File 545

HOAHOC.
ORG NG XUN QUYNH

09798.17.8.85 09367.17.8.85 - netthubuon Website: www.hoahoc.org - admin@hoahoc.org
XY DJNG HJ THNG CU HOI V BI TAP PHAN NHJT HO HC
DNG CHO HC SINH CHUYN HO
Trch theo ti liu ca: Trng THPT chuyn Nguyn Hu - H Ni
I. MO DAU
Trong qu trnh giang day o truong ph thng nhim vu pht trin tu duy cho hoc sinh l nhim vu
rt quan trong, di hoi tin hnh dng b o cc mn, trong d Ha hoc l mn khoa hoc thuc nghim d cp
dn nhiu vn d cua khoa hoc, s gp phn rn luyn tu duy cho hoc sinh o moi gc d dc bit l qua phn
bi tp ha hoc. Bi tp ha hoc khng nhung c tc dung rn luyn k nng vn dung, do su v mo rng
kin thuc d hoc mt cch sinh dng, phong ph m cn thng qua d d n tp, rn luyn mt s k nng
cn thit v ha hoc, rn luyn tnh tch cuc, tu luc, tr thng minh sng tao cho hoc sinh, gip hoc sinh hung
th trong hoc tp. Qua bi tp ha hoc gio vin kim tra, dnh gi vic nm vung kin thuc v k nng ha
hoc cua hoc sinh.
D gio vin bi dung hoc sinh kh, gioi o truong chuyn du thi hoc sinh gioi cp Tinh v cp
Quc gia duoc tt th nhu cu cp thit l cn c mt h thng cu hoi v bi tp cho tt ca cc chuyn d
nhu : cu tao cht, nhit ho hoc, dng ho hoc, cn bng ho hoc,....
V vy , trong qu trnh giang day di tuyn hoc sinh gioi Tinh v Quc gia ti d suu tm v tp hop lai
mt s cu hoi v bi tp theo mt s chuyn d, trong d c phn dng d luyn tp cho hoc sinh phn
Nhit ho hoc
II. MJC DCH CUA DE TI
Xy dung h thng cu hoi v bi tp phn Nhit ho hocdng cho hoc sinh lop chuyn Ho hoc o
bc THPT gip hoc tr hoc tt hon v chun bi tt hon cho cc ky thi hoc sinh gioi Ha hoc ca v l thuyt
bi tp phuong php giai, gp phn nng cao cht luong giang day v hoc tp mn Ha hoc.
III. NI DUNG
A- CO SO L THUYET :
Truoc khi dua ra h thng bi tp cho hoc tr luyn tp th gio vin cn phai yu cu hoc tr nho lai
mt s khi nim v ni dung l thuyt co ban cua phn Nhit ho hoc nhu sau:
1) KH L TUONG:
* Kh l tuong l cht kh m khoang cch giua cc phn tu kh xa nhau, c th bo qua tuong tc giua chng.
* Voi kh l tuong th c th p dung :
- Phuong trnh trang 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
X
X
X
2) HJ V MI TRUNG:
- H mo: h trao di cht v nng luong voi mi truong.
- H kn: H chi trao di nng luong voi mi truong.
- H don nhit: H khng trao di nhit voi mi truong.
* Quy uc:
H nhn nng luong cua mi truong nng luong mang du +
H nhuong nng luong cho mi truong nng luong mang du -
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HOAHOC.ORG NG XUN QUYNH
3) BIEN DOI THUAN NGHJCH:
Nu h chuyn tu trang thi cn bng ny sang trang thi cn bng khc mt cch v cng
chm qua lin tip cc trang thi cn bng th su bin di ny duoc goi l thun nghich. Dy l su bin di l
tuong khng c trong thuc t.
4) SJ BIEN DOI BT THUAN NGHJCH: l su bin di duoc tin hnh voi vn tc dng k. Nhung
phan ung trong thuc t du l bin di bt thun nghich.
5) HM TRANG THI: l hm m gi tri cua n chi phu thuc vo cc thng s trang thi cua h, khng
phu thuc vo nhung su bin di truoc d.
V du: P.V = hm trang thi
P
1
.V
1
= n.RT
1
; P
2
.V
2
= n.R.T
2
6) CNG (W) V NHIJT (Q)
- L 2 hnh thuc trao di nng luong.
- W, Q khng phai l hm trang thi v gi tri cua chng phu thuc vo cch bin di.
V du: Cng cua su gin no kh l tuong tu th tch V
1
dn V
2
o t
o
= const trong 1 xilanh kn nho 1 pittng
duoc tnh bng cng thuc:
W = - dV P
n
.
2
1
}
(P
n
: p sut bn ngoi)
* Nu su bin di l BTN th P
n
= P
kq
= const
W
BTN
= - P
kq
. dV
}
2
1
= - P
kq
. AV = - P
kq
.(V
2
- V
1
)
* Nu su bin di l thun nghich: Giam P
n
nhung luong v cng b d th tch kh tng nhung luong v
cng b. Khi d P
n
mi lc thuc t = P o 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 nghich sinh cng lon nht khi h bin di tu trang thi 1 sang trang thi 2. Luong cng
ny dng bng luong cng cn thit dua h v trang thi ban du mt cch thun nghich.
7) NI NNG U:
- U cua mt cht hay mt h gm dng nng cua cc phn tu v th nng tuong tc giua cc phn tu trong h
d.
- U l dai luong dung d v l hm trang thi
- U cua n mol kh l tuong chi phu thuc vo nhit d.
8) NGUYN L I CUA NHIJT DNG HC: (SJ BIEN DOI NI NNG CUA HJ).
AU = U
2
- U
1
= W + Q
- Di voi su bin di v cng nho: dU = o
W
+ o
Q
(o: Chi nhung hm khng phai l hm trang thi)
- Thuong gp cng duoc thuc hin chi do su bin di th tch nn: o
W
= -P.dV
dU = o
Q
= P .dV
}
dU = Q - dV P.
2
1
}
AU = Q - dV P.
2
1
}
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* Nhit dng tch: Nu h bin di o V = const dV = 0
AU = Q
V
Q
V
l 1 hm trang thi.
* Nhit dng p: Nu h bin di o P = const th:
dV P.
2
1
}
= P . dV
}
2
1
= P. V
2
- P. V
1
AU = U
2
- U
1
= Q
P
- P. V
2
+ P .V
1
Q
P
= (U
2
+ P.V
2
) - (U
1
+ P .V
1
)
Dt U + P.V = H = entanpi = hm trang thi
Q
P
= H
2
- H
1
= AH = su bin thin entanpi cua h.
* Nhit phan ng:
Xt 1 h kn trong d c phan ung: aA + bB cC + dD
Nhit phan ung cua phan ung ny l nhit luong trao di voi mi truong khi a mol A phan ung voi b mol B
tao ra c mol C v d mol D o T = const.
- Nu phan ung duoc thuc hin o P = const th nhit phan ung duoc goi l nhit phan ung dng p Q
P
= AH
- Nu phan ung duoc thuc hin o V = const th nhit phan ung duoc goi l nhit phan ung dng tch Q
V
=AU
* Quan h giua Q
P
v Q
V
Q
P
= AH = A(U + PV)P = AU + P. AV AH = AU + P . AV = AU + An .RT
Q
P
= QV + An .RT ( An = n
kh sp
- n
kh pu
)
Khi An = 0 Q
P
= Q
V
hay AH = AU
U = Q
V
= n .C
V
. T A A
H = Q
P
= n .C
P
. T A A
* Nhit dung mol dng p (C
P
) l nhit luong cn cung cp d lm 1 mol cht nng thm 1
o
trong diu kin
dng p (m trong qu trnh khng c su bin di trang thi).
* Tuong tu voi C
V
: AH =
}
2
1
.
T
T
P
dT C ; AU =
}
2
1
.
T
T
T
dT C
C
P
, C
V
l hm cua nhit d.
Voi 1 mol kh l tuong: C
P
=
T
H
A
A
; C
V
=
T
U
A
A
M AU = AH - P. AV C
P
=
T
H
A
A
=
T
U
A
A
+
T
V P
A
A .
= C
V
+ R
Q, W: Khng phai l hm trng thi
Q
V
= AU; Q
P
= AH Q
V
, Q
P
l hm trng thi ch ph thuc vo trng thi du v trng thi cui
cua h m khng ph thuc vo qu trnh bin di l thun nghjch hay khng thun nghjch.
9) DJNH LUAT HESS: AH (AU) cua 1 qu trnh chi phu thuc vo trang thi du v trang thi cui cua h
m khng phu thuc vo duong di.
AHpu = AHs (san phm) - AHs (cht du) = AHc (cht du) - AHc (san phm)
10) DJNH LUAT KIRCHHOFF:
A
A
A
n
1
A + n
2
B n
3
C + n
4
D
T
2
H
2
H
a
H
b
A
n
1
A + n
2
B n
3
C + n
4
D
T
1
H
1
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Theo dinh lut Hess: AH
2
= AH
a
+ AH
1
+ AH
b
M:
AH
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
AH
b
=
}
+
2
1
). . . (
4 3
T
T
P P
dT C n C n
D C
AH
2
= AH
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
= AH
1
+
}
A
2
1
.
T
T
P
dT C
- AH
1
thuong duoc xc dinh o diu kin chun: AH
o
T
= AH
o
298
+
}
A
T
o
P
dT C
298
.
