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GIAO TRlNH HOA Ll
T,o.p HAl
N H I ~ T fJQNG Ll/C HQC HOA HQC
(T ai bdn idn thit ba)
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CHOONGVII
TRliNG CHUNG CUA DUNG D!CH
HON H<;IP KHI
A- DAI COONG vE DUNG D!CH
1. l!NH NGHiA DUNG D!CH
Dung djch 19. nhfing h4 dOng thl, bin nhit d9ng, g6m khOng it bon
hai chAt b thtii pJuin tdn phdn til va thi'mh pMn c6 the bitn thien
lien IJ!C trong nhii'ng giCri. x3.c dinb.
M6i dung dich Ia ml)t pha. bO qua nhfing hiu Ung M va tac
dt,mg ella nhGng truCmg ngoi\i (trQng tnrCmg, din tnWng, tlr tntbng) th1
d6i vffi mOi dung dich 0 tn.mg thai cAn bRng, th8.nh ph!in va ccic thut)c
tinh vi mO ciia n613 hodn todn gidng nhau (dOng nlult) b kh!p mQi ditm.
Trong dung dich, cac cha:t 0 thai phdn ttin phdn tli, tdc 13. 0 drrUi
fling tilu phdn (phan tir, tir hay ion) rieng re. b du<ri
dl,Ulgnhfrng nh6m nhO g6m mQt s6 it cac titiu phfin d6.
Tnr6c kia, h keo ciing gqi lit "dung dich keo'', nhung d613 dung dfch gid,-v1 h keo
\A nhUng h vi dj thl chU khOng phlii h\ h d6ng 1hf, ngoai ra h keo thuOng khl'lng ben
nhit dQng, c6 xu huVng bi6n ddi theo thOi gian. COn dung djch djnh nghia nhu Ia
dung djch t/!4t (dung djch chinh th(rc).
NhOng cMt cao phlin tlr c6 h1nh lhimh dung djch tMt veri dung mt')i nay va dung
djch keo v<ri. dung mOi kia. Thi d1,1, cao su thitn tan trong benzen cho dung djch
nhung tan trong mrOc thl cho dung dich,keo (lat6ch). Khi dung djch cao phan tir Iii:
3
dung dich th41 thl. chUng cilng tu!n theo nhling quy lu41 nhi1 dl)ng nhtr de dung djch
tMng thulmg cUa nhfing chat c6 ph:ln tt'r thil'p. Di nhitn, chUng cOn c6 nhfing thul)c tinh
thil ritng, glin litn v&i kfch thmR: phlln tlr lc'm ella chil't tan.
D!nh nghia dung d!ch kh6ng h<}ll dung phai fa &
lOng. Tlly theo tr:p1g thRi hqp ella pha (khf, lOng hay rB.n), ta c6
nhiing dung d!ch khf, dung dich lOng va dung rim.
N6i chung a cip sua:t khOng cao lAm, c8.c khi lutm luOn c6 the boa tan
kh6ng hlp]. vao nhau va do d6, nguyen tic, c<ic h6n hqp khi can
b&ng Ut dung djch khi.
Dung djch r&n (cling gQi ta tinh thl lflP hf/P) duqc hlnh th3.nh khi cac
ca:u tir chi nen mQt pha d.n duy nha:t. Dung d!ch rAn thuOng chi t6n
up trong nhiing vimg n6ng d() xac djnh, tuy cling c6 m()t s6 chat nhu
vang va d6ng va vang v.v ... c6 th6 boa tan vao nhau a the Tin
thea Mt kl ti nao. Dung djch rio dugc hlnh thB.nh trong SJ! ke't tinh tfr
nhiing h8n hqp lOng nhiing cA'u tir cila chOng.
D6i vOi dung djch lOng, nguffi ta phan dung cMt khi trong
chA't lOng, cha't d.n trong cha't lOng vi\ cha't lOng trong cMt lOng. C6 the
kh6ng m()t cha't ni\o a the lOng. Thi dt} c6 the duqc dung djch nuOc
ella NaO bang each trn nuOc eta vOi tinh NaO.
CUng m()t dung d!ch c6 the thu duqc ti.r nhieu cha't dau khlic nhau.
Thi d\1 dung d!ch nUOc ella axit sunfuric c6 the che' _tfr H
2
S0
4
va
H
2
0 ti.r S0
3
va H
2
0. Do d6 vic chQn nhUng chat nAo ll\m ca:u tir
ella dung cttch c6 theta tU.y Y- Nhung trong s6 3 cMt H
2
0, S03. H
2
S0
4
thl chi 2 Ia d()c D6 ta s6 t6i thieu nhiing cha:t hqp phAn rna ti.r d6 c6
the thu duqc dung cJ1ch axit sunfuric c6 thB.nh phAn Mt kl. S6 cha:t hqp
phAn d()c Ia so' cdU tU cUa hf D6 mOi Ia con s6 quan trqng trong
nhit d()ng li!C hQC.
ThttCtng thl ca:e tir n.io c6 trong dung dich vOi luqng 16n nha't so
vOi C<ic ca'u tir kbac thi gQi Ia dung mOi cOn cac ca:u tir k.ia gQi lil chdt tan.
D6i vOi dung dich cha:t khi hay chA't d.n trong cha:t lOng, nguai ta
thttCtng coi cha:t lOng lil dung mOi vl chat khi hay cMt rAn chi boil tan c6
hl_lll vao dung m6i. Ngay khi cMt khf hay cha't rAn bOO. tan v6'i lw;tn.g
4

tuong d6i IC1n trong chAt lOng tam cho Iugng tuong d6i ella chAt lOng trd
tbanh be hdn., nguOi ta vAn til!p tl}C coi cha:t lOng lil dung mOi.
Du& da.y, ta se nghien cUu l.1U tien dung djch 2 caU tli, thfi.nhAt vl d6
ta dung djch d<1n gi!n nhAt s61uqng cAu tir, thlt hai vl nhif!u quy
thu dlll;1C c6 th.! mb r<)ng ch.o dung djch cAu tlr hdn..
2. THANH PHAN DUNG D!CH
Mi)t trong nhiing tnmg quan trQng ella dung cijch Ia thlmh pMn
ella n6. Tlulnh phdn djnh tinh cho bit bin chAt cac cAu tir ella dung
djch, cOn tlulnh pluin djnh lu{fllg cho bit mOi cAu tir duqc chUa trong
dung cijch v6i nhiing n6ng d(J tile lil nhiing luqng tu<1n.g d6i lil bao nhieu,
nhiing Iuqng nay, cllng v6i nhit d() va ap suAt, Iil nhiing tham s6
nhit di)ng oo bin ella dung djch. C6 each bi.!u thi n6ng ru, cac
cAu tir ella dung djch, n6i chong c6 tM ehia tam hai : m(lt lo<;ri quy
luqng ella cAu tir m(lt luqng x.ic djnh ella dung djch, thU hai quy
Iuqng ella cAu tir ve m(lt luqng xac djnh ella dung ffi()i nguyen cMt.
Gi<l thir b T, p da cho, m(?t kh6i luqng G gam dung cijch, chim th.!
tich V, chUa nhiing ca'u tir l, 2, ... , i ... , c6 kh6i Iuqngg
1
, g
2
, ... g
1
... , c6 the
tfch 0 nguyen chAt lil V
1
, V
2
... , V
1
... , s6 mol cac cAu tir 18. n
1
n
2
... ,
n
1
... di nhien n
1
= g/M
1
b day Mi lil kh6i lm;mg phAn tir ella i. Kh6i
Iuqng dung d!ch 1a G = Lg
1
.
NguOi ta quy u(1c gQi 1 mol dung djch Ia luqng dung djch trong d6
t6ng s6 mol cic cAu tir bAng l (Ln
1
= 1 ). Klufi lll{fllg mol trung binh ella
dung d!ch 18. :
M = n
1
M
1
+ n
2
M
2
+ ... =

Ln
1
- Lni
(VII.!)
Ba.y gia xet nhiing c.ich bieu th! n6ng d(l ella cac cAu tir.
1. Luqng ca'u tlr quy v8 m9t luqng xic d!nh dung djch
1) Pluln mol 4 (thuUng cling ki lA Yi h* N) ella ctl'u tir i lil ti s6
gifra s6 mol Dj_ ella n6 v6i t6ng s6 mol Lllj ella c<ic cAu tir trong dung djch :
5
(VII.2)
C6 th8 n6i phiin mol x
1
lil s6 mol ella i trong 1 mol dung <4ch. Di
nhien ta c6 :
:Exi = x
1
+ x
2
+ ... = -EL + ~ + ... = :Eni = 1
Eni Ini I:ni
(Vll.3)
dod6:
l:dx; = 0 (VII.4)
D ~ c bit, d6i v6i dung djch 2 ca:u tir :
x
1
+ Xz = 1 ; x
1
= 1- Xz; dx
1
= -dxz (Vll.5)
Tir (VII.l) suy ra kh6i lw;mg mol trung binh ella dung djch :
2) Phdn triim mol ella i 18:
n
lOOxi = -
1
.100
:Eni
(VII.6)
3) PMn khOi lll{fng w
1
18 kh6i hrqng ella i trong dan vj kh6i luqng
ella dung d!ch :
(VII.7)
Di nhien :EW
1
= 1
4) Phdn trdm khbl!U{fflg cUa i 18. kh6i luqng ella i trong 100 dan vi
kh6i hrqng ella dung djch :
(Vll.8)
6
N6 OO.ng s6 gam_ ella i trong 100 gam dung <ij_ch. Thi d\1 dunf dich
axit axetic 5% Ut dung d}ch chUa 5 gam axit axetic nguyen cha':t trong
100 gam dung dich.
5) Phdn thl tich qli 13. tich ella i nguyen chlft tfnh d6i vOi 1 dcm vi
the tich dung djch :
v,
:::....:..L.
v
6) Phdn trdm thi tich cUa i Ut:
y.
1()()q>j = -
1
.100
v
N6 OO.ng s6 cm
3
i nguyen cMt trong lOOcm
3
dung djch.
(VII.9)
(VII.IO)
Dq m{lnh ciia n.rgu trong de h6n hgp nu6c ru.;ru duqc bi6u thi theo
each d6. Thi nrgu 90 13. h6n hqp chUa 90cm
3
rw;ru nguyen cha:t trong
3 -
lOOcm hOn hgp nu6c rugu.
7) N&ngdi) nwl-thi tich C; la s6 mol i trong 1 dan vj. tM tich dung dich:
C = ni
' v
(VII.Jl)
K.hi _chqn dcm vi the tlch 13. 1ft thi C; Ut n6ng d mol/1ft. D6i vm dung
djch 2 ca':u ti.r, nu 1 lit dung d!ch chUa 1 mol cha':t tan, dung dich gqi 13.
dung dich 1 mol, ki 13. 1M. Dung d}ch 2M chUa 2 mol cMt tan
trong 1 lit dung dich.
8) N6ng dq nguyen chudn 13. s6 dliDilg lUi;fng gam ella i trong 1 lit
dung djch. Thi d\1, dung djch c6 d() nguyen chuan 0,1N chrta 0,1 dUdn.g
lu<JO.g gam cMt tan i trong llit dung djch.
2. Lut;tng c&u tlt quy m9t IUt;tng Xic djnh dung mOl
9) N6ng d9 molan milA s6 mol ella i trong 1000 gam dung mOi (dung
moi ta cA"u ti.r 1):
ffij = ni . l()()Q = ni 1000 ::: Xj 10()()
gl nlMl XJMl
(VII.l2)
7
D6i Vffi dung dich ra:t loiing, X 1 :::::: 1, do d6 c6 SJ! ti gifra D1j v8. Xj :
1000
m
' Mt '
(VIL13)
Ghi chU.. N6ng di) dlii;IC dUng ilhat trong 1i lhuy(tlli. n&ng plutn mol Xj, lh6'
nh!t vi nhi!u lhul)c tinh cUa dung djch duqc bit!u lhi 0 dlplg dan giin nhi't khi dUng s6
tuang cUe pbrm tir, lhU hai vi n6ng dQ khOng phylhul)c vAo tht! tfch vii. d.
N6ng d molan m; ciing khOng phy thul)c vao T v8 V, do d6 cling thuOng duqc dUng
d6i veri dung djch loiing, khi sif phAn giila dung mOi va cMt tan 18 ro rimg.
3. Llin ht gllta nhlmg nOng de} c, x vil m d61 vlfl dung d!ch 2 ci'u tlr
Khi chuyt!n ti:r c sang x hay m va thl dn bi(t kh6i hrqng ritng ti 1:h6i
(ciing gQi ll m*t d) cUa dung djch.
I) Uin h giila mz va x
2
. Tir (VIL12) suy ra :
IOOOx
2
IOODx
2
mz=---
M
1
x
1
M
1
(1-xz)
(VILI4)
2) Liin giila c
2
vti x
2
. Tht! tfch dung djch Iii. V Ht V.IOOOml, c6 kMi
luc;mg G = g
1
+ g
2
g3.111. Kh6i luc;mg ritng p cUa dung djcb, tUc ll s6 gam cUa lml dung
dich ta:
(VII.lS)
rird6
C;! = = IOOOpnz lOOOpxz
V n
1
M
1
+ DzM
2
x
1
M
1
+xzMz
Nhung x
1
=I - x
2
, v*y:
cz = HXX)pxz (VII.l6)
M
1
+(M
2
M
1
)x
2
3) Liin hf giila mz va c
2
I 1ft dung dich, tUc ta lOOOp gam dung djch ch6'a M
2
C:2
gam ca:u tU 2. V*y (lOOOp- M
2
C:2} gam dung mOi. chiia ez mol ca:u tit 2. Do d6 s6 mol
cfu tU 2 trong 1000 gam dung mOi, tUc 18 d(l molan 111z ta :
(VII.l7)
8
4) Tntimg htJp tbtng djch rtft loiing. Nhitng b thik tren cbo thfy kMng c6 sl{ ti If
giila m
2
va x
2
, giila va x
2
, giita m
2
Oti d6i vOi dung djch rtft loiing (kbi x
2
-+ 0;
I - x
2
-+ 1), nhitng n6ng dQ d6 m6i ti 1 v6i nbau:
. 1000 M
m2 = Mt x2 b X2 =
(Vll.l8)
IOOOp
c2 = x2 = IOOOp c2
(VII.l9)
D6i vffi (VII.l7) c6 thi b? qua
0 miU<s6vl n6 rft be so v6i lOOOp, dod6:

m
2
=C:z
. p
(Vll.20)
Nu dung mOi lA nuifc thl kMi lugng rieng cUa dung djch rft loing thi!C t lA khOi
lm;mg ritng cila nuc'Jc gin nhu nguyen cMt, ntc lA p"' I trong difu ldn thui'Jng. khi d6 :
1000 1000
m2 =C:z =--x2 =--x2 =55,5Ix
2
(VI1.21)
Mt 18,016
Bdng VII-I
Llin h+ gllta c
2
, m
2
ri x
2
d6i v41 dung djc:h 2 cf"u tlr
"
m,
,,
,,
ldoopx
2
"
I000+M
2
m
2
Mt+(M2-Mt)x2
lOOOc;: IOOOx2
m,
IOOOp" M2c2
m,
Mt(l
,,)
M
1
c, M
1
m;:
,,
1000p-(M2-Mt>c:z 1000+ M
1
m
2
,,
9
B - D,O.I MOL RIENG PHAN
3. D!NH NGHiA VA THUQC TINH
CUA LliQNG MOL PHAN
1. O!nh nghia
MQi thuc tinh khue'ch d() X (tihu V, S, U, H, G, v.v ... ) ella dung
dich dtu c6 th! thi lit ham cUa'T, p vR ella s6 mol n
1
, n
2
, ... , n
1
ella
eRe ca:u tir trong dung djch :
X= X(T, p, n1, n2 ni ... )
Vi pha.n toAn. phAn ella X Ia :
dX=(:t dT+(:t dp+E[(:.t . ,dn;]
Chi s6 N CJ chAn c6 nghia 18. thanb dung <4ch hofm toan kh6ng
d6i, cOn chi s6 nj 0 chAn c6 nghia 18. s6 mol cac ca:u tir j (:;e i) khOng d6i,
trlr ca:u tir i dang xet c6 s6 mol thay d6i. 0 T, p const, ta c6:
dXT,p = E[(:.) . dn;] (VII.22)
T,p,nJ
Liuyt (G.N. Lewis) (1907) gQi nhiing hitm rieng 8X/On
1
Ut giil tri
mol plu!n cila hJQng X ella dung <fich d6i v6i ca:u tir i ella dung
dich va ki hiu 18. Xi :
10
x,=(ax)
ani T,p,ni
do d6, (VIl.22) tr/1 th.\nh:
dXT,p = E(X;dn.}
(VII.23)
(VII.24)
Ghi chU. 1M ding B.p (hay hlm Gipxo) mol ritog phht G; cila cAu tit i khOng gl
khac 111. thl!hrni hgc J.li. ella n6 (xem O...V, 6) (V.49):
lli =(::) =0;
l T,p,nj
Trong s6 tift cit Clic dq.i IUQIIg mol ritng philn tbl chi duy nhl"t G; mffi d6ng nMt vffi
tMhOO. hQC J.li. ci:Ja c(u tir i, cOn de hrqn.g mol pbiln kh!c nh11 U;,H;,ii;, v.v ...
khOng c6 tfnh d6. Cbi so s8nh djnh nghia v.! th hrni hqc v&. lugng mol
rieng phAn 1a thlfy ro. Thf d1,1 :
(
au} - (au}
li;=- *-Ui=- .
On; S,V,Dj On; T,P,IIj
0.3 kh!c nhau oo blin lil theo djnh nghia cila Liuyt thl dgi IIL{1ng mol riing phdn bao
gill ci1ng :We dinh JT, p const cOn d6i vOi. tht ho8. hqc 1-Li n6lil h!un ritng ella mQt
hlim tnmg U, H, F J;tay G theo s6 mol ella i khi tham s6 dUQC gilt c6 dinh Iii c*p
nhilng bi(n w nhitn ella hilm tnmg iy. Chi d6i v6i hiun Gipxo 0 thl tham s6 nay
m6i IAT, p.
2. Y nghia viiit li
1) Dt de hieu, ta xet thl tich mol rieng phdn Vi . KMi nim nay
dugc dua ra Ia vi n6i chung tM tfch V ella dung djch khOng Mng t6ng
th! tfch ella cac tir rieng re cUa n6 (d nguyen cha:t). Thf d1,1
d p = 1bar vA. t = 25C, nu trn 100 ml rlli.JU etylic nguyen cha:t v6i
lOOml m.Wc nguyen cMt th) th! tich cUa dung dj.ch thu dugc kh6ng bAng
100 + 100 = 200m! rna chi bAng c6 chitng 190 mi. Ciing khi
clorofoc (lOng). va ete (lOng) trn vao nhau th) c6 SJ! co tM tic h. Tr8.i
khi boa tan etyl iodua vffi etyl axetat thi c6 Sl,l' tang the tich. DQ bin
thien th! tich do Sl,l' trn c8c ca:u tir vilo nhau gAy ra pht,I thu()c vilo hn;mg
tuang d6i cUa chUng hie trn.
thi!C cha:t, th! tfch mol rieng pMn Vi ella ca:u tir i cho bit tM
tfch V ella dung <ijch bin thien bao nhieu khi them 1 mol i vao ml)t
lugng ra:t lOn dung djch c6 thimh pMn da cho, luqng ra:t lOn dm;:K: lit
sao cho thAnh pMn ella dung d!ch thi!C t c6 the coi nhu kh6ng d6i khi
them 1 mol i vito, d T, p const. Thi d1,1 the tich 1 mol metanol nguyen
11

cMt 18. V1 = 40.5cm
3
. Ne'u I mol metanol d6 v8o mQt hrgng rlt
IOn dung djch nUCtc metanol c6 thanh phAo metanol x
2
= 0,2 thi thi! tfch
V ella dung d!ch d6 chi tang them c6 37,7 cm
3
chU' khOng tAng them
40,5cm
3
. Ta n6i thi! tfch mol ri.eng phAn cUa metanol 13. Vz = 3'7,7 cm
3
d6i v& dung djch c6 tJtanh ph'" x
2
= 0.2 dii cho. D6i v(ri dung dich c6
thant> man khac thl Vz se nl$1 nhiing gia tri khac.
N6i chong, thi! tich mol phlin Vi ci:Ja i trong dung dich kMc
v(ri t1i tich mol Vf ci:Ja i nguyen chlt l:J cilng T, p va d'mg tr{Ulg thai
hqp nhu dung (ne'u 18. dung dich lOng thl phili Ufy i nguyen cha't a
tr4Dg thai lOng). Chi trong m(>t s6 trUCmg hqp Vi m6i bolng
Vf . Ne'u Vi == Vf d6i v6i m<;>i i thl dung djch duqc hlnh thanh tU cac
c!u tir nguyen ch!t khOng c6 bie'n thien thl! tich : thi! tfch dung dich se
bAng dUng tOng tich ale ca'u tir cMt. D6 18. tn.tCtng hqp dung
djch li tucYng, dung djch d!u hoii (Hildebrand, 1929), dung djch nita li
tuJng (Guggenheim) v.v ...
Nhung trong tnrbng hqp chung, Vi * Vi
0
, .1 Vi =Vi - Vf 7: 0 va
.1 VM = Eni .1 Vi 7: 0, nghla 18. dung djch duqc hlnh thanb til ciic ca'u tlr
nguyen cha't c6 bie'n the tich. Khi d6 tM tfch khOng c6 cng tinh .
.1 yM gQi Ia thl tich N6l8. bin thien tM tich ci:Ja dung cijch ga.y
ra do S\f bOn hqp, S\l tr()n ale c4u tlr vao nhau aT, p const va c6 cUng
thai 1\lp hqp nhu dung djch.
2) N6i chung, dqi tur;ng .1XM lit giUa gia tJi ella X d6i v6i
M sau khi t$1 cac ca'u tir va gia tri ci:Ja X tnrCrc khi trn cac cA'u tti aT, p
const va c6 cbng tri;Ulg th;ii hqp nhu dung djch .
.1XM = Lni Xi -.EniXf = Lni AXi (VII.25)
Khi .1XM = 0, X c6 cng tinh ; khi !V{M * 0, khong c6 cQng tfnh.
3) Cu6i cling, c4n chU 9 18. cdc luqng mol rieng phdn diu Ia
lutjng culmg bbi vi Mt luqng khuch d nao khi quy v6 mt')t
dan vj kh6i luqng (mol hay gam) cling d6u trO' thanh lttQrig cU'Ong d.
12
3. M9t sO thu9c tinh va h thll'c co bin cUa d'i IU"qng mol
riing ph.tn
1) Ung cUa hOm thu&n nhtit. Tlft ca. cae luqng khue'ch dl) X
ella dung dich d T, p const, deu lA h8.m nM't nhlft d6i v6i s6
mol n
1
, "2> ni ... ella elic ca:u tir trong dung d!ch (xem Ch.V.6) :
X(kn
1
, kn
2
, ... ) = kX (n
1
, n
2
,. .. )
Do d6, theo dinh li Ole (V.52) ta c6:
ax ax ax
X(n
1
, n
2
, ... ) = n
1
- + nz- + ... = :Eni -.-
&1 &z &i
tUc 18 d T, p const :
X= n
1
X1 + nz Xz + ... = :Eni Xi
(VII.26)
,.\p d\ffig (VII.26) cho X Ia V, S, U, H, F, G, S, cila dung djch ta dugc:
H = l:n;H;
F=En;F;
G = En; G; = l:n;Jli
<; = :EniCpi
(VII.27)
Ne'u chia mOi s6 h!;lllg trong (VII.26) v6i. tOng s6 mol Lllj_ trong dung
dich se duqc bit!u th(Jc d6i v6i 1 mol dung d!ch :
X=xtXI +xzX2 + ... =:ExiXi
d da.y X Ill t4i luqng khue'ch dQ ella 1 mol dung djch.
Ghi chU : D6i v6i dung djch 2 cf'u tU, (VII.26) viltlil ;
X=n
1
X1 +n
2
Xz
(VII.28)
Nlu dung mOi lit ntn'i'c vii. n6ng dl) molao cUa chit tan lit m
2
thi trong 1000 gam H
2
0
Ung vOi n
1
= (1000/18,016) = 55,51 mol H
2
0 c6 n
2
= m
2
mol chit tan (cf'u tir2), do d6;
(Vll.29)
13
2) Phucmg trinh Gipxu- Duhem. Til (VJI.26) :
X= n
1
Xt + n
2
Xz + ... =I:(niXi)
nc!u coi n
1
, n
2
, .. JA c8c bic!n vi X
1
, X
2
... ciing la nh\ing bic!n, tUc Ut giil
th!.nh phlln dung djch thay d6i thl vi phlln (Vll.26) aT, p const
se cho:
dXT,p = l:(n;dX;) + l:{Xidn;)
So sanh bi!!u th(tc nay vm (Vll.24) : dXT,p = l:(X;dn;), ta ke"t lu(\n,
OT,pconst:
l:(n;dX;) =0 (T,pccnst) (Vll.30)
H thUc nay gQi 18. phuctng trinh Gipxa (1876) - Duhem (1886). N(u
chia mOi s6 trong (VII.30) v6i Lllj se dll'tJC p.tr. Gipxo-Duhem
trong d6 thanh mOi ca:u til dugc bieu tbi bAng pMn mol xi ella n6 :
(VII.30a)
3) Slf chuyln nhilng thUc dtJng cUa cJu!t nguyen ch5t sang
nhib1g ccfu til trong dung d.ich. Nu d6i v6i chtlt choit, y va z Ut
hai lugng khue'ch dQ lien v6i nhau qua m()t luqng cuOng d<? x
theo phuang trinh :
iJz
y=-
ilx
thi c6 tht! chuy& sang d(u tir i trong dung nhu sao :
Do d6, nu d6i v&i cha:t nguyen chai y = Bz/Bx thl d6i veri. ca:u tir i
trong dung djch, ta c6 SJ! ph\J thuQc hrnln toan tuang n.r. tUc Ia Yi = .
Du6i dAy 18. m(lt s6 thi d1,1 :
14
Clu1t nguyin nlu1t Cdu ti i trong dung djch
in.
- ""
(VII.31)
y=-
Y;=-&
Ox
c, Cp =(:)
(Vll.32)
p
V=l:l
v, =(:l =[:l
(VIL33)
-s=(:;J,
=(i;J,
(Vll.34)

!(*)=-
(VII.35)
N6i chong, nhilng h tMc nhit d(lng dUng cho cMt nguyen chit c6 tht lip d1,mg cho
cic dfu tir ctia dung djch nhung phii thay nhilng IOVDg mol (chi tinh khukh
dt') m6i. c6 lovng mol) bhtg nhilng lovng mol rieng phd.n. 1bi dJl, ti:r G = H- TS
ta duqc:
J..l;=G;=H;-TS;
CDng v$y:
F;=U;-TS;
NgoAi ra cilng c6 tht 14p :
0 dAy fj lA hOl!ot lip i.
(Vll.36)
(VII.37i
t\'11.38)
4. PHliQNG PHAP xAc fliNH fl_,.l LliQNG MOL
Rlt:NG PHAN
1. PhiMng phap dung d'il'"l'ng mol bliu kli'n
a) D{li ltl{mg mol bilu kiln dUQC dUng rQng riii de 18m tfnh d6i v6i
dung djch 2 c{u tir, kbi d6 n6 thutmg duqc dilng cho cMt tan. dung
15
djch g6m n
1
mol dung mOi (ca:u tit I) va n
2
mol cha:t tan (ca:u tit 2) th'i
khi hofm toAn cba:t tan ra ldtbi dung djch, se cOn n
1
mol dung
mOi nguyen cha:t. Ngw:ri. ta gqi lw;mg mol biiu kiln' ella mQt thuQc
tinh khue'ch dQ X nao d6 ella dung dich dOi vai eM!: tan Ia.d;p lugng:
X-(Xln
2
=0
.Px (V1!.39)
2 ">
(Xln
2
=0 Iii gia ttj cila X khi dii Io(li hoiin toiin c!u ni 2 (cMt tan) ra khoi
dung d(ch, nhrr tM (Xln
2
0
n
1
X\' , iJ day X? Iii gill tri cila X d6i vai
I mol dung moi nguyen chlt. Do d6 :
_X-n
1
XI
x-
2 "2
ne'u dung mOi 18. nu(rc H:zO:
ol>x X-55,5IX?
2 m2
(VII.40)
(V!I.4l)
m
2
= n
2
Ia dQ molan ella cMt tan, cOn n
1
= 55,51 ta s6 mol H
2
0 trong
1000 gam nUOc.
Kbi X Iii tbl! tfch V cita duog dich 2 c!u til thl (VIl.40) Ia:
"'- ,.. V-n1vt
v - (V1!.42)
2 "2
Tir d6 c6 suy ra mQt cich giAi thich Y nghia ella thltich mol bilu
kie'n cUa cMt tan nhu san : Ne'u nhu dung mOi giU nguyen nhfrng
tinh ella n6 a thai nguyen cha:t thl the tfch ella n6Ift DJ vr va ch(t
tan dtrCm.g nhu c6 the tfch (V- n
1
\7? ), do d6 ne'u quy I mol chat tan,
nghla ta chia cho n
2
se the tich bien kie'n d6i v& 1 mol chat tan,
oi>v
2
(V - n, Vf )/ n2 . Til d6 suy m phnnng lrlnh bil!u thl v6 hlnh thrno
cog tfnh cila tbl! tfch v d6i vm dung djch 2 c!u tit :
16
V n1 Vf +

(VII.43)
Trong lrUOng hgp chung, d6i vm d;U hf\1Ilg X, tir (VII.40) suy ra:
(VII.44)
b) Tlnh lllqng mol riing phJn cUa cluft tan. Thi d\J; d6i v6'i dung djch NaO trong
nu6c, sl,l' xac djnh tbt tfch mol bil!!u kiln ella NaO 6 I8C cho phep bil'!u thi d{ti lugng
niiy bAng mc')t hlim giii tfch (tbl!! tfCh tfnh ra cm
3
):
Tir d6 suy ra :
+
_V-55,5IVt
"
' m,
2
16,4 + 2,5mz -1,2m
2
V = 55,51Vf + 16,4m
2
+ -1,2mi
b d:iy VIii thf tfch dung djch; Vf Ji thi!! tfch I mol H
2
0 nguyen cht = const; mzlli s6
mol NaQ trong 1000 gam(= 55,51 mol) H
2
0 = dQ molan ella NaO. Sau kbi d{lO ham
pbuang trlnh lrtn then m
2
(n
1
= 55,51 mol H
2
0 = const) se duqc:
- iJV 2
V2 = Omz = 16,4 +5m
2
- 3,6m
2
D6i v6i. m
2
= 0,5 tbl Vz = 18,0 cm
3
; d6i v{ri m
2
= O,l, V2 = 16,9cm
3
.
2. Phltdng phip giao dlim hay phU'CJng ph8p ti6p tuy&n 18. mt
phoong phap d6 thi do RbwbOm (Roozeboom) ra. H1nh VII-1 minh
ho{l. ccich de djnh tich mol rieng phlifl VI v8. V 2 d6i vOi dung dich
2 ca:u tir. Tru&: he't x3.c dinh bAng thJ!C tich V ciia 1 mol
dung dich d6i vOi mt day thruth phltn x
2
kM.c nhau (x
2
la phltn mol ella
ca'u tir 2). Sau d6 ve dUCtng cong V = f(x
2
) bit!u tl4 SJ! phl,l thul)c ella V
vao x
2
. Gqi PMQ 18. dubng cong d6. N6 dt nhihlg tn,Ic tung 4-i P iing v&
AP = V1 (x
2
= 0) va Q l{n.g v& BQ = V2 (x
2
= 1), Vf va 13. the
tich mol ella ca:u tir 1 va 2 nguyen cha't.
diem M ella duCmg cong U:ng v& dung <fich c6 tbanh ph.in x
2
n8.o
d6, ve tie'p tuye'n CMD v6i duOng cong. Tie'p tuyn nay cAt nhUng tr1,1c
17
v
I
a tung difm C (mg v6i Xz = 0 W
! di.!m D tJng vm Xz = I. C6 thi
chUng minh rAng :
- -- -
V
1
= AC va Y2 = BD
(sJ! chUng minh khOng kh6 khan
nh1Illg hcti d3.i, ta bO qua).
Ac_ __ _j_ ___ -!B
0 1
Neu Iuqng khuch d() X
kh6ng ph:ii Ia the' tich V th'i c!ich
li\m vAn nhu trtn, chi phili thay V
blmgX va:
Hinh VII-I- Phucmg pMp tie'p tuy!n xac
djnh d!.li hrqng mol ril!ng"phtin.
Xt =AC: X2 =BD
3. PhlfCfng ph&p dUng hf thli'c Gipxd - Duhem. D6i vrn dung djch 2 ca:u tt':r 0
T, p oonst, h thUc Gipxo- Duhem (VII.30a) vift Ill:
x
1
dX1 + x
2
dX2 =0
H thUc nay cho pbep tfnh X1 til: X2 ngUQC l!.li) khi Xz (hoi: Xt) dii duqc
bi!t d6i v6i m(lt diiy th!mh phn khlic nhau ella dung djch :
18
d'Xt
'
St! tfch phin l1 T, p const gilta 2 tqng thtii A va B se cho :
B
<}(,)a= <'Xt)A - J-;:
2
d:Xz
Ax,
Tfch Jilin se de djnh bAng {t!Umtg PJ,3pd6 thj.
(VII.45)
C- H6N HQP KHI
5. HON HQP KH[ Li Tl/ONG
I- DUNG D[CH Lf HONG
a) Djnh nghla. C6 thl! dinh nghia dung djch li tudng (hay hoiin chlnh)
19. dung dich thOO. man 3 dieu sau d6i v6i tOO.n khOO.ng thB.nh phAn :
1) V = EniVi
0
; 2) U = LniUf; 3) S = Lni (Sf - Rlnxi), b dAy V,
U, S 18. the' tich, n(li nang, entrOpi ella dung djch, Vi
0
, Uf, Sf 18. thl! tich,
n(:li nang va entrOpi ella 1 mol i nguyen cha:t i:J cU.ng T, p va cilng
th3.i hqp nhu dung dich, xi 18. phAn mol cUa i trong dung djch, R Ia
hAng s6khi.
b) H qwi. D6i v& mQi dung djch Mt kl, 0 T, p const, V V;, U "':En; U;,
H = :Eo;H;, S = :En;S;, F = I:n;Fi, v.v ... Do d6 d6i v& dung djch If tllUng, tir dii!u
- M --o -
1) suy ra : V; = V;
0
, 11V = l:n; (V; -Vi)= :En; AV; = 0 (khOng c6 bio!n thien
thi! tfch) ; tit dil!u 3) suy ra :
- o M - o -
U;=U;. 11U =l:n;(U;-U;)=Ui;AU;=O
Tir I) va 2) I:P. suy ra lJ T, p const :
H = U + pV = :En;(U[ + pV;
0
) = In;Hj ; Hj = Uf + pVt; H; =Hi,
AHM = QP =:En;<}!; -Hi)= :En; Mi; = 0 (khOng c6 hi?u 11ng nhi?t).
dHd,,.., dH[ o-
Tird6: C =-=-(:Enn: )=Ln -=l:nC = :En-c,.
PdTdT'' 'dT 'Pi''
Cp;
Tir kiln 3) suy ra:
(Vll.46)
19
Tir 2) vii 3) suy ra:
F = U- TS == In; (Uf - TSf + RT!nx;) = :En; (F," + RT/nx;)
Fi = ur -TSf. Nhltng F = :En; F;, V$y F; = F," + RT/nx;
M . -
ap ==In;(f;-Ff)=:En;6.F; =RT:En;lnx; <0
Tlr 1), 2) va 3) suy ra:
0 = U + pV- TS= I:n;.(Uf + pyt' -T'Sj
0
+ RT!nx;) =
= :En; <Of + RT/nx;)
kM.c 0 = I:ni!Li. , = 0;, !1. = Of + RT/nx;. Of, bilm Gipxa hay tbt! dAng
lip ella I mol i nguyen chit, lahitm ciia Tva p,jo d6 c6 the Of= 1-Lf (T,p). Khi d6
tbt! hoi hQC , cUa i trong dung djch If tulmg c6 dl!Jlg dt dan giAn :
1.1; = 1.1f (T, p) + RT/nx;. (VII.47)
c) Kei l!14n. Dung dich li tubng Ia dung djch duqc hlnh thanh tir cac
clfu tU nguyen chlft khOng c6 bin thien tich. khOng c6 bin thien ni
nang, khOng c6 hiu Ung nhit nhtmg c6 bic!n thien entrOpi xcic dinh bOi
(VII.46):
20
fd" = > 0
D6i vOi m6i clfu t1r i cUa dung dich li tuimg ta c6 :
Ui == Uf
Hi= Hf
Cp-, = C"
Pi
Si = Sf - Rlnxi
pi=
Gi = Gf (T,p) + RTlnxi
lli = Gi = llf(T,p) + RT/nxi
(VIL48)
II - HON HQP KH1 Lf T!XlNG
H6n hi]p(ll cac k:hf H mOng kMng duong nhitn Iii. dung d!ch If urbng (bOn hgp li
tuOn.g cUa cac khf) c6 dll.y dU clc tieu chu!n ella dung dich nliy. HOn hgp cac khf If
tulmg chi tbmi. min nhUng lieu chu!n d6 ntu ta tbila mQt s6 gill thilt, m()t s6 titn de
(xem diiCri. di!.y). Khi d6, h6n hi1P cac kblll tubng m6i. d6ng thai Iii him hqp (dung djch) H
tuCm.g ciia cic khf. b dil.y, ta thi:ra nhitng gii thilt (tien de d6) vii dUng tbu$t ngfr
h6n hgp H tuOng ella khf va him hqp.ciia cac khi li tm'mg lheo nghia nhu nhau.
1. Ap suit riing phln
Theo Dantdn, cip rieng phitn Pi ella khi i trong mQt bOn hqp khi
blft ld (li tOOng hay khOng) 19. 8.p su!'t rnA khi i d6 se t3.c d1,lllg nu nhu n6
mt mlnh toan bQ tM tich V ella bOn hqp 6 cU.ng d(l T nhu
h6n hgp.
D6i v6i h6n hqp khi li tt.Wn.g, d!nh nghia d6 din t6i djnh lw,it Dantdn
(Dalton, 1805) ve cng tinh ella cic lip sulft ritng pMn.
Gi<i sir h6n hqp khi' If tOOn.g g6m n
1
mol khi 1, n
2
mol khi 2, ... , c6 the
tich chung 18. V, ap suAt chung (tOOn phlin) 18. p l:J d T. C6 the bieu
thi phuong trlnh thai ella bOn hqp khi li tul:Jng gi6ng nhu d6i v6i
khi li tuimg chAt :
pV = nRT= (n
1
+ n
2
+ ... ) RT=:EniRT (VII.49)
tir d6:
D
P
= I;.::L RT = EcRT
v '
(VII.50)
Nhung theo d!nh nghia DantdD ap suAt phAn Pi ella khi li
tul:Jng i :
(VII.51)
(1) Trong nhit c!Qng l\fC hqc, thu._t ngU Mn hqp va dung d!ch thuCmg diJI!C dUng
d6ng nghia.
21
tac6:
p=pt +P2+ ... (Vll.52)
tUc J.a : O.p sw1t toiin phdn cUa h6n h{1p khi /i tudng bOng tdng dp sudt
riing phdn Pi cUa ting khi trong hJn hqp. D618 n(Ji dung ella dinh
Danton, phin 8nh tinh cng duqc cUa clic lip su!"t rieng pMn d6i v6i bOn
bgp khf If nrimg.
Til (VII.51) va (VII.50) suy ra:
J2__ = ....!2_ = Xj tiic lA : I Pi = PXj I
:Epi . .
(VII.53)
Nhu Up sw1t rieng phdn P; cUa khi i trong h6n h{1p khi li hldng
bdng llp sudt toiin phdn p cUa Mn lu;rp nhdn vUi phdn mol x; cUa n6
trong h6n h{1p /chi.
Ghi ciul. Ap sua\ ll thuQc cllitng d6 lip sut ritng pb&l kMng c6Iien quan
ci deD hn;mg mol rieng ph4o (cbi thuQc tfnh khuLch mt'ii c6 IUQDg mol ritng
phdn). .
2. Thi tlch
Til (VII.49) suy ra :
RT
0
V = l:ni- = :Enivi
p
(VII.54)
v, = RT 1 p Ia thi! tfch I mol.khf If tuimg i nguyen cba:t a cilng T, p nhu
bOn hqp. Nhung V = Lni Vi, Vi lA tM tfch mol pMn ella i trong
b6nbgp.
3. Nql nlng
D6i vm the tfch, thl nhu tren dlllam, tir phuang trlnh thai cila
bOn hqp khf H tuOng suy ra dugc Vi = Vi
0
. COn d6i veri. ni nang, khOng
suy ra duqc Ui = Uf. qua nAy phRi duqc tbira nl$1 nhu m"t tien
trong d<)ng 11/C hQC c6 dien, ttic Ia ta phii thi\'a :
22
(VII .55)
4. Entr6pi
Theo (V1.5a), entrOpi Sf ella 1 mol khf li _tmJng nguyen cha:'t c6 d(Ulg
Sf = sf (T) - Rlnp, sf (T) lil s6 chi Jil.\1 thuQc vao bim chA't khi v8.
vito T. dQng li}'C hqc thl:ra nl$1 rAng entrOpi mol rieng pMn Si cita
m6i khi i trong bOn hgp khi li tubng vAn c6 gi6ng nhu entrOpi mol
Sf ella khf li n.Wng i nguyen cMt nhlRlg phiti thay .ip suAt p ella khi
nguyen cha't b!ng lip sua:t ritng pMn Pi ella khi i trong bOn hgp, tlic Ia :
(VII. 56)
S\f thira nl$1 oily lA m)i dung ella djnh li Gipxu vl entrOpi ella h6n
hgp khf li tulmg. Vl Pi = px
1
nen (V!I.56) c6 tM vi!t :
Si = sf (T) - Rlnp- Rlnxi = sf - Rlnxi, do d6 _:
S = :Eni Si = :Eni (sf - Rlnxi) (VII .57)
Nhu trong ba.tieu chudn (hay dit!u kin) ella dung d\ch If tuOng
thl chi tieu chuAn th! tfch (VII.54) m6i duqc nit ra tir phmmg trlnh
thii ella h6n hqp khf li tOOng, cOn tieu chuAn nang (VIL55) va
entr6pi (VII.57) pluli thi.ra nhu nhiing tien dt! d6i v6i bOn hgp khf If
tuOn.g. Chi vOi dit!u nhu thi mOi khf If tubng i trong bOn hgp
m6i c6 !:My di:J cic thu()c tinh (Vll.48).
Ghi chU : I) Theo (Vl.7), hAm Gipxu hay tb ding ap cil.a I mol kbf If tuOng i
nguyen cMt c6 G[ ""gj (T)+ RTfnp. De'! chuyfn sang th. d&ng ap mol ritng ph4n
ella khi li tuOng i c6 ap suft ritog ph4n Pi troog h6o hgp, ta chi thay p bAng Pi :
0; = g;
0
(T) + RTlnp; (VII.58)
Vl Pi = PXj nen :
0; = gj'(T) + RT/np + RT/m:; = Gj' + RTI11X;
2) VI Pi = qRT otn (VH.58) c6 thf vit :
23
G; = gf(T) + RTlnRT + RTlnc; = g.o(T) + RTlnc; (Vll.59)
v{ri : gf(T) = gf(T) + RTlnRT
3) Vi J.l; = G; n!n tb bOO bQC lli cUa. khi If t!Kmg i trong bOn bC1(l khf If t!Kmg c6 the
bitu tbi du6i m('lt trong nhilng :
J.l; = J.lf (T) + RTlnp;
J.l; = J.l 'f(T) + RTlnc1
J.l; = J.lf(T, p) + RTlnx;
troog d6 J.lf(T) = gf(T) ; J.l.o(T) = g'f(T) ;
J.lf (T, p) = Gf(T,p).
(VII.60)
&. HON HQP CAC KH[ THI!C (KHONG L[ TIJONG}
1. Ap su&t rling phtfin
D6i vOi bOn hqp khf thJ!C, ;ip phAn dinh nghia theo Dantdn
khOng c6 cQng tinh, tUc 18. khOng tulln theo d!nh Dantoo :
p * :!:Pi (Daiitan)
ngoai ra:
P; (Danton) * PX;
Sb cfi nhu Hi. vi ap ritng phAn (diflh nghia theo Danton) cUa
cac khi thJ!C trong bOn hgp khi Ut khOng dQc ; giita c8.c phan tit ella
nhllng khf thl)C luOn luOn c6 nhilng tuang tile khOng tM b6 qua nhu d6i
vOi khf lf tuOng.
Dt bio toan tinh c()ng dw;rc ella clic lip sua':t rieng phAn thl trong
tntC1ng hgp chung, d6i vOi bOn hqp khi li tltdng cling nhu kh6ng li tltdng,
ta c6 tht dinh ngliia Op sutft phdp hinh thUc p, Ia ap su!t thoit man
thac:
(VII.61)
24
Di nbien, d6i vm hOn hgp khi li tuimg, Pi djnh nghia theo each niiy
trlm.g v6'i: Pi d!nh nghia theo Danton.
D6i v6i h6n hqp khi th\f'C thi til (VII.61} ra duqc :
Ep, (hinh thllc) = Ep><; = pl:xi = p
tile 13. suy ra duqc cng tinh cic ap rieng phin hlnh thiic, nhlffig
khOng the suy ra dugc Pi hinh thiic IR lip su&:t rna khf i trong bOn hqp khf
tht,rc se c6 ne'u nhu n6 chie'm ml)t minh tOO.n b the tich V Gila bOn hqp 0
clmg dQ T : N6i each kMc, d6i vm hi\n hgp khf th\IC. Pi (hinh thllc)
* Pi (Dant<111). D6 18. do c6 tUdng tac giiia c8.c phAn til khf thl!C, va khi
th\IC khOng tuAn theo phuong trinh lf!JI8 thai cila khi li tuimg. Chi /1 ap
suit dll tMp, chfnh xac Ia khi p --7 o, m6i. c6 the 00 qua nhilng nrong tac
d6, khi d6 khi th\lC d11qc tinh li tubng vR Pi (hlnh thiic) m6i d6ng
nMt v6i Pi (Danton).
2. Hoc;.t Bp rling phlln (th1.1'0ng chi gQi tit 13. hofll tip)
Tit nay, d6i v6i mOi khi i trong bOn hqp khi li tuOng cling nhll khOng
li tuOng, ta <leu djnh nghia lip rieng pMn Pi theo each th6ng nha:t
(VII.61):
Pi= PXi
hiln hgp Ia if tuimg, boa hQC cila khi If tu/1ng i trong hiln hgp

1!; = (T) + RTinp, (VII.62)
S6 J.Lf (T) chi thuQc vloo Tva bang hQC ella i khl Pi= I.
Ne'u bOn- hqp 13. khOng H tuOng, cip sui't rieng pMn Pi ella khf thi}'C i
trung hiln hgp khOng dllng (VII.62). bio toiin don gii.n
(VII.62) ella the' bOO. hQC, ta thay Pi ella kbi thJ!C bAng lUQng fi sao
cho th boa bQC J..li ella khi thqc i trong bOn bqp bing :
).1; = flf (T) + RTJnfi (VII.63)
25
vil sao cho khi ap sWft toiln pMn p cua bOn hqp ti&. d&n tOi khOng (ngllla
Ia khi bOn hqp khi ti(n d&n Mn tr'llll! thai li tulmg) thl f; -> Pi nlc Ia :
lim(f) r (r,) r 1
p--+0 Pi = pxi = Yi =
(Vli.64)
lm;mg fi ngh'ia nhu g<;>i 18 ho{lt O.p rieng phcin cita khf i
trong hiln hqp kbJ. Ti s6 y = f/p gQi lil s6 hOf!t cua kbJ i.
(V1J.64) c6 nghia lA d6i v6i bOn hqp khi If tubn.g, fi = Pi va Yi = 1.
Trong t:rOOng bgp chung, 8p fi ella khi th!JC 18 h8m ella nhit cJO,
ap sWft va thAnb pMn cua biln hqp.
Khi bOn hqp khi thvc khf>ng c6 sai so vO:i tfnh If tubng, c6
8p di,Ulg quy t&c gdn dUng sau :
(VI!.65)
tile lA: trong bOn hqp khi thJ!C, ho.,t 3.p-fi ciia m6i khi i x!p xi bAng
mol xt ciia n6 trong h6n hgp khi nhatt v6i 8.p if ella khf i nguytn
chlft, 0 nhit dQ vA ap suA't bang nhit d() vA 8.p su!t tOO.n phfut ella b6n
hqp khi. Trong (VII.65) chi s6 K chi pha kbJ (hay hoi) ; khi khOng sg
nhllm Ian vOi pha long (dung djch long) thl hi> khOng can ghi K.
lip fi
0
ella khf i chlft c6 the tinh ti:r <ip su!t pf vA tir h
s6 h04t dQ Yi cUa n6 theo phuang trlnh :
7. Sl/ HOA TAN CHE CUA
cAc KHiVAO NHAU
(VII.66)
Ml)t lhlJi gian dli, ngll(ri ta cho ring tAt ci c8c khi d!u c6 tM tl'l)n lin holm to!m vlo
nhau theo bft klli nlo. Nhtmg ngay ti:t 1894, Van de Van di tien doan rAng cac khi c6
26
thi khOng trQn lin ho8n to8n vio nhau vi c6 thi tich ra thMh hai lOp {h$ pha kh0 ca:.,
bAng v6i nhau;, trtn dl) t6i hfll. ella cac khi. Un diu tien (1941) cic nhlt hac
Lien xo LR. Krichepili, P.E. &nsacop va D.X. Xiklixo di kh6m ph8 ra bing th\fC
nghim tioh tao hfll. cht ciia cic khi Mi. v6i Mn hqp NH
3
vA N
2
khi 4p sufl dtt t6i vlti
nghln bar vlt vlti nlm sau tim tMy tm;m.g d60 nhieu h6n hqpkhf k:h4c. N6i chung
511 blob thltnh 16p;, nhilng h6n d6 tuAn theo nhilng quy dii bitt VI! Sl,l chia liTp;,
nhllng h6n hqp llmg (xem Ch..XIV, 6).
27
CHOONGVIII
DUNG D!CH L6NG VO CUNG LOANG
St,r nghien cUu tb\fe va li thuyl!t dung djch loing dil n6i len hling diu a
cu6i tM ki 19 diu tht ki 20. Nhil'ng dinh lu$t djch lOOng Iii nliitng d{nh fu4t giiti
h{:ln, chi dUng chlnh Xll.c d6i v{ri. dung dich v6 cUng lOOng, cOn d6i vOi. dung djch cO dQ
Joiing hihl tbl bai. tinh thi,{C Iii pb;\i xAc dinh xem ohimg djnb luj).t c6
lip d\Jng trong chirng m\fC nilo rna khOng ga.y ra sai s6 dang Ice.
1. CAN BANG DUNG D!CH LOANG - HOI
BAO HOA. flQ AP SUAT HOI.
flQ TANG SOl CUA DUNG D!CH LOANG
1. Ap su8t hoi bio hoi cUa dung djch lOng
Hai cAn bAng v6i dung dich lOng gQi Ja hdi baa hotl (ggi tAt 13. hm)
ella dung djch. N6u n6 chiia mQi clu tir ella dung dich thl Rp hai se
blng tOng ap suG:t hcri ritng ph3.n ella cac ca:u tir. Mt)t s6 clio tfr c6 tM
khOng bay hoi (boJc chi bay hai khOng dang ke) b dQ scit va
tht!C t6 Ul khOng c6 trong hoi.
2. )jnh Raun v8 sl,l' flp su8t hC:Si cUa dung mOl tr8n dung
djch
a) Trlllmg lufp hdi. Ia li tllling. Nam 1886, nh8. Me hQc Phap Raun
(F .M.Raoult) tlm tMy bAng th\IC dp sudt hdi. cUa dung mOi trett
dung dich lodng be lum tip sULi't hdi. cUa dung mOi lOng nguyen chtit d
cUng (v8. C:J cllng tip su:ft ngoAi).
D6i veri dung dich 1oing, tip su:ft hcri p
1
ella dung m6i ti veri ph!in
mol x
1
ella n6 trong dung djch:
Pt =kt Xt
28
.,
Khi x
1
= 1 (dung mbi lOng nguyen ehlft), PI= pf = kt, \1.Y k
1
chinh
la lip sua:t hoi pf ella dung mbi lOng (ea:u tir 1) nguyen eba:t l:J ci:mg
Dod6:
I Pt P? Xj I (VIII.l)
GQi x
2
18. phin mol ella tan (ea:u tir 2) trong dung djch. D6i v6i
dung djeb 2 c!u tir, X 1 + X2 = 1, do d6 X 1 = 1 - x2 v8 (VIII. I) c6 the :
(VIII.2)
ghi p
1
tren tn,Ie tung, x
2
tren tn,Ie hoanh, duCmg bieu 18. mt
dllOng thOng. Tlr (VIII.2) ll!i suy ra:
0
Pt -Pt._ x
- 2
P?
(VIII.3)
Nhilng phuong triuh til (VIII.l) Mn (VIII.3) Ia nhilng bi!!u thllc cua
dinh Raun. 8p1 = pf - PI gQi Ia d(J h{z tuy4t dtli 3.p sulft hoi
ella dung mbi va do bAng nhilng dan vi nhu mmHg. COn
(pf - Pt) I pf = 8p1/ pf gQi Ill d(J /u;l tUdng dbJ lip sua:t hoi ella dung
n6 Ill mQt dJ!i luqng c6 thu nguyen. 0 <4ng (VIII.3) djnh
Raun c6 tho! pbat bi!!u :
D(J /u;l tlltmg dOi ilp sudt hai cUa dung m6i tren dung djch lo5ng lxing
phdn mol cUa chdt tan trong dung dich.
D6i v& dung djch rlt loiing, n
2
n
1
, (VIII.3) c6 tho! vit :
8p1 = P? -pi =

= n2 _n_z
pf pf Dt +n2 Dt
(VIII.4)
m
2
Ia d molan, tUc Ia st5 mol ddt tan trong 1000 gam dung moi
th1 n2 = m2 v8. Dt = 1000/M
1
.Mt Ia kht5i lm;mg phan tir ella dung mOL
Khid6:
29
(VIIl.5)
0 nay, djnh Raun c6 th<! phat bi<!u :
Dr! ht;l tllung dtli clp sudt hdi cUa dung m6i dung djch ln5ng ti
viii dr! molan tUa clutt tan trOng dung djch, stf tl Ka lxing kM'i
lu(lllg phdn tlicUa dung m6i chia clw 1000.
(Vlll.4) c6 tM vie"t :
n, g,/M
2
--=xz
pf Dt 81/Mt
(Vll1.6)
thUc nay cho pbep xac dinh kh6i lw;mg pha.n tir M
2
ciia chlft tan
khi da bi(t Mt Apt/P? va lw;mg 82 gam chl'ft tan trong g
1
gam dung
mOi.
b) Tntimg h(lp /uti Ia khong li tudng. Khi d6 phlti thay ap bAng
h"'!t ap va djnh Raun (VIll.l) chuy<!n thanh:
(Vlll.7)
f
1
Ut 8.p cUa hoi dung mOi tren dung djch loing, tf 18. ho!_Lt B.p ella
hoi dwtg moi lOng nguyen cMt 6 cUng d va ap sulft ngoai nhU
dWlg dich. (VIII. 7) gqi 18. djnh Raun tdng quat.
Ghi chU. Nbiing dung djch lOng tuAn theo cit: djnh lu;)l Raun (VIIl.l),
(VIIL2) hay (VIII.7) l1 mQi n6ng dO gQi Ill du.ng djch li tlldng (hay dung dich hodn
chinh). D6 lA dung djch lOng dan giin nMt Nhitng dung djcb lOng khOng hoM
chinh chi tullo theo djnh lu$1 Raun khi dung dich lA dli loing (chfnh Xlic Ill vO cllng
loing). C6 th.! n6i dung djch khOng ho3n chinh lA II nrbng chi d6i vm dung mOi khi dung
dich Ill lOOng.
3. E>!nh Henry v8 flip suit hell cUa chit tan
a) D6i vOi dung dich loing, nc!u cMt tan ciing bay hcri thl n6 tua.n
theo djnh Henry (1803). Nlu hcri lA li tU'Cm.g, dlnh nAy vilt lA:
P2 = k2x2
(VIll.8)
30
tii'c 18. 3.p sua:t hai rieng pMn P2 ella ehlft tan ti 1 v& ph:tn mol x
2
ella
n6 trong dung cij.ch lOOng, h s6 ti 1 k
2
g<_>i 18. sd Henry. Ch6 khac
nhau can ban v& dinh Raun 18. k
2
chi 18. mi)t hAng s6 nao d6, tu)'
thuc vao kin t6n ella M (T, p ngoai da cho), N(u d6i v& dinh
Raun p
1
= k
1
x
1
= pfx
1
, tllc 18. k
1
= pf thi d6i v6i Henry
Pz = k2x2, k2 :1:- khi dung <4ch 13. khOng li tubng v8. ra:t loing (Xz 0),
do d6 kh6ng the suy t6i.n6ng d x
2
=I.
Ne"upha hai Ill kh6ng li tubng, phii thay lip sua:t P2 bAng lip f
2
va
(VIII.8) vit Ia :
f2 = kzx2
(VIII.9) 18. djnh lll4t Henry tcfng quat.
(VIII.9)
b) Dinb Raun va dinh Henry dll'<JC tim thl!y dc nhau
nh11D.g c6 the: chUng minh r8ng del vdi dung djch loiing, ne'u dung m6i
tudn theo d!nh luljt Raun thi clu1t tan tdt ye'u phdi tudn theo dinh lur;it
Henry va ngiiiJC
c) Ne"u dung dich 18. If tuUng (ho8.n chinh), nghia Ill n(u dinh
Raun dUng v& m<_>i n6ng d thi dplh Henry cfing dUng v& mqi n6ng
d. Khi d6 c6 the ngoiP. suy t6"j x
2
= 1 (chlft tan b tllDg thai lOng nguyen
1
2
= k
2
= If vii (VIII.9) tr6 thilnh:
(VIII.IO)
Nhu th(, dOl vdi dung d!ch lOng li tliUng, nqi dung cUa hai djnh lut)t
Raun vd Henry trUng nhau. D618. hqp nhllng phuang trlnh f1 = ffxt
va f
2
= ffx
2
gQi lA dinh Raun- Henry tOng qu8.t hqp nhal, thOOng
chi g<.>i cit 18. dinb Raun. Khi pha hai 18. If tui:rng, ap trimg v& ap
sua:t, khi d6 p
1
= pfx
1
va p
2
=
31
4. Thi" ho6 hqc cua c6c cifu to/ trong dung dfch loing
Kbi c6 cAn bAng dung djch long vai hai biio boil cila n6 thl tM boa
hQC ella ca:'u til i trong ci hai pha pluii bAng nhau 1-l:iL = J..Lf (L =
lbng, K = khi (hai)). lbl!hoa h<,>e cila i trong pha hai c6 di!Dg:
I';K = l'i'CT) + RTinfi
D6i v6i dung mOi 1, theo dinb Raun ft = tfxi, vn:
/Jt = J.lf = J.lf = J.Lf(T)+ RT/nf
1
+ RT/nx
1
.
<'ip tf ella hoi dung mOi cha:t chi ph\! thul)c vi\o Tva p
ngoili, do d6 c6 tht gQp 2 s6 v phlli phuang trinh Wn thilnh
mQt s6h(Ulg chong:
flf (T, p) = flf (T) + RTinff
va. :
I IJ.t = JJ.f (T,p) + RT/nx
1
I
(Vlll.ll)
J..Lf(T,p) 18. tht!hOO.hQc clladungmOi (khi x
1
= 1). N6
PhtJ. thuQc chil vao T, ra:t it vao p, vi B.p su!t chi c6 anb hui1ng ra:t nhO
d6i v6i ch(t lOng.
D6i vf1i. ch!t tan trong dung djch lOOng, theo djnh Henry
f
2
= k
2
x
2
(kz-* tf):
J..l2 = = = (T) + RT/nk
2
+ RTlnx
2
Henry k
2
Ia hAm ella T va p, do d6 cfing c6 tM :
(T, p) = (T) + RTink2
va duqc:

