Bi kim tra iu kin mn: L THUYT HO V C CAO

bi:
Cu 1: Dng Excel v gin Ellingham ca cc h: Ag2O, CuO, FeO, ZnO, CCO2,
CCO, COCO2 , SiO2, TiO2, Al2O3, MgO, CaO.
Cu 2: Xc nh bng th y nhit thp nht c th kh ZnO n Zn bng C
Cu 3:Xy dng th Frost cho h Clo t th Latimer
Cu 4:Xy dng th Frost cho h Mn trong mi trng axit (Mn, Mn2+, Mn3+, MnO2,
H2MnO4, HMnO4). T nhn xt bn ca Mn(VI)v Mn(III), s dng tnh ton
chng minh nhn xt .
Bi lm:
Cu 1:Ta c:

H S0 : O2 = 0, 0; Zn( r ) = 0, 0; ZnO( r ) = 347,3KJ / mol

S 0 : O2 = 205, 0; Zn( r ) = 41, 63; ZnO( r ) = 43, 6 J / molK
2Zn + O2 = 2 ZnO
0
H 0 = 2 H ZnO
= 2 *( 347,3) = 694, 6( KJ / mol) = 694600( J / mol )
0
0
S 0 = 2 SZnO
SO02 2 SZn
= 201( J / molK )

G 0 = H 0 T S 0 = 694600 + 201*T

H S0 :O 2= 0, 0; Ag (r=) 0,0; Ag 2O =
(r )

30,57KJ / mol

S 0 :O 2 = 205,0; Ag ( )r= 42,7; Ag 2O ( =)r 121,71J / molK

4 Ag +O 2 = 2 Ag 2O
H 0 = 2 H 0AgO= 2*(
30,57)
= 61,14 KJ
( / mol=
S 0 = 2S 0Ag 2O S 0O2 4S 0Ag
= 132,38 J( / molK
G 0 = H 0 T S 0=

HV: Nguyn Th Vn Anh

61140(J / mol )

6114 0 +132,38* T

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

H S0 : O2 =0, 0; Cu( r)
S 0 : O2 = 205, 0; Cur(

=0, 0; CuO( r)
)

=33, 30; CuOr(

=155,
2 KJ / mol
=43, 51 J / molK

2Cu + O2 = 2CuO
0
H 0 =2 HCuO

=2 * ( 155,
2)

0
S 0 =2 SCuO
SO20

2 SCu0

=310,
(4 KJ / mol
)

310400
=(
J / mol
)

=184,
58
( J / molK
)

G 0 = H 0 T S 0 =310400

184+, 58 *T
H S0 :O 2= 0,0; Fe (r=) 0,0; FeO=
(r )

272KJ / mol

S 0 :O 2 =205,0; Fe ( )=
r 27, 29; FeO(=
)r 83,3J / molK
2 Fe +O 2 = 2 FeO
H 0= 2
H 0FeO
= 2*(
272)
=

544 KJ
=
( /mol

S 0 = 2S 0FeO S 0O2 2S 0=
92,98 J ( /molK
Fe
0
G 0 = H 0 T S=

544000 J /mol
(

544000
+
92,98*
T

H S0 : O2 = 0, 0; Mg ( r ) = 0, 0; MgO( r ) = 601,83KJ / mol

S 0 : O2 = 205, 0; Mg (r ) = 32,51; MgO(r ) = 26,8 J / molK
2 Mg + O2 = 2 MgO
0
H 0 = 2 H MgO
= 2*( 601,83) = 1203, 66 ( KJ / mol ) = 1203660( J / mol)
0
0
S 0 = 2 S MgO
SO02 2 S Mg
= 216, 42 ( J / molK )

G 0 = H 0 T S 0 = 1203660 + 216, 42*T

H S0 : O2 = 0, 0; Ca( r ) = 0, 0; CaO ( r ) = 635, 09 KJ / mol
S 0 : O2 = 205, 0; Ca ( r ) = 41, 63; CaO ( r ) = 39, 7 J / molK
2Ca + O2 = 2CaO
0
H 0 = 2H CaO
= 2*( 635, 09) = 1270,18 ( KJ / mol )= 1270180 ( J / mol
0
0
S 0 = 2S CaO
S O02 2S Ca
= 208,86 ( J / molK