Voi AC
o
P
= C
o
P
(sp) - C
o
P
(tham gia)
C
o
P
l nhit dung mol dng p o diu kin chun (1atm).
- Trong khoang hep cua nhit d c th coi AC
o
P
= const
Th: AH
2
= AH
1
+ AC
P
.(T
2
-T
1
)
AH
o
T
= AH
o
298
+ AC
o
P
(T - 298)
11) ENTROPI (S)
- Trong su bin di thun nghich v cng nho o T = const h trao di voi mi truong mt luong nhit oQ
TN
th su bin thin entropi trong qu trnh ny l: d
S
=
T
Q
TN
o
S l hm trang thi (J/mol.K)
- Nu su bin di l bt thun nghich th d
S
>
T
Q
TN
o
- V l hm trang thi nn khi chuyn tu trang thi 1 sang trang thi 2 bng bin thin thun nghich hay bt
thun nghich th :
S
2
- S
1
= AS =
}
2
1
T
Q
TN
o
(AS
TN
= AS
BTN
)
12) NGUYN L II CUA NHIJT DNG HC:
dS >
T
Q o
- Trong h c lp oQ = 0. nn:
+ dS = 0: trong h c lp entropi cua h khng di nu xay ra qu trnh thun nghich.
+ dS > 0 : trong h c lp, qu trnh tu xay ra (BTN) theo chiu tng entropi cua h v tng cho toi khi dat
gi tri max th h s dat trang thi cn bng.
* Entropi l thuoc do d hn dn cua h: D hn dn cua 1 h hay 1 cht cng lon khi h hay cht d gm
nhung hat v su dao dng cua cc hat cng manh (khi lin kt giua cc hat 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 dai luong dung d.
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13) SJ BIEN THIN S TRONG QU TRNH BIEN DOI TRANG THI CUA CHT:
Khi cht nguyn cht nng chay hoc si o P = const th:
T = const AS =
}
2
1
T
Q o
=
T
H A
AH = nhit bin thin trang thi = L
n/c
hoc L
h
14) AS TRONG QU TRNH GIN NO DANG NHIJT KH L TUONG:
Xt n mol kh l tuong gin no th tch tu V
1
V
2
o t
o
= const. V ni nng cua kh l tuong chi phu thuc
nhit d nn trong su bin di ny:
AU = Q
TN
+ W
TN
= Q
BTN
+ W
BTN
= 0
Q
TN
= - W
TN
= nRT. ln
1
2
V
V
( = -(- P. AV) = dV
V
nRT
.
2
1
}
).
T = const AS =
T
Q
TN
= nRln
1
2
V
V
= n.R.ln
2
1
P
P
15) SJ BIEN THIN ENTROPI CUA CHT NGUYN CHT THEO NHIJT D.
- Qu trnh P = const:
Dun nng 1 cht nguyn cht tu T
1
T
2
, khng c su chuyn pha:
AS =
}
2
1
T
T
TN
T
Q o
Voi oQ = oQ
P
= dH = n.C
P
.dT
AS =
T
dT
C n
T
T
P
. .
2
1
}
* Trong khoang nhit d hep, coi C
P
= const
AS = n.C
P
.ln
1
2
T
T
- Qu trnh: V = const AS = n .C
V
.ln
1
2
T
T
16) ENTROPI TUYJT DI
* Nguyn l III cua nhit dng hc:
- Entropi cua cht nguyn cht duoi dang tinh th hon chinh o 0(K) bng 0: S
(T = 0)
= 0
* Xut pht tu tin d trn ta c th tnh duoc entropi tuyt di cua cc cht o cc nhit d khc nhau.
VD: Tnh S cua 1 cht o nhit d T no d, ta hnh dung cht d duoc dun nng tu 0(K) T(K) xt o
P=const. Nu trong qu trnh dun nng c su chuyn pha th:
AS = AS
T
- AS
(T = 0)
= S
T
=

=
A
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 tri entropi duoc xc dinh o P = 1 atm = const v o nhit d T no d duoc
goi l gi tri entropi chun, k hiu l S
0
T
, thuong T = 298K S
0
298
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17) SJ BIEN THIN ENTROPI TRONG PHAN UNG HO HC:
+ Khi phan ung thuc hin o P = const, T = const th: AS = XS(sp) - XS(t/g)
+ Nu o diu kin chun v 25
0
C th: AS
0
298
= XS
0
298
(sp) - XS
0
298
(t/g)
+ V S cua cht kh >> cht rn, long nn nu s mol kh san phm (sp) > s mol
kh tham gia th AS > 0 v nguoc lai. Cn trong truong hop s mol kh o 2 v
bng nhau hoc phan ung khng c cht kh th AS c gi tri nho.
18) THE NHIJT DNG
ASc lp = AS h + AS mt _ 0
a)Th dng p G:
Xt h xay ra su bin di o P, T du khng di trong qu trnh ny mi truong nhn cua h mt nhit luong
AH
mt
do h toa ra AH
mt
= - AH
h
= - AH
AS
mt
= -
T
H A
+ Diu kin tu din bin cua h:
AS
c lp
= AS
h
-
T
H A
> 0 AH T. AS < 0
+ H o trang thi cn bng khi AH T. AS = 0
+ Dt G = H TS o nhit d, P khng di th qu trnh xay ra theo chiu c
AG = AH T. AS < 0
V dat toi trang thi cn bng khi AG = 0.
b) Th dng tch: (Nng lung Helmholtz)
Nu h bin di o diu kin T, V khng di nhit dng tch m mi truong nhn cua cc h l AU
mt
AS
mt
= -
T
U
mt
A
diu kin tu din bin cua h trong qu trnh dng nhit, dng tch l
AF = AU T. AS < 0
V dat trang thi cn bng khi AF = 0
Trong d : F = U TS
V H = U + PV G = H TS = U TS + PV G = F + PV
+ Di voi qu trnh T,P = const AG = Wmax
+ Di voi qu trnh T, V = const AS = Wmax
TM LAI :
* Qu trnh dng p: P = const
- Cng: oWP = - P.dV = -n.R.dT WP = - P. AV = - nRAT
- Nhit: oQP = dH = n.
P
C .dT QP = AH = n. dT C
T
T
P
.
2
1
}
- Ni nng: dU = oQ + oW AU = AH P. AV = AH n.R. AT
- Entropi: dS _
T
Q
TN
o
AS _
}
2
1
T
Q
TN
o
AS
TN
=
T
dT
C n
T
T
P
. .
2
1
}
= T d C n
T
T
P
ln . .
2
1
}
Nu
P
C = const AS
TN
= n.
P
C .ln
1
2
T
T
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* Qu trnh dng tch:
- Cng: oW
V
= - P.dV = 0 W
V
= 0
- Nhit: oQ
V
= dU
V
= n.
V
C .dT Q
V
= AU
V
= dT n C
T
T
V
. .
2
1
}
Nu
V
C = const Q
V
= n.
V
C .AT
- Ni nng: AU
V
= Q
V
+ W
- Entropi: AS _
T
Q
V
= =
}
T
dT
C n
T
T
V
. .
2
1
T d C n
T
T
V
ln . .
2
1
}
AS _ 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)
AH = AU + V . AP
* Qu trnh dng nhit:
- Cng: oW
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: AU
T
= Q
T
+ W
T
= 0 Q
T
= - W
T
= nRT ln
1
2
V
V
- Ni nng: AU
T
= 0
- Entanpi: AH
T
= AU
T
+ A(PV)
T
= AU
T
+ nR. AT = 0
- Entropi: AS
TN
=
nc
nc TN
T
L
T
Q
= hoc =
S
h
T
L
* Voi qu trnh dn no kh l tuong thun nghich
AS = =
A
=
T
W U
T
Q
TN
+
}
T
dT
C n
V
T
T
. .
2
1
dV
V
nRT
V
V
}
2
1
Nu C
V
= const AS = n.
1
2
ln
T
T
C
V
+ nRT ln
1
2
V
V
V T = const AS = nRT ln
1
2
V
V
= nRT.ln
2
1
P
P
* Qu trnh doan nhit:
- Nhit: Q = 0
- Ni nng v cng: dU = oQ + oW = oW = -PdV =
T
dT
C n
V
T
T
. .
2
1
}
+Qu trnh bt thun nghich:
dU
BTN
= oW
BTN
= -P
ng
.dV = -P
2
.dV
AU
BTN
= W
BTN
= -P
ng
.(V
2
V
1
) = n.C
V
. AT
* PT Poisson: (Dng cho qu trnh thun nghich)
T .
