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85 Bi 30

XC NH HM LNG ST TRONG NC T NHIN

I. C s phng php C nhiu loi thuc th c th to phc mu vi ion st c gi tr trong phng php o quang. Bn cnh phc gia Fe(III) vi axit sunfosalixilic nghin cu trong cc bi trn th phc mu cam c to thnh gia Fe(II) v 1, 10 phenanthroline (orthophenanthroline) c coi l phng php tiu chun xc nh hm lng trong nc t nhin. Phn ng to thnh phc c vit ngn gn nh sau: Fe2+ + 3phenH+ Fe(phen)32+ + 3H+ Hng s cn bng ca phn ng l 2,5.106 (ti 25oC). Phc c hnh thnh trong khong pH t 3 ti 9, ti u l 3,5. Trong phn tch nh lng cn cho d tc nhn kh nh hydroxylamin hay hydroquynon chuyn hon ton cc dng Fe(III) v Fe(II). Phc to thnh trong cc iu kin ti u rt bn (hng s khng bn K=5.1022) c gi tr ln trong phn tch o quang. Phc c hp th quang cc i ti 508nm, vi cc my so mu n gin c th s dng knh lc mu xanh l cy. II. Cch tin hnh 1. Xy dng ng chun u tin dng pipet ly chnh xc 10,00ml dung dch Fe2+ 40g/ml cho vo cc loi 100ml ri thm khong 25ml nc; a cc vo my o pH ri s dng dung dch citrat natri iu chnh pH ca dung dch ti 3,5. c th tch dung dch citrat natri tiu tn v ghi li vo s tay th nghim (Gi s dung dch citrat natri tiu tn l Vml). T lng dung dch citrat natri cn iu chnh pH cho 10ml Fe2+ s suy ra lng dung dch citrat natri cn ly cho cc lng dung dch st chun t hoc nhiu hn. Chun b 5 bnh nh mc loi 50ml, cho vo cc loi ha cht theo th t sau
ml
B1 B2 B3 B4 B5

Fe2+ 40g/ml Citrat natri Hydroxylamin Orthophenanthroline

1,0 V/10

2,0 V/5

3,0 V/3,3 1 2

4,0 V/2,5

5,0 V/2

yn 5 pht ri nh mc bng nc ct va ti vch ri lc u Tin hnh o quang ti bc sng 508nm vi dung dch trng gm cc thnh phn tr khng c st trong cc cuvet c b dy l=1cm. Xy dng th chun AC.

86 2. Xc nh hm lng st trong nc Ty thuc vo hm lng thc t ca mu nc m ta ly lng mu tin hnh phn tch cho ph hp. Vi cc mu nc sinh hot, thng thng ta ly chnh xc 100ml mu, cho vo cc chu nhit, thm 1~2 git HNO3 c ri un nh trn bp in ti th tch khong 20ml. ngui ri chuyn ton b dung dch mu c vo bnh nh mc loi 50ml, thm mt th tch dung dch citrat natri ti khi t pH=3,5. Thm 1ml dung dch hydroxylamin v 2ml dung dch orthophenanthroline vo bnh, yn 5 pht ri nh mc bng nc ct ti vch. Tin hnh o quang ti 508nm vi dung dch trng ph hp. T gi tr hp th quang o c v th chun xc nh hm lng st c trong mu nc phn tch. III. Ha cht v dng c - Dung dch Fe2+ 40g/ml: cn chnh xc 0,2810g FeSO4.(NH4)2SO4.6H2O vo cc kh, thm 1ml H2SO4 c ri khuy u, thm nc ct ti va 1lt. - Dung dch citrat natri 25g/l. - Dung dch hydroxylamin hydroclorit 10%. Dung dch bn c khong 1 tun. Lu y l cht c, khi lm vic cn cn trng. - Othophenanthroline: cn 2,5g orthophenanthroline ha tan trong 100ml ethanol 96%, thm nc ct ti 1lt. Dung dch bn trn 1 thng nu trong bng ti.

