, - , .
, , , DH = 0 DG -T×DS. , DS>0, DG < 0 , , .
II :
[7].
( ) (16), ( ).
( ) 1 , . : ΔGo.(2) = 0; ΔGo.(2) = 0.
, .
, :
aA + bB = cC + dD
(17) | |
(18) |
, ΔG- < 0, , ∆G- > 0, , .
, - :
, :
+ = + ; ΔG0- = +21 .
, .. ΔGo- > 0. :
+ 2 = + 34; ΔGo- = ‑30,5 .
1 ( ) DH DS.
1. DH DS.
() | ||||
DH | DS | DG | ||
- | + | - | C6H6 + 7,5O2 = 6CO2 + 3H2O | |
+ | - | + | N2 + 2O2 = 2NO2 | |
- | - | 3H2 + N2 = 2NH3 | ||
+ | + | N2O4 = 2NO2 |
, , , , ΔS < 0. , , .
. 6000 , . 70 .
|
|
, , , . , 8400-12000 , - 16700-20900 .
, 1 : - 39,5 , - 17,1 , - 22,3 .
, . , . , .
.
1
, , 40 60 . , , , , . 1420 /.
.
(), , :
40×39,5 + 60×17,1 = 2606 .
, :
. , (, ) :
6H12O6(.) + 6O2() = 6CO2() + 6H2O(.),
I :
= (6× CO2 + 6× H2O) - 6H12O6 =
= (6×(-394) + 6×(-286)) - (-1274) = -2806 /.
- 1 . , , :
DH = n×DH0,
n - .
:
,
( ):
DH = 0,33×(-2806) -926 .
, .
- - :
+ H2O = + 34; DG0 = -30,5 /
, .
. , -6- :
1) + 34 -6- + 2;
ΔG0 = +13,8 /
(2), , :
|
|
2) + H2O + 34 ΔG0 = -30,5 /.
(1) (2) :
3) + -6- +
ΔG0 = -16,7 /.
1
. , .
.
, .. DG < 0. DG :
DG = DH - T×DS
(DS < 0), . , . :
1) DH < 0 ( );
2) .
2
-. , .
.
1) , DH > 0.
2) , DS > 0.
3) , DG < 0.
3
, Thiobacillus denitrificans:
6KNO3(.) + 5S(.) + 2CaCO3(.) = 3K2SO4(.) + 2CaSO4(.) + 2CO2() + 3N2()
:
K2SO4 | CaSO4 | CO2 | KNO3 | CaCO3 | |
, / | -1438 | -1432 | -393,5 | -493 | -1207 |
, (- ) .
.
, :
= (3× K2SO4 + 2× CaSO4 + 2× CO2) -
- (6× KNO3 + 2× CaCO3) = 3×(-1438) + 2×(-1432) +
+ 2×(-393,5) - [6×(-493) + 2×(-1207)] = -2593 .
< 0, .
4
:
2C2H5OH(.) = C2H5OC2H5(.) + H2O(.)
:
C2H5OH = -1368 /;
C2H5OC2H5 = -2727 /.
.
, ( ) :
= 2× C2H5OH - C2H5OC2H5 =
= 2× (-1368) - (-2727) = -9 .
, .
5
(II) :
(1) | C(.) + 2() = 2(); | = -393,5 /; |
(2) | () + 0,52() = 2(); | = -283,0 /. |
.
(1) , CO2.
(2):
= CO2 - CO.
:
CO = CO2 - .
:
CO = -293,5 - (-283) = -110,5 /.
.
, :
(1) - (2) | C(.) + 0,52() = (); | CO = -110,5 /. |
6
:
CH4() + Cl2() = CH3Cl() + HCl(),
:
CH3Cl | HCl | CH4 | Cl2 | |
, /(×K) |
.
(17):
= ( CH3Cl + HCl) - ( CH4 + Cl2) = 234 + 187 - (186 +
+ 223) = 12 /(×K).
|
|
7
:
C2H5OH(.) + H2O2(.) = CH3COH() + 2H2O(.)