1
V = const
P.V
= const
V
P
C
C
=
C
lic
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* 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
AU = W = .... V
2
* Qu trnh thun nghich: W = AU = 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: AH = n .C
P
(T
2
T
1
)
- Entropi: AS
TN
=
T
Q
TN
= 0
* G = H TS = U + PV TS
=
|
.
|
\
|
c
A c
P
T
G
- AS ; =
|
.
|
\
|
c
A c
T
P
G
- AV
Voi phan ung oxi ho khu c th din ra trong pin din: AG = - nEF
dT
G dA
= - nF.
dT
dE
= - AS AS = nF.
dT
dE
AH = AG + T. AS = nF( T.
dT
dE
- E)
19) NGHA VAT L CUA AG:
G = H TS = U + PV TS
dG = dU + P.dV + V.dP T.dS SdT = (oW + oQ) + PdV + VdP T.dS SdT
V oW = oW + (-PdV)
oQ _ T.dS dG _ oW + VdP SdT
Du = ung voi qu trnh thun nghich v cng lon nht.
dG = oW
max
+ VdP SdT
* Di voi qu trnh dng nhit, dng p dP = dT = 0
dG
T,P
= oW
max
AG = W
max
* Di voi qu trnh BTN: W giam; Q tng khi hon ton BTN W = 0
20) MT S TNH CHT CUA HM G:
dG = V.dP SdT ( coi W = 0)
a) S ph thuc cua AG vo T:
- Khi P = const
P
T
G
|
.
|
\
|
c
c
= - S
P
T
G
|
.
|
\
|
c
A c
= - AS
AG = AH T. AS = AH + T.
P
T
G
|
.
|
\
|
c
A c
T.
P
T
G
|
.
|
\
|
c
A c
- AG = -AH
2 2
.
T
H
T
G
T
G
T
P
A
=
A |
.
|
\
|
c
A c
2
T
H
T
T
G
P
A
=
c
|
.
|
\
| A
c
dT
T
H
T
G
d
T
T
T
G
T
G
T
T
. .
2
1
2
2
1
2
1
} }
A
=
A
A
A
dT
T
G
T
G
T
G
T
T
T T
.
2
1
1 2
2
1 2
}
A
=
A
=
A
Nu coi AH
o
khng phu thuc vo nhit d th: |
.
|
\
|
A
A
=
A
298
1 1
298
298
T
H
G
T
G
o
o
T
C
lic
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b) S ph thuc vo P:
Khi T = const V
P
G
T
=
|
.
|
\
|
c
c

, ) , )
} } }
= =
2
1
1
2
1
2
. .
2
1
P
P
P T
P
P
P T
dP V G G dP V dG
- Voi cht rn, long coi V = const khi P bin thin (tru min p sut lon) th:
, ) , )
) (
1 2
1 2
P P V G G
P T P T
+ =
- Voi cht kh l tuong V =
P
nRT
, ) , )
1
2
ln .
1 2
P
P
nRT G G
P T P T
+ =
Nu p sut bnh thuong: P
1
= P
o
= 1bar (1 atm) G
T(P)
= G
o
T
+ nRT.lnP
(P tnh bng bar (atm)).
21) TNH AG CUA MT S QU TRNH:
a) Gin nn dng nhit kh l tuong
AG = nRT.ln
1
2
P
P
= nRT.ln
2
1
V
V
b) Trn ln dng nhit, dng p 2 kh l tuong:
AG = n
A
.RTlnx
A
+ n
B
.RTlnx
B
c) Qu trnh chuyn pha thun ngh|ch (ti nhit d chuyn pha): AG
cf
= 0
d) Qu trnh chuyn pha thun ngh|ch o T = T
cf
Nguyn tc: p dung chu trnh nhit dng. V G l hm trang thi nn AG chi phu thuc trang thi du, trang
thi cui, khng phu thuc vo qu trnh bin thin.
e) AG cua phan ng ho hc: AG
o
pu
= XAG
o
S(san phm)
- XAG
o
S(tham gia)
C
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B - HJ THNG CC CU HOI V BI TAP PHAN NHIJT HA HC :
Bi 1:
Cho 100 g N
2
o 0
o
C, 1atm. Tnh Q, W, AU, AH trong cc bin di sau dy duoc tin hnh thun nghich
nhit dng:
a) Nung nng dng tch toi P = 1,5atm.
b) Gin dng p toi V = 2V ban du.
c) Gin dng nhit toi V = 200l
d) Gin doan nhit toi V = 200l
Chp nhn rng N
2
l kh l tuong v nhit dung dng p khng di trong qu trnh th nghim v bng
29,1J/mol.K
Giai
a) V = const W =
}
= 0 .dV P
AU = QV = n
V
C .AT = ( 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. AV = -1(160 80) = -80 (l.at) = -80 .101,33 = -8106,4(J)
Q
P
= AH = P C .n .AT =
|
|
.
|
\
|
1 1
1
2
. . 1 , 29 .
28
100
T T
V
V
= 29,1.
28
100
(2.273,15 273,15) = 28388,1(J)
AU = Q + W = 28388,1 = 8106,4 = 20281,7(J)
c) T = const AU = 0; AH = 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)
AU = 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
Voi 4 , 1
314 , 8 1 , 29
1 , 29
~
=
+
= =
P
P
V
P
C R
C
C
C
W = AU = n.
V
C (T
2
T
1
) =
28
100
(29,1-8,314).(189,33 -273,15) = 6222,4(J)
AH = n
P
C .AT =
28
100
.29,1(189,33 273,15) = - 8711,3(J)
Bi 2:
Tnh
o
S
H
298 ,
A cua Cl
-
(aq)
. Bit:
(a):
2
1
H
2
+
2
1
Cl
2(k)
HCl
(k)
o
S
H
298 ,
A = -92,2(kJ)
(b): HCl
(k)
+ aq H
+
(aq)
+ Cl
-
(aq)
o
S
H
298 ,
A = -75,13(kJ)
(c):
2
1
H
2
+ aq H
+
(aq)
+ e
o
S
H
298 ,
A = 0
C
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N
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Giai:
Ly (a) + (b) (c) :
2
1
Cl
2
+ e + aq = Cl
-
(aq)
o
S
H
298 ,
A = - 167,33(kJ)
Bi 3:
Tnh hiu ung nhit cua phan ung:
3Fe(NO
3
)
2(aq)
+ 4HNO
3(aq)
3Fe(NO
3
)
3(aq)
+ NO
(k)
+ 2H
2
O (l)
Din ra trong nuoc o 25
o
C. Cho bit:
Fe
2+
(aq)
Fe
3+
(aq)
NO
3
-
(aq)
NO
(k)
H
2
O
(l)
o
S
H
298 ,
A (kJ/mol) -87,86 - 47,7 -206,57 90,25 -285,6
Giai:
Phuong trnh ion cua phan ung:
3Fe
2+
(aq)
+ 4H
+
(aq)
+ NO
3
-
(aq)
3Fe
3+
(aq)
+ NO
(k)
+ 2H
2
O
(l)
AH=3.
o
S
H
298 ,
A (Fe
3+
,aq
)+
o
S
H
298 ,
A (NO)+2.
o
S
H
298 ,
A (H
2
O
(l)
)3.
o
S
H
298 ,
A (Fe
2+
,aq
)-
o
S
H
298 ,
A (NO
3
-
, aq
)
= 3.(-47,7) + 90,25 + 2.(-285,6) + 3.87,6 + 206,57 = -153,9(kJ)
Bi 4:
1) So snh AH, AU cua cc phan ung: C
n
H
2n
+ H
2
C
n
H
2n+2
2) Khi dt chy hon ton 2 anome o v | cua D glucozo mi thu 1 mol o p sut khng di,
nguoi ta do duoc hiu ung nhit cua cc phan ung o 500K ln luot bng:
-2790,0kJ v - 2805,1kJ
a) Tnh AU di voi mi phan ung.
b) Trong 2 dang glucozo, dang no bn hon?
Giai:
1) AH = AU + P. AV = AU + An.RT
Phan ung trn c: An = 1-2 = -1 AH = AU RT AH < AU
2) C
6
H
12
O
6
+ 6O
2
6CO
2
+ 6H
2
O
AU
(o)
= AH
(o)
- An.RT = - 2799 6.8,314.10
-3
.500 = -2824(kJ)
AU
(|)
= AH
(|)
- An.RT = - 2805,1 6.8,314.10
-3
.500 = -2830 (kJ)
o
H
o
A = 6.
o
CO S
H
) (
2
A + 6.
o
O H S
H
) (
2
A -
o
S
H
) (o
A
o
H
|
A = 6.
o
CO S
H
) (
2
A + 6.
o
O H S
H
) (
2
A -
o
S
H
) ( |
A
o
S
H
) (o
A -
o
S
H
) ( |
A =
o
H
|
A -
o
H
o
A = -2805,1 + 2799 = -6,1(kJ)
o
S
H
) (o
A <
o
S
H
) ( |
A Dang o - glucozo c
o
S
H A nho hon nn bn hon.
Bi 5:
1) Th no l entanpi sinh cua don cht? Tnh
o
O S
H
) (
3
A v
o
kimcuong S
H
) (
A v du don hoat tnh ho hoc cua
chng tu cc du kin sau:
(a): C
than ch
+ O
2(k)
CO
2(k)
o
H
298
A = -393,14(kJ)
(b): C
kim cuong
+ O
2(k)
CO
2(k)
o
H
298
A = -395,03(kJ)
(c): 3As
2
O
3 (r)
+ 3O
2(k)
3As
2
O
5(r)
o
H
298
A = -811,34(kJ)
(d): 3As
2
O
3 (r)
+ 2O
3(k)
3As
2
O
5(r)
o
H
298
A = -1090,98(kJ)
2) Tu kt qua trn v cc du kin sau:
AH
(O O)
tnh tu O
2
= - 493,24kJ/mol; AH
(O O)
tnh tu H
2
O
2
= - 137,94kJ/mol
Chng minh rng: Khng th gn cho O
3
cu trc vng kn.
