Hoa Dai Cuong D

CHNG 1 CC KHI NIM V NH LUT C BN CA HA HC A. MC TIU, NHIM V 1.
MC TIU Hc xong chng 1 sinh vin bit v hiu: - Cc khi nim c bn: Cht, nguyn t, nguyn t, phn t, khi lng nguyn t, khi lng phn t, khi lng mol, ng lng... - H n v. - Mt s nh lut c bn ca ho hc. - Mt s phng php xc nh khi lng phn t v khi lng nguyn t. 2. NHIM V Tm hiu v cc khi nim c bn ca ho hc, h n v SI, cc nh lut c bn ca ho hc, cc phng php xc nh khi lng phn t v khi lng nguyn t t hiu c v c kh nng vn dng c cc kin thc ca chng vo thc hnh v luyn tp. 3. V PHNG PHP Kt hp cht ch gia s hng dn ca gio vin vi s t hc, t nghin cuca sinh vin. Cn ht sc coi trng khu luyn tp v thc hnh nm vng c cc vn ca chng ny. 4. TI LIU THAM KHO - Ho hc i cng 1: Trn Thnh Hu, nh xut bn i hc s phm - Ho hc i cng: Nguyn c Chuy, nh xut bn gio dc - Ho hc i cng: o nh Thc, nh xut bn i hc Quc gia H Ni - Bi tp ho hc i cng: o nh Thc, nh xut bn gio dc - Bi tp ho i cng : Dng Vn m, nh xut bn Gio dc - Ho hc i cng : L Mu Quyn, nh xut bn Gio dc - C s l thuyt ho hc- Phn bi tp: L Mu Quyn, nh xut bn khoa hc v k thut
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B. NI DUNG 1. MT S KHI NIM C BN CA HA HC 1.1. Cht: Cht l tp hp cc tiu phn c thnh phn, cu to, tnh cht xc nh v c th tn ti c lp trong nhng iu kin nht nh. V d 1: C6H6, O2, H2O,... Cht m phn t c cu to bi mt loi nguyn t c gi l n cht. V d 2: Ag, O2, O3, ... Cht m phn t c cu to bi hai loi nguyn t tr ln c gi l hp cht. V d 3: NaCl, H2O, CaCO3, C2H5OH,... T cc khi nim v n cht, hp cht va c cp trn kt hp vi cc kin thc c, ta c s sau (hnh 1.1)
HNH 1.1. S h thng phn loi cc cht Tp hp ca cc phn t cng loi c gi l nguyn cht, nh kh H2 nguyn cht; nc (H2O) nguyn cht;.... Tp hp gm cc phn t khc loi c gi l hn hp, khng kh l hn hp gm rt nhiu kh khc nhau trong N2 v O2 chim t l ln nht (mt cch gn ng ngi ta coi khng kh gm 4/5 nit, 1/5 oxi v th tch) Cc khi nim ny c minh ha hnh 1.2. Tp hp vt cht c th l h ng th hoc h d th. Khng kh l h ng th, hp kim inox l h ng th, mt cc nc c c nc lng v nc l h d th.
Trng i hc cng nghip h ni
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HNH 1.2. Minh ha cc khi nim n cht, hp cht, hn hp 1.2. Nguyn t, nguyn t ho hc, phn t 1.2.1. Nguyn t: l ht nh nht ca nguyn t ho hc m khng th phn chia c v mt ho hc. V d 5: nguyn t H, O, Na, Cl... Nguyn t l loi ht rt Nh v rt nh. Tu thuc vo mi nguyn t ho hc m khi lng ca mt nguyn t 10-23 10-21 g, cn ng knh ca mt nguyn t vo khong 10-8 cm. hnh dung v th tch ca mt nguyn t, c th hnh dung nh sau: Nu coi mi nguyn t u c dng hnh cu c ng knh 10-8 cm th qu bng bn c ng knh 4 cm c th cha c khong 1024 nguyn t. Nguyn t ca cc nguyn t ho hc khc nhau th c khi lng v kch thc khc nhau. Chng ta tha nhn nguyn t c cu to bi 3 loi ht c bn l: electron (e), proton (p) v ntron (n), bng 1.2 cho chng ta bit c im c bn ca ba loi ht .
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BNG 1.1. Bn knh cng ho tr (A0) v khi lng nguyn t ca mt s nguyn t ha hc

Nguyn t H O S Cl Br I R (A0) 0,30 0,66 1,04 0,99 1,14 1,33 M(1,673.10-23) 1,008 15,994 32,064 35,453 79,904 126,904
BNG 1.2. Khi lng, in tch ca electron, proton, ntron
KHI LNG Kg Electron Proton Ntron 9,109.10

-31
IN TCH Culong -1,6021.10 0,0

-19
vC (u) 5,55.10 1,007 1,009

-4
Quy c -1 +1 0,0
1,672.10-27 1,675.10-27
+ 1,6021.10-19
bng 1.2 im cn ch l: in tch ca cc ht c bn. Ntron l ht khng mang in, tc l ht trung ho in, c k hiu l -19 Culong. in tch ny 0n. Mi ht proton mang in tch dng l +1,6021.10 chnh l in tch c bn, thng c k hiu l e0. Tr s ny c quy c chn lm n v nn: mi ht proton mang mt n v in tch dng, c k hiu l 1p. Mi ht electron mang mt n v in tch c tr s tuyt i bng tr s in tch ca mt ht proton nhng ngc du. V th mi electron mang mt n v in tch m, k hiu l e. Cng cn ch , khi lng ca electron rt nh so vi khi lng ca proton, ntron. T s liu ca bng 1.2, ta c t l cc khi lng nh sau:
m1 p me = 1835,5 (ln) m0 n me = 1838,8 (ln)
V vy trong cc php tnh thng thng, ta coi me 0. Cng t bng trn ta thy m n > m p . Trong cc php tnh thng thng ta chp nhn s gn ng: m n m p 1 (vC)
0 1
0 1
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1,6021.10-19 l in tnh nh nht nn c gi l n v in tnh nguyn t v c k hiu l e0. M hnh nguyn t c tha nhn rng ri hin nay l: Nguyn t c hnh dng ca mt khi cu. Tm ca nguyn t l ht nhn tch in dng. V ca nguyn t gm cc electron chuyn ng quanh ht nhn. S n v in tch dng ca ht nhn bng s n v in tch m ca v. Nguyn t trung ha v in V d 6: Ht nhn nguyn t natri (Na) c 11 n v in tch dng (k hiu Z = 11), v nguyn t Na c 11e, tc l c 11 n v in tch m. Vy nguyn t Na trung ha v in, c vit l Na0 hay Na. Nu v mt l do no v nguyn t Na cn 10e, ta c ion dng hay cation natri, c vit l Na+. Tng t, ht nhn nguyn t Clo (Cl) c 17 in tch dng (Z = 17), v nguyn t Cl c 17e nhng nu c nguyn t Cl c thm mt e tr thnh 18e, nguyn t Cl khi ny khng cn trung ha v in na, ta c ion m, hay anion clo, ClBiu din qu trnh bin i nguyn t trung ha in thnh ion nu trn nh sau: Na - e Na+ Cl + e Cl1.2.2. Nguyn t ha hc: Tp hp cc loi nguyn t m ht nhn c cng s n v in tnh dng (Z) l mt nguyn t ha hc. V d 7: Nguyn t oxi c s n v in tch dng ca ht nhn bng 8. Trong thc t c 3 nguyn t oxi vi khi lng khc nhau l 16, 17, 18 nhng u c s n v in tch dng ca ht nhn bng 18, l cc nguyn t khc nhau - cc ng v ca nguyn t oxi. 3 nguyn t ny c vit nh sau: 17 18 hay 8O16 8O 8O Nh vy s n v in tch dng ca ht nhn (Z) l yu t quyt nh ca mt nguyn t ha hc. Tr s Z thay i d ch 1 n v ng ngha vi vic chuyn t nguyn t ha hc ny sang nguyn t ha hc khc. V d 8: Hai nguyn t c cng khi lng nguyn t l 40 (vC), mt nguyn t c Z = 19, nguyn t kia c Z = 20. l 2 nguyn t ca hai nguyn t ho hc, mt l 19K40 (ng v thng gp ca K) v mt l 20Ca40. Cn phn bit cc khi nim nguyn t, nguyn t, n cht V d 9: K hiu O dng ch 1 nguyn t ca nguyn t oxi. cng l k hiu ca nguyn t oxi. K hiu O2- (gi s xut hin trong qu trnh in phn nhm oxit nng chy) ch 1 ion oxi. ion ny c to ra t nguyn t ca nguyn t oxi. l 2 dng th hnh ca oxi. K hiu O2 ch 1 phn t n cht oxi. K hiu O3 ch 1 phn t n cht ozon. O2 v O3 K hiu H2O ch 1 phn t nc. H2O l mt hp cht v trong thnh phn phn t c 2 nguyn t l hiro v oxi.
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Xt tng t vi cc trng hp khc, c th khi qut nh sau: Nguyn t ha hc l khi nim rng, dng ch cc ht v cng nh: nguyn t, ion c cng s n v in tch dng ca ht nhn. Nguyn t l mt khi nim ch mt dng tn ti c th ca nguyn t ho hc. V th, khi ni n nguyn t c th th cng c ngha l ni n mt nguyn t ho hc. n cht l khi nim ch mt dng tn ti c th ca nguyn t ha hc. Khi ni n mt n cht cng c ngha l ni n mt nguyn t ha hc. 1.2.3. Phn t: l phn t nh nht ca mt cht c th tn ti c lp nhng vn gi nguyn tnh cht ca cht . V d 10: H2 l phn t H2, chy c v dng lm nhin liu. 2H2 + O2 2H2O H < 0 (to nhit) CO2 l phn t cacbon ioxit, khng chy c. Phn t c to nn t cc ht nh hn (nguyn t hay ion) Phn t c to ra t cc nguyn t ca cng mt nguyn t ha hc l phn t n cht. V d 11: Cl2. O2, O3, P4, S8,... Cc n cht khc nhau ca mt nguyn t ha hc c gi l cc dng th hnh ca nguyn t . V d 12: Nguyn t oxi c 2 dng th hnh thng gp l oxi (O2) v ozon (O3). Nguyn t cacbon c 2 dng th hnh ph bin l than ch v kim cng, ... Phn t c to ra t hai loi nguyn t ca 2 nguyn t ha hc tr ln l phn t hp cht. V d 13: HCl, HClO,... Phn t c th c to ra t 1 nguyn t th l phn t n nguyn t. V d 14: kh him Mt s c im v phn t: - V khi lng phn t: C nhng phn t rt nh (H2), c nhng phn t nng nh ng glucoz C6H12O6 (180 vC) v cng c nhng phn t siu nng nh polime (c khi lng phn t trung bnh c hng chc vn vC). Chi tit c trnh by phn sau. - V in tch: th phn t trung ha v in. V th cn phi phn bit phn t vi gc t do: K hiu SO3 ch phn t anhirit sunfuric; k hiu ch gc t do c to thnh tc thi (thi gian tn ti v cng ngn) trong phn ng. - V cu to ha hc: y l mt vn ln, phn ny ch xt mt s c im v hin tng ng phn. ng phn l hin tng cc cht c cng cng thc phn t, nhng c cu to khc nhau nn c tnh cht khc nhau, cc cht l cc ng phn Xut pht t c im v cu trc, ta c ng phn cu to v ng phn khng gian.
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V d 15: t cng thc C2H6O ta c 2 ng phn cu to l ru etylic CH3CH2OH v imetyl ete CH3OCH3; t cng thc abC = Cab ta c 2 loi ng phn khng gian l cis v trans. Trong ng phn cu to c ng phn mch cacbon; v tr (nhm chc, lin kt bi,...), ng phn nhm nh chc. Trong ng phn khng gian c ng phn hnh hc, ng phn quang hc v vn v cu dng. Ch : Khi xt phn t cn quan tm ti hnh dng hay hnh hc phn t. Thc nghim xc nh c gc lin kt v di lin kt. Cc yu t hnh hc thng gn lin vi di v tnh cht ca phn t. Mt s hnh dng phn t thng gp nh: ng thng (cc nguyn t trong phn t c phn b trn mt ng thng); c gc (cc nguyn t thng l 3 hay 4 nguyn t lin kt vi nhau to ra gc khc gc 1800); lp th (khi khng gian nh thp tam gic, t din u, bt din u,...), minh ha hnh 1.3.
HNH 1.3. Mt s hnh dng phn t a) CO; b) CO2, phn t thng c) H2O, phn t gc d) NH3, phn t thp tam gic e) CH4, phn t t din 1.3. Khi lng nguyn t, khi lng phn t, khi lng mol 1.3.1. Khi lng nguyn t: l khi lng ca mt nguyn t, khi lng nguyn t c xc nh bng tng khi lng ca tt c cc ht to thnh nguyn t . Cn phn bit khi lng nguyn t tng i v khi lng nguyn t tuyt i. a) Khi lng nguyn t tuyt i: l khi lng thc ca mt nguyn t trong khng gian c tnh bng kilogam. V d 16: mS = 5,3.10-23g = 5,3.10-26 kg mFe = 9,274.10-23g = 9,274.10-26 kg mC = 19,9206.10-24g = 19,9206.10-27kg
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Khi lng ny cc k nh b, khng thun tin cho vic cn, o, ong, m c nn gp kh khn khi phi tnh ton trong cc bi ton ha hc. thun tin cho vic tnh ton ngi ta dng mt h khc, gi l khi lng nguyn t tng i. b) Khi lng nguyn t tng i (nguyn t khi): A Chn
1 ln khi lng ca mt nguyn t cacbon ng v 12 (C12) lm 12
mt n v khi lng v c gi l n v cacbon (vC hay u), ta c:

1dvC =
m12C
12
19,9260.10 27 kg = 1,6605.10 27 kg 12
AC =
m12C
1,6605.10 27 kg
= 12
9,274.10 26 kg = 56 AFe = 1,6605.10 27 kg 5,3.10 26 kg = 32 AS = 1,6605.10 27 kg
Nh vy, khi lng nguyn t tng i l mt tr s khng c th nguyn. Nhng trong thc t ta vn hay dng mt cch ngn gn Fe= 56vC hay 56u (dng n v cacbon: vC) v coi
1 m12 l 1vC (1u). 12 C
T cc v d trn cn nh: khi lng nguyn t tng i (klt) = khi lng nguyn t tuyt i (klt) : s Avgar (N) KLT = klt : N 1.3.2. Khi lng phn t: ly khi lng ca 1 phn t chia cho 1 n v khi lng th c khi lng phn t tng i ca phn t . Hoc: ly tng khi lng nguyn t tng i ca tt c cc nguyn t to nn phn t . Thng c k hiu l: M V d 17: M CO = 12 + 16.2 = 44 (hay: 44 vc), thng vit l CO2 = 44 1.3.3. Mol - Khi lng mol a) mol: Mol l lng cht cha 6,023.1023 ht vi m. T khi nim ny khi dng mol cn phi ch r loi ht vi m. V d 18: 1mol nguyn t H, 1mol phn t H2, 1mol ion H+,... b) Khi lng mol: Khi lng mol nguyn t ca mt nguyn t (A) l khi lng ca 1 mol nguyn t ca nguyn t . n v g/mol V d 19: khi lng mol nguyn t ca hiro bng 1,008 g/mol ( hay AH = 1,008 g/mol) Khi lng mol phn t ca mt cht (M) l khi lng ca 1 mol phn t cht . V d 20: Khi lng ca 1 mol phn t nc bng 18,015 g/mol (hay M H O = 18,015 g / mol 18 g / mol ).
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Cch tnh s mol:
nX =
mX M X ( AX )
y: m X l khi lng ca X . Nu X l nguyn t th dng AX l khi lng mol nguyn t ca X . Nu X l mt cht th M X l khi lng mol phn t ca X . 1.4. ng lng 1.4.1. ng lng ca mt nguyn t: L s phn khi lng ca nguyn t c th kt hp hoc thay th 1,008 phn khi lng ca hiro hoc tm phn khi lng ca oxi. K hiu ng lng l: Theo nh ngha trn, ta c:
H = 1,008 1 ; O = 8,00
Na = 23 ; Ca = 20
T nh ngha trn d dng xc nh c: ng lng ca C trong CO2 l 3 cn trong CO l 6. C th tnh ng lng ca mt nguyn t theo cng thc:
i = Ai ni
Trong : Ai l khi lng nguyn t ca nguyn t; ni l ha tr ca nguyn t. 1.4.2. ng lng ca mt hp cht: L s phn khi lng ca hp cht tc dng va vi mt ng lng ca cht khc. V d 21: Bit Al = 9 . T phn ng: 2Al + 6HCl 2AlCl3 + 3H2, d dng tnh c HCl = 36,5 Bit NaOH = 40 . T phn ng: 2NaOH + H2SO4 Na2SO4 + 2H2O, tnh c H SO = 49 1.4.3. Cch tnh ng lng:
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a) Trng hp chung:
A( M ) n
Trong : A(M ) l khi lng nguyn t hay khi lng phn t. n l s e trao i b) Cc trng hp c th: + i vi nguyn t ho hc: = hc. + i vi hp cht: =
M n A H
vi H l ha tr ca nguyn t ha
vi n l s electron trao i.
Nu hp cht l: - Oxit: Th n l tng ha tr ca oxi c trong oxit. - Axit: Th n l s nguyn t hiro c trong axit c thay th. - Baz: Th n l ha tr ca kim loi c trong baz. - Mui: Th n l tng ha tr ca kim loi c trong mui.
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V d 22: ng lng ca Fe2O3 l:
Fe2O3 =
ng lng ca H2SO4 trong phn ng:
160 = 26,7 2 + 2 + 2 = 3.2
ng lng ca Fe, trong phn ng: Fe + 2H+ Fe2+ + H2 l Fe = 56 : 2 = 28 Cn trong phn ng: 2Fe + 3Cl2 2FeCl3 l Fe = 56 : 3 = 18,67 Ch : Theo nh ngha v ng lng th ng lng l mt i lng khng c n v. 1.4.4. ng lng gam: ng lng gam ca mt cht (n cht hay hp cht) l lng cht c tnh bng gam v c tr s ng bng ng lng ca cht . Nu k hiu ng lng gam l lg, ta c: lgAl = 9g v Al = 9 1.4.5. S ng lng gam(s lg): c xc nh bng s gam chia cho ng lng gam. Cng thc tnh: S lg = s gam : lg Cho mHCl = 18,25g S lgHCl = 18,25g/36,5g = 0,5 Nh vy s ng lng gam cng l i lng khng c n v. 2. H N V Mt trong cc vn ca ha hc, l bi ton ha hc. Bi ton ha hc c t ra da trn yu cu ca thc t i sng, thng qua cc thc nghim ha hc. V th cc kt qu thng qua cc con s phi c ngha xc nh. Cho nn cc con s ny buc phi c n v. Ch c p s bng s ng th cha m cn cn phi c n v ng. Mt lng vt cht lun c biu th bng tr s c km theo n v. Lng vt cht = Tr s. n v Hin nay, c hai xu hng: Dng h n v quc t (h SI) v dng n v theo thi quen.Trong qu trnh hi nhp vi quc t, chng ta nn dng h n v quc t (h SI) 2.1. H n v quc t (h SI) i hi v o lng quc t hp ti Pari vo thng 10 nm 1960 thng qua cc quy c v n v o v cc khi nim tng ng. Trong chng ny ch xt h n v c th. 2.1.1. H SI c s Gm by i lng c chn lm c s cng vi n v ca mi i lng km theo, c a ra bng 1.3
98 = 49 2 98 NaOH + H2SO4 NaHSO4 + H2O l H 2 SO4 = = 98 1 74 ng lng ca Ca(OH)2 l: Ca (OH )2 = = 37 2 310 ng lng ca Ca3(PO4)2 l: Ca3 ( PO4 )2 = = 51,7 2 + 2 + 2 = 3.2
2NaOH + H2SO4 Na2SO4 + 2H2O l H SO =

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BNG1.3. By i lng c bn ca h o lng quc t (h SI)

I LNG Tn gi Chiu di Khi lng Thi gian Cng dng in Nhit Lng cht Cng nh sng K hiu
l
N V O Tn gi mt kilogam giy Ampe Kelvin Mol Cadela (nn) K hiu Quc t m kg s A K mol cd Vit Nam m kg s (giy) A K mol cd
m t I T n I
Ngoi ra cn c hai n v b sung thng dng l

Gc phng Gc khi radian sterdian rad sr Rad sr
2.1.2. n v dn xut t n v SI c s Cc n v dn xut t h n v SI c s c xc nh ph hp vi cc nh lut vt l cng nh quan h gia cc i lng lin quan. V d 23: n v ca lc F, theo nh lut th 2 ca Niutn: F = m.a l lc gy ra mt gia tc l 1 m/s2 cho vt c khi lng tnh 1kg. Vy lc F s c n v l kg.m.s-2, c k hiu l Niutn, ngha l: 1N = 1 kg.m.s-2 BNG 1.4. Mt s n v dn xut t n v SI c s a) n v c tn ring
I LNG Lc p sut Nng lng Cng sut in tch in th Tn s N V Niutn (Newton) Patcan (Pascal) Jun (Joule) Oat (Watt) Culong (Coulomb) Von (Volt) Hec (Hertz) K HIU N Pa J W C V Hz KHI NIM kg.m.s-2 N.m2 (hay kg.m-1.s-2) kg.m2.s-2 J.s-1 (hay kg.m2.s-3) A.s J.C-1 (hay J.A-1.s-1) s-1
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b) Cc i lng khng c tn ring

I LNG Din tch Th tch Vn tc Gia tc Khi lng ring Cng in trng N V mt vung mt khi mt/giy mt/giy2 kilogam/met khi von/mt K HIU m2 m3 m.s-1 m.s-2 kg.m-3 V.m-1
2.2. n v phi SI T thi quen hng ngy trong cuc sng m mt s n v khng thuc h SI vn thng xuyn c dng. Tuy nhin khi dng cc n v ny cn phi tm mi lin h qua li gia chng. Mt s n v phi SI thng dng BNG1.5. Mt s n v phi SI
N V I LNG Tn Chiu di Th tch Nhit Thi gian Angstrom lit bch phn pht gi atmotphe bar mm thy ngn ec calo oat gi kiloat gi electron Von n v tnh in cgs bai (Debye) K hiu A0 C min h atm bar mmHg erg cal Wh kWh eV ues cgs o D
0
THA S I V N V SI C S HAY DN XUT 10-10m 10-3m3 t (0C) =T - 273,15 1 min = 60s 1h = 3600s 1 atm = 1,013.105Pa 1 bar = 105Pa (1atm) (1mmHg =1/760 atm) 10-7J 4,184J 3600J 3600kJ 1,602.10-19J
p sut
Nng lng
in tch Gc phng Momen lng cc in
(/180)rad 1/2,9979.10-29c.m
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2.3. Cc hng s vt l BNG 1.6. Cc hng s vt l thng dng

HNG S Hng s Avgar (Avogadro) n v khi lng nguyn t Khi lng electron Khi lng proton Khi lng ntron in tch nguyn t Hng s Faraday Hng s Plng (Planck) Vn tvs nh sng (trong chn khng) Th tch mol phn t cc cht kh Hng s kh K HIU NA u me mp mn e0 F h c V0 R GI TR 6,0223.1023/mol 1g/N = 1,6605.10-24g 9,1095.10-28g 5,4858.10-4u 1,67258.10-24g 1,00724u 1,6748.10-24g 1,00862u 1,6021.10-19C 4,8.10-10ues cgs 96487,0 C/mol 96500 C/mol 6,6256.10-34 Js 2,99725.1018m/s km/s = 300.000
22,41 l/mol = 0,02241 m3/mol 8,3144J/mol.K 8,2054.10-2 1atm/mol.K 1,98 cal/mol.K
Hng s Bnxman(Bolzman) Hng s Ritbe (Rydberg) Manhton Bo (Bohr) Bn knh Bo (Bohr)
k RH B a0
1,38054.10-23 J/K 109677,57 c.m-1 9,2732.10-24 J/T 5,29167.10-19cm = 0,529 A0
2.4. H n v nguyn t Trong ha hc lng t (nhng ni dung v cu to ca vt cht) chng ta dng h n v nguyn t (vn hay au). Trong h ny quy c cc lng sau y bng n v: 12
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Hng s Plng rt gn h =
Bn knh Bo th nht a0 0,529 1,0 Khi lng ca mt electron, me =9,109.10-31kg 1 in tch c bn e0 = 1,6021.10-19culong 1 Tch 40 = 1 (quy c ny c th dng chung vi bn quy c trn hoc dng ring mnh n). T cc quy c trn ta c n v ca nng lng tng ng s l vn hay au hay l hactri (hartree). V d 24: Gii phng trnh sring cho h 1 electron 1 ht nhn (H, + He , Li2+,...) tm c biu thc tnh nng lng l:
En =
4 h mZ 2 e0 1 trong h = 2 2 2 2n h (4 0 ) 2
h 1,0 (vi h = 6,625.10-34J.s) 2
a)Hy tnh nng lng ng vi n = 1 cho: H, He+, Li2+ b) Hy tm mi lin h gia hai n v nng lng l vn vi eV Tr li: T s liu cc bng trn, ta c: me = 9,1095.10-28g = 9,1095.10-31kg h = 6,6256.10-34J.s e0 = 1,6021.10-19C 40 = 1,112650056.10-10J-1.C2.m-1 a) Thay cc s liu vo biu thc tnh nng lng En ta c: E1 = -13,6xZ2 (eV) hay E1 = Vi H: Z = 1 E1 = - 13,6 (eV) hay E1 = - 0,5 (vn) Vi He+: Z = 2 E1 = - 54,4 (eV) hay E1 = - 2,0 (vn) Vi Li: Z = 3 E1 = - 122,4 (eV) hay E1 = - 4,5 (vn) b) T cc kt qu trn ta c mi lin h: 1(vn) = 27,2(eV) 3. MT S NH LUT C BN CA HA HC 3.1. nh lut bo ton khi lng (Lmnxp nh bc hc Nga v Loavazi nh bc hc Php) Bo ton vt cht l quy lut chung ca t nhin, trong cuc sng hng ngy hiu mt cch n gin l quy lut tng khng i. Ha hc l khoa hc v cc cht v s bin i gia cc cht, nn quy lut v bo ton vt cht c th hin rt y . Trong ha hc l nh lut bo ton khi lng. nh lut ny c nhiu cch pht biu khc nhau: Tng khi lng cc cht tham gia phn ng bng tng khi lng cc cht thu c sau phn ng. Mt cch tng qut : C s bo ton vt cht trong cc phn ng ha hc. Xt phn ng dng tng qut:
0 l hng s in mi trong chn khng
1 Z 2 vn (hay hactri) 2
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gio trnh ho i cng
Th lun c: m A1 + m A1 + ... + m A n = m B1 + m B 2 + ... + m B n ' Hay:
A1 + A2 + + An B1 + B2 + + Bn
m Ai = m Ai '
i =1 i '=1
n'
Xt v phng din l thuyt th khi lng cc cht thc s khng c bo ton, v phn ng ha hc lun lun km theo qu trnh gii phng hay hp th nng lng di dng nhit. Nm 1905, Anhstanh ch ra rng: Khi lng ca mt vt v nng lng ca n lin h vi nhau bi h thc E = mc2. Trong c l vn tc nh sng bng 3.108m/s. Nu gi E l nng lng km theo ca phn ng ha hc th s thay i khi lng trong phn ng ha hc s l: E = m.c2 m = E/c2, do E rt nh, c rt ln nn m l v cng b (khng ng k). Do khng pht hin thy s thay i khi lng ca phn ng ha hc (m), nn nh lut bo ton khi lng ca Lmnxp vn c tha nhn. ng dng ca nh lut: Gii nhanh bi ton ha hc bng phng php bo ton khi lng. Ch khi gii bi, khng tnh khi lng ca phn khng tham gia phn ng, cng nh phn cht c sn, v d nh nc c sn trong dung dch. V d 1: Hn hp X gm Fe, FeO, Fe2O3. Cho lung CO i qua ng ng m(g) hn hp X nung nng. Sau khi kt thc th nghim thu c 64,0g cht rn A trong ng s v 12,32 lt kh B ( 27,3oC; 1atm) c t khi so vi H2 l 20,4. Tm m? Tr li: Phng trnh phn ng chung: X + CO = A + CO2 m 64,0
nB = 12,32.1.273 = 0,5(mol ) 1.(273 + 27,3).22,4
Gi x l s mol CO2 ta c: 44x+28(0,5x)/0,5=20,4.2=40,4 x=0,4 (mol). Theo nh lut bo ton khi lng ta c: mX + mCO = mA + mCO2 mX = mA + mCO2 - mCO = 64 + 0,4.44 - 0,4.28 = 70,4(g) V d 2: Cho hn hp axit hu c A, B tc dng vi ru a chc C thu c hn hp nhiu este, trong c este E. t chy ht 1,88 g E cn mt lng va l 1,904 lt oxi ( ktc) thu c CO2 v hi H2O vi t l th tch tng ng l 4/3. Xc nh cng thc phn t ca E bit t khi ca E so vi khng kh nh hn 6,5. Tr li: Phng trnh phn ng chung E + O2 CO2 + H2O Theo nh lut bo ton, ta c:
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gio trnh ho i cng
mE + mO2 = mCO2 + mH2O=1,88+(1,904/22,4).32=4,6 (g) Gi a l s mol CO2 th 3a/4 l s mol H2O. Vy: 44a + (3a/4).18 = 4,6 a = 0,08 (mol) mC = 0,08.12 = 0,96 (g) mH = (3/4).0,08.2 = 0,12 (g) mO = 1,88 - 0,96-0,12 = 0,8 (g) x:y:z=
0,96 0,12 0,8 : : = 8 : 12 : 5 12 1 16
Do cng thc n gin nht ca E l C8H12O5 v cng thc phn t l (C8H12O5)n. Theo : mE < 29x6,5 = 188,5 n=1 Vy cng thc phn t ca E l: C8H12O5 V d 3: C mt chn A cha dung dch Na2CO3 c khi lng l g1, cn chn B cha dung dch HCl c khi lng g2. t gt = g1 + g2 Trn dung dch trong chn A vi chn B, lc u cho phn ng xy ra hon ton ri cn c hai cc v ha cht c khi lng tng cng l gs. a) C th c nhng trng hp no v mi quan h gia hai tr s gt v gs? Ti sao? b) C th xy ra trng hp gt < gs khng? ti sao? Tr li: a) Xy ra mt trong hai trng hp sau: Trng hp 1: gt > gs v xy ra phn ng Na2CO3 + 2HCl 2NaCl + H2O + CO2 Lng CO2 thot ra khi dung dch lm gim khi lng cc cht cn li trong cc sau phn ng. Trng hp 2: gt = gs v xy ra phn ng Na2CO3 + HCl NaCl + NaHCO3 Khng c cht no thot ra khi chn, nn khi lng trc v sau phn ng bng nhau. b) Khng th xy ra trng hp gt < gs v iu ny tri vi nh lut bo ton khi lng. 3.2. nh lut thnh phn khng i (Prt-nh bc hc Php) Mt hp cht ha hc d c iu ch bng cch no cng u c thnh phn khng i. Gii thch: Nu chp nhn quan im v cu to nguyn t v cu to phn t th thnh phn ca mt cht bt k chnh l thnh phn ca mt phn t cht . Trong mt phn t ca mt cht xc nh, th s nguyn t ca nguyn t l xc nh, khng i. V vy thnh phn khi lng ca nguyn t cng khng i. Vai tr ca nh lut: cho php phn bit mt cht ha hc vi mt hn hp ch: Thnh phn ca mt cht khng thay i cn thnh phn ca hn hp thay i theo phng php iu ch.
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gio trnh ho i cng
Hn ch ca nh lut: ch ng khi cht c cu trc phn t hay cu trc tinh th hon chnh, khng ng i vi hp cht khng nh thc. V d 4: T ni dung ca nh lut d thy H2O c t l v s nguyn t trong phn t H : O = 2 : 1 Nc c iu ch theo mt s cch sau:
2 H 2 + O 2 t 2 H 2 O 2 Na 2 SO 4 + H 2 SO 4 Na 2 SO 4 + H 2 O CH 4 + 2O 2 t CO 2 + 2 H 2 O
0 0
3.3. nh lut t l bi nh lut ny c nh bc hc Prut a ra vo nm 1806. Nu hai nguyn t ha hc to vi nhau mt s hp cht th cc lng ca mt nguyn t kt hp vi cng mt lng ca nguyn t kia t l vi nhau nh cc s nguyn nh. V d 5: Xt hp cht gia C v O l CO v CO2. D thy lng O kt hp vi cng lng C lp thnh t s l 1: 2. V d 6: Xt cc oxit ca nit bng sau1.7. BNG 1.7. Mt s kt qu thc nghim thu c khi xc nh thnh phn nguyn t trong cc oxit ca nit
Tn oxit init oxit Nit oxit init trioxit Nit ioxit init pentoxit Thnh phn % khi lng N 63,7 46,7 36,8 30,4 25,9 O 36,3 53,3 63,2 69,2 74,1 S phn khi lng oxi ng vi mt phn khi lng nit 0,57 1,14 1,71 2,28 2,85 T l lng oxi
1 2 3 4 5
T cc kt qu thc ngim thu c bng 3.1, ta ly:

0,57 1,14 1,71 2,28 2,85 : : : : = 1: 2 : 3 : 4 : 5 0,57 o,57 0,57 0,57 0,57
Nh vy t l khi lng oxi ng vi 1 phn khi lng nit trong cc oxit trn l 1:2:3:4:5 Cng c th xc nh c cc s ny bng cch thng qua thnh phn % v khi lng gia nit v oxi, d dng xc nh c cng thc ca cc oxit tng ng: init oxit: N2O, Nit oxit: NO, init trioxit: N2O3, Nit ioxit: NO2 v init pentoxit: N2O5 T cc cng thc ny,nu ly cng mt lng nit tng ng nh nhau (gi s 2 mol nit) th s mol oxi tng ng NO N2O3 NO2 N2O5 N2O
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gio trnh ho i cng
2 1
2 2
2 3
2 4
2 5
S mol tng ng ca oxi s l 1:2:3:4:5 ng nhin t l ny cng l t l v s nguyn t oxi trong cc oxit tng ng khi kt hp vi hai nguyn t nit. V d 7: Vn dng nh lut thnh phn khng i v nh lut t l bi cho SO2 v SO3. + iu ch SO2: S + O2 SO2 Na2SO3 + H2SO4 Na2SO4 + H2O + SO2 CuSO3 CuO + SO2 + iu ch SO3: SO2 + O2 2SO3 Fe2(SO4)3 Fe2O3 + 3SO3 + D dng xc nh c cc lng oxi kt hp cng vi mt lng lu hunh lp thnh t s 2 : 3 ( hoc cc lng lu hunh kt hp vi mt lng oxi lp thnh t s 3 : 2). 3.4. nh lut Avgaro: (ch p dng cho cht kh) 3.4.1. nh lut Avgar Nh khoa hc ngi Italia - Avgar a ra mt gi thuyt v cht kh, v sau c gi l nh lut v mang tn ng: nh lut Avgar. Trong cng iu kin v nhit v p sut, nhng th tch bng nhau ca cc cht kh u cha cng mt s phn t. H qu: 00C, 1atm (760 mmHg) 1mol kh bt k chim th tch l 22,4 lt. nhng iu kin nh nhau v nhit v p sut 1 mol kh bt k u c th tch bng nhau. V vy: Th tch m 1 mol kh chim ch c gi l th tch mol phn t ca kh. Th tch mol phn t ca mi cht kh 00C, 1atm l 22,4 lt. nh lut ny ch p dng cho cht kh, k c hn hp cc kh. Cc kh u c chung c im: Khong cch gia cc kh rt ln, kch thc ca cc kh li rt nh v vy c th b qua kch thc ca cc phn t kh khi cc phn t kh c coi nh nhng cht im. T c im ny, thy rng: cng iu kin v nhit ,p sut tc dng ln cc kh l nh nhau th trong nhng th tch bng nhau ca cc kh s cha cng mt s lng nh nhau v cc phn t kh. T d dng thy c s phn t kh t l thun vi s mol kh. Cho nn khi lm cc bi ton v cht kh thng dng mi lin h sau: cng iu kin v nhit v p sut, nhng th tch bng nhau ca mi cht kh u cha cng mt s mol kh. V d 8: Np y vo mt bnh kn 0,5 mol kh H2 ri cn ton b bnh. Sau khi tho ht H2 ra, v lm th nghim nh trn vi kh CO2. Hai ln cn thy khi lng khc nhau l m gam. Tm m.
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gio trnh ho i cng
Nu cng lm th nghim nh trn vi 0,5 mol kh H2, nhng mun hai ln cn m m = 0 th cn dng bao nhiu mol CO2? Bit cc th nghim u c tin hnh cng iu kin v nhit v p sut. Tr li: Theo nh lut Avgar, th nghim trc mi kh u c 0,5 mol. Theo cng thc: 1 mol CO2 nhiu hn 1 mol H2 l 42 gam Vy 0,5 mol CO2 nhiu hn 0,5 mol H2 l m = 0,5.42 = 21(g) trong th nghim sau, m = 0 th mCO = mH = 1( g ) Vy nCO = 1 : 44 = 0,0227(mol ) Cn ch rng: iu kin tiu chun (ktc), t = 00C hay T = 273,15 K; P = 1atm, mt mol kh bt k u chim th tch l 22,4 dm3 (hay22,4 lt) 3.4.2. Phng trnh trng thi ca kh l tng Khi khong cch gia cc phn t kh l rt ln, kch thc ca cc phn t l khng ng k (b qua) th lc tng tc gia cc phn t kh cng khng ng k (b qua) khi kh c gi l kh l tng. Phng trnh lin h gia nhit T, p sut P v th tch V ca kh c gi l phng trnh trng thi ca kh l tng: PV = Rt vi 1 mol kh PV = nRT vi n mol kh
2 2 2
Hoc PV =
m m d RT P = RT = RT ; trong d l khi lng ring M VM M
ca kh. Trong trng hp c mt hn hp kh l tng chim mt th tch V nhit T , th p sut ton phn c xc nh bi nh lut alton: PT = Pi , vi Pi l p sut ring phn ca kh i
i
RT PT = V
n , vi n l s mol ca kh i
i i i
R l hng s kh, tr s R ph thuc vo n v o p sut, th tch cn T phi biu th theo nhit Kenvin. Hng s kh R c s dng rt rng ri trong tnh ton, v vy cn lu cch biu th n v ca n sao cho thng nht. T phng trnh trng thi,ta c:
R= PV 1(mol ).T
T phng trnh ny ch cn thay cc gi tr bng s ca P, V, T th tm c gi tr ca hng s kh R. Theo h thng n v hp php ca nc ta, khi lc o bng Niutn trn 2 1m (N.m-2) cn nng lng o bng Jun (J) cn th tch o bng mt khi (m3), th: P = 1,01324.105Pa = 1,01324.105N.m-2 = 1,01324.105kg/m.s2 V = 0,022415m3 Thay vo, ta c:
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gio trnh ho i cng
R=
PV = 1mol.T
1,01324.10 5
kg .0,022415m 3 2 kg.m 2 m.s = 8,314 2 .mol 1 .K 1 = 8,314 J .mol 1 .K _ 1 1mol.273,15K s
( v 1J = N.m; 1N = 1kg.m/s2 1J = kg.m2/s2) Tuy nhin, hin nay trong nhiu ti liu cn dng nhiu h thng n v khc nhau, nn cng cn phi bit thm. Nu biu din R bng n v calo th da vo mi lin h 1cal =4,184J 1J =1/4,184 = 0,239cal. Thay vo trn ta c: R = 8,314.0,239cal.mol-1.K-1 = 1,987cal.mol-1.K-1. Nu p sut o bng dyn/cm2 v th tch tnh bng cm3 (theo h CGS: di o bng centimt (cm), khi lng o bng gam (g), thi gian o bng giy (s). Khi lc tnh bng dyn, p sut tnh bng dyn/cm2, nng lng tnh bng ec, 1ec =1dyn.cm = 10-7J, cn th tch o bng C.m3). Thay cc s liu vo biu thc (P =1,01324.106dyn/cm2; V = 22413cm3; T = 273,15K), ta c:
R= 1,01324.10 6 dyn .22413cm 3 cm 2 = 8,314.10 7 dyn.cm.mol 1 .K 1 = 8,314.10 7 ec.mol 1 .K 1 1mol.273,15K
Trong trng hp p sut tnh bng atmotphe vt l v th tch o bng lt, th:
R= 1atm.22,415l = 0,08205atm.l.mol 1 .K 1 1mol.273,15K
Nh vy tu thuc vo n v o ca p sut v th tch m hng s kh R c cc gi tr khc nhau. (Cc gi tr ca R c xc nh iu kin tiu chun) V d 9: tm khi lng ring ca kh flo 1atm v 25oC. Tr li: Trc tin tm th tch ca 1mol flo 1atm v 25oC.
RT P M M .P d= = V RT V=
T = 273,15 + 25 = 298,15 K Vy: d =

38,00 g.mol 1 .1atm 1,55( g.l 1 ) 1 1 0,082atm.l.mol .K
3.5. nh lut ng lng Nh bc hc alton ngi Anh pht biu nh lut vo nm 1792, c ni dung nh sau: Cc nguyn t ha hc kt hp vi nhau hay thay th cho nhau theo nhng phn khi lng t l vi ng lng ca chng. Xt phn ng: A + B AB
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gio trnh ho i cng
Ta lun c:
mA A m m = hay A = B mB B A B
hay
s lgA = s lgB
nh lut c pht biu bng cch khc: Cc cht tc dng vi nhau theo cng mt s ng lng gam. Tc l: Trong phn ng ha hc mt ng lng gam ca cht ny ch kt hp hoc thay th mt ng lng gam ca cht khc. V d 10: Oxi ho cn thn 0,253 g Mg thu c 0,420 g MgO. Tm ng lng ca Mg? Tr li: p dng nh lut bo ton khi lng cc cht, ta c:
mMg + mO2 = mMgO
2
Thay s: 0,253 + mO = 0,420 mO = 0,167 g

2
p dng nh lut ng lng:
Mg O
mMg mO
Mg =
m Ng mO
O =
0.253 8 = 12,12 0,167
V khi lng ca oxi c trong oxit bng khi lng ca oxi tham gia phn ng V d 11: Phn tch st oxit, thy t l Fe l 70% v khi lng. Tm ng lng ca Fe ? Tr li: p dng nh lut ng lng, ta c:
Fe = mFe 70 O = 8 = 18,67 100 70 mO Fe mFe = O mO
Nhn xt: T v d 10 thy rng nh lut ng lng gip cho vic gii nhanh bi ton ha hc m khng cn phi cn bng phng trnh phn ng ha hc. 4. MT S PHNG PHP XC NH KHI LNG MOL PHN T CA CHT KH V CHT LNG D BAY HI Xc nh khi lng mol phn t ca mt hp cht l mt vic lm cn thit khi lp cng thc phn t ca mt hp cht. C hai phng php thng dng khi xc nh khi lng phn t ca cht kh v cht lng d bay hi. 4.1. Da vo t khi hi 4.1.1. Khi lng ring ca mt cht kh Khi lng (tnh theo gam) ca mt n v th tch kh (tnh theo lt hay 3 dm ) ti mt nhit xc nh v p sut xc nh, c gi l khi lng ring ca kh . K hiu: DX l khi lng ring ca kh X. T nh ngha, ta c: D X =
mX VX
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gio trnh ho i cng
Trong mX l khi lng ca kh X chim th tch l VX ti nhit v p sut ang xt. Nu xt 1 mol kh ti iu kin tiu chun, ta c:
DX = MX 22,4
Mx = 22,4.DX
Vi: MX l khi lng mol phn t ca kh X. 4.1.2. T khi hi T khi hi ca kh A so vi kh B l t s khi lng ring ca kh A so vi kh B cng iu kin v nhit v p sut. Hay: T khi hi ca kh A so vi kh B l t s khi lng ca V lt kh A so vi V lt kh B cng iu kin v nhit v p sut. K hiu t khi hi ca kh A so vi kh B l: dA/B, theo nh ngha ta c:
d A/ B = DA DB MA M A = d A / B .M B MB
Kt hp vi biu thc trn, ta c: d A / B =
Ch : khi xc nh t khi hi ca kh A vi kh B th phi a v cng th tch nh nhau, th khi t s: d A =

B
mA M A mi l t khi. Cn khi khc = mB M B
m M nhau v th tch th t s khi lng A A khng phi l t khi. mB M B
V d 1: Lng hi ca mt cht A nng hn lng kh nit cng iu kin v nhit v p sut l 2 ln. Hy xc nh: a) Khi lng phn t ca cht A. b) Khi lng ring ca A ti 1atm v 250C Tr li: a) ta c M N = 28 , theo phng trnh M A = d A / B .M B Tm c: M A = d A / N .M N = 2 28 = 56 b) C MA = 56 (g/mol)
2 2 2
T phng trnh: Vy:
PoVo PV P V T 1.22,4.298,15 = V= o o = 24,45(l ) 1.273,15 To T To P M 56 DA = A = 2,29( g / l ) 24,45 V
4.2. Da vo phng trnh trng thi ca kh l tng T phng trnh trng thi ca kh l tng: PV = nRT = M=
m RT PV m RT M
T biu thc ny ,chng ta tnh c khi lng mol phn t ca kh cn kho st.
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gio trnh ho i cng
V d 2: C 3 gam mt cht lng c ho hi hon ton, lng hi ny chim mt th tch l 1,232 lt 250C, 1 atm. Xc nh khi lng mol phn t ca cht . Tr li: T phng trnh : PV = nRT , n =m/M
m.R.T 3 g.0,082atm.l.mol 1 .K 1 .298,15 K = 59,5( g / mol ) M= P.V 1atm.1,232l
5. MT S PHNG PHP XC NH KHI LNG NGUYN T CA CC NGUYN T 5.1. Phng php Canizaro Canizaro lm nh sau: ly mt s hp cht ca nguyn t cn kho st em i xc nh khi lng phn t ca cc hp cht , sau phn tch ha hc xc nh s n v khi lng ca nguyn t kho st c trong tng phn t. Gi tr nh nht trong cc gi tr khi lng tm c ca cc hp cht trn s l khi lng nguyn t ca nguyn t . V d 1: Xc nh khi lng nguyn t ca cacbon, bng 1.8. C s l lun ca phng php Canizaro: trong cc phn t hp cht khc nhau ca cng mt nguyn t phi c mt phn t ca mt hp cht ch cha mt nguyn t ca nguyn t . V vy, nu ly c cng nhiu hp cht khc nhau ca mt nguyn t em i xc nh nguyn t khi ca nguyn t th s c nhiu kh nng c c mt hp cht m mt phn t hp cht ch cha mt nguyn t ca nguyn t cn xc nh nguyn t khi. BNG 1.8. Nguyn t khi ca cacbon
S n v nguyn t cacbon c trong 1 phn t hp cht (44.27,27)/100=12 12 24 72 36
Tn hp cht Cacbondioxit Cacbonoxit Axetylen Benzen Axeton
Phn t khi 44 28 26 78 58
% khi lng 27,27 42,86 92,31 92,31 62,67
T kt qu thu c bng 1.8 cho thy nguyn t khi ca cacbon phi l 12.
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gio trnh ho i cng
T cc kt qu thc nghim thu c bng 1.8, d dng xc nh c cng thc phn t ca : Cacbon ioxit: CO2, cacbon oxit: CO, Axetilen: C2H2, benzen: C6H6 v axeton l C3H6O. Hp cht ch cha mt nguyn t cacbon trong th nghim trn l CO2 v CO. T c s l lun trn thy rng chnh xc ca phng php khng c cao v kt qu xc nh nguyn t khi ph thuc vo khi lng cc cht em i kho st. V th nu ly c cng nhiu cht khc nhau th kt qu thu c s cng cao. Tuy nhin, phng php ny c hn ch ch khng xc nh c nguyn t khi ca cc kim loi v a s cc kim loi khng to c cc hp cht th kh hay d bay hi. 5.2. Phng php uy Lng- Pti 5.2.1. Phng php uy Lng- Pti a) Nhit dung nguyn t: nhit dung ca mt nguyn t l nhit lng cn thit nng nhit ca mt mol nguyn t ca nguyn t ln 1. b) Nhit dung ring (t nhit): Nhit dung ring l nhit lng nng nhit ca mt gam cht rn ln 10. Thc nghim xc nh c gn ng nhit dung nguyn t ca n cht rn l: 265 J/mol.K 6,3 cal/mol.K Nu k hiu nhit dung ring l C, th: C.A 6,3 A
6,3 C
Bit c C th xc nh c A, y l phng php gn ng v nhit dung nguyn t ch p dng c cho mi n cht rn. 5.2.2. Phng php uy Long - Pti kt hp vi ng lng Cc bc tin hnh Bc 1: Da vo phng php uy Lng- Pti tm khi lng nguyn t gn ng ( A) :
A
6,3 C
Bc 2: Da vo nh lut ng lng tm ng lng ng: Bc 3: Xc nh ho tr gn ng H bng biu thc: H =

A
mA A = mB B
Bc 4: T H suy ra ho tr chnh xc (H) bng cch: ch ly phn nguyn ca H v ho tr l s nguyn. Bc 5: Bit c ho tr chnh xc H, th tm c khi lng nguyn t chnh xc (A) bng biu thc: A = H. V d 2: Mt kim loi c t nhit l 0,22. Khi oxi ho 0,162 g kim loi th thu c 0,306 g oxit. Xc nh nguyn t lng chnh xc ca kim loi: Tr li: Khi lng nguyn t gn ng ca kim loi l: A =
6,3 = 28,64 0,22
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gio trnh ho i cng
ng lng chnh xc ca kim loi l:
Vy ho tr chnh xc ca kim loi l: H = 3 Do khi lng nguyn t chnh xc l: A = H. = 3.9 = 27 (Al) 5.3. Phng php khi ph L mt trong nhng phng php tt nht xc nh khi lng nguyn t. S n gin ca my khi ph gm c 3 phn (hnh 1.4). B phn ngun in vi hiu in th U to dng ion dng ca cc kim loi cn xc nh khi lng nguyn t (A), tip n l ng cong vi p sut kh trong ng rt thp. ng cong c t trong mt t trng vi cng t trng l B tch thnh cc dng ion ca cc ng v. Cui cng l b phn c gn knh nh thu v tr ca cng dng ion dng.
0,162 m m = = O = 8 = 9 0,306 0,162 mO O mO A 28,64 Ho tr gn ng ca kim loi l: H = = = 3,18 9
HNH 1.4. S cc b phn chnh ca khi ph Aston Nguyn tc lm vic ca my khi ph: Da vo mi quan h ca bn knh r ca qu o chuyn ng ca ion dng c in tch q vi khi lng A ca ion dng :
A= q ( Br ) 2 2u
T kt qu xc nh c A v t l ca ng v tng ng, t xc nh c khi lng nguyn t tng i ca ng v kho st. Chng hn khi tm khi lng nguyn t ca cacbon, php o khi ph cho bit trong t nhin cacbon gm hai ng v l 12C v 13C vi t l tng ng l 98,982% v 1,108%. T cc d kin thc nghim ny, xc nh c khi lng nguyn t ca cacbon trong t nhin l:
12.98,892 + 13.1,108 = 12,01108 12 100
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gio trnh ho i cng
C. H THNG BI TP I. Bi tp t lun (c li gii v khng c li gii) I.1. Bi tp c li gii Bi 1 Cho bit s khi, s proton, s ntron v s electron ca cc nguyn 23 32 t 11 Na v 16 S Li gii
23 11
Na
32 16
S khi A 23 32 S protron 11 16 S ntron N 12 16 S electron 11 16 Bi 2 1. Trong phng th nghim ngi ta thu c 27g nc. Hy cho bit: a) C bao nhiu mol nc? b) C bao nhiu nguyn t hiro? 2. Tnh khi lng nguyn t tuyt i ca oxi,bit rng nguyn t ca nguyn t ny c khi lng nguyn t tng i bng 15,9994. Cho N = 6,022.1023 mol-1 Li gii 1. S mol nc l: S phn t nc c trong 1,5 mol nc l: 1,5mol.6,022.1023 phn t.mol-1 = 9,0345.1023 phn t S nguyn t hiro l: 9,0345.1023.2 = 1,8069.1024 nguyn t 2. Khi lng nguyn t tuyt i ca oxi bng: 15,9994/6,022.1023 = 26,564.10-24 g Bi 3 Mt nguyn t ca nguyn t X c bn knh l 1,44 Ao, c khi lng ring thc l19,36 g/cm3. Nguyn t ny ch chim 74% th tch ca tinh th, phn cn li l rng. a) Xc nh khi lng ring trung bnh ca ton nguyn t , t suy ra khi lng mol nguyn t. b) Bit nguyn t ang xt c 118 ntron v khi lng mol nguyn t bmg tng khi lng proton v ntron. Tnh s proton. Li gii a) Khi lng ring trung bnh ca ton nguyn t l:
d =
100 100 74 d d= d = 19,36 = 26,16 g/cm3 74 74 100
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gio trnh ho i cng
Vi gi thuyt nguyn t c dng hnh cu, bn knh bng 1,44 Ao, th tch nguyn t c tnh bi cng thc V = r 3 , do khi lng nguyn t l:
m=
4 3,1416 (1,44.10 8 ) 3 26,16 = 32,704.10 23 g 3 4 3
Khi lng mol nguyn t l:

M = N .m = 6,022.10 23 32,704.10 23 = 196,796 g.mol 1 hay M = 197 g .mol 1
b) Theo bi, ta c: M = m p + mn = Z + N = Z + 118 = 197 Z = 79 Bi 4 207 a) Trong s cc ht nhn nguyn t ch ( 82 Pb) c t s N/Z l cc i v heli ( 4 He) c N/Z l cc tiu. Hy thit lp t s N/Z cho cc nguyn t vi 2 b) Mt nguyn t ca nguyn t X c tng s ht l 55, s khi nh hn 40. Xc nh s proton v s ntron ca nguyn t . Li gii a) T h thc A = N + Z , suy ra N = A Z Vi nguyn t ch th t s: Vi nguyn t heli: Vy t s
N 207 82 = = 1,524 (cc i) 82 Z N 2 = = 1 (cc tiu) Z 2
2 Z < 82.
N i vi cc nguyn t c Z nm trong khong 2 Z < 82 l; Z
N < 1,524 Z
b) V nguyn t ang xt c tng s ht l 58 nn Z phi nm trong gii hn 2Z <82, p dng t l 1 Do : t s Gi S l tng s ht, th S = p + e + n = 2p + n n = S - 2p
S S N S 2p = < p < . Vi S = 58, ta c: 3,524 3 Z p N < 1,524 Z
16,459 < p < 19,333 v 2p + n = 58 T hai phng trnh ny, bng cch lp bng s tm c s proton v s ntron.
p n A Kt lun 17 24 41 Loi 18 22 40 Loi 19 20 39 Nhn
Bi 5 Mt bnh cu th tch 247,2cm3, cha y khng kh, c khi lng 25,201g. Cho mt lng benzen vo bnh cu ri un nng ti 1000C. Benzen
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gio trnh ho i cng
bay hi v ui khng kh ra khi bnh. Lm lnh bnh ti nhit phng, cn li c khi lng 25,817g. p sut kh quyn o trn p k l 742 mmHg. Tnh khi lng mol ca benzen. Xc nh cng thc phn t ca benzen. Li gii Da vo phng trnh trng thi ca kh l tng, tnh s mol benzen:
742 0,2472 PV 760 n= = = 7,83.10 3 (mol ) RT 0,082 373
Khi lng benzen = 25,817 - 25,201 = 0,616 (g) Khi lng mol ca benzen l: M =
0,616 m = = 78,2( g.mol 1 ) M 7,88.10 3
Gi s cng thc phn t ca benzen l: (CH)n, th (12,02 +1).n = 78,2 Suy ra: n = 6. Vy cng thc ca ben zen l C6H6. Bi 6 Mt bnh c dung tch 2 lt cha 3g CO2 v 0,1g He 170C. Tm p sut ring phn ca CO2 v ca He, t xc nh p sut chung ca hn hp kh. Li gii Xc nh s mol mi hn hp kh:
nCO2 =
3 = 0,0682(mol ) 44,01
nHe =
0,1 = 0,025(mol ) 4,003
p sut ring phn ca mi kh trong hn hp:

PCO2 =
0,0682 0,0821 290 = 0,812(atm) 2 V n .RT 0,025 0,0821 290 PHe = He = = 0,30(atm) 2 V
nCO2 .RT
p sut chung ca hn hp kh: P = PCO + PHe = 0,812 + 0,30 = 1,11(atm)

2
Bi 7 Mt bnh cu dung tch 1lt cha 2,69g PCl5 c lm bay hi hon ton 250oC. p sut o c nhit ny l 1 atm. nhit ny PCl5 c th b phn ly theo phn ng: PCl5(k) PCl3(k) + Cl2(k) Hy cho bit iu kin th nghim trn p sut ring phn ca cc kh PCl5, PCl3, v Cl2 l bao nhiu? Li gii Tnh s mol PCl5 khi cha xy ra phn ng phn ly
nPCl5 = m 2,69 = = 0,0129(mol ) M 208
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gio trnh ho i cng
0 p sut ca PCl5 khi cha phn ng ( p PCl )

5
0 PPCl5 =
nPCl5 RT V
0,0129 0,082 523 = 0,553(atm) 1

5 3 2
p sut ny nh hn p sut thc t o c l 1 atm. Vy, khi phn ng xy ra ta c: P = PPCl + PPCl + PCl = 1(atm) T phng trnh phn ng phn ly PCl5
PCl5(k) PCl3(k) + Cl2(k)
Ban u Phn ng
0 p PCl5 = 0,553(atm)
-x
5 5
0 +x
0 +x
0 Ti thi im o x x PPCl = PPCl x 0 Ta c: P = PPCl x + x + x = PPCl + x = 0,553 + x = 1 Vy: x = 1 - 0,553 = 0,447 PPCl = P = x = o,447(atm) Do :
5 5 3 Cl 2
PPCl5 = 0,553 x = 0,553 0,447 = 0,106(atm)
Bi 8 Cho 3,2 g ng tc dng vi oxi thu c 3,6 g mt oxit ca ng. Xc nh ng lng ca ng v cng thc ca ng oxit to thnh. Li gii Khi lng oxi tham gia phn ng l: 3,6 - 3,2 = 0,4(g) Da vo nh lut ng lng, ta c:
Cu mCu m 3.2 = 8 = 64 Cu = Cu O = 0,4 mO mO O A 64 Ha tr ca Cu l: H = = = 1 64
Vy cng thc ca ng oxit to thnh l: Cu2O Bi9 Mun trung ha 10 g mt dung dch axit nng 10% cn dng 10g dung dch KOH 12,47%. Tnh ng lng ca axit.
maxit m = axit axit = axit KOH mKOH KOH mKOH T cc d kin ca bi: maxit = 1g ; mKOH = 1,247 g ; KOH = 561 = 56 Thay cc gi tri ny vo cng thc tnh c: axit = 45
Li gii
Theo nh lut ng lng, ta c:
Bi 10 Ha tan hon 1,44 g mt kim loi M ha tr II Vo 150 ml dung dch H2SO4 0,5M c dung dch A. trung ha dung dch A cn 30 ml dung dch NaOH 1M. Xc nh tn ca kim loi tham gia phn ng. Li gii Phng trnh phn ng: M + H2SO4 MSO4 + H2 (1)
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gio trnh ho i cng
Phn ng ca axit d c trong dung dch A vi NaOH: H2SO4 + 2NaOH Na2SO4 + 2H2O (2) S mol H2SO4 em dng: nH SO = 0,15.0,5 = 0,075(mol ) S mol NaOH tham gia phn ng (2): n NaOH = 0.03.1 = 0.03(mol )
2 4
S mol H2SO4 d: nH SO
2
1 n NaOH = 0,015(mol ) 2 S mol H2SO4 tham gia phn ng (1): nH 2SO4 (1) = 0,075 0,012 = 0,06(mol )
4
d-
Theo (1): nM = nH SO (1) = 0,06(mol ) , tng ng vi 1,41 g. T tnh c khi lng nguyn t kim loi: AM = 1,41:0,06 = 24 g/mol (Mg)
2 4
I.2. Bi tp khngc li gii Bi 1 in vo bng sau:

K hiu nguyn t S khi S in tch ht nhn S proton S electron S ntron
24 12
Mg
106 47
Ag
137 56
Ba
Bi 2 Nguyn t ca mt nguyn t k hiu l X, c tng s cc loi ht l 193, trong s proton l 56. a) Hy xc nh s khi ca X. b) Tnh khi lng nguyn t v khi lng ht nhn ca nguyn t X va tm c. Cho bit t s khi lng nguyn t v khi lng ht nhn t cho nhn xt. Bi 3 Da vo nh ngha hy xc nh khi lng nguyn t ra kg cho mt n v khi lng nguyn t (1u). T kt qu tnh c hy suy ra khi lng nguyn t tuyt i ca oxi, bit oxi c khi lng nguyn t tng i l 15,99749u. Bi 4 a) Tnh khi lng mol nguyn t ca Mg v ca P nu bit khi lng nguyn t tuyt i (KLT) ca chng l 40,358.10-27 kg v 51,417.10-27 kg. b) Xc nhkhi lng tuyt i ca N v Al nu bit khi lng tng i (klt) ca chng l 14,007u v 26,982u. Bi 5: Tnh ng lng ca axit v baz trong cc phn ng sau: a) Ca(OH)2 + H3PO4 CaHPO4 + 2H2O b) 3NaOH + H3PO4 Na3PO4 + 3H2O c) Ba(OH)2 + 2H3PO4 Ba(H2PO4)2 + 2H2O
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gio trnh ho i cng
Bi 6 Cn bng phng trnh v tnh ng lng ca cc cht oxi ha v cht kh trong cc phn ng sau: a) KMnO4 + H2C2O4 + H2SO4 K2SO4 + MnSO4 + CO2 + H2O b) KMnO4 + Na2CO3 + H2SO4 MnO2 + Na2SO4 + KOH c) K2Cr2O7 + FeSO4 + H2SO4 Cr2(SO4)3 + Fe2(SO4)3 + K2SO4 + H2O d) CrCl3 + Br2 + KOH K2CrO4 + KBr + KCl + H2O Bi 7 Mt kim loi M tc dng va vi 4,032 lt kh Cl2 iu kin tiu chun, thu c 16,02g MCl3 theo phng trnh phn ng: 2M + 3Cl2 2MCl3 a) Xc nh khi lng nguyn t ca kim loi M. b) Tnh khi lng ring ca M, Suy ra t l phn trm ca th tch thc s so vi th tch ca tinh th, bit rng M c bn knh r = 1,43 A0 v khi lng ring thc l 2,7g/cm3. Bi 8 C quan nghin cu v tr NASA cho rng c th dng BaO2 cung cp O2 cho tu v tr do phn ng: 2BaO2 2BaO + O2 a) Hy cho bit cung cp oxi cho con tu c th tch 10.000 lt 250C v 0,20 atm th khi lng BaO2 l bao nhiu? b) Hi sau bao lu th lng oxi s c dng ht, nu 200C on phi hnh tiu th 1 lt oxi trong 1 pht. Bi 9 Mt bnh cu c th tch V cha mt kh l tng p sut 650 mmHg. Ngi ta rt mt lng kh c th tch 1,52 cm3 p sut 1atm. Kh cn li trong bnh gy ra mt p sut 600 mmHg. Xc nh th tch V ca bnh vi gi thit l mi php o u tin hnh cng mt nhit . Bi 10 Ly 2,70g hn hp A gm canxi cacbua v nhm cacbua ho tan trong dung dch HCl 2M th thu c mt lng kh c t khi hi so vi hiro bng 10. a) Xc hn thnh phn phn trm ca hn hp A. b) Tnh th tch kh thu c 270C v 836 mmHg. c) Tnh p sut ring phn ca tng kh trong hn hp kh thu c iu kin cho. II. Bi tp trc nghim Bi 1 Trong 280 g st c bao nhiu nguyn t st? Khi lng ca mt nguyn t st l bao nhiu gam? p n a) 3.1024 nguyn t;9,33.10-23 g b) 3.1024 nguyn t; 8,54.10-23 g c) 3,5.1023 nguyn t; 9,68.10-23 g d) 3,5.1023 nguyn t; 8,97.10-23 g Bi 2 C bao nhiu mol phn t N2 trong 280 g N2? ktc, lng nit trn chim th tch l bao nhiu lt? p n a) 9,94 mol; 224 b) 10 mol; 224 c) 10 mol; 225 d) 9,95 mol; 225 Bi 3 trung ho 7 g axit cn 8 g KOH. Xc nh ng lng ca axit.
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gio trnh ho i cng
p n a) 48,80 b) 48,85 c) 49,00 d) 49,00 Bi 4 Xc nh ng lng ca lu hunh trong cc oxit cha 40% v 50% lu hunh v khi lng. p n a) 5,34 v 8,00 b) 5,30 v 8,20 c) 5,37 v 7,95 d) 5,33 v 8,00 Bi 5 Mt bnh cu cha 7 kg oxi di p sut 35 atm. Khi oxi c rt ra khi bnh th p sut gim xung ti 12 atm. Hi c bao nhiu kg oxi c ly ra? p n a) 4,54 kg b) 4,75 kg c) 4,85 kg d) 4,60 kg Bi 6 Mt bnh cu c y kn cha 200g oxi di p sut 3,5 atm v 0 7 C. Tnh khi lng cacbon ioxit trong cng th tch , cng nhit nhng di p sut 2,8 atm. p n a) 215 g b) 218 g c) 220 g d) 222 g Bi 7 Xc nh thnh phn th tch ca hn hp oxi v ozon, bit t khi hi ca hn hp ny i vi hiro bng 17,6. p n:
a) VO : VO = 2 : 1
2 3
b) VO : VO = 4 : 1
2 3
c) VO : VO = 3 : 1
2 3
d) VO : VO = 1 : 1
2 3
Bi 8 Mt hn hp kh nit v hiro c t khi hi so vi hiro l 3,6. Sau khi un nng vi bt st 5500C th t khi ca hn hp so vi hiro tng ln bng 4,5. 1. Xc nh thnh phn theo t l v s mol ca hn hp kh trc v sau phn ng. 2. Tnh phn trm th tch ca nit v hiro tham gia phn ng. p n 1. a) n N : nH = 1 : 4 ; n N : nH : nNH = 1 : 5 : 2
2 2 2 2 3
b) n N : nH = 1 : 3 ; n N : nH : n NH = 1 : 3 : 2
2 2 2 2 3
c) n N : nH = 2 : 3 ; n N : nH : n NH = 2 : 3 : 2
2 2 2 2 3
d) n N : nH = 1 : 2 ; n N : nH : n NH = 1 : 3 : 1
2 2 2 2 3
2. a) 50% N2 v 36,5% H2 c) 45,5% N2 v 37,5% H2

b) 50% N2 v 37,5% H2 d) 45,5% N2 v 36,5% H2 31

gio trnh ho i cng
Bi 9 Magie c khi lng mol l 24,31g/mol, c khi lng ring l 1,738 g/cm3 20oC. Tnh: 1. Khi lng nguyn t trung bnh ca mt nguyn t Mg 2. Th tch ca mt mol nguyn t Mg 3. Th tch trung bnh ca mt nguyn t Mg 4. Bn (knh tnh ra picomet) gn ng ca nguyn t Mg, bit nguyn t Mg c dng hnh cu p n 1. a) 4,030.10-23 g b) 4,030.10-22 g c) 4,037.10-23 g d) 4,037.10-23 g b) 14,00 cm3/g 2. a) 13,88 cm3/mol c)12,87 cm3/g d) 13,99 cm3/g 3. a) 2,340.10-23 cm3 b) 2,340.10-22 cm3 c) 2,323.10-23 cm3 d) 2,323. 10-22cm3 4. a) 178 pm b) 177 pm c) 176 pm d) 179 pm Bi 10 Khi in phn nc, thu c 3,6g mt hn hp kh. Lng kh ny chim mt th tch l 6 lt 170C. Tnh p sut ring ca oxi v hiro. p n
a) PH = 0,7920atm , PO = 0,3920atm
2 2
b) PH = 0,7827atm , PO = 0,3863atm
2 2
c) PH = 0,7927atm , PO = 0,3963atm
2 2
d) PH = 0,7929atm , PO = 0,3969atm
2 2
Bi 11 Mt bnh kn c dung tch 1 lt cha 2,34 g CO v 1,56 g CO2 0 30 C. Xc nh p sut ring phn ca mi kh v p sut ton phn. p n a) 2,18 atm, 0,96 atm v 3,14 atm b) 2,08 atm, 0,88 atm v 2,96 atm c) 2,08 atm, 0,981 atm v 3,061 atm d) 2,08 atm, 0,88 atm v 3,061 atm
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gio trnh ho i cng
CHNG 2 CU TO NGUYN T V H THNG TUN HON CC NGUYN T HA HC A. MC TIU NHIM 1. MC TIU Hc xong chng 2 sinh vin bit v hiu: - Thuyt lng t Plng. - Lng tnh sng ht ca nh sng. - Thuyt Bri. - Nguyn l bt nh Haixenbec. - Tin v hm sng - Bi ton h 1 electron, 1 ht nhn - Cc khi nim: Mt xc sut, obitan nguyn t (AO), spin electrron, obitan spin (ASO),... - Hnh dng cc obitan s, p, d - Bn s lng t v mi quan h gia bn s lng t - Cu hnh electron ca nguyn t. Cc c s vit ng cu hnh electron ca nguyn t. - Cc vn v ht nhn nguyn t. - nh lut tun hon v h thng tun hon, cc tnh cht bin i tun hon. 2. NHIM V Tm hiu v cc mt s vn tin c hc lng t, c hc lng t v cu to nguyn t, t hiu c v c kh nng vn dng c cc kin thc ca chng vo thc hnh v luyn tp. 3. PHNG PHP Thng xuyn s dng cc phng php quy np v loi suy vo vic nghin cu cc kin thc ca chng ny di s hng dn ca gio vin. Cn tng cng rn luyn thng qua cc bi tp luyn tp v thc hnh hiu su hn v cc vn ca chng, t nng cao c nng lc t duy ca ngi hc. B. NI DUNG M u: Nguyn t l phn t nh nht ca mt nguyn t ha hc m vn mang cc tnh cht ha hc ca nguyn t , v mt in tch th nguyn t trung ha v in. V thnh phn th nguyn t gm c ht nhn mang in tch dng do cc ht proton v ntron to thnh, cn v mang in tch m do cc
33
gio trnh ho i cng
ht electron to nn. chng ny trc tin chng ta tm hiu v lp v ca ht nhn trc sau mi nghin cu ht nhn sau. 1. MT S VN TIN C HC LNG T V CU TO CA VT CHT 1.1. Lng tnh sng ht ca nh sng. Thuyt lng t ca M. Planck 1.1.1. Thuyt sng nh sng - nh sng l sng in t, lan truyn trong chn khng vi c = 3.108m/s = 300.000km/s, c c trng bng: + Bc sng (khong cch lan truyn trong mt dao ng) + Tn s dao ng : = + S sng v: =
1
(2.1) (s dao ng trong 1 giy: s-1)
c mt on l , n v: Cm3) c im ca nh sng: Khi truyn t mi trng vt cht ny sang mi trng vt cht khc, vn tc nh sng gim nhng tn s khng thay i. u im: Gii thch c nhng hin tng c lin quan n s truyn sng nh: giao thoa, nhiu x, hin tng quang in. Nhc im: Khng gii thch c cc d kin thc nghim v s hp th v pht sng khi i qua mi trng vt cht. 1.1.2. Thuyt lng t ca M. Planck (Nh bc hc c 1858 1947, Nobel vt l 1918) Vo nhng nm u ca th k 20 vi hng lot cc pht minh mi ra i. Trong cc pht minh ny nu dng cc nh lut v c hc v nng lng ca Niutn th khng gii thch c. Nm 1900 nh Vt l hc ngi c l M.Planck a ra thuyt lng t mang tn ng: "Mt dao ng t vi tn s ch c th pht ra hay hp th nng lng theo tng n v nguyn vn, tng lng gin on, c gi l lng t nng lng. Lng t nng lng t l thun vi tn s ca dao ng". Ni cch khc, nh sng c tnh cht ht v n mang nng lng: = h (2.3)
h l h s t l, hin nay gi l hng s Plng
(2.2) (s dao ng c thc hin khi sng truyn
h = 6,625.10 34 J.s
ngha quan trng ca thuyt lng t Plng l pht hin ra tnh cht gin on hay tnh cht lng t ho ca nng lng trong cc h vi m. T , Plng cho bit nh sng ngoi tnh cht sng cn c tnh cht ht. Tnh cht ht c da ra di dng gi thuyt.
l nng lng ca photon -1 l tn s nh sng (s )
34
gio trnh ho i cng
V d 1: Hy cho bit v sao hng s Plng h c th nguyn l [nng lng].[thi gian]? Tr li: T h thc = h , ta c h = M = 1 T (T l khong thi gian dao ng t thc hin c 1 dao ng - chu k dao ng) Vy h = T . T biu thc ny chng t h phi c th nguyn l [nng lng].[thi gian] T thy rng, Tnh cht gin on ca nng lng c gi l tnh cht lng t ha ca nng lng . S lng t ha ny l tnh cht chung ca cc i lng vt l. Theo thuyt lng t ca Plng, mt dao ng t khi dao ng vi tn s phi c nng lng b lng t ha l E vi cc gi tr gin on l s nguyn ln lng t tc dng, tc l:
0, 1, 2,..., n
(2.4)
Hay: 0 , h , 2h , ..., nh Vy c th biu din mt cch tng qut nng lng E theo cng thc E = nh ; vi n = 0; 1; 2;... V d 2: Mt bc x in t c tn s = 3,7717.1014 s-1. Tm nng lng do bc x gy ra vi n = 1; 2; 3. Tnh cho 1 vi ht v 1 mol vi ht. Tr li: Vi 1 vi ht, ta c: E = nh Vi 1 mol vi ht, ta c: Emol = N.E = 6.023.1023.nh Thay s, ta c:
n = 1: n = 2: n = 3: E1 = 1.6,625.10-34J.s.3,7717.1014s-1 2,49875.10-19 J Emol 1,505.105 J/mol E2 4,9975.10-19 J Emol 3,01.103 J/mol E3 7,49625.10-19 J Emol 4,515.105 J/mol
1.1.3. Lng tnh sng, ht ca nh sng Theo thuyt tng i ca Anhxtanh nmg lng v vn tc c ca nh sng c lin h vi nhau qua biu thc: = mc 2 (2.5) Mt khc, theo h thc ca Plng: = h
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gio trnh ho i cng
Kt hp hai h thc trn, ta c:

h = mc 2 hay =
c mc 2 , = h h = mC
Nn :
(2.6)
H thc (2.6) th hin tnh cht sng - ht ca nh sng hay tnh cht nh nguyn sng - ht ca nh sng: Tnh cht sng c th hin ch khi lan truyn trong khng gian vi vn tc c th c bc sng , cn tnh cht ht th hin ch mi ht photon mang mt khi lng l m. Nh vy, khi thuyt tng i ca Anhxtanh ra i chng minh cho gi thuyt ca Plng v tnh cht ht ca nh sng l hon ton ng n. T cc biu thc trn t c:
= mc 2 = h
c
Tch s c.m chnh l xung lng (p) ca photon ang xt, tc l: Xung lng p biu th cho tnh cht ca ht photon, ( hay ) biu th cho tnh cht sng ca photon. V th phng trnh (2.7) cng biu th cho s thng nht v tnh cht sng v ht ca nh sng. V d 3: Tnh nng lng v xung lng p ca photon vng nh sng xanh (=6,66.1014s-1) ca by sc cu vng. Tr li: Ta c
= h = 6,625.10 34 J .s 6,66.1014 s 1 4,41225.10 19 J
c
c.m =h/
p = m.c = h/ p = h/ (2.7)
Ta c p =
v =
nn p = h
Do : p =
6,625.10 34 kg.m 2 .s 2 .s.6,66.1014 s 1 1,47075kg.m.s 1 3.108 ms 1
Lu : 1J = kg.m2.s-2
V d 4: Hy cho bit kin sau y ng hay sai? ti sao? "Photon l mt loi ht c bn nn n phi c khi lng m c nh" Tr li:
T h thc p = c.m =
h
, ta c m =
h 1 c
m l khi lng ca photon, h v c l cc hng s bit, nn:

m=
1 6,625.10 34 kg.m 2 .s 1 .s 1 m = 2,21.10 42. (kg ) 8 3.10 m.s
36
gio trnh ho i cng
Nh vy, khi lng m ca photon c tr s ph thuc vo tr s ca bc sng . Do khng th ni nh trn c. Xt cho v d 3, tnh c m = 4,911.10-36kg. 1.2. H thc Bri. Nguyn l bt nh Haixenbec 1.2.1. H thc Bri Xut pht t c im ca electron trong nguyn t, nm 1924 bng phng php loi suy Bri suy rng tnh cht sng-ht ca nh sng khng phi l tnh cht ring bit ca nh sng, m l tnh cht chung cho mi ht vt cht bt k nh: electron, proton, rtron,... T ng a ra gi thuyt: S chuyn ng ca mi ht vt cht c khi lng m v vn tc v u lin kt vi mt sng c bc sng c xc nh theo h thc:
=
h m.v
(2.8)
Ni mt cch n gin: Mi dng vt cht vi m u c tnh cht sng v tnh cht ht. Trong biu thc (2.8) iukin ht vi m hay vt th v m c tnh cht sng l: Vn tc v phi l v cng ln V nguyn tc, h thc Bri c nghim ng cho mi ht vi m cng nh vt th v m. Tuy nhin cc vt th v m khc ht vi m ch cc vt th v m c khi lng rt ln cn vn tc chuyn ng li rt nh nn bc sng ca sng lin kt tnh theo h thc trn c gi tr v cng nh, do tnh cht sng khng cn c ngha. V d 5: p dng h thc Bri, hy tnh bc sng cho cc trng hp di y ri rt ra kt lun cn thit. a) Mt electron c khi lng me = 9,1.10-31 kg, chuyn ng vi vn tc v = 106m.s-1. b) Mt chic xe vn ti khi lng bng 1 tn, chuyn ng vi vn tc v = 100 km.h-1. Li gii: a) =
h 6,625.10 34 kg.m 2 .s 2 .s = = 7,28.10 10 m = 7,28 A0 1 31 6 mc 9,1.10 kg.10 m.s
Nhn xt: Vi di sng lin kt tnh c, th sng lin kt Bri c mt ngha quan trng v lun i km vi h vi m. V kch thc ca nguyn t rt nh c 10-10 m = 1A0. b) =
6,625.10 34 kg.m 2 .s 2 .s h = = 2,385.10 28 A0 5 m.c 10 3 kg.10 m 3600s
Nhn xt: Xe vn ti thuc h v m, sng lin kt cc k nh, nn khng c ngha. V d 6: Hy xc nh bc sng cho hai trng hp sau: a) Khi electron chuyn ng vi nng lngl 1eV b) Khi proton chuyn ng c nng lng l 1eV
37
gio trnh ho i cng
Li gii a) xc nh bc sng ca electron, ta phi xc nh c vn tc v ca n. Khi electron chuyn ng n mang mt ng nng l:

mv 2 2T v= T= m 2
Vy:
=
h h 6,625.10 34 kg.m 2 .s 2 .s = = = 1,22676.10 19 m = 12,26.10 10 m = 1226 A0 31 19 mv 2mT 2 9,2.10 1,6.10
b, Khi proton chuyn ng ta c th p dng cng thc:

hc E 34 6,625.10 3.10 8 = 1,2412.10 6 m = 12412.10 10 m = 12412 A0 Thay s, ta c: E = 1,6.10 19 E = h = hc
1.2.2. Nguyn l bt nh bt nh Haixenbec T cc kt qu trn chng ta thy: Cc vt th v m do c khi lng rt ln (c th coi l mt v cng ln so vi ht vi m), nhng vn tc chuyn ng ca chng li rt nh, v vy da vo c hc c in ca Niutn hon ton xc nh c chnh xc qu o chuyn ng ca cc vt th v m. Tc l xc nh c chnh xc c ta ln vn tc (xung lng) ca vt th v m. Nguyn nhn chnh y l do vn tc chuyn ng ca vt th v m rt nh, nn vt th v m khng c tnh cht sng. i vi cc ht vi m, v d nh electron lun tn ti mt sng vt cht lin i i km (do vn tc ca ht vi m l v cng ln). Nn trong th gii chuyn ng ca ht vi m khng cn tn ti khi nim qu o hnh hc thng thng. Nh vy khi nim qu o hon ton khng cn c ngha trong vic m t chuyn ng ca electron hay mt ht vi m bt k. T , Haixenbec a ra nguyn l c ni dung nh sau:"Khng th xc nh c ng thi chnh xc c ta ln vn tc (hay xung lng) ca ht vi m, do khng th xc nh c chnh xc qu o chuyn ng ca ht". Ni dung ny c pht biu vo nm 1927. H thc ca nguyn l: q.v
h m (2.9)
h m
Cng c th a ra h thc ca nguyn l di dng:

q.p h
(2.10) vi
h=
Trong :
q: bt nh v ta .
v: bt nh v vn tc (hay bt nh v xung lng)
38
gio trnh ho i cng
T biu thc (2.9) nhn thy, vi ht vi m chn, t l :

q = const v
h = const, do m
T h thc ny ta thy, nu q cng nh tc l ta q ca ht c xc nh cng chnh th vn tc v ca n cng thiu chnh xc, tc l v cng ln v ngc li. Nh vy, i vi ht vi m, khi bit c chnh xc vn tc chuyn ng ca n, th khng th xc nh c chnh xc to (q), ng i ca n (tc l khng xc nh c chnh xc qu o chuyn ng ca n). T khi nim qu o tr nn khng cn c ngha khi nghin cu cc ht vi m. Thay vo , ch c th ni n xc sut c mt ca n mt v tr no trong khng gian. V d 7: Da vo nguyn l Haixenbec, hy th tnh bt nh v v tr q ri cho nhn xt vi cc trng hp sau: a) Gi thit ve = 3.106m/s ; me = 9,1.10-31kg b) Mt vin n sng sn vi m = 1g chuyn ng vi vn tc 30m/s. Gi thuyt rng sai s tng i v vn tc cho c 2 trng hp l v/v = 10-5. Li gii a)Vi e: q
=
h h = v.m v.10 5.m