G 0 = H 0 T S 0 = 1270180 + 208,86*T
HV: Nguyn Th Vn Anh

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

H S0 : O 2= 0,0; Si (r =
0,0; SiO 2(r=) 859, 4KJ / mol
)
S 0 : O 2 = 205,0; Si ( r) = 18,70; SiO 2( =
41,84J / molK
r)
Si + O 2 = SiO 2
H 0 = H 0SiO2= 859, 4 KJ
( /mol= ) 859400 J( /mol
S 0 = S 0SiO2 S O0 2 S 0Si= 181,86J( molK
/

G 0 = H 0 T S 0= 859400
+ 181,86*T
H S0 :O =
0,0; Ti (=
2
r)

0,0; TiO=
2(r )

944KJ / mol

S 0 :O 2 =205,0; Ti ( )=
r 30,72; TiO 2(=) r 50,62J / molK
Ti +O 2= TiO 2
H 0= H 0TiO=
2

944KJ
/ =
( mol

0
S 0= S 0TiO2 S 0O2 S=
Ti
0
G 0= H 0 T
S=

944000(
J mol
/
)

185,1J ( molK
/

944000
+
185,1*
T

H S0 : O2 = 0, 0; Al( r ) = 0, 0; Al2 O3( r ) = 1669, 79 KJ / mol

S 0 : O2 = 205, 0; Al(r ) = 28, 32; Al2 O3(r ) = 50,99 J / molK
4
2
Al + O2 = Al2 O3
3
3
2
2
H 0 = H Al0 2O3 = *( 1669, 79) = 1113,19( KJ / mol) = 1113190( J / mol)
3
3
2
4
S 0 = S Al0 2O3 SO02 S Al0 = 208, 77 ( J / molK )
3
3
G 0 = H 0 T S 0 = 1113190 + 208, 77 * T

HV: Nguyn Th Vn Anh

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

H S0 : O2 =0, 0; C( r)
S 0 : O2 = 205, 0; Cr(

0,
= 0; CO( K)
=5, 69; COK(

110,
= 52 KJ / mol
)

197,
= 91 J / molK

2C + O2 = 2CO
H 0 =2 HCO0
S 0 =2 SCO0

=2 * ( 110,
52)

221040
=(
J)/ mol

2 SC0 179,
= 44
( J / molK
)

SO20

G 0 = H 0 T S 0

H S0 : O2

=221,
(04 KJ / )mol

221040
=
179, 44 * T

=0, 0; CO( K)

S 0 : O2 = 205, 0; CO
K(

=110,
52; CO2 ( K)
)

=197, 91; COK2 (

393,
= 51 KJ / mol
213,
= 64 J / molK

2CO + O2 = 2CO2
H 0 =2 HCO02

2 HCO0

H 0 =2 * ( 393,
51) 2* ( 110,
52)
S 0 =2 SCO0 2

SO20

2SCO0

565,
= ( 98 KJ /) mol

565980
( = )J / mol

=173,
54
( J / molK)

G 0 = H 0 T S0 565980
=
173,+54 * T
H S0 :O 2= 0,0; C (R=) 0,0; CO 2(=
K)

393,51KJ / mol

S 0 :O 2 =205,0; C ( R)= 5,69; CO 2( =K) 213,64J / molK

C +O 2 = CO 2
H 0 = H 0CO=
393,51KJ
( /mol= )
2

393510 J ( /mol

0
S 0 = S 0CO S 0O2 S =
C

2,95J( molK
/

0
G 0 = H 0 T S =

393510

2,95*
T

HV: Nguyn Th Vn Anh

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

th biu din s ph thuc ca G vo T
Ag - Ag2O
Cu-CuO

100000

-100000

500

1000

1500

2000
2500
COCO2 Zn-ZnO

3000

Fe-FeO

CCO
-300000
CCO2
-500000

Ti-TiO2

Mg-MgO

Al -Al2O3
-700000

Si-SiO2

-900000

Ca-CaO

-1100000

-1300000
Nhit d T

Cu 2:Theo th ta thy kh ZnO v Zn th ta c 2 trng hp:

