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I HC THI NGUYN

TRNG I HC S PHM
------------------------------

NGUYN THANH TUN


XY DNG H THNG CU HI V BI TP
MT S CHNG TRONG PHN TCH L HO

Chuyn ngnh: Ho phn tch
M s: 60 44 29


LUN VN THC S KHOA HC HO HC


NGI HNG DN KHOA HC:
TS. NG XUN TH






Thi Nguyn, nm 2008

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MC LC


M u 1
I.
L do chn ti 1
II.
Ni dung chnh ca ti 2
III.
Nhim v ca ti 2
Ch-ng I Tng quan 3
I.1
ngha ca h thng bi tp
3
I.1.1 Tng hp v n luyn kin thc 3
I.1.2 Phn loi bi tp v cu hi ho hc 5
I.1.3 Tc dng ca bi tp ho hc 6
I.1.4 Vn dng kin thc gii bi tp 7
I.2 Dy hc ch trng ph-ng php t hc 7
I.2.1 Dy hc ch trng rn luyn ph- ng php t hc 8
I.2.2 Hc thng qua t chc cc hot ng ca sinh vin 8
I.2.3 Tng c- ng hc tp c th, phi hp vi hc tp hp tc 9
I.3 Xu h-ng pht trin ca bi tp Ho hc hin nay 9
I.4 C s phn loi cu hi v bi tp cn c vo mc
nhn thc v t- duy
10
Ch-ng II Ph-ng php phn tch quang ph hp th nguyn
t
13
II.1 C s l thuyt 13
II.1.1 c im chung ca ph- ng php o quang ph hp
th nguyn t 13
II.1.2 iu kin to thnh ph hp th nguyn t 13
II.1.2.1 Qu trnh nguyn t ho mu 13
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II.1.2.2 Cc ph- ng php nguyn t ho 14
II.1.2.3 S hp th bc x cng h- ng 15
II.1.2.4 Ph- ng php phn tch ph hp th nguyn t 15
II.1.3 Cch loi tr sai s do cc nguyn t i km v sai s
phng 17
II.2 Cu hi t lun 18
II.3 Bi tp chng II 37
Chng III Ph-ng php phn tch quang ph pht x nguyn t 60
III.1 C s l thuyt 60
III.1.1 c im chung ca phng php quang ph pht x
nguyn t 60
III.1.2 S to thnh ph AES 60
III.1.3 Bn cht ca ph- ng php ph pht x nguyn t 61
III.1.4 S kch thch, s pht x v c- ng vch pht x
nguyn t
62
III.2 Cu hi t lun 63
III.3 Bi tp chng III 79
Chng IV Cc ph-ng php tch, chit v phn chia 97
IV.1 C s l thuyt ca ph-ng php chit 97
IV.1.1 nh ngha v h s phn b 97
IV.1.2 Hng s chit 97
IV.1.3 Cc yu t nh h- ng n qu trnh chit ho hc 98
IV.1.3.1
nh h- ng ca H
+
trong pha n- c
98
IV.1.3.2
nh h- ng ca hiu ng mui
99
IV.1.3.3
nh h- ng ca tc nhn chit
100
IV.1.3.4 iu kin chit 101
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IV.2 C s l thuyt ca ph-ng php sc k 101
IV.2.1 Thi gian l- u 102
IV.2.2. Th tch l- u 104
IV.2.3 Sc k kh (GC) 105
IV.2.3.1 Sc k kh - rn (GSC) 105
IV.2.3.2 Sc k kh - lng (GLC) 105
IV.3 C s l thuyt ca ph-ng php tch 106
IV.3.1 Tch cht bng ph- ng php ch- ng ct 106
IV.3.1.1 Cn bng lng hi ca h hai hay nhiu cu t 106
IV.3.1.2 Xc nh s a l thuyt v t s hi l- u bng ph- ng
php MC Cabe Thielo
106
IV.3.1.3 Xc nh s a l thuyt cc tiu v t s hi l- u cc
tiu theo ph- ng php MC Cabe Thielo
107
IV.3.1.4 Xc nh - ng knh ca ct ch- ng ct v chiu cao
ca ct ch- ng ct cho yu cu tch cho
107
IV.4 Cu hi t lun 108
IV.5 Bi tp chng IV 131

KT LUN 151

TI LIU THAM KHO







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Li cm n

Sau mt thi gian hc tp v nghin cu, ti hon thnh lun vn thc s
khoa hc ha hc Xy dng h thng cu hi v bi tp mt s chng trong
phn tch l ha. Vi s gip tn tnh ca cc thy c gio trong khoa Ha
ca trng HSP Thi nguyn v thy c trong t b mn Ha phn tch trng
HSP H Ni v c bit l s gip ca thy gio TS ng Xun Th, Thy
dnh nhiu thi gian cng sc ch bo ti trong sut qu trnh thc hin ti.
Thy c bn tho nhiu ln, sa cha, b sung v ng gp kin qu bu
ti hon thnh ti ny.
Ti xin by t li cm n chn thnh nht ti TS ng Xun Th v cc
thy c khoa Ha HSP Thi Nguyn, trng HSP H Ni, cc bn b ng
nghip, th vin trng HSP Thi Nguyn, th vin trng HSP H Ni, th-
vin tr- ng HKHTN H Ni. Ti xin gi li cm n ti Phng qun l sau i
hc trng HSP Thi Nguyn, Ban ch nhim Khoa Ha trng HSP Thi
Nguyn to cc iu kin thun li nht trong sut thi gian ti nghin cu,
thc hin ti.

Thi Nguyn, ngy 27 thng 08 nm 2008
Tc gi


Nguyn Thanh Tun

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1
PHN M U
I L do chn ti:
Trong cng cuc cng nghip ho, hin i ho t nc, nn kinh t
nc ta ang chuyn i t c ch k hoch ha tp trung sang c ch th
trng c s qun l ca Nh nc. Cng cuc i mi ny ra nhng yu
cu mi i vi h thng gio dc. Cng vi s pht trin ca khoa hc k
thut, thng tin lin lc trn th gii rt pht trin ko theo s thay i v
cng to ln v yu t con ngi trong x hi. Trong x hi mi, tri thc l
yu t quyt nh, con ngi l yu t trung tm, l ch th ca ton x hi,
do gio dc con ngi ng vai tr quan trng trong s pht trin ca t
nc [26].
p ng yu cu con ngi - ngun nhn lc, yu t quyt nh s
pht trin ca t nc trong thi k cng nghip ha, hin i ha cn to
ra nhng chuyn bin c bn, ton din v gio dc v o to. Trong nhng
nm gn y, B gio dc v o to khuyn khch vic s dng a dng
cc phng php dy hc tch cc nhm hot ng ha ngi hc. Mun
c nh th, ngun bi tp, cu hi cho ni dung kin thc phi phong ph,
a dng.
Tuy vy, vi nhng mn hc c mc t duy cao v mt kh nng
vn dng kin thc tng hp th vic chun b dng cu TNKQ l dng nh
cha y , cha c s sng to, nhy bn v s pht trin t duy khoa hc
cao. Do vy, trong trng hp ny cn duy tr v pht trin h thng cu hi
v bi tp t lun x l thng tin v lnh hi tri thc mn hc.[17]
V nhng l do trn y, chng ti mnh dn la chn ti Xy
dng h thng cu hi v bi tp mt s chng trong phn tch l ha
v s dng chng theo hng dy v hc tch cc pht trin nng lc t
duy, c lp, sng to ca ngi hc.

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II Ni dung chnh ca ti:
H thng cu hi v bi tp t lun mn phn tch l ho ca 3
chng:
- Chng I: Phng php phn tch quang ph hp th nguyn t.
- Chng II: Phng php phn tch quang ph pht x nguyn t.
- Chng III: Cc phng php tch, chit v phn chia.
III Nhim v ca ti:
- Nghin cu c s l lun ca ti.
- Nghin cu a ra h thng cu hi v bi tp trong ni dung ti.
- Nghin cu hng dn cch gii.
Phn loi thnh cc nhm bi tp theo ch , t h thng ha kin thc
v bao qut c ni dung mn hc ca 3 chng ny.
T nng cao cht lng ging dy hc phn Phn tch l ha
trong cc trng HSP, CSP v HKHTN, c s dng hc phn
phn tch ha l.


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Ch-ng I
TNG QUAN

I.1 ngha ca h thng bi tp:
UNESCO tng nhn mnh rng: tri vi thng l c truyn vic
ging dy phi thch nghi vi ngi hc, ch khng phi buc ngi hc
tun theo cc quy nh sn c t trc trong vic dy hc. Ngi hc v
cng chng ni chung cn c ting ni nhiu hn trong vic quyt nh cc
vn lin quan n gio dc. T nhng nm 1980 tr li y, ni bt ln
mt hng mi: vic ging dy phi m bo cho ngi hc tr thnh ngi
cng dn c trch nhim v hnh ng hiu qu. Nh vy mc ch ca vic
hc tp pht trin t hc hiu n hc hnh ri n hc thnh
ngi - mt con ngi t ch, nng ng v sng to. V th vic hc tp
gii quyt vn trong hc tp, trong thc tin i hi con ngi phi c c
kin thc v phng php t duy.[19]
I.1.1 Tng hp v n luyn kin thc:
Vic dy hc, c bit dy hc i hc khng th thiu bi tp, s
dng bi tp l mt bin php ht sc quan trng nng cao cht lng dy
hc. H thng cu hi v bi tp c nhng ngha, tc dng to ln v nhiu
mt:
- Lm chnh xc ha cc khi nim ha hc, cng c, o su v m
rng kin thc mt cch sinh ng, phong ph, hp dn. Khi ngi hc vn
dng kin thc vo vic gii bi tp, h mi nm kin thc mt cch su sc.
- n tp, h thng ha kin thc mt cch tch cc nht. Khi n tp,
ngi hc s khng tp trung nu gi n tp ch yu cu h nhc li cc
kin thc c hc. Thc t cho thy ngi hc (hc sinh, sinh vin) ch
thch tr li cc cu hi suy lun v gii bi tp trong gi n tp.
- Rn luyn cc k nng khoa hc ha hc ca mn hc nh cn bng
phng trnh phn ng, phng trnh ion, tnh ton theo cng thc ha hc,
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p dng cc nh lut, phng php xc nh nh lng cc cht Nu l
bi tp thc nghim s rn cc k nng thc hnh, gp phn vo vic gio
dc k thut tng hp cho ngi hc.
- Rn luyn kh nng vn dng kin thc vo thc tin i sng, lao
ng sn xut v bo v mi trng.
- Rn luyn k nng s dng ngn ng ha hc v cc thao tc t duy.
Pht trin hc sinh cc nng lc t duy logic, bin chng, khi qut, c
lp, thng minh, sng to.
- Rn luyn c tnh chnh xc, kin nhn, trung thc v lng say m
khoa hc.
C kh nng tng hp v khi qut ha kin thc:
Thng qua vic tr li cc cu hi v gii cc bi tp trong ni dung
hc phn hc tng ng, ngi sinh vin s t khi qut ha kin thc mt
cch tt nht di s c vn, ch o ca ngi thy.
hnh thnh cho sinh vin nhng khi qut ng n, tiu biu cn
m bo cc iu kin sau:
- Lm bin thin hoc m nht nhng du hiu khng bn cht ca vt
hay hin tng kho st, ng thi gi khng i du hiu bn cht.
- Chn nhng dng bi tp a ra c s bin thin hp l nht
nu bt c du hiu bn cht v tru tng ha du hiu th yu.
- C th s dng nhng cch bin thin khc nhau c cng mt
ngha tm l hc, nhng li hiu nghim. Qua th hin c s mm do
ca t duy.
- Phi cho ngi hc t mnh pht biu c thnh li nguyn tc bin
thin v nu c tnh ca nhng du hiu khng bn cht. iu cng
chng t rng sinh vin nhn thc c du hiu bn cht. Ngoi vic bo
m nhng iu kin trn y, gio vin cn tp luyn cho ngi hc pht
trin t duy khi qut bng nhng hnh thc quen thuc nh lp dn , xy
dng nhng kt lun v tm tt ni dung cc bi, cc chng.[26]
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I.1.2 Phn loi bi tp v cu hi ha hc:
Da vo ni dung v hnh thc th hin c th phn loi bi tp ha
hc thnh 2 loi:
- Bi tp nh tnh.
- Bi tp nh lng.
Cu hi c th phn loi thnh:
- Cu hi ti hin kin thc
- Cu hi vn dng kin thc
- Cu hi suy l, chng minh.
* Bi tp nh tnh: L cc dng bi tp c lin h vi s quan st
m t, gii thch cc hin tng ha hc. Cc bi tp nh tnh cng c rt
nhiu cc bi tp thc tin gip hc sinh gii quyt cc vn thc tin sinh
ng.
* Bi tp nh lng (bi ton ha hc): L loi bi tp cn vn dng
k nng ton hc kt hp vi k nng ha hc (nh lut, nguyn l, quy tc,
) gii.
* Cu hi ti hin kin tc l dng cu hi ngi hc ch cn ti hin
trnh by li nhng ni dung m mnh tip thu c.
* Cu hi vn dng kin thc l cu hi m ngi hc cn phi
nghin cu k phn kin thc c s l thuyt, t vn dng linh hot trong
khi nghin cu gii quyt bi ton.
* Cu hi suy l, chng minh l cu hi m ngi hc phi nm vng
l thuyt, bit vn dng cc ni dung kin thc c lin quan gii quyt bi
ton.[9]
I.1.3 Tc dng ca bi tp ha hc:
* Tc dng tr dc:
- Bi tp ho hc c tc dng lm chnh xc, cng nh hiu su hn
cc khi nim v nh lut hc.
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- Gip cho sinh vin nng ng sng to trong hc tp, pht huy nng
lc nhn thc v t duy, tng tr thng minh v l phng tin ngi hc
vn ti nh cao tri thc.
- L con ng ni lin gia kin thc thc t v l thuyt to ra mt
th hon chnh thng nht bin chng trong c qu trnh nghin cu. o
su, m rng s hiu bit mt cch sinh ng, phong ph khng lm nng n
thm khi lng kin thc cho ngi hc. Ch c vn dng kin thc vo
vic gii bi tp, sinh vin mi nm kin thc su sc.
- L phng tin n tp, cng c, h thng ha, kim tra nh gi
vic nm bt kin thc mt cch tt nht (ch ng, sng to).
- To iu kin pht trin t duy cho ngi hc: khi gii bi tp bt
buc ngi hc phi suy lun, quy np, din dch hoc cc thao tc t duy
u c vn dng.
Trong thc t hc tp, c nhng vn buc ngi hc phi o su
suy ngh mi hiu c trn vn. Thng thng khi gii mt bi ton nn
yu cu hoc khuyn khch ngi hc gii bng nhiu cch - tm ra cch gii
ngn nht, hay nht.
* Tc dng gio dc:
- Bi tp ha hc c tc dng gio dc t tng cho hc sinh, sinh
vin v thng qua gii bi tp rn luyn cho HS, SV tnh kin nhn, trung
thc trong hc tp, tnh sng to khi x l v vn dng trong cc vn hc
tp. Mt khc, qua vic gii bi tp rn luyn cho cc em tnh chnh xc khoa
hc v nng cao hng th hc b mn.
- Cc bi tp ha hc cn c s dng nh mt phng tin nghin
cu ti liu mi, ngoi ra cc bi c ni dung thc nghim c tc dng rn
luyn tnh tch cc, t lc lnh hi tri thc v tnh cn thn, tun th trit
quy nh khoa hc, chng tc phong lum thum, vi phm nhng nguyn tc
khoa hc.[25]
I.1.4 Vn dng kin thc gii bi tp:
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gii bi tp ngi hc phi bit vn dng l thuyt hc ni
dung cc chng cc bi, qu trnh ny thc cht i hi ngi hc phi c
mt k nng nhn thc v t duy nht nh. Hot ng nhn thc v pht
trin t duy ca sinh vin trong qu trnh dy hc ha hc.
Nhn thc l mt trong ba mt c bn ca i sng tm l con ngi
(nhn thc, tnh cm, l tr). N l tin ca hai mt kia v ng thi c
mi lin h cht ch vi chng v cc hin tng tm l khc.
T duy l mt qu trnh tm l phn nh nhng thuc tnh bn cht,
nhng mi lin h bn trong c tnh quy lut ca s vt hin tng trong
hin thc khch quan m trc ta cha bit.
Theo M.N.Sacacop: T duy l s nhn thc khi qut gin tip cc s vt
v hin tng trong nhng du hiu, nhng thuc tnh chung v bn cht ca
chng. T duy cng l s nhn thc sng to nhng s vt hin tng mi,
ring l ca hin thc trn c s nhng kin thc khi qut ha thu nhn
c.[9]
I.2 Dy hc ch trng phng php t hc:
Tnh tch cc l mt phm cht vn c ca con ngi trong i sng
x hi, khc vi ng vt con ngi khng ch tiu th nhng g c sn trong
thin nhin m ch ng to ra c s vt cht cn thit cho s tn ti v pht
trin ca x hi.

I.2.1 Dy hc ch trng rn luyn phng php t hc:
Phng php tch cc xem vic rn luyn phng php hc tp cho
hc sinh khng ch l mt bin php nng cao hiu qu dy hc m cn l
mt mc tiu dy hc. Trong mt x hi hin i ang bin i nhanh cng
vi s bng n thng tin, khoa hc, k thut, cng ngh pht trin vi tc
cc k nhanh chng, chng ta thc s cn phi quan tm dy cho sinh vin
phng php hc tp, phng php nhn thc.
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Nu rn luyn cho ngi hc c c phng php, k nng, thi
quen, ch t hc th s to cho h lng ham hc, khi dy ni lc vn c
trong mi ngi th kt qu hc tp s c nng ln gp bi. V vy, vi
phng php dy hc ngy nay rt nhn mnh hot ng t hc, n lc to
ra s chuyn bin t hc tp th ng sang t hc ch ng c s hng dn
ca ngi thy. Bn cnh vic hc tp l sut i, ngi hc khng ch
hc trong nh trng, m cn hc mi lc, mi ni, sau khi ri gh nh
trng cn phi tip tc hc tp b sung cp nht kin thc.[10]
I.2.2 Hc thng qua t chc cc hot ng hc tp ca hc sinh:
Trong phng php dy hc tch cc, ngi hc l i tng ca hot
ng dy, nhng ng thi cng l ch th ca hot ng hc c cun vo
cc hot ng hc tp do gio vin t chc v ch o, do m sinh vin t
khm ph nhng iu mnh cha r ch khng phi tip thu nhng tri thc
c gio vin sp t sn. Khi t vo nhng tnh hung thc t, ngi
hc trc tip quan st, tho lun, gii quyt vn t ra theo nhng suy
ngh ring ca mnh, t sinh vin va nm kin thc, va nm phng
php lm ra kin thc m khng theo nhng khun mu sn c. Vi cch
dy hc ny, Thy khng ch n gin l truyn t tri thc m s dy hc
phi gip cho tng sinh vin bit hnh ng v tch cc tham gia cc chng
trnh hnh ng cng tp th.[10]
I.2.3 Tng cng hc tp c th, phi hp vi hc tp hp tc:
Khi trong mt lp hc m trnh kin thc, t duy ca sinh vin
khng ng u mt cch tuyt i th khi p dng phng php dy hc
tch cc buc phi chp nhn s phn ha v cng , tin hon thnh
nhim v hc tp, nht l cc bi hc c thit k thnh mt chui cc hot
ng c lp. Khi p dng phng php tch cc trnh cao th s phn
ha cng ln. Vic s dng cc cng ngh thng tin trong nh trng s p
ng nhu cu c th ha hot ng hc tp theo nhu cu v kh nng ca mi
hc sinh, sinh vin.
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Tuy nhin, trong hc tp khng phi mi tri thc, k nng, thi u
c hnh thnh bng nhng hot ng c lp ca mi c nhn. Lp hc l
mt mi trng giao tip thy - tr, to nn mi quan h hp tc gia cc c
nhn trn con ng chim lnh nhng ni dung hc tp. Thng qua tho
lun, tranh lun trong tp th, kin c nhn c bc l, khng nh hay
bc b, qua ngi hc c nng mnh ln mt trnh mi. Ngi hc
s vn dng vn hiu bit, kinh ngim sng ca mi c nhn v ca c tp
th lp ch khng phi ch da trn vn hiu bit v kinh nghim sng ca
gio vin.
Hnh thc hc tp theo nhm khng lm hn ch sc mnh, hng th
hc tp ca mi c nhn m tri li to mnh m tnh tch cc, ch ng
ca mi c nhn, gip h chuyn t i tng gio dc thnh ch th gio
dc.[25]
I.3. Xu hng pht trin ca bi tp ha hc hin nay:
Bi tp ha hc va l mc tiu, va l mc ch, va l ni dung va
l phng php dy hc hu hiu do vy cn c quan tm, ch trng trong
cc bi hc. N cung cp cho hc sinh khng nhng kin thc, nim say m
b mn m cn gip ngi hc con ng ginh ly kin thc, l bc m
cho qu trnh nghin cu khoa hc, hnh thnh v pht trin c hiu qu
trong hot ng nhn thc ca hc sinh.
Bng h thng bi tp s thc y s hiu bit ca sinh vin, s vn
dng nhng hiu bit vo thc tin, s l yu t c bn ca qu trnh pht
trin x hi, tng trng kinh t nhanh v bn vng.
Xu hng pht trin ca bi tp ho hc hin nay hng n rn luyn
kh nng vn dng kin thc, pht trin t duy ho hc. Nhng bi tp c
tnh cht hc thuc trong cc cu hi l thuyt s gim dn m c thay
bng cc cu hi i hi s t duy, tm ti.
Dy hc ch trng rn luyn phng php t hc trng i hc
c xem l rt quan trng v c nhiu trng coi trng p dng. Ngoi
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ra, trong thi gian gn y, mt s chin lc i mi phng php dy hc
c th nghim l dy hc hng vo ngi hc, hot ng ha
ngi hc, tip cn kin to trong dy hc [6]

I.4. C s phn loi cu hi v bi tp cn c vo mc nhn thc v
t duy:
Vn dng cc quan im v vic phn loi mc nhn thc v t
duy ca GS.Bloom v GS.Nguyn Ngc Quang, cn c vo thc tin dy
hc Vit Nam, chng ti thy vic kt hp vn dng hai quan im trn
cho ph hp l cn thit.
Vic phn loi sp xp cc cu hi v bi tp hc phn phn tch l ha
cn c vo cc mc nhn thc v t duy ca qu trnh lnh hi kin thc
k nng k xo chng ti thy c th sp xp thnh 4 dng sau:
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Dng
bi
Nng lc nhn thc Nng lc t duy K nng
I
Bit (nh li nhng
kin thc hc mt
cch my mc v
nhc li)
T duy c th Bt chc theo mu
II
Hiu (ti hin kin
thc, din gii kin
thc, m t kin thc)
T duy logic (suy
lun, phn tch,
so snh, nhn
xt)
Pht huy sng kin
(hon thnh k nng
theo ch dn, khng
cn bt chc my
mc)
III
Vn dng T duy h thng
(suy lun tng
t, tng hp, so
snh, khi qut
ha)
i mi (lp li k
nng no mt cch
chnh xc, nhp
nhng)
IV
Vn dng sng to
(phn tch, tng hp,
nh gi)
T duy tru
tng (suy lun
mt cch sng
to)
Sng to (hon thnh
k nng mt cch d
dng c sng to, t
ti trnh cao)

Vic s dng cu hi v bi tp trong dy hc c bit l dy hc i
hc c tm quan trng c bit. i vi sinh vin y l phng php hc
tp tch cc, hiu qu v khng c g thay th c, gip cho sinh vin nm
vng kin thc mn hc, pht trin t duy, hnh thnh khi nim, kh nng
ng dng ha hc vo thc tin, lm gim nh s nng n cng thng ca
khi lng kin thc v gy hng th cho sinh vin trong hc tp.
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12
Tuy nhin hiu qu ca vic s dng h thng cu hi v bi tp ha
hc cn ph thuc vo nhiu yu t nh: tnh t gic, tnh va sc v hng
th hc tp ca sinh vin. Cng nh vn hc tp, nu nh cu hi v bi
tp d qu hoc kh qu u khng c sc li cun hc sinh, sinh vin. V
vy trong qu trnh dy hc, tt c cc kiu bi ln lp khc nhau, ngi
gio vin phi bit s dng cu hi v bi tp c s phn ha ph hp vi
tng i tng tc l gp phn rn luyn v pht trin t duy cho ngi hc.
Ty theo mc ch dy hc, tnh phc tp v quy m ca tng loi bi,
gio vin c th s dng h thng cu hi v bi tp theo 4 bc ca qu trnh
nhn thc v t duy nh trn. [9]















CHNG II
PHNG PHP PHN TCH QUANG PH HP TH NGUYN T

II.1. C S L THUYT:
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13
I.1.1. c dim chung ca phng php phn tch quang ph hp th
nguyn t (AAS):[7]
- Phng php AAS (Atomic Absorption Spectroscopy) da trn kh nng
hp th chn lc cc bc x cng hng ca nguyn t trng thi t do.
Cc nguyn t t do c to ra do tc dng ca ngun nhit bin cc cht
t trng thi tp hp bt k thnh trng thi nguyn t, l qu trnh nguyn
t ho.
- Cc nguyn t t do s hp th bc x in t tun theo nh lut hp th
bc x (nh lut Bouguer Lambert Beer):

A = lg
I
I
0
= C l. .

c
Trong : A: mt quang.
I
0
, I: cng nh sng trc v sau khi b nguyn t t do hp
th.

c : h s hp th mol phn t, ph thuc bc sng .


l: dy lp hi nguyn t.
- chnh xc ca php o ph hp th nguyn t rt cao.
- Phng php phn tch n gin, nhanh, i khi khng cn sinh ch mu,
p dng rng ri trong nhiu lnh vc khoa hc.
II.1.2. iu kin to thnh ph hp th nguyn t: [11]
II.1.2.1. Qu trnh nguyn t ho:
- Bin mt cht trng thi tp hp bt k thnh trng thi nguyn t t do
gi l qu trnh nguyn t ho.
- Gi thit kim loi nghin cu Me nm trong dung dch dng mui MeX.
Dung dch MeX c phun vo ngn la n kh dng aeroson. Trong
ngn la n kh s xy ra qu trnh nhit phn: MeX Me + X
- Trong ngn la c th xy ra qu trnh ion ho nguyn t to thnh lm
gim nhy ca php phn tch. hn ch s ion ho ny, phi a vo
dung dch phn tch cc cht d b ion ho tng nn electron trong bu
kh.
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14
II.1.2.2. Cc phng php nguyn t ho:
* Nguyn t ho mu bng ngn la:
- Ngi ta dng nng lng nhit ca ngn la n kh ha hi v nguyn
t ho mu phn tch. V th mi qu trnh xy ra trong khi nguyn t ho
mu ph thuc vo cc c trng v tnh cht ca ngn la n kh, nhng
ch yu l nhit ca ngn la. l yu t quyt nh hiu sut nguyn
t ho mu phn tch v mi yu t nh hng n nhit ca ngn la n
kh u nh hng n kt qu ca phng php phn tch.
- Trong php o ph hp th nguyn t, ngn la l mi trng hp th. N
c nhim v ho hi nguyn t ho mu phn tch, to ra m hi ca cc
nguyn t t do c kh nng hp th bc x n sc to ra ph hp th
nguyn t, v th ngn la n kh c dng vo mc ch ho hi v
nguyn t ho mu phn tch th:
+ Ngn la n kh phi lm nng u c mu phn tch.
+ Ngn la n kh phi ln v n nh theo thi gian.
+ Ngn la n kh phi thun khit.
+ Ngn la n kh phi c b dy ln.
* Nguyn t ho mu khng dng ngn la:
- K thut nguyn t ho mu khng dng ngn la hin nay ang c ng
dng rt rng ri v c nhy rt cao. Do vy, khi phn tch lng vt cc
kim loi trong nhiu trng hp khng cn thit phi lm giu s b cc
nguyn t cn xc nh. c bit l khi xc nh cc nguyn t vi lng
trong cc loi mu ca y hc, sinh hc .
- Tuy nhin, n nh ca php o khng dng ngn la km hn php o
dng ngn la. nh hng ca ph nn thng rt ln. Khoa hc pht trin,
th vic khc phc nhng nhc im ny l khng kh khn.
- Php o khng ngn la i hi mt lng mu tng i nh (mi ln o
khong 20 - 50 L).
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15
- Nguyn t ho mu khng dng ngn la l qu trnh nguyn t ho tc
khc trong thi gian rt ngn nh nng lng ca dng in cng sut ln v
trong mi trng kh tr.
II.1.2.3. S hp th bc x cng hng:
- Khi hng vo lp hi nguyn t t do Me chm bc x in t (chnh l
cc tia pht x pht ra t n catot rng lm bng chnh kim loi cn xc
nh) c tn s ng bng tn s cng hng ca nguyn t kim loi Me, s
xy ra hin tng hp th cng hng chuyn ln cc mc nng lng
kch thch gn nhau: Me + v h Me
*

Qu trnh ny tun theo nh lut Bouguer Lambert Beer.
- Trong ph hp th nguyn t, ch mt s nguyn t c kh nng hp th
bc x cng hng thc t bng s nguyn t chung ca nguyn t cn xc
nh v t b nh hng ca nhit ngun nhit nn phng php ny c
nhy cao.
II.1.2.4. Phng php phn tch quang ph hp th nguyn t:

Hnh 2.1: S khi ca ph k hp th nguyn t dng ngn la

1. Ngun bc x (n catot) 4. Detector quang
2. n 5. Cu trc ghi ph
3. My lc nh sng n sc
- Cu to ca n catot rng:
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16

Hnh 2.2: n catot rng
1. Bng thu tinh 2. Anot
3. Catot 4. Ca s thch anh

n catot rng l mt bng thu tinh hnh tr, ng knh 3 - 5cm, c
ca s bng thu tinh hay thch anh. Anot c ch to t thanh kim loi.
C hai cc c t trong bng thu tinh c cha kh tr (agon hay neon)
vi p sut khng ln (0,2 2MPa). n catot rng c ni vi dng in
300 500V, n nh v phi c n nh cao. Dng phng ca n thng
l vi miliampe. Khi n lm vic, mt dng mt bn trong catot cao
hn mt ngoi. V vy ti l m ca catot s pht sng. Catot ca n c
ch to t kim loi, hp kim kh nng chy c cha nguyn t cn xc nh.
- Vic gim cng ca bc x cng hng do hin tng hp th ca cc
nguyn t t do ca nguyn t nghin cu tun theo nh lut hp th bc x
nguyn t Bouguer - Lambert - Beer:

A = lg
I
I
0
= C l. .

c
Mt quang t l thun vi nng cht nghin cu trong mu.
Ta xc nh nh lng theo 2 phng php:
+ Phng php ng chun: Ngi ta o mt quang ca vi dung
dch chun ri xy dng th A = f(C
TC
). Sau o mt quang ca dung
dch nghin cu vi cng iu kin o dung dch chun ri da vo th
xc nh C
X
ca dung dch nghin cu.
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17
+ Phng php thm: Tin hnh nh trong php o ph pht x
nguyn t, ch khc l thay cho S A ( en), ta xy dng s ph thuc mt
quang ti vch ph cng hng ( ):

A = f(C
CT
) v ngoi suy n

A =
0.
Nu dng mt dung dch chun, u tin o

X
A ca dung dch nghin cu,
sau thm vo dung dch nghin cu mt nng ca dung dch tiu
chun nguyn t nghin cu, o mt quang ca dung dch thm c
A
X + Ch
.
T cc kt qu ta c:
A
X
=
X
C l. .

c
A
X + Ch
= ) ( . .
ch X
C C l +

c C
X
= C
ch

X ch X
X
A A
A

+

II.1.3. Cc loi tr sai s do cc nguyn t i km v sai s phng:[11]
Trong php o ph hp th nguyn t, ngi ta khc phc sai s
phng bng cch dng 2 phng php hiu chnh sai s ca phng nn nh
sau:
- Hiu chnh sai s phng dng n teri (hiu chnh nh sng c bc sng
lin tc).
- Phng php t o: y dng in nh sng c cng thp, ta o
c tng tn hiu ca hp th nguyn t v tn hiu phng. Cn khi dng
dng in nh sng c cng cao xut hin tn hiu hp th ca phng.
Sau my t ng tr i tn hiu tng phn tn hiu phng v nh vy ta
ch o c tn hiu hp th nguyn t ca nguyn t nghin cu.