C
lic
k
t
o
b
u
y
N
O
W
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Giai:
1)- Entanpi sinh cua cc don cht bn o diu kin chun = 0
- Di voi nhung nguyn t c nhiu dang th hnh th khi chuyn tu dang ny sang dang khc bao gio cung
km theo 1 hiu ung nhit. Hiu ung nhit cua qu trnh hnh thnh don cht (dang th hnh km bn) tu
dang th hnh bn o diu kin nht dinh duoc coi l nhit sinh cua don cht trong nhung diu kin d.
o
S
H A cua O
3
v kim cuong l hiu ung nhit quy v diu kin chun cua cc qu trnh:
2
3
O
2
O
3(k) ;
C
than ch
C
kim cuong
- Ly (a) (b):
C
than ch
C
kim cuong
o
kc S
H
) (
A = 1,89 kJ/mol
- Ly (c) - (d):
2
3
O
2(k)
O
3(k)
o
O S
H
) (
3
A = 139,82 kJ/mol
2) Nu coi O
3
c cu trc vng kn:
o
O S
H
) (
3
A =
o
O lk
H
) (
3
A -
2
3
o
O lk
H
) (
2
A
= 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 duoc.
Bi 6:
Entanpi sinh tiu chun cua CH
4(k)
v C
2
H
6(k)
ln luot bng -74,80 v -84,60 kJ/mol. Tnh entanpi tiu chun
cua C
4
H
10 (k)
. Bin lun v kt qua thu duoc. Cho bit entanpi thng hoa cua than ch v nng luong lin kt
H- H ln luot bng: 710,6 v - 431,65 kJ/mol.
Giai:
* (1) C
than ch
+ 2H
2 (k)
CH
4(k)
o
CH S
H
4
,
A =-74,8kJ
(2) C
than ch
C
(k)
o
th
H A = 710,6 kJ
(3) H
2 (k)
2H
(k)
lk
H A = 431,65 kJ
Ly (1) [(2) + 2.(3)] ta duoc:
C
(k)
+ 4H
(k)
CH
4(k)
o
CH tu ng S
H
4
, / ,
A = -1648,7(kJ/mol)
Nng luong lin kt trung bnh cua 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
A = -84,6 (kJ/mol)
Ly (4) [2 .(2) + 3.(3)] ta duoc: 2C
(k)
+ 6H
(k)
C
2
H
6 (k)
o
H C tu ng S
H
6
2
, / ,
A = -2800,75 (kJ/mol)
Coi E
C H
trong CH
4
v C
2
H
6
nhu nhau th: E
C- C
= =1800,75 6(- 412,175) = -327,7(kJ/mol)
* Coi E
C-H
; E
C- C
trong cc cht CH
4
, C
2
H
6
, C
4
H
10
du nhu nhau th:
o
H C tu ng S
H
10
4
, / ,
A = 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
, / ,
A = -5110,6 (kJ/mol)
Ly (2). 4 + (3).5 + (5) ta duoc:
4Cthan ch
+ 5H
2(k)
C
4
H
10(k)
o
H C S
H
10
4
,
A = -109,95(kJ/mol)
* Kt qua thu duoc chi l gn dng do d coi E
lk(C C)
, E
lk(C- H)
trong moi truong hop l nhu nhau.
V v vy s khng tnh r duoc
o
S
H A cua cc dng phn khc nhau.
C
lic
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Bi 7: Tnh AH
o
cua cc phan ung 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
,
A = -822,2 kJ/mol;
o
O Al S
r
H
) ( 3 2
,
A = -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
A = -296,6 kJ
(4): 2SO
2(k)
+ O
2(k)
2SO
3(k)
o
H
298
A = -195,96 kJ
Tu kt qua thu duoc v kha nng din bin thuc t cua 2 phan ung trn c th rt ra kt lun g?
Giai:
1)
o
pu
H
) 1 (
A =
o
O Al S
r
H
) ( 3 2
,
A -
o
O Fe S
r
H
) ( 3 2
,
A = -1676 + 822,2 = - 853,8(kJ)
2)
o
pu
H
) 2 (
A =
o
pu
H
) 3 (
A +
2
1
o
pu
H
) 4 (
A = -296,6 -
2
1
.195,96 = -394,58 (kJ)
KL: Hai phan ung (1), (2) du toa nhit manh. Song trn thuc t 2 phan ung d khng tu xay ra. Nhu vy,
chi dua vo AH khng du d khng dinh chiu cua 1 qu trnh ho hoc (tuy nhin trong nhiu truong hop, du
don theo tiu chun ny l dng).
Bi 8:
1) Tnh hiu ung nhit dng tch tiu chun cua cc phan ung sau o 25
o
C.
a) Fe
2
O
3(r)
+ 3CO
(k)
2Fe
(r)
+ 3CO
2(k)
o
H
298
A = 28,17 (kJ)
b) C
than ch
+ O
2(k)
CO
2 (k)
o
H
298
A = -393,1(kJ)
c) Zn
(r)
+ S
(r)
ZnS
(r)
o
H
298
A = -202,9(kJ)
d) 2SO
2(k)
+ O
2(k)
2SO
3(k)
o
H
298
A = -195,96 (kJ)
2) Khi cho 32,69g Zn tc dung voi dung dich H
2
SO
4
long du trong bom nhit luong k o 25
o
C, nguoi ta
thy c thot ra mt nhit luong l 71,48 kJ. Tnh hiu ung nhit o nhit d d. Cho Zn = 65,38
Giai:
1) AH = AU + An.RT
Do cc phan ung a), b), c) c An = 0 nn AU
o
= AH
o
Phan ung d): AU
o
= AH
o
- An.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 luong k c V = const.
AU = - 71,48.
38 , 65 / 69 , 32
1
= -142,96 (kJ/mol)
AH = AU + An.RT = - 142,96 + 1. 8,314 .298,15 .10
-3
= - 140,5 (kJ/mol)
Bi 9: Tnh AH
o
cua phan ung tng hop 1 mol adenine C
5
H
5
N
5(r)
tu 5 mol HCN
(k)
.
Cho bit
o
k CH S
H
) , ,
4
A = - 74,8 (kJ/mol);
o
k NH S
H
, ,
3
A = -46,1kJ/mol;
o
r adenin S
H
) ( ,
A = 91,1 kJ/mol
V CH
4(k)
+ NH
3(k)
HCN
(k)
+ 3H
2(k)
AH
o
= 251,2 kJ.mol
-1
Giai:
(a) : C
gr
+ 2H
2(k)
CH
4
o
k CH S
H
) , ,
4
A = -74,8 (kJ/mol)
(b) :
2
1
N
2(k)
+
2
3
H
2(k)
NH
3(k)
o
k NH S
H
, ,
3
A = - 46,1kJ/mol
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
(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
) ( ,
A = 91,1 kJ.mol
-1
(d) : CH
4(k)
+ NH
3(k)
HCN
(k)
+ 3H
2(k)
AH
o
= 251,2 kJ.mol
-1
Ta ly: -5 .(a) + [-5 .(b)] + (c) + [-5.(d)] ta duoc: 5HCN
(k)
C
5
H
5
N
5(r)
AH
o
(4)
= 251,2 kJ/mol
Bi 10:
Tnh nhit thot ra khi tng hop 17kg NH
3
o 1000K. Bit
o
k NH S
H
) , ( 298 ,
3
A = -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
Giai:
2
1
N
2(k)
+
2
3
H
2(k)
NH
3(k)
o
k NH S
H
, ,
3
A = - 46,2kJ/mol
AC
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
= A
o
H
1000
o
H
298
A + dT C
P
,
1000
298
}
A =
o
H
298
A + dT T) 10 . 541 , 31 1 , 32 (
1000
298
3
}

+
=
o
H
298
A + )
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 hop 17 kg NH
3
th nhit luong toa ra l: Q =
17
17000
.(-54364,183 .10
-3
) = -54364,183 (kJ)
Bi 11:
Tnh nng luong mang luoi tinh th BaCl
2
tu 2 t hop du kin sau:
1) Entanpi sinh cua BaCl
2
tinh th: - 859,41 kJ/mol
Entanpi phn li cua Cl
2
: 238,26 kJ/mol Entanpi thng hoa cua Ba: 192,28 kJ/mol
Nng luong ion ho thu nht cua Ba: 500,76 kJ/mol Nng luong ion ho thu hai cua Ba: 961,40 kJ/mol
i luc electron cua Cl : - 363,66 kJ/mol
2) Hiu ung nhit cua qu trnh ho tan 1 mol BaCl
2
vo mol H
2
O l: -10,16kJ/mol.
Nhit hidrat ho ion Ba
2+
: - 1344 kJ/mol Nhit hidrat ho ion Cl
-
: - 363 kJ/mol
Trong cc kt qua thu duoc, kt qua no dng tin cy hon.
Giai:
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
A
A A
S(BaCl
2
, tt)
pl (Cl
2
)
A A A
o
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
A
2) BaCl
2 (tt)
Ba
(aq)
+ 2Cl
(aq)
- U
ml
+

H 2
O
H
1 H
2
Ba
2+
+ 2Cl
-
H
ht(BaCl
2
)
A
A
2+
-
U
ml
= H
1
+ H
2
- H
= -1344 - 2.363 + 10,16 = -2059,84 (kJ/mol )
A A A
ht(BaCl
2
)
Kt qua 1) dng tin cy hon, kt qua tnh theo m hnh 2) chi l gn dng do m hnh ny khng m ta ht
cc qu trnh din ra trong dung dich, cc ion nht l cation t nhiu cn c tuong tc ln nhau hoc tuong
tc voi H
2
O.
