I.

M u
Trong qu trnh ging dy trng ph thng nhim v pht trin
t duy cho hc sinh l nhim v rt quan trng, i hi tin hnh ng
b cc mn, trong Ha hc l mn khoa hc thc nghim cp
n nhiu vn ca khoa hc, s gp phn rn luyn t duy cho hc
sinh mi gc c bit l qua phn bi tp ha hc. Bi tp ha
hc khng nhng c tc dng rn luyn k nng vn dng, o su v
m rng kin thc hc mt cch sinh ng, phong ph m cn
thng qua n tp, rn luyn mt s k nng cn thit v ha
hc, rn luyn tnh tch cc, t lc, tr thng minh sng to cho hc
sinh, gip hc sinh hng th trong hc tp. Qua bi tp ha hc gio vin
kim tra, nh gi vic nm vng kin thc v k nng ha hc ca
hc sinh.
gio vin bi dng hc sinh kh, gii trng chuyn d thi hc
sinh gii cp Tnh v cp Quc gia c tt th nhu cu cp thit l cn
c mt h thng cu hi v bi tp cho tt c cc chuyn nh : cu
to cht, nhit ho hc, ng ho hc, cn bng ho hc,....
V vy , trong qu trnh ging dy i tuyn hc sinh gii Tnh
v Quc gia ti su tm v tp hp li mt s cu hi v bi tp theo
mt s chuyn , trong c phn dng luyn tp cho hc sinh
phn Nhit ho hc
II. Mc ch ca ti
Xy dng h thng cu hi v bi tp phn Nhit ho hcdng
cho hc sinh lp chuyn Ho hc bc THPT gip hc tr hc tt hn v
chun b tt hn cho cc k thi hc sinh gii Ha hc c v l thuyt
bi tp phng php gii, gp phn nng cao cht lng ging dy v
hc tp mn Ha hc.
III. Ni dung
A- C s L thuyt :
Trc khi a ra h thng bi tp cho hc tr luyn tp th gio vin
cn phi yu cu hc tr nh li mt s khi nim v ni dung l thuyt
c bn ca phn Nhit ho hc nh sau:
- 1 -
1) Kh l tng:
* Kh l tng l cht kh m khong cch gia cc phn t kh xa
nhau, c th b qua tng tc gia chng.
* Vi kh l tng th c th p dng :
- Phng trnh trng thi: P.V = nRT (R = 8,314 J/mol.K =
0,082 l.atm/mol.K)
- Trong bnh c hn h p khth: P = P
i
=
V
n
i
.RT
cn
P
i
= N
i
.P = .P
n
i
n
i

2) H v mi trng:
- H m: h trao i cht v nng lng vi mi trng.
- H kn: H ch trao i nng lng vi mi trng.
- H on nhit: H khng trao i nhit vi mi trng.
* Quy c:
H nhn nng lng ca mi trng nng lng mang du +
H nhng nng lng cho mi trng nng lng mang du -
3) Bin i thun nghch:
Nu h chuyn t trng thi cn bng ny sang trng thi cn bng
khc mt cch v cng
chm qua lin tip cc trng thi cn bng th s bin i ny c gi
l thun nghch. y l s bin i l tng khng c trong thc t.
4) S bin i bt thun nghch: l s bin i c tin hnh vi
vn tc ng k. Nhng phn ng trong thc t u l bin i bt
thun nghch.
5) Hm trng thi: l hm m gi tr ca n ch ph thuc vo cc
thng s trng thi ca h, khng ph thuc vo nhng s bin i tr-
c .
V d: P.V = hm trng thi
P
1
.V
1
= n.RT
1
; P
2
.V
2
= n.R.T
2
6) Cng (W) v nhit (Q)
- L 2 hnh thc trao i nng lng.
- 2 -
- W, Q khng phi l hm trng thi v gi tr ca chng ph thuc vo
cch bin i.
V d: Cng ca s gin n kh l tng t th tch V
1
n V
2
t
o
=
const trong 1 xilanh kn nh 1 pittng c tnh bng cng thc:
W = -
dV P
n
.
2
1

(P
n
: p sut bn
ngoi)
* Nu s bin i l BTN th P
n
= P
kq
= const
W
BTN
= - P
kq
.
dV

2
1
= - P
kq
. V = - P
kq
.(V
2
- V
1
)
* Nu s bin i l thun nghch: Gim P
n
nhng lng v cng b
th tch kh tng nhng lng v cng b. Khi P
n
mi lc thc t = P
bn trong xi lanh = P
k
P
n
= P
k
= n.RT/V
W
TN
= -
dV P
n
.
2
1

= - nRT .

2
1
V
dV
= - nRT .ln
1
2
V
V
W
BTN
W
TN
* Cc qu trnh thun nghch sinh cng ln nht khi h bin i t
trng thi 1 sang trng thi 2. Lng cng ny ng bng lng cng cn
thit a h v trng thi ban u mt cch thun nghch.
7) Ni nng U:
- U ca mt cht hay mt h gm ng nng ca cc phn t v th
nng tng tc gia cc phn t trong h .
- U l i lng dung v l hm trng thi
- U ca n mol kh l tng ch ph thuc vo nhit .
8) Nguyn l I ca nhit ng hc: (S bin i ni nng ca
h).
U = U
2
- U
1
= W + Q
- i vi s bin i v cng nh: dU =
W
+
Q

( : Ch nhng hm khng phi l hm
trng thi)
- 3 -
- Thng gp cng c thc hin ch do s bin i th tch nn:

W
= -P.dV
dU =
Q
= P .dV
dU
= Q -
dV P.
2
1

U = Q -
dV P.
2
1

* Nhit ng tch: Nu h bin i V = const dV = 0

U = Q
V
Q
V
l 1 hm trng thi.
* Nhit ng p: Nu h bin i P = const th:

dV P.
2
1

= P .
dV

2
1
= P. V
2
- P. V
1
U = U
2
- U
1
= Q
P
- P. V
2
+ P .V
1
Q
P
= (U
2
+ P.V
2
) - (U
1
+
P .V
1
)
t U + P.V = H = entanpi = hm trng thi
Q
P
= H
2
- H
1
= H = s bin thin entanpi ca h.
* Nhit phn ng:
Xt 1 h kn trong c phn ng: aA + bB cC + dD
Nhit phn ng ca phn ng ny l nhit lng trao i vi mi trng
khi a mol A phn ng vi b mol B to ra c mol C v d mol D T = const.
- Nu phn ng c thc hin P = const th nhit phn ng c gi
l nhit phn ng ng p Q
P
= H
- Nu phn ng c thc hin V = const th nhit phn ng c gi
l nhit phn ng ng tch Q
V
= U
* Quan h gia Q
P
v Q
V
Q
P
= H = (U + PV)P = U + P. V H = U + P . V =
U + n .RT
Q
P
= QV + n .RT ( n = n
kh sp
- n
kh p
)
Khi n = 0 Q
P
= Q
V
hay H = U
U = Q
V
= n .C
V
. T
H = Q
P
= n .C
P
. T
- 4 -
* Nhit dung mol ng p (C
P
) l nhit lng cn cung cp lm 1
mol cht nng thm 1
o
trong iu kin ng p (m trong qu trnh
khng c s bin i trng thi).
* Tng t vi C
V
: H =

2
1
.
T
T
P
dT C
; U =

2
1
.
T
T
T
dT C
C
P
, C
V
l hm ca nhit .
Vi 1 mol kh l tng: C
P
=
T
H

; C
V
=
T
U

M U = H - P. V C
P
=
T
H

=
T
U

+
T
V P

.
= C
V
+ R
Q, W: Khng phi l hm trng thi
Q
V
= U; Q
P
= H Q
V
, Q
P
l hm trng thi ch ph thuc
vo trng thi u v trng thi cui ca h m khng ph thuc
vo qu trnh bin i l thun nghch hay khng thun
nghch.
9) nh lut Hess: H ( U) ca 1 qu trnh ch ph thuc vo trng
thi u v trng thi cui ca h m khng ph thuc vo ng i.
Hp = Hs (sn phm) - Hs (cht u) = Hc (cht u) -
Hc (sn phm)
10) nh lut Kirchhoff:

n
1
A + n
2
B n
3
C + n
4
D
T
2
H
2
H
a
H
b

n
1
A + n
2
B n
3
C + n
4
D
T
1
H
1
Theo nh lut Hess: H
2
= H
a
+ H
1
+ H
b
M:
H
a
=

+
2
1
). . . (
2 1
T
T
P P
dT C n C n
b A
= -

+
2
1
). . . (
2 1
T
T
P P
dT C n C n
B A
H
b
=

+
2
1
). . . (
4 3
T
T
P P
dT C n C n
D C

- 5 -
H
2
= H
1
+

+ +
2
1
)]. ( ) . . [(
2 1 4 3
T
T
P P P P
dT C n C n C n C n
B A D C
= H
1
+

2
1
.
T
T
P
dT C
- H
1
thng c xc nh iu kin chun: H
o
T
= H
o
298
+

T
o
P
dT C
298
.
Vi C
o
P
= C
o
P
(sp) - C
o
P
(tham gia)
C
o
P
l nhit dung mol ng p iu kin chun (1atm).
- Trong khong hp ca nhit c th coi C
o
P
= const
Th: H
2
= H
1
+ C
P
.(T
2
-T
1
)
H
o
T
= H
o
298
+ C
o
P
(T - 298)
11) Entropi (S)
- Trong s bin i thun nghch v cng nh T = const h trao i
vi mi trng mt lng nhit Q
TN
th s bin thin entropi trong qu
trnh ny l: d
S
=
T
Q
TN

S l hm trng thi (J/mol.K)

- Nu s bin i l bt thun nghch th d
S
>
T
Q
TN

- V l hm trng thi nn khi chuyn t trng thi 1 sang trng thi 2

bng bin thin thun nghch hay bt thun nghch th S
2
- S
1
= S =

2
1
T
Q
TN

( S
TN
= S
BTN
)
12) Nguyn l II ca nhit ng hc:
dS
T
Q
- Trong h c lp Q = 0. nn:
+ dS = 0: trong h c lp entropi ca h khng i nu xy ra qu
trnh thun nghch.
+ dS > 0 : trong h c lp, qu trnh t xy ra (BTN) theo chiu tng
entropi ca h v tng cho ti khi t gi tr max th h s t trng
thi cn bng.
- 6 -
* Entropi l thc o hn n ca h: hn n ca 1 h hay 1
cht cng ln khi h hay cht gm nhng ht v s dao ng ca
cc ht cng mnh (khi lin kt gia cc ht cng yu).
VD: S < S < S
S < S < S
H
2
(k) O
2
(k) O
3
(k)
H
2
O(r)
H
2
O (l)
H
2
O (h)
S l 1 i lng dung .
13) S bin thin S trong qu trnh bin i trng thi ca
cht:
Khi cht nguyn cht nng chy hoc si P = const th:
T = const S =

