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Giao Trinh Hoa Ly 2

Giao Trinh Hoa Ly 2

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NGUytN niNH HU~

GIAo TRlNH HOA LI

T~HAI

. NHI~T f)QNG UJC HQC HOA HQC (T di ban ldn thu ba)

NHA XUAT BAN GIAo Due

CHOONGVII

D~C TRlING CHUNG ClIA DUNG DICH HON HQP KHI

'"

A - DA,I cumo VE DUNG DlCH

§1. £lINH NGHiA DUNG DICH

Dung dich la nhtrng h4 dong thl, be'll nhi¢t d9ng, g6m khong it hon hai chAt a trang thai phdn tan phdn til va thanh phan c6 tbe bi€1l thien lien tuc trong nhtrng gici han xac dinh.

M6i dung dich la mot pha. Neu bo qua nhfing hieu tmg M mat va tic dung cua nhtrng tnrong ngoai (trong tnrong, dien tnrong, ttr wang) thl d6i veri. m6i dung dich b trang thai can bang. thanh phan va cac thuoc tinh vi mO cua no la hoan toan gidng nhau (dong Illuft) b kh!p moi diem.

Trong dung dich, cac chAt a trang thai phdll tan phon 'ii, tde la a drrUi dang tung tilu phdn (phan tir, nguyen tir hay ion) rieng re, hoac a diroi dang'nhtmg nh6m nho g6m mot s6 it cac tieu phan d6.

Tnr6c kia, h¢ keo cting goi lit "dung dieh keo", nhung d61it dung die" gid.-vl h¢ keo lit nhUng h¢ vi di thl chu khOng phai Ii\ h¢ dOng the, ngom ra h¢ keo thuong khOng ben nhiet dong, c6 xu hirong bien ddi theo thm gian. COn dung dieh dinh nghia nhu tren Ill. dung die" th4t (dung dich chinh there).

NhUng eMt cao phlio lir c6 the hlnh thimh dung djch th~t veri dung rnoi nay va dung dich keo v<ri. dung mOi kia, Thf dl,l, cao su thien nhien tan trong ben zen cho dung dich th~l nhung tan trong mroc thl cho dung dich.keo (latech), Khi dung dich coo phan til' Iii:

3

dung dich th41 thl chung cilng tuan theo nhUng quy lu41 nhiet dl)ng nhu cac dung dich tMng thirong cua nhUng chat co phan tt'r thil'p. Di nhien, chung con c6 nhUng thuoc Hnh d~ Ihi! neng, gao lien vm kfch IhmR; phan tic Ic'm cua chil't tan.

Dinh nghia tren v~ dung dich khong han che' dung dich phai fa & th~ long. Tuy theo trang thai tap hop cua pha (khf, long hay ran), ta c6 nhiing loai dung dich klu, dung dich long va dung dich ran.

Noi chung a ap suat khong cao lam, cac khi luon luon co the hoa tan khong han che vao nhau va do d6, v~ nguyen t~c, cac h6n hop khf can bang d~u HI dung dich khi.

Dung dich ran (cling goi la tinhthl tap hap} diroc hinh thanh khi cac cau til chi tao nen mot pha ran duy nhat, Dung dich rAn thuong chi 16n tai trong nhiing vung n6ng d¢ xac dinh, toy cling co mot s6 c~p chat nhu vang va bac, hoac d6ng va vang V.v ••. co the boa tan vao nhau a tM dn theo bAt kl ti I~ nao, Dung dich randugc hlnh thanh trong sl! kel tinh tir

nhiing h8n hop long nhiing cau til' cua chung, .

D6i voi dung dich lOng, nguoi ta phan bi~t dung dich cMt khf trong chat long, chat d.n trong chAt long va chat long trong char long. C6 the khong mot chat d~u nao 6 the: long. Thf du c6 the duqc dung dich nUae cua NaG bang each tr¢n nucc eta voi tinh th~ NaG.

Cung mot dung dich co tM thu duqc tir nhieu cha:l dau khac nhau, Thi du dung dich nuoc cua axit sunfuric c6 the di~u che' .tir H2SO4 va H20 hoac tir S03 va H20. Do do viec chon nhiing cha:t nao HUn cau tit cua dung dich co the Iii tuy y. Nhung trong s6 3 cMt H20, S03' H2SO4 thl chi 2 la d¢C lap, DO la s6 t6i thieu nhiing chat hop phAn rna til' do c6 the thu diroc dung dich axit sunfuric co thanh phan Mt kl, S6 chat hop phAn dQc l~p Iii so' cau tu cua hf D6 moi l3. con s6 quan trong trong nhiet dl)ng II!C hQC_

Thuong thl cAe til nolo co mat trong dung dich voi hrong Ian nhat so vOi cac cau tir khac thi goi l8. dung moi con cac cau tir kia goi la chat Ian.

D6i voi dung dich cha:t khi hay chat ran trong chilt long. nguoi ta thuong coi chat long la dung moi vi chat khi hay cMt ran chi hoa tan co han vao dung moi. Ngay khi cMt khf hay chAt rAn hoa tan v6'i hrong

4

tuong d6i l(m trong chAt long lam cho luong urong d6i cua chat long tro thanh be hon, nguoi ta van tiep tuc coi chat long la dung mOi.

Dum day, ta se nghien ceu l.1U tien dung dich 2 can tli, th(i:nhAt vi d6 la dung dich don gian nhAt v~ s61uqng CAU tir, thlt hai vi nhieu quy luat

thu dUc;1C c6 the mb rong cho dung dich nhieu cAU tu hon, .

§ 2. THANH PHAN DUNG DICH

Mi)t trong nhimg d~ tnrng quan trong cua dung dich la thanh phan cua n6. Thanh phon dinh tinh cho biet v~ ban chAt cac cau tir cua dung dich, con tlulnh phdn dinh luang cho bi€t m6i CAU tir duqc chtia trong dung dich voi nhtmg nang d(J tlk la nhirng hrong tuong d6i la bao nhieu, nhtmg dai lueng nay, cung voi nhiet d() va ap suAt, la. nhtrng tham s6 nhiet dong 00 han cua dung dich. CO nhii!u each bieu thi nong ru, cac cau til cua dung dich, n6i chung c6 tM ehia lam hai loai : mot loai quy hrong cua CAU til vi! mot hrong xac dinh cua dung dich, loai thil hai quy hrong cua CAll tir vi! m(lt hrong xac dinh cua dung moi nguyen cMt.

Gia thil b T, p da cho, mot kh6i luong G gam dung dich, chiem the tich V, chua nhtmg cau til 1, 2, ... , i ... , c6 kh6i luong: g l' g2 •... gj"" c6 the tfch b dang nguyen chat la VI' V 2"" V j ... , s6 mol cac CAll til til "I' "2"" nj .... di nhien nj = g/Mj• b day M, la kh6i luong phan tu cua i. Kh6i hrong dung dich la G = Lgi .

Ngiroi ta quy uoc goi I mol dung die" la hrong dung dich trong d6 tcing s6 mol cac cau til bAng 1 (:Enj = 1). KIll'li lllf/l1g mol trung binh cua dung dich la :

M = niM. + n2M2 + ... = ~niMj

Ln· - :En·

I I

BAy gia xet nheng each biell thi nong d(l cua cac CAll til.

1. Luqng cau tu quy va mqt luqng xic d!nh dung djch

1) Phdn mol Xj_ (thuong cling kf hieu la Yi hoac N) cua cau til i Ia ti s6 gifra s6 mol OJ ciia n6 vOi t6ng s6 mol :EIlj ciia cac CAll til trong dung dich :

(VII. I)

5

(VII.2)

C6 thi! n6i phan mol xi lil s6 mol cua i trong 1 mol dung dich, Di nhien ta e6 :

LXj = xl + x2 + ... = -EL + ~ + ... = Lnj = 1

Lni In i Lni

(VIL3)

dod6:

llixi = 0 (VII.4)

D~e bier, d6i v6i dung dich 2 cau til :

xl + x2 = 1 : xl = 1 - x2; dx, = -dx2 (VIL5)

Tir (VII. 1 ) suy ra kh6i hrong mol trung blnh cua dung dich :

2) Phdn tram mol ella i lit :

looxj =-' .100 Lni

(VII.6)

3) Phdn kho; luang Wi lit kh6i hrong eua i trong dan vi kh6i hrong eua dung dich :

(VII.7)

Di nhien :EW j = 1

4) Phdn tram khblill{J1lg cua i 18. kh6i luong cua i trong 100 dan vi kh6i lw;mg cua dung dich :

(VII.g)

6

N6 oong s6 gam. ciia i trong 100 gam dung dich, 1111 du dung dich axit axetic 5% lit dung dich chira 5 gam axit axetic nguyen eha':t trong 100 gam dung dich,

5) POOn thl tich (Jlj 13. th~ tfch ella i nguyen chat tfnh d6i vci I don vi the tieh dung dich :

v. ~i=-I V

6) Phdn tram thl tich coo ita:

I ()()q>j = _I • 100

V

(VII.9)

(VII. 10)

N6 bang s6 cm3 i nguyen cMt trong lOOcm3 dung dich.

D¢ manl: ella nrou trong cac h6n hop nu6c ruou duoc bieu thi theo each d6. Thi du nrou 90° 13. hOn hop chua 90cm 3 nrou nguyen eha':t trong IOOcm 3 h6n hop nu6c nrou.

7) N 6r1g di) mol - tM tich C j 13. 56 mol i trong I dan vi. 1M tfch dung dich :

n· Cj=_1

V

(VII. 11)

Khi chon dan vi the tfch 13. lit thi C; la n6ng d¢ mol/lit. D6i vrn. dung dich 2 ca':u tir, n€u 1 lit dung dich chua 1 mol cMt tan, dung dich goi 13. dung dich I mol, lei hieu 13. 1M. Dung dich 2M chua 2 mol eMt tan trong 1 lit dung dich,

8) N611g d¢ nguyen chudn 13. s6 dirong luong gam cua i trong I lit dung dich, Thi du, dung dich c6 dt) nguyen ehuan O,IN chua 0,1 duong luong gam chat tan i trong 1 lit dung dich,

2. Luqng cau - ta quy v~ mqt luqng d.c djnh dung mol

9) N 6ng d9 molan mi III s6 mol ella i trong 1000 gam dung moi (dung moi la cA"u tir 1) :

(VII. 12)

7

D6i vOi dung dich ra:t loang, xl:::::: 1, do d6 co sl,l ti l~ gitta D1j va xi : 1000

m· :::::: -- X· (VII. 13)

I M] I

Ghi eM. NOng di) dlIl;lC dung nhi~u i1Mllrong Ii thuY(1 la ndng ~ phdn mol Xj' th6' nhat vi nhieu thul)!: tinh eua dung dich duge hieu th] u dang dan gian nhi't khi dung s6 nrong ~tii cae pb(m tir, thu bai vi nOng d~ d6 khong ph\, thuec V30 the tfeb va nhi~t d¢.

N6ng dq mo/an rnj enng khOng ph\' tbul)!: vao T va V. do d6 cling thuong dut;JC dung d6i veri dung dich loang, kbi si! phAn biet giua dung mOi va eMt tan la to rang.

3. Llin ht gilta nhOng nong de} c, x va m d61 vbl dung d!ch 2 ci'u tu

Kbi ehuyen til e sang x hay m va nguqc I~ thl dn bi(t kh6i hrqng rieng hoac ti 1:h6i (ding goi la m*t d¢) ella dung dich,

I) Uin h¢ giila mz va xz. Til (VILI2) suy ra :

(VILl4)

2) Lien h~ giila Cz va xz' The tfch dung djch la V Ht ho~c V.IOOOml, c6 kMi luc;mg G = g, + gz g3.IJI. Kh6i luc;mg rieng p ella dung dich, tUc la s6 gam ciia lml dung dich la:

p=~va..!.= IDODp = lOOOp

V.lOOO V gt + g2 D,M, + D2 M2

(VII.lS)

C;! = ~ = lOOOpnz lOOOpx2

V n,M, + n1M2 x.M. +x1M2

Nhung x, = I . x2' v*y:

e2 = lOOOpx1 (VII.16)

M, +(Mz -M,)x2

3) Lun hf giila mz va cz. I 1ft dung dieh. ute la lOOOp gam duog djeb chna M1Cz gam du tu 2. V.y (lOOOp - M1Cz) gam dungmoi ehiia Cz mol du tit 2. Do d6 s6 mol efu tu 2 trong 1000 gam dung mOi, roc la d(I molan mz la :

(VII.l7)

8

4) TTI/Ung htJp tbtng djch rat loiing. Nhitng b¢ thik tren ebo th(y khOng c6 sl! ti If giila m2 va x2, gifra ~ va. x2' giita m2 va~. ali d6i vm dungdjch rat lOOng (kbi X2 -+0; I - x2 -+ I), nhitng n6ng dQ d6 mm ti I¢ v6i nbau :

-, 1000 M

m2 ""--X2 b* X2 =-'-ml (Vn.18)

MI tOoo .

lOOOp M,

C2 = """"M;-~2 bo~e x2 = "iQOOpc2

Wi vm (VII.l7) c6 thi.b? qua M2~ a mall's6 vi n6 rift be so v6i lOOOp, do dO :

(VII.19)

(Vn.20)

N€u dung mOi Iii nuifc thl kMi hrgng rieng eua dung dich tit loing thl!C t€ II. kb6i lugng neng cila nuc'Jc gAn nhu nguyen chat, tik Iii p'" I trong dieu kien thlli'mg. khi d6 :

1000 1000

m2 = ~ = --X2 = --x2 = 55,5lx2 (VII.2l)

M, 18,016

&Ing VII-I

Ll6n h+ glrta e2• mz va Xz d6i vc)' dung dlc:h 2 c:f"u tu

~ m2 X2
c2 l000pm~ lOOopx2
~ lOOO+M2m2 M, +(M2 - M, )x2
ID2 l000c1 m2 1OOOx2
I OOOp:"M2C2 M,(1-x2)
x2 MIC~ Mlm~ X2
I 000p':"(M2 - Ml >c:z lOOO+M1m2 9

B -·I)~I LWNG MOL RiliNG ·PHAN

§ 3. alNH NGHIA vA THUQC TINH CUA £)~I LllQNG MOL RI~NG PHAN

1. Olnh nghia

MQi thuoc tfnh khuech d() X (nhu V, S, U, H, G, ~, v.v ... ) cua dung dich deu co th! bi!u thi lit ham cuaT, p va Clla s6 mol ni. n2 ..... ni cua cac cau tir trong dung dich :

X = X(T. p,n I. n2 ... ·• ni •... ) Vi phan toan phan cua X 18.:

dX=(:t ~+(:t dP+E[(:.t,njdn;]

Chi s6 N CJ chan co nghia Iii thanh ph~ dung dich hoan toan khong d6i, con chi s6 nj a chan c6 nghia Iii s6 mol cac cau tir j (* i) khong d6i. trir cau tir i dang xet co s6 mol thay d6i. 0 T. p const, ta co:

dXT,p = ~[( : ) . dni] (VII.22)

T,p,nJ

Liuyt (G.N. Lewis) (1907) goi nhimg dao ham rieng8X/fJni U. gia tri mol rieng phdn cua dai lirong X cua dung dich d6i voi ca:u til i cua dung

dich va ki hieu Iii Xi :

Xi = (ox)

ani T,P.fij

do do. (VII.22) lIb thanh :

dXT,p = ~(XidnJ

(VII.23)

(VII.24)

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Ohi ehU. TM dAng ap (hay ham Gipxo) mol ritng phhJ. Oi cua cAu tit i khOng gi khac 111. thehOO: h9C J.li ciia 06 (xem Ch, V, §6) h~· thll"c (V.49) :

).ti =(::) ,,,OJ

( T,p,lIj

Trong s6 Uft cit cac dqi IUQIlg mol rieng philn thl chi duy nhA"t Oi mci d6ng nMt vm thE hOO: h9C J.li. cua cA"u tit i, cOn cac dqi IUQIlg mol ritug pbiln khac nhu Vi,Hi ,Fi , v.v ... ~hl khong c6 d~ tfnh d6. a..i vi~ so sanh dinh nghia v.! the' hoa hoc va. ~ ~ hrong mol ritng phAn !a thA"y rO. Thf dl,l :

0.3 khac nhau C(I ban Iii theo dinh nghia cua Liuyt thl dgi l/L{11lg mol rieng phdn bao git! ciIl1g xae dink J. T, p cowl cOD d6i vOi. the' hoa. hoc J.lj, n6 lil dao ham rieng cua mQl bam d~c tnmg U, H, F hay 0 theo s6 mol cua i khi ~p tharn s6 dUQC gilt co dinh lil c,p nhilng bien W nhien cua ham d~ tnmg $.y. Chi d6i vm ham Gipxc 0 tbl cap tharn s6 nay mm la T, p.

2. Y nghia viiit Ii

1) Dt de hien, ta xet thl tich mol rieng phdn Vi. Khai niem nay duoc dua ra la vi n6i chung tM tich Vella dung dich khong bang t6ng the tich cua cac c~u tir rieng re ella n6 (d dang nguyen chat). 111f du

d p = lbar va t = 25°C. n€u tron 100 ml nrou etylie nguyen eha:t vm l00ml nuoc nguyen eMt th) the tich ella dung dich thu duc;fC khong bang 100 + 100 = 200m1 rna chi bAng c6 ehimg 190 ml. Ciing vay, khi c1orofoc (long)· va ete (long) tron vao nhau tht c6 sl! eo tM tich, Trai lai khi hoa tan etyl iodua voietyl axetat thi e6 S1,l tang tM tich, DQ bien thien tM tfch do s1,l tren cac can tiI vao nhau gAy ra phu thuoc vao hn;m.g tuong d6i ella chnng hie tron,

V~ thuc chat, the tich mol rieng phan Vi ella cau tiI i cho bi€t tM tfch V cua dung dich bien thien bao nhieu khi them 1 mol i vao mot luong ra:t Ian dung dich e6 thanh phan da cho, luqng rai Ian dm;:FC hieu lit sao eho thanh phan cua dung dich thuc t€ c6 the coi nhu khong dOi khi them 1 mol i vito, d T, p canst. Thf du the tfch 1 mol metanol nguyen

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eMt lil V1. = 4O,5cm3. Neu them 1 mol metanol d6w mOt Iugng rlt IOn dung dich nuoc metanol c6 thanh phtn metanol x2 = O,2thl tM tieh Vella dung dich do chi tang them c637,7 em3 ehl1' khong tAng them 4O,5cm3. Ta noi the tfch mol rieng ph~ cua metanol la V2 = 3'7,7 em3 d6i voi dung dich co thanh ph~ x2 = 0,2 da cho, D6i vOi dung dich co

- .

~ phin We thi V2 se nhan nbUng gia tri khac.

N6i chung, tM nch mol rieng phan Vi cua i trong dung dich khac v& the tfch mol Vf cua i nguyen cha't l:J cang T, p va cung trang thai ~p hop nhu dung dich (neu la dung dich long th] phai l!iy i nguyen chat 0 trang thai long). Chi trong mot s6 trUOng hop ~c biet Vi rom bAng Via . N€u Vi == Via d6i vOi moi i thi dung dich dug<; hlnh thanh tu cac clfu tu nguyen cha't khong c6 bien thien tM tich : tM tfch dung dich se bang dung tdng thi tfch cac cA""u tu nguyen eMt. 0.6 Ut truong hop dung dich li tudng, dung djch deu hod (Hildebrand, 1929), dung dich Illia li ludng (Guggenheim) V.V •..

Nhung trong tnrong hop chung, Vi 'I; Via , .1. Vi = Vi - Via 7: 0 va A VM = Enj 6. Vi "* 0 , nghia 1a dung dich du€JC hinh thanh til" cac csu tu nguyen chift co bien thien the rich. Khi d6 tM rich khong c6 ceng tinh.

A VM goi lA thl tich tr¢n. N6 18. bien thien tM tich cua dung dich gay ra do s\l hOn hop, SlJ tn')n cac cau tu vao nhau aT, p const va c6 cung tr~g thai ~p hop nhu dung dich,

2) N6i chung, dI:li bif!ngtr¢n ax_M la hieu giila gia tri cua X d6i vOi M sau khi tr¢n eac cau tit va gia tri cua X tnroc khi tren cac cAu til a T, p const va c6 cimg trang tMi ~p hop nhu dung dich,

~XM = Ln' XI' -Ln'X~ = Ln' ax· (VII.25)

I I II I

Khi A}(M = 0, X c6 cong tinh ; khi l\XM"# 0, khong c6 cong tinh.

3) Cu6i cung, can clui "9 la cdc d~j luong mol rieng phdn deu IQ dai luang cllitng dt) bbi vi bat luan dai luong khuech d¢ nan khi quy ve mot don vi kh6i Iuong (mol hay gam) cling d~u trl:J thanh dai luong cuong d¢.

12

3. M9t so thu9c tinh va h., thue ee ban eua d,i luqng mol riing ph'n

1) Ung dung cua ham thudn nhdt, Tat ci cac dai Iugng khuech dl) X cua dung dich d T. P const, deu IA ham th~ nM't bac nha't d6i vOi s6

mol nl' "2>'" nj'" cua cac cau tir trong dung dich (xem Ch.V.§6) :

X(knl• kn2 ... ·) = 10 (nl' n2 ... .) Do do. theo dinh li die (V.52) ta co :

ax ax ax

X(nl' n2,"') = nl - +"2 - + ... = Lni -_-

ani an2 ani

tiic 18 b T. p const :

X ="1 XI + n2 X2 + ... = Lni Xi

(VII.26)

Ap dung (Vll.26) cho X IA V. S. U. H, F, G, ~ Clla dung dich ta dugc :

F = Lfij Fi

G = ~ni Gi = LlljPi <; = LnjCpi

(VII.27)

H = LlljHi

Neu chia mOi s6 hang trong (VII.26) v6i. t6ng s6 mol Lllj trong dung dich se duoc bit!u thtre d6i vOi 1 mol dung dich :

X=XIXI +x2X2 + ... =:ExjXj

a day x III dai lirong khuech d¢ cua 1 mol dung dich.

(VII.28)

Ghi chu : D6i v6i dung dich 2 c(u tiI, (VII.26) vitI III ; X = nJ X, + n2X2

Nlu dung mOi III nuoc va n6ng dl) molao eua ehi't tan III m2 thl trong 1000 gam H20 Iffig vm n[ = (1000/18,016) '" 55,51 mol H20 cO n2 = m2 mol eMt tan (ei'u t{r2), do d6;

X = 55,5 IX, + m2X2

(Vll.29)

13

2) PIuJO'1lg trinh Gipxa - Duhem. Til (VII.26) :

X = nlXI + n2X2 + ... =I:(njXi)

neu eoi nl' n2 •... ]A cae bien vi XI. X2 •... ciing 'La nhnng bic!n, tac Ii gia thic!t thanh phan dung dich thay d6i thl sl1 vi phan (Vll.26) aT, p eonst sf: eho:

dXT,p = k( nidXi) + k{Xidnj)

So sanh bieu thuc nay v6i (VIl.24) : dXT,p = k(Xjdnj), ta ket luan, e r, p const:

(VII.30)

H¢ thlic nay goi 18. phuang trinh Gipxa (1876) - Duhem (1886). Neu ehia mOi s6 hang trong (VII.30) voi kDj sf: d11tJC p.tr. Gipxo-Duhern trong d6 thrum phan mOi cau til duqc bieu thi bAng pMn mol xi ella n6 :

k(xjdXi) = 0 (T,p const) (VII.30a)

3) S,! chuyln nhilng h¢ thue nhi¢t dt)ng clla eMt nguyen chat sang nhiing CelU til trong dung dich. Neu d6i v6i. chat nguyen chat, y va z la hai dai luong khuech dt) lien h~ v6i nhau qua mot dai hrong cuong d() x theo pmrong trinh :

Oz y=ax

thi co the chuyen sang ctfu tir i trong dung dich nhu sau :

Yi = ayi =~(az)=~(~)= Oz;

ani ani ax ax ani ax

Do d6, neu d6i voi chtft nguyen chat y = Buax thi d6i voi ctfu til i trong dung dich, ta co 51! phu thuoc hoan loan nrong 1\1. tire III Yi = ~ . Dum dAy la mot 56 thi du :

14

eh4t nguyen nh41 cs« Ii i trong dung djch
Oz - in; (VIL31)
y=- Yi=,&
Ox
Cp=(:l Cp=(:) (VII.32)
p
V=(:)T Vi =(:1 =(:)T (VIU3)
-S=(:)p -Si =( ~l =(: )p (Vll.34)
~(~)=-; ~(~)= ~(*)=- ~ (Vll.35) N6i chung, nhilng h¢ (Me nhi¢t dQng dUng eho chM nguyen chit c6 the ap d1,lng cho cac du til etia dung djeh nhung phii tbay nhilng d~ hrqng mol (chi thu~ tmb khukh dt') m6i. e6 d~ IUQllg mol) bhtg nhillig dl!i lm;mg mol rieng phdn. lbi d'l. ti:r G '" H - 1'8 ta duqc:

J.1j =OJ = Hj -TSj

(VII.36)

CUng v$y:

Pi = Ui - TS; NgoAi ra cilng c6 the thi~t '4p :

(Ol;i)T =:~

(VII.37>,

~II.38)

o dAy fi 11 hoat ap ~a i,

§4. PHlIqNG PHAp xAc ElINH El~1 LlIQNG MOL RI~NG PHAN

1. PhllO'ng phap dung a,1 h/qng mol bYu klan

a) D{li ltl{mg mol bilu kiln duqc dimg rQng riii de lam tfnh d6i v6i dung dich 2 clfu tir, khi d6 n6 thuang duqc dung cho cltlft tan. N~u dung

15

dich g6m nl mol dung moi (cau tit I) va n2 mol cMt tan (cau tit 2) thl khi Ioai hoan toan chat tan ra Icbbi dung dich, se con 1~ nl mol dung mOi nguyen chat, Ngtroi ta goi d(}i luang mol bilu kiln ciia m~t thuoc tinh khuech dl) X nao d6 ciia dung dich d6i vm eM!: tan 18..d:p. lugng :

X-(X)n2~

+X = (VII.39)

2 n1

(X)n2~ la gia til ella x khi di loai hoan loan e(u tit 2 (eMt tan) ra khoi dung dich, nhu tht (X)n2 =0 = nl Xf ' b dAy Xr Ia gm tri coo X d6i voi I mol dung moi nguyen cha:t. Do do :

... _ X-ntXf 'l'X -

2 n2

(VII.40)

ho~ n~u dung mOi 18. nt:r(fc H20 : cjlx2 = X-55,51Xf m2

(VII.41)

m2 = "2 18. d¢ molan cua chat tan, con "I = 55,51 18. s6 mol H20 trong 1000 gam O1We.

Khi X 18 tM tfch V cua dung dich 2 e(u til thl (Vn.40) vi6t 18. :

~ = V -nl Vf (VU.42)

2 n2

TIr d6 e6 tM suy ra m¢t each goo thfch y nghia ella Ihllich mol hiEu kie'n Clla cM! Ian nhu san: Neu nhu dung moi giu nguyen nhUng thuoc

tinh cua n6 b trang thai nguyen eMt thl th8 tfch cua n6 18. nl V1° va. chat

. tan dttCmg nhu c6 tM tich (V - nl V1o), do d6 neu quy v~ 1 mol cMt tan, nghia 13 chia eho n2 se d~ tM tich bieu ki€n d6i vdi. 1 mol ehKt tan, +v2 = (V - nIVf)/n2' TIt d6 suy ra phuang trinh bieu thi v~ hmh ·thuc c¢ng tinh ella tM rich V d6i vdi dung dich 2 Call ti'r :

16

v = nt vf + n2tPV2 (VII.43)

Trong tnrong hqp chung, d6i v6i dai hrong X, tir (VII.40) suy fa:

(VII.44)

b) Tlnb d~i lllqllg mol ding pMn eua eMf tan. Thi d\ll deli v6'i dung dich NaO lrong nu6c, s\I' xae djnh 1M tlch mol bitu kiln eua NaO 618°C eho phep bieu thi d{ti hrong nay bang mc')t ham giro tlch (thi tfch tfnb ra eml) :

A. - V-55,51Vt -16,4 25 -12 2

.,v2 - - +, m2 , m2

m2

Til d6suy ra:

v = 55,51 Vf + 16,4m2 + 2,5m~ -1,2m~

b day v Iii Ihe tich dung djeh ; Vf Ii 1M tfcb 1 mol H20 nguyen eh«t = coast ; m2 Ii SIS mol NaO trong 1000 gam (= 55,51 mol) H20 = de') molan eua NaCI. Sau khi d{lO ham pbuang trmh trtn theo m2(n I = 55,51 mol H20 = const) se duoc :

- - av 2

V2 = Om2 = 16,4 + 5m2 - 3,6m2

D6i v6i. m2 = 0,5 thl V2 = 18,0 em] ; deli v6i. m2 = 0,1, V2 = 16,9cmJ•

2. Phltdng phap giao dlim hay phltdng phap tiep tuyan 18. mot phuong phap d6 thi do Rozobom (Roozeboom) d~ fa. Hlnh VII-l minh

hoa each xac dinh th~ tich mol rieng phan V I va V 2 d6i vCri dung dich 2 cau tiro Tnroc h€t xac dinh bang thuc nghiem th~ tfch V cua 1 mol dung dich d6i voi m¢t day thanh phan x2 khac nhau (x2 IS. phan mol cua cau tir 2). Sau d6 ve duong cong V = f(x2) bi~u thi 51! ph\! thuoc cua V vao x2' GQi PMQ la dubng eong d6. N6 cAt nhtrng tn:le tung tai P iing voi AP = Vlo (x2 = 0) va tai Q i{ng voi BQ = vi (X2 = 1), Vf va V~ lit the tich mol cua CAu tir 1 va 2 nguyen chat,

Tai diem M cua duong cong iing v6i dung dich c6 thanh phan x2 nao d6, ve tiep tuyen CMD voi dirong congo Tiep tuyen nay ciit nheng true

17

AL- J...._ ______JB

o 1

-X2

Hinh VI/-J - Phuong pbap tiep tuy!n xac dinh dai hrong mol riengphan.

tung tai diem C trng v6i X2 = 0 va tai diem D 6ng vm X2 = 1. C6 tM chimg minh rAng :

- -- -

VI = ACva V 2 = BD

(su chimg minh khong kh6 khan nhung hoi dai, ta bo qua).

Neu dai Iuong khuech dl) X khong phai la the tfch V thl each lam van nhu tren, chi phai thay V bang X va :

x. = AC ; X2 = BD

3. PhuCfng phap dung h, thU'c GipXCf - Duhem. Wi vCli dung dich 2 ca:u tit 0 T, P const, h¢ thuc Gipxo - Duhem (VII.30a) vi!t la :

x[dXI + X2dX2 =0

H¢ Ibue nay eho phep tfuh XI til: X2 (hogc nguoe lai) khi X2 (hoac XI) dii duqc bitt d6i v6i met day thaah pMn khac nhau eua dung djeh :

dXI ==-~dX2

XI

51! tfch phan 11 T, P const gilta 2 trang thai A va B se eho :

B

6(1)s '" 6(I)A - £2 dX2

A xI

(VIlAS)

TIeh phAn se de dinh bang phuong phapd6 th].

18

c - H6N HQP KHi

§5. HON HQP KH[ u lUONG

I - DUNG DlCH u TuJNG

a) Djnh nghia. C6 the dinh nghia dung dicn Ii tuJng (hay hoan ch'lllh) la dung dich thoa man 3 dieu kien sau d6i voi toan khoang thanh phan :

1) V = Eni Vio; 2) U = LniUf; 3) S = Eni (Sf - Rlnxj), b day v, U, S la the' tich, noi nang, entropi cua dung dich, Vio, Vf. Sf la the tfch, n(li nang va entropi cua 1 mol i nguyen chat b cung T, p va ding trang thai t~p hop nhu dung dich, xi Ia phan mol cua i trong dung dich, R la hang s6khi.

b) H¢ qua. D6i v& moi dung dich Mt kl, aT. p const, V ~ :Eni Vi, 0", :Eni Ui, H '" LniH;, S = :En;S;, F", :En;Fi, v.v ... Do d6 d6'i v6i dung dich If tmmg, lif di!u

- M - ~ '-

kien 1) suy ra: Vi =Vio. tN =:Eni(V; -V;)=:EniliVi =0 (khong co bien thien

thi tich) ; tir <Ii!u ki~n 3) suy ra :

- ° M - ° -

Vi '" ur. liU =:Eni (Ui - Ui ) ",:Eo; liU; =: 0

TIr I) va 2) lai suy ra aT. p const :

H =: U + pV =: :En;(Ui' + pV;o) '" :En;Hi' ; Hi' '" OJ + pvt; H; '" Hi', mM '" Qp =:En; (H; - Hi') "':En; Mi; = 0 (khong c6 hieu l10g nhiet).

TIrd6: C '" dH '" ~ (:En.ffi') = :En. dHj = :En·Co '" :En. Cpo

PdTdT II 'dT 'Pi I,

CPi "'C~i

TIr diiu kiln 3) suy ra:

- ° M - ° -

Si '" S; - R/nxi' liS '" :En; (S; - Si ) = :En; liS; =: - R:Enjlnx;

(Vll.46)

19

TIl' 2) va 3) suy ra:

F = V - TS == In; (Vi - TSi + RTlnx;) = In; (If' + RTlnx;)

Fi = Vi - TSi· Nhung F == In; F;. V$y F; = If' + RTlnx;

.apM "" Inj (I'; --Fi) = Inj 6.F; = RT:Eo;lnx; < 0

Tu I), 2) va 3) suy ra:

0= U + pV - TS = I:n;.(Uf + pyt' _T'Sj0 + RTlnx;) =

= In; (oj + RTlnx;)

Of = vi + pvt - TSi . Nhung 0= I:n;O; v~y

OJ = of + RTlnx; ; .6.0M = I:n;(Oj - Of) = In;.6.0; =

Mij,t khac G = I:ni!li' !li = Oi. vJj.y !li '" or + RTlnXi' or, bam Gipxe bay Ibl! dAng lip eua 1 mol i nguyen ehil, la ham ella T va P,jo d6 c6 the d~ 0i = Ilj (T,p). Khi d6 Ibl! hoa hQC Il:i eua i trong dung djeh If IU(mg c6 dang [(I dan gian :

Il; = III (T, p) + RTlnxi'

(VIlA7)

c) Kei lu4n. Dung dich lf nnmg III dung dich duqe hlnh thanh tir cac cau tU nguyen chat khOng c6 bien thien th~ tfch, khOng e6 bien thien n¢i nang. khOng e6 hieu tmg nhiet nhung c6 bien thien entrOpi xac dinh hOi (VII.46) :

~ = -RI:DjlnXj :> 0

D6i vOi m6i cau tU i eua dung dich If urong ta e6 :

V· - VO 1- i

u -Uo 1- i

H' -Ho I - i

Cp., =co . Pi

20

Si = S? - Rlnxi Pi = ~o- RTlnxi

Gt = G? (T,p) + RTlnxi

).li = Gt = ).If(T,p) + RTlnXi

(VIlAS)

II - HON HQP KH1 LI rmNG

HOn hW(1) cac khi 11 lUang khong duong nhien la dung dich If urlmg (bon hop 11 nrong ci1a cac khf) c6 dlly du cac tieu cilllAn ciia loai dung dich nay. HOn hgp cac khl If IUlmgehi thmi. min nhUng tieu ehuAn iJ6 neu ta thtra nh~ mQt s6 gia thilt, mQt 56 tien de (xem dlICri. day). Khi d6. hOn hop eae kbl 11 nrong mm d6ng tbM la him hop (dung dich) 11 tuerng eua cae khf. b day. ta thila nh~ nhitng gii thilt (tien de d6) va dung thu .. t ngit hOn hep 11 lUang cua khf va hOn hop cua cac khf If lUc'mg thea nghia nhu nhau.

1. Ap suit riang phin

Theo Danton, ap s~t rieng phan Pi cua khi i trong mot hOn hop khi ba:t ld (li tOOng hay khOng) la ap s~t rna khi i d6 se tac dung neu nhu n6 chiem m¢t mmh toan bQ tM tich V ciia hOn hqp 6 cung nhi~t d(l T nhu h6nhqp.

D6i v6i h6n hop khl lf tOOng, dinh nghia d6 dan tm djnh IUt,it Danton (Dalton, 1805) ve cong tinh cua cac ap suat rieng phan,

Gid sir h6n hop khi Ii tu6ng g6m n I mol khi 1, n2 mol khi 2, ... , c6 the tich chung la V, ap suAt chung (toan phan) 18. p l:J nhiet dQ T. CO the hieu thi phuong trmh trang thai cua h6n hop khi Ii nrong gi6ng nhu d6i vOi khi If tOOng nguyen chat :

pV = nRT = (nl + n2 + ... ) RT = LniRT

(VII.49)

tir d6:

P = L nj RT = Lc·RT

V 1

Nhung thee dinh nghia Danton ve ap sulft rieng pMn Pi ella khi Ii lOOng i :

(VII.50)

RT

Pi= ni V = ciRT

(VII.51)

(1) Trong nhi¢t dQng 1\fC hoc, thu.t ngu Mn hqp va dung djch thuemg dlll,1C dung d6ngnghia.

21

taro :

(VII.52)

tee la : ap sual loan phdn ella h6n h{1p khi Ii IfLelng bOng lting ap sudt rieng phdn Pi ella f,mg khi trong h6n h{1p. D6 18 n(Ji dung Clla dinh l~t Danton, phan anh tinh ceng duqc cua cac ap suA"t riengpMn d6i v6i hOn

hqp kill Ii tuCmg. .

TIr (VII.51) va (Vll.50) suy ra:

J2__ = ....!2_ = xi tUc J.a : I Pi = PXj I EPi :Enj . .

Nhu v~y, up suat rieng phdn Pi eua khi i trong h6n h{1p khi Ii hieing' bdng ap sudl loan phdn p ella Mn h{1p nhan vu; phdn mol Xi ella n6 trong h6n h{1p khi.

Ghi clul. Ap suM. III thuQc ~ cllitng ~, do d6 lip sua't rieng pb&l kMng c6 lien quail ca deD d~ brc;mg mol rieng ph&l (cbi thuQc lmh khuLch d~ mlii c6 dll-i iUQDS mol rieng

ph&l). .

(VII.53)

2. Thitfch

TIr (VTIA9) suy ra :

RT . 0

V = Eni -. = Enj Vi

P

Vio = RT I P Ia th~ rich 1 mol kht If tubng i nguyen cMt lJ cung T, P nhu hOn hop, Nhung V = :Eni Vi, Vi 18 tM tfch mol rieng pMo. cua i trong hOn hqp. V4y :

(VII.54)

3. Nqlnlng

D6i v6i th~ rich, thl nhu tren dii lam, tit phuong trlnh trang thai cua hOn hop khi If tulJng suy ra dugc Vi = ViO• COn d6i v6i n¢i nang, kbOng

suy ra duqc U i = uf. K~t qua nay phai dugc tbm n1$l nhu m"t tien ~ trong nhi~t d~g 11;fC hQC cO di~n. tUc 18 ta phRi tbira nh~ :

22

(Vil.55)

4. Entr6pi

Theo (VI.5a), entropi Sf cua 1 mol khf Ii .tillmg nguyen ehoit c6 dang sf = sf (T) - Rlnp, sf (T) 18 s6 hang chi phu thuoc V80 ban ehA't khi va V80 T. Nhiet dong 11}'C hoc thira nhan rAng entropi mol rieng phdn Sj cua moi khi i trong hOn hop khi Ii tubng vAn co dang gi6ng nhu entropi mol

sf cua khi Ii tuOng i nguyen cMt nhung phai thay ap suA't p cua khi

nguyen chat bang ap suat rieng pMn Pi cua khi i trong hOn hop, tIi'c 13. :

(VII. 56)

Sl! thira nhan nay 18 noi dung cua dink Ii Gipxa vi' entrap; cua hOn hop khi li tulmg. Vi Pi = pXi nen (VII.56) c6 the: vi!!t :

Si = sf (T) - Rlnp - Rlnxj = sf - R1nxi, do do:

S = Lnj Si = Lnj (Sf - RlnXi) (VII.57)

Nhu vay, trong ba.tieu chuan (hay dit!u kien) cua dung dich Ii tubng thi chi tieu chusn the: tich (VII. 54) moi duqc rut ra tit phuong trlnh trang thai ciia hOn hop khi Ii tuang, con tieu chusn nQi nang (VIL55) va entropi (VII.57) ph8.i thira nhan nhu nhiing tien dt! d6i vOi hOn hop khf If tuang. Chi voi dieu kien nhu v~y thi mOi khi If tuang i trong hOn hop moi e6 iUy du cac thuoc tinh (VII.48).

Ghi chu ." 1) Theo (VI.7). ham Oipxo hay th€ ding ap cil.a 1 mol khf If tuang i nguyen cMt c6 dang Gr ee gi(T)+RTlnp. Dt chuyen sang th'€ ding ap mol rieng ph4n

cua khi Ii tltang i c6 ap suft rieng ph4n Pi troag h6n hgp. ta chi vj~c thay p bang Pi :

Oi =: &0 (T) + RTlnPi (VII.58)

VI Pi = PXj nen :

OJ "" gf (T) + RTlnp + RT/m:; = OJ' + RTIIIXj

2) VI Pi = qRT nen (Yn.58) c6 the vi€t :

23

Gi = gf (T) + RTlnRT + RTlnci = s .o(T) + RTlnci

(VII. 59)

v{ri :' g f (T) = gf (T) + RTlnRT

3) Vi J.lj = Gi nen th€ hoa hQC Ili CO"" khi If t!lOng i trong hOn hC1(l khf If t!lOng c6 tM bieu thi du6i m('ll trong nhilng dang :

J.li = J.lf (T) + RTlnPi

J.li = u i (T) + RTIIICI

(VIL60)

J.li = J.li(T, p) + RTlnxj

troag d6 J.li (T) '" gf (T) ; J.l.o (T) = g i (T) ; J.lf (T, p) = Gf (T,p).

§&. HON HQP cAe KH[ THVC (KHONG L( TtJONG)

1. Ap suat rling ph'n

D6i vOi hOn hop khf thuc, ap s~t rieng phan dinh nghia theo Danton khong c6 cong tinh, tUc 18. khOng tuan thee dinh lu~t Danton :

p '* ZPi (Danton)

• ngoai ra:

Pi (Danton) :# PX;

Sb cfi nhu v~y la vi ap suai rieng phan (dinh nghia theo Danton) cua cac khi thuc trong hOn hgp khi Ul khOng dQc l~p ; gilra cac phan tii cua nhiing khf thuc luon luOn co nhilng nrong tac khOng tM b6 qua nhu d6i voi khi If tuang.

Dt bio toan tinh cc)ng duqc cua cac ap sulit rieng phan thl trong tnrong hop chung, d6i v6i bOn hqp lthi If tttdng cling nhu khong If nnmg, ta co the dinh nghia ap stuff rieng poop hinh thue Pi la ap su!t thoa man M thrrc :

(VIl.61)

24

Di nhien, d6i vro hOn hop khi If tuang. Pi dinh nghia theo each nAy trung v6'i: Pi dinh nghia theo Danton.

D6i voi h6n hop khi thuc thl til (VII.61) suy ra duqc :

l:Pi (hinh thirc) = l:pXj = Pl:xi = P

tlic la suy ra duqc cong tinh c~ cac tip s~t rieng pM.o. hlnh thuc, nhung khong the suy ra duoc Pi hinh thuc lit tip suB:t rna khi i trong hOn hop khi thirc se c6 ne'u nhu n6 chiem mot mlnh toan hi) tM tich V Gila hOn hop a

cung nhiet dQ T : N6i each khac, d6i vro hOn hop khi thuc, Pi (hinh thee) "# Pi (Danton). D6 lit do co tuong tolc giiia cac phan til khi thee, va khi th1!C khOng tuAn theo plurong trinh trang thai Clla khi Ii tui1ng. Chi a ap suat dll IMP. chfnh xac la khi p --7 0, rom co the 00 qua nhilng tUdng tac

d6, khi do khi thuc ~t duqc tinh Ii tuang va Pi (hlnh tlnrc) rom d6ng oMt voi Pi (Danton).

2. HOCilt ap rling ph'n (thtmng chi goi tit ia hoat ap)

Tit nay. d6i vro mOi khi i trong hOn hop khi If tuang cling nhu khOng Ii tuang. ta _deu dinh nghia ap s~t rieng phan Pi theo each th6ng nhat (VII.61):

Pi = pXi

Neu hOn hop la Ii tuang. the' hoa hQC cua khi If tubng i trong hOnhgp co dang :

~ = ~ (T) + RTlnPi

(VII.62)

S6 hang J.l.f (T) chi phI) thuoc vao T va bang the'bOO. hQC cua i khi Pi = l. Neu hOn- hop 13. khong Ii luang. ap sual rieng pMn Pi cua lchf thuc i trong bOn hop kh6ng nghiem dUng (VII.62). ~ bio toan dang dan gian

(VII.62) clla the' boa hQC. 18 tbay Pi cua kbi thuc bAng dai lueng fj sao cho the' boa bQC J..li cua khi thuc i trong hOn hop bAng:

).l; = flf (T) + RTlnfj

(VII.63)

25

va sao cho khi ap s~t toan pMn P cua hOn hqpti6n c:& Wi khOng (nghla la khi hOn hop khf tit!n dAn dt!n trang thai li nr<mg) tbl fi ~ Pi. roc Ii :

lim ( fj ) I' (fi) I' 1

- = lID - = 1m Yi :::

p-+O Pi P-+0PXi p-+O

(Vll.64)

Dai I~g fj dinh nghia nhtr ~y goi la hoat ap rieng phon cUa khf i trong hOn hep khl. Ti s6 Y ::: flp goi la h~ sf! hoar dtJ ella khi i. Di~u kien (Yn.64) c6 nghia la d6i v6i hOn hop khi Ii tuOng. fj = Pi va Yi = 1.

Trong tn.rCmg hop chung, hoar ap fi cua khi thgc la ham ella nhi¢t dO. ap sdt va thanh pMn ella hOn hop,

Khi hOn hqp khi thVC khong c6 sai lechnhieu so vm tinh If tubng, c6 tb~ ap dung quy tdc gan dung sau :

(Vll.65)

ttIc la : trong hOn hop khi thuc, hoar ap,fi cua mOi khi i x!'p xi bAng phful mol Xj cua n6 trong hon hop khf nhan v6i hoat ap if cua khf i nguyen chat, a nhiet dQ vA ap s~t bang nhiet dQ va ap su!'t roan ph!n cua bOn hop khf. Trong (VII.65) chi s6 K chi pha khf (hay hoi) ; khi khong sg nham Ian v6i pba long (dun~ dich long) thl bO kh6ng can ghi K.

Hoar ap fr ella kh£ i nguyen cMt c6 tM tfnh tir ap su!'t pf va tir M s6 hoat dQ Yj cua n6 theo phuong trlnh :

e yO. i ::: iPi

(VII. 66)

§7. SV HoA TAN H~N CHE COA cAc KHI VAO NHAU

MQt thlJi gian dai, ngum la eho rang tft ca cac khi deu c6 the tl'l)n lin bolm toan vao nhau tbeo bft kl ti I~ naa. Nhung ngay ti:t l894, Van de Van di tien ooan rang cac kbi c6

26

the thOng trQn lin hoan toan v80 nhau va c6 the tich ra thMb hai lOp (h_pha khf) ctJ, bAng v6i nhau;' trtn ohi~t dl) lOi hfll Clla cac khi. Un diu tien (1941) cac nha hac hoc - Lien Xo LR. Krichepili. P.E. BonsacOp va n.x. Xiklixo di kh6m_ pb8 fa bing thlfC nghi¢m Hob tao hfll chi ciia ci1.c khf Mi vOi - Mn hqp NH3 va Nz khi 4p sufl dtt t6i viti nghln bar va viti nlm sau l{li tim !My hi~n tuc;mg d611 nmeu h6n hqp khf khie. N6i chnag SI1 hlnh thanh ltip ;, ohiloS h6n _h~ d6 tuAn theo ohiloS quy 1U$t dii bitt VI! 511 ehiu /iTp ;, ohllog h6n hW limg (xem Ch.XlV. §6).

27

CHWNG VIII

DUNG DICH L6NG vO CUNG LOANG

S\! nghien CUu tbl!C nghiem va li thuyl!t dung dich loang dil n6i b~ len haag diu 'a cu6i thl! ki 19 diu tM ki 20. Nhil'ng dinh lu .. t ~ dung dich lOOng la nliil'ng dinh fu4t gim hgn, chi dung chfnh DC d6i v{ri. dung dich v6 cung lodng, cOn d6i v{ri. dung dich cO dQ loang hihl han tbl bhl tinh thl,fC ngbiem la phii xac dinh xem ohil'ng dinh 1u$t ~y c6 tb~ lip dung trong chirng mire nao rna khOng gay ra sai s6 dang te.

§1. CAN BANG DUNG DICH LOANG - HOI BAa HOA. DO H~ Ap SUAT HOI.

llO TANG lll~M SOl ClIA DUNG DICH LOANG

1. Ap suat hoi bao hoi ella dung d!eh long

Hoi can Mng vOi dung dich long goi la hai baa hoa (goi tat la hai) cua dung dich, N6u n6 chua moi csu tir cua dung dich th) ap 5u~t hoi se bang tong ap su~t hoi rieng phan cua cac csu tiro Mt)t 56 cau tir co tM khOng bay hoi (hoac chi bay hoi khong dang ke) b nhiet dt) ~ao sat va th,!c t61a khOng c6 m~t trong hoi.

2. D!nh lu~t Raun ve sl! h, flip suat hoi eLla dung mol tren dung dieh

a) Truang Iufp hdi ttl Ii tuOng. Nam 1886, nha bac hoc Phap Raun (F.M.Raoult) 11m th9:y bAng thuc nghiem ap suat hai CUll dung moi tren dung dich lodng be han ap sud! hoi cua dung moi LOng nguyen cMt d cung nhj~t d~ (va a cimg ap su~t ngoai).

D6i veri dung dich loing, ap suat hoi PI cua dung mOi ti l~ veri phan mol Xl ella n6 trong dung dich :

PI = k] Xl

28

Khi XI = I (dung moi long nguyen chat), PI = pj = kl• \1.y ki chinh la ap sulft hoi pj cua dung rnoi long (clfu til 1) nguyen cMt l:J cung nhiet d<'). Dod6:

I PI = pj Xl I (VIII. I)

OQi x21a phan mol cua cMt tan (csu tir 2) trong dung dich, D6i voi dung dich 2 cau tir, X I + x2 = 1. do d6 x I = I - x2 va (VIII. I) c6 the vi~t :

(VIII.2)

N~u ghi PI tren true tung. x2 tren true hoanh, duCmg bieu di~n ta mot dOOng thing. TIc (VIII.2) lai suy ra :

o

PI - Pl. - X - 2

pj

(VIII. 3)

Nhtmg phuong trlnh tu (VIII.I) d~n (VII!'3) la nhflng bieu thrrc cua

dinh luat Raun. Hieu 8Pl' = Pt - PI goi Ia d(J h{l tuy4t 4tii ap sulft hoi ella dung moi va do bAng nhtmg dan vi nhu mmHg. COn (pj - PI) / pj = 8Pl/ pj goi La d(J /u;l tuong db'j ap sulft hoi cua dung rnoi, n6 Ia me)t dai luong khong c6 thu nguyen. 0 dang (Vlll.S) dinh lu~t Raun c6 th~ phat bieu :

D(J ha tuang doi ap suat hoi cua dung m6i tren dung dicb lodng lxing phdn mol cUa cluft tan trong dung dich.

D6i vm dung dich rift loang, n2 « n I' (VII!'3) c6 the vi~t :

(vm.4)

Neu m21a de) molan, tUc Ia s6 mol ddt tan trong 1000 gam dung' mOi thl n2 = m2 va nl = l000/Ml,MI Ia kh6i luqng phan til ella dung mOL Khid6 :

29

(VID.5)

o dang nay, dinh luat Raun c6 the phat bieu :

Dr! ht;l tuang dtli ap suat hai eua dung m6i tren dung dich [nang tl [~ viii dr! molan tUa eMt tan trong dung dich, h~ stf Ii l~ Ka lxing kh61 lU(IIIg phdn Iu-eua dung moi chia eho 1000.

(VITIA) co the viet:

apt n2 g2/M2

-=x2 ~-=

P1 nl gl/Ml

H~ thUc nay cho phep xac dinh kh6i hrong phan tir M2 cua cMt tan khi da biet MI' Apl/p1 va luong g2 gam chit tan trong gl gam dung

(VIII.6)

moi,

b) Truong hf./p IUli ta khong li tudng. Khi do phai thay lip sulft bang hoat lip va dinh luat Raun (VIILl) chuyen thanh :

(VIII.?)

f I ta hoat lip cua hoi dung moi tren dung dich loang, if lil hoar ap cua hoi dung moi long nguyen chl'ft6 cung nhiet d¢ va ap sulft ngoai nhu dung dich. (VID.7) goi III dinh lU~1 Raun Idng quat.

Ghi chll. Nbiing dung dich Ibng tuAn thee tri~t cit: cljnh lu;)l Raun dang (VIII.I), (VIIL2) hay (VIII.7) a mei ndng dO gQi III tiu.ng djch Ii IlIemg (bay dung d;ch hoan chinh). DO III l~ dung djch Ibng dan gian nMt. NhUng dung dich lbng khOng hoan chinb cbi tuAn theo dinh lU$! Raun khi dung dich III dli loing (chfnh xac III vO cUng loing). C6 tht: n6i dung dich khOng hoan chinh III II tubng chi d6i vm dung mOi khi dung djch III loang.

3. E>!nh lu~ Henry ve flip suit hClI cua chit tan

a) D6i vOi dung dich Icing. neu cMt tan cling bay hoi thl no tuan theo djnh lu~t Henry (1803). Nlu hoi la Ii tU'Cm.g. dinh lu~t nay vilt Ill:

1'2 =k2x2

(VIII.S)

30

tuc la ap sulft hoi rieng pMo P2 cua cha:t tan ti l¢ v6i phan mol x2 ella n6 trong dung dich Ioang, he s6 Ii l¢ k2 goi la h~ s6' Henry. Ch6 khac nhau can ban voi dinh l~t Raun la k2 chi la mot hAng s6 nao d6, tuy thuoc vao di~u kien t60 tai ella h¢ (T, p ngoai da: cho), Nell d6i v6i dinh

luat Raun PI = k 1 x 1 = pfx I' nic Ia k I = pf thl d6i v6i dinh luat Henry

P2 = k2x2, k2:F- p~ khi dung dich la khOng Ii tuOng va rtft loang (x2 ~ 0), do d6 khong tM ngoai suy toinong d¢ X2 = 1.

Neupha hoi Ia khong If tOOng, phii thay ap sulft P2 bang hoat ap f2 va (VIII.g) viet la :

f2 = k2x2 (VIII.9) la dinh lw)t Henry Mng quat.

b) Dinh luat Raun va dinh lu~t Henry dlT<JC tim thay di)c lap nhau nhung c6 the: clnmg minh rang dOl vdi dungdick lodng, m(u dung rna; tudn theo dinh lu{jt Raun thi chdt tan tat yeu phdi tudn theo dinh lut,'it Henry va nguac lai.

c) Neu dung dich la If tuOng (hOM chinh), nghia Ia nell dinh luat Raun dung v& moi n6ng d¢ thi dinh luat Henry cling dung v6i moi n6ng

d¢. Khi d6 c6 the ngoai suy t6"j x2 = 1 (chat tan b trang thai long nguyen chat), f2 = k2 = ff va (VIII.9) trb thanh :

(VIII.9)

(VIII. 10)

Nhu th€, dOl v6'i dung dich lOng Ii lllUng, nqi dung Clla hai dinh lUi)!

Raun va Henry trung nhau. Do la ~p hop nheng phuong trinh f1 = ffxI va f2 = ffx2 goi lil dinh luat Raun - Henry t6ng quat hop nhaI, thuong chi goi cit lil dinh l~t Raun. Khi pha hoi la If tuirng, hoat ap trung v6i ap

suat, khi d6 PI = PYXI va P2 = P~X2·

31

4. The hoi h9C eua cAe c8u tu trong dung dleh loing

KID c6 can bAng dung dich long vdi hoi bao hoa cua n6 tbl the' hoa hQC cua mo~ c(u til i trong ca hai pha phiti bAng nhau ~L == ~f (L == lOng, K = khi (hoi». The! hoa hQC coo i trong pha hoi c6 dang' :

lJiK = ~ (T) + RTlnfj

D6i v6i dung moi 1, theo dinh lu~t Raun f1 = floXI, vay :

III = J.lf = J.lf = J.l?(T) + RTlnff + RTlnxl·

Hoat ap flo cua hoi dung moi nguyen cMt chi phu thuoc vao T va. p ngoai, do do c6 thi g¢p 2 sO hang d'-u v6 ph8i phuong trinh tren thanh mQt sO hang chung :

Jlf (T, p) = Il? (T) + RTlnflo

va :

I j.11 == J.1f (T.p) + RTlnxl I

(VIII.it)

j.1? (T. p) 18. the hoa hQC cua dung moi long nguyen ch!t (kbi x I = 1). No phu thuec chu y6u vao T, cit it vao P. VI ap su!t chi co anh huang r:ft nho d6i voi chat long.

D6i vOi. chilt tan trong dung dich loang, theo dinh Iuat Henry fz == k2x2 (k2-yt ff) :

J.l2 == Il~ == j.l.~ = j.l.~ (T) + RTlnk2 + RTlnx2 H¢·s6 Henry k218. ham cua Tva. p, do do cung co tM d~t : j.l.~ (T. p) == j.l.~ (T) + RTlnk2

va duoc :

1r-J.l-2-=-j.l.-~-(-T-. -p-) -+-R-T-ln-x-2---r

(VIII. 12)

32

Qui y rang d6i vm dung dich khong 1£ tOOng va lOOng, J.l~ (T,p) khOng e6 y nghia Il the hod hQC ella ch~t tan (c~u til 2) long nguyen eh~t vl khong th~ ngoai suy tm nOng d() X2 = 1. S61i~ J-lt (T, p) cling phu thuoc Chll y~u V3.0 T, rnt it V3.0 p.

5.1)9 tiling dii'm sol eua dung djeh IOing,chat tan kh6ng bay hel a} Nhi~t d~ sbi cUa pha long. Mt cli pha long nao, nguyen cMt hay dung dich cling deu bAt cUu sei l:J nhiet d¢ rna tai d6 ap s~t hoi bao hoa Clla n6 tr6 thanh bAng ap suat ngoai, Nc!u ap sua:t ngoai bang 1,013 bar, nhiet dt) soi goi 18 nhi~t d~ sbi chudn hay dilm sbi (hay phi dilm) chudn.

D6i voi coot long nguyin CMt, khi ap suat ngoai khOng dOi thl nhiet dt) soi ding khOng doi su6t thm gian soi cho den khi toan l:X) chat long chuyen bet thanh hoi, Nhu vay, d6i vm chat long nguyen chat, nhiet d:¢ bAt tUu soi va nhiet d¢ k~t thiic su sOi la mot, Nhung d6i vm dung dich, l:J ap sUlit ngoai khong dOi, trong tnrong hgp chung, nhiet dt) bAt d1iu va k~t thuc sg soi lA khac nhau va nhiet dt) soi thay doi lien tuc trong su6t qua trlnh sOi.

D6i voi dung dich lodng chd: tan khbng bay hoi, hoi bao hoa ella dung dich chi g6m e6 hoi

bao boa cua dung moi va theo dinh luat Raun, ap suat hoi baa boa d6 luon luOn thap han ap sullt hoi p =1,013 barl-----r------::;,if------::;-r--bao hoa cua dung moi long nguyen chat 0 cung nhiet d() va cung p ngoai,

Hlnh VIII-I bieu thi sl! phu thuoc ap suat hoi bao hoa cua dung moi nguyen

chat (dmmg cong AB) va

cua dung dich loang c6 Hinh V III - 1. SI! tang dil'!m soi coo dung djch ioang

nong dt) khac nhau (dmmg chft tan khong bay hoi.

p

r

B

B'

B"

33

cong A'B' va A"B") vao nhiet dQ. Nong d¢ pMo mol x2 cua chat tan trong dung dich cang 16n (nhung dung dich van dll loang) thi duang cong ap suat hoi cua dung dich cang phan b6 thA"p hon so vill duemg cong ap suat hoi cua dung rnoi nguyen chat.

Dt xac dinh nhiet dQ soi chuan, ta ve tren gian d6 hmh vm -1 duang ding ap ling vill Po = 1,013 bar. Nhiet d¢ rna tai do duang dAng ap nay dt nhilng duang cong AB, A'B', A"B" V.v ... tai nhiing diem C. C, C', ... la nhiet dQ sCi chuan cua nhilng pha long nrong lhlg. Ta thay rang nhiet

dQ sOi chuan d6i vci dung dich loang (T s) Iuon luon Ian hon so vOi dung rnoi nguyen cha't (Ti) va hieu giita chung ~Ts = T, - Ti S15 cang 160 neu n6ng dQ x2 cua chat tan cang 160 (trong pham vi dung dich van Icing).

b) Thilt /f)p cong thue dOl vOi ~Ts' D6i v6:i nhilng dung dich dll loang d~ co the ap dung dinh l~t Raun, ta co, khi ap suat hoi p cua dung dich

bang ap suat ngoai Po = 1,013 bar:

P = PI = pjxl = Po = 1,013bar = const

Sau khi Ia'y logarit phuong trlnh nay r6i dao ham theo T se duqc :

dlnp = dlnpy + dinxi = dlnpo = 0

dT dT dT dT

(a)

pj la ap suAt hoi bao hoa cua dung moi long nguyen chat, n6 tuan theo phuong trinh Claperon - Claudiuxo dang :

d/npj Lh,l ~=RT2

(b)

~.l 18. nhiet hoa hoi cua 1 mol dung moi long nguyen chat. Do d6 k€t hop (b) v6i (a) se duqc :

dlnpj Lb,1 _ -dlnxi _ dln(l - x2)

~ = RT2 - -""dT - dT

34

boac :

Lh! dT ~d/n(1 ~ Xl) = _, - .-

R Tl

Khi tfch phan plurong trinh nay trong khoang nhiet d¢ nho, til nhiet di) sOi chuAn T~ cua dung moi nguyen chat (Xl = 0) d~n nhiet di) bat dAu sOi chudn T, cua dung dich loang c6 phdn mol Xl eua dung rnoi bang (1 - Xl) thi c6 the chap nhan 4,1 = const, do d6 :

X2 L Ts dT

- J dlll(l- Xl) = ~ J-

o R 'If-r2

-111(1 _ x2) = Lh,1 (Ts - T~) Rr~ Tso

(c)

D6i vai dung dich rift loang, xl« 1, c6 the chap nhan cong thiic gful dung:

-In (1 - Xl)::::: X2

M~t khac, vi hieu (T, - T~) 13. be, c6 tbe chap nhan TsTso = (T~)l va phuong trlnh (c) t:rO thanh :

Lb,! rr; -~)

Xl = ---=.!.::,.._-=------=--

R(~)l

GQi 3.Ts = Ts - T~ la d~ tang diim soi cUa dung djch :

AT- _R(T~)2

LJ. s - Xl

Lb,!

D6i v6i dung dich rat loang c6 di) molan m2 (s6 mol cMt tan trong 1000 gam dung moi), theo (VII. IS) :

(VIII.13)

Xl =~m2 1000

35

&Ts = R(Tso)2 Ml m2 = R(~)2 m2

lOOOLh•1 lO(X)I."h.1

A.h,l = ~~l la nhiet hoa hoi rieng (t11'c la d6i vdi 1 gam) cua dung moi

(VllI.14)

nguyen ehA't (bi~u thi ra JIg). Vl n6 III mQt Mng 56 a nhiet d¢ T~ Me dinh nen c6 tM ~t :

r-I-&-T-s =-K-sm-2 ..... 1 rvmrsi

tee la d~ tiing dilm· s6i Clla dung dich lodng Ii If vcii nong tU) molan m2 clla cMt tan trong dung dich, H¢ s6 ti l¢ Ks goi la Mng s6' nghiim soi (hay phi nghi~m) Clla dung mOi nguyen cMt. Gia hi li thuy€t Clla no la :

K, = R(T~)2 = 0.0083(~)2 (Vlll.16)

10Cl0 A.h.l A.h. I

1Xri. vi

__!_ = 8.314 :::: 0 0083

1000 1000 •

Hang s6 Ks chi t4c tnmg cho dung moi, khOng phu thuoc vao ban cMt cua chA't tan. Thi du, d6i v6i dung mol Iii. mroc H20. K, (thuc nghiem) = 0,51 ; gia hi If thuyet tinh thee (VIII. 16) Iii. K, = 0.513.

c) Phep nghifm s6i (hay phi nghifm). N€u g2 gam la Im;mg cMt tan trong gl gam dung mOi thl luong cMt tan trong 1000 gam dung mOi la 1000 g2lg1 va s6 mol chat tan trong 1000 gam dung moi, t11'c Iii. d¢ rnolan mj la :

. g2 1000

m2 =-.--

gl M2

M2 la kh6i luong phan til cMt tan. Dua gm tri (VIII.17) cua m2 vao (VIII.15) se dugc :

(Vlll.17)

36

(VIII.IS)

tudo:

M2 = K, 82 . 1000_ gl ~Ts

Phuong phap MC dinh M2 dua vao phuong trinh nay bAng each do _d(> tang diem sOi ~Ts ella dung dich toling la mot tmg dung cua phep nghiern 50L

CAn luu Y nhilng M' thtrc tren chi dung lchi khong c6 51! phan li hay lien hop phan tir ella cMt tan trong dung dich,

(VTIl.lSa)

§2. CAN BANG DUNG DICH LOANG Val

.:! ., A

TINH THE CUA DUNG MOl.

DQ H~ BANG DIEM CliA DUNG D!CH LOANG

1. £)9 h' bAng dlim cua dung d!ch loing

o ap 5ufft lchi quyen ngdai Po = const, khi lam ha dit thap nhiet d(> cua dung dich loang thl c6 the dat tm nhie; dQ bAt tUu ket tinh (hoa rAn) cua dung dich rna tai do hat tinh the tUu tien hi~n ra, can bang vci dung dich. Nhiet d(> do goi la nhiet d(> bAt <Mu dong tJ4c (dong bdng] khi no

thap han. nbi¢t di) trong phong. Khi Po = 1.013 bar, n6 gQi Ia nhi¢t d¢ bdt ddu dong d{ic chudn.

KMc vOi cha't long nguyen cMt bat dau va kc!t tluic 51! kgt tinh (j nhier di) khong d6i khi Po = const, nhiet di) kgt tinh cua dung dich thirong thay d6i, noi chung ha thap dan khi SI! kc!t tinh phat trien va thirong thap han. so vci dung moi nguyen chat (LOmOnOxOp la nguUi dau tien, b thg ki IS, nhan tha:y bang diem cua dung dich tha'p hem cua dung moi nguyen chat).

37

Khi dung dich loang bat dAu ktt tinh, nhtmg tinh the: hien ra c6 the la cua dung moi nguyen chat hoac c6 the la tinh the: tap hop (dung dich ran) gom c8. dung mOi va chat tan. o day chi xet truang hap dung dich cho tach ra nhiing tinh (hi cua dung moi nguyen cluft. D6i veri mrong

hop nay, nhiet d¢ bat ddu ktt tinh hay bang die:m Tb cua dung dich bao gia cling iMp h<1D cua dung moi long nguyen chat (T~) a cung lip smt

ngoai Po nhu nhau. Hieu 8 T b == Tg - T b goi ·18 dO ha nhiet dO bit d4u ktt tinh, hay goi tAt la dq ha bang dilm cua dung dich loing (so veri dung mOi nguyen chat).

C6 the: chung minh (xem Ch, X, §7) rang cOng thuc d6i veri 8Tb cting

tuang tt}' nhir d6i voi 8Ts:

R(To)2 0,0083 (Tg)2

18Tb=Kbffi2( Kb= b

. . 1000 Aoc.1 Aoc,l

(VIII. 19)

"-nc,! = Loc,!/M1 13. nhiet n6ng chay rieng (d6i veri 1 gam) ella dung mOi nguyen chfft ; Kb la hang so' nghirm lanh hay hang sf/ han nghi~m cua dung mOi nguyen chat., Thi du, d6i veri mroc, Kb (thuc nghiem) = 1,84, Kb (li thuyet) tinh theo (VIII.19) la 1,86; d6i b6i benzen, Kb thee nghiem va Ii thuylt 18. 4.9 va 5,15.

2. Phep nghitm I,nh (hay him nghi,m)

Han nghiem hay phep nghiem lanh la phuong pMp thee nghiem do d¢ ~ bang diem cua dung dich loang, TIt d6 cO the xac dinh khO, luang

phdn ui M2 cua cMt tan trong dung dich. Nlu g2 Ia s6 gam chat tan trong gl gam dung moi thitheo (Vll.l7) c6 the bitu thi 8T b nhu sau :

g2 1000

8Tb = Kb· m2 = Kb - . -- (VIII.20)

, gl M2

tird6 :

(VII1.20a)

38

VI phuong phap Iian nghiem chfnh xac han phuong phap phi nghiem (phep nghiem soi) nen n6 dttqC dung rong rii.

D6i v6i dung dich loang, nhUng M thUe tren chi dung khi khong co s\l' phan li hay lien hop phan tu cua chAt tan trong dung dich.

§3. Ap SUAT THAM THAU

1. Ap suat thi'm thau. Can blng mitng

D6i v6i dung mOi nguyen char, neu nhiet dQ.18. T, ap su6t khi quy~n ngoai hic dQ11g len n6 lit P == P" thl ap suA't hoi cua n6 lit Pt = f(T,Po) va th~ hoa hQC cua n6 bang :

~t = Ilt (T) + RTlnPt

N~u dung moi d6 khOng a dang nguyen chAt rna a trong mot dung dich trongd6 phan mol cua no Ia Xl < 1 thl cling vAn trong di~u kien T, p khOng d6i nhu tren, ap sullt hoi cua n6 tren

dung dich se tuan theo dinh lu~t Raun neu

dung dich la dllioang, tUe lit bi ha di va bing

p} = PtXI = Pt (l- x2), do d6 th~ hoa hQC Clla dung moi trong dung dich b8.ng :

~l = ~t (T) + RTlnpI

Nhu vay, a T va P ngoai khong d6i, th~ hoa hQC cua dung moi trong dung dich be han th~ hoa hQC cua dung moi nguyen cMt m¢t lugng bang :

o

.6.1l1 = I-1t - III = RT11I.£L PI

Do d6, neu dung dich va dung moi nguyen, chllt tiep xuc nhau qua mot mang

(VIII.21)

2 3

Hini: VII/-2 - Dung cu dan giin de do ap su!t thAm. thau ; I, dung dich mr6c duang; 2, nude nguyen cMt : 3, msng

ban thim : 4, 6ng hep,

39

ban thdm (hlnh VIII-2) thi chua th~ c6 can bang lx1i vi the' hoa hQC cua dung moi b hai ben mang chua bang nhau,

Mlng ban tMm (Ihf du mAng colodion) chi cho dung moi (nu6c) di qua. con eha'i tan (dU'Cmg) khong.d! qua dugc. NIlOe c6 thi !Ii qua mang ban tham ti:r ca hai phia, nhung t6c dQ' ella nu6c tir blnh ngow (nllOe nguyen cha't) vito blnh trong (dung dich) 16n hon lir blnh trong ra binh ngoai. Do d6 trong th¢: t€, ta quan sat dlIQC bien nrong tl! chuyen ciia nuoc (hoac m()t dung m6i khac) vao dung dich qua mOl mang ban thain. Hien nrong nay gQi II. tlufm tMu_ N6 II! dien ra theo e~i.!u tir dung moi nguyen chit (e6 the' hoa hQC ).I] 16n) vao dung dich (trong d6 dung mol e6 thl hoa hQe).l, < IJ.I >.

Do c6 su tham tMu, mite dung dich trong 6ng hep dang Ito, lam tang ap suit thuj' tinh eua dung djch, do d6 tao nen mOt lip suat phl} lam tang t6c d¢ chuytn cac pb!ln tir nu6c tir btnh troag ra blnh ngoai, tU"c la lam can lro d4n sl! tham th4'u. Khi mac dung dich trong 6ng hep dll-t tm ditm A each mtk OIlOe trong blnh ngoai met d¢ eao h Dao d6 (htnh VIII-2) thi ap suit phI}. dat tm gia tri rna llI-i d6SI! tham th!u di:rng IlI-i (t6c d¢ ehuyen eac ph!ln tir nuOe tir bmh trong ra blnh Dgoru va tir binh ngoai vao binh trong tW tbanh bang nhau). NhlltM la can bang dUf!<: thilt I*p giiia dung dich va dung mOi nguyen cbit each nhau bang mOt mang ban thain. Khi d6, giiia bai ditm M' va M I!y (, cuag mite trong dung dich (ditm M') va trong dung mOi nguyen eMt (ditm M I!y if m~ thoang cua • nllOe) e6 mot hieu lip su!t P' - P. Vl lip suit t(I.i A va M bang nhau va bAng ap su!t khi quytn ngoai P nen hi~u P' - P do Mog d¢ caoh clla cQt dung dich, tU"c la b8ng tip sutft thuy rInk cua c(lt dung dich d6. N6 _ bang P' - P :::: hpg, p Ia kb6i 11II1Dg rieng ella duog dieh, g la gia t6c trong tnJOog a noi lam thi nghiem, BCri VI lip suft d6 lam dimg Sl! tham thfu, n6 can b8ng v6i ap suat tMm llUiu 1[ Clia dung dich,

Trong th\fC tl, ngtn'ri ta thui'mg do lip suft tham tha'u b8ng each do lip sufI thuy tinh d6. Vl tM c6 tht dinh nghia ap su4t tMm tMu 10 ap suat phl} pluii lac dl}ng len dung djch co n6ng dtJ dii eho dl dung dieh can Mng vOi dung ",oi nguyin chtft each nhau bOng ~t mang ban tlu1m (trong di.!u ki~n nhi~t d¢ va ap suitt khi quytn ngow kbOng d6i). H~ cling e6 tht n6i b T = const, mu6n cho dung dich cAn bAng qua mang ban tham v6i. dung mOi nguyen chtrt clla n6 thl ap sutrt P' tlic dung Itn dung dich phai 160 hon ap sua't P tlic dyng len dung mOi mQt hlQllg b3ng lip suit tMm thfu. Ntu P' < P + 1[, dung m6i sf cbuyio qua nWl:g ban thain vAo dung dieh, Ntu P' > P + 1[, dung mOi sf tir, dung dich chuy6t ra DgOOi. NEll P' ::: P + 1[ thl c6 can hI\ng (cAn b3ng mAng).

2. t»jnh lu,t Van Hop ve ~p suit thim thiu

Nam 1886, bAng thuc nghiem, Dba bac hQC Ha Lan Van HOp (Van't Hoff) da tim fa phuong trlnh d6i voi lip suar tham thau 1t cua dung dich Loong:

!1t=C2RT I

(VIII.22)

~ la nO,ng dQ mol- th~ tich ella cha:t tan, ~ = n2N = g:z/(M2V), n218. 56 mol cha:t tan trong th~ tich V ella dung dich, g2 la kh6i luong eMt tan.

40

trong the: tfch V d6, M2 18 kh6i hrong phan tit e.lla cMt tan con R la hAng s6 khi. Neu V tinb fa lit, ap suAt 1t fa atm thl R =O,0821.atm/K..mol Dinh lu~t Van HOp e6 the: phat bieu :

Ap suat thdm thdu 7rcuadung djch.iming co s6' tri bdng ap suat rna s6' mol cluft tan se co neu no a trang tMi khi li tudng chiem thl tich bang thl tich V CM dung dich va a cung nhift d~ T nhudung dich.

3. Nhi,t dqng h,re hQc ve'ap suit thim thau ,

Tren da n6i ap suat P b dung dich chi c6 the tang nbc) xuA't hien them mot ap suA't phu (thf du ap suA't thuy tinh cua C¢t dung dich). Khi ap suA't phu nay can bang vm ap suA't th&m thA'u 1t cua dung dich thl moi c6 can bang giua dung dich va dung 'moi each nhau bAng mot mang ban tham va khi d6 the hoa hQC cua dung mOi b hai ben mang m6i tra thanh

bang nhau. Nhu vay, a dung dich, chi sau khi P tang tU gia tri Po Mn giR

tri P' = Po + 1t thl moi c6 ding thee Ilf = J.lI'

~ xac dinh su phu thuoc cua III vao P, ta dung h¢ thUe (VII.33) :

(a; \ = VI tll"c ladlll = VldP aT= const

V ~ nguyen tAc, V I c6 ph~ thuocvao P nbung rtlt it bbi vi pha lOng l3. dt kh6 nen, do d6 c6 tM chap nhan V I = const. Khi d6 S\l' dch phan se cho :

1t

&Ill = VI IdP:::: 1tVI o

Klt hop voi (VllI.21) duqc :

o

XVI = RTinh PI,

D6i v6i dung dich loang, PI = pf XI. tUc IS. (Pl/pf) = xI. do d6 :

(VIII. 23)

41

Vi X2 « 1 nen -In(l ;- x2) ~ x2 va :

1tVp:,:: xzRT I'::: °2 RT ho4.c 1t(01 VI) 1':::02RT "1

DOi v(ri dung dich rlt loang, c6 th~ coi g~ dUng "1 VI bAng the tfch V cua dung dich, do d6 :

1tV = "2RT. h~c 1t =- '; RT= c2RT (Vrn.24)

DO chinh lit plnrong ttlnh Van HOp d6i voi ap suIt tMm thlu cua dung dich loang.

Ghi dui. Dt'Si v6i. dung djeh loang, c6 MUng lbuQc tinh btu nhu chi phu IhuQc vao stf l/l?llg li{u pMn ella cMt tan, kbOng ph\.! tb* via ban chit eua eMI nay. Nhilng thuec Imh nhu 1M gQi 1a thu~ doh tQ.p thl eua dung dieh (tu ehil La TInh coiligatus = i4p 1M, t$pdOOn).

Loai thuQc tinh I$p the eua dung dich loang g6m c6 d¢ h. luang d6i ap sufi hm cua duog mel, dt) lAng diem s6i, dt) h. bing diim va ap suat th&m IMu cua dung djeh loiog :

APl __ Ml m2

ATs=Ksm2

PI 1000

1t=ezRT

B6n Ihu¢c tiob d6 ti 1~ vai nhau va ttr thuec tinh nay e6 Ihe suy ra rhuoc tfnh kia, Moi m¢t troog obUog thu¢c tlnh Ify d~u e6 1M dung de xac dinh kb6i luc;mg phan lir cua eb{1 tan.

§4. cAN BANG DUNG DtCH LOANG VOl DUNG DICH LOANG c6 MOT CAU III CHUNG. £)INH LU~T PHAN BO. SV CHIET

1. Djnh lu,t phin bo d~ng dan gian

Gia thu hai chIt long I va 2 khong hoa tan vao nhau hoac chi boa tan rat it.lchOng ruing ke. Them vao M d6 m¢t lugng nho cau tiI tha ba (rAn h~c long) tan duoc rieng re trong ca hai chit long 1 va 2. Sau khi lAc

42

manh ~ SI! hoa tan dugc nhanh chong wi de yen cho can bang dU'QC thiet I~p a T, p const thi se hinh thanh hai 16p mongo M6i 16p J.a mot dung dich loing cau til thu ba rna dung moi 13. chat long 1 a 16p nay va cMt long 2 a 16p kia. Hai pha long d6 can bang vdi nhau, lap co ti kh6i be hOn thi nOi len tren,

Di~u kien can bang la th~ hoa hQC cua cau til thu ba ¢ hai pha (') va. (") phai bang nhau : ~'= u", Khi chi hoa tan nhUng lugng nho chat d6 d~ dugc nhUng dung dich loang thi cMt tan (CAU til 3) Ulan theo dinh luat Henry va thl boa hQC CUa n6 trong dung dich loang co dang (VIII.12). Nhu vay, dieu kien can bang la :

J.L0• (T, p) + RTlnx' = J.LO" rr, p) + RT/nx"

md6 :

,0" O'

In!_ = J.I. (T,p) - ~ (T,p) = rn(T p)

x " RT T •

aT, p const, ~i lugng d6 la mot hAng s6 va :

x'

- = f(T, p) = const

x"

(Vffi.25)

.

(VIII.26)

N~u dung dich ta du lodng thi n6ng d¢ phdn mol x -ti l¢ vdi n6ng d¢ mol- th~ tich c. Khi <f6, a T, p const :

B

Nhimg phuong trlnh (VIII.26) va (VIII.27) Ia bi~u thnc dinh lugng

cua dinh I~t phdn b6, thuong goi 13 djnh l~t phdn bd Necxa (Nemst, 1891). Nhtmg thirc ra, dang (VIII.27) da duqe Bectolo (Berthelot) va

Junglaiso (Jungfleiscb) tlm ra tir 1872 khi nghien cnu s\1 phan b6 iOt 12 giOa nu6c va m¢t dung moi hltu co (~) khOng tan trong nuoc,

Hang s6 K goi la ~ stf phdn b6~ (1 T, P const, n6 chi phu thuoc vao ban cMt Clla chAt tan va cua cac dung mOi, khOng ph\! thuoc vao luong cua chung, Trong th\l'C ~, K ph\! thuec chu ylu vao T, mt it V80 p. Do d6

dinh luat phan 1>6 c6 the phat bilu : .

(VIII.27)

43

(j nhift d9 thOng ddi, ti sl)' nang d9 clio cdu tit thit ba trong hai pha lOng c-dn bdng /a n0t dt;li luang khOng Mi, khOng ph~ thu{5c vao luong tuwt dlfi hay tuong d6i cUa cac cdu tit, khidungdich lei du IOOng.

C6 th~ cheng minh ring h~ s6 phdn b6 K bdng tt s6 d9 tan rieng re clla cdu tu thit ba trong hai ch4t lOng 1 va 2 khi nhang d9 tan do Iii be :

~ = (c ') bao hoil = ~= K (Vm.28)

c" (c It) hilo hoa s2

s 1 1il d¢ tan cua clfu tit thu ba trong chat long 1 va s2 lil d¢ tan cua n6 trong chlft long 2 a cimg nhiet d¢. d¢ tan lil n6ng d¢ chlft tan trong dung dich bao boil cblft d6 (dung dich tuy bao boil nhung van rlft loang),

Dinh lu~t phan b6 dang dan gian (VIIL26) hay (VIII.27) chi ap dung cho nhUng pbAn til cua cMt tan c6 d¢ Ian nhu nhau u ca hai pha long.

2. ejnh 'uijlt phin b6 d~ng 16ng quat. Khi phan tir chAt tan c6 dt') 16n trung blnh khac nbau a hai pha long, do nhOOg hien ureng pbAu Ii hay Iitn hqp pbAu tlr gAy ra thl hoac la phll.i thay o6og dt') trong (Vlll.26) va (VIIl.27) bang 1w9t dt) (khw uiem oay se nghien c11'u a Ch.X), hoac neu giii' n6Dg dl) th] them nhitng M s6 nao do phan anh mal! dQ nbiiog qua trlnh phan li hay Iitn hop phan tir vA xac dinh trong mOi tru<mg hop bang tb"c nghiem, Khi d6 dinh lugt phOn btf u d9ng t6ng qudt co thi biiu thi bang phuong trlnh :

(C')D --=const = K c"

..

(VIII.29)

(VIII.29) goi la dillh lugt phdn b6 Necxa -SiMp. Gia tri caa n co thi bang bo~ khac s6 nguyen ; n6 bang n = M"/M', a day M' vA M" la kh6i Im;mg phan tll' trung btnh cua chat tan trong pha long thu nbM (') va tha hai. ("),

N€u n :> I, cha:t tan c6 kh6i hnmg phan tir trung bloh a pha (") )do bon a pha (,), d~ bi¢t n€u 0 pita (') no c6 pban tir blah thubog (dang don phAu, monome) thl trong pita (") n6 pbai co pilAu tit litn bqp. Trai lai, n€u n < I, tbl M" < M' va nl!u aplla (') phan tir c6

d~ ldo blnb tbubog thll:J pha (") no phw. phAu li, .

I>l!-c bi¢t, niu trong dung m6i I. cha:t tan c6 phan tU binh thuCmg. ron trong dung mOi 2, n6 t6n ~ chit y€u, gm 100% duOi dll-Dg pilAu tll' kep dOi (Iu6ng phan, dime) c6 dl'> 16n ga:p dOi thl dinh lu.t phan hIS bieu thi bang plnwng trlnh :

(c,)2

- = K (VIII.30)

c"

Pbuung.trlnh nay cia ~ thl,fC nghiem xik nb~ d6i v6i slf phan b6 axit benzoic trong Dlwe va trong benzen 1ft dung mOi hihl co col nhu kheng tan trong nu6c. Axit benzoic tan trong nu& cbu y5u a dang phan tir don phAu (monome) ~H5COOH, thuc ra

44

n6 c6 phAn Ii m~t ph4n nhung sl! phAn Ii nAy IA y6u, ta bO qua. Trong benzen thl n61ien hgp. cM ylu od~g lu6ng phAn (dime}bay pbAn titkepd6i (ct;H~H>:z, chi c6 m~ ti I¢ nh6 dcm phan tl! do C#lsCUOH. Oqi c' IA n6ng ~. axit benzoic trong om vA c" Iii ndng d~ axit benzoic trong benzen thl c' yA c" thoA man p.tr. (Vill.30).

Khi khOng c6 hi¢n ~g phAn Ii hay lien hgp phAn tit thl n '" 1 va (Vill.29) trO ~ ~g dcm gian (Vill.27).

Nhung vi thuong thOng bilt trut'ic duc;Ic IA c6 bay thOng c6 hi¢n tugug pbAn Ii hay lien bgp phAn tit cho nen. trong truimg hep chung, ta cln sir d1}llg djnb 11$ pbAn M a ~g tOng qamt (Vm.29) vA ti61 bARb do bAng thlfC nghi¢m ~t diy giA tri ndng dQ c' vA c" cua cMt tan trong hai pba lOng (vA loang) 11 cang nbi¢t ~ (vl nguyen tic 2 gia tri cua c' va 2 gii trj nrong Ung cua c" IA dU). Sau d6, tir (Vm.29) suy ra :

19c" "" nlgc' - IgK

rvm.sn

Bieu thlk nAy la m¢t pbiWllg trlnb duimg thing. C6 ngbia IA nlu tir tbl,l'C ngbi¢m xly dl!Dg d6 thj Igc" "" f(/gc') sf dugc mi)t duimg thing c6 h¢ sO g6c bAng n cOn tung dQ gtJc bAug-lgK.

3. Mqt Il'ng dt;lng cua dlnh lu~t phin bo: 511 chitt

TIl dinh lu~t phan b6 suy ra mot phmmg phap nit m(lt cMt tim ra khoi mot dung moi nho them vao d6 met dung moi thu hai khong tan trong dung moi thtl nha:t nhung hoa tan dugc cMt khao sat. Phuong phap nay goila s\l chi€t. NguO'i ta dung n6 ~ ~ b6t m()t hop pMo vO Ich hti4c de la:y ra a dang giau han m()t hgp pMo c6 fch nao d6 cua dung, dich.

Dung mOi chi!t cln chon saocho s\l chi!i dUQC nbanh nhat, hieu qua nMt va it t6n nha:t. N6 ph8.i khOng tan h* chi tan mt it vao dung moi Clla dung dich c&n chi!t va phlli c6 M s6 phan b6 cang cao cang t6t d6i

v6i dung mOi nay. Ete etylic va m¢t s6 dung moi hihI co khac (CCl4, CSz, ~ v.v ... ) thuong dap tmg t6t nhUng yell cliu d6 khi clio chiet cha:t htiu co ra khai dung dich nuOc.

Sau khi da chon dung moi chi!t r6i thl each ti!n hanb s\l chi!t cling ra:t quan trong, D6i v6i cung mOt hl<;fIlg dung moi chiet da cho, hieu sua:t chiet se dugc nang cao han neu ti!n hanh s\l chi!t bang tirng lm;mg nho mot, chtl khong nen dung toan b¢ trong m()t 140. chiet duy nha:t.

De don gian, ta gilt thilt cac tiE:u phAn Clla chtrt tan c6 dO 1& gi6ng nbau khi tan trong bai dung mOi va cac cAll tit Clla h¢ thOng c6 tiWllg tic boa bQC v6i nbau.

Gia 1M ~ V A 1ft dung dich chUa So gam chft i trong dung mOi A vA c4n cbiel cbft i ra khoi dung djch d6. Them vso d6 VB 1ft dung mOi B hoA tan dugc i nbung IchOng tan vAo trong dung mOi A. Oqi gl IA luvng cbtrt i con I. trong VA 1ft dung djcb d4u. N6ng ~ cua i trong dung dich nAy. tlnb fa gam/lft la :

45

Di nhien, Im;lllg chat i phlin M trong VB 1ft dung mol B la go - gl' Do d6 n6ng dl) (gamJlit) cUa i trong pha long nay Ii:

cB = &I - gj

I VB

GQi K Itt h¢ 56 ph:1n b6 ch<ft I gliia hal pha long A va B. Theo dinh lu~ phan b6, & T:::consi:

tir d6 :

(VIII.32)

D6 la iUQIlg cMt chiet i cOn I~ troog V A lit dung dich d4u sau hin chill tM nMt.

Tach rieng V A lit dung dich d6 (cbUa gl gam chAt i) ra khoi lap dung dich B (nhet dung pheu cbill c6 khoa), Bay gib xu<ft ph't tif dung dich V A nay, ta tiln hanh sl! chill 140 1M hai, ding dung VB lit dung mOi nguyen cMt B blng dung l!in mroc. VI h¢ s6 ph:1n b6 K khong dOi cbo nen hrong g2 gam ch!l't i cOn I~ trong V A 1ft dung dich sau Mn cbilt tbu hai nay bAng :

(VIII.33)

Trong trui'Yng hep chung, sao n l!in cbilt, lin nao ctfng bAng mQt hrgng khong dol VB ciia dung rnoi B nguyen eMt tac dung v(ij lugog V A dung dich tach rieng sau mOi I!n chill, tbllUQIlg in gam ch!l't i con s6t I~ trong dung dich A se III :

( KV )8

ID = 80 KV A : VB

(VIIL34)

TIt d6 suy ra logog cMi dii chit.: ra dUQC sau n 140 chiet :

(Vm.35)

46

CHl)JNGIX

DUNG DICH LrTlJONG vA DUNG DICH THlJC

. . .

§1. £lINH NGHIA vA THUQC TfNH CUA DUNG DICH LfTUONG

1. Nhrtng each khac nhau dlnh nghTa dung dich Ii tuifng a) Djnh nghfa dung dich Ii tudng theo 3 tieu chudn.

o chuong VII. §5, ta da dinh nghia dung dich If nnmg (hay hoan chlnh) la dung dich thoa man 3 di~u kien (hay tieu chuan) sau b moi

thanh phan : .

1) V = l:niVr : 2) U = :EniU?: 3) S = l:ndSf - Rlnxj) Ba di~u kien d6 dAn tm:

V· - vr . U· - UO. H' - HO • -C - CO ~. - SO Rlnx·· 1 - l' I - i' 1 - i' Pi - p.l , ...... - j - i, '

Gi = Gf + RTlnxj :I-li = Gi = Jlf (T,p) + RTlnxj. V.v ...

b) Djnh nghfa dung dicn Ii tudng thea tieu chudn duy nMt vi thi" hod hoc. CO tM sii dung tieu chuan duy nhAt v~ thl hoa hQC d~ dinh nghia dung dich If nxmg nhu sao:

Dung djch li tlidng (hoan chinh) Iii dung djch trong dO thi"hoa hoc Pi cua m(jt cdu tit; btlt k'i ngh;~m dung h~ thuc sau u moi Xj "

II-li = I-lf (T,p) + RTlpxj I (IX. 1) -

C6 tM chrrng minh rang nlu ~Qt csu tlr i nao d6 thoa milo (IX.I) b moi xi thi tAt ca cac cau tii We trong dung dich bAt buec cOng phai thai man (IX. 1) cr moi thanh pb4n. Nhu v~y dilu ki~n du dl CM m<Jt'dung dich ta If tudng ia thl hoa hQC cua met cAu tii i nao d6 nghiem d6ng

(IX.1) b moi Xj.

47

D6i vdi dung dich a trang thai ngung tu (long hoac do), anh hu6ng cUa lip suAl no th~ hoa hQC kbOng gi6ng nhu d6i vdi khf : anh huOng d6

be han nhi~u. D6i v6i. i trong dung dich long h~ rAn, th~ hoa hQC Jli vA do d6 s6 hang ~ (T, p) phu thuoc chu y€u vao T, rAt it vao p, -do d6 trong sl! gcin dUng tha nMt, c6 th~ b6 qua 8nh huang cua ap suAt.

TIt (IX.l), c6 thi suy ra IllQi thU¢C tfnh khlic cUa dUng djcb Ii ttWog. Thi du, vl RTlnx;_ khOng pby. thu¢<: vilo p nen tir{IX.l) suy ra :

(~)T=( a~O}T

Nhung '( 4af ,ap>-r '" (aof lap >-r "" vr "" the tfcb mol cUa i nguyen eMt va theo (VII.33) (8J1/t3p>-r:::: Vi = the ticb mol rieng ph<in ciia i trong dung dieh, V'_y Vi '" Vi', AVM = rtli AVi = :En; (Vi - vj) = 0, v.v ...

c) Djnh nghia dung djch li tudng theo quan dilm phdn tli. Theo nhiing quan di~m th6ng ke, dung dich lOng (hoac ran) se la If tuOng, nghia la th€ hoa hQC J.li se thoa miin (IX.1) vOi moi Xj khi luang lAc giila cac phan til cang dang vA khac dang cua cac cau til d~u bAng nhau a khap moi di~m trong dung dich, tac 18. khi tAt ci cac phan nr deu c6 tnrong 11!C nh,u nhau. TIll du, d6i v6i. dung dich 2 cau til A vA B, nang hrong tuong tac E gina cac phan til cung dang va khac dang phai hoan toan gi6ng nhau, EA-A = EB-B = EA-B•

N6i cMt che thl khOng m(lt dung dich th¥'c nao c6 chinh xac nhimg thuoc tinh ciia dung dich II ttWog, rna chi c6 the d"t g<in tm dil!u kien If ttWog " mac dO nao d6. Nhimg dung djcb lOng d,t kha t6t dil!u ki~n if ttWng la nhDng dung dieh rna cae et(u tir cua n6 c6 ct(u tao phan tir va nbiing thuec tinb v~ If va hoa hQC gi6ng nhau ho¥ dt glln nhau, Thi du :

1) h6n hqp nhilng d6ng phan quang hQC;

2) dung dich nhilng cAu tLr chi kbac nhau vI! thsnh phlln d6ng vi nhu H20 + ~O ;

3) dung dich nbitog cMI d6ng ding canh nbaunhu benzen + toluen, hexan + beptan • . dibromopropan + dibromoetan v. \I ••.

d) Djnh nghia dung dich Ii tudngtheo djnh l~ Raun. D6i voi dung djch long li tudng, vi ta:t cll cac phan nr diu c6 truong 1VC nhu nhau cho nen tinh chat cua m6i phan til trong dung dich Ii tuang khOng phu thuoc vao viec n6 duqc phan b6 giila nhfmg phan til nao, Vi v~y, kha nang cua phan til i trong viec chuy~n tit dung dich If tuimg sang pha hoi phai gi6ng nhu khi cau nr i a trang thai long nguyen chAt (a cung T va p

48

ngoai nhu nbau). Kha nang dO chi phu thuec vao hl'qI1g tuong d6i ella i trong pba long. Do do, .st;r chuyen i tit dung dich sang hoi, do bbi. hoat ap

fj ella n6, se cang Ian neu d¢ chua tuangd6i ella i trong pha long cang 160, uk la fj ella i trong hoi ph8i ti I¢ vOi n6ng d(> phAn mol Xj cua i trong dung dich long, nghia la fj :=:l kjXj, kj la h¢ s6 ti l¢. H¢ thee nay phai dung vOl. moi Xj' ke ca Xj = 1 (cau ttl i nguyen chat). Tit d6 suy ra gia tri ella h¢ s6 ti le k = ft' va :

(IX.2)

DO lA bieu thuc C_lla dinh. lu{it Raun t6ng quat (dOi khi cling goi la dinh lu~t Raun - Henry t6ng quat hop nhtft).

Nhu v~y, co the dinh nghia dung dich lOng li tudng ld dung dich ma m¢t eau tu- i bat ki ella n6 tuan theo trjft d€ djnh lud; Raun ufng quat u moi ndng dQ.

Chi can mot elfu tir i nao do tuan thee triet cit! dinh luat Raun l:J moi n6ng d() la dll de cho dung dich III H tu'Ong bdi vi co tM clnrng minh rang khi d6 cac du tir khac cua dung dich bAt buoc cling phai tuan thee triet de dinh luat Raun b moi thanh phdn (xern §3).

2. Ap sust hoi biohoa·cua dung.djeh long 0 tUOng

Gia thir hOn hop haichat long 1 va 2 la dung dich long 11 tubng.

Trong tnrong hop chung, gia thit!t ca hai cau tir d~u bay hoi. Neu ap sulft hoi ella cluing la du be de pha hoi can bang voi dung dich c6 the coi Ia hOn hop khi Ii nrong thl khi d6 hoat lip trung voi lip suiff rieng phan,

fl = Pi va f2 = Pz. D6i voi dung dich long Ii lubng, nhilng lip suat rieng phan nay phai tuan thee triet cit! dinh l~t Rauo b rnoi nong d(>:

(IX.3) (IXA)

Nhir v~y, P I va P2 d~u lA ham ~c nhlft ciia thanh phan cua dung dich long. bieu thi bang phan mol x2 ciia cau lir 2. DuOng. bieD dien cua

49

chang trong giin dO ap smt - thanh pUn cua dung dich long (hinh IX-I) Ia nhtmg duang thing. do d6 ve nguyen lAc chi dn dugc xac dinh bCri 2 dit!m IA

dU. thi du d6i v6i. x2 = 0 (cAu tir 1 nguyen chAt) vA x2 = I (cAU tlr 2 nguyen chai),

.A.p su~t hoi toan phan cua dung dich bang :

P=PI +Pz= pf(l-X2)+P~X2

P = pr + (p~ - pr) x2 (IX.5) V~y ap su~t hoi toan phan cua dung dich long Ii tu6ng cfing lA ham bac nhat cua x2 vA cnng bit!u thi bang mot duang thing (blob IX-I).

T=const

o (Ioloon)

1 (benzen)

0,5

---- x (benzen)

Hi"h Ilf.l. s., phl.l thuec lip suft hoi rieng phln va loan pbAu vao thMh pbAu dung dich lOng Ii tubng

§2.DUNG DICH THVC. SAl LeCH DUONG VA AM SO VOl BINH LU~T RAUN

1. Sai I~ dlfdng va. Am so val djnh lu,t Raun

D6i v6i. dung dich thuc (khOng If tuOng), lip su~t hoi rieng phdn p (n~u hoi IA If tuang) h~c hoat lip fj (n~u hcti la khong lf tOOog) c6 nhtmg gili tri Ian han (sai lech dlJdng) ~c be han (sai lech dm) sovoi nhGng gia tri tlnh theo dinh lu~t RaUD •

. a) Hlnh IX-2 trlnh bay nhtmg dubng ding nhiet (duang cong net lien) bieu dieD sl,l pb1} thuec ap suAt hoi rieng pMn vA roan phdnvao thanh pbln cua dung dich benzen-axeton lA m¢t trong nbGng he c6 sa;

50

l~ch duang v~ ap suat hoi so vm dinh lu~t Raun. Nhitng duong thAng cham cham trng vOi truang hop neu dung dich la li tOOng.

t=25°C

Chti y rang phia ben trai

gUm d6 la vimg dung dich 250

loang axeton trong benzen. 200

o day, d6i voi xaxelon be, ¥ 150 benzen d6ng vai trO la dung ~ 100

c:

!pOi c6 ap sua't hoi PI tuan 50

theo dinh lu~t Raun tren ml)t t khuc duang nbc (phan 1-

duCtng cong lip suat hoi PI

cua benzen trang vm duang thing cham cham) (hlnh IX-3), con axeton Ia chat

tan. ap suat hoi P2 cua n6

0,2 0,4 0,6 0,8 1,0

(CH3hCO

__ X2

Hinh' IX-2. A.p su4"1 hoi trong M benzen - axeton (sai l¢Ch duong)

tuan theo dinh luat Henry. P2 = Paxeton = kxaxeton (duong cong lip suat hoi P:2 cua axeton a d6la mot khuc duang thang).

o phia phai gian del ctlng c6 mot vimg dung dich loang benzen trong axeton. 0 day d6i vOi nhUng nong de} be cua benzen (xI < 0;1) axe ton d6ng vai tro la dung moi, lip suat hoi P2 cira n6 tuan theo dinh lu~t Raun (pMu duemg cong P2 cua axeton trung voi duong thing cham cham) con benzen d6ng vai tro la cMt tan, lip suat hoi PI cua n6 toAn theo dinh luat Henry.

p

vClng djnh IUQt Raun

t

Hinh 1X-3. ~ minh hoa vung dinh lu.' Raun va vung dinh 1~ Henry trong h¢ benzen - axeton (sai Iech dirong)

5l

t=1rc
400
300
C)
:J:
E 200
E
Ii
100
1 0

CHCIJ (C2Hs)20 -+ x2

Hillh 1X-4. Ap sui'l hoi trong M clorofoc-ete etylic (sai l~h Am)

t=29,2"C

600~~ __ ~ __ ~ __ ~~

500 1----1---"7"F---+---~!orrr_I

:E'

E 300 E

ci

° 0 (CHshCO

0,2 0,4

0,6 0,8

-

Htnn IX-5. Ap suat hoi trong h~ axeton-cacboo sunfua (sai 1~ duong c6 Cl,I'c d~).

52

D6i vCri. nhiing M co sal lech duong, a nhung vimg dung dich loang, lip suat hoi cua eMt tan 100 han so voi lip sua't tfnh nt!u dung dich l3. If

tuimg (k > p~).

b) Hinh IX -4 trlnh bay gian d6 lip suat hoi - thanh phan d6i v6i h¢ clorofoc-ete etylie Ia h~ c6 sai /¢ch am so vm dinh l~t Raun. Nhfing vang dung dich loing Ia ldui rO d6i v6i xCH03 < 0,05 va d6i vOi

Xete < 0,1. a nbOng vimg dO, ap suat hoi ella chat tan be han so vm dung dich If ttWng

(k < p~).

c) CO nhiing h¢ rna su sai lech so vtri dinh luat Raun Ia du Ian. lam eho duang eong ap SMt hoi toan phan c6 cue dai (hmh IX-5, h¢ axeton - cacbon sunfua) hoac cue tilu (hinb IX-6. h¢ ~ -clorofoc).

Ap sua't hoi bao hoa cua nhiing cau til long nguyen chat rna cang gful nbau (6 cimg nhiet d()) thi nhimg sai lech nho ve phia duong ding nhu am so v6i dinh luat Raun Ia da co the lam xullt hien cue dai hoac cue titu tren d~g bi~u di~n lip suat hoi toan pUn eua he theo thanh phoin ella dung'dich,

d) Nhfing dung dich c6 sai l~ch duang ve ap suat hoi thubng hOp thu nhi~t khi cluing dl1QC hinh thanh til' nhiing cau tir nguyen chat, n6i each Wc, nhiet hlnh thanh dung dich c6 dA"u duong (theo quy UC1c ve da:u trong nhiet dong 11,lC hoc). "Trai lai, d6i vci dung dich c6 sai l~ch am. nhiet hinh thanb dung dich thuong e6 dau am, tac la s\f hlnh thanh dung dich nay tod IIhi¢t. N6i chung, dA"u cua sai lech so vdi dinh luat Raun va dau cua nhiet hmh thanh dung dich thuong trung nhau,

0> I E E a:

200

r

o

o 0,2 0,4 0,6 0,8 1,0

CHCb

Hinh' IX~. Ap suM hoi trong h¢ axeton-clorofoc (sai lech Am cO cue litu)

2. Nguyen nhAn. Neu nhtrng phan ti'r A va B trong dung dich hut nhau vUiI\fc yeu han hrc hut giila nhihl.g phan tu A vUi nhau hoac B v{ri nhau thl di nhien cluing ri:ri. bO pha long de chuyen thanh hoi tuong d6i de dang han so vm nhimg cau tii" 16ng nguyen chit, do d6 gAy ra nlurng sai lech duong ve ap suit hoi so vm djnh luat Raun. Tnrtmg hQp do thuOng gi;lp khi co s\f khac nhau ro r¢t v~ ap sm.t n(li hoac Vf tinh pnan CI,fC cua hai cau tir long, thl du nhu khi hoa tan mot ch:ll co cue vao m(ll dung mei khong cue (tnrong hop axeton trong C$z). VI su rm xa nhau cua nhitng phan tii" A hoac B trong qua trmh hmh thanh dung dich doi hoi phai tieu thu nang IUl!llg Iii" ngoai dum dang nhiet cho nen dung dich co sai lech duong thui':tng Up thu nhi~l. Ngoai fa, n€u khong co nhtrng yeu 16 khac lam phuc tap them th] s\f hmh thanh loai dung d!ch d6 c6 the co kern su tang 11I1'ich do chb cac phan tiI 6 xa nhau han so vOi. khi chang b trong cac cau tit long nguyen chat (tuy nhien, dieu nay chua thanh m¢t quy tic ro ret).

Neu nhtrng phan tiI A va B trong dung dich hut nhau vm nhiJog II,fC manh hon II!C hut giiia A vOi A hoac giira B vm B trong dfu tu long nguyen chit thl khii nang chuyen chung to- dung dich long len pha hoi se gi:im di, do do co sai 14ch am ve ap sual hoi so v6i dinh luat Raun. 5\f ll!-i gan nhau han cua cac phan IU trong dung dich giai phong nang

53

hn;mg loa ra ngoai dlJ6i dang nhiet, do d6 nbi¢1 hlnh thanh I~ dung dieh nay thmmg c6 dlfu am (toti II/u·¢t). Trong mQI s6 tntOng hop, nrong tic hut giua cac cA'u tli c6 thi din tm nbUng qua trlnh hoa hQC (sonvat hoa, hlnh thanh lien ktl hidro, hlnh thilnh hgp chat hoa hQC v.v ... ). NhUng tntOng hop nay lit xay ra trong nhUng he rna ca hai cA'u tli lMu c6 cue, thi du axeton va clorofoc c6 the hlnh thanh lien ktl hidro giita chung vm nbau va tao nen pink hop 03CH ... OC(CH3)2' Trong nhiing he nhu v*y, sq hlnh thilnh dung dich thMg loa ra nhieu nhiet va ap suA'1 hot c6 sai I¢ch am manh so vm dinh IU*1 Raun ..

CAn luu Y Iii nhUng ytu t6 glly ra sai lech dirong va am c6 tht tac dung d6ng thM troag dung dich, do d6 nhilng sai lech quan sal dltg.: thMg III ktl qua t6 hgp nhUng sai l¢ch mau thuAn nhau vt dA'u.

§3. HeTHLrC aUHEM - MACGULEXa (MarguJes)

1. Thiet I,p h., th(rc £)uhem - Macgulexo

Theo ·h~ thUc Gipxo - Duhem, d6i v61 dung dich long hai c~u tir 1 va 2, b T. P const, ta c6 :

(IX.6)

Vi tht hoa hQC cua cac cau tii trong dung dich long chi thay dt'Si dt it thee bien thien cua ap su~t chung nen co th~ ap dung (IX.6) b T = const d6i v61 toan b(1 day thanh phan cua h¢ rna khong dn ph8i ke t61 anh huong cua ap suat chung, mien la hieu gitta ap suat hoi rieng pMn cua hai cau tli ph8i khOng qua Ian.

Di~u kien can bang gitta dung dich long va hoi bao hoa cua no la :

).! = Jl~ = ).!f = Jlf (T) + RTlnfj

(L = pha long, K = pha khi (hoi)). Do d6 bitn thien ding nhiet ella th6 hoa hQC c6 dang :

d).!j = RTdlnfj (T = const)

Sau khi loai bO s6 hang RT = const, (IX.6) tra thanh :

(T = const)

(IX.7)

tit do:

54

(T = const)

(IX.8)-

(IX.7) c6 the vi~t :

dfl df2

xI-+ X2-=O

fl f2

Chia hai ve VOl dx1 va nha fang dXI = --dx2 (VI d6i VOl dung dich 2

(T == const)

(IX.9)

cau tir, xI + x2 = 1) se duqc :

~ dfl = x2 df2 fl dXI f2 dX2

hoac :

dfll dxl = df21 dX2 (T = const)

fll xl f21 x2

Nhimg h¢ thuc til (IX.7) den (lX.IO) dtu goi 13. h¢ thite Duhem - Macgulexa, la mot bien each cua h~ tluic Gipxo - Duhem (IX.6) d6i voi dung dich long hai cau tir. N6 cho Sl! lien M dan gian gilra hoat ap rieng phan cua hai cA"u til d6i vOi cac thanh phan khac nhau cua dung dich long d T = const. H~ thee Duhem - Macgulexo thuong diroc dung khi

pha hoi cua dung dich co the coi Ia hOn hop khf If tlldng. Khi do ft = PI'

(IX.IO)

f2 = P2 va M tlurc Duhem - Macgulexo se co nhung dang :

xldlnPI + x2d1nP2 = 0 (T = const) (IX.7a)
db,P2 = - ~ dinPI (T = const) (IX.Sa)
X2
xI dPI + X2 dP2 =0 (T = const) (IX.9a)
Pl P2
dpl!dxl :::: dp2!dx2 (T= const) (IX.10a)
PI! XI P2!x2
55 2: Ap dl,lng h, thlh: E>uhem - Macgulexa cho dung djch If tttO:ng

a) Nhdc vephuang trill" bdc "hat, dang y = ax. Dao ham cua n6 Iii : dy/dx = a, nhung y/x = a, vay dy/dx = y/x. DO Iii phuong trlnh duong thang di qua g6c toa d¢.

b) Ap dung. Nhu dt«}C biet, d6i voi dung dich long li urong, duong bitiu dien PI theo thanh phan dung dich Iii mot duong thang di qua g6c toa do, t1ic Iii dPI/dxl =_ PI/xI. Khi XI = 1 (cfu tir 1 nguyen eMt) thi PI = PY dad6 :

dpi =.EL = pf

dXl XI 1

tit d6 PI = pfXI' d6 chfnh 1ii dinh lu~t Raun. Khi he thrrc nay dlt<JC nghiem dung vm moi Xl (duOng bieu dien la duOng thAng) thi thea he thdc Duhem - Macgulexo (IX. lOa), Mt buoc cilng phai c6:

dP2 :::: P2 = p~

dx2 x2 1

t1ic Iii P2 :::: P3X2 . Chi can mot cau tir nghiem dung dinh luat Raun b moi nong d¢ Iii cau tir thu hai cung phai tuan thea dinh luat Raun b moi ndng dt).

§4. £)INH LU~T KONOVALOP (1881).

SO SANH THANH PHAN HOI Val THANH PHAN DUNG DtCH LONG

1, Quan h, gilia ap suM hCfi bao hoa va nhi~ dQ sei eLla chat long

Trb lai hinh VIII-I, ta thay rang trong cac chAt long dem so sanh vOi nhau (nguyen chAt ding nhu hOn hop), chat long nao co ap suat hoi baa hoa caa nhat cr cung nhiet d¢. cMt long d6 se c6 nhiet d¢ soi thAp nhat.

56

D6i vOi dung dich long 2 cau tu, ap suat hoi toan phan cua no phu thuoc vao thanh phan cua dung dich, do d6 nhiet de? soi cling Ul ham cua thanh phan. Khi ap suat hoi di qua cue dai tai mot thanh phan xac dinh nao do thl d6i voi thanh phdn nay, nhiet d(} sci cua dung dich di qua eire tieu. Ngiroc lai, khi dung dich c6 ap sullt hoi toan phan cue tieu thl nhier de) soi cua no phai cue dai,

2. 51! khac nhau giU'a thilnh ph'n cua dung d!ch long va. thanh ph'n hCfi bia hoa cua n6. £)!nh lu,t Konovalop

a) Pha LOng Ia dung djch li luting. Pha hoi La h6n hop khi li luang.

GQi x 1 va x2 18. phan mol cua cau tu 1 va 2 trong dung djch long, YI va Y2 la phan mol cua chung trong pha hoi can bang voi dung dich long a T = const, PI va P21a ap sullt hoi rieng phan cua chung trong pha hoi. A.p suat hoi toan phan cUa dung dich la p = PI + Pl. Ta 'co, d6i vdi pha hoi :

P2 =PY2

Mat khac, vi dung dich long la Ii tuong, nen c6 dinh Iuat Raun :

dod6 :

o / 0

2:l_ = £l. = P2X2 hoac = Y2 YI = £l.

YI PI pfxI . X2/xl pf

H¢ thirc nay cho thay :

1) Neu P ~ = p f thi Y2/y I = x2/x I' nghia la d6i voi dung dich Ii tuong .eua 2 chllt long 1 va 2 chi khi nao ap sullt hoi bao hoa cua chung a dang nguyen chlft bang nhau (p f = p ~) a cung nhiet dQ thi thanh phan pha hoi moi bang dung thanh phan cua dung dich a moi nhiet d¢. Truong hop d6 rlft hiern, thf du co th~ MP- a hOn hop 2 chlft long d6ng phan quang hQC. Khi d6 ap suat hoi toan phan cua dung dich a T = const la

(IX.1l)

hang s6 va luOn luon bang p f . Thuc vay :

57

P= PI +1'2 =PYXI + P~X2 = PY(XI + X2) = PY (vi PY = p~ va Xl + X2 = I).

Duang bi!u dien ella P trong gian dO P - x la mot duong thAng ngang, song song voi true x. Nhiet d¢ soi ella dung dich d6 (0 P = eonst) cung la hAng so.

2) Neu p~ "* pf thl thlmli phan pha hoi se khac thanh phan dung dich long. Gia thi€t cau til 2 de bay hoi han cau tit 1, tlk ta p~ > PY (kbi them n6 vao dung dich If tuang n6 se lam tang lip suat hoi toan phan cUa dung dich). Khi d6, theo (lX.ll) :

'l1.>~ YI Xl

Ktt qua nay din tm dinh luat quan trong goi lit dinh lu4t KonovaLOp thu nlui't, do nha bac hQC Nga D. P. KOn6va16p (1856 - 1929), hoc tro cua D. L Mendeleep, kham pha fa nam 1881. Dinh lul~t Konovalop thu nhat c6 tM phat bieu :

Trong dung dich. hai eMt long, pha hai so voi pha long can bdng vOi 110 se tuong dOl giau cdu tu nao ma su them cau tu do vao dung dicit a nhi¢t d¢ khong ddi lam tang ap suat hoi tOOIi phdn eua dung dich, Utc Ja lam gidm nhi¢t d9 so; cUa dung dici: tai ap sud: do cho.

b) Pha long Ja dung dicit khong li tudng, pha hai la hon hap khi Ii tllung. Khi pha long la dung dich khong Ii nnmg, thl khong c6 he thirc t6ng quat c6 dang don gian (IX. I I ) nhu d6'i voi dung dich li tuang. Tuy nhien. dinh l~t KOn6va16p I van luon luon dung. Ngoai ra, trong mot s6 truong hop, c6 the c6 them dinh luat Konovalop II (khong c6 dinh luat , KOnOvalOp II d6i voi dung dich If luang ; chi dung dich khOng If nrong m6i c6 thtc6). Clthai dinh l~t t:Mu do D, P. Konovalop fun ra nam 1881.

D6i voi dung dichkhong Ii nrong, c6 the thiet l~p ca 2 dinh luat KOnOva10p mot each dan gian dua vito M thirc Duhem - Macgulexo

(IX. lOa) trong d6 ta thaY,xI bang l-x2 va thay dx) bang dx, = -dx2 0 T = const:

58

dpl! dXI == dP11 d(l - X2) = dp2! dx2

PI/XI PI!(I-X2) P2/X2

tUc Iii;

dPl dP2 PI x2

d(I- x2) = dX2 .p;- 1- x2

QUI y rAng ap sus:'t hoi 'PI va P2 ti l~ veri. pMn mol trong pha hoi, tUc Ul PI/Pz = yI/Y2 = (1- Y2)/Y2. do do, M thtk tren c6 th~ viet :

dPI dP2

-=- -

dX2 dX2

Tir P = PI + P2 suy ra dp = dPI + dPz. Chia 2 vt cua ding thee nay veri. dX2 va thay dPl/dx2 bAng bi~u thuc tren se duqc:

d?2 = t [1- L:~2 . 1~~2)]

= Y2 - x2Y2 - x2 + x2Y2 = Y2 - x2

(1- X2}Y2 (1- x2)Y2

dod6 :

~ = dP2 Y2 - x2 (T = const) (IX.12)

dX2 dx2· (1 - x2)Y2

Tir M thU"c nay nit ra 2 ktt It$l :

1) Neu (dp/dx2) > 0 thi bAt buoc (dPz/dx2) > 0 vi khi tang x2 (them dlin can til 2 vao dung dich long a T = coast), Pz c6 tang thi P toan phS! moi c6 the tang duqc. Khi 46. theo (IX.I2) phai co Y2 > X2 (hOi vi a mAt

5~

s6 co Y2 > 0 va (1 - x2) > O}. Nhu v~y Ia da thi.!t l~p duqc dinh' ludt Konovalop J d61 vOi dung dich long khong Ii tudng, phiu biEu nhu sau :

DOl voi dung dich long Ii tllUng ciing nhu khong Ii tudng, pha hoi so vm dung djch long can Mng vOi n6 luon iuon tuang d61 giau cau IU nao rna su them vao dung dich lam tang up suat hoi toan phdn cua h¢ a nhi¢t drJ khong ddi.

2) Neu (dp/dx2) = 0 thl vi (dPz1dx2) "# 0 va (1 - x2)Y2 "# 0 cho nen thea (IX.12) phai c6 Y2 = x2' Khi xay dung duOng bitu di~n p = f(x2)' tai nbUng dil~rn x2 nao rna (dp/dX2) = 0 thi tai d6, dtrong bi~u dien phai di qua eire tri (cue dai hoac cue tieu). Theo k€t qua vira rut ra thi tai nhfrng di~Ii1 cue tri do, thanh phAn pha hoi phai bang dung thanh phan pha long can bAng v6i nO (Y2 = x2)' Di~u nay cling phai xay ra tai nhtmg di~rn irng vOi eire dai hay cue ti~u tren duemg cong nhiet d(l soi cua dung dich theo thanh phan dung dich (bbi VI eire dai v~ap suat hoi cua chat long trng vOi eire tieu v~ nhiet d<) soi cua no va ngiroc lai),

Ket qua do dAn tOi dinh. lu<it Konovalop II d6i voi nhfrng dung dich khong If nrong nao rna ap suat hoi roan phan co sai lech duong (so voi dinh luat Raun) tm rmrc co cue dai hoac co sai lech Am toi mire co cue tieu. Dinh luat Konovalop II phat bi~u nhir sau :

Diem cue dai hay cue tiiu tren duang cong bitu dien rip sua' hoi toan phdn (11O{ic nhift d¢ soi} cua dung dicl: theo thanl: phon ctia dung dich ung vOi nhiing dung dich co thanh phon bang thanh phdn ctia hoi call Mng vai n6.

Nhtrng dung dich nhtr the goi la dung djch dang phi.

3. Hbn h~p ding phi. Dung dich hoac hOn hop dang phi con dUQ'c goi la Mil h'1P ;so; khOug d6i (azeotrope, tu nhttng chir Hilap Zeo "" s6i. a"" khong va tropes "" thay d6i). nghia la nhttng hOn hep long do soi (} nhi¢t d¢ c6 djnh, khong doi, gi6ng nhu chat long n¥uy~n chit (dl nhien dum ap suat khf quy~n ngoai khong doi). Khi cat nhfhig hOn hqp dang phi th] ta thu dug<: ngung dich co thanh phAn gi6ng het thanh phan hOn hqp do. Do do, v~ nguyen uie, khong th~ nao tach dllQ'c hoan toan nhnng du tu ciia hOn hop dang phi bang SI! cit "ding ap", nghla Iii. tip suit khong dilL

D6i voi hOn hop dang phi, khi lam thay d6iap suit thl khong nhtrng nhi¢t d(l sol thay doi, rna ca thanh ph;'!,n cua hOn hop dang phf ding thay dOi, di~u nay chung {o Mil h'1fJ ddng phi khong phdi 10 nhiarg IU1P chdt hail hoc co thanh phAn xac dlnh nhu tnroc kia

60

ngum 18 tUang lAm (dlWi. nhilng ap su& khac nbau, nbilng bi;1p ch~ xac dinh sOi a nhUng

nbi~t d(l khac nhau nhung thAnh ph~ clla cbung kbOng thay dOi). __

Thi d1.l diEn hlnh ve hOn bgp ding phi la Mn hlfp nlliK rllflU ety/ic CzHsOH. hOn bgp , nay sOi {J t '" 78,15°C (cl,TC titu nbi~t d(l sOi, vl nbi¢t d(l sOi Clla mwe nguytn chit la , I = 100°C va cua ru(ru etylic nguyen cb~ lit t = 73.3°C) ,tP ap suA"t kbi quytn ngoBi 1 atm, I'tng vm thAnb phan ding phi lA 95,57% kh6i hJQIlg CzHsOH, tac la 89,4% mol CzHsOH trong bOn hqp ding phi. Thanh ph~ ding phi Clla hOn hop ding phi nuac - JUQ'U etylic thay d6r theo ap sU(1 nhu sau : '

Ap sliA"t, aim 1,0 0,5 0,25 0,125

% mol CzHsOH 89,4 91,5 94,1 99,7

lItc la thanh phl10 ding phi cbuyto dich d4n ve phia ruqu etylic nguyen eMI khi lam btl th4'p d4n ap su4't. BAng each d6 c6 the thu dugc IUQU etylic thl,TC tl nguyen cb4't. Toy nhitn phuong pIIap nay thOng kinh It,

Cu6i cUng, ve h6n hgp ding phf, 18 c6 tht dua ra nh$n )tel sau day: HtIn hlfp ddng phi ld Mn hlfp co sai {feh to, da so vill tlnh Ii tlfdng rna van bdo toan dllrfC tinh tan hocln toan VelO nhau thea Mt ki Ii If noo cua hai cdu tU lOng; m(ll sai l~b nbo, ph1,l them, d6i v6i doh If tuOng, se lam cho h6n hqp tacb ra thanh boo 1~ long ritng re (hi~ lUQIlg chia Idp), tiic la lam xu4't hien nhiing vlmg c6 tfoh tan h~ eM clla hai t(u tit long.

4. Gilm do ap sui:t .: thanh ph'n, nhltt, dQ sol - thanh ph'n. IDnh lX-7 trinh baygian dO ap sulft hoi toan phancua dung dich theo thanh

ph~ (cQt A), gian dO nhi~t d¢ soi - thSnh pMn (C¢t B) va gian d6 Y2 - x2 v~ quan M so sanh gina thanh pMn pha hoi va pha long (C¢t C) d6i v61 nhiing truong hop Wc nhau nhu sau :

Hang I - Dung dich If tubng ;

Hang n - Dung dich khOng If tuang c6 sai lech dirong ve ap sulft hoi chua t61 rmrc c6 cue dai ;

- Hang III - Dung dich khong if tulmg c6 sai lech am v~ ap solft hoi chua t6i mec c6 cue tieu ;

Hang IV - Dung dich khong- if tuang c6 sai lech duong tm mac as cue dai ap sulft hoi va do d6 c6 cue tieu nhi~t dO soi.

Hang V - Dung dich khong if tuang c6 sai lech Am t6i rmrc c6 C\IC tieu ap suat hoi va do d6 c6 C\IC dai nhiet d() soi.

CQt A III nbilng dmmg ding nhi~t ve ap sua:t boi loan ph4n Clla dung djcb theo thAnl pMn dung djch (dmmg mSI li~n p - x2) va theo tbltnb ph4n cfla hoi_ (dubng cham chfn

61

p - Y2)' ThAnh phlln dung dieh long meu thi qua phlln mol x2 ciia c{u tir 2 va. thanh phan cua hoi bieu Ihi qua pblln mol Y2 Clla c6u Iii 2 trong pha hoi ~u dUl;lC ghi tren ding m~t fn#: lwanh. ani y dog hai dm:mg p - x2 va. p - Y2 bao gii':! cling g~p nhau I~ hai dl1u mut pi va ~ I'mg v6i cll"u tir I va 2 nguyen chil"I : thAnh ph40 pha long va hoi eua eung mQt cbll"t nguyen cbll"t bao gib ciing bang nhau.

Cling chu y ring dm:mg P-Y2 (cUm cham) bao gio cling a dmii duang p - X2 (nel Ii~n). Dtrong ding nbi~t p-x2 gQi III dJlilng lOng (Iitng La Tinh liquidus = duang long). N6 III bien gioi eua vimg pha long "d6ng the 11 nen n6. DLri':Ing ding nbi(!t p - Y2 goi la dJlitng /wi bay dJlilng suang, N6 III bien gim· cila vimg pha hoi d6ng the 11 dmji n6. Vung mUn giita dlti':log Ibng va dlti':log hoi la vung di Ihe c6 hai pha long va hoi t6n tai d6ng!hOi. -

ani y ring duang P - Y2 bao gii':! cling III m¢t duang cong, du ring dWog P-X2 luang I'mg v& n6 c6 the la duang thing (llUang ~qp dung dieh If tuOn_g).

CQI Bill nhllng dUt'Jog ding ap v~ nhi(!t de) bAt d'u s6i Clia dung dich theo thltnh phlln dung dich (duang nelli~n I-X2) va theo thanh pb!n Clla hoi. (duang cMm cham I-Y2)' Thanh phlln dung djcb 10Dg (X2) va thltnh pUn hoi (Y2) duqc gbi tren caeg mI)l trqc hoanh gi6ng nhu lruang hqp nhilng giAn dIS thu¢<; CQI A.

Clni y khi cbuyen Ilr.:(ll A sang B th] quan h(! bi dAo nguoc, Q(u Iii I nguyen chat c6 ap sull"l hoi bio hoa thll"p thi e6 nhi(!l dl) s6i cao con cll"u Iii 2 nguyen cbll"t c6 ap suM hoi bie hoa cao thi c6 nbi~l' dl) sOi IMp (0 cae giAn dIS tren hloh IX-7), c6u tir 2 luon luon duoc gil thit't Ill. c4'u tir c6 ap sull"l hoi bio hoa cao), Duang t-Y2 (thanh ph4u hoi, duang cbll"m ehll"m) Iuon 0 tren d~ l-x2 (thllnh ph40 dung dich long, duang Det li~n). Duong t - X2 la duilng lOng. bien gimcua vung pha Umg d6ng the a dmii n6, con duang t-Y2 1ft duemg hdi hay 4J101lg suang, bien gim eiia viing pha hoi d6ng tM 0 tren n6. Vr.ng ben trong duang Ibng va duang hoi 1ft vung di the hai pba long vll hoi can bang vm nhau.

Diem C\!e dai trtn duOng cong ap sull"l hoi Ung vm CI!C tieu tren (luang cong nhi(!1 dO s6i va nguqc lai, T~ nbllng diem d6, thee dinh lu~t Konovalop n, dung dich Urng va hoi bie holl ciia n6 c6 thsnh ph40 b~g nhau, x2 = Y2 (dung dich ding phf), N6i each khac, ~ nhllng diem 116, diWng nelli~ (thAnb ph4u dung djch long) va duang cham cbll"m (thllnh ph40 hoi) phii glJ,p nhau,

D6i v6i giin d6 nhi~t dl) sOi - thsnh pb4u (CQI B) cac duang l-x2 (net 1i61) vi t-Y2 (chll"m cham) c:Uu III dtWng cong (k6 ci trui':lng hep dung dieh If tltang. TIl"I eli chi c6 3 d~g gian d6 nhi¢t d~ wi -Ihilnh pilAu, dang thu nhf'1 III met hlnh Ihoi khong co cl!C tri, Ung v& 3 hang ,diu It II vll III, ~ thfr hai, Ung vm bang IV c6 Cl!C tieu va dang thu ba, Ung v& hang V, c6 cucdai,

62

A B C
Pt ri'2
q

I ~
pOl >-
° X2 Y2 O_ -X2 ° - X2 (l)
---- X2
4JtI~'
II "
....
....
............. -",. .... ". III

IV

V

Hlnh /X-7. NhDng ~ gian d6 kh6c nhau ~ can bAng lorig - boi a h~ 2 eMf lOng boa tan hoan tosn vao nhau thOng h~ eM.

......... -. ... ,

....

....

.....

<,

.... ...

63

§S. SVCAT HON HQP HAl CHAT L6NG

Khi. nang tach dung dich thanh nhihIg clu tit Clla n6 nho chung eft dJ!3cbu y€u vao s., khac nhau ~ thanh ph4n can bang cua pba long va pha hoi.

1. ca phin d~n

ScI do nguyen tic edt ph4n do~n trlnb bay treo hlnh IX-S. H60 hW loog ban dau

'thanb phAn xI soi 0 diem LI can bAng v6i. luqug hoi oho dAu tien HI thlmh pilau Y I· 51! agung t\l W: c8. lugng hoi nay cbo luqug nbo ngilllg dich dju tien L.! thanb pb!lo lt2 "'" y I· Dem c4t ngilllg dich nay 14n thu bai, thu lugng nbo hoi dau tien H2 cua n6, thloh pbAn Y2 r6i lai lam agung t\l tat ca luqug hoi nay. dUQC hrong nho ngirng dich thu hai ~ thanb puIn x3 = Y2. Dem ca't ngung (ijch nay 140 thU' ba, v» ... cU' th€ titp t\lc mai, cu6i cimg thu duqc mOt lugng nh6 ngimg dich chua clu tii B (de bay

hoi) nguyen cblt. Nhtr v~y. ct{t phan doan la s., I*p di I~ I~ cal nhieu ltin nhilng dOng tic sa cf"p hoa hoi va ngung tu, MC,i dOng tic boa bai. va ngung t\l duqc phan anh tren giim dO bAng mQt b4c thang, thi d\l LI HI ~.

TID I~ bOn hW loog ban to B dau. VI n6 mi't mOt lugng nM

hai HI nen diem bieu ditn x 4 1 ciia .06 dich sang ben trai

ditm LI mOt ft, thf du L~ (hlnh IX-9). s., ci't pilau

f· A

p=const

1

o A

x,

------- xB

Htnh !X...JJ. Nguyen cic Ct{1 phAn doan bOn hop 2chW loog

1

o A

x' ,

Hinh fX:.9. art phi1n do;pt

64

do~ ti6t hAnh d6i v6i. chAt Ibng L~ Mng dufu1g b~ thang L; H; t.; H; L; ... cling se cho rrn)t hrqng nho B nguyen chft ce)ng them vao hrgng nho c:fAu ti~n dii thu dlll}C theo dufu1g * thang LIHI~H2~H3'" (nen hlnh IX-9, dUCntg nay gbi bAng net IMn). Chft long L; tro thlob L~ a ben trai L; m()t it. Nhb c!t phan d~ n6 I~ cho mOt hrgng nM B nguyen chIn. Nhu v~y Illgng cau tir nay d4n dAn tang len trong khi diim biiu dien clla chft long ban d4u chuyen dieh dAn ve diem tA' nghia la blah cit ban dlu cu6i cung sf chtta chft lbng A (kh6 bay hOi.) nguyen cMt. COng bAng each d6, nhOng ph4n chin Umg ~, ~ •... L;, L; •... clIng chuytn dich dlin ~ phia diem tA va Cling cho A nguyen chft. Nhu v~y sf tach dlRJC hon hop long ban dAu thanh A nguyen chit u binh cft va B nguyen ch!i a blnh ngung hoi,

Trong san xuat cung nhu trong phong thi nghiern, Sl! c!t phAn doipl duqc ti~n hAnh dllm dang m()t qua tr'inh lien tuc trong d6 nhfmg dOng tac hoa hoi. va ngllng tl.! tUng ph40 dllgc lI! de)ng hoa, ngoai ra con v~ dung cl phlWllg phap dQj luu, nghia la biw dam cho hai pha (long va hoi) chuytn de)ng thanh hai dong nguoc chieu nhau va ti~p xuc nhau. Qua trinh gQi la tinh cat.

2. Ttl.tCJng hqp hbn hqp ding phi Htnh IX-to iiog v6i. h(! c6

CIfC til" IIhi~t ~ s6i. Gia thit ta xuft phat til mQI hOn hqp a ben tnii diem dAng phi e. Khi pha long L sOi a nhi(!t de) t, hoi. can bAng v6i. n6 c6 thsnh ph40 H, chua nrong d6i nhieu ciu lit B han pha long. Do d6 n~u tiep We sl! eft theo k.¢u cit phan doan thl phlfu chil long con I~ trong binh cM se titn dlfu den A nguyen cMt con ngung dich se tien lUi 11611 Iufp ddllg phi c6 thanh phan Ung vm diem e, tm dAy hOn hop dAng phi sOi khOng thay dOi thanh ph!n nila (a lip suit khong ddi) va do d6 khOng c6 dQng Il!c cho sl! chung cit nita. Nhu v~y khOng lhi nao tach dllgc hoan toan 2 dfu ni A va B CM h6n hgp ban d4u.

: e

,

o (A)

1 (B)

m~ih IX-IO. Gian d6nhi(!t dQ sOi - thanh ph'" d6i v6i. h~ 2 c4"u ni c6 CI!C tieu nhiet de) s()i

Ciing c6 thi n6i nrong nr nhu v~y nc!u h6nbgp ban dliu a ben phai diem ding phi e.

Pha long L' sOi a nhi¢t de) r va chUa tlWllg d6i nhieu ciu tir B han hoi. H' can bing vm

65

n6. Do d6 ph&! chili long con 1~ trong bloh clll se lien din Wi. B nguyen chili trong khi nglmg dich tit;1 dan tili Mil h(1p ddllg phi e.

ve M co qIC tieu nhi¢1 dt') sOi c6 tM ke b¢ H20 - CzH~OH ; H20 - CHQ) V.v ..•

D6i v& M co clfC d~ nhi¢t d¢ s6i, ta cfing Ihu dugc: nhltog ket qua ttrong tJ,I nlnr tren nhung dao nguqc I~. Nhitng h¢ nay .thu<mg (I g@ han h? c6 c!JC tieu nhj~1 dt') sOi. CO the ke h¢ H20 - HQ va M H20 - HN03•

Ell! t6m tat, c6 lhi! n6i MIl h{1p dt$lIg phi co clfC tiiu IIhi¢t d¢ so; Iii IIgtlng dich cum cUlig trong s/f cdt phtill doan 0 ap suat kMng d!1i con Mn h(1p ddng phi coclfC d(}i nhi/t d¢ so; Iii phdn COli Igi cu(J1 cilng trong billh cat trong s/f cdt phdn doan do.

66

CHillNGX PHUONG PHAp HO~TaQ

§ 1. HO~T ElQ vA He s6 HO~T ElO

1. Thi' hoa hqc cua cau til trong dung d!ch If "'dng vi trong· dung d!ch thvc nhung loing

D6i vm moi dung dich long, ll tlrang hay kbOng, can bang vm hen 00.0 hoa cua no, U Tva p ngoai kbOng dOi, neu cfu ti:r i cO ~t ci trong pha lOng (L) va hen (K) thl dieu kien can bang la :

(X.I)

fi la hoat ap cua i trong ben; ~j (1) Ia 56 hang chi phI.! thuoc vito ban cMt cua i va vao T,

a) Nlu dung dich Iti Ii tuUng. ta co dlnh lujj.t Raun fj = f{'Xi v6i moi xi, do do (X.!) tro tbanh :

fiO la hoat ap cua i long nguyen chll:t U cung T va p ngoai nhu dung djch ~ vi fj chi phu thll¢C vao i va vito T, p, nen cO Ihe g~p 2 50 hang d!u v€ phai ding Ihllc tren thanh mQt s6 hi;lllg chung :

~j (T, p) = ~j (T) + RTln fio (X.2)

dodo:

~ = ~j (T, p) + RTlnxi

(X.3)

ani Y Ill' (T. p) la Ih€ hoa hQC cua i long nguyen chft (xi = I). n6 phu thuec cM yeu vao T, rtt II vao p,

b) Ntu dung dich IQ khong Ii tflfing nhung lodng' (chfnh xac la vO cung loang), dung mOi I vin tuan theo djnh lu*1 Raun, do do Ih€ hoi hQC cna dung mOi van co dang (X.3).

COn chft tan i (i ~ 2) tbllulln theo dinh IU*1 Henry fj = kiXj. he s6 Henry kj '#- fio, nola

hWig s6 a T,p const, tllY theo tnri:mg hop, kj cO the Urn han hay be han fio• Khi do d6i vOi' chit tao j trong dung dich loang, (X.I) 1rc'J thanh :

67

J.li = Ilf (1) + RTlnkj + RTlnxj

Vl kj chi pbl} thU¢C vao i va vllo T, p nen cOng c6 tb! dil.t :

Ili (1', p) '" Ili (1) + RTlnkj

(X.4)

Khi d6 tbl! hoa hQC Clla cMt tao i trong dung djch thl.lC va loing ding se c6 dang (X.3). Nbung Ilf (1', p) trong (X.4) thOng phii la tMho! hQC ciJa ddt tan j nguyen chID: vl khong the ng~ suy tm xi = l. .

2. Ho9t d9 VB h; so ho,t dq

D6i v6i dung .dich thuc va khOng du loang thi fj la mot ham phuc tap eua xi' do d6. theo (X.l), th~hoa hoc IJ.i = J.lf(T) + RTlnfj cung la mot

ham phec tap cua xi. clnr khOng e6 dang dan gian (X.3). ~ bao toan dang dan gian (X.3) cho th€ hoa hQC J.li nhu d6i vm dung dich If tuang va dung dich loang, ta thay nong dO xi bang mot dai hrong moi ~ goi Iii.

hoat dt) cua i sao cho : .

J.li = J.lf + RT/n~

(X.5)

J.lf 18. th~ hoa hQC cua i a trang thai chudn (c = chuan) la mot trang thai quy UOc rna tai d6 J.li = J.lf. Khi d6. tu (X.5) suy ra ~ = 1. V~y a trang thai chudn, hoat dt) cua i pMi bOng dan vi.

Dua V8.0 (X. 1 ) c6 th~ vi€t. d6i v6i trang tMi chudn cling nhu d6i vm M"t ki trang thai can bAng 08.0 We :

J.l~ = J.l? (1) + RT/n f.c

I I I

Uy (X.l) tnr di phoong trlnh nay. se dugc:

c fi

J.li - J.lj = RTln -

fF

1

Tir (X.5) ta e6 :

J.li - J.lf = RTln~

68

CiI cLJ

(X.6)

Hoat d(j ai cila m(jt tau ta j oong tl s6' giiia boa: tip cila i trong hai bdo hoa Ctta dung djch va hoa: tip cua j if trang tluii chudn if cung T va p ngoai nhu dtfi vUi dung d!ch .:

Mac dO sai l¢ch cua i trong dung dich thuc so vOi nhitng dinh lu~t v~ dung dich Ii tuang hay dung dich loang c6 th~ ~c tnmg bang h¢ s6' hou dtj Yi la ti s6 gina hoar dO va nong d() cua i trong dung dich thuc :

a f·

Yj=_=_l_

X· fex·

1 i I

(X.7)

3. Y nghTa cua ho.t dQ

Trong dung dich thuc, nong dl) khong con 18. d4i hlQ'ng d4c tnrng da.y do cho dung dicn nhu d6i vm dung dich Ii nrong hay dung dich loang,

Hoat d() IS. ham duoc dua ra(l) de thay cho n6ng d¢ trong dung dich thuc, CUng nhu nong d¢, hoat dt) Ia fTiQl d{li luang cuang d9. D6i voi dung dich thirc, viec thay nong d¢ hang hoat dO ding gi6ng nhu viec thay ap su~t bang hoat ap d6i voi cac khi thuc,

CO the coi hoat dl) la mot thii n6ng dl) hOu hieu, mot thii nong d¢ hoar dong, mot th(i n6ng de) da hieu chinh rna tai d6 dung dich thuc dat diroc nhtmg thuoc tinh eoa dung dich If unmg hay cua dung dich loang,

an h.ru y lit viec thay n6ng d{l bang hoat d¢ cling nbu thay ap suat bang hoat ap la chi duqc pbep a nhtmg phucmg trlnh d*"c tnmg cho can bang va suy ra tnrc tilp hay gian tilp til' viec sir dung the' hoa hQC cua cac cAu tiro Thi du, d6i vdi dung dich th11C. dinh IJl4t pluin b6 se bieu thi dutti dang :

a'

- ==const a"

(I) Hoat dl) la do Liuyt (G.N .Lewis) de ra nam 1907.

69

§2. CHQN T~NG THAI CHuAN

Trang thai chuAn la trang thai rna tai d6 J.li = J..I.f va. ~ = 1. D6i voi hoat dQ va h¢ 56 hoat do, viec chon trang thai chuan cua cac cau tiI Ia tuy y b rnec d¢ naO-d6.

N6i chung, nen chon trang thai chudn sao cho khi dung dich thuc dat duoc tinh cMt cUa dung dicit Ii tWng hay cUa dung dich lodng thi hoa: diJ trung vcn n6ng df). khi do hf si/ hoa: diJ n = 1. C6 hai each chon,

De don gian, ta gia thiet pha hdi Id ii tUdng. khi d6 fi = P. (X.6) va (X.7) trb thanh :

p' ~=_I

pf

(X.6a)

'Yi = ~:=....£L '(X.7a)

X. c

I PjXj

Tren hlnh Xe-I, duemg cong net 1i~n la duemg bi~u dien ap suat hoi Pi (gm thi€t c6 sai lech duong so. vOi dinh lu~t Raun) b

p, I

T=const ~ .. /

''>.'l.;;::.<:A,,~/'

"p "

.... ,,,,.~"

"

",~,""--~ _..-~

k· I

o

CAB

Hinh X-l. Hai each chon tr,plg thai chuan.

T = const cua cliu til i

trong dung dich khOng li tubng theo thanh phan Xi cua dung dich, Nhtmg duang tMng chech cham cMm Ia nhitng dubng Raun va Henry.

Goi Pi la ap suat hoi tai diem c6 nOng d~ Xi = OA .

1. each I chen tl1jlng thai chuln

N6u i xiI sl,l' If lubng, n6 se co ap suat hoi Pi tai nong d¢ ung v6i OB

- - I

sao. ChD Pi = pf .OB (dinh lu~t Raun). D~t OB = a • ta dttgc :

70

a~ =!.L

1 °

p.

I

rxs:

So sanh voi (X.6a) ta tba:y pf = pf. nghia 130 trang thai chudn CM i [Q. trang thOi CM i nguyen chat a cung T va p ngoai nhu dung dich ; a: 130 hoat dl) cua i khi trang thai chuAn cua i dugc chon nhir vay (goi la each I). Khi d6(X.7a) trO thanh :

I

I 8i Pi

y. =-=--

I X. pOx.

I i I

(X.9)

(x.g) va (X.9) cho tha:y OJ va r; di~ khong co thu nguyen.

D6i vm dung dich Ii tudng, Pi = pf Xi' do d6 'Y! = 1 va a: = xi' Neu dung dich thuc co sai l¢ch dudng so vOi dinh 11$ Raun, Pi > p f xt till 'Yi > 1 va a;_ > Xj' Trong trlJI3ng hop co sai lfch tim, Pi <. p f xt. 'Yj < 1 va 8j < Xi·

CM Y khi chon trang thai cua i nguyen cba:t lam trang thai chuan,

nghia la c6 aj = 1 khi Xi = 1 thl tir (X.3) va (X.5) suy ra flf = flf (T. p), do d6 (X.5) tra thanh :

Ili = ~f (T, p) + RTlna;_

(X.IO)

Vi Ili = Gi va J.lf (T. p) = G f la ham Gipxo hay thl! dAng ap d6i v6i 1 mol i nguyen cba:t, cho nen :

Gj = G? + RTltl8j 2.C~chllch9ntr,ngthaichuin

N~u i tuan theo dinh l~t Henry. n6 see6 ap suat hoi Pi tai nong d(> img voi OC sao eho Pi = kj. OC (hlnh x-n. D~t OC = a:', ta duqc :

(X.Il) .

a~l = Ei (X.l2)

I ki

So sanh voi (X.6a). ta thay pf = ki• nghia 18 trang thai chuAn cua i la trang thai tim dl1l;"C bang each ngoai suy dltOng th!ng Henry tren hmh X-I

71

cho tm xi = 1. Trong thirc t~. i chi tuan thee dinh l~t Henry khi n6 18. ' chat tan trong dung dich loang, D6i v61 dung dich thuc, khOng du Ioang, ~c bier khi xi --+ 1, dinh luat Henry khOng ton tai, Do d6, trang thai thu duoc bang each ngoai suy dubng thAng Henry cho t61 xi = 1 chi Ia mot trang thai gia dinh, khOng c6 thuc, Nhung chinh trang thai gia dinh nay lIP duqc chon lam trang thai chuan thee each II. N6 thuong duqc dung khi i ro ret Ut chat tan, chi tan c6 han vao dung moi (coiu tll 1) va khong hinh thAnh dung dich li tuOng v61 dung mOL Khi d6, trang thai chudn Clla chd: tan i (i 22) La trang thai khang co thuc cua dung diet: co n6ng d9 cua i bdng dan vj (xi = 1) rna tai do ap suQr hoi cua i Mng h~ sf! Henry kj cua i trong dung djch VD cung IOOng.

Cach chon trang thai chuAn nhu v~y lam cho h~ s6 hoat d¢ Yi ' theo (X.7a) co dang :

a· p. p'x·

Yi =_1 =_1_=_1_1

X· k.x, *x·

1 1 I Pi i

(X.13)

om * Ung v6i dung dich yO cllng loang trong dO, thee dinh ll$ Henry, pi = kj xi . ~ thlk (X. 13) cho tM'y aj va n aeu kMng co llui nguyen.

D6i vm vung dung dich loang tuan thea dinh luat Henry thl <Lj = xi va Yi = 1. D6i v6'i moi vung khac, Sl! sai lech cua he s6 hoat d¢ Yi so v6'i 1 se cho mot y ki6t v~ sl,l sai lech so v6i dinh lu~t Henry.

The hoa hQC cua cMt tan 2 trong dung dich khOng lf tuOng c6 dang :

J.L2 = J.L1 (T,p) + RT/na2 = J.L~ (T.p) + RT/ny2x2 (X.14)

J.L~ (T.p) khOng ph8i Ia the hoa hQC cua cau tir 2 nguyen chat rna la th~ hoa hQC cua cau tiI 2 b trang thai chuat. (khi a2 = 1). The hoa hQC cua cac choit tan i khac (i <:: 2) ciing c6 dang tuong lJ! nhu vay,

Chu y rang d6i v& trang thai khOng c6 thuc cua dung dich dllgC chon lam trang thai chuan, <Lj = 1. Yi = 1, thl trai lai, d6i v6i trang thai c6 thuc Clla i nguyen eMt (khOng ph8.i 1A ~ thai chuan), ta co (X; = 1, P = pf) :

72

(X.15)

3. Kift lu~n

Dt ket lu~ va rna r(tog nbUng ket qua tren, ta xet tnrCmg hQp tdng qual khi pha hCJi kh6ng phdi Iii Mil hf/P khlli luUng. Khi d6 cae h¢ IMe l£tn van dung, nhung phlU thay p; bbgf;.

D6i vOi moi du tir i, chi c6 met djnhnghia duy nhit ~ hoar dQ ella n6 ; II; =: fi/f~· Tuy nhien tuy then each chen I~g tbai eliub rna II; se nb~ nhUng gia tr1 bing 56 khac nbau.

Theo cach J, thutm.g duqc dung khi cac eMt long i hoa tan vao nhau then Mt kl Ii I¢ nao va dOng va; Ira tuang duung nhau trong cac thuQc tfuh ella dung djch. ~g thai. ehu4n coa i la trang thlii thuc clla i nguyen chit CJ cling T va p ngosl nhu dung dich (f = fi). Khid6 :

I f· I p.

a: = ..:L hoac a = _..!._ (Illu hoi III Ii" Illbng)

, fO . 0

i Pi

Khi cae caw lli'dong vai Ira kMng 'U(lIIg dUcl1lg nhau. nghia la c6 m(»: ellu lli r6 ~t fa dung mOi (cA"u lli I) cOn cac c4"u IU khac II. cMt Ian {gQi III du ta i, i :!: 2), nhUng ciu ta nay chi tan c6 hliUl vao dung moi, thi tl1IDg thai chulln Clla dung mOi 1 van theo each 1, Idc III tr~g thai th9"C cUa dung moi I nguyen chit.

Chl d6i vm cool tan i (i 2: 2) khOng hlnh thanh dung dich li Illbng v6i dung mOi ngum fa mm chen ~g thai chuAn theo cach JJ:tl1IDg thai chu4nn. t~g thai thOng c6 th9"C clla dung dich c6 n6ng de) coa i bing don vi rna tl!-i d6 heat lip (bo~ lip suit hail Clla

i bing h¢ 56 Henry ki clla n6 trong dung dich vO cuag loing (fic = kj). Kbi d6 :

a!l· = .!L hoac a!' = Pi (nlu hci Ill. If tllbng)

, ki ., ki

NhOng gia tr1 Clla 3j thea hai each thac nhau.ehen tl1IDg thai chub lUOn luon a vic

mQt ti I¢ khOng dOi. thong phI:! thuec vic Xi. Th9"C v~y :

a! k· a! k·

-' = _..!. = const boac -t = --;, = eonst (X. 16)

a~ fi ai Pi

Ghi chu. DOl vm Mn hqp khi. nguM ta chon t~g thai. chudn coa khf i la traag ihAi ciia khf i nguyen chit b coog T va P cbung nbu trong h6n hQp va chip nhan a trang thai

nay fic = fj = I.

Vi II; = f,;f. it dAy Cf = I, do d6 d6i v6i khi i, II; = fj tile la 1w{1.1 dq Clla khJ bdng hOf!t apcUan6.

73

D6i v& khi II tuang, ho~ lip bAng lip suj(t, fi '" Pi' v~y Il; :: Pi, tuc la ho(Jt d~ cua khi Ii ,"nng bdng tip suat cua lit}.

§3. HO~T aO vA He s6 HO~T aO THEO NHUNG THANG N6NG £)9 KHAc NHAU

o tren da trlnh bay ho .. t d() va M s6 h~t dQ theo thang n6ng d() ph4n mol x. Khi i chi tan c6 han V30 dung mOi va ro ret IA cha:t tan thl ngom thang x, ngum ta con dung hoar de) va h~ s6 h~t d¢ thee nhilng thang n6ng de) molen m va n60g dQ mol- tilt tich c.

Thang n6ng dQ x : !lx = 1 x·x Thang n60g dQ m : a.., :: ym·m Thang n6ng de) c : 3c = y c'c

Khi d6 the hoa hQC Jl clla chj(t tan cO th~ bitu thi thee me)t trong ba each sau (ta ki hi~u Jl thay cho Ili cho ti~n) :

Jl = Jl~ - + RTillax = Jl~ + RT/1I1x'x

(X.17)

D6i v6i mQt chat tan lrong dung dieh aT. p va thlnh ph4n dii cho, the hoa hQC Jl clla n6 chi c6 mQI gia trio Nhung vi x ~ m ~ c va Il~ ~ Jl~ ~ Jl~ cho nen cac hoat dQ!lx. a.." 3c nh~ duqc nhilng gii trj khac nhau; d6i v& Y". 1m. 1c cOng ~y.

Yx goi Ill. h~ s6 h~ de) thudn li, 1m gQi Ill. h~s6 hoat d() tlu!c d,!ng hay h~ s6 ho~ dQ molan, dove dimg phO bien cho chj(t di~n phan trong dung dich cMI di~ phan, con Y c £1 dung han.

D6i v6i cMt tan, each chQII trang tbai ehuAn trong thang m hay c cling tien hanh d~ do dinb lu.t Henry nbu trong thang X. b trang thai chu4n. Jl = Jl~ (hoac Jl~) va a.., (h* ~) = I. Oii thiet pha hoi lil " tuOng. Trong mOi trlKmg hgp, ngum ta ciing x;1y d\lllg nhitng dui'mg bitu dien ap sulft hoi P2 theo n6Dg dO m h~e c (hlnh X-2) a vimg o6og dQ tMp ma tai d6 dinh lu.t Henry Pi = km .m" hoac pi = kc _'c· dugc tuan theo r6i ngoai suy cho t& n60g dQ dan vi bAng each gii dinh clog a n6ng d() DAy, van c6 dinh 1u4t Henry. d ~g thai giadjnh nay. chlft tan se cO ap sufi hoi boog km ho~ k..-

74

Nbu V.y. d6i v6i cbAt tao, t~g thai chuAn trong ca 3 thang nOng dQ x, m hay c Iii trang thai gii djnh (khOng c6 thl,l'C) cua dung dich c6 ndng dQ ella ch4't tao bAng dan vi rna t;p d6 ap suKt hoi cua chAt tan bing h~ 56 Henry cua n6 trong dung dich

vO cung loing. .

V.y ~ = km = P2/m· h* P2 = ke = Pi Ic· (chu Y phart biet chi 56 e 6 can la chi trang thai chUAn v6i. chi 56 c a chan la chi nong dQ mol- the tfeb c).

Theo djnh nghia, ho., dQ cia chAt tan lila = P21 P2. TIt d6 ;

1

_m

Hlnh X-2. TI'II-Qg thai chuan dOl v6i. chA't tan trong dung dich kbOng Ii tu6ng theo thang m.

a =h

m km'

am P2/m P2/m

1 =-=--=--

m m "m P;/m·

(X.18)

Nhilng M thltcnay gi6ng het nhitng M thm: (X.12) va (X.13) di thu duqc treng thang ndng dQ x.

Qul Y rAng, ddi vOi cluft tan, ni'u hoq.t ~ theo thang x Ic2 ~ d¢ IlI{1ng kMng co thit nguyen thi, traj I(li, hO(lt d~ theo thang m va c td t1t;Ji lll¢g co tht nguyen ella nAng~.

'" '"

ThI,l'C v.y, theo tbang molan m, h~ 56 Henry Iii k", = p 1m ,do d6 ;

a =h=!2.m·

m km Pi

Vi ti 56 P21 Pi IchOng c6 thlt nguyen. nen 3m c6 tM nguyen cila ndog dQ molan m (moVIOOOg dung mOil. Cilng tuang tl,I nhu v.y, ke = .,; Ic· va:

a =~= P2 c·

e k •

e P2

do d6 ~ c6 thlt nguyen Clla n6ng dQ c (molrl),

Cic he 56 ho.,t dQ lx, lm.le thlluOn loOn la nbitng d!.li hrqng thOng c6 thd' nguyen. D6i v6i. chfl tan l1 ~g thai chuAn, ho"," dQ bing nong dQ va bing dan vi, di~u nay dung trong ci 3 thang x, m va c:

75

a.._=x=:l;

a",=m= 1;

a.,=c::1

Yx = I Ym = I Yc = I

H~ s6 hoat de) cua chft tan cUng bAng I trong dung dich vO· cung loing; Y; = 1, a~ = x": y~ = I ; a~ = m": y~ = 1 ; a~ = c",

D6i v6i dung dich du loing de cac n6ng d¢ x, m va c tl I~ v6i nhau, cac h~ s6 hoat dQ YX' Ym va Yc dp xi bing nhau. Ntu dung dich dqrn d~ hen Ihl My gio YX' Ym va Yc f6

nbUng gia tli khac nhau ro ret, .

§4. PHUONG PHAp xAe IlINH HO~TIlQ vA He s6 HO~T eQ

HOI)( dQ va h¢ s6 hoar d¢ cua cac C!"U tlr trong dung dieh c6 Ihe :dc dinh Ill" nhOng pblWl1g pUp thl!C n8hi~m. thf du phuoug pM.p lip suft hoi, phuong pbiip dinh lu~ phan b6, phllODg phap blm nghiem v.v ...

D6i veri dung dich 2 cfu Iii, co tM tfoh hoat de) cua c!"u tit nay khi da bie'l hoar d¢ ciia ci"u. Iii kia bang each sli dung h¢ thlit: Gipxo-Duhem.

C6 the tinh Ii thUyii hoat d¢ va h¢ s6 boat de) btn CCf sa nhfrng gii Ibuytt nao d6 ve ban cha:t va tac dung cua nhilng life gAy ra nhilng sai I¢Ch cua dung djch so v6i tfnh If Mmg. Qich lfoh nay bien mm chi thanb cong 16t d6i vc'ii. dung dich rA"t loang cbfl di¢n phan (thf dl:l xem thuytl Dabai.-Huclcen trong Dien hoa hoc).

1. Phlldng phap ap suit hCfi

Neu chon trang thai chufn theo each I thl a; = Pi I pf khi hoi la If tuC1ng. each nay thuong lip dung cho dung rnoi, Neu xac dinh ap suat hoi Pi tren dung dich c6 n6ng d¢ Xi va do lip suat hoi Pi cua i nguyen chat a clang T va P ngoai nhu dung dich thi c6 tM xac dinh tnrc tiep hoar d¢ 3j cua i.

N~u chon trang thai chub thea each II thl a; = Pi~' Dt xac dinh a; thea each nay. dn phai xac dinh h¢ s6 Henry ki = pi lxi, dau :I< ling v6i dung dich vO cung loang. Mu6n vay, xac dinh Pi d cac Xi khac nhau,

76

ghi p/Xj a true tung va Xi tren true how r6i ngoai suy duCtng bi~u dien cho t61 xi = 0 se dugc ~. [)6 18. gioi han cua ti s6 p/Xj khi Xj ~ 0 (hinh X-3). H¢. s6 Henry l:J day irng v6i thang n6ng dQ x.

Trang thuc t~. khi lam giam d~

n6ng dQ rna thay ti s6 p/Xj tien d~n mot gia tri c6 dinh thl ta cba'p nhan gia tri nay cho h¢ s6 Henry.

PhlK1I1g phap ap suA"t hoi tbuong dugc dung khi chi c6 met mlnh c,"u

ti:r i trong dung dich 18. bay boi hay c6 ap s~t hoi rO ~t 1&1 han cac cau tirkMc.

2. Phl.lCJng phip djnh lu.t phin bo

Khi c6 s\!, phAn b6 can bang mot ch,"t tan i gitla hai dung mOi (') va (") khOng tan vao nhau va vm nhUng dung mOi nay. cM"t tan i hlnh thanh nhUng dung dich khOng If tOOng va khOng do loang, thi dinh l~t phan b6 pbai bi.!u thi qua hoat dQ a' va a" cua i trong 2 pha long d6:

a' -=K a"

(T = const)

t

o

--- X;

Hinh X-3. Di xac dinh b¢ s6 Henry k,

(X. 19)

K la hang s6 phan b6. Do d6 n~u da bi~t s\!' phu thuoc ho .... t d('l cua i V80 n6ng dQ d6i veri. dung moi nay thl c6 the tim th,"y S\1' phu tbuec d6 d6i v6i dung mOi kia. Mu6n v~y, c~ phai MC dinh h¢. 's6 phan b6 K tir di~u kien gieri. han, Vi b dQ loang vO han a" = c" cho nen :

.* t*

a c

K=-=-

u* u*

a c

3. Phl.lCJng phip tfnh ho~ dq cua cau til' nay tLl h~ dq cua c8U tli kia d\f8 vao h, thd'c Glpxcs - £)uhem

a) Hf thue Gipxa-Duhem vi hoa: d~. Theo h~ thac Gipxo-Duhem b T, p const, Ln;d~ = O. Cac ~ c6 dang-u, = ~o (T.P) + RTlnaj • cac

77

-~ (T.P) chi phu thuoc vao Tva P, do d6 aT. P const, cac d~ bang khOng, con lai :

dlJi = RTdJn~

Dua gia tri nay cua dlJi vao kDjdJ.li. = 0 va sau khi loai bb RT se dircc h~ tht'rc Gipxa-Duhem v~ hoat dl) cua cac cau til trong dung dich :

:Enidlnai = 0

D6i'vm dung dich 2 ~u til (X.20) vilt 18 :

nld1nal + n2d1na2 = 0

ttr d6 :

(X.20)

d/nal :::: - n2 d1na2 :::: - x2 dlna2

'n1 xI

Trong th1JC tl. ap sua:t chi c6 imh huang khOng dang k~ Mn J.Ii. va do d6 Mn ~ cua cac i trong dung dich long, do d6 chi ~ nghien ctm a T = const.

(X.21)

b) Tinh a] khi dii bitt a2 va nguac lai. D6i voi (X.21) c6 th~ thay logarit t\1 nhien bang logarit thap phan r6i la:y tfch phan giiia 2 trang thai A va BaT = canst se dll'qC :

B

19(al)B :::: Ig(al)A - JX2 dlga2 A Xl

Neu Iga2 da dugc xac dinh d6i voi nhieu thanh pUn khac

nhau (tt'rc Ia d6i v6i nhieu xzlxI khac nhau) thl chi viec dung

dOOng cong x']/x 1 = f( -lga2) bang each ghi x21x I tren true

78

t

o

Hlnh X-4. Xac djnh a1 tit 3:z bang tfch phan dO thj

tung va -lga2 tren true hoanh. Saudo xac dinh gM. tri cua tich phan theo phtrong phap d6 thi (do dien tfch gach cheo tren hlnh X-4) tht c6 tbe xac dinh 19a1 d6i v6i bjft ki trang thai B nao, mien la n6 dB. dugc bi~t tai mot trang thai A nao d6.

Neu chon trang thai A IA dung dich vo cung loing (x2 ~ 0, al ~ xl = 1) thl 19(al)A = O .. Khi d6 hoat d¢ cr rn¢t trang thai B Mt Id, c6 x2 if; 0 se tinh theo h¢ tlnrc :

(X.22)

H~ th1lc nay cho phep tfnh al til' a2 va ngugc 14i. Nhuoc di~rn cQa phuong phap IA cr viing dung dich loang, khi x2 ~ 0, Xl ~ 1 thl ~ ~ 0, Xl

d6ng thm. a2 ~ 0, do dolga2 ~ -00, nhu v~y co met S1,l batdinh nao do, t1lc la sg xac dinh se kern chinh xac a vimg dung dich loang,

§5. cAN BANG DUNG DICH L6NG - CAU TU KHL £)Q TAN ellA KH[ TRONG CHAT L6NG

1. each biiu thl dq tan cua khf trong chat long .

Cling nhu ch9:"t rin, eh9:"t khf chi hoa tan co han vao chjft long. N6ng d¢ khf trong dung dich bio hoa no la dr) tan cua khi. Hien nay chua co dan vi nao dugc chap nhan lam dan vi chinh th1lc d~ bi~u thi d¢ tan cua khf. NguCri. ta thucm.g dung h¢ s6 tan va mot s6 each bi~uthi We.

H~ so tan a cua khf trong chA't long a nhiet d¢ Tva du6i ap suA't rieng phan p cua khi tren chA't long khi co can bAng l8. thl tich khi tim-

trong dan vi thltich cUa dung moi. N~u V tan (do aT, p) l8. th~ tich khf tan trong the tieh V ella dung moi, M s6 tan ella khf se l8. :

79

V,

a = _!m!..

V

(X.23)

H~ s6 tan a cho bilt mot tM tfch dung moi long boa tan dtn;IC bao nhieu the tfch khf a T va. p da cho.

2. A.nh hlJO:ng eua;ip suit lind'Q tan eua khl. Olnh lu,t Henry

GQi khi co khi nang hoa tan vao dung mOi long la c~u tlr 2, goi Ilf va J.l} la thl hoa hQC cua n6 trong pha khi va trong dung dich long can bang v6i. nhau :

J.lf = ~K (T) + RTlnf2

. J.l} = J.l~L (T, p) + RTlna2 Tit di~u kien can b8.ng Ilf = J.l~ suy ra :

In!1_ = J.l~L (T, p) - J.l~K (T) = Ink

a2 RT

(X.24)

hoac : f2 = lea2 (X. 25)

k Ii .. bam cua T va p. N~u 00 qua 3nh. bubng r~t nho cua p vito thl boa bQC cua khf 2 trong pba long thi c6 tM cMp nhan k la hAng s6 b T = const ; k goi la ~ sobo*c hdng so Henry.

a) Dung dich ta khong Ii luUng nhung lodng (d() tan he cua khi)

1) Khi tren dung dich xU- sf! Ii lueing : dinh lurJt Henry ve dt) Ian CLla kIIi trong chat lOng. Khi khi chi tan It, e6 th~ cb~p nhan hoat d() a2 bang ndng d() x2 cua khf trong phalong, Vi khi la If tubngnen f2 = P2 Ia ap su~t cua khi tren dung dich can bing voi khf. Khi d6 (X.25) trb thanh :

(T = const)

(X.26)

D61a. dinh lugl Henry do Henry tim ra bang thirc nghiem nam 1803, 06 mO t8. sl! phu thuoc giita lip suat khf P2 va d() tan x2 ella khi trong ch~t long. Bieu thee d6 hoan toan trang voi hf Ihuc Henry (VIII.8) P2 = k2x2 mO t8. ap su~t hoi bao hoa P2 cua ch~t tan 2 trong dung dich loang.

80

can bAng trong .hai qua trinh hoa tan khi 2 vao chat long va hoa hcri cua chat tan 2 til dung dich long la hoan toan luang duang nhau v~ m~t nhiet d()ng. M()t ben la can bang giita.khi va dung dich bao boa cua no, mot ben la can bAng giua dung dich long va hi:ri bao hoa cua cMt tan. ca hai can bang nay d~u tuan theo dinh lU~1 Henry khi dung dich Ia loang, TIt (X.26) suy ra a T = const :

x2 '= KP2 . (K = 11k) (X.27)

D6i v6i dung dich loang, x2 ti l¢ v6i m2 va C2, do d6 ciing c6 the vi~t aT = const :

(X.28)

N~u M2 18 kh6i luqng phan til cua khi 2 thl kh6i luong khi tan trong dan V! the tich dung dich (ho~c dung mOi) a T da cho la qz = M2c2. va theo (X.28) n6 bAng :

qz = M2Cz = M2K"P2 = K"'P2

(X.29)

(d6i voi dung dich loang, c6 th~ chap nhan 1 lit dung dich bAng 1 lit dung mOi). Du6i nhilng dang (X.27), (X.28) va (X.29) dinh l~t Henry c6 th~ phat bieu: •

Dtii vbi khi hinh tlulnh dung djch khOng Ii tliOng vbi dung moi va chi tan it trong dung moi, dq tan Clla khi bilu thj bdng nong dq x, m hay c, ho{ic bdng khoi luang khi tan trong dim vi thl ttcb dung moi la m(it dqi llI{1I1g ti If thu(m vbi ap suat tan bdng Clla khi tren dung dich,

Ghi chu. Nhimg sai lech d6i voi dinh luat Henry dugc nhan tMy khi khf hoa tan tham gia vao nrong me boa hoc voi dung moi, hoac phan li

bang ion, thi du tru'Ong hop NH3, HO, S02 v.V ... tan trong rnroc. Khi d6 d() tan toan phan thuong 16'0 va khong tuan theo dinh lust Henry.

2} H¢ qua cua dinh lUl't Henry. GQi V tan la tM tfch kM tan trong the tfch V eiia dung mei l! nbi~t d~ T va dum ap sun P2 eiia khf. Vi khf duqc coi 180 If till'mg, ta c6 :

81

P:2Vtan:= n2RT= ~ RT M2

g2 1iL kh6i lugng khi" tan trong thi tieh V eiia dung mei, dem ehia v6i. V liS dugc khci IU(1ng khf q2 tan trong dan vi tM tfch dung mei :

P2 Viall g2 RT RT

--=--=q2-

V V M2 M2

Theo dinh nghia (X.23) a := V tanN til h~ s6 tan a eiia khf, do do n€u k€t hgp v6i. (X.29) se diroc :

a= VlaII =S1..~=K'" RT =f(T)

V P2 M2 M2

Nbu v~y, d{Jl vdi kh( coi nhu khi Ii ruang va rudn thea dinh lugt Henry, h~ s(/ tan a cua n6 trong eMt lOng chi phI! thuqc vuo nhi~r dq, kMng phI! thuqc vuo ap suat. Dieu niLy ~ nghia til a nhi~t d¢ khOng d6i. m¢t the tfch nhf't dinh eua kbl (dum lip suru can Mng cua khf) dltgc hoa tan trong dan vj thi tfeh dung mOi. kheng ph\! thu!)c vao gili trj cUa ap sufI.

b) Dung dich. la li IUdng. Di) tan 1£ luting cUa khi. Ntu dung dich 18. Ii

(X. 30)

tttCmg (a2 = x2 6 moi x2) va neu khi cung xu SI! Ii nnmg (f2 = 1>2) thl tir (X.26) 1>2 = kx2 suy fa k = p~ (ung v6i x2 = 1). Nhu vay, neu khi 2 hinh thanh dung dich Iftu6ng v6i dung moi thl k c6 _y nghla vl}.t If 13. ap suat noi bao boa cua c6u tiI 2 nguyen chat 6 trang thai boo long 6 nhiet d¢ T ella thi nghiem do d¢ tan. Do d6 6 T const :

P2 = p~ X2 hoac X2 = P!

P2

D6 la hieu tlnrc cua dinh lw,it Raun .... Henry vi d~ tan Ii lliOng clio khi trong cMt long.

(X.31)

§6. CAN BANG DUNG DICH LONG - CAU Tlr RAN

1. Cin b~ng dung d!ch long vbl tinh thi cua ciu tii i

Ta xet bai tinh can bang di th! gitra m¢t pha ran chi chtra mot cau tiI i nguyen eMt va met pha long e6 hai elfu tiI (dung dich) trong d6 e6 elfu

82

tiI i. Khi d6 dung dich la bao hoa d6i v6'i i. N6ng d¢ xi cua i trong dung dich do la d9 tan caa i b Tva p ngoai da cho (p chi co anh hubng rA"t be).

GQi ~~ Iii thl! hoa hoc cua i trong pha long (dung dich) va JlfR la thl! hoa hQC cua i trong pha rAn nguyen chat. Dieu kien can bang la ~fR = Jl~; JlfR chi phu thuoc vao T va p vi i trong pha r&D lam nguyen

eMt. con Jl~ phu thuoc ca vao .thrum pMn cua-dung dich theo bieu thac :

~~ = JlfL (T. p) + RT/naj Dieu kien can bang JlfR ::= Jl~ dan tm : . JlPR _ JlPL

Ina. = 1 1

1 RT

Tit do, d1J3. vao (VII.35) lAy dao bam theo T b p ::= eonst trong dieu kien can bang van t60 tai, nghia 18. dung djch vAn 111 biio hoa d6i voi i se dU<JC :

=

(bh ::= bao hoa) ; hoac :

(al0a.-)' H~L _ HPR

__ I _ 1 I

or p.bh RT2

rx, 32)

HfR 18. entanpi cua 1 mol i ran nguyen chat con H?L la entapi mol rieng phan cua i trong dung dich b trang thai chuan. Neu khi tinh hoat d¢ aj cua CAU tiI i trong dung dich, ta lAy trang thai cua cau tiI i long nguyen chat lam trang thai chuan (nrc Iii l\j_ = 1 khi Xi ::= 1)

thl HfL = HfL = entanpi clla 1 mol i long nguyen chAt. Khi do Mlj = HfL._ HfR se la bien thien entanpi trong qua trlnh chuyen 1 mol

83

til trang thai i rin nguyen chat sang trang thai i long nguyen chat. N6i khac, Alij 18. nhift n6ng cluiy Loc,i cua 1 mol i rio nguyen chat, do d6 (X.32) vi€t Ia :

(atnai) = (alnYiXi) = Loc~

aT p.bh er p.bh RT

H¢ thiic (X.33) c6 th~ xet.hai each khac nhau toy theo i 18. dung mOi hay cha:t tan.

(X.33)

2, Him nghi,m

Slf k£t tinh Clla dung moi til dung djch lodng chd: tan. D6i v6i dung djch 100ng. khi lam ha thap nhiet d¢ tm bang diem T cua dung dich thl dung dich bit dan k€t tinh (dong bang). a day chi xet tnrong hop tinh the hien ra la cua dung mOi 1 nguyen chat can bang v6i dung dich long; dieu nay c6 nghia 18. b nhiet d¢ T (bang diem), dung dich trb thanh 00.0 hoa d6i v6i dung moi va phan mol xI cua dung mOi trong dung dich bao boa d6 bl~U thi d~ tan cua dung mOi trong dung dich,

D6i v6i dung dich loang (chfnb xac l8. VO cUng loang), 11 = 1 va at = x rhe thiic (X.33) trb thanh :

(alnXI ) = Loc•l

er p,bh RT2

(X.34)

H¢ thiic nay la tnrong hop rieng cua phuang trinh SriJde-/.."u Satdli; bil!u thi s,! phu thuoc d~ tan Clla cae cdu tli trong dung dich Ii IlIdng theo nbi¢t d¢.

a lip suat khi quyl!n ngoai p = Po = const, (X.34) c6 the viet :

dJ Loc.I dT UX! =R· T2

&! tfch phan pboong trinh nay til bang diem T cua dung dich (c6 thana phdn XI) d€n bang diem To Clla dung mOi 1 nguyen cMt (t'ing v6i Xl = I) se cho (kbi coi Loc,1 nhu khOng d6i trong khoang nb.i¢t d¢ nbo d6):

84

1 L To

Jdl nc.l J dT

nXl =-- --

R T2

XI _ T

- Lnc } (To - T)

lnXI = ___;;;;..:.:.';.......,;;:.._--

RITo

D6i v6i dung dich 2 cau tiI rilt loang c:lu til 2. ta co the chap nhan hai

su glin dung:

1) T rilt glin To de d~t ITo l':l T;

2) lnxl = In(1 - X2) l':l -x2 (vi x2 «1)

Khi d6 n€u d~t e = ~ T b = To - T va goi la d~ ha biing dilm cua dung dich so v6i dung moi nguyen chat, se duoc :

RT.2 e=~Tb= _o-x2

Lnc,}

hoac, neu chuyen tll' n6ng d(.l x2 sang n6ng d(.l molan m2 (d6i v6i dung dich loang, x2 = M,m2/l(00) :

RT2M RT2

e = .6.Tb = K~2 ; Kb = 0 '= 0 (X.35)

10Cl0 Lnc.! 10Cl0 Anc,l

Kb la hang s6 han nghiem ; Aac,} = Lac,l/M,la nhiet nong duly rieng d6i vci 1 gam cua dung moi nguyen chat, C6ng thrrc (X.35) trung v6i (VIII.19) da gioi thieu i'J chuang VIII.

3. Xic djnh h~t dQ va ~ sCi h~ dQ bang phamng ph6p han nghjfm D6i vm dung dich thuc, ta phai dung M thac (X.33). H¢ thuc Day cung cap mot trong nhi1ng each xac dinh hoar di) va he s6 hoat di) bang phuong phap han nghiern,

a) .xac dinh hoat d~ cua dung moi : Theo (X.33), i'J p = const :

85

dlnal Lnc,1

--=--

dT RTZ

SI! tich phan gifi'a hai bang diem To (cua dung moi nguyen chat, trng voi al = 1) va T (cua dung dich loang, Ung v6i mot gia IIi at nao d6), T va To rAt gan nhau, cho phep chap nhan Lnc,t = const, Khi do se dugc :

I _ Loc,1 T - To Loe,l,€1

nal - R' TIo = RTTo (X.36)

€I = i.\Tb = To - T la dQ ha bang diem cua dung dich xac dinh bang thuc nghiern (han nghiem). Tit do suy ra at va 11 = a1/x 1

b) Me djnh hog! d¢ va h¢ St" hog! d¢ cua chdt tan. Theo (X.33) d6i v6i. dung rnOi :

Lnc I d/nal = --2 dT

RT

Tir e = To - T suy fa de = -dT (vi To = const), do d6 :

Lnc,1 Lnc.l

-d/MI = -- de ... --de

RT2 RT2

o

. -

BAy gic'1 chuyen sang boat dQ ella char tan dira vito h~ tbue Gipxo - Duhem (X.21) :

01 nl Lnc 1 e

d/na2 == -- d/nal = - --' d

112 02 RT;

Oi! tbu o6ng do.) cb4"t tan bieu thi Mng dQ molan mZ' Khi d6 n I = I<XXl/M] va 112 = rn2' Mila kh6i hrgng pban IU cua dung mOL Ta dugc :

dina = 1000 Lnc.1 de

. 2 2

RT"M]rn2

Nhung theo (X.35) hang s6 han nghiem 11 :

K _ RT;MI b-

tOOOLnc,1

v*y:

(X.37)

86

ttr d6 c6 tM xac djnh (~>S ntu da bitt a:z q m(tt tr\lllg thai A nso d6 va neu da do diroc e lJ met day n6ng d¢ mz khac nhau :

B

In(aZ)B = In(aZ)A + _1-. J de Kb dm2 A

Phuong phap nay c6 nmroc diem ta khi chon dung dich v6 cuag loang lam trang IMi A thl mz ~ 0, a ~ 0, dong thm s6 hang I/~ cua nch pMn va In(~)A ciing trlJ thanh CIJ, do d6 Sl! tfch phan se thitu chlnh xac,

Dl!tninh tinh trang do, ta dung ham ph \I Irq :

j = I __ 9_ (X.39)

Kbmz

(X.38)

v« y nghia v~1 Ii Ihl j ia d¢ do Ifnh sai lech so v6i nhfrng thuoc tinh 'Cua dung dich loang, £)6j viti dung dieh vO cung loang 9 '= K~2 va j = 0. D6i viti dung dich thuc khong du loang, 9 ¢ Kb m2 va j ¢ O.

Tit (X.39) suy ra e = (I - j)'K~2' do d6:

de = (I - j) Kb dm2 - KJ>lD2dj

DI1a gia tri nay cua de vao (X.37) sf dlfQ"e :

dl 1 de . dm2 di dm2 .dm2 di na2 =-.-=(1-J)--- J=---J--- ~

x, m2 m2 m2 m2

GlOyen dm~m2 = d/llm2 sang ve tnii : dill ~ = dllrr2 = _.l... dm2 - dj

rn2 m2

Khi rn2 = 0, j = 0, dOng thCri 1'2 = 1 va 19'f2 = 0 (dung dieh v6 cung loang), Do d6 neu tich phan phirong trlnh tren lit m2 = 0 Mn rnz da cho, ta dtrQC :

(XAO)

lJ da.y sif tfch phan khong g*p kho khan vi khi m2 ~ 0, j ~ 0, tl s6 j/rn2 van giU duec m¢1 gia trj hiiu han. Ta xac dinh ttch phan (X:40) theo phuong phap dO th], Tnroc het xac dinh e va do d6 j d6i vui m¢t day dung dich co nOng d¢ m2 khacnhau va be dlln. DJ!l1g dO thi j/m2 theo rnz. Ngoai suy cho 1m m2 = O. Dien tich dum duemg cong thu dune gitta m2 = 0 va met gia trj m2 dii cho nao do se ling v6i gia tri ella tich phan phai tim. Tu do suy ra 1'2 va az = )12m2'

R7

D6i v& nhilng dung dich rft loing, Ii s6 j/m2 dll-t duqc gia'1li g4n nhu hAng s6 va c6 tnt! dua ra ngoai dtru tfch pbAn eua (X.40) va he lhlk nay Irb thanh :

(X.4I)

3. £)9 tan Ii t..mng clla chat rin trong chit long

Ta t:rls lai (X.33) khi i l~ eMt rAn (i <:! 2) tan trong dung moi long 1.

Gill thitt dung djch la Ii tudng. Khi d6 1i = 1 va ~ = '4, (X.33) t:rls thanh :

(a~xlbh = ~~

(X.42) a phuang trtnh SrOde-ld Satoli«, do SrOde (Schroder, 1890) va La Satolie (1894) lam viec d<>c 14p dii tim ra. N6 bieu thi quy l~t

bien thien d¢ tan xi cua i rio tan trong dung dich If tOOng theo nhi¢t d¢.

Vi IyC,i luon luon > 0 cho nen ta (X.42) suy ra ring d¢ tan Ii tudng xi cua coot ran tang theo nhi~t d(J T. Ngoai ra, a p canst. df) ian Ii tuOng Xj chi phI! thuf)c vao T, khong phI! thuf)c vao bdn cMf cUa CDU til khiic i, d(ic bift khOng phl;l thu(Jc VtW dung mOi.

Neu coi Lnc.i la nhiet n6ng chaycua 1 mol i rim nguyen chlft a nhiet d¢ n6ng

cbsy To va chap nhan gin dung rang n6 khOng d6i trong toan khoang nhiet dt') tit

, To dln T thl S\l tich phan (X.42) giita 2 nhiet d¢ nay a p const se cho :

Inxj = L~.i (;0 -~)

Lnc,i T-To =R· TIo

(X.43)

Vi Xj_ < 1. InXj < 0, oon Lnc.i > 0 cho nen ti:r (X.43) suy rarang T < To.

88

(X.42)

-

-

T

. Hinh X-5. SV phy lhU¢C dQ tan Ii tuimg cUa eMt tin trong cMt long vao nhi~t dQ.

COng thuc (X.43) cho phep rut ra quy tic sau My v~ dO tan If tulmg cuacMtran :

Logarit cua d¢ tan xi 10 ham b(ic nluft cua 1 rr, c6 the dung logarit - th$p phAn va chuydn (X.43) sang dang :

19x. - Lnc,i (_1 _ _!_)

I - 8~314x2,303 To T

h~c:

19x. = Lnc,i -. Lnc,i = B _ A

I 8,314 x 2,303To 8,314'x 2,303T T

trong d6 L.c.i tinh ra jun. Neu hieu dien 19xi theo Iff se duqc m~t dl1Un~ tMng co dt) d6c bAng -~c,/8,314 x 2,303 (hlnh X-5).

CHOONGXI

CAN BANG HoA HQC

§1. AI LI!C HoA HOC

1. Nguyen If Becto:lo

Ai lJ.!C boa hoc bieu thi khci nang phan tmg cua cac cMt vm nhau, Tomxen (Thomsen, Dan mach, 1853) va sao do Bectolo (Berthelot. Phap, 1867) de nghi do ai luc hoa hQC bang nhiet luong toa ra trong phan 11ng hoa hQC. Y kien nay dugc Bectole dungthanh nguyen Ii cong cue dai, thuong goi la nguyen Ii BeC(C1io (1867) : "Mt;Ji hie'n ddi hod hoc xdy ra rna khong co sif can thiep cua hen ngoai deu co xu hll6ng dien ra thea chieu san ra mqt chat hay m~t h~ chat toa ra nhiiu nhi¢t nhdt", Nhu vay, theo nguyen Ii Bectolo, cac phan Ung xay ra nr nhien d~u phai la phan ling toa nhiet va ai II,fC hoa hQC c6 tM do bang hieu irng nhiet cua phan tmg.

Neu goi cIIv va clip Ia d(> do ai luc hoa hQC trong cac phan irng dAng tfch va dAng ap thl thea nguyen Ii tren :

dfv = - Qv = -liU; dip = - Qp = -liH

Thea nguyen If d6. phan ling chi c6 the xay ra tl! nhien a v = canst neu Qv < 0 hoac dU < 0 va b p = canst nell Qp < 0 hoac dH < O.

Trang thuc te, mot s6100 phan ung xay fa b nhiet d(> thuong hay gao nhietdo thtrong III nhtrng phanrmg toa nhiet, Nhtrng co mot s6 khong it phan irng thu nhiet van dien ra duqc tl,l nhien, nhat III cr nhiet d(> cao. Ngoai ra, nguyen If Bectolo mau thuan voi str tOn tai nhOng phan img thuan nghich, dien ra theo ca hai chieu cr cung nhiet dQ, nheng phan ling nay da.'duqc Bectole (Berthollet, Phap) neu ranr 1801, do d6 neu phan ling la t6a nhiet theo chien nay. no phai III thu nhiet thea chieu kia.

Mendeleep (1875) va d~c biet la Potulitxin (1874) da: co vai tro co han trong viec vach rO sai l!tm cua nguyen li Betolo trong tnrong hop

90

t6ng quat. Potulitxin chi ro nguyen Ii d6 chi III mot dinh luat gioi han aT = OK.

2. Thuyit dOng dan ve il IVC hoi hqc

Nguyen lf BectC110 dua tren mot tien d~ dung: cac qua trinh t\l nhien (khong c6 su can thiep cuaben ngoaijdeu dien ra theo chieu nao san ra dugc nhieu cOng nMt (nguyen Ii cong eire dai), Nh1IIlg sai lAm cua BectolO Ia b ch6 da d6ng nMt cong cue dai cua phan ltog voi hieu img nhiet cua phan Ung.

Chi tren co sa nguyen lf II moi c6 d1I<JC rnl)t thuyet dinh IU<JOg <tung dAn v~ lii l~ hoa hQC. do Gipxo (1876) va Hemhon (1884) ~ ra. Van HOp pUt trik thuyet nay (1885) va cho n6 rnl)t dang toan hQC khi suy luan ra dinh l~t tac dung kh6i lU<JOg b!ng nhiet dl)ng Il!C hQC (dinh l~t nay hie tnr6'c chi d1I<JC cac nha khoa hQC Thuy dien Gunbe (Gulberg) va Vagio (Waage) thi~t l~p (1867) bang con duimg nghien ctru t6c dl) cira phan rmg) .

. DI) do ai luc hoa hQC khong phai la hieu tmg nhiet cua phan Ung rna Ia cong c6 the thu d1I<JC k:hi ti~n hanh phan img theo each thuan nghich nhiet dQng. tac lA hang dl) giam cua cac th€ nhiet dong tuong lhlg :

dlv = -,1F = Tt\S - dU = Av,max dip = -t\G = Tt\S - dR = A'p, max

(XI.I) (XI.2)

Tir (XI.I) va (XI.2) ta tMy nguyen Ii Bectolo dung trong hai tnrong hop rieng :

1) Khi T = OK. khi d6 dlv = -,1F = -t\U ;

dip = -dG = -dR. V~y a OK. nguyen Ii Bectolo dung khong c6 ngoai le va khong co qua trlnh thu nhiet nao xay ra tl! nhien a OK d1I<JC.

T cang grut OK thl dai luong dR cang bieu thi chfnh xac d~-I1I<JI1g dO va xac SuAt cua qua trlnh thea chi~u tba nhiet cang IOn.

2) Khi AS = 0, nghia Ia khi, phil hop v6'i (adG I OT)p = -t\S = 0, cong

c6 Ich Cl,TC dai (A'p,max = -t\5) khong phu thuoc vao T.

91

Cach dinh nghia dung dAn ai IJ!C hoa hoc cung giai thich tai sao m(lt qua trlnh thu nhiet I~ c6 the xay ra nr nhien : .6.U va MI trong tnrong hop nay c6 gia tri duong, qua trlnh mu6n di~n ra dtn;1C chi c~ c6 mot bien thien entropi .6.S va mot nhi¢t d(l T du cao de lam cho T.6.S 100 han .6.Uho~MI.

§2. al~u KleN CAN BANG HoA HQC

Phdn rmg thu4n nghjch hoa hoc g6m hai phan rmg dan gian han : mot phan tmg thu~ va mot phan Ung nghich dien ra d6ng thoi thea hai chieu nguoc nhau v6i t6c dQ khac nhau. Phan Ung thuan nghich tOng quat mlli 16c Ia k~t qua t6ng hop cua hai phan img thuan va nghich d6. Tuy theo dieu kien, mQt trong hai chieu, thuan hay nghich c6 the chiem uu thl! va phan tmg thuan nghich tOng quat se dien ra thea chieu d6 cho tm khi dat t6i trang thai can bAng hoa hQC. can bang nay la mQt can b&ng df)llg vi hai qua trinh thuan va nghich van di~n ra nhung v6i t6c d¢ bAng nhau cho nen thanh phdn cua cac chat c6 m~t trong phan l'rng ke tit 16c d6 khong thay d6i nita.

C3.c phan rmg hoa hQC n6i chung deu la phan l'rng thuan nghich hoa hQC. Tuy nhien c6 nhtmg phan U'ng trong d6 m¢t trong hai chieu rat yl!u khong dang ke va nhtmg phan 6ng do thuc t€ la phan irng mot chieu, di~n ra cho d€n cung,

D6i v6i nhttng M trong d6 c6 phan rmg boa hoc dien ra, nhtmg qua trinh vO cung nbc trong h¢ 6ng v6i nhtmg he thtrc sao:

dF = -SdT - pdV + l:lJidnj dG = -SdT + Vdp + LJ..I;dDj

Neu qua trinh trong M dien ra a T. v canst hay aT, p = const nhGng he thdc tren trlJ thanh :

(XI.3)

dFT,V = dGT,p = LlJidnj (XI.4)

Trong nhGng dieu kien tuong tmg, qua trlnh chi c6 tM dien ra tl! nhien theo chieu lam cho LJ..I;dDj < 0 va can bang trong he se dat tm khi LJ..I;~=O,

92

Gii thir trong M e6 nhO'ng eMt AI' A2, ... , BI, 8:2, ... eo kha nang ph8n Ung v6i ohau theo phuong trlnh hoa hQC :

vIAl + v2A2 + ... = v'lBl + v'2Bz + ... (XI.5)

Neu ph.in Ung t6ng qual di~n fa theo chieu thuq.n (tir trai sang phii) thl AI' A2, ... J.a nhtmg ehAt <ltu, BI, Hz ... 18 nhtmg ehAt cu6i hay sin pl$n eua phan Ung._ Vi nhttng blen taien dnl, dn2, ... dn'[, dn'2"'. v~ s6 mol cua cluing IA do phan Ung ga.y fa eho nen phai ti l¢ v6i nhO'ng M s6 ti hrong

vI' v2.·· .• v'l' v'2". cua chung trong phuong trinh phan ling t1ic 1A :

_ dnl ::: _ dn2 ::: ... ::: dn'l = dn '2 = ... = d", > 0 (XI.6)

VI V2 V'l V'2

cr day. d6i v6i nhO'ng eh~t eu6i (eMt dUQC hlnh thanh) d11j_'> 0 eon d6i v6i nhtrng eMt ~u (chat mat bOt di) dn, < 0, do do da:u "Am" d~t t:ru<Jc nhtrng ti s6 dn/Vj va dAu "duong" ~t truce nhO'ng ti s6 dnj'/ Vi' bao dim cho dA. co gm tri duong. Nhilng ti s6 do lit gi6ng nhau d6i v6i moi chat trong phin tmg va e6 the viet duOi dang vi phan eua met dai luqng A. nao d6. D~ hrqng nay goi la d~ tien triln cua phan img. No eho hiet v~ kh6i lUt;1l1g eua m6i eMt trong phan tmg tai thoi diem dang xer va do bAng nhtmg dan vi. tuong duong nhau, tmg v6i phuong trlnh phan Ung. Thf d\J trong phan Ung :

N2 + 3H2 = 2NH3

dan vi kh6i luong nrong duong d6i v6i cac eMt 1A (N2), (3H2), (2NH3) nghia 1A 1 mol N2, 3 mol H2 vA 2mol NH3. ru 1 mol N2 mlft di thl n6 m~t di d6ng thai voi 3mol H2 va sinh ra 2mol NH3. D6i v6i cimg m¢t pbin img, bien thien v~ kh6i IUt;1l1g, do bang nhUng dan vi nnmg duong lit gi6ng nhau d6i v6i moi chlft a Mt k.1 thm diem nOO.

D¢ tie:n trien A. bien thien trong pharn vi ttr 0 den 1. Neu dA ::: 0, phan Ung chua dien ra, neu dA -i'A A. ::: 1 thl :

dn~ ::: dn~ -i' An~ = An~ = ... = An~ = AA. = 1

, , • t r

VI V2 VI V2 Vi

93

, ,

tuc la Mj = Vi va do d6 dnj == Vj

DQ tien trien hoa hoc A. chi d~c tnmg cho mot phan trng nhat dinh.

Neu trong he dien ra nhieu phan Ung thl mOi phan Ung d~c tnrng bang

mot di) tien trien rieng (1.'1' /..z,,,.).

Dira nhttng gia tri cua dn, rut ra ti:r (XI.6) vao t6ng LJ.lidnj se diroc :

, I

== - vll..lA] dA - v2~A2 dA - ... + vI~B] dA. + v2J.lB2 dA + ... =

= [( V~~Bl + V~~B2 + ... ) - (vl~A] + V2J.lA2 + ... )]dA =

= (l:V:J.lB. - :EVj J.lA. )dA = A~A.

1 1

v6i :

(XI.7)

(XI.S)

l:Vi~Ai la t6ng th€ h~ hQC cua nhihlg chat cU.u lay theo nhimg he s6 ti lueng ella chung, l:VjJ.lIlj la t6ng th€ hoa hoc cua nhihlg chat cu6i (nhihlg san pham cua phan Ung) cung lay theo nhimg M s6 ti hrong cjia chung. (TI.r (XI.4) va (XI.7) ta diroc, d6i voi phan img hoa hQC :

(X1.9)

ti:rd6 :

(:)T,V = (~)T.P = A~

Vi da s6 phiin dog dien ra (1 T,p const, nen ta se chi chu y d€n ham Gipxo hay th€ dAng ap 0.0 T.p const, pbiin dog dien ra tl,l' nhien theo

(XI.lO)

chieu dog voi dO T,p < 0. do d6 :

dJ.l = l:v~J.ls. - l:VjIJA < 0 (XI.ll)

1 1

bCri vi, thea dinh nghia, dA > 0. Dieu kien (XI.II) tuang duong vOi

94

· ,

_l:viJ.lA- > l:viJ.la. (XI. 11 a)

1 I

Nhu v~y phan (ing hoa hoc chi c6 tM dien ra nr nhien theo chieu lam giam LVi J.lA; ,86 hang nay phai c6 gia hi Ian d6i voi he nhiing chat ~u han la h~ nhiing chatcuoi. Chimg 03.0 phan iing con chua can bang thl

LVi J.lA- con giam, d6ng thm l:v;J.lB. con tang. Cu6i cung khi LVi J.lA-

I , I

tm thanh bang l:v;J.lB; thl he dat t6i trang thai can bdng hoa hoc, ung v6i di~u kien dGT,p = AJ..LdA. = O. VI dA *- 0 nen di~u ki~n can bAng la :

1* = l:v;J.lB. - l:viJ.lA- = 0 (XI.12)

1 1

Dieu kien nay tuang iing v6i cue ti~u cua ham G = f (A.) a T,p const, rut ra til (XI. 1 0) :

(00) = dJ.l = 0 (XI.13)

aA. T,p

Ciing luang tl! nhu v~y. di~u kien cua can bAng hoa hQC a T,V const se la :

(8F) = dJ1 = 0

aA. T,V

(XI.14)

I

dGT,p = (G' - G),..P = l:viJ.lBi - LVi J.1Ai = AJ.l _ (XI.15)

D~ hmng dGT,p goi la thE d&ng ap Clla phdn ·Wig, n6 bang bi€n thien the! ding ap cua he do ph8.n. l'rng gay ra khi 56 mol cac cha:t bAng h¢ s6 ti luong cua clning trong phuong trlnh phan l'rng. Dinh nghia nay la mot quy wc rna ta c~ phii nha khi lam cac phep tinh v~ can bang hoa hQC.

The'd&ng dp chudn AGo cua phan l'rng Ia gia ttl Clla AG khi ta:t ca cac cMt ~u d\lQC Ia:y a trang thai chuAtf-:

95

(XI. 16)

Chu y rang the' d&n~ ap AG cua phan tmg phu thuoc vao T va p nhung the'ddng ap chudn AG cua ph8.n Ung chi phu thuoc vao T vi a trang thai chuin cac ap suai d~u nhan gia tri e6 dinh bAng I atm (N6i dung thl chua e6 quy dinh th6ng nhKt v~ ap SImt chuin d6i v6i eMt tan trong dung dich long, tuy nhien thl! hoa hQC cua nhUng chit nay chi phu thuoc ehu yl!u vao T, rft it vao p, do d6 c6 the bO qua 8nh huang cua ap suat, eoi nhu ap sua:t vAn bang I atm).

§3. a!NH LU~T lAc DVNG KHOI LlIQNG VA PHUONG TRiNH aANG NHlel CUA PHAN liNG HoA HQC

1. Thii"t·l"p d,ng tang quat nhat eua djnh lu~ theo phwng phap - the nhl,t dqng

N€u a T,p const dien ra phan rmg (XI.S) :

. .

vIAl + v2A2 + ... = vJBl + v2B2 + ...

thl th€ dAng ap AG cua phan Ung xac dinh bbi (XI. IS) :

.

AG = :EviJ-lS. - :EviJ-lA-

I I

Neu moi chat Mu a trang thai chuan, trung v6i trang thai chuan cua eliu - tiI nguyen chat, thl th€ dAng ap chuan AGo cua phan Ung diroc xac dinh bbi (XI.16):

dod6

o . 0 0

AG r: AG = :Ev· (J-lB. - uz, ) - :Ev· (J-lA. - J-l )

I I '-lSi I I Aj

Phuong trinh nay dung v6i moi he Wt kl, ddng tM cilng nhu di tM. _

96

Vi bien thien th€ hoa hQC khi chuyen Imol cha:t i tll' trang thai chuan sang trang thai da cho bang:

. f· -

J.li - I-lf = RTln _I = RTlnaj £0

I

cho nen :

. ,

VI V2

AG - AGo = RTfn as, aS2 ,.. = RTlnTIa

VI V2

aAI aA2··•

(XI.17)

(XLI!!)

V· a'

I1~

V· a' A;

la tfch cac s6 hang c6 dang a~i. chia cho tich cac s6 hang

I

co dang a~ ..

,

. Khi c6 can bang hoa hQC, AG = 0, do do :

AGo =-RTln (a~~ a~ ... J (XI. 19)

- VI V2

aA aA •. ,

. I 2 cb

Oic aAj, as. ... trong (XI. 19) Ia nhimg hoat d¢ khi co can bang boa hQC (cb = can bing), khac voi nhttng gia hi aAj, as; ... trong (XLI7) hay trong (XI. IS) chi la hoat d¢ ung v6i m¢t giai doan dien bi€n bct"t kl nao d6 cua ph8n img, c6 tM 13. trang thai diu cua phan tmg chang han, (XI.19) cO tM vi€t:

( . . J

VI Vl

3S a8:2 .. , AGo

111 I = --- = f(T)

VI V2 RT

3A aA .,.

I 2 cb

Vi AGo chi phu thuoc vao T, nen v€ phii phuong trlnh nay 13. bam chi cua T; a T const n6 13. mQt hAng s6, v~y v€ trai cung Ia m¢t bang 50 va.

97

ban than dai luong sao dAD In cling la mot bang s6 goi la hOng so' can bang hod hoc Ka:

( '] ("]

Vi VI V2

al\ aB aBz'"

Ka(T)==TI - == I.

Vi VI v2

aA. aA aA ...

..... cb I 2 cb

(XI.20)

Sau nay, khi khong so nham IAn thl bo khong can ghi kf hieu cb a chan. Phil hop voi (XI.20), phUC1I1g trlnh (XI. 19) co th~ vit!t :

I .6.Go = - RTlnKal (XI.21)

va (XI.17) co th~ vi€t :

I .6.G = RT(ln IIa -lnKa) I

(XI.22)

PhUC1I1g trlnh (XI.20) la bi~u thirc t6ng quat oMt cua djnh lut_it tdc dung kh6i luang,

sv: suy 1\$ fa phuong trlnh (XI.20) va (XI.22) 18. hoan toan t6ng quat va khong dua vao mot quan niem 118.0 v~ co eh€ cua qua trinh.

PhllC1I1.g trlnh (XI.22) goi lil phuang trinh d&ng nhifl cua phon ung hoa hoc, hay phuang trinh Van Hop, 18. mot trong nhiing phuong trlnh quan trong cua nhiet dong IJ!C boa hQC.

Du6i day ta Sf! xet nhiing tnrong hop rieng,

2. Can bAng hoa hQc dong thi trong pha khl I( tU'lJng

a) Hang so' can bang Kp. D6i vci khi If tuang, <lj_ = fi = Pi. do do d6i voi phan dog trong pha khf If tuang K, = Kp = f (T).

l v;, J l v~ v~ J

PB- PB PB ...

K =II _, := I 2

P Vi VI V2

PA . PA PA'"

, cb I 2 cb

(XI.23)

D6i v6i khi If urong, bang s6 can bang Kp chi phu thuoc vao T.

98

Du6i dang (XI.23), dinh luat tac dung kh6i luong bieu thi m6i lien he dinh luong giii'a nhiing ap suat rieng phan cua cac khi trong hOn hop khf Ii tuOng khi co colo bang hoa hQC. Thi du, d6i voi phan irng tong hop.

amoniac : N2 + 3H2 = 2NH3 :

2 PNH3 Kp=--'~3-

. PN2 PH2

a day bO khong ghi ky hieu tat cb (colo bang) a chan, nhung cAn nho 13 khi tfnh Kp bao gio cOng phai lAy nhUng gia tri cua ap .SU~ rieng phan khi co colo bang hoa hQC ; d6i voi cac hang s6 colo bang khac cnng vay.

Phuong trmh ding nhier (XI.22) cua phan irng viet la :

DoG = RT(ln IIp -III Kp) (XI.24)

a day

v, v! V2

PB' PB! PB2 •••

InIl =IIIIl-' :=; III--=---~-

P Vi vI v2

PA; PAl PA2'"

trong do cac ap suAt rieng phdn lAy a mot giai doan tuy y khong phai la trang thai can bang hoa hQC.

b) Hdng sf/ can bang Kc- Giira Pi va nong dQ cicua khi i trong hOn hop khi Ii tUdng, co h¢ thirc Pi = c.R'I', Dua gia tri nay cua Pi van (XI.23) va neu d~t:

(XI.25)

Dov = (v~ + v~ + ... ) - (vl + v2 + ... ) = const thl se dllQC :

( , . J

vI V2

K (T) = CHI cSz'" . (RT )IlV

p vI V2

cA cA .,.

1 2 cb

Vi Kp la hang s6 chi £hl). thuoc van T nen ve phai cling phai co tinh cMt nay ; ave phai (RT) v Hi. mot hang s6 aT const, do d6 phan con lai

(XI.26)

99

ella ve phai efing phai III mot hang s6 chi phu thuoc vao T, goi III iuJng s6' can baTlg Kc

( c;~ J ( c;~ c~~ ... J

K = II _, = _ ..... 1 _~-=--l_

c vi vI v2

CA CA CA ...

1 cb I 2 cb

(XI.27) 13 mot dang cua dinh lu~t tac dung kh6i hrong rna Gunbe va Vagio da thu diroc nam 1867 ; a day no hitu thi rn6i lien M dinh hrong giira n6ng d¢ c, cua cac khi trong hOn hop Ii nnmg khi co can bang hoa hoc,

(XI.27)

Dua Kc VIlO (XI.26) se dugc phuong trlnh lien he Kp veri. Kc a cung nhiet dl) T d6i vm phan WIg khao sat:

Kp = Kc(RT)'~v (XI.28)

Neu v tinh ra lit, P ra atm thi R = 0.0821.atmld¢.rnol.

c) Dai luang Kr Giiia Pi va phanmol Xi cua khi i trong h6n hop khf If luang co M thuc Pi = PXi, pia ap suat toan pMn cua hOn hop khf. Dua gia tri do cua Pi vao (XI.23) se duoc :

Kp = Kxp6V x, co dang :

(XI.29)

(Xl. 30)

K K -Av x = p-P

(Xl.29a)

Vl Kp chi phu thuoc vao T nen (XI.29a) cho thay rang dai luong Kx' khac voi Kp' kh6ng nhtrng phu thuoc vao T, rna con phu thuoc ca. vao ap suat loan pMn p cua he. N6i khac, b T = const, trong khi Kp lit hang s6,

100

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