:
CH3COH | C2H5OH | H2O | H2O2 | |
, / | -128 | -175 | 237 | 121 |
, .
.
(18):
= ( CH3COH + 2× H2O) - ( C2H5OH + H2O2) = -128 + 2× (-237) - [(-175) + (-121)] = -306 /.
< 0, .
8
:
6H12O6(.) + 6O2() = 6CO2() + 6H2O(.).
:
H2O | CO2 | 6H12O6 | O2 | |
, / | -286 | -393,5 | 1274,5 | |
, /(×K) |
.
:
= 6× CO2 + 6× H2O - 6H12O6 - 6 O2 =
= 6×(-393,5) + 6×(-286) - (-1274,5) - 6×0 = -2803 ;
= 6× 2 + 6× H2O - 6H12O6 - 6× O2 =
= 6×214 + 6×70 - 212 - 6×205 = 262 /K = 0,262 /K.
:
= - T× = -2803 - 298,15 K×0,262 /K =
= -2881 .
9
250, DH0 = -6,08 /; DS0 = -5,85 /(×K). .
.
:
DG0 = DH0 - T×DS0.
, :
DG0 = -6,08 / - 298 K×(-5,85×10-3) /(×K) =
= -4,34 /.
, - . , , .., .
10
, , = 283 /, = 288 /(×K).
.
, :
, - . - , :
, T > 983 K.
1. ? - ?
2. . ? ?
3. ? , ?
4. ? -?
5. ? ?
6. ? ?
7. ? .
8. ? .
9. ? - ?
10. ? ?
11. ? ?
12. ? ? ?
|
|
13. ? -?
14. . ?
15. . () ?
16. . ?
1
1. , Nitrosomonas:
NH3() + 1,5O2() = HNO2(-) + H2O(.),
:
NH3 | HNO2 | H2O | |
, / | -46 | -119 | -286 |
- ?
2. :
2H6() + H2() = 2CH4(),
:
C2H6 | CH4 | H2 | |
, / | -1560 | -890 | -286 |
, /(×K) |
3. b- 250, DH0 = -6,75 , DS0 = -9,74 /K. . , .
2
1. :
NH2CH2COOH() + 1,5O2() = 2O2() + H2O(.) + NH3(),
:
NH2CH2COOH | O2 | H2O | NH3 | |
, / | -537 | -394 | -286 | -46 |
- ?
2. :
2H2() + 2H2() = C2H6(),
:
C2H2 | C2H6 | H2 | |
, / | -1300 | -1560 | -286 |
, / | -33 |
3. 500, DH0 = 417 , DS0 = 1,32 /K. . , .
3
1. , , 3000 . , :
12H22O11(-) + 12O2() = 12CO2() + 11H2O(.),
:
12H22O11(-) | CO2() | H2O(.) | |
, / | -2215 | -394 | -286 |
2. , .., :
C6H6 | C6H12 | H2 | |
, / | -156 | ||
, / | -3268 | -3920 | -286 |
- ?
3. (IV):
CH3COCOOH(-) = CH3COH() + CO2()
, :
CH3COCOOH | CH3COH | CO2 | |
, / | -596 | -166 | -394 |
, /(×K) | 171,5 |
. , .
4
1. , - Beggiatoa Thiothrix, :
2H2S() + O2() = 2H2O(.) + 2S(.);
2S(.) + 3O2() + 2H2O(.) = 2H2SO4(.),
:
H2S | H2O | H2SO4 | |
, / | -20 | -286 | -814 |
2. :
3C2H2() = C6H6(.),
:
C2H2 | C6H6 | |
, / | -1300 | -3268 |
, /(×K) |
- ?
3. :
CO(NH2)2 (-) + 2(.) = 2NH3 (-) + 2 (-)
:
CO(NH2)2 | 2 | NH3 | 2 | |
, / | -319 | -286 | -80 | -414 |
, /(×K) |
, .
