I HC HU TRUNG TM GING DY V THC HNH C BN B MN HA

BI GING

HA HC I CNG
(Dnh cho sinh vin khng chuyn ngnh ha)

ThS. NGUYN PH HUYN CHU ThS. NGUYN TH MINH MINH ThS. TRN TH HA

Hu 2006

MC LC

NI DUNG BI M U CHNG I: NHNG KHI NIM V NH LUT C BN CA HO HC

TRANG 01 02

I. Nhng khi nim c bn

1. Khi nim nguyn t - phn t 2. Khi nim nguyn t khi, phn t khi 3. Khi nim nguyn t gam, phn t gam, ion gam 4. K hiu ho hc - Cng thc ho hc 5. n cht - Hp cht - Dng th hnh ca mt nguyn t 6. Nguyn cht - Tp cht - cht tinh khit 7. Phng trnh ho hc

02
02 02 02 03 03 03 03

II. Cc nh lut c bn ca ho hc
1. nh lut bo ton khi lng (Lomonossov 1756) 2. nh lut thnh phn khng i (Dalton - 1799) 3. Phng trnh trng thi kh l tng 4. nh lut Avgadr 5. nh lut ng lng CHNG II: CU TO NGUYN T V H THNG TUN HON CC NGUYN T HO HC

04
04 04 04 05 06 08

I. Nhng c s vt l nghin cu cu to nguyn t

1. Thnh phn nguyn t 2. Thuyt lng t planck 3. Bn cht sng v ht ca ecletron

08
08 08 09

II. Hm sng v phng trnh sng ca electron

1. Hm sng () 2. Phng trnh sng Schrodinger

10
10 10

3. Kt qu gii phng trnh sng Schrodinger 4. Cc s lng t v ngha 5. Nng lng ca electron

11 11 13

III. Orbitan nguyn t - hnh dng cc orbital nguyn t

1. Khi nim v orbital nguyn t (AO) 2. Hnh dng cc electron

13
13 14

IV. Nguyn t nhiu electron - s phn b electron trong nguyn t nhiu electron
1. Khi nim v lp, phn lp v lng t 2. Cc qui lut phn b electron trong nguyn t nhiu electron

15
15 16

V. Cu to ht nhn nguyn t - ng v
1. Cu to ht nhn nguyn t 2. Hin tng ng v 3. Hin tng phng x t nhin 4. Phn ng ht nhn 5. ng dng ca ng v phng x nhn to

18
18 19 19 19 19

VI. Cu to nguyn t v h thng tun hon cc nguyn t ho hc

1. nh lut tun hon 2. Bng h thng tun hon cc nguyn t 3. S bin i tun hon tnh cht cc nguyn t 4. Quan h gia cu hnh electron v v tr ca nguyn t trong bng h thng tun hon CHNG III: CU TO PHN T V LIN KT HO HC

20
20 20 21 22 24

I. Mt s khi nim
1. Khi nim v phn t 2. m in 3. Mt s c trng ca lin kt

24
24 24 25

II. Lin kt ion

1. nh ngha 2. iu kin to thnh lin kt ion 3. c im ca lin kt ion 4. Ho tr ca nguyn t trong hp cht ion

26
26 27 27 27

III. Lin kt cng ho tr

1. Thuyt Lewis v lin kt cng ho tr 2. Quan im ca c hc lng t v lin kt cng ho tr

27
27 28

3. Lin kt phi tr

38

IV. Tng tc gia cc phn t

1. Lin kt hydro 2. Lc Vanderwaals

38
38 40

V. S lc v trng thi tp hp ca cc cht

1. Trng thi kh 2. Trng thi lng 3. Trng thi rn CHNG IV. NHIT NG HC HO HC

41
41 41 41

I. Mt s khi nim c bn
1. H nhit ng 2. Cu t 3. Pha (tng) 4. Trng thi 5. Hm trng thi 6. Qu trnh 7. Qu trnh t din bin v qu trnh khng t din bin 8. Qu trnh thun nghch v qu trnh khng thun nghch 9. Nng lng

42
42 42 42 42 43 43 43 43

II. Nguyn l th nht ca nhit ng hc

1. Ni nng ca h(U) 2. Nguyn l th nht ca nhit ng hc 3. Entanpi (H) 4. Quan h gia U v H

44
44 44 45 45

III. Nhit ha hc
1. Hiu ng nhit ca phn ng 2. Sinh nhit (nhit to thnh) (Hs) 3. Thiu nhit (nhit t chy) (H0 c) 4. Nhit phn hu (H0ph) 5. nh lut Hess

45
45 46 46 47 47

IV. Nguyn l II ca nhit ng hc

1. Ni dung 2. Entropi 3. Biu thc ton hc ca nguyn l II

48
48 48 49

4. Cch trnh entropi ca mt s qu trnh thun nghch

50

V. Th ng p v chiu t din bin ca qu trnh ha hc

1. Tc ng ca yu t entanpi v entropi ln chiu hng ca qu trnh 2. Th ng p - ng nhit (Nng lng t do Gibbs) 3. Cch tnh bin thin th ng p ca qu trnh CHNG V. NG HO HC

50
50 50 51 52

I. Mt s khi nim
1. Tc phn ng 2. Phn ng n gin v phn ng phc tp 3. Phn t s v bc phn ng 4. Phn ng ng th v phn ng d th

52
52 52 53 54

II. Cc yu t nh hng n tc phn ng

1. nh hng ca nng n tc phn ng 2. nh hng ca nhit n vn tc phn ng 3. nh hng ca cc cht xc tc n phn ng

54
54 55 56

III. Phng trnh ng hc ca phn ng

1. Phn ng bc mt 2. Phn ng bc 2 3. Phn ng bc 3 4. Phn ng bc 0

59
59 60 61 61

IV. Mt s phn ng khc

1. Phn ng quang ho 2. Phn ng dy chuyn 3. Phn ng ni tip 4. Phn ng song song CHNG VI. CN BNG HO HC

61
62 62 63 63 64

I. Phn ng thun nghch v phn ng mt chiu

1. Phn ng mt chiu 2. Phn ng thun nghch

64
64 64

II. Cn bng ho hc - hng s cn bng

1. Khi nim v cn bng ho hc 2. Hng s cn bng

64
64 65

III. S chuyn dch cn bng v nguyn l chuyn dch cn bng

66

1. Khi nim v s chuyn dch cn bng. Nguyn l chuyn dch cn bng 66 2. Xt mt s v d v chuyn dch cn bng 67

CHNG VII. DUNG DCH

69

I. Nng v tan ca dung dch

1. Nng 2. tan v cc yu t nh hng n tan

69
69 71

II. p sut hi bo ha ca dung dch cha cht tan khng in li v khng bay hi. nh lut RAOULT II
1. Khi nim v p sut hi bo ha 2. p sut hi bo ho ca dung dch cha cht tan khng bay hi, khng in li

72
72 72

III. Nhit si v nhit ng c ca dung dch nh lut Raoult II IV. p sut thm thu ca dung dch

73 74
74 75 75 77 77 77 77 78 78

1. Hin tng thm thu 2. nh lut Vant Hoff v p sut thm thu 3. ng dng hin tng thm thu v p sut thm thu CHNG VIII. DUNG DCH IN LI I. Thuyt in li 1. Tnh cht ca dung dch in li 2. Thuyt in li 3. in li 4. Quan h gia in li v h s Van' t Hoff I

II. Cn bng trong dung dch cht in li yu

1. Hng s in li 78 2. Mi lin h gia hng s in li v in li

78

79

III. c im in li ca axit v baz

1. Quan im ca Arrhenius 2. Quan im axit - baz ca Bronsted IV. Dung dch phc cht 1. nh ngha 2. Cu to phc cht 3. Hng s khng bn ca phc cht

79
79 81 82 82 82 82

V. Cht in li t tan - tch s tan

1. nh ngha tch s tan 2. iu kin ho tan mt cht in li t tan 3. iu kin kt ta ca mt cht in li t tan

83
83 83 84

VI. Tch s ion ca nc - pH ca mt s dung dch

1. Tch s ion ca nc 2. Ph 3. Cht ch th v pH 4. pH ca mt s dung dch

84
84 84 84 84

VII. S thu phn ca mui

1. nh ngha phn ng thu phn 2. iu kin xy ra phn ng thu phn 3. Cc loi mui thu phn (tho mn iu kin thu phn)

86
86 86 86

VII. Dung dch m

1. nh ngha 2. Phn loi 3. C ch tc dng m 4. pH ca h m 87 5. ngha v vai tr ca dung dch m i vi i sng sinh vt

87
87 87 87

87

IX. Phn ng trao i v phng php phn tch th tch

1. iu kin xy ra phn ng trao i 2. Phn ng trao i v phng php phn tch th tch CHNG IX. HO KEO

88
88 88 90

I. Phn loi

90

1. Phn loi theo trng thi tp hp 90 2. Phn loi da trn s tng tc gia cc cht phn tn v mi trng phn tn

II. Cc phng php iu ch v tinh ch keo

1. Phng php phn tn 2. Phng php ngng t 3. Tinh ch dung dch keo

91
91 91 92

III. Tnh cht ng hc ca h keo

1. Chuyn ng Brown 2. p sut thm thu 3. ng dng ca hin tng khuch tn v p sut thm thu

92
92 93 93

IV. Tnh cht quang hc ca h keo

1. S phn tn nh sng 2. S hp th nh sng 3. Mu sc ca h keo

94
94 94 96

V. Tnh cht in ca h keo

1. Cc hin tng in ng hc

96
96

2. Cu to ca ht keo - Tnh bn ca cc dung dch keo 3. Cc loi th xut hin trn b mt mixen keo

96 96

VI. c tnh b mt v s hp ph ca dung dch keo

1. Sc cng b mt 2. S hp ph

99
99 100

VII. S ng t keo
1. S lm ng t keo bng cht in li 2. S lm ng t keo bng keo tch in tri du 3. S lm ng t keo bng cch un nng

102
102 102 103

VIII. S pepti ha
CHNG X: IN HA HC I. Phn ng oxi ha kh 1. Phn ng oxi ha kh 2. Cp oxi ha kh 3. Cn bng phng trnh oxi ha kh 4.ng lng gam ca phn ng oxi ha kh

103
104

104
104 104 105 105

II. Phn ng ha hc v dng in. Nguyn t Galvani

1. S xut hin th in cc 2. Nguyn t Daniel Jacobi ( pin Cu-Zn ) 3.Sc in ng ca nguyn t Galvani 4. Lin h gia sc in ng ca nguyn t Galvani v nng lng t do ( G) 5. Chiu ca phn ng oxi ha kh 6. Hng s cn bng ca phn ng oxi ha kh 7. Xc nh th in cc, th oxi ha kh, sc in ng ca pin iu kin khc chun. Phng trnh Nersnt

106
106 106 106
107

107 108 108

III. Cc loi in cc
1. in cc kim loi - ion kim loi 2. in cc oxi ha kh 112 3. in cc kh ion 4. i n cc calomen: Hg/Hg2Cl2,Cl5. in cc thy tinh

111
111

113 113 113

IV. ng dng ca nguyn t Galvani

1. Xc nh th in cc tiu chun ca in cc kim loi v in cc oxi ha kh tiu chun 2. Xc nh PH bng phng php in ha

113
113 114

3. Xc nh bin thin th ng p tiu chun (G0) ca mt phn ng 4. Phng php chun o th

115 115

III. S in phn
1. nh ngha 2. Hin tng in phn: 3. Cc trng hp in phn 4. nh lut Faraday 5. ng dng ca s in phn Ph lc Ti liu tham kho

115
115 115 116 118 119 120 135

BI M U

I.

i tng nghin cu

Ho hc l ngnh khoa hc t nhin, nghin cu v thnh phn cu to v tnh cht ca cc cht v cc qu trnh bin i t cht ny sang cht khc. Ho hc lin quan n hu ht cc lnh vc ca i sng con ngi. Ha hc cung cp nhng kin thc c bn cho nhiu ngnh khoa hc khc nhau. V d: ho hc mi trng, ho thc phm, ho dc, ho hc nng nghip, ho hc vt liu, ho a cht, ho sinh hc V vy ho hc c vai tr rt ln i vi nn kinh t quc dn. V rt nhiu ngnh, nhiu lnh vc cng nng nghip u lin quan n ho hc. Mt khc vic nm vng nhng kin thc v cc qu trnh ho hc, cc yu t nh hng n cc qu trnh trong cc lnh vc sn xut, sinh hc s gip cho con ngi c nhng tc ng tch cc theo hng c li cho nhng mc tiu m cc nh khoa hc cn t c. Do vic nm vng nhng kin thc c bn v ho hc l rt cn thit. Vi nhng kin thc ny ngi ta c th s dng phc v tt cho cng vic chuyn mn ca mnh.

II. Vai tr v nhim v ca mn ho i cng

Cung cp mt cch c h thng kin thc c bn v cu to cc cht ho hc, v s tng tc v cch thc vn ng ca chng trong t nhin. Gip cho sinh vin nm c mt s quy lut v s vn ng ca cc cht. D on kh nng, chiu hng v gii hn ca cc qu trnh ho hc, nhng hin tng km theo cng nh cc yu t thc y hoc km hm cc qu trnh . Tng bc gip sinh vin lm quen vi cc thao tc thc hnh c bn, cc cng vic trong phng th nghim, tp s dng cc dng c, ho cht, tp ghi chp v x l cc d liu thu c khi lm th nghim.

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CHNG I

NHNG KHI NIM V NH LUT C BN CA HO HC

I. Nhng khi nim c bn
1. Khi nim nguyn t - phn t Cc cht ho hc trong t nhin rt phong ph, gm hng ngn, hng vn cc cht v c, hu c. Cc cht ny c to nn do s kt hp ca hn 90 nguyn t bn. Mi nguyn t c c trng bng s tn ti ca hng triu nguyn t ging ht nhau v mt ho hc. 1.1. Nguyn t ho hc L khi nim c trng cho mi loi nguyn t c in tch ht nhn xc nh, biu th bng nhng k hiu ho hc ring. 1.2. Nguyn t L phn t nh nht ca mt nguyn t ho hc, tham gia vo thnh phn phn t ca cc n cht v hp cht. V d: H, O, Na 1.3. Phn t L phn t nh nht ca mt cht, c kh nng tn ti c lp v c y tnh cht ho hc ca cht . V d: H2, H2O, Na 2. Khi nim nguyn t khi, phn t khi - Nguyn t khi l khi lng ca mt nguyn t tnh theo n v C. V d: Nguyn t khi ca Hydr = 1 n v C Nguyn t khi ca Oxi = 8 n v C - Phn t khi l khi lng ca mt phn t tnh theo n v C. V d: Phn t khi ca HCl = 36,5 n v C 3. Khi nim nguyn t gam, phn t gam, ion gam 3.1. Nguyn t gam L khi lng ca mt mol nguyn t tnh bng gam (nguyn t gam v nguyn t khi c cng tr s nhng khc n v). V d: Oxi c nguyn t khi = 16 .v C nguyn t gam = 16g 3.2. Phn t gam: L khi lng ca mt mol phn t tnh bng gam V d: H2SO4 c phn t khi = 98 .v C phn t gam = 98g (Phn t khi v phn t gam c cng tr s nhng khc n v)

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4. K hiu ho hc - Cng thc ho hc 4.1. K hiu ho hc Mi nguyn t c biu din bng mt k hiu gi l k hiu ho hc V d: Na, O, Ne, Ar 4.2. Cng thc ho hc Mi cht ho hc c biu th bng mt cng thc - Cng thc phn t: biu th thnh phn nh tnh v nh lng ca cc cht. V d: H2O, NaCl, KMnO4 - Cng thc cu to: biu din th t kt hp ca cc nguyn t trong phn t. Ru: CH3 - CH2 - OH V d: C2H6O Ete : CH3 - O - CH3 5. n cht - Hp cht - Dng th hnh ca mt nguyn t 5.1. n cht L cht m phn t ca n ch gm cc nguyn t ca mt nguyn tt lin kt vi nhau. V d: lu hunh, cacbon, hidr 5.2. Hp cht L cht m phn t ca n gm nhng nguyn t ca cc nguyn t khc loi lin kt vi nhau. V d: NaCl, H2O, KMnO4 5.3. Dng th hnh ca mt nguyn t L nhng dng n cht khc nhau ca cng mt nguyn t ho hc. V d: xi v zn Than ch, kim cng, than v nh hnh 6. Nguyn cht - Tp cht - cht tinh khit - Nguyn cht : L cht m khi trong cht khng ln bt k mt cht no khc. V d: nc nguyn cht, ng nguyn cht - Tp cht: l mt lng nh cc cht b ln vo mt cht khc. V d: vng 99,9 ngha l trong 100g vng c 0,1 g cc tp cht Ag, Cu Trong khoa hc chnh xc hn ngi ta dng khi nim cht tinh khit, siu tinh khit. - Cht tinh khit: l cht ho hc khng ln cc cht khc. Thc t kh c cht t tinh khit 100%. Nu trong mt cht m lng cht cng t ta ni n c tinh khit cng cao. Trong nghin cu tu theo yu cu, ngi ta c th dng cc loi ho cht c tinh khit khc nhau.

Ngi ta thng phn thnh:

- Ho cht tinh khit - Ho cht k thut (lng cht l trong cht chnh c mt gii hn no )

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7. Phng trnh ho hc biu din s tng tc gia cc cht ngi ta dng phng trnh ho hc. V d: NaOH + HCl = NaCl + H2O Qua phng trnh trn ta thy: - Tng khi lng cc cht tham gia phn ng bng tng khi lng ca cc cht to thnh sau phn ng. - Tng s nguyn t ca cc nguyn t 2 v bng nhau.

II. Cc nh lut c bn ca ho hc
1. nh lut bo ton khi lng (Lomonossov 1756) - nh lut: Khi lng ca cc cht tham gia phn ng bng khi lng ca cc cht to thnh sau phn ng. - ng dng: - Dng cn bng cc phng trnh phn ng - Tnh khi lng cc cht tham gia v to thnh sau phn ng. 2. nh lut thnh phn khng i (Dalton - 1799) nh lut: l mt hp cht ho hc d c iu ch bng cch no th bao gi cng c thnh phn khng i. V d: Nc d iu ch bng nhiu cch khc nhau nh t hidr v xi trong khng kh, thc hin phn ng gia mt axit v mt baz, t cht hydrcacbon cng lun lun u cha hydr v xi theo t l khi lng hydr v xi 1:8. 3. Phng trnh trng thi kh l tng Nhng nghin cu v tnh cht ca cc cht kh cho thy rng nhit khng qu thp v p sut khng qu cao (so vi nhit v p sut thng), phn ln cc kh u tun theo mt h thc gi l phng trnh trng thi kh l tng. PV = nRT P: p sut cht kh V: th tch cht kh n: s mol kh T: 0K (T = t0 + 273) R: hng s kh

Trong :

(Khi P tnh bng atm, V tnh bng lt th R = 0,082lt atm/mol ) (Khi P tnh bng mmHg, V tnh bng ml th R = 62400ml mmHg/mol )

ng dng: m m mRT PV = RT M = M M PV V vy nh lut ny c ng dng xc nh phn t gam ca cc cht kh bng thc nghim. Ta bit n =

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4. nh lut Avgadr - nh lut: cng mt iu kin nht nh v nhit v p sut, nhng th tch bng nhau ca cc cht kh u cha cng mt s phn t. T iu kin chun (.v phn ng xy ra gia cc cht kh) ta c " iu kin chun 0 (O C, 1 atm), mt mol ca bt k mt cht kh no cng u chim mt th tch bng nhau v bng 22,4lt". - ng dng: T cng thc: m = V.D Nu D l khi lng ring ca cht kh iu kin chun ta c: M = 22,4.D T ta c th xc nh phn t gam ca cht kh khi bit D ca cht cht iu kin chun. 5. nh lut ng lng 5.1. ng lng ca mt nguyn t Trong cc phn ng ho hc, cc nguyn t kt hp vi nhau theo nhng t l xc nh gi l t l kt hp hay ng lng ca chng. Vy "ng lng ca mt nguyn t l s phn khi lng ca nguyn tt c th tc dng hoc thay th va vi mt phn khi lng hydr hoc 8 phn khi lng xi . ng lng k hiu l . V d: HCl c Cl = 35,5 v H = 1 ng lng ca mt nguyn t thc cht l s phn khi lng ca nguyn t ng vi mt n v ho tr m n tham gia phn ng. A = n Trong : A: khi lng mol nguyn t : ng lng ca nguyn t n : ho tr ca nguyn t * Ch : V ho tr ca mt nguyn t c th thay i nn ng lng ca n cng thay i. V d: ng lng ca C trong CO l C = 12/2 = 6 ng lng ca C trong CO2 l cC = 12/4 = 3 i vi cc nguyn t c ho tr khng i th ng lng cng khng i. - ng lng gam ca mt nguyn t l khi lng ca nguyn t tnh ra gam ng lng ca nguyn t . 5.2. ng lng ca mt hp cht ng lng ca mt hp cht l s phn khi lng ca cht tc dng va vi mt ng lng ca mt nguyn t hay mt hp cht khc bt k.

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ng lng ca mt hp cht thng c tnh theo cng thc: M = n Trong : M: khi lng mol phn t ca hp cht - Trong phn ng trao i n: - s ion H+ m mt phn t axit tham gia trao i - s ion OH- m mt phn t baz tham gia trao i - Tng s in tch ion m hoc dng m mt phn t mui tham gia trao i. - Trong phn ng xi ho kh n: s ecletron m mt phn t cht xi ho thu vo hay mt phn t cht kh mt i. V d: ng lng gam ca KMnO4 trong cc mi trng nh sau M - Mi trng axit: MnO4- + 5e + 8H+ = Mn2+ + 4H2O KMnO4 = 5 M - Mi trng trung tnh: MnO-4 + 3e- + 2H2O = MnO2 + 4OH- = 3 M - Mi trng baz: MnO-4 + 1e- = MnO2-4 = 1 - ng lng gam ca mt hp cht l gi tr ng lng ca cht tnh ra gam. V d: ng lng gam ca HCl bng 36,5gam ng lng gam ca H2 bng 2gam 5.3. Nng ng lng (N) Nng ng lng gam ca mt dung dch l s ng lng gam ca cht tan c trong mt lt dung dch. V d: dd HCl 1N c 36,5gam HCl nguyn cht trong mt lt. dd H2SO4 0,1N c 4,9 gam H2SO4 trong 1 lt 5.4. nh lut ng lng "Cc cht phn ng vi nhau theo nhng khi lng t l vi ng lng ca chng" hay "cc cht tham gia phn ng vi nhau theo nhng s lng ng lng gam nh nhau". mA Ta c mB = A B hay mA A = mB B

Trong , mA, mB l khi lng hai cht A, B phn ng va vi nhau. A, B l ng lng ca hai cht A, B.

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p dng nh lut ng lng cho phn ng xy ra trong dung dch:

Gi s c 2 cht A v B phn ng vi nhau theo phng trnh: A+BC Gi NA, NB ln lt l nng ng lng ca dd A v B. VA, VB l th tch ca dung dch A v dung dch B phn ng va vi nhau. Theo nh lut ng lng ta c: cc cht A v B phn ng va vi nhau theo s ng lng nh nhau nn: VA.NA = VB.NB T y ta c th xc nh nng ng lng ca mt cht khi bit nng ng lng ca cht kia bng thc nghim.

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CHNG II

CU TO NGUYN T V H THNG TUN HON CC NGUYN T HO HC

Cho n gia th k XVIII ngi ta cho rng nguyn t l ht nh nht cu to nn vt cht v khng th phn chia nh hn na. Nhng n cui th k XIX nhiu cng trnh khoa hc thc nghim chng t rng nguyn t c cu to phc to t nhiu loi ht c bn khc nhau.

I. Nhng c s vt l nghin cu cu to nguyn t

1. Thnh phn nguyn t Nh nhng thnh tu ca vt l hc, cc nh khoa hc khng nh rng nguyn t gm hai thnh phn chnh l electron v ht nhn nguyn t. 1.1. Electron (k hiu l e): V nguyn t gm cc electron - Khi lng ca e eclectron 1 me = 9,109.10-28g = .v C 1837 - in tch ca electron: qe = -1,602.10-19C in tch ca e l in tch nh nht gp nn n c chn lm n v in tch. qe = -1 n v in tch hay = -1 1.2. Ht nhn nguyn t L phn trung tm ca nguyn t, gm cc ht proton v neutron. Ht nhn mang in tch dng, s n v in tch dng ca ht nhn bng s electron trong v nguyn t. Khi lng ca ht nhn xp x khi lng nguyn t. - Proton (k hiu p) Khi lng: mp = 1,672.10-24 = 1,008 .v C in tch : qp = 1,602.10-19C = +1 - Neutron (k hiu n) Khi lng: mn = 1,672.10-24g = 1,00 vC Neutron khng mang in 2. Thuyt lng t planck Nm 1900 Planck trnh by quan im lng t u tin v cho rng: "nh sng hay bc x in t ni chung gm nhng lng t nng lng pht i t ngun sng". C E = h = h Trong E: lng t nng lng h: hng s Planck (h = 6,625.10-34 J.S) : tn s ca bc x : bc sng bc x C: tc nh sng

9
Bc sng cng ln th tn s sng cng gim v ngc li, E gi l lng t nng lng v vi mi bc x d pht ra hoc hp th u bng mt s nguyn ln ca E. 2.2. H thc tng i Einstein (1903) Nm 1903 Einstein tm ra mi quan h gia vn tc v khi lng ca vt chuyn ng vi nng lng ca n qua biu thc". E = mC2 Kt hp vi trc ta c: C C E = h mC 2 = h h h mC = hay = mC l bc sng ca bc x, cng ln th tn s sng cng b, nng lng cng nh v ngc li. 3. Bn cht sng v ht ca ecletron 3.1. Mu nguyn t Bohr (1913) Bng vic p dng ng thi c c hc c in v c hc lng t khi nghin cu cu to nguyn t nm 1913, Niels Bohr xy dng mu nguyn t vi ni dung sau: - Trong nguyn t electron chuyn ng trn nhng qu o c bn knh xc nh. Khi chuyn ng trn cc qu o ny nng lng ca elctron c bo ton. - Mi qu o ng vi mt mc nng lng ca electron cng xa ht nhn th nng lng ca electron cng cao. - Khi electron chuyn t qu o ny sang qu o khc n s thu hoc pht ra nng lng bng hiu gia 2 mc di dng mt bc x c tn s . E = h = En' - En Vy: chuyn ng ca electron trong nguyn t gn lin vi vic thu hoc pht ra nng lng di dng bc x nn electron cng c tnh cht sng v ht nh bc x. 3.2. H thc De Broglie (1924) Khi pht biu v thuyt lng t, 1924 De Broglie nu gi thuyt "khng ch c bc x m cc ht nh trong nguyn t nh e, p cng c bn cht nng v ht, c c trng bng bc sng xc nh". h = mv Vi: m: khi lng ca ht v: tc chuyn ng ca ht Nhng nghin cu v sua cho thy gi thuyt ca De Broglie l ng n. V electron cng c bn cht nng v ht nn mi phng trnh m t chuyn ng ca electron phi tho mn ng thi c hai tnh cht . 3.3. H thc bt nh Heisenberg (1927) T tnh cht nng v ht ca cc ht vi m, 1927 nh vt l hc c Heisenberg chng minh nguyn l bt nh. "V nguyn tc khng th xc nh ng thi chnh xc c to v vn tc ca ht, do khng th xc nh hon ton chnh xc cc qu o chuyn ng ca ht". Nu gi sai s ca php o v tc ca ht theo phng x l vx v sai s ca php o to theo phng x l x th ta c biu thc ca h thc bt nh l :

10
h m Trong h: hng s Planck m: khi lng ca ht Theo biu thc ny ta thy vx v x bin thin thun nghch vi nhau. Nu x cng nh (x 0) ngha l cng xc nh chnh xc v tr ca ht th vx cng ln (vx ), ngha l khng th xc nh chnh xc gi tr tc ca elctron. x.vx

II. Hm sng v phng trnh sng ca electron

Cng trnh ca De Broglie t nn mng cho mt mn c hc mi dng m t chuyn ng ca cc ht vi m. Nm 1925 - 1926, Heisenberg v Schrodinger c lp nhau ra 2 phng php ca mn c hc ny v u t kt qu nh nhau nhng phng php ca Schrodinger n gin hn nhiu. Mn hc mi da theo phng php Schrodinger m t chuyn ng ca cc ht vi m gi l mn c hc lng t. Cc kt qu thu c ca mn c hc ny khi p dng cho cc h vi m u ph hp vi thc nghim. 1. Hm sng () Trng thi chuyn ng ca hi vi m c m t bng hm s (x,y,z,t) l mt hm xc nh, n v v lin tc gi l hm sng. - ngha vt l ca hm sng: Ta khng th xc nh chnh xc electron c mt to no nhng c th bit xc sut tm thy electron nhiu nht vng m phn ln thi gian electron c mt . V hm sng (x,y,z,t) c th l hm thc hoc phc nn n khng c ngha vt l trc tip. Ch c bnh phng modun ca hm sng l ||2 (thc v lun lun dng) mi c ngha l mt xc xut tm thy ht ti to tng ng. |(x,y,z,t)|2 d cho bit xc sut tm thy ti thi im t trong nguyn t th tch d c tm l M (x,y,z). Hnh nh ca hm mt xc sut trong khng gian gi l m my in t. Hm sng phi tho mn cc iu kin sau: - Hm sng phi n tr (ti mi im trong khng gian ng vi to (x,y,z) ch c mt gi tr duy nht cho xc sut tm thy electron ti ch c mt gi tr tng ng). - Hm sng phi hu hn v lin tc (ngha l khng th bng bt k to no nhng c th bng 0).

- Hm sng phi tho mn iu kin:

+

| d = 1

cho tng xc sut tm thy electron t - + phi lun lun bng 1, gi l hm sng chun ho. 2. Phng trnh sng Schrodinger tm c hm sng m t chuyn ng ca ht vi m th phi gii phng trnh sng gi l phng trnh Schodinger. l phng trnh c bn ca c hc lng t c nh vt l ngi o Schrodinger a ra nm 1926.

11
l phng trnh vi phn bc 2 ca hm c dng nh sau i vi ht (hay h ht) dng thi dng: h2 8 2 m + V = E (*) Trong : -V: th nng ca ht ti to x,y,z E: nng lng ton phn ca ht trong ton h

2 2 + + 2 : ton t Laplace: = 2 2 x y z
m: khi lng ca ht Trong trng hp tng qut c th vit phng trnh Schrodinger di dng: H = E * Trng thi dng l trng thi m nng lng ca h khng ph thuc thi gian ngha l E ca h khng i. Khi gii phng trnh Schrodinger ta s thu c cc hm sng m t cc trng thi chuyn ng ca electron trong nguyn t v cc gi tr nng lng E ng vi cc hm . 3. Kt qu gii phng trnh sng Schrodinger Bi ton n gin nht c cc nh khoa hc thc hin l bi ton ca nguyn t hydr. Sau khi xy dng hm th nng v a vo phng trnh (*) ngi ta gii phng trnh ny v thu c hm sng n,l,ml nghim ca phng trnh sng m t trng thi chuyn ng ca electron nguyn t gi l orbital nguyn t. Khi gii phng trnh ny, ngi ta nhn c ng thi cc cp nghim E v cng cc i lng vt l xc nh hm , c trng cho trng thi v v tr chuyn ng ca electron trong nguyn t l cc s lng t n, l, ml. ng vi mt gi tr ca E c mt hm sng , mi t hp (E, ) c trng cho mt trng thi ca electron. Trng hp nhiu hm cng ng vi mt gi tr nng lng E th ta gi l c s suy bin nng lng. * Ch : Phng trnh Schrodinger ch gii c chnh xc vi nguyn t hydr v cc ion n nguyn t ging hydr. Cn vi cc nguyn t nhiu electron th phi s dng cc phng php gn ng. 4. Cc s lng t v ngha Khi gii phng trnh Schrodinger ngi ta thy xut hin cc s lng t xc nh hm , chng xut hin do cc iu kin ton hc bi ton c nghim ch khng phi bi p t, cc hm ph thuc vo cc s lng t ny. 4.1. S lng t chnh (n) - V tr s: nhn cc gi tr nguyn dng: 1, 2 ... - V ngha: xc nh nng lng ca electron En = 2 2 me 4 n 2h 2

12
Trong : n: s lng t chnh m: khi lng ca electron e: in tch ca electron R 2 2 me 4 Nu thay R = ta c E = - 2 2 n h Ta thy vi n cng ln th nng lng E cng ln, electron cng cch xa nhn. Nhng electron c cng gi tr n tc l cng mc nng lng to thnh mt lp electron. S lng t chnh n Mc nng lng tng ng 1 K 2 L 3 M 4 N 5 O 6 P 7 Q

4.2. S lng t orbital (l) (s lng t momen gc) - V tr s: l nhn cc gi tr nguyn t O n (n - 1). ng vi mt gi tr ca n th c n gi tr ca l. - V ngha: Xc nh hnh dng v tn ca orbital. Nhng electron c cng gi tr l lp nn mt phn lp v c nng lng nh nhau. Lp th n c n phn lp. S lng t orbital (l) Phn lp 0 s 1 p 2 d 3 f 4 g

phn bit nng lng ca cc phn lp cng tn nhng khc lp ta ghi thm gi tr s lng t chnh trc k hiu phn lp: v d: 1s, 2s, 2p, 3s ... 4.3. S lng t t ml: - V tr s: l mt s nguyn c gi tr t -l n +l k c gi tr 0. + Vi mt gi tr ca l, th ml c (2l + 1) gi tr. V d: l = 1; ml c 3 gi tr l -1, 0, 1 l = 2; ml c 5 gi tr l -2, -1, 0, +1, +2 Mt gi tr ca ml ng vi mt orbtal (AO) - V ngha: c trng cho s nh hng ca orbital trong khng gian chung quanh ht nhn. Tm li, khi gii phng trnh Schrodinger, ngi ta tm thy 3 s lng t c trng cho trng thi chuyn ng ca electron trong nguyn t v tm c hm sng n,l,ml gi l orbital nguyn t, k hiu AO. Hm ny ph thuc vo 3 s lng t n, l, ml. B ba s lng t n, l, ml xc nh mc nng lng (theo n); phn mc nng lng (theo l) v hng ca orbital trong khng gian (theo ml). Cc s lng t ny c quan h ph thuc nhau v chi phi ln nhau. T n ta bit s gi tr ca l, t bit s gi tr ca ml, suy ra s AO c trong phn lp v c trong lp . 4.3. S lng t t spin ms Ngoi 3 s lng t trn, khi nghin cu cu trc tinh t ca cc ph nguyn t, ngi ta thy cn phi b sung mt s lng t na l s lng t t spin ms c th m t mt cch duy nht chuyn ng ca electron trong nguyn t.