87 Bi 31
XC NH MnO4 V Cr2O72 TRONG DUNG DCH HN HP

I. C s phng php ng cong quang ph hp th Cr2O72 c cc i 1max = 440nm; di sng ny MnO4 cng b hp th mt phn. Ion MnO4 hp th nhiu nht 2max = 525nm nhng y s hp th Cr2O72 khng ng k.
A

(1)

A(2)
A"(1) (3)

(2) A'(1) C1 C2

Hnh 24: Dng th chun v ph hp th ca MnO4+ Cr2O72

Do c th xc nh nng ca cc ion ny nh sau: 1. o hp th quang ca dy dung dch chun KMnO4 1max v 2max dng hai ng A-C ng vi hai di sng (ng 1 v 2) 2. o hp th quang ca dy dung dch chun K2Cr2O7 1max A-C ng vi di sng (ng 3) 3. o hp th quang ca dung dch hn hp c 1max v 2max c cc gi tr tng ng l A(1) v A(2). V 2max ion Cr2O72 hp th khng ng k nh sng nn A(2) l hp th quang ch ca MnO4- trong hn hp. Da vo ng chun 2, tm c nng ca MnO4 l C1. Khi tm c nng C1, da vo ng chun 1 tm c hp th quang A'(1) ca MnO4A(1) l hp th quang ca c hai ion di sng 1 nn: A(1) - A'(1) = A"(1 Cr2O72-) A"(1 Cr2O72) l hp th quang ca Cr2O72 1max . T ng chun 3 tm c nng Cr2O72 trong dung dch hn hp C2.

88 II. Cch tin hnh 1) Xy dng ng chun ca KMnO4 v K2Cr2O7 * Chun b 4 bnh nh mc c dung tch 25,0ml ly vo ln lt 0,5 1,0 1,5 2,0ml dung dch chun KMnO4 0,01N. Thm nc ct va ti vch nh mc ri lc u. o hp th quang trn my ti = 525nm v = 440nm * Tip theo, chun b 4 bnh nh mc c dung tch 25,0ml ly vo ln lt 0,5 1,0 1,5 2,0ml dung dch chun K2Cr2O7 0,05N. Thm nc ct va ti vch nh mc ri lc u. o hp th quang trn my ti = 440nm V 3 th chun trn giy milimet trn cng mt h trc ta . ( th phi l mt ng thng i qua gc ta ) 2) Xc nh hm lng Cr v Mn trong dung dch hn hp Ly chnh xc 2,0 hoc 3,0ml dung dch hn hp phn tch - o tng hp th quang ti max1 v max2 ri xc nh hm lng Mn v Cr c trong dung dch phn tch. Tnh nng cc ion theo mg/ml II. Ha cht - Dung dch chun KMnO4 0,01N khi pha cho thm ~5ml H2SO4+5ml H3PO4. - Dung dch chun K2Cr2O7 0,05N khi pha cho thm ~5ml H2SO4+5ml H3PO4. - Dung dch hn hp phn tch KMnO4+K2Cr2O7

Bi 32
XC NH Ni2+ BNG DIMETYLGLYOXIM

I. C s phng php Dimetylglyoxim (thuc th Trugaep) to vi Ni2+ mi trng kim khi trong dung dch c cht oxy ha (I2, Br2, S2O82-, H2O2) mt hp cht c mu tm. y Ni2+ b oxy ha thnh Ni3+; hp cht ny c thnh phn Ni3+:DM2 = 1:3 c cc i hp th ti bc sng max=470nm, =13000. Phn ng to phc rt nhy nhng b nhiu ion nh Fe3+, Cu2+, Al3+ cn tr. Tuy nhin trong thc t xc nh Ni2+ nu dng cc cht che nh tatrat, citrat c th loi tr c mt s cc ion gy cn tr php xc nh. II. Cch tin hnh 1. Xy dng th chun Chun b 6 bnh nh mc dung tch 50ml pha ch mt dy dung dch c thnh phn nh bng sau

89
ml Bnh

B1 0 0,5 2,5 0,5

B2 1 0,5 2,5 0,5

B3 2 20 0,5 2,5 0,5

B4 3 0,5 2,5 0,5

B5 4 0,5 2,5 0,5

B6 5 0,5 2,5 0,5

Ni2+ 0,01 mg/ml Nc ct It 0,05M NaOH 1N Dimetylglyoxim Nc ct

nh mc va ti vch lc u

Ly cc dung dch trong cc bnh nh mc cho ra cuvet c b dy l=1,0cm. o hp th quang ca cc dung dch trn my quang ph o quang ti bc sng =470nm vi dung dch trng l bnh s 1. V th A-C trn giy milimet ( th phi l mt ng thng i qua gc ta ) 2. Xc nh nng Ni2+ Dung dch Ni2+ cha bit nng cng chun b vi trnh t v lng thuc th nh dy dung dch chun trong bnh nh mc 50ml. Cho dung dch trong bnh nh mc ra cuvet 1cm, o hp th ti =470nm vi dung dch trng l bnh 1. T kt qu hp th o c tnh nng Ni2+ trong mu kim tra. III. Ha cht v dng c - Dung dch chun Ni2+ 0,01 mg/ml Cn 0,4786gam NiSO4.7H2O ha tan trong nc c axit ha bng 2 3ml H2SO4 c v pha bng nc ct ti vch trong bnh nh mc 1lt. Nng dung dch ny l 0,1mg/ml khi cn pha long 10 ln. - Dung dch It 0,05M - Dung dch NaOH 1N - Dung dch dimetylglyoxim 0,05M pha trong etanol

Bi 33
XC NH AMONI TRONG NC

I. Nguyn tc xc nh Nm 1856, J.Nessler ln u tin xut phng php xc nh amoni bng phng php so mu vi dung dch kim thy ngn (II) iotdit. Khi thuc th Nessler c thm vo dung dch amoni th amoni t do trong dung dch s phn ng rt nhanh vi tc nhn ny, tuy nhin khng phi ton b lng amoni t do u phn ng ngay lp tc do vy cn c mt thi gian tc ht keo mu vng c to thnh hon ton.

90 Ion st, mangan trong mu cng to phc mu vng vi thuc th Nessler do vy cn phi cho dung dch kali hoc natri tactrat vo che cc ion ny. Phn ng vi thuc th Nessler, dung dch kim ca kali tetraiodo thy ngn, vi amoni: 2NH3 + 2K2[HgI4] = Hg2NH2I3 + 4KI + NH4I Thuc th cho phn ng rt nhy vi amoni, phng php ch c p dng vi dung dch c hm lng amoni rt nh (0,1mg/l) II. Cch xc nh 1. Xy dng ng chun: Chun b 5 bnh nh mc loi 50ml pha ch dy dung dch chun theo ng th t v c thnh phn nh bng sau: B1 Nc ct NH4+ 25mg/l K4NaC4H4O6 10% Thuc th Nessler Nc ct khng c amoni 0 1,0 B2 B3 Khong 25ml 2,0 2,0ml ly bng pipet 2,0ml ly bng pipet nh mc va ti vch ri lc u 3,0 4,0 B4 B5

yn dung dch khong 5 pht ri cho ra cuvet c b dy l=1cm em o quang trn my o quang bc sng 400nm vi dung dch trng gm mi thnh phn tr amoni. T cc s liu hp th quang thu c xy dng th chun ACNH + trn giy milimet.
4

Lu rng trc khi o quang cn quan st dung dch nu thy dung dch c hin tng c, m (khng trong sut) th phi lm li th nghim. 2. Xc nh nng NH4+ trong nc: Tu thuc vo nng NH4+ trong mu phn tch ln hay nh m ta ly vo bnh nh mc 50ml sao cho nng NH4+ khng qu 5mg/l. Pha long dung dch bng nc ct khng c amoni trc khi cho vo 2,0ml K4NaC4H4O6 10% v 2,0ml thuc th Nessler. nh mc bng nc ct va ti vch lc u. yn 5 pht sau o quang trn my so mu bc sng 400nm. T cc s liu hp th quang (A) thu c da vo th chun ta s tnh c nng NH4+ (mg/l) trong mu phn tch. III. Ho cht v dng c Dung dch chun NH4+ : Cn 0,7414g NH4Cl sy kh ti khi lng khng i 105oC ha tan hon ton bng nc ct khng cha amoni ri chuyn ton b dung dch vo bnh nh mc 1000ml. Sau khi pha c dung dch ny li dng pipet ly chnh xc

91 10,00ml cho vo bnh nh mc 100ml dng nc ct khng c amoni thm va ti vch lc u. Nh vy c 100ml dung dch NH4+ 25mg/l. Dung dch K4NaC4H4O6 10% : Cn 10g tinh th K4NaC4H4O6 pha vo 90ml nc ct khng c amoni. Thuc th Nessler: Cn 45,5g HgI2 v 35g KI tm t, khuy trn u ti khi tan hon ton. Thm tip 112g KOH khuy n tan ri thm nc ct ti va 1lt. yn dung dch 24 gi gn ly phn dung dch trong em i lm thuc th. Thuc th ny rt c nn khi lm vic cn thn trng v bo qun trong bnh nu c nt nhm. Bnh nh mc 50, 100, 1000ml ng ong, pipet, qu bp cao su

Bi 34:
XC NH Cl BNG THY NGN THYOXYANATE

I. C s phng php Phng php cho php xc nh lng vt anion clorit trong dung dch. Nguyn tc l ion thyocyanat ca mui thy ngn thyoxyanat b chim ch bi ion clorit v gii phng ra ion thyoxyanat t do. Vi s c mt ca ion Fe(III) trong dung dch s to ra phc c mu mu. Cng mu ca phc st vi thyoxyanat tng ng vi hm lng ion clorit trong dung dch. 2Cl + Hg(SCN)2 + 2Fe3+ = HgCl2 II. Cch tin hnh 1. Xy dng ng chun Chun 5 bnh nh mc dung tch 25ml cho vo cc loi ha cht sau
ml Bnh

+ 2[Fe(SCN)]2+

B1 0 2 2

B2 0,5 2 2

B3 1,0 2 2

B4 1,5 2 2

B5 2,0 2 2

Cl 2,5 mg/ml Phn amoni st(III) 0,25M Hg(SCN)2 bo ha Nc ct

nh mc va ti vch lc u

yn dung dch 10 pht ri a ra cuvet v o hp th quang ti bc sng = 460nm vi dung dch trng bnh 1. Xy dng th chun A C.

92 2. Xc nh Cl trong mu Vi cc mu nc t nhin ta ly 20ml mu cho vo bnh nh mc 25ml, thm 2ml phn st(III) amoni sunfat, thm 2ml Hg(SCN)2 bo ha. yn mu 10 pht ri nh mc bng nc ct ti vch. o quang ti =460nm vi dung dch trng l bnh 1. T hp th quang o c, da vo ng chun s xc nh c hm lng gc ion Cl trong dung dch. III. Ha cht cn chun b Dung dch Cl chun 2,5mg/ml: Sy kh tinh th NaCl (tkpt) 180oC trong khong 30 pht, cn chnh xc 4,1213g NaCl pha vo 1lt nc ct. Phn amoni st(III) 0,25M: cn 120g NH4Fe(SO4)2.12H2O ha tan v nh mc bng dung dch HNO3 6N. Hg(SCN)2 bo ha c pha trong ethanol

Bi 35
PHNG PHP O QUANG XC NH THNH PHN PHC PHC Cu(II) NITROZO-R-SOL

I. C s phng php Khi hp th bc x in t t min t ngoi ti min trng thy, cc phn t cc cht hp th t b phn hy, t xy ra s b gy lin kt ha hc. iu ny cho php ng dng phng php ph hp th nghin cu thnh phn, trng thi cn bng ca dung dch. Nguyn tc chung p dng phng php ny l gii phng trnh lin quan ti hai nh lut: nh lut tc dng khi lng v nh lut hp th nh sng. c im chung ca phng php l da vo th thnh phn tnh cht dung dch xc nh h s ha hc trong phn ng to phc cht. Cc phng php c bn l phng php dy ng phn t gam, phng php ng cong bo ha. 1. Phng php dy ng phn t gam Phng php ng phn t gam c s dng rt ph bin xc nh thnh phn ca cc phc. Ni dung ca phng php l cho cht phn tch X tc dng vi thuc th R sinh ra hp cht phc c dng phn t XnRm th nguyn tc c th l: - Pha mt dung dch cht X v mt dung dch thuc th R c cng nng phn t gam. - Pha mt dy dung dch cc hn hp ca X v R bng cch em trn chng vi nhau theo cc t l th tch khc nhau, nhng c tng th tch l nh nhau cho cc mu u c tng nng (CX+CR) l nh nhau.