3.10 m.s .9,1.10
6
1
V:
31
v = 10 5 v
6,625.10 34 kg.m 2 .s 2 .s kg
= 2,2.10 9 m = 22.10 8 m = 22 A0
b)Vi vin n:
q = 6,625.10 34 kg.m 2 .s 2 .s = 2,21.10 27 m = 2,21.10 19 A0 5 1 3 30.10 m.s .10 kg
Gi tr ny qu b khng mt thit b no o c. Vy nguyn l bt nh Haixenbec vi h v m khng c ngha. V d 8: Mt ht c ng knh c 1 micron, khi lng 10-10g. Ht chuyn ng Braon vi vn tc khong 10-4 cm/s. Gi thuyt php o ta t mc chnh xc vo khong 1% kch thc ht. C th xem ht l ht vi m (nh electron) c hay khng? Hy gii thch. Li gii Nu mt ht xc nh c chnh xc c ta ln vn tc (xung lng) ca ht mt trng thi chuyn ng th khng th coi ht l ht vi m. Xt c th: K hiu ng knh ca ht l x, ta c: x = 1m = 10-6m Nn x = 1%.x = 10-2.10-6m = 10-8m. Theo bi: m = 10-10 g = 10-13kg
h h 6,625.10 34 kg.m 2 .s 2 .s v x = = = = 6,625.10 13 m s = 6,625.10 11 cm s 8 13 q.m x.m 10 m.10 kg
39
gio trnh ho i cng
v x = 6,625.10 11 cm s v = 10 4 cm s
Vn tc chuyn ng ca ht ny c sai s rt nh so vi chnh gi tr ca vn tc . iu ny c ngha l vn tc (hay xung lng) ca ht cng c xc nh hon ton chnh xc nh ta . V vy ht ny l ht v m ch khng phi l ht vi m (vi ht) V d 9: Gi s php o ta x ca electron c chnh xc vo khong 10-3, ng knh nguyn t (khong 10-8cm). C th xc nh c chnh xc vn tc chuyn ng vx ca electron hay khng? Li gii Theo bi: x = 10-3.10-8cm = 10-11cm Ta c: v x =
8
h 6,625.10 34 kg.m 2 .s 2 .s = = 6,625.1010 m s 13 31 x.m 10 m.9,1.10 kg
So snh gi tr v x va tm c vi vn tc nh sng trong chn khng l 3.10 m/s, nhn thy v x > c. Vy khng th xc nh c vn tc vx ca electron khi bit chnh xc ta ca n. Nh vy khi nim qu o chuyn ng ca electron l khng c ngha. 2. MT S NGUYN L V TIN CA C HC LNG T 2.1. Tin v hm sng. Nguyn l chng cht trng thi 2.1.1. Tin v hm sng Mi trng thi ca mt ht vi m (electron) c m t bng 1 hm s xc nh ph thuc vo ta q v thi gian t , k hiu l (q, t ) c gi l hm sng hay hm trng thi. Trong trng hp ht vi m trng thi dng - l trng thi m nng lng ca h khng phi l mt hm s ca thi gian t - hm sng hay hm trng thi ca ht vi m ch l hm s ca ta q , khi hm trng thi c vit l (q) . T y, chng ta ch xt hm sng trng thi dng V nguyn tc: Mi thng tin v ht vi m u thu c t hm (q) * ngha ca hm sng (q) : + Hm sng (q) khng c ngha vt l trc tip nhng bnh phng m 2 un ca hm sng (q) cho bit mt xc sut tm thy ht ti ta tng ng no trong khng gian. + Xc sut tm thy ht trong mt phn t th tch dV bao quanh mt 2 im no trong khng gian l d = dV Nh vy mt xc sut c xc nh bi h thc: =
2
d dV
+ Nu ly tch phn trong ton b khng gian th xc sut tm thy ht trong ton b khng gian bng 1 (theo l thuyt xc sut). 2 (2.11) dV = 1
khng gian
40
gio trnh ho i cng
Biu thc (2.11) c gi l iu kin chun ho ca hm sng. Hm sng khi tho mn iu kin ny c gi l hm chun ha. Ch : Hm sng (q) phi tho mn mt s iu kin: n tr, lin tc, hu hn v kh vi. 2.1.2. Nguyn l chng cht trng thi Nguyn l ny bao gm cc ni dung sau: 1. Nu mt ht vi m vo trng thi c m t bi hm sng ( q ) th trng thi cng c th c m t bi hm sng c (q) , vi c l tha s (hng s). T ngi ta ni: trng thi ca mt ht vi m c th c m t bi cc hm sng m cc hm ny ch khc nhau mt hng s. 2. Nu mt ht vi m vo trng thi c m t bi hm sng 1 (q) hoc vo trng thi c m t bi hm sng 2 (q) th ht vi m cng c th c m t bi hm sng (q) , vi: (q) = c11 (q) + c2 2 (q ) (2.12) c1, c2 l cc hng s c gi l h s t hp hm sng m cc h s t hp c ngha l t l (hay trng s) ng gp ca cc hm sng tng ng vo hm sng (q) . Biu thc (2.12) c pht biu l: hm sng (q) l t hp tuyn tnh cc hm 1 (q) , 2 (q) . Nu ht vi m ang xt c th vo nhiu hn hai trng thi, chng hn n trng thi m mi trng thi c m t bng mt hm sng fi, tc l: f1, f2,..., fi,..., fn th ht vi m ny cng c th vo trng thi:
f = c1 f1 + c2 f 2 + ... + ci f i + cn f n = ci f i
i =1 n
(2.13)
V d 1: S lai hoa sp l s lai ha trong c s t hp tuyn tnh mt hm obitan nguyn t (AO) s vi mt hm AO-p (c th ly AO-px, AO-py, hoc AO-pz), kt qu c hai hm sng lai ha:
1 = cs .s + c p . p = 2 = cs .s c p . p =
1 1 1 s+ p= ( s + p) 2 2 2 1 1 1 s p= (s p) 2 2 2
Ti sao cs = cp? Ti sao cs v cp u bng
1 2
Li gii Hai hm sng AO-s v AO-p hon ton bnh ng trong vic m t chuyn ng ca electron trong nguyn t. Do khi electron c xt vo trng thi c m t bi mt trong hai hm t hp tuyn tnh trn, th tng hm AO-s v hm AO-p u ng gp mt cch bnh ng nhau vo hm sng t hp tuyn tnh. Vy buc phi c cs = Cp
41
gio trnh ho i cng
Theo ngha vt l ca hm sng th s ng gp ca cc hm s v p vo hm sng t hp tuyn tnh l ng gp v xc sut, tc l:

1 1 c = v c 2 = p 2 2
2 s 2 2
Ta d thy mi lng trn u bng 1/2. Kt qu ny tng ng trong mi hm lai ha sp th tng hm s, hm p ng gp mt na, tc 50%. 2.2. Tin v phng trnh Sring Nm 1926, Sring l ngi u tin a ra mt phng trnh v sau mang tn ng. y l mt trong nhng phng trnh u tin v quan trng ca c hc lng t. Hm sng m t trng thichuyn ng ca ht vi m phi tho mn phng trnh: H (q) = E (q) (2.14) Phng trnh (1) l phng trnh Sring khng ph thuc thi gian (phng trnh Sring trng thi dng) Trong : H =
h2
8 m
2
2 + U c gi l ton t Hamintn.
8 2 m ( E U ) = 0 h2
T phng trnh Sring c th vit di dng

2 +
(2.15)
Phng trnh (2.14) v (2.15) l phng trnh Sring trng thi dng. Trong : m l khi lng ca ht vi m E l nng lng ton phn U l th nng ca ht. h l hng s Planck
2 = = 2 2 2 + 2+ 2 x 2 y z
c gi l ton t Laplace
Phng trnh (2.14) v (2.15) l phng trnh vi phn o hm ring cp 2. Mi thng tin v h ht vi m u s c bit, nu gii c phng trnh ny,c ngha l tm c cc gi tr ca hm v nng lng E tng ng. Gii phng trnh Sring s thu c v s nghim 1, 1... n l nhng nghim c lp, t nguyn l chng cht trng thi, ta c: = C1. 1 + C2. 2 + ... Cnn cng l nghim ca phng trnh v thu c cc gi tr nng lng tng ng l E1, E2, ...., En ca ht vi m ng vi cc trng thi . Ch : Ch nhn nhng hm ph hp vi iu kin chun ho hm sng (phng trnh (2.11)). 3. H 1 E, 1 HT NHN (nguyn t H v cc ion ging H) 3.1. Mt s khi nim cn bit 3.1.1. H ta cu
42
gio trnh ho i cng
a)H ta cc C cc trc x, y, z tng ng vi cc bin s x, y, z. z
r r
x
HNH 2.1.H ta cu v ta cc
b) H ta cu C ba bin s: r Gc : c to bi chiu dng ca trc Oz vi vc t v tr r r Gc : c to bi hnh chiu ca vc t r trong mt phng xOy vi chiu dng ca trc Ox r di r hay r (cn gi l moun ca vc t )
= 0 = 0 2
r = r = 0
Tr s ca cc bin s:
(2.16)
c) Mi lin h gia ta cc v ta cu
x = r sin cos y = r sin sin z = r cos
(2.17)
3.1.2. Trng lc i xng xuyn tm Trng lc c gi l trng lc i xng xuyn tm khi lc tc dng ln ht chuyn ng trong trng i qua mt im c nh c chn lm tm ca trng (im c nh ny c chn lm gc ta ). Trong trng lc i xng xuyn tm, ln ca lc tc dng ch ph thuc vo khong cch t v tr ca ht v tm ca trng m khng ph thuc vo phng. r r Do th nng U (r ) ca ht ch l hm ca khong cch r , tc l: U = U(r) (2.18)
43
gio trnh ho i cng
3.1.3. H 1e, 1 ht nhn Nguyn t H v nhng ion m lp v ch c 1e ging nh H, nh: He+, Li2+, He3+, nhng h ny ch khc nhau v s in tch ht nhn (Z). V d 1: in tch (+) ca ht nhn nguyn t H l +e, cn cc ht nhn khc l +Ze. Nhn xt: Bi ton v chuyn ng ca electron trong nguyn t hiro l bi tonc bn nht ca c hc lng t v cu to nguyn t. Nhng kt qu thu c ca bi ton ny s l c s cho vic xy dng l thuyt chung v cu to nguyn t. 3.2. Bi ton h 1e, 1 ht nhn H gm : + 1 ht nhn tch in dng vi s n v din tch dng l Z Ze0 (e0 l in tch nguyn t). Vi nguyn t H ht nhn ch c 1 proton, cc ht nhn khc c Z proton. + Mt electron, c in tch -e0, c k hiu l e chuyn ng quanh ht nhn. Electron c khi lng l:
me =
1 1 mp = mH = 9,1.10 31 kg 1840 1840
e Ze0
r r
HNH 2.2. M hnh h 1e, 1 ht nhn r r : vc t v tr ca electron C th m t h ny nh s hnh 2.2. Trong hnh ny, n gin coi ht nhn ng yn v nm ti gc ta (gc O). Cn electron chuyn ng xung quanh ht nhn vi v tr ca n so vi gc ta c xc nh r bng vc t v tr r . Th nng U ca h c tnh theo biu thc:
U = U (r ) =
2 e0 r
(2.19a)
(vi nguyn t hiro, Z = 1)
2 Ze0 (2.19b) (vi ion ging hiro, Z = 2, 3, 4,...) U = r r Trong r r l moun hay di ca vc t v tr, r l di ca
khong cch (ca v tr) t v tr ca electron n ht nhn. Nh vy thc cht ca h ny l: Xt chuyn ng ca electron trong trng lc ht nhn c s n v in tch dng Ze0. Phng trnh Sring ca h c dng:
44
gio trnh ho i cng
h2 2 2 2 2 2 + 2 + 2 + U = E x y z 8 m
(2.20)
V nguyn t c tnh cht i xng cu nn vic gii phng trnh (2.20) trong h ta cc gp nhiu kh khn nn chuyn (2.20) sang h ta cu vi cc bin s mi r, , s thun tin hn. Khi chuyn sang ta cu (2.20), c dng:
1 2 1 8 2 m r 2 r r r + r 2 + h 2 ( E U ( r ) ) = 0 Trong : (lam a) l phn gc ca ton t Laplace (2) 1 1 2 = 2 r 2 + 2 r r r r 2 1 1 = sin 2 + 2 sin sin
(2.21)
(2.22)
T (2.21) v (2.22) phng trnh Sring (2.21) c vit gn thnh:

2 8 2 m + 2 (E U (r )) = 0 h
(2.23)
3.3 Nguyn tc gii phng trnh Sring y l mt trong s t cc phng trnh ca c hc lng t c c li gii chnh xc. gii c phng trnhg Sring (2.23), cn tin hnh theo cc bc: Bc 1: chp nhn (r , , ) = R(r ).Y ( , ) (2.24) Trong : Y ( , ) l phng trnh ph thuc gc R(r ) L phng trnh ph thuc bn knh Bc 2: Thay (2.24) vo (2.23) ri bin i ton hc ta s c mt phng trnh mi l tch ca hai phng trnh. Mt phng trnh ph thuc gc-phng trnh hm gc v mt phng trnh ph thuc vo bn knh-phng trnh hm bn knh. Bc 3: Gii tng phng trnh + Gii phng trnh hm gc, ta c v s nghim l cc hm gc
Y ( , )
+ Gii phng trnh hm bn knh, ta c v s nghim l cc hm bn knh R(r ) Bc 4: Ly tch cc hm R(r ).Y ( , ) mt cch ph hp v mi quan h gia cc s lng t (trnh by phn sau), ta s c v s nghim l cc hm sng (r , , ) . Ch : Ch ly cc nghim ph hp vi u kin chun ho ca hm sng 2 (2.11) d = 1
Ton khng gian nguy n t
T cc nghim ca phng trnh String s c gi tr hu hn. 3.4. Kt qu gii bi ton 1e, 1 ht nhn
45
gio trnh ho i cng
Gii phng trnh Sring cho h 1e, 1ht nhn thu c a) Hm bn knh Phng trnh hm bn knh (ch ph thuc khong cch r) c dng: Vi: = l(l + 1) Vic gii phng trnh ny cho ta nghim l hm bn knh Rn,l (r ) hay Rnl (r ) , c dng:
4(n l 1)! Z Rnl (r ) = 3 n 4 [(n + 1)!] a0
3 2
2mr r 2 r R + 2 [E U (r )] = R h
(2.25)
2 Zr Zr na0 na e 0
2 l +1
2Zr n +1 o
L na
(2.26)
n l s lng t chnh; cn l l s lng t ph (s lng t obitan) Z l s n v in tch dng ca ht nhn a0 l bn knh Bo th nht, a0 =
2 l +1
h2 = 0,529.10 8 cm = 0,529 A0 o,53 A0 2 me0
e l c s lgarit t nhin 2 Zr L1 na0 l a thc Lagher n+
r l bin s ch khong cch t ht nhn n v tr ca electron ang xt Hm bn knh Rnl(r) l cc hm ton hc c chun ho, cc hm ny l cc hm thc ph thuc vo bn knh r v hai s lng t chnh n v s lng t ph l . ng vi mi mt b hai s lng t n, l ph hp nhau v mi quan h ta s c mt hm Rnl(r) ph thuc vo bn knh r. C v s b hai s n, l nn s c v s hm bn knh Rnl(r). Mt s hm Rnl(r) cchun ho ca h mt electron, mt ht nhn + n = 1; l = 0: + n = 2; l = 0: + n = 2; l = 1: + n = 3; l = 0: + n = 3; l = 1:
Z 2 R10 (r ) = R1s = 2 .e a0 a 0
3 Zr
1 Z R20 (r ) = R2 s = 2 2 a0 R21 (r ) = R2 p
3 2
Zr . 2 .e a0 a0
5 Zr
Zr
1 Z 2 a0 .r.e = 2 6 a0
3
2 Z 2 R30 (r ) = 81 3 a0 R31 (r ) = R3 p
Zr Z 2r 27 18 + 2 2 e 3a0 a0 a0
3
Zr
4 Z 2 = 81 6 a0
Zr Z 2 r 3a0 6 a a 2 e 0 0
gio trnh ho i cng
Zr
46
+ n = 3; l = 2:
4 Z 2 Z 2 r 2 3a0 2 e R32 (r ) = R3d = a0 81 30 a0
Zr
tr:
* S lng t chnh n + S lng t chnh (n) l cc s nguyn dng, khc 0; n nhn cc gi n = 1, 2, 3, 4...., . + nha ca s lng t chnh n: - Xc nh khong cch trung bnh ca electron n ht nhn.
r = n2. a0 z 1 l (l + 1) 1 + 1 n 2 2
- Xc nh cc mc nng lng trong nguyn t:

En =
4 2. 2 .m.z 2 e0 1 cc e cng mt lp c E nh nhau. 2 2 n h (4 0 ) 2
- Xc nh tng s mt nt ca Obitan = (n-1) khng k s mt nt xa v cc. Mt nt: L khu vc khng gian (thng l mt phng) m hm sng 2 trit tiu, (q) = 0 (q) = 0 . Tc l ngay trong khng gian nguyn t cng c nhng khu vc khng tm thy electron. - c trng cho lp Obitan (lp electron): Tt c cc obitan nguyn t (AO) c cng s lng t chnh (n) th thuc cng 1 lp. Tr s ca n= 1 2 3 4 5 6 7 ...... Lp electron K L M N O P Q ...... * S lng t ph l (s lng t obitan) + S lng t ph l l cc s nguyn, l nhn cc gi tr: l = 0, 1, 2, ..., (n-1). + Quan h gia s lng t ph l v s lng t chnh n ng vi 1 gi tr ca s lng t chnh n, th s lng t ph l nhn n gi tr t: l = 0 (n-1), tc l 0 l (n-1) V d 1: n = 1 l = 0 c 1 gi tr ca l = 0 n = 2 l = 0; l = 1 c 2 gi tr ca l = 0, 1 n = 3 l = 0; l = 1; l = 2 c 3 gi tr ca l = 0, 1, 2 + ngha ca s lng t ph l : - Xc nh phn lp electron trong nguyn t: Tr s ca l K hiu ca phn lp electron 0 s 1 p 2 d 3 f 4 g ... ...
D thy: Vi 1 gi tr ca s lng t chnh n th c n phn lp electron. c 1 phn lp (k hiu l phn lp 1s) V d 2: n = 1 l = 0 n = 2 l = 0; l = 1 c 2 phn lp (k hiu l phn lp 2s, 2p)
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gio trnh ho i cng
Cc hm bn knh tng ng ln lt c k hiu l: R30(r); R31(r); R32(r) Ch : Ch cc AO c cng s lng t chnh n v s lng t ph l mi thuc cng mt phn lp. - Xc nh hnh dng hay tnh cht i xng ca cc AO AO-s : hnh cu, i xng cu (c tm i xng) AO-p : hnh s 8, i xng trc (c trc i xng) - Xc nh momen ng lng Obitan (M) ca electron: M = l (l + 1) . M= 2
h 2
n = 3 l = 0; l = 1; l = 2 c 3 phn lp (k hiu l phn lp 3s,3p.3d)
V d 3: Khi electron obitan c l = 0, th M = 0; obitan c l = 1 th, Ch : 1, T mi quan h ca n v l phng trnh (2.26), ta thy cho cn bc hai c ngha th biu thc trong cn bc hai phi dng, nn 2, Vic gii hm bn knh dn n vic xut hin hai s lng t n, l mt cch hon ton t nhin. b) Hm gc(hm cu) Phng trnh hm gc (ch ph thuc v gc , ) c dng:
Y = Y + Y = 0 Y
n l 1 0 l n 1
h 2
(2.27)
l
Vic gii phng trnh (2.27) thu c nghim l hm gc Yl ,m ( , ) hay Ylm ( , ) . Hm gc Yl ,m ( , ) : - Ph thuc vo hai bin s gc , - Ph thuc vo hai tham s l s lng t ph l v s lng t t ml * S lng t t + ml l cc s nguyn nhn cc gi tr: ml = - l , (- l +1),..., -1, 0, 1,...., ( l -1), l . + Mi quan h gia l v ml : l = 0 ml = 0 l = 1 ml = -1, 0, 1 l = 2 ml = -2, -1, 0, 1, 2 Vy: ng vi mt gi tr ca l , th ml s nhn (2 l + 1) gi tr. Nh th th ng vi mt gi tr ca s lng t chnh n s c bao nhiu gi tr ca ml ? n = 1 l = 0 ml = 0 c 12 = 1 gi tr ca ml n =2 l = 0 ml = 0 2 l = 1 ml = -1, 0, 1 c 2 = 4 gi tr ca ml
l l
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gio trnh ho i cng
Vy: ng vi 1 gi tr ca s lng t chnh n s c n2 gi tr ca s lng t t ml + ngha ca s lng t t ml - Xc nh s Obitan nguyn t (AO) c trong 1 phn lp: Vi 1 gi tr ca l c (2 l +1) gi tr ca ml . Tc l phn lp l c (2 l +1) AO. - Xc nh hnh chiu ca m men ng lng Obitan trn trc z
M z = ml
Biu thc ca mt s hm gc (hm cu) chun ha:

+ l = 0; ml = 0 + l =1; ml = 0
ml = 1 ml = -1 Y00 ( , ) =
Y10 ( , ) = Y11 ( , ) = Y11 ( , ) = Y20 ( , ) = Y21 ( , ) = Y21 ( , ) = Y22 ( , ) = Y22 ( , ) =
h 2
1 4
3 cos 4 3 sin .e i 8 3 sin .e i 8 5 (3 cos 2 1) 16 15 sin cos .e i 8 15 sin cos .e i 8 15 sin 2 .e 2i 32 15 sin 2 .e 2i 32
z
(1) (2)
+ l = 2; ml = 0
ml = 1 ml = -1 ml = 2 ml = -2
Cc hm (1), (2) c k hiu: s = Y00 ; p = Y10
Cc hm cu cha s o i (s o i2 = - 1 i = 1 ) l hm phc. Trong trng hp s phc, khi t hp tuyn tnh cc hm ny mt cch thch hp th c cc hm thc. Cc hm khng cha s o i lun l hm thc nn khng cn t hp tuyn tnh, l cc hm cu c ml = 0. Chuyn cc hm cu phc thnh hm thc v k hiu tng ng ( n gin khng ghi bin s )
+ l = 0; ml = 0 s = Y00 =
1 4
gio trnh ho i cng
49
+ l = 1; ml = 0 + l = 1; ml = 1 + l = 1; ml = -1 + l = 2; ml = 0 + l = 2; ml = 1 + l = 2; ml = -1 + l = 2; ml = 2 + l =2; ml = -2
p z = Y10 =
3 cos 4
px = py =
1 3 (Y11 + Y11 ) = sin cos 4 2 1 3 (Y11 Y11 ) = sin sin 4 i 2

5 (3 cos 2 1) 16
d z 2 = Y20 =
d xz = d yz =
1 15 (Y21 + Y21 ) = sin cos cos 4 2 1 15 (Y21 Y21 ) = sin cos sin 4 i 2 1 15 (Y22 + Y22 ) = sin 2 (cos 2 sin 2 ) 16 2
d x2 y 2 = d xy =
1 15 (Y22 Y2 2 ) = sin 2 cos sin 4 i 2
c) Hm sng: nlm (r , , )
l
Hm sng m t trng thi ca electron trong h 1e, 1ht nhn l tch ca hm bn knh Rnl (r ) v hm cu Ylm ( , ) :
nlml (r , , ) = Rnl (r ).Ylml ( , )
l
Vic ly tch ca hm bn knh v hm cu phi ph hp v mi quan h gia 3 s lng t n, l , ml . V d 4:

100 z = 1s = R10 .Y00 = 2. e a 0
3 2 Zr a0
1 1 z a0 e = a0 4
3 2
Zr
Lm tng t ta c
200
1 = 2 s = R20 .Y00 = 4 2
Z 2 Zr 2 e 2 a0 a a0 0
Zr
Vi hiro Z=1, xt trong h n v nguyn t th a0 = 1 khi

100 =
e r
Vi 200 ,... lm tng t nh trn.

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gio trnh ho i cng
d) Cc mc nng lng tm c Gii phng trnh hm bn knh, cn thu c biu thc tnh nng lng
En =
4 4 2 2 me0 Z 2 mZ 2 e0 1 1 = (erg) 2 2 2 2 2 2n h (4 0 ) n h (4 0 ) 2 h Vi: h = 2
(2.28)
Trong : n l s lng t chnh m l khi lng ca 1 electron h l hng s Plng Trong biu thc tnh nng lng tt c cc i lng u tnh theo n v ca h cgs. n v ca nng lng l ec hay erg: 1ec = 1erg = 10-7J. Du (-) biu th nng lng ca e cn chu tc dng ca lc ht ht nhn nguyn t ng vi in tch Z . En cng thp (cng m), tc l s lng t chnh n cng b th h cng bn. H bn nht khi En thp nht (En cc tiu), ng vi n = 1. Nu xt trong h n v nguyn t (vn hay au), vi quy c cc i lng sau u bng n v: + in tch c bn e0 = 1 + Khi lng ca 1electron bng 1; me = 1 + Hng s Plng bng rt gn + Bn knh Bo th nht a0 = 0,529A0 = 1 + Hng s in mi trong chn khng 0 v tch 40 = 1 Nu tnh theo h n v nguyn t, th:
1 Z2 En = 2 (vn) 2 n
(2.29)
Nu nng lng tnh ra eV, th:

E n = 13,6 Z2 (eV) n2
(2.30)
V d 5: Hy tnh E1, E2, E3,... theo n v eV cho nguyn t H. Vi n bng bao nhiu th En c gi tr m nht. Li gii Vi nguyn t hir Z=1, th:
E n = 13,6
12 (eV ) n2
Vy: E1 = -13,6 (eV); E2 = - 3,4 (eV); E3 = - 1,15 (eV); E4 = - 0,85 (eV); E5 = - 0,544 (eV); ...; E = 0. Vi n = 1 th E1 = -13,6 (eV) l m nht.
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gio trnh ho i cng
Nhn xt: - Nng lng En ch nhn nhng gi tr gin on, tc l nng lng b lng t ho. - E1 c gi tr m nht (hay mc nng lng ng vi n = 1 l thp nht). y l trng thi c bn ca electron trong nguyn t hiro, trng thi ny electron lin kt bn nht vi ht nhn nguyn t. V vy c th ni:" H bn l h c nng lng cc tiu". - Vi n = 2, 3, 4, ... l cc trng thi kch thch ca electron trong nguyn t hiro. - Khi n = , En = 0, electron chuyn sang trng thi khng lin kt vi ht nhn, khi ny electron khng b ht nhn ht na, tc l electron tch ra khi nguyn t v chuyn ng t do, cn nguyn t th bin thnh ion dng. 3.5. p dng kt qu ca bi ton h 1e, 1 ht nhn gii thch quang ph vch ca nguyn t hiro 3.5.1. Cc trng thi nng lng ca e trong nguyn t H Nng lng En ph thuc vo s lng t chnh n. n=1 lp K ( trng thi c bn) E1 = - 13,6eV n=2 lp L ( trng thi kch thch) E2 = - 3,4eV n=3 lp M ( trng thi kch thch) E3 = - 1,5eV n=4 lp N ( trng thi kch thch) E4 = - 0,8eV . .............................................. ................... n= En = 0 Khi ny electron tch ra khi trng lc ht ca ht nhn, nguyn t s chuyn thnh ion dng (+). 3.5.2 M t quang ph ca nguyn t hiro Quang ph ca nguyn t hiro - mt quang ph pht x n gin nht, c th to ra c bng cch: Phng in qua mt ng mao qun cha kh hiro p sut rt thp, c vi mmHg, nh mt my quang ph lng knh m thu c quang ph vch. mt vng vi bc sng xc nh, ta c mt dy tng ng gm cc vch ph di nhau. Cc vch ph di nhau l du hiu c trng ca quang ph nguyn t - quang ph vch Trong vng nh sng nhn thy (vng kh kin), thc nghim cho kt qu dy Banme c hnh nh nh sau:
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gio trnh ho i cng
HNH 2.3. Cc vch ca dy Banme trong vng nhn thy ca quang ph nguyn t hiro 3.5.3. Gii thch quang ph vch ca nguyn t hiro T biu thc tnh nng lng (2.28) tm c khi gii phng trnh Sring. Vi nguyn t hiro Z = 1, ta c:
En =
4 mZ 2 e0 2n 2 h 2
(2.31a) (2.31b)
h=
h 2
nn
En =
4 2 2 me0 n2h2
Nh vy, khi electron trong nguyn t hiro trng thi ng vi hm sng ( c l p-xi) c gi tr n xc nh x c mt nng lng xc nh. Gi s c hai trng thi sau: - Trng thi c n nh (thp), k hiu l nt , nng lng tng ng l Et - Trng thi c n ln (cao), k hiu l nc , nng lng tng ng l Ec Theo (2.31b), ta c:
Ec =
4 2 2 me0 ; nc h 2
Et =
4 2 2 me0 nt h 2
T biu thc (2.28), ta thy n cng cao th nng lng En tng ng cng cao. Vy Ec cao hn Et. Do khi electron mc nng lng Ec chuyn v trng thi c mc nng lng Et thp hn s gii phng ra mt nng lng E.
E = Ec Et
Plng
Nng lng ny c pht ra di dng sng in t c tn s , theo

E = h
M: = , vi c l vn tc nh sng trong chn khng. Thay cc biu thc ny vo biu thc E = Ec Et , ta c:

hc 1
= E c Et =
4 2 2 meo 1 1 2 2 2 n h c nt
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gio trnh ho i cng
Vy K hiu:
4 2 2 meo 1 1 2 2 = 3 n h c t nc
(3.18a)
RH =
4 2 2 me0 = 109678cm 1 3 hc
RH c gi l hng s Ritbe (v tt c cc i lng v phi u l hng s),do :

=
1 1 = RH 2 2 n t nc 1
(3.18b)
Trong c gi l s sng. Ch : Vi ion ging H th:

1 1 = R H .Z . 2 2 n t nc 1
(3.19)
V d 6: Hy tnh tr s, c km theo n v ca hng s Ritbe t: a) Cc s liu ca hng s c trong bng 1.6 (trang 12) b) Thc nghim cho bit vch c 6565 A0 Li gii a) T bng 1.6 (trang 12), ta c: h = 6,625.10-27 erg.s; c = 2,99792458.1010 cm.s-1; e0 = 4,803.10-10 ues cgs; m 9,1093897.10-28 g Thay cc hng s ny vo biu thc tnh RH, c:
2(3,1416) 2 .9,1093897.10 28.(4,803.10 10 ) 4 RH = 109772,35cm 1 23 3 10 (6,625.10 ) .2,99792458.10
b) Vch trong quang ph vch ca hiro ng vi s chuyn di electron t nc = 3 v nt = 2. Theo biu thc (3.18b): Vy:
1 1 = RH 2 2 2 3 36 RH = = 109622cm 1 8 5.5636.10
Nh vy, RH tnh theo thc nghim nh hn tnh theo l thuyt mt t. Da vo mi lin h gia s chuyn di electron vi bc x nng lng km theo,ta c s cc dy vch quang ph pht x ca nguyn t hiro hnh 2.4 (trang 56). + Dy Laiman gm cc vch ng vi s chuyn di electron t mc nng lng c n 2 v mc n = 1. Dy ny trong vng t ngoi (tm). + Dy Banme gm cc vch ng vi s chuyn di electron t mc nng lng c n 3 v mc n = 2. Dy ny trong vng kh kin. + Dy Pasen gm cc vch ng vi s chuyn di electron t mc nng lng c n 4 v mc n = 3. Dy ny nm trong vng hng ngoi.
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gio trnh ho i cng
Trong mi dy li gm c mt s vch tch ri nhau, v cn c mt s vch khng tch di nhau, to ra vng ph lin tc (hnh 3.1). Min lin tc ny nm vng c bc sng ngn hn trong gii hn ca dy. Chng ta ch xt phn gm cc vch tch di nhau. V d 7: Hy tnh bc sng v s sng ca vch ph u v vch ph cui ca dy Laiman, ca dy Banme. Li gii Xt dy Laiman Vch u: nt = 1; nc = 2. Theo biu thc (3.18b), tnh c:
= RH
1 1 2 = 0,75.RH 82258,5cm 1 2 2 1
HNH 2.4. Mt s dy quang ph vch ca hiro

=
1
1 1215.10 8 cm = 1215 A0 1 82258,5cm
Vch cui cng: nt = 1; nc = . Vn s dng (3.18b)

2 12 1 1 1 = = RH 2 2 = RH 2 1 2 = RH = 109678cm 1 1
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gio trnh ho i cng
Xt dy Banme: Lm tng t, th c (vi nt = 2) Vch u:

15233,06cm 1 ; 6560 A0
1 911,7.18 8 cm = 911,7 A0 10678cm 1
Vch cui: 27419,5cm 1 ; 3640 A0 3.6. Cc khi nim c bn c rt ra t vic gii bi ton h 1e, 1 ht nhn 3.6.1. Cc Obitan nguyn t, ngha, cch biu din. a) Obitan nguyn t (AO): L nhng hm sng m t trng thi chuyn ng ca e trong nguyn t. 2 b) ngha: cho bit mt xc sut c mt e ti mt ta no trong khng gian nguyn t. c) Cch biu din: C th dng nhiu cch * C 2 cch ph bin: 1. Dng th phn gc ca cc AO biu din chnh cc AO . 2. Dng th hm mt xc sut theo gc: C dng tng t phn gc ca cc AO nhng khc ch ch tt c cc min ca th u mang du dng hoc bng khng ( 0) v cng dng biu din cc AO. * Hnh dng cc AO v du ca n AO-s: Dng hnh cu
HNH 2.5: Hnh dng cc AO-1s, AO-2s, AO-3s
HNH 2.6. Hnh dng hm cu 2p, v hm mt xc sut , biu din cc AO-p

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gio trnh ho i cng
AO-p: Dng hnh s 8 ni (cc AO-px, AO-py, AO-pz hng theo trc x, y, z tng ng).
Y10 = p z = 3 cos 4
Nu coi
1 lm n v, ta c: Y10 = p z = 3 cos , khi ny hm mt xc 4

Y10 =
2
sut tng ng l:
3 cos
Xt s to thnh hnh nh khi kho st hm Y10: Khi = 0 900, hnh nh ca hm ny l hnh cu ng knh 3 . Hnh cu ny nm phn dng ca trc z. Khi = 900 1800, hnh nh hm Y10 tng t trn, nhng nm phn m ca trc z. Hai hnh tip xc vi nhau ti gc to , nh vy trong mt phng xOy (mt phng vung gc vi trc z) khng c im biu din ca hm pz; ta ni hm pz trit tiu (bng 0) trong mt phng xOy. Dng khi nim mt nt nu trn,vy mt phng xOy l mt phng nt hay mt nt ca hm Y10 hay hm pz.
HNH 2.7. Hnh dng cc AO-2px, AO-2py, AO-2pz, biu din theo hm mt xc sut Cc AO-2px, AO-2py, AO-2pz c hnh dng ging nhau, c nng lng bng nhau, nhng khc nhau v hng trong khng gian.
HNH 2.8. Hnh dng cc AO-d, biu din theo hm mt xc sut

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gio trnh ho i cng
Trong 5AO-d, 3 AO-dxy, dxz, dyz c hnh dng ging nhau. 3AO ny mi AO u gm c 4 qu cu tip xc vi nhau gc ta , trong c hai qu cu mt c tm nm trn ng phn gic ca cc gc to nn bi hai trc ta . V d, tm ca bn qu cu ca AO-dxy nm trn hai ng phn gic ca cc gc to nn bi trc x v trc y. AO d x y cng gm c 4 qu cu tip gip
2 2
vi nhau gc ta , nhng tm ca chng nm ngay trn trc x v trc y. Cn AO d z gm c hai qu cu tip gip vi nhau gc ta , c tm nm trn trc z v c mt vnh trn nm trn mt phng xy.
2
3.6.2. Spin ca electron, hm Obitan-Spin (ASO) a) Spin ca electron Thc nghim cho bit, vi my quang ph c nng sut phn gii cao cho php thu c quang ph pht x trong mi vch thc ra l gm mt s vch st nhau. Chng hn vch D trong quang ph ca Na gm hai vch st nhau vi bc sng l 5889,95 A0 v 5895,93 A0. Kt qu tnh l thuyt theo phng trnh Sring khng gii thch c s tch i cc vch ph ny. Vo nm 1925, Uylembec v Gaoxmit a ra gi thuyt: r Ngoi chuyn ng obitan to ra m men ng lng M , electron cn c chuyn ng spin to ra m men ng lng spin. Gi thuyt ny n nay vn c dng. T c th hnh dung electron lun tham gia ng thi vo hai chuyn ng: + Chuyn ng quay quanh ht nhn c c trng bng m men ng lng (ging nh tri t quay quanh mt tri) + Chuyn ng ring - chuyn ng quay quanh mnh n - chuyn ng spin (ging nh chuyn ng ca tri t quay quanh mnh tri t) Chuyn ng spin lm xut hin s lng t spin ms c hai gi tr: ms = +1/2 electron quay cng chiu kim ng h, quay phi. Nu quy c biu din electron bng mi tn, th mi tn c nh hng ln trn: ms = -1/2 electron quay ngc chiu kim ng h, quay tri v mi tn c nh hng xung di: S dng cc vn nu ra trn, c th a ra s gii thch s tch mt vch thnh hai nh sau:
Spin xung; ms = -1/2
Spin ln; ms = +1/2
HNH 2.9. S gii thch s tch i ca mt vch ph trong quang ph pht x ca nguyn t b) Hm Obitan spin (hm Obitan ton phn): K hiu l ASO
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gio trnh ho i cng
T cc vn nu ra trn, ta thy: i vi mi electron trong nguyn t u c mt hm sng nlm (r , , ) (hay AO), vi mt b ba s lng t n, l, ml m t chuyn ng khng gian (hay chuyn ng obitan) ca electron quanh ht nhn. Cn s lng t th t - s lng t spin, k hiu l ms m t chuyn ng ring ca electron - chuyn ng quay xung quanh mnh n. n ,l ,m l (r , , ) c gi l hm Obitan khng gian (AO) Vy Hm sng ton phn hay hm obitan spin (ASO )vi mt b bn s lng t n, l, ml, ms m t y trng thi chuyn ng ca electron trong nguyn t phi l tch ca:
l
nlml ms (r , , , ) = nlml (r , , ). ms ( )
l
s
(3.20)
Trong : n,l ,m ,m (r , , , ) l hm obitan spin hay hm sng ton phn (ASO) n ,l ,m (r , , ) l hm obitan khng gian (AO) m ( ) l hm spin m ( ) l hm m t chuyn ng ring ca electron, vi bin s . Vic
l
s s
gii ring hm ny s cho ta s lng t spin ms =
1 2
nh trnh by trn.
T biu thc (3.20), cho thy: ng vi 1 obitan (1 AO) - mt hm khng gian ta c hai hm obitan spin (2 ASO). Hai hm ny c ba s lng t n, l, ml nh nhau, ch khc nhau s lng t spin. Mt hm c ms = +1/2 cn mt hm ms = -1/2. Tc l: 1AO th c 2ASO, do trong 1AO ch c 2 electron, hai electron ny phi c spin khc nhau. * ngha ca s lng t spin (ms) - c trng cho mmen ng lng ring ca electron
M s = s ( s + 1) . h 2
- V hnh chiu ca m men ng lng ring ca e trn trc z

M s ( z ) = ms .
h 2
; ms = s = 1 / 2
- S gi tr ca s lng t spin ms cho bit s electron ti a c trong mt obitan, t d dng tnh c s electron ti a c trong mt phn lp, mt lp. * Mi quan h gia s lng t spin vi cc s lng t khc - Vi mt gi tr ca s lng t t ml c hai gi tr ca ms, mt gi tr ms = +1/2 v mt gi tr ms = -1/2 - Vi mt gi tr ca s lng t ph l s c 2(2 l +1) gi tr ca ms, tc l s electron ti a trong mt phn lp l 2(2 l +1). - Vi mt gi tr ca s lng t chnh n s c 2n2 gi tr ca ms, tc l c ti a 2n2 electron trong mt lp.
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gio trnh ho i cng
V d 8: Tnh s electron ti a trong phn lp s, p, d, f v s electron ti a trong cc lp K (n = 1), L (n = 2), M (n = 3) Li gii Phn lp s: l = 0 s electron ti a = 2(2.0 + 1) = 2 Phn lp p: l = 1 s electron ti a = 2(2.1 + 1) = 6 Phn lp d: l = 2 s electron ti a = 2(2.2 + 1) = 10 Phn lp f: l = 3 s electron ti a = 2(2.3 + 1) = 14 ... ... ... ... ..... .... .... ... ... ... ... ... ... ... ... .... Lp K (n = 1) s electron ti a = 2.12 = 2 Lp L (n = 2) s electron ti a = 2.22 = 8 Lp M (n = 3) s electron ti a = 2.32 = 18 ... ... ... ... ... ... ... ... ... ... .... .... 4. NGUYN T NHIU ELECTRON 4.1. M hnh cc ht c lp (m hnh trng xuyn tm) cc obitan nguyn t 4.1.1. Nhn xt R12 e1 e2 r1 + HNH 2.10. M hnh cho h nguyn t nhiu electron - Trong nguyn t, ngoi tng tc ht gia cc electron vi ht nhn, cn c tng tc y gia cc electron vi nhau, gia cc ht nhn vi nhau. - En khng nhng ph thuc vo khong cch ca n n ht nhn m cn ph thuc vo khong cch ca n vi cc electron khc ( y: Ht nhn c coi l ng yn v nm ti gc ta ). - Ton t Hanintn H c dng rt phc tp, nn bi ton nguyn t nhiu electron khng th gii chnh xc c. * Khc phc: gii bi ton h nguyn t nhiu e, ngi ta phi xy dng nhng phng php gii gn ng. Mt trong cc cch gii gn ng l m hnh cc ht c lp. 4.1.2. M hnh cc ht c lp M hnh ny do hai nh khoa hc l Bocn v penhaim a ra, nn cn c gi l s gn ng Bocn - penhaim. M hnh ny tha nhn: Trong nguyn t nhiu e, ht nhn c coi l ng yn nm ti gc ta , xt chuyn ng ca tng electron trong trng lc c to ra bi ht nhn v cc electron cn li. + Trn c s , ngi ta xy dng ring trng thi ca tng electron, c gi l trng thi n electrron. + Trng thi n electrron cng c c trng bng 1 hm sng n ,l ,m (r , , ) (c gi l AO).
l
r2
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gio trnh ho i cng
- H qu: T m hnh v cc ht c lp, bi ton nguyn t nhiu elec trron (n electron) c chuyn thnh n bi ton 1 electron (n e) ging nh bi ton v nguyn t H. - Kt qu: Khi gii n bi ton ny cho ta: + Cc hm sng n electrron n,l ,m (r , , ) (AO) v nng lng Enl , cng sut hin cc s lng t v mi quan h gi cc s lng t cng nh ngha ca n. + Hnh dng cc AO c quyt nh bi hm cu, hnh dng AO trong nguyn t nhiu e cng ging hnh dng cc AO trong nguyn t H.
l
4.2. Nguyn l phn i xng - nguyn l Pauli Hm sng ton phn m t trng thi ca h nhiu electron phi l hm phn i xng. T Paoli rt ra kt lun: Trong mt nguyn t khng th c 2 hay nhiu e m trng thi ca chng c c trng bi cng tp hp 4 s lng t n, l , ml , ms , nh nhau . 4.3. Cc mc nng lng trong nguyn t nhiu electron. Quy tc Klechkowski. Bng l thuyt v thc nghim, xc nh c cc mc nng lng En ca AO trong nguyn t nhiu electron tng dn theo s , hnh 2.11. Th t sp xp cc phn mc nng lng Enl theo mc nng lng thng c xc nh bi quy tc Klechkowski nh sau: Nng lngca cc phn mc Enl tng ln theo th t tng ( n + l ), nu hai phn mc (phn lp) c cng gi tr tng ( n + l ) th Enl tng theo n".
En
Lp O n=5 5s
5p 4d 4p
Lp M n=3
4s 3s
3p 2p
3d
Lp L n=2 Lp K n=1
2s
HNH 2.11. S biu din cc mc nng lng ca cc AO trong nguyn t nhiu electrron
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gio trnh ho i cng
C th c th ho s trn bng cch:
HNH 2.12. Quy tc Klechkowski T hnh 2.10 ta thy c s chn nng lng (giao thoa nng lng) gia cc lp M v N. Tc l gia cc lp c s lng t chnh n 3, khng c s chn mc nng lng gia cc lp K (n = 1), L (n = 2) v M (n = 3) v cc lp ny nng lng ca chng tng i xa nhau. T s ny vit c th t tng dn mc nng lng nh sau: 1s 2s2p 3s3p 4s3d4p .... S ny cng l th t in cc electrron vo cc AO, n cho php vit c cu hnh electron ca nguyn t v hiu c cu to ca bng tun hon cng nh nguyn nhn gy ra s bin i tun hon cc nguyn t ho hc. Quy tc Klechkowski cho thy nng lng ca electron trong nguyn t nhiu electron ph thuc vo c s lng t chnh v s lng t ph (Enl). Nhng cn nh trong nguyn t c 1 electron (nguyn t H) nng lng ch ph thuc vo s lng t chnh (En). 4.4. Cu hnh electron ca nguyn t nhiu electron S sp xp cc electron vo nguyn t nhiu electron l mt trong nhng vn quan trng khi xt nguyn t c nhiu electron. Kt qu ca s sp xp c biu din bng cu hnh electron. 4.4.1. Cu hnh electron Cu hnh electrron ca nguyn t l s sp xp cc electron vo cc obitan ca nguyn t nhiu electron trng thi c bn (trng thi c nng lng cc tiu, Emin). 4.4.2. Cch biu din cu hnh electron ca nguyn t Thng biu din bng 2 cch sau
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gio trnh ho i cng
* Cch 1: dng nl a , n , l ,b ,... Trong : n l s lng t chnh thng biu th bng cc ch s 1, 2, 3, ...; l l s lng t ph thng biu th bng cc k hiu s, p, d, f, ...; a, b l s electron ca cc phn lp ng vi s lng t chnh n v s lng t ph l V d 1: Cu hnh electron ca H: 1s2 Cu hnh electron ca C: 1s2 2s22p4 * Cch 2: dng lng t. lng t l mt biu tng mang tnh quy c dng biu din cc obitan (thay cho vic phi dng hnh dng ca cc obitan, trnh s phc tp khi biu din) C th dng mt trong cc biu tng sau biu din lng t: + Hnh vung: + Hnh trn: + gch ni: AO-s AO-p AO-d Nu mt hnh vung ng ring r th l AO-s, ba hnh vung ng lin nhau l AO-p, nm hnh vung ng lin nhau l AO-d, by hnh vung ng lin nhau l AO-f,...; Vi biu tng l ng trn hoc gch ni cng vy. V d 2: Hy biu din cu hnh electron ca H v C bng lng t Tr li
H (Z=1)
C (Z=6)
1s
1s
2s
2p
By gi chng ta cng nhau xem xt u im v nhc im ca hai cch biu din ny. + Cch biu din th nht c u im l nhanh, gip cho xc nh c ngay s electron c trong mt phn lp, mt lp. Nhng cch ny li khng xc nh c s electron c thn v s cp electron ghp i. Mun bit thng tin v electron s 5 ca nguyn t C th cng ch xc nh c electron ny nm phn lp 2p, nn c s lng t chnh n = 2 v s lng t ph l = 1, khng xc nh c s lng t t ml v s lng t spin ms . Nh vy khi vit cu hnh electron theo cch mt ch xc nh c hai s lng t chnh v s lng t ph. + Trong cch biu din th hai: Dng lng t, cch ny khi vit mt nhiu thi gian hn nhng li cho chng ta bit c nhiu thng tin hn nh: Xc nh c s cp electron cng nh s electron c thn lp v ngoi cng. V d 3: T cu hnh electron ca nguyn t cacbon, xc nh c lp ngoi cng c: 2 electron c thn nm AO-2p v mt cp ghp i nm AO-2s. Cch biu din ny cng gip xc nh c y bn s lng t m t trng thi ca mt electron. Chng hn electron s 6 ca cacbon (e6) c: e6: n = 2; l = 1; ml = 0; ms = +1/2
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gio trnh ho i cng
Xc nh cc s lng t chnh n, s lng t ph l v s lng t spin ms rt d dng. Vic xc nh s lng t t ml cn tun theo nguyn tc sau: + Electron thuc phn lp s (c 1 AO-s) lun c s lng t t ml = 0. + Electron thuc phn lp p (c 3 AO-p) v thuc phn lp d ( c 5 AOd), gi tr ca s lng t t c xc nh theo chiu t m sang dng, tc l theo chiu tng dn( tnh t tri sang phi). y l quy c chung khi xc nh ml V d 4: Xc nh s lng t t ml ca phn lp p, d Tr li S lng t t c xc nh theo quy c sau: T m n dng ml = -1 0 +1 -2 -1 0 +1 +2 Theo quy c trn, ta c: ml = -1 0 +1 ml = -2 -1 0 +1 +2 4.4.3. Cc c s vit cu hnh electron ca nguyn t C bn c s chi phi s phn b electron trong nguyn t nhiu electron. Mi c s c mt v tr nht nh v gia chng li c mi lin h vi nhau. a) Nguyn l vng bn: Trong nguyn t nhiu elctrron, electron c in vo cc AO c mc nng lng thp trc, sau mi c in vo cc AO c mc nng lng cao hn, trng thi c bn Emin. Trng thi c bn l trng thi h nguyn t c nng lng thp nht, hay cc tiu, y l trng thi bn vng nht ca h lng t ni chung v h nguyn t ni ring. Nguyn l cc tiu nng lng l quy lut thng gp ca th gii t nhin l lun c xu hng t n s bn vng nht, n nh nht. Nguyn l vng bn khng cho bit AO no c nng lng thp, AO no c nng lng cao. Mun bit c iu ny cn da vo quy tc Klechkowski b) Quy tc Klechkowski: Xem mc 4.3 V d5: Xt nguyn t H, nguyn t ny ch c 1electron. Electron ny c xp vo AO-1s m khng c xp vo AO-2s v nng lng ca AO-1s nh hn AO-2s. V d 6: Cho cc phn lp 3s, 3d, 4s, 5d, 4p. Hy tnh tng (n + l) ri sp xp cc phn lp ny theo trt t tng dn mc nng lng Tr li Tnh tng: 3s c (n + l) = 3 + 0 = 3 3d c (n + l) = 3 + 2 = 5 4s c (n + l) = 4 + 0 = 4 5d c (n + l) = 5 + 2 = 7 4p c (n + l) = 4 + 1 = 5 Trt t nng lng: 3s < 4s < 3d < 4p < 5d c) Nguyn l loi tr Pauli: Trong mt nguyn t khng th c t 2 electron bt k tr ln c 4 s lng t nh nhau.
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Tc l: "Trong cng mt nguyn t khng th c 2 electron c cng mt trng thi ging ht nhau. Hay:Trong cng mt AO ch c ti a 2e v 2e ny phi c spin khc nhau. V d 7: Xt nguyn t He. Nguyn t He c cu hnh electron: 1s2 Hai electron ny u nm trn AO-1s, do c cng b ba s lng t l: Nn hai electron ny phi khc nhau s lng t spin: Mt electron c s lng t spin ms = +1/2, cn mt electron c s lng t spin ms = -1/2. d) Quy tc Hun 1: C ba quy tc Hun c p dng khi xt cu to ca nguyn t nhiu electron. Chng ta ch xt quy tc Hun 1:"Trong cng mt phn lp vi nhiu obitan nguyn t (AO) c cng mc nng lng nh nhau, cc electron s c phn b sao cho to ra c nhiu electron c thn nht". V d 8: Xt trng hp c 2 electron v hai AO c nng lng bng nhau Tr li C hai kh nng phn b 2 e ny: + Trng hp 1: C hai e cng chim 1 AO, l s ghp i electron, trng hp ny s c 1 AO khng c electron (AO trng) thn. hoc hoc
n = 1; l = 0; ml = 0
+ Trng hp 2: Mi electron chim 1 obitan, l cc electron c
Quy tc Hun 1 ch ra rng khuynh hng phn b electron theo trng hp hai (s electron c thn nhiu nht) chim u th. V d 9: Trong nguyn t nit c 3 electron thuc phn lp 2p a) C nhng khuynh hng no trong vic phn b 3e ny? (mi khuynh hng ly hai v d minh ha). b) Trong hai (hay nhiu hn) trng hp ca khuynh hng chim u th theo quy tc Hun 1, Hy ch ra tng hp ng vi trng thi c bn ca nguyn t nit. Ti sao trng hp li ng vi trng thi c bn? Tr li Phn lp 2p c 3AO c cng mc nng lng (v c cng n, l ) a) Hai khuynh hng phn b 3 e ny l: + c thn; a1 a2 + C s ghp i:
;..... khuynh hng ny chim u th 65

gio trnh ho i cng
b) a1 l trng hp ng vi trng thi c bn ca nit v c 3e u trng thi spin hng ln (ms = +1/2) l trng thi c nng lng thp nht. Mi electron c s lng t spin ms = +1/2. Vi nguyn t nhiu electron th spin tng S c tnh theo h thc:
S = n
1 2
(4.1)
Trong : n l s electron c thn. D dng thy rng khi c nhiu s electron c thn nht, tc l n = nmax , th:
S max = nmax
1 2
(4.2)
T , quy tc Hun 1 cn c pht biu theo cch sau: "Cc eletron c phn b vo cc obitan ca cng mt phn lp sao cho tng spin ca chng t gi tr ln nht (gi tr cc i)" V vy quy tc Hun 1 cn c gi l quy tc tng spin cc i (quy tc Smax) 4.4.4. Cch vit cu hnh electron ca nguyn t a) Trc ht cn xc nh ng tng s electron ca nguyn t Tng s electron = s n v in tch dng ht nhn Z Ch : Cn phn bit gia nguyn t vi ion. V d 10: Nguyn t Na c Z = 11, do c 11e; ion Na+, c Z = 11 ch c 10e Theo nguyn l Pauli, trong 1AO c nhiu nht 2e vi s lng t spin khc du nhau. Trong mt phn lp, s electron nhiu nht l 2(2l + 1) . Phn lp electron (cn gi l v electron) c s electron cc i c gi l phn lp bo ha (v bo ha). V bo ha c gi l v kn, v cha bo ha c gi l v h. V d 11: T cu hnh electron ca nguyn t nit (Z = 7): 1s2 2s22p3 cho bit, phn lp 1s, 2s l cc phn lp bo ha (v kn) cn phn lp 2p cha bo ha (v h) V d 12: Hy tnh s electron bo ha cho v s, p, d, f v vit cu hnh electron cho mi v . Tr li p dng cng thc tnh s e ti a cho mt phn lp = 2(2l + 1) , ta c; Phn lp s, l = 0 2(2.0 + 1) = 2 cu hnh v kn: ns2 Phn lp p, l = 1 2(2.1 + 1) = 6 cu hnh v kn: np6 Phn lp d, l = 2 2(2.2 + 1) = 10 cu hnh v kn: nd10 Phn lp f, l = 3 2(2.3 + 1) = 14 cu hnh v kn: nf14 Cn nh tng s electron nhiu nht trong mt lp = 2n2 vi n l s lng t chnh. Ch : S lng ny c khi lp bo ha, cn trong qu trnh xy dng cu hnh, vi n 3 s lng ny cha ng (xem v d 14)
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b)Khi vit cu hnh electron Cn da vo bn c s gm nguyn l vng bn, nguyn l Pauli, quy tc Klechkowski, quy tc Hun 1 nu trn v s lng electron. V d 13: Xt cu hnh electron ca: a) F; b) K Ta c: a) F c Z = 9 c 9e. Dng lng t biu din cu hnh electron ca F: Hay: 1s2 2s22p5. V 1s2 ng vi s bo ho s e lp th nht (n = 1), cng l cu hnh electron ca nguyn t He, nn c th vit: F 1s2 2s22p5 hay [He] 2s22p5 b) Tng t nh trn, ta c K vi z = 19 c 19e Dng lng t biu din
[Ar] Vy cu hnh ca K l: K: 1s2 2s22p6 3s23p6 4s1 hay [Ar] 4s1 Cn lu : Phi in electron th 19 (e19) vo AO-4s ch khng phi AO3d, v nng lng ca AO-4s nh hn AO-3d. Trong cu hnh electron ca K, phn lp 4s ch c 1e, cha bo ha, phn lp ny li nm ngoi cng nn electron phn lp 4s c gi l electron ha tr ca K Nhn vo cu hnh electron ca F, lp L (n = 2) c 7e, cha bo ha (thiu 1e). Lp L ngoi cng nn 7e ny c gi l electron ha tr ca F. Nh vy: Electron phn lp hay lp ngoi cng cha bo ha c gi l electron ha tr ca nguyn t. V d 14: a) Hy vit cu hnh electron ca: Ca, Cr, Fe. T cc kt qu c th rt ra c nhng trng hp no c th c khi xt cu hnh electron ca nguyn t? b) T cu hnh electron ca Cr v Fe c th rt ra c kt lun no v electron ha tr? Kt hp vi kt lun va xt v d 13, c th khi qut ha khi nim electron ha tr nh th no? Tr li a) Ca c Z = 20, nguyn t ni tip K trong bng h thng tun hon, nn d dng xc nh c cu hnh electron ca Ca l: [Ar] 4s2 Cr c Z = 24 Cr c 24e. Lm tng t nh vi K, ta c:
1s2

2s2 2p6
[Ar]
3d5
4s1
3s2
3p6
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Vy cu hnh electron ca Cr l: [Ar]3d5 4s1 Khi vit cu hnh electron ca Cr cn lu hai im sau: + Trong cu hnh electron ca Ca va xt c s bo ha phn lp (v) 2 4s , cn cu hnh electron ca Cr li ch c 4s1, cha bo ha, mc d Cr vi Z = 24 ng sau Ca vi Z = 20. Nh vy: Cu hnh electron ca Cr l mt trng hp bt thng. + So snh vi cu hnh electron ca Ca, sau [Ar] tip n 4s2, cn Cr th sau [Ar] phi n 3d5 mi ti 4s1 y l kt qu ca s sp xp li th t nng lng cc phn lp sau khi in electron. Th t ny b o gia hai phn lp ns v (n-1)d trong trt t nng lng nu ra quy tc Klechkowski Fe tng t nh trn ta c cu hnh electron ca Fe l [Ar]3d6 4s2 S sp xp 3d6 trc 4s2 l do c s o th t nh va xt vi Cr. T cc kt qu va xt, nhn thy c hai trng hp xy ra khi vit cu hnh electron ca nguyn t: Trng hp 1: Bnh thng, c ch n s o th t AO sau khi in electron nh Fe. Trng hp 2: Bt thng v s lng electron mt s phn lp hay lp, nh Cr. b) Vi Cr v 3d c 5e, v 4s c 1e. Hai v ny u cha bo ha, hai lp khc nhau (n = 3 v n = 4). C 6e u c vai tr l electron ha tr (dn chng: Cr to ra c hp cht trong Cr c s oxi ha +6, nh K2Cr2O7, ...). Vi Fe cng tng t Cr, Fe c v 3d vi 6e v v 4s vi 2e. C 8e ny u c th ng vai tr l electron ha tr. Cng xy ra tnh trng ny i vi cc nguyn t khc m nguyn t c cu hnh electron trong c v (n - 1)d cha bo ha, cn v ns bn ngoi bo ha (ns2) hay cha bo ha (ns1). C th biu din cu hnh nh sau: ... (n - 1)d10-xns2 hay ..... (n - 1)d10-xns1 Trong : x nguyn, 0 < x < 10 T cc trng hp nu ra trn, c th rt ra kt lun: Electron ha tr(ngoi)thuc lp, phn lp cha bo ha.. Khi vit cu hnh electron cn ch , nu khng vit dng lng t th kh xc nh c l cu hnh c ng vi trng thi c bn ca nguyn t hay khng. Do nn xt ng thi c cch vit dng thu gn ( nl a nlb ... )v dng lng t, xem cc v d trn. Trng thi kch thch ca mt h lng t (nguyn t, ion, phn t) thng c hiu l trng thi c s chuyn di ca electron t phn mc hay mc nng lng thp ln mc hay phn mc nng lng cao hn. V d 15: Trng thi c bn ca C l: Trng thi kch thch ca C l:
1s
2s
2p
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Khi nim "Trng thi kch thch ca mt nguyn t" l mt khi nim rng, rng hn khi nim trng thi ha tr hay trng thi lai ha. c) Xc nh cu hnh e lectron khi bit 4 s lng t ca electron cui cng in vo v nguyn t V d 16: Cho b 4 s lng t ca electron cui cng in vo nguyn t: 1. n = 2; l = 1; ml = 0; ms = 1/2 2. n = 2; l = 1; ml = 0; ms = -1/2 3. n = 3; l = 2; ml = 2; ms = -1/2 Hy xc nh s hiu nguyn t ca cc nguyn t ng vi cc b s lng t trn. Tr li Electron ny thuc phn lp 2p ( v n = 2; l = 1) Xc nh v tr ca electron ny trn phn lp 2p da vo ml v ms ml = -1 0 1 Vy phn lp 2p c 2e, vi cu hnh 2p2 (v mun c electron ng vi s lng t ml = 0, th electron c s lng t ml = -1 phi c in trc, theo quy tc Hun 1) Do cu hnh electron y ca nguyn t ng vi electron ny l: 2 2 1s 2s 2p2 Cui cng, m s electron (6e = 2 + 2 + 2) Z = 6 ( nguyn t: C) Trng hp 2 v 3 ca v d 16 cc bn sinh vin hy t lm. T hy t rt ra cc bc cn tin hnh khi gp bi ton dng ny. Cc bn cng c th t ra ly bi kim tra cho mnh nhng cn ch ly cc gi tr ca cc s lng t sao cho ph hp nhau v mi quan h. 4.5. Phng php Slater xc nh cc AO v nng lng ca electron Nm 1930, Slater a ra mt phng php gn ng xc nh hm bn knh Rnl v nng lng tng ng ca obitan l nl ( nl l nng lng ca mt electron) Vic xc nh hm bn knh v cc mc nng lng ca electron da vo phng trnh kinh nghim ca Slater.
Rnl (r ) = cr
n* 1
.e
_( Z b ) r a0 n*
(4.3) (4.4)
nl =
2 ( Z b) 2 .e0 ( Z b) 2 (eV ) = 13,6 ( n * ) 2 2 a0 (n* ) 2
Trong :
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Z l s n v in tch ca nguyn t (s th t ca nguyn t trong bng h thng tun hon) b l hng s chn (Z- b ) l s n v in tch ht nhn hiu dng c l hng s a0 l bn knh Bo th nht e l c s logarit t nhin e0 l in tch c bn Trong hai biu thc trn cn xc nh n* v b Quy tc gn ng xc nh n* v b a) Xc nh s lng t chnh hiu dng n* theo bng 2.1 BNG 2.1. S lng t chnh hiu dng
n
1 1
2 2
3 3
4 3,7
5 4,0
6... 4,2...
n*
(n l s lng t chnh vn c) b) Xc nh hng s chn b *) Cc electron c chia thnh cc nhm sau (1s); (2s, 2p); (3s, 3p); (3d); (4s, 4p); (4d, 4f); ... Cc AO trong cng mt nhm c hm bn knh Rnl (r ) nh nhau *) Gi tr hng s chn b i vi 1e ang xt s bng tng cc gi tr ng gp ca cc electron khc, nh sau: + Cc e nhm AO pha ngoi nhm AO ang xt c tr s ng gp bng 0 (khng ng gp vo ) V d 17: Xt AO-1s th tt c cc e t AO-2s tr ra u c tr s ng gp bng 0 + Mi e cng nhm AO vi e ang xt ng gp mt lng l 0,35 ring 1e trn cng AO-1s ch gp mt lng l 0,30. + Lng ng gp ca mi e AO bn trong so vi AO ang xt: - lp n c tr s nh hn n ca lp ang xt 1 n v, ng gp 0,85 - lp n c tr s nh hn n ca lp ang xt t 2 n v tr ln (tc l su hn, gn ht nhn hn), ng gp 1,0. + Nu AO ang xt l AO-d hay AO-f th mi e AO bn trong ng gp 1,0 vo b . V d 18: Hy s dng phng php gn ng Slater xc nh biu thc hm bn knh Rnl (r ) v nng lng nl tng ng i vi Li. Tr li Li c Z = 3 Li c 3e, cu hnh electron ca Li l: 1s2 2s1
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a) Xt AO-1s: Khng k 2s1 nm bn ngoi, Trong AO-1s c 2e th 1e ang xt b e cn li chn, nn n* = n = 1 v b = 1.0,3 = 0,3 Z - b = 3,0 - 0,3 = 2,7 Vy hm R1s (r ) = cr 11e 2,7 r / a = cr 0 e 2,7 r / a = ce 2,7 r / a Trong h n v nguyn t, a0 = 1 nn R1s (r ) = ce 2,7 r
0 0 0
Nng lng 1s = Hay
2 (3 0,3) 2 eo = 7,29(dvn) = 7,29.13,6(eV ) = 99,144(eV ) 12 2a 0
1s = 13,6
(3 0,3) 2 (eV ) = 99,144(eV ) 12
Ch : 1s l nng lng 1e AO-1s b) Xt AO-2s: trn AO ny c 1e, nhm bn trong c 2e chn e ang xt, nn: n* = n = 2 b = 2.0,85 = 1,7 Z - b =3,0 - 1,7 = 1,3 Vy hm R2 s (r ) = cr e = cre Trong h vn, th R2 s (r ) = cre 0,65 r
2 1 1, 3 r 2 a 0 r 0 , 65 a0
Nng lng 2 s = Hay
2 (3,0 1,7) 2 e0 = 0,4425(dvn) 22 2a 0
(3,0 1,7) 2 (eV ) = 5,75(eV ) 22 (Thc nghim xc nh c 2 s = 5,4(eV ) . So snh kt qu tnh theo l
2 s = 13,6
thuyt ca Slater vi thc nghim, chng t phng php Slater chp nhn c) Nng lng electron ca nguyn t Li bng :
E = 2 1s + 2 s = 2.(99,144) + (5,75) = 204,38(eV ) 204(eV )
V d 19: Tng t v d 16, nhng xt cho nguyn t C Nguyn t C c cu hnh: 1s2 2s22p2 Xt cho AO-1s, ch c 1e chn 1e ang xt, nn: n* = n = 1 b = 1.0,3 = 0,3 Z - b = 6 -0,3 = 5,7 Nn: Hm bn knh thu c R1s (r ) = cr e
11 60 , 3 r a0 1
= ce
5, 7 r a0
Nng lng
1s = 13,6
(6 0,3) (eV ) = 441,86(eV ) 12