32
(V!II.12)
Cln! y rAng d6i vm dung djch kMng If tulmg va Ieang, (T,p)
khOng c6 y nghla I! hot hQC ella tan (clfu tir 2) lOng nguyen ch!t
v1 khbng suy tt'Ji nOng d() x
2
= l. (T, p) cling ph\1
thuc chU ye'u vao T, rf"t it vao p.
s.aq tiling dii'm sOl cUa dung djch loing_ chit tan kh6ng bay hdi
a) dtj sbi cUa pha lOng. &t eli pha lOng nao. nguyen cMt hay
dung d!.ch ciing <leu bAt d&u sOi l:J nhit d rnA d6 8.p hcri biio holt
cUa n6 tr6 thanh bAng 8.p sulft ngoOO.. Nc!u 3.p sua:t ngOO.i bQng 1,013 bar,
nhit d sOi gqi 18 dtj s6i chudn hay dilm sbi (hay phi dilm)
chudn.
D6i vai chdt lOng nguyin cluft, khi lip su4t ngohl khOng d6i thl nhit
dt) sOi ciing khOng d6i su6t thCri gian sOi cho dc!n khi toan b(l cMt lOng
chuyen hc!t tbanh hdi. Nhu d6i v6i cMt lOng nguyen chlft, d:
bAt dSu sOi vA nhit d ke't thllc SJ! s6i 18. mt)t. Nhlfng d6i v6i dung djch,
lJ 3.p sulft ngohl khOng d6i, trong tn.rOng hW chong, nhit dQ bAt dfiu va
ke't thiie sg s6i 18. kh!ie nhau va nhit d(t s6i thay d6i t1,1e trong su6t
qua trlnh s6i.
D6i vOi dung djch lcxing cMt tan kh6ng bay hdi, hoi blio bOO. ella
dung djeh chi g6m c6 hoi
bao bOO ella dung m6i va
theo dplh Raun, lip
sua:t hoi bao bOO. d6 lu6n
p
1
B B'
B"
luon tMp han ap su!t hai p barf--------;,1'-7'{-7{--
ba:o bOO. ella dung m6i lOng
eha:t 0 ellng nhit
d(t va cilng p ngoai.
lfinh VIII-1 bieu thi sl!
phy thuQc ap sua't hai biio
boa ella dung m6i
eha:t (duUng eong AB) va
T,
T'
'-T
ella dung d!eh lo3.ng e6 Hinh Vlll- 1. S1. tang dil'!m soi cUa dung djch Joang
n6ng d(t kh!ie nhau (duUng chft tan khOng bay hai.
33
eong A'B' va A"B") vao d. N6ng d pMn mol x
2
ella ehft"t tan
trong dung d!eh c3.ng IOn (nhllng dung d!eh vAn dll loing) thi dltOng
cong ap sua't hai ella dung dieh ea.ng phAn b6 tha'p bon so v6i dll(mg
eong <ip suft"t hoi ella dung mCi nguy.en ehft"t.
Dt xae dinh d s6i ehudn, ta ve tren giAn d6 hlnh Vlll-1 dll(mg
ding cip ling vUi Po= 1,013 bar. d rna d6 dufmg d!ng <ip nay
dt nhilng dufmg eong AB, A'Ii', A"B" v.v ... tc;ri nhiing diem C. C, C', ...
Ia d sCi ehutln ella nhiing pha lOng tuong lhlg. Ta thA"y rlng
d s6i ehuAn d6i vUi dung d!eh loiing (T
5
) lu6n lu6n tan bon so vUi dung
m6i nguyen eha't (T
8
) va giii'a ehUng = T
8
- T
8
se eang IOn
neu n6ng d x
2
ella eht"t tan cAng IOn (trong vi dung dieh van
loang).
b) Thiel /f)p cOng thUc dOl vOi
D6i v& nhiing dung dich dll lOOng

c6 the <ip dl,IIlg dinh Raun, ta e6, khi ap sua:t hai p ella dung dtch
bAng lip suft"t ngoai p
0
= 1,013 bar:
P = Pt = pjxl =Po = 1,013bar = eonst
Sau khi Illy logarit phuong trinh nay r6i d<itO bam theo T se duqc :
dlnp = dlnpj' + dlnx1 = d/np
0
=
0
dT dT dT dT
(a)
pj 18. lip suAt hcri bao bOO ella dung moi lOng nguyen cha't, n6 tuAn theo
phuong trlnh aaperon - Qaudiuxa :
d/npy Lh,l
--=- (b)
dT RT
2
Ltt.t 18. nhiet bOO. hai ella 1 mol dung mbi lOng nguyen chft"t. Do d6
ktt hgp (b) viii (a) se dlllJC :
d/npj Lb,l dlnx1 dln(l- xz)
---;r[ = RT
2
= ----;rr = - dT
34

Lhl dT
-dln(1- x
2
) = -'-.. -
R T2
Khi tich pha.n phlWng trlnh nay trong khoAng nhit d nbO. ti:r
di) sOi chuAn ciia dung mOi chA:t (x
2
= 0) di) biit
d!iu sOi chuAn Ts ella dung dich lo1ing c6 pMn mol x
1
ella dung m6i
bang (1 - x
2
) thi c6 th<! chOCp Lt,,
1
= const, do d6 :
x2 L Ts dT
- J-
0 R 1fT'
L (1: T
0
)
I (1 )
- h,l s - s
-n - x
2
-
Tso
(c)
D6i vai dung djch r!t lo1ing, x
2
<< 1, c6 th6 cha:p nM.n cOng thllc gful
dUng:
-In (1 - x
2
) Xz
kbac, vl (f
8
- !a be, c6 the ch!p T
8
T
8
=

va phuung trlnb (c) trO th8.nb:
Lh I (T, - T,')
Xz = --"'"-'-"':--,;--'-"
R(T,')2
GQi dT
8
= T
8
- 13. tdng diim sOi cUa dung djch :
R(To)2
' Xz
Lh,l
AT,
(VIII.13)
D6i v6i dung djch r!t lo1ing c6 dl) molan m
2
(s6 mol cMt tan trong
1000 gam dung mOi), theo (VII.18):
x2
1000
35
(Vlll.14)
L
A.h,l = 13. bOO. hcri. rieng (t11'c 13. d6i vdi 1 gam) ella dung moi
nguyen chit thj ra J/g). Vl n6 1a Mng s6 b nhit xac
d1nh nen c6 the :
'I =-K-,m'zl
(VIII.15).
tUc 18. tiing dilm"s6i cUa dung dfch lodng ti vcTi n6ng molan m
2
cUa chdt tan trong dung dfch. s6 ti I Ks &Qi 13. lulng stl nghifm s6i
(hay phi nghifm) ella dung mOi nguyen cMt. Gia tri li thuyl!t ella n6ta:
K, = = 0,0083(1-;')2 (VIII.16)
1000'-h,l '-h,l
bbi vi
__!__ = 8,314 0 0083
1000 1000 '
lUng s6 Ks chi t4c trung cho dung mOi, khOng ph\1 thu()c v8.o b3.n
cMt ella tan. Thi d9, d6i v<li dung mOi Ia mKtc H
2
0, Ks (thl,lC
nghim) = 0,51 ; gill tri lf thuyt tinh theo (VIII.16) !A Kg= 0,513.
c) Phip nghifm siJi (hay phi nghifm). Nu g
2
gam 13. lm;mg cMt tan
trong g
1
gam dung mOi thl hn;mg cMt tan trong 1000 gam dung mOi 13.
1000 g2fg
1
va s6 mol chtft tan trong 1000 gam dung rnoi, nic Ia d
molanm2l8.:
g
2
1000
m2=-.--
&t M2
(VIII.17)
M
2
1a kh6i hn;mg phAn tir chit tan. Dua giA tri (Vlll.17) cira m
2
vao
(VlJI.l 5) se dugc :
36
tir d6 :
Mz = Ks 82 . 1000_
gl
(VIII.l8)
(VIII.l8a)
Phuong phap Xlic djnh M
2
dJ!a vao phuang trinh oily bAng each do_d(>
tang diem sOi ATs ella dung dich loiing 13. m(>t iing d1.1ng cita pbep
nghim soi.
CAn hiu Y nhilng h thU'c tren chi dUng lchi khOng c6 SJ! ph!n li hay
lien hqp phan tir ella cMt tan trong dung djch.
2. CAN BANG DUNG DICH LOANG VOl
, -
TINH THE CUA DUNG MOl.
DQ H.o?- BANG DIM CUA DUNG D!CH LOA.NG
1. aq h' bAng dlim cUa dung djch loing
0 lip sufft khi ngdru. P
0
= const, khi li\m dit thffp nhit d
ciia dung dich lOOng thl c6 the t6i dQ bAt tU.u klt tinh (bOO r.ln)
pla dung <ijch rna d6 tinh th.! dAu tien ra, can bhlg v6i dung
djch. Nhit d d6 gQi 18. d bAt dAu d6ng d4c (dOng biing) khi n6
thlfp han nhit di) trong phOng. Khi P
0
= 1,013 bar, n6 gQi Ia nhit d biit
ddu dOng d{ic chua'n.
Kbac v6i cha't lOng nguyen cMt bit d&u va kc!t thllc Sl}' kgt tinh (1
nhit d kMng d6i khi P
0
= const, nhit d kt!t tinh cUa dung djch
thuOng tbay d6i, n6i chung tha'p dlln khi sv kt tinh phat trien va
thuOng tha'p han so vOi dung mOi nguyen cha't (LOmOnOxOp 18. nguUi dliu
tien, b th ki 18, tha'y bang cUa dung djch tha'p hem cua dung
mai nguyen cha't).
37
Khi dung cijch IOO.ng Mt kc!t tinh, nhitng tinh the: hin ra c6 the 18.
ella dung mOi nguyen chfft hoij.c c6 the 18. tinh the: l<!.P hgp (dung dich
r!n) g6m c8. dung moi va chfft tan. d day chi .xit trlltmg ht!P dung djch
cho tOch ra nhiing tinh thl cUa dung mOi nguyen cluft. D6i veri tru'Ong
hgp oily, nhit d bit dliu kl!t tinh hay bang die:m Tb ella dung dich bao
giO cfing tMp h<1n ella duni moi lOng nguyen chlft a cUng lip suA't
ngohl P
0
nhu nhau. Hiu dT b = Tg - T b gQi 18 d() nhit bit d4u
kc!t tinh, hay gQi tAt Ia dq h(l bdng dilm ella dung dich loing (so vai
dung moi nguyen cha't).
C6 tM chllng minh (xem 01. X, 7) rAng cOng thtlc d6i vOi aTb cfing
tuangtqnhud6i v6idT
5
:
R(T
0
)
2
0, 0083 )
2
I
ATb=Kbmzl Kb = b =
. . lOOOA.nc,l Anc,l
(VIII.I9)
Au.c,l = Lnc,tfMt 13. nhit n6ng cMy ritng (d6i v6i 1 gam) CU.a dung
mOi nguyen chfft ; Kb 18. hting stl nghifm lt;mh hay hOng sil hiin
ella dung mOi nguyen chit.. Thi d\1, d6i v6i nuOC, Kb (th\lC nghim) =
1,84, Kb (li thuyt) tinh theo (VIII.I9) Ia 1,86; d6i hOi benzen, Kb thi/C
nghim va li thuylt ta 4,9 va 5,15.
2. Philp nghitm l,nh (hay han nghitm)
Han hay phep I!Jlh Ia phuang pbap thi!C do
dQ bmg difm cila dung djch lOOng. Til d6 c6 thf xac d\flh khO!IIf(Yllg
phdn tri M
2
ella cMt tan trong dung dich. Nlu g
2
Ia s6 gam cMt tan
trong g
1
gam dung moi thi theo (Vill.17) c6 the bifu thj .6.T hnhu sau:
g, 1000
aTb = Kb. m
2
= Kb-. -- (VIII.20)
. 81 M2
ti:rd6:
(VIII.20a)
38
Vl phuong pMp bAn nghim chlnh J<Ac han phuong pMp phi nghim
(pMp nghil}m sOi) n6 dttqe dUng r(lng rii.
D6i v6i dung di.ch lOO.ng, nhUng M thUc tren chi dUng khi khOng c6
sl,l' phan li hay lien hgp phAn tlr cU.a chA't tan trong dung dich.
3. AP SUAT THAM THAU
1. Ap sui't thi'm thi'u. can blng mitng
D6i v6i dung mOi nguyen chAt, nhit dQ 18. T, aip khi
ngoai hie dQllg len n618 P = P., thl lip suA't hdi cUa n61A pf = f(T,P
0
)
va tht! hoi hQC cUa n6 b8.ng :.
= llf (T) + RTJnpf
Nu dung mOi d6 khOng 0 nguyen chAt mil d trong m()t dung
trong d6 ph!n mol cila n6lll x
1
< 1 thi cling vAn trong T,
p khOng d6i nhu tren, ap su!lt hcri cU.a n6 tren
dung dich se tuan theo djnh Raun ne'u
dung <ijch Ill dU.lOO.ng, tUc 18 bi di va bing
Pl =pfxl = pf{l-x
2
}, dod6the'h00hQC
ella dung mOi trong dung dich bang :
1-lt = 1-lf (T) + RT/npl
Nhu 0 T va P ngo3.i khOng d6i, the'
bOO. hQC cUa dung mOi trong dung dich be
han tM hoci hQC ella dung mOi nguyen cM't
mt lugng b!ng :
0
.6.J..L
1
= J..Lf - J..Lt = RT/11 L
Pi
(Vlll.21)
Do d6, nu dung dich va dung mOi
chA't tip xU.c nhau qua ml)t miing
4
h
2
3
Hi11h Vl//-2- Dt,ing C\1 dan
giin df do Ap suit thim th!fu ;
I, dungdich mr6c duOng; 2,
nude nguyen ch(t: 3, mling
ban lhim ; 4, 6ng hc;:p.
39
ban tMm (hlnh VIII-2) thi chua tM c6 can bilng bbi vi tM boa hQC cila
dung mbi a hai ben m8.ng chua b8ng nhau.
Mlng ban tMm (thf dl}. mAng colodion) chi cho dung mOi (nu6c) di qua, cOn chal: tan
(dtrCmg) kh6ng_di qua dugc. Nu6c c6 thi di qua mang ban thfm ti:r ci hai pbia, nhung t6c
dQ' ella ni.R'ic tir blnh ngoii (mr&: nguyen chit) vao blnh trong (dung djch) 16n hem tlr blnh
trong ra blnh ngoAi. Do d6 trong thJ!i: t, ta quan sit duqc ttn;mg II! chuyin ella

gQi 18. tlufm tlufu_ N6 tl! dibl ra theo ti.r dung mOi nguyen chit (c6 the' hoi hQC ).I]
16n) vito dung djch (trong d6 dung m6i c6 thl hOli hQc ).1
1
< J.LiJ
Do c6 S\f lb&n tba:u, mlk dung djch trong 6ng h'"p dang Ito, !fun tang ap sutli: thuj
tinh ella dli.ng djch, do d6 nen mQt Qp sudt Iilm tang t6c d chuyin cac pb!ln tir
ntWc tlr blnh trong ra blnh ngoai, tUc Ia liim cin tri:J dd.n SIJ tbam thi'u. Khi mac dung djch
trong 6ng h"p dllot t&i ditrn A each rntk nll6c lrong blnh ngoru mt d cao h nlo d6 (hlnh
VIII-2) thi 3p suft ph\1 d._t t&i gi3 trj d6 SJ,l' thfun th!u di:rng (t6c dt') chuyl!n clic
phao tlr nuOc ti:r b1nh trong ra blnh ngoai va ti:r b1nb ngOOi vito blnh trong tW thlmh bing
nhau). Nhu tM Ilk can bang duqc thi!t l*p giiia dung djch va dung mOi nguytn chit each
nhau b8ng mt')t milng ban thi'm. Khi d6, gill'a bai dibn M' via M lfy 0 cUng mUc trong
dung djch (dil:m M') via trong dung mOi nguytn cha:t (ditrn M Ja:y 0 tholing ciia
nuOc) c6 ml')t bien lip soft P'- P. Vi lip suit t(l.i Ava M bang nhau va b!ng lip su!t khi
quyl:n ngoW P ntn hi(!u P' - P do bing d() cao h cUa cl')t dung djch, tUc Ill bAng tip sutft
thuj tfnh ella c(ll dung djch d6. N6 bang P'- P = hpg, p Ja kh6i I1111Jlg ritng cUa dung
djch, g Ill gia t6c trQng tru'Ong 0 noi liim tbi nghim. BCri v1 lip suft d6 lAm di:rng SJ! th4m
thfu, n6 can bang v&i &p su4t tMm tiUfu 1t clia dung djch.
Trong th\fC t!, ngtn'ri ta thtri'mg do lip suft thlm tMu bang each do lip suft thuj tinh
d6. V1 th! c6 thl: djoh nghia &p su.ft tMm tMu ltl &p su4t ph!J phdi tdc dr.mg len dung
djch cO n6ng dtJ dii cho dl dung dich cdn bdng vOi dung mOi nguyin cluft cdch nhau
b&ng mtlng bdn tlufm (trong k:i(!o dt') via lip su!t khi quyl:n ngoW khOog
d6i). cling c6 thl! o6i b T = const, mu6n cho dung djch cAn bAng qua milng ban
thi'm v6i. dung mOi nguyen chit clia n6 thlip suit P' llic dl,Ulg Ito dung djch pha.i 16n ban
Ap sult P llic dyng ltn dung mOi m()t b3ng lip suit !ham tMu. Ntu P' < P + 1t, dung mOi
se cbuyio qua nWig ban thain vao dung djcb. Ntu P' > P + x, dung mOi se tir dung djcb
chuytn ra ngoW. NtU P' "'P + x thl c6 can hl\ng (cAn bang nUmg).
2. tjnh lu@it Van HOp v& suit thim thiu
NOm 1886, bilng thl!C nbil bac hQC Hil Lan Van HOp (Van't
Hoff) da tim ra phuang trlnh d6i vCti ap sua:t thftm tMu 1t cila dung
djch lodng:
I n=c
2
RT I
(Vlll.22)
18. n6.ng dQ mol- tich ella chlft n
2
N = g:zf(M
2
V), n
2
18. s6
mol chlft tan trong tich V ella dung <ij.ch, g
2
18. kh6i lugng cMt tan
40

trong the: tich V d6, M
2
ta kh6i hrqng pha.n tit c,Ua cM't tan cOn R 18. hAng
s6 khi. N(u V tinh ra lit, Rp suAt 1t ra atm thl R =0,082l.atm/K..mol.
D!nh Van Hop c6 the: ph!it bieu :
Ap sudt thdm thOu 1r cUa dung djch lming c6 s6' trj bOng lip sut1t mel
s6' mol chdt tan se c6 ne'u n6 a thai khi li tudng chie'm thi tich
bOng thi tich V cUa dung djch vel a cUng nhift T nhu dung djch.
3. Nhift dqng h,rc hqc v8.8p suit thim thiu ,
Tren da n6i 3.p suA't P b dung djch chi c6 the tang nhO xuA't them
mQt Rp sua:t (thi d\1 3.p suA't thuj tinh ella ct dung djch). Khi 3.p sua:t
nay cAn bang vai ap suA't thlirn th6u 1t ella dung djch thl m6i c6 cAn
bAng gilta dung d!ch va dung moi c3.ch nhau bAng mQt. m8.ng b3.n
thffm v8. khi d6 th( bOO. hQC ella dung moi b hai ben m8.ng m6i trb thanb
bAng nhau. Nhu b dung dlch, chi sau khi P tang tU gi8. tri P
0
Mn gia
triP'= P
0
+ 1t thl mai c6 di.ng thUc J.Lf = J.lt
dinb S\1' thuQc ciia Ill vao P, ta dUng h thUc (VII.33) :
(a;\ =VttUcl8.dJ.L
1
=VtdPbT=const
W nguyen tile, v, c6 ph
0
thu(>c vao P nhung rAi it hili vi pba limg la ri!t
kh6 nen, do d6 c6 the cMp n1$l V 1 = const. Khi d6 s\1' tfch phAn se cho :
'
&J.Lt = Vt JdP = 1tV1
0
Ktt hQP vm (VIII.21) duqc:
- 0
1tV1 = RTln.L
PI
(VIII.23)
D6i v6i dung d!ch loiing, p
1
= pf x
1
, tUc 18. (p
1
/ pf) = x
1
, do d6 :
=- RTin.!'L = -RTinx
1
= -RTin(l- x
2
)
Pl'
41
Vl x
2
<< 1 nen -ln(l- x
2
) x
2
va:

- n -
1t V 11:::1 x
2
RT RT n(n
1
VI) n
2
RT
.,
D6i vm dung djch r!t loang, c6 tho! coi giln dUng n, v, bang tho! tfcb
v cua dung djcb, do d6:
nV = n
2
RT, b<>i!c n = ':_; RT = c
2
RT (Vill.24)
D6 chinb Ia phuong Irlnh Van HOp dOi vm ap su!t tMm th!u cita
dung djcb loing.
Ghi clui. D6i v6i. dung djeh Iaing, c6 nbftng lbu(k: tinb h!u nbu chi ph1,1lhu(k: vao stf
IU(fl1g ti/u phan ella cMt tan, kbOng ph1,1lb* vAo ban eMt eila chit nay. Nhilng thu(k:
tfnh nhu lbe' gQi lA lbul)c tfnh thl ctia dung djch (tU chil La Tinh col!igatus = lbi!:,
t$p dotm).
lbul)c tfnh tM etia dung djeh loing g6m c6 dl) hi!- Iuong d6.i ip suit hai eila
dung mOi, dt) tAng dil!:m sOi, dt) h{l bang dii!:m va tip suit th&m thiu ella dung dich Iaing:
dpl_ M1
---m2 .1.T
5
=Ksm2
pj 1000

B6n thul)c tfnb d6 ti vO'i nhau vAtU thul)e tinh nAy c6thi!: suy ra thuc tfnb kia.
MOi mQt trong nhilng thu(le tlnh iy c6 the diing di!: xie djnh kh6I luc;mg pha.n tir
eUa chit tan.
4. cAN BANG DUNG D!CH LOANG VOl
DUNG D!CH LOANG C6 MQT CAU Tlt CHUNG.
l!NH T PHAN BO. Sl,l CHIET
1. Djnh lu;t ph in bO dan giin
Gill thlr hai cha't lOng 1 va 2 kh6ng boa tan vao nhau chi bOO. tan
ra't it, kh6ng dang kt. Them vAo M d6 ml)t nhO ca'u tir th(r ba (rAn
lOng) tan daqc rieng re trong c8. hai lOng 1 va 2. Sau lchi Iac
42
slJ boil tan dugc nhanh chOng r6i de yen cho can bAng duqc
b T, p const thi se h1nh thanh hai 16p mOng. Mbi 16p 1.8 m()t
dung cijch loing ca-u tir thU ba mil dung mOi 13. cMt lOng 1 a 16p nay va
cMt 2 a 16p kia. Hai pha lOng d6 can b8ng v& nhau, lOp c6 ti kh6i
be han thi n6i Itn tren.
cAn b8ng lit ho3 hQC ciia ca:u tir thU ba hai pha (') va
(") phili bang nhau : = Khi chi boa tan nhiing IUQilg nho ch!t d6
duqc nhiing dung djch Ieang thl cMt tan (ciu tir 3) tuan theo dinh
Henry vil th boa hQC ciJa n6 trong dung djch Joang c6 (VIll.l2).
can hilng lil:
(T, p) + RTinX' = .. (f, p) + RTinx"
tir d6 :
' 0" 0'
In!_= (T,p)- (f,p) = (T p)
x" RT 'I' '
(Vill.25)
aT, p const, hrqng d618. m()t hAng sO va :
x'
- = f(T, p) = const
x"
.
(VIll.26)
dung dfch Ia dU lOOng thi n6ng d pMn mol x -ti 1 v& n6ng d
mol- tich c. Khi <f6,0T, pconst:
B
(VIII.27)
Nhiing phUQilg trlnh (VIII.26) vil (VIII.27) Ia th<ic djnh !UQilg
ciia djnh phdn b6, thtWng gQi Ia djnh phdn bd Necxu (Nemst,
1891). th\fC ra, <4flg (VIII.27) dii duqc Becta!O (Berthelot) vil
Junglaisa (Jungfleisch) thn ra tlr 1872 khi nghitn ciin sq phan b6 iOt 1
2
giOa nu6c va m()t dung moi hUu ca khOng tan trong n..WC.
Hlng s6 K gQi 18. stf phdn 0 T, p const, n6 chi ph\1 thu()c vao
ban cMt ciia chAt tan vacUa cAc dung moi, khOng ph\1 thuc vao hrqng
ciia chOng. Trong thlJC K ph\1 thuc chU ylu vao T, nft it v8.o p. Do d6
djnh pban b6 c6 the plu\t bilu :
43
0 nhift d9 khOng ddi, ti stl 'nong d9 cUa cdu tU thii ba trong hai pha
lOng cdn bJng Ia ff0t dt;li luqng kMng dtli, khOng thu9c vdo-lllt;mg
dlli hay tlldng d6i cUa cUe cdu tU, khi dung dfch lei dU IOting.
C6 chttng minh ring s6 phdn b6 K bJng tt sci d9 tan riing re
cUa cdu tU thii ba trong hai cluit lOng 1 va 2 khi nhilng d9 tan dO Ia be :
= (c ') biio boil = = K (Vll.ZS)
c" (c") bilo boa sz
s
1
ta d tan ci:Ja ca:u tit thU ba trong cMt lOng 1 va s
2
ta d tan ci:Ja n6
trong cbA:t lOng 2 a clmg nhit d, d tan ta n6ng d cbA:t tan trong dung
dich bOO bOO. cbA:t d6 (dung dicb toy bio bOO. nhung van ra:t loing).
Djnh phOn b6 don giim (VIII.26) hay (Vll.27) chi ap dung
cbo nhUng phAn tir ci:Ja cMt tan c6 d IOn nhu nhau U ci hai pba lOng.
2. Jjnh luijlt phin b6 t6ng quat. Khi pbAn tU chtrt tan c6 dt') 16n trung
blnh khk nbau a hai pha lOng, do nhiing tUQD.g pb!o li hay lito hqp pb!o tlr gAy ra
thl lA phlli. tbay n6ng dt') trong (Vlll.26) vA (VIII.27) bAng hmp dt) (khW nim nAy
se nghitn cll'u a Ch.X), hol!-c nu gi.ii' n6ng dl) thl thtm nhitng h s6 nilo d6 phin 3nh
mil'\! dQ nhiing qua trlnh pbAn li bay lito hqp ph!n tir vA xac djnh trong mOi truCmg hgp
bing thl,l'c nghim. Khi d6 djnh fugt phOn btf U dt;mg tdng qudt c6 thi biiu thj b!ng
phuong trlnh :
(c')n
--=const=K
, ..
(VIII.29)
(VIII.29) gQi lA djnh lu4t phdn b6 Necxn -SifOp. Gi3 trj ella n c6 thi b!ng kh!ic s6
ngoytn; n6 b!ng n = M"/M', a dAy M' va M" Ill kh6i lm;tng pb!o tlr trung blnh ella chift
tan trong ph a lOng thU nh& (') vA thU hai. (").
Nu n > I, cha:t tan c6 kh6i tm;mg ph!n tU trung blnh a pha (") 16n bon a pba ('),
bit nu 0 pha (')n6 c6 phan tir blnh thubng don phAn, monome) thl trong pha (")
n6 pb.W c6 ph!n tU lito bgp. TrW ntu n < 1. thl M" < M' vil nl!o 0 pha (') ph!n tir c6
16n blnh thubng thll:J pha (") rt6 phW. ph!o li..
l>l!-c bit, nl!n trong dung I. cha:t tan c6 ph!n tir binh thuCmg, cOn trong dung mOi.
2, n6 t6n chU yu, gUt 100% dtWi dli-Og ph!n tUkepdOi. (lufmg ph!n, dime) c6dl'> 16n
ga:p dOi thl djnh lu*t phAn b6 bieu thi b3ng plnwng trlnh :
(c')2
--= K (VIII.30)
c"
Phuong trlnh nAy da thi,IC nghim xik nh;)n d6i. v6i Slf ph!n b6 axit benzoic
trong nU{jc vil trong Ill dung mOi hihl ca ooi nbu khOng tan trong nu6c. Axil
benzoic tan trong nu& chii y5u a dll-fig ph!n tir dcm ph!n (monome) thl!c ra
44
n6 c6 phAn li ph4n nhung sJ! phAn li nAy lA y6u, ta bO qua. Trong benzen thl n6 lien
bgp, cbU y(u 0 IuOng phAn (dime} !lay pbAn tU ktp d6i ({t;HsOOOH>:z, chi c6 mQt ti
nh6 dcm PJ,An t do (#lsCXXJH. Gqi c' lA n6ng axit benzoic trong nu& vlt c" Ill
ndng axit benzoic trong benzen thl c' yl c" thoi min p.tr. (Vill.30).
Khi khOng c6 bi11 phAn li hay lien hgp phAn tU thl n "' l vl (Vill.29) tr(t
dcm gihl (Vll.27).
Nhung vl thU'Ong khOng bitt trut'ic duQc lA c6 bay khOng c6 ttrgng pbAn li hay
lien bgp phAn tU cho nen, trong truimg hgp chung, ta cln sir d1p1g djnb II$ pbAn M 0
tdng (Vill.29) vA ti61 bAnb do bAng thlfC nghim diy giA tri ndng dl) c' va
c" cUa cb!t tan trong bai pba lOng (vl loing) l1 cUng (vl nguyen tic 2 giB trj clia
c' va 2 gia trj twng Ung ella c" lA dU). Sau d6, tir (Vll.29) suy ra :
Jgc""" nlgc'- lgK (Vll.31)
Bil!u thlk nAy lA m(lt pbiWilg trlnb duimg thing. C6 nghia lA n(u tir thi,I'C ngbim xly
di!Jlg d6 thj lgc" = f(lgc') se dugc ml)t dll'img thing c6 s6 g6c bAng n cOn tung dQ gtJc
bAog-lgK.
3. M9t ll'ng cUa djnh ph in bO: Sl/ chii"t
Tir dinh phan b6 suy ra m(lt phmmg pbap nit m(lt cMt tan ra kbOi
m(lt dung moi nhb' them v8.o d6 m(lt dung mOi thU hai khon8: tan trong
dung mOi nMt nhung holt tan dugc cMt klulo sat. Phuong pMp nay
gQi Ia chiel. NguOi ta diing n6 1M 1xlt philo vo feb 1>$
1M I!y ra iJ <4ng giau han pMo c6 ich olto d6 cila dung. djch.
Dung mOi chi!t cln chqn sao cho SJ! chi!i duc;Jc nhanh nMt, hiu qui
nMt v8. it t6n N6 ph8.i khOng tan h* chi tan dt it v8.o dung mOi
cUa dung djch c&n chi!t va phlli c6 M s6 phan b6 dmg cao c8ng t6t d6i
v6i dung mOi nay. Ete etylic va m(lt s6 dung moi hUu. ca kluic (CC4,
CSz, c,;H,; v.v ... ) thulmg dap oog t6t nhiing yeu du d6 khi din
htiu cOra khOi dung dich nuOc.
Sau khi di chQn dung mOi chi!t r6i thl each ti!n h8.nh sJ! chi!t ding
quan trQng. D6i v6i cUng m(lt hn;mg dung mOi chi!t da cho, hiu
chi!t se dugc n!ng cao han n!u ti!n h8.nh SJ! chi!t bAng tirng lm;m.g nhO
m(lt, chlt khong nen di:mg toan b(l trong m(lt l&n chi!t duy
De don gia\n, ta gilt tbi(t cac tiE:u phAn cila chft tan c6 dQ lmt gi6ng nbau kbi tan
trong bai dung moi vA cic ciu tU cila b khOng c6 tiWllg tac hoi bQC v6i nbau.
Gii thU c6 VA lit dung djcb chUa&. gam cbft i trong dung mOi A vA c4n cbiet cbft i
ra kbOi dung djcb d6. Them vAo d6 V
8
lit dung moi B holt tan dugc i nbung khOng tan
vio trong dung mOi A. Gqi g
1
lA luvng cb!t i cOn I. trong VA 1ft dung djcb d4u. Ndng
cUa i trong dung djch nAy, tlnh ra gam/1ft lA:
45
Di nhitn, lm;mg ch.ft i phlin M trong Va 1ft dung moi B Ja g
0
- g
1
Do d6 n6ng dl)
(gam/lit) cila i trong pha lOng nay lA:
CB=&-gl
' v.
GQi K Ia h s6 ph:ln b6 ch.ft i giiia hai pha lOng A va B. Theo djnh l u ~ pban b6, &
T::: cons(:
tir d6 :
(VIII.32)
D6 Ia IUQng cMt cbift i cOn I ~ troog VA lit dwtg djch d4u sau Mn chilt tM nh!t.
Tach rieng VA lit dwtg d!ch d6 (chUa g
1
gam ch& i) ra khOi lOp dung djch B (nh(1 dUng
phtu cbilt c6 kho3). Bay gii'Y xu.ft phat tU dung djch VA nay, ta tifn barth S\1' chilt Uln tM
bai, ciing dUng Va lit dung mOi nguyen cMt B bing dUng !!in tru&:. Vl b s6 ph:ln b6 K
kb{)ng dOi cbo nen IUQng g
2
gam ch!l't i cOn I ~ trong VA 1ft dwtg djch sau Mn cbilt thU
hai nay bAng :
(VIII.33)
Trong trui'Yng hgp chong, sau n !!in cbilt, lfn nAo ciing bAng mQt hrqng kbOng dOi VB
ella dung m{)i B nguyen eMt tac d\lllg v& lugng VA dung djch tach ritng sau mOi lin
chilt, thliUQng in gam ch!l't i cOn s6t I ~ trong dwtg djch A se Ill :
(VIIL34)
Tit d6 suy ra luqng cMi dii chitl: ra dUQC sau n 14n chilt :
g;=g,- .. = .. [ ~ - ( KVA J]
KVA+Vs
(VIII.35}
46 http://hhud.tvu.edu.vn
CHOONGIX
DUNG DICH LfTIJONG VA DUNG DICH THIJC
. . .
1. l!NH NGHTA VA THUQC TINH
CUA DUNG D!CH Li TUONG
1. Nhltng d.ch khilc nhau djnh nghTa dung djch 1i tllhng
a) Djnh nghfa dung djch li tudng theo 3 tieu chuiln.
0 chlWng VII, 5, ta d1i djnh nghia dung djch li tuOng (hay ho3n
chlnh) 13. dung d!ch thoit min 3 kin (hay tieu chudn) sau b mQi
thi!.nh ph:!n :
1) v = l:nivf: 2) u = :Eniur: 3) s = :EndSf- Rlnxi>
Ba kin d6 d!n tm :
V. -v U -u H -H
0
-c -C
0
c. -s Rlnx
I- j I- i I- i Pi- p,l '"'1.- i - i
Gi = Gf + RT/nxi ; 1-li = Gi = Jlf (T,p} + RT/nxi. v.v ...
.
b) Djnh nghla dung djch li tudng theo tieu chuiln duy nhilt vi the' hod
hr;x:. C6 the si'r dt,mg tieu chuAn duy nhAt thl bQa hQC djnh nghia
dung dlch li tuOng nlur sau :
Dung djch li tudng (hotln chinh) Iii dung djch trong d6 the' hoG hqc Pi
cUa m(jt cdu til i Mt ki nghifm dUng hf thilc sau U m(Ji xi :
I lli = Jlf (T,p) + RT/pxi j . (IX.l)
C6 tM chllng minh rAng mQt ca"u n"r i nao d6 tho! mi!n (IX. I) a
mQi xi thi W ci c8.c clfu tir klu\c trong dung <ijch bAt buQc cDng pb;li thoi
mi!n (IX. I) a ffi9i thi!.nh ph:!n. Nhu dilu du dl clw miJtdung
djch Ia If tudng 13. hot hQC cU.a mt c(u tir i n3.o d6 ddng
(IX.l} lJ IDQi Xj.
47
IJ6i vm dung djch iJ tri!D!l thai ngung (long cln), imh huimg
cila lip sulft vao holi hQC kbOng gi6ng nhu d6i vOi khl : imh huiJng d6
be han D6i vm i trong dung djch long h$ rAn, holi hQC f'; va
do d6 s6 h<J.Ilg (T, p) phy. thut>c chU yl!u .vao T, rAt ft vao p, -do d6
trong sv gin dling thu nMt, c6 th<! bO qua imh huiJng cila lip sulft
Tir (IX.l), c6 thi suy ra lllQi thuc tfnh khac cUa dung djcb li tu<mg. Thf d1,1, vl
RTlnX; khOng phy. thuc vao p nen tir{IX.l) suy ra:

Nhung '<4af /ilp}r "'(aGifOp>-r = Vf = the tich mol cUa i nguytn chat va theo
(VII.33) (8J118p).y- = V; = tht tfcb mol rieng ph<in ciia i trong dung djcb. v._y V; =Vi,
AVM = rtl; .6. V; = :En; ('V; - vj) = 0, v.v ..
c) Djnh ngh'ia dung d_ich li tuOng theo quan dilm phdn tli. Theo
nhiing quan th6ng ke, dung <ijch lOng r&n) se 18. lf tuCm.g,
nghia 18 thl! hoB. hQC J.li se thoA miin (IX.l) veri. mQi x, khi tuong tac giila
c3.c pMn tir cUng c4Jlg va khlic dl;lllg ella cac ca:u tir deu bAng nhau a
kMp mQi dii!m trong dung dich, trtc 18. khi ta:t ci cac pha.n ttr dtu c6
-trubng llf'C nhp nhau. Till dy., d6i vai dung djch 2 ca:u tir A va B. nang
lUQDg tuang tac E giiia clic phAn tir cU.ng dl;lllg va kluic phc\i boan
toAn gi6ng nhau, EA-A = Es-B = EA-B
N6i cMt cbe th'l kbOng m(lt dung dich thi,Ic nil.o c6 chfnh xlic nhUng thu(lc tfnh ella
dung djch u tulmg, rna chi c6 thi d!!.t gb. t6i dic!u If tulmg (J mac d(l nil.o d6. NhUng
dung djch lt'mg dt kh;i. t6t dic!u lf ttrOng la nhDng dung dich mil clc ctru tir ella n6
c6 ctru pha.n tir va nbfrng thuQc tlnb I{ va ho;i hQC gi6ng nbau ho dt gb. nhau.

l) h6n bqp nbilng d6ng phln quang hQC ;
2) dung djch nhltng tircbi kb;ic nhau vc! thlmh phb. d6ng vj. nhu +
3) dUng dich nbitng cMt d6ng ding q.nh nhau nbu benzen + toluen, hexan + heptan,
dibromopropan + dibromoetan v. \1
d) Dinh nghfa dung djch li tudng theo djnh lupt Raun. D6i vai dung
djch lOng li tllcfng, vi ta:t ell c3.c phAn ri':r diu c6 tn.tem.g lt,tc nhu nhau cho
tinh cba:t ella m6i phan til trong dung dich li tubng khOng thu(lc
vao n6 duqc phan b6 giUa nhfing pha.n til nao. Vi khll nang ella
phan til i trong tit dung dlch li tui:mg sang pha hai phili
gi6ng nhu khi clfu tir i 0 thAi lOng nguyen chlft (0 cilng T va p
48
ngoAi nhlt nhau). Khii niing d6 chi ph1,1 thu<)c vao h.rqng tlWllg d6i ciia i
trong pha lOng. Do d6, _st;r i tir dung djch sang hai, do 1Xri. lip
fi ella n6, se cang lCm. d chUa tuong d6i ella i trong pha lOng dmg
16n, tiic 18. fi ella i trong hoi pMi ti 1 v6i. n6ng d ph!n mol Xj ella i trong
dung djch lOng, nghla 18. fi kjXj, 18. h s6 ti 1. H thiic nay phiii dUng
v6i. mQi xi, ke cii xi= 1 (ctfu tlr i nguyen cha:t). Tir d6 soy ra gili trj ella h
s6tilk= ft' va:
(IX.2)
D6 ta bieu thUc c_iia djnh IU<;it Raun tbng quat (doi khi cfing gQi 18.
d!nh Raun - Henry t6ng qulit hqp nhtft).
Nhu c6 the dlnh nghia dung dich lOng li tudng ld dung dfch mtl
m()t cdu tti i bdt ki cUa nO tudn theo trift di d_inh lu{l.t Raun ufng qutit U
m(Ji n6ng dQ.
Chi dn mt ca:u tir i nao d6 tua.n theo trit dt! djnh Raun l:J mQi
n6ng d 18. dll dt! cho dung d!ch 1a H tuimg bdi vi c6 the chiing minh r8ng
khi d6 clic ca:u tir kh3.c ella dung djch bAt buc cling phiii tua.n theo trit
de dinh Ratio l:J mQi thanh ph!n (xem 3).
2. Ap suit heli bio hoacua dung dfeh lOng n tUdng
Giii thir bOn hQll hai cha:t lOng 1 va 2 18. dung d!ch lOng H tubng.
Trong truCm.g hqp chong, gi8 thit!t cii hai ctfu tlr bay hoi. Nt!u 8.p sutft
hoi ella chUng 18. dll be de pha hoi ca.n b8ng v6i. dung dich c6 the coi 18.
bOn hgp khi li tulmg thl khi d6 lip trlmg v6i. ap suift ritng pMn,
ft = Pt va f
2
= Pz D6i v6i. dung djch lOng H tubng, nhilng lip sutft ritng
pMn nay phii. tua.n theo trit dt! dioh Raun b mQi n6ng d :
(IX.3)
(IX.4)
p
1
va P:z ta h8.m nhtftciia thanh ph&l ciia dung djch
lOng, bieu thi b!ng phAn mol x
2
ella ctfu tir 2. DuOng bieu dien ciia
49
p',
chUng trong giin dO B.p smt -
T=const
thanb ella dung lOng
p' (hlnh IX -I) Ia nhiing duimg

2
thing. do d6 ve nguyen tAc chi
clin duac. xlic di. nh biri 2 Ia
0,5
----- x (benzen)
1
(benzen)
dU, thi d1,1 d6i v6i x
2
= 0 (cAn tlr 1
nguyen chlt) va xz = 1 (ca'u tlr 2
nguyen chAt).
Ap su!t hoi toan phiin ella
dung djch bAng :
P=Pt+Pz=
Hiflh /lf.J. S., ph1.1 thu<: lip suft hoi rieng
phln va lOOn pbAo vao thMh phfn
dung dich lOng li tubng
P = Pr + - Pr> xz <IX.s>
lip su!t hoi toan phlin ella
dung djch lOng li tOOng cfing lit ham nha:t ciia x
2
va ciing thj.
bAng rnQtdulmg thing (hlnh IX-I).
2, DUNG D!CH THI,fC. SAl DUONG VA AM
SO VCJI OJNH RAUN
1. Sai dlfdng va im so vOI djnh lu;t Raun
D6i vdi dung dich thl!C (khOng If tubng), lip su4"t hai rieng phltn p
hoi Ia li tuimg) h"'!t lip f; hoi Ia khOng li IuOng) c6 nhiing
gili tri Ian han (sai lch duong) be han (sai lch dm) so vOi nhiing
gia trj tlnh theo djnh Raun.
a) Hinh IX-2 trlnh hily nhiing duimg ding (dulmg cong net
bien dic!n Sl,l pb1} thuc cip SUA't hoi ritng pMn vi toAn plcln Vfto
thanh. phln cila dung dich benzen-axeton 18 mt trong nhDng c6 sai
50
duung lip sua't hcri so vai dj.nh Raun. Nhfing duOng tbAng
Ung vOi trUOng hgp nu dung d!ch ta li tu(mg.
CluJ y r-Rng phia ben tr<ii
giim d6 Ia vimg dung dich
loing axeton trong benzen.
0 day, d6i vOi Xaxeton be,
benzen d6ng vai trO 18. dung
c:
mOi c6 ap sua't hcri PI UlAn
'
theo djnh Raun trtn ml)t
khuc du<mg nhi> (pUn
1
250
200
150
100
50
0
_/-.
[.?
0 0,2
1=25"C
..-
..
4
,....

v ..

...
........

0,4 0,6 0,8 1,0
dUOng cong lip sua't hoi PI CsHs (CH
3
)
2
CO
cila benzen trling vOi dUOng
thilng chain chain) (hlnh
IX-3), cOn axeton Ia cha't
tan, ap sua't hoi P2 ella 06
_,,
Hlnh IX-2. Ap su!'t hai trong M benzen -
axeton (sai 1ch dlWII.g)
tua.n theo djnh Henry, P2 = Paxeton = kxaxeton (dtWng cong lip sua't
hoi P:2 cila axeton b d6 Hl m()t khl1c duOng thing).
0 phfa phoii giim d6 p
Cilng c6 ml)t vllng dung t
dich loang benzen trong 1
axeton. 0 day d6i v6i
nhiing n6ng be cila
benzen (xi < 0,1) axeton
d6ng vai trO 18. dung moi,
.
vClng djnh luQt
Raun
8.p su6t hoi P2 cUa n6 tuAn
theo djnh Raun (pMn
duOng cong P2 cUa axeton
trU.ng vCii duOng thing
chilin chffm) cOn benzen
d6ng vai trO Ia cMt tan, 8.p
sua't hoi p
1
cUa n6 tuAn
theo djnh Henry.
. :.< vilng dinh '' /.
Henry
Hinh IX-3. minh vUng dinh lu*t Raun
vi\ viing djnh Henry trong h
benzen- axeton (sai dlWII.g)
51

4{)0
300
t=1rc
........

.
E 200
E
/
.
.

'/
<i
1
100
0
.

p;o:
K .. ;:,
..
..
..
0 0,2 0,4 0,6 0,8 1,0
- x,
Hi11h /X-4. A.p sui't hcri trong M clorofoc-ete
etylic (sai Am)

E
E
<i
I
t=29,2"C
600
IIT::::+:::::II
soo f--+-?"F-v---1--f'>.--1
/ '\
400
300 I

----- .
/ ..
......
200
I
. ...._
... .. ...
100 ....
(/ .. .\1
o o"'-:-'---,--L-,-L-,-L..:." .,.
0,2 0,4 0,6 0,8 1,0
(CH,),CO cs
2
"cs,
-
Hi11h /X-5. Ap suat hcri trong axeton-cacboo
sunfua (sai duong c6 C1fC
52
D6i v6i nhtlng M c6 sai
lch duang, a nhilng vimg
dung cijch lOOng, lip sullt hcti
clia cMt tan IOn han so v(ri ap
sullt tfnh nt!u dung cijch 13. li
tuimg (k >
b) Hinh IX-4 trlnh bay
giin d6 lip sullt hcri. - thB.nh
phful d6i v6i h clorofoc--ete
etylic Ia c6 sai /fch dm so
v6i d!flh Raun. Nhnng vUng
dung dich loiing la kM ro d6i
v6i xrna3 < 0,05 va d6i vOi
"ere< 0.1. o nhilng vi1ng d6, ap
sullt hcri. ctia chllt tan be han
so v6i dung djch If tuimg
(k < P3).
c) C6 nhtlng h rna sv sai
lch so vbi dWt Raun 18.
dU Ian, tam cho duUng cong
lip sua"t hcri. tOOn phful c6 cifC
d(li (hlnh IX-5, h axeton -
cacbon sunfua) cl{c tilu
(hinh IX-6, haxetrn -clorofoc).
Ap sullt hcJi bao ho8 ella
nhtlng c4u ti'r lOng nguyen ch4t
rna cang gl!n nhau (11 dmg
dQ) thi nhilng sai nho vt
phia duang ciing nhu am so
v6i dinh Raun 13. da c6 thf
tam xullt hin cl[C <4i ho4c
cgc titu tren dt.rtm.g bitu dif!n
lip sullt hcri. to8n ph&t clia M
theo th8nh phful cUa dung' cijch.
d) Nhiing dung djch c6
!iai ductng ve ap sulft
hoi thuCmg hdp thl!-
khi chllng dltQC hlnh th:lnh
tU nhiing dlu tir nguyen
cha:t, n6i each kM.c, nhit
hlnh tbanh dung djch c6
dA"u dttcmg (theo quy tWc
ve d{(u trong nhit dQng
h!C hqc). Tr8.i l'}i, d6i v6i
dung djch c6 sai lfch dm,
nhit hinh thlmh dung dich
thuOng c6 da'u ilm, t\k Ia
S\f hlnh thlmh dung dich
nay tod nhift. N6i chong,
dA"u cUa sai lch so vdi
djnh Raun va da:u ella
nhit hlnh dung djch
thudng trUng nhau.
200
l
50
0
0
(CH
3
)
2
CO
0,2 0,4
0,6
0,8 1,0
CHCIJ
Hinh lX--6. Ap suM hai trong h axeton-clorofoc
(sai lch :l.m c6 c\fe ti6u)
2. Nguyen nhin. N6u nhitng phan tlr Ava B trong dung djeh hUt nhau v&i life ye"u
han hre hUt giila nhitng ph an tlr A v&i nhau B vtri nhau thl di nhien ehling ri:ri. 00 pha
lOng dC chuy6n thilnh hai nrang d6i de dilng han vffi nhitng ea:u tlr lOng nguyen ehlft,
do d6 gil.y ra nhiing sai leh duang vt lip sua:t hoi so v& djnh lul).t Raun. TruOng hQp d6
thuOng gi;lp khi e6 S\1" kh3.e nhau ro lip suilt n()i vf tinh ph!ln qrc ella hai ciiu tlr
lOng, thi dl). nhu khi boil tan mt ch:lt e6 C\fc v3.o m1 dung mOi khOng elfe (truCmg hap
axeton trong CSz). V1 su rOi xa nhau ella nhitng ph;ln tlr A ho\le B trong qua trinh hl.nh
thilnh dung djeh dOi h6i ph8.i titu thl!- nang lul!llg tir ngoili du6i d;.tng nhi1 eho ntn dung
djeh c6 sai Iech duang thuCmg Mp thl!- nhit. Ngo!li ra, nt"u khOng c6 nhitng y6u t6 kink
Jam phUe l;.tp them thl S\1" hl.nh thlmh io.p dung djch d6 c6 thC c6 kern slf tiing till ticlz do
chO c;ic ph:ln ttl 6 xa nhau han v6i khi chUng b trong clic du tit lOng nguyen chiit (tuy
nhifn, dieu nay chua th3.nh mt quy tic rO rt).
Neu nhifng pM.n tlr A va B trong dung djch hUt nhau v6i nhUng llfC h<111li!C hUt
giUa A v6i A ho\lc giila B v6i B trong diu tlr 16ng nguyen chlft thl kba. nang chuyn
chUng tlr dung djch lOng len pha hoi se gi:im di, do d6 c6 sai dm ve lip suiit hoi so
v6i djnh Raun. Slf gin nhau bOll cUa c3c ph :in tU trong dung d!ch gi3.i ph6ng nii.ng
53
hn;mg tOa ra ngoili d!J6i nhi1, do d6 nbi1 hlnh thAnh dung djch nily thmlng c6
dlfu am (tod 11lu"t). Trong m!)t s6 tntOng hgp, tllCmg tac hUt giila c3c c!'u tli c6 thi din tai.
nbiing qwi trlnh hoi hQC (sonvat bOO, hlnh thilnh litn k(t hidro, hinh thilnh hgp chat bOO
hQC v.v ... ). Nbiing tnrOng hgp nily lit xiy ra trong nhiing he mil eli hai cA"u tli !Mu c6 ClfC,
thi d1,1 axeton va clorofoc c6 the hlnh thimb lien k!t hidro giita chllng v6i nbau vil tl,lO nen
plu'i'c hgp a3CH ... OC(CH3)2. Trong nhiing h nhll V*Y SJ! hlnh thilnh dung djch thltOng
toi ra nhifu nhi1 vii ip suA"t hcri c6 sai 1ch am so vm. djnh lu*t Raun.
CAn Juu Y Iii nhiing y(u t6 g!ly ra sai lch di.WII.g va am c6 thi llic d1,1ng d6ng thM
trong dung djch, do d6 nhilng sai lch quan sat d11gc thltOng Ill k!t qua tO hgp nhiing sai
1ch m!lu thuAn nhau vt dA"u.
3. He THCfC OUHEM- MACGULEXO (Margules)
1. Thi&t l'p h thUc EJuhem - Macgulexo
Theo thUc Gipxo - Duhem, d6i v6i dung djch lOng hai tir 1 va
2, b T, p const, ta c6 :
(IX.6)
Vl th.! bOO. hQC ella cac ti'r trong dung dich lOng chi thay d6i dt it
theo bi.!n thien ella ap chung c6 3.p dt,mg (IX.6) b T = const
d6i v6i toAn 1>(1 diy thanh pMn ella rna khOng dn pluli ke t6i 8nh
hubng cUa ap suA't chung, Ia giUa ap suAt hcri rieng pMn ella
hai ti:r pluli khOng quft IOn.
can bAng giUa dung dich lOng va hcri bao bOO. ella n6 18. :
).! = = ).!f = llf (T) + RTlnfi
(L pha long. K pha khi (hoi)). Do d6 thi'n ding cua
th6 ho8. hQC c6 :
dJ.li = RTdlnfi (T = const)
Sau khi 00 s6 hl;l11g RT = const, (IX.6) trCJ thanh :
(T = const) (IX.7)
tit d6:
54
(T = const) (IX. B)
(IX. 7) c6 thi vilt :
Xt + xz dfz = 0
ft f2
(T = const)
(IX.9)
Chia hai v v6i dxl va nh6' rRng dxl = --dxz (vi d6i v6i dung djch 2
tfr, Xt + Xz = 1) se duqc:

df
1
= x
2
df
2
f
1
dx
1
f
2
dx
2
dftf dxt = dfz/ dxz (T = const)
ftlxt fz/xz
(IX.IO)
Nhiing h thUc tir (IX.7) dn (IX.lO) dtu gQi 13. h thitc Duhem -
Macgulexu, ta mQt bin clich ella thUc Gipxa- Duhem (IX.6) d6i vOi
dung djch lOng hai clfu tlr. N6 cho SJ! lien M dan giim giUa ho{l.t cip rieng
phtln ella hai cA"u tir d6i v6i cac thanh phAn khac nhau ella dung dich
lOng d T = const. thl'rc Duhem - Macgulexo thuCrn.g duqc dUng khi
pha hai ella dung dich c6 the coi Ia bOn hqp khf If tuCmg. Khi d6 f
1
= p
1
,
f
2
= Pz va M thUc Duhem- Macgulexo se c6 nhiing :
x
1
dlnp
1
+ x
2
dLnP2 = 0 (T = const) (IX.7a)
dlnrz =- dlnp
1
(T =canst) (IX.8a)
x2
XI dpl + Xz dpz =0
(T = const) (!X.9a)
PI P2
dp
1
/dx
1
=
dp
2
/dxz
(T= canst) (!X. lOa)
Ptf Xt pzlxz
55
2. Ap d&,rng h' thLR:: E>uhem - Macgulexa cho dung djch If tt.rdng
a) Nh&c vlphlllhlg trinh bf}c nhtlt, y =ax. hfun ella n6Iii:
dy/dx = a, nhlDlg y/x = a, dy/dx = y/x. D6 Ia phuang ttinh dubng
thing di qua g6c tQa d.
b) Ap dl}ng. Nhll duqc bil!t, d6i v6i dung d!ch lOng 1i tllimg, duUng
bitiu ditn p
1
theo thiinh phcin dung Iii mt)t duOng thing di qua g6c
d, tll'c Iii dp
1
/dx I = p
1
/x
1
Khi X
1
= 1 ( ca'u tir 1 nguyen cMt) thl Pt = pf
dod6:
dp1 _ Pt pf
---=-
dxl x
1
1
tit d6 p
1
= pfxt, d6 cbinh 1ii djnh Raun. Khi h thll'c niiy dlt<JC
nghim dUng v6"i mQi x
1
( duOng bi6u dien Ht duOng thing) thi thea h
thdc Duhem- Macgu1exa (IX. lOa), Mt buc ding phiii c6:

dx
2
x
2
1
tiic Iii P2 = p3x2. Chi can mt ca'u tirnghim Raun bmQi
ndng d Iii ca'u tir tbli hai ding pbai tua.n thea djnb Raun b mQi
n6ng dt).
4.l!NH KONOVALOP (1881).
SO SANH THANH PHAN HOI VCII
THANH PHAN DUNG D!CH LONG
1. Quan h' gilla ap suat hefi bio hoil va dQ sCi cUa chat lOng
Trb ll;li binh VIII-1, ta tMy rAng trong cac cha't lOng dem so sB.nh v6i
nhau (nguyen cha't ciing nhu bOn hqp), cba't lOng niio c6 3.p sua't hai baa
boA cao nha:"t 0 cilng nhit d, cMt lOng d6 se c6 nhit d sOi tba'p nha't.
56
D6i v6i dung djch lOng 2 ca:u tlr, <ip sua:t hoi toan phin ella n6
thu(?c vao th8nh phan ella dung djch, do d6 nhit dQ sOi ding 18. bam ella
thanh ph<in. Khi <ip sullt hoi di qua cJ!C diP ml)t thanh phan xac djnh
nao d6 th'i. d6i v6i th8.nh ph!tn nAy, d(} sCi ella dung dlch di qua CJ!C
titu. Nguqc l<)i, khi dung djch c6 ap sua:t hoi toan phAn CJ!C titu th'i. nhit
de) sOi ella n6 phiii Cl,IC d;;ti.
2. 51! khiic nhau gili'a thilnh phan cUa dung djch lOng va thinh
ph4n hefi bio hoa cUa n6. D!nh lu-'t KOnOvaiOp
a) Pha lOng Ia dung djch li tudng. Pha hui ld hJn hlfp khi li tudng.
GQi x
1
va x2 18. ph<in mol ella cllu tlr l va 2 trong dung djch lOng, y
1
va
y
2
Ia ph<in mol ella chllng trong pha hoi can bAng v6i dung d!ch lOng a
T = const, p
1
va P2la ap sullt hoi rieng phin cii.a chOng trong pha hoi. Ap
sullt hoi toan ph&n cUa dung djch Ia p = p
1
+ P2 Ta co, d6i v6i pha hoi :
khlic, vi dung djch lOng Iali tJJCm.g, nen c6 dinh lui).t Raun:
dodO:
0
11_ = 1. = P2x2 boac=
0 .
Yt PI PJXJ
H thUc nay cho thlly :
0
PI
(IX.ll)
1) N6u p = p f thl y
2
/y
1
= x
2
/x
1
, nghia 18. d6i vCti dung dlch 1i tubng
.ella 2 chllt lOng I va 2 chi khi nao <ip sullt hO'i biio bOO ci:Ja chUng 0 d<;tng
nguyen chlft bAng nhau (pf = 0 cUng dQ thl thanh phin pha
hoi mCti bang dUng thanh phAn ella dung djch a mQi nhit d. TruOng
hqp d6 hitm, thf c6 thi g4p a h6n hqp 2 cMt long d6ng ph<ln
quang hQC. Khi d6 ap sulft hoi tortll ph!tn ci:Ja dung djch lJ T = const 18.
hAng s6 va loOn loOn bAng p f. Thi!C :
57
0 0 0( ) 0
p=pt +P2=Pt x1 + P2x2 =Pt Xt + xz = Pt
(vi pf = V8 Xt + Xz = 1).
DUCm.g bi!u dien ella p trong gi!n. dO p - x 18 m()t d\.tUng thing
ngang, song song vai nvc x. d s6i ella dung (ijch d6 (0 p = const)
ciing Ut hAng s6.
2) Ne'u pf thl thlmli pban pha hoi se khlic thanh pMn dung
djch lOng. Gici thic!t cS:u tir 2 de bay hai han clfu tit 1, ttk ta > pf
(khi tMm n6 vito dung djch li tu<mg n6 se 18m tang 8p suilt hai toAn phAn
cila dung dich). Khi d6, theo (IX.ll) :
Y2 xz
->-
Yt Xt
Ke't qui\ n8y din tdi dinh quan trQng gQi 18 djnh lu4t K6n6val0p
thU nlui't, do nhil hac hQC Nga D.P. KOn6val6p (1856- 1929), hQc trO
ella D. I. Mendelrep, kMm pba ra nam 1881. Dinb KOnOvalOp thU
nMt c6 th<! pbat bi<!u :
Trong dung djch hai clu1t lOng, pha hai so vbi pha lOng cdn bOng v6i
n6 se tlldng dOt giclu cdu tU niio ma S/f them cdu ttl d6 vtlo dung djch a
nhit d kh6ng ddi lam tdng Op sudt hdi toiln pluin cUa dung djch, ttlc Iii
ltlm gidm nhift d(J s6i cUa dung dfch t(li tip suOt dii cho.
b) Pha lOng Ja dung djch kh6ng li tlldng, pha hui Ia hOn hf!p khi li
tuUng. Khi pha lOng Ia dung djch khOng 1i tubng, thl khOng c6 h thUc
t6ng quat c6 c4ng don giim (IX.Il) nhu d6i v6i dung djch li tudng. Tuy
nhien, djnh Konoval6p I vAn luOn Iuon dUng. Ngo8i ra, trong mt)t s6
truC:mg hgp, c6 c6 them <4nh KOnOvalOp II (khOng c6 djnh _
KOnOvalOp II d6i vOi dung djch li tudng ; chi dung dich khOng li tubng
m<li c6 th<! c6). Cit hai djnh diu do D. P. Koo6val6p tlm ra rulm 1881.
D6i v6i dung dich khOng li tudng, c6 thie't d 2 djnh lu*t
KonovalOp mt)t each don giiin dl!<l vao M thUc Duhem - MacguleXC1
(IX. lOa) trong d6 ta thay .x
1
b8.ng 1-x
2
va thay dxl bang dx1 = -dxz iJ
T = const:
58
dp
1
idx
1
dp,id(I-x2) dp2/dx2
= =
p
1
ix
1
p
1
/(I-x
2
) P2ix2
nlc la:
dpl _ dp2 Pt x2
d(l- x
2
)- dx
2
p;- 1- x2
Clu1 y rAng ap hoi p
1
va P2 ti veri pMn mol trong pha hoi, tUc
la p
1
/p, = y
1
/y
2
=(I- y
2
)/y
2
, do d6, thtlc c6 vit:
dp, = - dp2 1-y2
dx2 dx2 1-x2 Y2
Ti::t p = p
1
+ P:2 suy ra dp = dp
1
+ dPz. Chia 2 vl ella ding thUc nay vOi
dx2 va thay dpt/dx2 bing bie:u thUc trtn se duqc:
d?2 =

