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BI TP NHIT NG HA HC-2

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

1. Tnh nhit to thnh ca N2H4 khi bit:


1
N 2( k) +
O2( k)NO2( k) =
H1
kJ 33,18
2
1
H 2( k) +O2( k)H 2O( k) =H
2
kJ 241,6
2
N 2H 4( )k +
O32( )kNO
2 2(+)k H22O
( )k=
H3
467,44
kJ
2. Trong nhin liu y tn la, hidrazin lng phn ng vi hidropeoxit lng to ra nit v hi nc.
Vit p v tnh nhit to ra khi 1m3(ktc) kh N2H4 phn ng, bit nhit to thnh ca H2O2(l) l :-187,8kJ/ mol.
0
Cu 8 : Butadien 1,3 trng thi kh trong iu kin 25 C v 100 kPa.
1
0
0
a) Tnh Nhit to thnh chun ca n 25 C khi bit:
H 298 K theo kJ.mol :
0
0
H t chy C4H6 = 2552,73 ; H sinh H2O (l) = 285,83;
0
0
H sinh CO2 (k) = 393,51; H thng hoa C(r) = 716,7
0
b) Tnh Nhit to thnh chun ca n 25 C khi bit cc tr s nng lng lin kt:
HH
CC C=C
CH
1
436
345
615
415
kJ. mol
c) So snh kt qu ca 2 phn trn v gii thch.
Cu 9 Mt ni hi bng thp c khi lng 900 kg. Ni hi cha 400 kg nc. Gi s hiu sut s dng
nhit ca ni hi l 70 %. Cn bao nhiu calo nhit nng nhit ca ni hi t 10oC ln 100oC ? Nhit
dung ring ca thp l 0,46 kJ/mol, nhit dung ring ca nc l 4,184 kJ/mol.
Cu 10 : tan ca Mg(OH)2 trong nc 180C l 9.10-3 g/ ; cn 1000C l 4.10-2 g/.
a/ Tnh tch s tan ca Mg(OH)2 2 nhit trn.
b/ Tnh cc i lng H0, G0 v S0 ca phn ng ha tan, gi s H0, S0 khng thay i theo nhit
. Bit R = 8,314 J.mol.k-1.
Cu 11:
1. a/ Khi trung ha 1mol axit mnh bng 1 mol baz mnh trong dd long , nhit ta ra H=-57,32kJ .
Entanpi to thnh nc lng l -285,81kJ/mol; Entanpi to thnh H+=0. Hy xc nh Entanpi to thnh OH-(aq)
b/ Khi trung ha 1mol HCN bng kim mnh , thy gii phng ra 12,13kJ nhit. Tnh H ca phn ng
in li HCN
2. a/ Vi phn ng tng hp NH3, 673K c hng s cn bng K1= 1,3.10-2 ; 773K c hng s cn bng K2=
3,8.10-3. Xc nh H trong khang nhit .
b/ Mun tng hiu sut phn ng tng hp NH3, nn tin hnh p nhng iu kin no v nhit , p sut ?
Cu 12: Cho phn ng
aA + bB
dD + eE
d
e
C .C
0
Bit G = G + RTln aD Eb Vi C l nng ti thi im ang xt.
CA .CB
c
CdD .CeE

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

Hi cc hn hp c thnh phn sau y s phn ng theo chiu no?


a) CH2 = 2,5mol / l ; CI2 = 4mol / l ; CHI = 10mol / l
b) CH2 = 0,2mol / l ; CI 2 = 0,8mol / l ;
c) CH2 = 0,25mol / l ; CI 2 = 2mol / l ;
HT

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

2) Ta thy vi phn ng:


0

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

G < 0 : phn ng xy ra theo chiu thun;

th

G > 0 : phn ng xy ra theo chiu nghch;

th

G = 0 : phn ng t ti trng thi cn bng.

(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

G 0 = 8,314.298 n 2,41.10 -11


T

G 0 = 60.573,7J.mol -1 = 60,5737 kJ.mol -1


G0 = - H0 T. S0
H 0 G 0 49243,8 60573,7
S 0 =
=
T
298
0
-1
-1
S = - 38,02 J.mol . k

P S
Nhit lng l 268405,7 kJ

GII
a) C4H6 + 5,5 O2 4CO2 + 3H2O
0

H (chyC4H6) = 4H (sinhCO2) + 3H (sinh H2O) H (sinhC4H6)


0

H (sinhC4H6) = 4 (393,51) + 3( 285,83) ( 2552,73) = 121,2 kJ/mol


0

b) H (sinhC4H6) = 4H (thng hoaCrn) + 3E(HH) 6 E(CH) E(CC) 2E(C=C )


