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Chng 1 NGUYN L TH NHT NHIT NG HC V P DNG VO HA HC

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1.1 MT S KHI NIM M U


1.1.1 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 = tC +273) R: Hng s kh l tng, ty theo n v ca P v V m c ga tr khc nhau:

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:

1.1.2 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.

1.1.3 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 ()

1.1.4 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: tC, 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 2

Thng s trng thi dung l nhng thng s trng thi t l vi lng cht,

v d th tch, khi lng.

Thng s trng thi cng khng t l vi lng cht, v d nhit p

sut, nng , nht.

1.1.5 Trng thi cn bng ca h


L trng thi ti cc thng s trng thi ca h khng i theo thi gian. V d phn ng thun nghch CH3COOH + C2H5OH <=> CH3COOC2H5 + H2O t trng thi cn bng khi nng ca 4 cht khng bin i.

1.1.6 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.

1.1.7 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.

1.1.8 Nhit v cng


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. 3

Cng gin n (cng chuyn dch).

Nu gin n bt thun nghch: Gin n chng li Pn khng i:

1.2 NGUYN L TH NHT NHIT NG HC P DNG VO HA HC


1.2.1 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 .

1.2.2 Pht biu nguyn l th nht ca nhit ng hc


Nguyn l th nht 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. Tn ti mt hm trng thi U gi l ni nng, dU l mt vi phn ton phn. 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).

i vi mt bin i v cng nh:

i vi mt bin i hu hn:

1.2.3 Nhit ng tch, nhit ng p


1.2.3.1Nhit ng tch (V = const) Xt 1 h kn, c T, V = const, h ch sinh cng c hc:

Qv l nhit ng tch, gi tr ca n ch ph thuc vo trng thi u v cui ca h. 1.2.3.2Nhit ng p (P = const) Xt h kn, thc hin c T, P =const, h ch sinh cng c hc:

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

1.3 NHIT PHN NG HA HC


1.3.1 Nhit phn ng
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 101,325 kPa (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 101,325 kPa, 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:

1.3.2 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 = 298K).

1.3.3 Nhit chy chun ca mt cht


L nhit ca qu trnh t chy han ton 1 mol cht bng O2 to thnh cc oxit 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).

1.4 NH LUT HESS V CC H QU


1.4.1 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.

1.4.2 Cc h qu
H qu 1: Hiu ng nhit ca phn ng thun bng hiu ng nhit ca phn ng nghch nhng ngc du. 8

H qu 2: Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc cht cui tr i tng nhit sinh ca cc cht u.

T nh ngha ny suy ra: Nhit sinh ca mt n cht bn vng iu kin chun bng khng:

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.

1.4.3 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 d 1: Khng th o c nhit ca phn ng Cgr + 1/2O2(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:

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

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:

V d 2: Xc nh nng lng mng lui tinh th ca NaCl(r) bit

xc nh nng lng mng li tinh th NaCl ta dng chu trnh nhit ng Born Haber:

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1.5 S PH THUC HIU NG NHIT VO NHIT . NH LUT KIRCHHOFF


1.5.1 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, ...).

1.5.2 Nhit chuyn pha


Chuyn pha: bay hi ,nng chy, ng c, thng hoa, ...

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Hcf 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.

1.5.3 nh lut Kirchhoff


Xt 1 h kn, P = const. Xt phn ng sau thc hin bng hai con ng:

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1.5.4 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 d 1: Ph v 1 mol thnh cc nguyn t c lp:

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Chng 2 NGUYN L TH HAI NHIT NG HC, CHIU V GII HN T DIN BIN CA QU TRNH
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2.1

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 th nht cho php tnh nhit ca cc phn ng nhng khng cho php tin on chiu v gii hn ca qu trnh. Nguyn l th hai cho php gii quyt cc vn ny.

2.2 NGUYN L TH HAI NHIT NG HC. HM ENTROPY


Nguyn l th hai (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: Nu l bin i thun nghch:

2.2.1

Nu l bin i bt thun nghch:

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Tng qut

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

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:

2.2.2

Nguyn l th hai 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. 15

Nu dS = 0, d2S < 0 (S max) h trng thi cn bng.

2.2.3

ngha hm entropy
Entropy l thc 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 S 2 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 --> S ln. Lin kt gia cc ht trong h cng yu --> hn n cng ln --> S ln. V d

S l hm trng thi v l i lng dung . 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. 16

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 th ba). S = kln k: hng s Boltzmann Nhn xt: Trong h c lp, qu trnh t din bin theo chiu tng xc sut nhit ng .

2.2.4

Bin thin entropy ca mt s qu trnh


Bin thin entropy 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:

Bin thin entropy ca qu trnh gin n ng nhit kh l tng T = const, dn n n mol kh l tng t V1-->V2

Nu P1 > P2 --> S > 0: qu trnh gin n ny t din bin. ==> Cch pht biu khc ca nguyn l th hai: Cc cht kh c th t chuyn di t ni c p sut cao n ni c p sut thp. Bin thin entropy ca cht nguyn cht theo nhit

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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

Trong iu kin V= const

2.3 NGUYN L TH BA 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.

2.3.1

Nguyn l th ba (tin Nernst)


Entropi ca mt cht nguyn cht di dng tinh th hon ho OK bng khng:

2.3.2

Entropy 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 S T?

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Nhn xt: Gi tr S cht nguyn cht lun > 0, tr khi xt cho ion trong dung dch, c th c Sion < 0.

2.3.3

Bin thin entropy ca cc phn ng ha hc


V S l hm trng thi v l i lng dung nn:

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.

2.4 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.

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H khng c lp: gm h + Mi trng --> a v 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 + Smt 0. Smt cha xc nh nhng c th a v cc thng s ca h bng cch tm 1 hm thay th cho c (S + Smt), 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.

2.4.1

Hm th ng nhit ng p
nh ngha Xt 1 h: T, P = const H thc hin mt bin i no .

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

ngha vt l ca G

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l phng trnh c bn ca nhit ng hc. Nu qu trnh l thun nghch --> cng l ln nht --> du =.

T v P = const => dT = 0 v dP = 0 c:

ngha ca G: G biu th cng hu ch ca qu trnh thun nghch ng nhit ng p.

2.4.2

Hm th ng nhit ng tch
nh ngha Xt 1 h T, V = const, h thc hin 1 bin i no .

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

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ngha A

Nu qu trnh l thun nghch --> cng l ln nht --> du =.

T v V =const => dT = 0 v dV = 0 c:

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:

Mi lin h gia G v A:

2.4.3

Bin thin th ng p

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=> 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) 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.

Tnh bin thin th ng p ca phn ng ha hc V G l hm trng thi v l i lng dung nn c:

Nu iu kin chun v 25C 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

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2.5 CC YU T NH HNG N TH NG P
nh hng ca nhit
Xt h: Ch c bin i thun nghch, khng sinh cng c ch, c P = const.

2.5.1

Phng trnh Gibbs - Helmholtz cho php xc nh G theo T:

Thng xt iu kin chun (p = 1atm) v T = 298K:

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2.5.2

nh hng ca p sut
Xt h: Bin i thun nghch, khng sinh cng hu ch, T = const.

i vi cht rn v cht lng --> coi V = const khi P bin i (tr min P ln) nn:

i vi cht kh (coi l kh l tng) --> V =

nRT P

V d: Nn 0,5 mol kh l tng t P = 1 atm n P = 2 atm 25C. Hi qu trnh nn c t xy ra c khng? 25

2.5.3

nh hng ca thnh phn cc cht. Khi nim th ha

ngha vt l ca i

Mt vi tnh cht ca th ho

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=> th ho cng l tiu chun xt chiu v gii hn ca cc qu trnh (phn ng xy ra theo chiu gim th ho).

2.5.4

Mi quan h gia du G v ln H, S v T

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V d

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Chng 3 CN BNG HA HC
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3.1

PHN NG THUN NGHCH V PHN NG 1 CHIU


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).

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.

Phn ng mt 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.

Trng thi cn bng ha hc


Mt phn ng khi t trng thi cn bng th: Xt v mt ng hc: vt = vn Xt v mt nhit ng: Gp = 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).

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Ti trng thi cn bng thnh phn ca cc ch t 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, t, p) khng i.

3.2 PHNG TRNH NG NHIT VANT HOFF. HNG S CN BNG K


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

Pi: p sut ring phn ca cc cht kh i = A, B, C, D

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Cc phng trnh (*) (**) v (***) c gi l cc dng khc nhau ca phng trnh ng nhit Vant Hoff

Phng trnh hng s cn bng K


Hng s cn bng Kp

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. Cc hng s cn bng khc

Ci: nng mol/lit cc cht trng thi cn bng. Kc ph thuc vo bn cht phn ng v nhit . 31

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 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.

