21 Co So LT Hoa Hoc DHBK HN PDF

Bi ging mn C s l thuyt Ha hc
PHN I: NHIT NG HO HC
Mun xt mt phn ng ho hc c thc hin c hay khng cn bit: - iu kin no th phn ng xy ra v xy ra n mc no? - Phn ng xy ra nh th no? Nhanh hay chm? Nhng yu t no nh hng n tc phn ng? Khi tr li c c hai cu hi ny, ngi ta c th iu khin c phn ng, tm c iu kin ti u thc hin phn ng, nhm t hiu qu cao nht. Cu hi th nht l i tng ca nhit ng ho hc, cn cu hi th hai l i tng ca ca ng ho hc. Nhit ng hc l b phn ca vt l hc, nghin cu cc hin tng c v nhit, cn nhit ng ho hc l b phn ca nhit ng hc nghin cu nhng quan h nng lng trong cc qu trnh ho hc.
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CHNG I: P DNG NGUYN L TH NHT CA NHIT NG HC VO HO HC

I. MT S KHI NIM M U 1. Kh l tng: Cht kh c coi l l tng khi m khong cch gia cc phn t kh xa nhau, c th b qua s tng tc gia chng v coi th tch ring ca cc phn t kh l khng ng k (kh c p sut thp). Phng trnh trng thi ca kh l tng: nu c n mol kh p sut P, nhit T v chim th tch V th: PV = nRT =
m RT M
(1.1)
trong : m- khi lng ca kh, g M: Khi lng mol ca kh, g T Nhit tuyt i, K ( T = t0C +273) R: Hng s kh l tng, ty theo n v ca P v V m c ga tr khc nhau: - Nu P (atm), V(dm3=l) - Nu P (Pa=N/m2), V(m3) R = 0,082 atm.l.K-1.mol1 R = 8,314 J.K-1.mol-1
1atm = 1,013. 105 Pa= 1,013. 105N/m2= 760 mmHg - Nu trong bnh c mt hn hp kh th mi kh gy nn mt p sut gi l p sut ring phn ca kh v c k hiu l Pi .Tng tt c cc p sut ring phn bng p sut chung P ca hn hp.Nu gi V l th tch chung ca hn hp kh ( bng dung tch bnh ng th phng trnh kh kh l tng c dng:
P = Pi = ni RT V
(1.2) : Tng s mol kh trong hn hp.
n i
p sut ring phn Pi ca kh i trong hn hp c th tnh:

Pi = ni
n RT hoc Pi= NiP vi Ni = i n i V
(1.3)
2. H v mi trng - H: H l i tng cn nghin cu cc tnh cht nhit ng hc. i km vi khi nim h l khi nim mi trng xung quanh, l ton b phn cn li ca v tr bao quanh h. H c phn cch vi mi trng xung quanh bng mt mt thc hay tng tng. - C 4 loi h: + H c lp: l h khng trao i cht v nng lng vi mi trng + H m: l h trao i cht v nng lng vi mi trng.
+ H kn l h ch trao i nng lng vi mi trng + H khng trao i nhit vi mi trng c gi l h on nhit. 3.Quy c v du trong qu trnh trao i nng lng Nng lng trao i gia h v mi trng c th l cng , nhit, nng lng in... H nhn nng lng: du (+) H nhng nng lng du ()
4.Trng thi ca h v cc thng s trng thi: - Trng thi v m ca mt h c c trng bng nhng i lng xc nh nh: t0C, P, V, C...Cc thng s ny c th o c, gi l cc thng s trng thi. v d: gia s mol kh n, nhit T v p sut P ca mt h kh (gi s l kh l tng) c mi quan h cht ch, c biu din bng phng trnh trng thi ca kh l tng PV=nRT. - C hai loi thng s trng thi: dung v cng + Thng s trng thi dung l nhng thng s trng thi t l vi lng cht, th d th tch, khi lng. + Thng s trng thi cng khng t l vi lng cht, v d nhit p sut, nng , nht. 5. Trng thi cn bng ca h L trng thi ti cc thng s trng thi ca h khng i theo thi gian. VD phn ng thun nghch CH3COOH + C2H5OH <=> CH3COOC2H5 + H2O t trng thi cn bng khi nng ca 4 cht khng bin i . 6. Bin i thun nghch v bin i bt thun nghch - Nu h chuyn t mt trng thi cn bng ny sang mt trng thi cn bng khc v cng chm qua lin tip cc trng thi cn bng th s bin i c gi l thun nghch.y l s bin i l tng khng c trong thc t. - Khc vi s bin i thun nghch l s bin i bt thun nghch. l nhng bin i c tin hnh vi vn tc ng k. Nhng bin i xy ra trong thc t u l bt thun nghch. 7.Hm trng thi - Mt hm F( P,V,T...) c gi l hm trng thi nu gi tr ca n ch ph thuc vo cc thng s trng thi ca h m khng ph thuc vo cch bin i ca h. - V d: n mol kh l tng: + trng thi 1 c c trng bng P1V1=nRT1 + trng thi 1 c c trng bng P2V2=nRT2 PV l mt hm trng thi, n khng ph thuc vo cch bin i t trng thi 1 sang trng thi 2.
8.Cng v nhit: L hai hnh thc trao i nng lng. Cng W (J, kJ) Nhit Q (J, kJ) Cng v nhit ni chung khng phi l nhng hm trng thi v gi tr ca chng ph thuc vo cch bin i. * Cng gin n ( cng chuyn dch)
W
= - Pngoi.dV =-PndV
2
(1.4) (1.5) W=0. (1.6)
W ph thuc vo Pn ( v h sinh cng nn c du -). Nu qu trnh l hu hn => W = Pn dV

1
Nu gin n trong chn khng Pn= const (Pn=Pkq) Wtn= Pn dV

V1 V2
Pn =0
Nu gin n bt thun nghch: gin n chng li Pn khng i: Wbtn = -Pn(V2-V1) (1.7) Nu gin n thun nghch: tc l Pn =Ph
Nu kh l l tng v gin n ng nhit c : Pn = Ph =

V2 V nRT dV => WTN = nRT = nRT ln 2 V1 V V1 V
Vy WTN =- nRT ln
V2 P =- nRT ln 1 V1 P2
(1.8)
II. NGUYN L I P DNG VO HA HC 1. Khi nim ni nng (U) Nng lng ca h gm 3 phn ng nng chuyn ng ca ton h Th nng ca h do h nm trong trng ngoi Ni nng ca h
Trong nhit ng ho hc nghin cu ch yu ni nng. Ni nng ca h gm: ng nng chuyn ng ca cc phn t, nguyn t, ht nhn v electron (tinh tin, quay..) Th nng tng tc (ht v y) ca cc phn t, nguyn t, ht nhn v electron. Nh th ni nng (U) ca h l mt i lng dung , gi tr ca n ch ph thuc vo trng thi vt l m khng ph thuc vo cch chuyn cht ti trng thi . N l mt hm trng thi.
Ni nng ca h ph thuc vo bn cht, lng ca n, p sut. nhit ,th tch v thnh phn. i vi kh l tng ni nng ca h ch ph thuc vo nhit . 2. Pht biu nguyn l I ca nhit ng hc Nguyn l I ca nhit ng hc v thc cht l nh lut bo ton nng lng: Nng lng ca mt h c lp lun lun bo ton. a.Tn ti mt hm trng thi U gi l ni nng. dU l mt vi phn ton phn. b. S bin i ni nng U ca h kn chuyn t trng thi 1 sang trng thi 2 bng tng i s ca tt c cc nng lng trao i vi mi trng trong qu trnh bin i ny (d l bin i thun nghch hay bt thun nghch).
U
= U2-U1 = WA + QA =WB + QB =...=const i vi mt bin i v cng nh
trong W l Q l cng v nhit lng m h trao i vi mi trng. dU= W + Q dU: vi phn ton phn
W v Q : khng phi l vi phn ton phn.
i vi mt bin i hu hn
U = dU = W + Q
1 2
(1.9)
Nu: + Trng thi u v cui nh nhau U = dU = 0 --> W+Q=0 + H c lp: W = Q = 0 --> U =0 3. Nhit ng tch, nhit ng p a.Nhit ng tch.( V = const) Xt 1 h kn, c T, V = const, h ch sinh cng c hc:
W = pdV v V = const W = pdV = 0
Theo nguyn l I: dU= W + Q Do : dU= Q v U =

v = const
Q = Q
(1.10)
Qv l nhit ng tch, gi tr ca n ch ph thuc vo trng thi u v cui ca h. b. Nhit ng p(P= const) Xt h kn, thc hin c T, P =const, h ch sinh cng c hc: W= pdV = P(V 2 V1 )
1 2
= U2-U1 = W + Q
U2 - U1 = Qp-P(V2-V1) hay Qp = (U2+PV2) (U1+PV1) QP: Gi l nhit ng p

H=U+PV (1.11)
Ta c: Qp= H2-H1 = H III. NHIT PHN NG HO HC. 1. Nhit phn ng
H c gi l entapi, n l hm trng thi v U v PV u l nhng hm trng thi.
L nhit lng thot ra hay thu vo khi phn ng xy ra theo ng h s t lng, cht tham gia v sn phm cng mt nhit T. c th so snh nhit ca cc phn ng cn ch r iu kin phn ng xy ra: Lng cc cht tham gia v sn phm to thnh theo h s t lng. Trng thi vt l ca cc cht
Vi mc ch ny ngi ta a ra khi nim trng thi chun. Trng thi chun ca mt cht nguyn cht l trng thi l hc di p sut 101,325kPa(1atm) v nhit kho st n bn nht. V d: Cacbon tn ti hai dng th hnh l graphit v kim cng. 298K v di p sut 101,325kPa, graphit l bin i th hnh bn nht do trng thi chun 298K ca cacbon l graphit. Nu phn ng c thc hin P=const th nhit phn ng c gi l nhit phn ng ng p Qp= H . Nu phn ng c c thc hin V=const th nhit phn ng c gi l nhit phn ng ng tch Qv= U . Phn ng ta nhit v phn ng thu nhit Phn ng ta nhit: l phn ng nhng nhit lng cho mi trng. Khi
H = QP <0 hoc U = QV <0. V d phn ng ti vi
Phn ng thu nhit: l phn ng nhn nhit lng t mi trng. Khi

H = QP >0 hoc U = QV >0. V d phn ng nung vi..
Quan h gia nhit ng tch v nhit ng p:

H = (U + pV ) p = U + pV
Qp= Qv+ nRT R = 8.314 J/mol.K: hng s kh l tng T: K V d: C6H6 (l) +

15 O2(k) = 6CO2(k) + 3H2O(l) 2
(1.12)
Trong : n = s mol sn phm kh s mol cht kh tham gia phn ng.
n= 6-7,5=-1,5.
C(r) + O2(k) = CO2(k)

n= 1- 1= 0
2. Nhit sinh chun ca mt cht: L nhit ca phn ng to thnh 1 mol cht t cc n cht bn iu kin chun (cht sn phm v cht phn ng phi l cc cht nguyn cht 1atm v gi P, T=const, cc s liu nhit ng chun trong cc ti liu thng c xc nh nhit T=298 K).
0 K hiu H T ,s (kJ.mol-1)
0 Nu T =298 => H 298, s
0 V d: H 298, s (CO2)=-393,51(kJmol-1). N l nhit phn ng ca phn ng sau 250C
khi pO = pCO = 1atm

2 2
Cgr + O2(k) = CO2(k). C graphit l n cht bn nht ca cacbon 1 atm v 298K. - T nh ngha trn ta suy ra nhit sinh chun ca n cht bn bng khng. 3. Nhit chy chun ca mt cht: L nhit ca qu trnh t chy han ton 1 mol cht bng O2 to thnh cc xit bn nht ( vi ha tr cao nht ca cc nguyn t), khi cc cht trong phn ng u nguyn cht P=1atm v gi T, P khng i (thng T=298K).
0 H T ,c (kJ.mol ) 0 V d: H 298,c (CH 4 ) =-890,34kJ.mol-1 ng vi nhit ca phn ng sau 250C v p=const
-1
khi PCH = PO = PCO = 1atm .

4 2 2
CH4 (k)+ 2O2 (k)
CO2 (k) + 2H2O(l)
Tt c cc xit bn vi ha tr cao nht ca cc nguyn t u khng c nhit chy. IV.NH LUT HESS V CC H QU 1.Pht biu: Hiu ng nhit ca mt phn ng ch ph thuc vo trng thi u v trng thi cui ca cc cht tham gia v cc cht to thnh ch khng ph thuc vo cc giai on trung gian, nu khng thc hin cng no khc ngoi cng gin n. V d: Cgr
H 1 H
O2(k)
H 2
CO2(k)
CO(k) + 1/2 O2(k) Theo nh lut Hess:

H = H 1 + H 2
(1.13)
2.Cc h qu
H qu 1: Hiu ng nhit ca phn ng thun bng hiu ng nhit ca phn ng nghch nhng ngc du.: H t = H n tng nhit sinh ca cc cht u.
H = H s (s nph m) H s (thamgia )
(1.14)
H qu 2: Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc cht cui tr i (1.15) (1.16)
Nu iu kin chun v T=298K th

H 0 298, pu = H 0 298,s (s nphm ) H 0 298,s (thamgia )
0 bng khng: H T , s (n cht) = 0.
T nh ngha ny suy ra: nhit sinh ca mt n cht bn vng iu kin chun V d: Tnh H0 ca phn ng: C2H4(k) + H2 (k) --> C2H6 298K?
0 Cho bit H 298, s ca cc cht (kJ.mol-1) nh sau:
C2H4(k): +52,30 C2H6(k): -84,68 Gii: Ta c:

0 H 298 0 0 0 = H 298, s (C2H6(k)) - [ H 298, s (C2H4(k)) + H 298, s (H2(k))]
=-84,68-52,30-0 =-136,98kJ.mol-1 H qu 3: Hiu ng nhit ca mt phn ng bng tng nhit chy ca cc cht u tr i tng nhit chy ca cc cht cui.
H p = H c (tg ) H c (sp)
(1.17) (1.18)
Nu iu kin chun v T=298K th

H 0 298, p = H 0 298,c (tg ) H 0 298,c (sp)
3.Cc ng dng * nh lut Hess v cc h qu ca n c mt ng dng rt ln trong Ho hc, n cho php tnh hiu ng nhit ca nhiu phn ng trong thc t khng th o c. V d1: khng th o c nhit ca phn ng Cgr + 1/2 O2(k) =CO(k) v khi t chy Cgr ngoi CO (k) ra cn to thnh CO2(k) nhng nhit ca cc phn ng sau y o c:
0 Cgr + O2(k) = CO2(k) H 298 =-393513,57 J.mol-1
0 CO(k) + O2(k) = CO2(k) H 298 =-282989,02 J.mol-1
tnh c nhit ca phn ng trn ta hnh dung s sau:
Bi ging mn C s l thuyt Ha hc Cgr + O2(k) x=? CO(k) + 1/2O2(k) CO2(k)
Trng thi u (Cgr+O2) v trng thi cui (CO2(k)) ca c hai cch bin i l nh nhau, do theo nh lut Hess: -393.513,57 = x 282.989,02 x=-110507,81J.mol-1 V d 2: Xc nh nng lng mng lui tinh th ca NaCl(r) bit + Nhit nguyn t ha Na(r) Na(r) Cl2(k) Na(h) Cl(k) + e Na(h) 2Cl(k) Na+(h) + e Cl-(k)
H1 = +108.724 J .mol 1 H 2 = +242.672 J .mol 1 H 3 = +489.528 J .mol 1 H 4 = 368.192 J .mol 1
+ Nhit phn ly Cl2(k) + Nng lng ion ha Na(h) +i lc i vi electron ca Cl(k) +Nhit ca phn ng Na(r) + 1/2 Cl2(k) Haber:
Trng thi u
Na(r) + 1/2 Cl2(k)
H1
H5
NaCl H 5 = 414.216 J .mol 1
xc nh nng lng mng li tinh th NaCl ta dng chu trnh nhit ng Born
Trng thi cui
NaCl(r)
1/2
x=?
H3
H4
Na(h) + Cl(k)
Na+(h) + Cl-(k)
Theo nh lut Hess ta c:

H 5 = H1 + 1 / 2H 2 + H 3 + H 4 + x
x= H 5 (H1 + 1 / 2H 2 + H 3 + H 4 ) x= -765.612J.mol-1
V. S PH THUC HIU NG NHIT VO NHIT .NH LUT KIRCHHOFF
1. Nhit dung mol ca 1 cht L nhit lng cn thit nng nhit ca 1 mol cht ln 1K v trong sut qu trnh ny khng c s bin i trng thi(nng chy, si, bin i th hnh...)
- n v thng dng ca C l: J.K-1mol-1 - Nhit dung mol ng p. Qu trnh c thc hin P=const.
dH H CP= = T p dT
2 2
=> dH=CpdT =>
dH = CP dT
1 1
==> H = C P dT
1
-Nhit dung mol ng tch. Qu trnh c thc hin V=const.

dU U Cv= = T v dT
=> dU=CvdT =>
U = Cv dT
1
==> U = C v dT
1
2.Nhit chuyn pha -Chuyn pha: bay hi ,nng chy, ng c, thng hoa... - H cf l nhit lng trao i vi mi trng khi 1 mol cht chuyn pha. P=const, khi mt cht nguyn cht chuyn pha th trong sut qu trnh chuyn pha, nhit khng thay i. 3. nh lut Kirchhoff Xt 1 h kn, P=const.. Xt phn ng sau thc hin bng hai con ng:
n1A + n2B
H 2
T2
n3C + n4D
H b
Ha
H1
n1A + n2B
T1
n3C + n4D
Theo nh lut Hess ta c H 2 = H1 + H a + H b

H a = (n1C PA + n 2 C PB ) dT = (n1C PA + n 2 CPB )dT
T2 T1 T1 T2
Hb = (n3CPC + n4CPD )dT

T1
T2
T H2 = H1 + [(n3CP + n4CP ) (n1CP + n2CP )]dT

C D A B
T2
T1
=> H T = H T + C P dT => Cng thc nh lut Kirchhoff

2 2
T2
T1
Vi: C P = C P (sp) C P (tg )
iu kin chun(P=1atm) v T1=298 K c:

T
H = H
0 T
0 298
0 + C P dT 298
0 Nu trong khong hp ca nhit => coi C P = const th 0 0 0 H T = H 298 + C P ( T 298)
4.Mi quan h gia nng lng lin kt v nhit phn ng C th quy uc nng lng lin kt (Elk) tng ng vi nng lng ph v lin kt hoc hnh thnh lin kt. y ta qui c Elk ng vi qu trnh ph v lin kt: nng lng lin kt l nng lng ng vi qu trnh ph v lin kt do nng lng lin kt cng ln th lin kt cng bn. - Mt phn ng ho hc bt k v bn cht l ph v lin kt c v hnh thnh cc lin kt mi do Hp c th c tnh qua Elk ca cc lin kt ho hc. V d1: Ph v 1 mol thnh cc nguyn t c lp: H2(k,cb) --> H(k,cb) + H (k,cb)
0 298K, p= 1atm => EH-H = +432kJ.mol-1 = H 298
Trong trng hp ny Elk coi nh hiu ng nhit ca qu trnh. V d2: Xt phn ng N2(k) + 3H2(k) => NH3(k). Thc hin bng 2 con ng
N2(k) + 3H2(k) EN-N 3EH-H
H
2NH3(k)
-6EN-H
2H(k) + 6H(k)
H = E N N + 3 E H H 6 E N H
Ti liu tham kho:

1. Nguyn nh Chi, C S L Thuyt Ha Hc, NXB GD, 2004. 2. Nguyn Hnh, , C S L Thuyt Ha Hc, Tp 2, NXB GD 1997. 3. L Mu Quyn, C S L Thuyt Ha Hc - Phn Bi Tp, NXB KHKT, 2000.
CHNG II: NGUYN L II CA NHIT NG HC CHIU V GII HN T DIN BIN CA QU TRNH M U Trong t nhin, cc qu trnh l hc v ho hc xy ra theo chiu hon ton xc nh. - Nhit t truyn t vt nng sang vt lnh hn - Kh t truyn t ni c p sut cao n ni c p sut thp - Cc phn ng ho hc t xy ra, v d: Zn + HCl --> ZnCl2 + H2 Cn cc qu trnh ngc li th khng t xy ra c. Nguyn l I cho php tnh nhit ca cc phn ng nhng khng cho php tin on chiu v gii hn ca qu trnh Nguyn l II cho php gii quyt cc vn ny. I.NGUYN L II. HM ENTROPY 1.Nguyn l II (Tiu chun xt chiu ca qu trnh) - Tn ti mt hm trng thi gi l entropi (S). - nhit T khng i, trong s bin i v cng nh, h trao i vi mi trng mt nhit lng Q th bin thin entropi ca qu trnh c xc nh: Q Nu l bin i thun nghch: dS = TN
T
Nu l bin i bt thun nghch: dS > Tng qut

dS
QbTN
T
Q
T
2
Du > : qu trnh bt thun nghch Du = : qu trnh thun nghch
S
1
Q
T
* Ch : V S l hm trng thi --> S ch ph thuc vo trng thi u v trng thi cui, tc l:

S BTN = S TN =
1 2
QTN
T
2
S TN = S BTN >
1
Qbtn
T
==> QTn> QBTN : Nhit qu trnh thun nghch ln hn nhit qu trnh bt thun nghch. + xc nh Sbtn , trc ht hnh dung mt qu trnh thun nghch c cng trng thi u v trng thi cui vi qu trnh bt thun nghch, sau tnh S theo cng thc:
S =
1 2
QTN
T
(khng xc nh c trc tip Sbtn)

2. Nguyn l II p dng trong h c lp i vi h c lp: Qtn= 0 --> S = 0 Qbtn=0 --> S > 0 Nh vy i vi h c lp: - Trong qu trnh thun nghch (cn bng), entropi ca h l khng i. - Trong qu trnh bt thun nghch ngha l t xy ra, entropi ca h tng. iu ny c ngha rng trong cc h c lp, entropy ca h tng cho ti khi t ti gi tr cc i th h t ti trng thi cn bng.o li ta c th ni: Trong h c lp: - Nu dS >0 ( S tng) h t din bin 2 - Nu dS=0, d S<0 (S max) h trng thi cn bng. 3. ngha hm entropi a. Entropi l thc o hn n ca h Xt 1 h c lp T=const, h gm 2 bnh c th tch bng nhau, ng 2 kh l tng A v B c pA=pB u thp. Hai bnh c ni vi nhau bng mt dy dn c kho K. M K--> 2 kh khuch tn vo nhau cho n khi c s phn b ng u trong ton b th tch ca 2 bnh. S khuch tn cc kh l tng vo nhau l qu trnh c T=const(Q=0) --> S > 0 (S2> S1) --> hn n ca trng thi cui (hn hp 2 kh) c trng bng S2 ln hn hn n ca trng thi u ( mi kh 1 bnh ring bit) c trng bng S1. Vy trong h c lp, qu trnh t xy ra theo chiu tng hn n ca h (tng entropi, S > 0 ). Qu trnh ngc li: Mi kh t tch ra khi hn hp kh tr li trng thi u khng th t xy ra. * Kt lun: - Entropi c trng cho hn n: hn n ca h cng ln th S cng ln. - Nu s ht trong h cng ln--> hn n cng ln--> Sln - Lin kt gia cc ht trong h cng yu --> hn n cng ln--> S ln. V d: SH2O(r) ,SH2O(l)< SH2O (k) . - S l hm trng thi v l i lng dung . b. ngha thng k ca S Trng thi ca mt tp hp bt k c th c c trng bng 2 cch: - Bng gi tr ca cc tnh cht o c : T, P,C...--> c gi l cc thng s trng thi v m. - Nhng c trng nht thi ca cc phn t to nn h c gi l cc thng s vi m.
* S thng s trng thi vi m ng vi mt trng thi v m c gi l xc sut nhit ng Nu s phn t trong h tng th S tng--> tng. Gia S v c quan h vi nhau thng qua h thc Bolzomann. H thc Boltzmann (l c s ca nguyn l III) S=kln k: hng s Boltzmann Nhn xt: Trong h c lp, qu trnh t din bin theo chiu tng xc sut nhit ng . 4.Bin thin entropi ca mt s qu trnh a. Bin thin entropi ca qu trnh bin i trng thi ca cht nguyn cht Trong sut qu trnh ny T=const ==> S ca mt mol cht nguyn cht trong qu trnh bin i trng thi xy ra P=const l
S =
1 2
Q
T
H cf Tcf
H cf nhit chuyn trng thi
b. Bin thin entropi ca qu trnh gin n ng nhit kh l tng T=const, dn n n mol kh l tng t V1-->V2
S =
1 2
QTN
T
QTN v T=const T
V2 V1
V T=const --> U = 0 WTN = nRT ln Theo nguyn l I: U = QTN + WTN = 0 ==> S = nR ln

V2 P = nR ln 1 V1 P2
--> QTN = WTN = + nRT ln
V2 V1
Nu P1>P2 --> S > 0 : qu trnh gin n ny t din bin ==> Cch pht biu khc ca nguyn l II: Cc cht kh c th t chuyn di t ni c p sut cao n ni c p sut thp. c. Bin thin entropi ca cht nguyn cht theo nhit : un nng n mol 1 cht nguyn cht t nhit T1-->T2 vi iu kin trong khong nhit cht ny khng thay i trng thi - Trong iu kin P = const:
S p =
1 2
Q p
dH dT = = nC p T T T 1 1
2
Vy S p = nC p
1
dT T
Trong iu kin V= const

S v =
1 2
Q v
dU dT = = nC v T T T 1 1
==> Vy S v = nC v
1
dT T
Nu coi Cp hoc Cv khng i theo T th:

S p = nC p ln S v = nC v ln T2 T1 T2 T1
II. Nguyn l III ca nhit ng hc Nhn xt: dng tinh th hon ho ca mt cht nguyn cht OK ng vi 1 trng thi v m ch c 1 trng thi vi m ==> OK th = 1 1. Nguyn l III (tin Nernst) Entropi ca mt cht nguyn cht di dng tinh th hon ho OK bng khng:
S (0 K ) = 0 = k ln
( = 1)
2.Entropi tuyt i ca cc cht nguyn cht cc nhit T V d: un nng n mol 1 cht nguyn cht 0K -->T K, trong khong ny xy ra cc qu trnh bin i trng thi v iu kin P=const. Tnh ST? 0 K---> Tnc--->Ts--->T
S = S T S T =0 = S T =
T =0
nC p
dT T
T T
S = S T S T =0 =
Tnc
0K
nC
p( r )
S H nc H s dT dT dT +n + nC p ( l ) +n + nC P ( h ) T TS T Tnc T Tnc TS
0 thng th P=1atm, T=298K, n=1mol ==> S 298 ( J .K 1 .mol 1 )
-->Bng entropi chun ca cc cht 25oC * Nhn xt: Gi tr S cht nguyn cht lun > 0, tr khi xt cho ion trong dung dch, c th c Sion<0. 3.Bin thin entropy ca cc phn ng ho hc V S l hm trng thi v l i lng dung nn:
S = S ( sp ) S ( tg )
0 0 S = S 298 (sp ) S 298 (tg )
( T, P =const)
Nu iu kin chun (P=1atm) v T=298K th: V Skh>>Slng,Srn ==> c th cn c vo s mol kh 2 v ca phn ng nh gi ln cng nh l du ca S ca phn ng.
n = 0 ==> S nh
n > 0 ==> S > 0 ==> phn ng tng S
n < 0 ==> S nh ==> phn ng gim S
V d:
SO2(k) + 1/2 O2(k) --> SO3(k) c n < 0 ==> S <0 C(gr) + O2(k) --> CO2(k) c n = 0 ==> S 0
III. HM TH NHIT NG. TIU CHUN XT CHIU CA QU TRNH - H c lp: S 0 --> tiu chun t din bin v gii hn ca qu trnh - H khng c lp: gm h + Mi trng --> av 1 h c lp mi bng cch gp h v mi trng thnh 1 h c lp. ==> tiu chun t din bin v gii hn ca h mi l : S + S mt 0
S mt
cha xc nh nhng c th a v cc thng s ca h bng cch tm 1
hm thay th cho c ( S + S mt ), hm thay th ny gi l hm th nhit ng. Thng gp h: + ng nhit, ng p ==> c hm th ng nhit ng p + ng nhit, ng tch==> c hm th ng nhit ng tch 1.Hm th ng nhit ng p a. nh ngha: Xt 1 h: T, P = const H thc hin mt bin i no
S + S mt = S + H mt H = S T T
H
H _Nhit lng trao i vi mi trng S _Bin thin entropi ca h.
Mi trng
H mt = H h = H
S mt = H mt H = T T
==> tiu chun t din bin v gii hn ca qu trnh l:

S + S mt 0 H 0 T
<=> S
<=> H TS 0 <=> (H TS ) 0 <=> G 0

G = H T S 0
t H-TS =G => G l hm trng thi : P,T=const ==> qu trnh t xy ra theo chiu G < 0 v
t cn bng khi G = 0 G c gi l : Nng lng Gibbs, Entanpi t do hay th ng p. b. ngha vt l ca G G = H TS = U +PV TS dG = dU + pdV + VdP- TdS SdT Nguyn l I => dU = Q + W , m dW = pdV + W ' ( W ' : cng hu ch)
=> dG = Q PdV + W '+ VdP + PdV TdS SdT
dG = Q + W '+ VdP TdS SdT
Nguyn l II => Q TdS ; => dG TdS + W '+ VdP TdS SdT
dU TdS PdV + W '
hay: dG W '+ VdP SdT l phng trnh c bn ca nhit ng hc. - Nu qu trnh l thun nghch-->cng l ln nht --> du = dG = W ' max + VdP SdT T v P =const => dT=0 v dP=0 c: dG T , P = Wmax '
G T , P = W ' max
ngha ca G: G biu th cng hu ch ca qu trnh thun nghch ng nhit ng p. 2. Hm th ng nhit ng tch (lm tng t G) a. nh ngha: Xt 1 h T, V =const, h thc hin 1 bin i no H Mi trng
U _Nng lng trao i vi mi trng S _Bin thin entropi ca qu trnh
U mt = U h = U
S = U Mt U = T T
Tiu chun t din bin v gii hn ca qu trnh l:

S h + S mt 0 U 0 T
<=> S
<=> U TS 0 <=> (U TS ) 0 t U - TS = A => A l th ng tch ( nng lng Helmholtz). <=> A 0 b. ngha A A = U TS dA = dU - TdS SdT ; dU = Q + W = Q PdV + W '
Q TdS
=>
dA TdS PdV + W ' TdS SdT
=> dA W ' PdV SdT - Nu qu trnh l thun nghch-->cng l ln nht --> du = dA = W ' max PdV SdT T v V =const => dT=0 v dV=0 c: dA = W ' max
A = W ' max
ngha ca A : Bin thin th ng tch A biu th cng c ch ca qa trnh thun nghch ng nhit ng tch. Tm li tiu chun t din bin v gii hn ca qu trnh l T,P = const => dG 0 T,V = const => dA 0 Mi lin h gia G v A G = H- TS U +PV TS =(U-TS) + PV =A + PV Vy G = A+PV 3.Bin thin th ng p: dG W '+ VdP SdT --> iu kin t din bin v gii hn => Qu trnh t din bin theo chiu lm gim G cho ti khi t gi tr Gmin: dG=0 (G=0) d2G>0 (G>0) a. Th ng p sinh chun ca 1 cht nhit T: L s bin thin th ng p ca phn ng to thnh 1 mol cht t cc n cht bn iu kin chun v nhit T ca phn ng.
0 K hiu: G T , s (J.mol-1 hoc kJ.mol-1) 0 Thng T=298K => G 298, s --> c bng th ng p sinh chun ca cc cht 250C.
dG 0
VD:
0 G 298, s (NH 3 ) =-16,65kJ.mol-1 ng vi qu trnh
3 1 H 2 (k ) + N 2 (k ) NH 3 (k ) 2 2
0 G 298, s ( HCl) =-95,5kJ.mol-1 ng vi qu trnh
1 1 H 2 (k ) + Cl 2 (k ) HCl(k ) 2 2
=> HCl(k) bn hn NH3(k) v nng lng to ra nh hn. T nh ngha => GT0, s (n cht) =0 b. Tnh bin thin th ng p ca phn ng ho hc V G l hm trng thi v l i lng dung nn c: G p = G s (sp) G s (tg ) G p = G 0 s, 298 (sp ) G 0 s ,298(tg )
G thun=- G nghch
Nu iu kin chun v 250C c:
G <0: phn ng xy ra theo chiu thun G =0: qu trnh cn bng
G >0; phn ng xy ra theo chiu nghch
- G T = H T TS T
0 0 0 G 298 = H 298 298.S 298
- GT = GT (cc qu trnh trung gian) IV. CC YU T NH HNG N TH NG P 1. nh hng ca nhit Xt h: ch c bin i thun nghch, khng sinh cng c ch, c P=const.
dG = W '+ VdP SdT , v W ' = 0 (khng sinh cng hu ch) v P=const G = S T P (G ) = S , T P
nn
=>
thay vo biu thc G = H TS ta c:
( G ) G = H + T T P
=> T
( G ) G = H T P
Chia c hai v cho T2 ta c:

(G ) T G T p T
2
H T2
=>
G H = 2 T T p T
Phng trnh Gibbs-Helmholtz
G T = H hoc l T T2 p
Phng trnh Gibbs- Helmholtz cho php xc nh G theo T:

d( G H ) = 2 dT T T
thng xt iu kin chun (p= 1atm) v T=298K:

d( G 0 H 0 0 ) = 2 dT -> ly tch phn t 298-->T v thng thng bit gi tr G 298 v T T
0 H T = f (T )
H T G 0 )= dT C: d ( 2 T 298 298 T
T T 0
==>
T 0 0 0 G T G 298 H T = 2 dT 298 T 298 T
0 H T = f ( T ) = a + bT + .....
=> G 0 = f (T ) 2. nh hng ca p sut: Xt h: bin i thun nghch, khng sinh cng hu ch, T=const. T biu thc: dG = W '+ VdP SdT , W ' = 0 , T= const
G =V P T
nn c
=> dG = Vdp
1 P1
P2
=> G TP 2 G TP1 = Vdp

P1
P2
i vi cht rn v cht lng --> coi V=const khi P bin i ( tr min P ln) nn : G T G T = V( P2 P1 )
P2 P1
G TP 2 = G TP1 + V( P2 P1 )
hay G = V( P2 P1 )
nRT P
i vi cht kh (coi l kh l tng) --> V =

G TP 2 G TP1 = nRT
P1 P2
P dP = nRT ln 2 P P1
Vy: G = nRT ln
P2 P1
hay G T = G T + nRT ln
P2 P1
P2 P1
0 Nu ban u P1=1atm (iu kin chun) th G T = G T

P2
G T = G + nRT ln P
0 T
VD: Nn 0,5 mol kh l tng t P=1atm n P= 2atm 250C. Hi qu trnh nn c t xy ra c khng?

