Phng php ly mu v phn tch cc cht c trong khng kh 2005

PHNG PHP QUAN TRC, LY MU V PHN TCH

CC CHT C TRONG KHNG KH
1.Phng php ly mu
1.1.a im v v tr ly mu
Trc ht cn phi iu tra ni pht sinh ra hi, kh c u,
trng thi tn ti ca cht c (th rn, lng hoc kh), ngun hi kh thi
pht sinh ra t khu no: chun b nguyn liu, qu trnh sn xut, cc cht
trung gian, tp cht hay sn phm
a im v v tr ly mu phi c chn trn c s khoa hc v
c h thng theo ng nh yu cu ca ni dung kho st nh gim st cht
lng mi trng, kim tra quy trnh sn xut hoc vic tun th php lut mi
trng hay nh gi tc ng c hi ca hot ng sn xut n sc khoe cng
ng v mi trng... Chng hn nh, khi nh gi tc ng mi trng ca
mt hot ng sn xut no , a im ly mu cn phi t gia khu vc cht
c bay ra, ni i li v lm vic ca cng nhn, ng thi cn phi trnh cc h
thng thong hi, ca s.
Khong cch t a im ly mu c th l 10, 50 hoc 100m so vi
ngun pht thi, nu xt thy cn xc nh mc nhim do ngun gy ra.
V tr ca cc im ly mu c chn bng vic s dng mng li i
xng cc vi ngun nm trung tm. lch cho php i vi cc v tr
chn theo cch c h thng cng c xc nh. Trong cc khu vc c a hnh
phc tp, v tr cc im ly mu c xc nh ch yu theo cc iu kin pht
tn cc b v phi xem xt cn thn trc khi nh v tr ly mu. Trong cc khu
vc nh vy mt cuc nghin cu vi qui m nh c tin hnh trc khi
la chn ln cui v tr cc im ly mu.
Ni chung, vic la chn cc a im quan trc v ly mu cn phi tun
th cc nguyn tc sau:
-Nu nh gi nh hng ca cc khu cng nghip n cht lng mi
trng khng kh th cc a im quan trc c chn phi l cc khu cng
nghip - ni m mi trng ang l vn thi s nng bng.
ng Kim Loan, HUS-VNU.VN
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

-a im phi phn nh c cht lng khng kh t cc hot ng
cng nghip. Mun vy, cn phi xt n 2 yu t l khng gian v thi gian:
+Vi yu t khng gian: s dng mng li i xng vi ngun nm
trung tm, xem xt v tr ca cc c s sn xut trong 1 khu cng nghip
chn a im t mu, ng thi phi ch n a hnh trnh cc tc ng
ca a hnh (tc l tm hiu c cc iu kin pht tn).
+Vi yu t thi gian: quan trc theo ma v cc p nh th no c
th phn nh ng nht nh hng ca khu cng nghip n cht lng khng
kh.
1.2. Chiu cao ly mu khng kh v chiu cao im o
Chiu cao ly mu khng kh v chiu cao im o c chn ngu nhin
hoc h thng so vi mt chiu cao qui chiu c chn ngu nhin. Ni
chung ti cc im ly mu, cc im o phi cao trn mt t 3 mt, nhng
khng nht thit phi p dng trong nhng khu vc c nh cao tng hoc ni m
nhim v kho st c qui nh cc mc cao khc. C th cc cuc iu tra v
mc nhim khng kh ng giao thng th vic ly mu cn c tin
hnh chiu cao ht th (thng thng ch di 2 mt hoc thm ch thp hn
xc nh cc mc nhim khng kh i vi i tng l tr em).
Khi tin hnh cc khu vc c t l phn trm cc nh cao tng ln, c
nhiu ngi sng nhng cao khc nhau m khi o nhim khng kh
mc cao 3 mt khng cho kt qu i din th cn thit sp xp ni ly mu
c t cc cao khc nhau. iu ny c bit quan trng khi cc nh cao
tng nh vy gn k cc ngun thi chnh.
cao im o v chiu cao ly mu phi phn nh c tc ng ca
nhim khng kh do hot ng cng nghip n cht lng khng kh phi tho
mn cc iu kin sau:
+khng gn ngun thi
+khng b nh hng ca a hnh
+phn nh ng nng nn ca khu vc (ch n yu t nh cao tng,
dn c v chiu cao ng khi).
ng Kim Loan, HUS-VNU.VN
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