13
V gi tr: ch nhn mt trong 2 gi tr +1/2 hay -1/2 v khng ph thuc g vo cc s lng t trn. V ngha: c trng cho dao ng t do ca electron c trng cho chuyn ng ni ti ca electron gn vi momen ng lng ring ca electron. Trong t trng ngoi trng thi ms = +1/2 c nng lng thp hn. 5. Nng lng ca electron Khi gii phng trnh Schrodinger cng vi , ta nhn c cc gi tr nng lng E tng ng. Vi nguyn t hidr, nng lng ca cc AO nguyn t c tnh theo biu thc: 2 2 me 4 n2h2 y nng lng ca electron l nhng gi tr gin on ph thuc vo s lng t chnh En = n. Khi n cng ln, th electron c nng lng cng cao. Ngi ta dng cc ch ci K, M, N k hiu cc mc nng lng ng vi cc s lng t chnh n = 1, 2, 3, 4

III. Orbitan nguyn t - hnh dng cc orbital nguyn t

1. Khi nim v orbital nguyn t (AO) AO l hm sng m t trng thi chuyn ng ca e trong nguynt , c biu th bng hm x,l,me. V d: vi n = 1, l = 0, ml ta c hm 1,0,0 ng vi AO 1s. vi n = 3, l = 2 ta c hm 3,2 AO 3d Tm li - mi gi tr ca ml ng vi 1AO - mt gi tr ca n c n gi tr ca l t l = 0 n l = n - 1. - mt gi tr ca l c (2l + 1) gi tr ca me v do c (2l + 1) AO khc nhau. Vy ng vi mt gi tr ca n (lp n) s AO c trong mi lp l:
( n 1)

(2l + 1) = n 2

l= 0

Vy lp thc n c n2 AO V d: Cho n = 3, hi c bao nhiu lp, phn lp, AO. - C 1 lp electron l lp th 3 (M) v n = 3 - l = 0, 1,2 nn c 3 phn lp: s, p,d - Vi mt gi tr ca l th c me c (2l + 1) gi tr nn s AO trong cc phn lp l: Phn lp 1 (l = 0) c 1AO Phn lp 2 (l = 1) c 3 AO Phn lp 3 (l = 3) c 5AO hay lp th 3 s AO nguyn t l 32 = 9AO Trn mi AO c th cha ti a 2e - c spin i song (1/2) vy trn lp n c n2AO v cha ti a 2n2 electron.

14
2. Hnh dng cc electron Hnh dng cc AO nguyn s ph thuc vo hm n,l,ml v k hiu theo s lng t l: s, p, d, f, g Trong h to x, y, z cc orbital s, p, d m hnh nh ca n l cc m my in t c dng nh sau: 2.1. AO s (xc nh bi l = 0; m l = 0): c dng hnh cu, tm l ht nhn nguyn t, hm s lun lun dng v mi pha ca trc to .

+ x

2.2. AO p (Xc nh bi l = 1; ml = -1, 0, +1 (Py, Pz, Px) l nhng cp hnh cu tip xc vi nhau im gc tm nm trn cc trc ta . Cc hm p lun lun dng v pha dng ca trc to v m vi cc gi tr to m.

z + -

+ x Px (ml =1)

y x

Py

(ml = -1)

Pz

(ml = 0)

15
2.3. AO d: xc nh bi l = 2, ml = -2, -1, 0, +1, +2 Cc AO d tr dz2 u c biu th bng hnh hoa th 4 cnh. me AO
x x + + +
2

+2 dx2-y2

-2 dxy

0 dz2

+1 dyz

-1 dxz

x + y + y z

dx y (ml = 2)
y +

dxy (ml = -2)

+ z

dxz (ml =1)

z +

dyz (ml = -1)

dz2 (ml = 0)

IV. Nguyn t nhiu electron - s phn b electron trong nguyn t nhiu electron
Bi ton v nguyn t nhiu electron phc tp hn nhiu so vi bi ton ca nguyn t ging hidr khi mi electron khng nhng chu lc ht ca ht nhn m cn chu lc y ca cc electron khc. V vy vic gii chnh xc bi ton bng phng php gii tch l khng th c nn ngi ta dng cc phng php gn ng. T xy dng c cc hm sng v phng trnh sng ny v thu c cc hm c dng tng t cc AO ca nguyn t hydr. 1. Khi nim v lp, phn lp v lng t - Lp: trong nguyn t cc electron c cng s lng t chnh n to thnh mt lp electron gi l lp n. Lp n c k hiu bng cc ch ci K, L, M, N ng vi cc gi tr ca n = 1, 2, 3, 4, - Phn lp: mi phn lp gm cc electron c cng s lng t l m mi gi tr ca n c n gi tr ca l nn mi lp c n phn lp. Lp K c 1 phn lp: 1s Lp L c 2 phn lp: 2s, 2p Lp M c 3 phn lp : 3s, 3p, 3d. V: Cc electron cng c l = 0 hp thnh phn lp s Cc electron cng c l = 1 hp thnh phn lp p

16
Cc electron cng c l = 2 hp thnh phn lp d Cc electron cng c l = 3 hp thnh phn lp f ch mt phn lp thuc lp no ngi ta dng k hiu ns, np V d: 2s, 2p. - lng t hay orbital: cc electron c 3 s lng t nh nhau (n, l, m l) c trng thi chuyn ng orbital ging nhau to thnh mt AO v c xp vo mt lng t - mi lng t c k hiu bng mt vung nh. S lng t trong mt phn lp bng s cc tr s ml ng vi gi tr l cho. V d: -Phn lp s c l = 0, me = 0 c 1 lng t - Phn lp p c l = 1, me = +1, 0, -1 c 3 lng t - Phn lp d c l = 2, me = +2, +1, 0, -1, -2 c 5 lng t 2. Cc qui lut phn b electron trong nguyn t nhiu electron 2.1. Nguyn l Pauli Ni dung: "Trong nguyn t khng th c hai hay nhiu electron c cng 4 s lng t". - Cc electron trong mt lng t c 3 s lng t n, l, me ging nhau nn s lng t ms phi khc nhau (+1/2 v -1/2) do s electron ti a trn mi AO l 2e-. Hai electron ny c spin tri du nhau v c k hiu bng hai mi tn ngc chiu nhau: ng vi ms = +1/2 v ng vi ms = -1/2 - Trong mt phn lp ng vi s lng t ph l c 2(l+1) AO nn cha ti a 2(2l + 1) electron. vy s electron ti a trong mt phn lp l 2(2l+1) electron. Ta c: Phn lp s p d f S electron ti a 2 6 10 14 - Lp th n c n2AO nn trong mi lp c ti a 2n2 electron. V d : n = 2 c s electron ti a l: 2.22 = 8e2.2. Nguyn l vng bn 2.2.1. Ni dung: "Trong mt nguyn t trng thi c bn, cc electron s xp vo cc phn lp c mc nng lng thp trc sau mi xp sang cc phn lp c mc nng lng cao hn. Nng lng ca cc phn lp c xc nh qua vic gii phng trnh Schrodinger. T , Klechkowski sp xp cc phn lp theo th t mc ny lng tng dn. 2.2.2. Qui tc Klechkowski Trong nguyn t, nng lng ca cc phn lp electron tng dn theo th t sau: 1s 2s 2p 3s 3p 4s 3d 5s 4d 5p 6s 4f 5d 6p 7s Theo quy tc ny th electron c in vo cc AO c gi tr (n + l) nh trc, nu 2 AO c cng gi tr (n + l) th electron s iu vo cc AO c gi tr n nh trc. V d: electron c in vo AO 4s trc AO 3d. C th m t qui tc Klechkowski nh sau: 7s 6s 5s 4s 3s 2s 7p 6p 5p 4p 3p 2p 7d 6d 5d 4d 3d 7f 6f 5f 4f

17
1s 2.3. Qui tc Hund 2.3.1. Qui tc Hund 1 (qui tc tng spin cc i) "Trong nguyn t dng trng thi c bn, cc electron thuc cng mt phn lp s c phn b u vo cc lng t sao cho tng spin S ca chng l cc i (tng s electron c thn l cc i)". S = ms V d: Nguyn t N (z = 7) c cu hnh: 1s2 2s2 sp3 C th phn b electron vo cc lng t theo cc cch sau: (1) (2) (3) Tng s spin S = +1/2 Tng s spin S = +3/2 (*) Tng s spin S = -3/2

Vy cch phn b th 2 ph hp vi qui tc Hund 1 2.3.2. Qui tc Hund 2: "Trong mt phn lp cc electron c khuynh hng in vo cc lng t c s lng t ml c gi tr ln nht trc". V d: Trng thi c bn ca nguyn t F (z = 9) l trng thi. 0 0 +1 0 -1

1s 2s 2p Ch khng phi l trng thi 0 0 -1 0

+1

1s 2s 2p 2.4. Cch biu din cu to v electron. Cu hnh electron ca nguyn t - Cu hnh eletron ca nguyn t c dng m t cc electron phn b nh th no vo cc lp, phn lp trong nguyn t. C 2 cch biu din: Cch 1: Dng ch v d O (Z = 8): 1s2 2s2 2p4 Trong cc s ng trc 1, 2 ch s th t ca lp n = 1,2, cc ch s s, p ch cc phn lp, cc s m ch s electron c trong phn lp. Cch 2: Dng lng t: O (Z = 8)

18

Cch ny cn cho bit s electron c thn trong nguyn t v nguyn t trng thi c bn hay trng thi kch thch. Da trn cc qui tc v nguyn l trn d dng vit c cu hnh electron ca nguyn t. V d: Cu hnh electron ca mt s nguyn t trng thi c bn. - i vi 20 nguyn t u (Z = 1 20) cu hnh electron trng vi th t mc nng lng (qui tc Klechkowski). - Bt u t nguyn t Z = 21 tr i do c s chn mc nng lng nn cu hnh electron ca cc nguyn t t phn lp 4s tr i khng cn trng vi th t mc nng lng (do vit ng cu hnh trc ht vit theo th t mc nng lng sau chuyn thnh cu hnh theo lp electron). V d: Fe (Z = 26). Theo th t mc nng lng 1s2 2s2 2p6 3s2 3p6 4s2 3d6 Cu hnh electron 1s2 2s2 2p6 3s2 3p6 3d6 4s2 - Khi mt AO c 2e- ta ni cc electron ghp i, nu ch c mt electron th electron l c thn. Cc trng hp ngoi l : Do cu hnh d10 (bo ho) v d5 (bn bo ho) bn, c nng lng thp nn cc nguyn t c cu hnh (n-1)d9ns2 s chuyn thnh cu hnh (n-1)d10ns1 hay cu hnh (n-1)d4ns2 s chuyn thnh (n-1)d5'ns1. V d: Nguyn t Cu hnh electron Cr (z = 24) 1s2 2s2 2p6 3s2 3p6 3d5 4s1 Cu (z = 29) 1s2 2s2 2p6 3s2 3p6 3d10 4s1

V. Cu to ht nhn nguyn t - ng v
Ht nhn nguyn t l thnh phn c bn ca nguyn t, gm cc proton v cc neutron. Trong cc bin i ho l, nu ht nhn vn nguyn vn th bn cht ca nguyn t c bo ton. Nu ht nhn b bin i th nguyn t ca nguyn t ny s chuyn thnh nguyn t ca nguyn t khc. 1. Cu to ht nhn nguyn t Ht nhn mang in tch dng. S n v in tch ht nhn bng s electron ca nguyn t. Ht nhn c khi lng xp x khi lng nguyn t v c th tch rt b so vi th tch ca nguyn t gm cc proton v cc neutron. Nu gi s proton trong ht nhn l Z v s ntron l N th khi lng ca ht nhn xp x bng khi lng nguyn t. A=Z+N

19

2. Hin tng ng v Nhng nguyn t c cng in tch ht nhn (cng s proton) nhng c s khi khc nhau (s neutron khc nhau) gi l cc ng v. V d
16 8

17 8

18 8

3. Hin tng phng x t nhin L hin tng chuyn ho t pht ng v khng bn ca mt nguyn t thnh ng v ca nguyn t khc c km theo s pht ra cc ht c bn hay cc ht nhn nguyn t. C 3 dng phng x c bn: - S phn hu (ht nhn phng ra cc ht )
226 88

Ra

4 2

222 He + 86 Rn 0

S phn hu - (phng ra ht e1 )
239 93

Np

0 1

e+

227 90

Rn
0 1

- S phn hu + (+: ht positon e )

55 27

Co

0 1

e + 55 26 Rn

Km theo cc tia hay l cc tia gm cc bc x in t c nng lng ln. 4. Phn ng ht nhn L phn ng m trong ht nhn ny b bin i thnh ht nhn khc ngha l nguyn t ny chuyn thnh nguyn t khc. Ngi ta thc hin phn ng ht nhn nhn to bng cch dng cc ht c bn nh , n, p bn ph vo cc bia l nhn ca mt nguyn t no . V d: Bn ph nit bng ht
4 2

He + 14 7 N

17 8

O+1 1 H

5. ng dng ca ng v phng x nhn to Bn cnh tc hi to ln ca s phng x n i sng ca con ngi nh cc tia phng x ph hu t bo, tch lu trong xng, gan (nht l cc tia , tia ntron) con ngi bit s dng cc ng v phng x phc v cho vic cha bnh, kch thch s tng trng ca cy trng, x l ht ging, sn xut nng lng V d: 61 Co dng tiu dit t bo ung th 131 I dng chn on bnh bu c 30 P dng theo di s hp thu phtpho ca cy 18 O dng nghin cu c ch ca cc phn ng ho hc v sinh hc

20
14 238

C dng xc nh tui ca cc c vt U dng trong lnh vc nng lng nguyn t.

VI. Cu to nguyn t v h thng tun hon cc nguyn t ho hc

1. nh lut tun hon "Tnh cht ca cc n cht, thnh phn v tnh cht ca cc hp cht ca cc nguyn t ho hc bin thin tun hon theo chiu tng ca in tch ht nhn nguyn t". Vy s bin i tun hon tnh cht ca cc nguyn s l do s bin i tun hon cu trc e- ca nguyn t ca cc nguyn t . 2. Bng h thng tun hon cc nguyn t (Xt bng h thng tun hon dng di) Bng h thng tun hon dng di c xy dng trn c s sau: - Cc nguyn t c xp theo chiu tng dn in tch ht nhn. - Cc nguyn t c cng s lp electron c xp thnh mt hng ngang gi l chu k. - Cc nguyn t c cng cc electron ho tr c xp thnh ct dc gi l nhm. 2.2. S th t cc nguyn t Mi nguyn t c xp vo 1 c s th t ng bng in tch ht nhn Z ca nguyn t . V d: Nguyn t S c Z = 16 c 16p nn c 16e- trng thi c bn. 2.3. Cu to bng h thng tun hon Cc nguyn t ho hc trong bng h thng tun hon c xp theo th t in tch ht nhn Z tng dn v c phn thnh cc chu k v nhm. - Chu k: L dy nguyn t xp theo hng ngang gm cc nguyn t c cng s (tr chu k 1 bt u bng Hydro) v kt thc v mt kh him. S th t ca chu k bng s lp electron m mi nguyn t trong chu k c. Hin nay bng h thng tun hon gm 7 chu k, nh s th t t 1 n 7. Trong : Chu k 1 gm 2 nguyn t H (Z = 1) v He (Z = 2) Chu k 2 gm 8 nguyn t t Li (Z = 3) n Ne (Z = 10) Chu k 3 gm 8 nguyn t t Na (Z = 11) n Ar (Z = 18) Chu k 4 gm 18 nguyn t t K (Z = 10) n Kr (Z =36) Chu k 5 gm 18 nguyn t t Rb (Z = 37) n Xe (Z = 54) Chu k 6 gm 32 nguyn t t Cr (Z = 55) n Rn (Z = 86) (c bit trong chu k 6 c 14 nguyn t xp sau La (Z = 57) c xp tch ring thnh 1 hng ngang di bng gi l h Lantan). - Chu k 7 gm cc nguyn t ang xy dng t Fr (Z = 87) tr i. (Trong chu k 7 c 14 nguyn t xp sau Ac (Z = 89) c tch ring thnh h Actini) * Nhm: Gm cc nguyn t c cng s electron ho tr s th t ca nhm bng s electron ho tr m cc nguyn t c. Mi nhm c chia thnh 2 phn nhm: chnh v ph. - Phn nhm chnh (nhm A): gm cc nguyn t s hoc p - Phn nhm ph (nhm B) gm cc nguyn t d hoc f

21
Cc xc nh s electron ho tr ca mt nguyn t Loi nguyn t s hoc p S electron ho tr - Tng s electron lp ngoi cng - S electron trn ns (nu (n-1) d bo ho - Tng s electron trn ns v (n-1)d [nu (n-1)d cha bo ho] V d: - Cu (z = 29) c cu hnh [Ar]3d104s1: thuc nhm IB - Zn (z = 30) c cu hnh [Ar]3d104s2: thuc nhm IIB - Fe (z = 26) c cu hnh [Ar]3d64s2: thuc nhm VIIIB - Li, Na, K c cu hnh ns1: thuc nhm IA * Khi: Ngy nay ngi ta thng xp cc nguyn t thnh cc khi da vo cu hnh electron ca chng, c 4 khi l: - Khi s: gm cc electron c cu hnh electron ngoi cng l ns 1, ns2 l cc nhm IA, IIA. - Khi p: gm cc nguyn t c cu hnh cc electron ngoi cng t ns 2np1 n ns2np6 tc l cc nguyn t thuc nhm IIIA n VIIIA. - Khi d: gm cc nguyn t c cu hnh (n-1)d1-10ns hoc 2 thuc cc nhm B - Khi f: gm 2 dy lantanic va actinic xp cui bng. 3. S bin i tun hon tnh cht cc nguyn t 3.1. Bin i tun hon cu hnh electron ca cc nguyn t - i vi cc nguyn t nhm A, cc electron lp ngoi cng tng dn t 1e - nhm IA n 8 electron lp VIIIA, iu ny c lp li tt c cc chu k. - i vi cc nguyn t nhm B: Cc electron lp ngoi cng ging nhau l ns2 (tr mt s trng hp ngoi l). + Cc nguyn t d th phn lp electron d tng t 1 electron nhm IIIB n 9 electron nhm IB v 10 electron nhm IIB. + Cc nguyn t f: cu hnh electron ngoi cng v h ngoi ging nhau ch khc nhau phn lp (n-2)f. 3.2. Bn knh nguyn t Trong mt chu k khi i t tri sang phi, in tch ht nhn tng dn nn lc ht gia ht nhn v in t ngoi cng tng dn, do bn knh nguyn t gim dn. Trong mt nhm khi i t trn xung bn knh nguyn t tng dn do s lp in t tng dn. 3.3. Nng lng ion ho (I) L nng lng ti thiu cn cung cp bc mt electron ra khi nguyn t trng thi c bn. - Trong mt chu k khi i t tri sang phi, in tch ht nhn, lc ht gia cc ht nhn v electron ngoi cng tng dn, electron b ht cht hn nn nng lng ion ho tng dn.

22
- Trong mt nhm khi i t trn xung do bn knh nguyn t tng nn khong cch gia ht nhn v electron ngoi cng tng dn, lc ht gia ht nhn v in t ngoi cng gim dn do nng lng ion ho gim dn. 3.4. i lc vi electron (E) L nng lng c gii phng khi nguyn t trng thi kh nhn thm mt electron tr thnh anion kh. A + e- = ACho n nay ngi ta ch mi xc nh c i lc i vi electron ca mt s t nguyn t. Trong cc nguyn t nhm VIIA c i lc vi electron ln nht. Cc nguyn t s 2, s2p6, s2p3 c i lc vi electron rt km. 3.5. S oxi ho - S oxi ho dng cao nht ca cc nguyn t bng s th t ca nhm cha chng (tr cc nhm VIIIB, IB, Lantanic, Actinic, O, F v kh him). - S oxi ho m thp nht hu nh ch c cc nguyn t phi kim v s oxi ho m thp nht ca nguyn t bng s th t ca nhm cha nguyn t tr i 8. V d: Nit c s oxi ho m thp nht l: 5 - 8 = -3 3.6. Hp cht vi hydro v oxi - Hp cht vi hydro: Cc kim loi nhm IA, IIA to cc ion H- (NaH, CaH2 ) Cc nguyn t phi kim thng to cc hp cht cng ho tr, trong hydr c xi ho +1, phi kim c s oxi ho m (CH4, NH3, H2O, HF, HCl )

Hp cht vi oxi: xi to c oxit vi hu ht cc nguyn t (tr Pt, Au). Trong mt chu k khi i t tri sang phi s oxi ho ca cc nguyn t to oxit tng dn t

1 n 7. V d: Chu k 3: Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl2O7 Cc baz v axit tng ng cng nh cc oxit c tnh axit tng dn t tri sang phi. NaOH Mg(OH)2 Al2(OH)3 H2SiO3 H3PO4 H2SO4 HClO4 tnh axit tng dn. Trong mt nhm khi i t trn xung tnh kim loi tng nn tnh baz ca mt oxit v hidroxit cng tng dn. BeO MgO Be(OH)2 Mg(OH)2 lng tnh baz CaO Ca(OH)2 SrO BaO Sr(OH)2 Ba(OH)2 baz mnh

4. Quan h gia cu hnh electron v v tr ca nguyn t trong bng h thng tun hon 4.1. Bit s in tch ht nhn ca nguyn t (Z) ta c th xc nh c nguyn t thuc chu k my, nhm my v cu hnh electron ca nguyn t . V d: Cho X c Z = 16

23
Ta c th vit cu hnh electron ca X: 1s2 2s2 2p6 3s2 2p4 Vy X thuc chu k 3, nhm VIA l nguyn t lu hunh (S). 4.2. Bit cu hnh electron ca nguyn t, c th xc nh in tch ht nhn Z, s th t ca nguyn t, chu k, nhm, hp cht vi hydro, hp cht vi oxi V d 1: Nguyn t X c cu hnh 1s2 2s2 2p6 3s2 3p5 Z = 17 V n = 3 nn nguyn t ny thuc chu k 3. S electron ho tr 2+5 = 7 thuc nhm VIIA l nguyn t Clo. - Hp cht vi hydro l HCl xit cao nht vi oxi l Cl2O7 V d 2: Nguyn t Y c cu hnh 1s2 2s2 2p6 3s2 3p6 3d5 4s2 Z = 25 V lp d cha bo ho nn Y thuc nhm B c e- ho tr l 2+5 = 7 nn Y thuc nhm VIIB c lp electron ngoi cng l 4 nn thuc chu k 4 l nguyn t Mn. - Khng c hp cht vi hydro - xit cao nht ca Mn vi xi l Mn2O7 4.3. Bit v tr ca nguyn t c th suy ra mt s tnh cht ho hc c bn ca mt s cc hp cht ca nguyn t . V d: Bit nguyn t M thuc chu k 4, nhm IIA vy l kim loi kim th, chng c th nhng 2 electron tr thnh cation: M - 2e = M2+ to c cc hp cht c lin kt ion l chnh, hp cht vi hydr c cng thc l MH2, hp cht vi xi l MO v hidroxit tng ng l M(OH)2.

24
CHNG III

CU TO PHN T V LIN KT HO HC

Phn t l phn t nh b nht ca cht, n c to nn t nhng nguyn t cng loi hoc khc loi. V vy nghin cu cu to phn t thc cht l nghin cu cc mi lin kt gia cc nguyn t trong phn t.

I. Mt s khi nim
1. Khi nim v phn t "Phn t l phn t nh nht ca mt cht c kh nng tn ti c lp m vn gi nguyn tnh cht ca cht ". Theo quan im hin i th "phn t bao gm mt s gii hn ca ht nhn v cc electron tng tc vi nhau v c phn b mt cch xc nh trong khng gian to thnh mt cu trc khng gian bn vng". Phn t khng ch l cc phn t trung ho nh H2, Cl2, CO2 m cn bao gm cc ion phn t nh H2+, NO3- 2. m in m in ca mt nguyn t l i lng c trng cho kh nng ca nguyn t ca nguyn t trong phn t ht cp electron dng chung v pha mnh. m in ca nguyn t cng ln th kh nng ht cp electron cng mnh, tnh phi kim ca nguyn t cng mnh. V d: Trong phn t HCl: gia hydro v Clo c mt cp electron dng chung, chng b lch v pha nguyn t Clo v Clo c m in ln hn hydro nn trong phn t HCl th hydro mang in dng v Clo mang in tch m. H+ Cl-

Ngi ta xy dng c thang m in ca cc nguyn t trong hydro c m in bng 2,1 v F c m in cao nht l 4. Trong thang ny th: - Trong mt chu k, m in ca cc nguyn t tng t tri sang phi. - Trong mt nhm m in ca nguyn t gim khi i t trn xung.

25
m in ca mt s nguyn t theo Pauling IA H 2,1 Li 1,0 Na 0,9 3 K 0,8 2 Rb 0,8 2 Cs 0,7 9 9 5 Ba 0,8 Tl 2,0 Pb 2,3 Bi 2,0 Po 2,0 At 2,2 5 Sr 0,9 In 1,8 Sn 2,0 Sb 2,4 Te 2,1 I 2,7 Ca 0,9 Ga 1,8 Ge 2,0 As 2,4 Se 2,1 Br 2,7 Be 1,6 Mg 1,3 B 2,0 Al 1,6 C 2,6 Si 2,0 N 3,0 P 2,2 O 3,4 S 2,6 F 4,0 Cl 3,0 IIA IIIA IVA VA VIA VIIA VIIIA

Ngi ta nhn thy : - Nu hiu s m in ca 2 nguyn t tham gia lin kt ln ( 2) th m my electron gn nh b lch v pha nguyn t c m in ln v hnh thnh lin kt ion. - Nu 2 nguyn t tham gia lin kt c m in bng nhau th my electron lin kt c phn b u gia 2 nguyn t tham gia lin kt v to thnh lin kt cng ho tr. - Nu 2 nguyn t c m in khc nhau khng nhiu lm (hiu s m in gia hai nguyn t <2) th hnh thnh lin kt cng ho tr phn cc. 3. Mt s c trng ca lin kt 3.1. Nng lng lin kt Nng lng ca mt lin kt ho hc l nng lng cn thit ph v lin kt v thnh nguyn t th kh. V d: Nng lng ca lin kt (H-H) trong phn t H2 chnh l hiu ng nhit ca qu trnh. H2 (k) H (k) + H (k) H = 104,2 kcal/mol Nng lng lin kt c trng cho bn ca lin kt, nng lng lin kt cng ln th lin kt cng bn. 3.2. di lin kt di lin kt c xc nh bi khong cch gia 2 ht nhn ca hai nguyn t tham gia lin kt, nu cc nguyn t tham gia lin kt nh nhau, th lin kt cng bn khi di lin kt cng b. V d: phn t F2 Cl2 Br2 I2

26
di lin kt X - X (A0) 1,42 1,99 2,28 2,68

3.3. Gc lin kt Gc lin kt l gc to bi 2 na ng thng xut pht t ht nhn ca mt nguyn t v i qua ht nhn ca 2 nguyn t khc lin kt trc tip vi nguyn t trn. V d: Trong phn t nc, gc lin kt HOH = 104030'. 3.5. Mmen lng cc ca phn t Trong nguyn t, cc electron bao quanh ht nhn c phn b ton ton i xng khp mi pha nn trng tm ca cc in tch trng vi tm ca ht nhn (trng tm ca in tch dng). Trong phn t, trng tm ca cc in tch m v dng c th trng nhau hoc khng trng nhau. - Nu trng tm in tch m v trng tm in tch m trong phn t trng nhau ta c phn t khng phn cc. V d: Phn t H2, N2, F2 - Nu trng tm in tch m v dng khng trng nhau th ta c phn t phn cc. Lc ny phn t c mt mmen lng cc, k hiu l , c n v o l Debye (D). V d: Phn t H-Cl

+
l

l: di lng cc : c tnh theo cng thc = .l Nu = e = 4.8.10-10 vtd CGS v l = 1A0 (10-8cm). Th = 4,8.10-18 vt d.cm Thng thng c gi tr t 0 n 10.10-18 vtd cm nn ngi ta chn 1.10-18 vtd.cm lm n v ca , v c gi l Debye. Mmen lng cc ca phn t c xc nh bng thc nghim, Mmen lng cc ca phn t cng ho tr nm trong khong 0 - 4D v ca cc phn t ion nm trong khong 4 - 11D. Mmen lng cc ca mt s phn t: Phn t: KCl KBr KI (D): 0,8 8,2 9,2

HCl 1,07

HBr 0,79

HI 0,38

II. Lin kt ion

Nh vt l hc ngi c Kossel nhn thy rng trong nhiu hp cht cc nguyn t c xu hng mt i hay nhn thm mt vi electron c cu hnh bn ca kh him ngay trc hay sau chng trong bng h thng tun hon. T ng cho rng c mt loi lin kt ho hc c hnh thnh trong phn t gi l lin kt ion. 1. nh ngha

27
"Lin kt ion l lin kt c hnh thnh do lc ht tnh in gia cc ion mang in tch tri du" V d: Na + Cl Na+ + Cl- NaCl Nhng hp cht to nn bng cch ny gi l hp cht ion. 2. iu kin to thnh lin kt ion m in ca 2 nguyn t tham gia lin kt phi khc nhau nhiu (hiu s m in 2). 3. c im ca lin kt ion - Lin kt ion khng c tnh nh hng: mi ion c th ht v pha mnh cc ion tri du theo mt phng bt k. - Lin kt ion khng c tnh bo ho: do tng tc tnh in gia cc ion ngc du khng dn n s trit tiu hon ton in trng ca nhau, do mt ion sau khi lin kit vi mt ion th 2 ngc du vi n vn cn kh nng lin kt vi cc ion ngc du khc theo cc phng khc, nn lin kt ion khng c tnh bo ho. Do hai tnh cht ny m cc phn t hp cht ion c khuynh hng t kt hp li mnh m, cc phn t ion ring l ch tn ti nhit cao. Cn nhit thng mi hp cht ion u tn ti trng thi rn, c cu trc tinh th v ton b tinh th c xem nh mt phn t khng l. V d: mui, oxit kim loi, hidroxit kim loi thng l cc hp cht ion. 4. Ho tr ca nguyn t trong hp cht ion - Ho tr ca nguyn t trong ion n bng in tch ion V d: Na+, Cl- th Na v Cl u c ho tr 1 - i vi ion a nguyn t: ta khng ni n ho tr ca tng nguyn t m ni n ho tr ca c ion. V d: NH4+, SO3-, ClO4- c ho tr 1 SO42-, HPO42- c ho tr 2

III. Lin kt cng ho tr

Trong 2 kiu lin kt chnh ca phn t, lin kt ion c gii thch bng thuyt tnh in ca Kossel cn lin kt cng ho tr l i tng nghin cu ca nhiu nh khoa hc sut t th k 19 n nay. Trong s cc thuyt ny c th k n 2 quan im ch yu l quan im ca Lewis v quan im ca c hc lng t. 1. Thuyt Lewis v lin kt cng ho tr Theo Lewis khi nguyn t ca 2 nguyn t c m in xp x nhau tham gia lin kt, chng s chung cc electron lm thnh cp electron dng chung cho c 2 nguyn t, khi chng cng c c cu hnh bn vng ca kh him, lin kt ny gi l lin kt cng ho tr - mi cp electron dng chung to thnh mt lin kt. V d: H + H H : H hay H - H H + Cl H Cl hay H - Cl Mi cp electron dng chung c k hiu bng mt vch ngang gi l vch ho tr. - Nu m in ca 2 nguyn t to lin kt bng nhau, cp electron dng chung c phn b u gia 2 nguyn t ta c lin kt cng ho tr khng phn cc (H2, Cl2 )

28
- Nu m in ca hai nguyn t to lin kt hi khc nhau, cp electron dng chung s b lch v pha nguyn t c m in ln hn ta c lin kt cng ho tr phn cc (HCl). * Ho tr ca mt nguyn t trong lin kt cng ho tr: l s lin kt hnh thnh gia mt mt nguyn t ca nguyn t vi cc nguyn t khc trong phn t. V d: Trong CO2 NH3 HCl Clo v hydr c ho tr 1, xi c ho tr 2, nit c ho tr 3 v cacbon c ho tr 4. Thuyt Lewis gii thch kh n gin, d hiu v s to thnh lin kt gia cc nguyn t trong phn t, gii thch c cc trng thi ho tr ca nguyn t trong cc hp cht. Tuy nhin thuyt ny cng gp mt s hn ch v khng gii thch c t tnh ca mt s cht. 2. Quan im ca c hc lng t v lin kt cng ho tr Hai thuyt gn ng ca c hc lng t c s dng rng ri gii thch bn cht ca lin kt cng ho tr l thuyt lin kt ho tr vit tt l VB (Valence Bond) v thuyt orbital phn t vit tt l MO (Molecular orbital). 2.1. Thuyt lin kt ho tr (VB) 2.1.1. Lin kt , lin kt , lin kt Thuyt VB dng s xen ph ca cc orbital nguyn t (AO) m t s to thnh cc lin kt. Tuy theo tnh i xng ca vng xen ph gia cc AO tham gia lin kt i vi trc lin kt (trc vi tm 2 ht nhn), ngi ta phn bit lin kt xch ma (), lin kt () v lin kt (). * Lin kt : nu s xen ph cc AO xy ra trn trc lin kt th lin kt ny gi l lin kt khi phn xen ph trong lin kt s nhn trc ni gia 2 ht nhn lm trc lin kt.

H -H (s-s)

H (s-p)

Cl

Cl (p-p)

Cl

Lin kt : Nu gia 2 nguyn t xut hin lin kt i hoc lin kt 3, th cc lin kt th 2, 3 do cc m my p cn li nh hng theo phng vung gc vi trc ni gia 2 ht nhn nguyn t, cc m my xen ph 2 bn trc lin kt gi l lin kt . V d: phn t nit (N2) c mt mi lin kt v 2 mi lin kt . Vy lin kt c to thnh do s xen ph cc AO ho tr 2 pha trc lin kt.

N (p-p)

N (p-p)

29
Gia 2 nguyn t lin kt vi nhau trong phn t bao gi cng ch tn ti mt lin kt v s lin kt c th c l 0, 1, 2. Lin kt : Lin kt ny t gp, l lin kt sut hin do s xen ph ca cc orbital d. 2.1.2. Lun im c bn ca thuyt VB - Bi ton phn t hydro Khi p dng c hc lng t gii quyt vn bn cht ca lin kt ho hc, nm 1927 hai nh bc hc W.Heiler v F. London gii bi ton tnh nng lng lin kt trong phn t hydr H2. Kt qu vic gii bi ton ny cho thy:

H (1Sa)

H (1Sb)

H2 ( nng lng thp)

Lin kt gia 2 nguyn t hydro c hnh thnh khi 2 electron ca 2 nguyn t hydro c spin ngc chiu nhau ghp i vi nhau. Khi nng lng ca phn t hydro thp hn nng lng ca hai nguyn t hydro c lp v mc nng lng ca hai phn t thp nht khi khong cch gia 2 tm ca hai nguyn t hydro l 0,74A0. Khi hnh thnh lin kt mt my electron khu vc khng gian gia hai ht nhn tng ln ging nh hai m my xen ph ln nhau, do mt in tch m ca khu vc tng ln, nn ht hai ht nhn li vi nhau v lin kt chng li tc l xut hin lin kt gia 2 nguyn t hydro to thnh phn t hydro (H2). T cc kt qu ny rt ra c lun im c bn ca thuyt VB nh sau: Trong phn t cc electron vn chuyn ng trn cc AO. Mi lin kt cng ho tr c to thnh do s ghp i 2 electron c thn c spin tri du ca 2 nguyn t khc nhau tng tc vi nhau, cp electron ny c xem nh chung cho c 2 nguyn t. Khi xy ra s xen ph gia 2 m my electron lin kt, s xen ph cng mnh th lin kt cng bn. Lin kt c phn b theo phng m ti s xen ph ln nhau gia cc AO tham gia lin kt l ln nht, v nh vy s c nhng phng c u tin trong khng gian ph hp vi cu hnh khng gian ca phn t v vy lin kt cng ho tr c tnh nh hng. Lin kt cng ho tr c tnh bo ho ngha l mi lin kt ch m bo bi 2 electron v mt nguyn t tham gia lin kt ch c mt s gii hn cc lin kt ho tr. V d: N kt hp vi H to NH3 , khng to ra cc phn t NH4, NH5 S lin kt vi H to H2S, khng to ra cc phn t H3S, H4S 2.1.3. Cc thuyt trong khun kh thuyt VB * Ho tr ca cc nguyn t theo VB. Thuyt spin v ho tr Ni dung:

30
Ho tr cng ho tr ca mt nguyn t c xc nh bng s electron c thn ca nguyn t ca nguyn t trng thi ang xt. V d: Na (Z = 11) c cu hnh electron: 1s2 2s2 2p6 3s1 c 1 electron c thn phn lp 3s c ho tr 1. O (Z = 8) c cu hnh electron: 1s2 2s2 2p4

phn lp 2p c 3AO cha 4 eletron trong c 2 electron c thn nn oxi c ho tr 2. Trong qu trnh phn ng khi c cung cp nng ln ln mt s electron ghp i c th b kch thch nhy ra cc AO cn trng cc phn mc nng lng ca n ang tn ti tr thnh c thn lm cho s electron c thn tng ln nn lm tng ho tr ca nguyn t. V d: C (Z = 6) - Trng thi c bn: 1s2 2s2 2p2 - Trng thi kch thch 1s2 2s2 2p2 ho tr 2

ho tr 4

Tuy nhin trong iu kin thng ca cc phn ng ho hc thng khng nng lng cho cc electron cc lp bn trong nhy ra cc lp c mc nng lng cao hn, do s kch thch ch c thc hin gia cc phn lp c mc nng lng bng nhau (trong cng mt lp). Nhn xt: Thuyt ho tr spin gip ta gii thch c ho tr ca nhiu nguyn t. Tuy vy n cng gp hn ch nhng khng gii thch c s hnh thnh lin kt trong cc ion phn t v t tnh ca mt s cht, khng gii thch c bn ca cc phn t * Thuyt lai ho orbital Khi nim lai ho c Pauling a ra trong khun kh thuyt VB gii thch s hnh thnh lin kt trong phn t CH4, BeF2 v cc hp cht tng t. Theo Pauling khi tham gia lin kt cc AO ho tr ca cc nguyn t khng tham gia ng thi bng cch trn ln vi nhau trc khi i vo lin kt. Hay ni cch khc l cc AO t hp vi nhau thnh cc t hp tt nht to lin kt bn nht. Cc t hp l cc hm sng tng ng nhau, c nng lng v hnh dng ging nhau v c nh hng r rt trong khng gian. Vy "S lai ho orbital l s t hp cc AO nguyn t trong mt nguyn t to thnh cc AO lai ho ging nhau v nng lng, hnh dng v nh hng r rt trong khng gian". iu kin cc AO lai ho bn l: - Nng lng ca cc AO tham gia lai ho phi xp x nhau - Nng lng ca cc AO tham gia lai ho thp - xen ph cc AO lai ho vi cc AO ca cc nguyn t khc tham gia lin kt phi ln. Cc kiu lai ho gia cc AO ns v np

31
- Lai ho sp: l s t hp gia mt AOs v mt AOp thuc cng mt lp nguyn t, to thnh 2 orbital lai ho c nng lng tng ng v hnh dng ging nhau, trc i xng ca 2 AO lai ho ny to vi nhau mt gc 1800. Trng hp lai ho ny thng xy ra trong nguyn t khi to thnh cc hp cht c dng ng thng nh BeF2, BeH2, BeCl2, CO2, C2H2 V d: Xt s to thnh lin kt trong phn t BeF2 Be (Z = 4): 1s2 2s2 Trng thi c bn sp Trng thi kch thch sp

Hai AO lai ho sp to thnh ca Be s xen ph vi 2 AO ho tr ca 2 nguyn t F (2py) to thnh 2 lin kt Be - F vi gc lin kt FBeF = 1800. F:

2py (F)

sp

Be

sp

2py (F)

Lai ho sp2 (Lai ho tam gic): L s lai ho gia mt AO s vi 2 AO p to ra 3AO lai ho sp 2 nm trong cng mt mt phng, trc i xng ca chng to vi nhau mt gc l 120 0 hng v 3 nh ca mt tam gic u. Lai ho sp2 c dng gii thch cu trc hnh hc ca cc phn t BH3, BF3, BCl3, SO2, SO3 v gii thch lin kt i ca cc nguyn t C trong cc hp cht hu c. V d:

32
Xt s to thnh lin kt trong phn t C2H4 C (Z = 6) Trng thi c bn Trng thi kch thch

Mi nguyn t C thc hin lai ho sp2 to 3 AO lai ho sp2. Gia 2 nguyn t C lin kt vi nhau bng s xen ph ca 2 AO lai ho sp2 to ra lin kt C-C, sau mt AO sp2 ca mi nguyn t C s to 2 lin kt C-H vi cc AO 1s ca 2 nguyn t hydro dc theo trc lin kt to ra b khung ca phn t. mi nguyn t C cn li 1 orbital p cha lai ho (c cha 1 electron c thn). V vy to c mt lin kt vi nhau theo phng vung gc vi trc lin kt c gc ho tr l 1200.
(sp2-s)

H H C
(p-p)

(sp2-s) hay l

H H

C
(sp -sp )
2 2

C C

H H

(sp2-s)

H (sp2-s)

- Lai ho sp3 (lai ho t din) l s lai ho gia mt AO s v 3 AO p to ra 4 AO lai ho sp3 hon ton ging nhau to thnh phn t c cu trc t din hoc gn t din nh CH4, CCl4, SiCl4, H2O, NH3 vi gc ho tr l 109028' hoc gn vi gc . sp3

sp3 sp3 1s + 3AOp V d: xt s to thnh lin kt trong phn t CH4 C (Z = 6) Trng thi c bn sp3

(sp3 s)

H H

33
Trng thi kch thch

Trong phn t CH4, nguyn t C lin kt vi 4 nguyn t H bng s xen ph gia 4 AO lai ho sp3 ca C vi cc AO 1s ca hydr to ra cc lin kt (C-H), phn t CH4 c dng t din u vi tm l C v 4 nguyn t H 4 nh, gc lin kt H-C-H = 109028'. 2.2. Thuyt orbital phn t (MO) Thuyt MO c xy dng hi mun hn thuyt VB bi cc nh bc hc Mucliken, Hund, Cenard - Jones. 2.2.1. Lun im c bn ca thuyt MO - Trong phn t cc electron chuyn ng trn cc hm sng chung ca phn t gi l cc MO. - Cc MO c thnh lp t s t hp cc AO ca hai nguyn t trong phn t: MO = Vi i: cc AO nguyn t Ci: l hng s ni ln s ng gp ca hm i vo MO - Cc AO tham gia t hp phi ph hp nhau v mt tnh i xng v c mc nng lng xp x nhau, khi tham gia t hp chng phi xen ph nhau r rt. - S MO thu c bng s AO tham gia t hp cc MO thu c sp xp theo th t tng dn mc nng lng. - T ta xy dng c gin mc nng lng v vit c cu hnh electron ca phn t. Nh vy theo thuyt ny, bi ton phn t qui v vic xc nh cc MO v cc mc nng lng tng ng ca chng. 2.2.2. Bi ton ion phn t H2+ Ion phn t H2+ l i tng nghin cu c bn v n gin nht ca thuyt MO. V hai nguyn t trong phn t ging nhau nn cc AO ho tr ca chng u ging nhau, ngha l chng c cng tnh cht i xng. Trong trng hp ny s t hp n AO s cho ra n/2 MO lin kt c nng lng thp hn, v n/2 MO phn lin kt c nng lng cao hn ny lng ca cc AO nguyn t trong t hp. V d: MO H + H+ = H2+ 1sA 1sB = C11sA + C21sB

i= 1

C i i

Gii phng trnh Schrodinger i vi hm ny ngi ta tm c hai nghim l: 1 ( 1sA 1sB ) l MO phn lin kt s ng vi nng lng cao hn (c mt + MO = 2 electron khong gia 2 ht nhn nh).

34
( 1sA 1sB ) l MO lin kt s ng vi nng lng thp hn khi trng thi 2 nguyn t (c s tp trung mt e khong gia 2 ht nhn cao). S t hp cc AO to thnh cc MO thng c biu din ln gin gi l gin nng lng cc MO. s l MO lin kt, s* l MO phn lin kt, ch ngha l lin kt H - H+ l lin kt , ch s ngha l lin kt c to thnh t cc AOs. Ta c gin mc nng lng theo thuyt MO ca ion phn t H2+ nh sau: + =
+ MO

1SA

1SB

s H H+2 H+

Ta thy trn gin khi to thnh phn t H2+ nng lng ca h c gim hn nng lng ca cc nguyn t v ion ring l ngha l h H2+ bn hn h H v H+ ring l. T ta c th vit c cu hnh ca H2+ l s1. Bc lin kt theo phng php MO: Theo phng php ny bc lin kt i vi phn t 2 nguyn t c tnh theo cng thc: (n n*) N= 2 Vi n: tng s cc electron trn cc MO lin kt n* : tng s cc electron trn cc MO phn lin kt Nu N = 0 th lin kt khng tn ti ngha l khng c phn ng . V d: He2 cho He (Z = 2): Phn t He2 c 4e(2 2) = 0 N= 2 Do khng tn ti phn t He (nn cc phn t kh him l phn t n nguyn t). 8 4 = 2 (ph hp vi thc nghim) - Trong phn t O2 c bc lin kt l N = 2 - Trong ion phn t H2+

35
N= 1 0 1 = (phn t H2+ c tn ti) 2 2

Bc lin kt cng ln th lin kt cng bn 2.2.3. Thuyt MO v phn t hai nguyn t thuc chu k 2 (phn t hai nguyn t ng hch dng A2). i vi nguyn t chu k 2, c cc AO ho tr l ns v np. - Lp cc MO: Cc MO c xy dng bng s t hp cc AO ho tr, cc MO c chia thnh dng v tu theo tnh i xng ca chng. Ta ch cn xt cc AO ho tr 2s, 2px, 2py v mi AO u c s nh hng r rt trong khng gian, nn ta chn mt h to thng nht cho cc phn t loi A2 vi trc z trng vi trc ca phn t. x x

(a) y

z y

(b)

T hp 2 AO 2s ca 2 nguyn t to 2 MO s v s*. T hp 2AO 2pz to 2 MO z v z* (c i xng trc trng vi trc ca phn t). T hp 2AO 2px v 2px' to cc MO x v x*. T hp 2AO 2py v 2p'y to cc MO y v y* (c trc i xng song song vi nhau v vung gc vi trc ni gia 2 ht nhn). Cc MO x v y, x* v y* tng i mt ch khc nhau v hng trong khng gian nn tng i mt chng c cng mc nng lng (x = y v x* = y*). - Gin cc MO: T 8 AO (2s', 2px', 2py', 2pz') v (2s, 2px, 2py, 2pz) ca 2 nguyn t ngi ta xy dng c 8 MO gm 4MO lin kt v 4MO phn lin kt. Ta c 2 gin . Gin 1: Th t mc nng lng ca phn t A2 cc nguyn t cui chu k 2 (O2, F2, Ne2) nh sau: s < s* < z < (x = y) < (x* = y*) < z* tng ng vi gin 1:

36
Gin 1: A E x A2 z y A

2p

2p

z H s* 2s 2s s

Gin 2: i vi cc nguyn t u chu k (t Li n N) do s chnh lch nng lng ca cc AO 2s v 2p khng ln lm nn c s xen ph gia AO 2s v 2pz lm cho MO z v z* tr nn km bn hn do nng lng ca z ln hn nng lng ca MO x, y: do th t mc nng lng ca cc phn t A2 ca nguyn t ny nh sau: s < s* < (x = y) < z < (x* = y*) < z*

T ta c gin 2 ca cc phn t ny

37
Gin 2 E x y A A2 z* A

2p z x y

2p

H s* 2s 2s s

* Tnh cht t ca phn t V mt t tnh ngi ta phn bit cht thun t v cht nghch t. - Nhng cht c cha electron c thn trong phn t thng b t thng ht gi l cc cht thun t. - Nhng cht m trong phn t tt c cc electron ghp i b t trng y gi l cht nghch t. T cu hnh electron ca phn t ta c th d on tnh cht t ca chng. p dng thuyt MO cho cc phn t A2 thuc chu k 2. V d 1: Phn t Li2: (vi Li (Z = 3) Li: 1s22s1 2 nguyn t Li c 6e- 2e- phn lp 2s. Cu hnh phn t Li2: s2 2 0 =1 N= 2 Khng c electron c thn nn phn t nghch t. V d 2: O2 cho O (Z = 8) Mi nguyn t O c 6e lp th 2, 2 nguyn t c 12e - sp xp vo cc mc nng lng nh sau:

38
s2 s*2 2z (2x = 2y)(x*1 y*1) 8 4 = 2 N= 2 Phn t c 2e- c thn nn c tnh thun t V d 3: Phn t Ne2 cho Ne (Z =10) Mi nguyn t Ne c 10 electron, 2 nguyn t Ne c 20 electron, vy c 16 electron sp xp nh sau: s2 s*2 2z (2x = 2y)(x*2 y*2) 8 8 = 0 N= 2 V vy phn t Ne2 khng tn ti 3. Lin kt phi tr L lin kt cng ho tr m cp electron dng chung ch do mt nguyn t a ra, nguyn t ny gi l nguyn t cho. y c s chuyn cp electron t do ca nguyn t cho v orbital trng ca nguyn t nhn. Lin kt phi tr c k hiu bng mt mi tn hng t nguyn t cho sang nguyn t nhn. V d: H3N: + H+ = [H3N : H]+ 1s hay [H3N H]+ hay NH4+ Trong thc t, khng th phn bit lin kt phi tr v lin kt cng ho tr thng thng. V d: trong NH4+, bn lin kt ca N vi H hon ton ging nhau v di lin kt v nng lng lin kt. Lin kt phi tr thng gp trong cc phc cht.

IV. Tng tc gia cc phn t

Ngoi cc lin kt chnh xt nh lin kt ion, lin kt cng ho tr cn c cc tng tc gia cc phn t nh lin kt hydr, lc Vanderwaals. 1. Lin kt hydro Nguyn t hydro ngoi kh nng tham gia lin kt cng ho tr thng thng, cn c kh nng to mt mi lin kt th hai vi mt nguyn t khc c m in ln v kch thc nh. Mi lie kt th hai ny km bn hn nhiu so vi lin kt cng ho tr thng thng v c gi l lin kt hydro, k hiu bng du ba chm () V d: - Lin kt hydro lin phn t F H F H F (HF)n H F H R O H O H H

Ru v nc

39
Trong phn t HF, nguyn t H sau khi lin kt vi nguyn t F bng mt lin kt cng ho tr cn hnh thnh mi lin kt th hai (lin kt hydr) vi nguyn t F ca phn t HF khc to nn phn t lin hp (HF)n. - Lin kt hydro ni phn t
N O O O H H C O

ortho nitrophenol

andehyt salicilic

* Nguyn nhn xut hin lin kt hydro Do c im cu to nguyn t ca hydro l ch c mt electron duy nht nn khi nguyn t hydro lin kt cng ho tr vi mt nguyn t ca nguyn t c m in ln th my electron ca hydro b ht lch mnh v pha nguyn t v lm nguyn t hydro b bin thnh ht tch in dng mc khc cn do kch thc ca hydro rt nh nn ion hydro d dng tin gn n cc nguyn t hay ion khc, thm ch thm nhp vo lp v electron ca cc nguyn t hay ion khc hnh thnh nn mi lin kt hydro. Nng lng ca lin kt hydro rt b (khong 2 - 10 kcal/mol) nn lin kt hydro km bn hn lin kt ho hc thng thng (khong hng trm kcal/mol). * nh hng ca lin kt hydro n tnh cht ca cc cht - Lm tng nhit nng chy, nhit si ca cc cht do lin kt hydro to nn lc ht gia cc phn t, gy nn s trng hp phn t lm phn t lng trung bnh ca cc cht tng nn nhit nng chy v nhit d si ca cc cht tng. V d: Cht HF HCl M 20 36,5 T0nc (0C) -83 -112 T0s (0C) 19,5 -84,9

Lm gim in li, gim tnh axit ca cc cht. V d: Trong dy HX cc axit HCl, HBr, HI l cc axit mnh nhng do trong cc phn t HF c lin kt hydro lin phn t nn HF l cht in li yu v c tnh axit trung bnh. - Lm tng tan ca cc cht: lin kt hydro gia cc phn t cht tan v dung mi lm tan ca cc cht tng do d hnh thnh solvat. V d: Gia ru v nc c lin kt hydro nn ru tan v hn trong nc, trong khi te (ROR) khng tan trong nc do gia te v nc khng c lin kt hidro. S hnh thnh lin kt hydro lin phn t cho php gii thch tnh d ho tan ca cc hp cht c nhm phn cc trong nhng dung mi phn cc nh nc, ru Ngoi ra lin kt hydro lin phn t cn lm gim tnh baz ca cc cht v gy nn s bin i bt thng v khi lng ring.

40
* Lin kt hydro mi phn t lm thu gn cc phn t li ng thi lm gim kh nng to lin kt hydro gia cht vi dung mi do lm gim nhit nng chy, nhit si v tan ca cc cht, lin kt ny cn lm gim tnh axit ca cc cht. 2. Lc Vanderwaals L lc tng tc gia cc phn t, n c bn cht tnh in. Lc Vanderwaals cng ln th mmen lng cc ca phn t, kch thc v khi lng ca phn t cng ln. Lc vanderwaals b hn vi nng lng ca lin kt ion v lin kt cng ho tr nn n ch c nh hng ch yu n mt s tnh cht l hc ca cc cht. V d: Theo dy F2, Cl2, Br2, I2 th kch thc v khi lng tng t u n cui dy nn lc vaderwaals tng dn do nhit si v nhit nng chy ca cc cht ny tng dn. Lc Vardenwaals bao gm cc thnh phn sau: * Lc nh hng: khi cc phn t phn cc gn nhau chng tng tc vi nhau bng lc tnh in lm cho cc phn t xoay hng sp xp mt cch c trt t nhm lm gim nng lng ca h.

* Lc cm ng: cc phn t phn cc tng tc vi cc phn t khng phn cc lm xut hin lng cc gia chng.

* Lc khuych tn: cc phn t khng phn cc gn nhau do chuyn ng ca cc electron lm cho mt electron lun lun bin i nn lm dch chuyn trng tm in tch dng v m nn lm xut hin cc lng cc tm thi v chng ht nhau bng lc ht tnh in.

Lc Vanderwaals gm E = E1 + E2 + E3

41
Lc Vanderwaals tuy nh nhng cng lm cho cc phn t ny buc nhau nn thng nh hng n tnh cht vt l ca cc cht nh nhau, nhit nng chy, nhit si

V. S lc v trng thi tp hp ca cc cht

Cc cht tn ti ba trng thi: rn, lng, kh 1. Trng thi kh c trng bi khong cch gia cc phn t ln, cc phn t xa nhau, chng chuyn ng t do hn lon theo mi phng v c th nn chng a cc phn t ny li gn nhau. V vy cc cht kh c th dn n v cng c th b nn nn chng gy ra p sut ln bnh vt cha. Trng thi v tnh cht vt l ca cc cht kh tun theo cc nh lut ring v cht kh. 2. Trng thi lng c trng bi khong cch gia cc phn t nh hn, cc phn t c th chuyn ng t do nhng khng th nn p c hc gim th tch ca chng. Trng thi lng linh ng, khng c hnh dng ring, di tc dng ca nhit, cc phn t cht lng c th ri khi trng thi lng v chuyn thnh hi (gi l s bay hi). Ngc li cng bng tc dng c th c nh cc phn t v chuyn cht lng thnh trng thi rn. 3. Trng thi rn Ngay iu kin thng nhiu cht tn ti trng thi rn. c trng ca trng thi ny l cc phn t gn nhau n mc khng th chuyn ng t do, chng ch dao ng quanh mt v tr cn bng no v vy cht rn c kh nng gi c hnh dng ca n. V mt cu trc cht rn gm 2 dng l cht rn tinh th v cht rn v nh hnh. * Cht rn tinh th: trong tinh th cc ht (nguyn t, phn t, ion, nhm nguyn t ) c sp xp theo mt trt t hon ton xc nh, chng hu nh khng chuyn dch tnh tin m ch dao ng chung quanh v tr cn bng. Cht rn tinh th c nhit nng chy xc nh. * Cht rn v nh hnh: l cht rn m phn t sp xp hn n gn vi trng thi lng, tuy vy n cng khc vi trng thi lng l ht ca cht v nh hnh khng c chuyn ng tnh tin v chuyn ng quay. Cht v nh hinh khng c nhit nng chy xc nh khi b un nng n mm ra, nho dn ri ho lng, di tc dng ca cc lc bn ngoi cht v nh hnh c th b bin dng. V d: Cc cht rn v nh hnh nh thu tinh, cao su

42
CHNG IV

NHIT NG HC HO HC
Nhit ng hc ha hc nghin cu cc quy lut chuyn bin gia ha nng v cc dng nng lng khc, cc iu kin b vng ca h ha hc v nhng quy lut thay i ca chng h t c trng thi cn bng, t c th iu kin qu trnh ha hc theo mun.

I. Mt s khi nim c bn
1. H nhit ng H nhit ng l mt vt th hay mt nhm vt th m ta kho st, cch bit vi mi trng xung quanh bng b mt thc s hay tng tng. Trong mt h xc nh, ngi ta thng xt n hai yu t: lng vt cht v cc dng nng lng d tr trong lng vt cht . Ngi ta phn bit: 1.1. H h (hay h m) H m l h c th trao i cht v nng lng vi mi trng xung quanh. 1.2. H kn (hay h ng) H kn l h khng trao i cht m ch c s trao i nng lng vi mi trng xung quanh. 1.3. H c lp H c lp l h khng trao i c cht v nng lng vi mi trng xung quanh. 1.4. H ng nht H ng nht l h m cc tnh cht cn xem xt u ging nhau vi mi trng xung quanh. 1.5. H d th H d th l h trong tn ti b mt phn chia gia cc phn trong h. 1.6. H ng th H ng th l h trong khng tn ti b mt phn chia gia cc phn t c trong h. 2. Cu t Mi phn t tn ti trong h ,ng nht v phng din ho hc, c th tch ra khi h v tn ti ngoi h gi l mt cu t. V d: dung dch nc mui c hai cu t 3. Pha (tng) Tp hp tt c nhng phn ng th ca h, ging nhau v thnh phn ho hc v tt c cc tnh cht nhit ng, ngn cch vi nhng phn khc nhau bng nhng b mt phn chia gi l pha (hay tng) ca h. H ng th bao gi cng c mt pha, cn h d th c nhiu pha. 4. Trng thi Trng thi ca mt h l ton b nhng tnh cht l ho ca h. Trng thi ca h c c trng bng cc thng s trng thi P, V, T, n. Cc thng s ny lin h vi nhau bng cng thc PV = nRT.

43
Cc thng s trng thi c chia thnh hai loi - Thng s trng thi khuch : t l vi lng cht - V d: th tch, khi lng. - Thng s trng thi cng : khng t l vi lng cht. V d: nhit , p sut, nng 5. Hm trng thi Mt i lng c gi l hm trng thi ca h nu bin thin ca i lng ch ph thuc vo trng thi u v trng thi cui ca h, khng ph thuc vo cch tin hnh. Ngc li, nu s bin i ca thng s cn ph thuc vo c cch tin hnh qu trnh th khng c gi l hm trng thi (i khi gi l hm qu trnh). V d: Nng lng l mt hm trng thi, nhng nhit v cng khng phi l hm trng thi. 6. Qu trnh Khi h chuyn t trng thi ny sang trng thi khc, ta ni h thc hin mt qu trnh. Nu sau mt s bin i, h tr v trng thi u th qu trnh c gi l vng (hay chu trnh), ngc li l qu trnh m. - Qu trnh xy ra nhit khng i (T-const) c gi l qu trnh ng nhit - Qu trnh xy ra p sut khng i (p = const) l qu trnh ng p - Qu trnh xy ra th tch khng i (V = const) l qu trnh ng tch. - Nu qu trnh khng trao i nhit vi mi trng, nhng c th trao i cng (khi dn n) c gi l qu trnh on nhit. 7. Qu trnh t din bin v qu trnh khng t din bin - Qu trnh t din bin l qu trnh thc hin trong h khng cn c s can thip t bn ngoi, ngha l khng cn tiu th cng t bn ngoi, tri li khi kt thc c th sinh ra cng. - Qu trnh khng t din bin l qu trnh khng thc hin c nu nh khng c s can thip t bn ngoi, ngha l phi tiu tn cng. 8. Qu trnh thun nghch v qu trnh khng thun nghch - Qu trnh 12 c gi l thun nghch nu nh c th thc hin c qu trnh ngc 21 i qua ng vi mi trng thi trung gian nh ln i thun, sao cho khi h tr v trng thi u th khng cn tn ti mt bin i no trong chnh h cng nh mi trng. - Qu trnh xy ra khng c kh nng tr li trng thi ban u gi l qu trnh bt thun nghch. Vi qu trnh bt thun nghch, cng v nhit sinh ra nh hn qu trnh thun nghch: qtn > qbtn ; Atn > Abtn

9. Nng lng Nng lng l thc o vn ng ca cht. C hai cch chuyn nng lng: - Nu s chuyn nng lng c lin quan n s di chuyn mt h c hc th s chuyn nng lng c thc hin di dng cng. K hiu A. - Nu s chuyn nng lng c lin quan n vic tng tc chuyn ng ca phn t vt nhn nng lng th s chuyn nng lng c thc hin di dng nhit. K hiu q. q, A l hm qu trnh, c o hm ring l q, A.

44
II. Nguyn l th nht ca nhit ng hc
1. Ni nng ca h(U) L tng nng lng d tr ca h bao gm nng lng ca mi dng chuyn ng v tng tc ca lng vt cht c trong h nh nng lng chuyn ng tnh tin, chuyn ng quay ca phn t, nng lng dao ng ca nguyn t, phn t, nng lng chuyn ng ca e trong nguyn t v phn t, nng lng lin kt ho hc, nng lng ht nhn. Vic tnh gi tr tuyt i ca ni nng trong h rt kh khn nhng bin thin ca n c th xc nh c v c nhiu ch li hn. Ni nng l hm trng thi (ph thuc trng thi u v cui), vi phn dU ca n l vi phn ton phn. 2. Nguyn l th nht ca nhit ng hc L tin rt ra t nhng kinh nghim thc tin ca con ngi. 2.1. Ni dung Nguyn l ny c th pht biu theo nhiu cch Cch 1: Nng lng khng th t sinh ra cng khng t mt i, n chuyn t dng ny sang dng khc theo nhng t l tng ng nghim ngt. Cch 2: Khng th c ng c vnh cu loi mt, l ng c c kh nng lin tc sinh cng m khng cn cung cp nng lng tng ng. Cch 3: Ni nng ca mt h c lp c bo ton 2.2. Biu thc ton hc ca nguyn l I Theo nguyn l I, khi cung cp mt lng nhit Q h chuyn t trng thi mt sang trng thi hai th lng nhit ny bin i ni nng ca h t U1 sang U2 v hon thnh mt cng A chng li cc lc bn ngoi. q = A + U U = U2 - U1 A = Adn n + A' Adn n : Cng chng li p sut mi trng A' : Cng chng li cc lc khc tc dng ln h

Nu vit di dng vi phn, ta c: q = dU + A

Sau y ta xt kh nng sinh cng ca h: - Trong h c lp, h khng nhn nhit (q = 0), khng sinh cng (A = 0) th U = 0. Vy trong h c lp, ni nng ca h c bo ton - Trong trng hp h khng nhn nhit (q = 0) li sinh cng (A > 0), khi ta c: A + U = 0 => A = -U > 0. Ngha l: (U2 - U1) > 0 U1 > U2: ni nng ca h phi gim. - Trong cc phn ng ho hc, thng thng cng A l cng dn n, chng li p sut bn ngoi.

45
A = P (V2 - V1) = PV Vy trong qu trnh ng tch: V = 0 A = 0 Do : qv = U - Kt lun: nhit to ra hay thu vo trong qu trnh ng tch ca phn ng ho hc bng bin thin ni nng ca h. 3. Entanpi (H) a s cc phn ng ho hc xy ra p sut khng i (v d: p sut kh quyn) th biu thc v lng nhit m h hp ph qp. qp = U + PV = (U2 - U1) + P (V2 - V1) = (U2 + PV2) - (U1 + PV1) t: H = U + PV qp = H2 - H1 = H H = U + PV i lng H c gi l entanpi ca h. Do U, P, V l hm trng thi nn H cng l hm trng thi, c trng cho trng thi ca h. - Kt lun: lng nhit to ra hay thu vo trong qu trnh ng p bng bin thin entanpi ca h. 4. Quan h gia U v H Ta c: qv = U v qp = H = U + PV - i vi nhng qu trnh ho hc ch c cht rn v cht lng tham gia th i lng V c gi tr khng ng k. Do khi qu trnh c thc hin p sut thp th PV rt nh: H U - i vi nhng qu trnh c cht phn ng hay sn phm phn ng th kh th U v H c th khc nhau. Tht vy, i vi kh gn l tng ta c: PV = nRT PV = nRT H = U + nRT Khi n = 0 U = H n 0 U H

III. Nhit ha hc
Nhit ho hc l mt lnh vc ca ho hc nghin cu v s bin i nhit lin quan n cc phn ng ho hc. Trong phn ng ho hc, v tng nng lng ca cc cht tham gia v cc cht to thnh khng bng nhau, ngha l c s bin i nng lng. S bin i nng lng (to ra hay hp th) c th hin di dng nhit nng, quang nng hay in nng, trong nhit nng ng vai tr quan trng nht. 1. Hiu ng nhit ca phn ng Hiu ng nhit ca mt phn ng ho hc l lng nhit to ra hay thu vo khi mt mol cht tham gia vo phn ng (hay mt mol sn phm c to thnh). Lng nhit to ra hay thu vo bng s tng hay gim entanpi ca h.

46
- n v o Kcal/mol KJ/mol - Qui c - Phn ng to nhit: Q> 0 - Phn ng thu nhit: Q < 0 Du ca nhit ng hc khc du ca nhit ho hc. * Ch : T cc biu thc ca nguyn l I v quy c tri du ca nhit ng hc vi nhit ho hc, ta c: Qp = - qp = -H Qv = - qv = - U Vy: nhng phn ng to nhit ra mi trng xung quanh ngha l lm nng mi trng xung quanh gi l phn ng to nhit. Trong trng hp ny h phn ng mt nhit nn: H < 0. V d: Cc phn ng t chy - Nhng phn ng ly nhit ca mi trng xung quanh, ngha l lm lnh mi trng xung quanh gi l phn ng thu nhit H > 0 V d: Phn ng nhit phn CaCO3 * Phng trnh ho hc c km theo hiu ng nhit gi l phng trnh nhit ho hc. Do hiu ng nhit ph thuc vo nhit nn so snh hiu ng nhit ca cc qu trnh, ngi ta s dng i lng hiu ng nhit tiu chun H0, l hiu ng nhit c xc nh iu kin chun 250C v 1atm. Trong phng trnh nhit ho hc thng ghi c trng thi ca cc cht trong phn ng. V d: Cth.ch + O2(k) = CO2 (k) H0 = - 94,052kcal/mol 2. Sinh nhit (nhit to thnh) (Hs) Sinh nhit hay nhit to thnh ca mt hp cht l hiu ng nhit ca phn ng to thnh mt mol hp cht t cc n cht iu kin chun. V d: H2(k) + 1/2O2 (k) = H2O (k) H0s(H2O) (k) = -57,8 kcal/mol * Ch : Sinh nhit ca cc n cht bn iu kin chun bng 0 3. Thiu nhit (nhit t chy) (H0 c) Thiu nhit ca mt cht l hiu ng nhit ca phn ng t chy mt mol cht bng oxi va to thnh oxit bn iu kin chun. i vi cc cht hu c, thiu nhit l hiu ng nhit ca phn ng t chy hon ton 1 mol cht thnh CO2 v hi nc (hay nc lng) v cc sn phm tng ng khc. V d: CH4 + 2O2 = CO2 + 2H2O H0c (CH4) = - 212,8kcal/mol * Ch : i vi cc nguyn t, thiu nhit ca mt nguyn t chnh l sinh nhit ca oxit bn ca n. V d: Cth.chi + O2(k) = CO2(k) H0 = -94,052 kcal/mol Ho - Sinh nhit ca CO2

47
- Thiu nhit ca C 4. Nhit phn hu (H0ph) Nhit phn hu ca mt hp cht l hiu ng nhit ca phn ng phn hu mt mol hp cht thnh cc n cht bn iu kin chun. 5. nh lut Hess 5.1. nh lut Nh bc hc Nga G. Hess (1802-1850) a ra c nh lut Hess nh sau: Hiu ng nhit ca qu trnh ho hc ch ph thuc vo bn cht v trng thi ca cc cht u v cc sn phm ch khng ph thuc vo cch thc hin phn ng. V d: A+B (trng thi u) A+B
H1

E+F E + F (trng thi cui)

H2

H3

C+D H1 = H2 + H3 5.2. H qu - Hiu ng nhit ca mt phn ng ho hc bng tng sinh nhit ca cc sn phm tr tng sinh nhit ca cc cht tham gia phn ng (cht u), km theo h s trong phng trnh phn ng. Hp = Hs (sp) - Hs (c) -Hiu ng nhit ca mt phn ng ho hc bng tng thiu nhit ca cc cht tham gia ( cht u) tr tng thiu nhit ca cc sn phm, km theo h s trong phng trnh phn ng. Hp = Hc (c) - Hc (sp) - Hi ng nhit ca mt phn ng bng tng nng lng lin kt c trong phn t cc cht tham gia t tng nng lng lin kt c trong phn t cc sn phm (km theo h s trong phng trnh phn ng). Hp = Hlk (c) - Hlk (sp) - Hiu ng nhit ca mt qu trnh vng bng khng. - Trong phn ng thun nghch: nu phn ng thun c hiu ng nhit l H th phn ng nghch c hiu ng nhit l - H. 5.3. ng dng ca nh lut Hess 1. Tnh hiu ng nhit ca phn ng theo Hsn, Htn, Hlk v ngc li 2. Tnh hiu ng nhit ca nhiu phn ng khng th o trc tip. 3. Tnh nng lng ca thc n a vo c th. V d: Glucoza khi vo c th, qua rt nhiu phn ng nhng sn phm cui cng l CO2 v H2O, do lng nhit do glucose cung cp cho c th bng lng nhit do cht ny to ra khi t n vi O2 bn ngoi c th, lng ny c th xc nh c do tnh c nng lng do glucose sinh ra. 5.4. nh lut Lavoisier - Laplace Nhit to thnh v nhit phn hu ca mt hp cht bng nhau v gi tr v ngc du.

48
IV. Nguyn l II ca nhit ng hc
Nguyn l th nht nhit ng hc i n kt lun: gia cc dng nng lng trong mt h nhit ng c th chuyn ho tng h theo mt t l nh lng nghim ngt. Tuy nhin nguyn l khng cho php xc nh chiu hng v gii hn ca qu trnh. Chnh nguyn l th hai xc nh nhng qu trnh no trong nhng iu kin cho c th t din bin v din bin ti gii hn no. 1. Ni dung C th pht biu nhiu cch: Cch 1: Nhit khng th t truyn t vt lnh sang vt nng hn. Cch 2: cng c th chuyn hon ton thnh nhit, cn nhit khng chuyn hon ton thnh cng. Cch 3: Khng th c ng c vnh cu loi 2, l loi ng c bin nhit hon ton thnh cng. 2. Entropi Xt 2 kh l tng A v B khng tng tc nhau, hai ngn ca bnh kn. Khi ct mng ngn, A v B s khuch tn t nhin vo nhau cho n khi trn u nhau, qu trnh ny khng km theo hiu ng nng lng no v y l kh l tng.

(trng thi ban u)

AB BA A thi cui) (trng

Ta thy s phn b cc phn t trng thi ban u c trt t cao hn trng thi cui hay trng thi cui c hn n cao hn. Nh vy, trong iu kin nng lng khng i, h c khuynh hng chuyn t trng thi c hn n thp sang trng thi c hn n cao hn. V mt ton hc, trng thi c hn n cao c xc sut tn ti ln hn, c gi l xc sut nhit ng ca trng thi hay xc sut trng thi, k hiu W. V xc sut trng thi ca mt trng thi v m c tr s rt ln, kh tnh ton nn ngi ta dng i lng entropi, k hiu S. S = RlnW R: hng s kh l tng. Trong iu kin nng lng ca h khng i, s xy ra qu trnh chuyn h t trng thi c xc sut nh (W1) sang trng thi c xc sut ln hn (W2): S1 = RlnW1 W2 S = S2 - S1 = Rln W1 S2 = RlnW2 W 2 > W 1 S2 > S1 Do h c khuynh hng chuyn cht t trng thi c entropi nh sang trng thi c entropi ln hn. S = S2 - S1 > 0 Vy entropi l mt hm trng thi, c trng cho mc hn n ca h. H s t trng thi bn nht khi entropi cc i.

49
3. Biu thc ton hc ca nguyn l II Q S T Q Biu thc vi phn: dS T Q: o hm ring nhit lng trao i T: nhit tuyt i S: entropi Du = ng vi qu trnh thun nghch S = S2 - S1 = Du > ng vi qu trnh bt thun nghch S >

Q T 1

Q T 1

Nh vy entropi l thc o thun nghch hay khng thun nghch ca qu trnh. * Ch - Entropi c tnh cht cng tnh: Sh =

i= 1

S i = S1 + S 2 + ... + S n

S1, S2 ... l entropi ca cc thnh phn - Entropi l mt hm trng thi nn i vi mt phn ng ho hc: Sp=Ssp - Sc (km theo h s trong phng trnh phn ng). - Khi nghin cu entropi ca cc cht, ngi ta thy Skh > Slng > Srn - Trong h c lp, Q = 0 => S 0 S = 0 qu trnh thun nghch S > 0: qu trnh khng thun nghch, S tng. Nh vy trong h c lp, nhng qu trnh t din bin l nhng qu trnh c km theo s tng S. 4. Cch tnh entropi ca mt s qu trnh thun nghch 4.1. Qu trnh thun nghch ng nhit (chuyn pha) Q S = T TN V d: Qu trnh nng chy: S = Qu trnh ho hi : S = 4.2. Qu trnh thun nghch ng tch T2 S = Cvln T1 Cv: nhit dung ng tch Qnc Tnc Qhh Thh

50
4.3. Qu trnh thun nghch ng p T2 S = Cpln T1 Cp: nhit lng ng p

V. Th ng p v chiu t din bin ca qu trnh ha hc

1. Tc ng ca yu t entanpi v entropi ln chiu hng ca qu trnh - Qu trnh d xy ra khi H < 0, ngha l khi nng lng ca h gim, cc tiu phn sp xp trt t hn, h tr nn bn hn. - Qu trnh xy ra khi S > 0, ngha l h c khuynh hng chuyn t trng thi c hn n thp sang trng thi c hn n cao. l hai qu trnh t nhin tc ng ng thi ln qu trnh ho hc nhng ngc nhau v trong mi qu trnh lun lun c s tranh ginh gia hai yu t , yu t no mnh hn s quyt nh chiu ca qu trnh. V vy, cn phi tm mt hm phn nh ng thi hai yu t , du v tr s ca hm ny c th dng lm tiu chun xc nh chiu hng v mc din bin ca qu trnh.. 2. Th ng p - ng nhit (Nng lng t do Gibbs) Gibbs (nh vt l ngi M (1839-1903) kt hp c hai yu t trong mt hm trng thi gi l th ng p - ng nhit G (gi tt l th ng p) hay cn gi l nng lng t do Gibbs: G = H - TS Tng t ni nng, entanpi v entropi, th ng p G cng l mt hm trng thi. - Khi S = 0, ngha l i vi qu trnh trong khng c s thay i mc hn n, hay s thay i l khng ng k => qu trnh ch chu nh hng ca yu t entanpi. => qu trnh s t din bin khi H < 0 => G = H => G < 0. - Khi H = 0 ngha l i vi nhng qu trnh khng c s hp th hay gii phng nng lng (v d qu trnh khuch tn cc kh), ch c yu t entropi nh hng n chiu hng din bin ca qu trnh. => qu trnh s t din bin khi S > 0, v H = 0 => G = -TS => G < 0. - Khi H < 0, S > 0: c hai yu t entropi v entanpi u thun li cho s din bin ca qu trnh: G = H - TS => G < 0. - Khi H > 0, S < 0: c hai yu t entropi v entanpi u khng thun li cho s din bin ca qu trnh. Qu trnh khng th t xy ra c. Do G = H - TS => G > 0. - Khi H < 0, S < 0: qu trnh c thc y bi yu t entanpi nhng b cn tr bi yu t entropi. Trong trng hp ny, qu trnh ch c th t din bin khi yu t entropi mnh hn yu t entanpi, hay |H| > |TS|, ngha l G = H - TS => G < 0. - Khi H > 0, S > 0: qu trnh s t din bin nu yu t entropi mnh hn yu t entanpi hay |TS| > || => G = H - TS => G < 0. Tm li, tiu chun xt qu trnh c th t din bin hay khng l: G < 0 hay H - TS < 0 => H < TS: qu trnh t din bin G > 0 hay H - TS > 0 => H > TS: qu trnh khng th t xy ra

51
G = 0 => G = TS = 0 => H = TS: qu trnh t cn bng 3. Cch tnh bin thin th ng p ca qu trnh 3.1. Tnh H v S ca qu trnh, sau tnh G = H - TS 3.2 Da vo th ng p hnh thnh chun G0 ca cc cht. Th ng p hnh thnh chun G0 ca mt cht l bin thin th ng p ca qu trnh to thnh mt mol cht t cc n cht bn iu kin chun. V G l hm trng thi nn G0 ca phn ng ho hc bng tng bin thin th ng p ca cc sn phm tr i tng bin thin th ng p ca cc cht u (km theo h s t lng). G0p = G0sp - G0c * Ch : G0 ca n cht trng thi bn vng bng 0 3.3. C th tnh G0p nh sau: Tnh hng s cn bng Kc hay Kp ca phn ng ri tnh G0 Gp = G0 + RTlnKc Gp = G0 + RTlnKp Ti trng thi cn bng: G = 0 => G0 = -RTlnKc hoc G0 = -RTlnKp - o sc in ng ca nguyn t ganvanic trong xy ra v phn ng ha hc v tnh G0 = -nE0F n: s e m mt phn t cht oxi ho nhn hy mt phn t kh nhng. F: s Faraday, F = 96.500Coulomb E0: sc in ng ca pin

G0:

52
CHNG V

NG HO HC
ng ho hc nghin cu tc ca cc phn ng ho hc v cc yu t nh hng n tc nh: nng , nhit , cht xc tc T cho php tm hiu v c ch ca cc phn ng ho hc.

I. Mt s khi nim
1. Tc phn ng biu th mc nhanh hay chm ca mt phn ng ngi ta dng khi nim tc phn ng. Tc ca mt phn ng ho hc c biu th bng bin thin nng ca cht tham gia phn ng hay sn phm ca phn ng trong mt n v thi gian. V d: Xt phn ng A + B C + D Nu phn ng thc hin nhit v th tch khng i, ti cc im t1 v t2, ta ly nng cht A tng ng l C1 v C2 th tc trung bnh ca cc phn ng trn trong khong thi gian (t2 -t1) l: v= C 2 C1 C = t 2 t1 t

V nng ca cc cht bin i lin tc, nn chnh xc hn ngi ta s dng tc tc thi ca phn ng (ngha l tc ti thi im t xc nh). Lc tc tc thi ca phn ng c tnh bng o hm bc nht ca nng theo thi gian. dC v= dt y nu C l nng cht tham gia phn ng ta phi t thm du tr, nu C l nng sn phm th ly du (+) m bo tc phn ng l mt i lng lun lun dng. 2. Phn ng n gin v phn ng phc tp - Phn ng n gin: l phn ng ch din ra qua mt giai on. V d: H2 + I2 2HINO + O3 NO2 + O2 - Phn ng phc tp: l phn ng xy ra qua nhiu giai on V d: 2N2O5 4NO2 + O2 l phn ng phc tp v gm 2 giai on ni tip nhau: N2O5 N2O3 + O2 (giai on 1)

53
N2O3 + N2O5 4NO2 (giai on 2) 3. Phn t s v bc phn ng tm ra cc qui lut chung v tc phn ng, ngi ta phn loi phn ng da theo bc v phn t s. * Phn t s L s tiu phn (phn t, nguyn t hay ion) ng thi tng tc vi nhau trong mt giai on ca phn ng. V vy phn t s l mt s nguyn. V d: CH3 - N = N - CH3 CH3 - CH3 + N2 tham gia vo tng tc ch c mt phn t. V vy phn t s l mt v c gi l phn ng n phn t. Nu s tng tc xy ra khi c s tham gia ca 2,3 phn t th c gi l phn ng lng phn t, tam phn t. V d: H 2 + I2 = 2HI (phn ng lng phn t) 2NO + H2 = N2O + H2O (phn ng tam phn t) Phn ng 4 phn t tr ln thng khng gp trong thc t v mun c xc phn ng cc phn t phi va chm nhau v xc sut va chm ca 4 phn t tr ln thng rt him nn i a s phn ng ho hc l n hoc lng phn t. * Bc phn ng Bc phn ng l tng cc s m ca nng vit trong biu thc ca nh lut tc dng khi lng ca mt phng trnh ng hc thc nghim (yu t nng thc s quyt nh tc ca mt phn ng). V d: O2 + 2H2 2H2O l phn ng bc 3 nh vy bc phn ng c th l s nguyn nhng cng c th l phn s. * Ch : i vi phn ng n gin, bc phn ng trng vi phn t s, i vi phn ng phc tp bc phn ng c xc nh da trn giai on no xy ra chm nht, lc c th bc phn ng khng trng vi phn t s ca phn ng. V d: 2N2O5 4NO2 + O2 l phn ng bc 1 mc d c phn t s l 2 v bc phn ng ny c xc nh a vo giai on 1 l giai on xy ra chm hn. N2O5 N2O3 + O2 Ngoi ra khi nng ca cc cht rt khc nhau th bc ca chng cng khng trng vi h s t lng ca cc cht phn ng. V d: phn ng thu phn ng saccoza C12H22O11 + H2O C6H12O6 + C6H12O6 (gluc) (Fructo)

54
l phn ng bc 1 v lng nc thu phn rt ln, nn nh hng ca nc n qu trnh hu nh khng i nn khng cn ch n. 4. Phn ng ng th v phn ng d th * Phn ng ng th: l phn ng xy ra trong h ng th. V d: N2 (k) + 3H2 (k) 2NH3 (k) * Phn ng d th: l phn ng xy ra trong h d th. C (r) + H2O (h) CO (k) + H2 (k) Phn ng d th xy ra phc tp lun phn ng ng th v ngoi qu trnh chuyn ho hc cn phi tnh n qu trnh chuyn vt th n bin gii tip xc gia hai pha v ngc li.

II. Cc yu t nh hng n tc phn ng

1. nh hng ca nng n tc phn ng 1.1. nh lut tc dng khi lng Mt phn ng ho hc mun xy ra, cc cht tham gia phn ng va chm nhau, nhng va chm dn n xy ra phn ng gi l cc va chm c hiu qu. Khi nng cc cht tng, s va chm c hiu qu cng tng dn nn phn ng xy ra nhanh hn. 1867 Gulberg v Waager a nh lut tc dng khi lng nn nh hng ca nng n tc ca phn ng c ni dung sau: " nhit xc nh, tc phn ng t l thun vi tch s nng ca cc cht tham gia phn ng, mi nng c s m l h s t lng ca cc cht trong phng trnh phn ng". V d: Vi phn ng tng qut: aA + bB cC + dD
a b C B hay v = [A]a [B]b Theo nh lut ny ta c: v = kC A

(Biu thc ny l phng trnh ng hc ca phn ng trn). Trong : - k: hng s tc , n ph thuc vo bn cht ca cht phn ng v nhit . - CA, Cb: nng ca cc cht tham gia phn ng tnh theo n v mol/l - Nu CA = CB = 1 th lc v = k lc ny k c gi l vn tc ring ca phn ng. * Ch : - i vi phn ng phc tp, bc ca phn ng c xc nh da vo giai on no xy ra chm nht do v ca phn ng s c xc nh bng v ca giai on chm nht. Ngha l: v = k[A]m[B]n Cc lu tha m, n s c xc nh bng con ng thc nghim cho giai on chm nht, cn trong trng hp phn ng n gin th n trng vi h s v b ca [A] v [B] trong phng trnh phn ng. i vi phn ng thun nghch: aA + bB cC + dD Tc phn ng ti 1 thi im nht nh bng hiu s cc tc ca phn ng thun nghch.

55
v = v t - vn Ti thi im cn bng th vt = vn vphn ng = 0 2. nh hng ca nhit n vn tc phn ng Ni chung tc ca cc phn ng ho hc thng tng ln khi nhit tng. 2.1. Qui tc Van't Hoff "Khi nhit ca phn ng tng ln 100 th hng s tc ca phn ng (hay l tc phn ng) tng ln t 2 n 4 ln. k + 10 = t = 2 4 kt kt = 10: hng s tc nhit t + 100 kt : hng s tc nhit t : h s nhit ca phn ng Trong trnghp tng qut, biu thc ca nh lut Van't Hoff c dng k + n.10 n = t kt vi V d: mt phn ng c h s nhit l = 3. Hi khi tng nhit ln 400 th tc ca phn ng tng ln bao nhiu ln. Gii: theo qui tc Van't Hoff ta c: k t + 4.10 = 34 = 81 kt Vy v phn ng tng ln 81 ln 2.2. Biu thc Arrhnius nh hng ca nhit n tc phn ng c biu th chnh xc hn v p dng c trong mt khong nhit rng hn qua biu thc Arrhnius: k = A.e-E*/RT R: hng s kh l tng (R = 1,98 cal/mol.k) A: hng s E*: hng s i vi mt phn ng xc nh cn c gi l nng lng hot ho ca phn ng, n ph thuc vo bn cht ca cht phn ng. e: c s logarit t nhin (e = 2,71) T biu thc ny ta thy khi nhit tng, tc phn ng tng v phn ng c nng lng hot ho cng b th phn ng cng d dng xy ra. 2.3. Thuyt hot ho (thuyt va chm hot ng) v nng lng hot ho Theo thuyt ny th khng phi tt c mi va chm u xy ra phn ng m ch c nhng va chm ca cc nguyn t hay phn t hot ng mi dn n phn ng. Cc nguyn t hay phn t hot ng l cc nguyn t hay phn t c mt nng lng d ln so vi nng lng trung bnh ca chng. Vy "nng lng hot ho ca mt phn ng l nng lng ti thiu m mt mol cht phn ng phi c chuyn phn t ca chng t trng thi bnh thng sang trng thi hot ng".

56
Nh vy, c th phn ng c vi nhau, phn t cc cht phn ng phi vt qua mt hng ro nng lng , chnh l nng lng hot ho ca phn ng. Nu nng lng hot ho cng nh th tc phn ng s cng ln. V vy khi xt kh nng phn ng ngi ta thng dng i lng ny so snh. n v nng lng hot ho l kcal/mol hoc kJ/mol. 3. nh hng ca cc cht xc tc n v phn ng 3.1. Mt s khi nim v xc tc 3.1.1. Xc tc l hin tng lm thay i tc ca cc phn ng ho hc c thc hin bi mt s cht c bit gi l cht xc tc, cc cht ny sau khi phn ng xy ra n c hon tr li v lng v cht. Thng thng "cht xc tc" c dng ch cc cht lm tng tc phn ng (gi l cht xc tc dng). V d: H2 + 1/2O2 bt Pt H2O MnO2, nhit 2KClO3 2KCl + 3O2 Cht xc tc lm gim tc phn ng gi l cht xc tc m (hay cht c ch). V d: Na2SO3 lu trong khng kh d b xi ho theo phn ng. 2Na2SO3 + O2 = 2Na2SO4 Nhng nu cho ng hoc SnCl4 th s lm gim vn tc ca phn ng ny rt nhiu. Tuy nhin khi ni n s xc tc, ch yu ng ta vn quan tm n cc cht xc tc dng. 3.1.2. Xc tc ng th v xc tc d th * Xc tc ng th: Cht xc tc v cht phn ng cng mt pha (lng hoc kh) phn ng xy ra trong ton b th tch ca h phn ng ngha l trong khng gian ba chiu. V d: SO2 + O2
NO

SO3

ng pha kh

* Xc tc d th: Cht xc tc v cht phn ng cc pha khc nhau. Thng th cht xc tc pha rn cn cc cht phn ng pha lng hoc kh. Phn ng ch xy ra trong khng gian hai chiu, trn b mt ca cht xc tc. Tc phn ng t l thun vi b mt cht xc tc. V d: 2H2O2 (l) MnO2 2H2O(l) + O2 (k) d th lng - rn 3.2. c im ca cht xc tc - Lng cht xc tc s dng rt b so vi lng cht phn ng. - Cht xc tc khng gy ra c phn ng ho hc - Ngha l i vi nhng phn ng khng c kh nng xy ra v mt nhit ng hc th khng th dng cht xc tc no lm cho phn ng xy ra c. - Trong phn ng thun nghch, cht xc tc lm bin i tc phn ng thun v phn ng nghch mt s ln nh nhau nn n ch lm cho qu trnh mau t n trng thi cn bng.

57
- Cht xc tc c tnh chn lc. mt cht xc tc thng ch c th xc tc cho mt phn ng hoc mt loi phn ng nht nh. . V d: T C2H5-OH c th iu ch C2H4 hoc CH3CHO tu theo cht xc tc em s dng. C2H4 + H2O (xt Al2O3; 3500C) C2H5OH CH3CHO + H2 (xt Cu, 2500C) * Ch : Khi s dng cht xc tc ta cn gp cc cht sau: - Cht tng hot: cht lm tng hot tnh ca xc tc. V d: Khi thm mt t Na2SO4 vo V2O5 th hot tnh xc tc ca V2O5 tng mnh. - Cht c xc tc: l cht m khi trn n vo cht xc tc th hot tnh ca cht xc tc mt i. V d: HCN l cht c ca xc tc As2S5. 3.3. C ch xc tc 3.3.1. C ch xc tc ng th Vai tr ca cht xc tc l lm gim nng lng hot ho ca phn ng ho hc, khi cc phn ng xc tc xy ra, cc cht xc tc tham gia to cc hp cht trung gian vi cc cht phn ng, sau cc hp cht trung gian s phn ng tip vi cc cht cn li hoc t phn hu to nn sn phm. Mc d phn ng c xc tc ng th xy ra theo nhiu giai on hn, nhng mi giai on li c nng lng hot ho b nn vn tc chung ca phn ng tng. V d: Xt phn ng A + B AB * Khi cha c xc tc A + B [A B] AB ; E1* (ng 1)

* Khi c mt xc tc K, qu trnh xy ra qua nhiu giai on A + K [A ... K] AK E2* AK + B [AK ... B] AB + K ,E3* (ng 2) Cc i lng E2*, E3* u rt nh so vi E1* nn cc phn ng ny xy ra nhanh hn do tc phn ng tng (sn phm cui cng vn l AB, cn cht xc tc K c khi phc nh c).

58

E E*1 [ A...B]

E*3 E*2

[A...K]

[ AK...B]

A +B A +B+K
AB AB+K ng phn ng

iu ny c m t qua gin nng lng nh trn 3.3.2. C ch xc tc d th C ch xc tc d th phc tp hn v c nhiu thuyt gii thch, trong thuyt hp ph l d dng nhn hn c. Ta bit b mt cht xc tc c kh nng hp ph cc cht phn ng, lm cho cc cht phn ng tin li gn nhau v di trng lc cc tiu phn b mt xc tc, hot tnh ho hc ca cc phn t tng ln, lm cho nng lng hot ho ca phn ng gim xung. Kt qu l phn ng xy ra trn b mt cht xc tc vi vn tc ln hn rt nhiu so vi khi khng c xc tc. Khng phi tt c cc phn trn b mt cht xc tc u c kh nng lm cho cc phn t cht phn ng tr nn hot ng m ch c mt s trung tm hot ng b mt xc tc to c hp cht trung gian hot ng gia cht xc tc v cht phn ng, cc hp cht ny s phn ng vi cc cht cn li to nn sn phm. tng thm s trung tm hot ng, ngi ta tng din tch b mt ca cht xc tc bng cch nghin nh xc tc, hoc cho xc tc dng xp hoc ko si rt mnh. C ch xc tc d th gm cc giai on sau: - Cc cht phn ng khuych tn n b mt cht xc tc s hp ph mt trong cc cht phn ng tng hot tnh ca cht phn ng.

59
- Phn ng xy ra trn b mt cht xc tc. - Cc sn phm phn ng to thnh v tch khi b mt cht xc tc v i vo trong h. 3.4. Xc tc enzim (xc tc men) Cc phn ng ho hc xy ra trong c th sng thng c s tham gia ca cc cht xc tc, l cc men hay enzim gi l xc tc men. Enzim l cht xc tc sinh hc, c bn cht protein. Trong xc tc enzim cc cht phn ng c gi l c cht. Phn ng gia enzim v c cht c thc hin cc trung tm hot ng ca cht xc tc. Xc tc enzim c mt s c im sau: - Kh nng xc tc ca enzim khng xy ra trn ton b phn t m xy ra cc trung tm hot ng c bit. Nhng trung tm c tnh xc tc thng cha cc hot ng nh: -SH, -OH, -NH2, -NH- ... hoc cc nguyn t chuyn tip nh Co, Mn, Mo, Fe ... s trung tm hot ng cng tng th kh nng xc tc ca enzim cng ln. - S tn ti v kh nng hot ng ca men ph thuc vo nhit , pH ca mi trng, s c mt ca cc cht x ... 1000C hu ht cc men u b phn hu. - Mt phn ng xy ra trong sinh hc thng c mt xc tc men ring nn vic tm ra cc enzim c hiu thc y cc qu trnh sinh hc theo hng c li l mt trong nhng mc tiu ca cng ngh sinh hc v vy xc tc men c tnh chn lc cao. V d: Men ureaza xc tc cho phn ng thu phn ure Co(NH2)2 + H2O CO2 + 2NH3 - Xc tc enzim xy ra nhit v p sut bnh thng vi hiu sut phn ng rt cao. Nu s dng chng trong sn xut th hiu qu kinh t s rt ln.

III. Phng trnh ng hc ca phn ng

Phng trnh ng hc m t quan h nh lng gia nng ca cc cht phn ng v thi gian - Da vo phng trnh ny ta c th xc nh c mt s thng s quan trng ca phn ng nh hng s tc , bc phn ng, chu k bn hu ca phn ng 1. Phn ng bc mt Phn ng bc mt c dng tng qut: A sn phm Theo nh khi lng ta c: d [ A] v= = k t [ A] dt d [ A] = kd T ta c: [ A] t t ln[A] ln[A0]

Gii phng trnh vi phn ny ta c - ln [A] + ln[Ao] = kt hay ln[A] = kt + ln[Ao] hay c th vit di dng: 1 [ Ao] k t = ln [ A] T Trong

tg = -kt

60
[A]: nng cht A ti thi im t [Ao]: nng cht A khi t = 0 th ln[A] = f(t) l mt ng thng m h s gc s cho bit gi tr ca hng s tc k ca phn ng. Hng s tc ca phn ng tc c th nguyn l 1/t. Phn ng bc 1 thng l phn ng phn hu cc cht. V d: C2H6 C2H4 + H2
232 90

Th

228 88

Ra + 4 2 He

Khi nghin cu cc phn ng bc 1 ngi ta thng ch n i lng chu k bn hy ca phn ng l thi gian m mt na lng ban u ca cht phn ng b tiu th. Gi t1/2 l thi gian nng ban u cn li mt na. [A] = 1/2[Ao] thay vo phng trnh (III.1) ta c: [ Ao] = kt = ln ln = 1/ 2 2 1 / 2[ Ao] hay ln 2 0,693 = k k Ngha l thi gian bn hu ca phn ng bc 1 khng ph thuc vo nng ban u m ph thuc vo bn cht phn ng. 2. Phn ng bc 2 Phn ng bc 2 c cc dng: 2A sn phm A + B sn phm t1 / 2 =

* Dng 2A v=

k2

d [ A] d [ A] 2 = k 2 [ A] = k dt dt [ A] 2 2

sn phm

Gii phng trnh vi phn trn ta c: 1 1 = k 2t + [ A] [ Ao] (III.2) 1 1 1 (III.3) k2 = t [ A] [ Ao] hng s tc ca phn ng bc 2 c th nguyn lt/mol -1/t-1 khi t = t1/2 ta c: 1 t1/2 = (III.4) k 2 [ Ao] hay Vy thi gian bn hu ca phn ng bc 2 ph thuc vo nng u ca cht phn ng. V d v phn ng bc 2:

61
2O3 3O2 2C4H6 C8H12 k2 * Dng A + B sn phm Nu [Ao] = [Bo] th ti mi thi im [A] = [B] v vy d [ A] 2 = k 2 [ A][ B ] = k 2 [ A] dt Do c th p dng cc phng trnh (III.2), (III.3); (III.4) Nu [A] = [B] th d [ A] d [ A] v= = k 2 [ A][ B ] = k dt dt [ A][ B] 2 v= Gii phng trnh vi phn ny ta c 1 [ Bo][ A] k 2t = ln [ Ao] [ Bo] [ Ao][ B] 3. Phn ng bc 3 k3 Cc phn ng bc 3 c dng 3A 2A + B A+B+ C Xt trng hp n gin nht: 3A v= d [ A] d [ A] 3 = k 3 [ A] = k 3 dt 3 dt A sn phm sn phm sn phm sn phm

[ ]

Gii phng trnh vi phn trn ta c 1 1 = 2k 3t + 2 [ A] [ Ao] 2 4. Phn ng bc 0 A

k0

sn phm

Tc phn ng khng ph thuc vo nng ca cht phn ng d [ A] v= = k 0 A 0 = k 0 dt dt Gii phng trnh trn ta c [A] = -k0t + [Ao]

[ ]

IV. Mt s phn ng khc

1. Phn ng quang ho 1.1. nh ngha Phn ng quang ho l phn ng ho hc xy ra di tc dng ca nh sng.

62
nh sng y c th l nh sng trng thy, bc x hng ngoi v bc x t ngoi. Bc x c bc sng cng ngn c nng lng cng ln th s c tc dng mnh n cc cht phn ng. Trong vng quang ph nhn thy, bc x c tc dng yu nht, bc x tm c tc dng mnh nht, bc x t ngoi c tc dng mnh hn nhiu. V d: AgBr Ag + 1/2Br2 H2 + Cl2 2HCl 1.2. nh lut ng lng quang ho Quan h gia nng lng nh sng c hp ph v lng cht phn ng c m t theo nh lut ng lng quang ho ca Einstein a ra vo nm 1912: "Mt phn t cht phn ng c th c hot ho v tr nn c kh nng phn ng do hp ph mt lng t nng lng ca nh sng". e = h T y ta tnh c nng lng E cn thit m mt mol cht phn ng hp ph t mt bc x no . C = E = N0h 10 C 0 C = 3,10 cm/s E=Nh h = 6,625.10-34 J/s Thay gi tr cc hng s vo, ta c: hay h = 1,58.10-34 cal/s 2,859 cal / mol E= N0 = 6,023.1023 phn t T y ta thy: - Da vo bc x hp th ta tnh c nng lng cn thit mt phn t gam cht tham gia phn ng. - Mi phn ng xy ra cn c mt nng lng xc nh nn phn ng quang ho c tnh chn lc. - Khi lng cht phn ng t l thun vi nng lng bc x b hp th. 1.3. Phn ng cm quang, s tng nhy Mt s phn ng quang ho ch xy ra khi trong h c mt mt cht khc, cht ny c vai tr gip cho cht tham gia phn ng hp th nng lng ca bc x. Cht ny c gi l cht tng nhy. Phn ng quang ho c cht tng nhy gi l phn ng cm quang. V d: Phn ng quang hp cy xanh, tng hp ng Glucza t CO2 v H2O vi cht tng nhy l clorophin (dip lc). 6CO2 + 6H2O C6H12O6 + 6O2 y l phn ng quan trng nht xy ra trn tri t v nh n m to ra oxi, tng hp c cc hydrocacbon l cc cht hu c, ngun nng lng cho tt c cc qu trnh sng ca sinh vt. 2. Phn ng dy chuyn Phn ng dy chuyn c lin quan n s xut hin cc gc t do. V vy ngi ta cn gi l phn ng gc t do. V d:

63
H2 + Cl2 2HCl Cl + H2 HCl + H H + Cl2 HCl + Cl y l phn ng dy chuyn dng khng phn nhnh V d 2: Phn ng dy chuyn phn nhnh Phn ng H2 + O2 H2O Phn ng H2O H H2O +O2 +H2 +H2

OH H2 + O2 OH

+H2

OH O

H2O OH H H

+H2 O2 O2

+H2

+O2

OH +H2

Giai on khi mo Giai on pht trin mch Mt phn ng gc t do thng c 3 giai on: khi mo, pht trin mnh v ngt mch. Giai on ngt mch l kt qu phn ng gia cc gc t do V d: OH + H H2O H + H H2 O + O O2 3. Phn ng ni tip L phn ng din ra theo nhiu giai on ni tip nhau: V d: Phn ng thu phn trisaccarit C18H32O16 C18H32O16 + H2O C12H22O11 + C6H12O6 C12H22O11 + H2O C6H12O6 + C6H12O6 Glucoza Fructoza Tc ca phn ng ni tip l tc ca giai on no chm nht trong cc phn ng thnh phn. 4. Phn ng song song T nhng cht ban u phn ng din ra theo mt s hng to ra cc sn phm khc nhau. V d: Khi nitro ho phenol ta thu c ng thi ba sn phm khc nhau: orto, meta v para nitro phenol. Trong loi phn ng ny nng ca cc sn phm t l vi tc ca cc phn ng thnh phn.

64
CHNG VI

CN BNG HO HC
I. Phn ng thun nghch v phn ng mt chiu
1. Phn ng mt chiu L phn ng xy ra n cng cho n khi tiu th ht hon ton mt trong cc cht tham gia phn ng. V d: Zn + 4HNO3 Zn(NO3)2 + 2NO2 + 2H2O Khi lng aixt HNO3 c th phn ng s kt thc khi lng km tan ht, ngc li nu sc kh NO2 vo dung dch th cng khng thu c kim loi v axit. 2. Phn ng thun nghch C nhng phn ng m sau mt thi gian phn ng ta cn tm thy c cht u v sn phm, ngha l phn ng khng xy ra n cng. V d: N2 + 3H2 t0,p,xt 2NH3 Fe3O4 + 4H2 3Fe + 4H2O Nhng phn ng ny gi l phn ng thun nghch. Trong loi phn ng ny ngi ta dng du hai mi tn ngc chiu nhau ( ) thng chiu t tri sang phi l chiu thun, chiu ngc li l chiu nghch. c im ca phn ng thun nghch l khng bao gi ht cc cht ban u v vy ni phn ng thun nghch l phn ng khng hon ton.

II. Cn bng ho hc - hng s cn bng

1. Khi nim v cn bng ho hc Xt phn ng thun nghch aA + bB cC + dD Ti thi im ban u: CA, CB 0 cn CC, CD = 0
a b a b Ta c: vt = k t C A C B hay vt = k t [ A] [ B ]

Ti thi im t 0, xut hin sn phm ngha l c phn ng nghch xy ra.

c d c d vn = k n CC CD hay vt = k n [ C ] [ D ]

Ngi ta gi trng thi ca phn ng thun nghch khi c vt = vn l trng thi cn bng ho hc. Khi h t trng thi cn bng ho hc th cc phn ng thun nghch vn xy ra vi vn tc bng nhau nn trng thi cn bng ho hc l trng thi cn bng ng.

65
2. Hng s cn bng 2.1. Hng s cn bng Khi h t trng thi cn bng ta c vt = vn kt = [A]a [B]b = kn [C]c [D]d
kt [ C ] [ D] = k n [ A] a [ B ] b
c d

T ta c: (II.1) Vy K l t s gia tch s nng cc cht sn phm phn ng v tch nng ca cc cht tham gia phn ng. mt nhit xc nh kt, kn l hng s nn KC cng l mt hng s v c gi l hng s cn bng ca phn ng. [II.1] l biu thc ca nh lut tc dng khi lng p dng cho cn bng ho hc. "Khi h t trng thi cn bng, tch s nng ca sn phm phn ng vi s m l h s t lng ca chng chia cho tch s nng ca cc cht tham gia phn ng vi s m l h s t lng tng ng lun lun l mt hng s mt nhit xc nh gi l hng s cn bng". K l i lng c trng cho mt cn bng, K cng ln cn bng cng chuyn theo chiu thun. K hiu: KC: khi hng s cn bng c biu th qua nng cc cht Kp: Khi hng s cn bng c biu th qua p sut Khi :
d PCc PD Kp = a b PA PB

KC =

Trong : PA, PB, PC, PD l p sut lc cn bng ca A, B, C, D trong h. 2.2. Quan h gia KC v KP T phng trnh: PV = nRT vi pi: p sut ring phn ca kh i ni RT Ta c: PiV = niRT pi = V pi = ciRT Thay cc gi tr ca pi vo biu thc tnh Kp ta c:
c d d PCc PD [ (C ) RT ] [ ( D) RT ] KP = a b = PA PB [ ( A) RT ] a [ ( B ) RT ] b

KP =

[ C ] c [ D ] d .( RT ) (c+ d ) ( a+ b) [ A] a [ B] b

Vy KP = KC.(RT)n Vi n = (c + d) - (a + b)

66
Khi n = 0 tc l s phn t kh 2 v bng nhau th KP = KC Khi n 0 th KP KC * Nu cht phn ng hoc sn phm l cht rn th nng hoc p sut ring phn xem nh khng i nn cc cht ny khng c mt trong biu thc hng s cn bng. V d: Fe3O4 (2) + 4H2 (k) KC = 4H2O v
(h)

+ 3Fe KP = P
4 PH 2

(2)

[ H 2 O] [H2 ]4

4 H 2O

* Ch : i vi cc loi cn bng khc nhau th hng s cn bng c tn gi khc nhau. - i vi cn bng axit baz, ta c Ka, Kb - i vi cn bng kt ta ta c tch s tan T - i vi cht in li ta c hng s in li : Kl - i vi phc cht ta c hng s khng bn: Kkhng bn 2.3. Hng s cn bng v cc i lng nhit ng Xt phn ng tng qut: aA + bB cC + dD * Nu A, B, C, D l cc cht tan trong dung dch lon ca chng ngi ta chng minh c: G = G
0

[ C ] c [ D] d + RTln [ A] a [ B] b

hay G = G0 + RTlnKp Chuyn sang logarit thp phn ta c: G = G0 + 2,3 RTlgKp Khi t h trng thi cn bng G phn ng = 0 th G0 = -2,3 RTlgKp Thay R = 1,98 vo ta c: G0 = -4,56 TlgKp y l biu thc quan h gia hng s cn bng v cc i lng nhit ng nh sau: G0 lgKp = _ 4,56 T hay KP = 10
G 0 / 4 , 56T

III. S chuyn dch cn bng v nguyn l chuyn dch cn bng

1. Khi nim v s chuyn dch cn bng. Nguyn l chuyn dch cn bng Ta thy mt h cn bng c c trng bng cc gi tr xc nh ca cc i lng nhit ng nh: nhit , p sut, s mol Nu ta thay i cc yu t ny th cn bng ca h s thay i v h s chuyn sang trng thi cn bng mi.

67
Mi s chuyn dch cn bng u tun theo nguyn l chuyn dch cn bng lechaterlier nh sau: "Khi mt h ang trng thi cn bng nu ta thay i mt trong cc yu t nh hng n cn bng nh nhit , p sut, s mol cn bng s chuyn v pha chng li s thay i ". Ta c th c th ho s chuyn dch cn bng nh sau: Yu t tc dng - Tng nhit - H nhit - Tng nng cht tham gia - Tng nng sn phm - Tng p sut - H p sut Cn bng chuyn v pha - Chiu phn ng thu nhit - Chiu phn ng pht nhit - Chiu thun - Chiu nghch - Chiu gim s ph t kh (gim P) - Chiu tng s phn t kh (tng P)

2. Xt mt s v d v chuyn dch cn bng 2.1. nh hng ca nng Xt phn ng: FeCl3 + KSCN Fe(SCN)3 + 3KCl mu ang trng thi cn bng. Nu tng nng FeCl3 hoc KSCN th tc phn ng thun tng cn tc phn ng nghch cha tng do to thnh nhiu Fe(SCN)3 hn nn ta thy mu ca dung dch tng ln, cn bng chuyn theo chiu gim nng ca FeCl3 v KSCN. Khi cho KCl vo, tc ca phn ng nghch tng nn mu ca dung dch gim hn so vi ban u v vy cn bng chuyn theo chiu nghch, chiu gim nng KCl. 2.2. nh hng ca p sut Xt phn ng thun nghch Xt phn ng thun nghch: 2NO (k) + O2 (k) 2NO2 (k) ang trng thi cn bng. Cn bng s chuyn theo chiu no nu ta tng p sut ca h ln 2 ln v gim p sut ca h xung 2 ln? Gi s h ang trng thi cn bng no ng vi nng cc cht l: [NO] = a; [O2] = b; [NO2] = c khi ta c: vt = kt [NO]2 [O2] vn = kn [NO2]2 ti trng thi cn bng: vt = vn nn kta2b = knc2 * Khi tng p sut ca h ln 2 ln th nng cc cht tng ln gp i ngha l: [NO] = 2a [O2] = 2b [NO2] = 2c 2 2 khi vt = kn (2a) (2b) = 8kta b (Tc phn ng thun tng ln 8 ln)

68
vn = kn (2c)2 = 4knc2 (Tc phn ng nghch tng ln 4 ln) Vy vt tng nhanh hn vn v cn bng chuyn theo chiu thun. Ngc li nu gim p sut ca h xung 2 ln, nng ca cc cht gim cn 1/2 so vi ban u, khi : [NO] = a/2 [O2] = b/2 [NO2] = c/2 2 2 Nn vt = kt (a/2) (b/2) = 1/8kta b (Tc phn ng thun gim 8 ln) vn = kn (c/2)2 = 1/4knc2 (Tc phn ng gim 4 ln) Vy vn ln hn vt do phn ng chuyn theo chiu nghch, chiu tng p sut ca h. * Ch : Trong trng hp tng s phn t kh 2 v ca phng trnh bng nhau. Vic tng hoc gim p sut ca h khng nh hng n trng thi cn bng. 2.3. nh hng ca nhit Khi tng nhit ngha l ta cung cp thm nng lng cho h, phn ng thu nhit (cn nng lng) c tng cng, khi vn tc ca phn ng thu nhit tng hn tc ca phn ng pht nhit, kt qu phn ng chy theo chiu phn ng thu nhit. V d: Khi tng nhit ca phn ng 2NO2 (k) N2O4 (k) H < 0 (nu) (khng mu) th phn ng s chuyn theo chiu chng li s tng nhit tc l chiu nghch (chiu phn ng thu nhit) ta thy kh NO2 c to nn nhiu hn, mu nu m dn. Ngc li khi h nhit , cn bng chuyn theo chiu thun, chiu tng nhit (phn ng pht nhit) mu nu nht dn, cn bng chuyn v pha to N2O4 nhiu hn.

69
CHNG VII

DUNG DCH
Dung dch l mt h ng nht gm cht tan v dung mi m thnh phn c th bin i trong mt gii hn rng Cc phn ng ha hc thng xy ra trong dung dch lng vi dung mi l nc. V vy vic tm hiu cc quy lut chi phi cc phn ng xy ra trong dung dch nc l iu rt cn thit.

I. Nng v tan ca dung dch

1. Nng biu th thnh phn ca mt dung dch, ngi ta dng nng dung dch. Vy nng dung dch l lng cht tan c trong mt lng xc nh dung dch hoc dung mi, lng cht tan ln to dung dch c, ngc li l dung dch long. 1.1.Nng % 1.1.1. Nng % theo khi lng Biu th s gam cht tan c trong 100g dung dch. mct: khi lng cht tan(g) mct C% = .100 mdd: khi lng dung dch (g) mdd V d: dung dch saccaroza 5% ngha l trong 100g dung dch c 5g saccaroza v 95g H2O. 1.1.2. Nng % theo th tch Biu th s ml cht tan c trong 100ml dung dch. V d: ancol etylic 700 ngha l trong 100ml dung dch ru ny cn c 70ml C2H5OH nguyn cht v 30ml H2O. 1.2. Nng mol / l(M). Biu th s mol cht tan c trong mt lt dung dch. n C M = ct V: th tch (l) Vdd n: s mol 1.3. Nng molan Biu th s mol cht tan c trong 1000g dung mi. V d: dung dch NaCl 0,2 molan: dung dch cha 2 mol (=11,7g) NaCl trong 1000 gam nc. 1.4. Nng phn mol (hoc phn s mol) Nng phn mol ca mt cht l t s gia s mol ca cht v tng s mol cc cht c trong dung dch. n nA A= A = n n A + nB

70
* Ch : Tng nng phn mol ca cc cht c trong dung dch bng 1. 1.5. Nng ng lng gam ( N ) Biu th s ng lng gam cht tan c trong mt lng dung dch. n N= V n': s ng lng gam cht tan c trong dung dch. V: th tch (l) V d: dung dch HCl 2N: l dung dch c cha 2 ng lng gam hoc 2x36,5g HCl nguyn cht. * p dng nh lut ng lng cho cc phn ng trong dung dch Gi s phn ng : A + B C Gi: NA, NB : Nng ng lng gam ca 2 dung dch A v B VA VB: Th tch ca 2 dung dch A v B phn ng va vi nhau Theo nh lut ng lng ta c: NA .VA = NB .VB y l biu thc ton hc p dng nh lut ng lng cho dung dch. 1.6. Mi quan h gia cc nng 1.6.1. Gia nng phn t gam v nng % CM = 10dC % M

M : khi lng phn t cht tan CM : nng mol ca dung dch D : khi lng ring ca dung dch C% : nng % ca dung dch 1.6.2. Gia nng ng lng v nng % ca dung dch 10dC = % C% : nng % ca dung dch : ng lng gam

CN

71
6.3. Gia CM v CN CN = n.CM n = S in tch m 1 ptg cht trao i hoc n = S e m 1 ptg cht trao i

2. tan v cc yu t nh hng n tan 2.1. Khi nim v tan mt nhit nht nh tan ca mt cht trong mt dung mi xc nh bng nng ca dung dch bo ha cht . Thng thng tan ca cht rn trong mt cht lng c biu th bng s mol cht tan c trong mt lt dung dch. i vi cht kh tan trong cht lng th tan c biu din bng th tch cht kh bo ha trong mt th tch xc nh ca dung mi. tan thng c k hiu l S - Khi dung dch c nng nh hn tan ta c dung dch cha bo ha, cht tan c th tan thm. - Khi dung dch c nng ln hn tan cng nhit th ta c dung dch qu bo ha. Cc dung dch qu bo ha khng bn, nu khuy, lc hoc thm vo dung dch mt vi tinh th cht rn s c s kt tinh cht tan t dung dch v dung dch s tr v trng thi bo ha. 2.2. Cc yu t nh hng n tan - Bn cht cht tan v bn cht dung mi: Cng mt cht tan nhng c th tan nhiu hay t khc nhau trong nhng dung mi khc nhau. Thng cc cht phn cc hoc hp cht ion tan trong cc dung mi phn cc, cn dung mi khng phn cc ha tan cc cht khng phn cc. - Nhit : tan ca mt cht tng khi nhit tng, nu qu trnh ha tan thu nhit. V d : NH4Cl, KNO3 tan nhiu khi un nng tan ca cht kh gim khi nhit tng v qu trnh ha tan ca cc cht kh pht nhit. tan ca cc cht kh t l vi p sut ring phn ca cht kh . S = K.Pi K : hng s t l Pi : p sut ring phn ca cht kh S : tan ca cht kh trong cht lng ( g/100g dung mi) y l ni dung ca nh lut Henry v tan ca cht kh trong cht lng .

72
II. p sut hi bo ha ca dung dch cha cht tan khng in li v khng bay hi. nh lut Raoult I
Dung dch khng in li l dung dch m trong cha cht tan tn ti di dng phn t. y l cc dung dch thc c dung mi lng, cht tan c th l cht rn, lng hoc kh. 1. Khi nim v p sut hi bo ha Do chuyn ng nhit, cc phn t cht lng tinh khit ng trong bnh kn s tch khi b mt cht lng v bin thnh hi. Qu trnh ny gi l qu trnh bay hi. Mt khc, cc phn t cht lng tinh khit A trng thi hi cng chuyn ng hn lon, va vo b mt cht lng v mt s phn t c th ngng t tr li, qu trnh ny gi l qu trnh ngng t. Khi vn tc hai qu trnh ny bng nhau th tn ti cn bng: Lng Hi; H > 0 Hi nm cn bng vi trng thi lng gi l hi bo ho, n gy ra p sut hi bo ho ca cht nguyn cht. Ti mt nhit xc nh, mi cht c mt gi tr p sut hi bo ho khc nhau, ph thuc bn cht ca cht. Qu trnh bay hi l qu trnh thu nhit, khi tng nhit th p sut hi bo ho ca cc cht tng. 2. p sut hi bo ho ca dung dch cha cht tan khng bay hi, khng in li Khi ho tan mt cht tan khng in li v khng bay hi vo mt dung mi th cc phn t cht tan s phn b ng u trong ton b th tch ca dung mi. Mt s phn t dung mi c trn mt thong c thay th bi cc phn t cht tan khng bay hi, mt s phn t dung mi bay hi gim v do p sut hi bo ho ca dung mi trong dung dch b hn so vi p sut hi bo ho ca dung mi nguyn cht. S phn t cht tan cng tng th s phn t dung mi thot ra cng t, do p sut hi bo ho ca dung dch (P 1) lun lun nh hn p sut hi bo ho ca dung mi nguyn cht (P0). S gim p sut hi bo ho ca dung dch tun theo nh lut Raoult I. "p sut hi bo ha ca dung dch bng p sut hi bo ho ca dung mi nguyn cht nhn vi phn mol ca dung mi trong dung dch".

P1 = P0 N dm = P0

n dm n dm + n ct

P1 : p sut hi bo ho ca dung dch P0 : p sut hi bo ho ca dung mi nguyn cht Ndm : phn mol ca dung mi trong dung dch Nu gi N cht tan l nng phn mol ca cht tan trong dung dch th: Ndm + Nct = 1 P : gim p sut hi bo ho ca dung dch P/Po : gim tng i p sut hi bo ho ca dung dch

N ct =

P0 P1 P = P0 P0

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Do , nh lut Raoult I c th pht biu cch khc: " Ti mt nhit xc nh, gim tng i p sut hi bo ho ca dung dch cha cht tan khng bay hi v khng in li bng nng phn mol ca cht tan trong dung dch ".

III. Nhit si v nhit ng c ca dung dch nh lut Raoult II

Nhit ca cht lng l nhit m ti p sut hi bo ho ca cht lng bng p sut hi bo ho ca kh quyn . - Nhit ng c (kt tinh) ca cht lng l nhit m ti p sut hi bo ho ca pha lng bng p sut hi bo ho ca pha rn. - Do dung dch c p sut hi bo ho nh hn p sut hi bo ho ca dung mi nguyn cht nn mun cho p sut hi bo ho ca dung dch bng p sut kh quyn cn phi tng nhit ca dung dch ln nn nhit si ca dung dch ln hn nhit si ca dung mi nguyn cht . - Do p sut hi bo ho ca dung dch nh hn p sut hi bo ho ca dung mi nguyn cht nn cho p sut hi bo ho trn pha rn bng p sut hi bo ho trn pha lng (ca dung dch) cn phi h nhit ng ca dung dch xung, ngha l: nhit ng ca dung dch nh hn nhit ng ca dung mi nguyn cht. V d: - Nc si 1000C, dung dch si t0s > 1000C - Nc ng 00C, dung dch ng t0 < 00C Gin v p sut hi bo ho ca dung dch v dung mi H2O nh sau: OA: p sut hi bo ha ca dung mi nguyn cht( H2O) O/A/: p sut hi bo ha ca dung dch ts = t0s dd - t0s dm ( tng im si) t = t0 dm - t0 dd ( h im ng) /

760mm Hg 4,6mm Hg

A
O

O' t ts

Khi kho st nhit ng ca dung mi v dung dch, " tng im si v h im ng ca dung dch t l vi nng molan ca cht tan trong dung dch". nh lut ny c h thc ho nh sau: ts = Ks .Cm t = Kd .Cm Trong

00 C

100 t 0 t s o 0 si v nhit C Raoult a ra nh lut II nh sau:

74
ts , td ( tng im si, h im ng ca dung dch so vi dung mi nguyn cht Cm : nng molan ca cht tan trong dung dch Ks, K : hng s nghim si v hng s nghim ng ca dung mi nguyn cht Gi tr Ks, K ch ph thuc vo bn cht ca dung mi. y l mt trong nhng phng php xc nh phn t lng ca cht tan bng thc nghim. Bng gi tr Ks, K ca mt s cht: Cht H2O C6H6 Dietylete Phenol Anilin K ( / mol) 1,86 5,12 1,79 7,27 5,78 Ks ( / mol) 0,516 2,67 2,11 3,04 3,22

V d: Tnh t0s, t0 ca dung dch cha 9g glucoza trong 100g H2O. Cho Ks(H2O) = 0,516 ; K(H2O) = 1,86 Gii: 9 1000 9 1000 Cm = = = 0,5 100 M glucoza 100 180 ts = 0,516 0,5 = 0,26 t = 1,86 . 0,5 = 0,930 Vy t0 si ca dung dch l: ts = 100+0,26 = 100,260C t0 ng ca dung dch l: t = 0 - 0,93 = - 0,930C

IV. p sut thm thu ca dung dch

1. Hin tng thm thu Hin tng thm thu xut hin khi cho dung dch tip xc vi dung mi qua mt mng bn thm - l mng ch cho cc phn t dung mi i qua m khng cho cc phn t cht tan i qua (do kch thc l ca mng nh). a s cc mng t bo u c tnh cht bn thm. - Th nghim: Dng mt phu c cung di, ming phu c bt kn bng mt mng bn thm. Cho nc ng bo ho vo trong phu, sau nhng phu vo trong chu nc, mc nc ca phu v chu ngang nhau. Sau vi gi, dung dch dng ln trong cun phu v mng bn thm cho cc phn t dung mi di qua. Khi t n cao h no th nc khng dng ln c na, v lng nc i qua mng bn thm t hai pha l nh nhau trong cng mt n v thi gian, lc ny hin tng thm thu dng li.

75
- Vy : Lc cn tc dng ln mt n v din tch ca mng bn thm lm trit tiu hin tng thm thu gi l p sut thm thu (k hiu ). p sut ny bng p sut thu tnh ca ct cht lng c chiu cao h gy ra. 2. nh lut Vant Hoff v p sut thm thu Nm 1887 Van't Hoff xc nh p sut thm thu ca dung dch tho mn phng trnh V = nRT V C= n/V nn ta c = CRT C: nng mol/l V: th tch dung dch R: hng s kh T: nhit tuyt i " p sut thm thu ca cht tan trong dung dch long c ln bng p sut gy bi cht nu nh cng nhit n trng thi kh v chim th tch bng th tch dung dch ''. nh lut ny ch p dng cho dung dch long cha cht tan khng bay hi v khi khng c s tng tc gia cc cht. p sut thm thu ch ph thuc vo nhit v nng cht tan. ng dng: Vic o p sut thm thu cng c s dng xc nh khi lng phn t cht tan. m mRT RT M = = CRT = MV V V d: Cho p sut thm thu ca mt dung dch cha 0,66g ur (NH 2)2CO trong 250ml dung dch 330C bng 836mmHg. Tnh phn t lng ca ur. Gii:

V =

m mRT 0.66 62400 306 RT M = = = 60,3 vC M T 836 250

3. ng dng hin tng thm thu v p sut thm thu Hin tng thm thu v p sut thm thu c ngha ln trong mt s qu trnh sinh hc. Thm thu l nguyn nhn trc tip ca qu trnh ht nc t mi trng v qu trnh vn chuyn nc trong c th sinh vt. Dch t bo ca mi c th sng c nng cc cht dinh dng xc nh nn c p sut thm thu xc dnh. Khi p sut thm thu ca dch t bo ln hn ca mi trng s gy ra s thm thu nc mi trng vo t bo v lm cho nc di chuyn t t bo n sang t bo kia. V d: i vi cy trng, s thot hi nc t l lm cho qu trnh thm thu nc t mi trng n ngn v l cy tng. Ngc li, khi mi trng c nng cht cao hn dung dch t bo, gy ra s thm thu nc t t bo ra mi trng, t bo co li v c th cht. Mi sinh vt ch pht trin

76
bnh thng trong mi trng c p sut thm thu thch hp. Do nu bn phn vi nng qu ln c th lm cy cht v mt nc. i vi con ngi mt s thay i nh v p sut thm thu ca mu c th gy nh hng nghim trng n qu trnh trao i cht trong c th. V d: Khi tim cc dung dch vo mu ngi bnh thng th dung dch phi c p sut thm thu bng p sut thm thu mu ( dung dch gi l dung dch ng trng). Nu ln hn hay nh hn p sut thm thu mu u gy ra hin tng ph v hng cu. - Nu dung dch u trng: dung dch c p sut thm thu ln hn p sut thm thu mu th hng cu teo li do nng mui ln nn nc i ra khi hng cu. - Nu dung dch nhc trng: dung dch c p sut thm thu nh hn p sut thm thu mu th nc i vo hng cu ( do nng mui b) nn hng cu phnh ra v v.

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CHNG VIII

DUNG DCH IN LI
I. Thuyt in li 1. Tnh cht ca dung dch in li i vi dung dch long ca cc axit, baz, mui c p sut thm thu, tng im si, h im ng o bng thc nghim lun lun ln hn so vi tnh theo cng thc ca Raoult v Van't Hoff. ph hp vi thc nghim, Van't Hoff a ra h s i gi l h s Van't Hoff ( hay h s ng trng ). ' = iCRT = i t's = its t' = it hay = iKsCm = iKdCm

i=

td ts = = ts td

H s i cho bit tng im si, h im ng ca dung dch o bng thc nghim ln hn tr s tnh theo l thuyt bao nhiu ln. H s ny xc nh bng thc nghim. 2. Thuyt in li Cc hin tng trn gii thch c nu gi thit khi ho tan vo nc, cc phn t cht tan phn li thnh cc phn t nh hn. 1877, Arrhenius a ra thuyt in li gii thch cc hin tng trn. Ni dung thuyt in li: - Nhng cht trng thi ho tan hoc nng chy c kh nng dn in gi l cht in li (khi ho tan cht in li vo H2O th chng phn li ra thnh cc ion, di tc dng ca in trng, chng chy v cc in cc). - Cc cht khc nhau c mc phn li khc nhau nn ta c cht in li mnh v cht in li yu. Do c s in li nn s phn t c trong dung dch tng ln; m , ts, t ca dung dch ph thuc nng tiu phn (ch khng ph thuc bn cht tiu phn) do trong thc t ,ts , t ln hn so vi tnh ton. Vy i =

t = t

H s i cho bit s tiu phn ho tan ln hn s phn t cht tan bao nhiu ln.

78
3. in li c trng cho mc phn li ca mt cht in li. in li l t s gia s phn t gam in li v tng s phn t cht ho tan (hoc t s C). S phn t in li

S = phn t ha tan

n C = n C0

C : nng (s phn t gam) cht in li C0 : nng (s phn t gam) cht ho tan - Dung dch cht khng in li: = 0 - Dung dch cht in li hon ton: = 1 - Cht in li yu: 0 < < 1 4. Quan h gia in li v h s Van' t Hoff i Gi s ho tan n phn t cht in li vo dung dch. Mi phn t phn li ra m ion. in li ca dung dch l th: - S phn t in li l n - S ion c trong dung dch l n.m - S phn t khng in li l n -n - Tng s phn t cht tan trong dung dch l: m + n - n .n.m + n n i 1 = m + 1 (i ) = (m 1) = Ta c : i = n m 1 m: s ion m mi phn t in li i: h s Van't Hoff : in li

II. Cn bng trong dung dch cht in li yu

1. Hng s in li S in li ca cht in li yu l mt qu trnh thun nghch nn ta c th p dng nh lut tc dng khi lng. Gi s c cn bng: HA = H+ + ATa c: H+, A- : nng mol Hng s cn bng K gi l hng s in li hoc hng s ion ho, c trng cho kh nng in li ca mt cht K; cng ln th s in li cng mnh, cht in li phn li ra cc ion cng nhiu v ngc li. K ph thuc bn cht ca cht in li, dung mi v nhit .

79
2. Mi lin h gia hng s in li v in li - nh lut pha long Otswald Gi C l nng mol ca cht in li HA: HA H+ + ABan u C 0 0 Khi c in li C C C Cn bng C - C C C : in li C : s phn t gam HA in li
K cb =

[ H ][ A ]
+

[ HA]

K cb =

C. C 2C 2 = C C C (1 )

2C K cb = 1 2 Khi << 1 th c th xem 1- 1 Khi ta c biu thc n gin hn l

k /c

T , nu bit in ly mt nng xc nh ta c th tnh c K bng ngc li. Biu thc ny cho thy: in li t l nghch vi cn bc 2 ca nng cht in li. l ni dng ca nh lut pha long Ostwald. Khi nng gim ngha l khi pha long th in li ca dung dch tng ln.

III. c im in li ca axit v baz

1. Quan im ca Arrhenius 1.1. Cht in li mnh v cht in li yu - Cht in li mnh: l cht c kh nng cht in li hon ton thnh cc ion ngha l trong dung dch khng cn phn t cha in li; gm: axit mnh, baz mnh v mui ca chng. - Cht in li yu: l cht ch in li mt phn thnh ion ( hoc ch c mt s phn t in li ra ion ); gm: axit yu, baz yu, mui ca baz yu v axit yu. 1.2. Axit v s in li

Axit l cht trong dung dch in li ra ion H+ (H3O+ ) v anion gc axit : HnA nH+ + AnHNO3 = H+ + NO3-

V d:

80
Tnh axit ca dung dch l do tnh cht ca ion H+ quyt nh, cht no in li cho cng nhiu ion H+ th tnh axit cng mnh. - Axit in li hon ton l axit mnh, axit yu in li khng hon ton. - i vi axit yu: HAc H+ + AcKA =

[ H ][ Ac ]
+

[ HAc]

KA gi l hng s cn bng axit, cc axit a chc yu s in li thnh nhiu nc, mi nc c mt hng s axit ring. Hng s axit chung ca ton b phn t bng tch cc hng s axit ring. V d: H3PO4 H++ H2PO4K1=

[ H ][ H
+

PO4 [ H 3 PO4 ]
2

H2PO4- H+ + HPO42K2= ....... HPO42- H+ + PO43K3= ....... Kax= K1 . K2 . K3 ca phn ng H3PO4 3H+ + PO43K1 >> K2 >> K3 tng qut: Kax= K1 . K2 Kn 1.3. Baz v s in li ca baz - Baz l cht trong dung dch in li ra anion OH- v cation kim loi. M(OH)n = Mn+ + nOHTnh baz do ion OH- quyt nh, cht in li cng nhiu ion OH- th tnh baz cng mnh. - Baz mnh l baz in li hon ton, baz yu in li khng hon ton. - i vi baz yu : qu trnh in li thun nghch; hng s cn bng in li ca baz gi l hng s baz. NH4OH NH4+ + OH-

[ NH ][OH ] K=
+ B

[ NH 4 OH ]

Cc baz a chc yu s in li thnh nhiu nc, mi nc c mt hng s baz ring. Hng s baz chung ca ton b phn t bng tch cc hng s baz ring. Mg(OH)2 Mg(OH) + OH
+ + 2+ -

[ MgOH ][OH ] K=
+ 1

[ Mg (OH ) 2 ]

Tng qut:

MgOH Mg + OH K2= ........... 2+ Mg(OH)2 Mg + 2OH K= K1K2 K1>>K2 Kb= K1K2 .........Kn K1>> K2>>.......>> Kn

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1.4. S in li ca cc hydroxit lng tnh - Cht lng tnh l cht nhng cht th hin c tnh axit ln tnh baz tc c kh nng in li cho c ion H+ v ion OH-. Cc cht c cng thc M(-O-H)n phn cc ca lin kt M-O v O-H tng ng nhau nn c th lin kt M-O b phn ct do n th hin tnh baz, nu lin kt O-H b phn ct n th hin tnh axit. V d: Al(OH)3 HAlO2.H2O Al(OH)3 Al3+ + 3OHHAlO2H2O H+ + AlO2- + H2O Cc hydroxit lng tnh: Zn(OH)2, Sn(OH)2, Sn(OH)4, Pb(OH)2, Sb(OH)4 v Be(OH)2, Al(OH)3,........... 1.5. Mui v s in li - Mui l sn phm ca s tc dng mt axit vi mt baz. Trong phn t c cha cation kim loi v cation gc axit.. - Mui trung tnh in li cho cation kim loi v anion gc axit khng cha H c th thay th c cation kim loi. Na2CO3 = 2Na+ + CO 32_ - Mui axit in li cho cation kim loi v anion gc axit c cha H c th thay th c bi cc cation kim loi. NaHCO3 = Na+ + HCO3HCO3- H+ + CO32_ - Mui baz khi in li cho anion gc axit v gc baz ( c cha OH) . Cu2(OH)2CO3 2CuOH+ + CO32CuOH+ Cu2+ + OH- Mui n: Trong phn t c kh nng in li hai loi ion n. Na2SO4 = 2Na+ + SO42- Mui kp: in li cho ba loi ion tr ln. NH4Fe(SO4)2 = NH4+ + Fe3+ + 2SO4- Mui phc: in li cho ion phc. K4[Fe(CN)6] = 4K+ + [Fe(CN)6]4- ion phc
ion phc

2. Quan im axit - baz ca Bronsted Quan im ca Arrhenius khng gii quyt c c nhng cht trong phn t khng cha nhm OH- nhng vn th hin c tnh cht ca mt baz hoc i vi h dung mi khng phi l nc, hoc i vi dung dch mui trong nc (do qu trnh thu phn). Bronsted m rng quan nim axit - baz nh sau: Axit l nhng cht trong dung dch c kh nng nhng proton H+ v baz l nhng cht c kh nng nhn H+. A = H+ + B-

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V d: CH3COOH H+ + CH3COOCc axit, baz c th l phn t trung ho hoc ion. Axit no d cho proton H+ l axit mnh, baz no d nhn proton H+ l baz mnh. Phng tnh tng qut: A1 + B2 = A2 + B1 Mt cht c th ng vai tr l axit, cng c th l baz. CH3COOH + H2O H3O+ + CH3COOAxit Baz CO32+ H2O HCO3- + OHBaz Axit Mi axit s c mt baz lin hp tng ng v ngc li chng c gi l axit- baz lin hp. Axit cng mnh th baz lin hp cng yu v ngc li: Axit H2O NH4+ HCl H3PO4 H2PO4HPO42HCO3Baz OHNH3 ClH2PO4HPO42PO43CO32Proton H+ H+ H+ H+ H+ H+ H+

+ + + + + + +

IV. Dung dch phc cht 1. nh ngha Phc cht l nhng cht phc tp to ra t hai mui n, khi ho tan trong dung dich th phn ly thnh ion n v ion phc. V d: K3[Fe(CN)6]: to ra t hai mui n. 3KCN + Fe(CN)3 = K3[Fe(CN)6] 2. Cu to phc cht Mi phn t gm mt ion trung tm hay cht to phc (thng l cation kim loi chuyn tip) lin kt vi cc nhm phi tr, thng l anion hoc phn t trung ho hoc nhng nhm chc trong cc hp cht hu c (gi l phi t) bng lin kt cng ho tr hoc lin kt phi tr to ion phc (cu ni), ion phc s lin kt vi cc ion tri du (cu ngoi) to phn t trung ho. - Phc anion: K3[Fe(CN)6] - Phc cation: [Cu(NH3)4]Cl2 Cc phi t ph bin: H2O, aqu NH3, amin NO, CO, OHnitrozil cacbolxyl hydroxo

83
3. Hng s khng bn ca phc cht Xt phc K3[Fe(CN)6] trong dung dch, chng phn li ra ion n K+ v ion phc [Fe(CN)6]3K3[Fe(CN)6] 3K+ + [Fe(CN)6]3v [Fe(CN)6]3- Fe3+ + 6CNKcb

[ Fe ][CN ] =
3+

[ Fe(CN ) 6 ] 3

Kcb gi l hng s khng bn ca phc (hng s phn li ca phc). Kcb cng nh th phc cng bn; cng ln th phc cng km bn ion phc phn li ra cc ion n cng nhiu.