5
1. :
2NH2CH2COOH(-) + 3O2() = O(NH2)2(-) + 3H2O(.) + 3CO2(),
:
NH2CH2COOH | H2O | O(NH2)2 | CO2 | |
, / | -523 | -286 | -319 | -394 |
- ?
|
|
2. :
6H5NO2(.) + 3H2() = 6H5NH2(.) + 2H2O(.),
:
6H5NO2 | 6H5NH2 | H2 | |
, / | -3093 | -3396 | -286 |
- ?
3. 500, DH0 = 283 , DS0 = 288 /K. . , .
6
1. , - Thiobacillus Thioparus:
5Na2S2O3×5H2O(.) + 7O2() = 5Na2SO4(.) + 3H2SO4(.) + 2S(.) + 22H2O(.),
:
Na2S2O3×5H2O | Na2SO4 | H2SO4 | H2O | |
, / | -2602 | -1389 | -814 | -286 |
- ?
2. :
CH3COH(.) + H2() = C2H5OH(.)
:
CH3COH | C2H5OH | H2 | |
, / | -1166 | -1368 | -286 |
, / | -128 | -175 |
3. -:
NH2CH2CONHCH2COOH(-) + H2O(.) = 2NH2CH2COOH(-)
-
, :
- | H2O(.) | NH2CH2COOH | |
, / | -734 | -523 | |
, /(×K) |
. , .
7
1. CH3OH :
CH3OH(.) + 1,5O2() = CO2() + 2H2O(.) DH0 = -726,5 ;
() + O2() = CO2() DH0 = -394 ;
H2() + 0,5O2() = H2O(.) DH0 = -286 .
2. CS2 :
CS2(.) + 3O2() = CO2() + 2SO2() DH0 = -1078 ;
SO2() + 0,5O2() = SO3() DH0 = -98 .
3. DG0 :
+ + = + 34 + ,
:
+ H2O = + 34 DG0 = 30,5 /;
+ = + H2O DG0 = 17,2 /.
.
8
1. DH0 :
1) C6H12O6(-) = 2C2H5OH(-) + 2CO2();
2) C6H12O6(-) = 23H6O3(-).
:
C6H12O6 | C2H5OH | CO2 | 3H6O3 | |
, / | -1275 | -278 | -394 | -686 |
?
2. :
3H6() + H2() = 3H8(),
:
C3H6 | 3H8 | H2 | |
, / | -2058 | -2220 | -286 |
, /(×K) |
3. CHCl3 :
CHCl3 () + O2() = CO2() + HCl () + Cl2 (),
, :
CHCl3 | CO2 | HCl | O2 | Cl2 | |
, / | -100 | -394 | -92 | ||
, /(×K) |
. , .
9
1. Ca3(PO4)2 :
3CaO(.) + P2O5(.) = Ca3(PO4)2(.) DH0 = -739 ;
P4(.) + 5O2() = 2P2O5(.) DH0 = -2984 ;
Ca(.) + 0,5O2() = CaO(.) DH0 = -636 .
2. 49 800 11,80. , 3,76 /(×K), .
3. :
2CO() + 2H2O() = CH3COOH() + O2(),
, :
CO | H2O | CH3COOH | O2 | |
, / | -110 | -286 | -485 | |
, /(×K) |
. , .
10
1. :
DH0.C2H5OH(.) = -1368 /;
() + O2() = CO2() +394 ;
H2() + 0,5O2() = H2O(.) +286 .
2. :
C4H8() + 2O2() = 2CH3COOH(.)
:
C4H8 | CH3COOH | O2 | |
, / | -2710 | -875 | |
, / | -390 |
3. 250, DH0 = -6,58 /, DS0 = -9,5 /(×). . , .
11
1. :
4NH3() + 5O2() = 4NO() + 6H2O(),
:
NH3 | NO | H2O | |
, / | -46 | -242 |
- ?
