Ch2-Nhiet Dong Hoc

Bi ging mn C s l thuyt Ha hc
CHNG II: NGUYN L II CA NHIT NG HC CHIU V GII HN

T DIN BIN CA QU TRNH

M U
Trong t nhin, cc qu trnh l hc v ho hc xy ra theo chiu hon ton xc nh.
- Nhit t truyn t vt nng sang vt lnh hn
- Kh t truyn t ni c p sut cao n ni c p sut thp
- Cc phn ng ho hc t xy ra, v d: Zn + HCl --> ZnCl
2
+ H
2

Cn cc qu trnh ngc li th khng t xy ra c.
Nguyn l I cho php tnh nhit ca cc phn ng nhng khng cho php tin
on chiu v gii hn ca qu trnh
Nguyn l II cho php gii quyt cc vn ny.
I.NGUYN L II. HM ENTROPY
1.Nguyn l II (Tiu chun xt chiu ca qu trnh)
- Tn ti mt hm trng thi gi l entropi (S).
- nhit T khng i, trong s bin i v cng nh, h trao i vi mi trng mt
nhit lng Q th bin thin entropi ca qu trnh c xc nh:
Nu l bin i thun nghch:
T
Q
dS
TN
=
Nu l bin i bt thun nghch:
T
Q
dS
bTN
>
Tng qut

T
Q
dS

Du > : qu trnh bt thun nghch

2
1
T
Q
S

Du = : qu trnh thun nghch
* Ch :
V S l hm trng thi --> S ch ph thuc vo trng thi u v trng thi cui, tc
l:
= =
2
1
T
Q
S S
TN
TN BTN
> =
2
1
T
Q
S S
btn
BTN TN

==> Q
Tn
> Q
BTN
: Nhit qu trnh thun nghch ln hn nhit qu trnh bt thun nghch.
+ xc nh S
btn
, trc ht hnh dung mt qu trnh thun nghch c cng trng
thi u v trng thi cui vi qu trnh bt thun nghch, sau tnh S theo cng thc:

=
2
1
T
Q
S
TN
(khng xc nh c trc tip S

btn
)

2. Nguyn l II p dng trong h c lp
i vi h c lp:
Qtn= 0 --> 0 = S
Qbtn=0 --> 0 > S
Nh vy i vi h c lp:
- Trong qu trnh thun nghch (cn bng), entropi ca h l khng i.
- Trong qu trnh bt thun nghch ngha l t xy ra, entropi ca h tng.
iu ny c ngha rng trong cc h c lp, entropy ca h tng cho ti khi t ti gi
tr cc i th h t ti trng thi cn bng.o li ta c th ni:
Trong h c lp:
- Nu dS >0 ( S tng) h t din bin
- Nu dS=0, d
2
S<0 (S max) h trng thi cn bng.
3. ngha hm entropi
a. Entropi l thc o hn n ca h
Xt 1 h c lp T=const, h gm 2 bnh c th tch bng nhau, ng 2 kh l tng
A v B c pA=pB u thp. Hai bnh c ni vi nhau bng mt dy dn c kho K.
M K--> 2 kh khuch tn vo nhau cho n khi c s phn b ng u trong ton b
th tch ca 2 bnh.
S khuch tn cc kh l tng vo nhau l qu trnh c T=const(Q=0) --> 0 > S
(S
2
> S
1
) --> hn n ca trng thi cui (hn hp 2 kh) c trng bng S
2
ln hn
hn n ca trng thi u ( mi kh 1 bnh ring bit) c trng bng S
1
.
Vy trong h c lp, qu trnh t xy ra theo chiu tng hn n ca h (tng
entropi, 0 > S ). Qu trnh ngc li: Mi kh t tch ra khi hn hp kh tr li trng
thi u khng th t xy ra.
* Kt lun:
- Entropi c trng cho hn n: hn n ca h cng ln th S cng ln.
- Nu s ht trong h cng ln--> hn n cng ln--> Sln
- Lin kt gia cc ht trong h cng yu --> hn n cng ln--> S ln. V d:
S
H2O(r)
,S
H2O(l)
< S
H2O

(k)
.
- S l hm trng thi v l i lng dung .
b. ngha thng k ca S
Trng thi ca mt tp hp bt k c th c c trng bng 2 cch:
- Bng gi tr ca cc tnh cht o c : T, P,C...--> c gi l cc thng s trng
thi v m.
- Nhng c trng nht thi ca cc phn t to nn h c gi l cc thng s vi
m.

