Chng VII

TH NG P
v CHIU CA CC QU TRNH HO HC

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QU TRNH THUN NGHCH V

BT THUN NGHCH
Tnh cht ca qu
trnh thun nghch:
Xy ra vi tc
v cng chm.
Cng h sinh ra l
cc i.

EOS

Cc qu trnh c xem gn nh l
qu trnh thun nghch
Qu trnh chuyn pha ng iu kin
nhit v p sut chuyn pha.
Qu trnh tng hay gim nhit v cng
chm.
Qu trnh dn n ng nhit v cng chm
ca kh l tng.
Cc phn ng ho hc din ra rt gn vi
iu kin cn bng.

XC SUT NHIT NG W
Trng thi v m- xc nh bng nhng thng s trng
thi nh : nhit , p sut , nng .

Trng thi vi m- xc nh bng nhng gi tr c

trng tc thi ca mi phn t nh v tr, tc ,
chiu chuyn ng.
Xc sut nhit ng W l tng s trng thi vi m ng
vi mi trng thi v m ca h.(W>>1)

Xc sut nhit ng W

Xc sut nhit ng W l thc o hn lon ca h.

II. KHI NIM V ENTROPY

1.nh ngha
2.Entropy tiu chun
3.Tnh cht

Cc qu trnh t pht
Nc chy theo chiu
lm gim th nng

H cha th xem l i
lng tiu chun tin
on chiu v gii hn
qu trnh.
qu

Qu trnh to nhit

trnh bay
hi nc t xy
ra l qu trnh
thu nhit

Trong h c lp, qu trnh khuch tn din ra theo chiu

hng lm tng hn lon ca h
T pht

Qu trnh khuch tn cc kh t din ra c

H=0
Khng t pht

Qu trnh nng chy, bay hi t din ra

c H >0

Trong h c lp, cc qu trnh t pht din ra theo

chiu hng i t trng thi c hn lon thp
n trng thi c hn lon cao.

Entropy
Entropy (S) l thc o hn lon trng thi ca h.
H THC BOLTZMANN
R
S k ln W
ln W
N0
Entropy l hm trng thi
Entropy l thng s dung .
K- hng s Boltzmann
= 1.38 x 10-23 J/K
W- xc sut nhit ng

S= RlnW (tnh cho mt mol cht)

nh lut Nernst
Nguyn l III ca nhit ng hc
khng tuyt i (0K) mi n cht cng nh
mi hp cht dng tinh th hon ho u c
entropy bng khng.
W=1 S0=0

Bin thin Entropy (S0) trong cc qu trnh

bin i cc cht dng tinh th hon ho
u bng khng 0K.
V d: 0K phn ng C(gr)+O2(r) = CO2(r) S0=0

ENTROPY tiu chun S0298

Trng thi chun 1atm, nhit 250C

K hiu S0298
n v J/mol.K hay cal/mol.K
1 cal/mol.K= 1.v.e

TNH CHT ENTROPY

H cng phc tp, phn t cng phc tp
th entropy cng ln.
V d : S0298(O) < S0298(O2) < S0298(O3)
S0298(NO) < S0298(NO2)

Entropy, S
Entropy ca cc hp cht tinh th
ion ph thuc vo lc ht tnh in.
SSoo (J/Kmol)
(J/Kmol)
MgO
MgO

26.9
26.9

NaF
NaF

51.5
51.5

 i vi cng mt cht th cc trng thi rn, lng,

kh entropi c gi tr khc nhau v tng dn.
S(rn) <S(lng) <S(kh)
SSoo298
(J/Kmol)
298 (J/Kmol)
H
H22O(lng)
O(lng) 69.91
69.91
H
H22O(kh)
O(kh) 188.8
188.8

ENTROPY tiu chun 298K

Cht

S 298 (J/mol.K)

Cht

S 298 (J/mol.K)

H2O(l)

69.9

NaCl(r)

72.3

H2O(k)

188.8

NaCl(aq)

115.5

I2(r)

116.7

Na2CO3(r)

136.0

I2(k)

260.6

CH4(k)

186.3

Na(r)

51.5

C2H6(k)

229.5

K(r)

64.7

C3H8(k)

269.9

Cs(r)

85.2

C4H10(k)

310.0

Nhit tng lm tng entropy, ngc li

p sut tng lm gim entropy
S0298H2O (lng) < S0350H2O (lng)
S400H2O (kh, 3 atm ) < S450H2O (kh, 1atm)

Entropy l hm
Entropy lun
tng theo nhit

tng nhanh
trong
sut qu
ca
nhit
trnh
chuyn pha.

Cc qu trnh
ny lm tng
entropy (S > 0)

Phn ng ho hc
C(gr) + CO2(k) = 2CO (k) ; n=1>0 V >0 Sp >0
N2(k) + 3H2(k) = 2NH3(k); n= -2<0 V<0 Sp <0

Q1

>

Q2

T
> Q
T
Q T Q
S ; dS
S
S
T
T S
T
> S
< S
T

S ~ Q
TN, QTN, ATN

S ~ 1/ T
Qu trnh thun nghch ng nhit
QTN / T = S

U1, S1,T

U2,S2,T

BTN, QBTN, ABTN

U = QTN - ATN = QBTN ABTN

ATN > ABTN QTN > QBTN

III. NGUYN L TH HAI CA NHIT

NG HC
S

Biu thc ton hc ca nguyn l II:

i vi qu trnh ng nhit

Q
T

Q
S
T

Qu trnh thun nghch, ng nhit

Qu trnh bt thun nghch, ng nhit

Q tn
S
T
Q btn
S
T

Entropy l tiu chun xt chiu trong h c lp

Trong h c lp, Q = 0 S 0
Qu trnh bt thun nghch t xy ra c km theo s tng
entropy S > 0, khi entropy t n gi tr cc i th h
s trng thi cn bng.
Nu h khng c lp ta c th c lp bng cch ghp thm
mi trng vo h.
Sc lp = Sh + S mi tng = Sh +
H - T.S 0