2
1
T
Q
=
T
H
H = nhit bin thin trng thi = L
n/c
hoc L
h
14) S trong qu trnh gin n ng nhit kh l tng:
Xt n mol kh l tng gin n th tch t V
1
V
2
t
o
= const. V ni
nng ca kh l tng ch ph thuc nhit nn trong s bin i
ny:
U = Q
TN
+ W
TN
= Q
BTN
+ W
BTN
= 0
Q
TN
= - W
TN
= nRT. ln
1
2
V
V
( = -(- P. V) =
dV
V
nRT
.
2
1

).
T = const S =
T
Q
TN
= nRln
1
2
V
V
= n.R.ln
2
1
P
P
15) S bin thin entropi ca cht nguyn cht theo nhit .
- Qu trnh P = const: un nng 1 cht nguyn cht t T
1
T
2
, khng c
s chuyn pha:
S =

2
1
T
T
TN
T
Q
Vi Q = Q
P
= dH = n.C
P
.dT
S =
T
dT
C n
T
T
P
. .
2
1

* Trong khong nhit hp, coi C

P
= const S = n.C
P
.ln
1
2
T
T
- 7 -
- Qu trnh: V = const S = n .C
V
.ln
1
2
T
T
16) Entropi tuyt i
* Nguyn l III ca nhit ng hc:
- Entropi ca cht nguyn cht di dng tinh th hon chnh 0(K) bng
0: S
(T = 0)
= 0
* Xut pht t tin trn ta c th tnh c entropi tuyt i ca cc
cht cc nhit khc nhau.
VD: Tnh S ca 1 cht nhit T no , ta hnh dung cht c
un nng t 0(K) T(K) xt P=const. Nu trong qu trnh un nng
c s chuyn pha th:
S = S
T
- S
(T = 0)
= S
T
=

5
1 i
i
S
S
T
=
T
dT
C n
T
L
n
T
dT
C n
T
L
n
T
dT
C n
T
T
h P
S
S
T
T
l P
nc
nc
T
r P
S
S
nc
nc
. . . . . . . .
) ( ) (
0
) (
1

+ + + +
Gi tr entropi c xc nh P = 1 atm = const v nhit T no
c
gi l gi tr entropi chun, k hiu l S
0
T
, thng T = 298K S
0
298
17) S bin thin entropi trong phn ng ho hc:
+ Khi phn ng thc hin P = const, T = const th: S = S(sp) -
S(t/g)
+ Nu iu kin chun v 25
0
C th: S
0
298
= S
0
298
(sp) -
S
0
298
(t/g)
+ V S ca cht kh >> cht rn, lng nn nu s mol kh sn phm
(sp) > s mol
kh tham gia th S > 0 v ngc li. Cn trong trng hp s mol kh 2
v
bng nhau hoc phn ng khng c cht kh th S c gi tr nh.
18) Th nhit ng
Sc lp = S h + S mt 0
a)Th ng p G:
- 8 -
Xt h xy ra s bin i P, T u khng i trong qu trnh ny
mi trng nhn ca h mt nhit lng H
mt
do h to ra H
mt
= - H
h
= - H
S
mt
= -
T
H
+ iu kin t din bin ca h:
S
c lp
= S
h
-
T
H
> 0 H T. S < 0
+ H trng thi cn bng khi H T. S = 0
+ t G = H TS nhit , P khng i th qu trnh xy ra theo
chiu c
G = H T. S < 0
V t ti trng thi cn bng khi G = 0.
b) Th ng tch: (Nng lng Helmholtz)
Nu h bin i iu kin T, V khng i nhit ng tch m
mi trng nhn ca cc h l U
mt
S
mt
= -
T
U
mt

iu kin t din bin ca h trong qu trnh ng nhit, ng

tch l
F = U T. S < 0
V t trng thi cn bng khi F = 0
Trong : F = U TS
V H = U + PV G = H TS = U TS + PV G = F + PV
+ i vi qu trnh T,P = const G = Wmax
+ i vi qu trnh T, V = const S = Wmax
Tm li :
* Qu trnh ng p: P = const
- Cng: WP = - P.dV = -n.R.dT WP = - P. V = - nR T
- Nhit: QP = dH = n.
P
C
.dT QP = H = n.
dT C
T
T
P
.
2
1

- Ni nng: dU = Q + W U = H P. V = H n.R. T
- 9 -
- Entropi: dS
T
Q
TN

2
1
T
Q
TN

S
TN
=
T
dT
C n
T
T
P
. .
2
1

=
T d C n
T
T
P
ln . .
2
1

Nu
P
C
= const S
TN
= n.
P
C
.ln
1
2
T
T
* Qu trnh ng tch:
- Cng: W
V
= - P.dV = 0 W
V
= 0
- Nhit: Q
V
= dU
V
= n. V
C
.dT Q
V
= U
V
=
dT n C
T
T
V
. .
2
1

Nu V
C
= const Q
V
= n. V
C
. T
- Ni nng: U
V
= Q
V
+ W
- Entropi: S
T
Q
V
=

T
dT
C n
T
T
V
. .
2
1
T d C n
T
T
V
ln . .
2
1

S n. V
C
.ln
1
2
T
T

(
V
C
= const)
- Entanpi: H = U + PV dH = dU + P.dV + V.dP = dU + V.dP
(dV = 0)
H = U + V . P
* Qu trnh ng nhit:
- Cng: W
T
= - PdV = -
dV
V
nRT
.
W
T
= -
1
2
2
1
1
2
ln ln ln . .
2
1
P
P
nRT
V
V
nRT
V
V
nRT
V
dV
RT n
V
V

- Nhit: U
T
= Q
T
+ W
T
= 0 Q
T
= - W
T
= nRT ln
1
2
V
V
- Ni nng: U
T
= 0
- Entanpi: H
T
= U
T
+ (PV)
T
= U
T
+ nR. T = 0
- Entropi: S
TN
=
nc
nc TN
T
L
T
Q

hoc =
S
h
T
L
* Vi qu trnh dn n kh l tng thun nghch
S =

T
W U
T
Q
TN
+

T
dT
C n
V
T
T
. .
2
1
dV
V
nRT
V
V

2
1
- 10 -
Nu C
V
= const S = n.
1
2
ln
T
T
C
V + nRT ln
1
2
V
V
V T = const S = nRT ln
1
2
V
V
= nRT.ln
2
1
P
P
* Qu trnh on nhit:
- Nhit: Q = 0
- Ni nng v cng: dU = Q + W = W = -PdV =
T
dT
C n
V
T
T
. .
2
1

+Qu trnh bt thun nghch:

dU
BTN
= W
BTN
= -P
ng
.dV = -P
2
.dV
U
BTN
= W
BTN
= -P
ng
.(V
2
V
1
) = n.C
V
. T
* PT Poisson: (Dng cho qu trnh thun nghch)
T .
1
V = const
P.V

= const

V
P
C
C

* W
BTN
= -P
2
(V
2
V
1
) = - P
2
.(
) ( )
1 2
1
1
2
2
T T nC
P
nRT
P
nRT
V

T
2
U = W =
.... V
2
* Qu trnh thun nghch: W = U = n.C
V
(T
2
- T
1
)
T
1
. V
1
1

= T
2
. V
1
2

T
2
= T
1
.(
2
1
V
V
)

-1
- Entanpi: H = n .C
P
(T
2
T
1
)
- Entropi: S
TN
=
T
Q
TN
= 0
* G = H TS = U + PV TS

,
_

P
T
G
- S ;

,
_

T
P
G
- V
Vi phn ng oxi ho kh c th din ra trong pin in: G = - nEF
dT
G d
= - nF.
dT
dE
= - S S = nF.
dT
dE
H = G + T. S = nF( T.
dT
dE
- E)
- 11 -
19) ngha vt l ca G:
G = H TS = U + PV TS
dG = dU + P.dV + V.dP T.dS SdT = ( W + Q) + PdV + VdP
T.dS SdT
V W = W + (-PdV)
Q T.dS dG W + VdP SdT
Du = ng vi qu trnh thun nghch v cng ln nht.
dG = W
max
+ VdP SdT
* i vi qu trnh ng nhit, ng p dP = dT = 0
dG
T,P
= W
max
G = W
max
* i vi qu trnh BTN: W gim; Q tng khi hon ton BTN W = 0
20) Mt s tnh cht ca hm G:
dG = V.dP SdT ( coi W = 0)
a) S ph thuc ca G vo T:
- Khi P = const
P
T
G

,
_

= - S
P
T
G

,
_

= - S
G = H T. S = H + T.
P
T
G

,
_

T.
P
T
G

,
_

- G = - H
2 2
.
T
H
T
G
T
G
T
P

,
_

2
T
H
T
T
G
P

,
_

dT
T
H
T
G
d
T
T
T
G
T
G
T
T
. .
2
1
2
2
1
2
1

dT
T
G
T
G
T
G
T
T
T T
.
2
1
1 2
2
1 2

Nu coi H
o
khng ph thuc vo nhit th:

,
_

298
1 1
298
298
T
H
G
T
G
o
o
T
b) S ph thuc vo P:
Khi T = const
V
P
G
T

,
_

( ) ( )


2
1
1
2
1
2
. .
2
1
P
P
P T
P
P
P T
dP V G G dP V dG
- 12 -
- Vi cht rn, lng coi V = const khi P bin thin (tr min p sut
ln) th:
( ) ( )
) (
1 2
1 2
P P V G G
P T P T
+
- Vi cht kh l tng V =
P
nRT

( ) ( )
1
2
ln .
1 2
P
P
nRT G G
P T P T
+
Nu p sut bnh thng: P
1
= P
o
= 1bar (1 atm) G
T(P)
= G
o
T
+ nRT.lnP
(P tnh bng bar (atm)).
21) Tnh G ca mt s qu trnh:
a) Gin nn ng nhit kh l tng
G = nRT.ln
1
2
P
P
= nRT.ln
2
1
V
V
b) Trn ln ng nhit, ng p 2 kh l tng:
G = n
A
.RTlnx
A
+ n
B
.RTlnx
B
c) Qu trnh chuyn pha thun nghch (ti nhit chuyn
pha): G
cf
= 0
d) Qu trnh chuyn pha thun nghch T T
cf
Nguyn tc: p dng chu trnh nhit ng. V G l hm trng thi nn
G ch ph thuc trng thi u, trng thi cui, khng ph thuc vo
qu trnh bin thin.
e) G ca phn ng ho hc: G
o
p
= G
o
S(sn phm)
- G
o
S(tham gia)
b - H thng cc cu hi v bi tp phn Nhit ha hc :
Bi 1:
Cho 100 g N
2
0
o
C, 1atm. Tnh Q, W, U, H trong cc bin i
sau y c tin hnh thun nghch nhit ng:
a) Nung nng ng tch ti P = 1,5atm.
b) Gin ng p ti V = 2V ban u.
c) Gin ng nhit ti V = 200l
d) Gin on nhit ti V = 200l
Chp nhn rng N
2
l kh l tng v nhit dung ng p khng i
trong qu trnh th nghim v bng 29,1J/mol.K
- 13 -
Gii
a) V = const W =
0 .dV P
U = QV = n V
C
. T = ( P C - R).(T
2
T
1
) .n
= (
P C - R).(
1
2
P
P
-1).T
1
.n = (29,1 - 8,314).(
) 1
1
5 , 1