V. Cht in li t tan - tch s tan

1. nh ngha tch s tan Xt s ho tan ca cht in li t tan AgCl: Cc ion Ag + v Cl- di tc dng ca cc phn t nc s tch khi tinh th v i vo dung dch, v ngc li chng c th va chm v kt hp nhau to thnh phn t AgCl. Khi vn tc ho tan bng vn tc kt ta th cht tan khng tan c na v xut hin cn bng: AgCl(r) Ag+ + ClHng s cn bng ca h d th ny l: K = [Ag+][Cl-] = TAgCl K trong trng hp ny l tch s tan v k hiu T. T khng ph thuc vo nng ca Ag+ v nng ca Cl- m ch ph thuc vo nhit . Vy trong dung dch bo ho ca cht in li t tan, tch s nng cc ion l mt hng s. nh ngha: "Tch s tan ca mt cht l tch s nng cc ion trong dung dch bo ho ca cht nhit nht nh, mi nng c s m bng s ion trong phn t cht . '' V d: Ag2CrO4 2Ag+ + CrO42TAg2CrO4 = [Ag+]2[CrO42-] Tch s tan cng ln th cht cng d tan. 2. iu kin ho tan mt cht in li t tan V d: Xt qu trnh ho tan FeS bng HCl. Trong dung dch FeS tn ti cn bng: FeS(r) Fe2+ + S 2 - (1) Lc ny TFeS = [Fe2+][S2-] tc l FeS khng tan. Khi thm HCl vo: HCl = H+ + ClH+ + S2- = HSH+ + HS-= H2S

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Nn lm nng S2- gim, do theo nguyn l chuyn dch cn bng th cn bng (1) chuyn dch theo chiu thun. FeS tip tc tan thm cho n khi TFeS = [Fe2+][S2-] th cn bng mi c thit lp. Nu tip tc thm HCl vo th FeS tip tc tan cho n ht. Vy mun ho tan mt cht in li t tan th phi thm vo dung dch mt cht no c kh nng kt hp vi mt trong cc ion ca cht in li t tan to thnh cht in li yu, sao cho tch s nng cc ion ca cht in li t tan (km theo s m ) phi lun lun nh hn tch s tan. 3. iu kin kt ta ca mt cht in li t tan Tng t , theo nguyn l chuyn dch cn bng, mun kt ta mt cht in li t tan th tch s nng cc ion phi ln hn tch s tan tc l phi tng nng ca mt trong hai ion to thnh kt ta.

VI. Tch s ion ca nc - pH ca mt s dung dch

1. Tch s ion ca nc Nc nguyn cht tuy vi mc rt nh, cng c kh nng dn in, trong nc tn ti cn bng. H2O H+ + OHp dng nh lut tc dng khi lng ta c: Do nc l cht in li yu nn c th xem K[H2O] = const = [H+][OH-] = Kn Kn gi l tch s ion ca nc Kn ph thuc vo nhit , 220C, Kn = 10-14 [H+] = [OH-] = 10 14 = 10 7 mol/l Ta c: - Dung dch trung tnh: [H+] = [OH-] = 10-7 - Dung dch axit: [H+] > 10-7 > [OH-] - Dung dch baz : [H+] < 10-7 < [OH-] 2. pH Do vic biu th tnh axit, baz ca dung dch bng nng ion H+ rt phc tp v c s m m nn trong thc t, ngi ta dng i lng pH = - lg[H+]. PH c gi l ch s hydr hay pH. pOH = - lg[OH-] pH + pOH = 14 Nh vy pH biu th tnh axit - baz ca dung dch. - Dung dch trung tnh: pH=7 - Dung dch axit: pH<7 - Dung dch baz: pH>7 3. Cht ch th v pH Nhiu phn ng ch xy ra mt pH xc nh. bit pH s b ca dung dch nghin cu, ngi ta thng dng cc cht ch th mu hay cht ch th v pH. 3.1. nh ngha Cht ch th v pH l nhng cht c mu sc ph thuc vo pH ca mi trng. l axit yu hay baz yu hu c m dng axit v dng baz lin hp ca chng c mu khc nhau.

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V d: HInd l cht ch th pH, trong dung dch tn ti cn bng HInd H+ + IndDng axit Dng baz - Nu mi trng axit th cn bng chuyn dch theo chiu nghch, cho n khi th dung dch c mu dng axit. - Nu mi trng baz th cn bng chuyn dch theo chiu thun, cho n khi th dung dch c mu dng baz. 3.2. Khong i mu ca cht ch th L khong pH t khi ch th bt u chuyn mu n chuyn mu hon ton. Khong i mu ca mt s cht ch th Cht ch th mu Metyl da cam Metyl Qu Phenolftalein Timolftalein 3,1 - 4,4 4,4 - 6,2 5-8 8 - 10 9,4 - 10,6 cam Khng mu Khng mu Vng Vng Xanh Hng Xanh Khong i Mu dng axit Mu dng baz

[ HInd ] 10

[ Ind ]

[ HInd ]

[ Ind ] 10

Ngoi ra ngi ta cn dng cht ch th vn nng l hn hp gm nhiu cht ch th khc nhau (phenolftalein, metyl , metyl vng, timolftalein,...) 4. pH ca mt s dung dch HnA nH+ + An4.1. Dung dch axit - Axit mnh: = 1 [H+] = n Ca pH = - lg[H+] PH = - lg(nCa) Ca: nng ban u ca axit (vi Ca>> 10-7 ( b qua s in li ca nc) n: s mol ion H+ m mt phn t axit phn li - Axit yu n chc: HA H+ + Anng ban u Ca nng axit phn li Ca Ca Ca nng axit cn li Ca(1- ) Ca Ca << 1 1- 1 [HA] Ca Ka =

[ H ][ A ] = [ H ] [ H ] = (1 )C C
+ + + a a

K aCa

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pH = ( pKa + lgCa ) i vi axit phn li nhiu nc th cc nc sau c th b qua v thay K a = K1 vo cng thc trn. 4.2. Dung dch baz M(OH)m Mm+ + mOH- Baz mnh: (Cb >> 10-7: Do b qua s in li ca nc.) [OH-] = Cb. m Cb: Nng ban u ca baz pOH = - lgmCb m: s ion OH- do mt phn t phn li pH = 14 - pOH -Dung dch baz yu n chc: tng t axit yu, ta c: pH = 14 - ( pKb lgCb ) Kb: hng s baz Cb: nng ban u ca baz

VII. S thu phn ca mui

1. nh ngha phn ng thu phn Phn ng thu phn l phn ng trao i cc ion ca mui vi cc ion ca nc to axit v baz. 2. iu kin xy ra phn ng thu phn Phn ng thu phn xy ra khi c s to thnh axit yu hoc baz yu, do pH ca mui s ph thuc vo tnh cht ca axit hoc baz to thnh. 3. Cc loi mui thu phn (tho mn iu kin thu phn) - Mui ca baz yu vi axit mnh: thu phn to baz yu v pH<7 pH = 7 ( pKb + lgCm ) Vi Cm: nng ban u ca mui V d: NH4Cl + H2O NH4OH + HCl Thc cht: NH4+ + H2O NH4OH + H+ pH ca dung dch c quyt nh bi H+ t do pH < 7 Mui ca baz mnh v axit yu : thu phn to axit yu, bn cht phn ng l s kt hp ion gc axit ca mui vi H+ ca nc v gii phng OH- nn pH >7. pH ca dung dch mui ny c tnh theo cng thc: pH = 7 + ( pKa + lgCm ) V d: CH3COONa, NaHCO3, ........ CH3COONa + H2O CH3COOH + NaOH CH3COO- + H2O CH3COOH + OH-

Mui ca baz yu v axit yu : phn ng thu phn xy ra to axit yu v baz yu.

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Dung dch c pH < 7 nu axit to thnh c tnh cht axit mnh hn v c pH > 7 nu baz to thnh c tnh cht baz mnh hn. V d: NH4CH3COO + H2O NH4OH + CH3COOH

VII. Dung dch m

1. nh ngha Dung dch m l dung dch c kh nng gi pH thay i khng ng k khi ta thm vo mt t axit mnh hay baz mnh hoc pha long. Nh vy dung dch m c kh nng lm n nh hoc duy tr pH ca mi trng. 2. Phn loi C hai loi h m: - H m baz : gm mt baz yu v mui ca n vi axit mnh. V d: h m amoni NH4OH/NH4Cl - H m axit : gm mt axit yu v mui ca n vi baz mnh. V d: h m axetat CH3COOH/CH3COONa Ngoi ra c h m gm hn hp hai mui c kh nng trao i H+ nh: NaHCO3/Na2CO3; NaH2PO4/Na2HPO4; Na2HPO4/Na3PO4, hn hp cc axit amin. 3. C ch tc dng m Xt h m axit: CH3COOH/CH3COONa CH3COONa Na+ + CH3COOCH3COOH H+ + CH3COO- (1) Khi thm mt t H+, tc l nng H+ tng. Cn bng (1) s chuyn dch theo chiu nghch to axit yu nn pH ca h hu nh khng i. H m cng bn khi nng CH 3COONa cng ln . Khi thm mt t OH-: th nng H+ gim do H+ kt hp vi OH- to thnh H2O nn cn bng (1) s dch chuyn theo chiu thun to H+ b vo lng H+ mt, do pH ca dung dch xem nh khng thay i. H m cng bn khi nng H+ cng ln. Khi pha long, nng axit v mui gim tng ng nn pH ca h hu nh khng thay i. Tm li mt h m axit gm hai thnh phn chnh: mt thnh phn ng vai tr axit phn ly ra H+, cn thnh phn kia c kh nng nhn H+. 4. pH ca h m - H m axit: pH = pKa + lgCm /Ca - H m baz: pH = 14 (pKb + lgCm /Cb ) 5. ngha v vai tr ca dung dch m i vi i sng sinh vt Mi sinh vt ch tn ti v pht trin trong mt mi trng c pH xc nh m dung dch m n nh pH ca mi trng phn ng. V vy, khi nui cy cc vi sinh vt, ngi ta phi chun b cc dung dch dinh dng c pH thch hp, cc men cng ch hot ng trong mt khong pH ph hp.

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i vi cy trng, mi loi cy pht trin bnh thng trong mt mi trng (t) c chua (pH) xc nh. Phn ln cc cy ch pht trin trong khong pH 4- 10. Ngoi gii hn ny chng s b cht. Trong t, do cha nhiu cht hu c nn tn ti nhiu qu trnh ho hc khc nhau c kh nng t iu ho nng H+ lm cho pH n nh nn mi loi t c th trng c nhiu loi cy khc nhau. Nh vy, t l mt h m axit - baz tt. Vic ci to t phi ph hp v khoa hc. Trong c th sinh vt cng vy, cc axit amin u c tc dng m. Trong mu ngi c rt nhiu h m, chng n nh pH ca mu m bo cho s cn bng axit- baz ca c th. Hng ngy cc phn ng chuyn ho trong c th xy ra to ra lng axit, nhng pH ca mu ch dao ng trong khong 7,3 - 7,4. Nu pH nh hn gi tr ny th b nhim axit ( toan mu), nu pH ln hn th b nhim kim. Mt s h m c trong mu: NaH2PO4 Na2HPO4 Hemoglobin oxi hemoglobin cc axit amin

IX. Phn ng trao i v phng php phn tch th tch

1. iu kin xy ra phn ng trao i Phn ng trao i ch xy ra khi c s to thnh cht in li yu, cht d bay hi, hoc cht t tan. V d: AgNO3 + HCl = AgCl + HNO3 NaOH + HCl = NaCl + H2O Na2CO3 + H2SO4 = Na2SO4 + CO2 + H2O 2. Phn ng trao i v phng php phn tch th tch Phng php phn tch th tch da trn phn ng: aA + bB = cC + dD Trong A l cht cn nh lng, B l cht c nng bit, gi l dung dch chun. Theo nh lut ng lng, khi cht B phn ng va vi cht A th s ng lng gam ca cc cht phi bng nhau, hay: NA . VA = NB . VB N: nng ng lng V: th tch (ml, l) Ban u ta bit th tch ca dung dch A; sau phn ng ta xc nh c th tch dung dch B phn ng va vi cht A s suy ra c nng cht A cn nh lng.

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Qu trnh thc hin xc nh th tch dung dch B phn ng gi l qu trnh chun . Thi im m ti hai cht phn ng va vi nhau gi l im tng ng. pht hin im tng ng, trong qu trnh chun ta dng cc cht ch th mu. C nhiu loi phn ng dng trong phn tch th tch, mi loi c c im ring ng vi cc cht ch th ring.

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CHNG IX

HO KEO

Ho keo l mt ngnh hc khoa hc nghin cu cc h phn tn trong kch thc ca ht phn tn nm trong khong 10-7 - 10-5cm gi l h phn tn keo. Ho keo c ngha ln trong th nhng, canh tc hc - t l mt h thng keo phc tp kch thc, hnh dng cng nh bn cht ca cc ht keo t quyt nh kh nng thm t, kh nng hp ph ca t. Trong cng nghip, ho keo c s dng rt nhiu: - K ngh gm s dng nguyn liu t st, cao lnh l mt loi huyn ph cc Aluminosilicat hidrat ho. - Cc ngnh sn xut giy, nhum, thuc da. - Ngnh cao su tng hp v cht do - Ngnh bo ch thuc - Ngnh ch bin thc n

I. Phn loi
1. Phn loi theo trng thi tp hp 1.1. Nu mi trng phn tn l kh, cn cc cht phn tn c th l rn, lng, kh, ngi ta gi l AEROSOL. V d: h bi (R/K), h sng m (L/K), h khi (K/K) 1.2. Nu mi trng phn tn l lng, cn cht tan l rn, lng, kh, ngi ta gi l LYOSOL. V d: dung dch bn (R/L), C6H6 trong nc (L/L), kh trong nc (K/L). 1.3. Nu mi trng phn tn l rn, cht phn tn l rn, lng, kh, ngi ta gi l XEROSOL. V d: Bt kh trong thy tinh (K/R), thu ngn trong phosphor (L/R), hp kim (R/R). 2. Phn loi da trn s tng tc gia cc cht phn tn v mi trng phn tn 2.1. Nu gia ht phn tn v mi trng phn tn c s tng tc, h keo c gi l h keo a lu, khi lm ng t thu c mt khi c gi l gel. V d: Keo protit 2.2. Nu gia ht phn tn v cc phn t dung mi khng c s tng tc, ngi ta gi l h keo ght lu V d: h keo v c 2.3. Nu mt h phn tn, trong iu kin ny l h phn tn tht, trong iu kin khc li l h phn tn keo, ngi ta gi l h bn keo. V d: dung dch x phng

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II. Cc phng php iu ch v tinh ch keo
Cc h keo cha nhng ht c kch thc trung gian gia cc phn t v cc ht th. t c phn tn keo, ngi ta c th s dng nhng phng php sau: - Phng php phn tn: chia nh vt cht - Phng php ngng t: lin kt cc ion, nguyn t hay phn t thnh nhng tp hp. 1. Phng php phn tn Phn tn l qu trnh dng nng lng (c nng, in nng, nng lng ca sng siu m ...) chia nh vt cht ri phn b vo mt mi trng ng nht no . Nng lng ny ch yu dng thng lc lin kt gia cc phn t ca tng b phn tn. Nhng phng php phn tn thng gp: 1.1. Phn tn c hc: nghin, xay cc ht rn bng ci xay keo cho n khi c kch thc ht keo. 1.2. Phn tn bng siu m: dao ng siu m c tn s cao hn dao ng m thng, di tc dng ca dao ng siu m, tiu phn th b dn v nn lin tc, do b gy thnh cc tiu phn c kch thc bng ht keo. 1.3. Phng php keo tn (s pepti ho) lm tan kt ta do s keo t gy ra - Phng php keo tn c thc hin bng cch lm gim lc lin kt gia cc ht ln bng cht in li no , kt qu nhng ht ln phn tn thnh nhng ht nh c kch thc ht keo. V d: Cho FeCl3 vo ng nghim ng keo th Fe(OH)3 v lc, mt lc sau dung dch c mu thm v kt ta bin mt. Trong thin nhin, s to thnh cc dung dch keo ch yu xy ra di tc dng ca cc yu t c hc nh s ra tri, s bo mn ... 2. Phng php ngng t Ht keo c hnh thnh do s ngng t cc phn t, nguyn t, ion thnh nhng ht c kch thc ht keo (khong 1m (10-7cm)). Qu trnh ngng t c 2 giai on: - Giai on to mm trong dung dch qu bo ho vi vn tc v 1: cho cc phn t tp trung vi nhau to mm. - Giai on pht trin mm vi tc v2. Cc phng php ngng t thng dng: 2.1. Phng php ho hc Ngng t bng phn ng ho hc V d: dung dch keo st (III) c iu ch bng phn ng thy phn FeCl3 khi un nng. FeCl3 + 3H2O Fe(OH)3 + 3HCl

Fe(OH)3 thu c khng tan trong nc, nhng khng b lng xung thnh kt ta, trong dung dch di dng keo trong sut c dng mu nu . 2.3. Phng php thay th dung mi Nu cht tan A ho tan trong dung mi B, dung mi B li tan trong dung mi C nhng cht A li khng tan trong C. Ta iu ch h keo A trong C nh sau: Cho A ho tan trong B, sau dung dch tht ny ho tan trong C, ch c B tan trong C, cn A khng tan trong C, n ngng t li thnh ht keo.

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V d: iu ch keo lu hunh trong nc S tan trong ru nhng khng tan trong nc. Ly mt t S ho tan trong ru sau cho dung dch ny vo bnh ng nc, lc u, do ru t, nc nhiu nn nc l dung mi, cc phn t S khng tan trong nc, kt hp li thnh keo S. 3. Tinh ch dung dch keo Trong dung dch keo mi iu ch cn ln tiu phn dung dch tht hay tiu phn th lm cho dung dch km bn, nn phi tin hnh tinh ch, tc loi b cc tiu phn ni trn. 3.1. Loi tiu phn th Do kch thc tiu phn th ln hn tiu phn keo nn loi tiu phn th, phi dng giy lc hoc phu lc xp c kch thc khong 10-5cm, khi ht keo v dung dch tht i qua, cn tiu phn th b gi li. Ngoi ra ngi ta dng phng php sng loi b nhng tiu phn th. 3.2. Loi tiu phn dung dch tht (phn t hay ion) Dng phng php thm tch Cho dung dch keo vo ti thm tch (thng l ti bng giy bng knh), nhng vo cc nc ct, cc tiu phn dung dch tht s i ra khi ti (do ti c kch thc l nh), cc ht keo b gi li. C nh vy, thay nc ct trong cc cho n khi dung dch trong ti tinh khit. Ngoi ra ngi ta cn dng phng php siu lc, lc di p sut rt thp, dng phu c l rt nh, nh hn kch thc ht keo.

III. Tnh cht ng hc ca h keo

1. Chuyn ng Brown Chuyn ng Brown l kt qu cc va chm gia tiu phn keo v tiu phn dung mi ang chuyn ng nhit. Vi knh hin vi c phng i cao, ng Brown quan st c ng i ca cc ht keo trong dung dch, l ng gp khc v khng c qui lut r rt, gi l chuyn ng Brown. Mi ht keo trong dung dch, ngoi chuyn ng v dao ng rt yu (do khi lng ln), n cn chu tc dng ca cc phn t dung mi theo nhng lc khng ng nht v mi pha nn hng ca ht keo thay i lin tc (106 ln/giy) c trng cho kh nng di chuyn ca ht keo, ngi ta dng khi nim dch chuyn bnh phng trung bnh. 2 = 2 Dt (do Einstein tm ra) 2 : dch chuyn bnh phng trung bnh ca ht D: h s khuch tn t: thi gian ht dch chuyn t im A n im B

(t1)A 1 2 2 =
2 2 2 1 + 2 + ... + n n

B(t1)

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* H s khuch tan D l lng cht khuch tn trong mt giy qua mt tit din thng 1cm2 khi gradient nng (bin thin nng ) bng n v. Do t nh lut Fich: dC Sdt dm = - D dx dC dC St nu khng ph thuc thi gian m = - D dx dx dC dC St nu =1 , S = 1, t = 1 m=-D dx dx => D = -m kT N = const ) D= (k = 6 r R : nht mi trng R: hng s kh r: bn knh ht keo N: s Avogadro T: nhit Bn knh tng th h s khuch tn gim, ht cng ln th khuch tn chuyn ng cng kh. A i vi ht keo trn D = 3 M A: hng s ph thuc nhit v dung mi M: khi lng phn t cht tan Khi lng phn t cht tan tng -> h s khuch tn gim M D(200) Ure 60 0,81 Saccharose 342 0,31 Hemoglobin 63000 0,059 2. p sut thm thu Theo nh lut Van't Hoff: = CRT Nu trong mt lt dung dch c n' tiu phn n' n' RT R = = kn' RT C= (k = ) N N N Vy ph thuc s tiu phn cht tan c trong mt n v th tch v nhit T. Khi dung dch tht v dung dch keo c nng khi lng cht tan nh nhau th trong cng mt n v th tch, s phn t tht ln hn s phn t keo rt nhiu => dung dch tht > dung dch keo. Tng t, ts v t ca dung dch keo u nh hn dung dch tht cng iu kin rt nhiu. 3. ng dng ca hin tng khuch tn v p sut thm thu Hin tng khuch tn v p sut thm thu c ngha ln trong s trao i cht in li qua mng sinh vt Donan.

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Gi thit mng sinh vt l mng thm tch ngn i bnh, mt bn l dung dch nc ca keo protein RNa, bn kia l dung dch in li NaCl. Mng ny cho php dung mi v nhng ion cht in gii i qua, khng cho ht keo i qua. I. dung dch RNa(C1) RNa+ Bu C1 C1 CBng C1 C1+x ClO x Mng sinh vt II. dung dch NaCl (C2) Na+ C2 C2-x ClC2 C2-x

(x: lng ion chy t II->I) Theo Donan, ti cn bng ta c: [Na+]I [Cl-]I = [Na+]II [Cl-]II (C1 + x)x = (C2 - x)2 C1x + x2 = C22 + x - 2C2 x => x(C1 + 2C2) = C22
2 C2 C2 x hay = x= C1 + 2C 2 C 2 C1 + 2C 2 2

x : s phn cht in li di chuyn t II n I C2 C hai trng hp xy ra: * Khi C2 <<C1 (nng cht in li << nng cht keo) x => 0: Hu nh khng c cht in li i qua mng. Vy khi yu cu v dinh dng C2 ca sinh vt cao, s cung cp dinh dng ca mi trng qu km th sinh vt kh tn ti hoc khng c nng sut cao. * Khi C2 >> C1 (nng cht in li >> nng cht keo) x => 1/2: cht in li hu nh khng c cht in li i qua mng. Nh vy trong iu C2 kin mi trng cung cp dinh dng mc ti a, lng cht dinh dng sinh vt c th hp th c khng qu 1/2. Vy mun tng nng sut cy trng hay vt nui, cn chm sc chng mt cch hp l chng pht trin tt v trnh lng ph.

IV. Tnh cht quang hc ca h keo

1. S phn tn nh sng 1.1. Hin tng - Khi chiu mt chm tia sng qua mt dung dch tht, mt phn b dung dch hp th, mt phn i qua hon ton v ta hng c nh ca ngun sng pha sau dung dch. - Khi chiu mt chm sng qua dung dch keo, ta lun c mt gii sng hnh nn ct trong dung dch keo, gi l hnh nn Tyndahl. Hin tng ny gi l hin tng Tyndahl.

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- Khi chiu mt chm sng qua dung dch th, mt phn b hp th, phn cn li b phn x tr li.

S
D dd tht

S
D dd keo

S
D dd th

1.2. Gii thch hin tng - dung dch tht, kch thc ht phn t tn nh hn bc sng ca nh sng, nn snh sng truyn qua d dng. - dung dch th, kch thc ht phn tn ln hn bc sng ca nh sng chiu vo nn nh sng khng i qua c, tr phn b hp th, phn cn li b phn x hon ton. - Vi dung dch keo, kch thc ht phn tn bng kch thc ca bc sng nh sng chiu vo nn khi cc ht keo nhn c nng lng ca bc x, chng tr thnh cc ngun sng th cp pht sng theo mi phng, gi l nh sng phn tn, v th hnh thnh hnh nn ct Tyndahl trong dung dch keo. Rayleigh a ra cng thc tnh cng nh sng phn tn i vi ht keo trn:

V2 4 Ipt: cng nh sng phn tn I0: cng nh sng ti K: hng s : nng ht V: Th tch ca ht phn tn : bc sng ca nh sng ti i vi dung dch keo, nu ta dng ngun sng nht nh (I0 v khng i) chiu vo dung dch keo c tiu phn nh nhau (V khng i) th cng nh sng khuch tn ch ph thuc vo nng ht, y l c s xc nh nng dung dch keo bng phng php o c. Da vo hin tng Tyndahl, ngi ta dng knh hin vi quan st tiu phn keo m mt thng khng nhn thy c. Trn nn ti cc im sng chuyn ng hn lon. Dng knh ny ta m c s ht trong mt th tch nht nh, tc l xc nh c nng keo. Bit nng khi lng ca dung dch keo, ta bit c khi lng ht keo v th tch ht keo. Nu ht keo hnh cu, ta tnh c bn knh. 2. S hp th nh sng Trn y ta ni n s phn tn nh sng bi cc ht keo khng dn in. i vi ht keo dn in, ngoi hin tng phn tn nh sng trn b mt ht, tun theo phng trnh Rayleigh m hiu ng ny thng nh, cn c hin tng hp th nh sng. Thng th hiu ng ny th hin mnh hn hiu ng trn. Xt ton b, do c hai hiu ng ny chng ln nhau, do i vi h cha cc ht dn in, vic dng phng trnh Rayleigh khng cn nghim ng na.
Ipt = KI 0

96
Khi c s hp th c bit mt tia sng no , s ph thuc gia I pt vo 4 v V2 b ph v, mc phn cc ca nh sng phn tn cng thay i. Trong ht dn in, t trng bin thin ca sng nh sng lm xut hin mt sc in ng cm ng, do trong ht xut hin dng in xoay chiu vi tn s ca sng in t - V c dng in , in nng bin thnh nhit nng - l s hp th nh sng. 3. Mu sc ca h keo Cc h keo thng c mu sc. Nhng qu c mu v trong c mt lng rt nh kim loi nng, hoc oxit ca chng phn tn di dng keo. V d trong ngc ta c hp cht st, trong ngc bch c hp cht crom. Nguyn nhn mu sc ca h keo rt phc tp - Bn cht ca tng phn tn, mi trng phn tn, phn tn ca ht, hnh dng v cu to ca chng u nh hng n mu sc ca h keo v nhng yu t u nh hng n s phn tn v hp th nh sng - mu sc ca cc h cn ph thuc vo iu kin quan st v cch iu ch chng.

V. Tnh cht in ca h keo

1. Cc hin tng in ng hc 1808, gio s Rit, nh vt l Nga, pht hin cc ht trong h keo c mang in tch. ng lm th nghim nh sau:

S th nghim ca Rit

Cm hai ng thu tinh trn mt tng t st nho, nc u v cm hai in cc vo hai ng ri cho dng in mt chiu chy qua. Mt lt sau, ng thy ng cm dng cc c, cn ng cm cc m vn trong nhng mc nc c cao hn trong ng cm cc dng mt t Qu trnh vn chuyn cc ht keo t chng t n tch in m. - Qu trnh vn chuyn ht keo gi l s in li - Song song vi qu trnh vn chuyn ht keo cn c s chuyn mi trng, qu trnh gi l s in thm. 2. Cu to ca ht keo - Tnh bn ca cc dung dch keo Cc ht keo c b mt ln nn v mt nhit ng hc l khng bn. Trong thc t, trong nhng iu kin nht nh, dung dch keo c th tn ti trong thi gian di do cu trc ht keo c nhng c im ca n. V d: khi cho AgNO3 tc dng vi dung dch KI d, ta c dung dch keo AgI. Qu trnh hnh thnh c m t nh sau: u tin c s hnh thnh phn t AgI, cc phn t ny tp hp vi nhau thnh ht c kch thc ln no lm xut hin b mt d th gia ht AgI v mi trng phn tn.

97
Cc ht ny ng vai tr l nhn keo. Trng hp ny dung dch d KI, nhn keo s hp ph mt lng ln ion I- ln b mt (ion I- c trong thnh phn nhn keo, b mt nhn keo s hp ph u tin nhng ion no trong thnh phn ca n) v lm nhn keo tch in m, v ta c keo m (Ion I- c gi l ion quyt nh th hiu). trung ho in, b mt nhn keo ht mt lng ln ion tri du (K+) n gn b mt v cc ion ny gn b tng i cht ch vi b mt nhn keo, hnh thnh lp in kp trn b mt nhn keo, cng l qu trnh hnh thnh ion keo. Ton b ion keo s c trung ho in bng mt lng tng ng cc ion K+ nm ri rc trong dung dch, lp ion K+ ny lm thnh tng khuch tn, ton b ion keo (ht keo) v ion tng khuch tn to thnh mixen keo trong dung dch.
+ + +

+ +

mAgI

+ + + +

S cu to mixen keo AgI Cng thc cu to keo AgI m [(mAgI) nI(n-x)K+]x-.

Nhn keo

xK+

ion quyt nh tng ion i tng khuch tn th hiu b hp ph mixen keo AgI

Cc ht keo tch in cng du s y nhau. l nguyn nhn ti sao dung dch keo li bn vng. Nh vy, tnh bn vng ca keo ght lu l do s tch in cng du ca cc ion keo quyt nh. i vi keo a lu, tnh bn vng ch yu do lp v sonvat quyt nh. Lp v ny ngn cn khng cho cc ht keo dnh li. Ngoi cc nguyn nhn trn, tnh bn vng ca cc dung dch keo cn do s chuyn ng nhit ca ion keo, nhng nguyn nhn ny l th yu. 3. Cc loi th xut hin trn b mt mixen keo 3.1. Th nhit ng Khi kho st s hnh thnh mixen keo, ta thy gia b mt tch in ca nhn keo vi cc ion i c trong dung dch (theo mt lng tng ng) to nn mt lp in kp v do xut

98
hin mt bc nhy th gia b mt nhn keo (pha rn) vi dung dch. Th c gi l th nhit ng . ln ca th ny ch ph thuc vo cc c trng nhit ng ca mixen keo v dung dch, c bit ph thuc vo mt ion quyt nh th trn b mt nhn keo. Th nhit ng khng nh hng nhiu n tnh bn ca h keo, gi tr ca n tng i n nh v c quyt nh ch yu tng hp ph. 3.2. Th in ng Trong cu to ca mixen keo, gia ht keo v ion tng khuch tn gn b khng tht cht ch vi nhau. Di tc dng ca nhng yu t nhit ng ca h, cc ht keo v ion tng khuch tn lun chuyn ng tng i vi nhau, ta c th xem ht keo l phn tnh, cc ion tng khuch tn l phn ng. Gia phn tnh v phn ng tng i, xut hin mt lp in kp v mt th tng ng. Th ny thay i theo s chuyn ng tng i so vi nhau gia ht keo v tng khuch tn, gi l th in ng . Vy th in ng l th xut hin gia tng hp ph v tng khuch tn khi chng chuyn ng tng i so vi nhau.

+ + + + + + + + + +
tng khuch tn

ln ca th in ng ph thuc vo b dy ca tng khuch tn, vo s c mt ca cc cht in li trong mi trng phn tn.

=k.

K' = 2

K' C1 Z i2

: b dy tng khuch tn : lc ion ca dng dung dch 1 2 = ci Z i 2

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Th in ng t l thun vi b dy tng khuch tn, t l nghch vi lc ion ca dung dch. V th, mun lm gim b dy tng khuch tn, ta tng lc ion ca dung dch bng cch thm cht in gii vo h keo.

VI. c tnh b mt v s hp ph ca dung dch keo

1. Sc cng b mt Cc phn t trong lng pha ngng t (rn, lng) chu tc dng trung bnh v mi pha cc lc nh nhau nn lc tng hp tc dng ln mt phn t bng khng, trong khi , vi cc phn t trn b mt hay st b mt, tng hp lc tc dng vo n khc khng v hng trong lng cht lng theo phng vung gc vi b mt ca pha ngng t. Vy nng lng "d" ca cc phn t trn b mt so vi cc phn t nm su trong lng cht gi l nng lng b mt. Gi s mt cht c b mt S, nng lng b mt ca n l ES th: ES = k.S Trong k l mt hng s ph thuc vo nhit v bn cht cht ca cht , gi l sc cng b mt, k hiu l .

F 0
Vy, sc cng b mt l nng lng b mt ca mt n v din tch. F= 0 ES = .S E Hay = S S Nu nng lng b mt o bng erg, din tch o bng cm2. = erg dyn.cm dyn = = cm 2 cm 2 cm

Vy sc cng b mt c th nguyn bng lc tc dng trn mt n v chiu di ca b mt. chnh l lc cn thit (erg) tch cc phn t nm trn 1cm chiu di trn b mt khi lc ht ca cc phn t trong lng cht . Thc nghim cho thy rng: sc cng b mt ca cht rn l ln nht, sau n cc cht khc theo th t: rn > lng > kh V lc gia cc phn t l nh nn sc cng b mt ca cc hp cht phn t nh v gim theo chiu: phn cc + lin kt hidro > phn cc > khng phn cc.

100
V l do ny m sc cng b mt ca nc rt ln v cc hidrocarbon c sc cng b mt nh. Cc cht in li nng chy v cc kim loi c sc cng b mt ln v lin kt gia cc phn t bn.