Bi 12:
Cho gin no 10 lt kh He o 0
o
C, 10atm dn p sut l 1atm theo 3 qu trnh sau:
a) Gin dng nhit thun nghich.
b) Gin doan nhit thun nghich.
c) Gin doan nhit khng thun nghich.
Cho nhit dung dng tch cua He C
V
=
2
3
R v chp nhn khng di trong diu kin d cho cua bi ton.
Tnh th tch cui cng cua h, nhit Q, bin thin ni nng AU v cng W trong mi qu trnh ni trn?
Giai:
a) T = const AU = 0; AH = 0 AU = Q + W = 0 Q = -W
W = -
} }
=
2
1
2
1
.
V
dV
nRT dV P = - nRTln
1
2
V
V
Voi kh l tuong: 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
AU = W = n.
V
C . AT =
2
3
.
.
.
1
1 1
T R
V P
.R(T
2
T
1
) AU = 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
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
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
A
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 AU = 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
=
AU = 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 :
Phan ung sau: Ag +
2
1
Cl
2
= AgCl
Xay ra duoi p sut 1 atm v o 25
o
C toa ra 1 nhit luong l 126,566 kJ.
Nu cho phan ung d xay ra trong 1 nguyn t ganvani o P, T = const th ho nng s duoc chuyn thnh
din nng v san ra cng W = 109,622 kJ.
Hy chung to rng trong ca 2 truong hop trn, bin thin ni nng cua h vn chi l mt, cn nhit th khc
nhau v tnh gi tri bin thin ni nng d.
Giai:
- Do U l hm trang thi nn AU = U
2
U
1
= const, cho d su bin di duoc thuc hin bng cch no. V
vy AU trong 2 truong hop trn chi l mt.
- V AU = Q + W = Q + W - PAV = Q + W - An.RT
Do AnRT = const; AU = const
Nn khi W (cng c ch) thay di th Q cung thay di
- AU = AH - AnRT = -126,566 +
2
1
. 8,314 .298,15.10
-3
= - 125,327 (kJ)
Bi 14:
Tnh cng cua su bin di dng nhit thun nghich v bt thun nghich 42g kh N
2
o 300K khi:
a) Gin no tu 5atm dn 1atm.
b) Nn tu 1atm dn 5atm.
(Kh duoc coi l l tuong). So snh cc kt qua v rt ra kt lun.
Giai:
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
. AV = -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
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
= - 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
. AV= -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 thuc hin (sinh) trong qu trnh bin thin thun nghich tu trang thi 1 dn trang thi 2
bng cng m h nhn khi tu trang thi 2 v trang thi 1. Cn trong qu trnh bin thin bt thun nghich th
cng h sinh nho hon cng h nhn.
- Trong su bin thin thun nghich th h sinh cng lon hon trong qu trnh bin thin bt thun nghich.
Bi 15: Phan ung: C
6
H
6
+
2
15
O
2(k)
6CO
2(k)
+ 3H
2
O
o 300K c Q
P
Q
V
= 1245(J). Hoi C
6
H
6
v H
2
O trong phan ung o trang thi long hay hoi?
Giai:
Q
P
Q
V
=AnRT = 1245(J) An =
300 . 314 , 8
1245
= 0,5 H
2
O v C
6
H
6
phai o th hoi th An = 0,5
Bi 16:
Tnh nhit luong cn thit d nng nhit d cua 0,5 mol H
2
O tu -50
o
C dn 500
o
C o
P = 1atm. Bit nhit nng chay cua nuoc o 273K l L
nc
= 6004J/mol,
nhit bay hoi cua nuoc o 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)
Giai:
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
A
A
A
A
A
AH
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
+ + + = A
} }
+
}
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 su bin thin entropi cua qu trnh dun nng 0,5 mol H
2
O tu 50
o
C dn 500
o
C o P = 1atm.
Bit nhit nng chay cua nuoc o 273K = 6004J/mol; nhit bay hoi cua nuoc o 273K = 40660J/mol. Nhit
dung mol dng p
o
P
C cua nuoc d v nuoc long ln luot bng 35,56 v 75,3J/molK;
o
P
C cua hoi nuoc l
(30,2 + 10
-2
T) J/molK
Giai:
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
A A
A
A
A
773K
373K 373K 273K 273K
223K
o
o o o o
S
2
S
3
S
4
S
5
A A A A
o o o o
= + + + +
S A
o
S
1
A
o
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
= n.
(
+ + + +
} } }
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.
(
+ + + + +

) 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)
Bi 18:Tnh su bin thin entropi khi trn ln 200g nuoc o 15
o
C voi 400g nuoc o 60
o
C. Bit rng h l c
lp v nhit dung mol cua nuoc long l 75,3 J/mol.K
Giai:
Goi T l nhit d cua h sau khi pha trn.
Do Q
thu
= Q
toa
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)
AS
h
= AS
1
+ AS
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 d ny tu xay ra.
Bi 19: Tnh su bin thin entropi v AG cua su hnh thnh 1 mol hn hop kh l tuong gm 20% N
2
; 50%H
2
v 30%NH
3
theo th tch. Bit rng hn hop kh duoc tao thnh do su khuch tn 3 kh vo nhau bng cch
ni 3 bnh dung 3 kh thng voi nhau. Nhit d v p sut cua cc kh lc du du o dkc (273K, 1atm).
Giai:
V kh l tuong khuch tn vo nhau nn qu trnh l dng nhit.
Goi th tch cua 1 mol hn hop kh l V th tch mi kh ban du (o cng diu 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.
- Su bin thin entropi duoc tnh theo CT: AS = nRln
1
2
V
V
2
N
S A = 0,2 .8,314.ln
V
V
2 , 0
= 2,676J/K
2
H
S A = 0,5.8,314.ln
V
V
5 , 0
= 2,881J/K
3
NH
S A = 0,3.8,314.ln
V
V
3 , 0
= 3,003J/K
AS =
2
N
S A +
2
H
S A +
3
NH
S A = 8,56(J/K)
* Qu trnh khuch tn kh l tuong l dng nhit nn AH = 0
AG
273
= AH T. AS = -273.8,56 = -2336,88(J)
Bi 20: Trong cc phan ung sau, nhung phan ung no c AS > 0; AS < 0 v AS = 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)
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Giai:
Phan ung (1) c An kh = 2 -1 = 1 > 0 AS > 0
Phan ung (2) c An kh = 1 -1-
2
1
< 0 AS <0
Phan ung (3), (4) c An kh = 0 AS = 0 t.
Bi 21: Cho bit pu:
C
2
H
4(k)
+ H
2
O
(h)
C
2
H
5
OH
(h)
v c c s l i u sau:
C
2
H
5
OH C
2
H
4(k)
H
2
O
(h)
) / (
298 ,
mol kJ G
o
S
A 168,6 68,12 - 228,59
) / (
298
mol kJ S
o
282,0 219,45 188,72
a) Hoi diu kin chun cua phan ung ny l diu kin nhu th no?
b) o diu kin chun v 25
o
C phan ung di theo chiu no?
c) Tnh
o
H
298
A cua phan ung. Phan ung toa nhit hay thu nhit?
Giai:
a) Diu kin chun:
) (
4 2
k H C
P =
) (
2
h O H
P =
) (
5 2
h OH H C
P = 1atm v phan ung duoc thuc hin o t
o
, P khng di.
b)
A
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 chi u thun
o
A A
A
A
c)
o
AS
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 nhi t
A A A
A A A
A
o
o
o o
Bi 22: Mt mol kh l tuong don nguyn tu o 300K v 15atm gin no toi p sut 1atm. Su gin no
duoc thuc hin bng con duong:
a) Dng nhit v thun nghich nhit dng. b) Dng nhit v khng thun nghich.
c) Doan nhit v thun nghich. d) Doan nhit bt thun nghich.
Trong cc qu trnh bt thun nghich, su gin no chng lai p sut 1atm. Tnh Q, W, AU, AH, AS
tp
cho mi
truong hop.
Giai:
a) T = const AU = 0 ; AH = 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 no thun nghich: AS
tp
= AS
mt
+ AS
h
= 0
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b) T = const AU = 0 ; AH = 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)
AS
tp
= AS
mt
+ AS
h
AS
h(BTN)
= AS
h(TN)
=
T
Q
TN
= =
A
T
W U
}
2
1
T
dT
nC
V
+ dV
V
nR
}
2
1
= nRln
1
2
V
V
= nRln
2
1
P
P
= 1.8,314 .ln
1
15
= 22,515(J/K)
AS
mt
=
T
Q
mt
= -
T
Q
he
=
300
92 , 2327
= -7,76(J/K) AS
tp
= 22,515 - 7,76 = 14,755 (J/K)
( Qu trnh gin no ny tu xay ra)
c) Doan nhit Q = 0
Doan nhit thun nghich 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-
Voi kh l tuong don nguyn tu 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
AU = W = nC
V
(T
2
- T
1
) = 1.