H h
0
T

(ng p , ng nhit)

Tnh S cho cc qu trnh vt l

( Qu trnh thun nghch )

Da vo h thc Boltzman ta c :

S n.R . ln

Wc
W

V d - tnh S ca qu trnh dn n ng nhit thun nghch

ca n mol kh l tng.
Trng thi 1 (n,P1, V1, T,U) Trng thi 2 (n,P2, V2, T,U)
W~ V hay W ~1/P nn S n.R. ln V2 n.R. ln P1
V1

P2

Hoc theo nguyn l I v II ta c : Q = A + U = A

2
2
Q A 1
1 n.R.T
V2
S

P.dV
n.R.Ln
T T T1
T1 V
V1

Bin thin entropy ca cht nguyn cht theo nhit

(Qu trnh thun nghch )
S

Q
T

Khi Cp= const, ta c

T2

n.C

T1

dT
T

T2
S n.C p ln
T1

V d- tnh S ca qu trnh un nng 2 mol nc lng

t 00C ln 250C.Cho bit Cp= 75,24J/mol.K
S = 2.75,24.ln(298/273) = 13,18 (J/K)

Tnh bin thin entropy trong qu trnh chuyn pha

(ng nhit , ng p, thun nghch )

Q
S
T

Q cp
T

H cp
T

V d - tnh S cho qu trnh nng chy 10 mol nc

273K , 1atm cho bit Q = - 6008,22J/mol
S = (6008,22.10)/ 273 = 22(J/K)

Bin thin entropy ca qu trnh bt thun nghch

1
S1 TN

SBTN

SBTN = S2 S1
SBTN = S2 S4+S4- S3 +S3 S1

S3 TN

SBTN = S3 + S2+ S1

4
S2 TN

Tnh S cho phn ng ho hc

oo
oo
SSooTT(p)
=

S
(sn
phm)

S
(cht u)
(p)= S TT(p
(p) )(sn phm) - S TT(p)
(p) (cht u)

2 H2(k) + O2(k) ---> 2 H2O(l)

; S <0
So = 2 So (H2O) - [2 So (H2) + So (O2)]
So = 2 mol (69.9 J/Kmol) - [2 mol (130.7 J/Kmol) +
1 mol (205.3 J/Kmol)]
So = -326.9 J/K

Entropy ca h gim v t 3mol kh chuyn

thnh 2 mol lng.

Tnh S cho phn ng ho hc nhit bt k.

T2 aA

ST2

+ bB

cC

dD

S(T)c
T1 aA
ST2(p) =

T2
S(T)sp

+ bB

ST1

ST1(p)

T2

cC

dD T1

c.C Pc d.C PD a.C PA b.C PB

T1

T2

ST2(p) =

ST1(p)

dT
C P .
T
T1

Cp = const ST2(p) =

ST1(p) + Cp.ln(T2/T1)

dT

T

TH NG P V CHIU DIN RA
CA CC QU TRNH HO HC
Xt qu trnh ng p, ng nhit.
Q = U + P.V +A
S Q/T Q T.S

U + P.V +A T. S

H T. S -A t G = H TS
G -A (A 0) G- th ng nhit ng p ( th ng p)
G 0

nng lng t do Gibbs

Phng trnh c bn ca nhit ng hc

G = H T. S

IU KIN T PHT CHO QU TRNH

NG NHIT NG P
G < 0 qu trnh t pht
G> 0 qu trnh khng t pht
nhng qu trnh ngc li l t pht
G = 0 h trng thi cn bng.

NH HNG NHIT N CHIU DIN

RA CA CC QU TRNH HO HC
Phng trnh c bn ca nhit ng hc
G = H T. S

nhit thp, |H| >>|T .S | nn du G ph thuc

vo du H.
nhit cao, |H| <<|T .S | nn du G ph thuc vo
du S.

T pht

Khng t pht

T thp T cao +

T pht
Khng t pht

T thp + Khng t pht

T cao - T pht

Kt lun

Th ng p tiu chun G0T

Trng thi chun
Nhit tu , thng chn 250C

Th ng p to thnh tiu chun (G0298)tt

l bin thin th ng p ca phn ng to thnh.
n v kJ/mol hay kcal/mol.

Th ng p to thnh tiu chun ca cc n

cht bn c qui c bng khng
V G l hm trng thi nn khi i chiu phn ng G i du.

CCH TNH G
Phn ng ho hc : aA + bB = cC + dD
G0298 = (G0298)tt sn phm - (G0298)tt cht u
G0T = H0T (p) T. S0T (p)
p k chun, nhit 298K
G0298= H0298 (p) T. S0298 (p)
p k chun, nhit T khng cao lm.
G0T H0298 (p) T.S0298 (p)

G0T = - RTlnKcb

G = -Amax = -nE F
0
T

G = G1 + G2

1
G1

2
3

G2

nh gi chiu hng qu trnh trong thc t

t G0298 p
+40kJ < G0298 p G > 0 : trong thc t phn ng c
th din ra theo chiu nghch.
- 40kJ > G0298 p : trong thc t phn ng c th din ra
theo chiu thun.
-40kJ < G0298 p < +40kJ : trong thc t phn ng din
ra thun nghch.