1.3.Nguyn tc ly mu
Vic ly mu kh v bi cn phi c thc hin theo ng tiu chun
php quy, mi a im nn ly hai mu song song cch nhau 20 cm. Chng hn
vic thu cc mu bi v kh nn thc hin theo TCVN 5973-1995 v ISO 93591998.
ng thi vi vic thu mu, nhm nghin cu cn phi quan trc v o
c cc yu t vi kh hu. Vic ly mu v phn tch c tin hnh theo ng
tiu chun Vit Nam TCVN 6152-1996, tiu chun ca B Y t - 52 TCN 35489 v cc tiu chun phn tch kh ca Nht Bn JIS Z-8808, K-0095, K-0096.
Vi bi: dng thit b thu bi c lu lng 30-40 lt/pht, hoc thit b
thu bi c lu lng cc ln (> 1000 lt/pht) thu v xc nh hm lng bi
trong cc khu dn c, th v khng kh xung quanh ni chung, cng nh
xc nh hm lng kim loi, cht hu c, sol kh c mt trong kh quyn.
Ngoi ra c th s dng thit b o nhanh phn tch bi phc v cho vic lp
cng thc hiu chnh, nh gi nhanh mi trng v thc hin chng trnh
gim st nhim khng kh.
K thut n gin nht ly mt mu kh l bm khng kh c cht c
vo trong mt dng c c th tch xc nh, hoc thng thng l ht khng kh
c cht c qua dng c thu gi (phin lc hoc ng hp th). Cc thit b thu
gi cht c thng c tc bm t 0,25 n 2,50 lt/pht.
Vi CO: c th s dng dung dch hp th hoc ly mu kh v phng th
nghim phn tch.
Vi cc kh khc nh NOx, SOx v O3 dng dung dch hp th ring cho
mi loi, thu mu v a v phn tch trong phng th nghim.
Nhn chung, vic xc nh cc thng s c thc hin theo cc TCVN
tng ng cho tng cht v phn tch theo Standard Methods ca nh xut bn
American Public Health Association, Washington, DC 20005.
1.4. Vn chuyn v bo qun mu
Khi ly mu bng dng c cha, dng c ny phi c gi trong cc hp
g c lt xp trnh v. Nn bo qun mu trong qu trnh vn chuyn v
ng Kim Loan, HUS-VNU.VN
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

thi gian i thu gom trong cc thit b lm mt hoc trong nc v trnh
nhng tc ng lm sai lch hm lng c t c mt trong mu (v d, trnh
nh sng mt tri khi thu mu phn tch ozn).
Khi ly mu bng ng hp th xong cn phi cha mu vo trong cc
bnh cha mu bng thy tinh, c nt nhm, dung tch t 25-50 ml. Vic vn
chuyn phi m bo an ton cho mu, trnh v, lm ln ln v mu b trng
ln vo nhau; ng thi cng cn phi bo qun lnh mu trong qu trnh di
chuyn. Mu nn chuyn v phng th nghim cng sm cng tt v bo qun
trong ngn mt ca t lnh. Tin hnh phn tch ngay (nu c th).
Ni chung, mu c th c php lu gi, nhng thi gian lu gi khng
nn qu 3 thng. Qu 3 thng, nu khng c iu g tr ngi, lp bin bn
hy mu.
2. Yu cu khoa hc v cht lng s liu.
Cht lng s liu quan trc mi trng c nh gi qua cc mt sau:
chnh xc
chnh xc ca s liu c nh gi thng qua kh nng phn nh
ng thc t n mc no. iu ny ph thuc vo trang thit b my mc,
qui trnh, qui phm quan trc, x l bo qun mu v trnh chuyn mn ca
ngi thc hin.
Tnh ng nht ca s liu.
Tnh ng nht ca s liu l i hi bt buc c th so snh hn km
gia cc s liu. iu ny rt quan trng trong trng hp cn nghin cu s
bin i theo khng gian v thi gian ca mt yu t mi trng no .
m bo tnh ng nht ca s liu cn phi:
- Thng nht phng php o c. Hin nay mt s yu t mi trng c
th c nhiu loi my o, v mi my c mt phng php o ring ca mnh.
- Thng nht qui trnh, qui phm quan trc. Cc yu t ny thay i theo
khng gian v thi gian, do khng thng nht v tr quan trc v thi im
ly mu s cho cc kt qu khc nhau.
ng Kim Loan, HUS-VNU.VN
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

Trn thc t, chng ta khng th t trm quan trc v ly mu tt c
mi im; do vy ch chn mt s im nht nh m t c th khng ch
cho ton b khu vc. Vn t ra l cn tm c mt h thng im o sao
cho s im l t nht m vn m bo yu cu trn. Tu theo cc iu kin cho
php, m chng ta c th gii quyt vn ny theo cc phng php sau:
Phn tch tng quan
Trong trng hp c mt lng s liu v mi trng ln, c thu
thp t mt mng li u khp, th chng ta c th chn h thng ti u bng
phng php phn tch tng quan. Ni dung ca phng php ny l tm mc
quan h ca cc yu t mi trng thu c t cc trm c bng thng k,
t tm ra cc trm tha, cc trm thiu trong h thng trm c.
y l phng php tt nht, song khng my thun li nu cng tc
mng li mi trong giai on ban u.
Nghin cu c ch tc ng
Cc yu t mi trng thng xuyn bin i theo khng gian v thi
gian di tc ng ca cc iu kin t nhin. V d trong khng kh cc cht
gy nhim bin i di tc dng ca gi, m, v.v. Mi mt nhn t tc
ng to nn mt bc tranh mi trng tng ng.
Cc cht nhim di chuyn do hon lu gi trn cao thng phn b u
v bao gm mt khng gian rng ln, cn do gi tng thp cc cht nhim
thng thu nh phn b quanh ngun thi. Nu nm c c ch tc ng cho
php nh ra c mt h thng trm hp l.
Phng php tnh ton trn m hnh
Cc cht gy nhim bn di chuyn v bin i c miu t bng cc
phng trnh ton hc nh s gip ca my tnh in t cho php gii c
cc bi ton . Cc kt qu tnh ton trn m hnh tuy cha t n mc chnh
xc cao do cc kh khn v d kin, s liu a vo, tuy vy kt qu tnh theo
m hnh s cho c mt bc tranh tng qut v tnh trng v mc nhim
khu vc nghin cu.

ng Kim Loan, HUS-VNU.VN

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

Trn bc tranh tng qut cho php nh ra c mt mng li kim
sot c mi trng trong vng c tnh. Thit lp h thng trm quan trc
bng cch tnh ton trn m hnh thng c s dng khi vng nghin cu hp
nh mt thnh ph, mt on sng chng hn. Trong thc t hin nay khng
cho php s dng ch mt trong ba phng php trn, m tu theo kh nng m
dng phng php ny hay phng php kia.
Theo di lin tc theo thi gian.
Hin nay mi trng trng thng xuyn thay i, do mt trong
nhng nhim v t ra cho cng tc mng li l thu c cc dy s liu m t
nh gi c bin i theo thi gian. Vn l t ra c cc thi im
quan trc sao cho khong cch gia cc thi im (cn gi l chu k quan
trc) khng qu nh hoc qu ln m vn cho php xc nh c mt cch gn
ng cc yu t mi trng bt k thi im no.
Tnh hon chnh ng b.
Hin nay nh gi tc ng mi trng ngi ta thng khng nh
gi tc ng ca tng yu t ring m s dng ch tiu tng hp P:
n

P
i 1

Ci
Cio

Trong Ci l nng ca yu t mi trng th i, Cio l nng cho

php ca yu t . nh gi tc ng bng ch tiu tng hp bt buc phi
quan trc ng thi nhiu yu t ca mi trng. Mt khc yu t mi trng
li chu s chi phi mnh m ca cc iu kin t nhin khc. Do vy ngoi
quan trc cc yu t mi trng cn cn phi quan trc cc yu t t nhin c
lin quan. V d trong quan trc mi trng khng kh cn phi quan trc gi,
nhit , m, v.v.,
Tnh c trng (i din) ca s liu.
S liu thu c ti trm s mt ht ngha nu n khng c trng cho
c mt vng xung quanh trm. ln ca vng ph thuc vo c im t
nhin ca khu vc. m bo tnh c trng, v tr t trm phi th hin sao

ng Kim Loan, HUS-VNU.VN

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

cho mi trng ti tng t nh mi trng chung cho ton khu vc cn
c quan trc.
Trong quan trc mi trng khng kh nn, im quan trc phi xa cc
ngun thi a phng.

D fi r1 , r2 ; t1 , t2 fi r2 , t2 fi r1 , t1

(1)

Trong fi l nng tng i tng cng ca yu t mi trng i ti 2

im khng gian - thi gian r1,t1 v r2 ,t2 .
Khong cch gia cp trm c xem l ti u nu hm cu trc (1) t
cc i ti khong cch

r r2 r1

ng vi khong thi gian = t2 - t1.

Nu tnh kh bin ca cc yu t mi trng tho mn tnh cht ca

trng ngu nhin ng nht th s khong cch ti u gia cc cp trm
c minh ho bng cc ng trn ng tm.
Kt qu tnh ton
Tnh ton cc gi tr hm cu trc i vi mi trng khng kh c tin
hnh trn my vi tnh COMPAQ PRESARIO 4506.
3.Thit b v cch ly mu kh
3.1. Thit b ly mu kh
xc nh hm lng SO2 trong khng kh, trc ht cn phi thu mt
th tch chnh xc khng kh v lm sao cho kh SO2 c hp th mt cch
nh lng hon ton vo mt th tch cht lng xc nh. Mu thu c em
xc nh lng kh SO2 hp th bng mt phng php tiu chun v t
tnh c hm lng SO2 trong khng kh ni ly mu.
Cc mi trng hp th v mt vi iu kin ly mu c th thay i ty
thuc vo phng php xc nh.
V kh SO2 rt d phn ng v phn ng kh nhanh vi cc cht hp th
c chn, cho nn thit b ch cn ti a 2 bnh hp th mc ni tip l bo

ng Kim Loan, HUS-VNU.VN

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

m hp th hon ton. Trnh t tng qut sp xp thit b c m t nh trn
hnh 1.

u ht

B lc bi

Bnh hp th

Bnh bo v

TB o

My bm

Hnh 1. H thng thit b ly mu kh

Nguyn tc hot ng ca thit b l: khng kh c ht vo t ming
ht, qua b lc bi trnh s cn tr cho phng php xc nh (bi tan hoc
tn ti l lng trong dung dch hp th). Khng kh tip tc i qua cc bnh hp
th cha sn cht lng hp th ph hp, sau qua bnh bo v, qua thit b
o lu lng kh ri qua my bm v ra ngoi.
u ht thng c lm bng nha PTFE, PP hay thy tinh v khi lp
th t quay ming xung. trnh nc ma hay tc ng khc, ngi ta
thng lp thm mt phu chp quay xung cng chiu.
B lc bi gm gi lc v mng lc. Gi lc c th s dng nhng b
thng thng c bn trn th trng hoc thng i cng vi my bm chuyn
dng cho vic ly mu kh. Mng lc phi c lm t vt liu tr i vi kh
lu hunh dioxit v khng ht m. Qu trnh lc qua b lc phi t hiu qu
cao (99%) i vi cc ht bi ln hn 0,3 m. B lc phi m bo thng
kh khng nh hng ti vic ly mu kh. Vt liu lm mng lc c th
dng l si polystyren hoc vt liu tr khc nhng khng nn dng bng hay
vi thy tinh.
Bnh hp th thng l hnh tr c th lm bng thy tinh, PS, PP hay
PTFE tu thuc vo yu cu ca phng php. Bnh phi c np/nt kn, c mt
ng dn kh vo v c u phn phi kh ph hp t v tr gn st y bnh v
mt ng dn kh ra c ming t pha trn ca bnh (cn ch trnh c
ng Kim Loan, HUS-VNU.VN
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

vic lm mt dung dch hp th dng sol kh). Trong khi ly mu c th s
dng 1 hoc 2 bnh hp th mc ni tip nhau.
Bnh bo v c dung ch yu trnh s xm nhp ca dung dch hp
th vo lm hi my bm cng nh thit b o. Hin nay cc my bm chuyn
dng thng gn lin vi bnh bo v v thit b o lu lng.
Trong trng hp phi lp thit b o lu lng kh ri, th phi lu
khng c s dng loi lu lng k lm bng vt liu d n mn.
Cc ng ni phi c lm bng vt liu tr i vi kh SO2 v khng
lm bn mu kh cng nh dung dch hp th. ng PTFE l tt nht song
thng cng, kh thao tc. Trong trng hp ny phi cn n cc u ni lm
sn. PE mm hoc silicon rt tin cho cng vic ny.
3.2. Ly mu kh (TCVN 5978-1995)
Ni ly mu (ni t thit b ly mu) cn phi trnh tip xc vi nhit
qu cao hoc qu thp hay trc tip b nh nng mt tri chiu trong thi gian
di. u ht kh phi c t sao cho trnh xa c mi chng ngi vt (k
c thit b ly mu), t nht l 1 m v cao t nht 1,5 m (thng l cao 3m) trn
mt vng rng, c b mt bng phng. V tr ly mu cn phi chn sao cho i
din c cho mt vng a l. S im ly mu cn thit phi bao trm c
vng nh theo mc ch v yu cu ca cng vic v ng thi cng l i
tng cho cc ch tiu khc c lin quan trong cng vic kho st v nh gi.
Sau khi chn v tr v lp t xong thit b th tin hnh in dung dch
hp th vo cc bnh hp th (ch bnh hp th phi c trng ra sch s v
tt nht l c sy kh trc khi s dng). Th tch dung dch hp th cn
c ong chnh xc vi mt lng ty thuc vo yu cu ca phng php
cng nh yu cu v thi gian ly mu (thng l t 10 cho n 150 ml). Bt
my bm v iu chnh nhanh tc ht kh chnh xc ph hp vi yu cu ca
php o. Thng thng lu lng kh qua bnh hp th l t 0,5 n 2,0 lt/pht.
Sau thi gian cn thit, tt my bm, chuyn mt cch nh lng ton b
dung dch sau hp th vo chai ng mu ri em bo qun hoc chuyn ngay
v phng th nghim phn tch. Chai ng mu c dung tch thng thng t
ng Kim Loan, HUS-VNU.VN
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

50 ml n 500 ml c np/nt kn tuyt i v thng c lm bng vt liu
nh vt liu lm bnh hp th.
4. Phn tch mu
4.1. Phn tch xc nh hm lng kh SO2 trong khng kh
Kh SO2 c xem l kh thi c hi nguy him nht khng phi v c
tnh ca n cao nht m v lng thi ca n l ln nht t rt nhiu ngun khc
nhau. Do vy m vic phn tch, kim tra nng kh SO2 trong kh quyn
thng c quan tm nhiu v c nhiu phng php c s dng xc
nh n.
i vi mi di hm lng SO2 khc nhau, ngi ta u c nhng
phng php ph hp cho tin cy cao. Di y l mt s phng php
thng dng.
4.1.1. Xc nh SO2 bng phng php TCM-PARAROSANILIN
(TCVN 5971-1995; ISO 6767:1990)
a. Nguyn l.
Kh SO2 khi hp th vo dung dch tetracloro thy ngn
(tetracloromercurat - TCM) s to thnh phc cht diclorosulfito thy ngn.
Ngi ta cho thm dung dch axit sulfamic vo dung dch mu ph hy ht
cc ion nitrit t khng kh b hp th theo vo mu. Tip , thm dung dch
pararosanilin hydroclorua axit ha vo mu cng vi dung dch formaldehit
s bin phc trn thnh axit pararosanilin-metyl-sunfonic c mu tm thm.
Phc ny c cc i hp th nh sng bc sng 550 nm. Dng my trc
quang hay UV-VIS spectrophotometer o hp th quang s xc nh c
hm lng SO2 c trong mu thng qua ng chun.
ng chun c th xy dng t hn hp kh SO2 chun vi cch to axit
mang mu nh trnh by trn; hoc c th dng dung dch sulfit mi c
pha v c chun li bng phng php chun oxi ha kh hay chun
in th xy dng ng chun.

ng Kim Loan, HUS-VNU.VN

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

Phng php Pararosanilin c p dng i vi vic kim sot hm
lng SO2 trong khng kh xung quanh. Vng xc nh tt nht l t 0,02 n
0,50 mg/m3 vi thi gian ly mu t 30 n 60 pht. Nu nng vt qu 2,00
mg/m3 th cn phi thn trng khi ly mu; tt nht l dng phng php khc
nh phng php Thorin c trnh by phn 4.1.3.
b. Thuc th.
- Dung dch TCM 0,04 M: ha tan 10,9 g thy ngn(II)clorua (HgCl2) vi
4,7 g NaCl, v 0,07 g mui dinatrietylendiamintetraacetat ngm 2 nc vo
khong 250 ml nc ct ng sn trong bnh nh mc 1000 ml. Lc k cho tan
ht, dng nc ct in n vch mc, lc u v y nt kn bo qun dng.
- Dung dch Pararosanilin 0,16 g/l: cn 0,20 g pararosanilin hydroclorua
ha tan trong 100 ml dung dch HCl c pha ch nh mc A di y. Lc
u cho tan ht. Ly 20 ml dung dch ny cho vo bnh nh mc dung tch 250
ml, thm 25 ml dung dich axit photphoric c pha nh mc B di; thm
nc ct n vch mc, lc u, y nt kn v trong ti. Dung dch s rt n
nh trong vng vi thng.
A. Dung dch HCl: ong chnh xc 86 ml axit HCl c (d = 1,19)
cho vo bnh nh mc dung tch 1000 ml. Thm nc ct n vch mc
v lc u.
B. Dung dch H3PO4: ong chnh xc 205 ml axit H3PO4 c 85%
(d = 1,69) cho vo bnh nh mc dung tch 1000 ml. Thm nc ct n
vch mc, lc u.
- Dung dch focmandehyd 2g/l: dng pipet ly 5 ml dung dch
focmandehyd 36-38% cho vo bnh nh mc dung tch 1000 ml. in nc ct
n vch mc, lc u.
- Dung dch axit sunfamic 6 g/l: cn 0,6 g axit sunfamic ha tan trong 100
ml nc ct. Dung dch bo qun sao cho trnh tip xc vi khng kh s n
nh c trong vng vi ngy.
- Dung dch chun sunfit: Cn 0,3 g natri disulfit (Na2S2O5) v ho tan
trong 500 ml nc ct sau khi ui ht kh tan trong (c th em un si
ng Kim Loan, HUS-VNU.VN
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

ri ngui). y l dung dch khng bn v c nng khng chnh xc nu
tnh ton theo lng cn. V vy dung dch sau khi pha xong phi xc nh li
nng chnh xc bng phng php chun iot - thiosunphat vi ch th l
h tinh bt. Thng thng 1 ml dung dch ny cha t 0,3 n 0,4 mg SO2.
c. Cch tin hnh o mu.
-Lp ng chun:
Chun b 5 bnh nh mc dung tch 25 ml kh v sch nh s t 1 n
5. Ln lt cho vo mi bnh 0 ml, 1 ml, 2 ml, 3 ml, 4 ml v 5ml dung dch
chun SO2 sau khi xc nh chnh xc nng nh trnh by phn trn. Ln
lt thm 1 ml dung dch axit sunfamic, lc u v cho phn ng trong 10
pht. Thm tip 2 ml dung dch focmandehyd v 5 ml dung dch pararosanilin,
thm nc ct loi sch kh n vch mc, lc u. yn dung dch khong
30 pht sau em o hp th quang bc sng 550 nm so vi mu trng
(mu c 0 ml dung dch disunfit).
Trong trng hp c mu kh chun th ly nhng th tch tng ng vi
lng SO2 tng dn v cho hp th vo dung dch TCM nh khi ly mu. Mu
trng trong trng hp ny l mu kh khng - khng cha SO2. Sau khi nhn
c dung dich mu chun ri th tin hnh nh trn.
Tt c cc gi tr o hp th quang (A) c a ln trc tung ca h
to vung gc v tng ng vi cc gi tr nng SO 2 trn trc honh.
ng chun phi l mt ng thng.
-Phn tch mu:
Mu sau khi ly xong, yn trong khong 20 pht nu c zon th
kp phn hy ht, trnh c nh hng ca n ti php xc nh sau ny.
Chuyn ton b lng dung dch mu (thng l 10 ml) vo bnh nh mc 25
ml; dng khong 5 ml nc ct trng k thu nt lng mu cn dnh bnh
ng. Ln lt tin hnh nh phn 1. hp th quang o c em i
chiu vi ng chun va dng xc nh nng SO2 c trong mu.
Nng SO2 trong khng kh biu th bng mg/m3 c tnh theo cng
thc:
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

C

m
m
.1000
.1000
V1
w.t

(1)

Trong m l hm lng SO2 trong mu tnh theo ng chun, V1 l th

tch khng kh tnh theo lt; w l lu lng khng kh khi ly mu tnh bng
lt/pht, t l thi gian ly mu tnh theo pht. Cng thc ny ng cho iu kin
chun l T=298oK; p =101,3 kPa ( 102 kPa).
Trong trng hp khc (khng phi iu kin tiu chun) th th tch
khng kh V1 c thay bng th tch tnh ton li V2 theo cng thc:

V2

298.V1. p
(273 T ).102

(2)

Trong p l p sut kh quyn (kPa), T l nhit khng kh khi ly

mu tnh bng C (oC).
4.1.2. Xc nh SO2 bng phng php chun H2O2/Ba(ClO4)2
(TCVN 5975-1995; ISO 7934:1989).
a. Nguyn l
Kh SO2 khi hp th vo trong dung dch hydroperoxyt s b oxi ha
thnh axit sunphuric. iu chnh pH dung dch v 3,5 bng dung dch NaOH
hoc dung dch axit pecloric. Sau nng ion sunpht c chun bng
dung dch bari peclorat vi ch th l thorin.
T kt qu chun s tnh c hm lng SO2 trong mu.
Phng php ny c ng dng i vi ni c nng SO 2 ti thiu l
30 mg/m3 v khong thi gian ly mu thng thng l 30 pht. Nng SO2
trong kt qu c tnh theo kh kh nhit 273,1oK v p sut l 101,3 kPa.
Nu cc iu kin khc th phi tnh th tch kh theo biu thc (2) phn c,
mc 4.1.1.
d. Ly mu

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

Tham kho trong mc 3.2. Trong phng php ny, do xc nh nhng
nng kh cao ca SO2 nn thng phi s dng 2 bnh hp th mc ni tip.
Th tch dung dch hp th thng dng l 80 ml chia i cho 2 bnh hp th
dung tch 100 ml hoc 160 ml chia i cho 2 bnh hp th dung tch 250 ml.
Nng SO2 v cc iu kin khuyn co trong phng php ny c th tham
kho trn bng 1.
Khi ly mu xong, dng my o pH kim tra pH dung dch mu. iu
chnh pH ca dung dch v 3,5 v chuyn ton b mu vo bnh cha mu ri
a ngay v phng th nghim phn tch.
4.1.3. Xc nh SO2 bng phng php trc quang dng Thorin
(TCVN 5978-1995, ISO 4221:1980)
a. Nguyn tc
Khi SO2 hp th vo dung dch hydroperoxit s to thnh axit sulfuric.
Dng mt lng chnh xc, d dung dch bari peclorat kt ta ion sunphat.
Lng d bari cho to phc mu vi thorin v em o hp th quang bc
sng 520 nm. Nng ion sunphat s t l nghch vi hp th quang.
Phng php ny c th xc nh c hm lng lu hunh dioxit trong
khng kh xung quanh c nng t 3,5 n 150 g/m3.
c. Ly mu.
Theo TCVN 5968-1995 v ISO 4210 trnh by phn trn.
4.1.4. Phng php hng ngoi.
Tt c phng php hng ngoi phn tch hm lng cc kh nh SO 2,
CO2 u da trn nguyn l o dao ng ca cc lin kt ca cc nguyn t
S, C ni trn vi nguyn t oxy.
V vy c th s dng cc phng php o trc tip trn c s phn tch
hng ngoi vi cc my chuyn dng hin ang bn trn th trng. Mi my
u c km theo hng dn c th (cookbook) t vic ly mu ti cc bc k
thut o v tnh kt qu. y l cc phng tin rt hiu qu v hu ch khi tin

ng Kim Loan, HUS-VNU.VN

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

hnh phn tch nhanh mu khng kh nh gi xu th bin ng, nh gi
nhanh mi trng...
4.2.Phn tch xc nh hm lng NOx trong khng kh
4.2.1. Phng php Griess
a. Nguyn l
Kh nit dioxit khi hp th vo dung dch kim NaOH s cho ion nitrit
theo phng trnh 1.
2NO2 + 2NaOH = NaNO2 + NaNO3 + H2O

(1)

Do ch c mt na lng NO2 c hp th hnh thnh ra nitrit, cho nn

khi tnh kt qu phn tch mu bng trc quang s phi nhn kt qu o c
vi 2. Axit ha dung dch NaOH hp th NO2 bng axit acetic s gii phng
ra axit nitr theo phng trnh 2 di y.
NaNO2 + CH3COOH = HNO2 + CH3COONa

(2)

Axit nitr ny tc dng vi axit sulphanilic v -naphtylamin s cho

mt hp cht azoic mu hng.
C6H4NH2SO3H + NaNO2 + CH3COOH = C6H4N2SO3Na.CH3COO + 2H2O
C6H4N2SO3Na.CH3COO + C10H7NH2 = C6H4N2SO3Na.C10H6NH2 + CH3COOH
Phng php ny c nhy 0,5 g NO2- hay 1,0 g NOx, so mu bc
sng 540nm.
C th thay thuc th Griess bng s dng tc nhn to mu khc l dung
dch cha 10 g sulphanilamid, 1 g N-(1-naphtyl)-etylendiamin trong 1 lt axit
phosphoric 10% v so mu bc sng 543 nm.
b. Ly mu
Ly mu kh v dng c thit b phc v cho vic ly mu c thc hin
nh trnh by phn 3.1. v 3.2.
c. Thuc th
- Thuc th Griess: thuc th Griess gm 2 dung dch A v B.
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

Griess A: cn 0,5 g axit sunphnilic ha tan trong 150 ml axit acetic
long (70 ml axit c ha tan trong 500 ml nc ct); un nh cho tan
ht.
Griess B: cn 0,1 g -naphtylamin cho vo 20 ml nc ct, un
cch thy 15 pht. ngui, lc ly phn dung dch trong sut v ha vi
150 ml axit acetic long nh trn.
Khi dng s trn u hai dung dch A v B vi cng th tch. Dng n
u trn n y v dung dch ny khng bn.
- Dung dch tiu chun natri nitrit: cn chnh xc 0,15 g natri nitrit tinh
khit v kh, ha tan trong nc ct cho va 1000 ml. y l dung dch gc
c nng tng ng 1ml bng 0,1 mg NO2. Khi cn s pha long c
nng ph hp.
- Dung dch axit acetic 0,5 M: ong 33 ml axit acetic c pha long bng
nc ct cho 1 lt.
- Dung dch natri hidroxit 0,5 M dng hp th NOx: cn 20 g NaOH
tinh khit ha tan trong 1000 ml nc ct. Khi cn pha long gp 5 ln c
dung dch 0,1 M.
d. Phn tch mu
Mu phn tch s c o bng phng php trc quang v hm lng
NO2- s c xc nh trn ng chun.
- Xy dng ng chun:
Dung dch tiu chun NaNO2 c pha long 200 ln c dung dch
NO2- 0,5 g/ml. Chun b 6 bnh nh mc dung tch 25 ml. Ln lt cho vo
cc bnh 0,00; 0,50; 1,00; 1,50; 2,00 v 2,50 ml dung dch nitrit va pha long
trn (lng NOx tng ng trong cc bnh l 0,0; 0,5; 1,0; 1,5; 2,0 v 2,5 g);
thm 2,5 ml Griess A; 2,5 ml Griess B v nc ct in n vch mc; lc u
sau em o hp th quang bc sng 540 nm.
Kt qu o c biu hin trn th vi trc tung l hp th quang
v trc honh l lng NOx. ng chun phi l mt ng thng.
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

-Phn tch mu:
Ht chnh xc 2 - 5 ml dung dch mu cho vo bnh nh mc 25 ml.
Thm mt lng axit acetic 5M theo t l c 1 ml NaOH 0,5 M th thm 0,5 ml
axit acetic. Sau tin hnh tng t nh khi lm mu chun.
Kt qu (tnh theo mg/m3) c tnh theo cng thc:

C NOx f .

Trong

m
V

CNOx l nng kh NO2 trong khng kh ni kho st

f l t s gia th tch dung dch mu sau hp th trn th

tch dung dch mu ly ra phn tch
V l th tch khng kh i qua bnh hp th (tnh bng m3)
m l lng NOx tnh c theo ng chun.
4.2.2. Phng php hunh quang o trc tip.
Ngoi phng php trnh by trn, c th s dng phng php hunh
quang phn tch trc tip NOx trong khng kh bng my phn tch chuyn
dng.
Quy trnh phn tch c hng dn c th km theo my ca tng hng.
4.3.Phn tch xc nh hm lng CO2 trong khng kh
Kh quyn ca Tri t cha khong 2,3 x1010 tn CO2. Cc ngun pht
sinh CO2 trong kh quyn thng l do:
-Hot ng ca ni la
-S trao i vi thu quyn
-H hp ca con ngi v ng thc vt
-t nhin liu, cc hot ng sn xut cng nghip.

ng Kim Loan, HUS-VNU.VN

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

Hng nm con ngi a vo kh quyn trn 1010 tn CO2 v cng mt
lng ny kh CO2 lun trng thi trao i gi kh quyn vi i dng. y
l ngun cacbon c bn trao i trong chu trnh cacbon.
Trong chu trnh cacbon, lng kh CO2 trong kh quyn c gi trng
thi cn bng trong hng triu nm do phn tch t ca cacbon dng ho thch
khng b tc ng. Ch trong th k va qua do s dng trit nhin liu ho
thch dn n s thay i ln ca nng CO2 trong kh quyn. Trong tng
s CO2 pht thi th 80% l do t chy hydrocacbon lng v than, 17% t kh
t nhin, cn li l do sn xut xi mng.
Nguyn nhn th hai gy gia tng nng CO2 trong kh quyn l do
cht ph v t chy rng qu mc, dn n lm nng lc hp th mt phn
CO2 ca thc vt sng v tng pht thi CO2 do t chy. Ngoi ra vic mt cn
bng lng CO2 trong nc bin cng gy ra vic tng nng kh ny trong kh
quyn. Gn y cc nh khoa hc tm ra lng CO2 rt ln tch tr trong lng
cc khi bng hai cc tri t v trn cc nh ni cao. D bo khi lng bng
ln tan ra th s gii phng mt lng khng nh CO2 vo kh quyn.
Nng CO2 trong kh quyn quan trc c nm 2004 vo khong
0,038% (v/v) hay 380 ppmv hoc 0,053% (w/w), tng ng vi 2,7 1012
tn CO2; ln hn rt nhiu 800.000 nm trc (< 180ppmv) v nm 1958 (316
ppmv).
4.3.1.Phng php hp th CO2 bng bary saccharat
a)Nguyn tc
Cacbon dioxit hp th vo dung dch bary saccharat, sau chun li
lng d tha ca dung dch hp th bng axit oxalic. T tnh ra nng
CO trong khng kh.
b)Quy nh chung
-Ha cht theo TCVN 1058-78, nc ct theo TCVN 2117-77.
-Cn phn tch c chnh xc 0,1 mg

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Phng php ly mu v phn tch cc cht c trong khng kh 2005

- chnh xc ca phng php l 0,1 %, sai s cho php trong phm vi
0,5 %.
c)Chun b dung dch phn tch
-Phenolphtalein 0,1%: 0,1 g/100 ml cn 90
-Axit oxalic: cn 5,632 g a. oxalic/1000 ml nc ct; 1 ml tng ng 1
ml kh cacbon dioxit.
-Dung dch bary saccharat: nghin 10 g Ba(OH)2.2H2O, 20g saccharose
(C12H22O11) to mt bt ng th. Thm vo mt phn nc ct un m
(40oC), ri pha long tip thnh 1 lt v lc. Trc khi dng, chun li bng
dung dch axit oxalic.
d)Tin hnh
-Ly mu: ly 2 ng hp th, mi ng cha 15 ml dung dch bary
saccharat ( chun) v thm 2 git phenolphtalein. Lp ni tip. Ht khng kh
qua vi tc 0,1 l/ph. Ly t 2-3 lt khng kh. Ngng ly, nu thy mu dung
dch phai i, ghi li th tch kh ly.
hm l, ging su cho php rng ng cao su ni vi ng hp th v ly
mu ngay ti ming l.
e)Cch xc nh: cho cn thn lng dung dch hp th khng kh
cha trong 2 ng hp th vo bnh nn. Trng ng hp th bng nc ct ri
vo bnh nn. Chun bng axit oxalic n mt mu.
f)Tnh kt qu: nng CO2 trong khng kh tnh bng phn nghn (%o)
theo cng thc
[CO2] = (N n) x 1 x 1000 / V
Trong N th tch dung dch axit oxalic em chun 20 ml dung
dch bary saccharat ban u (ml); n - th tch dung dch axit oxalic em chun
dung dch bary saccharat hp th CO2 (ml), v V - th tch khng kh ht
(ml) tnh iu kin tiu chun ( 0oC, 760 mmHg).
4.3.2.Phng php hp th bng baryt
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Phng php ly mu v phn tch cc cht c trong khng kh 2005

a)Nguyn tc
Cacbon dioxit tc dng vi dung dch bary hydroxit to thnh kt ta bary
cacbonat theo phn ng:
CO2 + Ba(OH)2

-------> BaCO3 + H2O

Da vo nguyn tc trn cho khng kh c CO2 tc dng vi mt lng

d dung dch bary hydroxit. Chun li lng d Ba(OH) 2 bng axit oxalic
nh phn ng:
Ba(OH)2 + HOOC-COOH -------> Ba(COO)2 + 2H2O
T tnh ra nng CO2 trong khng kh.
b)Quy nh chung (nh mc 4.3.1b)
.

5. nh gi kt qu
Phn nh gi kt qu thc tp do sinh vin t lm, bao gm vit tng
trnh v bo co ming (presentation) kt qu thc nghim (khi c yu cu).
Vic vit tng trnh phi bao gm:
-Nu yu cu mc ch ca th nghim
-C s khoa hc ca php phn tch gm: l thuyt v phng php xc
nh (phng php th tch, trng lng, trc quang hay hp th nguyn t),
nguyn l v cc phn ng xy ra trong php xc nh, gii hn pht hin v
nh lng ca phng php s dng.
-Cch ly mu, bo qun, thi gian ly mu, lu lng hoc th tch kh
ly.
-Kt qu phn tch v bin lun
-Biu din cc kt qu tnh ton theo 2 n v ppm v mg/m3.

ng Kim Loan, HUS-VNU.VN

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