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Gio trnh C s l thuyt ho hc c vit nhm phc v cho mn hc ny bc i hc thuc cc chuyn ngnh k thut (xy dng, mi trng, c kh, nhit, in...), h o to chnh quy tp trung. Gio trnh trnh by tp hp cc khi nim, nh ngha, l thuyt, quy lut bin i... trong ho hc nhm cung cp cho ngi hc nhng kin thc c bn nht v ho hc vn dng trong cc lnh vc chuyn mn ca mnh. Gio trnh gm c 9 chng. Bn chng u (1 4) trnh by cc vn v bn cht cu to ca nguyn t, phn t; quan h ph thuc v s bin i cc tnh cht vt l, ho hc ca cc hp cht vo quy lut sp xp electron trong cc nguyn t, phn t. Da trn c s cc quy lut bin i , nu ln ngha ca bng bin thin tun hon cc nguyn t di nh sng ca thuyt c hc lng t hin i. Chng 5 7 trnh by cc vn v nhit ng v ng ho hc. Ba nguyn l nhit ng hc c trnh by n gin nhm mc ch ng dng trong cc h ho hc. Phn ng hc v cn bng ho hc a ra mt s cng thc tnh vn tc phn ng, hng s cn bng v yu t nh hng n cc i lng . Chng 8 chng dung dch trnh by cc vn v qu trnh ho tan, nng , pH...; mi quan h gia cc loi dung dch vi nhau. Mt s vn lin quan n cc qu trnh bin i in ho c trnh by trong chng cui cng chng 9. T cc m hnh th nghim bin i ho nng thnh in nng v in nng thnh ho nng a ra cc phng php tnh, quy lut bin i th in cc, in phn... v trn c s nu ln mt s ng dng c bn ca cc qu trnh in ho. Gio trnh ny c bin son ln u tin nn chc chn cn nhiu thiu st. Tc gi rt mong nhn c cc kin nhn xt ca cc bn ng nghip, anh ch em sinh vin v cc c gi. Nng 7 - 2006 o Hng Cng
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Mc lc
Trang Chng 1. M u . ..............................................................................................1 1.1. Ho hc v nhim v ca ho hc . ............................................................2 1.2. Mt s khi nim c bn trong ho hc . ...................................................2 1.3. Mt s n v o trong ho hc. .................................................................2 Chng 2. Cu to nguyn t . .....................................................................................6 2.1. Nguyn t . ................................................................................................6 2.2. M hnh nguyn t c ht nhn. .................................................................6 2.3. M hnh nguyn t ca Bohr . ....................................................................9 2.4. Thuyt c hc lng t v cu to nguyn t . ..........................................9 Chng 3. S bin thin tun hon cu to nguyn t. Bng h thng tun hon Meneleep . .....................................................18 3.1. S bin thin . ...........................................................................................18 3.2. Bng h thng tun hon cc nguyn t ho hc Meneleep . .................22 Chng 4. Lin kt ho hc . .....................................................................................28 4.1. Mt s khi nim c bn ca lin kt ho hc . .......................................28 4.2. Lin kt ion . ............................................................................................30 4.3. Lin kt cng ho tr . ..............................................................................32 4.4. Cu to phn t . ......................................................................................42 Chng 5. Nhit ng ho hc . .................................................................................57 5.1. Mt s khi nim c bn v nhit ng hc . ...........................................47 5.2. Pht biu nguyn l I nhit ng hc . ....................................................50 5.3. Nhit ng tch, ng p . ........................................................................51 5.4. nh lut Hess v cch xc nh nhit phn ng theo h qu ca nh lut Hess . .................................................................................53 5.5. S ph thuc ca hiu ng nhit vo nhit . ........................................55 5.6. Nguyn l II nhit ng hc. Entropi . .....................................................57 5.7. Nguyn l III nhit ng hc. Entropi tuyt i . ....................................61 5.8. Th ng nhit - ng p . ........................................................................62 Chng 6. ng ho hc . .............................................................................................65 6.1. Vn tc phn ng ho hc . ......................................................................65 6.2. Cc yu t nh hng n vn tc phn ng ............................................66
Chng 7. Cn bng ho hc v cn bng pha . ...........................................................70 7.1. Cn bng ho hc . ...................................................................................70 7.2. Hng s cn bng . ....................................................................................70 2
7.3. S chuyn dch cn bng. Nguyn l chuyn dch cn bng Le Chatelier . ........................................72 7.4. Cn bng pha . ...........................................................................................75 Chng 8. Dung dch . ..................................................................................................78 8.1. Mt s khi nim chung . .........................................................................78 8.2. Tnh cht ca dung dch cht khng in li . ..........................................86 8.3.Tnh cht ca dung dch cht in li . .......................................................90 8.4. Thuyt axt - baz . ...................................................................................95 8.5. Cht ch th mu . ...................................................................................103 8.6. Tch s ho tan . .....................................................................................104 8.7. Dung dch keo . ......................................................................................105
Chng 9. Phn ng oxi ho kh v in ho . ........................................................110 9.1 Phn ng xi ho kh. Cp xi ho - kh . ...........................................110 9.2. Th xi ho kh trong dung dch. th tiu chun . .................................110 9.3. Qa trnh bin i ho nng thnh in nng . ...................................120 9.4. Pin v acquy ..........................................................................................126 9.5. n mn in ho v cch chng n mn in ho . ..............................129
Chng 1 M U
1.1. HO HC V NHIM V CA HO HC: Ho hc l mt trong nhng mn khoa hc c bn nghin cu cc quy lut v hnh thc vn ng, bin i ca th gii t nhin: trong qu trnh phn ng ho hc mt cht b mt i v thay vo l xut hin mt cht mi. Trong qu trnh ny va xy ra s bin i thnh phn ca hp cht (thay i thnh phn nguyn t ca phn t), va xy ra s thay i v cu to ca phn t. Do vy, nhim v ca ho hc l nghin cu cc hnh thc vn ng, cc quy lut bin i ca vt cht trn c s tm cch iu khin chng. Cc qu trnh ho hc xy ra lun km theo cc hin tng vt l. V d, nh sng s pht ra khi t chy magie, nng lng s thot ra khi t chy nhin liu. Trong nguyn t ganvani, qu trnh ho hc chnh l nguyn nhn gy ra dng in.... V vy nghin cu nhng hin tng ny cng chnh l mt trong nhng nhim v ca ho hc. Ho hc cn c mt nhim v rt c bn, quan trng na l thu nhn, tng hp cc hp cht ho hc phc v thit thc cho i sng con ngi nh: kim loi, hp kim, phn bn, thuc cha bnh, thuc nhum, hp cht cao phn t, nhin liu, thu tinh, cao su, hng liu, thc phm... nc ta hin nay, vic thc hin bn Chng trnh trng im Quc gia trong c hai chng trnh (cng ngh vt liu v cng ngh ch bin sau thu hoch) ang t ra cho ngnh ho hc nhng c hi v thch thc to ln trong qu trnh pht trin ca mnh. 1.2. MT S KHI NIM C BN TRONG HO HC:
1.2.1. Vt cht: Vt cht l mt khi nim tng qut, chung (ting Latinh: mater rerum ngi m ca mi vt). Vt cht tn ti di hai hnh thc: cht v trng.
- Cht l tng hp nhng cu thnh gin on c khi lng tnh di dng ht nh electron, proton, ntron, nguyn t, phn t... - Trng l lc tng tc gia cc vt, cc tia... c c trng bng tnh lin tc (truyn i trong khng gian di dng sng) v c khi lng tnh bng khng. 1.2.2. Nguyn t, phn t, cht ho hc: a) Nguyn t l phn t nh nht ca nguyn t ho hc c trong thnh phn ca n cht v hp cht. b) Phn t l ht vi m i din cho cht c kh nng tn ti c lp v mang y tnh cht ho hc ca cht. Do vy, nu phn t b chia nh th n khng cn c tnh cht ho hc ca cht. Thng thng, phn t gm 2 nguyn t tr ln lin kt vi nhau (ngoi tr kh tr gm 1 nguyn t). Nhng nguyn t ny c th l cng loi nh phn t oxi hay khc loi nh phn t nc, phn t kh cacbonc... Cc n cht ca mt kim loi l tp hp nhng nguyn t ca kim loi , v vy trong kim loi, nguyn t cng chnh l phn t. 1.3. MT S N V O TRONG HO HC: Cng nh cc ngnh khoa hc khc, ho hc s dng tt c cc n v o ca H thng o lng quc t (SI). Ngoi ra ho hc cn s dng mt s n v o ring nh sau: 1.3.1. n v khi lng nguyn t, phn t n v khi lng nguyn t (n v cacbon - .v.C) c khi lng bng 1/12 khi lng ca nguyn t cacbon 12C. Nh vy, 1 n v khi lng nguyn t = 1 .v.C = 1,66.10-27kg, c ngha l trong 1 gam c cha 6,022.1023 .v.C. Ga tr 6,022.1023 c gi l s Avogaro (NA). * Khi lng nguyn t tng i ca nguyn t: Khi lng nguyn t tng i ca nguyn t l khi lng trung bnh tnh theo .v.C ca nguyn t ca nguyn t . T gi tr ny s tnh ra c khi lng nguyn t kilogam (theo n v SI). V d, khi lng tng i ca nguyn t lu hunh bng 32 c ngha l khi lung ca mt nguyn t lu hunh l 32 .v.C tng ng vi: 5
1,66.10-27kg 32 = 53,12.10-27kg. * Khi lng phn t tng i ca hp cht: Khi lng phn t tng i ca hp cht l khi lng trung bnh tnh theo .v.C phn t ca hp cht. T gi tr ny s tnh ra c khi lng phn t kilogam (theo n v SI). V d, khi lng phn t tng i ca CaCO3 bng 100 c ngha l mt phn t CaCO3 c khi lng 100 .v.C, tng ng vi: 1,66.10-27kg 100 = 1,66.10-25kg. 1.3.2. Mol: Mol l lng vt cht cha 6,022.1023 ht vi m (phn t, nguyn t, ion, electron, photon...). * Mol nguyn t: Mol nguyn t l gi tr tnh ra gam ca khi lng nguyn t tng i ca nguyn t (n chnh bng s .v.C nguyn t tnh ra gam). V d, t khi lng tng i ca nguyn t Na bng 23 suy ra khi lng mt mol nguyn t Na l 23 gam. * Mol phn t: Mol phn t l tng khi lng ca 6.1023 phn t ca hp cht tnh ra gam (n chnh bng s .v.C ca phn t tnh ra gam). V d, t khi lng tng i ca phn t ng glucoz C12H22O11 l 342 suy ra khi lng mt mol phn t glucoz l 342 gam. 1.3.3. ng lng: - ng lng ca mt nguyn t l s lng nguyn t c th kt hp hoc thay th mt mol nguyn t hyro trong phn ng ho hc. V d, trong cc hp cht HCl, H2O, PH3, CH4 ng lng ca cc nguyn t Cl, O, P, C ln lt l 1, 1/2, 1/3, 1/4 mol nguyn t ca nguyn t . - Khi lng ng lng () hay cn gi l ng lng khi ca mt nguyn t l khi lng tnh ra gam ca mt ng lng ca nguyn t . - Cch tnh ng lng khi: + ng lng khi ca mt nguyn t bng khi lng nguyn t (AZ) ca nguyn t chia cho ho tr (n) ca n: 6
Z =
Z n
(1-1)
Trong trng hp nguyn t c nhiu ho tr th Z cng c nhiu gi tr khc nhau. V d, Fe c hai ho tr (2, 3) nn Fe s c cc gi tr 56/2, 56/3. + ng lng khi ca mt baz bng khi lng phn t ca baz (MB) chia cho s nhm OH (n) ca n: B =
B n
(1-2)
+ ng lng khi ca mt axit bng khi lng phn t ca axit (MA) chia cho s nguyn t H (n) ca n: A =
A n
(1-3)
Trong trng hp axit c nhiu nguyn t hyro tham gia phn ng th n c tnh bng s nguyn t H tham gia vo phn ng ho hc . V d, A ca H3PO4 (M = 98) trong 3 phn ng sau: H3PO4 + NaOH H3PO4 + 2NaOH H3PO4 + 3NaOH ln lt l 98/1, 98/2, 98/3. + ng lng khi ca mt xit bng khi lng phn t ca xit (MO) chia cho (n) tch ca s nguyn t xi vi 2 (tng ho tr ca kim loi trong cng thc ca oxit): O =
O n
= NaH2PO4 + H2O = Na2HPO4 + 2H2O = Na3PO4 + 3H2O
(1-4)
+ ng lng khi ca mt mui bng khi lng phn t ca mui (MM) chia cho (n) tch ca s nguyn t kim loi nhn vi ho tr ca n: M = 1.3.4. S xi ho S xi ho (ch s xi ho, bc xi ho) l gi tr in tch nguyn t ca mt nguyn t c c nu gi s rng tt c cc lin kt vi nguyn t u l lin kt ion. 7
n
(1-5)
S xi ho c trng cho kh nng chuyn dch in t t mt nguyn t ny sang mt nguyn t khc. S xi ha c cc gi tr m, dng hoc bng khng. S xi ho cao nht ca mt nguyn t chnh bng ch s nhm m nguyn t chim ch trong bng tun hon Meneleep. xc nh s xi ho trong ho hc ngi ta s dng cc quy tc sau: 1. S xi ho cc nguyn t trong cc n cht bng khng. V d, N2, S, Cr ... ). 2. Kim loi lun lun c s xi ho dng. S xi ho ca kim loi kim lun lun bng +1. 3. Hyro lun c s xi ho +1, tr cc hp cht hyrua (NaH, CaH2, ...) hyr c s xi ho -1. 4. xi lun c s xi ho bng -2, tr cc hp cht peoxit cha nhm OO ( H2O2, Na2O2, ...), trong xi c s xi ho bng -1. 5. S xi ho ca cc nguyn t cn li c th c gi tr dng hoc m. 6. Tng cc gi tr s xi ho ca cc nguyn t trong mt phn t bng khng.
Chng 2 CU TO NGUYN T
2.1. NGUYN T C s l thuyt c bn nht v cu to vt cht - l kh nng phn chia vt l cc cht thnh nhng phn nh m mi phn vn gi nguyn tnh cht ho hc ca n. Cc phn nh c gi l phn t. Nu tip tc phn chia phn t th nhn c nhng phn nh hn - l nhng nguyn t. Mt lot cc pht hin vo cui th k th XIX v u th k th XX cho thy rng nguyn t c cu to rt phc tp. Khi cho dng in i qua cht kh v cht lng ngi ta nhn thy trong c phn t ln nguyn t u c mt thnh phn chung - l in t. Bng phng php dng catt xc nh c in t c khi lng 9,1095. 10-28gam v c in tch -1,6.10-19 Culong. Bng phng php cho dng in i qua dung dch in li cng m ra cc nh lut in phn v pht hin ra s tn ti cc nguyn t mang in tch dng v mang in tch m (cc cation v anion). Kt qu cc thc nghim trn y cho thy rng nguyn t c cu to rt phc tp t mt thnh phn l in t mang in tch m v mt phn khc mang in tch dng. Vy vn t ra l quan h sp xp nh th no gia in vi phn mang in tch dng ca nguyn t? tr li cu hi ny, trn c s ca cc th nghim cc nh khoa hc ngh cc m hnh cu to nguyn t. 2.2. M HNH NGUYN T C HT NHN: 2.2.1. M hnh Thomson Thomson nhn thy rng khi dng mt chm tia X bn ph qua l kim loi mng th chm tia X b tn x khng ln lm khi hng i ban u. T th nghim ny Thomson ngh m hnh : Nguyn t l mt hnh cu in tch dng c gn vi nhng ht electron in tch m. Cc phn t tch in dng cng nh cc electron phn tn u trong mt khi cu trn cc lp v ng tm khc nhau. 9
2.2.2. M hnh Hagaoka : Hagaoka cho rng nguyn t c cu to ging nh sao Th v cc qu o chuyn ng ca n. Ngha l gm mt hnh cu mang in tch dng v cc electron chuyn ng theo nhng qu o trn xung quanh. 2.2.3. M hnh Rozfo (Rutherforrd). Rozfo lm th nghim bn ph qua l vng mng bng chm tia a (hnh 2.1).
Hnh 2.1. S tn x ca tia a
Kt qu th nghim cho thy c mt s tia a b lch khi hng ban u, mt s tia b quay tr li nhng c gc lch nh hn so vi lch ca electron trong th nghim ca Thomson. T th nghim ny, Rozfo cho rng phn in tch dng trong nguyn t c khi lng ln nhng c bn knh nh. Rozfo t tn cho phn ny l ht nhn. Rozfo ngh m hnh cu to nguyn t gm ht nhn nm trung tm nguyn t, xung quanh c cc electron chuyn ng trn nhng qu o ging nh cc hnh tinh quay quanh mt tri. u im: cc m hnh nguyn t trn y u cho thy cu to ca nguyn t gm c hai phn c bn: vng trung tm in tch dng (ht nhn) v vng chuyn ng xung quanh ht nhn mang in tch m (electron). Nhc im: C hai nhc im chnh: - Khng gii thch c bn vng ca nguyn t. Khi quay quanh ht nhn, electron cn phi bc x mt phn nng lng di dng sng in t. iu ny dn n s mt cn bng gia lc ht tnh in ca electron vi ht nhn v lc hng tm. Kt qu l electron b gn vo ht nhn, chuyn ng b trit tiu. - Khng gii thch c ph ca nguyn t - vch nh sng cha tt c cc mu sc ca cu vng. Theo m hnh ca Rozfo, electron bc x nng lng mt cch lin tc nn 10
ph ca n cng phi c cc vch lin tc cch u nhau. Thc t cho thy rng, ph ca cc nguyn t khng phi l nhng vch lin tc cch u nhau (hnh 2.2).
o H 700 650 600 550 Xanh H 500 450 H H 400 T m H
8
350 nm
Hnh 2.2 Ph ca nguyn t hyro
Mt khc, cc nguyn t khc nhau c ph nguyn t hon ton khc nhau. 2.3. M HNH NGUYN T CA BOHR 2.3.1. Thuyt Planck v lng t nng lng Nm 1900, khi quan st hin tng hp th v bc x nh sng ca cc vt en tuyt i, Planck nhn thy rng nh sng tham gia tng phn nh nng lng vo cc hin tng trn. Nhng phn nh nng lng ny Planck gi l cc lng t nng lng. Trn c s ca pht hin ny, Planck a ra gi thuyt: Nng lng bc x c gii phng hoc hp th di dng nhng nng lng gin on gi l cc lng t nng lng . = h = - bc sng - tn s bc x h - hng s Planck (6,63.10-34 J.s) c - vn tc nh sng (300.000 km/s). * M hnh cu to nguyn t ca Bohr Vn dng thuyt lng t ca Planck, Bohr ngh mt m hnh cu to nguyn t trong cc in t: - Chuyn ng trn nhng qu o xc nh v khi quay trn cc qu o nng lng c bo ton (trng thi dng).
hc
(2-1)
11
- Mi qu o ng vi mt mc nng lng c xc nh bi nng lng ca nguyn t. Vi nguyn t hyro mc nng lng ca electron c tnh theo cng thc sau: En = -13,6
1 (eV) trong : n = 1,2,3... n2
(2-2)
- Qu o gn ht nhn nguyn t c nng lng thp, qu o xa c nng lng cao. Khi electron chuyn t qu o ny sang qu o khc s xy ra s hp th hoc gii phng nng lng: e = h = En - En, u im m hnh nguyn t ca Bohr: - Gii thch c ph vch ca hyro v cc nguyn t tng t hyro. - Tnh c bn knh ca nguyn t hyro (rH). Nhc im: - Khng gii thch c ph ca cc nguyn t phc tp, c nhiu electron v nh hng ca ph di tc dng ca trng in t. - Thuyt Bohr c tnh cht c on. 2.4. THUYT C HC LNG T V CU TO NGUYN T: 2.4.1. Tnh cht sng v ht ca nh sng: Vo cui th k th XIX u th k th XX, cc nh khoa hc vt l kt lun nh sng mang tnh cht lng tnh: - nh sng mang tnh cht ht: l tp hp ca cc photon (ht) c khi lng m, c xc nh bng ng nng: e = mc2. nh sng mang tnh cht sng: th hin qua cc hin tng nhiu x, giao thoa vi vn tc truyn sng: c = lg Mi quan h tnh cht sng ht (quan h nh nguyn) c biu th bng biu thc Enstein-Planck sau: l =
h mc
(2-3)
(2-4)
12
2.4.2. Tnh cht sng ca cc ht vi m: Khi nghin cu tnh cht chung v chuyn ng ca vt cht, Broglie nhn thy rng tnh sng - ht khng phi ch tn ti duy nht nh sng m n c bt k mt ht no khc. Trn c s nhn nh ny, Broglie a ra gi thuyt: mi vt cht chuyn ng u c th coi nh qu trnh sng c trng bng bc sng l c tnh theo h thc De Broglie: =
h mv
(2-5)
m khi lng ca ht v - vn tc chuyn ng ca vt cht Tnh cht sng - ht ny c tt c cc ht vi m: electron, proton... 2.4.3. Nguyn l bt nh ca Heisenberg: V c tnh sng - ht nn v nguyn tc khng th xc nh ng thi chnh xc c ta ln vn tc chuyn ng ca ht. Do khng th v hon ton chnh xc qu o chuyn ng ca ht. iu ny c th hin qua nguyn l bt nh ca Heisenberg: X . VX
h m
(2-6)
trong : X - sai s php o ta VX - sai s php o vn tc V b gii hn bi h/m nn nu DX cng nh ( php o ta cng chnh xc) th VX cng ln (php o vn tc cng khng chnh xc). 2.4.4. Khi nim v c hc lng t: 2.4.4.1. Hm sng: V chuyn ng ca electron c tnh cht sng nn c hc lng t biu din s chuyn ng ca electron trong nguyn t bng hm sng Y (x,y,z,t) trong x, y, z l cc gi tr to ca im, t l thi gian. V ngha vt l ca hm sng n nay cha c xc nh nhng i lng Y2dV l xc sut tm thy ht ti thi im t, trong yu t th tch dV = dxdydz c tm l M(x,y,z). 13
din t trng thi tn ti ca electron trong nguyn t ngi ta s dng m hnh m my in t. m my in t thng c biu din di dng mt b mt c gii hn (xc sut tm thy in t trong gii hn ny l khong 90%). Khong khng gian xung quanh ht nhn nguyn t m xc sut tm thy in t l ln nht c gi l orbital. Vic tnh xc sut tm thy in t ti mt im trong nguyn t hoc phn t v xc nh nng lng ca n l mt vn rt phc tp. Vn ny c th gii quyt bng s gip ca phng trnh sng Schrodinger. 2.4.4.2. Phng trnh sng Schrodinger: Phng trnh sng Schrodinger (1926) biu th mi quan h gia th nng U ca in t v nng lng ton phn E ca n: 2 + trong :
2
8 2 m (E - U) = 0 h2
2 + y 2 2 + z 2
(2-7)
2 = x 2
m - khi lng ca in t h - hng s Planck Nghim ca phng trnh sng Schrodinger l cc hm s 1, 2, 3, .... n tng ng vi cc mc nng lng E1, E2, E3, .... En. Nh vy, t nghim ca phng trnh sng Schrodinger s tnh c lng t nng lng ca cc ht vi m . A0 l nghim ca phng trnh Schrodinger. A0 = 1. 2n A0 = (n,l,m) 2.4.5. Orbital nguyn t (AO). Cc s lng t: Orbital nguyn t c th vit di dng cc s nguyn c gi l cc s lng t: n s lng t chnh l s lng t orbital (s lng t ph). m s lng t t. 14
Cc s lng t ny l nhng tham s trong cc nghim ca phng trnh sng Schrodinger. 2.4.5.1. S lng t chnh Nng lng En tng ng vi nghim n ca phng trnh sng Schrodinger ca nguyn t hyro c dng: En = 2 m e 4 n2h2
(2-8)
trong m khi lng in t e - in tch ca in t n s nguyn bt k t 1 n c gi l s lng t chnh v c k hiu thnh cc lp tng ng: S lng t chnh n : Lp: 1 2 3 4... . K L M N . ...
Nh vy, s lng t chnh n xc nh nng lng ca cc lp in t. Trng thi lng t ca nguyn t c mc nng lng thp nht E1 (tng ng vi lp n = 1) c gi l trng thi c bn. Cc trng thi lng t ca nguyn t c mc nng lng cao hn E2, E3, ... c gi l cc trng thi kch thch. 2.4.5.2. S lng t orbital: S lng t orbital l (s lng t ph) l tham s c trng cho hnh dng ca cc orbital tc l hnh dng ca cc m my in t c gi tr: l = 0, 1, 2, 3, ... , (n - 1). S lng t orbital c ngha xc nh ln momen ng lng chuyn ng | M | ca in t:
| M | = 1(1 + 1) . h 2
(2-9)
15
z y x
z y
s z y x
z y x
px z y x
py z y x
pz
d z2 z y x z
d x 2-y 2 z y x y x
dxz
dyz
d xy
Hnh 2.3. Hnh dng cc my in t s, p v d
S lng t orbital thng c k hiu bng cc ch ci gi l cc phn lp: S lng t orbital l: Phn lp: 0 1 2 3 4 5 .... s p d f g h ...
16
T s lng t chnh s suy ra s lng t ph v cc phn lp nh sau: ng vi mt gi tr ca n s c n gi tr ca l. S lng t chnh n 1 2 3 4 (dng hnh cu); lp L (n = 2) c hai hnh dng my in t s (dng hnh cu) v p (dng qu t i); lp M (n = 3) c ba hnh dng my in t ... v c hnh dng rt phc tp (hnh 2.3). 2.4.5.3. S lng t t : S lng t t (m) l s lng t c trng cho s phn b cc orbital trong khng gian. ng vi mt gi tr ca l c (2l+1) gi tr ca m. N c cc gi tr: m = 0, 1, 2, 3, ..., l S lng t t xc nh gi tr ln hnh chiu ca momen ng lng MZ trn trc z: MZ =
mh 2
S lng t ph l 0 0, 1 0, 1, 2 0, 1, 2, 3
phn lp 1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f
Nh vy, lp K (n = 1) cc in t ch c duy nht mt hnh dng my in t s
(2-10)
T s lng t ph l s suy ra m v s orbital ( lng t) nh sau: S lng t ph l 0 1 2 3 S lng t t m 0 -1, 0, 1 -2, -1, 0, 1, 2 -3, -2, -1, 0, 1, 2, 3 S lng t 1 3 5 7
Trng thi s c 1 lng t; p 3 lng t (px, py, pz); d 5 lng t (dx2-y2, dz2, dxy, dyz, dxz); f 7 lng t...(hnh 2.3). 17
2.4.5.4. S lng t spin: Khi nghin cu cu to ph ca cc nguyn t ngi ta nhn thy rng ngoi nhng s khc nhau v kch thc, hnh dng, hng phn b trong khng gian cc in t cn c mt momen ng lng ring spin (ms), c gi tr bng -1/2 v +1/2. Nh vy, mt in t trong nguyn t c xc nh bng 4 s lng t: n, l, m, ms. Cc s lng t ny c trng cho nng lng, th tch, hnh dng v spin ca in t. Khi nguyn t thay i t trng thi lng t ny sang trng thi lng t khc th gi tr ca cc s lng t cng thay i v my in t s c sp xp li. 2.4.6. S phn b in t trong nguyn t: S phn b in t trong nguyn t tun theo hai nguyn l (nguyn l Pauli, nguyn l bn vng) v quy tc Hun. 2.4.6.1. Nguyn l Pauli: Nm 1925, Pauli pht biu nguyn l: Trong mt nguyn t khng th c 2 in t c 4 s lng t hon ton ging nhau. T nguyn l Pauli c th d dng nhn thy rng, trn mt orbital ch c th c 2 in t vi s spin (-1/2) v (+1/2). Nh vy, phn lp s (c 1 orbital) ch c th c ti a 2 in t; p (3 orbital) 6 in t; d (5 orbital) 10 in t; f (7 orbital) 14 in t ... 2.4.6.2. Nguyn l bn vng: Trong nguyn t cc in t c xu hng chim cc lng t thuc nhng phn lp c mc nng lng thp nht. Khi nguyn t c mc nng lng thp nht l nguyn t ang nm trng thi bn nht. Trng thi ny c gi l trng thi c bn. S phn b cc in t theo nng lng tun theo quy tc Klexcopxki (hnh 2.4)
18
7s 6s 5s 4s 3s 2s 1s
7p 6p 5p 4p 3p 2p
7d 6d 5d 4d 3d
7f 6f 5f 4f
Hnh 2.4. Quy tc sp xp nng lng Klexcopxki
2.4.6.3. Quy tc Hun: Th t phn b in t trong cc phn lp tun theo quy tc Hun: Trong mt phn lp cc in t phn b sao cho tng gi tr spin l cc i sao cho s in t t do l nhiu nht. V d, ba in t ca phn lp np3 c th phn b vo cc orbital theo 4 phng n sau: 1 2 3 4
Theo quy tc Hun, ch c phng n 1 l hp l. 2.4.6.4. Cng thc in t: Cng thc in t c vit di hai dng: cu hnh in t v cu hnh lng t. * Cu hnh in t Dng cng thc ny c vit theo th t sau: Vit s ch s lng t chnh tng ng vi mc nng lng ca in t Vit ch ch phn lp: s, p, d, f, ... Vit ch s tng ng vi tng s in t c trn cc phn lp . 19
V d: 3s2 tc l trn lp M (n = 3) phn lp s (l = 0) c 2 in t (phn lp ny c lm y). 4d3 tc l trn lp N (n = 4) phn lp d (l = 2) c 3 in t (phn lp ny cha c lm y v s in t bo ho ca phn lp ny l 10 in t). * Cu hnh lng t Dng cng thc ny c vit nh sau: - Mi lng t c biu din bng mt hnh vung - Mi in t c biu din bng mt mi tn vi ms = +1/2 (-) hoc ms = -1/2 (). V d: Nguyn t H (Z =1): Cu hnh in t: Cu hnh lng t: Nguyn t Cl (Z = 17): Cu hnh in t: 1s22s22p63s23p5 Cu hnh lng t: 3s2 3p5 2s2 2p6 1s2 3d 1s1 -
20
Chng 3
S BIN THIN TUN HON CU TO NGUYN T BNG H THNG TUN HON MENELEEP
3.1. S BIN THIN Cu to nguyn t ca cc nguyn t ho hc bin thin tun hon theo quy lut: C sau s sp xp mt lp in t th li bt u hnh thnh mt lp in t mi, tc l s hnh thnh xy ra c tnh chu k. 3.1.1. Chu k 1. Theo cng thc tnh s in t ca mi lp N = n2, chu k 1 ( n = 1) c 2 nguyn t hyro v heli:
Z
2 He 1s
1S2
Y X
n = 1
s
He 1s
1 1s
n = 1
s
Y X
3.1.2. Chu k 2. chu k ny ang xy ra s phn b in t ca lp L (n = 2). Do vy, chu k ny c 8 nguyn t (t Li n Ne) vi cc phn lp 2s v 2p. Di y l cng thc in t v hnh dng orbital ca mt s nguyn t:
21
z
5B
1 s22 s22 p 1 2s2 p
y x
n = 2 n = 1 s
2p1 z
7N
1 s22 s22 p 3 2s2 p 2py1 2 p z1 z 2px