* S thng s trng thi vi m ng vi mt trng thi v m c gi l xc sut nhit
ng
Nu s phn t trong h tng th S tng--> tng. Gia S v c quan h vi nhau
thng qua h thc Bolzomann.
H thc Boltzmann (l c s ca nguyn l III)
S=kln
k: hng s Boltzmann
Nhn xt: Trong h c lp, qu trnh t din bin theo chiu tng xc sut nhit ng .
4.Bin thin entropi ca mt s qu trnh
a. Bin thin entropi ca qu trnh bin i trng thi ca cht nguyn cht
Trong sut qu trnh ny T=const ==> S ca mt mol cht nguyn cht trong qu
trnh bin i trng thi xy ra P=const l

= =
2
1 cf
cf
T
H
T
Q
S

cf
H nhit chuyn trng thi
b. Bin thin entropi ca qu trnh gin n ng nhit kh l tng
T=const, dn n n mol kh l tng t V
1
-->V
2

= =
2
1
T
Q
T
Q
S
TN TN
v T=const
V T=const --> 0 = U
1
2
V
V
nRT W
TN
ln =
Theo nguyn l I: 0 = + =
TN TN
W Q U -->
1
2
V
V
nRT W Q
TN TN
ln + = =
==>
2
1
1
2
P
P
nR
V
V
nR S ln ln = =
Nu P
1
>P
2
--> 0 > S : qu trnh gin n ny t din bin
==> Cch pht biu khc ca nguyn l II: Cc cht kh c th t chuyn di t ni c p
sut cao n ni c p sut thp.
c. Bin thin entropi ca cht nguyn cht theo nhit :
un nng n mol 1 cht nguyn cht t nhit T
1
-->T
2
vi iu kin trong khong
nhit cht ny khng thay i trng thi
- Trong iu kin P = const:

= = =
2
1
2
1
2
1
T
dT
nC
T
dH
T
Q
S
p
p
p

Vy
=
2
1
T
dT
nC S
p p

- Trong iu kin V= const

= = =
2
1
2
1
2
1
T
dT
nC
T
dU
T
Q
S
v
v
v
==> Vy
=
2
1
T
dT
nC S
v v

Nu coi Cp hoc Cv

khng i theo T th:

1
2
T
T
nC S
p p
ln =

1
2
T
T
nC S
v v
ln =
II. Nguyn l III ca nhit ng hc
Nhn xt: dng tinh th hon ho ca mt cht nguyn cht OK ng vi 1 trng thi
v m ch c 1 trng thi vi m ==> OK th 1 =
1. Nguyn l III (tin Nernst)
Entropi ca mt cht nguyn cht di dng tinh th hon ho OK bng khng:
( )
= = ln 0
0
k S
K
( 1 = )
2.Entropi tuyt i ca cc cht nguyn cht cc nhit T
V d: un nng n mol 1 cht nguyn cht 0K -->T

K, trong khong ny xy ra cc qu
trnh bin i trng thi v iu kin P=const. Tnh ST?
0

K---> Tnc--->Ts--->T
=
=
= = =
T
T
p T T T
T
dT
nC S S S S
0
0

+
+ +
+ = =
=
nc S
nc S
T
K
T
T
T
T
h P
S
s
l p
nc
nc
r p T T
T
dT
nC
T
H
n
T
dT
nC
T
H
n
T
dT
nC S S S
0
0 ) ( ) ( ) (

thng th P=1atm, T=298K, n=1mol ==> ) . . (
1 1 0
298

mol K J S
-->Bng entropi chun ca cc cht 25
oC

* Nhn xt: Gi tr S cht nguyn cht lun > 0, tr khi xt cho ion trong dung dch, c
th c Sion<0.
3.Bin thin entropy ca cc phn ng ho hc
V S l hm trng thi v l i lng dung nn:

=
) ( ) ( tg sp
S S S ( T, P =const)
Nu iu kin chun (P=1atm) v T=298K th:

= ) ( ) ( tg S sp S S
0
298
0
298

V Skh>>Slng,Srn ==> c th cn c vo s mol kh 2 v ca phn ng nh
gi ln cng nh l du ca S ca phn ng.
0 = n ==> S nh
0 > n ==> S > 0 ==> phn ng tng S

0 < n ==> S nh ==> phn ng gim S
V d: SO
2
(k) + 1/2 O
2
(k) --> SO
3
(k) c 0 < n ==> S <0
C(gr) + O
2
(k) --> CO
2
(k) c 0 = n ==> 0 S
III. HM TH NHIT NG. TIU CHUN XT CHIU CA QU TRNH
- H c lp: 0 S --> tiu chun t din bin v gii hn ca qu trnh
- H khng c lp: gm h + Mi trng --> av 1 h c lp mi bng cch gp
h v mi trng thnh 1 h c lp.
==> tiu chun t din bin v gii hn ca h mi l : 0 +
mt
S S

mt
S cha xc nh nhng c th a v cc thng s ca h bng cch tm 1
hm thay th cho c (
mt
S S + ), hm thay th ny gi l hm th nhit ng. Thng
gp h:
+ ng nhit, ng p ==> c hm th ng nhit ng p
+ ng nhit, ng tch==> c hm th ng nhit ng tch
1.Hm th ng nhit ng p
a. nh ngha: Xt 1 h: T, P = const
H thc hin mt bin i no

T
H
S
T
H
S S S
mt
mt

=
+ = +
H Mi trng
H _Nhit lng trao i vi mi trng H H H
h mt
= =
S _Bin thin entropi ca h.
T
H
T
H
S
mt
mt

=
=
==> tiu chun t din bin v gii hn ca qu trnh l:
0 +
mt
S S
<=> 0

T
H
S
<=> 0 S T H
<=> ( ) 0 TS H t H-TS =G => G l hm trng thi
<=> 0 G
0 = S T H G : P,T=const ==> qu trnh t xy ra theo chiu 0 < G v
t cn bng khi 0 = G
G c gi l : Nng lng Gibbs, Entanpi t do hay th ng p.
b. ngha vt l ca G
G = H TS = U +PV TS
dG = dU + pdV + VdP- TdS SdT
Nguyn l I => W Q dU + = , m ' W pdV dW + = ( ' W : cng hu ch)

=> SdT TdS PdV VdP W PdV Q dG + + + = '
SdT TdS VdP W Q dG + + = '
Nguyn l II => TdS Q ; ' W PdV TdS dU +
=> SdT TdS VdP W TdS dG + + '
hay: SdT VdP W dG + '
l phng trnh c bn ca nhit ng hc.
- Nu qu trnh l thun nghch-->cng l ln nht --> du =
SdT VdP W dG + =
max
'
- T v P =const => dT=0 v dP=0 c:
'
max ,
W dG
P T
=

max ,
' W G
P T
=
ngha ca G: G biu th cng hu ch ca qu trnh thun nghch ng nhit ng
p.
2. Hm th ng nhit ng tch (lm tng t G)
a. nh ngha: Xt 1 h T, V =const, h thc hin 1 bin i no
H Mi trng
U _Nng lng trao i vi mi trng U U U
h mt
= =
S _Bin thin entropi ca qu trnh
T
U
T
U
S
Mt

=
=
Tiu chun t din bin v gii hn ca qu trnh l:
0 +
mt h
S S
<=> 0

T
U
S
<=> 0 S T U
<=> ( ) 0 TS U t U - TS = A => A l th ng tch ( nng lng Helmholtz).
<=> 0 A
b. ngha A
A = U TS
dA = dU - TdS SdT ; ' W PdV Q W Q dU + = + =
TdS Q => SdT TdS W PdV TdS dA + '
=> SdT PdV W dA '
- Nu qu trnh l thun nghch-->cng l ln nht --> du =
SdT PdV W dA =
max
'
- T v V =const => dT=0 v dV=0 c:

max
' W dA =

max
' W A =
ngha ca A : Bin thin th ng tch A biu th cng c ch ca qa trnh
thun nghch ng nhit ng tch.
Tm li tiu chun t din bin v gii hn ca qu trnh l
T,P = const => 0 dG
T,V = const => 0 dA
Mi lin h gia G v A
G = H- TS U +PV TS =(U-TS) + PV =A + PV
Vy G = A+PV
3.Bin thin th ng p:
SdT VdP W dG + '
0 dG --> iu kin t din bin v gii hn
=> Qu trnh t din bin theo chiu lm gim G cho ti khi t gi tr Gmin: dG=0
(G=0)
d
2
G>0 (G>0)
a. Th ng p sinh chun ca 1 cht nhit T:
L s bin thin th ng p ca phn ng to thnh 1 mol cht t cc n cht
bn iu kin chun v nhit T ca phn ng.
K hiu:
0
s T
G
,
(J.mol
-1
hoc kJ.mol
-1
)
Thng T=298K =>
0
298 s
G
,
--> c bng th ng p sinh chun ca cc cht 25
0
C.
VD:
) (
, 3
0
298
NH G
s
=-16,65kJ.mol
-1
ng vi qu trnh ) ( ) ( ) ( k NH k N k H
3 2 2
2
1
2
3
+
) (
,
HCl G
s
0
298
=-95,5kJ.mol
-1
ng vi qu trnh ) ( ) ( ) ( k HCl k Cl k H +
2 2
2
1
2
1

