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Chng 4

CN BNG PHA
4.1. Mt s khi nim c bn
Pha: l tp hp nhng phn ng th ca mt h, c cng thnh phn ha hc v tnh
cht l ha mi im. S pha k hiu l f
S cu t: l s ti thiu hp phn to ra h. K hiu l k
t do ca mt h l thng s nhit ng c lp xc nh h cn bng. K
hiu l c.
4.2. Qui tc pha Gibbs
Bc t do ca h:
c=k-f+n
Trong :
k: s cu t
f: s pha
n: s thng s bn ngoi tc ng ln h
4.3. Gin pha v cc qui tc cn bng pha
4.3.1. Biu din thnh phn ca h 2 cu t
Thnh phn ca cc cu t trn gin pha thng dng l phn mol x i hay phn trm
khi lng yi. Trong h hai cu t, dng mt on thng c chia thnh 100% nh sau:

Hnh 4.1. Gin pha h hai cu t


Trn trc to ch cn biu din cho mt cu t v thnh phn ca cu t cn li c
xc nh theo cng thc: xA + xB = 1 hay y1 + y2 = 100%
Khi im biu din ca h cng gn cu t no th hm lng ca cu t cng ln.
4.3.2. Biu din thnh phn ca h 3 cu t
Thnh phn ca h 3 cu t thng c biu din bng mt tam gic u nh sau:

Hnh 4.2. Gin pha h ba cu t


Ba nh ca tam gic l ba im h ca cc cu t nguyn cht A, B v C.
Ba cnh ca tam gic biu din ba h hai cu t tng ng l AB, AC v BC.
Mi im trong tam gic biu din h 3 cu t.
Cch biu din im P(40%A, 40%B, 20%C) trn gin tam gic u ABC.
Trn cnh AC, ta v ng thng i qua im 40% v song song vi cnh BC.
Trn cnh AB, ta v ng thng i qua im 40% v song song vi cnh AC.
Trn cnh BC, ta v ng thng i qua im 20% v song song vi cnh AB.
Ta thy 3 ng thng trn ct nhau ti P. Vy P l im biu din ca h c thnh phn
(40%A, 40%B, 20%C).
4.4. Cc qui tc ca gin pha
4.4.1. Qui tc lin tc

Hnh 4.3. Gin nhit - thi gian ca cht nguyn cht.


Cc ng hoc cc mt trn gin pha biu din s ph thuc gia cc thng s nhit
ng ca h s lin tc nu trong h khng xy ra s bin i cht, s thay i s pha hoc
dng cc pha.
Nh vy ta c th suy ra, nu trong h c s thay i v pha hay s thay i v dng pha th
trn cc ng hay cc mt s xut hin cc im gy, lm cho th khng cn lin tc.
2

4.4.2. Qui tc ng thng lin hp


Trong iu kin ng nhit v ng p nu h phn chia thnh hai h con (hay c sinh
ra t hai h con) th im biu din ca ba h ny phi nm trn cng mt ng thng,
ng thng ny gi l ng thng lin hp.

EMBED Visio.Drawing.11
Hnh 4.4. Minh ha quy tc ng thng lin hip
V d: h H = h M + h N. Th im biu din cc h H, M v N nm thng hng.
4.4.3. Qui tc n by
Nu c ba im h lin hp M, H v N th lng tng i ca chng c tnh theo qui
tc n by nh sau:

EMBED Visio.Drawing.11
Hnh 4.5. Minh ha quy tc n by
p dng quy tc n by, ta c:
gM
HN

gN
HM

Trong : gM: Khi lng ca h M


gN: Khi lng ca h N
4.4.4. Qui tc khi tm
Nu mt h gm n h con th im biu din ca n phi nm khi tm vt l ca a
gic c nh l cc im biu din ca n h con.
V d: H H gm ba h con l H1, H2 v H3. vi khi lng tng ng l:
g = g1 + g2 + g3

Hnh 4.6. Minh ha quy tc khi tm

Nh vy, H phi nm khi tm vt l ca tam gic H 1H2H3. u tin ta xc nh im


biu din ca h K, tha mn iu kin:
H K

g1 H2K

g2
H1K

h H1

h H2

Tip theo ta xc nh im H tha mn iu kin sau:


H H

h K

h H3

gK g1 g 2 HH3

g3
g3
KH

4.5. nh hng ca p sut n nhit chuyn pha


Phng trnh Clausius Claypeyron I:
dT T. V

dP

Trong :
T: nhit chuyn pha (K)
: nhit chuyn pha (cal/mol hoc J/mol)
V = V2 V1: bin thin th tch (ml)
Nu V c tnh bng ml, c tnh bng cal v 1cal = 41,3 ml.atm, nn phng trnh
Clausius Claypeyron tr thnh:
dT
T.V

dP
41,3.