G = nRT ln P2 2 = nRT ln > 0 1 P1
==> qu trnh nn khng t xy ra. 3. nh hng ca thnh phn cc cht. Khi nim th ho Xt h gm i cht: i = 1, n vi s mol tng ng l n1, n2, ...ni. G=G(T, P, n1, n2...ni)
dG = ( G G G ) P , N dT + dP + n T P T , N 1 T ,, P ,, n G G dn1 + dn 2 + ... + n n 1 T ,, P ,, n j 2 i j 1 dn i T , , P ,, n j i
dG = SdT + Vdp + W '
Ch s N ch ra rng n1,n2, n3...ni l khng i, ch s nj#i ch ra rng ch c ni l bin i. t:

G = Gi = i ni T ,, P ,,n j i
Trong : G i th ng p mol ring ca cht i trong h

i Th ho ca cht i
==> W ' = i dn i => i dn i l 1 dng cng hu ch ==> gi l cng ho T : dG = VdP SdT + i dn i * ngha vt l ca i : Th ho ca cht i ( i ) l th ng p mol ring phn ca i trong hn hp
i l tng kh nng sinh cng hu ch ca h khi thm 1 lng v cng nh
cht i vo h trong iu kin P,T v thnh phn (s mol) ca cc cht khc l khng i.
i c tnh cho 1 mol cht.
i:
i l i lng cng nhng dni l i lng dung
dn
i
c th lm tiu chun xt chiu v gii hn trong iu kin T,P khng
dn <0: Qu trnh t din bin + dn =0: Qu trnh cn bng

i i i i
Phn ng xy ra theo chiu gim th ho. * Mt vi tnh cht ca th ho:

i = Gi
--> i ph thuc vo T, P (ging Gi)

G = =V P T P T
Nu h ch gm 1 cht kh th th ho chnh l th ng p ca 1 mol cht: G= . do :
T lm tng t nh hm G, s thu c phng trnh ca T (ging GT):

0 T = T + RT ln P 0 T
P(atm) (i vi 1 mol kh).
: th ho chun ca cht kh nhit T, P=1atm v tnh cho 1 mol.

ni ) ni
Nu h gm 1 hn hp kh c p sut chung l P th p sut ring phn ca kh i trong hn hp l Pi=Ni.P ( vi N i =
i ( T ) = i0( T ) + RT ln Pi = i0( T ) + RT ln(N i P ) i ( T ) = i0( T ) + RT ln P + RT ln N i
=> i ( T ) = i0( T , P ) + RT ln N i i vi phn ng ho hc: aA + bB --> cC + dD

G p = i (sp ) i (tg )
0 G p = i0 (sp ) i0 (tg )
iu kin chun:
Vy trong iu kin ng nhit, ng p:

(sp) < (tg) : phn ng t din bin (t tri qua phi) +Nu (sp) = (tg ) phn ng trng thi cn bng
+ Nu
i i i i
=> th ho cng l tiu chun xt chiu v gii hn ca cc qu trnh (phn ng xy ra theo chiu gim th ho) 4.Mi quan h gia du G v ln H , S v T: T=const --> G T = H T TS T
G < 0
: Qu trnh t xy ra
S > 0 : chiu tng hn lon
<=> H < 0 : chiu tng bn lin kt STT 1 2 3 4 V d: - phn ng: CaCO3(r) <=> CaO(r) + CO (k) - phn ng: SO2(k) + 1/2 O2 (k) --> SO3(k) tc khng ln --> phn ng khng xy ra ngay c ==> iu kin: nhit khng qu thp
0 H p = +178,22kJ
Du H + +
Du S + +
Du G + ? ?
D on chiu Phn ng t xy ra mi nhit Phn ng khng t xy ra mi nhit Phn ng t xy ra nhit thp phn ng t xy ra nhit cao
n = 1 > S > 0 --> phn ng ch xy ra nhit cao

0 H p = 99,12kJ
n = 0,5 > S < 0 --> phn ng xy ra nhit thp, nhng nu thp qu th vn
Ti liu tham kho:

CHNG III: CN BNG HO HC

I.PHN NG THUN NGHCH V PHN NG 1 CHIU
1.Phn ng thun nghch L phn ng xy ra theo hai chiu tri ngc nhau trong cng mt iu kin (c im ca phn ng thun nghch: khng tin hnh n cng m dn n cn bng) V d: N2O4(k) <=> 2NO2(k) Khi ly kh NO2 (hoc N2O4) nghin cu --> lun thu c ng thi c kh N2O4 (hoc NO2) trong bnh ngay nhit thng do tn ti s chuyn ho gia hai kh trn -> gi phn ng trn l phn ng thun nghch. 2.Phn ng 1 chiu: L phn ng ch xy ra theo mt chiu xc nh V d: Phn ng phn hu KClO3(xc tc MnO2) : KClO3 --> KCl + 3/2O2 c im: tin hnh ti cng 3.Trng thi cn bng ho hc Mt phn ng khi t trng thi cn bng th: Xt v mt ng hc: vt=vn -
Xt v mt nhit ng: G p = 0
* Vy trng thi cn bng ho hc: l trng thi ca phn ng thun nghch khi tc phn ng thun bng tc phn ng nghch (hoc khi bin thin th ng p bng khng). * c im ca trng thi cn bng ho hc: - L cn bng ng (phn ng vn xy ra theo 2 chiu ngc nhau nhng vt=vn). -Ti trng thi cn bng thnh phn ca cc cht khng thay i: cht tham gia phn ng mt i bao nhiu theo phn ng thun th li c sinh ra by nhiu theo phn ng nghch). - Trng thi cn bng ch tn ti khi cc iu kin thc hin phn ng (C, t0,p) khng i.
II.PHNG TRNH NG NHIT VANT HOFF. HNG S CN BNG K
1.Thit lp phng trnh ng nhit Vant Hoff Xt phn ng: aA + bB <=> cC + dD T=const v A,B,C,D l cc kh l tng Ta c: G T = i (sp) i (tg ) = (c C + d D ) (a A + b B ) M: i ( T ) = i0( T ,) + RT ln Pi (i vi 1 mol)
0 0 => c C ( T ) = c C ( T ) + cRT ln PC = c C ( T ) + RT ln PCc (cho c mol)
Tng t:
B (T )
= b
0 B (T )
+ RT ln P Bb :
0 d d D ( T ) = d D ( T ) + RT ln PD
a
A(T )
= a
0 A(T )
+ RT ln P Aa
=>
0 0 0 0 d G T = [(c C ( T ) + RT ln PCc ) + (d D ( T ) + RT ln PD )] [(a A ( T ) + RT ln PAa ) + (b B ( T ) + RT ln PBb )]
d PCc .PD G T = [(c (C) + d ( D) (a ( A) + b ( B )] + RT ln a b PA .PB 0 T 0 T 0 T 0 T
bd
d PCc .PD a b G T = G + RT ln PA .PB 0 T
bd
Pi: p sut ring phn ca cc cht kh i= A,B,C,D)

d PCc .PD t a b PA .PB
=P bd
0 => G T = G T + RT ln P
(*)
0 T
d PCc .PD - Ti trng thi cn bng==> G T = 0 => G = RT ln a b PA .PB d PCc .PD t: a b PA .PB
cb
= K p = const T=const (v trng thi cn bng, thnh phn cc cb
cht khng bin i na)

0 ==> G T = RT ln K P
(**) (***)
v GT = RT ln Trong :
P
KP
0 G T , , G T (J)
R=8,314J.K-1mol-1 P (atm) Cc phng trnh (*) (**) v (***) c gi l cc dng khc nhau ca phng trnh ng nhit Vant Hoff 2.Phng trnh hng s cn bng K: a.Hng s cn bng Kp
d PCc .PD Kp = a b PA .PB
cb
Pi: p sut cc kh trng thi CB
KP khng c n v. Kp ch ph thuc vo bn cht phn ng v nhit . i vi 1 phn ng xc nh, T=const --> Kp=const --> gi l hng s cn bng ca phn ng.
b.Cc hng s cn bng khc
c d CC .C D * KC = a b C A .C B
cb
Ci: nng mol/lit cc cht trng thi cn bng
KC ph thuc vo bn cht phn ng v nhit . i vi 1 phn ng xc nh --> KC =f(T): KC ch ph thuc vo nhit ni; s mol kh i trng thi cn bng
* Kn = C D n a .n b A B cb
n c .n d
Kn ph thuc vo bn cht cc cht , T v P chung ca h khi cn bng v tng s mol kh ca h khi cn bng * K N = C D Ni: nng phn mol ca kh i: N i = i N a .N b ni A B cb KN ph thuc vo bn cht cc cht , T v P chung ca h khi cn bng c.Mi quan h gia cc hng s cn bng - Ta c PiV=niRT (V th tch hn hp kh (lt)) => Pi =
KP
n i RT = Ci RT V
N c .N d
thay vo phng trnh Kp ta c

=
c d CC .C D
(CC RT )c (C D RT )d = (C B RT )b (C A RT )a
K P = K c .( RT ) n
C .C
b B
a A
RT [(c + d )(b + a )] = K c .( RT ) n
n = s mol kh sn phm- s mol kh tham gia (da vo phng trnh phn ng)
Vy
(vi R= 0,082 atm.l.mol-1K-1)
-Mt khc ta c:
Pi = N i .P = ni .P --> thay vo Kp ta c: ni
K P = K N .Pcbn
KP
= K n .
P ni
cb
( n i )cb tng s mol kh c mt trong h phn ng khi cn bng. Vy c:

K P = K C ( RT ) n = K N .Pcbn
P = K n . n i
cb
*Nhn xt: - Khi n = 0 (tng s mol kh 2 v phn ng bng nhau) --> Kp=KC=Kn=KN=K=f(T) - i vi 1 phn ng cho th: + Kp,KC ch ph thuc vo nhit + KN ph thuc vo nhit , P chung ca h khi cn bng
+Kn ph thuc vo T,P chung ca h khi cn bng, tng s mol kh ca h khi cn bng. * Ch : - Gi tr hng s cn bng K ca phn ng u phi gn vi 1 phn ng c th no . V d: SO2(k) + 1/2O2(k) <=> SO3(k)
KP = PSO3 PSO2 .PO22
2 PSO3 2 SO2 2 = KP 1
2SO2(k) + O2(k) <=> 2SO3(k)
K' P =
.PO2
1
SO3(k) <=> SO2(k) + 1/2O2(k)
K =
'' P
PSO2 .PO22 PSO3
= K P1
- Nu K c gi tr kh ln --> coi phn ng xy ra hon ton, K nh -> phn ng thun nghch. - Nu phn ng c cht rn hoc cht lng tham gia (v khng tan ln vo cc cht khc) th chng khng c mt trong phng trnh hng s cn bng ( v i ( T ) = i0( T ) trong sut qu trnh phn ng--> khng cn RTlnPi) V d: Fe2O3(r) + 3 CO(k) <=> 2Fe(r) + 3 CO2(k) Kp= Hg(l) + 1/2 O2(k) <=> HgO(r) 3. Cc phng php xc nh hng s cn bng a.Xc nh theo thnh phn cc cht ti thi im cn bng V d: CaCO3(r) <=> CaO(r) + CO2(k) Nung CaCO3 nhit T , khi cn bng: PCO = 740mmHg .Tnh Kp
2
3 PCO2 3 PCO
KP =
1 PO22
1
Gii:
K P = PCO2 = 740 760
b.Xc nh thng qua 1 s i lng nhit ng

0 G T = RT ln K P 0 G T RT
==> K P = exp

0 bit G 298,s (NH3 ) = 16,65kJ.mol 1
V d: Tnh Kp ca phn ng sau 250C: 2NH3(k) <=> N2(k) + 3H2(k) Gii:
0 0 G 298 = 2G 298,s (NH3 ) = (2)(16,65) = +33,3kJ .mol 1
0 G 298 33,3.10 3 6 = exp K P = exp 8,314.298 = 1,45.10 R.298
c. Xc nh theo phng php gin tip: Phn tch qu trnh theo 1 chu trnh kn V d:
Cgr O2(k) K1 CO(k)
0 G 0 = G10 + G 2
KP=?
CO2(k) K2
1/2 O2(k)
RT ln K P = ( RT ln K 1 ) + ( RT ln K 2 )
lnKP=lnK1+lnK2
==> K=K1.K2
III.S CHUYN DCH CN BNG. NGUYN L LE CHATIELIER
1.S chuyn dch cn bng - Xt v mt nhit ng, khi phn ng t trng thi cn bng--> G = 0 -->
P
KP = 1 khi
h ang trng thi cn bng nu ta thay i mt trong cc thng s trng thi (P,T,C) ca h --> G 0 => cn bng b ph v, qu trnh s tin hnh theo chiu G < 0 t ti trng thi cn bng mi ng vi cc thng s mi (P,T,C). - Xt v mt ng hc, khi phn ng t trng thi cn bng --> vt=vn => v=0. Khi h t trng thi cn bng, ta thay i 1 trong cc thng s trng thi (P,C,T) => vt vn ==> qu trnh tin hnh theo chiu v > 0 t trng thi cn bng mi ng vi cc thng s mi. ==> gi l s chuyn dch cn bng. nh ngha: S chuyn dch cn bng l s chuyn t trng thi cn bng ny sang trng thi cn bng khc di nh hng ca cc tc ng bn ngoi (P,T,C) ln h. 2.nh hng ca nhit ti s chuyn dch cn bng. Phng trnh ng p Vant Hoff Xt phn ng: aA + bB <=> cC + dD
0 G T Ta c: ln K P = RT
P=const
Mt khc:
0 GT T
H 0 = 2T T P
do : =>
ln K P T
0 H T = 2 P RT
=> phng trnh ng p Vant Hoff
0 - Nu H T > 0 (phn ng thu nhit) --> hm ng bin
+ Khi nhit tng --> Kp tng --> cn bng chuyn dch theo chiu thun ( chiu thu nhit) + Nu T gim --> Kp gim ==> cn bng chuyn dch theo chiu nghch ( chiu to nhit)
0 - Nu H T < 0 (phn ng to nhit) --> hm nghch bin:
+Khi nhit tng --> Kp gim --> cn bng chuyn dch theo chiu nghch ( chiu thu nhit) +Nu T gim --> Kp gim ==> cn bng chuyn dch theo chiu thun ( chiu to nhit) * Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi: + Khi nhit tng th cn bng chuyn dch theo chiu lm gim nhit ca h l chiu thu nhit c H T > 0 + Khi nhit gim th cn bng chuyn dch theo chiu lm tng nhit ca h l chiu to nhit c H T < 0 * T phng trnh Vant Hoff suy ra:
ln K P =
0 H T
RT 2
.T
0 Nu trong khong nhit T1-->T2 hp -->c th coi H T = const th:

T2
H 0 d ln K P = R T1
K PT
2
T2
T1
dT
2
=> ln
K PT
H 0 1 1 = R T1 T2
vi H 0 (J) v R=8,314 J.K-1mol-1 3. nh hng ca p sut n s chuyn dch cn bng

Ta c: K P = K N .Pcbn
V Kp khng ph thuc vo P--> thay i P th Kp=const nn: - Nu n > 0 : khi tng P--> KN gim ( gi Kp=const) => chuyn dch cn bng theo chiu nghch ( lm gim s mol kh) v ngc li - Nu n < 0 : khi tng P--> KN tng ( gi Kp=const) => chuyn dch cn bng theo chiu thun ( lm gim s mol kh) v ngc li khi P gim --> KN gim --> cn bng dch chuyn theo chiu nghch ( lm tng s mol kh) - Nu n = 0 => P khng nh hng ti s chuyn dch cn bng * Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi:
Nu P tng => cn bng chuyn dch theo chiu P gim (gim s mol kh
n < 0 )
Nu P gim => cn bng chuyn dch theo chiu tng P (tng s mol kh
n > 0 )
4. nh hng ca nng Xt phn ng: aA + bB <=> cC + dD c K C = C D = const T=const C a .C b A B cb

C c .C d
- Nu tng CA, CB => cn bng chuyn dch theo chiu tng CC,CD ( gi KC=const) => cn bng chuyn dch theo chiu thun lm gim CA,CB - Nu gim CA, CB => cn bng chuyn dch theo chiu gim CC,CD ( gi KC=const) => cn bng chuyn dch theo chiu nghch lm tng CA,CB * Nhn xt: Kt qu ca s chuyn dch cn bng l chng li thay i bn ngoi.Nu tng Ci th cn bng chuyn dch theo chiu lm gim Ci v ngc li. 5. Nguyn l chuyn dch cn bng Le Chatelier Khi mt h ang trng thi cn bng, nu ta thay i 1 trong cc thng s trng thi ca h ( T, P hoc C) th cn bng s chuyn dch theo chiu chng li s thay i .
Ti liu tham kho:

Chng IV: Cn bng pha

I. Mt s khi nim 1. Pha ( ) l phn ng th ca h c thnh phn, tnh cht l hc , tnh cht ho hc
ging nhau mi im ca phn ng th v c b mt phn chia vi cc phn khc ca h. - Pha ch gm 1 cht gi l pha nguyn cht (pha n) cn pha gm 2 cht tr ln--> gi l pha phc tp. - H gm 1 pha --> h ng th. - H 2 pha -> h d th. V d: H gm H2O + H2O lng + H2O hi => gm 3 pha: rn, lng, hi. H gm CaCO3(r), CaO(r),CO2(k) --> 3 pha: 2 fa rn + 1 pha kh 2. Cu t: L phn hp thnh ca h c th c tch ra khi h v tn ti c bn ngoi h. S cu t trong h k hiu l R V d: dung dch NaCl gm 2 cu t l NaCl v H2O --> R=2 3.S cu t c lp (K): L s ti thiu cc cu t xc nh thnh phn ca tt c cc pha trong h. - Nu cc cu t khng phn ng vi nhau v nu pha c thnh phn khc nhau th K=R (trong h khng c phng trnh lin h nng cc cu t) V d: dung dch NaCl => R=K=2. -Nu cc cu t tng tc vi nhau v nm cn bngvi nhau--> chng khng cn c lp vi nhau na--> K=R-q q: s h thc lin h gia cc nng ( q c th l phng trnh hng s cn bng, iu kin u v nng ca cc cu t) V d: H gm 3 cu t HCl, Cl2, H2 u l cc cht kh c tng tc,nm cn bng vi nhau: 2HCl(k) <=> H2(k) + Cl2(k)
KC =
[H 2 ][Cl2 ] [HCl]2
=> bit c nng ca 2 cu t s bit c nng
ca cu t cn li. Vy h c: R=3, q=1, ==> K= R-q=2 Nu gi thit ban u h ch c HCl ( hoc cho t l mol H2:Cl2 ban u) => q=2 => K=1 4.Bc t do ca h(C): L s ti thiu cc thng s trng thi cng (P,T,C) xc nh trng thi cn bng ca 1 h ( l s thng s trng thi cng c th thay i 1cch c lp m khng lm bin i s pha ca h) V d: H2O(l) <=> H2O(k) ==> cn bng c 2 pha==> C=1 v + C th thay i 1 trong 2 thng s P hoc T m khng lm thay i s pha ca h.
+ Hoc: mt nhit xc nh th P hi H2O nm cn bng vi H2O lng l xc nh, tc l ch cn bit 1 trong 2 thng s T hoc P th xc nh c trng thi cn bng ca h. 5.Cn bng pha: Cn bng trong cc h d th, cc cu t khng phn ng ho hc vi nhau nhng xy ra cc qu trnh bin i pha ca cc cu t => cn bng pha.
II. Quy tc pha Gibbs.
Xt h gm R cu t 1,2,....R c phn b trong pha ( , , ,..., pha) 1.iu kin cc pha nm cn bng vi nhau: m bo cc cn bng sau: - Cn bng nhit: nhit cc pha bng nhau
T = T = T = ... = T
-Cn bng c: p sut cc pha bng nhau

