I HC NNG TRNG I HC S PHM -----

BI GING MN

NHIT NG HA HC

Ngi son: Giang Th Kim Lin

Nng, 2009 1

CHNG 1. NGUYN L TH NHT NHIT NG HC V P DNG VO HA HC (NHIT HA HC) Nhit ng hc nghin cu dng nhit ca chuyn ng vt cht v nhng qui lut ca chuyn ng . Nhit ha hc l mt phn ca nhit ng hc nhm mc ch kho st s trao i nng lng i km theo nhng bin i vt l, ha hc ca vt cht. Nhit ha hc nghin cu mi lin h gia dng nhit v dng ha hc ca chuyn ng vt cht; gip tin on trong mt s trng hp mt bin i c th xy ra c hay khng; p dng nhng nh lut c bn ca nhit ng lc hc vo cc hin tng ha hc v c bit l cc hin tng ha l (cn bng ha hc, nh hng ca cc yu t khc nhau n qu trnh ha hc, cc tnh cht nhit ng ca cc cht, cc h). Nghin cu v l thuyt dung dch; cu to v tnh cht dung dch ca cc cht khng in ly; quy tc pha.. I. MT S KHI NIM 1. H nhit ng (H thng - system) Khi nim h nhit ng: H nhit ng l mt phn ca v tr c gii hn xc nh ang c kho st v phng din trao i nng lng v vt cht, l tp hp ca mt s ln cc tiu phn. Phn cn li ca v tr l mi trng ngoi i vi h. H c th trao i nng lng (nhit, cng) v vt cht vi mi trng ngoi. V d: Mt bnh cha hn hp gm hai ha cht ang phn ng vi nhau. H l cc cht c mt trong bnh phn ng, gii hn ca h l thnh bnh, phn v tr ngoi ng l mi trng ngoi. Phn loi h: + H h (h m): l h c th trao i c nng lng ln vt cht vi mi trng ngoi. V d: un si mt m nc, nhit c cung cp vo h, h mt vt cht ra mi trng ngoi di dng hi nc. + H kn (h ng): l h ch trao i nng lng vi mi trng ngoi nhng khng trao i vt cht vi mi trng ngoi. V d: h gm cc ha cht ang cho phn ng trong mt ng thy tinh hn kn. H khng mt vt cht nhng c th nhn nhit t mi trng vo (nu phn ng thu nhit) hoc cung cp nhit cho mi trng (nu phn ng ta nhit).

+ H c lp: l h khng trao i c nng lng ln vt cht vi mi trng ngoi. V d: mt bnh cha ha cht c y kn v c bao ph bng mt lp vt liu cch nhit cho vt cht v nhit lng khng th trao i vi mi trng ngoi. + H on nhit: C s trao i cht nhng khng c s trao i nhit vi mi trng. + H ng th: c tnh cht ng nht tt c mi im ca h. V d: kh nn trong bnh, ru cha trong chai... + H d th: c tnh cht khng ng nht trong cc phn khc nhau ca h c phn chia vi nhau bng b mt vt l. V d, nc v nc 0oC... + H vt l: h m trong xy ra cc qu trnh thay i vt l nhng khng c s thay i v bn cht ho hc. V d, s bin i cc trng thi vt cht nhit nng chy, nhit si. + H ho hc: h m trong c mt phn hoc tt c cc thnh phn ho hc tc dng vi nhau c s thay i v bn cht ho hc. V d, Zn v H2SO4 cha trong cc thu tinh. 2. Trng thi v thng s trng thi Trng thi l mt tp hp trc tip hay gin tip ca cc thng s trng thi, ni ln c im ca h ang c kho st. Mt h c trng thi xc nh khi nhng thng s xc nh nhng i lng ca h c bit mt cch chnh xc nh nhit , th tch, p sut, khi lng ring... cc i lng ny c gi l thng s trng thi ca h. Trng thi ca h s thay i nu t nht c mt trong nhng thng s trng thi thay i. V d: 200cm3 nc 25oC, 1atm cho bit trng thi ca h nc ang xt. Ch trng thi y khc vi trng thi tp hp ca vt cht (pha, tng) l rn, lng, kh. V d h nc trn c un nng n 50oC, cng p sut 1atm th h ny c trng thi khc: th tch nc ln hn 200cm3 mt t, nhit 50oC, p sut 1atm. Nhng trong c hai trng thi ca h nc trn th nc ca h u pha lng.

Thng s trng thi l cc i lng: nhit T, p sut P, th tch V, khi lng m, thnh phn ho hc... C 2 loi thng s trng thi: thng s dung v thng s cng : * Thng s dung (khuch ):
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Thng s dung - tnh cht ca h vt cht c th tnh c t cc tnh cht ca cc thnh phn tng ng cu to nn n, c gi tr bng tng cc thng s ca cc thnh phn. V d, khi lng phn t bng tng khi lng cc nguyn t; in tch ht nhn nguyn t bng tng in tch ca cc proton... *Thng s cng : Thng s cng khng c tnh cng, khng ph thuc vo yu t dung . V d, nhit ca nc (cng ) khng ph thuc vo th tch v khi lng ca n. Trang thi cn bng nhit ng: Mt h trng thi cn bng nhit ng khi gi tr ca cc thng s trng thi mi im trong h u nh nhau v khng bin i theo thi gian hoc nu c bin i th bin i v cng nh. 3. Qu trnh nhit ng (Bin i) Mt h nhit ng hc bin i (hay thc hin mt qu trnh) khi trng thi ca h thay i. Trng thi ca h thay i nu t nht c mt thng s trng thi ca h thay i. Bin i c xc nh nu bit r trng thi u v trng thi cui. Qu trnh c xc nh khi bit c trng thi u, trng thi cui v tt c nhng trng thi trung gian m h tri qua. Phn loi cc loi qu trnh: - Qu trnh h (m): l bin i m trng thi u v trng thi cui ca h khc nhau. V d: 200cm3 nc 20oC, 1atm c un nng n 50oC, 1atm. - Qu trnh kn (ng) - chu trnh: l bin i em h t trng thi u n trng thi cui ging nhau. V d: 200cm3 nc 20oC, 1atm c un nng n 50oC, 1atm..ri li c lm ngui v 20oC, 1atm. - Qu trnh thun nghch: l bin i m cc trng thi trung gian ca h tri qua c xem nh do cc qu trnh cn bng. Mt cch n gin xc nh tnh cht thun nghch ca mt bin i l kho st xem bin i ngc li c th xy ra c hay khng khi ch thay i rt t iu kin thc nghim. Nu bin i ngc xy ra c th l bin i thun nghch, nu bin i ngc khng xy ra c th l bin i bt thun nghch (hay bin i t nhin).
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V d: s truyn nhit t ngun nng sang ngun lnh l mt bin i bt thun nghch hay t nhin v bin i ngc li, tc s truyn nhit t ngun lnh sang ngun nng khng th thc hin mt cch t nhin. S ri t do di tc dng ca trng trng cng l mt bin i t nhin hay bt thun nghch. S ng c ca nc 0oC, 1atm l mt bin i thun nghch v bin i ngc li ng vi nc nng chy 0oC, 1atm cng c th thc hin c. - Bin i ng tch: l bin i c thc hin trong iu kin th tch ca h khng thay i. V d: mt phn ng ha hc c thc hin trong ng hn kn. - Bin i ng p: l bin i c thc hin trong iu kin p sut khng i. V d: phn ng c thc hin trong bnh cu n thng vi kh quyn bn ngoi. - Bin i ng nhit: l bin i c thc hin trong iu kin nhit khng i. V d: phn ng c thc hin trong mt bnh cu nh c t trong bnh iu nhit(*) gi nhit xc nh. - Bin i on nhit: l bin i c thc hin trong iu kin khng c s trao i nhit lng gia h vi mi trng ngoi. V d: phn ng c thc hin trong bnh Dewar y kn, c bao quanh bi cc lp cch nhit tht dy.

4. Hm s trng thi Mt i lng c gi l hm s trng thi ca h nu bin thin ca i lng ch ph thuc vo trng thi u v trng thi cui ca h m khng ph thuc vo cch tin hnh qu trnh (nh thun nghch hay bt thun nghch). Ni chung, tt c cc thng s trng thi ca h nh nhit T, p sut p, th tch V.... u l nhng hm s trng thi ca h v nhng thng s ch c trng cho trng thi ang xt ca h. Khi h chuyn t trng thi u sang trng thi cui, bin thin ca nhng thng s trng thi ca h ch ph thuc vo nhng trng thi , khng ph thuc vo cc trng thi trung gian m h tri qua.
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Mt bin thin hu hn (tng i ln) ca mt thng s trng thi x trong qu trnh c ghi l x = x2 - x1 trong x1, x2 l gi tr ca x trng thi u v trng thi cui. Mt bin thin v cng nh ca thng s trng thi x s c ghi l dx hoc x C nhng i lng khng phi l hm s trng thi ca h trong trng hp tng qut nh nhit lng q, cng A. Nhit lng q v cng A m h trao i vi mi trng ngoi khng nhng ph thuc vo trng thi u, trng thi cui ca h m cn ph thuc vo cch tin hnh qu trnh. Chng c trng cho qu trnh ch khng phi l thng s trng thi ca h. Chng ta qui c dng k hiu ch nhng lng v cng nh ca nhng i lng no khng phi l hm s trng thi ca h, V d: v dng k hiu d hoc cho nhng bin thin v cng nh ca nhng thng s l hm s trng thi ca h, V d: dT, dp, dV,... 5. Nhit v cng Trong s tng tc gia h vi mi trng ngoi c th c xy ra s trao i nng lng. Khi c hai cch khc nhau trong s chuyn nng lng t vt ny sang vt khc. Nu s chuyn nng lng c lin quan n s thay i cng chuyn ng phn t ca h th s chuyn nng lng ny c thc hin di dng nhit. Nu s chuyn nng lng c lin quan n s chuyn dch nhng khi lng vt cht v m di tc dng ca nhng lc no th s chuyn nng lng ny c thc hin di dng cng. V d: t nng mt h kh cha trong mt xy lanh kn th cc phn t kh s gia tng chuyn ng: h nhn nng lng di dng nhit. Kh gin n y piston (c khi lng) i ln mt on: h cung cp ra mi trng ngoi nng lng di dng cng. Cn nu dng lc nn piston i xung mt on: h nhn nng lng t mi trng ngoi di dng cng; cc phn t kh chuyn ng hn ch trong mt th tch nh hn nn c s va chm gia cc phn t kh nhiu hn v kt qu l h nng ln: h cung cp nng lng cho mi trng ngoi di dng nhit. Theo qui c v du ca nhit ng hc: - Nu h ta nhit th nhit c tr s m, q < 0. - Nu h thu nhit th nhit c tr s dng, q > 0. - Nu h to cng th cng c tr s m, W < 0. - Nu h nhn cng th cng c tr s dng, W > 0.
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a. Nhit Nhit lng q cn dng em m gam ha cht tng ln mt khong nhit tng i nh t T1 n T2 l: q = mc(T2 - T1) Vi c l nhit dung ring) ca ha cht, l lng nhit cn em mt gam ha cht tng ln mt , c xem nh khng i trong khong nhit trn. Thng ngi ta o nhit lng q p sut khng i hoc th tch khng i, lc t nhit c s l t nhit ng p hoc t nhit ng tch .

Nu m = M, phn t gam (khi lng mol phn t tnh bng gam), th c t nhit mol ng p hoc t nhit mol ng tch , l lng nhit cn em mt mol ha cht tng ln mt iu kin p sut khng i hoc th tch khng i. Mcp =
p

McV =

Trn thc t, thng

thay i theo nhit . Trong trng hp ny, ngi ta xem , trong t nhit mol trung bnh l v .

mt khong nhit tng i nh ng vi mt mol ha cht, ta c:

ln lt l nhit lng cn em mt mol ha cht tng ln ng p, ng tch.

iu kin

=> Tr s t nhit mol ng p , t nhit mol ng tch ti nhit xt l:

Vi n mol ha cht:

b. Cng Ta thit lp biu thc tnh cng gin p ca h. - Trng hp p sut ngoi khng i:

Xem mt h cha kh gin n nh hnh v trn t th tch V1 n th tch V2. Gi s piston c khi lng khng ng k v h ch chu tc dng ca p sut ngoi khng i to nn bi s ln ca trng lng mg, vi m l khi lng ca mt vt nh c t trn b mt piston, g l gia tc trng trng, S l tit din ca piston. p sut ngoi l:

Ghi ch: p sut l p lc tc dng ln mt n v din tch. Lc p thng gc vi din tch mt b p c gi l p lc. Cng gin n ca kh khi piston di chuyn ln mt on h l: W = - mgh (Cng = lc x on ng. Thm du - cng to c tr s m)

V2 - V1: tng th tch ng vi s di chuyn ca piston ln mt on h. Nu V2 - V1 > 0 => W < 0: h to cng Nu V2 - V1 < 0 => W > 0: h nhn cng ( nn piston i xung) W < 0: cng gin n ca h chng p sut ngoi. W > 0: cng p, h nhn cng bi p sut ngoi ln. Nu = 0 => W = 0 => S gin n kh trong chn khng khng cung cp cng.

- Trng hp p sut ngoi thay i theo th tch V: Trong trng hp ny ta xem mt on di chuyn nh dh ng vi mt tng th tch nh c th xem nh khng i. dV trong p sut ngoi Cng tng ng l:

[Dng k hiu (W v cng A khng phi l mt hm s trng thi, n thay i ty theo ng bin i] Nu h cha kh l tng v bin i ng nhit, thun nghch, ta c:

Ngoi ra ngi ta cng chng minh c rng cng gin n thun nghch l cng cc i (v tr s tuyt i) cn cng cn cung cp nn p h mt cch thun nghch l cng cc tiu (v tr s tuyt i). Ngha l cng trng thi u, trng thi cui nh nhau, nu h gin n thun nghch th cng to c tr s m hn so vi cng gin n bt thun nghch. Nu h b nn p thun nghch th cng cn cung cp t dng hn so vi bin i nn p bt thun nghch. Do xt theo du i s th II. NGUYN L TH NHT NHIT NG HC. NI NNG U V ENTANPI H 1. Nguyn l th nht nhit ng hc v ni nng U Xem mt h bin i t trng thi (1) n trng thi (2) theo nhiu ng bin i khc nhau. Gi q1, W1; q2, W2; ...; qi, Wi l nhit v cng trao i gia h vi mi trng ngoi theo cc ng bin i 1, 2, ..., i. Nguyn l th nht nhit ng hc c pht biu nh sau: Nu qi v Wi l nhit v cng trao i gia h vi mi trng ngoi theo ng bin i i th qi v Wi ring r thay i theo ng bin i nhng tng s qi+Wi lun lun l mt hng s khng ty thuc ng bin i m ch ty thuc vo trng thi u v trng thi cui ca h m thi. Q1 + W1 = q2 + W2 = .... = qi + Wi = const (hng s) V phng tin ton hc, biu thc trn ch rng ta c th tm c mt hm s nng lng U ca h nghim ng iu kin:

[Lu l nu qui c du ca cng A ngc vi gio trnh ny (nh trong hu ht cc gio trnh ha l trc y), ngha l cng A m h nhn th c tr s m, cn cng A m h to th c tr s dng, th biu thc ca nguyn l th nht s l: =q-W] U2 v U1 ln lt l tr s ca U trng thi cui v trng thi u ca h.
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q v W l nhit v cng trao i gia h vi mi trng ngoi theo bt c ng bin i no h i t trng thi u n trng thi cui. Hm s U ny biu din ni nng ca h tc nng lng sn cha trong h. [Ni nng ca h do: - ng nng chuyn ng phn t: tnh tin, quay, dao ng. - Nng lng tng tc gia cc phn t: ht, y. - Nng lng cc in t trong phn t. - Nng lng d tr ca ht nhn nguyn t...] ng vi mt bin i nh, ta c:

Ghi ch: - Nguyn l th nht nhit ng hc ch xc nh bin i ni nng tnh c tr s tuyt i ca ni nng U. ch khng th

- Nu h bin i t trng thi (1) n trng thi (2) theo cc cch bin i thun nghch u ging nhau. Cn q, W tri li hay bt thun nghch, th trong cc cch bin i y c tr s khc nhau ty theo cch bin i. - Xem mt h bin i t trng thi (1) n trng thi (2) theo hai ng bin i khc nhau: mt thun nghch v mt bt thun nghch ta c:

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Ngha l nhit trao i cch bt thun nghch nh hn cch thun nghch theo i s. [Nhit m h nhn trong qu thun nghch ln hn so vi trong qu trnh bt thun nghch cn nhit m h ta ra trong qu trnh thun nghch nh hn so vi trong qu trnh bt thun nghch ]. - Trong trng hp trng thi u v trng thi cui ging nhau, tc h thc hin mt chu trnh bin i kn, ta c:

H thc ny l cch pht biu nguyn l tng ng: Mt h bin i theo chu trnh kn v nu ch c nhit v cng trao i gia h vi mi trng ngoi, nu h thu nhit, n s to cng, nu h nhn cng, n s to nhit. Cng v nhit tng ng nhau. [q > 0 W < 0; W > 0 q < 0; |w| = |q| ] - Ngi ta chng minh rng i vi kh l tng, ni nng ca n ch ty thuc vo nhit .

Do , trong mt bin i ng nhit ca kh l tng khng c phn ng ha hc, th bin i ni nng

Cc phn ng ha hc thng c thc hin trong iu kin ng tch hay ng p. 2. Entalpi a. Bin i ng tch.
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 ngha: Trong mt bin i ng tch, tng ni nng ca h nhit m h nhn vo , hoc gim ni nng ca h m h phng thch cho mi trng ngoi . b. Bin i ng p.

bng lng bng lng nhit

Vi mt bin i xc nh:

H c gi l hm s nng lng entalpi ca h V U, pV u l cc hm s trng thi, nn H cng l hm s trng thi. Do bin i entalpi ca h ch ph thuc trng thi u, trng thi cui ca h, ch khng ph thuc vo cch bin i.

ngha: tng entalpi ca h iu kin ng p bng lng nhit m h nhn vo iu kin ng p . Ngc li, gim entalpi ca h iu kin ng p ng p bng lng nhit m h phng thch cho mi trng ngoi iu kin .

Vi kh l tng: pV = nRT
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T: H = U + pV => H = U + nRT

=> Entalpi ca kh l tng ch ph thuc vo nhit T. T (Tng qut q khng phi l hm s trng thi, nhng iu kin ng tch th qV l hm s trng thi).

M: Vi n mol ha cht:

T: (Tng qut q khng phi l hm s trng thi, nhng iu kin ng p, qp l hm s trng thi).

M:

Vi n mol ha cht:
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c. H thc lin h gia Vi kh l tng:

vi

ca kh l tng

III. KHO ST VI BIN I 1. Bin i ng nhit, thun nghch ca h kh l tng, ch c cng gin p T const

V bin i thun nghch

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( T const

Nh vy vi h kh l tng, ng vi mt bin i ng nhit, thun nghch, ch c cng gin p:

2. Bin i on nhit, thun nghch, kh l tng, ch c cng gin p

(1.22) Chia hai v cho :

=>

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m kh l tng:

(1.23)

Tm li: vi h kh l tng, bin i on nhit, thun nghch, ch c cng gin p:

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BI TP CHNG 1 Cu hi. 1. Thit lp biu thc ton hc ca nguyn l 1? 2. Thit lp cng thc tnh cng v nhit cho qu trnh dn n ng nhit ca kh l tng? 3. Thit lp cng thc tnh cng v nhit cho qu trnh dn n ng p v ng tch ca kh l tng? 4. nh lut Hecx v cc h qu. 5. Thit lp mi quan h gia nhit dung ng p v nhit dung ng tch? 6. Khi nim entanpi. Mi quan h gia Qv v Qp? 7. S ph thuc ca hiu ng nhit vo nhit . Phng trnh Kichp ? 8. Thit lp quy tc tnh hiu ng nhit ca phn ng da vo sinh nhit v thiu nhit? 9. Thit lp phng trnh on nhit cho kh l tng Bi tp Cu 1. Tnh U v H cho cc qu trnh sau y: a. Mt mol nc ng c 0oC v 1 atm b. Mt mol nc si 100oC v 1 atm Bit rng: nhit ng c v nhit bay hi ca 1 mol nc tng ng bng -6,01 kJ v 40,79 kJ; th tch mol ca nc lng v nc bng 0,0180 lit v 0,0195 lit. Chp nhn hi l l tng. ( R = 0,082 atm.l/K.mol ; p =1 atm = 101300 Pa ; 1atm.l = 101,3 J = 0,101kJ) Cu 2. Nhit trung ho NaOH v dung dch NH3 bng axit HCl tng ng l -55,9 v 51,34 kJ/mol. Xc nh nhit in ly ca amoniac. Cu 3. Hiu ng nhit ca phn ng Na vi H2O (d) l H01=-183,8 kJ/mol; ca phn ng Na2O vi H2O (d) l H02= -237,9 kJ/mol. Bit: Hos,H2O = -285,8 kJ/mol. Hy tnh H0298 ca phn ng: 2 Na + 1/2 O2 = Na2O Cu 4. Nhit hnh thnh ca Fe2O3 (R) bng -821,3 kJ/mol; ca Al2O3 bng -1675 kJ/mol. Tnh hiu ng nhit ca s kh 1 mol Fe2O3 bng nhm kim loi. Cu 5. Nhit trung ho axit HNO3 bng xt l 55,9 kJ. Cng lng dung dch xt trn c dng trung ho axit CHCl2COOH th hiu ng nhit nhn c bng -62,05 kJ. Nu cho 1 ng lng NaOH vo dung dch cha 1 ng lng HNO3 v 1 ng lng CHCl2COOH th to ra 58,4 kJ. Xc nh s ng lng gam HNO3 phn ng vi NaOH. Cu 6. Nhit hnh thnh kh amoniac 298 K bng -46,2kJ/mol. Nhit dung mol ca H2, N2, NH3 trong khong nhit 250-450 K c cho di y:
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CP, H2 = 29,1 + 0,002 T J/mol.K CP, N2 = 27,1 + 0,006 T J/mol.K CP, NH3 = 25,9 + 0,032 T J/mol.K Tnh H v U i vi phn ng to ra amoniac 398 K. Cu 7. Cho phn ng v cc s liu sau: CO2(k) + 2 H2O (k) CH3OH(k) + 3/2 O2(k) = o H 298 (KJ/mol) -201,2 0 -393,5 -241,8 Cp (J/mol.) 49,4 29,4 37,1 33,6 o Tnh hiu ng nhit ca phn ng 500 K v 1atm Cu 8. Nhit hnh thnh ca nc lng v ca CO2 bng -285,8 v -393,5 kJ/mol 250C, 1 atm, nhit t chy ca CH4 bng -890,3 kJ/mol. Tnh nhit hnh thnh ca CH4 t cc nguyn t iu kin ng p v ng tch. Cu 9. 10 g kh O2 l tng iu kin 298 K c nn on nhit t th tch 8 lit n 5 lit. Xc nh nhit cui cng, cng tiu tn, U v H, bit CV = 5/2 R. Cu 10. Tnh cng ca s bin i ng nhit thun nghch v bt thun nghch 42g kh N2 300K khi: - gin n t 5 atm xung 1 atm - nn t 1 atm n 5 atm Kh c coi l l tng, so snh kt qu.. Cu 11. 25oC, phn ng sau: 2H2(k) + O2 (k) = 2H2O(h) to ra nhit lng l 483,66kJ trong iu kin p sut ring phn ca mi kh trong phn ng l 1 atm v phn ng thc hin trong iu kin ng p. Nhit bay hi ca nc lng 25oC, 1 atm l 44,01 kJ/mol. - Tnh nhit sinh chun ca H2O (l) v H2O (h) 25oC. - Tnh nhit lng to ra khi dng 6 g H2 phn ng to thnh H2O(l). Cu 12. t chy mt lng xc nh C2H5OH(l) P = const = 1 atm v 273K trong s c mt ca 22,4 m3 O2 to ra 243 kJ. - Tnh s mol C2H5OH dng bit rng sau phn ng cn li 5,6m3 O2 ktc. - tnh nhit chy chun ca C2H5OH 273K. - Tnh Ho273 ca phn ng: C2H5OH (l) + O2 (k) = CH3COOH (l) + H2O (l) Cu 13. Tnh Ho298 v Uo298 ca phn ng sau: 4Cgr + 3H2 + 2O2(k) = C4H6O4(r)
Cho Ho298,C(kJ/mol) -393,51 -285,84 -1487

Cu 14. Phn ng: C6H6 + 15/2O2(k) = 6CO2(k) + 3H2O 300K c QP - QV = 1245J. Hi C6H6 v H2O trong phn ng trng thi lng hay hi? Cu 15. Tnh Ho473 ca phn ng sau:
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CO(k) + 1/2 O2(k) = CO2(k) cho bit ca CO(k) v CO2(k) ln lt l -110,52 v -393,51 kJ/mol; CoP (J/mol.K) ca cc cht nh sau: CoP(CO) = 26,53 + 7,7.10-3T - 1,17.10-6T2 CoP (CO2) = 26,78 + 42,26,10-3T - 14,23.10-6T2 CoP (O2) = 26,52 + 13,6.10-3T - 4,27.10-6 T2 Ho298,S Cu 16. Tnh Ho298,s ca CH4(k), bit rng nng lng lin kt H-H trong H2 l 436kJ/mol, nng lng lin kt trung bnh C-H trong CH4 l 410kJ/mol v nhit nguyn t ho Ho298,a ca Cgr l: Cgr --> C (k) , Ho298,s = 718,4 kJ/mol. Cc gi tr trn ly iu kin chun v 25oC. Cu 17. Tnh nhit lng cn thit nng nhit ca 0,5mol nc t -50oC n 500oC P = 1 atm. Bit rng nhit nng chy ca nc 273K l 6004J/mol; nhit bay hi ca nc 373K l 40660 J/mol; cc gi tr nhit dung (J/mol.K ) l: CoP,R = 35,56; CoP,L = 75,3 v CoP,H = 30,2 + 10-2T.

20

Chng 2. NGUYN L TH HAI NHIT NG HC V P DNG VO HA HC Nguyn l th nht nhit ng hc gip xc nh bin i ni nng , bin i ca mt qu trnh nhng ni chung khng gip d on c qu trnh ny c entalpi t xy ra c hay khng. Nguyn l th hai nhit ng hc gip khng nh c iu ny. p dng vo ha hc, nguyn l th hai nhit ng hc gip tin on mt phn ng ha hc c th xy ra c hay khng mt iu kin xc nh no . I. KHI NIM V ENTROPI Xem mt h gm cc phn t mt cht kh ang nhit thp, nu ta t nng h tc cung cp mt nhit lng q vo, cc phn t kh s gia tng chuyn ng, c s xo trn hay mt trt t nhiu trong h so vi trc khi cung cp q. Nhit lng q cng nhiu th s xo trn cng ln, tc s bin thin xo trn t l thun vi nhit lng q c cung cp vo h. Nu cng mt lng nhit q nhng nu cung cp vo h trn ang nhit cao, th s bin thin xo trn s t hn so vi lc h ang nhit thp. Nh vy s bin thin xo trn t l nghch vi nhit T. Ngi ta dng mt hm s trng thi o mc xo trn hay t do ca mt h. l hm s entropi S m trong mt bin i nh c cho bi:

thun nghch l lng nhit c cung cp vo h mt cch thun nghch lm tng hm s entropi S ca h ln mt lng dS hoc l lng nhit c ly ra khi h mt cch thun nghch lm gim hm s entropi S ca h mt lng dS. nhit khng i, vi mt bin i thun nghch xc nh:

Khi nhit T thay i:

21

V l hm s trng thi, ging nh hm s ni nng U, hm s entalpi H, nn bin i entropi khng ty thuc ng bin i m ch ty thuc trng thi u v trng thi cui ca h m thi.

Trong phm vi ha hc, hm s entropi c dng vi ngha c nh t do ca mt h ha hc. Mt h bin i t trng thi u n trng thi cui, vi trng thi cui t t do hn trng thi u th Ngc li, nu trng thi cui t do hn trng thi u th V d:

II. PHT BIU NGUYN L TH HAI NHIT NG HC Nguyn l th hai nhit ng hc c th c pht biu nh sau:

22

- Mi h c xc nh bng mt i lng gi l entropi S m bin i dS trong mt bin i nh l:

Vi mt bin i xc nh t trng thi (1) n trng thi (2), bin i entropi

l:

qthun nghch l nhit trao i khi h bin i trong mt bin i nh theo mt ng bin i thun nghch.

Trong mt bin i ng nhit, thun nghch, bin i entropi

l:

- Trong mt bin i thun nghch: * Nu h c lp, th bin i entropi ca h l:

* Nu h khng c lp th h cng mi trng ngoi to thnh mt h c lp, nn tng s bin i entropi ca h v ca mi trng ngoi bng khng.

- Trong mt bin i t nhin (bt thun nghch): * Nu h c lp, th bin i entropi ca h dng:

23

* Nu h khng c lp th tng s bin i entropi ca h v ca mi trng ngoi dng.

III. CCH TNH BIN I ENTROPI Hm s entropi S ph thuc vo cc thng s nhit T, th tch V hay p sut p. S = S(T,V) hay S = S(T,p) 1. S = S(T,V)

- Vi bin i ng nhit To: (dT = 0)

- Vi bin i ng tch th tch khng i V0: (dV = 0)

24

Nu t nhit mol ng tch

khng i trong khong nhit (T1,T2):

2. S = S(T,p)

dS = [Coi nh ch c cng gin p]

dS =

Vi trng hp kh l tng:

- Vi bin i ng nhit T0:

- Vi bin i ng p p0:

Nu t nhit mol ng p

khng i trong khong nhit (T1,T2):

25

Ghi ch: - p dng cc cng thc trn phi ch n cc iu kin thc hin bin i. - Tuy iu kin thit lp cc cng thc trn l h kh l tng nhng cng c th p dng tnh bin i entropi cho ha cht trong iu kin thch hp khong nhit khng ln lm. 3. Cch tnh bin i entropi trong s thay i trng thi a. Qu trnh nng chy:

Gi nhit nng chy ca ha cht l nhit ti c s cn bng pha gia dng rn v dng lng ca ha cht di p sut 1 atm. nhit nng chy mol ca ha cht, l nhit lng cn cung cp mt mol ha cht (A) t dng rn thnh dng lng nhit nng chy , p sut 1atm. , , 1atm).

cng l nhit lng phng thch khi mt mol ha cht ng c t dng lng

b. Qu trnh bay hi:

Gi TS: nhit si (oK) ca ha cht (A), l nhit ti c s cn bng pha gia dng lng v dng hi ca ha cht di p sut 1atm.
26

S:

nhit ha hi mol ca ha cht, l nhit lng cn cung cp mt mol ha cht (A)

t dng lng thnh hi nhit si TS di p sut 1atm. cng l nhit lng phng thch khi mt mol A dng hi ngng t thnh dng lng TS, 1atm). y l mt bin i ng nhit, ng p, thun nghch.

IV. NGUYN L TH BA NHIT NG HC. ENTROPI CA HA CHT 1. Nguyn l th ba nhit ng hc "Entropi ca mt tinh th hon ho bng khng 0oK" Tinh th hon ho l tinh th trong cc phn t ch c mt cch sp xp duy nht 0oK. Nhiu ha cht c tinh th khng hon ho 0oK nh H2 (orto, para), CO, N2O, H2O... Nguyn l th ba nhit ng hc gip tnh entropi ca mt ha cht nhit xc nh.

2. Cch tnh bin i Entropi ca mt ha cht Xt hai trng hp sau y: a. Khng c s thay i trng thi trong khong nhit (0, T)

Nu chn

v tinh th cht thuc loi hon ho

27

V t nhit mol ng p theo thng s

ph thuc nhit T, ta v ng biu din ca hm s

b. C s thay i trng thi trong khong nhit (0, T)

28

T th, o cc din tch nhit ToK.

, cng li s bit c entropi mol ca ha cht

Da vo cch tnh , c th tnh c entropi mol ca ha cht mt nhit xc nh (nhit ti ha cht cha b phn hy). Sau y l tr s entropi mol iu kin chun thc (298 K, 1atm) ca mt s ha cht

Ha cht Ag(r) AgCl(r) Al(r) Al2O3(r) C(r,graphit) CO(k) CO2(k) CH4(k) CH3Cl(k) CH3OH(l)

0 298 K

Ha cht cal/mol.K 10,17 23,00 6,77 12,19 1,36 47,30 51,06 44,50 55,97 30,30 25,00 48,00 52,54 54,85 H2O(k) H2O(l) HCl(k) HNO3(l) H2SO4(l) CH3COOH(l) Hg(l) Hg(k) K(r) KCl(r) K2SO4(r) N2(k) NH3(k) NH4Cl(r)

0 298 K

J/mol.K 42,55 96,20 28,30 51,00 5,69 197,90 213,60 186,20 234,20 126,80

J/mol.K 188,70 69,96 186,70 155,60 157,00 160,00 76,10 175,00 64,18 82,59 176,00 191,50 192,50 94,60

cal/mol.K 45,11 16,72 44,62 37,19 37,50 38,20 18,20 41,80 15,34 19,74 42,00 45,77 46,01 22,60

CO(NH2)2(r,ure) 104,60 C2H2(k) C2H4(k) C2H6(k) 200,80 219,80 229,50

29

C2H5OH(l) Ca(r) CaCO3(r) CaCl2(r) CaO(r) Ca(OH)2(r) CaSO4(r) CaSO4.2H2O(r) Cl2(k) Fe(r) Fe2O3(r) H2(k) S(r) C(r,kim cng)

161,00 41,40 92,90 114,00 40,00 76,10 107,00 194,00 223,00 27,00 90,00 130,60 31,90 2,40

38,40 9,89 22,20 27,20 9,50 18,20 25,50 46,36 53,29 6,50 21,50 31,21 7,62 0,57

NO(k) NO2(k) N2O(k) N2O4(k) Na(r) Na2CO3(r) NaHCO3(r) NaCl(r) NaOH(r) Na2SO4(r) O2(k) PbO(r) SO2(k) SO3(k)

210,60 240,50 220,00 304,00 51,00 136,00 102,00 72,38 64,18 149,40 205,00 67,80 248,50 256,20

50,34 57,47 52,58 72,70 12,20 32,50 24,40 17,30 15,34 35,70 49,00 16,20 59,40 61,24

[Theo sch "Fundamentals of Chemistry" ca James E.Brady v John R.Holum (ti bn ln 3, nm 1988)] Nhn xt:

- Cng trng thi nh nhau (rn, lng hoc kh), cht no c cu to phc tp hn th c tr s ln hn.

p dng bng tr s entropi mol chun thc ca cc cht ta c th tnh c bin i entropi ca mt phn ng iu kin chun thc.
30

Vi phn ng: mA + nB -> pC + qD

2.26

V d 1:

V d 2:

[Ph hp vi d on, v bn sn phm c 1 mol kh trong khi bn tc cht c 2 mol khi nn t c s xo trn hn]. 3. Bin i ca bin i Entropi theo nhit Bit nhit To, tnh nhit T ca mt phn ng.

Xem phn ng: mA + nB -> pC + qD

T (2.17) =>
31

Nu T0 l nhit iu kin chun thc (298 K) v nu p sut l 1atm, th:

Nu

khng i theo nhit T trong khong (298 K, T) th:

32

CHNG 3. TH NHIT NG TH HA HC IU KIN CN BNG V DIN BIN CA QU TRNH I. HM NNG LNG T DO G (TH NG NHIT NG P, HM GIBBS) 1. Hm s nng lng t do v bin i Trn nguyn tc nu tnh c ca h v ca mi trng ngoi km theo mt bin i th ta c th xc nh bin i c xy ra t nhin (bt thun nghch) hay khng. Tuy nhin, s xc nh ca mi trng ngoi khng phi lc no cng d dng do ngi ta tm cch da trn chnh h kho st kt lun. Mt h c khuynh hng bin i t nhin (bt thun nghch) khi tha mn hai iu kin sau y: - iu kin v hay : mt bin i c khuynh hng xy ra nu ta nhit ( , ty iu kin th nghim ng p hay ng tch). - iu kin v ( ). : mt bin i c khuynh hng xy ra nu c s tng entropi ca h

. Tuy nhin, Vy iu kin u i mt bin i p, T khng i l c trng hp (thu nhit) hoc (gim entropi ca h), bin i cng c th xy ra c, nu yu t cn li ln p hn (tc trong trng hp bin i thu nhit v trong trng hp c s gim entropi ca h). Mt hm s trng thi c chn gp hai iu kin trn li, l hm s nng lng t do G, c nh ngha nh sau:
3.1

=> dG = dH - TdS - SdT iu kin ng p: iu kin ng nhit: dT = 0

33

Cc bin i xy ra theo hai trng hp: a- Nu bin i thun nghch:

3.2

Vi mt bin i xc nh:
3.3

b- Nu bin i bt thun nghch (bin i t nhin): (2.31)

3.4

Vi mt bin i xc nh:
3.5

Tm li:

Vi biu thc trn, c th kt lun l mt bin i c th xy ra t nhin nu mt trong ba trng hp sau y c tha ( T, p khng i):

C ba trng hp trn trong thc t u c ghi nhn. [ Ngi ta chng minh c: gim hm s G T, p khng i bng vi cng thun nghch m h to cho mi trng ngoi, khng k cng lm thay i th tch ca h, cng ny c th c s dng ty nghi, nn c gi l nng lng t do ].
34

2. Vi phn ca hm th ng nhit ng p G T biu thc G = H - TS => dG = dH - TdS - SdT (2.36) m H = U + pV => dH = dU + pdV + Vdp

(Coi nh ch c cng gin p)

3.6

(2.36) => dG = TdS + Vdp - TdS - SdT

3.7

3. Bin i ca nng lng t do theo nhit v p sut a. Bin i ca nng lng t do theo p sut iu kin ng nhit T dG = Vdp - SdT iu kin ng nhit: dT = 0 => dGT = Vdp

Vi kh l tng:

35

(2.39)

3.8

[Cng thc trn p dng cho kh l tng, nhng c th p dng cho ha cht vi iu kin nhit T, ha cht trng thi kh v coi nh l kh l tng]. Nu p1 = 1 atm

Vi 1 mol:
3.9

[p: p sut, tnh bng atm. Ty theo th nguyn ca R mT c th nguyn thch hp tng ng]. b. Bin i ca G theo nhit iu kin ng p G = H - TS

36

3.10

Trong mt phn ng ha hc: mA + nB -> pC + qD

Theo kt qu chng minh trn:

37

=>

3.11

3.12

bt c nhit no iu y l h thc Gibbs - Helmholtz, h thc ny gip tnh kin ng p, khi bit mt nhit xc nh v bit ca qu trnh. 4. Nng lng t do mol chun trong mt bin i, ngi ta cng chn trng thi chun c th tnh bin thin nh trng hp entalpi. Trng thi chun ca mt ha cht l dng bn nht ca ha cht 25oC, 1atm. V d trng thi chun thc ca carbon (25oC, 1atm) l carbon graphit (than ch), ch khng phi l carbon kim cng. Ngi ta qui c, nng lng t do ca n cht trng thi chun bng khng. Da vo qui c ny, ngi ta xc nh c nng lng t do mol chun ca cc hp cht. Nng lng t do mol chun c biu din bng k hiu V d: .

38

M: Tnh c [Cn c vo tr s entalpi mol chun v entropi mol chun ca cc cht] Th T = 298 K Tnh c Di y l tr s nng lng t do mol chun ca mt s cht Ha cht
298 K

Ha cht
298 K

Ag(r) AgCl(r) Al(r) Al2O3(r) C(r,graphit) CO(k) CO2(k) CH4(k) CH3Cl(k) CH3OH(l) CO(NH2)2(r) CO(NH2)2(aq) C2H2(k)

KJ/mol 0,00 - 109,70 0,00

Kcal/mol 0,00 - 26,22 0,00

H2O(k) H2O(l) HCl(k) HNO3(l) H2SO4(l) CH3COOH(l) Hg(l) Hg(k) K(r) KCl(r) K2SO4(r) N2(k) NH3(k)

KJ/mol - 228,60 - 237,20 - 95,27 - 79,91 - 689,90 - 392,50 0,00 + 31,80 0,00 - 408,30

Kcal/mol - 54,64 - 56,69 - 22,77 - 19,10 - 164,90 - 93,80 0,00 + 7,59 0,00 - 97,59

- 1576,40 - 376,77 0,00 - 137,30 - 394,40 - 50,79 - 58,60 - 166,20 - 197,20 - 203,80 0,00 - 32,81 - 94,26 - 12,14 - 14,00 - 39,73 - 47,12 - 48,72

- 1316,40 - 314,62 0,00 - 16,70 0,00 - 3,98

+ 209,00 + 50,00

39

C2H4(k) C2H6(k) C2H5OH(l) C8H18(l) Ca(r) CaCO3(r) CaCl2(r) CaO(r) Ca(OH)2(r) CaSO4(r)

+ 68,12 - 32,90 - 174,80 + 17,30 0,00

+ 16,28 - 7,86 - 41,77 + 4,14 0,00

NH4Cl(r) NO(k) NO2(k) N2O(k) N2O4(k) Na(r) Na2CO3(r) NaHCO3(r) NaOH(r) NaCl(r) Na2SO4(r) O2(k) PbO(r) S(r) SO2(k) SO3(k)

- 203,90 + 86,69 + 51,84

- 48,73 + 20,72 + 12,39

+ 103,60 + 24,76 + 98,28 0,00 + 23,49 0,00

- 1128,80 - 269,78 - 750,20 - 604,20 - 896,76 - 179,30 - 144,40 - 214,33

- 1048,00 - 250,40 - 851,90 - 382,00 - 384,00 - 203,60 - 91,40 - 94,79

- 1320,30 - 315,56

CaSO4.1/2H2O(r) - 1435,20 - 343,02 CaSO4.2H2O(r) Cl2(k) Fe(r) Fe2O3(r) H2(k) - 1795,70 - 429,19 0,00 0,00 - 741,00 0,00 0,00 0,00 - 177,10 0,00

- 1266,80 - 302,78 0,00 - 189,30 0,00 - 300,40 - 370,40 0,00 - 45,25 0,00 - 71,79 - 88,52

[ Theo sch Fundamentals of Chemistry ca James E. Brady v John R. Holum, ti bn ln 3 - nm 1988 ] II. P DNG NNG LNG T DO CHUN C th p dng bng tr s nng lng t do mol chun thc ca ha cht tnh c bin i nng lng t do ca mt qu trnh iu kin chun thc . Hoc c th i t nh ngha ri p dng bng tr s

40

ca cc ha cht tnh . T tr s tnh c c th kt lun phn ng c xy ra c iu kin chun thc (250C, 1atm) hay khng.

Vi phn ng: mA + nB -> pC + qD

3.13

V d 1: Vi phn ng NO(k) + 1/2 O2(k) -> NO2(k) Cch 1: Tnh ca phn ng da vo ca cc cht

[ iu ny ph hp vi thc t, kh NO khng mu tc dng d dng vi O2 ca khng kh to kh NO2 c mu nu. Khi cho kim loi ng (Cu) vo dung dch HNO3 d m c hay long u c to kh mu nu NO2 nu phn ng xy ra trong kh quyn. V tuy vi dung dch long c to NO nhng NO tc dng tip vi O2 ca khng kh to NO2.

41

Cch 2: Tnh

ca phn ng da vo

ca cc cht.

V d 2: Tnh

ca phn ng

CH2=CH2(k) + H2(k) -> CH3-CH3(k) Cch 1: Tnh ca phn ng cn c vo tr s ca cc cht.

42

[ Nhng trong thc t phn ng ny khng xy ra c 25oC, 1atm. Nguyn nhn l vn tc phn ng qu chm iu kin ny nn thc t phn ng nh cha xy ra. Phi dng cht xc tc thch hp, thc hin phn ng nhit thch hp thc y vn tc phn ng xy ra nhanh hn. Trng hp ny ngi ta ni yu t nhit ng hc cho php phn ng xy ra nhng yu t ng ha hc cha cho php]. Cch 2: Tnh trc ri tnh sau:

III. HA TH (TH HA HC) 1. nh ngha ha th Nhng h thc va nu trn p dng cho nhng h trong lng mi ha cht ca h khng thay i. Trn thc t, qu trnh ha hc km theo s thay i lng ca mi cht. Nng lng t do (th ng nhit ng p) chng nhng ph thuc vo nhit T, p sut p m cn ty thuc vo s mol ca cc cht c trong h.

43

3.14

c gi l ha th ca cu t i hay th ng nhit ng p mol ring phn ca cu t i hay nng lng t do mol ring phn ca cu t i ca hn hp. 2. ngha ca ha th Trong mt h iu kin ng nhit, ng p, nu thm vo h mt lng tht nh s mol dni ca cu t i th th ng nhit ng p hay nng lng t do ca h tng ln mt lng l (idni. Ni chung, ngi ta ch rng:
3.15

Nh vy, chnh l phn ng gp ring vo nng lng t do ca h ca 1 mol cu t i trng thi hn hp vi cc cu t khc, thay i vi thnh phn ca hn hp. Gi s mt cu t i ca h c hai tr s l khc nhau hai trng thi A v B ca h trong iu kin ng nhit v ng p, vi tt c s mol ca nhng cu t khc khng i, khi mol ca i chuyn t A sang B:

[ Dng du - v c

mol i khng cn trng thi A]

S chuyn s xy ra t nhin nu

Vy vt cht chuyn t trng thi c cao n trng thi c thp tng t nh dng in di chuyn t cc c in th cao n cc c in th thp, do m t ha th c gn cho . ng v mt phn ng ha hc, ha th cn do tim nng ca cu t cho phn ng ha hc, v bin i ha hc iu kin ng nhit v ng p xy ra t nhin, i km theo vi s gim nng lng t do v ha th th c ng gp vo nng lng t do.

44

3. Biu thc ca ha th a. Kh l tng nguyn cht Trong trng hp ny, ha th chnh l nng lng t do mol ca cu t i nguyn cht.

[ coi (2.39), (2.41) ]

Nu ly

bng atm, ta c:
3.16

l ha th ca cu t i nguyn cht nhit T v p sut p sut ca i, tnh bng atm. b. Kh l tng trng thi hn hp Ngi ta chng minh h thc:
3.17

Vi pi l p sut ring phn ca cu t i. Theo nh lut Dalton, l phn mol ca cu t i v p l p sut ton phn ca h.

(2.49)
3.18

Vi:
3.19

45

l ha th ca cu t i nguyn cht nhit T v p sut p bng p sut ton phn ca h. c. Dung dch trng thi dung dch long vi cu t i ha tan trong dung mi c nng l Ci, th c th s dng h thc:
3.20

l ha th ca i ng vi nng bng 1mol/l. Cc cng thc trong phn cn bng ha hc v dung dch u i t ha th. BI TP CHNG 2 V 3 Cu 1. Cc anh ch ngh sao v nhng cu sau y:

a). b).

u ng trong tt c mi bin i. u ng trong tt c mi bin i. ng vi s bc hi ca mt mol toluen 110oC di

Cu 2. Tnh q, p sut 1atm.

Cho bit: nhit bc hi ca toluen trong iu kin th nghim trn l nhit si ca toluen l 110oC, coi hi toluen l kh l tng v ly C = 12; H = 1

Cu 3. D on du ca (S trong nhng bin i sau y:

46

a) NO(k) +

O2(k) -> NO2(k)

b) C2H4(k) + HCl(k) -> C2H5Cl(k) c) N2(k) + 3H2(k) -> 2NH3(k) d) CaCO3(r) -> CO2(k) + CaO(r) e) 2CuO(r) + C(r) -> 2Cu(r) + CO2(k)

f) Ca(r) +

O2(k) -> CaO(r) n

Cu 4. Mt mol kh l tng gin ng nhit v thun nghch t th tch

Cu 5. Mt mol kh l tng c mang t trng thi (22,4l; 273 K) n trng thi (2atm; 303 K). Tnh ca bin i trn.

khi cho mt lng kh argon 25oC, 1atm c th tch 500cm3 gin n Cu 6. Tnh n 1000 cm3 ng thi t nng n 100oC .

Cu 7. Tnh (S0298 K ca cc phn ng sau:

47

a) Ca(r) +

O2(k) -> CaO(r)

b) CaCO3(r) -> CaO(r) + CO2(k)

c) NO(k) + Cho bit:

O2(k) -> NO2(k)

Cu 8. a) Tnh H2O(k) + CO(k) -> H2(k) + CO2(k)

cho phn ng:

b) Nu xem cc kh trn nh kh l tng, tnh c) Bin lun s kh thc hin ca phn ng.

Cu 9. Gii thch du ca

trong cc bin i sau:

a) H2O(l, - 10oC, 1atm) -> H2O(r, - 10oC, 1atm) b) H2O(l, 100oC, 1atm) -> H2O(h, 100oC, 1atm) Cu 10. Tnh q, nhit bc hi ca
48

v 1atm. Cho bit , nhit si ca CS2 l 46,2oC.

Cu 11. Tnh

cho bin i:

CH3OH(l, 64oC; 1atm) -> CH3OH (h, 64oC; 0,5 atm) Bit rng nhit si ca CH3OH l 64oC v nhit bc hi ca CH3OH 64oC, 1atm l

Coi hi CH3OH nh kh l tng.

Cu 12. Xem phn ng: CaCO3 (r) -> CaO (r) + CO2 (k) a) Tnh bin i b) Phn ng trn c thc hin c 25oC hay khng? c) Ti sao phn ng ny c th thc hin c nhit cao? d) Gi s khng i theo nhit , phng tnh nhit thp nht m phn ng c th thc hin c. e) Kt qu tnh c c ph hp vi iu kin thc nghim ch to vi sng hay khng? Cho bit:

49

Cu 13. D on du ca

trong cc qu trnh sau, c gii thch:

a) O2(k; 25oC; 1atm) -> O2(k; 25oC; 0,1atm) b) NH4Cl(r) -> NH3(k) + HCl(k) c) CO(k) + H2O(h) -> CO2(k) + H2(k) d) CH4(k) + 2O2(k) -> CO2(k) + 2H2O(h) e) CH4(k) + 2O2(k) -> CO2(k) + 2H2O(l) f) N2(k)(25oC; 1atm) -> N2(k)(0oC; 1atm) g) N2(k)(25oC; 1atm) -> N2(k)(25oC; 2atm) h) 2H2(k) + O2(k) -> 2H2O(h) Cu 14. D on entropi ca cc h sau y s tng hay gim khi cc qu trnh vt l xy ra iu kin nhit v p sut khng i: a) Benzen lng ng c thnh benzen rn. b) Benzen lng bay hi. c) Pentan, mt cht lng, c ha tan trong hexan, cng l mt cht lng. Cu 15. Hy ch r cht no trong cc cht di y c tr s entropi mol chun thc
0 298 K

cao hn. Gii thch:

a) Ca(r) v Mg(r) b) H2O(k) v H2S(k) c) PCl3(k) v PCl5(k) d) Cl2(k) v F2(k)

50

e) Br2(l) v I2(r) Cu 16. a) Th hnh (a hnh) l g? Cc d kin v hai cht th hnh ca phosphor sau:

b) Dng th hnh no bn hn? c) Dng th hnh no hin din nhiu hn? Gii thch. Cu 17. Hidrazin, , c dng lm nhin liu cho ha tin. Hidrazin lng c

a) Hidrzin c th iu ch theo phn ng sau y hay khng: Gii thch. b) Da vo s liu sau, tnh ton khng nh cu tr li trn:

Cu 18. Phn ng ca NO2 vi nc, to acid nitric, gp phn to ma acid. 3NO2(k) + H2O(l) -> 2HNO3 (dd) + NO(k) Tnh ca phn ng ny 25oC. Phn ng c xy ra c iu kin chun

thc hay khng? Cho:

51

Cu 19. Cc ng v ca Uranium thng c tch ra bng cch dng hin tng r r (effusion) ca cng nh ch to bom nguyn t. 99,28% v s nguyn t trong t nhin. Hi c dng trong l phn ng ht nhn chim c vn tc r r ln hn hi

ln. S r r ny xy ra t nhin mc d bin i entalpi ca qu trnh ny gn bng khng. Du ca bin i entropi ca qu trnh ny phi nh th no? Cu 20. Ngi ta ni trong mt bin i t nhin thun nghch th =0. iu ny c ng khng? lun lun dng v nu bin i

Ngi ta em 1 mol nc lng v bin n thnh nc mt cch thun nghch 0oC, 1atm. Bit rng nhit phng thch l 1436 cal, tnh .

Cu 21. Trong mt h khng c lp v gi s iu kin l tng c tha. a) Tnh n V2. trong mt bin i ng nhit v thun nghch, gi s c s gin t th tch V1

b) Tnh trong mt bin i ng nhit v bt thun nghch c trng thi u v trng thi cui ging nh cu (a)
52

c) Tnh

trong mt bin i theo mt chu trnh kn.

Cu 22. Phn ng: Da trn

xy ra vi

nh th no?

, ta c quyn kt lun phn ng khng xy ra c hay khng?

Cu 23. V phng din nng lng t do, tm mt h thc tng ng vi cc s kin ghi sau y: a) Nc lng si 100oC di p sut 1atm. b) Ciclohexan dng gh bn hn Ciclohexan dng tu .

c) Vng c nhit nng chy cao hn bc. Cu 24. Cho bit nhng cu sau y ng hay sai v gii thch: a) S gin n kh l tng ng nhit trong chn khng l mt bin i on nhit. b) S bin i trn (gin n kh l tng ng nhit trong chn khng) i km vi c) Entropi ca kh l tng khng ty thuc vo p sut. Cu 25. Xem phn ng: C + O2 -> CO2 (I) 2C + O2 -> 2CO (II) 2Zn + O2 -> 2ZnO (III) .

1) a) Phn ng no xy ra vi s gim entalpi nhiu nht?

53

b) Phn ng no xy ra vi s bin i entropi nhiu nht? 2) a) C th kt lun nh th no v hai phn ng (I), (II) nhit thp? b) Tr li cu hi tng t nhng nhit cao? c) C th kt lun nh th no v i lc ca C v Zn i vi O2 nhit cao? Suy ra mt p dng quan trng trong k ngh ha hc. 3) a) Tnh bin i entropi khi 1 mol cng dng lng. Cho b) Nhit nng chy Tnh (S cho bin i: H2O(r, 0oC, 1atm) -> H2O(h, 100oC, 1atm) Tr s trn c xc nh bin i xy ra t nhin (bt thun nghch) hay khng? , nhit bc hi mol ca H2O l p sut 1atm

Cu 26. Cho phn ng: Cl2(k) + ClF3(k) -> 3Cl-F(k) 1) Tnh nhit phn ng da trn nng lng lin kt 298 K. 2) Phn ng ny c d on nh th no v phng din entropi? 3) Gi s ca phn ng khng thay i nhiu theo nhit . D on l thuyt xem phn ng c th xy ra 250oC c hay khng?

4) Th nghim cho bit:

54

Da trn cc d kin thc nghim, th sinh c th kt lun g v s kh thc hin ca phn ng trn 250oC? 5) C th kt lun g v nng lng lin kt Cl-F trong ClF v ClF3. Cho bit EF-F = 38 Kcal.mol-1. 6) Suy ra mt kt lun chung v bng nng lng lin kt cho trong phn gio khoa?

Cu 27. Tnh s thay i ca ha th khi 1 mol nc bc hi 1 bar v 25oC.

Cu 28. Hy cho bit s thay i ha th ca mt kh l tng khi nn ng nhit kh ny t 1,8 atm n 29,5 atm 40oC.

55

Chng 4

CN BNG HA HC

Phn ng c gi l phn ng cn bng hay thun nghch khi n xy ra theo hai chiu ngc nhau trong cng mt iu kin. Do , phn ng cn bng xy ra khng hon ton, ngha l sau phn ng khng nhng thu c sn phm (C, D) m cn c c cc tc cht (A, B). V d: Vi phn ng ester ha gia acid acetic vi ru etilic

CH3-COOH + CH3-CH2-OH

CH3-COO-CH2-CH3 + H2O

Nu ly 1mol cho tc dng vi 1mol th sau khi phn ng t mc cn bng (coi nh phn ng xong), ta thu c 2/3 mol ester mol ru

Phn ng cn bng c gi l t trng thi cn bng khi trong cng mt n v thi gian nu c bao nhiu phn t tc cht (A, B) mt i do tham gia phn ng thun to sn phm (C, D) th cng c by nhiu phn t tc cht (A, B) c to tr li t phn ng nghch, lc vn tc phn ng thun v vn tc phn ng nghch bng nhau, lc ny nng cc cht trong phn ng khng thay i na. Cn bng ha hc c gi l cn bng ng v thc ra lun lun c phn ng thun v nghch xy ra nhng do lng cc cht trong h phn ng khng thay i khi phn ng t trng thi cn bng nn phn ng c coi nh xong. Hn na, c th lm thay i trng thi cn bng ca phn ng bng cch thay i cc yu t nh nng cc cht, nhit , p sut. I. NH LUT TC DNG KHI LNG nh lut ny do Gulberg, Waage (Na Uy) a ra nm 1864, nhm xc nh trng thi cn bng ca mt phn ng cn bng. 1. Trng hp cn bng gia cc kh c th xem nh kh l tng a. Hng s cn bng KC
56

Xt phn ng cn bng:

Gi ln lt l hng s vn tc ca phn ng thun v nghch. Gi s phn ng thun cng nh phn ng nghch u thuc loi n gin (ngha l phn ng ch xy ra trong mt giai on, bc phn ng ring phn ca mi tc cht bng h s t lng nguyn ti gin ng trc mi tc cht trong phn ng). Vn tc phn ng thun l: v1 = k1[A][B] Vn tc phn ng nghch l: v-1 = k - 1[C][D] Gi s lc bt u phn ng, ch c A, B hin din. Vn tc phn ng thun lc u rt ln, vn tc phn ng nghch bng khng. Phn ng cng xy ra lu, nng cc tc cht A, B cng gim , nng cc sn phm C, D cng tng . Nh vy, gim dn theo thi gian, cn tng dn theo thi gian. Sau mt thi gian vn tc phn ng thun v1 s bng vn tc phn ng nghch , lc ny phn ng t trng thi cn bng, phn ng c coi nh xong. v1 = v- 1 => k1[A][B] = k_ 1[C][D]

=> V l cc hng s vn tc phn ng, ch ty thuc nhit (v ty thuc bn cht ca phn ng), cho nn ng vi mt nhit xc nh (v mt phn ng xc nh), ta c:

57

cb: cn bng, ch nng cc cht C, D, A, B lc t trng thi cn bng. KC c gi l hng s cn bng ca phn ng lin h n nng (mol/l). KC ch ph thuc nhit v bn cht ca phn ng, m khng ph thuc vo nng cc cht trong phn ng. H thc trn biu din s lin h gia nng ha cht (tc khi lng ca ha cht) lc cn bng, chnh l ni dung ca nh lut tc dng khi lng. C th pht biu nh lut ny nh sau: Khi mt phn ng ng th t trng thi cn bng th t s tch s nng sn phm vi tch s nng tc cht l mt hng s mt nhit xc nh. Tng qut vi phn ng: mA + nB pC + qD

ngi ta chng minh rng, gi tr KC:

T khng i l mt hng s, Vi [A], [B], [C], [D] l nng ca A, B, C, D lc cn bng. V d: vi phn ng: 2NOCl(k) 2NO(k) + Cl2(k) th hng s cn bng KC l:

b. Hng s cn bng KP Hng s cn bng ny lin h n p sut ring phn ca ha cht th kh lc cn bng (lc t trng thi cn bng). [p sut ring phn ca mi cu t ca hn hp c th tch chung l V l p sut m cu t y c khi n ng ring mt mnh v cng chim th tch V ca hn hp cng nhit ].
58

Xt phn ng: Gi PA, PB, PC, PD ln lt l p sut ring phn ca cc kh A, B, C, D c th xem , ln lt l s mol ca A, B, C, D hin din nh kh l tng lc cn bng trong th tch V ca h phn ng (bnh phn ng) lc cn bng nhit T (oK). T ta c:

Thay [A], [B], [C], [D] vo biu thc ca hng s cn bng KC:

(4-3)

Do KC ch ph thuc nhit nn KP cng ch ph thuc nhit T. c. Hng s cn bng Kx

59

Hng s cn bng ny lin h n phn s mol (phn mol, phn mol) ca cc cht trong phn ng. [Phn s mol (phn mol hay phn mol) x ca cu t i trong hn hp gm nhiu cu t l t s gia s mol ca i vi tng s mol ca cc cu t c trong hn hp.

Xt phn ng: Gi P l p sut ca hn hp kh lc cn bng; xA, xB, xC, xC ln lt l phn s mol ca A, B, C, D lc cn bng.

Vi

l tng s mol hn hp gm cc kh A, B, C, D lc cn bng.

Th

ca phn ng:

60

: Tng h s mol kh sn phm = tng h s mol kh tc cht Nh vy hng s cn bng Kx ph thuc vo nhit T v p sut tng qut P ca hn hp kh lc cn bng. Nu => p + q = m + n => Tng h s mol kh bn sn phm = Tng h s mol kh bn tc cht

Ch thch: - Ngi ta ch rng trong biu thc ca cc hng s cn bng lin h n kh nu trn, ta khng ch n cc cht lng v cht rn. V d: - Vi phn ng: CaCO3(r) CaO(r) + CO2(k)

Th hng s cn bng l Kp = PCO2 - Vi phn ng: NH4Cl(r) HCl(k) + NH3(k)

Th hng s cn bng l Kp = PHCl.PNH3 - Vi phn ng: HCl(k) + NH3(k) NH4Cl(r)

Th hng s cn bng l Kp = - Hng s cn bng K cng ln, phn ng cng thin v chiu thun, hng s cn bng K cng nh phn ng cng thin v chiu nghch

61

- Ty theo h s ca phn ng m hng s cn bng ca cng mt phn ng c th khc nhau. V d: - Vi phn ng:

- Vi phn ng:

2. Trng hp cn bng trong dung dch lng Trong trng hp ny, thng hng s cn bng KC c p dng cho dung dch long. Vi phn ng: mA(dd) + nB(dd) pC(dd) + pD(dd)

Hng s cn bng KC tnh theo cng thc sau:

Vi [C], [D], [A], [B] ln lt l nng ca C, D, A, B trong dung dch lc phn ng t trng thi cn bng. Trong trng hp dung dch lng nu trong h phn ng c hin din cht rn th ta khng ch n cht rn. V d:

62

Vi

, trong dung dch c cn bng vi pha rn AgCl. ca phn ng

3. S lin h gia hng s cn bng K vi bin i nng lng t do Xt phn ng cn bng ca cc cht th kh: mA(k) + nB(k) pC(k) + qD(k)

Bin i nng lng t do G ca phn ng l: (4-12) Vi kh c th xem nh kh l tng, iu kin ng nhit, s ph thuc ca hm nng lng t do G theo p sut P l:

Trong

l tr s nng lng t do ca 1 mol i 1atm, ng vi nhit T.

(4-13) Khi phn ng t trng thi cn bng p sut P, nhit T th:

63

l bin i nng lng t do iu kin chun thc (p sut P = 1 atm, nhit T xc nh). ph thuc vo nhit T. H thc trn cho bit c th tnh c hng s cn bng da vo cc i lng nhit ng hc ca ha cht. T biu thc 4-14 cho thy: - Nu Do , vi nhng phn ng cn bng tng ng vi rt m c khuynh hng xy ra gn trn vn, mc cn bng, nng sn phm rt ln. - Nu Vy nhng phn ng cn bng ng vi cng dng th cng xy ra khng trn vn, mc cn bng, nng sn phm tng ng rt nh. Vi trng hp dung dch lng v long vi phn ng: mA(dd) + nB(dd) pC(dd) + qD(dd)

trng thi chun thch hp, ngi ta cng chng minh c h thc:

64

Lc phn ng t trng thi cn bng, ta c:

II. NGUYN L CHUYN DCH CN BNG LE CHTELIER "Khi h t trng thi cn bng, s thay i mt yu t lm ph v cn bng s lm qu trnh chuyn dch theo chiu chng li s thay i y t c trng thi cn bng mi". Xt mt s yu t c th lm thay i mc cn bng: 1. nh hng ca nng S thay i nng ca mt cht s lm cn bng di i theo chiu chng li s thay i y. Ngha l nu lm tng nng mt cht th cn bng s dch chuyn theo chiu lm gim nng ca cht ny xung, tc l chiu cht ny tham gia phn ng; cn nu lm gim nng ca mt cht (nh ly bt cht ny ra khi h phn ng) th cn bng s dch chuyn theo chiu lm tng nng cht ny ln, tc l chiu phn ng to ra thm cht ny. Xt phn ng cn bng: A+B C+D

Khi phn ng t trng thi cn bng, ta c:

Nu thm cht A vo h phn ng th

vn gi nguyn tr s c

(khng i) th phi tng, nn phn ng cn bng s di i theo chiu lm gim A, to ra thm C, D cho n khi no cc nng mi t c tr s nh th no cho:

65

Tng t, sau khi phn ng t c trng thi cn bng, by gi nu ta ly bt C hoc D ra khi mi trng phn ng, th cn bng s b ph v v cn bng mi s c thit lp theo hng to ra thm C, D. Ni chung mun phn ng cn bng: A+B C+D

Cho ra nhiu sn phm C, D th ngi ta c th: - Lm tng nng cc cht tham gia A, B. - Hay lm gim nng sn phm C, D. 2. nh hng ca p sut Trong mt phn ng cn bng c lin h n kh, khi lm tng p sut th mc cn bng s di i theo chiu chng li s tng p sut, tc l chiu lm gim s mol kh, cn khi lm gim p sut th mc cn bng s di i theo chiu lm tng p sut ln, tc l chiu to ra nhiu s mol kh hn.

(4-16)

Vi * Nu

tng s h s mol kh sn phm - tng s h s mol kh tc cht. => s mol kh bn sn phm < s mol kh bn tc cht.
66

phn ng thin v chiu thun (chiu t s mol kh hn). phn ng thin v chiu nghch (chiu to ra nhiu s mol kh hn). V d:

=> ngi ta thc hin phn ng tng hp 300atm. * Nu T:

p sut rt cao khong 200-

S mol kh bn sn phm = s mol kh bn tc cht.

S thay i p sut trong trng hp ny khng nh hng n s di i mc cn bng. V d:

S di i mc cn bng ca phn ng ny khng nh hng bi yu t p sut.

67

* Nu T:

S mol kh bn sn phm > s mol kh bn tc cht.

* P tng hn). * P gim hn). V d:

phn ng thin v chiu nghch (chiu t s mol kh

phn ng thin v chiu thun (chiu c nhiu s mol kh

khi p sut gim, phn ng s thin v chiu to sn phm. 3. nh hng ca nhit Trong mt phn ng cn bng, khi tng nhit mc cn bng s di i theo chiu chng li s tng nhit tc l chiu lm nhit h xung, chiu thu nhit. Tri li, khi h nhit mc cn bng s di i theo chiu lm nhit tng ln, chiu ta nhit. V d: vi phn ng: , nn phn ng ta nhit theo chiu to SO3 vy khi h nhit th cn bng s di i theo chiu to ra thm SO3. Tuy nhin, trn thc t, ta khng th h qu thp nhit v lc by gi, vn tc phn ng s qu nh, phn ng xy ra rt chm, khng c li v phng din thi gian. * Cch tnh nhit phn ng ca phn ng cn bng:

68

Phn ng ta nhit Phn ng thu nhit H = Ea1 - Ea - 1 < 0; Gi H = Ea1 - Ea - 1 > 0

ln lt l nng lng kch ng ca phn ng thun v phn ng nghch.

iu kin ng p, ta c:

Theo Arrhnius: k1 = A1e-Ea1/RT k_1 = A_1e-Ea-1/RT Trng hp ny

69

Mun xc nh nhit phn ng H ngi ta o hng s cn bng K nhiu nhit T khc nhau, ri v ng biu din lgK theo 1/T , s c mt ng thng m h s gc l , tung gc l C, t xc nh c H ca phn ng (coi H nh khng i trong khong nhit T kho st).

Vi gim ngha l khi T tng, ph hp vi s kin cn bng di i theo chiu thu nhit khi nhit tng.

tng ngha l khi T gim, ph hp vi s kin Vi cn bng di i theo chiu ta nhit khi nhit gim. 4. p dng nguyn l chuyn dch cn bng

70

Ngi ta vn dng nguyn l chuyn dch cn bng ca Le Chtelier iu khin phn ng cn bng thin nhiu v chiu no m ngi ta mun c. V d: Vi phn ng tng hp amoniac

Phn ng ny ta nhit v c s gim s phn t kh (theo chiu thun). Do mun to ra kh nhiu NH3, ngi ta phi: - Tng nng N2 hay H2, lm gim nng NH3 - Tng p sut. - H nhit phn ng, tuy nhin khng th h nhit qu thp v nh th vn tc phn ng s rt chm, nn ngi ta cn chn nhit ti u va thu c nhiu NH3 trong thi gian cng nhanh cng tt. - Dng cht xc tc thch hp thc y vn tc phn ng xy ra nhanh hn. Trong thc t iu kin thc hin phn ng tng hp amoniac l: - Nhit khong 450 - 500oC. - p sut khong 200 - 300 atm. - Dng cht xc tc bt Fe c hot ha bng hn hp Vi mt phn ng cn bng thi im t bt k, bit phn ng ang trng thi cn bng hay ang dch chuyn theo chiu no th ta tnh thng s Q ca phn ng ri so snh vi hng s cn bng K tng ng ca phn ng. Nu Q = K: phn ng trng thi cn bng. Nu Q < K: phn ng ang dch chuyn theo chiu thun nhm t trng thi cn bng. Nu Q > K: phn ng ang dch chuyn theo chiu nghch nhm t trng thi cn bng. mA(k) + nB(k) pC(k) + qD(k)

71

BI TP CHNG 4 Cu 1. Cho phn ng cn bng:

Biu thc vn tc ca phn ng thun l:

Hy vit biu thc vn tc ca phn ng nghch.

Cu 2. Cho phn ng cn bng:

Biu thc vn tc ca phn ng thun l: v1 = k1[ CO ] [ Cl2 ] 3/2 Hy vit biu thc vn tc ca phn ng nghch.

Cu 3. Cho phn ng cn bng:

72

H2(k) + I2(k)

2HI(k)

763 K c hng s cn bng Kc = 45,9 v hng s vn tc phn ng thun l kt = 0,37M - 1.s- 1. Tm gi tr hng s vn tc phn ng nghch kn 763 K.

Cu 4. Vi phn ng: 2CH3I(k) -> CH3-CH3 (k) + I2(k) biu thc vn tc phn ng l: v = k [ CH3-I ] a) Hy cho bit biu thc vn tc ca phn ng nghch. b) Tnh gi tr ca phn ng thun 300oC.

c) Phn ng thun c xy ra c 300oC hay khng? Gii thch. d) nhit no th phn ng nghch xy ra c? e) Vi qu trnh cn bng: 2CH3I(k) CH3-CH3(k) + I2(k) .

Hy cho bit s lin h gia f) Tnh 300oC.

g) Trong s nghin cu vn tc phn ng trn, c cn thit n phn ng nghch 300oC hay khng? Cho: Cht CH3I(k) CH3 - CH3(k) I2(k)

73

20,5 (KJ/mol) (J/K. mol) Coi 254,6

- 84,67 229,5

62,24 260,58

khng i theo nhit .

R = 8,315 J/mol.K.

Cu 5. Vit hng s cn bng Cho bit h thc lin h gia a) 2NOCl (k) b) Zn(r) + CO2(k) c) MgSO4(r) d) 2NO(k) 2NO(k) + Cl2(k) ZnO(r) + CO(k) MgO(r) + SO3(k) N2(k) + O2(k) Co(r) + H2O(k)

(nu p sut tnh bng atm). ca cc phn ng sau:

e) CoO(r) + H2(k)

f) NOBr(k)

NO(k) +

Br2(k)

g) 2SO2(k) + O2(k)

2SO3(k)

h) SO2(k) +

O2(k)

SO3(k) 2NH3(k)

i) N2(k) + 3H2(k) j) BaCO3(r)

BaO(r) + CO2(k)
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Cu 6. Cho bit nh hng ca p sut trong cc phn ng cn bng sau: a) 2SO2(k) + O2(k) b) CO(k) + H2O(k) c) COCl2(k) d) N2(k) + 3H2(k) e) 2NO2(k) 2SO3(k) H2(k) + CO2(k) CO(k) + Cl2(k) 2NH3(k) N2O4(k)

Cu 7. Xem qu trnh: Cl2(k) 2Cl(k)

Mc cn bng ca qu trnh trn s di i nh th no khi tng nhit ? Gii thch. S: Chiu thun. Cu 8. Xem phn ng: A(k) B(k) + C(k)

300oC, Kp = 11,5atm 500oC, Kp = 33 atm a) Phn ng trn thu nhit hay ta nhit? b) Gi s phn ng trn xy ra trong mt giai on th nng lng kch ng Ea ca phn ng c tr s ti thiu bng bao nhiu? Ly ; phng trnh Van't Hoff cho bit lin h Kp theo nhit T l:

Cu 9. 2000 K, phn ng:

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H2(k) + CO2(k)

H2O(k) + CO(k)

Tnh nng ca mi ha cht mc cn bng nu mt bnh 10lt cha lc u .

Cu 10. S nhit phn carbamat amonium c biu din bng phng trnh:

a) 25oC, p sut tng qut ca kh cn bng vi cht rn l 0,116atm. Tnh Kp ca phn ng. b) Gi s khi cn bng t c, ngi ta thm vo mt lng kh CO2 c p sut ring phn l 0,1atm. Hi p sut cui cng ca CO2 nh hn hay ln hn 0,1 atm? p sut ca NH3 gim hay tng?

Cu 11. Xem phn ng: COCl2(k) CO(k) + Cl2(k)

a) Tr s

cho trn c hp l khng?

b) D on phn ng trn thu nhit hay ta nhit? c) D on nh hng ca nhit n mc cn bng. d) Tnh .

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e) Tnh h s phn ly phn t c lc u)

l t s gia s

Cu 12. Nng lng t do mol chun thc ca 12,39 .

ln lt l 20,72 v

a) Tnh Kt lun. b) Tnh

ca phn ng:

Tnh t s

. Kt lun.

c) Khi cho acid nitric long tc dng vi kim loi ng ngoi kh tri th nhn thy hin tng g? Da vo kt qu trn gii thch.

Cu 13. Cho bit: Cht

298 K

CO(k) - 26,42

CO2(k) - 94,05

Pb(r) 0

PbO(r) - 52,40

(Kcal.mol- 1)
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- 32,81
298 K p

- 94,26 8,76

0 6,34

- 45,25 11,07

(Kcal.mol ) 6,95

-1

(cal.K- 1.mol- 1)

Gi s t nhit mol ng p khng i trong khong nhit t 25oC n 127oC. a) Tnh PbO(r) + CO(k) b) Vit biu thc c) Tnh ca phn ng: Pb(r) + CO2(k) .

Cho bit phng trnh Van't Hoff lin h gia

Cu 14. a) Cho phn ng:

Tnh p sut tng qut lc cn bng c b) p sut tng qut 1atm. Tnh Kp. Nu p sut tng qut gim xung cn 0,5atm, th phn ly bin i nh th no? Nu thm Argon vo mi trng iu kin ng p (1atm) th phn ly tng hay gim?
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Cu 15. Xem cn bng: CO2(k) + H2(k) CO(k) + H2O(k)

Gi s ng c th tch Tnh: a)

khng thay i bao nhiu vi nhit . Ngi ta cho vo bnh cu phn .

b) p sut tng qut lc cn bng. c) S mol ca mi loi ha cht sau khi cn bng t c. d)

Cu 16. Vit biu thc hng s cn bng Kc i vi mi qu trnh cn bng sau: a) 4NH3(k) + 3O2(k) 2N2(k) + 6H2O (k)

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c) 2SO3(k)

2SO2(k) + O2(k)

f) N2(k) + 3H2(k) <v:shape id="_

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Chng 5. DUNG DCH

1. Khi nim v dung dch Ngy nay dung dch khng phi l mt khi nim xa l nh tnh ph bin ca n. Tuy nhin hiu ng v dung dch khng phi l chuyn n gin. Vi cc l thuyt hin i v ha hc n nay vn cha gii thch c r rng mt s vn v dung dch nh: tnh tan ca cc cht trong dung mi, cc tnh cht ca dung dch c nng cht tan ln,... Do vn d tm hiu dung dch khng ch xut pht t yu cu v mt thc tin m cn do yu cu v mt l thuyt. a). Cc h phn tn v dung dch Dung dch l cc h phn tn nhng khng phi h phn tn no cng l dung dch. H phn tn l nhng h trong c t nht mt cht phn b (gi l cht phn tn) vo mt cht khc( gi l mi trng phn tn) di dng cc ht c kch thc nh. Cc h phn tn c th c phn loi theo trng thi tp hp ca cht phn tn vo mi trng phn tn, hoc theo kch thc ca cc ht trong h phn tn, hoc theo cng tng tc gia cc ht trong h phn tn,... Ty thuc vo trng thi tp hp ca cht phn tn v mi trng phn tn m ta s c cc h phn tn sau ( K =kh, L = lng, R =rn ) K-K L- K R-K K-L L-L R-L K-R L-R R-R

Tuy nhin do tnh cht ca h phn tn ph thuc rt ln vo kch thc ca cc ht nn s phn loi theo kch thc cc ht l c ngha hn c. H phn tn th: kch thc cc ht> cm, do c th nhn thy cc ht bng mt thng hoc bng knh hin vi quang hc. Ty thuc trng thi ca cht phn tn m ngi ta phn bit dng huyn ph hay nh tng. Dng huyn ph thu c khi c s phn b ht cht rn trong cht lng, v d cc ht t st l lng trong nc. Dng nh tng thu c khi c s phn b ht cht lng trong cht lng, v d sa l h nh tng in hnh gm cc ht m l lng trong cht lng. Cc h phn tn th khng bn v cc ht phn tn c kch thc qu ln so vi cc phn t, ion nn d dng lng xung.
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H phn tn cao hay h keo: Cc ht phn tn c kch thc trong khong

, do quan st c cc ht phi dng knh siu hin vi c phng i ln. V d cho loi h ny l gelatine, keo dn, sng m, khi. Cc h keo cng khng bn v cc ht keo d lin hp nhau thnh ht c kch thc ln hn v lng xung. Cc h keo c nhiu tnh cht rt c bit v c rt nhiu ng dng quan trng trong i sng, do vic nghin cu h keo tr thnh mt lnh vc nghin cu c lp gi l ha keo. Dung dch: khi cc ht c kch thc c phn t hay ion, ngha l c kch th h phn tn tr thnh ng th v c gi n gin l dung dch. Kch thc< thc v cng b nh ca cc ht lm cho chng phn b ng u trong mi trng v dn n s ng nht v thnh phn, cu to v tnh cht trong ton b th tch ca h, cng nh lm cho h rt bn khng b ph hy khi yn theo thi gian. V d khi ha tan ng v mui n vo nc, cc ht ng phn tn di dng phn t, cn cc ht mui phn tn di dng ion. T cc c im nu ta c th nh ngha dung dch nh sau: Dung dch l h ng th gm hai hay nhiu cht m thnh phn ca chng c th thay i trong mt gii hn rng. nh ngha ny cho thy dung dch ging hp cht v tnh ng nht nhng khc ch c thnh phn thay i, trong khi ging hn hp c hc ch c thnh phn thay i nhng khc tnh ng nht. Bng 5.1. Phn loi h phn tn theo kch thc ca tiu phn Kch thc tiu phn. bn theo V d n v cm thi gian -5 H phn tn th >10 Khng bn -Ht st l lng trong nc. -Huyn ph -Nh tng H keo Dung dch -Sa H

10-5 - 10-7 <10-7

Khng bn Bn

Gelatin NaCl tan trong nc

b). Trng thi dung dch

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Trong ho hc chng ta thng lm vic vi cc dung dch lng, do , i vi nhiu ngi dung dch c hiu l trng thi lng. Thc ra v mt trng thi tp hp, dung dch c th trng thi kh, lng hoc rn. Bng 5.2. Cc trng thi tp hp ca dung dch V d Khng kh Ru trong nc Thp Nc ng Soda H2 tan trong Pd Trng thi ca dung Trng thi ca cht Trng thi ca dung dch tan mi Kh Kh Kh Lng Lng Lng Rn Lng Lng Rn Rn Rn Kh Kh Rn Lng Lng Rn

c). Cht tan v dung mi Nh trnh by dung dch l h ng nht gm cc cht phn tn vo nhau. Cht ng vai tr mi trng phn tn, gi l dung mi. Cc cht cn li ng vai tr cht phn tn, gi l cht tan. Vi nh ngha ny ta thy ranh gii phn bit gia cht tan v dung mi l khng r rt. Thng thng dung mi c hiu l cht c trng thi tp hp khng thay i khi hnh thnh dung dch nu cc cht ban u khc nhau v trng thi, hoc dung mi l cht chim lng ln khi to thnh dung dch nu cc cht ban u cng trng thi. i khi ngi ta c th s dng mt tnh cht c th no xc nh dung mi, v d: i vi cc h rn-lng, kh-lng th dung mi l cht lng hoc dung mi s l cht kt tinh u tin khi lm lnh dung dch. d). Dung dch long, m c, cha bo ha, qu bo ha, tan Khi ho tan ng vo nc, ng ng vai tr cht tan, nc ng vai tr dung mi. Nu lng ng tan trong nc t, ta c dung dch nc ng long. Nu lng ng tan trong nc tht nhiu, ta c dung dch nc ng m c. Vy ta c th hiu: - Dung dch long l dung dch cha mt lng t cht tan. - Dung dch m c l dung dch cha mt lng ln cht tan.

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Nu tip tc thm ng vo dung dch, ta thy ng tip tc tan ra, dung dch by gi s cha mt lng ng nhiu hn ban u. Nhng nu tip tc thm ng n mt lc no ta thy ng khng th ha tan thm c na mt nhit xc nh, lc ny ta c dung dch nc ng bo ha v lc ny lng ng c trong dung dch bng tan ca n. Tng qut ta hiu nh sau: - Dung dch cha bo ha l dung dch m cht tan c th tip tc tan thm. - Dung dch bo ha l dung dch m cht tan khng th tan thm c na mt nhit xc nh. - tan l lng cht tan c vo dung dch to ra mt dung dch bo ha mt nhit xc nh. Nu nng nhit dung dch ln cao hn, ng s tip tc ha tan . Khi lm ngui dung dch v nhit ban u t0C th lng ng d so vi tan nhit t0C s kt tinh tch ra khi dung dch v c s hnh thnh tr li dung dch bo ha. Trong mt s trng hp, qu trnh kt tinh c th xy ra lp tc hoc s xy ra khi ta thm vo vi tinh th ca cht tan, hoc lc dung dch. Dung dch cha mt lng cht tan vt qu so vi tan c gi l dung dch qu bo ha, Sir l dung dch nc ng qu bo ha m chng ta thng gp. 2. Thnh phn ca dung dch Do thnh phn ca dung dch c th thay i nn mi quan h v lng ca cc cht trong dung dch phi c xc nh r rng v c nhiu cch khc nhau xc nh mi quan h . a). Nng phn trm khi lng (%) S gam cht tan trong 100 gam dung dch.

V d 5.1. Dung dch NaOH 20% ngha l c 100g dung dch th c 20g NaOH tan trong . b). Phn mol

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L t l gia s mol cht no vi tng s mol ca cc cht trong dung dch. i vi dung dch to thnh t hai cht A, B vi s mol tng ng l mol nh sau: , ta c biu thc phn

c). Nng molan (m) S mol ca cht tan c trong 1kg hoc 1000g dung mi.

d). Nng mol S mol cht tan c trong 1 lt dung dch

V d 5.2. Dung dch . Ta c th chn mt loi nng no s dng sao cho tin li vi yu cu nh lng. V d 5.3. Khi trn ln 1,00g etanol vi 100,0g nc ta thu c dung dch c th tch l 101ml. Tnh: nng molan. Phn mol ca etanol trong dung dch. Gii:

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e). Nng ng lng Mt loi nng khc thng c s dng tnh ton trong cc phng php phn tch th tch l nng ng lng c nh ngha l s ng lng gam ca cht tan trong mt lt dung dch. T nng mol ta c th d dng tnh c nng ng lng theo biu thc:

l s ng lng gam ng vi 1 mol cht tan. V d 5.4. Ta c dung dch Do Ni chung ta u c th thc hin s chuyn i qua li gia cc loi nng , v qua bit c thnh phn ca dung dch. V d 5.5. Dung dch s dng bnh acqui l dung dch H2SO4 3,75M, c khi lng ring l: 1,230 g/ml. Tnh nng %, nng molan v nng ng lng ca H2SO4 trong dung dch trn. Gii: Khi lng ca 1 lt dung dch: 1000 x 1,230 = 1230g. Khi lng ca H2SO4 trong 1 lt dung dch: 3,75 x 98 = 368g. Khi lng ca H2O trong 1 lt dung dch: 1230 - 368 = 862g. Do :
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ng vi s ng lng gam l 2.

3. Tng tc gia cht tan v dung mi a). Nhit ha tan Khi ha tan NaOH vo nc ta thy dung dch nng ln, ngc li khi ha tan ur vo nc th ta li thy dung dch lnh i. iu ny chng t khi ha tan cht tan vo dung mi khng ch n thun xy ra qu trnh khuch tn cc tiu phn cht tan vo cc tiu phn ca dung mi, m cn xy ra qu trnh tng tc gia cc tiu phn vi nhau. Nhng lc tng tc gia cc tiu phn ca cht tan v dung mi cng chnh l nhng lc tng tc quyt nh trng thi tp hp ca cc cht. Chng c bn cht vt l nh lc ht tnh in, lc Van Der Waals... Hoc bn cht ha hc nh tng tc cho-nhn, lc lin kt hydro... Cc lc tng tc th nht gn lin vi cc qu trnh vt l v ch th hin trn nhng khong cch ln hn kch thc phn t. Nhng lc tng tc th hai c thc hin trn nhng khong cch gn vi s tham gia ca cc obitan nguyn t v phn t. S khuch tn cc tiu phn cht tan vo dung mi l nguyn nhn lm cho nng dung dch ng u trong ton b th tch dung dch. Trong trng hp tng qut cc qu trnh vt l bao gm cc qu trnh ph v mng tinh th, qu trnh khuch tn cht tan vo dung mi,... Gi chung l qu trnh chuyn pha. Qu trnh ha hc bao gm tt c cc qu trnh tng tc to thnh nhng hp cht c thnh phn thay i gia cht tan v dung mi c gi l s solvat ha, nu dung mi l nc th c gi l s hidrat ha. Trong a s trng hp cc qu trnh vt l thng tng ng vi qu trnh thu nhit, cn cc qu trnh ha hc thng ng vi qu trnh ta nhit. Ty cht tan v dung mi, cng nh ty nhit v p sut m mt trong hai qu trnh s chim u th, kt qu dn n l qu trnh ha tan s ta nhit hay thu nhit. Ngi ta nh ngha Lng nhit thu vo hay pht ra khi ha tan mt mol cht tan c gi l nhit ha tan.

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 hiu r hn ta xt trng hp ha tan cht rn vo dung mi lng, v d ha tan NaCl vo nc, qu trnh c th chia lm 3 bc: Bc 1 Ph v cu trc tinh th ca cht tan to thnh tiu phn ring bit. Qu trnh ny c trng bng gi tr Bc 2 Ph v lc lin kt lin phn t gia cc phn t dung mi to ra cc khong trng cho cc tiu phn ca cc cht tan xm nhp. Qu trnh c c trng bng

Bc 3 Xy ra tng tc gia cc tiu phn ca cht tan v cc phn t ca dung mi to thnh dung dch, tc xy ra qu trnh solvat ha. Qu trnh ny c trng bng gi tr . chnh l tng ca 3 gi tr trn.

Ty qu trnh no chim u th m gi tr qu trnh ha tan thu nhit hoc ta nhit.

c th (+) hoc (-) hay ni cch khc

i vi qu trnh ha tan NaCl trong nc, gi tr

phi ln v c du (+) do cng rt

phi tn nhiu nng lng b gy lc ht gia cc ion trong tinh th. Gi tr ln v c du (-) v xy ra tng tc rt mnh gia cc ion

vi cc phn t H2O.

T y ta c nhit ha tan NaCl trong nc l:

V mt nhit ng hc, mt qu trnh nu i hi cung cp nng lng cng ln th cng kh xy ra. Qu trnh ha tan NaCl vo nc ch i hi mt nng lng tng i nh, do c th xy ra mt cch t nhin. Gi tr trnh ha tan. chnh l bin i entalpi ca qu

Tuy nhin y cha th gii thch c ti sao NaCl tan tt trong nc. Theo nguyn l II ca nhit ng lc hc mt qu trnh xy ra t nhin l mt qu trnh tin n
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mt trng thi xo trn cao hn. Do NaCl tan tt v tuy phi cung cp mt nng lng nh nhng trng thi dung dch t xo trn ln hn rt nhiu so vi ban u, kt qu l c s hnh thnh dung dch NaCl khi ha tan NaCl vo nc. Cc kt qu thu c y hon ton ph hp vi qui lut kinh nghim v tan l <Cc cht c cng tnh phn cc th ha tan tt vo nhau>. Bng 5.3. Yu t nng lng ca qu trnh hnh thnh dung dch t cc cht tan v dung mi khc nhau Bn cht ca cc cht Dung mi phn cc-cht tan phn cc Dung mi phn cc-cht tan khng phn cc Dung mi khng phn cc-cht tan khng phn cc Dung mi khng phn cc-cht tan phn cc b). Dung dch l tng Khi kho st qu trnh ha tan v phng din ng lc hc nh trnh by ngi ta nhn thy c nhng trng hp m dung dch c hnh thnh vi . l trng hp khi ha tan vo nhau cc cht khng cc v ging nhau v cu trc, lin kt ha hc, v d nh pental v hexan. Trong nhng dung dch nh th lc tng tc ca nhng phn t cng loi v khc loi ging nhau. Nhng dung dch nh vy c gi l dung dch l tng. ng lc duy nht a n s hnh thnh cc dung dch l tng chnh l s gia tng xo trn, tc gia tng entropy ca dung dch vi cc cht ring l ban u. i vi dung dch l tng tnh cht ca dung dch khng ph thuc vo bn cht ca cht tan m ch ph thuc vo nng ca chng. c). nh hng ca cu trc cht tan n tan Nh cp <cht c cng bn cht phn cc ha tan tt vo nhau>, m s s phn cc ca mt cht c xc nh bi cu trc ca n, do , gia cu trc v tan c mt mi quan h xc nh. Cc vitamin l nhng v d tiu biu cho thy nh hng ca cu trc n tan.
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DH1 (+) ln (+) nh (+) nh (+) ln

DH2 (+) ln (+) ln (+) nh (+) nh

DH3 (-) ln (-) nh (-) nh (-) nh nh (+) ln nh ln (+)

Kt qu Hnh thnh dung dch Kh hnh thnh dung dch Hnh thnh dung dch

Kh hnh thnh dung dch

Ta c th phn vitamin ra lm hai nhm chnh: tan trong du (vitamin A, D, E, K) v tan trong nc (vitamin B, C). Vitamin A c cu to ch yu bi C v H, c i lc electron tng ng nhau nn trong phn t khng xy ra s phn cc lin kt ng k v do l cht khng phn cc. iu ny cho thy chng d dng tan trong cc dung mi khng phn cc, v d nh du m, v khng tan trong cc dung mi phn cc, v d nh nc.

Hnh 5.1 Cu to ca Vitamin A v Vitamin C

Cc vitamin tan trong du c th hnh thnh v tch tr ti cc m m trong c th. Do ta chu ng c mt thi gian di nu trong ch n ung thiu cc loi vitamin trn. Ngc li, nu chng qu d c th dn n chng bnh gi l tha vitamin (hypervitaminosis). i vi cc vitamin tan trong nc, chng d dng b c th thi b v do phi c b sung thng xuyn. Trc y ngi ta pht hin bnh ph chy mu ca cc thy th sng xa t lin do thiu vitamin C, cn bnh ny c chn ng bng cch b sung y vitamin C. d). nh hng ca p sut n tan p sut nh hng khng ng k n tan ca cht rn hoc lng, nhng c tc ng ln n tan ca cht kh. Cc loi nc gii kht cha ga khi ng chai phi p sut CO2 cao nhm bo m t c mt nng ln ca CO2 trong dung dch. Khi m np, do p sut ca CO2 trong kh quyn b nn xy ra s thot CO2 khi dung dch to nn ting bt v c trng. S gia tng tan ca kh trong dung dch c th c minh ha trong v d sau: gi s ang xy ra cn bng gia cht kh v cht lng, ngha l s phn t kh thot ra hoc tan vo dung dch vi tc bng nhau. Nu ta lm tng p sut, s phn t kh trong mt n v th tch s gia tng, kh s tan vo dung dch vi tc ln hn tc thot ra, lc ny nng kh tan trong dung dch s tng cho n khi mt cn bng mi c thit lp, v d nhin lc ny dung dch s cha mt lng kh tan nhiu hn.
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Mi lin h gia p sut v nng kh tan trong dung dch c th hin qua phng trnh: P = kC. Vi P l p sut ring phn ca kh tan trn b mt dung dch. C l nng ca kh tan trong dung dch k l hng s c trng ca mi loi dung dch. y l phng trnh ton hc ca nh lut Henry, n th hin ni dung sau: <lng kh tan trong dung dch t l vi p sut ring phn ca n>. iu quan trng cn phi ch l nh lut Henry ch ng trong trng hp kh tan khng phn ng vi dung mi, v d: ng vi trng hp kh O2 tan trong nc, nhng khng ng vi trng hp HCl tan trong nc v y xy ra s phn ly ca HCl.

V d 5.6. Mt loi nc gii kht c ng np 250C cha kh CO2 vi p sut trn b mt dung dch l 5 atm. Nu p sut ring phn ca CO2 trong kh quyn l 4,0.10-4 atm, hy tnh nng CO2 trong dung dch trc v sau khi m np. Hng s Henry ca CO2 trong dung dch l 32 l.atm/mol 250C. Gii: p dng nh lut Henry ta c:

K = 32 l.atm/mol.

Khi m np, CO2 trong dung dch thot ra v t n trng thi cn bng vi p sut ca atm, do :

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e). nh hng ca nhit n tan Vic ha tan cc cht rn vo nc, v d ha tan ng hay mui vo nc, m ta gp hng ngy c th lm ta i n kt lun rng tan ca cc cht tng theo nhit . Thc s khng phi nh vy. Nhit cao gip qu trnh ha tan xy ra nhanh hn nhng lng cht tan c th gim i theo nhit . nh hng ca nhit n tan ca cc mt s cht tan rn trong nc c trnh by hnh 5.2. Ta thy rng a s cc cht c tan tng khi tng nhit , nhng cng c mt s cht c tan gim khi tng nhit nh: Na2SO4, Ce2(SO4)3... Rt kh m tin on s ph thuc ca tan ca mt cht theo nhit . Do phng php tt nht l kim tra bng thc nghim.

Hnh 5.2. S ph thuc ca tan ca mt s cht rn theo nhit Hnh 5.3. S ph thuc tan ca cc cht kh khc nhau trong nc theo nhit p sut 1 atm i vi cht kh th hu nh l tan gim khi tng nhit .

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nh hng ca nhit i vi tan ca cc cht kh c ngha quan trng v mt mi trng. Mt lng ln nc c s dng lm ngui trong cc qui trnh cng nghip, sau khi s dng s b nng ln v c thi tr li sng h. Do nng hn nn nc s cha t lng O2 ha tan hn, iu ny lm ph v cn bng hp ph O2, lm gim lng O2 ha tan trong nc v do vy nh hng n hot ng sng ca cc sinh vt sng trong nc. 4. Tnh cht ca dung dch khng in ly Do kt qu tng tc xy ra gia cc tiu phn ca cht tan v dung mi, cng nh do s gim nng cc tiu phn t do ca dung mi trong qu trnh to thnh dung dch m tnh cht ca cht tan, dung mi thay i v khc vi tnh cht ca dung dch thu c. iu ny c chng minh r rng vi hiu ng nhit, hiu ng th tch, tng nhit si, h nhit ng c ca dung dch so vi dung mi tinh cht. Khi nng cht tan tng, nh hng ca cc yu t ni trn tng mnh lm cho tnh cht ca dung dch tr nn phc tp hn. Vic nghin cu tnh cht ca cc dung dch rt kh, do , n nay vn cha c l thuyt nh lng i vi nhng dung dch c nng cao. i vi cc dung dch c nng cht tan nh, c bit nhng nng rt nh, cc nh hng ca nhng yu t ni trn c th b qua, do dung dch tr thnh gn vi l tng, ngha l khng c hiu ng nhit v hiu ng th tch. Trong nhng trng hp nh vy tnh cht ca dung mi hu nh khng thay i, cn cc tnh cht ca dung dch th c mt s thay i ph thuc bn cht cht tan, v d nh s thay i mu sc, nhng c mt s tnh cht khc ch ph thuc nng cht tan nh p sut hi bo ha, nhit si, nhit ng c, p sut thm thu. Vic nghin cu cc tnh cht ny tng i n gin v xy dng c l thuyt nh lng hon chnh v chng i vi cc dung dch lng v long. Di y s ln lt kho st cc tnh cht . a). p sut hi ca dung dch Cc dung dch lng c p sut hi khc ng k so vi dung mi tinh cht. hiu c s nh hng ny chng ta xem xt th nghim sau:

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Hnh 5.4. Th nghim kho st nh hng ca cht tan n tnh cht ca dung mi C hai cc: mt cc ng nc tinh cht v mt cc ng dung dch nc ng, t trong mt chu thy tinh nh hnh 5.4. Sau mt thi gian ta thy th tch ca nc gim cn th tch ca dung dch nc ng tng. iu ny ch c th gii thch c khi p sut hi ca dung mi tinh cht phi ln hn p sut hi ca dung dch cha cht tan khng bay hi, ngha l nu hai bnh c lp nhau th khi cn bng lng hi c thit lp p sut hi to ra trn b mt dung mi tinh cht phi ln hn p sut hi to ra trn b mt dung dch. Do trong mt h kn s ha hi mnh ca dung mi tinh cht lm cn bng lng hi ca dung dch b dch chuyn theo chiu dung dch phi hp th hi lm gim p sut hi trn b mt dung dch. S hp th hi dung mi trn b mt dung dch lm gim p sut hi ca dung mi trong h. t cn bng lng hi tr li dung mi tinh cht phi bc hi thm, do cn bng lng hi ca dung mi tinh cht b dch chuyn theo chiu lm tng p sut hi ca dung mi tinh cht, kt qu l xy ra s chuyn dung mi tinh cht sang dung dch. S hin din ca cht tan trong dung dch lm gim s phn t dung mi t do trong mt n v th tch, do lm gim s phn t dung mi trn b mt v do lm gim kh nng ha hi ca dung mi. Cc nghin cu v p sut hi ca dung dch lng l tng cha cht tan khng bay hi c thc hin bi Francois M.Raoult v c cng thc ha nh sau:

94

ng biu din phng trnh ca nh lut Raoult c dng ng thng: y = ax + b. Vi: V d 5.7. Tnh p sut hi ca dung dch c to thnh bng cch ha tan 158,0g ng Saccaroz (M = 342,3g) trong 643,5cm3 nc 250C, bit 250C khi lng ring ca nc tinh cht l 0.9971g/cm3 v p sut hi ca nc tinh cht l 23,76mmHg. Gii:

Trong trng hp cht tan bay hi, thng gp i vi cc dung dch lng-lng l tng, phng trnh m rng ca dnh lut Raoult c dng.

Vi:

Cc dung dch l tng nghim ng phng trnh ca nh lut Raoult. Nu phng trnh khng c nghim ng ta c s sai lch. S sai lch ny c th m hoc dng, ngha l p sut hi dung dch c th nh hn hoc ln hn so vi khi tnh ton bng phng trnh Raoult. i vi dung dch cha cht tan khng bay hi thng gp s sai lch nhiu hn so vi dung dch cha cht tan bay hi. th biu din s ph thuc p sut hi ca dung dch cha cht tan bay hi theo phn mol ca dung mi v cht tan c th hin hnh 5.5.
95

Hnh 5.5. S ph thuc ca p sut hi ca dung dch cha cht tan bay hi theo phn mol ca dung mi v cht tan trong trng hp l tng v c xy ra sai lch 1: p sut hi dung dch. 2: p sut ring phn ca B. 3: p sut ring phn ca A. i vi cc dung dch m tng tc gia cht tan- cht tan, dung mi-dung mi, cht tan- dung mi c cng bn cht th tnh cht ca dung dch cng gn vi tnh cht ca dung dch l tng. Trong trng hp ny cht tan ch lm nhim v pha long dung mi v ngc li. V d 5.8. Dung dch benzen-toluen chng c cng bn cht l khng phn cc. Entanpy ha tan coi nh bng 0, dung dch ny rt gn dung dch l tng v c th xem l dung dch l tng. Trong mt s trng hp dung mi c th c nhng i lc c bit i vi cht tan, v d nh to c lin kt hydro i vi cht tan, lc ny kh nng ha hi ca cht tan cng nh dung mi trong dung dch u gim v do p sut hi ca dung dch nh hn so vi tnh ton bng phng trnh Raoult, ta c s sai lch m, v d: dung dch aceton trong nc c sai lch m v xy ra lin kt hydro gia aceton v nc.

Ngc li nu tng tc gia cht tan-dung mi yu hn tng tc gia cc phn t ca cht tinh cht th khi hnh thnh dung dch nhit ha tan thng c gi tr (+) v cn nng lng lm dn khong cch gia cc phn t cht tan v dung mi khi chng c trn ln vo nhau. Trong trng hp ny cc phn t cht tan cng nh dung mi c khuynh hng ha hi mnh hn, ta c dung dch sai lch (+), ngha l p sut hi ca dung dch s ln hn so vi gi tr tnh ton bng phng trnh Raoult. V d v trng hp ny l dung dch etanol-hexan. Cc phn t etanol phn cc, cc phn t hexan khng
96

phn cc, chng tng tc vi nhau rt yu. Entanpy ha tan c gi tr (+)xy ra s sai lch dng. Bng 5.4. Bng tm tt tnh cht ca cc loi dung dch khc nhau

V d 5.9. Mt dung dch c iu ch bng cch ha tan 5,81g aceton vo 11,9g Cloroform. 350C dung dch c p sut hi l 260mmHg. y l dung dch l tng hay khng? Bit p sut hi ca aceton v cloroform 350C l 345 v 293mmHg. Gii: Mun bit dung dch c l tng khng ta tnh p sut hi ca dung dch theo phng trnh Raoult ri so snh vi gi tr thc nghim.

Theo thc nghim gi tr o c l 260mmHg, vy y l dung dch khng l tng.

y c s gim p sut hi ca dung dch nhiu hn d kin tc xy ra s sai lch m. iu ny cho thy gia cht tan v dung mi phi tng tc nhau mnh. Thc vy, gia aceton v cloroform hnh thnh lin kt hydrogen. ngha ca s gim p sut hi ca dung dch cha cht tan khng bay hi cho ta mt phng php thc tin m s phn t v qua gip ta xc nh c phn t lng ca mt cht cha bit. Dng phng trnh Raoult chng ta bit c s phn t
97

cht tan hin din, v do chng ta bit khi lng tng ng nn s xc nh c phn t lng. V d 5.10. Mt dung dch c iu ch bng cch ha tan 20,0g urea vo 125g nc 250C. p sut hi ca dung dch o c 250C l 22,67mmHg. Xc nh phn t lngca urea bit p sut hi ca nc tinh cht nhit trn l 23,76mmHg.

Phn t lng ng ca urea l 60,0. Kt qu thc nghim ph hp tt vi thc t. Mt ngha khc na l c th dng nh lut Raoult nghin cu tnh cht ca dung dch. Khi ha tan 1 mol NaCl vo nc th ngi ta thy rng p sut hi dung dch gim gp 2 ln so vi d kin bi v cc phn t NaCl khi ha tan vo nc phn ly hon ton thnh ion nn tiu phn trong dung dch tng ln gp i, m gim p sut hi ca dung dch th t l vi s lng tiu phn c trong dung dch. Th nghim ny khng nh NaCl phn ly hon ton khi ha tan vo nc l ng. V d 5.11. D on p sut hi ca dung dch c iu ch bng cch ha tan

Gii:

Khi ha tan vo nc, 1 mol Na2SO4 phn ly cho 2 mol Na+ v 1 mol SO42-, do s tiu phn tan trong dung dch tng ln 3 ln nn cng s ng vi s mol l:

98

b). tng nhit si Nhit si bnh thng ca mt cht lng c nh ngha l nhit lc p sut hi ca cht lng t c 1 atm. Cc cht tan khng bay hi lm gim p sut hi ca dung dch, do dung dch phi c un nng n nhit cao hn nhit si ca dung mi tinh cht mi c th t c p sut 1atm. iu ny c ngha l cht tan khng bay hi lm tng nhit si ca dung mi. Mc gia tng nhit si ph thuc vo nng ca cht tan trong dung dch. i vi cc dung dch long mi quan h c biu din bng phng trnh: Ts = ks.mct Vi: Ts: tng nhit si so vi dung mi tinh cht. ks gi l hng s nghim si ph thuc vo bn cht dung mi. mct nng molan ca cht tan trong dung dch. Bng 5.5. Gi tr ks v k ca mt s dung mi khc nhau Dung mi Nc CCl4 CHCl3 C6 H 6 CS2 te etylic Camphor Nhit si (C) 100,0 76,5 61,2 80,1 46,2 34,5 208,0 ks0C.Kg/mol 0,51 5,03 3,63 2,53 2,34 2,02 5,95 Nhit 0 -22,99 -63,5 5,5 -111,5 -116,2 179,8 kd0C.Kg/mol 1,86 3,00 4,70 5,12 3,83 1,79 40

Da vo tng nhit si so vi dung mi tinh cht ta c th xc nh c phn t lng ca cht tan trong dung dch.

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V d 5.12. Mt dung dch c iu ch bng cch ha tan 18,00g Gluc trong 150,00g nc. Dung dch c nhit si l 100,340C. xc nh phn t lng ca Gluc, bit hng s nghim si ca nc l 0,510C.Kg/mol. Gii:

c). h nhit ng c Ngi ta nh ngha nhit ng c ca mt cht lng l nhit m lc p sut hi ca pha lng bng vi p sut hi ca pha rn, c th i vi nc tinh cht c nhit ng c l 00C (chnh xc l 0,00990C) ng vi p sut hi bo ha ca nc v nc lng l 0,006atm. Vic ha tan cht tan vo nc s lm cho dung dch c nhit ng c thp hn nc tinh cht, bi v s hin din ca cht tan trong nc s lm cho p sut hi ca nc trong dung dch thp hn p sut hi ca nc , do ti nhit ny dung dch khng th ng c v khng c s bng nhau ca p sut hi gia pha lng v pha rn. Nu ta h nhit , p sut hi ca pha rn gim nhanh hn pha lng, kt qu s dn n s cn bng p sut hi ca 2 pha lng v rn v lc ny dung dch s ng c. Do cht tan lm h nhit ng c ca nc, nn cc cht nh NaCl, CaCl2 thng c ri trn va h hoc ng trnh s ng bng trong ma ng cc nc Chu u, d nhin vi iu kin nhit bn ngoi khng qu thp.

100

Hnh 5.6. Gin pha ca cn bng lng / hi v lng / rn ca dung dch nc cha cht tan khng bay hi T gin ta c th kt lun: s hin din ca cht tan khng bay hi lm m rng khong nhit m dung dch tn ti trng thi lng-cng ging nh tng nhit si- h nhit ng c ca dung dch so vi dung mi tinh cht ph thuc vo nng ca cht tan, phng trnh biu din s lin h, i vi dung dch long, cng c dng tng t v cng c dng xc nh phn t lng ca cc cht tan. T = k.mct T h nhit ng c ca dung dch so vi dung mi tinh cht. k hng s nghim ng ph thuc vo bn cht dung mi. mct : nng molan ca cht tan. Gi tr hng s K ca mt s dung dch khc nhau c trnh by bng 5.5. V d 5.13a. Tnh gn ng khi lng ca etylen glycol cn thm vo 10 lt nc thu c mt dung dch c nhit ng c l ring ca nc 1g/ml, hng s nghim ng ca nc Gii: . Khi lng

101

V d 5.13b. Ha tan 0,546g thyroxin (mt loi hocmon ng vt) vo 15,0g benzen. Dung dch thu c c h nhit ng c l 0,2400C. xc nh phn t lng ca thyroxin. Gii:

d). p sut thm thu Ta xt th nghim sau y: mt ng thy tinh hnh ch U c ngn cch bi mt mng bn thm gia (mng bn thm l mt loi mng ngn c tnh cht c bit l ch cho cc phn t dung mi thm qua nhng khng cho cc phn t cht tan thm qua). Cho vo hai bn ng th tch bng nhau ca dung mi tinh cht v dung dch cha cht tan. Sau mt thi gian th tch ca dung dch tng cn th tch ca dung mi tinh cht gim. Qu trnh chuyn dung mi tinh cht sang dung dch thng qua mng bn thm c gi s thm thu. n mt lc no mc cht lng bn phn ng ng dung dch khng dng cao ln na, qu trnh thm thu t n cn bng. Mc cht lng trong ng ng dung dch cao hn trong phn ng ng dung mi tinh cht, iu ny c ngha l p sut tnh ca dung dch ln hn ca dung mi tinh cht. Phn p sut chnh lch c gi l p sut thm thu.

Hnh 5.7. Th nghim xc nh p sut thm thu Chng ta c th xt mt th nghim khc nh sau: chng ta cng b tr th nghim tng t th nghim trn, v c th ngn chn s thm thu bng cch p t ln dung dch mt p sut xc nh no . p sut cn p t ln dung dch ngn chn s thm thu phi bng vi p sut thm thu. 102

Khi 2 cht lng tip xc nhau qua mng bn thm, c s chuyn cc phn t dung mi t dung mi tinh cht sang dung dch v ngc li. Do trong dung dch c xy ra s tng tc gia cc phn t cht tan v dung mi nn tc chuyn cc phn t dung mi t dung dch vo dung mi tinh cht s nh hn tc ca qu trnh ngc li. Kt qu l s phn t dung mi s chuyn vo dung dch nhiu hn, lm tng th tch dung dch. S gia tng th tch dung dch, s to nn mt p sut c tc ng lm tng vn tc ca qu trnh chuyn cc phn t dung mi t dung dch tr li dung mi tinh cht. Khi vn tc ca hai qu trnh ny bng nhau, h t cn bng v th tch dung dch khng gia tng c na. T iu ny cho thy p sut thm thu cng ph thuc vo nng cht tan trong dung dch. i vi cc dung dch long mi lin h c biu din bng phng trnh:

p sut thm thu cng c s dng xc nh phn t lng ca cht tan v c dng nhiu hn cc phng php khc bi v ch cn mt nng nh ca cht tan cng to nn c mt p sut thm thu c gi tr ng k. V d 5.14. ha tan 10-3 g mt protein vo nc v chnh n th tch 1ml. Dung dch thu c c p sut thm thu l 1,12mmHg 250C, tnh phn t lng ca protein. Gii:

Qu trnh thm thu tng t c nghin cu thy xy ra thnh t bo ca thc vt v ng vt, nhng trong trng hp ny mng bn thm cho php cc phn t dung mi, cc ion v cc phn t cht tan c kch thc nh thm qua. Mt trong nhng ng
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dng quan trng ca s thm thu l to ra my lc mu cho nhng bnh nhn b bnh thn. Mu c cho chy qua mt ng lm bng cellophane, ng vai tr mng bn thm, ng c t trong dung dch ra (dialyzing). Dung dch ny cha cc ion cng nh cha cc cht tan c nng bng nng ca chng trong mu, do s thm thu cc cht thy s thm qua mng i vo dung dch v do mu c lc sch. Dung dch c p sut thm thu nh nhau gi l dung dch ng trng. Cc cht lng bm vo mu phi ng trng vi cht lng trong mu. Nu t bo c ngm vo dung dch u trng, ngha l dung dch c p sut thm thu ln hn cht lng trong t bo, th t bo s b co li do s mt nc. Ngc li, nu t bo c ngm vo dung dch nhc trng, tc dung dch c p sut thm thu nh hn cht lng ca t bo, t bo s b trng phng v v ra do s thm nhp ca nc. Khi p tht, c bng mui, chng ta to ra mt dung dch u trng so vi dung dch trong t bo vi khun do xy ra qu trnh loi nc khi cc t bo ca vi khun lm vi khun b co rt li v cht, nn chng ta c th dng mui bo qun tht, c... By gi nu chng ta cho nc tinh cht tip xc vi dung dch nc mui thng qua mt mng bn thm v tc ng ln dung dch nc mui mt p sut ln hn p sut thm thu ca dung dch nc mui th s xy ra qu trnh thm thu ngc ngha l nc s chuyn t dung dch vo nc tinh cht. ng dng ny c ngha thc tin ln. Cc my kh mui xch tay ng dng nguyn tc trn cho php lc c 5 lt nc t nc bin trong 1 gi, ngha l c th cu sng 25 ngi. BI TP CHNG 5

Bi 1. Hng s phn b ca SO2 gia nc v CHCl3 bng 0,953. Hi phi cn bao nhiu nc vo 1 lt dung dch SO2 trong CHCl3 tch c 25% SO2. Bi 2. 200C; CH3OH (Me) v C2H5OH (E) c p sut hi = 96 v 44 mmHg. Xc nh thnh phn hi trn dung dch c hnh thnh t nhng th tch bng nhau ca 2 ru. Cho bit: khi lng ring ca 2 ru ldMe = 0,7915 v dE = 0,7894 Bi 3. Hng s phn b ru etylic (C2H5OH) gia CCl4 v H2O bng 0,0244. Tnh nng ru ca mi lp, nu 0,1 mol C2H5OH ru phn b gia 300ml H2O v 500ml CCl4.

104

Bi 4. tan ca I2 trong H2O 250C l 0,34 g/l. H s phn b I2 gia CS2 v H2O l 590. Tm lng I2 cn li trong 100ml dung dch I2 trong nc sau khi lc dung dch ny vi 100ml dung dch CS2. Bi 5. Thm vo 500ml dung dch I2 trong te cha 1,7272 g I2 mt th tch 200 ml dung dch I2 trong glyxerin cha 2,0726 g I2. Xc nh nng mol/lit cc dung dch I2 cn bng , bit hng s phn b ca I2 gia glyxerin v te l 0,2.

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CHNG 6. CN BNG PHA (PHASE, TNG) Cn bng pha l s cn bng gia cc pha c trong mt h. Chng ta tm hiu iu kin cc pha cng tn ti cn bng trong mt h v iu kin c s chuyn pha ca cc cht ring bit trong h. 1. Mt s khi nim a. Pha (Tng, Trng tng) Pha l tp hp nhng phn ng th trong h c ngn cch vi cc phn khc ca h bng nhng b mt phn chia. H ng th ch gm mt pha, h d th gm hai pha hay nhiu pha. V d: - Kh oxi (O2) l h mt pha. - Khng kh l h ng th mt pha trong gm hn hp cc kh N2, O2, CO2, hi nc, kh him... m gia cc kh ny khng c b mt phn chia. - Vng ty (hp kim Au - Ag) l h ng th mt pha. - Hn hp bt kim loi vng (Au) v bt kim loi bc (Ag) nghin mn l h d th hai pha. - H gm nc p nh ang ha tan trong nc lng l h d th gm hai pha v gia b mt nc v nc lng c b mt phn chia. b. Hp phn Hp phn l cc ha cht c mt trong h v c th c lp ring r ngoi h. V d: - Trong dung dch nc ng th nc chng c kh nng tn ti c lp ngoi h. l hai hp phn ca h,

- Trong dung dch mui n trong nc th mui n (NaCl) v nc (H2O) l hai hp phn ca h nhng cc ion ion khng phi l cc hp phn ca h trn v ion
106

cng nh

khng c lp c mt mnh ngoi h.

- Khi ha tan hai mui NaCl v KBr vo nc th c mt h gm 5 hp phn, l: v cc ha cht ny c mt trong h v v nguyn tc c th tch ra khi h cc ha cht ny. NaCl (dd) + KBr (dd) c. Cu t (Cu t c lp) Cu t hay cu t c lp l s hp phn ti thiu m qua c th xc nh c thnh phn ca c h [ hay t cc hp phn t nht ny c th bit c cc hp phn khc ca c h ]. V d: - Dung dch nc ng th s cu t l 2 v cn phi c nc v ng mi to c dung dch ny. - Mt bnh cha hn hp hai kh l h gm hai hp phn nhng l h c mt cu t v trong h c phn ng ha hc xy ra gia hai hp phn trn, thnh phn ca chng khng c lp m ph thuc nhau. NaBr (dd) + KCl (dd)

Nh vy, ch cn bit thnh phn ca mt ha cht (mt hp phn

hoc

) th c ca h trn.

th bit c thnh phn ca ha cht cn li nh tr s hng s cn bng [ Hay c th hiu trong bnh c cha

nn ch cn bit c

- H dung dch gm 5 hp phn l phng trnh lin h gia cc hp phn trn: NaCl (dd) + KBr (dd) NaBr (dd) + KCl (dd)

th c 4 cu t v c mt

107

Ngha l ch cn bit thnh phn ca 4 cht th s bit c thnh phn ca c h (5 cht) nh biu thc hng s cn bng Kc trn. [ Hoc c th hiu l h dung dch trn nu bit c 4 cht (nh H2O, NaCl, KBr, NaBr) th cng phi c cht th 5 trong h l KCl ]. - Cng h dung dch trn m xut pht lc u do ha tan NaCl, KBr vo nc th s thm phng trnh na lin h l s mol hay nng ca NaBr v KCl bng nhau: [NaBr] = [KCl] Th s cu t ca h by gi l 3. V ch cn bit thnh phn ca 3 cht, nh hai h thc trn s tm c thnh phn ca c h (5 cht). [ C th hiu, ch cn ly 3 cht H2O, NaCl, KBr trn vo nhau th s thu c h gm 5 cht l H2O, NaCl, KBr, NaBr, KCl ]. Ni chung, s cu t (C) ca mt h bng s hp phn (H) ca h tr bt i s phng trnh lin h (L) gia cc hp phn y gm biu thc hng s cn bng v nhng h thc v thnh phn cc ha cht (hp phn) trong cng mt pha. C=HL (6-1)

V d: - Xem h:

NH4Cl(r)

NH3(k) + HCl(k)

Vi nng NH3 v HCl bt k ta c h thc: Kp = PNH3.PHCl H gm 3 hp phn l NH4Cl, NH3, HCl. H ny c: 3 - 1 = 2 cu t Nhng nu ch nung nng NH4Cl lc u th c thm h thc na l:
108

PNH3 = PHCl => S cu t cn l: 3 - 2 = 1 - Nu ch nung nng CaCO3 lc u, ta cng ch c mt biu thc lin h nn s cu t ca h vn l 2. H thc (n: s mol) khng c tnh v CaO(r) v CO2(k) hai pha khc nhau. Tht vy, nhit xc nh, PCO2 c tr s xc nh m khng ph thuc vo iu kin trong 3 ha cht hin din. Do , ta ch xc nh c h trn khi bit 2

CaCO3(r)

CaO(r) + CO2(k)

d. Bc t do ( t do, Bin , Bin t ) Bc t do ca mt h bng s thng s trng thi (thng s trng thi) (nh nhit , p sut, nng ...) c th t do thay i m khng lm thay i s pha v bn cht cc pha trong h. V d: - Xem h gm nc lng 25oC v 1atm, ta c th thay i cng mt lc nhit v p sut trong nhng gii hn thch hp m vn cn c nc lng (nh 30oC v 1,2atm chng hn). Vy h c 2 bc t do trong trng hp ny. - H gm nc cn bng vi nc lng 0oC v 1atm th c mt bc t do v h va c c nc ln nc lng th ta ch c th thay i t do nhit (hoc p sut) (thng s trng thi cn li thay i tng ng theo) ch khng th thay i ty (t do) c nhit ln p sut c. - H gm nc , nc lng, hi nc ch c th cng tn ti nhit 0,0098oC v p sut 4,58mmHg. H ny c bc t do bng 0 (h v bin, bt bin) v duy tr h gm 3 pha ny khng th thay i c thng s trng thi nhit hay p sut no c m ch c tr s nhit , p sut xc nh trn. 2. iu kin cn bng pha cc pha cn bng bn vi nhau, ngha l khng c s truyn nhit hay chuyn cht gia cc pha th phi tha mn cc iu kin sau:
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- Nhit cc pha phi bng nhau (cn bng nhit). - p sut cc pha phi bng nhau (cn bng c). - Ha th (th ha) ca mi cu t trong tt c cc pha phi bng nhau (cn bng ha hc). [Gi s mt cu t i ca h c hai tr s ha th khc nhau trong hai vng

A v B ca h nu th cu t i s di chuyn mt cch bt thun nghch t A n B. Ngha l vt cht di chuyn mt cch t nhin t vng c ha th cao n vng c ha th thp tng t nh dng in di chuyn t vng c in th cao n vng c in th thp. Do , mi cu t trong cc pha cn bng nhau th ha th ca cu t ny trong cc pha phi bng nhau ]. 3. Qui tc pha Qui tc pha do nh bc hc M Gibbs a ra nm 1876, n biu din s lin h gia s pha (F), s cu t (C) v bc t do (f) ca mt h. Gi X l tng s thng s trng thi ca h. Y l s phng trnh lin h gia cc thng s trng thi. Th s bc t do f ca h l: f=X-Y . S thng s trng thi nhit F pha l F. . S thng s trng thi p sut F pha l F. . S thng s trng thi v thnh phn ca C cu t F pha l CF. Vy tng s thng s X ca h l: X = F + F + CF = 2F + CF. S phng trnh lin h cc thng s trng thi trn gm: - iu kin cn bng nhit :
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=> c (F - 1) phng trnh. - iu kin cn bng p sut:

- iu kin cn bng ha th ca C cu t trong F pha:

- iu kin tng thnh phn cc cht trong mt pha phi bng 100% => c F phng trnh (v mi pha c 1 phng trnh). Nh vy, tng s phng trnh Y l: Y = (F - 1) + (F - 1) + C(F - 1) + F Y = 3F + CF - C - 2 Bc t do f l: f=X-Y f = 2F + CF - (3F + CF - C - 2) T : f=CF + 2 (6-2)

Biu thc ny thng c gi l qui tc pha ca Gibbs c th pht biu nh sau: "S bc t do ca mt h m ch chu nh hng ca hai thng s trng thi l nhit v p sut th bng s cu t tr i s pha c trong h v cng hai". Vi nhng bin i p sut khng i bng p sut kh quyn chng hn th bc t f s l: f=CF + 1
111

(6-3)

Vi bin i ng p v ng nhit th: f=CF (6-4)

Da vo qui tc pha, c th phn loi cc h theo mt trong ba tiu chun l: s cu t, s pha hay s bc t do. - Da vo s cu t, ngi ta phn bit h mt cu t, h hai cu t, h ba cu t... ty theo h c cha mt, hai hay ba cu t. - Da vo s pha, ngi ta phn bit h ng th (h mt pha), h d th (h hai pha, h ba pha...) ty theo h c cha mt pha, hai pha, ba pha... - Da vo s bc t do, ngi ta phn bit h khng bin (v bin, bt bin), h mt bin, h hai bin, h nhiu bin (a bin) ty theo h c bc t do bng 0, 1, 2 hay nhiu bc t do. 4. Cn bng pha trong h mt cu t a. Khi nim v phn tch ha l Nhim v ca ha hc l nghin cu nhng bin i ha hc khi cho hai hay nhiu cht tng tc vi nhau. Tng qut s tng tc ny c th dn n mt trong ba trng hp sau: - To thnh cht ha hc mi c tnh cht c xc nh r. - To thnh hn hp ng th c thnh phn thay i m c gi l dung dch. - To thnh hn hp d th. nghin cu kt qu ca cc tng tc trn, ngi ta thng tch tt c cc pha trong h ra khi nhau ri mi tin hnh phn tch thnh phn, cu to v tnh cht. Tuy nhin, nhiu khi khng th tinh ch c nh i vi cht d b phn tch khi un nng th
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kh tch ra khi c cn hay chng ct nhm kt tinh n hay ly n ra khi h. Phng php trn cng gp kh khn khi nghin cu hp kim, thy tinh, dung dch... Do , c mt phng php khc cho php xc nh bn cht v thnh phn ca cc pha c trong h m khng cn tch n ra. Phng php ny c gi l phng php phn tch ha l. Phng php phn tch ha l nghin cu s ph thuc cc tnh cht vt l ca h vo nhng thng s trng thi ca h nh nhit T, p sut P, thnh phn x. Ta c hm s:

n gin, ngi ta thng nghin cu s ph thuc ca mt s tnh cht vt l no vo thnh phn nhit v p sut khng i. Hm s trn tr thnh:

Kt qu nghin cu c trnh by di dng gin . Dng gin d cho thy s ph thuc gia cc yu t m ta mun kho st. Nu thng s l thnh phn th l gin thnh phn - tnh cht. Da trn gin thu c, ta c th bit c trng tng tc xy ra nh s pha c to thnh, tnh cht, thnh phn v gii hn tn ti ca chng trong h. b. Cc phng trnh nhit ng hc lin h p sut v nhit ca s chuyn pha Nhit chuyn pha l nhit ti cc pha nm cn bng vi nhau p sut xc nh. Gi s c mt cht ang hai pha (1) v (2) ang nm cn bng, V d thay i p sut t P n P + dP th mun cho hai pha vn nm cn bng vi nhau, yu t th hai l nhit phi bin i tng ng t T tr thnh T + dT. Khi nng lng t do ca cht trong hai pha s c tr s mi nhng vn bng nhau:

(6-5)

Ta bit vi phn hm s G ca mt cht l:

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(6-6)

Khi h t trng thi cn bng iu kin ng nhit, ng p th:

(6-7)

H thc ny c gi l phng trnh Clapeyron c nhiu ng dng khi kho st qu trnh chuyn pha. + nh hng ca p sut n nhit nng chy Qu trnh nng chy l qu trnh chuyn mt cht t trng thi rn sang trng thi lng. Nhit nng chy ca mt cht l nhit ti c s cn bng gia hai pha rn v lng p sut xc nh ( nu khng cho bit p sut no th hiu l bng p sut kh quyn 1atm ).

Qu trnh nng chy thu nhit - Nu th tch cht lng ln hn th tch cht rn th:

t:

=> T, P ng bin.

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- Nu th tch cht lng nh hn th tch cht rn (cht ny khi nng chy c s co th tch hay gim th tch), th:

V d: p sut 1atm, nc nng chy 0oC. p sut 2atm, nc nng chy - 0,0076oC.

T c th suy ra mt cch gn ng, mun nc nng chy - 1oC th p sut phi tng ln n 132 atm.

+ nh hng ca nhit n nhit si Qu trnh si ca mt cht l qu trnh bin i cht t dng lng thnh dng hi. Th tch hi ln hn rt nhiu so vi th tch cht khi dng lng.

Qu trnh si l qu trnh thu nhit

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+ nh hng ca nhit n p sut hi bo ha p sut hi bo ha ca mt cht l p sut ti cht lng hoc cht rn cn bng vi hi ca n nhit xc nh. Khi p sut hi bo ha bng p sut kh quyn th cht lng si, nhit lc l nhit si ca cht lng. Trong s thng hoa, p sut hi bo ha l p sut ti cht rn cn bng vi hi ca n. Nu p sut ca hi cha t ti gi tr p sut hi bo ha th hi gi l hi kh, cc phn t cht lng tip tc bay hi. Qu trnh bay hi thu nhit (s bay hi lm tng th tch)

V d: Nc c p sut hi bo ha bng 17,5 mmHg 20oC 760 mmHg (1atm) 100oC 2 atm 120oC 4 atm 143oC

Nu xt 1 mol cht, v coi hi cht thu c l kh l tng th:

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(6-8)

(6-9)

(Phng trnh Clapeyron - Clausius)

(6-10)

V lgP theo 1/T ta c mt ng thng m dc (h s gc) l C'), t xc nh c Vi s si (s bc hi):

(6-11)

(tung gc l

Vi s thng hoa:
(6-12)

V d: p sut hi ca clorur tert-butil nghim ng h thc:

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Tnh Gii:

ca clorur tert-butil.

Phng trnh Clapeyron - Clausius ly tch phn ch p dng c trong khong nhit nh v tht ra ph thuc vo nhit T.

c. Gin trng thi h mt cu t Gin pha c to ra da trn c s cc s liu thc nghim. Gin pha ca h mt cu t c biu din trong ta phng p sut - nhit . T: f = C ( F + 2 Vi h 1 cu t => C = 1 => f = 1 - F + 2
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=> f = 3 - F V l 3. i vi h 1 cu t th s pha F nhiu nht c th

=> s bc t do ln nht trong h 1 cu t l 2. Di y l gin pha ca nc:

ng OA l ng thng hoa ca H2O rn, biu din s cn bng gia nc vi hi nc, ngha l trn (ng vi nhit , p sut thch hp) c s cn bng tn ti ng thi gia nc pha rn v nc pha hi. ng OB biu din s cn bng gia nc vi nc lng. ng OC biu din s cn bng gia nc lng vi hi nc. O l ta ti c s cn bng tn ti ng thi c 3 pha rn, lng, hi ca nc, l v tr c nhit 0,0098oC, p sut 4,58mmHg v c gi l im ba ca nc. vng H2O rn (hoc nc lng hoc hi nc) c s pha F = 1. => s bc t do trong vng l: f = 3 - F = 3 - 1 = 2 Ngha l trong cc vng ny ta c th t do thay i 2 thng s nhit v p sut (trong chng mc no ) m s pha ca h vn l 1. Cn trn ng cn bng hai pha (OA, OB, OC) lc s pha F = 2.
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=> S bc t do trn : f = 3 - F = 3 - 2 = 1. Ngha l trn cc ng ny ch c th thay i t do 1 thng s nhit (hoc p sut), thng s kia thay i tng ng theo, v h vn cn cn bng tn ti hai pha. Cn im ba (0), s pha F = 3 => S bc t do: f = 3 - F = 3 - 3 = 0 => Ti y khng th thay i thng s nhit hay p sut c m ch c mt tr s xc nh (0,0098oC; 4,58mmHg) nc tn ti ng thi 3 pha. dc cc ng OA, OB, OC c th c gii thch khi da vo phng trnh Clapeyron:

Cn c vo du ca bin v cn c vo ln ca

m bit c P, T ng bin hay nghch m ng biu din dc nhiu hay t.

5. Cn bng trong h nhiu cu t Trong h nhiu cu t, ngoi cc thng s trng thi l nhit v p sut cn c cc thng s v thnh phn ca cc cu t trong h. Cn bng pha trong trng hp ny ch yu c nghin cu da vo gin trng thi. V c nhiu thng s nn gin cng cn nhiu trc biu din nn rt phc tp v kh thy. n gin, ngi ta nghin cu cn bng pha trong iu kin c nh mt hay mt s thng s trng thi gin ch cn li hai hay ba chiu. Sau y chng ta xem gin ca hai cu t mui n trong nc

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Gin c chia lm 6 vng (min): - Vng (1): H ng th mt pha: dung dch NaCl trong nc. - Vng (2): H hai pha cn bng nhau: dung dch lng Vng (3): H hai pha cn bng nhau: dung dch lng - Vng (4): H hai pha cn bng nhau: dung dch lng - Vng (5): H hai pha ring: Tinh th - Vng (6): H hai pha ring: Tinh th NaCl v tinh th tinh th H2O. tinh th NaCl. tinh th . . .

T gin trn ta c th xc nh c nhiu tnh cht ca h cn bng. V d: Lm lnh mt dung dch mui n c nng khong 15% t nhit 40oC (im A), t nc kt tinh thnh tinh th H2O. Do H2O kt tinh tch khi dung dch nn nng NaCl trong dung dch tng dn theo s gim nhit , tc im biu din (ta ) ca dung dch lng chuyn dn t
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. T y dung dch bt u kt tinh thm tinh th . Do gin c xy dng trong iu kin p sut khng i v c tr s ln ( xem nh dung dch khng bay hi ) nn cng thc tnh bc t do f ca h l: f = C - F + 1 ( Khi T hoc P khng i ) (C = 2; F = 3) => f = 2 - 3 + 1 = 0 V vy, khi h c 3 pha cn bng th bc t do ca h bng 0 (h v bin). Nh vy, trong thi gian h kt tinh ng thi hai loi tinh th th nhit cng nh thnh phn cc pha khng i. Hn hp Mui - Nc ng vi im E, cng nh cc h hai, ba t bt k c tnh cht nh vy (kt tinh ng vi nhit v thnh phn cc pha khng i, tng t nh mt cht nguyn cht) c gi l hn hp eutectic (eutectique, -tec-ti, xut pht t ting Hy Lp eutektos, c ngha l d nng chy). Qu trnh kt tinh kt thc ti im E. Nu c mt hn hp nc ang tan ( 0oC; 1atm ) m li thm dn mui n vo th im cn bng hai pha (dung dch lng nc ) cng s chuyn dn v im E, ng vi nhit cn bng thp dn. Bng cch thm mui vo nc , ngi ta c th to c hn hp sinh hn (lm lnh) c nhit thp hn 0oC, m trong trng hp l tng c th t n - 21oC.

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TI LIU THAM KHO

1. Nguyn Hu Ph, Ha l v ha keo, NXB KH-KT, 2002 2. Trn Vn Nhn, Nguyn Thc Su, Nguyn Vn Tu, Ha l tp 1, Nh xut bn Gio dc, 1998. 3. Nguyn nh Hu - Gio Trnh Ha l T1,2. Nh xut bn Gio dc, 2000 . 4. Nguyn Vn Du - Nhit ng hc NXBGD H Ni 1989. 5. Nguyn Vn Du - Trn Nguyn Hip Hi . Bi Tp Ha l NXBGD 1977 6. La ng Minh - Cu hi v bi tp ha l. NXBGD 1973. 7. Lm Ngc Thim - Bi tp ho l c s, Nh xut bn khoa hc k thut, 2003. 8. P.W. Atkins; Physical chemistry, Oxford university press 1998.

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