4.6. nh hng ca nhit n p sut hi bo ha


Phng trnh Clausius Claypeyron II
dlnP

dT
RT 2

Ly tch phn 2 v, ta c:
ln

P2
1
1


P1
R T2 T1

Trong :
T: nhit (K)
P: p sut (atm)
: nhit ha hi (cal/mol hoc J/mol)
R: l hng s kh

4.7. Bi tp mu
V d 1. 00C nhit nng chy ca nc l 1434,6 cal/mol. Th tch ring ca nc v
nc lng ln lt l 1,098 v 1,001 ml/g. Xc nh h s nh hng ca p sut n nhit
nng chy ca nc v tnh nhit nng chy ca nc 4 atm.
Gii
p dng phng trnh:

dT T. V

dP

Vi: V = Vlng Vrn


= 1,001 1,098 = - 0,097 (ml/g)
Hoc: V = 18.(- 0,097) = -1,746 (ml/mol)
dT 273 1,746

0,0081
dP
1434,6 41,3

(K/atm)

Nh vy, c tng p sut ln 1 atm th nhit nng chy ca nc gim 0,0081K.


Mt cch gn ng, 4atm, nhit nng chy ca nc l:
T = 273 + (-0,0081) x (4 - 1)
= 272,9757K = - 0,02430C
V d 2. Tnh nhit si ca nc 2 atm, bit nhit ha hi ca n l 538,1 cal/g (coi nhit
ha hi khng thay i trong khang t 1 atm n 2 atm).
Gii
Nhit ha hi: = 538,1x18 = 9685,8 (cal/mol)
P2
1
1


P1
R T2 T1
2
9685,8 1
1

ln

1
1,987 T 100 273

p dng cng thc: ln

T tnh c: T = 394K = 1210C


V d 3. Tnh nhit nng chy ca 1 mol diphenylamin nu 1kg diphenylamin nng chy lm
tng th tch ln 9,58.10-5m3 cho bit dT/dP = 2,67.10 -7 K.m2/N. Nhit nng chy ca
diphenylamin l 540C, khi lng mol ca cht ny l 169.
Gii
p dng cng thc:

T.V

dT
dP

dT T.V

dP

169
9,58.10 5
1000
19,83.10 3 (J/mol)
7
2,67.10

273 54

V d 4. p sut hi bo ha ca axit xyanhydric HCN ph thuc vo nhit theo phng


trnh:
5

lgP(mmHg) 7,04

1237
T

Xc nh nhit si v nhit ha hi ca n iu kin thng.


Gii
Nhit si ca axit HCN p sut 760 mmHg:
Ta c:

lg(760) 7,04

1237
T

T = 297,4K

Vy nhit si ca axit HCN l 24,40C.


Ly o hm hai v phng trnh theo T, ta c:
dlgP 1237

dT
T2
dlgP

dT
4,575.T 2

M:
Suy ra:

1237

2
4,575.T
T2

= 5659 (cal/mol)

V d 5. Trn 200g hn hp gm 3 cht A, B, C cha 20% A, khi cn bng hn hp chia lm


hai lp.
Lp th nht c khi lng 60g v bao gm 50% A v 20% B.
Lp th hai cha 80%B.
Hy xc nh im biu din ca ba cu t A, B, C trn gin tam gic u trong hai lp
trn.
Gii
c gi t v hnh
Khi lng ca cht A trong hn hp ban u:
mAo = 20% 200 = 40 (g)
Phn trm ca cht C trong lp th 1:
%C = 100 - 50 - 20 = 30 (%)
Vy im biu din ca lp 1: I1 (50%A, 20%B, 30%C)
Khi lng lp th 2:
m = 200 60 = 140 (g)
Khi lng ca cht A trong lp th 1:
mA1 = 50% 60 = 30 (g)
Khi lng ca cht A trong lp th 2:
mA2 = 40 - 30 = 10 (g)
Khi lng ca cht B trong lp th 2:
6

mB2 = 80% 140 = 112 (g)