2
i vi AO-2s hay AO-2p nm cng nhm, nn c 3e chn 1e ang xt, nhm bn trong th c 2e chn 1e ang xt, nn: n* = n = 1 b = 3.0,35 + 2.0,85 = 2,75 ? Z - b = 6 - 2,75 = 3,25 Vy: Hm bn knh thu c R2 s (r ) = cr e
2 1 ( 6 2 , 75 ) r a0 2
= cre
1, 625 r a0
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Nng lng
2 s = 2 p = 13,6
(6 2,75) 2 (eV ) = 35,91(eV ) 22
Nng lng electron ca nguyn t cacbon bng
E = 2 1s + 2 2 s + 2 2 p = 2.(441,86) + 4(35,92) = 1027,4(eV )
Cc bn hy lm tng t vi cc nguyn t N (Z = 7), O (Z = 8), F (Z =9),... 5. HT NHN NGUYN T Ht nhn nguyn t hin nay tr thnh mt lnh vc khoa hc va c c s l thuyt su sc va c ng dng thc tin ngy cng rng ri c trong khoa hc, cng ngh ln i sng. 5.1. Nguyn t * Nguyn t l phn t nh nht ca mt nguyn t m vn mang tnh cht ho hc ca nguyn t . V d 1: Hy vit phng trnh phn ng chng minh s khc nhau v tnh cht ho hc: a) Gia Na v Na+ b) Gia Cl v ClChng minh bng phng trnh: 2Na + Cl2 2NaCl
NaCl dtnfc Na +Cl2
Nguyn t c 3 c trng quan trng l in tch, khi lng, kch thc. V in tch: Nguyn t trung ha v in. 1 nguyn t ha hc c s th t trong bng h thng tun hon l Z th: Ht nhn nguyn t hay ion ca nguyn t c s n v in tch (+) l Z.e0; S n v in tch (-) l - Z.e0 (e0 = 1,6.10-19 C = 1 n v in tch nguyn t). Trong nguyn t ca nguyn t c Z electron. V d 2: Cho bit s ging nhau v khc nhau gia cc cp sau: a) Ca vi Ca2+ b) F vi FTr li a) Gia Ca v Ca2+ Ging nhau: u c s n v in tch ht nhn bng +20 Khc nhau: - Ca c 20 e, nn c s n v in tch m l -20, nguyn t Ca trung ho v in - Ca2+ c 18e, nn c s n v in tch m l -18, ion Ca2+ mang in tch +2 - Ca ch th hin tnh kh, cn Ca2+ ch th hin tnh cht oxi ho. Ca - 2e Ca2+
Ca2+ + 2e Ca
Phng trnh phn ng :
Ca + 2H+ Ca2+ + H2
Ca 2+ + 2Cl dfnc Ca + Cl 2
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gio trnh ho i cng
b) Vi F v F- cc bn t lm V khi lng: Khi lng ca nguyn t c coi l tp trung ht nhn, khi lng ht nhn ca mt nguyn t c coi l khi lng nguyn t ca nguyn t . V s o khi lng nguyn t c 2 tr s c cp. Th nht: S khi, c 2 quan nim v s khi: S khi (ca 1 nguyn t) = tng s ht Proton + S ht ca n tron to nn ht nhn nguyn t ca nguyn t nn s khi l s nguyn. Th hai: Khi lng ca nguyn t hay nguyn t khi. Tr s ny l trung bnh cng theo t l s khi ca ng v nn thng l s khng nguyn. S khi l s nguyn gn nht vi khi lng ca nguyn t . V kch thc: Cn lu hai vn sau. Xt gn ng: ng knh ca nguyn t khong 10-8cm; ng knh ca ht nhn khong 10-13cm, nn trong nguyn t khong khng gian e chuyn ng l rt ln. V vy d dng hnh dung c s bin dng v bin i ca mt nguyn t khi tham gia lin kt ha hc. biu th kch thc ca nguyn t, chng ta dng bn knh cng ha tr ca n: Bn knh cng ha tr ca mt nguyn t bng mt na khong cch gia hai ht nhn nguyn t trong phn t c to ra t hai nguyn t . V d 3: dBr-Br = 0,228 nm rBr = 0,114 nm 5.2. Mt s vn v ho hc ht nhn 5.2.1. Cc c trng c bn ca ht nhn a) in tch: e0 = 1,6021.10-19C = 1 (vt nguyn t) Nh vy mt ht proton mang mt in tch dng bng 1,6.10-19C = 1 Ntron l ht khng mang in. Do s n v in tch (+) ca mt ht nhn = Z.e0 = Z = P Hin nay trong Bng h thng tun hon c 114 nguyn t (trong nhiu nguyn t c to ra bng con ng nhn to, l cc nguyn t c Z = 43, 64, 85 v Z > 92). b) Khi lng: S o c s ca cc ht c bn l khi lng ngh ca electron, kh hiu m0; m0 = 9,108.10-28g = 9,108.10-31Kg. Nh vy: khi lng ca 1 ht proton bng: mp = 1836,12. m0 = 1,672.10-27 kg = 1,0072 (u) =1 (u) Khi lng ca mt ht ntron bng: mn = 1,6750.10-27 kg = 1, 0086 (u) = 1 (u) Theo quy c quc t mi tr s u c coi bng n v (1u). Vy khi lng tng i ca mt ht nhn l: A = P + N Trong : P l s ht proton v N l s ht ntron c trong mt ht nhn. V d 4: Khi lng tng i ca ht nhn oxi bng 8 + 8 = 16; ca vng = 79 +118 = 197 (79 l s ht proton, 118 l s ht ntron c trong ht nhn nguyn t vng).
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gio trnh ho i cng
Khi lng ca ht nhn nh hn khi lng nguyn t tng ng 1 lng l Z.m0 (khi lng ca e v). c) Cc ng v: Cc ng v l cc nguyn t ca cng mt nguyn t m ht nhn c cng s proton, khc nhau s ntron. V d 5: Trong nguyn t hiro, ht nhn c 1 proton, khng c ntron (A = 1) Trong teri, ht nhn c 1 proton, 1 ntron (A = 2) Trong triti, ht nhn c 1 proton, 2 ntron (A = 3) Vy hiro, teri, triti l cc ng v ca nguyn t hiro; trong hai ng v hiro v teri bn hn ng v triti. C nhng nguyn t ch c mt ng v bn nh Be, F, P; c hai ng v bn nh hiro; c by ng v bn nh thu ngn; c mi ng v bn nh thic;.... Hin nay c khong 1080 ng v, bao gm cc ng v c sn trong t nhin hoc c tng hp bng con ng nhn to. d) Quy c cch vit k hiu nguyn t ca mt nguyn t Mt nguyn t ho hc X c s n v in tch dng ht nhn bng Z, s khi A c k hiu:
Z
XA
hay
A Z
Trong mt s trng hp, nu ch quan tm n khi lng A (s khi A), th c k hiu:

XA hay AX
V d 6: Cacbon c hai ng v l C12 (12C) v C13 (13C) Phn trn cho thy electron c khi lng ngh rt nh so vi khi lng ngh ca proton hay ntron: mp = 1836,12 me Do , mt cch gn ng: Khi lng ca mt ht nhn nguyn t c coi l khi lng ca chnh nguyn t . Thc nghim cho bit, trong t nhin cc nguyn t ho hc tn ti ng thi mt s ng v. Do , khi lng nguyn t ca mt nguyn t thc t l khi lng ca mt hn hp vi t l khc nhau ca cc ng v. V th khi lng bao gi cng l mt s khng nguyn. ) Bn knh v khi lng ring ca ht nhn Cc kt qu thc nghim cho bit th tch ca ht nhn xp x t l vi s nucleon ca n, v vy bn knh ht nhn cng xp x t l vi cn bc ba ca s khi. Trong : R l bn knh ht nhn H s t l k = (1,2 1,5).10-13 cm. V d 7: Xt ht nhn U238 C R 1,5.10-13.2381/3 10-12 cm Bn knh ca ht nhn nguyn t 10-13 cm 10-12 cm Bn knh ca nguyn t 10-8 cm (1A0), ngha l:
R k.A1/3
(5.1)
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gio trnh ho i cng
Rnguyn t/Rht nhn = 1 10 vn ln V t l th tch ca ht nhn xp x t l vi s nucleon, v cc nucleon c khi lng xp x bng nhau, nn ht nhn c khi lng ring gn nh khng i. Tnh khi lng ring ca ht nhn nh sau: Mt nguyn t c s khi A, khi lng ca n l:
A 6,022.10 23 1 4 V = R 3 = (1,5.10 13 ) 3 A 3 3 m A d= = 1,16.1014 g cm 3 4 V 6,022.10 23. .3,38.10 39 A 3 m=
Th tch ca n l:
Nh vy, 1cm3 ht nhn nng khong 116 triu tn. 5.2.2. Cu trc proton - ntron ca ht nhn a) Thuyt proton- ntron Thc nghim xc nhn gi thuyt ca cc nh khoa hc Haixenbec (ngi c) v Ivanenko (ngi Nga) a ra: Ht nhn gm proton v ntron. Nu s proton trong mt ht nhn l Z v s khi l A th s ntron N l N=AZ (5.2) 3 V d 8: Mt ht nhn ca nguyn t triti 1H c 1proton v 2 ntron. Mt ht nhn nguyn t oxi c 8 proton, 8 ntron. Cc ht to nn ht nhn c gi chung l cc ht nucleon. b) Mt s quy lut v mi quan h gia s nucleon c bit bn l cc ht nhn c: Z = N = 2 ; 8 ; 20. l cc ht nhn "hai ln k diu" C bn cao l cc ht nhn: Z = 28, 50, 82 hay N = 50 ; 82 ; 126 cc ht nhn mt ln k diu V d 9: 2He4 (2p, 2n); 8O16 (8p, 8n); 20Ca40 (20p, 20n); 28Ni60 (28p, 32n); ... Tng s cc ht nhn c Z chn ln hn nhiu so vi tng s cc ht nhn c Z l. Tng s cc ht nhn c A chn ln hn nhiu so vi tng s cc ht nhn c A l. Hu ht cc ht nhn c A chn u c Z chn (tr 1D2, 3Li6, 5B10,7N16). c) ht khi lng, nng lng lin kt ht nhn K hiu khi lng ca mt proton l m p , mt ntron l mn Nu ht nhn c Z ht proton v N ht ntron, th khi lng ca ht nhn s l:
Zm p + Nmn
y l khi lng cc nucleon trong ht nhn. Cn thc nghim o c khi lng ht nhn l:
A mhn
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gio trnh ho i cng
So snh hai khi lng ht nhn trn, trong bt c trng hp no cng cho kt qu: A Zm p + Nmn > Z mhn Tc l: Khi lng cu mt ht nhn o c lun nh hn tng khi lng ca cc ht nucleon ca chnh ht nhn . Hiu s ca hai khi lng trn c gi l ht khi m ( ht khi lng)
A m = Zm p + Nmn Z mhn
Vn cn c nu ra l: Nguyn nhn no m c s ht khi ca ht nhn? Da vo cc kt qu thc nghim, cc nh khoa hc cho bit l do 1 phn khi lng ca cc ht nucleon ban u bin thnh nng lng v truyn cho mi trng ngoi. Nh vy: Khi hnh thnh mt ht nhn mi t cc ht nucleon l mt qu trnh gii phng nng lng Theo Anhxtanh: (5.3) E = mc 2 2 Do E = mc (5.4) E l nng lng c gii phng trong khi hnh thnh mt ht nhn, km theo ht khi lng l m . Nu tin hnh qu trnh ngc li, tc l ph v ht nhn (xt trong cng mt iu kin ging nh khi hnh thnh mt ht nhn) ta phi tiu tn mt nng lng chnh bng E . Vy: E c trng cho s bn vng ca ht nhn. E c gi l nng lng lin kt ht nhn. Mt ht nhn c E cng ln tc l c m cng ln th ht nhn s cng bn vng 54 V d 10: Thc nghim xc nh c 25 mhn = 53,956(u ) ; 54 238 v 92U238 92 mhn = 238,125(u ) . Tnh nng lng lin kt ht nhn ca 26Fe Tr li Vi 26Fe56 c 26 proton, 28 ntron Do : m = (26.1,00728 + 28.1,00866) 53,956 = 0,47576(u )
1g 1kg 3,0.108 m.s 1 E = mc 2 = 0,47576. 23 6,023.10 1000 g
7,11.10 11 J
Vi 92U238 c 92 proton, 146 ntron Vy m = (92.1,00728 + 146.1,00866) 238,15 = 1,78412
1g 1kg 3,0.10 8 m.s 1 E = mc 2 = 1,78412. 23 6,023.10 1000 g
= 2,666.10 11 J
Cc gi tr nng lng va tnh c ng vi mt ht nhn. D dng tnh c nng lng gii phng ra khi hnh thnh mt mol ht nhn. Vi 1mol 26Fe54: Vi 1mol 92U238:
E = E.6,023.10 23 = 7,11.10 11.6,023.10 23 = 42,7633.1012 J = 42,7633.10 9 kJ E = 42,7633.109 kJ = 1.19.10 7 kWh
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gio trnh ho i cng
E = E.6,023.10 23 = 2,666.10 11.6,023.10 23 = 16,057.1012 J = 16,057.10 9 kJ E = 16,057.10 9 kJ = 4,46.10 6 kWh
(l nng lng lin kt ca 1mol ht nhn) Nh vy nng lng lin kt to ra mt mol ht nhn l rt ln, ln hn hng triu ln so vi mt phn ng ha hc thng thng. Vi mt ht nhn c A nucleon, gi l nng lng lin kt ht nhn ng vi 1 nucleon,th: E c gi l nng lng lin kt ht nhn ng vi 1nucleon hay nng lng lin kt ht nhn ring.
E =
E A
(5.5)
Qua vic kho st mi quan h gia E v A rt ra kt lun sau: Cc nguyn t c s khi A = 20 200, E cao, tc l cc ht nhn ca cc nguyn t ny bn vng hn so vi cc ht nhn nh hn hay nng hn n y, c hai xu hng c ch : - Tng hp cc ht nhn nh thnh cc ht nhn trung bnh - Phn r cc ht nhn nng thnh cc ht nhn trung bnh 5.2.3. Lc lin kt ht nhn (cn ang c nghin cu) Theo Nikedi Yukawa (1935-Nht Bn) th lc lin kt gia cc ht nucleon trong ht nhn sinh ra l do qu trnh bin ha qua li gia cc proton v ntron, c km theo s lin tc hnh thnh v ph hu cc ht meson + hay - (khi lng ca mt ht meson bng 270 ln khi lng ca electron), cc meson li phn hy ngay bin thnh cc posison (e+) v negatron (e) v ntrino (0: ht ny khng mang in, c khi lng bng 1/500 ln khi lng ca electron).
1 1 1 0
p =1 n + + 0 n =1 p + 1
; + = e+ + 0 ; = e + 0
5.2.4. Phng x ht nhn a) Phng x t nhin: L kh nng cc cht cha cc nguyn t xc nh t pht ra cc bc x khng nhn thy c thnh phn phc tp. Hin tng ny c nh bc hc Php Henri Beckren pht hin ra vo nm 1896, qua nghin cu hp cht ca Uran. Sau , c b Mari Quyri tin hnh nghin cu mt cch c h thng. b)Thnh phn ca tia phng x: Bc x do cc tia phng x pht ra c thnh phn phc tp. Cc kt qu nghin cu khng nh bc x gm: Tia : Thc cht l ht nhn ca nguyn t heli: 2He4 (mang in +) Tia : Thc cht l dng e (mang in -). Tia : Thc cht l dng photon (khng mang in, khi lng photon rt b, nng lng rt ln). Nng lng ca cc photon c xc nh t phng trnh:
= h =
(5.6)
gio trnh ho i cng
77
Cc tia khc nhau v kh nng m xuyn v gy ion ha: Tia c kh nng m xuyn mnh nht l , yu nht l ; Tia c kh nng gy ion ho mnh nht l , yu nht l . Mt im cn ch : S phng x l mt qu trnh ni ht nhn. Tc l qu trnh phng x khng ph thuc vo dng cht, khng ph thuc vo trng thi ca cht, nhit , p sut, t trng, .... ch c th tc ng vo qu trnh phng x t nhin bng cch lm thay i trng thi ht nhn nh bn pha ht nhn bng ht ntron. Khi qu trnh phng x pht ra tia th khng c v ngc li. Tia bao gi cng i km vi 2 tia trn. Tnh cht ca cc tia: C kh nng xuyn qua vt cht, l qu trnh ni ht nhn. c) nh lut chuyn di Quy c: - Nguyn t u pht ra tia phng x l nguyn t m. - Sn phm c to thnh ca nguyn t m l mt nguyn t mi c th c hay khng c tnh phng. Nu c tnh phng x th gi l nguyn t con. nh lut c m t bng s : Nguyn t m nguyn t con + ( 2 He 4 ) (1) Hoc: Nguyn t m nguyn t con + (e) (2) Nu phng x ra tia th nguyn t m gim 2 n v in tch ht nhn v 4 n v ca s khi nn nguyn t con dch chuyn 2 v bn tri ca nguyn t m trong h thng tun hon. Nu phng x tia th nguyn t m khng b thay i s khi, nhng s n v in tch ht nhn tng thm 1 n v nn nguyn t con c to thnh c s khi bng s khi ca nguyn t m v dch chuyn mt v bn phi ca nguyn t m trong bng h thng tun hon. V d 11: 88Ra226 phng x ra tia : 88Ra226 86Rn222 + 2He4 40 phng x ra tia : 19 K 40 20 Ca 40 + 1 e 0 (e) 19 K T ta c s :
ZX A ZX A
Z-2Y
A-4
+ 2He4 (ht )
Z+1Y
+ e- (ht )
Ni dung ca nh lut chuyn di thc cht c bt ngun t nh lut bo ton s khi v nh lut bo ton in tch (nh lut bo ton khi lng). ) Cc h phng x Trong thc t c hin tng nguyn t m to ra nguyn t con 1, n lt nguyn t con 1 l nguyn t phng x v to ra nguyn t con 2, nguyn t con 2 li to ra nguyn t con 3 .... qu trnh tip din cho ti lc t c ng v bn th kt thc. Ton b qu trnh ny lp thnh 1 dy- dy phng x (h phng x). Hin nay c 4 dy: 3 dy c trong t nhin v 1 dy nhn to. H Uran: 92 U 238 (m) kt thc 82 Pb 206
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S khi ca h ny c lin h qua biu thc A = 4n + 2; 51 n 59; n nguyn. Trong h ny c 88Ra226, 86Rn222, 84Po208 H Thori: 90 Th 232 (m) kt thc 82 Pb 208 S khi ca h ny c lin h qua biu thc A = 4n; 52 n 58; n nguyn. H Actini: 92 U 235 (m) kt thc 82 Pb 207 S khi ca h ny c lin h qua biu thc A = 4n + 3; 51 n 59; n nguyn. H Neptun (nhn to): 93 Np 237 (m) kt thc 83 Bi 209 S khi ca h ny c lin h qua biu thc A= 4n + 1; 52 n 59; n nguyn. e) ng hc v s phn r phng x Phng trnh phn ng: nguyn t m nguyn t con + tia phng x Hay: A sn phm (5.7) L phn ng 1 chiu bc 1, trong A l cht u hay cht tham gia phn ng Nh vy quy lut ng hc ca s phn r phng x l quy lut ca phn ng mt chiu bc nht. Phng trnh ng hc ca phn ng c dng:
v= dx = k (a x) dt
(5.8)
Trong : v l vn tc ca phn ng o ti thi im t

dx l o hm bc nht ca nng cht phn ng (cht A) theo dt
thi gian phn ng a l nng cht A lc bt u phn ng ( t = 0) x nng cht A b mt i sau thi gian phn ng t (a-x) l nng cht A o ti thi im t k l hng s vn tc ca phn ng Bng cc php bin i ton hc phng trnh (5.8), th thu c phng trnh: Phng trnh (5.9) vit di dng hm s m (5.9b) p dng cc phng trnh (5.9a), (5.9b) cho qu trnh phn r phng x, chng ta s dng cc k hiu sau: (5.10b) Trong : k hay l hng s vn tc ca qu trnh phn r phng x N0 l s ht nhn phng x gc thi im ban u (t = 0)
1 a k = ln t ax
(5.9a)
(a x) = a.e kt
1 N k = = ln 0 t N N = N 0 e kt = N 0 e t
( 5.10a)
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N l s ht nhn c ti thi im t Mt i lng quan trng i vi ng ha hc ni chung cng nh qu trnh phn r phng x ni ring, l thi gian na phn ng (chu k bn hu). * Thi gian na phn ng t 1 L thi gian lng cht ban u (a hay
2
N0) ca cht phn ng gim i mt na. Tc l x = a/2 hay N = N0/2) c gi l thi gian na phn ng (chu k bn hu). Thi gian na phn ng c k hiu l: t 1 hay (c l t)
2
Thay N = N0/2 vo (5.10a) v i logarit t nhin (ln) sang logarit thp phn (lg), ta c:
k=
1
t1 2
ln 2 t1 2 =
0,6932 k
(5.11)
V d 12: ng v phng x ca 53I131 c dng trong cc nghin cu y hc v cha bnh bu c. Mt mu th ban u c 1,00mg 53I131. Sau 13,3 ngy lng it cn li l 0,32mg. Hy tnh thi gian na phn ng (chu k bn hy) ca it phng x. Tr li: Xc nh k da vo (5.10a)
1,00 1 N 1 m 1 k = ln 0 = ln 0 = ln t N t m 13,3 0,32
Tm t 1 da vo (5.11)
2
t1 2 =
0,6932.13,3 0,6932 0,6932 = = = 8,08 ngy 1,00 1 k 1,44 ln 13,3 0,32
Quy lut ng hc ca s phng x cn c ng dng nhiu trong khoa hc v i sng, nh xc nh nin i ca cc mu kho st, ca cc c vt da vo phn r phng x. V d 13: Mt mu cha 17,4 g U238 v 1,45g Pb206. Bit rng chu k bn hu ca U238 l 4,51.109 nm. Hy cho bit mu tn ti c bao nhiu nm? Tr li T mi lin h c bn: Ta c:
murran = mch .
Auran muran = Ach mch
AAuran 238 = 1,45. 1,68(g ) Ach 206
Vy khi lng uran ban u l: m(uran)u = 17,4 + 1,68 = 19,08 (g) T (5.11), xc nh c k:
0,6932 0,6932 -1 = = 0,1537.10 9 (nm ) 9 t1 2 4,51.10 nm 19,08 2,303 N 0 2,303 2,303 N 0 M: k = t = = 6,58.108 (nm) lg lg lg 9 k N 0,1537.10 nm 17,4 t N
k=
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Trong lnh vc kho c hc, mun xc nh nin i ca cc c vt ta da vo ng v phng x ca cacbon 14. ng v phng x cacbon 14 phn r theo phng trnh: Chu k bn hu ca C14 bng 5730 nm. Trong t nhin C14 c hnh thnh bng phn ng: V C14 c hnh thnh thng tng ca lp kh quyn theo mt vn tc khng i v li b phn hu theo mt vn tc khng i khc, do trong kh quyn lun c mt lng nh 14CO2 khng thay i. Thc vt s dng mt lng 14CO2 trong quang hp. V th cng c mt lng nh khng thay i 14C trong c th ng vt, thc vt. Khi ng vt, thc vt cht i lng14C ny thot dn ra ngoi nn lng 14C c trong c th cht s gim dn mt cch u n theo thi gian. Vy t lng 14C cn li trong xc ng vt, thc vt ta c th tnh c khong thi gian k t lc sinh vt ny cht i, tc l xc nh c khong thi gian hnh thnh di vt kho st. Ngi ta xc nh c: Trong kh quyn, trong mi c th ng thc vt ang sng, c 1 giy trong 1 gam cacbon c 15,3 phn hu ca 14C. Chu k bn hu ca 14C l 5730 nm. S phn hu 14C ti thi im l t l vi s ht nhn 14C c ti thi im (l N) Vy:
t= t1 2 t1 2 N R 1 N0 ln = ln 0 = ln 0 k N 0,6932 N 0,6932 R
7 14 6
C 14 N + 7
N 14 + 0 n1 6 C 14 +1 H 1
(5.12)
Trong : R0 = 15,3 phn hu 14C trong mt giy vi 1,0 gam cacbon. Bin i thch hp (5.12) ta c phng trnh xc nh thi gian t ca c vt hay ho thch ( cha 14C) l;
t= 5730 15,3 ln 0,6932 R
t = 19 ,0451 . lg
15 ,3 (nm) R
(5.13)
V d 14: Mt mu than ly c t hang ng ca ngi Plinexian c i ti Ha oai c vn tc phn hu 14C l 13,6 (tnh vi 1,0 gam cacbon trong 1 giy). Hy cho bit nin i ca mu than . Tr li T (5.13), tnh c:
t = 19,04581. lg 15,3 974 (nm) 13.6
Nh vy ngi Plinexian c Ha oai sng vo khong nhng nm 1034 sau cng nguyn tr v trc. f) Phng x nhn to Phng x nhn to l hin tng dng mt loi ht lm n bn vo ht nhn lm bia to ra ht nhn mi vi tia phng x c gi l hin tng phng x nhn to.
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V d 15: Dng ht (2He4) lm n bn vo cc bia, xy ra hin tng phng x nh sau: 10 4 14 7 N 13 + 0 n1 (5.14a) 5 B + 2 He [ 7 N ] Bia n 27 4 31 1 30 (5.14b) 13 Al + 2 He [15 P ] 15 P + 0 n 24 4 28 27 1 (5.14c) 12 Mg + 2 He [14 Si ] 14 Si + 0 n Cc ht nhn mi c to thnh [7 N 14 ] , [15 P 31 ], ... khng bn b phn hu tip:
7
N 14 7 N 13 + 0 n1 P 31 15 P 30 + 0 n1
15 14
Si 28 14 Si 27 + 0 n1
Cc phng trnh (5.14a, 5.14b, 5.14c) l cc qu trnh s cp. Tip theo l cc qu trnh th cp:
7
N 13 6 C 13 + + P 30 14 Si 30 + + Si 27 13 Al 27 + +
15 14
+ hay 0e+ l electron dng hay cn gi l ht posison l phn ht ca electron e-. Hin tng phng x ngy cng c nhiu ng dng trong thc tin v i 59 1 60 sng, nh: 27 Co + 0 n 27 Co
27
Co 60 28 Ni 60 + ;
h = 1,25MeV
MeV c l mega-electron Von; 1MeV = 10 6 eV
Bc x c nng lng cao, do c dng cha bnh ung th (thng ni l chiu x cacbon), chp nh, ... Nh vy, trong hin tng phng x nhn to thng bao gm qu trnh s cp v qu trnh th cp. Qu trnh s cp to ra nguyn t mi km bn, nguyn t mi ny l nguyn nhn to ra hin tng th cp. 5.2.4. i cng v phn ng ht nhn a) Khi nim Phn ng ht nhn l s tng tc gia ht nhn nguyn t vi cc ht to thnh nguyn t ca nguyn t mi. Phng trnh phn ng tng qut:
Bia + n [Ht nhn trung gian] sn phm
(5.15)
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82
V d 16: 7 N 14 + 2 He 4 [9 F 18 ] 8 O17 +1 H 1 (1 p1 ) + E (hv) (5.15) cn vit di dng :
Bia (n, ht to thnh) nguyn t mi (5.15a) 14 17 V d 16 cn c vit nh sau: 7 N ( , p) 8 O Hoc vit gn hn ch gm: n v ht to thnh b) Mt s phn ng thng gp Trong cc v d di y khi cp n phn ng ch nhc n n - Cc phn ng gy ra bi ht , hay gp cc phn ng
+ , p: V d trn + , n0:
4
Be 9 + 2 He 4
[ C ] C
13 6 6 19 18 3 9
12
+ 0 n1
- Cc phn ng gy ra bi ht p, hay gp cc phn ng

+ p, n:
8
O18 + 1 H1
+ p, : 3 Li 6 +1 H1
[ F ] F + n [ Be ] He + He
1 9 0 7 4 2 2
4 3 2 1 1
- Cc phn ng gy ra bi teri (1D2), thng gp

+ d, p: + d, n: + d, :
1
D 2 +1 D 2
2 2 1
6 2
[ He ] H (hay: T D + D [ He ] He + n Li + D [ Be ] 2 He
4 3 1 2 2 0
8 4 3 1 4 2
) +1 H 1
(*) (**)
Cc phn ng (*), (**) l c s thc hin phn ng nhit hch. Ch : Phn ng ht nhn cng ging nh bt c mt phn ng ha hc thng thng khc ch: Cc phn ng u tun theo nh lut bo ton in tch v nh lut bo ton khi lng (hay s khi). 5.2.5. S phn hch ht nhn (phn chia ht nhn) Xy ra trong bom nguyn t a) Khi nim Hin tng khi bn mt ht no (th d ht ) lm cho ht nhn b v ra lm 1 s mnh c gi l s phn hch ht nhn. Xem cc v d phn 5.2.3; 5.2.4 b) S phn hnh ht nhn dy chuyn Ngoi cc phn ng nu trn, phn ng phn hch ht nhn cn xy ra theo kiu phn ng dy chuyn.
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HNH 2.13. S minh ho phn ng phn hch ht nhn dy chuyn Nh vy, phn ng phn hch ht nhn dy chuyn l mt qu trnh bt u t s lng vi t ht lm n, sau c tip tc vi s lng tng ln (c th v hn hay v s hn). Cc ht lm n nn phn ng xy ra rt mnh, vn tc rt ln. l s phn hch ht nhn dy chuyn phn nhnh. V d 17: H2 + Cl2 2HCl l phn ng xy ra theo kiu dy chuyn. phn ng phn hch ht nhn xy ra cn: Nguyn liu ht nhn phi c tinh ch, ng thi phi tho mn iu kin v khi lng: V d vi U235 th cn khi lng khong: 900 1000g. Khi phn ng vi lng t 900 1000g xy ra s gii phng 1 nng lng gn bng 8,4.1013J. Tng ng vi sc cng ph ca 20.000 tn thuc n TNT. C 2 trng hp xy ra phn ng ht nhn dy chuyn: + iu khin c: l cc nh my in nguyn t. + Khng iu khin: l cc qu trnh xy ra trong bom nguyn t (bom A). 5.2.6. Phn ng nhit hch xy ra trong bom khinh kh (Bom H) a) Khi nim Phn ng nhit hch l qu trnh tng hp ht nhn, thng l cc ht nhn nh to thnh cc ht nhn nng hn m trong cc ht nhn c un nng ti nhit rt cao trc khi phn ng xy ra gi l phn ng tng hp ht nhn (phn ng nhit hch). cc ht nhn tin li c gn nhau v thng c lc y culng gia chng th nhit cn t c ti khong 108 K th phn ng nhit hch mi xy ra. iu ny c ngha l kp n ca bom khinh kh (bom H) phi l bom nguyn t (bomA). b) Mt s phn ng nhit hch thng gp
H 1 +1 H 3 2 He 4 2 3 4 1 1 D + 1 T 2 He + 0 n
1 3
H = 19,8Mev H = 17,6 Mev
Li 6 +1 D 2 2 2 He 4
H = 22,0 Mev
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gio trnh ho i cng
Ngi n ca bom H l bom A vi sc cng ph ca bom H ln gp vi ngn ln bom A. 6. NH LUT TUN HON V H THNG TUN HON CC NGUYN T HA HC 6.1. Sp xp tun hon cc nguyn t theo cu hnh electrron 6.1.1. Nguyn tc sp xp Xp cc nguyn t theo chiu tng ca s hiu nguyn t (Z). Xp cc nguyn t c cng s lp electron (cng s lng t chnh n) thnh tng hng gi l chu k. Xp cc nguyn t c cng cu hnh electron lp ngoi cng tng t nhau (c tnh cht ho hc ging nhau) thnh tng ct gi l nhm. Da vo mc nng lng ca cc AO (theo quy tc Klechkowski) vit c cu hnh electron tng qut cho tng hng t xc nh c chu k v s nguyn t trong chu k, bng 2.2: BNG 2.2. Cu hnh electron tng qut ca cc chu k
Chu k 1 2 3 4 5 6 7 Cu hnh electron tng qut 1s1- 2 2s1- 2 2p1- 6 3s1- 2 3p1-6 4s1- 2 3d1-10 4p1-6 5s
1- 2
Z 1, 2 3-10 11-18 19-36 37-54 55-86 87-105
S nguyn t trong mt chu k 2 8 8 18 18 32 19
4d
1-10
5p
1-6
6s1- 2 4f1-14 5d1-10 6p1-6 7s1- 2 5f1-14 6d1-3
6.1.2. nh lut tun hon Tnh cht ca cc nguyn t cng nh tnh cht ca cc n cht v hp cht c to nn t cc nguyn t bin thin tun hon theo chiu tng dn ca s in tch ht nhn (Z). C s ca s bin thin tun hon l do c s bin thin tun hon s e c in vo lp, phn lp ngoi cng theo chiu tng dn s hiu nguyn t (Z). 6.1.3. Bng h thng tun hon cc nguyn t ho hc C 92 nguyn t trong thin nhin, t hiro (Z = 1), n uran (Z = 92) v c trn 10 nguyn t nhn to (hin nay nguyn t th 118 c nu ra trong mt s ti liu). Cc nguyn t ny c xp trong bng h thng tun hon. Bng cu to gm:
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gio trnh ho i cng
a) (hay s th t ca nguyn t) Mi nguyn t ho hc c xp vo mt trong bng h thng tun hon.
HNH 2.14. Minh ho mt gm 4 ni dung thng c trong bng h thng tun hon cc nguyn t Mt cho bit: + S hiu nguyn t ca nguyn t (chnh l s th t ca trong bng tun hon) S th t ca nguyn t ng bng s n v in tch dng ht nhn Z ca nguyn t nguyn t . S th t cng chnh l s electron c trong nguyn t ca nguyn t . + K hiu ca nguyn t, tn ca nguyn t ho hc. + Khi lng nguyn t trung bnh ca nguyn t ho hc. + S electron mi lp trong v nguyn t ca nguyn t. Bn ni dung va nu thng c th hin trong mt , c minh ho hnh 2.14. Mt s trng hp cn cho bit thm mt s thng tin sau: - Tnh cht ho hc ca nguyn t (c th hin thng qua mu sc). - Dng tinh th ca n cht c to ra t cc nguyn t . b) Chu k c xp thnh hng ngang theo chiu tng dn ca s n v in tch ht nhn Z, bt u bng kim loi kim (ns1) v kt thc bng kh him (np6). Ni cch khc: Chu k l tp hp cc nguyn t c cng s lp electron. S th t ca chu k bng s lp electrron v bng s lng t chnh n. V d 1: Chu k 3 gm cc nguyn t 11Na (kim loi kim) 12Mg 13Al 14Si 15P 16S 17Cl 18Ar (Kh him) Bng tun hon hin nay c 7 chu k, c chia thnh 3 loi: Chu k 1: chu k c bit, ch c 2 nguyn t 1H v 2He. Chu k 2, 3: c gi l chu k nh (ch c cc nguyn t h s v h p), mi chu k gm 8 nguyn t. Chu k 4, 5, 6: c gi l chu k ln gm cc nguyn t h s, p, d, f. + Chu k 4, 5 mi chu k gm 18 nguyn t (ch c cc nguyn t h s, p,d). + Chu k 6 c 32 nguyn t (gm cc nguynt h s, p, d, f). + Cn chu k 7 hin nay cha hon thnh. Nu chu k 7 hon thnh cng phi gm 32 nguyn t, ging nh chu k 6.
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gio trnh ho i cng
c) Nhm Nhm l tp hp cc nguyn t c xp theo ct dc v theo chiu tng dn ca s n v in tch ht nhn Z (t trn xung), c cng s e lp ngoi cng nn c cng s oxy ho dng cao nht vi oxi. Ni cch khc: Nhm gm nhng nguyn t c cu hnh e lp ngoi cng tng t nhau, do c tnh cht ho hc ging nhau. Hay: Nhm l tp hp cc nguyn t c cng ho tr C mt s quan im v phn loi nhm nguyn t. Theo dng bng ngn th bng H thng tun hon c chia thnh 8 nhm A, mi nhm gm 1 ct v c nh s th t t IA n VIIIA v c 8 nhm B cng c nh s t IB n VIIIB, mi nhm B cng gm 1 ct (tr nhm VIIIB gm 3 ct to thnh). Trong cch phn chia ny th kh him c chn lm nhm VIIIA. Bng tun hon dng ngn cng c th chia thnh 9 nhm, t nhm I n nhm VIII c nhm A v B ging nh trn, nhng khc trn ch nhm 9 c gi l nhm s 0 (ch cha kh him). Theo quan im ny th cc nguyn t thuc nhm A c gi l phn nhm chnh (Nhm A ch cha cc nguyn t h s v h p). Cn cc nguyn t thuc nhm B c gi l phn nhm ph. Chu k c th xp thnh 1 hng hoc 2 hng (nu xp thnh 2 hng th c nh s th t theo hng chn, hng l). C mt quan im khc v xp cc nguyn t trong bng h thng tun hon ch mi chu k ch xp thnh 1 hng (k c chu k ln v chu k nh). Khi ny nhm (k c nhm A v nhm B) gm cc nguyn t c s electron ho tr dng cao nht bng nhau v bng s th t ca nhm. V d 2: Xt cc hp cht ca mi nguyn t chu k 2, chu k 3 vi H, Cl. T hy nu nhn xt v ho tr ca c nguyn t trong hai chu k trn theo nhm. Tr li Hp cht vi hiro (hirua): BH3 CH4 NH3 H2O HF LiH BeH2 NaH MgH2 AlH3 SiH4 PH3 H2S HCl Hp cht vi clo (clorua) BCl3 CCl4 NCl3 OCl2 FCl LiCl BeCl2 NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl2 Cl2 T kt qu bi tp p dng trn, c bng 2.3 Theo quan nim v kh him, coi cc nguyn t nhm ny c ho tr 0, v nguyn t ca chng u c 8e lp ngoi cng (ring He c 2e) T bng 2.3 ta thy cc nguyn t trong cng mt phn nhm chnh c cng ho tr.
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gio trnh ho i cng
BNG 2.3. Ho tr ca cc nguyn t thuc phn nhm chnh

Nhm Mt s nguyn t Ha tr 1 (H) Li Na 1 Be Mg 2 B Al 3 C Si 4 N P 3 O S 2 Cl F 1 2 3 4 5 6 7 8 (He) Ne Ar (0)
6.1.4. Cc h nguyn t ho hc Electron cui cng ca nguyn t c in vo phn lp no ca cu hnh electron th thuc h nguyn t ho hc . V d 3: Nguyn t ca nguyn t Na c cu hnh electron: 1s2 2s22p6 3s1 ta thy electron cui cng (electron s 11c k hiu l e11) c in vo phn lp 3s. Vy Na thuc h s Tng t, cu hnh electron nguyn t ca nguyn t Cl:1s2 2s22p6 3s23p5 electron cui cng ( electron s 17 k hiu l e17) in vo phn lp 3p. Nguyn t Cl thuc h p Da vo s electron in vo mt phn lp xc nh c s h nguyn t ho hc: + H s: C cu hnh electron tng qut l ns12, c ti a 2 electron in vo phn lp s nn c hai nhm nguyn t h s: Nhm c cu hnh electron tng qut ns1 l cc nguyn t kim loi kim; Nhm c cu hnh electron tng qut ns2 l cc nguyn t kim loi kim th. + H p: C cu hnh electron tng qut l ns2np16 c ti a 6 electron in vo phn lp p, nn c 6 nhm nguyn t h p: Nhm c cu hnh electron tng qut ns2np5l cc nguyn t halogen, nhm c cu hnh electron tng qut ns2np4 l cc nguyn t nhm VIA- nhm oxi-lu hunh, ... Nh vy: - C 2 h s, 6 h p tng ng vi 8 nhm (k c nhm kh him) - Cc nguyn t h s, h p u thucnhm A (phn nhm chnh), cc nguyn t ny l kim loi hoc phi kim . + H d: C cu hnh electron tng qut l (n - 1)d110ns2 (hoc (n 1)d110ns1 vi cc nguyn t c cu hnh electron c bit nh 24Cr, 29Cu, ...), c ti a 10 electron in vo phn lp d, t chu k 4 mi c cc nguyn t h d, mi chu k c 10 nguyn t h d, c xp vo nhm B (phn nhm ph), c 8 nhm B c nh s th t t IB VIIIB. Mi nhm l 1 ct, ring nhm VIIIB c 3 ct ng, v cc nguyn t nhm VIIIB tnh cht ging nhau c hng ngang v hng ng. Cn nh: Cc nguyn t h d l kim loi cn gi l cc nguyn t kim loi chuyn tip. + H f: Gm 2 h nguyn t
88
gio trnh ho i cng
- H Latan: c xp vo cng vi ca latan ( 57) v t ngoi bng theo hng ngang gm 14 nguyn t, vi s in e vo A0-4f. - H Actini: c xp vo cng vi ca actini ( 89) v t ngoi bng theo hng ngang gm 14 nguyn t, vi s in e vo A0-5f. * Mun xc nh v tr, tnh cht ca mt nguyn t trong h thng tun hon cn tin hnh theo cc bc sau: + T s hiu nguyn t (Z) vit cu hnh electron. + Da vo cu hnh electron xc nh v tr trong h thng tun hon: - Xc nh chu k: Cn c vo s lng t chnh ln nht c trong cu hnh electron. - Xc nh nhm: Phi xc nh c nguyn t thuc h no, t mi xc nh c v tr trong nhm. + Cc nguyn t h s, p thuc nhm A: V tr ca nhm bng s electron lp ngoi cng. + Cc nguyn t h d thuc nhm B: V tr c xc nh da vo bng 2.4 BNG 2.4. V tr cc nguyn t h d c cu hnh electron tng qut (n - 1)dxnsy
Nhm x+y IIIB 3 IVB 4 VB 5 VIB 6 VIIB 7
VIIIB 13 2
IB 11
IIB 12
8;9;10
+ Mun xc nh tnh cht ca cc nguyn t cn c vo s electron lp ngoi cng. V d 3: T cu hnh electron ca Na v Cl v d 18, bit c: - Na v Cl u thuc chu k 3 ( v n = 3) - Na v Cl u thuc nhm A ( v Na thuc h s, Cl h p). Na nm nhm IA (c 1e lp ngoi cng), Cl nm nhm VIIA (c 7e lp ngoi cng). - Na l kim loi (c 1e lp ngoi cng). C tnh kh mnh: Na - 1e Na+ C th: 2Na + 2HCl 2NaCl + H2 2Na + Cl2 2NaCl - Cl l phi kim (c 7e lp ngoi cng). C tnh oxi ho mnh: Cl + 1e ClC th: Mg + Cl2 MgCl2 2FeCl2 + Cl2 2FeCl3 V d 4: Fe c s hiu nguyn t l 26. Hy xc nh: V tr ca Fe trong bng h thng tun hon, ho tr, tnh cht ho hc ca Fe. Tr li Fe (Z = 20), c cu hnh electron: 1s2 2s22p6 3s23p63d6 4s2 V tr trong h thng tun hon: + Chu k : 4 (n = 4) + Nhm VIIIB: v Fe l nguyn t h d, c x + y = 6 + 2 + 8
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gio trnh ho i cng
Fe c ho tr II v c 2e lp ngoi cng. Fe cn c ho tr 3,4,...,8. Thng gp l ho tr II v III. Hin nay tng hp c hp cht ca Fe c ho tr VI. Tnh cht ho hc ca Fe, tnh kh: Fe - 2e Fe2+ Fe - 3e Fe3+ Cc bn sinh vin t ly v d minh ho cho tnh cht ho hc ca Fe. Ch : Khng ly v d cho cc nguyn t h latan v h Actini (cc nguyn t ngoi bng) 6.2. S bin i tun hon mt s tnh cht ca cc nguyn t V s electron ngoi cng bin i tun hon theo chiu tng ca s n v in tch ht nhn Z, nn tnh cht ho hc ca cc nguyn t c quyt nh bi s electrron lp ngoi cng. Tnh cht ca cc nguyn t c chia thnh 2 nhm; + Nhm 1: L nhng tnh cht bin i tun hon, nhm ny tnh cht ph thuc trc tip vo cu hnh e ca nguyn t (tc l ph thuc vo s e ca lp ngoi cng). + Nhm 2: L nhng tnh cht bin i khng tun hon, nhm ny ph thuc n iu vo s n v in tch ht nhn Z. Nhng tnh cht thuc nhm 2 khng nhiu nh s bin i s sng ca quang ph tia X, nhit dung nguyn t, khi lng nguyn t, khi lng ring, ... 6.2.1.Tnh cht ho hc a) Tnh cht ho hc * Kim loi: L nhng nguyn t m nguyn t ca chng nhng electron ho tr trong cc phn ng ho hc tr thnh ion dng Ch : Nguyn t kim loi khng th thu thm electron tr thnh ion m. K hiu kim koi l M, ta c: M - 1e Mn+ ; (n = 1 3) V d 5: Na -1e Na+ Mg -2e Mg2+ Al - 3e Al3+ Nguyn t ca nguyn t M cng d nhng electron ha tr tr thnh ion dng, nguyn t M cng c tnh kim loi mnh. * Phi kim: L nhng nguyn t m nguyn t ca chng thu thm electron vo lp ngoi cng khi tham gia phn ng ha hc tr thnh ion m Nu k hiu phi kim l X, ta c: X + me Xm-; (m hu ht bng 1) V d 6:
1 Cl 2 + e Cl 2
.... .... .... .... .... Nguyn t ca nguyn t X cng d nhn electron vo lp ngoi cng, nguyn t cng c tnh phi kim mnh. b) Quy lut bin thin trong h thng tun hon
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* Trong chu k: Theo chiu tng dn ca s n v in tch dng ht nhn Z (theo chiu t tri sang phi ca chu k), tnh kim loi gim, tnh phi kim tng. V d 7: Ch r s bin thin tnh cht ha hc ca cc nguyn t trong chu k 3, chu k 4 minh ha quy lut v s bin i tnh cht ca cc nguyn t trong chu k. Hy so snh mc bin i tnh cht ca chu k 3 v chu k 4. Tr li BNG 2.5. Tnh cht ca cc nguyn t chu k 3
Nguyn t Tnhcht
11Na 12Mg 13Al 14Si 15P 16S 17Cl 18Ar
Kim loi in hnh
Kim loi mnh
Kim loi hot ng
Phi kim rt yu
... ... ...
Phi kim trung bnh
phi kim in hnh
kh him
Bng 2.6. Tnh cht ca cc nguyn t chu k 4

Nguyn t Ynh cht
19K 20Ca 21Sc......30Zn 31Ga 32Ge 35Br 36Kr
Kim loi in hnh
Kim loi mnh
Kim loi chuyn tip
Kim loi
Phi kim rt yu
Phi kim in hnh
Kh him
T cc thng tin a ra bng 2.5 v 2.6: Nhn thy s bin i tnh cht ca cc nguyn t trong mi chu k trn ph hp vi quy lut chung. So snh hai bng ta thy s bin i trong chu k 4 xy ra chm hn so vi trong chu k 3, l do chu k 4 xut hin 10 nguyn t chuyn tip h d ( t 21Sc 30Zn) chuyn t kim loi sang phi kim: + Chu k 3 ch qua 3 nguyn t, t 12Mg n 14Si. + Chu k 4 phi qua 13 nguyn t, t 20Ca n 32Ge. * Trong phn nhm chnh Theo chiu tng ca s n v in tch dng ca ht nhn (t trn xung), tnh kim loi tng, tnh phi kim gim. V d 8: T s bin i tnh cht ca hiroxit ca cc nguyn t nhm IIA, chng minh quy lut bin thin tnh cht ca cc nguyn t trong nhm, Tr li Cc hiroxit ca cc nguyn t nhm 2 u c cng thc chung M(OH)2. Be(OH)2 axit yu Mg(OH)2 Kt ta () Ca(OH)2 t tan
Tnh baz tng 91
4Be 20Ca 12Mg
Tnh kim loi
gio trnh ho i cng
Sr(OH)2 Ba(OH)2
tan mnh tan mmh
56Ba
38Sr
tng
HNH 6.2. Quy lut bin i tnh baz ca cc M(OH)2 Quy lut bin i tnh cht ca cc hiroxit v tnh cht ca cc nguyn t trong nhm IIA, hnh 6.2 6.2.2. Bn knh cng ha tr ca nguyn t a) Khi nim Bn knh cng ha tr ca mt nguyn t c xc nh bng na di lin kt cng ha tr n gia hai nguyn t cng loi. V d 9: di ca lin kt cng ha tr n trong H2 l 0,74 A0, bn knh cng ha tr ca H l:
rH = d H H 0,74 A0 = = 0,37 A0 2 2
Vi kim loi: c xc nh bng 1/2 di ca khong cch ngn nht gia 2 nguyn t trong tinh th kim loi.
rLi = d Li Li 3,10 A 0 = = 1,55 A0 2 2
T s liu ca bng 2.7 cho thy r quy lut biu th mi lin h gia bn knh cng ha tr vi v tr ca nguyn t trong bng h thng tun hon. b) Quy lut bin thin trong h thng tun hon * Trong chu k Trong chu k khi s hiu nguyn t (Z) tng th bn knh cng ho tr(r) gim v Z tng th in tch hiu dng (Z*) tng, lc ht ca ht nhn n e lp ngoi cng tng. BNG 2.7. Bn knh cng ha tr ca mt s nguyn t (tnh theo A0)
Nhm Chu k 1 Chu k 2 Chu k 3 Chu k 4 Chu k 5 I H 0,37 Li 1,55 Na 1,90 K 2,35 Rb 2,48 Be 1,12 Mg 1,60 Ca 1,97 Sr 2,15 B 0,98 Al 1,43 Ga 1,41 In 1,66 C 0,91 Si 1,32 Ge 1,37 Sn 1,62 N 0,92 P 1,28 As 1,39 Sb 1,59 O 0,66 S 1,27 Se 1,40 Te 1,60 F 0,64 Cl 0,99 Br 1,14 I 1,33 Ne Ar Kr 1,11 Xe 1,30 II III IV V VI VII VIII
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* Trong phn nhm chnh Trong phn nhm chnh (nhm A) theo chiu tng dn ca Z (t trn xung) th bn knh cng ha tr tng do c s tng s lp electron. 6.2.2. Nng lng ion ha I (eV) a) Khi nim Nng lng ion ha th nht I1 ca mt nguyn t l nng lng cn thit tch mt electron ra khi nguyn t t do th kh trng thi c bn. Nu nguyn t c t 2 electron tr ln th ta c I1, I2, I3,.... Nng lng ion ha I2 l nng lng cn thit tch e th hai ra khi cation mi c to thnh. V d 10:
Li( k ) Li + + 1e; I1 = 5,39(eV ) I 2 > I1 2+ + Li Li + 1e; I 2 = 75,62(eV ) + H H + 1e; I1 = I H = E1 = (13,6) = 13,6(eV )
V d 11: Vi E1 l nng lng lin kt ca electron trong nguyn t hiro trng thi c bn. T v d 10, thy rng nng lng ion ho I1 chnh bng nng lng lin kt ca electron vi ht nhn nhng ngc du Ch : Thng dng n v eV tnh cho mt nguyn t, dng n v kcal/mol tnh cho 1mol nguyn t. Dng php i n v: 1 kcal = 2,62.1022 eV, ta c:
1eV = 1kcal 2,62.10 22
Thay gi tr ny vo nng lng ion ho I1 ca Li, c:

5,39.1kcal / nguy n t .6,022.10 23 nguy nt / mol I1 ( Li ) = = 123,88(kcal / mol ) 2,62.10 22 I 2 ( Li ) = 75,62.kcal / ion.6,022.10 23 ion / mol = 1738,12 kcal / mol 2,62.10 22
b) Quy lut bin thin trong h thng tun hon BNG 2.8. Nng lng ion ho th nht I1(kcal/mol)
NhM Chu k 1 Chu k 2 Chu k 3 Chu k 4 Chu k 5 I H 313 Li 124 Na 119 Be 215 B 191 Mg 176 C 260 N 336 O 314 P 254 S 239 Se 225 F 402 Cl 300 Br 273 I 241 II III IV V VI VII VIII He 567 Ne 497 Ar 363 Kr 323 Xe 280
Al 138 Si 188
K 100 Ca 142 Ga 138 Rb 96 Sr 131
Ge 187 As 231
In 152 Sn 169
Sb 199 Te 208
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T s liu ca bng 2.8 cho thy quy lut sau: * Trong chu k Trong mt chu k theo chiu tng in tch ht nhn Z nng lng ion ho I1 tng. * Trong phn nhm chnh Trong mt phn nhm chnh i t trn xung di nng lng ion ho I1 gim. V d 12: Hy ch ra v gii thch cc trng hp tri quy lut ca s liu trong bng 2.8. Tr li C cc trng hp tri quy lut xy ra trong bng 2.8: Chu k 2: Be (215), B (191) v N (336), O (314) Chu k 3: Mg (176), Al (138) v P (254), S (239) Nguyn nhn l do cu hnh electron ca nguyn t c xt Xt Be v B: Be: 1s2 2s2 v ho tr 2s2 , biu din bng lng t B: 1s2 2s22p1 v ho tr 2p1, ch c 1e c thn Vy s tch 1e ca B tn t nng lng hn ca Be, kt qu I1(Be) > I1(B) mc d B ng sau Be trong chu k 2. Bng cch l gii tng t, cc bn sinh vin hy t gii thch cho cc trng hp cn li. c) Cc yu t nh hng n nng lng ion ha Nng lng ion ha ca mt nguyn t v tr s bng nng lng ca electron xa ht nhn nht (lin kt yu nht vi ht nhn) nhng ngc du.
Z 2 2 2 me 4 I = -E = 2 . n h2
Trong : Z l in tch ht nhn nguyn t. n l s lng t chnh. h l hng s planck. m, e l khi lng v in tch ca electron. T biu thc trn thy rng nu nguyn t ch gm c 1e v 1 ht nhn th nng lng ion ha ch ph thuc vo s in tch ht nhn Z v s lng t chnh n. Nu nguyn t gm nhiu e th nng lng ion ha cn ph thuc vo hiu ng chn (b) v hiu ng xm nhp. Hiu ng chn: Trong : (Z - b) = Z* c gi l in tch hiu dng; n* c gi l s lng t chnh hiu dng. phng trnh ny b ph thuc vo s e, nu s e cng nhiu th b cng ln th Z*=(Z - b) cng nh. Cc e cc phn lp khc nhau th c mc chn cng khc nhau, cc e cc lp bn trong chn mnh hn cc e cng lp,
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gio trnh ho i cng
trong cng mt lp th cc es chn mnh hn cc ep, cc ep chn mnh hn cc ed (xem chi tit phn quy tc Slater). Hiu ng xm nhp: Theo c hc lng t mt e c th bt k ch no trong khng gian xung quanh ht nhn nguyn t. Tt c cc e, k c e ngoi cng, v th c th ni rng cc e bn ngoi xm nhp qua cc lp bn trong vo gn ht nhn. S xm nhp ny lm cho bn lin kt gia e bn ngoi v ht nhn tng ln. Trong cng mt lp th mc xm nhp ca es l ln nht v ef l yu nht. 6.2.3. i lc electron (Rt kh xc nh c chnh xc bng thc nghim) a) Khi nim i lc electron l nng lng km theo qu trnh khi mt nguyn t t do trng thi c bn thu mt electron tr thnh ion m. K hiu i lc electron l E. S tng qut l: X kh + e X kh ; E Vic i lc electron l nng lng cn cung cp (E > 0) hoc c gii phng (E < 0) ph thuc vo cu hnh e ca nguyn t khi nhn e. Vic E > 0 hay E < 0 hon ton ph thuc vo ion c to ra cu hnh ca n bn hay khng bn. Khi to ra mt anion bn, qu trnh gii phng ra mt nng lng. V d 13: F + 1e F- (ion bn) E1 = -328 KJ/mol (pht E) Nng lng cng m th kh nng nhn e ca X cng mnh v X s c tnh cht phi kim hay tnh oxi ho cng ln. Khi to ra mt anion khng bn, qu trnh cn cung cp nng lng. V d 14: Be + 1e Be- (ion khng bn) E1 = 241KJ/mol (thu E) Ch : Quy c v du c dng y ph hp vi quy c v du ca nhit ng lc hc khi p dng cho h ang xt: + Nng lng cn gii phng c du - (m) + Nng lngcn cung cp c du dng + (dng) i lc e kh c xc nh v khi nguyn t thu thm e th xut hin hiu ng y nhau gia cc e, do tc dng ca hiu ng ny m cc h thu c km bn. V vy, trong thc t cc h c in tch -2, -3 hu nh khng tn ti ( th kh). V d nh khng tn ti ion O2- (kh) m ch tn ti ion OH-(trong dung dch) tc l ion O2- phi kt hp vi ion H+ thnh OH- mi bn c. V th, xc nh i lc vi e bng con ng gin tip thng qua vic xt chu trnh Boocn-Hab.
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gio trnh ho i cng
b) Quy lut bin thin trong h thng tun hon BNG 2.9. i lc vi electron (theo kcal/mol)ca 20 nguyn t u trong bng h thng tun hon
Nhm Chu k 1 H -17,22 Chu k 2 Li -2,03 Chu k 3 Na -8,72 Chu k 4 K -7,18 Be +50,10 Mg +50,79 Ca +43,65 B -4,61 Al -7,29 Ga C -28,82 Si -45,60 Ge N +2,31 P -16,14 As O -33,89 S -47,73 Se F -79,55 Cl -83,24 Br I II III IV V VI VII VIII He +2,20 Ne +6,93 Ar +5,86 Kr -
T cc s liu ca bng 2.9 nhn thy: Du i s ca i lc vi electron E lin quan mt thit n cu hnh electron ca nguyn t. Cc nguyn t ca cc nguyn t c cu hnh electron hay phn lp ngoi bo ha kh thu thm electron nn c i lc eletron dng. Cn nguyn t c cu hnh electron hay phn lp ngoi cha bo ho, d thu thm electron nn c i lc electron m. * Trong chu k Trong chu k khi s in tch ht nhn nguyn t tng th i lc vi electron tng (tc l i lc vi cc e ngy cng m) * Trong phn nhm chnh Trong phn nhm khi s in tch ht nhn nguyn t tng th i lc vi e gim (i lc c gi tr km m hn). E2 > 0 Ch : X- + 1e X2V qu trnh ny lun thu nhit do lc y nhau gia e vi ion m vt qu lc ht ca ht nhn. 6.2.4. m in ( : khi) a)Khi nim m in l kh nng ca nguyn t trong phn t ht e v pha nguyn t . Hay: m in ca mt nguyn t trong phn t l kh nng ca nguyn t ht cc electron ca mt lin kt v pha nguyn t . Tr s m in cho bit kh nng ht e ca nguyn t trong phn t l mnh hay yu. V d F = 4 , H = 2,1 cho thy flo ht e (ca cp e lin kt) trong phn t HF mnh hn hidro. b) Thang m in ca Pauling c xy dng da trn cc d kin thc nghim khi xt nng lng phn li lin kt gia 2 nguyn t trong phn t AB. T , Pauling a ra biu thc sau:
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gio trnh ho i cng
= A B = 0,208
Trong :
= D A B
1 [D A A + DBB ] 2
D l nng lng phn li lin kt AA, BB, AB l lin kt gia hai nguyn t tng ng. 0,208 l h s chuyn nng lng lin kt D biu th theo kcal/mol sang thang khng c n v (theo m in). Nu nng lng c tnh theo kJ/mol th dng h s 0,102. V bit c D nn v phi ca h thc hon ton xc nh c. Phng trnh trn l phng trnh bc nht hai n. Mun gii th phi tm c mt phng trnh na. Nhng Pauling ch a ra c mt phng trnh, v vy xc nh c tr s ca m in th phi quy c mt nguyn t A hoc B bit m in, v th thang m in ca Pauling l thang tng i, khng c n v. Pauling chn m in ca F ln nht lm chun, quy c F = 4,0 . T tnh c m in ca cc nguyn t khc v lp thnh bng m in ca cc nguyn t, bng 2.10. BNG 2.10. m in ca cc nguyn t phn nhm chnh
Nhm I H 2,1 Li 1,0 Na 0,9 K 0,8 Rb 0,8 Nhm II Be Mg Ca Sr 1,5 1,2 1,0 1,0 Nhm III B 2,0 Al 1,5 Ga 1,6 In 1,5 Nhm IV C 2,5 Si 1,8 Ge 1,8 Sn 1,7 Nhm V N P As Sb 3,0 2,1 2,0 1,8 Nhm VI O S Se Te 3,5 2,5 2,4 2,0 Nhm VIII He F 4,0 Ne Cl 3,0 Ar Br 2,8 Kr 3,1 I 2,2 Xe 2,4 Nhm VII
T bng 2.10, rt ra quy lut sau: * trong mt chu k Trong mt chu k khi in tch ht nhn nguyn t tng th m in tng * Trong mt phn nhm chnh Trong phn nhm chnh khi in tch ht nhn nguyn t tng th m in gim. Thang m in ca Pauling dng : Xc nh % c tnh ion ca lin kt ho hc, xc nh bn ca lin kt v s phn b mt electron trong phn t. Theo quy c, khi 2 nguyn t A v B lin kt vi nhau to thnh phn t AB m hiu m in : = A B > 1,7 : Lin kt gia A v B l lin kt ion. 0 < = A B < 1,7 : Lin kt gia A v B l lin kt cng ho tr phn cc. = A B = 0 : Lin kt gia A v B l lin kt cng ho tr phn cc khng phn cc.
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= A B cng ln th lin kt gia AB cng bn nn phn ng
to thnh AB to nhit cng ln v ngc li. H2 + F2 2HF H = - 128Kcal/mol H2 + Cl2 2HCl H = - 44Kcal/mol H2 + Br2 2HBr H = - 25Kcal/mol H2 + I2 2HI H > 0 Qua cc s liu ny, ta thy bn nhit gim dn t HF n HI C. H THNG BI TP I. Bi tp t lun (c li gii v khng c li gii) I.1. Bi tp c li gii Bi 1. Trong quang ph pht x ca nguyn t hiro, bc sng tia Hl 4861A0. a) Hy xc nh tn s sng (s-1) v s sng (cm-1) b) Tnh nng lng bc x , khi lng ht photon m, cho c = 3.108 m/s; h = 6,62.10-34Js Li gii Gia , c, v c cc mi lin h sau
3.108 cm.s 1 = = = 6,17.10 14 s 1 10 4861.10 cm c
= =
=
1 = 20571,9cm 1 4861.10 10 cm
hc
= h = 6,62.10 34 Js.6,17.10 14 s 1 = 4,08.10 19 J
h h 6,62.10 34 Js m= = = 4,54.10 36 J .s 2 .m 2 = 10 8 1 c 4861.10 m.3.10 m.s mc 36 = 4,54.10 kg.m 2 .s 2 .s 2 .m 2 = 4,54.10 36 kg
Ch : Khi lm bi tp cn quan tm ti mi quan h gia cc n v. Khi tnh khi lng m ta c php i n v: 1J = kg.m2.s-2 Bi 2. Khi chiu chm nh sng n sc vo b mt kim loi kali (K) vi bc sng = 4861A0 th electron b bt ra khi kim loi v chuyn ng vi vn tc v. Hy xc nh vn tc . Bit tn s ngng quang in ca K l 5,5.1014 s-1 Cho h = 6,62.10-34Js; c = 3.108m/s; me = 9,1.10-31 kg Li gii Trc tin cn tnh nng lng ca nh sng p vo b mt kim loi K
=
h
Mun khng nh hiu ng quang in xy ra ta cn kim tra nng lng ?0 ng vi ngng quang in
0 = h = 6,62.10-34Js.5,5.1014 = 3,641.10-19J
hc
6,62.10 34 Js.3.108 m.s 1 = 4,0856.10 19 J 4861.10 10 m
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gio trnh ho i cng
Vy > 0 chng t hiu ng quang in xy ra. Khi electron bt ra khi b mt kim loi K v chuyn ng vi ng nng Theo Anhxtanh: = 0 + T T = mv2/2 = - 0. T , ta c:
v=
2( 0 ) = m
2(4,085 3,614).10 19 J = 9,1.10 31 kg
2(4,085 3,614).10 19 kg.m 2 .s 2 = 9,1.10 31 kg
Bi 3. Mt electron chuyn ng vi vn tc v trong mt in trng c hiu in th U = 10 kV. Hy: a) Xc nh vn tc chuyn ng ca electron. b) Tnh bc sng ra A0 Cho h = 6,62.10-34Js; me = 9,1.10-31kg; q = 1,6.10-19C Li gii Khi electron chuyn ng trong in trng s c ng nng T cn bng vi nng lng in:
mv 2 T= = q.U 2
2qU 2.1,6.10 19 C.10 4 V 2.1,6.10 19 C.10 4 J = = = m 9,1.10 31 kg 9,1.10 31 kg.C 2.1,6.10 19.10 4 kg. 9,1kg m2 s 2 = 5,93.10 7 m.s 1
v=
a)
=
b)
=
h 6,62.10 Js = = = 0,122.10 10 m = 0,122 A0 m m mv 9,1.10 31 kg.5,93.10 7 9,1.10 31 kg.5,93.10 7 s s
34
6,62.10 34 kg
m2 s s2
Bi 4. S hp th nh sng ion ha nguyn t X cn mt nng lng l 3,44.10-18J. Hy xc nh bc sng (A0) ca nh sng hp th khi electron bt ra v chuyn ng vi vn tc v = 1,02.106 m/s. Li gii Khi nh sng p vo nguyn t X electron bt ra th nng lng cn dng chnh l nng lng ion ha I. Vy:
= 0 + T hay h = I +
=
mv 2 2
hc 6,62.10 34 3.108 = = 5,06.10 8 m = 506.10 10 m = 506 A0 mv 2 3,44.10 18 + 0,5.9,1.10 31.(1,03.10 6 ) 2 I+ 2
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Bi 5. Hy xc nh nng lng photon v nng lng mol photon i vi bc x ca cc bc sng tng ng sau: 600 nm (); 550 nm (vng); 400 nm (xanh da tri); 200 nm (tm); 0,150 nm (tia X) v 1cm (vi sng). Cho: h = 6,62.10-34Js; c = 3.108m/s; NA = 6,02.1023 mol-1. Li gii Gi nng lng ca photon l E, ca 1 mol photon l EA, ta c:
E = h = hc
; E A = N A .E = N A
hc
Tnh: hc = 6,62.10-34Js.3.108m/s = 1,986.10-25 J.m

NA.hc = 6,02.1023. 1,986.10-25 = 0,1196 J.m.mol-1 Vy E =
1,986.10 25 0,1196
v E A =
Kt qu tnh c a ra bng sau

(nm) E (J) EA (kJ/mol) 600 3,31.10-19 199,3 550 3,61.10-19 217,5 400 3,97.10-19 299,0 200 3,93.10-19 598,0 0,150 1,32.10-15 7,98.108 1,0 (cm) 1,99.10-23 0,012
Bi 6. a) Cho bit electron c khi lng me = 9,1.10-31kg, chuyn ng vi vn tc 2,2.106 m/s. Xc nh bc sng chuyn ng ca electron. b) Gi s mt qu bng c khi lng 1 kg, chuyn ng vi vn tc 3 m/s. Xc nh bc sng chuyn ng ca qu bng. c) T kt qu thu c, rt ra nhn xt v s chuyn ng ca ht vi m v v m? Li gi p dng h thc Bri = a) Electron:
h , cho: mv h 6,625.10 34 = = 3.3.10 10 m = 3,3 A0 = 31 6 mv 9,1.10 .2,2.10 h 6,625.10 34 = = 6,625.10 37 m = 6,625.10 37 A0 3 1.10 mv
b) Qu bng: =
c) Nhn xt: T kt qu ca cu a, ta thy bc sng chuyn ng ca electron l tng i ng k so vi kch thc ca nguyn t. Cn cu b, bc sng chuyn ng ca qu bng (vt th v m) v cng nh so vi kch thc ca n. V vy chuyn ng ca vt th v m khng c tnh cht sng, nn khng th m t c bng c hc lng t m tun theo c hc c in ca Niutn. Bi 7: a) Gi s khi electron chuyn ng, vn tc ca n xc nh chnh xc n m/s. Hy tnh sai s ta ca electron trong chuyn ng.
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b) Mt vt c khi lng 1 kg chuyn ng vi sai s vn tc l 0,1 m/s. Tnh sai s ta ca vt trong chuyn ng. T cc kt qu thu c hy rt ra nhn xt. Li gii
h 6,62.10 34 a) q = = = 1,2.10 4 (m) 31 2m.v 9,1.10 .2.3,14.1
b) q =
h 6,62.10 34 = = 1,55.10 33 (m) 2m.v 2.3,14.1.0,1
T kt qu cu (a), nhn thy q ln hn rt nhiu so vi bn knh nguyn t, v vy electron s ri ra ngoi trng lc ht ca ht nhn nguyn t. iu ny khng th xy ra c v khi h nguyn t s khng cn tn ti. Tc l sai s vn tc n 1m/s l khng c. Kt qu cu (b), cho thy sai s v ta ca vt th trong chuyn ng ca vt l rt nh. Nn vic xc nh ng thi c ta ln vn tc c chnh xc rt cao. Bi 8: Mt s vch ph ca nguyn t H nm trong vng UV c c trng bng nhng bc chuyn t cc mc L, M, N, O v mc K tng ng vi cc bc sng i : 1 = 1215,7 A0 ; 2 = 1025,6 A0 ; 3 = 972,6 A0 ; 4 = 946,9 A0 a) Hy xc nh nng lng ra eV ng vi tng mc L, M, N, O i vi H v biu din n trn gin . b) T kt qu nng lng tnh c cu (a), hy suy ra cc mc nng lng K, L, M, N, O cho ion Li+. Cho nng lng ca H trng thi c bn l -13,6 eV; h = 6,62.10-34J.s; c = 3.108m/s. Li gii
a) E j i = E j Ei =
hc
E - 0,55 eV
i
hc
O N M L
- 0,85 eV - 1,51 eV - 3,4 eV
Vi bc chuyn L K, ta c:
E L K = E L Ek = hc
6,62.10 34.3.108 = = 10,2(eV ) 1215,7.10 10.1,6.10 19
Vy:
E L = E L K + E K = 10,2 13,6 = = 3,4(eV )
- 13,6 eV
Mt cch tng t, ta c:
E M = 1,51(eV ) ; E M = 0,85(eV ) ; EO = 0,55(eV ) .
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gio trnh ho i cng
b) T kt qu Ei va tnh c, suy ra Ei tng ng vi Z = 3 theo biu thc:

Vi lp K, ta c: Lp L Lp M Lp N Lp O
13,6 Ei = Z 2 2 n 13,6 E1 = 32 2 = 122,4(eV ) 1 E 2 = 30,6(eV )
E3 = 13,59(eV )
E 4 = 7,65(eV ) E5 = 4,95(eV )
Bi 9: Cho nguyn t H. Hy xc nh cc i lng sau: a) Nng lng kch thch dng chuyn electron t trng thi c bn ln trng thi ng vi n = 3. b) Nng lng ion ha tch electron n = 3 ti xa . c) Bc sng (nm) khi electron chuyn t n = 3 v n = 2. Li gii p dng cng thc:
1 1 E = Ec Et = E H 2 2 nc nt
EH l nng lng ca H trng thi c bn: EH = -13,6 (eV)

a) i vi bc chuyn t 1 3 nng lng tng ng l: n=3 a) Nng lng ion ha ng vi bc chuyn 3 l:
1 1 13,6 E3 = E E3 = 13,6 2 = = 9 3 = 1,52(eV )
n= n=4 n=3 n=2 13 n=1 32
c) Bc sng 32 khi electron chuyn t 3 2:

E32 = E3 E2 = h = h
32
1 1 = 13,6 2 2 3 2
Suy ra 32 = 36
hc = 6,57.10 7 (m) 5.13,6.1,6.10 19
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gio trnh ho i cng
nlml (r , , )
Bi 10: i vi nguyn t H, bit cc AO sau: 100 ; 210 ; 321 . a) Cn c vo l thuyt hc hy v hnh dng cc AO tng ng trn. b) Tnh nng lng v m men ng lng ca cc AO . Li gii Theo kt qu li gii phng trnh Sring xc nh c cc gi tr
Khi vit ngha l: n = 2; l = 1; ml = 0. y l AO-2pZ cc obitan p u c dng hnh s 8 ni c n = 1; l = 0; ml = 0 l AO-1s c dng hnh cu c n = 3; l = 2; ml = 1 l AO-3dxy Hnh dng ca cc AO-s; AO-p; AO-d xem hnh 2.7, 2.7, 2.8 (trang 61). Tnh nng lng E v momen ng lng tng ng nh sau: + Vi AO-1s: E =
13,6 = 13,6(eV ) ; M l = 0(0 + 1)h = 0 12 13,6 + Vi AO-2p: E = 2 = 3,4(eV ) ; M l = 1(1 + 1)h = 2h 2 13,6 + Vi AO-3d: E = 2 = 1,5(eV ) ; M l = 2(2 + 1)h = 6h 3
Bi 11: 1) Cn c vo cc nguyn l, quy tc hc, hy in vo cc v tr c nh du hi cc s liu thch hp. a) Z = ? 1s2 2s22p6 3s23p3 b) Z = 40 1s2 2s22p6 3s23p6 4s23d104p65s24d? c) Z = ? 1s2 2s22p? 3s23p6 4s23d?4p65s24d?5p4 d) Z = 83 [Xe]6s?4f?5s?6p? 2) Trong s cc cu hnh electron di y cho Mo (Z = 42) th cu hnh no ng, cu hnh no sai? L do? a) [Kr]5s14d5 b) [Kr]5s24d5 c) [Kr]3d14 4s24p8 d) [Ar]3d10 4s24p64d6 Li gii 1) a) Z = 15 ng vi 1s2 2s22p6 3s23p3 b) Z = 40 ng vi 1s2 2s22p6 3s23p6 4s23d104p65s24d2 c) Z = 52 ng vi 1s2 2s22p6 3s23p6 4s23d104p65s24d105p4 d) Z = 83 ng vi [Xe]6s24f145s26p3 2) a) ng v cch vit tn trng cc nguyn l v quy tc. Hn na, lp 4d t c trng thi na bo ha l phn mc nng lng bn. b) Sai, v tng s electron bng 43 > 42. c) Sai v trn phn lp 3d ch c ti a l 10 electron v 4p ch c ti a l 6 electron.
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gio trnh ho i cng
d) Sai v sau phn lp 4p l phn lp 5s ch khng phi l 4d (quy tc Klechkowski). Bi 12: T cu hnh electron ca He 1s2, hy: a) Tnh nng lng ca He theo eV. b) Tnh gi tr nng lng ca He theo phng php Slater ri so snh vi kt qu tnh cu a v vi gi tr thc nghim E He = 79(eV ). c) Xc nh nng lng ion ho th nht I1 ca He ri so snh vi gi tr thc nghim E He = 24,6(eV ). Li gii
+
a) E He
13,6.Z 2 13,6 2 2 = 2 = 108,8(eV ). = 2. n2 12
b) Theo Slater:
Z1*s = Z bi = 2 0,3 = 1,7.
13,6Z *2 13,6 1,7 2 * = 2 = 78,6(eV ). E He = 2 n *2 12
Kt qu ny kh ph hp vi thc nghim E He = 79(eV ) , nhng sai lch vi cch tnh cu a khi cha hiu chnh hng s chn bi . c) Nng lng ion ho: He - e He+ He+ l ion nguyn t ging H do vy:
13,6 Z 2 13,6 2 2 = = 54,4(eV ) 12 n2 * * I1 = E He+ E He = 54,4 (78,6) = 24,2(eV ).
* E He+ =
Kt qu ny ph hp vi thc nghim. Bi 13: Da vo phng php gn ng Slater. Hy xc nh in tch hiu dng Z* cho cc trng hp sau y: a) N (Z = 7); b) Fe (Z = 26). Li gii a) Cu hnh electron ca N l 1s2 2s22p3.
Z1*s = 7 1 0,3 = 6,70
* Z 2 s , 2 p = 7 (4 0,35 + 2 0,85) = 3,9
b) Cu hnh electron ca Fe: 1s2 2s22p6 3s23p63d6 4s2. Khi tnh in tch hiu dng Z* ngi ta xp cu hnh electron theo lp: (1s2) (2s22p6) (3s23p6) (3d6) (4s2) Vy gi tr Z* c tnh l:
Z1*s = 26 1 0,3 = 25,70
* Z 2 s , 2 p = 26 (7 0,35 + 2 0,85) = 21,85
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gio trnh ho i cng
* Z 3s ,3 p = 26 (7 0,35 + 8 0,85 + 2 1,00) = 14,75 * Z 3d = 26 (5 0,3 + 18 1,00) = 6,25
* Z 4 s = 26 (1 0,35 + 14 0,85 + 10 1,00) = 4,60
Bi 14: Cu hnh electron ngoi cng ca nguyn t ca mt nguyn t X l 5p . T s ntron v in tch ht nhn bng 1,3962. S ntron ca X bng 3,7 ln s ntron ca nguyn t thuc nguyn t Y. Khi cho 4,29 g Y tc dng vi lng d X th thu c 18,26g sn phm c cng thc l XY. Hy xc nh in tch ht nhn Z ca X v Y v vit cu hnh electron ca Y tm c. Li gii Cu hnh electron ca X l: 1s2 2s22p6 3s23p63d10 4s23p64d105s25p5 T cu hnh electron xc nh c: ZX = 53 = PX (s proton)
5
Mt khc:
Ta bit:
NX = 1,3962 N X 74. PX AX = PX + N X = 53 + 74 = 127 NX = 3,7 N Y = 20 NY
MY M M + 127 4,29 = Y = Y M Y = 39 4,29 18,26 M XY 18,26
Y + X = XY 4,29 18,26 MY MXY
S khi ca Y l 39 t suy ra: AY = PY + N Y 39 = PY + 20 PY = 19 Vy cu hnh electron ca nguyn t Y l: 1s 2s 2p 3s 3p6 4s1 Bi 15: Hy cho bit 4 s lng t tng ng i vi electron c in sau cng vo cu hnh electron trng thi c bn thuc cc nguyn t sau y: Be (Z = 4); F (Z = 9). Li gii Cu hnh electron ca: Be: F:
1 2 1 Vi F: n = 2, l = 1, ml = 0, ms = 2
2 2 6 2
Z Y = 19
Vi Be: n = 2, l = 0, ml = 0, ms =
Bi 16: Cho nguyn t X c Z = 52 1. Vit cu hnh electron ca X 2. Dng phng phap Slater hy: a) Xc nh hm bn knh R ca mt electron trn AO-5s b) Tnh nng lng ra eV ca electron ny. Li gii
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1. X (Z = 52): 1s2 2s22p6 3s23p63d10 4s24p64d10 5s25p4 2. a) Z 5*s = 52 (1 0,35 + 18 0,85 + 28 1) = 8,35
R5 s = cr e
3 8, 35 r 4 a0
= cr e
3
2 , 08 r a0
b) Nng lng ca 1e trn AO-5s: 5 s 1.2 Bi tp khng c li gii
8,35 2 = 13,6 2 = 59,26(eV ) 4
Bi 1. 1) Trong s t hp ca cc s lng t sau y, t hp no ng, t hp no sai? l do?

n a b c 2 2 2 l 1 2 0 ml 0 -1 -1
2) Cn c vo cc s liu trong bng di y. Hy vit cc phn mc tng ng v xp th t cc phn mc y theo chiu tng ca nng lng.
n a b c 2 4 5 l 2 0 2 ml -1 0 0
Bi 2. Trong s cc nguyn t c s electron bng hoc t hn 20 electron, hy xc nh xem c bao nhiu nguyn t tho mn iu kin cu hnh electron ca n tho mn c 2 electron c thn trng thi c bn? Bi 3. a) Hy cho bit gi tr ca cc s lng t c trng cho cc trng thi sau: 2s; 3p; 3d; 3f; 4d v cho nhn xt. b) in tip gi tr s lng t ml v tnh s AO c th c trn tng phn lp. c, T cc AO xc lp c, hy sp xp chng theo th t tng dn mc nng lng. Bi 4. 1) Cho nguyn t Cs (Z = 55) a) Nu gi thuyt mi obitan tn ti 3 electron ng thi th cu hnh electron nh th no? Hy vit n v cho nhn xt. b, Da vo cc nguyn l v quy tc, hy vit cu hnh electron thc ca trng hp ny. 2) Hon thnh cu hnh electron sau y:
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gio trnh ho i cng
a) 1s2 2s22p6 3s23p6... bit Z = 26 b) Tnh Z khi bit cu hnh electron: 1s2 2s22p6 3s23p63d?4s24p3 Bi 5. Cho nguyn t Cl (Z = 17); Ni (Z = 28). Hy: a) Vit cu hnh electron ca cc ion Cl- v Ni2+. b) Vi cu hnh electron ca Ni2+ tm c cu a, hy cho bit c bao nhiu electron c thn. Bi 6. Hai nguyn t A v B c cc phn lp electron ngoi cng l 3p v 4s tng ng. Tng s electron ca hai phn lp bng 5 v hiu bng 3. Hy vit cu hnh electron ca hai nguyn t ri tnh gi tr Z ca A v B. Bi 7. Cho nguyn t A vi phn lp ngoi cng l 4px v nguyn t B c phn lp ngoi cng l 4sy. Hy xc nh s in tch ht nhn Z ca A v B, bit tng s electron trn hai phn lp nu trn l 7 v nguyn t A khng phi l kh him. Bi 8. 1) Cho bit trong s cc b s lng t cho di y, th trng hp no ng? trng hp no sai?
n a b c d e f 2 2 2 1 2 0 l 0 1 1 0 4 0 ml 0 1 0 1 -1 0
2) Trong ba cu hnh electron di y th cu hnh no ng? cu hnh no sai? Nu sai th cho bit cu hnh vi phm quy tc no? nguyn l no? a) b) c) Bi 9. a) Hy vit cu hnh electron ca nguyn t v ion sau y: Cd (Z = 48); Sr (Z = 38); Cr (Z = 24); Al3+ (Z = 13) b) Cho cc nguyn t sau y: Ba (Z = 56); O (Z = 8); As (Z = 33); I (Z = 53); Rb (Z = 37). Hy cho bit cc ion no ca cc nguyn t ng vi cu hnh electron bn vng nht? Bi 10. Trn c s ca quy tc gn ng Slater hy xc nh cc in tch hiu dng Z* ng vi cc nhm phn lp tng ng c th c v tng nng lng i vi nguyn t Cl (Z = 17) trng thi c bn. Bi 11. Hy cho bit ni dung v c s C hc lng t ca nh lut tun hon cc nguyn t ha hc. Bi 12. Hy cho bit c th ca tng ni dung ca bng Menlep.
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Bi 13. Ha tr ca cc nguyn t trong phn nhm chnh, trong chu k c c im no? Trnh by c th v minh ha. Bi 14. Hy cho bit ni dung, v d minh ha, c s ca quy lut bin thin tnh cht ca nguyn t trong chu k, trong nhm. Bi 15. Hai nguyn t ho hc X, Y iu kin thng u l cht rn. S mol X c trong 8,4 g nhiu hn 0,15 mol so vi s mol Y c trong 6,4 g. Bit khi lng mol ca X nh hn khi lng mol ca Y l 8,0 g. a) Hy cho bit k hiu ha hc ca X v Y. b) Tm s mol mi nguyn t xt trn. c) Trn hai lng cht trn ri nung ti nhit thch hp, khng c oxi, tnh lng cht to thnh sau s nung . Bi 16. Bn knh cng ha tr l g? Hy cho bit quy lut lin h gia tr s ny vi v tr nguyn t trong bng h thng tun hon. Bi 17. Th no l nguyn t h s, p, d, f? Cu hnh electron c th c ca cc nguyn t mi h trn? Bi 18. Th no l nng lng ion ha? Hy so snh cc tr s nng lng ion ha c th c ca nguyn t Bo v gii thch th t cc tr s . Bi 19. Hy tm h s chuyn n v nng lng eV thnh kJ.mol-1. Bi 20. Hy cho bit ni dung v gii thch quy lut bin i nng lng ion ha th nht I1 ca cc nguyn t theo tr s in tch ht nhn Z. Bi 21. Hy gii thch cc ngoi l v tr s I1 ca cc nguyn t O, Al, S trong bng 6.6. Bi 22. Theo Pauling, m in l g? Hy nu v gii thch quy lut bin i tr s m in theo s hiu nguyn t (Z) ca cc nguyn t. Bi 23. Lin kt no l ion, cng ha tr phn cc, cng ha tr khng phn cc trong s lin kt gia cc cp nguyn t sau y: LiH, LiF, CH, NH, OH, NN, RbBr, SiH, CaO? Lin kt no c phn cc ln nht? Bi 24. a) Hy cho bit cu hnh electron ca mt nguyn t chuyn tip, bit rng nguyn t ny c 3 electron nm phn lp d v thuc chu k 4 ca bng h thng tun hon. b) Nit (Z = 7) bit cu hnh electron v nm chu k 2 ca bng tun hon. Hy xc nh s hiu nguyn t Z v vit cu hnh electron ca nguyn t asen, bit rng nguyn t ny nm cng nhm vi nit v thuc chu k 4. Bi 25. Cu hnh electron ca nguyn t A c phn lp ngoi cng l 3p. Nguyn t B cng c phn lp 3p trong cu hnh electron ca mnh v phn lp tip theo c 2 electron. Hai phn lp 3p ca A v B cch nhau 1 electron. Hy xc nh s th t ca A v B v cho bit nguyn t no l kim loi? l phi kim? l kh him? Bi 26. a) Hy vit cu hnh electron ca cc nguyn t c Z 18 v c 1 e c thn trng thi c bn.
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b) Da vo cu hnh electron ca Na (Z = 11), hy xc nh s hiu nguyn t ca nguyn t X, bit rng nguyn t ny cng chu k vi Na v cng nhm vi ini (49In). Bi 27. a) Gii thch ti sao ch Pb (Z = 82) v cacbon C (Z = 6) cng thuc mt nhm trong bng h thng tun hon nhng ch l kim loi cn cacbon l phi kim. b) Trong s cc nguyn t thuc chu k 4 ca bng h thng tun hon (19 Z 36), nguyn t no c cu hnh electron trng thi c bn tho mn iu kin c 2 electron c thn. Bi 28. a) Gii thch ti sao nguyn t km Zn (Z = 30) v canxi Ca (Z = 20) c cng cu hnh electron lp ngoi cng nh nhau nhng li khng thuc cng mt phn nhm? b) Hy xc nh s th t Z ca mt nguyn t X, bit rng nguyn t ny chim 1 cng vi chu k ca Li (Z = 3) v cng nhm vi thic Sn (Z = 50). Bi 29. Cho cc nguyn t He (Z = 2); H (Z = 1); Li (Z = 3); O (Z = 8); F (Z = 9); Rb (Z = 37). Cn c vo quy lut bin thin tun hon m in trong bng tun hon, hy gn cc gi tr cho tng nguyn t k trn v xp chng theo chu k v nhm . : 0,8; 0,4; 0,9; 2,1; 1,0; 3,5; 3,0 bit F = 4,0 . Bi 30. 1) Cho cc nguyn t say y: Cl; Al; Na; P; F. Cn c vo s bin thin tnh cht ca cc nguyn t trong mt chu k v trong mt nhm ca bng tun hon. a) Hy sp xp theo th t tng dn ca bn knh nguyn t i vi cc nguyn t trn. b) Cho bit th t tng dn v m in ca cc nguyn t kho st ni trn. 2) Cn c vo cu hnh electron ca Na+ (Z = 11) v Ne (Z = 10) hy so snh bn knh ca chng. Bi 31. 1) Vit cu hnh electron trng thi c bn cho cc nguyn t sau: Mg (Z = 12); Ca (Z = 20); Sr (Z = 38); Zn (Z = 30); Cd (Z = 48). 2) Cho cc gi tr nng lng ion ha th nht I1 (kJ/mol). Cn c vo quy lut bin thin i lng I1 trong bng tun hon, hy gn cc gi tr y cho cc nguyn t cu hi 1) I1 (kJ/mol): 548; 585; 736; 903. 3)Bit rng Sr (Z = 38) khi mt 2e s c cu hnh electron bn vng; trong khi nguyn t st Fe (Z = 26) li cho hai dng cu hnh electron bn vng khi mt electron. Hy vit cu hnh electron cho 3 trng hp trn v ch r s electron c thn cho tng trng hp. Bi 32. Tm s proton, ntron, electron c trong: a) Fe, Fe2+, Fe3+. b) N3-, N-, N, N+, N2+, N3+, N4+, N5+
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Bi 33. Da vo bn cht ht v , hy gii thch nh lut chuyn di trong s bin i phng x. Bi 34. Ht nhn 35Br80 c th bin i bng cch: a) Bc x 1e b) Bc x 1 pozitron c) ot 1e Hy vit phng trnh phn ng to thnh nguyn t mi mi trng hp trn. Bi 35. Vit y phng trnh phn ng ht nhn sau y (c gii thch cho mi trng hp).
a) 15P32 ? + b) 19K43 c) 84Po210
0 -1e
; ; ; ; + ?
e) 11Na22 1e0 + ? f) 12Mg27 g) 17Cl36 h)94Pu239

0 -1e
43 20Ca 82Pb 206
+ ?
+ ? + ? +
36 18Ar 235 93Ur
d) 9F17 ? + 1e0
Bi 36. ng v 84Po207c th b phn hu theo 3 cch: a) ot 1e; b) Bc x 1 pozitson; c) Bc x 1 ht . Hy vit phng trnh cho mi trng hp . Bi 37. Sau 85 ngy mt mu 45g 86Rn222 cn li bao nhiu, nu bit t 1
2
= 3,8 ngy? Bi 38. Mt mu Co60 ban u c 0,3mg, sau 1,40 nm cn li 0,25mg. Tm chu k bn r ca Co60. Bi 39. Xesi - 137 l mt ng v thng c trong l phn ng ht nhn. Chu k bn r ca Cs - 137 bng 30,2 nm. Cs - 137 l mt trong cc ng v b pht tn nhiu ti chu u sau tai nn ht nhn Trecnbn. Hy x nh sau bao lu lng cht c ny cn1% k t khi tai nn xy ra? Bi 40. Mt mu cha 13,2g U238 v 3,42g Pb206. Chu k bn r ca U238 l 4,51.109 nm. Tnh tui ca mu . II. Bi tp trc nghim Bi 1. Trng thi c bn ca lu hunh c cuhnh electron l: B) 1s2 2s22p6 3s23p4 A) 1s2 2s22p6 3s23p2 C) 1s2 2s22p6 3s23p33d1 D) 1s2 2s22p6 3s13p5 Bi 2. Electron ho tr l: A) e ngoi cng B) e gn ht nhn nht C) e phn lp ngoi cha bo ho D) e v s Bi 3. m in ca N, O, F, Cl, Mg tng ng bng 3,0; 3,5; 4,0; 3,0; 1,2. Dy c th t ng v s tng phn cc lin kt trong phn t l: B) NCl3, FCl, Mg2N3, MgF A) MgCl2, O2, NF3, MgO C) Cl2, MgF2, NO, NCl3 D) MgO, FCl, F2O, MgCl2 Bi 4. S obitan c trong phn lp s l: A) 1 obitan B) 2 obitan
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gio trnh ho i cng
C) 3 obitan D) 4 obitan Bi 5. S electron ti a c trong cc phn lp s, p, d, f l: A) 2, 4, 6, 8 B) 2, 6, 10, 12 C) 2, 6, 10, 14 D) 2, 6, 8, 12 Bi 6. S AO c trong cc phn lp s, p, d, f l: A) 1, 2, 3, 4 B) 1, 3, 5, 7 C) 2, 3 4, 5 D) 2, 3, 5, 7 Bi 7. Pht biu no di y l ng: A) Cc nguyn t c cng in tch ht nhn, c s khi nh nhau c gi l cc ng v. B) Vi mi nguyn t, s lng proton trong ht nhn nguyn t l c nh, song c th khc nhau v s lng ntron, gi l hin tng ng v. C) Cc nguyn t c s khi nh nhau, song s proton ca ht nhn li khc nhau c gi l cc ng v. D) C th tch cc ng v ca cng mt nguyn t bng phng php ho hc. Bi 8. Cho cc nguyn t: 92U238, 94Pu244, 93Np237, 95Am243. Cp nguyn t cha nhiu ntron nht v t ntron nht l: A) Pu v Np B) U v Am C) Am v Np D) Pu v U 35 37 Bi 9. Cho cc nguyn t: 17A , 17B , 18C36, 18D38. Khng cng tn nguyn t l cc cp nguyn t sau: A) A, B B) C, D C) B, C D) A,C; A,D; B,C; B,D 90 2+ 82 Bi 10. Cho hai ion: 38 Sr , 35 Br . S electron, s ntron ca hai ion ny tng ng l: A) 38 v 85; 35 v 47 B) 38 v 50; 45 v 49 C) 36 v 52; 36 v 47 D) 36 v 50; 36 v 49 Bi 11. Pht biu no di y l sai: A) S lng t chnh n c th nhn gi tr nguyn dng (1, 2, 3, ...). Nhng electron c cng s lng t chnh n lp nn mt lp electron. n = 1 lp K, n = 2 lp L, ... B) S lng t ph (s lng t obitan) l c th nhn cc gi tr t 0 n ( n -1), ngha l nhn tng cng n gi tr. Nhng electron c cng s lng t ph l lp thnh mt phn lp. l = 0 phn lp s, l = 1 phn lp p, ... S lng t ph l xc nh hnh dng v tn ca obitan nguyn t. l = 0 obitan s, hnh cu; l = 1 obitan - p, hnh s tm ni;... C) S lng t t ml nhn cc gi tr t - l n + l , k c gi tr 0, tc l gm (2 l +1) gi tr. S lng t t ml xc nh s obitan nguyn t c trong mt phn lp. Phn lp s ( l = 0) c 1 obitan nguyn t. Phn lp p ( l = 1) c 2 obitan nguyn t.
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Phn lp ( l = 2) c 3 obitan nguyn t. D) S lng t spin ms nhn 1 trong hai gi tr +1/2 hay -1/2. Bi 12. B bn s lng t no di y c th chp nhn c: A) n = 3, l = 3, ml = +1, ms = +1/2 B) n = 3, l = +1, ml = +2, ms = +1/2 C) n = 2, l = +1, ml = -1, ms = -1/2 D) n = 4, l = +3, ml = -4, ms = -1/2 Bi 13.Trong bn b s lng t cho di y: 1, n = 4, l = 3, ml = 0 2, n = 3, l = 3, ml = -1 3, n = 1, l = 0, ml = 1 4, n = 3, l = 2, ml = -2 Nhng b s lng t c th chp nhn c l: A) (1) B) (2) v (3) C) (1) v (4) D) (4) Bi 14. Pht biu no di y l sai: A) Phn gc ca obitan - s c i xng cu. B) Phn gc ca mi mt obitan - p c mt trc i xng: chnh l trc ta cac. C) Phn gc ca nm obitan - d c hnh dng tng t nhau. D) Phn gc ca obitan - d z c trc Oz l trc i xng. Bi 15. Mt obitan nguyn t 3d tng ng vi b hai s lng t no sau y: B) n = 3, l = 2 A) n = 2, l = 3 C) n = 2, l = 2 D) n = 3, l = 1 Bi 16. Pht biu no di y l ng A) Trong mt nguyn t c th c hai electron cng c c trng bng mt b bn s lng t nh nhau. B) trng thi c bn, cc electron s chim mc nng lng thp trc ri mi n mc nng lng cao hn. C) Khi in tch ht nhn tng, cc electron s chim mc nng lng c tng ( n + l ) tng dn. i vi cc phn lp c tng ( n + l ) bng nhau th electron c in vo phn lp c tr s n nh trc, sau mi in vo phn lp c n ln hn. D) Trong mt phn lp, cc electron c xp sao cho c mt s ti a electron c thn. Bi 17. Nguyn t ca nguyn t c Z = 35 c cu hnh electron tng ng l: B) [Ne]3s23p63d3 4s2 A) [Ne] 3s23p1 C) [Ne] 3s23p63d10 4s24p5 D) [Ar] 4s24p64d7 5s2
2
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Bi 18. Nguyn t R thuc chu k 3, nhm V, c cu hnh electron tng ng l: A) 1s2 2s22p3 B) [Ne] 3s23p2 D) [Ne] 3s23p3 C) 1s2 2s22p6 3s23d3 Bi 19. Electron c b bn s lng t n = 4, l = 2, ml = +1, ms = -1/2 (gi tr ml c xp tng dn) l electron thuc: A) Lp N, phn lp p , l electron th 2 thuc phn lp ny. B) Lp N, phn lp d , l electron th 6 thuc phn lp ny. C) LpN, phn lp f, l electron th 1 thuc phn lp ny. D) Lp N, phn lp d , l electron th 9 thuc phn lp ny. Bi 20. Electron cui cng in vo cu hnh electron ca nguyn t c Z = 23 (gi tr ml c xp tng dn) c b bn s lng t l: A) n = 2, l = 1, ml = -1, ms = -1/2 B) n = 3, l = 2, ml = +1, ms = +1/2 C) n = 3, l = 1, ml = -1, ms = -1/2 D) n = 2, l = 1, ml = 0 , ms = +1/2 Bi 22. Electron cui cng in vo cu hnh electron ca nguyn t X c b bn s lng t: n = 3, l = 2, ml = -2, ms = -1/2. Nguyn t X c s hiu nguyn t Z l: A) 24 B) 26 C) 30 D) 28 Bi 23. Pht biu no sau y l sai: A) Tnh cht ca nguyn t ph thuc tun hon vo in tch ht nhn nguyn t. B) in tch ht nhn nguyn t ca bt k nguyn t no v tr s bng s th t ca nguyn t trong h thng tun hon. C) Tnh cht cc n cht, thnh phn v tnh cht cc hp cht bin thin tun hon theo chiu tng ca khi lng nguyn t. D) Da vo cu hnh electron, cc nguyn t c chia thnh 4 h: s , p ,
d , f.
Bi 24. Pht biu no di y l ng: A) Nguyn t ca cc nguyn t cng nhm A bao gi cng c s electron lp ngoi cng bng nhau v bng s nhm. B) Nguyn t ca cc nguyn t trong cng nhm B bao gi cng c s electron lp ngoi cng bng nhau. C) Cc nguyn t s, p, d l kim loi cn nguyn t p l phi kim. D) Tnh cht ha hc ca cc nguyn t trong cng nhm A (hoc cng nhm B) bao gi cng ging nhau ( mc nht nh). Bi 25. B 3 nguyn t sau thuc chu k 4, nhm VIIIB: Fe (Z = 26), Co (Z = 27), Ni (Z = 28). Pht biu no di y l ng vi cc nguyn t ny: A) S electron lp ngoi cng ca chng l nh nhau. B) S electron ha tr ca chng bng nhau. C) S oxi ho dng cc i ca chng bng nhau.
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D) Chng u l nhng kim loi c tnh kh mnh. Bi 26. Trong dy no di y, i lc vi electron c xp theo th t gim dn. A) Na, K, Li B) K, Na, Li C) F, Cl, Br, I D) Cl, F, Br, I
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CHNG 3 CU TO PHN T V LIN KT HA HC A. MC TIU, NHIM V 1. MC TIU Hc xong chng 3 sinh vin phi tr li c cc cu hi: - Lin kt ho hc c nhng c trng ch yu no? - Th no l lin kt cng ha tr, lin kt ion? - Xt tng i v lin kt ion th cn nhng ni dung no? - Hnh hc phn t l g? Sinh vin phi nm vng cc kin thc sau: - Lun im c bn ca thuyt VB. Cc thuyt trong phm vi thuyt VB, c bit l thuyt spin v ha tr v thuyt lai ha. S ha tr l mt cch biu din cng thc cu to theo thuyt VB. - Lun im c bn ca thuyt MO. p dng thuyt MO gii thch lin kt ha hc trong h phn t A2 v mt s phn t hp cht dng ABn. V nhn thc lun: Thng qua s pht trin ca cc thuyt v lin kt ho hc, ngi hc nhn thy c quy lut pht trin ca nhn thc t n gin n phc tp, thng qua s k tha v pht trin ca cc hc thuyt. 2. NHIM V Tm hiu mt s vn v: - Lin kt ha hc, lin kt cng ha tr, lin kt ion. - Cc thuyt VB v MO v lin kt ha tr 3. PHNG PHP Ch trng phng php tin : Nm vng cc kin thc c bn t c kh nng vn dng cc kin thc c hc vo thc tin. B. NI DUNG M u: Mt trong nhng vn quan trng nht ca ha hc l cn tr li c cu hi:" Bn cht ca lin kt ho hc l g?" Theo thi gian, cng vi s pht trin ca khoa hc ni chung, ha hc ni ring, vn ny ngy cng c sng t Chng ny gm mt s vn sau: 1. Mt s vn chung. 2. Lin kt ion. 3. Mt s vn v cng thc ha hc v hnh hc phn t. 4. Thuyt VB v thuyt MO v lin kt cng ha tr. 1. CC C TRNG C BN CA LIN KT HA 1.1. i cng v phn t v lin kt ha hc 1.1.1. Hai c im quan trng ca h phn t * c im 1: C t 2 ht nhn tr ln C t 2 electron tr ln (c bit, h phn t ch c 1e l ion phn t + H2 ) Vy phn t l h nhiu ht nhn.
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* c im 2: Tng tc trong h phn t l tng tc ht v y, cc tng tc ny c gi l tng tc tnh in. Trong tng tc ht mnh hn nhiu so vi tng tc y th phn t mi c hnh thnh. 1.1.2. Cng thc ha hc C cc loi sau: + Cng thc phn t: + Cng thc n gin nht (cng thc thc nghim): v d CH + Cng thc tng qut: (CH)n + Cng thc nguyn: n c xc nh. + Cng thc cu to: cho bit trt t sp xp ca cc nguyn t trong phn t. y l cng thc rt quan trng v c mi lin h cht ch gia cu to v tnh cht. 1.2. Cc c trng c bn ca lin kt ha hc 1.2.1. Khi nim v lin kt ho hc S hnh thnh phn t (tc l hnh thnh cc lin kt ha hc) xut hin do tc dng tng h ca tt c cc ht nhn v cc electron ca cc nguyn t tham gia to thnh phn t, t hnh thnh mt cu trc mi (phn t) bn vng v c nng lng cc tiu. Lin kt ha hc l mt vn xuyn sut trong ton b cc vn ca ha hc v nm vng c lin kt ho hc s gip ta bit c trung tm phn ng cng nh hng phn ng ca cc phn t tham gia. 1.2.2. Cc c trng c bn ca lin kt ha hc a) Nng lng lin kt y l yu t quan trng nht ca ho hc. * Khi nim Nng lng lin kt l nng lng gii phng ra khi hnh thnh lin kt ha hc (hnh thnh phn t) t 2 nguyn t trung ha hay 2 gc t do. n v o: eV/1phn t; kJ/1 mol phn t hoc kcal/1 mol phn t. V d 1: Nng lng lin kt gia 2 nguyn t H l, EHH = - 436 kJ/mol (hnh3.1).
E (Kj/mol) d d(A0)
0,74A0
2.EH
-436
HNH 3.1. Qu trnh hnh thnh phn t H2 t 2 nguyn t H xa nhau v cc Theo khi nim trn th nng lng lin kt cng thp (cng m) th lin kt cng bn; h phn t trng thi c bn khi nng lng ca n cc tiu, do nng lng dng ph v lin kt cng ln.
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ln ca Elk (khng xt du -) c trng cho bn ca lin kt , tc l lin kt no c tr s nng lng lin kt cng ln th lin kt cng bn. Gi D: l nng lng phn ly lin kt ha hc. Khi , nng lng ph v lin kt HH ca phn t H2, to ra 2 nguy t H 0(K) l:
DH 2 = 2.E H E H 2 = 2.0 (436) = 436 kJ mol
HF = 563; HCl = 432; HBr = 366; HI = 299 So snh cc tr s ny, ta thy lin kt HF bn nht, cn HI km bn nht.Nh vy, qu trnh phn ly lin kt v qu trnh hnh thnh lin kt l 2 qu trnh ngc nhau. * Nng lng lin kt trung bnh Trong ho hc c nhiu trng hp mt phn t c ng thi nhiu lin kt, nh CH4 c 4 lin kt CH. Nng lng lin kt c xc nh, ECH 410 kJ/mol l nng lng lin kt trung bnh ca mt lin kt CH. Thc nghim xc nh c, nng lng lin kt CH mi lin kt trong CH4 nh sau: C + H C H; EC H 334,4kJ .mol 1 HC + H HC H; E HC H 514,2kJ .mol 1 H2C + H H2C H; E H C H 367,8kJ .mol 1
2
H3C + H H3C H; E H C H 422,2kJ .mol 1 T cc s liu trn thy rng, s hnh thnh mi mt lin kt CH c nng lng khng ging nhau. V vy gi tr - 410 kJ/mol l nng lng trung bnh hnh thnh mi mt lin kt CH trong phn t CH4. BNG 3.1. Nng lng lin kt trung bnh tnh theo kJ.mol-1 ca mt s lin kt ph bin
3
Nng lng lin kt trung bnh (kJ.mol-1) CH 415 CF 441 NH 391 OO 143 C=C 615 CC 812 CC 344 C Cl 328 OH 463 NN 159 C=O 725 CN 890 CO 350 C Br 276 SH 368 N Cl 200 C=N 615 NN 946 CN 292 CI 240 SS 266 HH 436 O=O 948 CS 259 FF 158 NO 175 Cl Cl 243
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Gia nng lng lin kt v bn lin kt c mi lin h: Nng lng trung bnh ca lin kt cng ln th lin kt cng bn. Lin kt bn cn c gi l lin kt mnh, lin kt km bn gi l lin kt yu. T cc s liu bng 3.1 cho thy gia 2 nguyn t nit to ra phn t N2, NN l lin kt rt bn (lin kt mnh). Cc lin kt c nng lng lin kt t 200 kJ.mol-1 tr ln c coi l lin kt mnh (bn). Nhm cn li c nng lng nh hn 200 kJ.mol-1 l lin kt yu (km bn). V d 2: S dng cc s liu bng 3.1, hy cho bit: a) Lin kt gia 2 nguyn t oxi l lin kt mnh (bn)? b) Tm quy lut lin h gia m in (ca nguyn t) vi nng lng lin kt. Tr li: a) Kt lun khng hon ton ng, v ch lin kt O = O mi bn (mnh) cn lin kt OO l lin kt yu. b) c quy lut: m in cng ln, nng lng lin kt cng ln, lin kt cng bn. Dn chng: Xt lin kt CX, X l halogen X F Cl Br I m in ( ) 4,0 3,0 2,8 2,2 441 328 276 240 ECX b) Tnh cht ca phn t b1) Hnh hc phn t * di lin kt: di ca mt lin kt trong phn t l khong cch gia hai ht nhn nguyn t to ra lin kt khi phn t trng thi nng lng cc tiu.
HNH 3.2. di lin kt trong phn t AB l dAB R l khong cch 2 ht nhn di lin kt thng k hiu l: d V d 3: Trong phn t H2 di lin kt d H H = 0,74 A0 Phn t H2O c d H O = 0,94 A0
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di ca cc lin kt gia cacbon-cacbon v nng lng lin kt tng ng:

d C C = 1,54 A0 d C =C = 1,34 A0 d C C = 1,20 A0
Ec-c = 83 kcal/mol Ec=c = 143 kcal/mol Ecc = 194 kcal/mol
T v d trn ta thy di lin kt gim khi bc lin kt tng v nng lng lin kt tng (lin kt cng bn) nhng khng c tnh cht cng tnh. *Bn knh lin kt:
d AB
1 (d AA + d BB ) 2 1 (d C C + d Cl Cl ) = 1 (1,54 + 1,99)A0 , 2 2
Vi dAA, dBB l di ca lin kt AA, BB tng ng. V d 4: Bit dClCl = 1,99 A0, vy dC Cl = dC Cl 1,765 A0, thc nghim o c dCCl = 1,766 A0, sai s php tnh bng l thuyt so vi thc nghim l khng ng k. Do coi nguyn t A. BNG 3.2. Bn knh lin kt r ca mt s nguyn t (theo Pauling; biu th bng A0)
Nguyn t Lin kt n Lin kt i Lin kt ba H C N O F P S Cl Br I 0,30 0,77 0,70 0,66 0,64 1,10 1,04 0,99 1,14 1,33 0,67 0,60 0,56 0,60 0,55 0,60 1,00 0,94 0,89 1,04 1,23
1 d AA 2
l bn knh lin kt hay bn knh cng ho tr rA ca
di lin kt HH o c bng 0,74A0 nhng bng trn rH = 0,30A0 ch khng phi rH = d H H = 0,37 A0 . Tr s rH = 0,30A0 gip cho vic d on ng hn di lin kt gia nguyn t H vi nguyn t ca cc nguyn t khc. Khi 2 nguyn t A, B khc nhau v m in, di lin kt dAB o c nh hn tr s tng (rA + rB). Nhng trng hp cn li c th d on kin kt theo tr s di dAB (rA + rB) * Gc lin kt: Gc lin kt l gc to bi hai na ng thng xut pht t mt ht nhn ca mt nguyn t i qua ht nhn ca 2 nguyn t lin kt vi nguyn t . Cc trng hp in hnh v gc lin kt theo nh ngha trn l: + Phn t thng, c gc lin kt bng 1800 nh C2H2, CO2, BeH2, ... + Phn t c gc, gc lin kt khc 1800, nh BF3, C2H4, ion , ,...c gc 1200, H2O c gc 104028 (104,50), ... + Phn t t din, c gc lin kt bng 109028, l CH4, , ,...
1 2
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Trong mt s trng hp, ngi ta ch n gc c to ra t 4 nguyn t hay 2 mt phng, l gc nh din. Hnh 3.3 m t phn t H2O2 c gc nh din HOOH bng 109,50.
HNH 3.3. di v gc lin kt ca phn t H2O2. * M hnh sc y gia cc cp electron v ha tr Mt trong nhng vn m ha hc quan tm l gii thch v tin on hnh dng, di lin kt, gc lin kt ca phn t. c mt s thuyt gii quyt vn ny. Trong phn ny chng ta nghin cu mt thuyt thng c p dng l m hnh s y gia cc cp electron v ha tr, hay thuyt VSEPR. V nguyn tc, lc tng tc gia cc ht nhn v cc electron trong phn t ch yu l lc tng tc tnh in. Chng ta u bit, lin kt ha hc c chia thnh 2 loi: lin kt cng ha tr v lin kt ion. Khng c ranh gii r dt gia 2 loi lin kt ny. Ion vn c coi l ht mang in v c i xng cu. Nh vy lc tnh in (lc y hay ht) ca mi ion l lc khng nh hng, tc l lc ny tc dng nh nhau v mi pha quanh ion . Lin kt ion c hnh thnh nh lc ht tnh in ca cc ion tch in tri du. Nh vy, v bn cht lin kt ion l lin kt khng nh hng khng gian. Do , cc iu kin c th, cc hp cht ion khng tn ti ring l tng phn t m tn ti di dng mng tinh th. V vy khng t vn xt hnh dng tng phn t c to ra t kin kt ion ch t vn v mng tinh th (s xt phn sau). chng ny, chng ta ch xt lin kt cng ha tr. Theo quan nim thng thng, mi lin kt cng ha tr gia 2 nguyn t c to thnh nh i electron lin kt hay i electron dng chung.i electron lin kt c phn b trong khong khng gian gia 2 ht nhn nguyn t to ra lin kt . Nh vy tri vi lin kt ion, lin kt cng ha tr l lin kt c tnh nh hng khng gian. Nh vy, mi phn t lin kt cng ha tr c hnh dng nht nh; hnh dng khc nhau cc phn t khc nhau. T cu to nguyn t, tr nguyn t H, cc nguyn t khc nhau khi gp chung electron to ra lin kt cn c electron cha lin kt hay electron ring. Xt phn t NH3, ch xt v ha tr (lp ngoi cng) ca N, ngoi 3 electron to 3 lin kt vi 3 nguy t H, N cn c 1 i electron ring. Dng k hiu hai chm (..) ch i electron ny. Ta c cng thc :NH3 hay NH3 (cng thc ny, i electron ring n, khng vit). T c th khi qut: v ho tr ca nguyn t (trong phn t ln kt cng ho tr) c i electron lin kt v i electron ring.
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Nu quy c: Trong phn t AXn, A l nguyn t trung tm, X l phi t; n l s phi t X c trong AXn. Nu A cn c m i electron ring, mi i c k hiu l E, khi ny ta c k hiu AXnEm. Vn cn phi xt l s phn b khng gian gia A v X vi E nh th no? Ni cch khc l phn t AXnEm c hnh dng ra sao? M hnh sc y electron v ha tr s gip chng ta tr li cu hi ny. Cn hnh dung l nguyn t trung tm A c hnh dng mt qu cu. Tm ca qu cu l ht nhn nguyn t A, v qu cu l lp electron ngoi cng hay lp electron ha tr. Mi cp electron v ha tr chim mt khong khng gian trn qu cu . Nh vy, mt mc nht nh, hnh dng ca phn t ph thuc vo khong khng gian chim bi cc cp electron v ha tr ca nguyn t trung tm A, tc l ph thuc vo s phn b cc cp electron v ho tr ca A. *M hnh s y gia cc cp electron v ha tr (m hnh VSEPR) Ni dung ca m hnh VSEPR l: Cc cp electron v ha tr c phn b cch nhau ti mc xa nht c th lc y gia chng l nh nht. Trong phn t, cn phn bit nguyn t trung tm vi phi t (cc nguyn t hoc nhm nguyn t lin kt vi nguyn t trung tm), s phn b v tr tng i gia nguyn t trung tm vi phi t s cho ta hnh nh v m hnh ca phn t. Trong m hnh trn, cn hnh dung nguyn t trung tm c i xng cu tc l mt ngoi ca nguyn t trung tm l mt mt cu, cc lin kt (e lin kt) v cc e ring (e khng lin kt) c phn b trong 1 khng gian trn mt cu . Mt cch gn ng, dng hnh nh my electron m t chuyn ng ca i electrron trong phn t. l i electrron lin kt hoc i electrron ring. Mi my electron ny c phn b (chim) trong khng gian quanh nguyn t trung tm m gii hn mt ngoi chnh l mt cu ca nguyn t trung tm. Hnh dng phn t c tin on hay gii thch da vo m hnh trn c gi l hnh dng m hnh s y gia cc cp electron v ho tr (VSEPR). M hnh ny khng p dng cho cc hp cht phc ca cc nguyn t chuyn tip c v ho tr d. Trc khi p dng m hnh ny, cn phn bit s khc nhau gia i electron lin kt v i electron ring: - i electron lin kt chu lc ht ng thi ca 2 ht nhn nguyn t A v X to ra lin kt . - i electron ring ch chu lc ht ca ht nhn A. Kt qu i electron ring chim mt th tch khng gian rng hn th tch khng gian chim bi i electron lin kt. ng thi lc y gia chng cng mnh hn so vi i electron lin kt, c minh ho hnh 3.4.
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(1) (2) (1) 4 i electron lin kt tng ng nhau (2) 1 i electron ring chim khng gian rng hn i electron lin kt HNH 3.4. S khc nhau gia i e lin kt v i e ring v ho tr Dng hnh hc ca 1 s loi phn t Xt mt s trng hp c bn, ch yu l lin kt n. + AXn vi n = 2 6 Trng hp ny nguyn t trung tm A khng c i electron ring. S phn b cc i electron lin kt cho ta hnh dng phn t tng ng, trong mi trng hp t n = 2 n n = 6 c biu din trong cc hnh tng ng t hnh 3.5 n hnh 3.9. y cn nhc li l: S phn b cc i electron lin kt cch xa nhau nht c th c lc y gia chng l nh nht. Trong mi hnh trn, c hai cch biu din: - S phn b cc i electron trn v ho tr - l v hnh cu. - Hnh dng khng gian ca phn t, c th:
Hnh 3.5. n =2 Hnh 3.6. n = 3 Hnh 3.7. n = 4 ng thng Tam gic T din n = 2: hai i electron c phn b trn ng thng. Phn t thng, nh BeH2. Gc lin kt XAX bng 1800. n = 3: ba i electron c phn b trn ba nh ca tam gic u. Phn t c hnh tam gic u, phng. Gc XAX bng 1200. Nh, BF3, AlCl3,... cc ion nh CO32 , NO3 ,... n = 4: Bn i electron c phn b bn nh ca hnh t din u, tm l A. Phn t c hnh t din. Gc XAX bng 109028. Nh CH4, ... Xt phn t dng AX5, vi n = 5
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(2) (3) HNH 3.8. n = 5 (1) S phn b 5 i electron v ha tr trn mt cu (2) Hnh lng thp tam gic c to ra t s phn b 5 i electron (3) V d minh ha, phn t PCl5 trong mt phng c gc <ClPCl = 1200 Theo m hnh VSEPR, nm i electron c phn b trn mt cu v ho tr nh sau: Ba i cng vi ht nhn A nm trong mt mt phng (mt phng vung gc vi mt phng giy), ba i ny nm ba nh ca mt tam gic u tm l A. Cc lin kt to ra trong mt phng ny gi l lin kt ngang. Hai i electron cn li c phn b hai u ca on thng nm trn mt phng giy v vung gc vi mt phng ca tam gic u ti A. Hai i electron ny to ra lin kt trc. Do s phn b ny m di lin kt ngang ngn hn di ca lin kt trc, hnh 3.8 (1). Kt qu ca s sp xp ny a ti mt kt qu v hnh nh ca phn t dng ny l mt lng thp tam gic m y l tam gic u tm A, hai nh l i electron to ra lin kt trc, hnh 3.8 (2). V d c th l phn t PCl5, hnh 3.8 (3). Xt phn t dng AX6, n = 6
(1)
(4)
(5)
(6)
HNH 3.9. n = 6 (4), S phn b 6 i electron trn mt cu v ho tr. (5), Hnh bt din u c to ra t s phn b 6 i electron ny. (6), V d minh ho, phn t SF6. Su i electron ca phn t ny c phn b trn v ho tr ca nguyn t A su nh ca mt hnh bt din u (hnh 3.9. 4 v 5), gc gia cc trc lin kt u bng nhau v bng 900, di ca cc lin kt u bng nhau, do khng c s phn bit lin kt ngang v lin kt trc.
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BNG 3.3 tng kt mt s hnh dng khng gian ca cc phn t AXn, vi n = 2 6 .
Bng 3.4 cung cp cho ngi hc mt s t liu xt lin kt ho hc v hnh dng ca mt s phn t. Trong thc t chng ta t gp cc phn t dng AXn vi n 7. Bng 3.3. Tng kt mt s hnh dng khng gian ca cc phn t dng AXn, vi n = 2 6 + Vi AXnEm Nguyn t trung tm A va c n i electron lin kt, va c m i electron khng lin kt c k hiu l E. Khi xt trng hp ny cn lu s khc nhau gia i electron lin kt v i electron ring. phn trc ch r i electron ring chim th tch trong khng gian ln hn i electron lin kt. V th trong hai trng hp AXn v AXnEm tuy c cng s i electron nhng hnh dng ca hai phn t li khng ging nhau hon ton. Chng ta xt mt s trng hp c th sau:
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BNG 3.4. Cu hnh electron v s oxi ha ca mt s nguyn t
Xt phn t dng AX2E
HNH 3.10. Phn t AX2E khng phng (phn t c gc) Ba nguyn t A, X, X khng cn nm trn cng mt ng thng ging nh trng hp AX2 (hnh 3.5), khi ny phn t c gc (hnh 3.10). Nguyn nhn l do i electron ring chim th tch khng gian ln nn y hai i electron lin kt v cng mt pha m gc lin kt ca n < 1800. V d, phn t SnCl2 c gc ClSnCl 1200.
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Xt phn t dng AX3E Nguyn t trung tm A c tng cng 4 i electron nhng phn t khng c hnh t din u nh trng hp AX4 (CH4) m li c hnh thp tam gic. in hnh cho trng hp ny l phn t NH3, c gc HNH 1070 (hnh 3.11). Xt phn t dng AX2E2 Trng hp ny nguyn t trung tm A cng c 4 i electron, nhng c 2 i electron ring nn hnh dng phn t khc vi AX4 v cng khc vi AX3E. Phn t AX2E2 c gc gn vi gc ca hnh t din, v d phn t H2O c gc HOH 104,50 (mt s ti liu ghi l 1040), hnh 3.12.
HNH 3.11. Hnh thp tam gic ca phn t NH3 (dng AX3E)
HNH 3.12. Phn t H2O c gc HOH 104,50 (dng AX2E2) Cc bn sinh vin hy s dng m hnh VSPER d on hnh dng phn t AXE3, ly phn t HF lm v d:
HNH 3.13. Phn t HF, phn t thng Nguyn t trung tm F (nguyn t A) c 4 i electron, nhng ch c mt i electron lin kt. Do hnh hc ca phn t HF ph thuc vo i electron lin kt. l phn t thng. Chng ta xt cc phn t m nguyn t trung tm A c 5 i electron. phn trc, phn t AX5 c dng hnh lng thp tam gic (hnh 3.8). Nhng khi c mt i electron ring th hnh s b bin dng i, ty thuc vo s i electron ring.
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+ Phn t dng AX4E: S phn b mt i electron ring v bn i electron lin kt c m t trn hnh 3.14.
HNH 3.14. Phn t AX4E c hnh dng ci bp bnh T hnh 3.14, ta thy phn t dng AX4E c dng hnh ci bp bnh, v d phn t SF4. + Phn t dng AX3E2: Phn t ny c 3 i electron lin kt v 2 i electron ring. 3 i electron lin kt to ra 3 lin kt AX. S y tng h gia 3 i electron lin kt v 2 i electron ring lm cho phn t c hnh ch T, hnh 3.15. V d, phn t ClF3, HClO2.
HNH 3.15. Phn t AX3E2 c hnh ch T Chng ta xt cc phn t m nguyn t trung tm A c 6 i electron + Phn t dng AX5E: Bn trong nm i electron lin kt c phn b trong mt mt phng, mt i electron lin kt cn li c phn b trn mt trc gn nh vung gc vi mt phng trn. V vy nm i electron lin kt to ra hnh thp vung. Phn t dng ny c lin kt ngang v lin kt trc khng tng ng nhau. Phn t BrF5, hnh 3.16.
HNH 3.16. Phn t BrF5, dng AX5E c dng hnh thp vung + Phn t dng AX4E2: Bn i electron lin kt c phn b trong mt mt phng to ra hnh vung phng, hai i electron ring c phn b v hai pha ca mt phng cha bn lin kt AX. V d phn t XeF4, hnh 3.17.
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HNH 3.17. Phn t XeF4, dng AX4E2 c dng hnh vung phng Hnh dng phn t lun gn lin vi tnh cht ca phn t, nh nhit nng chy, nhit si, hot tnh sinh hc, ... * nh hng ca m in n ln ca gc lin kt m in ca nguyn t trung tm A v phi t X u c nh hng n ln ca gc lin kt, tc l c nh hng n hnh dng ca phn t. Hnh dng phn t lun gn lin vi tnh cht ca phn t, nh nhit nng chy, nhit si, hot tnh sinh hc, ... V nguyn tc: A c m in cng ln th n ht my ca i electron lin kt v pha n cng mnh do lm tng ln ca gc lin kt, v my e lin kt cng gn A th chng y nhau cng mnh. Nu phi t X c m in ln th gy tc dng ngc li. V d 5: HOH = 1040 ; FOF = 1030; HSH = 920 (AX2E2) 0 NH3 = 107 ; NF3 = 1020; PH3 = 930 Xt dy sau PI3, PBr3 , PCl3, PF3 gc lin kt gim theo trt t 1020, 1010, 1000, 970 * Hnh dng ca 1 s phn t cha lin kt bi Trong trng hp ny quy c cch tnh s i electron trong phn t nh sau: - Mi i electrron lin kt to 1 lin kt n, hay 1 i electrron ring vn tnh l 1 i electrron nh trn. - Hai i electrron to lin kt i ( = ), c tnh l 1 i electron - Ba i electron to lin kt ba (), c tnh l 1 i electrron S i electrron trn tnh cho tng nguyn t trung tm, sau quy v mt trong cc phn t xt, t suy ra hnh dng ca phn t. Ch : vi cc phn t phc tp ta phi quy cc nhm nguyn t thnh tng phn ring bit, khi s gii thch c gc lin kt. V d 6: C2H6 c cng thc cu to l CH3 CH3 quy v dng AX3X hay AX4 t din vi C l nguyn t trung tm. V d 7: CHCH quy v dng CHXhay CX2 phn t thng.
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b2) Momen lng cc Lun c s lin h mt thit gia momen lng cc ca phn t vi lin kt ha hc, cu to, hnh dng ca phn t. * M men lng cc ca phn t Phn t bao gn cc ht nhn mang in tch dng (+) v cc electron mang in tch m (-). Tr s tng cng cc in tch dng bng +Q, cn in tch m bng -Q. V phn t lun trung ha v in nn Q-Q. Hai trng tm ca hai r in tch cch nhau bng mt khong cch c xc nh bi vc t r , gi s hng t Q n -Q (hnh 3.18)
HNH 3.18. M hnh xc nh chiu ca vc t v tr r gia hai trung tm in tch ca phn t r Momen lng cc ca phn t, k hiu l , c nh ngha nh sau: r r = Qr (3.1) Nh vy momen lng cc l mt i lng vc t, c chiu t in tch dng (+) n in tch m (-). Tr s hay ln ca momen lng cc c biu th theo biu thc: = Qr (3.2) Trong h SI (h n v o lng quc t), n v ca l Cm (Culong.mt). Theo thi quen, chng ta hay dng n v bai, k hiu l D. Gia D v Cm c mi lin h: 1D 3,33.10-30Cm - Nu phn t c = 0, phn t l phn t khng phn cc nh H2, CO2, CH4, C6H6, ... - Nu phn t c 0, phn t l phn t phn cc. cng ln th phn t phn cc cng nhiu. BNG 3.5. Tr s momen lng cc (tnh theo D) ca mt s phn t thng gp
Phn t HCl Hbr HI H2O H2S SO2 NO2 0,38 1,84 0,78 1,67 0,32
Phn t NH3 NF3 C2H5OH C6H5Cl C6H5NH2 C6H5NO2 C6H5CN
1,08 0.79
1,47 0.24 1,58 1,53 1,60 3,90 4,14
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* Momen lin kt i vi phn t 2 nguyn t H2, HCl, ... momen lng cc ca phn t cng chnh l momen lng cc ca lin kt gia hai nguyn t HH hay HCl. i vi phn t c t 3 nguyn t tr nn, cn phi phn bit momen lng cc ca lin kt vi momen lng cc ca phn t. Momen lng cc ca lin kt gi tt l momen lin kt Xt phn t 3 nguyn t ABC (nh H2O), c 2 lin kt AB v AC. Hai r r momen lin kt tng ng l 1 v 2 , c gc lin kt l .
HNH 3.19. Mi lin h gia momen lng cc ca phn t r r vi cc momen lin kt 1 v 2 r r r Momen lng cc ca phn t l c lin h vi 1 v 2 (hnh 3.19) Mt cch gn ng, p dng phng php cng momen (theo quy tc hnh bnh hnh, ging nh trong tng hp lc) tnh momen lng cc ca phn t t cc momen lin kt, ta s dng cng thc: 2 (3.3) = 12 + 21 2 cos + 2 Cn ch n chiu ca momen lin kt. Vi phn t CO2 l phn t thng ta c: r r
O 1 C 2 O Cc lin kt C = O phn cc mnh ( C =O = 2,7( D)) nhng v phn t c cu
to i xng nn momen lng cc ca chng b tr nhau, do kt qu cng momen lng cc ca phn t bng khng ( CO = 0 ) v phn t CO2 khng phn cc. Php cng momen p dng cho mi phn t. Vi phn t CH4, tng tr s ca 3 momen ca 3 lin kt C H bng tr s nhng ngc chiu vi momen lin kt ca lin kt cn li. Kt qu cng momen cho c phn t CH4 hay HCH3 bng 0 , CH = 0 Tng t nh CO2v CH4 nhng phn t i xng khc nh CS2, HgCl2, BeH2, SiF6, ... u l nhng phn t khng c cc. Ngc li nhng phn t c cu to khng i xng nh H2O, SO2, NO2, ...nhng vc t momen lin kt trong phn t khi cng khng b tr nhau nn phn t u c cc. Da vo biu thc (3.3) d dng tnh c momen lin kt trong phn t H2O khi bit momen lng cc ca H2O bng 1,84(D), H O = 1,84( D) v gc lin kt bng 104,50. S dng biu thc (3.3) tnh c:
2 4 2
2 2 2 H O = H O + 2 H O + H O = 1,84 H O = 1,58( D)
2
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b3) T tnh ca phn t Da vo vic mt cht chu tc dng nh th no ca t trng, m phn chia cc cht lm ba loi: cht nghch t, cht thun t v cht st t. * Cht nhgch t cn ng sc ca t trng mnh hn so vi chn khng nn b t trng y. * Cht thun t cho ng sc ca t trng i qua n d dng hn so vi chn khng, nn t trng c su hng ko di n ra. * Cht st t l cht thun t c bit mnh, y l tnh cht ca tinh th kim loi st. Tnh cht t ca st th hin ch n b nam chm ht, v bn thn n cng tr thnh nam chm vnh cu khi c dng in mt chiu vi cng ln i qua n. Khi t vo gia hai cc ca nam chm, cht nghch t nm theo phng vung gc vi ng sc, cht thun t nm dc theo ng sc (hnh 3.20), cn cht st t b nam chm ht hn v mt cc.
HNH 3.20. Cht nghch t (a) v cht thun t (b) i vi t trng S khc nhau v t tnh ca cc cht l do s khc nhau ca t trng bn trong mi cht gy ra. Chng ta u bit, electron trong nguyn t cng nh bt k in tch no khi chuyn ng s to nn t trng. Bi vy mt electron trong nguyn t l mt nam chm c bn. N c mt momen t spin to nn bi s quay quanh trc ring ca n v mt momen t obitan to nn bi s chuyn ng ca electron xung quanh ht nhn nguyn t. n v o momen t l maneton Bo, k hiu l B v bng:
B =
e v m l in tch v khi lng ca electron, h l hng s Plng, C l vn tc nh sng. Momen t ca nguyn t, phn t hay ion l tng vc t nhng momen t spin v momen t obitan ca tt c cc electron c trong . Momen t ca nhng electron ghp i obitan nguyn t (AO) hay obitan phn t (MO) s b tr nhau. Nhng nguyn t, phn t hay ion ch gm
eh 4mC
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nhng electron ghp i c momen t bng khng nn l cht nghch t. Nhng nguyn t, phn t hay ion c mt hay vi electron c thn lun c momen t vnh cu, nn l cht thun t. Trong trng hp ny nu momen t obitan ca electron bng 0 hoc khng ng k, th momen t spin tng hp ca nguyn t, phn t hay ion c xc nh theo biu thc:
= n ( n + 2) B
n l s electron c thn. V vy xc nh momen t l mt vic lm quan trng bit s electron c thn c trong mt cht. Nhng n cht kh nh H2, N2, Cl2, v kh him, nhng n cht rn nh kim cng, lu hunh v bitmut, nhng ion c cu hnh electron ca kh him, nhng hp cht nh CO2, HCl v nhiu hp cht hu c l cht nghch t v trong cc cht tt c cc electron u ghp i. Nhng nguyn t nh H, Cl, N, nhng kim loi nh K, Sn, Al,..., nhiu kim loi chuyn tip, nhng phn t nh NO, NO2, O2 l nhng cht thun t v chng c electron c thn. Mt vi kim loi nh Fe, Co, Ni, mt s hp kim v vi hp cht c tnh st t. c im ca cht st t l sau khi c t vo t trng nu b t trng i, n vn cn gi c t trng ring ca n. Cn ch : Tnh cht st t l tnh cht ca mng li tinh th ch khng phi l tnh cht ca nguyn t, phn t. Cn tnh thun t, tnh nghch t l tnh cht ca phn t, nguyn t. 2. LIN KT CNG HA TR V LIN KT ION 2.1. Quy tc bt t 2.1.1. Cc dng lin kt ho hc Lin kt ha hc c bn dng ch yu sau: - Lin kt cng ha tr (lin kt nguyn t) - Lin kt ion (lin kt in ha tr) - Lin kt kim loi - Lin kt hiro, tng tc Van ec Van gi chung l tng tc yu gia cc phn t . Khng c ranh gii phn bit r rt. Tuy nhin, thun li ngi ta thng tch ring tng dng ra cho d nghin cu. trong lin kt cng ha tr v lin kt ion c nghin cu nhiu hn. 2.1.2. Nhn xt Heli: c 2e lp th nht (1s2), lp ny bo ha (lp ngoi cng) nn bn. Cc kh him khc c 8e lp ngoi cng (ns2np6) bo ha nn n cng bn. V vy kh him l h m phn t ch c mt nguyn t, c electron lp ngoi cng bo ha nn rt t hot ng v mt ha hc (tr). T cc kt qu a ra trn thy rng cu trc 8e lp ngoi cng l 1 cu trc c bit bn vng.
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2.1.3. Quy tc bt t "Cc nguyn t ca cc nguyn t c khuynh hng lin kt vi cc nguyn t khc t cu trc electron vng bn ca cc kh him vi 8e (hoc vi 2 ging He) lp ngoi cng". Hn ch ca quy tc ny ch, quy tc khng c tnh tng qut do ch p dng c cho mt s t nguyn t, ch yu l cc nguyn t ca chu k 2. 2.2. Thuyt electron v ho tr - S Lewis (thi k tin c hc lng t) (Lewis ngi M sinh nm 1875 mt nm 1946) * Nhn xt: T quy tc bt t nhn thy c 2 cch t c cu hnh bn ca kh him. Th nht: C s chuyn electron t nguyn t ny sang nguyn t khc t hnh thnh lin kt ion. Th hai: C s gp chung cc cp electron t hnh thnh lin kt cng ha tr. Quy tc bt t v s hnh thnh 2 loi lin kt ny l do Lewis xut, sau ny c Langmuir pht trin thnh thuyt electron v ha tr. Ha tr ion l s electron m nguyn t ca nguyn t nhng ( thnh ion dng) hoc nhn thm ( tr thnh ion m) t hnh thnh nn khi nim v ha tr ca nguyn t v in tch ca ion. Cng ha tr l s cp electron m cc nguyn t em ra gp chung. 2.2.1. Thuyt Lewis Nm 1916 Lewis a ra gi thuyt: Phn t c to ra t cc nguyn t phi kim, lin kt ha hc gia hai nguyn t c thc hin bi cp electron dng chung, nh m mi nguyn t u c c cu hnh lp ngoi cng bn vng ca nguyn t kh him, vi 8e. Electron ca mi nguyn t c th tham gia c vo vic hnh thnh lin kt ha hc gi l electron ha tr. i electron dng chung to lin kt phi c spin i nhau (ngc nhau). Phn t Cl2 c mt lin kt gia hai nguyn t Cl c thc hin nh i electron..dng chung .. :Cl : Cl: hay Cl : Cl i electron ny l i electron lin kt, c k hiu .. .. l hay ; cc electron cn li c gi l cc electron ring. 2.2.2. S c bn ca lin kt cng ho tr a) S thun tu cng ho tr Xt s hnh thnh phn t H2, Cl2, NH3, H2O .. .. .. .. . + . Cl: :Cl : Cl: :Cl .. .. .. .. Cl-Cl hay Cl-Cl Cng thc cu to ca Cl2: Mun dng chung cc cp electron, cc obitan nguyn t phi xen ph vi nhau. Vy bn cht ca lin kt cng ha tr l s xen ph cc obitan. Cc obitan nguyn t (AO) mun tham gian xen ph c vi nhau phi c 1 e c thn hoc khng c e.
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b) S phi t (lin kt phi tr hay lin kt cho nhn) iu kin: - 1 nguyn t phi c 2 electron trn 1 AO - Nguyn t kia c AO trng V d 1: Ion NH 4+ , H3O+ in tch (+) c phn b trn ton b ion NH 4+ th ion NH 4+ mi bn vng, ch khng c tp trung bt k nguyn t no trong h NH 4+ (nguyn l cc tiu nng lng). Vy iu kin to lin kt cng ho tr l c hai nguyn t u phi c electron c thn lp ngoi cng (lin kt cng ho tr thun tu) hoc mt nguyn t c cp electron khng lin kt cn nguyn t kia phi c A0 trng (lin kt cng ho tr phi tr). c) Electron lin kt, electrron khng lin kt (khng phn chia) Cp electron lin kt cn gi l cp electron chung, cp electron khng lin kt cn gi l cp electron ring. V d 2: trong phn t NH3 c 3 cp electron lin kt gia nit v hiro, c mt cp electron khng lin kt nm ti nguyn t nit. i vi phn t H2O c 2 cp electrron lin kt gia oxi v hidro, nguyn t oxi c 2 cp electron khng lin kt. d) Lin kt n, lin kt bi (i, ba) Gia hai nguyn t tham gia lin kt vi nhau c mt cp electron dng chung th gi l lin kt n, c hai cp electron dng chung l lin kt i v c ba cp electron dng chung l lin kt ba. V d 3: Trong phn t Cl2, gia hai nguyn t Cl c mt cp dng chung ta c lin kt n. Trong phn t CO2 c hai cp dng chung gia C v O, cn trong N2 th c ba cp dng chung gia hai nguyn t nit. Cl Cl ; O=C=O; NN 2.2.3. Biu din lin kt cng ha tr bng lng t Da vo cu hnh e lp ngoi cng ca nguyn t v dng lng t () biu din 1 A0. - Quy c: Lin kt CHT: Lin kt phi tr: V d 4: xt H2S H: 1s1 S: [Ne] 3s23p4 S 3s 3p HSH
H
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Xt HClO
3s Cl:
3p
O 2s 2p H
H O Cl
T cc v d trn nhn thy cch biu din ny nng n v mt hnh thc, khng m t c cu trc thc ca phn t, do c nhiu cch biu din khc nhau. * Trng thi ha tr ca mt nguyn t l trng thi gi nh ca nguyn t dng gii thch cu to thc ca phn t. Trng thi ha tr khng phi l trng thi thc. V d 5: CH4 : Gii thch 4 lin kt cng ho tr ca C th phi dng trng thi gi nh. C: C*:
Trng thi c bn Trng thi ha tr
C* 2s
H H C H H
V d 6: PCl3 v PCl5 P: 3s 3p
* Cl* Cl* Cl
Cl
P Cl
Cl
Vi PCl5; cu hnh electron ca P trng thi c bn nh sau: P: 3s 3p 3d Khi c kch thch 1e obitan 1s nhy ln obitan 3d, lc ny P trng thi kch thch (trng thi ha tr) c 5e c thn, c 5e ny u tham gia to lin kt vi cc nguyn t Cl hnh thnh phn t PCl5. 3s 3p 3d * P
* * * * Cl* Cl Cl Cl Cl
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Trong cc v d trn, trng thi ha tr, cc electron c thn (electrron ha tr) tng ln, ngc li cng c th ghp i c cc lng t trng trng thi ho tr. * Hn ch: Vi cc cht c lin kt i, ba, nhiu khi phi dng nhiu cu trc gii hn, khng c thc m t mt cch nng n phn t. Khng gii thch v tin on c cu trc hnh hc ca phn t, s khc nhau c bn v lin kt v lin kt . Khng gii thch c 4 lin kt n l nh nhau trong phn t metan. Khng gii thch c trong phn t H 2+ lin kt ch c 1e v phn t O2 li c tnh thun t (theo Lewis th O2 khng c electrron c thn nn l phn t nghch t). 2.2.4. Phn loi lin kt cng ha tr Cn c vo v tr ca cp electron dng chung so vi hai ht nhn nguyn t tham gia lin kt, m phn chia lin kt thnh hai loi. a) Lin kt cng ha tr khng phn cc (hay khng c cc) Cp electron dng chung nm gia khong cch hai ht nhn nguyn t. l lin kt trong cc phn t n cht nh H2, Cl2, N2, ...hoc gia hai nguyn t ca hai nguyn t khc nhau th m din ca chng phi bng nhau. b) Lin kt cng ha tr c cc (hay phn cc) Cp electron dng chung nm lch v pha nguyn t ca nguyn t phi kim c m in mnh hn (c tnh phi kim mnh hn). l lin kt ha hc hnh thnh trong cc phn t nh H2O, NH3, CH4, ... 2.2.5. Tnh nh hng khng gian ca lin kt cng ha tr Trong lin kt cng ha tr, cp electron dng chung (i electron dng chung) c phn b khong khng gian gia hai ht nhn tham gia lin kt. V vy chng ta ni: Lin kt cng ha tr c tnh nh hng khng gian. T c im ny m s nguyn t lin kt vi mt nguyn t cho trc b hn ch bi ha tr ca nguyn t . y chnh l nguyn nhn gy ra tnh bo ha ca lin kt cng ha tr. Trong hp cht gia Cl v H, ch c mt nguyn t H lin kt vi mt nguyn t Cl to thnh HCl, khng th c nhiu hn mt nguyn t H lin kt vi mt nguyn t Cl. 2.3. S phn cc ca lin kt cng ha tr. S to thnh lin kt ion 2.3.1. Thuyt Cxen Nm 1916, Cxen a ra gi thuyt: Trong cc phn ng ha hc xc nh, cc nguyn t c xu hng thu thm hay nhng bt electron t ti cu hnh electron bn vng ca nguyn t kh him vi 8e lp ngoi cng. Cc nguyn t tr thnh ion, chng ht nhau to thnh hp cht c lin kt ion. i vi phn t 2 nguyn t c m in khc nhau nhiu th phn t b phn cc ho, kt qu to thnh 2 ion: A. + .B A+ + :B- (B c m in hn A)
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2 ion ht nhau to nn phn t ion AB (lin kt c to nn do tng tc tnh in gia cc ion). V d 7: Na + 1/2Cl2 NaCl
Na 1e Na + Na + + Cl NaCl Cl + 1e Cl
c 8e lp ngoi cng, nguyn t kim loi nhng bt mt s electron lp v ho tr tr thnh ion dng:
M ne M n + Trong thc t, thng gp n = 1 (kim loi kim); n = 2 (kim loi kim th, Zn, Fe, ...); cc trng hp khc t gp hn, nh n = 3 (Al, Cr); ...
Trong khi phi kim thu thm 1e (do nguyn t phi kim vn c nhiu electron ho tr v) tr thnh ion m:
X + ne X n Thc t, ch yu xy ra trng hp n = 1 (cc nguyn t ca cc nguyn t halogen). Vi n 2 , cc ion m t c kh nng tn ti do c s y ln nhau gia
cc electron v lm cho ion km bn ( Trongbng 3.2), cc ion ny c t trong ngoc n). V d 8: Khng c ion O2- m ch c ion OH- do ion O2- kt hp vi ion H+ m thnh. BNG 3.6. Mt s ion n nguyn t ca mt s nguyn t phn nhm chnh
Nhm I Li+ Na+ K+ Rb+ Cs+ II Be2+ Mg2+ Ca2+ Sr2+ Ba2+ Al3+ III IV V (N3-) (P3-) VI (O2-) (S2-) VII FClBrI-
Lin kt ion ch l trng hp gii hn (s phn cc ho) ca lin kt cng ha tr. Thc t khng c lin kt ion 100%. V d lin kt ion ca NaF ch t c 91%; NaCl: 85%. Da vo hiu m in xt c tnh ion ca mt lin kt n: Gi s c hp cht AB, c B > A khi lin kt phn cc t A sang B + A B-: Hiu m in B A = 1,8 3,2 th % ion = 55% 92% Vi B A > 1,7 coi lin kt A B l lin kt ion B A < 1,7 coi lin kt A B l lin kt cng ha tr. tnh % ion ca 1 lin kt, da vo biu thc: (%) =
tn 100 lt
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Chng ta cng nhau tr li cu hi: Ti sao nguyn t A li nhng electron cho nguyn t B? Nguyn nhn no gy ra? C mi quan h g gia lin kt cng ho tr v lin kt ion khng? Xt mt s phn t dng: A2 gm cc phn t H2, Cl2, Na2 c cng thc electron: H : H Cl : Cl Na : Na Cc cp electron dng chung nm gia hai ht nhn, vy cc phn t H2, Cl2, Na2 l phn t khng phn cc, A = 0 . AB gm HCl, NaCl c cng thc electron: H : Cl Na :Cl Chng ta thy, do s chnh lch v m in m cp electron dng chung phn t NaCl lch hn v Cl. Chnh iu ny cho thy khi c s phn cc mnh cp electron dng chung m lin kt cng ho tr bin thnh lin kt ion.
2
2.3.2. Mt s c im ca lin kt ion v hp cht ion a) Lc lin kt l lc tnh in Do cc ion tch in tri du ht nhau to ra hp cht ion. Lc lin kt trong hp cht ion ch yu l lc tnh in b) Khng c tnh nh hng khng gian v khng c tnh bo ha Nu coi cc ion c dng hnh qu cu. Lc tnh in m cc ion tc dng c phn b u v tt c cc phng. V th m lc tng tc tnh in khng c tnh nh hng khng gian t khng c tnh bo ha. Lin kt ion khng c tnh nh hng khng gian, tc l mi ion c th ht v mnh cc ion tri du theo mt phng bt k. Lin kt ion khng c tnh bo ho, tc l 1 ion (+), c th lin kt vi nhiu ion m (-) quanh n v ngc li. T 2 c im ny cho kt qu l mt ion c bao quanh n bi mt s ion tch in tri du. Kt qu cc phn t ion c xu hng lin kt vi nhau mnh m to thnh mng li tinh th ion trng thi rn c nhit nng chy cao. Trong mng li tinh th ny khng th nhn bit c tng phn t ring r. Nn vic vit cng thc hp cht ion nh vn thng dng, nh NaCl, MgO, CaCl2,..., Ch l quy c. Cc cng thc ny c gi l cng thc kinh nghim. c) Lun trung ho v in Hp cht ion khi vit di dng cng thc thc nghim hay khi xt cho c mng tinh th, u trung ho v in. V d 8: xt cng thc MgCl2, ta thy : MgCl2 Mg2+ + 2Cl-
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Tng cc in tch dng v m bng khng, tc l phn t c biu din bng cng thc kinh nghim trung ho in . Nu xt trong c mng tinh th MgCl2 cng c s trung ho in. 3. MT S VN CA THUYT LIN KT HA TR (thuyt VB) Thuyt lin kt ha tr, l mt trong s t thuyt c p dng tng i rng ri hin nay. Nh bc hc M L. Pauling (hai ln c gii Noben) l mt trong s cc nh khoa hc c cng xy dng v pht trin thuyt ny. u im ln nht ca thuyt ny l m hnh ca n n gin, d nh v gii thch thnh cng hnh dng c bn ca phn t. Nhng hn ch ch khng gii thch c s tn ti ca ion phn t H 2+ v tnh thun t ca phn t O2. 3.1. Mt s lun im c s ca thuyt lin kt ha tr (thuyt VB hay thuyt cp electron) 1) Trong phn t, cc electron vn chuyn ng trn cc obitan nguyn t (AO). Khi 2 AO ha tr ca 2 nguyn t xen ph vi nhau to ra lin kt ha hc th vng xen ph l vng chung cho c 2 nguyn t. 2) Mt lin kt ha hc gia 2 nguyn t c m bo bng 1 i electron c spin i song ( hoc ); Trong trng hp chung i electron gm 2 electron thuc 2 nguyn t ring r (1 nguyn t phi c t nht 1 AO c 1 e c thn) trc khi tham gia lin kt. 3) Trong s xen ph cc AO to ra lin kt ho hc gia 2 nguyn t, phng c u tin l ng ni tm 2 ht nhn (thuyt ha tr nh hng). 4) Trong s xen ph nu 1 AO xen ph vi AO kia mnh hn th lin kt ha hc s bn hn (nguyn l xen ph cc i). 5) Lin kt ha hc gia 2 nguyn t khng th hnh thnh c nu c 1 electron hoc 3e tr nn (tnh bo ha ca lin kt cng ha tr). Nh vy, theo thuyt VB, khng th c ion phn t H 2+ (c 1e) hoc H 2 ( c 3e). 3.2. Mt s thuyt trong phm vi thuyt VB 3.2.1. Thuyt Spin v ha tr Ha tr l mt trong nhng khi nim quan trng ca ha hc. V vy khi bn n vn ny th cn phi bit: Ha tr lun c xt trong mt phm vi nht nh. Ha tr cp trong chng ny l cng ha tr tc l ha tr ca cc nguyn t trong hp cht cng ha tr. a) Ni dung S electron c thn ca nguyn t trng thi ang xt (trng thi ha tr) xc nh s n v ha tr ca nguyn t . Thuyt spin v ha tr dng d on nhng trng thi ha tr c th c ca mt nguyn t trong phn t trng thi ang xt. Thuyt ny khng dng xc nh ha tr ca mt nguyn t c th no trong phn t, v mun bit ha tr cn phi xc nh c ng cng thc cu to ca phn t ang xt. b) Xt cc trng hp c th * Xt cc nguyn t chu k 2: Cc nguyn t ca cc nguyn t ny c cu hnh electron lp ngoi cng l 2s1-22p1-6
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S AO ha tr ca cc nguyn t chu k 2 l 4: 2s 2px 2py 2pz Do nguyn t ca cc nguyn t chu k 2 c nhiu nht 4e c thn. Vy S n v ha tr ti a ca cc nguyn t ca cc nguyn t thuc chu k 2 l 4. V d 9: Cacbon c cu hnh e : 1s2 2s22p2 C
E = hv
C*
trng thi c bn C c 2e c thn, vy C c ha tr 2; trng thi ha tr C c 4 e c thn, vy C c ha tr 4. V d 10: Nit c cu hnh e : 1s22s2 2p3
Trng thi c bn, N c 3e c thn nn N c ha tr 3. N c ho tr 4 khi cp electron ring tham gia to lin kt phi tr vi mt nguyn t khc c AO trng. Cng c th gii thch ha tr 4 ca nit bng cch nit nhng 1 electron tr thnh N+ c cu hnh: N+ : Vy ho tr ti a ca N l 4 v trong 4 lin kt to thnh th 1 lin kt l lin kt phi tr, v d: NH 4+ , HNO3, NO3 , ...
H H NH H
+
O HON O
V vy, khng th ni nit c ho tr 5 nhng c th ni s oxi ho ca nit cao nht bng nm th li ng. V d 11: Nguyn t O Cu hnh electron trng thi c bn l: 1s2 2s22p4 S electron c phn b trn cc AO: Vy O c ha tr 2 ( TTCB). Oxi cng c th c ha tr mt khi oxi trng thi kch thch, hay trng thi ha tr (O*), O* trng thi ny (O*), O* c mt obitan trng nn c kh nng to thnh lin kt phi tr vi mt nguyn t khc c 1 cp electron khng lin kt, nh trong ion NH 4+ , HNO3 . V d 12: Nguyn t F, c cu hnh electron 1s2 2s22p5 ch c ho tr 1 * Xt cc nguyn t thuc chu k III 3s Cc nguyn t ny c 9 AO ho tr
3p
3d
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Do , v nguyn tc c 9e c thn dn ti ha tr ti a phi l 9. S e ti a lp ngoi cng l 8, nhng cc nguyn t thuc chu k III ha tr cao nht t c ch bng 7. V d 13: P [Ne]3s2 3p33d0 3s 3d E = h 3p
TTHT TTCB C 3e c thn c ho tr 3 C 5e c thn c ho tr 5 Xt tng t th lu hunh c cc ha tr l 2, 4, 6 cn Clo v cc halogen c ha tr l 1, 3, 5, 7 (tr Flo ch c ha tr 1) Cc nguyn t thuc chu k 3 c ha tr ti a l 7 Khi xt qu trnh hnh thnh lin kt ha hc theo quan im ca VB, ngi ta khi qut thnh: S lin kt cng ha tr m nguyn t tham gia cho bit s n v ha tr ca nguyn t trng thi ang xt. V d 14: Xt phn t NH3 th N c ha tr 3, cn vi NH 4+ th N c ha tr 4. T thy rng: Mun xc nh c ha tr ca nguyn t th bt buc phi xc nh c cu to ca phn t. T nhng iu trnh by trn nhn thy: 1. Ha tr l 1 khi nim c tnh quy c nn vic xc nh s n v ha tr ca mt nguyn t 1 trng thi no cng ch c tnh quy c, do xt ho tr cn phi da vo 1 cht c th. 2. Trong ha hc ngoi ha tr ngi ta cn a vo cc khi nim gi nh nh: s xi ha, in tch hnh thc, tu tng trng hp c th m dng khi nim no cho ph hp. 3. Thuyt spin v ho tr c mt s vai tr sau: + S dng n gin nn c dng rng ri trong ha hc v c v hu c. + Gip gii thch tng i tha ng cc c ch v vic hnh thnh v b gy cc lin kt ho hc. 3.2.2. Thuyt ha tr nh hng a) Ni dung Trong phn t hng c u tin cho vic hnh thnh lin kt ha hc l ng ni tm 2 ht nhn. Do c s nh hng ny m phn t c t 3 nguyn t tr ln th c hnh dng, di lin kt v gc lin kt (iu ny l ng nhin) xc nh. b) p dng Mt trong nhng tnh cht v phn t m thc nghim pht hin c l gc lin kt. Da vo thuyt ha tr nh hng c th gii thch c cc kt qu thc nghim.
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thch?
V d 15: Xt phn t H2S Thc nghim xc nh c phn t H2S c gc HSH 920. Hy gii
Tr li: Lu hunh c cu hnh electron l: [Ne] 3s23p4. S c 6 electron ho tr c phn b trong 4 AO: Hiro c cu hnh electron l: 1s1 Theo thuyt VB, 2 electron c thn ca S to vi 2 electron ca 2 nguyn t H 2 lin kt SH. 2 AO c 2 electron c thn ny c trc vung gc vi nhau (gi s AO - 3px, AO - 3py), tc to vi nhau gc 900. V AO - s c i xng cu, nn vng xen ph ca AO - s vi AO - 3p s phn b trn trc ca AO - p tng ng. Tc l gc ca H2S phi bng 900, tuy nhin 2 vng xen ph ny c mt electron cao nm cnh nhau (do m in ca S ln) s y nhau.
HNH 3. 21. Gc lin kt trong H2S theo thuyt ho tr nh hng S y mnh nhau ny lm cho gc HSH m rng ra, kt qu gc bng 0 92 nh kt qu thc nghim, minh ho hnh 3.21. Cng nhm VIA vi S cn c Se, Te u to hp cht vi H l H2Se, H2Te c gc tng ng l HSeH 910, HTeH 900. 3.2.3. Nguyn l xen ph cc i a) M u Nguyn l xen ph cc i l mt phn quan trng ca thuyt VB. Thuyt ny gip cho vic m rng hn na kh nng p dng ca thuyt VB trong vic gii thch cc kt qu thc nghim.
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hiu c phn ny, cn nh thuyt VB cho rng lin kt ho hc gia 2 nguyn t hnh thnh c l do c s xen ph ca 2 AO ha tr, mi AO c 1 electron c thn. hnh dung r iu ny, chng ta xt mt s giai on trong qu trnh hnh thnh phn t H2 t 2 nguyn t H t do, hnh 3.22.
HNH 3.22. Qu trnh hnh thnh H2 t cc nguyn t H *) 2 nguyn t H cc giai on (1), (2), (3). **) 2 AO (2 hm sng) ca 2 nguyn t H cc giai on tng ng. (1) Khi 2 nguyn t H xa nhau. (2) Khi 2 nguyn t H tin li gn nhau, khi ny c s xen ph 2 AO nhng cha ti mc to ra lin kt bn. (3) 2 nguyn t tin li gn nhau, khi khong cch gia 2 ht nhn l R0, s xen ph khi ny mnh, to lin kt bn, phn t H2 c hnh thnh v tn ti. T c th kt lun: Mc xen ph 2 AO ca 2 nguyn t tham gia lin kt c trng cho bn ca lin kt. V vy c th ni: Lin kt ha hc c to ra cng bn, nu s xen ph gia 2 AO cng mnh. Cng cn lu l hai ht nhn khng th tin li gn nhau vi mt khong cch nh hn R0, v khi lc y gia cc ht nhn vi nhau v lc y gia cc electron vi nhau mnh hn lc ht gia cc ht nhn v cc electron lm cho nng lng ca h phn t tng t bin (hnh 3.1 v 3.2), h tr nn khng bn. Vi phm nguyn l cc tiu v nng lng. b) Ni dung Trong s xen ph 2 AO to thnh 1 lin kt, th lin kt s c phn b theo 1 hng no m mc xen ph cc AO to lin kt c gi tr cc i. Ch : S xen ph cc i ny ch thc hin c vi cc thu c cng du ca AO v nh hng theo mt phng xc nh. V d 16: Tr s nng lng lin kt ca mt s lin kt nh sau: FF l 158; ClCl l 243; HH l 436 (kJ/mol). 1) Gi thit trong s hnh thnh lin kt c s xen ph : H2: 2 AO - 1s; F2: 2 AO - 2pz; Cl2: 2 AO -3pz. Hy dng hnh nh tng t nh hnh nh ca hnh 3.22 m t mc xen ph cc AO to lin kt trong 3 phn t .
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2) Tr s nng lng lin kt v m t 1) c gi g cho vic xp th t hot ng ca cc phn t trn. Hy a ra s sp xp ? Tr li 1) Chng ta k hiu khong khng gian trong c s xen ph 2 AO to lin kt trong H2 l S1, trong F2 l S2 cn trong Cl2 l S3, ta c: S1 > S3 > S2 ( cc bn sinh vin t v hnh) 2) T kt qu trn cho thy mc hot ng ho hc cng mt iu kin nh nhau l: F2 > Cl2 > H2 Nguyn nhn l do nng lng lin kt cng b (cng thp), phn t cng km bn, lin kt cng d b ct t th cng d to ra nguyn t c kh nng hot ng mnh hn phn t. 3.2.4. Thuyt lai ha (s lai ha cc AO) a) Khi nim Lai ha l s t hp tuyn tnh (trn ln) ca cc AO ha tr thun khit ca cng mt nguyn t trong phn t ch c s lng t ph (l) khc nhau to ra cc AO mi c c nng lng bng nhau. b) Mt s c im + iu kin cc AO ha tr tham gia lai ha c vi nhau l phi c nng lng gn bng nhau. T cc AO lai ha phi thuc cng mt lp (c cng s lng t chnh n) hoc thuc hai phn lp gn nhau (khc nhau s lng t ph l ). + S AO lai ha thu c bng s cc AO thun khit tham gia t hp tuyn tnh. + Cc AO lai ha thu c l cc AO suy bin, tc l cc AO ny c cng nng lng. + V mt hnh hc cc AO lai ha c hai thy (hai u) ngc nhau, mt thy n rng (thy to) cn thy kia thu hp (thy nh). c) Cc dng lai ha c bn Trong thc t, thng xt hp cht ca cc nguyn t thuc chu k 2. Cc AO ha tr ca mi nguyn t ca nguyn t chu k 2 l 2s, 2px, 2py, 2pz. Chng ta xt cc dng lai ha c cc AO ha tr ny tham gia. * Dng lai ha sp (lai ho thng): Gc lin kt 1800 Lai ho sp: Lai ha sp l lai ha trong mt AO-s t hp tuyn tnh vi mt AO-p (thng dng AO-pz) to ra hai AO lai ha, K hiu l AO-sp. C th hnh dung qu trnh lai ha xy ra nh sau E 2p 2p 2 p 2p 2 p
z x y x y