II.2. CU HI:
Cu 1: Hy cho bit nguyn tc ca php o AAS?
HDTL:
Phng php phn tch da trn c s o ph hp th nguyn t ca
mt nguyn t c gi l php o ph hp th nguyn t (php o AAS).
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18
C s l thuyt ca php o ny l s hp th nng lng (bc x n sc)
ca nguyn t t do trng thi hi (kh) khi chiu chm tia bc x qua m
hi ca nguyn t y trong mi trng hp th. thc hin php o AAS
phi thc hin 3 nguyn tc sau:
+ Chn cc iu kin v mt loi trang b ph hp chuyn mu phn tch
t trng thi ban u (rn hay dung dch) thnh trng thi hi ca cc nguyn
t t do. l qu trnh ho hi v nguyn t ho mu.
+ Chiu chm tia sng bc x c trng ca nguyn t cn phn tch qua
m hi nguyn t va iu ch c trn. Cc nguyn t ca nguyn t
cn xc nh trong m hi s hp th chn lc nhng bc x nht nh
v to ra ph hp th ca n. y, phn cng ca chm tia sng b
nguyn t hp th ph thuc vo nng ca n trong mi trng hp th.
Ngun cung cp chm tia sng pht x ca nguyn t cn nghin cu c
gi l ngun pht bc x n sc hay bc x cng hng.
+ Tip , nh mt h thng my quang ph, ngi ta thu ton b chm
sng, phn li v chn mt vch ph hp th ca nguyn t cn nghin cu
o cng ca n. Cng chnh l tn hiu hp th ca vch ph hp
th nguyn t. Trong mt gii hn nht nh ca nng C, gi tr cng
ny l ph thuc tuyn tnh vo nng C ca nguyn t trong mu phn
tch theo phng trnh:
A

= a.C
b
a = K.K
a
: hng s thc
nghim
b: hng s bn cht, 0 < b s 1
Thng thng, ngi ta thng s dng trong khong nhit b = 1
(khng ph thuc tuyn tnh) ng dng phn tch.

Cu 2: thc hin c php o ph hp th nguyn t, h thng my o
ph hp th nguyn t phi bao gm cc phn c bn no?
HDTL:
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19
Mun thc hin c php o ph hp th nguyn t, h thng my
o ph hp th nguyn t phi bao gm 4 phn c bn sau:
+ Phn 1: Ngun pht tia pht x cng hng (vch ph pht x c trng
ca nguyn t cn phn tch), chiu vo mi trng hp th cha cc
nguyn t t do ca nguyn t. chnh l cc n catot rng (HCL), cc
n phng in khng cc (EDL), hay ngun pht bc x lin tc c
bin iu.
+ Phn 2: H thng nguyn t ho mu phn tch. H thng ny c ch to
theo hai loi k thut nguyn t ho mu. l k thut nguyn t ho bng
ngn la n kh (lc ny ta c php o F - AAS) v k thut nguyn t ho
khng ngn la (lc ny c php o ETA - AAS).
+ Phn 3: L my quang ph, n l b n sc, c nhim v thu, phn li v
chn tia sng (vch ph) cn o hng vo nhn quang in pht tn hiu
hp th AAS ca vch ph.
+ Phn 4: L h thng ch tn hiu hp th ca vch ph (tc l cng ca
vch ph hp th hay nng nguyn t phn tch). H thng ny c th l
cc trang b:
- n gin nht l mt in k ch nng lng hp th (E) ca vch
ph.
- mt my t ghi pic ca vch ph.
- hoc b hin s digiltal.
- hay b my in (printer).
- hoc my tch phn.
Cu 3: Hy nu nhng u, nhc im ca php o AAS?
HDTL:
* u im:
- Php o ph hp th nguyn t c nhy v chn
lc cao. Gn 60 nguyn t ho hc c th c xc nh bng phng php
ny vi nhy t 1.10
-4
n 1.10
-5
%. c bit, nu s dng k thut
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20
nguyn t ho khng ngn la th c th t n nhy n.10
-7
%. Chnh v
nhy cao, nn phng php phn tch ny c s dng rng ri trong
nhiu lnh vc xc nh lng vt cc kim loi. c bit l trong phn
tch cc nguyn t vi lng trong cc i tng mu y hc, sinh hc, nng
nghip, kim tra cc ho cht c tinh khit cao.
- ng thi cng do c nhy cao nn trong nhiu
trng hp khng phi lm giu nguyn t cn xc nh trc khi phn tch.
Do tn t nguyn liu mu, tn t thi gian khng cn phi dng nhiu ha
cht tinh khit cao khi lm giu mu. Mt khc cng trnh c s nhim
bn mu khi x l qua cc giai on phc tp. cng l mt u im ln
ca php o ph hp th nguyn t.
- Cc ng tc thc hin nh nhng. Cc kt qu phn
tch li c th ghi li trn bng giy hay gin lu gi li sau ny. ng
thi, vi cc trang thit b hin nay, ngi ta c th xc nh ng thi hay
lin tip nhiu nguyn t trong
mt mu. Cc kt qu phn tch li rt n nh, sai s nh.
* Nhc im:
- Php o AAS ch cho ta bit thnh phn nguyn t ca
cht trong mu m khng ch ra trng thi lin kt ca nguyn t trong
mu. V th n ch l phng php phn tch thnh phn ho hc ca nguyn
t.
- Mun thc hin php o AAS cn phi c mt h thng
my AAS tng i t tin. Do nhiu c s khng iu kin xy
dng phng th nghim v mua sm my mc.
- Php o c nhy cao nn s nhim bn rt c
ngha i vi kt qu phn tch hm lng vt. V th mi trng khng kh
phng th nghim phi khng c bi, cc dng c ho cht dng trong php
o phi c tinh khit cao.
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21
Cu 4: Nu nhng yu cu v nhim v ca ngn la trong k thut nguyn
t ho mu?
HDTL:
Trong php o ph hp th nguyn t, ngn la l mi trng hp th.
N c nhim v ho hi v nguyn t ho mu phn tch to ra m hi ca
cc nguyn t t do c kh nng hp th bc x n sc to ra ph hp
th nguyn t, v th ngn la n kh mun dng vo mc ch ho hi
v nguyn t ho mu phn tch n cn phi tho mn mt s yu cu sau:
+ Ngn la n kh phi lm nng u c mu
phn tch. Ho hi v nguyn t ho mu phn tch vi hiu sut cao, m
bo cho php phn tch t chnh xc v nhy cao.
+ Nng lng (nhit ) ca ngn la phi ln
v c th iu chnh c tu theo tng mc ch phn tch mi nguyn t.
ng thi li phi n nh theo thi gian v lp li c trong cc ln phn
tch khc nhau m bo cho php phn tch t kt qu ng n.
+ Ngn la phi thun khit.
+ Ngn la phi c b dy ln c c lp
hp th dy lm tng nhy ca php o.
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Cu 5: Hy trnh by cu to ca ngn la n kh?
HDTL:

Hnh 2.3 : Cu to ca ngn la n kh.

Ngn la n kh gm 3 phn chnh l:
+ Phn ti ca ngn la. Trong phn ny hn hp kh
c trn u v t nng cng vi cc ht sol kh (th aerosol) ca mu
phn tch. Phn ny c nhit thp (700 - 1200
o
C). Dung mi ho tan mu
s bay hi trong phn ny v mu c sy nng.
+ Vng trung tm ca ngn la. Phn ny c nhit
cao v thng khng c mu hoc c mu xanh rt nht. Trong phn ny hn
hp kh c t chy tt nht v khng c phn ng th cp. V th trong
php o ph hp th nguyn t ngi ta phi a mu vo phn ny
nguyn t ho v thc hin php o. Ngha l ngun n sc phi chiu qua
phn ny ca ngn la.
+ Phn v v ui ca ngn la: vng ny c nhit
thp, ngn la c mu vng v thng xy ra nhiu phn ng th cp khng
c li cho php o ph hp th nguyn t.

Cu 6: Hy trnh by nhng qu trnh xy ra trong ngn la?
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23
HDTL:
Ngn la l mi trng nguyn t ho mu ca php o ph hp th
nguyn t (F-AAS). Trong ngn la c nhiu qu trnh xy ra ng thi: c
qu trnh chnh v cng c qu trnh ph. Trong nhit ca ngn la l
yu t quyt nh mi din bin ca cc qu trnh.
Trc ht, khi mu th sol kh c dn ln n nguyn t ho, di tc
dng nhit ca ngn la, ming n, l s bay hi ca dung mi ho tan
mu v cc cht hu c trong th sol kh. Nh vy, mu cn li l cc ht rn
rt nh mn trong ngn la v n c dn tip vo vng trung tm ngn la.
Tip l qu trnh ho hi v nguyn t ho ca cc ht mu bt kh .
y cc cht s c cc qu trnh chnh sinh ra ph v qu trnh ph khng
sinh ra ph din bin theo tnh cht nhit ho ca cht mu.
* Yu t quyt nh cc qu trnh chnh l:
- Nhit ca ngn la.
- Bn cht ca cht mu v thnh phn ca cht mu.
- Tc dng nh hng ca cht ph gia thm vo mu.
* Cc qu trnh ph tuy c mc khc nhau, nhng trong mt mi
tng quan nht nh trong ngn la, c bit l nhit ngn la, th tt
c cc qu trnh u c th xy ra cng vi cc qu trnh chnh ca
php o F-AAS. Do phi chn cc iu kin ph hp hn ch n
mc nh nht cc qu trnh ph v gi cho n khng i sut trong mt
php o xc nh mt nguyn t.
Cu 7: Hy cho bit c ch ca cc qu trnh xy ra trong ngn la?
HDTL:
Cc qu trnh xy ra trong ngn la thng theo 2 c ch chnh:
+ Nu E
h
< E
a
tc l nng lng ho hi (E
h
) ca cc hp
phn c trong mu nh hn nng lng nguyn t ho (E
a
) ca n, th trc
ht cc hp phn ny s ho hi dng phn t. Sau cc phn t kh ny
mi b phn li (nguyn t ho) thnh cc nguyn t t do (c ch I).
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24
+ Nu E
h
> E
a
tc l nng lng phn li E
a
ca cc hp
phn ca mu l nh hn nng lng ho hi E
h
ca chnh n, th trc ht
cc hp phn ny s b phn li thnh cc nguyn t t do, ri sau mi ho
hi (c ch II).
C ch I:
M
n
A
m
(l) M
n
A
m
(k) n.M (k) + m.A (k)
M (k) + n (hv ) ph AAS
C ch II:
M
n
A
m
(l) n.M (r,l) + m.A (l,r) n.M (k)
M (k) + n (hv ) ph AAS
Cu 8: Hy tm tt cc qu trnh nguyn t ho mu?
HDTL: Cc qu trnh nguyn t ho mu:
1. Dn mu vo bung Aersol ho.
2. Qu trnh aerosol ho mu.
3. Ho hi, nguyn t ho: MeA (r) MeA (l) MeA (k)
4. S phn li, kch thch, hp th, ion ho, pht x:
Me
o
+ A
.
(phn li)
Me
o
+ hv (hp th bc x)
MeA Me
o
+ E (kch thch)
Me
o
e (ion ho)
Me
o
+ .
5. S kh oxi ca oxit bi cacbon:
MeO + C Me + CO
6. Cc phn ng ho hc khc (hp cht bn nhit monoxit):
Me + O MeO
Me + xC MeC
x

Cu 9: Hy nu nhng yu cu i vi h thng nguyn t ho mu?
HDTL: H thng nguyn t ho mu c 5 yu cu:
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25
1. H thng nguyn t ho hi v nguyn t ho mu phn tch vi
hiu sut cao v n nh, m bo cho php o c nhy cao
v lp li tt.
2. Phi cung cp c nng lng ln v c th iu chnh c
d dng theo yu cu c th nguyn t ho c nhiu loi mu
v phn tch c nhiu nguyn t.
3. Cuvet cha mu nguyn t ho phi c tinh khit cao. Khng
lm nhim bn mu, khng c ph ph gy kh khn cho php o
ca nguyn t cn phn tch.
4. Hn ch, c t hay khng c cc qu trnh ph trong qu trnh
nguyn t ho mu thc hin php o.
5. Tiu tn t mu phn tch.
Cu 10: Nu nhng yu cu ti thiu m ngun pht tia bc x n sc
trong php o ph AAS phi tho mn?
HDTL: C 4 yu cu:
- Ngun pht tia bc x n sc phi to ra c cc tia pht x nhy
(cc vch pht x nhy, c trng) ca nguyn t cn phn tch.
Chm tia pht x phi c cng n nh, phi lp li trong
cc ln o khc nhau trong cng iu kin, phi iu chnh c
vi cng mong mun cho mi php o.
- Ngun pht tia bc x phi cung cp c mt chm tia pht x
thun khit ch bao gm mt s vch nhy c trng ca nguyn t
phn tch. Ph nn ca n phi khng ng k. C nh th mi hn
ch c nhng nh hng v vt l v v ph cho php o AAS.
- Chm tia sng n sc do ngun cung cp phi c cng
cao. Nhng li phi bn vng theo thi gian v phi khng b cc
yu t vt l khc nhiu lon, t b nh hng bi cc dao ng ca
iu kin lm vic.
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26
- Ngun pht tia bc x n sc phi bn lu, khng qu t tin v
khng qu phc tp cho ngi s dng.
Cu 11: Nu nhng yu t c th nh hng n kt qu phn tch trong
php o ph hp th nguyn t?
HDTL:
Nhm 1: L cc thng s ca h my o ph. Cc thng s ny cn c
kho st v chn cho tng trng hp c th. Thc hin cng vic
ny chnh l qu trnh ti u ho cc thng s ca my o cho mt
i tng phn tch.
Nhm 2: L cc iu kin nguyn t ho mu. Cc yu t ny th hin rt
khc nhau tu thuc vo k thut c chn thc hin qu trnh
nguyn t ho mu.
Nhm 3: L k thut v phng php c chn x l mu. Trong cng
vic ny nu lm khng cn thn s c th lm mt hay lm nhim
bn thm nguyn t phn tch vo mu.
Nhm 4: Cc nh hng v ph.
Nhm 5: Cc yu t nh hng vt l.
Nhm 6: Cc yu t nh hng ho hc.
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27
Cu 12: Cc yu t v ph c nh hng nh th no trong php o AAS?
HDTL: Cc yu t v ph gm:
- S hp th nn: yu t ny c trng hp xut hin r rng nhng
cng c th khng xut hin. N ph thuc vo vch ph c chn o
nm trong vng ph no. Ni chung trong vng kh kin th yu t ny th
hin r rng, cn trong vng t ngoi th nh hng ny t xut hin do ph
nn trong vng t ngoi l yu. Hn na s hp th nn cn ph thuc vo
thnh phn nn ca mu phn tch.
V d: Khi xc nh Pb trong mu sinh hc bng php o ngn la th
s hp th nn l khng ng k. Khi xc nh Pb trong nc bin th nh
hng ny li l v cng ln.
- S chen ln ca vch ph: yu t ny xut hin khi cc nguyn t th
ba trong mu phn tch c nng ln v thng l nguyn t c s
ca mu. Tuy nguyn t ny c cc vch ph khng nhy nhng do nng
ln nn cc vch ny vn xut hin vi rng ln.
- S hp th ca cc ht rn: trong mi trng hp th, c bit l trong
ngn la n kh, nhiu khi cn c cha c cc ht rn rt nh li ti ca vt
cht mu cha b ho hi v nguyn t ho, hay cc ht mui cacbon ca
nhin liu cha c t chy hon ton. Cc loi ht ny thng c th c
lp v ca ngn la. Yu t ny gi l hp th gi. N th hin rt r rng
khi chn khng ng chiu cao ca n nguyn t ho mu v khi hn hp
kh chy khng c t chy tt.
Cu 13: nh hng ca yu t vt l trong php o AAS? Bin php loi
tr?
HDTL:
- nht v sc cng b mt ca dung dch mu: yu t ny nh hng
nhiu n tc dn mu vo bung aerosol ho ca mu, t nh hng
n kt qu phn tch. Tc dn mu t l nghch vi nht ca dung
dch mu.
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28

Hnh 2.4 : nh hng ca nht n tc dn mu (1cp 1g/m.s)
Trong mi qu trnh phn tch mt nguyn t, nht thit phi m bo
cho mu phn tch v cc mu u lp ng chun phi c cng nng
axit, loi axit v thnh phn ho hc, vt l ca cc nguyn t khc, nht l
cht nn ca mu. loi tr nh hng ny, ngi ta dng cc bin php
sau:
+ o v xc nh theo phng php thm tiu chun.
+ Pha long mu bng mt dung mi hay mt nn ph hp.
+ Thm vo mu mt cht m c nng ln.
+ Dng bm y mu vi mt tc xc nh m ta mong mun.
- Hiu ng lu: yu t ny th hin r rng trong php
o ph khng ngn la. N ph thuc vo bn cht cc nguyn t. Mun loi
tr nh hng ny, ngi ta lm nh sau:
+ Lm sch cuvet sau mi ln nguyn t ho mu.
+ Dng cc cuvet c ch to t cc loi graphit c hot ho
ton phn, c b mt chc v mn.
+ Khi phn tch nn o cc mu c nng nh trc.
+ Thm vo mu nhng cht m c nng ph hp.
+ Trng b mt trong ca cuvet graphit bng mt lp cc hp cht bn
nhit.
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29
- S ion ho: qu trnh ion ho thng lm gim s
nguyn t t do ca nguyn t phn tch trong mi trng hp th to ra ph.
loi tr yu t ny, ngi ta lm nh sau:
+ Chn iu kin nguyn t ho c nhit thp.
+ Thm vo mu phn tch mt cht m cho s ion ho.
- S kch thch ph pht x: yu t ny lm gim nng
ca cc nguyn t trung ho c kh nng hp th bc x trong mi trng
hp th. Do cng lm gim cng ca vch ph hp th. loi tr
n, ngi ta lm nh sau:
+ Chn nhit nguyn t ho mu thp ph hp m ti nhit
s kch ph pht x l khng ng k hoc khng xy ra i vi
nguyn t phn tch.
+ Thm vo mu cc cht m hn ch s pht x ca nguyn t
phn tch.

Cu 14: Cc yu t ho hc c nh hng nh th no trong php o AAS?
HDTL:
Trong php o AAS, cc nh hng ho hc cng
rt a dng v phc tp. N xut hin cng rt khc nhau trong mi trng
hp c th v cng c nhiu trng hp khng xut hin. Cc nh hng ca
ho hc c th lm kt qu xy ra theo cc hng sau:
- Lm gim cng ca vch ph ca nguyn t phn
tch, do s to thnh cc hp cht bn nhit, kh ho hi v kh nguyn t
ho. V d, nh hng ca cc ion silicat, sunfat, photphat, florua.
- Lm gim cng ca vch ph, do s to thnh
cc hp cht d ho hi v d nguyn t ho hay do hn ch c nh hng
ca s ion ho v s kch thch ph pht x ca nguyn t phn tch.
chnh l tc dng ca mt s hp cht, ch yu l mui halogen ca kim loi
kim v kim th hay lantan clorua.
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30
- S tng cng vch ph khi nguyn t phn tch
tn ti trong nn ca mu l nhng hp cht d ho hi. Lc cc cht nn
ny c tc dng nh l mt cht mang cho s ho hi ca nguyn t phn
tch v lm n c ho hi vi hiu sut cao hn.
- S gim cng vch ph khi nguyn t phn tch
tn ti trong nn ca mu l nhng hp cht bn nhit, kh ho hi. Lc ny
cc nguyn t nn km hm s ho hi ca nguyn t phn tch. Cc cht nn
ny thng l nhng hp cht bn vi nhit ca cc nguyn t nh Al, t
him ....
Cu 15: Phng trnh c bn ca php o AAS?
HDTL:
Trong php o ph hp th nguyn t, mi quan h gia cng ca
mt vch ph hp th ca mt nguyn t phn tch v nng ca n trong
mi trng hp th tun theo nh lut hp th quang Lambert - Beer. Ngha
l nu chiu chm tia sng n sc cng I
0
i qua mt mi trng cha
mt loi nguyn t t do nng N v c b dy L (cm), th mi quan h
gia I
0
v phn cng sng I i qua mi trng :
lg
I
I
0
= K

. N . L
lg
I
I
0
: nng lng ca tia sng b mt i do s hp th ca cc
nguyn t t do trong mi trng , n chnh l cng ca
vch hp th A

.
Ta c: A

= K . N . L
Gi C l nng ca nguyn t trong mu phn tch:
N = k . C
b


k: hng s thc nghim, ph thuc tt c cc iu kin ho hi v
nguyn t ho mu. (k = const)
b: hng s bn cht, ph thuc C (0 < b s 1)
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31
A

= K . L . C
b
; K = K.k gi l hng s thc nghim ca php o
AAS.
Tng qut: A

= a . C
b
l phng trnh c s ca phng php phn
tch nh lng da theo vic o ph hp th ca mt nguyn t xc nh
nng (hm lng) ca n.
Khong nng 0 s C s C
0
(C
0
l nng gii hn khi b bt u khc 1)
gi l khong tuyn tnh.

Cu 16: Trong php o AAS, nng ca nguyn t phn tch thng c
biu din nh th no?
HDTL:
Trong php o AAS, nng ca nguyn t phn tch c biu din
theo 4 cch sau:
* Nng phn trm (%): c biu th bng s gam ca cht phn tch c
trong 100 gam mu em phn tch: C% =
m
m
X
.100
m
X
: s gam cht phn tch c trong mu ly phn
tch m: s gam mu
phn tch.
* Nng microgam/mL hay microgam/L: c s dng ph bin trong
phn tch lng vt v c biu th theo hai cch:
+ S microgam ca cht phn tch c trong mt lit dung dch mu
( g/L) hay s microgam cht phn tch c trong mt mililit dung
dch mu ( g/L).
V d: C
Pb
= 1,2 g/L ngha l trong 1 lit dung dch mu c 1,2 g ca
Pb
+ S g ca cht phn tch c trong 1 gam mu (hoc 1kg mu).
V d: C
Pb
= 2,5

g/L th c ngha l trong 1 gam mu c 2,5

g Pb.
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32
* Nng ppm v c s ca n:
+ Vi mu rn: nu 1 gam mu c cha 10
-6

gam cht phn tch th gi
tr ny (10
-6
g) c gi l ppm. Cc c s ca n v ppm l ppb,
ppp, ppa (cc n v km nhau 1000 ln).
+ Vi mu lng: nu 1 ml mu c cha 10
-6

gam cht phn tch v khi
t trng ca dung dch mu bng 1 th i lng 10
-6
g/ml mu cng
c nh ngha l 1 ppm.
* Nng mol/l (M): biu th s phn t gam cht phn tch c trong 1 lit
dung dch mu: C
M
=
V
n

Cu 17: nhy l g? nhy ph thuc vo nhng yu t no?
HDTL:
* nhy l mt i lng ch ra kh nng ca mt
phng php phn tch theo mt k thut o no c p dng cho
phng php phn tch . Phng php phn tch c nhy cao tc l
nng gii hn di c th phn tch c l nh.
* nhy ph thuc vo nhiu yu t khc nhau nh:
+ Cc c trng, tnh cht ca h thng my o nh h
quang hc, dng c thu nhn v pht tn hiu o. chnh l cc c trng
k thut ca h thng my quang ph.
+ Cc iu kin v k thut thc hin nguyn t ho mu
o ph. V th phng php nguyn t ho trong ngn la c nhy
km hn phng php nguyn t khng ngn la.
+ Kh nng v tnh cht hp th bc x ca mi vch ph,
ca mi nguyn t. Vch ph no c kh nng hp th cng mnh th php
o theo vch c nhy cng cao. i vi mt nguyn t cc vch ph
khc nhau cng s c nhy khc nhau.
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33
Ngoi ra cn mt s yu t khc cng nh hng n nhy ca mt
phng php phn tch nh: axit ca mu, nguyn t cn tr c trong
mu.
Cu 18: Xc nh nng ca mt nguyn t trong mu phn tch theo
php o ph hp th nguyn t, ngi ta thc hin theo nhng
phng php no?
HDTL:
Da theo phng trnh nh lng c bn ca php o AAS qua vic
o cng ca vch hp th ca nguyn t phn tch v xc nh nng
ca cht phn tch trong mu o ph theo mt trong hai phng php chun
ho sau:
* Phng php ng chun: cn gi l phng php 3
mu u.
Nguyn tc: da vo phng trnh c bn ca php o: A =
K.C v mt dy mu u xy dng mt ng chun v t ng chun
ny v gi tr A
X
xc nh nng C
X
ca nguyn t cn phn tch trong
mu o ph, ri t tnh c nng ca n trong mu phn tch.
Cch x l: Trc ht ngi ta phi chun b mt dy mu
u, dy mu chun (thng thng l 5 mu u) v cc mu phn tch trong
cng mt iu kin. Sau chn cc iu kin ph hp v o cng ca
mt vch ph hp th ca nguyn t phn tch trong tt c cc mu u v
mu phn tch c chun b trn. Ta dng c mt ng biu th
mi quan h gia cc gi tr cng ng vi cc nng tng ng. l
ng chun ca phng php.
* Phng php thm tiu chun:
Nguyn tc: dng ngay mu phn tch lm nn chun b
mt dy mu u, bng cch ly mt lng mu phn tch nht nh v gia
thm vo nhng lng nht nh ca nguyn t cn xc nh theo tng
bc nng (theo cp s cng).
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34
Cch x l: Trc ht thm lng vo mu u. Tip ,
chn cc iu kin th nghim ph hp v mt vch ph ca nguyn t phn
tch, tin hnh ghi vch ph theo tt c dy mu u. T cc gi tr cng
ng vi cc nng thm vo ca nguyn t phn tch, ta dng c mt
ng, chnh l ng chun ca phng php thm.
Cu 19: Cc thng s ca h my o ph AAS thng bao gm cc yu t
no?
HDTL: Cc thng s ca h my o ph AAS thng bao gm cc yu t:
- Vch ph: vch ph c chn xc nh nguyn t m
mnh mong mun. Vch ph ny phi tho mn iu kin:
+ Khng b cc vch khc chen ln, gy nhiu hay trng lp.
+ Phi r rng v nt, c di sng chnh xc.
+ Cng vch ph hp th A phi ph thuc tuyn tnh vo nng
C trong mt vng nng nht nh.
+ Vch ph phi nm trn mt nn khng qu ti.
+ Tt nhin khi cn xc nh cc nng rt nh th phi chn vch
ph c nhy cao v ngc li.
- Cng n n catot rng (HCL): cng dng in
lm vic ca HCL nn chn cng dng nm trong vng t 60% - 85%
so vi cng cc i ghi trn HCL. Khi cn nhy cao th chn cn
di, khi cn n nh th chn cn trn.
- Khe o ca my quang ph: nn chn mt gi tr ph hp
nht cho php o nh lng mt nguyn t theo vch ph c chn,
lm sao ch cho va vch ph cn o vo khe o l tt nht.
- Chiu cao n nguyn t ho mu: Burner head Hight.
- Thi gian o: ph thuc c trng k thut tng my o
ph.
- Lng mu: tc dn mu, lng mu bm vo.
- Vng tuyn tnh: c chn nh lng.
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35
- Phng tin ch th kt qu o.
- B chnh nn khi o: ph thuc vo vch ph khi o.
- Nhn quang nhn tn hiu AAS: l thang nng lng hp
th ca php o AAS.
Cu 20: Cc phng php xc nh trc tip theo AAS gm my giai on?
cc giai on xy ra nh th no?
HDTL:
V nguyn tc th tt c cc nguyn t v cc cht c ph hp th
nguyn t chng ta u c th xc nh n mt cch trc tip theo ph hp
th nguyn t ca n t dung dch mu phn tch. Ngha l cc phng php
xc nh trc tip ch ph hp cho vic xc nh cc kim loi c vch ph
hp th nguyn t. V cc kim loi u c ph hp th nguyn t ca trong
nhng iu kin nht nh.
V d: cc mu v c l qung, t, , khong liu, mui, oxit, kim
loi, xi mng, hp kim, nc, khng kh v cc mu hu c l cc mu thc
phm, ng .... Khi phn tch cc loi mu ny th nguyn tc chung gm 2
giai on:
* Giai on 1: X l mu a nguyn t kim loi cn xc nh c trong
mu v trng thi dung dch ca cc cation theo mt k thut ph hp
chuyn c hon ton nguyn t cn xc nh vo dung dch o ph.
* Giai on 2: Phn tch nguyn t cn thit theo ph hp th nguyn t ca
n theo nhng iu kin nht nh ph hp c nghin cu v chn ra.
y, giai on 1 l cc k quan trng. V nu x l mu khng tt
th c th lm mt nguyn t cn phn tch hay lm nhim bn thm vo.
Ngha l vic x l mu khng ng s ngun sai s rt ln cho kt qu phn
tch, mc d phng php phn tch chn ph hp.
Cu 21: Ti sao n catot rng l ngun c s dng ph bin nht?
HDTL:
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36
- n pht tia bc x n sc c dng sm nht v ph
bin nht trong php o AAS l n catot rng v n ny ch pht ra nhng
tia pht x nhy ca nguyn t kim loi lm catot rng. Cc vch pht x
nhy ca mt nguyn t thng l cc vch cng hng. V th n catot
rng cng c gi l ngun pht tia bc x cng hng. N l ph pht x
ca cc nguyn t trong mi trng kh km.
- Cu to ca n catot rng:

Hnh 2.5 n catot rng
1. Bng thu tinh. 2. Anot 3.Catot 4.Ca s thch anh
n catot rng l mt bng thu tinh hnh tr, ng knh 3 - 5cm, c
ca s bng thu tinh hay thch anh. Anot c ch to t thanh kim loi.
C hai cc c t trong bng thu tinh c cha kh tr (agon hay neon)
vi p sut khng ln (0,2 - 2MPa). n catot rng c ni vi dng in
300 - 500V, n nh v phi c n nh cao. Dng phng ca n thng
l vi miliampe. Khi n lm vic, mt dng mt bn trong catot cao
hn mt ngoi. V vy ti l m ca catot s pht sng. Catot ca n c
ch to ca kim loi, hp kim kh nng chy c cha nguyn t cn xc
nh.

