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Cu 1. Phn ng nh hp NO2 :
2NO2 (k) N2O4 (k)
Bit H0S (kcal/mol) :
8,091
2,309
0
1
1
S (cal.mol .K ) :
57,2
72,2
Tnh bin thin nng lng t do ca p 00C v 1000C. Cho bit chiu t din bin ti nhng nhit .
X nhit no th G = 0 ? Xc nh chiu ca phn ng nhit cao hn v thp hn nhit .
Gi thit H v S ca cc cht thay i theo nhit khng ng k.
Cu 2: Cho:
O2(k)
Cl2(k)
HCl(k)
H2O(k)
0
205,03
222,9
186,7
188,7
S 298 (J/mol.K)
0
0
0
-92,31
-241,83
H 298
(kJ/mol)
1. Tnh hng s cn bng ca phn ng 2980K
4HCl(k)
+ O2(k) 2Cl2(k
+ 2H2O(k)
2. Gi thit H v S khng ph thuc vo nhit , tnh hng s cn bng ca phn ng 6980K.
3. Mun tng hiu sut phn ng oxi ha HCl th nn tin hnh phn ng nhng iu kin no?
Cau 3: Ti 25oC, G o to thnh cc cht nh sau: (theo kJ.mol-1)
H2O(k)
CO2(k)
CO(k)
H2O(l)
-228,374
-394,007
-137,133
-236,964
CO2( k ) + CO2( K ) ti 25oC
a. Tnh Kp ca phn ng: CO( K ) + H2O ( l )
b. Tnh p sut hi nc ti 25oC
c. Hn hp gm cc kh CO, CO2, H2 m mi kh u c p sut ring phn l 1 atm c trn vi nc (lng,
d). Tnh p sut ring phn mi kh c trong hn hp cn bng ti 25oC, bit qu trnh xy ra khi V = const.
Cu 4: iu kin chun, entanpi phn ng v entropi ca cc cht c gi tr nh sau:
Phn ng
H0298(kJ)
2NH3 + 3N2O 4N2 + 3H2O
-1011
N2O + 3H2 N2H4 + H2O
-317
2NH3 + O2
N2H4 + H2O
-143
H2 + O2 H2O
-286
0
0
S 298(N2H4) = 240 J/mol. K
S 298(H2O) = 66,6 J/mol. K
S0298(N2) = 191 J/mol. K
S0298(O2) = 205 J/mol. K
a) Tnh entanpi to thnh ca H0298 ca N2H4, N2O v NH3, S0298
b) Vit phng trnh ca phn ng chy hirazin to thnh nc v nit
c) Tnh nhit phn ng chy ng p 298K v tnh G0298 v tnh hng s cn bng K
d) Nu hn hp ban u gm 2 mol NH3 v 0,5 mol O2 th nhit phn ng 3 th tch khng i l bao nhiu?
Cu 5 :
1./ Cho bit sinh nhit chun ( Ho ) ca ( O3 ) kh = +34Kcal/mol ,
o
( H ) ca ( CO2 ) kh = -94,05 Kcal/mol,
( Ho ) ca ( NH3 ) kh = -11,04 Kcal/mol
( Ho ) ca ( HI ) kh = + 6,2Kcal/mol
a./ Sp xp theo th t tnh bn tng dn ca cc n cht hp cht : O3 , CO2 ,NH3 ,v HI gii thch ?.
b./ Tnh nng lng lin kt E N-N ,bit EH-H = 104Kcal/mol v EN-H = 93 Kcal/mol
2./Cho phn ng :
H2O ( k ) + CO ( k ) H2 ( k ) + CO2 ( k )
o
o
Tnh H 298oK v E 298oK bit rng H o 298oK cu CO2 ( k ); H2O ( k ) , CO ( k ) ln lt l -94,05 , 57,79 ; - 26,41 Kcal/ mol
Cu 6: Cho cc s liu nhit ng ca mt s phn ng sau 298oK.
2NH3 + 3N2O 4N2 + 3H2O H1= -1011KJ/mol
N2O + 3H2
N2H4 + H2O H2= -317KJ/mol
2NH3 + 0,5O2 N2H4 + H2O H3= -143KJ/mol
H2 + 0,5O2
H2O
H4= -286KJ/mol
Hy tnh nhit to thnh ca N2H4, N2O v NH3.
Cu 7 :Cht lng N2H4 c th dng lm nhin liu y tn la
S th t
1
2
3
4
G
=
RTln
=
1) Chng minh rng:
Vi c
v Kc l hng s cn bng ca phn ng.
Kc
CaA .CBb
0
425 C
2HI(k)
2) vi phn ng: H2(k) + I 2(k)
K C = 50
CHI = 5mol / l
CHI = 5mol / l
GII
0
1) Theo bi, ta c G = G + RTlnc (1)
G0 = RTlnC
Khi h t ti cn bng th G = 0
G0 = RTlnK C
Lc c tr thnh Kc nn
Vy thay G0 vo (1) ta c: G = RTlnK c + RTlnc = RTln
c
(0,25)
Kc
425 C
2HI(k)
H2(k) + I 2(k)
Xt t s
K C = 50
c
:
Kc
c
<1 c < K c
Kc
c
nu
>1 c > K c
Kc
c
nu
=1 c = K c
Kc
nu
th
th
th
(10)2
= 10 < 50
ne
n
G < 0 phn ng xy ra theo chiu thun
2,5.4
(5)2
= 156,25 > 50
ne
n
G > 0 phn ng xy ra theo chiu nghch
T b) c =
0,2.0,8
(5)2
=
= 50 = K c
ne
n
G = 0 h ang trng thi cn bng
T c)
c
0,25.2
T a) c =
GII
1. a/ Phn ng trung ha : H+(aq) + OH-(aq) H2O(l) H = -57,32kJ
ttOH = ttH 2O ttH + = 285,81 0 + 57,32 = 228, 49kJ / mol
b/ Phn ng trung ha HCN bng kim mnh :
H1= -12,13 kJ
(1) HCN(dd) + OH- H2O(l) + CN-(aq)
H2 = -57,32kJ
(2) H+(aq) + OH-(aq) H2O(l)
Ly (1) - (2) HCN(dd) H+(aq) + CN-(aq) H3 =-12,13-(-57,32)= 45,19kJ
2.a/
p
dng
phng
0
K
1 1
log 2 =
K1
2,303R T2 T1
3,8.103
0 1
1
=
2
1,3.10
2,303.R 673 773
0, 47.2,303.8.314
0 =
= 4, 68.104 J
1,932.104
b/ N2(K) + 3H2(K) 2NH3(K)
H < 0
Mun tng hiu sut tng hp NH3 cn phi :
- Tng p sut ca h
- Gim nhit ca h
log
GII
Trong dung dch :
trnh :
Mg( OH ) 2( R )
s
][
Mg 2 + 2OH
ks
2s
k s = Mg 2+ OH
= s.( 2 s ) = 4 s 3
- 180C hay 291k :
9.10 3
s=
mol/
58
- 2
9.10 3
11
k s1 =
= 1,495.10
58
- 1000C hay 372k :
s=
4.10 2
mol/
58
3
k s2
4.10 2
9
=
= 1,31210
58
b/ T G0 = H0 T. S0
v G0 = - RT nks
0
v H , S0 khng thay i theo nhit , nn :
G 0
H 0 S 0
nk s1 =
=
+
RT1
RT1
R
nk s 2 =
G 0
H 0 S 0
=
+
RT2
RT2
R
H 0 H 0
RT2 RT1
H 0 1
1
=
R T2 T1
nk s 2 nk s1 =
ln =
k s2
k s2
H 0 = R.
ks
T1 .T2
ln 2
T1 - T2 k s 2
H 0 = 8,314.
291.373 1,312.10 9
ln
= 49243,8J.mol -1
11
373 291 1,495.10
H 0 = 49,2438kJ.mol -1
Mun tnh G0 phi tnh tch s tan ks 298k (250C)
T
T
T
ks
H 0
=
ks1
R
1 1
49243,8 1
1
=
= 0,4781
8,314 298 291
T T1
ks
= 0,4781 k s = 2,41.10 11
-11
1,495.10
G0 = - RTnks
n
P S
Nhit lng l 268405,7 kJ
GII
a) C4H6 + 5,5 O2 4CO2 + 3H2O
0
CH
CH
CH2
1
S khc nhau gia 2 nhit to thnh c gi l nng lng cng hng ca phn t = 11,4 kJ. mol .
GII
a/ Phng trnh cn tm:
N2 + 2H2 N2H4
-Xp cc phn ng
4N2 + 3H2O 2NH3 + 3N2O
3N2O + 3.3H2 3.N2H4 + 3H2O
2NH3 + 0,5O2 N2H4 + H2O
H2O H2+ 0,5O2
-H1
3.H2
H3
-H4
H 3 = 2 H NO
2( k )
+ 2 H H O H N H
3 HO
2 4( k )
2 (k)
2( k )
H N H
= (2 H NO
+ 2 H H O ) +3 HO
H3
2 4( k )
2 (k)
2( k )
2( k )
= [(2.33,18) + 2. ( 241, 6)] + 0 ( 467, 44)
= 50, 6 kJ / mol
2. N2H4(k) + H2O2(k) N2(k) + 2H2O(k)
H pu = 2H H O (k ) [( H H O (k ) + H N H )]
2 4( k )
2
2 2
= 2(241, 6) [( 187,8) + 50, 6]
= 346 kJ
l:
Khi 1 mol kh N2H4 phn ng to ra 346 kJ. Vy nhit lng to ra khi t chy 1m3 kh N2H4 (ktc)
1000.( 346)
= 15.44, 43 kJ
22, 4
GII
a./ V sinh nhit cng m tc nng lng cng ta nhit ra nhiu th hp cht cng bn . Do th t bn
tng dn l : O3 < HI < NH3 < CO2
b./ Xt phn ng N2 + 3H2 2NH3 th H P = 2.-11,04Kcal
Ta c : E N-N + 3 x E H-H - 2 x E N-H = 2 x -11,04
Suy ra E N-N = - 22,08 (3 . 104 -6 . 93 ) = 223,92 Kcal/mol
2./
a) Tnh Ho 298oK
Ho = Ho CO2 - Ho H2O - Ho CO
= -94,05 - ( -57,79 ) - ( - 26,41 ) = -9,85Kcal
b) Tnh Eo 298oK
Ta c Ho = Eo + RT n vi n = 2 - 2 = 0
Vy Ho = Eo = -9,85Kcal ( 1 )
GII
a) Ta c (1) + 3(2) + (3) (4) 4N2 + 8H2 4N2H4
H0298 = 1011 + 3.(-317) + ( -143) + 286 = 203kJ
N2 + 2H2 N2H4
H0298 = 50,8kJ / mol
* T 2 : 0 + H0298 (N2O) 50,8 + 286 = 317
H0298 (N2O) = 81,88kJ / mol
* T 3: 50,8 286 -2. H0298 (NH3) = -143
H0298 (NH3) = -45,6 kJ / mol
b) N2H4 + O2 N2 + 2H2O
c) H0298 = -2.286 -50,8 = -623 kJ
S0298 = 191 + 2.66,6 205 240 = 121 J/K
G0298 = H0298 + T. S0298 = -623 + 298.121 = -587kJ
587000
GTo
2,303. RT
= 10
19,91.103
2,303.8,314.298
= 3, 49
H 2 O( h)
H 2O( l )
o
o
o
1
G298
pu = GH 2O( h ) GH 2O( l ) = 228,374 + 236,964 = 8,59 kJ .mol
K p = 10
[PH 2O ( h ) ]
[PH 2O (l ) ]
GTo
2,303. RT
= 10
8,59
2,303.8,314.10 3.298
= 0, 0312
= 0, 0312
+
O2
2
2
PCl2 .PH 2O
2Cl2
2H2O
4
PHCl
.PO2
0
0
H 0 Phn ng = 2H ( H 2O ) 4H ( HCl ) = 114,42kJ
0
0
0
0
S 0 Phn ng = 2S(Cl2 ) + 2S(H2O) (4S(HCl) + S(O2 ) ) = 128,63(J / K )
G 0 = H 0 T .S 0
=-114420 + 298.128,63 = -76088,26(J)
G
= 13,34 K P = 1013,34
Vy : lg K P =
2,3.K .T
K 698
K 698
H 1
1
=
= 26,47
2. ln
ln
K 298
R 698 298
K 298
hay KP(698) = 101,8