.273,15 = 14194,04(J)
b) V
o
=
) ( 80 4 , 22 .
28
100
l
V= 2V
o
= 160 (l)
W = -P. V = -1(160 80) = -80 (l.at) = -80 .101,33 = -8106,4(J)
Q
P
= H = P C .n . T =

,
_

1 1
1
2
. . 1 , 29 .
28
100
T T
V
V
= 29,1.
28
100
(2.273,15
273,15) = 28388,1(J)
U = Q + W = 28388,1 = 8106,4 = 20281,7(J)
c) T = const U = 0; H = 0
W = -

2
1
.
V
dV
nRT
= - nRT.ln
1
2
V
V
W = -
28
100
.8,314 .273,15.ln
80
200
= -7431,67(J)
U = Q + W = 0 Q = -W = 7431,67(J)
d) Q = 0 (S = const)
Theo PT poisson: T
1
. V
1
1

= T
2
. V
1
2

T
2
= T
1
.(
2
1
V
V
)

-1
Vi
4 , 1
314 , 8 1 , 29
1 , 29

+

P
P
V
P
C R
C
C
C

W = U = n. V
C
(T
2
T
1
) =
28
100
(29,1-8,314).(189,33 -273,15) =
6222,4(J)
H = n
P
C
. T =
28
100
.29,1(189,33 273,15) = - 8711,3(J)
Bi 2:
Tnh
o
S
H
298 ,

ca Cl
-
(aq)
. Bit:
(a):
2
1
H
2
+
2
1
Cl
2(k)
HCl
(k)

o
S
H
298 ,

= -92,2(kJ)
(b): HCl
(k)
+ aq H
+
(aq)
+ Cl
-
(aq)

o
S
H
298 ,

= -75,13(kJ)
- 14 -
(c):
2
1
H
2
+ aq H
+
(aq)
+ e
o
S
H
298 ,

= 0
Gii:
Ly (a) + (b) (c) :
2
1
Cl
2
+ e + aq = Cl
-
(aq)

o
S
H
298 ,

= - 167,33(kJ)
Bi 3:
Tnh hiu ng nhit ca phn ng:
3Fe(NO
3
)
2(aq)
+ 4HNO
3(aq)
3Fe(NO
3
)
3(aq)
+ NO
(k)
+ 2H
2
O (l)
Din ra trong nc 25
o
C. Cho bit:
Fe
2+
(aq)
Fe
3+
(aq)
NO
3
-
(aq)
NO
(k)
H
2
O
(l)
o
S
H
298 ,

(kJ/mol) -87,86 - 47,7 -206,57 90,25 -285,6

Gii:
Phng trnh ion ca phn ng:
3Fe
2+
(aq)
+ 4H
+
(aq)
+ NO
3
-
(aq)
3Fe
3+
(aq)
+ NO
(k)
+ 2H
2
O
(l)
H=3.
o
S
H
298 ,

(Fe
3+
,aq
)+
o
S
H
298 ,

(NO)+2.
o
S
H
298 ,

(H
2
O
(l)
)3.
o
S
H
298 ,

(Fe
2+
,aq
)-
o
S
H
298 ,

(NO
3
-
, aq
)
= 3.(-47,7) + 90,25 + 2.(-285,6) + 3.87,6 + 206,57 = -153,9(kJ)
Bi 4:
1) So snh H, U ca cc phn ng: C
n
H
2n
+ H
2
C
n
H
2n+2
2) Khi t chy hon ton 2 anome v ca D glucoz mi
th 1 mol p sut khng i, ngi ta o c hiu ng nhit ca cc
phn ng 500K ln lt bng:
-2790,0kJ v - 2805,1kJ
a) Tnh U i vi mi phn ng.
b) Trong 2 dng glucoz, dng no bn hn?
Gii:
1) H = U + P. V = U + n.RT
Phn ng trn c: n = 1-2 = -1 H = U RT H <
U
- 15 -
2) C
6
H
12
O
6
+ 6O
2
6CO
2
+ 6H
2
O
U
( )
= H
( )
- n.RT = - 2799 6.8,314.10
-3
.500 = -2824(kJ)
U
( )
= H
( )
- n.RT = - 2805,1 6.8,314.10
-3
.500 = -2830 (kJ)
o
H

= 6.
o
CO S
H
) (
2

+ 6.
o
O H S
H
) (
2

-
o
S
H
) (

o
H

= 6.
o
CO S
H
) (
2

+ 6.
o
O H S
H
) (
2

-
o
S
H
) (

o
S
H
) (

-
o
S
H
) (

=
o
H

-
o
H

= -2805,1 + 2799 = -6,1(kJ)

o
S
H
) (

<
o
S
H
) (

Dng - glucoz c
o
S
H
nh hn nn bn
hn.
Bi 5:
1) Th no l entanpi sinh ca n cht? Tnh
o
O S
H
) (
3

v
o
kimcuong S
H
) (

v d on hot tnh ho hc ca chng t cc d kin sau:

(a): C
than ch
+ O
2(k)
CO
2(k)

o
H
298

= -393,14(kJ)
(b): C
kim cng
+ O
2(k)
CO
2(k)

o
H
298

= -395,03(kJ)
(c): 3As
2
O
3 (r)
+ 3O
2(k)
3As
2
O
5(r)

o
H
298

= -811,34(kJ)
(d): 3As
2
O
3

(r)
+ 2O
3(k)
3As
2
O
5(r)

o
H
298

= -1090,98(kJ)
2) T kt qu trn v cc d kin sau:
H
(O O)
tnh t O
2
= - 493,24kJ/mol; H
(O O)
tnh t H
2
O
2
= -
137,94kJ/mol
Chng minh rng: Khng th gn cho O
3
cu trc vng kn.
Gii:
1)- Entanpi sinh ca cc n cht bn iu kin chun = 0
- i vi nhng nguyn t c nhiu dng th hnh th khi chuyn t dng
ny sang dng khc bao gi cng km theo 1 hiu ng nhit. Hiu ng
nhit ca qu trnh hnh thnh n cht (dng th hnh km bn) t
dng th hnh bn iu kin nht nh c coi l nhit sinh ca
n cht trong nhng iu kin .

o
S
H
ca O
3
v kim cng l hiu ng nhit quy v iu kin chun
ca cc qu trnh:

2
3
O
2
O
3(k) ;
C
than ch
C
kim cng
- 16 -
- Ly (a) (b):
C
than ch
C
kim cng

o
kc S
H
) (

= 1,89 kJ/mol
- Ly (c) - (d):

2
3
O
2(k)
O
3(k)

o
O S
H
) (
3

= 139,82 kJ/mol
2) Nu coi O
3
c cu trc vng kn:

o
O S
H
) (
3

=
o
O lk
H
) (
3

-
2
3
o
O lk
H
) (
2

= 3.(-137,94) -
2
3
.(- 493,24) = 326,04 (kJ/mol) >
139,82(kJ/mol)
O
3
c cu trc vng kn rt khng bn cu trc ny khng chp
nhn c.
Bi 6:
Entanpi sinh tiu chun ca CH
4(k)
v C
2
H
6(k)
ln lt bng -74,80 v
-84,60 kJ/mol. Tnh entanpi tiu chun ca C
4
H
10

(k)
. Bin lun v kt
qu thu c. Cho bit entanpi thng hoa ca than ch v nng lng lin
kt H- H ln lt bng: 710,6 v - 431,65 kJ/mol.
Gii:
* (1) C
than ch
+ 2H
2 (k)
CH
4(k)

o
CH S
H
4
,

=-74,8kJ
(2) C
than ch
C
(k)

o
th
H
= 710,6 kJ
(3) H
2 (k)
2H
(k)
lk
H
= 431,65 kJ
Ly (1) [(2) + 2.(3)] ta c:
C
(k)
+ 4H
(k)
CH
4(k)

o
CH tu ng S
H
4
, / ,

= -1648,7(kJ/mol)
Nng lng lin kt trung bnh ca lin kt C H l:
4
1
(-1648,7) = -
412,175 (J/mol).
* (4) 2C
than ch
+ 3H
2
C
2
H
6(k)

o
K H C S
H
) , (
6 2

= -84,6 (kJ/mol)
Ly (4) [2 .(2) + 3.(3)] ta c:
2C
(k)
+ 6H
(k)
C
2
H
6

(k)

o
H C tu ng S
H
6
2
, / ,

= -2800,75 (kJ/mol)
Coi E
C H
trong CH
4
v C
2
H
6
nh nhau th:
E
C- C
= =1800,75 6(- 412,175) = -327,7(kJ/mol)
- 17 -
* Coi E
C-H
; E
C- C
trong cc cht CH
4
, C
2
H
6
, C
4
H
10
u nh nhau th:
o
H C tu ng S
H
10
4
, / ,

= 3. E
C- C
+ 10.E
C- H
= 3.(- 327,7) + 10( -412,75) = -5110,6
(kJ/mol)
* (5) 4C
(k)
+ 10 H
(k)
C
4
H
10

(k)

o
H C tu ng S
H
10
4
, / ,

= -5110,6 (kJ/mol)
Ly (2). 4 + (3).5 + (5) ta c:
4Cthan ch
+ 5H
2(k)
C
4
H
10(k)

o
H C S
H
10
4
,

= -109,95(kJ/mol)
* Kt qu thu c ch l gn ng do coi E
lk(C C)
, E
lk(C- H)
trong mi tr-
ng hp l nh nhau. V v vy s khng tnh r c
o
S
H
ca cc ng
phn khc nhau.
Bi 7:
Tnh H
o
ca cc phn ng sau:
1) Fe
2
O
3(r)
+ 2Al
(r)
2Fe
(r)
+ Al
2
O
3(r)
( 1)
Cho bit
o
O Fe S
r
H
) ( 3 2
,

= -822,2 kJ/mol;
o
O Al S
r
H
) ( 3 2
,

= -1676 (kJ/mol)
2) S
(r)
+
2
3
O
2(k)
SO
3(k)
(2)
Bit (3) : S
(r)
+ O
2(k)
SO
2(k)

o
H
298

= -296,6 kJ
(4): 2SO
2(k)
+ O
2(k)
2SO
3(k)

o
H
298

= -195,96 kJ
T kt qu thu c v kh nng din bin thc t ca 2 phn ng trn
c th rt ra kt lun g?
Gii:
1)
o
pu
H
) 1 (