93 - Chn cc iu kin o quang thch hp ri tin hnh o hp th quang ca dy dung dch. - V ng cong biu din mi quan h A CX/CR. Nu trong khong nng nghin cu cht X tc dng vi thuc th R ch to thnh mt phc cht c thnh phn nht nh th cc ng tng ng vi cc dy ng phn t gam ca X v R c nng khc nhau ch c mt t l nng ca X v R. Tc l cc cc i ca dy ng phn t gam vi nng khc nhau chng u nm trn mt ng thng song song vi trc tung v vung gc vi trc honh. Nu cc nng khc nhau ca dy ng phn t gam ca X v R m cc i ca cc ng cong c honh khc nhau, tc l t s (CX/CR) khc nhau, th iu chng t khi pha long thnh phn hp cht phc b thay i. Ngha l mi t l nng khc nhau ca X v R phc sinh ra c thnh phn khc nhau. 2. Phng php ng cong bo ha Nguyn tc ca phng php l gi cho mt thnh phn khng i (thng l cht phn tch X) cn thnh phn kia (thuc th R) s c bin i lin tc t nh ti ln. Cch lm theo cch thc sau: - Pha mt dy cc dung dch chun ca cht X m gi tr nng ca cht X l nh nhau trong cc mu. Cn nng thuc th R th c thay i tng dn. - Chn cc iu kin o quang thch hp ri tin hnh o hp th quang ca dy dung dch. - Dng ng cong biu din mi quan h A CX/CR. Thnh phn ca phc XnRm c xc nh bng cch v cc ng tip tuyn ng vi phn ng cong c hp th quang tng nhanh v phn ng cong gn nh song song vi trc tung ( hp th quang khng tng hoc tng khng ng k). II. Cch tin hnh 1. Phng php dy ng phn t gam Ly 9 bnh nh mc c dung tch 25,0ml pha ch 1 dy dung dch c cc thnh phn nh bng sau:
ml Bnh

B1 9,0 1,0

B2 8,0 2,0

B3 7,0 3,0

B4 6,0 4,0

B5 5,0 5,0 5,0

B6 4,0 6,0

B7 3,0 7,0

B8 2,0 8,0

B9 1,0 9,0

Nitrozo-R-sol 103M CuSO4 103M Na2SO4 0,05M H2SO4 pH = 4

Thm va n vch nh mc ri lc u

94 Tin hnh o hp th quang ca phc mi bnh ti bc sng =470nm vi dung dch so snh l nc ct hoc dung dch H2SO4 pH=4. Xy dng th ph thuc ca A vi VCu/VHR. Tm cc i v xc nh thnh phn ca phc to thnh.

A
0,8 0,6 0,4 0,2 0 0 1 2 3 4 5 6 7 8 9

VMe VR

Hnh 25: th m t s ph thuc A-VMe/VR theo phng php dy ng phn t

2. Phng php ng cong bo ha Ly 8 bnh nh mc 25ml pha ch mt dy dung dch c thnh phn nh bng sau
ml Bnh

B1 0,5

B2 1,0

B3 1,5

B4 2,0 2,0 5,0

B5 2,5

B6 3,0

B7 3,5

B8 4,0

Nitrozo-R-sol 103M CuSO4 10 M Na2SO4 0,05M H2SO4 pH = 4


3

Thm ti vch nh mc ri lc u

Tin hnh o hp th quang ca phc mi bnh ti bc sng =470nm vi dung dch so snh l nc ct hoc dung dch H2SO4 pH=4. Lp th h to A VR/VCu. T th ny tnh ton v xc nh thnh phn phc theo phng php ng cong bo ha.
0,5 0,4 0,3 0,2 0,1 0 0 0,5 1 1,5 2 2,5 3 3,5 4