2pz
Lai ha sp
2AO-sp
2s
Gin nng lng
2 AO lai ha sp
HNH 3. 23. Gin nng lng biu din qu trnh lai ho sp

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Biu din hnh dng v s phn b khng gian ca cc AO lai ha, hnh 3.25 H ta biu th 3 AO - px, py, pz c minh ha hnh 3.24. AO - pz i xng trn trc z, AO - s c i xng cu. T hp tuyn tnh (trn ln) 2 AO ny ta c 2 AO mi cng nm trn trc z nhng ngc nhau v to thnh gc 1800, do lai ha sp cn gi l lai ha ng thng. 2 AO ny c hnh dng ging nhau mt thy m rng cn mt thy thu hp (hnh 3.25)
HNH 3.24. H ta ca 3AO: x, y, z.
HNH 3.25. Hnh dng v s phn b cc AO lai ha sp a) AO - s lai ha vi AO - pz b) AO lai ha thu c: (1) AO lai ha sp th nht, di1 (2) AO lai ha sp th 2, di2 (3) C 2 AO di1, di2 cng c t trn mt ng thng (trc z) Nhn xt: 1. 2AO lai ha sp1, sp2 chung nhau trc z v nm cng trn 1 ng thng, do lai ha sp cn gi l lai ha ng thng. 2. V 1AO-s 1AO-p 2AO-sp c 50% ging AO-s v 50% ging AOp. 3. Phng trnh ton hc ca hai AO lai ha sp
sp a = 1 (s + p z ) 2
(*)
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spb =
1 (s pz ) 2
(**)
s v p z ln lt l cc AO-s v AO-pZ.
4. Lai ha sp c dng gii thch s hnh thnh lin kt ha hc trong cc phn t BeH2, C2H2, v cc nguyn t mang mt lin kt 3 hoc hai lin kt i trong phn t. * Dng lai ha sp2 (lai ha tam gic): Gc lin kt 1200 Lai ho sp2: Lai ha sp2l lai ha trong mt AO-s t hp tuyn tnh vi hai AO-p (thng chn l AO-px hoc AO-py)to ra ba AO lai ha, k hiu l sp2. Nhn xt: 1. Tng t nh AO lai ha sp, AO-sp cng b bin dng so vi AO c bn, mt thy m rng v mt thy thu hp hnh 3.27). 2. Ba AO-sp2 c ba trc ca n cng nm trong mt mt phng, gc to bi hai trc ca hai AO cnh nhau l 1200. Do lai ha sp2 c gi l lai ha tam gic. k hiu cc AO lai ha sp2 ln lt l spa2 , spb2 , spc2 , (hnh 3.27). C th hnh dung qu trnh lai ha nh sau
E AO-p AO-p
Lai ha sp2 AO-s
3AO-sp2
HNH 3.26. Gin nng lng biu din qu trnh lai ha - sp2 Hnh dng v s phn b khng gian cc AO lai ha sp2 (hnh v trn)
(1) (2) (3) HNH3.27. S phn b khng gian cc AO lai ho sp2 (1) 3 trc to ca cc 3AO - px, py, pz (2), (3) hnh nh ca 3 AO lai ha v cc trc t1, t2, t3 tng ng vi cc AO - spa2 , spb2 , spc2 . Cc trc (t1, t2, t3) ny nm trong mt phng xy l mt phng vung gc vi mt phng giy cha trc z.
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3. Biu thc ton hc ca mi AO l:

2 sp a = 2 spb =
1 s + 2 py 3 3 1 s 1 p y + 1 px 3 6 2 1 s 1 p y 1 px 3 6 2
spc2 =
4. Lai ha sp2 c p dng gii thch lin kt ha hc trong cc phn t anken CnH2n (n 2), benzen C6H6, cc nguyn t mang mt lin kt i trong phn t, nh BX3 (X l cc nguyn t Halogen), C2H4 ..., NO2, SO2, cc ion nh
CO32 , NO32 , ...
* Dng lai ha sp3 (lai ha t din): Gc lin kt 109028 Lai ho sp3: Lai ha sp3 l lai ha trog mt AO-s t hp tuyn tnh vi ba AO-p to ra bn AO mi c cng nng lng c gi l lai ha sp3. C th hnh dung qu trnh lai ha nh sau, hnh 3.28.
E
AO-p Lai ha AO-s 4AO-sp3
HNH 3.28. Gin nng lng biu din qu trnh lai ha - sp3 Nhn xt: 1. Hnh dng ca mi AO lai ha sp3 cng tng t hnh dng AO lai ha sp, sp2 xt trn. 4 AO lai ha sp3 hng ra 4 nh ca hnh t din u m tm ca t din l nguyn t (chnh xc hn l ht nhn nguyn t) c cc AO lai ha. Do lai ha sp3 c gi l lai ha t din.
(1)
(2)
(3)
HNH 3.29. S phn b khng gian cc AO - sp3 (1) : Quy c h trc ta (2) v (3): S nh hng khng gian ca 4 AO - sp3 Cc gc nh ca hnh t din (gc T) u bng nhau v bng 109028
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2. Biu thc ton hc ca mi AO lai ho sp3 l:

3 te1 = spa =
1 (s p x p y + p z ) 2 1 (s p x + p y p z ) 2
3 te2 = spb =
te3 = spc3 =
1 (s + p x + p y + p z ) 2 1 3 te4 = spd = (s + p x p y p z ) 2
3. Lai ha sp3 dng gii thch lin kt ha hc trong cc ankan CnH2n +2 nh CH4, ngoi ra lai ho sp3 cn dng p dng cho cc phn t nh H2O, NH3, SnCl4, ..., cc ion nh SO42 , PO43 ,... d) Mt s dng lai ha khc Lai ha sp2d: Lai ha sp2d l lai ha trong mt AO - s t hp tuyn tnh vi 2 AO - p v mt AO - d to ra 4 AO lai ho, k hiu l sp2d Dng hnh hc ca lai ha sp2d: Vung phng Lai ha sp3d: Lai ha sp3d l lai ha trong mt AO - s t hp tuyn tnh vi ba AO - p v mt AO - d to ra 5 AO lai ha, K hiu l sp3d. Dng hnh hc ca lai ha sp3d: lng thp tam gic. Lai ha sp3d2: Lai ho sp3d2 l lai ha trong mt AO - s t hp tuyn rnh vi ba AO-p v hai AO-d to ra su AO lai as, K hiu l sp3d2. Dng hnh hc ca lai ha sp3d2: hnh bt din u. Ch : - Lai ha trong: L trng hp cc AO (n - 1)d, ns, np ca cng mt nguyn t (hoc ion) lai ho vi nhau. AO - d tham gia vo lai ho ny thuc lp bn trong ca AO - s v AO - p, l cc trng hp dsp2, dsp3, d2sp3. - Lai ha ngoi: L trng hp cc AO - ns, np, (n + 1)p ca cng mt nguyn t (hoc ion) t hp tuyn tnh vi nhau. AO - (n +1)d tham gia vo lai ha nm lp ngoi so vi AO - ns, np, do AO - (n + 1)d c nng lng cao hn AO - ns, np. V vy s lai ha ny kh thc hin hn so vi lai ha trong. l cc trng hp sp2d, sp3d, sp3d2. e) c im ca cc lin kt ha hc do AO lai ha thc hin. Cc AO lai ha bao gi cng c phn b trn cc trc, nn c i xng trc v vy cc lin kt c AO lai ha tham gia u l lin kt ?. Cc AO lai ha c mt thy c m rng, nn s xen ph ca cc AO lai ha khi tham gia lin kt ha hc thun li hn AO khng lai ha (AO thun khit), do cc lin kt c AO lai ha tham gia bn hn cc lin kt khc (nguyn l xen ph cc i). 3.3. Lin kt xich ma, lin kt pi. S ha tr s chng cht s ha tr a) Lin kt xich ma, lin kt pi Trong phn ny chng ta dng thuyt VB gii thch s hnh thnh cc lin kt c th trong ha hc. Trc ht cn thng nht mt s khi nim
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Theo thuyt VB, lin kt ha hc gia hai nguyn t c hnh thnh do s xen ph ca hai AO ha tr ca hai nguyn t lin kt vi nhau. Theo nguyn l xen ph cc i v thuyt ha tr nh hng, vng xen ph ca cc AO, tc lin kt ha gia hai nguyn t phi c phn b c nh hng, tc l theo mt trc xc nh, gi l trc lin kt; hay vng c gii hn bi mt phng, gi l mt phng lin kt. s xen ph cc AO dn n s hnh thnh cc lin kt ha hc, c 3 iu kin cn c tho mn ng thi: - Cc AO tham gia xen ph to thnh lin kt ha hc cn phi c nng lng xp x nhau (tc l gn nhau v mt nng lng). - Cc AO phi ph hp nhau v tnh i xng. Trong thc t ch c th xen ph 2 AO-px vi nhau, khng th c s xen ph 1AO-px vi 1AO-py v trc ca 2 AO ny vung gc vi nhau. - xen ph gia hai AO phi ln. * Lin kt xich ma: Lin kt ha hc gia hai nguyn t m vng xen ph ca 2 AO c phn b dc ng ni tm 2 ht nhn ca hai nguyn t , c gi l lin kt xch ma, k hiu l . ng ni tm 2 ht nhn c gi l trc lin kt . Trc ny nm trong mt phng c gi l mt phng . c im ca lin kt : + Lin kt l lin kt bn. + C tnh i xng vi trc lin kt, tc l cc nguyn t (hay nhm nguyn t) c th quay c t do quanh trc lin kt m khng lm nh hng n lin kt. Nhng AO c th xen ph vi nhau to lin kt + AO - s: - 2 AO - s xen ph vi nhau, xem hnh 3.22 - 1 AO - s xen ph vi 1 trong cc AO sau: ++ AO - p, v nguyn tc c th ly AO-p bt k, tuy nhin hay dng AO-pz. ++ AO lai ho sp, sp2, hoc sp3 + AO-pz: - 2 AO-pz vi nhau. Xt phn t Cl2 trong hnh 3.30.
HNH 3.30. Xen ph 2 AO - pz to lin kt p - p trong phn t Cl2 - 1 AO-pz vi 1 AO-s hay vi 1 AO lai ha. + AO lai ha sp, sp2, sp3: - 2 AO lai ha xen ph vi nhau (xem C2H4 phn lin kt pi) - 1 AO lai ha vi 1 AO-s hay vi 1 AO-p * Lin kt pi: L lin kt c to ra t s xen ph 2 AO-p thun khit ca hai nguyn t tham gia lin kt (thng l 2 AO-px vi nhau; 2 AO-pz vi
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nhau) m mt phng cha lin kt ny vung gc vi trc lin kt ? gia hai nguyn t , c gi l lin kt pi, k hiu l . Mt phng cha lin kt pi c gi l mt phng . Cn lu n du ca AO-p, trong s xen ph 2 AO-p to lin kt hnh thnh 2 phn: Phn dng c to thnh t s xen ph 2 phn dng (+) ca 2 AO-p ang xt; tng t, ta cng c phn m c hnh thnh t s xen ph 2 phn m (-) ca 2 AO-p ang xt. Mt phng phn ct hai phn l mt phng nt ca lin kt . Mt phng nt ny chnh l mt phng ca hai nguyn t ang xt. Nh vy, nu ta dng khi nim mt phng ch lin kt th cn nh mt phng ny b ct lm hai phn bi mt phng nt (mt phng ): mt phn l dng (+) cn mt phn l m (-). Xt s hnh thnh lin kt trong phn t C2H4. Thc nghim xc nh c, trong C2H4 c gc <HCC = 1200. Mun gii thch c s liu ny, cn gi thit C trong C2H4 nm trng thi lai ho sp2. Nh th mi C c 3 AO-sp2, trong 3 AO-sp2 ny c 2 AO-sp2 xen ph vi 2 AOs ca 2 nguyn t H to ra 2 lin kt , 1 AO-sp2 cn li xen ph vi 1 AOsp2 ca nguyn t C kia to ra lin kt . Kt qu ta c 5 lin kt cng nm trong mt phng (hnh 3.31). Mi nguyn t C cn c 1 AO-p (px, hoc py) nguyn cht. Trc ca AO-p ny vung gc vi mt phng , tc l vung gc vi trc lin kt gia 2 nguy t C. 2 AO-p ca 2 nguyn t C xen ph vi nhau to ra 1lin kt m mt phng cha lin kt ny vung gc vi mt phng ca lin kt ni trn. Lin kt mi ny chnh l lin kt gia 2 nguyn t C (hnh 3.31)
(2) Mt phng (mt phng cha lin kt )l mt phng giy vung gc vi mt phng (3) Phn dng (+) v m (-) ca vng xen ph gia 2 AO - pz to lin kt 2 pha ca mt phng , mt phng ng thi l mt phng nt ca lin kt . (4) Lin kt i ca hai nguyn t C trong C2H2 Phn dng (+) v m (-) ca vng xen ph 2 AO-pz to lin kt c phn b v 2 pha ca mt phng ( l mt phng nt), hnh 3.31. Nh vy gia 2 C trong C2H4 c 1 lin kt v mt lin kt , tc l c mt lin kt i gia 2 C (hnh 3.31)
HNH 3.31. Minh ho cc lin kt , trong phn t C2H4 (1) Cc lin kt C - C, C - H v mt phng (mt phng cha cc lin kt
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T cc s liu bng 3.1 ta thy lin kt i C = C bn hn lin kt n C C , nhng khng phi l bn gp i. C nhng phn t c ti 2 lin kt gia 2 nguyn t, nh N2. Mun gii thch lin kt ha hc trong N2 theo thuyt VB, ta dng 3 AO ha tr ca mi nguyn t l 2px, 2py, 2pz. 2 AO-2pz xen ph to mt lin kt gia 2 nguyn t N, 2 AO-px xen ph to mt lin kt , k hiu l x, 2 AO-py xen ph vi nhau to mt lin kt , k hiu l y. 2 lin kt trong 2 mt phng x v y vung gc vi nhau. Vy trong N2 c lin kt ba, N N.
HNH 3.32. S hnh thnh cc lin kt tronh phn t N2 (1) S xen ph cc AO - p to cc lin kt , (2) Hai mt phng , vung gc vi nhau c im ca lin kt + Cc AO-p to lin kt khng i xng vi trc lin kt m ch i xng qua mt phng . Do lin kt cn tr s quay t do ca nguyn t xung quanh trc lin kt . V s quay t do ca cc nguyn t hay nhm nguyn t s vi phm s xen ph cc i, tc l lm thay i s tng tc ca cc obitan. Ni cch khc, cc nguyn t hay nhm nguyn t b c nh (cng nhc) so vi lin kt (so vi mt phng lin kt ). y chnh l nguyn nhn lm xut hin tng ng phn hnh hc (cis, trans) ca cc hp cht m trong c lin kt v c cc nguyn t hay nhm nguyn t khc nhau. V d: CH3 CH = CH CH3 c hai ng phn hnh hc.
(dng cis)
(dng trans)
+ Lin kt km bn, d b phn cc nn cc hp cht lin kt c kh nng phn ng cao. b) S ho tr Khi nim:
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* Vch ho tr: Theo quy c ca lewis, mi i electron (2e) c k hiu bng mt vch ( hay | hay /, ...). Vch biu din mt i electron (2e) ha tr, l i electron ring hay i electron lin kt, c coi l vch ha tr. V d 17: Trong phn t NH3, quanh N c bn i e ho tr, gm mt i e ring v 3 i electron lin kt: N N H : : H Biu din bng vch ha r H H H H * S ha tr (hay cng thc ha tr): S trong k hiu cc nguyn t c vit theo mt th t xc nh v ni vi nhau bng nhng vch ha tr thnh tng cp 2 nguyn t sao cho v nguyn tc, c nhiu nht s lin kt, s lng vch xut pht t mi nguyn t phi ng ng ha tr ca nguyn t v s ha tr phi c ngha. V d 18: vi HCNc th c cc cch vit sau: H C N; H C = N; H C N; C = N H; ... (1) (2) (3) (4) Theo quan nim trn, ch c cng thc (3) mi ng l s ha tr ca HCN. S ha tr va xt, trong trng hp cng thc ha tr ch c mt s ha tr l cng thc cu to vn thng c s dng. Vi v d trn, cng thc (3) l cng thc cu to ca HCN. * S chng cht s ha tr: C nhng cng thc ha hc ch c mt s ho tr. y l cc trng hp m trong c th ch c mt cch duy nht vic biu din cc lin kt c nh (khu tr) 2 tm (2 ht nhn). Cc cng thc xt trn vi NH3, HCN thuc trng hp ny, vi axit axetic cng th H H H C C O H O
Tuy nhin, c nhiu cng thc trong c cc lin kt khng c nh (khng khu tr) th khng th biu din bng mt s ha tr i vi mt cng thc. Trong cc phn t ny, b khung lin kt c coi l c nh, ta ch xt st ha tr c to ra t h cc lin kt . Trong phn t benzen, C6H6. Cc nguyn t C trng thi lai ha sp2. Cc AO lai ha ca C xen ph vi nhau to ra b khung cacbon l cc lin kt , cc nguyn t cacbon cn c 1 AO - p thun khit c 1 electron (gi l e-p). Mi electron ny c k hiu bng 1 ch ci a, b, c, d, e, f. Theo thuyt VB, 6 electron ny xen ph i mt vi nhau to lin kt . C 5 kh nng to ra 3 lin kt ny, c k hiu l I, II, III, IV, V. Hnh 3.32
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HNH 3.32. Cc kh nng to ra 3 lin kt tromg C6H6 Kt hp vi b khung lin kt , mi kh nng trn cho ta mt s ha tr ca benzen, hnh 3.32.
I II III IV V S I, II l cng thc cu to ca benzen do Kkul ngh, nn c gi l cng thc Kkul, cc s III, IV, V l cng thc do ioa ngh- cng thc ioa. Cc kt qu thc nhim cho bit: - C6H6 c 6 cnh bng nhau v cng nm trong mt phng, di ca cc lin kt cng bng nhau v bng 1,397 A0 (so vi di ca lin kt n dC C = 1,54 A0 th ngn hn, cn so vi di ca lin kt i dC = C = 1,33 A0 th di hn). - V mt nng lng th C6H6 tng i bn, cn v kh nng phn ng th C6H6 khng tham gia phn ng trng hp nh cc hp cht c lin kt i C=C, kh b oxi ha nhng li d tham gia phn ng th. T cc d kin ny, chng t C6H6 khng th c cu to thc l mt trong cc s ho tr trn. T gi thuyt c mi ngi chp nhn l: Cng thc cu to thc ca benzen l kt qu ca s chng cht 5 s ho tr xt trn. V vy, m t tt nht cu to thc ca benzen, nn dng cng thc cu to gii to (hnh 3.33). Thng thng chng ta vn dng cng thc ca Kkul, khng nn dng cng thc ca ioa.
HNH 3. 33. Mt s cch biu din cng thc cu to ca C6H6 3.4. nh gi s lc v thuyt VB * Thnh cng: Ln u tin bi ton c hc lng t p dng vo ha hc cho kt qu gn vi thc nghim. T , thuyt VB c xy dng gip gii
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quyt nhng kt qu thc nghim, gp phn m ra mt giai on pht trin mi ca ha hc. Vic biu din cng thc phn t theo s ha tr tuy rt gn ng nhng c u im ch: trc quan, thun li cho ngi hc nn vn c s dng lin tc. * Hn ch: Vi quan im mi lin kt c 2 e, nn thuyt ny khng gii thch c s tn ti ca cc h m thc nghim xc nhn nh H2+, tnh thun t ca O2 (thiu st ny ca VB s c khc phc bng thuyt MO). 4. Mt s vn ca thuyt obitan phn t (MO) 4.1. Mt s lun im c s ca thuyt MO 1. Thuyt MO cho rng trong phn t gm mt s c hn cc ht nhn nguyn t v cc electron chuyn ng khng ngng, lin kt vi nhau thnh mt th thng nht. Trong cc electron chuyn ng trn cc obitan chung ca ton phn t, c gi tt l obitan phn t (MO) (thyt ny khng tha nhn s tn ti ca cc obitan nguyn t trong phn t, tri vi thuyt VB). 2. Mt cch gn ng, cc obitan phn t (MO) c xy dng nh sau: Obitan chung ca ton phn t c hnh thnh l do s t hp tuyn tnh cc MO ch c 1e; cc MO c 1e ny c ly gn ng nh sau. Khi 1e chuyn ng gn 1 ht nhn nguyn t ny hn so cc ht nhn nguyn t khc th obitan nguyn t (AO) tng ng vi e c coi l MO c 1e ca e ny. Vy MO chung ca ton phn t l t hp tuyn tnh cc obitan nguyn t (AO). Ni dung va trnh by trn c biu din bng biu thc:
i = cr r
r =1
(4.1a)
Trong : i l MO th i ca phn t, r l AO th r, cr l h s t hp ca hm sng, cr cho bit t l ng gp ca AO th r vo MO. V nguyn tc, s AO tham gia t hp cng nhiu (biu thc 4.1a) th s gn ng cng tt. Tuy nhin nu s lng AO nhiu qu th s kh khn cho vic tnh ton, do trong thc t thng gii hn s lngcc AO em t hp, v vy (4.1a) c vit:
i = cr r
r =1 k
(4.1b)
S lng MO thu c lun bng tng s AO ca tt c cc nguyn t trong phn t tham gia t hp tuyn tnh. Trong s t hp ny nguyn l xen ph cc i lun c tun th nghim ngt. Khi ly mt s lng hn ch cc AO em i t hp tuyn tnh, th l s gn ng cc obitan phn t, thng c vit tt l MO - LCAO. 3. Cc MO ny c xp theo th t nng lng t thp ln cao, to thnh gin nng lng cc MO. MO ng vi nng lng thp c gi l MO lin kt, MO ng vi nng lng cao c gi l MO phn lin kt, s lng ca hai loi MO ny lun bng nhau. Cc electron c in vo cc MO da vo nguyn l vng bn, nguyn l Pauli v quy tc Hun, kt qu ta c cu hnh electron ca phn t. Minh ha cho cc lun im ny c trnh by phn sau.
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gio trnh ho i cng
4.2. Thuyt MO gii thch lin kt trong mt s phn t n cht dng A2 4.2.1. S lin kt hiu dng, lin kt xichma v lin kt pi Phn t n cht ng hch A2 l h gm 2 nguyn t ca cng mt nguyn t A. Ngoi nhng vn c a ra phn 4.1 ca chng 3. Phn ny cn a ra mt s vn sau: * S lin kt hiu dng (N), c tnh bng biu thc:
n n* N= 2
(4.2)
Trong : - n l tng s electron ca cc MO lin kt - n* l tng s electron ca MO phn lin kt Khi xt lin kt gia 2 nguyn t (lin kt 2 tm), xc nh c s lin kt hiu dng (N) th c th kt lun: N = 1 c mt lin kt hnh thnh gia 2 nguyn t, l lin kt n (lin kt ) N = 2 c hai lin kt hnh thnh gia 2 nguyn t, l lin kt i (mt lin kt , mt lin kt ) N = 3 c ba lin kt hnh thnh gia 2 nguyn t, l lin kt ba (mt lin kt , hai lin kt ) N = 0,5 c 0,5 lin kt hnh thnh gia 2 nguyn t hay c 1 lin kt hnh thnh gia 2 nguyn t, lin kt ny ch c 1 electron. N = 1,5 c 1,5 lin kt hnh thnh gia 2 nguyn t, hay l c 1 lin kt c 2 electron v mt na lin kt c 1 electron, hay l c mt lin kt c 3 electron. Trng hp N = 2,5 v N = 3 cc bn sinh vin t nhn xt . Nh vy, t biut thc 4.2 v cc kt qu va trnh by trn, cho thy thuyt MO chp nhn cc lin kt gia 2 nguyn t c th l 1e, 2e hoc 3e. Chnh iu ny gip cho thuyt MO d dng gii thch c cc hin tng thc nghim m thuyt VB khng th gii thch c. Trong trng hp N 0 th kt lun: Lin kt khng c hnh thnh gia 2 nguyn t, tc l khng tn ti phn t A2. * Lin kt xichma v lin kt pi: Thuyt MO cng a ra cc khi nim v lin kt xichma (), lin kt pi (), v c im i xng cng cho kt qu ging nh trong thuyt VB, nhng cn c thm cc c im c th trong thuyt MO, l: - Lin kt xichma l lin kt c hnh thnh do cc electron c in vo MO - lin kt. - Lin kt pi l lin kt c hnh thnh do cc electron c in vo MO - lin kt. Cn ch : + cc MO c k hiu nh sau: MO lin kt xichma k hiu l , MO lin kt pi k hiu l . MO phn lin kt xich ma k hiu l *, MO phn lin kt pi k hiu l *. + Mi mt MO dng mt k hiu , hoc *, *.
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4.2.2. S lc bi ton ion phn t H 2+ Thc nghim xc nhn s tn ti ca ion phn t H 2+ trong quang ph mt tri v trong cc vng c tia la in dn ti phn t H 2+ l c tht. Vic xy dng v gii bi ton cho ion phn t H 2+ gm cc bc. 1) M hnh h gm: 2 ht nhn a, b 1e ra a e R rb b
HNH 4.1. M hnh h ion phn t H 2+ Trong hnh 4.1, R l khong cch gia hai ht nhn a v b; ra, rb l khong cch t e n ht nhn a, b. 2) Ton t Hamintn: Trong h n v nguyn t (vn) c dng:
b = 1 2 1 + 1 H 2 R =a r
(4.2)
3) Hm sng: T hai hm khng gian - hai obitan 1s k hiu l a, b (v c 2 ht nhn ). Ta c 2 t hp: + = = - = * = 1 (a + b) 2 (4.3)
1 (a - b) (4.4) 2 Cc hm + , phi kt hp vi cc hm spin s cho ta hm sng ton phn m t trng thi ca h. Theo nguyn l Pauli hm sng ton phn m t trng thi ca h phi l hm phn i xng. V ton t Hamintn H khng tc dng vo phn spin ca hm sng ton phn, nn ch cn xt phn khng gian + v . 4) Phng trnh Sroing v li gii: Ta c H = E (4.5) Thay cc biu thc 4.1; 4.2; 4.3; 4.4 vo 4.5 ri gii. 5) Kt qu Vi hm + hay thu c E+, c 2 tnh hung xy ra vi E+
E+ =
Nu s = 0 , th: Vi hm - hay * thu c EE =
1+ s E+ = +
(4.6) (4.7) (4.8) (4.9)

gio trnh ho i cng
Nu s = 0 , th:
1 s E =
156
Trong : = EH c gi l tch phn culong; l tch phn trao i. C , < 0 ; < ; s l tch phn xen ph 0 s 1. Cc hm + hay v hay * chnh l cc obitan phn t (MO) ca + H2 . 4.2.3. Gii thch s hnh thnh lin kt trong theo thuyt MO a) Biu din ng cong nng lng E+, E- theo R (R l khong cch gia 2 ht nhn), hnh 4.2.
HNH 4.2. ng cong nng lng E+, E- ca ion phn t H 2+ Hnh 4.2, cho thy ng cong nng lng E- khng xut hin cc tiu, E> 0. Vy E- khng ng vi s to thnh lin kt gia 2 ht nhn khi hai ht nhn tin li gn nhau (R gim) v khi ny lc y gia 2 ht nhn mnh hn lc ht gia 2 ht nhn vi electron. Ngc li trn ng E+, xut hin cc tiu nng lng phn m (-), ng vi cc tiu nng lng ny l gi tr R0 ca R. R0 l di lin kt ca H 2+ . Emin = E+ l nng lng gii phng khi H 2+ c hnh thnh, chnh l nng lng lin kt ca H 2+ . Vy E+ m t nng lng ca s hnh thnh H 2+ . Kt qu tnh bng con ng l thuyt (phng php MO) ch t chnh xc vo khong 63% so vi thc nghim. V y l mt phng php gn ng, cng cn nhc li rng, c hc lng t ch gii chnh xc cho bi ton nguyn t H. K t khi thuyt MO ra i n nay, cng vi s pht trin ca khoa hc k thut, c bit l nhng thnh tu v khoa hc my tnh gip cho thuyt MO ngy cng cho cc kt qu gn vi thc nghim hn. Ngy nay, thuyt MO khng nhng gii thch c cc hn ch ca VB m cn gii thch c mt cch thu o v hnh hc phn t cng nh cc c trng khc ca phn t, v vy thuyt MO ngy cng c ng dng rng ri. b) Biu din E+, E- ti R0, hnh 4.3. V E+ c gi tr m, tc nng lng thp nn + l MO lin kt. Ngc li E- c gi tr dng, nng lng cao nn l MO phn lin kt.
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gio trnh ho i cng
Ea
Eb
EH
EH E+
+
a +
E+
khi s = 0 khi s 0 + HNH 4.3. Gin nng lng cc MO ca H 2 khi s = 0 v s 0 Hnh 4.3 l gin nng lng cc MO + , , khi s = 0. trong trng hp ny 2 MO c phn b cch u v tr EH = 0. Trong trng hp s 0, ta thy v tr ca + tin gn n EH = 0, cn li tin ra xa. Trong trng hp ny nng lng E- ng vi cch EH = 0 xa hn so vi nng lng E+ ng vi + . T chng ta c th kt lun: Tc dng phn lin kt ca MO phn lin kt ( ) mnh hn tc dng lin kt ca MO lin kt ( + ). c) hiu r hn v cc hm MO, chng ta xt hnh nh ca cc hm + , , v hm mt xc sut tng ng ca hai hm , Hnh 4.4.
HNH 4.4. Minh ha s to thnh MO lin kt + , MO phn lin kt v hm mt xc sut tng ng ca chng 1 Hai AO ring r; 2 cc Mo lin kt , phn lin kt ; 3 hm mt + 2 2 2 xc sut + , . Hm cho thy gia hai ht nhn hiro mt xc sut tm thy electron bng 0 nn h khng th hnh thnh c, tc l l hm phn lin kt. d) in electron vo MO H H 2+ c 1e. Da vo cc c s trnh by trn, e ny c in vo MO hay MO-1s nh hnh 4.5. Vy cu hnh electron ca H 2+ l: 11s e) Tnh s lin kt v kt lun
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* 1s
a=1sa
b=1sb
+ 1s
HNH 4.5. S in e vo MO trong h H 2+ (e ban u c th AO-1sb) (dng lng t l gch ngang biu din AO v MO) Theo 4.2, ta c:
N H2 = 1 0 = 0,5 > 0 2
Vy h ion phn t H 2+ tn ti c, tc l gia 2 ht nhn hnh thnh mt na lin kt hay do 1e to ra. Cng thc cu to ca H 2+ c biu din nh sau: [H H ]+ By gi, chng ta v gin nng lng ca cc MO, xc nh cu hnh electron v tnh s lin kt cho cc h sau: H2, H 2 a) H2 b) H 2 +*1s a +1s b a +1s* b +1s
HNH 4.6. Minh ha s in e vo H2 v H 2 Vy, cu hnh electron ca H2 l: 12s ; cn ca H 2 l 12s 1*s1 . S lin kt l:
:
N H2 = NH
2 2
H H2 c N H = 1 , vy H2 bn. H2 c cng thc electron H:H v cng thc cu to HH, H2 l phn t nghch t v 2e cp i. H H 2 mc d c N H = 0,5 nh H 2+ nhng nh kt lun trn th h H 2
2
20 =1> 0 2 2 1 = = 0,5 > 0 2
km bn hn h H 2+ rt nhiu v c 1e nm trn MO phn lin kt. Trong thc t cha tm thy H 2 , cn H 2+ th c trong h mt tri v con ngi cng tm thy trong tia m cc vo cui th k 19. 4.2.4. Gii thch s hnh thnh lin kt trong phn t ng hch A2 Thc t thng xt trng hp phn t A2, vi A l nguyn t ca cc nguyn t chu k 2. Tc A l: Li, Be, B, C, N, O, F, Ne.
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gio trnh ho i cng
Cn lu cc MO c to thnh t s t hp tuyn tnh ca cc AO tng ng c tnh i xng ging nhau. Ch nhng AO c tnh i xng ging nhau mi c kh nng xen ph vi nhau hnh thnh 1 MO lin kt v 1 MO phn lin kt tu thuc vo du ca chng ging nhau hay khc nhau vng xen ph.i vi nhng AO khng c tnh i xng ging nhau th khng c s xen ph. a) S to thnh cc MO Vi cc nguyn t thuc chu k 2, ta ch cn xt cc AO ho tr: 2s, 2px, 2py, 2pz. Do cc MO c to thnh t s t hp tuyn tnh cc AO c tnh i xng ging nhau, v th ta ch c th t hp cc AO sau y vi nhau: * T hp tuyn tnh: 2sa 2sb cho ta 2 MO k hiu l 2 s , 2 s * 2 p z 2 p z cho ta 2 MO k hiu l 2 p , 2 p * 2 p x 2 p x cho ta 2 MO k hiu l 2 p , 2 p * 2 p y 2 p y cho ta 2 MO k hiu l 2 p , 2 p Chng ta thng chn trc z l trc lin kt nn cc MO c hnh thnh t s t hp tuyn tnh cc AO-2pz cho ta cc MO- c i xng trc, cn t hp tuyn tnh cc AO-2px, AO-2py s cho cc MO-. Nh vy, t 8 AO em t hp cho ta 8 MO. Trong , nng lng ca MO 2 p = MO 2 p MO:
a b z z a b x x a b
y y x y
MO
* 2 px
= MO
* 2 py
* * * n gin, dng k hiu: 2 p z ; 2 p z* ; 2 p x ; 2 p x ;

z z x x
* 2p y ; 2p * . y
y y
b) Gin nng lng ca cc MO v cu hnh e ca cc phn t A2 Cc MO c xp theo 2 gin nng lng sau y: Gin I: Gin bnh thng, c p dng cho cc phn t O2, F2, Ne2. Trong trng hp ny cc AO - 2p, AO - 2s c hiu nng lng cch nhau tng i ln ( 20eV), v vy mc d cc AO - p v AO -s c tnh i xng ging nhau i vi trc z nhng chng ta ch t hp ch cc AO - p ring vi nhau v cc AO - s ring vi nhau. V mt trong cc iu kin cho cc AO t hp c vi nhau l c nng lng gn bng nhau. Gin II: Gin bt thng, c p dng cho cc phn t, Li2, Be2, B2, C2, N2. Trong trng hp ny do c s di chuyn mnh e t AO -2p v AO 2s, nn hiu nng lng ca 2 mc ny l E2p - E2s 1,8 eV, tng i nh. V vy, trong s t hp 2sa 2sb cn lu n s tham gia ca cc AO - 2pz(a) v 2pz(b), ngc li i vi t hp 2pz(a) 2pz(b) cn ch n s tham gia ca cc AO -2sa, 2sb. Chnh v c s tham gia ny m trong gin 2 nng lng ca MO - 2s cao hn MO - x, y.
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gio trnh ho i cng
AO
MO *z *x *y
AO
AO
MO *z *x *y
AO
2p
2p
2p
x y z I *2s
z x y II *2s
2p
2s
2s
2s
2s
2s I A2
2s II A2
HNH4.7. Gin nng lng MO ca phn t A2 (A l cc nguyn t ca chu k 2) T hnh 4.7. Nhn thy trt t nng lng ca cc MO 2 gin ny nh sau: Gin I:
* * * 2 s 2 s z x = y x = * z y
* * Gin II: 2 s 2 s x = y z x = * z* y (chiu t tri sang phi l chiu tng dn mc nng lng)
c) Vn dng * Xt phn t N2: + T cu hnh electron ca N: 1s2 2s22p3 cho bit N c 5e lp ngoi cng (5 e ho tr). + Vy, phn t N2 c 2.5 = 10 e ho tr. 10 e ny c in vo cc MO da trn 3 c s nu phn 4.1 ca chng 3. S dng gin II vit cu hnh electron, kt qu ta c cu hnh electron ca N2 nh sau: * 2 N2: 22s 22 x2 y z2 s S lin kt ca N2 l: N N =
2
, 2 lin kt ). Cng thc electron ca N2 l:
82 = 3 . Vy trong N2 c lin kt 3 (1 lin kt 2
:N:::N: v cng thc cu to l

161
NN
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Nhn xt: N2 l phn t nghch t v tt c cc electron u ghp i, N2 c s lin kt bng 3 nn di lin kt b (1,1 A0) v nng lng lin kt rt ln (942 kJ/mol) v vy N2 rt bn, km hot ng ho hc. * Xt phn t O2: + Tin hnh tng t nh i vi N2, nhng s dng gin nng lng I. Ta c cu hnh electron ca O2 nh sau: * 2 * O2: 22s 22 z2 x2 y x 1 *1 s y T cu hnh electron ca O2, ta thy O2 c 2 e c thn. Vy O2 l cht thun t. Kt qu ny ph hp vi thc nghim, Nh vy thuyt MO gii thch thnh cng cu to ca phn t O2 ( thuyt VB khng gii thch c tnh thun t ca O2). Tnh s lin kt ca O2: N O =
2
84 = 2 vy c th kt lun trong phn t O2 2
c lin kt i. ph hp vi cu hnh electron ca O2, c th biu din cng thc cu to ca O2 nh sau: . .. . O: :O Trong nhiu trng hp nu khng cn xt qu cht ch, th ch cn dng gin I cho cc phn t A2. d)Mt s phn t A2 thuc cc chu k khc Cc gin I v II cng c th dng xt cu hnh electron ca cc phn t A2 thuc cc chu k khc. Ging nh Li2, cc phn t A2 thuc phn nhm chnh nhm I (Na2, K2, 2 Rb2, Cs2) trng thi c bn u c cu hnh electron l: ns , cc phn t ny u c 1 lin kt . Tng t nh trng hp ca F2, cc phn t halogen khc nh Cl2, Br2, 2 * 2 * I2 trng thi c bn u c cu hnh: ns ns2 z2 x2 y x 2 *2 , cc phn t ny ch y c 1 lin kt . 4.3. Thuyt MO gii thch lin kt ho hc trong phn t cc hp cht 4.3.1. Cc phn t 2 nguyn t d hch AB a) A, B l cc nguyn t thuc chu k 2 Hnh 4.8. l gin nng lng ca cc phn t AB, trong A, B l cc nguyn t ca chu k 2 vi gi thuyt B c m in hn A, do nng lng ca cc phn lp 2s, 2p ca B thp hn ca A (cc AO v MO c biu din bng trn). T hnh 4.8 (trang 163) , ta c trt t nng lng * * sau: 2 s 2 s x = y z x = * z* . So snh trt t nng lng ca cc MO trong phn y t AB so vi gin II th chung ging nhau
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AB *z *x*y
2p 2p z x y *2s 2s 2s 2s HNH 4.8. Gin nng lng cho h phn t AB Vit cu hnh electron ca phn t CO: D dng xc nh c phn t CO c 10 e v ha tr (v C c 4 cn O c 6) ging N2. V Oxi c m in hn Cacbon nn oxi l B, cn cacbon l A, cu hnh electron ca CO l: * 2 CO: 22s 22 x2 = y z2 s T cu hnh electron ca CO d dng xc nh c s lin kt ca CO bng 3. V c s e ging nhau, nn CO v N2 c nhiu tnh cht ging nhau, nh: D thy NO , CN- cng ging nh CO v N2 cc phn t ny u nghch t. Cn vi NO phn t c 11 e ha tr, nn cu hnh electron s l 0 2 * 2 2 s 22 x2 = y z2 *1 , s lin kt bng 2,5, di lin kt bng 1,15 A , nng s lng lin kt bng 162 kcal/mol. Vi cc phn t v ion BO, CN, CO+, cc * 2 phn t ny u c 9 e ha tr, c cu hnh electron 22s 22 x2 = y 1 , cng c s s z lin kt bng 2,5. Cc phn t ny u c 1e c thn nn l cht thun t. b) A, B l cc nguyn t c m in ln in hnh nht cho trng hp ny l phn t HF. Vn dng thuyt MO gii thch s hnh thnh cc lin kt ha hc trong phn t HF s cho ta nhiu iu th v.
Trng i hc cng nghip h ni +
E N 2 = 255kcal / mol ; ECO = 255,8kcal / mol
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Nguyn t H c 1AO - 1s, c 1e; F c cu hnh electron lp ngoi cng l: 2s 2p5, F c 1 AO -2s v 3 AO - 2px,2py,2pz v c 7 e lp ngoi cng. F c = 4 ln hn nhiu so vi m in ca H, = 2,1.V vy AO - 2s ca F c nng lng nh hn rt nhiu so vi nng lng ca AO - 1s ca H, nn 2 AO ny coi nh khng tham gia t hp c vi nhau. Trong 3 AO - 2px, 2py, 2pz , nu chn trc z l trc lin kt th AO - 2pz c cng kiu i xng vi AO - 1s ca H, khi AO - 2px, 2py khng ph hp vi AO - 1s v mt i xng. Do t hp tuyn tnh gia AO - 1s ca H vi AO - 2pz ca H cho ta 2 MO, mt l MO lin kt z, mt l MO phn lin kt z* . Cc AO - 2px, 2py th chuyn thnh cc MO 0 khng lin kt, k hiu l x0 , y . T cc kt qu va phn tch trn, ta c gin nng lng cc MO ca HF, hnh 4.9. *z
2
1s
0x z
2p
2s
H HF F
HNH 4.9. Gin nng lng MO v cu hmh electron ca HF 2 0 2 Vy cu hnh electron ca HF l: [2s ] z2 ( x0 ) ( y ) d thy s lin kt ca HF l 1, tc phn t HF c 1 lin kt . 4.3.2. Cc phn t c t 3 nguyn t tr ln Khi xt cc phn t c t 3 nguyn t tr ln dng ABn (n 2), cn ch 2 iu kin sau: + Cc yu t i xng ca phn t (tm, trc, mt phng) + S t hp cc AO ca nguyn t B t c cc MO thch hp vi AO ca A. Di y chng ta xt mt s phn t quen thuc a) Phn t CH4. Phn t c hnh t din u in hnh Mi H c 1 AO - 1s, vy 4 nguyn t H s c 4 AO - 1s. 4 AO ny s t hp cng v tr thch hp vi 4 AO ho tr ca C l AO - 2s, 2px, 2py, 2pz (khng xt AO - 1s ca C). Nh vy CH4 c 8 MO, 8 MO ny c to ra t 8 AO ho tr ca C v H. Tt c 8 MO u l MO - . C 4 MO - c nng lng thp l cc MO lin kt v 4 MO - * l cc MO phn lin kt c nng lng cao, Hnh 4.10.
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*x *y *z *s
2p 1s 2s x y z s
4H
CH4
HNH 4.10. Gin nng lng cc MO v cu hnh electron ca CH4 2 Cu hnh electron ca CH4 l: s2 x2 y z2 , vy CH4 c 4 lin kt c bn khng bng nhau (thc nghim cho thy iu ny l ng) b) phn t H2O. L phn t c gc <HOH 104028 2 nguyn t H c 2 AO - 1s s tham gia t hp tuyn tnh (cng v tr) vi cc AO ha tr ca O. O c 4 AO ha tr 2s, 2px, 2py, 2pz. gii thch c gc thc nghim ca H2O, ngi ta gi thuyt O ttrng thi lai ho sp3. Cc AO lai ho ca O t hp vi AO - 1s ca H to thnh cc MO. Hai t hp ca 2 AO - 1s ca H vi 2 trong 4 AO - sp3 ca O to ra 4 MO - gm 2 MO lin kt v 2 MO phn lin kt, 2 AO - sp3 cn li s chuyn thnh cc MO khng lin kt k hiu l te3, te4 (ging nh HF). Gin nng lng cc MO ca H2O c a ra * hnh 4.11 1 2
*
1s
2p te1 te2 te3 te4 4 AO thun khit 4 AO-sp3
te te
2s
H2 H
HNH 4.11. Gin nng lng cc MO v cu hnh electron ca H2O Ta c cu hnh electron ca H2O l: [1s 2 ] 12 22te32te42 . Vy trong phn t nc c 2 lin kt .
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c) Phn t CO2. Mt phn t thng Thc nghim xc nh c gc lin kt trong phn t CO2 l 1800. gii thch gc lin kt trong phn t CO2, chng ta gi thit C trng thi lai ho sp. Nh vy C c 2 AO lai ho sp, k hiu l spa, spb v 2 AO - p thun khit l 2px, 2py. V m in ca O ln hn ca C, nn ngi ta cho rng AO - 2s ca O c nng lng thp s khng tham gia vo t hp vi C to thnh MO. Vy mi O ch c 3 AO - 2p tham gia t hp. Tng cp 2 AO - 2p tng ng ca 2 O s t hp vi nhau trc: 2px vi 2px, 2py vi 2py, 2pz vi 2pz nh vy c tt c 6 t hp (v c t hp cng (+) v t hp tr(-)). 2 t hp ca 2 AO - 2pz ca O t hp vi 2 AO lai ho spa v spb ca C (v chng ph hp nhau v mt i xng) cho ta 4 MO - : Trong c 2 MO * lin kt k hiu l 1, 2 v 2 MO phn lin kt k hiu l 1* , 2 . 1 t hp cng (+) ca 2 AO - 2px ca O t hp vi 1 AO - 2px thun khit ca C cho ta 2 MO - x: 1 MO lin kt k hiu l x, 1 MO phn lin kt k hiu * l x . 1 t hp cng (+) ca 2 AO - 2py ca O t hp vi 1 AO - 2py thun khit ca C cho ta 2 MO - y: 1 MO lin kt k hiu l y, 1 MO phn lin kt k hiu l * . 2 t hp tr (-) ca 2 AO, 1 ca 2 AO - 2px, 1 ca 2 AO - 2py th chuyn y
0 thnh 2 MO - khng lin kt, k hiu l x0 , y . Nh vy CO2 c 10 MO, trt t nng lng ca 10 MO ny c biu din trn gin nng lng (hnh 4.12). S in electron vo cc MO ca CO2 cng c biu din trn hnh 4.12.
*1 *2
0x 0y
2px 2py
2p 2s
spa
spb
0 0x y
2p
x y
2 2s
CO2
HNH 4.12. Gin nng lng cc MO v cu hnh electron ca CO2

166
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2 0 Ta c cu hnh electron ca CO2: [2s 2 2 s 2 ] 12 22 x2 y ( x0 ) ( y ) 2
S lin kt trong CO2l: N CO =

2
v C c 1 mi lin kt i: 1 lin kt , 1 lin kt . Nh vy, .. th biu din cng thc cu to ca CO2 nh sau: c .. O = C = .. O hay O=C=O .. Cn lu , 2 lin kt ny khng c nh 2 nguyn t m l chung cho c 3 nguyn t. Chng ta ni cc lin kt ny l lin kt khng nh ch hay cc lin kt c gii ta. Cng c th biu din cng thc cu to ca CO2 bng cch:
O C O
80 = 4 tc l gia mi mt nguyn t O 2
(Dng k hiu ch lin kt khng nh ch) d) Phn t BeH2, cng l mt phn t thng BeH2 c gc lin kt o bng thc nghim l 1800. Khi xt s thnh lp cc MO t cc AO ca Be v H cn ch n tnh cht i xng ca phn t.
*z *s
2p
0x 0y
2s
1 sa 1 sb z s
Be
BeH2
Ha Ha
HNH 4.13. Gin nng lng cc MO v cu hnh electron ca BeH2 Nguyn t Be c cc AO ha tr: 2s, 2px, 2py, 2pz. 2 nguyn t Ha, Hb mi nguyn t c 1 AO ha tr c k hiu l 1sa, 1sb. AO - 2s ca Be t hp cng hoc tr vi t hp (1sa+1sb) ca 2 nguyn t H cho ta 2 MO: 1 MO lin kt k hiu l s v 1MO phn lin kt k hiu l s* .
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2 AO - 2pz ca Be s t hp cng hoc tr vi t hp (1sa-1sb) ca 2 nguyn t H cho ta 2 MO: 1 MO lin kt k hiu l z , 1 MO phn lin kt k hiu l z* . Cc AO - 2px, 2py c trc vung gc vi trc phn t nn khng xen ph vi cc AO -1s ca Ha, Hb v th cho ta cc MO khng lin kt, k hiu l x0 , 0 y . T , ta c gin nng lng ca BeH2, hnh 4.13 (trang 166). Cu hnh electron ca BeH2 trng thi c bn l: s2 z2 . Vy s lin kt ca BeH2 l: N BeH =
2
40 = 2 , do BeH2 c 2 lin kt v c cng thc electron 2
v cng thc cu to: H : Be : H ; H Be H 4.4. Thnh cng v hn ch ca thuyt MO * Thnh cng: Vi m hnh lin kt gii ta (v sau b sung thm m hnh lin kt nh c). Thuyt MO gii thch c cc kt qu thc nghim m cc thuyt trc cha gii thch c nh s tn ti ion phn t H 2+ , tnh thun t ca phn t O2, B2H6 l m hnh lin kt thiu electron. Vi phng din lm ton, cng vi s tr gip ca my tnh, thuyt MO cho php tnh c nhng kt qu v tnh cht ha hc lng t nh: nng lng, mt e, hnh hc phn t... cc kt qu mt mt gii thch kt qu thc nghim, mt khc tin on c chiu hng ca thc nghim. * Hn ch: Kh tru tng v kh v thut ton nn khng thun li cho ngi hc. C. H THNG BI TP I. Bi tp t lun (c li gii v khng c li gii) I.1. Bi tp c li gii Bi 1. Hy biu din lin kt cng ha tr ca cc phn t H2S, BeCl2 , N2 theo s lewis. Cho: 1H, 4Be, 7N, 17Cl Li gii Mun biu din lin kt cng ha tr ca phn t, trc tin phi vit cu hnh electron ca nguyn t ca cc nguyn t tham gia to lin kt. H: 1s1 H Be: 1s2 2s2 trng thi kch thch B*: 1s2 2s12p1 Be* c 2 e c thn: Be 2 2 2 C: 1s 2s 2p trng thi kch thch C*: 1s2 2s12p3 C* c 4 e c thn. C N: 1s2 2s22p3 N c 1 cp e ghp i, 3 e c thn. :N hay N O: 1s2 2s42p4 O c 2 cp e ghp i, 2 e c thn.
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T cu hnh electron trn ta s xy c c s lin kt ca cc phn t theo lewis: H:S:H hay H S H H2S: BeCl2: Cl: Be :Cl hay Cl Be H N2: N ::: N hay N N Bi 2. Vi phn t CO c in tch d trn C v O. Hy biu din s cu to lewis v ch hng ca momen lng cc. Cho: 6C, 8O Li gii T cu hnh electron ca C, O bi 1, ta c: C :: O hay C = O Vi cch biu din ny, C khng tha mn quy tc bt t. V vy C s r xut hin in tch d: v + + C O hay C = O C O Bi 3. Bit phn t O3 l phn t c gc, khng ng vng, cho bit s lewis ca phn t ny. Li gii i vi O3 gi thit phn t ng vng O O O3 l: Song thc nghim cho bit O3 khng ng vng, Vy s cu to ca O+ O +O O O
:O: hay O S: 1s 2s 2p 3s 3p S c 2 cp e ghp i, 2 e c thn. :S: hay S Cl: 1s2 2s22p6 3s23p5 Cl c 3 cp e ghp i, 1 e c thn :Cl hay Cl
2 2 6 2 4
Cc dng h bin (mesome)
Bi 4. Hai phn t NH3 v NF3 u c cu trc hnh thp tam gic. a) Hy cho bit trng thi lai ha ca N trong c 2 trng hp v biu din chng bng s .
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b) Gii thch ti sao momen lng cc ca NH3 (1,46D) ln hn nhiu so vi NF3 (0,2D). Cho: ZH = 1 ; ZN = 7; ZF = 9; v gc lin kt o bng thc nghim HNH = 1070 ; FNF = 1020 ; F > N > H Li gii a) H: 1s1 biu din dng lng t N: 1s2 2s22p3 hay F: 1s2 2s22p5 hay
Khi hnh thnh lin kt, N trong c 2 phn t u trng thi lai ha sp3, v gc lin kt ca 2 phn t gn vi gc 109028. E 2p 2s 4AO lai ha sp3
Ba AO lai ha sp3 ca N xen ph vi 3 AO - 1s ca H i mt to ra 3 lin kt trong phn t NH3. Ba AO lai ha sp3 ca N xen ph vi 3 AO - 2p ca F i mt to ra 3 lin kt trong phn t NF3. C 2 trng hp ny, N vn cng i e khng lin kt nm trn 1 AO 3 sp . 2 phn t ny c biu din bng s .
N H H N F F
N F
b) Nhn t hnh v ta nhn thy hng ca vc t momen lng cc ca cc lin kt N H v ca cp electron khng phn chia cng chiu vi nhau. Trong khi hng ca vc t momen lng cc ca cc lin kt N F v ca cp electron khng phn chia ngc chiu vi nhau, do F > N > H . Khi tng hp cc vc t th thu c momen lng cc ca phn t NH3 ln hn ca NF3. Bi 5. Dng thuyt lai ha m t dng hnh hc ca phn t NO2 tn ti 2 dng, cho ZN = 7 ; ZO = 8 v gc thc nghim o c NON = 1190. Bit phn t c mt lin kt .
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Li gii Cu hnh electron ca N v O N: 1s2 2s22p3 biu din bng lng t O: 1s2 2s22p4 biu din bng lng t
Biu din phn t NO2 bng lng t. c mt lin kt th N v mt nguyn t oxi phi trng thi lai ha sp2. N p Lai ha sp2 3AO lai ha sp2
Lai ha sp
p 3AO lai ha sp2
Lai ha sp3
4AO lai ha sp3
S chung m t s hnh thnh lin kt trong phn t NO2 p O (sp2) N (sp2) O (sp3) p NO2
(Mi tn 1 chiu ch lin kt cng ha tr cho nhn, 2 chiu ch lin kt cng ha tr thun ty). T m hnh phn t NO2, nhn thy NO2 c 1 lin kt cng ha tr N-O thun ty, 1 lin kt cng ha tr NO cho nhn, 1 lin kt N-O. nguyn t N cn 1 e c thn chim AO -sp2, Vy phn t NO2 thun t.
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Do , biu din cng thc cu to ca NO2 bng 2 dng h bin sau (v khng phn bit c nguyn t O no mang lin kt ).
N O O O
N O
Cng c th biu din bng cch sau: N O O O
N O
T 2 dng h bin ny, c th thay bng 1 cng thc sau: N O O
(Gch ----- biu din lin kt khng nh ch) Bi 6. T cng thc cu to ca NO2 hy: a) suy ra cng thc cu to ca SO2. b) Gii thch ti sao phn t NO2 li i me ha cho N2O4, trong khi SO2 li khng c c iu ny? c) Suy ra cng thc cu to ca N2O5, HNO3. Bi 7. Cho cc hp cht: OF2, NF3, BF3 bit gc thc nghim o c FOF = 103015 ; FNF = 109028 ; FBF = 1200. Hy cho bit: S cp electron lin kt v khng lin kt. Kiu lai ho. Dng tng qut AXnEm Cu trc khng gian. Gii thch ti sao gc ho tr tng dn t OF2 n BF3. Bi 8. Biu din lin kt cng ho tr bng s lewis ca : SO2, SF4, Al2(CO3)2, NO2, AlCl4 . Bi 9. Da vo quan im lai ho trong thuyt VB cho bit trng thi lai ho ca Be trong BeH2, ca B trong BF3, ca C trong CH4.
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Bi 10. Vit cng thc cu to lewis, tnh in tch hnh thc mi nguyn t v c h; tnh bc lin kt cho mi lin kt ca h (phn t hay ion) sau y: a. C2H4 ; C4H6 ; C6H6 b. CH3OH ; CH3CHO ; CH3COOH c. NH4+ ; SO32- ; CO32-. Bi 11. Hy vit cng thc cu to lewis cho mi h sau, s cng hng cu to th hin y nh th no ? phn tch c th: NO3 , CO. Phn bi tp ca Tm an Bi 12. Cn c vo quan nim hin i v s to thnh lin kt ha hc hy cho bit ngha ca du v ln ca s xen ph cc obitan nguyn t (AO) trong qu trnh kho st s hnh thnh lin kt ha hc gia cc nguyn t. Th no l s xen ph dng, s xen ph m, s xen ph bng khng? Cho hai th d minh ha v mi loi . Bi 13. Da vo thuyt lin kt ha tr (thuyt VB) ha m t s hnh thnh lin kt trong cc phn t PH3, AsH3. Bit gc lin kt ca PH3 l 930, ca AsH3 l 920. Bi 14. Da vo thuyt lin kt ho tr hy m t s hnh thnh lin kt trong cc phn t H2S, H2Se, H2Te. So snh di lin kt v gc lin kt ca chng. Bi 15. Cn c vo thuyt lin kt ho tr v vo cu to nguyn t ca cc nguyn t h p, hy cho bit: 1) V sao cc electron cc lp th hai, th ba k t bn ngoi khng th than gia vo vic hnh thnh lin kt ha hc. 2) V sao a s cc nguyn t h p c nhiu ha tr v cc gi tr ca chng chnh lch nhau 2 n v 3) Khng th khng nh c rng: cc nguyn t c cu trc v electron ngoi cng nh nhau s c cng ha tr. 4) Khuynh hng biu hin ha tr cc i, s oxi ha cc i ca cc nguyn t ny thay i nh th no trong phm vi mt phn nhm. Bi 16. Da vo thuyt spin v ha tr hy: 1) Trnh by cc ha tr c th c ca cc nguyn t thuc chu k 2 ca bng h thng tun hon. 2) Gii thch v sao cc nguyn t Cl, S, P v ni chung cc nguyn t ng d chng trong cng mt phn nhm c th c ho tr cc i bng s th t nhm, trong khi cc nguyn t u nhm (F, N, O) khng c kh nng . Bi 17. Dng lng t hy biu din qu trnh hnh thnh lin kt ha hc trong cc phn t FO, F2O2, HOF, HFO2, H3N.BF3, (t NH3 v BF3). T vit cng thc electron ca cc phn t v cho bit phn t no c kh nng phn ng mnh nht? phn t no c khuynh hng ime ho. Bi 18. Trong trng hp tng qut ha tr ca mt nguyn t c xc nh bng s cc obitan c dng to ra lin kt ha hc. Theo quan im hy: 1) Xc nh ha tr ca cc nguyn t trong cc trng hp a ra bi 17.
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2) Cho bit cng ha tr cc i ca cc nguyn t chu k 2 c th bng bao nhiu? Khng k kh him, nhng nguyn t no ca chu k thc t khng c c gi tr ny? v sao? Bi 18. 1) Da vo thuyt lin kt ha tr m t s hnh thnh lin kt trong cc trng hp sau: a, CF4, CCl4, CBr4. b, Si(CH3)4, Sn(CH3)4, Pb(CH3)4. 2) So snh di v nng lng lin kt ca cc lin kt trong mi dy. Bi 19. Kho st phn t CO2 theo thuyt lin kt ha tr. T kt qu kho st hy d on nhit ha lng v ha rn ca kh cacbonic. Bi 20. Kho st phn t SO2 theo thuyt lin kt ha tr. T kt hp vi bi 19 hy so snh nhit ha lng v ha rn ca SO2 v CO2. Bi 21. 1) Hy m t s hnh thnh lin kt trong phn t BF3 v cu to ca phn t theo thuyt lin kt ho tr. 2) Vi cch m t hy a ra phn (1) c gii thch tha ng s rt ngn rt nhiu khong cch gia cc nguyn t B, F lin kt hay khng? Cho d B F = 1,29 A0 , rB = 0,759 A0 , rF = 0,709 A0 . Bi 22. 1) Hy m t s hnh thnh lin kt cc phn t BCl3, BBr3. 2) So snh rt ngn ca cc lin kt B X khi X thay i t F n I. Bi 23. 1) C th xp H vo cng mt phn nhm vi cc nguyn t halogen c khng? Hy gii thch. a, Ti sao c cc phn t BF3, BCl3, BBr3 nhng li khng c phn t BH3? b, Ti sao li tn ti c phn t B2H6. 2) B, Al l 2 nguyn t nm lin k nhau phn nhm chnh nhm III. Gii thch ti sao c phn t Al2Cl6 nhng li khng c phn t B2Cl6.
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CHNG 4 CC TRNG THI TP HP CA VT CHT A. MC TIU, NHIM V 1. MC TIU Hc xong chng 4 sinh vin phi tr li c cc cu hi: - Lc tng tc gia cc phn t l g? Lc Van e Van l g? Ngun gc c lc Van e Van? - Lin kt hiro l g? - Vt cht tn ti cc trng thi no? Sinh vin phi nm vng cc kin thc sau: - Lc tng tc gia cc phn t, lc Van e Van, Lin kt hiro, cc trng thi tp hp ca vt cht. - Cc kiu lin kt hiro: Lin kt hiro n phn t v lin kt hiro ni phn t. 2. NHIM V Hc xong chng ny ngi hc phi gii thch c: - S khc nhau v trng thi tp hp ca cc cht? - S khc nhau v nhit nng chy, nhit si. - Cc hin tng nh hin tng a hnh, hin tng ng hnh, s chm si, s chm ha rn,... 3. PHNG PHP Nm vng cc kin thc c bn t c kh nng vn dng cc kin thc c hc vo thc tin. B.NI DUNG M u: Mt trong nhng vn ca ho hc cn tr li l cc phn t tng tc vi nhau nh th no, cng nh nh hng ca tng tc gia cc phn t n trng thi tp hp ca vt cht? Chng ny cung cp cho ngi hc mt s vn sau: 1. Lc tng tc gia cc phn t: Lc Van e Van v lin kt hiro. 2. Cc trng thi tp hp ca vt cht: Trng thi kh, rn v lng. 1. LC TNG TC GIA CC PHN T phn cu to nguyn t, ch r s tn ti ca nguyn t l do lc lin kt gia cc ht proton v ntron trong ht nhn. Cn phn t tn ti c l do lc lin kt ha hc gia cc nguyn t trong phn t (200 kJ/mol). Cn gia cc phn t li c lc lin kt yu hn (10 20 kJ/mol) c gi l lc tng tc tng tc gia cc phn t hay lc Van e Van ( ghi nh nh bc hc vt l ngi H Lan l Van e Van: Van der Waals, 1837 - 1923, gii thng Nobel v vt l nm 1910, ngi u tin pht hin ra nhng lc ). Theo Van e Van tng tc gia cc phn t mang bn cht tnh in, tc l gm c lc ht v
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lc y. Cc phn t khc nhau th lc Van e Van s khc nhau do cc phn t s tn ti cc trng thi khc nhau nh: rn, lng, kh. Ngoi ra cn c 1 tng tc gia cc phn t nhng mnh hn lc Vandevan l lin kt hiro. 1.1. Lc Van e Van Bao gm 3 loi lc (3 loi tng tc) gia cc phn t. 1.1.1. Lc nh hng (tng tc lng cc vi lng cc) Nm 1912, Kenxom cho rng nguyn nhn gy ra lc Van e Van l do momen lng cc vnh cu ca cc phn t () gy ra, hnh 4.1.
HNH 4.1. M hnh v s nh hng ca cc lng cc Khi nhng phn t c cc n gn nhau, do tng tc tnh in gia cc lng cc lm cho nhng phn t xoay hng cho nhng u khc du ca cc lng cc gn nhau dn ti xut hin lc ht gia cc lng cc lm cho nng lng ca h nh nht (cc tiu). Tng tc nh vy gi l tng tc nh hng. Tng tc ny cng ln khi momen lng cc ca phn t cng ln, v d lc nh hng ca H2O ln hn ca CO v H O = 1,84 > CO = 0,12 . Nng lng ca tng tc nh hng c tnh theo h thc:
2
Trong : l momen lng cc; r l khong cch t tm ca lng cc ny n tm ca lng cc khc (hnh 4.1); k l hng s Bnxman; T l nhit tuyt i (nhit Kenvin). T biu thc 4.1, thy rng nng lng tng tc nh hng t l nghch vi nhit T v t l thun vi momen lng cc ca phn t. Khi nhit tng th vn tc chuyn ng nhit ca phn t tng lm cn tr s nh hng ca cc lng cc, cn lc nh hng cng mnh khi momen lng cc cng ln. 0 Lc nh hng lm tng nhit si (t s0 ) v nhit nng chy (t nc ) .
0 tn
2 4 Uh = 6 3r kT
(4.1)
V d 1: Butan (C4H10) - 1380C - 0,50C Axeton (CH3COCH3) - 950C + 560C (kt qu thc nghim o p = 1atm) 1.1.2. Lc cm ng (tng tc lng cc cm ng) Nguyn nhn th hai gy ra lc Van e Van l do lc cm ng: Lc cm ng xut hin khi mt phn t khng phn cc ( = 0) bn cnh mt phn t phn cc ( 0). Do tc dng ca in trng c to ra bi phn t phn cc ( 0) lm cho phn t khng phn cc ( = 0) b phn cc, s phn cc ny
t s0
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c gi l s phn cc do cm ng (c 0), hnh 4.2. Khi ny cc phn t ht nhau bi lc cm ng.
HNH 4.2. M hnh v s phn cc do cm ng Nm 1920, bai a ra biu thc tnh nng lng ca lc tng tc cm ng: Uc = Trong : v r c ngha nh trn, l phn cc ho ( l hng s), gi tr ln ca cho bit phn t d b phn cc hay kh b phn cc. cng ln phn t cng d b phn cc nn Uc cng ln. Tr s ca mt s phn t CO: 1,99.10-24cm3; HBr: 5,38.10-24cm3;... Trong thc t lc cm ng thng rt nh, nh hn c lc khuch tn (bng 4.1) 1.1.3. Lc khuch tn Hai loi lc trn u khng gii thch c s tn ti cc trng thi rn, trng thi lng ca cc kh nh H2, O2, N2, kh him. V vy cn a thm mt loi tng tc th ba gii thch hin tng ny, l lc khuch tn. Lc ny c lnn gii thch theo quan im hin i v cu to nguyn t v cu to phn t nh sau: Trong phn t, cc electron chuyn ng lin tc cn ht nhn th dao ng quanh v tr cn bng. C mt thi im s chuyn ng v dao ng s lm cho s phn b in tch dng v m lch khi v tr cn bng, dn n xut hin mt lng cc tm thi. Cc lng cc tm thi ny s tng tc vi nhau cho s nh hng ca cc phn t thun li hn v mt nng lng.
2 2 r6
(4.2)
HNH 4.3. M hnh v s nh hng ca cc lng cc c to ra do lc khuch tn Th nng tng tc ca lc khuch tn c tnh theo h thc: Ukt =
3h 0 2 4r 6
(4.3)
Trong : , r c ngha nh trn cn h l hng s Plng, 0 l tn s dao ng ng vi dao ng im 0 ca phn t.