)J
Nhung:
= (l-x2)y2 -x2(1-y2) =
l-x2 Y2 ) (l-x2lY2
dod6:
dp dp2 Y2 - x2
dx
2
= dx
2
(I- x2lY2
Th M thUc nay nit ra 2 ke't 11$1 :
(T = const) (IX.l2)
I) Nu (dp/dx
2
) > 0 thl bAt buc (dl'2idx
2
) > 0 vi khi lAng x
2
(!herr
dlin c!u tir 2 vao dung djch lOng b T = const), P2 c6 tln.g thl p tOOn ph&!
mm c6 the tang duqc. Khi 46, theo (IX.I2) phili c6 Y2 > x2 (biri vi 11 mih
5'
s6 c6 Y2 > 0 vlt ( 1 - Xz) > 0). NhU Ill da thit dUQ'C djnh lutj.t
K6n6val0p I dOl vOi dung djch lOng khtJng li tuting, philt bilu nhll sau :
DOl vOi dung djch lOng li ruJng ding nhll kh6ng li tUdng, pha hoi so
vOi dung djch lOng ctin bting vUi n6 lu6n lutJn tttang dOl gitlu c(fu tU ndo
rna Sl{ them vao dung djch ldm tdng Up sud( htYi toim p/u!m cUa II d
d{J kh6ng ddi.
2) N!u (dp/dx
2
) = 0 thi vi (dp,/dx
2
) * 0 vit (I - x
2
)y
2
* 0 cho nen
theo (IX.12) ph3.i c6 y
2
= x
2
. Khi xa.y dl!Ilg duOng bitu p = f(x
2
), tl,li
nhtl'ng dhim Xz nlto rna (dp/dXz) = 0 thi ti;Li d6, dUC1ng ph8.i di
qua qrc tri- (clJC d!,li hoi,lc qrc tii!u). Theo kt qua vita rUt ra thl nhfrng
cqc tr! d6, thanh phAn pha hcri phiii b8.ng dUng phAn pha lOng
cAn bAng v6i n6 (y
2
= x
2
). nay cling ph3.i x:iy ra nhilng
Ung v6i cgc di;Li hay qrc Wn duCmg cong nhit d(l s6i ella dung dich
theo thi'mh phAn dung d!ch (bbi vl qrc <ip suat hcri ella chAt lOng
Ung vOi qrc tieu nhit d<) sOi n6 va nguqc
qua d6 dAn tOi d!nh lut,it KOnOvalOp II d6i v6i nhUng dung d!ch
kh6ng If tubng nao rna cip smlt hcti toan phAn c6 sai lch duong (so v6i
dinh Raun) tOi mUc c6 c\Jc c6 sai lch a.m tai. mUc c6 Cl{c
tieu. Djnh KOn6valOp II phat bitiu nhu sau :
Die'm ctfc dq.i hay ctfc tiiu trett duCmg cong biiu dien rip swl't hoi toiin
phdn (lw{ic nhift d sOi) cUa dung djch theo thiinh phdn cUa dung dfch
Ung vb"i nhiing dung dich c6 thiinh pluin bdng thiinh pluin cUa hoi cdn
bdng vdi n6.
Nhiing dung d!ch nhu th gQi 18. dung djch ddng phi.
3, Hi>n ding phi. Dung djch bOn ding phf cOn du<;n: gqi Iii. Mn h'7p
:s6i kMugddi (azeotrope, tU" nhihlg chli: Zeo == s6i, a== khtlng vii. tropos,. thay d6i),
nghia Iii. nhilng bOn hgp lOng d6 s6i 0 nhit d c6 djnh, kh6ng dOi, gi6ng nhll ch!t Umg
chit (dT nhien du6i lip suilt khf ngo3.i khl'lng d6i). Khi c:ft nhilng bOn hqp
ding phi thEta thu dugc ngltllg djch c6 thimh phAn gi6ng thlinh phAn h6n hgp d6. Do
d6, nguyen uic, kh6ng the'! n3.o t<ich dtrqc hoil.n toim nhfing du tlr ciia bOn hgp ding
phi bilng slf cit "ding flp'', nghia Iii. tip suift khl'lng d6i.
D6i vOi bOn ding phf, khi l!un thay d6i <ip suift thl khl'tng nhli:ng nhi1 d(l Sl'li thay
d6i, rna d. thimh pMn cUa bOn dQng pbf cilng thay d6i, ditu nay chUng tO Mn IUJp
d&ng phi kh6ng phdi 10 nhil11g h<!p cluft ho<i hQc c6 th3.nh phAn Xlk djnh nhu tmOC kia
60
ngui'ri ta t\wng lAm (du& nhiing ap su& khlic nbau, nbiing bi;tp x3c d!nh sOia nhUng
d(l kh3c nhau nhung thlmb cita cbling kbOng thay d6i).
Thi dl,l ditn blnb ve bOn bgp ding phi lit Mn hlfp nlliK rllf!U etylic <;Hs')H, bOn hqp
nlty sOi {J t"' 78,l5C (clfC ti!u d(l sOi, vl nhit d(l sOi cita mWc nguytn cbA"t lit
I= l00C vlt cita rugu etylic nguytn lit t = 73,3C) t;p 3p suA"t kbi ngoili I atm.
l'tng vt'Ji thAnb ding phi lA 95,57% kh6i htQD.g CzHs<JH, Ilk Ia 89,4% mol CzH
5
0H
trong bOn bqp ding phi. Th3.nh ding phi ella bOn bqp ding phi nuOc - JUQ'U etylic
thay d6f theo ap suA"t nbu sau :
Ap suA"t, atm 1,0 0,5 0,25
%mol <;H
5
0H 89,4 91,5 94,1
0,125
99,7
utc Ill th3nh ding phi cbuytn d!ch d4n vt phia rugu etylic nguyen chA"t khi 13m h'-
tb4'p d4n ap su4't. BAng each d6 c6 thi thu dugc IUQU etylic thi,TC tl nguytn cb4't. Tuy
nhitn phuong phlip niiy khOng kinh te'.
Cu6i ci).ng, vt Mn hqp ding ph(, ta c6 th! dua ra nb$0 xet sau day : Ht5n hlfp d&ng
phi ld Mn hlfp cO sal t6i da so vUi tinh li tiMng md vdn bdo todn dllf!C tinh tan hodn
totln vdo nhau thea Mt ki ti ndo cUa hai cd'u tU lOng ; m(ll sai nbO, ph1,1 them, d6i
v6i tfnh lftubng, se tam cho Mn bqptacb ra thAnh bai lOng rieng re tm;mg chia
ldpJ, tiic 13. Uun xult nhiing vlmg c6 tfnh eM cita hai cA"u tir lOng.
4. Glim dO ip sui:t -- th3nh ph,n, nhltl dQ sOl - thimh phllin. IDnh
IX-7 trinh b3.y giin dO cip sulft hoi toan phin cU.a dung dlch theo thanh
philn A). gii!n d6 nhit d sOi- thAnh phi!n B) va gii!n d6 Yz- Xz
quan h so saoh giiia thAoh philn pha hoi va pha loog C) d6i v6i
nhUng tnWn.g hQp We nhau nhu sau :
HAog I - Dung djch If tuimg ;
HAng ll - Dung djch khOng lf tuOng c6 sai duang ve cip sulft hoi
chua tdi mUc c6 C\IC ;
HAog lii - Dung djch khOng If tuimg c6 sai lch 11m vt ap sua:t hoi
chua t6i. mUc c6 C\l'C tieu ;
HAog IV - Dung djch khOnglf tuimg c6 sai lch dtrong t6i mUc c<'
c\fC 8p sM't hoi va do d6 c6 cl,IC tieu dO soi.
Hang V - Dung djch khOng lf tuOng c6 sai Am t6i mUc c6 CJ!C
tieu 8.p sulft hoi v8. do d6 c6 C\IC d(l sOi.
C(lt A 13. nbiing dWng ding vt Ap sua:t bai toan ph4n cita dung djcb theo thAn!
pMn dung djch (d!Wng mSt p - x
2
) va theo thlnb ph4n cfla hai_ (dtrong chatn chfn
6
p- y
2
). ThAnh ph4n dung djch lOng bitu thi qua ph4n mol x
2
ella cfu til 2 va thilnh phlin
cUa hoi biiu lhj qua pb4n mol y
2
ella ciu llr 2 lrong pha hoi dltl;IC ghi trin ding
fn#: lwanh. Onl Y dog hai dll(mg p- x
2
vi p - y
2
bao gii':l ciing nhau li,li hai dliu
mUt pj va ling v6i cA"u til I vi 2 nguytn chA"I: thanh ph4n lOng vi hoi aia cUng
ml)t chit nguyen chit bao gii':l" ciing b!ng nhau.
Cling eM Y ring dlli':lng p-y
2
(chfm ehA"m) bao gii':l ciing 0 dmii dui':lng p - x
2
(net
Dubng ding p-x
2
gqi llt dllhng lOng (tit'ng La Tinh liquidus = dui':lng lOng).
N6 llt bien gidi. ella vilng pha lOng "d6ng thi 0 trtn n6. Dlri':lng ding nbi(!t p - y
2
gQi
Ill dllitng hai bay dllilng sfll1ng. N6 llt bien gi& ella vilng pha hoi d6ng thi 0 dlltn n6.
VUng m\m giUa dlti':lng lOng vll dlti':lng hoi ill vUng dj 1hi c6 hai pha lOng vi hoi t6n ti,li
d6ng !)li':li..
Cl:ni y ring dui':lng p- y
2
bao gii':l cling Ill mt dulmg cong, dU ring dUCrng p-x
2
luang
ling v& n6 c6 thi Ill dui':lng thing (tru<mg djeh If tuOn,g).
CQt BIll nhllng dllt'Jng ding ip nhi(!t de) bit d4u s6i clia dung djch theo thltnh ph4n
dung djch (dui'mg net t-x
2
) vll theo tbAnb pb!n clia hai. (dui'Jng ch!m eMm t-y
2
).
ThAnh ph4n dung djcb lOng (x
2
) vll thanb pUn hoi (y
2
) dlli;JC ghi trtn cUng m1 lf\IC
hoAnb gi6ng nhu tru(mg hqp nhilng giAn d6 tbuc CQt A.
Clni Y khi cbuyin tlr c(ll A sang B thl quan h(! bj dAo nguQC. Clfu llr I nguyen chat c6
ap su<fl hoi bio boil thl"p tbl e6 nbi(!t dl) s6i cao cOn cA"u tlr 2 nguyen cbKt c6 lip suA"! hoi
bio boil cao thl c6 s6i IMp (0 c3c giin d6 trtn hlnh IX-7), ciu tit 2 luOn lu6n
dugc gii thit't lA c4'u tiJ c6 ip suA"t hoi bio boil cao). DuOng t-y
2
(lhilnb ph4n hoi, dul'mg
cba:tn eha:tn) lu6n 0 tren 1-x
2
(thllnh ph4n dung djch lOng, du(mg net DuOng
t - x
2
Ill duilng lOng, bien gi&i ella vilng pha Umg d6ng lhi 0 dmii n6, cOn dlri':lng t-y
2
1ft
duimg hdi hay duOng sud/lg, bit'n gi&: eiia vil.ng pha hoi d6ng the 0 tren n6. VUng ben
trong dui':lng lOng vll duOng hoi 1ft vilng di thi hai pba lOng va hoi can bing v&: nhau.
Diim Cl}'e di,li tren duOng cong ip suft hoi Ung v&i CIJC tiiu trtn dui':lng cong nhi(!t d
sOi vA nguqc li,li. Ti,li nbllng diim d6, theo djnh KOnOvalOp ll, dung djcb lOng via hai
bio boil ella n6 c6 thilnh ph4n nhau, x
2
= y
2
(dong djcb ding phO. N6i Clicb khac,
nhllng ditrn d6, d!Wng net ii&! (thilnh ph4n dung djch lOng) va dui'mg chain cha:tn
(thllnh ph4n hoi) phii nhau.
D6i v6i giin d6 dQ sOi - thilnh pb4n (CQt B) cae duimg 1-x
2
(net lil!n) vi t-y
2
(cha:tn chain) c:Uu Ill dtWng cong (k6 ci tnrong hgp dung djcb If tuOng. Ta:t eli chi c6 3
giiln d6 nhit d sOi - tbiloh phio, thU nhft Ill mt blnh lhoi kh6ng c6 cl,(C trj,
lmg v& 3 bAng-dlu I, II via lhU hai. Ung v& hAng IV c6 C1!C tiiu lhUba,
Ung v& bilng V, c6 CIJc-di,li.
62
PI
I
p",
0
II
III
IV
v
0
A B
c
p",
~ ,
\:"
..
q ..
~ c
~
"'
' .. ~
1
: ,,
~ ,
'
' '
x, y,
0
-x,
0
- x, (L)
-x,
,.-/
_.

..
............
0
e
'-..
Xe
1
- x,
...
..........
.

..........
..
..

...

' 1
-x,
- ,,
Hlnh IX-7. NhDng ~ giin d6 khic nhau ~ c a n bAng lOng- bai
0 h ~ 2 chAt lOng hoi tan hoiin toAn vao nhau khOO.g h ~ eM.
x,
63
5. Sl,fCAT HON HQP HAl CHAT L6NG
Khi. nang tich dung djth thMh nhihl.g clu tit ella n6 nbO ch!lDg eft d1J3 chU yu vao
Sl! khli.c nhau thW!h ph4n cAn bAng ella pba lOng vi pha hoi.
1. Ci"t phin
Sa dO nguyen tic edt
ph4n trlnb bay trtn h1nh
IX-8. H6n bqp lOng ban dAu
thlnh ph4n X l sOi 0 ditm L
1
can bAng v6i luqng hoi nhO
diu lien H
1
thlmh pbln y
1
. 54!
ngung l\1 W: ca lugng hoi nay
cbo lm;mg ilhb ngung djch
dju titn I...! thlnh pb!ln lt
2
= y
1
.
Dem eft ngung djcb nAy 14n
thU hai, thu tugng nhO hoi d4u
titn H
2
ella n6, thlmh phM y
2
r6i 13m ngung 11,1 tit cii.
hn;mg hoi nAy, diJVC hn;mg
nh6 ngung djch thli hai
thiinh puin X3 = Y2 Dem cfr:
ngung (ijch nay 14n lhU' ba, v.v ...
0
A
x,
-xs
x, 1
B
Hi11h /X-8. Nguyen cie ca:t phan doi!ll bOn bqp
2 ehW lOng
cii tbt titp l\JC miii., cu6i cUng thu duqc ml)t hrqng nh6 ngimg djch chU'a c!u til B (dt bay
1
64
rs:
--
--
L' H' 1 ,
hai) nguytn chilL NbU Vlj.y,
ci't phln Ill SlJ l*p di
cal nhMu ltln nhilng dl)ng
tac sa cf"p hai hoi W ngung
M3i d!)ng tic bOO hoi va
ngung dnqc phin 3nh trtn
gi3n dO bAng mQt IJ4c thang,
thf d1,1 L
1
H
1
Lz.
0
A
1 --
---
...... H'
L'2 - _______ .. .. 2
Trc'J bOn hqp lOng ban
t
0
B diu, vl n6 mi't m<)t luqng nh6
hcri H
1
n!n diim biiu di&l
4 1 ella .n6 djeh sang btn tnii
diim L
1
m(lt it, thf diJ
(hlnh IX-9). St.r eft phan
"'>u----
___ H'3
L, --.... '
;"-'
'
x,
X
3
X
Hillh /X:-9. CA"t ph An do;pt
ti61 hAnh d6i v6i. chAt lt'mg L; Mng dWng b9-c thang L; H; t.; H; L; ... cling
se cho rrn)t hrqng nhO B nguyen ch!t cc)ng thtrn vAo lugng nhO diu dii thu dlli}C theo
dWng * thang

... (trtn hlnh IX-9, dUCntg nay gbi bAng net IMn). Chit
lOng L; tro thlnb a ben trai L; m(rt it. Nhb c!t phAn n6 cho mc)t Jugng nhO
8 nguyen chlrt. Nh11 lugng c!u tir nAy d4n d!n tang len trong khi diim bil!u ditn cUa
chit lOng ban d4u chuyl!n djch d!n ve dil!m tA, nghia lA binh cit ban diu cu6i cling se
chtta chft lt'mg A (kh6 bay hoi) cUt. COng bAng eAch d6, nhilng ph4n chafl llmg
... L;, L; , ... cling chuy!n dich d4n phia dil!m tA. va cling cho A nguyen chal.
Nhll se tach diRJC bOn hqp lOng ban d!u thlnh A nguytn chit U binh cit va 8
chit a blnh nglltlg hcri..
Trong sAn xuit ciing nhll trong phOng thi Sl! cit phAn duqc hAnh
dllffi m(rt qua tiinh lien 1:\JC trong d6 nhlmg dc)ng tic hoi hoi va ngltllg 1:1.1 ti:mg phain
dllgc t1f dc)ng h6a. ngoai ra cOn d1:1ng cl phiWIIg pbap dQi htu, nghia ll biw dam cho
hai pha (lOng va hcri) chuyl!n dc)ng thlnh hai dOng ngiRJC chifu nhau vA xUc nhau.
Qllli trinh gQi ll tinh edt.
2. Ttl.(c}ng hqp hbn hqp ding phi
IDnh IX-10 iing v& c6
0
(A)
-x,
: e
'
1
(B)
cl{c tilu d4 s6i. Gii lblr ta
xuft ph3t tir mQt hOn hqp a ben
tnii dK!m ding phf e. Khi pha
lOng L sOi 0 de) t, hcri. cAn
bAng v6i n6 c6 thimh phain H,
chUa ttrong d6i nhitu ciu ti'r B
hC1D pha lOng. Do d6 tic!p we
sl! eft theo k.i,i!u cit phAn thl
phlfu chit lOng cOn trong binh
eM se ti!n dlfu de'n A nguyen cha:t
cim ngung dich se titn tili Mn
hqp d&ng phf c6 thimh phdn iing
v6i dil!m e, t6i dlly h6n hqp ding
phi sOi khOng thay ddi thlmh
ph!n nil'a (a 3p suit khOng d6i)
vii. do d6 khOng c6 dQng ll!c cho
Sl! chlltlg cit nita. Nh11 khOng
thl! nao tach dllgc hoAn toan 2 diU
ni A va B cUa h6n hgp ban dd.u.
Hb1h IX-10. GiM d6 dQ sOi- th!ulh ph4n d6i
v& 2 cA"u ti'r c6 CI!C ti!u nhit d(l sc"'i
Ciing c6 thl! n6i tiMig 1:1! nh11 nc!u bOn hgp ban dliu l1 ben pbai dil!m ding phf e.
Pha lOng L' sOia nhit de) t' vii chUa tllOIIg d6i nhitu ciu tUB hC1D hcri. H' cAn bing v6i
65
n6. Do d6 ph&! chllt lOng cOn trong blnh cllt se titn din Wi. B nguyen chill trong khi
ng1mg djch titi1 ddn tili luJn h(Yp ddng phi e.
Vt M c6 qrc til!u nhitdt') sOi c6 the kl! b HzO- HzO- CH03 v.v ...
D6i v& M cO ClfC nhit d s6i, ta ciing thu dugc: ohltng kt't qwl. ttrong tJ,I nhu tren
nhung dAo nguqc Nhitng 11 nay _thu<mg Its@ han h? c6 C\lC til!u d() sOi. C6 thl!
kl! h H
2
0- HQ va h HzO- HN0
3
.
Dl! tOm tat, c6 thl! n6i M11 h{tp dt$ng phi cO clfe tiiu nhit d s6i Iii ngttng djch cu6i
cling trong slf edt phtln do(ln 0 dp sudt kMng Mi cOn Mn hqp d&ng phi cO Clfe d(}i nhi/t
d s6i Iii phdn cOn lgi cufJ'i cilng trong binh edt trong Slf edt phdn dogn dO.
66
CHWNGX
PHliONG PHAP BQ
1. DQ VA He SO DQ
1. Thi' hoa hqc cUa cau til trong dung djch If t..rdng vi trong dung djch
th!JC nhllrlg Iaing
D6i v&i mQi dung djch lOng, H tuOng hay kbOng, can bang v6i. hoi bio boll cUa n6, U
Tva p ngoai khOng d6i, n!u c(u ti:r i c6 ci trong pha J6ng (L) va hai (K) thl ditu
can bAng Ill:
ll; = = 11f = 1-lf(T) + RT/nf;
(X. I)
fi Ja 3.p cUa i trong hai ; Ill' (1) 13. s6 chi pb1.1 thul)c vito ban cha"t cUa i va
...,T.
a) Niu dung djch lti li tuUng, ta c6 djnh !u41 Raun fi = f;'x; v6i mqi Xj, do d6 (X. I)
trotbMh:
J.l.j = ).lj (T) + RTfn f;
0
+ RT/IIXj
f;
0
lA 3.p ctia i lOng ng"uyen cMt b cUng Tva p ngo3.i nhu dung djch ; vi fj chl
pbiJ thuc vAo i va vao T, p, nen c6 the 2 s6 diu v ph&i ding thlk trtn thiinh
m()t s6 bi;lllg chong :
}.If (T, p) = J,tj (1) + RT/n f;
0
(X.2)
dod6:
lli = Ill (f, p) + RT/nxi
(X.3)
Cl:ni Y Ill' (T, p) ta th ho!i hQC cUa i 16ng nguyen chft (xi = 1), n6 eM y!u
vAo T, rft ft vao p.
b) Ni'u dung dich lQ khtmg li tfld/Jg nlutng /oiing (chfnh de Iii vO cimg loiing), dung
mOi I vAn tuin theo djnh lu*t Raun, do d6 the' hoi hQC ciia dung mOi van c6 (X.3).
COn ch!lt tan i (i 2) thltulln theo djnh lu*t Henry fi = kjXj, h s6 Henry ki '#- f;
0
, n6Jil
hW!g s6 0 T, p const, tUy theo tnri:mg hgp, ki c6 thl! J(m han hay be han f;
0
Khi d6 d6i
vOi chft tao i trong dung djch loiing, (X. I) trc'J thAnh:
67
J.li = llf (1) + RT/nki + RT/nxi
Vl ki chi phi} thuc vlo i va vlo T, p ntn cOng c6 tb! dl!.t :
llf (1', p) = llf (1) + RT/nki (X.4)
Khi d6 thi! bOO hQC ella cba:t tao i trong dung djch vll loing ciing se c6
(X.3). Nbung llf (1', p} trong (X.4) kbOng phii Ill tb6bo! bQC cila ddt tan i nguyen chit
vl khOng tbl! suy tlfi Xj = I.
2. Ho9t d9 va hf sO ho'-t d9
D6i v6i dung .djeh th\l'e vA khOng dll lOOng thi fi lA m()t ham phUc
ella xi do d6. theo (X.l), hQc lli = J.lf{T} + RT/nfi ci.ing I.a m()t
h8.m phUc ella xi chU khOng c6 c4ng dan giAn (X.3). bio to3n
dan giin (X.3) eho th hoi hQC Jli nhu d6i v6i dung dich lf tubng
va dung dich loing, ta thay n6ng d() xi bAng m()t lugng m6i <l:i gQi lit
hO{lt dt) ella i sao eho :
Jli = J.lf + RT/n<Lj
(X.5)
J.lf IA hot hQC ella i a tMi ehuAn (c = chuAn) 13. m()t thai
quy UOc d6 J.li = J.lf. Khi d6, tU (X.5) suy ra <Lj = 1. a trqng
thai chwfn, hDf;zt dt) cUa i pluli b&ng dcm vj.
Dga v8o (X.l) e6 vit, d6i v6i thai chu!n ding nhu d6i v6i
b{t ki thai cAn bAng n8o kM.c :
68
J.lf = J.lf (1)+RT/nfic
Ufy (X. I) trir di pbuang trinh nay, se duqc:
' Jli - J.li
Ti:r (X.5) ta c6:
f
=RT/n -'
fF
'
Jli- J.lf = RT/n<Lj
CII
t.=i_j
(X.6)
HOlJI d9 ai ctia m(it cd'u tli i Mng ti s6' giiia ho{lt dp cUa i trong hui
bao hod cUa dung djch va hoflt clp cUa i if tr{lng tluii J ding T vd p
ngodi nhu dtfi vUi dung die h.
MUc <1(> sai lch cU.a i trong dung dich th\fC so vOi nhi.tng djnh
dung djch li tubng hay dung djch lOOng c6 t11111g bang h st{hO{lt
d(J Yi 18. ti s6 gifia d va n6ng dQ ella i trong dung djch th\fC :
a f

x f'x
I j I
3. Y nghTa cUa dQ
(X.7)
Trong dung djch thlJC, n6ng dQ kh6ng cbn 18. d4i h.rqng d4c tnmg dAy
dit cho dung d\ch nhu d6i vOi dung djch li tuOng hay dung djch lOO:ng.
d 18. ham dw;:IC dua ra (I) de thay cho n6ng dQ trong dung d,.lch
thl,fC. Cllng nhu n6ng d, ho{lt d(J Ia ml)t d{li lutJng cllimg d(J. D6i vdi
dung <ij.ch thvc, thay n6ng d bang ho!_lt d cOng gi6ng nhll vic
thay ap b!ing hoi_Lt cip d6i v6i cac khf thqc.
C6 the coi d(lia mQt thli n6ng d hilu mt thU n6ng d
dng, mt thU n6ng dQ da chinh rna t<.ti d6 dung dich thgc d'llt
nhUng thu()c tinh ella dung djch li tuCmg hay ella dung dich lOOng.
<:rut h.ru y Hl thay n6ng d(? bilng ho'ltt d ciing nhu thay Rp suAt
b!ng hO'ltt lip Ia chi duqc pbep C:J nhilng phucmg trinh trtmg cho Cftn
blng va suy ra trgc tip hay ghln tip tit sir d\).ng th boa hQC ella lAic
clfu tir. Thf ely, d6i vm dung d!ch thl)t, djnh philn b6 se bi<iu thj dum d;mg :
..
- =const
a:
(I) dl) 11ldo Liuyt (G.N.Lewis) dt ra nAm 1907.
69
2. CHQN THAI CHUAN
Tn;mg thai chuAn lA trc,ng thai rna d6 J.Li = J.i.f va = 1. D6i v6i
dQ v8. h s6 dQ, vic chQD thai chuin ciJa c8.c c4u tir 18. tU.y
y i1 milt: d nao.d6.
N6i chong, nen cht;m trqng thai chuiln sao cho khi dung djch thlfc dt;lt
duqc tinh clu1t cUa dung djch U tuOng hay cUa dung djch loiing thi
dl) tril.ng vcfi n6ng dl), khi d6 hf sil hoqt dl) n = 1. C6 hai c8.ch chQn.
De dan gi!.n. ta gilt pha /uti ld li tudng. lchi d6 f; = p. (X.6) va
(X. 7) tri1 th!.nh :
p

pf
(X.6a)
Tren hinh X-1.
dUCmg cong net 18
dUOng dien ap
smt hai Pi (gia thit
c6 sai dUdng so
vm dinh Raun) a
T = const cita cliu tU i
P,
t
T=const
0
C A B
Hinh X-1. Hai c8ch chyn tbai chuio.
trong dung djch khOng li tuCmg theo thAnh ph!n xi ella dung djch. NhUng
dui1ng th!ng ch<!ch cbain cbain Ia nhilng duimg Rann vii. Henry.
GQi p-
1
ta lip hoi diem c6 n6ng d() xi = OA .
1. each 1 chqn t11ng thai chuin
N6u i xir sl,l' If tuOng, n6 se c6 lip su4t hoi Pi n6ng d(l Ung v6i OB
- - I
sao cho Pi= pf. OB (dinh Raun). OB =a , ta dttgc:
70
= !.L
0
P;
(X.8)
So s8.nh v6i (X.6a} ta tba:y pf = pf, nghia lA th4i chudn cda i
ta thai cda i nguyen chcft U cilng Tva p ngotii nhu dung ;
lA dl) ella i khi thai chuAn cUa i dugc chQn nhu (gQi lA
each 1). Khi d6 (X.7a) tri1 thiinh:
I
I ai Pi
Y =-=--
X p.
I j AI
(X.9)
(X.8} va (X.9) cho t:My a; va r; khOng cO thU nguye11.
D6i v6i dung dich li tudng, Pi= pf Xj, do d6 r! = 1 va a: = Xj. Nl!u
dung <ijch thi,IC c6 sai lch dudng so vOi dpth ll$ Raun, Pi > p f xt thl 'Yi > 1
va a;,> Xj Trong trll(mg hqpc6 sai /fch tim, Pi<. pf xt 'Yi <I va <lj < Xj.
CM y khi chQn thai ella i nguyen chAt lAm thai chuAn,
nghia Ia c6 ai = I khi xi= I thl tlr (X.3) va (X.5) suy ra flf = flf (T, p),
do d6 (X.5) tri1 thiinh :
I';= (T, p) + RTina;
(X.IO)
Vi J.l; = Gi va flf (T, p) = Gf 18 ham Gipxa hay tbl! dAng <ip d6i v6i
1 mol i nguyen chAt, cho nen :
Gi = Gf + RT/ttitj
2. II chqn tr,ng thii chuin
(X.ll)
Nl!u i tuAn theo dinh Henry, n6 se c6 <ip sua't hai Pi tl;li n6ng d(>
Ung v6'i OC sao cho Pi= ki. OC (hlnh OC = a:'. ta duqc:
= Ei (X.l2)
k

So slinh v(ri (X.6a}, ta t:My pf = ki, nghia 18 thai chuAn cUa i 18.
trang tMi thu du;x: b.lng aich ngol)i suy dl!Ong !hAng Henry tren hlnh X -1
71
cho t6i xi = I. Trong i chi tuAn theo dj.nh Henry khi n6 18.
ch.t't tan trong dung djch lo8ng. D6i v6i dung djch khOng dU loang,
d4c khi xi -+ I. dj.nh Henry khOng t6n t].i. Do d6, tha.i thu
duqc bAng eAch suy dt.Wng thAng Henry cho t6i xi = I chi 18. mt
thai gi8 djnh. khOng c6 thJ!c. NhlDlg chinh trl.Ulg thai gi8 dinh nay
liP duQc ch<;m Uun thai chuAn theo each II. N6 tht.Wng duqc dllng
khi i rO rt Ut chtit tan, chi tan c6 v8o dung mOi (c.t'u tir 1) v8 khOng
hinh thAnh dung djch 1i tuOng v6i dung mOi. Khi d6, trt,lng thai chudn
cUa chat tan i (i .? 2) La trr,mg thai khbng c6 thl/c cUa dung djch c6 n6ng
d9 cUa i b&ng ddn vi (x; = 1) md tt,li d6 clp sud( hoi cUa i b&ng hf stf
Henry k; cUa i trong dung djch vO cUng loting.
Oich chqn tha.i chu!n nhu 18m cho s6 ho!;lt d Yi , theo
(X.7a) c6
a p px
Y
. =-' --'-=-' -'
' -
Xj kjXj p:tx:"
' '
(X.l3)
lllfu Ung V<li dWlg dich VO c:Ung lo!!ng trong dO, theo djnh II$ Heruy,
pj = kixj. va ndlukMngc6tluinguyen.
D6i v6i Wng dung dich loing tu!n theo dj.nh lu4t Henry thl <Lj = Xj va
Yi = 1. D6i v6i mQi vllng kMc, Sl! sai ella s6 d Yi so v6i I se
cho mt Y ki61 S\l sai so v6i djnh Henry.
Tht! ho8. hqc cUa cMt tan 2 trong dung dich khOng 1i tuOng c6 dl.lJlg :
I'Z = f'2 (T,p) + RTina
2
= (T,p) + RTiny
2
x
2
(X.l4)
(T,p) khOng ph& Ia th bOO. bqc ella c4u tir 2 nguyen cMt rna
bOO. bqc cUa clfu til 2 b thai cbuAn (khi a
2
= 1). Tht! bo8. bqc ella
cac cb.t't tan i khlic (i <::: 2) ciing c6 d!;lllg toong lJ! nhlf
Qui Y rAng d6i v6i thai k:hOng c6 thl,lC ciia dung dicb dllge cbqn
Uun tr!;lllg thAi cbuAn, <Lj = l, Yi = 1, thi tr!i ll:ri, d6i vai lrl.lJlg th!i c6 thl,lC
CUa i nguy&l chlft (khOng pbai lA- tluiicbuan), Ia c6 (l\ = [, p= pfl:
72
(X.15)
3. Kift
Dt ke't va mi:J r(tog nbUng kt qui tren, la xet tnrem.g bQp tOng qwlt khi pha hCJi
kh6ng phdi Iii h611 hf/P khlli tuUng. Khi d6 cAc 11 tMc trtn vAn dUng, nbung phii lhay P;
bbgf;.
D6i vUi mQi clu tlr i, chi c6 mOt djnh nghla duy nhA"t ho(ll d ella n6: a;=
Tuy tu)' theo cich CbQD tb<ii cliu!ln rna 3;_ si: nh$11 nbitng gi;i lfl bing s6 kb3.c
nbau.
Theo cdch I. tbutm.g duqc dUng khi Clic cMt lOng i boa tan vlo nbau tbeo Mt kl ti I
nao va dOng vai trb tUOTig duung nhau trong cic thu(ic tfuh ella dwtg djch. thAi chu4n
cUa i Ia thlii thl.fc ella i nguyen chit a cimg T va p ngoai nhll dung djch (f = fi ).
Khi d6:
I f. I p-
a; = .:L boac a = _.!,_ (nlu hoi lA H tubng)
rt Pi
Khi c6c cdu tU dOng vai trO kh/Jng tfl(llig dllclng nhau, nghia lA c6 cfu lli r6
dung mOi (c;fu tir I) cOn clc c&J til khac 18. cMt tan (gqi lA cA"u tU i, i :!: 2), nhfrng cll"u tir
nay chi tan c6 hliUl vao dung mOi, thi tl11D& thai chuln cUa dung mOi I vAn theo clch 1,
tt1c lA thai thi{C cUa dung mOi I nguytn cbft.
Oti d6i vm chdt tan i (i 2: 2) khOng hlnh th8oh dung djch li tuimg v6i dung ml'li
ng!Wi ta mm chQn thai chuin theo cdch II: thai chub. ta thlii kMng 00
thi{C ella dung djch 00 n6ng de) ella i bing don vi rna fl!.i d6 lip suM hoi) ella
i bing h s6 Henry k:i ella n6 trong dung djch vl'l ciing loing ( f;c "'kj). Khi d6 :
a !I "' .!L boac a!
1
= P; (n!"u hoi 18 tr tuimg)
I k; . I k;
Nhim.g gia trj cUa llj_ theo bai c6cb khk nhau ChQD tM.i chub. lul'ln lul'ln a vic
mi)t ti 1 kMng ddi, kMng thuQc vao xi. Thi!C
a! k a! k
-
1
= __.!. = const -tJ "' --L = const (X.l6)
fi a; pf
Ghi chU. D6i v6i Mn hqp khi, nguM ta chQD thai cbudn cUa khf i 18 ih6i
ella kbf i nguytn cbft a cUng Tva p chong nhu trong h6n hgp va chfp nh$11 a tr.p1g thai
nAy f;c = fj "' I.
V1 a; "' f,;f, b dAy tf "' I, do d6 d6i v6i khi i, a; = f; tile Ill. lw{l.t dq cUa khJ bdng hOf!t
tipcUa nO.
73
D6i v& khi II tuCmg, lip hAng lip sulft, f; "'P;. a;:: P;. tUc ll ho(lt cUa khi li
tlldng bting tip su4t cUa mJ.
3. lQ VA SO lQ THEO
NHUNG THANG NONG lQ KHAC NHAU
b trtn dii trlnh biy hot d() vl M s6 dQ tbeo thang n6ng d() ph4n mol x. Khi i
chi tan c6 hq.n vlo dung m6i vl ro ret lA cha:t tan thl ngoai thang x. nguai ta cOn dUng
h"" de) vl M s6 d(l theo nhilng thang n6ng de) mOian m va n6ng dQ mol- tilt tich c.
Thang n6ng de) X : llx : y xX
Thangn6ngd()m :a.r,=Ymm
Thang n6ng dQ c: 3c =Ycc
Khi d6 the' boa hQC Jl ella chlft tan c6 bifu thj theo m(lt trong ba cich sau (ta kl
Jl tbay cbo lli cbo :
Jl = + RT/11ax = + RT/nYxX
(X.17)
D6i v6i m(lt chat tan trong dung djcb aT, p vil thlnh ph4n dii cho, thl bOO hQC Jl ella
n6 chi c6 m(lt gili tQ. Nhllng vl x m c vii cho ntn de de) llx
a..,. 3c nh;)n duqc nhilng gii tri khlic nhau; d6i. v& y,, Ym Yc cling
Yx gQi Iii. s6 dQ thudn li, Ym gQi Iii. s6 dQ t/ufc d!!ng hay s6 ho!)1 dQ
molan, duqc dimg phd biln chochlft phAn trong dung dich cha:t dien phAn, ci'm Yc ft
dUng han.
D6i v6i cht tan, cich ChQII trq.ng thai chuAn trong thang m hay c cling tiln hlnh
vllo djnh lu*t Henry nbu trong thang x. b trq.ng thlii chu4n. ll = (ito ) va a..,
(b* a,) = I. Gii thie't pba hoi 18 II tmJng. Trong mOi trlKmg hgp, ngtWi ta cling xay
diJDg nhitng dui'mg bifu diet! lip sdt hoi P:z theo n6ng dQ m c (hlnh X-2) a vimg
n6ng dQ tba:P mil d6 lu$t Henry Pi= km .m* h* Pi = kc ."c dugc tuAn theo
r6i suy cho Wi n6ng d() dan vi bAng clich gii djnh clog a n6ng d() nay, v!n c6 djnh
1\$ Henry."' thai gii.djnh nAy, cblft tan se c6 lip su!t hoi bW!g km hoiJc k..-
74
Nbu vll-y, d6i v6i chAt tao,
thai chuA:n. trong cii 3 thang n6ng d(l
x. m hay c Iii thW gili. dinh
(khOng c6 thi,I'C) ella dung djch c6
n6ng d(l ella ch4't tao bAng dan vi mil
t;p d6 ap su!t hai ella ch4't tan bing
s6 Henry ella n6 trong dung djch
vO ciing loing.
P,
l
Vll-y ho
P2 = kc =Pi /c (chli Y phan
chi s6 c 6 cao Iii chi thai chUA:n.
v6i chi s6 c 0 chan Iii chi n6ng d(l
mol- thf tfch c).
Theo djnh nghia, ho11-t d(l cita
ch4't tan lila= p
2
/P2. Thd6:
Hlnh X-2. TI'II-Qg thai chdn dO:i v6i chAt tan
trong dung dich kbOng li tu6ng theo tbang m.
a.n 1>2/m 1>2/m
'=-=--=--
m m "-m
(X.l8)
Nhitng be tbltc nily gi6ng bet nhitng h tbli'c (X.l2) vii (X.l3) dii tbu duqc trong
tbang n6ng x.
On1j dng, ddi vOi cluft tan, ni'u hoq.t theo thang x lc2 d lll{tng kMng cOthil
nguyin thl, tr6i l(Ji, ho(Jt theo thang m vO c ld dt!i IU{111g cO tht nguyin ella

Thi,I'C vll-y, theo thang molan m, s6 Henry !ilk,= p /m , do d6:
a = h = !2. m
m
m 1'2
Vi ti s6 p
2
/ P2 khOng c6 tblt nguyen, ntn 3m c6 tM nguyen cila n6ng d molan m
(moVIOOOg dung mOi). Cilng tuang tt,r nhuv11-y, kc = p; /c vi:
P2 c
kc Pi
do d6 a., c6 thtt nguyen ella n6ng d(l c (moVl).
Oc he d(l Yx Ymlc thlluOn lulJn lilnhilng d!\i luqng khOng c6 tbd'nguytn.
D6i vffl. chfl tan 0 thai chuin, boll-f. dl) bing n6ng d(l vii bing dan nily
dUng trong d. 3 thang x, m vii c :
75
a.._=x=:l;
Yx=l
a,=m= 1;
Ym = l
a.,=c=l
Yc =I
s6 dQ cUa chit tan cling bAng l trong dung dich vO cling loing ; r; = 1,
=c".
D6i v6i dung dich dU loing dt: cac n6ng d(l x, m va c ti v6i nhau, cac s6
dQ Yx Ym vR Yc dp xi bAng nhau. Ntu dung djch dq.m bon th'i My giOyx, Ym va Ycf6
nhilng gili tri khac nhau ro rl
4. PHliONG PHAP xAC El!NH EJQ
VA SO 9Q
Ho!)t d(l va h s6 hrnj.t d(l cUa cac c!'u tlr trong dung dich c6 tht: :de djnh tlr nhilng
pturong phap thlfe lhf dl) phiWng phap lip sui't hoi, phiWng phiip djnh phAn
b6, phiWng pluip blm v.v ...
D6i vCri dung djcb 2 ci'u tli, c61ht: ti'nh dQ cUa c!'u tir nay khi dii bi1 ho!_ll d ella
c!u.tli kia bing ciich sli dq.ng lhli'c Gipxa-Duhem.
C6 lht: tinh /i thuyii hrnj.l d(l vlt s6 hrnj.l d trtn CCI sCr nhilng gil\ tbuy(t ni!o d6 vt
ban chi't vi tlic dq.ng cUa nhilng life gay ra nhilng sai ella dung djch so v6i tfnh If
tll(mg. Qich ti'nh nay m6i chi lhlulb cOng t6t d6i v6i dung dich ri't loing cbi't
pbin (lhi dq. xem lhuy!t Dabai.-Hucken trong hoi hqc).
1. Phlldng ph8p ap suit hcti
ChQn tn;mg thai chuAn theo each I thi a; = Pi I pf khi hoi 18. If
t!Wng. Cich nay thuOn.g lip d1,mg cho dung mfii. xlic dinh ap sua:t hoi
Pi tren dung d!ch c6 n6ng d Xj va do lip suA't hoi Pi ella i nguyen cha:t b
cU.ng Tva p ngoai nhu dung djch thi c6 tM xac dinh trl,le ho<].t d a;
ella i.
chQn trl].Ilg thai chua'n thea clich II thl a;_ = f>t xcic dinh a;_
thea each nay, dn pluii x8.c dinh h s6 Henry ki = pj_ /xj, dllu *ling
v6i dung dich VO cii.ng lOOng. Mu6n xac d!nh Pi b clic xi khac nhau,
76
ghi P/Xi a tfl:IC tung va Xj tren tfl:lc hoanh r6i suy duUng dien
cho t6i xi = 0 se dugc D6 18. giCri. hc;m ella ti s6 P/xt khi xi 0 (hinh
X-3). H s6 Henry 11 dAy ling v<li thang n6ng dQ x.
Trang th\IC khi lam gilun
n6ng dQ rna th4y ti s6 P/X; tie"n den
m(>t gici tti c6 dinh thl ta cba'p
gia trj nay cho h s6 Henry.
Phuong pMp ap su!t hoi !huang
dugc dimg khi chi c6 mQt minh c'"u
ti:r i trong dung djch 18. bay hoi hay
c6 ap hoi rO l&J. han cac c3:u
tt'rkMc.
2. Ph\ldng phip djnh lu.t phin bO
1 . .
..
..

OL__ ___ _

HinhX-3. Di xic djnh M s6 Henry k;
Khi c6 sv phAn b6 can Mng m(>t ch'"t tan i giUa hai dung mOi (') va
(") khOng tan vlt.o nhau vil vCri. nhUng dung mOi niy, cMi: tan i hlnh thanh
nhilng dung dich khOng I! lUOng va khOng du Ieang. thi dinh phan
b6 pbai thi qua d(> a' va a" ella i trong 2 pha lOng d6:
a'
-=K
a"
(T = const) (X.l9)
K 18. hAng s6 pban b6. Do d6 di S\1' ph\1 thu()c ho<.Lt d(l ciia i vao
n6ng dQ d6i veri. dung mOi nay thl c6 tht tim th'"y S\1' ph\1 thuQc d6 d6i
v6i dung mOi kia. Mu6n phlii x8.c dinh h s6 phan b6 K tU diW
giCri. bc;m. Vi b d(> loing vo hc;m a = c'" cho nen:
* *
a c
K=-=-
, ...
a c
3. Ph\ldng phip tfnh d9 cUa cBu tlr nay tLr d9 cUa cBu
tlr kia d\f& vao hf th'll'c Glpxcs - E>uhem
a) Hf thUc Gip.xo-lJuhem vi ho{lt Theo M thttc GipxCf-!)uhem b
T, p const, = 0. Qic c6 = (T,P) + RTlnai , ccic
77
-fll' (T,P) chi thul)c vao Tva P, do d6 aT, P const, clic dfll' bAng
khOng, cOn :
dfli = RTd/na;
Dua gici trj. nay ella dJ..Ii vito I:D.jdJ.li. = 0 va sau khi lo{li bb RT se duqc
tht'rc Gipxa-Duhem hrn;tt dl) ella c.tc til trong dung djch :
:Enidlnai = 0
D6i' v6i dung cijch 2 ti:r (X.20) vit Ia :
n
1
d/na
1
+ n
2
d/na
2
= 0
tir d6 :
(X-20)
(X21)
Trong th'!C tl. <i.p suift chi c6 imh huimg khOng dang Mn J.1i. vlt do
d6 Mn a;_ ella cac i trong dung d!ch lOng, do d6 chi nghien elm b
T = const.
b) Tinh a
1
khi dii bitt a
2
vO ngu(lc D6i vcri (X.21) c6 the thay
logarit l\f nhien bAng logarit phAn r6i lify tich ph!n giUa 2 thai
Ava BOT= canst se dll'qC:
B x,
/g(al)B = /g(at)A - Jx
2
dlgaz x;-
A Xt
Nu /ga
2
di dugc Xlic dinh d6i
v6i thanh pUn kM.c
nhau (tU'c Ia d6i v6i xz!x
1
kh3.c nhau) thl chi d\filg
duang cong x,}x
1
= fHsaz)
bang ccich ghi x
2
/x
1
t:r!n tr1,1c
78
1
0
H'mh X-4. xac djnh a
1
tit a:z b!ng tkh
phAn d6 thj
tung va -lga
2
tren hOOnb. Sau"d6 xac djnh gia tti ci:Ja tich pha.n theo
phlWilg phcip d6 thj (do din tich cheo trtn hlnh X-4) thi c6 the xcic
dinh lga
1
d6i v6i bjft ki th8i B nilo, Iii n6 da dugc mt
thai A nho d6.
chqn thai A lA dung djch vo ciing loing (x
2
0,
al 1) thi fg(al)A = o .. Khi d6 d Omt thai B Mt ld, c6
x
2
0 se tinh theo h thUc :
(X.22)
thUc nily cho phep tinh a
1
ti:r a
2
va ngugc J4i. Nhugc cQa
pb.m:1D.g phcip 18. cr vim.g dung dich loing, khi x2 0, xl 1 thl 0,
x,
d6ng thUi. a
2
0, do d6lga
2
--oo, nhu c6 mt Sl,l' bjft d1nh na.o d6,
tUc Ia Sl,l' xac dinh se kern chinh xac a vim.g dung djch loing.
5. CAN BANG DUNG D!CH L6NG - CAU TU KHL
flQ TAN CUA KHi TRONG CHAT L6NG
1. each biiu thl d9 tan cUa khf trong chit lOng .
Ciing nhu chlt rdn, chlt khf chi boa tan c6 vito cMt long. N6ng
d khi trong dung djch bio boa n6 18. dr) tan ci:Ja khi. Hin nay chua c6
dan vi na.o dugc cbA'p 13m dan vi chfnh thUc tlq d tan ci:Ja
khi. NguCri. ta tht.Wng dUng h s6 taD. vA mt s6 each thi kbac.
sO tan a cUa. khi trong cMt lOng a d TVa du6i 8p suA't
ritng phAn p ci:Ja khi trtn cMt lOng khi c6 can bAng 18. thl tich khi tim-
trong dctn vi thltich cUa dung mOi. Vtan (do aT, p) 1A tich khi
tan trong the tich v cila dung moi, s6 tan cila khf se Ia :
79
v
a = ....:.!l!n.
v
(X.23)
H s6 tan a cho hilt m()t tich dung mOi lOng hoi tan dtn;IC bao
nhieu the' tich khf I:J T va p da cho.
2. Anh hi.IO:ng cUa ip suit lin d'9 tan cUa khl. D!nh lu't Henry
Gqi khi c6 kh3. nang boa .tan vao dung moi lOng 13. tlr 2, gQi
llf V8J.l} 18. the'hrni hqc ella n6 trong pha khi va trong dung djch lOng
can bAng v6i nhau :
11f = (T) + RT/nf2
J.t} = (T. p) + RTJna
2
Tit can b8.ng = suy ra :
ln.!l_ = {T, p)- (T) =Ink
a
2
RT
(X.24)
(X.25)
k lit bam ctia Tva p. 00 qua 8nh hUCmg nhO cU.a p vito tht! bOO. hqc
ella khf 2 trong pha lOng thi c6 the chAp k 18. hAng s6l:J T = const ;
k gQi 18 s6ho*c hJng s6 Henry.
a) Dung d{ch Ia khOng li tudng nhung loiing (d tan be ella khi)
1) Khi tdn dung djch xU' Slf li tllcing : djnh /urJt Henry ve dt) tan cUa
khi trong chd"t lOng. Khi khi chi tan ft, c6 chA'p nMn d a
2
bAng
ndng dQ x
2
ella khi Wng pha lOng. Vi khi 18 li ttrOng nen f
2
= P2 13. cip
ella kbf Wn dung cJ1ch can bAng v6i khf. Khi d6 (X.25) trO thAnh :
(T = const) (X.26)
D6 18 djnh lu(it Henry do Henry tlm ra bAng thgc nghim DAm 1803,
n6 mO ti S\1 ph1,1 thuQc giita lip sua:t khf P2 vA dt> tan x
2
ciia khi trong chAt
lOng. Bie'u thl1'c d6 hoAn toAn t:riing vOi hf thlic Henry (VII1.8) P2 = kzx
2
mo tit lip suAt hoi biio boa P2 ella cha:t tan 2 trong dung djch lOOng.
80
can bAng trong_bai qua tiinh boa tan khi 2 vao cblft lOng va bOO. bcri
cU.a cba:t tan 2 tir dung djch lOng 13. hoAn tolm tucmg duang nhau
nhit d()ng. M()t ben 13. can bing giita.khi va dung dicb bio boa ciia n6,
m(>t ben 18. can bAng giUa dung djcb lOng va bi:ri bio boa ella cMt tan. ca.
hai can bang nay tua.n theo dinh Henry khi dung dicb 18. lo8ng.
Tir (X.26) suy ra aT = const :
x
2
= KP2 (K = 1/k)
(X.27)
D6i v6i dung djcb lo8ng, x
2
ti 1 v6i m
2
va c
2
, do d6 ciing c6 th!
OT=const:
m
2
= K'P2 Cz = K"P2
(X.28)
M
2
18. kh6i luqng pban tir ciia khi 2 thl kh6i luqng khi tan trong
dan v! th! ticb dung djcb dung mOi) 0 T da cbo 18. CQ = M
2
c2. va
theo (X.28) n6 bAng :
qz = M
2
ez = M
2
K"P2 = K"'P2
(X.29)
(d6i v6i dung d!cb lo3ng, c6 cblfp I lit dung djcb bing 1 lit
dung mOi). J)mjj nhiing d(Ulg (X.27), (X28) va (X29) djnh Henry
c6 the pMt bii!u :
Dtii vbi khi hinh tlulnh dung djch khOng Ji tuOng viii dung mOi va chi
tan it trong dung mOi, dq tan cUa khi bilu thj bdng n6ng dq x, m hay c,
ho{ic bdng khOl llllftlg khi tan trong dun vj thl tich dung mOi Ja m{jt dqi
ll4fng ti 1 thu{in vbi Op sutlt cdn Mng cUa khi trin dung dfch.
Ghi chU. NhUng sai lcb d6i v6i dinh Henry duqc tMy khi
khi boA tan tham gia vao niong me bOO. hqc v6i dung mt">i, pba.n li
bAng ion, thi d\1 tru'Ong hqp NH3, HO, S02 v.v ... tan trong nuUc. Khi d6
d() tan toAn pMn thuOng 16n va klu"mg tuan theo dinh Henry.
2} H qud cUa djnh lw#t Henry. GQi V tan Iii tM tfch khi tan trong the tfch V ciia
duilg mOil! Tva du6i ap sun P2 ciia khf. Vi kbf duqc coi Iii If tlll'mg, ta c6 :
81
P:2 V tan = n
2
RT = RT
M,
g
2
lA k:h6i \ugng k:hl tan trong thi tich V ciia dung moi, dem chia v6i. V se dugc kh6i
IU(1ng k:hi q
2
tan trong dan vi tbt tich dung mOi :
P2V1an g2 RT RT
----=q2-
v V M
2
M2
Theo d!nh nghia (X.23) a = V tanfV lA s6 tan a cUa k:hf, do d6 nu k:et hgp v6i.
(X.29) se dugc :
(X.30)
Nhu dlJ1 vdi kht coi nhll khi li Mlng va tudn theo dinh lugt Henry, s(/ tan a
cUa 116 trong cluft lOng chi phf! thuqc vdo dtj, kMng phf! thuqc vdo dp sud't. Dieu
nAy c6 nghia lA a d khOng d6i, m(lt thi tich nhli't d!nh ella kbl (duffi lip suM c!n
bhig 'ella khf) dugc hoA tan trong dan vj thi tich dung mOi, kMng ph \I thul)c vao gili trj
cila lip suli't.
b) Dung dich Iilli tudng. D(J tan If tltdng cUa khi. Ntu dung djch 18. li
tll&ng (a
2
= x
2
6 x
2
) va ni!u khf ciing xU sg li tubng (f
2
= P2) thl tir
(X.26) P2 = kx
2
suy ra k = (Ung v6i x
2
= 1). Nhu vl}.y, nu khi 2 hinh
th3.nh dung dich 11 tubng v6i dung mbi thl k c6 _y ngh1a vl}.t If lil lip
hdi blio boa ella c6u tU 2 nguyen cMt 0 thai hoi lOng lJ d T
ella thf do d tan. Do d6 b T const :
P2 = x
2
x
2
=
P2
(X.31)
D6 13. bieu thUc ella djnh lw)t Raun -Henry vi tan If tudng cUa
khi trong duft lOng.
6. CAN BANG DUNG D!CH LONG - CAU Tlr RAN
1. Cin dung d!ch lOng vbi tinh thi cUa ciu tlr i
Ta xet bai tinh cln bAng dj th! giila m()t pha ran chi chUa mt clfu tir i
nguyen cMt va mt pha lOng c6 hai clfu tir (dung dich) trong d6 c6 clfu
82
tir i. Khi d6 dung <ijcb ta biio hOO. d6i v6'i i. N6ng d xi ella i trong dung
d!ch d618 d(J tan ciia i b T v8 p ngohl da cho (p chi c6 inh bubng rA"t be).
Gqi 18. tht! boR bqc ella i trong pha lOng (dung djch) vii J.LfR Ia th(
boa hQC ella i trong pha rAn nguyen cha:t. Dieu can bang 18.
1-lfR = ; JlfR chi pb1,1 thuc vito T vii p vl i trong pha r&D 13m nguyen
cMt, cOn pb1,1 thuc ca. vao _thrum pMn ciia-dung d!ch theo thrtc :
1-lf = 1-1fL (T, p) +
Dieu kin can blmg 1-1?R = ll-[ dfin tm :
. JlpR _ j.lpL
lnai=l I
RT
Tit d6, d1J3. vao (VII.35) lAy bam theo T b p = const trong dieu
kin cAn blmg vAn t6n ngbia 18. dung djch vAn lA biio hoii d6i vdi i
se dm;tc :
(
a In a;) = _!_ [_!___ ( flioR J _ _!___( flioL J1 =
aT p,bh R aT T aT T
=
(bh = bao bOa) ; :
(
8lna-)' HPL - HPR
__ 1 _I I
Of p,bh RT
2
(X.32)
HfR 18. entanpi ella 1 mol i r!n nguyen chAt cOn HfL 18. entapi mol
rieng phin ella i trong dung djch b thai chuAn. Nt!u khi tinb
d ai ella ca::u tir i trong dung dicb, ta lAy thai ella ca::u tir i
lOng nguyen cha:t lAm thai chu4.n (tUc 18. l\j_ = 1 khi xi = 1)
thl HfL = HfL = entanpi ella 1 mol i lOng nguyen chAt. Khi d6
Mli = HfL - HjR se 18. bit!n thien entanpi trong qua trlnh chuytn 1 ffiol
83
til blDg thai i rio nguyen chAt sang tr<).llg thlii i lOng nguyen cha:t. N6i
khlic, A1ij 18. nhift n6ng cluiy Luc,i ella 1 mol i rio nguyen chcit, do d6
(X.32) vit Ia :
(a:;;, t. = ( 8/";;x' t. =
(X.33)
H thiic (X.33) c6 xet.bai c8.ch We nhau toY theo i 18. dung mOi
hay cMt tan.
2. Him nghifm
Slf ket tinh cUa dung mbi til dung djch IOting ch.ttt tan. D6i v6i dung
djch lOting, khi tam tha:p nhit d t6i bilng di8m T ella dung dich thl
dung djch bit dau kt tinh (dong bang). 0 dfty chi xet tnrimg hqp tinh
the hin ra 18. ella dung mOi 1 nguyen chAt cAn bang v6i dung djch lOng ;
ditu nay c6 nghla Ia a T (bang dil!m). dung djch nil thilnh biio
boa d6i v6i dung moi va phlin mol x
1
ella dung mOi trong dung dlch bao
boa d6 th! tan ella dung mOi trong dung dlch.
D6i vOi dung djch loiing (chinh xac !avO cilng loiing). y
1
= I va a
1
= x
1
,
M thllc (X.33) tril thilnh :
(
8/nxl) = Lno,l
or p,bh RT
2
(X.34)
H thiic nay 13. trtKmg hqp rieng ella phuang trinh SriJde-l.,u Satdlie
bil!u thj S1}' ph\1 thuc tan cUa ctlc cdu tlf trong dung djch Ji tudng theo

0 lip sui't khi ngoai p = P
0
= const, (X.34) c6 th8 vit:
dlnxl = Lnc,l . d;
R T
So! tich phftn phuang trinh nay tfi bang diem T cua dung djch (c6
th3.nh pUn x
1
) dn bang di8m T
0
ella dung moi 1 nguyen cba:t (t'ing v6i
Xt = 1) se cho (khi coi Luc,l nhu khOng d6i trong khoc\ng nh.it d nhO
d6):
84
1 L To
Jdl
_ no,! J dT
nx
1
--- --
R T
2
x, T
=
L"'"'"'':O;(T:2
0
0;--__:T:..)
Jnx
1
= '
RTTO
D6i v6i dung d!ch 2 tir r:lt loing ctfu tir 2, ta c6 tht cba:p hai
SJ! glin dUng :

T;
2) lnx
1
= ln(l- x
2
) -x
2
(vi x
2
<< 1)
Khi d6 nu 9 = T b = T
0
- T va gQi 18. ht;l biing dilm ella dung
d!ch so v6i dung mOi cha:'t, se dugc :
RT
2
9=dTb= -
0
-x
2
Lnc,l
ne'u chuyen tlt n6ng d(.l x
2
sang n6ng dt') molan m
2
(d6i v6i dung
djch lafulg, x
2
= M
1
m
2
!1000):
RT; Mt

9=.6.Tb=Kttnz;Kb= =:-: o
lOClOLnc.l lOOOAnc,l
(X.35)
Kb Ht hAng s6 hiln Anc,l = "Lnc,liMtla n6ng cluly rieng
d6i vOi 1 gam ella dung mOi nguyen chllt. C6ng thUc (X.35) trllng v6i
(VIII.19) da gi6i thiu i'J chuang VIII.
3. xac djnh dQ va s6 dQ biang phamng phBp hitn nghjfm
D6i v6i dung djch thJ!C, ta phi'ti dUng M thl'rc (X.33). H thUc nay
cung cAp mt')t trong nhilng each xlic d!nh di) va s6 ho{lt dQ bang
phllang pbap him nghim.
a) .xtlc djnh dt) cUa dung mOi : Theo (X.33), iJ p = const:
85
SJ! tich phan gifi'a hai bang ditm T
0
(ella dung mOi nguyen chit, Ung
v(ri a
1
= 1) vaT (ella dung lofulg, Ung v6i mt gici tti 3.
1
n8.o d6), T
va T
0
rAt giln nhau, cho phep chAp Lnc,l = const. Khi d6 se dugc :
Lnc I T - T
0
Lnc,l .1
Ina, -- (X.36)
R 1T
0
RTI
0
1 = t.\Tb = T
0
- T 18. dQ hl,l bang diem ella dung djch xcic d!nh bang
(ban Tir d6 suy ra a
1
va y
1
= a
1
/x1
b) Me djnh hogt vO h stf hogt cUa chtft tan. Theo (X.33) d6i v6i. dung mOi :
L
dllm
1