=
o
O Al S
r
H
) ( 3 2
,

-
o
O Fe S
r
H
) ( 3 2
,

= -1676 + 822,2 = - 853,8(kJ)

2)
o
pu
H
) 2 (

=
o
pu
H
) 3 (

+
2
1
o
pu
H
) 4 (

= -296,6 -
2
1
.195,96 = -394,58 (kJ)
KL: Hai phn ng (1), (2) u to nhit mnh. Song trn thc t 2 phn
ng khng t xy ra. Nh vy, ch da vo H khng khng
nh chiu ca 1 qu trnh ho hc (tuy nhin trong nhiu trng hp,
d on theo tiu chun ny l ng).
Bi 8:
1) Tnh hiu ng nhit ng tch tiu chun ca cc phn ng
sau 25
o
C.
- 18 -
a) Fe
2
O
3(r)
+ 3CO
(k)
2Fe
(r)
+ 3CO
2(k)

o
H
298

= 28,17 (kJ)
b) C
than ch
+ O
2(k)
CO
2 (k)

o
H
298

= -393,1(kJ)
c) Zn
(r)
+ S
(r)
ZnS
(r)

o
H
298

= -202,9(kJ)
d) 2SO
2(k)
+ O
2(k)
2SO
3(k)

o
H
298

= -195,96 (kJ)
2) Khi cho 32,69g Zn tc dng vi dung dch H
2
SO
4
long d trong
bom nhit lng k 25
o
C, ngi ta thy c thot ra mt nhit lng l
71,48 kJ. Tnh hiu ng nhit nhit . Cho Zn = 65,38
Gii:
1) H = U + n.RT
Do cc phn ng a), b), c) c n = 0 nn U
o
= H
o
Phn ng d): U
o
= H
o
- n.RT = -195,96 + 1.8,314. 298,15. 10
-3
=
-193,5 (kJ)
2) Zn
(r)
+ H
2
SO
4

(dd)
H
2(k)
+ ZnSO
4(dd)
Trong bom nhit lng k c V = const.
U = - 71,48.
38 , 65 / 69 , 32
1
= -142,96 (kJ/mol)
H = U + n.RT = - 142,96 + 1. 8,314 .298,15 .10
-3
= - 140,5
(kJ/mol)
Bi 9:
Tnh H
o
ca phn ng tng hp 1 mol adenine C
5
H
5
N
5(r)
t 5 mol
HCN
(k)
.
Cho bit
o
k CH S
H
) , ,
4

= - 74,8 (kJ/mol);
o
k NH S
H
, ,
3

= -46,1kJ/mol;
o
r adenin S
H
) ( ,

=
91,1 kJ/mol
V CH
4(k)
+ NH
3(k)
HCN
(k)
+ 3H
2(k)
H
o
= 251,2 kJ.mol
-1
Gii:
(a) : C
gr
+ 2H
2(k)
CH
4

o
k CH S
H
) , ,
4

= -74,8 (kJ/mol)
(b) :
2
1
N
2(k)
+
2
3
H
2(k)
NH
3(k)

o
k NH S
H
, ,
3

= - 46,1kJ/mol
(c) : 5C
gr
+
2
5
H
2(k)
+
2
5
N
2(k)
C
5
H
5
N
5(r)

o
r adenin S
H
) ( ,

= 91,1 kJ.mol
-1
(d) : CH
4(k)
+ NH
3(k)
HCN
(k)
+ 3H
2(k)
H
o
= 251,2 kJ.mol
-1
Ta ly: -5 .(a) + [-5 .(b)] + (c) + [-5.(d)] ta c:
- 19 -
5HCN
(k)
C
5
H
5
N
5(r)
H
o
(4)
= 251,2 kJ/mol
Bi 10:
Tnh nhit thot ra khi tng hp 17kg NH
3
1000K. Bit
o
k NH S
H
) , ( 298 ,
3

=
-46,2 kJ.mol
-1
) , (
3
k NH P
C
= 24,7 + 37,48.10
-3
T Jmol
-1
K
-1
) , (
2
k N P
C
= 27,8 + 4,184.10
-3
T Jmol
-1
K
-1
) , (
2
k H P
C
= 286 + 1,17.10
-3
T Jmol
-1
K
-1
Gii:
2
1
N
2(k)
+
2
3
H
2(k)
NH
3(k)

o
k NH S
H
, ,
3

= - 46,2kJ/mol
C
P
= ) , (
3
k NH P
C
-
2
1
) , (
2
k N P
C
-
2
3
) , (
2
k H P
C
= - 24,7 + 37,48.10
-3
T -
2
1
[27,8 + 4,184.10
-3
] -
2
3
[28,6 + 1,17 .10
-
3
T]
= - 32,1 + 31,541.10
-3
T

o
H
1000
o
H
298

+
dT C
P
,
1000
298

=
o
H
298

+
dT T) 10 . 541 , 31 1 , 32 (
1000
298
3

+
=
o
H
298

+
)
2
10 . 541 , 31 1 , 32 (
2 1000
298
3
T
T

+
= - 46,2.10
3
+31,541 .10
-3
.
2
1
(1000
2
-198
2
) 32,1(1000 298)= -
54364,183 (J/mol)
Khi tng hp 17 kg NH
3
th nhit lng to ra l:
Q =
17
17000
.(-54364,183 .10
-3
) = -54364,183 (kJ)
Bi 11:
Tnh nng lng mng li tinh th BaCl
2
t 2 t hp d kin sau:
1) Entanpi sinh ca BaCl
2
tinh th: - 859,41 kJ/mol
Entanpi phn li ca Cl
2
: 238,26 kJ/mol
Entanpi thng hoa ca Ba: 192,28 kJ/mol
Nng lng ion ho th nht ca Ba: 500,76 kJ/mol
Nng lng ion ho th hai ca Ba: 961,40 kJ/mol
- 20 -
i lc electron ca Cl : - 363,66 kJ/mol
2) Hiu ng nhit ca qu trnh ho tan 1 mol BaCl
2
vo mol H
2
O l:
-10,16kJ/mol.
Nhit hirat ho ion Ba
2+
: - 1344 kJ/mol
Nhit hirat ho ion Cl
-
: - 363 kJ/mol
Trong cc kt qu thu c, kt qu no ng tin cy hn.
Gii:
Ba
(r)
+ Cl
2(k)
BaCl
2

(tt)
H
th(Ba) U
ml
Ba
(k)
+2Cl
(k)
Ba
2+
+2Cl
-
I
1
(Ba) +I
2
(Ba)
2. A
Cl
U
ml
= H - H
th (Ba)
- H - I
1(Ba)
- I
2(Ba)
- 2A
Cl
=- 859,41 - 192,28 - 238,26 - 500,76 - 961,40 +2 .363,66
=- 2024,79 (kJ /mol)
H
S(BaCl
2
, tt)
H
pl(Cl
2
)
o

S(BaCl
2
, tt)
pl(Cl
2
)

o

2) BaCl
2 (tt)
Ba
(aq)
+2Cl
(aq)
- U
ml
+

H2
O
H
1 H
2
Ba
2+
+2Cl
-
H
ht(BaCl
2
)

2+
-

U
ml
= H
1
+ H
2
- H
=-1344 - 2.363 +10,16 =-2059,84 (kJ/mol)

ht(BaCl
2
)
Kt qu 1) ng tin cy hn, kt qu tnh theo m hnh 2) ch l gn
ng do m hnh ny khng m t ht cc qu trnh din ra trong
dung dch, cc ion nht l cation t nhiu cn c tng tc ln nhau
hoc tng tc vi H
2
O.
Bi 12:
Cho gin n 10 lt kh He 0
o
C, 10atm n p sut l 1atm theo
3 qu trnh sau:
a) Gin ng nhit thun nghch.
b) Gin on nhit thun nghch.
c) Gin on nhit khng thun nghch.
- 21 -
Cho nhit dung ng tch ca He C
V
=
2
3
R v chp nhn khng i
trong iu kin cho ca bi ton.
Tnh th tch cui cng ca h, nhit Q, bin thin ni nng U v
cng W trong mi qu trnh ni trn?
Gii:
a) T = const U = 0; H = 0
U = Q + W = 0 Q = -W
W = -


2
1
2
1
.
V
dV
nRT dV P
= - nRTln
1
2
V
V
Vi kh l tng: P
1
.V
1
= P
2
.V
2

1
2
V
V
=
2
1
P
P
V
2
=
2
1
P
P
. V
1
=
1
10
. 10 =
100(l)
W = -(nRT).ln
2
1
P
P
= -10.10 .ln 10 = 230,259 (l.at)
W = 230,259 .101,33 .10
-3
= 23,332 (kJ)
Q = - W = -23,332 (kJ)
b) Q = 0
U = W = n. V
C
. T =
2
3
.
.
.
1
1 1
T R
V P
.R(T
2
T
1
)
U = W =
2
3
.
.
1
1 1
T
V P
(T
2
T
1
)
Theo PT poisson: T.V

- 1
= const
M V =
P
nRT
T.
1

,
_

P
nRT
= const T

.P

- 1
= const
T
1
.P
1
=T
2
.P
2
T
1
T
2
=
P
2
P
1

T
1
T
2
P
2
P
1
=

1-
1-

1-

1-

T
2
=T
1
.
=273,15 .
P
2
P
1

1-
10
1

1-
=
C
P
C
V
C
V
+R
C
V
3
2
R +R
R
=
5
3
=
1 -
=- 0,4
=
=
3
2

1-
5
3
5
3
3
2
T
2
=273,15 .(10)
-0,4
=108,74 (K)
U =W = . (108,74 - 273,15) .101,33 =9148,6(J)
273,16
10 .10

- 22 -
V
2
= = 39,81 (l)
1 .273,15
10.10.108,74
P
2
.T
1
P
1
.V
1.
T
2
~
~
c) Q = 0 U = W
n. V
C
(T
2
T
1
) = -P
ng
.(V
2
V
1
) = -P
2
.

