬɪɢɱɟɫɬɜɚ ɢ ɤɨɥɢɱɟɫɬɜɨɦ ɜɟɳɟɫɬɜɚ, ɢɫɩɵɬɚɜɲɟɦ ɯɢɦɢɱɟɫɤɢɟ ɩɪɟɜɪɚɳɟɧɢɹ ɧɚ ɷɥɟɤɬɪɨɞɟ. ɋɨɝɥɚɫɧɨ ɫɨɜɪɟɦɟɧɧɨɣ ɬɟɪɦɢɧɨɥɨɝɢɢ, ɡɚɤɨɧɵ Ɏɚɪɚɞɟɹ ɦɨɠɧɨ ɫɮɨɪɦɭɥɢɪɨɜɚɬɶ ɜ ɫɥɟɞɭɸɳɟɦ
ɜɢɞɟ.
1. Ɇɚɫɫɚ ɜɟɳɟɫɬɜɚ m, ɢɫɩɵɬɚɜɲɟɝɨ ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢɟ ɩɪɟɜɪɚɳɟɧɢɹ
ɧɚ ɷɥɟɤɬɪɨɞɟ, ɩɪɹɦɨ ɩɪɨɩɨɪɰɢɨɧɚɥɶɧɚ ɤɨɥɢɱɟɫɬɜɭ ɩɪɨɲɟɞɲɟɝɨ ɷɥɟɤɬɪɢɱɟɫɬɜɚ
Q = IÂt (ɫɢɥɟ
ɬɨɤɚ ɢ ɜɪɟɦɟɧɢ):
,mkQkIt
ɝɞɟ k – ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢɣ ɷɤɜɢɜɚɥɟɧɬ ɜɟɳɟɫɬɜɚ. ɗɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢɣ ɷɤɜɢɜɚɥɟɧɬ ɜɟɳɟɫɬɜɚ k
ɱɢɫɥɟɧɧɨ ɪɚɜɟɧ ɦɚɫɫɟ ɜɟɳɟɫɬɜɚ, ɜɵɞɟɥɢɜɲɟɝɨɫɹ ɧɚ ɷɥɟɤɬɪɨɞɟ
ɩɪɢ ɩɪɨɯɨɠɞɟɧɢɢ ɨɞɧɨɝɨ ɤɭɥɨɧɚ (Ʉɥ) ɷɥɟɤɬɪɢɱɟɫɬɜɚ ɱɟɪɟɡ ɷɥɟɤɬɪɨɥɢɬ.
2. Ɇɚɫɫɵ ɩɪɨɪɟɚɝɢɪɨɜɚɜɲɢɯ ɧɚ ɷɥɟɤɬɪɨɞɚɯ ɜɟɳɟɫɬɜ ɩɪɢ ɩɨɫɬɨɹɧɧɨɦ ɤɨɥɢɱɟɫɬɜɟ ɷɥɟɤɬɪɢɱɟɫɬɜɚ ɨɬɧɨɫɹɬɫɹ ɞɪɭɝ ɤ ɞɪɭɝɭ ɤɚɤ ɦɨɥɹɪɧɵɟ ɦɚɫɫɵ ɢɯ ɷɤɜɢɜɚɥɟɧɬɨɜ:
ȿɫɥɢ Q = const, ɬɨ
mk
ɗ1
11
mM k
2 ɗ22
ɢɥɢ
M
ɗ1 ɗ2
kk
12
.
M
Ⱦɥɹ ɜɵɞɟɥɟɧɢɹ ɧɚ ɷɥɟɤɬɪɨɞɟ ɨɞɧɨɝɨ ɦɨɥɹ ɷɤɜɢɜɚɥɟɧɬɚ ɥɸɛɨɝɨ ɜɟɳɟɫɬɜɚ
ɬɪɟɛɭɟɬɫɹ ɨɞɢɧɚɤɨɜɨɟ ɤɨɥɢɱɟɫɬɜɨ ɷɥɟɤɬɪɢɱɟɫɬɜɚ, ɪɚɜɧɨɟ 96 484 Ʉɥ ɢɥɢ ɩɪɢɛɥɢɠɟɧɧɨ 96 500 Ʉɥ. Ɍɨɝɞɚ ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢɣ ɷɤɜɢɜɚɥɟɧɬ ɜɟɳɟɫɬɜɚ k
ɢɥɢ
M
ɗ
96 500 Ʉɥ / ɦɨɥɶ.