RT'
Tir9 = T
0
- T suy ra d9 = -dT(vl T
0
=const), do d6:
LIIC,l Lnc.l
-dina
1
=--dO --dO
RT
2
RT
2
0
BAy gicJchuy!n sang dQ ella ch!t tan d!!a vito b thUc Gipxcr- Duhem (X.21):
n
1
n, Lnc 1 O
dlna
2
=--dina
1
=--- d
n2 nz R-r,;
Gii tlui n6ngd() cba"t tan bil!u thi Mng dQ molan m2. Khi d6 n
1
= I<XXl/M
1
v8n
2
= m
2
,
M
1
Ia kh6i Iuqng pban tlrcUa dung moi. Ta duqc:
86
dina
2
=
1
LIIC,, d9
RTuM1m2
Nhung theo (X.35) bing s6 han ngbim Ja:
K
_ RT;M,
,-
IOOOLnc,l
(X.37)
ti:r d6 c6 tht x'.c djnh ne'u dii bitt q m(lt tr\lfig thai A nao d6 vit neu dido duqc e
lJ m(lt diiy n6ng d(l m
2
khic nhau:
B
I I d9
/n(a
2
)s = ln(a2)A +- --
Kb dm
2
A
(X.38)
Phuong phap nity c6 nhuqc ditm lil. khi chqn dung djch v6 ding lOOng litm fr\lJlg thai
A thl m
2
-+ 0, 9-+ 0, d6ng thOi. s6 hl).llg cUa tfch pban vi ciing trlJ thitnh
aJ, do d6 SJ! tfch phAn se thie'u chinll xik.
Dl! tninh t1nh d6, ta dUng h3m phl,llfq :
. 9
J=l--- (X.39)
Kbm
2
ve y nghia li thl j lit d do tinh sai 1ch so v6i nhfrng thuc tinh -cUa dung djch
loiing. D6i vm dung djch vO cUng loiing 9 = K!P1
2
va j = 0. D6i vm dung djch lhJ!c
khOng dU lOOng, 9 Kb m2 va j 0.
Tit (X.39) suy ra 9 =(I - j)"KIP1
2
, do d6 :
d9 =(I- j) Kb dm2- KJ>l02dj
Dlla gili trj nay cUa d9 v3o (X.37) se dUQc :
I d9 . dm
2
. dm
2
.dm2 .
d/na
2
=- .-=(1- J)---dJ=--- J---dJ
Kb m2 m2 m2 m2
Omytn

= d/nm2 sang ve tnii :
dln..!L= dlll"f
2
= _ _Ldm2 -dj
m2 m2
Khi m
2
= 0, j = 0, d6ng thCri y
2
= I va lg-f2 = 0 (dung djch v6 cUng loiing). Do d6 ntu
tfch phAn phuong tr1nh tltn tit m
2
= 0 dtn m
2
dii cho, ta dtrQC :
(X.40)
lJ dll.y SJ! tfch phlin kh6ng g*p kh6 khan Vi khi ID2 -+ 0, j -+ 0, ti s6 j/m2 vAn giii' dUQ'C
m(lt gili lrj hUu hl!-n. Ta X!ic djnh tlch phAn (X:40) theo phuong phip d6 thj. Tru&c hCt Xlic
djnh 9 va do d6 j d6i vOi m1 diiy dung djch c6 n6ng d m
2
kh3.c nhau va be d!in. OJ!Og
d6 thj j/m
2
lheo m
2
. Ngo!).i suy cho t6i m
2
= 0. Din tfch du6i dui'mg cong thu dUQc giila
m
2
= 0 va m1 gili lrj m
2
dii cho nito d6 se ling v6i gi;i tri cUa tfch phll.n ph8.i tim. TU d6
suy ra Y2 va a2 = Y2m2.
R7
D6i v& nhilng dung dicb rft loing, ti s6 j/m
2
dl!-t duqc gi<i'tlj g4n nhu hAng s6 va c6
tnt! dua ra ngoai dl(u tfch pbAn ella (X.40) va he lhlk nay trb lhilnh :
lrry
2

m,
(X.4l)
3. aq tan li ttmng cUa chit trong chit tOng
Ta t:rls (X.33) khi i cMt rAn (i <:! 2) tan trong dung mOi lOng 1.
Gia dung djch Ia 1i t<idng. Khi d6y; = I va a; = X;. (X.33) tri1 tbanh :
(
5) =
i'll' p,bh RT
2
(X.42)
(X.42) Ja phlldng trlnh Srdde-Lu SaUJlii, do SrOde (Schroder, 1890)
va La Satalie (1894) lam dl)c lAP da tlm ra. N6 bitu thj quy
biln thien d tan Xj cua i rio tan trong dung <ijch If tulmg theo nhit d.
Vi Iyc,i luOn luOn > 0 cho nen tlr (X.42) suy ra. ring d tan li tuUng x;
cUa cluit r&n tdng theo d(J T. Ngo3.i ra, a p const. df) tan 1i tuUng x;
chi phlf thuf)c vdo T, khlmg phlf thuf)c vdo bdn clutt cda cdu tU khdc i,
dij.c kMng phlf thuf)c vdo dung mOi.
Nlu coi Lnc,i 18. nhit n6ng clu\y clia
l mol i rAn nguyen ch!ft a nhit dQ n6ng
cbily T
0
va chAp glin dJ!ng ri!ng n6
khong d6i ttong roan khoilng nhiet dQ til
T
0
Mn T thl sq tfch phan (X.42) giila 2
nhit dQ nay a p const se cho :
L
00
;( I IJ
lnxi=R To-T
- Lnc,i T-To
-R. 1T
0
(X.43)
Vl X;< I, lnX; < 0, con Lno,i > 0 cho
nen tiJ (X.43) suy ra.dng T < T
0

88
-
T
.HinhX-5. Sl,rphy lhuc dQ tan li
tuOng cUa cMt dn trong cMtlOng
vao dQ.
COng tblic (X.43) cho phep nlt ra quy tic sau diy <I tan If tuimg
ella cMt rAn:
Logarit cUa dt) tan X; 10 hdm nluft cUa 1 rr' c6 the dUng logarit
pbAn vil chuyl!n (X.43) sang :
lgx _ Lno,i (-1 _ _1_)
1
- T
0
T

lgxi = Luc,i _ Luc,i = B _ A
8,314x2,303T
0
8,314x2,303T T
trong d6 Lnc,i tinh ra jun. Nlu bieu di!n lgxi theo l(f se duqc
thing c6 d6c bAng -L,d8,314 x 2,303 (hlnh X-5).
CHOONGXI
cAN sANG HOA HQC
1. AI Ll,fC HOA H9C
1. Nguyen If Becto:IO
Ai IJ!C hoa hQc bitu khci nang phAn Ung cUa aic cMt v6i nhau. Tomxen
(Thomsen, Dan ffi!_lch; 1853) vA sau d6 Bectol6 (Berthelot, Phap, 1867)
de nghj do ai 11}'c hoi hQC bang nhit luqng tOa ra trong phin Ung holi
hQC. Y kit'!n nAy dugc Bectole, d\ffig thanh nguyen If cOng ctfC dqi, thOOng
gQi Iii nguyen li BectC1l6 (1867) : "M9i bie'n ddi hod hqc xdy ra md kh6ng
c6 slf can thip cUa ben ngotli diu c6 xu hiiUng diin ra theo chiiu sdn ra
mtjt cluit hay m{Jt hf chd't tOa ra nhiiu nhit nhdt". Nhu theo
1i Bectalo, cac phin Ung dy ra n_r nhien phai 18. phiin ling tOa
nhit va 3.i ll,fC boa hQC c6 th6 do b3.qg hiu Ung nhit ella ph.ln iing.
Nc!u gqi clfv va dip lil d(> do <ii h,rc ho3. hQC trong c<ic phiin Ung d.ing
tfch va dAng ii.p thl theo nguyen li tren :
dfv =- Qv = -CiU; dip=- Qp = -dH
Theo nguyen If d6, ph:in lffig chi c6 the xAy ra tl! nhien a V = const
nc!u Qy < 0 hO?c dU < 0 va b p =canst nu QP < 0 AH < 0.
Trong tht!C t, m('t s616n phiin Ung xay ra a nhit d(' thl!Cm.g hay giln
nhit d thl.Wng lA nhfing phiin-Ung tOa nhit. Nhtmg c6 m('t s6 kh6ng it
pban Ung tho nhit van ra duqc tl,l nhift lA a nhit d cao.
Ngoai ra, If Bectcrl6 mAo thuin v6i SJ! t6n t!;li nhOng phan Ung
ngh!ch. dien ra theo ca hai chieo a cUng nhit dQ, nhfrng pban Ung
nAy da:duqc Bect6M (Berthollet, Phap) ra tir 1801, do d6 no philo
llng lA t6a nhit theo chieu nay, n6 phili lA tho nhit thea chieu kia.
(1875) va bit lA POtulitxin (1874) da c6 vai trO co
han trong vic V!;lCh rO sai l!tm ella nguyen If Betcrl6 trong truCmg hqp
90
tOng quat. POtulitxin chi rO nguyen li d6 chi Ut ml)t dinh gi6'i
&T =OK.
2. Thuyift dOng d&n ve 61 lo,rc ho6 h9c
Nguyen li Bectalo di,TR trfn ml)t tien dUng : cac qua trinh t\l nhien
(khOng c6 Sl! can ella ben ngOO.i) dien ra theo nilo sin ra
duqc cOng nMt (nguyen 1i cOng cgc Nhung sai lAm ella
BectolO 13. lJ ch6 di d6ng oMt cOng C\fC ella pbin ltng VOi Ung
nhit ella phlm Ung.
Chi tren co sO nguyen 1i II mm c6 dU<JC ml)t dioh lw;mg <tUng
dan lii li!C ho6 hQC, do Gipxa (1876) vil Hemhon (1884) 1M ra. Van Hop
phcit trik nAy (1885) v8 cho n6 ml)t tOO.n hQC khi suy ra
dinh tlic d1,1ng kh6i lw;mg b!ng dl)ng h!c hQC (dioh My lllc
tl116'c chi dU<JC cac nhll khoa hQC Th1,1y di4!n Gunbe (Golberg) v3 Vagio
(Waage) thi(t (1867) b!ng con duimg ngbien cUu t6c dl) ella ph3n
Ong) .
. [}I) do ai ll!C bOO. hQC kh6ng phcli 18. hiu Ung cUa ph3n Ung rna
18 c6ng c6 th! thu dU<JC khi h8.nh phlm (mg theo each thl$1 ngh!ch
dQng. tUc lA blng dl) giAm ella cac tb( nhit dQng tuong lhlg :
dlv = -.1F = Tt\S- dU = Av,max
dip= -t\G = Tt\S- dH = A'p, max
(XI.l)
(Xl.2)
Tir (XI.l) va (XI.2) ta tMy nguyen 1i Bectol6 dUng trong hai truCmg
hqp rieng :
1) Khi T= OK,khi d6dlv = -M'=-AU;
dip = -dG = -.MI. b OK, nguyen li Bectol6 dUng kh6ng c6
1 va kh6ng c6 quli trinh thu nhit n3o dy ra tJ! nhien b OK dU<JC.
T dmg OK thl lw;mg dH c3.ng bitu th! chinh xcic
dG va xlic suAt ella qua trlnh theo tba nhit ci'tng IOn.
2) Khi AS= 0, nghla Ia khi, pM hQP v<li (BAG I BT)p =-AS= 0, cong
c6 ich C\fC (A'p,max = -85) kh6ng ph\] thul)c vao T.
91
each dinh nghia dUng dAn ai IJ!C bOO hqc cOng giAi thich sao m(lt
trinh thu c6 the xiy ra tq nhien : ..1U va MI trOng tn:rUng
hqp nay c6 gia tti dUdng, qwi trinh mu6n ra dtn;1e chi c6 ml)t
bil!n thien entrOpi .6.S va m()t nhit d() T dU cao de Jam cho T.6.S IOn han
LI.U ho(!c MI.
2. CAN BANG HOA HQC
Phdn Ung thU(in nghjch hoQ hr;c g6m hai phin llng dan gi3.n han :
ml)t pM.n lln.g va ml)t phin Ung ngh!ch ra d6ng th<Ji theo hai
chieu nguqc nhau v6i t6c d(l kbac nhau. Phin llng ngbich tOng
qwit m6i hk Ia qu3. t6ng hqp ella hai phin Ung va nghich d6.
Tlly theo rueu kin, m(lt trong hai chieu, hay nghich c6 the chim
tru thl! va phin Ung nglqch t6ng qwit se dien ra theo chieu d6 cho
tffi khi t6i trl;Ulg tluii c;in bAng boa hQC. 0\n bAng nay 18. m(lt cdn
b&ng dl)ng vi hai qwi trinh va nghich viln ditn ra nhtrn.g v6i t6c d
bAng nhau cho nen thanb ella cac cha:t c6 trong pban Ung ke tir
h1c d6 khOng thay d6i nita.
O.c plu\n Ung bOO hqc n6i chung deu 18. phin Ung nghich bOO
hQC. Tuy nhien c6 nhfing phiin Ung trong d6 m(lt trong hai chieu rflt yl!u
khOng dang ke va nhGng phin 6ng d6 thqc t Ia phiin 6ng m(lt chit!u,
dien ra cho dn cllng.
D6i v6i nhilng h trong d6 c6 pMn 6ng bOO hQc dien ra, nhilng qua
trinh vO cllng nhO trong h Ung v6i nhGng h thUc sau :
dF = -SdT - pdV +
dG = -SdT + V dp +
(XI.3)
Nu qwi trinh trong h dien ra aT. V const hay aT, p = const nhGng
M tht!c tren triJ thiinh :
dFT,V = dGT,p = (XI.4)
Trong nhling dit!u tuang l'tng, qua trinh chi c6 the ra tq
nhien theo chieu 13.m cho :EJ.lidnj < 0 va cAn bAng trong h se t6i khi
= 0.
92
Gi.i thir trong h c6 nhUng cMt A
1
, A
2
, .. , B
1
, :8:2 ... c6 kh.i nang
pbim llng vm ohau theo phuung trluh boa hQC :
v
1
A
1
+ v
2
A
2
+ ... = v'
1
B
1
+ v'
2
Bz + ... (Xl.5)
Ne'u ph.in Un.g tOng qua.t ra theo thuq.n (tir tnli sang ph.ii)
thl A
1
, Az, ... Ia nhilng chlft dJiu, B
1
, B, ... Ia nhilng chlft cu6i hay san pl$n
cUa ph.in Un.g. Vi nhO'n.g b'ie'n dn
1
, dn
2
, ... dn'
1
, dn'
2
, ... s6 mol cUa
chOng lA do ph.in Un.g ga.y ra cho nen phili ti 1 v6i nhO'n.g h s6 ti 1Ut;111g
v
1
, v
2
, ... , v'
1
, v'
2
... cUa chllng trong phuong b"inh ph.in Un.g tUc 1A:
_ dn
1
= _ dn
2
= ... = dn't = dn'z = ... =dA>O (Xl.
6
)
v
2
v'
1

0 da.y, d6i v6i nhUng cu6i (cMt dUQC hlnh th8.nh) dllj_'> 0 cOn d6i v6i
nhilng chit dJiu (ch!t m!t bOt di) dn; < 0, do d6 dJiu "Am" lrUOC
nhfrng ti s6 dn/vi va dAu "duong" tnWc nhO'n.g ti s6 dni'/ Vj
1
b.io dam
cho dA c6 gii tri duong. Nhilng ti s6 d6 lA gi6ng nhau d6i v6i mQi ch!ft
trong ph.in Un.g v3. c6 th! vit duOi vi phAn cUa mt <4i luqng A nAo
d6. hrqng nAy gQi IA tifn triln cUa phlin Un.g. N6 cho bit kh6i
11.lQD.g cUa m6i cha't trong ph.in Un.g thO:i di!m dang xet va do bAng
nhO'n.g dan vi nrcmg duong nhau, Un.g v6i phuong trinh ph.in Un.g. Thi d\J
trong phim llng :
N
2
+ 3H
2
= 2NH
3
dan vi kh6i luqng tuung duung d6i vm cac chit Ia (N
2
), (3H
2
), (2NH
3
)
nghla 1A 1 mol N
2
, 3 mol H
2
vA 2mol NH
3
. ru I mol N
2
m!ft di thl n6
di d6ng thai v6i 3mol H
2
va sinh ra 2mol NH
3
. D6i v6i cUng mt
ph.in Un.g, bie"n thien kh6i lllQD.g, do bAng nhfrng dan vi nrang duong
lit gi6ng nhau d6i v6i mQi ch!ft 0 Mt k.1 thCri diem nito.
!)(\ tin triin ). biEn thien trong pli'!ffi vi til 0 I. N!u dA = 0, phim
Un.g chU'a dien ra, di.. --i>A A = 1 thl :
= --i> ... = =M= I
I I I I I
Vt Vz Vt Vz Vj
93
' '
tllc 18. &nj = Vj v8. do d6 .6.Dj = Vj
DQ tit!n boa hQC A chi trung cho mi)t pluin Ung nhA"t d!nh.
Nu trong ra nhitu ph8.n Ung thi mOi phlm Ung tntng bang
mQt dQ tritn ritng (),
1
, A,, ... ).
Dua nhihlg gici tri ella dni rUt ra ti:r (Xl.6) vito t6ng LJ.Lidni se duqc :
' '
= (( VtJ.lB
1
+ V2J.lB
2
+ ... ) ( Vti-1A
1
+ V2J.lA
2
+ ... )]d}. =
= ( - flA; )dl. = Afldl. (XI.7)
v6i:
(XI.8)
:EvillA; 18. t6ng tht! hQC ella nhihlg cba:t cU.u IA"y theo nhii'ng h s6 ti
luqng ella chUng, LviJ..I.Ilj 18. t6ng th hoci hQc ella nhihlg cha't cu6i
(nhiing slm phAm ella ph_;.\n Ung) cfing IA"y theo nhfing M s6 ti hrqng ella
chOng. (Tir (XI A) va (XI.?) ta dugc, d6i v&i phiin ling hoci hQc:
(Xl.9)
ti:rd6:
(!l.v = =Aft
(XI.IO)
Vida s6 ph:ln Ung dien ra (I T,p const. nen ta se chi chll y Mn ham
Gipxa hay th dAng ap G. 0 T,p const, phim iing dien ra tl,l' nhien theo
chieu Ung vOi dG T,p < 0, do d6 :
&J.l = :Ev;J.ls. - EviiJA < 0
' '
(XI.ll)
bCri vl, theo d!nh nghia, d/.. > 0. Dieu kin (XI.ll) tUC1Dg doong vOi
94
. '
l:ViJ.lA- > LviJ.lR (XI.lla)
' '
Nhu phAn l'rng bOO. hQc chi c6 the dien ra t\1 nhien theo li:l.m
giiun Lvi J.l.A; , s6 h!.lng nay phii c6 gili tti IOn d6i v6i nhiing cUt
han 13. h nhiing e;Mt cu6i. ChUng nao phoin iing cOn chua cAn bAng th1
I: vi J.l.A- cOn giiun, d6ng thai Lv;J.!B cOn tang. Cu6i cilng khi I: vi J.lA
' ' '
trO thanh bWtg Lv;J..LB; thi h t6i thai cdn b&ng ho6 hl}c, Ung
v6i dGT,p = AJ.l(IA. = 0. Vl dA 0 nen kin cAn bAng 18. :
(XI.l2)
kin nay tucmg Ung v& qrc ctia hilm G = f (A) 0 T,p const,
rUtrati:r(XI.lO):
(
00
) = = o <XI.l3)
8/- T,p
Ciing tuang liJ nhu dil!u kin ella can bing bOO. hQC 0 T,V const
se 18:
(
BF) = = 0
ifA. T,V
(XI.14)
- '
G' = Lvi GB; = LviJ..I.B; v3. :-
. (XI.15)
D{li luqng AGT,p gQi ll thE d&ng tip cUa phdn 'Ung, n6 blng bin thien
the! ding lip ella h do ph8n Ung gAy ra khi s6 mol c8c chA:t bAng h s6 ti
luqng ella chU.ng trong phuang trinh pban Ung. Dinb nghia n3.y Hi ml)t
quy uUc rna ta phii nh6' khi 18m cac pbep dnh vi! can bAng bOO. hQC.
Thl d&ng tip chuJn 1!0 ella phan Wg l8 gili tti ella khi tit cA eck
ch>t <U!u dU<JC 11 trl!Dg thai chulfn:
95
(XI.16)
Chll y rAng the' dp AG ella pbin Ung ph\1 thuQc vao Tva p nhung
thE d&ng clp chudn .6.0 ella ph8.n Ung chi ph1,1 thuQc vao T vi b tllJlg thai
chuin cac ap sui"t nl$1 gill tri c6 djnh bang I atm (N6i dfutg thl
chua c6 quy djnh th6ng nMt ap SMt chuin d6i vm cMt tan trong
dung djch lOng, tuy nhien thl! bOO. hQC ella nhfing chit My chi ph1,1 thuQc
chU yl!u vao T, rft it vao p, do d6 c6 the bO qua 8nh hubng ella lip sua:t,
coi nhu lip sua:t vAn bAng 1 atm).
3. O!NH TAC DI,JNG KHOI LliQNG VA
PHUONG TRiNH OANG NHieT CUA
PHAN liNG HOA HQC
1. Thii"t l._p dCJing t&ng quat nhat cUa djnh theo phwng phap
thi" nhl;t dqng
Nl!u b T,p canst dit!n ra pbin Ung (XI.S) :
v
1
A
1
+ v
2
A
2
+ ... = v;B
1
+

+ ...
thl th dAng lipdG ella phin Ung xic dili lX1i (Xll5):
.
AG = :EViJ.lB- - LViJ.I.A-
' '
Nu mQi cMt di!u b trlplg tM.i cbuAn, tri:Ing vOi thai chuAn ella clio
ti:r nguyen cha:t, thl th dAng 8.p chuAn /10 ella phiin Ung duqc xac d!nh
biJi (XI.16):
dod6
0 ' 0 0
AG.- AG = -u:c)- )
I I '"H; I I Aj
Phoong trinh nay dUng v<Ji mqi h Wt kl, ddng cilng nhu di the.
96
Vi bin thien th bOO. hQC khi chuy6n I mol cha:t i tlr thai chulin
sang thai da cho bang :
cho nen:
V
a'
. f,
J.li - 1-1f = RT/n -
1
= RTlnai
fo
'
. '
VI V2
AG- AG
0
= RTln
881 882
= RT/nTia
v
1
v
2
a AI aA2 ...
(XLI7)
(XI.l8)

v
a'
A;
18. tich cac s6 c6
'
chia cho tich c<ic s6
c6
'
Khi c6 cAn bOng hoa hqc, AG = 0, do d6 :
AG
0
=-RT/n (XI.l9)
VI V2
aA aA ...
. ' 2 cb
Oic a A;, a
8
i. trong (XI.19) Ia nhihlg d khi c6 can bAng bOO.
hqc (cb = cAn bOng), klulc vUi nhilng gia tri aA, , as, ... trong (XLl7)
hay trong (XI.l8) chi 18. d ling v6i mt giai dien bin b<t"t kl
nao d6 cUa ph8n ling, c6 the 18. thai dciu clia ph8n ling cbing
(XI.l9) c6 th<! vit:
(
' ' J
v
1
vl
aB a8:2 ... AGo
In
1
= --- = f(T)
v, v2 RT
aA aA ...
I 2 cb
Vi AG
0
chi phi} thuc vllo T, nen v phii pbuang trlnh nay 18. b8.m chi
cila T; iJ T const n6 18. mQt hAng s6, v trai cUng Ia mt bang s6 va
97
ban than h.tqng sau dAu In cling 13. mQt bang s6 gqi 13. Juing sO' cdn
bdng hoti hqc Ka :

(Xl.20)
Sau nay, khi khOng SQ' nMm IAn thl b6 khOng cAn ghi lei hiu cb a
chiln. Phil hqp vm (Xl.20), phuong trinh (Xl.l9) c6 tM viet:
I dG
0
=- RTlnKal
va (Xl.l7) c6 thi viet :
.---------,
I dG=RT(lniia -lnKa) I
(Xl.21)
(Xl.22)
Phucmg trinh (XI.20) 13. bie'u thUc t6ng quat nMt ella djnh lut.it ttic
khtii llllfllg.
SV: suy ra phlllJilg trlnh (XI.20) va (XI.22) 18. ho.fm toan t6ng quat
va kh6ng d1,la vao mQt quan nao co eh ella qua trlnh.
PhlllJilg trinh (XI.22) gQi lil phllang trlnh d&ng nhift cUa phdn Ung
hoil ht:Jc, hay phuang trinh Van HOp, 18. mQt ti'ong nhiing phlllJilg trlnh
quan trQng ella nhit dQng lJ!C hOO. hqc.
DuOi da.y ta se xet nhiing truOng hqp
2. Cin bAng hoB hqc dOng thi trong pha khl U tll'lJng
a) H&ng so' cdn b&ng Kp D6i vdi khi If tuCmg, <lj_ = fi = Pi do d6 d6i
vm phl.n ilng trong pha khf If tuimg K, = KP = f (D.
l
. J l . . J
Vf v
1
v
2
Ps PaPs ...
K =II __ , = I 2
P vi v
1
v
2
PA PA PA ...
'cb
12
cb
(Xl.23)
D6i v6i khi li tuimg, bang s6 ca.n bAng KP chi thut"?c vao T.
98
DuOi <4flg (XI.23), djnh tac dl}.ng kh6i lm;m.g thj. m6i lien h
djnh hrqng giii'a nhiing ap sua:t rieng ph<in ella cac khi trong bOn hqp khf
1i tuOng khi c6 can bAng ho8. hQC. Thi dl)., d6i vOi philo Ung t6ng hqp_
amoniac : N
2
+ 3H
2
= 2NH3 :
2
PNH3
Kp= 3
. PNz PH2
a dAy 00 kh6ng ghi k:Y hiu cit cb (can b8ng) a cha.n, nhun.g cAn nh6' Ia
khi tinh KP bao giO cfing ph:li ta:y nhling gia tri ella ap rieng phAn
khi c6 can b8ng bOO hqc ; d6i vOi cac hAng s6 can bang kh<i.c cfing
Phuong trinh dAng nhit (XI.22) ella phan Ung vit ta:
dG = RT(In liP -In Kp) (XI.24)
a dAy
(XI.25)
b) Hdng st/ cdn being Kc- Giii"a Pi va ndng dQ ci ella khi i trong h6n
hQp khi li ttKmg, c6 h thUc Pi = ciRT. Dua gi8. tr! nay ella Pi vao (XI.23)
va nu
Av = ( + + ... )- ( v
1
+ v
2
+ ... ) = const
thl se dUQC :
[
. . J
VI V2
K (T) = cB, ell,... . (RTlv
p VI V2
CA CA ..
l 2 cb
(XI.26)
Vl Kv ta hAng s6 chi hi} thuc vao T nen v ph3.i cling phcii c6 tinh
cMt nay; av phiii (RT) vIa mQt hAng s6 &Tconst, do d6 pMn cOn
99
cUa ve pb3.i cfing pbi'ri Ia rnt hAng s6 chi pb1,1 thu(M; vao T, gqi lA h&ng
s6' can Kc
J o;, J
K =II-' =
c v; v
1
v
2
CA CA CA ...
'cb
12
cb
(Xl.27)
(XI.27) 13 rnt cUa dlnli tic d1,1ng kb6i Iugng rna Gun be va
Vagia da tbu dugc narn 1867 ; b dAy n6 bitu thi rn6i lien M d!nh
lugng giii'a n6ng d C; cUa cic khi trong bOn hgp li tubng khi c6 cAn
bing boa hQc.
Dua Kc vao (XI.26) se dugc pbJJCmg trlnh lien h KP veri. Kc (1 cU.ng
nhit dl) T d6i v&i pb3.n Wtg kh8.o sat :
Kp = K,(RT)
6
v (Xl.28)
Neu V tinh ra lit, p ra atm thi R = 0,082/.atm/d.rnol.
c) D{li lll(lng K:r Giiia Pi va phAnmol xi ella khi i trong h6n hgp khf If
tubng c6 M thUc Pi = pxi, p 1a ap suai toan pMn cUa bOn hgp khf. Dua
gi<i d6 cUa Pi vao (Xl.23) se dugc :
Kp =KxP6v
Kx
K K
-6v
X= pP
(Xl.29)
(Xl.30)
(Xl.29a)
Vi KP chi ph1,1 vao T nen (XI.29a) cho tha:y rAng lugng Kx,
kbac v&i Kp, kh6ng nhUng ph1,1 thuc vao T, rna cOn ph1,1 thu(M; c8. vao ap
sua:t to8n pMn p cUa N6i khac, b T = const, trong khi KP 13. hAng s6,
100
khfmg ph1,1 thuc vao p thl Kx. bic!n thien theo p, tt'rc ta Kx kh6ng phdi Iii
h&ng s6' cdn b&ng (mQt d!_Li hrQDg K chi 19. bang s6 cAn bang khi rt6 19.
bang s6 (J T = const).
Kx chi 19.-hll.ng s6 can bAng khi Av = 0 (ph<in Ung kh6ng c6 Sl! thay
d6i s6 mol khi), khi d6 n6 d6ng vai KP. COn khi Av * 0 rna gqi Kx
Ia hAng s6 can bAng thl clich gQi nay Ia kh6ng chinh xlic.
d) Lien h giaa KP' Kc vii Kx :
I Kp K,(RT)"v KxP"vl (Xl.31)
Chi trong trubng hgp duy nhllt, khi Av = 0, nghia ta d6i vOi nhiing
phatl Ung kh6ng c6 Sl! thay d6i s6 mol khi thl 3 d!_Li luqng KP, Kc va Kx.
mai Mngnhau:
KP = Kc= Kx (khi Av = 0)
Khi Av * 0 (pban Ung c6 Sl! thay d6i s6 mol khi), KP c6 bAng Kx
khi p ; th<i biing Ko khi RT khi d6 1/R ]ftJ,082 12,2 K.
e) v e gid trj b&ng stl vii thituguyen cUa KP' Kc va Kx. V1 pM.n mol X
Ia mQt d<1-i luQDg ti d6i, khong c6 thU nguyen nen Kx cfing khOng c6 thU
nguyen.
Khi Av = 0 thl KP = Kc = Kx, do d6 KP va Kc trong truCmg hCJP nay
ci1ng Ia nhiing d<1-i hrQDg khOng c6 thU nguyen, gi6ng nhu Kx.
Khi Av * 0 thl n6i chung, clic hAng s6 can bAng KP, Kc ta nhiing d<1-i
IUQDg c6 thU nguyen.
Nhtmg dU c6 thU nguyen h3.y khOng thi d6i vOi cUng mQt phin Ung,
tlly theo chieu phAn Ung duqc xet va tlly theo clich ghi clic M s6 ti IUQDg
ella phB.n ling rna mQt Mng s6 can bang c6 the nhiing gia tri bang
s6 khlic nhau.
Thi d1,1 1. d 450C. d6i v6i phlin ling t6ng hqp (hay phftn li) NH
1
:
101
I)
IXri vl :
2)
3)
[Kd == [lip su!li:] hip su.rtr'
[;ip suaif
N2 + 3H2 == 2NH3
' PNH
3
' PN
2
PH
2
= K ~ = 0,421.10-4 atm-
2
K,
I
K
3
=-= =154,latm
K, 0,00649atm-
1
4) = K ~ -
- K'
K
4
= 2,37 . 10
4
atm
2
.
Thi d!J 2. 0 t"" 830"C vA p = Iatm, ph8o lrng trong pha khf:
ZH2S = 2H2 + .5:!
c6 hAng s6 can bAng :
Kc c6 thd' nguytn:
[Kcl = [n6ng dl)t' = [n6ng dl)]
[n6ng dOl'
'
NEu ddi don vj n6ng dr) ra milimol/1 =
1
~ moJ/1 thl n6ng d se bitu thj bing gill.
tri m& 16n han gia trj cillOOO 1411, do d6 :
102
Kc = 0,79. 10-s. Hf milimoVf
= 0,79. r0
2
milimoVI.
3. Cin blng hoi hQc dOng thi trong pha khf khOng If tl.ldng (h6n .
h<;fp khl th\10)
D6t v6i khi thl!C i, ai = fi, tUc 18. hrn,t.t dl) ai cUa khi chfnh Ia hrn,t.t 8p fi
cUa n6, do d6, d6i v6i phan Ung trong bOn hqp khi thJ!C, Ka = Kr ; b day
Kr 18. htmg s6 can bttng chi phi) thuQc vao T vii c6 dl;lllg :
(
fv' J
K,(T)=D
fvi
A
' ob
= (r;; r;;.J
f
v, fv2
A A ...
l 2 cb
Phmmg trinh ding cU.a pban Ung (XI.22) tW tbanh :
AG=RT(InDf -InK,)
v(1i :
va:
.1.G
0
= - RTlnKr
C6tM tlnh fi theo quy t!c gin dUng (VII.65);
f; = fA.
'
(Xl.32)
(Xl.33)
(Xl.34)
0 day fi' Ja ap ella khf i nguyen chit 0 cUng T nhu bOn hqp khf va c6 ap su8t pf
bang lip sUittOO.n ph:1n pella h6n hgp ; Iuqng f;
0
c6 thl! tfnh theo (VIL66) ;
ft = Y;P\' = Y;P
Yi Ia h s6 d ella khf i nguyen chit t,P lip suit pf = p. D6i vOi khf i nguyen
chit, 0 thai chu:in f,O = pf = p-== !atm. khi d6 Yj =I ; {J cic thii khac, c6
the tfnh g&n dUng fi theo nguyen If thai tuang ling (xem ch. VI, 2).
Kt h'!P (VII.65) vOi (VII.66) dugc ;
f; = Y;PX; = Y;P; (XL35)
til" d6, nu dua f, = Y;P; vim (XI.32) se dugc ;
(XI.36)
103
trong d6:
(XI.37)
D6i vlri. cAn bang holi hQC trong h6n hqp khf thl,TC b T = const, de d1_1.i lw;mg Ky va KP
n6i chong dtu khOng phW lit hling s6 vi chUng dtu thay d6i theo lip su!t tofm phlln p cUa
h6n hqp. Nhllllg tich cUa Ky vOi KP' tUc lit Kr thi dUng lit hAng s6 (J T = const, khOng
thuc vito p.
Ne"u dtra gili trj f; "' Y; p x; tir (XI.35) vito (XI.32) se dugc :
(XI.38)
D6i vlri. bOn hqp khf lhJ!c, Kx trong (XI38) ciing khOng ph3i lit bing s6 UT = const,
vi n6 cling thay d6i theo p.
T6m ll).i, ddi v&i cd11 btmg hoil hqc tro11g h&n htfp khi thf!c, chi K
1
mm duy nluft fr)
hJng st/dT = co11st, khOng pht} thu(ic vito p. Gill. tri cUa Krd6ng nMt v6i IS, khi p= I atm.
Kr giit nguyen gia tri nay cr nhitng lip suift cao han, mien IS T = const, trong khi d6thi KP
thay d6i theo p, va Kx cling
4. can bAng hoi hqc dOng thi trong pha lOng
a) Dung djch li tu&ng. D6i v& ciu tir i trong dung djch li tuOng,
(thang n6ng dQ ph<in mol xi), do d6 d6i v(ii cAn bAng boa hQC trong
dung dtch li tuUng, Ka = Kx va phtrctng trillh ctitng cUa phcin Ung c6
AG=RT(Inii, -InK,) (Xl.39)
104
.1.G
0
= -RTln K
'
v, J
XB:! ..
v,
XA ..
' ob
(Xl.40)
(Xl.41)
C6 tht chuyl!n ti'r Kx sang Kc nhu sau : N6ng d(l mol - thl! tich Cj ella i trong dung
djch 13 ci = DjN. "i Ja s6 mol i trong the tl'ch V cUa dung djch, do d6 Rj = CjV vi:
n cV c
X; = -' = -' - = -' =
rn; 1:c;V I:c;
kc; v6i. k = -
1
-
>:c;
Dtra gii tri nay cUa xi vao (X1.40) dugc :
0\U Y rang:
(XI.42)
(XI.43)
(XI.44)
(XI.43a)
(XI.45)
CJ dAy Mo Ia lch6i IUQI!g tilful tit ella dung m{)i cOn Mi ta kh6i IUQng Jit;ln tit cac ch!t i (i ;;:>: I)
1rong pbim Ung (Xl.S) vi tan trong dung mOi dii cOO. p lA kh6i Im,mg ritng ella dung tJ\ch.
b) Dung dich thifc: HMg s6 can bMg chi phy thul)c vl!.o T 13 Ka.
Trong thang n6ng d(l X; thl a;= Yx,i. X;; Yx.i 13 h ~ s6 h o ~ t d(l cUa i trong thang X. Dtra
gii trj d6 cUa a; vito bil!u thUc (Xl.20) cUa Ka se dugc :
(XI.46)
trong d6:
(XI.47)
Vi de h s6 h ~ t de) Yx.i v3do d6 KYx phy thuc vito n6ng d(l X; cUa de chit i trong
dung d!ch th\fC cho ntn theo (XI.46) Kx = Ka I K.r. ciing phy thul)c vao de n6ng de)
x;. N6i khic, 0 T = const, Kx v3 Ky._ thay d6i theo n6ng de). Oil K
3
= Ky._ . K .. m& 13
hMg s6 b T = const.
105
Tr0ng lhang n6ng molan m; hay n6ng mol - lht tid!. c; thl a;= Ym,i m;
11; = c;, U day Ym.i bay Yc,i lit M s6h0ll-1 dQ trong tbang n6ng d t!l(1Dg Ung. Khi d6:
(XI.48)
Ky.., KYc c6 di!Jlg 1Jl(1Dg llf (Xl.47), chi pbai. thay Yx bihlg Ym ho4c Yc Gic d{li
Jugng Ky.., , K,. Kc cling deu thay d6i theo n6ng d. Chi duy nlult Ka mdi Iii luing
:r6 U T = C0/1!11 dOi vUi cti11 bang hod lu;c trong dung djch thlfe.
c) djcll tlll{c va IoOng. D6i vOi dung d!ch rAt lOOng, c<lc Yx,
Ym, Yc cteu bing 1, c<ic Kyx, Kym, Kyc ciing dtu hang 1. Khi d6 Kx,
Km, Kc mdi tr0 thfmh bang s6 0 T = const. Gic gia trj bAng s6 cUa Kx
Kro va Kc Ia khac nhau nhung ti 1 v& nhau.
Trong trOOng hqp chung:
m c
Xj =-'- =-'
Lmi. :Eci
(XI.49)
trong d6:
!000
+ ... +--
Mo
(Xl.50)
. I
Lei =cA
1
+cA
2
+ ... +c
81
+c
82
+ ... + M (lOOOp-:EciMi)
0
H thUc cu6i nily h thUc (XI.45) da trinh bay 6 tren. Tir d6 .
suy ra dt dang :
(Xl.51)
D6i vai dung djch vO cimg lOOng :
!000 IOOOp
:Em::::::- va :Ec ::::::--
1 M ; M
0 0
(XI.52)
dod6:
(XI.53)
106
4.UNG DI,ING CUA PHLIONG TRiNH ElANG
VACUA ElANG AP CHUAN CUA PHAN UNG
1. Phlle1ng trinh ding nhit vii c:hia;u cUa phin Li'ng
Phuong trlnh ding nhit ella phcin Ung cho phcSp danb gi3. kh8. nang.
nguyen cic, th\fC phiin Ung theo ltB.o d6. D6i v6i pluln Ung
. .
(XI.S): v
1
A
1
+ v
2
A
2
+ ... = v
1
B
1
+ v
2
B
2
+ ...
6 T, p di cho, ta tfnh AG ella phoin Ung v6i gili thh!t phiin Ung ditn ra
theo chieu thul}n (tit tr8i sang JiiAi) :
1) nl!u .6.0 < 0, phin Ung c6 khii nang ditn ra tJ! nhien theo di
giii thil!t ;
2) nu AG > 0, ph!n Ung kh6ng thi! dit!n ra theo d.i gi<i thit,
chi c6 khii nang ditn ra theo ngbich (tit phai sang tr8i) ;
3) nl!u .6.0 = 0, M b vko lrfPlg thoii cAn bAng boa hQC.
Thf d1.1 xet phin Ung: co+ Hp (k) = C0
2
+ H
2
Gii tbll 14"y CO i1 10 bar, hai nu6'c H
2
0 0 5 bar cho vlto pbOng phin Ung lJ 700C
v6i m1,1c dfch mu6n dieu chl C0
2
va H
2
0 1,5 bar, bie't rlng U 700C, pbin ling d6 c6
KP = 0,71.
De danh gili kh3. nang li thuytt cila qu8 trlnh, ta gii thitt cac khi 18 li tulrng va tinh
.6.0 theo pbuong trlnh ding (Xl24) ella pbin dng :
6.0 = RT[/n

-/nKPl
Poo PH
2
0
AG=8,314.973(/nl,S.l,S -ln0,1ll
10.5
AG =- 22315,78 J < 0. V.y plu\n Ung c6 kha\ nAng xa\y ra vt nguytn lie: Clni j rAng
dAy mt'ii chi ta kbi nang ve nguytn lie. Phin Ung c6 lhl;lC sl,l' diln ra bay kbOng, diliu nay
cOn tu)' tbul)c vao nhihtg yfu t6 d(lng bQC (t6c d(l phin Ung). Ne'u 6.0 0 rna pbin Ung
khOng die!n ra, d6 13 do '1:6 nhihtg cin tiD vt dc)ng hQC. Thi U t = 25"c, p = 1 bar,
,. ..... ,
107
I
H
2
+-0
2
= H
2
0 (I)
2
c6 6CJ2
911
=- 228,378 klhnol, song ptu\n lhlg kh6ng di!n ra. Nhung dua vito M m(lt
chlft xllc tac thich hqp thi phAn ling se di!n ra v6i t6c do.';116n vli. lhiJC t cho dn ht.
2. The ding ip chuin va chieu cUa phin !lng
C6 tM dUng mt each tin I(;ri th( ding ap chuAn !'!G
0
cila ph3.n iing
r
danh gia kh3. nang th1JC philo iing vl t...G
0
de tinh hem !!.G.
1) Khi .6.0 0 thi, phU hqp vm 1!.0 = - hang s6 cAn bAng
Ka se rift IOn va phi'm iing c6 khci nang ve nguyful tic thl,TC khOng
nhihlg chi trong chuAn, rna ca trong nhiing difu kin ba't ld bCri
vi M c6 tht d6i dllqC d&u ella 6-G thl ph8i tam tang gia tri tuyt d6i s6
h;p1g thd nhllt v ph<ii phlWllg trlnh dAng nhit ella ph<in Ung :
V
1
Vz
aB aS.: ..
D.G = RT/n
1
-RTlnKa
v, v2
8
A
1
8
Az
m()t lm;:mg thi!C t( khbng tM nao duqc.
Kt nay 18. dUng, bit, d6i v6i phdn Ung hinh thimh lufp chdt
til dcm chdt. Do d6 c6 thi n6i hqp ch!lt 18. ben hay kh6ng binnhi4t dt)ng,
tuy thea tht dAng cip chwin hlnh thimh h1;1p chAt tlr dan chAt, dG
0
0
(hop cMt b<ln) !J.G
0
0 (hop cMt khOng b<ln). Hop cMt b<ln Ia
hqp chAt c6 khi nAng hlnh thltnh tir dan chat; hqp chAt khOng ben 13. hQp
chAt c6 khi nang phan tich thanh ddll. cha.'t.
2) N6u 6.G
0
0 thl ph Ung se dien ra b mUc khOng doing
neu ll.G
0
rAt lOn thl khong 11.10 ra dll'qc nhtlng dieu e6 lqi
eho sv dien bin ella phiin Ung.
3) Nu .6.G
0
be ve gi3. trj tuyt d6i (dG
0
c6 thi > 0 hoi}.e < 0) thl
khOng tht! rUt ra kt lul).n gl ve ehieu ella qua trlnh. Thf d1,1, d6i vOi phan
Ung t6ng hqp NH
3
, .6.Gg
73
=24,16 kJ/mol > 0. Nh\rng 0 400C, vOi chAt
xUc tac thich hqp, thl vAn th\fC dtrqc phiin Ung t6ng hqp NH
3
.
108
Di tfnh thf ddng "' chulin cila phan ling tit nhilng th dAng ap chuiin
hinh thimh hqp cMt tit ddn ch!lt, ta c6 dUng quy tAc tll'cmg f\l nhu quy
cic tinh hi?u ling nhi?t cila phiulllng til cac sinh nhi?t (nhi?t hlnh thanh) :
=
(XI. 54)
3. Sl! til hqp cin blng va tinh gian tiep cin blng
feb lqi thJ!C titn co bAn clc ding ip chu&t !l.G
0
ella phim ling
Ht n6 cho khii nang t6 hqp clic can b&ng va tinh h&ng s6 can bAng d6i v&
nhUng pbim ling chua c6 dU thi,IC hay khOng tht! ciiu
trJ1C tip bing thl,IC Cich tinh ciing tin banh toon.g u;r nhll tinh
Ung nhit ella ph;in Ung theo d!flh Hetxa.
VI. G Ht ham thai ciia h nen !l.G
0
chi ph\1 thuc vao thai
dAu va cu6i ella kh6ng ph\1 thu(>c vao duUng di.
Thi Xet nhitng ph!ln Ung b cllog nhit T :
2C(graphit) + 2H
2
= C
2
H
4
C2H4 + H2 ""C2H6
2C(graphit) + 3H
2
""C
2
Ht;
ot th!i:y rAng phin Ung (Ill) 111. t6ng cila 2 phin lffig (I) va (II)
(Ill)= (I)+ (Il)
dod6:
60?
11
= AG? + AG?
1
(I)
(II)
(Ill)
tUc la c6 lhi di tb!ng tlr C (graphit) va H
2
dln etan Czlit; batlg phim Ung (III) qu:
trung gian hlnh thllnh etilen CzR! theo phlin ling (1) r6i sau d6 hidro hoi etilen theo
ling (ll),!J.G
0
trong hai etch dO phai bing nhau.
Tird6:
-RT/nKm =-RT(InK, + lnKu)
lnKm = lnK
1
+ lnKu Km = K
1
. K
11
Bang c8.ch d6 tlnh dllqe gilin titp hang s6 can bAng Km cila pbiin \rng (UI) dl,lll vi
nhrmg gia tri dii bit"t K
1
vi'l Kn cUa pbiin \tng (I) vi'l (II).
11
5. ANH HlJONG COA AP SUAT LEN
CAN BANG HOA Hc;>C
Ap suitt kh6ng c6 rum hubng dang kl! len can OOng bOO hQC trong pha
lOng vl pha lOng lit kh6 nen. Do d6, ta chi xet oinh hul:mg ella lip suAt len
can btulg hoi hQC trong pha khi va de! dan giiin la gi3. thit pha khi HL
h6n hQp khi H tu<':mg. D6i v6i cAn bAng hoii h9c trong khi H
tulmg, ta c6 :
K K
-ov
X::::: p .p
tir dO :
lnKx = lnKp - !lv/np
U:y hiun theo p lJ T = const :
( Bl:x )T 8/:p )T -Av( 8:p )T
D6i v(ri khi lf tudn.g, KP chi ph1,1 thu<)c vao T, kh6ng phi} thu(K:
vao p. do d6 (8/nKp /8plr 0 con 8/np Bp/p va 8/np/Bp 1/p.
( Bl:x l _ :v _ (XI.55)
vi pAV AvRT. TU (XI.55) suy ra:
1) m!u !:J.v = 0 (pluln Ung khOng c6 S\f thay d6i s6 mol khi) th'i Kx
kh6ng thay d6i theo p. tlrc lit SlJ' thay d6i lip sua:t aT = const khOng Uun
thay d6i vi tri ella cAn Mng bOO. h<;>c :
2) m!u Av < 0 (pban Ung c6 st,t gi3.m s6 mol khf) thl
(81:, )T >0
la 0 T = const, Kx biln thitn cllng chit!u v& p. Nlu p tang thl Kx
tAng theo tttc lit can bAng chuyl!n dich theo chieu tir tni.i sang ph!i,
110
ta chitu lam -gii'un s6 mol IdU (tUc ta chil!u tam gii'un bOt ap sulft) : dhiing
h.tc.;tng nilo d6 nhilng cMt d!u A
1
, A
2
, ... phiin Ung vCti nhau de.hlnh thimh
them nhfing luqng m6i nhfing cha:t cu6i B
1
, Bz, ...
3) Ta ciing se dll\"C nhfing kt qua tuang tJ! nhung nguqc Av> 0
(phiin Ung c6 SJ! tAng s6 mol khf).
Nhfing dil!u n6i tren phil hqp v6i nguyen 1i chuye:n djch cAn bfmg
Ld Satalie - Braun. Do d6 c6 the xem (XI.55) ta bie:u thllc djnh luqng
cUa nguyen li nay ap dl}tig cho sJ! chuyen djch can OO.ng ho3. hQC du6i
tic dl,mg ella ap sulft.
6. CAN BANG HOA HQC D! THE
1. D!nh nghia vii thi d1,1
CAn bang hOO hQC dj tM 111 cAn bAng trong nhiing M rna clc chft pblin ling c6 a
nhUng pha khic nhau. Thi d\1, cAn b&ng trong phlm ling khU FeO bAng khi CO :
FeO(r) +CO= Fe(r) + C02
b day c6 2 pba nin : m6i cha:t nin nguyen chit FeO vi Fe lA ml)t pha rieng (pha nin
nguyen chat) khOng hQp thlmh dung djch nin vOi nbau vOi pha khf; cOn de khf CO
va C0
2
thl hQp lh!mh mQt pha khf duy nhat.
MQt thf d\1 kbac. SIJ' phAn ella CaC0
3
(nung vOi) :
. (II)
a day c6 3 pha, mOi pha lA mN chat nguyen cbft : pha nin CaC0
3
, pha nin CaO vA pha
khfC02.
2. Ojnh tic d1,1ng khOi IU"qng d6i vdi can bing hoiil hqC dj th'
Plnwng trlnh (X1.20) :
[
i;*J
K (T) = -":''-:"""-
a vl "2
aA a A ...
' ' "'
(XI.20)
lA bitu th11c tOng quit nba't ciia djnh llic kMi luqng, dUng cbo mQi b ba:t kl,
d6ng )hi cDng nh11 di lhi.
Ill
ThOng thtWng nbl't, nhUng pha rAn vii. dOi khi nhUng pha lOng c6 lrong ptuin ling
dj tM Ja nhUng chl't bOO hQC (nhUng ca nh4n hoi h91=) thlfc tt' nguyen chit, hOl:lt d ella
chOng chi ph1,1 thu(lc vllo nbit d (lip sul't chi c6 inh huim.g rl't nhO, khOng dang k dOi
v6i nhUng pha nglfllg 1\1). 0 T = const, hot d ella nhUng cba:t d6 Iii. nhUng bing s6, c6
tM g(lp vOO hAng s6 can bAng cila phuang trinh (X1.20). N!u nii.y xli.y ra d6i v6i mQi
pha ngung 11,1 cUa phin ling th1 a phuang lrinh (X1.20) se chi cOn c6 d cUa cdc
cl'u tir khf khi c6 can bang vi a; = f; dOi v6i khi thlfc i, a; = P; d6i vOi khf If 1uim.g i, cOn
nhUng dl1 tnmg cUa Clic c(u tir ngUng w se khOng biiu thi a dl!Jlg r5 dog trong phuang
trinh loy.
Thf dl.l. d6i v6i phin ling (1), hl\ng s6 cAn bang Iii.:
K
' Poo
vii. dOi v6i phin ling (II) (nung vOi), hAng s6 cAn bang Iii. :
KP = PC0:2
E>Oi v(jj Slf nung vOi, a m6i d T, lip suift PC0:2 Iii. m1 bing s6 khOng phi.J thuc
vao lm;mg CaC0
3
vii. CaO c6 trong he. Ap sWfl can bing d6 ( PC'Ih ) gQi Ja Op sud't
phdn fi.
Ta cfing duqc k!t qui tuang {If d6i vOi nhihlg phM ling dj the chi c6 m1 cfu tU U
II"l!Jlg thlii khf. nhUng phin 6ng phao li cacbonat, hidrat (linh nude),
amoniacat, mt s6 sunfua v.v ... tMu thu(lc d6. Thi nhUng phlln llng:
MgC03(r) = MgO(r) + C02
4CuO(r) = 2Cu
2
0(r) +02
MgS04. ?H20 (r)= MgS04 .6H20 (r) + H20{k)
ll2
CHUJNGXII
ANH HllcJNG CUA NHieT DQ LEN cAN BANG
HOA HQC. NGUYEN Ll THU BA CUA
NHIET DONG LliC HOC
. . . .
l. 51,1 PHI,J THUQC CUA HANG 56 CAN BANG
vAo NHieT>(l
1. Phwng trlnh ding 8p va ding tfch cUa phin U'ng hoc\ hqc
Ta phuong trinh Gipxa - Hemhon (V .25) d6i v6i phim Ung chuAn
se duqc :
(XII.!)
6.0 13. th dAng ap chuAn ella pban Cmg, trong tnrOng hqp t6ng quat
c6 :
0
dG =- RT/n Ka
Dua gia tri nay ella 6.0 vao (XII.l) se dU'Qc phudng trinh Van HOp :
d!nKa dH
0
RT
2
(XII.2)
Mf 18. entanpi chuAn ci'la philo Ung : d6 Ia bin thien entanpi
hiu llng nhit ella phin Ung 0 p = canst) khi cac chAt dli:u ella ph<ln Ung
b thai chuAn cho chAt cu6i cling b thai chuAn b 3p su!t
latm. V1 hiu Ung nhit ella phin Ung chi ph1,1 thuQc khOng dang kti vao
lip sulft, nen ta c6 bO chi s6 "o" b hiu Ung nhit. dH va
co th<l thay (XII.2) bOng:
113
(XIl.3)
Phucmg trinh nay gqi 18. phuung trinh d&ng cip cUa plldn Ung. Vl Ka
chi ph1,1 thuQc vao T, kh6ng phl} thuQc vao p. nen y nghia ella phuang
trlnh dilng ap chi Ht C1 chiS trong_ phuang trinh c6 Ung dAng ap
ella phin Ung.
D6i vdi pban Ung trong h6n hqp khi li tu<mg, Ka = KP. plut(mg trinh
ddng tip ella phiin lmg c6 d;.mg :
--- (Xll.4)
(
iJIIiJTK, ), __ t<H QP
RT
2
- RT
2
D6i v6i phiin Ung a the tich kh6ng d6i, ta se duqc phllo'llg trlnh d&ng
tich cUa Phdn Ung :
ChUng minh :
iJ/nK, = l<H = Qy (Xll.5)
iJT RT
2
RT
2
dinK d/nKP d/nRT
__ , =- __ ,, __
dT dT dT
d/nRT = dRT = RdT = dT --+ d/nRT = .!_
RTRTT dTT
bbi vl theo (111.3) QP == Qy + .O.vRT
Phuang trlnh dAng lip va d!ng tfch ella pban Ung boa hqc duqc
Van H6p thit dciu tien (1885).
114
2. 51! chuyin djch can bang hoa hQc dltd'i tac d\Jng cUa nhi't dQ
C6 the! gl)p hai phuang trinh ding ap va dc\ng tich cUa ph<ln Ung thanh
mt phuang trlnh chung nhu sau :
dinK Q
--=--
dT RT2
K seta Kp nu Q = Qp vase Kc nu Q = Qy.
Phuong trinh nay cho phep tien dmin chieu d!ch can bAng hOO.
hqc du6i t<lc dl)ng cUa nhit d. Gi<i thlr phan Ung sau, tlr tnii sang phai
ta thu nhit (Q > 0) :
A+B=C+D (Q > 0)
Khi d6 dinK > 0, tUc ta nu T tang th1/nK va do d6 K tang theo. K
dT
tang c6 nghla Ia lw;mg c<ic chA't san ph!\m C va D tang cOn luc;mg cac
ch<lt dau Ava B giiim di. slf tiing nhit d9 Jam clw cdn bdng chuyln
dfch sang clu"iu ling vdi phdn Ung thu nhit, diCu nay phil hqp v6i
nguyen li chuytin d!ch can bang La Satc11ie - Braun. Do d6 c6 the! n6i
phuang trlnh ding <ip va ding tich cUa phiin Ung ta thUc djnh luqng
cUa nguyen If Lo Satcrlie - Braun <ip d1,mg cho sl,l' d!ch cUa cAn
b3.ng ho<i hqc du6i tic dl}ng cU.a nhit dQ.
3. Tfch phan g3n dUng phlldng trinh Van HOp
Nu gi<i thit dH = const (dCP = 0) thl tir (XIL4) :
Llli dT
dinK =-.-
P R T2
InK =dH f dT +I'=- L!H +I'
P R T2 RT
I' Ia hAng s6 tfch phAn. Chuyen sang logarit philo :
Llli I'
lgKP =- +--
8,3I4.2,303T 2,303
(XII.4a)
I 15
A
lgKP =-+ B
T
(Xil.6)
A=- Ml/(8,314.2,303) va B = I'/2,303Ia nhilng bang s6. (Xll.6) cho th>y
lgKP phv thuo)c theo dl!Ong thing vao I (f. Dt) d6c cua dl!Ong thing bing:
&I
tga =- =A
8,314.2,303
Neu A> o (tiic 1a m < lgKp
ph3.n Ung tOa thl lgKP'
va do d6 KP se tang khi T
giiim, tiic 1a khi 1/f tang (hinh
XII-la).
1
ll.H<O(a)
ll.H>O(b)

1
T
Nu A< 0 (tU'c lit dH> 0,
pban Ung thu thl lgKP
va do d6 KP se giiim khi 1/f
tOng (hinh XII -I b).
COn bang s6 B thl b!lng
tung dt') g6c ella dUOng thing.
C6 the tich phOn phllllllg trinh
ffillh.M/-l.S.qtu,athueyccUa /gKP vilo t
a) khi .O.H < 0 (toii. nhi1)
b) khi .O.H > 0 (thu nhi?t)
(XII.4a) gilla hai d() T
1
va T
2
se duqc :
In Kp,T, =&I (_!_ __ 1 )
Kp,TI R Tt Tz
(XII.?)
lg Kp,T, - &I (-' __ 1 )
Kp,T, 8,314.2,303 Tt T
2
(XIl.7a)
Trong nhti'ng phucmg trinh nay, llli ta gia tr! trung blnh ella U:ng
ella phan ling gifia hai dt') T
1
va T
2
:
I
&I +&IT)
2 ' '
116
Nhilng phuang trlnh (XII. 7) cho phep lam hai tinh :
a) Xlic d!nh Kp,T
2
khi dii bit Kp.T, (thuOng T
1
= 298K) va L!H ella
philo Ung;
b) X:ic dinh MI ella ph8.n U'ng khi dii bie't Kp T va Kp T .
' I 2
4. Tich phiin chinh x3c hdn phlldng trlnh Van HOp
De liy tich phiin chinh xac boo, dn phii ke' de"n su phl) thu(X: C.H elm ph<in ling vao T.
Theo di.nh Iuat Kiec Hop (III.8) .
d"H
d'f"'l!.CP haydl!.H= ACrdT
tit d6:
L'l.H
0
Iii hiing s6 tich ph!m. ACP thu?mg c6 (lll.l3) :
,,.
t.Cr = Aa + t.bT + h.cT
2
+-
T'
Khi d6:
I 2 I 3 6c'
= 6aT+-6.bT +-L'!.cT --
2 3 T
Dua (XII. I 0) vao (XU.8) :
I 2 I l lk'
t.HT = C.H
0
+ l!.aT + -L'!.bT +-AcT --
2 3 T
TU (Xll.4a), liy tich ph!n :
InK =_.!._ fl!.HTdT +I'
r R T
2
Thay t.H trong (XILI2) hang thtl:c (XII. II) :
I 2 I 3 6c'
(XII.S)
(XI1.9)
(XILIO)
(XILII)
(XILI2)
I fAH
0
+6aT+-IlbT +-L'l.cT --
fnKp=R 2 3 T dT +I'=
T'
- --+-+-6b+-&:T-- dT+I"' I f("H" "" I I "") ,
Rr1T23 T3
117

=- Mio + .1a l11T+ dbT+ /'J.cT
2
+

+I'
RTR 2R 6R 2R
6.H
0
.1a Ab /'J.c 2
lgK "'---+--lgT+--T+--T +
I' 19,15T 8.314 38.29 ll4,88
&' T-
2
I"
+-- +
38,29
trong d6 I" "'I'/2,303.
<XII.n>
(XII.I4)
khli.e, 6.0 = -RT/11 KP, do d6 n!'u nhan 2 v ella (XII.13) v{ri (- Rn se dugc :
o I 2 I 3 I ,
6.0 =6.H
0
-&Th1T--LlbT --/'J.cT - -/'J.c'r +IT (XII.IS)
2 6 2
trong d61 =- RI' =- 8,314 I'
Dt tinh KP 6.0;, T b!ft kl, trong tnrUng hW ehung, dn bit :
I) S., thu(K: c;, vito T d6i v6i mQi eh!i"t trong phim ling ;
2) Mt giii tJi ella dH U nhi1 dl) T dl! xie djnh LlH
0
theo (XII. II)
3) M()t giii tri ella KP 6.0;, nhi1 d T. Khi d6, th (Kp}r vao (XII.14) ho: the'
(Ll0}r vito (XII. IS) se tim dugc hang s6 tfeh phan I" I.
Sau khi dii xRc djnh duqc Lltfo va eae Mng s6 tfeh phan thl e6 khi nang tlnh dugc KP
h04 6.0 0 mQi T b!ft k'i.
2. fl!NH Lf CUA NECXO. NGUYEN Lf THLr BA
CUA flQNG LI,/C HQC
1. Md diu
ve II$ ljeh sit, djnh If nhit ella Neexa (Nemst) ra dOi. niim 1906 nhhn dC giii quy!'t
v!fn df 3i ii!C ho3 hQC. Nhu dii n6i, 'dl) do 3.i h!e hOO. hQe ella de eh(l trong tuang tkhOO.
hQe khOng phii Ia hiu ling nhi1 elm phin ling nhu nguyen li Beeta!O (1867) dii khing
dinh sai rna lit eOng eUa ph8n ling, tU'e ta b!ng d giim ella eae the nhit dng, nhu
Oipxa (1876), Hemhon (1884) vii. Van HOp (1885) dli ehling minh dUng din:
118