Khi lng ca cht C trong lp th 2
mC2 = 140 - 122 = 17 (g)
im biu in lp 2: I2 (7,15%A, 80%B,12,85%C)
V d 6. Khi lng ring ca phenol dng rn v dng lng ln lt l 1,072 v 1,056 g/ml,
nhit nng chy ca phenol l 24,93 cal/g, nhit kt tinh ca n 1 atm l 41 0C. Tnh nhit
nng chy ca phenol 500 atm.
Gii
p dng phng trnh:
1

dT T. V

dP

Vi: V 1,056 1,072 0,014 (mol/g)


dT
314 0,014

4,26.10 3
dP
24,93 41,3

Ta c:

(K/atm)

Nh vy, c tng p sut ln 1 atm th nhit nng chy ca phenol tng 4,26.10 -3K.
Mt cch gn ng, 500atm, nhit nng chy ca phenol l:
T = 314 + 4,26.10-3(500 - 1)
= 316,13K = 43,130C
V d 7. p sut thng, nhit si ca nc v cloroform ln lt l 1000C v 600C, nhit
ha hi tng ng l 12,0 v 7,0 kcal/mol. Tnh nhit m 2 cht lng trn c cng p
sut?
Gii
Gi T l nhit m ti 2 cht lng c cng p sut:
1

Ta c: 1 T T 2 T T
1

Vi: 1 = 12 (Kcal/mol), T1 = 273 + 100 = 3730K


2 = 7 (Kcal/mol), T2 = 273 + 60 = 3330K
Th cc gi tr vo phng trnh trn, ta c:

1
1
1
1
7

373 T
333 T

12

Suy ra: T = 448,40K


4.8. Bi tp t gii
1.

Xc nh nhit ha hi ca H2O 4 atm nu 1000C nhit ha hi ca nc bng


2254,757 J/g.
7

2.

Xc nh nhit si ca benzoatetyl (C9H10O2) p sut 200 mmHg bit rng nhit


si chun ca benzoatetyl l 2130C v nhit ha hi bng 44157,52 (J/mol).
S: T = 433,10K

3.

Nhit nng chy chun ca Bi l 271 0C. iu kin khi lng ring ca Bi rn v
lng l 9,673 v 10 g/cm3. Mt khc khi p sut tng ln 1 atm th nhit nng chy
gim i 0,00354K. Tnh nhit nng chy ca Bi.
S: 11 kJ/mol.

4.

Ti 1270C HgI2 b chuyn dng th hnh t dng sang dng vng. Nhit chuyn ha l
1250 J/mol, V = 5,4 cm3.mol-1, dng c t trng ln hn dng vng. Xc nh dT/dP
ti 1270C.
S: -1,73.10-6 K/Pa

5.

Khi un nng lu hunh rombic chuyn thnh lu hunh n t km theo bin thin th
tch V = 0,0000138 m3/kg. Nhit chuyn ha chun bng 96,70C v dT/dP = 3,25.10-7
K/Pa. Xc nh nhit chuyn pha.
S: = 501,24 kJ/kg

6.

Xc nh th tch ring ca thic lng ti nhit nng chy chun 232 0C nu nhit nng
chy ring l 59,413 J/g, khi lng ring ca thic rn l 7,18 g/cm 3 v

dT/dP =

3,2567.10-8 K/Pa.
S: 0,147 cm3/g
7.

200 mmHg metanol si 34,7 0C cn khi tng p sut ln gp i th nhit si l


49,90C. Tnh nhit si chun ca metanol.
S: 65,40C

8.

Tnh p sut cn thit nhit si ca nc t c 120 0C. Cho bit nhit ha hi


ca nc l 539 cal/g.
S: P = 2 atm

9.

Cho gin pha ca h 3 cu t (hnh di). Xc nh thnh phn ca A, B, C khi im


h chung l im P v hy kt lun v thnh phn ca A, B khi im h dch chuyn theo
ng thng ni t nh C vi im I.

S: %A = 40%, %B = 40%, %C = 20%


Nc nguyn cht c th tn ti 9 dng pha khc nhau (kh, lng v 7 dng rn). Tnh s
pha ti a ca nc c th ng thi nm cn bng vi nhau.