Cu 22: Hy nu nhng thnh phn chnh ca n catot rng?
HDTL:
n catot rng gm 3 phn chnh: (xem hnh 2.5)
Phn 1 l thn n v ca s.
Phn 2 l cc in cc cato v anot.
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37
Phn 3 l kh cha trong n. l kh tr He, Ar hay Nit.
+ Thn v v: Thn n gm c v n, ca s v b
cc in cc anot v catot. B bng nha PVC. Thn v v n bng thu
tinh hay thch anh. Ca s S ca n c th l thu tinh hay thch anh trong
sut trong vng UV hay VIS l tu thuc vo loi n ca tng nguyn t
pht ra chm tia pht x nm trong vng ph no.
+ in cc: in cc ca n l catot v anot. Anot c
ch to bng kim loi tr v bn nhit nh W hay Pt. Catot c ch to c
dng hnh xylanh hay hnh ng rng c ng knh t 3 - 5mm, di 5 - 6mm
v chnh bng kim loi cn phn tch vi tinh khit cao (t nht 99,9%).
Dy dn ca catot cng l kim loi W hay Pt. Ngun nui l ngun 1 chiu
c th 220 - 240V.
+ Kh trong n: Trong n phi ht ht khng kh v np
thay vo l mt kh tr vi p sut t 5 - 15mmHg. Kh tr l agon,
heli hay nit nhng phi c sch cao hn 99,99%. Kh np vo n phi
khng pht ra ph lm nh hng n chm tia pht x ca n v khi lm
vic trong iu kin nht nh th t s tu thuc vo tng loi n v tng
nguyn t kim loi lm catot rng. Cng lm vic ca n catot rng
thng l t 3 - 50mA.
II.3. BI TP:
Dng 1: Xc nh nng ca kim loi trong mu, khi bit hm lng kim
loi trong dung dch chun v hp th.

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38
Cch gii:
p dng phng php hi quy tuyn tnh theo nguyn l bnh phng
ti thiu, ta xy dng ng chun: A = aC + b.
Tnh a, b?
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
; b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.

Bi 1: Ngy nay, xc nh s nhim thu ngn ca cc dung dch nc
bng phng php hp th nguyn t ngi ta dng phng php khng
ngn la mi ca s phun m. Thit b gm mt bnh kh thu ngn ni
vi mt cuvet hp th. 10ml mu nc vo bnh kh thu ngn v pha
long n 100ml, sau thm vo 25ml axit sunfuric c v 10ml dung dch
thic (II) sunfat 10%, axit sunfuric 0,25M (dung dch cui ny dng lm cht
kh). Thu ngn b kh n trng thi nguyn t (nguyn t) v c
chuyn vo cuvet hp th bi dng khng kh, ngi ta cho dng khng kh
ny i qua dung dch trong bnh kh thu ngn. Cui cng, dng n
catot rng lm ngun, ngi ta o s hp th ca cc nguyn t thu ngn
bc sng 2537A
0
, s hp th t c mc cc i gn 3 pht.
Ngi ta nhn c cc gi tr sau ca hp th i vi dy cc dung dch
chun ca thu ngn (II):
Hm lng Hg trong dung dch chun, g hp th
0,00 0,002
0,30 0,090
0,60 0,175
1,00 0,268
2,00 0,440

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39
Cc gi tr ca hp th ca hai mu nc bng 0,040 v 0,305 tng ng.
Vy hm lng ca thu ngn trong tng mu bng bao nhiu? Nng
( ml g / ) ca thu ngn trong tng mu bng bao nhiu? [28]
Gii:
Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l bnh
phng ti thiu A = aC + b :

STT Hm lng Hg (C) hp th (A) A.C C
2
1 0,00 0,002 0,000 0,000

2 0,30 0,090 0,027 0,090
3 0,60 0,175 0,105 0,360
4 1,00 0,268 0,268 1,000
5 2,00 0,440 0,880 4,000
n=5
C

= 3,9 A

= 0,975 AC

=1,28
2
C

= 5,45

n n n
i i i i
i 1 i 1 i 1
2 2
n n
2
i i
i 1 i 1
n A C A C
5.1, 28 0, 975.3, 9
a
5.5, 45 3.9
n C C
= = =
= =

= =

| |

|
|
\ .


= 0,2157
n n n n
2
i i i i i
i 1 i 1 i 1 i 1
2 2
n n
2
i i
i 1 i 1
A C A C C
0, 975.5, 45 1, 28.3, 9
b
5.5, 45 3.9
n C C
= = = =
= =

= =

| |

|
|
\ .


= 0,02672

Phng trnh hi quy thu c l: A = 0,2157C + 0,0267
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
40
* Vi A = 0,040 thay vo phng trnh thu c hm lng thu ngn:
0,040 = 0,2157C + 0,02672
Suy ra C = 0,0617 g ng vi nng 0,00617 g/ml.
* Vi A = 0,305 thay vo phng trnh thu c hm lng thu ngn:
0,305 = 0,2157C + 0,02672
Suy ra C = 1,2902 g ng vi nng 0,12902 g/ml.

Bi 2: C th dng php o ph hp th nguyn t xc nh cc vt cc
kim loi nng trong du mazut. phn tch 5,000 gam mu ca loi du
mazut dng, ngi ta t vo mt bnh nh mc c dung tch 25,00 ml,
ho tan vo 2 - metyl - 4 - pentanol v bng dung mi ny a th tch trong
bnh n vch. Sau phun m dung dch nhn c trong ngn la khng
kh - axetylen. xc nh ng v ch cn dng cc n catot rng vi cc
vch pht x 324,7 v 283,3 nm tng ng. nhn c cc th chun
cn mt dy cc dung dch chun cha nhng lng bit ca ng v ch
trong hn hp tng ng vi du mazut cha dng v 2-metyl-4-pentanol.
Xy dng phng trnh hi quy ca ng v ch trong 5,000 gam mu du
mazut dng theo cc s liu sau:

Dung dch
hp th
283,3 nm (Pb) 324,7 nm (Cu)
a, Chun: 19,5 ml g / Pb 5,25 ml g / Cu 0,356 0,514
b, Chun: 4,00 ml g / Pb 4,00 ml g / Cu 0,073 0,392
c, Chun: 12,1 ml g / Pb 6,27 ml g / Cu 0,220 0,612
d, Chun: 8,50 ml g / Pb 0,155 0,101
, Chun: 15,2 ml g / Pb 2,40 ml g / Cu 0,277 0,232
e, Cha bit 0,247 0,371
Gii:
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
41
Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l bnh
phng ti thiu A = aC + b :
Stt Hm lng ch (C) hp th (A) A.C C
2
1 4,00 0,073 0,292 16,000
2 8,50 0,155 1,318 72,250
3 12,1 0,220 2,662 146,410
4 0,00 0,247 0,000 0,000
5 15,2 0,277 4,210 231,040
6 19,5 0,356 6,942 380,250

C = 59,3 A = 1,382 AC = 15,424 C
2
= 845,950
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
3 , 59 950 , 845 . 6
3 , 59 . 328 , 1 424 , 15 . 6

= 0,1099
b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
3 , 59 950 , 845 . 6
3 , 59 . 424 , 15 95 , 845 . 328 , 1

= 0,1339
Phng trnh hi quy thu c l: A = 0,1099C + 0,1339
Stt Hm lng ng (C) hp th (A) A.C C
2
1 0,00 0,101 0,000 0,000
2 2,40 0,232 0,557 5,760
3 0,00 0,371 0,000 0,000
4 4,00 0,392 1,568 16,000
5 5,25 0,514 2,699 27,563
6 6,27 0,612 3,837 39,313
C = 17,92 A = 2,222 AC = 8,661 C
2
= 88,635
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
92 , 17 635 , 88 . 6
92 , 17 . 222 , 2 661 , 8 . 6

= 0,0557
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
42
b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
92 , 17 635 , 88 . 6
92 , 17 . 661 , 8 635 , 88 . 222 , 2

= 0,1981
Phng trnh hi quy thu c l: A = 0,0557C + 0,1981
Bi 3: xc nh hm lng ng trong mu FFDT (mu cht bo t do
kh thu c t dch chit khp chn), ngi ta dng 11,23 mg FFDT pha
trong bnh 5,00 ml bng dung dch HNO
3
0,75 M n vch. Tin hnh o
ph hp th nguyn t dng ngn la khng kh - axetylen thu c hp
th 0,023 bc sng 324,8 nm. Tin hnh o cc dung dch chun trong
iu kin tng t, kt qu thu c nh sau :
ppm Cu 0,000 0,100 0,200 0,300 0,400 0,500 0,600 0,700 1,000
hp th 0,000 0,006 0,013 0,020 0,026 0,033 0,039 0,046 0,066
Nng ca ng (g/gam FFDT) l bao nhiu?
Gii: Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l
bnh phng ti thiu A = aC + b :
Stt Hm lng ng (C) hp th (A) A.C C
2
1 0,000 0,000 0,000 0,000
2 0,100 0,006 0,001 0,010
3 0,200 0,013 0,003 0,040
4 0,300 0,020 0,006 0,090
5 0,400 0,026 0,010 0,160
6 0,500 0,033 0,017 0,250
7 0,600 0,039 0,023 0,360
8 0,700 0,046 0,032 0,490
9 1,000 0,066 0,066 1,000
n = 9
C = 3,800 A = 0,249 AC = 0,158 C
2
=
2,400
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
43
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
800 , 3 400 , 2 . 9
800 , 3 . 249 , 0 158 , 0 . 9

= 0,0665
b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
800 , 3 400 , 2 . 9
800 , 3 . 158 , 0 400 . 2 . 249 , 0

= - 0,00039
Phng trnh hi quy thu c l: A = 0,0665C - 0,00039
(C l nng ppm Cu) thay A = 0,023
C = 0,352 ppm = 0,352 g/ml
Hm lng Cu :
gam
ml ml g
01123 , 0
5 . / 352 , 0
= 157 gCu/gam FFDT.
Bi 4: Mt nh phn tch a ra kt qu d liu xy dng ng chun
phn tch hm lng photpho bng ph hp th nguyn t ngn la :
ppm P 2130 4260 6400 8530
hp th 0,048 0,110 0,173 0,230

xc nh tinh khit ca mu Na
2
HPO
4
, ngi ta ho tan 2,469 gam
mu vo nc, chuyn vo bnh nh mc 100,00 ml v nh mc n vch.
hp th nguyn t ca mu thu c l 0,135. Xc nh tinh khit ca
mu Na
2
HPO
4
.

Gii:
Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l bnh
phng ti thiu A = aC + b:
Stt Hm lng
phot pho (C)
hp th
(A)
A.C C
2
1 2130 0,048
102,2400 4536900
2 4260 0,110
468,6000 18147600
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
44
3 6400 0,173
1107,2000 40960000
4 8530 0,230
1961,9000 72760900
n =4
C = 21320 A = 0,561 AC = 3639,940 C
2
= 136405400
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
21320 136405400 . 4
21320 . 561 , 0 940 , 3639 . 4

= 2,854.10
-5
b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
21320 136405400 . 4
21320 . 940 , 3639 136405400 . 561 , 0

= -0,0119
Phng trnh hi quy thu c l: A = 2,854.10
-5
C - 0,0119
(C l nng ppm Cu) thay A = 0,135
C = 4896,7 ppm = 4896,7 g/ml
Hm lng P : 4896,7 g/ml . 100,00ml = 489670 g ~ 0,490g
Khi lng Na
2
HPO
4
tinh khit l:
31
490 , 0
.142 = 2,243gam, tinh khit
91%.
Bi 5: Ch c xc nh bng phng php hp th nguyn t ngn la.
gim nh hng nhiu, phng php thm chun c s dng. Tin hnh
chun b ba mu, mi mu cha 5,00 ml dung dch mu cn xc nh hm
lng ch, trong mu th nht thm vo 5,00 ml nc ct. Mu th hai c
thm 1,00 ml dung dch ch nitrat 10,0 M v 4,00 ml nc ct. Cn mu th
ba c thm 2,00 ml dung dch ch nitrat 10,0 M v 4,00 ml nc ct. Ba
mu em o ph hp th nguyn t, hp th thu c ln lt l: 0,13;
0,30 v 0,47. Hy xc nh hm lng ch trong mu ban u?
Gii:
- Gi nng ch trong mu ban u l C
o
(M), trong mu th nht l:
C
X
=
5, 00
5, 00 5, 00 +
C
o
= 0,5C
o

S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
45
- Nng ch trong mu th 2 l C
X
+
1, 00.10, 0
5, 00 1, 00 4, 00 + +
= C
X
+ 1,00 (M)
- Nng ch trong mu th 3 l C
X
+
2, 00.10, 0
5, 00 2, 00 3, 00 + +
= C
X
+ 2,00 (M)
V hp th ph thuc tuyn tnh vo nng nn s dng phng php
th theo bng s liu :
hp th 0,13 0,30 0,47
Nng ch (M ) 0 1,00 2,00
(Ngoi suy th, im ct trc honh l -C
x
= 0,5C
o
;) hoc xy dng ng
hi qui tuyn tnh A = aC + b v cho A = 0 thu c C
X
= - C.
Stt Hm lng P (C) hp th (A) A.C C
2
1 0 0,13
0,0000 0,00
2 1,00 0,30
0,3000 1,00
3 2,00 0,47
0,9400 4,00
n =3
C = 3,00 A = 0,90 AC = 1,24 C
2
= 5,00
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
00 , 3 00 , 5 . 3
00 , 3 . 90 , 0 24 , 1 . 3

= 0,17

b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
00 , 3 00 , 5 . 3
00 , 3 . 24 , 1 00 , 5 . 90 , 0

= 0,13
Phng trnh hi quy thu c l: A = 0,17C + 0,13
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
46
y = 0,17x + 0,13
R
2
= 1
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
0,5
-2 -1 0 1 2 3

Hnh 2.6: ng thm chun xc nh hm lng ch
Kt qu thu c A = 0,17C + 0,13 - C = C
X
= 0,7647 = 0,5C
o
.
Vy nng ch trong mu ban u l: C
o
= 1,5294 M.

Bi 6: Canxi trong dung dch mu c xc nh bng phng php quang
ph hp th nguyn t. Dung dch chun c chun b bng cch ho tan
1,834 gam CaCl
2
.2H
2
O trong nc, pha long thnh 1,00 lt, dung dch ny
c pha long 1: 10. Cc dung dch chun o c chun b bng cch
pha long dung dch th hai theo t l 1:20; 1:10 v 1:5. Mu c pha long
theo t l 1:25. Dung dch SrCl
2
c thm vo cc dung dch trc khi pha
long t 1% (gam/100ml) trnh nh hng photphat. Mu trng c
chun b l dung dch SrCl
2
1%. Tn hiu hp th c ghi khi cc dung
dch c phun vo ngn la khng kh - axetylen cho kt qu sau :
Mu Trng Mu 1:20 Mu 1:10 Mu 1:5 Mu phn tch
hp th 1,5 10,6 20,1 38,5 29,6
Xc nh nng canxi trong mu di dng ppm?
Gii:
- Nng Ca trong dung dch chun:
+ Dung dch thu c khi pha 1,834 gam/L l:
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
47
1,834
.40
147
gam Ca/L
+ Dung dch thu c khi pha t l 1:10 l:
1,834
.4
147
= 0.050 gam Ca/L = 50 mg Ca/L.
hay nng Canxi theo ppm l: 50 ppm.
- Gi nng Ca trong mu phn tch l C
o
(ppm).
Nng Ca trong cc dung dch o v tn hiu hp th tng ng l:
Mu Trng Mu 1:20 Mu 1:10 Mu 1:5 Mu phn tch
Nng (ppm) 0 2,5 5,0 10,0 C
o
/25
hp th 1,5 10,6 20,1 38,5 29,6
- Xy dng s ph thuc hp th A vo nng da trn nguyn l bnh
phng ti thiu A = aC + b:
Mu Nng
(C)
hp th (A) A.C C
2
Trng 0 1,5 0 0
Mu 1:20 2,5 10,6 26,5 6,25
Mu 1:10 5,0 20,1 100,5 25,0
Mu 1:5 10,0 38,5 385,0 100,0
n =4
C = 17,5 A = 70,7 AC = 512,0 C
2
= 131,25
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
5 , 17 25 , 131 . 4
5 , 17 . 7 , 70 0 , 512 . 4

= 3,7063

b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
5 , 17 25 , 131 . 4
5 , 17 . 0 , 512 25 , 131 . 7 , 70

= 1,46
- Phng trnh hi qui thu c: A = 3,7063.C + 1,46
- Hm lng Ca trong mu:
o
C A 1, 46 29, 6 1, 46
25 3, 7063 3, 7063

= = C
o
= 189,8 ppm.
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
48
Bi 7: Clorua trong mu nc c xc nh gin tip bng phng php
quang ph hp th nguyn t bng cch lm kt ta hon ton n di dng
AgCl vi lng d chnh xc AgNO
3
, lc b kt ta o nng cn li ca
Ag trong dung dch nc lc. 10,00 ml ca cc dung dch mu v dung dch
chun 100 ppm clorua c cho vo bnh eclen 100,0 ml kh, thm vo mi
bnh 25,0 ml dung dch AgNO
3
, sau mt thi gian kt ta hon ton, lc
chuyn cc hn hp sang cc ng li tm kh v em li tm. Mi dung dch
nc lc (sau li tm) c phun vo bung nguyn t ho xc nh
hp th. Mu trng c chun b tng t khi dng 10,0 ml nc ct. Kt
qu thu c trn bng sau:
Mu Mu trng Mu chun Mu phn tch
hp th (chiu cao
vch hp th (cm))
12,8 5,7 6,8
Nng ca clorua trong mu phn tch ban u l bao nhiu ?

Gii:
- Gi nng ca AgNO
3
trong dung dch chun gc l C
01
mM.
- Phn ng xy ra trong qu trnh chun b mu l :
Ag
+
+ Cl
-
AgCl
- Nng Ag
+
trong mu trng :
25, 0
V
C
01
= C
1
(mM)
- Nng Ag
+
trong mu chun :
o1
100
25, 0C 10
35, 5
V

= C
2
(mM)
- Nng Ag
+
trong mu phn tch :
o1 o
X
25, 0C 10, 0C
V

= C
3
(mM)
- Nng v tn hiu ca cc dung dch o:
Mu Mu trng Mu chun Mu phn tch
Nng C
1
C
2
C
3
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
49
hp th (chiu cao
vch hp th (cm))
12,8 5,7 6,8
- Ta c : A
1
= KC
1
= 12,8 (1)
A
2
= KC
2
= 5,7 (2)
A
3
= KC
3
= 6,8 (3)

o1
1
o1
2
C 12, 8 25C
100
C 5, 7
25C 10
35, 5
= =

C
01
= 2,0313 mM.

1
3
C 12,8
C 6,8
= =
o1
o1 o
X
25, 0C
25, 0C 10, 0C
C
X
o
= 2,3804 mM.
Hm lng clorua trong mu l: 2,3804.35,5 = 84,5 ppm.

Bi 8: Bonert and Pohl bo co kt qu phn tch ph hp th nguyn t i
vi mt s kim loi trong cc sn phm ph ca qu trnh sn xut soda bng
phng php ammonia-soda.
a, Nng ca Cu c xc nh bng cch axit ho 200 ml mu bng 20,0
ml dung dch HNO
3
, thm vo 1,0 ml dung dch H
2
O
2
27% (khi lng/th
tch) v un si trong 30 pht. Dung dch thu c c pha long thnh
500 ml v em phn tch hp th nguyn t. Kt qu phn tch cho trn bng:
Mu Nng Cu (ppm) hp th
trng 0 0.007
chun 1 0.200 0.014
chun 2 0.500 0.036
chun 3 1.000 0.072
chun 4 2.000 0.146
phn tch 0.027
Hy xc nh nng ca Cu trong mu phn tch?
b, Nng ca Cr c xc nh bng cch axit ho 200 ml mu bng 20,0
ml dung dch HNO
3
, thm vo 0,20 gam Na
2
SO
3
v un si trong 30 pht.
Lng Cr c tch t mu bng cch thm 20 ml NH
3
to ra kt ta cha
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50
Cr v mt s oxit khc. Kt ta c tch ra, ra chuyn qua vi nc ra
vo cc. Sau khi c axit ho bng 10 ml dung dch HNO
3
, c lm bay
hi n kh. Cn rn c ho tan li bng dung dch HNO
3
v HCl, lm
bay hi n kh. Cui cng cn rn c ho tan trong 5,00 ml dung dch
HCl v pha long thnh 50,00 ml. Dung dch thu c em phn tch bng
phng php thm chun. Kt qu hp th nguyn t c tng hp trn
bng sau:
Mu Nng Cr thm (ppm) hp th
trng 0 0.001
mu 0 0.045
thm chun 1 0.200 0.083
thm chun 2 0.500 0.118
thm chun 3 1.000 0.192
Hy xc nh nng ca Cu trong mu phn tch?
Gii:
a) - Xy dng s ph thuc hp th A vo nng da trn nguyn l
bnh phng ti thiu A = aC + b:
Mu Nng (C) hp th (A) A.C C
2
Trng 0 0,007 0 0
Chun 1 0,200 0,014 0,003 0,040
Chun 2 0,500 0,036 0,018 0,250
Chun 3 1,000 0,072 0,072 1,000
Chun 4 2,00 0,146 0,292 4,000
n =5
C = 3,700 A = 0,275 AC = 0,385 C
2
= 5,290
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
700 , 3 290 , 5 . 5
700 , 3 . 275 , 0 385 , 0 . 5

= 0,071

S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
51
b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
700 , 3 290 , 5 . 5
700 , 3 . 385 , 0 290 , 5 . 275 , 0

= 0,0024
- Phng trnh hi qui thu c: A = 0,071C + 0,0024 C = 0,3465 ppm
- Hm lng Cu trong mu :
o
500, 00.C
C 0,866ppm
200, 00
= = .
b) Xy dng th thm chun vi s hiu chnh mu trng:
V hp th ph thuc tuyn tnh vo nng nn s dng phng php
th theo bng s liu:
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52

Mu Nng (C) hp th (A) A.C C
2
Mu 0 0,045 0,001 0 0
Chun 1 0,200 0,083 0,001 0,016 0,040
Chun 2 0,500 0,118 0,001 0,059 0,250
Chun 3 1,000 0,192 0,001 0,191 1,000
n = 4
C = 1,700 A = 0,434 AC = 0,266 C
2
= 1,290

(Ngoi suy th, im ct trc honh l -C
x
= 0,5C
o
;) hoc xy dng ng
hi qui tuyn tnh A = aC + b v cho A = 0 thu c C
X
= - C.
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
700 , 1 290 , 1 . 4
700 , 1 . 434 , 0 266 , 0 . 4

= 0,1435

b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
700 , 1 290 , 1 . 4
7 , 1 . 268 , 0 290 , 1 . 438 , 0

= 0,0475
- Phng trnh hi qui thu c: A = 0,1435C + 0,0475
y = 0.1435x + 0.0475
R
2
= 0.9957
0
0.05
0.1
0.15
0.2
0.25
-1 -0.5 0 0.5 1 1.5

Hnh 2.7: ng thm chun xc nh hm lng ng
Kt qu thu c A = 0,1435C + 0,0475 - C = C
X
= 0,331.
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53
Vy nng ch trong mu ban u l: C
o
=
50, 00.0, 331
200, 00
= 0,0828 ppm.

Bi 9: Quigley v Vernon bo co kt qu xc nh lng vt kim loi trong
nc bin bng quang ph hp th nguyn t dng l graphit s dng
phng php thm chun. Lng vt cc kim loi u tin c tch t cc
phc ca chng, lng mui ln c ng kt ta vi Fe
3+
. Theo phng
php

ny 5,0 ml dung dch Fe
3+
2000 ppm c thm vo 1,00 lt nc bin.
Dng NH
3
iu chnh pH dung dch n 9,0 v kt ta Fe(OH)
3
c qua
m. Sau khi tch, ra kt ta, Fe(OH)
3
v lng cc kim loi ng kt ta
c ho tan trong 2,0 ml HNO
3
c v pha long thnh 50,00 ml. phn
tch Mn
2+
, 1,00 ml mu thu c c pha long thnh 100,0 ml v bm
mu vo l graphit v phn tch :
Mu hp th
2,5 l mu + 2,5 l dung dch 0 ppb Mn
2+
chun 0.223
2,5 l mu + 2,5 l dung dch 2,5 ppb Mn
2+
chun 0.294
2,5 l mu + 2,5 l dung dch 5,0 ppb Mn
2+
chun 0.361

Hy tnh kt qu theo part per billion (ppb) ca Mn
2+
trong mu nc bin?
Gii:
- Nng Mn
2+
trong 100,0 ml l C
X
(ppb)
- Nng Mn
2+
trong mu o 1 l 0,5C
X

- Nng Mn
2+
trong mu o 2 l 0,5C
X
+ 1,25 (ppb)
- Nng Mn
2+
trong mu o 3 l 0,5C
X
+ 2,50 (ppb)
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54

Mu Nng (C) hp th (A) A.C C
2
Chun 1 0 0,223 0 0
Chun 2 2,5/2 0,294 0,368 1,563
Chun 3 5,0/2 0,361 0,903 6,250
n = 3 3,75 0,878 1,270 7,813
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
75 , 3 813 , 7 . 3
75 , 3 . 878 , 0 270 , 1 . 3

= 0,0552
b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
75 , 3 813 , 7 . 3
75 , 3 . 270 , 1 813 , 7 . 878 , 0

= 0,2237
y = 0.0552x + 0.2237
R
2
= 0.9997
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
-8 -6 -4 -2 0 2 4 6

Hnh 2.8: ng thm chun xc nh hm lng mangan
Da trn th hay phng trnh ng thm chun A = 0,0552C + 0,2237
ta tnh c: 0,5C
X
= -C = 4,0525 ppb C
X
= 8,105 ppb.

Hm lng Mn
2+
trong nc bin l :
100, 00.8,105 50, 00
.
1, 00 1000
= 40,525 ppb.