=> HCl(k) bn hn NH
3
(k) v nng lng to ra nh hn.
- T nh ngha =>
0
,s T
G (n cht) =0
b. Tnh bin thin th ng p ca phn ng ho hc
V G l hm trng thi v l i lng dung nn c:
-

= ) ( ) ( tg G sp G G
s s p

Nu iu kin chun v 25
0
C c:
-

= ) ( , ) ( , tg G sp G G s s
p
298
0
298
0

G
thun
=- G
nghch

G <0: phn ng xy ra theo chiu thun
G =0: qu trnh cn bng

G >0; phn ng xy ra theo chiu nghch
-
T T T
S T H G =
0
298
0
298
0
298
298 S H G = .
-
=
T T
G G (cc qu trnh trung gian)
IV. CC YU T NH HNG N TH NG P
1. nh hng ca nhit
Xt h: ch c bin i thun nghch, khng sinh cng c ch, c P=const.
SdT VdP W dG + = ' , v 0 = ' W (khng sinh cng hu ch) v P=const
nn S
T
G
P
=
=> S
T
G
P
=
) (
, thay vo biu thc S T H G = ta c:
P
T
G
T H G

+ =
) (

=> H G
T
G
T
P
=
) (

Chia c hai v cho T
2
ta c:
2 2
T
H
T
G
T
G
T
p

=

) (

=>
2
T
H
T
G
T
p

hoc l
2
T
H
T
T
G
p

Phng trnh Gibbs- Helmholtz cho php xc nh G theo T:
dT
T
H
T
G
d
2
) (
thng xt iu kin chun (p= 1atm) v T=298K:
dT
T
H
T
G
d
2
0 0
) ( -> ly tch phn t 298-->T v thng thng bit gi tr

0
298
G v
) (T f H
T
=
0

C:

=
T
T
T
dT
T
H
T
G
d
298
2
0
298
0
) (
==>
T
T T
dT
T
H G
T
G
298
2
0 0
298
0
298
..... ) ( + + = = bT a T f H
T
0

Phng trnh Gibbs-Helmholtz

=> ) (T f G =
0

2. nh hng ca p sut:
Xt h: bin i thun nghch, khng sinh cng hu ch, T=const.
T biu thc: SdT VdP W dG + = ' , 0 = ' W , T= const nn c
V
P
G
T
=
=>

=
2
1
2
1
P
P
Vdp dG
=>
=
2
1
1 2
P
P
T T
Vdp G G
P P

- i vi cht rn v cht lng --> coi V=const khi P bin i ( tr min P ln) nn
: ) (
1 2
1 2
P P V G G
P P
T T
=
) (
1 2
1 2
P P V G G
P P
T T
+ = hay ) (
1 2
P P V G =
- i vi cht kh (coi l kh l tng) -->
P
nRT
V =

1
2
2
1
1 2
P
P
nRT
P
dP
nRT G G
P
P
T T
P P
ln = =

Vy:
1
2
P
P
nRT G ln = hay
1
2
1 2
P
P
nRT G G
P P
T T
ln + =
Nu ban u P
1
=1atm (iu kin chun) th
0
2
T T
G G
P
=
P nRT G G
T T
ln + =
0

VD: Nn 0,5 mol kh l tng t P=1atm n P= 2atm 25
0
C. Hi qu trnh nn c t
xy ra c khng?
0
1
2
1
2
> = = ln ln nRT
P
P
nRT G
==> qu trnh nn khng t xy ra.
3. nh hng ca thnh phn cc cht. Khi nim th ho
Xt h gm i cht: n i , 1 = vi s mol tng ng l n
1
, n
2
, ...ni.
G=G(T, P, n
1
, n
2
...ni)

i
i n P T
i
n P T n P T
N T
N P
dn
n
G
dn
n
G
dn
n
G
dP
P
G
dT
T
G
dG
j j j

+ +
=
, , , , , , , , , , , ,
,
,
... ) (
2
2
1
1
1
1

' W Vdp SdT dG + + =
Ch s N ch ra rng n
1
,n
2
, n
3
...ni l khng i, ch s nj
#i
ch ra rng ch c ni l bin i.
t:
i
i n P T
G
ni
G
j
=
, , , ,
=
i

