, . , , , .. .
. , , , ..
(, ) (, ). , , , .
: , , , , . , . U, H, S, G .
4.1.1. .
. , , . (+), (), :
H2() + l2() = 2Hl() + 183,6
1/2H2 ()+ 1/2l2()= HCl () + 91,8 ∙-1
N2 ()+ 2()= 2N() 180,4
1/2N2 ()+ 2()= N() 90,2 ∙-1
, (-), - (+).
, 1 ; , 1 ; - , 1 .
- , ΔU
2 0. (298 ) 1,013∙105 . , .
.
(U) , . , U , , , ..
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c Q, U1 , , (), .. U2 =U1 +Q-A ΔU =Q-A, ΔU= U2 -U1.
, .. , , : ΔU =Qv. V . ΔU, , Qv , .
, , ΔV, , ΔV. - , =U+pΔV. Δ = ΔU+pΔV.
Δ Δ0298. Δ , .
(=ΔV), ΔU= Δ pΔV ΔU= Δ A, ΔU=Q A, Δ=Qp ( p ). Δ , Qp.
, .. , ΔV . pΔV=0, , Δ=ΔV. : Qv =Q.
= const V= const .
(1840): , , .
2: Δ=Δ1+Δ2,
Δ 2
Δ1 Δ2
.. . , .
: :
Δ0298()=∑ Δ0298(.) -∑Δ0298(.).
(2, l2 .) . . ,
2()+ r2() → 2Hr() Δ0298=2(-36,3)- (0+0)= -72,6 ,
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.. r .
, . , , .. 2. 2 CO 2:
+ 2 → 2 Δ =-393,5 /
+ 1/22→ C2 Δ1 =-283,0 /
+ 1/22→ Δ2 =?
, Δ= Δ1 +Δ2, Δ2 = Δ - Δ1 = - 393,5 (-283,0) = -110,5 /.
: .
(, , ) , . S. ΔS , 1 2,
R- .
, , , . ( ) ( ). , .
, . , , 2 1, .. , . ΔS - , .. S .
, .. . , , , .
, , , 25 0 (298 ) 1 . S0298 .
. ,
+bB+= dD++
ΔS= (dSD + eSE+)-(aSA + bSB+...) ΔS= ∑S. - ∑S.
. , ½ ()+½ 2()=() ΔV>0; , ΔS> 0 (ΔS0298=87,7 /∙). 3N 3/2 2 ()+1/2 N2 ()= H3N() , ΔV<0; , ΔS<0 (ΔS0298=99,1/∙).
, ,
l()+Sb()=lSb(), (ΔS0298=4,03/∙). , , , ()+ 2 ()= 2 (), ΔS=2,9/∙.
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4.1.3.
: (-∆H) , , S.
∆H , . ∆G=∆H-T∆S. G , T=const p=const.
, : ∆P=∆U-T∆S. , ∆G ∆P , ∆H ∆U , p∆V.
∆G . ∆G<0, .. , . ∆G>0, .. , . ∆G=0, .
∆S , , T∆S G : ) , .. ; ) ∆, , ∆<T∆S, .. , , .
∆S ∆G=∆H-T∆S T∆S , (+∆) , ∆G . (-∆) , ∆, .. , -∆+(-∆S) .
∆S , , . , ∆G ∆.
, ∆G. ∆ S , , ∆G ∆Go298=∆H o298-T∆S o298 [3].
1. .
, 100 25, , :
∆H o298, CaO() = -635,1 ∙-1;
∆H o298, H2O() = -285,84 ∙-1;
∆H o298, Ca(O)2() = -986,2 ∙-1.
. : ()+2()=()2(). :
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=
=-986,2-(-635,1)-(-285,84) = 65,26 ∙-1
, 1 65,26, 1 65260 . () = 56∙-1=56∙-1; m() = 100;
100 100/56∙65260=116536.
2. .
()2 :
3→+2+∆1; +2→()2+∆2.
. ∆ ∆1 ∆2, ∆=∆1+∆2;
∆1=∆+∆(2)-∆3 = +177,83 ∙-1;
∆2=∆()2-∆-∆2 = -65,2 ∙-1;
∆= +177,83 65,2 = +113,61 ∙-1.
3. : 2S() + 3/2O2=2() + S2()
1)S() + 2 = 2S(); ∆1= -20,17
2)2 + 1/2 O2 = H2O(); ∆2= -286,0
3)S() + 2 = S2(); ∆3= -297
. 1-3 1 2S(), 2(), S2() : =298 =101,325 , ∆H o298. 2 3 1,
2S() + 3/2 O2 = H2O() + SO2() ∆=∆1+∆2-∆3
2S() , 2(), SO2(), ∆= -286 -297 (-20,17) = = -562,8 . , .
.
2S() + 3/22 = 2() + SO2() + 562,8 . .
4. . Na2O+SiO2=Na2SiO3 298.
. =298, S o298, Na2O()=42,09∙-1∙-1:
S o298, SiO2 () = 71,1∙-1∙-1;
S o298, Na2SiO3 ()=113,8∙-1∙-1. .
So298 .. = So298, Na2SiO3() So298, SiO2 () - So298, Na2O() = 113,8-71,1-42,09=0,61 ∙-1∙-1
5. . 1 1986, 744,05 ∙r-1.
. : , ∆- .
S2-S1=∆S= = = 0,238∙-1∙-1.
6. 2SO2()+2()↔2SO3(). ?
, SO2() = -300,37 ∙-1;
, SO3() = -370,37 ∙-1
.
, SO3.
1. (V) 13 . 111,4 . .
. , , , . , , Qp, ∆. ∆ , . : , , . , .
, ∆ < 0. , :
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15() + 2() = l 3() + 21(); ∆ = -111,4
3
()
- | ∆ , / | - | ∆ , / | ||
22 S2 N 66 24 2S N3 4 26 l | +226,75 +115,28 +90,37 +82,93 +52,28 -20,15 -46,19 -74,85 -84,62 -92,31 | 3 25 2 2 N4l 2 F23 i2 ()2 l23 | -110,52 -201,17 -235,31 -241,83 -285,84 -315,39 -393,51 -822,10 -943,90 -986,50 -1669,80 |
2. 26() + 3 ½ 2 = 2 2() + 3 2(); = -1559,87 .
, 2() 2() (. . 5).
. () 1 , . , .. 25 (298 ) 1,013∙105 ∆ . , ∆. , ,
2 () + 2() - 26(); ∆=?
:
) 26() + 3'/22() = 22() + 2(); ∆= -1559,87 ;
) () + 2() = 2(); ∆ = -393,51 ;
) 2() + ½ O2 = 2(); ∆ = - 285,84 .
, . () 2, () 3, ():
26 + 3722 - 2C - 22-2 -3/22 = 22 + 2 -22 - 2
∆ = -1559,87 -2(-393,51)-3(-285,84) = +84,67 ;
∆ = -1559,87 + 787,02 + 857,52; 26 = 2 + 2; ∆= + 84,67 .
, ∆ () = -84,67 . , :
∆ = 2∆2 + ∆2 - ∆26 - 3 ½ ∆2
, ∆26 = 2∆ + ∆ - ∆
∆26 = 2(-393,51) + 3(-285,84) + 1559,87 = -84,67;
∆ () = -84,67
3.
25() + 2() = 22() + 2(); ∆=?
, , 25() +42,36 , 25(), 2(), 2() . . 5.
. ∆ 25(). :
25() = 25(); ∆= +42,36 +42,36=-235,31-∆25 ();
∆25 () = -235,31 - 42,36 = -277,67 .
, :
∆ = 2(-393,51) + 3(-285,84) + 277,67 = -1366,87 .
4. 1 : ?
. . (, ) , . 1 1 ; . - , 1 1 .
5. 4() + 2 2() + 22()
. ∆G0298 . ∆G0298 4. , ∆G ∆G , , , ∆G0298 : ∆G0298 = 2(-137,27) + 2(0) - (-50,79 - 394,38) = + 170,63 .
∆G0298 > 0, = 298 , 1,013 ∙105 (760 . . = 1 ).
4
, / | / | ||||
S4 | -1138,8 | FeO | -244,3 | ||
3 | -1128,75 | H2O | -237,19 | ||
F34 | -1014,2 | H2O | -228,59 | ||
3 | -944,75 | PbO2 | -219,0 | ||
-604,2 | CO | -137,27 | |||
-581,61 | CH4 | -50,79 | |||
NF | -541,0 | NO2 | +51,84 | ||
-528,4 | NO | +86,69 | |||
2 | -394,38 | C2H2 | +209,20 | ||
NaCl | -384,03 | ||||
ZnO | -318,2 |
5
/ (∙) | /(∙) | ||||
2.44 | H2O | 188,72 | |||
5.69 | N2 | 191,49 | |||
Fe | 27.2 | NH3 | 192,50 | ||
Ti | 30.7 | CO | 197,91 | ||
S | 31.9 | C2H2 | 200,82 | ||
TiO2 | 50.3 | O2 | 205,03 | ||
FeO | 54.0 | H2S | 205,64 | ||
H2O | 69.94 | NO | 210,20 | ||
Fe2O3 | 89.96 | CO2 | 213,65 | ||
NH4Cl | 94.5 | C2H4 | 219,45 | ||
CH3OH | 126.8 | Cl2 | 222,95 | ||
H2 | 130.59 | NO2 | 240,46 | ||
Fe3O4 | 146.4 | PCl3 | 311,66 | ||
CH4 | 186.19 | PCl5 | 352,71 | ||
HCl | 186.69 |
6. (. . 3) (. 5) ∆S0298 , () + 2() = 2() + 2()
. ∆G0 = ∆ - ∆S0; ∆ ∆S ,
∆ 0.. = (-393,51+0) (-110,52-285,84) = +2,85
∆S 0.. =(213.65 + 130.59) (197.91 + 69.94) = +79.39 = 0.07639/(∙)
∆G0 = +2,85 298 ∙ 0,07639 = - 19,91 .
7. Fe2O3 Fe2O3()+ 3H2() = 2Fe() + 2(); ∆= +96,61
, ∆S = 0,1387 /(∙)? Fe23?
. ∆G0 : ∆G =∆H-T∆S = 96,61 -298 ∙ 0,1387 = +55,28 .
∆G > 0, ; , (). , ∆G =0:
∆ = ∆S;
, ≈ 696,5 Fe2O3. .
8. ∆Ͱ, ∆S ∆G0 , Fe2O3() + = 2Fe + . Fe2O3 500 1000 ?
. ∆ 0.. ∆S 0.. (1) (2):
∆ = [3(-110.52)+2∙0]-[-822.10+3∙0]
∆G500= 490,54 -500 = +219,99
∆G1000 = 490,54 - 1000 = -50.56
∆G500 >0, ∆G1000 <0, Fe2O3 1000 500.