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55
Dng 2: Xc nh hp th ca nguyn t kim loi.
Cch gii:
p dng nh lut Bouguer Lambert Beer:

A = lg
I
I
0
= C l. .

c
Trong : A: mt quang.
I
0
, I: cng nh sng trc v sau khi b nguyn t t do hp
th.

c : h s hp th mol phn t, ph thuc bc sng .


l: dy lp hi nguyn t.
Bi 10: Dung dch 12 ppm ca ch cho tn hiu hp th nguyn t l 8%,
nhy hp th nguyn t ca ch l bao nhiu? (Bit nhy hp th nguyn
t l
lng ti thiu ca cht hp th hp th l 1%).

Gii:
Ta c : A =
I
I
0
lg =
thu hap
I I
I

0
0
lg = K.C
K =
C
1
lg
8 100
100

=
12
1
lg
8 100
100

= 3,0177.10
-3

Mt khc: khi hp th l 1% th gi tr ca nng l nhy hp th
nguyn t :
o
3
I 1 1 100
C lg lg
K I 100 1
3, 0177.10

= = =

1,45 ppm.

Bi 11: nhy hp th nguyn t ca bc l 0,050 ppm trong mt iu
kin xc nh. hp th thu c s l bao nhiu i vi dung dch cha
0,70 ppm bc?
Gii:
o
I 100
A lg KC K.0, 050 lg
I 100 1
= = =


K = 8,7296.10
-2

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56

o
I
A lg KC 0, 0611
I
= = =

o
ht
I 100
A lg lg 0, 0611
I 100 I
= = =


I
ht
= 13,13%.
Bi 12: xc nh hm lng ch trong nc tiu nh php o ph hp th
nguyn t c th dng phng php thm chun. Tng 50,00ml nc tiu
c chuyn vo mi phu di c dung tch 100ml, thm vo mt phu
300 l dung dch chun cha 50,0 mg/l ch. Sau pH ca mi hn hp
c a n 2,8 bng cch thm tng git dung dch HCl. Trong mi phu
ngi ta a vo 500 l dung dch amoni pyroliinithiocacbaminat mi
chun b 4% trong metyl- n - amylxeton, trn cn thn cc pha nc v pha
hu c chit ch. Hm lng ca ch trong pha hu c c xc nh
bng phng php hp th nguyn t, mt khc ngi ta dng n catot rng
vi ng hp th 283,3 nm. Nng ch bng bao nhiu mg/l trong mu
nc tiu ban u, nu s hp th ca dch chit ca mu khng thm ch l
0,325, cn dch chit ca mu pha thm lng bit ca ch l 0,670?
Gii:
Gi s nng ch trong mu nc tiu l C
o
g/ml, khi chit vo 0,5 ml
metyl-n-amylxeton th nng trong pha hu c l : C
X
= 100C
o
.
Khi thm vo dung dch 0,3 ml dung dch ch 50,0 g/ml, khi chit vo 0,5
ml metyl-n-amylxeton th nng trong pha hu c l:
C = 100C
o
+ 30,0
hp th trong vng tuyn tnh nn:
o
x x
o
t t
A C 100C 0, 325
A C 0, 670
100C 30
= = =
+
= 0,02826 g/ml

Dng 3: Xc nh bc sng (m); tn s (s
-1
) hay (hec); s sng (cm
-1
); nng
lng (J.mol-1), khi bit mt trong cc s liu trn.
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57
Cch gii:
* p dng cng thc:

hc
E = A
v v h E= A

v
c
=
s sng
v

1
(cm
-1
)
Trong : c: tc nh sng = 3.10
8
m/s
: bc sng ca bc x.
v : tn s ca bc x.
* Qui i n v:
1cm = 10
-2
m ; 1 m = 10
-6
m ; 1nm = 10
-9
m ; 1
o
A = 10
-10
m ;


Bi 13: Hy tnh tn s v (trong giy
-1
) tng ng vi mi mt trong cc
bc sng sau ca bc x n sc?
a, 222nm b, 530nm c, 17
o
A

Gii:
a, Ta c: 222nm = 222.10
-9
m
p dng cng thc:

v
c
= =
9
8
10 . 222
10 . 3

= 1,35.10
15
giy
-1

b, Ta c: 530nm = 530.10
-9
m
p dng cng thc:

v
c
= =
9
8
10 . 530
10 . 3

= 5,66.10
14
giy
-1

c, Ta c: 17
o
A = 17.10
-10
m
p dng cng thc:

v
c
= =
10
8
10 . 17
10 . 3

= 1,76.10
17
giy
-1

Bi 14: Hy tnh tn s v (trong hec) tng ng vi mi mt trong cc bc
sng sau ca bc x n sc?
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58
a, 0,030cm b, 1,3.10
-7
cm c, 6,1 m
Gii:
a, Ta c: 0,030cm = 3.10
-4
m
p dng cng thc:

v
c
= =
4
8
10 . 3
10 . 3

= 1.10
12
hec
b, Ta c: 1,3.10
-7
cm = 1,3.10
-9
m
p dng cng thc:

v
c
= =
9
8
10 . 3 , 1
10 . 3

= 2,31.10
17
hec
c, Ta c: 6,1 m = 6,1.10
-6
m
p dng cng thc:

v
c
= =
6
8
10 . 1 , 6
10 . 3

= 4,92.10
13
hec

Bi 15: Hy tnh s sng

v (trong cm
-1
) cc bc sng v xc nh vng
ph tng ng?
a, 1,3.10
-7
cm b, 5,6 m c, 530nm

Gii:
p dng cng thc:
c
v

v = =

1
v da vo s phn b cc dng bc x theo
cc bc sng v s sng:
a, Ta c: 1,3.10
-7
cm

v =
7
10 . 3 , 1
1

= 7,69.10
6
cm
-1
vng Rnghen
b, Ta c: 5,6 m = 5,6.10
-4
cm

v =
4
10 . 6 , 5
1

= 1,79.10
5
cm
-1
vng hng ngoi gn
c, Ta c: 530nm = 5,30.10
-5
cm

v =
5
10 . 3 , 5
1

= 1,89.10
4
cm
-1
vng nhn thy
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59
Bi 16: Hy tnh di sng (trong cm v nm) tng ng vi cc tn s sau
ca bc x in t?
a, 1,97.10
9
hec
b, 4,86.10
15
hec
Gii:
p dng cng thc:

v
c
=
v

c
=
a, =
9
8
10 . 97 , 1
10 . 3
= 1,52.10
-1
m = 15,2cm = 1,52.10
8
nm
b, =
15
8
10 . 86 , 4
10 . 3
= 6,17.10
-6
cm = 61,7 nm
Bi 17: Hy tnh s sng (trong cm
-1
) trong cc trng hp sau v xc nh
vng ph ca n?
a, 7,32.10
19
hec
b, 2,31.10
17
hec
Gii:
p dng cng thc:
c
v
v =

v da vo s phn b cc dng bc x theo cc


bc sng v s sng:
a,

v =
8
19
10 . 3
10 . 32 , 7
= 2,44.10
9
cm
-1
vng
b,

v =
8
17
10 . 3
10 . 31 , 2
= 7,7.10
7
cm
-1
vng Rnghen
Bi 18: B sung nhng gi tr cn thiu trong bng sau :
Bc sng (nm) Tn s s
-1
S sng (cm
-1
) Nng lng (J.mol
-1
)
1,01.10
-8



1,33.10
15



3215


7,20.10
-19
Gii:
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60
Bc sng (m) Tn s s
-1
S sng (cm
-1
) Nng lng (J.mol
-1
)
4,50.10
-9
6,67.10
16
2,22.10
6
4,42.10
-17
2,26.10
-7
1,33.10
15
4,42.10
4
8,81.10
-19
3,11.10
-6
9,65.10
13
3215 6,39.10
-20
2,76.10
-7
1,09.10
15
3,62.10
4
7,20.10
-19
Bi 19: B sung nhng gi tr cn thiu trong bng sau :
Bc sng (nm) Tn s (hec)

S sng (cm
-1
) Nng lng (J.mol
-1
)

1,97.10
-24


42

1,18.10
10
3,02.10
6

Gii:
Bc sng (nm) Tn s (hec)

S sng (cm
-1
) Nng lng (J.mol
-1
)
1,01.10
8
2,97.10
9
99.10
-3
1,97.10
-24
2,38.10
5
1,26.10
12
42 8,35.10
-22

2,55.10
7
1,18.10
10
39,2.10
-2
7,82.10
-14
3,02.10
6
0,99.10
11
33.10
-1
6,56.10
-23

Kt lun chng II: Chng Phng php phn tch Quang ph hp
th nguyn t : xy dng h thng cu hi t lun v h thng bi tp
c phn loi theo cc dng bi tp v xut cch gii: Xc nh nng
ca kim loi trong mu, khi bit hm lng kim loi trong dung dch chun
v hp th. Xc nh hp th ca nguyn t kim loi. Xc nh bc
sng (m); tn s (s
-1
) hay (hec); s sng (cm
-1
); nng lng (J.mol
-1
).
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61
CHNG III:
PHNG PHP PHN TCH QUANG PH PHT X NGUYN T

III.1 C S L THUYT:
III.1.1 c im chung ca phng php:[7]
- Phng php phn tch quang ph pht x nguyn t (AES - Atomic
Emission Spectroscopy) c s dng nh lng hu ht cc kim loi v
nhiu phi kim nh: P, Si, As, C, B vi nhy nh hn hoc bng 0,001%.
- Phng php AES c u im l mt ln phn tch c th xc nh ng
thi c nhiu nguyn t v phn tch c cc i tng phn tch xa
da vo nh sng pht x t cc i tng .

III.1.2 S to thnh ph AES:[7]
- Phng php AES da vo vic o bc sng, cng v cc c trng
khc ca cc bc x in t do cc nguyn t hay ion trng thi hi pht
ra. Vic pht ra cc bc x in t trong min nh sng quang hc ca cc
nguyn t l do s thay i trng thi nng lng ca nguyn t.
- Theo thuyt cu to nguyn t, cc nguyn t ch c th c mt s mc
nng lng gin on E
0,
E
1
, E
2
m khng c cc trng thi nng lng
trung gian.
Trong iu kin bnh thng, cc nguyn t trng thi nng lng c
bn. Khi ta cp nng lng cho nguyn t mt cch no , cc nguyn t c
th chuyn sang mc nng lng cao hn. Khi nguyn t b kch thch.
N tn ti trng thi kch thch khong 10
-8
giy. Sau n lun lun c
xu hng tr v trng thi c bn ban u bn vng. Ngha l gii phng
nng lng m chng hp th c trong qu trnh trn di dng ca cc
bc x quang hc. Bc x ny chnh l ph pht x nguyn t, n c tn s
c tnh theo cng thc:
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62
E A = (E
n
E
0
) = hv hay E A =

hc

Trong : E
n
, E
0
l nng lng ca nguyn t trng thi c bn (E
0
) v
trng thi kch thch (E
n
)
h l hng s Planck (6,626.10
-27
erk.s) hay h = 4,1.10
-15
eV.s
c: tc nh sng (3.10
8
m/s); v : tn s ca bc x .
: bc sng ca bc x .

III.1.3 Bn cht ca phng php quang ph pht x nguyn t:[11]
- Trong ngn la nhit cao (hay l graphit, tia la in, in h quang ...),
t cc phn t cht nghin cu to cc nguyn t t do, cc nguyn t t do
ny do hp th nng lng bn ngoi chuyn t trng thi c bn ln cc
mc nng lng kch thch, lc tr v km theo s pht ph pht x nguyn
t c trng cho nguyn t cn xc nh.
- Ph pht x nguyn t c dng phn tch nh tnh, bn nh lng v
nh lng.

Hnh 3.1 S ph k pht x nguyn t dng ngn la.
III.1.4 S kch thch, s pht x v cng vch pht x nguyn
t:[11]
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63
* nhn c nhy cao, trong php o ph pht x nguyn t cn cung
cp ngn la c nhit cao. Phng trnh Boltzman:
N
m
*
= N
m

|
|
.
|

\
|
) (T B
Gu
. e
-Eu/KT

Trong :
N
m
*
l s nguyn t b kch thch trong ngn la.
N
m
l s cc nguyn t t do trong ngn la.
Gu l trng lng thng k (tch ra) ca trng thi nguyn t b kch
thch.
B(T) l hm phn b ca cc nguyn t theo tt c cc trng thi.
Eu l nng lng ca trng thi kch thch.
K l hng s Botlzman.
T l nhit tuyt i.
T phng trnh Boltzman: khi tng nhit (T) th s cc nguyn t b kch
thch N
*
tng, nhy tng.
Cng sut ca ph pht x nguyn t (P
T
) c tnh theo cng thc:
P
T
= (h
0
v ).(N
*
, A
T
)
trong : h
0
v l nng lng E ca mi ln chuyn.
h: hng s Planck (6,624.10
-34
J.s)
0
v : tn s (giy
-1
) ca pic quan st c.
A
T
: h s Anhxtanh (s chuyn trong mt giy m nguyn t b
kch thch phi c).
* Cng vch ph pht x:
+ Cng vch quang ph c c trng bng chi sng ca
vch quang ph v cng vch quang ph, k hiu l I.
+ Cng I ca vch pht x nguyn t ph thuc vo:
- iu kin kch thch ph.
- Trng thi vt l ca mu nghin cu.
- Ph thuc vo nng ca nguyn t nghin cu trong mu.
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64
+ S ph thuc ca cng vch pht x nguyn t vi nng
c biu din bng phng trnh Lomakin: I = a.c
b

Trong : a, b: hng s ph thuc iu kin kch thch v trng thi vt
l ca mu nghin cu.
Ta c: lgI = lga + blgc
lgI l hm tuyn tnh ca lgc: lgI = f(lgc). y l biu thc c s cho
phng php phn tch ph nh lng.

III.2 CU HI:
Cu 1: Nu nguyn tc ca php o AES?
HDTL:
+ Mu phn tch cn c chuyn thnh hi (kh) ca nguyn t t do trong
mi trng kch thch. l qu trnh ho hi v nguyn t ho mu. Sau
dng ngun nng lng ph hp kch thch m hi nguyn t
chng pht x. l qu trnh kch thch ph mu.
+ Thu, phn li v ghi ton b ph pht x ca vt mu nh my quang ph.
Trc y, ph c ghi ln knh nh hay phim nh. Chnh my quang ph
s lm nhim v ny. Nhng nhng trang b hin i ngy nay c th thu v
ghi trc tip cc tn hiu cng pht x ca mt vch ph di dng ca
pic trn bng giy hay ch ra cc s o cng vch ph trn my in hoc
ghi li vo a t ca my tnh.
+ nh gi ph ghi v mt nh tnh v nh lng theo nhng yu cu
t ra. y l cng vic cui cng ca php o.

Cu 2: Hy nu nhng u im v nhc im ca php o AES?
HDTL:
* u im:
+ Php o AES c nhy cao, c dng kim tra, nh gi
tinh khit ca nhiu ho cht v nguyn liu tinh khit cao, phn tch
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65
lng vt cc kim loi nng c hi trong i tng thc phm, nc
gii kht, mi trng.
+ C th phn tch ng thi nhiu nguyn t trong mt mu, m
khng cn tch ring chng ra khi nhau. Mt khc, li khng tn
nhiu thi gian, c bit l ng dng phn tch nh tnh v bn nh
lng.
+ L php o chnh xc tng i cao.
+ L phng php phn tch tiu tn t mu, ch cn t 1 n vi chc
miligam mu l .
+ C th kim tra c ng nht v thnh phn ca vt mu
nhng v tr khc nhau. V th cng c ng dng kim tra
ng nht ca b mt vt liu.
+ Ph ca mu nghin cu thng c ghi li trn phim nh, knh
nh hay trn bng giy. N l ti liu lu tr v khi cn thit c th
nh gi hay xem xt m khng cn phi c mu phn tch.
* Nhc im:
+ AES ch cho bit thnh phn nguyn t ca mu phn tch, m
khng ch ra c trng thi lin kt ca n trong mu.
+ chnh xc ca php phn tch ph thuc vo nng chnh xc
ca thnh phn ca dy mu u v cc kt qu nh lng u phi
da theo cc ng chun ca dy mu u c ch to sn
trc.

Cu 3: Nu nhng yu cu ca ngun kch thch ph AES ?
HDTL:
Mt ngun sng mun dng c lm ngun kch thch ph pht x
n cn cn phi tho mn mt s yu cu sau:
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+ Ngun sng phi m bo cho php phn tch c nhy cao v cng
ca vch ph phi nhy vi s bin thin nng ca nguyn t phn tch,
nhng li khng nhy vi s dao ng ca iu kin lm vic.
+ Ngun nng lng phi n nh v bn vng theo thi gian, m bo
cho phng php c lp li v n nh cao. Ngha l cc thng s ca
ngun sng chn nht thit phi duy tr v lp li c.
+ Ngun nng lng phi khng a thm ph ph vo lm ln vi ph ca
mu nghin cu. Nu khng s lm kh khn thm cng vic nh gi nh
tnh v nh lng v c khi lm sai lc c kt qu phn tch.
+ Ngun kch thch phi c s cu to khng qu phc tp, nhng li c
kh nng thay i c nhiu thng s c th chn c nhng iu kin
ph hp theo tng i tng phn tch.
+ Ngun nng lng kch thch phi lm tiu hao t mu phn tch.

Cu 4: Hy nu hai qu trnh chnh ca qu trnh kch thch ph trong ngn
la trong ph AES?
HDTL:
Trong ph AES, nu dng ngn la lm ngun kch thch th mu
phn tch phi chun b dng dung dch. Hai qu trnh chnh ca qu trnh
kch thch ph trong ngn la:
* Nu E
h
< E
nt
th mu phn tch s ho hi, nguyn t ho to ra cc nguyn
t t do, chng b kch thch v pht x c ph pht x.
Me
n
X
m
(r) Me
n
X
m
(k) mMe (k) + nX (k)
Me (k) + E Me (k)
*
Me
0
+ n(hv )
Nng lng kch thch Chm tia pht x
C ch 1 ny cho nhy v n nh cao ca s pht x. Cc hp cht
mui halogen (tr F), axetat, mt s nitrat, sunfat ca kim loi thng
theo c ch ny.
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67
* Nu E
h
> E
nt
th mu s b nguyn t ho trc, sau ho hi thnh
nguyn t, ri b kch ph sinh ra ph pht x.
Me
n
X
m
(r) Me
n
(r) + X
m
(r) mMe (k) + nX (k)
Me (k) + E Me (k)
*
Me
0
+ n(hv )
Nng lng kch thch Chm tia pht x

C ch 2 ny cho nhy v n nh km hn c ch 1. Cc hp cht
mui SiO
2
3
, PO
3
4
, F
-
, mt s nitrat, sunfat ca kim loi thng theo c
ch ny.

Cu 5: Hy cho bit c im ca h quang in c dng lm ngun
nng lng kch thch cho phng php ph AES?
HDTL:
- H quang l ngun kch thch c nng lng trung bnh v cng l ngun
kch thch vn nng. N c kh nng kch thch c c mu dn in v
khng dn in. Nhit ca h quang ph thuc rt nhiu vo bn cht ca
nguyn liu lm in cc. Cng dng in trong mch h quang l yu
t quyt nh nhit ca h quang.
- H quang l ngun kch thch cho nhy tng i cao.
- H quang l ngun kch thch c s mch tng i n gin, nhng li
c nhiu thng s c th iu chnh c chn c mt nhit tng
i ph hp cho php phn tch mi cht.
- H quang l s phng in gia hai in cc c th thp (di 260V) v
dng cao (t 8 - 20A). Th v dng lin h vi nhau qua biu thc:
U = A +
m
I
B
v I
m
=
2 1
R R
U
+

A, B: cc hng s.
R
1
l in tr plasma h quang.
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68
Cng thc ny gii thch ti sao h quang km bn vng. V th phi a
vo mch h quang mt bin tr ph R
2
tht ln (R
2
>> R
1
) hn ch s
thay i cng dng in trong mch v gi cho h quang n nh.

Cu 6: Yu t no quyt nh nhit ca plasma h quang?
HDTL:
- Yu t th nht quyt nh nhit ca h quang l cng dng in
trong mch h quang. Trong mt khong nht nh ca nhit , khi tng
cng ca dng in th nhit ca h quang cng tng theo:
T = k.I k: h s t l
T: nhit ca h quang (
o
C)
- Yu t th hai quyt nh nhit ca h quang l bn cht ca nguyn
liu lm in cc.
- Yu t th ba l th ion ho ca cc cht c trong mu phn tch. Nguyn
t no c th ion ho cng nh th lm gim nhit ca h quang nhiu.
- Trong plasma ca h quang thng lun xy ra cc phn ng ho hc v
cc qu trnh vt l. l qu trnh phn li, ion ho, t hp phn t v s
kch thch ph. Nhng qu trnh ny thng l cc qu trnh nhit ng hc.
V m hi trong plasma cng c mt nhit nht nh ng vi nhng
thng s xc nh ca my pht h quang c chn. Nhit m
bo cho plasma c mt p lc in t xc nh duy tr s kch thch ph.

Cu 7: Hy cho bit nguyn tc v cch chn ngun kch thch ph?
HDTL:
Cc iu kin kch thch ph l nhng yu t c nh hng trc tip
n cng ca vch ph v nhy ca phng php phn tch. chn
c nhng iu kin, ngun kch thch ph ph hp cho mt i tng
phn tch no , cn da vo mt s nguyn tc sau:
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69
+ Phi xut pht t i tng phn tch thuc dng mu no (bt, rn, hay
dung dch), cng nh tnh cht c l ca tng loi mu.
V d:
Khi phn tch mu bt (qung, t ...) th h quang in c dng trn
10A l thun li.
+ Phi da vo tnh cht v c trng s kch thch ph ca mi nguyn t
cn xc nh m chn ngun nng lng kch thch v cc thng s ca
ngun kch thch.
Vi d: Phn tch kim loi kim th nn dng ngn la n kh, hay h quang
gin on. V th kch thch ph pht x ca cc kim loi kim l khng ln
(3-5 eV).
+ Khi chn ngun kch thch phi m bo cho php phn tch c nhy
cao, n nh, c th d dng phn tch c cc nguyn t c nng
nh.
+ Chn ngun phn tch phi m bo cho php phn tch tiu tn t mu, v
khi cn phi khng ph hy mu.

Cu 8: Hy nu cc yu t to ra bc x nn trong ph pht x?
HDTL:
Khi kch thch mu phn tch ta thu c ph pht x ca n. Ph ny bao
gm c ph vch ca nguyn t v ion, ph m ca phn t v nhm phn
t. Sau n ph nn hay gi l bc x nn. Bc x nn thng l ph lin
tc. T kt qu nghin cu, ngi ta thy c 4 yu t to ra bc x nn:
- S pht sng ca ht vt rn c t nng trong plasma.
- Tc dng ca nh sng trng.
- S bc x ca in t trong plasma.
- S pht x ca in cc b t nng nhit cao.
-
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70
Cu 9: Hy cho bit nguyn tc ca phng php quan st trc tip trn mn
nh?
HDTL:
Nguyn tc ca phng php quan st trc tip trn mn nh l: trn
mn nh ca my quang ph ngi ta t mt mng m, trn mng m ny
c nh du v tr cc vch c trng ca mt s nguyn t nht nh. ng
thi b tr mt h thng thu knh lp phng i quan st trc tip mn
nh . Nh vy, mun nh tnh mt mu no , ta thu ph ca mu phn
tch, khi kch thch chng bng mt ngun nng lng ph hp v quan st
ph mt cch trc tip trn mn nh ca my nh h thng knh lp phng
i. Khi da theo cc vch ph c trng nh du trn mng m m
kt lun c mt hay khng c mt nguyn t trong mu phn tch.
Phng php ny nhanh, n gin. Nhng ch gii hn trong nhng
mu n gin v nhng nguyn t cn phn tch c nh du cc vch
ph c trng ca n trn mng m ca my quang ph.

Cu 10: Trnh by nhng ng dng c bn ca phng php o ph AES?
HDTL:
Phng php o ph AES l mt phng php phn tch quan trng
thng c s dng rng ri trong mt s lnh vc sau:
- Xc nh cc kim loi kim, kim th trong cc mu phn tch
bnh vin. Phng php phn tch nhanh, tin li, nhy,
ng tt, thch hp cho php phn tch nhiu mu.
- Xc nh hm lng cc ion kim loi trong cc loi nc thi khc
nhau.
- Xc nh cng ca nc.
- Xc nh s b thnh phn ca mu phn tch chn quy trnh
phn tch thch hp.
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71
- Phn tch nguyn liu, bn thnh phm v thnh phm, trong luyn
kim, phn tch t, trong ngnh a cht, k thut khai khong,
phn tch nc ngun, nc cng nghip, cc i tng mi trng
...

Cu 11: Ngi ta thng s dng cht ph gia khc nhau thm vo mu
phn tch trong php o quang AES vi mc ch g?
HDTL:
Mc ch ca vic thm vo mu phn tch cc cht ph gia khc nhau l:
- To iu kin cho qu trnh ho hi, nguyn t ho mu, kch thch ph n
nh, m bo cho php phn tch t chnh xc cao v lp li cao,
ngha l thu c kt qu tt.
- Tng cng vch ph ca nguyn t nghin cu, ngha l tng nhy
ca phng php phn tch c th xc nh c nhng nng nh m
khng phi lm giu mu phn tch.
- Loi tr bt nhng nh hng ca cc hp phn cn tr, nh ph nn lin
tc, nh hng ca nguyn t c s, nguyn t th ba.
- Pha long mu phn tch loi b nh hng ca hin tng t o, hoc
lm n gin ph ca mu phn tch d quan st nh tnh v nh lng.

Cu 12: Nguyn tc chung ca phn tch quang ph pht x nh tnh?
HDTL:
Khi cung cp nng lng ho hi, nguyn t ho mu phn tch v kch
thch m hi nguyn t i n pht x th chng ta s thu c ph pht
x ca mu phn tch. Ph gm 3 phn:
- Ph vch ca nguyn t v ion.
- Ph m ca phn t v nhm phn t.
- Ph nn lin tc.
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72
Trong , ph vch l thnh phn chnh c trng cho nguyn t v ion
trng thi hi t do, khi chng b kch thch, ngha l trng thi hi. Khi b
kch thch cc nguyn t v ion s pht ra mt chm bc x quang hc bao
gm nhng tia c bc sng khc nhau nm trong di ph quang hc (190 -
1100nm). Nu thu, phn li v ghi chm sng li ta s c mt di ph
gm cc vch pht x ca nguyn t v ion ca cc nguyn t trong mu.
Trong tp hp cc vch ph , th mi loi nguyn t hay ion li c mt s
vch c trng ring cho n. Cc vch ph c gi l cc vch ph pht
x c trng ca mi loi nguyn t y.
V d: Khi b kch thch :
- Nguyn t Al pht ra vch c trng trong vng UV: 308,215; 309,271
nm.
- Nguyn t Cu pht ra vch c trng trong vng UV: 324,754; 327,396
nm.
Nh cc vch ph c trng ny, ngi ta nhn ra c s c mt hay
vng mt ca mt nguyn t no trong mu phn tch qua vic quan st
ph pht x ca mu phn tch v tm xem c cc vch ph c trng ca n
hay khng, ngha l da vo cc vch ph pht x c trng ca tng nguyn
t nhn bit chng. chnh l nguyn tc ca phng php phn tch
quang ph pht x nh tnh.

Cu 13: Qu trnh phn tch quang ph pht x nh tnh gm my giai
on?
HDTL:
C 3 giai on trong qu tnh phn tch quang ph pht x nh tnh:
* Cung cp nng lng ho hi, nguyn t ho mu phn tch to ra m
hi nguyn t t do v kch thch m hi pht ra ph pht x ca chng.
* Thu chm sng pht x , phn li v ghi ph pht x ca mu phn tch.
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73
* Quan st ph thu c ca mu phn tch theo cc vch c trng ca cc
nguyn t pht hin chng.

Cu 14: Nu cc iu kin chn vch ph chng minh nh tnh?
HDTL:
xc nhn s c mt hay khng ca mt nguyn t no trong mu
phn tch, ngi ta phi tm mt s vch ph c trng ca nguyn t v
gi l vch chng minh ca nguyn t . Cc vch ph ny phi tho mn
iu kin sau:
* Nhng vch ph ny phi r rng v khng trng ln vi cc vch ca
nguyn t khc, nht l nguyn t nng ln.
* N phi l nhng vch ph nhy, c th pht hin c cc nguyn t
trong mu vi nng nh.
* Vic chn cc vch ph chng minh cho mt nguyn t phi xut pht t
ngun nng lng dng kch thch ph ca mu phn tch, v trong
ngun kch thch c nng lng thp th ph ca nguyn t l ch yu v
vch nguyn t ca n thng l nhng vch nhy. Nu trong ngun kch
thch giu nng lng th ph ca ion l ch yu. V th, tu thuc vo
ngun nng lng dng kch thch ph m chn vch chng minh l
vch nguyn t hay vch ion.
* Phi cn c vo my quang ph c th thu, phn li v ghi c trong vng
sng no m chn vch chng minh cho mt nguyn t nht nh.
V d: chng minh Na, nu ph mu c ghi trn my Q - 24 (vng
ph 200 - 400nm) th ta phi chn hai vch Na 330,30nm v Na 330,27nm.
Nu ghi trn my lng knh thu tinh (vng ph 360 - 780nm), th li phi
chn hai vch Na 589,60nm v 589,00nm. Nu dng my cch t PGS - 2
(vng ph 200 - 1100nm) th chn 4 vch trn u c.