2. S hp ph 2.1. Khi nim v s hp ph Nhng cht m s tn ti ca n c hnh thnh b mt s c nng lng d tr cao hn nhng cht khng tn ti b mt. Theo nguyn l II, cc h c tn ti b mt khng bn, khi gp cc iu kin c th, chng s t din bin tr v trng thi c nng lng thp hn. Theo biu thc: ES = .S, mun lm gim nng lng b mt c th t lm gim b mt S hay lm gim sc cng b mt . S t lm gim b mt S gii thch ti sao trong qu trnh ri t do, cc cht lng t kin ton khi cu v khi cu c b mt nh nht, ng vi cng mt khi lng vt cht. Khi khng c kh nng lm gim b mt S, h c th t din gim sc cng b mt bng cch hp ph cc cht khc c sc cng b mt nh hn. Vy s hp ph l s tp trung (t din bin) mt cht ny ln b mt cht khc thng lm gim nng lng b mt. - Nu qu trnh hp ph dn n s gim nng lng b mt ca vt hp gi l s hp ph dng (v d nc hp ph ru). - Nu s hp ph dn n s tng nng lng b mt ca vt hp gi l s hp ph m (v d: du hp ph ru). 2.2. hp ph hp ph l lng cht c hp ph trn mt n v din tch hay mt n v khi lng vt hp trng thi cn bng hp ph. Cht b hp ph ch to mt lp trn b mt cht hp ph gi l s hp ph n lp. Nu lc hp ph gia cht hp ph v cht b hp ph qu ln khin cho s hp ph to nn nhiu lp cht b hp ph trn b mt cht hp ph gi l s hp ph a lp. Tu thuc vo bn cht ca lc tng tc gia cht hp ph v cht b hp ph ngi ta chia ra s hp ph l hc v s hp ph ho hc. 2.3. S hp ph l hc Thc cht ca s hp ph l hc l s hp ph phn t. S hp ph xy ra do lc ht phn t (lc Vander Waals) quyt nh. V d: than hot tnh hp ph kh Clo trong cc mt n phng c. S hp ph l hc c nhng c im sau: - Lc hp ph nh nn s hp ph mang tnh thun nghch. - S hp ph to nhit nn khi nhit tng, hp ph gim v qu trnh phn hp ph c tng cng. l nguyn tc phc hi li cc mt n phng c. 2.4. S hp ph ho hc Thc cht ca s hp ph ho hc l s hp ph ion. Cc ion b hp ph to nn cc hp cht ho hc kh tan trn b mt cht hp ph. S hp ph ho hc c cc c im sau: - B mt cht hp ph b hp ph nhng ion c in tch tri du vi in tch ca b mt cht hp ph.

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- Lc hp ph rt ln, nn s hp ph ho hc c tnh cht bt thun nghch, nhit hp ph tng ng vi nhit ca phn ng ho hc. Ni chung khi nhit tng, hp ph tng. - S hp ph ho hc mang tnh cht ho hc, s chn lc tun theo nhng quy tc sau y: - Vi nhng ion c cng in tch, cht hp ph u tin hp ph cc ion c trong thnh phn ca cht hp ph - Vic hp ph nhng ion c trong thnh phn cht hp ph to iu kin thun li cho vic xy dng mng li tinh th. - Vi nhng ion c in tch khc nhau, b mt u tin hp ph c ion in tch tri du vi in tch b mt. Cn lu l gia hp ph l hc v hp ph ho hc khng c ranh gii r rt m s phn chia ch c tnh tng i. 2.5. S hp ph trn ranh gii phn chia dung dch - kh. Cht hot ng b mt Tu theo kh nng b hp ph trn ranh gii phn chia dung dch - kh m ngi ta chia ra lm cht hot dng b mt (vit tt l HBM) v cht khng hot ng b mt (KHBM). - Cht HBM l cht c kh nng b hp ph trn b mt phn chia hai pha. S hp ph cht HBM l hin tng b mt nn n ch xy ra khi cht HBM lm gim sc cng b mt ca dung mi. Do c th nh ngha cht HBM l cht lm gim sc cng b mt ca dung mi. Vy cht HBM phi c sc cng b mt nh hn so vi dung mi v t ho tan, v nu khng, n c xu hng ri khi b mt m tan su vo trong cht lng. Cc cht HBM i vi nc thng l cc hp cht hu c m phn t ca chng c nhm phn cc -COOH, -NH2, -NO2, -SO3H ... v nhm khng phn cc CnHm (vi n kh ln). Nhm phn cc a nc nn quay vo b mt ca nc, trong khi nhm khng phn cc k nc nn b y ra ngoi. T ta hiu v sao cc cht HBM rt t tan trong nc. Cc cht HBM c ng dng rng ri khng nhng lm bn cc h nh tng, huen ph m cn c dng lm cht ty ra, lm cht n mn (pha thm mt lng nh ca mt s cht HBM vo trong du, m s lm gim tc n mn ca thp nhiu ln). Nu cc phn t ca cht tan khng tp trung trn b mt m i su vo trong lng dung mi v lm tng sc cng b mt ca dung mi th gi l cht khng hot ng b mt. l cc cht c sc cng b mt ln hn dung mi v tan nhiu trong dung mi . Nu dung mi l nc th l cc axit, baz v mui v c tan. Trong phn t cc cht ny khng c phn k nc (m bo cho chng i su vo trong lng ca nc v lm tng sc cng b mt ca nc), t suy ra rng: Ion b hidrat ho cng mnh th kh nng lm tng sc cng b mt dung mi ca n cng ln. Cl- > Br- > I; Li+ > Na+ > K+ ; Ca2+ > Na+ Ngoi ra cn c nhng cht tan khng lm bin i sc cng b mt, v c sc cng b mt gn bng sc cng b mt ca dung mi. V d ng saccharose hu nh khng lm bin i sc cng b mt ca nc. 2.6. S hp ph trao i Cc ion tng khuch tn cng nh cc ion b vt rn hp ph rt c th tham gia trao i vi cc ion c trong mi trng - ngi ta gi l s hp ph trao i. S hp ph trao i c nhng c im sau: a. S hp ph trao i ch xy ra i vi mt s ion xc nh. Ngi ta phn bit cht hp ph axit v cht hp ph baz - Cht hp ph axit, v d SiO2, SnO2 x s nh axit, c kh nng trao i vi cation. - Cht hp ph baz, v d Al(OH)3, Fe(OH)3, x s nh baz, c kh nng trao i vi anion.

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i vi cht hp ph lng tnh, tu theo pH ca mi trng m n c kh nng hp ph trao i vi cation v anion- v d Aluminosilicat. b. S hp ph trao i khng phi lun lun thun nghch c. Xy ra chm hn nhiu so vi hp ph phn t, nht l i vi cc ion nm su trong cht hp ph. d. C th lm thay i pH ca mi trng khi ion trao i l H+ hay OH-. [CHP-]H+ + Na+ + Cl[CHP-]Na+ + H+ + Cl[CHP+]OH- + Na+ + Cl[CHP+]Cl- + Na+ + OHS hp ph trao i c ngha rt ln trong vic nghin cu t trong sinh vt hc cng nh trong k thut. Trong t c keo lng tnh, do s hp ph trao i, t c kh nng gip cy trng gi c phn bn v gii phng dn cung cp cho cy trong iu kin cn thit, do phn bn khng b ra tri - Vi t bc mu, keo t dng hu c c t nn kh nng gi phn bn km, phn d b ra tri. Trong k thut, s hp ph trao i c ngha rt ln. V d trong qu trnh nhum nhng si bng thc vt hp ph t mi trng cc cation mu v y vo dung dch cc ion Ca2+. Nhng cht c kh nng hp ph trao i vi cation gi l Cationit, nhng cht c kh nng hp ph trao i vi anion gi l Anionit - Vic s dng cc cationit v anionit ang c p dng rng ri lm sch nc, thu hi cc kim loi qu t dng dch v cng long cc kim loi .

VII. S ng t keo
V nguyn tc, nu ta loi b cc yu t duy tr tnh bn ca h keo s dn n s keo t, cc ht keo dnh li vi nhau v to thnh kt ta. Cc kt ta keo c kin trc khc nhau. Loi keo ght lu khi lng xung khng ko theo dung mi v kt ta di dng bt rt nh hoc di dng nh bng. Ngc li, cc keo a lu, khi lng xung ko theo mt lng dung mi tng i ln nn kt ta c tnh nhy. Mt s keo a lu khi ng t, tt c tr thnh mt khi nhy. Nu dung mi l nc th gi l hidrogel. Tht ng l mt v d in hnh v hidrogel. Sau y ta xt mt s phng php lm ng t keo. 1. S lm ng t keo bng cht in li 1.1 i vi keo ght lu Khi cho mt cht in li vo dung dch keo ght lu, do nng ion trong dung dch tng ln, cc ht keo s hp ph thm cc ion tri du do in tch ca chng gim nhanh, kt qu l keo s ng t. Th d: S to thnh cc chu th ca sng ra bin l kt qu ca s ng t keo bng cht in li ko di trong nhiu nm. 1.2. i vi keo a lu, s lm ng t keo kh hn nhiu v lp v solvat rt bn vng. Mun lm ng t keo a lu phi thm mt lng ln cht in li ly mt lp v solvat. Th d: Trong nh my x phng, ngi ta ph keo x phng bng cch cho mt lng ln tinh th mui n vo. Tc dng lm ng t keo ca cc cht in li ph thuc nhiu vo in tch ca ion ngc du vi ht keo. in tch ca ion ny cng cao th tc dng lm ng t keo cng mnh, do lng cht in li dng lm ng t keo cng nh. Th d: tc dng lm ng t keo m As2S3 ca cc cation nh sau: K+ : Ba2+ : Al3+ = 1 : 20 : 1000 2. S lm ng t keo bng keo tch in tri du

103
Khi trn hai dung dch keo tch in tri du th cc keo tch in tri du s trung ho ln nhau v kt ta lng xung. Trong trng hp ny cn ch rng mun ng t keo hon ton phi dng mt t l nht nh cc dung dch keo. Th d: Ngi ta dng phn nhm (K2SO4.Al2(SO4)3.24H2O) lm trong nc. Cc ht t st, ct ... trong nc sng tch in m khi gp cc ht keo nhm hidroxit (do s thy phn ca ion Al3+) tch in dng s lng xung thnh kt ta. 3. S lm ng t keo bng cch un nng Khi nhit tng lm tng tc chuyn ng nhit ca cc ht keo, do lm gim kh nng hp ph ca lp hp ph v lm ht keo tch in km. V vy khi va chm chng d kt hp v ng t. Tuy nhin, tnh bn ca cc dung dch keo i vi nhit l khc nhau. Th d: keo As2S3 d b ng t khi un nng nhng keo Fe(OH)3 khng bin i khi un nng.

VIII. S pepti ha
Cc kt ta keo khi tip xc vi nc t chuyn thnh dung dch keo gi l cc keo thun nghch. Ngc li, cc kt ta keo khi tip xc vi nc khng th chuyn li thnh dng dch keo gi l keo bt thun nghch (th d: keo Fe(OH)3). Tuy nhin, i khi thm vo mt lng nh cc cht in li, kt ta keo bt thun nghch c th chuyn thnh dung dch keo. S to thnh dung dch keo bng cch cho mt lng nh cht in li tc dng vi kt ta keo bt thun nghch c gi l s peptit ho. Hin tng ny c gii thch nh sau: Khi cho mt cht in li vo th cc ht ca kt ta keo s hp ph cng mt loi ion, do chng tch in cng du. Cc ht in tch cng du ny s y nhau v i vo dung dch. S pepti ho l mt trong nhng phng php phn tn quan trng nht iu ch cc dung dch keo.

104 CHNG X

IN HA HC

Nng lng ha hc c th chuyn thnh in nng trong cc pin.Ngc li, di tc dng ca dng in (s in phn),mt phn ng ha hc c th oc thc hin. l hai mt tng quan gia ha nng v in nng.

I. Phn ng oxi ha kh
1. Phn ng oxi ha kh L cc phn ng ha hc trong c s thay i s oxi ha ca cc nguyn t trc v sau phn ng. V d: 2Mg + O2 = 2MgO 2Al + Fe2O3 = Al2O3 + 2Fe 2HgO = 2Hg + O2 2KMnO4 + 16HCl = 5Cl2 + 2MnCl2 + 2KCl + 8H2O 3Cl2 + 6KOH = 5KCl + KClO3 + 3H2O Trong mt phn ng oxi ha kh c hai qu trnh xy ra ng thi - S oxi ha l s nhng electron ca cc cht - S kh l s nhn eletron ca cc cht V tng ng ta c - Cht kh l cht nhng electron (tng s oxi ha ) - Cht oxi ha l cht nhn electron (gim s oxi ha) Trong cc v d trn cc cht oxi ha l: O2, Fe2O3, KMnO4 v cht kh l Mg, Al, HCl... Nhng cht oxi ha in hnh nh: HNO3, K2Cr2O7, KMnO4, PbO2 v.v... Nhng cht kh in hnh nh cc ion: SO 32_-,NO2-, nhng cation c s oxi ha thp nh Sn2+, Fe2+ v mt s cht nhit cao nh C, H2, CO, Al. 2. Cp oxi ha kh Hai dng trc v sau phn ng to thnh mt cp oxi ho kh lin hp. Dng oxi ha (c s oxi ha cao hn) c vit trn v dng kh (c s oxi ha thp) c vit di. Sau phn ng dng oxi ha chuyn thnh dng kh tng ng v ngc li KhI + OxII OxI + KhII

OxI v KhI, OxII v KhII c gi l cp oxi ha kh ca cc cht I v II v c vit l OxI/KhI v OxII/KhII

105
V d: Zn +CuSO4=Cu +ZnSO4 Trong phn ng ny ta c: Zn2+/Zn v Cu2+/Cu c gi l cp oxi ha kh ca km v ng. Vy trong mt phn ng oxi ha kh dng oxi ha ca cp oxi ha kh ny phn ng vi dng kh ca cp oxi ha kh kia. 3. Cn bng phng trnh oxi ha kh Nguyn tc: tng s electron m m cc cht kh mt i bng tng s electron m cc cht oxi ha thu vo Ta thc hin cc bc sau: - Xt s thay i s oxi ha ca cc nguyn t. - Vit phng trnh thu, nhn electron t xc nh h s ca phng trnh - Cn bng phng trnh phn t. V d: cn bng phng trnh phn ng KMnO4 + Na2SO3 + H2SO4 2 Mn+7 5 + 5e S+4 2 Mn+7 + MnSO4 + K2SO4 +Na2SO4 + H2O Mn+2 2e 5S+4 S+6 2 Mn+2 + 5S+6

Phng trnh phn t: 2 KMnO4 + 5 Na2SO3 + 3H2SO4 = 2MnSO4 + K2SO4 + 5Na2SO4 + 3H2O 4.ng lng gam ca phn ng oxi ha kh ng lng gam ca cht oxi ha hoc cht kh c tnh phn t gam ca cht chia cho s electron m mt phn t cht cho hoc nhn. Trong v d trn: MKMnO4 KMnO4 =

2
MNa2SO3

Na2S03

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II. Phn ng ha hc v dng in. Nguyn t Galvani
nh ngha: Nguyn t Galvani l thit b bin i ha nng thnh in nng. Dng in sinh ra trong pin l do nhng phn ng oxi ha kh xy ra trn b mt tip xc gia kim loi v dung dch cht in li. 1. S xut hin th in cc Khi nhng mt thanh kim loi vo nc, di tc dng ca cc phn t nc lng cc, cc ion s tch khi b mt kim loi v i vo dung dch di dng cc ion b hydrat ha, khi cc electron cn li trn b mt lm bn kim loi tch in m. Cc ion Mn+ ca kim loi s b bn in m ny ht v ta c cn bng ng sau y: M Mn+ + ne S ion ny khng lan truyn ra xa v chng to thnh mt lp in kp trn ranh gii tip xc gia nc v bn kim loi. Lp in kp cng xut hin khi nhng thanh kim loi vo dung dch mui ca n. Vy khi nhng mt thanh kim loi vo nc hay vo dung dch mui ca n th trn ranh gii tip xc gia kim loi v dung dch s hnh thnh mt lp in kp, ti y xut hin mt hiu in th gi l th in cc. 2. Nguyn t Daniel Jacobi ( pin Cu-Zn ) Xt nguyn t Galvani n gin l pin (Cu-Zn). Gm mt in cc Zn v mt in cc Cu nhng vo dung dch mui sulfat ca chng. Hai dung dch ny c ni vi nhau bi cu mui dn in KCl. Khi ni hai in cc bng mt dy dn c mc Vn k, ta thy c mt dng in chy t cc Cu sang cc Zn. Khi , trn in cc Zn xy ra phn ng oxi ha: Zn Zn2+ + 2e Zn tan vo dung dch di dng ion li cc electron trn in cc, cc electron ny theo dy dn chuyn sang in cc Cu. Trn in cc Cu xy ra phn ng kh: Cu2+ + 2e Cu 2+ Nh vy, cc ion Cu i t dung dch vo in cc, nhn electron chuyn thnh Cu kim loi bm trn in cc. Ta c phng trnh phn ng tng cng: Zn + Cu2+ = Zn2+ + Cu Do phn ng ny m xut hin dng in trong pin. Nguyn nhn sinh ra dng in trong pin l do s chnh lch v th in cc ca kim loi. S chnh lch ny cng ln ngha l hot ng ca cc kim loi cng khc nhau th phn ng oxi ha kh xy ra trong pin cng mnh. in cc m xy ra qu trnh oxi ha ( mt electron) l cc m. Trong phn ng trn, in cc Zn l cc m. in cc m xy ra qu trnh kh l ( nhn electron) l cc dng.

107
Trong phn ng trn, in cc Cu l cc dng. Nguyn t Galvani c k hiu nh sau: (-) Kim loi 1 dd mui kim loi 1 dd mui kim loi 2 Kim loi 2(+) V d: Pin (Cu-Zn) (-) Zn dd ZnSO4 dd ZnSO4 Cu (+) 3.Sc in ng ca nguyn t Galvani Nu ta ghp 2 bn phn ng xy ra trong pin to thnh mt nguyn t Galvani th sc in ng E ca mt nguyn t Galvani bt k bng hiu s th in cc ca hai in cc trong pin.

- (-) Vi E: l sc in ng ca pin
E=
(+)

: th in cc ca in cc m (in cc xy ra qu trnh oxi ha) Sc in ng tiu chun ca pin l sc in ng ca pin o iu kin tiu chun (P= 1atm, t= 25oC, C= 1 M) V d: Pin (Cu Zn)
(-)

(+)

: th in cc ca in cc dng (in cc xy ra qu trnh kh)

E0 =
G)

(+)

(-)

= 0,34V (-0,76) = 1,1V

4. Lin h gia sc in ng ca nguyn t Galvani v nng lng t do (

G ca phn ng cho bit phn ng c th xy ra hay khng. Gia G ca phn ng v sc in ng ca pin c mi lin h sau: G0= -nE0F

Nh vy da vo gi tr sc in ng ca pin ta c th bit phn ng oxi ha kh c th xy ra hay khng. iu kin tiu chun ta c th c:

G0= -nE0F Vi n: s e m 1 phn t trao i trong phn ng trao i in cc F: l s Faraday = 96500 Coulomb E0: l sc in ng tiu chun ca pin V vy c th ni E0 ca nguyn t Galvani l thc o chiu xy ra ca phn ng oxi ha kh iu kin tiu chun. Nu E0 > 0 th G0 v phn ng xy ra theo chiu thun. 5. Chiu ca phn ng oxi ha kh

108
Nguyn tc: Khi cho 2 cp oxi ha kh tip xc vi nhau th dng oxi ha ca cp c th in cc cao phn ng vi dng kh ca cp c th in cc thp. 6. Hng s cn bng ca phn ng oxi ha kh

OxI + KhII

KhI + OxII

Trong OxI/ KhI c th in cc l

cc l

v OxII/KhII c th in

0 2

Ta c: Vy: G0 = -nE F = - RTlnK -lnK = - nE0F/RT lnK = nE0F/RT

250C v chuyn sang logarit thp phn: lgK = nE0/0.059 K = 10 nE0 / 0,059 K = 10 Vi:
n ( 0(+) 0(-)

) / 0.059

0 0

(+) (-)

: th in cc tiu chun ca in cc dng

: th in cc tiu chun ca in cc m

7. Xc nh th in cc, th oxi ha kh, sc in ng ca pin iu kin khc chun. Phng trnh Nersnt Khi xt iu kin khc chun, Nersnt a ra phng trnh nu ln mi lin h gia th in cc kim loi v cp oxi ha kh vi nng ca cc in c trong dung dch nh sau: 7.1 Th in cc ca in cc kim loi 250C v nng ca ion kim loi 1M.

V d :

Mn+/M

Mn+ / M

0.059 n+ n lg[M ]

Zn2+ + 2e

= =

Zn
0

Zn

2+

/ Zn

Zn

2+

/ Zn

0.059 2+ n lg[Zn ]

7.2 Th oxi kh ca mt cp oxi ho kh . Trong mt cp oxi ho kh c phng trnh lin h nh sau

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aOx + Ta c: ne b Kh

Ox/Kh

Ox/ Kh

0.059 [Ox]a + n [ Kh]b Fe3+ + 1e Fe2+

V d :

Fe

3+

2+ /Fe

3+ 2+ Fe / Fe

[ Fe + 3 ] + 0,059 lg [ Fe 2+ ]

7.3 Th oxi ha kh ca mt cp oxi ho kh c mi trng tham gia. Phng trnh lin h c dng: aOx + ne + CH+ bKh + c/2H2O
[Ox]a [ H + ] b lg [ Kh]
c

V d:

Ox/Kh

Ox/ Kh

0.059 n

MnO4- + 5e + 8H+

Mn2+ + 4H2O

MnO4-/Mn2+

MnO4-/ Mn2+

[ MnO4 ] [ H + ]8 0.059 [ Mn 2+ ] + 5 lg

7.4 Sut in ng ca nguyn t galvani iu kin chun. i vi mt phn ng oxi ha kh tng qut ta c: E pin = E0 pin +
0.059 n

lg

[Ox]a [ Kh]b

V d : pin (Cu-Zn) 250C c sut in ng l

0.059 [Cu 2+ ] Epin =E pin + lg 2 [ Zn 2+ ]
0

Vi [Cu2+] v [Zn2+] 1M Hoc tnh theo cng thc. E pin =

Vi
(-)

: (+)

(+)

(-)

th ca in cc xy ra qu trnh kh

: th ca in cc xy ra qu trnh oxi ha

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Mt s v d: V d 1: Xt xem thic kim loi c th tan trong dung dch axit mnh c nng =1 mol/l) hay khng? Qua bng cc th in cc chun, ta thy nhit thng: Na phn ng: Sn++ + 2e = Sn c th in cc chun = -0,14 V V na phn ng: H+ + e = H2 c th in cc chun = 0,00V Nh vy, trong pin thic - hiro, in cc hiro l in cc dng v in cc thic l in cc m, ngha l Sn chuyn electron sang in cc Hiro v pin c sc in ng: E0 = 0,00 - (-0,14) = 0,14 V Sc in ng ca pin c gi tr dng ( E>0 hayG <0) cho thy phn ng: Sn + 2H+ = Sn2+ + H2 Xy ra mt cch t pht, ngha l thic kim loi c th tan trong axit c nng 1N. Khi ghp hai in cc vi nhau, in cc c th ln, na phn ng xy ra theo chiu thun v in cc c th b, na phn ng xy ra theo chiu nghch. Trong trng hp pin thic - hiro ta c: 2H+ + 2e = H2 V: Sn = Sn2+ + 2e Qua v d ny rt ra mt kt lun chung: Nhng kim loi c th in cc chun
0 0

0<0 c th tan trong dung dch axit gii phng hiro.

V d 2: Crom kim loi c th y c st ra khi dung dch ca mui st (III) hay khng? Qua bng cc th in cc chun ta thy: Na phn ng: Cr3+ + 3e = Cr c th in cc chun = -0,74 V V na phn ng: Fe3+ + 3e = Fe c th in cc = 0,04 V V -0,04 V > -0,74 Nn na phn ng th hai xy ra theo chiu thun v na phn ng th nht xy ra theo chiu nghch: Cr = Cr3+ + 3e Fe3++ 3e = Fe Hay phn ng: Cr + Fe3+ = Fe + Cr3+ Xy ra, ngha l crm kim loi tan v st kim loi c kt ta v phn ng 0 c: E = -0,04 + (-0,74)= 0,70 V Vy: Kim loi c th in cc chun b y c kim loi c th in cc chun ln hn ra khi dung dch mui ca n. V d 3: Trong cc mui kali halogenua ( k hiu KX), mui no s tc dng vi FeCl3? Qua bng cc th in cc chun, ta thy:
0 0

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Fe3+ + e = Fe2+ , 0 = + 0,77 V F2 + 2e = F- , 0 = + 2,86 V Cl2 + 2e = 2Cl-,0 = + 1,36 V Br2 + 2e = 2Br-, 0 = + 1,07 V I2 + 2e = 2I-, 0 = + 0,54 V Phn ng gi KX v FeCl3 nu c xy ra th theo phng trnh ion sau y: 2X- + 2Fe3+= X2 + 2Fe2+ Trong trng hp KX l KF, th 0 = 0,77 - 2,86 = - 2,09 V Trong trng hp KX l KCl, th 0= 0,77 - 1,36 = -0,59 V Trong trng hp KX l KBr, th 0= 0,77 - 1,07 = - 0,30 V Trong trng hp KX l KI, th 0= 0,77 - 0,54 = 0,23 V Vy ch c KI c th kh c FeCl3 = 2FeCl2 + I2 + 2KCl V phn ng c E0 > 0 ngha l G 0<0 V d 4: Tnh nng cn bng ca ion Fe2+ khi nhng mt thanh st vo dung dung dch ZnSO4 1M Phn ng c th xy ra l Fe + Zn2+ = Fe2+ + Zn Sut in ng chun gi thit ca pin l: E0 =

2+ Zn / Zn

2+ Fe / Fe

= - 0,76 - (- 0,4 4) = - 0,32 V

Hng s cn bng ca phn ng l: KC = CFe2+ = 1,4.10-11M KC = 1,4 . 10-11 Ngha l khi: CZn2+ = 1M th CFe2+ = 1,4.10-11M Nh th phn ng thun hu nh khng xy ra.Trn thc t,Zn y c Fe ra khi dung dch cha ion Fe2+, ngha l xy ra phn ng ngc li vi phn ng gi thit trn.

III. Cc loi in cc
in cc l h gm mt thanh dn in tip xc vi mt cp oxi ha kh Thng gp cc loi in cc sau: 1. in cc kim loi - ion kim loi Gm mt thanh kim loi tip xc vi dung dch cha ion ca n. Trn din cc xy ra phn ng: Mn+ + ne = M

112
Th in cc c tnh theo phng trnh sau:

n+ M /M

n+ M /M

0.059 n

lg [M n+]

V d: Thanh km tip xc vi dung dch ZnSO4. Phn ng in cc l: Zn -2e = Zn2+ K hiu: Zn2+ Zn 0.059 Zn2+ / Zn = 0Zn2+/ Zn + 2 lg[Zn2+] Nu nng dung dch Zn2+ = 1M th ta c in cc Zn tiu chun. 2. in cc oxi ha kh Gm mt dy kim loi tr (Pt) tip xc vi dung dch cha ng thi 2 dng oxi ha v kh ca mt cp oxi ha kh . Kim loi tr ng vai tr tip nhn v chuyn electron gia 2 dng oxi ha v dng kh.

Ox/Kh

Ox/ Kh

0.059 n

lg

[Ox]a [ Kh]b

V d: in cc Fe3+/ Fe2+ Gia tm Pt v dung dch xut hin mt hiu s in th do cn bng: Fe2+ - 1e = Fe3+

Fe3+/ Fe2+

Fe3+/ Fe2+

[ Fe + 3 ] + 0,059 lg [ Fe 2+ ]

Nu CFe3+= CFe2+= 1M, t0=250C, ta c in cc oxi ha kh tiu chun ca cp Fe3+/ Fe2+ 3. in cc kh - ion L in cc gm cht kh tip xc vi cation ca n trong dung dch. V d: in cc hydro: Gm 1 bn Pt ph mui Pt c phun kh H2 tip xc vi dung dch cha ion H+. Nh vy c th xem in cc hydro nh mt tm hydro nhng vo dung dch cha ion H+. Phn ng in cc: H2 2H+ + 2e

+ 2H / H2

+ 2H / H2

0.059 + 2 2 lg[H ]

Nu CH+ = 1 mol/l ta c in cc hydro tiu chun:

0 ( H /2H
2

= 0,00V)

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Ngi ta dng in cc hydro tiu chun xc nh th in cc ca cc in cc khc bng cch ghp in cc hydro tiu chun vi in cc cn xc nh th in cc tiu chun ri o hiu in th gia hai in cc. 4. i n c c calomen: Hg/Hg2Cl2,Clin cc calomen c th c hnh dng khc nhau nhng lun lun gm thy ngn nm cn bng vi ion Cl- gin tip qua mui kh tan Hg2Cl2 (calomen) Trn in cc xy ra phn ng: Hg22+ +2e = 2Hg Th ca in cc Hg c tnh theo cng thc: 0.059 Hg2+ = 0 + 2 lg [Hg22+ ] Nhng trong lp calomen c cn bng: Hg2Cl2 = Hg22+ + 2ClTa li c: [Hg22+] =THg2Cl2 / [Cl-]2. Thay nng ny vo cng thc trn, sau khi rt gn ta c cng thc th in cc ca in cc calomen l:

i. Khi [Cl- ] bo ha th

cal

cal

- 0,059 lg[Cl-]

V vy mun gi cho nng Cl- c nh th th ca in cc calomen khng

cal

= 0,25V

in cc calomen thng c dng lm in cc so snh trong cc phng php chun o th hay xc nh pH bng phng php in ha. N cng c dng thay cho in cc hydro tiu chun. 5. in cc thy tinh Gm mt ng thy tinh u c thi thnh mt bu hnh cu rt mng, bn trong cha dung dch c nng H+ xc nh v mt in cc Ag ph AgCl. Khi nhng in cc ny vo mt dung dch th mt phn cch thy tinh - dung dch pht sinh mt in th m tr s ca n ph thuc vo nng ion H + theo ph ng trnh:

= 0
tt

tt

+ 0,059 lg[ H+ ]

Trong 0tt l mt hng s i vi mi in cc . V vy trc khi dng cn phi xc nh li th ca chng bng nhng dung dch m bit pH

IV. ng dng ca nguyn t Galvani

1. Xc nh th in cc tiu chun ca in cc kim loi v in cc oxi ha kh tiu chun Cho n nay cha c cch no xc nh chnh xc th in cc m ngi ta ch xc nh th in cc tng i ca mt in cc khi so snh n vi mt in cc khc m in cc ny qui c c 0 = 0. l in cc hydro tiu chun. 1.1. Xc nh th in cc tiu chun cu in cc kim loi

114
Ghp in cc kim loi tiu chun vi in cc hydro tiu chun thnh mt nguyn t Galvani, o sut in ng ca nguyn t v xc nh chiu ca dng in.

V d: o th incc tiu chun ca in cc Zn Lp pin gm in cc km tiu chun v in cc hyro tiu chun ([H +] = [Zn2+] = 1M) (-) Zn Zn2+ H+ H2(Pt) (+)
Thc nghim cho thy phi kim hot ng th in cc hyro tiu chun l cc dng v in cc km tiu chun l cc m. o sut in ng ca pin ny ta c E0 = 0,736V E0 pin =
0
2H+/ H2

- 0 Zn2+/ Zn = 0,736V

Vy 0 Zn2+/ Zn = 2H+/ H2 - E0 pin = 0 0,763 = -0,763V 1.2 Xc nh th in cc tiu chun ca in cc oxi ha kh: ta lp pin gm in cc oxi ha kh tiu chun v in cc hyro tiu chun. V d: in cc Fe3+/Fe2+ thc nghim cho thy E0 pin = 0,77V v khi pin hot ng th mch ngoi electron chuyn t in cc hyro tiu chun sang in cc oxi ha kh tiu chun. Vy in cc oxi ha kh tiu chun l cc dng. E0 pin = 0 Fe3+/Fe2+ - 2H+/ H2 = 0,77 0 = 0,77V Bng cch tng t ngi ta xc nh c th in cc tiu chun ca cc in cc kim loi v cc cp oxi ha kh ri xp thnh bng th in cc tiu chun ca kim loi v cc cp oxi ha kh (xem phn ph lc) Da vo bng ny ta thy: - Kim loi ng trc hyro c th in cc chun m nn y c hyro ra khi dung dch axit. - Kim loi c th in cc cng b th cng d mt electron tr thnh cation. - Kim loi xp sau hyro c th in cc dng khng y c hyro ra khi axit. - Kim loi c th in cc thp y c kim loi c th in cc cao ra khi dung dch mui. Trong mt cp oxi ha kh nu dng oxi ha cng mnh th dng kh cng yu v ngc li 2. Xc nh PH bng phng php in ha V nguyn tc, o PH ca mt dung dch bng phng php ny, ngi ta cn s dng hai in cc thch hp. Trong , mt th in cc ph thuc vo nng ion H+ (ngha l ph thuc vo PH) nh in cc hyro, in cc thy tinh, cn in cc kia c th xc nh v khng i, thng l din cc calomen. Hai in cc ny ghp thnh nguyn t Galvani. o sc in ng ca pin v suy ra PH. V d: o PH bng cp hidro calomen Nhng vo dung dch cn o PH mt in cc calomen v mt in cc Pt. Thi mt lung kh hyro c p sut 1 atm vo in cc Pt. Khi ta c nguyn t Galvani sau
0

(-) (Pt) H2 H+ KCl, Hg2Cl2 Hg (+)

Sut din ng ca nguyn t ny l

115
E=

cal

H2

M th ca in cc hyro 250C l Nn E=

H2

= 0,059 lg CH+

cal + 0,059 PH
E-

cal

T ta c:

PH = 0,059

V d 2: o PH bng cp in cc thy tinh calomen Lp nguyn t Galvani gm din cc thy tinh (bu thy tinh nhng trong dung dch cn o PH) v in cc calomen. Trong nguyn t ny, in cc calomen l cc dng. Sut in ng ca nguyn t l E=

cal = cal 0
tt

tt

+ 0,059 PH

T ta c: EPH = 0,059 3. Xc nh bin thin th ng p tiu chun (G0) ca mt phn ng Ta bit bin thin th ng p tiu chun ca phn ng oxi ha kh lin h vi sut in ng ca pin nh sau: G0 = - nE0F Do nu bit th oxi ha tiu chun ca cc cp oxi ha kh trong mt phn ng ta c th tnh c bin thin th ng p ca phn ng 4. Phng php chun o th Trong phng php ny, im tng ng c pht hin qua s pht hin t ngt v th, to ra mt bc nhy th trn ng cong chun . V nguyn tc, tin hnh chun ngi ta thit lp mt nguyn t Galvani gm mt in cc c th ph thuc vo nng ion mun chun (gi l in cc ch th) v th in cc khng i (gi l in cc so snh). o sut in ng ca n trong sut qu trnh chun . V ng cong chun t xc nh im tng ng V d: Xc nh nng ca dung dch NaCl bng phng php chun o th vi dung dch chun l dung dch AgNO3 Thit lp nguyn t Galvani gm mt in cc bc nhng trong mt th tch xc nh dung dch AgNO3 v mt in cc calomen chun. T buret cha dung dch NaCl cha bit nng , thm dn vo cc cha hai in cc. Sau mi ln thm NaCl li o sut in ng. E=

cal -

0tt

Ag+/Ag

Cal

116
+ + 0,059 lg [Ag ] - Cal Trong qu trnh chun , nng [Ag+] gim dn. Do E o c gim dn. Ti im tng ng nng Ag+ v cng b lm cho sut in ng gim mt cch t ngt. V ng cong chun v tm im tng ng trn ng cong . T xc nh c nng ca dung dch NaCl.