VR VMe

Hnh 26: th m t s ph thuc A-VMe/VR theo phng php ng cong bo ha

95 III. Chun b thuc th - Dung dch CuSO4 103mol/l. Cn chnh xc 0,2600g CuSO4.5H2O ha tan bng dung dch H2SO4 c pH=4 n 1lt. - Nitrozo-R-sol 103M. Cn chnh xc 0,3773g Nitrozo-R-sol loi tinh khit ha hc pha trong nc ct ti 1lt. - Dung dch H2SO4 pH=4. Ly khong 1ml H2SO4 0,1M ha tan vo gn 2lt nc ct. o pH ca dung dch trn my o pH. iu chnh pH ca dung dch t n 3,90,1 bng cch cho tng git dung dch H2SO4 0,1M hoc dung dch NaOH 0,1M. - Dung dch Na2SO4 0,05M c pH=4. Cn 16,1g Na2SO4.10H2O hoc 7,1g Na2SO4 khan ha tan vo 1lt nc ct. Thm tng git H2SO4 0,1M hoc NaOH 0,1M iu chnh sao cho pH = 4,0 0,1 trn my o pH.

Bi 36
XC NH NG THEO PHNG PHP O QUANG VI SAI

I. C s phng php Hm lng ng trong hp kim c xc nh theo phng php quang ph o quang vi sai dng phc Cu(NH3 )4
2+ 2+

. Phc Cu(NH3 )4

2+

c cc i hp th

max=620nm. hp th quang dung dch phn tch c o vi dung dch so snh l dung dch phc Cu(NH3 )4 c nng C0 bit. C hai cch xc nh nng theo phng php o vi sai l phng php th chun v phng php tnh. II. Cch tin hnh 1) Phng php th chun Chun b 5 bnh nh mc loi 25ml pha ch dy dung dch chun c thnh phn nh bng sau:
ml Bnh

B1 1,0

B2 2,0

B3 3,0

B4 4,0

B5 5,0

CuSO4 0,05M NH4OH 10% Nc ct hp th

Khong 5ml, ly bng ng ong Thm va ti vch ri lc u A0 A1 A2 A3 A4

A1 A2 A3 A4 l hp th ca cc dung dch chun vi dung dch so snh c nng C0 (B1) ti =620nm. Ta c phng trnh tnh sau:

96 A1 = A1 - A0 = l (C1 - C0) A2 = A2 - A0 = l (C2 - C0) . An = An - A0 = l (Cn - C0) Trong A0 , A1 , A2 An l hp th ca cc dung dch nu o vi dung dch trng theo phng php o quang thng thng. Ta lp th h to A C trn giy milimet Ly chnh xc mt th tch Vx dung dch CuSO4 (mu phn tch), thm khong 5ml dung dch NH4OH 10% em o quang vi dung dch so snh nh trn ti =620nm. Gi s ta o c hp th quang ca dung dch nghin cu l Ax ta s c biu thc tnh sau: Ax = Ax - A0 = l (Cx C0) (3) (1) (2)

Da vo th chun A C ta d dng tnh c nng Cx . 2) Phng php tnh Chun b 3 bnh nh mc c dung tch 25,0ml pha ch mt dy dung dch c thnh phn nh bng sau: Dung dch chun 5,0ml CuSO4 NH4OH 10% Nc ct hp th Ai Ci = 3.10-2M Dung dch so snh C0 = 1.10-2M Khong 5ml, ly bng ng ong Thm va ti vch ri lc u 0,00 Ax MKT C=x

o hp th quang ca cc dung dch trn bc sng = 620nm.


' ' Ax Cx C0 Ax suy ra: Cx = ' (Ci C0 ) + C0 T biu thc (2) (3) ta c: ' = Ai Ci C0 Ai C C0 hay c th vit: Cx = F . AX + C0 (F = i ) Ai

Nh vy vi phng php tnh ton ta ch cn o hp th quang ca dung dch phn tch v hp th quang ca mt dung dch chun c nng Ci thay cho vic phi o hp th quang ca nhiu dung dch chun nh phng php th chun. T cc kt qu thu c tnh ton nng CuSO4 trong mu kim tra theo phng php tnh.

97 Bi 37
PH IN T CA ION NO2

I. Ni dung nghin cu Cc phn t, nhm phn t ca cc cht, n cht hay hp cht, cng u c cu to t cc nguyn t theo nhng cch, kiu lin kt ha hc nht nh ca cc in t (electron) ha tr (cc electron lp ngoi cng) ca cc nguyn t. Tuy c hng vn cht c to thnh t cc nguyn t, phn t nhng trong phn t ch c ba loi lin kt ha hc, l lin kt xicma (), lin kt pi () v lin kt phi tr (cho-nhn). Ngoi ra, nu trong phn t cha cc nguyn t nh nit, oxy, lu hunh th nguyn t ny c th c mt hoc hai i in t ha tr cha tham gia lin kt v c k hiu l cp electron n. Cc electron ha tr khi lin kt trong phn t hnh thnh cc lin kt loi v . Cc in t ha tr ca lin kt nm trong cc phn lp p, d, f v l cc lin kt loi pp, dd, ff, df, df. Trong phn t hay nhm nguyn t cc lin kt c nng lng lin kt ln nht (bn nht); sau , km hn l cc lin kt v cc i in t t do n. Cc phn t iu kin bnh thng chng tn ti trng thi c bn, trng thi bn vng. Theo c hc lng t, trng thi c bn phn t khng thu v khng pht bc x. Nhng khi b chiu mt chm nh sng (chm proton) c nng lng thch hp (kch thch) th cc in t ha tr trong cc lin kt , v i in t n trong phn t s hp th nng lng ca chm nh sng (tng tc khng n hi) v chuyn n ln trng thi kch thch c mc nng lng cao hn. Khi phn t b kch thch nh th chng s c s chuyn mc nng lng: n * n * * *

Kch thch

C bn

Hnh 27: S cc mc nng lng v bc chuyn nng lng trong ph in t

98 Hiu s gia hai mc nng lng c bn E0 v mc kch thch E* chnh l nng lng m phn t hp th c t ngun sng (chm sng) v tc ng vo chng theo biu thc: Ee = E* E0 = .h = (h.c)/ Song trong qu trnh phn t b kch thch, tc l phn t cht hp th nng lng ca chm nh sng chiu vo n, cng vi s chuyn mc nng lng ca electron lin kt trong phn t cn km theo c s quay v dao ng ca nguyn t trong phn t. V th tng nng lng m phn t ca cht nhn c khi b kch thch l bao gm ba thnh phn Etf = E*tf E0tf = (E*e E0e) + (E*v E0v) + (E*j E0j) = Ee + Ev + Ej V chnh nng lng b mt i ny ca chm nh sng kch thch b cht hp th to thnh ph hp th phn t ca cht. Tng nng lng (Etf) chnh l tng ng vi nng lng ca cc chm nh sng nm trong vng bc sng 190800nm (vng UVVis). V th ph hp th loi ny c gi l ph hp th phn t UVVis. Trong ba thnh phn ny th Ee>>Ev>>Ej v ch c thnh phn Ee l c lng t ha, theo cc mc nng lng nht nh ca cc obital phn t (MO). Cn hai thnh phn kia khng c lng t ha, v th ph hp th phn t ca cc cht trong vng UVVis khng phi l ph vch v khng n sc nh ph pht x hay ph hp th nguyn t. Ph y l ph bng, c rng t 10 ti 80nm v c cc gi tr cc i v cc tiu ti nhng sng nht nh, ty thuc vo cu to phn t ca mi cht. Cc cht no c nhiu lin kt v lin kt lin hp th s hp th quang ca n cng mnh. Kh nng hp th quang ny c c trng bi h s hp th ca n. Ngha l gi tr ca phn t mt cht c lin quan cht ch n cc loi lin kt ha hc ca nguyn t c trong phn t ca cht, tc l cu trc phn t. V th ph hp th quang phn t vng UVVis cng l mt i lng c trng cho cu trc phn t ca cht, nhng cht khc nhau s c nhng nhm ph, nhng cc i hp th quang ca ring n. Da vo min ph ta phn on, phn nh loi bc chuyn nng lng cng vi m ph hp th (gn bc chuyn nng lng cho m ph) Da vo cng m ph (o bng h s tt phn t ): - Nu ln (>103) m ph vi cng ln - Nu b (<102) m ph vi cng b Ta c mt s nt c trng c th dng phn bit cc bc chuyn nng lng cho cc m ph: - Chuyn mc n * c nhng c im: cng b, mc ph t ngoi gn, nhn thy.

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