,
_

1
1
2
2
P
nRT
P
nRT
n.
2
3
R(T
2
T
1
) = -nR.1

,
_

10 1
1 2
T T
T
2
= 0,64T
1
V
2
= = 64(l)
T
1
. 1
10.10.0,64T
1
P
2
.T
1
P
1
.V
1.
T
2
=
U = W = -P
ng
(V
2
V
1
) = -1(64 10) = -54(l.atm)
= -54(l.atm) .101,33 .J/l.atm =
- 5471,82 (J)
Bi 13 :
Phn ng sau: Ag +
2
1
Cl
2
= AgCl
Xy ra di p sut 1 atm v 25
o
C to ra 1 nhit lng l 126,566 kJ.
Nu cho phn ng xy ra trong 1 nguyn t ganvani P, T = const
th ho nng s c chuyn thnh in nng v sn ra cng W =
109,622 kJ.
Hy chng t rng trong c 2 trng hp trn, bin thin ni nng ca h
vn ch l mt, cn nhit th khc nhau v tnh gi tr bin thin ni
nng .
Gii:
- Do U l hm trng thi nn U = U
2
U
1
= const, cho d s bin i
c thc hin bng cch no. V vy U trong 2 trng hp trn ch l
mt.
- V U = Q + W = Q + W - P V = Q + W - n.RT
Do nRT = const; U = const
Nn khi W (cng c ch) thay i th Q cng thay i
- U = H - nRT = -126,566 +
2
1
. 8,314 .298,15.10
-3
= - 125,327 (kJ)
Bi 14:
Tnh cng ca s bin i ng nhit thun nghch v bt
thun nghch 42g kh N
2
300K khi:
- 23 -
a) Gin n t 5atm n 1atm.
b) Nn t 1atm n 5atm.
(Kh c coi l l tng). So snh cc kt qu v rt ra kt lun.
Gii:
a) * W
TN
= -
1
2
1
2
2
1
2
1
ln ln
P
P
nRT
V
V
nRT
V
dV
nRT PdV

W
TN
=
28
42
.8,314 .300. ln
5
1
= -6201,39(J)
*W
BTN
= - P
ng
. V = -P
ng
(V
2
V
1
) = -P
ng

,
_

1
2
1 1
V
P
V P
= - P
2
.V
1

,
_

1
2
1
P
P
= - P
2
.

,
_

,
_

1
2
2
1
1
1 1 .
P
P
nRT
P
P
P
nRT
= -
28
42
.8,314 .300
,
_

5
1
1
= -2993,04
(J)
b) W
TN
= nRTln
1
2
P
P
=
28
42
.8,314 .300.ln
1
5
= 6201,39(J)
W
BTN
= - P
ng
. V= -P
ng
(V
2
V
1
) = -P
ng

,
_

1 2
P
nRT
P
nRT
= -nRT.P
2

,
_

1 2
1 1
P P
= -nRT

,
_

1
2
1
P
P
= -
28
42
.8,314 .300
,
_

1
5
1
=
14965,2 (J)
KL: - Cng m h thc hin (sinh) trong qu trnh bin thin thun
nghch t trng thi 1 n trng thi 2 bng cng m h nhn khi t
trng thi 2 v trng thi 1. Cn trong qu trnh bin thin bt thun
nghch th cng h sinh nh hn cng h nhn.
- Trong s bin thin thun nghch th h sinh cng ln hn trong qu
trnh bin thin bt thun nghch.
Bi 15: Phn ng: C
6
H
6
+
2
15
O
2(k)
6CO
2(k)
+ 3H
2
O
300K c Q
P
Q
V
= 1245(J). Hi C
6
H
6
v H
2
O trong phn ng trng thi
lng hay hi?
Gii:
Q
P
Q
V
= nRT = 1245(J) n =
300 . 314 , 8
1245
= 0,5
H
2
O v C
6
H
6
phi th hi th n = 0,5
- 24 -
Bi 16:
Tnh nhit lng cn thit nng nhit ca 0,5 mol H
2
O t
-50
o
C n 500
o
C
P = 1atm. Bit nhit nng chy ca nc 273K l L
nc
= 6004J/mol,
nhit bay hi ca nc 373K l L
h
= 40660 J/mol.
o
h O H P
C
) , (
2
= 30,2 + 10
-2
T(J/molK) ;
o
r O H P
C
) , (
2
= 35,56(J/molK);
o
l O H P
C
) , (
2
=
75,3(J/molK)
Gii:
H
2
O
(r)
H
2
O
(r)
H
2
O
(l)
H
2
O
(l)
H
2
O
(h)
H
2
O
(h)
(500
o
C)
H
1
H
2
H
3
H
4
H
5
-50
o
C 0
o
C 0
o
C 100
o
C 100
o
C

H
o
= h
o
l P nc
o
r P
L n dT C n L n dT C n H . . . . . .
373
273
) (
273
223
) (
5
1
+ + +

+

773
373
) (
. . dT C n
o
h P
= 0,5 .35,56(273 223) + 0,5 .6004 + 0,5 .75,3 .(373 273) + 0,5 .
40660 +
+ 0,5.30,2 .(773 373) +
2
10
2
.0,5 (773
2
373
2
) = 35172(J)
Bi 17:
Tnh s bin thin entropi ca qu trnh un nng 0,5 mol H
2
O t
50
o
C n 500
o
C P = 1atm. Bit nhit nng chy ca nc 273K =
6004J/mol; nhit bay hi ca nc 273K = 40660J/mol. Nhit dung mol
ng p
o
P
C ca nc v nc lng ln lt bng 35,56 v 75,3J/molK;
o
P
C ca hi nc l (30,2 + 10
-2
T) J/molK
Gii:
H
2
O
(r)
H
2
O
(r)
H
2
O
(l)
H
2
O
(l)
H
2
O
(h)
H
2
O
(h)
S
1 S
2
S
3
S
4
S
5

773K
373K 373K 273K 273K
223K
o
o o o o
S
2
S
3
S
4
S
5

o o o o
= + + + +
S
o
S
1

o
= n.
1
]
1

+ + + +

273
223
373
273
773
373
) ( ) ( ) (
.
373
.
273
.
T
dT
C
L
T
dT
C
L
T
dT
C
h P
h
l P
nc
r P
=0,5.
1
]
1

+ + + + +

) 373 773 ( 10
373
773
ln . 2 , 30
373
40660
273
373
ln . 3 , 75
273
6004
223
273
ln . 56 , 35
2
=
93,85(J/K)
- 25 -
Bi 18:
Tnh s bin thin entropi khi trn ln 200g nc 15
o
C vi 400g nc
60
o
C. Bit rng h l c lp v nhit dung mol ca nc lng l 75,3
J/mol.K
Gii:
Gi T l nhit ca h sau khi pha trn.
Do Q
thu
= Q
to
nn:
18
200
.
P
C (T 288) =
18
400
.
P
C (333 T)
T 288 = 2.333 2T T =
3
288 333 . 2 +
= 318(K)
S
h
= S
1
+ S
2
=
T
dT
. 3 , 75 .
18
200
318
288

+
T
dT
. 3 , 75 .
18
400
318
333

=
18
200
.75,3 ln
288
318
+
18
400
.75,3 ln
333
318
= 5,78 (J/K) > 0
Qu trnh san bng nhit ny t xy ra.
Bi 19:
Tnh s bin thin entropi v G ca s hnh thnh 1 mol hn hp
kh l tng gm 20% N
2
; 50%H
2
v 30%NH
3
theo th tch. Bit rng
hn hp kh c to thnh do s khuch tn 3 kh vo nhau bng cch
ni 3 bnh ng 3 kh thng vi nhau. Nhit v p sut ca cc kh
lc u u kc (273K, 1atm).
Gii:
V kh l tng khuch tn vo nhau nn qu trnh l ng nhit.
Gi th tch ca 1 mol hn hp kh l V th tch mi kh ban u (
cng iu kin) l
2
N
V
= 0,2V;
3
NH
V
= 0,3V;
2
H
V
= 0,5V.
Do %V = %n
2
N
n
= 0,2 mol;
2
H
n
= 0,5 mol;
3
NH
n
= 0,3mol.
- S bin thin entropi c tnh theo CT: S = nRln
1
2
V
V
2
N
S
= 0,2 .8,314.ln
V
V
2 , 0
= 2,676J/K
2
H
S
= 0,5.8,314.ln
V
V
5 , 0
= 2,881J/K
3
NH
S
= 0,3.8,314.ln
V
V
3 , 0
= 3,003J/K
- 26 -
S =
2
N
S
+
2
H
S
+
3
NH
S
= 8,56(J/K)
* Qu trnh khuch tn kh l tng l ng nhit nn H = 0
G
273
= H T. S = -273.8,56 = -2336,88(J)
Bi 20: Trong cc phn ng sau, nhng phn ng no c S > 0;
S < 0 v S 0 t.
C
(r)
+ CO
2(k)
2CO
(k)
(1)
CO
(k)
+
2
1
O
2(k)
CO
2(k)
(2)
H
2(k)
+ Cl
2(k)
2HCl
(k)
(3)
S
(r)
+ O
2(k)
SO
2(k)
(4)
Gii:
Phn ng (1) c n kh = 2 -1 = 1 > 0 S > 0
Phn ng (2) c n kh = 1 -1-
2
1
< 0 S <0
Phn ng (3), (4) c n kh = 0 S 0 t.
Bi 2 1: Cho bit p:

C
2
H
4(k)
+H
2
O
(h)
C
2
H
5
OH
(h)
v cc s liu sau:
C
2
H
5
OH C
2
H
4(k)
H
2
O
(h)

) / (
298 ,
mol kJ G
o
S

168,6 68,12 - 228,59

) / (
298
mol kJ S
o
282,0 219,45 188,72
a) Hi iu kin chun ca phn ng ny l iu kin nh th no?
b) iu kin chun v 25
o
C phn ng i theo chiu no?
c) Tnh
o
H
298

ca phn ng. Phn ng to nhit hay thu nhit?

Gii:
a) iu kin chun: ) (
4 2
k H C
P
= ) (
2
h O H
P
= ) (
5 2
h OH H C
P
= 1atm v phn ng -
c thc hin t
o
, P khng i.
b)

G
p
= G
o
- G
o
- G
o
o
S,298(C
2
H
5
OH
h
)
S,298(C
2
H
4k
) S,298(H
2
O
h
)
=168,6 - 68,12 +228,59 = - 8,13 (kJ )
G
p (298)
=-8,13kJ <0 Phn ng xy ra theo chiu thun
o

c)
- 27 -
o
S
298,p
=S
o
- S
o
- S
o
298(H
2
O)
298(C
2
H
4
)
298(C
2
H
5
OH)
=282 - 219,45 - 188,72 =- 126,17(J /K)
G = H - T. S
H
298,p
= G
298,p
+T. S
298,p
=-8,13 +298(- 126,17 .10
-3
) =- 45,72866(kJ )
H
298,p
<0 phn ng to nhit

o
o
o o
Bi 22: Mt mol kh l tng n nguyn t 300K v 15atm gin
n ti p sut 1atm. S gin n c thc hin bng con ng:
a) ng nhit v thun nghch nhit ng.
b) ng nhit v khng thun nghch.
c) on nhit v thun nghch.
d) on nhit bt thun nghch.
Trong cc qu trnh bt thun nghch, s gin n chng li p sut
1atm. Tnh Q, W, U, H, S
tp
cho mi trng hp.
Gii:
a) T = const U = 0 ; H = 0
WTN = -

2
1
PdV
= - nRTln
1
2
V
V
= -nRTln
2
1
P
P
W
TN
= -1(mol).8,314 (J.mol
-1
K
-1
) .ln
1
15
.300(K) = -6754,42(J)
Q = -W = 6754,42(J)
Qu trnh gin n thun nghch: S
tp
= S
mt
+ S
h
= 0
b) T = const U = 0 ; H = 0
W
BTN
= -P
ng
(V
2
- V
1
) = -P
2
(
2
P
nRT
-
1
P
nRT
) = nRT(
1
2
P
P
- 1) = 1. 8,314.300.(
15
1
-
1)= -2327,92(J)
Q
BTN
= -W = 2327,92(J)
S
tp
= S
mt
+ S
h
S
h(BTN)
= S
h(TN)
=
T
Q
TN
=

T
W U

2
1
T
dT
nC
V
+
dV
V
nR

2
1
= nRln
1
2
V
V
=
nRln
2
1
P
P
- 28 -
= 1.8,314 .ln
1
15
= 22,515(J/K)
S
mt
=
T
Q
mt
= -
T
Q
he
=
300
92 , 2327
= -7,76(J/K) S
tp
= 22,515 - 7,76 =
14,755 (J/K)
( Qu trnh gin n ny t xy ra)
c) on nhit Q = 0
on nhit thun nghch Theo Poisson T.V

- 1
= const
M V =
P
nRT
T.
1

,
_

P
nRT
= const T

.P
1-

= const
T
1
.P
1
=T
2
.P
2
T
1
T
2
=
P
2
P
1

T
1
T
2
P
2
P
1
=

1-
1-

1-

1-
T
2
=T
1
.
P
2
P
1

1-
Vi kh l tng n nguyn t th C
V
=
2
3
R; C
P
=
2
5
R

= =
C
P
C
V
5
3
1 -
=
1 -
= -0,4
T
2
= 300.
-0,4
= 101,55(K)

5
3
5
3
15
1
U = W = nC
V
(T
2
- T
1
) = 1.
2
3
.8,314.(101,55 - 300) = -2474,87(J)
H = nC
P
(T
2
- T
1
) = 1.
2
5
.8,314 .(101,55 - 300)= - 4124,78(J)
S
TN
=
T
Q
= 0
d) on nhit Q = 0
on nhit, khng thun nghch khng p dng c PT poisson
U = W nC
V
. T = -P
ng
. V
- 29 -
n.
2
3
.R(T
2
- T
1
) = -P
2
(
2
2
P
nRT
-
1
1
P
nRT
)

2
3
(T
2
- 300) = -( T
2
-
1
2
P
P
.T
1
)

2
3
T
2
- 450 = -T
2
+
15
1
.300
V
2
=
2
2
P
nRT
=
1
188 . 082 , 0 . 1
= 15,416(l)
V
1
=
2
2
P
nRT
= 1,64(l)
U = W = 1.
2
3
.8,314.(188- 300) = -1396,752(J)
S
tp
= S
h
=
T
Q
TN
=

T
W U

2
1
T
T
V
T
dT
nC
+
dV
T
P
V
V

2
1
=

2
1
ln
T
T
V
T d nC
+
dV
V
nR
V
V

2
1
= nC
V
ln
1
2
T
T
+ nRln
1
2
V
V
= 1.
2
3
.8,314.ln
300
188
+ 1. 8,314 .ln
64 , 1
416 , 15
=
12,801(J/K) > 0
Bi 2 3: Tnh
0
273
G
ca phn ng: CH
4(k)
+ H
2
O
(k)
CO
(k)
+ 3H
2(k)
Bit: CH
4(k)
H
2
O (k) CO(k) H
2(k)
0
298 , S
H
(kJ/mol) - 74,8 - 241,8 -110,5 0
0
298
S
(J/molK) 186,2 188,7 197,6 130,684
a) T gi tr G
0
tm c c th kt lun g v kh nng t din bin
ca kh nng phn ng 373
o
K?
b) Ti nhit no th phn ng cho t xy ra iu kin chun?
(Coi H
0
, S
0
khng ph thuc T)
Gii:
0
pu
H
= 3.0 + 1(-110,5) -(-74,8) -(-241,8) = 206,1(kJ)
0
pu
S
= 3.(130,684) + 197,6 - 188,7 - 186,2 = 214,752 (J/K)
Do H
0
, S
0
khng ph thuc vo T nn:

0
273
G
= H
0
- T. S
0
= 206,1 = 373.214,752.10
-3
=125,9975(kJ) > 0
- 30 -
kc v T = 373K Phn ng khng th t din bin.
b) phn ng t din bin nhit T(K) th:
0
T
G < 0 H
0
- T.
S
0
< 0
T >
0
0
S
H

=
752 , 214
10 . 1 , 206
3
=
959,71(K)
Bi 2 4:
Entanpi t do chun ca phn ng to thnh H
2
O t cc n
cht ph thuc vo T theo phng trnh sau:
0
,T S
G
= -240000 +
6,95T + 12,9TlgT (J/mol)
Tnh G
0
, S
0
v H
0
ca phn ng to thnh H
2
O 2000K
Gii:

0
2000 , S
G
= -240000 + 6,95.2000 + 129.2000lg2000= -140933,426(J/mol)
dG = VdP - SdT
P
T
G

,
_

= -S

0
2000
S
= -
P
T
G

,
_

0
= 6,95 + 12,5.lgT + 12,9T.
10 ln .
1
T
= 6,95 + 12,9lgT +
10 ln
9 , 12
= 6,95 + 12,9lg2000 +
10 ln
9 , 12
= 55,1357(J/molK)

0
2000
H
=
0
2000
G
+ T.
0
2000
S
= -140933,426 + 2000. 55,1357 =
-30662,054 (J/mol)
Bi 25:
Mt Hc sinh khi lm bi tng trnh th nghim o nhit
t chy mt hp cht hu c cho rng: H = U + P. V. S t
chy trong bom nhit lng k lm cho V = 0, do H = U. Kt
lun ny sai u?
Gii:
H = U + P.V H = U + (PV) = U + P. V + V. P
Hay H = U + (nRT)
- 31 -
Trong bom nhit lng k th: V = 0 nn: H = U + V. P = U +
(nRT)
Bi 2 6: Hy ch ra nhng mnh sai:
a) i vi 1 h kn, qu trnh gin n kh l on nhit h l c lp
Q = 0; S = 0.
b) Mt h bt k c th t din bin ti trng thi c entanpi thp hn
( H < 0) v entropi ln hn ( S > 0). Hay h c th din bin theo
chiu gim entanpi t do ( G < 0).
c)
0
T
G =
0
T
H - T.
0
T
S
Vi phn ng ho hc T = const. Nu
0
G
> 0 Phn ng t din bin
theo chiu nghch.
0
G
= 0 : Phn ng trng thi cn bng.
0
G
< 0 : Phn ng t xy ra theo chiu thun.
Gii:
a) Sai . Do S = 0 ch khi qu trnh bin i thun nghch.
Cn vi qu trnh bin i bt thun nghch th S >
T
Q
S > 0.
b) Sai . Do mnh ny ch ng trong iu kin T, P = const.
Cn vi qu trnh bin i m V, T = const th phi xt F.
c) Sai. Do vi qu trnh ho hc th phi xt gi tr:
G = G
0
+ RTlnQ ch khng phi da vo G
0
.
(Tuy nhin, c th coi rng
0
T
G << 0 th qu trnh c th xy
ra c c iu kin chun v iu kin thc. Khi
0
T
G << 0
th v nguyn tc ch c qu trnh ngc li mi xy ra, khng
th xc nh c chnh xc gii hn ca
0
T
G m theo qu
trnh xy ra theo chiu ny hay chiu khc. Mt cch gn ng
c th coi rng cc gii hn ny khong chng t 40 kJ/mol).
Bi 27:
- 32 -
Mt kh l tng c C
V
= 3R khng ph thuc T c gin n on
nhit trong chn khng ti th tch gp i. Hc sinh A l lun rng
i vi qu trnh on nhit th
1
2
1
1
2

,
_

V
V
T
T
vi =
3
4
do T
2
=
3
1
1
2
T
Hc sinh B cho rng: U = Q + A = 0 + 0 = n.C
V
. T T = 0 T
2
=
T
1
Hc sinh no ni ng? Hy ch ra li sai ca Hc sinh kia.
Gii:
- Hc sinh B ni ng.
- Hc sinh A ni sai : V qu trnh gin n trong chn khng l qu
trnh bt thun nghch nn khng s dng c phng trnh poisson.
Bi 2 8:
Tnh cht nhit ng ca mt s phn t v ion trng thi tiu
chun ti 25
o
C nh sau:
C
3
H
8(k)
O
2(k)
CO
2(k)
H
2
O
(l)

2
3
CO
(aq)
OH
-
(aq)
0
S
H
(kJ/mol) -101,85 0 - 393,51 - 285,83 - 677,14 -
229,99
S
0
(J/molK) 269,91 205,138 213,74 69,91 - 56,9 -
10,75
Xt qu trnh oxi ho hon ton 1 mol C
3
H
8
(k) vi O
2
(k) to thnh theo 2
cch :
a) Bt thun nghch
b) Thun nghch (trong 1 t bo in ho)
1) Tnh H
0
, U
0
, S
0
, G
0
ca phn ng trong mi cch ni trn?
2) Tnh nhit, cng th tch, cng phi th tch (tc l cng hu ch)
m h trao i vi mi trng trong mi cch?
3) Tnh S ca mi trng v S tng cng ca v tr khi tin hnh
qu trnh theo mi cch.
4) Mt m hnh t bo in ho khc lm vic da trn phn ng oxi
ho C
3
H
8
(k) bi O
2
(k) khi c mt dung dch KOH 5M vi in cc Pt. Cc
- 33 -
loi phn t v ion (tr KOH) u trng thi tiu chun. Hy vit cc
na phn ng catot v anot v phn ng tng cng trong t bo
in ho. Nu t t bo in ho , 25
o
C, ta thu c dng in
100mA. Hy tnh cng sut cc i c th t c.
Gii:
C
3
H
8(k)
+ 5O
2(k)
3CO
2(k)
+ 4H
2
O
(l)
1) Do cc hm H, U, S, G l hm trng thi nn d tin hnh theo cch
no th cc gi tr U, H, S, G cng nh nhau vi cng trng thi
u v cui. Vy:
0
pu
H
= 3
0
) ( ,
2
k CO S
H
+ 4.
0
) ( ,
2
l O H S
H
-
0
) ( ,
8 3
k H C S
H
- 5.
0
) ( ,
2
k O S
H
= -3. 393,51 - 285,83 .4 + 103,85 = -2220 (kJ)
0
pu
H
= 213,74. 3 + 4.69,91 - 269,91 - 5. 205,138 = -374,74 (J/K)
0
pu
G
= H
0
- T. S
0
= -2220 + 298,15 .374,74.10
-3
= -2108,27 (kJ)
U
0
= H
0
- (PV) = H
0
- nRT = -2220 - (-3).8,314.298,15.10
-3
=
-2212,56(kJ)
2) a) Qu trnh bt thun nghch:
- Nhit m h trao i vi mi trng l Q
BTN
= H
0
= -2220 (kJ)
- W
tt
= -

2
1
.dV P
= -P. V = - n
(k)
.RT
= 3. 8,3145.298,15 = 7436,9(J)
- W = 0
b) Qu trnh thun nghch:
- Q
TN
= T. S = 298,15 (-374,74) = - 111728,731(J)
- W
max
= G = -2108,27(kJ) < 0 : H sinh cng
- W
tt
= - n
(k)
.RT = 7436,9(J) > 0: h nhn cng
3) a) Qu trnh bt thun nghch:
S
mt
=
T
Q
mt
= -
T
Q
BTN
= -
T
H
0

= -
15 , 298
10 . 2220
3
= 7445, 916 (J/K)
S
v tr
= S
mt
+ S
h
= 7445,916 - 374,74 = 7071,176(J/K)
b) Qu trnh thun nghch:
S
mt
=
T
Q
mt
= -
T
Q
TN
=
) / ( 74 , 374
15 , 298
731 , 111728
K J
S
v tr
= S
mt
+ S
h
= 0
- 34 -
4) Cc na phn ng:
Anot: C
3
H
8
+ 26OH
-
3
2
3
CO
+ 17H
2
O + 20e
Catot: O
2
+ 2H
2
O + 4e 4OH
-
Phn ng tng cng:
C
3
H
8(k
) + 5O
2(k)
+ 6OH
-
(aq)
3
2
) ( 3 aq
CO
+ 7H
2
O
(l)
S pin:
(-) Pt, C
3
H
8
(1atm)/KOH(5M), K
2
CO
3
(1M)/ O
2
(1atm), Pt (+)
0
pu
H
= 3(-677,14) + 7.(-285,83) + 103,85 - 5.0 - 6(-229,99) =
-2548,44(KJ)
0
pu
S
= 3.(-56,9) + 7.69,91 - 269,91 - 5.205,138- 6(-10,74) = -912,43(KJ)
0
pu
G
=
0
pu
H
= T.
0
pu
S
= -2548,44 + 298,15.912,43.10
-3
= -
2276,399(KJ)

0
pu
E
= -
nF
G
0

=
96485 . 20
2276399
= 1,18(V)
E = E
0
-
5 6
3 2
3
2 8 3
. . ] [
] [
lg
20
0592 , 0
O H C
P P OH
CO

= 1,18 -
20
0592 , 0
lg(5)
-6
= 1,19(V)
P = E .I = 1,19 .0,1 = 0,119(W)
Bi 2 9:
Tnh bin thin entropi khi chuyn 418,4J nhit t vt c t
0
= 150
o
C
n vt c t
0
= 50
o
C.
Gii:
Qu trnh bin i trn l khng thun nghch c coi nh gm 3 qu
trnh bin thin thun nghch:
1) Vt 150
o
C truyn nhit thun nghch T = const.
S
1
=
T
Q
=
15 , 273 150
4 , 418
+

= - 0,989(J/K)
2) H bin thin on nhit t 150
o
C n 50
o
C
S
2
= 0
3) Vt 50
o
C nhn nhit thun nghch T = const
S
3
= -
T
Q
=
15 , 273 50
4 , 418
+
= 1,295(J/K)
Do S l hm trng thi nn:
- 35 -
S
BTN
= S
TN
= S
1
+ S
2
+ S
3
= 0,306(J/K)
Bi 30: Bit -15
o
C, P
hi
(H
2
O, l) = 1,428 (torr)
-15
o
C, P
hi
(H
2
O,r) = 1,215(torr)
Hy tnh G ca qu trnh ng c 1 mol H
2
O
(l)
thnh nc -15
o
C
v 1atm.
Gii:
15
o
C, 1 mol H
2
O l
-15
o
C, 1mol H
2
O(r)
(3)
G
BTN
=?
(1)
(Qu trnh TN do
H
2
O hi, b o ho
nm cn bng v i H
2
O(l))
- 15
o
C, 1mol H
2
O
1,428 Torr
(2)
-15
o
C, 1mol H
2
O (h)
1,215 Torr

(1), (3) l qu trnh chuyn pha thun nghch

G
1
= G
3
= 0
G = G
2
= nRTln
1
2
P
P
= 1.8,314. 258,15 ln
428 , 1
215 , 1
= -346,687(J)
Bi 31: C 1 mol O
2
nguyn cht 25
o
C, 2atm
1 mol O
2
nguyn cht 25
o
C, 1atm
1 mol O
2
25
o
C trong khng kh trn mt t (P = 1atm,
O
2
chim 21% V khng kh)
- So snh gi tr hm G ca 1 mol O
2
trong 3 trng hp trn hn km
nhau bao nhiu J?. T rt ra kt lun: Kh nng phn ng ca O
2
trong mi trng hp trn cao hay thp hn so vi trng hp khc?
Gii:
* G
0
l hm Gibb ca 1 mol O
2
1atm
- 1 mol O
2
, 1atm, 25
o
C 1 mol O
2
, 2atm, 25
o
C
(G
0
) (G
1
)
G
1
= G
1
- G
0
= nRTln
1
2
P
P
= 1. 8,3145 .298,15.ln
1
2
= 1718,29(J)
G
1
> G
0
.
- Gi G
2
l hm Gibb ca 1mol O
2
25
o
C trong khng kh (0,21 atm)
- 36 -
1mol O
2
, 25
o
C, 1atm 1 mol O
2
, 25
o
C, 0,21atm
(G
0
) (G
2
)
G
2
= G
2
- G
0
= 1. 8,3145 .298,15.ln
1
21 , 0
= -3868,8(J)
G
2
< G
0
.
Vy:
G
2
(1mol O
2
, 25
o
C, 0,21atm) < G
0
(1 mol O
2
, 25
o
C, 1atm) < G
1
(1 mol H
2
O,
25oC, 2atm)
- 1 cht c hm G cng cao th cng km bn 1 mol O
2
25
o
C, 2atm
c kh nng phn ng cao nht cn 1 mol O
2
nm trong khng kh th
b nht c kh nng phn ng km nht.
Bi 32:
Nhit ho tan ( H
ht
) 0,672g phenol trong 135,9g clorofom l -88J
v ca 1,56g phenol trong 148,69g clorofom l -172J.
Tnh nhit pha long i vi dung dch c nng nh dung dch th 2
cha 1 mol phenol khi pha long n nng ca dung dch th nht
bng clorofom.
Gii:
94g phenol +CHCl
3
dd 2 dd 1
H pha lo ng
+CHCl
3
H
ht (2)
H
ht(1)
H
pha lo ng
= H
ht(1)
- H
ht(2)
=- .(-172) + (-88) =- 2004,87(J )
0,672
94
1,569
94

Bi 33:
Nhit ho tan 1 mol KCl trong 200 ml nc di p sut P = 1amt l:
t
0
C 21 23
H 18,154 17,824 (kJ)
Xc nh H
298
v so snh vi gi tr thc nghim l 17,578 (kJ)
Gii:
Theo nh lut Kirchhoff:
H
294
= H
298
+ C
P
.(294 - 298) = 18,454 (kJ)
- 37 -
H
286
= H
298
+ C
P
.(296 - 298) = 17,824(kJ)

H
298
= 17,494 (kJ)
C
P
= -0,165 (kJ/K)
H
298(LT)
- H
298(TN)
H
298(TN)
0,48%
~
~

Vy H
298
tnh c theo l thuyt sai khc vi gi tr TN l 0,48%.
Bi 34: Tnh S ca qu trnh ho hi 3 mol H
2
O (l) 25
o
C,
1atm.
Cho: H
hh
,
H2O(l)
= 40,656 kJ/mol; ) ( ,
2
l O H P
C
= 75,291 (J/K.mol); ) ( ,
2
h O H P
C
=
33,58 (J/molK)
Gii:
Xt chu trnh:
25
o
C, 3 mol H
2
O
(l)
, 1atm 25
o
C, 3 mol H
2
O
(r)
, 1atm
100
o
C, 3mol H
2
O
(l)
,1atm 100
o
C, 3mol H
2
O
(h)
,
1atm
S
S
1
S
2
S
3
S
1
=
T
Q
1
=

2
1
. .
) (
T
T
l P
T
dT
C n
= nC
P(l)
ln
1
2
T
T
= 3. 75,291.ln
15 , 298
15 , 373
=
50,6822(J/K)
S
2
=
T
Q
2
=
T
H n
l hh.
.
= 3.
15 , 373
10 , 656 , 40
3
= 326,8605(J/K)
S
3
=
T
Q
3
=

1
2
. .
) (
T
T
h P
T
dT
C n
= nC
P(h)
ln
1
2
T
T
= 3. 33,58.ln
15 , 373
15 , 298
= -
22,6044(J/K)
S = S
1
+ S
2
+ S
3
= 354,9383 (J/K)
Bi 35:
a) Tnh cng trong qu trnh t chy 1 mol ru etylic kc v
25
o
C.
b) Nu H
2
O dng hi th cng km theo qu trnh ny l bao
nhiu?
- 38 -
Gii:
a) C
2
H
5
OH
(l)
+ 3O
2 (k)
2CO
2 (k)
+ 3H
2
O
(l)
n = -1
W = -P
ng
. V = -P
ng
.
ng
P
RT n.
= R.T = 8,314.29815 = 2478,82 (J)
b) Nu H
2
O dng hi th: n = 2.
W = - n. RT = -2 .8,314 .298,15 = - 4957,64(J)
Bi 36:
Tnh S, G trong qu trnh gin khng thun nghch 2 mol
kh l tng t 4lt n 20 lt 54
o
C.
Gii:
V S, G l cc hm trng thi nn S, G khng ph thuc vo qu
trnh bin thin l thun nghch hay bt thun nghch m ch ph
thuc vo trng thi u v trng thi cui. V vy:
S = nRln
1
2
V
V
= 2. 8,314.ln
4
20
= 26,76 (J/K)
T = const H = 0; U = 0
G = H - T. S = 0 -(273,15 + 54) .26,76 = - 8755,1 (J)
Bi 37:
Mt bnh c th tch V = 5(l) c ngn lm 2 phn bng nhau.
Phn 1 cha N
2
298K v p sut 2atm, phn 2 298K v p sut
1atm. Tnh G, H, S ca qu trnh trn ln 2 kh khi ngi ta b
vch ngn i.
Gii:
T = 298K ; V
b
(N
2
) = V
b
(O
2
) =
2
5
(l)
S = S(N
2
) + S(O
2
) =
2
N
n
.Rln
1
2
V
V
+
2
O
n
Rln
1
2
V
V
=
RT
V P
N N
2 2
.
Rln
5 , 2
5
+
RT
V P
O O
2 2
.
Rln
5 , 2
5
- 39 -
= 2 ln
. .
2 2 2 2
T
V P V P
O O N N
+
= 0,0174(l.at/K) = 0,0174 .101,325 = 1,763
(J/K)
- Qu trnh ng nhit H = 0
G = H - T. S = - 298 .1,763 = - 525,374 (J)
Bi 38:
Cho cc d liu sau y 298K
Cht
0
S
H
(kJ/molK) S
0
(J/molK) V(m
3
/mol)
C
than ch
0,00 5,696 5,31.10
6
C
kim cng
1,90 2,427 3,416.10
-6
1) 298K c th c mt phn rt nh kim cng cng tn ti vi than ch
c khng?
2) Tnh p sut ti thiu phi dng c th iu ch c kim cng
298K?
Gii
1)

C
kim c ng
C
than ch
G
0
=?
298

H
o
= H
o

than ch
- H
o

kim cng
= 0 - 1,9 = -1,9 (kJ)
S
o
= S
o

than ch
- S
o
kim cng
= 5,696 - 2,427 = 3,269 (J/K)

0
, 298 pu
G
= H
o
- T. S
o
= -1900 - 298.3,269 = -2874,162(J)
G
o
< 0 (Tuy nhin G
o
khng qu m)
Phn ng t xy ra theo chiu thun khng tn ti mt lng nh kim
cng cng vi than ch.
2)

G
0
=+2874,162 (J )
298

C
than ch
C
kim c ng
V = V
KC
- V
TC
= 3,416.10
-6
- 5,31.10
-6
= 1,894.10
-6
(m
3
/mol)
Ta c: dG = VdP - SdT

T
P
G

,
_

= V
T
P
G

,
_

= V

2
P
G
-
1
P
G
= V(P
2
- P
1
)
- 40 -
iu ch c kim cng t than ch th:
2
P
G
0

1
P
G
+ V(P
2
- P
1
) 0
P
2
- P
1
-
V
G
P

1
(Do V < 0)
P
2
P
1
-
V
G
P

1
= 1 +
325 , 101 . 10 . 894 , 1
162 , 2874
3
P
2
14977,65 (atm)
Vy p sut ti thiu phi dng iu ch c kim cng t than ch
l 14977,65atm.

Nh vy 25
o
C, cn bng than ch kim c ng tn ti p sut khong
15000 atm. p sut cao hn qu trnh chuyn than ch thnh kim c-
ng l t din bin, mc du vi tc rt chm. Mun tng tc
phi tng nhit v p sut, trong thc t qu trnh chuyn than
ch thnh kim cng c tin hnh khi c xc tc (Ni + Cr + ) nhit
trn 1500
o
C v P 50000atm.
Bi 39: Phn ng gia Zn v dd CuSO
4
xy ra trong ng nghim
to ra lng nhit 230,736kJ. Cng phn ng trn cho xy ra trong pin
in th mt phn ho nng chuyn thnh in nng. Cng in ca
pin l 210,672kJ. Chng minh rng: U ca 2 qu trnh khng i, nh-
ng nhit to ra thay i. Tnh S ca phn ng, S
mt
v S
tp
? Cho T
= 300K
Gii:
Zn + CuSO
4
= ZnSO
4
+ Cu
- Khi thc hin trong ng nghim: (Tin hnh bt thun nghch)
V
Zn
V
Cu
W
tt
= 0 ; W = 0
U
BTN
= Q
BTN
= H = -230,736kJ
- Khi thc hin phn ng trong pin in (qu trnh thun nghch)
W
max
= - 210,672 (kJ) G = W
max
= -210,672(kJ)
H
TN
= H
BTN
= - 230,736(kJ)
Q
TN
= T. S = H - G = -230,736 + 210,672 = -20,064(kJ)
- 41 -
U
TN
= Q + W + P. V = -20,064 = 210,672 + 0 = -230,736 (kJ) =
U
BTN
- S
h
=
T
Q
TN
= -
300
10 . 064 , 20
3
= 66,88(J/K)
S
mtBTN
= -
T
Q
BTN
=
300
10 . 736 , 230
3
= 769,12(J/K)
S
tp(BTN)
= 702,24(J/K)
S
mt(TN)
= -
T
Q
TN
= - S
h
S
tp(TN)
= 0
Bi 40:
- G
p
= W
max
Xt 1 phn ng thun nghch trong pin in th G
p
= W
max
< 0
- Nhng mt hc sinh vit rng:
Trong mi qu trnh lun c: S
v tr
= S
mt
+ S
h
(1)
H
mt
= - H
h
(2)
S
mt
=
T
H
mt

= -
T
H
he

S
v tr
= -
T
H
he

+ S
h
T. S
v tr
= - H
h
+ T. S
h
= - G
h
Vi qu trnh thun nghch th S
v tr
= 0 G
h
= 0 G
p
=
0
Hy gii thch mu thun ny.
Gii:
(2) ch ng khi ngoi cng gin n h khng thc hin cng no khc:
H = U + P. V U = H - P. V
Q = U - W = ( H - P. V) - (-P. V + W)
Q
h
= H
h
- W = - H
mt
Ch khi W = 0 th H
mt
= - H
h
* Trong pin: W
max
= G < 0 nn H
mt
H
h
.
Bi 41: Xt phn ng: Zn
(r)
+ Cu
2+
(aq)
Zn
2+
(aq)
+ Cu
(r)
din ra trong ktc 25
o
C.
a) Tnh W, Q, U, H, G, S ca phn ng iu kin trn.
Bit: Zn
2+
(aq)
Zn
(r)
Cu
(r)
Cu
2+
(aq)
0
298 , S
H
(kJ/mol) -152,4 0 0 64,39
- 42 -
0
298
S
(J/mol.K) - 106,5 41,6 33,3 - 98,7
b) Xt kh nng t din bin ca phn ng theo 2 cch khc nhau.
c) Nu thc hin phn ng trn 1 cch thun nghch trong pin in
th cc kt qu trn c g thay i? Tnh E
pin
?
Gii:
a)
0
pu
H
=
0
,
2+

Zn S
H
+
0
,Cu S
H
-
+
0
,Zn S
H
0
,
2+

Cu S
H
= -152,4 - 64,39 = -216,79
(kJ)

0
pu
S
=
0
) (
2
aq Zn
S
+
+
0
) (r Cu
S
-
0
) (r Zn
S
-
0
) (
2
aq Cu
S
+
= -106,5 + 33,3 - 41,6 + 98,7 =
-16,1 (J/K)

0
pu
G
=
0
H
- T.
0
S
= -216,79 + 298,15 .16,1.10
-3
= -211,99(kJ)
U
o
= Q
P
=
0
pu
H
= -216,79 (kJ)
W = 0; qu trnh BTN; W = 0
b) *
0
pu
G
= -211,99 (kJ) << 0 ( - 40 kJ)
Do
0
pu
G
rt m nn phn ng t xy ra khng nhng kc m cn c
cc iu kin khc na.
* S
mt
=
T
Q
mt
=
T
H
he
0

=
15 , 298
10 . 79 , 216
3
= 727,12 (J/K)
S
v tr
= S
h
+ S
mt
= -16,1 + 727,12 = 711,02 (J/K)
V S
h c lp
= S
v tr
= 711,02 (J/K) > 0
Qu trnh l bt thun nghch phn ng t xy ra.
c) Khi thc hin phn ng trn TN trong pin in th cc gi tr H
0
,
S
0
, G
0
, U
0
khng thay i do H, S, G, U l cc hm trng thi nn
khng ph thuc qu trnh bin i l thun nghch hay bt thun
nghch nhng cc gi tr Q, W th thay i.
C th: W
tt
= 0; W
max
= G0 = -211,99(kJ)
Q = T. S = 298,15 .(-16,1) = - 4800,215 (J)
S
mt
=
T
Q
mt
=
T
Q
he

= 16,1 (J/K) S
v tr
= S
mt
+ S
h
=
0
E
pin
= -
nF
G
0

=
96485 . 2
211990
1,1(V)
Bi 42:
- 43 -
i vi nguyn t anien 15
o
C ngi ta xc nh c sc in ng
E = 1,09337V v h s nhit ca sc in ng
T
E

= 0,000429
V/K. Hy tnh hiu ng nhit ca phn ng ho hc?
Gii:
G = - nEF
T
G

= - nF.
T
E

= - S S = nF .
T
E

H = G + T. S = nF.(T.
T
E

- E)
H = 2. 96485 .(298,15.0,000429 - 1,09337) - - 187162,5(J)
Bi 43: Cho phn ng ho hc: Zn + Cu
2+
Zn
2+
+ Cu
xy ra mt cch thun nghch ng nhit, ng p 25
o
C trong
nguyn t Ganvani.
Sc in ng ca nguyn t o c l 1,1V v h s nhit ca
sc in ng l
P
T
E

,
_

= 3,3.10
-5
(V/K).
a) Tnh hiu ng nhit Q, bin thin Gipx G v bin thin entropi
S ca phn ng ho hc cho.
b) Tnh Q
tn
ca qu trnh?
c) Nu cng phn ng ho hc trn thc hin cng nhit v cng p
sut nhng trong mt bnh cu thng th cc gi tr ca G, S s l
bao nhiu?
Gii:
a) G = - nEF = - 2 .1,1 .96485 = - 212267(J)
S = -
T
G

= n.F .
T
E

= 2 .96485 .3,3 .10

-5
= 6,368 (J/K)
H = G + T. S = 212267 + 298,15 .6,368 = -210368,4(J)
b) Q
tn
= T . S = 298,15 .6,368 = 1898,62 (J)
c) Nu phn ng ho hc thc hin cng nhit , p sut nhng trong
1 bnh cu thng tc l thc hin qu trnh mt cch bt thun
nghch th G, S ca phn ng vn nh cu (a). Do G, S l cc hm
trng thi gi tr ca G, S khng ph thuc vo qu trnh bin
thin.
- 44 -
iv- KT LUN - kin ngh :
Trn y l h thng cu hi v bi tp phn Nhit ho hc
m ti p dng trong ging dy. N tng i ph hp vi yu cu v
mc ch ging dy, bi dng hc sinh kh, gii trng chuyn chun
b d thi hc sinh gii cc cp . N c th dng lm ti liu hc tp cho
hc sinh cc lp chuyn Ho hc v ti liu tham kho cho cc thy c
gio trong ging dy v bi dng hc sinh gii Ho hc bc THPT gp
phn nng cao cht lng ging dy v hc tp mn Ho hc.
Tuy nhin, y ch l mt phn rt nh trong chng trnh n
luyn cho hc sinh chun b tham gia vo cc k thi hc sinh gii cc
cp. V vy, ti rt mong cc Thy , C ng nghip gp kin cho ti
v chuyn ny v cng nhau pht trin sang cc chuyn khc
hc tr chuyn Ho ngy cng c nhiu ti liu hc tp mt cch h
thng hn.
**************************************************
- 45 -