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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:
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
g1 H2K
g2
H1K
h H1
h H2
h K
h H3
gK g1 g 2 HH3
g3
g3
KH
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.
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
0,0081
dP
1434,6 41,3
(K/atm)
ln
1
1,987 T 100 273
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
lgP(mmHg) 7,04
1237
T
lg(760) 7,04
1237
T
T = 297,4K
dT
T2
dlgP
dT
4,575.T 2
M:
Suy ra:
1237
2
4,575.T
T2
= 5659 (cal/mol)
dT T. V
dP
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
1
1
1
1
7
373 T
333 T
12
2.
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.
8.
9.