Trong :
i
G th ng p mol ring ca cht i trong h

i
Th ho ca cht i
==>
=
i i
dn W ' =>
i i
dn l 1 dng cng hu ch ==> gi l cng ho
T :
+ =
i i
dn SdT VdP dG
* ngha vt l ca
i
:
- Th ho ca cht i (
i
) l th ng p mol ring phn ca i trong hn hp
-
i
l tng kh nng sinh cng hu ch ca h khi thm 1 lng v cng nh
cht i vo h trong iu kin P,T v thnh phn (s mol) ca cc cht khc l khng i.
i
c tnh cho 1 mol cht.
-
i
l i lng cng nhng dni l i lng dung
-
i i
dn c th lm tiu chun xt chiu v gii hn trong iu kin T,P khng
i:
+
i i
dn <0: Qu trnh t din bin
+
i i
dn =0: Qu trnh cn bng
Phn ng xy ra theo chiu gim th ho.
* Mt vi tnh cht ca th ho:

i i
G = -->
i
ph thuc vo T, P (ging Gi)
- Nu h ch gm 1 cht kh th th ho chnh l th ng p ca 1 mol cht: G= .
do : V
P P
G
T T
=

T lm tng t nh hm G, s thu c phng trnh ca
T
(ging GT):
P RT
T T
ln + =
0
P(atm) (i vi 1 mol kh).
0
T
: th ho chun ca cht kh nhit T, P=1atm v tnh cho 1 mol.
- Nu h gm 1 hn hp kh c p sut chung l P th p sut ring phn ca kh i
trong hn hp l Pi=Ni.P ( vi
=
i
i
i
n
n
N )
) ln( ln
) ( ) ( ) (
P N RT P RT
i T i i T i T i
+ = + =
0 0

i T i T i
N RT P RT ln ln
) ( ) (
+ + =
0

=>
i P T i T i
N RT ln
) , ( ) (
+ =
0

- i vi phn ng ho hc: aA + bB --> cC + dD

= ) ( ) (
tg sp G
i i p

iu kin chun:

= ) ( ) (
tg sp G
i i p
0 0 0

Vy trong iu kin ng nhit, ng p:

+ Nu

< ) ( ) ( tg sp
i i
: phn ng t din bin (t tri qua phi)
+Nu

= ) ( ) ( tg sp
i i
phn ng trng thi cn bng
=> th ho cng l tiu chun xt chiu v gii hn ca cc qu trnh (phn ng xy ra
theo chiu gim th ho)
4.Mi quan h gia du G v ln S H , v T:
T=const -->
T T T
S T H G =
0 < G : Qu trnh t xy ra
<=> 0 < H : chiu tng bn lin kt
0 > S : chiu tng hn lon
STT Du H Du S Du G D on chiu
1 - + - Phn ng t xy ra mi nhit
2 + - + Phn ng khng t xy ra mi nhit
3 - - ? Phn ng t xy ra nhit thp
4 + + ? phn ng t xy ra nhit cao

V d:
- phn ng: CaCO
3
(r) <=> CaO(r) + CO

(k) kJ H
p
22 178
0
,
+ =
0 1 > > = S n --> phn ng ch xy ra nhit cao
- phn ng: SO
2
(k) + 1/2 O
2
(k) --> SO
3
(k) kJ H
p
12 99
0
,
=
0 5 0 < > = S n , --> phn ng xy ra nhit thp, nhng nu thp qu th vn
tc khng ln --> phn ng khng xy ra ngay c
==> iu kin: nhit khng qu thp

Ti liu tham kho:

1. Nguyn nh Chi, C S L Thuyt Ha Hc, NXB GD, 2004.
2. Nguyn Hnh, , C S L Thuyt Ha Hc, Tp 2, NXB GD 1997.
3. L Mu Quyn, C S L Thuyt Ha Hc - Phn Bi Tp, NXB KHKT, 2000.

Ch2-Nhiet Dong Hoc

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Available Formats

Bi ging mn C s l thuyt Ha hc

CHNG II: NGUYN L II CA NHIT NG HC CHIU V GII HN

(khng xc nh c trc tip S

) ( -> ly tch phn t 298-->T v thng thng bit gi tr

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