>61. v6i LlO, til" phuong trlnb Gipxa-Hemhon (V .25)
AH
dT T T
2
tac6
Iay tfch phAn :
6.G,_fllH dT+I
T T
2
tUc Ia
6.0= -T dT+ IT
(XII.I6)
I lit bing s6 tlch phan khOng x;ic djnb. Nguyen H I vii II kh6ng cho kh3. ning linh dugc I
Mug If thuyt.
Cilng v!)y, d6i vai l!.F, tir phtrong trinh Gipxa-Hemhon:
6.U
dT T T
2
Sl! tfch ph :in cilng !lim xuHt tfch pMn khOng xac djnh I'
LlF= -T dT+IT
(Xll.l7)
Nhu kht"lng the tlm dUQC gia tfi tuyt d6i ella Iii boa hQc ""'P &v. Kh6
khan nay chi dm;tc kb:ic phl.lc nhG djnh If nhi1 ella Necxa.
Kh6 khan tuang II! ciing dli MP phii khi xac djnh gili tri tuyt d6i ella entr6pi. Theo
nguyen If II. entrOpi dugc djnh nghla bang m1 phuang trlnh vi pban :
dS= &J
T
d6i vOi mqi qua trlnh nghjch trong h can bMg: 0 p = const, SQ = CfT. do d6:
T
ST =So+ :r-? dT
"
Nguyen li I va II ciing khOng cho khi nang tinh dugc gili trj ci.La hAng s6 S
0
va nhu
till kh6ng tinh duqc gi!i tr! d6i ci.La entrOpi.
'
119
SJ! lich phim phuong lrlnh 3.p ho;'!.c ding tich ctia phlin Ung de tfnh himg s6 can
hii.ng Kp hay Kc a cic nhi1 d!) khk nhau ding lilm xu:lt hin himg s6 tich phim bat djnh
nhu 0 lhUc (XII.I4) (XII. IS) :
D<lloai hllng s6 tfch phim nily thl phii bit fl nhtlt mQt gi3. tri cUa Kp (hay Kc) 6 mQt
dQ T nilo d6. Nhung do Kp Kc) Iii. m!)t c6ng vic kh6 khan, phUc
bon vic do hiu Ung nhi1 /HI (hay AU) cUa ph;in Ung do nhit dung cUa de chtlt
nlt nhiu.
S(! pbal triEn manh me cUa nt'n c6ng nghip holi hQc vii ngilnh luyn kim h6i diu th
ki 20 dOi hOi phai (;6 ngay nhiu s6 liu ve c:l.n bimg iJ c3.c nhi1 d<} kMc nhau. Do d6,
m('!l y4!u c:lu ca"p bach ra hk btly giO lil lilm sao c6 tM lfnh dugc c:ln bang hoiln toiln
chi dl,fa vilo cic dai lugng nhit (hiu Ung nhit vii. nhitl dung), trinh con duOng do
de bang s6 c:l.n biing Ia con duOng kh6 khan vat vii va dbi hOi r.lt nhiu thOi gian.
Djnh If nhi1 cUa Necxa ra dOi ciing lil de dip Ung yCu c:iu nily.
2. thll' nha't djnh li Necxd
Slf kin thvc nghim da b G
/M
tOi djnh li nhit nhu sau.
St,r so s<inh hiu Ung nhit dH
va the' <ip dO ella nhihlg
phlm Un.g ra trong eae pha
ngung t\). b nhfrng dQ khae
nhau cho tbay b vfmg d
thap, gAo dQ kh6ng d6i, gia
tri ella dH va dO ella eU.ng mt
phim Ung tie'n gAo nhau (hlnh
Xll-2).
D!nh li nhit ella Neexo 1a
mQt tii!n dC thira ding khi
dQ thap han nUa, 6.0 va
b.H
1
0
/
/
-.::.:: __________ _
---
--
--
',"' b.H

Hnh X/1-2. NhUn.g dm'm.g cong AH = f(T)
vil AG = f(I) iJvUng nhi1 dQ thilp (duimg
cham ch:lm iing v6i sl,f khOng c6 dil kin
thl,fc nghiCm)
6.H ella cling mQt ph8.n Un.g tie'p t\).e gAo nhau, sao cho b OK, d.c
dtK:mg tie'p xlic nhau, c6 mt tie'p tuye'n chung song song vOi
tr\).c nhit dQ (hlnh Xll-2).
0 tmin hQC, diCu khAng d!nh d6 c6 tit nhu sau. D6i vOi
cac phim Un.g (va cac qua trlnh dAng n6i chong) trong h ngung t\1
b T = const g<in OK thl :
120
(XII.l8)
va
lim lim
T or T --)>o or
(Xll.19)
tlrc 1a 6.G va .t!H kh6ng thay dcii theo T nUa (nu nhfing duCmg cong L't.G
va L't.H c6 tip tuyn chung nhung kh6ng song song v6i T thl L't.G va
L't.H vAn cOn bin thien theo T).
NhUng kt -qua tucmg 11! ci1ng thu duqc dOi v6i hiu Ung nhit AU vii
th ding tich .6.F ella phi'm Ung eRe ngtmg 11,1 0 glin OK :
LIF = LIU aT---> 0 (Xll.20)
I" (BLIF) I" (BLIU) O
Of y = 0T y =
(Xll.21)
Nhu th(r nha't d!nh If nhit ella Necxo c6 c6ng thlrc hocl
g<;>n nhU' sau : Di/i v6i nhang phdn ii'ng hod lu?c (vd cdc qua trt'nh d&ng
nhit n6i chung) trong cdc II ngllng JT--+ 0, dJ = &1, &' = ,1U vd
cdc dgi {tftJng mly kluJng cOn ph'! thu(Jc vdo d{'J nUa.
ChU y ding nhi1ng d<ing thUc L't.G = AH va M' = AU 0 T ----) 0, c6 nghla
ta nguyen li Bectolo chi dUng chfnh xac b T ----)0, day chi nhUn.g phan
Ung tOa nhit mffi c6 xiiy ra.
3. thli hai djnh li Necxd
D!nh li Necxo c6 th6 bie:u th! duOi di;tng thU hai, holm toan tucmg
dttcmg vdi dl;Ulg thU nhrlt. Vi (OG I 8T)p = - S (8dG I OT)p =- dS,
ciing tU (8F I Of)v = -S, suy ra (86.F 16.T)v =- 6.S ; ngoai ra, theo
dinh Kiec H6p (8LIH/BT)p LICP, (8LIU/8T)v LICy, do d6
(XILI9) va (XII.21) triHhanh o
lim 6.S = lim dCP = 0
T T
(X11.22)
lim dS = lim 6.Cy = 0
T T
(XII.23)
121
nglifa Iii, d T 0, ctlc phdn Ung (vd cdc qud trinh d&ng n6i
chu11g), trong cdc ng1111g giUa ctlc chiit rcU1 hay cluft lOng nguyen
chdt diin ra k/16ng c6 bie/1 thien entr6pi va k116ng c6 bie'n thien nhit
dung. N6i khlic, 0 T-). 0 entrOpi va dung cU:a M ngllllg tl) khOng
thay d6i du6i Mt ki tac dl,lllg nao niia.
4. DQng thU' ba djnh If Necxd
Tit .6.<1, = 0 va dCv = 0 0 T --i> 0, Necxo sang

lim CP =lim Cv =0
T --l-0 T --l-0
(Xl1.24)
nghia U1. cho rAng 0 T--) 0, kh6ng nhiing tlCP hay llCv ci'la M ngllllg tl):
bAng khbng rna chinh CP va Cv ci'la m6i chat ngung tl): chllt (mOi
eli nhAn ho3. hC?C) cilng bAng khOng.
Da.y 18. ml)t mO:i ci'la d!nh If nhit;t ci'la Necxo, khOng rUt ra tirhai
di;Lilg tren, nhllllg dtn;JC thira nhu mQt tien dl:fa vao nhiing dii'
kin thJ!C nghim Sl! phi): thuQc ci'la nhit dung vao nhit dQ va vao If
luqng tlr ella nhit dung.
5. Tlin de Piing (Planck)
No1m 1912, Pliing d1i phat d!nh 1i nhit ella Necxo them mQt
buOC bilng clich tit kin cUa Necxo i\S = 0 0 T __. 0 sang
dit!u kin :
limS =0 S
0
= 0
T-->0
(Xll.25)
Nhu tien dt! Plang Ia st,r thira nh4n r&ng U T 0. khOng nhUng LiS
cUa phdn Ung (cUa cdc eMf ngung llf) b&ng k110ng, mii chinh emr6pi
S cUa m6i chiil nglhlg lif. nguyen cluil cilng b!lng khOng.
Tien M Pliing kh6ng rUt ra tit d!nh li nhit ci'la Necxo rna lA mQt b6
sung cho djnh If Necxo. Tuy nhien, tien de Plang va djnh If Necxo
khOng pbai Ia hoi\n toi\n dc nhau, v) tir tien Pliing S = 0 0 T--) 0
suy ra di;Lilg thU ba ci'la dinh li N ecxo <; va Cy --) 0 0 T --) 0. Thqc v*y
theo djnh nghia ella nhit dung :
122
Cv =T(:)v va c, =T(:),
ta dtn;IC, theo tien Plang :
. CdT TfCdT
oV=const,dS=TS= T
0
, C pdT TfC,dT
o p = const, dS = ----:r-, S = --:r---
0
(XII.26)
(XII.27)
Tir (XII.26) va (XII.27) suy ra iJ T -->0, nu Cy va C, khOng -->0 thl
Cy!f va Cpff va do d6 entropi se IOn v6
Nhu tien dt'! Plang va dinh li ella Necxo 13. hai van c6lien
quan vCti nhau. Do d6 khi n6i d!nh If nhit cUa Necxo. nguffi ta
thubng hieu rQng ra 13. n6 bao g6m c3 tien Plang.
Ghi chU : Nhilng diiu n6i vf entrOpi trong PJang chi dUng chfnh xlic d6i vUi
nhiing chll:t hoi hQC nguyen cha"t, tUc Iii tirng eli nhan hmi hQC rna m{lng tinh the ella
chUng dugc xll.y di,Illg li tulmg, nghia Ill trong tinh thf, mQi nUt rn!u dugc chie'm dfu
bOi. cac tifu ph!ln (phAn ti'r, nguyen tlr hay ion), cic ti!u phlln nAy phdn b6 vii djnh hu6ng
c6 quy Mu Nhilng tinh thi nliy gQi Ia v{lt r&n li ruU11g hay hoii11 chinh. Nhii'ng
tinh thl! lhi!C kh6ng ph&i li\ tinh the'! If nr6ng vl m{lng tinh thi ella cht1ng kh6ng dllqc xi\y
d\fJig m(lt cich If tuimg.
Trong tinh tht th\fc mQt s6 nUt khOng dugc chie'm bOi nbiing til!u ph:ln ella linb
tbl!, de til!u phan c6 the dich chuyl!n ra khOi vi tJi can bAng va dinh huOng khOng theo
quy dfu v.v,. de Plang khOng ap d\lng cbo nhfrng tinh tht khOng hoan.
chinh d6. de Plang cilng khOng &p d\lng cho nhfrng dung n\n, nhiing bOn hqp,
hqp kim, nhiing tinh thl! gi6i in (ciln bAng gill), nhiing tr{lflg thlii thUy tinh, nhfrng
v:)l n\n vO dinh hlnh, mi)t s6 hgp chit rin Cl nhit d thi'p nhu CO, NO v.v ... D6i v6i
nhfrng chi't d6, S
0
ella chling lltn hem. khOng, S
0
> 0.
6. Nguyin If thU' ba cUa nhi't dQng llfC h9c
Djnh li cUa Necxo bao g6m cl dt PHing thmlng duqc coi 13
nguyM 1i thli ba cUa d(mg h,rc hQC vi n6 kh6ng the rUt ra tlr
1i Iva II rna bieu thi ml')t djnh m6i cUa tV nhien.
Vt tAm v6c, n6 klJPng c6 tinh t6ng quat nhu nguyen li I va II. KMc
v6i nhilng nguyen If nay. n6 kh6ng dAn t6i sv thit nhiing ham
123
dQng ca bin nao nhu nQi nang d6i vai nguyen li I va entrbpi d6i vOi
nguyen li II. N6 chi xac gi<i trj giOi S
0
ella entr6pi 0 theo
(XII.25). D6ng thOi n6 cling chi ra ding a gao OK, cac ngung c6
mQt nhfing thut')c tfnh bit, thi dJ..l nhu G, H, F, U, CP, Cv v.v ...
kh6ng cOn thuQc vao nhit dQ nfra.
Nguyen li thU ba cU.a nhit dQng h}'c hqc ciing thmJng duqc gQi Ia
nguyen If khong thl d9t titi OK. Nhfing thuQc tinh ella c<ic a
gAn OK tam cho chUng a vao tr!,lng thai kh6ng tM nao d!,lt tOi OK. ThJ!c
"*Y tru& khi t6i T =OK, dungS, cling nhu Cy ella c<ic da 0,
do d6 kh6ng thi! nao IA"y bOt duqc nhit M duqc chfnh x<ic OK. .
Trong thvc t, chi c6 tM thl!c hin duqc nhfing nhit d(l sieu thfi'p,
cJ!c k1 giin OK, nhung kh6ng bao giG d!,lt t6i dUng OK.
7. SIJ suy bie'n cUa khi li tudng
Bieu thU:c d6i v& enlr6pi ella khlli tUI'mg S"' S
0
+ RlnV + Cyl11T thu duqc tlt phtrong
trlnh thai pV = RT khOng thba miln dC PIAng bbi vl b T--+ 0 n6 khOng di\n 1&
S --t 0 rna dAn tai S --+ -<:() Dieu nay n6i ri\ng cr nhiing nhi1 dQ tM"p, gAil OK, khf If
tuCmg khOng cOn tua.n theo Ji!m:mg tr)nh pV"' RT rna xU: SJ! m(lt
each khac. thai d*c bi1 elm khf If tubng 0 nhil"ng nhi1 d() thilp giln OK kh6ng tua.n
theo nhil"ng djnh lu$t c6 di.Sn gqi Ja sl( suy bie'n (hay thOOi h6a) cUa khf If tubng.
3. AP DI,.ING Lf TH(/ BA lE TfNH
CAN BANG HOA HQC
l. PHllJNG PHAP cAc HANG s6 HOA HOC
Truc'Jc khi n6i vt phm::mg pMp Clic bang s6 bOO hqc, ta hliy xet Sl! ap d\Jng li
thU: bade'! cUu ph !in Ung trong cac h ngiiTig w.
1. Phin Ctng trong cac h. ngung tt,t
D6i v6i nhit dung cUa chat ngung l\1 a gdn OK, khOng the'! dUng 00ng thll't: D()i suy d1g :
,.
cp"'a+bT+rl
biJi. vl crT--+ 0, cOng thU:c d6 se din t6i CP --+ oo , mAu thuin v6i li thU: ba. Chi c6
thi dUng ctlng thU:c
124
Cr=a+bT+cT
2
+ ...
Theo nguyen li thU ba, 0 T-+ 0, S, -+ 0, do d6 a = 0. d6i vlri. chit ngtmg 11,1, 0-
g&-. OK, S, chi c6 th! c6 :
c;,"' bT + c'f + ... (XIL28)
Ntu ta chi gi& 0 hai s6 hl).ng d1u c)ia (Xll.28) thi: 6Ci> cUa phM lhlg giita cic
ch(l ngung II!- 0 g:\n OK c6 dl).llg:
AS,= AbT + Ac'f
vi'l cOng thUc (XII. II) d6i v& AH cUa phlin lhlg se chuy!n tblinh :
AH = AH
0
+..!_AbT
2
+!&:T
3
2 3
(XIL29)
b dAy AH., c6 y ngh"ia li'l hiu lhlg nhit cUa phlin ftng 0 T-+ 0.
Troug truOng bgp chong, AG ella phM lhlg tlnh tbeo phuong trlnh (XII.l6):
AG=-T
D6i vffi ph;in lhlg giiia cic chat ngung b g:\n OK, ta diia bi!u thUc (XII.29) cUa AH
vao(XII.t6) se dugc :
I 2 I 3
AH
0
--AbT --AcT +IT
2 6
(XII.30)
Uy dl).o bam bat v6theo T:
dMJ =-AbT-.!_&:T
2
+I
dT 2
Theo djnh If Necxa
lim (""
0
) 0
T.....O dT
do d6 hAng s6 tich phrm I = 0. Nhu v*y 13. djnh If Necxa cho phep tlnh duqc bing lf
thuy(t hAng s6tich phAn I trong phuong tr1nh (XIl.l6) d6i v& phim lhlg gifra cac chat
ngung t1.1 vi'llchi d6 (Xll.t6) trb thlinh :
AG= -T fAH dT (XII.31)
T'
K6t ni'ly rll"t quan tl"Qng vi: n6 bb duqc tlnh b1ft djnh cUa phuong trinh d6i vffi
AG cUa phlin lhlg trong clic h ngung l\1 va mOra lchil nang tinh duqc can b!ng tuang ling
0 nhiing nhi1 dl) lchlic nhau holin tolin chi d\f3. vilo cdc luqng nbit. Thi dJ.I, c6 the!
tfnh AG theo (XII.30) trong d6 I= 0 :
125
I 2 I 3

--AcT
2 6
(XII.32}
ChU y rang (XII.31) dUng v6"i hilt ki T ni'lo v6"i dit'u kin ph.tn ling phai ra trong
h ngung 11,1 va khi chuyen tlr nhiN d thap, gAn OK ltn nhihlg nhit d T cao h(JJI, thl
phiii kh6ng c6 nhiing bin d6i pha, t(tc Ill chat dang 0 thai ngung ni'lo (rAn hay
lOng) thl phiii. giU: nguyen thii ngung 11,1 lf.y 6 T cao h(JJI.
2. Phan Ung khf vel phan Ung dj thi. Phuang phip cic hiing sO
hoil hQc
Nguyen If thli ba kh6ng <ip dl}ng tn,tc tip cho khf. D6i v6'i phB.n Ung
e6 eha't khf tham gia thl :
6.G = -T JMI dT+ 1Tv6'i I*- 0
T'
Tuy nhien, di,Ia vao pha.t Ung trong eae ogling tl}, Necxo da chUng
minh duqe rAng d6i v6'i pha.t Ung c6 cha:t khi tham gia thl
I= -Rt.j'
6j' Ia t6ng bang s6 bOO hQe ella eae eh;lt khf eu6i (san philm ella pban
ling) trlr di t6ng hllng s6 hOO hQe ella eae eMt khi dAu. Nhu :
t.G =-T JMJ dT -RT l'>j' (XII.33)
T'
va th d!ng ap ehu<in 6.G
0
cUa phim ling c6 ch;lt khi tham gia se e6 :
tlr d6 :
6.G
0
=-T JLllio dT- RT 6.j'
T'
6.G
0
1 Llli
0
lnKp=- RT =Rf-:rr-dT+6.j'
Trong truOng hqp ehung, 6.H
0
e6 dl,lng :
126
T
6.H
0
= + J6.CPdT
0
(XII.34)
(XII.35)
dan gicin SJ! tfnh, Necx.o dua ra mt lo<;It gici thit sau d6i vdi phcin
Ung c6 chtlt khi tham gia :
1) = const, tir d6

= va (Xll.35) tn1 :

In Kp = ---
0
+ __ P lnT +
RT R
(XII.36)

"Hg "c
/gKp=-
!9,IST 8,3!4
(XII.37)
d dAy bang s6 ho;i hQc j = j'/2,303.
2) chtlp nMn rang ::::.
3) cho rang ccic chat khi c6 cp bang nhau va bang
Cp=l4,63J/mol.K, do d6 = 14,63 dn, Ill bien thien ella s6 mol
khi do pban (mg gAy ra.
dCP ""' 14,63&1 1'/:i
1 76
&1
8,314 8,314 '
4) do c6 nhU:ng giil thit nhieu nh11 cho nen phiii dUng c:ic
s6 boA h9c quy uiic (kinh nghim) i thay cho c:ic hAng s6 boa hQC
dUng j va c<ic hAng s6 i dtrqe chqn sao cho kt quil tinh phil hqp vdi thJ!c
nghi?rn. Khi d6 (XII.37) tn) tbanh :
lUI" .
lgKp=-
298
+1,76!\n/gT+M
19,1ST
(X1!.38)
D1y ta cOng thUc rM dan giim trong s6 nhil'ng cOng thUc khac nhau rna Nee XCI dii dua
ra dt tinh KP Cl ck T khlic nhau dOi vOi nhil'ng ph3n ling c6 chA:t khi tham gia. COng thtic
nay cho phep tinh va do d61:J.G
0
hoi'ln tOOn chi d\ffi vao cle d!rl luqng nhit (I:J.H.Ns,)
va cle hartg s6 bOO hqc quy UOc i, clc hartg s6 nay de djnh tlr s\f do nhit bOO hoi va
nhit tMng boa ella de chit bOO hqc.
C.Ong thUc (Xll.38) ella Necxo chi lA mQt eOng thUe g:in dUng. Tuy nhien r.d eho
phep tinh KP d"t nhanh, do d6 duqc dUng dt dlinh gill ling ehirng KP trong de phep tlnh
127
IX). Trong m(lt s6 tnmg hc;tp, n6 ciing cho nhilng ktt qui gin v6i. lhl;lC
khi &a = O. Khi d6 (XII.38) trO thRnh :
IK a
g p =- 19,15T + I
Thi di:J, d6i vm pluin tmg :
Theo (XII.39) :
C02(k) + =CO(k)+ H20 (k)
3,2 1,6 3,5 3,6
.1.H2
98
= 42477,161
lgKp=- 42477.16 +(3,5+3,6-3,2-1,6)
19,15T
I K =- 42477,16 +
23
g p 19,15T '
(XII.39)
Khi T = 1073 K (tUc 13.800C), JS, = 1,7, rift sat v6i. gia tti th-.rc lA 1,8.
Trong nhii'ng tnr<m.g hqp kh:ic thl COng thU'c Necxa c6 the d!n dtn nhfrng sai s6t. Do
d6 phucmg phiip clc hMg s6 hOO. hqc khOng dugc phd c*p vA COng thUc gAo dUng
(Xll.38) hay (XII.39) chi nen dUng trong nhfrn.g phep tlnh sa IX).
II - PHUlNG PHAP ENTROPI T!JYtr 001
Phuong pbap thlr hai d1,1ng li III di tfnh cAn bang boa
'
hqc hoi'm to3.n chi dUng nhiing d<.ti Iuqn.g Ia phuong pbap dlJa
Sl! X!ic dlnh gi3. tri d6i cUa entrOpi cila tilt d. cac chAt tham
gia ph8.n llng. Phl1t11lg pbap nay hin nay duqc dUng chU yeu trong
nhiing tinh toan chinh xac cho mqi phiin llng ba":t kl, c6 ho*c kh6ng c6
chAt khi tham gia.
1. Tinh gi;i tr! tuyt dOi cUa antrOpi
Tien Plang cho phip de djnh dugc gia tti tuyt d6i entropi cita de chit a nhfrng
nhi1 dQ Mt kl nu bitt si,I thuc')c nhit dung ella chting vAo nhit dQ, kt ca. a nhfrn.g
nhit dQ rit thifp va bitt hiu Ung nhit ciing nhu nhit dQ cUa tift ca cac qua trlnh chuyti!
pha cUa chift nu nhfrng qml trlnh nAy Xi\y ra trong khOiing nhi1 dQ kh3o sit (sau oily ta
chi gQi entrOpi tuyt d6i lA entrOpi).
128
Giai thlr mt chft chi c6 mt tinb thi. Khi d6, phil hqp vdi pbucmg trlnb :
T
-sT = :r-fdr
entropi cUa chft d6 a thai khf a d T xac djnh nJ:nr sau :
T""c T,c Tc
S-r = J ,.:;.:!:_dT + Luc + f .=l:!..dr + h. + J-=C!!.dr
T Tnc. T T, T
(XII.40)
o Toc T,
trong d6 L..c vaT"" Ja va nhi1 d n6ng chiiy cUa chit a tinh L. va r. lit
va nhit d sOi cUa cha:t 0 tM lOng,<;.,.. CJ,,
1
va <;.k Iii dung cita
rAn, lOng vii. khf.
Y.ic do chfnh de nhit dung dUQC Mn hiilnh cho tffi nhfrng nhit d r!t thfp,
10 hay 15K, ft nhft ding ph3.i tffi BOK.
Nhfrng tfch phAn trong (XII.40) thm'mg dUQC de djnh tbeo phucmg pluip d6 thj bang
c<ich xa.y dl,lllg du(mg cong trong M lol1- dQ CP-/t' T (hlnh Xll-3) trong M tol1- d.
c,
T -T.
DuOng cong ABCDEF ling vffi Cp
nhfrng gi!i trj thl,l"c nghim cUa S. 1
A ling vffi nhi1 d<) th.ifp nhit rna 1<!-i d6
c6 the do chfnh xac <; cUa chill
khOO sat.
dm'mg cong OA iJ gAo OK Ill
philo khOng c6 s61iu thl,I"C nghim.
D
F
Nhit lhlng a gAo OK c6 tM tlm
Mmg each ngo<!-i suy theo phuong trlnh Oc.,--::::__;__'-'ic--;::';c---o:c.-
phuong cila Dabai (Debyc) (xem Ch. lnT nc lnT s lnT
Xlll. 4). Thea phuong trinh nay, a gAn
OK, dung ti 1 vbi Hiy thim 3 cUa
nhi1 d T. Vi nhit dung cUa r.in
gi!im dt nhanh 6 T <'IOK nen phAn nay
cUa duOng cong khOng c6 imh hutmg gl
Hini!X//-3. X:ic d!nh entn'lpi Mug
tfch pha.n d6 rh! -lnT
nhifu de"n d chfnh xlic cila ke"t qua chung. tfch giCri hl!ll OOi dtrOng cong
OABCDEF, /nT va tung dQ Ung vOi nhit dQ T khiio sit chota gi3. trj cUa clc tfch
pha.n trong (XU.40).
Phuong ph3.p x3.c djnh entrOpi nhu vlra tr'inh bay g9i Iii pluru11g phap nl!i1 hod 1uJc
(dUng nhi1 lm;m.g ke).
Sg xac d!nh entr6pi d6i cila m1 s6 chat cOn c6 th thl,l"c hin bilng pi!UU11g pluip
tinll ki (xem Ch.XUI, phAn C) dlfol trtn nhitng dii" kin vc! quang ph6 va cau t{lo
chit.
!29
2. Tinh hling;&6 cin bling theo entrOpi tuy+t dOi 0: m,Qt nhitt dQ T
Bai to<in nay Ia dan giiln AGSf ella phin Ung x<ie dlnh theo
phudng trlnh :
AGt =Mit - TAST
Khi T = 298K, ta e6 sir d1,1ng sinh nhit ehuin

va entrf:lpi
ehuAn

ella cac trong philn Ung, thuOng duqc cho trong cac
bilng d;p luqng chudn, de tfnh hiu Ung nhit chuAn va bin
thien entrOpi chuAn

)pU ella philo Ung.
D6i veri mt phin Ung dii cho, ta c6 the'! ghi cac d!.ll !ugng chudn tu-12
98
va S2% a
ngay du{ri phlll1Itg tr'inh phin Ung vii. Ung v{ri mOi chd"t trong phiin Ung. Thl d\1, d6i v{ri
phart Ung hidro hoa etilen thlmh etan :
.0. H29!1 (J/mol)
S29s (J/moi.K)
Tl.rd6 suy ra;
H2 (k) + C2H4 (k) = C2H6 (k)
0 52241,64 - 84586,48
130,46 219,24 229,27
(.O.H2
911
> = -84586,48- 52241,64 =- 136828,12 J
(.O.Sin> = 229,27- (130,46 + 219,24) =- 120,43 J/moi.K
(.0.029K)pll' = (.O.Hlon> -298,2 (.O.Si9!1)poj =
=- 136828,12 + 298,2.120,43 = -100915,89 J
(.O.G2w.> = -100915,89 = -RTfn KP = -8,314. 298,2 fn Kp
tl.rd6 suy ra;
"
Kp=4,76.10
Gia tri rlft I On nay cUa KP cho thlfy ph lin Ung thl!c te' Ja m1 til: tnii sang ph!ii va
ditn ra cho de'n he't.
Ghi eM : Gic bing chu11n thui'mg cling cho ll'l!c tiCp the' ding lip chu;in hlnh thanh
.0.02
911
cUa de h(.fp ch!t (IIWllg II! nh11 sinh nhi1 chuin tu-I29s ella chllng). Khi d6 c6
tfnh thing t.G2
98
cUa phim Ung. Thf d1.1 dOl v& ph3n Ung trtn ;
130
AG29M (kJ/mol)
Tl.rd6 suy ra:
0 68,113 - 32, 854
(AG2
98
)po:r == (AG29ll)c
2
H
6
-

==- 32,854- 68,113 "'- 100,967 kJ
Kt qua nay thi!C tt lit phil. hqp v&i kt qua trtn thu dugc bang cich tfnh
(AG29H )po:r == (AH29ll )po:r - 298,2 (AS29H = - I 00915,891.
3. Tfnh h).ng sO can bling theo entrOpi dOi d cilc T khi.c nhau
Khi da tinh duqc hAng s6 can bAng 11.0 ctla phcin Ung theo
entr6pi d6i a m(?t nhit d(' th1 c6 tM tinh dU'Q'c bang s6 ca.n bang a
eRe nhit dl) T khB.c.
Gill sir da tinh duqc 6.0398 ci'.ta phiin Ung thea entr6pi tuyt d6i a
T = 298,15K (25C). Ta dua giB. trj nay ella 6.G39s vao ()\11.15) se xac
d!flh duqc gi3 tr! ci'.!a bang s6 tich phAn I nhu sau :
0 I 2
AG298 = AH
0
- Aa 298,2/n 298,2- -Ab.298,2 -
2
- .!.t.c.298 2
3
-.!.. + 1.298,2
6 , 2 298,2
Sau khi dB: xac d!nh duqc I thl dl!<l vao (XII.l5) c6 the tinh duqc
a nhit d(' T bilt ki. C8.ch llun nay hoan toan chi d113- vao nhilng
dl,li hrqng nhit, kh6ng phiii dUng ml)t gia tr! do dl,lc ni'to ci'.ta bang s6
can Mng.
N6i chung, b8.i tinh can bAng 6 eRe nhit dl) kbac nhau 18. kh<i vAt vii.
Bai tinh nay c6 tilt duqc dan giim di rilt nhO dUng nhUng biing ph1,1
bit do hai nh8. Me hQc Lien X6 M.T.Temkin va L.A.Svacxman xay
di!Jlg nam 1948.
131
4. Phllc:lng phip TemkinSvacxman {1948)
Phoong pbap Temkin-Svacxman lit m(lt phoong pbap tfnh chinh xac.
m sir dl).ng phoong ph3.p nity d.n bit

va

cUa ph<ln Ung
vft SJ! ph1,1 tbUQc dung ella c;ic cba:t trong ph<\n ling vito dQ.
a)Tac6:
AGT = AHT - TAST
oH"T = AH2...., + r AC AST = +
"" k98 p '
!
T OC
-'dT
" T
AGT = Mf298- r6529s + rT Acrdr - r rT Acr dT
h98 h98 T
b) C6 tht chLlng minli ring:
JocpdT- T
dT =-T JacpdT
ciing :
JacpdT- J:;; JacpdT
Mu6n vb. ta dUng phlMlg phap tich phan tUng phlin:
I udv = uv - /vdu utc Iii uv = I udv + f vdu
I dT
Datu=-, --
. T T'
v = I .1CPdT , tir d6 dv = .1CPdT. vQ.y :
uv = J.1cp =
dT - J.1crdT
dodO: .'_ J.1c dT - J.1C P dT = - fdT J.1c dT
T P T y2 P
Vjj.y (XII.41 ) trb tbAnb :
!32
(X11.41)
(XII.42)
(XII.42a)
(XII.43)
(XII.43a)
c) C6 the bifu thj AS, ella phlin !'rng dlWi dl!Jlg ml)t chuOi liiy thlra ella T :
ACP == Aa + AbT + AcT
2
+ ... + AnTn (XI1.44)
Khid6:
... +
vii.;
+'"[I- 2982]+ '[T- 2983J+ ... + ~ [ T n + l _ 298n+llldT ==
2 T2 3 T2 n+l T2
[
(
T 298 l ob[ 298
2
]
== -T Aa fn-+--1 +- T-2{298)+-- +
298T 2 T
+ Oo [r2 -3. (298)2 + 2.(298)3] + ... + ~ [ T n - (n +I) 298n + 298n+lll
2.3 T n+l n n T
(XIL45)
d) (XII.43a) trO thlmh pl111t1ng tri11h Temkin-Svacxmnn nhu sau :
AGT =AH298 -TAS29s -T(AaM
0
+AbM1 +AcM2 + ... +AnMn)
(Xll.46)
trong d6:
T 298
M =ln-+--1
o 298 T
(XIl.47)
T 298
2
M1 =--298+--
2 2T
{Xll.48)
(XIL49)
133
C6ng thtk (Xll.49) dUng chon= I ,2,3 ... kti c:i khi n = -2, nhlfllg kh6ng ap d1.1ng cho
n = 0; d6i vO:i tntimg h<!P nay (n = 0) phlii dUng c6ng thtk (XIL47). ChU Y riing trong
cac c6ng thtk trtn, chi ghi 298 cho dcm giim, nhlfllg khi tfnh Cl.l thf thi thay 298 bAng
298.2,
2) trinh bay phucmg phap Temkin-Svacxman c6 vi: phtl"c 1'!-P Tuy nhit';n vic sir
d1.1ng phucmg phap d6 l"i 'r:tt dcm gilin. Ta chi vic tinh AGT cUa ph:in Ung d\fa vao
(Xll.46) trong d6 c:ic h M
0
. M
1
.. Mn Iii nhitng ham chi elm T, de h s6 nily dii d!lqc
tlnh siln 6 de T kh:ic nhau vit dii duqc th.itnh bling (xem bang XII. I). Thl d6i v6i
phlin Ung:
I
2HCI+202=H20 (k)+CI2
AH2
9
K =- 57391,4 J; AS2n =- 63,954
ACP = Aa + AbT + Ac'T"
2
Aa = -2,26; Ab = 1,52.10-
3
; Ac' = 0,94.10
5
Giii. thfr cAn x:ic djnh AG
0
ella ph lin Ung 6 T = I OOOK. lJng v6i Aa, Ah vit l'!.c' c6 c<i.c
h s6 M.,. Mt va M.
2
. Tra bling XII-I cJT=!OOOK, tad11gc:
M
0
=0,5088, M
1
=0,2463.W
1
, M.
2
=0,2783.10.
5
The nhUng d"i lugng d6 vAo (XIL46) :
Aa;'om =-57391,4 + 1000.63,954- 1000{ -2,26. 0,5088 + 1,52. 10-
3
. 0,2463. w'
+ 0,94. 10
5
.0,2783. 10-
5
] = 7076,5J

C6c sO" trong phu011g trinh TemkinSvacxman (Xll.46)
T,K
Mo
M
1
.10.
3
M
2
.10
-
M.2-IO '
300 0,0000 0,0000 0,0000 0,0000
400 0,0392 0,0130 0,0043 0,0364
500 0,1133 0,0407 0,149 0,0916
600 0,1962 0,0759 0,0303 0,1423
700 0,2794 0,1153 0,0498 0,1853
800 0,3597 0,1574 0,0733 0,2213
900 0,4361 0,2012 0,1004 0,2521
1000 0,5088 0,2463 0,1134 0,2783
1100 0,5765 0,2922 0,1652 0,2988
1200 0,6410 0,3389 0,2029 0,3176
134
5. Nhltng phuang pha.p tinh g'n dUng
Phuong trlnh tinh chfnh xac 6.Gt ella pluln Ung chi dga vao
nhUng dU' nhit ta phucmg trinh :
T T
o. o o JdT f Cd
6.GT = 6.H
298
- T6..S
298
- T
2
6. p T
298 T 298
Khi c6 dll dii kin d.n thlGt v6 S\1' phl,l thuQc nhit dung ella de chAt
vao nhit dQ thi sJ! tinh chfnh xic iiGt c6 the tin nhu da liim
trong phuang phap Temk.in-Svacxman trlnh bay b tre:n.
a) Nhlltlg khi khOng c6 dU dil thlfc nghim dn thit, b
nhit dQ cao, thl c6 thti chd'p nlujn gdn dUng liC P :::::: const. Khi d6:
T
f t.C,dT t.C, (T- 298)
298
Tf dT Tf Tf t.C,(T- 298)
z 6..CpdT =
2
dT =
298 T 298 298 T
t.c,[ f ctT -298 f ct;] l
298 T 298 T
298
T 298
T 298
= 6.Cp(tn
298
+T-l)=M
0
6..CP
b d&y:
T 298
M =in-+- -I
0
298 T
lit h s6 trong phuang trinh Temkin - Svacxman (XIl.46) da thimh
bang (thi dl;l bang XII- l).
D6i vG:i T :-;;; 1600K, M
0
c6 tfnh gl:in dUng theo :
135
(M.,}r ~ 1600 ~ 0,0007T- 0,20
Phuong trlnh (XII.43) tr/1 thilnh:
&Gt = MI1
98
- TdS1
98
- M
0
aCP T (XII. 50)
b) Thtri1ng c6 the chKp nh*" A<;= A<;.
298
=cons{. Khi d6 (XII.50)
c6 r4ng:
(XII.50a)
c) Khi n h i ~ t dung cila mQt s6 chAt trong phAn Ung holm tOO.n kh6ng
duqc bie't thi pbai dUng m()t c6ng thUc kern chinh xac han nO'a btmg clich
cMp nh*" A<; = 0. Khi d6 tir (XII.50) suy ra :
(XII.51)
136
CHIX!NG Xlll
NHIET >0NG LliC HOC THONG KE
. . . .
A- Cel SO PHIX!NG PHAP THONG KE
5I! ktt hqp fi thOng ke (ciing gQi Ill Cd thOng ki) vm m()t s6 ph4n ella
dng lqc hQC c6 ditn dAn t6i SJ! thift mOo nhift li!C lu}c thdng kl, duqc phD.t
tritn 0 pb!n tu thli hai ella tM kj' 20. dng li1C hqc lh6ng sir nhihlg
phuong pMp ciia v*t li thOng cho khli nilng tfnh dugc nhOng gi3 tri bAng s6 ella cli.c
ham dOng vA dl! cUa hAng s6 can b!ng thOng qua nhiing dil' kin vt quang ph6
phAn tir va ve c(u chit, d61A ditu mil nhiet dng IJ!C hqc cO ditn khOng Uun duqc.
1. xAc SUAT flQNG vA ENTROPI
1. xac sui't nhitt d9ng
D6i v6i. cilng m()t vi mfi, m6i thai nhit dng (tlk 13. m6i
trlilllg thai vi mO) c6 tbe th\fC b&ng nhieu vi tM.i kM.c nhau,
nghia Ut bAng nhit!u each phl\n b6 kMc nhau gi11a cac pha.n tlr ella
Xet h 4 pMn tir a,b,c,d dQng
h6n loc;m trong mt)t binh rna ta tuCmg '
tuqng chia Uun hai phatl bAng nhau. Di
nhien, b m6i nita blnh chi c6 the c6
nhGng eAch phan b6 "vi mO" Ung vOi
4- 0, 3-1, va 2-2: a m6i clich d6, con slS
tlui nMt chi slS phan tir b nira blnh kh3.o
sat, con slS thlt hai chi slS pha.n tir a nl'ra
blnh kia. thai "vi mO" 4- 0 Ung v6i
m"t vi thai duy 18. c8. 4 pha.n
tir trung b m"t nira binh (abed).
tluii "vi mO" 3-1 Ung v6i. 4 vi
I
HillhX/II-1. B6ncicbpbllnb6
vi mo v6i ciing ml)t tbai
"vim0"4-l.
131
thai c6 c6 CJ mt nlra binh ta abc, abd, acd va bed (hlnh XIII-I).
COn tr;p1g thai "vi m6" 2-2 Ung v6i. 6 vi tr;p1g thai ab, ac, ad, be, bd, cd.
Chll y dng sg hoan vj 2 phAn tlr thu(.lc 2 nlra binh kh<ic nhau dan tdi mQt
vi tr<:).ng thai m6i, nhung sJ.! hoan 2 pha.n til CJ cling mt pban binh
kh6ng dfin tOi vi tr;;tng thai mdi.
Nu quan sat m(.lt thOi gian dll Iau thi c6 thAy nlng m6i mQt trong
de vi tr;;tng thai d6 duqc g<\i,p .trung blnh vOi mQt sO tan nhu nhau bCJi vi
dng ella pha.n tlr Ia hoan toan h6n to1;1.n. Do d6 tdf cd cdc vi
tn;mg thdi di!U c6 xdc sudt nl11tnhau, tUc Ia vi tr1;1.ng thai nao ciing c6 khii
nAng nhu vi tr;p1g thai nilo. D6 ta til:n de quan tn;mg tam ca sO cho li
th6ng ke.
BOi vi mqi vi tr1;1.ng thai deu c6 xac suAt nhu nhau nen tr;p1g thai "vi
mo" thU ba (2-2) duqc 6 tan nhieu han tqng thai "vi mO" thlr nha't
(4-0) va tr;,tng thai "vi m6" thU hai (3-1) duqc 4 Ian nhieu han tr1).ng
th<ii "vi m6" thU nha't.
Stf vi tn;mg tluii khdc nhau Ung vOi cUng mf)t tn;mg thdi vi mO cUa h
gqi ld xdc sudt nhit dng W cUa tn;ng thai vi mO dii clw.
Trang thi d1,1 tr(:n, xac suAt nhit dQng ella nhihlg tr1;1.ng thai "vi m6"
2-2, 3-l va 4-0 Ia 6,4 va 1. X& sudf nhit dQng ta mt s6 nguyen duang
1, lchac vdi xdc sudt todn luJc, xac suAt nay ta ti sO diiC1llg giila s6
trub'n.g hqp chO dqi va t6ng sO tnrOng hqp c6 xiiy ra. Xiic suAt tOO.n
hqc c6 gi<i trj trong gi6i hl;ln tlr 0 dn l. Nhu th 1 Ut IOn nha't ella xac
sua't tOO.n hqc (hin tuqng hoan toan chic chan) trong khi d6, d6i vOi x<ic
suAt nhit dt)ng thl 1 I1;1.i 13. trj be nhAt.
D6i vOi nhfrng h c6 nhieu pha.n tir thl xac xuAt nhit dng 13. nhiing
s6 nguyen rAt IOn. Trang thi d1,1 tren, ta da chqn h c6 4 phAn tir M SlJ
trlnh bay duqc dan giiin, nhung thl}'c ra h 4 pha.n tir khOng phiii 18.. h vi
m6, do d6 khi n6i ve tr;p1g thai "vi mO" ella d6, ta da ghi "vl m6"
trong kCp. COn vi m6 thl,IC ph8.i chUa hang pha.n tir.
N6i chung, nu h vi mO c6 N phAn tir phAn b6 thanh N
1
phAn tir b
phAn. the tich thU nMt, N
2
phAn tir b pMn the tich thU hai, ... , N
0
ph!ln tir
b pban the tich thU n, cac phan tich Mng nhau thl dl,l'a vao d1;1.i s6
138
t6 hqp, c6 chOng minh r!ng xac su<ft dQng W ella tri:Ulg thai vi
m6 da cho tfnh theo c6ng thUc :
N!
w =
Nl !N
2
! ... Ni ! ...
(XIII.!)
Dl}c bit, nu h chia 18m hai ni'ra, nila thU nh<ft chUa N
1
phAn til, ni:ra
thU hai chUa N
2
= N- N
1
phan til thl xac su<ft nhit dQng W ella tri:Ulg
thai vi rna se bang :
Nt !(N -N
1
)!
W=
N!
(XIII.2)
Nhb c6ng thiic nay c6 the th<fy nhOng "xac sua:t nhit dQng" tWJng
Ung v6i nhihlg thai "vi mo" 22, 3-1 va 4-0 trong thi d\1 trtn Mng
6,4vat.
Slf phAn b6 kh6ng dOng deu nhA"t (c6 tl}' nh<ft) c6 xac sua:t be nh<ft.
Khi d6 t<ft ell N phAn til trung 0 d vao mQt phlin tich, thi d\1 b vao
phlin thUnM't, dod6 N
1
=N. N
2
=N
3
= ... =Ova:
W
N! N! 1 ( 0
= =-= Vl !=l)
N!O!O!... N!
Sl! phAn b6 d6ng deu nh<ft (bOn nhlft ) c6 xac sua:t 16n nh&t. Khi
d6 m6i phAn tich chUa mQt s6 phan til b!ng nhau. Nu s6 ph<in
tich tan thl m6i ph<in chUa N/n phAn til, tiic taN
1
= N
2
= ... = N
0
= N/n
vii (XIII -1) tr/1 tbanh :
W=
N!
(XIII.3)
thiic nay Ia cJ.!c di;Li ella (XIII.l) d6i v6i N da cho.
D6i v6i 4 pha.n ti'r, sl[ phAn b6 d6ng nhlrt thii "vi mO" 2-2) c6 xac suit gifp
6 IM sv pha.n b6 khOng d6ng nhM thlii "vi mO" 4-0).
Khi c6 12 phAn ti'r, 2 truOng hgp gi6i c&ng kh3c nhau xac suit:
sv pha.n b6 d6ng diu nhit (h6n nhtfi) c6 de sulrt gip 924 IM sv phan b6 khOng
d6ng nhlft (c6 tv
139
D6i v& 20 phAn tl:r, ti s6 Mic suit d6 bAng 184756:1 van6 tAng r!t nhanh khi s6 phAn
tir tAng. D6i v6i vi mO c6 h8ng phAn tl:r thi ti s6 d6 CJ!C ki !On. Do d6, d6i
veri I mol khi II u.r6ng 00 ll).p veri mQi tlic d1,mg ben ngoAi, c6 thi! xem nhu holm to8n chile
chin rAng khl se deu loAn b(l thl! tfch, khOng thl! nlio c6 Sl! '*P trung tM ca cac
phan tlr khl vlio mN ph4n thi! tfch bf't kl nlio d6. Nhilng Sl,l khlic nhau rat nhO ve ti kh6i
giiia nhilng phlin r!t nhO cUa thi! tfch chi c6 tht phlit hi11 bAng nhilng phuang phip nlt
d4c Nhilng Sl! sai lch d6, gqi Ill thiing giO.ng, se c8ng nhO s6 phan tit c!mg 16n.
NgoAi. blii tinh vi Sl! phart b6 thee thi! tlch, blii tinh ve SJ! phatl b6 ph;ln tl:r thee nAng
hn;mg hay theo t6c d(l x.ung luqng) cOn c6 t!im quan trqng l6n han. S6 vi thai
W. bing de suit d(lng ciia thai vi mO da cho, vAn xac d!nh bAng OOng thttc
(XIII. I). D6i vdi Sl! phAn b6 c6 xic suit 16n nh!t, n6 d!n t& djnh lul).t ph an b6 theo n<lng
luqng ciia Bonxman (si! xet dueri dAy) va djnh phAn b6theo t6c d(l ciia Macxoen.
an chU Y ring sg phll.n b6 c6 de sullt 16n nh:lt theo t6c d theo nang Jm;mg
holm tolm khOng Ung vai m1 s6 phAn tlr bing nhau trong m6i phAn tOe d(l nang
luc;mg. nhu dieu x3.y ra d6i veri Sl! ph An b6 theo.nhilng ph4n thi! tfch.
0 chung han vii ch41 che han, nhilng blii tinh d6 duqc giii trong v411i thOng kl!
dl{a vao kbai k.Mng gian pha do Gipxct de ra, thu._t ngit "pha" dugc dUng a day
d6ng nghia v& tbai.
2. EntrOpi va xac su8t nhi9t dQng
cac tM.i tl! nhien d6u di,en ra theo chitu ti:r thai c6 it xac
suift sang thai c6 nhitu xac suift hem, d6ng thO:i cilng nhO'ng hin
tl[(!ng d6 trong h c6 chi c6 tl! dien ra theo chitu tang ella
entr6pi. Nhu trong nhO'ng qwi trlnh d6, cii hai d:;li hrqng S va W d6u
tang, chiing duqc gia tr! qrc khi h t& thai can bang.
gili'a S va W phiii c6 m()t m6i quan h dinh ll[(!ng nao d6. C6 the
vit!t S Ia m()t ham ella w :

Vl entr6pi S ta mt tho<: tfnh khuch dQ, c6 c()ng tinh cho nen
entr6pi ella m()t h hQp bbi 2 h kM.c nhau. dQc c6 entr6pi sl va Sz
va c6 xac su!ft nhit dQng w
1
. W
2
se I a :

f(W) f(W
1
) + f(W
2
)
Theo li Xlic su!ft, xac suift ella h phUc bang tich xac suift
ella cac h dan giin dii cifu ra n6 :
140
dodO:
S= f(W
1
W
2
) = f(W
1
) + f(W
2
)
Tir d6 suy ra dng ham entrOpi S pbai 18. m<)t hlun logarit bCri vl trong
toAn hQC, hatn logarit Ht hlun duy nM't c6 tinh : logarit ciia m()t tich
bang t6ng logarit cua tUng s6 h(lllg. Do d6 c6 :
S=klnW (XIII.4)
C6 chtlng minh rfutg S6 til? k Iillulng so'&nxman, k = R/NA,R
18. hAng s6 khi, NA 18. s6 AvOgadro. COng thUc (XIII.4) gQi la cOng thUc
Bonxman. D6 18 m()t trong nhUn.g phuong trlnh co b;ln ella nhit d()ng
hqc th6ng kt.
2. l!NH PHAN BO BONXMAN
1. ThOng ki c6 diin (Macxoen-Bonxman)
a) Djnh phdn bO' Bonxman dqng dan gidn
Gi8. thil mt thl tich cO lt;2p chUa N pban til khi 1i ttWn.g d6ng nhA"t,
trong d6 N
0
pMn til c6 nAng luqng &
0
, N 1 pMn tir c6 nAng luqng &
1
, . Ni
phan tir c6 nAng luqng &i, ... Gi3 thit nang 1uqng ella nhUn.g phan til
re chi c6 the nhUng gi.ti trj gicln do{ln (rai f'll ). Ph!i tlm SJ! pha.n b6
phAn til theo nang luqng sao cho phan b6 d6 c6 x8.c suA"t IOn nMt.
M6i phan b6 18. mt thcii vi mb c6 xac suA"t nhit dng W x8.c
dinh bbi (XIII.l) :
(chii 9 a da.y Sl,l' danh s6 thU tq Mt eMu tit No> D6i v6i N ldn, c6 tht
dUng cfjng thUc gdn dUng Stialinh (Stirling) :
InN! =NlnN -N (XIII.5)
Til do :
141
lnW=InN!-l:lnNi! =NinN-N-(l:NilnNi -l:Ni)=
= NlnN- l:Ni/nNi bCri vl l:Ni = N
S = klnW = kN/nN- kLN;InN;
Phai tlm N
0
, N
1
, ... sao cho S ta cJ!C dl,ti trong dieu N = const vii
U = const (vl he dll(!c gici thit Iii cO 11_\p). Mu6n v1_\y pbai giai d6ng thOi
M 3 phuang trinh :
{
=const
U = LNiEi = const
Sl! gi3.i kMng kh6 nhung dili, ta b6 qua.
Kt quii nhu sau :
u
S=kNinQ +-
T
(XIIl.6)
(XIIl.7)
trong d6 N; 18. s6 phAn tlr c6 nang hrgng Ei ; k = R/NA Iii hAng s6
Bonxman ; T Iii dQ d6i, cOn Q, gQi 13. tdng tr{lng thtli (hay
tdng thdng ke), c6 c4ng:
Q
'<' -<lkT
=""'e '
(XIII.8)
t6ng L dtK;fC 1a:y tlr i = 0 dn i = oo.
(XIIL6) 18. thUc ella mQt trong nhUng djnh lu1_\t quan trQng ella
V1_\t H th6ng ke, dfnh lu1_\t Bonxman (thit l!'.lp mlm 1877) ve SI!J>hAn b6 c6
Xlic sua:'t 16n nha:t phAn ti'r theo nang lw;mg. Theo d!nh lu!'.lt nay, trong
cAn bAng, s6 phAn ti'r c6 nang lugng Ei ti vOi thira s6 e -e; /l.:T , gQi Iii
thita s6' Bonxman.
b) Djnh phdn b6" Bonxman d{lng tdng qutlt
MQt s6 tr<,lng thai ella phAn ti'r c6 the c6 nang Iugng Ei ra:'t gatl nhau tOi
mli'c trong th!Jc t khOng tht1 phan bit duqc nhfmg nAng luqng nay va
142
pbai nMn lA chOng trUng nha!J. Nhilng thai d6 hQp th8.nh
nh6m. S6 vi thai trong nh6m gQi ta tn;mg ili{Jng thOng keg; hay
suy bi11 ella mlic nang luqng Ej.
Trong t:nrCmg hgp nAy, tinh xac sua't d(}ng W, tUc Ia s6 vi
tr<].Ilg thai Ung vm cU.ng m(lt th!ii vi mO, thay cho (XIII. I) phiii
dUng cOng thllc :
N
0
N, N;
W = N! go gl ... gi
N
0
!Nt !. .. Ni ! ..
(XIll.9)
Khi d6, sJ! phAn b6 c6 xac IOn phAn tir theo nang luqng Un.g
v6i dieu kin :
N = Nge-E;IkT
' Q'
trong d6 t6ng thai Q c6 d<].ng :
(XIII.!O)
Q = :!:g;e-;ikT (XIll.ll)
(XIII.IO) ta thUc cUa djnh phAn b6 Bonxman t6ng
quat.
2. ThOng ki c6 dii'n va thOng ki hrqng tti
Ta gQi chung C<ic ph!n tlr, nguyen tlr, ion, nh!n nguyen tU, electron, proton,
natron, photon. v.v ... Ia tilu phdn hay hqt.
cac th6ng ke khlic nhau each tinh s6 vi thai. Trong tMng ke c6 difn
(Mtlcxoen-Bonxman), de dil d6ng nMt (gi6ng nhau) vAn dlli!C xem lA c6 ci tinh,
nghia Ia pban bit dtrqe. Trong th6ng ke hrqng tU, cac d6ng nha:t duvc xem 111 khOng
c6 ca tinh tU'c Iii khOng tM ph!n bi1 duqc.
Th6ng ke lugng ti'r Bozcr (Bose)- Anhstanh (Einstein) 3.p d1,mg cho nhii'ng c6
bW!g 0 bW!g s6 nguyen I ,2, ... thi dLJ. photon. Trong tMng kt nAy cilng nhu trong
th6ng ke c6 difn, s6 a mOi vi thai khOng chi!", tU'c 111 bao nhieu cilng dw;Je.
Th6ng ke lugng tlr Fecmi (Fenni)- Dirie (Dirac) ;ip d1,mg cho nhii'ng c6 spin Ia
nlra s6 nguyen, %% ... nhu electron, proton, natron v.v .... , n6i chung mqi tuAn
theo nguyen If trit Paoli. Trong th6ng ke Fecmi Dirac, m6i vi thai chi c6 thli
c6 nha:t Ia mt
Thi dLJ. xtt cac each ph!n b6 khac nhau 2 d6ng nMt (N = 2) giita hai thai
hrgng ti'r khlic nhau nhiiDg c6 cling mlic nllng lm;mg, mlic nay nhu v$y c6 ttQDg hrgng
th6ng kt g = 2 (m6i thii lugng tlr hlnh dung bAng 10).
143
M.B.