KN ph thuc vo bn cht cc cht, T v P chung ca h khi cn bng. Mi quan h gia cc hng s cn bng

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Cc phng php xc nh hng s cn bng


Xc nh theo thnh phn cc cht ti thi im cn bng V d: CaCO3(r) <=> CaO(r) + CO2(k)

Xc nh thng qua 1 s i lng nhit ng

V d: Tnh Kp ca phn ng sau 25C:

Xc nh theo phng php gin tip: Phn tch qu trnh theo 1 chu trnh kn V d 34

3.3 S CHUYN DCH CN BNG. NGUYN L LE CHATIELIER


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.

3.3.2 nh hng ca nhit ti s chuyn dch cn bng. Phng trnh ng p Vant Hoff
Xt phn ng: aA + bB <=> cC + dD P = const

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Khi nhit tng --> Kp tng --> cn bng chuyn dch theo chiu thun (chiu thu nhit). nhit). Nu T gim --> Kp gim ==> cn bng chuyn dch theo chiu nghch (chiu to

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 HT > 0. Khi nhit gim th cn bng chuyn dch theo chiu lm tng nhit ca h l chiu to nhit c HT < 0. T phng trnh Vant Hoff suy ra:

36

3.3.3 nh hng ca p sut n s chuyn dch cn bng

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 < 0). Nu P gim => cn bng chuyn dch theo chiu tng P (tng s mol kh n > 0). n

3.3.4 nh hng ca nng

Nu tng CA, CB => cn bng chuyn dch theo chiu tng CC, CD ( gi = const) => cn bng chuyn dch theo chiu thun lm gim CA, CB.

KC

37

Nu gim CA, CB => cn bng chuyn dch theo chiu gim CC, CD ( gi = const) => cn bng chuyn dch theo chiu nghch lm tng CA, CB.

KC

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.

3.3.5 Nguyn l chuyn dch cn bng Le Chatielier


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 .

38

Chng 4 CN BNG PHA


------

4.1

MT S KHI NIM
Pha
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 pha rn + 1 pha kh

Cu t
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

S cu t c lp K
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 39

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).

=> 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.

Bc t do ca h C
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 aei 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.

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 aei pha ca cc cu t => cn bng pha.

4.2

QUY TC PHA GIBBS


Xt h gm R cu t 1,2, ... R c phn b trong pha (, , , ..., pha).

iu kin cc pha nm cn bng vi nhau


m bo cc cn bng sau: - Cn bng nhit: nhit cc pha bng nhau: 40

- Cn bng c: p sut cc pha bng nhau:

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

Quy 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).

=> 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. 41

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 d 1: 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 1 nhit xc nh th P ca hi nc l xc nh) V d 2: 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 2O ( h ) .

4.3

CN BNG PHA TRONG H 1 CU T


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:

42

=> 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 pha Tcf, nhit ny khng b bin i trong sut qu trnh chuyn pha. Khi p sut thay i => Tcf thay i theo. V d: P = 1atm, nc nguyn cht ng c 0C v si 100C P = 2atm, nc nguyn cht ng c 0,0076C v si 120C - 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:

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.

4.3.2 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:

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:

43

4.3.3 nh hng ca nhit n p sut hi bo ha ca cht nguyn cht

44

45

Chng 5 DUNG DCH


--- ---

5.1

H PHN TN
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. V d: 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: H phn tn th Kch thc ht t 10-7-10-4 m - c im: Khng bn,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. Dung dch keo
Kch thc ht t 10-7 10-9 m c im: tng i bn.

Dung dch thc (dung dch) Kch thc ht 10-10 m (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. 46

c im: H ny rt bn.

Cc loi nng

5.2

NG LNG
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

nh ngha ng lng
- 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.

Cch tnh ng lng


ng lng ca nguyn t

47

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. ng lng ca hp cht

nh lut ng lng

48

5.3

HA TAN
Qu trnh ha tan. Nhit ha 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 :

49

nh hng ca bn cht cht tan v dung mi n S

nh hng ca nhit n tan

50

nh hng ca P (i vi cht kh). nh lut Henry

5.4

TNH CHT CA DUNG DCH

51

p sut hi bo ha ca dung dch. nh lut Rault I

p sut hi bo ha ca dung mi nguyn cht ( P o ) 1

p sut hi bo ha ca dung dch P1

52

nh lut Rault I

5.4.2 Nhit si v nhit ng c ca dung dch. inh lut Rault II


Nhit si ca dung dch

53

Nhit ng c ca dung dch cha cht tan khng bay hi

5.4.3 S thm thu v p sut thm thu


S thm thu

p sut thm thu

54

55

Chng 6 DUNG DCH CHT IN LY


------

6.1

TNH CHT CA DUNG DCH IN LY


Cht in ly

Cht in ly mnh

Cht in ly yu

56

6.1.4 Tnh cht bt thng ca dung dch cht in ly so vi dung dch cht khng in ly

6.2

IN LY

6.2.1 nh ngha

57

6.2.2 Cch xc inh

58

6.3

CN BNG TRONG DUNG DCH CHT IN LY YU


6.3.1 Hng s in ly

6.3.2 Mi lin h gia K v . nh lut pha long Ostwald

59

6.3.3 Dch chuyn cn bng trong dung dch cht in ly yu

6.4

THUYT AXIT-BAZ CA BRONSTED


6.4.1 nh ngha axit-baz

60

6.4.2 Tch s ion ca nc ch s hydro (pH)

6.4.3 Hng s in ly axit-baz


Hng s in ly ca axit Ka

Hng s in ly ca baz Kb

61

6.4.4 Mi lin h gia Ka, Kb ca mt cp axit-baz

6.4.5 Ch s hydro pH

62

6.5

TNH pH CA CC DUNG DCH AXIT-BAZ-MUI


6.5.1 Tnh pH ca dung dch axit mnh 1 bc

6.5.2 Tnh pH ca dung dch baz mnh 1 bc

63

6.5.3 Tnh pH ca axit yu 1 bc

64

6.5.4 Tnh pH ca baz yu 1 bc

6.5.5 Tnh pH ca dung dch mui

65

66

67

6.5.6 Tnh pH ca dung dch axit nhiu bc

6.6 CN BNG TRONG DUNG DCH CHT IN LY T TAN


6.6.1 Tch s ha tan ca cht in ly t tan

6.6.2 Mi quan h gia tch s tan Ks v ha tan S

68

6.6.3 iu kin to thnh kt ta v ha tan kt ta

69

70

Chng 7 NG HA HC
------

7.1

KHI NIM V VN TC PHN NG


nh ngha vn tc phn ng

71

Cc yu t nh hng ln vn tc

7.2

THUYT VA CHM HOT NG


Ni dng

Phn b Boltzman

72

7.3 NH HNG CA NNG CC CHT THAM GIA PHN NG N VN TC V NH LUT TC DNG KHI LNG
nh lut tc dng khi lng

Bc phn ng

73

7.4 NH HNG CA NHIT LN VN TC PHN NG


Quy tc Vant Hoff

74

Phng trnh Arrhenius

75

7.5 NH HNG CA XC TC LN VN TC PHN NG


nh ngha

76

c im xc tc

Gii thch c ch ca xc tc
i vi xc tc ng th

77

i vi xc tc d th

7.6 CC PHNG TRNH NG HC CA PHN NG HA HC

Phn ng bc mt

78

Cc phn ng bc hai

79

Chng 8 CC QU TRNH IN HA
------

8.1

NGUYN TC BIN HA NNG THNH IN NNG


Phn ng oxy ha kh

Nguyn tc bin ha nng thnh in nng

80

Cu to hot ng ca pin Cu-Zn


Cu to

Hot ng

8.2

CC LOI IN CC
in cc kim loi

81

in cc tr nhng trong dung dch cha cp oxy ha kh

in cc kh

82

8.3

SUT IN NG CA PIN
nh ngha

Cc yu t nh hng n E cng thc Nernst

83

8.4

TH IN CC (TH KH)
Cp oxy ha kh

Th kh

84

85

Cc yu t nh hng n th in cc

86

8.5 CHIU V TRNG THI CN BNG CA PHN NG OXY HA KH XY RA TRONG DUNG DCH NC
Chiu ca phn ng oxy ha kh

87

88

Trng thi cn bng ca phn ng oxy ha kh

8.6 QU TRNH IN PHN


nh ngha

89

S phn cc

S phn cc v nng

S phn cc ha hc

S phn cc in ha

90

Th phn hy

S in phn cht in ly nng chy

in phn dung dch cc cht in ly

Qu trnh catod

91

Qu trnh anod

TI LIU THAM KHO


------

92

(1) Ho i cng Nguyn nh Soa Trng i hc Bch Khoa Thnh ph H Ch Minh. (2) Ho V c (Tp 1) Hong Nhm Nh xut bn Gio dc. (3) Ho i cng N. L. Glinca (bn dch) Nh xut bn Gio dc.

93

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