2
3
.8,314.(101,55 - 300) = -2474,87(J)
AH = nC
P
(T
2
- T
1
) = 1.
2
5
.8,314 .(101,55 - 300)= - 4124,78(J) AS
TN
=
T
Q
= 0
d) Doan nhit Q = 0
Doan nhit, khng thun nghich khng p dung duoc PT poisson
AU = W nC
V
. AT = -P
ng
. AV
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)
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AU = W = 1.
2
3
.8,314.(188- 300) = -1396,752(J)
AS
tp
= AS
h
=
T
Q
TN
= =
A
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 23: Tnh
0
273
G A cua phan ung: 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 A (kJ/mol) - 74,8 - 241,8 -110,5 0
0
298
S (J/molK) 186,2 188,7 197,6 130,684
a) Tu gi tri AG
0
tm duoc c th kt lun g v kha nng tu din bin cua kha nng phan ung o 373
o
K?
b) Tai nhit d no th phan ung d cho tu xay ra o diu kin chun?
(Coi AH
0
, AS
0
khng phu thuc T)
Giai:
0
pu
H A = 3.0 + 1(-110,5) -(-74,8) -(-241,8) = 206,1(kJ)
0
pu
S A = 3.(130,684) + 197,6 - 188,7 - 186,2 = 214,752 (J/K)
Do AH
0
, AS
0
khng phu thuc vo T nn:
0
273
G A = AH
0
- T. AS
0
= 206,1 = 373.214,752.10
-3
=125,9975(kJ) > 0
o dkc v T = 373K Phan ung khng th tu din bin.
b) D phan ung tu din bin o nhit d T(K) th:
0
T
G A < 0 AH
0
- T. AS
0
< 0
T >
0
0
S
H
A
A
=
752 , 214
10 . 1 , 206
3
= 959,71(K)
Bi 24: Entanpi tu do chun cua phan ung tao thnh H
2
O tu cc don cht phu thuc vo T theo phuong
trnh sau:
0
,T S
G A = -240000 + 6,95T + 12,9TlgT (J/mol)
Tnh AG
0
, AS
0
v AH
0
cua phan ung tao thnh H
2
O o 2000K
Giai:
0
2000 , S
G A = -240000 + 6,95.2000 + 129.2000lg2000= -140933,426(J/mol) dG = VdP - SdT
P
T
G
|
.
|
\
|
c
c
= -S
0
2000
S A = -
P
T
G
|
|
.
|
\
|
c
A c
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 A =
0
2000
G A + T.
0
2000
S A = -140933,426 + 2000. 55,1357 = -30662,054 (J/mol)
Bi 25: Mt Hoc sinh khi lm bi tuong trnh th nghim do nhit d dt chy mt hop cht huu co cho
rng: AH = AU + P. AV. Su dt chy trong bom nhit luong k lm cho AV = 0, do d AH = AU. Kt lun
ny sai o du?
Giai:
H = U + P.V AH = AU + A(PV) = AU + P. AV + V. AP
Hay AH = AU + A(nRT)
Trong bom nhit luong k th: AV = 0 nn: AH = AU + V. AP = AU + A(nRT)
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Bi 26: Hy chi ra nhung mnh d sai:
a) Di voi 1 h kn, qu trnh gin no kh l doan nhit h l c lp Q = 0; AS = 0.
b) Mt h bt ky c th tu din bin toi trang thi c entanpi thp hon (AH < 0) v entropi lon hon (AS > 0).
Hay h c th din bin theo chiu giam entanpi tu do (AG < 0).
c)
0
T
G A =
0
T
H A - T.
0
T
S A
Voi phan ung ho hoc o T = const. Nu
0
G A > 0 Phan ung tu din bin theo chiu nghich.
0
G A = 0 : Phan ung o trang thi cn bng.
0
G A < 0 : Phan ung tu xay ra theo chiu thun.
Giai:
a) Sai . Do AS = 0 chi khi qu trnh bin di thun nghich.
Cn voi qu trnh bin di bt thun nghich th AS >
T
Q
AS > 0.
b) Sai . Do mnh d ny chi dng trong diu kin T, P = const.
Cn voi qu trnh bin di m V, T = const th phai xt AF.
c) Sai. Do voi qu trnh ho hoc th phai xt gi tri:
AG = AG
0
+ RTlnQ chu khng phai dua vo AG
0
.
(Tuy nhin, c th coi rng
0
T
G A << 0 th qu trnh c th xay ra duc ca o diu kin chun v diu kin
thc. Khi
0
T
G A << 0 th v nguyn tc ch c qu trnh nguc li mi xay ra, khng th xc djnh duc
chnh xc gii hn cua
0
T
G A m theo d qu trnh xay ra theo chiu ny hay chiu khc. Mt cch gn
dng c th coi rng cc gii hn ny khoang chng 40 kJ/mol).
Bi 27: Mt kh l tuong c C
V
= 3R khng phu thuc T duoc gin no doan nhit trong chn khng toi th
tch gp di. Hoc sinh A l lun rng di voi qu trnh doan nhit th
1
2
1
1
2
|
|
.
|
\
|
=

V
V
T
T
voi =
3
4
do d T
2
=
3
1
1
2
T
Hoc sinh B cho rng: AU = Q + A = 0 + 0 = n.C
V
. AT AT = 0 T
2
= T
1
Hoc sinh no ni dng? Hy chi ra li sai cua Hoc sinh kia.
Giai:
- Hoc sinh B ni dng.
- Hoc sinh A ni sai : V qu trnh gin no trong chn khng l qu trnh bt thun nghich nn khng su
dung duoc phuong trnh poisson.
Bi 28: Tnh cht nhit dng cua mt s phn tu v ion o trang thi tiu chun tai 25
o
C nhu 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 A (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) voi O
2
(k) tao thnh theo 2 cch :
a) Bt thun nghich b) Thun nghich (trong 1 t bo din ho)
1) Tnh AH
0
, AU
0
, AS
0
, AG
0
cua phan ung trong mi cch ni trn?
2) Tnh nhit, cng th tch, cng phi th tch (tuc l cng huu ch) m h trao di voi mi truong trong mi
cch?
3) Tnh AS cua mi truong v AS tng cng cua vu tru khi tin hnh qu trnh theo mi cch.
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4) Mt m hnh t bo din ho khc lm vic dua trn phan ung oxi ho C
3
H
8
(k) boi O
2
(k) khi c mt dung
dich KOH 5M voi din cuc Pt. Cc loai phn tu v ion (tru KOH) du o trang thi tiu chun. Hy vit cc
nua phan ung o catot v anot v phan ung tng cng trong t bo din ho. Nu tu t bo din ho d, o
25
o
C, ta thu duoc dng din 100mA. Hy tnh cng sut cuc dai c th dat duoc.
Giai:
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 trang thi nn d tin hnh theo cch no th cc gi tri AU, AH, AS, AG
cung nhu nhau voi cng trang thi du v cui. Vy:
0
pu
H A = 3
0
) ( ,
2
k CO S
H A + 4.
0
) ( ,
2
l O H S
H A -
0
) ( ,
8 3
k H C S
H A - 5.
0
) ( ,
2
k O S
H A
= -3. 393,51 - 285,83 .4 + 103,85 = -2220 (kJ)
0
pu
H A = 213,74. 3 + 4.69,91 - 269,91 - 5. 205,138 = -374,74 (J/K)
0
pu
G A = AH
0
- T. AS
0
= -2220 + 298,15 .374,74.10
-3
= -2108,27 (kJ)
AU
0
= AH
0
- A(PV) = AH
0
- AnRT = -2220 - (-3).8,314.298,15.10
-3
= -2212,56(kJ)
2) a) Qu trnh bt thun nghich:
- Nhit m h trao di voi mi truong l Q
BTN
= AH
0
= -2220 (kJ)
- W
tt
= -
}
2
1
.dV P = -P. AV = -An
(k)
.RT
= 3. 8,3145.298,15 = 7436,9(J)
- W = 0
b) Qu trnh thun nghich:
- Q
TN
= T. AS = 298,15 (-374,74) = - 111728,731(J)
- W
max
= AG = -2108,27(kJ) < 0 : H sinh cng
- W
tt
= - An
(k)
.RT = 7436,9(J) > 0: h nhn cng
3) a) Qu trnh bt thun nghich:
AS
mt
=
T
Q
mt
= -
T
Q
BTN
= -
T
H
0
A
= -
15 , 298
10 . 2220
3
= 7445, 916 (J/K)
AS
vu tru
= AS
mt
+ AS
h
= 7445,916 - 374,74 = 7071,176(J/K)
b) Qu trnh thun nghich:
AS
mt
=
T
Q
mt
= -
T
Q
TN
= ) / ( 74 , 374
15 , 298
731 , 111728
K J =
AS
vu tru
= AS
mt
+ AS
h
= 0
4) Cc nua phan ung:
Anot: C
3
H
8
+ 26OH
-
3
2
3
CO + 17H
2
O + 20e
Catot: O
2
+ 2H
2
O + 4e 4OH
-
Phan ung tng cng:
C
3
H
8(k
) + 5O
2(k)
+ 6OH
-
(aq)
3
2
) ( 3 aq
CO + 7H
2
O
(l)
So d pin:
(-) Pt, C
3
H
8
(1atm)/KOH(5M), K
2
CO
3
(1M)/ O
2
(1atm), Pt (+)
0
pu
H A = 3(-677,14) + 7.(-285,83) + 103,85 - 5.0 - 6(-229,99) = -2548,44(KJ)
0
pu
S A = 3.(-56,9) + 7.69,91 - 269,91 - 5.205,138- 6(-10,74) = -912,43(KJ)
0
pu
G A =
0
pu
H A = T.