4c6ch
B.A.
EEJ
3cdch
F.8. EE
1 cdch
Trong tntOng hgp chong, . ..6 deb khac nhau phAn b6 N hl,ll d6ng nhtl't ella M thinh
N
0
vito g., thai hn;mg tirkhac nhau dm mU'c EQ, N
1
vi1.0 g
1
thai ltrqng tlr
khac nhau ella mll'c &
1
, ... ,v.v .. bang de nhit W tfnh tbeo OOng thUc;
N
0
N, N;
th6ng kt Miicxoen-Bonxman W = N! 8o g, ... gi
N
0
!N,! ... N;! ...
M.B
(N +g -I)'
th6ng ke Bo:ro-Anhstanh W = n ' ' '
i N; !(g; -I)!
B.A
g'
th6ng ke Fecmi-Dirac w = n I .
i (g;--N;)!N;!
F.D
Khi de mOe nang lugng dl!u gicin va :
N = :EN;= const
U = :EN; &j = const
(XIII.9)
(XIII.l2)
(XIII.IJ)
thi d6i v6i. 3 th6ng ke MS. BA vlt FD, phln b6 c6 de su<!t !On nhit cac h!_!t thea nang
lugng thj bAng mN c6ng llnic chung c6 :
(XIIl.I4)
eA lit hllng s6tu)' thuc v!w blin chit ella a= 0 d6i vOi th6ng ke MB, a=- I d6i
v& th6ng ke BA va a=+ 1 d6i v6i th6ng ke
144
Trir nhiing electron l\1' do (khl electron) trong kim c3c khf (suy bi(n) i:J gil.n OK
vil khl photon. cOn n6i chung dOi vc'ri. de ldui.c el.. .e&; /kT > I . Khi d6 c6 thi bO qua
u b m!u s6 (Xlll.l4) va hai th6ng kt lw;mg til dfu dl\n tCii cllng m(lt k(t qua nhu th6ng
kt c6 ditn M!lcxoen-Bonxman :
N
-A -&/kT
,"' e g; e '
Vl e-1. =constnenN= LN;=c-ALg;e-&,lkT ,e-J..Q
Q= Lg;e-&/kT 1i tOng lri;lJig thai vii e-A.= NIQ.
N
N -&/kT
;=Qg;e'
(XIII. IS)
Nhu trong Mu h1 c3c mrCmg hap, d ba th6ng ke dfu c6 cUng d[nh lu*t phAn b6
clic hi!.t thea nang \UQng, tUc Iii d!nh lul).l phlin b6 Bonxman (XIII. IS), cOng thUc nlly
d6ng nbil:t vCri (XIII.IO). Nhung cac tb6ng ke d6 kMc nhau vf clich tinh de su3t
d(lng W vii do d6 ve C<ich llnh entr6pi S = k/11W cUa
>6i vOi th6ng kC c6 diCn, S = kNinQ + (XIII.?)
D6i vOi cic thOng ke Iuong til, S = kN/11 Q + + kN
. N T
(XIII.l6)_
8- THUYih CO DIEN VA THUYET LUQNG TlJVE NHIET DUNG
CUA CHAT KHi v A CHAT RAN
TruOC khi trlnh bay phuO'llg pMp th6ng tinh clic ham nhi(:t ta qua
nhiing kCt qua ella tbuyt dng hQc pMn tlr (13. tiCn th:l.n ciia H th6ng ke) va cila
thuyt lm;tng tlr di (khOng phai Ill ca hQC lm;mg tic) v nhi(:t dung ciia khi If urCmg va elm
chat rill.
3. NHI$T DUNG CUA KHi Li TUONG
1. Nguyen li ph&n b6 deu nang htc;Jng
Nhi(:t dung Cv ella khi li tm'mg c6 d11-ng :
Cv = <=t +C" +CJ
145
c;.c.., Cd lit nhilng hqp pho1n cUa dung ling vffi chuyin d()ng.tjnh ti!n (t), quay
(q) va dao dng (d) cUa phAn tlr (ta bO khOng xet cac chuyt'!n dng kbac nhrr chuyt'!n
dng ciia electron trong phAn t(r),
It xk djnh phlin nhit dung ling v6i tUng chuyt'!n dng, thuy!t d(mg hqc ph:l.n
tii:dl.fa vilo nguyinli phiin brJ'diu tulng luqng. Theo nguyen If nily, pMn ni nang ling vm
m6i W do ciia chuyt'!n dng bAng d6i vm I mol khf H tuimg. Thl.fc nghirn chi
xac kt't quii. oily d6i v6i chuytn. dng tinh tie'n va quay.
Nhu dugc bitt, rnqi chuyt'!n dng c6tM phAn tfch g:in dUng thanh nhil'ng s6 h\lng
chuyCn dng dc s6 cUa chUng gqi l!t so' b{lc t1f do ella chuyl!n dng khlio sit. N6
triing v6i s61Qll de) cln thi!t dl! xiic djnh dan tri vj tri ella h 6 mqi thi'ri dit'!m bat kl.
Thi d1.1, chuyM dng tjnh tie'n ella I phAn tlr .. trong khOng gian c6 3 bi).c tl.f do (nhUng
s6 theo 3 lri.IC to\! dQ vuOng g6c nhau dOi m(lt), do d6 pho1n n(li nang ttrong ling
bAng U
1
=% RT . PhAn tlr I nguyt'!n tlr (nhu cic khf tro va hoi cUa da s6 kim IU\Ii) chi c6
chuyl!n d(lng tjnh tin (khOng kl! chuyt'!n d(lng electron), do d6 Cv mol cUa n6 bAng:
dU 3
Cv=c;=-t=-R
dT 2
PhAn tfr nguyen tir thing (trong d6 c6 pha.n tit 2 nguyen tir), ngoiti 3 bl}c II! do
chuyl!n dng tjnh ti6J cOn c6 2 IIJ do quay xung quanh 2 tr1.1c vu6ng g6c nhau
vil vu6ng g6c v6i IIl,IC phlln 1lr vil c6 d. chuyl!n dng dao d(lng, do d6 ni nang ctia n6

5
U=U
1
+Uq+Ud= 2RT +Ud
va nhi1 dung Cv mol cUa n6 bAng :
dU 5
Cv =-=C
1
+Cq +Cd=-
2
R + Cd
dT
D6i v6i JElln 1lr nguyen tir kh6ng lhang, ngoiii 3 w do ljnh li6J va nhilng
W do dao dng, cOn c6 3 11,1' do quay xung quanh 3 lri.IC vu6ng g6c nhau, do d6 :
U=3RT+Cd;
Ph4n nhi1 dung cU.a khi g<ln lien v6i chuyl!n -dl)ng dao dc)ng cUa de nguytn lfr
trong JilAn tir khOng tulln theo nguytn li pbAn b6 nllng htqng.
2. Thuyi"t nhi+t dung cUa Anhstanh
Anhstanh (1907) Ia nguiri d;iu titn dli. linh duqc b!ng li thuyt!t pho1n nhi1 dung Cd
tren CO' sO nhilng quan dil!m ella thuyt hrqng tlr cU (ttic IH thuy!t hrqng tlr cUa Pla.ng
(1900), drrqc phiit tril!n lrong nhilng c6ng trlnh cUa Anhstanh). Theo Anhstanh :
146
(XIII.17)
trong d6 CE (9!f) 13 hilm An!ISlan.h dOi vffi I IJ! do dao d(lng ; 8 = hv/k: Iii
d9 dl)c trttng ; v 13 Uin s6 dao d(mg Ung vffi W do dao dQng da eho ; h Iii. hdng s6
Plang, k Iii. hling s6 Bonxman ; m Iii s6 tL! do dao dqng ella phfin tlr. D6i v6i phfin tlr
n nguytn tlr, tift c3. e6 3n II! do chuyc'!n d(lng, nfu dem trlr di s6 W do t!nh tifn vii
quay se tlm duqc s6 W do dao d()ng. v6i jEAn tlr n nguytn tit kh6ng thling:
m = 3n - 6 va d6i vm pha.n tic n nguyen tir thdng, m = 3n - S. bi1 phll.n tir 2 nguyen
tlrehi c6 I bl)eWdodaodQng, m= 3. 2 S =I.
Vic dUng hil.m Anhstanh CE(8{f) khOng c6 gl kh6 khan bit vl. de gi:i tri ella
h.lm d6 then T/0 theo El{f dil dugc tfnh sii:n thfmh bang.
MOi IJ! do dao dQng trong ph!ln tit t'rng v6i mt t;in s6 v Xlic djnh vii. m(lt nhi1 dQ
trung xac dinh. Tan s6 v x:ic djnh ttl nhiing dU ki(;n quang ph6. Khi ph:l.n tt'r c6 ciu
ll.I-O d6i xt'rng thl hai nhieu t.fu s6 c6 thi trimg nhau. Nhiing dao dng tuong t'rng gqi
lit suy bie'n 21itn, Un, v.v ... Khi d6, trong bilu tbUc eila CJ, chUng tham gia v6i hi; s6 2,
h s6 3 v.v ...
4. DUNG CUA CHAT RAN
Trong m;,mg tinh the ella chill cin, kh6ng c6 ehuyln dng tinh ti(n, thmJng cilng
khOng c6 chuyin dQng quay, chi c6 chuyin d(lng dao d(lng, do d6 c6thc'! chifp
Cv = Cd d6i vUi cMt cin (00 qua cii. chuyin d(lng electron kich thlch).
1. Phttc:sng trinh Anhstanh
C6 thl! nghi dUng lfl!C ti(p plurong trlnh Anhstanh (XIII.l7) di tfnh nhi1 dung cUa
cha"t rAn. D6i v6i ffil1-Jig tinh thi kh6ng gian 3 chieu, dao dng c6 3 b;(lc II! do, v;(ly :
Cv ==3CE<am
Phuong trlnh nity bifu thj giin dUng d:ing bil!n thitn Cv ella dan ch!t cin theo T.
No cho gi:i trj 9 0 v3 Cv 3R aT dU cao. Nh1111g 0 vU:ng T tMp, phuang
147
trlnh Anhstanh milu thutin nhifu v& th\fC Khi gAn t& OK, Cv kh6ng gili.m qua
nhanh nhu tinh theo phlJ!rng trlnh Anhstanh.
2. Phttdng trinh f>dbai
Nam 1912, Dabai d1i tlm duqc phuong trlnh cho pbtp tfnh 161 han Cv ella chat riln c6
tinh thl! nguyen tlr. Do'bai cho n\ng trong tinh d.c til!u ph1ln khOng dao dQng
v6i cimg nhilng tAn s6 nhu nhau (nhu trong thuyet dung ella Anhstanh) m1i dao
dng v6i nhilng t;in s6 kMc nhau hQP thimh m(lt ph6 tan s6 lien tir v = 0 den mQt tri
CIJC d!)l Vmax n1io d6. Phuong trlnh D<Jbai c6 d:.mg:
Cv = 3Co (8/T) = 3Co (Xm)
' 12R Ixm x
3
dx
Co(Xm) = Co (8/T) '=' -
3
- --
xm " ex-!
h'
x
kT ' m
(XIII. IS)
Co (8tr) Hl ham Ddbai, ciing duqc tinh siln thimh bang d6i v6i c:ic giR tri S(f
khac nhau.
a nhit d nlt thf'p, khi T--+ 0, Xm--+ DO, khi d6, theo giUi tlch toRn ;
I
"' x
3
dx = n
4
Oex-1 15
121t
4
R 3 3
Cv=3C
0
(8/T)=--
3
-T =aT
59
121t
4
R 1943,66
--
3
- --
3
- J/K.mol = const
se e
(XIll.l9)
(Xlll.l9) gQi Iii phU"t1ng triuh l(ip phu(mg cUa D<Jbai, tile Ia 6 vU.ng T nlt thifp (tir g!in
OK den JOK), Cy ella chill ria ti v& T\ phuang trlnh nay phU h<;lp vffi nghim.
3. St! chuy&n ti:r Cv sang CP
D6i vOi. d.c ch:lt rio, c6 tM dUng phuang trinh kinh :
cP = cv(l + 0,0214Cv
(XIIL20)
T n = nhi1 d n6ng chlly ella chill rio.
148
4. PhiiCing_ trinh Taratxop
d T gin OK, phUl11lg trlnh l*p phlWilg ella Dabai dUng cho nhilng chitt r3n c6
tinh th! 3 chitu.
Nlm 1945, nhA hie hQC Utn XO V.V. Taratxop dii. chUng minh rang i:JT g4n OK, dOi
v<ri nhilng tinh tM c6 cOu mic ld, nhu mica {flllg 2 chitu) :
Cv = bT
2
{b=const) (Xlll.2l)
va d6i v&i nhilng tinh the c6 edit trUes (I chiiu):
Cv =cT {c =const) (XIII.22)
Nhil'ng chAt c6 citu trUe sqi 13. nhDng phln tit polime tuytn tfnh, thi dl} cao su {i:J
400 - 500K, Cv ella cao su vAn Ph\1 tbeo du<ntg thing vao 1), mitn, nhDng
hidrocacbon da nguytn tit khOng c6 mi1h nhoinh v.v ...
C- TiNH cAc HAM NHI(iT DQNG VA HANG so
CAN BANG THEO PHUONG PHAP THONG KE
5. QUAN GIUA CAC HAM DQNG
vA TONG THAI
C6 tM bi6u thi cac hAm nhit dQng CC1 bcin theo tOng thcii
Q va theo cac ham ella Q theo T. D6i v6i 1 mol cMt, N = NA
kN = kN A = R, N A Ia s6 AvOgadrO. R Ia hAng s6 khi. Theo (XIII. 7),
entrOpi mol S c6 :
u
S = RlnQ + - (Xlll.23)
T
Tit d6 :
F=U -TS=-RT/nQ (Xlll.24)
ilF olnQ
S=-- =R/nQ+RT--
i!T or
(XII1.25)
149
Cv
U=F+TS= RT
2
atnQ
aT
= au = R[T2 B
2
1nQ + ZT BlnQ]
aT aT2 aT
Tic!p theo, d6i veri. 1 mol khi li tltdng, pV == RT, do d6 :
:,., atnQ
H=U + pV=U +RT=R> -- + RT
aT
(XIII.26)
(XIII.27)
(XIII.28)
G = F+pV = F + RT = -RT(lnQ -I)= -RT(lnQ- /ne)
G=-RT/n Q
e
vl/ne = l; e = 2,718la co s6 ella logarit t\1'
(XIII.29)
Oic h thUc dUQC rUt ra tl.r th6ng ke c6 Macxoen Bonxman.
Khi d6, entrOpi mol S tfnh theo (XIII.23) (XIII.25) khOng phil hap
t6t v(ri thJ!C nghim va can duqc hiu chinh (xem 7).
6. TfNH TONG THAI CUA KHi Lf TUONG
1. clkfng
De tinh t6ng thai Q hilt cac mUc nang Iw;m.g si va trQng
hn;mg th6ng ke gi tuong ling, nhiing hlQng n8.y x<i.c dlnh ti.r SJ! nghien
cllu quang ph6 pha.n tir va CC1 hQC hn;mg tlr.
C6 thira nhl)n g&l dUng nang hrqng E; ella pha.n tU lit. tOng ella
nang luqng s
1
Ung vm chuyt1n dng tinh tic!n ella phAn tir va En{)i ta nang
lw;m.g Un.g v6i chuyen dng be!! trong pha.n tii g6m nang Iuqng quay Eq
ella pha.n tir, nang luqng dao dng Ed ella cac nguyen tir hay nb6m
nguyen tlr trong pha.n tlr va nang lugng E. ella ca.c electron trong phan tir
(khOng kt cac nang hn;mg kMc nhu nang luqng urong tac c6 ngu6n
g6c lA spin ella nha.n v.v ... ):
Ej =Et +En(li::: E
1
+Eq +Ed +Ee
150
(JOg v& m6i dl;lllg dQng d6 c6 mt trQng luqng th6ng ke
rieng. Trqng lm_mg th6ng ke g
1
Ung v& &
1
(tinh tin) lu6n lu6n bRng 1.
TOng trc.mg tluii Q se c6 Wptg :
Q=Q,QoQi=Q,Q,Q.,Q,
Qj= u-E1/kT ;<4.= Lgqe-Eq/kT
Q
_ l.:g e-Ed/kT . Q _ e-&JkT
d- d e
2. Tling trillng thii tjnh tie'n
D6i vm Q
1
ciia 1 mol khf li tubng, li th6ng ke cho gili tri sao :
Q, = (2mkT)
312
V =

h3 h3N3/2
A
(XIIl.30)
trong d6 k Ia bang s6 Bonxman, h 13. hAng s6 Plang, M Ht kh6i luqng
1 mol khi, m = M/NA, NA Iii s6 Av6gadr6, m 13. kh6i lm;mg 1 phAn tir,
V 13. tich I mol khi.
3. T6ng thii quay
TntOc ht, ca:n xlic dfnh st/ dOl xlfng o-ciia philn tir tile 13. s6 ca'u hlnh
trltng nhau cila pba.n tir khi lilm philn tir quay 360 IAn luqt quanh cic
quay. Thi d1,1, d6i v(ri nhUng phAn tii th&ng d6i xUng nhu H
2
, a
2
,
0
2
, C0
2
,
cr =2 vl khi quay 360 quanh tr1,1c d6i xUng ciia chUng,

chOng hai tan 0 vao nhUng v! tri trUng nhau. Nhllllg d6i v6i. phAn tlr
th&ng khOng d6i xlffig nhu HO hay CO thl a =1. D6i v(1i phAn tlr hlnh
thlip day tam gilic deu nhu NH
3
hay As0
3
thl a =3. D6i vC1i phftn tlr tU
c:f4 thl a =12 vi SJ! quay xung quanh m6i mt trong 4 ba
cho 3 cofu hlnh trimg nhau.
D6i v6i. phftn tlr 2 nguyen tlr va phan tlr n nguyen tlr th!ng, c6 momen
qucin tinh I, tOng t:M.i quay Qd c6 tht tinh dU chinh x<ic theo cOng
thUc gAo dUng :
151
Q = 8n
2
KTI
q crh
2
(XIII.3l)
D6i v& phan tir n nguyen ti'r khOng thing, Qq c6 tinh dUng
kha t6t theo cOng thlic :
8n
2
(kT)
312
(8n
3
I I I )
112
Q = A B c (XIII.32)
q crh
3
trong d6 lA, 1
8
, Ic 18. 3 momen qu3.n tinh chinh cUa pha.n tir.
4. T6ng thoii dao dQng
Bieu thUc Cd hQC lm;mg tir dO"t v6i nAng luqn.g ella dao d()ng tir
ho3. tuyn tinh (c6 1 l\f do dao dng) 18 :
Ed= ( v + hv (XIII.33)
v = 0,1,2,3 ... 13. s6luqn.g tir dao dng, vIa tAn s6 dao d()ng rieng ella dao
dng tir bOa. Tir (XIII.33) tMy r8.ng khi v = 0, vi\n cOn nang lm;mg
dao dng Cl,lc Eo,d = gQi ld niing illt;tng dao d(jng ki!Ong,
ngay OK cling khOng tieu. Thuffilg thi hv duqc gp vao nang
Iugng "khOng" t6ng quat Eo va nang luqn.g dao dng Ed duqc tinh tU mtlc
kh6ng nay:
&d = vhv
Trong SIJ' gftn dUng khao sat 6 da.y, c6 tM 00 qua SJ! chinh
tinh kMng hoB. cUa dao dQng. TrQng lm;mg th6ng Ice gd d6i vOi ccic
mUc dao dng bAng 1 d6i vdi r!n, d6i v6i phan tir 2 nguyen tit va da
s6 phAn tir n nguyen til, do d6 t6ng trc.mg tMi dao dQng Qd c6 the vit :
(XIII.34)
6 dAy e = hv/k 13. nhi1 d4c trllng, ti 1 v6i s6 dao dQng v. Cho v
tan luqt nbilng gia tri v = 0, 1, 2, 3 ... , se dugc :
J52
Q=l+e-9/T + e-29/T +e-39/T + .....
X= e-err ta dugc:
2 3
Qd=l+x+x +x + ...
Vl x << 1 nen ta ap d1,1ng duqc cOng thlk d6i v6i ca'p s6 nhan:
2 00 1
l+X+X + .... +X =--
1-X
(XIII.35)
COng thl'tc nity ap dt,mg cho phAn tir 2 nguyen tir (c6 1 tl! do dao
d(lng). !l6i v6i phan tir n nguyen tir (n 2 3) t6ng- thai dao d(lng 0., lit :
m 19
Q=n .,.
i=ll-e
1
(XIII.36)
Tich ll dugc la'y cho m t1J do dao dt')ng ciia phan tir (m = 3n - 5
d6i v6i phAn ti:r th!ng Va m = 3n - 6 d6i v6i phan tir khOng thing) ;
8i = hv/k. V; lit W.n s6 thut')c b*c 11,1 do dao dng thU i.
5. T6ng tn;mg thiti electron Ce c6 dc.mg :
Oe= :Egee-c/kT = goe-eo/kT + g,e-1/kT + g2e-2/kT + ... (XD137)
Nang hrqng electron trong pha.n tir c6 Ee = E
0
,e-

Ia ni\ng lm;mg "khOng" ella electron, nghia lit nang lm;mg b mOe
tha'p nha't cila electron trong phan tir iJ - thAi ca bim, khOng hi kich lhich,
0 de) kh6ng d6i. TU thqc tl'tc lit ti:r ccic dU quang ph6,
kh6ng the x<ic djnh dm;tc Eo,e chi c6 x<ic d!nh dm;tc hiu E'e = f:.e - Eo,e
Khi tinh Q.,, ta cha'p nl$1 lily 1\,o = 0 nghia lit tinh rulng hn;mg electron tit
mOe quy u0c d6, dO d6 kbOng ph<li lit tfnh '4 rna lit tinh :
153
= :Egee -e:'JkT = go + gle -e:',/kT + g2e -e:'2/kT + ... (XIII.37a)
hOi vi &'
0
= Eo,= 0. S1J so s<inh hai bic$u tht'ic Qe Q'e cho tha:y:
= e
(XIII.38)
Vl mt'ic nang lm;m.g electron kich thich tht'i nha:t E'
1
ra:t l6n so v6i mt'ic
ca bim !ffi6ng kich thich, cac mt'ic kich thfch tie'p theo &'
2
, e:'
3
... l<,!i cang
IOn nen: 6 T < 2000K c6 the bO qua s6 hl,!llg th(l hai va ciic s6 hl:ffig sao
cU. (XIII.37a). Khi d6:
Eo.e = N A .Eo,e
kT NA-kT
Uo
=-
u
In = In g
0
- ---2..
RT
RT
(XIII.39)
(XIII.40)
(XIII.4l)
g
0
13 tr<;mg ltn;m.g th6ng ke ella mile nang Iuqng electron ca bim kh6ng
kich thich ella phAn tlr. D6i v& da s6 pha.n tii 2 nguyen tlr, & = 1. d6i v6i
phAn tir02, & = 3 v.v ...
Ghi chU. Khi n6i ve nang hrqng "kh6ng" ella phAn tlr, thOOng nguai ta
chi ki hiu Ilt e:
0
, n6 bao g6m khOng nhiing rulng lm;m.g khOng ella
electron rna cA nang luqng khOng hv ella dao d()ng.
7. TINH cAc HAM NHleT 1QNG CUA KHI Li TUONG
THEO TONG THAI
1. Hl+u chinh cOng thll'c tinh entrOpi S cUa khi If tllllng
De cho kft qul!. tinh phU hqp t6t v6i th\fC entrOpi mol ella khi If tuUng clln
dm;rc tfnh theo cOng thd'c sau :
154
S=ESi+R-R/nNA
atnQ
s. = RflrQ. + RT=:::!!
I I i1J'
(XIII.42)
(XIII.43)
Si Ia ph4n ella entrOpi Ung v6i tirng chuyl!n dl)ng ritng re (nhll = enuOpi
tjnh tiln, Sq = entrOpi quay v.v ... ). Si vAn tinh theo (Xlll.25) ella th6ng kt c6
2. NhUng him nhit dqng .cUa khi li ttdJng don nguyin til'
D6i v6i khf li tm'm.g dan nguyen til, tUc Ia phAn tit chi c6 1 nguyen tlr (nhu cac khf tro
vii hoi ciia n.hitu kim khOng c6 chuytn dl)ng quay va dao do d6 mQi lhu(lc
tinh dl)ng ciia n6 chi do chuy6! dng tinh tiln va chuy6\ dng electron quy djnh.
a) Hf!p phdn tjnh til"n cUa c&c hiim nhi(t d9ng. Theo (X111.30) t6ng ll"l!llg th6.i t!nh
titn 1a:
(
2
xMk.T)Jf2y
Q,= ,dod6

(2xk)
312
3 3
/trQl = lr1 .,.,..,
12
+ -lnM +-tnT+ lnV
hNA 2 2
atnQ
1
3 d/t1T 3
--=---=-
ar 2dT 2T
Tlr d6, Ia tinh dugc U
1
theo (XIII.26) :
U
1
= RT
2
attrQ
1
=
i1I' 2
dU 3
Cv
1
= -
1
= -R= 12,471 J/K.mol
' dT 2
S. tinh theo (XIIL43) : S. = RtrrQ
1
+ RT at:;
1
=
(27tk)3/2 3
= Rln ,
12
+ -RlnM
b
3
NA"' 2
3
+ 2R/nT + R/nV
D6i v6i. 1 mol khi If tm'm.g V = RT/p, do d6 :
R/nV = R In R + Rln T- R In p
3
+ -R.
2
3
+ -R + RfnR
2
3 5
+ -RfnM + -R/nT - R In p
2 2
(XIII.44)
(XIII.45)
(XIII.46)
!55
b) Hw pluln electron cUa cdc ham dqng. Theo (XIIL40) tOng tnptg thai
electron Ja Oc "' goe -to . lkT . ve thyc chlft, dl[li lm;mg nay chi Ung v& mite electron CCI
bim, khOng kich thlch ciia phAn tit, cOn de mUc kich thieh dtu bO qua. Theo
(XIIL41) ln0e "'lnSo- UJRT, do d6:
tir d6 : "'const
(XIII.47)
Cv "' dUe = 0
,e dT

(XIII.48)
c) Nlliing hiim dl)ng todn pluln doi v6i I mol khi li tilting dun nguyin tU.
3
Cv"'Cvt+Cv.,"'Cvt=-R =12,471J/K.mol.
' ' ' 2
(XIII.49)
D6i v& entrOpi, sau khi e1>ng S. v& Sc, phai b6 sung th!m s6 ehinh bMlg
R - R/11NA, lite Iii tinh S tolin ph&n tbeo (XIII.42) :
(21tk)312 3
S=S
1
+Se+R-RlnNA=Rin
3 312
+-R+RinR +
h NA 2
-9,6725 (J)
3 5
+-R/nM + -RinT
2 2
(XIII .50)
(XIII.50) lil thUc Xad.uru- TitrOI (Sackur Tetrode, 1912).
Tl[li lip sual chuin p =1,013 bar, Rll1p = 0, tadugc:
3 5
S
0
=2RinM +2RinT + Rlng
0
- 2,314
(Xlll.51)
0
S ::: 6,863/gM + 11.437/gT + 4,515lgSo 2,314
(XIII.52)
156
0 T = 298,15K (=25C):

= 6,8631gM + + 26,0
Titp theo, la tfnh :
5 5
H=U+RT= U
0
+-RT=H
0
+-RT
2 2
T
U
0
=Ho OOi.vllJ= U
0
+ JcvdT vilH=U+RT=
'
T
= U
0
+ J<cv + R)dT =
'
T
MJ!.t khac H= H
0
+ JcpdT,dod6 U
0
=H
0
'
theo:
5
C =Cv + R =-R =20,7851/K.mol
' 2
(XIIL53)
(XIII.54)
(XIIl.55)
() () () () 5 3 5
G = H - TS = H
0
+
2
RT -
2
RT/nM -
2
RT/nT - RT/11 g
0
+ 2,314T (XIII.56)
d-H8 5 3 "i
T = 2R -2R/nM Rln&) + 2,314 (XIII.57)
=- 6,863/gM- 11,437/gT- 4,515/g &o + 7,282 (XIII.58)
Hilm "(0- thllOng gQi lit tM chuOn rUt gt;m vii dUng di tinh cAn boa
hQC (xem 8).
3. Nhltng hilm dc}ng cUa khi li tU'd:ng da nguyen tlf
06i v6i khi li tuimg da nguyen tlr, tVc lit phan tlr c6 n nguyen tlr (n <! 2), nhitng hgp
phlin tinh ti(n vit electron ctia cic hitm nhit gi6ng nhu ctia khi li mbng dan nguyen
til dii tinh (J trtn. Ngoai ra cOn c6 nhilng hgp phlin quay vilo dao
ChU y lit d6i v6i nhilng hgp ph:i.n ni phAn tlr (quay, dao dng) vl H = U + RT
nen H =HI+ = ul + un(li + RT, nhung HI = ul + RT. do d6 :
H,6i = un(l;
(XIII.59)
dHoo; dUn(li
c;,n(li = ----;r[ = = Cv,n(li
(Xlll.60)
!57
Gn(li = Hn;- = Un<)i- = Fnoi (Xlll.61)
a) Hqp pluin quay cUa cdc hOm nhift dng:
l) DOl' vdi p/riin ttl 2 nguyen rU vJ phdtt ttl nnguyen ttl tlulng. Theo (XIII.3l) tOng
thai quay \11. Qq = SikT IJnh
2
, do d6:
8n
2
k I
= Itt -
2
- + . fnT + ln-
h 0
O!nQq = dinT =
aT dT T
tit d6 ta tfnh duqc nhUng hqp pMn quay cUa Clic hli.m nhi1 d(lng :
U = H = RT
2
OlnO.q =RT
' ' or
Cv.q = cp.q = R
iJ/nQ
+ RT--' =
or
I
RlnT + Rln-+
0
8n
2
k
+Rln -
2
- + R

= 742,66 (1)
G
__9_ = - RlnQ
T q
I
= - R/nT - Rln - - 175,68
0
(XIIl.62)
(XIIL63)
(XIII.64)
(XIll.65)
2) DOi vdi phdn ttl n nguytn ttl kMng t/uing. D1,ra vilo t6ng thai quay .(XIII.32)
va ding tlnh nhu se duqc :
3
Uq = Hq = 2RT
3
Cv,q = cp,q =
2
R
3 I
s, = -RinT + -Rin
2 2
bJ HlfP pluin dao dng cUa cdc hilm nhit t!ng.
(XIIJ.66)
(XIll.67)
+267,67 (XIII.68)
I) 01}1 vdi phattti'l 2 nguyinti'l(c6 I 11/ dng), tit tOng thlii dao d(mg
(XIII.35) ta c6 :
lnQd = - ln(I - e-
11
/T)
!58
A.p d11-ng quy t!c tfnh d1:1o h!un eUa bilm_ hqp se tlm tMy ;
Thd6;
d/nQd I 9/T
dT"'Teetr_l
dU
0
.
Cvd =C,o o- oR OIT , "'C(8/T)
' dT (e -1)
Fd = Gd = -RT/nQd = RT/n(l-e-e1T) =
d/nQd
sd = RlnQd + =
oR[ -/n(l-e-etr)] = S(9/T)
' -1
(XIII.69)
(XIII.70)
(XIII.?!)
(XIII.72)
UE(8/T), CE(8/T), vll. SE(8/T) Ill nhihlg hiim Anlwanh nrong Ung v6i
n(li nAng Ud, dung Cv,d' nilng hrgng 11! do Fd va entr6pi Sd d6i vl'ri I fl! do dao
d(lng. ChU Y r3ng d6i vl'ri hqp phM dao dl'>ng Cv,d ella dung Cv eUa kbi If tubng,
phllOJig ph3.p thOng kc'! eho kc'!'t qua trU.ng v& thuy1 dung ella Anhstanh.
Oie h!un Anhstanh tinb sin thimh bang nblmg gi3. trj 0 eRe 8{f kh3.e nhau.
2) D6i vOi pitOn tU 11 nguyen tU (n 3), s6 t1! do dao dl)ng Ut m = 3n - 5 d6i v&
pban tir thing va Ill m = 3n - 6 d6i vc'li pMn tir kMng thfulg. Khi d6 <J.t c6 <4ng (Xlll.36) va :
m m 8/T-
Ud = Hd = Lu(8;/T)=
ial e l -I
(XII1.73)
(XII1.74)
(XIII.75)
(XIIL76)
!59
c) Nlliing luim 11hit dng todn plui11 dol vUi lmol klli It tudng da nguylntU. ~ thu
dtrqc nhUng hli.m nhit d()ng toim phAn cila khi If tii('Jng da nguyl!n tlr, ta Jay nhUng hli.m
nhit d()ng tOO.n philn cUa khi d<m nguytn tlr (dii g6m hQ'P phAn tjnh tin va hQ'P ph:ln
electron) c(lng thtm nhUng hQ'P ph:l.n quay vii. dao d()ng.
Thf d1,1, d6i v6i phti11 rU 2 nguyen u( sC dugc :
s
Cv = '2R + CE(G/T)"
7
H = Ho + 2RT + UE(G/T) ; Ho Uo
CP = ~ R + CE(G/T)
3 7
S
0
= -R/nM + -R/nT + Rln lgo +SE(G/T)+ 175,36
0
G" - H ~
T
2 2
= - ~ R/nM _7_ RlnT- R/n lg" + R/n(l - e -ll/T)- !68,40
2 2 0
=- 6,863/gM- 16,0!5/gT- 4,575/g lgo +
0
+ 4,575 /g(l-e-
91
T) - 168,40
(XIII.77)
(Xlll.78)
(XIll.79)
(XIIL80)
(XIll.8l)
(XIIl.82)
(XIII.83)
8. T[NH CAN BANG HOA HQC TRONG KH[ Li TlfdNG
D6i v6i 6.Gt cUa pban Ung, ta c6 the vit :
6.Go 6.Go 6.Ho 6.Ho
____I. = ___I. ___ o + __ o
TUc Ia :
b day
160
T T T T
lllio
__ o
T
(Xlll.84)
va = 18. hiu Ung nhit chwin ella phi\n Ung giA djnh d p = 1 atm
vil T =OK.
khlic:
tUd6:
RIK
---- np
T
InK =-_l_ t.G!f =-_1_[,-.(G!f
P RT R T T
(XIII.86)
Nhu tinh Kp pbai bit the chua.t rUt gqn (Gt - d6i
v(ri mQi chAt trong pban Ung va ph<li bit hiu Ung nhit gi<l djnh
ella pluin Ung.
Th chua.t n1t gQn ella eMt khi d clic T khclc nhau thuOng duqc
th3.nh bang trong d6 c6 cii sinh nhit chu&n Ung nhit hlnh
thlmh) ella nhfrng hqp ch:ft khf (d6i vOi dan chAt = 0). Khi
d6 c6 tinh ella ph8.n Ung theo quy tk sinh nhit thOng thuOng :
(Xlll.87)
Khi khOng e6 dll ella cac hgp chAt khi thi c6 tht tlnh
ella ph<in Ung theo h thUc sau :
(M-Ig)pU = (M-I29s)pu- L\(H29s- Hg)
Ba.y giO xet m()t thl Tim KP cUa ph lin Unl:
C,H,(k)= C,H,(k) + H,(k)
iJ IOOOK batlg cich s{J nhitng dil sau :
(XIII.88)
161
Hg)/T AH"
. "
UT"' IOOOK kJ/mol
Jhnol.K
H, 135,43 0.
C1H2
-217,40
227,10
C1H4
239,47
60,69
Gilii 0 1000K
A( G'f; = ( 217,40 135,43) ( = 113,36 Jhnoi.K
= 227,10-60,69 = 166,41 kJ/mol

T
= 166,41 kJ/mol "'166,41 Jhnol
!000
AGj. = ::-ll3,36+166,41=53,05J/moi.K
T T T
I K ::- MiT
g P 2,303RT

19,147 T 19,147 '
tlrd6:
KP = I, 7.10-
3
162
CHUJNGXIV
QUY TAC PHA. GIAN DO PHA
A-QUYTACPHA
1. MQT SO KHAI
1. Pha
hqp nhfing phrut dOng gi6ng nhau ella mt h hQp thAnh mt
pha (hay tilling), giOi ht,m vOi nhfing pMn kh<ic bang nhlrng W pha.n
chia (xem C11.1.2).
2. Chilt hc;fp ph4n cUa h'
Ut nhfing chAt hrnl hqc trong h, c6 the tach ra khOi M va tOn 0
mQt thbi gian la.u b ngoRi h. Thf d1,1, d6i vOi dung djch NaCI
trong mr6'c, nhfi!:tg cha't hqp phan 13. H
2
0 va NaCI; nhiing ion Na + va 0-
tuy t6n trong h duOi d;.tng nhfing titu phAn chuyen dQng dQc
nhlDlg khe.ng the xem Ia nhti'ng chAt hqp phcln vl kh6ng tht! tach rieng ra
khOi h va t6n b co b ngOO.i
3. cau til
S6 clu tir ella h Ut s6 nhO nha':t nhfrng chat hqp pMn dll de xac
thfmh phcln ml)t pha bA"t kl ella h, s6 ca:u tir lit s6 chAt hqp pM.n rna
n6ng d c6 the thay-d6i dQc trong m6i pha cUa h.
N!u c<ic chilt hqp phan kMng tudng tac bOO. hQC v6i nhau (khOng c6
ph8.n. iing bOO. hQc) va nu c8.c pha c6 thanh pban khcic nhau thl sO cAu tir
bc\ng sO chAt hqp phlln. Nu c6 phiin Ung bOO. hQC trong thllugng ella
nhilng chAt hqp pM.n tham gia vao can bAng phili ph1,1 thuQc vao nhau.
Khi d6 khOng dn bit hrQ'Ilg ella ta't c3 inQi chAt hqp phAn, chi dn bit
163
luqng cUa mt s6 nao dO chAt hqp phlin 18 dO xB.c d!nh ..hilnh pMn pha
cUa cAn bang. NhOng chfft hgp phlin nay gQi lA clu1t hlfP phtill dt)c
-_ cUa ht}. S6 cUa ch6ng chinh lit stf diu titcUa hf. nguyen llJa
chQn chcit hqp ph!n n8o tam cifu tlr cU.a h 18 tUy y lJ mile dl) nao dO.
Vffn de quan tn;mg kh6ng ph8.i 18 c:ta chQn chfft hqp phlin nao lam cffu
tlt, rna 18 a chO M c6 bao nhitu cAu tlr (tUc 18 c6 bao nhieu chAt hqp phlin
d()c Ne'u trong h c6.ph8.n Ung hoB. hQC thi s6 cau tir bAng s6 chAt
hqp phlin trir di s6 phin iing d()c nOi chong ta trir di s6 phuang
trinh lien n6ng dl) cUa eRe chAt dO trong h can b8.ng.
Thi dl! 1. Xtt 2 pha c6 nhihlg chi"t hgp phin Ja NH
4
a cin va nhihlg khi NH
3
va
HQ hQp thi"mh pha khf 6 trtn pha cin NH
4
a. Tdng s6 chi"t hgp ph!n ella ta 3. Trong
pha khf, khOng c6 hoi NH
4
Q vi khi NH
4
0 (cin) thang boa, thl n6 phAn li thJ!C t hoi"m
toi"m theo phuang lrlnh:
NH
4
Q(r) = HO(k) + NH
3
(k)
Khi cAn b;ing, n6ng d(l cUa nhiing chi"t hlnh thi"mh neJl pha khi !ien v6i. nhau bbg
mQI phuang trlnh:
[NH3] [HQ] = K
Do d6 s6 ci"u tlr cUa bAng 3 - 1 = 2, nghia Ja dl! xAy dl10g nen M hai pha d6 chi
dn hai chi"t Mt kl chQn tUy Y trong s6 ba chi"t hgp ph!n cUa n6111. dU, thf diJ c6 the chQn
NH40 va HQ hole HQ va NH
3
v.v ...
N(u them difu thU hai [NH
3
] = [HO], nghia Ill them m(lt phuang trlnh lien
ndng d ciic cha:t, thl s6 ciu t{r cUa giim. I dan vj tl1c Ill bbg 3 - 2 = I. tho3 miin
d hai phuang trlnh d6 Ill thu d119'C ti:r NH
4
a (rin); ti:r cha"t nay c6 th! xa.y d110g dugc
cit hai pha cUa (pha r-Jn va pha khf).
Thi dl! 2. Trtn 28C, dung djch nu&c cUa N8;!S0
4
va KN0
3
khOng hlnh thlinh hidrat.
Gifra N3:2S04 va KN03 trongdung djch c6 fililn Cmg:
()
S6 chit hgp phlin cUa h Ia 5 gdm H
2
Q, Na
2
S0
4
, KN0
3
, K
2
S0
4
va NaN0
3
. S6 philo
dog ll't I. V$y s6 ciu tli cUa Ill 5-1 = 4.
Thip han 28C, hidrat Na
2
S0
4
.JOH
2
0 c6 thll t3.ch ra khOi dung djch. Khi d6 t6ng s6
chit hgp pUn Ill 6 nhung s6 ci"u tli vln Ill 4 vl, ngoai. philo Ung (a), c6 them phin Ung
m6i., dqc
(b)
164
2. QUY TAC PHA
Ta xet tnWng h<Jp t6ng quAt nhlit ella mQt d! g6m K tl:r
ph!ID b6 trong + pha, trong m6i pha deu c6 W:t d K c!lu tir. Khi c6
cOn bAng uong h d! thi thl :
1) nhit d\,1 ciia tilt ca mQi pha phch blmg nhau;
2) :ip suAt 0 mQi pha ciing ph3.i batlg nhau;
3) the! boA hoc ella m6i ca:u til i pruli b&ng nhau 0 ffiQi pha.
1. Thi8t 1'-p quy tic pha
Dt thie't quy ta.c pha, ta xet:
a) St/ tham s6 cOn bdng. Hai tham s6 cubng dl) quan trQng nhlit c6
cinh hllbng de'n can b&ng ta d T va ap sua:t p. Thanh phatl m6i pha
ella ciing 1a nhGng tham sO ca.n Mng quan trQng. Nu bieu thi hiQ'Ilg
ella m6i clfu tir trong m6i pha b8.ng d chUa % chAng th1 d6i v6i. m6i
pha chUa K c!lu til, chi cAn dl) chUa % ella (K - l) ca.'u tir 18. dll. Do
d6, d6i v6i $ pha, s6 n6ng di) di)c la $ (K- 1). t6ng s6 tham s6
cAn bang lit 2 + $ (K-1).
b) Si/phlldng trinh lien h ctic tham sO cdn bdng. Khi c6 ca.n bAng the'
-boA hQC ella m6i clfu tir i trong d clic pha phlli bAng nhau. Nfu dUng
nhiing Mu phiy d6 ki hiu cac pha va dUng nhfing chi s6 1, 2 ... K
chi c8.c t\r thl d6i v6i Sl! pha.n b6 can bing ella K diu t\r trong pha,
tac6:
' " +
= ...
0 ..
K bang ...
K ($- l) phtiDng trlnh
165
M6i hang c6 (lfl - 1) phudng trinh, ca. c6 K hfulg, lring s6
phuung trinh lien h clic the boa hQC lil K( lfl- 1 ). D6i vdi m6i pha, the
boa hqc ella m6i cA'u tir i 18. ham ella T, p va ella thilnh pMn ella pha d6.
Nhu s6 K( lfl- 1) phuung trinh lien h cac tht'! boa hqc khi c6 can
M.ng cling d6ng thffi Ill s6 phuung trlnh lien h cac tham s6 can bang.
c) Bie'n d{5 hay si/ fl! do nhift dng cUa hf
T6ng s6 tham s6 ca.n bing ciia lil 2 + q, (K- 1). T6ng s6 phudng
trlnh lien h chOng Ia K( tfl- 1 ).
s6 tham s6 cAn bing dQc ll).p, kh6ng hi mQt Sl! rang buQc nao Ia :
f= 2 + -I) -I)= 2 + +K

(XIV.!)
f gqi la stf b9.c llf do nhit d{5ng cUa h, v&n tat han, stf b{ic tlf do
hay bie'n d9 cUa b. D6 ta sO tOi da nhUng tham sO dQe c6 bi6n
thien tU.y y (di nhien trong giCri hc;m nao d6) rna vein khOng xam
vilo cAn bing ella h di Cling c6 tht! n6i f ta sO nhUng tham s6 w,mg
thai ella M rna ta c6 chqn tUy y gia tri ciia chiing (trong giCri hc;m nao
d6) rna kh6ng Jam thay deli sO pha cUa h. (XIV.l) lit thUc cUa quy
tdc pha do Gipxa thi6t (1876) va c6 tht! pbat bit!u :
Si{ lxjc tlf do f cUa h b&ng so caU tli K, ct)ng 2 va trli di s6'pha tfl cUa h.
Danh tl.r "quy tiic" thubng duqc hieu Ia rnQt quy rieng, gAn dUng.
0 dAy thl khOng phiii nhu vl).y. Quy t3.c pha Ia mQt d!nh chfnh xac,
dUng cho rnqi can bAng pha. N6 lB. d!nh co bAn trong IInh vt!C
nghien ciiu nay.
N6u m(?t trong hai tham s6 p T duqc gifi' c6 djnh thl s6 11! do
ella h gii'un bdt I dan vi :
(XIV.2)
Khi d6 fdk gqi Ia si/ b{ic llf do cO die'u kin (dk = diCu kin). N6u d
hai tham s6 p vaT dCu kh6ng d6i thi s6 11! do c6 diCu kin (kt!p) ella
bilng:
(XIV.3)
166
Vl s6 tl! do f cUa h kh6ng Ia am (dieu nay kh6ng c6 nghia)
:ho nen tU (XIV.1) suy ra:
(XIV.4)
Nu K = 1, 4t ::; 3, nghia Ia h 1 d(u tir (thi dq cMt nguyen chA"t) chi
c6 the t6n t{li du6i 3 pha cAn bi\ng d6ng thffi v6i nhau 13. nhieu nha"t.
Quy tic pha ella Gipxa duc;1e thit v6i gici thit m&i cAu tir c6 the
chuyen t!J do (kh6ng b! dm rriJ) tlr pha nay sang pha khac. Do d6 n6
khong ap dt,mg cho nhilng h g6m nhihlg chat (dung djch) ngan each
nhau bCri nhiing mang ban thAm.
2. Phin cac hi; nhii;t dQng
cac h nhit dQng c6 the phtm
a) Theo sii ccfu tti: h 1 cAu tlr hay nhAt, h 2 d(u tlr hay h
hai, h 3 ccfu tli hay 11 ba, v.v ...
b) Theo st{pha: h 1 pha, 2 pha, 3 pha, v.v ...
c) Theo st/ tl( do (bin dQ): h khtmg bin hay heft bin (kh6ng c6
bl)c I biln(f= l),he2 biln(f=2),he 3 biln(f= 3)
v.v ...
B - GIAN DO PHA H$ MQT CAU TIJ
3. GIAN >0 PHA CUA NUOC
1. Nghiin clru lJvUng ap sua't trung binh
Hmh XIV - 1 trlnh bay gian d6 pha (cfing gqi 1a gicin d6 th3.i)
ella nude H
2
0 trong pruing p, t 0 vUng <ip suM kh6ng cao 1.\m
(p < 2000 bar). N6 trung b ch6 icbac v6i tuyt d;:ti da s6 cac chAt
lOng khk, nude c6 the tich rieng iJ lOng be han b thti d.n.
ffinh XIV - I dUtJC tr'inh bay lJ d1p1g rAt sa luqc, nghla Ia kh6ng theo
nhihlg ti 1 cMt che. DuOng cong RI 1a dut'Jng thiing hoa, cOn IN la
167
duimg n6ng chdy va IK ta du&ng hoti hoi. Ba dllCfng d6 nhau 0 die;m
I 13. dilm ba ella nuOc. ChUng phan chia gi<in d6 ra tam 3 vU.ng (hay
m&i vUng Ung vOi Sl! t6n ella mt pha : miDc da, mrOc lOng va
hoi nuOc. 0 m6i vimg d6, c6 hai tl;l' do : p va T c6 the;
re nhilng gia Ui tUy Y. COn bin than m6i dmJng bie;u dil!n 18. quy tich
nhUng ditm Ung v& Sl! t6n t(li d6ng thCri ella 2 pha can bAng : dmJng
thiing boa RI Ung vOi can bAng rAn - hoi, duUng hoci hoi IK v& can bang
lOng - hoi va duUng n6ng ch<iy IN v& can bclng rAn - lOng. m6i
dubng cong d6, h _chi cOn c6 m1 tl,l' do : trong hai lm:;mg p va T,
chi mt Ht dc s1,1 ph1,1 thuc I8.n nhau giila p va T duqc xac dinh IXri
phUC1ng trlnh Oaperon- Oaudiuxa.
p
N
218 bar
K
Hi11h XIV -1. Giin d6 pha cUa HP trong IQa d p, 1 b vU.ng iip su!t trung b1nh
DUOng hoci hoi IK dUng t<_ti dilm tiri h{ln KUng v6i Pk = 220,88 bar,
tk = 374C = 647 ,2K. S1,1 hoci lOng (ngung 11).) ella hoi nuOc chi c6 tht!
x!y ra du6i nhit d t6i hi;Lll 374C. Vuqt qua nhit d Wi hl;Ul thl kMng
the n.ao lam cho hoi nuOc boa lOng dUQ'c. DuOng cong chMl chiDn IB Hi
168
kOO dai ciia dUC:mg bOO. hoi IK. N6 xRc dinb ;ip sua':t hoi OO.o boA
tren nuUc d6ng (can biing giOi an). thcii nay 18. k6m nMt
v8. nuOc dOng luOn luOn c6 cip su!t hoi ( va do d6 c6 tht! hoB. hQC)
16n han nuOc da d cU.ng d.
Trong truCmg hqp chung, c6 chUng minh rAng Qp sutil hdi cUa pha
giOi dn bao giif ciing cao lum cUa pha bin (n6i khac, dtWng thang boa
RI luOn luOn d6c han du<m.g.hOO. hoi BIK 0 gAo di!m B).
t"c-
10000
8000
I
4000
2000
0
III+
"00
2000
'-!6' 0
t:"'
0
'";do
"'
-50
-25 0
25 50
-------.. t
0
c
Hlnh XIV -2. GiM d6 kMng gian vt th8i ella H
2
0 b vllng tip cao
(lheo Karapetchien)
Du<:m.g n6ng chay IN ciia nuOc dci d6c 1ch sang phia tren ben tnii.
nay chUngtO nOOc dli. c6 tich rieng lcin han ciia nu&c lOng
ti kh6i nuOc da (p:::::: 0,92) b6 han ciia nude lOng (p:::::: 1). Do d6 theo
phuang trlnh Oap!ron - Oaudiuxo (VL31) nhit d n6ng duly ciia nuOc
dli. phai giam khi lip suA"t tAng.
169
Nhong tqa dQ Ung vOi ba I cUa nu& Ia P
1
= 4,579mmHg =
= 0,006099 bar va t
1
= 0,0098C (tinh trim lA O,Ol
0
C). Do d6 nu gcin
cho n6 dQ 273,16K th1 nhit dQ n6ng chily chudn cUa nuOc dci phii
bang dUng 273,15K.
2. Nghien cau d vUng iip suit cao
Hiuh XlV-2 Ut mb hlnh
khong gian ve trq.ry; lhlii ella
nuOc b nhOng lip cho tOi
10130 bar. Giim d6 XIV- 3 13.
hlnh chie"u ella m6 hlnh khOng
gian IC!n phing p, t. Cfing
nhu dOi vOi m6 hlnh khl'mg
gian, trtn gioin d6 phing p, t
kh6ng tht ghi duOng hoi hoi IK
va dui':mg thang boa RI ctia nu6c
di thuOng (nuOc di I) bUi vi
nhOng ;ip suit hoi luang Ung Ill
rat lh:fp so vOi thang ;ip su:ft
ductc chQn trong gilin d6, do d6
nhilng dui':mg bOO hoi va lhiing
boa thl,fC If Ill lriing vOi lfl!.C
hoimh.
NgtWi ta phil hin ra nhitu
nuOC di mOi : mr<rc di II.
III, V, VIva VII 0 vUng ap su:lt
cao (tlr 2()(X) bar cho tOi 50000
bar). Khic vOi nuOC d3. I (nuOC
dli thui':mg) tilt eli cic nUOc
di d6 dtu cO th6 tfch rieng be
ffi

"-
1
8000
VI
6000
4000
NuUc lOng
2000
I

------...- t
0
c
Hinh XlV -3. Gilin d6 pha ella H
2
0 0 vUng lip suit
cao trong phiing p, t.
han ctia nuOC lOng, 1Uc Ill c6 ti khOi !On hem cUa nu<rc lOng va do d6 ne"u c6 dubng n6ng
ch<iy thl dui':mg nlly 1ch sang ben ph<ii (rie!ng ntrOc d;i II kh6ng c6 dui':mg n6ng ch;iy).
NUOc d<i II dm;:1c phat hin ra tnr6c tie!n b vimg 3.p suit cao, sau d6 de'n nuOc dli III,
cOnS\!' t6n fl!.i ella nuOc dli IV vt sau b! jll.U n6 khOng lmg v6i rn(lt Mn mOi,
rna tO ra chi Ill dq.ng giOi An {kern ella nhilng nu(rc d;i II va III. NUOC dli VII chi t6n
tq.i 0 lip su:ftrtft cao nen khOng duqc ghi trong gi<io d6 XIV-3.
DuOi day 13. ti kh6ttrung blnh clic dl1Jlg nUOc dli.
NUOcdli
Ti khOi 0,92
II
1,12
Ill
1,03
v
1,09
VI
1,13
VII
1,5
Bang XIV- I tr'inh bity nhOng dii: kin vi de difrn ba ella mrOC. CO tit ca 7 dii!m ba: I
0 lip suit thllp va 6 0 vUng lip suit cao.
170
,BdngXTV
Nhimg dilm ba cUa ntt6c
Ditm ba Phac6
Ap suill (bar); Nhit dO ('C)
Nuc'rc da I, nuOc, hal 0,006099 +0,0098
A I, III, nuOc
2072
-22,0
B III, V, nu6c
3464 -17,0
A' I. II, lii
2127
-34,7
B' II, III, V
3445
-24,3
c V, VI, nuc'rc 6256 + 0,16
D VI, VII, miDc 22696 +81,6
c - GIAN DO PHA HAl CAU TIJ
4. 1,1).1 Cl10NG VE HAl CAU Tll
1. Thiinh philn
Th3.nh pMn mOi pha cila h 2 ctfu tir A va B dlng nhu thanb pMn cUa
h t6ng quat c6 the xac djnh bang Iuqng tuang d6i ella m()t trong hai ctfu
tir, thi d1,1 ella B. Luqng tuang d6i thubng lil : 1) pMn kh6i luqng hay %
kh6i hrqng (hay trQng luqng) ella B; 2) philn mol hay % mol %
nguyen tir) ella B.
Oich thlt hai c6 lq:i lil cho khi nang suy ra dang thilnh ph<in
hoa hQC ella nhling hqp chtft c6 thti sinh ra trong h. Thi d1,1 hqp chtft AB
lrng vbi 50% mol B, hqp cMt AB:2 (Jog v6i 66,6% mol B, v.v ...
Thanh pban ella h tOng quat va thilnh phAn cac pha ella h deu duqc
ghi tren cimg m()t tr1,1c tqa d().
2. Quy tic dOn biy
D6 18. quy tAc cho x<ic d!nh luqng tmmg d6i ella hai pha can
bang thuc cimg m()t h.
171
Gqi M, Ma va Mb 18. nhihlg wen cUa h tOng qwit va cUa
hai pha a va b trong gicin d6 p- x hay t- x (hinh XIV-4). Nhihlg
Ma va Mb thUCmg gqi 13. dim lien hf/P. Dmmg thing MaMb gQi 13. duimg
mit dllimg dOng nUt. Quy cic dOn bAy khing djnh rAng :
luqng pha b = MM, (XIV-S)
htqng pha a MMb
tUc Ia ill(lng m6i pha ti 1 nghjch vai
khodng ctich til dilm biiU' diln cUa
n6 tOi dilm bilu diln cUa fl4 tdng quO!.
0
A
1
B
GQi m Iii s6 mol ella m(lt bOn hgp 2 c{u
tlr A va B trong d6 phi1n mol ella 8 Iii. x
8
= x.
Giil thlr 0 p, 1 di eho, d6 ehia lilm 2 pha a
vit b. GQi ma Iii. s6 mol ella ehuyin vito
pha a vit mb = m - m. lit s6 mol ella
-clluyin vito Jila b; x. v3 xb lit phi1n mol eUa B
trong pha a va pba b. Hiin nhien ring s6 mol
ella B trong h xWft phlit ph8i. bing tdng sO
mol ella B trong 2 pha, tile lit :
Hi11h XlV-4. Quy tile dOn bfiy
mx = m.x. + m.,xb
Phuong trlnh nay e6 di;lllg trlmg v6i. pbuong trlnh eUa dOn bily lOlli 1 trong ea hqc.
Dua m = m,. + mb vao pbuong trlnh utn :
<m. + mt)x = m.x. + m.,xb
Qia 2 vtvm ma:
h<*:
tit d6 :

m.
'
mb x.-x. MMa
-=--=--
m. x-xb MMh
Nh11 V$y Ill di thie"t 14ip dll9C quy lie dOn bAy (XIV- 5).
172
5. HAl CAU Tlt HOA TAN KHONG CHE
VAO NHAU 0 L6NG,
c6 PHA RAN KHONG PHAI LA DUNG D!CH RAN
I - KHONG PHAI LA DUNG D!CH N!Klc (KHONG CO H,O)
1. Ht 2 clu tii khOng hinh thimh hqp chit hoi hQC, c6 otecti
don giin
a) Phdn tich hoO Ji va phdn tich Duimg ngu{)i. PMn tich boa li
la phucmg pMp nghien ciiu nhilng thui)c tinh H ella M theo thanh
phdn ella NhUng tinh dugc nghien ciiu c6 tht ta ap suA:t hai,
nhit d s6i, d(J kl!t tinh (hay n6ng cbay), dQ tan, ti kh6i, d din
v.v ... si Lien XO N. X. Cuarcmac6p dli c6 nhieu d6ng g6p quan
h'Qng trong xa.y d\fllg phan tich hoa li.
fC
--- th<:ri gian
a)
0 ""
A
-
b)
B
x,
Hinh Xay di!Jig gilio d6 klt tinh ella M 2 c!lu ti'r Ava B theo dulmg ngu(li
0 p = const. a) Nbitng dui'mg ngu(li d- thi'ri gian) (rng v6i nhilng thMh pb!o kb3c
nhau ella he, b) Gi3n d6 k!t tinh (h* o6ng chiy) ella 2 du til c6 atecti dan gi&n
173
M()t trong nhihtg dc.mg ph6 nMt cUa phAn tich bOO li Ia phdn tich
D6 Ia hqp nhilng phoong phlip thlfC nghim X<ic djnh nhit d(l,
t;.ti d6 trong h c6 s1,1 thay d6i s6 pha. Hlnh XIV -5 trlnh bay m()t c<ich
xAy dJ!Dg giAn dd pha (giRo dO ke't tinh) cUa 2 du tir Ava B c6 atecti
dC10. giRo nhO nhDng phuC1D.g phlip phAn tich nhit.
au tU r.in A hay B nguyen chili h'* h6n hgp 2 c!u tlr r.in A vit B theo nhfrng thitnh
ph<in kbac nhau dm;tc dun n6ng cho n6ng chil.y th!tnh thi lOng 0 p = const r6i de
yen cho ngut)i di. Theo dOi nhi.(it dQ ella chUng theo thCri. gian (thf d!.i cU' 30 giay ghi
dQ l<in), ta dugc nhilng duCmg cong nhi1 dQ - thbi gian gqi 111 d1rilng ugui
(hlnh XIV-5a).
DuOng ngut)i ella A nguytn ch!t (dtWng I) hay B nguyen chiD: (du(mg 7) gOm nhil'ng
nhanh g:ln nhu dOc thing d(mg, chUng tb Sl,l" ngu(li kM nhanh, khi t& nhi1 dt) kl!t tinh
(hay n6ng chiy) lA d6i vOi A vii 1
8
d6i vOi B thl c6 m1 thing ngang ch(mg tb nhit
d khOng d6i; d613. do c6 tinh (bAng vii ngugc d!u vc'ii nhi(!t n6ng cbay) dugc
tba ra bU vao ch6 mti't nhit do ngu{)i w nhitn, kt qua HtA hay B nguyen ch!t tinh a
nhi(!t d kht'lng ddi (du6i lip su!t p ngoill khOng d6i); sau khi dii tinh xong thl nhi1
dQ mUi l;,t.i tifp ll,JC th;(p, do d6 111-i c6 m1 nhanh d6c, nhung kern d6c hcrn nhlinh
d:i.u tien.
D6i v6i h6n hgp 2 ca:u tlr A vft B theo nhfrng th3nh ph<in khlic nhau, duOng ngu{)i elm
chUng 13. nhfrng du(mg 2, 3, 4, 5, 6 trtn hlnh XIV-5a. N6i chung, nhfrng duCmg ngut)i
nily d:i.u ciing g6m mQt nhanh d6c g:ln th&ng dUng (ngu(li nhanh), khi t6i nhift d
b&t ddu kef tinh ella d!ch n6ng ch3.y (pha lOng ci'J.a h6n hgp 2 dn tU A va B) thl ngut)i
111-i do c6 kt!"t tinh dugc u)a ra nhung chua dii de 111m cho nhi(!t dt) khOng d6i,
dieu nay dt.n;JC ph3.n 3.nh tren duOng ng01)i bAng mt)t nhlinh d6c ft han so vOi nhlinh diiu
tien (trir duCmg ngut)i 4). SJ! ke't tinh tlr djch n6ng chil.y sC cho tinh the:! A nguyen cb;(t hay
B nguyen ch!t tiiy theo thltnh PJ<in xB cUa djch chiy b6 han xE (dubng ngui 2 vii 3) hay
1&1 han x
8
(dubng ngut)i 5 va 6).
H6n h<;rp lOng c6 th3nh ph<in bAng dUng x
8
gqi 1ft Mu h{lp mecti ldtlg, n6 ke't tinh 6
dQ tE gqi lit dq utecti. 13. nhit dt) thilp nhl'ft so vOi nhi1 d() bit d:iu ktt tinh ciia
cic djch n6ng chil.y kMc, kl! eli. ella A va 8 nguyen chl'ft. H6n hqp atecti lOng thu(mg chi
gqi dan giin Ja mecti !dug. Khi atecti lOng kt tinh, n6 cho dtecti r&u Iii. h6n hgp nbfrng
tinh the:! A va B sinh ra dOng thCri.. O.U Y rdng mecti lOng Iii mt plla !Oug (theo gi3. thie't,
2 dfu tU A vii 8 boil tan vao nhau theo b!t kl ti 1 n!to a the:! lOng) cOu utecti r&u g6m 2
pha : pha tinh thl A vd p/Ja tb1h tM B. Nhu llloi dil!m atecti E c6 can bAng dOng thbi
giiia 3 plra song song lit: I pha lOng (bOn hgp atecti lOng chua ke't tinh htt) vii 2
pha rio (tinh thi A vll. tinb the:! B). Vl sg klt tinh dil!n ra a p = const, ntn s6 IJ! do c6
dil!u kin aia h 2 c!u tlr c6 3 ph a 13. f
4
= 2 + I - 41 = 3 - 3 = 0. dil!m atecti E Ung
vOi cAn bAng khOng bie'n (b!'t bie'n), khOng c6 W do m\o ella 3 pha song song tOn ll).i.
174
N6i k:hac, S\f k(t tinh ciia lOng phai difn ra iJ nhi1 d() atecti le khOng d6i gi6ng
nhu ciia cbl(t nguyen chl(t. DuOng ngu(li 4 ciia otecti lOng c6 gi6ng nhu ciia A hay
B nguyen cMt.
Nhilng djcb n6ng chiy c6 tbim.h ph:in kbic nbau bit d&J k(t tinh a nhfrng nhi1 dl)
kb3.c nhaU (du(mg ngul)i 2, 3, 5, 6) nhung tl(t d.IMu kfttb6c SJ! k(ttinb a dl) atecti
le. nhi1 dl) nAy, bit dAu xul(t bin tinh the B (hay A) d6i vm nhilng djch n6ng cbay
dli cho k(t tinh truOC tien A (hay 8) .. Nhllthl, nhi1 d(l te c6 3 pha ; I pha lOng
(djch n6ng chity) va 2 pha tinh thl'! A va B. h Iii khOng biln (c6 ditu kin, tllc lA iJ
p"' const), nhi1 dl) te khOng d6i, ditu nAy Ung vUi m(ll dO{UI thAog ngang trtn cic dubng
ngu(li 2, 3, 5 vii 6 cho tUi khi djch n6ng chiy k(t tinh xong, khi d6 nhi1 d() tilp II}C
hl;l nhung dAn vl hiu nhit d() cUa h va cUa mOi trui'Jng xung quanh da
gi!im nhilu.
Trtn giM d6 nhi1 d(l klt tinh -tMnb phin (hlnh XIV- 5b) nlu n6i litn cic ditm I,
2, 3, 4, 5, 6, 7 Ung vm nhi1 d(l bit dAu klt. tinb theo nhitng thlmh phin x
8
kbac nhau cUa
b 2 ca:u tii, ta se dll(JC d!Wng cong tAEt
8
ciia h 2 cl(u tii c6 atecti dan giin.
b) Gicin d6 pha cUa 2 cdu tU cO utecti dcm gidn
gicin d6 nAy tnmg cbo nhilng h 2 tir A va B boA tan
bOOn toin v8o nhau khOng cbt! 0 the lOng va khi kl!t tinh khOng binh
thlmh dung djch rio, cfing kbOng hinh tbanh hqp bOO. hQC. Thi dl,l
Cd- Bi, h Pb- Ag.
M
0
Pha lang L
ctiaAva B
-#."'
"'"'
\. l+B
'E
_,8
HinhXIV -6. Oiin d6 phab 2 cA'u tiic6 otecti dan giin
175 http://hhud.tvu.edu.vn
Nhit d klt tinh n6ng chiy) cila AvA B cMt 18. tA va
t
8
. Trtn gi8.n d6 XIV- 6, dUCmg cong tAE lA quy tich nhfing nhit d Mt
diu kl!t tinh cila A tlr djch n6ng chiy (bOn hgp hai tlr A vA B n6ng
ch8.y thlmh pha lOng L), m&i diem ella tAE th! dl) tan cila A trong
djch n6ng chay L bio hoA A b nhit d toong Ung.
DUOng cong taB cfing 18. qUy tich nhihlg nhit d bib dliu klt tinh ella
B tlr djch n6ng chiy L : mOi dit!:m cila dUCmg cong d6 bit!:u thi d tan ella
B trong djch n6ng chay L. Nhihlg dUCmg cong tAE va t
8
E hQp thAnh
dutmg lOng (tilng La Tinh Ia liquidus). Dit!m atecti E 13. giao die'm ella
hai duUng cong tAE va t
8
E. DUOng thing ngang RES gQi lA dutmg otecti
hay duimg r&n (tilng La Tinh 18. solidus).
Nhihlg dUCmg lOng tAEt
8
va dUCmg rAn RES chia gi8.n d6 ra lAm 4
vUng (hay miln, hay tniitng) (hlnh XIV-6). VUng b dUCmg lOng
tAEt
8
18. vi:mg d6ng ella dich n6ng cbay L (1 pha lOng), ba vUng cOn
lA nhiing vUng dj nhieu pha, vi:J.ng tAER : djeh n6ng duly L + tinh
the A; vi:mg t
8
ES : L + tinh the B; vi:mg ARSB : tinh 1M A + tinh the B.
Ta xet qua trinh klt tinh ella djch n6ng chiy L Ung vOi diem bieu
dien M tren hinh XIV - 6. Khi nhit d thifp, diem bieu men M cila
h t6ng qwit chuyen djch dQC theo dUCmg thing dUng Mabcd. Khi t6i
dit!:m a thi qwi trinh ke't tinh Mt va tinh the dAu tien ella A tach ra
khOi djch n6ng chay L. T6i nhit d Ung v6i diem b (dilim bit!:u ditn ella
t6ng qu3.t), thi di&n dit!n ella pha rAn (tinh tht! A) 13. r va ella pha
lOng L (djch n6ng ifciy) cAn bang v6i tinh tht!: A 18. I, dit'!m nay cho tha'y
dich n6ng chay ngay c8.ng giau B. Luqng tucmg d6i ella pha lOng va d.n
dlll;1C xcic d!nh theo quy tAc dOn bdy :
ltrqng pha lOng L br
-
Im:mg pha riln (tinh tht A) bl
Khi bAt dAu t6i diem c, Ung v6i. nhit 9 atecti tE, luqng tucmg d6i
cUa hai pha 13. : .
176
hrgng pha lOng L
.,----=?"-'7":..::::::S--:-:- =
lQng pha ri.n (tinh tht A)
cR
cE
DOng thCri xuilt tinh the dSu tien ella B. trb tlllmh 3 pha va
khOng c6 11,1' do nao nita (fdk = 3 3 ==:' 0), nghia 18. d() atecti tE
khOng d6i thi\nh phli.n ateeti xE ella pha lOng L ci1ng khOng duqc thay
d6i. Kt tirlUe tinh the B bat d:iu xuilt hin, cae tinh the A va B khbng
nglrng dugc sinh ra d6ng. thCri tlr pha lOng L, nhun.g ti 1 kh6i hrqng ella
ehUng ph<li bAng dUng ti 1 kh6i luqng mil ehllng e6 trong tbanh phli.n XE
ella h6n hqp ateeti lOng, c6 nhtt mffi b3.o dim tbanh ph!in xE ella pha
lOng khOng d6i eho tOi giQt eu6i ellng. Sau khi pha lOng trong h da biCn
he't, h l<1-i trb thlmh h 2 eilu tir 2 pha (tinh tht A vi\ B) e6 1 tl,l' do e6
diCu kin, nhit dQ 1'1-i tiCp 11,1c thilp nhun.g ehl}m hem h1c d:iu.
Trong Sl,l' kCt tinh ella ateeti lOng 6 nhi1 dQ tE khOng d6i, ca.e tinh the
A va B sinh ra d6ng thb"i khOng c6 diCu kin de 16n len, eho nen cnecti
rAn e6 ea:u trUe hl:lt tinh tht nhO, m!n, deu Do d6 c6 y kiCn cho dng
ngU oteeti theo g6c Hi Ll:lP eutektos e6 the hieu ta "c6 ctlu trUe
deu, df!p" (eu =dUng, tektos = ea:u trUe). MQt Y kiCn kh8.c eho di.ng
eutektos 18. dt! n6ng ebay, tlre 18. otecti rAn ta bOn hqp dt! n6ng eMy nhat
(c6 nhit dQ n6ng ehiy thilp nhilt) so vcJi cac h6n hqp kh<ie ella 2 ea:u ti'r
A va B dii cho.
Con dub"ng cho biCt Sl! thay d6i thi\nh pba.n ella pha lOng tir khi hit
diu kCt tinh eho dCn khi kCt tinh xong gQi li\ duUng ke't tinh dlltJC chi tren
hlnh XIV -6 bAng dubng cong e6 miii ten alE.
2. Hi; 2 c8u til hlnh thimh hqp ch8t hoi hQc
a) HlJP chtlt n6ng chdy hodn nguyen (khtmg bi phiin Jui.y)
Hai c4u tlr A va B c6 the hlnh thll.nh hqp chilt rAn c6 diem n6ng ehiy
de djnh. Trong nhieu trub"ng hqp, nhiing chilt nay li't ben va n6ng ehiy
khbng b! phan bUy, thanb ph:in eUa hqp chilt rAn va thatth phAn ella pha
lOng thu dugc 18. trimg nhau. S1,l n6ng eh<iy nay gQi li\ n6ng chdy :fwan
nguyen (fusion eongruente) (tiCng Latinh congruentis Hi trii.ng nhau).
Thi d1,1 Cua- Fe0
3
, giin d6 pha cUa h nay Ung vffi hlnh XIV-7.
177
DUOng lOng c6 ml)t cifc dfli C Ung v6i s" hinh tbanh hqp chat CuCI .
Fect
3
. Gian d6 XIV - 7 c6 the eoi nhu SIJ gbep vao nhau ella 2 gian d6
rieng re ella 2 h, m6i M c6 l atecti dan gi_an: h eua- cua. Fe03 c6
ateeti Eva h CuO. Fe0
3
- Fe0
3
c6 atecti E'. Hai giAn d6 ghep vao
nhau theo tung dl) chung C, lmg vOi hqp cha:t CuO. Fe0
3
.
1
cuc1 424
tC
l
304 298
tFeCI
3
-
u
263
w

u
E'

"
0
50 100
-
%mol FeCI
3
Hinh XIV -7. Giin d6 pha h CuO- Fe0
3
c6.syb1nh thinh mQt hgpch(t CuO. FeCl
1
N6i dUng thl trong da s6 tnrCmg hqp, hqp chat hmi hQC khi n6ng cbay
cO phdn li m(JI it, thf tnrCmg hqp ella Cu0-Fe0
3
. Trong trUCm.g
h1;1p nay, nhting dUCm.g CE va CE' trcm ehu tit dUCm.g nay sang
dUCm.g kia : chUng 13. 2 nMnh ella ci:mg mt)t duOng eong va qrc C
khOng nhqn.
Nlu hqp cha:t hrni hQC rdt ben, khi n6ng cbay ho3.n to3.n khOng phiin
1i thl fJ hai ben ranh giOi Ung v6i hqp cha:t d6, klt tinh ella hqp
cha:t ra:t kh<le nhau. Ditu nay duqc quan sat chAng hl,lll trong S\1' kl!t tinh
ella hqp cha't K
3
Sb (hlnh XIV-8). Gian d6 nay chi rtmg dt) d6c ella
nhfing dUCm.g cong OK va CE diem C kht'mg gi6ng nhau vil C la mt
dinh nhqn, tllc Ia C 13. mQt ld d! ella dUCm.g eong bAt dAu ktt tinh.
Tn:ri:mg hqp nay hil!m. H K-Sb cOn c6 mt)t hqp cMt rAn thU hai, KSb
(rng v6i C\J'C C' binh thuUng, tran chu, khOng e6 dinh nhQD, nghia 13.
kern ben han K
3
Sb.
178
Hi11h X/V-8. Gh\n d6 pha K- Sb c6 Sl! hlnh tbanh 2 hgp chAt hOO hQc.
hai cA'u tir c6 tM hlnh tbanh rA't hqp chA't hoci hqc khcic
nhau. Khi d6 giiin d6 pha la mQt hqp nhieu giiin d6 rieng re c6 atecti
dan giiin ghep n6i vao nhau theo nhihlg tung dQ chung Ung vOi ccic diem
qrc (hgp chA't hoci hQc ).
b) Ht;tp clu.ft n6ng cluiy kh6ng hotln nguyen (bi phdn liuYJ
Trong nhieu truOng hqp, tinh the ella hqp chAt hoci hQc khi tO:i mQt
nhit xcic dinh thl bit d3.u n6ng ch<iy va tach ra th!mh pha tinh the va
pha lOng c6 thimh phlin khcic nhau. S\f n6ng cbay nay gQi I.a n6ng chdy
kh6ng hoiin nguyen (fusion iricongruente) nghla 1a Sl! n6ng chiiy trong
d6 thanh pMn ella pha rin ban dAu va thanh phlin ella pha lOng thu dUQC
khOng trimg nhau.
Gicin d6 pha ella mQt trong nhfing h 2 cA'u tir c6 hqp chAt n6ng cbay
khOng ho3.n nguyen lrng v6i hlnh XIV-9. GQi K h't hqp chA't.
NhUng duOng lOng tUc 1.3. duCmg bAt dliu ke't tinh ella cAu tir B
khOng gi;\p nhcinh di xu6ng CE' rna nlu\nh di len EC tlrc ta duOng bat
dliu kt tinh ella hqp chA't K diem P gQi 13. diem peritecti. Nhcinh EC
chi t6n tirE dn P cOn PC (chain chAm) I.a iio va qtc C lmg v6i
thl\nh ph:in xk ella hqp chft K cling I.a mQt diem iio. Nhu v*y gi:ln d6 pha
chi c6 1 diem atecti E, khOng c6 dil!m c:necti E'. Toan b duCmg lOng
(liquidus) U1. tAEPt
8
, vUng lJ teen dttbng nay I.a vU.ng t6n cUR pha lOng
L (djch n6ng cbay), cOn dtrong r!l.n (solidus) 18. GEHKR.
179
Hqp cha't rein n6ng chay khOng ho<ln nguyen K chi t6n ben (1 nhit
d() tha'p han nhit d() peritecti tP. Khi lam tang nhit d ten tOi 1p. n6
phan hiiy tba.nh 2 pha: pha tinh B, difn 13. R vii pha lOng P
n6ng chiiy) c6 thanh phful peritecti xp.
t"C
fC
.I
a' i II ___ _t_ - II
1
L
'
' '
' c '
_________ P
b. [ K [ b'
' '
' ' L+A L+K I I
1
E
'
' A+K I
R
:-------'----L--''-....J B
A
0
'p
-xB
- thOigian

Hi11hX1V --9. a) Giin d6 pha h 2 cA"u tlrc6 hgp cba:t n6ng chli.y khOng hofm nguytn;
b) dUOng ngll('li."
I) Ta xet qua tr\nh ke't tinh ella djch n6ng chay c6 thimh ph<in Ung v& I trtn dm'mg
thing dUng di qua khming giii'a ditm P vll K. Khi nhi1 d thifp Ung vOi diem a trtn
duCmg lOng tBP (h'lnh XIV -9a), tinh the B bi\.t diu xuM Trong kbming nhi1 d\';1 gifia
nhUng a v8. b, he Ill 112 dfu tlr 2 pba I bitn .. oo dieu k$1 (vl. p = const), fdk = 3-2 =I.
khi rom bM dlu tai dil!m b, Ung vOi nhi1 d peritecti lr Ia c6 m1 pha rAn R (tinh thi B)
va m1 pha lOng P. gqi ta Mtl hf!p peritecti lOng c6 thlinh pMn peritecti xl'. Lugng luang
d6i 2 pha nay Xlic djnh theo quy lk dOn b!y:
lugng pha lOng P , bR
lugng tinh thi B (pha R) bP
hie hllugng ph a lOng nhi&. han lugng tinh thi B.
Ciing tlr hlc d6, hqp ch!t hOO hQC K c6 th1mh phlin xl< Ung v& dii!m K btlt db
tinh va tach ra khOi pha lOng P. lri:J thanh 2 c!i:u tlr 3 pha : I pba lOng P, l pba r3.n
R (tinh tht B) va I Pha tinh thf K (hQp chat hOO hQC), do d6 h lA bat cO
180
.,
f.tk=J- 3 = 0, nghla li'l nhit d() peritecti tP, thilnh phl1n peritec.ti x.P ella pha lOng P vU
thilnh ph:in x.k ctia hgp chAt (ditm k) phai khOng d6i.
Vlthilnh ph:in x.k ella hi;Jp chit chUa cau n'r B bon thanh ph :in x.P ella pha lOng P
nen khi hgp ch:ft k(t tilih tir pha lOng P vii t:ich ra khOi pha lOng P thl thilnh ph;in pha
lOng P oily thay deli theo hu&tg gi:im d;in ct'lu tU B.
IX! cho thlmh pUn x.P ella pha lOng P kh6ng thay deli trong khi nhiing tinh thl! ella
hgp chill K kMng tach ra khOi pha lOng P thl nhfmg tinh tht'! ci.La B dugc hlnh
thlmh tlr truCK:, bily gi& phliihoa tan vao pha lOng P de bio d!im cho lugng tuong d6i
cUa B trong pha lOng P dm;IC giil khOng deli.
Chli y rang dit'!m peritecti P cling nhu tl.li. diim E c6 can bang d6ng thbi
giiia pha lOng v6i hai pha r.in. Nhlffig qua trinh klt tinh trong hai 'truCmg hgp kbic ni)au
can bOO.() nbit d otecti, bai pha rAn klt tinh d6ng thbi, cOn 6 nhit dQ peritecti, mt
pha ran klt tinh, cOn m1 pha cln ll.li boil tan. duOng ngui (hlnh XIV- 9b, duCmg I)
(rug v6i nhi1 d(l peritecti tP (dit'!m b) c6 m(lt thing ngang, cbCrng tO tP khOng d6i.
Vliugng tinb tht'! B it bon lugng pha lOng P nen toim bQ lm;mg tinh tht'! B dm;1c hlnh
thimh tir tnt6c se boa tan h6t trong pha lOng P. Khi d6 h tr6" thlulh h 2 pha g6m pha
lOng vii pha tinh tht'! ella hgp ch:lt K. Nhi1 dQ ella h tilp ty.c hl,l mip vi\ nhUng tinh thl!
elm hgp chit K tilp ta,c tach ra khbi pba lOng, thimb ph!ln nii.y ba.y gi(J biln thitn lie!n ll!-C theo
nhit dQ, m6i nhi1 d Ung v6i m(lttbimh phlin x:ic dinh cUa pha lOng (dulmg cong PE).
Khi nhit dQ hl,l tbifp t& nhit dO atccti IE, h (bit'!u ditn bbi dit'!m d) g6m c6 pha lOng
Iii. atccti lOng E, pha tinh th K ella hgp chft (dit'!m H), ngOO.i ra pha linh tht'! A (diEm G)
cfing bit d3.u xuat hin. Nhu h l').i c6 3 ph a vii. triJ thilnh b&:t biln c6 dit'!u kin,
dQ ll,li kh6ng d6i, dit'!u nii.y Ung v6i doan thing ngang t').i d trtn dllCmg ngui I, cbo dln
khi toiln b pha lOng kt tinh xong, nhi1 mOi l!li titp II,IC h\l milp.
2) Khi dit'!m ditn II cila pha lOng ban dliu 0 trtn mQt dutmg thing dUng di qua
khrn\ng giila dil!m K vii. R thl khi 16i a' tttn dlllmg lOng tBP, tinh mt'! diu titn ella B xult
hin. T6i b' trtn nMnb du?mg rln KR, nbfmg tinh tht'! ciia bgp cMt 00 H cfing b!t dlu
hin ra, dil!m bifu diln 13 K. H ll,li c6 3 pha va trO thlulh blt biln c6 kin: nhilng
tinh tht'! B hlnh thii.nh hie truUc ll,li boil. tan vli.o pha !Ong.P bio dim thimh phlin Xp ella
pba lbng duc;rc giil khbng d6i trong khi nhilng tinh tM ella hgp chift K kh6ng nglmg tach
ra khOi pba lOng P.
Nhlffig i1 day vi b' nam giiia K vlt R nen theo quy tik dOn bAy:
lugng pha lOng P b'R
lugng tinb me B (pha R) b'P
t(i"c Iii. lugng ph a lOng PrO r1 ft bon lugng tinh thi B. Do dO, kMng phii Iii. tinh me B boil.
tan het vao pha lOng P nhu trong tnrCmg hgp I, mil Iii. pha lOng P se biln ht truOc pha
tinh me B. Ket qwi. ta dm;c mt tt ran 1a h6n hQpnhOng tinh 1MB va tinh 1M cita h<;rpchat K.
Ghi chil:
I) Diim peritecti 1a diki thilp nb:lt cU.a duim.g bit d!i.u k6t tinh pha (du?mg tBP)
vii. Iii. diim cao nhilt cUa dutmg kttinh pha kM.c (dulmg EP) cOn dil!m otecti lit diim
lhilp nhil. cita ci bai dui:mg klt tinh (duOng k1: tinh tAEcita A vltduirng EPcUa b<;rpchil. K).
181
2) Thf d1,1 h c6 ditm peritecti lA It QISi0
3
-BaSi.0
3
, nhOng cfu tit nay blnh thinb
hgp cha't Ca
2
BaSi
3
0
9
chi btn 0 dQ th(p han 1320C.
II- TROONG H<;JP DUNG DjCH N00c
ve thi!, gian d6 pha cila 2 cl"u nudc va chat tan cfing c6
nhihlg c4flg tuoilg tl! nhu tl'ic 18 cung c6 nhfin.g diem atecti hay
diem C\fC hay diem peritecti nhung v(}i m()t s6 diem
1. va chit tan khOng hlnh thinh hqp chit xic djnh (khOng
hlnh th8nh tinh thi ng'm nlia:c hay hidrat), cO dtecti don giin.
Tliln hinh XIV-!0, duang long hay duang bOt <Mu kt tinh tAEgQi Ia
dllirng d(j tan ella A vil duUng t
8
E gQi li dQ tan ella B.
o obi< thuang e
(khoang 25C), n.Alt (clu tir A)
;, the lOng cOn da s6 cha:t tan.
bit 18 c8.c mu6i
chlt (clu tir B) 11 tM rAn. Khi
d6 nhtinh cpt
8
bieu ditn sq ph11
thul)c d tan cU.a ca:u tlr B
trong nude vio nhit d(); tlr
dQ thuOng e cho dn
d() n6ng clilly t
8
ella B
nguyen cMt.
0 d() cao han tB thi A
(nude) v3 B (cha:t tan nguyen
cha:t 0 thai lOng) boil tan
vito nhau theo Mt k1 ti 1 nao.
fC
t
L
e ---------------
A
(H
2
0)
E
-xB
(Chfttan)
Hi11h XIV -/D. Gilin d6 ph aM nuc'fc- chlft tan
c6 otecti dan giin.
Tha:p han nhit d() thuUng 8, duUng cong d tan cUa chA't tan B trong
nuOC bieu ttl! bi:Ji nbanh <pE, EtB lA duUng cong <My dU vf. d tan
cUa ca:u tir B trong nude. COn duUng liquidus tAE bieu ditn can bAng
giila nhfin.g tinh the A (nlnk) v6i dung djch bao boa A gQi lil dllilng
htlnnghirm.
182
Trang nhUng hQp biri nuUc va chlft tan, atecti E duqc gQi mQt1
each kluic 13 dilm cryohidrat, va atecti rAn, san phAm ella S\1
(k(t tinh) c6 thanh pMn d6 gQi Ill cryohidraL
an phAn cryohidrat v6i tinh nOOc (cristallohidrat).
Trong cryohidrat, ta c6, a d\Uig san pham ran. mQt bOn hQp 2 pha riln
g6m nhO'ng tinh thi! nOOc d3. va nhilng tinh the clfu tit B. cOn tinh thl
ngfjm nui!c 18. m(lt hqp chlft bOO hQC tic d!nh 0 thi! rAn ( 1 pha riin), mOi
tinh thi! nuOc chUa d6Iig thi:ri ca. nuOc va ca:u tir B lien kt bOO hQC
v6i nhau.
Vi nOOc thUOng bay hai hcrn chAt tan nen trong da s6 truOng hqp, a
p = 1,013 bar, khi tOi m(lt dQ nao d6 th!p bon dQ n6ng ch3y
t
8
ella B nguyen cMt, dung djch nuUc bio boa B di sOi va nOOC (c!u tir A)
bay hcti hlt tnrCic khi B dc;tt t6i th8.i lOng nguyen cba:t. Do d6 gilln
d6 pha ella 2 ca:u tir nOOc va chAt tan it khi dUQC dlty dU trQn
dUOng cong dQ tan cUa B
thOOng khOng d<:tt t&. dii!m t
8
,
rna b! dUng l<:ti 0 dii!m G, Ung
vai dQ d6 nuUc di bay
hoi bEt.
Gi3n d6 pha ella m(lf trong
nhilng H,O- KCI
Ung vOi hlnh XIV -11. T<:ti
1,013 bar cr 0C, dQ tan ciia
KCI trong mrac Ill 21,9% kh6i
lrn;mg a), a 180C, dung
d!ch biio boa KO chUa 43,3%
KO sOi va mnlc bay hai hlt
(dii!m G), do d6 dUOng cong
d(l tan BaG ella KO dlmg 1<:ti a
diimG.
2. Hcln hqp sinh him
Kbi tr(m mWc da (hay tuytt) v6i
t"jc l
1180
. '
20
G

/
/
21,9%
40 60 0
H
2
o
- % kh6i IU'Qng KCI
80 100
KCI
Hiflh XIV -11. Giin d6 pha h H
2
0 - KO
c6 cryohidrat
tinh thl! KO, ntr6c eta tan ra, mu6i Ka ho3 tan Vi\o mrlJc va nlu c6 dU lut;mg nu6c dli vi
mu6i c4n tbilt se hlnh tblnh mQt h(! 3 pba g6m mrOc dli, tinb tbl'!: K9 va dung djch mWc
183
biio boil KCI. 2 cau tU 3 pha nay Iii kh6ng biefl (bat bic!n) c6 dieu kin (vl b p = const),
nghia Iii tOn cAn bang dOng thb'i v&i nhau b d(l cryohidnll boi'm toan xlic d!nh,
- II, I C vii tffig v&i thilnti phiin dung d!ch 19,8% KCI (lhi'mh phAn cryohidral) cling
;oitn toiin x.lic dinh. Do d6 chlmg niio trong vAn c6 3 pha c:\n bang dOng thlri thl nhi1
d dugc giii' vilng 0- Jl,l''c. D6Iii. nguyen tic cUa vic dUng nhii'ng dungdjch mWc cUa
nhilng mu6i c6thi'mh pbAn cryohidrat diS difu nhfmg bOn hgp sinh hAn (lflm
H H
2
0 - NaCI dtrqc dUng ph<l lil.m h6n hqp sinh hiin (nhi1 d
cryohidral, -2I,2''c, tbi'mh pMn cryohidrat, 22,4% kh6i ht(,Jilg NaCI). H niiy ngoiti
dilm mecli (cryohidrat) cOn c6 ca dilm peritecti, tOe h\ c6 Slf hlnh thilnh m1 tinh tM
ngj).m mWc NaCI. 2H
2
0. n6ng chay khOng bOOn nguytn (b! phAn hlly) b + 0,25C.
. .
6. HAl CAU TIJ CO HAl PHA LONG. 51/ HOA TAN
CO CUA HAl CHAT LONG vAo NHAU
1. TnrOng hqp 1 : khOng c6 diim hoit tan tbi h,n (hinh XN-12)
mt)t nhit <11) t
xac d!nh ta xua't phat tU
A cha't
wen 13. Ao va them
dAn B se duqc mt)t dung
dich ella A ng3.y cang
gi3.u B. dien
cila, h d!ch dAn
tren dtrCmg th!ng ngang
di qua A
0
va t = const.
T6'i diem a, dung d!ch
trb th3.nh bao boa cMt B
c6 thanh phAn Xa va Mt
dAu xua't hin giQt dan
cU.a lOp lOng thU hai

t
0
A
,.
x,
b"
% kh6i !Ltgng B
100
B
Hi11hMV-J2. Sq boil tan c6 cUa 2 cha't lOng
A va B kb6ng c6 ditm bOO tan t&i
c6 th3.nh phAn xb hoAn to3.n dplh vt dien bbi b.
184
Nu tip t1,1c tMm -B thl bieu Mella h telng quat
dich tren duUng th!ng ngang ab nhung thanb ph<in Xa va xb ella 2 16p
lOng can bAng kh6ng deli. S1,r tMm B kb6ng 18.m thay d6i thanb pMn 2
pha lOng cllo bUng, chi tam thay d6i luqng tU'Ong d6i ella chling. ThJ!c
theo quy tAc dOn bAy, luQilg nrcmg d6i ella lOp cfi a) va lOp
m6i (diem b) ti 1 ngh!ch vdi nhihlg khoAng each Ma va Mb, nghia Ia
neu db B thl hrQilg lOp cfi giitm dcin trong kbi lm_mg 16p m6i tang
dan. Khi dll B M M tdi b thlldp cfi thJ!C tt! ln4"t Mn, chi cOn
1<!-i lOp m6i va ti.r hie d6, M 1<!-i trO thanh 1 pha, Sl,l' ti(p B kh6ng
g"a.y ra lOp m& nao khcic.
Ngugc l{li, nu xu&t ph3.t ti.r B nguyen ch&t (ditm B
0
) ta them dAn A 0
t = const, se dugc m()t dung d!ch ella B ngay dmg giau A. Diim bitu
di8n ella h t6ng quat chuyin dich d!'in tren duOng th!ng ngang BJl.--TOi. b,
dung dlch trO thtmh bao boa A, Ung vdi thanb phfut xb va M b&t dAu cho
tAch ra lOp lOng md:i c6 thanh ph<in Xa hoAn toan xac djnh, lttQilg lOp m6i
ngay c3.ng tang, khi tO:i diim a thll6p cfi thi,IC t m&t h_An v. v ...
T6m 0 t = const, 2 ch&t lOng 13. d6ng tht (1 pha lOng) ti.r Ao d(n
a va tlr b d(n B
0
; h Ia di the (tach ra tam 2 pha lOng) ti.r a d(n b. Hai
ditim a va b gQi Ia di{m lien hf!p va duCm.g thing ab gQi Ia dllilng lien ht;tp
hay duttng d6ng mit.
Khi d() t thay deli, diim a seve nhanh du(mg conga' a a" (bitu
th! dt) tan ella B trong A) cOn ditm b se ve nhanh b'bb" (biiu th! dt) tan
ella A trong B). Nhihlg nMnh duCm.g cong d6 gQi 1a duttng cong chia
lifp. Vimg ben trong nhiing nbanh d6 ta vUng d! tht 2 16p ; 0 ngOO.i 13.
vimg d6ng thi! (I lap).
2. TI1./0ng hQp 2: c6 diim hoil tan tdi h'-n trin (hinh
Trang tn.rOng hqp, khi t tang. -d() tan lin nhau ella 2 cMt lOng
tang theo, hai nh3nh du(mg chia l6p g!'in nhau, c6 tht g@ nhau
1<!-i ditim K gQi 18. di/m hail Ian tiri h9n tren. nay, tblmh pMn 2
lOp trb thanh nhau. d() tK Ung v6i diem K gQi 18. nhit df) hoii
tall t&i h{ln trell. Cao han nhit nay. vUng chia lOp m&t hin di, hai
!85
cba:t lOng boa tan bo8.n toAn vao .
nhau theo Mt kY ti nilo (blnh
XIV - 13). Nhu duimg cong
cbia 16p a' K b' cbia ghin d6 ra
lam 2 viing : viing lxln trong
dtWng cong 18. vUng chia 16p
(2 pba). vUng ngoai dOOng c'?ng
la vilng d6ng tlu! (l pha).
Thf d1,1, d6i v6i M nu6c
phenol, thilnh phl!n 2 lap lit 8%
va 70% kh6i hn;mg 0 l5C, dit!m
boa tan t6i trert ling v6i 66C
va c6 th8nh pMn 34% Ptenol.
40
30
20
1- K
------=
1- a"
1-
1-
a
a'
b"
b
b'
020406080
............... % kh6i luang C
6
H
5
0H
H(! ntr6c- phenol c6
diim hoi tan t& tren
3. Tru'Gng hqp 3: c6 dii'm hoi tan tdi h"n dlldi (hlnh 14)
Nhilng nMnh duimg
cong cbia ldp nhau
iJ phia nhit dQ tMp.
Khi d6. CI!C tit'!:u K ella
duimg cong chia l6p gQi
ll dilm hod tan tili h(ln
dum. Nhilng truimg h<iP
nay hil!m bon tnrCm.g
h<iP trtn. Thf h
nu6c trietylamin c6
tK= 18,5C.
4. Tl'lllfng hqp 4 :
0 10
80

1 20
0
\
\
""
20
40
I
/
I
\
1
7
K
80 80 100
Hi111! X/V-14. H(! mr6c- trietylamin c6 diim hoi tan

c6 dii'm hoi tan tdi trin vi dlldi kh6p kin (blnh
Hai nhanh duimg cong chia lap c6 tht! hinh thilnh mOt duimg cong
khep kin c6 d(et\1 boil tan tm hl)l1 tren (K) vil dum (K').
Thi M nu6c - nicotin (C
10
H
14
N
2
) c6 K va K' dlng llng v6i 32%
kh6i hn;tn.g nicotin, nhtrn.g tK = 210C va tK' = 61 C.
186
5. Quy tc dtlilng klnh thing
Nam 1886, nha Me hqc Nga
. Y.F. Alecxeep dii tlm ra mt quy
tic gin dUng, gQi 13. quy t&c dubng
kinh thdng, theo quy tAc nay. trung
binh ct)ng cUa tlulnh pluln 2 pha
lOng can b&ng U ctic nhift dt) khdc
nhau dutfc pluin b6 tren mt)t duimg
gdn thting gt;'i 10. dUUng kinh thdng
di qua dilm hod tan tili hqn.
Thf tren hlnh XIV - 13,
trung cUa nhfing dol_lll thing
d6ng nUt ab, a'b', a"b", ... hQp thAnh
mQt duilng gAo tMng di qua
boa tan tm mm K.
Quy tAc Alecxeep chi 8p d9ng
khi thiinh phJin bitu thj hAng %
fC
K
180
140
100
60
K'
0 20 40 60 100
(H
2
0) (nicOtin)
---.. % kh6i luqng nic6tin
Hi11h XIV -15. nll6c niOOtin c6
vimg chia l{Jp khep kin
kh6i liJI!Dg, khOng ap cho ln!Ong hgp thiinh phJin thi hAng
%mol.
,;: A,..,.
D- GIAN DO PHA HI;; BA CAU TU
7. NHO'NG eAcH BIEU TH! THANH PHAN
BACAUTlf
1'hanh phn M 3 dfu tit A,B,C thOOng dugc bifu dien bAng m(lt tam
gi8.c ABC (hlnh XIV - 16). Tir cac dinh, h{l nhUng dllbng cao
Af, Bg, Ck. r6i chia m6i duCmg cao tam 10 dol_lll bang nhaU (mOi dO{lll
n3.y chia lAm 10 nhali, nh6 hem), qua m6i V{I.Ch d6 kf:
nhrtng duOng thing song song vOi. cc.mh ella tam gi<ic ABC se duqc mt
lu6i tam gi8.c.
187
DUng m<:tng lu&i nay c6 m<)t c3.ch dan gioln thanb pba.n
cUa 3 ca'u tir. Ba dinh tam gioic Ung vOi 3 ca'u tlr A,B,C nguyen cha't.
M6i qmh Ung vOi mQt h 2 ca'u tir ghi a 2 dinh rna Cl;lnh d6 n6i lien
(hoan toan kh6ng c6 ca'u tir thU ba). M6i ditm ben trong tam gicic Ung
vOi mQt thilnh pMn xcic cUa h 3 ca'u tir. Ngugc l<:ti m6i thaoh pban
x3.c djnh cUa h 3 ca'u tir Ung vOi mQt ben trong tam gi3.c. Th.anh
phAn nay c6 the bieu thi theo 2 phuong ph<ip kbac nhau.
c
-%8
0
"c>
\
Hinh XIV -16. Tam gi3c GipxC1- Rowb6m di biiu ditn 1hlmh pMn 3 ciu llr
I. Phumtg pluip Gipxd tren thuQc tinh cUa tam gicic deu Ia to'ng 3
klwdng ccich tU m{Jt dilm P bd't k"i trong tam gicic de/1 3 cr;mh b&ng duimg
cao cUa tam gicic. C6 tht thilt d3.ng thuQc tinh d6 nhu sau (hinh
XIV- 17).
Gqi a Ia dl;l dai cUa cl;lnh tam giac Mu ABC va h lA dl;l dai cUa dUOng
cao Ck.. Din tich S cUa tam gi<ic ABC Ia :
188
S = .!. ah
2
Tir ml)t P Mt ki ben
trong tam gilic, 3 th!ng
dUng Pa, Ph, Pc xu6ng 3 cl;lfih
tam gicic.
T6ng tich 3 tam giac con
PBC. PCA,. P AB bAng di11 tich
tam gicic ABC va bllng :
I I
S= - a(Pa+Pb+ Pc)=- ah
2 2
tUd6:
Pa+Pb+Pc=h
. .
b
A ,,
/ ---
/
c
c k
a
---
--
--
--
B
Hlnh XIV -17. MC>t thu{)c tfnh ciia tam gilic
qmh
quy uOc dl) d3.i duOng cao cUa tam gi8.c mtg vdi 1 100, thi
d1,1 bang 100, thl dl) chUa ella m6i tir trong 3 tir bllng dl) dai
ella kholmg each t6i d6i v6i dinh ella tir. Thi dl}., tren hlnh
(XIV -16) diem P ilng voi thiinh ph:in 20% tir A ( do(lll Pa), 50%
tir B (do<J.ll Pb) va 30% cAu tir C Pc). Khi dUng theo phucmg pbap
Gipxa thl tam gilic dien thanh ph!n 3 tir thuCmg gqi 1a tam
gitic Gipxu.
2. Tam gitic Rt5zdblJm dUng theo phuang phdp ROzctb6m, phuang
phap nay sir dl,lilg thul)c tinh ella tam gi8.e deu ta tdng 3 do{ln th&ng ve tit
mt)t dilm P bdt ki trong tam gitlc song song val C{lnh d6i val dlnll
ccfu tti bdng d(J ddi cUa c{lnh tam gidc. quy udc dQ dai ella qmh tam
gh\c Ung vOi 1 100 thl P hlnh 16 Ung vOi thilnh
phAn 20% dlu tir A Pa'), 50% tir B (do<!-n Pb'), 30% ti'r C
(do(lll Pc').
Chll Y rllng Pa' = c'B, Pb' = Ak, Pc' = kc', do d6 :
Pa' + Pb' + Pc' = c'B + Ak.+ kc' = AB = 100
Thy theo trulntg hQ!l c6 the quy u<x: AB = 100% kh6i Im;mg
100% mol.
C6 hai dinh H danh rieng cho nhiing gi3.n d6 tam giac thanh pMn.
D[nh Ji 1. Ml)t duCmg thing bat ld di qua m1 dinh tam gicic c6 thu()c
tinh lil m9i-diem clla-n6 dtu mtg vOi mQt khOng d6i ve 'dQ chUa ella
2 cAu ti'r kia.
189
Thf d!.J, dubn.g thing Cz (hlnh XIV- 16) lrng v6i nhilng M trong d6
d chUa% ella 2ci"u tir Ava B ti 1 v6i nhau theo 7:3.
Djnh li 2. Mt dui'Jng thlng hAt kl song song v6i mt C!.lnh tam gi:ic
c6 thuc tinh li\ mQi ditm ella n6 Ung v6i mt d chUa khOng d6i
ciia ca:u tir bieu blri dinh d6i din v6i d6. Thi d1,1, dui'Jng thilng
xy (hlnh XIV -16) llng v6i nhilng lrongd6 di)chllaciJa cifu tit !a 75%.
Quy t&c dOn bJy cling 3p d1,1ilg cho giRo d6 h 3 cA'u tir gi6ng nhu n6
da ap dl,mg cho M 2 ca:u tir. Thf d1,1 nu dii!m S (hinh XIV-16) lrng v6i
thanh phAn t6ng qu:it ella h vi\ M tach ra thanh hai pha bieu bbi
nhiing diem R v3. T thi :
htqng pha R Sf
=
1uqng pha T SR
Ghi chU. Trang mt s6 tnrOng hqp, thilnh ph!n M 3 ca:u ti'r duqc bieu
dit!n trong nhiing tqa dQ vufmg g6c, dh!u nay Him c_ho vic tinh hn;mg
ella m6i pha ritng re dugc dan gian ri"t nhieu. Gich ni\y thuimg dUng de
bieu dien th8.nh phftn ella h 2 mu6i khi c6 1 ion chung.
8. BA c.O:u ni HiNH THANH HON HQP
OTECTI BA
Thanh phiin h 3 cA'u tir duqc bieu dien bang tam gi:ic di'!u
Nhit d duqc ghi tren nhiing ttvc thilng g6c v6i phAng tam giac hQp
thanh mt rn6 hlnh khOng gian du6i mt lAng trl;l tam gi8.c. M6i
lang tn) li\ rnt gi3n d6 pha ella mt h 2 ca:u tir tuang Ung, cOn
nhihlg diem ben trong the tich lang tfl!. thi bieu nhiing 3 cA'u tlr.
Ta xet trui'Jng hqp dan giin nhi"t khi 3 ca'u ti'r A, B, C khOng hlnh
thanh h<JP cMt boA hQC, khOng hlnh th&th dung d!ch rein vi\ cling kh6ng
c6 SJ! chia 16p trong pha lOng. Hlnh XIV -18 bieu ella mt
giim d6 kh6ng gian nbu d6i vCri h Bi-Sn-Pb (de dan giRo, ta gia
thilt trong h nay khOng c6 SJ! hlnh thi\nh dung d!ch r8.n; thJ!c ra
Sn - Pb c6 hinh th3.nh dung d!ch r&n, song ta 00 qua).
190
Sn
Hi11il .JaV-18. Gilin d6 pba khOng gian Bi- Sn- Pb c6 Cllecti ba
ben trai cUa lang lf\l bitu dien giin d6 ella hai Bi-Sn c6
atecti E
1
, ben ph8.i bieu dien giim d6 ella Sn-Pb c6 cnecti va
sau bitl:u dien gi8n d6 ella h Bi-Pb, c6 atecti E
3
. Cic atecti

deu 13 otecti bt;ic hai, nghia Ia ella 2 ca'u tir.
Trong h ba ca'u tit Bi-Sn-Pb c6 ml)t atecti bqc ba E
4
v6i thanh pMn
hgp kim de n6ng chily nMt ella h ba da cho, hqp kim d6 c6 nhit
dQ n6ng chAy 96C vii chtla 52,5%Bi, 32%Pb vii 15,5%Sn. Nhiing
tBi Et E4 E3, tSn va 18. nhilng M liquidus vi\
cho bit ca'u tir na.o ella hqp kim va b nhit dQ uao thl hilt diu kt tinh tit
h6n hqp lOng c6 thanb. phAn _da cho. & t
8
i E
1
E
4
E
3
18 vUng (miln
hay trutmg) kt tinh cUa Bi, M m*t t5n EzE
4
E
1
lA vUng kt tinh ella Sn va
tPb E
3
E
4
Ez 18 vUng kt tinh ella Ph. Phdn khOng gian b du6i
nhitng M d6 lA vilng t6n nhGng h 2 pha g6m dich n6ng chiy
(pha lOng) va pha tinh tht ci:Ja kim tuang ling.
191
NGu cit giiin d6
khCng gian b3.ng nhtlng
pbing ngang
nhilng nhit d kbae
nhau va ebiu nhO'ng
duCmg d.t ella nhilng
mat pMng d6 vm nhtlng
be liquidus lfn
'd!iy ella blnh lang trl,l se
thu duqc nhfing duCmg
ding nhi1 ella blnh
ehiGu eho pbep suy
dOO.n ve trAe d ella
nhilng be liquidus
va ngbien eUu qua trlnh
kGt tinh ella djeb n6ng
cbay (hinh XIV-19).
Sn

Hi11h X/V-19. Gian dO pha tam giac h Bi-Sn-Pb
c6 otecti bl).c ba
NhOng diem e
1
, e
2
, e
3
, tnrng eho th8nh phAn ella nhUng ateeti
bai tuang ling. Diem e
4
Ung vm thlmh pM.n ella atecti ba.
9. 51,1 HOA TAN C6 HI).N CUA BA CHAT LONG
1. Trl/Ong hqp chi c6 1 ci[ip ch8t lOng hoi tan c6 h'n vao nhau
xet M 3 ca'u tit lOng A, B, c. Gi3. thit A va c bOO. tan khCng cb
v3.o nhau, c3. B vit C cfing cOn A va B thl boa tan c6 bi_I.Il vito nhau. 0
t,p const, nu trn A va B vao nhau thl se hlnh thanb 2 lOp lOng
nhitng thlmh pb.tn xae djnh bc1i nbitng dit'!m a va b trfn qnh ABella gi3.n
d6 tam giac (hinh XIV-20).
Them vao M 2 ea:u tit d6 ca'u tir thU ba c. ea'u tit nay boa tan ritng re
duqc vao 2 lOp lOng, kt qwi Ul e6 Sl,l" blnh thanb 2 dung djeh lOng 3 ea'u
tir 11,1 can bAng vai nhau gQi 13. nhitng dung djch lien htJp cUa nhau. Bang
c!ich them nbfing hn;mg khlic nhau ella ca'u tir C, c6 tM thu mt diiy
192
nhfrng dung djchJien hqp ba (dung djch ba U1. dung djch 3 ca:u
ti'r). N6i Hen nhlmg cUa giim d6 tam gi8.c Ong v6'i thanh phAn ella
nhflng dung djch lien hgp, ta dm;IC dOOng cong chia lOp akb (hlnh
XIV-20b). DuOng cong nily chia gi<in d6 tam giac thilnh 2 vimg d6ng
va di Mqi bOn hqp cUa 3 ca:u tir A,B,C, mi\ th8.nh ditn
hOi m iJ ben trong vUng di the deu t<ich ra thruth 2 dung djch ba
hqp cAn bAng v6'i nhau, thanh philo dien biJi nhflng dim a' va
b'. Khi tMm ca'u tl:r C thl tan IAn nhau ella hai ca'u tir A va B tang len.
qua li\ thi\nh phAn 2 dung djch ba lien hgp dAn dAn khB.c nhau it
di, cu6i cUng khi tCti diti'm K gqi 13. dilm hod tan ttli Ju;m, thl thanh
phAn hai dung djCh tr6' thi\nh bAng nhau.
a)
B
Hinh XIV-20. Gi!ln dO pha h 3 ch!l lOng c6
mQt cJ!.p holt tan c6 vilo nhau : a) giiln d6
kMng gian ; b) gilin dO tam giic l1 mN
nhi1 d(l x;ic d!nh
Trong nhieu tnrOng hqp,
thilnh phAn nhO'ng dung djch
lien hqp Ung v6i m ben
trong duOng cong chia lt'Jp c6
the x8.c d!nh gAn dUng dl}'a v3.o
quy t&c TaraxencOp, theo quy
t8.c ni\y. neU keo diii nhiing
dulmg th&ng dOng mit (hay
dUCm.g lien hqp, tt!c li\ nhiing
di.Wng thing n6i lien nhilng
ditm nhrr m va a', b') thi chU11g
se c&t nhau xOp xt 19i m9t
dilm D (hinh XIV-20b).
trong nhfrng dl.IOng dOng nUt
13. ab cUa mQt qnh tam
gi<i.c, do d6 giao ditm D ci:Ja
mQi dl.IOng d6ng nUt nicn tren
duUng keo di\i ci:Ja
tam gicic. Tit D
v6'i dt.Kmg cong
chia 1(1p aa' b'b se duqc ditm
hoi\ tan t6'i h{ln K. Quy tic
TaraxencOp cho phep xac
djnh tbanh philo cac pha bang
dO thf.
193
c
D
A a
B
b)
Khi tang d(> thl d(_) tan liln nhau ella cac ca:u tlr thay d6i va khi
tOi nhit d tai tK th1 h tr6 thanh d6ng tht'!' b mQi thanh phan. tUc
Ut3 c&u tlr lOng boa tan hoan vao nhau (hlnh XIV-20a).
Trang giin d6 kh6ng gian h 3 du tir lOng, vimg d6ng tM va dj tM
duqc phAn c<ich nhau bbi be ml.lt chia lOp. Dubng cong kk'K lit quy tfch
clic diem t6i 0 nhitng nhit d khac nhau.
Ghi clul. Khi them cllu n:r thU' ba vito h 2 ch.!t!Ong chi hOO. tan c6 hl!Jl vilo nhau,
cfu n'r thU ba ho3. tan dugc rieng re vao d. hai ch:it lOng thl dt') tan lin nhau ella 2 chit
lOng nay se duqc tang ICn. D6 hl truOng hqp cUa giii.n d6 XIV-20 d!i xet b trCn. N(u cllu
ti'r thli ba chi hoA tan dm;rc vlio mt')t trong 2 chit lOng thl dt') hoD. tan !lin nhau ella 2 chit
lOng nay giim di.
2. Trt.I'Ong hc;;:p cO 2 hay 3 chit lOng hoa tan c6 h'lln vao nhau
Trang ht;: lOng 3 ca'u tir A,B,C, c6 c6 2 chAt lOng thf d1,1 ci_i.p A
va C tan c6 hl).n vao nhau, c<}p B va C ci1ng cOn hai chat lOng Ava B
thl boa tan khe,ng hl:lfl eM vao nhau. M(>t trong nhihlg giB.n d6 pha
lOng 3 ca"u tlr nhu ling vOi hlnh XIV-2la va cho tha"y c6 2 vimg chia
lOp vOi 2 t6'i h{l!l kt va kz.
194
c
c
a)
b)
Hinh XIV-21. Giiin dO pha h 3 cMt lOng rna 2 boa tan c6 vii.o nhau
H mWc - IUQU etylic - nitril cUa
axit sucxinic b nhit trong kho!lng
20C va 30C dUQ'c bieu dien bAng mt
gicin d6 tuang tJ!nhu hlnh XIV-21a.
H benzen - bromofoc - axit fomic
duQC bitu dien bB.ng mt gi3.n d6 gi6ng
nhuhinh XIV-2lb.
lfmh XIV-22 Ung vOi tnrUng hqp 3
ch&t lOng A.B.C rna eli 3 C*-P A-B, B-C
va C-A dtiu boa tan c6 vao nhau.
Thi d1,1 Fe-Zn, Pb h mr&: -
ete- nitril cUa axit sucxinic v.v ...
c
Hinh XIV-22. Gi8n d6 pha 3 chift
lOng hoA tan c6 vao nhau tUng
dOi m(lt
195
CHOONGXV
TliQNG BE HAP PHI,I
1. CUONG VE s(lc CANG BE VA
HAP PHI,J
Hin IUQIIg be va hap phl:l c6 y nghia to !On vt If thuyft ciing nhu thi,IC
d: bi1 trong dQng hQC cUa nhifu qua trlnh boll hQC vii trong xUc tic dj thl!.
I.Avit lA nguCri. d!lu titn ( 1785) dUng than cUi dt !Am dung djch khOi chat b&..
N.D.Ztlinxki Ia nguCri d!lu Lien dUng than dl! hUt cic chat d()c h\li.
1. SUe cing b8 m'-t
L6p be ella mt cha:t lu6n luOn c6 nhihlg thuQc tinh kh<ic it nhi6u
so v(ri phAn be:n trong ella n6. Thi d1,1, b be m*t pha.n chia chfft Umg -
kh6ng khi - nhiing pha.n tir chfft lOng b 16p hi! ch!u mt sUe hUt tir
phia nhihlg phAn tir ben trong IOn hdll Ut tir phia cic phan tir khi vl ccic
phAn tir khi nay b treyng th8.i loang. rfft xa nhau.
SUe hUt d6 phin 8.nh SJ! t6n <ip snit nQi cUa cMt lOng thlWng -nit
IOn (c6 thli t6i h8.ng nghin bar), c6 xu huOng keo ccic phan ti'I vao ben
trong choft lOng theo hu6ng vu6ng g6c vffi be Uun gi3.m M dln
mlic t6i trong nhO'ng kin da cho.
De: lam tang be chAt lOng, plcii t6n c6ng thAng cac lgc
phAn iii ga.y nen ap sua:t [)() l6n ella cOng nay. quy ve lcm
2
be gQi
la sUe cling bi mt, ki hiu 18. a va thj bAng ec/cm
2
. V1 ec = din.cm
nen a ciing c6 the bitu thi bAng din/em. Nhu vi}.y sUe cang M c6
bieu thi nhu 18. life tren dun vf d diii nhu niing Iut;tng trb1 don vj
difn tich. SUe cling M c6 vai trO trong de hin tuqng be m*t nhu ap
suAt c6 vai trO trong cac hin tuqng the tich. Thi d1,1 c6ng gian nO tM tich
SA= pdV cOn c6ng tang din tich be m*t mQt luqng ds bang SA'= ads.
Theo li I, dU = SQ + OA ; d6i v6i qua trinh can bang SQ = TdS,
cOn OA = pdV + OA'. D6i vCti l(1p be kh6ng c6 nhO'ng hiu lm.g
tich, do d6 pdV = 0, chi c6 nhO'ng hiu (mg M do d6 :
l%
dU = TdS + crds (XV. I)
>6i v6i h c6 s6 mol thay d6i, cOn pbai them s6 L!J;dn; vao dU
ella lOp be :
(XV.2)
DUOi inh btKmg sUe cAng be kh6i lugng chcft lOng se hu6ng t6i
c6 hlnh c!iu vi be cAu Ia be nhAt d6i v6i mt)t the
tich da cho.
LUtJllg chAt lOng cB.ng be, hiu Ung d6 dmg rO. Nhfing giQt chcft lOng
dU be c6 hlnh du ngay trong m6i truOng khi, thi d1,1 nhfing giQt mua hay
sU'Cfllg mO.. Thlly ngan c6 sUe cang be bit cao (cr = 472 ec/cm
2
a
20C d6i v&i Hg, trong khi cr = 73 ec/cm
2
d6i v&i nuac va cr = 29 ec/cm
2
d6i v6i benzen a 20C) nl:n Hg ra't hlnh thanh nhfrng giqt hlnh cAu.
2. H8p phi}
a) Dinlz nghia. St! hd'p phi} (dUCfllg) lB. sl,l' t*p t1,1 cha't tren be phAn
chia hai pha tich (d.n-IOng, dn-khi, IOng-khi). Cha't rna tren M mi,i.t
ella n6 SJ! ha'p ph1,1 xily ra gqi 111 cluft hay hd'p phiJ, cOn cha't duqc
11,1 pha.n chia g\)i ta chd't bj hd'p phiJ.
tinh vOi 1 gam hcfp ph1,1 gqi Ia bC mijt rieng ella n6.
Nhihlg kh6ng c6 16 x6p c6 be rieng tit vai m
2
/g dn v3.i tram
m
2
/g. Nhihlg c6 h th6ng 16 x6p va mao ph:it nhu than
tinh, silicagien, zMlit v.v ... c6 th6 c6 be rieng t6i trtn
2
IOOOm /g.
b) Life Ju1p phl}. Nguffi ta pha.n bit hd'p phl} w,it If hay lu1p phl}
Van de Van va lufp phl} hoti hqc hay ho<i htfp pht.J.
Trang hd'p phtJ Ji, cac pha.n tir bj hcfp ph1,1 lien kt v(1i nhihlg ti6u
pha.n (nguyen tir, pha.n tir, ion) 0 be Mp ph1,1 1Xri nhihlg life
Van de Van yeU c6 cimg biln cha't v6i nhihlg lJ!C quy djnh s1,1 sai lch ella
khi thl,lc so v(1i khi li tubng va gAy ne:n SJ! nglffig 11,1 ella khi thB.nh cha't
lOng. Sl,l ha'p ph1,1 li lu6n lu6n nghjch.
197
Thui'mg cGng c6 S\l hlnh th3nh lien kef hidro gilia phAn tir b! ha:p ph1,1
va nhilng ion hay nh6m thfch hqp (nhu OH) be v4t hAp phq.
Nang lm;mg lien kt hidro thui'mg nit be, th(p bon 41,8kJ/mol.
Trong help phi! hoti h<Jc, c6 nhiing IJ!C boa tti kt ion, lien
kt c()ng bOO. ke't Jii6i tri),litn ke't nhilng phAn tir b! hAp phq v(1i
nhilng tie:u phAn cUa v*t Mp ph\1 thanb nhilng h{JP chdt be' mijt. Nang
lm;mg nhilng lien ke't nay c6 the t& hilng trAm kJ/mol.
c) H6p phi! va gidi hiip phi!. Trong h6p vt li, cha:t b! ha:p ph1,1 c6
xu htt6ng chim toAn b be m*t cUa hAp ph1,1. Nhung n6 b! qwi trlnh
ngm.;tc dm trO. d6 18. S\l gidi hti'p (hay kluf help Giili hAp ph1,1l8.
qua trlnh cac phan tir b! ha:p ph\1 ri1i bb be ml[lt hAp ph\J.
D6i vOi hd'p phi! hoO luJc, do cac lJ!C bOO. tri m;pili quy c:finh ntn SJ!
giili Mp ph\1 xily ra ra:t kh6. 0 dAy, SJ! giili hAp phi,! thl,fC chat 18. pMi pba
vo lien ke't giii'a nhilng phAn tir b! hAp ph1,1 v(1i nhilng tieu phan cUa
lOp be m*t nay thuOng lAm bin d6i mi_j.t hoi hQC chAt hi gi8.i hAp
ph1,1. Do d6 ba:p ph1,1 boa hQC thui'mg khOng ngh!ch. S1,r Mp ph1,1 oxi
trM than Ia mQt thl dl,l men hlnh cho hAp phi,! hoci hQC. Khi thJ!C hin SJ!
giili ha:p ph\1 bc\ng each dun n6ng thl khOng pMi oxi ri1i khOi mi).t rna
li\ cac oxit cUa cacbon.
d) Anh hildt1g ella nhit d len luip Hip Phi.! If va bOO. hQC tOa nhit,
a hip ph" V*tlf (vii kJ/mol) u hli'p Phi.' boii hQC (c6thl! tc'ri himg triDn kJ/mol, vao
cU Ung nhit ella phin Ung bOO. hQC). Vl st! hifp phy. tOa nhi1, nen, tbeo nguyen If
cbuyin d!ch cAn b!ng,Juqng ch!t b! hli'p phi!- phlli giim kbi dQ tang.
Tuy nhil!n, 0 nhit dQ thip, hA'p ph1.1 bOO hQC thuOng ditn ra va khi nhi1 dl)
rang thl t&: d tufp phy. c6 thi tang theo. Difu nay c6 lien quan dtn hdng rdo /w{lt hod
(41,8-125,4kJ/mol) tnmg cho tuang tac bOO h9C gifra ciic pban tir bj Mp phy. vii. cac
tiiu PIAn cUa I(tp M htmg rlto h6a, xem phdn Dng hoi hQC).
Hllp ph1,1 bOO hQc mil t6c d pb1.1 thul)c vilo himg rlto ho<;tt bOO gQi 13 Mp p/IJ! hogt
h6a. HA'p pht.J boa h9C c6 tMiil hip ph ho<;tt holi nhung khOng phlli bao giU cfing lit hA'p
ph\1 boa.
Hlnh XV-I mota s\f thuQc ella hrqng khf OJ bj hip ph1.1 tren mij_t kim ICl;:li
paladi vao nhi1 d T (L<,li iip sui't p == I50rnmHg khOng d6i). 0 T tbip, bit diu xliy ra
truOC S\f hA'p pb1.1 v*' If; khi T tang, n6 gilim (nhiinh AB cUa duUng cong).
Khi T tie'p Uj.c tang, thl dutmg cong cJ!C t'ttu t<,li 8, d6 c6 st! chuytn til hip
v*l II sang hli'p ph\) ho<;tt hoii va hip ph1.1 ho<;tt hrni tAng theo nhi1 dQ (nbanh BC). TOi C\fC
d<,li C. ha'p hCl;:lt hrni t&i tl'<,lOg thiii cAn til d6 gi3 trj cUa lm;tng CO bj hip ph1,1
bOO. hQC giiim theo nhiinh CD khi T tang.
198
Sl,r t6n tf,li nhitng C\fC ti.!u vii CJ!C trtn
duOng bifu diln cM'ng tO c6 nhfrng qua trlnh
bOO di tham gia vito qmi trlnh Mp ph11-.
e) Nl!ilng cdch nghien cUu slf Mp phi:'
KhOng tUy tltu()c vilo hlfp ph1,1 13. If hay
bOO hqc, nguOi ta nghien t:Uu ; I) S\f hip phi}
trtn be chat lOng (hay dung djch) ; 2) 'S1!
hlfp phi/- khf hay hoi trtn bt m*t rAn ; 3) slf
Mp ph1,1 chft tan tir dung djch len be v41
rAn nhUng vito dung djch.
Sll'c citng be mi,\t chi c6 vai trO q uan
trong S\f hlfp ph\(ltn be chlft lOng hay dung
d!ch. D6i vm cln, khOng c6 phucrng pM.p
chfnh x;ic, dU tin c._y dido site c<blg be
C6 tht nghitn ct'iu S\f ella hrgng a
chllt hi Mp ph\1 vao d T i:J ip sulft can
bAng p khOng d6i h<* b n6ng d can bAng c
khOng d6i. DuOng bitu ditn a= f(T) 0 p = const
gQi Ill. duOng ddng dp lu1p ph'.l va 0 c = const
gQi Ia duCtng d&ng m1ng (dt)) ht[p ph!J. DuOng
A
\
c
1
D
T
-
Hinh AV-1. 51! ph\1 thuc cUa
khf CO bj h!fp ph\1 tren pa]adi vao T
a p = const
cong trtn hinh XV-I chinh lil. mt dlplg (phUc ll,lp) cUa dllimg ding 3p hap (phUc ll!-P
vl c6 lhtm qu8. trlnh ho11-1 h6a).
Phd bil!n hC1n, ngtiOi. ta tnmg ph1.1 bang ph1.1 thuc cUa lm;mg a cha't bi
Mp phlJ vao ap can bang p n6ng dQ can bang c cUa d6 trong pba th tich
khi c6 can bartg phlJ aT= const. Dtrong bii!u a= f(p) a= f(c) aT= const
gQi Ia duCmg d&ng nhit Mp ph!J.
3. f)lfCfng ding nhi't ha'p ph!J - f)!nh lut Henry. Phlfcmg trinh
di.ng nhi+t h&p ph!J PhrOinlich
Vi<: cliu nhiing
duCmg ding nhit c6 tAm quan
trqng hang dAu va mqi thuyt
ha'p pholl gi!i quyt uu
vcfu M nay.
Hlnh XV-2 Ia m(lt trong
nhling di.Lilg difn hinh (
Langmua) ella dUOng ding
ha'p phl,l g6m hai phAn thing va
m(:lt pba.n cong.
a
1
B c
A
0
-- p(ho?c c)
Hinh XV-2. M1 d11-0g dii!n hlnh (d11-0g
Langmua) cUa dui'mg ding nhit hip phlJ
199
Ph&n OA cho thAy d vUng Qp sudt (Ju)(J.c n6ng d)
tlufp, dr) Jufp ti If b{ic nhdt viii tip sudt (hot;Ic n6ng d{J). D6 H1. vUng
djnh Henry.
Ph&n thing BC g:in nhu nfun ngang, song song vOi tn,1c hoarth Ung v6i
p (hay c) IOn : hk d6 M ha'p ph1,1 da to3.n bao boa b6i. chit
bi hAp ph1,1, luqng chAt nay (tltc d<> ha'p ph1,1) khong tang bon nila.
Pbrut cong trung gian AB c6 hoi gi6ng duCmg parabol
PhrOinlich (Freundlich) da dua ra phuong trlnh kinh nghim sau d"
dien n6:
kpl/n
m
(XV.3)
x 13. lU<}ng (s6 gam hay s6 mol) chAt khf bi Mp ph1,1 ; m lit kh6i luqng
(gam) hAp. ph1,1 ; p 13. B.p suat can bAng ella khf trong pha the tich ella
n6 (khi bi hAp ph1,1 tlr pha th6. tich ha'p ph1,1) ; k van 13. nhilng
hAng s6 xac dinh bang thqc
Nu coi khf Ut khi 1i tuimg th1 B.p suAt p ti vOi n6ng dl> c ella khf va
phuong trlnh dAng ha'p ph1,1 PhrOinlich se vit lB.:
kcl/n
m
(XV.4)
Di k van trong (XV.4) se nhilng gi3. tr! hlmg s6 khRc v6i.
nhilng gia tti (XV.3).
Phuong trlnh Phr6inlich (XV.4) cling thuCmg dugc dUng de tinh
luqng chert tan bi ha'p ph1,1 tlr dung dich len M mi).t rAn nhllng vao
dung dich.
Phuong trinh Phr6inlich kh6ng duqc th.ing nghieng OA
va nilm ngang BC ella duOng bieu dit!n XV-2. Doi_Ul thilng nghieng
chi c6 thu duqc ntu n = 1, khi d6 = kp kc) djnh
m
Henry . Do{ln thilng ngang ling vOi vllng bao boa chi c6 thu dugc ntu
(1/n) = 0, tltc 13. khi n-+ oo.
V1 1/n 13. bAng s6 v3. ncim trong giOi hi_Ul 0,2 - 1 d6i vOi SJ! ha'p phl,l
trong m6i trubng khi va 0,1-0,5 d6i vffi SIJ hAp phl,l trong dung dich
200
phi.Mlg trlnh PhrOinlich chi thich hqp cho vi:mg ap suA"t hay n6ng d
trung blnh.
Phuong trlnh PhrOinlich c6 dua
ve d{lng tuyln tinh bAng each lA"y.
lOgarit hai v cUa (XV.3) chAng ,
X l
lg- = lgk + - lgp (XV.S)
m n.
tUc Ut /g.!_ ph1,1 thuc theo duCmg
m
thl.ng vao /gp (hlnh XV-3). Duimg
thing niiy dt tn)c tung t<.ti diEm A
sao cho:
OA = /gk
COn d d6c cUa duCmg th&ng, tUc 13.
tg a. thl bing 1/n :
l
tga. =-
n
lg ___!___
m
1 A
0
-lgp
Hinh .W-3. tuye"n tinh ella
phmmg trinh Mp PhrOinlich
BAng each d6 tlm duqc de dang gi8. tri cUa cic bang s6 k va n. DuOng
ding nhit ph1,1 hlnh 'XV-2 thuCmg gQi Ia duCmg ding nhit
phl,l Langmua vi ve tOOn b n6 dugc mo t8. t6t hem 1Xri phuang trlnh
Langmua rna ta xet b 6.
2. DIEU cAN BANG DQNG LOP BE
T VOl HAl PHA THE TiCH GIAP NHAU
1. Lop be mijt
Hinh XV-4 trlnh bay so d6 lOp khOng d6ng (thea phap tuyn
vffi be phan chia) c6 tich s giila hai pha tich Iva II tip gi3.p
nhau. Be dily "t cUa l6p be rlt be vl hiu nhitng lt!C phan tir b be
phAn chia gAy ra tinh khbng d6ng ella llJp be giAm nhanh thea
20!
khOO.ng each tdi m<}.t.
Ta chqn be dAy t' va t" b
hai ben be phAn chia
sao cho & ngoAi gidi hi;Lil
cUa chling (AA' d6i vOi
pha I va BB' d6i vdi pha
II) thl nhihtg pha I va II
Ia hoan toRn d6ng nha't,
cOn tit AA' de'n BB',
nhilng thuQc tinh cUa 16p
be bie'n litn t1,1c
tl.r nhilng thuQc tinh cUa
pha I nguyen chat (AA')
Hinh.W --4. Sod616p giihl hai pha the tfch
I vi II
de'n nhilng thuQc tinh cUa pha II nguyen cha't (BB').
2. )igu kifn cin bing
Xet h dj th.! c6 g6m hai pha the tfch I va II va 16p be giila
chllng. Tit ki(!n cAn bi\ng t6ng quat ella dt th.! suy ra 13. khi c6
cAn bi\ng, nhit d l:J khAp mQi phAn cU.a h, kti cii b 16p be phiii
nhu nhau:
T=T'=T (XV.6)
T va T" 18. nhit d cU.a pha the tich I va II cOn T lA nhit d cUa I6p
be
The' bOO. hQC cU.a m6i ca'u tlr i cUa h cling phai nhu nhau b kh8.p mQi
phati cUa M. tUc 18. :
1'\ = = f1; (XV.7)
COn kin thll ba cAn OO.ng ca hQC, u:tc Ia ap sua't cfing phiii
bang nhau b khAp mQi phan cUa h d! the thl chi dUng khi h dj thti
kh6ng bao g6m 16p be
Khi c6 be phAn chia thl ap sua't p' va p" cila hai pha the tich I va
II b hai btn be phAn chia n6i chung 18. khac nhau. Ta se chUng minh
nay diJa vao kin d\n bAng cU.a h c6 D6i vOi qua trlnh cAn
bang trong h c6 entr6pi chung, the tich chung va t6ng s6 mol m6i
ca'u til i cUa h phii kh6ng d6i, tUc Ia :
202
dV' + dV" = 0
dS'+dS"+dS=O
dn'i + dnj' + dni = 0
(XV.8)
(XV.9)
'(XV.!O)
Khi d6, dieu kin can bclng ella M c6 lA nang cUa h phiii
Cq'C titu:
d(U' + U" + U) = dU' +dU" +dU = 0 (XV.ll)
Gi8. thlr trong qua trlnh can bAng, phan chia s biln thien m()t
luqng ds vi\ gAy ra nhling bin thien the tich dV' vi\ dV" 0 hai pha tht
tich I va II. Khi d6, d6i vdi cac pha the tich (kh6ng c6 hiu Ung be :
dU' = TdS- p'dV' + (XV.l2)
dU" = TdS"- p"dV" + = TdS" + p"dV' + l:J.lidnj' (XV.l3)
vi theo (XV.8) dV" = -dV'. COn d6i vOi lOp be (kh6ng c6 hiu Ung
tM tich), theo (XV.2) :
(XV.l4)
q,ng ccic bieu thUc d6i vOi dU', dU" vi\ dU, ta duqc dieu kin d6i v6i
cqc tieu nl)i nang ella ca
dU' + dU" + dU = T(dS' + dS" + dS)- (p'- p")dV' + crds
+ + dn'\ + dni) = 0
Do (XV.9) va (XV.IO), phuong trlnh tren rUt cOn:
ti:rd6:
- (p'-p")dV' + crds = 0
, ., ds
p-p=crdV'
(XV.l5)
Ditu can bAng oo hQC nB.y cho tha'y lip suA't p' va p" b hai pha the'
tich I va II ccich nhau tx'ri phAn chia s n6i chong Ia kh3.c imau.
luqng ds/dV' do d(> cong ella be phAn chia quy dinh :
203
1) Ne'u bl m{it phdn chia s ttl be' mijt cdu thi:
2

r
r Ia ban kinh l114t du. Khi d6 (XV.15) tro thAnh :
I . .. 2a I p -p
r
(XV.I6)
r tinh lA duang nu d() 16m ella hu6ng v6 pha (') ne'u tAm ella
d lorn nrun iJ pha o.
2) Ne'u be' mijt phdn chia s ltl mtjt m{it cong bat ki thi c6 the chUng
minh r.lng:
r
1
va r
2
1a nhfrng ban kinh chinh khUc ella phttn chia. Khi d6
(XV.I5) trothimh, r--------.,
, , ( I I )
p-p=cr-+-
rl r2
(XV.l7)
(XV .17) ld plultYilg trlnh cu b&n cUa can b&ng cu h9c dol v6i bl mfit
pluin chia lOng - klli. Khi r
1
= r
2
= r du) thl (XV.I7) tnJ tMnh
(XY.l6).
D
. I ( I I ) h 2a (d6' " L< . ' ) . ]' ,
uqng cr - + - - 1 VOl uc:: cau gqt a ap suat
r
1
r
2
r
hay tip suOt Lap/axu (Laplace).
3) NeU hi mijt phdn chia lit m{it phdng (r-----+oo) thl <ip smlt Laplaxo
b8ng kMng va cAn bang co hqc (p' = p") trUng vai dieu
khi khtlng tinh dn hin tuqn.g he
204
3. NHUNG TliQNG lAM liOT VA MAO DAN
1. Hl+n tllqng lim Wt
NbO chft lOng Ito phing ngang Sl!b cUa m(lt r.in. GiQI chft lOng se ntn
v6i. m*t v$f- r!n ml)t g6c can bang a gQi lA gOc /XI hay g6c ltim udt, g6c oily dW?C do ve
phfa chll"t lOng.
Khi a < 90, ta n6i chat lOng ldm
uiJt v4! rin (h1nh XV - 5a). TnWng hJ;1p
nay xay ra khi cac pMn tit chii lOng tumg
tic vm cic ritu phAn ella r!n
hctn lA giUa chOng veri. nhau. 5I! hm u6t
se bOOn toim nu a = 0 (cos a =+I).
Khi d6 chit lOng chiy Jan ra c6 xu .
hu&lg phil hlt bt miJ.t ran cho d!n -
khi ldp chai Jlmg chi cOn 18. m()t l(jp don
phAn tU, thf d1,1, nhu nh6 nuOc ltn a) b)
taffi kfnh
Khi a > 90 (thl dv thUy ngl\n trtn
kinh), ta n6i chft lOng khfmg him
udr V$1 r!n (hlnb XV-5b). Trui'mg hgp
nAy xiy ra khi cic phlln tlr ch4"t lOng
tuong tAc vm nbau bon 13. veri. ctic
Hi11h G6c linn uat. a) ch&!Ong lAm
uat ran; b) chit lOng kMng Jam u6t
vljt rio
titu ,nan cUa r.in. Khi d6 Sl! chily ian se khOng xlty ra. CMt lOng se co thilnh giQt
c6 h1nh citu dirt ft nhieu (do uic d1,mg cila tn;mg tnrOng) va chuytn d(lng df dimg
tren v*' rAn. 51! khOng Jam ll6t se hoim tolm khi a = 180 (coso: = 1 ).
Cling m(lt chit lOng c6 thi liun lll'it rM nay, khOng lllm lll'it ran kia. Thf dl!-
nuOc li'lm lll'it m(lt thtiy tinh S{teh nhli'J\g kMng linn ll6t dm;Je parafin. Thtiy ngAn
khOng liun mJr: thiiy tinh (va n6i chung Clic bt phi kim) nhll'llg Hun u6t m(lt m!J( b3ng
sit
2. Hi'n tuqng mao dim
Nhllng m(>t d;iu 6ng nhO (mao qmln) vAo trong chAt lOng chUa trong
m(>t blnh r(>ng (hlnh XV -6). Nu chAt lOng tam uUt th3.nh 6ng thl chAt
lOng dang len trong 6ng t6i d(l cao h yit c6 khum lOrn. V& 6ng c6
tit din trim, khum gOO 13. m(>t pMn h1nh cAu. Vl tAm cUa d(llfim b
pha khOng khi nen theo (XV.l6):
, " 2a
0 p-p=->
r
205
Mu (') ling vm pha kh6ng khi (pha !),
dau (") ling voi cMt long (ph a II),
a lil sUe cang_ miJt ella chAt lOng :
. 3
B=rcosahoacr= --
. cosa
0 Ut ban kinh ella mao quill, a Ht
g6c Iam OOt.
Titd6:
2crcosa
p' - p" =.::o:=
3
Vl lip suA"t khOng khi p' IOn han
cip stmt cha't lOng p" trong mao quim
nen cM"t lOng ph<ii dang len trong
h
_--;...._.-
Hi11h.W-6. S., dAug cir.t chatlbng
llun u6t thlmh mao quan
mao quiin cho t&i dt) cao h, v(ri dQ cao nAy ap suii't ella ct chAL lOng can
bang v6i lip sua't Laplaxe1 p'-p", tli'c Ut:
p' -p" pgh
p lA kh6i luqng rieng ella cha't lOng, g lA gia t6c trqng truOng. Tird6:
h = 2crcosa
pBg
(XV.l8)
ch!t lOng dAng ten c3ng cao ne'u sUe cAng a ella n6 c8.ng
IOn, kh6i hrqng rieng p ella n6 dmg be, ban kinh 6 cUa mao qu::\n dmg
be va g6c lAm u6t a dmg gitn 0.
Q)ng tht!c (XV.l8) cho phep do sUe cang be a ella cha't lOng khi
da bie't h, a, p, 15 va g.
Nu 90< a< 180 thl cosa < 0 (chAt lOng khOng lAm uOt thatlh 6ng)
va thea (XV.l8), h < o,oo nghia Ia chA't lOng xu6ng trong mao qulin
chU khOng dAng len (tniDng hgp thlly ngl\n trong mao quiln thlly tinh ;
khi d6 khum cUa cha't lOng trong mao qulin khOng lOrn xu6ng mil l6i
ln).
206
3. A.p su&t hCii bio hoil trennhUng gi9t nhO
a) 0Qi p
1
va P2 Ill ap suit hoi biio boil tren hai gi91 cUa cling m1 chit lOng c6 ban
k.fnh r
1
va r
1
va gia thiCt hcri Ia If tuCmg. C6 thf chling minh dng :
luh =o 2crV m [_!_- _!_l
Pt RT r2 r
1
(XV.19)
b d1y o- lit ciing be va V m 13. tM tlch mol cUa chi'ft lOng, R \3. hang s6 khL Nhu
the, nu r
2
< r
1
thl P2> p
1
. GiQt ding nhO, ap suit hoi baa boa trtn giQt d6 dmg 1&1.
b) NCu thay cho giQt thfr nh!lt, Ia c6 m(lt M ph an g. utc Ill r
1
=co cOn r
2
= r, vil. gQi
P2 = P!o; V<d p
1
= Ppb (ph= ph:ing), ta duqc :
111
Pt6i = 2o.Ym
Pph rRT
(XV.20)
Ding thU'c nay gQi Iii cbng tMc T omxQn (= Kenvin). N6 cho tMy 3.p su!"t hoi bio hob.
cUa cha:t lOng trtn bt miit ph:ing cUa chilt lOng luOn luOn b6 han lip su& hoi bio bOO. trtn
be !Oi cUa chill !On8 d6 va do d6 thai c6 be mi).t ph:ing Iii thai ben han.
Nhil'ng giQt nh0-.;::6 lip su!lt hoi bao holt !On se IL! chuyl'!n d:l.n tbanh nhiffig giQt 16n hon va
thfmh m6t be m"!-t phling eiia chat lOng.
4. Sl! ngllng mao qui.n
Ciing tli(JJig 1\f nhu (XV .20) nhung vOi diu IDn Ia c6 cOng thUc Tomxon :
ln P10m "" _ 2aYm
Pph rRT
(XV.21)
tU:c Ia ap sm\t hoi hiio holt ella chat lOng bC mi_it 10m ella chit lOng bao giO ciing be
hontrtn be m"!-1 phlog ella chilt!Ong d6.
Trong nhihlg mao quim nu chit lOng !11111 116t t6t thimh mao qulin thl m"!-1 khum
ella n6 bao giO ciing lOrn. Khi d6, lip suit hoi biio boil ella chit lOng tren m"!-t khum !Om
se be hon trtn be m;(l.t pbing. Ke't quii. Ja tuy hcri chlla dUQC ;ip suit bil.o holt d6i vdi bC
phang nhung dii c6 tM lA biio boa qua biio holt d6i v6i chllt lOng nAm trong
nhihlg mao quim nhO, do d6 c6 the ngung trong nhiing 6ng d6 vil litm d.iy dli.n 6ng.
Hin lui!Jlg nay ggi lil .rtf ngung tlj mao qudn va c6 tht xiiy ra d6ng thbi v6i Sl:f hap
hoi ella cha:t lOng.
207
4. NHONG PHliONG TRiNH NHieT OQNG
CO BAN 001 VOl LOP PHUONG TRiNH
DANG HAP PHV GIPXO
1. Nhlmg d'i luq:ng dll cUa IC:Sp be mlJit
SJ! bilfu thien ella tnn:mg 1\fC pban tir 0 ldp giUa hai pha the
tfch Iva Ii tam cho ni nang U, entrOpi S, s6 mol c<lu til i, v.v ... ella lOp
M khac v6i nhilng hrqng t\Mlg ling trong cic pha tM tich I va II.
Do d6, ngU'Cri ta thltCmg khOng n6i to3.n 1.X) nc)i nang U, tOOn b
entrOpi S va to8.n b luqng mOi tir i ella lOp rna chi n6i
d du ella ni nang, ella entr6pi va ella s6 mol cifu tir i trong the tfch 'tS
cUa ldp (xem l{l.i hlnh X.V-4) so v6i nhihlg luqng nrong tbl.g
trong nhfing tht! tich tuang ling ella nhUng pha I va II, Ia trong tht!
tich ella pha I bAng ,;'s v8. trong tht tich ella pha II b8ng 't"s.
Ta ki hiu nhilng d dlt d6 ella ni nang, entrOpi vacUa s6 mol cA"u tii
i 13. u<sl. s<s> va C6 the biiu thi chUng qua cila tOOn b ni
nang U, toiln b entr6pi S va t6ng s6 mol ca'u tir i ella lOp be 'tS vOi
nhilng hiQilg tuong Ung trong tht! tfeh 's Va "s ben trong nhllng pha
the tieh 1 va 11.
u<s) = U-U'-U"
1')=5-S-S"'
(XV.22)
(XV.23)
(XV.24)
)(? du n(li nang tfsl gQi 18. niing lut;mg bi m4t todn phd11 ella ldp M
dl) du entrOpi S(s) gQl Ht entrOpi bl mfit va dl) du clu tir i gQi 18. dtj
lufp phf!. ella tir i trong ldp Chinh nhllng d du d6 ella nl)i
nAng, ella entrOpi vA ella s6 mol e6u tir i m6i tnmg eho SIJ khae nhau
giila 16p be va eae pha tht! tieh. Nhllng d du nay e6 tht! 18. dlK10g
bay Am.
Cling e6 tht! <ij.nh nghia nhllng dl) dlt tuang t\l d6i v6i nhllng hAm
dQng kMe nhu entanpi H. nang hn;mg t\l do F, da.ng :ip G v.v ...
208
NhUng luqng u<s>. s<s) va n(s) dinh nghia nhu ph\1 thuc vao
tich s ella be mi).t pha.n chia. so sinh chUng d6i vOi nhiing khic
nhau, c6 tht quy chOng don vi din tich be mi).t pMn chia :
tf'>t, = U, (XV.25)
_(s)/ r-
n, s 1
(XV.26)
(XV.27)
Us va S
8
gQi 18. nang luqng be mi,lt, entropi be d6i vOi 1 don vi din
tich be
luqng ri lit dl) du s6 mol cAu tir i trong tht tich ella l(tp bt c6
flin tich s = 1 so vOi s6 mol ca:u tir i cling trong thti tich d6 ne'u cac pha
thti tich I va II tdi. nhau bt phan chia s rna tinh d6ng nhtlt ella
chling vAn khOng d6i nhu khi cOn 0 trong lOng cac pha d6. lm;mg ri
gQi lit dq hci'p plltJ Gipw ella cAu tir i, thuCm.g chi gQi gQn 18. dQ Jui'p pi!If
ella i d6i vOi l don vi din tich bt
2. Nhftng phU'dng trinh nhi't dQng cd bitn dOi vOi lOp b8 m't
Tuong t\}' nhu (XV .14) th! bie'n thien dU ella tOOn bQ nl)i nang U
ella ldp bt mi,lt, c6 thti vie't thUc d6i vdi. bie'n thien dl) du ni nang
dU(s) ella ldp nhu sau :
d
- "'> Td--''t - d <>
u = :-; + +""'IJ.i ni
(XV.28)
Phuong trlnh nay cho thAy rWtg dQ du nl)i nang be mi,lt (cOn gQi ta
nang luqng be tOOn ph!n) ta ham dan tri nhAt ella cac thi.ra
s6 khue'ch dl) s va n/
8
>. Do d6, tfs> ti 1 v6'i c3.c thi.ra s6 d6, tUc 18.
!heo (XV.28) ta c6 the
u<s> = TS(s) +us+ :En-n.<s)

Vi pha.n toiln ph&n ella u<s> c6 :
(XV.29)
dtfs) = TdS(s) + _s(s)dT + uds + sdu + :Endn(s) + :En(s)d"
rl ;&- I rl
Bitu thUc nay chi d6ng nhAt vOi (XV .28) ne'u :
209
_s(s)dT + sdu + :E df.J.j = 0
_Tit d6 suy ra 0 T = const:
(XV.30)
sdu + :En;(s)j..l; = 0 (XV.31)
Nhilng phllO!lg trinh (XV.28), (XV.29) va (XV.30) Ia nhilng phuung
trinh cd bdn cU.a Gipxo d6i v6i lOp duqc Gipxo thit
nam 1876. Phuong trinh (XV.31) thi tuang tu phllO!lg trinh
Gipxo- Duhem 0 cac pha the tich.
Dt suy ra cJF's> ta dUng phep bin d6i Lagiangdro them -d(TS<s>) vAo
2 v cua (XV.28) se dugc :
dF(s) =d(U(s) - TS(s)) =- s<s)dT + ods + :EJ.lidni(s) (XV.32)
p<s> gQi lA d(l dtr nang luc;tng tq do (hay th ding tich) cU.a lOp M m;}t,
thUUng cOng gQi IA ndng lllf/118 /If do be' m{it. Tit (XV.32) suy ra :
cr = ( (s) ... (XV.33)
T,n
va c6 djnh nghla sl(c cling be' rrujt u nhu ld ruing lw.;mg /If do be' rrujt
cUa ddn vf hi mijt.
p<s) ciing c6 the suy ra til (XV .29) theo M thUc :
p<s) = tfs)- TS(s} =us+ :EJ.lini(s}
3. Phuong trinh ding nhift hip Gipxa
0 T= const. nu chia 2 v cU.a (XV.31) v6i sse duqc:
n.(s)
do + :E,....!.__dJ.li = 0
s
(T= const)
tUc lA d6i v6i dan vi ta c6 b T = const :
- du = :EridJ.li (T = const)
(XV.35) lA phuang trlnh ding phtJ cU.a Gipxo.
210
(XV.34)
(XV.35)
5. lfNG DI,ING CUA PHUONG TRiNH HAP PHI,I
GIPXO. 51,1' HAP PHI,I TRf:N BE LONG-KHi.
CHAT DQNG VA KHONG DQNG
1. H8p ph1,1 hc:Ji cUa mQt chit trin b8 m't chit tOng khOng hoa
tan ch8t d6
Xet SJ! hfip ph\1 tren be ciJa nu(fc (cl'u tiJ 1) hOi ella m1 chcft
cMt nao d6 (c!lu tU 2) kh6ng boa tan trong mWc, thi d1,1 ella mQt
hidrocacOOn no. Trong truCmg hgp nay, phuang trinh h!lp ph1,1 Gipxo
(XV.35) vit Ia:
(XV.36)
Vl nuOc tht,rc t khOng boa tan hidrocacbon no the' bOO hqc ella
n6 trong tht! tich va do d6 be kMng thay d6i,

= 0. Nhtr
(XV.36) thanh:
- dcr = r
2
dJ.1.z
Cho rAng hcri 13. khJ: li tucJng, c6 th hrni hQc bang :
J.Lz = Jl = ).1 + RT!np
p 18. ap su3t hcri, ta se duqc 6 T = const :
d!'
2
RTdlnp
Dua bit!u thii'c nay ella vao (XV.JJ):
r
2
_ ar ikr
OJ'z RT 8/np RT iJp
(XV.37)
(XV.38)
Nu bit Sl! ph1,1 thuC?c sUe cang be cr ella cMlt lOng 1 vao ap suA't
hoi pella ccfu tir 2 kh6ng tan trong chtltlOng 1 thl nhO (XV.38) c6 tht!
xac djnh dUtJC d h!lp hoi ella c!lu ti'r d6.
2. Hip phv tren be mf,t chit lOng mt?t chit tan trong chat lOng
Nu cifu. tlr 2 boa tan trong pba tht!f tlch cUa ca:u tir l, tbi d1,1 neu rm;ru
tba:p nhu ruqu etylic tan trong nuOc tbl th bOO hQC cUa mWc thay d6i.
211
Tuy nhien trong tru<:tng hqp nay, vAn c6 the dUng phuan.g trinh Gipxo
don gian (XV.37J thay cho phuong trinh d:iy du (XV.36) bhg
each chQn vj tri ella be phAn chia s sao cho so v6i vj tri nay, dQ hip
ph!J. r
1
ella dung mOi b3.ng khOng (r
1
= 0). Dieu d6 c6 thl!C
b3.ng each Uun dich be pba.n chia s sang Jiiia pha I pha
II cho t6i khi d<) du dlldllg ella ctlu til I theo m<)t phia be philn chia s
duqc bll chinh xac OOi. d<? du am ella n6 theo phia kia. Khi d6 :
- dcr =
(XV.39)
ki r
2
(l) c6 nghia 18. da chQn vi tri ella be phAn chia s sao_cho
d6i v6i. vj tri nay r
1
= 0. each chQn nay chi dUng duqc 0 vltng n6ng d<)
thtlp ella cMt tan vl chi a vimg nay n6 m6i khOng gay ra sai s6 dang ke.
Khi d6:
= RTdlna
2
a
2
18. dQ ella ctlu tir 2 trong tich ella dung d!ch II. Do d6 theo
(XV.39):
(I) 1 00 a2 00 c2 00
r, =----=--- = ---
RT Olna2 RT Ba2 RT iJc2
(XV.40)
Theo OOng thUc nay c6 tfnh dlft!C d<? Mp ph1,1 ding nhit r
2
(!) = f(c
2
)
nu bit SJ! thu<)c cr = <p(c2) aT= const.
3. Chit dQng va khOng ho,t dQng be
a) Clui't d9ng bl m{it ta ctuft khi tan vao dung mOi Jam giiim sUe
cang be cr ella dung mOi Ocr I Oc
2
< 0 va do d6 theo (XV .40) c6 d<)
hA'p ph\1 duang (r 2 (I) > 0), tUc ta c6 khi nlng t1,1 a lOp be ella
dung d!ch.
Thi dl,l ve chit dng be d6i v6i nuOc, c6 tht! lily nbieu hqp
cMt hilu co nhu cac axit beo, cac ruqu va amin c6 g6c hidrocacbon kha
IOn. Nhilng phan tir ella chUng c6 hai phAn: m<)t phAn khOng c6 CJ!C (d6
ta g6c hidrocacbon), mt phAn c6 C\fC, d6 ta nhilng nh6m OH (ruqu),
COOH (axit hihl co), NH
2
(amin) v.v ... (dung djch nu&: ella cic chA't d6
c6 sai dUC1Ilg so v6i d!nh Raun).
212
Tacmg tic giUa nhUng phAn tir mroc v6i nhau trong the tich dung djch;
1&1 han tUCIDg tic gina nhling phAn tU nuDe va nhiing phAn tU hilu Ct1 d6,
do d6 nhling phAn tir nay hi d!iy tir tM tich dung djch len dung
djch, va dQ h&p ph!J. ella chU.ng li\ diJOilg. Sl)' 11,1 ella nhUng phAn tir n8.y
b lOp be lam nhling tucmg lAc phAn ti:r b lOp be do d6 siic
cang gii\m khi n6ng dQ ella chllng tang len .
. b) Chdt kh6ng. hotrrt dt)ng. be m{it 18. ch&t khi tan vao dung moi lam
tang sUe cmig be ella dung mOi (00 0) va do d6 theo (XV.40)
c6 dQ Mp ph\1 am ( < 0 ). tiic 18. c6 xu hUOng rOi b6 thotng
di vao tM tich dung djch.
Oic ch&t khOng dQng M so vai nuDe Ia t&t c:l clic cha:t din
phA.n vO oo : axit, baw, mu6i. ThuCmg th1 nhling ion n8.o hidrat hot dlng
th1 cang gAy ra sl)' tang siic cang be :
O>Br>l; Li>Na>K.
c) CJui't kh6ng cO dnh Jutdng dfn sUe cdng be' mt;it cUa dung djch.
D6 Ia. nhllng cha':t phAn b6 deu c8 tren lOp va d trong the .tich
dung dich, do d6 dQ ha':p Ph\1 f = 0. Nhllng ch&t ni\y thuOng c6 siic
cang be gln Mng sli'c ca.ng be ella dung mOi. Thi dl} duOng
saccarow khi tan vao nuOc Mu nhu khOng tam thay d6i sOc cang M
ella nu6c.
4. Sl/ thu9c slk clng vio n6ng 49 ch'"t holjlt 49ng be mtt
d cic n6ng dl) c be ella chM. dl)ng be m*t, sik cAng be o cUa dung djch
gifun tl thu4n vai c :
o.,-o=kc (X"/.41)
0
0
11 sUe cang be m*t cUa dung mOi nguyen ch(l ; k 11 hAng s6
d cac n6ng dl) JOn han, d(l gifun ella o theo sy tang ella c biiu lhj bAng plurong trinh
do Sisc6pxJ:i flm thiy bAng lh\fC nAm 1908 :
0
0
-a=Aln(l +Be) (XV.42)
trong d6 A va B Iii nhiing hAng s6 dii tnmg cho mOi chit d(lng be m*t.
5. Ming dcm phin tti. Khf hai chl'u
Phln tir cUa nhiing chit dng be m*t lhlKm.g c6 si,J djnh hu6ng dft dii tnmg so
v6i be ella mr<tc. Thf dy trong si,J hip phy nu;ru h* axil beo, nbiing nh6m c6 ci,JC
213
OH COOH (bit'!u ditn bilng 0 tren hinh XV-7) do tfoh ua nu<rc VA c6 khii. nang
hidrat hoi n!n se nhllng vito mWc cOn g&: hidrocacbon khOng c.,c (bit'!u di!n bingO)
ngang tren nmk khi n6ng c cMt dl)ng bt mi!:t cOn M (hlnh XV-7a).
00 v& n6ng dl) c l&:t, clc g6c
hidrocacbon phan b6 thing g6c v6i bt
ra ngoiii khOng khi (hinh
cac phAn ti:r d6 ella chM. dl)ng
bt mil thilnh Illl)l thU' mt111g ddll
phil11 tli(mimg ml)t l&p phAn lir).
---
b)
Khi bt mrOC nt"t Jtjn, clc phAn 111
ella mmtg phan tan xa nhau utn
nmk vi't do chuyin dQng bOn
se chuyt'!n d(lng trtn mij.t nuUc dQc li!:P
v6i nhau va gAy nen m(tt iip stdt bt
MQI m8ng nhu vi!:y e6 thl! coi nhu ml)t
khi ll tlldng hai ehilu (hal chil!u vi" clc
pbAn lir khOng rOi 00 dllQC bt mi!:t ciia
mnk, chi e6 tht ehuyl!n dQng lrfn
nu6c). N(u n6ng dl) tang, ciie phAn tlr
gAo nhau hO'n thl c6 tht'! eoi mang dO'n
phAn tir nhulhi thlfC hai chiiu.
Hi11h W-7. djnh htWng ella nhilng ph An
ti:r chA"t dl)ng bt ml!t b bt ella nlf6c
00 v& n6ng dl) e be, theo (XV .41) :
:n:=0"
0
-G=kc
Uy vi phAn:
d:n: = d(a
0
- a)=- do-= kdc
Dua bit'!u thlle nliy ella -da vito ph!lOllg trlnh ha'p ph1,1 GipllO' (XV.40):
[=.- da = _o_d:n: = ekdc = .2:_
RT de RT de RTdc RT
(XV.43)
Qqi ID lA M m!ll mil I mol cMI dl)ng bt m{il ehie'm duOi. khf hai cbiliu, ta
c6 r = 1/ID. Dlragiii lrj nliy
I
- - ho!c1UI)=RT
ro RT .
(XV.44)
Phuang lrlnh nAy tuang 11,r phuang lrlnh thiii Oap!ron-Mend!ltep d6i v6i I mol
kbf 1i IuOng :
pV=RT
cr dAy v 18 lhl! tfcb khf 3 ebil!u, pIll iip suft khi, cOn lrong (XV .44), tfcb ID d6ng vai
lrO lA "1M tich" kbi 2 chitu va :n:, d giiim sli-c c!ng bl! ffii!:t cUa nu&, d6ng Vai trO 13 "iip
suft bt mi!:t" ella khf 2 ehil!u.
214
D6i vOi khi tbJ!c 3 chieu, phuang trlnh tqng thlii 13 phuang trinh Van de Van:
( p + :
2
) (V- b)= RT
D6i v& khi 2 chitu khOng II urOng, sT XO Phrumkin chi ra clog c6 thl
dUng m()l phiWilg trlnh tuang IJ!:
(x+:
2
)(ro-(l)=RT (XV.45)
a. va pItt ohllng h!ng 's6t1Wllg w a va b trong phuang trlnh Van de Van.
6. HAP PHI,J KHfVA HOI TREN RAN.
THUYET HAP PHI,! DON PHAN TIJ l.ANGMUA
(LANGMUIR)
1. Nhli'ng diim co bin ella thuy&t hip ph1,1 Lingmua
'
Thuyt h<lp ph1,1 Langmua (1916) xa.y dJ!Og tren ca sb thuyt dng
hQC pha.n tir g6m ba dii!m chfnh:
1) & ran g6m ml)l so" c6 h{lll nhilng vi tri hd"p phlf dl)c lt,lp
(nhGng trung tAm dng), nhGng vi trf Mp ph1,1 nay c6 lit nhiing
dinh, nhiing ch6 nhO cao c6 b ba.'t k1 be r&l nao dU da miti rAt
nhiln; thi dl,l gUC1Dg b6ng nhiin van c6 nhitng ch6 nhO cao 10 -?em.
M6i vj tri chi hQp phlf ml)t phdn tU khi. Tinh dc ella clic v! tri c6
nghia Ht sl,l' c6 mi}.t ci'ta mt phan tir khf b mt v! tri ha.'p ph1,1 khOng ilnh
hubng gl dn clic vj tri ha.'p phg kbac. Nhu qua trinh ha.'p ph1,1 khi bay

2) Ok v! tri ha.'p ph1,1 c6 ai Ivc nhu nhau d6i vai khf duqc ha.'p
pht;z; tUc Ia be ha.'p ph1,1lit d6'ng nhd't, bit clic vj tri M"p ph1,1
dCu c6 nhit Mp ph1,1 nhu nhau.
3) Khong c6 tUC1Dg tic giUa clic phArr tit d1i dli<!C ha.'p ph g.
2. Phwng trinh ding nhi;t hip ph1,1 Lingmua dOi vdi m9t khi
a) Thief lt,lp plutung trinh. 0 T = const, gQi 8 =a/am lit dl) diin ddy be
ella ha.'p ph\1. a lit Iuc;mg khi b! Mp phg trtn be d1i cho,(tinh
215
ra s6 mol khi dOi vOi 1 gam hifp 3m 18. h.rqng qrc khi h! ha:p
khi e = holm toiln).
Nhu a thj phrut bt hi ccic pbAn tir chim, do d6 phrut bt
m*-t cOn tr6ng 18. 1- a.
Dt c6 dugc bifp pba.n tir khi pbili va vao M bifp
va rai vao vj tri cOn tr6ng. Vi sO Ian va ti vOi 3.p suift p
cUa khi trong pha khi cOn xlic sua! rai vao vj trf tr6ng ti vOi phan M
ml,it cOn tr6ng 1- a cho t6c d() hAp v-1.- bAng :

k
1
Ia hAng s6 t6c Mp b T dii cho.
PhAn tir khi hi hAp se thrnit ra khOi bt m*t ha'p (qua trlnh
gi8i hifp neu nang lw;mg cUa n6 dU de n6 VU'Q't ra khOi M miJ_t. S6
nhlrn.g phan tir nhu the ti vOi s6 nhihl.g phan tir dii hi ha'p
urc 13. v6'i pban a cUa bt da bj khf chim. Do d6 t6c d() gi8i hAp
vt hAng:
vt = k
2
e
k
2
Ia h_ilng s6 t6c d() gi<li hAp b T dii cho.
Khi t6c d() cUa hai qwi trlnh nglll;1C nhau, hifp va gi3i hip
hAng nhau. =vt. Wi tn)ng thaiclln hAng Khid6:
tlr d6 :
k
2
e = k
1
(1-9)p
k
2
9 = k
1
p- k
1
9p
!J(k, + k,p) = k,p
9
= k
1
p = (k1/k
2
)p
k
2
+k
1
p l+(k
1
/k
2
)p
DiJ_t b = k
1
/k
2
, b gQi 18. bilng s6 can bAng hAp (dl:li khi th!
hAng K thay cho b), ta dUtJC :
(XV.46)
216
(XV .46) gQi lA plutung trinh d&ng Mp Ldngmua d6i v61
mt khi.
b) Nhilng tnrbug /uJp rieug
I) VUug He11ry. Khi s1,1 htlp ph1,1 yu (b be) vii: 4i oip suit can Mng p bC ella khl b! hip
I I +bp..,I.Khid6:
0 = bp (XV .47)
s., hip ph1,1 khf tU"c 13 d<) ditn dAy be e ti vOi. ap suit can b!ng pella khf
trong thl'! tich etta pha khf. D6 Ill nQi dung ella djnh lu!).t Henry va (XV.47) gQi Ill phlfdllg
tri11h d&11g uhift hiip phlf Heury, phuong trinh nay cilng c6 thl'! vitt ;
' 9=-
'm
(XV.48)
tUc I !I. iJ oip suit thip. lugng a chift hi hip ph\J. (tfnhd6i v6i 1 Mp ph!,!) ti I v6i ap
su!"t can bing pella khf lrong pha khl (nhlinh OA trtn hlnh XV-2).
VUug lufp phlf biio hOa. Khi S\1" hifp phL:J. ffi'1Jlh (b l&t) v.i!. U vllng p !6n, I + hp.., bp,
(theo XV .46) 0 = I. Khi d6 be duqc ditn dAy hoM loAn bUi chat hi hip phL:J. v.i!. S\1"
tang lip su!"t ella khf hem nita trong pha khf khOng c6 3nh hmJng nita dn lugng ch!U
bj b:lp ph1,1 lrtn be ml!-1 cln (vilng BC trtn hlnh XV-2). VUng nay Ill vUng hifp pb1,1
biio hOa.
Nhu v$,y, khoic vOi phuang trlnh h:lp pb\i. PhrOinlich chi dUng cho vUng lip suifttrung
blnh, phuong trlnb hip ph\1 Langmua ml'l t3. lf'Qn duOng ding nhit hip ph\1 ella hlnb
XV-2 tir vUng lip sutlt thip dtn vllng lip sutlt cao.
c) Dt,mg tuye'n tiflh cUa plutdng trinll Liingmua. (XV.46) c6 viet:
= a.+abp
Chia hai ve v(ri se dUtJC :
. = _t_ + L
a
(XV.49)
Day Ut tuyen tfnh ella phuang trlnh l.Angmua (XV.46). DuCmg
bieu dibt p/a theo p 13. mt duCmg thing c6 d d6c OO.ng cOn I !bam
13. tung d g6c. Tlr d6 xac dinb dUtJC b va <lm
d) Phucmg trinh Liingmua dr,mg c6 nOng d9. Khi khi hay hoi c6 the
coi 13. li tui:mg thi ap sucft p ti vdi n6ng d() c ella khi :
n
p= -RT =cRT
v
(XV.SO)
217
Khi d6 phl1C1Ilg trlnh Ungmua (XV.46) c6 tM thi duOi d"-ng:
a be
9 = - = -- (XV.5l)
am l+bc
Di nhien 0 day hAng s6 b c6 gi<i tti b8.ng s6 kluic v&.i b trong (XV .46).
e) Chu,en ttL phu,mg trinh Gipxd sang phllthlg trinh Ldngmua.
Tir phuang trlnh Sisc6pxki (XV.42):
Jfy vi phAn :
tlrc 1!1.:
ao - a.= Aln(l +be)
Ad(l + be)
d(cr
0
- a) == -dcr "" Ad/n(l + be)= '-":"-'-;-"'"
I + oc
Abdc da Ab
--do=- boAc--=--
l+bc de l+lx:
Dua bil'!u thlrc nay cim- dcr/dc vao phUODg trlnh ding ha:p Gipx.o (XV.40).,
cdo" A be
f=- -- =-.-- (XV .52)
RT de RT l+bc
D6i v6i Sl! hip phi.J khi tren bl! mij.t rin,IUQDg khi bj ha'p 16n do d6 luc;tng dtr
r thlfC II! trllng vUi lugng d6i, tlrc Ja :
A oc A
f ==a= RT. I+ be dat am = RT, ta duqc:
a oc
=-=-
am l+bc
Nhu v4y nhO" trlnh Siscl'lpx.ki,ta chuyen duqc tU phuang trlnh dlng h!p
phi,! Gipx.o x.ay di!Ilg thmin ttiy bAng d(lng h,rc hqc sang phUODg trlnh ding hd"p
ph1,1 Ungmua xll.y di!Ilg thu!n ttiy bang thuyf't dl)ng bQC khi.
f) Ap plutung trlnh Liingmua di xdc djnh bi mf]t riing cUa
hdp phi!. Be rieng 13. he tinh d6i vm 1 gam ha'p ph\].. D<;ti
luqng tUc 13. Iuqng cha't b! ha'p ph1,1 (tfnh ra s6 mol cha't bj hap ph1,1 d6i
vOi l gam ha'p ph\1) phil kin he ha'p ph1,1 bang m()t lOp dan
pha.n tlr day dil, gQi lA dung tich lilp dun. D<;ti hiQilg n3.y cho phep xB.c
djnh he rieng s cUa ha'p phl.J neu bit din tich rom cho<in b6i mC>t
phAn tir cha't b! ha'p ph1,1 trtn 16p dan :
218
s
NA 18. s6 AvOgadrO.
(XV.53)
luqng rom tim duqc tlr kfch thuOc Van de Van ella phlin tir.
3. Phltdng trinh Uingmua d6i vifi him hqp khi
Ne'u khOng ph3i m(ll khi rna ta:mQt h6n hqp khf duqc h!lp plw trtn be ran thl
d diin d!ly 9; be; v()! nin bOi khi i tinh theo phuong trinh :
(XV.54)
i'J d!'ly t6ng duqc l!ly tbeo mqi clfu ti:r i cUa bOn hqp khi. Thi d1,1 d6i v6i bOn hc;YP hai khl
1 va 2:
9= b;p;
' l+b!Pl
Nbu SL! thtm c:lu tit vito h Uun giiun sl{ h!lp ph\1 ella clfu ti:r kbac. D6 lli bien
tugng qmh tranh Mp Ph1,1.
4. NhUng thi6u sot cUa thuyit h&p phi} Uingmua
MO h1nh h!lp phl,ll.Angmua ditn duqc nhUng net quan tiQng ella hin tuqng h!lp
ph1,1. Nhung ngay sau khi n6 cOng b6, nguCri. ta dii phiit bin bAng sl{ kin m!'lu
thu3n vOi eli ba ditm co ban cUa thuytt d6. bit thQ"c t cho th!ly : I) sl! bll"p ph1,1
c6 tht xiy ra lheo 16-p da phM ti:r; 2) be v!)t h:J:p thuCmg kMng d6ng nh!lt ve
nang luqng, tlic hi c3.c vi trl h!lp ph1,1 c6 th! c6 nhUng nhiet ph1,1 Q khac nhau; 3) c6
lht c6 tuong hie gilla clic phM tUb! h!lp ph\) thu()c cUng m(lt l{Jp dun. _
Nhu vi).y Sl! phit triin thuytt Mp ph1,1 Ungmua dAn den ktt qui 111. phai hiu chfnh
thuytt d6 theo ci ba bu6ng. Du(1l d!'ly, ta chi xet hu6ng pMt tri!n theo co cht da phAn ti:r.
7. HAP PHI) HOI. THUYT HAP.PHI)
f>A PHAN TIJ B. E. T
Khi va hoi khOng kMc nhau. Tuy nhi8n ta thUOng gqi"IA khi nhiing
chat khOng t6n 0 tr<;Ulg tM.i lOng trong k.in thUOng, thi d\1 nhfing
khi 02,H2oN2, CO,C02 v.v ... COn hoi thl tnmg cho nhiing chat b
tr<:mg th<ii lOng b dQ thucmg, thi d\J. hai nuOc, hai benzen v.v ... T!.li
m6i nhit dQ, chat lOng cMt c6 ap sdt hai Mo ho8. ho8.n tOOn
xac dinh.
219
1. Slf ki'n nghi'm
nghim cho thi'y
dll'img ding nhit hi'p ph1,1
hcri thll(mg c6 chO' S,
khOng c6 doc.m thlng ngang
song song vffi tn,JC lip sui't,
tUc Ut khOng c6 giai
bao boa (hinh XV-8).
N6 c6 dilim u6n A va
nbanh AB tip t1,1c cong vt
phfa tren.
Nu hi'p ph1,1 c6 m()t
h th6ng 16 x6p va mao
a
1
8
A
0 '--------:
p
Hinh XV --8. chlt S cil.a duc.'.rng dling nhi1
h.a"p
ri't phlit tritin thl c6 the giii thich tinh kh6ng bao boil cUa sq h<lp
ph1,1 hcri 13. do trong sq ha'p ph1,1 c6 hin tuqng ngtmg tl,l mao qu:in cllng
xlly ra,Iam cho htqng cMt dugc giii 0 M ha'p ph\1 tang
Tuy dll(mg ding nhit ha'p phl} hcri chU S cfing xAy ra b
c8c Mp phi,! khOng x6p, b da.y khOng the c6 Slf ngtmg tiJ mao quito.
Do d6 pMi gUll thich sl! ha'p ph1,1 theo ca ch da pMn tit.
2. Thuyift hip da phon tit B.E.T.
Thuyt My do ba tic giii Brunaue (Brunauer), Emmet (Emmett) vii
Tela (Teller) xa.y dlfllg nam 1938 (B.E.T. 18. ba chU cai ditu ten cU.a
m6i ngOOi).
vt oo bin, thuyt B.E.T vAn giii nguyen 2 trong 3 cUa
thuyt Langmua :
1) hap phlJ 13. dOng nMt ve nang luqn.g, ttrc 18. cac
trung tArn hap phy c6 ba:p phy Q nhu nhau ;
2) Kh6ng c6 tuang tac giila cac pha.n tit bi hap phg thuc cUng mQt
lOp dan, tUc li't khOng c6 tuang tic ngang.
Thuyt B.E.T. kha.c thuyt Ungmua vt ll$1 dilim sau :
3) MOi phAn tli lOp thU nMt li't m()t trung tAm cho sJ! ha'p ph!} lOp thU
hai, mbi phi!n tir lap tM hai Ia trung tArn su ba:p phy lap thu ba v.v ...
220
BAng each d6, SlJ Mp phJ,l dit!n ra theo lap da pha.n ti':r. Qui y ra.ng
B.E.T kMng c6ng nMn c6 tuang tac ngang gifra cac phAn tir bt hap phl}
cling mt lap, nhung c6ng c6 tuang tac dqc gilla nhihlg
pha.n ti':r thu()c lap va lap duUi.
Theo thuyt B.E.T, dit!m u6n A (hlnh XV-8) ke't thtic philn cong du6'i
cUa dubn.g dAng hap ph1,1 ling vai SlJ bao bOO. lap dan pha.n ti':r, cOn
nh3.nh AB ella dubn.g cong ling vai Sl! hlnh th8.nh lap da pha.n ti':r.
lfrnh XV -9 18. m6 hlnh lOp da pha.n ti':r.
Hi11h XV -9. MO h1nh lOp da phAn tir
3. Phuang trinh ding nhii1t hi'p ph1,1 B.E.T
each tinh cling tllang 11! nhll trong thuye't Litngmua nhung c6 pht'ic
han ml)t chtit, vl c6 16p Mp ph1,1. each tinh ca sb s616'p 18.
v6 dAn tai phuang trlnh dAng nhit hap ph\} B.E.T c6 d1_1.11g sau :
6 = ...!._ = Cp/pbh (XV.SS)
m (1-p/pbh) [I+ (C-I)p/pbhl
a 18. hr<}Ilg hai bj hAp ph1,1 (tinh ra s6 mol hoi d6i vai 1 gam hAp ph1,1);
lit hn;m.g hoi bi Mp ph1,1 khi be hAp phQ. da dtrqc phil hOO.n
tOO.n bbi ml)t lOp dan pha.n tlr, gQi 18. dung tich 16p dan; p 19. ap suAt
cAn bAng cUa hoi trong pha hai hAp phl} b nhit T = const ;
Pbh 19. ap suA't hai bao boa ella chfft lOng b T da cho; CIa bang s6.
Khi p/J'bh be va C I thl phll<1Ilg trlnh B.E.T (XV.SS) chuytn thanh
phuang trlnh Langmua. ThJ!C khi d6, c6 tht! vit:
e = ...!._ = Cp I Pbh = _J>E__
am l+Cp/pbh l+bp
221
vOi
c
b=- =const
Pbh
>t xac djnh nhfing hAng s6 C va 3.m , ta dua phuang trlnh RE.T
(XV.55) vt! dt;zng tuytn tinh bAng each viEt:
PiPbh l+(C-l)p/pbh
-
a(l-p/pbh) Cam
PiPbh l C-l p
=--+--.-
a(l- PiPbh) Cam Cam Pbh
(XV .56)
DUCtng bitu d<;ri luqng 6 v tnii phuang trlnh (XV.56) theo p/pbh
lit mt duimg thong c6 d d6c h>ng va c6 tung d g6c bAng
Tit d6 xac dinb duqc c va "m
Sau khi di xac d!nh duqc 3.m, c6 tht tfnh duvc be s ella
rOn Mp theo cOng !hire (XV.53) :
s = 3.rn.NArom
rom 13. tich chim OOi 1 phan tir hoi bj ba:p ph1,1 ttt:n lOp don, N A 13.
s6 A v6gadr0.
222
TAl THAM KHAo
1. AA.Ak6pian, dl).ng 1\IC hqc hot\ hQC, NXB hQC,
MatxcaVa, 1%3 (ting Nga).
2. B.laAndriep, Bai gi8ng hot lf, in rOneo tnWng hQC
T6ng hqp Ha NQi, nam hQC 1960-61 (d1ch tlr bin ting
Nga).
3. J.P.Bazarbp, Nhit d(>ng ll!C hQC, NXB Khoa hQC ki Ha
NQi 1975 {djch tit nguyen bin tie'ng Nga).
4. Al.Br6txki, bOO. li, t.1 va 2, NXB hot hQC, Matxcava, 1948
(ti(ng Nga).
5. M.P.BukalOvich, l.l.N6vic6p, Nhit d(mg llJC hQC, NXB Ch
mciy, Matxcova, 1972 (tie'ng Nga).
6. V.P.Drivinh, /aA.Kalasnhic6p, Quy t!c pha, NXB TruOng
DHIH Matxccrva, 1963 (ting Nga).
7. la./.Gheraxim6p (chU bien), Giao trlnh HOO. If, t.l NXB Hmi
hQC, Matxcava-Uningrat, 1964 (tilng Nga).
8. A.AJukhOvitxki, L.A.Svacxman, Hot If, NXB Khoa hQC ki
Ha NQi, 1977 (djch ti:r nguyen ban tie'ng Nga).
9. M.Kh.Karapetchien, Nhit d(mg ll!C hqc bOO. hQC, NXB Ho3.
hQC, Matxc<Wa, 1975 (tie'ng Nga).
10. M.Kh.Karapetchien, Thi d1,1 va bai dng h,tc hQC bOO
hQc, NXB MatxCCNa, 1953 Nga).
11. V A.Kireep, Giao trinh HOO Ii. t2, NXBGD, Ha Ni, 1963 (djch
tlt nguyen bim tilng Nga).
12. l.R.Krichepxki, Nhiln.g kMi nim va CC1 sO d(mg h,tc hQC
hOO hQC, NXB HOO hqc, Matxwva, 1962 Nga).
13. A.GXtrombec, D.P Xemchenc6, HOO li, NXB hQC, Matxccrva
1973 (ting Nga)c
223
14. R.Brdicka, Grundlagen der physikalischen Chemie, VEB,
Berlin, 1958.
15. R.Havemann, Einftihrung in die chemische Thermodynamik
Berlin, 1957.
16. G.Emschwiller, Chimie physique, t.l, Presses universitaires de
France, Paris, 1951.
17. P.Souchay, Chimie physique, Thermodynamique chimique,
Masson, 3!: ed, Paris, 1968.
18. D.E.Dodge, Chemical engineering Thermodynamics, Me Graw
Hill, New York, 1944.
19. G.N.Lewis, M.Randall, Thermodynamics, 2d ed. Revised by
K.S.Pitzer and L.Brewer, Me Graw Hill, New York, 1961.
224
A- D{li clfrmg vi d1mg d!ch
1. Dinh nghia dung djch
2. ThAnh ph4n dung djch
B- Dqi luqng mol rii11g plu111
MI)CLI)C
3. Djnh nghia vii thuc tfnh ella d\li luqng mol phll.n
4. Phuong phlip de djnh hrqng mol ril!ng phAn
C- H6n ht;tp kh(
5. H6n hqp khf lftuimg
6. H6n hqp Clic khi thgc (khOng li ur6ng)
7. s., bOO. tan chE ciia cac khf vao nhau
C/11Idng VIII- DUNG DJCH L6NG y(j ClJNG LOANG
I. CAn bilng dung djch loiing-hai bio bOa. I)() h:J. ip suM hoi.>
tang dic'!:m s6i ella dung djcb loiing
2. On rn\ng dung djch loiing vOi tinh tM ella dung mOi. D('l hlJ.
bang dilim ella dung djch loiing
3. Ap suA1 thAm th4u
4. an bilng dung djch loiing vOi dung djch loiing c6 m(lt clu tlr
chung. Djnh lu$J phfln b6. S\f cbif"t
Clillo11glX- DUNG DlCHLf 1"IilNG VA DUNG DlCHTH\t
I. Djnh nghia vii thuO<; tfnh cUa dung djch li tuimg
2. Dung djch thi!C- Sai diWII.g va Am so vOi. djnh Raun
3. H thU'c Duhem-Macgulexo (Margules)
4. D!nh KOnOvalOp (1881). So sinh thanh ph!n hai v&i thlmh
phil.n dung d!ch lOng
Trang
3
3
3
5
10
10
15
19
19
24
26
28
28
37
39
42
47
47
50
54
56
225
5; 3l.r eM b6n bgp bai cbtrt lOng
ChucmgX- PHUJNG
I. d va b d
2. Ch.Qn thii cbuAn
3. d(l va b dQ tbeo nbii'ng thang n6ng d() khac nbau
4. Phll<mg pblip x.ac djnb dQ va M s6 d
5. can bAng dung djcb lOng- ctfu tir kbf. f)() tan cUa khl trong cbtft
lOng
6. an dung djcb lOng- ctfu til rio
Chucmg XI- cAN BANG HOA HOC
1. Ai h,rc bOO bQC
2. Ditu kin c<\n bing bOO hQC
3. Dinh tic d11ng kh6i luqng vil phuang trlnh dfutg nbit cUa
phftn ltng bOO bQC
4. Uhg cUa phuang trinb dang nhit vacUa thl ding ap cbuAn
cUa phim Ung
5. Anh huOng cUa ip sutft c;\n b!ng boa bQC
6. an b!ng hOO hQC di
Chucmg XII- ANH HLONG cUA NHI.tr DQ LEN cAN BANG
HOA HQC. NGUYEN Lf THO"BA CiJA NHier DQNG Ll,t HQC
I. Sl! pb\1. thuo.')c cUa h!ng sO can b!ng vilo d
2. Djnb If nbi1 ella Necxa. Nguyen H thU ba cUa nhi1 d()ng
h,rc hQC
3. Ap If lhlt ba dl'! tinh can b!ng bOO hQC
ChUtJr1g XIII- NlfltT D(>NG LT,:C HQC TH6NG KE
A-Cd sd ph!Ldl1g plulp tlu'l11g ki
I. xac suft nhi1 dQng v3. entrl'lpi
2. Djnh lu*l phan b6 Bonxman
B- Thuyi't c6 dil11 vO thuyi't ilf{!llg tU ve 11hit du11g cUa cluli khi va
cMtr&11
226
3. Nhi1 dung cUa khi li tui:mg
4. Nhit dung cUa cM1 rin
64
67
67
70
74
76
79
82
90
90
92
96
107
110
Jll
113
113
liB
124
137
137
137
141
145
145
147
cdc hilm nh_ift dt)ng vd M11g sO can bting theo p/iU(111g pluip
5. Quan h giila cac hi'lm nhit dl)ng va tOng thai
6. Tinb tOng tr!}llg thai cUa khi li tut.'mg
7. Tinb cac hlim nbit d('mg cila kbf li tut.'mg theo tOng tMi
8. Tfnh can bAng boil bQC trong kbf If tut.'mg
Chur.mg XIV- QUY TA.c PHA. GIAN 00 PHA
A-Quyt&c p/la
I. Ml)t sO kh3i nim
2. Quy tic pba
8-Gidn d& pha hf mt)t c.fu tU
3. Gilin d6 ph a ci:Ja nu&:
C-Gidn d& pha hf hai c.fu tU
4. cuong ve h hai clu tlr
5 .. H hai c!"u tlr boil tan kbong h!}ll chl vito nhau 0 tht lOng, c6
pha rio kbong phii Ill dung djch rio
6. H hai c!"u tl:r c6 hai pba 101\g. SV holi tan c6 h!}ll ella hai chat
lOng vito nhau
D -Gidn d& pha hf ba c.fu tU
7. Nhiing each bitu thj lhi'mh ph4n h ba clu tti
8. H ba c!"u tti hinh thAnh h6n hgp otecti ba
9. S., holt tan c6 h!}ll cUa ba ch!"t lOng
ChU(111g 1V- meN TVQNG MAT. HAP PHI.,J
I. DiP cuong vt slic cling bt va h!p ph1,1
2. kin c!n bAng nhit dl)ng lOp hai pha thi tich
tilp giap nhau
3. Nhitng hin tuqng lmt !WI va mao dAn
4. Nhiing phuong trlnh nhit dQng co biln d6i vm lOp M
Pbu(Jilg trlnh ding nhi1 hlfp ph\1 Gipxa
5. O"ng dyng cUa phuong trinh h!"p phQ Gipxa. Sl,r hip phQ lrtn
Cli!"t dng vii khOng dng
6. H!"p phy khi va hoi trtn bt rfm. Thuylt hii"p ph\1 d(Jil
phan ti'r Ungmua
7. HA"p ph\l hoi. Thuylt hfp ph\l da phan ti'r B.E.T
149
149
!50
!54
160
163
163
163
165
167
167
171
171
173
184
187
!87
190
192
196
196
201
205
208
211
215
219
227
Chju trrich nhim xucit biin:
Chii tich HDQT kiem T6ng Gi3.m dO"c: NG6 TRA.N AI
Ph6 To'ng Giitm dO"c kiem To'ng bien V0 DUONG THl;'Y
Bien t(lp l&n d&u:
NGO THI SONG HAO
Bien ti).p trii biin:
NGUYEN THANH GIANG
Trinh bay Ma, ve hinh:
DOANHONG
Siia bdn in:
PH6NG SUA BAI (NXB GIAO D1}C)
Che'bdn:
PHONG CH!l BAN (NXB G!AO DT,lC)
GIAO TRINH HOA Li - TAP HAl
D<)NG Ll/C HOC HOA HQC
Ma sO": 7K493T4
In 1.500 bfm, kh6 14,3 x 20,3 em, Nhi'l in h9c QuO"c gia Hll NQi.
SO xua't bim: 502/74- 03 CXB
In xong va nQp Ju:u th3.ng 9 nam 2004.
G IOI THIEU TOM TAT TIEU su
CO GIAO SU f>lNH
Gl6o su Dinh sinh ngoy 27 thong 12 nom 1920 tol
Ho N1.
Nom 1944 ong du cv nh6n toi truong f>oi hoc Khoo hoc thuc f>ol
h
0
c Dong Duong {U.I) Ong glong day trong Hnh vvc H6o- Von
(H6o -Sinh), ve sou Ong tOm vao linh vvc H6o li cue H6o
hoc Ong lam Hiu trvong truong Coo o6ng Su phom f>Ong Duong
cho toi nom 1954 Hoc binh 1p loi. Ong tinh o lol mien
86c g6p phon xOy dvng d moi do cy Ho Cht Minh lanh
doo.Thoi glen dau ong giong d
0
y H6a li cho Truong f>ol hoc Su
phom- Khoo hQc.Sou khi Truong f>ol hQc Su phom va f>ol hQc TOng
hQp duoc t6ch ro.Ong ve 16m Truong b mOn H6o If khoo H6o hQC
Truong f)QI hoc Su phom tv nom 1958 toi luc ve hvu,198l . Cung
val nhvng bai giong sue tkh hln mt trlnh d r6t coo ve khoo
hoc va phuong ph6p su phom. Ong trvc tiep soon c6c b gi6o
trlnh c6 gi6 trl cho tol ngay nay :
- B Gl6o trlnh cAtJ Tf;\0 v.;n 0-iAT gam 4 cuOn.
- B Gl6o trlnh f>NG UJC H6A HQC gom 4 cu6n.
Ong cung quon tam nheu tal c6c linh vvc H6o li khoc nhu f>ng
h6o h
0
c, f>in h6o hoc ....
C6 sv cng t6c rua cac nha H6a hoc khac. Ong chu tri djch gl6o
trinh H6a If cue Keriev tv Ngo song tieng Vlt Ong them gio
bten soan Tv H6a hoc Nga. Anh -Vit aau tlen.
Trang nhieu nom, Ong 16 Truong bon H6o li trvc thuc Uy bon
Khoct hoc v6 KT thut Nha nuoc, Ong cung Ia uy cue Uy bon
nay
cu61 dol, mc dub! ngheo keo dai, Ong v6n soy suo
bien soon glee trlnh, huang d6n nghlen ct.iu sinh, hoot dng khoo
hQC .
Ngooi cOng tee chuyen mOn, khoo hoc, eng con Ia Chu tich Mt
trn T6 qu6c qun Bo f>lnh, Ha Ni nhfeu nom
GIOo su f>lnh Ia mt t6m guong song ve long nong
non yeu nvcc, soy me hoot dng khoa h
0
c va c6 nhieu d6ng g6p
len cho nen glOp dye nuac nh6.
...
I 1469

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0 miU<s6vl n6 rft be so v6i lOOOp, dod6:

D6i v& nhiing dung dich dll lOOng

cr =2 vl khi quay 360 quanh tr1,1c d6i xUng ciia chUng,

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