Trng hp 1: C kh ZnO c Zn v kh CO2 bt u t nhit 1450 0K
2C + 2ZnO 2Zn + CO2
Trng hp 2: C kh ZnO c Zn v kh CO bt u t nhit 1245 0K
C + ZnO Zn + CO
Da vo th ta thy nhit thp nht c th kh ZnO n Zn bng C l 12450K v
to ra sn phm kh l CO chim u th hn.
Cu 3:
E

7+

6 4 4 4 4 4 4 4 4 4( ClO73 /Cl42 ) 4 4 4 4 4 4 4 48

+1.20

5+

3+

+1.18

+1.70

1+

+1.63

+1.36
Cl O
Cl O
Cl O
H Cl O
Cl2
Cl
1 4 4 4 4 44 2 4 4 4 4 4 43
E

1 4 4 4 4 4 4 4 4 4 4 4 4 2 4 4 4 4 4( ClO42 /Cl42 ) 4 4 4 4 43
E

( ClO4 /Cl2 )

Bi lm

HV: Nguyn Th Vn Anh

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

2 HClO + 2e Cl 2 + 2OH ; E ( HClO/ Cl2)= + 1.63

Cl

+
e2C2
l E; =
+

1,36

( Cl /2Cl )

2ClO2 + 8 H + + 6e Cl2 + 4 H2 O; G1 = nEF= 6 E (ClO / Cl )F

2

m :
G 1=nE
G1= 4E

F nE

( ClO 2/ HClO)

2E (

( ClO 2/ HClO)

10,06

10,06 F
=
6 F

10,06 F

E( ClO / Cl
=)

/HClO
) Cl

/HClO
) Cl

G1= 4 1,7

F 2 1,63
=
F
6 E( ClO / Cl=
F
)

1,676

2ClO3 +12 H + + 10e Cl2 + 6 H 2 O; G2 = nEF= 10 E ( ClO / Cl F

)
3

m : G2 = nE( ClO / ClO ) F nE(ClO / HClO ) F nE( HClO/ Cl2) F

3

G2 = 4 E( ClO / ClO ) F 4 E(ClO / HClO ) F 2 E( HClO/ Cl2) F

3

G2 = 4 1,18F 4 1, 7 F 2 1, 63F = 14, 78

10 E( ClO=/
F
Cl )
3

E( ClO =
/Cl )
3

14,78 F

14,78 F
=
10 F

1,478

2ClO4 + 16 H + + 14e Cl2 + 8 H 2 O; G3 = nEF = 14 E(ClO / Cl ) F

4

HV: Nguyn Th Vn Anh

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

m : G 3 = nE (ClO 2 / ClO F
nE
)
4

G3 = 4E ( ClO 2 / ClO )F 4E ( ClO

4

F nE

( ClO3 / ClO
2 )

F
4E ( ClO

/ ClO
2 )

F nE (

/ HClO )

G3 = 4 1, 2F 4 1,18F 4 1, 7F
2 1,63=
F

14 E( ClO / Cl
=
F
)
4

19,58 F
=
14 F

2E (

HClO
/
)Cl 2

HClO
/
)Cl 2

19,58

19,58 F

E( ClO / Cl
=)

( ClO
2 / HClO )

1,4

S OXH
(n)
+7
+5
+3
+1
-1

nE
9,8
7,93
5,028
1,63
-1,36

th Frost ca Clo

10

(ClO4)-

(ClO3)-

nE0,V

(ClO2)-

Series1

4
2

Cl2

0
-2

-1 Cl- 0
-2

S OXH

Cu 4:

HV: Nguyn Th Vn Anh

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

2+

E ( MnO 4 /Mn )
6 4 4 4 4 4 4 4 4 4 4 4 4 4 44
7 4 4 4 4 4 4 4 4 4 4 4 4 4 4 48
E
/ Mn )
6 4 4 4 4 4 4 4 44( MnO
7 24
4 4 4 4 4 4 4 48

+0.56

2
+ 2.27
+ 0.95
+3
+ 1.51
+2
1.18
MnO4
MnO4
MnO2
Mn
1 4
4 4
4 44Mn
2 4
4 4
4 4Mn
43

3+

1 4 4 4 4 4 4 4 4 4 4 44 2 4 4 4 4 4 4( Mn4/Mn4) 4 4 4 43
E

( MnO42/ Mn )