0
pu
S A = -2548,44 + 298,15.912,43.10
-3
= - 2276,399(KJ)
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g
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cu-trac
k
.c
o
m
0
pu
E = -
nF
G
0
A
=
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 29: Tnh bin thin entropi khi chuyn 418,4J nhit tu vt c t
0
= 150
o
C dn vt c t
0
= 50
o
C.
Giai:
Qu trnh bin di trn l khng thun nghich duoc coi nhu gm 3 qu trnh bin thin thun nghich:
1) Vt o 150
o
C truyn nhit thun nghich o T = const.
AS
1
=
T
Q
=
15 , 273 150
4 , 418
+
= - 0,989(J/K)
2) H bin thin doan nhit tu 150
o
C dn 50
o
C
AS
2
= 0
3) Vt o 50
o
C nhn nhit thun nghich o T = const
AS
3
= -
T
Q
=
15 , 273 50
4 , 418
+
= 1,295(J/K)
Do S l hm trang thi nn:
AS
BTN
= AS
TN
= AS
1
+ AS
2
+ AS
3
= 0,306(J/K)
Bi 30: Bit o -15
o
C, P
hoi
(H
2
O, l) = 1,428 (torr)
o -15
o
C, P
hoi
(H
2
O,r) = 1,215(torr)
Hy tnh AG cua qu trnh dng dc 1 mol H
2
O
(l)
thnh nuoc d o -15
o
C v 1atm.
Giai:
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
A
(1), (3) l qu trnh chuyn pha thun nghich
AG
1
= AG
3
= 0
AG = AG
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 o 25
o
C, 2atm, 1 mol O
2
nguyn cht o 25
o
C, 1atm
1 mol O
2
o 25
o
C trong khng kh trn mt dt (P = 1atm, O
2
chim 21% V khng kh)
- So snh gi tri hm G cua 1 mol O
2
trong 3 truong hop trn hon km nhau bao nhiu J?. Tu d rt ra kt
lun: Kha nng phan ung cua O
2
trong mi truong hop trn cao hay thp hon so voi truong hop khc?
Giai:
* G
0
l hm Gibb cua 1 mol O
2
o 1atm
- 1 mol O
2
, 1atm, 25
o
C 1 mol O
2
, 2atm, 25
o
C
(G
0
) (G
1
)
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k
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o
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AG
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
.
- Goi G
2
l hm Gibb cua 1mol O
2
o 25
o
C trong khng kh (0,21 atm)
1mol O
2
, 25
o
C, 1atm 1 mol O
2
, 25
o
C, 0,21atm
(G
0
) (G
2
)
AG
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
o 25
o
C, 2atm c kha nng phan ung cao nht cn
1 mol O
2
nm trong khng kh th b nht c kha nng phan ung km nht.
Bi 32: Nhit ho tan (AH
ht
) 0,672g phenol trong 135,9g clorofom l -88J v cua 1,56g phenol trong
148,69g clorofom l -172J.
Tnh nhit pha long di voi dung dich c nng d nhu dung dich thu 2 chua 1 mol phenol khi pha long
dn nng d cua dung dich thu nht bng clorofom.
Giai:
94g phenol + CHCl
3
dd 2 dd 1
H pha l o ng
+ CHCl
3
H
ht (2)
H
ht(1)
H
pha l o ng
= H
ht(1)
- H
ht(2)
= - .(-172) + (-88) = - 2004,87(J)
0,672
94
1,569
94
A
A
A A A
A
Bi 33: Nhit ho tan 1 mol KCl trong 200 ml nuoc duoi p sut P = 1amt l:
t
0
C 21 23
AH 18,154 17,824 (kJ)
Xc dinh AH
298
v so snh voi gi tri thuc nghim l 17,578 (kJ)
Giai:
Theo dinh lut Kirchhoff: AH
294
= AH
298
+ AC
P
.(294 - 298) = 18,454 (kJ)
AH
286
= AH
298
+ AC
P
.(296 - 298) = 17,824(kJ)
A
A
H
298
= 17,494 (kJ)
C
P
= -0,165 (kJ/K)
H
298(LT)
- H
298(TN)
H
298(TN)
0,48%
~
~
A A
A
Vy AH
298
tnh duoc theo l thuyt sai khc voi gi tri TN l 0,48%.
Bi 34: Tnh AS cua qu trnh ho hoi 3 mol H
2
O (l) o 25
o
C, 1atm.
Cho: AH
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)
Giai:
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
AS
AS
1
AS
2
AS
3
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k
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k
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o
m
AS
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)
AS
2
=
T
Q
2
=
T
H n
l hh.
.A
= 3.
15 , 373
10 , 656 , 40
3
= 326,8605(J/K)
AS
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)
AS = AS
1
+ AS
2
+ AS
3
= 354,9383 (J/K)
Bi 35:
a) Tnh cng trong qu trnh dt chy 1 mol ruou etylic o dkc v 25
o
C.
b) Nu H
2
O o dang hoi th cng km theo qu trnh ny l bao nhiu?
Giai:
a) C
2
H
5
OH
(l)
+ 3O
2 (k)
2CO
2 (k)
+ 3H
2
O
(l)
An = -1
W = -P
ng
. AV = -P
ng
.
ng
P
RT n. A
= R.T = 8,314.29815 = 2478,82 (J)
b) Nu H
2
O o dang hoi th: An = 2.
W = - An. RT = -2 .8,314 .298,15 = - 4957,64(J)
Bi 36: Tnh AS, AG trong qu trnh gin khng thun nghich 2 mol kh l tuong tu 4lt dn 20 lt o 54
o
C.
Giai:
V S, G l cc hm trang thi nn AS, AG khng phu thuc vo qu trnh bin thin l thun nghich hay bt
thun nghich m chi phu thuc vo trang thi du v trang thi cui. V vy:
AS = nRln
1
2
V
V
= 2. 8,314.ln
4
20
= 26,76 (J/K)
T = const AH = 0; AU = 0
AG = AH - T. AS = 0 -(273,15 + 54) .26,76 = - 8755,1 (J)
Bi 37: Mt bnh c th tch V = 5(l) duoc ngn lm 2 phn bng nhau. Phn 1 chua N
2
o 298K v p
sut 2atm, phn 2 o 298K v p sut 1atm. Tnh AG, AH, AS cua qu trnh trn ln 2 kh khi nguoi ta bo
vch ngn di.
Giai:
o T = 298K ; V
bd
(N
2
) = V
bd
(O
2
) =
2
5
(l)
AS = AS(N
2
) + AS(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
= 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 dng nhit AH = 0 AG = AH - T. AS = - 298 .1,763 = - 525,374 (J)
Bi 38: Cho cc du liu sau dy o 298K
Cht
0
S
H A (kJ/molK) S
0
(J/molK) V(m
3
/mol)
C
than ch
0,00 5,696 5,31.10
6
C
kim cuong
1,90 2,427 3,416.10
-6
1) o 298K c th c mt phn rt nho kim cuong cng tn tai voi than ch duoc khng?
2) Tnh p sut ti thiu phai dng d c th diu ch duoc kim cuong o 298K?
C
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k
.c
o
m
Giai
1)
C
ki m c- ng
C
than ch
G
0
= ?
298
A
AH
o
= AH
o
than ch
- AH
o
kim cuong
= 0 - 1,9 = -1,9 (kJ)
AS
o
= S
o
than ch
- S
o
kim cuong
= 5,696 - 2,427 = 3,269 (J/K)
0
, 298 pu
G A = AH
o
- T. AS
o
= -1900 - 298.3,269 = -2874,162(J)
AG
o
< 0 (Tuy nhin AG
o
khng qu m)
Phan ung tu xay ra theo chiu thun khng tn tai mt luong nho kim cuong cng voi than ch.
2)
G
0
= +2874,162 (J)
298
A
C
than ch
C
ki m c- ng
AV = 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
|
.
|
\
|
c
c
= V
T
P
G
|
.
|
\
|
c
A c
= AV
2
P
G A -
1
P
G A = AV(P
2
- P
1
)
D diu ch duoc kim cuong tu than ch th:
2
P
G A _ 0
1
P
G A + AV(P
2
- P
1
) _ 0
P
2
- P
1
_ -
V
G
P
A
A
1
(Do AV < 0) P
2
_ P
1
-
V
G
P
A
A
1
= 1 +
325 , 101 . 10 . 894 , 1
162 , 2874
3
P
2
_ 14977,65 (atm)
Vy p sut ti thiu phai dng d diu ch duoc kim cuong tu than ch l 14977,65atm.
Nh- vy 25
o
C, cn bng than ch ki m c- ng tn t i p sut khong
15000 atm. o p sut cao hon qu trnh chuyn than ch thnh kim cuong l tu din bin, mc du voi tc d
rt chm. Mun tng tc d phai tng nhit d v p sut, trong thuc t qu trnh chuyn than ch thnh kim
cuong duoc tin hnh khi c xc tc (Ni + Cr + ) o nhit d trn 1500
o
C v P ~ 50000atm.