= (4 2866,8) + (3 436) (6 415) (345) (2 615) = 109,8 kJ/mol
c) Nng lng lin kt theo tnh ton khng ph hp vi kt qu thc nghim (lch ti 10%), ln hn thng
thng do c s khng nh v ca my lm cho phn t bn vng hn so vi m hnh lin kt cng ho tr
nh v.
CH2

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

4N2 + 8H2 4N2H4


H
H= -H1+3H3+H3-H4
= 1011-3.317-143+286
=203KJ.
- Nhit to thnh N2H4:
HN2H4 = 203/4 = 50,75KJ.mol-1
b/
N2O + 3H2 N2H4 + H2O
H2= -317
H2= HN2H4 + HH2O HN2O
HN2O= HN2H4 + HH2O H2
= 50,75 286 + 317
= 81,75KJ.mol-1
c/

2HN3 + 0,5O2 N2H4 + H2O


H3
H3=HN2H4 + HH2O 2.HNH3
=> HNH3=(HN2H4 + HH2O H3)/2
HNH3=(50,75-286+143)/2
=-46,125KJ.mol-1.
GII
1.Nhit to thnh ca N2H4 l
Ta c:

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

K = e 8,314.298 = e 237 = 10103


d) H = U + p. v = U + nRT
U = H - nRT trong n = 1 2,5 = -1,5
U = -143000 + 1,5. 8,314. 298 = -139kJ
GII
CO( k ) + H 2 O(l ) H 2( k ) + CO2( k )
a/
o
o
o
o
o
G298
pu = GH 2( k ) + GCO2( k ) GCO( k ) GH 2O( l )

= 0 + (-394,007) + 137,133 + 236,964 = -19,91 kJ.mol-1..


p dng phng trnh ng nhit Van Hoff, ta c:
GTo = RT ln K p = RT .2,303.lg K p
K p = 10

GTo
2,303. RT

= 10

19,91.103
2,303.8,314.298

= 3, 49

b/ xt PH 2O ( h ) 25oC ta xt cn bng 25oC.

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

V PH 2O (l ) = const = 1atm PH 2O ( h ) = 0, 0312atm ( 25oC)


c/ V iu kin T; V = const p sut ring phn t l vi s mol mi kh nn c th tnh p sut ring phn
theo phn ng:
CO( k ) + H 2 O( l ) (d) H 2( k ) + CO2( k )
Ban u:
1
1
1
(atm)
Cn bng: 1 x
1+x
1+x
[PH 2 ].[PCO2 ] (1 + x ) 2
Kp =
=
= 3, 49 x = 0,421
[PCO ]
1 x
Vy ti thi im cn bng 25oC:
[PCO ] = 1 x = 0,579 (atm)
[PH 2 ]=[PCO2 ] = 1 + x = 1,579 (atm)
GII
1. 4HCl
KP =

+
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

3. Da vo cc s liu bi ton, suy ra


Mun tng hiu sut oxi ha HCl cn:
- H nhit .
- Tng p sut
- Tng nng O2
Gii
iu kin chun (1 atm v 250C) :
0
0
H0p = HS(N 2O4 ) 2 HS(NO2 ) = 2309 2.8091 = 13873 (cal/mol)..
0
0
S0p = S( N2O4 ) 2 S( NO 2 ) = 72,7 2.57,5 = 42,2 (cal.mol1.K1) .
p dng : G0T = H0p TS0p tnh G cc nhit khc nhau. (V H0 v S0 bin thin khng ng
k theo nhit , nn c th s dng tnh G cc nhit khc nhau theo cng thc nu ra.)
a) 00C, tc 273K :
G0273 = 13873 + 42,2.273 = 2352 (cal/mol) . .
G0273 < 0, vy nhit ny phn ng din ra theo chiu thun
b) 1000C, tc 373K :
G0373 = 13873 + 42,2.373 = +1868 (cal/mol) > 0 ..
Vy phn ng lc ny din ra theo chiu nghch. .
c) Khi phn ng t trng thi cn bng nhit T no th G0T = 0.
Khi : 13873 + 42,2.T = 0
13873
T=
= 329 (K) hay 560C ..
42, 2
nhit t > 560C (hay T > 329K) th :
G0T = 13873 + 42,2T > 0, phn ng din ra theo chiu nghch.
nhit t < 560C (hay T < 329K) th :
G0T = 13873 + 42,2T < 0, phn ng din ra theo chiu thun

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