Fk
ɝɞɟ M
M
ɗ
– ɦɨɥɹɪɧɚɹ ɦɚɫɫɚ ɯɢɦɢɱɟɫɤɨɝɨ ɷɤɜɢɜɚɥɟɧɬɚ ɜɟɳɟɫɬɜɚ;
ɗ
nF
ɪɚɜɟɧ:
M – ɦɨɥɹɪɧɚɹ ɦɚɫɫɚ ɜɟɳɟɫɬɜɚ;
n – ɱɢɫɥɨ ɷɥɟɤɬɪɨɧɨɜ, ɭɱɚɫɬɜɭɸɳɢɯ ɜ ɷɥɟɤɬɪɨɞɧɨɦ ɩɪɨɰɟɫɫɟ;
F – ɩɨɫɬɨɹɧɧɚɹ Ɏɚɪɚɞɟɹ.
146
ɉɨɫɬɨɹɧɧɭɸ Ɏɚɪɚɞɟɹ ɦɨɠɧɨ ɪɚɫɫɱɢɬɚɬɶ, ɤɚɤ ɩɪɨɢɡɜɟɞɟɧɢɟ ɩɨɫɬɨɹɧɧɨɣ
M
F
M
F
K
K
Ⱥɜɨɝɚɞɪɨ N
ɢ ɜɟɥɢɱɢɧɵ ɷɥɟɦɟɧɬɚɪɧɨɝɨ ɡɚɪɹɞɚ Ɲ = 1,602 ā 10
A
F = 6,022 ā 10
23
ɦɨɥɶ–1 ā1,602 ā 10
–19
Ʉɥ = 96 484 Ʉɥ/ɦɨɥɶ.
–19
Ʉɥ:
Ⱦɥɹ ɪɚɡɥɢɱɧɵɯ ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢɯ ɪɚɫɱɟɬɨɜ ɲɢɪɨɤɨ ɢɫɩɨɥɶɡɭɸɬ ɨɛɴɟɞɢɧɟɧɧɨɟ ɭɪɚɜɧɟɧɢɟ ɞɜɭɯ ɡɚɤɨɧɨɜ Ɏɚɪɚɞɟɹ:
MIt
ɷ
m
It
.
(10.1)
nF
ɇɚ ɩɪɚɤɬɢɤɟ ɜɫɥɟɞɫɬɜɢɟ ɩɚɪɚɥɥɟɥɶɧɨ ɩɪɨɬɟɤɚɸɳɢɯ ɩɪɨɰɟɫɫɨɜ ɧɚ ɷɥɟɤɬɪɨɞɟ
ɮɚɤɬɢɱɟɫɤɚɹ ɦɚɫɫɚ ɨɛɪɚɡɭɸɳɟɝɨɫɹ ɢɥɢ ɪɚɫɯɨɞɭɸɳɟɝɨɫɹ ɜɟɳɟɫɬɜɚ m
ɮɚɤɬ
ɱɚɫɬɨ
ɦɟɧɶɲɟ, ɱɟɦ ɪɚɫɫɱɢɬɚɧɧɚɹ ɩɨ ɡɚɤɨɧɚɦ Ɏɚɪɚɞɟɹ m. ɉɨɷɬɨɦɭ ɞɥɹ ɩɪɚɤɬɢɱɟɫɤɢɯ
ɰɟɥɟɣ ɜɜɟɞɟɧɨ ɩɨɧɹɬɢɟ ɜɵɯɨɞɚ ɜɟɳɟɫɬɜɚ ɩɨ ɬɨɤɭ K ɜ ɞɨɥɹɯ ɨɬ ɟɞɢɧɢɰɵ ɢɥɢ ɜ
ɩɪɨɰɟɧɬɚɯ:
m
ɮɚɤɬ
K
ɢɥɢ
m
m
ɮɚɤɬ
m
100 %.
K
Ɍɨɝɞɚ ɮɨɪɦɭɥɚ (10.1) ɩɪɢɧɢɦɚɟɬ ɜɢɞ:
MIt
m
ɮɚɤɬ
ɗ
It
nF
. (10.2)
10.2. ɉɨɫɥɟɞɨɜɚɬɟɥɶɧɨɫɬɶ ɷɥɟɤɬɪɨɞɧɵɯ ɩɪɨɰɟɫɫɨɜ
ɩɪɢ ɷɥɟɤɬɪɨɥɢɡɟ
ɑɚɫɬɨ ɜ ɷɥɟɤɬɪɨɥɢɬɟ ɩɪɢɫɭɬɫɬɜɭɸɬ ɧɟɫɤɨɥɶɤɨ ɜɢɞɨɜ ɤɚɬɢɨɧɨɜ ɢ ɚɧɢɨɧɨɜ.
ɇɚɩɪɢɦɟɪ, ɜ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɫɨɥɟɣ ɤɪɨɦɟ ɚɧɢɨɧɨɜ ɢ ɤɚɬɢɨɧɨɜ ɫɨɥɢ ɜɫɟɝɞɚ
+
ɢɦɟɸɬɫɹ ɢɨɧɵ H
ɢ OH:
H
O ɏ H+ + OH.
2
Ɍɚɤ ɤɚɤ ɩɪɨɰɟɫɫ ɞɢɫɫɨɰɢɚɰɢɢ ɜɨɞɵ ɩɪɨɬɟɤɚɟɬ ɜ ɧɟɡɧɚɱɢɬɟɥɶɧɨɣ ɫɬɟɩɟɧɢ, ɬɨ
ɷɥɟɤɬɪɨɞɧɵɟ ɪɟɚɤɰɢɢ ɦɨɠɧɨ ɪɚɫɫɦɚɬɪɢɜɚɬɶ ɫ ɭɱɚɫɬɢɟɦ ɦɨɥɟɤɭɥ ɜɨɞɵ, ɩɪɟɧɟ-
+
ɛɪɟɝɚɹ ɦɚɥɵɦɢ ɤɨɧɰɟɧɬɪɚɰɢɹɦɢ ɢɨɧɨɜ H
ɢ OH ɜ ɧɟɣɬɪɚɥɶɧɨɣ ɫɪɟɞɟ.
ɉɪɢ ɧɚɥɢɱɢɢ ɧɟɫɤɨɥɶɤɢɯ ɜɢɞɨɜ ɢɨɧɨɜ ɢɥɢ ɦɨɥɟɤɭɥ ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɢ ɚɤ-
ɬɢɜɧɵɯ ɜɟɳɟɫɬɜ (ɧɚɩɪɢɦɟɪ, ɇ
Ɉ) ɜɨɡɦɨɠɧɨ ɩɪɨɬɟɤɚɧɢɟ ɧɟɫɤɨɥɶɤɢɯ ɷɥɟɤɬɪɨɞ-
2
ɧɵɯ ɪɟɚɤɰɢɣ. Ɋɚɫɫɦɨɬɪɢɦ ɢɯ ɩɨɫɥɟɞɨɜɚɬɟɥɶɧɨɫɬɶ.
Ɍɚɤ ɤɚɤ
ɧɚ ɤɚɬɨɞɟ ɢɞɺɬ ɪɟɚɤɰɢɹ ɜɨɫɫɬɚɧɨɜɥɟɧɢɹ, ɬɨ ɟɫɬɶ ɩɪɢɺɦ ɷɥɟɤɬɪɨɧɨɜ
ɨɤɢɫɥɢɬɟɥɟɦ, ɬɨ ɜ ɩɟɪɜɭɸ ɨɱɟɪɟɞɶ ɞɨɥɠɧɵ ɪɟɚɝɢɪɨɜɚɬɶ ɧɚɢɛɨɥɟɟ ɫɢɥɶɧɵɟ
ɨɤɢɫɥɢɬɟɥɢ. ɇɚ ɤɚɬɨɞɟ, ɩɪɟɠɞɟ ɜɫɟɝɨ, ɩɪɨɬɟɤɚɟɬ ɪɟɚɤɰɢɹ ɫ ɧɚɢɛɨɥɟɟ ɩɨɥɨɠɢɬɟɥɶɧɵɦ ɩɨɬɟɧɰɢɚɥɨɦ.
ȿɫɥɢ ɫɢɫɬɟɦɚ, ɜ ɤɨɬɨɪɨɣ ɩɪɨɜɨɞɹɬ ɷɥɟɤɬɪɨɥɢɡ, ɫɨɞɟɪɠɢɬ ɪɚɡɥɢɱɧɵɟ ɨɤɢɫɥɢɬɟɥɢ, ɬɨ ɧɚ ɤɚɬɨɞɟ ɛɭɞɟɬ ɜɨɫɫɬɚɧɚɜɥɢɜɚɬɶɫɹ ɱɚɫɬɢɰɚ, ɤɨɬɨɪɨɣ ɨɬɜɟɱɚɟɬ
ɧɚɢɛɨɥɶɲɟɟ ɡɧɚɱɟɧɢɟ ɷɥɟɤɬɪɨɞɧɨɝɨ ɩɨɬɟɧɰɢɚɥɚ.
ɉɪɢ ɜɵɛɨɪɟ ɩɪɨɰɟɫɫɚ ɤɚɬɨɞɧɨɝɨ ɜɨɫɫɬɚɧɨɜɥɟɧɢɹ ɧɟɨɛɯɨɞɢɦɨ ɭɱɢɬɵɜɚɬɶ
ɡɚɜɢɫɢɦɨɫɬɶ ɩɨɬɟɧɰɢɚɥɚ ɜɨɞɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɨɬ ɪɇ ɫɪɟɞɵ.
147
ȼ ɧɟɣɬɪɚɥɶɧɨɣ ɫɪɟɞɟ ɩɨɬɟɧɰɢɚɥ ɜɨɞɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɩɪɢ p(ɇ
) = 105 ɉɚ
2
ɢ 25 qɋ ɪɚɜɟɧ:
0,059pH 0, 059 7 0, 41B.E
|
HH
2
Ɍɨɝɞɚ ɩɪɢ ɷɥɟɤɬɪɨɥɢɡɟ ɜɨɞɧɨɝɨ ɪɚɫɬɜɨɪɚ ɷɥɟɤɬɪɨɥɢɬɚ ɜɫɟ ɨɤɢɫɥɢɬɟɥɢ ɦɨɠɧɨ ɪɚɡɞɟɥɢɬɶ ɧɚ ɬɪɢ ɝɪɭɩɩɵ.
I ɝɪɭɩɩɚ – ɤɚɬɢɨɧɵ, ɢɦɟɸɳɢɟ ɩɨɬɟɧɰɢɚɥ ɛɨɥɶɲɟ ɩɨɬɟɧɰɢɚɥɚ ɜɨɞɨɪɨɞɧɨɝɨ
ɷɥɟɤɬɪɨɞɚ. ȼ ɧɟɣɬɪɚɥɶɧɨɣ ɫɪɟɞɟ ɤ ɧɢɦ ɦɨɝɭɬ ɛɵɬɶ ɨɬɧɟɫɟɧɵ ɤɚɬɢɨɧɵ, ɢɦɟɸ-
0
ɳɢɟ ɩɨɬɟɧɰɢɚɥ ɛɨɥɶɲɟ (– 0,41) ȼ [E
2+
Cu
, Ag+ ɢ ɞɪ., ɚ ɬɚɤɠɟ ɤɢɫɥɨɪɨɞ, ɝɚɥɨɝɟɧɵ, PbO2, MnO
Ʉɚɬɢɨɧɵ ɦɟɬɚɥɥɨɜ, ɨɬɧɨɫɹɳɢɟɫɹ ɤ ɷɬɨɣ ɝɪɭɩɩɟ, ɪɚɡɪɹɠɚɸɬɫɹ ɧɚ ɤɚɬɨɞɟ
ɪɚɧɶɲɟ ɢɨɧɨɜ ɜɨɞɨɪɨɞɚ, ɢ ɜɨɫɫɬɚɧɨɜɥɟɧɢɹ ɦɨɥɟɤɭɥ ɜɨɞɵ ɢɥɢ ɢɨɧɨɜ H
! (í 0,41) ȼ)]: Cd2+, Co2+, Ni2+, Sn2+, Pb2+,
ɢ ɞɪ.
4
+
ɧɟ ɩɪɨ-
ɢɫɯɨɞɢɬ. Ʉɚɬɨɞɧɵɣ ɩɪɨɰɟɫɫ:
n+
+ ne o Mɟ.
Mɟ
II ɝɪɭɩɩɚ – ɤɚɬɢɨɧɵ ɦɟɬɚɥɥɨɜ, ɩɨɬɟɧɰɢɚɥ ɤɨɬɨɪɵɯ ɨɬɧɨɫɢɬɟɥɶɧɨ ɦɚɥɨ ɨɬ-
ɥɢɱɚɟɬɫɹ ɨɬ ɩɨɬɟɧɰɢɚɥɚ ɜɨɞɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ:
[(í 1,22 ȼ) E
ȼ ɪɹɞɭ ɫɬɚɧɞɚɪɬɧɵɯ ɷɥɟɤɬɪɨɞɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ ɷɬɢ ɦɟɬɚɥɥɵ ɧɚɯɨɞɹɬɫɹ
ɦɟɠɞɭ ɤɚɞɦɢɟɦ ɢ ɚɥɸɦɢɧɢɟɦ. Ʉ ɧɢɦ ɨɬɧɨɫɹɬɫɹ ɢɨɧɵ Ti
0
(í 0,41 ȼ)].
3+
, Mn2+, Zn2+, Cr3+, Fe2+
ɢ ɞɪ. ɇɚ ɤɚɬɨɞɟ ɩɪɢ ɷɥɟɤɬɪɨɥɢɡɟ ɨɞɧɨɜɪɟɦɟɧɧɨ ɜɵɞɟɥɹɸɬɫɹ ɦɟɬɚɥɥ ɢ ɜɨɞɨɪɨɞ:
Ʉɚɬɨɞɧɵɣ ɩɪɨɰɟɫɫ:
n+
Mɟ
+ ne = Mɟ,
2H
O + 2e = 2OH + H2.
2
ɋɨɨɬɧɨɲɟɧɢɟ ɩɪɨɬɟɤɚɸɳɢɯ ɩɪɨɰɟɫɫɨɜ ɡɚɜɢɫɢɬ ɨɬ ɭɫɥɨɜɢɣ ɷɥɟɤɬɪɨɥɢɡɚ.
III ɝɪɭɩɩɚ – ɤɚɬɢɨɧɵ ɦɟɬɚɥɥɨɜ, ɩɨɬɟɧɰɢɚɥ ɤɨɬɨɪɵɯ ɫɭɳɟɫɬɜɟɧɧɨ ɦɟɧɶɲɟ,
ɱɟɦ ɩɨɬɟɧɰɢɚɥ ɜɨɞɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ. Ʉ ɧɢɦ ɨɬɧɨɫɹɬɫɹ ɢɨɧɵ ɳɟɥɨɱɧɵɯ ɢ ɳɟɥɨɱɧɨɡɟɦɟɥɶɧɵɯ ɦɟɬɚɥɥɨɜ (Na
ɫɬɚɧɞɚɪɬɧɵɣ ɷɥɟɤɬɪɨɞɧɵɣ ɩɨɬɟɧɰɢɚɥ ɦɟɧɶɲɟ, ɱɟɦ ɭ ɚɥɸɦɢɧɢɹ [(E
+
, K+, Mg2+ ɢ ɞɪ.), Al ɢ ɞɪɭɝɢɟ ɦɟɬɚɥɥɵ, ɭ ɤɨɬɨɪɵɯ
0
(í 1,22) ȼ)].
ȼ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɚɯ ɪɚɡɪɹɞ ɷɬɢɯ ɢɨɧɨɜ ɩɪɚɤɬɢɱɟɫɤɢ ɧɟ ɩɪɨɢɫɯɨɞɢɬ, ɬɚɤ ɤɚɤ ɧɚ
ɤɚɬɨɞɟ ɜɵɞɟɥɹɟɬɫɹ ɜɨɞɨɪɨɞ:
O + 2e = 2OH + H2 (ɧɟɣɬɪɚɥɶɧɚɹ ɢ ɳɟɥɨɱɧɚɹ ɫɪɟɞɵ);
2H
2
+
+ 2e = H2 (ɤɢɫɥɨɬɧɚɹ ɫɪɟɞɚ).
2H
ȿɫɥɢ ɜ ɪɚɫɬɜɨɪɟ ɟɫɬɶ ɫɦɟɫɶ ɤɚɬɢɨɧɨɜ ɪɚɡɥɢɱɧɵɯ ɝɪɭɩɩ, ɬɨ ɧɚ ɤɚɬɨɞɟ ɜ
ɩɟɪɜɭɸ ɨɱɟɪɟɞɶ ɜɨɫɫɬɚɧɚɜɥɢɜɚɟɬɫɹ ɤɚɬɢɨɧ ɦɟɬɚɥɥɚ, ɢɦɟɸɳɢɣ ɧɚɢɛɨɥɶɲɟɟ
ɡɧɚɱɟɧɢɟ ɷɥɟɤɬɪɨɞɧɨɝɨ ɩɨɬɟɧɰɢɚɥɚ.
ȿɫɥɢ ɫɢɫɬɟɦɚ, ɜ ɤɨɬɨɪɨɣ ɩɪɨɜɨɞɹɬ ɷɥɟɤɬɪɨɥɢɡ, ɫɨɞɟɪɠɢɬ ɪɚɡɥɢɱɧɵɟ ɜɨɫɫɬɚɧɨɜɢɬɟɥɢ, ɬɨ
ɧɚ ɚɧɨɞɟ ɛɭɞɟɬ ɨɤɢɫɥɹɬɶɫɹ ɧɚɢɛɨɥɟɟ ɚɤɬɢɜɧɵɣ ɢɡ ɧɢɯ, ɬɨ ɟɫɬɶ
ɜɨɫɫɬɚɧɨɜɥɟɧɧɚɹ ɮɨɪɦɚ ɬɨɣ ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɨɣ ɫɢɫɬɟɦɵ, ɤɨɬɨɪɨɣ ɨɬɜɟɱɚɟɬ
ɧɚɢɦɟɧɶɲɟɟ ɡɧɚɱɟɧɢɟ ɷɥɟɤɬɪɨɞɧɨɝɨ ɩɨɬɟɧɰɢɚɥɚ.
ɉɪɢ ɜɵɛɨɪɟ ɩɨɫɥɟɞɨɜɚɬɟɥɶɧɨɫɬɢ ɩɪɨɰɟɫɫɨɜ ɚɧɨɞɧɨɝɨ ɨɤɢɫɥɟɧɢɹ ɧɟɨɛɯɨɞɢɦɨ ɭɱɢɬɵɜɚɬɶ ɡɧɚɱɟɧɢɟ ɩɨɬɟɧɰɢɚɥɚ ɤɢɫɥɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɩɪɢ Ɍ = 298 K ɢ
148
ɞɚɜɥɟɧɢɢ ɤɢɫɥɨɪɨɞɚ p(O
) = 1 ɛɚɪ, ɤɨɬɨɪɵɣ ɥɢɧɟɣɧɨ ɡɚɜɢɫɢɬ ɨɬ ɪɇ ɫɨɝɥɚɫɧɨ
2
ɭɪɚɜɧɟɧɢɸ:
1, 229 0,059pH.E
OOH
2
ȼ ɧɟɣɬɪɚɥɶɧɨɣ ɫɪɟɞɟ ɩɨɬɟɧɰɢɚɥ ɤɢɫɥɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɪɚɜɟɧ:
1,229 0,059 7 0,8 ȼ.E
|
OOH
2
Ɋɚɫɫɦɨɬɪɢɦ ɞɜɚ ɜɨɡɦɨɠɧɵɯ ɜɚɪɢɚɧɬɚ.
1. ɂɧɟɪɬɧɵɣ ɚɧɨɞ (ɝɪɚɮɢɬ C, ɩɥɚɬɢɧɚ Pt).
ɉɨ ɫɩɨɫɨɛɧɨɫɬɢ ɤ ɪɟɚɤɰɢɢ ɨɤɢɫɥɟɧɢɹ ɧɚ ɚɧɨɞɟ ɚɧɢɨɧɵ ɦɨɠɧɨ ɪɚɡɞɟɥɢɬɶ
ɧɚ 2 ɝɪɭɩɩɵ.
I ɝɪɭɩɩɚ – ɤɢɫɥɨɪɨɞɨɫɨɞɟɪɠɚɳɢɟ ɚɧɢɨɧɵ ɢ ɮɬɨɪɢɞ-ɚɧɢɨɧ:
)2–, (PO4)3–, (SO3)2–, (NO3)–, (NO2)–, (SiO3)2– ɢ ɞɪ., F
(SO
4
–
ɧɚ ɚɧɨɞɟ ɧɟ ɨɤɢɫ-
ɱ
ɥɹɸɬɫɹ. ɉɪɢ ɷɥɟɤɬɪɨɥɢɡɟ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɨɜ ɷɥɟɤɬɪɨɥɢɬɨɜ, ɫɨɞɟɪɠɚɳɢɯ ɭɤɚɡɚɧɧɵɟ ɢɨɧɵ, ɩɪɨɢɫɯɨɞɢɬ ɨɤɢɫɥɟɧɢɟ ɦɨɥɟɤɭɥ ɜɨɞɵ (ɜ ɧɟɣɬɪɚɥɶɧɨɣ ɢɥɢ ɤɢɫɥɨɬɧɨɣ
ɫɪɟɞɚɯ):
O – 4e o O2 + 4ɇ+
2H
2
ɢɥɢ ɢɨɧɨɜ ɝɢɞɪɨɤɫɢɞɚ Ɉɇ
II ɝɪɭɩɩɚ – ɛɟɫɤɢɫɥɨɪɨɞɧɵɟ ɚɧɢɨɧɵ: S
–
ɜ ɳɟɥɨɱɧɵɯ ɪɚɫɬɜɨɪɚɯ:
4Ɉɇ
í 4e o O2 + 2H2O.
2
, Cl–, Br–, I–.
ɉɪɢ ɷɥɟɤɬɪɨɥɢɡɟ ɜɨɞɧɵɯ ɪɚɫɬɜɨɪɨɜ ɷɥɟɤɬɪɨɥɢɬɨɜ, ɫɨɞɟɪɠɚɳɢɯ ɭɤɚɡɚɧɧɵɟ
ɢɨɧɵ, ɩɪɨɬɟɤɚɟɬ, ɫ ɭɱɟɬɨɦ ɩɨɥɹɪɢɡɚɰɢɢ ɷɥɟɤɬɪɨɞɨɜ, ɚɧɨɞɧɵɣ ɩɪɨɰɟɫɫ – ɨɤɢɫɥɟɧɢɟ ɛɟɫɤɢɫɥɨɪɨɞɧɨɝɨ ɚɧɢɨɧɚ ɩɨ ɦɟɪɟ ɭɜɟɥɢɱɟɧɢɹ ɢɯ ɫɬɚɧɞɚɪɬɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ
2
, I , Br, Cl) (ɬɚɛɥ. ɉ8) ɫ ɜɵɞɟɥɟɧɢɟɦ ɩɪɨɫɬɵɯ ɜɟɳɟɫɬɜ (S, I2, Br2, Cl2).
(S
ɇɚɩɪɢɦɟɪ: 2Cl
í 2Ɲ = Cl2 .
Ɋɟɚɤɰɢɢ ɨɤɢɫɥɟɧɢɹ ɚɧɢɨɧɨɜ II ɝɪɭɩɩɵ ɢɦɟɸɬ ɩɨɬɟɧɰɢɚɥɵ ɦɟɧɶɲɟ, ɱɟɦ ɩɨɬɟɧɰɢɚɥɵ ɤɢɫɥɨɪɨɞɨɫɨɞɟɪɠɚɳɢɯ ɚɧɢɨɧɨɜ ɢ ɮɬɨɪɢɞ-ɢɨɧɚ.
ȿɫɥɢ ɜ ɪɚɫɬɜɨɪɟ ɩɪɢɫɭɬɫɬɜɭɸɬ ɨɞɧɨɜɪɟɦɟɧɧɨ ɢɨɧɵ ɝɚɥɨɝɟɧɨɜ (I
ɬɨ ɜɧɚɱɚɥɟ ɨɤɢɫɥɹɸɬɫɹ ɢɨɧɵ I
, ɡɚɬɟɦ Br, ɡɚɬɟɦ Cl.
, Br, Cl),
ȿɫɥɢ ɜ ɪɚɫɬɜɨɪɟ ɟɫɬɶ ɫɦɟɫɶ ɚɧɢɨɧɨɜ I ɢ II ɝɪɭɩɩ, ɬɨ ɧɚ ɚɧɨɞɟ ɜ ɩɟɪɜɭɸ ɨɱɟɪɟɞɶ ɨɤɢɫɥɹɸɬɫɹ ɛɟɫɤɢɫɥɨɪɨɞɧɵɟ ɚɧɢɨɧɵ (ɚɧɢɨɧɵ II ɝɪɭɩɩɵ).
2. Ⱥɤɬɢɜɧɵɣ (ɪɚɫɬɜɨɪɢɦɵɣ) ɚɧɨɞ (Ni, Zn, Cu, Ag ɢ ɞɪ.).
ȿɫɥɢ ɩɨɬɟɧɰɢɚɥ ɦɟɬɚɥɥɢɱɟɫɤɨɝɨ ɚɧɨɞɚ ɢɦɟɟɬ ɦɟɧɶɲɟɟ ɡɧɚɱɟɧɢɟ, ɱɟɦ ɩɨɬɟɧɰɢɚɥ ɤɢɫɥɨɪɨɞɧɨɝɨ ɷɥɟɤɬɪɨɞɚ ɜ ɧɟɣɬɪɚɥɶɧɨɣ ɫɪɟɞɟ
[(E0 < (0,8) ȼ)], ɬɨ ɩɪɨɢɫ-
ɯɨɞɢɬ ɪɚɫɬɜɨɪɟɧɢɟ ɦɟɬɚɥɥɚ, ɢɡ ɤɨɬɨɪɨɝɨ ɢɡɝɨɬɨɜɥɟɧ ɚɧɨɞ. ɉɪɢ ɷɬɨɦ ɩɪɨɬɟɤɚɟɬ
ɷɥɟɤɬɪɨɥɢɡ ɫ ɪɚɫɬɜɨɪɢɦɵɦ ɚɧɨɞɨɦ:
n+
Me – ne o Me
.
149
K
ɉɪɢɦɟɪɵ ɪɟɲɟɧɢɹ ɡɚɞɚɱ
ɉɪɢɦɟɪ 10.1. Ɉɩɪɟɞɟɥɢɬɶ, ɤɚɤɨɟ ɤɨɥɢɱɟɫɬɜɨ ɦɟɞɢ ɜɵɞɟɥɢɬɫɹ ɧɚ ɤɚɬɨɞɟ ɩɪɢ
ɩɪɨɩɭɫɤɚɧɢɢ ɬɨɤɚ ɫɢɥɨɣ 5 Ⱥ ɜ ɬɟɱɟɧɢɟ 45 ɦɢɧɭɬ ɱɟɪɟɡ ɪɚɫɬɜɨɪ ɫɭɥɶɮɚɬɚ ɦɟɞɢ
(II). ȼɵɯɨɞ ɦɟɬɚɥɥɚ ɩɨ ɬɨɤɭ ɪɚɜɟɧ 1. ɗɥɟɤɬɪɨɞɵ ɢɧɟɪɬɧɵɟ.
Ɋɟɲɟɧɢɟ. ɇɚ ɤɚɬɨɞɟ ɩɪɨɬɟɤɚɟɬ ɩɪɨɰɟɫɫ ɜɨɫɫɬɚɧɨɜɥɟɧɢɹ ɦɟɞɢ:
2+
+ 2Ɲ o Cu, n = 2.
Cu
ɉɨ ɡɚɤɨɧɭ Ɏɚɪɚɞɟɹ (2) ɦɚɫɫɚ ɜɵɞɟɥɢɜɲɟɣɫɹ ɦɟɞɢ m
MIt
CCu
u
nF
ɝɞɟ M
m
Cu
– ɦɨɥɹɪɧɚɹ (ɚɬɨɦɧɚɹ) ɦɚɫɫɚ ɦɟɞɢ, ɝ/ɦɨɥɶ;
Cu
,
ɪɚɜɧɚ:
Cu
I – ɫɢɥɚ ɬɨɤɚ, Ⱥ;
t – ɜɪɟɦɹ, ɫ;
– ɜɵɯɨɞ ɦɟɞɢ ɩɨ ɬɨɤɭ;
K
Cu
n – ɱɢɫɥɨ ɷɥɟɤɬɪɨɧɨɜ, ɭɱɚɫɬɜɭɸɳɢɯ ɜ ɷɥɟɤɬɪɨɞɧɨɦ ɩɪɨɰɟɫɫɟ;
F – ɩɨɫɬɨɹɧɧɚɹ Ɏɚɪɚɞɟɹ.
ȼɵɱɢɫɥɹɟɦ ɦɚɫɫɭ ɜɨɫɫɬɚɧɨɜɥɟɧɧɨɣ ɦɟɞɢ:
63,5 ɝ/ɦɨɥɶ 5Ⱥ (45 60) ɫ 1
m
Cu
2 96 500 Ʉɥ/ɦɨɥɶ
4, 44 ɝ.
ɉɪɢɦɟɪ 10.2.
ɩɪɢ ɷɥɟɤɬɪɨɥɢɡɟ ɜɨɞɧɨɝɨ ɪɚɫɬɜɨɪɚ, ɫɨɞɟɪɠɚɳɟɝɨ ɫɦɟɫɶ ɤɚɬɢɨɧɨɜ Ni
3+
, Cu2+, Zn2+, Mn2+ ɩɪɢ ɢɯ ɨɞɢɧɚɤɨɜɨɣ ɦɨɥɹɪɧɨɣ ɤɨɧɰɟɧɬɪɚɰɢɢ. ȼ ɤɚɤɨɣ ɩɨ-
Al
ɇɚɩɢɫɚɬɶ ɭɪɚɜɧɟɧɢɹ ɤɚɬɨɞɧɵɯ ɩɪɨɰɟɫɫɨɜ, ɩɪɨɬɟɤɚɸɳɢɯ
2+
, Na+,
ɫɥɟɞɨɜɚɬɟɥɶɧɨɫɬɢ ɛɭɞɭɬ ɪɚɡɪɹɠɚɬɶɫɹ ɧɚ ɤɚɬɨɞɟ ɤɚɬɢɨɧɵ ɦɟɬɚɥɥɨɜ? Ɂɧɚɱɟɧɢɹ
ɷɥɟɤɬɪɨɞɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ ɫɦ. ɜ ɬɚɛɥ. ɉ6 (ɉɪɢɥɨɠɟɧɢɹ).
Ɋɟɲɟɧɢɟ. Ɂɧɚɱɟɧɢɹ ɷɥɟɤɬɪɨɞɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ:
0000
2 32
Ni /Ni Na /Na Al /Al Cu /Cu
2+
, Cu
Ni
2+
, Mn2+– II ɝɪɭɩɩɚ ɤɚɬɢɨɧɨɜ;
Zn
+
, Al3+ – III ɝɪɭɩɩɚ ɤɚɬɢɨɧɨɜ.
Na
ɉɨɫɥɟɞɨɜɚɬɟɥɶɧɨɫɬɶ ɤɚɬɨɞɧɵɯ ɩɪɨɰɟɫɫɨɜ:
1) Cu
2) Ni
3) Zn
2H
4) Mn
2H
5) 2H
0, 26B, 2, 71B, 1, 66B, 0, 34B,EEEE
00 0
22
Zn /Zn Mn /Mn H / H
2+
– I ɝɪɭɩɩɚ ɤɚɬɢɨɧɨɜ;
2+
+ 2e ĺ Cu;
2+
+ 2e ĺ Ni;
2+
+ 2e ĺ Zn;
O + 2e = 2OH + H2;
2
2+
+ 2e ĺ Mn;
O + 2e = 2OH + H2;
2
O + 2e = 2OH + H2 (ɜɦɟɫɬɨ ɤɚɬɢɨɧɨɜ Na+ ɢ Al3+).
2
0, 76B, 1,19B, 0, 41B.EEE
2
150
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