PHN TCH MI TRNG

B mn: K thut mi trng

Khoa Qun l cng nghip v Mi trng
Mc ch mn hc
Cung cp kin thc v:

- Ch th mi trng
- Tiu chun nh gi cht lng mi trng
- Phng php x l v phn tch cc thng s
cht lng mi trng.
- m bo cht lng v kim sot cht lng
trong phn tch mi trng.
Ni dung
Chng I. Ch th mi trng v tiu chun nh
gi cht lng mi trng
Chng II. Cc phng php o c v phn
tch cc thng s cht lng mi trng
Chng III. X l mu
Chng IV. m bo cht lng v kim sot
cht lng trong phn tch mi trng
Chng V. Cc bi th nghim v thc hnh
Ti liu tham kho
. Hunh Trung Hi - Bi ging Phn tch mi trng - Vin Khoa
hc cng ngh Mi trng Bch khoa.
Vin th nhng nng ho. S tay phn tch t, nc, phn bn
v cy trng. Nh xut bn nng nghip, 1998.
Trn T Hiu - Gio trnh Ha phn tch - Trng i hc khoa hc
tng hp H Ni - 1992.
Cc TCVN v mi trng.
APHA. Standard Methods for the Examination of Water and
Wastewater. 19th Edition, 1995.
Hong Minh Chu, T Vn Mc, T Vng Nghi. C s Ha hc
Phn tch. Nh xut bn Khoa hc v K thut, H Ni, 2002.
Trang web:
http://www.nea.gov.vn
Chng I: Ch th mi trng v tiu
chun nh gi cht lng mi trng

I.1. Khi nim v ch th mi trng
I.2. Tiu chun cht lng mi trng
I.1. Khi nim v ch th mi trng
* Ch th (indicator) l g ?
Khi bn b m v b st, s tng thn nhit ca bn
chnh l mt ch th.
Mt ch th mi trng cng tng t nh mt thc o
nhit mi trng.
Nng xy thp ca mt con sng l ch th cho thy mt
lng ln cht hu c c thi vo con sng .
Vy, vic truyn t thng tin chnh l chc nng chnh ca
cc ch th.
Ch th mi trng l c s lng ha cht lng mi
trng, theo di din bin cht lng mi trng, lp bo co
hin trng mi trng. B Ti nguyn v Mi trng ban hnh
b ch th mi trng quc gia p dng trong c nc.
- Theo UNEP: Ch th mi trng (CTMT, Environmental
Indicator) l mt o tp hp mt s s liu v mi tr-
ng thnh mt thng tin tng hp (Aggregate) v mt
kha cnh mi trng ca mt quc gia hoc mt a ph-
ng.
-Theo Lut Bo v Mi trng s 52/2005/QH11 ngy 29 thng
11 nm 2005: Ch th mi trng l mt hoc tp hp thng
s v mi trng ch ra c trng ca mi trng.
* Khi nim v ch th mi trng
Nhiu ch th mi trng hp li thnh mt b CTMT ca mt
nc, hoc mt vng, mt a phng.
1. Ch th p lc mi trng: din tch rng b mt trong
nm (ha, % tng din tch ca nm trc)
2. Ch th trng thi mi trng: tng din tch rng
hin c (ha, % tng din tch lnh th)
3. Ch th p ng ca x hi: Din tch rng trng/nm
(ha)
Th d v mt s ch th mi trng lin quan n suy
thoi ti nguyn rng:
* Chc nng:
o Cung cp thng tin cho cc chnh tr gia, cc nh hoch nh
chnh sch:
Vn ang tin trin th no?
Cc tin t c so vi mc tiu ra?
Quy hoch v d bo ni chung mi lin h gia pht trin
kinh t v qun l mi trng.
o Hoch nh chnh sch:
t ra cc mc tiu, ch tiu
Theo di vic thc hin chnh sch
Hoch nh, thc thi, nh gi hiu qu ca chnh sch
o Cung cp thng tin cho cng ng
Chuyn ti thng tin, tuyn truyn, nng cao nhn thc v
thay i hnh vi ca cng ng.
* Qu trnh xy dng ch th mi trng v cc tiu ch
la chn ch th mi trng:
Qu trnh xy dng ch th mi trng:
Theo GS.L Thc Cn: Trong qu trnh xc nh cc
ch th ph hp v kh thi, ly nhu cu ca ngi s
dng vi cng v l nh qun l mi trng lm
xut pht im, c th cch tip cn di y s gip
ch:
Trong lnh vc mi trng ang cp ti, xc nh cc
vn v/hoc cc c tnh quan trng nht.
Xc nh mc ch thng tin u tin cn c t ch th.
Xc nh nhng ch th mang tnh chin lc nht (vi
mt s lng t nht cc ch th c th phc v nhiu nht
cc mc ch thng tin) t c cc mc ch thng tin
trn.
Kim tra li tnh sn c ca cc d liu hin ti v xem xt
cc kha cnh lin quan n cht lng ch th.
Nu cn, kim tra cc kh nng ci thin tnh sn c ca
d liu: cc kh nng trc mt cng nh trong thi gian
ngn hn.
La chn cc ch th.
+ M hnh ng lc - p lc - Hin trng - Tc ng - p
ng (Dynamic - Pressures - State - Impacts Response: m hnh
DPSIR) trong xy dng ch th mi trng.
M hnh DPSIR m t mi quan h tng h gia:
- ng lc trc tip hoc gin tip (D - Driving forces ): V d: s gia
tng dn s, s pht trin nng nghip, cng nghip, giao thng vn
ti...
- p lc do con ngi gy ra (P- Pressures): V d: S x thi cc
cht thi gy nhim. Cc ngnh/ tc nhn/ quy trnh ang ng
vai tr nh th no?
-Hin trng mi trng (S -State of the Environment ): tnh trng l,
ha, sinh ca mi trng.. Vn ang din bin nh th no?
- Tc ng (I- Impacts) ca s thay i hin trng mi trng: V d:
tc ng ln h sinh thi, sc khe con ngi, kinh t, s pht trin...
Cc tc ng ang din bin nh th no?
- Phn hi (R- Response) t x hi vi nhng tc ng khng mong
mun: V d: Cc hot ng ca x hi nhm bo v mi trng... tnh
hiu qu ca cc bin php p ng?
S m hnh DPSIR:

- Nng
nghip
- Cng
nghip
- Nng
lng
- H gia
nh
.
Sn xut
v c cu
sn xut

S dng
cng ngh

Tiu dng

Cht thi





S dng
ti nguyn
thin nhin

Hin trng
sinh hc

- a dng
sinh hc
Trng thi t
nhin
- Thy vn
- a hnh
- Ti nguyn


Trng thi
ha hc
- Cht lng
khng kh
- Cht lng
nc
- Cht lng
t
Chc nng
ca h sinh
thi
- Nc bin
- Nc trong
lc a
- Rng

D
Kinh t

Tc ng n
mi trng
- Cc ch th
p ng
- Tc ng
n cc vn
khc


Tc ng n
nn kinh t
- Chi ph cho
nhng bin
php khc
phc
- Hu qu v
kinh t
Cc cng
c kinh t
v m
Chnh sch
cho tng
lnh vc c
th
Chnh sch
v mi
trng
Xc nh
mc tiu
u tin
chnh sch v k hoch hnh ng
P
Thin nhin v mi trng
S
I
R
Cc tiu ch la chn ch th mi trng: (lin quan
n vic xem xt mc ch v cht lng ca ch th)
Ph hp v chnh sch: c kim nghim thng qua vic xem xt
tham kho cc vn bn chnh sch, cc k hoch, lut nh
Tnh sn c ca d liu: vic thu thp cc d liu phc v cho ch
th cn mang tnh kh thi c v mt chuyn mn cng nh ti chnh.
C th so snh: v d nh so snh gia cc tnh (nh gi bng
chm im).
c ti liu ha y v qun l c cht lng: tiu ch ny
c nh gi thng qua cng tc ti liu ha i vi ch th cng nh
mc cp nht cc ti liu ny.
C c s v mt khi nim cng nh phng php lun. iu ny
phi c th hin trong cc m t v phng php lun v cng
thc s dng, cc tham kho khoa hc cho phng php lun v
cng thc , cc m t ny cn phi a vo phn ti liu ha ca
ch th.
n gin v d hiu nh c mt nh ngha r rng v
thng nht v ch th, trnh by ch th mt cch hp l,
lun lun c s i chiu gia cc ch th vi nhau.
Cho thy tin t c so vi mc tiu ra: c
kim nghim thng qua cc thng tin trong cc vn bn
chnh sch. Trong trng hp thiu cc mc tiu, c th
s dng mc ngng.
Mc bao ph v khng gian v thi gian: nht qun
v khng gian v c tnh n cc tnh ph hp i vi
mt vn mi trng nht nh. Ch th bao ph mt
khong thi gian c th cho thy xu hng theo
thi gian.
Ph hp vi cp tnh v mang tnh i din cho cc
tnh nhm h tr vic so snh.
Ch th mi trng khng kh:

Tc ng
Nng nghip lin k
vng nhim

Din bin cc h sinh
thi trong th


Ri ro v phi nhim
nhim khng kh i vi
sc kho cng ng
ng lc
Pht trin dn s
Din bin GDP
hng nm
Cc lnh vc c lin
quan
- Giao thng
- Cng nghip
- Xy dng
- Sinh hot th
- Nng lng
p lc
Ngun thi cc cht
nhim: NO
2
, SO
2
, bi
(TSP, PM
10
), CO,
VOC
Hin trng mi trng
Nng cc cht
nhim
(NO
2
, SO
2
, bi (TSP,
PM
10
), CO, O
3
,
nmVOC) trong mi
trng khng kh th
S ngy c nng vt
qu tr s cho php
th i vi NO
2
, SO
2
, bi
(TSP, PM
10
), CO
p ng:
- Hiu sut nng lng: nng lng tiu th so vi pht trin kinh t
- Cc chnh sch mi trng t c mc tiu ca quc gia v mi trng (VD: tiu chun, tiu ch nhm
iu tit p lc)
- Cc chnh sch i vi ngnh (cc gii hn v kim sot s tng trng ca ngnh nhm lm gim hoc
thay i cc hot ng hay cc p lc m cc hot ng ny gy ra)
- S dng nhin liu sch hn
- Ngun nng lng sch hn
- u t cho BVMT
- Din tch cy xanh th
- Nhn thc mi trng
- Chnh sch xa i, gim ngho c th

Ch th mi trng nc:
ng lc
S gia tng dn s ni
chung.
Cc lnh vc c lin quan
- Nng nghip
-Ng nghip
-Thy in
-Nc sinh hot
-Cng nghip
-Dch v
-Xy dng
-H gia nh
-Khai thc m
-Lm nghip
-Giao thng ng thy
-nh bt thy sn nc
ngt
p lc
S dng nc cho nng
nghip, tiu dng v
cng nghip
-Thi cc cht nhim
vo sng h
-Xy dng p, cng...
-Xi mn
-Khai thc cc ngun
thy sn

Tc ng:
Tnh a dng sinh hc
H sinh thi: t ngp
nc, rng ngp mn

Ti nguyn thin nhin:
thy sn nc ngt, t
nng nghip b nhim
v mn ha

Con ngi: nhim
nc ung, bnh tt do
nhim nc, gim thu
nhp/dinh dng t
nh bt thy sn nc
ngt v hot ng nng
nghip, ti nh c, l lt,
kh hn.
Hin trng mi trng
- Tr lng nc v dng
chy
-Ngp ng, l lt
-Lu chuyn trm tch, lng
ng bn
-Hnh thi sng ngi
-Cht lng nc
-Cc cht gy bnh
-Ph dng, bng pht to
-Tnh a dng v hin trng
thm thc vt, ng vt v sinh
vt ph du, c.
-Xm thc mn nc sng v
nc ngm

p ng
- Hnh ng gim thiu
- Cc chnh sch mi trng t c mc tiu ca quc gia v mi trng (VD: cc tiu chun, cc tiu ch nhm
iu tit p lc)
-Cc chnh sch i vi ngnh (cc gii hn v kim sot s tng trng ca ngnh nhm lm gim hoc thay i cc
hot ng hay cc p lc m cc hot ng ny gy ra)
- Nhn thc mi trng
- Chnh sch xa i, gim ngho c th
- Qun l tng hp cc thy vc

Ch th mi trng t:
nhim mi trng t c xem l tt c cc hin
tng lm nhim bn mi trng t bi cc cht
nhim: do cc cht thi sinh hot, do cht thi cng
nghip, hot ng nng nghip.
Phn loi nhim t theo cc tc nhn gy nhim:
nhim t do tc nhn ha hc: Bao gm phn bn
N, P (d lng phn bn trong t), thuc tr su (clo
hu c, DDT, linan, P hu c), cht thi cng nghip
v sinh hot (kim loi nng, kim, axit)
nhim t do tc nhn sinh hc: Trc khun l,
thng hn, cc loi k sinh trng (giun, sn,)
nhim t do tc nhn vt l: Nhit (nh hng
n tc phn hy cht thi ca sinh vt), cht
phng x (Uran, Thori)
Tiu chun cht lng mi trng: l gii hn cho php ti a
v liu lng hoc nng ca cc tc nhn gy nhim cho
tng khu vc c th hoc cho tng thnh phn mi trng.
Tiu chun mi trng xung quanh
Tiu chun thi
Thng s cht lng mi trng: l nhng thng s th
hin nhng c tnh c bn ca mi trng.
Thng qua vic xc nh gi tr ca cc thng s mi trng v
cn c vo tiu chun cht lng mi trng c th nh gi
cht lng mi trng v gim st tnh trng nhim mi
trng.
Mi mi trng c cc thng s cht lng mi trng c
trng ring.
I.2. Tiu chun cht lng mi trng
V d: Tiu chun cht lng nc:
1. TCVN 5942:1995 - Tiu chun cht lng nc mt
2. TCVN 5944:1995 - Tiu chun cht lng nc ngm
3. TCVN 5945:2005 - Tiu chun nc thi cng nghip
Chng II:
Cc phng php o c v phn tch cc
thng s cht lng mi trng
* Phng php vt l
Phng php khi lng
Phng php phn tch th tch
Phng php phn tch bng cng c
* Phng php ha hc
- Nguyn tc: Xc nh cc thng s cht lng
mi trng (kh, nc, t) m khng lm thay
i thnh phn (bn cht) ca mu mi trng
tng ng.
V d: - Xc nh SS, TSS: lc mu, sy mu
- Xc nh ting n...
- Xc nh dn in ca nc
- Xc nh nhit ca nc, khng kh
II.1. Phng php vt l
II.2.1. Phng php khi lng
Nguyn tc:
- Kt ta thnh phn cn xc nh di dng hp
cht t tan, khng tan.
- Lm sch kt ta: lc, ra,
- Sy, nung kt ta nhit cao n khi lng
khng i.
- Cn sn phm thu c v tnh hm lng
thnh phn cn xc nh.
II.2. Phng php ha hc
Mt s iu kin quan trng trong qu trnh phn
tch bng khi lng:
- S kt ta hon ton:
Chn iu kin thch hp kt ta hon ton
cht cn xc nh (kt ta trong iu kin ti u)
nh nhit , dung mi, kch thc ht kt ta to
thnh, lng thuc kt ta, pH ca dung dch, s
tn ti cht in li l.
- sch ca kt ta:
Kt ta to thnh phi c tinh khit cao, do
cn ch n s hp ph v cng kt ca kt ta.
ng dng trong phn tch mi trng
- V d: phn tch SO
4
2-
trong nc
B sung dung dch BaCl
2
long t t vo nc cn
xc nh SO
4
2-
cho thm HCl
un n gn si
ngui khong 12h
(hoc em un cch thy 2-3h)
Lc kt ta
Ra sch ion Cl
-
Nung kt ta 800 - 900
0
C n khi lng khng i
Cn kt ta
Tnh SO
4
2-
theo cng thc ha hc
Nguyn tc:
- xc nh nng cht A, s dng dung dch
cha cht B bit trc nng (dung dch
chun). Cho dung dch B tc dng vi dung dch A
theo s phn ng: A + B = C + D. Khi B tc
dng va ht vi A th ngng li, khng thm tip
dung dch B vo dung dch A na. Da vo
V(ddA), V(ddB) v C(ddB), tnh c C(ddA).
- Qu trnh ny gi l qu trnh chun .
- Thi im hai cht A v B tc dng ht vi nhau gi l
im tng ng.
II.2.2. Phng php phn tch th tch
im tng ng xc nh nh nhng tn
hiu c bit c th nhn thy c, v d s
thay i mu ca loi cht c thm vo vi
mt lng rt nh gi l cht ch th, hoc s
thay i t ngt ch s my o (in th,
dn,).
Cc phng php phn tch th tch: trung
ha, oxi ha - kh, kt ta, to phc.

Nguyn tc:
- Trong qu trnh chun , [H
+
] (pH) ca dung dch thay
i. im tng ng dung dch c pH xc nh.
Bng cch no xc nh c thi im no trong
qu trnh chun pH t n gi tr ny v lc ta
kt thc chun . Mun th c th dng my o pH,
my o in th hoc dng cht ch th axit-baz (mu
chuyn i theo pH).
(1). Chun theo phng php trung ha (chun
axit-baz):
- Chn cht ch th axit-baz:
+ Chun axit mnh bng baz mnh hoc ngc li,
pH im tng ng bng 7, bc nhy pH trong
khong 4 10; do c th dng cht ch th thng
dng l Metyl da cam hoc Phenolphtalein xc nh
im tng ng.
+ Chun baz yu bng axit mnh, im tng
ng pH nm trong min axit, bc nhy pH ngn
nn cht ch th thng dng l Metyl da cam (v d
chun dung dch NH
3
bng HCl).
+ Chun axit yu bng baz mnh, im tng
ng pH nm trong min baz, bc nhy ngn nn
cht ch th thng dng l Phenoltalein.
+ Phng php ny da vo phn ng gia 2 cp oxi
ha kh: OX
1
/Kh
1
v OX
2
/Kh
2
:
n
2
OX
1
+ n
1
Kh
2
n
2
Kh
1
+ n
1
OX
2

+ Trong qu trnh chun in th oxi ha kh ca
dung dch thay i v im tng ng in th
c mt gi tr xc nh (Et).
gn im tng ng c bc nhy in th.
Nu chn c cht ch th m s thay i mu ca
n xy ra ng lc qu trnh chun to ra bc
nhy in th th c th xc nh im tng
ng.
(2).Chun theo phng php oxy ha kh:
Nguyn tc:
+ Cc phn ng oxi ha kh c dng trong
chun phi tha mn cc iu kin sau:
Phn ng xy ra nhanh
Phn ng hon ton v theo mt t lng nht nh, theo
chiu hng xc nh
Khng xy ra phn ng ph
Phi c cch hoc cht ch th thch hp xc nh c
im tng ng.

- Nhng cht ny ni chung cng l nhng cht oxi ha kh v
ngi ta thng chn nhng cht c E
0
(in th oxi ha kh tiu
chun ca cht ch th) nm trong bc nhy in th ca qu trnh
chun .
Cht ch th l cc cht hu c c tnh cht oxi ha kh, c mu
dng oxi ha v dng kh khc nhau, v thay i ph thuc vo th
oxi ha ca dung dch.
- Cc cht ch th c kh nng cho php nhn ra im cui ca s
chun , nhng s thay i mu khng ph thuc vo th ca
dung dch.
V d: Dng dd KMnO
4
chun cc cht kh nh Fe
2+
, H
2
O
2
..., sau
im tng ng d mt git dung dch KMnO
4
th dd s nhum
mu hng.
Dung dch h tinh bt to vi I
2
t do mt hp cht mu xanh...
* Cc cht ch th:
Phn tch COD:

+ Phng php ny da vo phn ng oxi ha cht hu c bng
Cr
2
O
7
2-
trong H
2
SO
4
m c, c mt cht xc tc Ag
2
SO
4
(v
HgSO
4
to phc vi Cl
-
ngn nga nh hng ca n).

Cht hu c + H
+
+ Cr
2
O
7
2-
2Cr
3+
+ CO
2
+ H
2
O

+ Sau chun lng Cr
2
O
7
2-
d bng dung dch mui Mo
(amoni sunfat: (NH
4
)
2
Fe(SO
4
)
2
.6H
2
O - FAS), vi cht ch th
Feroin dd chuyn t mu xanh lam sang mu nu nht.
Cr
2
O
7
2-
+ 14H
+
+ 6Fe
2+
2Cr
3+
+ 7H
2
O + 6Fe
3+
* ng dng trong phn tch mi trng:
Cc phn ng kt ta phi p ng nhiu yu cu rt
cht ch nh:
+ Kt ta khng tan
+ Phn ng to xy ra nhanh, khng c hin tng qu
bo ha
+ Xc nh c chnh xc im tng ng (khng b
nh hng ca hin tng cng kt)
V nguyn tc, xc nh im tng ng ngi ta
cng tin hnh tng t nh hai phng php trn.
(3). Chun theo phng php kt ta:
M
+
+ A
-
MA
Nguyn tc: da vo phn ng to kt ta
+ V d: Phn tch hm lng Cl
-
trong nc:
Chun Cl
-
bng dung dch AgNO
3
c th dng
K
2
CrO
4
lm cht ch th v sau im tng ng,
Ag
+
d s to kt ta gch Ag
2
CrO
4
.
Ag
+
+ Cl
-
AgCl trng
2Ag
+
+ CrO
4
2-
Ag
2
CrO
4
gch
C th Chun Ag
+
bng dung dch CNS
-
, dng cht
ch th l Fe
3+
to phc Fe(CNS)
3
mu sau im
tng ng.
Ag
+
+ CNS
-
AgCNS trng
Fe
3+
+ 3CNS Fe(CNS)
3 +

- ng dng:
II.2.2. Phng php phn tch bng cng c
Cc cng c phn tch, gii thiu y l nhng thit b
dng tin hnh vic phn tch bng cc phng php
vt l v ha l.
B pht
tn hiu
B cm
bin tn
hiu vo
B cm
bin tn
hiu
B chuyn
i tn hiu
Thng thng mi b thit b nh th gm 4 phn chnh
nh s sau:
B cm bin tn hiu vo: chuyn i cc tham s ha hc hoc
vt l thnh 1 dng tn hiu khc, thng l tn hiu in.
B pht tn hiu:
- Tn hiu pht sinh t chnh i tng cn phn tch
V d s pht bc x mu vng ca Na khi t nng cc mu
c cha nguyn t ny trong quang k ngn la.
- Tn hiu khng pht sinh t mu phn tch nhng khi i qua mu
phn tch tn hiu b bin i m s bin i c lin quan n
cu to cng nh nng cc thnh phn trong mu.
B chuyn i tn hiu: chuyn cc tn hiu in c ci
bin thnh thng tin c th c c, ghi c t ngi
phn tch c th din gii c nhng vn cn tm hiu i vi
mu phn tch.
B cm bin tn hiu: l khi thit b in t thc hin cc thao
tc nh khuych i, lc tn hiu.
Cc phng php phn tch bng cng c:
- Phng php quang ph pht x nguyn t
- Phng php quang ph hp th nguyn t
- Phng php quang ph hp th in t
- Phng php phn tch theo ph dao ng
- Phng php in th/ Phng php in cc ion
chn lc
- Phng php phn tch Von Ampe
-Phng php sc k
II.2.2.1. Phng php quang ph pht x nguyn t
Nguyn tc:
S to thnh ph pht x:
+ trng thi bnh thng, cc electron trong nguyn t chuyn ng
xung quanh ht nhn trn nhng orbital vi nhng mc nng lng
b nht. Trng thi ny gi l trng thi c bn.
+ Khi nguyn t c cp thm mt ngun nng lng t bn ngoi,
cc e chuyn ln mc nng lng cao hn ty thuc vo nng
lng hp th c. Nguyn t chuyn sang trng thi kch thch.
Trng thi ny khng bn, sau mt thi gian rt ngn (10
-7
10
-9
s)
nu cc electron khng b mt nng lng do va chm hay phn ng
ha hc n s tr v trng thi nng lng thp hn (trng thi c
bn hay trng thi kch thch vi mc nng lng thp). Nng lng
d c gii phng di dng bc x in t (quang ph pht x:
E = E
e
E
f
= h.v v v = E/h (E
e
v E
f
: nng lng ca trng thi
kch thch v nng lng mc thp hn; h: hng s Planck; v : tn
s ca bc x (cm
-1
), (tc l ca vch quang ph).
+ Khi mt e thc hin mt chuyn dch t mc nng lng cao v
mc nng lng thp hn, bc x pht ra c (hay v) xc nh.
+ C rt nhiu kiu dch chuyn nh trn, do s pht x ca
mt nguyn t khi b kch thch khng phi ch to ra mt vch
(mt tia) m l mt s vch c tn s khc nhau ng vi cc E
khc nhau.
+ V mi nguyn t c h thng nng lng nguyn t ring nn
ph pht x nguyn t cng c trng cho nguyn t ca
nguyn t .
+ ng dng trong php phn tch nh lng ngi ta chn ly
mt vch ph c trng nht tc l vch ph xut hin cui cng
khi gim dn nng cht. S thay i cng ca vch ny
s xc nh lng nguyn t cn phn tch.
Tnh a dng ca ph pht x nguyn t:
I: cng ca vch ph
A: hng s
N
0
: s nguyn t ca nguyn t trng thi hi c trong 1 cm
3

hi nguyn t .

K: hng s Bolzman (1,38.10
-23
J)
E
k
: th kch thch
T: nhit
/KT .e A.N I
k
E
0

=
Cng ca vch quang ph:
+ I ph thuc N
0
(tc cng l ph thuc nng C), th kch thch,
nhit . S ph thuc I vo C c biu din bi h thc
Lomakin:
I = a.C.b
a, b: l h s ch s ph thuc iu kin kch thch v vch
quang ph cng nh trng thi vt l ca mu nghin cu.
C : l nng ca nguyn t cn xc nh trong mu.

lgI = lga + blgC, l biu thc c s cho php phn tch quang
ph nh lng.
lgI
lgC
th mi quan h gia I v C
c dng ng thng
Ngi ta thy rng: Khi tng nng
nguyn t c th xy ra hin tng t
hp th pht x, tc l nhng nguyn t
khng b kch thch s hp th mt phn
nng lng bc x. V vy bt u t
mt giai hn nng no (xc nh
i vi mi nguyn t) th quan h gia I
v C s khng l tuyn tnh. Do ,
phng php ny ch gn trong mt
phm vi nht inh v nng vi tng
nguyn t. Nn th s c dng:
lgI
lgC
l nng ca nguyn t phn tch m khi thu
c vch ph c trng cho nguyn t .
S thay i cng vch ph ny s xc nh
lng nguyn t cn phn tch.
Xc nh C
0
: Pha long dn dung dch n nng
C
min
= C
0
nhiu vch ph mt i do cng b, ch
cn 1 vch ph gi l vch cng hng.
Nu pha long tip n nng C<C
0
th vch
cng hng mt i, thit b khng pht hin c,
l ngng pht hin ca thit b.
- Nng C
0
ban u:
Ngun kch thch: Lm cho mu chuyn thnh hi, nguyn t
ha mu, kch thch nguyn t chuyn ln trng thi nng lng
cao hn.
Ngun kch
thch
Mu H tn
sc
B thu v x l
tn hiu
Thit b quang ph pht x nguyn t:
Detector: ghi quang ph. Trong cc my quang ph ngi ta
thng dng Detector l t bo quang in v tt nht l dng cc
ng nhn quang (PMT: PhotoMultiplier Tube). Cc ng nhn quang
va c chc nng chuyn i t nh sng thnh dng in, va
c chc nng khuch i tn hiu (c th khuch i 1 triu ln).
H tn sc (b phn tch tia n sc): Thng dng lng knh
hoc cch t nhiu x. B phn ny c chc nng phn ly cc
chm bc x a sc thnh tia n sc.
Phn tch nh tnh: so snh ph ca mu vi
cc ph chun, tm cc vch ph cui cng.

Phn tch bng phng php quang ph pht x
nguyn t:
Phn tch nh lng: xy dng ng chun
gia nng v cng vch ph, t xc nh
nng ca cht cn phn tch c trong mu. C th
xc nh c hu ht cc nguyn t tr C, O, H, N.

II.2.2.2. Phng php quang ph hp th nguyn t
Nguyn tc:
Di tc dng ca ngun nhit khng cao lm, cc cht ha hi,
cc phn t b phn ly thnh nguyn t v a s cc nguyn t
trng thi khng b kch thch (trng thi c bn), ch mt phn
nh nguyn t b kch thch v chng chim khong 10
-5
- 10
-7

phn.
Cc nguyn t ca mt nguyn t trng thi c bn c c tnh
l c kh nng hp th mt cch chn lc cc bc x do chnh
n pht ra, c bit l bc x cng hng. Bi vy nu lm cho
mt cht ha hi v chuyn thnh cc nguyn t trng thi c
bn ri cho tia cng hng ca chnh nguyn t pht ra i
qua, th cc nguyn t trng thi c bn s hp th mt phn
nng lng ca bc x cng hng. Kt qu l cng ca
bc x gim i.
- Gi I
0
l cng ca bc x cng hng chiu
vo mi trng hp th (l bu hi nguyn t
trng thi c bn)
- I l cng bc x sau khi qua mi trng hp
th th p dng nh lut c bn v hp th bc
x, ta c:
lg(I
0
/I) = A = k.b.C
A: hp th;
k: h s hp th;
b: khong ng nh sng b hp th (v d
chiu rng ca ngn la);
C: nng (c th tnh theo mol/l, g/l...).
Cng ca bc x cng hng:
Phn tch nh tnh: Da trn c s l cc nguyn
t to ra trong b nguyn t ha mu hp th hay
khng hp th tia cng hng pht ra t n catt
rng lm bng mt nguyn t no nhn bit
trong mu phn tch c hay khng c nguyn t .
Phn tch nh lng:
+ Da vo h thc: lg(I/I
o
) = A = k.b.C
hay A = lg(I/I
o
) = K.C
+ o hp th A c th xc nh C (nng ), c th
tin hnh tnh C theo hai cch: Xy dng ng
chun v phng php thm chun
Phn tch bng phng php quan ph hp th
nguyn t
o Ngn la hay l graphit hay ha hi lnh.
o di sng cn chn.
o Thnh phn ca mu, c khi s c mt ca mt ion c
th gy kh khn cho s nguyn t ha v do nh
hng n s hp th bc x ca mt nguyn t
khc, v d ion PO
4
3-
nh hng n s nguyn t
ha ca Mg, Ca
o S ion ha: mt s nguyn t d b kch thch, d b
ion ha nh Na, K lm gim nhy. khc phc,
ngi ta thng thm vo nhng cht d ion ha hn
nh Li (gi l cht kh ion ha hay cht m bc x).
Ch c nhiu nh hng khc nhau nn phi tm
cc iu kin ti u v:
II.2.2.3. Phng php quang ph hp th in t
Bc x t ngoi UV bao gm: cc tia c nm
trong vng t 100 nm n 400 nm:
100 200 nm: Vng t ngoi xa: t 100 200 nm, c
nng lng rt ln nhng t dng trong cc phng
php phn tch.
200 400 nm: Vng t ngoi gn, c nng lng thp
c s dng nhiu trong php phn tch.
Vis (Visiable - Vng nhn thy): 400 800 nm c nng
lng thp c s dng nhiu trong php phn tch.
- Gii thiu:
S hp th bc x t ngoi v trng thy:
+ Phn t ca cc cht c kh nng hp th mt cch chn
lc cc bc x chiu qua n. Khi hp th nng lng bc
x, trong phn t xy ra cc bc chuyn nng lng ca
in t, bc chuyn nng lng dao ng, bc chuyn
nng lng quay ca ton phn t ph hp th rt phc
tp, khng c dng vch sc nhn m l nhng bng ph
tri rng.
+ s hp th in t: s hp th bc x lm bin i nng
lng ca in t.
+ Trong phn t, cc e (lp ngoi) c vai tr khc nhau: tham
gia lin kt gi l in t ha tr, khng tham gia lin kt gi
l cc in t khng chia hay in t c thn.
- Nguyn tc:
+ Cc e ha tr c th to lin kt hoc ; cc e khng
tham gia lin kt lp v e ngoi k hiu l n. Khi e ha
tr tham gia lin kt s to thnh cc obital phn t: obital
lin kt v obital phn lin kt ( v
*
, v
*
). Cc e
ny c th cc mc nng lng khc nhau ty thuc
cc obital to thnh; trong obital c nng lng thp
nht cn obital
*
c mc nng lng cao nht.
+ Trong iu kin thng cc phn t tn ti mc nng
lng thp (trng thi c bn), cc e mc nng lng
thp nht. Khi phn t hp th nng lng s chuyn t
trng thi c bn sang trng thi kch thch, cc e t mc
nng lng thp chuyn ln mc nng lng cao:
+ iu kin xy ra bc chuyn nng lng e l
E = h., E l bin thin nng lng ng vi bc
chuyn, l tn s bc x in t. C th xy ra cc
bc chuyn
*
, -
*
, n -
*
, n -
*
.
+ Khi phn t hp th bc x in t gy ra cc bc
chuyn nng lng in t to nn hiu ng ph hp
th.

*

n

nh lut c bn ca s hp th nh sng (nh lut
Lambe Bia):
+ H thc c bn:







I
o

I
b
C
lg(I
o
/I) = A = a.b.C = K.C
+ Cc yu t nh hng n s sai lch i vi h thc
c bn: gia A v C khng cn quan h tuyn tnh.
Cc nguyn nhn chnh l:
o nh sng khng n sc: nu dng nh sng c khong rng
th kt qu o s c lch m. Bi vy c kt qu o chnh
xc ngi ta phi tin hnh o vi nh sng c khong cng
hp cng tt, tt nht l n sc, v chn bc sng c hp
th ln nht (
max
).
o nh hng ca nng cht cn xc nh: i vi mi cht gia
A v C ch c quan h tuyn tnh trong mt khong nng xc
nh.
o pH ca dung dch: pH thay i c th lm cn bng to phc thay
i, do nng cc phn t hp th nh sng thay i theo.
o S c mt cc cht l: c th nh hng n s hp th nh
sng ca cc cht cn xc nh theo nhiu c ch khc nhau.
1 2
3
4
5
a
b
c
1. Ngun chiu sng
2. H tn sc
3. Cuvt ng dung dch (mu)
4. Detect (t bo quan in, nhn quang)
5. B ghi o (a. in k, b. my t ghi hay hin s, c. my tnh)
- My trc quang UV-Vis:
Ngun chiu sng: to ph lin tc, nu o trong vng kh kin th
dng n si t W. Nu cn o trong vng t ngoi th dng n
hiro, teri hay n thy ngn. Ngun chiu sng phi c cng
n nh.
H tn sc: Dng tch tia n sc, b hp th mnh khi qua dung
dch o. Thng dng lng knh hoc tt hn l dng cch t nhiu
x.
Cuvt ng dung dch: Trong cc my hin nay thng dng cuvt
c khong gia 2 thnh trong 1cm ( di b). Nu cn o trong vng
nh sng t ngoi th phi c cuvt l bng thch anh.
Detector: chuyn nh sng thnh dng in, thng dng t bo
quang in, tt nht l nhn quang in t. Cc my trc quang hin
i thng c km my tnh iu khin cc qu trnh chn iu
kin o v x l kt qu.
Xc nh nng theo phng php trc quang:
C s l h thc A = KC
Phng php ng chun.
Phng php vi sai: xc nh mt cht c nng l C
x
,
th ngi ta ly mt dung dch bit nng C
1
m C
1
<
C
x
(C
x
khng ln hn C
1
nhiu) lm dung dch so snh. Li
pha mt dung dch c nng C
2
cng bit chnh xc
(C
2
> C
1
). o A
2
ca dung dch ny, ly dung dch c nng
C
1
so snh. o A
x
ca dung dch nng C
x
vi
dung dch so snh, nng C
1

A
2
= abC
2
abC
1

A
x
= abC
x
abC
1

C
x

II.2.2.4. Phng php phn tch theo ph dao ng
Gii thiu:
Bc x hng ngoi c s sng t 13000 n 10 cm
-1

hoc c trong khong 0,8 n 1000 m.
thun tin ngi ta chia vng ph rng ny thnh:
Vng hng ngoi gn (13000 4000 cm
-1
)
Vng hng ngoi gia (4000 400 cm
-1
)
Vng hng ngoi xa (400 10 cm
-1
)
+ Gi s c phn t AB do 2 nguyn t A v B lin kt vi nhau
to thnh. Xem 2 nguyn t A, B l 2 khi cu ni vi nhau bng
mt l xo, A c khi lng m
1
, B - m
2
. Khong cch gia 2 nhn
nguyn t A, B l r. khong cch r khng phi khng i m khi A,
B dao ng theo trc AB, khong cch ny s dao ng t gi tr
nh nht r
min
n gi tr ln nht r
max
quanh gi tr cn bng r
0
(l
gi tr c xc sut ln nht ca r); dao ng ny gi l dao ng
lin kt hay dao ng co gin tun hon.
Dao ng ca phn t 2 nguyn t:
Nguyn tc:

A, m
1 B, m
2
r
A B
r
0

Ar
A



+ Nu AB b ko dn thnh AB, bin thin khong cch l r, khi s
xut hin mt lc f c khuynh hng ko A, B tr v v tr cn bng;
lc f gi l lc hi phc, f t l vi r v c hng ngc chiu vi
chiu chuyn dch ca A,B.
f = - K. r, vi K: gi l hng s lc (dyn.cm
-1
)
+ Khi r b, dao ng ca A,B c coi l dao ng iu ha v h A-B
gi l h dao ng iu ha. Tn s dao ng ca dao ng ny (tn
s dao ng ring) tnh theo h thc:

2 1
2 1
m m
.m m
M
+
=

M
K
2
1

s
=
M: gi l khi lng thu gn ca A,B v c tnh nh sau:
+ Tn s dao ng cng ln khi M cng nh v K cng
ln.
+ i vi cc lin kt bi =, hng s lc gp 2, 3 ln lin
kt n, do tn s dao ng gp 2, 3 ln.
v: l s lng t dao ng, v = 0, 1, 2, 3, mc
nng lng dao ng thp nht: v = 0, phn t vn c
nng lng dao ng.
+i vi dao ng iu ha, nng lng dao ng ch c
th nhn mt dy gi tr gin on, theo h thc:

|
.
|

\
|
+ =
|
.
|

\
|
+ =
2
1
v h
2
1
v
M
K
2
h
E
s v
iu kin hp th bc x hng ngoi:
c bc chuyn nng lng dao ng ch cn nng
lng tng i b, tng ng vi bc x hng
ngoi, do thng gi ph dao ng l ph hng
ngoi. Tuy nhin khng phi bt k phn t no cng
c kh nng hp th tia hng ngoi cho hiu ng
ph dao ng, m cn c mt s iu kin:
o Cc phn t ch hp th bc x hng ngoi
chuyn sang trng thi kch thch khi s dao ng lm
thay i momen lng cc. Bi vy cc phn t nh
N
2
(NN), O
2
(O=O) khng hp th bc x hng ngoi
v chng c mmen lng cc bng 0, n khng b
mmen lng cc lm thay i.

o Cc phn t hp th tia hng ngoi c tn s ng bng
tn s dao ng ring ca n. a s cc trng hp phn
t nhit thng ng vi mc v = 0. Khi hp th bc
x hng ngoi c tn s chuyn ln mc v = 1 tc l
chuyn ln mc c nng lng E
v=1
, hiu nng lng (hay
bin thin nng lng): E
v=1
E
v=0
=hv
s
(1+1/2)-hv
s
/2 =
hv
s
=hv. Tn s v ny l tn s c bn.
iu ni trn cng c ngha l cc phn t hp th tia hng
ngoi chuyn ln mc nng lng dao ng ng vi
quy tc ny ng dng cho cc dao ng iu ha. Trong
thc t, dao ng ca cc phn t khng phi l dao ng
iu ha cho nn khng tun theo qui tc trn, m mi
chuyn dch gia cc mc nng lng u c th xy ra,
tc l c th v = +2, +3, ... v tn s tng ng vi cc
bc chuyn xp x 2v
s
, 3v
s
gi l cc m bi
(overtone).
Dao ng ca phn t nhiu nguyn t:
Trong phn t 2 nguyn t, chuyn ng dao ng c
bn duy nht l dao ng co dn mt cch tun hon
(gi l dao ng lin kt hay dao ng ha tr) lm thay
i di lin kt. i vi phn t c nhiu nguyn t,
chuyn ng dao ng rt phc tp. Trong cc phn t
ny ngoi dao ng ha tr cn c cc dao ng bin
dng lm thay i gc lin kt theo cc kiu khc nhau.
+
X
X
A
X X
A
X X
A
X X
A
X
X
A
X
X
A
Dao ng lin kt
khng i xng
Dao ng bin dng
kiu li ko (trong
mt phng)
Dao ng bin i
kiu con lc (trong
mt phng)
Dao ng bin dng vung gc v hai pha
mt phng kiu ci qut (ngoi mt phng)
Dao ng bin dng kiu xon (ngoi
mt phng)
Dao ng lin kt
i xng
+
-
+
minh ha ta xt dao ng ca mt phn t ba nguyn
t: AX
2
+ Tuy nhin c th phn mt chuyn ng dao ng
phc tp thnh mt s hu hn nhng dao ng n
gin hn gi l dao ng c bn hay dao ng chun.
Gi s phn t c N nguyn t, mi nguyn t c
xc nh bi 3 phng chuyn ng trong ta
cc (Descartes) tc l c 3N bc t do, trong 3
bc t do m t chuyn ng tnh tin v 3 bc t do
m t chuyn ng quay ca phn t xung quanh
trc. Nh vy ni chung phn t c N nguyn t s
c 3N-6 dao ng c bn (trong c N 1 dao ng
ha tr, hay dao ng co dn lin kt).
+ Trng hp N nguyn t nm trn mt ng thng
th ch c 2 bc t do xc nh trng thi quay ca
phn t, nn s dao ng c bn s l 3N 5. V d
phn t nc (H2O) c 3 nguyn t khng thng hng
s c 3x3-6 = 3 dao ng c bn.
+ Tuy nhin trong cc phn t nhiu nguyn t s kiu
dao ng thc t c th tng hoc gim nhiu so vi
s dao ng c bn do nhiu l do khc nhau, v d
s xut hin cc bi m, t hp m (do cc dao
ng tng tc vi nhau) hoc khng xut hin trn
ph do dao ng khng lm thay i momen lng
cc, hoc nhng dao ng c bn c cng tn s
(dao ng suy bin) ...
Ph dao ng v cu to phn t:
+ Cc kiu dao ng v tn s dao ng lin quan n
cu trc phn t.
V d: T 4000 2500 cm
-1
: s hp th c trng cho dao
ng co dn ca nguyn t H vi cc nguyn t c khi
lng 19.
V d lin kt C H trong C C H tn s dao ng co
dn lin kt xut hin 3300 cm
-1
, trong hp cht vng
thm v cha no khong 3000 3100 cm
-1
. Vng tn
s trung gian 2500 1540 cm
-1
thng l vng cha
no.
V d: Lin kt c m ph hp th 2500 2000 cm
-1
,
Lin kt = c m ph hp th 2000 1540 cm
-1
.
+ Tn s dao ng ca nhm nguyn t no trong phn t t ph
thuc vo phn cn li c gi l tn s c trng cho nhm v
thng dng pht hin cc nhm chc trong phn t. Tn s c
trng ca nhm t thay i th khng c ngha l
max
hp th khng
i m l
max
dao ng trong mt vng ph kh hp, v thc ra tn
s c trng cng chu nhiu nh hng khc nh thay i trng
thi (kh, lng), nh hng ca dung mi, tng tc gia cc phn
t
Nhm Tn s cm
-1
Nhm Tn s cm
-1

O-H 3650-3250 CC 2200
N-H 3500-2900 C=O 1850-1650
C-H 3300-2700 C=C 1650
S-H 2550 C-O- 1300-1000
Bng tn s dao ng ha tr ca mt s nhm nguyn t:
My quang ph hng ngoi :









1

2
2
3

4
5
| | | |
Truyn
quang
(%)
100
4000 3000 2000 1000 cm
-1

0
S sng
Ch thch:
1.Ngun bc x hng
ngoi
2. Cuvet ng mu
2. Cuvet ng dung dch
so snh
3. Quang k n sc
4. Detector
5. Cu trc ghi ph
S ph quang k hng ngoi hai tia sng:







+ Pic 3000 cm
-1
: Dao ng co dn lin kt C-H trong -CH
3
.
+ Pic 1430, 1370 cm
-1
: Dao ng i xng v bt i xng ca CH
3
.
+ Pic 1724 cm
-1
: Dao ng ca CO.
+ Pic 1218 cm
-1
: Dao ng ca t hp nhm C-(C=O)-C
+ Hp cht ny l CH
3
(C=O)CH
3




u , cm
-1
| | | | |
1724
1430
1370
1218
5000

3000

Ph hng
ngoi ca
C
3
H
6
O
ng dng ca phng php ph dao ng:
Nhn bit cc cht :
\ Xc nh tp cht :
+ Khi mt cht c ln tp cht, s xut hin thm cc m
ph s lm nhe ph. Khi tp cht hp th mnh mt
bc x IR m thnh phn chnh khng hp th th
vic xc nh rt thun li, v d trong mt hidrocacbon
c ln mt lng nh xeton th tn s hp th 1720
cm
-1
chng t iu v hidrocacbon thc t khng
hp th vng ph ny.
Phn tch nh lng:
Vic phn tch nh lng cng da vo h thc Lambert
Beer: A = lg(I
o
/I) = abC
II.2.2.5. Phng php in th
Nguyn tc chung:
Nguyn tc ca phng php l o in th cn bng ca cc ch th
xc nh nng cn bng ca cht cn phn tch hoc theo di
s bin thin nng ca n khi cht tham gia phn ng vi mt
cht khc (phng php chun in th).
T nm 1966, phng php phn tch o in th c mt bc tin
ln nh s pht minh ra mt loi in cc mi gi l in cc chn
lc ion (sau y s k hiu l CLI) tc l cc in cc phn hi mt
cch chn lc i vi cc ion khc nhau.
Khi o in th, ta khng xc nh th cn bng tuyt i ca mt
cc ring bit m ch xc nh th ca n so vi th ca mt cc
dng lm chun, c th khng thay i nh cc Ag/AgCl hay
Hg/HgCl
2
, gi l in cc so snh. Cc m th ca n bin thin theo
nng (chnh xc l hot ca cht cn o gi l cc ch th).
Nh vy in th o c E =
ct

ss
+
j
Trong :

ct
: th ca in cc ch th;
ss
: th ca in cc so snh;

j
: th khuch tn.
ss
v
j
khng i trong qu trnh o.
II.2.2.5.1. Phng php in th/cc loi in cc chn lc
ion
Gii thiu:
in cc mng rn: c th l mng ng th hay d th. Cc mng rn
ng th thng c ch to t cc loi n tinh th, v d n tinh
th LaF3, t mui nng chy ng rn, t bt mui nn di p sut
cao. in cc mng rn d th: tinh th cc cht c kh nng dn in
bng ion c phn b u vo khung to mng thch hp nh
polietilen, PVC, ...
in cc mng rn ng th tuy cho lp li v chnh xc cao
nhng kh ch to, in cc mng rn d th v mng mng ch to
hn.
Mng ch?n l?c Ion
Dung d?ch
trong
C?c so snh trong
Ag/AgCl
Mng polyme
Ch?t l?ng h?u c
trao ?i ion
C?c Ag/AgCl
a b

Dung dch
trong
Cc so snh trong
Mng chn lc ion
Cht lng hu c
trao i ion

Cc Ag/AgCl
in cc chn lc mng
rn
in cc chn lc mng
lng
in cc mng lng c kh nng trao i ion: l mt mng polime
mng cha cht trao i ion.
in Cc chn lc mng lng xc nh Ca
2+
dung dch trong l
CaCl
2
nng khng i, trong c in cc so snh trong
Ag/AgCl. Mng xp polime k nc cha ionit lng hu c ca Ca
2+
,
mt pha tip xc vi dung dch trong, pha kia tip xc vi dung
dch phn tch.
Nguyn l lm vic ca in cc mng rn: s b tr mch o

C?c so
snh trong

2
Dung d?ch
trong (2)
aj (2)
Mng ClI

M

Dung d?ch
phn tch (1)
aj (1)
C?c so
snh ngoi

1
C?c ClI
Cc CLI
Cc so Dung dch Dung dch Cc so
Khi ni cc CLI vi cc so snh ngoi, sc in ng ca pin:
E =
2
+
M

1
(
M
: in th mng,
2
+
M
=
CLI
).
Trong trng hp n gin nht, dung dch ch cha ion j v khng
c ion cn tr th


a
j(1)
, a
j(2)
l hot ion j trong cc dung dch tng ng; a
j(2)
=
constant v Z l in tch ion nn c th rt gn biu thc trn

CLI
= f(lna
j(1)
)
Nu trong dung dch c cc ion cn tr l i, hot l a
i
, h s chn
lc ca ion j i vi i l K
ij
th theo cng thc Niconsky, ta c:


Nh vy trong trng hp n gin v php o thc hin 25
0
C th
thay tt c cc s hng l hng s vo cng thc trn ta s c:


) 2 ( j
) 1 ( j
M
a
a
ln
ZF
RT
= A
(

E + + =
i
j
i j i j
j
CLI
Z
Z
a K a ln
F Z
RT
const
) 1 ( j a
a lg
Z
059 , 0
E E + =
E
a
l hng s ca ring tng in cc CLI
Phn tch nh lng:
Phng php ng chun: T biu thc trn c th xc nh c a
+ Nhng gi tr cn tm l C, a= f.C. Khi xy dng ng chun ta pha cc
dung dch c C bit trc nn t a suy ra C tng ng, phi gi h
s f (h s hot ) khng i, m:



C
i
, Z
i
l nng v in tch ca cc ion trong dung dch. Do , mun
gi f khng i ta phi gi khng i. Mun vy, ngi ta thm vo
dung dch in ly c nng tng i ln v khng i (ting Anh vit
tt l TISAB: Total Ionic Strength Adjustment Buffer: dung dch m
chnh lc ion). Khi chun b cc dung dch u phi thm dung dch m
ny nh nhau. T ng chun E C, vi dung dch c nng C
x
sau
khi o c E
x
ta c th tm c C
x
.


1
0,5Z
lgf
2
+

=
2
i i
Z C
2
1
E =
v
Phng php thm chun: xc nh nng C
x
ca
mt ion (dung dch ta c chun b vi lc ion khng
i), ly mt th tch V
o
, o c E
1
. Sau thm mt
th tch rt nh v nng C
a
bit. o li in th,
c E
2
. T biu thc quan h nng v in th d
dng tm c C
x
.
Dung d?ch trong
C?c so snh trong
Ag/AgCl
Mng th?y tinh
Dung dch
trong
Cc so snh
trong (Ag/AgCl)
Mng thy tinh
Cu to in cc thy
tinh
ng dng:
o pH bng in cc thy tinh:
+ in cc thy tinh l loi in cc chn
lc ion (ion H
+
) ra i sm nht. Mng
chn lc ion H
+
l mng thy tinh c cu
to theo s hnh sau. S mch o
cng tng t mch o in th in cc
chon lc ion, ch khc l dung dch trong l
mt dung dch m c xc nh. Cng lp
cc php tnh nh i vi in cc chn
lc ion, cui cng ta s c:
E = const = 0,059 pH (vi pH = - lga
H+
).
+ in cc thy tinh l in cc tt nht
o pH trong khong pH = 2 10. T pH
11, php o khng chnh xc v nh hng
ca cc ion Na
+
, K
+


II.2.2.5.2. Phng php phn tch Von Ampe (pp
cc ph)
Phng php Von Ampe l tn gi chung ca nhm cc
phng php phn tch da vo vic nghin cu ng
cong phn cc biu din quan h gia in th v
cng dng khi in phn dung dch nghin cu vi
cc in cc lm vic c bit: mt trong 2 in cc c din
tch b mt rt nh v nh hn nhiu ln so vi din tch b mt ca
cc kia. in cc b gi l vi in cc, c th l catt hay ant.
Phng php Von Ampe da trn qu trnh in phn vi in
cc git Hg thng c gi l phng php cc ph.
* Nguyn tc chung:
+ Xt trng hp ip phn vi vi
in cc l git Hg, ng vai tr
catt v ant l mt lp Hg y
bnh in phn. Sau ny ngi ta
hay dng ant l cc Calomen.
+ Gi E l in th gia 2 cc,
A
l
th ant,
K
l th catt, R l in
tr ton mch, I l cng dng,
lc : E =
A

K
+ IR
+ I thng rt b (10
-5
10
-7
A), R rt
nh nn c th b qua s hng IR.
V in cc ant c b mt rt ln,
mt dng rt nh nn hu nh
khng c phn ng in cc xy ra
ant v
A
c th coi nh khng
i. Do c th coi nh E = -
K
=
f(I).
1. Ngun in 2. Bnh in phn
3. Ant 4. Catt
5. in k 6. Bin tr
Git Hg chy ra t mao qun, ng knh
trong khong 0,03 mm, tc chy 3 4
giy/git. in phn bng dng in 1 chiu,
in th t vo 2 cc c th iu chnh nh
bin tr 6.
2 4
3
1
5
6
* S phn cc trn in cc git Hg
-
+
Ta nghin cu mt trng hp c th, v d in phn dung
dch ZnSO
4
10
-3
M. Tng in th t t theo tc u, ghi
dng tng ng.
* Sng cc ph.
+ Tip tc tng in th th xy ra phn ng: Zn
2+
+ 2e = Zn(Hg) (hn hng Zn).
Nng ca ion kim loi lp st in cc gim, s chnh lch gia C
O
su trong
dung dch v C
M
st in cc tng, dn n s khuch tn tng v cng dng
cng tng (on BC). Nhng khi tng in th n mt gi tr no , vn tc khuch
tn bng vn tc kh, lc C
0
- C
M
= 0 v do dng rt nh (~10
-5
A) nn C
O
thc t
khng i v th sau d tng in th th dng hu nh khng i Dng ny gi
l dng gii hn v cng ph thuc C
O
(on CD). ng cong ABCD gi l sng
cc ph.

A B
C D I
E
1/2
V
Sng cc ph.
+ Khi in th cha t n gi tr xy ra phn ng kh ion
H
+
, ta thy xut hin dng rt b gn nh nm ngang (on AB)
gi l dng d Ir Dng d ny gm dng t Ic v dng
Faraday If, cng khong 10
-7
A. Dng t sinh ra do b
mt in cc xut hin lp in kp coi nh l mt t in
Dng Faraday do s kh cc vt tp cht, oxy
Vy, dng d Ir = Ic + If.
+ Tuy nhin, thc t dng gii hn gm 2 thnh phn:
o Dng khuch tn I
kt
ph thuc vo vn tc khuch tn, (chnh
lch nng ).
o Dng vn chuyn I
vc
do tc dng ca in trng (in tch
m ca catt ht in tch dng l ion dng).
+ Cc phng trnh tnh ton sau ny ch p dng cho trng
hp khi khng cn dng vn chuyn I
vc
, tc l dng gii hn
I
d
ch hon ton do hin tng khuch tn (I
d
= I
kt
)
+ loi b dng vn chuyn ngi ta thm vo dung dch
nhng cht in li tr (khng c phn ng in cc) nng
tng i ln nh KCl, Na
2
SO
4
, NH
4
Cl (v cc cht to
phc, dung dch m ...) gi l cht nn cc ph; cc ion
K
+
, Na
+
to thnh tng chn in trng tc dng ln
cc ion dng (ion kim loi), nu in cc git lm catt.
+ Nhiu khi sng cc ph b bin dng do xut hin s
tng t ngt dng khuch tn, gi l cc cc i:
cc i xut hin trong mt khong th hp (loi 1), cc
i xut hin v ko di trong mt khong th kh rng
(loi 2).
Cc yu t nh hng n dng sng cc ph:
E
I
a
b
a: Cc i loi 1
b: Cc i loi 2
Cc cc i trn sng cc ph
+ Cc i loi 1: S tng t ngt ca
dng trong mt khong th rt hp. Do
chuyn ng b mt ca git Hg lm
tng cng dng khuch tn.
loi b cc cc i, ngi ta thm 1
lng rt nh cc cht hot ng b
mt nh gelatin, aga
+ Cc i loi 2: S tng t ngt ca
dng trong mt khong th rng. Do
trong dung dch nghin cu lun lun
c oxi ho tan m O
2
trong mi trng
axit cng nh mi trng kim khi b
kh to ra 2 sng.
trnh sng nhiu ca O
2
cn loi b n trc khi ghi sng cc ph.
Mun vy ngi ta cho kh tr sch O
2
nh N
2
, H
2
, Ar thi qua dung dch
mt thi gian. Trong mi trng kim c th thm mt t tinh th Na
2
SO
3

tinh khit vo dung dch.
Phn tch bng phng php cc ph:
Phn tch nh tnh:



I
E E
1/2
Xc nh E
1/2
trn
sng cc ph
1/2
E

E


I
I I
d
ln


+ Th ng vi chiu cao sng cc
ph l mt i lng khng i,
ch ph thuc bn cht cc cht
nghin cu v cht nn cc
ph. Do c th da vo th
na sng (
1/2
) nhn bit cc
cht (trong thc t gi tr o c
l E
1/2
khi so snh vi th in cc
Calomen c khng i).
+ C th tm E
1/2
nh hnh trn
hay theo phng trnh sng cc
ph:

(khi I =1/2 I
d
, th E=E
1/2
)
I
I I
nF
RT
E E
d

+ = ln
2
1
(I
d
: cng dng
gii hn )
+ Quan h gia I
d
v C
M
(nng ion kim loi) c biu din
bi phng trnh Inkovitch:
I
d
= 605.n.D
1/2
.m
2/3
.t
1/6
.C
M
Trong :
o n: s e tham gia phn ng kh in cc.
o D: h s khuch tn, cm
2
.s
-1
o m: khi lng Hg chy ra t mao qun trong 1 giy (mg.s
-1
)
o t: thi gian to git Hg (s), C
M
: nng ion kim loi (mmol/l)
+ Nu duy tr D, m, t khng i th phng trnh trn c dng
thu gn: I
d
= K.C
M

+ Da vo h thc ny c th xc nh nng C
M
theo ng
chun I
d
C
M
, hoc theo phng php thm chun.
Phn tch nh lng:
II.2.2.6. Phng php sc k
Nguyn tc:
+ Phng php sc k l phng php tch cc cht da vo
s phn b ca chng gia hai pha ng v tnh tip xc vi
nhau nhng khng trn ln. Trong h thng sc k pha tnh
khng di chuyn, pha ng di chuyn qua sc k. Cc thnh
phn c trong mu phn tch khi tip xc vi hai pha tnh v
ng s tng tc vi hai pha ny v phn b trong hai pha
. S tng tc ny lp i lp li khi cc thnh phn ny di
chuyn theo pha ng. Thnh phn no tng tc mnh
(phn b nhiu) vi pha tnh s di chuyn chm, ngc li
thnh phn no tng tc yu vi pha tnh (phn b vo pha
tnh t) s di chuyn nhanh. Kt qu l cc thnh phn c
trong mu s c tch ra thnh tng di trong pha ng.
+ C nhiu nguyn nhn khc nhau dn n s phn b trong hai pha
nh kh nng ha tan ca cc thnh phn trong hai pha, kh nng
hp ph, trao i ion, kch thc cc phn t,..nhng chnh s lp
i lp li hin tng hp ph - phn hp ph ca cc cht khi dng
pha ng chuyn ng qua pha tnh l nguyn nhn ch yu ca
vic tch sc k.
+ Pha ng l cc lu th (cc cht trng thi kh hoc lng), pha
tnh c th l cc cht trng thi lng gi trn mt cht mang rn
hoc rn.
- Phn loi cc phng php sc k:
* Ty theo cc dng pha tnh v pha ng v c ch phn b ngi ta
c th chia cc phng php sc k thnh mt s nhm chnh sau:
Sc k lng: Sc k lng - lng; Sc k lng - rn
Sc kh kh: Sc k kh - lng; Sc k kh - rn
* Theo hin tng sc k: gm c: sc k hp ph, sc k phn b, sc
k trao i ion, sc k theo loi c.
+ H s phn b:
H s phn b D c xc nh bi i lc ca cht tan i vi
hai pha. Trong sc k D l t s nng tng ca cht tan trong
pha tnh C
S
v pha ng C
M
:
D= C
S
/C
M
D cng ln th cht phn b cng nhiu trong pha tnh v di
chuyn cng chm.
+ Th tch lu v thi gian lu:
o Thi gian lu t
r
(retention time) l thi gian t khi np cht tan
vo ct sc k n khi xut hin nng cc i detector.
o Th tch lu tng ng V
R
(retention volume) t l vi t
R

V
R
= t
R
x F
c
(trong F
c
l lu tc, ml/pht)
- c trng ca cht tan:
Tc di chuyn ca mt cht c th c c trng bi h s
phn b D ca n gia hai pha hoc bi cc i lng v s
lu gi ca cht trn pha tnh (thi gian lu, th tch lu)
o Gi t
M
l thi gian i qua ct sc k ca cht tan khng b lu, th
cng l thi gian lu ca pha ng (coi nh thi gian cht). V
M
gi l
th tch cht cng chnh l th tch pha ng i qua ct.
o Ngi ta cn dng mt tham s khc l t s phn b K, l t s s
mol cht tan trong pha tnh v pha ng: K= (C
s
.V
s
)/(C
m
.V
m
) =
D.(V
s
/V
m
). Trong phng php sc k ngi ta thng phi chn
iu kin iu chnh sao cho K nh hn khong 20, nu khng
thi gian lu qu di khng chp nhn c.


t
M

t
R


N
?
n
g


?


Thi im
np mu
Thi gian lu, pht
Nng

Sc
ca mt
cht
+ GC da trn nguyn tc sau: khi mt hn hp cc cht
bay hi c kh mang (pha ng) vn chuyn qua ct
cha mt cht hp ph rn hoc thng thng hn l
qua mt pha lng hp ph ln mt cht rn (pha tnh),
mi thnh phn hi c phn b trong kh mang v
cht rn hoc cht lng.
+ Ty theo thi gian lu, mi thnh phn hi s thot ra
khi ct sc k cc thi gian khc nhau v c xc
nh bi detector thch hp, c th xc nh nh tnh
cng nh nh lng.
Nguyn tc:
- Sc k kh (GC):

Kh nng phn tch rt cao, ngay c i vi nhng hn
hp phc tp;
nhy, chnh xc v tin cy rt cao;
Thi gian phn tch ngn,
C th phn tch hng lot.
+ u im :
Thit b GC:
6
1 3 4 5 7 8 9 2
1. B cung cp kh mang; 2. B iu chnh p sut;
3. B o lu lng; 4. B np mu;
5. Ct sc k; 6. Bung n nhit;
7. Detector; 8. B khuch i in t;
9. B x l tn hiu
o Ct nhi:
Thng ch to dng ng bng thp khng g, thy tinh. ng knh
1,6 9,5 mm, chiu di khong 3m. Trong sc k kh rn vt liu
nhi ct thng l Silicagel, polime xp hoc sng phn t nh
Zeolit. Trong sc k kh lng cht nhi ct ng vai tr cht mang
pha lng (pha tnh), cht lng l cht khng bay hi c tm ln
cht mang thnh mt lp mng. Cht lng thng dng l du
Silicol, polietilen glycol Cht mang thng l t Diatomit, gch
chu la nghin.
+ Ct sc k: C hai ct: ct nhi v ct h hay ct mao qun.
o Ct mao qun:
Thng dng l ct mao qun h, trn thnh ct c mt lp cht
lng mng, u, ng knh trong ca ct nh hn 1mm, chiu
di t 30 90 mm. Ct thng c ch to t kim loi, thy tinh
hoc cht do.
+ Kh mang:
Trong GC, kh mang l kh dng vn chuyn cc cht kh
nghin cu qua ct sc k, chnh l pha ng. Kh mang phi
l cc kh tr, khng tng tc vi mu, vi pha tnh, vi cc b
phn tip xc, phi c tinh khit cao (t nht l 99,995%), phi
chn cho ph hp vi Detector v cc yu cu khc v phn
tch. Ngoi ra phi chn kh mang c gi thnh r v an ton, ty
tng trng hp c th dng N
2
, H
2
, He, Ar, O
2
v khng kh.
+ Detector:
Ghi cc tn hiu thu c t qu trnh sc k, phn tch tn hiu v
bit c cc cht cn phn tch, tch.
Trong GC hin nay ngi ta s dng Detector dn nhit, Detector
ion ha ngn la, Detector hp th electron
* Detector ion ha ngn la (FID: Flame Ionization
Detetor): Da vo s thay i dn in ca ngn la H
2

t trong mt in trng khi c cht hu c cn tch chuyn
qua. Trong ngn la ca ring H
2
v khng kh, dn in
thp nn dng in o c b. Khi c cc cht c kh nng
ion ha mnh hn t ct sc k ra i vo ngn la, b t
nng, b ion ha, dng in s tng mnh. Detector ny c
nhy cao gp hng trm n hng nghn ln so vi TCD v
phn hi vi hu ht cc cht hu c tr axit fomic,
andehitfomic. C th o c nhng dng in n 10
-12
A,
pht hin c n 10
-9
gam.
* Detector cng kt in t (ECD: Electron Capture
Detector): Da vo i lc khc nhau ca cc cht i vi cc
electron t do, c bit rt thch hp i vi cc hp cht Clo
ha, Alkyl ch c th xc nh c mt s thuc tr su clo
ha n mc picogam (10
-12
gam). nhy cao.
Phn tch bng GC:
+ Phn tch nh tnh:T sc k ta s nhn c cc tn hiu
ng vi tng cu t gi l cc pic sc k. Thi gian lu hay th
tch lu ca pic l c trng nh tnh cho cht cn tch. So snh
thi gian lu (th tch lu) ca mu th vi mu chun ghi cng
iu kin.
+ Phn tch nh lng: Tn hiu thu c Detector t l vi
nng hoc hm lng cc cu t. Tn hiu y thng l
chiu cao pic, din tch pic. t c hiu qu phn tch ng,
iu cn thit l phi tch cc cu t cn nghin cu mt cch
hon chnh, khng c s xen ph pic ny vi pic khc.
ng dng ca phng php sc k:
Phn tch sc k c ng dng tch phn li, phn tch nhiu
hp cht khc nhau, v c cng nh hu c, c bit l phn tch
cc hp cht hu c.
Phng php ny c th tch v phn tch nhiu hn hp phc tp.