Bi 39: Phan ung giua Zn v dd CuSO
4
xay ra trong ng nghim toa ra luong nhit 230,736kJ. Cung
phan ung trn cho xay ra trong pin din th mt phn ho nng chuyn thnh din nng. Cng din cua pin l
210,672kJ. Chung minh rng: AU cua 2 qu trnh khng di, nhung nhit toa ra thay di. Tnh AS cua phan
ung, AS
mt
v AS
tp
? Cho T = 300K
Giai:
Zn + CuSO
4
= ZnSO
4
+ Cu
- Khi thuc hin trong ng nghim: (Tin hnh bt thun nghich)
V
Zn
~ V
Cu
W
tt
= 0 ; W = 0
AU
BTN
= Q
BTN
= AH = -230,736kJ
- Khi thuc hin phan ung trong pin din (qu trnh thun nghich)
W
max
= - 210,672 (kJ) AG = W
max
= -210,672(kJ)
AH
TN
= AH
BTN
= - 230,736(kJ) Q
TN
= T. AS = AH - AG = -230,736 + 210,672 = -20,064(kJ)
AU
TN
= Q + W + P. AV = -20,064 = 210,672 + 0 = -230,736 (kJ) = AU
BTN
- AS
h
=
T
Q
TN
= -
300
10 . 064 , 20
3
= 66,88(J/K)
AS
mtBTN
= -
T
Q
BTN
=
300
10 . 736 , 230
3
= 769,12(J/K) AS
tp(BTN)
= 702,24(J/K)
AS
mt(TN)
= -
T
Q
TN
= -AS
h
AS
tp(TN)
= 0
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Bi 40:
- AG
p
= W
max
Xt 1 phan ung thun nghich trong pin din th AG
p
= W
max
< 0
- Nhung mt hoc sinh vit rng:
Trong moi qu trnh lun c: AS
vu tru
= AS
mt
+ AS
h
(1)
AH
mt
= - AH
h
(2)
AS
mt
=
T
H
mt
A
= -
T
H
he
A
AS
vu tru
= -
T
H
he
A
+ AS
h
T. AS
vu tru
= - AH
h
+ T. AS
h
= -AG
h
Voi qu trnh thun nghich th AS
vu tru
= 0 AG
h
= 0 AG
p
= 0
Hy giai thch mu thun ny.
Giai:
(2) chi dng khi ngoi cng gin no h khng thuc hin cng no khc:
AH = AU + P. AV AU = AH - P. AV
Q = AU - W = (AH - P. AV) - (-P. AV + W)
Q
h
= AH
h
- W = - AH
mt
Chi khi W = 0 th AH
mt
= - AH
h
* Trong pin: W
max
= AG < 0 nn AH
mt
= AH
h
.
Bi 41: Xt phan ung: Zn
(r)
+ Cu
2+
(aq)
Zn
2+
(aq)
+ Cu
(r)
din ra trong dktc o 25
o
C.
a) Tnh W, Q, AU, AH, AG, AS cua phan ung o diu kin trn.
Bit: Zn
2+
(aq)
Zn
(r)
Cu
(r)
Cu
2+
(aq)
0
298 , S
H A (kJ/mol) -152,4 0 0 64,39
0
298
S (J/mol.K) - 106,5 41,6 33,3 - 98,7
b) Xt kha nng tu din bin cua phan ung theo 2 cch khc nhau.
c) Nu thuc hin phan ung trn 1 cch thun nghich trong pin din th cc kt qua trn c g thay di? Tnh
E
pin
?
Giai:
a)
0
pu
H A =
0
,
2+
A
Zn S
H +
0
,Cu S
H A - + A
0
,Zn S
H
0
,
2+
A
Cu S
H = -152,4 - 64,39 = -216,79 (kJ)
0
pu
S A =
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 A =
0
H A - T.
0
S A = -216,79 + 298,15 .16,1.10
-3
= -211,99(kJ)
AU
o
= Q
P
=
0
pu
H A = -216,79 (kJ) W = 0; qu trnh BTN; W = 0
b) *
0
pu
G A = -211,99 (kJ) << 0 ( _ - 40 kJ)
Do
0
pu
G A rt m nn phan ung tu xay ra khng nhung o dkc m cn ca o cc diu kin khc nua.
* AS
mt
=
T
Q
mt
=
T
H
he
0
A
=
15 , 298
10 . 79 , 216
3
= 727,12 (J/K)
AS
vu tru
= AS
h
+ AS
mt
= -16,1 + 727,12 = 711,02 (J/K)
V AS
h c lp
= AS
vu tru
= 711,02 (J/K) > 0 Qu trnh l bt thun nghich phan ung tu xay ra.
c) Khi thuc hin phan ung trn TN trong pin din th cc gi tri AH
0
, AS
0
, AG
0
, AU
0
khng thay di do H, S,
G, U l cc hm trang thi nn khng phu thuc qu trnh bin di l thun nghich hay bt thun nghich
nhung cc gi tri Q, W th thay di.
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cu-trac
k
.c
o
m
Cu th: W
tt
= 0; W
max
= AG0 = -211,99(kJ) => Q = T. AS = 298,15 .(-16,1) = - 4800,215 (J)
AS
mt
=
T
Q
mt
=
T
Q
he
= 16,1 (J/K) AS
vu tru
= AS
mt
+ AS
h
= 0 =>E
pin
= -
nF
G
0
A
=
96485 . 2
211990
~ 1,1(V)
Bi 42:
Di voi nguyn t Danien o 15
o
C nguoi ta xc dinh duoc suc din dng E = 1,09337V v h s nhit d
cua suc din dng
T
E
c
c
= 0,000429 V/K. Hy tnh hiu ung nhit cua phan ung ho hoc?
Giai:
AG = - nEF
T
G
c
c
= - nF.
T
E
c
c
= - AS AS = nF .
T
E
c
c
AH = AG + T. AS = nF.(T.
T
E
c
c
- E) AH = 2. 96485 .(298,15.0,000429 - 1,09337) - - 187162,5(J)
Bi 43: Cho phan ung ho hoc: Zn + Cu
2+
Zn
2+
+ Cu
xay ra mt cch thun nghich dng nhit, dng p o 25
o
C trong nguyn t Ganvani.
Suc din dng cua nguyn t do duoc l 1,1V v h s nhit d cua suc din dng l :
P
T
E
|
.
|
\
|
c
c
= 3,3.10
-5
(V/K).
a) Tnh hiu ung nhit Q, bin thin Gipxo AG v bin thin entropi AS cua phan ung ho hoc d cho.
b) Tnh Q
tn
cua qu trnh?
c) Nu cung phan ung ho hoc trn thuc hin o cng nhit d v cng p sut nhung trong mt bnh cu
thuong th cc gi tri cua AG, AS s l bao nhiu?
Giai:
a) AG = - nEF = - 2 .1,1 .96485 = - 212267(J)
AS = -
T
G
c
A c
= n.F .
T
E
c
c
= 2 .96485 .3,3 .10
-5
= 6,368 (J/K)
AH = AG + T. AS = 212267 + 298,15 .6,368 = -210368,4(J)
b) Q
tn
= T . AS = 298,15 .6,368 = 1898,62 (J)
c) Nu phan ung ho hoc thuc hin o cng nhit d, p sut nhung trong 1 bnh cu thuong tuc l thuc hin
qu trnh mt cch bt thun nghich th AG, AS cua phan ung vn nhu o cu (a). Do G, S l cc hm trang
thi gi tri cua AG, AS khng phu thuc vo qu trnh bin thin.
Bi 44: Tnh cng cua su bin di dng nhit thun nghich v bt thun nghich cua 48 gam kh O
2
duoc
coi l l tuong o nhit d 25
0
C khi:
a. Gin no tu 10atm xung 1atm b. Nn tu 1atm dn 10atm
Dp s: a. W
tn
= -8,6.10
-3
J; W
btn
=-3,3.10
3
J b. W
tn
= 8,6.10
-3
; W
btn
= 3,3.10
4
J.
IV- KET LUAN - KIEN NGHJ :
Trn dy l h thng cu hoi v bi tp phn Nhit ho hoc m ti d p dung trong giang day. N tuong
di ph hop voi yu cu v muc dch giang day, bi dung hoc sinh kh, gioi o truong chuyn chun bi du
thi hoc sinh gioi cc cp . N c th dng lm ti liu hoc tp cho hoc sinh cc lop chuyn Ho hoc v ti
liu tham khao cho cc thy c gio trong giang day v bi dung hoc sinh gioi Ho hoc o bc THPT gp
phn nng cao cht luong giang day v hoc tp mn Ho hoc.
Tuy nhin, dy chi l mt phn rt nho trong chuong trnh n luyn cho hoc sinh chun bi tham gia vo cc
ky thi hoc sinh gioi cc cp.
V vy, ti rt mong cc Thy, C dng nghip gp kin cho ti v chuyn d ny v cng nhau pht trin
sang cc chuyn d khc d hoc tr chuyn Ho ngy cng c nhiu ti liu hoc tp mt cch h thng hon.
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m
C
lic
k
t
o
b
u
y
N
O
W
!
P
D
F
-XChan
g
e
w
w
w
.d
o
cu-trac
k
.c
o
m

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