2. :
1) C2H5OH(-) + 0,5O2() = CH3COH(-) + H2O(.) DH0 = -256 ;
2) CH3COH(-) + 0,5O2() = CH3COOH(-) DH0 = -237 .
.
3. 370C DH0 DG0 +24,3 -30,5 /. , .
12
1.
4NH3() + 3O2() = 2N2() + 6H2O(.)
2,24 76,5 . NH3, H2O = -286 /.
2. :
O() + 3H2() = H4() + H2O(),
:
O | H4 | H2 | H2O | |
, / | -284 | -890 | -286 | |
, /(×K) |
3. :
D- + = D--6- + ,
:
D- + = D--6- +
DG0 16,7 /, :
D--6- = D--6-
DG0 +1,7 /.
13
1. :
4L-(-) + 15O2 = 12CO2 + 14H2O(.) + 2N2
:
L- | CO2 | H2O | |
, / | -563 | -394 | -286 |
- ?
2. :
CH4() + CO2() = 2CO() + 2H2()
:
CH4 | CO2 | CO | H2 | |
, / | -890 | -284 | -286 | |
, / | -51 | -394 | -137 |
3. , 370:
C6H12O6(-) = C3H7COOH(-) + 2CO2() + 2H2()
:
C6H12O6 | CO2 | C3H7COOH | H2 | |
, / | -1264 | -524 | ||
, /(×K) |
. , .
14
1. :
C6H8O7(-) + 5O2 = 12CO2 + 14H2O(.)
:
C6H8O7 | CO2 | H2O | |
, / | -1838 | -394 | -286 |
- ?
2. :
CO() + 2H2() = CH3OH(.),
:
O | H2 | CH3OH | |
, / | -284 | -286 | -726 |
, /(×K) |
3. DS0 = -100 /(×K); DH0 = -50 /. 2270. . , .
15
1. :
3MgO(.) + 2H3PO4(-) = Mg3(PO4)2 (.) + 3H2O(.)
, :
MgO | H3PO4 | Mg3(PO4)2 | H2O | |
, / | -602 | -1277 | -3384 | -286 |
- ?
2. :
2C2H5OH(.) = C4H6() + 2H2O(.) + H2()
:
C4H6 | C2H5OH | H2 | H2O | |
, / | -2544 | -1368 | -286 | |
, /(×K) |
3. , :
CaSO4(.) + 2H2O(.) = CaSO4×2H2O(.)
:
CaSO4 | CaSO4×2H2O | H2O | |
, / | -1432 | -1762 | -286 |
, /(×K) |
. , .
16
1. L- :
45H9O4N(-) + 21O2 () = 20CO2 () + 18H2O(.) + 2N2 ()
, :
5H9O4N | CO2 | H2O | |
, / | -982 | -394 | -286 |
- ?
2. :
C4H8() + H2() = C4H10()
:
C4H10 | C4H8 | H2 | |
, / | -2878 | -2717 | -286 |
, / | -17 |
3. , DG0 = 4508 /; DH0 = 5659 /. . , .
17
1. :
2NH3×2 (-) + 2 () = CO(NH2)2 () + 32 (.)
, :
NH3×2 | 2 | CO(NH2)2 | 2 | |
, / | -264 | -394 | -197 | -286 |
- ?
2. CuSO4, CuSO4×H2O, CuSO4×5H2O : -67; -39; +12 /. CuSO4 .
3. :
+ = + ,
:
+ H2O = + 34; DG0 = 43 /;
+ H2O = + 34; DG0 = 30,5 /.
18
1. , :
C54H110O6 (-) + 3H2O (.) = 3C17H35COOH (-) + C3H8O3 (-),
: (C54H110O6) = -37760 /; (CO2) = -394 /; (H2O) = -286 /; (C17H35COOH) = -949 /; (C3H8O3) = -669 /.
2. , :
4NH3() + 3O2() = 2N2() + 6H2O() + 1226 ;
2H2() + O2() = 2H2O() + 484 .
3. , , 50 (40%- 0,94 /). , , -1368 /. , , , 2100 /.