1
y x
n = 2 n = 1 s
8O
1 s22 s22 p 4 2s2 p 2py1 2 p z2 2 p x1 y x
n = 2 n = 1 s
3.1.3. Chu k 3: chu k 3 ang xy ra s phn b in t ca lp M (n = 3) gm 8 nguyn t (t Na n Ar) vi 3 phn lp 3s, 3p v 3d:
22
1s22s22p1
11Na
[1s22s 22p6]3s1 3s
3p
3d
15P
[1s22s22p6]3s23p3 3s
3p
3d
18Ar
[1s22s22p6]3s23p6 3s
3p
3d
Khc vi chu k 2, phn lp 3d ca chu k ny hon ton khng c in t. 3.1.4. Chu k 4 chu k 4 ang xy ra s phn b in t ca lp N (n = 4) gm 18 nguyn t (t Z =19 n Z = 36). Nhng chu k c t 18 nguyn t tr ln c gi l chu k ln. 2 nguyn t u ca chu k ny ang xy ra s sp xp in t vo phn lp 4s, trong khi phn lp 3d cn hon ton cha c in t:
19 20
K 1s22s22p63s23p64s1 Ca 1s22s22p63s23p64s2
T nguyn t Z = 21 (Sc - Scandi) bt u phn b in t trn phn lp 3d cho n Z = 30 (Zn - Km):

21
Sc 1s22s22p63s23p6 3d14s2 Fe 1s22s22p63s23p6 3d64s2
..........................................
26
...........................................
30
Zn 1s22s22p63s23p6 3d104s2
T nguyn t Z = 31 (Ga - Gali) bt u phn b in t trn phn lp 4p cho n Z = 36 (Kr - Kripton). Cc nguyn t t Sc n Zn gi l nguyn t chuyn tip. Nguyn t chuyn tip l nhng nguyn t m xy ra s phn b in t phn lp d hoc f nm bn trong
23
mt hoc nhiu phn lp bn ngoi c lm y (bo ho). Cc nguyn t chuyn tip c chia thnh 3 nhm: 1. Nhm c bn hay cn gi l nhm d gm c 3 dy vi mi dy 10 nguyn t: - Dy 3d: - Dy 4d: - Dy 5d:
21 39 57
Sc (Scandi) 30Zn (Km) Y (Ytri) 48Cd (Cadimi) La (Lantan) 80Hg (Thu ngn)
59
2. Nhm Lantanoit gm 14 nguyn t 4f: 3. Nhm Actinoit gm 14 nguyn t 5f: 3.1.5. Chu k 5.
Ce (Ceri) 71Lu (Lutexi)
90
Th (Thori) 103Lr (Lorenxi)
Chu k 5 gm c 32 nguyn t. S phn b in t cc lp v phn lp ca chu k ny xy ra tng t nh chu k 4: hai nguyn t u (37Rb - Rubidi, 38Sr - Stroni) in t phn b trn 5s; su nguyn t cui (49In - Indi 54Xe - Xenon) trn 5p. Gia cc nguyn t s v p ny cc nguyn t chuyn tip dy 4d: 3.1.6. Chu k 6. Chu k ny gm c 32 nguyn t. S phn b in t cc lp v phn lp ca chu k ny bt u t phn lp 6s ca hai nguyn t ( 55Cs - Cezi, 56Ca - Canxi), tip theo 10 nguyn t dy 5d (57La - Lantan 80Hg - Thu ngn), 14 nguyn t nhm Lantanoit 4f: (59Ce - Ceri 71Lu -Lutexi) v cui cng l su nguyn t ca phn lp 6p (81Tl Tali 86Rn - Radon). 3.1.7. Chu k 7. Chu k 7 c bt u bng hai nguyn t s (88Fr - Franxi, 89Ra - Radi), tip theo nguyn t d (89Ac - Actini), 14 nguyn t f nhm Actinoit (90Th - Thori Lorenxi), sau li tr v cc nguyn t d (104Rf - Rutefodi, Seabrgi). Chu k ny n nay vn cn cha hon thnh. 3.1.8. Nhn xt Qua s phn b in t trn cc lp v phn lp trong nguyn t ca cc nguyn t c th rt ra mt s nhn xt sau: 24
105 103 106 39
Y (Ytri) 48Cd (Cadimi).
Lr -
Db - Dubni,
Sg -
- S hnh thnh v in t ca cc nguyn t c tnh cht tun hon: c sau mt dy nguyn t li bt u hnh thnh mt lp in t mi. Dy nguyn t trong ang xy ra s hnh thnh mt lp in t mi c gi l chu k. S phn b in t ca chu k n c bt u t nguyn t u tin trn phn lp ns v kt thc nguyn t cui cng vi phn lp bo ho np. - S sp xp in t trong nguyn t ca cc nguyn t nhn chung tun theo quy tc nng lng Klexcopxki nhng c mt s trng hp ngoi l. V d, trong nguyn t (3d94s2) th li phn b 3d104s1:
29 29
Cu, thay v phn b in t vo phn lp 3d, 4s l
Cu 1s22s22p63s23p63d104s1
24
S sp xp c tnh ngoi l ny xy ra tng t 3.2.
Cr, 42Mo, 47Ag, 79Au...
BNG H THNG TUN HON CC NGUYN T HO HC MENELEEP
3.2.1. nh lut tun hon Meneleep v nguyn tc sp xp: * nh lut: Tnh cht ca cc nguyn t v tnh cht ca cc n cht, hp cht ca cc nguyn t ph thuc tun hon vo in tch ht nhn. * Nguyn tc sp xp: Meneleep sp xp bng h thng tun hon cc nguyn t ho hc theo 3 nguyn tc sau: Cc nguyn t c xp theo chiu tng ca in tch ht nhn Z Cc nguyn t thuc cng mt chu k c xp theo hng ngang Cc nguyn t c tnh cht ging nhau c xp theo hng dc (nhm) Ngy nay, di nh sng ca thuyt c hc lng t c th rt ra mt s nhn xt v s sp xp cc nguyn t ho hc ca bng tun hon Meneleep nh sau: in tch ht nhn nguyn t Z l c tnh c bn nht xc nh bn cht ca nguyn t.
25
S ch gi tr in tch ht nhn trng vi s th t ca nguyn t trong bng tun hon Meneleep. in tch ht nhn chnh bng tng s ht proton ca nguyn t. Khi s lng ht proton thay i th tnh cht ca nguyn t cng thay i, s th t ca nguyn t thay i. S in t trong mt nguyn t trung ho in tch bng s in tch ht nhn (th t Z). Thay i s in t khng lm thay i gi tr Z (khng lm thay i bn cht nguyn t), nhng lm thay i trng thi in tch ca nguyn t. Tnh cht ho hc, vt l ca nguyn t khng phi c xc nh bi s lng in t trong nguyn t m bi cu hnh lp v ca cc in t. S chu k m nguyn t c sp xp chnh bng s lp in t ca nguyn t (tr paladi). S nhm m nguyn t c sp xp chnh bng ho tr cao nht ca nguyn t . Cc nguyn t s v p l nhng nguyn t thuc nhm chnh (nhm A), cc nguyn t d v f thuc nguyn t nhm ph (nhm B). 3.2.2. S bin thin tun hon tnh cht ca cc nguyn t: 3.2.2.1. Nng lng ion ho
I, eV 25
He Ne 20 F N 15 H 10 Be Mg B 5 Li Na Al Si C O Cl P S Zn Ca Ti Sc K Co Cu V Mn Fe Ni Cr As Br Ge Se Ga Rb Kr Ar
11 13 15
17 19
21 23 25 27 29 31 33 35 37
Hnh 3.1. S ph thuc I vo s th t Z
26
Nng lng ion ho I l nng lng cn thit tch mt in t ra khi nguyn t nm trng thi c bn: Z Z+ + e Nng lng ion ho c gi tr dng. i vi nguyn t c nhiu in t, nng lng ion ho ln lt c cc gi tr I1, I2, I3,... tng ng vi in t th nht, th hai, th ba ... trong I1 < I2 < I3... Nng lng ion ho bin i c tnh chu k v nhn chung theo quy lut: cc nguyn t u chu k c nng lng ion ho thp, cui chu k c nng lng cao (hnh 3.1). 3.2.2.2. i lc vi in t i lc vi in t e l nng lng to ra hay thu vo khi mt nguyn t nhn mt electron. Z + e Zi lc vi in t c gi tr bng nng lng ion ho nhng khc du ( du m). i lc vi in t bin i c tnh cht tun hon. S tun hon ph thuc vo cu hnh in t ca nguyn t - s th t Z (hnh 3.2).
I1,F 1
30
20
10
I1 F 1
-10
1 H
2 3 He Li
4 5 Be B
6 C
7 N
8 O
9 F
10 11 12 13 Ne Na Mg Al
14 Si
15 P
16 S
17 Cl
18 Ar
19 K
20 Ca
Hnh 3.2. S bin i tun hon I v E theo Z
27
3.2.2.3. m in m in l kh nng ht in t v pha mnh ca mt nguyn t ny so vi nguyn t khc trong mt phn t. Theo Mallikel, m in c c th c xc nh theo cng thc sau:
1 2
trong - I l nng lng ion ho th nht - E i lc vi in t Hin ti c kh nhiu thang o m in khc nhau (khong 20 thang o) nhng thang o theo Flo (c = 4) thng hay c s dng. S bin i m in ca cc nguyn t theo thang o ny ( m in theo Pauling) c trnh by trn hnh 3.3.
CHU KY 1 2 3 4 5 6 Li 1,0 Be 1,5 B 2,0 H C 2,5 N 3,0 Cl 3,0 O 3,5 F 4,0
Na Mg Al Si P S 0,9 1,2 1,5 1,8 2,1 2,5 K Ca Sc Ti Ge As 0,81,0 1,31,6 1,7 2,0
Se Br 2,4 2,8
Rb Sr Y Zr Sn Sb Te I 0,81,0 1,31,6 1,8 2,1 2,6 1,7 Cs Ba 0,7 0,9 1,0 2,0 3,0 4,0
Hnh 3.3. S bin i m in theo Pauling
m in ca cc nguyn t tng t tri sang phi theo chu k v nhn chung tng t di ln trn theo phn nhm. Cc nguyn t s ca nhm I c m in nh nht, cc nguyn t p ca nhm VII c m in ln nht.
28
K 7S Ra
Rb
Cs Fr
5S Ca
Na
Li
Ba Ce Nd LaSm Eu Dy Gd Er Yb Lu Hf Ta
3.2.2.4. Bn knh nguyn t v bn knh ion:
Hnh 3.4. S thay i bn knh nguyn t theo Z

Sr Y Te Nb In Zr Mn Ru Te Rh Ag 4P Cd Sn Sb Te I Xe
P S Cl Al Kr As Se Br 15 20 25 30 40 50 60 70
Be
Sc 3S Ti Cr Ga V Mn Fe K Al Cu Mg Co Zn Si Ni Ge
Ac Pa 7S ThU Pu Am Np Cm Cf Md
W Ti Re OsPt Pb IrAu HgBi Po Al Rn
F O
Ne
10
80
90
100
29
S thay i bn knh nguyn t v bn knh ion (rZ) ca cc nguyn t theo s th t Z c tnh cht tun hon (hnh 3.4): tng t trn xung di theo phn nhm v gim t tri sang phi theo chu k. 3.2.2.5. Tun hon th cp v tun hon ni chu k: S bin i cc tnh cht (nng lng ion ho, bn knh nguyn t...) ca cc nguyn t theo phn nhm xy ra khng u n (hnh 3.5). S bin i ny c gi l tun hon th cp.
(I +I +I +I ) 1 2 3 4 150 130 110 90 70
eV
0 r, A
1,5 1,0 0,5 10 30 50 1 1
Hnh 3.5. S bin i I v rZ ca cc nguyn t nhm IV theo Z
Tun hon ni chu k l s bin thin tnh cht mt cch u n cc nguyn t p, d, f do qu trnh sp xp in t vo cc phn lp ny xy ra theo hai giai on (quy tc Hun). V d, tun hon ca cc nguyn t thuc h Lantanit
30
Chng 4 LIN KT HO HC
4.1. MT S KHI NIM C BN CA LIN KT HO HC Lin kt ho hc l mt nhim v rt quan trng ca ho hc v rng, nu khng bit c bn cht ca s tng tc gia cc nguyn t ln nhau trong phn t th khng th hiu c nguyn nhn to thnh v s hp cht khc nhau, thnh phn, cu to, kh nng phn ng... ca chng. Bn cht ca s to thnh lin kt gia cc nguyn t chnh l lc ht tnh in gia ht nhn nguyn t v electron. Lc ht tnh in ny ph thuc vo mt electron. Ph thuc vo s phn b mt electron trong hp cht ngi ta phn thnh 3 loi lin kt trong ho hc: lin kt ion, lin kt cng ho tr v lin kt kim loi. S phn b mt in t c th xc nh c qua gi tr m in ca cc nguyn t: Nu m in ca 2 nguyn t tham gia to lin kt khc nhau ln Nu m in ca 2 nguyn t tham gia to lin kt 0Dc<2 th lin kt l (Dc 2) th lin kt l lin kt ion. lin kt cng ho tr (cng ho tr khng phn cc Dc=0; cng ho tr phn cc 0< Dc<2). 4.1.1. Cc thng s c bn ca phn t: Cu to phn t ca hp cht c th c xc nh qua vic nghin cu tnh cht ho hc, vt l ca n. Ngoi ra, bng phng php phn tch vt l ngi ta xc nh cc thng s c bn ca phn t: di lin kt, gc ho tr v cu hnh hnh hc phn t. - di lin kt l khong cch gia hai tm ht nhn ca hai nguyn t lin kt ho hc vi nhau. V d : di lin kt gia nguyn t hyr v xi trong phn t H2O l 0,92AO. - Gc ho tr l gc to bi ng thng tng tng i qua tm cc nguyn t lin kt ho hc vi nhau. V d, gc lin kt ho tr ca phn t nc H2O l 04,5o. - Nng lng lin kt l c tnh quan trng ca lin kt ho hc, xc nh bn ca lin kt. V gi tr, nng lng lin kt c tnh bng nng lng gii phng khi ph v mt lin kt.
31
Nng lng lin kt ca phn t c hai nguyn t chnh bng nng lng phn ly ca phn t thnh nguyn t. Nng lng lin kt ca lin kt A-B trong phn t ABn l gi tr trung bnh EA-B:
AB
AB
(4
-1)
4.1.2. Gin th nng ca phn t: Lin kt ho hc ch c th to thnh trong trng hp nu s lng cc nguyn t tham gia lin kt vi nhau ( 2). S to thnh lin kt lm cho nng lng ca h (ng nng v th nng) gim xung h bn hn. Xem xt s thay i th nng ca h v khong cch gia cc nguyn t tham gia lin kt c th d on c cu to ca phn t. S thay i th nng ca h gm hai nguyn t hyro c trnh by trn hnh 4.1.
E (kJ/mol) 800 400 -400
0,74 1
o (A )
Hnh 4.1. S ph thuc th nng E vo khong cch r gia 2 nguyn t hyro
S to thnh phn t hyro c th gii thch da trn c s gin bin i th nng hnh 4.1. Khi 2 nguyn t hyro tin li gn nhau th gia chng s xut hin 2 loi lc: 1. Lc ht gia ht nhn nguyn t ny vi in t ca nguyn t kia 2. Lc y gia hai ht nhn v gia hai in t ca 2 nguyn t vi nhau
32
giai on u lc ht chim u th, giai on cui lc y li chim u th v kt qu ti mt khong cch nht nh th nng s c gi tr cc tiu (phn t trng thi bn nht). Khong cch ny chnh l di lin kt (i vi hyro l 0,74 AO) ca phn t. Tuy nhin qu trnh thay i ny ch xy ra gia hai electron c spin i nhau. i vi trng hp hai electron c spin song song vi nhau th khi nguyn t xch li gn nhau gia chng ch xut hin lc y phn t s khng c to thnh. S to thnh phn t hyro c gii thch bng s xen ph my electron ca cc nguyn t vi nhau. Ti v tr xen ph, mt electron l ln nht, lc ht gia cc ht nhn vi in t tng ln (hnh 4.2).
Hnh 4.2. S phn b in t trong phn t H2
4.2.
LIN KT ION Lin kt ion l loi lin kt c trng gia cc nguyn t c m in khc nhau
4.2.1. S hnh thnh lin kt ion ln ( 2). Loi lin kt ny thng c to thnh bi tc dng ca cc kim loi kim vi cc nguyn t halogen. V d s to thnh phn t NaCl t nguyn t Na v Cl: Na (Z = 11) 1s22s22p63s1 khng. Cl (Z = 17) 1s22s22p63s23p5
Tng in tch trong nguyn t ca 2 nguyn t ny trng thi c bn bng
33
Khi hai nguyn t ny tc dng vi nhau, cc phn lp 3s23p5 ca clo c s in t gn bo ho (b bt t ca Ar) nn n ko in t 3s1 ca nguyn t natri v pha mnh to thnh anion Cl-. Nguyn t natri cho i mt in t tr thnh cation Na+ c cu hnh in t ca Ne: Cation Na+ 1s22s22p6 Anion Cl1s22s22p63s23p6
Cc ion Na+ v Cl- lin kt vi nhau bi lc ht tnh in to thnh phn t NaCl. Na+ + Cl- = NaCl S ion ho to thnh cation v anion ca cc nguyn t tun theo quy lut: - Xu hng to thnh cation cng tng khi nguyn t cng v pha bn tri v pha di ca bng tun hon. - Xu hng to thnh anion cng tng khi nguyn t cng v pha bn phi v pha trn ca bng tun hon. 4.2.2. c im ca lin kt ion: - Cc hp cht to thnh bng lin kt ion trng thi rn tn ti di dng tinh th trong cc cation v anion c phn b mt cch u n (v d, mng tinh th khi hnh lp phng ca NaCl). - C nhit nng chy, nhit si cao hn so vi cc hp cht lin kt cng ho tr. - Dng nng chy ca cc hp cht lin kt ion c tnh dn in. - C xu hng ho tan tt trong cc dung mi phn cc ( v d H2O). - Khng bn, khng c tnh bo ho v khng c tnh nh hng. 4.3. LIN KT CNG HO TR Nh ni trn, khng th gii chnh xc phng trnh Shrodinger cho h thng nguyn t trong cc phn t. V vy tm quy lut phn b in t trong phn t ngi ta dng mt s phng php gn ng. Hai phng php thng c s dng nht l phng php lin kt ho tr v phng php orbital phn t.
34
4.3.1. Phng php lin kt ho tr (VB). C s ca phng php cng ho tr xut pht t quan im: hai nguyn t trong phn t lin kt vi nhau bng s gp chung ca mt hoc nhiu cp electron vi nhau. Phng php cng ho tr c c trng cc c tnh: tnh bo ho, tnh nh hng v tnh phn cc. Cc quan im v lin kt cng ho tr c th hin di ba tin c bn sau: 1. Lin kt cng ho tr c hnh thnh do s ghp chung ca hai in t c spin i nhau ca hai nguyn t tham gia lin kt. 2. Mc xen ph gia hai my in t cng ln, lin kt cng bn. 3. Lin kt cng ho tr c phn b theo phng c kh nng xen ph cc i. 4.3.1.1. Tnh bo ho B 2s2 2p1
2 2 2 C 2s2 2p2 2 N 2s2 2p3 2
trng thi kch thch: Bo c ho tr 3, cacbon ho tr 4: B* 2s2 2p1