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74
Cu 15: V sao cc cht ph gia trong phn tch ph pht x c th lm tng
hoc gim cng vch ph ca mt nguyn t?
HDTL:
V s thay i thnh phn ho hc ca mu thng nh hng n mi qu
trnh trong khi kch thch ph, nh:
+ S thay i nhit plasma.
+ Thay i nng in t (Pe) trong plasma.
+ S khuch tn v chuyn vn ca cc phn t.
+ Cc phn ng ho hc in cc v plasma.
+ Qu trnh ho hi ca cht mu.
+ S bay hi v nguyn t ho cht mu.
+ Thi gian tn ti ca cc phn t trong plasma.
+ S ion ho, s phn li ca cc cht.
+ S kch thch ph ca cc phn t trong plasma.
, s thay i p lc in t (Pe) v nhit ca plasma l yu t
chnh, c
tnh cht quyt nh.

Cu 16: Hy trnh by cch xc nh di sng ca mt vch ph bng
phng php ni suy?
HDTL:
Theo phng php ni suy, di sng
x
ca mt vch ph c th
c xc nh theo cng thc sau:

x
=
1
+
) (
) (
1 2
1 2
d d

(d
x
d
1
)
Trong :
1 2
, : l hai vch ph bit di sng chnh xc.
d
1
, d
2
, d
x
: l khong cch ca 3 vch
1 2
, ,
x
trn knh nh
n tm.
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75
- Phng php ny ch c dng trong iu kin hai vch ph
1
v
2

gn nhau (khng xa nhau qu 10mm trn knh nh) v vch ph
x
cn xc
nh cn phi nm gia hai vch . Mt khc, hai vch
1
v
2
phi nt, r
rng, mnh v en khng ln. Nu khng tho mn nhng iu kin
th vch
x
xc nh c s sai s ln.


d
1
1 x 2

dx

d
2



Hnh 3.2: V tr cc vch ph bit v cha bit trn knh nh

Cu 17: Hy so snh ph hp th nguyn t v php o ph pht x nguyn
t?
HDTL:
* c im chung ca 2 phng php: l phi c ngn la (hay l graphit)
c nhit cao tin hnh nguyn t ho mu, chuyn mu nghin cu (
trng thi tp hp bt k) thnh dng nguyn t t do.
* c im ring ca 2 phng php:
- Phng php o ph hp th nguyn t v pht x nguyn t khng cnh
tranh nhau m b sung cho nhau.
+ Ph pht x nguyn t ng dng cho cc nguyn t c nng lng
kch thch thp vng bc sng 400 - 800nm.
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76
+ Ph hp th nguyn t ng dng cho cc nguyn t c nng lng
kch thch cao vng bc sng 200 - 300nm.
Trong vng bc sng 300 - 400nm, c hai phng php ph hp
th nguyn t ny u c th s dng c.
+ Php o ph hp th nguyn t thng c s dng phn tch
70 nguyn t. V d: Be, Mg, Ca, Pt, Ah, Au, Cd, Pb, Hg, Si, As, Sb, Bi, Te,
Sn .
+ Php o ph hp th nguyn t thng c s dng phn tch
nhiu nguyn t. V d: Li, Na, K, Sr, Ba, Y, La, Ce, Pr, Th, V, Sm
+ C 2 phng php u p dng xc nh c cc nguyn t sau:
Rb, Cs, Ca, Ra, Se, Ac, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Nd,
Fe, Ru, Os, Rh, La, Ni, Pb, Cu, Ga, Su, Tl, Nd, Dy, Ho, Er, Tm, Yb, Lu
+ C 2 phng php u khng p dng c phn tch cc
nguyn t sau: H, Fr, Pm, Np, Am, Cm, Bk, Cf, C, No, F, Cl, I, Br, He, Ne,
Ar, Xe, Po, Es, Fm.
+ Phng php o ph hp th nguyn t c nhy cao hn v t
ph thuc vo ngn la hn so vi php o ph pht x nguyn t.
+ Php o ph hp th nguyn t cho sai s b hn php o ph pht
x nguyn t, do vy php o ph hp th nguyn t thng c s dng
cho phn tch nh lng hm lng nh, cn php o ph pht x nguyn t
thng c s dng cho php o ph nh tnh v bn nh lng.
- Gi thnh ph k hp th nguyn t t hn nhiu ph k pht x nguyn
t.
- Ph pht x nguyn t ph thuc vo nhit ngn la nhiu hn ph hp
th nguyn t.
- chnh xc: ph hp th nguyn t % 1 , 0 ; ph pht x nguyn t % 5 1

Cu 18: Cc yu t nh hng n kt qu phn tch trong php o ph
pht x nguyn t c xp thnh my nhm?
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77
HDTL:
Cc yu t nh hng n kt qu phn tch trong php o ph pht x
nguyn t c xp thnh 6 nhm:
- Nhm 1: L cc thng s ca h my o ph. Cc thng s ny cn
c kho st v chn ph hp cho tng trng hp c th. Thc
hin cng vic chnh l qu trnh ti u ho cc thng s ca my
quang ph cho mt i tng phn tch, v d vch ph o, khe o,
iu kin ghi ph
- Nhm 2: L cch a mu, cc iu kin ho hi, nguyn t ho
mu v kch thch ph. Cc yu t ny th hin rt khc nhau tu
thuc vo k thut c chn thc hin qu trnh ho hi,
nguyn t ho, kch thch ph.
- Nhm 3: L k thut v phng php c chn x l, chun b
mu vic o ph. Trong cng vic ny nu lm khng cn thn
s c th mt hoc lm nhim bn thm nguyn t phn tch vo
mu. Nh vic dng cc ho cht khng m bo tinh khit cao,
mi trng chun b mu . Do kt qu phn tch thu c l
khng ng vi thc t ca nguyn t phn tch tn ti trong mu.
V th vi mi mt loi mu ta phi nghin cu v phi chn mt
qui trnh x l ph hp nht, c c ng thnh phn ca mu
v khng lm nhim bn mu.
- Nhm 4: Cc nh hng v ph.
- Nhm 5: Cc yu t nh hng vt l.
- Nhm 6: Cc yu t ho hc.

Cu 19: S pht x nn c nh hng nh th no trong php o ph pht x
nguyn t?
HDTL:
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78
S pht x nn c trng hp xut hin r rng, c trng hp khng
xut hin. iu ny ph thuc vo vng ph v vch ph c chn o
nm trong vng ph no. Ni chung, trong vng kh kin th yu t ny th
hin r rng, tc l ph nn rt m. Cn trong vng t ngoi th nh hng
ny t xut hin, hay c xut hin th cng m nht. V ph nn trong vng t
ngoi thng l yu. Hn na s pht x nn cn ph thuc rt nhiu vo
thnh phn nn ca mu phn tch, c bit l matrix ca mu, ngha l
nguyn t c s ca mu, v ngun nng lng kch thch ph.
V d: khi xc nh ch trong mu sinh hc bng php o ngn la th s
pht x nn l khng ng k. Nhng khi xc nh ch trong nc bin (nn
2,9% NaCl) th nh hng ny li l v cng ln. Hay kch thch ph ca
mu bng h quang in in cc than th nn l rt m trong vng kh
kin (340 - 800nm).
Do trong mi trng hp c th phi xem xt tm bin php loi
tr. loi tr ph nn, ngy nay ngi ta lp thm vo my quang ph pht
x nguyn t c h thng b chnh nn t ng, c th dng khi cn thit.
Hoc a vo mu cc cht ph gia thch hp lm gim s pht x ca
ph nn lin tc.
Cu 20: nh hng ca nht v sc cng b mt ca dung dch mu
trong php o ph pht x nguyn t nh th no?
HDTL:
Trong php o ph pht x nguyn t th nht v sc cng b mt
ca dung dch mu nh hng nhiu n tc dn mu vo bung aerosol
ho v hiu sut aerosol ho ca mu v t m nh hng n kt qu
phn tch. Ni chung tc dn mu t l nghch vi nht ca dung dch
mu. Chnh s khc nhau v nng axit, loi axit, nng cht nn ca
mu, thnh phn ca cc cht c trong dung dch mu l nguyn nhn gy ra
s khc nhau v nht ca dung dch mu. V th trong mi qu trnh phn
tch mt nguyn t, nu mu dng dung dch th nht thit phi m bo
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
79
sao cho mu phn tch v cc mu u lp ng chun phi c cng nng
axit, loi axit v thnh phn ha hc, vt l ca tt c cc nguyn t khc,
nht l cht nn ca mu. loi tr nh hng ny chng ta c th dng
cc bin php sau y:
- o v xc nh theo phng php thm tiu chun.
- Pha long mu bng mt dung mi.
- Thm vo mu mt cht nn ph hp khc.
- Thm vo mu mt cht m c nng ln.
- Dng bm y muc vi mt tc xc nh m chng ta mong
mun.
Cu 21: Cc yu t ho hc c nh hng nh th no trong php o ph
pht x nguyn t ?
HDTL:
Trong php o ph pht x nguyn t cc nh hng ho hc cng rt a
dng v phong ph v phc tp. N xut hin cng rt khc nhau trong mi
trng hp c th v cng nhiu trng hp khng xut hin. Cc nh hng
ho hc thng c th dn n kt qu theo bn hng sau y:
- Lm gim cng ca vch ph ca nguyn t phn tch, do s
to thnh cc hp cht bn nhit, kh ho hi v kh nguyn t
ho. V d nh nh hng ca cc ion silicat, sunfat, photphat,
florua.
- Lm tng cng ca vch ph, do s to thnh cc hp cht d
ho hi v d nguyn t ho, hay do hn ch c nh hng ca
s ion ho v s kch thch ph pht x ca nguyn t phn tch.
chnh l tc dng ca mt s hp cht, ch yu l mui halogen
ca kim loi kim v kim th hay clorua hu c.
- S tng cng vch ph khi nguyn t phn tch tn ti trong nn
ca mu l nhng hp cht d ho hi ca nguyn t phn tch v
lm n c ho hi vi hiu sut cao hn.
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80
- S gim cng ca vch ph khi nguyn t phn tch tn ti
trong nn ca mu l nhng hp cht bn nhit, kh ho hi. Lc
ny cc nguyn t nn km hm s ho hi ca nguyn t phn
tch. Cc cht nn ny thng l nhng hp cht bn nhit ca cc
nguyn t nh Al, t him .

III. BI TP:
Dng 1: Xc nh gi tr nguyn t ng vi mc nng lng m electron
chuyn ti.
Cch gii:
p dng cng thc: (E
c
v E
t
mc nng lng tng ng vi mc cao v
thp)

1
=
hc
me
2
4
2
|
|
.
|

\
|

2 2
1 1
c t
n n
= R
H

|
|
.
|

\
|

2 2
1 1
c t
n n

R
H
: hng s Rydberg; n
t
v n
c
- s lng t ng vi mc nng lng
thp hay cao. (R
n
= 109678,76 cm
-1
).
- bc sng cn tm cho tng dy ph tng ng.
- i vi cc h mt electron ca cc ion ta c:

o
1
= = Z
2
R
|
|
.
|

\
|

2 2
1 1
n n
t


Bi 1: Tnh hiu nng lng gia hai mc trong ph pht x ca H vi cc
s liu sau:
a, n
t
= 1 v n
c
= 2
b, n
t
= 10 v n
c
= 11
So snh kt qu thu c vi 2 mc a v b.

Gii:
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
81
a, Ta c
1
E A = -13,6.
|
|
.
|

\
|

2 2
1 1
t c
n n
= -13,6
|
.
|

\
|

1
1
4
1
= 10,2 eV
b, Ta c
2
E A = -13,6.
|
|
.
|

\
|

2 2
1 1
t c
n n
= -13,6
|
.
|

\
|

2 2
10
1
11
1
= 0,0236 eV
nng lng gia 2 mc trong ph pht x ca H a) gp 432 ln b).

Bi 2: T kt qu tnh nng lng i vi nguyn t H trong bi ton trng
xuyn tm hy:
1. Thit lp cng thc tnh bc sng ca ph pht x hiro v gii thch
cc k hiu tm c?
2. Cho bit bc sng ca vch gii hn cui trong ph pht x i vi
ion Heli (He
+
) l 2050
0
A. Hy xc nh gi tr nguyn t ng vi mc nng
lng thp m electron chuyn ti.

Gii:
1. Xut pht t E =
2 2
4
2 n
me
i vi nguyn t ta c th xc nh c .
E A = E
c
E
t
=
2 2
4
2
c
n
me

+
2 2
4
2
t
n
me

= hc

1

(E
c
v E
t
mc nng lng tng ng vi mc cao v thp)

1
=
hc
me
2
4
2
|
|
.
|

\
|

2 2
1 1
c t
n n
= R
H

|
|
.
|

\
|

2 2
1 1
c t
n n

R
H
: hng s Rydberg; n
t
v n
c
- s lng t ng vi mc nng lng
thp hay cao. (R
n
= 109678,76 cm
-1
).
- bc sng cn tm cho tng dy ph tng ng.
2. p dng cng thc trn vi ion He
+
(Z = 2). i vi cc h mt electron
ca cc ion ta c:

o
1
= = Z
2
R
|
|
.
|

\
|

2 2
1 1
n n
t

S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
82

8
10 . 2050
1

= 109700
|
|
.
|

\
|

n n
t
1 1
2
2
2

Sau khi bin i ta c n
t
~ 3 ng vi mc m electron chuyn ti.

Bi 3: Hy xc nh cng thc tng qut tnh cc vch gii hn cho cc
dy ph Lyman, Balmer v Paschen. T cc kt qu thu c hy rt ra kt
lun cn thit v s dch chuyn ca ph thuc cc dy ph kho st?
Cho R
H
= 1,09775.10
7
m
-1
.
Gii:
Ta k hiu cc vch gii hn trong cc dy ph:
Vch u:

+ =
=
1 n n
n n
c
t

_
v
n,n+1
= R
H

|
|
.
|

\
|
+

2 2
) 1 (
1 1
n n
= R
H

2 2
) 1 (
1 2
+
+
n n
n
=
1 ,
1
+ n n



1 , + n n
=
) 1 2 (
) 1 (
2 2
+
+
n R
n n
H
(1)
Vch cui:

=
=
c
t
n
n n


_
v
n,
= R
H

|
.
|

\
|
2
1
n
=
,
1
n


, n
=
H
R
n
2
(2)

Thay cc gi tr bng s vo (1) v (2) ta thu c cc gi tr trong bng sau:
Dy ph Lyman Balmer Paschen
1 , + n n

121nm 656nm 1876nm
, n

91 365 821
Vng ph UV Trng thy IR
A 30 291 1055

S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
83
Nhn vo gi tr A r rng s chuyn dch ca cc bc sng tng t
vng UV n IR.

Bi 4: T cc d kin sau y thuc ph pht x ca hiro. Hy xc nh
31

v
41
thuc dy Lyman. Bit
21
= 1215
0
A thuc dy Lyman;
32
= 65663
0
A
(vch H
o
):
42
= 4861
0
A (vch
o
H thuc dy Balmer).
Gii:
Theo s di y ta c th tnh c cc bc sng
31
v
41
:
n = 4

n = 3

32

42

n = 2
Dy Balmer

21

31

41

n = 1
Dy Lyman

Hnh 3.3 Gin nng lng pht x nguyn t ca Hiro

T cng thc chung tnh nng lng cho cc photon v h E= A ta vit:
E A
2 1
= E
2
E
1
= h
21
v =
21

hc
(1)
E A
3 2
= E
3
E
2
= h
32
v =
32

hc
(2)
E A
4 2
= E
4
E
2
= h
42
v =
42

hc
(3)
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
84
xc nh hai bc sng
31
v
41
thuc dy Lyman ta c th t hp cc
biu thc trn: E A
3 1
= h
31
v = E
3
E
1
= (E
3
E
2
) + (E
2
E
1
)
T (2) v (1) ta c:
31

hc
=
32

hc
+
21

hc

31
1

=
32
1

+
21
1



31
=
21 32
21 32


+
=
1215 65663
1215 . 65663
+
= 1193
0
A
T (3) v (4) ta c:
41

hc
=
42

hc
+
21

hc

41
1

=
42
1

+
21
1



41
=
21 42
21 42


+
=
1215 4861
1215 . 4861
+
= 972
0
A

Bi 5: Trong mt th nghim ngi ta cung cp mt nng lng gp 1,5
ln nng lng ti thiu bt mt electron ra khi trng thi c bn ca
nguyn t hiro. Hi bc sng theo
0
A ca bc x trong trng hp ny
bng bao nhiu? Cho h = 6,62.10
-34
J.s ; m
e
= 9,1.10
-31
kg; c = 3.10
-8
m/s.

Gii:
Khi cung cp mt nng lng gp 1,5 ln nng lng ti thiu, E
H
(nng
lng i vi H trng thi c bn) lm bt electron ra khi H th nng
lng ny c chia lm 2 phn. E
1
l nng lng dng bt electron
(nng lng ion ho). E
2
l nng lng dng lm cho electron chuyn
ng.
Ta c: E = E
1
+ E
2

1,5E
H
= E
H
+
2
2
mv

2
1
E
H
=
2
1
mv
2

mE
H
= (mv)
2

mv =
H
mE

S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
85
xc nh bc sng ta p dng h thc De Broglio:
=
mv
h
hay =
H
mE
h

Thay s vo biu thc ta c: =
19 31
34
10 . 6 , 1 . 6 , 13 . 10 . 1 , 9
10 . 62 , 6

= 4,7 . 10
-10
m =
4,7
0
A
Bi 6:
a, Cho phn t nit chuyn ng trong hp th mt chiu vi L = 5cm, hy
xc nh hiu nng lng (theo J) gia hai mc nng lng thp nht?
Cho h = 6,62.10
-34
J.s ; m
e
= 9,1.10
-31
kg; c = 3.10
-8
m/s.
b, Tnh xem phn ng vi gi tr n bng bao nhiu th nng lng ca phn
t nit t c gi tr
2
3
kT 300
0
K.
c, Ti mc nng lng tng ng vi n va tm c th nng lng tch
bng bao nhiu khi N
2
chuyn v mc nng lng thp k tip.
Cho k = 1,381.10
-23
J/K
-1
; h = 6,62.10
-34
J.s ; N = 14 ; m
e
= 9,1.10
-31
kg;
1u = 1,66.10
-27
kg
Gii:
a, Ta c: E A
2 1
= E
2
- E
1
= 4
2
2
8mL
h
- 1
2
2
8mL
h

E A = 3
2
2
8mL
h
= 3
2 2 27
2 34
) 10 . 5 .( 10 . 66 , 1 . 28 . 8
) 10 . 62 , 6 (

= 3 . 4,714.10
-40
= 1,41.10
-39
J
E
E A
n n 1




E A
2 1

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86
Hnh 3.4 Gin hiu mc nng lng thp nht ca phn t Nit
b, khi E t c
2
3
kT 300
0
K, ngha l:
E = n
2
2
2
8mL
h
=
2
3
kT n
2
. 4,714.10
-40
=
2
3
kT
n =
40
10 . 714 , 4 . 2
3

kT
=
40
23
10 . 714 , 4 . 2
300 . 10 . 381 , 1 . 3

= 3,63.10
-9
c, E A
n n 1
= E
n
E
n 1
= [n
2
(n - 1)
2
]
2
2
8mL
h
= (2n - 1)
2
2
8mL
h

Do n >> 1:
E A
n
= 2n
2
2
8mL
h
= 2.3,63.10
9
.4,714.10
-40
= 3,42.10
-30
J
Bi 7: T li gii phng trnh Schrodinger cho h mt electron, mt ht
nhn v lin h E A gia hai mc nng lng
c
n
E v
t
n
E (k hiu n
c
v n
t
ch
mc nng lng ng vi s lng t n cao hoc thp) ta thu c biu thc:
|
|
.
|

\
|
=
2 2
1 1
c t
H
n n
R v (1)
Trong :
v l tn s vch ph (theo Hz) trong quang ph vch H.
R
H
l hng s Ritbe cho hiro.
1. Biu thc (1) tnh vch ph hp th hay pht x? Ti sao?
2. Hy cho bit cng thc c th ca R
H
?
3. Cho R
H
= 3,29.10
15
Hz. Hy tnh v ca mt vch trong dy Lyman vi
n
c
= 7?
Gii:
1.Li gii phng trnh Schrodinger cho h mt electron, mt ht nhn thu
c biu thc: E
n
= -
2
0
2 2
4 2
) 4 ( 2 tc n
e mZ
(a)
Mt khc. c E A =
c
n
E -
t
n
E = hv (b)
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87
Kt hp hai biu thc (a), (b) ta c biu thc
|
|
.
|

\
|
=
2 2
1 1
c t
H
n n
R v (1)
Vy (1) l biu thc tnh tn s v ca mt vch ph pht x (ta xt vi H nn
Z = 1).
2. Kt hp hai biu thc (a), (b) v 4
0
tc = 1 ; =
t 2
h
ta thu c biu thc
ca hng s Ritbe cho H l R
H
=
c h
me
3
4 2
2t
(2)
3. Dy Lyman c n
t
= 1 ; vi n
c
= 7 thay vo (1) ta c:
v = 3,29.10
15
(1 -
49
1
)Hz = 3,22.10
15
Hz
Bi 8:
a, Hy vit biu thc tnh nng lng (E) ca electron trong nguyn t H t
vic gii phng trnh chrodinger?
b, T biu thc nng lng hy rt ra biu thc tnh s sng

v ca cc
vch ph pht x ca nguyn t H?
Gii:
a, Li gii phng trnh Schrodinger cho h mt electron, mt ht nhn thu
c biu thc: E
n
= -
2
0
2 2
4 2
) 4 ( 2 tc n
e mZ

Trong : Z = 1; 4
0
tc = 1 ; =
t 2
h

Biu thc tnh nng lng (E) ca electron trong nguyn t H t vic gii
phng trnh chrodinger: E
n
= -
2 2
4 2
2
h n
me t
= -
2
6 , 13
n
eV
b, E A =
c
E -
t
E ; E A = hv =

c
h =
_
v hc

hc
E E
t c

=
_
v =
|
|
.
|

\
|

2 2 3
4 2
1 1 2
c t
n n c h
me t
= R
H

|
|
.
|

\
|

2 2
1 1
c t
n n

vi R
H
=
c h
me
3
4 2
2t
= 109195,16 cm
-1
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
88
Bi 9: ph v lin kt I I trong 1 mol iot i hi phi cung cp mt
nng lng l 150,48 kJ di dng ca nh sng kch thch. Hy tnh bc
sng ng vi gi tr l bao nhiu theo nm. Cho h = 6,62.10
-34
J.s ; c =
3.10
8
m/s ; N
A
= 6,022.10
23
mol
-1
.
Gii:
Phng trnh: hv + I
2
2I
Ta c: E = v h =
23
10 . 022 , 6
150480
= 24,98.10
-20
J
Mt khc:
E
hc
= =
20
8 34
10 . 98 , 24
10 . 3 . 10 . 625 , 6

= 0,795.10
-6
m = 795nm.

Dng 2: Tnh nng lng photon ca cc bc sng ca bc x n sc.
Cch gii:
* p dng cng thc: v h E= A
v

v
c
=
Trong : h: hng s Plank, h = 6,626.10
-27
ec.s
C: tc nh sng = 3.10
8
m/s
: bc sng ca bc x.
v : tn s ca bc x.
Bi 10: Hy tnh nng lng ca photon (trong ec) ca cc bc sng sau:
a, 803nm
b, 999
0
A
Gii:
p dng cng thc: v h E= A trong

v
c
= ta c:
a, 803nm = 803.10
-9
m
tn s sng

v
c
= =
9
8
10 . 803
10 . 3

= 3,74.10
14
s
-1

Nng lng photon:
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
89
v h E= A = 6,626.10
-27
. 3,74.10
14
= 2,48.10
-12
ec
b, 999
0
A = 999.10
-10
m
tn s sng

v
c
= =
10
8
10 . 999
10 . 3

= 3.10
15
s
-1

Nng lng photon:
v h E= A = 6,626.10
-27
. 3.10
15
= 2.10
-9
ec
Bi 11: Thc nghim xc nh c di bc sng ca hi Natri l
= 5900
0
A. Hy xc nh:
a, Nng lng ca cc quang electron (photon) pht ra theo J v eV?
b, Tn s sng v theo Hz?
Gii:
a, p dng cng thc:

hc
E = A =
10
8 34
10 . 5900
10 . 3 10 . 626 , 6

= 3,36.10
-19
J
v 1 eV = 1,6.10
-19
J 3,36.10
-19
J = 2,1 eV
b, Ta c: v h E= A

h
E A
= v =
34
19
10 . 626 , 6
10 . 36 , 3

= 5,08.10
14
Hz hoc

v
c
= = 5,08Hz
Bi 12: Trong trng hp i vi nguyn t H, hy xc nh cc i lng
sau:
a, Nng lng kch thch dng chuyn electron trng thi c bn ln
trng thi ng vi n = 3.
b, Nng lng ion ho tch electron n = 3 ti xa .
c, Bc sng (nm) khi electron chuyn t n = 3 v n = 2.
Gii:
Trong trng hp chung, ta c th p dng cng thc:
E A = E
c
E
t
= E
H

|
|
.
|

\
|

2 2
1 1
c t
n n

y E
H
l nng lng ca H trng thi c bn. E
H
= -13,6eV.

S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
90
n =

3

n = 4

n = 3

32

n = 2

13


n = 1

Hnh 3.5 Gin nng lng nguyn t H

a, i vi bc chuyn 1 3 nng lng tng ng l:
E A
1 3
= E
3
E
1
= -13,6
|
|
.
|

\
|

2 2
1
1
3
1
= 12,09 eV.
b, Nng lng ion ho ng vi bc chuyn 3 l:
E A
3
= E

E
3
= -13,6
|
.
|

\
|

9
1 1
= 1,5 eV.
c, Bc sng
32
khi electron chuyn t 3 2 l:
E A
3 2
= E
3
E
2
= hv = h
32

C
= -13,6
|
.
|

\
|

4
1
9
1

32
= 36
19
10 . 6 , 1 . 6 , 13 . 5

hC
= 6,57.10
-7
m hay
32
= 657nm.
Bi 13: Vch ph ng vi bc chuyn n
t
= 1 v n
c
= 2 i vi ion He
+
c
bc sng tng ng = 30,3.10
-9
m.
a, Hy xc nh gi tr
+
He
R ?
b, Tnh nng lng trng thi c bn theo J v eV i vi ion He
+
?
Gii:
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
91
a, i 30,3.10
-9
m = 30,3.10
-7
cm
Ta c:

1
=
|
|
.
|

\
|

+
2 2
1 1
c t
He
n n
R

7
10 . 3 , 30
1

=
|
.
|

\
|

+
4
1
1
1
He
R

+
He
R = 0,044.10
7
cm
-1
= 4,4.10
5
cm
-1
.
b, p dng cng thc: E = -13,6.
2
2
n
Z

Ta c: E = -13,6.
2
2
1
2
= -54,4 eV
nng lng trng thi c bn i vi He
+
l 54,4 eV = 87,04.10
-19
J

Dng 3: Xc nh % ca kim loi trong mu bng phng php chun, khi
bit cng pht x.
Cch gii:
Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l bnh
phng ti thiu A = aC + b:
Trong : a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
; b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.

T phng trnh hi quy tuyn tnh ta suy ra nng C, t suy ra t l %.
Bi 14 Nng Na trong cy c th c xc nh bng phng php quang
photphat x nguyn t. Mu phn tch c chun b bng cch nghin nh,
homogen ho v lm kh 103
o
C. Mt mu khong 4 gam c chuyn vo
bnh thch anh nung trn a phn hu hp cht hu c. Mu c nung
trong l nung 550
o
C trong vi gi, sau khi a v nhit phng, phn tro
c ho tan trong 2,0 ml dung dch HNO
3
1:1 v lm bay hi n kh.
Phn cn rn c ho tan li bng 10,0 ml dung dch HNO
3
1:9, lc v pha
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92
long n 50,00 ml. Cc d liu thc nghim thu c khi phn tch nh trn
vi 4,0264 gam mu cnh cy si :
Mu ppm Na pht x
Mu trng 0 0
Mu chun 1 2,00 90,30
Mu chun 2 4,00 181,0
Mu chun 3 6,00 272,0
Mu chun 4 8,00 363,0
Mu chun 5 10,00 448,0
Mu phn tch 238,0
Hy xc nh hm lng Na theo ppm trong cnh cy si.
Gii:
Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l bnh
phng ti thiu A = aC + b:
Mu
Hm lng
Na (C)
hp th (A) A.C C
2
Mu trng 0,00 0,00
0,000
0,000

Mu chun 1 2,00 90,30
180,600
4,00
Mu chun 2 4,00 181,0
724,000
16,00
Mu chun 3 6,00 272,0
1632,000
36,00
Mu chun 4 8,00 363,0
2904,000
64,00
Mu chun 5 10,00 448,0
4480,000
100,00
Mu phn tch 238,0
n = 6
C

= 30,0 A

= 1354,3 AC

= 9920,6
2
C

= 220
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
30 220 . 6
30 . 3 , 1354 6 , 9920 . 6

= 44,987

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93
b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
30 220 . 6
30 . 6 , 9920 220 . 354 , 1

= 0,781

y = 44,987x + 0,781
R
2
= 0,9999
0
50
100
150
200
250
300
350
400
450
500
0 2 4 6 8 10 12

Hnh 3.6 ng chun xc nh hm lng Na trong mu cy si.