E=

Ag+/Ag

III. S in phn
1. nh ngha S in phn l qu trnh oxy ha - kh xy ra trn b mt in cc khi cho dng in mt chiu i qua dung dch cht in ly hay qua cht in ly nng chy v c km theo s bin i in nng thnh ha nng. 2. Hin tng in phn: hiu r bn cht s in phn, ta quan st hin tng xy ra khi in phn NaCl nng chy. Khi nng chy, NaCl phn li thnh cc ion Na+ v Cl- chuyn ng hn lon. - Trong bnh in phn, nu ta p t vo bnh 1 in trng tc l ni vi ngun in mt chiu th cc ion khng chuyn ng t do m chuyn ng nh hng: cc cation hng v Catod (cc m) v cc anion v Anod (cc dng).

- Catod: 2Na+ + 1e 2Na ( p/ Catod) - Anod: 2Cl- Cl2 + 2e (p/ Anod)

2Na+ + 2Cl- 2Na + Cl2 hay 2NaCl dpnc 2Na + Cl2 + Cc ion Na v Cl ng vai tr dn in gia cc in cc, kh Cl2 thot ra khi bnh in phn, cn Na nng chy b tch ra vng Catod. 3. Cc trng hp in phn 3.1 in phn nng chy: in phn nng chy dng in phn mt s mui (ch yu mui halogenua), oxit, hirxit ca kim loi kim, kim th, nhm nhm mc ch iu ch nhng kim loi v mt s phi kim nh F2. V d 1: in phn Al2O3: Al2O3 nc 2Al3+ + 3O2Catod: Al3+ + 3e Al x4 2Anod: 2O O2 + 4e x 3 2Al2O3 V d 2: in phn NaOH: Catod: Anod: NaOH nc Na+ + OHNa + 1e Na x4 4OH O2 + 2H2O + 4e x1 4NaOH
dpnc dpnc

4Al + 3O2

O2 + 2H2O + 4Na

117
3.2 in phn dung dch: V d: in phn dung dch NaCl, c nhng qu trnh in ha no xy ra cc in cc? C s gii p cc vn t ra l so snh cc i lng th in cc ca nhng cp oxi ha - kh tng ng c kh nng tham gia vo cc qu trnh oxi ha hay kh trn in cc khi in phn v i lng th in cc c trng cho kh nng oxi ha hay kh ca cc cp oxi ha - kh. Catod: trong qu trnh in phn s din ra qu trnh kh dng oxi ha ca cp oxi ha - kh. Khi c mt nhiu dng oxi ha th trc ht phi b kh (+ne) dng oxi ha ca cp oxi ha - kh no c kh nng oxi ha mnh nht, ngha l c th in cc ln nht. Dng oxi ha l cc Men+ v H+ ca dung dch cht in li Mun bit qu trnh no xy ra (ion no s phng in) cn so snh th in cc (th kim loi) ca kim lai vi th in cc ca Hir. ( CH+ = 10-7M) 0.059 H2 = 0H2 + lg [H+] = -0,059 pH = -0,059 x 7 = -0,41 V 1 Trong dung dch trung tnh, nu kim loi c th ln hn -0,41V th n s kt ta (so vi dy th in cc ca kim loi iu ny ch c th xy ra i vi nhng kim loi t Sn tr v cui dy) Men+ + ne Me Nu kim loi c th nh hn -0,41V th H2 s bay ln (nhng kim loi t Ti tr v u dy): 2H+ + 2e H2 (i vi mi trng axit) Hay 2H2O + 2e H2 + 2OH- (i vi mi trng trung tnh hay baz) Cn nu kim loi c th tng ng -0,41V th c th kim loi kt ta hay kh H2 bay ln ty theo nng v iu kin tin hnh (i vi kim loi t Zn Ni) Anod: trong trng hp ny dng kh chnh l cc anion gc axit v hyrxyl ca dung dch cht in li. Ngoi ra cn lu ty vt liu dng lm in cc m n c th b oxi ha (-ne) khi in phn. V vy cn xt qu trnh anod theo 2 in cc : anod tr (khng b oxi ha nh graphit, platin...) v anod tan (b oxi ha nh niken...)

- i vi anod tr: da theo th in cc ca cc cp oxi ha - kh tng

ng cng nh m t s yu t khc, ta c nhn xt: + B oxi ha trc ht l cc anion khng cha oxi (I-, Br-, Cl-...) + Sau n OH+ Cui cng l anion cha oxi (SO32-, SO42-...) Ch : Trong trng hp ny anion khng cha oxi ch b oxi ha (-ne) khi s dng th hiu in phn rt ln), cn khi in phn dung dch nc ca axit v mui khng cha oxi (t axit HF v mui ca n), th cc anion gc axit s b oxi ha. V d 3: in phn dung dch nc NiSO4 vi anod tan Niken 0Ni2+/Ni = -0,250V ( >-0,41V) nhng km hn th oxi ha nc nhiu: 2H2O - 4e = 4H+ + O2 0= 1,228V nn catod xut hin kt ta Niken, cn anod in cc Niken s ha tan.

118
NiSO4 Catod Ni2+ + SO42- Anod Ni2++ 2e = Ni Ni - 2e = Ni2+ i vi anod tan: c th xy ra qu trnh phng in (-ne) ca anion (qu trnh oxi ha amin) hay ha tan anod. Qu trnh no s xy ra ty thuc v tr ca cp oxi ha - kh tng ng trong bng th in cc tiu chun. - Nu kim loi anod c th nh hn (tnh kh mnh hn) th in cc ca cc cp oxi ha - kh th anod s b ha tan: Me - ne = Men+ Cn nu ngc li th hoc anion gc axit hay anion OH- b oxi ha . V d 4: in phn dung dch mui CuCl2 vi anod tr: Cu c th 0,34V, ln hn -0,41V nhiu: CuCl2 Catod Cu2++ 2Cl- Anod Cu2+ +2e = Cu 2Cl- - 2e = Cl2

V d 5: in phn dung dch mui K2SO4 vi anod tr: catod kim loi K c th -2,92V < -0,41V nhiu, do H+ b kh cho H2 bay ra v trong khng gian catod to thnh KOH do s tch ly cc ion K+ v OH-. Cn anod c oxi bay ra do ion OH- b oxi ha ( - ne) v trong khng gian anod to thnh H2SO4 nh s tch ly cc ion H+ v SO4-. 2 K2SO4 Catod 4K+ + 2SO4- Anod 4K+ 2SO424H2O + 4e = 4OH- + 4H 2H2O - 4e = 4H+ + 2O 4H = 2H2 2O = O2 V d 6: in phn vi anod tan. Nu khi in phn ta dng anod lm bng kim loi hay hp kim th lc anod b tan dn do kim loi b xi ha thnh ion kim loi. in phn dung dch AgNO3 vi anod l bc th cc phn ng in cc l: Catod : Ag+ + 1e = Ag Anod : Ag = Ag+ +1e Da trn nguyn tc ny ngi ta tinh luyn kim loi. V d: c ng nguyn cht th t ng b ln cc kim loi qu nh Ag, Au, Pt... ta tin hnh in phn dung dch CuSO4 vi anod ng c ln tp cht, lc phn ng i cc l: catod: Cu2+ + 2e = Cu anod: Cu = Cu2+ + 2e 4. nh lut Faraday

119
Lng cht thot ra in cc t l thun vi khi lng mol nguyn t hay khi lng mol phn t ca cht thot ra in cc, vi in lng i qua dung dch v t l nghch vi s electron tham gia phn ng in cc. nh lut Faraday c vit di dng biu thc nh sau: MIt m= n 0F m: khi lng cht thot ra in cc (tnh theo gam) M: khi lng mol kh hay mol phn t ca cht thot ra in cc t: thi gian in phn (giy,s) I: cng dng in (Ampe) Q = It : in lng (Coulomb) F: s Faraday (=96500 coulomb/mol) no: s electron tham gia phn ng in cc V d: tnh khi lng Al thu c catod v th tch kh clo thu c anod sau khi in phn 2gi vi cng dng in 20A, khi in phn nng chy AlCl3. Ta c phng trnh phn ng in phn: 2AlCl3 pnc 2Al + 3Cl2 Catod: Al + 3e Al Anod: 2Cl- Cl2 +2e 27.20.2.3.3600 Khi lng Al: m = = 14,43 g 3.96500
3+

S mol Cl2 bay ra: n= It m = n 0F M = 20.2.3600 = 0,746 mol 2.96500

Th tch kh Clo = 0,746 . 22,4 = 16,71 l 5. ng dng ca s in phn in phn c ng dng rt rng ri trong nhiu lnh vc khc nhau - iu ch nhiu cht v c cng nh hu c nh H2, O2, Cl2, NaOH, H2O2 - iu ch cc kim loi - Tinh luyn cc kim loi - M in

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PH LC
BNG 1

Sinh nhit tiu chun ca mt s hp cht

Cht H2 O H2 O CO CO2 SO2 SO3 SO3 NO NO2 NH3 HCl HI H2 S CH4 C2 H6 C2 H4 C2 H2 nC6H4 C6 H6 C6 H6 CH3OH C2H5OH CH3COOH NaOH NaF NaCl NaBr Trng thi k l k k k k l k k k k k k k k k k l k l l l l r r r r H0s (kcal/mol) -57,.800 -68,320 -26,420 -94,050 -70,96 -94,45 -110,52 +21,600 +8,090 -11,040 -22,060 +6,200 -4.820 -17,890 -20,240 +12,500 +54,190 -39,96 +19,89 +11,720 -57,02 -66,35 -115,7 -102,00 -136,5 -98,23 -86,45 Cht Na2SO4 KCl KOH NaI MgO Mg(OH)2 MgCl2 MgCO3 MgSO4 CaO Ca(OH)2 CaCO3 canxit CaF2 CaCl2 Al2O3 Al2(SO4)3 FeO Fe2O3 FeS FeSO4 CuO CuSO4 MnO MnSO4 AgNO3 BaCO3 BaSO4 Fe2O3 ZnO Trng thi r r r r r r r r r r r r r r r r r r r r r r r r r r r r r H0s (kcal/mol) -330.500 -104.180 -102.000 -69.3 -143.84 -221.00 -153.4 -266 -305.5 -151.9 -235.8 -288.45 -290.3 -190.0 -399.09 -820.98 -64.30 -196.50 -22.80 -220,5 -37.1 -184.0 -92.1 -254,2 -29,400 -290,703 -352,103 -77,486 -82,036

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BNG 2

Nhit t chy tiu chun ca mt s hp cht hu c

Cht Metan Eptan Protan n-Butan n-Pentan Etylen Axetylen Benzen Toluen Naptalen Saccaroz Metanol Etanol Axit axetic Axit benzonic

Cng thc CH4 C2 H6 C3 H8 C4H10 C5H12 C2 H4 C2 H2 C6 H6 C6 H6 C7 H8 C10H8 C12H12O11 CH3OH C2H5OH CH3COOH C5H5COOH

Trng H0c thi (kcal/mol) k -212.800 k -372.820 k -530.600 k -678.980 k -845.16 k -337.230 k -310.620 k -787.200 l -780.980 l -934.500 r -1228.18 r -1348.900 l -173.670 l -326.700 l -208.340 r -771.200

BNG 3

Entropy tiu chun ca mt s cht

Cht H H2 C C2 N N2 O O2 O3 Trng thi k k k k k k k k k So (Cal/mol ) 27.391 31.208 37.759 47.636 36.613 45.769 38.476 49.003 57.079 Cht F F2 S Cl Cl2 Br Br2 I I2 Trng thi k k k k k k k k K So (Cal/mol ) 37.917 48.439 56.917 39.457 53.288 41.805 58.641 43.184 62.280

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BNG 4

Entropy tiu chun ca mt s cht

n cht rn Cht Cgraphit Ckim cng Natt Sthoi Sn t Hp cht v c kh Cht H2 O H2O2 NH3 HCl HI CO CO2 Trng thi k k k k k k k So (Cal/mol ) 45.104 55.593 45.970 44.646 49.351 47.219 51.059 NO NO2 N2 O SO2 SO3 ClO ClO2 Cht Trng thi k k k k k k k So (Cal/mol ) 50.347 57.349 52.519 59.300 61.367 54.140 61.386 Trng thi r r r r r So (Cal/mol ) 1.372 0.568 12.239 7.600 7.832 Catt Fett Cutt Zntt Agtt Cht Trng thi r r r r r So (Cal/mol ) 9.900 6.520 7.923 9.950 10.170

Hp cht v c lng - rn Cht H2 O H2O2 SO3 Trng thi L L L So (Cal/mol ) 16.709 26.915 27.199 Cht CaOtt Ca(OH)2tt CaCO3,canxit BaCO3 BaSO4tt Fe2O3,hematit CuOtt Trng thi r r r r r r r So (Cal/mol ) 9.500 19.931 22.204 26.793 31.597 20.889 10.189

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ZnOtt AgCltt r r 10.430 22.922

Hp cht hu c kh Cht CH4 (metan) C2H6 (etan) C2H4 (etilen) C2H2 (axetilen) C3H8 (propan) C3H6 (propylen) C4H10 (isobutan) C4H8 (1-buten) C4H8 (cis-2-buten) C4H8 (trans-2-buten) C6H6 (benzen) Trng thi k k k k k k k k k k k So (Cal/mol ) 44.998 54.760 52.390 47.990 47.421 63.719 70.600 73.573 71.869 70.698 64.400

Hp cht hu c lng Cht CH3OH (metanol) C2H5oh (etanol) CH3COOH (axit axetic) C6H6 (benzen) Trng thi l l l l So (Cal/mol ) 30.306 38.408 38.193 64.400

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BNG 5 Th ng p to thnh tiu chun Go298,tt (kcal/mol)

Cht H H2 C C2 N N2 O O2 O3 H2 O H2O2 NH3 HCl HI CO CO2 H2 O H2O2 SO3 CaOtt Ca(OH)2tt CaCO3 Canxit BaCo3 BaSO4tt Trng thi k k k k k k k k k k k k k k k k L L L r r r r r r Gott (kcal/mol) 48.51 0 160.442 185.449 108.886 0 55.389 0 39.006 -54.634 -25.239 -3.939 -22.777 0.411 -32.780 -94.254 -56.687 -28.781 -89.340 -44.371 -214.76 -269.80 -271.89 -325.57 Cht F F2 S Cl Cl2 Br Br2 I I2 NO NO2 N2 O SO SO2 SO3 ClO ClO2 Trng thi k k k k k k k k k k k k k k k k k Gott (kcal/mol) 14.806 0 56.946 25.262 0 19.701 0.751 16.789 4.627 20.686 12.259 24.900 -4.693 -71.748 -88.689 23.449 28.800

Fe2O3 Hematit CuOtt ZnOtt AgCltt

r r r r r

-177.39 -31.00 -76.08 -26.244

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BNG 6 Th ng p to thnh tiu chun ca mt s hp cht hu c Cht CH4 (metan) C2H6 (etan) C2H4 (etilen) C2H2 (axetilen) C3H8 (propan) C3H6 (propylen) C4H10 (n-butan) C4H10 (isobutan) C4H8 (1-buten) C4H8 (cis-2-buten) C4H8 (trans-2-buten) C6H6 (benzen) CH3OH (Metanol) C2H5OH (Etanol) CH3COOH (Axit axetic) C5H5COOH (Axit benzonic) Trng thi k k k k k k k k k k k k l l l l Gott (kcal/mol) -12.146 -7.636 16.355 50.184 -5.832 14.847 -3.958 -4.962 16.788 15.655 15.153 30.987 -39.759 -41.800 -93.212 29.737

BNG 7 Hng s in li ca mt s axit v baz trong dung dch nc 250C

Cht in ly HNO2 C6H5COOH H3BO3 H2B4O7 Phng trnh in ly HNO2 H+ + HSeO4 C6H5COOH H3BO3 C6H5COO- + H+ H+ + H2BO-3 Ka v Kb K1= 5,1.10-4 K1= 2,0.10-5 K1 = 5,8.10-10 K1 = 1,8.10-4 K2 = 1,5.10-5 K1 = 5,0.10-10 K2 = 2,0.10-13 K1 = 1,6.10-1 K1= 1,7.10-4

H+ + HB4O-7 H2B4O7 H+ + B4O2-7 HB4O-7

H2GeO3

H2GeO3

H+ + GeO-3

HIO3 HCOOH HCOOH

H+ + GeO2-3 HGeO3 H+ + IO-3 HIO3 H+ + HCOO

126
H3AsO4 H3AsO4 H2AsO-4 HAsO-4 H2O2 HF CH3COOH H2O2 HF CH3COOH H+ + H2AsO4 H+ + HAsO2-4 H+ + AsO3-4 H+ + HO-2 H+ + F CH3COO- + H+ CH3CH2COO- + H+ H+ + CNS H+ + HSeO-3 H+ + SeO2-3 H+ + HSeO-4 H+ + SeO2-4 H+ + HSO-4 H + SO H+ + HSO-3
+ 23

K1 = 6,0.10-3 K2 = 1,1.10-7 K3 = 4,0.10-12 K1 = 2,0.10-12 K1 = 6,8.10-4 K1= 1,8.10-5 K1= 2,0.10-5 K1= 1,4.10-1 K1 = 2,4.10-3 K2 = 4,8.10-9

CH3CH2COOH CH3CH2COOH HCNS H2SeO3 HCNS H2SeO3 HSeO-3 H2SeO4 H2SO4 H2SO3 H2S H2TeO3 H2TeO4 H2S2O3 H2CO3 C6H5OH H3PO3 H2SeO4 HSeO4 H2SO4 HSO
4

K2 = 8,9.10-3 in ly hon ton K2 = 1,2.10-2 K1 = 1,3.10-2 K2 = 6,3.10-8 K1 = 8,9.10-8 K2 = 1,3.10-13 K1 = 3,2.10-3 K2 = 2,0.10-8 K1 = 2,5.10-9 K2 = 4,1.10-11 K1 = 2,5.10-1 K2 = 1,9.10-2 K1 = 4,5.10-7 K2 = 4,7.10-11 K1= 1,3.10-10 K1 = 1,6.10-2

H2SO3 HSO-3 H2S HSH2TeO3 HTeO3 H2TeO4 HTeO4H2S2O3 H2SO3H2CO3 HCO3C6H5OH H3PO3

H+ + SO2-3 H+ + HS H+ + S2 H+ + HTeO3 H+ + TeO33 H+ + HTeO4 H+ + TeO32 H+ + HS2O3 H+ + S2O32H+ + HCO3-

H+ + CO32 C6H5O- + H H+ + H2PO3

127
H2 PO32H3PO4 H3PO4 H2PO3HPO42H4P2O7 H4P2O7 H3P2O72H2P2O72HP2O73HClO HClO2 H2CrO4 HClO HClO2 H2CrO4 HCrO-4 2HCrO-4 H2C2O4 H2C2O4 HC2O-4 NH4OH C6H5NH2 CH3NH2 C2H5NH2 NH4OH C6H5NH2 CH3NH2 C2H5NH2 + H2O H+ + HPO32 H+ + H2PO4 H+ + HPO42 H+ + PO43 H+ + H3P2O7 H+ + H2P2O72 H+ + HP2O73 H+ + P2O74 H+ + ClO H+ + ClO2 H- + CrO4 H+ + CrO42 Cr2O72- + H2O H+ + HC2O4 H+ + C2O42 NH4+ + OH C6H5NH3 + OH CH3NH3 + OH C2H5NH3+ + OH K2 = 2.0.10-7 K1 = 7,6.10-3 K2 = 6,2.10-8 K3 = 4,4.10-13 K1 = 3,0.10-2 K2 = 4,4.10-3 K3 = 2,5.10-7 K4 = 5,6.10-10 K1 = 3,0.10-8 K1 = 1,1.10-2 K1 = 1,8.10-1 K2 =3,2.10-7 3,0.10-2 K1 = 5,6.10-2 K2 = 5,1.10-5 K1= 1,8.10-5 K1= 4,2.10-10 K1= 4,8.10-4 K1= 4,7 .10-4

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BNG 7

Tch s tan trong nc ca mt s cht 250C

Cht in li AgCl AgBr AgI AgCN AgIO3 Ag2S Al(OH)3 Al(OH)3 As2S3 BaCO3 BaCO4 BaSO4 Be(OH)2 H2BeO2 Bi(OH)3 BiOCl Bi2S3 CaCO3 Ca(OH)2 CaSO4 AgCl AgBr AgI AgCN AgIO Ag2S Al(OH)3 Al(OH)3 As2S3 BaCO3 BaCO4 BaSO4 Be(OH)2 H2BeO2 Bi(OH)3 BiOCl Bi2S3 CaCO3 Ca(OH)2 CaSO4 Phng trnh in li
Ag+ + Cl Ag+ + Cl Ag+ + I Ag+ + CN Ag+ + IO3 2Ag+ + S2 Al3+ + 3OH H+ + (AlO2.H2O) 2As3+ + 3S2 Ba2+ + CO32 Ba2+ + CrO42 Ba2+ + SO42 Be2+ + 2OH H+ + BeO22 Bi3+ + 3OH Cl- + BiO+ 2Bi3+ + 3S2 Ca2+ + CO32 Ca2+ + 2HO Ca2+ + SO42

Ka v Kb 1,1.10-11 6,3.10-13 1,5.10-16 7.10-15 3,2.10-8 5,7.10-51 1,9.10-33 1,1.10-15 4.10-29 ( 180C) 7.10 -9 2,3.10-10 1,08.10-10 2,7.10-10 2.10-30 1,3.10-31 ( 180C) 7.10-9 1,6.10-72 ( 180C) 4,8.10-9 3,1.10-5 6,26.10-5

129
CaSO4.2H2O Ca3(PO4 )2 Cd(OH)2 Co(OH)2 Co(OH)3 CoS Cr(OH)3 Cr(OH)3 CuCO3 Cu(OH)2 Cu2Cl2 Cu2I2 Cu2S CuS FeCO3 Fe(OH)2 Fe(OH)3 FeS Hg2Cl2 Hg2I2 Hg2O
CaSO4.2H2O 2H2O

Ca2+ + SO42- +

1,3.10-4 1.10-4 2,4.10-13 ( 180C) 1,6.10-18 ( 180C) 2,5.10-43 3,1.10-23 6,7.10-31 9.10-17 5,6.10-10 5,6.10-20 1,8.10-7 1,1.10-12 2.10-47 ( 180C) 4.10-38 2,11.10-11 4,8.10-16 ( 180C) 3,8.10-38 ( 180C) 3,7.10-19 1,1.10-18 3,7.10-29 1,6.10-23

Ca3(PO4)2 Cd(OH)2 Co(OH)2 Co(OH)3 CoS Cr(OH)3 Cr(OH)3 CuCO3 Cu(OH)2 CuCl2 Cu2I2 Cu2S CuS FeCO3 Fe(OH)2 Fe(OH)3 FeS Hg2Cl2 Hg2I2

3Ca2+ + 2PO43 Cd2+ + 2OH Co2+ + 2OH Co3+ + 3OH Co2+ + S2 Cr3+ + 3OH CrO2- + H+ + H2O Cu2+ + CO32 Cu2+ + 2OH Cu22+ + 2Cl Cu22+ + 2I Cu22+ + S2 Cu2+ + S2 Fe2+ + CO33 Fe2+ + 2OH Fe3+ + 3OH Fe2+ + S2 Hg22+ + 2Cl Hg22+ + 2l

Hg22+ + 2OHHg2O + H2O

130
HgO Hg2S HgS KClO4 Li2CO3 MgCO3.3H2O MgS Mg(OH)2 MnCO2 Mn(OH)2 MnS Ni(OH)2 NiS PbCO3 PbCl2 PbBr2 PbI2 PbCrO4 PbO PbS PbSO4
Hg2+ + 2OHHgO + H2O

1,7.10-26 1,0.10-47 ( 180C) 4,0.10-53 ( 180C) 1,07.10-2 1,66.10-3 1,0.10-5 2,0.10-15 5,5.10-12 5,05.10-10 4.10-14 ( 180C) 5,6.10-16 ( 180C) 1,6.10-14 3.10-21 (180C) 1,5.10-13 1,7.10-5 6,3.10-5 8,7.10-9 1,77.10-14 5,5.10-16 1,1.10-29 1,8.10-8

Hg2S HgS KClO4 Li2CO3

Hg22+ + S2+ Hg2+ + S2 K+ + ClO4 2Li+ + CO32

MgCO3.3H2O 3H2O

Mg2+ + CO32- +

MgS Mg(OH)2 MnCO2 Mn(OH)2 MnS Ni(OH)2 NiS PbCO3 PbCl2 PbBr2 PbI2 PbCrO4

Mg2+ + S2 Mg2+ + 2OH Mn2+ + CO32 Mn2+ + CO32 Mn2+ + S2 Ni2+ + 2OH Ni2+ + S2 Pb2+ + CO32 Pb2+ + 2Cl Pb2+ + 2Br Pb2+ + 21 Pb2+ + CrO42

Pb2+ + 2OHPbO + H2O

PbS PbSO4

Pb2+ + S2 Pb2+ + SO42

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Pt(OH)2 Sb(OH)3 Sb2S3 H2SiO3 Sn(OH)2 Sn(OH)4 SnS SrCO3 SrSO4 TeO(OH)2 Te(OH)4 TiO(OH)
2

Pt(OH)2 Sb(OH)3 Sb2S3 H2SiO3 Sn(OH)2 Sn(OH)4 SnS SrCO3 SrSO4 TeO(OH)2 Te(OH)4 TiO(OH)2 ZnCO3 Zn(OH)2 ZnS

Pt2+ + 2OH Sb3+ + 3OH 2Sb3+ + 3S2 HSiO3+ + H Sn4+ + 4OH Sn4+ + 4OH Sn2+ + S2 Sr2+ + CO32 Sr2+ + SO42 TeO2+ + 2OH Te4+ + 4OH TiO2+ + 2OH Zn2+ + CO32 Zn2+ + 2OH Zn2+ + S2

102-5 4,0.10-42 1.10-30 1.10-30 5.10-26 1..10-56 1.10-28 9,42.10-10 2,8.10-7 1.10-11 7.10 - 53 ( 180C) 1.10-30 6.10-11 4.10-16 6,9.10-26

ZnCO3 Zn(OH)2 ZnS

BNG 8

Th in cc chun ( 25 0C)
in cc Li+/Li Hb+/Rb Cs+/Cs K+/K Phn ng in cc Li+ + e Rb+ + e Cs+ + e K+ + e
Li Rb Cs K

0 (Vn) -3,04 -2,92 -2,92 -2,92

132
Ra2+/Ra Ba2+/Ba Ca2+/Ca Na+/Na La3+/La Mg2+/Mg Be2+/Be HfO2, H+/Hf Al3+/Al Ti2+/Ti Zr4+/Zr V2+/V Mn2+/Mn WO42-/W Se2-/Se Zn2+/Zn Cr3+/Cr SbO2/Sb Ga3+/Ga S2?S Fe2+/Fe Cr3+/Cr2+/ Pt Cd2+/Cd Ra2+ + 2e Ba2+ + 2e Ca2+ + 2e Na+ + e La3+ + 3e Mg2+ + 2e Be2+ + 2e HfO2 + 4H+ + 4e Al3+ + 3e Ti2+ + 2e Zr4+ + 4e V2+ + 2e Mn2+ + 2e
Ra Ba Ca Na La Mg Be Hf + 2H2O Al Ti Zr V Mn

-2,92 -2,90 -2,87 -2,713 -2,52 -2,38 -1,85 -1,7 -1,66 -1,63 -1,53 -1,18 -1,18 -1,05 -0,92 -0,763 -0,74 -0,67 -0,53 -0,51 -0,44 -0,410 -0,402

W + 8OHWO42- + 6e + 4H2O

Se3+ + 2e Zn2+ + 2e Cr3+ + 3e

Se2 Zn Cr

Sb + 4OHSbO2- + 3e + 2H2O

Ga3+ + 3e S + 2e Fe2+ + 2e Cr3+ + e Cd2+ + 2e

Ga S2 Fe Cr2+ Cd

133
Ti3+, Ti2+/Pt Tl+/Tl Co2+/Co Ni2+/Ni Mo3+/Mo Sn4+/Sn Pb2+/Pb Ti4+, Ti3+/Pt H+, H2/Pt Ge2+/Ge Cu2+, Cu+/Pt Sn4+, Sn2+/Pt Cu2+/Cu
-

Ti3+ + e Tl+ + e Co2+ + 2e Ni2+ + 2e Mo2+ + 3e Sn2+ + 2e Pb2+ + 2e Ti4+ + e 2H+ + 2e Ge2+ + 2e Cu2+ + e Sn4+ + 2e Cu2+ + 2e Fe(CN)63- + e O2 + 2H2O + 4e Cu+ + e I2 + 2e Te4+ + 4e MnO4- + e

Ti2+ Tl Co Ni Mo Sn Pb Ti3+ H2 Ge Cu+ Sn2+ Cu Fe(CN)64 4OH Cu 2I2 Te MnO42

-0,37 - 0,335 - 0,27 - 0,24 - 0,2 - 0,136 - 0,126 - 0,04 0,000 + 0,01 + 0,153 + 0,154 + 0,337 + 0,36 + 0,401 + 0,52 + 0,536 + 0,56 + 0,561

Fe(CN)63 , Fe(CN)64-/Pt OH-/O2, Pt Cu+, Cu 2I-/I2 Te4+/Te MnO4-, MnO42-

/Pt Rh2+/Rh Fe3+, Rh2+ + e Fe3+ + e

Rh Fe2+

+ 0,6 + 0,771

134
Fe3+/Pt Hg22+/Hg Ag+/Ag Hg2+/Hg Hg2+, Hg+/Pt Pd2/Pd 2Br-/Br2, Pt Pt2+/P2 Mn2+, H+/MnO2, Pt Cr2O72-, Cr3+/Pt Ti3+, Ti+/Pt Cl-/Cl2, Pt Pb2+/Pb O2 , Pb Au3+/Au MnO4-, H+/Mn2+,Pt MnO4-, H+, MnO2 Au3+ + 3e
Au

Hg22+ + 2e Ag+ + e Hg2+ + e Hg2 + e Pd2 + 2e Br2 + 2e Pt2+ + 2e

2Hg Ag Hg Hg+ Pd 2Br Pt

+ 0,798 + 0,799 + 0,854 + 0,91 +0,987 +1,066 +1,2 + 1,236 + + 1,33 + 1,247 + 1,359 + 1,455

Mn2+ + 2H2O MnO2 + 4H+ + 2e Cr2O72- + 14H+ + 6e 7H2O

2Cr3+

Ti3+ + 2e Cl2 + 2e PbO2 + 4H+ + 2e

Ti+ 2Cl Pb2+ + 2H2O

+1,50 +1,51 +1,695

MnO2 + 2H2O MnO4- + 8H+ + 5e

MnO4- + 4H+

MnO2 + 2H2O

135

TI LIU THAM KHO

1. Phan An l thuyt c s ca ha hc Trng i hc Y H Ni 2001 2. Nguyn nh Chi Phm Thc Cn - C s l thuyt ha hc NXB i hc v trung hc chuyn nghip H Ni 1979 3. Nguyn c Chung Cu hi v bi tp trc nghim ha i cng - NBX Khoa hc k thut 2000 4. PGS V ng - C s l thuyt cc qu trnh ho hc - NXB i hc v trung hc chuyn nghip H Ni 2000 5. Hong Nhm Ha hc v c tp 1 NXB Gio dc H Ni 2000 6. Nguyn Hnh - C s l thuyt ho hc - NXB Gio dc 1994 7. Phan Th Hong Oanh. Bi ging cu to nguyn t v lin kt ha hc Trng i hc Khoa hc Hu 2005 8. Nguyn nh Soa - Ho i cng trng H Bch khoa TP HCM 1996 9. L Nguyn To - L Tin Hon - Gio Trnh ho hc cht keo - trng H tng hp H Ni 1990

136
10. Nguyn Vn Tu - V Vn Son NXB i hc v gio dc chuyn nghip H Ni 1994 11. o nh Thc Cu to nguyn t v lin kt ha hc Tp 1 v 2 NXB bn i hc v gio dc chuyn nghip H Ni 1980 12. Rene Didier Ha i cng tp 1, 2, 3 NXB Gio dc H Ni 1997

BIN SON
1. Nguyn Ph Huyn Chu Chng I: Nhng khi nim v nh lut c bn ca ha hc Chng II: Cu to nguyn t v lin kt ha hc Chng III: Cu to phn t v lin kt ha hc Chng V: ng ha hc Chng VI: Cn bng ha hc Chng X: in ha hc (Phn ng oxi ha kh v nguyn t Galvani) 2. Nguyn Th Minh Minh Chng IV: Nhit ng hc ha hc Chng IX: Ha keo Chng X: in ha hc (S in phn) 3. Trn Th Ha Chng VII: Dung dch Chng VIII: Dung dch in ly Chng X: in ha hc (Mt s v d)

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