2 2 2 C* 2s2 2p2 2
Tnh bo ho trong lin kt cng ho tr c quyt nh bi s in t c thn ca orbital nguyn t. Trong nguyn t cc electron c thn tn ti di hai trng thi: c bn v kch thch. V d: trng thi c bn, bo c ho tr 1, cacbon c ho tr 2 v nit c ho tr 3: 4.3.1.2. Tnh nh hng V my in t c hnh dng khc nhau nn s xen ph ca chng vi nhau to thnh lin s xy ra theo hng xen ph cc i. Tu thuc vo phng php xen ph v tnh i xng cc lin kt cng ho tr c chia thnh: lin kt s v p (hnh 4.3)
35
p -p
p -p
p -p
s-s
d -d d -d
Hnh 4.3. S xen ph to thnh cc lin kt s, p v d
4.3.1.3. Thuyt lai ho Thng thng cc orbital nguyn t tham gia to lin kt cng ho tr c nng lng khc nhau. V d, nguyn t Be s dng 2 phn lp 2s12p1, nguyn t B (2s12p2), nguyn t C (2s12p3) nhng to lin kt, cc phn lp ny t hp li trn cng mt mc nng lng v cng yu t i xng. S t hp cc trng thi electron ban u khng ging nhau thnh cc trng thi ging nhau trong lin kt cng ho tr c gi l s lai ho. Nh vy, khi lai ho cc nguyn t thay i hnh dng v nng lng orbital in t to thnh nhng orbital mi c hnh dng v nng lng nh nhau gi l orbital lai ho.(hnh 4.4)
36
1800 (s + p )-o rb ita l s p -o rb ita l
(s + p + p )-o rb ita l
s p 2 -o rb ita l
109028' (s + p + p + p )-o r b ita l s p 3 - o rb ita l
Hnh 4.4. Hnh dng orbital lai ho sp, sp2, sp3
Hnh dng orbital sp trn hnh 4.4 cho thy mt in t phn b v mt pha ln hn pha bn kia. Kt qu l s xen ph ca pha c mt in t ln s to ra lin kt bn hn so vi s xen ph ca s v p ring bit. 4.3.1.4. Cc loi lai ho * Lai ho sp3 lm r vic t hp ca cc phn lp electron theo m hnh lai ho sp3, ngi ta xt s to thnh phn t CH4. Nguyn t cacbon trng thi c bn c ho tr 2 vi cu hnh electron 1s22s22p2. to thnh phn t CH4, nguyn t cacbon phi chuyn sang trng thi kch thch C* c ho tr 4 vi cu hnh electron 1s22s12p3. Trong trng hp ny phn t CH4 c to thnh bi ba in t 2p3, mt in t 2s1 ca nguyn t cacbon vi bn in t 1s1 ca 4 nguyn t hyro: 37
12
2s1 2px 2py 2pz C* CH4
Nh vy, trong phn t CH4 s c 2 loi lin kt: 3 lin kt loi s-p v 1 lin kt loi s-s. Thc t cho thy rng trong phn CH4 ch c duy nht mt loi lin kt ( 4 lin kt hon ton ging nhau).
3 1 + s px + 2 py + pz
(s+ p + p + p )-o rb ita l 3 1 1
2 1 0 9 0 ,5
Hnh 4.5. Lai ho sp3
iu ny c gii thch bng thuyt lai ho: to thnh phn t CH4, mt orbital s t hp vi ba orbital to thnh 4 orbital lai ho sp3 c hnh dng v nng lng hon ton nh nhau. Cc orbital sp3 ny khng ging orbital s v p ban u, c kh nng xen ph cao hn to thnh lin kt bn hn. Cc orbital lai ho u c in tch cng du v do vy chng s y ln nhau n mt khong cch xa nht. i vi lai ho sp3, s phn b xa nht ca bn orbital ny chng c phn b di nhng gc 109,28O, gc t tm ca t din u (hnh 4.5). S lai ho sp3 tng t xy ra nguyn t N ca phn t NH3, nguyn t O ca phn t H2O (hnh 4.6).
38
H C H H 109 28'
0
CH
N H H
H 3N H H H
H 2O
H 1 0 4 ,5 0
1 0 7 ,3 0
Hnh 4.6 S xen ph orbital trong phn t CH4, NH3, H2O
Nguyn t N trng thi lai ho sp3 c 5 in t trong c mt cp in t khng phn chia nm trn mt orbital lai ho. Lc y ca cp in t ny vi cc orbital lai ho cn li lm cho gc lin kt gim xung cn 107,3O (< 109,28O). Nguyn t O trng thi lai ho sp3 c 6 in t trong c hai cp in t khng phn chia nm trn 2 orbital lai ho. Lc y gia 2 cp in t ny vi cc orbital lai ho cn li mnh hn, lm cho gc lin kt gim nhiu hn ( cn 104,5O). * Lai ho sp2 y l lai ho ca mt orbital s vi hai orbital p to thnh ba orbital lai ho sp2 nm trong mt mt phng. V d lai ho nguyn t B trong phn t BCl3 (hnh 4.7).
Cl B Cl Cl
0 12
12
Hnh 4.7. Phn t BCl3
a. Orbital lai ho sp2
b. Cu hnh hnh hc
Gc lin kt trong phn t BCl3 l 1200, lai ho sp2 l loi lai ho tam gic u. * Lai ho sp Lai ho sp l lai ho ca mt orbital s v mt orbital p to thnh hai orbital sp nm trn mt ng thng vi gc lai ho 1800 (hnh 4.8).
39
+ s p s ,p 1800 sp
Hnh 4.8. lai ho sp
V d, trong phn t BeCl2, hai lin kt c to thnh do s xen ph ca my in t lai ho sp ca Be v p ca Cl. Phn t BeCl2 c cu hnh hnh hc ng thng Cl Be Cl.
1
Be Cl 2
Cl
Phn t BeCl2 4.3.2. Phng php orbital phn t 4.3.2.1. Lun im c bn ca phng php Mo Phng php MO xemphn t nh l mt tp hp ca cc ht nhn v electron trong mi electron chuyn ng trong in trng ca tt c cc ht nhn v in t khc. Tt c cc electron phn t (tng t nh trong nguyn t) c phn b vo cc 40
orbital phn t theo cc trng thi nng lng xc nh. Mi orbital c vit bi cc s lng t c trng cho tnh cht ca in t trng thi nng lng . Nh vy, v c bn phng php MO l s vn dng m rng ca phng php AO, ch khc l orbital phn t c nhiu trung tm ht nhn. V orbital phn t c nhiu tm nn hnh dng ca n rt phc tp. n gin ho, trong phng php gn ng ngi ta xem orbital phn t nh l mt t hp tuyn tnh ca cc orbital nguyn t. iu ny c ngha l orbital phn t c to thnh bi kt qu php cng + v php tr - cc orbital nguyn t. V d, nu orbital ca 2 nguyn t A, B c k hiu l A , B th orbital phn t AB c to thnh t Av B s l: + = c1A + c2B - = c1A - c2B (4-2a) (4-2b)
trong c1 v c2 l phn orbital nguyn t tng ng tham gia to thnh phn t. Tng t nh trong phng php AO, ngi ta s dng cc ch ci s, p, d, f... biu din cc orbital phn lp th trong phng php MO ngi ta s dng cc ch ci Hy lp s, p, d, j... biu din cc loi orbital lin kt. Biu din phn t theo phng php MO c ngha l xc nh dng orbital phn t , mc nng lng ca chng v c tnh phn b in t trong cc orbital . Quy lut phn b in t trong MO cng cng tun theo 2 nguyn l (nguyn l Pauli, nguyn l bn vng ) v qui tc Hund nh trong AO. im khc bit y l s phn b in t theo mc nng lng xy ra kh phc tp . i vi cc nguyn t chu k 1 v cc nguyn t t liti n nit thuc chu k 2, cc in t c phn b theo quy lut mc nng lng sau :
* * * * 1S < 1S < 2 S < 2S < x = y < P < x = * < P y
i vi 2 nguyn t cui chu k 2 (oxi v flo) c qui lut phn b nh sau:

* * * * 1S < 1S < 2 S < 2S < P < x = y < x = * < P y
4.3.2.2. Cc loi orbital lin kt trong phn t Hnh dng my in t v mc nng lng ca phn t to thnh t hai electron 1s1 ca 2 nguyn t theo phng php MO c biu din trn hnh 4.9.
41
MO
+ AO Xen ph? AO
s ls
+ + AO
s ls
Hnh 4.9. S to thnh lin kt v
Tng t nh cc electron s, hnh dng my in t v mc nng lng xen ph ca 2 electron p c biu din trn hnh 4.10 v 4.11.
MO AO
+ + -
Tr
cg n
s *2Px
2Px
2Px
s 2Px
42
AO
MO X Z X
2P z 2P z
r t c n g
S to thnh cc orbital phn t t cc nguyn t thng c biu din di dng gin nng lng (hnh 4.12, 4.13). z
Nng l ng E
_ s ls
1SA 1SB s ls
-E E
Hnh 4.12. Gin nng lng ca nguyn t v phn t hyro
43
AO
MO p*x p*y 2P pz py s *s
AO AO 2P
Nng l ng E
MO s *x sx s *s
AO 2P
2P
2S ss
2S
2S
2S ss
Hnh 4.13. Gin nng lng nguyn t v phn t ca cc nguyn t chu k 2
Trn c s ca cu hnh in t hoc gin nng lng ca phn t ngi ta tnh c bc lin kt phn t (N) theo cng thc: N=
1 (n - n*) 2
(4-3)
Trong : n - s in t nm orbital lin kt n* - s in t nm orbital phn lin kt Cn c vo gi tr bc lin kt phn t s so snh c bn ca cc phn t: i vi cc phn t c to thnh t mt loi nguyn t, phn t c bc lin kt cng ln th n cng bn. 4.4. CU TO PHN T 4.4.1. Phn t khng phn cc v phn cc Ph thuc vo s phn b mt in t trong phn t, ngi ta chia phn t thnh loi phn cc v khng phn cc.- Phn t khng phn cc l loi phn t trong trng tm ca in tch dng trng vi trng tm ca in tch m . V d, cc phn H2, N2, O2... - Phn t phn cc l loi phn t trong trng tm ca in tch dng v in tch m khng trng vi nhau. V d, cc phn t HCl, H2 O, C2H5OH... l nhng phn t phn cc. phn cc ca phn t c xc nh bng i lng momen lng cc () v tnh theo n v Debai ( 1D = 0,33.10-29 C.m):
44
= lq trong l - di phn cc q - in tch
(4-4)
Momen lng cc ca phn t bng tng vect momen lng cc ca tt c cc lin kt. Do vy, ph thuc vo cu to ca phn t, momen lng cc c th bng khng (m = 0) hoc khc khng (m 0). V d, phn t CO2 c m = 0, phn t H2O c m= 1,84 D. 4.4.2. S phn cc ho phn t v ion Di tc dng ca in trng ngoi, s phn b mt electron ca phn t, ion thay i dn n lm thay i momen lng cc c gi l s phn cc ho. 4.4.2.1 S phn cc ho bin dng (phn cc cm ng) l s phn cc ca cc phn t khng phn cc khi chng c t trong mt in trng ngoi: phn mang in tch dng ca phn t b ht v pha cc m ca in trng, phn mang in tch m b ht v pha cc dng (hnh 4.14). pha cc d-ng (hnh 4.14). + + + -
Hnh 4.14. S phn cc bin dng
Momen lng cc ca s phn cc bin dng c xc nh theo cng thc: C = E trong a - phn cc ho E cng in trng (4-5)
45
4.4.2.2. S phn cc ho nh hng y l s phn cc ho gia cc phn t phn cc khi chng chuyn t trng thi chuyn ng nhit hn lon sang trng thi sp xp trt t di tc dng ca in trng ngoi (hnh 4.15).
+ + - + -
+ + +
Hnh 4.15. S phn cc ho nh hng
4.4.2.3. S phn cc ho tng h y l s phn cc gia cc ion khi chng xch li gn nhau: ion ny gy ra s phn cc ho i vi ion kia. Hin tng ny lm tng tnh cht cng ho tr ca ion v do lm tng bn ca lin kt ion. 4.4.3. Lin kt cho nhn: Nu mt phn t c cp electron cha tham gia lin kt v phn t (hoc nguyn t) khc c orbital trng th gia chng s c th lin kt vi nhau bng lin kt cho nhn. Loi lin kt ny thng gp trong phc cht hoc trong cc trng thi chuyn tip. V d, cc hp cht: I2.NH3, I2.O(CH3)2, AlCl3.NH3, AlCl3.O(C2H5)2... C ch to thnh lin kt ny ph thuc vo loi orbital tham gia cho nhn. V d, trong s to thnh phn t NH4+, phn t NH3 s dng cp in t khng phn chia ca mnh cho vo orbital trng ca H+ H H N: H mnh cho vo orbital trng ca BF3: H H-N: H + F B- F F H F H - NB - F H F + H+ H H N H H +
Trong phc cht BF3.NH3, phn t NH3 s dng cp in t khng phn chia ca
46
4.4.4. Lin kt hyro: Tn gi lin kt hyro xut pht t thc t loi lin kt ny c hnh thnh qua nguyn t hyro. lin kt ny, nguyn t hyro lm cu ni gia hai nguyn t c bn knh nh nhng c m in ln, trong mt bn l lin kt cng ho tr v bn kia l lc ht tnh in. Nhng nguyn t c kh nng to lin kt hyro ln nht l N, O, F. V d, s to thnh lin kt hyro ga cc phn t H2O, HF: ...H-O...H- O...H-O... H H H ...H-F...H-F...H-F...
* Lin kt hyro c cc c im sau: - Thuc loi lin kt c bn thp , khong (40 kJ/mol). - Lm tng nhit si, nhit nng chy, nhit ho hi, nhit dung ca cc cht ho hc (nu khng c lin kt hyro th nc s si 80 0C). - Gy ra s bin i bt thng khi lng ring ca nc (nc c khi lng ring ln nht 1 g/ml 4 0C). - nh hng n ho tan ca cc cht tan (ru etylic tan v hn trong nc).ng vai tr rt quan trng trong s tn ti v hot ng ca c th sng. 4.4.5. Lin kt Van der Waals : Lc Van der Waals l lc tc dng ln nhau gia cc phn t. Lc ny c t hp t 3 loi lc: lc nh hng, lc cm ng v lc khuych tn. Tng th nng ca lc Van der Waals l: E t = E + E C + EK ng to thnh. Lc khuych tn c to thnh do s xut hin momen lng cc tm thi gia cc phn t. Do electron lun lun chuyn ng dn n s phn b in tch dng v in tch m lch khi v tr cn bng nn sinh ra momen lng cc tm thi. (4-5) Lc nh hng v lc cm ng l do s phn cc nh hng v s phn cc cm
47
* c im ca lc Van der Waals - Khng c tnh chn lc v tnh bo ho. - Nng lng tng tc ca lc Van der Waals tng i nh (khong di 40 kJ/mol). - Gim nhanh khi khong cch gia cc phn t tng ln (t l vi r-6, trong r l khong cch gia tm im 2 phn t). - Tng ln khi kch thc v khi lng phn t tng.
48
Chng 5 NHIT NG HO HC
Nhit ng hc nghin cu quy lut iu khin s trao i nng lng bao gm 2 quan im: 1. Quan im c in: ch thit lp h thc nng lng vi p sut (P), th tch (V), nhit (T) m khng ch n cu to ca nguyn t, phn t v c ch chuyn ho. 2. Quan im nhit ng hc thng k: Xc nh nng lng da vo tnh cht ca cc nguyn t v phn t. Nhit ng hc p dng vo ho hc c gi l nhit ng hc ho hc. Ni dung ch yu ca nhit ng ho hc da trn ba nguyn l c bn ca nhit ng hc. Trn c s vn dng ba nguyn l c bn ny, nhit ng ho hc cho php :- Tnh c nng lng trao i ca phn ng ho hc- Tin on c chiu ca ca phn ng ho hcGii hn t din bin ca mt phn ng ho hc. 5.1. MT S KHI NIM C BN V NHIT NG HC 5.1.1. H v mi trng H l mt vt, mt nhm vt c tch ring ra c thc hoc bng s tng tng nghin cu; phn cn li l mi trng. H nhit ng hc c phn chia thnh nhiu loi khc nhau: * H ng th: c tnh cht ng nht tt c mi im ca h. V d, kh nn trong bnh, ru cha trong chai... (mt pha) * H d th (h c hai pha tr ln): c tnh cht khng ng nht trong cc phn khc nhau ca h c phn chia vi nhau bng b mt vt l. V d, nc v nc 0 OC... * H vt l: h m trong xy ra cc qu trnh thay i vt l nhng khng c s thay i v bn cht ho hc. V d, s bin i cc trng thi vt cht nhit nng chy, nhit si.
49
* H ho hc: h m trong c mt phn hoc tt c cc thnh phn ho hc tc dng vi nhau c s thay i v bn cht ho hc. V d, Zn v H2SO4 cha trong cc thu tinh.H h: c s trao i cht v trao i nhit vi mi trng. * H kn: c s trao i nhit nhng khng trao i cht vi mi trng. * H on nhit: C s trao i cht nhng khng c s trao i nhit vi mi trng. * H c lp: Khng c s trao i cht v khng c s trao i nhit vi mi trng. Trn thc t h ny rt kh tn ti. V d, h gn ng cho trng hp ny l qu trnh n ca mt qu bom. y, s cho v nhn nng lng gia h v mi trng xy ra qu nhanh so vi s thay i nng lng ca h theo th gian. 5.1.2. Quy c v du ca nng lng trao i : Cc loi nng lng trao i: c nng, nhit nng, in nng, nng lng bc x. n v: Jun (n v th nguyn h SI). 1J l cng do lc 1N thc hin trn qung ng 1 m. Nng lng gii phng ( pht nhit, to nhit, bc x nhit ) c du m (-). Nng lng thu vo (hp th nhit, thu nhit) c du dng (+). 5.1.3. Trng thi v thng s trng thi : Trng thi l mt tp hp trc tip hay gin tip ca cc thng s trng thiThng s trng thi l cc i lng: nhit T, p sut P, th tch V, khi lng m, thnh phn ho hc... C 2 loi thng s trng thi: thng s dung v thng s cng : * Thng s dung : Thng s dung (ting Latinh, additio ngha l cng) - tnh cht ca h vt cht c th tnh c t cc tnh cht ca cc thnh phn tng ng cu to nn n. V d, khi lng phn t bng tng khi lng cc nguyn t; in tch ht nhn nguyn t bng tng in tch ca cc proton...
50
*Thng s cng : Thng s cng khng c tnh cht cng tnh, khng ph thuc vo yu t dung . V d, nhit ca nc (cng ) khng ph thuc vo th tch v khi lng ca n. * Cn bng nhit ng: Mt h trng thi cn bng nhit ng khi gi tr ca cc thng s trng mi im u nh nhau v khng bin i theo thi gian. 5.1.4. Bin i thun nghch v bt thun nghch : * Bin i thun nghch: Mt h ang trng thi cn bng (P,V,T) chuyn qua cn bng mi (P,V,T1) bng s thay i T T1 qua nhiu bc Ti khc nhau: (P,V,T) (P,V,T1) (P,V,T1) (P,V,T1) ... (P,V,T1) c gi l s bin i thun nghch (do c s thay i v cng nh nn trong tng bc h c th tr li trng thi ban u). * Bin i bt thun nghch: Bin i bt thun nghch l bin i ch xy ra nhanh, qua mt bc ln. N hon ton ngc li vi bin i thun nghch l h khng th tr li trng thi ban u. Vy: Bin i thun nghch l qu trnh cn bng; Bin i bt thun nghch l qu trnh t din bin. 5.1.5. Hm trng thi : Mt hm nhit ng c gi l hm trng thi nu s thay i gi tr ca n ch ph thuc vo cc gi tr thng s trng u v cui m khng ph thuc vo cch thc bin i ca qu trnh. V d, nu F (P,V,T,...) l hm trng thi th khi: F1 (P1,V1, T1,...) F2 (P2,V2,T2,...), ta c: F = F 2 - F1
51
5.2. PHT BIU NGUYN L I NHIT NG HC : Gi s ta c mt lng kh nm trong mt bnh kn c gn vi mt pitng v nhn t bn ngoi mt nng lng Q ( hnh 5.1) P /////////////////////////// V P /////////////////////////// V2 V1
Hnh 5.1. S thay i nng lng ca h gin n
Khi kh b nung nng, h nhn mt nng lng Q lm cht kh n ra thm th tch DV, tc l thc hin mt cng gin n PDV chng li p sut bn ngoi P (h ng p). Phn nng lng Q cn li lm tng ni nng DU ca h (lm tng nhit , bin i trng thi...). Do vy c th vit: Q = DU + PDV Hay: DU = Q - PDV i vi mt s bin i v cng nh, ta c: dU = dQ - PdV * Pht biu nguyn l I S tng ni nng ca h bng nng lng t bn ngoi cung cp cho h tr i cng gin n m h thc hin trong qu trnh . Biu thc (5-1a) l biu thc ton hc ca nguyn l I nhit ng hc. 5.3. NHIT NG TCH, NG P : * Nhit ng tch: Nhit ng tch l nhit lng thu vo hay thot ra ca h trong qua trnh bin i ng tch (V = const). T (5.1a ): DU = Q - PDV, vi V = const, suy ra: 52 (5-1b) (5.1a)
QV = DU Vy nhit ng tch chnh bng s bin i ni nng ca h. * Nhit bin i ng p:
(5-2)
Nhit bin i ng p l nhit lng thu vo hay thot ra ca h trong qua trnh bin i ng p (P = const). T (5-1a ): DU = Q - PDV, vi P = const, suy ra: QP = DU + PDV QP = (U2 - U1) + P(V2 - V1) QP = (U2 - PV2) - (U1 - PV1) t H = U + PV, ta c: QP = H2 - H1 = H entanpi ca h. Entanpi thng c biu th bng kJ/mol (hoc kcal/mol). Entanpi c o iu kin: T = 298K v P = 1amt c gi l entanpi trng thi chun. S bin i entanpi trng thi chun c k hiu l HO298. Trong trng hp tng qut, s bin i entanpi ca h s l:
H = U + PV + VP
(5-3)
i lng H c gi l Entanpi. Vy nhit ng p chnh bng s bin i
* Quan h gia nhit ng tch v nhit ng p: T H = U + PV, ta c:

H = (U + PV) = U + PV
QP = QV + P V Nu thay: PV = nRT, ta c: QP = QV + nRT i vi mt phn ng dng tng qut: aA + bB = eE + qQ Ta c: QV = U = (eUE + qUQ) - (aUA + bUB)
(5-4a) (5-4b)
trong : n = (mol tham gia phn ng) - (s mol kh to thnh sau phn ng)
53
QP = H = (eHE + qHQ) - (aHA + bHB)

n = (e + q) - (a + b)
Nu QP > 0 v QV > 0 th y l qu trnh (phn ng) thu nhit. Nu QP < 0 v QV < 0 th y l qu trnh (phn ng) to nhit. 5.4. NH LUT HESS V CCH XC NH NHIT PHN NG THEO H QU CA NH LUT HESS : 5.4.1. nh lut Hess : Pht biu: Hiu ng nhit khng ph thuc vo cch thc m theo qu trnh bin i xy ra m ch ph thuc vo trng thi u v trng thi cui ca qu trnh. V d, phn t CO2 c th c to thnh bng phn ng trc tip gia graphit vi xi, hoc c th bng kt qu ca hai phn ng trung gian (hnh 5.2): C (gr) + O2 (k) DH2 CO (k) + O2 (k) DH1 CO2(k) DH3
Hnh 5.2. Cch thc to thnh phn t CO2
Nh vy theo nh lut Hess, ta c: H1 = H2 +H3 5.4.2. Cch xc nh nhit phn ng theo h qu ca nh lut Hess : * H qu 1: Hiu ng nhit ca phn ng thun bng hiu ng nhit ca phn ng nghch nhng ngc du (hnh 5.3).
54
Hthun Hthun + Hnghch = 0
F2
Hnghch
F1
Hnh 5.3. Hiu ng nhit ca phn ng thun nghch
* Nhit sinh: Nhit sinh (nhit to thnh) ca mt hp cht l nhit lng thot ra hay thu vo khi to thnh mt mol cht t cc n cht bn vng ban u iu kin xc nh, c k hiu: DHs Nhit sinh xc nh trng thi chun gi l nhit sinh chun, c k hiu: DH0298,s. Nhit sinh chun ca cc n cht bng khng: DH0298,s(n cht) = 0. n v: J/mol; cal/mol. * H qu 2: Hiu ng nhit ca mt phn ng bng tng nhit sinh ca cc cht to thnh tr i tng nhit sinh ca cc cht tham gia. i vi phn ng tng qut: Ta c: * Nhit chy: Nhit chy ca mt cht l nhit lng thot ra khi t chy hon ton mt mol cht thnh cc xit cao nht iu kin xc nh, c k hiu: DHc. Nhit chy xc nh trng thi chun gi l nhit chy chun, c k hiu:
H0298,c.
aA + bB = eE + qQ
Hs = (eHE,s + qHQ,s) - (aHA,s + bHB,s)
n v: J/mol, cal/mol. * H qu 3: Hiu ng nhit ca mt phn ng bng tng nhit chy ca cc cht tham gia tr i tng nhit chy ca cc cht to thnh. V d, hiu ng nhit DH ca phn ng: C2H4 + H2 = C2H6 55
c tnh bng nhit chy nh sau: C2H4(k) + 3O2(k) H2(k) + 1/2O2(k) Suy ra: = 2CO2(k) + 2H2O(h) = H2O(h) DH1,c DH2,c DH3,C
C2H6(k) + 7/2O2(k) = 2CO2(k) + 3H2O(h) DH = (DH1,c + DH2,c ) - DH3,c
* Nng lng ca mng li tinh th ion Nng lng ca mng li tinh th ion l nng lng cn thit phi cung cp ph v mng li tinh th thnh cc ion cu to nn mng li tinh th. Nng lng ca mng li tinh th khng th xc nh c bng thc nghim nhng c th tnh c theo chu trnh Born Haber. V d, xc nh nng lng mng li tinh th natri clorua (ENaCl = - DHNaCl ) theo chu trnh Born Haber trn hnh 5.4. y tinh th ion NaCl c th c to thnh bng phn ng trc tip ca natri vi clo hoc qua cc giai on t kim loi natri v kh clo to thnh cc ion ri tc dng vi nhau: Na (r) + 1/2Cl2 (k) DH4
H2 Na (k) H1
NaCl (r) DHNaCl
Cl (k)
H3
H5
Cl- (k) +
Na+ (k)
Hnh 5.4. Chu trnh Born-Haber xc nh mng li tinh th NaCl
Theo nh lut Hess v s hnh 5.4 ta c:

H1 = H2 + H3 + H4 + H5 + HNaCl
Suy ra:
ENaCl = -HNaCl = -H1 + H2 + H3 + H4 + H5
* Nhit bin i trng thi: Nhit bin i trng thi (nhit nng chy Hnc v nhit ho hi DHh) l nhit lng ca h trao i vi mi trng iu kin ng p khi thay i trng thi (T = const). Nhit bin i trng thi c gi tr dng.
56
5.5.
S PH THUC CA HIU NG NHIT VO NHIT :
5.5.1. Nhit dung phn t ng p Nhit dung phn t ng p (CP) l nhit lng cn thit nng nhit ca mt mol cht nguyn cht ln 1K iu kin p sut khng i (P =const) v trong khong nhit khng xy ra s chuyn pha.
Cp = H T
(5-5) (5-6)
QP = DH = CPdT 5.5.2. Nhit dung phn t ng tch :
Nhit dung phn t ng tch (CV) l nhit lng cn thit nng nhit ca mt mol cht nguyn cht ln 1K iu kin th tch khng i (V =const) v trong khong nhit khng xy ra s chuyn pha.
CV = U
(5-7) (5-8)
Suy ra:
QV = DU = CVdT
5.5.3. nh lut Kirchhoff : nh lut Kirchhof biu th s ph thuc ca hiu ng nhit phn ng vo nhit . Xt phng trnh phn ng tng qut: aA + bB = eE + qQ xy ra nhit (T = const), ta c:
= [e
T ,S
(E ) + q T , S (Q )] [a T , S ( A ) + b T , S (B )]
Suy ra :
(Q ) (B ) (E ) ( A ) +q a +b = e P P P = [eC P (E ) + qC P
2 P 2
(Q )] [aC P ( A ) + bC P (B )] =
dT
C P
57
d =
P http://hhud.tvu.edu.vn 1
Trong : CP Suy ra:

=
ao + a1T + a2T2 + .... = anTn
(5-9)
an = an (cui) - an (u)
2 = 1 + a n n d
1
(5-10)
Da vo biu thc ton hc trn y, Kirchhoff pht biu nh lut: C th tnh c hiu ng nhit bt k mt nhit T nu bit hiu ng nhit ca mt phn ng mt nhit no v bit phng trnh CP = f(T). 5.6. tng: 1. Chuyn i nng lng: - Nht t truyn t nng sang lnh - Qu bi t ln t cao xung thp 2. Thay i trt t v tr sp xp ca cc ht i vi nhau: - Hai cht kh t trn ln vo nhau (khng c s thay i nng lng) - a s cc phn ng ho hc t xy ra km theo s gii phng nng lng Tt cc cc qu trnh trn y nu mun thc hin ngc li u phi cung cp mt nng lng cn thit. Do i a s cc phn ng ho hc t xy ra m chng ta bit u km theo s gii phng nng lng (DH < 0) nn gia th k XIX, Bertlo v Tomxen a ra nguyn l: Bt k mt qu trnh ho hc no xy ra cng km theo s gii phng nng lng. Tuy nhin, nguyn l ny khng ng trong nhiu trng hp thc t. V d: - Qu trnh ho tan 1mol NaCl vo H2O xy ra vi s thu nng lng (DH = 5kJ/mol); hoc phn ng: C (r) + H2O (k) = CO (k) + H2 (k), c DH > 0. 58 NGUYN L II NHIT NG HC. ENTROPI Trong t nhin a s cc qu trnh l hc v ho hc xy ra c c trng bi 2 hin
- S trn ln 2 cht kh vo nhau nh ni trn c DH = 0. Nh vy, nguyn l I ch th hin c tnh bo ton v chuyn ho nng lng, cho php xc nh c nng lng DH ca cc phn ng nhng khng cho php xc nh iu kin t din bin ca qu trnh v hng xy ra ca n. gii quyt vn ny ngi ta a ra nguyn l II nhit ng hc. 5.6.1. Entropi : 1. Gi s c 2 cht kh He v Ar (tr, cng mt p sut v cng nhit ) c tch ra khi nhau v cnh nhau - trng thi 1 (hnh 5.5a). He He Ar Ar a. trng thi 1 b. trng thi 2
Hnh 5.5. S t trn ln ca cht kh
Mc du 2 cht kh ny khng tng tc vi nhau, cng mt p sut v cng mt nhit nh nhau, c ranh gii phn chia hon ton nh nhau nhng ch sau mt thi gian He v Ar s t trn ln vo nhau - trng thi 2 (hnh 5.5.b). Hin tng t xy ra trn y cho thy: cc cht kh trc khi trn ln (trng thi 1) c mc hn lon nh hn sau khi trn ln (trng thi 2). Vy qu trnh t din bin vi s khng thay i nng lng ca h DH = 0 (gi nguyn nng lng d tr ca h) xy ra theo hng lm tng mc hn lon ca h. Trong thc t kh c th hnh dung c rng 2 cht kh c tch ra, cnh nhau m khng trn ln vo nhau (trng thi 1). Ni cch khc l kh nng ny rt t (c xc xut rt sut nh). 2. Nu trn 2 cht kh tr c mc nng lng d tr khc nhau th nng lng ca hn hp kh thu c s bng tng nng lng ca cc cht kh ban u. Cng tng t nh vy, nu t hp 2 h c mc nng lng khc nhau li vi nhau th nng lng ca h mi thu c s bng tng nng lng ban u ca cc h. Tuy nhin trong tng hp
59
ny xc sut nhit ng ca h mi to thnh (W) khng phi bng tng m l bng tch xc sut ban u ca cc h. V d, nu 2 h c xc sut nhit ng tng ng l W1 v W2 th ta c: W = W 1 . W2 V vy cn phi tm mt hm s xc sut sao cho khi ly cc gi tr xc sut nhn vi nhau th s thu c gi tr ca hm bng tng cc gi tr cc hm tng ng vi xc sut cng li vi nhau. S ph thuc ch c th biu din bng hm logarit. Hm s logarit ny c gi l Entropi, k hiu l S: S = klnW trong k l hng s Bozman: k = R/NO Vy entropi hm logarit xc sut nhit ng ca h. V ngha, entropi l s o mc hn lon ca h, tc l h c xu hng t din bin t trng thi c trt t sang trng thi t c trt t hn. 5.6.2. Pht biu nguyn l 2 nhit ng hc : Tu thuc vo cc lnh vc ng dng khc nhau (vt l, ho hc, nhit hc, in ng hc...) nguyn l 2 c pht biu di cc dng khc nhau. Di quan im ca nhit ng ho hc, hm logarit trn y biu th xc sut tn ti ca cc hp cht v dng tn ti ca n. Gi s trong h 2 cht kh (hnh 5.5), trng thi 1 c entropi S1: S1 = klnW1 trng thi 2 c entropi S2: S2 = klnW2 th s bin i entropi khi h chuyn t trng thi 1 sang trng thi 2 s l: (5-11)
S = S 2 S1 = K ln W2 K ln W1 = K ln W12 W
Nh ni trn, y l mt h t din bin t trng thi 1 c xc sut W1 nh hn sang trng thi 2 c xc sut W2 ln hn: W2 > W1 nn suy ra S > 0. Vy trong h nhit ng c lp, ch c nhng qu trnh (k c phn ng ho hc ni ring) xy ra vi s tng entropi mi t din bin. 60
Entropi l mt thng s dung , n c gi tr bng tng entropi ca tt c cc thnh phn ca h. Thng s cng tng ng vi entropi l nhit . Do vy, nhit nng Q s l: Q = S.T Suy ra:
S = Q T
(5-12)
Entropi ca h c tnh bng n v J/K .mol. 5.6.3. Mt s phng php tnh s bin i ca entropi : 5.6.3.1. S bin i ca entropi ca qa trnh gin n thun nghch, ng nhit kh l tng T nguyn l 1 ta c: U = Qtn + Wtn V h ang xt l kh l tng (U = 0) Nn: Qtn + Wtn = 0 Qtn = -Wtn = PdV Thay ta c: Suy ra: , Qtn =
RT
dV V
= RT
ln
V2 V1
S =
Q tn V V RT = ln 2 = R ln 2 T T V1 V1
(5-13)
V qu trnh gin n (V2 > V1) nn S > 0. Vy qa trnh gin n thun nghch, ng nhit kh l tng t trng thi 1 (tng ng vi V1) sang trng thi 2 (tng ng vi V2) l qu trnh t din bin. Mt khc, V2 > V1 P1 > P2 suy ra: kh chuyn ng t ni c p sut cao n ni c p sut thp. 5.6.3.2. S bin i ca entropi ca qu trnh thay i trng thi mt cht nguyn cht Nu nhit bin i trng thi ca mt mol cht nguyn cht iu kin T = const v P = const l H th ta c entropi bin i trng thi l:
61
S =
(5-14)
5.6.3.3. S bin i ca entropi ca mt cht nguyn cht theo nhit diu kin ng p (P = const) ta c:
Q T
T2
T P
2
C
1
dT T
(5-15) (5-16)
Nu CP thay i t (CP const) th:
S = C P
T1
dT T = C P ln 2 T T1
Tng t, s bin i ca entropi ca mt cht nguyn cht V = const:
S = CV
T2
dT T = CV ln 2 T T1 T1
(5-17)
Khi nhit T2 > T1 ta c DS > 0 H t din bin. iu ny c ngha l nhit lun lun truyn t ni c nhit cao v ni c nhit thp. 5.7. NGUYN L III NHIT NG HC. ENTROPI TUYT I :
5.7.1. Pht biu nguyn l 3 nhit ng hc : Entropi l s o mc hn lon ca h. Nh ni trn, mc hn lon ny ph thuc vo nhit . Khi nhit gim xung th cc chuyn ng ca cc nguyn t, phn t gim xung, entropi gim xung. Vy gii hn ca entropi l bao nhiu v nhit no? Ni dung tr li cu hi ny chnh l nguyn l 3 nhit ng hc. Theo quan im nhit ng hc phn t, khi nhit gim gn n khng tuyt i (T0 = 0 K), mi vt tn ti di dng mt cu trc tinh th hon ho (cc dng chuyn ng u ngng li), h c nng lng thp nht. Vi iu kin ny th ch c mt h ng vi nng lng thp nht v xc sut nhit ng ca n bng 1. Suy ra:
62
S0 = klnW = kln1 = 0 khng tuyt i bng khng. 5.7.2. Entropi tuyt i :
(5-18)
Vy entropi ca cc cht nguyn cht di dng tinh th hon ho nhit
T iu kin (khi T = 0 K S0 = 0) ngi ta tnh c entropi cc nhit khc nhau. Entropi tnh c trong trng hp ny c gi l entropi tuyt i. Entropi tuyt i tnh 298 K (25 0C) v 1atm (760 mmHg) oc gi l entropi chun S0298. 5.7.3. Cch tnh entropi cc phn phn ng ho hc : Cho phn ng tng qut xy ra nhit T, (P = const): aA + bB = eE + qQ V entropi l hm trng thi nn ta c: ST (phn ng = [eST (E) + qST (Q)] - [aST (A) + bST (B)] ST (phn ng) = ST (cht to thnh) - ST (cht tham gia). 5.8. TH NG NHIT - NG P :
5.8.1. Khi nim th ng nhit - ng p : Trong cc qu trnh ho hc, cng mt lc c hai khuynh hng xy ra: 1. Khuynh hng cc ht kt hp li vi nhau lm gim entropi 2. Khuynh hng cc ht tch ra khi nhau lm tng entropi Tng ca hai khuynh hng tri ngc ny ca cc qu trnh ho hc xy ra nhit v p sut khng i (T = const, P = const) c c trng bng bi hm th nhit ng gi l th nhit ng ng nhit - ng p (gi tt l th ng p; nng lng Gibbs; entanpi t do) k hiu l G: G = H - TS Do khng xc nh c ga tr tuyt i th ng p nn trong cc phn ng ho hc ngi ta ch c th xc nh s bin i (DG) ca n: G = H - TS (5-19) 63
Da vo gi tr G c th tin on c chiu t din bin hoc khng t din bin ca qu trnh: - Qa trnh t din bin (phn ng t xy ra) l qu trnh gim entanpi t do: G < 0 - Qa trnh khng t din bin (khng t xy ra) l qu trnh tng entanpi t do: G > 0 Qa trnh cn bng xy ra khi: G = 0 Nh vy du ca DG xc nh chiu ca phn ng ho hc. 1. Nu H < 0 ( phn ng to nhit) v S > 0, suy ra G < 0, phn ng t din bin. 2. Nu H > 0 (phn ng thu nhit) v S < 0, suy ra G > 0, phn ng khng t xy ra. 3. Trong 2 trng hp cn li (H < 0, S < 0 v H > 0, DS > 0) du ca G ph thuc vo quan h gia H v TS. Phn ng ch xy ra trong trng hp G < 0. 5.8.2. Cch tnh s bin i th ng nhit - ng p ca cc phn ng ho hc Tng t nh entanpi v entropi, entanpi t do l mt hm trng thi nn s bin i ca n ch ph thuc vo trng thi u v trng thi cui m khng ph thuc vo cch thc xy ra phn ng. V vy i vi phn ng tng qut: aA + bB = eE + qQ s bin i entropi t do s l: G (phn ng) = (eGE + qGQ) - (aGA + bGB) Hay: G (phn ng) = G(cht to thnh) - G(cht tham gia) S bin i entanpi t do ca phn ng to thnh mt mol cht t cc n cht ban u iu kin chun (T = 298 K, P = 1atm) c gi l entanpi t do chun, c k hiu: G0298. Entropi t do chun to thnh cc n cht bng 0
64
Chng 6 NG HO HC
ng ho hc l mn khoa hc nghin cu v quy lut xy ra (din bin) ca cc qu trnh ho hc trong c vn tc phn ng ho hc v cc yu t nh hng n vn tc . Vic nghin cu ny nhm mc ch iu khin phn ng xy ra vi vn tc cao t c hiu sut phn ng ln nht. 6.1. VN TC PHN NG HO HC Vn tc phn ng thng c o bng bin thin nng ca mt trong cc cht tham gia hoc to thnh trong mt n v thi gian. Vn tc phn ng c biu th bng n v mol/l.s. Vn tc phn ng cng c th biu din bng s thay i ca mt trong cc tnh cht khc ca h nh mu sc, dn in, p sut... Nu ti thi im t1 v t2 nng ca mt trong cc hp cht ca h phn ng c gi tr tng ng l C1 v C2 , ta c vn tc v ca phn ng l:
v =
C 2 C1 C = t 2 t1 t
(6-1)
Trong cng thc trn, du (+) c s dng khi tnh theo cht to thnh sau phn ng; du (-) khi tnh theo cht tham gia phn ng. Trong cc phn ng ho hc, nng ca cc cht lun lun thay i nn thng ngi ta hay s dng cng thc tnh vn tc tc thi:
v =
dC dt
(6-2)
V d, i vi phn ng tng qut: aA + bB = eE + qQ ta c vn tc tc thi ca phn ng l:

dC q dCQ b dCB e dCE v= A = =+ =+ dt a dt a dt a dt
(6-3) 65
6.2.
CC YU T NH HNG N VN TC PHN NG
6.2.1. nh hng ca nng n vn tc phn ng. nh lut tc dng khi lng S ph thuc ca vn tc phn ng vo nng c xc nh bng nh lut tc dng khi lng Gulberg v Waage: Vn tc ca mt phn ng xy ra trong mi trng ng th mt nhit xc nh t l thun vi tch nng ca cc cht tham gia phn ng. V d : vn tc ca phn ng: H2 (k) + I2 (k) = 2HI c tnh theo nh lut tc dng khi lng l: (6-4) i vi phn ng tng qut: mA + nB = C ta c:
v = kC
m A
n CB
(6-5)
trong : k hng s vn tc CA v CB - nng tng ng vi cc hp cht A v B. 6.2.2. nh hng ca nhit n vn tc phn ng S tng nhit trong a s cc trng hp u lm tng vn tc phn ng. T kt qu nghin cu mt s lng ln phn ng, Vant Hoff rt ra quy tc kinh nghim sau: Nu nhit phn ng tng thm 10 0C th vn tc ca a s phn ng s tng 2 4 ln. Quy tc kinh nghim Vant Hoff c biu din bng cng thc sau:
v2 =
T 2 T1 10
v1
(6-6)
trong : v1 v v2 l vn tc phn ng tng ng vi nhit T1 v T2. g - ch s nhit (h s Vant Hoff).
66
Vn tc phn ng tnh theo cng thc Vant Hoff c gi tr gn ng. c gi tr chnh xc hn, ngui ta xc nh vn tc phn ng theo phng trnh Arrhenius:
k = C e
trong : k hng s vn tc C hng s trc lu tha Ea nng lng hot ho 6.2.3. Thuyt va chm hot ng :
Ea RT
(6-7)
Thc nghim cho thy vn tc phn ng khng phi ph thuc vo tn s va chm (s va chm trong mt n v thi gian) gia cc phn t ca cc cht tham gia phn ng m ch ph thuc vo tn s va chm gia cc phn t hot ng cao. l nhng phn t c to thnh do s tng nng lng nhit ng ca phn t, s tng ni nng, s phn ly thnh cc gc t do hoc cc ion. Nng lng cn thit cung cp cho cc phn t c trong mt mol (s Avogadro) chuyn tt c chng thnh cc phn t hot ng c gi l nng lng hot ho ca phn ng, c k hiu Ea. Ni cch khc n l nng lng cn tiu tn chuyn phn t ca cc cht tham gia phn ng thnh phc cht hot ng (hnh 6.1). E (kJ/mol) . ......................... phc cht hot ng
Ea ....... sn phm DH > 0 (phn ng thu nhit) . ........................................... cht u DH < 0 (phn ng to nhit) ........ .sn phm Tin trnh phn ng
Hnh 6.1. Gin nng lng ca phn ng ho hc
67
6.2.4. nh hng ca xc tc n vn tc phn ng Mt trong nhng phng php ph bin dng lm thay i vn tc phn ng ho hc, l s dng xc tc. Xc tc l nhng cht ho hc lm thay i vn tc phn ng bi s tham gia ca n vo vic to thnh phc cht hot ng nhng khng c mt trong thnh phn ca sn phm to thnh. Vai tr ca xc tc trong cc phn ng ho hc l lm thay i nng lng hot ho ca phn ng. Xc tc dng lm gim nng lng hot ho dn n lm tng vn tc phn ng, tri li xc tc m lm tng nng lng hot ho - lm gim vn tc phn ng. V d: ixit mangan MnO2 l cht xc tc dng ca phn ng phn hu clorat kali: 2KClO3 2KCl + 3O2 Ru etylic l cht xc tc m ca phn ng xi ho sunfit natri: 2Na2SO3 + O2 2 Na2SO4 Mt trong nhng c tnh quan trng ca xc tc l n c tnh chn lc rt cao c bit l xc tc men. V d, t ru etylic vi xc tc khc nhau s thu c sn phm khc nhau: Al2O3 CH3-CH2-OH CuO CH 3-CHO + H2 Tc dng ca xc tc dng lm gim nng lng hot ho xy ra nh sau. Ga s hai hp cht A v B c kh nng phn ng vi nhau qua bc to thnh phc hot ng A ... B, cho sn phm AB (DG < 0): A + B A ... B AB Nhng do nng lng hot ho ca phn ng ny rt ln nn thc t vn tc phn ng gn nh bng khng. lm tng vn tc phn ng ngi ta cho thm cht xc tc K. Cht ny d dng phn ng vi A to ra phc hot ng A ... K (phn ng xy ra d dng tc l phn ng c nng lng hot ho thp): A + K A ... K AK CH2=CH2 + H2O
68
Hp cht AK d dng phn ng vi B to ra sn phm AB (hnh 6.2).
A...B
B...AK
A+B A+B+K AK H AB+K

H
2 AB
Hnh 6.2. Gin nng lng ca phn ng c xc tc dng
Kt qu trn hnh 6.2 cho thy s c mt ca xc tc K lm gim nng lng hot ho ca phn ng.
69
Chng 7 CN BNG HO HC V CN BNG PHA

7.1. CN BNG HO HC : a s cc phn ng u xy ra theo 2 chiu v khi vn tc phn ng thun bng vn tc phn ng nghch, phn ng t trng thi cn bng. Ti y c phn ng thun ln phn ng nghch vn tip tc xy ra nn cn bng loi ny c gi l cn bng ng. V d, cn bng trong cc phn ng to thnh HI t H2 v I2 (hnh 7.1): H2 + I 2
% [HI]
2 HI
100 80 60 40 20 20 40 60 80 100 t (ph)
Hnh 7.1. S to thnh (1) v phn hu (2) ca HI theo thi gian
7.2. HNG S CN BNG Xt phn ng thun nghch: aA + bB vn tc phn ng thun: vn tc phn ng nghch: eE + qQ Theo nh lut tc dng khi lng ta c:
a
v1 = k 1 [ ] [B ]
e q
v 2 = k 2 [E ] [Q ]
Khi phn ng t cn bng: v1 = v2 (G = 0), ta c:
70
Suy ra:
k1 [] [B] = k 2 [E ] [Q ]
a b e
k1 [E ] [Q ] = k2 [ A ]a [B ]b
e
T l
k1 l mt hng s c gi l hng s cn bng, k hiu l KC k2

C
[E ]e [Q ]q = [A ]a [B ]b
(7-1)
KC l hng s cn bng tnh theo nng M (mol/l). Trong thc t ngi ta cn s dng cc loi hng s cn bng khc nh: cn bng tnh theo p sut KP, cn bng tnh theo nng mol phn KN, cn bng tnh theo s mol ca cc cht tham gia v to thnh trong phn ng Kn. Gia cc hng s cn bng ny c cc mi quan h sau:
K P = K C (RT )
vi
( 7-2)
e q E Q a b A B
trong n = (nE + nQ) - (nA + nB)
K P = K N P n
= NE NQ N
a A e q b
(7-3)
vi
NB
trong nng mol phn:
Ni =
KP
ni n A + n B + n E + nQ
P = Kn n i
e
(7-4)
q b
vi
n E nQ nA nB
a
trong : ni s mol ca cc cht P - p sut chung ca phn ng 71
Nu phn ng c n = 0 th cc hng s cn bng s bng nhau: KP = KC = KN = Kn. 7.3. S CHUYN DCH CN BNG. NGUYN L CHUYN DCH CN BNG LE CHATELIER 7.3.1. S chuyn dch cn bng Nh ni trn, cn bng ho hc l s cn bng ng. V d phn ng tng qut: aA + bB eE + qQ ang trng thi cn bng 1 (G1 = 0). Nu ta thay i ch mt trong cc thng s trng thi (P, C hoc T...) th cn bng s b ph v (G 0): phn ng s xy ra theo mt chiu (gi s chiu thun): aA + bB eE + qQ cho n khi thit lp c mt cn bng mi 2 (G2 = 0) tng ng vi iu kin mi. Vy s chuyn t mt trng thi cn bng ny sang mt trng thi cn bng khc di tc ng ca cc yu t iu kin phn ng c gi l s chuyn dch cn bng. 7.3.2. nh hng ca cc yu t iu kin phn ng n chuyn dch cn bng Ba yu t c nh hng ln nht n s chuyn dch cn bng l nng , nhit v p sut. 7.3.2.1. nh hng ca nng T biu thc tnh hng s cn bng theo nng :
[E ]e [Q ]q [A ]a [B ]b
Ta thy vi KC = const, nu tng [A] hoc [B] th cn bng s chuyn dch theo chiu t tri qua phi lm tng [E] v [Q] (lm gim [A] hoc [B]). Nu gim [A] hoc [B] th cn bng s chuyn dch theo chiu t phi qua tri lm gim [E] v [Q] (lm tng [A] hoc [B]).
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Nh vy, tng nng ca mt trong cc cht ca trng thi cn bng, cn bng s chuyn dch theo chiu lm gim cht . Gim nng ca mt trong cc cht ca trng thi cn bng, cn bng s chuyn dch theo chiu lm tng cht . 7.3.2.2. nh hng ca nhit Quan h gia entanpi t do v hng s cn bng c biu th qua cng thc:
G = -RTlnK hay H - TS = -RTlnK

Suy ra:
d ln K = dT RT
(7-5)
T biu thc trn ta nhn thy: Vi H > 0, nu T tng th K s gim. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm tng K (chiu t tri qua phi lm gim T). Vi H < 0, nu T tng th K s tng. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm gim K (chiu t phi qua tri lm gim T). Nh vy, nu phn ng ang trng thi cn bng m ta thay i nhit ca phn ng th cn bng s chuyn dch theo chiu chng li s thay i nhit . 7.3.2.3. nh hng ca p sut T biu thc: V T = const, ta c:
KP = KN Pn
d ln K N n = dP P
ta c: lnKP = lnKN + nlnP lnKN = lnKP - nlnP (7-6)
T biu thc trn ta nhn thy: Nu n > 0, khi P tng th KN tng. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm gim KN (chiu t phi qua tri lm gim P). Nu n < 0, khi P tng th KN gim. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm tng KN (chiu tri qua phi lm gim P). Nh vy, nu phn ng ang trng thi cn bng m ta thay i p sut chung ca phn ng th cn bng s chuyn dch theo chiu chng li s thay i p sut .
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7.3.3. Nguyn l chuyn dch cn bng Le Chatelier Nghin cu nh hng ca cc yu t n s chuyn dch cn bng phn ng, nm 1884 Le Chatelier da ra nguyn l chuyn dch cn bng: Mt h ang trng thi cn bng, nu ta thay i mt trong cc thng s trng thi ca h th cn bng s chuyn dch theo chiu chng li s thay i . 7.4. CN BNG PHA 7.4.1. Mt s khi nim c bn * Pha: Tp hp tt c cc phn ng th ca h c thnh phn,tnh cht vt l, ho hc ging nhau v c b mt phn chia vi cc phn khc ca h gi l pha. V d, h nc v nc l h c 2 pha trong mt pha l nc lng v mt pha l nc . H ny dc gi l h d th v c 2 pha; nc lng hoc nc l h ng th v ch c mt pha. * Cn bng pha: Cn bng trong cc h d th m khng xy ra phn ng ho hc gia cc cu t vi nhau nhng xy ra cc qu trnh bin i pha ca cc cu t c gi l cn bng pha. * Cu t: Phn hp thnh l nhng hp cht ho hc ng nht ca h c th tch ra v tn ti c lp bn ngoi h gi l cu t, c k hiu R. V d, dung dch mui n c 2 cu t l H2O v NaCl (cc ion Na+, Cl-... khng phi cu t ). * S cu t c lp: S nh nht cc cu t m t thnh phn ca tt c cc pha c trong h gi l s cu t c lp, c k hiu K. K=R-q S cu t c lp K c khi bng R nhng cng c khi khc R. Khi xt mt h m trong khng xy ra s chuyn i ho hc ( cc cu t khng tc dng vi nhau) ta
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c: R = K. Trong v d dung dch mui n trn y R = K = 2. Mt khc, nu xt h m trong xy cc tng tc ho hc th ta c R K. V d, i vi h phn ng: 2H2 + O2 = 2H2O ta c: R = 3, K c th l 1 hoc 2. K=R-1=3-1=2 v bt k mt cu t no ca h cng c th xc nh c bng 2 cu t kia. 7.4.2. Quy tc pha Gibbs Nh ta bit, s cn bng ca h ph thuc vo cc iu kin (nhit , p sut, nng ). S iu kin c th thay i mt cch c lp m khng lm thay i s pha v loi pha ca h c gi l s bc t do, c k hiu C. Nghin cu cn bng pha ca h d th, Gibbs da ra quy tc sau: Trong h cn bng, s lng pha f, s bc t do C v s cu t c lp K lin h vi nhau qua biu thc: C=K-+2 7.4.3. Cn bng pha trong h mt cu t Trong nghin cu cn bng pha ngi ta thng hay chn phng php th bng cch xy dng gin trng thi trn c s ca cc gi tr thc nghim. Gin trng thi c th xy dng cho mt hp cht bt k v n cho php xc nh iu kin bn ca pha hoc cn bng pha. Hnh 7.2 di y l gin trng thi ca nc. P mmHg 760 ............B. ...................... C lng (L) rn (R) 4,579 . ............... O hi (H) A 0 t 0C
Hnh 7.2. Gin trng thi ca nc
(7-7)
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Trn hnh 7.2 cho thy mi mt min c gii hn bi cc ng cn bng pha, tng ng vi mt pha xc nh (, lng, hi). S bc t do theo quy tc pha Gibbs trn mi min l: C=K-+2 = 1-1+2 = 2 H c C = 2 c gi l h nh bin, c ngha l s cn bng ca h trong trng hp ny ph thuc vo 2 iu kin. Nu C = 0 h v bin; C = 1 h nht bin ... ng OA biu th s cn bng gia 2 pha R H; OB gia R L; OC gia L H. Mi mt ng tng ng vi 2 pha v do s bc t do theo quy tc pha Gibbs trn mi ng l: C=K-+2 = 1-2+2 = 1 im O l im ct ca 3 ng (im ba). im ny tng ng vi cn bng gia 3 pha: R L H
S bc t do tnh theo quy tc pha Gibbs ti im ny l: C=K-+2 = 1-3+2 = 0
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Chng 8 DUNG DCH

8.1. MT S KHI NIM CHUNG
8.1.1. H phn tn Mt h gm hai (hay nhiu tiu phn ) trong mt tiu phn dng cc ht b tn nh c phn b vo trong tiu phn kia th h c gi l h phn tn Cht phn b c gi l pha phn tn, cn cht trong c pha phn tn phn b gi l mi trng phn tn. Mi trng phn tn c th l cht kh, cht lng hoc cht rn. V d : H phn tn bi, khng kh (pha phn tn - cc ht bi, mi trng phn tn- khng kh) Tnh cht ca mt h phn tn , c bit tnh bn ca n ph thuc vo kch thc ca pha phn tn. Pha phn tn c kch thc ht cng ln th h phn tn cng t bn v ngc li h c pha phn tn c kch thc ht cng nh th cng bn. Da vo kch thc ht ca pha phn tn ngi ta phn chia thnh cc h phn tn sau: * H th: Trong h ny ny ht pha phn tn c kch thc ht t 10-7 n 10-4 m. H ny gm c huyn ph v nh tng, h ny khng bn. - Huyn ph l h c to thnh bi pha phn tn th (cht rn) v mi trng phn tn (cht lng ) . V d: Nc c - Nh tng l h c to thnh t hai cht lng trong cht ny c phn b vo trong cht kia . V d: Sa ng vt. * H keo: L h phn tn c cc ht pha phn tn c kch thc t 10-7 n 10 -9m. Nhng ht ny khng b lng xung theo thi gian, i qua c giy lc v khng quan st c bng knh hin vi thng thng...
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* H phn tn phn t : L h phn tn c cc ht pha phn tn c kch thc bc phn t . y cht ho tan c phn chia thnh cc phn t ring bit V d : cc dung dch tht ca ng, ru, axeton... * H phn tn ion: Trong h ny cc ht pha phn tn tn ti di dng nhng ion ring bit . Trng hp ny c c trng cho dung dch ca cc cht in li nh NaCl, KNO3, KCl... Kch thc ca ht phn tn v ca mi trng phn tn l bng nhau. 8.1.2. nh ngha dung dch Trong ho hc hai h phn tn c ngha nht l phn t v ion c gi l dung dch: Dung dch l mt h ng th c thnh phn bin i trong mt phm vi tng i rng gm khng t hn hai cht trng thi phn t hay dng ion * Dung mi: Mt h ng th c ngha l cc tiu phn ca h c phn tn vo nhau di dng phn t , nguyn t v ion..Tiu phn c trng thi khng thay i khi to thnh dung dich c gi l dung mi. Trong trng hp dung dch c to thnh bng phng php trn cht kh vi cht kh , cht lng vi cht lng , cht rn vi cht rn th dung mi l tiu phn no c khi lng tri hn , cht cn li l cht tan. Cn c vo trng thi tn ti, dung dch c chia thnh dung dch kh, dung dch lng, dung dch rn * Dung dch kh: iu kin p sut thng dung dch kh c xem nh l mt hn hp kh . V d khng kh l mt hn hp gm cc cht kh ho tan vo nhau (Nit 78%, Oxi 21%, kh tr 1%, ioxit cacbon, hi nc...) * Dung dch rn: Dung dch rn c to thnh khi lm lnh mt hp kim lng ca cc kim loi ( c cng mt loi mng li tinh th v c kch thc nguyn t xp x nhau...) ho tan trong 78
nhau theo bt k mi t l ( ging nh ru ho tan trong nc ) l nhng hp kim nh: Ag-Cu; Cu-Ni; Mn-Fe; Ag-Au; Pt-Au... * Dung dch lng: Dung dch lng c to thnh khi cht tan l kh , lng hoc rn cn dung mi l cht lng. Trong ho hc loi dung dch ny c ngha rt ln v c quan tm nghin cu nhiu nht. 8.1.3. Cc phng php biu din nng ca dung dch Mt trong nhng c tnh quan trng ca dung dch l thnh phn ca n. Thnh phn nh tnh cho bit v bn cht cc cu t ca dung dch cn thnh phn nh lng cho bit mi cu t c cha trong dung dch vi nhng nng l bao nhiu . Nng ca dung dch l lng cht tan c trong mt n v khi lng hoc mt n v th tch dung dch hay trong mt n v khi lng dung mi. C nhng cch biu din nng khc nhau v di y l mt s phng php biu din thng c dng nhiu trong thc t: * Nng phn trm: Nng phn trm Ci l khi lng gam cht tan c trong 100 gam dung dch.
Ci =
mi 100 (%) m
(8-1)
Trong : mi - Khi lng cht tan (gam) m - Khi lng dung dch bao gm c cht tan (gam) * Nng molan: Nng molan e l s mol cht tan i trong 1000 gam dung mi :
ni 1000 (molan) m
(8-2)
Trong : - ni l s mol cht tan trong m gam dung mi. * Nng mol: Nng mol M l s mol cht tan c trong 1 lt dung dch. 79
V d: dung dch HCl 1M c ngha l trong 1 lt dung dch c 1 mol HCl * Nng ng lng: Nng ng lng N l s ng lng gam ca cht tan trong 1 lt dung dch.
V d: dung dch KOH 1N c ngha l trong lt dung dch c 1 ng lng gam KOH.
Trong phng php nh phn ngi ta thng s dng rng ri biu thc v nh lut ng lng sau y: Nu cho VA ml dung dch A nng NA tc dng va vi VB ml dung dch B vi nng NB th ta c: NA.VA= NB.VB * Nng phn mol ca cht tan i: Nng phn mol Ni hay cn gi l nng mol phn l t s gia s mol ni ca n vi tng s mol ni ca tt c cc cht to nn dung dch. (8-3)
Ni =
ni n = i n1 + n2 + n3 + L ni
Ni = 1
(8-4)
T biu thc (8-4) suy ra:
8.1.4. Tng tc gia dung mi v cht tan, ho tan 8.1.4.1. Tng tc gia dung mi v cht tan Ho tan l s phn tn cht tan di dng ion, nguyn t phn t vo trong khp th tch ca dung mi bng 2 qu trnh : ph v trng thi tp hp ca cht tan v tng tc ca dung mi vi cc ht ho tan to thnh cc sonvat (nu dung mi l nc th gi l cc hyrat) (Hnh 8.1)
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Na +
-
Cl+
Na+
-
Cl+
+
-
+ -
Na + Cl-
ClNa +
Na+ Cl-
Cl+
+ -
Hnh 8.1. S ho tan tinh th NaCl vo nc.
S ho tan t xy ra v khng thun nghch cho n khi h t trng thi cn bng (dung dch bo ho). Do vy trong qu trnh ho tan ta c:
G = Hht - TS < 0
Trong
Hht = Hs + HCT S = Spt + SS

Entropi phn tn c gi tr dng (Hpt > 0); (8-7)
Entropi sonvat c ga tr m (HS < 0) v |(Hpt | > | HS | nn theo (8-7) ta c
S > 0. Nhng gi tr S khng ln lm nn gn nh khng gy nh hng n entropi

ho tan Hht . Entropi sonvat ho c gi tr m (HS < 0) cn entropi ph v cu trc tinh th c gi tr dng (HCT > 0) nn theo (8-6) Hht c th m hoc dng Nhit lng thot ra hay thu vo khi ho tan mt mol ca mt cht gi l nhit ho tan S ho tan ca cht rn vo cht lng, cht lng vo cht rn cht kh vo cht lng thng xy ra vi s to nhit (Hht < 0) 81
Na+
+
Cl+ +
Cl
Na
Cl
Na
Na +
+ +
+
+
+ -
+ -
+ -
+ -
(8-5) (8-6)
Tuy nhin trong mt s trng hp s ho tan ca cht rn vo cht lng xy ra vi s thu nhit (Hht > 0) . V d s ho tan ca cc mui NaCl, NH4OH vo nc. iu ny c gii thch bi gi tr ca TS > Hht 8.1.4.2. ho tan Nu ta cho mt cht A ho tan vo trong mt cht B mt iu kin xc nh th qu trnh t xy ra khng thun nghch cho n khi h t trng thi cn bng (G =0). Dung dch thu c ny gi l dung dch bo ho. Nng ca dung dch bo ho c gi tr khng i v c gi l ho tan.Thng ho tan c k hiu s l s gam cht tan trong 100 gam dung mi Cho ti nay cha c mt inh lut tng qut v ho tan nhng nhn chung ho tan ca cc cht khc nhau th khc nhau v ph thuc vo nhit . Mt khc mt mc nht nh c th p dng qui tc kinh nghim : cc cht c cu to phn t ging nhau th d ho tan trong nhau (cc cht khng phn cc hoc t phn cc th d ho tan trong dung mi khng phn cc ; cc cht phn cc th d ho tan trong dung mi phn cc. * ho tan cht kh vo cht lng: ho tan ca cc cht kh trong cc cht lng thng rt khc nhau v khi nhit tng ln th ho tan ca cc cht kh trong cc dung mi phn cc gim cn trong cc dung mi khng phn cc li tng ln. Mt khc ho tan ca cc cht kh trong cc cht lng t l thun vi p sut ca n trn b mt cht lng theo nh lut Henry: m= kp Trong : m- Khi lng kh ho tan trong mt th tch xc nh ca cht lng k- H s t l ph thuc vo bn cht ca cht kh v dung mi * ho tan cht lng vo cht lng: ho tan ca cht lng vo cht lng c th l v hn (ho tan ca ru etylic vo nc), nhng thng th c gii hn (ho tan ete vo nc). (8-8)
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Mt khc khi nhit tng th ho tan ca cht lng vo trong cht lng c th tng (ho tan nc vo ete) hoc c th gim (ete vo nc). * ho tan cht rn vo cht lng:
tan, g/100g n c hoa
180 160 140 120