P = P = P = ... = P
-Cn bng ho: th ho ca mi cu t trong cc pha bng nhau:

i i = = i = ... = i
2.Qui tc pha Gibbs - Cc thng s trng thi cng xc nh trng thi ca h l T,P, C Gi Ni l nng mol phn ca cu t i trong 1 pha th N1+N2+N3+...+Ni=1 => Vy xc nh nng ca R cu t trong 1 pha cn bit nng ca (R-1) cu t. V c pha => xc nh nng ca R cu t trong pha th s nng cn bit l (R-1). T s thng s trng thi cng xc nh trng thi ca h l (R-1)+ 2 trong s 2: biu th 2 thng s bn ngoi l T v P xc nh trng thi ca h V cc pha nm cn bng vi nhau => cc thng s khng c lp vi nhau na: c lin h vi nng m khi cn bng th ca mi cu t trong cc pha phi bng nhau ( iu kin cn bng ho)
1 ( ) = 1 ( ) = ... = 1 ( ) 2 ( ) = 2 ( ) = ... = 2 ( ) R ( ) = R ( ) = ... = R ( )
=> Mi cu t c ( -1) phng trnh lin h ==> R cu t c c R( -1) phng trnh lin h gia cc thng s. Nu c thm q phng trnh lin h nng cc cu t, v d: khi c phn ng ho hc gia cc cu t th s phng trnh lin h cc thng s trng thi cng ca h l: R( -1) + q
Bc t do ca h = Cc thng s trng thi s phng trnh lin h gia cc thng s C= [ (R-1)+2]-[R( -1)+q] C=R-q- +2 C= K - q + 2 => Biu thc ton hc ca quy tc pha Gibbs * Nhn xt: + Khi K tng, => C tng, tng v C gim. + Bc t do C 0 K + 2 +Nu trong iu kin ng nhit hoc ng p th: C =K - + 1 (Nu phng trnh c n = 0 => P khng nh hng ti phn ng --> dng phng trnh ny) +Nu h va ng nhit va ng p th C=K- V d1: Xt h 1 cu t (R=K=1), v d nc nguyn cht - Nu trng thi hi => =1 => C= K- +2= 1-1+2=2 => trng thi ca hi nc c xc nh bi 2 thng s trng thi cng l T v P - Nu hi nc nm cn bng vi nc lng th =2=> C=1-2+2=1 => trng thi ca h gm H2O lng v hi c xc nh bi 1 trong 2 thng s l T hoc P ( v 1nhit xc nh th P ca hi nc l xc nh) V d2: Xt h gm: Mg(OH)2 (r) <=> MgO (r) + H2O(k) =2 pha rn + 1 pha kh =3 pha C=R-q+2=3-1-3+2=1 => c php thay i 1 trong 2 thng s l T hoc P m khng lm thay i s pha ca h hoc trng thi cn bng c xc nh bng 1 trong 2 thng s T hoc PH O(h )
2
III.Cn bng pha trong h 1 cu t 1.Cn bng pha trong h 1 cu t Xt h gm 1 cht nguyn cht, khi trong h c 2 pha nm cn bng nhau: Rn(R) <=> Lng(L) Lng(L)<=>Hi (H) Rn (R)<=>Hi (H) ( R ( ) R ( ) ) => v h 1 cu t, s pha 3 (3 K + 2 ) => C= K- +2 =1-2+2 =1 (R=K-1) trng thi cn bng gia hai pha c c trng bi hoc T hoc P, tc l nu 1 trong 2 thng s trng thi l P hoc T bin i th thng s kia phi bin i theo: p=f(T) hoc T=f(P). C th l : - P=const=> cht nguyn cht nng chy, si hoc chuyn trng thi tinh th 1 nhit nht nh, c gi l nhit chuyn phaTcf, nhit ny khng b bin i trong sut qu trnh chuyn pha. Khi p sut thay i => Tcf thay i theo. Vd: P=1atm, nc nguyn cht ng c 00C v si 1000C P=2atm, nc nguyn cht ng c 0,00760C v si 1200C
- T=const, hi nm cn bng vi lng v rn c P nht nh gi l P hi bo ho (hi c goi l hi bo ho) Cc ng cong biu th s ph thuc ca Phi bo ho ca pha rn vo nhit , ca pha lng vo nhit v nhit nng chy vo P ct nhau ti 1 im gi l im ba, im ba ny ba pha rn lng hi (R, L, H) nm cn bng vi nhau:
R L
Khi C=1-3+2 =0 => v tr im ba khng ph thuc vo T v P m ch ph thuc vo bn cht cht nghin cu. 2. nh hng ca p sut n nhit nng chy, si v chuyn dng tinh th ca cht nguyn cht V h 1 cu t nn th ha ng nht vi th ng p mol (Gi= i ). Khi T, P khng i iu kin cn bng gia hai pha v l:
G ( ) = G ( )
V h c C=1 nn nu mt thng s bin i, v d, p sut bin i mt lng dP th mun hai pha tn ti cn bng, nhit cng phi bin i mt lng dT. Khi th ng p mol phi bin i:
G ( ) > G ( ) + dG ( ) G ( ) > G ( ) + dG ( )
Sao cho: G ( ) + dG ( ) = G ( ) + dG ( ) => dG ( ) = dG ( ) Thay vo cng thc: dG= VdP SdT ta c:
V ( ) dP S ( ) dT = V ( ) dP S ( ) dT
dT V ( ) V ( ) V => = = S dP S ( ) S () H C S = suy ra: T dT Tcf V = phng trnh Clapeyron dP H cf

Trong H c tnh bng J th V tnh bng m3, T bng K v P bng Pa. - Khi mt cht si th V =Vh- Vl >0 v H hh>0 (hh:ha hi), nn p sut bn ngoi tng th nhit si tng theo. - Khi nng chy H nc >0 v a s trng hp V = Vl-Vr >0, do P tng th nhit nng chy tng. i vi nc Vl<Vr nn V <0 ngha l p sut tng th nhit nng chy ca nc gim.
3. nh hng ca nhit n p sut hi bo ho ca cht nguyn cht Xt cc trng hp: L <=> H R <=> H V Vr,Vl << Vh => V = Vh Vl Vh v V = Vh Vr Vh Nu hi c coi l kh l tng,xt i vi 1 mol c:
Vh = RT thay vo phng trnh Clayperon c: P
H cf H cf dP H cf = = = 2 .P dT Tcf .V Tcf .V Tcf .R
=>
dP H = dT P RT 2
(v
dP = d ln P ) nn c: P
d ln P H = dT RT 2
-> phng trnhClaypeyron-Clausius
Trong khong nhit hp -> c th coi H = const khi c

ln P2 H 1 1 = P1 R T1 T2
(*)
P1,P2 : cng n v R=8,314J.K-1.mol-1 H : J
Biu thc (*) cho bit c th: - Tnh p sut hi bo ho nhit T2(hoc T1) khi bit P nhit T1 v H cf - Tnh nhit si P bt k khi bit nhit si mt p sut no v H bay hi. Tnh H bng cch o P1 v P2 2 nhit khc nhau.
Ti liu tham kho:

Chng V Dung dch

I.H phn tn
1.nh ngha: L h gm 2 hay nhiu cht trong cht ny c phn b trong cht kia di dng nhng ht rt nh. - Cht phn b c gi l cht phn tn, cht kia l mi trng phn tn. Cht phn tn v mi trng phn tn c th 1 trong 3 trng thi: rn, lng hay hi. Vd: ng tan trong nc => ng l cht phn tn, H2O l mi trng phn tn - Da vo kch thc ca ht phn tn, chia lm 3 h phn tn: a.H phn tn th: Kch thc ht t 10-7-10-4m -c im: Khngbn,cht phn tn d tch ra khi mi trng phn tn. -C 2 dng: + Huyn ph: cht phn tn l rn, pha phn tn l lng. v d: nc ph sa + Nh tng: cht phn tn l lng, mi trng phn tn cng l lng v d: sa c ln nhng ht m l lng b.Dung dch keo: (H keo): Kch thc ht t 10-7 10-9m - c im: tng i bn c. Dung dch thc (dung dch): Kch thc ht 10-10m (bng kch thc phn t hoc ion), trong cht phn tn v mi trng phn tn c phn b vo nhau di dng phn t hoc ion, gia chng khng cn b mt phn chia, to thnh 1 khi ng th gi l dung dch thc Cht phn tn c gi l cht tan, mi trng phn tn c gi l dung mi -c im: H ny rt bn 2.Cc loi nng -Nng % (C%): l t l % khi lng cht tan so vi khi lng dung dch (C%chnh l lng cht tan c trong 100g(100kg) dung dch)
C% = a .100 % a+b
a,b lng cht tan v lng dung mi, tnh bng g (kg)
-Nng mol/lit (CM): l s mol cht tan c trong 1 lit dung dch -Nng ng lng (CN):S mol ng lng cht tan c trong 1 lt dung dch -Nng molan ( ) l s mol cht tan c trong 1000gam dung mi -Nng phn mol: N i =
II. ng lng ()
ni ni
Trong cc phn ng ho hc, cc cht tc dng va vi nhau theo nhng s phn khi lng tng ng gi l ng lng. Chn ng lng ca H lm n v H=1 1.nh ngha nglng - ng lng ca mt cht hoc ca 1 nguyn t l phn khi lng ca cht hoc nguyn t tc dng va vi 1 ng lng ca H. V khng phi mi cht u phn ng vi H => nh ngha c m rng nh sau:
ng lng ca 1 nguyn t hay 1 hp cht l s phn khi lng ca n tc dng va vi 1 ng lng ca 1 cht bt k V d: Cl2 + H2 = 2HCl Cl2 + Zn =ZnCl2 => 71 phn khi lng ca Cl2 tc dng vi 2 phn khi lng ca H Vy kt hp vi 1 ng lng ca H ch cn 1 khi lng ca Cl2 bng khi lng nguyn t ca n => Cl=35,5, Zn= 32,5 -Mol ng lng ca mt cht: l khi lng tnh ra g c gi tr ng bng ng lng V d: O=8g 2.Cch tnh ng lng a.ng lng ca nguyn t
= A n
A: khi lng nguyn t nguyn t n: ho tr nguyn t
Vi nguyn t c nhiu ho tr khc nhau s c nhiu ng lng v ng lng ca chng gn vi 1 phn ng c th m chng tham gia. b.ng lng ca hp cht
= M n
M: khi lng phn n: tu tng trng hp
Cch xc nh n - i vi phn ng oxi ho kh: n l s e trao i ng vi 1 phn t cht (n l s e m 1 phn t trao i trong phn ng) - i vi phn ng trao i: n l s in tch (+) hoc (-) m 1 phn t cht trao i trong phn ng = NaHSO4 + H2O (1) V d: H2SO4 + NaOH
H 2 SO4 (1) =
NaOH (1) =
M H 2 SO4 1
M NaOH 1
98 = 98 1 40 = = 40 1 =
H2SO4 + 2NaOH
H 2 SO4 ( 2 ) =
NaOH ( 2 ) =
Na2SO4
+ H2O
(2)
M H 2 SO4 2
M NaOH 1
98 = 49 2 40 = = 40 1 =
i vi trng hp tnh ng lng ca mt cht khng c phn ng c th th:

= M n
+ i vi axit: n l s H axit trong phn t + i vi baz: n l s nhm OH- baz trong phn t
+ i vi mui: n l s in tch (+) hoc in tch (-) m cc ion mang trong 1 phn t. V d: Na SO =
2 4
M Na2 SO4 2
Al2 ( SO4 )3 =
M Al2 ( SO4 )3 6
CN n
+Mi quan h gia CM v CN:
CM=
3.nh lut ng lng Cc cht tc dng va vi nhau theo cc khi lng t l vi ng lng ca chng. => =>
mA A = mB B
mA l khi lng cht A tc dng va vi khi lng mB cht B
mA mB => n ng lng cht A phn ng va vi n ng lng cht B ( S = A B
ng lng cht A bng s ng lng cht B) => Nu c VA(l) cht A nng mol ng lng l C N phn ng va vi VB(l) cht
A
B nng mol ng lng l C N th

B
VA. C N =VB. C N
A
-> ng dng nhiu trong chun th tch
V d: trung ho 25ml NaOH cn 28ml dung dch axit 0,1N => tnh lng NaOH c trong 1l dung dch ? Gii Gi x l nng ng lng mol ca NaOH => x.25=0,1.28 =>x=28.0,1/25 NaOH=40=> s g NaOH c trong 1 lt dung dch l m=40.x=40.28.0,1/25=4,48g III. ho tan 1.Qu trnh ho tan. Nhit ho tan ca mt cht Qu trnh ho tan (khng phi l qu trnh trn ln) gm qu trnh + Qu trnh phn tn cht tan( di dng nguyn t, phn t,ion) vo trong khp th tch dung mi. +Qu trnh tng tc gia cc phn t ca dung mi vi cc phn t ca cht tan => to thnh dung dch (hp cht ho hc) Hp cht ho hc to thnh gi l hp cht sonvat, nu dung mi l nc th gi l hp cht hydrat. => Qu trnh ho tan c s ph v lin kt cng loi to lin kt khc loi v c th biu din bng s : H ht
T_T + dm T_dm
H pt > 0
T+T + dm
H sv < 0
Trong :
T cht tan
dm dung mi H pt nng lng phn tn ( cn tiu tn -> H pt > 0 )

H sv nng lng qu trnh sovat (Qu trnh l to nhit --> H sv < 0 )
(Nu dung mi l nc -> H sv = H h nhit hidrat ho)

H ht nhit ho tan
Theo s trn ta c:
H ht = H pt + H sv
(do H sv < 0 , H pt > 0 --> H ht c th m hoc dng)
+Nu H pt > H sv H ht > 0 : qu trnh ho tan thu nhit, l qu trnh ho tan ca a s cht rn vo trong nc. +Nu H pt < H sv H ht < 0 :qu trnh ho tan to nhit, l qu trnh ho tan ca a s cht kh vo trong nc. +Nu H pt = H sv H ht = 0 : Trn ln l tng ( i vi dung dch l tng) - nh ngha nhit ho tan ca mt cht: L lng nhit to ra hay thu vo khi ho tan 1 mol cht vo 1 lng dung mi ln nhit v P xc nh. Vd: Khi ho tan 1 mol CaCl2 vo H2O thot ra 1 nhit lng l 72,802 kJ, vy
H ht (CaCl 2 ) = 72,802kJ .mol 1
ha tan: Qu trnh ha tan: cht tan + dm <-> dung dch l mt qu trnh thun nghch, khi t cn bng cht tan khng tan thm na to thnh dung dch bo ha. - ha tan ca mt cht c tnh bng nng ca dung dch bo ha cht iu kin cho v k hiu l s. - S c th biu din bng mi cch biu din nng . - ha tan s ca mt cht ph thuc vo: + Bn cht ca dung mi v cht tan. + Nhit + p sut: (nu cht tan l cht kh). a. nh hng ca bn cht cht tan v dung mi n s - Cc cht c cu to phn t tng t nhau d ha tan vo nhau, phn t dung mi phn cc ln th ha tan tt cc cht phn cc v ngc li. ch ha tan cc cht m fn t phn - VD: Dung mi l H2O l phn t phn cc cc hoc hp cht ion nh HCl, NaCl.. H2O t ha tan I2 v I2 khng phn cc Benzen khng phn cc benzen thc t khng tan trong H2O. I2 tan tt trong benzen c mu tm. C th ng dng tnh cht ny trong tch, chit hu c. b. nh hng ca nhit ti tan CT + Dm <=> Dd , H ht Nu H ht >0 (ha tan a s cc cht rn):
+ Khi nhit tng -> cn bng chuyn dch theo chiu thun tan tng. + Khi nhit gim -> cn bng chuyn dch theo chiu nghch tan gim. Trong mt s trng hp c th iu ch dung dch qu bo ha c nng ln hn ha tan s nhit T dung dch qu bo ha khng bn. - Nu H ht <0 (ha tan a s cht kh) + Khi nhit tng -> cn bng chuyn dch theo chiu nghch tan gim. + Khi nhit gim -> cn bng chuyn dch theo chiu thun tan tng. c. nh hng ca P (i vi cht kh). nh lut Henry CT(kh) + dm <=> dd (*) qu trnh ha tan cht kh lm gim n nn: + Khi P tng => ha tan s tng +Khi P gim => ha tan s gim T cn bng (*) thy rng: S tng P s dn n s chuyn dch cn bng sang phi. Nu tng P ln n ln th ha tan ca cht kh cng tng ln n ln. nh lut Henry: mt nhit khng i, khi lng cht kh ha tan trong 1 th tch cht lng xc nh t l thun vi P ca n trn b mt cht lng. m= k.P trong : k- h s t l ph thuc vo bn cht ca cht kh, dung mi v nhit -> gi l h s Henry. P p sut ring phn ca cht kh trn mt cht lng. Nu trn mt cht lng c 1 hn hp kh th s ca mi kh t l vi P ring phn ca tng kh. nh lut Henry ch ng cho cht kh c s nh, P khng ln v kh khng tc dng ha hc vi dung mi. IV. Tnh cht ca dung dch. - Ch xt dung dch: + long + cht tan khng bay hi + cht tan khng to dung dch rn vi dung mi. VD: dd mui hoc dd ng khi un ch c H2O bay hi. Dung dch l tng: l dung dch m ca n tun theo nh lut tng t nh i vi kh l tng. Cc dung dch rt long c coi nh dung dch l tng. ca cu t i trong dung dch l tng c tnh theo cng thc ging nh i vi kh l tng: i ( T ) = i0 + RT ln Ni .
( T ,P)
Tuy nhin v P nh hng rt t n tnh cht ca cht lng nn y i0 v hu nh ch ph thuc vo T. dung dch xt y l (rt) long-> coi l dung dch l tng. 1. p sut hi bo ha ca dung dch. nh lut Raun I.
Kho st h 2 cu t: dung mi ch cha 1 cht tan ( cc kt lun rt ra cng ng cho h nhiu cu t). K hiu: 2 l cht tan, 1 l dung mi 10 : th ha ca dung mi nguyncht.
i
: th ha ca dung mi trong dung dch.
1 = 10 + RT ln N1
V N1<1 => khi c mt cht tan , ca dungdch s gim i 1 lng l (RTlnNi). a. p sut hi bo ha ca dung mi nguyn cht ( P10 ) L H(dm) ( vi cht lng L l dung mi nguyn cht) Hi nm cn bng vi lng gi l hi bo ha, hi bo ha gy P hi bo ha C=12+2=1: p sut hi bo ha ca dung mi nguyn cht ch ph thuc vo nhit . cng 1 nhit , cht no cng d bay hi th P hi bo ha cng ln Qu trnh bay hi l qu trnh c H > 0 => khi nhit tng th Phi bo ha cng tng. b. p sut hi bo ha ca dung dch ( P1 ) Ch xt dung dch cha 1cht tan v 1 dung mi: dd (L) <=> H C=2-2+2 =2 Phi bo ha ca dung dch ph thuc vo c T v C. iu kin cn bng pha (ca cht lng v hi ca n) t0C, P xc nh l: ih = il m ih = i0 h + RT ln Pi (tnh cho 1 mol).
il = i0 l + RT ln N i ih = il => 0= ioh i0 l + RT ln
R ln
Pi Ni
0 l i0 h Pi = i = const Ni RT
Pi = k i = const Ni
t0C xc nh. => Pi= ki.Ni
Ngha l
Khi Ni =1 (cht nguyn cht) th ki= Pi0 l p sut hi ca cu t i nguyn cht. T c: Pi= Pi0.Ni Kt lun: - Khi Ni<1 (thm cht tan vo dung dch) => Pi < Pi0: dung dch cha cht tan khng bay hi th Pp sut hi bo ha ca dung dch lun nh hn Pp sut hi bo ha ca dung mi nguyn cht cng nhit . Nu nng dung dch cng ln => Pp sut hi bo ha ca dung dch cng nh. c. nh lut Rault I Gi N1 l nng phn mol ca dung dch P1 v P1,0 ln lt l Pp sut hi bo ha ca dung dch v dung mi nguyn cht cng mt t0C. Th: P1 =N1.P1,0
V N1= 1-N2 =>

P1,0 P1 P1,0 = n2 P P = N 2 => = N2 = P1,0 P1,0 n1 + n 2
P l gim p sut hi bo ho tng i ca dung dch P1,0
Trong : P : gim p sut hi bo ho ca dung dch so vi dung mi.
n2: s mol cht ho tan n1: s mol dung mi. Nu dung dch long(N1-> 1)=> n1>>n2 th:
P n 2 = => Biu thc ca nh lut Rault I P1,0 n1
Pht biu: gim tng i ca dung dch cha cht ho tan khng bay hi t l vi s mol cht tan c trong 1 lng dung mi xc nh. 2. Nhit si v nhit ng c ca dung dch. nh lut Rault II a.Nhit si ca dung dch * Nhit si ca cht lng: L nhit p sut hi bo ha ca cht lng bng p sut bn ngoi. Xt cn bng L H C=2+2-2 =2 Vy nhit si ca dung dch ngoi s ph thuc vo p sut bn ngai cn ph thuc vo nng cht ha tan. - p sut bn ngoi nh nhau, khi dung mi nguyn cht si th dung dch cha cht tan khng bay hi s cha si v p sut hi bo ha ca dung dch lun lun nh hn p sut hi bo ha ca dung mi nguyn cht cng 1 nhit . Vy dung dch cha cht tan khng bay hi c nhit si cao hn dung mi nguyn cht. - tng nhit si ca dung dch so vi dung mi nguyn cht t s c tnh theo cng thc Rault 2:
t s = k s = k s m M
trong t s =ts,dd-ts,dm (ts,dd: nhit si dung dch, ts,dm: nhit si dung mi nguyn cht, nng molan; ks: hng s nghim si (ch ph thuc vo bn cht dung mi). - Khi dung dch si th hi bay ra l ca dung mi nn nng dung dch tng dn, do nhit si ca dung dch tng dn, nhng khi t n dung dch bo ha th hi dung mi bay ra lm cho cht ha tan kt tinh li, lc ny nng dung dch khng thay i v nhit si ca dung dch khng bin i na. Vn dng quy tc pha ta c: C=2-3+2 =1. Ngha l khi xut hin tinh th cht tan th nhit si ca dung dch ch cn ph thuc vo p sut bn ngoi. b. Nhit ng c ca dung dch cha cht tan khng bay hi Nhit ng c ca cht lng l nhit c cn bng sau: R
i vi dung dch ta c: C=2+2-2 =2 Vy ng c ca dung dch ngoi s ph thuc vo p sut bn ngai cn ph thuc vo nng cht ha tan. Nhit ng c ca dung dch cha cht tan khng bay hi lun thp hn dung mi nguyn cht. V tun theo nh lut Rault 2:
t d = k d = k d m M
trong t s =ts,dd-ts,dm ,ks: hng s nghim ng (ch ph thuc vo bn cht dung mi). 3. S thm thu v p sut thm thu: a. S thm thu L s khuch tn mt chiu ca cc phn t dung mi qua mng bn thm (mng bn thm l mng ch cho cc phn t dung mi i qua m khng cho cc phn t cht ha tan lt qua). Hin tng ny thy rt r khi hai bn ca mng bn thm cha dung dch c nng khc nhau hoc 1 bn l dung dch cn bn kia l dung mi nguyn cht; khi cc phn t dung mi s khuch tn t dung dch long hoc t dung mi nguyn cht sang pha bn kia nhiu hn s khuch tn theo qu trnh ngc li, do lm tng th tch ca dung dch pha bn kia. b. p sut thm thu Hin tng thm thu lm cho mc dung dch mt pha ca mng bn thm dng ln cao. Chiu cao ca ct dung dch ny to nn mt p sut lm cho hin tng thm thu ngng li. p sut c to ra bi ct dung dch ny c trng nh lng cho s thm thu v c gi l p sut thm thu P. N c tnh theo cng thc: PV=nRT=
m RT M
Trong : V l th tch ca dung dch

n= m : s mol cht ha tan. M
R: Hng s kh l tng.
Chng IX: Dung dch cht in ly

I.Tnh cht ca dung dch in li 1.Cht in ly L cht khi ha tan trong nc, cc phn t ca n phn ly nhiu hay t thnh cc ion. Nguyn nhn c bn ca s phn li phn t thnh ion l do tng tc gia cc cht in li v cc phn t dung mi to thnh cc ion b hidrat ha. V d: NaCl + mH2O = Na+.nH2O + Cl-(m-n)H2O. Cc gi tr m, n thng khng xc nh c v ph thuc vo nng v nhit nn thng c vit: NaCl + aq = Na+.aq + Cl-.aq aq: Lng nc khng xc nh 2. Cht in li mnh: L cht khi tan trong nc, tt c cc phn t ca n phn ly thnh ion. V d: cht in ly mnh bao gm: + cc mui trung tnh: NaCl, NaBr, Na2SO4, NaNO3,...; + Cc axit mnh: HCl, HBr, HI, HNO3, H2SO4, HClO4; + Cc baz mnh: NaOH, KOH,... ch s in li mnh, trong phng trnh in li c ghi bng du V d: NaCl + aq Na+.aq + Cl-.aq Ngi ta thng vit phng trnh ny mt cch n gin nh sau: NaCl Na+ + Cl3. Cht in li yu: cc axit hu c HCOOH, CH3COOH, mt s axit v c: H2S, H2CO3, H2SO3, HClO, HClO2, HClO3, H2SiO3, HF..., cc baz yu v baz t tan: NH3, Mg(OH)2, Fe(OH)3, cc mui t tan: HgCl2, Hg(CN)2, CdCl2,... L cht khi ho tan ch c mt phn cc phn t b phn ly thnh ion, trong dung dch cht in ly yu tn ti cn bng ng gia cc cc ion v cc phn t khng b phn ly. biu th s in ly khng hon ton, trong phng trnh in ly ca cht in ly yu dng du V d: Trong dung dch axit acetic tn ti cn bng CH3COOH H+ + CH3COO4. Tnh cht bt thng ca dung dch cht in li so vi dung dch cht khng in li Dung dch cht in li dn in tt, l do trong dung dch c cc phn t mang in l ion.
Dung dch cht in li c gim p sut hi P' , tng nhit si t ''s , gim nhit ng c t' d v p sut thm thu P u ln hn so vi dung dch cht khng in li cng nng :
P' t ' P' = = = i >1 P t P
Tnh cht bt thng ny do cc phn t cht in li phn li thnh cc ion lm s phn t trong dung dch tng ln. Cc tnh cht trn ca dung dch ph thuc vo nng cc phn t ny. T c th tnh i bng cch sau:
i = --------------------------------------
S phn t c trong dung dch
S phn t ho tan S phn t trong dung dch bng s ion c to thnh cng vi s phn t cha b phn li thnh ion.
II. in ly
nh gi mc in ly ca tng cht a ra khi nim in ly . 1.nh ngha: S phn t b phn ly = -------------------------------- (0 < 1) Tng s phn t b ho tan - i vi cht in ly yu: <1. - i vi cht in ly mnh: theo l thuyt => =1 nhng trong thc t o c bng thc nghim lun <1 (ch dung dch rt long mi c =1). Gi tr o c bng thc nghim lun <1 c gi l in ly biu kin. * Gii thch: - i vi cht in ly yu => s ion c mt trong dung dch t => khong cch gia cc ion ln => b qua lc tng tc tnh in gia cc ion. - i vi cht in ly mnh: + Trong dung dch long -> khong cch gia cc ion ln => b qua tng tc tnh in gia cc ion. + Trong dung dch c -> s ion c mt trong dung dch nhiu => khong cch gia cc ion nh =>Khng b qua tng tc tnh in gia cc ion, cc ion ht hoc y nhau dn n hin tng bao quanh 1 ion c th c nhiu ion tri du to kh quyn ion => c hin tng nh 1 s phn t khng in ly. 2.Cch xc nh Gi N l s phn t ho tan, q l s ion m 1 phn t phn ly ra. S phn t b phn ly l N, do s ion to thnh l .N.q S phn t cn li khng phn ly l N - .N S phn t c trong dung dch l N= S ion + s fn t khng phn ly = q N + (N -N)
q. .N + N - .N q. - + 1 => i = -------------------------- = ----------------N 1 i 1 = q 1 Da vo cng thc ny ta c th tnh c I c th xc nh bng thc nghim t vic o gim nhit ng c hoc gim Phi bo ha hoc t t s
' ' t s' t d P i= = = t s t d P
nhng i o c t vic o t s hoc P cho kt qa km chnh xc so vi vic o t d ' nn thng xc nh i t vic o t d ' : i =
' t d . Bit i tnh c v ngc li. t d
V d: Mt dung dch cha 8g NaOH ho tan trong 1000g nc ng c -0,677oC. Hy xc nh . Gii: V q= 2 t i = ----t = t(dm) - t(dd) = 0- (-0,677) = 0,677oC t t = k.C = 1,86.
8 = 0,372 = 40
1,821 = 0,82 hay 82%. 2 1
III. Cn bng trong dung dch cht in ly yu
1. Hng s in ly Trong dung dch cht in ly yu AB tn ti cn bng sau: AB A+ + B-
[A ][B ] . Hng s in ly ca phn ng K =

+
[AB]
K ph thuc vo bn cht ca cht AB v nhit . i vi mi cht nht nh T= const th K l hng s. K c trng cho kh nng in ly ca cht in ly yu, K cng ln th kh nng in ly ca cht in ly cng mnh v ngc li. 2. Mi lin h gia K v . nh lut pha long Ostwald AB A+ + BBan u: C 0 0 Cn bng C- C C C
K=
(C)2
C C
K=
2 .C 1
Cng thc ton hc ca nh lut pha long
Ostwald T cng thc ny nhn thy rng C cng nh th cng ln, c ngha l dung dch cng long th in ly cng ln. Khi long 1/C th i vi cht in ly yu nng v cng long th c th coi qu trnh in ly l hon ton. C th xc nh c cc C khc nhau nu bit K v ngc li
1/C
Nu < 0,05 th 1- 1 2.C = K =
K C
3. Dch chuyn cn bng trong dung dch cht in ly yu - S in ly ca cht in ly yu l phn ng thun nghch => cn bng trong dung dch cht in ly yu cng tun theo mi qui lut ca cn bng ho hc. VD: xt cn bng trong dung dch CH3COOH CH3COO- + H+ CH3COOH Nu tng thm nng ca ion axetat bng cch thm mt vi tinh th mui axetat natri th theo nguyn l dch chuyn cn bng cn bng s dch chuyn t phi sang tri, sao cho nng ca ion axetat gim i, ngha l lm gim in ly ca axit. * Kt lun: Khi tng nng ca ion ng loi vi ion ca cht in ly th in ly ca cht in ly yu gim i.
IV. Thuyt axit- baz ca Bronsted
1.nh ngha axit-baz Axit l tiu phn (ion hay phn t) c kh nng cho H+ (proton). Baz l cht c kh nng nhn H+. V d 1: Trong dung dch HCl HCl + H2O = Cl- + H3O+ (1) axit1 baz2 baz1 axit2 ax1 - bz1: HCl/Cl
ax2 - bz2: H3O+/H2O l 2 cp axit baz lin hp V d 2: Trong dung dch NH3 NH3+ H2O NH4+ + OHbz1 ax2 ax1 bz2 ax1- bz1- NH4+/NH3 ax2- bz2- H2O/OHNhn xt: - nh ngha axit baz ch c tnh cht tng i: H2O (1) l 1 baz nhng (2) th H2O li l 1 axit. - mnh ca 1 cp axit baz ngoi s ph thuc vo bn cht ca cp cn ph thuc vo mnh ca cp cng tn ti vi n trong dung dch. - i vi mt cp axit baz lin hp nu axit cng mnh th baz lin hp ca n cng yu v ngc li. 2. Tch s ion ca nc - ch s hydro (pH) Nc l cht in ly rt yu, va c tnh axit v va c tnh baz: H2O + H2O OH- + H3O+ => K C =
[H O ][OH ]
+
3
[H 2 O]
V H2O l cht in ly rt yu => [H2O]cb C H O ban u. => K C [H 2 O] = [H 3 O ][OH

+
2
] = const= K = Tch s ion ca H O. => Trong nc nguyn cht : [H O ] = [OH ] = K
H2O
H2O
Trong nc nguyn cht(mi trng trung tnh) : [H 3 O + ] = [OH ] = K H O

2
K H2O
ch ph thuc vo nhit : K H O =10-14 250C.

2
Vy: - Mi trng trung tnh l mi trng trong [H 3 O + ] = [OH ] v 250C
250C [H 3 O + ] = [OH ] = K H O = 10 14 = 10 7 (mol / l)

2
[H O ] = 10
+ 3
Mi trng baz l mi trng trong [H 3 O + ] < [OH ] v 250C [H 3 O + ] < 10 7 M.
Mi trng axit l mi trng trong [H 3 O + ] > [OH ] v 250C [H 3 O + ] > 10 7 M.
M.
3. Hng s in ly axit-baz a. Hng s in ly ca axit Ka Trong dung dch ca axit yu HA tn ti cn bng ng sau: HA + H2O A- + H3O+
Ka
[H O ][A ] =const T= const . =

+ 3
[HA]
Ka l hng s in ly ca axit trong nc, c trng cho mnh ca axit. Ka cng cao th axit cng mnh. Ka ph thuc vo bn cht ca axit v ph thuc vo nhit . - Axit mnh : khng dng Ka v coi 1 . - Axit yu ( 0 < < 1 ) c hng s cn bng Ka. b. Hng s in ly ca baz Kb Trong dung dch ca baz yu B tn ti cn bng ng sau B + H2O BH+ + OH-
[BH ][OH ] . K =
+ b
[B]
Kb l hng s in ly ca baz B, ph thuc vo bn cht ca baz v nhit . T= const th Kb = const. 4.Mi lin h gia Ka Kb ca 1 cp axit-baz lin hp Xt mt cp A/B lin hp. Khi ho tan trong nc xy ra qu trnh in ly nh sau: B + H3O+ Ka A + H2O Kb B + H2O A + OH
[B].[H 3O + ] Ka = [A]
[B].[H3O+ ]. [A].[OH ] = [H O+ ][OH ] = K =1014 . Ka .Kb = 25 C 3 HO [A] [B]