Xy dng ng chun: y = 44,987C + 0,781
C = 5,273 ppm; khi lng Na trong mu: m = 5,273.50,0 = 263,65 g
Hm lng Na trong mu cnh cy si :
263, 65
4, 0264
= 65,48 ppm.
Bi 15: Gluodenis m t phng php s dng ICP phn tch lng Pb v
Ni trong mu ng thau.
a) Vic xc nh Pb theo phng php chun ngoi chun b t mu ng
thau cha lng Pb cha bit. Kt qu phn tch cho trn bng sau:

Stt %W/W Pb Cng pht x (I.10
-4
)
1 0.000 4.39
2 0.0100 18.7
3 0.0200 32.0
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94
4 0.0650 128
5 0.3500 622
6 0.7000 1260
7 1.0400 1770
8 2.2400 3880
9 3.1500 5610
10 9.2500 16400

Thnh phn % khi lng ca Pb trong mu l bao nhiu khi cng pht
x ca mu l 9.25.10
4
?

b). Vic xc nh Ni theo phng php chun trong chun b t mu ng
thau cha lng Ni cha bit. Kt qu phn tch cho trn bng sau:

Stt %W/W Ni T s ca cng pht
x
1 0.000 0.00267
2 0.0140 0.00154
3 0.0330 0.00312
4 0.1300 0.12000
5 0.2800 0.24600
6 0.2800 0.24700
7 0.5600 0.53000
8 1.3000 1.20000
9 4.8200 4.40000

Thnh phn % khi lng ca Ni trong mu l bao nhiu khi t s cng
pht x ca mu l 1,10.10
-3
?
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95

Gii:
a, Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l bnh
phng ti thiu I = aC + b:
Stt
%W/W Pb
Cng pht x
(I.10
-4
)
I.C C
2
1 0,000 4,39 0,000 0,0000
2 0,010 18,7 0,187 0,0001
3 0,020 32,0 0,640 0,0004
4 0,065 128,0 8,320 0,0042
5 0,350 622,0 217,7 0,1225
6 0,700 1260,0 882,0 0,4900
7 1,040 1770,0 1840,8 1,0816
8 2,240 3880,0 8691,2 5,0176
9 3,150 5610,0 17671,5 9,9225
10 9,250 16400,0 151700 85,5625
n=10 C=15,68 A=29670 AC=181012,35 C
2
=102,2
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
68 , 15 2 , 102 . 10
68 , 15 . 29670 35 , 181012 . 10

= 1772,8


b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
68 , 15 2 , 102 . 10
68 , 15 . 35 , 181012 2 , 102 . 29670

= -10,266

Xy dng ng chun thu c: I = (1772,8C 10,266).10
4

Ta c: I = 9,25.10
-4
tnh c C% = 0,011%

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96
b) Tin hnh xy dng ng chun, hi qui tuyn tnh theo nguyn l bnh
phng ti thiu K = aC + b:

Stt %W/W Ni Cng pht x A.C C
2

1 0,000 0,00267 0,0000 0,0000
2 0,014 0,00154 0,0000 0,0002
3 0,033 0,00312 0,0001 0,0011
4 0,130 0,12000 0,0156 0,0169
5 0,280 0,24600 0,0689 0,0784
6 0,280 0,24700 0,0692 0,0784
7 0,560 0,53000 0,2968 0,3136
8 1,300 1,20000 1,5600 1,6900
9 4,280 4,40000 18,8320 18,3184
n=9 C=6,877 A=6,75033 AC=20,8426 C
2
=20,4970
a =


= =
= = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i
n
i
i i
C C n
C A C A n
1
2
1
2
1 1 1
=
2
877 , 6 497 , 20 . 9
887 , 6 . 8426 , 20 8462 , 20 . 9

= 0,9149

b =


= =
= = = =
|
.
|

\
|

n
i
n
i
i i
n
i
n
i
i i i
n
i
n
i
i i
C C n
C C A C A
1
2
1
2
1 1 1 1
2
.
=
2
877 , 6 497 , 20 . 9
887 , 6 . 8426 , 20 497 , 20 . 75033 , 6

= 0,0039
Xy dng ng chun thu c: K = 0,9149C- 0,0039 C = 5,465.10
-3


Kt lun chng III: Chng Phng php phn tch Quang ph pht
x nguyn t : xy dng h thng cu hi t lun v h thng bi tp c
phn loi theo cc dng bi tp v xut cch gii: Xc nh gi tr nguyn
t ng vi mc nng lng m electron chuyn ti, tnh nng lng photon
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97
ca cc bc sng ca bc x n sc, xc nh % ca kim loi trong mu
bng phng php chun, khi bit cng pht x.






CHNG IV
CC PHNG PHP TCH, CHIT V PHN CHIA

IV.1 C S L THUYT CA PHNG PHP CHIT:
IV.1.1 nh ngha v h s phn b:[16]
- Chit l phng php tch, phn chia, lm giu cht da vo qu trnh
chuyn chn lc cht phn tch t pha ny sang pha khc. Tu theo cht tan,
ngi ta c th s dng cc dung mi chit, cng nh tc nhn chit khc
nhau.
- c im chung ca qu trnh chit: hai pha khng trn ln; cht tan
chuyn t pha ny sang pha khc; cht tan phn u tin vo pha no c tnh
cht tng t n.
- Gi s c mt cht tan A c ho tan trong hai dung mi (1) v (2) khng
trn ln vi nhau. Cht tan A s c phn b gia hai dung mi:
A (1) A (2) (IV.1)
Thng thng dung mi (1) l nc. Dung mi (2) l dung mi hu c. Qu
trnh cht tan A chuyn t dung mi (1) sang dung mi (2) c gi l qu
trnh chit.
p dng nh lut tc dng khi lng cho cn bng (V.1) ta c biu thc:
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98
D =
( )
( )
) 1 (
) 2 (

A
A
(IV.2)
(A)
(2)
: nng cht tan A trong dung mi (2).
(A)
(1)
: nng cht tan A trong dung mi (1).
xt i vi trng hp mt dng ca A phn b 2 pha khc nhau:
K
D
=
) 1 (
) 2 (
] [
] [
A
A
K
D
:gi l hng s phn b.
IV.1.2 Hng s chit:[27]
Cho ion kim loi M
n+
to phc vi phn t X
-
sau em chit bng dung
mi hu c, cn bng chit xy ra nh sau:
M
+ n
nc
+ n(HX)
hc
(MX
n
)
hc
+ nH
+
nc

K
ex
=
n
hc nc
n
n
nc hc n
HX M
H MX
] [ . ] [
] [ . ] [
+
+
(IV.13)
K
ex
= | . .
n
MX
n
HX
a
D
D
K
|
|
.
|

\
|
(IV.14)
K
ex
: hng s chit.
| : hng s bn phc MX
n
.
D
HX
: h s phn b ca phc HX.

n
MX
D : h s phn b ca phc MX
n
.
K
a
: hng s phn li ca axt HX.
Hng s chit c trng cho kh nng tch ion kim loi ra khi pha nc
gi tr K
ex
cng ln th kh nng chit cng tt.

IV.1.3. Cc yu t nh hng n qu trnh chit ho hc:[11]
IV.1.3.1. nh hng ca nng H
+
trong pha nc:
Trng hp H
+

tham gia chit: khi axit ho dung dch, H
+
i vo lin
kt vi tc nhn chit, tr thnh ion dng ngay trn b mt phn chia gia
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99
hai pha; tip theo, chng lin kt bn vng vi cc ion i trong pha nc l
cc cht cn chit v chuyn vo pha hu c.
Th d: Chit Fe
3+
bng ete trong mi trng axit:
(Fe
3+
)
nc
+ 4(Cl
-
)
nc
+ (H
+
)
nc
+ xS
hc
= ( H [FeCl
4
]S
x
)
hc
K
ex
=
x
hc nc nc nc
hc x
S H Cl Fe
S FeCl H
] [ ] [ ] [ ] [
) ] [ (
4 3
4
+ +

Tuy nhin Fe (III) cn tn ti dng t do.
H s phn b iu kin: D =
nc x nc
hc x
S FeCl H Fe
S FeCl H
) ] [ ( ] [
) ] [ (
4
3
4
+
+

Gi s c bao nhiu Fe
3+
u chuyn thnh FeCl

4
sau u to dng chit
H(FeCl
4
)S
x
v chuyn ln pha hu c by nhiu v c nng thch hp
khng c sn phm ph, lc : D =
nc
hc x
Fe
S FeCl H
] [
] ] ( [
3
4
+

Thay D vo K
ex
ta c: K
ex
=
x
hc nc nc
S H Cl
D
] .[ ] .[ ] [
4 +

Nu trong iu kin th nghim khng i, K
ex
= const, nng [Cl
-
] ln
= const D ch ph thuc vo [H
+
].
lgD = lgK
ex
+ 4lg[Cl
-
]
nc
+ lg[H
+
]
nc
+ xlg[S]
hc
Biu din s ph thuc lgD vo lg[H
+
] c biu din bng th:
A = (lgK
ex
+ 4lg[Cl
-
]
nc
+ xlg[S]
hc
) = const

Hnh 4.1: nh hng ca nng H
+
trong pha nc
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100
Nu c z H
+
tham gia phn ng, ta c: tgo = z; lgD = A + lgH
+

IV.1.3.2. nh hng ca hiu ng mui:
* Cc mui khng to phc:
Gi s c cc h s chit Th(NO
3
)
4
hoc UO
2
(NO
3
)
2
/ NO

3
/ TBP.
Nu c thm cc mui trong pha nc v d NH
4
NO
3
, Ca(NO
3
)
2
,
Al(NO
3
)
3
.
Cc mui ny khng b chit ln pha hu c nhng n c nh hng nh
sau:
- Hng s in mi, c thay i.
- Lc ion ca nc thay i.
- T trng hai pha thay i.
* Cc mui to phc vi ion kim loi trong pha nc:
Gi s c ion kim loi ngoi vic to phc vi tc nhn chit HR cn to
phc vi cht to phc ph X: D = K
ex

x
x
H
HR
] [
] [
+

Gi s ion kim loi to phc vi X, ta c: | =
] ][ [
] [
X M
MX

[MX] = | [M] [X]
D =
] [ ] [ ] [
] [
X M M
M
nc nc
hc
| +
=
]) [ 1 ( ] [
] [
X M
M
nc
hc
| +
=
]) [ 1 ( X
D
| +

K
ex
=
|o + 1
D
.
x
x
HR
H
] [
] [
+

Nh vy, khi | tng K
ex
gim.
IV.1.3.3. nh hng ca tc nhn chit:
* Nng tc nhn chit:
lgD = lgK
ex
+ npH + lg[HR]
hc
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101

Hnh 4.2: nh hng ca nng tc nhn chit.
Khi [HR] tng lgD tng, tuy nhin khi t ti mc nht nh th khng
tng na, mt khc pH
1/2
gim, c ngha l c th chit mi trng axit
hn.
* nh hng bn cht ca cu t chit:
+ Cht ni phc: v tr ca nhm chc, loi nhm chc c th hnh
thnh lin kt bn cht v kt qu c th gy nh hng khc.
+ Chit theo kiu A
+
, B
-
.
* nh hng ca nhit :
K
ex
=
2
1
f
f
exp
RT
M M ) (
0
1
0
2

; T tng D gim.

IV.1.3.4. iu kin chit:
* H s tch cng khc 1 cng tt:
o =
B
A
D
D
= 1
* H s tp cht =
A
B
E
E
cng nh cng tt.

IV.2. C s l thuyt ca phng php sc k:[26]
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102
Khi pha ng cha mt phn t cht cn phn tch A c cho chy qua
ct cha pha tnh th cht cn phn tch s c phn b gia 2 pha theo h
s phn b D: A
m
= A
(ng)
- A
( tnh)
= A
S

D =
d
t
A
A
] [
] [
=
m
S
A
A
] [
] [
(1)
[A]
t
l nng cht A trong pha tnh ti thi im ny trong ct v [A]

l
nng cht A trong pha ng. A ch c th chuyn ng qua ct khi n
trong pha ng. Ni cch khc, nu D

rt ln th cht A s ch yu pha tnh
v s b gii hp rt chm. Mun bit mt cht cn phn tch s b gii hp
nhanh hay chm ra sao, ta cn bit t l thi gian m n s pha ng. T l
ny n gin l t l ca cht A trong pha ng ti bt k thi im no. Do
:
f = t l thi gian trong pha ng =
mmol A trong pha ng
Tng mmol A trong ct
f =
S S m m
m m
V A V A
V A
] [ ] [
] [
+
(2)
trong : V
m
, V
S
l th tch pha ng v pha tnh tng ng. C th n
gin ho phng trnh (2) bng cch chia c t v mu s cho [A]
m
V
m
:
f =
m m S S
V A V A ] [ / ] [ 1
1
+
=
m S
V DV / 1
1
+
(3)
T (3) ta thy, mc d [A]
S
v [A]
m
bin i khi i qua ct nhng t s
[A]
S
/[A]
m
bao gi cng bng D khi t ti cn bng. S hng DV
S
/V
m

c dng di dng tha s dung tch k, v th nn: f =
' 1
1
k +
(4)
Vn tc U
A
ca A i qua ct s bng vn tc U ca pha ng trong sut thi
gian m cht A cn trong pha ng v s bng khng khi n pha tnh.
Do vy: U
A
= U
f
= U (
' 1
1
k +
) (5)
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103
S hng
' 1
1
k +
1 v k 0; v th vn tc ca A khng bao gi c th ln
hn vn tc ca pha ng (dung mi ra gii).

IV.2.1 Thi gian lu:
Cht cn phn tch A cui cng s c gii hp ra khi ct mt thi
im t
R
gi l thi gian lu. T vn tc ca A v chiu di ca ct, c th
tnh c thi gian lu l:
t
R
=
chiu di ct (cm)
vn tc ca A (cm/s)
t
R
=
A
U
L
=
U
L
(1 + k) (6)


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104
Hnh 4.3: Tch sc k do Michael Txvet thc hin, cc hp phn A, B, C
c th c quan st theo trc din khong cch (A) v trc din thi gian
(B).

Pha ng s chy qua ct vi vn tc U nn thi gian n lu li trong ct
t
m
l: t
m
=
U
L
(7)
c th t hp cc phng trnh (6), (7) c:
t
R
= t
m
(1 + k) (8)
Thi gian lu ca bt k cht no khng b gi pha tnh (D = 0 k = 0)
cng s l t
m
. iu ny cho php ta o c t
m
bng cch theo di vn tc
ca cht khng b ct gi, chng hn nh khng kh trong ct sc k kh tiu
biu.

IV.2.3. Th tch lu:
Th tch lu ph thuc vo tc chy (F) ca pha ng qua ct l mt
bin s thc nghim thng bin i t th nghim ny qua th nghim kia.
Mt khc, th tch pha ng cn ra gii cht phn tch s khng ph
thuc vo tc chy. Th tch lu V
R
s l:
V
R
(ml) = t
R
(s) . F (ml/s) (9)
ng thi, th tch ca pha ng V
m
trong ct l:
V
m
(ml) = t
m
(s) . F (ml/s) (10)
V
m
cng c coi l th tch trng trong ct v bt k th tch no trong ct
m khng b pha tnh chim s b pha ng chim. T hp (8), (10) ta c:
t
R
= t
m
(1 + k)

F
V
R
=
F
V
m
(1 + k) V
R
= V
m
(1 + k) (11)
V
R
= V
m
+ V
m
k
V
R
= V
m
+
m
S m
V
DV V

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105
V
R
= V
m
+ DV
S
(12)
Th tch lu ph thuc vo th tch pha ng trong ct, th tch pha tnh v
h s phn b. Hiu s V
R
- V
m
l quan trng hn c. l th tch ra gii
khng tnh th tch cn lp khong trng trong ct, n c coi l th tch
lu hiu chnh V
R
:
V
R
= V
R
- V
m
= D V
S
(13)
Th tch lu hiu chnh t l thun vi hng s cn bng ca qu trnh tch.
Hng s t l l th tch pha tnh trong ct n s khng i i vi bt k mt
ct nht nh no. Nu bit th tch pha tnh th c th chia th tch lu
hiu chnh cho V
S
c th tch lu c trng V
g
:
V
g
=
S
R
V
V
= D (14)
V
g
cn l th tch lu ra gii cht phn tch trong mt n v th tch
hoc trong mt n v v lng pha tnh. Trong thc t, c th dng trng
lng pha tnh thay cho V
S
xc nh th tch lu c trng:
V
g
=

D
: t trng ca pha tnh
IV.2.3. Sc k kh (GC):[25]
IV.2.3.1. Sc k kh rn (GSC):
Trong GSC cht mang rn l pha tnh v in hnh l polime,
silicagel, nhm oxit. Hin tng hp ph gi vai tr chnh v thng to ra
nhng pha sc k i xng (to ui cho di) v D thng ph thuc nng
trong cn bng hp ph.
- Ct c nhi cht rn hp ph mnh cht cn phn tch c th
c thi gian lu lu hn nhiu so vi thi gian lu trong GLC, do
m nhng cht bay hi c th c tch d dng.
- Cc ht rn c dng nht l Silicagen hoc nhm oxit u c th
tc dng nh nhng cht xc tc lm cho cc phn ng ho hc
din bin c trong ct vi cht cn phn tch.
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106

IV.2.3.2. Sc k kh lng (GLC):
Ct nhi - khi s dng pha tnh lng n phi c gi trn mt s
cht mang rn ngn khng cho n di chuyn qua ct theo pha ng. Cht
dng lm cht mang thng thng nht l t lng nguyn, mt cht liu
ca silic cha khung hai nguyn t. Cht liu ny l thnh phn chnh trong
gch chu la, bn nhit cao.
IV.3. C s l thuyt ca phng php tch:[12]
IV.3.1. Tch cht bng phng php chng ct:
IV.3.1.1. Cn bng lng hi ca h hai hay nhiu cu t:
xc nh s a l thuyt v t s hi lu phi c cc du hiu cn bng
lng - hi ca h cht cn tch p sut cn chng ct. Thnh phn ca pha
hi v pha lng phi khc nhau.
Khi h cht cn tch l l tng th cn bng lng - hi c tnh theo nh
lut Raoult: P
i
= x
i
P
oi

P
oi
: p sut hi bo ho ca cu t i trng thi nguyn cht;
P
i
: p sut hi ring phn ca cu t i ti hn hp c thnh phn x
i
.
x
i
: phn s mol ca cu t.
i: pha lng x
i
=
i
i
n
n
E

tnh s cn bng ng p ca h hai cu t l tng phi c phng
trnh p sut hi ca hai cu t, theo phng trnh Clausius Clopayron:
lgP = A -
T
B
= A -
RT
H
V
. 303 , 2
A

Nu hn hp hai cu t khng phi l dung dch l tng th phi xc nh
cn bng lng hi p sut cho trc.

IV.3.1.2. Xc nh s a l thuyt v t s hi lu bng phng php MC
Cabe - Thielo:
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107
T s hi lu l t s gia phn cht hi lu li v phn cht c
chng ct ra:
=
D
R

Phng php MC Cabe - Thielo da trn s y/x xc nh s a l
thuyt v t s hi lu.
xc nh s a l thuyt, trc ht ta xy dng ng lm vic ca
phn trn ct ct bng cch ni im x = x
D
ng cho h trc to vi
im y =
u + 1
1
.x
D
trc tung (x
D
: phn s mol ca cu t d bay hi trong
phn ct ra).
IV.3.1.3. Xc nh s a l thuyt cc tiu v t s hi lu cc tiu theo
phng php MC Cabe - Thielo:
th nghim ct chng ct ngi ta thng lm vic vi t s hi lu
phn ton lng v ly mt lng rt nh cht phn tch, t xc nh
s a l thuyt bng phng php MC Cabe - Thielo khi dng ng cho
ca h to chnh l ng lm vic ca ct chng ct.
xc nh t s hi lu cc tiu, ngi ta xy dng ng lm vic ca
phn trn ct ct, ng ny ct ng cn bng lng hi. T on ct ca
ng ny trn trc y ta tnh c t s hi lu cc tiu:
min
=
y
x
D
- 1
Nh vy trong qu trnh chng ct s xy ra hai trng hp cho mt nhim
v tch l:
+ Nu tin hnh chng ct vi t s hi lu cc ln th ch cn s a l
thuyt nh v ngc li.
+ Vi t s hi lu nh th s a l thuyt phi ln.

IV.3.1.4. Xc nh ng knh ca ct chng ct v chiu cao ca ct
chng ct cho yu cu tch cho:
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108
xc nh ng knh ca ct chng ct trc ht da trn lng ct ly
ra D. Khi lng dng ca hi bay ln bao gm c phn cht bay ct ra D v
phn hi lu R: n = D + R m v =
D
R
nn n = (1 + v )D
th tch dng vi phn: V = n
P
RT

Vi R = 0,0826 l.at.mmol
-1
.k
-1
; P: p sut ; T:
o
K
M V = A.W trong A l thit din ca ct chng ct:
A = tx
2
= t
4
2
d
nn d = t / 4A
Chiu cao ca ct chng ct c suy ra t s a l thuyt (thng 3 a l
thuyt c chiu cao 1m).

--------------- v: vn tc dng
v d: ng knh ct chng ct
---------------
d


V.4 CU HI:
Cu 1: Nguyn tc ca chit vt l l gi?
HDTL:
- Chit vt l phi m bo c nguyn tc l cht tan c dng chit
ging vi chnh n pha ban u, ngoi ra cht tan khng tham gia cc phn
ng ph. H chit khi c xem l l tng, cn bng cht tan ch xy ra
gia hai pha khng trn ln. Khi p dng qui tc Gibbs m t qu trnh
ny:
N + F = C + 2
N: s pha c trong h; C: s cu t; F: s bc t do ca h
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- i vi h chit gm pha nc v pha hu c, N= 2, nu c mt cht tan
c trong h th C = 3. S bc t do chnh l cc iu kin chit: nhit , p
sut v nng cu t, F = 3.
- H chit tin hnh iu kin T = const; P = const, h ch ph thuc vo
nng , khi t s nng ca cht tan gia hai pha l mt hng s.
- Cc cht tan thng l cc hp cht hu c phn cc hoc khng phn
cc, n tng tc vi cc hp cht phn cc hay khng phn cc khc trong
pha hu c to nn cc lin kt phn cc, lin kt phn tn.
Th d: chit phenol t nc vo CHCl
3
; cc phn t hu c phn cc lin
kt vi phenol v ko chng vo pha hu c, trong thc t ngi ta dng hn
hp tc nhn chit khc nhau gm nhiu loi dung mi c phn cc khc
nhau.

Cu 2: iu kin ca phng trnh Nernst cho qu trnh chit vt l?
HDTL: Nernst chng minh c rng: t s nng ca cht tan hai
pha khng trn ln trong iu kin nht nh l mt hng s hay:
1
2
C
C
= const.
iu kin ca phng trnh Nernst:
+ Hai dung mi khng trn ln.
+ Nng cht tan long.
+ Dng tn ti ca cht tan.
Nernst xem qu tnh chit l qu trnh cn bng cht tan gia hai pha
khng trn ln vo nhau. Khi cn bng pha thit lp, ho th ca cht tan
trong pha 1 bng ho th ca cht tan pha 2:
1
=
2
hay
0
1
+ RT lna
1
=
0
2
+ RT lna
2

0
1
,
0
2
: ho th ca cht tan pha 1 v pha 2 iu kin tiu chun.
R = 8,3144 J/mol: hng s kh. C
2
T: nhit tuyt i (K).
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110
a
1
, a
2
: l hot ca cht tan pha 1 v pha 2.
a = f . C
ta c:
1
2
C
C
=
2
1
f
f
exp(
RT
) (
0
1
0
2

) tgo = K
P

C
1

Trong iu kin 2 pha khng trn ln, ta c
0
1
=
0
2
= const, mt khc trong
iu kin ng nhit v ng p P = const; T = const.

Phng trnh phn b Nernst:
1
2
C
C
= K
P
= const hay C
2
= K
P
. C
1

Cu 3: H s phn b iu kin l g? Cho 2 v d minh ho?
HDTL:
Trong thc t cht tan thng c nhng cn bng khc ngoi cn bng
phn b cht tan gia hai pha lm cho cht tan c nhiu dng ngoi dng
chit thng thng.
H s phn b iu kin D:
D =
nc
hc
C
C

=
tng nng cht phn tch trong pha hu c
tng nng cht phn tch trong pha nc

V d 1: I
2
phn b qua pha nc v pha hu c, trong trng hp pha nc
c I
-
, ta c cn bng sau: I
2
+ I
-
= I
3
-

V vy h s phn b iu kin l: D =
n n
hc
I I
I
] [ ] [
] [
3
2

+

V d 2: R COOH l axit hu c c cn bng:
pha nc: R COOH R COO
-
+ H
+

pha hu c: 2R COOH (R COOH)
2 hc
vi D =
n n
hc hc
RCOO RCOOH
RCOOH RCOOH
] [ ] [
] ) [( ] [
2

+
+

D ph thuc vo nhit , pH, phn ng ph.

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111
Cu 4: Qu trnh ha hc gm cc giai on no? Thit lp mi quan h
gia cc hng s ca cc qu trnh chit?
HDTL:
Qu trnh chit l qu trnh tng hp ca nhiu giai on:
* Chuyn tc nhn chit t pha hu c sang pha nc hay pha rn, chnh xc
hn l sang b mt phn chia gia hai pha:
S
hc
S
nc
K
1
=
nc
hc
S
S
] [
] [

* Phn ng gia tc nhn chit v cht tan:
xS
nc
+ Na
+
nc
+ (NO

3
)
nc
{(S
x
Na
+
)NO

3
}
nc
K
2
=
nc nc
x
n
nc x
NO Na S
NO Na S
] [ . ] [ . ] [
] ) ... [(
3
3
+
+

* Vn chuyn dng chit vo pha hu c:
[(S
x
Na
+
)NO

3
]
nc
[(S
x
Na
+
)NO

3
]
hc
K
3
=
nc x
hc x
NO Na S
NO Na S
] . ... [(
] ) ... [(
3
3
+
+

Thay K
2
vo K
3
ta c: K
3
=
nc nc
x
nc
hc x
NO Na S K
NO Na S
] [ . ] [ ] [
] ) ... [(
3 2
3
+
+

Thay K
1
vo K
3
ta c: K
3
=
2
1
K
K
.
nc nc
x
hc
hc x
NO Na S
NO Na S
] [ . ] [ ] [
] ) ... [(
3
3
+
+

Qu trnh trn c th xem nh l mt phn ng ho hc v da vo nh lut
tc dng khi lng xc nh hng s chit. Cht tan NaNO
3
phn ng
vi xeton (S) i vo pha hu c. Oxi trong phn t xeton cn cp electron
c th lin kt phi tr vi Na
+
v v vy phn t tr thnh tch in dng v
duy tr phi c NO
3
-
theo kiu sonvat.
Phn ng tng hp c th vit nh sau:
x(S)
nc
+ (Na
+
)
nc
+ (NO

3
)
nc
{(S
x
Na
+
)NO

3
}
hc

K
ex
=
nc nc
x
hc
hc x
NO Na S
NO Na S
] [ . ] [ . ] [
] ) ... [(
3
3
+
+

Mi lin h gia cc hng s ca cc qu trnh chit l:
K
ex
=
1
3 2
.
K
K K

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112
Cu 5: pH c nh hng n h s phn b nh th no? Hy xy dng
th biu din s ph thuc phn trm chit (E%) vo pH?
HDTL:
Ta xt qu trnh chit phc kim loi M
n+
c to thnh gia ion M
n
+
vi thuc th to phc HQ bng dung mi hu c.
Cc cn bng xy ra trong 2 pha hu c nh sau:
Phn b thuc th HQ:
HQ
hc
= HQ
nc
(5.1)
D
HQ
=
nc
hc
HQ
HQ
] [
] [
(5.2)
Phn li thuc th to phc HQ trong pha nc:
HQ + H
2
O H
3
O
+
+ Q
-
(5.3)

HQ
a
K =
nc
nc
HQ
Q O H
] [
] ][ [
3
+
(5.4)
Phn ng to phc: M
n+
+ nQ
-
MQ
n
| =
n n
n
Q M
MQ
] ][ [
] [
+

(5.5)
Phn b phc MQ
n
gia hai pha:
MQ
n

(hc)
= MQ
n (nc)

n
HQ
D =
nc n
hc n
HQ
MQ
] [
] [
(5.6)
Trong pha hu c ch tn ti mt dng MQ
n
v i b phn phc MQ
n
c
chit ln pha hu c. Nn ta c th vit hng s phn b iu kin K
D
nh
sau: K
D
=
nc
n
nc n
hc n
M MQ
MQ
] [ ] [
] [
+
+
=
nc
n
hc n
M
MQ
] [
] [
+

(5.7)

nc n
MQ ] [ <<
nc
M ] [
+

Thng thng trong phng php chit, ngi ta s dng lng thuc th
to phc bao gi cng ln so vi nng kim loi. Thuc th bao gi cng
ho tan tt trong dung mi hu c nn nng ca n trong pha nc nh.
Vy ta c th vit [HQ]
hc
>> [HQ]
nc
.
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113
Gi thit rng, C
HQ
= [HQ]
hc
(5.8)
Theo nh lut phn b ta c:

nc n
MQ ] [ =
n
MQ
D .
nc n
MQ ] [ (5.9)
Theo phn t (5.5):
nc n
MQ ] [ = | .
nc
n
M ] [
+
.
n
nc
Q ] [

(5.10)
Thay (5.10) v (5.9):
hc n
MQ ] [ = | .
n
MQ
D .
nc
n
M ] [
+
.
n
nc
Q ] [

(5.11)
Thay (5.11) v (5.7):
K
D
=
nc
n
n
nc nc
n
MQ
M
Q M D
n
] [
] [ ] [ .
+
+
|
=
n
nc MQ
Q D
n
] [ .

| (5.12)
Ta c:
nc
Q ] [

=
] [
] [
3
+
O H
HQ K
nc a
(5.13)
Thay (5.13) v (5.12):
K
D
=
n
n
nc n
a MQ
O H
HQ
K D
n
] [
] [
. . .
3
+
| (5.14)
Theo (5.2): [HQ]
hc
= D
HQ
. [HQ]
nc

hay [HQ]
nc
=
HQ
hc
D
HQ] [
(5.15)
K
D
=
n
n
hc
n
HQ
n
a
MQ
O H
HQ
D
K
D
n
] [
] [
. . .
3
+
| (5.16)
Cc gi tr | ,
n
MQ
D ,
HQ
D ,
hc
HQ] [ ,
a
K coi nh bng const, k hiu chung
bng K
*
K
D
= K
*
.[H
3
O
+
]
-

(5.17)
gi s V
nc
= V
hc
theo phng trnh D =
E
E
100
.
hc
nc
V
V

D = K
*
[H
3
O
+
]
-n
=
E
E
100
(5.18)
lgE lg(100 - E) = lgK
*
+ npH
t (5.17) th ph thuc E% vo pH vi nghing n. Gi tr pH ti
E = 50%. k hiu pH
1/2
(D=1): pH
1/2
= -
n
1
lgK
*
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114

Hnh 4.4: ng cong c trng v s ph thuc phn trm chit vo pH

Cu 6: Nghin cu phn ng chit Thori bng axetyl axeton trong benzen.
Trong dung dch nc ch xt s tn ti ca cc dng phc bc thp nht ca
Thori: ThX
3+
; ThX
2
2+
; ThX
3
+
. Khng xt n cc phc hiroxo. Hy thit lp
h s phn b iu kin?
HDTL:
H s phn b iu kin D c th vit :
D =

=
=
+
1
0
] [ ] [
] [
n i
i
nc i nc n
hc n
MX MX
MX

t

=
=

=
1
0
] [
1
n i
i
i
nc i
X K
o
v K
o
= 1
D =
o
nc
n
nc n
hc n
M
MX
MX
] [
] [
] [
+
+
= K
D
.
o . ] [
] [
1
1
nc n
nc
n
MX
M
+
+
(6.1)
Phng trnh (6.1) ch p dng trng hp bit nng anion to phc X
-
.
pH thp, thuc th HX tn ti ch yu dng khng phn li HX c
chit ln pha hu c vi h s phn b, v vy:
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115
[X
-
]
nc
=
nc HX
hc a
nc
nc a
H D
HX K
H
HX K
] [
] [ .
] [
] [
+ +
= (6.2)

=
=
=
1
0
1
n i
i
i
K
o
i
nc HX
hc a
H D
HX K
|
|
.
|

\
|
+
] [
] .[
(6.3)
Sau khi bin i ta c h s phn b iu kin:
D =
n
nc
n
a
n
nc D
D
HX K
H K
K
HX
MX
] .[ . .
] .[
1
| o
+
+
(6.4)

Cu 7: Cn c vo u phn loi h chit? H chit c phn thnh
my loi? Cho v d?
HDTL: Da vo bn cht hay tnh cht chung ca cc hp cht c th chit,
ngi ta phn thnh mt s h chnh sau y:
* Chit cc cht v c n gin, chng c phn b gia 2 tng theo nh
lut phn b.
V d: I
2
c phn b gia dung mi hu c (benzen) v dung mi
nc.
* Chit cc phc cht dng vng cng (chelat). y l loi hp cht c
ng dng ph bin nht chit cc ion kim loi. Cc phi t to phc:
8-oxiquinolin, ithizon, ietyl ithiocacbonat, iphenyl cacbazit l nhng
phi t to phc vng cng vi cc ion kim loi thnh cc phc cht khng
mang in tch v b chit ln pha hu c.
* H chit lin hp ion: Hp cht c chit vo pha hu c l hp cht hnh
thnh nh lin hp ion. C 3 kiu lin hp:
- Kiu 1: Ion kim loi tham gia vo thnh phn trong c hp cht hu c
phc tp.
V d: Cu (I) phn ng vi 2,9 - imetyl phenantrolin mang in tch ha
tr 1+ n kt hp vi ion nitrat hay peclorat thnh hp cht trung tnh c
chit ln pha hu c (CHCl
3
) hay ion ZnCl
4
2-
kt hp vi 2 ion
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116
tribenzilamoni [(C
6
H
5
CH
2
)
3
NH
+
] thnh hp cht khng mang in tch c
chit bng xilen.
- Kiu 2: dung mi hu c ng vai tr rt quan trng. Vic hnh thnh hp
cht b chit ph thuc vo s c mt ca cc anion th d halogenua,
thioxyanat, nitrat, cng nh cc hp cht hu c cha oxi, th d ancol, ete,
xeton, hay cc ete phc tp.
V d: Phc FeCl
4
-
c chit bi ete ietyl t dung dch HCl dng sau:
[(C
2
H
5
)
2
O: H
+
FeCl
4
[(C
2
H
5
)
2
O]
-
].
Nguyn t oxi ca phn t dung mi phi tr vi ion kim loi nn cn gi h
ny l h oxoni. Dung mi hu c tham gia vo thnh phn hp cht b chit.
- Kiu 3: Ion kim loi kt hp vi cc hp cht hu c c khi lng phn t
ln c ha tan trong dung mi hu c. Th d: Chit uran, molipen bng
cc amin c khi lng phn t ln c ha tan trong kerosin.

Cu 8: Cc yu t nh hng n vic hnh thnh dng phc vng cng?
HDTL: Cc yu t sau y nh hng n vic hnh thnh phc:
- baz ca nhm chc.
- m in ca cc nguyn t tham gia lin kt.
- Kch thc vng to thnh.
Gia baz ca phi t v tnh n nh ca phc c quan h gn b vi
nhau.
V d: axetyl axeton (pK
a
= 9,7) to phc vng cng vi ion kim loi bn
vng hn phc hnh thnh gia ion kim loi vi thiophen cacbonyl trifloro
axeton (pK
a
= 6,2) v axyl axeton c tnh baz mnh hn.
m in ca nguyn t to ln lin kt vi ion kim loi v bn phc
vng cng ln c quan h tng phn. Phi t cha nguyn t c m in
cng km th phc hnh thnh cng bn.
Th d: iphenyl thio cacbazon to phc vng cng bn hn phc c phi t
hu c cha oxi iphenyl cacbazon.
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117
Mt yu t gy nh hng n bn phc l kch thc ca vng to
thnh.
V d: Phc c vng 5 cnh v phc c vng 6 cnh u l nhng phc bn.

Cu 9: Cn bng trong h chit vng cng c xc nh nh th no?
HDTL: chit cc ion kim loi, ngi ta phi s dng cc thuc th c
kh nng to phc vng cng, c tnh axit yu, v d cuferon, ithizon,
thng c ho tan trong dung mi hu c. Nu ta k hiu thuc th to
phc vng cng HR v c ho tan trong cc dung mi hu c. N c kh
nng to phc vng cng vi cc ion kim loi. Cc phn ng xy ra nh sau:
1. Phn li thuc th:
HR H
+
+ R
-
K
i
=
] [
] ][ [
HR
R H
+
(9.1)
2. To phc vng cng:
M
n+
+ R
-
MR
(n -1)+
K
1
=
] [
] [
) 1 (
+
+
n
n
M
MR
(9.2)
MR
+
n-1
+ R
-
MR

n
K
n
=
] [ ] [
] [
1
+

R M
MR
n
n

| = K
1
.K
2


K
n

3. Cc phn ng to phc vi phi t l:
M
n+
+ OH
-
= M(OH)
(n-1)+

M
n+
+ X
-
MX
(n-1)+
X
-
: Cl
-
, NO

3
, SO
2
4
, ...
S phn b ca thuc th v phc vng cng gia hai dung mi.
4. S phn b bn thn thuc th:
D
R
=
] [
] [
HR
HR
hc
(9.3)
5. S phn b phc vng cng: D
MR
=
] [
] [
n
hc n
MR
MR
(9.4)
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118
D =
] [
) ( ) ) ( (
...
] [
] [
] [
] [
] [
] [
) ( ) (
) 1 ( 1
n
i j
j n
j
i n
i
n
n
n
n
n
hc n
MR
MX OH M
MR
MR
MR
M
MR
MR

+ +
+ +
+
+ + +


Cu 10: Th no l qu trnh gii chit? Cho v d?
HDTL:
Gii chit l qu trnh ngc li qu trnh chit, c ngha tch cc nguyn
t cn chit khi pha hu c, c th xc nh chng bng cc phng
php thch hp. Nh qu trnh gii chit, ngi ta c th tip tc tch trit
nguyn t cn tr khi nguyn t cn xc nh.
V d: Mt hn hp gm 2 nguyn t X v Y, em chit bng dung mi hu
c c h s phn b khc nhau. Gi s nguyn t X c chit vi h s
phn b 1000, cn nguyn t Y c chit vi h s phn b nh hn: 0,01.
Khi chit 2 nguyn t trong cng iu kin th trong pha hu c c 99%
lng nguyn t X v khong 1% lng nguyn t Y. Nh vy, chit khng
c hon ton. Nhng nu chng ta trn pha hu c vi th tch pha
nc nh ln trc, nhng trong pha ny khng c cha nguyn t X v Y,
th sau ln gii chit ny pha hu c s c 99,8% lng ban u ca nguyn
t X v ch c 0,01 % lng ban u nguyn t Y. Nh vy, nh gii chit
thc t tch c kh hon ton X khi Y. Khi tin hnh gii chit, ngi
ta dng nc c thnh phn (cht to phc, pH) khc vi thnh phn pha
nc dng chit.
Th d: Khi chit Pb
2+
, Cu
2+
, Fe
2+
di dng ietyl ithio cacbamat trong pha
nc pH = 4 11. Sau gii chit cc nguyn t khi pha hu c bng cc
dung dch nc khc nhau.
Th d : Dung dch HCl 0,4M th gii chit c Zn, HCl 4M th gii chit
c Pb, cn Fe, Cu vn li trong pha hu c.

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119
Cu 11: Phng php chit lng - lng l g? Gia chit v chng ct c mt
im ging nhau l g?
HDTL:
+ Chit lng - lng hay cn gi l chit dung mi, l mt phng php tch
da vo s phn b khc nhau ca nhng cht cn tch gia hai pha lng
khng trn ln. Bi khng th thu c cht sch ch qua 1 ln t cn bng
nn ngi ta tng hiu qu tch bng cch, chit ngc dng trong ct hoc
thc hin tch qua nhiu bc ni tip nhau
+ Gia chit v chng ct c mt im ging nhau l c hai phng php
cn tch phn b vi lng khc nhau trong c hai pha. C iu trong chng
ct khi pha th hai (pha hi) cha mt thnh phn ca pha lng ban u th
phng php chit to ra pha th hai (pha lng) ngi ta phi a cht
vo, l a dung mi vo. Cht ny tham d vo cn bng cht ca
phng php v xc nh s c trng ca phng php tch thng qua quan
h ca n vi cht cn tch. Trong phng php chit, iu ny th hin n
gin nht trong h 3 cu t.
Cu 12: c tnh chung ca phng php chit cu t a lng?
HDTL:
- Php c c ca vt vi lng bng cch chit cu t a lng da trn kh
nng tin hnh php chit ny mt cch chn lc (cc nguyn t vi lng cn
phi cn li mt cch nh lng trong pha nc).
- Cu t a lng cn phi c hon ton loi tr t pha nc, tuy nhin
vic tun theo iu kin ny trong mt s trng hp, c bit trong cc
php xc nh ha quang ph th khng nht thit. Ngoi ra phn cn li ca
nguyn t a lng c khi c dng lm cht mang.
- Php chit cc nguyn t a lng c th dng tt c c, v nguyn tc
ch c p dng khi m mu cn phn tch c thnh phn tng i n
gin v cc cu t a lng.
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120
- Vic tch cht c bn khng lm nhim bn pha nc, do vy cn lm vic
mt cch hp l vi mt s lng nh nht v mt lng c th nh nht ca
cc thuc th v vi cc thuc th d dng nhn c dng sch.
- V d: Vic chit cc axit phc kim loi halogenua nh HGaCl
4
,

HFeCl
4
,

HInBr
4
v cc axit phc khc ch cn dng mt dung mi c cha oxi vi
dung lng chit ln s thun li hn so vi vic chit cc hp cht ni
phc. Cc hp cht ni phc kh ha tan trong dung mi hu c.
Ngoi ra, chit chng cn mt s ln cc thuc th, c bit l cc thuc
th chelat, dung mi hu c v cc thuc th iu chnh pH.
- Hiu qu ca c c chit da trn s chit cu t a lng mt mc
ng k ph thuc vo vic gii quyt nhiu vn l thuyt chung. Thuc
nhm cc vn ny, trc ht phi k n vn nh hng ca cu t a
lng ln chit ca cc cu t vi lng (nh hng tng h ca cc nguyn
t ln vic chit) v nh hng ca nng nguyn t a lng ln h s
phn b ca n.

Cu 13: Hy nu cc phng php c c?
HDTL: c c chit, ngi ta dng ch yu cc phng php chit sau
trong cc h lng - lng:
1. Chit chu k trong cht c chit c chuyn t mt pha vo
mt pha khc khi c s lc hai pha.
2. Chit lin tc trong dung mi chit i qua dung dch phn tch lin
tc.
3. Chit ngc dng, trong s c chit ngc dng tun hon.
4. Sc k chit.
Cu 14: Hy cho bit phng trnh Van Deemter c ngha nh th no?
HDTL:
T l thuyt a, c th xc nh c cc i lng c trng quan
trng l n (s a l thuyt) v h ( cao ca mt a l thuyt) nhng khng
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121
cho bit nh hng ca cc iu kin lm vic (nhit , p sut, tc
dng) n cc i lng ni trn. Ch sau khi c s h tr ca l thuyt
ng hc, c bit l vi s ra i ca phng trnh Van Deemter, th mi
nh ca cc thng s thc nghim ln cc i lng ni trn mi c lm
sng t. Phng trnh Van Deemter c biu din nh sau: h = 2 d
p
+
u
D
G
2
+ u
D k
d k
f i
f i
.
) 1 (
8
2 2
2
+ H

Trong : u : tc trung bnh ca dng kh mang.
: khng ng nht ca cht nhi ct.
d
p
:

ng knh trung bnh ca ht cht mang.
: h s Labyrinth v ng i ca kh trong ct.
D
G
: h s khuch tn phn t trong pha kh .
D
F
: h s khuch tn phn t trong pha lng.
k
i
: h s dung lng.
d
f
: dy ca lp phim pha tnh trn cht mang.
Phng trnh Van Deemter thu gn c th c din t nh sau:
h = A +

u
B
+ C u
Trong :
A: i din cho s khuch tn tn x (cn gi l khuch tn
Eddy), cho nhng thng tin v ng i khc nhau ca kh do
cht nhi ct quyt nh.
B: i din cho nhng ch dn v s khuch tn phn t trong pha
kh.
C: biu th tr khng ca ct trong qu trnh chuyn khi trong
pha ng cng nh trong pha tnh.
Cu 15: c tnh chung ca phng php chit - hunh quang l g?
HDTL:
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122
- Cc phng php phn tch da trn s chit cc hp cht ni phc v
vic o hunh quang trong dch chit v ph bin v ngha th km hn
cc phng php chit - trc quang. Tuy nhin, c im quan trng v u
vit ca chng so vi cc phng php chit - trc quang l nhy cao hn.
- S ln nht cc phng php chit - hunh quang trong c dng cc
hp cht ni phc c nghin cu cho Al va Ga. Ngi ta cng bit cc
phng php i vi Ini, cc nguyn t t him v mt s nguyn t khc.
- Cc phng php chit - hunh quang c mt s u im so vi cc
phng php hunh quang trong pha nc, cc u im, mt mc ng
k tng t cc u im lu i vi cc phng php chit trc quang.
- Khng t phng php chit - hunh quang m bo c nhy cao ca
php xc nh. V d, nhy ca php xc nh chit - hunh quang ca Ga
i vi lumogalion 3,5 ln cao hn nhy ca php xc nh trong dung
dch nc.
- Cng hunh quang tng khi chit cc hp cht ny ca Ga vi cc
thuc th tng t. Khi chit phc ca Zn vi 8 - (n - tozilamino) - quinolin
th cng hunh quang cng tng ln.
- S tng chn lc ca php xc nh c th c m bo bng cch
phn chia chit bnh thng cc nguyn t cn xc nh v cn tr.
- Cng nh trong tt c cc phng php da trn s chit cc hp cht ni
phc, nh hng ca dung mi trong cc php xc nh chit - hunh quang
lun lun phi tnh n. Trc ht iu ny c lin quan n vic chn dung
mi theo quan im chit c hon ton nguyn t.

Cu 16: Lm th no c th tm c din tch di pic?
HDTL:
Phn ln cc my sc k hin nay c trang b my tch phn in t.
Tuy nhin nu khng c my tch phn th c 2 phng php gn ng c
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123
th p dng rt tt v cho kt qu ch khc vi phn trm so vi din tch
thc.
Hnh 4.5 (A): Pic c lm gn ng bng mt tam gic.
Hnh 4.5 (B): Pic c lm gn ng bng mt hnh ch nht.
Trong c 2 phng php, ngi ta u gi thit rng phn din tch pic b b
qua s bng mt din tch hnh hc nm bn ngoi pic. Phng php hnh
ch nht ca hnh 4.5 (B) ng hn v c dng nhiu hn phng php
tam gic. R rng c hai phng php u i hi pic c b ngang va phi
cho gi tr din tch ng tin cy. Phng php tch phn in t c th
cho c nhng gi tr din tch ng tin cy. Phng php tch phn in t
c th cho c nhng gi tr din tch ng lp li tt hn 1 % cn cc
phng php tnh din tch gn ng thng lp li t 3 n 4%...

Hnh 4.5
o din tch ca pic: (A): din tch pic = din tch tam gic =
2
1
a.W.
(B): din tch pic = din tch hnh ch nht = h.W
1/2
W
1/2
:Chiu ngang ca pic na cao.
Khi chiu ngang pic qu b nh phn tch c th da vo vic o chiu cao
pic. Chiu cao pic s t l thun vi din tch pic (v do s t l vi lng
cht phn tch) nu mi bin s u c gim st cht ch. Tuy vy ch mt
thay i nh trong vn tc chy, vn tc phun mu hoc nhit c gy
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124
thay i ng k cho chiu cao pic mc d din tch vn gi hu nh khng
i; v th vic ch o chiu cao pic c th dn ti nhng sai s ln.

Cu 17: Ly mt mu nha dng H
+
ri cho n vo 1 dung dch c cha
Na
+
nng cao va phi. Phn ng trao i sau s xy ra:
R-H + Na
+
+ H
2
O R-Na + H
3
O
+
(*)
Thit lp biu thc tnh hng s cn bng D? v cho bit nhng yu t no s
xc nh D?
HDTL:
* H s phn b ca phn ng trao i vn l tch ca cc cht tham gia
phn ng ging nh bt k hng s cn bng no nhng trong trng hp
ny phi k n cc phn t tch in. Vi mi in tch ion chuyn c t
pha ng vo pha tnh th phi c mt in tch chuyn theo hng ngc
li. Hng s cn bng biu th phng trnh (*). (b qua hot ca H
2
O)
K =
] ][ [
] ][ [
3
+
+

Na H R
O H Na R

K

cng c gi l hng s chn lc ca phn ng trao i ion.
* Nhng yu t no s xc nh D?
T phng trnh (*), H
+
trn cht trao i cation b thay th bi mt ion kim
loi no , th K s tng ln trong nhng iu kin sau:
1. in tch trn M
n+
tng.
2. Bn knh ion hirat ho ca M
n+
gim.
3. Lin kt ngang ca nha ln hn (khi mch lin kt ngang gim i th
mi gi tr K

tin ti 1).
4. C hiu ng hp ph, chng hn vi nhng ion hu c phn t lng
ln.
- Yu t 1 cho thy cc cht lm mm nc hot c tt v nhng ion
lm cng nc u 2+, trong khi nha (hoc khong t nhin trao i
ion) cha cc ion 1+.
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125
- Yu t 2 s c ngha quan trng khi cc ion c tnh cht ho hc ging
nhau, chng hn nh khi cn tch cc t him hoc cc actinit. Khi K

tng, ion s b gii hp khi ct chm hn v th vi dy ion kim loi
tng t th cc ion s b ra gii theo trnh t ngc vi bn knh ion
(ion ln nht s b ra gii trc tin).

Cu 18: Gi s c cha 1 mu cha cht cn phn tch A
+
c a ln
nh ct trao i ion v lin tc thm dung mi ra gii dng lm pha ng
vo. Cn phi dng 1 th tch pha ng l bao nhiu trc khi cht A
+
b ra
gii?
HDTL:
V nguyn tc th IEC (sc k trao i ion) khng khc g cc phng
php sc k khc v c p dng phng trnh: V
R
= V
m
(1+ k

)
Trong , V
R
l th tch lu (hoc ra gii); V
m
l th tch pha ng c
cha trong ct (th tch trng) v k l tha s dung lng, tha s ny l:
k=
m
S
A mol m
A mol m
) (
) (
+
+

Trong IEC, k cng c bit di dng D, t s phn b. Tuy nhin trong
trao i ion c s cnh tranh nn ks ph thuc vo bn cht v nng ca
ion tham gia v d nh H
3
O
+
trong phng trnh:
R-H + Na
+
+ H
2
O R-Na + H
3
O
+

Nh vy thi gian lu s ph thuc vo nng cc ion trong dung mi ra
gii.

Cu 19. Hy cho bit cc mi lin h c bn d on s phn b ca
cht tan trong phn b lng - lng?
HDTL:
* Lut phn b Nernst: Bt k mt hp phn trung tnh no cng s phn b
gia 2 dung mi trn ln vi t s nng trong 2 pha l mt hng s.
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126
D =
n
hc
A
A
] [
] [

D: hng s phnb.
[A]
hc
: nng ca cht A trong pha hu c.
[A]
n
: nng ca cht A trong pha nc.
* Phn cht A chit c:
u =
V D
V D
V A V A
V A
n n hc hc
hc hc
. 1
.
. ] [ . ] [
. ] [
+
=
+

V: T s pha (V= V
hc
/V
n
)
V
hc
: Th tch pha hu c.
V
n
: Th tch pha nc.
* Phn chit c sau n ln chit:
u = 1- [
V D. 1
1
+
]
n

D.V = 1099% cht tan c chit vi n = 2
D.V = 0,150% cht tan c chit vi n = 7
* Phn b dng ngc :
Mi lin h gia hng s phn b D ca cht tan trong qu trnh chit
v nng ca cht tan trong cc phu chit hoc cc phn on tch khc
nhau c th hin trong cc phng trnh sau:
[u ] + (1-u )
n
] = 1
Phn chit T
n, r
ca cht tan c mt trong phn on r vi s ln chit n c
xc nh theo phng trnh:
T
n, r
=
n
V D
V D
r n n
n
) . 1 (
.
.
! ) ( !
!
+

Cu 20. Nu mt s u im, nhc im ca k thut ion ho theo c ch
gii hp s dng ngun Laze vi s tr gip nn (MALDI)?
HDTL:
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127
Khi ph - ion ho theo c ch gii hp vi s tr gip nn (Mitrix -
asisted Laser Desorption/Ionization Mass spectrometry: MALDI - MS) cho
php phn tch cc hp cht c phn t lng ln vi nhy cao.
K thut ion ho theo c ch gii hp s dng ngun Laze vi s tr gip
nn cho php phn tch ch vi 1 lng mu kh nh. Hn na, u im ca
tng k thut ny l c th phn tch cc mu khng ng nht. Ngoi ra, k
thut ny cn c s dng hu hiu khi ghp ni vi thit b sc k lng
hiu nng cao (HPLC). Sau y l cc u nhc im ca k thut MALDI:
* u im:
- Khong khi lng c th phn tch ln n 300.000 Da.
- nhy c trng khong t thp hn femtomol n picomol, c
th t n attomol.
- y l mt k thut ion ha mm, thng t hoc khng phn
mnh.
- Ph hp cho phn tch cc hn hp phc tp.
* Nhc im:
- phn gii thp. Mt s thit b MALDI c phn gii cao hn
nhng ch phn tch c khong khi lng thp v nhy s gim.
- Nu mu c th gy kh khn khi phn tch cc hp cht c khi lng
di 1000 Da. nh hng nn ny ph thuc nhiu vo vt liu nn.
- C th b phn hu quang hc do ion ho - gii hp Laze.

V.5 Bi tp:
Dng 1: Tnh nng ca axit cn li trong pha nc, khi bit hng s phn
li axit v h s phn b.
Cch gii:
p dng phng trnh: K
D
= D .
nc a
nc
O H K
O H
] [
] [
3
3
+
+
+
(1)
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128
v K
D
=
nc
hc
HA
HA
C
C
(2)
T (1) v (2)
nc
HA
C

Bi 1: Tnh nng axit axetic cn li trong pha nc nu ta cho 60,0 ml
axit axetic 0,04M chit bng 30,0 ml imetyl ete pH = 3,0 v pH = 8,0.
Bit h s phn b ca axit axetic gia nc v imetyl ete l 780.
K
a
= 1,60.10
-5
.
Gii:
* Ta c: pH = 3,0 [H
3
O
+
] = 1,0.10
-3
M
p dng phng trnh:
K
D
= D .
nc a
nc
O H K
O H
] [
] [
3
3
+
+
+
= 780 .
5 3
3
10 . 6 , 1 10 . 0 , 1
10 . 0 , 1

+
= 768
S mmol CH
3
COOH ban u = 0,04 . 60 = 2,40 mmol.
S mmol CH
3
COOH b phn b gia 2 dung mi:
60,0 .
nc
COOH CH
C
3
+ 30,0 .
hc
COOH CH
C
3
= 2,40 (*)
Ta li c: K
D
=
nc
hc
COOH CH
COOH CH
C
C
3
3
= 768
T (*): 60,0 .
nc
COOH CH
C
3
+ 30,0 . 768 .
COOHnc CH
C
3
= 2,40

nc
COOH CH
C
3
= 1,04 . 10
-4
M
* Ta c: pH = 8,0 [H
3
O
+
] = 1,0.10
-8
M
p dng phng trnh:
K
D
= D .
nc a
nc
O H K
O H
] [
] [
3
3
+
+
+
= 780 .
5 8
8
10 . 6 , 1 10 . 0 , 1
10 . 0 , 1

+
= 0,487
60,0 .
nc
COOH CH
C
3
+ 30,0 . 0,487 .
nc
COOH CH
C
3
= 2,40

nc
COOH CH
C
3
= 3,22 . 10
-2
M

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129
Bi 2: H s phn b ca axit acrylic gia H
2
O v etyl metyl ete l 1200.
Hng s phn li axit K
a
= 1,125.10
-5
. Nu ta em 100,0 ml CH
2
=CHCOOH
0,05M chit bng 50,0 ml etyl metyl ete pH = 4,0 th nng ca axit
acrylic cn li trong pha nc l bao nhiu?
Gii:
Ta c: pH = 4,0 [H
3
O
+
] = 1,0.10
-4
M
Theo phng trnh:
K
D
= D .
nc a
nc
O H K
O H
] [
] [
3
3
+
+
+
= 1200
5 4
4
10 . 125 , 1 10 . 0 , 1
10 . 0 , 1

+
= 1079
Mt khc: K
D
=
nc
hc
COOH CH CH
COOH CH CH
C
C
=
=
2
2
= 1079
S mmol axit acrylic ban u = 0,05 . 100 = 5,0 mmol.
S mmol axit acrylic c phn b gia 2 dung mi:
5,0 = 100,0
nc
HA
C + 50,0 . 768 .
hc
HA
C

hc
HA
C v
nc
HA
C : tng nng ca axt acrylic trong pha hu c v pha nc.


hc
HA
C = 1079 .
nc
HA
C
5,0 = 100,0
nc
HA
C + 50,0 . 1079 .
nc
HA
C

nc
HA
C = 9,25 . 10
-5
M.
Bi 5: H s phn b D ca axit yu HA gia nc v ietyl ete l 800.
Hng s phn li axit K
a
= 1,50.10
-5
. Tnh nng axit HA cn li trong pha
nc nu ta em 50ml axit HA 0,050M chit bng 25,0ml ietyl ete pH =
2,0 v pH = 8,0.
Gii:
Ta bit pH = 2,0 [H
3
O
+
] = 1,0.10
-2
M
p dng phng trnh:
K
D
= D .
nc a
nc
O H K
O H
] [
] [
3
3
+
+
+
= 800 .
5 2
2
10 . 5 , 1 10 . 0 , 1
10 . 0 , 1

+
= 799
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130
S mmol HA ban u = 0,050 . 50 = 2,50 mmol.
S mmol HA c phn b gia 2 dung mi:
50,0 .
nc
HA
C + 25,0 .
hc
HA
C = 2,50

hc
HA
C v
nc
HA
C : tng nng ca axit HA trong pha hu c v pha
nc.
Mt khc ta c: K
D
=
nc
hc
HA
HA
C
C
= 799

hc
HA
C = 799 .
nc
HA
C
2,50 = 50,0
nc
HA
C + 25,0 . 799 .
nc
HA
C

nc
HA
C = 1,25 . 10
-4
M.
* Ta c: pH = 8,0 [H
3
O
+
] = 1,0.10
-8
M
p dng phng trnh:
K
D
= D .
nc a
nc
O H K
O H
] [
] [
3
3
+
+
+
= 800 .
5 8
8
10 . 5 , 1 10 . 0 , 1
10 . 0 , 1