KN
2.4 2.2 2.0 1.8 1.6 1.4

l 4C NHaCl N
O3
CaSO4
100 80 60 40 20 0
1.2 1.0 0.8 0.6 0 20 40 60

o
O4 CuS lO3 Cl2 KC Hg
20 40 60 80 100
Nhi C t , a
o
80
100
120
Nhi C t , b
Hnh 8.2 : S ph thuc ho tan ca mt s cht vo nhit
ho tan ca hu ht cht rn vo cht lng tng ln khi nhit tng (Hnh 8.2 a ). Tuy nhin trong mt s trng hp khi nhit tng ho tan ca cht rn gim (Hnh 8.2 b) Khi nhit gim th ho tan ca cht rn gim. Gi s nhit t1 ho tan ca cht rn l s1 v nhit t2 l s2 . Vy khi nhit gim t t2 n t1 th c mt lng cht rn a = s2 - s1 kt tinh li . Tuy nhin trong mt s trng hp nu ta lm ngui tht cn thn dung dch bo ho ca mt s cht th khi n nhit gim n t1 ta khng thu c mt lng cht rn a kt tinh li. Dung dch nh vy gi l dung dch qu bo ho - dung dch c nng ln ho tan nhit . Dung qu bo ho khng bn do ch cn khuy nh hoc cho vo dung dch ny mt mt vi tinh th mm kt tinh th lng cht rn a s kt tinh li v dung dch s tr thnh bo ho.
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8.2.
TNH CHT CA DUNG DCH CHT KHNG IN LI
8.2.1. p sut hi ca dung dch long cht khng in li v khng bay hi Hi cn bng vi dung dch lng gi l hi bo ho ca dung dch. Nu n cha mi cu t ca dung dch th p sut hi s bng tng p sut hi ring phn ca cc cu t. i vi dung dch khng bay hi h 2 cu di y, p sut hi bo ho l p sut ca dung mi nguyn cht. 8.2.2. nh lut Raoult v gim p sut hi ca dung mi trn dung dch Nm 1886 bng thc nghim Raoult tm thy p sut hi ca dung mi trn dung dch long b hn p sut ca dung mi lng nguyn cht cng nht v p sut ngoi. i vi dung dch lng p sut hi P1 ca dung mi t l vi phn mol N1 ca n: P1= k1. N1 hi P10 ca dung mi lng (cu t 1) nguyn cht cng nhit : P1 = P10 . N1 c : N1 + N 2 = 1 suy ra: N1 = 1 - N2 P1 = P10 .(1- N2) Thay N1 vo (8-10), ta c: (8-10) Gi N2 l phn mol ca cht tan (cu t 2 trong dung dch) , i vi h 2 cu t ta (8-9) Khi N1 = 1 (dung mi lng nguyn cht) P1 = P10 = k1 c ngh l k1 chnh l p sut
10 1 = 2 10
hay
= 2 10
(8-11)
Hiu P = P10 - P1 gi l gim tuyt i p sut hi ca dung mi 84
Cn P/ P10 gi l gim tng i p sut hi ca dung mi v dng (8-11) nh lut Raoult c th pht biu : gim tng i p sut hi ca dung mi trn dung dch long khng in li bng phn mol ca cht tan trong dung dch i vi dung dch rt long , n2 << n1 , (8-11) c th vit :
Trong :
n2 n m = 2 = 2 = 0 n1 + n2 n1 n1 M 1
(8-12)
m - khi lng cht tan c trong n1 mol dung mi M : Khi lng mol ca cht tan dng (8-12) nh lut Raoult c th pht biu : gim tng i p sut hi ca dung mi trn dung dch long khng in li t l vi s mol ca cht ho tan c trong mt lng dung mi xc nh 8.2.3. gim nhit ng c v tng nhit si ca dung dch long cht tan khng bay hi:
1atm A A' A''

t2
O ' O
'' O
t1
t,0C
Hnh 8.3 : Gin tng nhit si ca dung dch
85
Bt c pha lng no nguyn cht hay dung dch cng bt u si nhit m ti p sut hi bo ho ca n bng p sut ngoi v ng c nhit m ti p sut hi ca n bng p sut ca tinh th cht rn ca pha lng Khi ta cho vo dung mi 1 cht tan khng bay hi th p sut hi ca dung mi trn dung dch s gim xung dn n lm tng nhit si v lm gim nhit ng c ca dung dch (so vi dung mi nguyn cht ) Trn hnh (8.3 ) biu din s ph thuc p sut hi ca dung mi nguyn cht (H2O - OA) v dung dch (O A,O A ) vo nhit . T gin ta thy dung dch ng c nhit thp hn v si nhit cao hn so vi dung mi nguyn cht . Gi tr nh lng lng ca s ph thuc c Raoult thit lp:
T = k . e T S = k S . e
trong :
(8-13) (8-14)
T ( gim nhit ng c) = T(dung mi) - T (dung dch) Ts ( tng nhit si) = Ts (dung dch) - Ts (dung mi)
k , kS - hng s nghim ng v hng s nghim si; e - nng molan (s mol cht tan trong 1000 gam dung mi). Nu gi m l khi lng gam cht tan c trong D gam dung mi , M khi lng mol cht tan th (8.13) v (8.14) c dng:
Td = k d
m . 1000 MD
(8-15) (8-16)
TS = k S
lnh hoc php nghim si
m . 1000 MD
Phng php xc nh M da vo (8-15) hoc (8-16) c gi l php nghim y l nhng phng php thc nghim c s dng rng ri trong thc t. 8.2.4. p sut thm thu: * Th nghim 1:
86
Gi s cho hp cht CuSO4.5H2O tip xc vi nc. Cc phn t ca cht tan s khuych tn vo dung mi cn cc phn t dung mi s khuych tn theo chiu ngc li: hng khuych tn ca phn t cc hp cht xy ra theo chiu t ni c nng cao n ni c nng thp. Kt qu ca s khuych tn hai chiu dn n lm cn bng nng trong tt c th tch dung dch. * Th nghim 2: Nu ta nhng bnh nghim 1 ng dung dch ng c y l mt mng bn thm (mng ch cho dung mi i qua cn cht tan khng i qua c) vo cc nc 2 (hnh 8.4).
1 2 h
Hnh 8.4 : Thit b n gin o p sut thm thu
Cc phn t nc t ni c nng cao (t cc nc 2) s khuych tn qua mng bn thm n ni c n c nng thp (bnh nghim 1). Hin tng khuych tn mt chiu cc phn t dung mi i qua mng bn thm gi l s thm thu. Lc tc dng ln mt n v b mt ngn cn cc phn t dung mi i qua mng bn thm gi l p sut thm thu. Trong th nghim trn p sut thm thu chnh bng p sut thu tnh ca ct dung dch c chiu cao l h Nm 1886 bng thc nghim Vant Hoff thit lp c phng trnh tnh p sut thm thu ca dung dch long : Pt = C RT Trong C l nng mol 87 (8-17)
Nu n2 l s mol cht tan c trong th tch V ca dung dch , m l s gam cht tan c trong th tch v M l khi lng phn t cht tan ta c :
Pt = nRT mRT = V MV
(8-18)
Vy nh lut Vant Hoff c th pht biu: p sut thm thu ca dung dch long c gi tr bng p sut m s mol cht tan c c nu nh trng thi kh l tng n chim mt th tch bng th tch V ca dung dch v cng mt nhit T nh dung dch. 8.3. TNH CHT CA DUNG DCH CHT IN LI
8.3.1. Thuyt in ly 8.3.1.1. Tnh cht bt thng ca dung dch in li Tt c cc hp cht c chia thnh 2 loi: cht in li v cht khng in li. Cht in li (axt, baz, mui) l nhng hp cht m trng thi dung dch lng hoc nng chy c kh nng dn in. Cht khng in li (ru, ete, hydrocacbon...) l nhng cht khng dn in. Trong phn tip theo ch nghin cu dung dch nc ca axt, baz v mui. Nghin cu tnh cht ca dung dch in li ngi ta nhn thy rng cc gi tr: gim p sut hi bo ho Dp', gim nhit ng c Dt', tng nhit si Dt's v p sut thm thu Pt' thu c bng thc nghim u ln hn Dp, Dt, Dts, P tng ng tnh theo l thuyt ca dung dch cht khng in li. 8.3.1.2. Thuyt in li ca Arrhennius Tnh cht bt thng trn y ca dung dch cht in li c Arrhenius gii thch bng thuyt in li. Theo ng khi ho tan trong nc cc phn t cht in li phn li thnh cc phn t mang in tch dng (ion dng) v cc phn t mang in tch m (ion m). Hin tng cc phn t phn li thnh cc ion gi l s in li hay s ion ho. Di tc dng ca dng in, cc ion dng chuyn n catot v cc ion m chuyn n anot dung dch dn in.
88
nh lng v tnh cht bt thng ca dung dch cht in li Van't Hoff a vo cc cng thc (8-11, 8-13, 8-14, 8-17) tha s hiu chnh i gi l h s Van't Hoff. Nh vy i vi dung dch cht in li ta c:
p' p = i 0 = i N2 0 p1 p1
t' = ik.C t's = iks.C

P' = ic2RT Suy ra: i=
p ' t ' t ' s ' = = = p t t s
(8-19)
Nh vy, i vi dung dch cht in li ta c i >1, dung dch cht khng in li i=1. ngha vt l ca h s Van't Hoff. I= S phn t c trong dung dch S phn t ho tan (8-20)
Thuyt in li ca Arrhenius tuy gii thch c tnh bt thng v tnh dn in ca cc dung dch axt, baz, mui bng s ion ho ca cht tan nhng cha nu ln c vai tr ca dung mi. Thiu st ca Arrhenius c b sung bng thuyt in li hin i ca Cablucp. 8.3.1.3. Thuyt in li Caclucp in li l qu trnh phn li phn t cht in li thnh cc ion di tc dng ca dung mi phn cc. S ion ho cht in li bi tc dng ca dung mi phn cc chia thnh 2 loi: 1. S in li ca hp cht ion V d: S ho tan ca NaCl trong H2O to thnh cc hydrat c trnh by trn hnh 8.1. y phng trnh in li ca NaCl c th vit: NaCl + mH2O = Na+.nH2O + Cl-(m-n)H2O 89
2. S in li ca hp cht phn cc V d: S ho tan ca HCl vo H2O (hnh 8.5 ) y di tc dng ca H2O phn t HCl tr thnh phn cc hn v dn dn chuyn thnh ion.
A
Cation
HCl + nH2O = H3O+ + Cl-(n-1)H2O S in li l mt qu trnh thun nghch (
Anion
Hnh 8.5 : S qu trnh hyrat ho v phn ly ca phn t phn cc dng HCl
) trong mi quan h v nng
gia cc phn t khng phn li v cc ion c nh lng bng in li . 8.3.1.4. in li. Hng s in li * in li: in li a l t s gia s phn t phn li trn s phn t ho tan. Nu tnh theo nng mol th:
=
Trong :
x x hoc = .100% n n
(8-21)
x - s mol phn t cht tan phn li; n - s mol phn t cht tan c trong dung dch. T (8-20) ta nhn thy 0 1 hoc 0 100%. Nh vy i vi cht khng in li = 0. i vi cc cht in li thng chia thnh 3 loi: Cht in li mnh > 30% Cht in li trung bnh a trong khong 2-30% 90
Cht in li yu < 2%. * Hng s in li: i vi cht in li yu c th vn dng nh lut tc dng khi lng tnh hng
s cn bng K. V d, hng s cn bng ca axt axtic: CH3COOH

+
CH3COO- + H+
_ 3
K=
[H ] [CH COO ]
[CH 3 COOH ]
Hng s cn bng ion trong dung dch cht in li gi l hng s in li. i vi cht in li yu K khng ph thuc vo nng dung dch m ch ph thuc vo nhit . *Quan h gia in li v hng s cn bng: Gi s trong v d trn dung dch axt axtic c nng C mol/lit v in li a, ti thi im cn bng ta c: Kation hydr ........................ [H+] = C.a Anion axit . ................[CH3COO-] = C.a S phn t khng phn li . ........................... [CH3COOH] = C(1-a) Suy ra:
[H + ][CH 3COO - ] C.C 2 = = .C K = [CH 3COOH] C (1 - ) 1 -
K=
2 .C 1-
(8-22)
Phng trnh (8-22) l biu thc ton hc n gin nht ca nh lut pha long Ostwald. Theo (8-22) ta thy nu a tng th K tng, do mun K = const th C phi gim. Tc phi lm long dung dch. i vi cht in li yu a c gi tr nh 1-a tnh gn ng bng 1 suy ra (8-22) c dng: K = 2.C (8-23)
91
8.3.1.5. Phng php xc nh in li in thng c xc nh t dn in. i vi dung dch long cht in li yu: a= Trong :

- dn in ng lng: dn in ca mt ng lng gam cht tan c

trong mt th tch V cm3 vng gia 2 in cc t cch nhau 1cm.
- dn in ng lng gii hn khi dung dch c lm long n v

cng (C 0; V ) in li cng c th xc nh qua mi quan h ph thuc ln nhau gia a v i. Gi s s mol cht in li trong mt th tch l N, s ion do mt phn t phn li l n th ta c s ion trong dung dch l naN, s mol cht in li khng phn li (N-aN), s phn t c trong dung dch (N-aN + naN). Theo (8-20) ta c i = Suy ra:
N N + nN N
i 1 n 1
(8-24)
Trong i xc nh bng thc nghim theo (8-19) ri thay vo (8-24) s tm c a. 8.4. THUYT AXT - BAZ Hu ht cc cht in li u biu hin hoc tnh axt hoc tnh baz. Tuy nhin cho n nay cha c mt nh ngha tng qut mang tnh cht c trng cho mi quan h tng tc axt - baz trong mi loi dung mi. Do vy cc thuyt axt - baz sau y ch cp n trng hp dung mi l nc. 8.4.1. Thuyt axt - baz Arrhenuis Axt l hp cht c cha nguyn t hyro, khi phn li trong nc cho ion H+ Baz l hp cht c cha nhm OH, khi phn li trong nc cho ion HO-
92
Quan im trn ca Arrhenuis gii thch tt c nhiu vn thc nghim. l dung dch cc axt (hoc baz) u c chung mt s tnh cht v u c cha H+ (hoc HO-); quan h tng tc axt - baz thc cht l phn ng trung ho: H+ + HO- = H2O dn in v tnh xc tc ca cc dung dch bin i t l vi ion H+. Tuy nhin thuyt axt - baz ca Arrhenuis c mt s mt hn ch. l phn t NH3 khng cha HO-, phn t CO2 khng cha H+ nhng khi ho tan trong nc NH3 th hin tnh baz, CO2 th hin tnh axt. axt v baz c th phn ng vi nhau m khng cn phn li thnh ion . V d, HCl khan phn ng vi NaOH khan. Mt s hp cht in li c cha hyr khi phn li trong dung dch ny th hin tnh axt nhng trong dung dch kia th hin tnh baz. V d: Anilin trong amnic th hin tnh axt: C6H5NH2 + NH3 Trong nc th hin tnh baz: C6H5NH2 + H2O ch n vai tr ca dung mi. 8.4.2. Thuyt axt - baz ca Bronsted Theo Bronsted, axt l cht c kh nng cho proton cn baz l cht c kh nng kt hp proton. Qu trnh ion ho l s tng tc ca cht tan vi dung mi trong dung mi c th ng vai tr hoc axt hoc baz. V d: NH3 baz HCl axt + + H2O axt NH3 baz 93

C6U5NH- + NH + 4
C6H5NH3+ + HO-
Nhng hn ch trn y ca thuyt axt - baz ca Arrhenuis l do ng khng
NH + 4
HOCl-
NH + 4
Nh vy nu i lc n proton ca dung mi ln hn cht tan th dung mi th hin tnh axt cn nu nh hn th th hin tnh baz. Tng t nh phn ng xi ho - kh phn ng ca cht ho tan vi dung mi c xem nh l tng ca hai qu trnh axt - baz lin hp (cp axt - baz lin hp). V d: HCl axt 1 + H2O baz 2 H3O+ axt 2 + Clbaz 1
HCl Cl- v H3O+ H2O l cc cp axt - baz lin hp. so snh mnh, yu ca cc cp axt - baz ngi ta thng ly cp H3O+ H2O lm chun gi l thang axt - baz i vi nc. 8.4.3. Tch s ion ca nc - ch s hyr ( pH) Cp H3O+ - H2O ca nc t ion ho H2O + baz 1 hay 2H2O H2O axt 2 H3O+ + H3O+ axt 1 HO+ HObaz 2
Ngi ta vit: = [H3O+] [HO-] v gi l tch s ion ca nc. Cc nng ion: [H3O+] = [HO-] = C c xc nh bng cch o dn in ca nc v dn in mol , ca cc ion 25oC: C =
H 2O H O+ + HO
3
5,5.10 6 1 , m 1 = 10 4 mol.m 3 = 10-7 M 4 1 2 1 (350 + 198)10 .m .mol
Suy ra:
K H2O = C 2 = [10-7]2 = 10-14 (M)
Ngi ta nh ngha pH l logarit thp phn hot proton hydrat ho. Nu [H3O+] << 1M ta c: pH = - lg[H3O+] i vi nc nguyn cht [H3O+] = [HO-] =
K H 2 O = 10-7
(8-25)
94
Suy ra:
pH = 7 mi trng trung tnh pH < 7 mi trng l axt pH > 7 mi trng l baz
Mt cch tng t, ngi ta nh ngha: pOH = -lg [HO-] V Suy ra: [H3O+] [HO-] = pH + pOH = p = 14 (8-27) (8-26)
8.4.4. mnh ca axt v baz Xt dung dch nc ca axt HA HA + H2O phn t HA (v d axt HCl, HNO3...) Trong trng hp nu HA phn li khng hon ton ta c: Ka =
[ H 3 O + ][ A ] [ HA]
H3O+ + A-
Axt mnh nu n phn li hon ton, tc l trong dung dch khng cn tn ti cc
(8-28)
Ka l hng s cn bng v thng gi l hng s axt. Ngi ta cng nh ngha: pKa = -lgKa Axt s cng mnh khi pKa cng b. Xt dung dch nc ca mt baz B + H2O c: Kb =
[BH + ][HO ] [B ]
(8-29)
BH+ + HO-
Baz mnh nu B phn li hon ton, v d NaOH, trong trng hp ngc li ta
(8-30)
Trong Kb l hng s baz. Ngi ta cng nh ngha: pKb = -lgKb Baz cng mnh khi pKb cng b. 95 (8-31)
Xt mi quan h gia pKa v pKb ca mt cp axt - baz ta c: i vi axt HA: HA + H2O Ka = i vi baz lin hp A- ca n: A- + H2O Kb = Tch: Suy ra: Ka.Kb = . = [H3O+][HO-] = pKa + pKb = 14 (8-32) HA + HOA- + H3O+
Nu axt HA tng i mnh (pKa b) th baz lin hp ca n A- yu v ngc li. 8.4.5. Tnh pH ca cc dung dch nc 8.4.5.1.Tnh pH ca axit * Axit mnh: Phn ng phn li axt mnh (phn li hon ton ): HA + H2O = H3O+ + APhn ng phn li nc: 2H2O H3O+ + HONu b qua cc ion H3O+ do nc phn li ta c: [H3O+] = [A-] = Ca Ca l nng mol ca axt Suy ra: * Axt yu: Phn ng phn li axt yu: HA + H2O Phn ng phn li nc: 2H2O Hng s phn li: Ka =
[H 3O + ][A ] [HA ]
pH = -lg[H3O+] = -lgCa
(8-33)
H3O+ + AH3O+ + HO-
96
Phn ng phn li y ch yu l: HA + H2O Do [H3O+] = [A-] Ca = [HA] + [A-] suy ra: Do :

[H 3O + ] Ka = C a [H 3 O + ]
H3O+ + A-
Nu Ca l nng axt th: [HA] = Ca - [H3O+]
Suy ra:
[H3O+] =
2 K a K a + 4K a C a 2
(8-34)
Nu axt rt yu v nng axt khng qu nh [A-] << [HA] C th vit [HA] Ca , ta c:

[H 3O + ]2 Ka = ca
Suy ra:
[H3O+] =
KaCa
(8-35)
8.4.5.2. Tnh pH ca baz * Baz mnh: Phn ng phn li ca dung dch baz mnh (phn li hon ton): 2H2O B + H3O+ H3O+ + HOBH+ + H2O
Nu b qua [H3O+] do nc phn li th theo nguyn l trung ho in ta c: [HO-] = [BH+] = Cb Cb l nng mol ca baz. T: Suy ra: pH = -lg[H3O+] = 14 + lgCb (8-36) [H3O+] =
97
* Baz yu: Phn ng phn li ca dung dch baz yu 2H2O B + H3O+ Cng (1) v (2) ta c: Do hng s phn li: Kb =
[BH + ][HO ] [B ]
H3O+ + HOBH+ + H2O BH+ + HO-
(1) (2)
B + H2O
Nu b qua nng [H3O+] do nc phn li, ta c [BH+] = [HO-] V t Cb = [B] + [BH+], ta c [B] = Cb - [BH+] Kb = Suy ra: [HO-] =
K b K 2 + 4K b C b b 2
[HO ]2 [C b [HO ]
(8-37)
Nu baz rt yu v nng baz khng qu nh [BH+] << [B] th c th vit [B] Cb v: Kb =

[HO ]2 Cb
Suy ra: [HO-] =
K bC b
(8-38)
T (8-37) v (8-38) tnh c pOH v pH theo cng thc: pH = 14 - pOH 8.4.5.3. Tnh pH ca cc dung dch mui Mui l hp cht c to thnh t cation kim loi hoc ion amoni NH + v anion 4 gc axt. Nghin cu tnh cht ca mui ngi ta nhn thy rng mt trong nhng tnh cht ho hc chung ca chng l s thu phn - tc l phn ng gia cc ion mui vi nc. Trong phn ng ny c th mt loi ion ca mui (cation hoc anion) c kh nng kt hp mnh hn vi ion H3O+ hoc HO- ca nc lm cho cn bng 2H2O H3O+ + HO98 (8-39)
chuyn dch v bn phi. Kt qu l sn phm ca s thu phn c th c tnh axt hoc baz dn n s thay i pH ca dung dch. Trong thc t thng gp ba trng hp mui b thu phn sau: 1. Nu mui c to thnh bi baz mnh v axt yu nh Na2CO3, K2CO3, CH3COONa, KCN... th khi thu phn dung dch mui s c pH >7. V d: CH3COONa = 2H2O CH3COO- + H3O+ Na+ + CH3COOCH3COOH + H2O H3O+ + HO-
S kt hp CH3COO- vi H3O+ to thnh cht in li yu CH3COOH lm chuyn dch cn bng in li ca nc, tc l lm tng HO-. Do vy dung dch c tnh baz (pH > 7). Trong trng hp ny, trnh thu phn cn phi cho thm kim. pH ca dung dch mui loi ny c tnh nh cch tnh pH ca dung dch baz yu (8-37; 8-38) 3. Nu mui c to thnh bi baz yu v axt mnh nh NH4Cl, NH4NO3, AlCl3, CuSO4... th khi thu phn dung dch mui s c pH < 7. V d: NH4Cl 2H2O
+ NH 4 + HO-
+ ClHO- + H3O+ NH4OH
S kt hp NH 4+ vi HO- to thnh cht in li yu NH4OH lm chuyn dch cn bng ca nc v bn phi lm tng ion H3O+, do vy dung dch c tnh axt (pH < 7). Trong trng hp ny, trnh thy phn th cn phi cho thm axt. pH ca dung dch mui loi ny c tnh theo cng thc tnh pH ca axt yu (8-34; 8-35). 3. Nu mui c to thnh bi mt baz yu v mt axt yu nh NH4CN, (NH4)2S, Al2S3, (CH3COO)3Fe... th khi thu phn dung dch mui s c 7 pH 7 tu thuc vo mi tng quan gia mnh yu ca cc axt - baz c to thnh trong dung dch. V d: CH3COONH4 + H2O K CH3COONH4 c pH = 7. D CH3COOH 1,76.10-5 + NH4OH 1,79.10-5
Hng s in li ca CH3COOH v NH4OH gn nh nhau nn dung dch
99
8.5.
CHT CH TH MU xc nh chnh xc pH ca dung dch in li ngi ta s dng phng php
pH met. Tuy nhin khi khng cn mt chnh xc cao lm v cn phi xc nh nhanh pH ngi ta dng cht ch th mu (Ctm) Cht ch th mu l cht m mu ca n bin i theo pH. Cht ch th mu c th l mt axt hoc baz hu c yu, nhng thng dng axt yu. V d, phn ng phn ly ca phm mu axit: HCtm + H2O mu axt Ka = Suy ra: hay
[H 3 O + ][Ct ] m [HCt m ]
[HCt m ] [Ct ] m
H3O+ + Ct m mu baz
[H3O+] = Ka. pH = pKa + lg
(8-40)
Nu [HCtm] = [ Ct ] (cn bng nng ca 2 dng mu) m Suy ra: pH = pKa l mu nhy cm Nu dng mu axt chim u th [HCtm] >> [ Ct ] th thc nghim cho thy iu m xy ra khi [HCtm] 10 [ Ct ], hay m pH pKa - 1 Nu dng mu baz chim u th [ Ct ] 10 [HCtm] hay m pH pKa + 1 Min pH nm gia pKa - 1 pH pKa + 1 (8-41) gi l min i mu (khong chuyn mu). i vi mi cht ch th mu (pKa c mt gi tr hon ton xc nh) c mt khong chuyn mu hon ton xc nh (min gch cho trong bng 8.1)
100
Bng 8.1: Khong chuyn mu ca mt s cht ch th mu pH Metyl da cam Qu Phenolphtalein 8.6. TCH S HO TAN Xt h cn bng gia cht rn t tan AgCl vi cc ion trong dung dch bo ho ca n: AgCl v
2
3,1
hng
4,4
da cam khng mu
9
vng
10
14
tm hng
xanh
v1
Ag+ + Cl-
Trong : v1 = K1.S v2 = K2.S (aAg, aCl ) K1, K2 - hng s S - din tch b mt cht rn Ti thi im cn bng v1 = v2 K1S = K2S a Ag.aClSuy ra :
K1 = aAg + a Cl K2
Gi tr khng i K1/K2 c gi l tch s ho tan (ki hiu l T) V cht in li tan rt t nn c th coi hot ca ion bng nng ca n. TAgCl = [Ag+][Cl-] Vy trong dung dch bo ho ca cht in li t tan, tch s nng cc ion l mt hng s. N chnh l tch s ho tan T. Trong trng hp cht in li cho nhiu ion: AnBm ta c:
TA n B m = [Am+]n .[Bn-]m
nAm+ + mBn(8-41)
Tch s ho tan T l hng s khng c ngha nng ca cc ion trong dung dch bo ho cng l hng s. V d nu trong trng hp trn ta thm HCl vo dung dch th nng ion Cl- s tng ln. Ti thi im ny ta c: 101
[Ag+] [Cl-] > TAgCl gi tr [Ag+][Cl-] = TAgCl th phi gim nng ion Cl-, ngha l cn bng chuyn dch theo chiu v2 : (Cl- + Ag+ AgCl),chiu to kt ta AgCl . Vy mt cht in li t tan ch c th kt ta khi tch s nng ion ca n ln hn tch s ho tan. Ngc li nu gim nng ca ion bn phi, v d Ag+ th lc : [Ag+] [Cl-] < TAgCl V cn bng s chuyn dch theo hng v1: (AgCl Ag+ + Cl-), hng ho tan kt ta. 8.7. DUNG DCH KEO Dung dch keo l h thng phn tn trong cc ht pha phn tn c kch thc t 10-7 n 10-9m. Cc ht pha phn tn ca h ny ch c th nhn thy di knh siu hin vi c gi l h siu vi d th. 8.7.1. iu ch dung dch keo C hai phng php iu ch dung dch keo: phng php phn tn v phng php ngng t. * Phng php phn tn: Phng php ny da vo s nghin cc ht ln thnh ht nh bng ci xay keo hoc cho phng tia la in gia 2 in cc bng kim loi ca pha phn tn nh vng, bc, platin di nc. Trong trng hp dng tia la in, vng h quang kim loi b bay hi v ngng t thnh cc vi v siu vi tinh th, chng hp th cc ion HO- v to thnh dung dch keo. * Phng php ngng t: y l phng php kt hp cc phn t, nguyn t, ion ring bit thnh cc tp hp ln hn. V d, nu thm tng git FeCl3 vo nc si th s thu c dung dch keo Fe(OH)3: FeCl3 + 3H2O = Fe(OH)3 + 3HCl
102
8.7.2. Cu to mixen ca dung dch keo

ClClCl O Fe
+
ClFeO+
ClClFe O+
ClClClClCli xe n
FeO +
ClFeO
+
ClQ ClCl-
[Fe(OH)3]m
Nh n
Hakeo t
Hnh 8.6. S cu to mixen ca ht keo hydroxyt st III
Nhng ht trung ho v in tch v tn ti c lp trong dung dch keo gi l mixen. Cng thc ca mixen cng c th biu din {[Fe(OH)3]m.
nhn ht keo mixen
Ta hy xem xt nhng c im cu to chung ca mixen qua v d iu ch dung dch keo bc ioua t bc nitrat v kali ioua. mAgNO3 + (m+n)KI = m[AgI]rI-(n-x)K+x-.xK+ + mKNO3 Cu to ca mixen c biu din trn hnh(8.6 ) 8.7.3. Tnh cht ca dung dch keo
O Fe
+
FeO
FeO+
Fe O+
FeO +
ClCl Cl -
FeO
ClClCl
-
Cl-
nFeO+(n-x)Cl-}+
lp b hp ph
xCllp khuych tn
103
- Cc ht keo c kch thc tng i ln so vi kch thc ca phn t v ion nn khi i qua mng bong bng ng vt th chng b gi li. Tnh cht ny thng c s dng lm sch keo. Khi chiu mt chm tia sng qua dung dch keo th s quan st thy mt vng nh sng trong dung dch. Hin tng ny c gi l hiu ng Tinan (hnh 8.7 H). Hiu ng ny c gy ra do s tn x ca cc ht keo trong dung dch. Nh tnh cht ny m c th quan st c cc ht keo di knh siu hin vi. Nhng tnh cht ca dung dch keo nh p sut thm thu, gim p sut hi bo ho, tng nhit si, gim nhit ng c u th hin yu hn so vi dung dch tht. iu ny c gii thch bi nu cng mt nng mol bng nhau th s phn t c trong mt n v th tch ca dung dch tht s ln hn dung dch keo. Tt c cc h keo c chia thnh hai nhm ln: Keo a lng v keo k lng.
Hnh 8.7 : Hiu ng Tinan
Keo a lng (liophil) l keo hp ph cc phn t mi trng to thnh mt lp v bc sonrat. Nu mi trng khuch tn l nc th gi l keo a nc (hydrophil): abumin, h tinh bt, protein... bn ca loi keo ny c quyt nh bi kh nng ngn cn khng cho cc ht keo kt dnh li vi nhau ca lp v hyrat.
104
Keo k lng (liophob) l keo hu nh khng hp ph cc phn t ca mi trng phn tn (nu mi trng nc th gi l keo k nc - hyrophob). bn ca keo b nc c quyt nh bi s tch in cng du ca cc ht keo. Cc keo ca cc hp cht kim loi nh Au, Ag, Cu, Pt... l nhng keo k nc. Trong v d trn keo AgI v Fe(OH)3 l keo k nc. - lm gim bn ca cc dung dch keo th ngi ta tm cch ph v lp v hyrat ca keo a nc hoc lm trung ho in tch ca keo k nc v lc xy ra s kt ta keo - s ng t keo. S ng t keo c th thc hin bng cch cho thm vo dung dch keo mt cht in li, trn dung dch keo vi mt dung dch keo khc tch in tri du hoc un nng cc dung dch keo. S ng t keo c th xy ra thun nghch hoc bt thun nghch. Nu cc ht keo kt ta khi tip xc vi nc li chuyn thnh dung dch keo th l s ng t thun nghch, cn nu khng chuyn thnh dung dch keo th gi l s ng t bt thun nghch. Trong mt s trng hp c th chuyn mt kt ta keo bt thun nghch thnh thun nghch bng cch cho thm mt lng nh cht in li vo nc. Hin tng ny c gi l s pepti ho.
105
Chng 9 PHN NG OXI HO KH V IN HO

9.1. PHN NG XI HO KH. CP XI HO - KH Phn ng xi ho - kh l loi phn ng xy ra cng vi s thay i s xi ho ca cc nguyn t c mt trong thnh phn ca hp cht tham gia phn ng. Trong phn ng oxi ho kh ng thi xy ra hai qu trnh s oxi ho v s kh. S xi ho mt cht l lm cho cht mt electron. Cht mt electron gi l cht kh. Cc cht kh quan trng nh kim loi (c bit l kim loi kim v kim th ), cc cht kh nh H2, CO v cc ion nh I-, S-, H-... S kh mt cht l lm cho cht nhn electron. Cht nhn electron l cht xi ho. Cc cht xi ho quan trng thng gp nh: cc hp cht n gin (F2, Cl2, Bv2, I2, O2, S...), cc axt (H2SO4), HNO3, HClO, HClO3, HClO4...), cc mui (KMnO4, K2Cr2O7, KClO3...), cc anhyrit, oxit v pexit (CrO3, Mn2O7, PbO2, MnO2, H2O2, Na2O2...) v cc ion kim loi chuyn tip Fe3+, Au3+, Cu2+... 9.2. TH XI HO KH TRONG DUNG DCH. TH TIU CHUN Thc t cho thy rng kh nng oxi ho ca cc cht xi ho v kh nng kh ca cc cht kh l rt khc nhau. Mt hp cht ho hc c th d dng b xi ho bi cht xi ho ny nhng hon ton khng b xi bi cht khc. iu ny c gii thch bi s khc nhau v kh nng cho hoc nhn electron ca cht kh hoc cht xi ho. nh lng kh nng cho hoc nhn electron ca cht kh hoc xi ho ngi ta dng th tiu chun xi ho kh. 9.2.1. Th in cc Nu ta nhng mt thanh kim loi (v d Zn) vo nc sch th cc ion trn b mt kim loi s b hyrat ho v i vo nc. Kim loi b ho tan: M + mH2O = Mn+ .mH2O + ne
106
Kt qu l electron cha trong kim loi d (kim loi tch in m), nc cha cation kim loi (tch in dng) v do lm xut hin mt lc ht tnh in trn ranh gii gia kim loi v cht lng (hnh 9.1). Ngi ta ni y xut hin mt lp in tch kp v hiu in th trn b mt ny c gi l th in cc.
Zn H2O
Hnh 9.1 : S ho tan ion kim loi bng s hyrat ho (a) v s xut hin th in tch kp (b)
9.2.2. Nguyn t ganvani S chuyn ho nng lng ho hc thnh in nng c thc hin trong nguyn t ganvani bng phn ng xi ho kh in cc. y thu c dng in th cn phi tin hnh qu trnh oxi ha v qu trnh kh trn hai in cc ring bit nhm to ra mt s chnh lch in th gia hai in cc. V d: Nguyn t ganvani ng - km (pin anien - Iacobi c s cu to nh sau: (hnh 9.2 )
e E02 i E01
2e
O Zn
2+
Cu2+ O
2e Cu
Zn-2eZn
Cu2+ +2eCu
Hnh 9.2. S cu to pin anien - Iacobin
107
Hai in cc km v ng c nhng vo 2 dung dch mui ZnSO4 v CuSO4 tng ng. Ni hai dung dch bng mt ng cha cht in li bo ho (KCl, NaCl...). Khi ni hai in cc bng mt dy dn kim loi th do th in cc gia hai cc khc nhau nn dng electron s chuyn dch t anot (cc km cho electron) sang catot (cc ng nhn electron). Vy iu kin cn thit cho mt nguyn t ganvani hot ng l hiu in th gia hai in cc. Hiu in th ny c gi l sut in ng (S). Mt nguyn t ganvani c k hiu: (-) ZnZn2+ Cu2+Cu(+) Trong vch n biu th ranh gii phn cch gia in cc vi dung dch, vch kp ranh gii gia cc dung dch, (-) v (+) l du ca cc in cc. 9.2.3. Th in cc tiu chun Th in cc ca tng in cc ring bit gi l th in cc tuyt i. Th in cc ny rt kh xc nh nn trn thc t ngi ta thng dng th in cc tng i. Th in cc tng i c tnh bng cch so snh th in cc tuyt i ca mt in cc cn xc nh vi mt in cc chun c th in cc qui c bng khng. Th in cc chun c s dng so snh l th in cc hydro, c cu to trn hnh 9.3 (phn bn tri). l mt ci bnh c hnh dng c th cha dung dch H2SO4 vi nng [H3O+] = 1 g-ion / lit. Mt thanh platin ph mui platin c nhng vo dung dch v thi hydro i qua bnh. Trn ranh gii phn cch Pt, H2H3O+ xut hin mt hiu in th xc nh c qui c bng khng ( iu kin 25OC, v 1atm).
Pt
H2
H+ SO4 2
Hnh 9.3 : in cc Hyr
108
Dng electron H2 Pt Cu
H2SO4
CuSO4
KCl H2
Hnh 9.4:S lp ghp xc nh th in cc chun ca ng
xc nh th in cc tng i ca mt in cc th ta lp rp theo s (hnh 9.3 v 9.4 ) Th in cc tng i o c trong trng hp ny gi l th in cc tiu chun ca kim loi, k hiu eo. Th in cc tiu chun kim loi l S ca pin to bi in cc hydro chun ghi bn tri v in cc kim loi nhng vo dung dch mui ca n c hot ion kim loi bng 1 ghi bn phi. eo = ephi - h
+
/ H 2 ( tra 'i )
(9-1)
Sut in ng ca pin c coi l dng nu dng in trong pin i t tri qua phi (dng electron ngc li i t phi sang tri), ngc li s l m. V d: Trn s hnh 9.3 ca pin (-)Pt, H2 H3O+ Vi phn ng to dng l: Cu2+ + H2 + 2H2O = Cu + 2H3O+ Thc nghim o c S l 0,337V c dng in i t tri qua phi nn:
o 2 + / Cu = + 0,337 V Cu
Cu2+ Cu (+)
109
Ngc li trn s hnh 9.4 ca pin (+) PT, H2H3O+ Vi phn ng to dng: Zn + 2H3O+ = Zn2+ + H2 - + H2O c dng in i t phi qua tri, suy ra:
o 2 + / Zn = -0,763V Zn
Zn2+ Zn (-)
Theo cng c quc t Stockholm 1968, phn ng in cc l phn ng kh: Mn+ + ne = M hay dng oxi ho + nc = dng kh Th in cc cn bng theo cng c ny l th kh. Trong bng 9.1 di y cho bit phn ng in cc, k hiu in cc v gi tr th in cc tiu chun ca mt s cht.
110
Bng 9.1.Th chun ca mt s phn ng in cc trong mi trng nc 250C K hiu in cc Li+ Li K+ K Rb+ Rb Cs+ Cs Ca2+ Ca Na+ Na Mg2+ Mg Be2+ Be Al3+ Al Mn2+ Mn Zn2+ Zn Cr3+ Cr Fe2+ Fe Cr3+,Cr2+ Pt PbSO4 Pb Co2+ Co Ni2+ Ni Sn2+ Sn Pb2+ Pb H3O+ H2 ,Pt Cu2+,Cu+ Pt Cu2+ Cu OH- O2, Pt Cu+ Cu I- I2, Pt Fe3+ ,Fe2+ Pt Li+ K+ Rb+ Cs+ Ca2+ Na+ Be2+ Al3+ Zn2+ Cr3+ Fe2+ Cr3+ Co2+ Ni2+ Sn2+ Pb2+ Phn ng in cc + e + e + e + e + e + 2e + 3e + 2e + 3e + 2e + e D D D D D D D D D D D D D D D D D D D Li K Rb Cs Ca Na Mg Be Al Mn Zn Cr Fe Cr2+ Pb + SO42Co Ni Sn Pb H2 + 2H2O Cu+ Cu Cu+ 2 IFe2+ (vn) -3,045 -2,925 -2,925 -2,923 -2,870 -2,714 -2,370 -1,850 -1,660 -1,180 -0,763 -0,740 -0,440 -0,410 -0,356 -0,277 -0,250 -0,136 -0,126 0(theo qui c) +0,153 +0,337 +0,401 +0,52 +0,536 +0,771
+ 2e D
Mg2+ + 2e
Mn2+ + 2e
PbSO4 + 2e + 2e + 2e + 2e
+ 2e D
2H3O+ + 2e Cu2+ + e
Cu2+ + 2e D Cu+ I2 Fe3+ + + e 2e D D D
1/2O2 + H2O +2e = 2OH-
+ e
111
Hg2+ Hg Ag+ Ag Hg2+ Hg Hg2+,Hg22+ Br- Br2,Pt Mn2+,H3O+ MnO2 ,Pt Cr2O72- ,Cr3+ Pt Cl- Cl2,Pt Pb2+ PbO2,Pb Au3+ Au MnO4-, H3O,Mn2+ Pt Ce4+,Ce3+ Pt Au+ Au F- F2,Pt Pt
Hg2+ + 2e Ag+ + e Hg2+ + 2e 2Hg2+ + 2e Br2 + 2e
D D D D D
2Hg Ag Hg2+ Hg22+ 2BrMn2+ + 2H2O 2Cr3+ +7H2O 2ClPb2+ + 2H2O Au Mn2+ +2H2O Ce3+ Au 2F-
+0,798 +0,799 +0,854 +0,91 +1,066 +1,236 +1,33 +1,359 +1,455 +1,50 +1,51 +1,61 +1,70 +2,87
MnO2 + 4H+ +2e D Cr2O7- + 14H+ +6e D Cl2 + 2e D D D D D PbO2 + 4H+ +2e D Au3+ + 3e Ce4+ Au+ F2 + e + e + 2e MnO4- + 4H+ +3e D
Qua bng gi tr ca th in cc tiu chun trn (sp xp theo th t eo tng dn) c th rt ra mt s nhn xt sau: 1. Th in cc tiu chun ca in cc no cng nh (tr s i s) th dng kh ca
o + / Na = -2,714V nn Na
n hot ng cng mnh, cn dng xi ho ca n hot ng cng yu v ngc li. V d:
Dng kh Na - e = Na+ hot ng rt mnh Dng oxi ho Na+ + e = Na rt kh Tri li cp MnO-4 Mn2+ c th in cc tiu chun rt ln
o MnO
4 4
Mn 2 + , Pt
= +1,507V
nn dng xi ho MnO-4 hot ng rt mnh cn dng kh Mn2+ hot ng yu. 2. Cp xi ho kh no c th in cc tiu chun ln th dng xi ho ca n c th
xi ho c dng kh ca cp c th in cc tiu chun nh hn.
112
V d:
o 2 + / Zn Zn
= -0,763V v = + 0,799V
nn phn ng xy ra l: Zn + 2Ag+ = Zn2+ + 2Ag Qua nhn xt ny suy ra ch nhng kim loi no c th in cc tiu chun nh hn khng mi y c hyro ra khi dung dch axt long. 9.2.3. Phng trnh Nernst Mt trong nhng nh hng ln n gi tr th in cc l nng ca ion kim loi lm in cc. S ph thuc c tnh bng cng thc Nernst
M n+ / M = o n+ / M + M
RT ln[M n + ] nF
(9-2)
Nu thay cc gi tr R, F v T = 298K ri tnh theo lganit thp phn, ta c:

M n+ / M = o n+ / M + M
0,059 lg[M n + ] n
(9-3)
Trong :
M n+ / M th in cc tiu chun ca kim loi
n S electron trao i trong phn ng in cc [Mn+] nng mol ca ion kim loi Trong trng hp tng qut i vi mt in cc bt k: niAi Th cng thc Nernst c dng: n'iA'i
0,059 [ Ai ] hi [oxi ] . lg n [ A'i ] n 'i [kh]
i = io +
(9-4)
9.2.4. Chiu ca phn ng oxi ho kh Nhit ng ho hc xc nh mi lin h quan trng gia DG v S ca cc cp xi ho kh.
GT = - nFE
nhit T = 298oK:
(9-5) (9-6)
G o = -nFEo 298
113
Nh vy phn ng xi ho kh ch c th t xy ra khi E > 0 - tc l DGT <0 (iu kin t din bin ca qu trnh). Sut in ng c tnh bng cng thc: S = el - eb Trong : el - th in cc cp oxi ho kh dng hn eb - th in cc cp oxi ho kh m hn Gi tr th in cc ca cc cp oxi ho kh trong dung dch nc c tnh theo cng thc (9.3) v (9.4). Trng hp phn ng in cc xy ra trong mi trng axt hoc baz th trong phng trnh Nernst s c mt ca [H3O+] hoc [HO-] V d, i vi phn ng: MnO-4 + 5e + 8H3O+ = Mn2+ + 12H2O Ta c:
MnO ,H O+ ,M2 + / Pt = o ,H O+ ,M2 + + MnO
4 3 n 4 3 n / Pt
(9-7)
0,059 [MnO ][H 3O + ]8 4 lg 5 [M 2 + ] n
Vi in cc kh HO-/O2, Pt O2 + H2O + 2e = 2HOTa c:

HO
/ O2 , Pt
o HO / O2 , pt
PO 2 0,059 + lg 2 [ HO ] 2
1/ 2
9.2.5. Mt s v d xt chiu phn ng oxi ho kh V d 1: Xt chiu ca phn ng oxi ho kh trong pin anien- Iacobi: (-) ZnZn2+ Vi o
Zn 2 + / Zn
Cu2+ Cu(+)
= -0,763V;
o 2 + / Cu = + 0,337V Cu
Ta c cc phn ng in cc: Cu2+ + 2e = Cu Zn2+ + 2e = Zn

o 2 + / Cu = +0,337V (1) Cu o 2 + / Zn = -0,763 Zn
(2)
Phn ng (2) ch t xy ra theo chiu ngc li v c eo < 0 nn ta c th vit: Cu2+ + 2e = Cu eo = +0,337 V
114
Zn - 2e = Zn2+ Chiu phn ng: Cu2+ + Zn Cu + Zn2+ V d 2: Xt chiu ca phn ng 2Cu2+ + 4I- = 2CuI + I2 Bit: v TCuI = 10-12
o = + 0,763V
E = 1,10V
o 2 + / Cu + = + 0,17V ; o I / I 2 = + 0,54V Cu 2
Theo bi ra nu ch xt theo th kh tiu chun o theo chiu I2 + 2CuI 2Cu2+ + 4I-
2 I / I2
> o
Cu 2 + / Cu +
th phn ng xy ra
Trn thc t do c s to thnh CuI t tan lm nng Cu+ gim dn n th ca cp

Cu 2 + / Cu +
thay i
Cu2 + / Cu + = o 2 + / Cu + + 0,059lg Cu
[Cu 2 + ] [Cu + ]
Thay [Cu+] =
TCuI ta c [I ]
Cu2 + / Cu + = 0,17 + 0,059lg
[Cu 2 + ][I ] TCuI
Nu (I-) = 10-1 mol/l th

Cu2 + / Cu + = 0,819 + 0,059 lg[Cu2+]
Th ny ln hn th cp 2I-/I2 do phn ng xy ra theo chiu ngc li: 2Cu2+ + 4I- I2 + 2CuI 9.2.6. Trng thi cn bng cc phn ng oxi ho kh Khi cn bng ca phn ng c thit lp ta c: DGoT = -nFEo = 0 Mt khc: DGoT = -RTlnK = -nFEo Suy ra:
115
lnK =
nFE o nE o hay lgK = RT 0,059
(9-8)
Trong : Eo - th in cc tiu chun n - s electron trao i trong phn ng. 9.3. QU TRNH BIN I HO NNG THNH IN NNG
9.3.1. in phn Trong cc phn trn y chng ta ch ch kho st trng thi cn bng gia in cc v dung dch khi khng c s lu thng dng in trong h in ho. Nu trong trng hp cc phn ng trn in cc c gy ra bng mt ngun in bn ngoi (trong h in ho c s lu thng dng in) th l s in phn. Vy s in phn l qu trnh oxi ho v kh xy ra in cc khi cho dng in mt chiu i qua cht in li nng chy hoc dung dch cht in li. Cc phn ng xy ra trn in cc l th nng lng in nng; trong catot cht kh v n cho cation electron, anot - cht oxi ho v n nhn electron. V d s in phn mui NaCl nng chy trn hnh 9.5
e- - + e-
Do g electron n
ANOT e Na+ eKATOT
S Nao
ClClo
K'
A'
Hnh 9.5: S in phn nng chy mui Clorua Natri
Trn catot xy ra qu trnh kh cation Na+ bng electron ca ngun in: Na+ + e = Na 116
ng thi trn anot xy ra phn ng oxi ho cn Cl- bng nng lng ca ngun in: 2Cl- - 2e = Cl2 hiu c r hn cc quy lut xy ra trn catot v anot, cn lm quen vi cc khi nim s phn cc in cc, th phn hu v qu th. 9.3.2. S phn cc Khi dng in i qua ranh gii phn chia in cc - dung dch th lm cho trng thi in ca in cc thay i. Hin tng gi l s phn cc in cc. nu s thay i th in cc dch chuyn v pha dng hn so vi th cn bng th gi l s phn cc anot v ngc li - s phn cc catot. S phn cc in cc c chia thnh cc loi nh: phn cc nng , phn cc ho hc, phn cc in ho. S phn cc nng sinh ra bi s bin i nng cn lp gn b mt in cc khi c mt ca dng in i qua. Trong trng hp ny th ca in cc anot tng (tr thnh dng hn) do nng ca ion kim loi ho tan tng ln, tri li th in cc catot gim (tr thnh m hn) do nng ion trn b mt ca n gim. S phn cc ho hc sinh ra do phn ng gia mi trng hoc cht in li vi vt liu lm in cc khi c dng in i qua lm bin i tnh cht ca b mt in cc dn n s thay i th. S phn cc in ho c sinh ra do dng electron (n catot ni vi cc m v ri anot ni vi cc dng ca ngun in) khng i qua c dung dch in li khi c in p gia 2 cc cha t c mt gi tr cn thit lm xut hin mt hiu in th ngc chiu vi chiu ca ngun in ngoi. 9.3.3. Th phn hu Nh ni trn y, s in phn ch bt u xy ra mt in p hon ton xc nh. in p ti thiu gia hai in cc s in phn bt u xy ra gi l th phn hu (k hiu eph). Th phn hu c xc nh bng thc nghim. Trn bng 9.2 l th phn hu ca mt s cht in phn.
117
Bng 9.2. Th phn hu mt s cht in phn vi nng cation 1g-ion/lit

Cht in phn eph(V) Cht in phn eph(V) Cht in phn eph(V)
HNO3 H2SO4 H3PO4 NaOH KOH
1,69 1,67 1,70 1,69 1,67
NaNO3 Na2SO4 HCl HBr HI
2,15 2,21 1,31 0,94 0,52
AgNO3 CuSO4 ZnSO4 NiCl2 NiSO4
0,70 1,49 2,35 1,85 2,09
9.3.4. Qu th Hai qu trnh in ho (mt xy ra trong nguyn t ganvani v mt trong in phn) u c chung mt bn cht. l phn ng oxi ho in cc. im khc nhau ca hai qu trnh ny l chng xy ra theo hng khc nhau. Do vy cho s in phn bt u xy ra, v mt l thuyt ch cn t mt in p c gi tr bng S ca nguyn t ganvani tng ng nhng ngc chiu. V d: S ca nguyn t ganvani: (-) Ni| Ni+2 2Cl-| Cl2 (+)
Vi o 2 + / Ni = -0,250V; o Cl / Cl 2 = + 1,359V tnh theo cng thc (9-7) l: Ni 2
E = 1,359 - (-0,250) = 1,609 (V) Vy v l thuyt ch cn t mt in p 1,609V ngc chiu l s in phn dung dch NiCl2 s xy ra. Trn thc t, gi tr thc nghim cn thit bng 9.2 l eph = 1,850V. Hiu s gia th phn hu v S ca pin gi l qu th:
qt = ph - E
Trong v d trn:
qt = 1,850 - 1,609 = 0,241 (V).

9.3.5. Cc loi in phn 9.3.5.1. in phn nng chy
118
in phn nng chy thng c s dng iu ch cc kim loi hot ng nh liti, natri, canxi... t cc mui clorua tng ng. Cc mui ny c nhit nng chy thp hn cc mui khc. i a s cc mui ny trng thi nng chy tn ti di dng ion c kh nng di chuyn tng t nh ion ca cc dung dch. V d di y l s in phn nng chy canxi clorua: CaCl2 = Ca+ + 2Cl(-) Katt: (+) Ant: 9.3.5.2. in phn dung dch Trong dung dch nc ngoi ion cc cht in li cn c cc ion phn li ca nc H3O+ v HO-. Do vy khi thit lp mt in p gia hai in cc th ion H3O+ cng vi cation kim loi s i v catot cn ion HO- vi anion s i v anot. Do vy trn cc in cc s xy ra cc phn ng cnh tranh gia cc ion ca nc vi cc ion ca cht in li. * Trn in cc catot: Nu th phng in ca cation dng hn th phng in ca H3O+ th s xy ra s kh kim loi: Mn+ + ne = M Trng hp ngc li th H3O+ s b kh H3O+ + e = H + H2O 2H = H2nhng nng H3O+ rt nh (10-7M) nn ngi ta coi nh H2O b kh 2H2O + 2e = H2 + 2HO- (2) Nh vy trn in cc catot c th xy ra ba trng hp 1. Nhng ion kim loi c th in cc tiu chun nh (t Li+ n Al3+) khng b kh trn catot m ch H2O b kh (phn ng 2) 2. Nhng ion kim loi c th en cc tiu chun nh hn hiro nhng ln hn nhm (t Al3+ n H3O+) b kh cng vi H2O trn in cc (phn ng1v 2) 3. Nhng ion kim loi c th in cc ln hn hidro (t Cu2+ n Au3+) b kh hon ton trn in cc (phn ng 1) 119 (1) Ca+ + 2e = Ca 2Cl- = Cl2 + 2e
Vy khi in phn dung dch nc, ch nhng kim loi no ng sau nhm v khng k nhm mi thot ra trn in cc. Nu dung dch cha cc ion kim loi khc nhau th phn ng kh s xy ra theo hng gim dn th in cc tiu chun tng ng vi kim loi. V d i vi hn hp Ag+, Cu2+, Fe2+ th Ag+ b kh trc ( o Ag tip n Cu2+ ( o Cu
2+ +
/ Ag
= +0,779V)
/ Cu
= + 0,337V) v cui cng l Fe2+ ( o Fe
2+
/ Fe
= - 0,440V)
* Trn in cc anot: Cc phn ng xy ra trn anot ngoi s ph thuc vo s c mt ca H2O cn ph thuc vo vt liu lm in cc: anot tan v khng tan. 1. Nu s dng anot tan nh Cu, Ag, Zn, Cd, Ni, Fe... th phn ng trn in cc l phn ng ho tan anot: M - ne = Mn+ ch khng phi anion dung dch b oxi ho. 2. Nu s dng anot khng tan (anot tr) nh than, graphit, Pt th trn in cc c th anion dung dch hoc ion HO- b xi ho: - Nu anion dung dch l nhng ion khng cha oxi (Cl-, Bv-, I-, S2-, CN-...) th chng s b oxi ho trn anot. V d: 2Cl- - 2e = 2Cl 2Cl CL2 Nu anion dung dch l nhng ion c cha oxi (NO3-, SO42-, PO43-...) th chng s khng b oxi ho trn anot m ch c HO- b oxi ho: HO- - 2e = H+ + O 2O = O2 - Nhng do nng HO- rt nh (10-7M) nn ngi ta coi nh phn t H2O b oxi ho: 2H2O - 4e = 4H+ + O2 Nu dung dch cha cc anion khc nhau th phn ng oxi ho trn anot s xy ra theo th t: u tin l cc anion khng cha oxi, tip n HO- v cui cng l cc anion cha oxi. V d: S in phn dung dch CuCl2 vi in cc graphit nh sau:
120
Catot: Cu2+ + 2e = Cu Anot: 2Cl- - 2e = Cl2 Cu2+ + 2Cl- = Cu + Cl2 Hay CuCl2 Cu + Cl2 Catot: 2H2O + 2e = H2 + 2HOAnot: 2H2O - 4e = O2 + 4H+ 6H2O = 2H2 + O2 + 4HO- + 4H+ Nh vy vng gn catot to thnh kim, vng gn anot to thnh axt. Nu in phn khng c mng ngn th ion H+ v HO- tc dng vi nhau to H2O nn phn ng cui cng ca s in phn K2SO4 l: 2H2O = 2H2 + O2 9.4. PIN V ACQUY Nh kho st trn y phn nguyn t ganvani, in nng c th sn xut trc tip t nng lng ca cc phn ng ho hc xy ra trong cc nguyn t in ho. Trn c s cc h oxi ho kh khc nhau, v nguyn tc c th thit lp c rt nhiu cc nguyn t in ho cho php bin i ho nng thnh in nng. Tuy nhin trong thc t ch c rt t mt s h in ho sinh ra dng in c ng dng. 9.4.1. Pin kh Pin l mt loi ngun in s cp c ch to trn c s cc phn ng khng thun nghch khin cho vic ti tch in khng thc hin c v mi khi phn ng trong pin kt thc th pin c b i. V d, loi pin Le Clanche hay cn gi l pin "kh" ang c dng ph bin hin nay c s mch nh sau: (-) Zn| NH4Cl(20%) ZnCL2| MnO2, C (+) Mt trong nhng hnh dng cu to ca pin c trnh by trn hnh 9.6 P. Cc phn ng c bn xy ra khi c s phng in trong pin nh sau: S in phn dung dch K2SO4 vi in cc tr
121
- Ti cc m: 2Zn 2Zn2+ + 4e 2Zn2+ + 4NH4Cl [Zn(NH3)4]Cl2 + ZnCl2 + 4H+ Ti cc dng: 2MnO2 + 4H+ + 4e 2MnO(OH)2 Loi pin ny c S khong t 1 - 1,5V
1 2 3 4 5 6
1. Cc dng (ng) 2. Phn cch in 3. Li than ch 4. Cc m (nhm) 5. Bt nho(NH4Cl) 6. Bt (MnO2) 7. Lp v ngoi
Hnh 9.6 : S cu to ca Pin kh
9.4.2. Pin nhin liu Pin nhin liu hay cn gi l my pht in ho l mt thit b trc tip bin ho nng thnh in nng b qua giai on tch t nng lng nh i vi cc ngun in ho hc khc (pin kh, acquy) V nguyn tc, ch to pin nguyn liu, ngi ta s dng oxi khng kh hay oxi tinh khit lm cht oxi ho, cn nhin liu th dng hydro, metanol, axt focmic... Hnh 9.7 m t s pin nhin liu loi hydro - oxi dng in cc niker nhng trong dung dch KOH: (-) Ni, H2 | KOH(30-40%) | O2, Ni (+)
122
Nhin li u
Cha t oxy hoa
Sa n pham
Hnh 9.7 : S Pin nhin liu
Khi pin lm vic: - Ti cc m xy ra phn ng in cc: 2H2 + 4HO- = 4H2O + 4e - Ti cc dng: O2 + 2H2O + 4e = 4HO2H2 + O2 = 2H2O Loi pin ny cho dng in mt chiu c in p 0,7 - 0,9V 9.4.3. Acquy ch Acquy l loi nguyn t ganvani ch to trn c s cc qu trnh in cc hu nh thun nghch. Mi qu trnh xy ra trong s phng in c th o ngc li trong s tch in. Mt trong nhng acquy c in nht v cng l ph bin nht l acquy ch c s sau: (-) Pb | H2SO4(32 - 34%) | PbO2, Pb (+) Qu trnh tch in v phng in xy ra theo phng trnh Pb + PbO2 + 2H2SO4
phng tch in
2PbSO4 + 2H2O
Sut in ng ca loi acquy ny c th t ti 2,1V. y l tr s S cao nht ca cc ngun in ho hc dng dung dch nc cc cht in li. Tuy nhin acquy ch c 123
nhc im c bn l dung lng ring nh v thi gian s dng tng i ngn do qu trnh t phng in khi acquy trng thi khng s dng to ra ch sunfat theo phn ng: Trn cc Pb: Pb + SO42- PbSO4 + 2e 2H3O+ + 2e 2H2O + H2 Trn cc PbO2: PbO2 + 2H2SO4 + 2e PbSO4 + 2H2O + SO42Pb + SO42- PbSO4 + 2e 9.4.4. Acquy kim Acquy kim cng l mt loi acquy kh ph bin c s dng trn thc t. V d acquy kim niken - st c s : (-) Fe | KOH (20%) | NiOOH, Ni (+) c S khong 1,4V Qu trnh tch in v phng in xy ra theo phng trnh:
tch
2Ni(OH)2 + Fe(OH)2
phng
2NiOOH + Fe + 2H2O
Ngoi ra ngi ta cng s dng tng i rng ri cc loi acquy kim nh: niken cadimi, niken - km, bc km. 9.5. N MN IN HO V CCH CHNG N MN IN HO n mn kim loi v hp kim l qu trnh t ph hu cu trc kim loi v hp kim di tc dng ca mi trng xung quanh. Tu theo c ch ph hu kim loi m ngi ta phn bit s n mn ho hc, n mn sinh hc v n mn in ho. S n mn in ho rt ph bin trong t nhin khi kim loi hay hp kim tip xc vi dung dch in phn (n mn trong cht lng), tip xc vi khng kh (n mn trong kh quyn) v tip xc vi t (n mn trong t) 9.5.1. n mn kim loi nguyn cht trong axt 124
S ho tan ca kim loi vo trong axt c xem l mt kiu n mn in ho. Xt s ho tan ca km vo axt Zn + 2H+ Zn2+ + H2 Trn y l phn ng tng qut ca qu trnh ho tan. Qu trnh c xy ra nh sau: Khi nhng km vo dung dch axt, thit lp mt s cn bng gia kim loi km v dung dch, mt s ion Zn2+ i vo dung dch Zn - 2e Zn2+ v do in cc, km tch in m (d electron) - dung dch tch in dng. S to thnh mt lp in cc kp m trong th in cc ca km m hn th in cc ca hydro s dn n s phng in ca ion H3O+ trn b mt thanh km theo phng trnh: H3O+ + e
1 H2 + H2O 2
S tiu th electron theo phng trnh ny khin cho mt electron trn km gim i v do , thit lp li th cn bng (tng mt electron) th km tip tc ho tan- km b n mn. Nh vy s n mn in ho c gy bi s ly i cc electron kim loi. Qu trnh ny khng ch xy ra di tc dng ca ion H3O+ m cn c th bi mt tc nhn oxi ho bt k, c bit l oxi ho tan trong mi trng n mn. Trong mi trng trung tnh hay kim s ion ho oxi xy ra theo phng trnh O2 + 4e + 2H2O 4HOCn trong mi trng axt: O2 + 4e + 4H3O+ 6H2O 9.5.2. n mn kim loi khng nguyn cht (kim loi nhim) Trong thc t rt t gp nhng kim loi hon ton tinh khit m thng mt mc no , kim loi c ln mt hoc nhiu cc kim loi tp cht. Cc kim loi nhim tp cht ny rt d b n mn. Xt s n mn st c ln ng xy ra trong mi trng axt HCl.
125
Fe
Cu
H2 H+ H+ Fe2+
Hnh 9.8 : S hot ng cp nguyn t gavani
Khi st v ng tip xc vi nhau, ta c cp pin: (-) Fe | HCl|Cu (+) Hnh 9.8 : St hot ng mnh hn chuyn electron cho cc nguyn t ng v i vo dung dch di dng ion Fe2+, cn ion hydro b kh trn cc ng: 2H3O+ + 2e = 2H2O + H2 Ion HO- trong dung dch tc dng vi Fe2+ Fe2+ + 2HO- = Fe-(OH)2 4Fe(OH)2 + 2H2O + O2 = 4Fe(OH)3 Mt phn ca hp cht Fe(OH)3 tch H2O theo phn ng
O
Fe(OH)3 = Fe
OH
+ H2O
Hp cht Fe
OH
hay Fe2O3. H2O l thnh phn chnh ca g st.
Qu trnh to g st cng c th gy ra bi phn ng kh oxi. O2 + 4e + 2H2O = 4HO-
126
9.5.3. Phng php chng n mn kim loi. chng n mn kim loi hoc hp kim ngy nay ngi ta s dng nhiu phng php khc nhau, ch yu l: - To ra trn b mt kim loi cn bo v mt lp ph l kim loi, phi kim loi, oxit... (cch li kim loi vi mi trng) - X l v thay i thnh phn mi trng, hoc thay i thnh phn kim loi (hp kim) - Bo v in ho (bo v catot v anot) 9.5.3.1. To lp ph kim loi bo v kim loi, ngi ta dng phng php m in (hoc m ho hc) ph ln kim loi nn mt lp ph kim loi khc. Trong s che ph anot, kim loi che ph cn phi c th cn bng eo m hn th cn bng ca kim loi nn. V d bo v st ngi ta dng km lm lp che ph. Ngc li trong s che ph catot, kim loi chn che phi cn c th cn bng dng hn kim loi nn. V d bo v st c th dng ng, km lm ho cht che ph. 9.5.3.2. To lp bo v phi kim loi Quan trng v n gin nht ca phng php ny l dng mt lp bo v bng nhng hp cht hu c nh du, m, vazlin, parapin... Thng trong cc cht trn ngi ta cn cho thm cc hp cht c ch n mn kim loi. Ngi ta cng s dng cc hp cht v c nh men, s... to lp ph b mt kim loi. Kim loi cng c th c bo v bi cc phn ng ho hc (in ho hc) gia kim loi vi mi trng to thnh cc oxit kim loi. V d, c th nhng cc vt liu st, thp cn bo v vo dung dch kim c to lp bo v Fe3O4 hoc FeO hoc to lp oxit Al2O3 bo v nhm bng phn ng oxi ho... 9.5.3.3. Thay i mi trng n mn Trong mt s iu kin thch hp c th bo v kim loi bng cch thay i mi trng n mn: gim hm lng cht kh hoc dng cc cht c ch:
127
- gim hm lng cht kh ta c th: hoc lm cho mi trng bt axt trnh n mn bi s kh phn cc hydro hoc loi oxi ho tan vo mi trng xm thc trnh n mn bi s kh phn cc oxi. - Vic s dng cht c ch thng cn c vo iu kin x l vt liu v mi trng. Ni chung cc cht c ch c dng hoc c tc dng lm gim tc ho tan anot kim loi hoc lm gim tc gii phng hydro trn catot. V d, bo v gang, thp trong nc hoc trong cc dung dch mui ngi ta dng NaNO2; bo v cc thit b lm lnh th dng K2Cr2O7, K2CrO4. Ngoi cc hp cht v c, mt s hp cht c ch thng c dng l cc amin hu c. 9.5.3.4. Bo v in ho Vic bo v in ho kim loi c th thc hin bng hai phng php: phng php bo v catot v phng php bo v anot - Phng php bo v catot c thc hin khi th ca kim loi chuyn dch v pha m hn gi tr th catot lm cho tc ho tan ca kim loi gim ng thi lm tng tc gii phng hydro. S phn cc catot c th thc hin nh mt ngun in ngoi hoc mt in cc "hi sinh"
+
Hnh 9.9. S bo v catot bng ngun in ngoi
Trong phng php bo v nh ngun in ngoi ngi ta ni vt liu kim loi cn bo v vi cc m ca ngun in, mt in cc ph c ni vi cc dng ca ngun in (hnh 9.9 ). Nu bo v s n mn kim loi trong t th t s l in cc ph. Trong phng php bo v catot vi vic thay ngun in bn ngoi bng mt in cc "hi sinh" c th cn bng m hn th cn bng ca kim loi cn bo v th ngi ta lp t chng nh hnh 9.10 . 128
ng g n
Zn2+
Zn2+
Me+
H+
Ke m
Hnh 9.10 : S lp t bo v st bng in cc hi sinh l km
y l phng php bo v protector, theo in cc "hi sinh" c ch to bng Mg, Al, Zn hoc nhng kim loi thch hp. V d trong hnh 9.10, st c bo v bng in cc "hi sinh" l km. Trong qu trnh lm vic, km s ph hu cn st c bo v. - Phng php bo v anot c thc hin bng cch chuyn kim loi cn bo v vo trng thi th ng, mt trng thi m ti th ca kim loi c th t ti mt gi tr xc nh ng vi gi tr cc tiu ca tc ho tan anot kim loi. Kim loi c th chuyn sang th ng bng con ng ho hc khi s dng mt s tc nhn oxi ho nh tc dng ca axt nitric ln thp, nhng cng c th bng con ng in ho khi phn cc anot kim loi v pha dng hn bi mt dng phn cc anot t bn ngoi.
129
TI LIU THAM KHO

[1] Nguyn nh Chi, C s l thuyt Ho hc - Phn 1. Cu to cht, NXB Gio dc (1997). [2] Nguyn nh Chi, C s l thuyt Ho hc - Phn 2, NXB Gio dc (1991). [3] V ng , C s l thuyt ho hc, NXB Gio dc (1994). [4] Nguyn Hnh, C s l thuyt ho hc - Tp 2, NXB Gio dc (1991). [5] Nguyn Hnh, C s l thuyt Ho hc - Tp 1. Cc qu trnh ho hc, NXB Gio dc (1991). [6] H Th Ngc Loan, Nguyn Khc Chnh, Thc hnh ha hc i cng, NXB Khoa hc K thut (2003). [7] L Mu Quyn, Bi tp C s l thuyt Ha hc, NXB Khoa hc K thut (1993). [8] L Mu Quyn, Ha hc i cng, NXB Gio dc (2005). [9] L Mu Quyn, C s l thuyt Ha hc - Phn 3, NXB Khoa hc K thut (1995). [10]Nguyn Minh Tuyn, L S Phng, Trng Vn Ng, Nguyn Th Lan, Ha hc i cng, NXB Khoa hc K thut (2002).
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LI NI U

= NaH2PO4 + H2O = Na2HPO4 + 2H2O = Na3PO4 + 3H2O

Hnh 2.1. S tn x ca tia a

Hnh 2.2 Ph ca nguyn t hyro

Hnh 2.3. Hnh dng cc my in t s, p v d

phn lp 1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f

Nh vy, lp K (n = 1) cc in t ch c duy nht mt hnh dng my in t s

Hnh 2.4. Quy tc sp xp nng lng Klexcopxki

1 s22 s22 p 1 2s2 p

1 s22 s22 p 3 2s2 p 2py1 2 p z1 z 2px

1 s22 s22 p 4 2s2 p 2py1 2 p z2 2 p x1 y x

T nguyn t Z = 21 (Sc - Scandi) bt u phn b in t trn phn lp 3d cho n Z = 30 (Zn - Km):

Sc 1s22s22p63s23p6 3d14s2 Fe 1s22s22p63s23p6 3d64s2

Ce (Ceri) 71Lu (Lutexi)

Th (Thori) 103Lr (Lorenxi)

Y (Ytri) 48Cd (Cadimi).

Cu, thay v phn b in t vo phn lp 3d, 4s l

S sp xp c tnh ngoi l ny xy ra tng t 3.2.

Cr, 42Mo, 47Ag, 79Au...

BNG H THNG TUN HON CC NGUYN T HO HC MENELEEP

Hnh 3.1. S ph thuc I vo s th t Z

Hnh 3.2. S bin i tun hon I v E theo Z

Hnh 3.3. S bin i m in theo Pauling

3.2.2.4. Bn knh nguyn t v bn knh ion:

Hnh 3.4. S thay i bn knh nguyn t theo Z

W Ti Re OsPt Pb IrAu HgBi Po Al Rn

(I +I +I +I ) 1 2 3 4 150 130 110 90 70

1,5 1,0 0,5 10 30 50 1 1

Hnh 3.5. S bin i I v rZ ca cc nguyn t nhm IV theo Z

E (kJ/mol) 800 400 -400

Hnh 4.1. S ph thuc th nng E vo khong cch r gia 2 nguyn t hyro

Hnh 4.2. S phn b in t trong phn t H2

Tng in tch trong nguyn t ca 2 nguyn t ny trng thi c bn bng

trng thi kch thch: Bo c ho tr 3, cacbon ho tr 4: B* 2s2 2p1

Hnh 4.3. S xen ph to thnh cc lin kt s, p v d

1800 (s + p )-o rb ita l s p -o rb ita l

109028' (s + p + p + p )-o r b ita l s p 3 - o rb ita l

Hnh 4.4. Hnh dng orbital lai ho sp, sp2, sp3

2s1 2px 2py 2pz C* CH4

(s+ p + p + p )-o rb ita l 3 1 1

Hnh 4.5. Lai ho sp3

Hnh 4.6 S xen ph orbital trong phn t CH4, NH3, H2O

Hnh 4.7. Phn t BCl3

a. Orbital lai ho sp2

Hnh 4.8. lai ho sp

i vi 2 nguyn t cui chu k 2 (oxi v flo) c qui lut phn b nh sau:

Hnh 4.10. S to thnh lin kt v

Hnh 4.11. S to thnh lin kt v

Hnh 4.12. Gin nng lng ca nguyn t v phn t hyro

Hnh 4.13. Gin nng lng nguyn t v phn t ca cc nguyn t chu k 2

= lq trong l - di phn cc q - in tch

Hnh 4.14. S phn cc bin dng

Hnh 4.15. S phn cc ho nh hng

Hnh 5.1. S thay i nng lng ca h gin n

QV = DU Vy nhit ng tch chnh bng s bin i ni nng ca h. * Nhit bin i ng p:

i lng H c gi l Entanpi. Vy nhit ng p chnh bng s bin i

* Quan h gia nhit ng tch v nhit ng p: T H = U + PV, ta c:

QP = H = (eHE + qHQ) - (aHA + bHB)

Hnh 5.2. Cch thc to thnh phn t CO2

Hthun Hthun + Hnghch = 0

Hnh 5.3. Hiu ng nhit ca phn ng thun nghch

Hs = (eHE,s + qHQ,s) - (aHA,s + bHB,s)

C2H6(k) + 7/2O2(k) = 2CO2(k) + 3H2O(h) DH = (DH1,c + DH2,c ) - DH3,c

NaCl (r) DHNaCl