MnO4 + 7e + 8H + Mn + 4 H 2O; G1 = nEF = 7 E( MnO / Mn ) F

4

m : G1 = nE
( MnO
4

G1 = 1.
E( MnO

/ MnO24 )

/ MnO24 )

nE
( MnO2

/ MnO
2 )

F 2 E( MnO2

/ MnO
2 )

nE

( MnO

F 1 E( MnO

/ MnO3

/ MnO3

F+ nE

( Mn3 / Mn2

F + 1 E( Mn3 / Mn2

7 E( MnO / Mn ) F = 5, 2 F
4

5, 2 F
= 0, 743
7 F

MnO42 + 6e + 8H + Mn + 4H 2O ; G2 = n EF= 6E ( MnO 2 / MnF

)
4

m: G2 = nE
( MnO2
4

G2 = 2 E( MnO2
4

/ MnO2 )

/ MnO2 )

nE
( MnO

F 1 E( MnO

/ MnO3 )

/ MnO3 )

nE

( Mn3

F 1 E( Mn3

G2 = 4.54

F 0,95 F 1, 51
F 2, 36
+ F

/ Mn2+ )

/ Mn2+ )

nE

F
( Mn2 / Mn0 ) +

F+ 2 E( Mn2 / Mn0 ) +F

4, 64
= F

6 E( MnO2 / Mn ) F = 4, 64 F
4

E( MnO2 / Mn ) =
4

4, 64 F
= 0, 773
6 F

MnO2 + 4 e + 4 H + Mn + 2 H2 O; G3 = nEF = 4 EMnO

(
2

m : G3 = nE
( MnO

G3 = 1 E( MnO

/ MnO3+ )

/ MnO3+ )

F 1 E( Mn3

nE
( Mn3
+

/ Mn2

G3 = 0,
95 F 1,51 F 2,+36 F

HV: Nguyn Th Vn Anh

/ Mn2

)+

)+

nE

( Mn2

F 2 E( Mn
2

+0
/ Mn
)

+0
/ Mn
)

Mn
/
)

0,1
= F

Lp: CH 19 ho hc

nE
+
( Mn2

F 2+ E( Mn2

G1 = 0,
56 F 4.54
F 0, 95 F 1, 51 2,
F 36F = + 5, 2F

E( MnO / Mn ) =

/M

/ Mn0 )

Bi kim tra iu kin mn: L THUYT HO V C CAO

4 E( MnO / Mn ) F = 0,1F
4

E( MnO2 / Mn ) =
4

0,1F
= 0, 025
4 F

Mn 3+ + 3e Mn; G 4 = n EF = 3E ( Mn3+ / Mn )F

m : G 4=nE
G4= 1E

nE

( Mn 3+/ Mn 2+ )

2E

( Mn 3+/ Mn 2+ )

G4= 1,51F
+

2,36
=F

+2
( Mn
/ Mn0)

+ 2
( Mn
/ Mn0)

0,85F

3E( Mn 3+/ Mn
=)F 0,85 F
0,85 F
=
0,283
3F
Mn 2+ + 2e Mn ;E ( Mn 2+/ Mn
=
1,18
)

E( Mn 3+/ Mn
=)

S OXH
(n)
+7
+6
+4
+3
+2
0

HV: Nguyn Th Vn Anh

nE
5,2
4,64
0,1
-0,849
-2,36
0

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

th Frost ca Mn
6
(MnO4)(MnO4)2-

5
4

E 0,V
n

3
2
Seri

1
0
-1
-2
-3

MnO2

Mn
0

4
Mn3+

Mn2+
s OXH

bn nhit ng i vi nhng trng thi bn di ca gin .nm v tr cng

thp trong gin , bn nhit ng cng cao Nhng hnh thi trn vng li ca
ng biu din thng km bn, c th thc hin s d phn
Ta c:

3MnO42 + 4 H + 2 MnO4 + MnO2 + 2 H 2O

(1)

Hng s cn bng ca phn ng l:

G0= - RTlnK1= - nE0 F
lgK1 = nE0 F/RT

HV: Nguyn Th Vn Anh

Lp: CH 19 ho hc

Bi kim tra iu kin mn: L THUYT HO V C CAO

2 Mn 3+ + 2 H 2O Mn 2+ + MnO 2 + 4 H+

HV: Nguyn Th Vn Anh

(2)

Lp: CH 19 ho hc