+
= 0,533
50,0 .
nc
HA
C + 25,0 . 0,533 .
nc
HA
C = 2,50

nc
HA
C = 3,95 . 10
-2
M

Bi 6: H s phn b ca I
2
gia CCl
4
v H
2
O bng 85. Tnh nng I
2
cn
li trong pha nc nu ta em 50,0 ml dung dch I
2
1,0.10
-3
M chit bng
CCl
4
theo cc cch sau:
Chit 1 ln bng 50,0 ml CCl
4
.
Chit 2 ln bng 25,0 ml CCl
4
.
Chit 4 ln bng 10,0 ml CCl
4
.
Gii:
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131
p dng cng thc: nu chit n ln mi ln V
2
ml dung mi hu c th sau n
ln chit cht A cn li trong pha nc: C
n
= C
0

n
V V D
|
|
.
|

\
|
+ ) / ( 1
1
1 2
= C
0

n
V
V
D

|
|
.
|

\
|
+
1
2
1
Ta tnh c I
2
cn li trong pha nc:
2
I
C
(1)
= 1,0.10
-3

1
0 , 50 . 85 . 0 , 50
0 , 50
|
.
|

\
|
= 1,16.10
-5
M
2
I
C
(2)
= 1,0.10
-3

2
0 , 50 . 85 . 0 , 50
0 , 50
|
.
|

\
|
= 5,28.10
-7
M

2
I
C
(3)
= 1,0.10
-3

5
0 , 50 . 85 . 0 , 50
0 , 50
|
.
|

\
|
= 5,29.10
-10
M
Phn cn li:
hc
nc
A
A
C
C


Hnh 4.6: Hiu qu ca s ln chit D = 2; V
nc
= 100 ml;
V
hc
=
n
100
; Tng V
dmhc
= 100 ml

Dng 3: Xc nh h s phn b, phn trm chit?
Cch gii: p dng cng thc:
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132
- H s phn b iu kin: D =
n
hc
n
a Y
n
HX
n
nc
MX
HX D
D H
D
n
] [ . .
. ] [
1
| o
+
+

- % chit: t D =
E
E
100
.
nc
hc
V
V
E =
D
V
V
D
nc
hc
+
100

Bi 7: Ngi ta chit thori axetyl axetonat bng etyl benzen iu kin
K
a
=1,17.10
-9
;
n
MX
D = 317;
HX
D = 5,75;
1
| = 8.10
7
;
2
| = 4,2.10
15
;
3
| =
8,3.10
21
;
Tnh % chit thori pH = 5 nu nng cn bng cui cng ca axetyl
axeton trong pha hu c 10
-2
M;
nc
hc
V
V
=
5
1
.
Gii:
p dng cng thc:
o
1
=

=
=
+ |
|
.
|

\
|
1
0
] [
] [
n i
i
i
HX
hc a
i
H D
HX K
K
Ta c:
nc HX
hc a
H D
HX K
] [
] [
=
5
2 9
10 . 75 , 5
10 . 10 . 17 , 1


= 2.10
-7


o
1
= 1 + 8.10
7
.2.10
-7
+ 4,2.10
15
.4.10
-14
+ 8,3.10
21
.8.10
-21
= 251,4
n
hc
n
a
n
H
n
HX K
D H
] [ . .
. ] [
| o
+
=
4
2 9
5
10 . 10 . 17 , 1
75 , 5 . 10
|
|
.
|

\
|

.
15
10 . 2 , 4 . 4 , 251
1
= 4,654
D =
E
E
100
.
nc
hc
V
V
=
654 , 4 1
317
+
= 56,07
E =
D
V
V
D
nc
hc
+
100
=
07 , 56
5
1
07 , 56 . 100
+
= 96,56 4 (%)
Bi 8: Ngi ta chit thori axetyl axetonat bng benzen iu kin
K
a
=1,17.10
-9
;
n
MX
D = 315;
HX
D = 5,95;
1
| = 7.10
7
;
2
| = 3,8.10
15
;
3
| =
7,2.10
21
;
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133
Tnh % chit thori pH = 6 nu nng cn bng cui cng ca axetyl
axeton trong pha hu c l 10
-3
M;
nc
hc
V
V
=
5
1
.
Gii:
p dng cng thc:
o
1
=

=
=
+ |
|
.
|

\
|
1
0
] [
] [
n i
i
i
HX
hc a
i
H D
HX K
K
Ta c:
nc HX
hc a
H D
HX K
] [
] [
=
6
3 9
10 . 95 , 5
10 . 10 . 17 , 1


= 2.10
-7

Ta c:
o
1
= 1 + 7.10
7
.2.10
-7
+ 3,8.10
15
.4.10
-14
+ 7,2.10
21
.8.10
-21
= 225
n
hc
n
a
n
H
n
HX K
D H
] [ . .
. ] [
| o
+
=
4
3 9
6
10 . 10 . 17 , 1
95 , 5 . 10
|
|
.
|

\
|

.
15
10 . 8 , 3 . 225
1
= 5,948
D =
E
E
100
.
nc
hc
V
V
=
948 , 5 1
315
+
= 45,34
E =
D
V
V
D
nc
hc
+
100
=
34 , 45
5
1
34 , 45 . 100
+
= 95,78 %
Bi 9: Ngi ta chit Cu
2+
10
-4
M bng ithizon (HX) c ho tan trong
CCl
4
c mt EDTA 10
-2
M. Tnh h s phn b iu kin D cc gi tr pH =
2 v pH= 4. Hng s bn phc Cu
2+
vi EDTA l 10
18,8
.

Gii:
* pH = 4 ta tm c - lg
Y
o = 8,48.
Hng s bn iu kin ca phc Cu
2+
vi EDTA pH = 4 l
'
CuY
| = 10
10,3
T tm c:
Y
o
1
= 1 + 10
10,3
. 0,01 = 2.10
-8

H s phn b iu kin: D =
n
hc
n
a Y
n
HX
n
nc
MX
HX K
D H
D
n
] .[ . .
. ] [
1
| o
+
+

Bit nng [HX] = 10
-4
M ; K
a
= 3.10
-5

D
HX
= 1,1 . 10
4
;
n
MX
D = 7.10
4

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134
| = 5.10
22
; n = 2
Thay gi tr vo biu thc trn: D =
538 1
10 . 7
4
+

= 130
* pH = 2 ta tm c - lg
Y
o = 13,44.

Y
o
1
= 2,3.10
3
D =
62 1
10 . 7
4
+
= 1,1.10
3

Bi 10: Xc nh s phn b ca cht A sau 3 ln chit. Bit V
hc
= 4ml,
V
nc
= 5ml v D = 2,5.

Gii: Ta c: [A
p
]
n
=
p
hc
A
Vn
V
D
C
|
.
|

\
|
+1
0

[A
1
]
n
=
|
.
|

\
|
+1
5
4
5 , 2
0
A
C
= 0,333
0
A
C pha nc chim 33,3%.
[A
2
]
n
=
2
0
1
5
4
5 , 2
|
.
|

\
|
+
A
C
= 0,111
0
A
C pha nc chim 11,1%
[A
3
]
n
=
3
0
1
5
4
5 , 2
|
.
|

\
|
+
A
C
= 0,037
0
A
C pha nc chim 3,7%
Dng 3: Xc nh s bc tch l thuyt (gi l a l thuyt).
Cch gii:
xc nh s bc tch l thuyt t l m
s
/m
R
cho trc th cn phi
bit ng cn bng m t thnh phn gia t l khi lng Y
ES
trong pha
cho v t l khi lng Y
ER
nm cn bng vi n trong pha nhn. Mi
quan h ny c p dng theo nh lut phn b Nernst: Y
ES
= k.Y
ER
k: h s phn b

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135
Bi 9: Trong mt thit b chit ngc dng, loi phenol khi nc thi
cha phenol, ngi ta cn chit phenol bng benzen.
Trong dung dch chy vo thit b (hn hp nguyn liu) t l khi lng
phenol/nc
ER
Y
vo
= 8.10
-3
. T l khi lng phenol/ nc trong dch b
li ra ca thit b cho php cha ti a
ra
ES
Y = 8.10
-4
. Trong dch chit
(benzen) ti li ra ca thit b cn t t l khi lng phenol/benzen.
ra
ES
Y = 2,85.10
-2

Cn tnh lng benzen i hi mi gi v s bc tch l thuyt khi dng
khi lng ca nc thi l 10.000 kg/gi.
Cho bit cc t l khi lng cn bng nh sau:
Y
ER
(phenol/nc) 0,427.10
-3
0,427.10
-3
5,75.10
-3

Y
ES
(phenol/benzen) 1,109.10
-3
4,97.10
-3
53,1.10
-3




Gii:
Ta c: m
R
= m
Z
( 1 -
ER
Y
vo
) = 10.000(1 0,008) = 9920kg/gi
m
Z
: dng khi lng ca nguyn liu.
m
R
: dng khi lng ca dung mi 1.
Cn bng cht trong ton thit b l:
m
R
(
ER
Y
vo
-
ra
ES
Y ) = m
S
(
ra
ES
Y -
ER
Y
vo
)
Ta c :
m
S
= [(
ER
Y
vo
-
ra
ES
Y )/(
ra
ES
Y -
ER
Y
vo
)].m
R
m
S
= [(0,008 0,0008)/(0,0285 - 0)].9920 = 2506 kg/gi (benzen).
S bc tch l thuyt s c xc nh bng th. Do vy, ta v ng lm
vic trong gin i vi cn bng phn b cho, ng ny xc nh qua
im A (
ES
Y
vo
= 0,008;
ra
ES
Y = 0,0285) v im B (
ra
ER
Y = 0,0008;
ER
Y
vo
= 0).
Gia ng lm vic v ng cn bng chng ta v cc bc thang v tnh
c s bc tch l thuyt theo nhim v tch ra n
th
= 7.
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136

Hnh 4.7 S xc nh s bc tch l thuyt

Lng dung mi cn thit ti thiu i vi nhim v tch t ra, c xc
nh t gi tr nghch o ca dc ca ng thng AB, ng thng ny
ct ng cn bng gi tr trc honh
ES
Y
vo
ng vi t l khi lng cht
tan/cht lng mang ca hn hp nguyn liu. Gi nghch o ca
dc c xem l t l dung mi ti thiu:
(m
S
/m
R
)
min
= (Y
ER
vo
- Y
ER
ra
)/(Y
ES, max
ra
Y
ES
vo
)
Y
ES, max
ra
l t l khi lng ln nht c th t gia cht tan/dung mi trong
dch chit ti t l dung mi ti thiu vi Y
ER
vo
v Y
ES
vo
cho trc cng nh
Y
ER
ra
i hi.
Cu 10: Trong mt hn hp clo ha lu hunh c phn khi lng ca
mono sunfo clorua W
ER
vo
= 0,15. T mt hn hp nguyn liu ny sunfo
clorua c chit ra bng metanol trong mt thit b ngc dng. Cc t l
cn bng gn nh tun theo nh lut phn b Nernst: Y
ES
= 1,3Y
ER
. T l
khi lng ti a mono sunfo clorua/cht lng mang trong dch b ti li
ra ca thit b chit l Y
ER
ra
= 0,0400.
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137
Cn tnh t l khi lng ti a mono sunfoclorua/cht lng mang
trong dch chit v t l dung mi ti thiu. ng thi xc nh s bc tch
l thuyt i hi khi t l dung mi bng 1,4 t l dung mi ti thiu. T l
khi lng Y
ES
ra
ca cht tan so vi dung mi trong dch chit ti li ra ca
thit b l bao nhiu?

HDTL: Trc ht ta tnh phn khi lng trong hn hp nguyn liu:
W
ER
vo
= 0,15 = (0,15/(0,15 + 0,85)) thnh t l khi lng:
Y
ER
vo
= 0,15/0,85 = 0,1765
T l khi lng ln nht Y
ES, max
ra
trong dch chit c th c c t gi tr
trn trc tung ca ng cn bng ti gi tr trc honh Y
ER
vo
.


Hnh 4.8 S xc nh s bc tch l thuyt
Tuy nhin trng hp ny ch gn nh tun theo nh lut phn b Nernst do
vy ta c th tch Y
ES,max
ra
:
Y
ES, max
ra
= 1,30 . Y
ER
vo
= 1,30. 0,1765 = 0,2295
Y
ES
ra
= 0,0400 v Y
ES
vo
= 0 l cc gi tr cho.

Theo phng trnh:
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138
(m
S
/m
R
)
min
= (Y
ER
vo
- Y
ER
ra
)/(Y
ES, max
ra
- Y
ES
vo
)
= (0,1765 - 0,0400)/(0,2295 - 0) = 0,5948
i vi t l dung mi m
S
/m
R
= 1,4.0 . 0,5948 = 0,8327 ta v c ng
lm vic nh hnh v ( dc 1/ 0,8327 = 1,201).
Theo phng php v bc thang, ngi ta xc nh c s bc tch l
thuyt n
th
= 3 vi s bc tch l thuyt ny v t l dung mi m
S
/m
R
=
0,8327 bit c t l khi lng cht tan/dung mi trong dch chit ti li
ra ca thit b Y
ES
ra
= 0,1638.
Cu 11:
T mt dung dch lng c thnh phn khi lng ca axeton (E) W
ER
vo
=
W
EZ
vo
= 0,50 ngi ta chit axeton bng clo benzen nguyn cht trong dng
ngc chiu lin tc sao cho dch b li ra ca thit b chit ch cn cha
phn khi lng ca axeton l W
ER
ra
= 0,10. Tnh:
a/ dng khi lng ti thiu ca dung mi.
b/ phn khi lng ti a ca axeton trong dch chit, thnh phn ca cc
pha cng tn ti cn bng nh sau:
Pha nc W
RR
0,9989 0,8979 0,7969 0,6942 0,5864 0,4628 0,2741 0,2566
W
ER
0 0,10 0,20 0,30 0,40 0,50 0,60 0,6058
Pha hu c W
RS
0,0018 0,0049 0,0079 0,0772 0,0305 0,0724 0,2285 0,2566
W
ES
0 0,1079 0,2223 0,3748 0,4944 0,5919 0,6107 0,6058

Gii:
Vi cc s liu pha nc v pha hu c, ngi ta v ng binodan v
ng conot i vi h 3 cu t nc (R) - axeton (E) - clo benzen (S).
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139

Hnh 4.9: ng binodan v ng conot i vi h
3 cu t nc (R) - axeton (E) - clo benzen (S).

Trong cc im: Z, R
n
(thnh phn dch b ti li ra) bit c t u
bi, ng thi k c ng thng R
n
S. im cc O ti dng dung mi ti
thiu nm trn ng thng ko di qua R
n
v S, im ny c xc nh qua
im ct ca mi ng conot vi ng thng qua R
n
v S cch xa gin
tam gic nht.
ng thng xut pht t O qua Z ct ng binoan ti im S
*
. im ny
cho bit thnh phn khi lng ti a ca axeton trong dch chit W
RS
ra
=
0.085 (nc trong dch chit) W
SS
ra
= 0,315 (clo benzen trong dch
chit).
ng thng qua cc im Z v S cng nh S
*
v R
n
cho bit im hn hp
P. T cc on PZ v PS theo quy tc n by ngi ta nhn c:
241 , 0 = =
PS
PZ
m
m
z
s
ngha l m
s
= 0,241m
z
.
l dng khi lng ti thiu ca dung mi thc hin nhim v tch
vi s bc tch v cng ln.
Cu 12:
T mt hn hp axeton - nc vi 1 t l khi lng axeton/nc Y
ER
vo
=
0,50 (E cht tan, l axeton) cn phi chit axeton trong dng ngc chiu
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140
bng clobenzen. Dch b cho php t l khi lng axeton nc cao nht l
Y
ER
ra
= 0,02. Cc dng khi lng chy vo ca nguyn liu v dung mi l
bng nhau (m
z
= m
s
vo
). Dng khi lng chy vo ca nguyn liu l 1000
kg/gi. S liu v thnh phn cc pha:
Pha nc W
RR
0,9989 0,8979 0,7969 0,6942 0,5864 0,4628 0,2741
0,2566
W
ER
0 0,10 0,20 0,30 0,40 0,50 0,60 0,6058
Pha hu c W
RS
0,0018 0,0049 0,0079 0,0772 0,0305 0,0724 0,2285 0,2566
W
ES
0 0,1079 0,2223 0,3748 0,4944 0,5919 0,6107 0,6058
Cn xc nh:
a/ s bc tch l thuyt.
b/ Dng khi lng ca dch chit.

Gii:

Hnh 4.10 ng binodan v ng conot i vi h
nc - axeton - clo benzen.
a/ Ta ni im Z (ng vi thnh phn ca nguyn liu) vi im S (ng vi
clobenzen nguyn cht) bng mt ng thng. Bi v m
z
= m
s
vo
do vy
im P nm gia ca ng ZS biu din thnh phn hp thnh ca
nguyn liu v dung mi. Thnh phn i hi cui cng ca dch b (R
n
) v
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141
ca dch chit S
1
l cho trc. on ko di ca ng thng ZS
1
v R
n
S ct
nhau ti im cc O. im ny l im ct chung ca tt c cc tia i qua
mi im ng vi thnh phn ca dch b ti mt bc bt k v thnh phn
ca dch chit bc tip theo. ng conot qua S
1
cho bit im R
1
. Tia cc
qua R
1
cho bit S
2
.... Cu trc ny c thc hin tip tc xung pha di
cho n khi t c thnh phn cui cng ca dch b Y
ER
ra
= 0,02. tr-
ng hp ny R
n
= R
4
; c ngha l i hi 4 bc tch l thuyt.
b/ Cc dng khi lng chy vo ca nguyn liu v dung mi c xc
nh l : m
z
+ m
s
vo
= 1000 + 1000 = 2000 kg/gi.
T t l cc on thng ta c: 049 , 3
15 , 7
8 , 21
4
1
1
4
= = =
R
S
m
m
PS
P R
(a)
Bi tng cc dng khi lng chy vo bng tng cc dng khi lng chy
ra, ta c : gi kg m m
R S
/ 2000
4 1
= + (b)
Gii (a), (b): gi kg m
S
/ 1506
049 , 3
1
1
2000
1
=
+
=

Dng 4: Da vo sc xc nh: thi gian lu, th tch lu, tc chy,
phn gii pic, s a l thuyt ca ct sc k.

Cch gii:
p dng cng thc:
- Thi gian lu: t
R
=
A
u
L
=
u
L
(1 + k)
trong : u
A
: vn tc ca cht cn phn tch.
L: chiu di ct (cm).
k: tha s dung tch, c f =
' 1
1
k +
; t
m
=
u
L

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142
- Th tch lu: V
R
(ml) = t
R
(s) . F (ml/s) F: tc chy.
- phn gii pic: R =
2 / ) (
B A
R
W W
t
+
A
W: chiu ngang pic.
- S a l thuyt: n =
H
L
H: chiu cao pic.

Bi tp: Cho s ca hn hp cht phn tch 4.11 (A) v 4.11 (B): (dng
cho bi tp 13; 14; 15; 16).
Vm
V
RA
V'
RA
V
RB
V'
RB
0 2 4 6 8 40 45 50 55 60
(W )
A
(W )
B

V1
V2 A B
V3


Hnh 4.11 (A): nng l hm ca th tch ra gii
N

n
g


c
h

t

p
h

n

t

c
h
,

m
o
l
/
l

Bm mu, V = 0 Th tch (ml)
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143
m
t
RA
t'
RA
t
RB
t'
RB
0 10 20 30 40 200 220 240 260 280 300
(W )
A
(W )
B
t1 t2 A B
t3

t


Hnh 4.11 (B): Tn hiu o ( c , o ) l hm ca thi gian
Bi 13: Dng sc trn hnh v (4.11A) v V
S
= 10 ml, hy tnh cc i l-
ng cho di y: t
R
; t
m
; V
R
; V
m
; F; V
R
; t
R
; o ; k; D?
Gii:
Lng Cch tnh v kt qu
t
R
Da vo hnh 4.11(A) ta c: 250s (A); 270s (B)
t
m
Da vo hnh 4.11(A) ta c: 30s
V
R
Da vo hnh 4.11(A) ta c: 50ml (A); 54ml (B)
V
m
Da vo hnh 4.11(A) ta c: 60ml
F
F =
R
R
t
V
=
250
50
= 0,2 ml/s
V
R

V
R
= V
R
- V
m
= 50 - 6 = 44 ml (A)
V
R
= V
R
- V
m
= 54 - 6 = 48 ml (B)
t
R

t
R
= t
R
- t
m
= 250 - 30 = 220 s (A)
t
R
= t
R
- t
m
= 270 - 30 = 240 s (B)
o (A l cht chun)
std
R
R
V
V
'
'
= o =
44
48
= 1,09 Hoc
std
R
R
t
t
'
'
= o =
220
240
= 1,09
T

n

h
i

u

Bm mu, t =
0
Thi gian (s)
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
144
o (B l cht
chun)
std
R
R
V
V
'
'
= o =
48
44
= 0,917
k
k =
m
R
V
V
- 1 = 1
6
50
= 7,33 (A)
hoc k =
m
R
t
t
- 1 = 1
30
250
= 7,33 (A)
k =
m
R
V
V
- 1 = 1
6
54
= 8,00 (B)
D
D =
S
m R
V
V V
=
10
6 50
= 4,4 (A)
D =
S
m R
V
V V
=
10
6 54
= 4,8 (B)

Bi 14:
a, Hy tnh s a l thuyt ca ct sc k cho sc hnh v (4.11A)?
b, Nu ct di 120cm th H ca ct l bao nhiu?
Gii:
a, T phng trnh: n =
2
4
|
|
|
|
.
|

\
|
W
t
R
=
2
4
|
.
|

\
|
W
t
R
v s liu hnh (a) ta thy rng:
i vi pic ca A ta c: n =
2
15
250 . 4
|
.
|

\
|
= 4,44.10
3
a l thuyt.
i vi pic ca B ta c: n =
2
17
270 . 4
|
.
|

\
|
= 4,04.10
3
a l thuyt.
b, Chiu cao ca pic: H =
n
L
=
3
10 . 2 , 4
120
= 0,029 cm/a l thuyt.

Bi 15: Tnh phn gii ca cc pic trong hnh (4.11)?
Gii:
Ta c: R =
2 / ) (
B A
R
W W
t
+
A
=
2 / ) 17 15 (
250 270
+

= 1,25
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145
phn gii ny l hp l i vi vic tch hon ton (< 2% A s trong
pic B v < 2% B s trong pic A) nhng khng tht hp l vi phn gii
ng y.

Bi 16: Tnh phn gii khi tch A v B nu dng ct di 200cm thay cho
ct 120cm ca cc pic trong hnh (4,11)?

Gii:
T phng trnh: t
R
=
A
u
L
=
u
L
(1 + k)
Ta thy thi gian lu t l thun vi chiu di ct L, cn tc v tha s
dung lng khng bin i theo chiu di ct. Do :
t
RA
= 250.
120
200
= 417s
t
RB
= 270.
120
200
= 450s
S a l thuyt cng t l vi chiu di ct:
n = 4,2.10
3
120
200
= 7,0.10
3

By gi c th tnh b ngang pic vi phng trnh:
n = =
2
4
|
.
|

\
|
W
t
R
W =
n
t
R
2
16

W
A
=
3
2
10 . 0 , 7
) 417 .( 16
= 20s
W
B
=
3
2
10 . 0 , 7
) 450 .( 16
= 22s
phn gii l:
R =
2 / ) (
B A
R
W W
t
+
A
=
2 / ) 22 20 (
417 450
+

= 1,57

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146
Bi 17: Mt ct sc k kh 150cm c nhi bng cc ht 50 m v cho
cc kt qu thc nghim di y khi ra gii mt cht phn tch. Hy xc
nh vn tc chy ti u v s a l thuyt cho ct khi c vn hnh
nhng iu kin ti u:
Ln chy u (cm/s) t
R
(s) W (s)
1 10 450 24
2 30 150 7,5
3 50 90 5

Gii:
Phng trnh Van Deemter cha 3 hng s A, B, C v do cn c mt cc
tiu ca 3 im xc nh chng. Cc gi tr ca H s c tnh trc ht
bng cch tnh s a l thuyt.
Ln chy 1: n =
2
4
|
.
|

\
|
W
t
R
=
24
450 . 4
= 5,6.10
3
H =
n
L
=
2
24
450 . 4
|
.
|

\
|
= 0,0267 cm
Ln chy 2: n =
2
4
|
.
|

\
|
W
t
R
=
2
5 , 7
150 . 4
|
.
|

\
|
= 6,4.10
3
H =
n
L
=
3
10 . 4 , 6
150
= 0,0234 cm
Ln chy 3: n =
2
4
|
.
|

\
|
W
t
R
=
2
5
90 . 4
|
.
|

\
|
= 5,2.10
3
H =
n
L
=
3
10 . 2 , 5
150
= 0,0289 cm
Cc gi tr ny ca H v nhng gi tr tng ng ca u c th c s dng
lp ng thi 3 phng trnh:
H = Cu
u
B
A + +
0,0267 = C
B
A 10
10
+ + A = 0,0067 cm
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147
0,0234 = C
B
A 30
30
+ + B = 0,163 cm
2
/s
0,0289 = C
B
A 50
50
+ + C = 3,8.10
- 4
s
Vn tc ti u l:
U
opt
=
C
B
=
4
10 . 8 , 3
163 , 0

= 21 cm/s
vn tc ti u, gi tr ca H l:
H
min
= A + 2 BC = 0,0067 + 2
4
10 . 8 , 3 . 163 , 0

= 0,0224 cm
vn tc ti u, s a l thuyt c tnh theo:
n =
H
L
=
0224 , 0
150
= 6,7.10
3
a l thuyt.

Bi 18: Mt hn hp ch cha benzen (C
6
H
6
) v brombenzen (C
6
H
5
Br) cho 2
pic 9,50 cm
2
v 4,78 cm
2
tng ng trn mt sc . Gi thit l c s p
ng mol nh nhau. Hy tnh s % mol v s % theo trng lng ca benzen
v brombenzen trong hn hp ?
Gii:

Din tch (cm
2
) % tng din tch (mol %)
Benzen 9,50 (9,50/14,28).100(%) = 66,5%
Brombenzen 4,79 (4,78/14,28).100(%) = 33,5%
Tng 14,28

Vi 100 mol hn hp, 66,5 mol l benzen v 33,5 mol l brombenzen.
Khi lng ca hn hp ny l:
S mol.M(g/mol) = g % khi lng
Benzen 66,5.78,11 = 5,194 (5,194/10,454).100(%) = 49,7%
Brombenzen 33,5.157,02 = 5,260 (5,260/10,454).100(%) = 50,3%
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148
Tng trng lng = 10,454


Dng 4: Xc nh lng cht tan cn li trong pha nc v lng cht tan i
vo pha hu c.

Cch gii:
Cht A phn b gia pha nc v pha hu c:
Gi s c m
0
mmol A sau khi chit vi V
hc
ml dung dch hu c t V
n
ml
dung dch nc, m
1,1
l lng cht tan cn li trong pha nc v m
0
- m
1,1

lng cht tan i vo pha hu c th:
[A]
hc
=
hc
V
m m
1 , 1 0

; [A]
n
=
n
V
m
1 , 1


D =
n
hc
V m
V m m
/
/
1 , 1
1 , 1 0

m
1,1
= m
0

|
|
|
|
.
|

\
|
+
n
hc
V
V
D 1
1

Bi 19: I
2
c th thu c chit t pha nc bng dung mi hu c. H s
phn b khi chit bng CCl
4
l 85. Nu 50 ml ca dung dch nc cha 2.10
-
2
mmol I
2
c tip xc vi 30 ml CCl
4
. Tnh lng I
2
trong pha nc v pha
hu c.

Gii: p dng cng thc: m
1,1
= m
0

|
|
|
|
.
|

\
|
+
n
hc
V
V
D 1
1

Ta c: lng cht tan cn li trong pha nc l:
S ha bi Trung tm Hc liu i hc Thi Nguyn http://www.lrc-tnu.edu.vn
149
m
1,1
= m
0

|
|
|
|
.
|

\
|
+
n
hc
V
V
D 1
1
= 2.10
-2
|
|
|
|
.
|

\
|
+
50
30
85 1
1
= 3,85.10
-4
mmol
Vy lng cht tan cn li trong pha hu c l:
m
0
m
1,1
= 2.10
-2
0,00385.10
-2
~ 1,96.10
-2
mmol

Bi 20: Mt cht A c th b chit t pha nc vo ete. H s phn b bng
10. Nu dung dch nc cha 2,5mg A.
a, Th tch pha nc bng pha hu c th chit c bao nhiu %A?
b, %A c th b chit bng bao nhiu nu chia V
hc
lm 4 phn v chit 4 ln?
Gii:
a, p dng cng thc: m
1,1
= m
0

|
|
|
|
.
|

\
|
+
n
hc
V
V
D 1
1

Ta c: lng cht tan cn li trong pha nc l:
m
1,1
= m
0

|
|
|
|
.
|

\
|
+
n
hc
V
V
D 1
1
= 2,5
|
|
|
|
.
|

\
|
+
1
1
10 1
1
= 0,23 mg
Vy lng cht tan cn li trong pha hu c l:
m
0
m
1,1
= 2,5 0,23 = 2,27 mg = 90,8%
b, Phn trm cn li khi gim V
hc
:
cn li % = 100
4
1
1
10 1
1
|
.
|

\
|
+
= 0,67%
% chit = 100 0,67 = 99,33%

Kt lun chng IV: Chng Cc phng php tch, chit v phn chia
: xy dng h thng cu hi t lun v h thng bi tp c phn loi theo
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150
cc dng bi tp v xut cch gii: Tnh nng ca axit cn li trong pha
nc khi bit hng s phn li axit v h s phn b; xc nh h s phn b
v phn trm chit; xc nh s bc tch l thuyt; xc nh thi gian lu, th
tch lu, tc chy, phn gii pic, s a l thuyt ca ct sc k, xc
nh lng cht tan cn li trong pha nc v lng cht tan i vo pha hu
c.

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