o
2
3
[A].[OH ] Kb = [B]
Vy i vi 1 cp A-B lin hp th Ka.Kb = [H3O+][OH-] = KH2O = 10-14 Trong 1 cp axit - baz lin hp nu axit cng mnh th baz cng yu v ngc li. VD: K a ( CH COOH ) = 1,75.10 5
K b ( CH COO ) = 10 14 / 1,75.10 5 = 5,71.10 10 > K b ( H2O)
3
CH3COO trong nc th hin tnh baz (yu): CH3COOH + OHCH3COO- + H2O 5. Ch s hydro - pH pH = -lg[H3O+] - Mi trng trung tnh [H 3 O + ] = 10 7 M => pH= 7 250C - Mi trng axit c - Mi trng baz
[H O ] > 10 [H O ] < 10
+ 3 + 3
M => pH <7 250C M => pH >7 250C
Cch xc nh pH: + Xc nh bng my o pH. + S dng giy o pH. - Cht ch th mu: L cht thay i mu theo gi tr pH. Thng gp cc ch th mu trong phng th nghim. +Qu tm. +Metyl da cam: ch th mi trng axit yu. +Phenol phatalein: ch th mi trng kim.
Khong chuyn mu: l khong pH trong mu ca ch th bin i c. i vi ch th mu c 1 khong chuyn mu xc nh. VD: phenolphtalein: + pH =0 8: khng mu. + pH =8-10 : hng +pH =10-14 thm Metyl da cam: + pH =0 3: hng + pH =3-4,4 : da cam + pH =4,4-14 vng.
V. Tnh pH ca cc dung dch axit- baz- mui
1. Tnh pH ca dung dch axit mnh 1 bc Xt dung dch axit mnh HA, nng Ca, trong dung dch tn ti cc cn bng: HA + H2O A- + H3O+ (1) + H3O + OH (2) 2H2O + Trong dung dch tn ti cc ion H3O , OH , A . Phng trnh bo ton in tch: [H 3 O + ] = [OH ] + [A ]. Suy ra, ta c h phng trnh sau
H 3 O + . OH = K H2O H 3 O + = OH + A = OH + C a
[ [
][ ] ] [ ] [ ] [
H2O + a 3
+ => H3O =
K ] [H O ] + C [H O ] C [H O ] K
+ 2 + 3 a 3
2 Ca + Ca + 4 K H2O
H2O
=0
=> [H 3 O ] =
+
Nu dung dch c Ca> 3,16.10-7 (M) (pH<6,5: Ty theo chnh xc yu cu m c cc iu kin gn ng khc nhau, y chp nhn nu pH<6,5 => mi trng axit): b qua cn bng (2): tc l b qua [H3O+] do nc phn ly ra so vi [H3O+] do axit phn ly. Do : [H3O+]=Ca => pH = -lg Ca V d: Tnh pH ca dungdch HCl 0,01M. HCl l axit mnh v Ca> 3,16.10-7 (M) pH =-lg Ca=-lg10-2=2. 2. Tnh pH ca dung dch baz mnh 1 bc Trong dung dch tn ti cn bng: BOH = B+ + OHH3O+ + OH2H2O Nu dung dch khng qu long Cb > 3,17.10-7M th b qua [OH-] do nc in ly. [OH-] = Cb p(OH) = - lgCb pH + p(OH) = 14 pH= 14 + lgCb
Nu dung dch qu long Cb < 3,17.10-7M th phi tnh n [OH-] do nc in ly ra, do gii da vo tnh trung ho v in tch v tch s ion ca nc
H3O+ . OH = KH2O OH = H3O+ + Na+ = H3O+ + Cb
][ ] [ ][ ][ ][
[ ] KH O] + C [OH
2 b
OH =
OH C b . OH K H2O = 0
Gii phng trnh tm c OH- pH VD: Tnh pH ca dung dch NaOH 0,01M => pH = 14+ lgCb =14-2=12. 3. Tnh pH ca axit yu 1 bc Axit HA c nng ban u l Ca A- + H3O+ (1) HA + H2O + H3O + OH (2) 2H2O
H 3 O + OH = K H 2 O H 3O + . A K = [HA ] => ta c h: a + = A + OH H 3O [HA ] = C A a
[ [
][ [
] ][ ]
] [ ] [ [ ]
Gii phng trnh bc 3 i vi [H3O+] tm c pH Tuy nhin khng phi gii phng trnh bc 3 m p dng cc phng php gn ng vi sai s < 5% * Nu Ca.Ka 10-12 v 0,1 < ch cn xt s in ly ca axit yu
Ca <100 th c th b qua s in ly ca nc, do Ka
HA + H2O B Ca cb Ca- x
A- + H3O+ 0 0 x x Gii ra tm c x pH
Ca > 10 0 Ka
Ka =
x2 Ca x
* Nu Ca.Ka 10-12 v
x2 Ka = Ca
axit rt yu x << Ca c th coi Ca-x Ca
x = Ka .Ca tnh pH
V d: Tnh pH ca dung dch CH3COOH 0,1 M bit Ka = 1,8.10-5 Ca.Ka = 0,1.1,8.10-5 = 10-6 > 10-12
Ca 10 1 = > 100 [H3O+] < < Ca 5 K a 1,8.10
CH3COOH + H2O
+ 3
[H O ] =
CH3COO- + H3O+
Ka .Ca = 1,8.105.101 pH = lg 1,8.10 6 = 2,87
4. Tnh pH ca baz yu 1 bc Xt cn bng trong dung dch baz yu B (A l axit lin hp ca B) B + H2O A + OHH3O+ + OH2H2O L lun tng t nh trng hp axit yu thy rng tm c [OH ] phi gii phng bc 3 . i n cc php gn ng: * Nu Cb.Kb 10-12 v 0,1 < B + H2O b Cb cb Cb-x
Cb < 100 Kb
th ch xt phng trnh in ly ca baz yu
A + OH- t [OH-] = x 0 0 x x gii ra tm c [OH-]
x2 Kb = Cb x
* Nu Cb.Kb 10-12 v
C K
b b
> 100
baz yu x<< Cb Cb - x Cb
x = [OH ] = Cb .Kb =
-
Cb .KH2O Ka
5. Tnh pH ca dung dch mui: Mui l sn phm ca phn ng trung ho gia 1 axit v 1 baz. Khi ho tan mui trong nc n phn ly thnh cc ion b hydrat ho. Tu vo bn cht ca cc ion m qu trnh dng li (pH=7) hoc cc ion tng tc vi nc lm thay i pH ca mi trng, tc l chng thc hin phn ng thu phn. nh ngha phn ng thy phn: L phn ng gia cation ca baz yu hoc anion ca axit yu vi nc lm thay i pH ca mi trng. V d: Al3+ l cation ca baz yu thc hin phn ng thu phn: Al3+.H2O + H2O Al2+OH + H3O+ Al(OH)2+ +H3O+ Al2+OH + H2O Al(OH)3 + H3O+ Al(OH)2+.H2O + H2O - c im: - Phn ng thu phn c tnh thun nghch
Nu ion ca axit yu hoc baz c nhiu in tch th s in ly thnh nhiu nc, nc sau yu hn nc trc. Nu dung dch khng qu long th cc nc sau c th b qua. Nu dung dch qu long th phn ng thu phn c th chuyn dch n mc hon ton. * Cc loi mui c th thu phn: - Mui to bi anion ca axit yu v cation ca baz mnh (to bi axit yu v baz mnh), khi ho tan trong nc to thnh mi trng kim. V d: NaCH3COO, Na2S, Na2CO3, NaClO NaCH3COO Na+ + CH3COOCH3COO- + H2O CH3COOH + OH- Mui to bi anion ca axit mnh vi cation ca baz yu, khi ho tan trong nc to mi trng axit. V d: NH4Cl, (NH4)2SO4, NH4NO3... NH4Cl NH4+ + ClNH3 + H3O+ NH4+ + H2O - Mui to bi anion ca axit yu v cation ca baz yu, khi ho tan c 2 gc u thu phn, pH ca mi trng cn ph thuc vo mc thu phn ca c 2 gc. Nu Ka(cation baz yu) > Kb(anion ca axit yu) th mi trng c pH < 7 Nu Ka(cation baz yu) < Kb(anion ca axit yu) th mi trng c pH > 7 Nu Ka(cation baz yu) = Kb(anion ca axit yu) th mi trng c pH = 7 V d: NH4CH3COO, NH4CH3COO NH4+ + CH3COONH3 + H3O+ Ka(NH4+) = 5,6.10-10 NH4+ + H2O Kb(CH3COO-) = 5,7.10-10 CH3COO- + H2O CH3COOH + OHC Ka(NH4+) = Kb(CH3COO-) nn pH = 7 NH4 NO2 NH4+ + NO2 NH3 + H3O+ Ka(NH4+) = 5,6.10-10 NH4+ + H2O HNO2 + OHKb(NO2-) = 2.10-11 NO2- + H2O C Ka(NH4+) > Kb(NO2-) nn pH < 7 - Mui to bi axit mnh v baz mnh khng thu phn: NaCl, NaClO4 - Mui axit l cht lng tnh. pH ca mi trng ca dung dch cha n ph thuc vo mnh ca tnh axit hay tnh baz. V d: Dung dch NaHCO3 l lng tnh v: HCO3- + H2O H2CO3 + OHKb(HCO3-) = 2,4.10-8 CO32- + H3O+ Ka2(H2CO3) = 4,8.10-11 HCO3- + H2O * Tnh pH ca dung dch mui: Nguyn tc: Ging nh cch tnh pH ca dung dch axit yu hoc baz yu V d 1: Tnh pH ca dung dch mui MCl3 0,1M. Bit rng ion M3+ c tnh axit, c hng s in ly Ka = 2.10-3 cc nc thy phn sau c th b qua. Ka.Ca = 2.10-3.10-1 > 10-12 Ca 0,1 = < 100 nn b qua [H3O+] do nc in ly Ka 2.103
M3+.H2O + 2H2O
Ka =
2+ 3+
[MOH ][H O ] = 2.10 . [M ]

+ 3
MOH2+ + H3O+
3
t x= [H3O+]
x2 Ka = = 2.103 x pH 0,1 x
V d 2: Cho dung dch K2CO3 0,2M, bit rng Ka2(H2CO3) = 5,6.10-11. Tnh pH ca dung dch, b qua nc in ly th 2 ca CO32-. K2CO3 2K+ + CO32CO32- + HOH HCO3- + OHCO32- l baz lin hp ca HCO3Ka.Kb = 10-14
14 14 Kb(CO32-) = 10 = 10 11 = 1,78 .10 4
Ka
5, 6 . 10
Kb.Cb = 0,2.1,78.10 > 10

Cb 0,2 = > 100 K b 1,78 .10 4
-4
-12
nn b qua s in ly ca nc
4 4 , OH = Kb .Cb = 1,78.10 .0,2 pH = 14+ lg 1,78.10 .0,2 = 117
[ ]
V d 3: Tnh pH ca NH4NO2 10-2 M, bit rng Ka ca NH4 + l 6,3. 10-10 v Kb ca NO2- l 2.10-11. V KaC v KbC u ln hn 10-14 rt nhiu nn phn ng ch yu trong dung dch l: NO2- <=> NH3 + HNO2 NH4- + -2 -2 Ban u: 10 M 10 M 0 0 -2 -2 10 -x x x Cn bng: 10 -x + Vy [NH4 ]=[NO2 ] v [NH3]=[HNO2] Ta bit rng K a ca NH4+ l: K a =
1 1
[NH3 ][ H 3 O + ] + [NH 4 ]
v K a ca NO2 l: K a
2
[ H O + ][NO2 ] = 3 [ HNO2 ]
1 2
=> K a .K a = [ H3 O + ]2 => [ H3 O + ] = K a . K a
1 2
=> K a =
2
10 14 = 5.10 4 ; [ H3 O + ] = 6,3.10 10.5.10 4 = 5,6.10 7 M 11 2.10
=> pH =6,25. 6.Tnh pH ca dung dch axit nhiu bc: - i vi axit nhiu bc nh H2S, H2SO3, H3PO4 s in ly theo nhiu nc, nc u tin mnh nht cn cc nc sau yu dn. V d: Nh s in ly ca axit H2S H2S + H2O HS- + H3O+ Ka1 = 10-7
HS- + H2O
S2- + H3O+ Ka2 = 10-13
Do nc 2 yu hn nhiu so vi nc 1 nn c th b qua s in ly ca nc 2 v a v bi ton tnh pH ca axit 1 bc.

VI. Cn bng trong dung dch cht in ly t tan
1.Tch s ha tan ca cht in ly t tan Xt dung dch bo ha cht in ly t tan AmBn: Trong dung dch lun tn ti cn bng gia phn rn khng tan v ion ca n trong dung dch: mAn+ + nBm- ( thc cht l AmBn (r) AmBn dd (tan) --> mAn+ + nBm- ). AmBn (r) Kc = [An+ ]m[Bm-]n Trong trng hp ny Kc c trng cho tnh tan ca cht in ly t tan v c gi l tch s ha tan ca cht in ly t tan Ks. * nh ngha: Tch s ha tan ca 1 cht in ly t tan l tch s nng ca cc ion trong dung dch bo ho cht in ly t tan (vi s m l h s tng ng trong phng trnh in ly). VD: CaSO4 Ca2+ + SO42- K s ,CaSo = [Ca 2+ ][ SO42 ]
4
Nh vy Ks l 1 trng hp ca hng s cn bng Kc, bn cht ca Ks l hng s cn bng K, do mi tnh cht ca K u p dng c i vi Ks. - Ks ph thuc vo bn cht tng cht v nhit . 2. Mi quan h gia tch s tan Ks v ho tan s Gi s l nng ca dung dch bo ho, v d i vi dung dch 2Ag+ + SO42Ag2SO4 2s s
K s,CaSO4 = [Ag + ]2 bh .[SO 4 2 ]bh = (2s)2.s = 4s3 s =
Ks 4
ho tan ca cht in ly t tan s gim i, nu thm vo dung dch mt lng ion ng loi. V d: Cho
K s, AgI
= 1,5.10-16 t = 250C. Tnh ho tan ca AgI trong nc
nguyn cht v trong dung dch KI 0,1M. Gii: ho tan ca AgI l s AgI Ag+ + I- (*) s s
Ks,AgI = Ag+ bh. I bh = s2 s = Ks ,AgI = 1,5.1016 = 1,22.108 M

Trong dung dch KI 0,1M KI = K+ + I0,1 0,1 Nng ca ion I- tng ln lm cho cn bng (*) dch chuyn theo chiu nghch lm cho ho tan ca AgI gim xung. Gi s l ho tan ca AgI trong dung dch KI
[ ] []
AgI
Ag+ + Is s + 0,1
K s , AgI = [ Ag + ][ I ] = s' (s'+0,1) = 1,5.10 16 V s << 0,1 b qua s so vi 0,1.
Vy s = 1,5.10-15M
s 1,22.108 = = 8,1.106 ln ho tan gim i 15 s' 1,5.10

3. iu kin to thnh kt ta v ho tan kt ta * iu kin to thnh kt ta: Mun to thnh kt ta cht in ly t tan th tch s nng ca cc ion ca chng trong dung dch vi s m thch hp phi ln hn tch s ho tan. V d: Trn 2 th tch bng nhau ca dung dch AgNO3 10-2M vi NaI 2.10-2 M. C to thnh kt ca AgI hay khng?
[ ]
+
102 Ag = = 5.103 M 2
2
[I ] = 2.10 2
= 102 M
+ 3 2 5 16 Vy Ag . I = 5.10 .10 = 5.10 > Ks ,AgI = 1,5.10 vy to thnh kt ta
[ ][ ]
b. iu kin ho tan kt ta V d: Ho tan FeS bng dung dch HCl FeS (r) S2- + Fe2+ (1) + HCl = H + Cl (2) 2+ S + 2H = H2S (3) 2Do (3) nn nng ca ion S gim xung lm [Fe2+].[S2-] < TFeS v lm cho cn bng dch chuyn theo chiu thun. Nh vy ho tan mt cht in ly t tan th phi thm vo dung dch mt cht no c kh nng kt hp vi mt trong cc ion ca cht in ly, lm cho tch s nng ca cc ion < tch s tan.
Ti liu tham kho:

Chng VII: ng ho hc
Nhit ng ho hc nghin cu phn trc ch mi cho php xt on chiu hng t din bin ca mt phn ng ho hc v ch kho st h trng thi cn bng, nn khng h cho bit mt tn hiu no v tc , ngha l s bin i cc tham s ca h theo thi gian. V d: Phn ng gia H2(K) + 1/2 O2(K) = H2O(l) c Go298 = -237,2 kJ/mol, Go298 ca phn ng rt m, c ngha l v mt nhit ng hc phn ng c th xy ra mt cch hon ton T= 298K v P = 1atm (K= 1041), song thc t cho thy phn ng hu nh khng xy ra iu kin cho, bi v tc ca phn ng cc k nh, do iu kin thng ngi ta tng phn ng ny khng xy ra. ng ho hc l mn khoa hc nghin cu v tc v c ch ca cc qu trnh ho hc.
I.khi nim v vn tc phn ng
1. nh ngha vn tc phn ng Vn tc trung bnh ca phn ng: c o bng bin thin nng ca mt trong cc cht tham gia phn ng hay to thnh sau phn ng trong mt n v thi gian. Xt phn ng: aA + bB cC + dD Gi s thi im t1 nng ca cc cht l CA1, CB1, CC1, CD1, thi im t2 th nng tng ng l CA2, CB2, CC2, CD2. Khi vn tc trung bnh ca phn ng l:
VA,tb = C A 2 C A1 t 2 t1
, VB,tb =
C B 2 C B1 t 2 t1
, VC,tb =
C C 2 C C1 t 2 t1
, VD,tb =
C D 2 C D1 t 2 t1
Vtb =
C t
(+)- ng vi cht kho st l sn phm (-) - ng vi cht kho st l cht tham gia Vn tc tc thi ca phn ng: C dC = V = lim t dt t 0 vn tc ca 1 phn ng l n tr:
V = 1 dC A 1 dC B 1 dC C 1 dC D = = = a dt b dt c dt d dt
2.Cc yu t nh hng ln vn tc Nng cc cht. Nhit Cht xc tc.
II. Thuyt va chm hot ng
1.Ni dung: Gi s xt phn ng A(K) + B(K) AB(K). phn ng xy ra th A v B phi va chm vi nhau. C 2 loi va chm: + Va chm gy phn ng: gi l va chm c hiu qu(s va chm ny nh). + Va chm khng gy phn ng: gi l va chm khng hiu qu(s va chm ny ln). gy va chm c hiu qu => cc phn t phi c nng lng ln hn nng lng trung bnh ca h => gi l cc phn t hot ng => vn tc phn ng t l vi tn s va chm gia cc phn t hot ng. 2.Phn b Boltzman: C kh l tng A vi tng s mol l N, trong c s phn t hot ng l N* th:
A N* = e RT => Biu thc nh lut phn b Boltzman. N E
Trong : EA- c gi l nng lng hot ho, n v J.mol-1 R - l hng s kh l tng, R = 8,314 J.K-1.mol-1
III. nh hng ca nng cc cht tham gia phn ng n vn tc v nh lut tc dng khi lng.
1. nh lut tc dng khi lng a. i vi h ng th( Cc cht phn ng cng 1 pha). * nh lut: Vn tc phn ng t l thun vi tch nng cc cht tham gia phn ng (vi s m thch hp). V d: aA +bB -> cC (1) => gi l phng trnh ng hc ca phn ng. => v =k[A]n[B]m trong [A], [B]: Nng mol/l ca A, B thi im xt. v : Vn tc tc thi thi im xt. n,m: Bc phn ng i vi cht A, B -> Xc nh bng thc nghim. (n+m): Bc chung ca phn ng. k: H s t l ph thuc vo bn cht ca cht tham gia v nhit. Vi 1 phn ng c th T =const -> k=const-> gi l hng s vn tc. Khi [A]=[B]=1mol/l-> v=k -> gi l v ring ca phn ng. b.i vi phn ng d th: Nu phn ng c cht rn tham gia -> coi nng cht rn = const v a vo hng s vn tc => cht rn khng c mt trong phng trnh ng hc ca phn ng. V d 1: C(gr) + O2(K) CO2(K) v = k'.const.[O 2 ]n = k[O2 ]n C. Gii thch: Khi nng tng th vn tc tng: Theo thuyt va chm hat ng: Khi nng cc cht tham gia phn ng tng th s phn t hot ng c trong 1 n v th tch tng -> dn n s va chm c hiu qu tng -> vn tc tng.
2.Bc phn ng: * Bc phn ng c xc nh bng tng s m trong phng trnh ng hc (m+n). Bc phn ng c th nguyn, hoc l s thp phn hoc bng 0. - Nu (m+n)=1: phn ng bc 1. - Nu (m+n)=2: phn ng bc 2. - Nu (m+n)=3: phn ng bc 3. * Cch xc nh bc phn ng: - Xc nh theo tng cht ri cng li: Dng phng php c lp: Coi nng cc cht # bng const ( ch c nng cht kho st bc thay i theo thi gian) bng cch cho nng cc cht ln hn rt nhiu nng cht xt. Mt phn ng ha hc l phn ng tng cng ca nhiu giai on trung gian. Mi giai on trung gian gi l 1 giai on s cp. Vn tc ca giai on s cp no chm cht s quyt nh vn tc ca c phn ng. S phn t tham gia vo 1 giai on s cp gi l phn t s ca giai on s cp . Phn t s ca giai on s cp chm nht xc nh bc chung ca phn ng. VD: 2HI + H2O2 = 2H2O + I2 (a) V=k[H2O2]n[HI]m Phn ng (a) xy ra theo theo 2 giai on s cp: HI + H2O2 -> HIO + H2O (1) xy ra chm HIO + HI -> I2 + H2O (2) xy ra nhanh. giai on (1) quyt nh bc phn ng -> phn t s ca (1) quyt nh bc ca phn ng (a). Phng trnh ng hc ca (a) cng l ca (1): v= k[H2O2][HI] Phn t s ca (1) v (2) u l 1+1=2. Bc ca p (a) l 1+1=2. * Ch : nu phn ng n gin ch xy ra theo 1 giai on th n=a, m=b (a, b l cc h s t lng trong phng trnh phn ng) => Bc phn ng (m+n) =(b+a).
IV. nh hng ca nhit ln vn tc phn ng
1.Quy tc Vant Hoff Bng thc nghim Vant Hoff cho thy rng nhit c tng thm 10oC th vn tc ca phn ng tng ln ln, trong khong t 2- 4.
Vt +10 = Vt
- l h s nhit cho bit vn tc tng ln bao nhiu ln khi nhit tng thm 10 C. Tng qut: nhit t1 vn tc ca phn ng l v1, nhit t2 vn tc ca phn ng l v2, ta c:
o
V2 =
t 2 t1 10
V1
l biu thc ton hc ca quy tc Vant Hoff
- Quy tc Vant Hoff ch gn ng trong khong nhit khng cao lm. 2. Phng trnh Arrhenius:
A lnk = + ln => k = .e T T
A
Trong : A v l nhng hng s c trng cho phn ng xc nh bng thc nghim. * Theo th lnk- 1/A vi tg = A * Da vo gi tr K hai nhit khc nhau:
lnK 2 = A + ln T2 1 1 K2 = A ln T T A K1 1 2 lnK 1 = + ln T1
* Gii thch nh hng ca nhit ti v theo thuyt va chm: Khi nhit thay i -> c s phn b li nng lng trong h-> s phn t hot ng thay i -> v thay i. C th: khi nhit tng vn tc tng do: chuyn ng nhit ca cc phn t tng ln tn s va chm ca cc cht tham gia tng v khi nhit cao th cc phn t km bn d phn ng vi nhau. * ngha ca A trong phng trnh Arrhenius Xt phn ng: A(k) + B(k) -> AB(k) c bc i vi A v B u bng 1. (a) Phng trnh ng hc: =kCA.CB
Ci* = Ci e
Ei
RT
(Ci mol/l ca phn t hat ng i).
Theo thuyt va chm hot ng v ch ph thuc vo Ci*

* * => v = C AC B = C A e
E Ai
RT
C B e
EA
RT
vi l h s t l.
=> v = C AC B e
( E A + EB )
RT
t EA + EB = Ea gi l nng lng hot ha ca phn ng. Ea l nng lng cn thit a mt mol cc cht tham gia phn ng c nng lng trung bnh tr thnh hot ng. => v = C AC B e
Ea
RT
(b)
=> So snh (a) v (b), c: k = e A=-Ea/R
Ea
RT
=> lnk =
Ea A + ln => lnk = + ln T RT
* ngha ca Ea: hiu r ngha ca Ea ta xt gin nng lng ca phn ng: I2(K) + H2(K) 2HI(K)
E K H2I2 Ea Ea http://hhud.tvu.edu.vn
Cc cht tham gia c nng lng ng vi mc I, mun phn ng c vi nhau phi vt qua hng ro th nng c cao l K. Hiu gia mc nng lng K v I chnh l nng lng hot ho ca phn ng thun Ea. Hiu gia mc nng lng K v II l nng lng ca phn ng nghch. Hiu gia mc I v II c gi l hiu ng nhit ca phn ng thun. Vy nng lng hot ho Ea: Chnh l hng ro th nng m cc cht tham gia phi vt qua hnh thnh cc sn phm phn ng. Nh vy, nu cc lin kt trong cc cht tham gia cng bn th nng lng hot ho ca phn ng cng ln.
V.nh hng ca xc tc ln vn tc phn ng
1. nh ngha: Cht xc tc l cht lm tng vn tc phn ng, nhng n khng b bin i v tiu tn do phn ng xy ra. Nu cht xc tc v cc cht tham gia phn ng trong cng mt pha th c gi l xc tc ng th. V d: 2SO2(K) + O2(K) 2SO3(K) Nu cht xc tc khc pha vi cc cht tham gia phn ng th c xc tc d th. V2O5(r) V d: 2SO2(K) + O2(K) 2SO3(K) Xc tc men ng vai tr quan trng i vi qu trnh qu trnh trao i cht: Phn ln cc phn ng sinh ho xy ra trong c th u di tc dng ca cc enzim 2. c im ca xc tc: - C tnh chn lc cao: Mt xc tc ch c th c tc dng i vi mt phn ng hay mt loi phn ng (cho v d) - Cht xc tc c tc dng lm gim nng lng hot ho ca phn ng - Cht xc tc lm xc tc cho phn ng thun th cng lm xc tc cho phn ng nghch, nn cht xc tc lm cho phn ng nhanh chng t ti trng thi cn bng, ch khng lm chuyn dch cn bng v n lm tng tc phn ng thun v phn ng nghch vi s ln bng nhau - i vi xc tc ng th: tc dng ca xc tc t l vi nng ca cht xc tc 3. Gii thch c ch ca xc tc a. i vi xc tc ng th:
NO
C ch ca xc tc ng th c gii thch bng l thuyt hp cht trung gian. Xt phn ng: A + B AB xy ra rt chm v c nng lng hot ho Ea rt cao, khi thm cht xc tc X tc ca phn ng tng ln, c ch ca phn ng nh sau: gm hai giai on A + X AX (hp cht trung gian) - giai on ny phn ng xy ra rt nhanh (c nng lng hot ho thp) AX + B AB + X - giai on ny xy ra rt nhanh, c nng lng hot ho thp Nh vy cht xc tc c tc dng a phn ng phi vt qua mt ro th nng cao thnh phn ng tri qua hai giai on vi ro th nng thp hn.
E K AX Ea
Ea2
A+B I
Ea1
AB II Tin trnh phn ng
Gi k1, 1, Ea - l hng s tc phn ng, vn tc v nng lng hot ho ca phn ng khi cha c xc tc k2, v2, Ea* - khi c xc tc Ta c: lnk1 =
Ea + ln RT E * lnk2 = a + ln RT (E E a *) k ln 2 = a k1 RT
v2 k2 = =e v1 k1
Ea Ea * RT
S ln vn tc tng ln khi c xc tc
b. i vi xc tc d th C ch ca mt phn ng xc tc d th rt phc tp, cho n nay cha c mt thuyt duy nht v xc tc d th. Mt phn ng xc tc d th xy ra gm nhiu giai on vt l v ho hc ni tip nhau - Giai on u: Xy ra s hp ph ca cc cht tham gia ln cc tm hot tnh ca cht xc tc - Giai on 2: Di tc dng ca cc lc ho hc trn b mt xc tc to ra cc hp cht b mt, dn ti thc hin phn ng trn b mt xc tc
VI. Cc phng trnh ng hc ca phn ng ha hc
Cc phng trnh ng hc m t mi quan h nh lng gia nng ca cc cht phn ng v thi gian trong cc phn ng bc khc nhau. 1. Phn ng bc mt
Phng trnh phn ng bc 1 c dng: A -> sn phm. Phng trnh ng hc vi phn ca phn ng c biu din bng:
v= d[ A] d[ A] = k[ A] hay = kdt dt [ A]
Ly tch phn phng trnh ny s thu c:

ln [ A] = kt [ A]0
y nng [A]0 l nng ban u ca A, [A] l nng ca n thi im t. Phn ng bc 1 thng l phn ng phn hy ca cc cht. V d: C2H6 C2H4 + H2 Cc phn ng phn hy phng x cng c xem l cc phn ng bc mt. V d:
232 90 4 Th 228 Ra+ 2 He 88
Khi nghin cu cc phn ng bc 1 ngi ta thng ch n mt i lng l thi gian na phn ng ( cn gi l chu k bn hy i vi phn ng phn hy phng x), k hiu l t1/2, l thi gian m mt na lng ban u ca cht phn ng b tiu th. p dng phng trnh ng hc ca phn ng bc 1 v t1/2 c [A] = [A] 0, ta c:
1 [ A]0 ln 2 0,693 ln 2 = kt1 / 2 => ln 2 = kt1 / 2 hay t1 / 2 = = [ A]0 k k
1 2
iu c ngha l thi gian na phn ng ca mt phn ng cho no l mt hng s c trng cho phn ng . ( mt nhit xc nh). Chu k bn hy l mt hng s vt l quan trng ca cc cht phng x. N c th dao ng trong mt khong rng t hng triu nm n my trm nm. V d: 14 C (phng x bta) t1/2 =5,7.103 nm. 8 He (phng x bta) t1/2 = 1,2 giy. Mt ng dng thc t quan trng ca i lng chu k bn hy l xc nh nin i ca cc vt c v tui ca cc khong vt. Cng vic ny ngy nay ch yu da trn phng php o cng phng x 14C.. 2. Cc phn ng bc hai Dng tng qut ca phn ng bc 2 l: A+ B -> sn phm Phng trnh ng hc vi phn ca phn ng c biu din bng:
d[ A] d[ B ] = = k[ A][ B] dt dt
y chng ta xt trng hp n gin nht l nng ban u ca A v B bng nhau. V vy c th vit:
d[ A] d[ A] d[ A] = k[ A] 2 hay = k dt . Ly tch phn 2 v = k dt 2 dt [ A] [ A] 2

1 = kt + const [ A]
1 = const . T : [ A]0
=>
khi t =0 th
1 1 = kt [ A] [ A]0 1 k[ A]0
1 1 1 k= ( ) t [ A] [ A]0
Gi t1/2 l thi gian na phn ng. Thay vo phng trnh trn ta c:

t1 / 2 =
Ti liu tham kho:

Chng VIII: cc qu trnh in ho

I.Nguyn tc bin ha nng thnh in nng
1. Phn ng oxy ho kh V d: Xt phn ng oxy ho kh thng thng xy ra trong dung dch khi nhng thanh Zn vo dd CuSO4 Zn + CuSO4 = ZnSO4 + Cu Zn + Cu2+ Zn2+ + Cu Ho = -230 KJ
2e
Cu2+ trc tip n thanh Zn nhn e Zn-2e =Zn2+ Qu trnh xi ha Qu trnh kh Cu2+ +2e = Cu c im ca phn ng xi ha kh: - e trc tip t cht kh sang cht xi ha. - Nng lng phn ng xi ha kh gii phng di dng nhit. Trong phn ng oxy ho kh ny cht kh v cht oxy ho c tip xc vi nhau, cc electron s c chuyn trc tip t cht kh sang cht oxy ho v nng lng ca phn ng ho hc c to ra di dng nhit. Nhng nu ta thc hin qu trnh oxy ho Zn v qu trnh kh Cu2+ 2 ni ring bit v cho e chuyn t Zn sang Cu2+ bng 1 dy dn in, c ngha l to nn mt dng e nht nh th nng lng ca phn ng ny c chuyn thnh in nng, lm xut hin trong dy dn 1 dng in ngc chiu vi dng electron. cng l qu trnh xy ra trong mi pin. 2. Nguyn tc bin ha nng thnh in nng Thc hin qu trnh xi ha 1 ni, qu trnh kh mt ni khc. Cho e chuyn t cht kh sang cht xi ha nh dy dn in th nng lng ca phn ng ha hc (gii phng di dng nhit) s bin thnh in nng c gi l 1 pin. Pin l 1 dng c thc hin nguyn tc bin ha nng thnh in nng. 3.Cu to hot ng ca pin Cu-Zn a. Cu to: gm 2 in cc + Mt cc l Zn nhng vo dung dch ZnSO4 + Mt cc l Cu nhng vo dung dch CuSO4 Hai in cc ny c ni vi nhau bng 1 dy dn in. Hai dung dch ZnSO4 v CuSO4 c ni vi nhau bng mt mng ngn. -
Thanh Zn c d e ( d tch -) hn thanh Cu => thanh Zn l cc m (-),, thanh Cu l in cc dng (+). b. Hot ng Cc (-):xy ra qu trnh oxy ho: Zn - 2e Zn2+ in cc Zn b n mn dn (in cc mn dn) v Zn2+ tng dn. Cc (+): xy ra qu trnh kh: Cu2+ + 2e Cu2+ . in cc Cu dy thm , nng Cu2+ gim Phn ng tng cng xy ra trong pin: Zn + Cu2+ = Zn2+ + Cu * K hiu pin: Vt liu lm Dd nhng Dd nhng Vt liu in cc 1 in cc 1 in cc 2 lm in cc 2 => s pin Cu-Zn: (-)Zn | ZnSO4 || CuSO4 | Cu (+) Khi ni in cc Cu v Zn bng 1 dy dn, cc e s chuyn t cc Zn (-) sang cc (+) do gia 2 cc c s chnh lch th, lm xut hin mt dng in di chuyn ngc chiu vi dng electron. Nh vy, to dng in trong pin th gia 2 in cc phi xut hin mt hiu s in th.
II. Cc loi in cc
1. in cc kim loi:
+ +
+ +
Khi nhng thanh kim loi M vo nc th do tng tc ca cc phn t nc c cc ->cc ion kim loi b tch ra khi b mt kim loi i vo dung dch cn cc e li trong thanh kim loi. Kt qu thanh kim loi s tch in m, cn dung dch st kim loi s tch in dng, to thnh mt lp in tch kp. Trong dung dch tn ti cn bng: M Mn+ + ne
Nu thm mui cha ion Mn+ vo dung dch trn th cn bng chuyn dch theo chiu nghch v s c mt s ion Mn+ t dung dch chuyn vo thanh kim loi v cn bng trn vn c thit lp. Khi cn bng, gia b mt kimloi- dung dch xut hin 1 hiu s in th gi l th in cc kim loi. Th in cc kim loi ph thuc vo: bn cht cu KL v dung mi, nng ion kim loi M v nhit . Nu xt cng 1 nhit , cng 1 dung mi, th in cc kim loi c trng cho bn cht kim loi: nu th in cc c gi tr cng (-) th kim loi hat ng cng mnh v ngc li. 2. in cc tr nhng trong dung dch cha cp oxy ho kh Cu to in cc tr: Kim loi lm in cc tr v mt ha hc. V d Au, Pt..
- V d: xt in cc oxy ho kh l mt thanh kim loi Pt c nhng vo dung dch cha cp oxy ho kh FeCl2, FeCl3. Khi Fe3+ s ly e ca thanh Pt v chuyn thnh Fe2+: Fe3+ + e Fe2+, nn thanh Pt s tch in dng, cn dung dch d Cl- s tch in m. Mt khc, thanh Pt tch in (+) s ngn cn Fe3+ tip tc ly thm e, nhng li c kh nng nhn thm e ca FeCl2 bin Fe2+ thnh Fe3+: Fe2+ - e Fe3+. Nh vy: cn bng Fe3+ +e Fe2+ nhanh chng c thit lp, do trn danh gii gia in cc v dung dch s xut hin mt hiu s in th, c trng cho tnh hot ng ca cp oxy ho kh. Hiu s in th ny ph thuc vo bn cht ca cp oxy ho kh, nng ca cht oxy ho, cht kh v nhit . 3. in cc kh: in cc kh l in cc tip xc vi kh v dung dch cha dng xi ha( hoc dng kh) ca n. iu kin: 1. Kim loi lm in cc tr 2. Khng tc dng ho hc vi kh 3. C kh nng hp ph kh v lm xc tc cho phn ng gia kh v ion ca n V d: in cc kh H2 c lm bng 1 thanh Pt trn c ph mt lp mui Pt c tc Pt dng hp ph kh H2 v c nhng vo dung dch H2SO4 in cc c cn bng sau:
H2
2H3O+ +2e H2 + 2H2O
Gia in cc v dung dch cng xut hin mt hiu s in th ph thuc vo nng ca ion H3O+, p sut ca H2 v H2 nhit . - in cc H2 chun: V khng th xc nh c gi tr tuyt i ca hiu s in th gia in cc v dung dch, nn phi quy c ly 1 in cc no lm chun v gn cho n mt gi tr hiu s in th. Ngi ta quy c ly in cc chun hidro lm chun. l in cc kh H2 c thm iu kin sau: P H = 1atm v [H3O+]=1M. Trong iu kin nh vy, hiu s
2
in th ca in cc vi dung dch nhit bt k c quy c bng 0,00(V) v c k hiu l 0 * iu kin chun ca cc loi in cc: Nng cc dng tham gia phn ng in cc bng 1M, nu l cht kh th P= 1atm. nhit xc nh.
V d in cc kim loi Cu2+ + 2e = Cu [Cu2+] = 1M hay in cc chun ca Cu l thanh Cu nhng trong dung dch Cu2+ nng 1mol/l.
IV. Sut in ng ca pin
1. nh ngha: Sut in ng (s) ca pin l gi tr hiu s in th ln nht gia 2 in cc ca pin, c o bng (V), k hiu l E. E = (+) - (-) Trong : (+)- in th ca in cc dng (-)- in th ca in cc m (Nu theo quy c trn E lun dng, trng hp tng qut E = in th in cc phi in th in cc tri) 2. Cc yu t nh hng n E- Cng thc Nernst Xt pin: (-) Pt | Sn4+, Sn2+ || Fe3+, Fe2+ | Pt (+) Cc (-): Xy ra qu trnh xi ha : Sn2+ - 2e = Sn4+ Cc (+): Xy ra qu trnh kh : 2Fe3+ + 2e = Fe2+ Phn ng trong pin l phn ng tng cng 2 qu trnh 2 in cc: 2Fe3+ + Sn2+ 2Fe2+ + Sn4+ (*) Nu pin lm vic thun nghch nhit ng T, P =const th:
' G = Wmax = n.E .F
Trong :
n- l s e trao i gia cht kh v cht oxy ho F- Hng s Faraday, F = 96.500 C.mol-1 E- Sut in ng ca pin.
G 0 G 0 nu iu kin chun => E = E= n.F nF

0 Vi phn ng (*) c G T = G T + RT ln
[ Sn 4+ ][ Fe 2+ ]2 [ Sn 2+ ][ Fe 3+ ]2
Chia c 2 v cho 2F c:
G T G o T RT [ Sn 4+ ][ Fe 2+ ]2 = ln 2.F 2F 2F [ Sn 2+ ][ Fe 3+ ]2
RT Sn 2 + Fe 3+ E=E + ln 2F Sn 4 + Fe 2+
o
[ [
][ ][
] ]
2 2
Tng qut: Phn ng xy ra trong pin l: aA + bB <=> cD +dD ( A, B, C, D l cht tan trong dung dch)
C E = E 0 +
RT [ A]a [ B ]b ln nF [C]c [ D]d
-> Cng thc Nernst biu th E =f(C,T).
cc yu t nh hng n E l: Nng v nhit . T = 298K, thay R = 8,314 J.K-1.mol-1, F = 96.484 C.mol-1 v i sang logarit thp phn.
E = E0 + 0.059 [ A]a [ B]b lg n [C]c [ D]d
V. Th in cc (th kh)
1. Cp xi ha kh: V d: Trong dung dch tn ti Cu2+ nhng trong phn ng th Cu2+ + 2e = Cu gi Cu2+/Cu l 1 cp xi ha kh. * nh ngha: Cp xi ha kh l mt cp gm cht xi ha v cht kh, chng c th bin i ln ra nhau trong qu trnh phn ng. - K hiu cp xi ha kh l cht xi ha/cht kh hoc cht xi ha, cht kh. - Vi cch quy c ny phn ng in cc bao gi cng l qu trnh kh xi ha + ne = Kh - Cp xi ha kh chun: L cp xi ha kh khi [xi ha] =[kh] = 1M ( nu l cht kh P= 1atm). 2. Th kh Quy c qu trnh in cc l qu trnh kh dng: Oxh + ne -> Kh Th o c gi l th kh ca cp oxiha kh. K hiu l ox
Kh
* Th kh l i lng c trng cho kh nng xi ha kh ca cp xi ha kh - Nu ox c gi tr cng ln (cng dng) -> dng oxi ha hot ng mnh, dng kh
Kh
yu. Nu ox yu.
c gi tr cng nh (cng m) -> dng kh hot ng mnh, dng xi ha

Kh
Th kh ca 1 cp oxiha kh chun gi l th kh chun 0 ox Kh * Cch xc nh th kh chun ca mt cp oxiha kh: Vic xc nh gi tr tuyt i th kh ca cc in cc l khng th lm c, nhng nu quy c th kh ca mt in cc no lm chun v bng cch so snh s xc nh c th kh ca cc in cc khc
2
- Quy c: Chn in cc kh hydro lm in cc so snh vi [H 3 O + ] = 1M, PH = 1atm v gn cho n gi tr in th = 0 mi nhit , k hiu th ny tng ng vi cn bng in cc: 2H3O+ + 2e
oH3O+/H2 = 0,00 (V). Hiu s in

H2 + 2H2O
xc nh th kh ca mt in cc ngi ta ghp in cc ny vi in cc chun H2 thnh mt pin, ri xc nh sut in ng ca pin to thnh. Gi tr sut in ng ca pin chnh l th in cc chun ca in cc cn xc nh in th. N c gi tr dng nu th ca in cc xc nh cao hn th ca in cc chun H2 v ngc li. VD: Pt, H2(1atm) || Cu2+ | Cu
2+
0 o c E0= 0,34 (V) = Cu
-0=0,34 (V). (v Cu l in cc dng ca pin)

Cu
Bng phng php ny ngi ta xc nh c th kh chun ca nhiu cht v lp thnh bng th kh chun. Vi cc nguyn t c nhiu mc xi ha khc nhau-> tnh 0 ca 1 cp da vo
0 ca cc cp khc bng cch lp chu k kh kn:
VD: Fe3+ + 1e Fe2+ + 2e Fe3+ + 3e Fe Fe
Fe2+ ,
0 Fe
3+
Fe 2 +
2+
= 0,77( V ) = 10
0 = 0,44( V ) = 2
0 Fe
Fe
0 Fe 3 + Fe
=?
tnh 0 ,lp chu trnh kh kn:

S xi ha (+) cao nht G10 +n1e +ne
G 0
S xi ha (+) thp nht

0 G 2
+n2e
S xi ha (+) trung gian

G = G + G
0 0 1 0 2
( G = nE 0 F = n 0 F )
0
0 => n 0 F = n1 10 F n 2 2 F
=> 0 =
0 n1 10 + n 2 2 n
C th v d trn:
G 0
Fe
3+
+3e
Fe
G10
+1e Fe2+
+2e G 0 2
0 G 0 = G10 + G 2 0 1 10 + 2 2 0,77 + 2(0,44) = = 0,036(v) 3 3
=>
0 =
3. Cc yu t nh hng n th in cc T v d trn vi phn ng: 2Fe3+ + Sn2+ 2Fe2+ + Sn4+

RT Sn 2 + Fe 3+ ln C E = E + 2F Sn 4 + Fe 2+
o
[ [
][ ][
] ]
2 2
M E = + v E 0 = 0 + 0 nn c:
+ = 0+ 0 +
Fe 3+ RT (ln 2F Fe 2+
=> + =
= 0
[ [ RT [Sn + ln 2F [Sn
Fe 3+ RT + ln 2F Fe 2+
4+ 2+
] ] ] ]
[ [
] ]
2 2
- ln
[Sn ]) [Sn ]
4+ 2+
2 2
Tng qut: C phn ng in cc: axh + ne => i = 0 i +

0
bKh
RT [Oxh] ln nF [Kh]b
0 i
25 C: i =
0,059 [Oxh] + lg n [Kh]b
M * i vi in cc kim loi: Mn+ + ne 0,059 =0 + lg[M n+ ] n * i vi in cc kh: v d : O2(k) + 4 e + 4 H+
2H2O
=0 +
0,059 lg([H + ]4 . pO2 ) 4
* i vi in cc tr trong dung dch xi ha kh: Nu trong phn ng kh c mt H+, OH=> pH thay i => pH lm thay i th kh. VD1: Sn2+ + 2e Sn4+
=0 +
0,059 Sn 4+ lg 2 Sn 2+
[ [
] ]
VD2: MnO4- + 5e + 8H+
Mn2+ + 4 H2O
0,059 [ MnO4 ][ H + ]8 lg = 0 + 5 [ Mn 2 + ]
V. Chiu v trng thi cn bng ca phn ng xi ha kh xy ra trong dung dch nc.
1. Chiu ca phn ng oxy ho kh: i vi phn ng oxy ho kh da vo mi lin h gia G v E xt chiu, bit rng G = -n.E.F. phn ng xy ra th G < 0 hay -n.E.F <0 E > 0 m i vi phn ng oxy ho kh th E = ox - kh ox > kh Trong : ox - Th kh ca cp oxy ho kh c dng oxy ho tham gia phn ng kh - th kh ca cp c dng kh tham gia phn ng Quy tc v chiu ca phn ng oxy ho kh: C 2 cp oxy ho kh ox1/kh1 v ox2/kh2, nu chiu: ox1 + kh2 ox2 + kh1. iu kin chun: Go = - n.Eo.F < 0 Eo >0 oox > okh Ch : Trong trng hp tng qut xt chiu ca phn ng oxy ho kh th phi tnh th kh ca cc cp oxy ho kh trong iu kin phn ng ri mi so snh v rt ra kt lun Theo cng thc Nernest th kh ca mt cp oxy ho kh ph thuc vo nng cc dng oxy ho, dng kh, ph thuc vo nhit v pH ca mi trng, nn khi thay i mt cc thng s trn th th kh ca cc cp s thay i v c th dn n lm thay i chiu ca phn ng oxy ho kh. Di y xt mt vi v d v chiu ca phn ng oxy ho kh. V d 1: Cho bit cn bng sau 25oC trong dung dch nc: 2Cr2+ + Cd2+ 2Cr3+ + Cd, bit o Cr
3+
ox / kh >ox / kh
1 1 2
th phn ng xy ra theo
/Cr 2 +
= 0,41V , o Cd 2 + /Cd = 0,4V
a. iu kin chun phn ng xy ra theo chiu no ? b. Trn 25 ml dung dch Cr(NO3)3 0,4M vi 50 ml dung dch Cr(NO3)2 0,02M, 25 ml dung dch Cd(NO3)2 0,04M v bt Cd. Hi chiu phn ng iu kin ny ? Gii: a. oox = o Cd2 + /Cd = 0,4V ; okh = o Cr
3+
/Cr 2 +
= 0,41V
oox > okh, vy iu kin chun phn ng xy ra theo chiu thun b. Tnh nng ca cc dng oxy ho v dng kh
, 0 . [Cr ] = 0,4.00,1025 = 0,1M ; [Cr ] = 0,02.,1,05 = 0,01M ; [Cd ] = 0,04001,025 = 0,01M 0 ,
3+ 2+ 2+
Cr 3 + /Cr 2 + = o Cr 3 + /Cr 2 + +
0,059 Cr 3+ 0,1 lg = 0,41 + 0,059lg = 0,351V 2+ 1 0,01 Cr
[ [
] ]
Cd 2 + /Cd = o Cd 2 + /Cd +
0,059 0,059 lg0,01 = 0,459V lg Cd 2 + = 0,4 + 2 2
ox = Cr 3 + /Cr 2 + = 0,351V ; kh = Cd 2 + /Cd = 0,459V , vy iu kin ny phn ng xy ra
theo chiu nghch. V d 2: nh hng ca nng ca dng oxy ho v dng kh ln chiu ca phn ng oxy ho kh Cu2+ + e Cu+ ; Sn4+ + 2e Sn2+; iu kin chun do Cu+ + Sn4+
o Cu2+/Cu+ = 0,153V
o Sn4+ /Sn2+ = 0,15V
+ oCu2+/Cu > oSn /Sn
4+ 2+
nn phn ng xy ra theo chiu Cu2+ + Sn2+
Nu tng nng ca [Sn 4 + ] hoc [Cu + ] th:
Sn4+ /Sn2+ =
Sn /Sn
4+
2+
Cu2+ /Cu+ = o Cu2+ /Cu+

n khi
[ ] [ ] [Cu ] + 0,059lg [Cu ]

2+ +
0,059 Sn4+ lg 2+ + 2 Sn
+ Sn4+/Sn2+ > Cu2+/Cu
hay
+ oSn4+/Sn2+ > Cu2+/Cu
th phn ng s xy ra theo chiu
nghch. 2. Trng thi cn bng ca phn ng oxy ho kh Phn ng oxy ho kh t n trng bng khi G = n.ET .F = 0 ET = 0 hay ox = kh. T Hng s cn bng ca phn ng xi ha kh:
G 0 = RT ln K
mt khc G 0 = nFE 0 => RT ln K = nFE 0 lnK =

n.E o .F (phn ng trong dung dch th K=Kp=KC). RT
n.E o T = 298K lgK = 0,059
Trong o: n- l s e trao i gia dng oxy ho v dng kh Eo = oox- okh V d: Tnh hng s cn bng K ca phn ng sau:
2Fe3+ + Sn2+
2Fe2+ + Sn4+ ;
o Fe3+ /Fe2 + = 0,77V ; o Sn
4+
/Sn 2 +
= 0,15V
2 oox = oFe3+/Fe2+ ; okh =oSn4+/Sn+
lg K =
2.(0,77 0,15) = 21 K= 1021 0,059
VI. Qu trnh in phn
1. nh ngha: in phn l qu trnh oxy ho v qu trnh kh xy ra trn b mt in cc khi cho dng in mt chiu i qu dung dch cht in ly hoc cht in ly nng chy. V d: in phn dung dch CuCl2 Khi cho dng in mt chiu i qua dung dch CuCl2 th di tc dng ca in trng cc cation Cu2+ i v cc m, cn anion Cl- i v cc dng. Ti cc in cc s xy ra hin tng phng in. Catt (-): Cu2+ + 2e Cu Ant (+): 2Cl- -2e Cl2 Cu2+ + 2Cl- Cu+ Cl2 y chnh l phn ng oxy ho kh xy ra khi in phn dung dch CuCl2. Phn ng ny khng t xy ra c, m n ch xy ra c di tc ng ca ngun in mt chiu bn ngoi. Do qu trnh in phn l qu trnh bin i in nng thnh ho nng. 2. S phn cc: Khi in phn trng thi in ca in cc (th v mt in tch ca lp in tch kp) b thay i. Th ca in cc s khc vi th ca n lc cn bng (khi cha c dng in). Hin tng ny c gi l s phn cc. Tu thuc vo tnh cht ca qu trnh lm thay i th ca in cc c 3 loi phn cc khc nhau: a. S phn cc v nng : Khi in phn nng ca cc ion catt v ant b thay i. ant do kim loi b ho tan, nng ca ion tng ln, cn catt xy ra s kh nn nng ca ion gim i, dn n th ca in cc gim. Nu mt dng in cng ln th s bin i nng ca cc ion cng ln, do s phn cc cng ln. Cn khuy mnh gim s phn cc. b. S phn cc ho hc: Khi in phn cc sn phm thot ra cc in cc dn ti s to thnh 1 pin c chiu ngc vi chiu dng in c. S phn cc in ho:
Khi nhng 2 in cc vo dung dch cht in ly v ni 2 in cc vi ngun in mt chiu th cc e s di ant (+) ti catt (-) nhng cc e khng t i qua dung dch c, nn nu trn cc in cc khng xy ra cc qu trnh in ho th mt in cc s tch in () do tha e, cn in cc kia tch in (+) lm cho cc lp in tch kp cc in cc b thay i, do gia 2 in cc s xut hin mt hiu s in th c chiu ngc vi chiu ngun in bn ngoi. V d: in phn dung dch CuCl2 (+) Ant: (-) Catt: 2Cl- -2e Cl2 Cu2+ +2e Cu Cu2+/Cu Xut hin Cl2/ClSn phm thot ra cc in cc dn ti s to thnh mt pin Epin = th phn cc = Efc. 3. Th phn hu: S in phn ch xy ra mt in p hon ton xc nh. in p ti thiu gia 2 in cc s in phn bt u xy ra c gi l th phn hu. Nh vy, v mt l thuyt th Efh = sut in ng ca pin to bi cc sn phm thot ra ant v catt = Efc, nhng thc t Efh > Efc v Efh = Efc + = Efh - Efc, c gi l qu th. ph thuc vo bn cht ca in cc, trng thi b mt in cc, thnh phn dung dch, mt dng, ... 4. S in phn cht in ly nng chy Khi cho dng in mt chiu i qua cht in ly nng chy th cc cation i v catt (-), cn cc anion i v ant v xy ra hin tng phng in. V d: in phn nng chy NaCl (-): Na+ (+): ClNa+ + e Na Cl- -e 1/2Cl2 NaCl Na + 1/2 Cl2 5. in phn dung dch cc cht in ly: Trong dung dch ngoi cc ion do cht in ly phn ly ra cn c ion H3O+ v OH- do nc in ly ra. Khi cho dng in mt chiu i qua dung dch cc cation kim loi Mn+ v ion H3O+ s i v catt cn cc anion gc axit v ion OH- s i v ant (-). a. Qu trnh catt: Xy ra phn ng kh cc cation Mn+ theo phn ng: Mn+ + ne M (1) hoc ion H3O+ theo phn ng 2H3O+ + 2e H2 + 2H2O (2) tu thuc vo kh nng oxy ho ca chng c nh gi bng th kh. Trong dung dch c pH = 7 th kh ca hydro l :
H O + /H = 0,059.pH = 0,413V . V pH =7 phng trnh (2) c vit di dng 2H2O 3 2

+ 2e -> H2 + 2OH-
Cc kim loi c th kh Mn + /M > H3O+ /H2 = 0,413V th b kh catt theo (1). Theo bng dy th in cc tiu chun l nhng kim loi ng sau st, nhng do qu th ca hydro nn b y n cc kim loi ng sau Al (khng k Al) b kh catt. Trng hp ngc li: Cc ion kim loi t Al tr v trc dy th kh s khng b kh m ion H3O+ s b kh theo phng trnh (2). b. Qu trnh ant: Xy ra s oxy ho hoc anion, hoc ion OH- hoc cht lm in cc tu thuc vo kh nng kh ca chng. Nu l in cc kim loi: Do kim loi c kh nng kh mnh cht nn ant s b tan ra thao phn ng: M- ne Mn+ Nu ant l in cc tr: Xy ra qu trnh oxi ho anion gc axit hoc ion OH- tu theo kh nng kh ca chng gim dn theo dy sau: S2- > I- >Br- > Cl- > F- > OH- > anion cha oxy. V d 1: Vit s in phn dung dch Na2SO4 dng graphit lm in cc( ant tr).
Catt H2O , 2Na+ 2H2O + 2e = H2 + 2OHNa2SO4 2Na+ + SO42Ant SO42- ,H2O 3H2O - 2e = 2H3O+ + 1/2 O2
T s inphn trn ta thy thc cht l s in phn nc. Vai tr ca Na2SO4 y ch l cht dn in. V d 2: Vit s in phn dung dch CuSO4 dng ant bng ng.
Catt H2O , Cu2+ Cu2+ + 2e = Cu Cu to thnh bm vo catt CuSO4 Cu2+ + SO42Ant (Cu) SO42- ,H2O Cu - 2e = Cu2+ Ant tan dn
Ti liu tham kho:


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Bi ging mn C s l thuyt Ha hc

CHNG I: P DNG NGUYN L TH NHT CA NHIT NG HC VO HO HC

(1.2) : Tng s mol kh trong hn hp.

p sut ring phn Pi ca kh i trong hn hp c th tnh:

(1.4) (1.5) W=0. (1.6)

W ph thuc vo Pn ( v h sinh cng nn c du -). Nu qu trnh l hu hn => W = Pn dV

Nu gin n trong chn khng Pn= const (Pn=Pkq) Wtn= Pn dV

Nu kh l l tng v gin n ng nhit c : Pn = Ph =

= U2-U1 = WA + QA =WB + QB =...=const i vi mt bin i v cng nh

Theo nguyn l I: dU= W + Q Do : dU= Q v U =

U2 - U1 = Qp-P(V2-V1) hay Qp = (U2+PV2) (U1+PV1) QP: Gi l nhit ng p

Ta c: Qp= H2-H1 = H III. NHIT PHN NG HO HC. 1. Nhit phn ng

H c gi l entapi, n l hm trng thi v U v PV u l nhng hm trng thi.

Phn ng thu nhit: l phn ng nhn nhit lng t mi trng. Khi

Quan h gia nhit ng tch v nhit ng p:

Qp= Qv+ nRT R = 8.314 J/mol.K: hng s kh l tng T: K V d: C6H6 (l) +

Trong : n = s mol sn phm kh s mol cht kh tham gia phn ng.

C(r) + O2(k) = CO2(k)

0 V d: H 298, s (CO2)=-393,51(kJmol-1). N l nhit phn ng ca phn ng sau 250C

khi pO = pCO = 1atm

khi PCH = PO = PCO = 1atm .

CH4 (k)+ 2O2 (k)

CO2 (k) + 2H2O(l)

CO(k) + 1/2 O2(k) Theo nh lut Hess:

Nu iu kin chun v T=298K th

C2H4(k): +52,30 C2H6(k): -84,68 Gii: Ta c:

Nu iu kin chun v T=298K th

tnh c nhit ca phn ng trn ta hnh dung s sau:

Bi ging mn C s l thuyt Ha hc Cgr + O2(k) x=? CO(k) + 1/2O2(k) CO2(k)

NaCl H 5 = 414.216 J .mol 1

Theo nh lut Hess ta c:

=> dH=CpdT =>

-Nhit dung mol ng tch. Qu trnh c thc hin V=const.

=> dU=CvdT =>

Theo nh lut Hess ta c H 2 = H1 + H a + H b

Hb = (n3CPC + n4CPD )dT

T H2 = H1 + [(n3CP + n4CP ) (n1CP + n2CP )]dT

=> H T = H T + C P dT => Cng thc nh lut Kirchhoff

Vi: C P = C P (sp) C P (tg )

iu kin chun(P=1atm) v T1=298 K c:

0 Nu trong khong hp ca nhit => coi C P = const th 0 0 0 H T = H 298 + C P ( T 298)

Ti liu tham kho:

Nu l bin i bt thun nghch: dS > Tng qut

Du > : qu trnh bt thun nghch Du = : qu trnh thun nghch

* Ch : V S l hm trng thi --> S ch ph thuc vo trng thi u v trng thi cui, tc l:

(khng xc nh c trc tip Sbtn)

H cf nhit chuyn trng thi

V T=const --> U = 0 WTN = nRT ln Theo nguyn l I: U = QTN + WTN = 0 ==> S = nR ln

--> QTN = WTN = + nRT ln

Trong iu kin V= const

Nu coi Cp hoc Cv khng i theo T th:

0 thng th P=1atm, T=298K, n=1mol ==> S 298 ( J .K 1 .mol 1 )

cha xc nh nhng c th a v cc thng s ca h bng cch tm 1

==> tiu chun t din bin v gii hn ca qu trnh l:

<=> H TS 0 <=> (H TS ) 0 <=> G 0

Nguyn l II => Q TdS ; => dG TdS + W '+ VdP TdS SdT

dU TdS PdV + W '

Tiu chun t din bin v gii hn ca qu trnh l:

dA TdS PdV + W ' TdS SdT

0 G 298, s ( HCl) =-95,5kJ.mol-1 ng vi qu trnh

Nu iu kin chun v 250C c:

G <0: phn ng xy ra theo chiu thun G =0: qu trnh cn bng

thay vo biu thc G = H TS ta c: