. . , [A j ], : [H+], [H3PO4], [PO43‑]. , , , , 0. ,
H2O Û H+ + OH‑, H3PO4 Û 3 H+ + PO43‑
0 Û ‑ H2O + H+ + OH‑, 0 Û ‑ H3PO4 + 3 H+ + PO43‑.
A j - , , (, ) -
0 Û a j A j,
a j - , , 0 , . j, , , , Br2 I3‑.
(),
= K,
aj = a (A j) - A j, K - . ,
aj = g j [A j ],
g j , . g j . aj [A j ], , , .
= K c = K / , lg K c = lg K ‑ a j lg g j.
, K c, , g j. K c, "c" . , .
, aj = 0 [A j ] = 0. , , . . - ( ). , aj = 1 - - , . , , , BaSO4(s), s - "solid" - , Hg(l), l - "liquid" - . (). , .
- , [A j ] 0. , 1,
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g j 1, aj [A j ], [A j ] 0.
. g j - . ,
I = {S zj 2 [A j ]} / 2,
zj - A j . , (, ), . , " ", . HCl, HClO4, HBr, HI, H2SO4 ( ), HNO3; Na+, K+, Rb+, Cs+, , ClO4‑.
,
lg g j = zj 2 lg g, lg g = ‑ 0,5 / (1 + ) + 0,15 I,
-. , . I > 0,5, . ,
lg K c = lg K ‑ { a j zj 2} lg g.
, . , , : - " " ( I = 0), - I = 1, . 25.
lg K (t, oC) = lg K (25 oC) + 5,88×10‑4×(t 25)× D H,
D H - , /.
. , (International Union of Pure and Applied Chemistry, IUPAC) , ,
K (H3PO4 Û 3 H+ + PO43‑), K (0 Û ‑ H3PO4 + 3 H+ + PO43‑).
, , . , K , . : , H+ - H, - a ( "acidity" - ), - s ( "solubility" - ), - D ( "distribution" - ). . - , M - ( "", , L - . L - , .. .
- - . () , () , ,
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Cr3+ + e‑ Û Cr2+, S4O62‑ + 2 e‑ Û 2 S2O32‑, 2 Hg2+ + 2 e‑ Û Hg22+, HCrO4‑ + 7 H+ + 3 e‑ Û Cr3+ + 4 H2O, Zn2+ + 2 e‑ Û Zn(s).
H+ - . pH, - E. pe = ‑ lg a (e),
E = q pe = ‑ q lg a (e).
q = ln (10) R T / F, (q = 0,05916 25 o),
ln (10) = 2,3026, R - , T - , F - . , 1
2 H+ + 2 e‑ Û H2(g), lg K = 0.
0 Û ae e- + a j A j, lg K,
E = E 0 ‑ (q / |ae|) a j lg aj = E 0 + (q / ae) a j lg aj.
, ‑ .
( ) | ||
1. | ||
m M + n L Û M m L n | b nm | |
2 Ag+ + 6 I‑ Û Ag2I64‑ | b62 | |
M + n L Û ML n | b n | m = 1 |
Ag+ + NH3 Û AgNH3+ | b1 | |
Ag+ + 2 NH3 Û Ag(NH3)2+ | b2 | |
ML n ‑1 + L Û ML n | Kn | K , Kn = b n / b n ‑1 |
Ag+ + NH3 Û AgNH3+ | K 1 | |
AgNH3+ + NH3 Û Ag(NH3)2+ | K 2 | |
2. - | ||
H2O Û H+ + OH‑ | Kw | |
m H+ + L Û H m L | bH m | L , H+ , bH m b1 m |
H+ + PO43‑ Û HPO42‑ | bH1 | |
2 H+ + PO43‑ Û H2PO4‑ | bH2 | |
3 H+ + PO43‑ Û H3PO4 | bH3 | |
H+ + H m ‑1L Û H m L | K H m | K H m K H m = bH m / bH(m ‑1) |
H+ + PO43‑ Û HPO42‑ | K H1 | |
H+ + HPO42‑ Û H2PO4‑ | K H2 | |
H+ + H2PO4‑ Û H3PO4 | K H3 | |
H m +1L Û H m L + H+ | Ka (N ‑ m) | H N L, Ka (N‑m) = 1 / K H(m +1) |
H3PO4 Û H+ + H2PO4‑ | Ka 1 | |
H2PO4‑ Û H+ + HPO42‑ | Ka 2 | |
HPO42‑ Û H+ + PO43‑ | Ka 3 | |
m M + n OH‑ Û M m (OH) n | b nm | ( ) |
2 Fe3+ + 2 OH‑ Û Fe2(OH)24+ | b22 | |
Hg2+ + OH‑ Û HgOH+ | b1 | |
Hg2+ + 2 OH‑ Û Hg(OH)2 | b2 | |
Hg2+ + 3 OH‑ Û Hg(OH)3‑ | b3 | |
m M + n H2O Û M m (OH) n + n H+ | *b nm | H2O *b nm = b nm K wn, m = 1 |
2 Fe3+ + 2 H2O Û Fe2(OH)24+ + 2 H+ | *b22 | |
M + n H2O Û M(OH) n + n H+ | *b n | |
Hg2+ + H2O Û HgOH+ + H+ | *b1 | |
Hg2+ + 2 H2O Û Hg(OH)2 + 2 H+ | *b2 | |
Hg2+ + 3 H2O Û Hg(OH)3‑ + 3 H+ | *b3 |
3. | ||
L Û L(), L Û , | K D | ( - ) |
Br2 Û Br2(CCl4), Br2 Û | ||
Al3+ + 3 HOxin () Û Û AlOxin3 ()+ 3 H+ | K ex | |
L(g) Û L | Kp | , p |
CO2(g) Û CO2 | ||
L(s) Û L, L(l) Û L, | Ks | (s , l ) |
I2(s) Û I2, Br2(l) Û Br2, | ||
M m L n (s) Û m ML q + (n m q) L | Ksq | (q = 0 ), Ksq = Ks 0 b q. - , Ks . |
HgI2(s) Û Hg2+ + 2 I‑ | Ks 0 | |
HgI2(s) Û HgI+ + I‑ | Ks 1 | |
HgI2(s) Û HgI2 | Ks 2 | |
HgI2(s) + I‑ Û HgI3‑ | Ks 3 | |
HgI2(s) + 2 I‑ Û HgI42‑ | Ks 4 | |
Cu3(OH)2(CO3)2(s) Û 3 Cu2+ + 2 OH‑ + 2 CO32‑, Ks (3 Cu2+, 2 OH‑, 2 CO32‑) |
, |ae|,
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‑ ae pe + a j lg aj = lg K = E 0 |ae| / q = ‑ E 0 ae / q.
. , . , , , , . , , , . - 0 . r , (r ‑ 1) .
.
Fe3+ + 2 F‑ Û FeF2+, lg b2 = 9,30; H+ + F‑ Û HF, lg K H = 3,17,
, F‑. ,
Fe3+ + 2 F‑ | Û | FeF2+, | lg b2 = 9,30, | |
‑ 2 | H+ + F‑ | Û | HF, | lg K H = 3,17 |
Fe3+ + 2 HF | Û | FeF2+, + 2 H+, | lg b2 2 lg K H = 2,96, |
- . -
‑ lg a (Fe3+) ‑ 2 lg a (F‑) + lg a (FeF2+) = lg b2 = 9,30, | |
‑2 | ‑ lg a (H+) ‑ lg a (F‑) + lg a (HF) = lg K H = 3,17, |
‑ lg a (F‑) ‑ 2 lg a (HF) + lg a (FeF2+) + 2 lg a (H+) =
= lg b2 2 lg K H = 2,96.
: ( )
. : (‑, - , , , ); - , , , ( ); - , . : +, .
1. | Marcus Y. Recommended symbols for solution equilibria. Analytical chemistry division. Commission of equilibrium data. // Pure Appl. Chem., 1959, v. 18, No. 3, . 459-464. |
2. | Martell A. E., Smith R. M. Critical stability constants. New York: Plenum. V. 1 Amino acids. 1974. 496 .; V. 2. Amines. 1975. 415 .; V. 3. Other organic ligands. 1977. 495 .; V. 4. Inorganic complexes. 1976. 257 .; V. 5. First supplement. 1982. 604 . |
3. | Kotrlý S., Šůcha L. Handbook of chemical equilibria in analytical chemistry. New York: Ellis, 1985. 414 . |
4. | Stary J., Freiser H. Equilibrium constants of liquid-liquid distribution reactions. Part IV. Chelating extractants. Oxford et al: Pergamon, 1978. 228 . |
5. | .., .., .. . : , 1983. - 257 . |
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