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Tng tc khuch tn khng nhng xut hin gia cc nguyn t (trng hp ca kh him) m cn xut hin gia cc phn t khng c cc (H2, N2, O2, ...) v cc phn t c cc (HCl, CO,...). * Tng hp 3 loi lc ny ta c nng lng tng tc ht gia cc phn t l:
A 2 2 0 = 6 U = Uh + Uc + Ukt= 6 + 6 + 6 3r kT r 4r r
4 2
3h 2
(4.4)
Trong : A =
3h 0 2 2 4 + 2 2 + 4 3kT
Nng lng tng tc mang du m, v y l lc ht gia cc phn t (nguyn t). Lc ht t l nghch vi r6 (khong cch gia cc phn t, nguyn t). Phn ng gp ca mi loi tng tc vo lc Van e Van ph thuc vo cu to ca phn t. Hai tnh cht quan trng nht ca phn t l momen lng cc v phn cc ho ca phn t. i vi nhng phn t c momen lng cc ln tng tc nh hng c vai tr cng ln. i vi nhng phn t cng d b cc ho () ln th tng tc khuch tn c vai tr cng tng. Trong khi tng tc cm ng ph thuc vo c hai yu t nhng ch c vai tr th yu. BNG 4.1. Nng lng ca 3 loi tng tc v nng lng Van e Van ca mt s cht (kJ/mol) Momen lng cc (D) He Ar Xe CO HCl HBr HI NH3 H2O 0 0 0 0,12 0,17 0,79 0,38 1,48 1,84 cc ha .10 (cm ) 0,20 1,63 4,00 1,99 2,63 3,58 5,4 2,21 1,4
-24 3
Cht
Lc nh hng 0 0 0 0 3,31 1,09 0,59 13,31 36,36
Lc cm ng 0 0 0 0 1,00 0,71 0,31 1,55 1,92
Lc khuch tn 0,21 8,49 18,41 8,74 16,82 28,45 60,92 14,73 9,00
Lc Van ec Van 0,21 8,49 18,41 8,74 21,13 30,25 61,82 29,59 47,28
T bng 4.1, ta thy tr H2O l phn t c cc rt mnh. Tng tc khuch tn c vai tr ln trong lc Van e Van. V vy lc Van e Van ph
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thuc rt nhiu vo phn cc ho . phn cc ho tng ln khi kch thc ca phn t hay nguyn t tng ( y l bn knh nguyn t hoc di lin kt ca phn t). y chnh l c s gii thch s tng nhit nngchy, nhit si ca cc n cht v hp cht tng t nh bin thin ca cc nguyn t t trn xung di trong bng h thng tun hon. V d 2: Kh him He Ne Ar Xe Rn 0 Nhit si, C -268,8 -246 -105,9 -109,1 -62 Cl2 Br2 I2 Halogen F2 0 Nhit si, C -187,9 -34,1 58,2 184,5 Hir halogenua HCl HBr HI 0 -84,9 -66,7 -35,8 Nhit si, C * Lc y gia cc nguyn t, phn t xut hin khi cc nguyn t, phn t tin li gn nhau n mt mc no . Khi nng lng ca tng tc y c biu th bng biu thc:
U =
m r 12
(4.5)
Vi m l hng s y. Phng trnh 4.5 cho thy, lc y cng ln khi r cng b. Nng lng ton phn c tnh bng biu thc:
U = A m + r 6 r 12
(4.6)
* Bn knh Van e Van: Thng c tnh bng mt na khong cch gia hai nguyn t thuc hai phn t khc nhau trong tinh th, hnh 1.4.
HNH 4.4. Bn knh Van e Van v bn knh cngho tr ca Clo Hnh 4.4 cho thy bn knh Van e Van ca nguyn t Cl l 1,80 A0 ln hn nhiu so vi bn knh cng ha tr ca Cl l 0,99 A0. Do lc Van e Van c
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nng lng yu hn nhiu so vi lin kt cng ha tr nn bn knh Van e Van ca nguyn t lun ln hn bn knh cng ha tr, bng 4.2. BNG 4.2. Bn knh Van e Van ca cc nguyn t phi kim(A0)
H N P As Sb 1,1 - 1,3 1,15 1,9 2,0 2,2 O S Se Te 1,40 1,85 2,00 2,20 F Cl Br I 1,35 1,80 1,95 2,15 He Ne Ar Kr Xe 1,22 1,50 1,91 2,01 2,20
Da vo lc Van e Van c th gii thch c s tn ti cc trng thi rn, lng kh ca cc cht. 1.2. Lin kt hiro (lin kt cu ni hiro) * M u: Nu ch da vo lc Van e Van th khng th no gii thch c s bt thng v mt s tnh cht nh nhit si, nhit ha hi,... ca cc hp cht nh HF, H2O, NH3. S tng nhit si ca dy CH4, SiH4, GeH4, SnH4 v ca kh him c gii thch bng s tng lc Van e Van khi khi lng phn t ca cc hirua EH4 v khi lng nguyn t ca cc khi him tng, hnh 4.5. Trong cc dy hirua EH, EH2, EH3, ti sao cc hp cht HF, H2O, NH3 li c nhit si cao hn hn so vi cc hp cht tng t trong cng mt dy? iu ny khng th gii thch c bng lc Van e Van m bng lin kt 0 C hiro.
100
H2O
HF
0
NH3
-100
HCl PH
3
H2S
H2Se
AsH3
H2Te SbH3 HI SnH4
HBr GeH4
SiH4 Kr
Xe
CH4
-200
Ar
Ne
HNH 4.5. Nhit si ca mt s dy hirua v ca kh him

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1.2.1. Khi nim Lin kt hyro l lin kt c to ra gia nguyn t H ca phn t ny vi cp electron khng lin kt ca nguyn t khc c m in mnh. Lin kt hiro c biu din bng s : X HY Lin kt hiro c biu din bng du ba chm () Ba nguyn t X, H, Y thng trn mt ng thng. V d 3: Trong H2O lng v HF lng c lin kt hiro
H-FH-FH-F O-HO-HO-H
H H H iu kin hnh thnh lin kt hiro l nguyn t X, Y phi c m in ln v bn knh nh, v vy X, Y thng l cc nguyn t thuc chu k 2. iu kin bt buc i vi nguyn t Y l Y phi c cp electron khng lin kt (cp electron ring). 1.2.2. Bn cht ca lin kt hiro a) Lin kt hiro c bn cht tnh in Khi nguyn t H lin kt vi nguyn t c m in mnh nh N, O, F th cp electron ca lin kt phn cc mnh v pha N, O, F lm cho nguyn t H mang mt phn in tch dng (H+) do H+ tr nn hot ng hn. Khi H+ gn mt nguyn t m in mnh v li c cp electron ring th H+ s lin kt vi nguyn t ny
+ -
+ -
+ -
:F-H+ :F-H+ :FH :FH

b) Lin kt hiro l mt lin kt yu V di lin kt: Lin kt hiro c di lin kt ln hn cc lin kt thng thng khc. V d 4: di ca lin kt hiro trong O H O l 2,7 A0 2,8 A0; trong O H N l 2,8 A0 2,9 A0 Do di ca lin kt hiro ln nn nng lng lin kt rt nh c t 10 30 kJ/mol 1.2.3. Cc kiu lin kt hidro a) Lin kt hiro lin phn t c hnh thnh gia cc phn t vi nhau. Trong trng hp ny, nguyn t H+ thuc mt phn t lin kt vi nguyn t c m in mnh thuc phn t khc.
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Cc phn t ny c th ca cng mt cht nh v d 3, hoc cc phn t ca hai cht khc nhau, nh: O H H H O H F R C O O C H O R
Gia hai phn t khc nhau Gia hai phn t axit ging nhau b) Lin kt hiro ni phn t c hnh thnh trong cng mt phn t Trong trng hp ny, nguyn t H+ lin kt vi mt nguyn t c m in trong cng mt phn t vi H+, nh trong phn t anehit salixilic, o flo phenol
H C O O H O H F
anehit salixilic o - flo phenol 1.2.4. Tnh cht ca cc hp cht c kh nng to lin kt hiro 0 a) Lm tng nhit si ( t s0 ) v nhit nng chy ( t nc ): v cc phn t lin kt li vi nhau thnh phn t ln. Xt s bt thng v nhit si ca cc cht sau iu kin tiu chun Cht H2O (18) H2S (34) CH3OCH3 (46) CH3OH (34) 0 ( C) 100 -62 -24 66 Trong ngoc n l khi lng mol phn t ca cc cht. Chng ta thy nhit si ca CH3OCH3 cao hn so vi H2S l do lc tng tc Van e Van gia cc phn t CH3OCH3 ln hn v c khi lng mol phn t ln hn. Trong khi Mc d c H2O v CH3OH u c lin kt hiro nhng nhit si ca H2O li cao hn nhiu l do nng lng ca lin kt hiro gia cc phn t H2O ln hn nhiu so vi cc phn t CH3OH vi nhau. Ti sao trong cng mt dy EHn (n = 1,2,3,4) cc hp cht HF, H2O, NH3 nhit si li cao hn so vi cc hp cht trong cng mt dy? iu ny c gii thch bng lin kt hiro. cc trng thi rn v lng, thm ch ngay c trng thi kh (HF) nhng phn t ca cc cht ny khng tn ti tng phn t ring r m kt hp vi nhau (nh lin kt hiro) thnh mt phn t ln nh (HF)n, (H2O)n, (NH3)n. y n c gi tr khc nhau i vi mi cht v gim dn khi nhit tng. Trong cc phn t ln ny, cc n phn phn t nh HF, H2O, NH3 lin kt vi nhau nh lin kt hiro b) Gii thch kh nng to ime ngay th hi ca axit hu c Thc nghim xc nhn ngoi dng ime, cc phn t axit hu c cn tn ti dng polime mnh di.
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O
C R
H O
O C R
H O
O C R
Cn ch , lin kt hiro lin phn t lm tng nhit nng chy, nhit si. Trong khi lin kt ni phn t khng c nh hng ny. V d 5: Cht oH2NC6H4OCH3 pH2NC6H4OCH3 0 0 205 243 ts ( C) c) tan Nu phn t cht tan to c lin kt hiro gia n vi dung mi th tan tng. Cc cht nh ru, amin, axit hu c (c khi lng phn t nh), glucoz, saccarz... tan tt trong H2O, v to c lin kt hiro vi nc. Trong khi cc phn t c lin kt hiro ni phn t li kh tan trong nc do khng to c lin kt hiro vi nc, d tan trong cc dung mi hu c khng phn cc. So snh t l v tan 600C ca 2 ng phn orto v para-nitro phenol (o/p) trong H2O v ancol butylic c kt qu ln lt l: 0,2 v 0,885 cn trong benzen l 127,5. Kt qu cho thy ng phn orto tan tt trong ru v benzen, cn ng phn para li tan tt trong nc. d) bn ca ng phn Lin kt hidro ni phn t lm tng bn ca ng phn. V d 6: o -flo phenol tn ti 2 dng sau:
H O F O H F
trans Cis Thc nghim xc nh c t l ng phn trans/cis = 1/56, iu ny chng t dng cis bn hn dng trans 2. CC TRNG THI TP HP CA VT CHT Tu thuc vo iu kin bn ngoi nh nhit (T), p sut (P) m mt cht c th tn ti cc trng thi kh, lng hoc rn. Nhng trng thi tn ti c gi l trng thi tp hp ca cht. S khc nhau v trng thi ca mt cht l do c s khc nhau v khong cch gia cc ht (ion, nguyn t, phn t) v lc tng tc gia cc ht , do dn n s khc nhau v quan h gia ng nng v th nng ca ht.
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2.1. Cht kh Trong cht kh, cc phn t (hay nguyn t, trng hp kh him) cch xa nhau, khong cch ny ln hn rt nhiu so vi kch thc ca phn t do lc tng tc Van de Van gia cc phn t kh l rt yu, nn cc phn t kh lun trng thi chuyn ng hn lon. V th, cht kh c th nn c v chim ton b th tch ca bnh ng. V lun chuyn ng, nhng phn t kh va chm vi nhau v va chm vi thnh bnh cha kh. S va chm vo thnh bnh xy ra thng xuyn v th lun to ra mt p lc tc ng ln thnh bnh cha kh. p lc ny, khi tnh trn mt n v din tch b mt c gi l p sut ca kh. p sut thp v nhit cao, cc phn t kh chuyn ng hn loi, do cc kh khc nhau c tnh cht gn nhau. p sut rt thp (gn chn khng), kch thc ca cc phn t so vi th tch chung ca kh v tng tc gia cc phn t kh rt b, nn c th b qua. Kh nh vy c gi l kh l tng. Kh l tng tun theo phng trnh trng thi ca kh l tng PV = RT (Tnh cho 1mol kh), cn PV = nRT (tnh cho n mol kh). Khi p sut cao v nhit thp, cc phn t kh s gn nhau, khi ny lc Van e Van mnh ln v khng b qua c na. Khi ny, c im ca kh th hin r rt hn. Kh nh vy, c gi l kh thc v kh thc tun theo phng trnh trng thi ca kh thc. a P + 2 (V - b) = RT (tnh cho 1mol kh thc) V a Trong 2 l i lng phn nh lc ht gia cc phn t kh, b phn V nh th tch ring ca cc phn t. (a, b c gi l cc hng s Van de Van). a) S ho lng cht kh Khi lm lnh cht kh p sut thng, cht kh s ho lng mt nhit xc nh. Nhit c gi l nhit ho lng ca kh p sut thng. Ngc li, khi un nng mt cht lng p sut thng, cht lng s ho hi, tc l si, cng ti nhit p sut thng. l nhit si ca cht lng. Nhit ho lng hay nhit si ca mt cht phc thuc rt nhiu vo p sut. Nhit ny tng ln khi tng p sut v gim xung khi gim p sut. V th, mun ho lng kh, ngi ta thng nn kh p sut rt cao v ng thi phi h thp nhit ca kh. y l nguyn tc chung ho lng kh. Tuy nhin, vic nng cao nhit ho lng nh vic nng cao p sut ca kh cng c mt gii hn nht nh. Qua nhit , cht lng s khng th tn ti d di bt c mt p sut no. Nhit cc i c gi l nhit ti hn (Tth), v p sut cn thit cht kh ho lng nhit c gi l p sut ti hn (Pth). cc iu kin ti hn th tch ca kh v lng bng nhau nn ti kh v lng c t khi bng nhau. Bng 1.3 cho bit nhit ti hn v p sut ti hn ca mt s cht
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BNG 4.3. Hng s ti hn ca mt s cht Cht He H2 N2 O2 CH4 CO2 Cl2 C2H6 NH3 SO2 C6H6 H2O Nhit si
0
Nhit ti hn, 0 C -267,90 -239,90 -147,00 -118,40 -82,10 -31,00 144,00 32,27 132,30 157,50 289,50 374,20
p sut ti hn atm 2,26 12,80 33,54 50,10 45,80 72,9 76,10 48,20 111,30 77,80 48,60 218,30
Th tch ti hn Cm3/mol 57,80 65,00 90,10 78,00 99,00 94,00 124,00 148,00 73,50 122,00 260,00 56,00
-268,44 -252,77 -198,82 -182,97 -162,58 -78,43 -34,06 -88,63 -33,43 -10,02 80,099 100,00
T bng, ta thy hi H2O ho lng 1000C di p sut thng (1atm). Khi tng p sut, H2O hi c th ho lng nhit thng v n 218,3atm th hi nc ho lng 374,20C. iu c ngha l vt qu nhit ti hn ca H2O (374,20C), th hi H2O khng th ho lng di bt k p sut no. 2.2. Cht lng Cht lng l trng thi trung gian gia trng thi kh v trng thi rn (tinh th). nhit cao cht lng c tnh cht gn vi cht kh, cn nhit thp gn vi cht rn (tinh th). Trong kin trc ca cht lng, ngoi nhng vng trong cc ht c xp lin nhau th cn c nhng khng gian trng (l trng), nhng l trng ny khng c hnh th v kch thc xc nh, n xut hin ch ny ri bin dng v di sang ch khc. V cc ht cht lng khng c sp xp lin nhau mt cch st sao nht. iu ny khc vi tinh th, trong tinh th cc ht c sp xp lin nhau mt cch xt sao nht (hnh 1.6), mi ht trong cng mt lp c 6 ht khc bao quanh. Chnh nhng l trng trong cht lng lm cho khong cch trung bnh gia cc ht trong cht lng ln hn trong cht rn. a s cc cht rn khi ha lng u tng th tch (ln khong 10%) ngha l khong cch trung bnh ca cc phn t trong cht lng ln hn trong cht rn (khong 3%). Nh vy, c th chp nhn khong cch gia cc ht trong cht lng xp x khong cch gia cc ht trong cht rn. V vy, lc tng tc Van e Van gia cc ht l kh ln, nhng vn cha ngn cn chuyn ng ca cc phn t cht lng, nn cc
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phn t cht lng vn chuyn ng hn lon. Chnh cu trc nh vy m cht lng t chu nn v khng c hnh dng xc nh ging nh cht rn.
HNH 4.6. M hnh so snh cu trc tinh th (a) v cu trc ca cht lng (b) 2.2.1. p sut hi bo ha ca cht lng Trn b mt thong ca cht lng, cc phn t cht lng lun b ht vo pha trong lng cht lng. Cc phn t trn b mt mun ri khi cht lng i vo khng kh (tc l bay hi), phn t cn phi c mt nng lng xc nh thng c lc ht . Ti mi mt thi im, ch c mt s t phn t c ng nng ln hn ng nng trung bnh ca cc phn t mi tch ra khi b mt thong v i vo khng kh. Bng cch ny cht lng bay hi. Khi nhit tng th s phn t bay hi cng nhiu. Song song vi qu trnh bay hi, cn c qu trnh ngng t ca cc phn t hi thnh lng. n mt thi im no s phn t kh pha hi khng thay i na (thi im vn tc bay hi bng vn tc ngng t) th cn bng gia pha lng v pha hi c thit lp. Khi ny p sut ca kh pha hi cng khng thay i do s mol kh pha hi khng thay i, p sut ny c gi l p sut hi bo ha. H c thit lp ti mt nhit Vy: p sut m ti cn bng L xc nh gi l p sut hi bo ha.
P(atm) 3 1) ietylete 2) n-hexan 2 1 2 3 4 3) Ru etylic 4) nc
0 -20
20
60
80
100
120
t (0C)
HNH 4.7. S ph thuc ca p sut hi bo ha vo nhit

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Hnh 4.7 cho thy ti mi mt nhit xc nh mi cht lng c mt p sut hi bo ha xc nh. p sut hi bo ha ny tng ln khi nhit tng. 2.2.2. Nhit si ca cht lng Nhit si ca cht lng l nhit ti p sut hi bo ha ca cht lng bng p sut ca kh quyn, tc l bng 1 atm V d 7: H2O si 1000C di p sut l 1atm, v nhit ny p sut hi bo ha ca H2O bng 1atm bng p sut kh quyn. Hnh 4.7 cn cho bit p sut thp th nhit si ca cht lng thp, cn p sut cao th nhit si ca cht lng cao, khi p sut kh quyn cng cao th p sut hi bo ha cng cao nhit si cng cao. Cc cht lng khc nhau th c nhit si khc nhau v c ng cong p sut hi bo ho khc nhau. Tai mt nhit xc nh, cht lng no c p sut hi bo ha cng cao th nhit si cng thp. Khi si qu trnh bay hi xy ra trong ton b th tch ca cht lng ch khng phi ch din ra trn b mt, v xut hin nhng bt hi khp trong lng cht lng. Mun cho bt hi c th sinh ra c v ln ln th p sut hi bn trong bt hi t nht phi bng p sut bn ngoi tc dng ln bt hi . p sut ny bng p sut ca kh quyn cng vi p sut gy nn bi ct cht lng trn bt hi tc dng ln bt hi. V vy, s to thnh bt hi v s si ch xy ra khi p sut hi ca cht lng bng p sut kh quyn. * Hin tng chm si: Ban u to ra nhng bt hi trong lng ca mt cht lng tinh khit (khng c kh ho tan) l rt kh khn, nguyn nhn l do nhng phn t c ng nng ln cn cho s bay hi khng tp trung li kt t li vi nhau c. V vy: khi un nng mt cht lng n nhit si ca n m cht lng vn khng si, tip tc un nng nhit ca cht lng tng ln cao hn nhit si, nhng cht lng vn khng si. Hin tng nh th c gi l s chm si V d 8: Nc tinh khit c th un nng n 1800C m vn khng si di p sut kh quyn l 1 atm. Cht lng khng th tn ti mi hin tng chm si, sm hay mun cht lng cng s phi si v si rt mnh lit, n mc c th gy n bnh cha cht lng gy nguy him. Trong thi im ny nhit ca cht lng gim t ngt n nhit si. Mun trnh hin tng chm si, trc khi chng ct mt cht lng no cn cho thm vo cht lng nhng mnh bt, nh mnh s, mnh vi. Nhng bt kh trong nm trong nhng l xp ca bt s thot ra to iu kin sinh ra nhng bt hi cht lng v cht lng s si. * Hin tng chm ha rn: Khi lm lnh ho rn mt cht lng, cch sp xp li cc ht cht lng bin i khng ng k, xem hnh 4.6. Tuy nhin i vi mt s cht , cch sp xp li ny thay i rt nhiu. Trong trng hp ny qu trnh kt tinh s kh thc hin. Khi s gy ra hin tng chm ha rn ca cht lng, tc l di nhit ho rn cht lng vn tn ti trng thi lng. Mc chm ha rn s cng ln khi cu trc ca trng thi rn v
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trng thi lng khc nhau cng nhiu. Da vo hin tng chm ha rn ca cht lng, c th bit c cu trc ca cht lng . i vi cht kh v cht rn chng ta c nhng hnh mu so snh l kh l tng v tinh th l tng. Cn vi cht lng th khng c hnh mu no c, nn c th ni cht lng c cu trc phc tp. 2.2.3. Nhit ha hi Khi un nng mt cht lng n nhit si ca n th cht lng s si, khi ny nhit si ca cht lng khng tng m tng lng cht lng s ha hi. Vy: Nhit ha hi l nhit lng cn cung cp lm ha hi mt mol cht lng ti nhit si ca cht lng . Nhit ho hi k hiu l: Hhh (hh: ha hi), n v o: J/mol, kJ/mol hay cal/mol, kcal/mol. Nhit ha hi dng thng lc ht gia cc phn t cht lng v lm tng ng nng cho cc phn t cht lng. Qu trnh ngng t ca hi thnh lng lun pht ra mt nhit lng ng bng nhit lng ca cht lng hp th ha hi ti cng mt nhit . Bng 1.4. cho bit nhit ha hi ca mt s cht lng nhit si ca n. Cht lng He H2 N2 O2 Cl2 Nhit ha hi (kJ/mol) 0,083 0,911 5,574 6,809 19,884 Cht lng NH3 CO2 C6H6 C2H5OH H2O Nhit ha hi (kJ/mol) 22,822 26,012 29,844 40,044 40,612
BNG 4.4. Nhit ha hi ca mt s cht lng nhit si (kJ/mol) 2.2.4. Tnh nht Tnh nht ca cht lng l do cc lp cht lng cn tr chuyn ng ca nhau gy ra. Tnh nht ph thuc vo nhit , khi nhit tng th tnh nht gim v khi tng nhit th khong cch trung bnh gia cc ht cht lng tng ln v lc tng tc gia cc ht gim xung. Mt trong nhng phng php o nht ca cht lng l da vo vn tc chuyn ng ca cht lng khi i qua ng mao dn ca nht k. .P.r 4 .t Biu thc o nht ( ): = 8.V.l Trong : P l hiu p sut 2 u ng mao qun; r l bn knh ng mao qun; l l chiu di ng mao qun; t l thi gian chy; V l th tch cht lng chy qua ng mao dn trong thi gian t.
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BNG 4.5. nht ca mt s cht lng o 200C (chn nht ca H2O = 1 lm n v o) Cht lng Axeton H2O Anilin H2SO4 Glixerin nht (Xentipra) 0,33 1,00 4,43 27 1499
2.2.5. Sc cng b mt Sc cng b mt l mt tnh cht c trng ca cht lng gy ln bi sc ht ln nhau gia cc ht v xut hin trn b mt phn chia gia hai pha (lng lng; lng kh; lng rn). Kh
Lng
P =0
P1
HNH 4.8. M hnh m phng s xut hin ca sc cng b mt Cc phn t cht lng nm bn trong lng cht lng khc vi nhng phn t nm bn trn b mt cht lng ch: Lc tng tc gia cc phn t nm bn trong vi cc phn t khc bao xung quanh n u bng nhau v b tr cho nhau, nn tng hp lc bng 0 (P = 0) , cn cc phn t nm trn b mt phn chia, tng hp lc tng tc gia chng khc 0 (P1 0) v hng xung di, vung gc vi b mt, hnh 4.8. V vy, nhng phn t nm b mt phn chia lun c xu hng b ko vo pha bn trong lng cht lng v vo mt trng thi lun chu mt sc cng - l sc cng b mt, k hiu l . Sc cng b mt () c trng cho nng lng ca b mt phn chia hay l cng cn tiu tn lm tng din tch b mt ca cht lng ln 1cm2. Mt trong nhng c im quan trng nht ca cht lng l cht lng lun c xu hng lm gim sc cng b mt ca n bng cch lm gim din tch b mt ca cht lng xung. Chnh v c im ny m cng mt th tch nh nhau
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th hnh cu c din tch b mt b nht do cht lng d dng to thnh git hnh cu. 2.2.6. Tnh mao dn Tnh mao dn l h qu ca sc cng b mt. Xut hin khi cht lng tip xc vi cht rn th xy ra hai trng hp. Nu lc ht gia phn t cht lng vi phn t cht rn mnh hn lc ht gia cc phn t cht lng vi nhau th mt thong ca cht lng trong ng thy tinh lm xung, hnh 4.9a. Ngc li,nu lc ht gia phn t cht lng vi phn t cht rn nh hn lc ht gia cc phn t cht lng vi nhau th mt thong ca cht lng trong ng thy tinh li ln, hnh 4.9b. Ngi ta ni, trng hp th nht xy ra khi ng thy tinh ng nc, cn trng hp th hai khi ng thy tinh ng thy ngn. Khi ny ngi ta ni nc thm t thy tinh cn thy ngn khng thm t thy tinh.
HNH 4.9. M hnh biu din sc cng b mt trong ng thy tinh Nu ta cm mt ng thy tinh c ng knh rt b (mao qun) vo mt cht lng thm t c ng th cht lng s dng ln trong ng - y l hin tng mao dn. Chiu cao ca ct cht lng s cng ln nu ng knh ca ng cng b. Da vo chiu cao ca ct cht lng trong ng mao qun, ngi ta d dng tnh c sc cng b mt ca ng mao qun . 2.3. Cht rn Trong cht rn, cc ht (ion, nguyn t, phn t) sp xp st nhau. Khong cch gia cc ht xp x kch thc ca ht. Khong cch ny b hn khong cch trung bnh gia cc ht trong cht lng v b hn rt nhiu so vi cht kh. V vy, tng tc gia cc ht ln hn do cc ht ch c th dao ng xung quanh v tr cn bng ca chng. V th, trong cht rn cc ht c sp xp theo mt trt t xc nh nn cht rn c hnh dng v th tch xc nh. 2.3.1. Nhit nng chy Khi un mt cht rn tinh khit n mt nhit xc nh, th cht rn s ho lng (nng chy), nhit ti cht rn nng chy gi l nhit nng chy ca cht rn. Nhit nng chy ca cht rn cng ph thuc vo p sut nhng mc thp hn nhiu so vi nhit si v s chnh lch v th tch gia cht rn v cht lng rt nh. Cht lng nu lm lnh cng ho rn ti chnh nhit nng chy ca cht rn.
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2.3.2. Nhit nng chy Vi mt cht rn dng tinh th, nhit nng chy ca n khng thay i trong sut qu trnh nng chy. Nhit lng cn cung cp cho 1 mol cht rn nng chy gi l nhit nng chy. Nhit nng chy k hiu l: Hnc (nc: nng chy), n v o l: kJ/mol hay kcal/mol. Ngc li vi qu trnh qu trnh nng chy l qu trnh ng c (ho rn), qu trnh ng c lun pht ra mt nhit lng ng bng nhit nng chy nhng ngc du. BNG 4.6. Nhit nng chy ca mt s cht rn (kJ/mol) Cht rn He H2 N2 O2 NH3 H2O C2H5OH C6H6 Nhit nng chy (0C) -271,4 -259,20 -210.01 -218,76 -77,76 0,00 -117 5,55 Nhit nng chy (kJ/mol) 0,020 0,117 0,708 0,443 6,647 6,002 4,598 9,781
So snh vi nhit ho hi, ta thy nhit nng chy ca mt cht lun b hn nhiu, v khi chuyn t trng thi rn sang trng thi lng, lc tng tc gia cc ht (ion, nguyn t, phn t) gim xung khng nhiu. Trong khi , chuyn t trng thi lng sang trng thi kh lc tng tc gim xung rt nhiu. Nu mt cht dng tinh th khng nng chy m chuyn thng thnh dng hi, tc l thng hoa. Lng nhit cn cung cp trong qu trnh ny gi l nhit thng hoa. Nhit thng hoa c tnh bng tng lng nhit nng chy v nhit ha hi ca cht . 2.3.3. Cht rn dng tinh th v cht rn dng v nh hnh Cht rn tn ti di hai dng l tinh th v v nh hnh. * Cht rn dng tinh th: L cc ht c nhiu mt ng nh, nhiu cnh v nhiu chp. Chng l cc cht rn c hnh th xc nh. V d nh mui n, ng phn,... cht dng tinh th lun nng chy mt nhit nht nh v c tnh d hng, tc l nhng tnh cht nh c, in, ch s khc x... ph thuc vo hng ngi ta o chng. * Cht rn dng v nh hnh: Khng c hnh th xc nh, v d nh thu tinh, cao su, nha. Ch v ca cc cht ny rt nhn, khng phng v hi khom. Khng c nhit nng chy xc nh, khi c t nng mi u n mm dn, hi chy v cui cng ha lng hon ton. Cht dng v nh hnh c
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tnh ng hng, tc l nhng tnh cht vt l nh in tr, ch s khc x, dn nhit u ging nhau theo mt hng. Dng v nh hnh v dng tinh th l nhng trng thi khc nhau ca cng mt cht, trong dng v nh hnh lun km bn hn so vi dng tinh th. Khi chuyn t cc trng thi khc sang trng thi rn, tu thuc vo iu kin m mt cht c th trng thi v nh hnh hay trng thi tinh th. Nh th trong nhng iu kin no ngi ta c th ch to c dng tinh th ca thu tinh hoc cao su. Nhng ht tinh th ring r ca mt cht, c gi l n tinh th. Cc n tinh th lun c hnh dng xc nh, nhng t gp chng trong t nhin m thng phi tng hp chng bng con ng nhn to. iu kin kt tinh cng nh hng rt nhiu n hnh dng ca tinh th.
HNH 4.10. Ba hnh dng khc nhau ca tinh th mui n Tinh th mui n NaCl c iu ch cn thn bng cch treo v lu mt tinh th NaCl trong dung dch qu bo ho ca n s c hnh lp phng, hnh 4.10a. Khi c kt tinh t y ca mt cc ng dung dch NaCl th tinh th NaCl c hnh mt khi vung, nhng b dy khng bng mt na ca khi lp phng, hnh 4.10b. iu ny xy ra v tinh th khng c pht trin ng u theo mi phng nh trong trng hp pht trin trn. Nu trong trng hp u, cho thm ur vo dung dch mui n, tinh th s c hnh bt din u, Hnh 4.10c. Nh vy,iu kin kt tinh nh hng rt mnh n hnh dng ca tinh th, nhng gc gia cc mt ca cc tinh th u bng nhau. Vi tinh th NaCl gc ny bng 900. y l ni dung ca nh lut gc khng i gia cc mt ca tinh th, mt nh lut quan trng ca tinh th hc. 2.3.4. Hin tng a hnh v hin tng ng hnh * Hin tng a hnh: Mt cht c th tn ti di mt s dng tinh th khc nhau c gi l hin tng a hnh. Nhng dng tinh th khc nhau v kin trc gi l dng a hnh. V d 9: Lu hunh c hai dng tinh th l lu hunh t phng (S) v lu hunh n t (S), Cacbon c hai dng tinh th l kim cng (h lp phng) v than ch (h lc phng), vi c hai dng tinh th l canxit (h t phng) v aragonit (h tam phng).
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Mi mt dng a hnh thng ch bn mt khong nhit nht nh. Mt dng a hnh ny c th chuyn thnh mt dng a hnh khc mt nhit xc nh. Cng cn phn bit hin tng a hnh v hin tng th hnh. Hin tng a hnh lin quan n cu trc mng tinh th ca n cht cng nh ca hp cht. Cn hin tng th hnh lin quan ti s khc nhau v cu to phn t hay cu trc tinh th ca n cht. V d 10: Oxi (O2) v ozon (O3) l hai dng th hnh ca nguyn t oxi. Lu hunh t phng S v lu hunh n t S l hai dng a hnh ca lu hunh, ng thi l hai dng th hnh ca lu hunh. Nh vt vi n cht rn c dng tinh th th hin tng th hnh ng nht vi hin tng a hnh. * Hin tng ng hnh: Khc vi hin tng a hnh, mt s cht khc nhau c thnh phn ho hc tng t nhau thng kt tinh dng tinh th ging nhau. Nhng cht nh vy c gi l cht ng hnh v hin tng cc cht khc nhau to ln thnh nhng tinh th ging nhau c gi l hin tng ng hnh. V d 11: CaCO3, MgCO3 ng hnh vi FeCO3. MgSO47H2O; ZnSO47H2O v NiSO47H2O ng hnh vi nhau. Cc mui kp K2SO4 Al2(SO4)324H2O v K2SO4Cr2(SO4)324H2O ng hnh vi nhau. T cc v d va nu, d thy nhng cht ng hnh vi nhau thng c cng thc ho hc tng t nhau. Tuy nhin, iu ny khng phi bao gi cng ng, nh LiCl v KCl khng ng hnh vi nhau v ion Li+ v K+ c kch thc khc nhau rt nhiu. Ni chung, nhng cht ng hnh vi nhau phi c kch thc ca cc cation tng ng nhau, cn cc anion cu to tng t nhau. Mt trong nhng tnh cht quan trng ca cc cht ng hnh l chng cng kt tinh vi nhau trong mt dung dch, khi s thu c tinh th hn hp (cn gi l dung dch rn). 3. Mt s vn v tinh th (c thm)
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Chng 5 NHIT NG HC 1. MT S KHI NIM C BN TRONG NHIT NG HC 1.1. H nhit ng H nhit ng c gi tt l h, l mt s rt ln cc tiu phn (nguyn t, phn t, ion) ang c nghin cu v c phn cch vi mi trng ngoi bng mt ranh gii xc nh (thc hoc o). * H c lp: Khng trao i cht, khng trao i nng lng vi mi trng ngoi di dng nhit v cng. H c lp c th tch khng i. * H kn (h ng): Khng trao i cht, nhng trao i nng lng vi mi trng ngoi, th tch ca h kn c th thay i. * H on nhit: Khng trao i cht v nhit vi mi trng ngoi, nhng trao i cng vi mi trng ngoi. * H h (h m): Trao i c cht v nng lng vi mi trng ngoi. * H ng th v h d th: H ng th l h m thuc tnh ca n hoc khng thay i hoc thay i t t lin tc t im ny qua im kia v hon ton khng c b mt phn chia trong h. Cn trong h c b mt phn chia th gi l h d th. Ni cch khc: H ng th ch c mt pha, cn h d th c nhiu pha. * H ng nht v khng ng nht: H ng nht l h c thnh phn nh nhau v tnh cht nh nhau khp mi im ca h. Ngc li l h khng ng nht. Nh vy: H ng nht chnh l h ng th, nhng h ng th th khng nht thit phi ng nht. 1.2. Pha Pha l nhng phn ng th ging nhau ca mt h hp thnh mt pha. Pha c gii hn vi nhng phn khc bng nhng b mt phn chia. Pha n gin ch cha mt cht, cn pha cha t hai cht tr ln c gi l pha phc tp. 1.3. Trng thi Trng thi ca mt h c xc nh bi tp hp cc thng s biu din cc tnh cht ca h nh nhit (T), p sut (P), th tch (V), ni nng (U), entanpi (H), entropi (S), th ng p (G). Thng s ca h c chia lm hai loi, l thng s cng v thng s khuych . Cc thng s cng nh: nhit , p sut, nng , chit sut, t khi, nht... chng khng t l thun vi khi lng ca h, tc l chng khng c tnh cng tnh. Cc thng s khuych nh: th tch, khi lng, ni nng (u),... chng t l thun vi khi lng ca h (tc l t l vi s mol ca h), c tnh cng tnh. 1.4. Bin i ca mt h
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Mt h nhit ng bin i khi trng thi ca h thay i. Tc l mt hay nhiu thng s ca h thay i. Bin i ca mt h xc nh nu bit r c trng thi u v trng thi cui ca h . ng i ch xc nh c khi trng thi u, trng thi cui cng nh tt c cc trng thi trung gian ca h u c xc nh. Khi trng thi u v trng thi cui khc nhau th qu trnh bin i c gi l bin i h. Cn trng thi u v cui trng nhau th gi l bin i kn chu trnh. Mt bin i c gi l on nhit nu n din ra trong iu kin khng trao i nhit vi mi trng ngoi. Mt bin i c coi nh thun nghch nu nhng trng thi trung gian m h i qua c xem nh trng thi cn bng. Khi bin i c thc hin trong iu kin ng p, th gi l bin i ng p, thc hin trong iu kin bin i ng tch th gi l bin i ng tch,... Mt bin i cn c gi l mt qu trnh. 1.5. Hm trng thi L mt i lng m bin thin ca chng ch ph thuc vo trng thi u v trng thi cui ca h m khng ph thuc vo ng i ca h - tc l khng ph thuc vo cch tin hnh qu trnh. Nu biu din hm trng thi bng ton hc th: Gi s c mt i lng X. Ly tch phn ca dX t trng thi 1 n trng thi 2 , ta c:
dX = X 2 X1 = X
1 2 1
, th ta ni X l hm trng thi
Cn X = X , th ta ni X khng phi l hm trng thi Trong trng hp ny X ph thuc vo cch tin hnh qu trnh cc i lng nh ni nng (U), entanpi (H), p sut (P), th tch (V),... l hm trng thi cn cng (A) v nhit (Q) khng phi l hm trng thi, v:
A = A
1
Q = Q
1
1.6. Nng lng Nng lng l thc o cho mi dng vn ng ca vt cht. Nng lng ca mt h bao gm 2 phn l ngoi nng v ni nng. Ngoi nng chnh l nng lng bn ngoi h n gm ng nng chuyn ng ca ton h (l dng nng lng c trng cho mt vt chuyn ng,
1 Ed = .mv 2 ) v th nng ca h c c do v tr ca n vi trng lc bn 2
ngoi, Et = mgh. Ni nng (U) ca h l tt c cc dng nng lng c d tr bn trong h nh: ng nng chuyn ng ca phn t, nguyn t,..., th nng tng tc (ht, y) ca cc phn t, nguyn t,...
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Trong nhit ng hc chng ta ch quan tm n ni nng ca h m khng cn quan tm n ngoi nng ca n. Chng ta kho st h khi h khng chuyn ng v tc dng ca trng ngoi n h l khng ng k. 1.7. Cng v nhit a) Cng (A) * Khi nim: Cng l mt i lng c trng cho mc trao i nng lng thng qua chuyn ng c hng ca h. Cng khng phi l hm trng thi v:
A = A
Quy c v du ca cng (A): + H nhn cng: A>0 + H nhng cng (sinh cng): A<0 Trong h n v SI, chng ta mn n v ca nng lng l Jun (k hiu l J) lm n v cho cng (A) chnh v vy m chng ta hay nhm cng l nng lng. Xin c nhc li cng v nhit ch l nhng dng truyn nng lc ca h vi mi trng ngoi ch khng phi l nng lng. * Tnh cng cho mt s qu trnh: Trong trng hp h sinh cng thc hin qu trnh gin n th tch + Qu trnh khng thun nghch Cng do h thc hin (h sinh cng):
A = Pe dV
(5.1a)
Trong : - Pe l p sut ngoi - dV l bin thin th tch cho mt qu trnh v cng nh Vi nhng bin i v cng chm th chp nhn Pe = P (P l p sut ca h), nn: A = P dV (5.1b) Khi a h t trng thi 1 n trng thi 2 (hnh v). Ly tch phn 2 v (5.1b), ta c cng gin n th tch ca h l:
1 2
2
A = PdV
1
(5.2) (5.3) (5.4)
- Vi qu trnh ng tch: V = const dV = 0, nn AV = 0 - Vi qu trnh ng p: P = const Ap = - P(V2 - V1) = -PV
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Ch : Nu Pngoi= Pe = 0, th A = 0 tc l s gin n ca kh trong chn khng khng sinh cng. Xt cho kh l tng th: PV = nRT (nu s mol kh khng thay i), khi : Ap = - nRT (5.5) - Vi qu trnh ng nhit: T = const Vi kh l tng , khi a h t trng thi 1 n trng thi 2 qu trnh bin thin th tch xy ra th phi c s thay i s mol. (5.6) Khi : AT = - nRT V: PV = nRT + Qu trnh thun nghch, ng nhit Xt cho 1 mol kh l tng, ta c:
AT = PdV
1 2
(*)
m PV = RT P =
AT = RT
2
RT V
thay vo biu thc (*), c: (5.7)
V dV = RT ln 2 V1 V 1
V T =const, nn
V2 P1 ~ do : V1 P2 P V AT = RT ln 2 = RT ln 1 P2 V1
(5.8)
V d 1: Gin n ng nhit 0,85 mol kh l tng t P1 = 15 atm ti P2 = 1 atm T = 300 K. Tnh cng gin n trong cc trng hp sau: a) chn khng b) Khi p sut ngoi khng i l 1atm. c) Khi qu trnh thun nghch Li gii a) Pe = 0 A = -PeV = 0 b) A = -Pe.( V2 - V1), m: V2 =
nRT nRT ; V1 = nn: P2 P1
1 1 V2 V1 = nRT P P 1 2
Do :
1 1 J 1 1 A = nRTPe = 0,85mol.8,314. .300 K .1atm. = 1980 J P P mol.K 1atm 15atm 1 2
c) V qu trnh thun nghch, nn p dng biu thc:

A = nRT ln P V2 J 15 = nRT ln 1 = 0,85mol.8,314. .300 K . ln = 5740 J mol.K P2 V1 1
Nhn xt: So snh cng do h thc hin phn b nh hn phn c. Vy: Cng ca qu trnh thun nghch l cng cc i
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b)Nhit (Q) Nhit cng nh cng l mt i lng c trng cho mc trao i nng lng ca h vi mi trng ngoi nhng khc cng ch s trao i nng lng c thc hin thng qua chuyn ng hn lon ca cc phn t. V d: nu ta cung cp cho h mt nhit lng Q (bng cch lm nng h) nhng gi cho th tch ca h khng i, khi nhit ca h s tng ln v chuyn ng hn loi ca cc phn t s mnh ln tc l ni nng ca h tng. H cng nhn nhiu nhit th nng lng ca h cng tng. Nhit khng phi l hm trng thi, ging nh cng. Tc l:
Q = Q
1
Nhit (Q) ph thuc vo cch tin hnh qu trnh. Trong h n v SI, nhit c o bng Jun (J). Tuy nhin cng c th dng n v Calo (Cal) o. Khi , cn nh: 1cal = 4,184Jun. Quy c v du ca nhit: - H nhn nhit (thu nhit): Q > 0 - H nhng nhit (to nhit): Q < 0 2. NGUYN L I CA NHIT NG HC Nguyn l th nht ca Nhit ng hc (c gi tt l nguyn l I) hay cn gi l nguyn l bo ton nng lng khng nh tnh cht bt din ca nng lng. Nguyn l ny c rt ra t vic tng kt kinh nghim hot ng thc tin ca con ngi v khng chng minh bng con ng l thuyt v bn thn n khng mu thun vi thc nghim, m mi h qu c rt ra t nguyn l I u ph hp vi thc nghim. 2.1. Biu thc ca nguyn l I. Hm ni nng (U) a) Biu thc ca nguyn l I Xt cho qu trnh v cng nh, ta c dng vi phn:
dU = Q + A
(5.9) (5.10)
Nu a h t trng thi 1 n trng thi 2, ta c dng tch phn:

U = Q + A = const
b) Hm ni nng: U Chng ta bit khi nim ni nng, nn phn ny ch ni n c im ca hm ni nng. Trc tin, ni nng (U) l hm trng thi, v:
dU = U
1
U1 = U
(5.11)
Khng th xc nh c gi tr tuyt i ni nng ca mt h khi h vo mt trng thi no , m ch xc nh c bin thin ca n (U ) khi h chuyn t trng thi ny sang trng thi khc. c) Pht biu nguyn l I T biu thc: U = Q + A = const cho ta thy, khi h nhn nhit (Q>0) th h phi sinh cng (A<0). T nguyn l 1 c pht biu nh sau:
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Khng th ch to c ng c vnh cu loi mt, l loi ng c khng tiu tn nng lng nh sinh cng mi mi. 2.2. Mt s trng hp cn ch khi dng nguyn l I a) Vi qu trnh on nhit: Q = 0, khi U = A tc l h khng nhn nhit m mun sinh cng th ni nng ca h phi gim v mt phn bin thnh cng A. c bit, vi chu trnh: U = A = 0 tc l, h chy theo chu trnh m khng trao i nhit vi mi trng ngoi th khng th sinh cng. b) Vi qu trnh ng tch: V = 0 Nu cng ch l cng gin n th tch th: A = -Pngoi.dV = 0 Tc l: dU V = QV 2 (5.12)
U V = QV = QV
1
bit: Q khng phi l hm trng thi, nhng trong iu kin ng tch th QV l hm trng thi, v QV = U . c) Qu trnh gin n trong chn khng Qu trnh ny din ra rt nhanh nn c coi l on nhit (Q = 0), v p sut ca chn khng bng 0, nn h khng sinh cng (A = 0), do : U = 0 Tc l, khi gin n trong chn khng ni nng ca h khng thay i (c bo ton). d) Vi chu trnh U = U2 - U1 = U1 = U1 = 0 Tc l A + Q = 0, nh vy h nhn nhit (Q>0), th ton b lng nhit phi bin thnh cng (H phi sinh cng: A < 0). ) H c lp lun c A = 0, Q = 0 nn U = 0 D thy ni nng ca h c lp c bo ton (khng i) e) Vi kh l tng Ni nng U l hm ca T, P, V nn U = U (P,V,T) nhng vi kh l tng th ni nng U ch l hm ca nhit (T), khng chng minh. U = U(T) Nu thc hin trong qu trnh ng nhit th: UT = 0 2.3. Hm trng thi entanpi (H) Nu h ch thc hin cng gin n th tch th:
dU = Q Png .dV
Trong qu trnh ng p, khi Png = Ph = P, ta c:

dU = Q P.dV
QP = dU + PdV = d (U + PV ) hay: v P = const t: H = U + PV (5.13) H c gi l hm entanpi ca h. H cng l hm trng thi v U, P, V u l hm trng thi.
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Nh vy:
QP = dH QP = H
(5.14)
Vi kh l tng th: PV = nRT Do : H = U + nRT = H(T). HT = 0. Nu T = const th Cng ging nh QV, QP cng l hm trng thi trong iu kin ng p. 2.4. Quan h gia QP v QV (hay l gia H v U) ca kh l tng Ta c: QV = UV QP = HP = UP + PV Do : QP - QV = UP - UV + PV. Vi cht lng, cht rn, khi T = const v p sut P khng ln qu th UP UV v V 0 nn QP = QV hay HP = UV Vi phn ng c cht kh tham gia, cc kh c coi l l tng v p sut thp (nh 1 atm chng hn) th: UP = UV v P.V = nRT. Khi : QP = QV + nRT (5.15) Hay HP = UV + nRT D thy: n = 0 th HP = UV 2.5. Nhit dung (C) a) Khi nim: Nhit dung l nhit lng cn thit lm nng h ln 1 . Nu quy h v: + 1 mol cht gi l nhit dung mol + 1 gam cht gi l nhit dung ring (t nhit) Khi n v tng ng o nhit dung l J/mol. K hay J/g.K. b) Biu thc tnh nhit dung. Nhit dung trung bnh (Ctb) ca mt h trong khong nhit t T1 n T2 c tnh bng biu thc sau:
Cct = Q Q = T2 T1 T
(5.16)
Trong , Q l nhit lng cn cung cp nng nhit ca h t nhit T1 n nhit T2. Khi T1 T2, tc l T dT th Q Q, ta s c nhit dung thc (C) ti nhit T l:
C=
Q
dT
(5.17)
T 5.17, ta thy C l hm ca nhit , C c xc nh bng thc nghim v c dng:
C = a + bT + cT2 + dT-2
QV
dT = dU dT
Nu thc hin trong qu trnh ng tch v h khng sinh cng c ch th:

CV =
(5.18)
Nu thc hin trong iu kin ng p v h ch thc hin gin n th tch, th:
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CP =
QP
dT
dH dT
(5.19)
dU = CV.dT (5.20) dH = CP.dT Vi kh l tng: U = U(T), H = H(T) Nn: CP CV = R (Tnh cho 1mol kh l tng) y: R l hng s kh Trong nhit ng hc cng dng t s: C = P CV v cng dng phng trnh Poisson: T.V -1 = const T1 .V1 1 = T2 .V2 1 (khi thc hin qu trnh on nhit). hay 0 V d 2: Cho 100g Nit 0 C v 1 atm. Hy tnh nhit Q, Cng A, bin thin ni nng U v bin thin entanpi H trong cc qu trnh sau y c tin hnh thun nghch nhit ng. a) un nng ng tch ti p sut bng 1,5 atm. b) Gin n ng p ti th tch gp hai ln th tch ban u. c) Gin n ng nhit ti th tch 200 lit. d) Gin n on nhit ti th tch 200 lit. Li gii a) V V = const nn A = 0 Nh vy:
U = QV = nCV (T2 T1 ) = n(C P R)(T2 T1 ) = n(C P R)( = P2 T1 T1 ) P1
1,5 100 (29,1 8,314)( .273,15 273,15) = 10138,74 J 1 28 P 1,5 100 H = nC P (T2 T1 ) = nC P ( 2 T1 T1 ) = .29,1.( .273,15 273,15) = 14194,05 J P1 1 28 H = nC P (T2 T1 ) = nC P (
b)
P2 1,5 100 T1 T1 ) = .29,1.( .273,15 273,15) = 14194,05 J P1 1 28 V 100 .29,1.(2.273,15 273,15) = 28388 J QP = H = nC P (T2 T1 ) = nC P ( 2 T1 T1 ) = V1 28 V2 100 T1 T1 ) = .8,314.273,15 = 8110,6 J V1 28 U = Q + A = 28388 + (8110,6) = 20277,4 J c) H = U = 0 Q+ A=0 A = PV = nR(T2 T1 ) = nR(
Q = A = PdV = + nRT
V1 V1 V2 V2
V dV = nRT ln 2 = V V1
100 .8,314.273,15.2,303 lg 28
200 = 7433J 100 22,4. 28

gio trnh ho i cng
201
A = -7433J d) i vi qu rnh on nhit Q = 0. Nn A = U = nCV(T2T1) Mun tnh T2, ta dng phng trnh Poisson:
TV 1 = h / s ; =
1 1
CP CV
V T1V1 = T2V2 T2 = T1 1 V 2 V lg T2 = lg T1 + ( 1) lg 1 V2 C 29,1 = P = = 1,4 CV 29,1 8,314 80 lg T2 = lg 273,15 + 0,4 lg T2 = 189,4 K 200 100 A = U = nCV (T2 T1 ) = .(29,1 8,314)(189,4 273) = 6207,3J 28 100 H = nC P (T2 T1 ) = .29,1(189,4 273) = 8688,4 J 28
2.6. p dng nguyn l I ca nhit ng hc vo ha hc 2.6.1. Nhit ca phn ng ha hc a) Khi nim: Nhit ca phn ng ha hc l lng nhit Q m phn ng trao i vi mi trng ngoi ti mt iu kin xc nh. b) Ch : Khi cc cht phn ng c ly theo t l hp thc, tc dng hon ton vi nhau to thnh sn phm cng theo t l hp thc. Lng nhit ny ph thuc vo cch tin hnh phn ng,v lng nhit ny l hm ca qu trnh. cho phn ng c gi tr xc nh, chng ta phi quy nh thng nht cc iu kin tin hnh phn ng, nh sau: + Phn ng c thc hin trong iu kin th tch hay p sut khng i. + Trong sut qu trnh phn ng khng c bt k mt cng no ngoi cng gin n th tch. + Nhit ca cc sn phm bng nhit cc cht ban u. Khi cc iu kin ny c tha mn, nhit phn ng s c gi tr hon ton xc nh. Khi thc hin phn ng trong iu kin ng tch, ta c nhit ng tch QV Khi thc hin phn ng trong iu kin ng p, ta c nhit ng p Qp phn trn, bit: QV = UV; QP = HP, do tnh nhit ng p, ng tch tc l tnh U, H. 2.6.2. Phng trnh ha hc v phng trnh nhit ha hc Phng trnh ha hc chng ta u quen bit, nh: C + O2 CO2 Mun vit mt phng trnh nhit ha hc, cn phi ghi r trng thi tp hp ca cc cht, cng nh lng nhit ca phn ng trao i vi mi trng ngoi.
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0 Ctc + O2 CO2; H 298 = 393,51kJ (1) 0 Ckc + O2 CO2; H 298 = 395,409kJ (2) 0 H 298 = 310,28kJ (3) C2H2 + H2 CO2; i vi phng trnh nhit ha hc, chng ta c php thc hin cc php bin i ton hc thng thng nh cng, tr, nhn, chia, i v trn phng trnh nhit ha hc. 2.6.3. nh lut Hess a) Ni dungca nh lut Hess:"Nhit ng tch QV, nhit ng p QP ca phn ng ha hc ch ph thuc vo bn cht v trng thi ca cc cht u v cht cui, hon ton khng ph thuc vo cch tin hnh phn ng" nh lut Hess c pht hin trc khi nguyn l 1 ra i, nhng n li l h qu ca nguyn l 1(mt trng hp c bit), v: QV = UV; QP = HP. Chng ta vit n gin l:QV = U; QP = H. Nhit lng Q ca phn ng ha hc ph thuc vo lng, trng thi ca cc cht, v cc iu kin tin hnh phn ng. thun tin v trnh cc sai st khi s dng nhit ca cc phn ng ha hc khc nhau, ngi ta thng tnh nhit lng Q i vi 1 mol sn phm ca phn ng v chp nhn quy chng v cc iu kin tiu chun di y: + Phn ng c thc hin gia cc cht ring bit (nguyn cht) vo trng thi tiu chun xc nh. Cc trng thi tiu chun ca cc cht rn, lng l cc trng thi bn ca chng iu kin thng khi p sut bng 1atm. Trng thi tiu chun ca kh l trng thi ca kh nguyn cht 1atm. i vi cht tan trong dung dch th nng ca n bng 1mol/lit (1M). + Trng thi tiu chun c th ng vi mt nhit bt k, nhng thng ng vi 298K (chnh xc l 298,15K) hay 250C Nhit lng Q ng vi trng thi tiu chun trn c gi l nhit tiu 0 0 chun v k hiu l: U 298 , H 298 . Trong thc t, cc phn ng ha hc thng din ra trong iu kin ng p, do chng ta hay dng nhit ng p v gi l bin thin entanpi ca phn ng (n gin hn gi l: entanpi ca phn ng). Khi bit entanpi ca phn ng th cng tnh c nhit ng tch ca phn ng cng mt nhit : V: QV = UV QP = HP = UP + PV QP - QV = UP - UV + PV Do : HP - UV = UP - UV + PV Khi phn ng din ra gia cc cht rn hoc cht lng, th UP UV ; V 0, nn: HP = UV Vi nhng phn ng c cht kh tham gia, p sut thp cc kh c coi l kh l tng. Khi : UP = UV (v ni nng ca kh l tng ch ph thuc
V d 3:
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gio trnh ho i cng
vo nhit ), PV = nRT trong ( n l bin thin s mol kh trong phn ng). Vi phn ng: 3H2 + N2 2NH3 th n = 2 + (3 +1) = -2<0 Do : HP = UV + nRT (n gin vit l: H = U + nRT) + Khi n = 0 th HP = UV + Khi n 0 th HP khc UV mt gi tr l nRT
b) Hai h qu ca nh lut Hess
H qu 1: Nhit ca phn ng thun bng nhit ca phn ng nghch nhng ngc du. Biu din bng s : Cht sn phm ; Hthun Cht phn ng Cht phn ng ; Hnghch = - Hthun Cht sn phm 0 V d 4: Ctc + O2 CO2; (1) H 298 = 393,51kJ 0 (1) CO2 Ctc + O2 ; H 298 = 393,51kJ H qu 2: c biu din bng s sau: Cht phn ng (1)
H12
Cht sn phm (2) Cht phn ng (2)

H23
H13
Cht sn phm (3) p dng nh lut Hess, ta c: H13 = H12 + H23 D dng tnh c :
H12 = H13 - H23
Tc l: Nu c cc cht phn ng (1) v cc cht phn ng (2) cng a n cht sn phm (3), th nhit ca phn ng chuyn cht phn ng (1) n cht phn ng (2) - cht sn phm (2) bng hiu ca nhit ca phn ng chuyn cht phn ng (1) n cht sn phm (3) tr i nhit ca ca phn ng chuyn cht phn ng (2) n cht sn phm (3). V d 5: Xc nh nhit ca phn ng chuyn than ch thnh kim cng:
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gio trnh ho i cng
Ctc Ckc Bit: Ctc + O2 CO2 Ckc + O2 CO2
(1) (2) (3)
H1 = ? H2 = - 393,513 kJ H3 = -395,409 kJ
Li gii Lp s qu trnh hnh thnh CO2 t Ctc v Ckc: Ctc + O2

H1
Ckc + O2
H2
H3
CO2 p dng h qu 2 ca nh lut Hes cho s , to thnh CO2 t Ctc v Ckc, ta c: H2 = H1 + H3

H1 = H2 - H3 = (-393,513) - (-395,409) = 1,9kJ Vy: T v d ny ta thy, iu kin thng khng th chuyn trc tip Ctc thnh Ckc c nn khng th o trc tip nhit ca phn ng ny. Nhng chng ta c th tnh c nhit ca phn ng ny bng con ng gin tip, thng qua nhit ca phn ng t chy Ctc v Ckc nh h qu 2 ca nh lut Hess. Cc bn sinh vin t lm cc v d sau. V d 6: Tnh nhit ca phn ng (1) H1 = ? Ctc + 0,5O2 CO; Bit: CO + 0,5O2 CO2; (2) H2 = -282,989 kJ (3) H3 = -393,513kJ Ctc + O2 CO2; p s: H1 = -110,524kJ V d 7: Tnh nhit ha hi ca nc H2O(l) H2O(h) (1) H1 = ? Bit nhit ca cc phn ng sau: H2 + 0,5O2 H2O(l) (2) H2 = -285,84kJ H2 + 0,5O2 H2O(h) (3) H3 = -241,83kJ p s: H1 = 44,01kJ Qua cc v d ny, ta thy da vo nh lut Hess v cc h qu ca n tnh c nhit ca cc phn ng khng xy ra trong thc t bng cch o nhit ca cc phn ng khc c lin quan n phn ng . 2.6.4.Tnh nhit ca phn ng ha hc da vo nhit hnh thnh v nhit t chy a) Nhit hnh thnh
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* Khi nim: Nhit hnh thnh ca mt hp cht l nhit ca phn ng to thnh 1 mol hp cht t cc n cht dng bn vng nht ca cc nguyn t, trong iu kin cho v nhit , p sut. Nu nhng iu kin ny l iu kin chun th nhit hnh thnh c gi 0 l nhit hnh thnh tiu chun, k hiu l: H 298,ht n v o l J/mol Ch o c trc tip c nhit hnh thnh ca mt s t trng hp nh ca CO2, HCl, H2O,... cn li phi tnh gin tip. Hin nay xc nh c nhit hnh thnh tiu chun ca 8000 cht v c lp thnh mt bng.... T nh ngha trn, nhit hnh thnh chun ca cc n cht bn iu kin tiu chun u bng 0 V d 8: Cho phn ng 0 H2 + 0,5O2 H2O(l) (2) H 298 = -285,84kJ T khi nim, d thy nhit hnh thnh chun ca nc lng l: (H0298,ht)H2O,long = -285,84kJ/mol V d 9: Nhit hnh thnh chun ca CaCO3 l nhit ca phn ng hnh thnh 1mol CaCO3 t Canxi kim loi, than ch v kh oxi iu kin tiu chun:
Vy:
Car + Ctc + 1,5O2 CaCO3 ;
H0298, p = -1207,68kJ
(H
0 298, ht CaCO3
= 1207,68kJ / mol
* Dng phn ng aA + bB + cC + AxByCz H0298, p = t (kJ) Trong A, B, C l n cht, sn phm ch c 1mol cht AxByCz to thnh., khi nhit hnh thnh ca AxByCz l:
(H
0 298, ht Ax B y C z
= t (kJ / mol )
* Tnh nhit ca phn ng ha hc da vo nhit hnh thnh Da vo nh lut Hess, rt ra quy tc sau: Nhit ca mt phn ng ha hc bng tng nhit hnh thnh ca cc cht cui tr i tng nhit hnh thnh ca cc cht u. V d 10: Tnh nhit ca phn ng CaO + CO2 CaCO3 (4) H0298, p(4) = ? (1) H0298, p(1) = -635,6kJ Cho: Ca + 0,5O2 CaO (2) H0298, p(2) = -393,1kJ Ctc + O2 CO2 (3) H0298, p(3) = -1207,68kJ Car + Ctc + 1,5O2 CaCO3
li gii Cch 1:Ly (3) - [(1) + (2)] s thu c phng trnh ca phn ng kho st, nh vy theo nh lut Hess ta c: H0298, p(4) = H0298, p(3) -( H0298, p(1) + H0298, p(2) ) = = -1207,68kJ - [(-635,6kJ) + (-393,1kJ) = -178kJ
Cch 2: Nhn thy nhit ca cc phn ng (1), (2), (3) l nhit hnh thnh ca CaO, CO2 v CaCO3:
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gio trnh ho i cng
(H (H (H
(
0 298, ht CaO 0 298, ht CO2
0 298, ht CaCO 3
) ) )
= 635,6kJ / mol
= 393,1kJ / mol
= 1207,68kJ / mol
p dng quy tc tnh nhit ca phn ng ha hc da vo nhit hnh thnh, ta c:

0 0 H 298,( 4 ) = 1mol. H 298,ht
CaCO3
0 1mol. H 298,ht
[ (
CaO
0 + 1mol H 298,ht
CO2
Thay s, ta c: H0298, p(4) = 1mol.(-1207,68kJ/mol) - [1mol.(-635,6kJ/mol) + 1mol.(- 393,1kJ/mol)] = -178kJ Ch : Khi tnh nhit ca phn ng da vo nhit hnh thnh, cn nhn nhit hnh thnh vi h s t lng tng ng c trong phng trnh phn ng. Tng qut:
Hp = (Hht)Cht sn phm - (Hht)Cht phn ng
b) Nhit t chy * Khi nim: Nhit t chy ca mt cht(n cht hoc hp cht)l phn ng t chy 1 mol cht bng oxi phn t to thnh cc dng oxi ha tng ng ca cc nguyn t. Nhng dng ny c quyt nh bi iu kin t chy trong bung phn ng ca nhit lng k. Vi hiro v cc bon thng b oxi ha n H2O v CO2, lu hunh ti SO2, nit ti NO2 hoc HNO3, cc cht cha halogen ti halogen hay hiro halogenua,... Nhit t chy ca cc cht khi quy v iu kin tiu chun c gi l nhit t chy tiu chun, k hiu l H0298,c. V d 11: Nhit t chy tiu chun ca metan l nhit ca phn ng t chy metan iu kin tiu chun: H0298,p = -890,34kJ CH4 + 2O2 CO2 + 2H2O(l) Vy, nhit t chy tiu chun ca metan l:
(H
0 298,dc CH 4
= 890,34kJ / mol
V d 12: Cho nhit ca cc phn ng sau Ctc + 0,5O2 CO; (1) H0298, p = -110,524kJ (2) H0298, p = -393,513kJ Ctc + O2 CO2; T khi nim, ta thy H0298, p (1) = =110,524kJ khng phi l nhit t chy ca Ctc. Nhit t chy ca Ctc chnh l nhit ca phn ng (2), vy:
) = 393,513kJ / mol ) = H = 393,513kJ / mol phn ng (2), ta thy : (H

0 298,dc Ctc
(H
0 298,ht CO2
0 298,( 2 )
Vy, vi n cht khi chy th nhit t chy ca n cht sng chnh l nhit hnh thnh ca sn phm c to thnh. Nhit t chy ca H2O bng khng, ca CO2 bng khng v H2O v CO2 l sn phm cui cng ca phn ng. Ni cch khc H2O v CO2 l cc sn phm khng chy c.
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gio trnh ho i cng
* Dng phn ng: X(n cht hoc hp cht) + O2 Sn phm 1 + sn phm 2 +... H0298, p = u(kJ) Khi ny nhit t chy ca X l: (H0298,c)X = u (kJ/mol) * Tnh nhit ca phn ng ha hc da vo nhit t chy Da vo nh lut hess, cng rt ra c quy tc sau: Nhit ca mt phn ng ha hc bng tng thiu nhit ca cc cht phn ng (cht u) tr i tng thiu nhit ca cc cht sn phm (cht cui). V d 13: Tnh nhit ca phn ng sau (xy ra iu kin tiu chun) C2H4 + H2 C2H6 (1) H0298, p(1) = ? Cho: C2H4 + 3O2 2CO2 + 2H2O(l) (2) H0298, p(2) = -1410,97 kJ (3) H0298, p(3) = -285,84 kJ H2 + 1/2O2 H2O(l) C2H6 + 7/2O2 2CO2 + 3H2O (4) H0298, p(4) = -1559,88 kJ Li gii Cch 1: Ly phn ng [(2) + (3)] - (4) th c phn ng (1), ta c: H0298, p(1) = [H0298, p(2) + H0298, p(3)] - H0298, p(4) = = [(-1410,97) + (-285,84)] - (-1559,88) = -136,93kJ Cch 2: Ta thy nhit ca cc phn ng (2), (3), (4) chnh l nhit t chy ca cccht: C2H4, H2, C2H6, tc l
(H (H (H
0 298,dc C2 H 4
0 298,dc H 2
0 298,dc C2 H 6
) ) )
= 1410,97kJ / mol = 1559,88kJ / mol
= 285,84kJ / mol
p dng quy tc tnh nhit ca phn ng ha hc da vo nhit t chy, ta c:

0 0 0 H0298, p(1) = [1mol. (H 298,dc )C H +1mol. (H 298,dc )H ] - 1mol. (H 298,dc )C H =
2 4 2 2 6
=[1mol.(-1410,97kJ/mol)+1mol.(-285,84kJ/mol)] -1mol.(-1559,88kJ/mol) = -136,93kJ Ch : Cng ging nh tnh nhit ca phn ng da vo nhit hnh thnh, cn nhn nhit t chy vi h s t lng tng ng c trong phng trnh phn ng. Hp = (Hc)Cht phn ng - (Hc)Cht sn phm Tng qut: Qua ni dung va trnh by, mt ln na khng nh rng quy tc tnh nhit ca phn ng ha hc da vo nhit hnh thnh, nhit t chy c rt ra t nh lut Hess. Mt s v d khng c li gii V d 14: Tnh nhit hnh thnh ca etan, bit: Ctc + O2 CO2 (1) H0 = -393,5 kJ
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gio trnh ho i cng
H2 +
2C2H6 + 7O2 4CO2 + 6H2O(l) (3) H0 = - 3119,6 kJ V d 15: Tnh nhit hnh thnh ca ru metanol nu bit nhit t chy ca CH3OH, Ctc v H2 ln lt bng -726,55 kJ/mol; -393,50kJ/mol; -285,85 kJ/mol. V d 16: Nhit ng p ca phn ng tng hp NH3: N2 + 3H2 2NH3 298K l - 92,382 kJ. Tnh nhit ca phn ng trong iu kin ng tch. V d 17: Tnh nhit ca phn ng: C2H4 + H2 C2H6 T cc d kin sau: a) Nhit hnh thnh chun ca C2H4, C2H6 ln lt bng: -12,5; -20,24 kcal/mol. b) Nhit t chy chun ca C2H4, C2H6, H2 ln lt bng -337,3; 372,86; -68,3 kcal/mol. 2.6.5. ngha ca nh lut Hess nh lut Hess gip cho chng ta tnh c nhit ca cc phn ng khng xy ra trong thc t; Tnh c: Nhit chuyn pha, nng lng lin kt, nng lng mng li tinh th, nhit ha tan,... 2.6.6. S ph thuc ca nhit ca phn ng ha hc vo nhit Nhit ca mt phn ng ha hc ph thuc vo nhit p sut. p sut cao s ph thuc ca nhit ca phn ng ha hc vo p sut mi ng k, do p sut thp, yu t p sut thng c b qua. Trong khi , s chnh lch v nhit thng gy nh hng ln n qu trnh. V vy khng th b qua c yu t ny. mc 2.5, chng ta bit nhit dung c tnh bng biu thc:
C=
1 O2 H2O(l) (2) 2
H0 = -2,885 kJ
Q
dT
i vi qu trnh bin i ng tch:

CV =
QV
dT
dU V dU = CV dT dT dH p dT dH = C P dT
i vi qu trnh bin i ng p:
Cp =
Q p
dT
i vi phn ng: aA + bB cC + dD Kirchoff thit lp c phng trnh biu din s ph thuc ca nhit ca phn ng ha hc vo nhit dng vi phn.
dH = C P dT T
(5.21)
Trong Cp l tng nhit dung ca cht cui tr i tng nhit dung ca cht u:
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gio trnh ho i cng
Cp = (cCp,C + dCp,D) - (aCp,A +bCp,B) (5.22) Ly tch phn phng trnh (5.21) t nhit T1 n nhit T2, ta c phng trnh Kirchoff dng tch phn.
H T2 = H T1 + C P dT
T1 T2 T2
(5.23)
Ch : i vi qu trnh bin i ng tch, phng trnh Kirchoff dng tch phn l:

U T2 = U T1 + CV dT
T1
(5.24)
V d 18:Tnh nhit ca phn ng 500K v 1atm 2H2 + CO CH3OH(k) H0500 =? 0 Bit: 1) H0298,ht (CO) = -110,5kJ.mol-1; H 298,ht (CH OH ) = 201,2kJ .mol 1
3 (k )
2) C P ( H ) = 27,28 + 3,26.10 T + 0,502.10 T J .mol 1.K 1

3
C P ( CO ) = 28,41 + 4,10.10 3 T 0,46.105 T 2 J .mol 1.K 1 C P ( CH 3OH ) = 15,28 + 105,2.10 3 T 3,104.10 5 T 2 J .mol 1.K 1
Li gii Trc tin, tnh nhit ca phn ng iu kin tiu chun da vo nhit hnh thnh: 0 0 H0298, p = [1mol. H 298,ht (CH OH ) ] - [2mol. H 298,ht ( H ) + H0298,ht (CO)] = = 1mol.(-201,2kJ.mol-1) -[2mol.(0 kJ.mol-1) + 1mol.(-110,5kJ.mol-1)] = = -90,7kJ = -90700J Tnh Cp ca phn ng: Cp, p = [1mol. C p (CH OH ) ] - [2mol. C P ( H ) + 1mol.Cp(CO)]= ?
3 (k ) 2 3 2
Cp, p = -67,69 +94,58.10-3T - 32,01.10-6T2 -0,544.105.T-2 Thay Cp, p vo biut thc (5.23), ri ly tch phn t T1 n T2, c:
0 0 H T2 = H T1 67,69.(T2 T1 ) +
V Cp l hm ca nhit , v c dng: Cp = a + bT + cT2 + dT-2 Nn Cp, p c dng: Cp, p = a + bT + cT2 + dT-2 Cn tnh a, b, c, d. a = 1.15,8 -(2.27,28 +1.28,41) = -67,69 b = [(1.105,2) - (2.3,26 +1.4,10)].10-3 =94,58.10-3 c = [(1.-3,104) - (2.0 +1.0)].10-5 = -31,04.10-6 d = [(1.0) - (2.0,502 +1.-0.46)]105 =-0,544.105 Thay cc gi tr va tm dc vo biu thc trn, c:
94,58.10 3 2 31,04.10 6 3 (T2 T12 ) (T2 T13 ) + 2 3
+ 0,544.105 (T21 T11 ) Thay H T01 = H0298, p = -90700J, T1 = 298, T2 = 500 vo, th tnh c:
H0500 =-97,75kJ
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gio trnh ho i cng
3. NGUYN L II CA NHIT NG HC 3.1. Pht biu nguynl II Cng nh nguyn l I, nguyn l II khng c chng minh bng con ng l thuyt m c rt ra t kinh nghim thc tin ca con ngi. Nguyn l II c nhiu cch pht biu khc nhau. Phn ny ch nu 2 ch pht biu sau. a) Cch 1: nh ca Clausius " Nhit khng th truyn t vt lnh sang vt nng". Mun c qu trnh ny xy ra bt buc phi c tc ng t bn ngoi vo, khi mi trng xung quanh s b bin i. b) Cch 2: nh ca Thomson "Khng th ch to c mt loi my lm vic theo chu trnh bng cch ly nhit t mt ngun rri bin hon ton thnh cng". Nu gi my ny l ng c vnh cu loi II, th pht biu nh sau:"Khng th c ng c vnh cu loi II" 3.2. Biu thc ca nguyn l II. Hm entropi
Dng vi phn: Dng tch phn:
dS
T Q S T
Xt cho qu trnh v cng nh

Tnh cho c qu trnh a h t trng thi 1
ti trng thi 2 Du = ng vi qu trnh thun nghch Du > ng vi qu trnh khng thun nghch 3.3. ngha vt l ca entropi Xt cho h c lp, ta lun c: Sh c lp 0 v Q = 0 Khi a h t trng thi 1 n trng thi 2: + Nu qu trnh t din bin th entropi tng, v Sh c lp= S2-S1 > 0 tc l S2 > S1 + Nu h t ti trng thi cn bng th: Sh c lp= S2-S1, tc S2 =S1 Nh vy: Trong h c lp cc qu trnh u t xy ra theo chiu tng mc hn lon ca h, tng entropi. Ngha l: ln ca bin thin entropi S l mc o tnh hn lon ca cc qu trnh xy ra trong h c lp. T ngha ca entropi nhn thy: Khi tng nhit th entropi tng, i vi cg mt cht th trng thi c cu trc hn lon c entropi cao hn trng thi c cu trc t hn lon (Slng > Srn). S tng s nguyn t trong phn t , s gim tnh i xng v tnh bn vng ca cc lin kt trong phn t u lm tng entropi. Cc qu trnh nng chy, un nng, cc phn ng c s tng s mol kh u lm tng entropi S > 0, cc q trnh kt tinh, h nhit th c S < 0. ngha ca entrpi xt cho h c lp cng ng khi p dng trong thc t. 3.4. Tnh bin thin entropi cho mt s qu trnh thun nghch Xt cho qu trnh thun nghch, th dng biu thc:
dS =
T Q S = T
(5.25)
3.4.1. Qu trnh bin i trng thi ca cht nguyn cht

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gio trnh ho i cng
Cc qu trnh bin i trng thi ca cht nguyn cht lun xy ra T = const, P = const, v th: QP = dH v QP = H, nn:
S =
H c gi l nhit chuyn pha. Vi qu trnh nng chy th gi l nhit nng chy, qu trnh thng hoa gi l nhit thng hoa,... V d 1: Tnh bin thin entropi khi: 1) Lm ng c 1mol Hg, bit nhit nng chy ca Hg l 234K v nhit nng chy ca n l 2,295kJ.mol-1. 2) lm nng chy 1 mol nc , bit nhit nng chy ca nc l 273K v nhit nng chy ca n bng 6,019kJ.mol-1. 3) Ha hi ete p sut kh quyn, bit nhit si ca ete l 350C v nhit ha hi ca n bng 27,17kJ.mol-1. Li gii
H T
(5.26)
1) S =
H dd H nc 2295 J .mol 1 = = = 9,81J .mol 1 .K 1 = 9,8 ve Tdd Tnc 234 K
(1ve = 1 n v entropi = 1J.mol-1.K-1)
H nc 6019 J .mol 1 = = 22,05 J .mol 1.K 1 = 22,05 ve Tnc 273K 27170 3) S = hh = = 82,21J .mol 1.K 1 = 82,21 ve Ts 308
2) S =
3.4.2. Qu trnh gin n ng nhit ca kh l tng
V U =U(T), nn T = const th UT = 0, nn Q + A = 0
Q = -A Q = A = nRT ln
V2 V1
(xt cho n mol kh) (5.27)
Do :
Q V P = nR ln 2 = nR ln 1 T V1 P2 1 P V v: P hay 1 = 2 khi T = const V P 2 V1 S =
V d 2:Tnh bin thin entropi trong qu trnh trn ng nhit 1kmol N2 v 1kmol O2 c p sut nh nhau nu c 2 kh u c coi nh kh l tng. Li gii V 2 kh c cng nhit v p sut nn c cng th tch. Khi pha trn th tch ca mi kh tng ln 2 ln, v vy coi mi kh gin n ng nhit t th tch V1 n th tch V2 = 2V1. Chp nhn cc qu trnh l bin i thun nghch, ta c:
S = Qtn V = nR ln 2 T V1 J ln 2 = 5763J .K 1 mol.K
Nh vy: S N = S O = 1000mol.8,314
2 2
Cho nn, s bin thin S ca c qu trnh s l:

S = S N 2 + S O2 = 2.5763 J .K 1 = 11526 J .K 1
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gio trnh ho i cng
3.4.3. Qu trnh un nng Khi un nng h t nhit T1 n nhit T2 vi iu kin trong khong nhit ny khng xy ra qu trnh chuyn pha: + Nu thc hin trong iu kin ng p P =const, th:
S =
T2 T1
QP
T
= CP
T1 T2
T2
dT T dT T
(5.28)
+ Nu thc hin trong iu kin ng tch V =const, th:

S =
T2 T1
QV
T
= CV
T1
(5.29)
V d 3: Tnh bin thin entropi khi 1mol CO c un nng ng p t 100K n 200K. Trong khong nhit ny Cp(CO) = 29,26J.mol-1.K-1 Li gii C th un nng n mol cht mt cch thun nghch, t (5.28) ta c:
S =
T2 T1
QP
T
= CP
T1
T2
dT T
V CP = const, nn: S = C P ln
V d 4: Tnh S ca qu trnh un nng 1 mol nhm t 250C n 6000C trong iu kin ng p. Bit nhit dung ca nhm c biu din bng phng trnh:
C P = 21,15 + 10,73.10 3 T ( J .mol 1 .K 1
T2 J 200 J ln = 29,26 = 20,28 T1 mol.K 100 mol.K
Li gii p dng 5.28 ta c:

873
S =
298
CP
dT dT dT = (21,15 + 10,73.10 3 T ) = 21,15 + 10,73.10 3 dT = T T T 298 298 298
873
873
873
= 21,15 ln
T2 873 J + 10,73.10 3 (T2 T1 ) = 21,15 ln + 10,73.10 3 (873 298) = 29,91 T1 298 mol.K
S = S T S 0 = C P
0
T
Ch : T 5.28, 5,29 nu thay T1 = 0 v T2 = T, ta c:

dT T dT T
(5.30) (5.31)
S = ST S 0 = CV
0
Theo nh ca Planck: Entropi ca nhng tinh th c cu trc hon chnh l tng 0K bng khng. Thay S0 = 0, ta c th tnh c entropi tuyt i ca cht nhit T:
ST = C P
0
T
dT T dT T
(5.32) (5.33)
ST = C P
0
213
gio trnh ho i cng
Nu trong khong nhit t 0 n T m c cc qu trnh chuyn pha th khi tnh ST phi cng thm bin thin entropi ca cc qu trnh chuyn pha. Chng hn: Cng thc tnh ST ca 1 mol kh trong khong nhit t 0K n TK, Khi tnh ST phi tri qua 3 trng thi rn, lng, kh s c dng:
S T = C P ,r
0
Tnc
dT H nc hh dT H hh dT + + C P ,l + + C P ,k T Tnc T Thh T Tnc Thh
(5.34)
Trong : Tnc, Thh l nhit nng chy, nhit ha hi; Hnc, Hhh l nhit nng chy v nhit ha hi ca cht. Thng chn iu kin tnh l nhit T bng 298,15K ( lm trn l 298K hay 150C) v p sut l 1,01325.105Pa (1atm). Khi ny entropi c k hiu l S0298 v c gi l entropi tiu chun. 3.4.4. Tnh bin thin entropi cho cc phn ng ha hc Nu phn ng c dng: aA + bB cC + dD Th bin thin entropi ca phn ng c tnh bng biu thc sau: S = (c.SC + d.SD) (a.SA + b.SB) (5.35) Hay: S = (n.Scui) - (m.Su) 0 Dng biu thc 5.35 v cc gi tr S 298 ca cc cht c trong phn ng s tnh c bin thin entropi tiu chun ca phn ng. V d 5: Cho phn ng: Cho: S0298 (J.mol-1.K-1) Li gii p dng 5.35, tnh c: S0298,p = 179,59 1 1 Ctc + CO2 CO 2 2
5,742 213,73 197,59
1 .(5,742 + 213,73) = 87,854J.mol-1.K-1 2
3.5. Tnh bin thin entropi cho qu trnh khng thun nghch Trong qu trnh thun nghch, ta c:
S > Qktn T
tnh S, chng ta cn hnh dung qu trnh i theo nhng giai on c thc hin mt cch thun nghch. Nu trng thi u v trng thi cui ca hai qu trnh trng nhau, th bin thin entropi S s c cng gi tr v entropi l hm trng thi khng ph thuc vo cch tin hnh qu trnh. V d 6: Tnh bin thin entropi ca qu trnh chuyn 9 g H2O(l) thnh hi khi thay i nhit t 00C n 1500C p sut 1,013.105.N.m-2 nu nhit ha hi ca nc l 2,255kJ.g-1, nhit dung mol ng p ca nc lng l 35,30J.mol-1.K-1v ca hi nc l: CP = 30,13 + 11,3.10-3T J.mol-1.K-1 Li gii: V qu trnh l khng thun nghch. Nn chia qu trnh ny thnh 3 qu trnh nh thun nghch nh sau: + Qu trnh 1: un nng nc lng t 00C n 1000C. + Qu trnh 2: Chuyn nc lng 1000C thnh hi nc 1000C. + Qu trnh 3: un nng hi nc t 1000C n 1500C. Chng ta biu din bng s sau:
214
gio trnh ho i cng
9 gH2O(l), 00C P = const
Sktn
9 gH2O(h), 1500C
S1 S2
S3
P = const
9 gH2O(l), 1000C
9 gH2O(h), 1000C
Tnh :
S1 = n. C P
T1 T2
T dT 9g 373 = n.C p ln 2 = .75,30 J .mol 1 .K 1 ln = 11,75 J .K 1 1 T T1 18 g.mol 273
S 2 =
H hh 1000.2,255 J .g 1 .9 g = = 54,41J .K 1 TS 373K

T2 T T T
2 2 2 dT dT S 3 = n. C P = n. (30,13 + 11,3.10 3 T ) = n 30,13d ln T + n. 11,3.10 3 dT = T T T1 T1 T1 T1
= n.30,13 ln
Vy: Sktn = S1 + S2 + S3 = 11,75 + 54,51 + 2,18 = 68,34J.K-1
T2 423 9 9 + n.11,13.10 3 (T2 T1 ) = .30,13 ln + .11,3.10 3 (423 373) = 2,18 J .K 1 T1 373 18 18
4. CHIU CA NHNG BIN I TRONG H KHNG C LP 4.1. Biu thc thng nht 2 nguyn l Biu thc ca nguyn l I: dU = Q + A = Q PdV Q = dU + PdV
Biu thc ca nguyn l II: dS Do : Hay:
Q
T
Q TdS
dU + PdV TdS dU TdS PdV dU TdS + A

(5.36)
4.2. Hm G. Chiu t din bin ca qu trnh v cn bng ca h Trong thc t, chng ta gp ch yu cc h khng c lp, trong xy ra cc qu trnh ng nhit ng p, hoc ng nhit ng tch. Chng ta quan tm ch yu n trng hp ng nhit ng p v hay gp hn. Chng ta dng entropi tiu chun kho st qu trnh bng cch: Gp h kho st vi mi trng c th tch ln ton b h thu c c th coi l h c lp, khi ny: (5.37) Sc lp = Sh kho st + Smi trng
215
gio trnh ho i cng
Gi s nhit T v p sut P khng i, h trao i vi mi trng mt nhit lng Q = H. Khi ny mi trng s nhn ca h mt nhit lng l H, v: Smi trng = Thay vo 3.57, ta c: Sc lp = Sh kho st
H T
H H = S T T
(5.38)
H > 0 hay H TS < 0, qu trnh t xy ra. T H = 0 hay H TS = 0, h trng thi cn + Sc lp = 0, tc l: S T
( n gin, Sh kho st c vit gn l: S) Kho st 5.37 nhn thy, khi:
+ Sc lp > 0, tc l: S
bng. Khi T = const, th: t:
H TS = (H TS)
G = H TS (5.39)
Cc i lng H, T, S l nhng hm trng thi, nn G cng l hm trng thi. Hm G c gi l th ng nhit ng p (gi tt l th ng p) hoc nng lng Gip-x. D thy: G = H TS (5.40)
+ Khi Sc lp > 0, tc l: G = H TS < 0 qu trnh t xy ra. n y, cc bn cn nh: T, P = const, khi G < 0 qu trnh t xy ra, khi G = 0, h trng thi cn bng. Ni cch khc:Nhng h nhit v p sut khng i, ch nhng qu trnh no km theo s gim nng lng Gip-x mi c th t xy ra, khi nng lng Gip-x t gi tr cc tiu h s t ti trng thi cn bng. Nh vy, t tiu chun entropi v chiu hng v gii hn trong h c lp, chng ta tm c tiu chun xt chiu hng v gii hn ca qu trnh trong h nhit v p sut khng i, l th ng p hm G. hiu r hn v hm G, cn tm hiu ngha v cch tnh hm G. 4.3. Th nhit ng ca hm G. ngha ca G. Th ha hc 4.3.1. Th nhit ng ca hm G T biu thc G = H TS = U + PV TS Ly vi phn 2 v ta c: dG = dU + d(PV) d(TS) = dU + PdV + VdP TdS SdT T biu thc 5.36 xt cho qu trnh thun nghch th: dU = TdS PdV TdS = dU + PdV thay vo trn, c: dG = dU + PdV + VdP (dU + PdV) SdT
216
gio trnh ho i cng
Vy:
dG = SdT + VdP
(5.41)
Biu thc 5.41 l th nhit ng ca hm G. 4.3.2. ngha ca G T biu thc 5.40: G = H TS Cho php xc nh c chiu hng ca qu trnh. Chiu hng ca qu trnh c quyt nh bi hai yu t l entanpi v entropi. Cc trng hp sau y c th xy ra: + Khi S = 0, qu trnh ny c mc hn lon khng thay i hoc thay i khng ng k, nn qu trnh ch chu nh hng ca yu t entanpi. Khi ny qu trnh t xy ra khi G = H < 0 tc l nng lng ca h gim. + Khi H = 0, qu trnh khng nhn hay pht nng lng. Khi ny ch c yu t entropi nh hng n chiu hng ca qu trnh. Qu trnh s t xy ra khi G = TS < 0 hay S > 0 tc l xy ra theo chiu lm tng mc hn lon ca qu trnh. + Khi H < 0, S > 0 c hai yu t entanpi v entropi u thc y chiu t din bin ca qu trnh. Khi G = H TS < 0 qu trnh t xy ra. + Khi H > 0, S < 0 th G > 0 qu trnh khng th t xy ra theo chiu thun. Khi ny chng ta ni qu trnh t xy ra theo chiu nghch. + Khi H < 0, S < 0 qu trnh c thc y bi yu t entanpi nhng b cn tr bi yu t entropi. Khi ny qu trnh s t xy ra nu entapi ln hn entropi, tc l khi H > TS . Khi ny G = H TS < 0. + Khi H > 0, S > 0 th yu t entanpi cn tr qu trnh cn yu t entropi thc y qu trnh. Khi ny qu trnh s t xy ra khi entropi ln hn entanpi, tc l TS > H . Khi ny G = H TS < 0. Ch : + Tnh G cho mt phn ng ha hc cng ging nh tnh nhit hnh thnh ca phn ng ha hc . + Khi nim th ng p hnh thnh ca mt cht cng ging nh khi nim nhit hnh thnh. Nh vy, trong mi mt qu trnh lun c s cnh tranh gia 2 yt t: entanpi lm gim nng lng ca h cn entropi lm tng mc hn lon ca h. Trong hai yu t ny yu t no mnh hn s thc y chiu hng ca qu trnh. Qu trnh s t ti trng thi cn bng khi c s b tr ln nhau gia 2 yu t ny, tc l khi G = H TS = 0. 4.3.3. Th ha hc T biu thc 5.41, ta thy th ng p G l hm ca nhit v p sut. iu ny ch ng vi h kn, l h ch trao i nng lng m khng trao i cht vi mi trng ngoi, tc l n = 0 ( khng c s bin thin s mol ca cc cht).
217
gio trnh ho i cng
Trong thc t, thng gp h m l h c s trao i nng lng v c trao i cht vi mi trng bn ngoi, tc l n 0. l cc h m xy ra cc phn ng ha hc hoc c s chuyn pha, ... Khi ny thnh phn ca h hay s mol ca cc cu t b thay i lm cho bin thin hm G cng thay i theo. Nu gi n1, n2, ..., ni l s mol ca cc cu t (cc cht) 1, 2, ..., i trong h th G l hm ca T, P v s mol ca cc cht trong h. G = G(T, P, n1, n2, ..., ni ) Ly vi phn ta c:
G G G G dG = dT + dP + dn1 + dn2 + ...(5.42) n n T P ,n1 ,n2 ,... P T ,n1 ,n2 ... 1 P ,T ,n j ( j i ) 2 T , P ,n j ( j 2 )
Kt hp vi 5.41, khi ny 5.42 c vit di dng: dG = SdT + VdP +idni Trong : i c gi l th ha hc ca cu t i

i = n i T , P ,n ( j i )
j
(5.43) (5.44)
Vy: Th ha hc ca cu t i l o hm ring ca hm G theo s mol ca cu t i khi nhit T, p sut P v s mol ca cc cu t khc (j i) khng i. Khi dni = 1 th i = (G ) P ,T ,n ( j i ) tc l th ha hc ca cu t i bng tng ca th ng p G khi thm vo h 1 mol i trong iu kin T, P v thnh phn (s mol) ca cc cu t khc c trong h khng thay i. T cn hiu: Th ha hc ca cu t i l th ng p ca 1 mol i i = Gi (5.45) T h thc 5.41: dG = SdT + VdP khi T = const th (5.46) dGT = VdP Xt cho 1 mol kh l tng, th: V = RT/P, khi :
j
dGT = RT
dP = RTd ln P P
(5.47)
(5.48) GT = G0T + RTlnP 0 Trong : G T l hng s tch phn c gi tr xc dnh ti mi nhit T xc nh. Tc l G0T ph thuc vo nhit T. S dng h thc 5.45, ta c: i = 0i(T) + RTlnPi (5.49) Trong : i l th ha hc ca cu t i trong hn hp. 0i(T) l th ha hc ca cu t i khi p sut rin phn ca i bng 1 (Pi = 1), 0i cng ph thuc vo T, tc l 0i c gi tr xc nh ti mi nhit T xc nh. Pi l p sut ring phn ca cu t i. T h thc 5.43, khi T, P = const, th:
Tch phn 5.47, ta c:
218
gio trnh ho i cng
dG = idni (5.50) bit: + Khi dG < 0 qu trnh (h) t xy ra (5.51) + Khi dG = 0 qu trnh (h) t n trng thi cn bng (5.52) T 5.50 ta thy: iu kin t din ra v iu kin cn bng ca qu trnh xy ra trong h m khi T, P =const l:
idni 0 (5.53)
Biu thc 5.53 l iu kin tng qut v chiu t din bin v cn bng ca cc qu trnh xy ra trong h m. Du < cho bit qu trnh t xy ra trong h. Du = cho bit qu trnh xy ra trong h t ti trng thi cn bng. By gi chng ta p dng 5.53 cho qu trnh chuyn pha v phn ng ha hc. * Cho qu trnh chuyn pha:
1, 2, 3, , i dni 1, 2, 3, , i
S chuyn cu t i t pha sang pha + Gi s c mt h gm hai pha v (hnh v), trong mi pha gm c mt s cu t . Trong iu kin T, P = const, nu c dni mol cu t i chuyn t pha sang pha , th th ng p ca pha s gim mt lng dG = i dni v pha s tng mt lng dG = i dni . Do bin thin th ng p ca ton b h s l: (5.54) dG = dG + dG = i dni + i dni Trong biu thc 5.54, i v i l th ha hc ca cu t i trong pha v pha ; dni v dni l bin thin s mol ca cu t i trong pha v pha (dni < 0 cn dni > 0). (5.55) ng nhin l: dni = dni do dG = (i i)dni Nu qu trnh chuyn cu t i t pha sang pha t xy ra th: dG < 0, nn i >i Nu qu trnh chuyn pha t n trng thi cn bng th: dG = 0, do i = i Nh vy cu t s chuyn t pha sang pha khi th ha hc ca cu t trong pha ln hn trong pha . S chuyn ny lm gim i v lamg tng i. Khi th ha hc ca cu t i trong hai pha bng nhau, th qu trnh chuyn pha t n trng thi cn bng.
219
gio trnh ho i cng
Chng ta m rng kt lun ny cho h nhiu cu t: Vi h nhiu cu t iu kin cn bng pha l th ha hc ca mi cu t trong cc pha phi bng nhau. Nu th ha hc ca mt cu t no trong pha A ln hn th ha hc ca chnh cu t trong pha B, th n cng d thot ra khi pha A chuyn sang pha B. Nh vy chng ta ni: Th ha hc i l i lng c trng cho kh nng ri i ca cu t i ra khi pha m n ang tn tai trong iu kin kho st. y l ngha vt l ca th ha hc. * Cho phn ng ha hc: aA + bB + cC + dD + Xy a iu kin T, P = const, khi ny bin thin th ng p ca phn ng s l: (5.56) G = idni Trong : i l th ha hc ca cht i; dni l bin thin s mol ca cht i (dni < 0 i vi cht phn ng, dni > 0 i vi cht sn phm). V dni phi t l vi h s t lng i (i l cc h s a, b, ..., c, d, ...), tc l: dni = ki (5.57) Do : G = iki Khi k = 1, th dni = i tc l bin thin s mol ca cc cht bng chnh h s t lng ca cht , th: (5.58) G = ii = (cC + dD + ) (aA +bB + ) T 5.58, ta thy: + Khi G < 0 hay (cC + dD + ) (aA +bB + ) < 0, tc l (aA +bB + ) > (cC + dD + ) phn ng t xy ra theo chiu thun (t tri sang phi). + Khi G = 0 hay (aA +bB + ) = (cC + dD + ) phn ng t n trng th cn bng. Nh vy: Phn ng ha hc t xy ra khi tng th ha hc ca cc cht phn ng ln hn tng th ha hc ca cc cht sn phm; khi tng th ha hc ca cc cht phn ng bng tng th ha hc ca cc cht sn phm th phn ng t ti trng thi cn bng. T cc iu trnh by trn ta thy: Th ha hc c vai tr cc k quan trng trong nghin cu cc qu trnh chuyn cht nh: s bin i ha hc, s chuyn pha, 5. CN BNG HA HC 5.1. Phn ng 1 chiu v phn ng 2 chiu aA + bB sn phm y, cc cht sn phm khng tc dng c vi nhau to thnh cc cht ph ng A, B c. Phn ng 1 chiu c c im nh sau: Nu cc cht Phn ng mt c dng:
220
gio trnh ho i cng
phn ng A, B c ly theo ng h s t lng, khi phn ng xy ra hon ton (hiu sut h =100%) th hn hp phn ng ch cn cc cht sn phm. Phn ng 2 chiu c dng: aA + bB cC + dD (5.59) y, cc cht sn phm C, D tc dng c vi nhau sinh ra cc cht phn ng A, B. V vy, hiu sut ca phn ng lun nh hn 100% (h < 100%). Trong hn hp phn ng lun thu c cc cht phn ng v cc cht sn phm. i vi phn ng 2 chiu, khi thnh phn ca cc cht khng trong hn hp phn ng khng thay i th h phn ng t ti trng thi cn bng (G = 0). Trng thi cn bng c cc c im sau: + L trng thi cn bng ng: Tc l khi phn ng t ti trng thi cn bng, th trng thi ny c gi bao lu cng c nu cc yu t quyt nh n cn bng nh nhit , p sut, nng khng thay i. + B chuyn dch khi c tc ng t bn ngoi: Khi mt trong cc yu t nh nhit , p sut, nng thay i th s c s chuyn dch cn bng. + Trng thi cn bng lun c nng lng cc tiu.
5.2. Quan h gia bin thin th ng p v hng s cn bng Gi s, c phn ng tng qut dng: aA + bB cC + dD (5.59) Xy ra T, P =const, Cc cht A, B, C, D u l kh l tng p dng biu thc 5.58: (5.58) G = ii = (cC + dD + ) (aA +bB + ) a) Khi phn ng cha t ti trng thi cn bng th:G 0 Tc l: G = ii = (cC + dD ) (aA +bB ) 0 (5.60) 0 i = i(T) + RTlnPi Theo 5.49: A = a0A + RTlnPA Do : B = b0B + RTlnPB C = c0C + RTlnPC D = d0D + RTlnPD Trong : PA, PB, PC, PD l p sut ring phn ca cc kh A, B, C, D khi cha cn bng. Thay cc biu thc vo 5.60 ri bin i, ta c:
G = c + d
0 C
[(
0 D
) (a
G0T
0 A
+ b
0 B
)]
d PCc .PD + RT ln a b PA .PB
Biu thc trong ngoc vung l GT0 (Bin thin th ng p iu kin chun, khi p sut ring phn ca cc kh u bng 1 atm). Vit gn, ta c:
221
gio trnh ho i cng
0 G = GT + RT ln
d PCc .DD PAa .PBb
(5.61)
b) Khi phn ng t ti trng thi cn bng: G = 0 Suy ra:

G
0 T
[PC ]c [PD ]d = RT ln [PA ]a [PB ]b
(5.62)
Trong : [PA], [PB], [PC], [PD] l p sut ring phn ca cc kh A, B, C, D ti trng thi cn bng. ng nhin [PA] PA; [PB] PB; [PC] PC; [PD] PD. V G0T ch ph thuc vo T, khi T = const th G0T = const. Do biu thc trong du ln cng ph thuc vo nhit T v l hng s khi T = const: t:
KP =
[PC ]c .[PD ]d [PA ]a .[PB ]b
= const
(5.63)
KP l hng s cn bng tnh theo p sut. Cn nh: KpT. T 5.63 ta thy: Kp cng ln th hiu sut ca phn ng cng cao. Thay 5.63 vo 5.63, c: G0T = RTlnKP (5.64) 0 0 Ch : T t di G T cho bit G T ph thuc vo T, n gin chng ta thng vit l G0. Thay 5.64 vo 5.61, ta c:
d PCc .PD ln a b ln K P G = RT PA .PB ' t: K P = d PCc .PD PAa .PBb
(5.65)
ri thay vo 5.65 c:
' G = RT (ln K P ln K P ) = RT ln ' KP KP
(5.66)
Cc phng trnh 5.61; 5.62; 5.64; 5.65; 5.66 c gi l phng trnh ng nhit ca phn ng ha hc phng trnh ng nhit Vant Hoff Ch : KP T cn KP T. Da vo phng trnh 5.66 xt c chiu hng v gii hn ca phn ng xy ra iu kin T, P = const. + Nu G < 0 KP < KP phn ng t xy ra theo chiu thun. + Nu G > 0 KP > KP phn ng t xy ra theo chiu nghch. + Nu G = 0 KP = KP phn ng t ti trng thi cn bng. C th xc nh c KP ca phn ng ha hc da vo thc nghim, bng cch xc nh G da vo 5.66 hoc 5.67 hoc tnh KP thi im kho st v so snh vi KP ca phn ng l bit c chiu hng v gii hn ca phn ng xy ra iu kin T, P = const. V d 1: Cho phn ng:
0 (G298,ht ) NH 3 = 16450 J .mol 1 .
1 3 N2(k) + H2(k) 2 2
NH3(k) xy ra 298K c
222
gio trnh ho i cng
a) Vit biu thc tnh hng s cn bng KP ca phn ng trn? b) Tnh KP 298K? Li gii a) b) Ta c: p dng 5.64: Ta c:
KP =
[P ] [P ] .[P ]
NH 3
1
N2
H2
0 0 G pu = (G298,ht ) NH 3 = 16450 J .mol 1
G0T = RTlnKP
G 0
T 0 GT 2 , 303. RT ln K P = K P = 10 RT
( 16450 )
K P = 10 2,303.8,314.298 = 10 2,88 Thay s: V d 2: Cho phn ng: CO(k) + H2O(k) CO2(k) + H2(k) c KP = 1,4 ti 1000K. Hy cho bit phn ng xy ra theo chiu no, khi p sut ring phn ca cc kh CO, H2O, CO2, H2 ln lt bng 0,5, 0,05, 0,2, 0,25atm. Li gii p dng 5.66, tnh K P:
' KP =
PCO2 .PH 2 PCO .PH 2O
0,2.0,25 =2 0,5.0,05
Nhn thy: KP = 2 > KP = 1,4 G > 0 Phn ng xy ra theo chiu nghch. Hoc: G = RT ln
' KP J 2 = 8,314 1000 K ln = 2968,1J .mol 1 > 0 Phn KP mol.K 1,4
ng xy ra theo chiu nghch. V d 3: Tnh KP ca phn ng sau 250C: 2H2O(h) + 2Cl2(k) 4HCl(k) + O2(k) H2O Cl2 Bit: Cht HCl O2 0 -1 H 298,ht(kJ.mol ): 92,3 241 0 -1 -1 188,7 223 S 298(J.mol .K ): 187 205 Li gii 0 0 T 5.40, ta c: G = H TS0 tnh c KP, cn tm H0, S0 v G0. Tnh H0: p dng quy tc tnh nhit ca phn ng ha hc da vo nhit hnh thnh, ta c: H0298,p = [2mol.(H0298,ht)H2O + 2mol.(H0298,ht)Cl2] [4mol.(H0298,ht)HCl + 1mol.(H0298,ht)O2] = [2mol.(241kJ.mol-1) + 2mol.(0kJ.mol-1)] [4mol.(92,3kJ.mol-1) + 1mol.(0kJ.mol-1)] = 482 + 369,2 = 112,8kJ Tnh S: 0 S 298,p = (2mol.S0298,H2O + 2mol.S0298,Cl2) (4mol.S0298,HCl +1mol.S0298, O2) = = (2mol.188,7J.mol-1.K-1 + 2mol.223J.mol-1.K-1) (4mol.187J.mol-1.K-1 + + 1mol.369,2J.mol-1.K-1) = 445,4J.K-1 Tnh G0:
223
gio trnh ho i cng
G0 = H0 TS0 = 112,8.1000J + 298K.445,4J.K-1 = 199.292J M: G0 = RTlnKP = 2,303 RTlgKP

K P = 10 = 10 = 10 0,035 = 1,084 V d 4: Cho phn ng: CaCO3(r) CaO(r) + CO2(k) 298K 0 -1 -1 38,1 213,7 Bit: S 298(J.mol .K ) 92,9 0 -1 H 298,ht(kJ.mol ) 1206,90 635,1 393,5 a) Phn ng xy ra theo chiu no 298K? b) Xc nh nhit ti CaCO3 bt u phn hy? Gi s H0, S0 ca phn ng khng ph thuc vo nhit . Li gii a)p dng biu thc: G0 = H0 TS0 Tnh: 0 H 298,p = [1mol.(H0298,ht)CaO + 1mol.(H0298,ht)CO2] [1mol(H0298,ht)CaCO3] = = [1mol. (635,1kJ.mol-1) + 1mol.(393,5kJ.mol-1] [1mol.(1206,90kJ.mol-1)] = 178,3 kJ S0298,p = [1mol.S0298,CaO + 1mol.S0298,CO2] [1mol.S0298,CaCO3] = = [1mol.38,1J.mol-1.K-1 + 1mol.213,7J.mol-1.K-1] [1mol.92,9J.mol-1.K-1] = 158,9 J.K-1 G0298,p = H0298,p TS0298,p = 178,3.1000J 298K.158,9J.K-1 = 130947,8J G0298,p = 130947,8J > 0 Phn ng trn xy ra theo chiu nghch. b) phn ng nhit phn CaCO3 xy ra theo chiu thun th: G0 = H0 TS0 < 0, Tc l: TS0 > H0 T>
H 0 178.3.100 J = = 1122 K S 0 158,9 J .K 1
G 0 2 , 303 RT ( 199 , 292 ) 2 , 303.8, 314.298
T nhit ln hn 1122K phn ng phn hy CaCO3 mi xy ra. 5.3. Hng s cn bng KC, KX, Kn v mi quan h gia cc hng s cn bng Nu phn ng din ra p sut khng i, p dng phng trnh:
Pi = ni RT = Ci RT V
Vo biu thc 5.63, ta s c biu thc ca hng s cn bng biu din theo nng nh sau:
[C ]c .[ D]d KC = [ A]a .[ B ]b
(5.67)
Cc i lng ghi trong ngoc [ ] ng vi nng ca cc cht thi im cn bng. KC ph thuc vo nhit , khng ph thuc vo nng . Cng c th biu din hng s cn bng qua nng phn mol xi ca cht i hoc qua s mol ca cht i:
[X C ]c .[X D ]d KX = [X A ]a .[X B ]b [n ]c .[n ]d Kn = C a D b [n A ] .[nB ]

224
(5.68) (5.69)
gio trnh ho i cng
Nng phn mol Xi ca cht i c xc nh bng s mol ni ca cht i chia cho tng s mol ca tt c cc cht c trong h (k c s mol ca dung mi).
Xi = ni
n
i =1
(5.70)
Xi 1, Xi = 1 khi h ch c mt cht Gia p sut ring phn Pi v nng phn mol ca cht i c mi lin h: (5.71) Pi = P.Xi P = P i (5.72) Trong P l p sut ton phn ca h. KP, KC, KX c mi lin h:
P n n KP = KC.(RT) = KX.P = Kn. m ni i =1
n
(5.73)
Cc bn hy dng 5.70; 5.71; 5.72 thit lp 5.73. Trong : n = (c + d) (a +b) T 5.73, d thy: KP =KC = KX = Kn khi n = (c + d) (a +b) = 0 V d 5: Tnh n cho cc phn ng sau CO + H2O CO2 + H2 n = (1 + 1) (1 + 1) = 0 2NH3 n = 2 (1 + 3) = -2 < 0 N2 + 3H2 PCl3 + Cl2 n = (1 + 1) 1 = 1 > 0 PCl5 Ch : i vi cc phn ng d th, trong cc biu thc tnh n v hng s cn bng khng c mt ca cc cht lng v cht rn: V d 6: cho cc phn ng: Fe(r) + CO2(k) FeO(r) + CO(k) CaCO3(r) CaO(r) + CO2(k) NH3(k) + HCl(k) NH4Cl(r) Phn ng th nht c: n = 1 1 = 0 v K P =
2
[P ]
[PCO ]
3
CO2
Phn ng th 2 c: n = 1 v K P = [PCO ] Phn ng th 3 c: n = 1 + 1 = 2 v K P = [PNH ].[PHCl ] 5.4. Chuyn dch cn bng. Nguyn l Lsatli 5.4.1. Khi nim v s chuyn dch cn bng: Mt phn ng ha hc ang trng thi cn bng (G = 0), nu tc ng vo phn ng mt yu t no nh nhit T, p sut P, ... th phn ng b mt cn bng (G 0). Ki ny h s chuy dch n mt trng thi cn bng mi (G = 0) ng vi cc thng s mi. 5.4.2. Cc yu t nh hng n chuyn dch cn bng a) nh hng ca nhit n hng s cn bng KP
225
gio trnh ho i cng
V KP ph thuc vo nhit , cn KP khng ph thuc vo nhit . Do , ly vi phn 5.66, ta c:

ln K P G ' = R ln K P R ln K P RT T P T P
(5.74) (5.74) (5.75)
M: dG = SdT + VdP, nn:

G = S T P
hay
G = S T T
Thay 5.74 vo h thc : G = H TS, ta c:

G G = H + T T P
Thay 5.74 vo 5.75, c:

ln K P ' G = H + RT ln K P RT ln K P RT 2 T P
M:
G = RT(lnKP lnKP) do :
H ln K P = 2 T P RT
(5.76)
Phng trnh 5.76 l phng trnh ng p Vant Hoff. Phng trnh ny biu din s ph thuc ca KP vo nhit T khi p sut P khng i. T phng trnh 5.76, ta thy: d ln K P < 0 (v R, T + i vi phn ng thun ta nhit (H < 0), th
dT
>0). Tc l o hm bc nht ca lnKP theo nhit T m. Cho nn, lnKP nghch bin vi T. V vy: Khi nhit tng th KP (hay lnKP) gim v ngc li. d ln K P > 0 , Tc l + i vi phn ng thun thu nhit (H > 0), th
dT
lnKP ng bin vi T. V vy: Khi nhit tng th KP (hay lnKP) tng v ngc li. y chnh l ni dung ca nguyn l chuyn dch cn bng Lsatli: Cn bng s chuyn dch v pha lm gim nh hng ca cc tc ng bn ngoi ln h. Nu H khng ph thuc nhit , phn ly bin s 5.76 ri ly tch phn 2 v, ta c:
T2 T1
d ln K
=
T2
T1
RT
H
2
dT
ln
K P ,T2 K P ,T1
H 0 1 1 . R T1 T2
(5.78)
Da vo 5.78 nu bit H0 v KP mt nhit cho trc th tnh c KP mt nhit bt k. So snh 2 gi tr KP ny s bit c phn ng chuyn dch theo chiu no.
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gio trnh ho i cng
V d 7: 500K, phn ng: SO2 + 1 O2

2
SO3
c KP,500K = 2,138.105. Tnh KP ca phn ng 700K. Bit, trong khong nhit nhit ca phn ng khng thay i v c gi tr bng 97,906kJ.mol-1. Li gii p dng phng trnh 5.78, ta c:
ln
K P ,700 K
2,138.10
5
97,906.10 3 J .mol 1 1 1 1 1 8,314 J .mol .K 500 K 700 K
KP,700K = 1,78.108
So snh KP,700K vi KP,500K nhn thy khi tng nhit cn bng chuyn dch theo chiu thun. b) nh hng ca p sut n hng s cn bng ha hc i vi phn ng xy ra gia cc kh l tng, KP ch ph thuc vo nhit , khng ph thuc vo p sut. V G0 = RTlnKP v G0 ch ph thuc vo nhit . Hng s cn bng KC = KP.(RT)n cng ch ph thuc vo nhit , khng ph thuc vo p sut v trong biu thc ny khng c mt ca p sut. Do , nghin cu nh hng ca p sut n hng s cn bng, chng ta phi xt qua hng s cn bng KX hoc Kn. T biu thc 5.73, ta c: KX = KP.Pn Ly loogarit t nhin 2 v, ta c: lnKX = lnKP nlnP Ly o hm 2 v theo p sut P, khi T = const:
n ln K X = P P T
Vit n gin l:
n = PV RT
d ln K X n = dP P
(5.79)
Vi kh l tng,ta c: PV = nRT PV = nRT Thay vo biu thc trn, ta c:
d ln K X V = dT RT
(5.80)
Cc phng trnh 5.79 v 5.80 ni v nh hng ca p sut n cn bng ha hc: + Nu phn ng thun tng th tch V > 0, tc l c s tng s mol d ln K X n = (c + d) (a + b) > 0 hay (c + d) > (a + b), th: < 0 khi p sut tng th KX gim cn bng chuyn dch theo chiu nghch, tc l theo chiu lm gim th tch hay l chiu lm gim s mol.
dP
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gio trnh ho i cng
+ Nu phn ng thun gim th tch V < 0, tc l c s gim s d ln K X mol n = (c + d) (a + b) < 0 hay (c + d) < (a + b), th: > 0 .Khi ny p sut tng th KX tng cn bng chuyn dch theo chiu thun, tc l theo chiu gim th tch hay l theo chiu lm gim s mol. Cc biu thc 5.79; 5.80 l nhng biu thc nh lng ca nguyn l chuyn dch cn bng Lsatli khi p sut thay i, nguyn l c pht biu: Khi tng p sut th cn bng chuyn dch theo chiu lm gim th tch, tc l chiu lm gim s mol hay l chiu chng li s tng p sut v ngc li. + Nu phn ng c V = 0 tc n = (c + d) (a + b) = 0 (phn ng d ln K X khng c s thay i s mol), khi ny = 0 lnKX = const, tc l KX = const. Ngha l KXP. Do khi p sut thay i cn bng khng chuyn dch. V d 8: Phn ng N2 + 3H2 2NH3 c V = 2 (1 + 3) = 2 <0, d ln K X do > 0 khi tng p sut th KX tng, tc cn bng ca phn
dP dP dP
ng chuyn dch theo chiu thun (chiu lm gim th tch hay l chiu lm gim s mol). iu ny cho thy phn ng tng hp NH3 c tin hnh p sut cao. c) nh hng ca nng n s chuyn dch cn bng ha hc kho st nh hng ca nng n s chuyn dich cn bng, chng ta xt v d sau:
V d 9: Hng s cn bng ca phn ng: PCl3(k) + Cl2(k) bng 33,3 7600C. Tnh nng cn bng ca PCl5(k) mi cht trong h nu nng ban u ca PCl5 = 0,05 M v PCl3 = 5,00M. Li gii
Ban u (C0): 0,05 5 Phn ng: x +x +x Ti TTCB: (0,05 x) (5 + x) x [PCl3 ][Cl2 ] = (5 + x).x = 33,3 x2 + 38,3x 1,665 = 0 . Ta c: K C =
PCl5(k)
PCl3(k) + Cl2(k) KC = 33,3 7600C
[PCl5 ]
(0,05 x)
Gii phng trnh bc 2 vi iu kin: 0 < x 0,05, ta c: x1 = 0,043; x2 = 38,34 < 0 loi. Vy: [PCl5] = 0,05 x = 0,05 0,043 = 0,007M [PCl3] = 5 + 0,043 = 5,043M [Cl2] = 0,043M
228
gio trnh ho i cng
Cu hi t ra cho trng hp ny l: Nu tng nng ca PCl5 t 0,007M ln n 0,1M th nng ca cc cht trng thi cn bng mi l bao nhiu? Hy cho nhn xt v s chuyn dch cn bng khi tng nng ca PCl5? Lm tng t nh trn: Ban u (C0): 0,1 5,043 0,043 Phn ng: y +y +y Ti TTCB: (0,1 y) (5,043 + y) (0,043 + y) [PCl3 ][Cl2 ] = (5,043 + y).(0,043 + y) = 33,3 . Ta c: K C =
PCl5(k) PCl3(k) + Cl2(k) KC = 33,3 7600C
[PCl5 ]
(0,1 y )
y2 + 38,343y 3,33 = 0 Gii phng trnh bc 2 vi iu kin: 0 < y 0,1, ta c: y1 = 0,086; y2 = 38,43 < 0 loi Ti trng thi cn bng mi, nng ca cc cht l: [PCl5] = 0,1 y = 0,1 0,086 = 0,014M [PCl3] = 5,043 + y = 5,043 + 0,086 = 5,129M [Cl2] = 0,043 + y = 0,043 + 0,086 = 0,129M Nhn xt: Khi tng nng ca PCl5 t 0,043M ln 0,1M th ti trng thi cn bng mi nng ca PCl5 ch cn 0,014M. Chng t phn ng chuyn dch theo chiu thun Khi qut: Khi thay i nng ca mt cht no th cn bng s chuyn dch theo chiu chng li s thay i cht . d) nh hng ca cht xc tc n s chuyn dch cn bng ha hc Cht xc tc khng lm chuyn dch cn bng (v cht xc tc lm tng vn tc ca phn ng thun cng nh phn ng nghch ln nhng lng bng nhau) m lm cho phn ng nhanh chng t ti trng thi cn bng. Mt s bi tp t lun khng c li gii Bi 1: Tnh Q, A, U khi nn ng nhit thun nghch 2 mol kh He t 1 n 4 atm 400K. Bi 2:
Bi 9: Tnh hng s cn bng ca phn ng: CO(k)+H2O(h) ? H2(k)+ CO2(k) 8500C Bit nng ban u ca cc cht nh sau: CO = 1mol/lit; H2O = 3mol/lit; v khi cn bng c thit lp th nng ca CO2 = 0,75mol/lit Bi 11: Cho phn ng 2HI(k) = H 2(k) + I2(k) 1000C c K = 2,71.10-3. Tnh % HI b phn hy nhit trn. Bi 12: Hng s cn bng ca phn ng iu ch NH3 t N2 v H2 5000C l 1,50.10-5 atm-2. Tnh xem c bao nhiu % hn hp ban u (N2 + 3H2)
229
gio trnh ho i cng
chuyn thnh NH3 nu phn ng c thc hin 500 atm, 1000 atm v cho nhn xt v kt qu thu c. Bi 13: 6000C di p sut 200atm, hn hp N2 + 3H2 cho php thu c NH3 theo phn ng: N2 + 3H2 ? NH3 l 8,25% th tch NH3 (So vi th tch ca hn hp khi cn bng). Tnh % th tch ca NH3 nu phn ng vn tin hnh bnh thng 6000C nh di p sut 1000 atm. Bi 14: 630C phn ng N2O4(k) ? 2NO2 (k) c KP = 1,27 Tnh thnh phn ca hn hp ra phn s mol khi P = 1atm; 10atm. Qua hy rt ra kt lun v nh hng ca P n s chuyn dch cn bng Bi 15: 270C v di p sut P = 1atm, phn ly ca N2O4 l 20% a. Tnh: KP = ? so snh vi gi tr KP ca bi 14 v cho bit phn ng l thu nhit hay ta nhit. phn ly p sut P = 0,05 atm. b. Cho 46g N2O4 vo 1 bnh 20 lit 270C. Tnh thnh phn ca hn hp kh lc cn bng? Cho N = 14; O = 16
230
gio trnh ho i cng
Chng 6
NG HA HC V XC TC 1. MT S KHI NIM M U 1.1. Phn ng ng th v phn ng d th * Phn ng ng th: Phn ng c gi l ng th khi chng din ra trong mt pha. l phn ng xy ra gia cc cht kh, gia cc cht lng hon ton trn ln vi nhau, cc phn ng xy ra trong dung dch. Phn ng ng th bao gi cng xy ra trong ton b th tch ca h phn ng. V d 1: Cho dung dch H2SO4 long tc dng vi dung dch natri thiosunfat theo phn ng: H2SO4 + Na2SO4 Na2SO4 + S + SO2 + H2O Lu hunh c gii phng t phn ng lm c ton b th tch ca bnh. * Phn ng d th: Phn ng c gi l d th khi cc cht tham gia phn ng khng nm cng mt pha. l phn ng xy ra trong h Rn - lng, rn - kh, ... Phn ng d th ch din ra trn ranh gii phn chia cc pha ca h. V d 2: Cho Km vo dung dch axit clohiric, bt kh hiro ch thot ra t b mt kim loi km. Trong cc phn tip theo ca chng ny, chng ta ch quan tm ti phn ng ng th. 1.2. Vn tc ca phn ng ho hc 1.2.1. Khi nim:Vn tc ca phn ng ha hc c o bng bin thin nng (hay lng cht) ca mt cht c trong phn ng trong mt n v thi gian. 1.2.2. n v ca vn tc phn ng: Theo khi nim trn, n v ca vn tc phn ng l: [nng .thi gian-1] Nu nng l mol.l-1 (hay M) cn thi gian l giy (s), th n v ca vn tc l: [mol.l-1.s-1] hay [M.s-1] Tuy nhin ty thuc vo phn ng ha hc xy ra nhanh hay chm m dng cc n v o thi gian khc nhau nh: pht, gi, ngy, thng nm. Th k, Ngoi ra n v ca vn tc cn dng l: [lng cht.thi gian-1] 1.2.3. Vn tc trung bnh v vn tc tc thi ca phn ng ha hc i vi mi phn ng xc nh, vn tc (v) l mt i lng xc nh v v 0
231
gio trnh ho i cng
Cho phn ng: aA + bB + eE + gG + (6.1) a) Vn tc trung bnh: vtb hay v Vn tc tiu th cc cht phn ng A, B, c xc nh bng biu thc:
vA = C A C B < 0 ; vB = < 0 ; t t
Vn tc hnh thnh cc cht sn phm E, G, c xc nh bng biu thc:

vE = C E C F > 0 ; vF = > 0; t t
Trong : C l bin thin nng ca cht trong phn ng, t l bin thin thi gian tng ng vi bin thin C. Vn tc tiu th ca cc cht phn ng < 0 v nng cc cht phn ng lun gim dn theo thi gian ( C A = C A(T ) C A(T ) < 0 ; C B = C B (T ) C B (T ) < 0 ; ). Cn vn tc hnh thnh cc cht sn phm th lun dng v: Csn phm > 0. V bin thin nng C ca cc cht trong 6.1 l khc nhau, nn: vA v B v E v F V nguyn tc, xc nh vn tc ca phn ng theo bt c cht no c trong phn ng 6.1 u c. Vic chn vn tc ca mt cht no l vn tc ca phn ng l khng c, v khi vi mt phn ng xc nh s c nhiu gi tr vn tc. Nh trn ni, vn tc ca phn ng l mt i lng xc nh. M bin thin nng ca cc cht lun t l vi h s t lng ca cc cht, do vn tc trung bnh ca phn ng c xc nh nh sau:
2 1 2 1
Hay:
vA vB vE vF = = ... = = = ... a b e f 1 C A 1 C B 1 C E 1 C F v= = = = = a t b t e t f t v=
Phi thm du tr vo biu thc, v vn tc ca cht phn ng < 0 cn vn tc phn ng lun dng. Biu thc trn c vit gn nh sau:
1 C v=m i t
(6.2)
Vi i l cc h s t lng ca cc cht c trong phn ng 6.1. b) Vn tc tc thi: vt hay v Vn tc tc thi l vn tc c o ti thi im t. Mun vy, chng ta xt gii hn ca vn tc trung bnh v Vit gn l:
C 1 1 dC v = lim v = m lim =m t 0 t 0 t i i dt
1 dC v=m i dt
(6.3)
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gio trnh ho i cng
1 dC A 1 dC 1 dC 1 dC v= = B = = E = F = a dT b dT e dT f dT dC Trong biu thc 6.3, i lng c gi l o hm bc nht ca dT
nng theo thi gian. V d 1: Cho phn ng 2NOBr(k) 2NO(k) +Br2(k) iu kin xc nh, thc nghim o c vn tc hnh thnh NO l -4 1,6.10 mol.l-1.s-1. Hy tnh: a) Vn tc ca phn ng trn. b) Vn tc tiu th NOBr(k). Li gii a) p dng 6.3, ta c:
v=
1 dC NO 1 = 1,6.10 4 mol.l 1 .s 1 = 8.10 5 mol.l 1 .s 1 2 dT 2
b) Theo h s t lng ca cc cht c trong 6.1, ch NOBr(k) l cht tham gia phn ng, ta c: vtiu th NOBr(k) = vhnh thnh NO(k) = 1,6.10-4 mol.l-1.s-1 1.3. nh hng ca nng n vn tc phn ng. nh lut tc dng khi lng Vn tc ca phn ng ha hc ph thuc vo cc yu t sau: + Bn cht ca phn ng (thc cht l bn cht ca cc cht phn ng, nu phn ng ang xt l phn ng n gin mt chiu bc 1). + Nhit T, p sut P + Nng ca cc cht phn ng. + Din tch b m tip xc (i vi phn ng d th) + Xc tc + in trng, t trng, ... nh hng ca in trng, t trng hin nay cha c nghin cu nhiu do khng cp n chng ny. Xc tc s xt mt mc ring, cn trong gii hn ca chng trnh khng xt phn ng d th nn khng cn quan tm ti din tch b mt tip xc. Nh vy i vi phn ng ng th, vn tc ca phn ng ph thuc vo: Bn cht ca phn ng, nhit T, p sut P v nng cc cht phn ng. Khi xt mt phn ng c th xy ra mottj nhit T, p sut T xc nh th vn tc ca phn ng ha hc ch ph thuc vo nhit . 1.3.1. nh lut tc dng khi lng C phn ng dng tng qut: aA + bB + sn phm (6.4) T cc kt qu thc nghim, xy dng c phng trnh sau:
v = kC C B ... A
(6.5)
6.5 l phng trnh ng hc ca nh lut tc dng khi lng Trong :

233
gio trnh ho i cng
+ v l vn tc ca phn ng o ti thi im t. + CA, CB, ... l nng cc cht A, B, ... o ti thi im t. + Ly tha , , ... l bc ring phn ca phn ng c xt theo cc cht A, B, .... , , ... l cc s nguyn (1,2,3), hay s thp phn (1/2,3/2,...) v c xc nh bng thc nghim. Tc , , ... l cc hng s. + n = + + c gi l bc ton phn ca phn ng (gi tt l bc phn ng). Bc phn ng (n) cng c xc nh bng thc nghim v nm trong khong: 0 n 3 + k l h s t l (sau ny l hng s vn tc ca phn ng). nh lut tc dng khi lng c pht biu nh sau: Vn tc ca phn ng ha hc t l thun vi tch nng ca cc cht phn ng vi ly tha l cc s , , ... c xc nh t thc nghim. 1.3.2. Hng s vn tc ca phn ng ha hc: k Thc nghim cho bit: H s t l k ph thuc 2 yu t sau: + Bn cht ca phn ng ha hc. + Nhit T. Nu kho st mt phn ng ha hc xc nh xy ra ti mt nhit T khng i, th k l mt hng s. V vy h s t l k c gi l hng s vn tc ca phn ng ha hc (gi tt l hng s vn tc phn ng) a) ngha ca hng s vn tc phn ng k: T 6.5 ta thy k chnh l vn tc ca phn ng ha hc khi CA = CB = = 1M. Trong trng hp ny th nguyn ca k chnh l n v ca vn tc: [mol.l-1,s-1] T ngha ca k, cho thy khi kho st mt phn ng c th chng ta thng quan tm ti hng s vn tc ca phn ng. b) Th nguyn ca k: Khi nng ca cc cht phn ng bng nhau, th 6.5 c vit gn thnh: v = kC( + + ) = kCn (6.5a) T 6.5 ta thy th nguyn ca k ph thuc vo n v ca vn tc, n v ca nng v gi tr ca bc phn ng n. T 6.5a, ta c:
k= v Cn
Thay n v ca v, c v cc gi tr khc nhau ca bc phn ng n, ta s c cc th nguyn khc nhau ca k: Vi n =1, th: k 1 mol.l
mol.l 1 .tg 1 = tg 1
mol.l 1 .tg 1 Vi n = 2, th: k = mol 1 .l.tg 1 1 1 mol.l .mol.l
Nh vy vi n = 1 th n v ca k l [tg-1] ( tg thi gian), cn n = 2 n v ca k l [mol-1.l.tg-1]. Vi cc gi tr khc ca bc phn ng n lm tng t nh trn cng tm c th nguyn ca k. 1.3.3. Phn loi phn ng theo bc phn ng Da vo bc phn ng n, ta c cc loi phn ng sau:
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gio trnh ho i cng
+ Phn ng bc 1 (n =1) + Phn ng bc 2 (n = 2) + Phn ng bc 3 (n = 3) + Phn ng bc 0 (n = 0) + Phn ng bc phn s (n = 1/2, 3/2, ...) V d 2: Phn ng N2O5(k) 2NO2(k) + O2(k)
2 5
n C phng trnh ng hc: v = kC N =O =1 ng bc 1. V d 3: Phn ng H2(k) + I2(k) 2HI(k) (**) C phng trnh ng hc: v = kC H C I vi = =1; n = + = 2. V vy ta ni phn ng (**) c bc ring phn ca H2 bng 1, ca I2 bng 1 v bc ca phn ng bng 2. V d 4: Phn ng H2(k) + Cl2(k) 2HCl(k) (***) 1 C phng trnh ng hc: v = kCH CCl2 vi = 1, =1/2; n = + = 3/2. V vy ta ni phn ng (***) c bc ring phn ca H2 bng 1, ca Cl2 bng 1/2 v bc ca phn ng bng 3/2. T 6.5, cho thy vn tc v ca phn ng lun gim dn theo thi gian, v nng ca cc cht phn ng lun gim dn. Nu biu din s ph thuc ca vn tc phn ng theo thi gian th ng biu din l ng cong v c dc nghing dn t tri sang phi (vi n 0), v 6.5 l hm s m. Trong thc t cn gp phn ng bc 0, tc l v = k = const (theo 6.5a). Trng hp ny vn tc khng ph thuc vo nng ca cc cht phn ng m ph thuc vo cc yu t khc nh: S hp th nh sng trong cc phn ng quang ha, vn tc khuch tn trong cc phn ng b mt. Phn ng bc 0 c dng ng thng nm song song vi trc honh (hnh 6.1). v
2 2 2 2
1 (*) 2 = kC N 2O5 ; = n = 1, nn (*) l phn
n0 n=0
Thi gian phn ng (t) Hnh 6.1: S ph thuc ca vn tc phn ng vo thi gian V d 5: Phn ng phn hy NH3 trn b mt W, Mo, Os 1000K, thc nghim xc nh l phn ng bc 0 T biu thc 6.5: v = kC C B ... A
235
gio trnh ho i cng
Da vo mi quan h gia vn tc phn ng v s thay i nng , s tm c , , ... t cng tm c bc phn ng n. Bng cch: Nu gi nguyn nng ca B, tng nng ca A ln gp i m vn tc tng gp 2 ln th = 1, vn tc tng gp 4 ln th = 2. Ngc li, gi nguyn nng ca A, tng nng ca B ln gp i m vn tc tng gp 2 ln th = 1, vn tc tng gp 4 ln th = 2. Nh vy, chng ta s tm c:bc phn ng n, hng s vn tc phn ng k v bit v,CA, CB,... v , ,... 1.3.4. Phn ng n gin, phn ng phc tp Trn quan im ng ha hc, cc phn ng ha hc c chia lm 2 loi: a) Phn ng n gin:L cc phn ng ch xy ra qua mt giai on. Dng phn ng: aA + bB + ... sn phm V d 6: Phn ng cng Diels Alder gia etilen v butaddien thnh xiclohexen: C2H4 + C4H6 C6H10 b) Phn ng phc tp:L cc ph ng xy ra qua nhiu giai on Dng phn ng: aA + bB + ... ... ... ... sn phm V mt ng hc lm th no bit c mt phn ng l n gin hay phc tp? T phn ng 6.5, nu xc nh c: =a 6.1 l phn ng n gin =b a 6.1 l phn ng phc tp b Nu = a, b th n gin vi A cn phc tp vi B. Khi ny 6.1 cng l phn ng phc tp. Trong cc v d 2, 3, 4. Phn ng (*), (**) l phn ng n gin, cn phn ng (***) l phn ng phc tp (n gin vi H2, phc tp vi Cl2). 2. PHNG TRNH NG HC CA PHN NG 1 CHIU Ch xt phn ng ng th n gin 1 chiu bc 1, bc 2. (Cc phn ng n gin bc 3, khc dng tham kho) * Phng trnh ng hc l phng trnh biu th mi quan h ca 3 i lng vn tc v (hay dng hng s vn tc k), nng C v thi gian phn ng t. 2.1. Phn ng n gin 1 chiu bc 1 Trong thc t, cc phn ng phn hy, ng phn ha, phng x, ... l phn ng n gin bc 1. Dng tng qut ca phn ng n gin 1 chiu bc 1 l: (I) nA sn phm (thng gp n = 1) p dng phng trnh 6.3 v 6.5 thit lp phng trnh ng hc cho phn ng n gin 1 chiu bc 1.
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Ta c: Hay:
Ly tch phn 2 v: Trong , A l hng s tch phn Xt ti thi im t = 0 (phn ng cha xy ra), th: A = lnC0, vi C0 l nng ban u v C l nng ca cht phn ng cng li ti thi im t. Thay A = lnC0 vo biu thc trn, c: lnC = kt + lnC0 hay :
kt = ln C0 C
dC dC dt = kC v = kC Ha dt dC = kdt dlnC = kdt C d ln C = kdt lnC = kt + A v=
(6.6a)
gian.
t: C0 = a th C = a x; vi x l nng cht A mt i sau t n v thi Khi 6.6a c vit l:

kt = ln a ax
(6.6b)
Thi gian cho lng cht ban u mt i mt na ( x = a/2) hay lng cht phn ng cn mt na, c gi l thi gian na phn ng (chu k bn hy hoc chu k bn r). Thay x = a/2 vo 6.6b, ta c:
t 12 = 0,693 k
(6.7)
V k l hng s ti mt nhit xc nh, nn t1/2 l mt hng s. Ch : Nu cht phn ng l cht kh, th thay nng C bng p sut P cc biu thc 6.6a v 6.6b. V d 7: Mt ng v phng x sau 1 gi phn hy mt 75%. Xc nh hng s vn tc phn hy, chu k bn hy, thi gian cn thit phn hy 87,5% v s phn trm b phn hy sau 15 pht. Li gii V qu trnh phng x xy ra theo quy lut ng hc ca phn ng 1 chiu n gin bc 1. p dng 6.6b, ta c:
1 1 100 a -1 k = ln = ln = 0,0231 pht t a x 60 phut 100 75
Tnh chu k bn hy, da vo 6.7:

t 12 =
0,693 0,693 = = 30 pht 0,0231 phut 1 k 1 100 ln = 90 pht 1 0,0231 phut 100 87,5
Thi gian cn thit phn hy 87,5% l:

t=
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gio trnh ho i cng
0,0231 pht-1.15 pht = ln
2.2. Phn ng n gin 1 chiu bc 2 Trong thc t, cc phn ng n gin 1 chiu bc 2 thng gp l: H2 + I2 2HI 2NO2 2NO + O2 V cc phn ng x phng ha, nh: CH3COOC2H5 + NaOH CH3COONa + C2H5OH C hai trng hp i vi loi phn ng ny. * Trng hp th nht: C dng tng qut: (II) nA sn phm (thng gp n = 2) Lm tng t nh phn ng n gin 1 chiu bc 1, ta c:
kt = x a(a x)
100 x = 29,27% 100 x
(6.8)
Thi gian na phn ng c xc nh bng biu thc:

t 12 =
1 k .a
(6.9)
Thi gian na phn ng ca dng (II) ph thuc vo nng ban u ca cc cht phn ng. Cho nn thi gian na phn ng ca dng 2 khng phi l mt hng s.
* Trng hp th hai: C dng tng qut A + B sn phm (III) Nu nng ban u ca A v B bng nhau (C0A = a = C0B = b), th phng trnh ng hc ca trng hp ny l cc biu thc (6.8), (6.9) ging nh trng hp th nht. Nu nng ban u ca A l C0A = a, ca B l C0B = b v a b th phng trnh ng hc ca phn ng dng (III) l:
kt = b( a x ) 1 ln (a b) a(b x)
(6.10)
iu kin ca 6.10 l: a b Khi s dng 6.10, cc bn nn chn cht A l cht c nng ln hn, cht B l cht c nng nh hn, th s thun tin cho vic lm ton. V d 8: Cho vo mt bnh cu 5.10-2 mol CH3COOCH3 v 5.10-2 mol NaOH tan trong 1 lt nc v gi nhit khng i, nhn thy: Sau mt thi gian l 3,70 pht CH3COOCH3 cn li l 2,5.10-2 mol. Tnh xem sau 15 pht c bao nhiu phn trm axetat metyl tham gia phn ng?
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gio trnh ho i cng
Cho bit: nu tng nng ca mt trong hai cht ln gp i th vn tc ca phn ng cng tng gp i. Li gii Theo bi, phn ng: CH3COOCH3 + NaOH CH3COONa + CH3OH l phn ng bc 2, v c thi gian na phn ng l: 3,7 pht Vy hng s vn tc ca phn ng ny l:
k=
1 = 5,4mol 1 .l. phut 1 1 5.10 mol.l .3,7 phut
2
Nng axetat metyl b phn hy sau 15 pht l:

5,4mol 1 .l. phut 1 .15 phut =
x 5.10 mol.l (5.10 2 mol.l 1 x)

2 1
x = 0,04 mol.l-1
0,04 .100 = 80% 5.10 1
Phn trm este phn ng l:
2.3. Mt s phn ng n gin mt chiu khc Phng trnh vn tc dng tng qut:
kt = t 12 =
1 1 1 ( n1) . ( n 1) n 1 (a x ) a 2 ( n1) 1 (n 1).(a x) ( n1) .k
(6.11) (6.12)
Trong : n l bc phn ng
3. NH HNG CA NHIT N VN TC PHN NG 3.1. nh hng ca nhit n vn tc phn ng Thc nghim cho bit: khi nhit tng th vn tc phn ng tng a) Quy tc thc nghim ca Vant Hoff T cc d kin thc nghim, Vant Hoff rt ra quy tc sau: nhit gn nhit phng, khi nhit tng thm 10 , vn tc phn ng tng thm t 2 n 4 ln T quy tc, ta c biu thc sau:
kT2 kT1
1
T2 T1 10
(6.13)
Trong: + kT l hng s vn tc phn ng nhit T2 , (T2 > T1) + kT l hng s vn tc phn ng nhit T1 + c gi l h s nhit ca vn tc phn ng. =24 y l quy tc gn ng. Quy tc ny c gii thch nh sau: S tng nhit lm cho chuyn ng nhit ca cc phn t tng, do lm tng s va
2
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gio trnh ho i cng
chm gia cc phn t cht phn ng, c bit lm tng nhanh s va chm c hiu qu nn vn tc phn ng tng. T 6.13 nu t
T2 T1 = n th T2 = 10n + T1. T n c ngha l s ln 10
tng nhit , mi ln tng 10 . T 6.13 c vit: kT + 10n = n.KT . Phng trnh ny cho bit: Vn tc ca phn ng xy ra nhit T + 10n ln gp n ln khi xy ra nhit T. V d 9: Khi tng nhit t 500C ln 1000C, vn tc ca phn ng tng ln 250 ln. Hy cho bit khi tng nhit t 500C ln 750C vn tc phn ng tng ln bao nhiu ln? Li gii p dng biu thc 6.13, ta c:
k1000 C k 500 C
7550 10
10050 10
= 5 = 250 = 250
Vy, khi tng nhit t 500C ln 750C, th:

k 750 C k 500 C
=
1 = 2,5 = 250 5 2,5
= 250
= 250 = 10,8 ln
b) Phng trnh ca Areniux Nm 1889, da vo cc kt qu thc nghim Areniux thit lp phng trnh biu th mi lin h gia hng s vn tc k v nhit T (theo Kenvin):
ln k =
B +C T
(6.14)
Trong : + B, C l cc hng s ch ph thuc vo bn cht ca phn ng, khng ph thuc vo nhit . + B=

Ea y, Ea l nng lng hot ng ha, R l hng s R
kh. V B l hng s, nn Ea cng l hng s i vi mi phn ng xc nh v khng ph thuc vo nhit . t: C = lnA ri thay vo 6.14, ta c:
ln k =
ln
k Ea = A RT
Ea + ln A RT
Ea RT
(6.15) (6.16)
Hay
k = A.e
V C l hng s, nn A cng l hng s i vi mi phn ng v khng ph thuc vo nhit . T phng trnh 6.16 cn c vit dng:
ln
kT2 kT1
Ea R
1 1 . T T 2 1
(6.17)
Ch : T 6.15 hon ton xc nh c Ea v A. V Ea, A l hng s nn phng trnh biu din s ph thuc ca lnk vo 1/T l hm bc nht do c dng ng thng. Vi dc bng
Ea Ea ( v bng nu chuy 6.15 sang R 2,303R
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gio trnh ho i cng
logarit thp phn) v ct trc tung ti gi tr lnA (hay lgA). T xc nh c A, Ea cho phn ng kho st. V d 10: Khi tin hnh 100C th mt phn ng kt thc sau 95s, cn tin hnh 200C th kt thc sau 60s. Tnh nng lng hot ha ca phn ng. Li gii V vn tc phn ng lun t l nghch vi thi gian tin hnh phn ng, nn:
kT2 kT1
=
k 200 C k100 C
t1 95 = = 1,583 t 2 60
p dng cng thc 6.17, ta c:

ln
k 200 C k100 C
= ln 1,583 =
Ea 1 1 Ea = 31.798,4 J 1 1 8,314 J .mol .K 283K 293K
3.2.Nng lng hot ha Nng lng hot ha l nng lng d ti thiu so vi nng lng trung bnh m phn t cn c to ra va chm c hiu qu lm cho phn ng ha hc xy ra c. Theo khi nim trn, mt phn ng ha hc c nng lng hot ha Ea cng nh (cng thp) th cng d xy ra (vn tc phn ng cng ln) v ngc li. Phn ng ha hc xy ra m khng cn ph v mt lin kt no th c Ea = 0. l trng hp 2 gc t do kt hp vi nhau: V d 11: Cl + Cl Cl2 Trong trng hp ny vn tc t c l v cng ln. Tuy nhin, c nhng phn ng c nng lng hot ha rt cao nh phn ng: CO2(k) CO(k) + O c Ea = 418,4kJ.mol-1 thng xy ra rt chm, chm ti mc khng th quan st c. V d 12: Phn ng phn hy CO(CH2COOH)2 l phn ng bc 1. 100C phn ng c k = 1,080.10-4s-1; 600C c k = 5,484.10-2s-1. Xc nh nng lng hot ha Ea v hng s vn tc ca phn ng xy ra 300C. Li gii
p dng biu thc 6.17: ln
1 1 T T kT1 2 1 2 1 V thay cc gi tr: kT2 = 5,484.10 s ; kT1 = 1,080.10 4 s 1 ; T2 = 273 + 60

kT2 = Ea R
=333; T1 = 273 + 10 =283 vo biu thc, ta c: Ea 81,17 kJ.mol-1. Thay Ea v chn mt trong 2 cp kT , T1 hoc kT , T2 lm kT , T1 vo biu thc 6.17, th tnh c: k303K = 1,67.10-3s-1. Chng ta xt mi quan h gia nhit phn ng HT vi nng lng hot ha Ea ca phn ng. Gia hng s vn tc ca phn ng thun, hng s vn tc ca phn ng nghch v hng s cn bng ca phn ng thun nghch c mi lin h sau:
1 2 1
K=
kt kn
(6.18)
gio trnh ho i cng
241
Ly logarit 2 v ri ly o hm c 2 v theo nhit T phng trnh 6.18, ta c:

d ln k t d ln k n d ln K = dT dT dT
(6.19)
Kt hp vi phng trnh 5.76 ca chng 5:

0 d ln K H T = dT RT 2 E d ln k = a2 dT RT 0 Ea ,t E H T a ,n2 = RT 2 RT RT 2
V phng trnh: Ta c:
(6.20)
Trong Ea,t v Ea,n l nng lng hot ha ca phn ng thun v phn ng nghch. Nu coi H0T khng ph thuc vo nhit khi b k hiu T trong H0T , th t 6.20 ta c: Ea,t Ea,n = H0 (6.21) Phng trnh 6.21 l phng trnh biu th mi quan h gia nng lng hot ha ca phn ng thun, phn ng nghch v nhit ca phn ng. C hai trng hp v mi lin h ny: Th nht: Phn ng ta nhit, H0 < 0 (hnh 6.2a) Th hai: phn ng thu nhit, H0 > 0 (hnh 6.3b) Nng lng Nng lng Ea, n Ea, t Ea, n Ea, t H0 < 0 H0 < 0 Tin trnh phn ng (a) Tin trnh phn ng (b)
HNH 6.2. Mi lin h gia nng lng hot ha Ea vi nhit phn ng H0

4. XC TC 4.1. Mt s khi nim chung Xc tc: L hin tng lm tng vn tc ca phn ng nh tc dng ca cht xc tc. Cht xc tc: L cht lm bin i vn tc phn ng bng cch tham gia vo cc giai on phn ng trung gian, sau lng v bn cht ha hc ca cht khng b bin i. V d 13: Phn ng phn hy H2O2 nh cht xc tc ITrng i hc cng nghip h ni
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gio trnh ho i cng
Ban u, c phn ng: H2O2 + IH2O + IOSau : H2O2 + IO- H2O + O2 + ICng c hai phn ng trn ta c: 1 I HO HO+ O
2 2 2
T v d va nu, ta thy xc tc tham gia vo cc qu trnh ha hc nhng khng b bin i v khi lng cng nh v mt ha hc. Tuy nhin, mt s trng hp b bin i v mt vt l. V d 14: Phn ng nhit phn KClO3 trn xc tc MnO2 3 MnO2 KClO3 KCl + O2
2
Trc khi phn ng MnO2 dng tinh th, sau phn ng tr thnh dng bt mn. Cht xc tc lm tng vn tc ca phn ng gi l cht xc tc dng, lm gim vn tc ca phn ng gi l cht xc tc m. Cn ch thut ng xc tc hu nh ch biu th cc cht lm tng vn tc ca phn ng. Nu cht xc tc nm cng pha vi cht phn ng th gi l xc tc ng th, cn nm khc phan vi cht phn ng gi l xc tc d th. V d 13, 14: I v MnO2 l xc tc ng th, cn phn ng tch H2O t ru etylic xy ra pha hi trn xc tc Al2O3 l phn ng xc tc d th. Al2O3 CH3CH2OH CH2 = CH2 + H2O 3500C Thng thng, cht xc tc l nhng cht c a vo cc phn ng ha hc. Tuy nhin c mt s trng hp, cht xc tc l mt trong cc sn phm c sinh ra t phn ng. trng hp ny c gi l phn ng xc tc. V d 15: Phn ng oxi ha axit oxalic bng dung dch KmnO4 trong mi trng axit: 2MnO4 + 5H2C2O4 + 6H+ 2Mn2+ + 10CO2 + 8H2O Cht xc tc ca phn ng ny l ion Mn2+. Ban u vn tc chm, khi nng Mn2+ ln th vn tc li xy ra nhanh hn. Hot tnh ca nhiu cht xc tc tng mnh khi chng cha thm mt lng nh cht kch thch. Cc cht ny bn thn n khng c tc dng xc tc nhng li lm tng c hot tnh xc tc ca cht xc tc. V d 16: i vi phn ng oxi ha SO2 thnh SO3 trn xc tc V2O5. V2O5(r) 2SO2 + O2 2SO3 Hot tnh ca xc tc V2O5 tng ln vi trm ln khi V2O5 c trn thm mt t mui sunfat ca kim loi kim. Hot tnh ca cht xc tc cng c th b gim i, thm ch c th mt hn nu b nhim bn bi cht c xc tc. v d 16, ch cn mt lng nh asen cng lm ng c V2O5 lm cho phn ng oxi ha SO2 thnh SO3 khng xy ra.
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gio trnh ho i cng
Cc phn ng xc tc rt quan trng trong i sng ca chng ta. Hu ht cc phn ng sinh ha trong c th ngi u l phn ng xc tc. Hu ht cc qu trnh ha hc xy ra trong cng nghip, c bit l cng nghip ha du u l phn ng xc tc. Khi Berzelius a ra khi nim v nh ngha v xc tc (nm 1835), n nay xc tc c mt qu trnh pht trin gn 200 nm. Nhng ch n nhng nm cui th k 19 xc tc mi c ng dng trong cng nghip. Ngy nay, xc tc em li cho cng nghip ha hc nhiu li nhun, do xc tc c coi l vt liu chin lc ca cng nghip ha hc. 4.2. Cc c im ca cht xc tc a) Cht xc tc tham gia vo phn ng, tn ti di dng hp cht trung gian. Cui phn ng xc tc li c ti sinh li. Hp cht trung gian c nhng c im sau: + Rt km bn, khng tn ti trong dung dch m ch c to thnh trong qu trnh xc tc. + L hp cht b mt, khng tn ti thnh pha c lp. S n gin m t mt phn ng xc tc nh sau: (*) A + K [AK] AK AK + B [AKB] AB + K (**) A + B AB (***) Trong : A, B l cc cht phn ng; AB l sn phm; K l cht xc tc. Phn ng (*),(**) xy ra vi vn tc rt nhanh so vi phn ng trc tip gia A v B khi khng c cht xc tc K. S n gin m t mt phn ng khng c xc tc nh sau: A + B [AB] AB b) Cht xc tc lm gim nng lng hot ha ca phn ng Phn ng (*),(**) c vn tc ln l do nng lng hot ha to ra [AK] v phn hy [AK] u nh hn nhiu nng lng hot ha to ra [AB] v phn hy [AB] khi khng c xc tc (hnh 6.3). Nng lng
[A B]
Ea
[AK] [AKB]
Ea
A+B AB
Tin trnh phn ng
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gio trnh ho i cng
Hnh 6.3. Nng lng hot ha ca phn ng ng lin: Phn ng khng c cht xc tc ng ri: Phn ng c cht xc tc Xc tc cng hot ng th vn tc ca phn ng c xc tc cng ln, khi xc tc K quay vng c cng nhiu. V vy trong phn ng xc tc lng xc tc K khng cn nhiu. C th nh gi hot tnh ca mt xc tc qua Ea. Ea cng nh th xc tc cng hot ng vn tc phn ng cng cao. c) Cht xc tc c kh nng lm tng vn tc ca phn ng vn d xy ra c (G < 0), khng lm thay i c bn cht nhit ng ca phn ng. Tc l, nu mt phn ng c G > 0 th khng c bt k mt xc tc no lm cho phn ng xy ra. d) Tnh chn lc ca xc tc Tnh chn lc ca xc tc th hin ch, mt cht xc tc ch xc tc cho mt phn ng nht nh. V d 17: T CH3CH2OH khi dng cc xc tc khc nhau s thu c cc sn phm thch hp theo s
Cu t0 Al2O3 t0 Al2O3/ZnO t0
CH3CHO + H2 CH2 = CH2 + H2 CH2 = CH CH = CH2 + 2H2O + H2
CH3CH2OH
Tnh chn lc ca xc tc c tc dng nh hng cho phn ng xy theo chiu mong mun. ) Cht xc tc khng lm thay i tr s ca hng s cn bng K. Theo quan im ca nhit ng hc, hn s cn bng K ph thuc vo G ca phn ng theo phng trnh G0 = RTlnK. Tc l cht xc tc ch c tc dng lm thay i con ng ca phn ng, tc l lm thay i trng thi trung gian m khng lm thay i trng thi u v trng thi cui ca phn ng. Do , Cht xc tc khng lm thay i tr s ca hng s cn bng K. Theo quan im ca ng ha hc, hng s cn bng K c tnh theo biu thc K =
kt . Cht xc tc lm tng hng svn tc (kt) thun ln bao nhiu kn
ln th cng lm tng hng s vn tc nghch (kn) ln by nhiu ln, nn cht xc tc khng lm thay i tr s ca hng s cn bng K. Cho n nay, cha c mt l thuyt chung no v xc tc gii thch chung cho mi hot ng ca xc tc khc nhau. V th, chng ta cha hiu ht c cc quy lut hnh thnh ca cc hp cht trung gian. Do , c nhiu l thuyt khc nhau c a ra gii thch cho tng dng xc tc c th. 4.3. Xc tc ng th 4.3.1. Khi nim Cht xc tc nm cng pha vi cht phn ng c gi l xc tc ng th.
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gio trnh ho i cng
4.3.2. Mt s phn ng xc tc ng th a) Xc tc ng th trong pha lng. Xc tc axit baz S chung biu din qu trnh xc tc axit, nh sau:
A + H+ AH+ + B
k1
k2 = k
k3
1 1
AH+ AB + H+
(nhanh) (chm)
Phn ng xc tc axit baz rt ph bin nh: Phn ng este ha, phn ng halogen ha vo v tr ca hp cht mono cacbonyl, phn ng tch nc t ru, ... RCOCH3 + I2
H+
RCOCH2I + HI
OH Hoc RCOCH3 + 3I2 RCOCI3 + 3HI b) Xc tc ng th trong pha kh Cc qu trnh xc tc ng th t khi xy ra trong pha kh. V d 18: S nhit phn etanal vi cht xc tc l hi iot I2(h) CH4 + CO CH3CHO V d 19: S phn hy ozon vi xc tc l init pentaoxit N2O5 3O2 2O3 4.4. Xc tc d th 4.4.1. Khi nim Cht xc tc nm khc pha vi h phn ng c gi l xc tc d th Trong thc t, thng gp xc tc nm pha rn, cn h phn ng nm phan kh hoc pha lng. V d 15 l phn ng xc tc ng th, v d 16 l phn ng xc tc d th. Xc tc d th khng nhng c nhiu ng dng thc tin trong cng nghip ha cht m cn c vai tr to ln trong nghin cu l thuyt. 4.1.2. c im ca xc tc d th + Phn ng xc tc xy ra trn b mt phn chia cc pha. + Phn ng xc tc d th gm nhiu giai on vt l v ha hc ni tip nhau. V vy, ty thuc vo iu kin phn ng m vn tc ca phn ng s c quyt nh bi giai on chuyn cht ti min phn ng (giai on khuch tn) hoc giai on xc tc b mt. + Cht xc tc c rt nhiu dng nh: kim loi (kim loi dng bt, cc kim loi trn cht mang, kim loi xp,...), cc oxit ( dng v nh hnh hoc dng tinh th, oxit axit hoc oxit baz c cu trc c kht hay c cu trc mao qun, dn in, bn dn hay cch in,...), cc zeolit, cc hirotanxit,... xt v phng din bn cht tm hot ng xc tc, cc hp cht trung gian b mt, th xc tc d th l mt lnh vc cc k phc tp. Cho nn, khng c mt l thuyt chung no cho xc tc d th t c th gii thch mi hnh vi ca xc tc,
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tin on, la chn cng nh iu ch xc tc tt cho cc phn ng ha hc. + Hp ph: L mt giai on quan trng ca xc tc d th. Ngi ta cho rng, cc cht lng hoc cht kh phi c hp ph ln trn b mt cht rn th mi c th dn n cc hot ng xc tc. 4.1.3. Mt s xc tc d th
Mt s bi tp: Bi 1. Th no l vn tc phn ng? hng s vn tc ca phn ng ha hc. Ti sao ni: hng s vn tc l vn tc ring ca phn ng. Cc yu t nh bn cht ca cc cht phn ng, nng ca cht phn ng, p sut nhit , xc tc nh hng nh th no n vn tc, hng s vn tc ca phn ng? Bi 2. Cho phn ng: H2(k) + I2(k) 2HI(k) (*) a) Vit biu thc ca nh lut tc dng khi lng i vi phn ng cho, Bit rng: + Tng nng ca H2 ln gp i v gi nguyn nng ca I2 th vn tc tng gp i. + Tng nng ca I2 ln gp i v gi nguyn nng ca H2 th vn tc cng tng gp i. Tnh bc ca phn ng i vi H2, I2 v bc ca phn ng. b) Phn ng (*) l phn ng n gin hay phc tp? c) 5080C khi nng cc cht tc dng [I2] = 0,05M, [H2] = 0,04M th vn tc ca phn ng bng 3,2.10-4 mol.l-1.s-1. Nu hn hp ban u c nng cc cht tc dng u bng 0,04M th cn phi mt thi gian bao lu cho 50% H2 phn ng? 75% H2 phn ng? d) Vn tc ca phn ng (*) s thay i nh th no nu th tch ca h phn ng gim xung 2 ln. ) C phn ng sau: H2(k) + Br2(k) 2HBr(k) (**) 1 2 Phng trnh biu th vn tc ca phn ng c dng: v = kC H C H2 Vy phn ng (**) l phn ng n gin hay phc tp?
2 2
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Bi 3. Khi tin hnh phn hu (CH3)2O trong 1 bnh kn 5040C v o p sut tng qut ca h , thu c kt qu : T(s) 0 1550 3100 400 800 1000 PT(mmHg) Da vo kt qu trn hy : a) Chng minh l bc nht b) Tnh hng s tc 5040C. c) Tnh p sut tng trong bnh v lng % (CH3)2O phn hu sau 460s. Bit: (CH3)2O CH4 + H2 + O2 p s:t1/2 = 1550s , k = 4,47.10-4s-1, PT=549,6 mmHg. Bi 4: Hot tnh phng x ca ng v 84Po210 gim 6,85% sau 14 ngy. Xc nh hng s vn tc phng x ca qu trnh phn hu 84Po210, thi gian na phn ng v thi gian cn thit 84Po210 phn hy 90%. p s: k= 0,00507 ( ngy)-1 t1/2 =137 ngy t = 454 ngy. Bi 5: Khi tin hnh phn ng ng phn hu CH3OCH3 theo thi gian, thu c kt qu sau: T( thi gian) 0 15 30 C(mol/l) 25,4 9,83 3,81. Xc nh xem bao nhiu lu lng CH3OCH3 gim 1 na v sau bao lu gim 1%. Bit : CH3OCH3 C2H4 + H2 + CO p s: k= 0,0633 pht-1, t1/2 =10,95 pht, t = 0,15 pht.
Mt s bi tp mu: Bi 6: Tnh h s nhit ca tc phn ng trong cc trng hp sau: a, 288K hng s tc ca phn ng = 2.10-2 s-1 cn 325K th = 0,38s-1
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b, Khi h nhit xung 450, phn ng chm i 25 ln c, 393K phn ng kt thc sau 18 pht, 453K phn ng kt thc sau 1,5s Bi 7: Cho phn ng A ? B + C l phn ng bc 1 288K c h/s tc = 2.10-2.s-1 cn 325K th = 0,38s-1 a, Tnh Ea ca phn ng b, Tnh thi gian phn ng hon thnh c 50%, 75% 303K Bi 8: Cho phn ng: 2N2O5 ? 4NO2 + O2 xy ra T(K). Cc kt qu thc nghim sau y c ghi nhn CN2O5 (mol/lit) vp (mol.l-1.s-1) 0,170 1,39.10-3 0,340 2,78.10-3 0,680 5,56.10-3 a, Vit biu thc ca tc phn ng b, Tnh hng s tc nhit T(K) c, Ea = 24,74 kcal.mol-1, hng s tc ca phn ng 298K bng 2,03.10-3s1. Tnh nhit T tin hnh th nghim. Mt s bi tp mu
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Chng 7 dung dch 1. Mt s khi nim chung v dung dch 1.1. H phn tn 1.1.1. nh ngha H phn tn l h trong mt hoc vi cht no phn b trong mt cht khc (mi trng) di dng nhng ht nh. V d: Dung dch NaCl - NaCl: cht phn tn - H2O: mi trng 1.1.2. Cc loi h phn tn: Ph thuc vo kch thc ht phn tn a. H phn tn th: Kch thc ht phn tn t 10-7 ? 104m: ln, khng bn. V d: huyn ph, nh tng, b. Dung dch keo: Kch thc ht phn tn t 10 -7 ? 10 9m: nh, tng i bn. V d: mc vit, mc bt bi, c. Dung dch tht: Kch thc ht phn tn khong 10 10(kch thc ca phn t) Dung dch tht l h ng th m cht phn tn tn ti dng phn t, nguyn t hoc ion. Dung dch tn ti 3 th: kh, lng, rn 1.2. Dung dch bo ho 1.2.1. Cn bng ho tan M(rn) M(dd) T =const
Khi t n trng thi cn bng (TTCB) th Vho tan = Vkt tinh C M dd max 1.2.2. Dung dch bo ho (DDBH): L dung dch ng vi TTCB ho tan c thit lp ti mt nhit xc nh c im: cht tan khng tan thm c 1.2.3. Dung dch cha bo ho: l dung dch cha t ti TTCB ho tan c im: cht tan cn tan thm c v C CT < C max 1.3. Nng dung dch - tan 1.3.1. Khi nim: Nng dung dch l lng cht tan c trong 1 lng dung dch dung mi hoc dung dch. 1.3.2. Cc cch biu din nng dung dch: a. Nng phn trm: s gam cht tan c trong 100g dung dch. C% = ( khng c n v) b. Nng mol ( M hoc CM): S mol cht tan trong 1 lt dung dch. CM = c. Nng mlan ( m hay Cm): S mol cht tan trong 1 kg dung mi (1000g dung mi). Cm = .
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d. Nng phn mol(X) : l s mol ca cht i chia cho tng s mol ca tt c cc lng phn ca d d.( k c dung mi) Gi s dung dch (h) gm n cht 1,2,3 th: X1= Do : Xi = , 0<Xi<=1, . . Nng ng lng (N hoc CN): s ng lng cht tan c trong 1 lt dung dch. CN = s ng lng cht tan / V( lt d d ) ( lg/lit). 1.3.3. Dung dch qu bo ho: Cct > C CT ca dung dch bo ho. Cch iu ch: ho tan nhit cao ri h nhit dn n nhit thp c im: khng bn d tr v dung dch bo ho. V d: Dung dch bo ho 1000C cha 231g Na2S2O3/ 100 ml H2O Dung dch qu bo ho 250C cha 231g Na2S2O3/ 100 ml H2O Gy mm kt tinh: dung dch bo ho 250C 50g Na2S2O3/ 100 ml H2O v 181g Na2S2O3 kt tinh 1.3.4. tan (S) v cc yu t nh hng a. tan: ca mt cht l nng dung dch bo ho cht ti mt nhit xc nh Thng thng: c biu din bng s gam cht tan/100 gam dung mi Quy c: S > 1 : cht tan 10 3< S < 1: cht t tan S < 10-3 b. Cc yu t nh hng n tan Bn cht ca cht tan: cc cht c xu hng tan nhiu trong cc dung mi c tnh cht ging vi chng. Nhit : - Cht rn: nhit tng th tan tng. - Cht lng: + Tan v hn: nhit khng nh hng. + C gii hn: nhit tng th tan tng. - Cht kh: Kh ? Kh ; ?Hht<0 (B mt lng) (trong dung dch) Khi nhit tng th tan gim, p sut tng th tan tng. m=k.P (biu thc ca nh lut Henry. Trong : m: nng molan. k: h s t l. P: p sut. Nhn xt nh vy mun ho tan kh th phi h nhit v tng p sut. 1.3.5. Dung dch l tng v dung dch tht a. Dung dch l tng: ?H = 0, ?V = 0. b. Dung dch tht: ?H ? 0, ?V ? 0. Bi tp p dng: a) Xc nh s gam CaCl2.6H2O iu ch c 200ml dung dch CaCl2 30% (d = 1,282). T tnh CM, CN, X v Cm.
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b) Trong phn th nghim c sn H2O, dung dch CaCl2 20% (d = 1.177) vi dung dch CaCl2 40% (d = 1,396). Tm cch pha 200ml dung dch trn bng 2 cch n gin khc nhau. 2. DUNG DCH ChA CHT TAN KHNG IN LY, KHNG BAY HI Dung dch ca cc cht tan khng in ly, khng bay hi c mt s tnh cht ph thuc vo bn cht ca cht tan m ch ph thuc vo nng ca n. l cc tnh cht: Phbh, tng t0s, gim nhit ng c v p sut thm thu 2.1. S gim p sut hi bo ho ca dung dch. nh lut Raoun 1 2.1.1. p sut hi bo ho: L p sut m ti cn bng lng hi c thit lp ti mt nhit xc nh L H 2.1.2. S gim p sut hi bo ho ca dung dch. nh lut Raoun 1 Khi cho thm mt t cht tan khng in ly, khng bay hi vo dung mi th cht tan c mt phn lng, khng c mt phn hi. Dung dch thu c l dung dch long (~ vi dung dch l tng) Pt < P0. Pt = PA0.XA XA: nng phn ca s mol ca dung dch. 2.2. tng t0s v gim t0 ca dung dch (nh lut Raoun 2): H qu ca s gim p sut hi lm cho t0s ca dung dch tng ln v t0 ca dung dch h xung ?ts = Ks.Cm ?t = K .Cm Ks, Km: ph thuc bn cht ca dung mi. 2.3. p sut thm thu 2.3.1. Mng bn thm: mng bn thm l nhng mng mng c c im l ch cho cc phn t dung mi qua n m khng cho phn t cht tan qua. V d: Bong bng ng vt, da ch, mng xp bng t st c tm Cr2[Fe(CN)6] 2.3.2. S thm thu: s thm thu l s thm dung mi qua mng bn thm t phn dung dch long sang phn dung dch c 2.3.3. p sut thm thu Th nghim: Cho dung mi c 2 nhnh
Khi cha cn bng Khi cn bng Dung mi thm dc qua mng, cht tan khng thm c qua mng. Nng cht tan nhnh B c hn nhnh A dn n hin tng dung mi thm thu quan mng bn thm t nhnh A sang nhnh B lm cho nng cht tan
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nhnh A tng ln cn nhnh B gim i. n khi t n trng thi cn bng th p sut tc dng ln b mt dung dch bng nhau. Ch u khi: trng lng ca phn cao hn ca cht lng nhnh B gy ra 1 p sut lm cho tc khuych tn dung mi t A ? B bng t B ? A, ngha l t ti trng thi cn bng th hin tng thm thu dng li Ch : nu 2 nhnh A, B cha dung dch vi nng khc nhau, cng xy ra hin tng tng t, vn tc khuych tn dung mi t pha dng dch long sang pha dung dch c ln hn t pha dung dch c sang dung dch long. n khi t c cn bng th nng 2 bn bng nhau. Vy p sut thm thu: l p sut cn tc ng v dung dch lm cho hin tng thm thu khng xy ra. Cng thc tnh: ?.v=nRT hay =C.RT y ? l p sut thm thu, v l th tch ca dung dch, n l s mol cht tan, T l nhit v R l hng s kh. 2.3.4. Xc nh phn t khi ca cht tan khng in ly, khng bay hi Da vo nh lut Raun-1, Raun-2 v p sut thm thm ?. + Da vo Raun-1: + Da vo ?ts, ?t: + Da vo p sut thm thu: 3. dung dch in ly 3.1. Tnh cht ca dung dch in ly a. Dung dch in ly dn c in b. Dung dch nc ca mui, axit, baz lun c: gim p sut ( P), tng nhit t0C; gim nhit t0 . c xc nh bng thc nghim ln hn cc gi tr l thuyt tnh theo Raun-1, Raun-2 v Vanhp. V d: c 0,1 mol KBr/1kgH2O t(tn) =0,3380, t (lt) =0,1860 Vy: s tiu phn t c mt trong dung dch KBr =1,82.0,1.6,022.1023 , tc l ln bng 1,28 ln s phn t c trong dung dch nn cho rng 0,1 mol KBr ho tan thnh 0,1.6,022.1023 phn t KBr. H s vanhp i = t (tn)/ t (lt)=. 3.2. Thuyt in ly 3.2.1. Ca Areniuyt: - Khi ho tan vo H2O, cc phn t axit, baz, mui b phn ly thnh ion. Kt qu: tng in tch (+) = tng in tch (-), dung dch trung ho v in. - S phn ly phn t cht in ly thnh ion l khng hon ton (0<?<1) v c c trng bng h s in ly K. u im: Gii thch c s tng ?t. ?p Gii thch c tnh dn in ca dung dch in ly. Nhc im: Cha ch r c nguyn nhn ca s in ly. B qua tng tc quan trng ca ion dung mi, ion ion, Ch ng vi dung dch nc.
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3.2.2. Ca Calcp - Tha nhn mi thnh tu ca Areniut. - B sung: Nguyn nhn ca s in ly l s tng tc ca phn t cht tan v dung mi V d: NaCl ? Na+ + Cl- Areniut NaCl + (n+m)H2O ? Na+(H2O)m + Cl-(H2O)n Calcp 3.3. in ly () v hng s in ly (K) 3.3.1. in ly: l t s gia s phn t b phn ly chia cho tng s phn t cht ha tan.
C: nng phn ly. C0: nng ban u. T nh ngha d thy: 0???1 ?=0: cht tan khng phn ly. ngha ca : c trng cho kh nng dn in mnh hay yu ca dung dch in ly. Phn loi cht in ly da vo : : cht in ly yu : cht in ly trung bnh : cht in ly mnh Cht in ly mnh: khi tan phn ly hu nh hon ton thnh ion. Cht in ly yu: khi tan phn ly 1 phn thnh ion. 3.3.2. Hng s in ly (K): xt qu trnh phn ly ca cht in ly yu ca AB. AB ? A+ + BTa c : K = ( l hng s in ly) ngha: K cng ln th cht in ly cng mnh. Quan h ca K vi G0 : G0 = -RTlnK. K ph thuc vo bn cht ca cht in ly, nhit . Lu : so snh K bit c cht no in ly manh hn. V d: HNO2 ?H++NO2-, K= 7,2.10-4 250C HCN ? H++CN-, K = 7,2.10-10, 250C. HNO2 l cht in ly mnh hn HCN. 3.3.3. nh hng ca nng dung dch n dung dch in ly Xt: AB ? A+ + BBan u: C0 Phn ly: C Cn bng [i]: C0-C C C M C0 = C Ta c: K = = , C0: l nng ban u ca AB khi cha phn ly. Nu AB l cht in ly yu v : <<1 th 1- 1 Nn: K = C.a2 ? Nu V l th tch (lt) cha mt mol cht tan, suy ra V= 1/C, khi : (biu thc ca nh lut Ot-van)
? C=?.C0
Trong :
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V tng th a tng v C gim. Ch : s pha long khng bin cht in ly yu thnh cht in ly mnh c. 3.4. Cn bng trong dung dch axit v baz 3.4.1.Thuyt v axit v baz a. Ca areniut (1859-1927): nh ho l Thu in tc gi thuyt in ly (1887). nobel ho hc 1903. + Axit: l nhng cht khi ho tan trong nc phn li cho ion H+ + Baz: l nhng cht khi ho tan trong nc phn ly cho ion OHV d: HCl H+ +ClNaOH Na+ + OHu im: gii thch c nhng d kin thc nghim nh: dung dch axit u c tnh cht ging nhau (tnh cht ca ion H+), dung dch baz u c tnh cht ging nhau (tnh cht ca ion OH-). Nhit ca phn ng gia axit v baz bng nhau v bng -57,6kj/mol. Nhc im: khng gii thch c nhng d kin thc nghim nh: axit tc dng vi baz m khng phi phn ly thnh ion, nhng cht trong phn t khng c nhm OH- (nh NH3, Na2CO3) vn th hin tnh baz Mt im hn ch ln nht l ch ng vi dung mi nc. b. Thuyt Bonsted v Laory + Axit: cht cho proton. + Baz: l cht nhn proton. V d 1: HNO3 +H2O H3O+ +NO3NaOH +(n+m)H2O Na+(H2O)m + OH-(H2O)n. OH- nhn H+ theo phng trnh: OH- +H+ =H2O Vy OH- l baz. V d 2: NH3 +H2O ?NH4+ +OH3.4.2.cp axit baz lin hp. * Baz lin hp l phn cn li khi mt H+ c tch ra khi axit. V d: Cl- l phn cn li ca HCl. H2O l phn cn li ca H3O+. * Axt lin hp l kt qu ca s gn 1 proton vo baz. V d: NH4+ l baz lin hp ca NH3 H2O l baz lin hp ca OH_. Cp axit-baz lin hp : HCl/Cl_ ; H3O+/H2O . Kt lun: Mi axit Bronsted c 1 baz lin hp vi n. Mi baz Bronted c 1 axit lin hp vi n. V d: CH3COOH + H2O ?CH3COO- + H3O+ Axit1 baz2 baz1 axit2 3.4.4. Thuc tnh axit baz ca H2O: H2O va l axit, va l baz. V d: HCl + H2O H3O+ + Cl_ NH3 + H2O NH4+ + OHH2O km dn in v l cht in ly yu; Do c phn ng: H2O +H2O ? H3O+ + OH-(*) S t ion ho ca H2O. Axit1 baz2 axit2 baz1
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Vn o c hng s K 250C. KC = 250C. V H2O l cht in ly rt yu (K=3,24.10-18) nn coi nng H2O khng i v: c gi l tch s ion ca nc, KW ch ph thuc vo nhit . Nn dung dch trung tnh : =10-7 Dung dch axit: Dung dch baz: 3.4.5. Thang pH: pH =-lg Nhn xt 1: pH l nhng s dng ch khi c gi tr rt nh. pH khng c th nguyn. Nhn xt2: da vo pH bit c 1 dung dch c mi trng l axit, baz hay trung tnh. + Baz pH >7. + Axit pH<7. + Trung tnh pH=7. 3.4.6. Axit mnh v baz mnh: l nhng cht in ly mnh phn ly hon ton thnh ion tan trong H2O. HCl +H2O =H3O+ + ClKhi cn bng, dung dch axit mnh khng cn cha cc phn t ca axit khng phn ly. Vi baz mnh cng vy: NaOH =Na+ + OHBa(OH)2 = Ba2+ + 2OH*Axit yu v baz yu phn ly rt hn ch trong H2O. Khi cn bng dung dch cha l cc phn t axit khng phn ly, cc ion H3O+ , ion baz lin hp. Vi baz yu cng vy. V d: CH3COOH + H2O ? H3O+ + CH3COONH3 +H2O ? NH4+ + OHCh : Nu l axit mnh th baz lin hp vi n rt yu. Nu l baz mnh th axit lin hp vi n rt yu. 3.4.7. Axit yu v baz yu. Hng s phn li K axit v K baz a. Axit yu: Xt s phn ly ca axit yu HA trong nc (?<1) HA +H2O ?H3O+ +AK= n gin: K Ka cng ln th axit cng mnh v nng H+ cng cao. Vy axit mnh c ch s pKa nh. V d: Ka(CH3COOH) =1,8.10-5; pKa =4,8. Ka(HCOOH) = 1,7.10-4; pKa =3,8 suy ra: HCOOH>CH3COOH. Ch : Bit c nng ban u (C0) v pH th tnh c Ka. Bit c nng ban u (C0) v Ka suy ra: [i] v pH ca dung dch. b. Baz yu: Cch lm tng t axit yu.
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Xt baz yu B, ta c cn bng: B + H2O ?BH+ + OHK= (*) Hng s phn ly baz. c. Mi quan h gia Ka v Kb: Xt BH+ l axit lin hp ca B, ta c: BH+ + H2O ?H3O+ + B Ka ca HB l: Ka = Nhn hai v vi KB c: V d: K =5,7.10-9 3.4.8. Tnh cht axit, baz ca mui. S thu phn nh ngha: Mui l sn phm ca phn ng gia mt axit v mt baz. Cu to: mui l hp cht ion. c im: + L cht in ly mnh. + Trong mt s trng hp mui cn phn ng vi dung mi (H2O). Trng hp ny gi l s thu phn ca mui: l phn ng ion dng hoc ion m do mui phn ly ra vi dung mi nc. Kt qu: S thu phn lm cho pH ca dung dch thay i. Xt mt s trng hp thu phn ca mui: a. Mui khng lm thay i pH khi ho tan: NaCl, NaNO3 ... b. Mui to mi trng baz (pH>7) khi ho tan: CH3COONa c. Mui to mi trng axit (pH<7): NH4Cl .. d. S thu phn mui to bi 1 axit yu vi 1 baz yu: NH4CH3COOH Trng hp ny c cation v anion u phn ng vi H2O. Nu xt nh tnh ch cn so snh Ka v Kb s bit c mi trng l axit, baz hay trung tnh. Kb > Ka dung dch l baz. Kb < Ka dung dch l axit. Kb = Ka dung dch trung tnh. 3.4.9. Dung dch m Dung dch m l dung dch cha mt hn hp ca axit yu v baz lin hp vi n hoc hn hp ca baz yu v axit lin hp. Hn hp ny c kh nng chng li mi bin i pH do mt lng nh axit hoc baz thm vo hn hp. V d: n . CH3COONa = CH3COO- + Na+ Nu thm axit (H+) vo th CH3COO- +H3O+ = CH3COOH + H2O Nu thm baz (OH-) vo th CH3COOH + OH- = CH3COO- +H2O Ch : biu th hiu qu ca dung dch m cn s dng i lng dung lng m + Dung lng m: ph thuc vo lng axit v baz lin hp c dng ch to h m. Lng cng ln th dung lng cng ln. + pH ca dung dch m c xc nh bng phng trnh: pH =pka + lg([baz lin hp ]/[axit])
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T phng trnh, nhn thy: pH = pKa khi [baz lin hp] = [axit] suy ra: mun c dung dch m c pH mong mun, ch cn chn 1 axit c Pka pH cn iu ch h m. 3.5. Thuyt axit v baz ca Liuyt Axit l cht c th nhn cp e suy ra c AO trng. Baz l cht c th cho cp e suy ra c cp e khng lin kt. V d: H3N +H+ =NH4+ Phn ng axit-baz Liuyt l phn ng c s chuyn cp e phn chia t cht ny sang cht khc. Kt qu: Khng to ra mui, khng sinh ra H2O. V d: F3B + :NH3 = F3B-NH3 3.6. Dung dc cha cht in ly t tan 3.6.1. Tch s tan: Xt cht in ly t tan MXAY(r) MXAY(r) ? xMy+ + yAxT Tch s tan ca MXAY Vy tnh s tan (T) l tch nng cc ion ca n trong dung dch bo ho mt nhit xc nh. Tch s tan ph thuc vo: bn cht ca cht tan, bn cht ca dung mi, nhit . 3.6.2. Quan h gia tch s tan (T) v tan (S) T v S u c trng cho kh nng ho tan ca cht. T ch phn nh tan ca cht trong dung dch bo ho nhit cho. S trc tip ni ln lng cht tan c mt trong dung dch bo ho nhit . Ch : T dng so sch tan ca cc cht vi nhau. Mun so snh chn cc cht c cng dng cng thc. V d 1: AgCl v ZnS, CaF2 v Fe(OH)2 . V d 2: 250C, tan ca PbSO4 trong H2O l 4,25.10-3 g/100ml nc. Hy tnh TPbSO4 t0C . Gii: Chuyn tan ra nng mol/l , M = 303,3g/mol S= PbSO4 ?Pb2+ + SO42V d 3: Tm tan ca AgCl trong dung dch bo ho 250C, bit T ca AgCl l: 1,8.10-10 Gii: Gi S l tan, t cn bng; ta c: AgCl ?Ag+ +Cls s T = s.s =s2 V d 4: 250C, tch s tan ca BaCrO4 l 1,2.10-10 ca Ag2CrO4 l 2,5.1012. a. Mui no tan trong H2O nhiu hn.
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b. Mui no tan nhiu hn trong dung dch cha CrO42- 0,1M. c. So snh tan ca cc mui trong 2 dung dch trn? gii thch? Gii: a. Tnh tan ca BaCrO4 v Ag2CrO4 trong H2O. BaCrO4(r) ?Ba2+ + CrO42Ag2CrO4(r) ? 2Ag+ + CrO42Vy: trong nc, Ag2CrO4 tan nhiu hn BaCrO4 gn 8 ln. b. Gi tan ca BaCrO4 v ca Ag2CrO4 trong dung dch CrO2-40,1M ln lt l: Sa, Sb Nng ca ion Ba2+trong dung dch bng Sa (mol/lt), ion Ag+ trong dung dch bng Sb (mol/lt). T V Sa 1,1.10-5 ? 0,1 + Sa ? 0,1 T Sa = Vy mc d T Nhng Ag2CrO4 li tan nhiu hn BaCrO4 >2000 ln (trong dung dch CrO4- 0,1M). c. S u gim khi c mt ca ion ng dng (CrO42-); Cn bng nh lng chuyn dch v bn tri 3.6.3. Tnh s tan v s kt ta Tnh s cc nng ion ca mi dung dch cha bo ho hoc t ti cn bng c gi l tch s ion. C dung dch bo ho. < T Dung dch cha bo ho. >T S xut hin kt ta CaSO4, v dng li. Khi C V d: Hy cho bit nhng g xy ra khi thm t t Na2CO3 rn vi dung dch cha ng thi ion Ba2+ 0,1M v ion Sr2+ 0,1M. bit: T Gii Xt 2 cn bng BaCO3?Ba2++ CO32SrCO3 ?Sr2+ + CO32T T - Khng c hin tng g xy ra khi C M. - Khi C = 5,2.10-9M , th C .C =T bt u xut hin kt ta. - SrCO3 tip tc kt ta khi C tng ln - Khi C t ti 2.10-10 M khi C th c BaCO3 v SrCO3 cng bt u gim . 3.6.4. Tnh s tan v s ho tan cc kt ta: Cc hp cht ion t tan trong nc c th c ho tan vo dung dch bng mt vi cch.
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Nguyn tc chung: lm gim nng ca 1 hoc c 2 ion bng phn ng ho hc sao cho tch s ion ca chung nh hn tch s tan. V d 1: Cho 0,01 mol Fe(OH)3 vo mt lt H2O. Hi cn phi thm axt mnh vo n pH bng bao nhiu ho tan hon ton khi lng Fe(OH)3. Bit T Gii Fe(OH)3 ?Fe3+ + 3OHT = =3.10-39, Khi Fe(OH)3 va tan ht th [Fe3+][OH-]3 =T Theo [Fe3+] = 0,01M nn [OH-] = M. Tnh [H+] da vo Vy: Phi thm axit mnh vo dung dch n pH =1,83 th 0,01 mol Fe(OH)3 mi tan ht. Chng 8 PHN ng oxy ho - kh v dng in 1. Phn ng oxy ho kh 1.1. S oxi ho (Mc oxi ho, bc oxi ho hay trng thi oxi ho). S oxi ho ca mt nguyn t trong hp cht l in tch ca nguyn t ca nguyn t trong phn t ca hp cht vi gi thit cc phn t u l lin kt ion. Vi khi nim va nu, ngi ta quy c mt cch hnh thc cp electron lin kt gia hai nguyn t c chuyn hn cho nguyn t ca nguyn t c m in hn. Khi , s oxi ho c th l s dng, s m hoc s khng. Quy c, cc phn t n cht c s oxi ho bng 0 v cp electron lin kt khng lch v pha nguyn t no. V d nh kim loi Na, Fe, Cu,... c s oxi ho bng 0, cc kh O2, Cl2, H2,... cng c s oxi ho bng 0. i vi cc hp cht ion c to thnh t cc ion n nguyn t th s oxi ho ca nguyn t bng in tch ca ion. Th d, trong hp cht NaCl th s oxi ho ca Na bng +1 v ca Cl bng 1. Trong mt hp cht th tng s s oxi ho ca cc nguyn t bng khng, cn trong mt ion tng s s oxi ho bng in tch ca ion. S oxi ho ca Oxi l -2 nu oxi lin kt vi cc nguyn t c m in b hn n, cn vi hir l +1 nu hiro lin kt vi cc nguyn t c m in ln hn n. Th d 1: Xc nh s oxi ho ca N trong axit HNO3 t s oxi ho ca N l x, ta c: (+1) + x + 3.(-2) = 0 ? x= +5 Th d 2: xc nh s oxi ho ca Cr trong ion Cr2 Tng t: 2x + 7(-2) = -2 ? x = +6 i vi cc cht c cha nhiu nguyn t ca cng mt nguyn t, nhng chng li cc trng thi oxi ho khc nhau. Trong trng hp ny, xc nh s xi ho ca nguyn t khng p dng c quy tc trn (v khi p dng ch xc nh
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c s oxi ho trung bnh ca nguyn t) m phi da vo cng thc cu to ca cht . Th d 3: Xc nh s oxi ho ca cacbon trong anehitaxetic. Anehit axetri c cng thc cu to:
Trong cng thc ny, cacbon ca nhm CH = 0 c s oxi ho +1 cn cacbon ca nhm CH3 l -3. Nu xc nh theo nguyn tc trn th s oxi ho trung bnh ca cacbon trong CH3CHO s l -1 (tc l bng (-3+1):2 = -1). Th d 4: Xc nh s oxi ho ca lu hunh trong axit thiosunfuric axit ny c cu to tng t nh axit sunfuric, nhng c m t c bi hai cng thc sau:
Trong cng thc (a) nguyn t S trung tm c s oxi ho +4, nguyn t S cn li c s oxi ho l 0. trong cng thc (b) nguyn t S trung tm c s oxi ho l +5 v nguyn t S kia l -1. Da vo s thay i s oxi ho ca cc nguyn t khi tham gia phn ng c th phn chia cc phn ng ho hc thnh 2 loi: loi th nht khng c s thay i s oxi ho c gi l phn ng trao i, loi th 2 c s thay i s oxi ho ca mt nguyn t c gi l phn ng oxi ho kh. Khi nim s oxi ho cng gip phn loi cc cht, v d chng ta xp cc hp cht H3PO4 v H4P2O7 vo mt nhm v s oxi ho ca photpho bng +5 cn H3PO3 v H4P2O5 c xp vo mt nhm v s oxi ho ca photpho bng +3. Ngoi ra s oxi ho cn dng lm c s nh ngha phn ng oxi ho - kh v cn bng phn ng oxi ho kh theo phng php cn bng electron v phng php ion electron. 1.2. Phn ng oxi ho kh. Phn ng ho hc trong c s thay i s oxi ho ca cc nguyn t, c gi l phn ng oxi ho kh. Ni cch khc: phn ng oxi ho kh l phn ng trong c s cho v nhn electron. Th d: Phn ng oxi ho - kh no cng gm hai qu trnh: qu trnh oxi ho (s oxi ho) v qu trnh kh (s kh). Trong phn ng trn. Qu trnh oxi ho l : 2+: S oxi ho tng Qu trnh kh l: 2+ + 2e ? Cu0 : S oxi ho gim Phn ng: Fe + Cu2+ ? Fe2+ + Cu
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Trong phn ng trn, Fe tng s oxi ho c gi l cht kh (nhng e), cn Cu2+ gim s oxi ho c gi l cht oxi ho (nhn e). Qua vic phn tch trn, c th a ra cc nh ngha sau. Cht m trong thnh phn ca n c nguyn t tng s oxi ho c gi l cht kh. Qu trnh oxi ho (s oxi ho) mt cht l qu trnh lm tng s oxi ho ca nguyn t c trong thnh phn ca cht . Cht m trong thnh phn ca n c nguyn t gim s oxi ho c gi l cht oxi ho. Qu trnh kh (s kh) mt cht l qu trnh lm gim s oxi ho ca nguyn t trong thnh phn ca cht . Trong mi phn ng oxi ho - kh, qu trnh oxi ho v qu trnh kh c gi l hai na phn ng v nu cng hai na ny vi nhau s c phn ng oxi ho - kh. Trong qu trnh kh, cht oxi ho b kh v bin thnh cht kh cn trong qu trnh oxi ho, cht kh b oxi ho v bin thnh cht oxi ho, cht oxi ho v cht kh ca cng mt qu trnh hp thnh mt cp oxi ho - kh (c k hiu l Ox/kh). V th trong mt phn ng oxi ho kh phi c t nht hai cp oxi ho kh. v d trn, hai cp l Cu2+/Cu v Fe2+/Fe Nu dng oxi ho Ox1 ca cp Ox1/Kh1 oxi ho dng Kh2 ca cp Ox2/Kh2 th phn ng oxi ho - kh c vit dng tng qut nh sau: n1Ox1 + n2Kh2 n1Kh1 + n2Ox2 1.3. Cn bng phn ng oxi ho kh. C nhiu phng php cn bng phn ng oxi ho - kh. Trong gio trnh ny ch gii thiu hai phng php ch yu. Th nht l phng php cn bng electron, th hai l phng php cn bng ion-electron. a. Phng php cn bng electron. Phng php ny da trn nguyn tc tng s electron m cht kh nhng i bng tng s electron cht oxi ho nhn. Mun cn bng phn ng oxi ho kh bng phng php ny, trc tin phi vit ng phng trnh phn ng dng phn t sau xc nh ng s oxi ho ca cc cht kh v cht oxi ho. Trn c s tm h s ca cht kh, cht oxi ho ri cui cng cn bng s nguyn t hai v th s tm c y cc h s. V d: Cn bng phng trnh phn ng sau: Sau khi xc nh c s oxi ho, phi vit c hai qu trnh oxi ho v qu trnh kh: Xc nh bi s chung nh nht ca 3 v 4 l 12. Ly 12:3 ta c h s ca Al l 4 v 12: 4 ta c h s ca O2 l 3. a cc h s ny vo hai na phn ng trn ri cng hai na phn ng vi nhau, ta c:
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3Al + 3O2 ? 4Al3+ + 2O2Cui cng a h s tm c vo phng trnh trn, khi phng trnh c cn bng. 4Al + 3O2 ? 2Al2O3 V d 2: Cn bng phn ng sau: Sau khi xc nh s oxi ho ca cc nguyn t trong phn ng, ch thy c mangan v st thay i s oxi ho. Ta vit hai qu trnh kh v qu trnh oxi ho: Mn+7 +5Fe2+ Mn+2 + 5Fe+3 Bi s chung nh nht ca 5 v 1 l 5, t ta tm c cc h s cho hai qu trnh trn. Vic a h s vo phng trnh phi nhn tip vi 2 v cng thc ca Fe2(SO4)3 c 2 nguyn t st. 2KMnO4 + 10FeSO4 + H2SO4 ? 2MnSO4 + 5Fe2(SO4)3 + K2SO4 + H2O Tip theo tm cc h s cn li, bng cch cn bng cc nguyn t ca cc nguyn t khc, y l K, S, H v O. 2KMnO4 + 10FeSO4 + 8H2SO4 ? 2MnSO4 + 5Fe2(SO4)3 + K2SO4 + 8H2O n y phng trnh phn ng c cn bng xong. Trong phn ng ho kh, cht tham gia vo phn ng khng ch ng vai tr l cht oxi ho hay cht kh m n cn ng vai tr l mi trng cho phn ng. V d 3: 4 x Zn 2e ?Zn2+ 1 x N+5 + 8e ? N-3 4Zn0 + N+5 ? 4Zn+2 + N-3 Nh vy, trong 10 phn t HNO3 phn ng, ch c mt phn t HNO3 lm nhim v oxi ho km, 9 phn t cn li ng vai tr l mi trng ni cch khc 9 phn t ny c nhim v kt hp vi cc ion Zn2+ v cho dung dch trung ho v in. b. Phng php ion electron. Phng php ny c u im l khng cn xc nh s oxi ho, khng cn vit phng trnh phn ng dng phn t. Ch cn bit c hai cp oxi ho - kh phn ng vi nhau vn cn bng c v hon thnh c phn ng dng phn t. Mun thc hin theo phng php ny cn m bo nguyn tc: Cc cht in ly mnh dng ion; cc cht khng in ly, in ly yu, cht kh, cht khng tan dng phn t, tc l cc cht tn ti dng tht ca n. Th d: Cn bng v hon thnh phn ng sau dng phn t T s , ta thy: ion Cl- b oxi ho thnh Cl2 cn ion b kh thnh ion Mn2+. Tc l c 2 cp oxi ho - kh phn ng vi nhau, l cp Mn /Mn2+ v Cl2/ClBy gi ta vit hai qu trnh kh v oxi ho: Cl- ? Cl2 (qu trnh oxi ho)
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Mn ? Mn2+ (qu trnh kh) Cn ch , khi cn bng bt c mt na phn ng no cng cn phi m bo hai nguyn tc: Th nht phi bo ton khi lng (tc l phi lm th no cho s nguyn t ca cng mt nguyn t hai v ca na phn ng phi bng nhau); th hai phi bo ton in tch (tc l in tch hai v phi bng nhau). m bo nguyn tc trn, trc tin phi cn bng s nguyn t 2 v pha trc sau mi cn bng in tch. v d trn, thm 2 vo Cl- th c: 2Cl ? Cl2 Nh vy v tri mang 2 in tch m (2.(-1)=-2), cn v phi trung ho in, v vy cn phi bt i v tri 2 e th c 2 v u trung ho in: 2Cl- - 2e ? Cl2 qu trnh kh, Mn hai v cn bng, v vy phi cn bng oxi bng cch thm vo v phi 4H2O, ta c: Khi , v phi tha 8H nn phi thm vo v tri 8H+ th s nguyn t H hai v bngnhau. By gi cn bng in tch, ta thy v phi mang in tch l +2 cn v tri l +7. trung ho in cn thm vo v tri 5e, th c: Kt hp hai na phn ng ri cn bng s electron cho v nhn, cng hai na phn ng vi nhau th c phng trnh dng ion. 5 x 2Cl- 2e ? Cl2 1 x Mn + 8H+ + 5e ? Mn2+ + 4H2O 2Mn + 10Cl- + 16H+?2Mn+2 + 5Cl2 + 8H2O (phng trnh ion) Mun vit phng trnh phn ng dng phn t, ta thm vo hai v cng mt lng ion trung ho in tch ca cc ion c trong phng trnh ion, c hai v u thm 2K+ v 6Cl-, th c: 2KMnO4 + 16HCl ? 2HCl + 2MnCl2 + 5Cl2 + 8H2O Phng trnh c hon thnh. 2. mt s qu trnh in ho Nng lng ca phn ng ho hc c th bin i thnh cc dng nng lng khc nh in nng, quang nng, nhit nng v ngc li c th bin cc dng nng lng khc thnh ho nng. Nu phn ng ho hc m E ca n ? in nng: h in ho. Nh dng in m phn ng xy ra ? h in phn 2.1. Nguyn tc bin i ho nng thnh in nng * Xt th nghim: Nhng Zn vo dung dch CuSO4 Zn + Cu2+ = Zn2+ + Cu ; ?H0298 = -230,12 kj/mol Zn nhng e trc tip cho Cu (v: Cu2+ n b mt Zn nhn 2e ?Cu kt ta). Khi ny nng lng ca phn ng ho hc thot ra di dng nhit nng. Thnh phn h gm: - Zn, Cu: tip xc trc tip vi nhau. - Zn2+, Cu2+ cng nm trong 1 dung dch.
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* Mun bin nhit ca phn ng trn thnh in nng, ta lm nh sau: Cho: Zn nhng vo dung dch Zn2+ Cu nhng vo dung dch Cu2+ Ni Zn vi Cu bng dy dn Hai dung dch c thng vi nhau nh cu mui l ng hnh ch U p ngc trong ng dung dch cht in ly tr (NH4NO3, KNO3 , KCl,). Cu mui c tc dng khng cho 2 dung dch trn ho trn vo nhau, nhng vn cho php cc ion i t in cc ny sang in cc kia Nh vy: mun cho Nng lng ca phn ng ho hc bin thnh in th cht kh phi nhng e gin tip cho cht oxy ho nh mt cht trung gian (dy dn kim loi). bit: Mun cho e chuyn t Zn ? Cu th phi c s chnh lch v hiu in th gia Zn v Cu. Nguyn nhn no xin mi tm hiu phn tip theo. 2.2. Th in cc ? Nhng thanh kim loi M vo dung dch cha mui ca n (M2+) th gia b mt kim loi v dung dch bao quanh kim loi lun pht sinh mt lp in kp. Khi t n trng thi cn bng: M ? Mn+ + ne th s xut hin mt hiu in th cn bng v tr s ca hiu in th cn bng ph thuc Bn cht ca kim loi. Nng ca ion kim loi Mn+ Nhit . Hiu in th ny c biu th ra Vn (V) v c gi l th in cc. Ch : khng th o c gi tr tuyt i ca th in cc. 2.3. Cc loi in cc: 2 loi in cc loi 1: l in cc lm vic thun nghch vi cation kim loi. Gm c: in cc kim loi: Mn+/M, phn ng trao i: Mn+ + ne ? M in cc oxy ho - kh: Oxh, Kh/Pt oxh +ne ? kh in cc kh: iu ch hir H+/ H2, Pt: H+ + 1e ? 1/2 H2 in cc loi 2: L in cc lm vic thun nghch vi anion c cu to bi mt kim loi bn ngoi c ph bng mui kh tan ca kim loi v nhng vo dung dch cha anion ca mui kh tan. V d: a, Ag, AgCl\Cl-: AgCl + 1e ? Ag + Clb, iu ch Calomen: Hg, Hg2Cl2\ Cl-; Hg2Cl2 + 2e ? 2Hg + 2Cl- SO42c, iu ch thu ngn ISunphat: Hg, Hg2 SO4(r) \ SO42Hg2 SO4 + 2e ? 2Hg + SO42Ch : Nu Cion = 1M (hoc Pkh = 1atm) v lm vic 250C c gi l in cc tiu chun. 2.4. H in ho (Pin Ganvani, nguyn t Ganvani, nguyn t, pin) a. Cu to ca Pin Ganvani
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Gm 2 in cc ghp vi nhau nh: dy dn ni 2 in cc v cu mui ni 2 dung dch. b. Quy c quc t v cch vit pin in v hot ng ca pin in Ranh gii gia in cc v dung dch c k hiu bi: | 1 gch thng ng. Ranh gii gia 2 dung dch c k hiu bi: ? 2 gch thng ng. V d: Pin Zn-Cu (pin danien jacobi: tn ring) (-) Zn | Zn2+ ? Cu2+ | Cu (+) Epin = 1,1(V) >0 in cc tri bao gi cng l cc m: ti cc ny lun xy ra s oxi ho. in cc phi bao gi cng l cc dng: ti cc ny lun xy ra s kh. Phn ng xy ra trong pin th d trn (theo chiu t din bin) l: + Cc (-): Zn 2e ? Zn2+ + Cc (+): Cu2+ + 2e ? Cu Phng trnh phn ng: Zn + Cu2+ ? Zn2+ + Cu? c. Sc in ng ca Pin Epin = ?P - ?T = ?c(+)- ?c(-) Epin: sc in ng ca pin. ?P: th in cc ca in cc phi. ?T: th in cc ca in cc tri. Ch : bao gi cng xc nh c rt d dng gi tr Epin v ch cn mi dng c o vi 2 in cc. 2.5. Quan h gia ?G v E ?G = - nE.F ?G0 = - nE0.F 2.6. Phng php xc nh th in cc. Th in cc tiu chun a. Xc nh th in cc ca cc in cc Nh trn ni, khng th o c th in cc m ch o c sc in ng ca pin. V vy mun xc nh th ca cc in cc, phi tun th cc Quy c sau: Ghp in cc cn xc nh th vi in cc hir tiu chun (aH+= CH+ = 1M; PH2 = 1atm) t bn tri v iu chnh cch xc nh th t bn phi V d: Xc nh ?0Zn2+/Zn=? (-) Pt, H2 | H+ (1M)? Zn2+ (1M)| Zn (+) 250C, P=1atm. E0= ?P- ?T = ?0Zn2+/Zn- ?0H+/H2= -0,76(v) Phn ng xy ra trong pin l: H2 + Zn+ = 2H+ + Zn E0 = -0,76(V) <0 Vy ?0Zn2+/Zn=E0+?0H+/H2= -0,76 (V) + ?0H+/H2 Nu bit c ?0H+/H2 th s bit c ?0Zn2+/Zn. Thc nghim khng o c gi tr ?0H+/H2, vy phy chp nhn quy c ?0H+/H2= 0,00(V). Khi ?0Zn2+/Zn= E0=-0,76(V) Vy: Th in cc ca mt in cc chnh l sc in ng ca pin in c ghp in cc vi in cc hiro tiu chun c t bn tri b. Bng th in cc tiu chun v ngha ca n:
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Lm tng t nh trn, v xc nh c th in cc chun (th kh chun) ca phn ng: oxh + ne ? kh. Nu lp thnh bng (bng th in cc chun dung dch H2O 298K) 2.7. nh hng ca nng n Th in cc v sc in ng ca pin Phng trnh Nernet Cho phn ng: n1Oxh1 + n2Kh2 ? n1Kh1 + n2Oxh2 ?G = ?G0 + KT ln Ckh1n1. COxh2n2 COxh1n1. Ckh2n 2 ?G = - nE.F ?G0 = - nE0.F => Epin = E0pin - RT .ln Ckh1n1. COxh2n2 NF COxh1n1. Ckh2n 2 Cho na phn ng: oxh + ne ? kh Hay - nh hng ca s thay i nng . - nh hng ca s to thnh hp cht t tan. - nh hng ca s to hp cht phc. - nh hng ca mi trng. 2.8. Chiu v trng thi cn bng ca phn ng oxy ho kh a. Chiu ca phn ng oxy ho - kh: Chiu t din bin l chiu c : Nu E=0 th phn ng t ti trng thi cn bng Nu E<0 th phn ng xy ra theo chiu nghch c. Hng s cn bng (K) ca phn ng oxi ho - kh
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mc lc Chng 1: Cc khi nim v nh lut c bn ca ho hc Trang 1 1. Cc khi nim c bn 1 1.1. Cht 1 1.2. Nguyn t, nguyn t, phn t 1 1.2.1. Nguyn t 1 1.2.2. Nguyn t ho hc 2 1.2.3. Phn t 2 1.3. Khi lng nguyn t, khi lng phn t, khi lng mol 2 1.3.1. Khi lng nguyn t 2 1.3.2. Khi lng phn t 3 1.3.3. Mol - Khi lng mol 3 1.4. ng lng 3 1.4.1. ng lng ca mt nguyn t 3 1.4.2. ng lng ca mt hp cht 3 1.4.3. Cch tnh ng lng 4 1.4.4. ng lng gam 4 1.4.5. S ng lng gam 4 2. H n v o lng quc t (H SI) 4 2.1. Cc h n v c bn 4 2.2. H n v dn xut c suy ra t n v c bn 4 2.3. Mt s n v phi SI thng gp 4 3. Mt s nh lut c bn ca ha hc 5 3.1. nh lut bo ton khi lng 5 3.2. nh lut thnh phn khng i 6 3.3. nh lut t l bi 7 3.4. nh lut Avgaro 7 3.5. nh lut ng lng 7 4. Mt s phng php xc nh khi lng mol phn t ca cht kh v cht lng d bay hi 8 4.1. Da vo t khi hi 8 4.1.1. Khi lng ring ca mt cht kh 8 4.1.2. T khi hi 8 4.2. Da vo phng trnh trng thi8 5. Mt s phng php xc nh nguyn t khi ca cc nguyn t 8
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5.1. Phng php Canizaro 8 5.2. Phng php uy Lng- Pti 9 5.2.1. Phng php uy lng- Pti 9 5.2.2. Phng php uy Long- Pti kt hp vi ng lng 9 5.3. Phng php khi ph 10 Chng 2: Cu to nguyn t v h thng tun hon cc nguyn t ho hc 11 1. Mt s vn tin c hc lng t cu to vt cht 11 11 1.1. Lng tnh sng ht ca nh sng. Thuyt lng t ca M. Planck 1.1.1. Thuyt sng nh sng 11 1.1.2. Thuyt lng t ca M. Planck 11 1.2. Bn cht sng v ht ca cc ht vi m. Thuyt bri 11 1.2.1. Bn cht sng- ht ca cc ht vi m 11 1.2.2. Thuyt bri 12 1.3. H thc bt nh Haizenbec 12 2. Mt s nguyn l v tin ca c hc lng t 14 2.1. Tin v hm sng v nguyn l chng cht trng thi 14 2.1.1. Tin v hm sng 14 2.1.2. Nguyn l chng cht trng thi 14 14 2.2. Tin v phng trnh String 2.2.1. Phng trnh String 15 2.2.2. Bi ton ht chuyn ng t do trong hp th mt chiu 15 3. H 1e, 1 ht nhn 18 3.1. Mt s khi nim cn bit 18 3.1.1. Trng xuyn tm 18 3.1.2. H 1e, 1 ht nhn 18 3.2. Bi ton h 1e, 1 ht nhn 18 3.3. p dng kt qu ca bi ton h 1e, 1 ht nhn gii thch quang ph vch ca nguyn t 23 3.3.1. Cc trng thi nng lng ca e trong nguyn t H 23 23 3.3.2. Ph pht x ca nguyn t H 3.4. Cc khi nim c bn c rt ra t vic gii bi ton h 1e, 1 ht nhn 24 3.4.1. Cc Obitan nguyn t, ngha, cch biu din 24 3.4.2. th hm mt xc sut theo gc 24 3.4.3. Sprin ca e, hm Obitan-Spin (ASO) 24 3.4.4. ngha ca cc s lng t 25 4. Nguyn t nhiu electron 26 4.1. M hnh cc ht c lp (m hnh trng xuyn tm) cc Obitan nguyn t 26 4.1.1. Nhn xt 26 4.1.2. M hnh cc ht c lp 26 4.2. Nguyn l phn i xng nguyn l Paoli 27 4.3. Cc mc nng lng trong nguyn t nhiu e. Quy tc Klechkopski 27 4.4. Cu hnh e ca nguyn t 28
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4.4.1. Cu hnh e 28 4.4.2. Cch biu din cu hnh e ca nguyn t 28 4.4.3. Cc c s vit cu hnh e ca nguyn t 28 4.5. Phng php Slater xc nh cc AO v nng lng cc e 29 5. Ht nhn nguyn t 30 5.1. Nguyn t 30 5.2. Mt s vn ho hc ht nhn 31 5.2.1. Cc c trng c bn ca ht nhn 31 5.2.2. Cu trc Proton- Ntron ca ht nhn 32 5.2.3. Phng x ht nhn 34 5.2.4. i cng v phn ng ht nhn 37 37 5.2.5. S phn hch ht nhn (phn chia ht nhn) 5.2.6. Phn ng nhit hch 38 6. nh lut tun hon v h thng tun hon38 6.1. Sp xp tun hon cc nguyn t theo cu hnh e ca chng 38 6.1.1. Nguyn tc sp xp 38 6.1.2. nh lut tun hon 39 6.1.3. Bng tun hon39 6.1.4. Cc h ho hc 40 6.2. S bin i tun hon mt s tnh cht ca cc nguyn t 40 6.2.1. Bn knh cng ho tr ca nguyn t 40 6.2.2. Nng lng ion ho I (eV) 41 42 6.2.3. i lc vi e 6.2.4. m in (X) 43 Chng 3: Cu to phn t v lin kt ho hc 46 1. Cc c trng c bn ca lin kt ho hc 46 1.1. i cng v phn t v lin kt ho hc 46 1.1.1. Hai c im quan trng ca h phn t 46 1.1.2. Cng thc ho hc 46 1.2. Cc c trng c bn ca lin kt ho hc 46 1.2.1. Khi nim v lin kt ho hc 46 46 1.2.2. Cc c trng c bn ca lin kt ho hc 2. Lin kt ho tr v lin kt ion 50 2.1. Quy tc bt t 50 2.1.1. Nhn xt 50 2.1.2. Quy tc bt t 50 2.2. Thuyt e v ho tr - S Lewis 50 2.2.1. S c bn ca lin kt cng ho tr 50 2.2.2. Biu din lin kt cng ho tr bng lng t 51 2.3. S phn cc ca lin kt cng ho tr lin kt ion 52 3. Mt s vn ca thuyt lin kt ho tr (VB) 53 3.1. Cc lun im c s ca thuyt lin kt ho tr (VB): thuyt cp e 3.2. Mt s thuyt trong phm vi thuyt VB 53 3.2.1. Thuyt Spin v ha tr 53
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3.2.2. Thuyt ho tr nh hng 56 3.2.3. Nguyn l xen ph cc i 56 3.2.4. Thuyt lai ha (s lai ho cc AO) 57 3.2.5. Thuyt sc y gia cc cp e. Quy tc Giletspi (VSEPR) 3.3. nh gi s lc v thuyt VB 64 3.3.1. Thnh cng 64 3.3.2. Hn ch 64 4. Mt s vn ca thuyt MO 66 4.1. Cc lun im c bn ca thuyt MO 66 4.2. S lc bi ton ion phn t H2+ 67 4.3. Thuyt MO gii thch lin kt trong cc phn t A2 68 4.3.1. Mt s vn chung 68 4.3.2. Xt cc MO v gin nng lng h A2 69 4.3.3. Yu t i xng v lin h vi MO 69 4.3.4. S lin kt hiu dng (bc lin kt) 70 4.3.5. Cc gin nng lng MO 70 4.3.6. Bi tp p dng 70 4.4. Thnh cng v hn ch ca thuyt MO 71 4.4.1. Thnh cng 71 4.4.2. Hn ch 71 Chng 4: Cc trng thi tp hp vt cht 72 1. Lc tng tc gia cc phn t 72 1.1. Lc Vandevan 72 1.1.1. Lc nh hng 72 1.1.2. Tng tc cm ng (Tng tc lng cc cm ng) 72 1.1.3. Tng tc khuych tn 72 1.2. Lin kt hidro 73 1.2.1. Khi nim 73 1.2.2. S tng qut 73 1.2.3. c im ca lin kt H 73 1.2.4. Cc kiu lin kt hidro 73 1.2.5. Tnh cht ca cc hp cht c kh nng to lin kt H 2. Cc trng thi tp hp ca vt cht 74 2.1. Cht kh 75 2.2. Cht lng 76 2.2.1. p sut hi bo ho ca cht lng 77 2.2.2. Nhit si ca cht lng 77 2.2.3. Nhit ho hi 77 2.2.4. Tnh nht 77 2.2.5. Sc cng b mt 78 2.2.6. Tnh mao dn 79 2.3. Cht rn 79 2.3.1. Nhit nng chy 79 2.3.2. Nhit nng chy 79
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2.3.3. Cht rn dng tinh th v cht rn dng v nh hnh 80 2.3.4. Hin tng a hnh v hin tng ng hnh 80 Chng 5: Nhit ng lc ho hc 82 1. Mt s khi nim c bn trong nhit ng lc hc 82 1.1. H nhit ng 82 1.2. Pha 82 1.3. Trng thi 82 1.4. Bin i ca mt h 83 1.5. Hm trng thi 83 1.6. Nng lng 83 1.7. Cng v nhit 84 2. Nguyn l th nht ca nhit ng hc 85 2.1. Biu thc ca nguyn l I. Hm ni nng (U) 85 2.2. Mt s trng hp cn ch khi dng nguyn l 1 86 2.3. Hm trng thi entanpi (H) 86 2.4. Quan h gia QP v QV (hay l gia H v U) ca kh l tng 87 2.5. Nhit dung (C) 87 Chng 6: Vn tc phn ng v cn bng ho hc 89 1. Tc ca phn ng ho hc 89 1.1. Vn tc trung bnh vn tc tc thi (Vtb v Vt) 89 1.1.1. Vn tc trung bnh 89 1.1.2. Vn tc tc thi 89 1.2. nh hng ca nng n Vp. nh lut tc dng khi lng 89 1.2.1. i vi phn ng ng th 89 1.2.2. i vi phn ng d th phn ng din ra 2 pha 89 1.2.3. Phn t s v bc phn ng 90 1.2.4. Phng trnh ng hc ca phn ng bc 1, 2, 3, 0, n 90 1.3. nh hng ca nhit n tc phn ng. Nng lng hot ng ho 93 1.3.1. Quy tc VantHp 93 1.3.2. Phng trnh ca Areniruyt 93 1.3.3. Bn cht ca Ea 94 1.3.4. nh hng ca xc tc n tc phn ng 94 2. Cn bng ho hc Nguyn l Lsatlie 95 2.1. Phn ng mt chiu v phn ng thun nghch 95 2.2. Hng s cn bng ha hc (K) ca phn ng thun nghch 95 2.3. Cc loi hng s cn bng ha hc v mi quan h 96 2.4. S chuyn dch cn bng. Nguyn l Lsatlie 97 Chng 7: Dung dch 99 1. Mt s khi nim chung v dung dch 99 1.1. H phn tn 99 1.1.1. nh ngha 99 1.1.2. Cc loi h phn tn 99
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1.2. Dung dch bo ho 99 1.2.1. Cn bng ho tan 99 1.2.2. Dung dch bo ho (DDBH) 99 1.2.3. Dung dch cha bo ho 99 1.3. Nng dung dch- tan 99 1.3.1. Khi nim 99 1.3.2. Cc cch biu din nng dung dch 99 1.3.3. Dung dch qu bo ho 100 1.3.4. tan (S) v cc yu t nh hng 100 1.3.5. Dung dch l tng v dung dch tht 101 2. Dung dch cha cht tan khng in ly, khng bay hi 101 2.1. S gim p sut hi bo ho ca dung dch. nh lut Raoun1 101 2.1.1. p sut hi bo ho 101 101 2.1.2. S gim p sut hi bo ho ca dung dch. nh lut Raoun1 2.2. tng t0s v gim t0 ca dung dch 102 2.3. p sut thm thu 102 2.3.1. Mng bn thm102 2.3.2. S thm thu 102 2.3.3. p sut thm thu 102 2.3.4. Xc nh phn t khi ca cht tan khng in ly, khng bay hi 103 3. dung dch in ly 103 3.1. Tnh cht ca dung dch in ly 103 3.2. Thuyt in ly 103 3.2.1. Ca Areniuyt 103 3.2.2. Ca Calcp 104 3.3. in ly v hng s cn bng 104 3.3.1. in ly 104 3.3.2. Hng s in ly (K) 104 3.3.3. nh hng ca nng dung dch n dung dch in ly 105 3.4. Cn bng trong dung dch axit v baz105 3.4.1.Thuyt v axit v baz 105 3.4.2. Cp axit baz lin hp 106 3.4.4. Thuc tnh axit baz ca H2O 106 3.4.5. Thang pH 107 3.4.6. Axit mnh v baz mnh 107 107 3.4.7. Axit yu v baz yu. Hng s phn li K axit v K baz 3.4.8. Tnh cht axit, baz ca mui. S thu phn 108 3.4.9. Dung dch m 109 3.5. Thuyt axit v baz ca Liuyt 109 3.6. Dung dch cht in ly t tan 109 3.6.1. Tch s tan 109 3.6.2. Quan h gia tch s tan (T) v tan (S) 110 3.6.3. Tnh s tan v s kt ta 111 3.6.4. Tnh s tan v s ho tan cc kt ta 112
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Chng 8: Phn ng oxy ho - kh v dng in 113 1. Phn ng oxy ho kh 113 1.1. S oxi ho (Mc oxi ho, bc oxi ho hay trng thi oxi ho) 113 1.2. Phn ng oxi ho kh 114 1.3. Cn bng phn ng oxi ho kh 115 2. Cc qu trnh in ho 118 2.1. Nguyn tc bin i ho nng thnh in nng 118 2.2. Th in cc ? 119 2.3. Cc loi in cc 119 2.4. H in ho 119 2.5. Quan h gia ?G v E 120 2.6. Phng php xc nh th in cc. Th in cc tiu chun 120 2.7. nh hng ca nng n Th in cc v sc in ng ca pin 2.8. Chiu v trng thi cn bng ca phn ng oxy ho kh 121
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Hoa Dai Cuong D

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CHNG 1 CC KHI NIM V NH LUT C BN CA HA HC A. MC TIU, NHIM V 1.

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Trng i hc cng nghip h ni

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BNG 1.1. Bn knh cng ho tr (A0) v khi lng nguyn t ca mt s nguyn t ha hc

BNG 1.2. Khi lng, in tch ca electron, proton, ntron

KHI LNG Kg Electron Proton Ntron 9,109.10

IN TCH Culong -1,6021.10 0,0

vC (u) 5,55.10 1,007 1,009

Trng i hc cng nghip h ni

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Trng i hc cng nghip h ni

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Trng i hc cng nghip h ni

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mt n v khi lng v c gi l n v cacbon (vC hay u), ta c:

9,274.10 26 kg = 56 AFe = 1,6605.10 27 kg 5,3.10 26 kg = 32 AS = 1,6605.10 27 kg

Trng i hc cng nghip h ni

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Cch tnh s mol:

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V d 22: ng lng ca Fe2O3 l:

ng lng ca H2SO4 trong phn ng:

160 = 26,7 2 + 2 + 2 = 3.2

2NaOH + H2SO4 Na2SO4 + 2H2O l H SO =

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BNG1.3. By i lng c bn ca h o lng quc t (h SI)

Ngoi ra cn c hai n v b sung thng dng l

Trng i hc cng nghip h ni

b) Cc i lng khng c tn ring

in tch Gc phng Momen lng cc in

Trng i hc cng nghip h ni

2.3. Cc hng s vt l BNG 1.6. Cc hng s vt l thng dng

22,41 l/mol = 0,02241 m3/mol 8,3144J/mol.K 8,2054.10-2 1atm/mol.K 1,98 cal/mol.K

Hng s Bnxman(Bolzman) Hng s Ritbe (Rydberg) Manhton Bo (Bohr) Bn knh Bo (Bohr)

1,38054.10-23 J/K 109677,57 c.m-1 9,2732.10-24 J/T 5,29167.10-19cm = 0,529 A0

Trng i hc cng nghip h ni

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h 1,0 (vi h = 6,625.10-34J.s) 2

0 l hng s in mi trong chn khng

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Th lun c: m A1 + m A1 + ... + m A n = m B1 + m B 2 + ... + m B n ' Hay:

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T cc kt qu thc ngim thu c bng 3.1, ta ly:

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m m d RT P = RT = RT ; trong d l khi lng ring M VM M

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kg .0,022415m 3 2 kg.m 2 m.s = 8,314 2 .mol 1 .K 1 = 8,314 J .mol 1 .K _ 1 1mol.273,15K s

T = 273,15 + 25 = 298,15 K Vy: d =

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Thay s: 0,253 + mO = 0,420 mO = 0,167 g

p dng nh lut ng lng:

0.253 8 = 12,12 0,167

Trng i hc cng nghip h ni

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Kt hp vi biu thc trn, ta c: d A / B =

Ch : khi xc nh t khi hi ca kh A vi kh B th phi a v cng th tch nh nhau, th khi t s: d A =

mA M A mi l t khi. Cn khi khc = mB M B

m M nhau v th tch th t s khi lng A A khng phi l t khi. mB M B

T phng trnh: Vy: