I HC QUC GIA H NI

TRNG I HC KHOA HC T NHIN

KHOA HA HC
-----*****-----

PGS. TS. T Th Tho

Gio trnh mn hc

THNG K TRONG HA PHN TCH

H Ni 2010
MC LC

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DANH MC CC K HIU VIT TT V CC I LNG THNG K

a- ( intercept) gi tr im ct trc tung trong phng trnh hi qui dng y= a+bx

: khng tin cy thng k

b- Slope: dc ca ng thng ( hay gradient ca phng trnh hi qui)
c- S ct trong phn tch phng sai hai yu t
d- chch (bias)
EA: sai s tuyt i
ER - sai s tng i
F- t s hai phng sai, gi tr chun Fisher
f- bc t do (degree of freedom)
h- s mu trong phn tch phng sai mt yu t

-gi tr thc hay gi tr c chp nhn hoc gi tr trung bnh ca mu tng th

n- s th nghim lp li cn gi l kch thc mu (sample size).
N: tng s th nghim lp li trong mu tng th
N- tng s th nghim trong phn tch phng sai hai yu t

P() mt xc sut ca i lng o, tin cy thng k.

Q- chun Dixon dng kim tra gi tr bt thng
r- h s tng quan (momen tch) gia hai i lng
r- s dng trong phn tch phng sai hai yu t
R: khong bin thin
R2 h s tng quan bnh phng xc nh c
R2 h s tng quan bnh phng hiu chnh
S- lch chunmu thng k
Sy/x- lch chun ca s sai khc y (t lch cc gi tr y tnh c theo phng
trnh hi qui v thc nghim)
Sa lch chun ca h s a trong phng trnh hi qui dng y= a+bx
Sb lch chun ca h s b trong phng trnh hi qui dng y= a+bx

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 S(y/x) w lch chun ca s sai khc gi tr y (t lch cc gi t y tnh c theo
phng trnh hi qui khi v thc nghim)

Sxo lch chun ca gi tr x tnh c dng phng trnh hi qui khi c gi trj y
SB lch chun ca cc th nghim o mu trng (nn)
SxE lch chun ca gi itrj x ngoi suy t th
Sxow lch chun ca gi t x tnh c khi s dng phgn tnh hi qui khi (c
trng s)

- lch chun ca tp s liu mu tng th

20- phng sai php phn tch lp li

21- phng sai mu

t- gi tr chun student dng trong tnh tin cy thng k v kim tra s khc nhau
c ngha ca cc gi tr trung bnh.
T- tng chung trong ANOVA
w- khong ga tr o

x gi trung bnh s hc ca tp s liu mu thng k

xo- ga tr x ca mu phn tch tnh c theo phng trnh hi qui

xE - gi tr x ngoi suy t ng chun
y - ga tr y tnh c t phng trnh hi qui

yB tn hiu o ca mu trng
z- phn b chun

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 M U

Lu nay, ho hc phn tch vn c xem l lnh vc ho hc lin quan n phn

tch nh tnh v nh lng cc cht. Tuy nhin, trn thc t nh ngha ny vn cha
phn nh y bn cht ca qu trnh phn tch. Mu cht ca qu trnh phn tch
khng hon ton ch gi gn vic phn tch mu v a ra s liu phn tch m cn
bao gm qu trnh nghin cu to ra quy trnh phn tch v x l nhng s liu thu
c t php phn tch nhm em li thng tin c ch nht. Theo thi gian nhng
phng php phn tch mi ra i p ng nhu cu phn tch trc mt v ri n dn
tr nn ph bin, bc l dn nhng hn ch khi phn tch cc i tng phc tp. Do
vy, cc nh phn tch vn ang n lc ci tin nhng phng php phn tch sn c,
xy dng v pht trin cc phng php phn tch mi cho i tng phn tch rng
hn cng vi vic xy dng cng c phn tch s liu mnh hn p ng c yu
cu thc t.
Vy thc cht ho phn tch l g? C th chp nhn mt nh ngha chnh xc
hn nh sau: Ho phn tch l khoa hc v cc php o trong ho hc. Trong thc t
phn tch s gp nhiu vn cn gii quyt t n gin nh hm lng Ca, Mg trong
nc ung l bao nhiu, khng kh c b nhim cc oxit nito hay khng? n
nhng vn gy tranh chp nh Hai mu qung ng nht th phi c cng hm
lng st, nhng kt qu phn tch ca hai phng th nghim vi cng mt mu phn
tch li khc nhau. Vy kt qu khc nhau nh th no th c th ni khc nhau khng
c ngha? Lm th no bit kt qu phn tch hm lng asen trong mu bnh nhn
c chnh xc khng? Thit b phn tch khng pht hin c Cd trong nc ung vy
ghi kt qu phn tch l bao nhiu? Bo co kt qu phn tch vi bao nhiu ch s sao
du phy thp phn C rt nhiu cu hi cn tr li trong thc t phn tch. V vy,
vic ng dng thng k trong x l s liu thc nghim thu c trong qu trnh phn
tch s gip cho cc kt lun thu c t phn tch c chnh xc cao v tin cy
mong mun. S pht trin ca phn mm my tnh cng gip cho vic tnh ton v x
l s liu n gin hn nu kt hp thng k v tin hc ng dng.
Vi mc tiu l ng dng nhng kin thc thng k v phn mm my tnh vo
cng vic x l s liu thc nghim thu c trong v sau khi phn tch nn chng ti
khng i su vo cc kin thc l thuyt v thng k, nhng c gng din gii n theo
cch thc hng ti ng dng c ch cho nh ha phn tch s dng. gip cho vic
x l s liu, trong gio trnh ny chng ti hng dn cch gii cc v d c th bng
phn mm MINITAB. y l phn mm thng k thng dng hin nay, l cng c
phn tch v trnh by s liu rt hiu qu, d cho ngi s dng. i vi vic s dng

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Excel hoc cc phn mm thng k khc, c ga c th tm thy trong ti liu tham
kho. Trong gio trnh bn cnh cc din gii ng dng c cp n rt nhiu cc v
d, hu ht c ly t cc bi bo trn cc tp ch phn tch cng b trong v
ngoi nc. Cc bi tp cui chng cng gip cho sinh vin c th hiu v vn dng
vo mc ch c th trong Ha phn tch.
V phn cc khi nim thng k v thut ng, gio trnh c gng Vit ha sao
cho mang ngha chnh xc nht v tun theo ti liu tiu chun v ph bin nht hin
nay c qui nh t TCVN 6910-1:2001 nhm mc ich thng nht cc s dng,
song c trch dn t ting Anh c th hiu ng ngha v tin cho sinh vin khi s
dng cc phn mm my tnh.
Ni dung ca gio trnh gm 7 chng. Chng 1 cp n cc khi nim c
bn v cc i lng thng k v cc ngun sai s thng gp trong Ha phn tch.
Chng 2 trnh by v cch tnh cc i lng thng k v ng dng trong x l s
liu trong phn tch. Chng 3 cp v l thuyt cc hm thng k v kh nng ng
dng trong x l thng k trong Ha phn tch. Chng 4 v cc phng php so snh
thng k v nh gi cc kt qu phn tch. Chng 5 v phn tch phng sai nhm
nh gi nh hng ca cc yu t n kt qu th nghim. Chng 6 v phn tch
tng quan hi qui v cch nh gi cc kt qu th nghim trong phn tch cng c.
Chng 7 v m bo cht lng v kim sot cht lng trong phng th nghim, cc
ni dung v tnh ton khng m bo o v xc nhn gi tr s dng ca phng
php phn tch theo yu cu ca ISO/IEC 17025. Mi chng c cc v d minh ha
c th d p dng.
Gio trnh ny nhm phc v cho cng tc ging dy v nghin cu khoa hc ca
sinh vin v hc vin cao hc chuyn ngnh ha phn tch. Qua gio trnh ny sinh
vin c th p dng cc phc v cho vic x l s liu trong qu trnh lm kha
lun tt nghip, lun vn thc s, lun n tin s. Ngoi ra cc cn b cc phng th
nghim phn tch c th tham kho phc v cho cng vic phn tch s liu, vic cng
nhn v m bo cht lng PTN theo tiu chun ISO 17025.
Gio trnh c chnh sa v hon chnh trong nhiu nm v s dng lm
gio trnh ging dy chuyn cho sinh vin b mn Ha phn tch.
Chng ti xin cm n cc ng nghip, sinh vin, hc vin cao hc v cc cn
b phn tch c, ng dng v gp , gi v ni dung ca gio trnh ny.

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Chng 1: MT S THUT NG V KHI NIM
TRONG X L S LIU PHN TCH

1.1. Qu trnh phn tch

Mt qu trnh phn tich bao gi cng phi tri qua cc bc sau:
Bc 1. Xc nh vn cn phn tch: Trc khi bt u thc hin php phn tch,
cn phi hiu c chng ta ang xc nh i lng no, nh tnh hay nh
lng, kt qu c dng lm g, ai s s dng thng tin v khi no cn
thng tin , ng v chnh xc cn t c l bao nhiu, gi thnh
phn tch...? i khi, ngi phn tch cn khuyn co khch hng cch ly
mu hiu qu cho ph hp vi phng php phn tch .
Bc 2. Chn phng php phn tch: Tiu ch chn phng php phn tch da trn
cc yu t sau:
- Loi mu phn tch: l cht rn, lng hay cht kh, dng ha tan, cn l
lng ?
- S lng mu cn phn tch v khi lng mu cn ly phn tch l bao
nhiu?
- C cn lm giu (nu hm lng cht phn tch qu nh) trc khi tin hnh
phn tch khng?
- chn lc ca phng php phn tch th no, nhng cht no s gy gy
cn tr php xc nh, cch loi tr?
- Phng php phn tch c p ng c yu cu v chm, ng (
chnh xc) hay khng ?
- Thit b v my mc dng cho phng php phn tch c sn c khng?
- Tay ngh ca i ng k thut vin?
- Gi thnh php phn tch v thi gian phn tch?
- Qui trnh phn tch c t ng ha phn tch nhiu mu, tit kim thi
gian hay khng?
- Phng php phn tch c sn trong ti liu tham kho hay l qui trnh
tiu chun hay khng tin cho vic cng b trong vic xc nhn gi tr s
dng ca phng php.
Bc 3. Ly mu : Trc khi ly mu cn xc nh xem

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 -Loi mu no
- Ly mu i din hay mu ngu nhin
- Kch thc mu (s lng v lng mu)
- Mu thng k hay mu tng th dng phn tch
- Sai s mc phi khi ly mu l bao nhiu?
Bc 4. Chun b mu phn tch : qui trnh bo qun v x l mu ty thuc vo:
- Mu l cht rn, lng hay cht kh
- Cht phn tch dng tan hay khng tan trong nc
- Tro ha kh hay x l mu theo phng php t
- Tch cht bng phng php ha hc hay che cc cht cn tr nu cn?
- C cn lm giu cht phn tch khng?
- Cn chuyn dng cht phn tch xc nh khng?
- Cn iu chnh mi trng mu phn tch? ( pH, thm thuc th)
Bc 5. Tch cht bng phng php ha hc khi cn thit. Cc phng php tch
cht phn tch ra khi cht cn tr i km trong nn mu phc tp c th gm:
- Chng ct
- Kt ta
- Chit bng dung mi
- Chit pha rn
- Tch sc k
- in di
Trong hai qu trnh sc k v in di thng c ghp ni vi detector
pht hin cht. V vy hai phng php ny c th cho ra kt qu phn tch .
Bc 6. Phn tch. i vi phn tch nh lng ngi ta chia thnh hai loi phng
php chnh l:
- Phn tch bng phng php ha hc: dng xc nh lng ln cc cht
da trn 4 loi cn bng ha hc xy ra trong dung dch gm:
- phng php phn tch trng lng
- phng php phn tch th tch (vi 4 k thut chun )

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 Trong phn tch ha hc, lng cht phn tch c xc nh trc tip thng
qua cht chun hay cht to thnh theo phng trnh ha hc.
- Phn tch cng c vi cc thit b o da trn tn hiu in thng qua vic
o cc i lng quang ph, cng dng hoc in th, hoc s
mdng xc nh lng vt v siu vt cc cht. Theo phng php
ny ch c th xc nh c lng cht phn tch nu c nh chun (tc l
tm c mi quan h tuyn tnh dng phng trnh hi qui gia i lng
o l tn hiu phn tch v nng cht phn tch trong dy cc dung dch
chun. Do vy, nh lng cn tri qua cc bc sau:
- Dng ng chun (tm quan h tuyn tnh gia tn hiu phn tch v nng
cht phn tch, xc lp phng trnh hi qui)
- Phn tch mu cha bit da trn phng trnh hi qui thu c
- Phn tch mu hiu chnh/mu chun kim tra v mu trng nh gi
ng ca phng php phn tch.
- Phn tch mu lp v mu thm chun kim tra lp li v hiu sut thu
hi.
Bc 7. X l s liu phn tch v bo co kt qu
T cc s liu phn tch thu c trong qu trnh th nghim, cn tin hnh x
l thng k s liu thc nghim v bo co kt qu phn tch.
Nh vy c c s liu phn tch nh lng, nh phn tch phi tra rt
nhiu bc trong qu trnh phn tch, trong x s liu thc nghim l khu
cui cng. Tuy nhin, s liu thu c mun chnh xc th tt c cc khu
trong qu trnh phn tch phi c m bo cht lng cng ging nh cht
lng ca sn phm xut xng ph thuc vo rt nhiu khu trong qu trnh
sn xut. Do vy tin cy ca kt qu phn tch cui cng ph thuc vo
tin cy ca tt c cc bc trong qu trnh phn tch.
1.2. Sai s v cch biu din sai s trong phn tch nh lng
Bi phn tch nh lng gm rt nhiu bc trong qui trnh phn tch v mi
bc trong qu trnh hoc bt k php o no trong qu trnh u km theo s
khng chc chn ca kt qu o hay gi l khng m bo o (uncertainty). Do
vy, kt qu phn tch s c tin cy nht nh (cao hoc thp) m khng phi tin
cy l 100% v khng phi khng c khng m bo.
V d nh phn tch tin hnh xc nh tng hm lng st trong mt mu nc
ngm bng phng php trc quang vi thuc th o- phenantrolin sau khi kh Fe3+

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c trong mu thnh Fe2+ ri to phc mu. Gi s kt qa o 1 ln th nghim l 20,1
ppm. Tuy nhin, nh phn tch nghi ng th nghim c th b nh hng ngu nhin
bi nhiu yu t xy ra trong qu trnh th nghim nn tin hnh th nghim li t mu
ban u. Kt qu phn tch li l 21,0 ppm. Vy gi tr no ng? Trong trng hp
ny khng c c s khng nh c kt qu thu c chnh xc cha v khng
c s liu no lm mc so snh. V cng khng th khng nh gi tr 20,1 ppm c
chnh xc khng hay c th km theo khng chc chn trong n.
Mt trng hp khc, mt nh ha hc tin hnh tng hp thuc th hu c dng
cho phn tch trc quang theo qui trnh tham kho trong ti liu. Kt qu xc nh bc
sng cc i ca ph hp th l max= 610 nm, trong khi ti liu tham kho cng b l
605 nm bi cng phng php v cng iu kin th nghim. Vy ti sao li c s sai
khc. Nu ti liu cng b kt qu o c th dao ng l 2 nm, c ngha l (605 2)
nm v kt qu th nghim t c c dao ng l (610 5 nm) th hai gi tr th
nghim c khc nhau hay ging nhau? Nguyn nhn no lm cho kt qu khc nhau v
s khc nhau ny c chp nhn c khng?
Vy hiu th no l sai s?
Sai s (error) l s sai khc gia cc gi tr thc nghim thu c so vi gi
tr mong mun. Tt c cc s liu phn tch thu c t thc nghim u mc sai
s. Sai s php o dn n khng chc chn hay khng m bo o ca s
liu phn tch.
Hai cch biu din sai s thc nghim c dng ch yu trong Ha phn tch
l sai s tuyt i v sai s tng i.
1.2.1.Sai s tuyt i (EA) (Absolute error)
Sai s tuyt i l s sai khc gia gi tr o c (xi) vi gi tr tht hay gi tr qui
chiu c chp nhn (k hiu l ).

EA = xi -

Sai s tuyt i c gi tr m hoc dng, cng th nguyn vi i lng o v

khng cho bit chnh xc ca php o.
Ch : - Gi tr o c th l mt gi tr n l hoc gi tr trung bnh ca nhiu ln o
lp li.
- Theo TCVN 6910-1:2001 th gi tr qui chiu c chp nhn (accepted
refrence value) l gi tr c chp nhn lm mc so snh, nhn c t:
a) gi tr l thuyt hoc gi tr c thit lp trn c s cc nguyn l khoa hc;

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 b) gi tr c n nh hoc chng nhn trn c s th nghim ca mt s t chc
quc gia hoc quc t; (v d cc mu chun c chng nhn CRM (certified
reference material) hoc mu chun i chng (standard referrence material SRM)
ca Vin tiu chun v cng ngh Quc Gia- M (National Institute of Standard and
Technology- NIST) hoc mt s t chc khc) lun c ghi gi tr chng nhn trn mu
da trn c s kt qu nhn c t nhiu phng th nghim c uy tn trn th gii)
c) gi tr tho thun hoc c chng nhn trn c s th nghim phi hp di
s bo tr ca mt nhm cc nh khoa hc hoc k thut;
d) k vng ca i lng (o c), ngha l trung bnh ca mt tp hp nht
nh cc php o khi cha c cc gi tr tham chiu theo mc a), b) v c) hay gi tr
trung bnh ca v s cc php o lp li)
1.2.2. Sai s tng i (ER) (Relative error)
Sai s tng i l t s gia sai s tuyt i v gi tr tht hay gi tr bit trc,
hay gi tr c chp nhn.
xi
ER =

C th biu din sai s tng i di dng phn trm sai s tng i

EA
ER % = . 100%

Hoc di dng phn nghn (parts per thousand-ppt)

EA
ER = . 1000 (ppt)

Sai s tng i cng c gi tr m hoc dng v khng c th nguyn, c

dng biu din ng ca phng php phn tch.

Th d 1.1: Kt qu xc nh hm lng aspirin trong mt mu chun c chng

nhn (CRM) sau nhiu ln lm lp li l 195; 198; 200; 202; 204; 205 v 210 mg/g.
Hm lng ng ca aspirin trong mu chun c chng nhn l 200 mg/g. Kt
qu th nghim c biu din trn trc s nh hnh 1.1.
Nh vy, php o mc sai s tuyt i t -5mg n +10mg v sai s tng i t -
2,5% n +5% (hay 20ppt n 50ppt).

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 195 200 205 210

(EA : mg) -5 0 5 10
(Er : % ) -2,5 0 2,5 5
Hnh 1.1: Sai s tuyt i v sai s tng i khi phn tch aspirin trong mu
chun.

1.3. Phn loi sai s

1.3.1. Sai s h thng hay sai s xc nh (Systematic or determinate error):
Sai s h thng l loi sai s do nhng nguyn nhn c nh gy ra, lm cho kt
qu phn tch cao hn gi tr thc (sai s h thng dng -positive bias) hoc thp hn
gi tr tht (sai s h thng mnegative bias).
Sai s h thng gm:
- Sai s h thng khng i (constant determinate error): loi sai s ny khng ph
thuc vo kch thc mu (lng mu nhiu hay t). Ni cch khc khi khi lng
mu ly phn tch tng th lng cht trong mu ly phn tch cng tng theo
lam cho phn trm cht phn tch trong mu vn khng i v lun cao hn hoc thp
hn gi tr phn trm tht ca n. Do , sai s ny c th c loi tr bng th
nghim vi mu trng (blank sample) hoc dng h s hiu chnh.
- Sai s h thng bin i (proportional determinate error): loi sai s ny t l vi
kch thc mu phn tch, khong cch gia cc tr o lun bin i theo hm lng
(nng ), do rt kh pht hin. Sai s h thng bin i rt kh pht hin tr khi
bit r thnh phn ho hc ca mu v c cch loi tr ion cn.
Sai s h thng khng i v bin i c biu din trn hnh 1.2.

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 Sai s h
Sai s h thng khng
thng bin i
i
Khi
lng
cht Gi tr ng
phn
tch
(mg)

Khi lng mu (g)

Hnh 1.2: Biu din sai s h thng khng i v bin i

Sai s h thng phn nh ng ca phng php phn tch hay phn nh s sai
khc ca gi tr o vi gi tr tht ca n. Hu ht cc sai s h thng c th nhn bit
c v c loi tr bng s hiu chnh nh phn tch mu chun hay loi tr nguyn
nhn gy ra sai s.
Cc nguyn nhn gy sai s h thng c th gm:
- Sai s do phng php hay quy trnh phn tch nh: Phn ng ho hc khng
hon ton, ch th i mu cha n im tng ng, do ion cn tr php xc
nh
- Sai s do dng c nh: dng c cha c chun ho, thit b phn tch sai, mi
trng phng th nghim khng sch.
- Sai s do ngi phn tch nh: mt nhn khng chnh xc, cu th trong thc
nghim, thiu hiu bit, s dng khong nng phn tch khng ph hp, cch ly
mu phin din, dng dung dch chun sai, ho cht khng tinh khit, do nh kin c
nhn (nh phn tch kt qu sau da trn kt qu trc) ...
-Sai s do nhiu ca thit b in t o, v d ng nn dng cao
* Cch loi tr sai s h thng:
- Tin hnh th nghim vi mu trng: Mu trng l mu khng c cht phn tch
nhng c thnh phn nn ging nh dung dch mu phn tch nh ha cht, thuc th,
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mi trng, nhiu tn hiu o ca thit b phn tch cng c. Bng cch ly kt qu
o c tr i kt qu phn tch mu trng ta c th loi tr nh hng c nh ca cc
yu t i km.
- Phn tch theo phng php thm chun loi tr nh hng ca cc cht cn
tr. Php phn tch ny c tin hnh trn c s thm mt lng cht phn tch bit
trc v mu phn tch (spiked sample) v tin hnh tt c cc bc nh vi mu
phn tch. S sai khc lun dng hay lun m gia gi tr tm li c v gi tr thm
chun ban u cho bit phng php c mc sai s h thng hay khng.
- Phn tch mu chun (hay mu chun c chng nhn (CRM): Mu chun ny
c xem l mu thc c hm lng cht cn phn tch bit trc, c dng
nh gi chnh xc ca phng php.
-Phn tch c lp: khi khng c mu chun th phi gi mu phn tch n phng
th nghim (PTN) khc, tin hnh phn tch c lp loi nhng sai s do ngi phn
tch v thit b phn tch, i khi c phng php gy nn, trn c s nh gi s sai
khc gia kt qu phn tch ca mnh vi kt qu ca PTN khc.
- Tham gia cc cuc thi th nghim thnh tho do h thng qun l PTN t chc.
- Thay i kch thc mu: pht hin sai s h thng khng i v bin i.
- Lun chun ha thit b v dng c o trc khi tin hnh th nghim, nng cao tay
ngh ca ngi lm th nghim.
1.3.2. Sai s ngu nhin hay sai s khng xc nh (random error or indeterminate):
y l nhng sai s gy nn bi nhng nguyn nhn khng c nh, khng bit
trc. Sai s ngu nhin thng gy ra do:
- Yu t khch quan: nhit tng t ngt, thay i kh quyn, i lng o
c chnh xc gii hn
- Yu t ch quan: thao tc th nghim khng chun xc (c th gy ra gi tr
bt thng); thnh phn cht nghin cu khng ng nht
Do sai s ngu nhin khng th bit trc c nn loi tr n cn phi lm
nhiu th nghim v tin hnh x l thng k s liu phn tch.
Sai s ngu nhin lm cho kt qu phn tch khng chc chn, cn sai s h
thng lm cho kt qu phn tch sai.

Th d 1.2: Mt mu chun huyt thanh ca ngi c chng nhn cha 42,0 g

albumin trong mt lt. Nm PTN A, B, C, D, E tin hnh phn tch mu chun ny.
Mi PTN lm lp li 6 ln (cng mt ngy) xc nh nng albumin trong mu

14
kt qu thu c nh sau:

PTN Ln1 Ln 2 Ln 3 Ln 4 Ln 5 Ln 6

A 42,5 41,6 42,1 41,9 41,1 42,2

B 39,8 43,6 42,1 40,1 43,9 41,9

C 43,5 42,8 43,8 43,1 42,7 43,3

D 35,0 43,0 37,1 40,5 36,8 42,2

E 42,2 41,6 42,0 41,8 42,6 39,0

Hy nhn xt xem kt qu ca PTN no mc sai s ngu nhin v sai s h thng.

Gii: Biu din kt qu o l hm lng albumin (g/l) ca cc phng th nghim trn
cc trc s so snh, ta c th thy s phn b cc gi tr o v gi tr chun nh
sau:
Phng th nghim A:

Phng th nghim B:

Phng th nghim C:

Phng th nghim D:

Phng th nghim E:

Nh vy, trong 5 PTN th ch c PTN C c c 6 kt qu phn tch u ln hn gi tr

c chp nhn, chng t PTN ny mc sai s h thng v l sai s h thng bin
i. Cc PTN cn li u mc sai s ngu nhin.

15
 1.3.3. Gi tr bt thng (outliers)v sai s th (gross error):
Gi tr bt thng l nhng gi tr thu c thng rt cao hoc rt thp so vi cc
gi tr cn li trong tp s liu lp li. Gi tr bt thng dn n kt qu thu c
bng cch tnh trung bnh t tt cc cc s liu s sai khc nhiu so vi gi t mong
mun. Trong th d 1.2 trn nu nhn vo cc trc s biu din kt qu o s d nhn
thy PTN D kt qu hm lng albumin l 35 g/l c gi tr thp hn nhiu so vi cc
gi tr khc chnh l gi tr bt thng.
Gi tr bt thng do nhng nguyn nhn bt thng xy ra trong qu trnh phn
tch gy nn. Do , trc khi x l s liu cn phi loi tr gi tr bt thng.
S sai khc ln gia gi tr bt thng v gi tr trung bnh hay gi tr thc c
gi l sai s th. Sai s th c pht hin khi tin hnh nhiu th nghim lp li.
1.4. khng m bo o (uncertainty) v lan truyn khng m bo o.
Kt qu phn tch nh lng c ngha rt quan trng khng ch trong nh gi
cht lng sn lng, kim tra vt liu theo yu cu k thut m cn cho thy sn phm
c p ng c gii hn qui nh ca tiu chun, lut php...hay khng. Bt c quyt
nh no da trn kt qu phn tch cng quan trng v vy kt qu phn tch c biu
th phi c cht lng, ni rng hn l c mc tin cy cho mc ch s dng. Trong
mt vi lnh vc th nghim ca ho hc phn tch hin nay, lut php yu cu cc
phng th nghim phi gii thiu bin php m bo cht lng m bo nng lc
cung cp cc d liu theo ng yu cu cht lng. Cc bin php bao gm: s dng
cc phng php phn tch c ph duyt; p dng cc th tc xc nh kim
sot c h t l n g n i b ; th a m g ia v o c c h th n g th n g h i m th n h th o (c h n g
trn h th nghim thnh tho); cng nhn theo ISO/IEC 17025 v thit lp lin kt chun
o lng ca cc kt qu. Cc yu cu ny s c xt chi tit trong chng 7.
Theo cc yu cu trn, mt trong nhng nhim v bt buc l nh phn tch phi
phi chng minh c cht lng kt qu th nghim ca h bng cch cng b mc
tin cy i km vi kt qu. M t tro n g c c c ch th n g d n g l c l n g k h n g
m bo o.
1.4.1. nh ngha khng m bo o
Theo o lng hc - thut ng chung v c bn(VIM) th khng m o l
thng s i km kt qu o, c trng cho phn tn ca cc gi tr o, c th qui
cho gi tr o mt cch hp l.

16
 Thng s ny c th l lch chun, sai chun, khong tin cy, hoc bi ca
chng v gm nhiu thnh phn (s xt trong cc chng tip theo). Khi bo co kt
qu phn tch, gi tr trung bnh phi vit km theo khng m o di dng x U.

khng m bo o cng c vit di dng khng m bo o tuyt

i v tng i.
- khng m bo o tuyt i biu th gii hn hay bin ca khng m
bo lin quan n php o. V d buret c vch chia 0,1 ml, c lng dung sai ca n
l 0,02 ml, tc l khi c trn buret th tch 11,04 ml th th tch thc s l t 11,02
n 11,06 ml. Khi ni rng 0,02 ml l khng m bo o tuyt i.
- khng m bo o tng i l l t s gia khng m bo o tuyt i
v gi tr o c, n cho php so snh ln ca khng tin cy trong kt qu o.
Cng ging nh sai s tng i, n c th biu din di dng phn trm. Trong kt
qu c th tch buret trn ta c khng m bo o tng i l 0,02/11,04=0,002
hay 0,2%. Th tch o cng ln th khng m bo o tng i cng nh.

Cch tnh chi tit cc khng m bo o thnh phn cch biu din
khng m bo o cui cng s c cp c th trong mt s phn v chng 7.
1.4.2. Lan truyn khng m bo o khi c sai s h thng
i vi cc i lng o gin tip t nhiu i lng m mi i lng c
khng m bo o thnh phn th c s lan truyn khng m bo o hay kt qa
cui cng s cha khng m bo o tng hp.
C hai cch tnh lan truyn khng m bo o khi trong qu trnh phn tch c
sai s ngu nhin v sai s h thng. i vi php phn tch mc sai s ngu nhin,
cc kt qu phi c x l thng k tm lch chun nn lan truyn khng
m bo o l lan truyn lch chun ca tng i lng o. Ni cch khc tng
thnh phn ng gp vo kt qu o cui cng l c lp ln nhau v khng m
o ca chng c xc nh t lch chun ca cc php o lp li . Phn ny s
xt trong chng 3.
Trng hp i lng o cui cng ph thuc vo cc i lng o thnh phn
v chng c quan h tuyn tnh tc l c s lan truyn sai s h thng (accumulated
error) n kt qu o gin tip, c lp th lan truyn khng m bo o s c x
l tng t nh lan truyn sai s h thng.
- Khi ch c kt hp tuyn tnh ca php o ngu nhin (s liu thu c l kt qu
cui cng ca php cng v tr) th sai s xc nh tuyt i ET l tng cc sai s
tuyt i ca php o ring r.

17
 Nu m= AB C th Em = EA +EB + EC
- Khi biu din nguyn nhn cc kt qu (kt qu o tnh t php nhn hoc chia),
ngi ta dng sai s xc nh tng i ETR

Em E A E B EC
Nu m= A(x/)B( x/) C th
m A B C

Th d 1.3:
a) Khi cn mu trn cn phn tch c c kt qu l 0,0001 gam, chnh xc ca
gi tr c c l 0,0002 gam th c kt qu nh sau:
mchn +mu= (21,1184 0,0002) gam ; mchn= (15,8465 0,0002) gam
vy khi lng mu s l
mmu= (21,1184 0,002) - (15,8465 0,002) = (5,2719 0,004) gam

b) Cho khi lng mol nguyn t ca Cl l 35,4530,002 g/mol th khi lng mol
phn t ca Cl2 l 70,906 0,004 g/mol
c) Khi lng dung dch c tnh theo cng thc m=V.d= (3,430,01).(5,660,01)=?
Ta c:
ERV= 0,01/3,43 ; ERd= 0,01/5,66; ERm= (0,01/3,43)+(0,01/5,66)

Do m=(3,43.5,66) [(0,01/3,43)+(0,01/5,66)]. (3,43.5,66)= 19,41380,0909

Nn m= (19,41 0,09) gam

1.5. S c ngha v cch ly gi tr gn ng

Mt gi tr s hc dng biu din kt qu phn tch s khng c ngha nu khng
bit chnh xc ca n. Do vy, khi biu din kt qu cn phi ghi r tin cy ca
s liu v cc s liu cn c lm trn ch chnh xc ca n ni cch khc s
liu ch c cha cc s c ngha.
1.5.1. Khi nim s c ngha
S c ngha trong mt dy s l tt c cc s chc chn ng v s khng chc
chn ng u tin.

Th d 1.4 : Khi c th tch dung dch ng trong buret 50 ml (cp chia 0,1
ml), chng ta c th thy vch cht lng v tr ln hn 30,2 ml v nh hn 30,3 ml.

18
Nu c th c on v tr vch cht lng cp chia khong 0,02 ml ( khng
m bo o) th c th ghi th tch l 30,24 0,02 ml.

Trong th d ny, 3 con s u tin l s chc chn ng, s cui cng l s

khng chc chn ng. Nh vy c th vit 30,24 ml hoc 0,03024 lit (4 s c ngha).

S c ngha c qui c nh sau :

+ Gm cc ch s t nhin 1,2,. 9
+ S 0 c th l s c ngha hoc khng phi l s c ngha tu thuc vo v tr ca
n trong dy s.
- Nu s 0 nm gia cc s c ngha l s c ngha.
- Nu s 0 nm cui dy s th ch l s c ngha nu ng sau du phy.
- Nu s 0 nm trc du thp phn th khng phi l s c ngha.

Th d 1.5 : 25,24 c 4 s c ngha 0,15 c 2 s c ngha

15,00 c 4 s c ngha 360 c 2 s c ngha
0,0241 c 3 s c ngha 150,00 c 5 s c ngha
Khi ly V=5,00 ml c ngha l khi tnh nng phi ly 3 s c ngha. Khi gi
tr nng tm c c th ghi l 0,0215; 2,15.10-2 hoc 21,5.10-3 hoc 215.10-4M)
Nu ghi th tch bnh l V= 2,0 lit th khi chuyn sang n v ml khng th ghi l
2000 ml (v trong con s ny ch ghi 1 s c ngha) m phi ghi l 2,0.103ml.

* Lm trn s: Khi bo co kt qu, ngi phn tch cn ghi ng s c ngha,

tc l phi l loi b cc s khng c ngha trong kt qu. V vy cn phi lm trn s.
Nguyn tc lm trn s l nu b cc s 6,7,8,9, th tng ga tr trc n ln 1 n
v. Nu loi b cc s 1,2,3,4, th khng thay i con s ng trc n. Nu loi b s
5 th lm trn s trc v s chn gn nht.
Th d: 2,25 lm trn thnh 2,2; 2,35 thnh 2,4; gi tr nng tm c t cng
thc tnh l 0,035785 M th khi vit 4 ch s c ngha s l: 0,03578M
1.5.2. Cch ly gi tr gn ng
* i lng o trc tip: y l cc gi tr nhn c do c hoc o, m c.
S liu th nghim c ghi theo nguyn tc s cui cng l s gn ng v s trc
s cui cng l s chnh xc.

19
V d khi lng cn cc trn cn phn tch (c cp c l 0,0001 gam) l
1,3501gam th s 1 cui cng l s gn ng. hp th quang trn my trc quang
hin th 4 ch s sau du phy l 0,5690.
* i lng o gin tip: y l kt qu tnh c t cc i lng o trc tip
nh cc php cng tr, nhn chia, logarit
V d kt qu cn khi lng mu t hai ln cn cc v cn c cc ln mu, tnh nng
t khi lng cn v th tch dung dch
- Php tnh cng v tr : tnh kt qu cui cng sau lm trn s v ghi s c
ngha sau du phy theo gi tr no c t s c ngha nht sau du phy.
- Php nhn v chia: kt qu ca php nhn v php chia c lm trn s sao
cho n cha s c ngha nh gi tr c t s c ngha nht.
- Php tnh logrit v ngc logrit:
+ logrit: ly cc ch s sau du phy bng tng cc s c ngha trong s ban u
ly logarit
+ ngc logarit: ly cc s c ngha bng s cc ch s sau du phy.

Th d 1.6: a) 3,4+0,020+7,31=10,73=10,7 y v 3,4 l s ch c 1 s c

ngha sau du phy nn trong kt qu ch ghi 1 s c ngha sau du phy.
35,63.0,5481.0.05300
b) .100% 88,5470578% =88,55%
1,1689

Trong dy s trn, khng m bo ca mi s l 1/3563; 1/5481; 1/5300 v

1/11689 Nh vy khng m bo ca s th nht ln hn so vi khng m
bo ca s th hai v th ba. Do , gi tr c t s c ngha nht l 35,63 (4 ch s
c ngha) nn kt qu cui cng phi c ghi l 88,55%
c) log(9,57.104)=4- log 9,57= 4,981 (gi tr 4 c 1 s c ngha; gi tr 9,57 c 3
s c ngha nn kt qu cui cng ly 3 ch s c ngha sau du phy )
log(4,000.10-5)=5- log4,000=-4,397940=-4,3479
Antilog(12,5)=3,162277.1012=3.1012= 30.1011= 300.1010
( gi tr 12,5 c 1 ch s c ngha sau du phy nn s cui cng ca php ngc
logarit ch c 1 ch s c ngha

Ch : Trong qu trnh tnh ton, i khi gi tr thu c ca i lng o gin

tip li c dng tnh ton trong cc php tnh khc na. Do vy, trnh sai s
gy ra do vic lm trn s, chng ta c th gi li thm 1 hoc nhiu hn mt s khng

20
c ngha na trong kt qu tnh, khi s ny c vit thp xung pha di
(subscipt) ca s c ngha. S khng c ngha c ghi thm ny cng nhc chng ta
bit s con s c ngha cn dng trong kt qu tnh cui cng.
Trong th d 1.6 c th ghi cc kt qu cc s nh sau: a) 10,73 ; b)88,547
1.6. lp li, ti lp, hi t, phn tn
1.6.1. lp li (repeatability)v ti lp ( reproducibility):
Trong phn tch, khi thc hin cc php th nghim trn nhng vt liu v trong
nhng tnh hung c xem l y ht nhau thng khng cho cc kt qu ging nhau.
iu ny do cc sai s ngu nhin khng th trnh c vn c trong mi quy trnh
phn tch gy ra v v khng th kim sot c hon ton tt c cc yu t nh hng
n u ra ca mt php o. Do vy, khi bo co cc d liu phn tch, cn xem xt
n nguyn nhn v kt qu s thay i ny.
Rt nhiu yu t khc nhau (khng k s thay i gia cc mu th c xem l
ging nhau) c th ng gp vo s thay i cc kt qu ca mt phng php phn
tch, bao gm:
a) ngi thao tc;
b) thit b c s dng;
c) vic hiu chun thit b;
d) mi trng (nhit , m, s nhim ca khng kh ...);
e) khong thi gian gia cc php o lp li
S thay i gia cc php o c thc hin bi nhng ngi thao tc khc nhau
v/hoc vi cc thit b khc nhau s thng ln hn s thay i gia cc php o do
cng mt ngi thc hin vi cc thit b nh nhau trong khong thi gian ngn.
* lp li: c trng cho mc gn nhau gia gi tr ring l xi tin hnh trn
cc mu th ging ht nhau, c tin hnh bng mt phng php phn tch, trong
cng iu kin th nghim (cng ngi phn tch, cng trang thit b, phng th
nghim, trong cc khong thi gian ngn) (within laboratory precision) .
* ti lp (reproducibility): c trng cho mc gn nhau gia gi tr ring l
xi tin hnh trn cc mu th ging ht nhau, c tin hnh bng mt phng php
phn tch, trong iu kin th nghim khc nhau (khc ngi phn tch, trang thit b,
phng th nghim, trong khong thi gian di) (between laboratory precision) .
Nh vy, nh gi lp li ca phng php phn tch cch tt nht l tin
hnh lm song song cc th nghim lp li t cng mu th ban u. (Cn cc lng

21
cn mu ban u khc nhau v tri qua cc bc ging ht nhau trong cng iu kin
th nghim). c bit, khng c hiu chun li thit b gia cc ln o tr khi vic
ny l mt phn cn thit ca tng php o ring r.
ti lp thng c xt n di dng cc th nghim nh gi lin phng (
ti lp gia cc PTN), hay ti lp gia cc ngy lm th nghim khc nhau (
nh gi n nh ca phng php phn tch hay thit b phn tch)

Vi cng mt phng php phn tch, thng xt n lp li hn l ti

lp.
1.6.2. hi t v phn tn
* hi t (convergence): ch s phn b s liu thc nghim xung quanh gi tr
trung bnh. Nu lp li tt th hi t tt.
* phn tn (dispersion): ch mc phn tn ca kt qu th nghim sau nhiu
ln o lp li. phn tn l nghch o ca lp li. Nu kt qu c lp li cao
tc l phn tn cc gi tr xung quanh gi tr trung bnh thp.
th d 1.2 PTN A c lp li tt nht v ch mc sai s ngu nhin, lp li ca
PTN C cng tt nhng li mc sai s h thng. Cc PTN khc nh D v E c kt qu
rt phn tn nn khng c xem l lp li.
1.7. chch (bias) (d) v hiu sut thu hi
1.7.1. chch: ch mc sai khc gia k vng ca cc kt qu th nghim
v gi tr qui chiu c chp nhn (ni cch khc l sai lch ca gi tr trung
bnh ca s ln cc kt qu o lp li v gi tr thc). Khi khng c mu chun i
chng (CRM), ngi ta thng xc nh chch bng cch tin hnh cc mu thm
chun (spiked) tc l thm mt lng cht chun bit trc trn nn mu thc (thng
gi l mu trng c thnh phn nh mu phn tch nhng khng c cht phn tch).
chch lin quan n sai s tuyt i v c rt nhiu thnh phn sai s h
thng ng gp vo chch.

Cng thc tnh chch: d x

C hai khi nim v chch:

- chch phng th nghim (laboratory bias): ch mc sai khc gia k
vng ca cc kt qu th nghim ti mt phng th nghim c th v gi tr quy chiu
c chp nhn.

22
 - chch phng php o (bias of the measurement method): ch mc sai
khc gia k vng ca cc kt qu th nghim nhn c t tt c cc phng th
nghim s dng phng php v gi tr quy chiu c chp nhn.
Ch : - chch ca phng php o c th khc nhau cc mc hm lng
khc nhau.
- Mc sai khc gia chch ca phng th nghim v chch ca
phng php o gi l chch gia cc PTN do yu t PTN gy nn (laboratory
component of bias).
1.7.2. Hiu sut thu hi (recovery): Hiu sut thu hi l cch khc biu din
chch di dng phn trm tng i ca lng tm li c. chch cng nh th
hiu sut thu hi cng ln.
Theo ng ngha ca t ny th thu hi c dng ch phn cht cn phn tch
c tch ra khi nn mu cng c ngha l phn cht c th nh lng c, mc d
khng phi thc s l ly ring ra cht phn tch.. Tuy nhin, khi thc hin qu trnh
x l mu, tch, chit v phn tch chng ta khng th bit chnh xc cht phn tch
c tch ra ht cha v khng c cch no bit xc nh c chnh xc bao
nhiu % trong s c sn trong mu. V vy, trong thc t ngi ta xc nh hiu sut
thu hi bng cch thm mt lng cht cn phn tch bit trc vo nn mu, trn u.
Nu gi thit rng nn mu thc c thm cht chun vo c cng c tnh phn tch
vi nn mu thc cn phn tch th hiu sut thu hi c nh ngha nh sau:
H%= 1005.( C cthmchun- Cnn)/Cchun c thm vo
Mc ch ca vic nh ga hiu sut thu hi l kim tra xem cht chun c
thm vo c trn u vi nn mu th no v tnh cht ca nn mu c ging vi
nn mu phn tch ban u hay khng.
1.8. chnh xc ( gm ng v chm) (theo ISO 3534-1)
* chm (precision): dng ch mc gn nhau ca cc gi tr ring l xi
ca cc php o lp li. Ni cch khc, chm c dng ch s sai khc gia cc
gi tr xi so vi gi tr trung bnh x .
Nh vy: - chm ch ph thuc vo phn b ca sai s ngu nhin v khng
lin quan ti gi tr thc hoc gi tr c chp nhn.
- thc o chm thng c th hin bng phn tn v c tnh
ton nh l lch chun ca cc kt qu th nghim. chm cng thp th lch
chun cng ln.

23
 Ba khi nim thng k c dng m t chm ca mt tp s liu l
lch chun, phng sai v h s bin thin (s xt sau). Tt c cc khi nim ny c
lin quan n chch ca s liu phn tch c lp khi gi tr trung bnh: di = xi x

Nu xt chm trong cc iu kin lp li th gi l lp li, trong iu kin ti lp

th gi l ti lp.
* ng (trueness): ch mc gn nhau gia gi tr trung bnh ca dy ln cc
kt qu th nghim v gi tr qui chiu c chp nhn. Do , thc o ng
thng k hiu bng chch hay nh gi qua sai s tng i.
* chnh xc (accuracy): l mc gn nhau ca kt qu th nghim (thng
l gi tr trung bnh x ca dy cc php o lp li) vi gi tr thc hay gi tr c
chp nhn xt hay .

Nh vy khi dng cho mt tp hp cc kt qu th nghim, chnh xc bao

gm t hp cc thnh phn sai s ngu nhin v sai s h thng hoc thnh phn
chch chung. Khi khng c sai s h thng th gi tr trung bnh tin ti gi tr thc
nu s php o rt ln ( N). V vy, c th ni chnh xc tu thuc vo s php
o trong th nghim ch c sai s ngu nhin.
Do vy mt kt qu th nghim c coi l chnh xc nu cc gi tr o lp li
ring r c chm tt v ng tt. chnh xc c biu din di dng sai s
tuyt i hoc sai s tng i.
Trong Ho phn tch, nh gi chnh xc ngi ta pha cc mu t to
(synthetic sample) bit trc hm lng (tc l c gi tr bit trc ) v lm th
nghim tm ra gi tr trung bnh. Nu cc th nghim c lp li v ti lp tt
th ch cn kim tra xem c s sai khc c ngha thng k gia gi tr trung bnh v
gi tr thc hay khng. Vn ny s c xt chng 4.
chm v ng (hay chnh xc) l nhng ch tiu quan trng nh
gi cht lng ca s liu phn tch. Thng thng, cn nh gi chm trc v
nu phng php phn tch mc sai s h thng th ch c dng nh lng khi
sai s ngu nhin ( phn tn) nh.
Tm li: chm biu th sai s ngu nhin, chch biu th sai s h thng
cn chnh xc biu th c hai loi sai s.
Trong th d 1.2 trn, kt qu ca cc PTN A n E c cc thng s c trng nh
sau:

24
PTN Hm lng Sai s tuyt i/ Sai s tng Nhn xt
trung bnh chch i

A 41,9 -0,1 -0,24% ng tt, chm

B 41,9 -0,1 -0,24% ng tt, khng chm

C 43,2 +1,2 +2,86% ng km, chm

D 39,1 -1,9 -4,52% Khng ng v khng chm

E 41,5 -0,5 -1,20% Khng ng v khng chm

Nh vy ch kt qu phn tch ca PTN A l tha mn c ng v chm ni cch

khc ch phng th nghim A c kt qu phn tch chnh xc.

25
Chng 2 CC I LNG THNG K
(Descriptive statistics)
i vi cc php phn tch lp li t mu ban u, c hai loi i lng dng
ch s phn b cc ga tr trong tp s liu l gi tr trung bnh v phn tn ca cc
gi tr di dng lch chun. Cc i lng thng k thng s dng nh gi tr
trung bnh, trung v, phng sai, lch chun, lch chun tng i, h s bin
thin Sau y chng ta ln lt xt cc khi nim ny
2.1. Cc i lngch s phn b ca cc gi tr o lp li

* Trung bnh s hc ( x ) (mean, arithmetic mean, average) l i lng dng

ch gi tr t c khi chia tng cc kt qu th nghim lp li cho s th nghim
lp li.
Gi s c tp s liu th nghim lp li gm n gi tr, k hiu t x 1, x2,, xn th
gi tr trung bnh s hc ca tp s liu gm n th nghim lp li l:
N

x x ... xn x
i 1
i
x = 1 2 = (2.1)
n n

Gi tr trung bnh c tnh cht sau:

- Tng lch gia cc gi tr ring r v gi tr trung bnh bng khng.

(x i x) 0

- Tng cc bnh phng lch nh hn tng bnh phng ca bt c lch no

gia gi tr n l v gi tr a no khng phi gi tr trung bnh.

(x i x) 2 < ( x a)
i
2
( vi a x )

* Trung bnh bnh phng ( x bp): vi tp s liu gm N s liu lp li x1,

x2,,xn ta c:

x12 x22 ... xn2

x bp = (2.2)
n

* Trung bnh hnh hc hay trung bnh nhn (geometric average) vi cc php
o c hm lng cn tm di dng logarit th:
1
lg x hh= (lg x1 lg x2 ... lg xn )
n

Do x hh= n x1.x2 ....xn ( 2.3)

26
Trong cc i lng trung bnh k trn, thng s dng trung bnh s hc
* Trung v (median) : Nu sp xp n gi tr lp li trong tp s liu theo th t tng dn
hoc gim dn t x1, x2, , xn th s nm gia tp s liu c gi l trung v.
- Nu n l s l th trung v chnh l s gia dy s.
- Nu n l s chn th trung v l trung bnh cng ca 2 gi tr nm gia dy
s.
Ch : Gi tr trung bnh hay trung v ca tp s liu c gi l cc gi tr trung
tm ca tp s liu. Cc tp s liu khc nhau c cng gi tr trung bnh c th rt khc
nhau v ga tr ring l v s th nghim. V vy, trung bnh v trung v khng cho ta
ci nhn tng qut v s phn b cc s trong tp s liu. Trong trng hp cn xt
n phn tn ( lch khi ga tr trung bnh).
* im t phn v (quartile): Nu sp xp cc s liu trong tp s liu t nh n
ln th mi tp s liu c 3 im t phn v: 25 % cc s trong tp s liu sp xp
c gi tr nh hn hoc bng im t phn v th nht, 75 % cc s trong tp s liu
sp xp c gi tr nh hn hoc bng im t phn v th ba, 50% cc s trong tp s
liu sp xp c gi tr nh hn hoc bng trung v (im t phn v th hai).
Khong gia im t phn v (interquartile) biu th s khc nhau gia im t phn
v th nht v th ba.
C th hnh dung im t phn v theo s sau:
Trung v

gi tr 0% 25% 50% 75% 100% gi tr cao

thp im t phn v th nht im t phn v th ba.
* S tri (mode): l s c tn s xut hin l ln nht trong tp s liu lp li.
Ch : Gi tr bt thng c nh hng ng k ti gi tr trung bnh nhng khng
nh hng n s trung v. Do vy, vi nhng tp s liu rt nh, (thng N<10)
nh ch phn tch lp 2 hoc 3 ln th nn s dng gi tr trung v thay cho gi tr
trung bnh v s trnh c gi tr bt thng.

Th d 2.1. Kt qu phn tch lp li hm lng Selen (g/g) trong thc phm sau 9
ln th nghim nh sau: 0,07; 0,07; 0,08; 0,07; 0,07; 0,08; 0,08; 0,09; 0,08. Tm cc
gi tr trung bnh, trung v, s tri v im t phn v th nht v th ba.

Gii: p dng cng thc tnh c gi tr trung bnh l 0,07677= 0,077 g/l

27
 Sp xp theo th t t thp n cao th s chnh gia l s th 5 v l 0,08g/l

S c tn s xut hin ln nht l 0,07g/l ( 4 ln) v 0,08g/l (4 ln).

im t phn v th nht l 0,07g/l (sau 2 s), im t phn v th ba l 0,08g/l

(s th 6)

- Mu thng k v mu tng th (statistical sample and population).

Trong thng k, mt s xc nh cc quan st thc nghim (hay kt qu ca
php o cc mu phn tch ring r t mu ban u) c gi l mu thng k. Gp tt
c nhng mu thng k gi l mu tng th. Nh vy c th xem phn tch mu
tng th l thc hin tt c nhng php o c th c v v cng ln (n).
Th d: Cn iu tra mc thiu iot trong hc sinh tiu hc thnh ph A. Tin
hnh ly mu nc tiu hc sinh mt s trng tiu hc trong thnh ph phn
tch hm lng it. Nh vy nc tiu ca mt s hc sinh tiu hc mi trng c
ly mu l cc mu thng k. Mu tng th y s l mu nc tiu ca hc sinh
tiu hc thnh ph A ni chung.

- Trung bnh mu x v trung bnh tp hp .

+ Trung bnh mu ( sampling fluctuation) ( x ) l gi tr trung bnh ca mt mu

thng k gii hn c rt ra t tp hp gm n s liu lp li v c xc nh theo
n

x i
cng thc: x i 1
.
n

+ Trung bnh tp hp (population average) () l gi tr trung bnh ca tp hp

gm N s liu lp li trong mu tng th, cng c xc nh theo phng trnh (2.1)
nhng vi N rt ln, gn t ti . Khi khng c sai s h thng th trung bnh tp hp
cng l gi tr tht ca php o.
N

x i
i 1
khi N . Thng thng khi N > 30 c th xem nh x
N

2.2. Cc i lng c trng cho phn tn ca tp s liu o lp li

* Khong bin thin hay quy m bin thin R (spread, range): l hiu s gia
gi tr ln nht v gi tr nh nht trong mt tp s liu.
R = xmax - xmin (2.4)

28
 ln ca R ph thuc vo kch thc mu. Vi cng sai s ngu nhin, khi s
php o tng, R s tng. Do , khong bin thin c dng c trng cho
phn tn ca tp s liu khi s php o nh.

* Phng sai (variance) ( 2 v S2): l gi tr trung bnh ca tng bnh phng s sai
khc gia cc gi tr ring r trong tp s liu so vi gi tr trung bnh. Phng sai
khng cng th nguyn vi cc i lng o.

Nu tp s liu ln (N ) th phng sai mu tng th c k hiu l 2 v c

x
N
2
i x
tnh theo cng thc 2 i 1

Nu tp s liu nh th phng sai mu thng k c k hiu l S2 v c tnh theo

n
x x
2
n
i
2
x
i
1 n 2 i 1
cng thc S 2 i
i 1
= x (2.5)
n 1 n 1 i 1 n

vi n-1=f c gi l s bc t do ( degree of freedom).

Khi c m tp s liu ca m mu thng k, mi tp s liu c cha k kt qu ca
k th nghim lp li i vi cng mt mu nh sau:
x11, x12, x13,, x1k
x21, x22, x23,, x2k

xj1, xj2, xj3,, xjk
xm1, xm2, xm3,., xmk

x
m k
2
ij xi
j 1 i 1
th phng sai chung ca m mu thng k ny l: S2
N m
(2.5)
vi N l tng tt c cc th nghim N=m.k
(Khi nim ny t dng trong ho hc)
Nu phng sai cng ln th tn mn ca cc gi tr o lp li cng ln hay
lp li ca php o km.
* lch chun (Standard deviation)

29
 - lch chun tp hp (Population standard deviation): () c trng cho
phn tn cc s liu trong tp hp cc gi tr o ca mu tng th so vi gi tr trung
bnh v c xc nh theo phng trnh:

x
N
2
i x
i 1
hay 2 (2.6)
N

vi N l s th nghim lp li ca tp hp, thc t trong Ha phn tch thng

xem cc tp cc s liu lp li khi N>30 l tp hp.
- lch chun mu c on (Sample estimate standard deviation): (S)

x x
n 2
i
S i 1
hay S S2 (2.7)
n 1

vi n l s th nghim trong mt mu thng k c rt ra t mu tng th. S

bc t do trong trng hp ny l f =n-1.

Nh vy, khi N th x v S . Ni cch khc khi N>30 c th xem S .

So vi phng sai, lch chun thng c dng o lp li hn do c cng

th nguyn vi i lng o.
Nu trng hp c m mu thng k, mi mu lm k th nghim lp li th:

x
m k
2
ij x
S 1 1
bc t do f=m(k-1) (gi thit Sj khc nhau khng ng
m.k m
k).

* Khi nim bc t do: Bc t do c th coi l s php o kim tra cn thit c

th xc nh c kt qu trong mt tp s liu. Mt cch khc, bc t do c
hiu l s cc quan st trong mt mu thng k c th t do thay i do bng
tng s cc gi tr trong tp s liu tr i 1 bc t do cho mi gi tr trung bnh
c tnh.
Nh vy vi 1 tp s liu mu thng k (c 1 gi tr trung bnh) th bc t do l
f= n-1. Vi hai mu thng k khi tnh phng sai chung th bc t do l f= n1+n2-
2 v c hai ga tr trung bnh c tnh. Vi mu tng th, khi s th nghim v
cng ln th gi tr trung bnh chnh l gi tr thc nn khng xt bc t do.
Mt cch khc, c th hiu bc t do xut hin trong biu thc tnh phng sai

30
ca mu thng k. biu thc tnh phng sai (2.5) gi tr phng sai tc l
trung bnh ca tng bnh phng th ch c n-1 gi tr tng bnh phng c tnh
nn f= n-1.
Thut ng bc t do cn c gii thch qua ch s chch bnh phng
( xi x) 2 ) c lp dng trong php tnh phng sai nh sau:

Gi s c ba kt qu phn tch lp li hm lng As trong nc ngm l 18,5;

17,3 v 19,2 g/l. Do gi tr trung bnh c tnh l 18,33 g/l.
Nh vy cc gi tr chch bnh phng ln lt l
d12= (18,5-18,33)2= 0,0289; d22= (17,3-18,33)2= 1,0609; d32= (19,2-18,33)2=
0,7569
Cc gi tr chch bnh phng ny khng phi l cc s c lp v khi thay i
t nht 1 gi tr trong 3 kt qu o th gi tr trung bnh thay i v ko theo cc
gi tr chch thay i, do khng th c 3 bc t do. Ni cch khc, nu
chng ta c gi tr trung bnh v hai gi tr kia th chng ta s tnh c gi tr
th ba. Nh vy, bc t do trong trng hp ny l f=3-1=2.

Khi tnh ton ch khng lm trn s liu ca lch chun cho n khi kt
thc php tnh ton v gi tr cui cng phi c ghi di dng s c ngha.

i vi tp s liu nh (N<10) th lch chun thng c tnh bng cch nhn

khong bin thin vi h s k (k factor).
SR =R.kR
Gi tr kR tu thuc vo s th nghim lp li n, c tnh theo bng 2.1.
Bng 2.1: Gi tr k (theo s th nghim) dng tnh nhanh lch chun .

n 2 3 4 5 6 7 8 9 10

k 0,89 0,59 0,49 0,43 0,39 0,37 0,35 0,34 0,32

* lch chun hp nht (hay lch chun gp) (Pooled standard deviaton)

x x x ....
n1 n2 n3
2 2 2
i1 x1 2j x2 3k x3
i 1 j 1 k 1
S pooled
n1 n 2 n3 ... m

Vi n1 l s cc s liu lp li trong tp s liu th nht, n 2 l s cc s liu

trong tp s liu th hai, m l s cc tp s liu c hp nht.

31
 * sai chun ( lch chun ca trung bnh) (standard deviation of a mean/
standard error):
Nu c nhiu dy s liu lp li (hay nhiu mu thng k), mi dy c n s liu
c ly ngu nhin t tp hp cc s liu lp li th s phn tn ca trung bnh tp
hp (vi N th nghim) c c trng bng sai chun m thay cho lch chun
trong tp hp. S phn tn ny gim khi N tng.

m l lch chun trung bnh hay sai chun v c tnh nh sau :

m=
N

Tuy nhin, i vi tp s liu hu hn (n<30) ta ch thu c s c lng S x thay

cho m.

x x
n 2

i
S2 S
Sx i 1

n n nn 1

sai chun thng c dng c trng cho khng m bo ca gi tr

trung bnh. sai chun m c dng c trng cho sai s ngu nhin ca phng
php phn tch. Tuy nhin, sai chun c trng cho sai s ngu nhin ca
phng php phn tch cn tin hnh cc php xc nh song song, khng ph thuc
nhau (nh thi gian phn tch khc nhau) nh gi ti lp ca phng php
phn tch v dng kt qu phn tch khng lm trn (vi 1 ch s cui cng l s
khng c ngha).
* lch chun tng i (Relative standard devition) (RSD%) v h s bin
thin (coefficient variation) (CV%).
lch chun tng i (RSD) l t s gia lch chun v gi tr trung
bnh. N thng c biu th bng phn nghn (nhn vi 1000 ppt) hay ph bin hn
l phn trm lch chun tng i (nhn vi 100%).
S S
RSD(%)= .100 % hay RSD= .1000 (ppt)
x x

RSD(%) cn c gi l h s bin thin (CV%). i lng ny c dng o

chm ca php phn tch.
Ngi ta thng s dng lch chun tng i (RSD) hn l lch chun
(S) do c th nh gi c lch chun chim bao nhiu phn trm gi tr trung
bnh v c ci nhn r hn v chm ca cc s liu trong tp s liu lp li.

32
Th d 2.2. (a) Mt sinh vin phn tch lp li 4 ln xc nh hm lng Sn trong
mt mu qung thic c cc kt qu nh sau: 51,3%, 55,6%, 49,9% v 52,0%.
Tnh gi tr trung bnh, lch chun v lch chun tng i
Gii: p dng cc cng thc ta c

Gi tr trung bnh: x = (51,3 + 55,6 + 49,9 + 52,0)/4=208,8/4= 52,2 (%)

lch chun

(51,3- 52,2)2 (55,6- 52,2)2 (49,9- 52,2)2 (52,0- 52,2)2 (-0,9)2 (3,4)2 (-2,3)2 (-0,2)2
S=
4 1 3

0,81 11,56 5,29 0,04

S= 5,9 =2,43
3

lch chun tng i %RSD = 100.S / x =4,65 (%)

(b). Cho kt qu phn tch lp li 35 ln hm lng nitrat (g/ml) trong mu nc

chun nh sau :
0,51 0,51 0,49 0,51 0,51 0,51 0,52 0,48 0,51 0,50 0,51 0,53 0,46 0,51 0,50
0,50 0,48 0,49 0,48 0,53 0,51 0,49 0,49 0,50 0,52 0,49 0,50 0,50 0,50 0,53
0,49 0,49 0,51 0,50 0,49
Hy tnh gi tr trung bnh, lch chun, sai chun v lch chun tng i
ca tp s liu trn.
Gii: Vi tp s liu trn khi N>30 th c th xem nh y l tp hp cc s liu khi
phn tch mu tng th. Do vy s c gi tr trung bnh tp hp, lch chun tp
hp, sai chun tnh nh sau:
N 35

xi x i
i 1
= i 1
0,504113 0,50 4 (g/ml)
N 35

x = 0,015 (g/ml) = = 0,0026(g/ml)

N
2
i x
i1 4 m
N 35

%RSD=100./=3,06%.

* lch chun lp li v lch chun ti lp: phn bit lch chun

ca cc th nghim song song trong cng iu kin v khc iu kin, ngi ta a ra
hai khi nim lch chun lp li (Sr) v lch chun ti lp (SR).

33
 - Trong mt tp s liu lp li (v d c n th nghim lp li) do cng mt k
thut vin trong 1 PTN tin hnh trn cng trang thit b, ha cht.. trong khong thi
gian ngn th lch chun lp li l:
n

(x i x) 2
Sr i 1

n 1

-Nu c nhiu tp s liu lp li nh ca k k thut vin (KTV) hay c k PTN th

cn thit tnh lch chun ti lp. tnh gi tr ny trc tin cn tnh phng sai
trung bnh c trng cho tng bnh phng s sai khc ca k PTN ny chnh l
trung bnh ca k gi tr phng sai ring r (gi l phng sai chung trong PTN-
(within laboratories) k hiu l MSwithin hoc S 2 r
Ta c: phng sai trong cng mu thng k: (cng PTN, cng KTV)
n n

(x x )
i 1
2
( x ki xk ) 2
Sr1 i 1
Sk i 1
2 2

n 1 n 1
Mi mu thng k hay mi ngi th nghim lm n th nghim lp li, do c
n-1 bc t do. Tng s mu thng k l k mu. Vy bc t do i din cho tt cc cc
mu l f0 =k(n-1).
Do vy, phng sai trong cng mu (within-sample estimation of variance/
within-sample mean square) s l:
k k n

Si (x x j )2
2
ij
j 1 j 1 i 1
S 2 r = MS within
k k (n 1)

Khi ly k gi tr trung bnh ca k KTV hay k PTN th cc gi tr trung bnh ny s

khc vi gi tr trung bnh chung hay cn gi l trung bnh tp hp nn phng sai
gia cc mu thng k (hay gia cc KTV, cc PTN) k hiu l MSbetween hay S2L
(between-sample estimation of variance) c tnh nh sau:
k

j 1
xi
Trung bnh tp hp l x
k
Khi phng sai gia cc mu (hay phng sai gp gia cc nhm):

34
 k
k ( x j x) 2
j 1
MS between
k 1
Khi phng sai ti lp l tng phng sai ca hai thnh phn phng gia cc
nhm v trung bnh phng sai trong mt nhm. T gi tr ny ly cn bc hai ca
phng sai s thu c lch chun ti lp v lch chun ti lp tng i
(%RSDR).

S2R= S2L + S 2 r = MSwithin + MSbetween

V %RSDR = 100.SR/ x (%)

Th d 2.3: Mt PTN thuc h thng cng nhn cc PTN Vit nam VILAS (PTN
c cng nhn cht lng ca Vn phng cng nhn cht lng thuc b ti
nguyn mi trng) cn nh gi lch chun lp li v lch chun ti lp
tin hnh xc nhn gi tr s dng ca phng php th mt loi thuc tr su
trong mu rau. Bn KTV khc nhau, mi ngi lm lp 10 ln vi mt mu rau
thm chun (l mu rau sch, khng cha cht cn phn tch v c thm cht
chun) c nng 100,0 ppb trn cng thit b, dng c v ha cht c sn trong
cng PTN..
Kt qu hm lng thuc tr su tm li c trong mu thm chun ny nh
sau:

STT KTV-1 KTV-2 KTV-3 KTV-4

1 99,07 99,68 99,51 99,55

2 99,06 99,69 99,54 99,62

3 99,03 99,74 99,51 99,56

4 99,06 99,61 99,54 99,62

5 99,07 99,73 99,53 99,57

6 99,07 99,68 99,54 99,58

7 99,06 99,74 99,53 99,57

8 99,05 99,76 99,54 99,56

9 99,06 99,64 99,51 99,58

10 99,06 99,74 99,49 99,54

35
- So snh chnh xc trong cc th nghim mi KTV, kt lun v sai s ngu
nhin hay sai s h thng.
- Hy tnh lch chun lp li v lch chun ti lp ca PTN ny.
Gii: + Trc tin tnh 4 gi tr trung bnh hm lng ca 4 KTV, lch chun
lp li v lch chun tng i ca mi KTV, ta c cc kt qu ln
lt nh sau :

KTV-1 KTV-2 KTV-3 KTV-4

x 99,06 99,70 99,52 99,58

Sr 0,0120 0,0493 0,0178 0,0268

%RSD 0,012 0,049 0,018 0,027

ER(%) -0,94 -0,30 -0,48 -0,42

Nh vy, cn c vo cc gi tr %RSD ca mi TKV c th kt lun,

chm hay lp li ca KTV-1 l tt nht v ca KTV-2 l km nht. Tuy nhin,
cc gi tr RSD l nh (<1%) nn c th ni mi KTV lm th nghim u cho
chm tt.

Da vo sai s tng i gia gi tr trung bnh tm c v gi tr ng =

100,0 ppb ban u c th kt lun kt qu phn tch ca c 4 KTV u mc sai s
h thng m. ng nh gi qua sai s tng i cho thy kt qu phn tch
ca KTV-2 l nh nht v KTV-1 l ln nht. Tuy nhin, c 4 gi tr sai s tng
i u thp (<1%) chng t cc KTV lm ng. Ni cch khc s liu ca 4 KTV
u chnh xc ( chm tt, ng cao).
+ Tnh lch chun ti lp ca PTN.
Dng cc cng thc nh nu phn trn s tnh c
MSwithin= 0,000902 ; MSbetween = 0,787043, phng sai ti lp S2R= 0,787945
lch chun ti lp l SR= 0,88766= 0,8877 vi gi tr trung bnh chung l

x = 99,465 ppb

lch chun ti lp tng i % RSDR= 0,89%

36
 Cch tnh ton cc i lng thng k s dng phn mm MINITAB:
Phn mm MINTAB l phn mm thng k in hnh, c s dng rng ri
trong x l thng k s liu phn tch, thch hp cc bng s liu c copy t word,
excel hoc chuyn cc file s liu dng ASCII sang.
tm cc i lng c trng thng k ca tp s liu lp li cn nhp s liu
di dng ct (mi tp s liu trong mt ct) v copy vo ct trong ca s lm vic
ca MINITAB, chn Stat Basic Statistics Display Descrative Statistics, chn ct
cha tp s liu v trong mc Statistics chn cc i lng mong mun. Khi kt
qu s c hin th trong ca s ca Session.

Th d 2.4.: Tnh cc i lng thng k c trng ca tp s liu cc PTN A, B,

C, D, E.
Sau khi nhp s liu, kt qu tnh bng phn mm MINTAB thu c nh sau:

PTN S TN Gi tr TB Sai chun lch chun Phng sai %CV Trung v Khong
bin thin
A 6 41,9 0,202 0,494 0,244 1,18 42,0 1,4
B 6 41,9 0,697 1,708 2,916 4,08 42,0 4,1
C 6 43,2 0,171 0,420 0,176 0,97 43,2 1,1
D 6 39,1 1,330 3,250 10,58 8,32 38,8 8,0
E 6 41,5 0,526 1,288 1,659 3,10 41,9 3,6

Ch : * Cc i lng trung bnh, chch v sai s tng i biu din ng

ca tp s liu, kim tra c xut hin sai s ngu nhin hay h thng th lch chun
tng i hay h s bin thin c dng nh gi chm.
* i vi cc phng php phn tch, ty theo nng cht phn tch m ISO
qui nh CV(%) ca mt phng php phn tch. Vi cc mu c nn phc tp, gi tr
CV(%) ln nht c php cho bng 2.1.

37
 Bng 2.1: Quan h gia nng cht phn tch v CV(%) cho php vi phng
php phn tch.

Hm 100 10 1 100 10 1 100 10 1 0,1

lng g/kg g/kg g/kg mg/kg mg/kg mg/kg g/kg g/kg g/kg g/kg

CVmax 2 3 4 5 7 11 15 21 30 43
(%)

Cng theo ISO, sai s tng i dng nh gi qua ng ca phng php

phn tch lng vt nh sau :

- Nu lm lng cht phn tch 1 ppb th sai s tng i cho php t -50 %
n +30 %
- Nu lm lng cht phn tch t 1 ppb n 10 ppb th sai s tng i cho
php t -30% n +10%
- Nu lm lng cht phn tch nh hn1 ppm th sai s tng i cho php t -
20% n +10%.
2.3. Lan truyn khng m bo o khi c sai s ngu nhin
Chng ta u bit, kt qu nh lng thu c t thc nghim trong rt nhiu
php o khng phi l kt qu ca php o trc tip m c th c tnh ton t mt
hay nhiu php o trc tip. Khi khng c sai s h thng th tt c cc kt qu phn
tch nh lng thu c t thc nghim u c cha sai s ngu nhin. Nh cp
cc gi tr c bo co phi c vit di dng gi tr trung bnh (ng s c ngha
km theo) khng m bo o. Khi ch c sai s ngu nhin th khng m bo
o c th l lch chun, sai chun, dung sai, hoc khong tin cy khi s dng
chun thng k no (s xt sau). Mt khc, mi s liu thu c trong cc php tnh
u c hoc lm lp li nhiu ln hoc c nhiu yu t sai s gy nn v c lch
chun ring, v vy phi xt n lan truyn sai s ngu nhin gy ra cho kt qu cui
cng.
Trong phn ny, chng ta s xt lan truyn khng m bo o theo lch
chun.
Gi s cc kt qu thc nghim thu c a, b, c, ... l cc s liu thu c t
cc php o trc tip M1, M2 , M3. Gi x l gi tr cui cng tnh ton c t cc
kt qu ring r a, b, c.Khi x l hm s ph thuc vo cc tham s a, b, c

38
 Gi a , b , c l lch chun ca cc php o trc tip khi xc nh a, b, c,
v gi thit l sai s trong cc php o ny c lp ln nhau th lch chun ca i
lng x l :
2 2

x [ x a 2 x b 2 ...]1 / 2 (theo nh lut lan truyn sai s, biu thc
a b
ny ng khi x l hm tuyn tnh ca cc php o a, b,c).
Cch tnh lch chun ca i lng x ny tu thuc vo dng cng thc tnh
em s dng. Kt qu o ca i lng x s c biu din di dng : x Sx
V d trong tp s liu th tch dung dch chun dng cho qu trnh chun , cc gi
tr th tch thu c l 10,09; 10,11; 10,09; 10,10; 10,12 ml, Nh vy, th tch dung
dch chun dng s l x S = 10,10 0,01 (vi N=5 th nghim lp li),

* lch chun ca tng v hiu:

Nu x = a1. a( Sa) + b 1.b( Sb) c1 .c( Sc) vi a1,b1, c1 l cc hng s
th lch chun ca x l

S x a1 .S a2 b1 .S b2 c1 .S c2 ...
2 2 2

* lch chun ca php nhn v chia:

2 2 2
a a1 .b b1 Sx 2 S 2 Sb 2 S
Nu x = th a1 . a b1 . c1 . c ...
c c1 x a b c

* lch chun ca php tnh logarit:

Sa
Nu x= k.lna vi k l hng s th Sx= k .
a

k Sa
Nu x= k.loga th Sx= .
2,30 a

Cc gi tr lch chun trong php o trn c gi l khng m bo o

Sa
tuyt i ca php o. i lng gi l khng m bo o tng i.
a

Th d 2.5: a) Tnh gi tr biu thc:

x=(65,060,07) +(16,130,01)-(22,680,02)= 58,51?
ta c S x 0,07 2 0,012 0,02 2 0,073 v biu din x = 58,51 0,07

39
 0,07
lch chun tng i ca php o l .100% 0,1%
58,51

b) x= 2,0164(0,0008)+1,233(0,002)-2,61(0,01)= ?
x= 0,6394= 0,64

Sx= 0,00082 0,002 2 0,012 = 0,01023.

Vit theo ng s c ngha cho x v Sx s l : x= 0,640,01

( v trong 3 s hng th s c t s c ngha nht sau du phy l 2 s)

(13,67 0,02).(120,4 0,2)

c) x 356,0 ?
4,623 0,006
2 2 2
Sx 0,02 0,2 0,006
ta c =0,0026
x 13,67 120,4 4,623

do vy Sx=356,0.0,0026=0,93
Kt qu cui cng s l x = 356,00,9
d) S lng t trong php o hunh quang , c tnh t biu thc sau:
= If /kclI0
trong cc i lng c tnh nh sau (km theo lch chun tng i)
I0 =cng tia ti (0,5%)
If = cng hunh quang (2%)
= h s hp th mol (1%)
c = nng (0,2%)
l = chiu di lp hp th (0,2%)
k l h s thit b.
T phng trnh trn, lch chun tng i c tnh nh sau:
RSD = (22 + 0,22 + 0,22 + 0,52 + 12) = 2,3%
Th d 2.6 : Tnh lch chun s mmol Cl- trong 250,0 ml dung dch mu, nu
ly 25,00 ml dung dch mu ny chun bng dung dch chun AgNO3 c nng
( 0,11670,0002) M. Th tch dung dch AgNO3 tiu tn sau 3 ln chun
lp li l 36,78; 36,82 v 36,75 ml.
Gii : - th tch dung dch chun AgNO3 trung bnh l: 36,78 ml

40
- p dng cng thc tnh lch chun th tch chun ta c S= 0,035
- Vy V AgNO 36,78 0,04 (ml)
3

- S mmol Cl- c chun trong 250 ml mu :

X= (0,11670,0002).((36,780,04).10= 42,92 ?

2 2
Sx 0,0002 0,04
Ta c : ( ).102 0,019
x 0,1167 36,78

Do Sx= 42,92.0,019=0,082
Kt qu s mmol Cl- trong 250 ml mu l (42,920,08) mmol
Ch : Trong qu trnh tnh ton v c s lan truyn sai s nn cn trnh lm
trn s khi vic tnh ton cha kt thc.

S c ngha trong cc php tnh phc tp c ghi km khng m bo o:

- Qui tc: S u tin trong lch chun l s c ngha cui cng trong kt qu
nhn c.
0,002664(0,000003)
+Cho php tnh 0,1066(0,0002)
0,02500(0,00005)

Trong php tnh trn, lch chun, s c ngha l s 2, khi gi tr 0,0002 c

4 ch s sau du phy nn kt qu c ghi vi 4 s sau du phy (con s ny c 4 s
c ngha).
0,8210(0,0020
+Vi php tnh sau 1,022(0,004) th kt qu c biu din ti
0,803(0,002)
4 ch s c ngha mc d s c ngha t nht trong s chia l 3 s v kt qu tnh
lch chun cui cng vi 1 s c ngha to ra s c 3 ch s sau du phy.
1,76(0,03) 0,59(0,02)
+Trong php tnh 0,619 0 ?
1,89(0,02)

Kt qu tnh ly n 2 ch s c ngha sau du phy cho kt qu ca t s nhng 3

s c ngha v c hai s trong php chia tip theo u c 3 ch s c ngha.
tnh Sx, s dng cng thc lan truyn sai s tng phn nh sau

lch chun ca t s: 0,032 0,022 = 0,036 nn t s vit l 1,17(0,036)

2 2
0,036 0,02
Nn Sx= 0,6190. =0,020135
1,17 1,89

41
 V khng m bo o ca cc s thnh phn ch 2 ch s sau du phy nn Sx
phi c vit l 0,020. Do vy kt qu cui cng phi biu din thnh 0,62(0,02) v
trong khng m bo o ch c 2 s c ngha sau du phy.

Th d 2.7: a) Dung dch HCl c c nng phn trm l 37,0(0,5)%, khi lng
ring 1,18(0,01) g/ml. c dung dch cha 0,050 mol HCl cn 4,18 ml dung dch
HCl c. Nu lch chun tng i ca 0,050 mol HCl l 2% th khng m
bo o ca 4,18 ml HCl c l bao nhiu? Bit khi lng nguyn t ca H l
1,00794(0,00007) v Cl l 35,453(0,002)
Gii: T gi tr lch chun tng i ca s mol HCl l 2% dng cng thc i
ra lch chun tuyt i S= 0,02.0,050= 0,001
s mol HCl trong 4,18 ml dung dch HCl c l:
V (ml ).d .C % molHCl.100.M
mol HCl= do V(ml)=
100.M d .C %

0,050(0,001).[1,00794(0,00007) 35,453(0,002)]
Ta c 4,18(x)=
1,18(0,01).0,370(0,005)

0,050(0,001).36,4609(0,0002)
=
1,18(0,01).0,37(0,005)

Ta c
2 2 2 2
0,001 0,01 0,005 0,0002
x= 4,18. =4,18.0,118258=0,494318 =
0,050 1,18 0,37 36,4609
0,49 (ml)
b) xc nh nng dung dch HCl sau khi pha long, ngi ta chun li bng
dung dch chun Na2CO3 vi ch th phenolphtalein. chun ht 27,350,04 ml
dung dch HCl cn (0,9674 0,0009) gam Na2CO3 (khi lng mol phn t l
105,9880,001). Tnh nng mol ca dung dch HCl.
Gii: Phng trnh phn ng vi ch th phenolphtalein l

2H+ + Na2CO3 2Na+ + H2O + CO2

m
Cng thc tnh nng mol HCl l: C= 2.
M .V (l )

2.0,9674(0,0009).1000
Do C= 0,66745
105,988(0,001).27,35(0,04)

42
 2 2 2
0,0009 0,001 0,04
SC= 0,66745. = 0,00116136
0,9674 105,988 27,35

Tuy cc gi tr tnh ton c t nht 4 ch s c ngha nhng khng m bo cui

cng c tnh bt u t s th ba sau du phy nn kt qu cui cng c vit
cso 3 ch s c ngha l 0,667(0,001) mol/l.

BI TP CHNG 2

43
Chng 3 HM PHN B V CHUN PHN B

3.1. Biu din s liu nh lng

Trong phn tch nh lng, s liu thc nghim l cc s liu thu c khi tin
hnh cc php phn tch nh lng. h thng ho nhng s liu ny nhm thu
c ci nhn tng qut hn hoc phc v cho nhng nghin cu tip theo, ngi ta
biu din chng di dng biu hoc th.
Cc loi s liu thc nghim thng gp l:
a- s liu c cha bin c lp v bin ph thuc lin tc nh kho st nh
hng ca hp th quang/ chiu cao pic/ din tch pic sc k/ cng dng/th ...
theo cc yu t nh hng nh pH dung dch, nng cht phn ng, cc yu t vt l
hay theo nng cht phn tch.
b- s liu thu c theo bin ri rc nh bin thin hm lng nng trong h
nhim theo thi gian, hm lng thuc tr su trong cc loi rau, hm lng oddi ho
tan (DO) ti cc v tr khc nhau...
c-s liu m t mi tng quan v lng gia cc bin vi nhau nh tng khi
lng cht thi in t so vi cc loi cht thi khc, phn trm thuc tr su DDT
trong mu so vi cc loi thuc tr su khc...
d- Cc s liu ring r trong tp s liu lp li nh gi tn sut.
Ty theo loi s liu thu c t thc nghim phn tch m c th dng cc loi
th khc nhau sao cho ph hp. V d trng hp (a), v y l quan h gia hm
v bin tc l c qui lut ton hc m t quan h ny nn phi dng dng th ng
(curve) biu din. Tuy nhin cn ch l cc s liu thc nghim lun cha
khng m bo o do vy khng c php ni cc im thc nghim vi nhau m ch
c th biu din cc im c th (y chnh l cc gi tr trung bnh thc nghim) v v
ng biu din ng nht i qua cc im, tc l phi c cc im nm trn v di
ng biu din v gi nh ch xut hin sai s ngu nhin. Cn nu l quan h tuyn
tnh th chnh l ng chun tm c theo phng php bnh phng ti thiu
(vn ny s xt chng 6). Cn nu ch gi nh c mi quan h gia tn hiu o
v i lng kho st nhng khng bit chnh xc dng phng trnh hi qui th c th
th cc dng ng biu din khc nhau c sn trong cc phn mm my tnh m t
nhng khng th dng phng trnh tm c tm mt trong hai i lng khi
khng c i lng kia. V khi , ng biu din ch gip chng ta c ci nhn tng
qut v mi quan h v chiu hng bin thin ca chng trong thc nghim. Cc

44
ng biu din ny c dng ph bin minh ha cc th nghim kho st iu
kin ti u ca phng php phn tch.
i vi cc s liu dng (b) thng hay dng biu ct hay biu hnh ch
nht (bar chart) nhm so snh mt cc nhanh nht v bin thin ca gi tr thc
nghim theo bin ri rc m chng ta chn kho st. Loi th ny ch cho php
kt lun c rng yu t ang xt nh thi gian, a im, loi cht ..c nh hng
ch khng cho php d on qui lut nh hng.
i vi cc s liu dng (c) ngi ta thng qui v gi tr phn trm ca mi
bin minh ha n chim bao nhiu phn trong tp s liu. Do thch hp nht l
loi th hnh qut hay hnh trn (pie chart). Tuy nhin, loi biu din ny ch ph
hp vi cc nghin cu thng k m t c gi tr trong Ha phn tch.
Hnh 3.1 l cc th d m t cc loi th thng gp trong thc nghim phn
tch.

Trungbnh%ccdnglinkttheoTessieretal
0.16

0.14
100%
0.12

0.10 80%
0.08 PD5
60% PD4
0.06
PD3
0.04 40% PD2
PD1
0.02
20%
0.00
0 1 2 3 4 5
0%
-5
CSO (x10 M)
3
2- Cr Mn Fe Co Ni Cu Zn As Cd Hg Pb

(a1). nh hng ca nng sunfit n s (b) Phn trm chit cc dng lin kt
chnh lch hp th quang ca hai dung ca 11 nguyn t trong t ly cnh
dch cha sunfit, fushin v khi c hoc khng chn ng tp kt rc thi in t theo
c Hg2+ qui trnh ca Tesier at al.

45
 Xng A95
benzen %
0.20 (TN1)
Toluen %
m-p xylene %
1.15 11.27
0.15 12.68 o xylene %
delta A khc %

0.10
Y=A+B* X
Parameter Value Error
16.39
---------------------------
0.05 A 0.00195 0.00277
B 0.16152 0.00377
----------------------------
R SD N P
0.00 ---------------------------
0.99918 0.00392 5 <0.0001

0.0 0.2 0.4 0.6 0.8 1.0 1.2 58.52

nong do nitrit (mg/l)

(a2) S ph thuc hp th quang dung (c) T l cc thnh phn cc hp cht

dch metyl khi c mt bromat trong mi hu c d bay hi trong xng A95
trng axit theo nng nitrit

Hnh 3.1. Cc loi th biu din s liu thc nghim trong Ha phn tch

Trong thc t, ngoi cch biu din s ph thuc kt qu o theo mt bin di

dng th dng hai chiu (2D) nh trn cn c th biu din di dng th khng
gian 3 chiu (3D) dng im hay dng mt c th nh gi c nh hng ca c
hai yu t n kt qu th nghim nh hnh 3.2.

HamluongcacdangCrtheoTessieretal(mg/kg)

60

40
Hamluong
20

5
0 4
3 Phandoan
1234 5 2
6 910 12 1
14 16 18
Mau(D)

(a) S phn b hm lng Mn trong cc (b) S ph thuc ca hp th quang

phn on chit khc nhau khi chit cc dung dch phc PAR v Pb2+ theo bc
mu t bng cc dung mi khc nhau. sng v pH dung dch

Hnh 3.2. th dng khng gian 3 chiu biu din s liu thc nghim

46
 Nu cc v d trn trnh by cch biu din gi tr thc nghim ca cc tp s
liu khc nhau s dng ln ca cc s liu th i vi tp s liu lm lp li ngi
ta li quan tm n tn s xut hin cc gi tr trong tp s liu. Khi s liu c
biu din di dng biu tn sut (historgram).
Trong phn trnh by di y s cp n biu biu din tn sut ca gi tr
trong tp s liu lp li di hai dng biu tn sut v biu dng ng th hin
qui lut ton hc .

Cch biu din th tn sut: Cc gi tr trong tp s liu lp li c chia

thnh cc nhm khc nhau (category) v kim tra tn sut ca gi tr biu din
kt qu o di dng im ring bit trn trc s (c chia tuyn tnh 1 chiu) v
nhn nh v mt cc im (trng hp ny gi l phn b 1 chiu) hoc biu din
dng bc thang (ct) bng cch tp hp cc gi tr ring r thnh k cp c b rng d
(5 < k < 20) (k cn bc hai tng cc gi tr o c).
Th d 3.1: Mt mu thp chun CRM c dng xc nh Al. Trong php
th nghim lin phng, mu chun ny c gi n 12 phng th nghim (PTN).
Mi PTN tin hnh phn tch lp li 5 ln t mu ban u trong nhng ngy khc
nhau. Cc gi tr ny c h thng ha nh bng 3.1:
Bng 3.1: Kt qu phn tch hm lng Al (%)
M
trong mu thp ca cc PTN M
M L
STT PTN X1 X2 X3 X4 X5 M L
M L L
1 A 0,016 0,015 0,017 0,016 0,019 I L K
2 B 0,017 0,016 0,016 0,016 0,018 H I K
H I K
3 C 0,015 0,014 0,014 0,014 0,015 H I I
4 D 0,011 0,007 0,008 0,010 0,009 G H F
G H C
5 E 0,011 0,011 0,013 0,012 0,012 G F C
F F B
6 F 0,012 0,014 0,013 0,013 0,015
E F B K
7 G 0,011 0,009 0,012 0,010 0,012 G E E B K
G E C A B
8 H 0,011 0,011 0,012 0,014 0,013 D D E C A B
Gii hn 8 10 12 14 16 18 20 .10-3%
9 I D D
0,012 0,014 0,015 0,013 0,014 trn ca cp D C A A A
ca
10 K 0,015 0,018 0,016 0,017 0,016 cp
Hnh 3.3: Phn phi tn sut khi xc nh ng
11 L 0,015 0,014 0,013 0,014 0,014 thi hm lng Al trong mu thp ti 12 PTN.
12 M 0,012 0,014 0,012 0,013 0,012

47
 Nh vy c tt c N=60 gi tr. Gi tr thp nht l ca PTN D vi

X D2 =0,007%. Gi tr cao nht thuc v PTN A l X A5 = 0,019%. Sau khi tp hp

cc s liu thnh k= 7 cp vi rng ca cp l d= 0,002 %Al ta c k N . Cp
th nht gm cc gi tr 0,007 v 0,008 % Al, cp th hai l 0,009 v 0,010 % Al....
Nh vy ta c th phn b tn sut thc nghim c trnh by hnh 3.3 v biu
tn sut phn trm hnh 3.4.

T dng phn b tn sut c

20 Mean 0.01345
StDev 0.002500
th thy c nh tnh v s xut
N 60
hin sai s ngu nhin. Khi sai s
15 ngu nhin ln th phn b rng,
sai s ngu nhin nh th phn b
Frequency(%)

hp v nhn, nhng trong trng

10
hp ny khng cho bit v sai s
h thng v sai s h thng khng
5 lm thay i dng phn b.

0
0.006 0.008 0.010 0.012 0.014 0.016 0.018 0.020
Al ( %)

Hnh 3.4. Biu phn trm tn sut hm lng

Al trong kt qu phn tch cc PTN
3.2. Cc hm phn b l thuyt
Khi h thng ho cc gi tr o v biu din chng trn th bng cch v tn
sut ca gi tr no vi mt trc l gi tr , ta lun thu c cc phn b dng ct
nh trn, c bit khi ch c sai s ngu nhin. Do , cho php gi thit c nhng qui
lut ton hc lm c s ca nhng phn b .
3.2.1. Phn b chun (Phn b Gauss- Gauss Distribution)
Gi s tin hnh rt nhiu th nghim lp li v thu c rt nhiu cc gi tr (N
) trong c mt s yu t ngu nhin nh hng n cc gi tr ny v cc
nguyn nhn gy nh hng c tnh cng tnh, nh hn gi tr o. Khi s th nghim
lp li ln, v rng ca lp nh dn (d 0) th phn b tn sut s tin dn ti

48
ng cong l tng (hnh 3.4) v c biu din bng hm ton hc v gi l hm
1 x 2
1 ( )
mt xc sut c dng nh sau: y ( x) e 2
(3.1)
2
trong : 3,1416; e 2,7183; l tham s v l lch chun, c trng
cho phn tn ca php o (measure of dispersion); l tham s v l gi tr tht
hay gi tr trung bnh tp hp, c trng cho php o v tr phn b (measure of
location) ; x l ta hoc gi tr o trn trc honh; Y: tung , chiu cao ca ng
biu din tung ng vi gi tr x th hin mt xc sut khi xut hin x.

V tr v dng ng cong c xc nh bi v . Cc i ca ng cong ti

im im x= , ng cong l phn b i xng. Cc im un l x1= - v x2 =
+ . Nu cho . th y = f(x). Khi y = 0 th x = . Tuy nhin, trn thc t c th b
qua cc gi tr ca trc tung khi x ngoi khong 3 .
t xc sut
M

Hnh 3.5: Phn b chun vi cc gi tr Hnh 3.6: Biu din hnh hc ca phn b
lch chun khc nhau. chun

x
Nu k hiu Z th Z l mt bin ngu nhin v hm phn b c dng

1
1 .Z 2
Y ( z) e 2 (3.2)
2

49
 khi h ta mi ny c Z=1 v z=0
Hm phn b Z ny c gi l phn b chun hay phn b Gauss. Phng trnh
(3.2) m t mt xc sut ca phn b, l tng din tch gia ng cong v trc
x l 1 n v. ng biu din cn c gi l ng cong sai s (error curve) (hnh
3.4).

Vi ng cong c =1 th khi ly tch phn trong khong t z=-2 n z=-1 s

c mt xc sut y= 0,136. Nu ly tch phn ca hm phn b chun t - n
+ th ton b phn din tch gii hn bi ng cong biu din xc sut xut hin cc
1
gi tr xi l 1 n v. Do vy h s trong phng trnh (3.2) c gi l h s
2
chun ha.

i vi cc tp s liu c cng gi tr thc s c cng din tch ng cong

Gauss, nhng nu cng nh th ng cong cng hp v cng nhn, chnh xc
cng ln (hnh 3.5).
Gi tr mt xc sut trong phn b chun gn lin vi tin cy thng k P.
Ni cch khc, phn din tch gii hn bi ng cong l tin cy thng k xut
hin xi trong khong tch phn. Xc sut gi tr o nm ngoi gii hn trn ca tch
phn gi l khng tin cy =1-P. Phn din tch P nu biu din theo % so vi tng
din tch th gi l tin cy thng k (%). Gi tr ny c trnh by chi tit trong
phn ph lc. Hnh 3.6 biu din tin cy thng k ca gi tr o.

Trong khong th mt xc sut chim 68,3 % din tch ca ng cong.

Trong khong 2 th mt xc sut chim 95,5 % din tch ca ng cong.

Trong khong 3 th mt xc sut chim 99,7 % din tch ca ng

cong. Nh vy xc xut xut hin gi tr o trong khong 2 l 95,5% (vi l
gi tr trung bnh tp hp). Ni cch khc, vi tin cy thng k l 95 % (thng s
dng trong thc t phn tch) v s th nghim lp li ln (N>30) (nhng khng phi l

v hn) th kt qu o s nm trong khong t x - 1,96( ) n x +1,96 ( ) . y
n n
chnh l khong tin cy c on ca gi tr trung bnh.

Nu k hiu tin cy thng k xut hin ga tr xi nm trong vng (-, xi) l

P(xi) th t hm phn b chun, khi cho gi tr Zi(x) ta s tnh c gi tr hm mt
sc xut v tin cy thng k Pi (ng vi din tch Pi) v ngc li. V vy, thay cho
tnh ton, ngi ta lp sn bng s tra gi tr Z khi bit P hoc ngc li (xem bng
1 phn ph lc).

50
 Trong thc t, a s cc kt qu o lp li trong phng php phn tch thng
thng u tun theo phn b chun (tr cc php m). Tuy nhin, khi x l thng
k, c bit trong cc php phn tch a bin khng c gi thit trc l c phn b
chun trong cc tp s liu thu c t cc phng php phn tch (nh phn tch
lng vt, phn tch bn nh lng... ) m phi kim tra xem tp s liu c tun theo
phn b chun hay khng.

Th d 3.2:Cho kt qu phn tch lp li 35 ln hm lng nitrat mg/kg) cc PTN

khc nhau thu c nh sau :
0,51 0,51 0,49 0,51 0,51 0,51 0,52 0,48 0,51 0,50 0,51 0,53 0,46 0,51 0,50
0,50 0,48 0,49 0,48 0,53 0,51 0,49 0,49 0,50 0,52 0,49 0,50 0,50 0,50 0,53
0,49 0,49 0,51 0,50 0,49. Hy biu din s phn b tp s liu qua th tn sut
v kim tra xem tp s liu c tun theo phn b chun hay khng.
Gii: S dng phn mm MINITAB, sau khi nhp s liu dng ct, chn mc
Graph Histograms, chn with Fit ( v th tn sut v dng c phn b chun
m tp s liu cn t c) ta c kt qu nh sau:

th ny cho thy mc hm lng 0,51

Normal
mg/kg xut hin vi tn s ln nht, gi
Mean 0.5014
10 StDev 0.01537 tr trung bnh ca tp s liu ny l 0,501
N 35
mg/kg v trung v l 0,50 mg/kg. Ba gi
8 tr ny gn ging nhau chng t tp s
liu ny tin ti phn b chun.
Frequency

6
kim tra s tun theo phn b chun
ca tp s liu, c th s dng mc
4
Normality Test trong ca s Stat
Descritive Statistics.
2
Kt qu kim tra theo chun
Kolmogorov- Smirnov cho thy ch s
0
0.46 0.47 0.48 0.49 0.50 0.51 0.52 0.53 KS=0,026 v tr s P (Pvalue > 0,150). Tr
Hmlngnitrit(m
g/kg) s P>0,05 chng t tin cy thng k
l 95% c th kt lun tp s liu tun
theo phn b chun..
(Chi tit tr s P v cch bin lun theo
tr s P s xt trong chng 4)

51
Hnh 3.7. th tn sut ca tp s liu hm lng nitrat

C mt cch khc c dng kim tra s tun theo phn b chun ca tp s

liu lp li l xt lch v nhn trong phn b tn sut cc s liu trong tp hp.
- lch (skewness) l i lng dng ch tnh bt i xng v tn sut ca
cc s liu trong tp hp. Nu gi tr ny gn bng khng th tp s liu c tnh cht
i xng. Nu gi tr ny nh hn khng th phn b lch tri m. Nu gi tr ny ln
hn khng th phn b lch phi dng,
- nhn (kurtosis): gi tr ny c dng biu th nhn ca s phn b cc
s liu trong tp hp. Nu gi tr nhn bng 0 th tp s liu tun theo phn phi
chun. Nu gi tr nhn nh hn khng th phn phi ny nhn hn phn phi
chun.

Vi tp s liu trong th d 3.2, s dng phn mm MINITAB bng cch vo Stat

Basic StatisticsDisplay Descritive Statistics s thu c lch l -0,20 v nhn

52
l 0,50. Nh vy, phn b ny gn i xng, lch tri m, t hn phn b chun. Gi
tr nhn nh c th kt lun phn b ny gn tin ti phn b chun.
Ch : -Trong thc nghim c nhng tp s liu lp li tuy khng ln nhng tun
theo phn b chun (gi tr trung bnh, trung v v s tri trng nhau). Tuy nhin cng
c mt s tp s liu khng theo phn b ny m theo phn b lch (skewed
distribution)(tn xut ca s tri>trung v>trung bnh). Khi gi tr skewed tin ti
khng th phn b lch tr thnh phn b chun. Nhng dng phn b lch ny c th
t c gn phn b chun nu chuyn cc kt qu sang dng logarit thp phn (
log(x)) hoc logarit t nhin(ln(x)) ri tnh gi tr trung bnh v lch chun. Phn
phi ny gi l phn b log-chun (log-normal distribution). iu ny hay gp trong
mt s tp s liu phn tch mi trng khi thnh phn mu khng phi ng nht (m
thng l ly ngu nhin ti cc a im khc nhau) v cn kim tra s tun theo
phn b chun trc khi tin hnh phn tch thng k a bin.
3.2.2. Phn b Poiison
Trong mt s phng php phn tch hin i, kt qu php o l cc i lng
nguyn ri rc, nh m xung vi phn trong Ho phng x, m lng t trong phn
tch ph Rn ghenS liu thc nghim trong cc phng php ny c c im nh
sau:
- Kt qu trong tp s liu l nhng s m cc s kin xy ra trong mt khong
thi gian.
- Xc sut xy ra s kin trong mt n v thi gian l nh nhau vi cc khong
thi gian khc nhau.
- S s kin xy ra trong khong thi gian ny c lp vi khong thi gian khc.
Nu lp li nhiu ln cng mt th nghim th mi quan h gia gi tr o v tn
xut c biu din bng hm phn b xc sut nh sau:

x .e
y . vi x= 0,1, 2, 3 v l trung bnh ca s cc s kin
x!
trong khong thi gian xt. Dng ng phn b nh hnh 3.8 c gi l phn b
Poisson. Cc i lng c trng thng k l:

- Gi tr trung bnh =

- Phng sai 2 =

- Gia v c quan h: = 1/2 vi l s thc v >0

53
 Hnh 3.8. Phn b Poisson vi cc gi tr trung bnh khc nhau.

Phn b Poisson l phn b ri rc. Khi nh th phn b c dng bt i xng.

S bt i xng gim nhanh khi tng v dng ng phn b tin ti phn b chun.
Thc t khi n > 15 th c th coi nh xp x phn b chun. ng vi bng phn b
chun s c 68,3 % cc gi tr trong gii hn - 1/2 v +1/2.

3.2.3. Phn b Student (t)

Nh thy, phn b chun xt trn ch thch hp vi trng hp s php o
ln (N). Khi s php o nh, mt phn b c th lch khi qui lut ca phn b
chun, do cn loi tr khng tin cy bng phn b i xng bin dng gi l
phn b student (t).
Hm ca phn b t c dng:
f 1
t2
Y (t , f ) B (1 ) 2
vi B l hng s v f l bc t do.
f

Hm phn b ny ph thuc bin t mt cch ngu nhin.

th ca hm t c dng ca hm phn b chun v c y tnh cht nh hm
phn b chun nhng nhn ca th hm phn b t ph thuc vo bc t do, cn
phn b chun khi N khng ph thuc bc t do (hnh 3.9).

54
 Phn phi chun

PP chun

Hnh 3.9: Phn b Student vi f=1; f=3, f=5, f=100 v phn phi chun.
Chiu cao v rng ca cc ng cong ca phn b t chun ho ph thuc
vo bc t do f ca lch chun. Bc t do f cng nh th ng cong cng t. Khi
N th S v phn b t chuyn thnh phn b chun Z (thc t ch cn xt vi
N>30). Cc gii hn tch phn ca phn b t ph thuc vo xc sut P v bc t do f
c cho trong ph lc 2. Khi bit hai gi tr f v P c th tra bng t tm gi tr tch
phn ca phn b t (khc vi chun Z ch ph thuc vo P). C hai loi bng tra gi tr
t tng ng vi phn b t mt pha hoc hai pha (hnh 3.10) trong phn ph lc. V
d, trong bng 2b, khi P=0,95, f=4 th t= 2,776 ( chun 2 pha).

xc sut P

/2 /2

Hnh 3.10 : Phn b Student 1 pha (1 sided) v hai pha (2 sided).

55
 Tng t nh phn b chun, mt sc xut tm c l P% nu gi tr trung
S
bnh trong khong t. S x hay do c th o li l tin cy thng k P
n
v bc t do f cho trc th gi tr thc ca php xc nh s nm trong khong
S
x t( P, f ) . ; gi tr t c tra trong bng t 2 pha. y chnh l khong tin cy c
n
on cho tp s liu nh c N<30.
Chun t (Student-test) c dng ngoi vic tnh khong tin cy ca s liu thc
nghim cn dng so snh gi tr trung bnh thc nghim vi gi tr c chp nhn,
so snh 2 gi tr trung bnh hoc tnh khng m bo o ca lch chun mu khi
s mu o nh.
3.2.4. Phn b Fisher (F)
Gi s c 2 tp s liu vi kch thc mu n1 v n2, phng sai tng ng l S12
v S22 , vi cc bc t do f1= n1-1 v f2= n2-1 v lp t s :
2
S1
F 2 ( sao cho F>1)
S2
f1 2
2
x
Y
th hm mt xc sut s c dng: ( x , f1 , f 2 )
A f1 f 2
f
(1 1 ) 2
f2

trong , x l bin ngu nhin (0 x +) v A l hng s ph thuc vo c

hai bc t do f1 v f2.
ng cong thu c mang c tnh ca mt pha, c v trong gc phn t th
nht gia x=0 v x= (hnh 3.11).

56
 1 2 3 4

Hnh 3.11. Phn b F vi hai bc t do f1 v f2.

Nu ly tch phn hm phn b trong gii hn 0...Fp ( Fp <) ta c P phn ca

2
s1
tng din tch di ng cong, n biu th xc sut gi tr tm c F 2
s2
nm gia 0 v Fp. Cc gii hn ca php tch phn F(P, f1, f2) vi P = 0,95 v P = 0,99
theo f1, f2 c cho ph lc 3. Gi tr F tra bng c dng khi so snh phng sai
ca hai tp s liu hoc nh gi tnh ph hp ca phng trnh hi qui (s st sau).

3.2.5. Phn b 2 ( chi - square distribution)

Cho i lng ngu nhin c cc gi tr x1, x2 ...xn. Nu tp s liu c phn b
chun th c th thu c i lng ngu nhin vi s bc do f=n-1 th hm 2 c
nh ngha t
n
xi x 2 s2
(
1
) ( n 1) 2 2


f 2
Hm mt phn b 2 c dng: Y ( 2 , f ) Ce 2
( 2 ) trong C l
2
hng s, f l bc t do v gi tr ca nm trong khong 0< <+

Hnh 3.12 m t dng ca hm phn b vi 2 nm trong gc phn t th nht

trong min t 2=0 n 2=, hnh dng ph thuc vo bc t do f. Ni cch khc y
l bin th ca hm f vi 2 tp s liu, mt l tp s liu hu hn, s th nghim t v
tp s liu kia c s th nghim rt ln tin ti phn b chun.

57
 Hnh 3.12. Hm phn b ca chun 2

Hm 2 c phn b lch phi dng (positive skewness) v ch 1 bc t do. Nu f

nh, ng cong bt i xng, nu f tng s bt i xng gim v khi f ta c
ng cong phn b chun Gauss vi >0.

Nu ly tch phn hm phn b trong gii hn t 0 n 2P (vi 2P<) ta c

phn tng din tch di ng cong ng vi xc sut gi tr 2 = P thu c t f
quan st c lp, ri vo khong (0,1...2P ). Cc gii hn ly tch phn hm 2 (, f)
vi P =0,95 v P =0,99 c cho trong bng 3, phn ph lc. Hm phn b vi 2
c dng kim tra phng sai hoc kim tra s sai khc ca cc hp phn vi
nhau.
3.3. Quan h gia cc phn b ring
Gia cc hm phn b xt trn c mi tng quan vi nhau th hin s di
y:

Phn phi F
Bc t do f1 v f2
F=S12/S22

f1=1; f2= f 58 f1=f; f2=

F t2 F2/f
3.4. Khong tin cy, gii hn tin cy
-Khong tin cy (confidence interval- CI) ca i lng o l gi tr thc biu th
khong tn ti gi tr trung bnh hay cn gi l khong bt nh ca s liu thc
nghim trung bnh.
-Gii hn tin cy (CL: confidence limit) l gi tr ln nht v nh nht ca khong
tin cy.
Vic tnh ton khong tin cy ca gi tr trung bnh ch c thc hin khi sai s
h thng xut hin khng ng k.
Vi mt tp s liu tun theo phn b chun (N>30 nhng xc nh), khi bit
lch chun , th s sai khc gia gi tr thc v gi tr trung bnh x khng ln hn Z
ln sai chun ca tp hp. Ni cch khc

x Z
N
Nh vy, gii hn tin cy ca gi tr thc c tnh theo phng trnh:

x z
N

59
 y Z l gi tr chun thng k Gauss, lin quan ti tin cy thng k, thng
l 90 %, 95 %, 99 ( tng ng vi xc sut xut hin gi tr x l 1,64; 1,96 v 2,58). V
d, vi mc tin cy thng k l 95% th gi tr thc tn ti trong khong :

( x 1, 96 ; x 1, 96 )
N N
i vi cc tp s liu nh (tc l cc mu thng k c s th nghim lp li
n<30), ngi ta s dng S ( lch chun mu) thay cho ( lch chun tp hp) v
gi tr chun student (t) thay cho chun Gauss Z .

S
Khi , gii hn tin cy c tnh l : x t
n
Gi tr t c tra trong bng phn b t hai pha (bng 2b, phn ph lc) vi tin
cy thng k 95% v bc t do f= n-1.

Nhn xt: - Khong tin cy t l nghch vi n , do vy s th nghim cng ln

th khong tin cy cng hp v gi tr trung bnh cng gn vi gi tr thc.
- tin cy thng k cng cao th khong tin cy cng ln v c Z v t
u tng. Khi tin cy thng k l 100 % th khong tin cy l . Trong thc t
phn tch, thng ch ly P= 95%
Ch : Vi tp s liu rt nh v d ch phn tch lp li 2-3 ln th gii hn tin
cy nu tnh theo chun t s rt ln v gi tr t ln nn thng c tnh t khong bin

thin R nh sau: x R .t R
Gi tr tR c tra tin cy thng k P=0,95 v P=0,99 nh bng 3.2.
Bng 3.2. Gi tr t tra theo khong bin thin R tin cy thng k 95% v 99%

n 2 3 4 5 6 7 8 9 10

tR (P=0,95) 6,4 1,3 0,72 0,51 0,40 0,33 0,29 0,26 0,23 0,00

tR (P=0,99) 31,83 3,01 1,32 0,84 0,63 0,51 0,43 0,37 0,33 0,00

3.6. Mt s th d lin quan khong tin cy

60
Th d 3.3: a)Kt qu phn tch tng hm lng asen v c trong mt mu nc ngm
ngoi thnh H Ni theo phng php ph hp th nguyn t ha hi lnh sau 5
ln lp li l: 24,75; 25,12; 24,76; 26,28; 25,15 g/l. Tm khong xc nh ca hm
lng thc asen trong mu nc ny.
Gii: - Vi n=5, tin cy thng k P= 95%, nu xem s liu ny tun theo phn b
Student th gii hn tin cy ca hm lng asen trong mu nc ngm l

S
xt tra bng t(P=0,95; f=4)= 2,776; gi tr trung bnh l 25,212 g/l,
n
lch chun S= 0,627
0,627
Thay vo cng thc trn ta c: = 25,212 2,776. = 25,212 0,778 g/l
5

b) Vn tp s liu trn, tm khong xc nh theo R v tR tin cy thng k l 95%.

- Ta c R= xmax-xmin= 1,53 ; tra bng c tR= 0,51.

Do = 25,212 1,53.0,51=25,212 0,780

Nh vy vi n= 5 v tp s liu khng qu phn tn th khong tin cy tnh theo c hai
cch l nh nhau.
Th d 3.4 : Kt qu phn tch hm lng MgO(%) trung bnh trong mu xi mng
c kim tra tnh ng nht ti 40 PTN c l xi mng thuc h thng phng th
nghim LAS-XD ca B Xy Dng thu c nh sau :

2.41 2.30 2.27 2.42 2.30 2.34 2.29 2.39 2.44 2.31

2.35 2.38 2.41 2.25 2.60 2.38 2.33 2.27 2.31 2.37

2.40 2.39 2.25 2.20 2.34 2.39 2.23 2.29 2.40 2.29

2.12 2.21 2.41 2.29 2.33 2.39 2.39 2.33 2.34 2.40

Hy tm gi tr thc hm lng MgO trong mu xi mng.

Gii : V cc PTN u c cp chng nhn PTN tiu chun nn kt qu phn tch
ca cc PTN c th tin cy c. Do gi tr trung bnh ca 40 PTN ny s gn tin
ti gi tr thc ca mu. Khong tin cy ca gi tr trung bnh tp hp ny ( tm da
trm chun Z) chnh l gi tr hm lng c chng nhn. Ni cch khc, mu ny
c th s dng lm mu chun c chng nhn (CRM) nu tp s liu khng c gi
tr bt thng v t ng nht (theo phn tch phng sai ANOVA) (vn ny s

61
c xt chng 4 v chng 5).

Ta c gi tr trung bnh tp hp l : x = 2,338 ( % MgO), lch chun =0,0823, s

th nghim N= 40.

Do gii hn tin cy tin cy thng k P=95%, khi N ln ( N th Z=1,96)

0,0823
l = 2,338 1,96. = 2,338 0,025 ( % MgO)
40

Th d 3.5 : Kt qu phn tch hm lng Ni(II) theo phng php von-ampe ho tan
xung vi phn hp ph trong mu nc Sng Hng ngy 26/4 nm 1997 sau 5 ln lm
lp li l 0,53; 0,50; 0,62; 0,48; 0,65 ppm. y l phng php phn tch n nh
c kim tra v xc nhn gi tr s dng ca phng php. H s bin thin ca
phng php phn tch Ni trong mu c hm lng t 0,1-1,0 ppm l 20 % . Hy biu
din kt qu phn tch ni trn.
Gii: y l bi ton tm khong tin cy khi bit lch chun ca phng php phn
tch.
- Nu s th nghim lp li n <30, th t dy s liu lp li s tnh c gi tr trung
bnh, khi bit lch chun S (hoc nu bit CV(%) trong khong nng xc nh
S
th tnh S theo cng thc CV (%) .100% ). Tra bng tm t(P,f) v tnh c
x
S
x t
N
- Nu s th nghim lp li N>30 th c th xem nh tp s liu ca mu thng k
l tp hp v tp s liu tun theo phn phi chun. Do vy, tin cy thng k 95%
ta c Z=1,96 nn khong tin cy s l:
S
x 1 , 96
N

Trong bi ton trn, vi CV%=20% v x =0,556 ta tnh c lch chun

S= 0,20.0,556= 0,1112.Tra bng t hai pha vi P=0,95 v f= 4 c t= 2,776.
Vy khong tin cy ca kt qu o l
S 0 ,1112
x t 0 , 55 6 2 , 776 . = 0,556 0,122
N 5

Nh vy hm lng Ni trong nc sng Hng ti thi im phn tch l (0,556

0,122 ) ppm vi tin cy thng k l 95%.

62
Th d 3.6. Xc nh s th nghim cn tin hnh thu c chnh xc mong
mun:

S
Nguyn tc: Trong cng thc: x t
N
S
Gi tr - x = t c gi l khng chc chn, hay khng m bo
N
o ca kt qu thc nghim. Khi s th nghim ln th gi tr ny gim c n bt
k gi tr no mong mun x . Ti mt mc hm lng cht cn phn tch c
th, gi tr - x v lch chun S l gi tr cn t c, cho trc (theo ISO), t
S
ta s tnh c i lng t . Tra bng vi t(P=0,95; n ) =1,96 (gi tr s th nghim
N
ln x , s tm c N kt qu thc nghim c tin cy cho trc.
Th d: Kt qu xc nh lng vt Pb (ppm) trong 10 mu t ly t cc v tr
ngu nhin ti tha rung nghin cu nh sau:
91, 95,104, 82, 95, 103, 97, 89,85, 89 ppm Pb.
- Tnh khong tin tp s liu trn.
- sai s ti a gia gi tr trung bnh v gi tr thc l 2 ppm th cn ly t
nht bao nhiu mu phn tch.
Gii: - Kt qu tnh gi tr trung bnh v lch chun, sai chun theo cng thc
(c th s dng phn mm thng k) ln lt l: 93; 7,20 v 2,28.
Tra bng chun t 2 pha vi P= 0,95 v f=9 ta c t= 2,262

Do = 93 2.262.2,28= 93 1,55= (93 1) ppm Pb

S
-Nu sai lch gia x v l 2 ppm tc l t = 2, thay s vi t=1,96, S=
N
2 2
t.S 1,96.7,20
7,20 ta c N= 49,8 50.
2 2

Nh vy cn tin hnh t nht 50 mu ti cc v tr ly mu ngu nhin khc

nhau th mi t c s sai khc gia gi tr trung bnh v gi tr thc l 2 ppm hay
sai s tng i l 2,2% khi hm lng trong mu c 93 ppm.
Th d 3.7. Chn phng php phn tch thch hp c sai s nh hn gii hn cho
trc .
Nguyn tc: ISO qui nh mi phng php phn tch khi p dng u c php mc

63
sai s tng i (nh ga ng khi kim tra vi mu CRM) v h s bin thin
(nh gi lp li v ti lp) ti a no ty theo cp hm lng. Hm lng
cng nh th sai s cho php cng ln. Bi ton t ra l cn chn phng php no
sau N ln th nghim lp li th t h s bin thin CV(%) mong mun.
S
Theo cng thc = t nu bit v N, s tnh c S sau , thay vo cng
N
thc trn xem c tho mn iu kin CV a % cho trc hay khng.
Th d: Mt sinh vin nghin cu xy dng phng php von-ampe ha tan catot trn
in cc thy ngn treo xc nh hm lng nifedipin(M= 346,335 g/mol) trong
cc tiu bnh nhn sau khi ung thuc. Khong tuyn tnh ca php xc nh l 3.10-8
M n 9.10-8M. Mt mu chun nc tiu t to (l mu nc tiu, khng c nifedipin
v thm lng bit trc 4,0.10-8M nifedipin vo mu) cho sai s tng i gia gi
tr tm c vi gi tr chun thm vo l 10% sau 5 ln lm lp li. Hy kim tra xem
phng php ny c tha mn yu cu v chm, t kt lun phng php c t
chnh xc phn tch lng vt hay khng.

x
Gii: Ta c sai s tng i E R .100% 10% v = 4,0.10 M
-8

S
Nn x = 4,1.10-8 M v x -= 0,4.10-8M==t. tra bng vi t(P=0,95; f=4)= 2,776
n

0,4.10 8. 5
0,322.10
-8
Do S=
2,776

Vi nng 4.10-8 M tc l 14 ppm th ISO cho php CV(%) <7%

S
i vi php phn tch ny th CV(%)= .100 = 8,05%
x

Nh vy, php phn tch tha mn yu cu v ng theo ISO tc l sai s tgn i

t -20% n +10%CV(%) nhng khng p ng yu cu v chm theo qui nh ca
ISO. Ni cch khc phng php ny c chnh xc cha schp nhn c.
Th d 3.8. Tm khong tin cy ca tp s liu khng tun theo phn b chun- Phn
b log- normal ditribution.
Trng hp cc s liu phn tch trong tp hp bt ngun t cc loi mu khc
nhau, m khng t mt mu ng nht ban u. V d kt qu phn tch hm lng
cht A no trong mu hoc nc tiu ca cc bnh nhn khc nhau, phn tch cht
B trong cc i tng mi trng nh t, nc, trm tch ti cc v tr khc nhau
trong cng khu vcth tp s liu kh tun theo phn b chun. Trong trng hp

64
ny, c th chuyn dng ca tp s liu thnh dng logarit thp phn ( log(x) hoc
logarit t nhin (ln(x). Khi th tn xut s c biu din theo logarit nng
t c phn b chun. Hnh 3.13a v 3.13b biu din th tn xut ca nng
khng th trong huyt thanh v sau khi ly log nng .

Hnh 3.13a: th biu din tn xut Hnh 3.13b: th biu din tn xut
theo nng (phn b bt i xng) theo log(nng ) (phn b chun)

tm khong tin cy cho tp s liu tun theo phn b log-chun, trc tin
cn ly logarit tt c cc s liu trong tp hp ban u thnh tp s liu mi sau
ly log(x) v tnh lch chun cho tp s liu mi ny, t tm khong tin cy
theo chun Z hoc chun t v qui i gii hn tin cy t log(x) thnh gi tr x.
Th d: Kt qu phn tch hm lng haptoglobin (g/l) trong mu huyt tng ly
ngu nhin t 8 ngi khe mnh thu c nh sau:
1,82 , 3,32 , 1,07 , 1,27 , 0,49 , 3,79 , 0,15 , 1,98
-Tnh cc i lng thng k v nhn xt s b xem tp s liu c tun theo phn b
chun hay khng.
-Gi s rng hm lng hatoglobin tun theo phn b logarit- chun. Hy biu din
khong tin cy ca hm lng hatoglobin theo phn b ny.
Gii: + kim tra phn b chun c th s dng phn kim tra trong phn mm
thng k hoc tm cc i lng trung bnh, trung v v s tri. Kt qu tnh ny nh
sau:
Gi tr trung bnh l 1,74, rt khc vi gi tr trung v l 1,55, ng thi khng c s

65
tri. Ch s lch skewness l 0,57 v nhn l -0,72 chng t phn b lch phi
dng v rt t, chng t tp s liu vi rt t gi tr ny cha tin ti phn b chun.
+Nu chuyn tp s liu trn v dng logarit c s 10 (log) th thu c tp s liu
mi nh sau:
0,26; 0,52; 0,03; 0,10; -0,31; 0,57, -0,82; 0,30
Tp s liu log ny c gi tr trung bnh l 0,082, trung v 0,182, lch chun l
0,462. Tra bng chun t vi P=0,95 v f=7 c t= 2,365.
S 0,462
Nh vy gii hn tin cy l : t. 2,365. = 0,413
n 7

Do khong tin cy ca logarit nng l : (0,082 0,413).

Ly ly tha x= 10logx ta c khong tin cy ca nng hatoglobin trong mu bnh
nhn l : (1,21 2,69 )g/l

BI TP CHNG 3

66
Chng 4: CC PHNG PHP KIM TRA THNG K

Nh chng 3 xt, khi s th nghim lp li ln ( N) v gi thit khng c

sai s h thng th gi tr trung bnh s tin ti gi tr thc. Tuy nhin, khi s th
nghim khng ln th lun c s sai khc gia gi tr trung bnh v gi tr c chp
nhn. Tuy nhin, lm th no bit s sai khc ny l c ngha thng k, ni cch
khc l xut hin sai s h thng trong php o. Khi , ngi ta p dng php
kim tra thng k (significant tests).
4.1. Nguyn tc php kim tra thng k
Mc ch ca cc php kim tra thng k l lm cho kt qu phn tch c din
gii mt cch khch quan nhm gii p cu hi c s khc nhau gia cc kt qu thu
c hay khng. Ni cch khc, cn kim tra xem gi thit thng k cc kt qu o
thuc cng tp hp (nh nhau) l ng hay sai?
Trong thc t phn tch, nh ho hc thng t ra gi thit v phn tch thng k
s liu a ra xc sut xy ra gi thit . Ni cch khc ta cho gi thit l ng
(v gi l gi thit o- null hypothesis,( k hiu l H0 ) v tnh ra xc sut gi thit
ng, hay i tm tr s P (probabality - Pvalue). Nu xc sut xy ra cng thp c
ngha l gi thit o c kh nng ng. Thng th gi thit o b loi b nu xc
sut s khc nhau xy ra vi c hi 5%. Trong trng hp , ngi ta ni rng s
khc nhau c ngha mc 5%. Nu mun tng quyt nh ng th c th s dng
mc cao hn nh 1% ( =0,01)
Cch tin hnh: Phn tch lp li N ln v thu c dy s liu x1, x2, .xN khi
s tnh c i lng cn kim tra l gi tr trung bnh l x v khong tin cy
thng k tnh theo phn b chun Gauss l Z./ N tin cy thng k P nh
trc. Gi thit t ra (H0) l i lng tm c ging vi i lng bit trc (gi
thit khng m ch khng c s khc nhau gia hai i lng cn so snh).

V mt l thuyt, nu nm ngoi khong tin cy ca gi tr x chn trn

th gi thit t ra (hai i lng ging nhau) b bc b v s khc nhau gia cc i
lng x v c gi l s khc nhau c ngha thng k, tin cy P. Tuy nhin,
iu ny c ngha l s phi th rt nhiu khong tin cy mi gi tr P. V vy, ngi
ta tnh xc sut P v so snh n vi tin cy thng k mong mun.
Khi kt lun ngi ta tun theo 3 qui tc sau:
- Gi thit o cn kim tra b bc b hon ton nu sai lm loi mt (b ci
ng) xut hin t hn 100 (1% tng trng hp) (hay tr s P tc l Pvalue<0,01), tc
67
l c t hn 1% tng trng hp chng ta loi b gi thit o mc d gi thit ny
ng th s khc nhau c ngha thng k tin cy thng k 99%.
- Gi thit o cn kim tra c chp nhn nu sai lm loi mt ln hn 5%
tng trng hp) (hay Pvalue> 0,05) th kt lun s khc nhau khng c ngha thng k,
tc l c xem nh ging nhau tin cy thng k 95%.
- Nu sai lm loi mt nm trong khong 5% v 1% (0,95 < P < 0,99 hay
0,01<Pvalue<0,05) th xem l ang nghi vn. Khi phi lm thm th nghim khng
nh.
Tuy nhin, trong thc t phn tch, ch cn xt kt lun thng k tin cy
95%, ni cch khc ch cn so snh tr s P vi gi tr = 0,05.

4.2. Loi b gi tr bt thng (outliers)

C 3 cch loi b gi tr bt thng:
Cch 1: Quan st mt cch khch quan tm nguyn nhn gy ra gi tr bt
thng v loi cc kt qu c cho l bt thng.
Cch 2: Gi li cc kt qu thc nghim khi ti thiu ho nh hng ca cc
yu t khch quan v ch quan bng cch dng gi tr trung v thay cho gi tr trung
bnh.
Cch 3: S dng chun thng k (chun Dixon hoc chun t) loi b s liu
bt thng.
Trong 3 cch trn, cch 1 v 2 thng c dng nu khng c nh kin c
nhn.
Th d khi quan st cc s liu thc nghim nu thy xut hin du hiu bt
thng th loi ngay (nh mu sc ca dung dch phn tch khc mu thng o, mu
sc ca 1 dung dch trong dy chun khng theo qui lut). Tuy nhin, trong a s
trng hp chng ta khng pht hin ra iu bt thng v vn tin hnh o, vn thu
c kt qu. Do , cch khc quan l x l thng k s liu loi gi tr bt
thng theo ba tiu chun thng k sau y.
* Tiu chun 1: chun Dixon ( Q-test)
Nguyn tc: Sp xp cc s liu thu c theo chiu tng hoc gim dn v dng
Q-test nh gi kt qu nghi ng khc xa bao nhiu so vi s cn li trong tp s
liu. Tnh gi tr Q ( k hiu l Qthc nghim hay Qtnh theo biu thc (4.1) v so snh vi
gi tr Q chun ( hay Qbng) tra trong bng 4.1.

68
 x nghi ngo x lan can
Qtnh= (4.1)
x max x min

So snh Qtnh v Qbng (P=0,90; n). Gi tr nghi ng s l gi tr bt thng nu

Qtnh > Qbng (P,n).
Bng 4.1 : Gi tr chun Q dng loi b gi tr bt thng.

N tin cy thng k

90% 95% 99%

3 0,89 0,94 0,99

4 0,68 0,77 0,89

5 0,56 0,64 0,76

6 0,48 0,56 0,70

7 0,43 0,51 0,64

8 0,47

9 0,44

10 0,41

Ch : Nu s php o ln (n >10) th cch pht hin theo chun Q khng

nhy, do trong php kim tra ny ch c gi tr nghi ng v hai gi tr khc ca php o
c s dng. Khi , kim tra s tn ti ca gi tr bt thng, ngi ta dng tiu
chun 2.

Th d 4.1 : Kt qu xc nh hm lng CaCO3 (%) trong mt mu olomit thu c

nh sau: 54,31;54,36; 54,40; 54,44 ; 54,59 %.
Hy kim tra xem gi tr nghi ng 54,99 c phi l gi tr bt thngkhng?
Gii: S ln cn ca gi tr 54,99 l 54,44.
54,99 54,44
Ta c: Qtnh= 0,8
54,99 54,31

Vi 5 lVi 5 ln th nghim v tin cy thng k P=0,90, tra bng chun Q ta c

Qchun=0,56. vy Qtnh >Qchun hay gi tr 54,59 l gi tr bt thng.

69
 * Tiu chun 2: (p dng cho tp s liu c s th nghim n>10)
Tiu chun ny da trn khong gii hn tin cy ca gi tr trung bnh tin
cy thng k 95% l x 2 ( qui tc 2) (vi x l gi tr trung bnh ca tp s liu
( loi b s liu nghi ng) v l lch chun tp hp). Nh vy, bt c gi tr
no nm ngoi khong x 2 s l gi tr bt thng v cn c loi b.

Th d 4.2: Kt qu phn tch hm lng Pb (mg/kg) trong cc mu t ( n= 26 ) ly

ti khu vc chn ng thu gom v ti ch rc thi in, in t thuc khu vc Triu
Khc, Thanh Tr, H Ni xc nh thep phng php ICP-MS nh sau: 11,9; 26,6;
39,1 ; 73,8 ; 43,3; 11,1; 17,0; 67,7; 51,5; 16,4; 11,1; 11,0; 40,1; 45,1; 33,2; 48,1;
31,7; 51,90; 202; 56,1; 273; 213; 121; 88,0; 42,9. Hy dng qui tc 2 kim tra xem
c nhng gi tr no c xem l bt thng nh sai s th, v tr ly mu b nhim
nghim trng.
Gii: V tp s liu c rt nhiu s hoc rt ln hoc rt nh nn cn ly gi tr
trung v thay cho trung bnh v lc b s b mt s gi tr bt thng tnh lch
chun ca tp s liu. Ta c trung v l (45,1+48,1)/2= = 46,6. Loi b cc gi tr nh
hn 31,7 v ln hn 121 sau tnh lch chun ta c S= 22,5. Vy khong bin
thin theo qui tc 2 l 46,6 2x22,5= (46,645,0) tc l nm trong khong (1,6-
91,6). Vy cc gi tr gm 121; 202; 213; 276 l cc gi tr ln bt thng cng loi
b khi x l thng k cc bc tip theo.

*Tiu chun 3: ISO gi c th s dng chun Grubb kim tra sai s th.
y l php kim tra da trn lch ca cc gi tr nghi ng vi gi tr trung
bnh v lch chun ca tp s liu.
Gi s tp s liu thc nghim c sp xp theo th t tng dn x L , x2, ,
xH . Tnh gi tr trung bnh x , lch chun S v kim tra cc gi tr nghi ng theo
cch sau:

xH x x xL
Trc tin tnh G i vi gi tr cao nghi ng v G vi cc gi tr
S S
thp nghi ng, trong x v S c tnh km theo c gi tr nghi ng.
Sau so snh gi tr Gtnh c vi gi tr Gbng (s php o l N) trong bng
4.2 mc khng tin cy = 5% v 1%. Nu Gtnh>Gchun th xL v xH l gi tr bt
thng cn loi b tin cy thng k cho. Cch lm ny t c p dng v phi
kim tra tng s liu nghi ng bt thng, tuy nhin c u im l p dng c cho
c tp s liu ln v nh.

70
 Bng 4.2: Gi tr G chun 5% v 1 % ca s khng ph hp vi gi tr bt thng
trong mu chun.

S php o (N) Gi tr chun S php o (N) Gi tr chun

5% 1% 5% 1%

3 1,15 1,15 15 2,41 2,71

4 1,46 1,49 16 2,44 2,75

5 1,67 1,75 18 2,50 2,82

6 1,82 1,94 20 2,56 2,88

7 1,94 2,10 30 2,74 3,10

8 2,03 2,22 40 2,87 3,24

9 2,11 2,32 50 2,96 3,34

10 2,18 2,41 60 3,03 3,41

12 2,29 2,55 100 3,21 3,60

14 2,37 2,66 120 3,27 3,66

Th d 4.3:. Ly cc gi tr thu c nh th d 4.2, gi thit cn kim tra gi tr

121.

xH x
Ta c: vi gi tr cao nghi ng T = (121- 46,6)/ 22,5= 3,3
S

Nu s php o l 26, th Tbang< 2,74. Vy Ttnh>Tbng nn gi tr 121 l gi tr bt

thng so vi cc gi tr cn li trong tp s liu trn. Do cc gi tr ln hn 121
cng l gi tr bt thng m khng cn tnh T.
Kim tra tng t vi gi tr ghi ng nh bt thng l 11,0 ta cng c
T= (46,6-11,0)/22,5= 1,36<2,74 vy y khng phi l gi tr bt thng.

Ngoi ra, cc gi tr bt thng c th c nhn bit bng cch dng th

boxplot trong phn mm thng k MINITAB (hnh 4.1) hoc dng phng php phn
tch thnh phn chnh s xt trong gio trnh khc).

71
 300

250

200
Pb(mg/kg)

150

100

50

Hnh 4.1.: th khi nh gi sai s th trong tp s liu lp li

(cc gi tr nh du * l cc gi tr bt thng)
4.3. S dng chun thng k trong cc php so snh
4.3.1. Cc php so snh ca mt tp s liu (1 sample)
4.3.1.1. Kim tra s tun theo phn b chun
Trong rt nhiu php tnh thng k, tp s liu cn phi tho mn iu kin tun
theo phn phi chun, tc l phi tho mn cc iu kin ca phn phi chun t ra.
Vic s dng cc phn mm thng k cho php n gin hn th tc tnh ton bng
cch xt ga tr lch (skewness) trong thng k m t hoc dng cc chun thng k
nh Kolmononov- Smirnov.

Th d 4.4. Kt qu phn tch hm lng Ni( mg/kg) trong mu t l mu chun

(CRM) nh sau: 22 15 18 25 21 12 23 20 20 42 22 31 22 13 8 33 12 23 12
16 30 36 15 17 28 26 26 16 23 26 15 17 17 14 14 18 12 35 30 15 13 14
14 14 13 7 43 59 25 37 7 10 8 13 2 14 11 19 5 12 19 11 15 2 15 31 9 11
26 33 27 13 12 20 26 16 15 22 6 10. Hy kim tra xem cc s liu trong tp s
liu trn c tun theo phn phi chun khng.
Gii: S dng phn mm Minitab 14 tnh cc i lng thng k trong thng
k m t..Kt qu thu c nh sau:
Variable Mean StDev CoefVar Minimum Median Maximum Skewness Kurtosis
Ni 18.99 9.91 52.17 2.00 16.00 59.00 1.22 2.51

72
 Biu tn sut xut hin cc gi tr trong tp s liu c dng:

Histogram (with Normal Curve) of Ni

25 Mean 18.99
StDev 9.907
N 80

20

15
Frequency

10

0
0 12 24 36 48 60
Ni

Gi tr skewness kh nh, ng biu din tn sut gn vi phn phi chun.

Nu s dng thut ton kim tra phn phi chun (Normality test) vi chun
Kolmogorov- Smirnov ta c cc gi tr: KS=0,119, P-value<0,01. Tr s P tnh c
nh hn mc ngha thng k =0,05 (5%) chng t c bng chng bc b gi
thit o. Ni cch khc, gin tip tha nhn tp s liu khng tun theo phn phi
chun.

4.3.1.2. So snh gi tr trung bnh tp hp v gi thc (chun Z)

Nu tin hnh cc th nghim lp li vi mu tng th v thu c gi tr trung
bnh tp hp l , lch chun tp hp bit l v gi thit thng k c s
dng l gi thit 2 pha (two- tail) th bi ton kim tra gi thit thng k c xem xt
qua cc bc sau:

- t mc ch th nghim: cn kim tra trung bnh tp hp thu c c

khc nhau c ngha vi gi tr thc cho trc 0 hay khng .

- t gi thit thng k l H0 : =0 , nu khng tho mn th > 0 hoc

<0 mc tin cy thng k cho trc.

- Quyt nh mc ngha , v chp nhn hay bc b H0 ty theo xc sut

tnh c.
- Quyt nh da trn mc tin cy thng k s dng trong trng hp phn
(x 0 )
phi chun: z N

-Tm phn phi mu ca gi tr thng k nu khng nh n ng.

73
 (x 0 )
( y phi gi nh rng z N c phn phi chun vi gi tr trung

bnh bng "khng" v phng sai bng "mt").
- Tnh gi tr Ztnh (hay Zthc nghim ) v so snh vi g tr Zbng (hay Zchun) trong
bng 4.3.
Bng 4.3: Gi tr Z cc mc tin cy thng k khc nhau.

Mc tin cy (%) 50 68 90 95 99 99,9

Z (2 sided) 0,67 1,000 1,645 1,960 2,576 3,29

Z (1 sided) 0,0 0,407 1,282 1,645 2,326 3,08

Nh vy nu n nh mc =0,05 th khi Ztnh <-1,96 hoc Ztnh >1,96 th loi b

gi thit o H0. Nu chn = 0,01 th xt khong Z tnh < -2,58 hoc Ztnh > +2,58.
Tuy nhin cn ch , phng php ny ch p dng cho tp s liu tun theo phn phi
chun.

Mt cch tng qut, nu Z tnh < Zbng th chp nhn gi thit o hay ni cch
khc v o khc nhau khng c ngha thng k. Cn nu s dng phn mm thng
k tnh ton xc sut th gi thit o c chp nhn nu Pvalue P ( thng chn
l 0,05 tc l khi gi thit ng m loi b th s mc sai lm loi mt ( tc l ging
nhau nhng kt lun l khc nhau) vi xc sut l %). Th d nu gi tr Pvalue=0,027
th c ngha l ch c 2,7% c hi o. Do vy, cn kt lun l o .
Ch : Khi cn so snh s khc nhau gia hai i lng th phn b xc sut
c dng l phn b 2 pha (2 sided). Trng hp hai i lng khc nhau th c th
dng phn phi xc sut 1 pha (1 sided) so snh gi tr no ln hn.

Th d 4.5: Vi cc s liu thu c khi phn tch hm lng MgO(%) trong mu xi

mng ng nht ti 40 PTN c l xi mng thuc h thng phng th nghim LAS-XD
ca B Xy Dng (th d 3.4) sau khi x thng k c x = 2,338 ( % MgO), lch
chun =0,0823, s th nghim N= 40. Hy so snh gi tr trung bnh thu c t 40
PTN c khc nhau c ngha vi gi tr c chp nhn tham chiu ca mu chun
cng b l 2,35 % MgO.
Gii: Vi s th nghim N= 40, tp s liu gi nh tun theo phn phi chun th

(x 0 ) 2,33 2,35
Z tnh N 40 1,53
0,0823

74
Nh vy Z<1,96 chng t khng c s khc nhau c ngha tin cy thng k
95%.

4.3.1.3. So snh gi tr trung bnh mu v gi tr c chp nhn (chun t).

Khi s th nghim lp li khng ln (thng n<30) th tp s liu tun theo phn
b l thuyt student. Do vy, chun student s c dng so snh xem c s khc
nhau c ngha gia gi tr trung bnh thng k (hay trung bnh thc nghim) x v gi
tr c chp nhn 0 hay khng. Do vy, phng php ny cng c dng so
snh kt qu trung bnh thc nghim vi gi tr chun trong mu kim tra cht lng
(quality control standard) v mu chun so snh (standard reference materials- SRM).
Cng tng nh nh khi so snh dng chun Z, php so snh ny da trn
khong tin cy ca gi tr trung bnh. Nu s khc nhau gia gi tr tm c x v gi
tr c chp nhn ln hn khng m bo o ca php o th th chng t c s
khc nhau c ngha gia hai gi tr ny tin cy thng k chn.
Nh vy, vi tp s liu ln c N >30 hoc khi bit lch chun tp hp th
Z .
s khc nhau khng c ngha gia hai i lng cn so snh l 0 th vi
N
t.S
tp s liu lp li nh c n <30 th s khc nhau ny l 0 x
n

t.S
Nh vy nu 0 x th xem nh 0 x (tc l chp nhn gi thit o
n
vi P=0,95%)

Mt cch khc, so snh 0 v x ngi ta tnh gi tr tthcnghim = 0 x. n /S

sau so snh vi gi tr tchun(P,f) (tra chun Student 2 pha).

Nu tthcnghim> tchun hoc Pvalue P th gi thit o b bc b tc l c s khc

nhau c ngha thng k gia gi tr trung bnh v gi tr c chp nhn.
Phng php ny cng c dng nh gi sai s h thng ca phng php
phn tch bng cch tin hnh phn tch lp li n th nghim t mu chun ( c gi
tr thc hay gi tr c chp nhn 0) v nh gi s sai khc gia gi tr x vi 0
x 0
bng cch tnh gi tr t theo biu thc t tnh n v so snh vi tbng (P,f) vi
S
f=n-1. Nu ttnh < tbng c th kt lun x khc 0 khng c ngha thng k hay phng

75
php ch mc sai s ngu nhin. Cn nu ttnh > tbng th phng php phn tch mc sai
s h thng.
Trong thc t cch so snh ny cn c p dng :
- nh gi ng ca phng php nghin cu bng cch so snh gi tr trung
bnh ca tp s liu lp li khi phn tch mu gi t to (thm mt lng cht phn
tch vo mu thc c xc nh l khng c cha cht phn tch) hay mu chun i
chng CRM bng phng php nghin cu ri so snh kt qu trung bnh t c vi
gi tr chun bit (vi mu t to) hay gi tr c chp nhn vi mu CRM.
- Xt nh hng ca nguyn t l (so snh khi c nguyn t l v khi khng c
nguyn t l)
- nh gi nh hng ca dung mi chun khi thm 1 dung mi khc.

Th d 4.6: Khi nghin cu phng php mi xc nh Se trong nc, cc tc gi

tin hnh phn tch lp li 5 ln mt mu nc my c thm Se chun mc hm
lng 50ng/ml. Kt qu thu c nh sau:
50,4 50,7 49,1 49,0 51,1 ng/ml
(Ngun t liu: Aller, A. J. and Robles, L. C. (1998). Analyst 123: 919).
Hy kim tra xem phng php nghin cu c mc phi sai s h thng hay
khng.
Gii: T tp s liu trn tnh c gi tr trung bnh l 50,06 v lch chun l
0,956. Nu chp nhn gi thit o l khng c sai s h thng v gi tr chun c
chp nhn l 0= 50 th

(50,06 50) 5
ttnh= 0,14
0,956

Tra bng tm gi tr chun t 2 pha P= 0,95 v f=4 c tbng= 2,78.

Vy ttnh<tbng nn gi thit o c chp nhn hay khng c bng chng kt
lun phng php mc sai s h thng.
Th d 4.7: Khi nghin cu phng php trc quang xc nh As(III) bng vi
thuc th bc ietylithiocacbamat sau khi hyrua ho bng k thut kh in ho,
cc tc gi phn tch As(III) trong mu t to (c mt As(V) sau 5 ln lp li. Kt
qu thu c (trung bnh lch chun) nh sau:

Mu As thm vo(g) As(III) tm thy(g)

76
 As(III) As(V)
Nc my 10 50 9,60,4
20 50 19,70,3
Nc bin nhn to 10 50 10,20,4
20 50 20 0,3
(Ngun t liu: M.H. Arbab-Zavar, M. Hashemi , Talanta, 52, (2000) 10071014.)
Hy kim tra xem phng php nghin cu c mc sai s h thng hay khng v
c nn p dng phn tch asen trong nc bin khng?

Gii: Tng ng vi 4 mc nng 0 thm vo trn nn mu thc, p dng cng

thc tnh gi tr t cho, ta c

(9,6 10) 5
+ mc thm 10 g As(III) vo mu nc my: ttnh= 2,24
0,4

(19,7 20) 5
+ mc thm 20 g As(III) vo mu nc my: ttnh= 2,24
0,3

+ mc thm 10 g As(III) vo mu nc bin nhn to:

(10,2 10) 5
ttnh= 1,11
0,4

+ mc thm 20 g As(III) vo mu nc bin nhn to:

(20 20) 5
ttnh= 0
0,3

Gi tr tbng(P=0,95;4)= 2,78. Nh vy c hai mc hm lng trn 2 nn mu thc

php phn tch u cho gi tr ttnh<tbng chng t khng c s khc nhau c ngha
gia gi tm c v gi tr thchay phng php khng mc sai s h thng v c th
dng xc nh As trong mu nc bin.

Nu s dng phn mm my tnh th ng thi vi gi tr ttinh c th thu c sc

xut. Cn c vo gi tr Pvalue v so snh vi = 0,05 kt lun chp nhn hay loi b
gi thit o.

Trong cc th d trn, gii theo phn mm MINITAB c th vo: Stat

Basic Statistics 1Z (nu N>30) hoc 1t (nu N<30); chn sample in column( vo s
liu theo ct (th d 4.6) hoc summaried data( vo s liu khi tnh thng k) (th
d 4.7 v 4.5). Kt qu thu c nh sau:

77
-Vi Th d 4.5:
Test of mu = 2.35 vs not = 2.35 ( im tra gi tr thc 2,35 hoc khng phi 2,35)
The assumed standard deviation = 0.0823 ( lch chun gi thit l 0,0823)
N Mean SE Mean 95% CI Z P
Trung bnh lch chun Khong tin cy Z tr s P
40 2.34000 0.01301 (2.31450, 2.36550) -0.77 0.442
- Vi th d 4.6:
Test of mu = 50 vs not = 50 (Kim tra vi gi tr thc =50 hoc khng phi 50)
Variable N Mean StDev SE Mean 95% CI T P
Bin Trung bnh lch chun sai chun Khong tin cy t tr s P
Se(ng/ml) 4 50.3250 0.8655 0.4328 (48.9477, 51.7023) 0.75 0.507
- Vi th d 4.7:
N Mean StDev SE Mean 95% CI T P
5 9.60000 0.40000 0.17889 (9.10333, 10.09667) -2.24 0.089

N Mean StDev SE Mean 95% CI T P

5 19.7000 0.3000 0.1342 (19.3275, 20.0725) -2.24 0.089

N Mean StDev SE Mean 95% CI T P

5 10.2000 0.4000 0.1789 (9.7033, 10.6967) 1.12 0.326

N Mean StDev SE Mean 95% CI T P

5 20.0000 0.3000 0.1342 (19.6275, 20.3725) 0.00 1.000

c ba th d trn, kt lun s khc nhau khng c ngha thng k th c th

xem xt cc kt qu thu c qua mt trong 3 cch sau y: gi tr thc c nm trong
khong tin cy (95%CI), gi tr Ztnh <1,96 hoc t tnh . c nh hn tbng =2,78 hay tr s
P >0,05. Nh vy, c th s dng phn mm thng k (kt lun theo tr s P) tnh Z, t
theo cng thc.

78
 Ch : Php so snh vi chun t 2 pha trn c dng nh gi s khc
nhau c ngha hay khng c ngha gia gi tr trung bnh thc nghim v gi tr c
chp nhn, tc l khng quan tm ti du ca chng. Tuy nhin, trong mt s trng
hp cn kim tra xem mt trong hai gi tr cn so snh l ln hn c ngha hay khng.
V d cn kim tra xem khi c mt xc tc tc phn ng c tng ng k khng, ion
cn c gy ra sai s h thng hay khng Khi cn s dng chun t mt pha.

Th d 4.8: Trong php chun axit bazo, sai s ch th thng gy ra sai s h

thng ca php phn tch v ch th i mu trc hoc sau im tng ng.
kim tra sai s ny, dng dung dch chun n axit 0,1M chun 25,00 ml dung
dch n ba z c nng chnh xc 0,1M v thu c cc kt qu sau (ml):
25,06 25,18 24,87 25,51 25,34 25,41
Hy kim tra xem c sai s h thng dng trong nhng kt qu ny khng kt lun
v i mu ch sau im tng ng.
Gii: Tp s liu c gi tr trung bnh l 25,228 ml, lch chun l 0,238 ml
t ga thit o H0 l khng c s khc nhau c ngha gia gi tr l thuyt l 25,00
ml v gi tr trung bnh th

ttnh== 25,228 25,00 6 2,35

0,238

so snh s ln hn c ngha ca gi tr trung bnh ngi ta kim tra ttnh vi

tbng (P=0,95; f= 5)= 2,02 ( chun t mt pha) cn tbng = 2,57 nu tra chun t hai pha.
Trong trng hp ny khi ttnh<tbng (chun 2 pha) th kt lun gi tr trung bnh v gi
tr thc sai khc nhau khng ng k tc l ng chp nhn c. Nhng gi tr
ttnh >tbng (chun t mt pha) nn kt lun rng c bng chng v s xut hin sai
s ch th dng i vi php chun .
Nu s dng phn mm MINITAB nh gi trung bnh c ln hn c ngha vi
gi tr thc hay khng th trong la chn so snh greater than hoc less than.
tp s liu trn, nu so snh hai gi tr trung bnh v gi tr thc khc nhau s c
Pvalue= 0,066 cn nu so snh gi tr trung bnh ln hn c ngha th Pvalue= 0,033, nu
chn nh hn c ngha th Pvalue= 0,967.
Nh vy nu xt Pvalue>0,05 chp nhn gi thit o th v d ny gi tr trung
bnh khng khc gi tr thc v cng khng nh hn nhng c xem ln hn c
ngha so vi gi tr thc.
Kt lun ni trn c v mu thun v khng khc nhau c ngha m li chp nhn l

79
ln hn ng k vi gi tr kia.Nhng cn hiu rng kt lun ch da trn chun thng
k v ty thuc vo mc chc chn ca n theo hng xc x. Tuy nhin, trong
trng hp ny cn nghi ng sai s h thng dng, ni cch khc quyt nh da trn
chun 2 pha hay mt pha cn thc hin trc khi th nghim. Thng thng trong
thng k lin quan n s liu th chun hai pha thng c s dng hn.

4.3.2. So snh vi hai tp s liu lp li (2 samples)

4.3.2.1. So snh phng sai ca hai tp s liu lp li (chun Fisher : 2 2 )

Chun thng k ngoi vic s dng kim tra sai s h thng (bng cch kim
tra s sai khc ca gi tr trung bnh vi gi tr thc) cn c dng kim tra sai s
ngu nhin ca hai tp s liu. Khi , chun Fisher s c dng so snh chm
(precision) ca hai tp s liu c tin hnh bi hai ngi th nghim khc nhau hai
PTN khc nhau hoc hai phng php khc nhau... Kt lun s phi ch ra l phng
php A chm hn phng php B (dng chun 1 pha) hay chm ca 2 phng
php A, B l khc nhau (chun 2 pha)
Gi s c hai tp hp kt qu phn tch thu c t hai ngi phn tch, hai PTN
phn tch hoc hai phng php vi hai gi tr phng sai l 1 2 v 2 2 , bc t do
tng ng f1 v f2. Nh vy, cn gii p cu hi 1 2 v 2 2 c phi l phng sai ca
cng tp hp khng?

Vy gi thit thng k H0 trong trng hp ny l 1 2 2 2 2 .

Vi cc tp s liu ca mu thng k c s th nghim xc nh v khng ln th

bi ton tr thnh so snh hai gi tr S1 2 v S 2 2 .
2
S1
Nu "gi thit o" tho mn th t s 2
phi tun theo phn phi chun Fisher
S2
vi cc bc t do l f1 = n1-1 v f2 = n2-1 v gi tr F c tnh theo cng thc:
2
S1
Ftnh= 2
s tin gn ti 1 (ch lun tnh vi F>1)
S2

Khi , s bc b gi thit kim tra nu Ftnh > Fbng (P, f1, f2) (chun 2 ui: 2-
tailed-test) hoc P < P. Ni cch khc, khi hai phng sai S1 2 v S 2 2 c s khc
nhau c ngha hay chm cc s liu thc nghim gia hai mu thng k (hoc hai
phng php) l khc nhau.

80
 Nu lp li hai phng php khc nhau th c th kim tra xem phng php
A c chm tt hn hay km hn phng php B (kim tra chun 1 ui: one-tailed-
test). Nu Fthc nghim > Fchun (P,f1, f2) th c th kt lun phng php A km chnh xc
hn phng php B.

Th d 4.5: nghin cu ng dng phng php mi xc nh nhu cu oxi ha

hc (COD) trong nc thi, cc tc gi so snh lp li ca phng php nghin
cu vi phng php thiu chun( phng php thy ngn). Cc kt qu lp li vi
cng mu nc thi thu c nh sau:
Phng php tiu chun: trung bnh : 72 (mg/l), S1= 3,31mg/l f1= 8
Phng php nghin cu: trung bnh : 72 (mg/l), S2 =1,51 mg/l; f2=12
(Ngun s liu: Ballinger, D., Lloyd, A. and Morrish, A. 1982. Analyst 107: 1047)
Hy kim tra xem chm ca phng php nghin cu c hn hn c ngha so
vi phng php tiu chun hay khng?
Gii: Tnh F theo cng thc F= 3,312/ 1,512=4,80
2
S1 4,3 2
Ta c F= 2
4,19
S2 2,12

Tra bng chun F ta c Fbng (0,95;7;7)=3,78

Vy Ftnh = 4,19 > 3,78 nn c th kt lun rng lp li ca hai php o khc
nhau c ngha.
kim tra phng sai ca phng php tiu chun ln hn c ngha so vi
phng sai ca phng php nghin cu hay khng th cn so snh Ftinh vi Fbng
dng chun 1 pha. Vi Fbng (P=0,95; 7; 7)= 2,78< Ftinh chng t lp li ca phng
php nghin cu ln hn c ngha so vi phng php tiu chun.

4.3.2 2. So snh 2 gi tr trung bnh thc nghim (Chun Student: 2t).

Gi s c hai gi tr trung bnh x A v x B thu c t hai dy php o ca cng 1

mu ban u vi s th nghim lp li l nA v nB c lp nhau. Gi thit o cn kim
tra l x A v x B ging nhau hay s khc nhau gia x A v x B l do sai s ngu nhin
gy ra? iu c ngha l cn kim tra xem c s khc nhau c ngha gia hiu ( x A
- x B ) v gi tr :0 hay khng.

Cch lm:

81
 Bc 1: Kim tra xem lp li ca hai tp s liu (qua phng sai S A 2 v S B 2 )
l ng nht hay khc nhau c ngha thng k? (chun F).

- Nu S A 2 v S B 2 ng nht (khc nhau khng c ngha) th tnh lch chun

gp Spooled theo bc 2 v kim tra theo chun t.
-Nu hai phng sai khng ng nht (khc nhau c ngha) th tin hnh bc 3,
s dng c phng sai ca A v B tnh gi tr t .

Bc 2: Nu S A 2 v S B 2 ng nht th tnh lch chun hp nht Spooled ca

hiu 2 gi tr trung bnh x A v x B vi s th nghim nA v nB <30.
nA nB

( x Ai x A ) 2 ( xBi xB ) 2 (n A 1) S A (nB 1) S B2
2
Sx S pooled i 1 1
(
A1 x B
n A nB 2 n A nB 2
4.4)

Khi s php o nh th hiu x A x B l i lng ngu nhin theo phn phi

t.

x A xB 1
Do , t tnh
S pooled 1 1

n A nB

v so snh vi tchun(P,f) vi bc t do f=(nA-1) + (nB-1)= nA+nB-2 (v c 2 tp s

liu vi s th nghim l nA v nB v hai gi tr trung bnh c tnh cho mi tp s
liu)

Nu tthcnghim > tchun(P,f) (tra chun t 2-pha) th s khc nhau gia x A v x B l

c ngha thng k v ngc li.

Nu tthcnghim > tchun(P,f) (tra chun t 1-pha) th s khc nhau gia x A > x B l c
ngha thng k.

Cng c th kt lun da vo Pvalue<0,05 th s khc nhau gia x A v x B l c

ngha thng k.

Bc 3: Nu S A 2 v S B 2 khc nhau c ngha th tnh gi tr ttnh theo cng thc

sau:

82
 x A xB
ttnh
sA2 sB2

nA nB
So snh vi ga tr tchun tra bng vi P=0,95 v bc t do f tnh theo cng thc
2
S A2 S B2

f A2 B
n n
2
sau a gi tr f v s nguyn.
SA 2
SB

n A nB
n A 1 nB 1

Lu : Cc phn mm my tnh cng thng c s khc nhau khi ly gi tr

nguyn cho f. V d nu tnh c f= 4,7 th MINITAB s s dng gi tr f=4 cn
EXCEL th li lm trn f=5).

Th d 4.6: Trong phng php xc nh thic trong thc phm, ngi ta tin
hnh un si hi lu mu vi HCl cc thi gian khc nhau. Kt qu thu c nh
sau:
Thi gian un hi lu( pht) Hm lng thic (mg/kg)
30 55; 57; 59; 56; 56; 59
75 57; 55; 58; 59; 59; 59
(Ngun s liu: Analytical Methods Committee. 1983. Analyst 108: 109)
Hy so snh xem hai gi tr trung bnh hm lng thic t c bi cng mu
phn tch khi un mu vi HCl cc thi gian khc nhau c khc nhau khng?
Gii:- Tnh cc i lng thng k c trng

+ Thi gian 30 pht : x = 57,00 ; phng sai SA2 = 2,80

+ Thi gian 75 pht x = 57,83 ; phng sai SB2 = 2,57

- Trc tin so snh hai phng sai:
2
SA 2,80 2
Ftnh= 1,04 so snh vi Fbng(P=0,95, fA = fB=5)= 5,05
S 2 B 2,57 2

Nh vy hai phng sai ny khc nhau khng c ngha thng k tin cy

thng k 95%

83
 - So snh hai gi tr trung bnh t c hai thi gian khc nhau bng
chun student p dng cho hai phng sai nh nhau:

x A xB 1
Ta c t tnh vi
S pooled 1 1

n A nB

(n A 1) S A (n B 1) S B2 5.2,80 2 5.2,57 2
2
Sx S pooled 1,65
A1 x B
n A nB 2 10

57,00 57,83
Do ttnh= = 0,88
1 1
1,64
6 6

Vi f=10 v P=0,95, chun 2 pha th tbng= 2,23>ttnh. Do vy, khng c s

khc nhau c ngha ca hai gi tr trung bnh thu c khi tin hnh x l mu ti
hai thi im khc nhau. Ni cch khc, ch cn un mu hi lu vi HCl trong 30
pht.
Trong th d ny nu s dng phn mm MINITAB, u tin cn kim tra s sai
khc (nu c) gia hai phng sai bng cch vo Stat Basic Statistics 2
variances sau khi nhp hai ct s liu cho hai tp s liu lp li l C1 v C2.
Trong ca s mc snh hai phng sai, chn phn vo s liu theo ct khc nhau
(samples in differen columns), mc option chn confident level l 95%, sau bm
OK.
Kt qu thu c nh sau:
Test for Equal Variances: C1, C2

95% Bonferroni confidence intervals for standard deviations

N Lower StDev Upper

C1 6 0.882753 1.50555 4.30728
C2 6 0.939356 1.60208 4.58347
F-Test (normal distribution)
Test statistic = 0.88, p-value = 0.895
Nh vy, vi 6 th nghim lp li ca mi tp s liu, gi tr Ftnh= 0,88 (cso th
t tra bng tm Fbng v tr s P l 0,895>0,05. Vy c th kt lun hai phng sai

84
khc nhau khng c ngha.
Sau khi c kt qu kim tra hai phng sai, kim tra s ging hay khc nhau
ca hai gi tr trung bnh, vo phn Stat Basic Statistics 2t. Trong ca s ny
cng chn vo s liu theo ct khc nhau v chn c mc gi thit hai phng sai
nh nhau (Asume equal variances). Nu hai phng sai khc nhau ( theo kt lun
phn so snh hai phng sai ) th khng chn mc ny.
Kt qu thu c l:
Two-sample T for C1 vs C2

N Mean StDev SE Mean

C1 6 57.00 1.67 0.68
C2 6 57.83 1.60 0.65

Difference = mu (C1) - mu (C2) (hiu hai gi tr trung bnh)

Estimate for difference: -0.833333
95% CI for difference: (-2.940597, 1.273931)
T-Test of difference = 0 (vs not =): T-Value = -0.88 P-Value = 0.399 DF = 10
Both use Pooled StDev = 1.6381

Nh vy, nu cn c vo gi tr Fbng hoc Pvalue= 0,399>0,05 th kt lun rng

hai gi tr trung bnh l khc nhau khng c ngha thng k.
Th d 4.7: so snh 2 phng php xc nh hirocacbon a vng thm
(phng php hunh quang v phng php UV) trong t, ngi ta tin hnh cc
php phn tch lp li 7 ln v 6 ln vi mi phng php tng ng. Gi tr trung
bnh thu c ca phng php hunh quang l 28,00 mg/kg, lch chun S = 0,30
mg/kg; ca phng php UV l 26,25 mg/kg; S= 0,76 mg/kg. Hi gi tr trung bnh
ca hai phng php c khc nhau c ngha hay khng?.
Gii: - Kt qu tnh Ftnh= 0,762/0,302 = 6,42 (trong phn mm MINITAB nhp
Stat Basic Statistics 2 variances, chn summarized data vo s liu dng
i lng thng k cho ct 1 l n= 6 v phng sai l 0,762= 0,5776 v ct 2 c n=7,
phng sai l 0,302= 0, ta c Ftnh= 6,42 v Pvalue= 0,043 < 0,05. Vy hai phng sai

85
 l khc nhau c ngha thng k.
- Trong phn so snh hai gi tr trung bnh, tnh t theo cng thc sau:

x A xB 28,00 26,25
ttnh 5,29
sA2 sB2 0,5776 0,09


nA nB 6 7
Khi so snh vi ga tr tchun tra bng vi P=0,95, bc t do f tnh theo cng
2
S A2 S B2

f A2 B
n n
thc 2
6 ta c tbng= 2,45.
SA 2
SB

n A nB
n A 1 nB 1

Kt qu tnh theo phn mm my tnh, (khng chn mc gii thit phng sai bng
nhau) nh sau:
Two-Sample T-Test and CI

Sample N Mean StDev SE Mean

1 7 28.000 0.300 0.11
2 6 26.250 0.760 0.31

Difference = mu (1) - mu (2)

Estimate for difference: 1.75000
95% CI for difference: (0.94169, 2.55831)
T-Test of difference = 0 (vs not =): T-Value = 5.30 P-Value = 0.002 DF = 6
Nh vy, vi Ftnh> Fbng hoc Pvalue<0,05 c th kt lun rng hai gi tr trung bnh
Cca cng mt mu t c bi 2 phng php phn tch l khc nhau c ngha
thng k. Ni cch khc, nu xem mt trong hai phng php l phng php tiu
chun th phng php cn li c ng khng chp nhn c. (Tuy nhin cng
cn ch ng ny mi ch c kim tra mt mc nng trong th nghim
trn)

86
 Trong thc t, vic so snh hai gi tr trung bnh c th p dng khi c hai mu
cn kim tra v c tin hnh so snh tay ngh hai ngi phn tch, ng ca
hai phng th nghim vi cng mu phn tch, nhng khng thch hp lm so snh
hai phng php phn tch v y ch l vic so snh hai gi tr trung bnh thc nghim
vi s mu hn ch, ti mt mc hm lng ca cht phn tch, m khng c trng
cho ton b vng nng kho st. Vic so snh phng php nghin cu vi 1
phng php khc (thng l phng php tiu chun) nh gi phng php phn
tch phi c thc hin nhiu mc nng theo phng php so snh tng cp
hoc so snh dng th.
4.4. So snh tng cp
Gi s chng ta nghin cu phng php A phn tch cht cha bit no .
Sau khi tm c cc iu kin ti u ca php xc nh, cn tin hnh nh gi
phng php phn tch vi phng php tiu chun. Nu s dng phng php so
snh hai gi tr trung bnh ca cng mu s khng thch hp v kt qu ph thuc vo
nh hng ca hm lng cht nn khc nhau c trong mu phn tch. Thng thng
cc kt qu phn tch ch cha sai s ngu nhin. Tuy nhin, chnh s khc nhau v
thnh phn nn mu v nh hng ca cc cht i km khc nhau vi mi phng
php khc nhau l khc nhau. D vy khi so snh mt mc nng cht phn tch
kt qu cho la hai phng php nh nhau nhng li c s khc nhau khi so snh cc
mc hm lng khc, c ngha l c th xut hin sai s h thng gia hai php o.
Khi , cn tin hnh th nghim theo tng cp vi nhiu mc hm lng khc nhau
thay i hm lng cc ion i km. Vi mi mu phn tch khi s c tin
hnh bi ng thi hai phng php: Phng php ang nghin cu v phng php
tiu chun. Cc gi tr thc nghim thu c ln lt l x1A, x1B; x2A, x2B..xiA v xiB..
Cc kt qu thu c c th so snh theo phng php tng cp hoc phng php
th (s xt trong chng 6).
Trong php so snh tng cp ngi ta s dng chun t tng cp (a paired- t-
test). Gi thit o trong trng hp ny l khng c s khc nhau c ngha v kt qu
phn tch cng hm lng cht phn tch trong cng mu ca hai phng php. Ni
cch khc, cn so snh hiu s trung bnh ca hai tp s liu c khc 0 c ngha hay
khng.
Cch lm: - Tnh lch gia tng cp gi tr theo cng thc di= xAi-xBi. Cc gi
tr di ny c gi nguyn du + hoc -.

- Tnh gi tr d (l trung bnh s sai khc gia cc cp gi tr di) theo cng thc

87
 n

d i
d i 1

- Tnh lch chun c on ca s sai khc ny theo cng thc:

sd
(d i d) 2
n 1

(d ) n
- Tnh gi tr t tng cp theo cng thc:
t calc
sd
Sau so snh gi tr ttnh v gi tr tbng c tra trong bng chun t vi tin
cy P=0,95 v (n -1 ) bc t do.

Nu ttinh<tchun hay gi tr Pvalue > P=0,05 th gi thit o c chp nhn, c ngha l

hai phng php khng c s khc nhau c ngha.

Th d 4.8: Kt qa phn tch hm lng Hg (g/l) trong mu nc bt bng phng

php FIA (Phng php A) v phng php thng thng (Phng php B) trong 20
mu thu c nh sau:

STT 1 2 3 4 5 6 7 8 9 10

PP A 47,5 29,5 74,4 5,5 30,9 9,8 25,5 2,9 8,6 23,8

PP B 51,8 27,4 71,6 6,0 29,2 8,0 23,2 3,2 8,8 23,5

STT 11 12 13 14 15 16 17 18 19 20

PP A 84,4 147,0 30,6 19,9 33,9 25,0 107,6 18,0 125,3 84,9

PP B 87,9 150,5 29,8 19,8 29,0 25,3 107,5 15,1 134,6 81,4

(Ngun s liu: T.Gao, J. Baasner, M.gradl, A. Kistner, Analytical Chimica Acta, 320,
(1996), 171-176.)
Hy dng phng php so snh tng cp xem cc kt qu xc nh ca hai phng
php c trng nhau khng?
Gii: Cch 1: Tnh theo cng thc:
- lch gia hai phng php A v B ln lt l
di: -4.3 2.1 2.8 -0.5 1.7 1.8 2.3 -0.3 -0.2 0.3 -3.5 -3.5
0.8 0.1 4.9 -0.3 0.1 2.9 -9.3 3.5

88
 nn lch trung bnh l: d =0,07
lch chun c on cho cc lch Sd= 3,236

0,07. 20
Do vy ttnh= 0,096
3,236

Kt qu tra bng tbng(P=0,95; f=19)= 2,1. Nh vy ttnh<tbng chng t phng

php A c ng nh phng php tiu chun hay kt qu phn tch theo phng
php A l ph hp.
Cch 2: X l s liu theo phn mm MINITAB.
Nhp s liu vo hai ct. Vo Stat Cho kt qu tnh theo phn mm MINITAB 14.0
nh sau: Stat Basic Statisticspaired t. Trong ca s ny vo nhp s liu theo ct
( Samples in columns), chn OK. Kt qu thu c nh sau:
N Trung bnh lch chun sai chun
ppA 20 46.7500 42.2895 9.4562
ppB 20 46.6800 43.9953 9.8376
Khc nhau: 20 0.070000 3.235836 0.723555
95% CI for mean difference: (-1.444418, 1.584418)
T-Test of mean difference = 0 (vs not = 0): T-Value = 0.10 P-Value = 0.924
Nh vy Pvalue>0,05 chng t kt qu hai phng php t c l nh nhau.
Th d 4.9: Nghin cu xc nh ng thi nitrat v nitrit trong mu nc bng
phng php ng hc xc tc trc quang s dng h phn tch dng chy (FIA), cc
tc gi tin hnh nh gi phng php phn tch bng cch phn tch ng thi
mt mu vi cng hai phng php (phng php nghin cu v phng php tiu
chun vi thuc th Griss). Kt qu xc nh hm lng nitrit thu c nh sau:

Th Mu Hm lng thm Phng php FIA Phng php tiu

nghim vo (g/ml) tm c chun tm c
(g/ml) (g/ml)

1 0,000 0,00015 0,0012

2 Nc 0,040 0,0392 0,0398
3 sng 0,060 0,0615 0,0602
4 0,080 0,0783 0,0806
5 0,100 0,1006 0,0994

89
 6 Nc 0,000 0,004 0,0006
7 my 0,040 0,0397 0,04
8 0,060 0,0567 0,059
9 0,080 0,0776 0,078
10 0,100 0,105 0,101

11 Xc xch 0,000 0,003 0,0003

12 0,040 0,037 0,0405
13 0,060 0,055 0,0601
14 0,080 0,0803 0,0799
15 0,100 0,103 0,0997

( Ngun s liu: A. A.Enfasi, B. Rezaei, S. Nouroozi. Analytical Sciences; 2004;

vol.20; 1749-1753)
Hy th kim tra xem kt qu phn tch vi cc loi mu khc nhau v cc hm
lng cht phn tch khc nhau t c bi hai phng php c nh nhau hay
khng?
Gii: so snh hai phng php phn tch, c th s dng phng php sp snh
tng cp vi chun t cho c 15 th nghim. Kt qu x l s liu theo phn mm
MINITAB nh sau
Paired T-Test and CI: C1, C2
N Mean StDev SE Mean
C4 15 0.056070 0.035583 0.009188
C5 15 0.056020 0.035310 0.009117
Difference 15 0.000050 0.002667 0.000688
95% CI for mean difference: (-0.001427, 0.001527)
T-Test of mean difference = 0 (vs not = 0): T-Value = 0.07 P-Value = 0.943
Nh vy, kt qu t c bi hai phng php khi so snh theo chun t tng cp c
Pvalue = 0,943>0,05 nn c th kt lun phng php FIA ang nghin cu cho kt qu
ph hp vi phng php tiu chun khi phn tch cc mc nng nitrit khc nhau
v cc loi mu khc nhau.

Ch : Phng php so snh tng cp nu trn khng yu cu chm ca 2 phng

php nh nhau nhng gi thit rng cc gi tr lch ca 2 tp s liu d i tun theo

90
phn b chun. Cc s liu ca mi mu phn tch c th l s liu lm 1 ln hoc s
liu lp li (n vi mi phng php lm lp li m v n th nghim khc nhau.

91
Chng 5: PHN TCH PHNG SAI

Trong chng trc chng ta xt bi ton so snh gi tr trung bnh ca hai tp

s liu thng k trong cng tp hp bng cch dng chun t. Vic so snh s chnh xc
hn nu cng nhiu tp s liu trong tp hp c xt n. Tuy nhin, nu cn so snh
nhiu hn hai gi tr trung bnh th chun t khng cn ph hp. V d cn so snh s
bin i hm lng trung bnh cc iu kin nhit khc nhau, bi cc PTN khc
nhau, bi nhiu phng php khc nhau Thc nghim s thy cc kt qu ny lun
km theo ngun sai s ngu nhin trong mi tp s liu thng k ( l sai s gy ra do
s sai khc gia cc kt qu o lp li trong cng iu kin). . Ngoi ra, mt ngun sai
s na l do nhng yu t nh hng c nh gy ra ( do s thay i t nhit ny
nhit khc, PTN ny sang PTN khc, phng php ny v phng php khc)
Do vy cn xt n nh hng ca cc yu t c nh ny trong cng mu thng k v
gia cc mu thng k trong cng tp hp. Phng php thng k ny thng c
gi l phn tch phng sai (analysis of variance- ANOVA) hn l s dng thut ng
phn tch trung bnh a nhm (multi-group means analysis).N cho php tch hay c
lng c bt k nhng nguyn nhn khc nhau gy ra s dao ng cc s liu
Nh vy, c th ni, phn tch phng sai l phn tch tc ng ca mt hay
nhiu yu t c nh n kt qu th nghim qua tham s phng sai. c th l nh
hng ca mt hay nhiu yu t hay nh hng tng h ca nhng yu t . Ngoi
vic dng so snh nhiu ga tr trung bnh, ANOVA cn c dng nh gi nh
hng ca nhng ngun sai s khc nhau n dy kt qu th nghim t nh gi
c nh hng ca cc ngun sai s n s phn b mu .
Ngun sai s c chia thnh hai dng:
- nh hng ngu nhin ca yu t thm vo.
- nh hng c nh hay c kim sot ca th nghim.
Ni cch khc, phn tch phng sai l lm th nghim theo qui hoch nh trc
nhm kho st nh hng c ngha ca cc yu t n kt qu th nghim qua vic
nh gi phng sai theo chun Fisher.
Nu ch so snh hai gi tr trung bnh th phn tch phng sai tr thnh php so
snh s dng chun t.
Cc bi ton v phn tch phng sai c 3 dng ch yu:
- So snh nhiu ga tr trung bnh: thc cht l bi ton mt yu t, k mc th
nghim, mi mc nghin cu lp li n ln (one way ANOVA or one - factor ANOVA).

92
 - Bi ton hai yu t A v B, yu t A c k mc th nghim, yu t B c m mc
th nghim, mi mc ca A v B lm lp li n ln (two-way ANOVA).
- Bi ton 3 yu t tr ln (Latin squares).

5.1. So snh mt s gi tr trung bnh

Gi s cn so snh s khc nhau c ngha thng k hay khng ca cc gi tr
trung bnh mu x1 , x2 , x3 , xk , trong cng tp hp. Cc trung bnh mu ny
thu c t n th nghim trong mi mu thng k.

Mu thng k 1: x11 , x12 , ., x1n v c gi tr trung bnh l x1

Mu thng k 2: x21 , x22 , ., x2n v c ga tr trung bnh l x 2

Mu thng k th i : xi1, xi2 ,., xij v c ga tr trung bnh l xi

Mu thng k k : xk1 , xk2 , , xkn v c ga tr trung bnh l x k

Gia cc gi tr trung bnh ny c lch nht nh so vi gi tr trung bnh

k

i1
xi
chung hay cn gi l trung bnh tp hp : X
k
Gi thit o trong trng hp ny l cc mu c ly t cng tp hp c trung
bnh mu l v phng sai tp hp l 2 . Ni cch khc cn kim tra gi thit o l
= x1 = x 2 == x k . Khi cc mu thng k thuc cng tp hp th phng sai trong
mi mu (within-sample) phi chnh l phng sai gia cc mu (between sample).
Vic so snh ny c thc hin qua chun F bng cch tnh t s hai phng sai gia
cc mu thng k v trong cng mu thng k ri so snh vi gi tr trong bng F
(hoc so snh ga tr P value vi ) a ra kt lun thng k.
* Phng sai trong cng mu thng k:

n n n

(x1 j x1)2
j 1
(xkj xk ) 2
j 1
(x
j 1
ij xi ) 2
S1 Sk S i1
2 2 2

n 1 n 1 n 1
Mi mu c n th nghim lp li, do c n-1 bc t do. Tng s mu thng k l
k mu. Vy bc t do i din cho tt cc cc mu l f0 =k(n-1).

93
 Do vy, phng sai trong cng mu (within-sample estimation of variance/
within-sample mean square) s l:
k k n

Si
2
(x
i 1 j 1
ij xi )2
S 2 within i 1

k k (n 1)

*Phng sai gia cc mu: (between-sample estimation of variance)

Nu cc gi t trung bnh mu c rt ra t cng tp hp c phng sai mu tng th
l 2 th phng sai do s sai khc ca mi gi tr trung bnh mu v trung bnh mu
v trung bnh chung l
k

(x i X )2
S 2 sample mean i 1
k 1
Tuy nhin, khi gi tr trung bnh chung thay i th phng sai mu tng th 2 cng
thay i theo nn phng sai gia cc mu (phng sai gp gia cc nhm):
k
k ( xi X ) 2
S 2 between i 1
bc t do f1=k-1
k 1
Nu gi thit o l ng th hai phng sai phi khng khc nhau hay nh nhau.
Cn nu ga thit o l sai th phng sai gia cc mu phi ln hn phng sai trong
cng mu thng k.
Ni cch khc ta tnh bi thc:

S 2between
Fcalculate 2 v so snh vi ga tr Fbng(P=0,95; f1=k-1; f0=k(n-1)
S wwithin
Nh vy nu Ftnh >Fbng th gi thit o b loi b, tc l cc ga tr trung bnh
ca cc mu thng k l khc nhau c ngha. iu ny c th do c mt gi tr trung
bnh khc vi cc gi tr trung bnh khc, hoc cc gi tr trung bnh khc ln nhau
hoc cc gi tr trung bnh phn thnh hai nhm ring bit. Mt cch n gin tm
ra nguyn nhn s khc nhau gia cc gi tr trung bnh l sp xp cc ga tr trung
bnh theo th t tng dn v so snh s khc nhau ca hai gi tr trung bnh cnh nhau
vi i lng biu th s khc nhau c ngha ti thiu (A). Nu hiu hai ga tr trung
bnh cnh nhau ln hn A th c ngha chng gy ra s khc nhau trong tp hp.

94
 2
i lng A c tnh theo cng thc sau: AS .t( p , f 0 )
k

Vi S l lch chun c on trong cc mu S S

2
within

t l gi tr chun student tra bng vi tin cy thng k P=0,95 v bc t do f0=

k(n-1).
Th d nu c 4 gi tr trung bnh cu 4 mu A, B, C, D ln lt l 92 , 97, 99 v
102. Tnh ton trn cho thy chng khc nhau c ngha . S th nghim lp li trong
mi mu l 3 v S= 3 th gi tr A= 3,26.
Hiu ca hai ga tr trung bnh gia hai mu sai khc nhau nhiu nht l 5 > 3,26.
Vy nguyn nhn cc gi tr trung bnh mu ny khc nhau l do hai mu A v D khc
nhau c ngha gy ra.
So snh cc ga tr trung bnh cng c th p dng cho bi ton c hai yu t v
nh ga c nh hng tng h ca hai yu t ny.

Th d 5.1: Mt PTN A cn ch to mu chun xi mng xc nh hm lng cc

kim loi theo phng php hunh quang tia X (XRF). Mu chun c ly ngu nhin
t cc bao xi mng, sau nghin nh v trn tht u ri gi i phn tch cc
PTN. nh gi ng u ca mu ngi ta chia mu chun ban u (c xem
nh tp hp) thnh 8 mu nhv gi n 8 PTN phn tch. Mi PTN phn tch hm
lng Al (tnh theo phn trm Al2O3) trong mi mu vi 6 ln lp li. Kt qu thu
c nh sau:

PTN/lp 1 2 3 4 5 6
li

1 A 4,5 3,9 4,9 5,3 5,1 4,9

2 B 5,3 5,1 4,8 5,0 4,6 4,9

3 C 5,5 5,2 5,0 4,7 4,6 5,2

4 D 4,9 5,2 5,2 4,7 4,3 4,5

5 E 5,3 5,6 5,7 5,1 4,9 5,1

6 F 4,9 4,6 5,1 5,3 4,8 5,0

95
 7 G 5,2 4,7 4,9 5,1 5,7 5,3

8 H 4,9 5,0 5,2 5,4 5,6 5,7

Hy dng phng php so snh cc gi tr trung bnh kim tra xem gi tr trung
bnh gia cc mu c ging nhau khng v kt lun thnh phn mu c p ng yu
cu v ng nht khng.
Gii: - Cch 1: Dng cc cng thc nu trn tnh ton v kt lun da vo
Ftnh v Fbng .
- Cch 2: Nhp s liu vo phn mm MINITAB di dng 2 ct. Ct C1 l %
Al2O3 c nhp theo th tu t tri sang phi v t trn xung di (ht 6 s liu ca
PTN A sau n 6 s liu ca PTN B ). Ct C2 nhp yu tnh hng l PTN, cc
s liu c k hiu l 18, trong vo theo th t ttrn xung di l 1 1 1 1 1 1;
2 2 2 2 2 2 8 8 8 8 8 8 .
x l s liu, vo Stat->ANOVA-> Analysis of Means, nhp response l
ct C1 cha %Al2O3. Trong Distribution of data chn Normal vi factor 1 l ct
C2 cha cc k hiu cc mu thng k, chn alpha-level l 0.05, v chn OK. Kt qu
thu c nh sau:

One-Way ANOM for Al2O3(%) by PTN

Alpha = 0.05

5.50

5.393

5.25

5.025
Mean

5.00

4.75
4.657

4.50
1 2 3 4 5 6 7 8
mau

Trong th trn, ng trung tm chnh l trung bnh chung (grand mean), vi

X =5,025, hai ng pha ngoi l gii hn quyt nh (decision limit), c trng cho
khong tin cy ca gi tr trung bnh chung. Nu cc im ch gi tr trung bnh ca

96
cc mu thng k nm trong gii hn quyt nh th kt lun l khng c bng
chng ni rng cc gi tr trung bnh mu l khc nhau. Ni cch khc cc mu
ny u thuc cng tp hp hay mu chun ban u tho mn tnh ng nht.

5.2. Phn tch phng sai mt yu t (one-way ANOVA)

Gi s vic thay i yu t A (c th l nng ion cn, phng th nghim trong
sn xut, iu kin t nhin, nhit ) c nh hng n kt qu thc nghim (nh
hp th quang, chiu cao pic, bn sn phm, nng ). Mc th nghim c th
l cc mc nng , cc phng sn xut khc nhau, cc cng on sn xut khc nhau,
nhit khc nhau). Bi ton ny l bi ton tng t nh khi so snh cc gi tr
trung bnh nhng kt lun s ging hay khc nhau ca cc gi tr trung bnh s cho
php rt ra c yu t A ang xt c nh hng hay khng n cc ga tr trung bnh
ny.
Cch tin hnh: nghin cu nh hng ca yu t A, ngi ta tin hnh k mc
th nghim (xem nh k nhm), mi mc (hay mi nhm) th nghim lp li n ln. Kt
qu th nghim l cc gi tr yij (vi i=1k v j= 1 n) c ghi vo bng 5.1.
Bng 5.1: Qui hoch thc nghim phn tch phng sai 1 yu t, k mc th nghim,
mi mc th nghim lp li n ln.

Mc S A1 a2 a3 ... ai ... ak
ln TN

1 y11 y21 y31 yi1 yk1

2 y12 y22 y32 yi2 yk2

3 y13 y23 y33 yi3 yk3

...

j y1j y2j y3j yij ykj

...

N y1n y2n y3n yin ykn

97
 so snh s sai khc gia cc kt qu th nghim khi thay i cc mc ca yu
t A, ngi ta so snh phng sai do s thay i cc mc nghin cu gy nn vi
phng sai chung 2 ca th nghim xem chng c khc nhau ng tin cy hay khng.
Nu s khc nhau khng ng tin cy th c th kt lun yu t A s nh khng ng
k n kt qu th nghim v ngc li.
Trng hp khng c s khc nhau gia cc gi tr trung binhg tc l tt c cc
s liu thuc cng tp hp th phng sai chung ca th nghim c th nghim c th
tnh theo cng thc:

( x ij X )2
2
i j

k (n 1)

Tuy nhin, cch tnh ny li khng c s dng trong Ha phn tch v vic tnh
ton ph thuc vo c s sai khc cc s liu ring r trong cng tp s liu v trong
cc nhm s liu khc nhau v c mi quan h gia tng cc sai khc v ngun gy ra
s sai khc nh sau:
Tng bnh phng cc s sai khc= tng bnh phng sai khc gia cc th
nghim lp li trong mt nhm v tng bnh phng s sai khc gia cc nhm l:
k

( xij X ) 2 = k ( xi X ) 2 +
i j i 1
( x
i j
ij xi ) 2

Do vy, phng sai c trng cho s sai khc gia cc th nghim lp li trong
nhm, gia trung bnh cc nhm vi nhau c th tm tt theo bng sau:
Bng 5.2: Bng tnh phng sai khi nghin cu nh hng ca yu t A

Ngun bin thin Bc t do Tng cc bnh phng Trung bnh bnh

(Source of variation) (Degree of (Sum of squares) phng
freedom) (mean of square)
(x i x) 2
(f) (S2)

Gia cc nhm k-1 T 2

i SS A
SA
T2 2
SS A i

(between- samples) n kn k 1
(do yu t A gy nn)

Trong cng nhm k(n-1) T 2

i
STN2=
SS B

(within-sample)
SSTN= xi j
2
ij - i
n
k (n 1)

98
Tng sai khc kn-1 T2 SS 0
SS 0 x 2 ij S02=
i j kn kn 1

Trong N=kn l tng s th nghim tin hnh

n n
Ti l tng cc cc php o trong nhm th i; T1= x1 j Tk=
j
k
j 1
kj

T l tng tt c cc php o Y= x
i j
ij

Vic so snh phng sai c thc hin qua chun F l t s gia phng sai
giu cc nhm v phng sai trong cng nhm
2
SA
Ftinh 2
>1 v so snh vi Fchun (P, fA, fB)
SB

trong SA2 l phng sai ca th nghim khi thay i cc mc khc nhau ca

yu t A.
STN2: l phng sai chung ca cc th nghim lp li trong cng nhm
fA: bc t do ca cc mc nghin cu ca yu t A lm; f= k-1
fTN: bc t do ca s nghin cu tin hnh trong qui hoch nghin cu : f2=
k(n-1)

Gi thit thng k H0 l: SA2STN2 v Ha: SA2 STN2

- Nu Ftinh <Fbang th Ftinh khng ng tin cy v c th xem SA2 v STN2 khc nhau
khng c ngha. Ni cch khc khi thay i cc mc ca yu t A t ra khng c
tc ng n kt qu nghin cu.
- Nu Ftnh >Fbng th Ftnh ng tin cy, tc l SA2 v STN2 khc nhau c ngha hay
yu t A c nh hng n kt qu nghin cu.

Trong phn mm thng k c th s dng tr s P (Pvalue) so snh vi P. nu

Pvalue< P=0,05 th khng nh rng khng phi tt c cc gi tr trung bnh cc mc
th nghim khc nhau u ging nhau. Ni cch khc l yu t A c nh hng n kt
qu th nghim.

Th d 5.2. Kt qu nh gi bn ca thuc th hunh quang gi trong 4 iu kin

khc nhau. Kt qu th nghim l cng hunh quang ca mi dung dch pha long
vi nng bng nhau, v c xc nh lp li 3 ln . Kt qu thu c nh sau:

99
 iu kin Kt qu o cng hunh quang /Trung bnh
A Dung dch mi pha 102; 100; 101 101
B Dung dch bo qun 1h trong bng ti 101; 101; 104 102
C Gi dung dch 1h trong nh sng du 97 ; 95 ; 99 97
D Gi dung dch 1h di nh sng trng 90 ; 92 ; 94 92
Trung bnh chung 98
tnh gi tr F, cn tnh qua cc bc trung gian sau u

xi - x Ti Ti2
A 2 0 1 3 9
B 1 1 4 6 36
C -3 -5 -1 -9 81
D -10 -8 -6 -24 576

T= -24 T
i
2
i 702

Vi n= 3; k=4, N= k.n=12; x 2
ij 258

Ngun bin thin Tng bnh phng Bc t do Phng sai

702 (24) 2
Gia cc mu =186 3 186/3= 62
3 12

Trong mt mu 210-186= 24 8 24/8=3

(24) 2
Tng 258 =210 11
12

Vy Ftnh= 62/3=27
Tra bng vi P=0,05 v f1=3 v f2=8 ta c Fbng= 4,066. Nh vy Ftnh >Fbng nn loi
b gi thit H0 do cc gi tr trung bnh mu khc nhau c ngha, ni cch khc
iu kin bo qun c nh hng n bn ca thuc th hunh quang.
Nu s dng phn mm MINITAB x l s liu theo cch nhp s liu phn so
snh cc gi tr trung bnh. Kt qu thu c nh sau:
Source DF SS MS F P
C8 3 186.00 62.00 20.67 0.000

100
Error 8 24.00 3.00
Total 11 210.00
S = 1.732 R-Sq = 88.57% R-Sq(adj) = 84.29%
Nh vy Pvalue= 0,000<0,05 chng t s khc nhau gia hai phng
sai l c ngha tc l cc gi tr trung bnh trong nhng iu kin khc nhau l khc
nhau.

5.3. Phn tch phng sai hai yu t (two-way ANOVA)

Nu ANOVA 1 yu t ch cho php nh gi nh hng ca mt yu t n kt
qu th nghim th bi ton ANOVA hai yu t s cho php nghin cu nh hng ca
c hai yu t i vi cng mt php th v nh hng tng h gia hai yu t n kt
qu th nghim.
Gi s c hai yu t nh hng n kt qu th nghim l A v B. Yu t A c k
mc nghin cu, yu t B c m mc nghin cu, mi mc th nghim lp li n ln (
ma trn s liu thu c l vung). Lp bng qui hoch nghin cu tc ng ca hai
yu t n kt qu th nghim nh bng 5.3:
Bng 5.3. Qui hoch thc nghim phn tch phng sai 2, yu t A c k mc th
nghim, yu t B c m mc; mi mc th nghim lp li n ln.

Yu t A

a1 a2 ... ai ... ak

b1 y111, y112, ..., y11n y211, y212, .. y21n yi11, yi12, .. yi1n yk11, yk12, .. yk1n

b2 y121, y122, .. y12n y221, y222, .. y22n yi21, yi22, .. yi2n yk21, yk22, .. yk2n

B ...

bj y1j1, y1j2, .. y1jn y2j1, y2j2, .. y2jn yj1, yij2, .. yijn ykj1, ykj2, .. ykjn

...

bm y1m1, y1m2, .. y1mn y2m1, y2m2, .. y2mn yim1, yim2, .. yimn ykm1, ykm2, ..
ykmn

Tng ct A1 A2 Ai Ak

101
 Khi tin hnh x l s liu theo ANOVA hai yu t cn tnh ln lt cc bc
nh sau:

- t Ai l tng cc kt qu mc i ca yu t A (i= 1k) hay cn gi l tng ct

m n m

Vi n th nghim lp li ta c Ai yiju Yij (tng cc kt qu nghin

j1 u1 j1

cu trong 1 ct).

- t Bj l tng cc kt qu mc j ca yu t B (i= 1m) hay cn gi l tng

hng
k n n

th tng cc kt qu nghin cu trong mt hng l Bj yiju Yij

i1 u1 i1

k m n k m
Yiju yiju Ai Bj
i1 j1 u1 i1 j1

- t (ABij) l tng cc gi tr mc i ca yu t A v mc j ca yu t B, gi
l tng cc .
Tng s cc th nghim ca A l kn v ca B l mn

n
Yij yiju (tng cc kt qu nghin cu trong 1 ) n
Yij ( y iju ) 2
2

u 1 u 1

(tng cc ct = tng cc hng)

k m n
1 k 1 m 2
SS1 y Ai SS3 k.n
2
SS 2
2
iju Bj
i1 j 1 u1 m .n i 1 j 1

1 k m n 1 k 2 1 m 2
SS4 (yiju) 2
(Ai ) (Bj )
k.m.n i1 j1 u1 k.m.n i1 k.m.n j1
Mu kt qu tnh ton ANOVA c trnh by trong bng 5.4

Bng 5.4: Bng phn tch phng sai hai yu t

102
Ngun bin thin Bc t do Tng cc bnh phng Trung bnh bnh
(Source of (Degrees of (Sum of squares) phng
variation) freedom) (Mean of square)
(x i x) 2
F S2

A k-1 SSA=SS2-SS4 SS A
SA
2

k 1

B m-1 SSB= SS3-SS4 SSB

SB
2

m1

AB (k-1).(m-1) SSAB= SStotal-SSA-SSB-SSe SSAB

SAB
2

SSAB =SS1-SS2-SS3+SS4 (k 1)(m1)

Sai s th nghim mk(n-1) SSe=SStotal-SSA-SSB SS e

Se
2

mk (n 1)
(Residue error) 1 k m 2
SSe= SS1 - Yij
n i1 j1

Tng mk(n-1) SStotal= SS1-SS4

nh gi nh hng c ngha ca cc yu t n kt qu th nghim cn su

dng chun F xt s khc nhau c ngha do phng sai thu c khi thay i cc
mc th nghim ca yu t A v B vi phng sai chung khi tin hnh th nghim.
2 2 2
S S S
FA A 2 ; FB B 2 ; FAB AB2
Se Se Se

Trong :
SA2 v SB2: phng sai c trng cho nh hng ca yu t A v B n kt qu
th nghim.
SAB2: phng sai c trng cho nh hng tng h ca c hai yu t A v B n
kt qu th nghim.
S e2 : phng sai c trng cho sai s ngu nhin ca cc th nghim.
V bc t do:
fA=k-1: fB = m-1 ; fAB= (k- 1).(m-1) ; fe = m.k.(n-1)

103
 So snh FA, FB, FAB vi gi tr Fbang vi P=0,95; f1= fA hoc fB hoc fAB v f2= fe
v kt lun v mc nh hng ca tng yu t n kt qu th nghim nh phn
5.1.

Th d 5.3: Trong thc nghim so snh kh nng tch loi Cu2+ trong nc ca
nha vng cng (% Cu2+) mt ngi phn tch lm th nghim phn tch phng sai 2
yu t l 5 ngy lm th nghim v 4 loi nha. Mi th nghim lm lp li hai ln. Kt
qu thu c bng di y.
Hy nh gi xem c s khc nhau c ngha ca cc loi nha theo thi gian hay
khng cng nh c s tng tc cu hai yu t nghin cu hay khng. Biu din kt
qu tnh c vo bng ANOVA. Ly P=0,95.

Loi 1 Loi 2 Loi 3 Loi 4

1 20,2 6,8 45,5 20,1

20,2 7,2 47,0 20,9

Ngy 2 28,1 22,6 15,5 7,5

29,6 23,5 16,0 8,6

3 8,7 38,7 6,7 52,7

9,0 38,2 7,1 53,0

4 30,4 50,6 18,9 60,4

30,9 51,1 17,6 61,2

5 50,7 18,8 30,5 67,6

50,5 18,5 30,9 67,2

Ngun:
( Sinh vin t gii theo cng thc tnh ton nu ).
Hng dn: S dng phn mm MINITAB, s liu c nhp vo dng sau:
Ct th nht l kt qu % Cu t trn xung di theo th t tng ngy v tng
loi
Ct th hai l ngy phn tch theo th t 8 s liu l 1( ngy th 1) sau n 8
s liu l 2 ( ngy th hai) Ct th ba l loi nhp theo th t 1, 1; 2, 2; 3, 3 ; 4, 4 ;

104
5, 5, ln lt t ngy 1 n ngy 5.
Vo Stat->ANOVA->2-way.
Chn response l %Cu
Row factor l ngy
Column factor l loi
V nh du vo dislay mean
Kt qu thu c nh sau:
Source DF SS MS F P
Ngay 4 3359.0 839.761 3205.20 0.000
Loai 3 1922.9 640.962 2446.42 0.000
nh hng tng h 12 8267.9 688.992 2629.74 0.000
Sai s chung (within) 20 5.2 0.262
Total 39 13555.1

S = 0.5119 R-Sq = 99.96% R-Sq(adj) = 99.92%

Individual 95% CIs For Mean Based on

Pooled StDev
Ngay Mean ---------+---------+---------+---------+
1 23.4875 *)
2 18.8500 *)
3 26.7625 (*
4 40.1375 (*)
5 41.8375 (*
---------+---------+---------+---------+
24.0 30.0 36.0 42.0
Individual 95% CIs For Mean Based on
Pooled StDev

105
Loai Mean ----+---------+---------+---------+-----
1 27.83 (*
2 27.60 *)
3 23.57 (*)
4 41.86 (*
----+---------+---------+---------+-----
25.0 30.0 35.0 40.0
Kt qu trn cho thy tt c cc tr s P ca ngy, loi v nh hng tng h
ca chng (interaction) u bng 0.000 tc l nh hn =0,05 chng t c nh hng
c ngha n kh nng loi Cu trong nc. S phn b gi tr trung bnh ca % Cu
theo ngy v theo loi nha u cho thy cng tng thi gian th kh nng hp th Cu
cng ln v tt nht loi nha th 5.

5.4. Bi ton phn tch phng sai 3 yu t tr ln- phng php vung Latinh
Trong trng hp cn nghin cu nh hng ca 3 yu t tr ln, xy dng
bng qui hoch thc nghim, ngi ta s dng phng php vung La tinh (Latin
square).
Nguyn tc: khng mt iu kin nghin cu xc nh lp li trong mt hng
hay mt ct. Ni cch khc trong bng qui hoch thc nghim khng c hai ging
nhau.
Gi thit c 3 yu t A, B, C, mi yu t c 4 mc nghin cu. Mi m t mt
iu kin nghin cu l t hp cc mc nghin cu ca 3 yu t. Th d: s 1 khi
lm th nghim ly mc a1, b1 v c1.
Ta c bng qui hoch thc nghim nh sau:
Bng 5.5: Qui hoch thc nghim phn tch phng sai 3 yu t, mi yu t 4 mc th
nghim.

b1 b2 b3 b4 Tng
hng

a1 c1 c2 c3 c4 A1
y1111; y1112; y1113 y2121; y2122; y2123 y3131 y3132; y3133; y4141 y4132; y4143

a2 c2 c3 c4 c1 A2

106
 y1221; y1222; y1223 y2231; y2232; y2233 y3241; y3242; y3243 y4211; y4212; y4213

a3 c3 c4 c1 c2 A3
y1331; y1332; y1333 y2341; y2342; y2343 y3311; y3312; y3313 y4321; y4322; y4323

a4 c4 c1 c2 c3 A4
y1441; y1442; y1443 y2411; y2412; y2413 y3421; y3422; y3423 y4431; y4432; y4433

Tng B1 B2 B3 B4 Y*
ct

Cch tnh cc gi tr trong bng trn nh sau:

A1= y111+y122+y133+y144
A1: tng cc gi tr y ( y l gi tr trung bnh ca 3 ln th nghim lp li ca cng
1 trong cng iu kin), c mc a1 ( tc l tng trung bnh ca cc kt qu ca cc
trong hng a1).
Tng t ta c cc gi tr khc:
A2, A3, A4 l tng cc kt qu c mc a2, a3, a4.
B1...B4 l tng cc kt qu c mc b1, b2, b3, b4.
C1...C4 l tng cc kt qu c mc c1, c2, c3, c4.
Y* = A1+A2+A3+A4 = B1+B2+B3+B4 = C1+C2+C3+C4
n n
SS1 yij (tng bnh phng cc ga tr c mt trong bng ).
2

j 1 i 1

1 n 2
SS 2 Ai
n i 1 S
2
FA A 2
1 n
SS3 Se
2
Bj 2
n j 1 SB
FB 2
1 n
Cq
Se
SS 4
2
2
n q 1 S
FC C 2
1 n 1 n 1 n Se
SS5 2
(
n i 1
Ai ) 2
2
(
n j 1
B j ) 2
2 q
( C )2
n qi 1

Bng phn tch phng sai trong trng hp ny c dng sau:

107
Bng 5.5: Bng phn tch phng sai ba yu t

Ngun bin thin Bc t do Tng cc bnh phng Trung bnh bnh

(Source of variation) (Degrees of (Sum of squares) phng
freedom) f (Mean of square)
(x2
i x)
S2

SS A
A n-1 SSA= SS2-SS5 SA
2

n 1
SS B
B n-1 SSB= SS3-SS5
2
SB
n 1
SS
C n-1 SSC= SS4-SS5 C
2
SC
n 1
Sai s th nghim (n-1)(n-2) SSe=SStotal-SSA-SSB-SSc SS e
Se
2

(n 1)(n 2)
(Residue error)

Tng n2-1 SStotal= SS1-SS5

So snh cc gi tr tnh ton vi gi tr tra bng Fbang (P,f1,f2) vi P=0,95 ; f1=n-1 v

f2= (n-1)(n-2) sau kt lun v mc nh hng ca tng yu t n kt qu th
nghim nh phn 5.1
Phng php ny c s dng nghin cu nh hng ca nhiu yu t trong
nng nghip, y hc sinh hc, x hi hc...

Th d 5.4: kho st nh hng ca nng thuc th o- phenantrolin (A), pH

dung dch (B) v nhit (C) n hp th quang ca dung dch phc mu Fe(II)-
o- phenantrolin , ngi ta tin hnh th nghim theo phng php vung la tinh vi
3 yu t nh hng, 4 mc th nghim. Kt qu trung bnh (sau 3 ln lm lp li) nh
sau:

b1 b2 b3 b4

a1 c1 C2 c3 c4
0, 351 0,522 0,24 5 0,248

108
 a2 c2 C3 c4 c1
0,356 0,258 0,452 0,526

a3 c3 C4 c1 c2
0,211 0,356 0,456 0,521

a4 c4 C1 c2 c3
0,169 0,254 0,255 0,452

Hy nh gi xem c nh hng c ngha ca cc yu t n hp th quang

ca dung dch phc mu hay khng? Biu din kt qu tnh c vo bng ANOVA.
Ly P=0,95.
Hng dn: Nhp cc s liu trong bng trn vo chng trnh MINITAB 14.
Ct kt qu c vo theo th t t tri sang phi v t trn xung di trong bng
tr n. Ba ct km theo l cc bin A, B, C. Trong ct A c nhp cc s 1,2 3, 4,
thay cho a1 a4 , tng t cho cc ct B v C. S liu sau khi nhp vo MINITAB c
dng:
Abs A B C
0.351 1 1 1
0.522 1 2 2
0.245 1 3 3
0.248 1 4 4
0.356 2 1 2
0.258 2 2 3
0.452 2 3 4
0.526 2 4 1
0.211 3 1 3
0.350 3 2 4

109
 0.456 3 3 1
0.521 3 4 2
0.169 4 1 4
0.254 4 2 1
0.255 4 3 2
0.452 4 4 3
V cc s liu khng phi l ma trn cn bng do vy khng dng balanced
ANOVA m phi dng dng General linear Model
Vo STAT->ANOVA->General linear Model. Nhp response l ct hp th
quang, Model l ct A, B, C, random factor chn A, B. Trong results chn: In
addition, coefficient for covariate terman table of unusal observation. V bm vo
OK. Kt qu thu c nh sau:
General Linear Model: Do hap thu quang versus A, B, C

Factor Type Levels Values

A random 4 1, 2, 3, 4
B random 4 1, 2, 3, 4
C fixed 4 1, 2, 3, 4
Analysis of Variance for Do hap thu quang, using Adjusted SS for Tests
Source DF Seq SS Adj SS Adj MS F P
A 3 0.03245 0.03245 0.01082 0.74 0.568
B 3 0.05463 0.05463 0.01821 1.24 0.375
C 3 0.04671 0.04671 0.01557 1.06 0.434
Error 6 0.08827 0.08827 0.01471
Total 15 0.22206
S = 0.121289 R-Sq = 60.25% R-Sq(adj) = 0.63%
Kt qu tnh ton cho thy c 3 yu t A, B, C u c gi tr P> 0,05 tc l c 3 3
yu t khng nh hng c ngha n kt qu th nghim.
( Sinh vin t gii bng cch tnh ton theo cng thc).

110
Th d 5.2: Kt qu phn tch tng hm lng Hg (g/g) bng phng php HPLC trong 3
loi ng vt thn mm (Rap., Nev., Sca.) 8 im ven b bin Bohai - Trung Quc thu
c nh sau:

a im 1 2 3 4 5 6 7 8
Loi

Rap. 0.042 0.063 0.059 0.038 0.053 0.199 0.060 0.038

Nev. 0.033 0.062 0.096 0.027 0.044 0.077 0.039 0.031

Sca. 0.005 0.044 0.068 0.016 0.014 0.099 0.021 0.026

Hy dng phng php phn tch phng sai mt yu t nh gi xem loi v a im

c nh hng n s tch lu Hg trong ng vt thn mm hay khng.
Ngun: W. Yawei et al. / Environmental Pollution 135 (2005) 457 - 467
( Nu s dng phn mm MINITAB 14 th kt qu vn tt thu c nh sau:
Ngun phng sai DF SS MS F P
Loi ( gia cc loi) 3 0.00476 0.00159 0.76 0.524
Sai s( trong mt loi) 28 0.05816 0.00208
Tng 31 0.06292

S = 0.04558 R-Sq = 7.57% R-Sq(adj) = 0.00%

Individual 95% CIs For Mean Based on

Pooled StDev
Level N Mean StDev ---------+---------+---------+---------+
1 8 0.06900 0.05348 (-------------*------------)
2 8 0.05113 0.02483 (------------*-------------)
3 8 0.03663 0.03212 (-------------*------------)

111
4 8 0.04263 0.06164 (------------*------------)
---------+---------+---------+---------+
0.025 0.050 0.075 0.100

Pooled StDev = 0.04558

Fisher 95% Individual Confidence Intervals
All Pairwise Comparisons among Levels of Muc
Simultaneous confidence level = 80.51%
Hy gii thch kt qu trn

112
Chng 6: PHN TCH TNG QUAN V HI QUI

Trong thc t phn tch, xc nh hm lng cht ngi ta thng s dng

phn tch ho hc c in (cn gi l phn tch ha t) v phn tch cng c.
- Phn tch ho hc c in c s dng rng ri do c chnh xc cao, lm t
th nghim vi s t mu, v c p dng phn tch nhng mu chun. Tuy nhin,
phng php ny c gii hn pht hin thp v tn nhiu thi gian phn tch.
- Phn tch cng c chim hn 90 % cc php phn tch do:
+ nhy cao, xc nh c ng thi nhiu nguyn t, phn tch c s
lng ln mu cng mt lc, v vy tn t thi gian phn tch, gi thnh phn
tch r hn so vi phn tch ho hc .
+ Phn tch cng c kt ni c vi my tnh, do c th t ng ho, x
l s liu trn my tnh, nh gi thng k v so snh c cc s liu lu tr
trong b nh.
Tuy nhin, cc phng php phn tch cng c lun cn nh chun (c mu
chun). T s liu thu c i vi cc mu chun, dng ng biu din tn hiu
phn tch theo nng ca mt cht nh phn tm phng trnh h qui n bin
(hin nay c rt nhiu phng php phn tch xc nh c ng thi nhiu cht
bng phng php hi qui a bin nhng gio trnh ny khng cp n) v
chnh xc ca phng php phn tch da trn phn tch hi qui. Mc d vy, khng
phi gia 2 bin ngu nhin lun c tng quan, do cn phi kim tra tng quan
ny bng phn phi 2 chiu. Ni cch khc, cn phi tr li c cc cu hi sau:
- ng chun c tuyn tnh khng (dng y= a+bx)? Nu l ng cong th
phng trnh ton hc biu din l g? ( c phi dng y= a+bx+cx2; y= 10x, y= ex; y=
a+ logx?)
- Mi im thc nghim(xi ,yi) khi dng xy dng ng chun u mc sai
s khi phn tch. Vy ng biu din no s i qua tt c cc im thc nghim ny
(ni cch khc cho sai s gia gi tr l thuyt tnh theo phng trnh hi qui v gi tr
thc nghim l nh nht?
- Gi thit ng chun l thc s tuyn tnh th sai s v gii hn tin cy ca
nng cht trong mu cha bit xc nh c khi c tn hiu o theo phng trnh
hi qui l bao nhiu?
113
 -Gii hn pht hin, khong tuyn tnh ca phng php l bao nhiu khi s
dng phng trnh ton hc v khng phi mi gi tr thc nghim y u cho gi tr x
tm c tin cy?

6.1. Phn tch tng quan (correlation analysis)

Phn tch tng quan c dng nh gi mi quan h gia hai hay nhiu bin
thng qua h s tng quan. Hai loi h s tng quan thng dng nht l h s
tng quan Pearson hoc Spearmen. Trong phm vi gio trnh ny ch xt n h s
tng quan Pearson .
H s tng quan r biu th mc quan h tuyn tnh gia hai bin v tnh c
nu tp s liu tho mn cc iu kin sau:
- Cc tp s liu ca cc bin tun theo phn phi chun.
- Cc gi tr trong mi tp s liu ca cc bin l c lp nhau.
- Phi loi b gi tr bt thng trc khi tnh h s tng quan cu hai tp s
liu.
(Trng hp nu khng tun theo phn phi chun th nn s dng h s tng
quan phn hng Spearmen).
* Cch tnh h s tng quan Pearson (the product-moment correlation coefficient)
Gi s c hai tp s liu X (x1, x2, xn) v Y(y1, y2, yn), trong mi gi tr
ca y tng ng vi mi gi tr ca x (v d t nng cht phn tch trong dung dch
chun xi o c tn hiu phn tch yi, hoc t mt mu phn tch xc nh c hm
lng ca hai hay nhiu cht)
Khi h s tng quan r gia hai tp s liu c tnh theo cng thc sau:
COV
r XY
(6.1)
S xS y

vi COV l ng phng sai ca hai tp s liu X v Y v c tnh theo cng

thc:

COV XY
(x i x)( y i y )
(6.2)
n

vi n l s cp gi tr trong tp s liu X v Y
Do vy, c th tnh r theo mt trong 3 cng thc khai trin sau :

114
 n xi y i ( xi ) 2 ( x x).( y y)
r
i i
(6.3)
( ( xi x ) )( ( y i y ) )
2 2
( ( x x ) )( ( y y )
i
2
i
2
)

1
x y n x y
i i i i

r (6.4)
(xi ) 2 ( yi ) 2
(xi )( yi
2 2

n n

Khi r = 1 th tp hp cc im (xi, yi) hu nh nm trn ng thng tc l hai

bin c tng quan tuyn tnh tuyt i.
Khi r>0 th x v y c quan h ng bin cn r<0 th x v y c quan h nghch
bin.
Khi r =0 th x v y khng c quan h tuyn tnh.
Gi tr tuyt i ca r cho bit mc quan h tuyn tnh ca x v y. Trong mt
s trng hp c th tnh h s xc nh (r2) tc l phn phng sai ca mt bin c
d on bi bin kia theo tng phng sai. V d, r2=0,88 c ngha l x chim 88 %
phng sai ca c x v y.
Mt s th d v mc tng quan hai bin x, y c biu din trn ta 2
chiu trong hnh 6.1, trong mi im thc nghim c xc nh t mt cp gi tr
x,y).

r r

r r

115
 Hnh 6.1: th biu din mc tng quan gia hai i lng o

Th d 6.1: Tin hnh phn tch hm lng gluco trong mu theo phng php
trc quang ng hc- xc tc, xy dng ng chun, ngi ta pha 6 dung dch
chun c nng gluco thay i nh trong bng di y v o gi tr hp th
quang ca dung dch phc mu tng ng. Kt qu thu c nh sau :

Nng gluco (mM) 0 2 4 6 8 10

hp th quang 0,002 0,150 0,294 0,434 0,570 0,704

Nu biu din s ph thuc

0.8
gia hp th quang (y)
0.7
theo nng gluco trong
0.6
dung dch theo tng quan 2
0.5 chiu (hnh 6.2) v vn dng
0.4 cng thc tnh h s tng
A

0.3 quan r nu trn s tnh c

0.2 h s tng quan Pearson
0.1
r=1,00. Vy gia nng
glucozo v hp th quang
0.0

0 2 4 6 8 10
ca dung dch phc mu c
nong-do-glucozo(mM)
tng quan tuyn tnh rt tt.

Trong nhiu trng hp h s tng quan r gia hai bin khng t n gn 1

nn tr li cu hi rng hai bin X v Y ang xt tht s c tng quan tuyn tnh
hay khng chng ta c th s dng chun student kim tra bng cch tnh gi tr t
v so snh vi gi tr t trong bng cho trc. Gi tr t c tnh theo cng thc sau :

r. n2
t (6.5)
(1 r 2 )

vi r l h s tng quan Pearson, n l s s liu trong mi bin hay l s th

nghim. Sau , so snh ga tr ttinh vi tchun tra bng tin cy thng k mong
mun (thng chn P=0,95), s bc t do f = n-2, v s dng chun t 2 pha ( cho bi
ton so snh s ging v khc nhau gia r v 0 .
116
 Gi thit "o" Ho ( tc l xem r0) l gi thit gia X v Y khng c tng
quan, t c khi ttinh < ttra bang . Cn nu ttinh > tbang th X v Y c tng quan tuyn
tnh.
Nu tnh ton bng cc phn mm thng k, c th s dng tr s P (Pvalue) v so
snh vi khng tin cy cho trc. Thng thng nu Pvalue<0,01 th kt lun rng
hai bin c tng quan tuyn tnh tin cy 99%. Kt lun tng t nu Pvalue<0,05.

Th d 6.2: Khi so snh kt qu phn tch cht M c tin hnh bi hai phng php
A v B (mi phng php lm 10 th nghim tng ng 10 mu c 10 mc nng
khc nhau) ngi ta tnh c h s tng quan r=0,65. S mc hm lng em
phn tch l n=11. Vi gi tr h s tng quan khng ln ny cha th kt lun
ngay l kt qu xc nh theo hai phng php c tng quan tuyn tnh. Do vy, cn
kim tra xem c tha mn theo chun t hay khng?
Theo cng thc trn c th tnh c:

0,65 11 2
t 5,57 ; tra bng gi tr t bc t do f=9 v tin cy thng k 95 %
(1 0,652 )
ta c t= 2,56
Nh vy gi tr ttnh vn ln hn ga tr t trong bng, ni cch khc c th xem phng
php A ph hp vi phng php B v ngc li.

i vi mt s trng hp, bi ton phn tch tng quan cn c th p dng cho

vic so snh tng quan tng cp trong tp s liu c nhiu hn hai bin. Khi kt
qu c th biu din di dng ma trn h s tng quan, c vit di dng mt na
ma trn v h s tng quan gia bin X v bin Y cng nh gia bin Y v bin X.
Phn mm MINITAB cho php nhp s liu, tnh h s tng quan r v kim tra
tnh tng quan ca hai i lng qua tr s P bng cch nhp s liu trong mi bin
vo cc ct, sau x l s liu trong mc Stat StatisticsCorrelation.

Th d 6.3: Khi phn tch hm lng cc kim loi (mg/kg mu kh) Ti, Mn, Fe, Cu,
Pb, Zn , Ni, Cr trong mu bn ly cc cng thot nc trong th theo phng
php ICP-AES, thu c cc kt qu sau:
Mu Ti Cr Mn Fe Ni Cu Zn Pb
1 1247,0 210,5 579,0 51156 31,9 113,0 1001,8 106,0
2 1022,0 88,7 420,0 22960 28,5 128,2 512,2 160,6

117
 3 1187,0 210,8 479,3 26494 73,7 243,1 965,0 *
4 1003,0 104,3 462,5 26079 34,4 249,3 497,6 103,6
5 767,7 147,0 379,2 37854 58,7 126,9 724,6 197,1
6 726,3 32,6300,7 20503 57,2207,7 667,8 56,5
7 972,2 45,1639,6 34584 38,7184,3 1257,0 104,9
8 * 73,8524,6 26171 35,3 156,1 839,1 196,0
9 943,0 * 510,0 36990 * 235,9 * 255,4
10 699,2 65,9 429,9 23760 29,2 378,5 810,464,0
11 614,4 49,7 295,1 24717 13,9 366,1 494,8199,3
12 1145,0 50,7 369,9 37912 27,1 259,8 1179,0 283,5
13 905,8 128,9 451,3 52115 32,2 356,5 * 378,6
14 * 59,6510,8 39931 38,0 131,3 706,5312,3
15 898,0 74,7377,7 26779 34,1 89,6 381,1108,6
16 558,9 101,8 397,9 21001 24,5 235,9 439,6183,9
17 1217,0 53,3 528,4 23656 23,8 139,0 990,583,6
18 1160,0 71,9633,5 31204 37,6 143,1 * 98,0
19 955,3 100,7 469,2 26171 30,5 189,7 839,1 207,8

Nhng s liu c k hiu du * l nhng gi tr ln bt thng (c ngha l nhng

mu cc v tr ny khng i din cho ton b mu cc phn tch, c loi b).
Khi tnh ton, thng thng phn mm thng k s xem nhng s liu ny c gi tr
bng gi tr trung bnh ca tp s liu.
S dng phn mm thng k MINITAB 14, vo Stat-> Basic Statistics->
Correlation. Nhp Variable l cc ct cha hm lng 8 kim loi v chn mc
display P-value.
Kt qu cc h s tng quan gia cc cp bin l hm lng hai kim loi(hng
trn) v tr s P(hng di) thu c nh sau:
Ti Cr Mn Fe Ni Cu Zn
Cr 0,334 (r)
0,205 (Pvalue)

118
Mn 0,638 0,184
0,006 0,465
Fe 0,356 0,424 0,345
0,161 0,079 0,147
Ni 0,151 0,434 0,034 0,028
0,578 0,072 0,894 0,911
Cu -0,452 -0,098 -0,365 -0,032 -0,218
0,068 0,697 0,124 0,898 0,385
Zn 0,592 0,087 0,595 0,477 0,173 -0,022
0,026 0,747 0,015 0,062 0,521 0,934
Pb -0,065 0,129 -0,113 0,551 -0,150 0,250 0,040
0,810 0,621 0,655 0,018 0,566 0,316 0,888
Nh vy ch nhng gi tr h s tng quan c tr s P <0,05 (h s r c in m
trong bng trn l c tng quan tuyn tnh. Cn c v cc h s r ny c th rt ra
c chiu hng v mc tng quan gia hm lng cc kim loi nu trn. Theo
kt qu ny ch c cc cp nguyn t Mn-Ti; Zn- Ti; Fe-Mn; Pb- Fe c mi tng
quan t l thun trong cc mu bn ly ti cng thot nc th. iu ny c ngha
l khi hm lng kim loi ny trong mu cao th hm lng kim loi c tng quan
cng ln. Nh vy c th kt lun cc kim loi c tng quan hm lng s c cng
ngun pht tn (c th do ngun gc t nhin nh Mn, Ti v Fe trong t, ct, Pb,
trong t nhin, Pb v Fe c th do ngun pht tn t cc hot ng giao thng...

6.2.ng chun v phng php bnh phng ti thiu trong phn tch nh
lng
Gi s c 2 tp s liu X v Y trong mi tp s liu c nhiu gi tr, mi gi tr
ca Y thu c t thc nghim khi thay i gi tr ca X.
X: x1 x2 x3 x4 x5 ... ( nng )
Y: y1 y2 y3 y4 y5 ... (tn hiu phn tch)
ng chun s l ng biu din s ph thuc tuyn tnh gia tn hiu o v
nng cht nh phn, nu phng trnh hi qui c dng y = a + bx, trong a l
im ct trc tung ca ng chun v b l dc ca ng chun. Trong thc t

119
phn tch, khi h s tng quan r > 0,99 c th xem c tng quan tuyn tnh tt gia
x v y v phng trnh hi qui c dng nh lng y theo x.
T cc im trn th ( x1; y1) ( x2; y2)........ (xn; yn) ta s tm c trng tm ca
tp s liu (centroid of all points) ( x ; y ).

Khi c quan h tuyn tnh gia bin c lp x (nng ) v bin ph thuc y (tn
hiu phn tch ) th vn quan trng l lm th no tm c ng thng ng
nht m phng trnh hi qui ca ng thng ny cho php tnh c gi tr l thuyt
c sai s so vi cc im thc nghim l nh nht (trong khi mi im thc nghim
u mc sai s)? Do , tm ng thng ny cn ti thiu ho chch (c gi tr
dng hoc m) gia cc gi tr thc nghim yi v gi tr yi (tnh c theo phng
trnh hi qui biu din quan h tuyn tnh gia v x v y) theo tng bnh phng
chch (sum of square of the residuals). V vy phng php ny cn gi l phng
php bnh phng ti thiu (hnh 6.2).

Hnh 6.2: Phng php bnh phng ti thiu

Nh vy, nu cc gi tr thc nghim c biu din bng phng trnh ton hc

dng y=ax +b trong a l im ct trc tung ca ng chun (intercept) v b l

120
dc ca ng chun (slope) th s sai khc gia gi tr thc nghim yi v gi tr y i
tnh theo phng trnh l:

yi = yi y i = yi a b.xi (6.6)

Bnh phng s sai khc ny c dng :

yi2 = (yi - a - b.xi)2 = yi2 + a2 + b2xi2 - 2ayi - 2bxiyi + 2abxi2. (6.7)

Ly tng cc gi tr yi2 ca n im thc nghim trn ng chun th :

n n n n n n

(y )
i 1
i
2
( y i ) 2 n.a 2 b 2 ( xi ) 2 2a y i 2b ( xi y i ) 2ab xi
i 1 i 1 i 1 i 1 i 1
(6.8)

s sai khc gia yi v y i l nh nht, ngi ta tm yi 0, hay

n
(y i )
2
n n
i 1 2 y i 2b xi 2n.a 0 (6.9)
a i 1 i 1
n
(y ) 2
i n n n

i 1

b
2
i 1
( x i . y i ) 2b
i 1
( x i ) 2
2 a
i 1
xi 0 (6.10)

Gii h hai phng trnh trn thu c

b
( x x )( y y ) n x y x y
i i i i i i
(6.11)
(x x) i n x ( x )
2 2
i i
2

n n n n

yi . xi2 xi . xi . yi
a y b.x i 1 i 1
n
i 1
n
i 1
(6.12)
n x ( xi )
2
i
2

i 1 i 1

Nh vy t cc gi tr thc nghim xi v yi s tm c phng trnh hi qui

tuyn tnh dng y=a+bx v h s tng quan r.

*Tnh sai s ca b v a trong phng trnh hi qui

Mi h s trong phng trnh hi qui nu trn c xc nh t thc nghim do
ph thuc vo bn thn chnh xc ca cc kt qu o xi v yi. V vy, lch
chun ca a v b tu thuc vo mi im thc nghim sai khc bao nhiu so vi im
l thuyt trn ng chun. Do vy hm tuyn tnh y=a+bx c khong tin cy d on
nh hnh 6.3.

121
 Tn hi

u o

Nng cht nh phn

Hnh 6.3: Phng trnh hi qui tuyn tnh (y=a+bx) vi khong tin cy c on.

Gi s gi s sai khc ( chch) gia gi tr thc nghim v gi tr tnh theo m

hnh ny l di, ta c: di = yi - y = yi - a - b.xi

Trong : yi gi tr thu c t thc nghim

y gi tr tnh theo phng trnh hi quy.

V a, b l cc i lng o gin tip, nn phng sai ca cc h s a v b l:

a 2 2 a 2 2 a 2 2
Sa 2 ( ) .Sy1 ( ) .Sy 2 ... ( ) .Sy n (6.13)
y1 y 2 y n

b 2 2 b 2 2 b 2 2
Sb 2 ( ) .Sy1 ( ) .Sy 2 ... ( ) .Sy n (6.14)
y1 y 2 y n

Nu xem phng sai tnh c ti cc gi tr thc nghim yi l nh nhau v l

phng sai chung ca m hnh th Sy12 = Sy 22 = ... = Sy n2 = Sy 2 .

Vi phng sai ca m hnh (variance of fit) tnh theo cng thc tnh phng sai l :

Sy 2
(y i a bxi ) 2
; (6.15)
n2

122
 n( x1 y1 ... x n y n ) xi ( y1 ... y n )
b
n xi2 ( xi ) 2
(6.16)

b 2 (nx1 xi )
2
n 2 x12 ( xi ) 2 2nx xi
Nh vy ( ) (6.17)
y1 MS 2 MS 2

vi MS n xi2 ( xi ) 2

b 2 (nx1 xi ) n 2 x 22 ( xi ) 2 2nx 2 . xi
2

Tng t : ( )
y 2 MS 2 MS 2
(6.18)
Do :

b 2 b 2 n xi n( xi ) 2n( xi ) n 2 xi2 n( xi ) 2
2 2 2 2
n
( ) ... ( )
y1 y n MS 2
MS 2
MS
(6.19)
2
n Sy
Vy Sb Sy . 2 2

n xi ( xi )
2 2
( xi x ) 2

n xi2 2 x 2

Sa 2 Sy 2 . Sy
i
(6.20)
n xi2 ( xi ) 2 ( x x )
i
2

(6.21)
T cc gi tr phng sai ca a v b c th tnh c lch chun Sa, Sb
Sy
Sb
(x
i
i x) 2

(6.22)

x
2
Sy i

Sa i
(6.23)
( xi x) 2
i

Khi , khong tin cy ca cc h s a v b c tnh l : b t. Sb v a t. Sa

Nh vy, phng trnh hi qui y c dng: y= (a t. Sa) + (b t. Sb) .x
Gi tr t tra trong bng chun student 2 pha vi tin cy thng k P= 0,95 v f= n-2

123
Th d 6.4: Kt qu xy dng ng chun phn tch hm lng Ca theo phng
php FIA thu c nh sau:

Nng (ppm) 0 2 4 6 8 10 12 x =7

xi - x -5 -3 -1 1 3 5

Chiu cao pic (cm) 2,1 5,0 9,0 12,6 17,3 21,0 24,7

y 2,9 6,9 10,5 15,2 18,9 22,6 y =12,8

yi- y -9,9 -5,9 -2,3 2,4 6,1 9,8

- x l s liu c th tnh trc tip theo cng thc hoc s dng phn mm
my tnh nh Excel, Minitab hoc Origin.
+ Kt qu tnh ton theo phn mm thng k Origin 6.0 thu c nh sau:

Par. Error

A 1,52786 0,29494 R SD N P

B 1,93036 0,0409 0,99888 0,43285 7 <0,001

+ Cc tnh ton trn phn mm Minitab nh sau:

Nhp hai ct s liu X v Y, vo Stat RegressionRegression. Trong ca s

ny, nhp Response l ct cha tp s liu Y v Predictors l ct cha s liu X,
phn results chn regression equation..
Kt qu thu c nh sau:
The regression equation is
y = 1.52 + 1.93 x
Predictor Coef SE Coef T P
Constant 1.5179 0.2949 5.15 0.004
x 1.93036 0.04090 47.20 0.000
S = 0.432848 R-Sq = 99.8% R-Sq(adj) = 99.7%
Analysis of Variance
Source DF SS MS F P

124
Regression 1 417.34 417.34 2227.53 0.000
Residual Error 5 0.94 0.19
Total 6 418.28
Kt qu bng phn tch phng sai cho thy gi tr Pvalue <0,05 ca hng s a, b
< 0,05 chng t x v y c quan h tuyn tnh. Tr s P trong kt qu nh gi ca
phng trnh hi qui (chun F) <0,05 cng chng t phng trnh trn chi s sai
khc gia l thuyt
Theo cc kt qu trn ta c: a=1,528 ; b= 1,930 ; Sa =0,295; Sb=0,041.
lch chun ca phng trnh l: Sy=0,4329. H s tng quan r=0,9988.
Tra bng gi tr chun t vi bc t do f=5, tin cy 95% c t=2,57 nn
phng trnh hi qui ca ng chun trn s c dng:Y=(1,530,76)
+(1,930,11)x.
Ngoi ra, cc thng s trong bng phn tch phng sai cng cho bit m
hnh xy dng c l ph hp vi thc nghim.

25

20
chiu cao pic (cm)

15
u cao pic

10
Chi

a=1,53
0
0 2 4 6 8 10 12
nng
Nng phn
cht cht ph
tchn t
ch (ppm)

Hnh 6.4: ng chun biu th quan h gia chiu cao pic v nng cht

125
 *Tnh nng cht nh phn:
- T phng trnh hi qui tm c, khi mu nh phn c gi tr i tn hiu
phn tch l y0 th c th tnh c nng cha bit x0.
- khng m bo o ca gi tr x0 tnh c theo phng php ng chun
s dng phng trnh y = a+ bx gy ra do 3 sai s ring phn v kt qu phn tch mc
sai s do a, b c cha sai s.
Theo nh lut lan truyn sai s, lch chun ca nng x0 c tnh nh sau:

Sy 1 ( y y)2
S x0 1 2 0
b n b ( xi x) 2
i

y : Sx0 l lch chun c on hay sai s bnh phng trung bnh ca x0

y0 l gi tr thc nghim thu c khi phn tch x0
n: s mu chun dng xy dng ng chun, phn tch khng lp li.

Nu mu cha bit c phn tch lp li m ln thu c gi tr y 0 th :

Sy 1 1 ( y y) 2
S x0 2 0
b m n b ( xi x) 2
i

Khi , kt qu phn tch mu cha bit s c vit di dng: x0 t.Sx0 vi bc

t do f=n-2.
Mt cch khc, tnh nng x0 khi c gi tr thc nghim y0 l tnh x0 theo
( y 0 Sy ) (a Sa )
cng thc xo v s dng quy lut lan truyn sai s tnh gi tr
(b Sb)
x0.

Th d 6.5: Trong php phn tch dng ng chun th d 6.4, nu c mt mu

phn tch o c chiu cao pic l y0 =7,3 th nng cht phn tch trong mu l
bao nhiu?
Gii: t tn hiu o ca mu cn phn tch, s dng phng trnh hi qui s
y 0 a 7,3 1,53
tnh c gi tr x0 2,98
b 1,93

126
 Sy/x 1 ( y0 y) 2
lch chun S x 1 2
0
b n b ( xi x) 2
i

y i
vi n=7 ; b= 1,93 Sy/x= 0,433 y i 1
13,1
7
7 2

( xi x)
i 1
83 ,9256

Thay s vo ta c: Sx0 = 0,25 vi t(P=0,95,f=55) =2,57

Vy khong xc nh ca x0 l: x0 = (2,980,64)
* Nu mu cn phn tch c xc nh lp li 3 ln v chiu cao pic trung bnh l
Sy/x 1 1 ( y y) 2
yo=7,3 th S x 2 0
0
b m n b ( xi x) 2
i

vi m=3 thay s nh trn ta c Sx0=0,28 v khong xc nh ca x0 l

x0= (2,98 0,72)

i vi ng chun, nh hng ca s im th nghim (khng lm lp li) trn

ng chun rt phc tp v khi n thay i c km theo s thay i gi tr t. Khi n nh
th gi tr 1/n ln, bc t do f= n-2 nh, nn tbng ln, lm cho khong tin cy ln. Ni
cch khc, tng chnh xc ca ng chun cn tng s im trn ng chun,
tc l tng n. Do vy, phng trnh hi qui t tin cy mong mun th s im
dng ng chun phi khong t 5-10 im v cc im trn ng chun nn
chia cch u nhau sai s thc nghim cc gi tr o khng qu ln v mun tng
chnh xc kt qu phn tch mu cn lm lp li nhiu th nghim xc nh x0 .

6.3. nh gi phng trnh hi qui ca ng chun

Trong phng trnh hi qui y = a + bx, trng hp l tng xy ra khi a=0 ( khi
khng c cht phn tch th khng c tn hiu). Tuy nhin, trong thc t cc s liu
phn tch thng mc sai s ngu nhin lun lm cho a0. Nu gi tr a khc 0 c
ngha thng k th phng php phn tch s mc sai s h thng. V vy, trc khi s
dng ng chun cho phn tch cng c cn kim tra xem s khc nhau gia gi tr a
v gi tr 0 khng c ngha thng k khng.
* Kim tra a vi gi tr 0 : theo chun thng k Fisher (chun F).
127
 Nu xem a0 th phng trnh y=a+bx c vit thnh phng trnh y=b'x. Thay
cc gi tr yi v xi vo phng trnh y=b' x ta s c cc ga tr b'i v tnh

b 'i
b i
trong n l s im trn ng chun, c tnh n im c nng
n 1
bng khng.
Phng sai ca hai phng trnh s c tnh nh sau:

Sy
2

(y i y i ) 2

(y i a bxi ) 2
n2 n2

S'y
2 (y i y ' i ) 2

(y i b ' xi ) 2
n3 n3

S sai khc phng sai ca hai phng trnh ny c so snh theo chun F (tnh
theo t s ca hai phng sai sao cho F>1 v so snh gi tr ny vi F(P,f1,f2) vi P=0,95
v f1 = n-3, f2 = n-2.
2
S'y
Ftinh 2
Sy

Nu Ftinh< F(P, f1, f2) th s khc nhau v phng sai ca hai phng trnh khng c
ngha thng k. Ni cch khc, c th xem nh a=0.
* Kim tra b v b: Khi khng c sai s h thng th phng trnh y=a+bx tr
thnh phng trnh y= a+b'x, tc l s khc nhau gia b v b' khng c ngha thng
k. Do vy, c th dng chun t kim tra nh s khc nhau ca 2 gi tr trung bnh.
Vi phng trnh y = a + bx khi chuyn c thnh phng trnh y=b'x th gp
cc tng bnh phng thu c v tnh phng sai chung nh sau:

Sg
2

(y i a bxi ) 2 ( y i b' xi ) 2
(m1 2) (m 2)

Ta c phng sai ca hiu b-b'

1 1
S g2
2
Sd
x2 1 ( x )2 1 2
1i m1 1i x 2i m ( x 2i )
2

bc t do f = (m1-2)+(m2-2) vi m1 v m2 l s th nghim tin hnh ng chun

trong hai phng trnh.

128
 b1 b2
kim tra ngha ca hiu b1-b2 ta tnh t v so snh vi t(P,f).
Sd

Th d 6.6 : Cc kt qu xy dng ng chun trong phng php trc quang xc

nh asen sau khi hirua ho bng thuc th leucocrystal violet thu c nh sau:

STT 1 2 3 4 5 6 7 8

CAs ppb 4 12 30 60 120 180 240 300

(.10-7M 0,53 1,6 4 8 16 24 32 40

A1 0,0021 0,0065 0,0170 0,0330 0,0681 0,1004 0,1287 0,1656

A2 0,0019 0,0067 0,1168 0,0333 0,0678 0,1007 0,1288 0,1660

A3 0,0023 0,0063 0,0169 0,0332 0,0682 0,1008 0,1285 0,1650

A 0,0021 0,0065 0,0169 0,0332 0,0680 0,1006 0,1287 0,1655

Kt qu tnh theo phn mm Origin 6.0 thu c phng trnh hi qui y ca

ng chun c dng y=A+Bx nh sau:
A =(0,00023 0,00304) + (0,00413 0,00014)CAs
Trong A l hp th quang v Cas l nng As (III) (10-7 M)

129
 0.18

0.16

0.14

0.12
Y = A + B* X
0.10
Parameter Value Error
0.08 ------------------------------------------------------------
Abs

A 2.31211E-4 0.00124
0.06
B 0.00413 5.89054E-5
0.04 ------------------------------------------------------------
0.02 R SD N P
0.00 ------------------------------------------------------------
0.99939 0.00232 8 <0.0001
-0.02
0 10 20 30 40
7
CAs.10 M

kim tra sai s h thng ca phng php cn so snh hng s a ca phng trnh
hi quy vi gi tr 0.Nu xem a = 0, phng trnh tr thnh y = Bx. Cc gi tr B
c tnh nh bng di y

x . 107, M 0,53 1,6 4 8 16 24 32 40

Y 0,0021 0,0065 0,0169 0,0332 0,0680 0,1006 0,1287 0,1655

B 0,0040 0,0040 0,0042 0,0041 0,0042 0,0041 0,0040 0,0041

6 3 5 5 9 2 4

Cc gi tr lin quan n h s s l

Mean Trung bnh 0,004148771

Standard Error sai chun 3,26289 E - 05

Standard Deviation lch chun 8,47405 E 05

Sample Virance Phng sai mu 7,18095 E 09

Sum Tng 0,02904

Confidence Level (95,0%) tin cy 7,83719 E 05

130
 Nu A 0 khng c ngha thng k mc tin cy 95%, phng trnh hi

quy c dng: y B' t.SB' x .

Ta c: y =(0,00415 2,45.3,26.10-5)x

SS
p dng cng thc: SS= y i A Bx i v S2=
2
ta c bng gi tr:
n2

Hm Tng cc bnh phng Bc t do Phng sai

Y = Bx SS=2,07.10-5 5 S2= 4,14.10-6

y = A + Bx SS = 1,83.10-5 6 S2= 3,05.10-6

S '2
C: Ftnh= = 4,14/3,05=1,35; Tra bng F(0,95;7;6)=4,3874 =>Ftnh <
S2
F(0,95;5;6) c ngha l s sai khc gia gi tr a v 0 khng c ngha thng k hay
phng php khng mc sai s h thng.

131
 * Kim tra chm ca cc th nghim xy dng ng chun :
ng chun m chng ta dng tnh cc gi tr x0 khi c gi tr o yo thng gi
thit khng chnh xc nu c l nh nh nhau ti mi im trn ng chun. Nu
phng sai khng ng nht s khng ch dn n chm khng ng nht m
khng chnh xc cng tng do thay i dc ca ng chun (hnh 6.5).

Tn hi

u o
Tn hi

u o

Nng Nng

Hnh 6.5. Phng sai khng ng nht cc nng khc nhau ca dung dch
chun
nh gi ng nht v phng sai, ngi ta tin hnh o lp li 10 ln cho
mi th nghim mc nng thp nht (x1) v cao nht (xn) c th. Sau tnh gi
tr trung bnh tn hiu phn tch ti hai mc nng ny ( y1 v y n ), cc gi tr
phng sai S12 v S2n sau kim tra s sai khc gia hai phng sai ny bng chun
F, vi
2
Sn
F= 2
v so snh vi Fbng (P=0,99; f1=9; f2=9)
S1

Nu Ftnh >Fbng tc l hai phng sai khc nhau c ngha th cn tin hnh theo cc
cch sau khc phc sai s :
- Chn khong nng hp hn xy dng ng chun v nh gi li
ng nht phng sai nh trn.
- Dng phng trnh hi qui khi (xem mc 6.7).

132
 - Dng phng trnh hi qui phi tuyn

6.4. Gii hn pht hin, gii hn nh lng, nhy, chn lc

Trong hu ht qui trnh phn tch, chm tuyt i ca gi tr o (hay kt qu
phn tch) s t c khi gim nng cht phn tch. Tuy nhin, vic phn tch
nhng nng rt nh (phn tch vt) s gp vn rc ri khi phi phn bit tn hiu
phn tch mu hay tn hiu mu trng chnh xc tin cy c. Khi , c th xy
ra cc kh nng sau :
- Mu khng cha cht phn tch ? Tn hiu quan st c ch l tn hiu sinh ra do
qui trnh phn tch khng chnh xc, hoc ca nn mu.
- Cht phn tch thc t c mt trong mu phn tch; cc php phn tch lp li vn
cho gi tr trung bnh nhng nm trong khong nghi ng, khng chnh xc.
Xc xut ca vic xc nh tn hiu nn v nng cht phn tch c th xc nh
thng k vi mi gi tr o chm (hay lch chun bit trc. Tiu chun quyt
nh hay bc b xc xut sai s l :
- Xc xut xy ra trng hp mu thc t khng cha cht phn tch thm ch khi c
tn hiu o c gi l sai s .
- Xc xut xy ra trng hp mu thc t c cht phn tch mc d kt qu phn tch
c xem bng 0 ( gi tr mu trng) c gi l sai s ( hnh 6.6)

Hnh 6.6 : Phn b ca cc gi tr mu trng v mu phn tch vi sai s v .

Trong thc t phn tch, c ba i lng c trng c thng tin khc nhau c
ffinhj ngha vi chnh xc c a ra l :

133
 - Gii hn quyt inh xDL
- gi tr nh nht pht hin c ( xLOD)
- gii hn nh lng ( xLOQ)
6.4.1. Gii hn pht hin (limit of detection- LOD)
Theo IUPAC v ISO, LOD c xem l nng nh nht ca cht phn tch m
phng php phn tch c th pht hin c Nh vy, LOD ph thuc v thnh phn
nn ca mu phn tch v do phi c nh gi cho mi loi nn mu khc nhau
khi s dng phng php phn tch v phi c cng b trong ti liu v xc nhn
gi tr s dng ca phng php (xem chng 7).
Nu xt php phn tch mu trng s thy khi s php o mu trng ln s cho ta
cc kt qu v phn b hm lng cht phn tch trong mu trng khc 0 (tc l
cng th nghim th nhiu nn cng tng) mc d phn b ny c th tun theo phn
b chun hoc khng. Nh vy sai lm mc phi l khi trong mu c cht phn tch
nhng khng pht hin c v xem khng c (sai lm loi I) l = 0,05. Gii hn ny
gi l gii hn cnh bo (critical limit) (hnh 6.7). Tuy nhin y khng th xem l
gii hn nh lng v khi mt na cc php o vi cc mu c nng s thp
hn Lcrit v b loi b. Do vy, cn chuyn nng thp nht pht hin c v pha
tng nng cho n khi xc sut xy ra sai lm loi I v sai lm loi II bng nhau
(hnh 6.8)

Hnh 6.7: Phn b ca cc php o mu trng khi khng c cht phn tch

134
 (Lcrit l nng ti xc sut mc phi sai lm loi mt (kt lun l c cht
phn tch nhng thc t khng c) l =0,05)

Hnh 6.8 : Gii hn pht hin ti xc sut ca sai lm loi I v loi II l nh

nhau. ( T tri qua phi: phn b ca cc php o vi nng cht phn tch bng
0; nng gii hn cnh bo v nng gii hn pht hin).

Nh vy c th c mt s cch xc nh LOD ca php phn tch nh sau:

6.4.1.1. Qui tc 3
LOD c xem l nng thp nht (xL) ca cht phn tch m h thng phn
tch cn cho tn hiu phn tch (yL) khc c ngha vi tn hiu ca mu trng hay tn
hiu nn (blank or background). Cn ch mu trng trong trng hp ny phi l
mu c thnh phn nn nh mu thc nhng khng cha cht phn tch

Tc l : yLOD= y B k .S B

Vi y B l tn hiu trung bnh ca mu trng sau nb th nghim (t nht 10 th

nghim c lp). SB l lch chun khi o lp li tn hiu ca mu trng, k l i
lng s hc c chn theo tin cy mong mun. Vi tin cy cn t l 99% th
k3
nB
1 1
yB
nB
y
j 1
Bj S 2B
nB 1 i
( y Bi y B ) 2

135
 Nh vy, nng nh nht m thit b phn tch c th pht hin c theo
phng trnh hi qui dng y= a+bx trong phng php ng chun l
y B 3S B a
x LOD
b

Mu trng (Blank) thng c to ra khi khng c cht phn tch. Tuy nhin,
trong nhiu trng hp khi khng c cht phn tch th khng th o c tn hiu o
nn c th thay mu trng bng mu thm chun (spiked) bng cch thm mt lng
bit trc cht phn tch nng nh nht c th ghi nhn c tn hiu vo nn
mu thc, sau o tn hiu phn tch v cng tnh lch chun tng t nh trn.
6.4.1.2. Xc nh LOD khi khng c mu trng
Mt cch khc c dng tnh gii hn pht hin v gii hn nh lng ca
cc php phn tch m tn hiu nn rt thp hoc khng phn tch mu trng l s
dng lch chun ca phng trnh hi qui thay v s dng lch chun ng
nn, tc l xem SB=Sy v tn hiu khi phn tch mu nn yB= a. Khi tn hiu thu
c ng vi nng pht hin YLOD= a+ 3. Sy. Sau dng phng trnh hi qui c
th tm c LOD.
3.S y
xLOD=
b

Ch : Mt yu t khc c ng gp vo sai s khi tnh LOD l im ct trc

tung ca ng chun (gi tr a trong phng trnh hi qui). (Nu tn hiu phn tch
c so snh vi mu trng v khng c sai s h thng th xem a=0 )
Do IUPAC a ra phng trnh tnh LOD nh sau:

k. (S 2 B S a )
2

LOD vi Sa l lch chun ca h s a.

b

Tuy nhin, nu ng chun c xy dng trong khong nng rt rng nh

cc php phn tch s dng ngun cao tn cm ng (ICP) th KB o khng phi l
hng s m t l thun vi nng th khng th dng phng trnh trn tnh ton.
6.4.1.3. Tnh LOD da trn ng chun
IUPAC gi c th dng cng thc sau tnh LOD hay DL (detection limit)
ca php xc nh:

136
 Vi t(=0,05, f=n-2) l gi tr t tra bng chun student 1 pha tin cy P=0,95 v
bc t do f=n-2; m l s th nghim o lp li ti LOD, n l s im xy dng ng
chun, x l gi tr trung bnh cc nng s dng lp ng chun ; b l dc
ng chun (trong phng trnh hi qui).
6.4.1.4. Xc nh LOD da trn t s tn hiu/nhiu ( S/N)
Cch ny ch p dng i vi cc quy trnh phn tch s dng cc phng php
phn tch cng c c nhiu ng nn. Thng thng cch tnh ny p dng ph bin
cho cc phng php sc k, in di.
xc nh LOD, trc tin cn phn tch mu (mu thc, mu thm chun hoc
mu chun) nng thp cn c th xut hin tn hiu ca cht phn tch v xc
nh t l tn hiu chia cho nhiu (S/N = Signal to noise),
trong S l chiu cao tn hiu ca cht phn tch,
N l nhiu ng nn
Nhiu ng nn c tnh v hai pha ca ng nn v tt nht l tnh nhiu
ln cn hai bn ca pc, b rng mi bn ti thiu gp 10 ln chiu rng ca pc ti na
chiu cao.
LOD c chp nhn ti nng m ti tn hiu ln gp 2-3 ln nhiu ng
nn, thng thng thng ly S/N =3

2H
S
N h

Hnh 6.9: Xc nh LOD bng cch tnh S/N

137
 6.4.2.Gii hn nh lng ( limit of quantity- LOQ)
LOD c xem l nng thp nht (xQ) ca cht phn tch m h thng phn
tch nh lng c vi tn hiu phn tch (yQ) khc c ngha nh lng vi tn
hiu ca mu trng hay tn hiu nn (blank or background).

yQ= y B + K. SB

Thng thng LOQ c tnh vi K=10 tc l CQ =10. SB /b

Tm li c 3 vng phn tch lin quan n nng cht phn tch
----------------------tn hiu phn tch ------------------>
XL XQ
Khng pht hin c cht phn tch vng pht hin c vng nh lng
CL CQ
--------------------------nng cht phn tch ------------------->

Th d 6.7: Tin hnh o hp th quang 20 mu trng trong php xc nh asen

nh th d 6.6, kt qu nh sau:

STT 1 2 3 4 5 6 7 8 9 10

Abl 0,0064 0,0063 0,0060 0,0063 0,0053 0,0057 0,0055 0,0061 0,0063 0,0059

STT 11 12 13 14 15 16 17 18 19 20

Abl 0,0061 0,0063 0,056 0,0063 0,0060 0,0058 0,0059 0,0062 0,0055 0,0063

T nhng kt qu ny chng ta c cc gi tr:

Mean Trung bnh 0,00598

Standard Error sai chun 0,00017146

Standard Deviation lch chun 0,00038341

Sample Virance Phng sai mu 1,47E-07

Confidence Level (95%) tin cy 0,000476606

138
 * Gii hn pht hin:
3S B 3.0,00038
LOD 0,2785.10 7 M (0,05g )
b 0,00413

SB: lch chun mu trng.

* Gii hn nh lng:
10S B 10.0,00038
LOQ 0,9284.10 7 M (0,17 g )
b 0,00413

Vi s liu th d 6.6, nu khng lm th nghim vi mu trng m tnh LOD v

LOQ qua lch chun ca phng trnh (Sy=0,00232) th s thu c cc gi tr
sau:
LOD= 3Sy/b = 1,68.10-7 M
LOQ= 10Sy/b=5,62.10-7 M
nhy php o m= b/Sy = 1,78.
Th d 6.8: ly tp s liu nh th d 6.4 vi phng trnh hi qui dng y=(1,520,30)
+(1,930,04)x; lch chun ca phng trnh hi qui l Sy= 0,433.
Theo nh ngha, tn hiu phn tch thu c t nng tng ng vi gii hn pht
hin l yL= yB + 3 SB= yB+ 3Sy = 1,52+ 3.0,433=2,82
Da vo phng trnh hi qui, vi gi tr ny s tnh c gii hn pht hin theo
cng thc x=(y-a)/b=0,67 pg/ml.

139
Hnh 6.9 : phng php xc nh LOD ca phng php phn tch

6.4.3. Gii hn tuyn tnh (limit of linearity- LOI)

Trong phn tch nh lng khi tng nng cht phn tch n gi tr no th
quan h gia tn hiu o v nng cht phn tch khng cn ph thuc tuyn tnh.
Ti nng ln nht ca cht phn tch m tn hiu phn tch cn tun theo phng
trnh tuyn tnh bc nht th gi l gii hn tuyn tnh. Khong nng cht phn tch
t gii hn nh lng n gii hn tuyn tnh gi l khong tuyn tnh hay khong
tuyn tnh (dynamic range).

140
 n tch
u ph
Tn hi

nng cht phn tch

Hnh 6.10. Gii hn pht hin, gii hn nh lng v khong tuyn tnh

6.4.4. nhy ( sensitivity):

Nh trn ni, phng php phn tch c xem l tt nu nng cht phn
tch c th pht hin c cng nh. V vy gii hn pht hin c th c xem l mt
trong nhng i lng c trng ca qu trnh phn tch. Tuy nhin khng d dng so
snh cc qu trnh phn tch ch da trn gii hn pht hin v rt nhiu bi bo nghin
cu phng php khng cng b gii hn pht hin.
nhy l tnh p ng ca h thng phn tch khi thay i nng cht phn
tch hay kh nng pht hin s thay i tn hiu khi c s thay i nh nht v nng
cht phn tch. Thng thng mt phng php phn tch hay thit b phn tch c
coi l nhy nu c gii hn pht hin thp. Do , trong nhiu trng hp c th xem
hai i lng ny ng ngha.
Hin c hai khi nim v nhy.
- nhy ca ng chun ( calibration sensitivity): chnh l dc ca ng
chun (khi phn tch hi qui tuyn tnh) v c xc nh ti bt k im no trn
dy
ng chun. Do , nhy ng chun c tnh theo cng thc m .
dx

Ni cch khc nhy ng chun n gin l s thay i tn hiu khi thay i

1 n v nng cht phn tch.
- nhy ca php phntch: V tnh xc nh ca ng chun b nh hng
bi phn tn lm cho kt qu o khng chnh xc. Do , php o nhy b nh
hng bi dc ca ng chun v chnh xc ca ng chun (tc l b nh

141
hng bi c tnh ca k thut o). V d, c th tng nhy bng cch tng chiu
dy lp hp th trong phn tch trc quang hoc thay i amplier trong phn tch in
ho.
Theo tc gi Mandel*, nhy php phn tch c xc nh l t s gia
dc ca ng chun v sai chun. Do , nhy tng nu dc tng v lch
chun gim. Nh vy c th so snh cc phng php phn tch v k thut phn tch
qua gi tr gii hn pht hin thp, khong tin cy hp v chnh xc cao.
Gia gii hn pht hin v nhy m c mi quan h nh sau:

y L y bl
m tg b vi xL l LOD
x L x bl

CL = ( xL- xbl )/m vi m l nhy php phn tch hay CL = K.Sbl /m v xbl =0
(*).
thu c LOD phn nh trung thnh kt qu phn tch th gi tr ca m trong
phng trnh (*) cn biu th l hm ca khong tin cy c ngha l mt.Sm vi Sm l
sai chun ca gc nghing. t l gi tr chun Student ng vi mc tin cy mong
mun, bc t do . Vi k=3 phng trnh (*) s cho mc tin cy 99,86 %. Vi k=2
phng trnh (*) s cho mc tin cy 89 %.
Theo nhng iu kin th phng trnh (*) c vit thnh:

CL = k.SB /( m t.Sm) v dng gi tr t.Sm biu th LOD. Tuy nhin nu

t.Sm=0 hoc t.Sm << m th CL c th tnh theo phng trnh (*).
nhy t khi l hng s trong khong nng ln, do ch c ngha trong
khong nng nht nh (gia nng thp nht v cao nht (trong khong tuyn
tnh). Tuy nhin, n vn c xem l thng s khi ni v chn lc ca phng php
phn tch.
6.4.5. chn lc ( selectivity):
Khi phn tch cht A trong mu, ngoi tn hiu phn tch do cht A to ra cn c
s ng gp ca rt nhiu cht B, Ccng c mt trong mu. Ngi ta gi y l
nhng cht cn tr.
Khi tn hiu phn tch chung s l
y= bA.CA + bB.CB + bC.CC++ ybl
y bA, bB, bC l cc h s nhy ca A, B, C.
CA , CB, CC l nng ca cht phn tch A v cc cht gy cn tr B, C

142
 ybl l tn hiu ca nn.
Khi mc gy nh hng ca B v C n php xc nh A c biu din
qua h s chn lc. H s ny cng nh th php phn tch cng chn lc.
kB,A = bB/bA kC,A= bC /bA
Phng trnh hi qui xc nh A c th c vit thnh:
Y= bA ( CA + kB,A. CB + kC/A.CC) + ybl

Th d :

6.5. Phng php thm chun (standard addition method) (spiking)

Nh trn thy, ng chun biu din mi quan h tuyn tnh gia nng
cht phn tch v tn hiu cht phn tch c xy dng da trn dung dch chun ch
cha duy nht cht phn tch v mi trng thch hp cho php o tn hiu phn tch.
Tuy nhin, trong mu thc t, ngoi cht cn phn tch, cc cht khc i km vi cht
phn tch cng cho tn hiu gy nhiu n kt qu phn tch. Ngi ta gi y l nh
hng ca nn mu (matrix). Khi tn hiu o ca cng mt nng cht phn tch
trong dung dch chun v trong dung dch phn tch khc nhau c ngha th vic dng
ng chun v xc nh nng cht theo phng php ng chun l v ngha.
pht hin iu ny cn nghin cu nh hng ca cc cht cn tr i km, s dng cc
mu CRM nh gi xem c s khc nhau c ngha gia ga tr trung bnh thc
nghim v gi tr c chng nhn hay khng ( tm xem c xut hin sai s h
thng) v thay i khi lng mu ly phn tch nhm pht hin sai s h thng
khng i hay bin i. Khi c sai s h thng trong phng php phn tch ang s
dng, cn gii quyt bng cc cch sau y:
- Cch 1: Pha dy dung dch chun c thnh phn nn nh vi nn mu phn tch
bng cch thm dn dung dch chun vo mu trng (c ngha l mu thc nhng c
xc nh l khng c cht phn tch, v d phn tch thuc tr su trong c chua, th s
dng c chua khng c thuc tr su lm mu trng sau khi ng nht mu ny) khi
s c dy mu chun. Tin hnh tt c cc bc trong qui trnh phn tch vi dy
mu chun ny (k c dung dch so snh phi l mu trng) v dng th biu din s
ph thuc tn hiu o vo nng cht chun hoc lng cht chun dng. Khi ,
thc cht chng ta vn ang s dng phng php ng chun nhng t mu chun
ch khng phi t dung dch chun. Tuy nhin, cn ch cch lm ny ch s dng
c vi trng hp nh hng ca cc cht i km trong nn mu l khng i ni
cch khc l ch c sai s h thng khng i vi mt loi nn mu.

143
 - Cch 2: Nu nh hng ca nn mu khng qu ln th c th phn tch theo
phng php thm chun gim bt nh hng cu nn mu. Theo phng php
ny, nng cht phn tch c th xc nh theo cch tnh theo cng thc hoc ngoi
suy t th hoc tm phng trnh hi qui dng y=a+bx theo phng php bnh
phng ti thiu.
phng php thm chun cho kt qu ng phi tin hnh thm dn lng
chnh xc cht chun vo cc mu phn tch c khi lng nh nhau, ri tin hnh tt
c cc bc trong qui trnh phn tch. Tuy nhin, cch lm ny i hi nn mu phi
nh nhau v mu phi c ng nht cao. Do vy, thng ngi ta thc hin ph 1 mu
sau lc ra, (tinh ch nu cn) nh mc thnh V0 (ml) dung dch v ly ra cc th
tch Vx ca dung dch ny tin hnh thm chun.
Gi s ly Vx (ml) mu phn tch c nng Cx vo cc bnh c th tch V ml.
Thm ln lt 0, V1 (ml), 2V1 (ml), 3V1 (ml)nV1 (ml) dung dch chun c nng
Cs vo cc bnh nh mc ny v nh mc n vch bng nc ct (cn ch cc
mc nng thm vo phi m bo nm trong khong tuyn tnh ca php o). o
tn hiu phn tch ca cc dung dch ny c cc i lng yx , yx1 , yx2yxn . Khi
nng cht phn tch Cx c tnh theo cc cch sau:
Cch 1: tnh theo cng thc
V trong khong nng kho st c mi tng quan tuyn tnh gia tn hiu
phn tch v nng nn c th thit lp cc mi tng quan sau:

yx VxCx /V

yx1 (VxCx+V1Cs)/V

yx2 ( VxCx +2V1Cs)/V

.
Nh vy c th lp cc t s:

yx VxCx
Do C x
yx V C
. 1 s
yx1 VxCx V1Cs y x1 y x V x

yx 2V C
Cx . 1 s
Tng t nh th s c
y x 2 y x Vx

yx nV C
Cx . 1 s
y xn y x V x

144
 Ly gi tr trung bnh cc nng Cxi ny ta s c nng Cx cn tm.
Cch 2: V ng thm chun v ngoi suy t th (hnh 6....)

Tn hi

u o
Tn hiu mu

Lng thm vo
Lng cht phn tch
trong mu

Hnh 6...: th ng thm chun xc nh cht cha bit

Bng cch ngoi suy t th s tm c gi tr nng Cx cn tm ti v tr c
gi tr y=0

145
Th d:

Hnh 6.11: th thm chun xc nh rutin trong vin thuc Novarrutina,

m pH=4, tc kt th 10mV/s v xung 50mV. Mu c chun b t
2,0.10-7 mol/l trong mu. Mi mu thm 7,3.10-7mol/l rutin c thm vo.

- Cch 3: S dng phng trnh hi qui:

Gi thit phng trnh ng thm chun c dng y=a+bx. Theo cng thc tnh

a
tg=b=a/CxVx ta s c Cx
b.V x
Khong tin cy ca nng cht phn tch trong mu xE l

2
Sy 1 y
S XE 2
xE t. SXE vi b n b ( xi x) 2
i

146
 Khi tng s th nghim n (s im thm trn ng chun) hoc tng bnh
phng hiu sai khc gia xi v x trung bnh th chnh xc ca php o tng. Thng
thng cn t nht 6 im trn th thm chun v th thm chun nn t c
gc gn 450.

Th d 6.8: Kt qu phn tch hm lng Ag trong mu nc ra nh theo

phng php thm chun trn thit b AAS nh sau:

Lng As thm vo 0 5 10 15 20 25 30
(g)

hp th quang A 0,32 0,41 0,52 0,60 0,70 0,77 0,89

Kt qu tnh ton theo phn mm thng k Origin thu c nh sau:

Par. Error

A 0,32179 0,00744 R SD N P

B 0,01864 4,128.10-4 0,99878 0,01092 7 <0,001

Tnh cc i lng khc ta c:

y 0,6014 SxE=0,749 x= A/B=17,3 g

tra bng t vi P=0,95 bc t do f=7-2=5 ta c t= 2,57

Nh vy nng cht phn tch trong mu l : x t.S XE (17,3 1,9) g

* Nhc im phng php thm chun:

- Kh t ng ho
- Dng lng ln mu v mt thi gian phn tch.
- Phng php ngoi suy km chnh xc hn phng php ni suy.
* nh gi hiu sut thu hi ca phng php phn tch da trn d liu
ca phng php thm chun:
Mc ch ca vic nh gi hiu sut thu hi l kim tra xem nh hng ca vic
thay i nn mu n kt qu phn tch ra sao. Do vy, cc th nghim cn tin hnh
trong ton khong tuyn tnh ca phng php phn tch. u tin, xy dng phng
trnh hi qui vi dung dch chun sau xy dng phng trnh hi qui vi mu chun
(nh trnh by cch 1). Thc t, phng php s c thu hi tt (t gn 100%)

147
nu 2 ng thng ny trng nhau. Nu 2 ng chun ny c chung h s gc b
nhng im ct trc tung khc nhau th phng php mc sai s h thng khng i,
cn nu h s gc khc nhau tc l phng php mc sai s h thng bin i (hnh
6.12).
C th tnh nhanh hiu sut thu hi t hai phng trnh hi qui nh nhau:
Gi s phng trnh hi qui s dng dung dch chun c dng y= aC+ bC.xC
Cn phng trnh hi qui ca dy mu chun l y = aj + bj.xf
th nng tnh c t tnh hiu o yf l
xf= (yf-aC)/bC
Nu v th biu din hai trc ta l xC v xf th phng trnh hi qui mi l

xf= (af+bf .xC) trng hp l tng xy ra khi af= 0 v bf= 1

Khi h s thu hi l R= xf.100%/xC= bf.100(%)

Hnh 6.12: ng biu din hiu sut thu hi (ng(1): af>0 v bf<1; ng
(2) af<0 v bf>1)

148
 Th d 6.9: xc nh hm lng Se trong mu huyt thanh, mu c phn hy
theo phng php t. xc nh nh hng ca nn mu n hiu sut thu hi,
ngi ta xc nh hm biu din hiu sut thu hi bng cch chia mu huyt thanh
thnh 6 phn, 5 phn mu c thm nhng lng cht chun khc nhau v sy kh
1000C v x l mu bng HNO3 v H2O2.

Sau , cc mu c chit qua

Hnh 6.12 : Hm biu din h s thu hi vic
xc nh Se trong huyt thanh
ct EXTRELUT v phn chit c
phn tch bng phng php
HPLC. Hiu sut thu hi thu c
qua hm ton hc sau:
xf= 10,609+1,002.xC
Khong tin cy ca hiu sut thu
hi l 0,87<bf<1,14 chng t
khng xut hin sai s h thng
bin i v khng i. Ni cch
khc, phng php xc nh khng
cn tin hnh di dng thm
chun

6.6. Phng php ni chun (internal standard method)

Trong cc php phn tch ng thi cc cht nh phng php GC, HPLC, ICP-
AES ...tn hiu phn tch thng b thay i rt ln do cc iu kin o khng lp li
gia cc ln o nh tc dng pha ng, th tch mu bm vo.. lm cho iu kin
o b thay i khng ging nh khi xy dng ng chun v vy kt qu o khng
chnh xc. Trong iu kin , ngi ta thng thm vo c dy mu chun v mu
phn tch mt cht ni chun v ng chun thay v s dng tn hiu phn tch th s
tnh t l gia tn hiu ca cht phn tch v cht ni chun.
- nh ngha cht ni chun: l lng xc nh cc cht khng phi cht phn
tch c thm vo mu phn tch, mu trng hay mu chun khi phn tch. Cc dung
dch ny c pha long vi cng th tch v o tn hiu ca cc mu, v th biu
th t s tn hiu ca cht chun v cht ni chun vi nng cht chun (hnh 6.13).
Phng php ny rt cn khi phn tch nhng mu c nn phc tp hoc trong cc
php o thay i theo thi gian.
- iu kin cht ni chun:

149
 + Khng c mt trong mu phn tch
+ bn thn cht ni chun khng gy ra s thay i nn mu
+ Tnh cht l ha ca cht ni chun phi cng tng t cht phn tch cng tt. V d
nhit si gn nhau (trong sc k kh) c thi gian lu c trng, kh nng
pht hin nh nhau
+ Thm cht ni chun vi hm lng cao trnh sai s th tch. Mt khc, th tch
thm vo trong mu cn phi c tnh n khi tnh kt qu phn tch
+ Qu trnh tnh ton khi c ni chun phi tng t nh khi c cht phn tch

Hnh 6.13: ng chun khi s dng cht ni chun

Th d 6.10:Phng php ni chun trong sc k kh lng.

Ngun:
http://zimmer.csufresno.edu/~davidz/Chem102/Sp98Web/Overhead/Separations/GLCI
ntStd/GLCIntStd.html)
Gi s cn nh phn hn hp hai cht A v B c thm cht ni chun c thm
vo l IS. Cc thng s o v nng cc cht c cho trong bng sau:

150
 Chun b cc dung dch chun c nng cht A thay i cn gi nguyn nng
(% th tch) ca B v IS. Khi bm mu vo thit b o, th tch bm khng th ly
chnh xc 1 l m c cc gi tr nh bng trn.
Chiu cao pic ca A = (Injection Volume)*(%Av/v)*(Detector Response
A)*(Sensitivity).
Mt s sc ca mu thu c nh sau:

151
 Hnh 6.14: Sc phn tch cht A khi c cht B v cht ni chun

Nu biu din s ph thuc chiu cao pic ca A theo nng (% th tch) th

ng biu din khng phi tuyn tnh. Nhng nu chia chiu cao pic ca cht A cho
chiu cao pic ca cht ni chun v biu din s ph thuc ny vo % th tch ca A
th ng biu din tuyn tnh (hnh 6.15).

Hnh 6.15: ng chunr xc nh cht A khi khng s dng tn hiu ni chun

v ni chun.
i vi cc mu cha bit khi cn phn tch hai cht A v B th thm vo mu
lng cht ni chun nh khi thm vo c dung dch chun v ghi chiu cao pic ca
c A v cht ni chun v tnh t l chiu cao pic v dng phng trnh hi qui tnh
nn cht A trong mu cha bit (hnh 6.16)

152
 Hnh 6.16: Sc khi phn tch mu cha bit v phng php ni suy t ng
chun

Cn ch vic s dng cht ni chun khng c ngha thay th cho vic nh gi

nh hng ca nn mu. Do , phng php thm chun cng c p dng cho c
khi c cht ni chun (hnh 6.17).

Hnh 6.17: th chun (ng A) v thm chun (ng B) khi xc nh phc

ascorbyl-HNE dng cht ni chun l phc ascorbyl octenal trong mu mu.

6.7. S dng ng hi qui trong so snh hai phng php phn tch
Khi nghin cu mt phng php mi, nh ha phn tch cn tin hnh xc nhn
gi tr s dng ca phng php phn tch (validation of method) trc khi c th p
dng phng php nghin cu xc nh cht phn tch trong cc i tng khc
nhau. Mc ch ca vic lm ny l tm xem c xut hin sai s h thng hay khng,
tc l phng php mi c cho kt qu phn tch lun thp hn hay cao hn qui trnh
phn tch chun thit lp.
Khi cn so snh hai phng php phn tch ngi ta c th s dng cc cch sau:

153
 * Cch 1: Dng chun thng k student (t-test) so snh ng ca 2 phng
php qua vic so snh hai gi tr trung bnh. Cch lm ny s khng thch hp cho
phn tch cng c v nng cc cht phn tch bin thin khong rng.
* Cch 2: Mi mu c tin hnh ng thi bi hai phng php v cc mu so
snh c hm lng cht phn tch thay i trong khong nng kho st. Sau s
dng chun t so snh tng cp (xem chng 4).
* Cch 3: Dng phng php th bng cch lm cc th nghim song song vi
mi mc nng vi c hai phng php, sau biu din trn h to hai chiu.
Mt trc ca th dng biu din kt qu ca phng php mi cn trc kia biu
din kt qu ca phng php tiu chun hoc s liu dng so snh. Mi im trn
th (x,y) i din cho 1 mu c phn tch bng 2 phng php c lp. i khi,
vi mi phng php ch phn tch 1 ln nhng cng c trng hp lm c phng
php lm nhiu th nghim lp li.
Trn c s hai tp s liu ny, dng phng php bnh phng ti thiu tnh
cc h s a, b, r v lp phng trnh hi qui dng y=a+bx. Trng hp l tng khi kt
qu ca hai phng php nh nhau i vi tt c cc mu th a= 0; b=r=1 (hnh 6.18).
Thc t, nu khng c sai s h thng th sai s ngu nhin s m bo 2 php phn
tch khng cho cng kt qu vi tt c cc mu v x , y s c quan h tuyn tnh (a0
; b=r 1)
Cc trng hp khng l tng c th xy ra gm:

+ b=1 nhng a 0: mt trong hai phng php phn tch lun c kt qu cao hn
hoc thp hn phng php kia hay ni rng xut hin sai s h thng khng i
gia hai phng php phn tch (c th do tn hiu mu nn khng chnh xc) (hnh b)
+ b>1 hoc b<1 c sai s h thng bin i xy ra vi dc ca ng biu
din mt trong 2 phng php (hnh c) hoc c c hai loi sai s h thng khng i
v bin i (hnh d)
+ Sai s h thng lm cho b1 tc l ng biu din c dng ng cong
(khng tuyn tnh) (hnh e).
+ Mt s trng hp c bit cho kt qu biu din dng hnh f, do cht phn tch
trong mu tn to cc dng khc nhau v t l cc dng ny thay i cc mu khc
nhau. Khi o phng php nghin cu ch pht hin c mt dng cn phng php
kia c th pht hin c hai dng tn ti .

154
 Phng php nghin c

Phng php chun

Hnh 6.18: ng dng phng trnh hi qui trong so snh hai phng php
(a)- hai phng php hon ton ph hp vi tt c cc mu

(b (f): c sai s h thng

Trong thc t, cc h s hi qui a, b tm c lun c tin cy nht nh nn
thng thng khi so snh hai phng php phn tch cn kim tra xem h s ca
phng trnh hi qui a c khc 0 v b c khc 1 c ngha hay khng kt lun
hai kt qu phn tch t c bi hai phng php thuc v trng hp no.

Th d 6.10: Trong nghin cu phng php FIA nh lng amoni, cc tc gi

phn tch 9 mu bng phng php nghin cu v gi 9 mu ny n phng th
nghim khc phn tch theo phng php tiu chun. Hm lng amoni trung bnh
(mg/l) ca 9 mu t c bi 2 phng php nh sau:

TT 1 2 3 4 5 6 7 8 9

PP nghin cu 30,12 36,20 52,88 60,70 78,10 34,67 80,20 94,90 87,12

155
 PP tiu chun 29,80 36,16 51,65 59,13 78,71 33,20 81,54 95,41 86,19

(Ngun: E.A.M. Kronka et al.; Analytica. Chimica. Acta 334 (1996) 287-293).
Bng cch biu din kt qa ca phng php tiu chun trc X v kt qu t
c bi phng php nghin cu trc Y, dng phn mm Origin 6.0, kt qu cc h
s ca phng trnh hi qui thu c nh sau:
a=1,56 ; b= 0.98 ; r= 0,999
Cc i lng thng k tng ng l:
Sy/x= 0,96236; sai chun SEa =0,89338 ; SEb =0,0136
Gi tr chun t vi 7 bc t do, tin cy 95 % l 2,36 v vy h s ca a v b
tng ng l: a= 1,562,11 v b=0,980,032

Kt qu ny cho thy cc ga tr a v b v r khng

100
khc nhau c ngha so vi ga tr 0 v 1. iu chng
90
t khng c bng chng v s khc nhau c ngha gia
80 hai tp s liu.
Y= A+ B* X
70 Cng nhng s liu trn c th so snh theo phng
phngphpFIA

Parameter Value Error

60 php chun t------------------------------------------------------------
tng cp v cng cho kt qu ca phng
A php
php ang nghin cu l ph hp vi phng 1.56502 0.89338
tiu chun.
50 B 0.98009 0.0136
------------------------------------------------------------
Ch : Mc
40 d phng php so snh s dng phng tnh hi qui c s dng rng
ri so snh hai phng php phn tchRnhng
SDkhng
N phiP chng khng c nhc
30 ------------------------------------------------------------
im. D nhn thy nht l mc d sai s 0.99933
ngu nhin 0.96236
xut hin 9c hai<0.0001
phng php
20
nhng khi 20
biu din
30 chng
40 ta 60b qua
50 70 sai 80
s xut
90 hin
100 trong phng php tiu chun
phphng
(trc x) v vy vic tnh ton ngphptiu chu
trnh n qui
hi phn no thiu chnh xc. V vy, cn
Phng php tiu chun
lu rng khi tin hnh so snh theo cch ny phi dng t nht 10 mu tri u trong
ton khong tuyn tnh ca phng php nghin cu.

6.8. ng hi qui khi (weighted regression lines)

Trong cc phn trc, khi biu din mi quan h gia i lng o v nng
cht phn tch, ti mi im thc nghim, chng ta ch s dng mt gi tr y tng ng
vi mt gi tr x. Khi tin hnh th nghim, gi tr y thu c c th l gi tr ca 1 th
nghim hoc gi tr trung bnh ca nhiu ln th nghim. Trn thc t khi nng cht
phn tch tng th sai s khi o ga tr y cng ln. V vy, cn biu din s dao ng

156
ca gi tr y (y y) ti mt gi tr x trong qu trnh lm th nghim lp li. ng hi
qui khi c gi l ng hi qui khi. Sai s ti mi im trn ng chun c
biu din bng thanh sai s (error bar). Thanh ny cng ln khi nng cht phn tch
cng cao (hnh 6.19).

Hnh 6.19: nh hng ca sai s vic o tn hiu phn tch (signal) trong tnh ton
phng trnh hi qui

Mi nng cht phn tch c lm lp li nhiu ln v tn hiu o c gi tr

phng sai tng ng S2. Tuy vy ngay c mi im ring bit c biu din bi to
d (xi, yi) u c lch chun tng ng si. V vy m gi tr khi ring phn c
biu din l wi v c tnh nh sau:
1 n
wi= 2
.
1
Si
S
i
2
i

Khi gi tr ca a , b trong phng trnh hi qui khi c tnh nh sau:

w x y i i i n xw y w
bw i
v a y w b x w
w x nxw
2 2
i i
i

157
 trong x w v y w l to im trung tm khi (weighted centroid) vi

w x
i
i i w y
i
i i
xw = v y w =
n n

Trong phng trnh hi qui khi, to im tm ( x w y w ) gn vi im u ca

th hn nn sai s nh hn.
Tuy nhin thc t cc nh phn tch khi dng phng php phn tch cng c
khng ng dng tnh ton hi qui tm cc h s a, b ca phng trnh v nng
mu phn tch m ch cn khong gi tr thc tn ti
Trong tnh ton hi qui khi, gi tr lch chun (Sxow) ca nng cn tm
c a ra bi phng trnh
1
2
S ( y / x)w 1 1 ( y o y w) 2
S xo w 2 2
b w0 n b w i xi n x w )
2

i
Trong phng trnh ny S(y/x)w c tnh nh sau:
1
( wi yi 2 n y w 2 ) b 2 ( wi xi 2 n x w 2 ) 2

S( y / x) w i i
vi x0 l xp x khi ca y0.
n2

Phng trnh ny cho thy im gn u ng chun (gi tr khi ln nht) v
im gn im tm ti (y0- y w) nh s c gii hn tin cy nh nht.

S khc nhau gia hai phng trnh hi qui l gi tr 1/w0. V w0 gim r rt khi y
tng nn tin cy tng khi y tng.
Nh vy c th kt lun rng mc d tnh ton trong phng trnh hi qui khi
phc tp hn nhng s thu c khong gii hn tin cy ca nng cht phn tch tin
cy hn trong phn tch cng c. Vi s h tr ca cc phn mm tnh ton trong thc
t phn tch c th s dng phng trnh hi qui khi tng tin cy ca kt qu
phn tch.

Th d 6.11: Khi xc nh cc mu quinin theo phng php hunh quang, mi nng

lm lp li 5 ln, gi tr trung bnh v lch chun thu c nh sau:

Nng (ng/ml) 0 10 20 30 40 50

158
 Cng hunh quang 4 22 44 60 75 104
3 20 46 63 81 109
4 21 45 60 79 107
5 22 44 63 78 101
4 21 44 63 77 105

Cng hunh quang trung bnh 4 21,2 44,6 61,8 78,0 105,2

lch chun 0,71 0,84 0,89 1,64 2,24 3,03

Dng phn mm Origin 6.0, nhp 3 ct s liu : x (nng ) ; y (cng hunh

quang) v lch chun. nh du ct lch chun, vo Column -> set as Y error.
tm ng hi qui v phng trnh hi qui khi, vo Tool ->Linear Fit, chn
error as weight.
Kt qu thu c hnh 6.8 v 6.9.

120

100

80
Y=A+B*X
cnghunhquangtrungbnh

60 Parameter Value Error

------------------------------------------------------------
40 A 2.20952 2.01184
B 1.99029 0.06645
------------------------------------------------------------
20
R SD N P
0
------------------------------------------------------------
0.99778 2.77976 6 <0.0001
0 10 20 30 40 50
nngquinin(ng/ml)

Hnh 6.8 :ng hi qui khng tnh n cc tn hiu o lp li

Nu khng tnh n lch chun th phng trnh hi qui biu th cng

159
hunh quang trung bnh theo nng quinin c dng: y= 2,21+1,99 x.

120

100

80

Parameter Value Error

60
cnghunhquang

------------------------------------------------------------
A 3.22566 0.87159
40 B 1.92587 0.05081
------------------------------------------------------------
20
R SD N P
------------------------------------------------------------
0 0.99861 1.44252 6 <0.0001
------------------------------------------------------------
0 10 20 30 40 50
nngquinin(ng/ml)

Hnh 6.9: ng hi qui khi xc nh

Kt qu ny so vi ng hi qui khng tnh n cc gi tr o lp li c s khc
nhau v cc h s a, b vi Y= 3,23 +1,93x
-SV hy thit lp phng trnh hi qui khi v phng trnh hi qui khng tnh
khi theo cng thc nu.
- Nu mu phn tch c hunh quang trung bnh l 41,3 th khong tin cy nng
quinin trong hai trng hp khi tnh v khng tnh n hi qui khi l bao nhiu.

160
161
Chng 7 : M BO CHT LNG TRONG
PHNG TH NGHIM PHN TCH

7.1. m bo cht lng v kim sot cht lng (QA/QC)

7.1.1. Khi nim m bo cht lng v kim sot cht lng
Kt qu phn tch ca phng th nghim (PTN) ng vai tr rt quan trng trong
hot cc ng kim tra cht lng sn phm, kim tra s nhim mi trng v trong
rt nhiu hot ng khc. V vy, mi kt qu phn tch do PTN a ra cn phi c
kim sot cht lng v m bo cht lng.
Do , c c kt qu tt, tin cy th trong qu trnh tin hnh th nghim,
PTN phi xy dng v p dng h thng cht lng, trong c s an xen, kt hp
ca cc hot ng QC, theo yu cu ca ISO/IEC Guide 25_ TCVN 5958: 1995 -Yu
cu chung v nng lc ca phng thc nghim/ hiu chun. Hin nay, tiu chun ny
c chuyn thnh tiu chun TCVN ISO/IEC 17025: 2007, bin son da trn
tiu chun quc t ISO/IEC 17025: 2005 gm hai nhm yu cu ln: yu cu v qun
l v yu cu v k thut nh trong bng 7.1. y cng l hai yu cu chnh m PTN
phi p ng c khi xin cng nhn cht lng PTN.
Bng7.1 : Yu cu v qun l v k thut khi tin hnh QA/QC.

Yu cu v qun l: Yu cu v k thut
1. T chc. 1. Yu cu chung
2. H thng cht lng. 2. Nhn s.
3. Kim sot ti liu. 3. Tin nghi v iu kin mi trng.

162
 4. Xem xt yu cu, ngh v hp ng. 4. Phng php th nghim, hiu
5. Hp ng ph v hiu chun v th chun v ph duyt phng php
nghim. 5. Thit b.
6. Dch v mua sm v ngun cung cp. 6. Lin kt chun o lng.
7. Dch v khch hng. 7. Ly mu.
8. Khiu ni. 8. Qun l mu th nghim, hiu
9. Kim sot cng vic th nghim hoc chun.
hiu chun khng ph hp. 9. m bo cht lng kt qu th
10. Bin php khc phc. nghim v hiu chun.

11. Bin php phng nga. 10. Bo co kt qu.

12. Kim sot h s.

13. nh gi ni b.
14. Xem xt ca lnh o.

Kim sot cht lng (quality control- QC) l cc hot ng c k hoch ha

nh gi, x l kim sot s liu phn tch, th nghim nhm cung cp cc iu
kin v bin php k thut cn thit gim st v kim sot cht lng ca mt qu
trnh no trong sn xut hay nghin cu khoa hc nhm m bo cht lng cho
sn phm, ng thi pht hin cc sai st tm cch khc phc cc sai st m
bo thu c kt qu ng mong mun v cung cp s liu c cht lng ca sn
phm khi ban hnh.
m bo cht lng (quality assurance-QA) l thut ng dng ch tt c cc
hot ng cn thit duy tr cht lng kt qu phn tch. Cc hot ng QA nh
hng n nhiu lnh vc nh t chc, o to, thit b, phng php...Ni cch khc,
QA l ton b h thng qun l m bo cho s thnh cng ca cc hot ng m
bo cht lng v kim sot cht lng. H thng QA l iu kin tin quyt cho vic
cng nhn PTN.
Tm li QA/QC l mt lot cc thao tc cn phi c tun th nghim tc k t
khi ly mu n khi phn tch, c th a ra c nhng s liu ng tin cy v
c kim sot.

163
7.1.2. Cc iu kin tin hnh QA/QC
Thc hin QA/QC trong PTN phn tch thc cht l xy dng h thng qun l
cht lng v t chc thc hin cc bin php kim sot, x l, nh gi v hiu chnh
cc s liu.
7.1.2.1. Nng lc qun l v thc thi cng vic ca phng th nghim .
PTN phi thit lp mt h thng cht lng c th hin bng h thng cc vn
bn, ti liu, gi chung l h thng ti liu cht lng. H thng ny bao gm: s tay
cht lng; cc qui nh; th tc iu hnh nhng hot ng; qu trnh c tnh cht
chung ca phng th nghim; cc qui nh; ti liu c tnh cht ch dn cng vic c
th. V PTN phi c mt c cu t chc, trch nhim v ngun nhn lc, c cc iu
kin v bin php thc hin qun l cht lng v vn hnh c h thng ny
trong ton b hot ng ca mnh.
PTN phi nh k tin hnh nh gi ni b theo cc thi hn (thng l mt
nm) v th tc nh kim tra xem hot ng ca PTN c lin tc tun th cc
yu cu ca h thng cht lng hay khng. Cn b qun l cht lng c trch nhim
lp k hoch v t chc nh gi theo chng trnh nh. Khi vic nh gi pht
hin ra nhng nghi ng v hiu qu ca cc hot ng hoc v s ng n ca cc kt
qu phn tch, o, th, PTN phi tin hnh cc hot ng khc phc kp thi , phi
thng bo bng vn bn cho cc c s c lin quan bit v nhng sai st ny hiu
chnh chng.
Lnh o PTN phi nh k (thng l mt nm) xem xt li h thng qun l,
cht lng v cc hot ng phn tch, o, th ca PTN m bo s ph hp lin
tc v tnh hiu qu ca chng v a ra nhng thay i hoc ci tin cn thit.
7.1.2.2. V c s vt cht.
C s vt cht ca PTN l yu t khng th thiu c m bo cho s thnh
cng ca QA/QC, n phn nh nng lc ca phng th nghim. V vy, ty theo yu
cu ca cng vic m PTN xy dng c s vt cht cho ph hp. iu kin c s vt
cht ti thiu ca mt PTN phn tch l :
*Tiu chun /phng php.
Cc tiu chun / phng php m PTN tun theo phi p ng c yu cu
c xc nh v ph hp vi php phn tch, o, th thuc phm vi hot ng ca
PTN, bao gm c ly mu, x l, vn chuyn, lu kho v chun b mu. V tiu
chun/phng php lun c s pht trin do PTN phi c s cp nht cc phng

164
php v c k hoch nng cp trang thit b c th thc hin tiu chun/phng
php tin tin. PTN phi xy dng mt phng php ph duyt tiu chun/phng
php bao gm nh gi sai s, lch, gii hn pht hin ca phng php v gii hn
tin cy, chn lc, kh nng chng li iu kin bn ngoi chn ra c nhng
tiu chun/phng php ph hp vi yu cu s dng.
* Chn la phng php :
Tt nht l s dng cc phng php tiu chun ha v phi s dng nhng n
phm mi nht ca cc tiu chun. l cc tiu chun quc t, tiu chun vng, tiu
chun quc gia. Khi cn thit, PTN phi hiu chnh li cc tiu chun ny bng nhng
chi tit b sung m bo s p dng thch hp. PTN cng c th chn cc phng
php thch hp c cng b trong cc sch v tp ch khoa hc. Cc phng php
ni b (do phng th nghim t xy dng) cng c th c s dng nu ph hp vi
yu cu qui nh v c kim nh li .
i vi cc phng php cha c cng b trong tiu chun hoc qui nh k
thut, cn phi c s tha thun ca c quan qun l chng trnh quan trc khi phi
s dng nhng phng php khng c trong cc qui nh k thut tiu chun. S tha
thun ny c biu hin bng mt vn bn qui nh r rng v cc yu cu v mc
ch ca phng php phn tch, o, th.
*Ph duyt phng php :
PTN phi kim tra li cc phng php tiu chun, khng tiu chun v cc
phng php mi khng nh cc phng php ny l ph hp vi vic s dng.
Phi ghi li cc kt qu ca vic ph chun v th tc thc hin vic ph duyt
ny.Vic ph duyt phi da trn cc thng tin v lp la, ti lp, cc c trng
tiu biu ca vic phn tch o, th v nh hng ca cc yu t my mc, con ngi
v mi trng n khng m bo ca kt qu v phi kt thc bng mt cng b
ca PTN rng phng php l ph hp vi yu cu s dng nh.
S ph hp ca phng php c th kim tra bng cch so snh vi cc yu cu
c trng cho vic s dng nh nh khng m bo ca kt qu, gii hn pht
hin, chn lc ca phng php, tuyn tnh, gii hn nh lng, lp li hoc
ti lp, kh nng chng li cc nh hng bn ngoi...
Cc k thut c s dng ph duyt mt phng php c th l mt
hoc mt s trong cc cch sau: s dng cc chun o lng hoc mu chun; so snh
kt qu vi cc phng php khc; so snh lin phng th nghim; nh gi mt cch
h thng nhng yu t nh hng n kt qu; nh gi khng m bo ca kt qu

165
da trn hiu bit khoa hc v cc nguyn tc l thuyt ca phng php v kinh
nghim thc t .
*c lng khng m bo o
PTN phi c th tc c lng khng m bo o ca tt c cc php phn
tch, o, th.
PTN phi quan tm n tt c cc thnh phn quan trng khi nh gi khng m
bo o bng cch s dng cc phng php ph hp. Ti liu c bn nh gi, trnh
by khng m bo ca php o hin nay l ISO/ TAG 4/WG3Guide to expression
of uncertainty in measurement ,1993 v b tiu chun ISO 5725
*Trang thit b
a/ Tt c trang thit b ca phng th nghim phi ph hp vi yu cu ca tiu
chun/phng php m phng th nghim m nhn, phi t chnh xc theo cc
qui nh k thut tng ng.
Phng th nghim phi giao vic vn hnh v bo dng trang thit b cho cc
cn b nng lc v c k hoch tng cng c s vt cht c nhng trang thit b
ph hp thc hin cc tiu chun mi ban hnh ng thi loi b nhng tiu
chun/phng php lc hu.
Trang thit b phi c h s ghi chp v phi c nh du, dn nhn, theo di,
kim tra qu trnh vn hnh ca chng pht hin kp thi nhng sai st v c s
hiu chnh hp l c nhng trang thit b c chnh xc theo cc qui nh k thut
tng ng.
b/ Trang thit b phi c nh du, dn nhn phn bit v nhn dng c d
dng, trong phn nh c tnh trng hiu chun, kim nh v thi hn hiu
chun, kim nh tip theo ca n. Phi duy tr v lu gi h s ca tng loi trang
thit b .
c/ Phi thit lp cc th tc bo dng v thc hin vic bo dng trang thit b
thng xuyn hay nh k .
Trang thit b sai hng phi c dn nhn phn bit vi cc trang thit b
bnh thng. Phi ngng s dng n cho n khi sa cha, hiu chnh xong v vic
hiu chun hoc kim nh sau chng minh thit b hot ng tt .
Khi v l do no , trang thit b vt ra ngoi phm vi kim sot trc tip ca
PTN trong mt thi gian nht nh, PTN phi kim tra m bo rng thit b vn
tt trc khi a vo hot ng tr li trong PTN.
d/ Phi m bo tnh lin kt chun o lng ca tt c cc trang thit b ca PTN.
166
 Thc cht ca yu cu m bo tnh lin kt chun chnh l vic thc hin mt chui
php hiu chun k tip nhau i vi tt c trang thit b ca PTN, lm cho cc trang
thit b ny u c so snh (trc tip hay gin tip) v tip l hiu chnh theo h
thng chun o lng quc gia hay quc t, t m bo cho trang thit b o, th,
phn tch lun tin cy v chnh xc. C th phng th nghim phi thc hin mt s
vic sau:
+PTN phi xy dng v thc hin chng trnh hiu chun cho tt c cc trang thit
b nh hng r rt n gi tr v chnh xc ca cc kt qu phn tch, o, th trc
khi a chng vo s dng cng nh trong sut qu trnh s dng chng. Chng
trnh hiu chun phi bao gm c cc phng tin o dng cho cc php o ph tr , v
d o cc iu kin mi trng .
+i vi cc trang thit b khng th thc hin c vic hiu chun nu trn,
phng th nghim c th p dng cc bin php sau:
- Tham gia mt chng trnh so snh lin PTN hoc cc cuc thi th nghim
thnh tho c bng chng v s ph hp ca cc trang thit b lin quan.
- S dng cc mu chun m cc gi tr v thnh phn v tnh cht ca n
c chng nhn kim tra trang thit b.
- S dng cc chun hoc cc phng php c cc bn lin quan tho
thun.
*Tin nghi v iu kin mi trng phng th nghim .
Mi trng PTN l yu t rt quan trng do PTN phi m bo cc yu cu v
bo qun trang thit b, nhy, nh sng, m, rung, ting n, nhiu x ph
hp vi tiu chun/phng php la chn. Yu cu chung l tin nghi ca PTN, bao
gm c cc iu kin v mi trng, chiu sng v cc ngun nng lng, phi ph
hp c th d dng thc hin mt cch ng n cc php phn tch theo yu cu.
Cn c s quan tm c bit khi vic ly mu, hoc vic phn tch c thc hin
nhng ni ngoi a im c nh ca PTN. Phi qui nh thnh vn bn cc yu cu
i vi cc tin nghi v iu kin mi trng c th nh hng n kt qu phn tch.
PTN phi p ng c yu cu phn tch ( mc nht nh). Cc nhn vin,
k thut vin phi c y trang thit b, iu kin thao tc cc cng vic c giao
m khng cn tr nhau. Khng gy nhim bn t ngun ny sang ngun khc.
PTN phi c cc th tc v thc hin vic gim st, kim tra chc chn rng
mi trng khng tc ng xu ti vic ly mu; vic tin hnh phn tch, o, th.
Vic thc hin cc php phn tch phi c dng li khi cc iu kin mi trng

167
khng ph hp. Cn c bit kim sot s ph hp vi cc yu cu ca cc yu t nh
s v trng v mt sinh hc, bi bn, nhng tn hiu in t gy nhiu, cht phng x,
vic cung ng in, nhit , m, rung ng, ting n v.v
Trng hp c nhng hot ng nh hng ln nhau, PTN phi phn lp mt
cch c hiu qu cc khu vc ny trnh nhng nh hng xu qua li.
PTN phi thc hin s kim sot i vi vic s dng v ra vo phng th
nghim m khng c nhim v hn ch nhng nh hng xu n kt qu phn
tch, c bit nhng ni c nh hng trc tip n cht lng cc php phn tch.
*Ha cht thuc th.
i vi PTN mi ch tiu, phng php u c yu cu v cp tinh khit ca
ha cht, thuc th s dng. c bit i vi trng hp phn tch lng vt th
tinh khit ca ha cht, thuc th, nc ct c dng l rt quan trng.
* Bo qun mu
Khi nhn vin PTN tip nhn mu phi c mt phng n qun l mu ph hp
nh phi ghi chp nhng thng s c lin quan, phi c cc k hiu i vi tng mu
trnh nhm ln v bo m cc tnh cht vn c ca n khng b thay i n tn
khi phn tch a ra nhng kt qu ph hp vi yu cu.
-PTN phi c cc th tc cho vic qun l mu thch hp vi tng thng s.
- PTN phi c cc cch nhn dng v phn bit mu. Nhng k hiu nhn
dng phi c duy tr trong sut thi gian tn ti ca mu trong PTN m bo
khng gy ra s nhm ln cc mu khi phn tch, khi lun chuyn, k c khi a vo
h s, ti liu.
- Khi tip nhn mu, PTN phi ghi li mi s khng bnh thng hoc sai lch so
vi m t trong cc phng php phn tch, o, th m PTN s dng; phi tham kho
kin ca cc b phn lin quan h cho cc hng dn c th khi c s nghi ng v
s ph hp ca mu.
PTN phi c cc th tc v tin nghi phng trnh cc h hng i vi mu
trong qu trnh lu gi, x l, chun b v tin hnh phn tch. Phi tun th cc hng
dn km theo mu.
*Mu QC.
T chc ly mu v phn tch mu QC l bin php cn thit ca h thng cht
lng kim sot qu trnh ly mu v phn tch. Cc mu QC thng dng l mu
QC thit b v mu QC phng php.

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 Cc mu QC thit b dng nh gi v kim tra cht lng kt qu do thit b
mang li. N bao gm chun kim tra (control standard), chun thm tra (verification
standard)v mu trng thit b (instrument blank).
- Mu trng thit b: mt lng nh dung mi, thng l nc ct, c
cho trc tip vo thit b o s nhim do thit b gy ra. Mu ny
thng dng nh gi n nh v nhiu ca thit b.
- Chun kim tra: l mu chun dng kim tra chnh xc ca cc
dung dch chun v c dng chun ha thit b .
- Chun thm tra: l mu chun theo di n nh ca thit b theo thi
gian.
Cc mu QC phng php c dng nh gi cht lng ca phng php
c dng trong PTN. N gm mu trng phng php (method blank), mu lp PTN
(replicate sample), mu thm vo phng php (additional sample)v mu chun
c chng nhn hay mu kim chng (certified reference material- CRM).
- Mu trng phng php: l mu bng vt liu sch c qua cc bc x l
ging nh cc mu phn tch. Mu ny c dng nh gi s nhim to ra
trong ton b qui trnh phn tch .
- Mu lp PTN: hai hoc nhiu hn cc phn ca cng mt mu phn tch c
chun b v phn tch ring r bi cng mt phng php. Mu ny dng nh
gi chm ca kt qu phn tch trong PTN.
- Mu thm phng php: l cc mu phn tch hoc vt liu sch c thm
vo mt lng cht phn tch bit trc v c x l ging nh khi phn tch.
Mu thm c dng nh gi mc sai lch gy ra do nh hng ca nn
v sai s ca PTN, cc sai s hiu chun, sai s chun b mu ....
- Mu chun c chng nhn (CRM): l nhng mu tin cy trong hm
lng ca cc cht c xc nh chnh xc bng cch tnh trung bnh t kt qu
ca nhiu k thut phn tch v nhiu PTN. Nhng mu ny thng c cung
cp bi t chc NIST (National Institute of Standard and Technology) v mt s
t chc khc v c bn trn th trng. Vic phn tch mu kim chng l
nh gi chnh xc, ng, sai s h thng ca phng php c s dng.
*Trnh nng lc ca th nghim vin.
Tt c cc k thut vin vn hnh trang thit b ca PTN phi c y nng lc,
trnh cn thit p ng yu cu ca cng vic, cc k thut vin phi c o to
ng chuyn ngnh v PTN thng xuyn phi c k hoch bi dng, b sung

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nhng k thut mi cho nhn vin d dng tip cn vi nhng phng php tin tin
nng cao trnh ph hp vi yu cu thc t.
Nng lc ca th nghim vin c phn nh qua n nh ca cc kt qu
trong nhng hot ng kim sot cht lng v trong nhng hot ng tham gia th
nghim lin PTN v th nghim thnh tho.
Nhim v ca cn b lnh o v k thut vin phi c phn cng r rng v
c th hin bng vn bn.
* T chc hot ng QA/QC:
T chc m PTN trc thuc cn phn tch r nhim v, trch nhim ca tng cn
b, nhn vin trong PTN, xc nh c th ngi no l cn b qun l k thut,
ngi no l cn b qun l cht lng v phi l nhng ngi c nng lc, kinh
nghim, hiu bit v x l thng k, bit lp k hoch QA/QC. Nh vy mi c th
pht hin nhanh nhng ch cha hp l ca QA/QC v c bin php khc phc kp
thi.
Cn hnh thnh QA/QC theo ngnh dc trong n v, trong ngi qun l chu
trch nhim chung v QA/QC cc chuyn ngnh nhm duy tr nhng hot ng
thanh tra cht lng ni b v nh gi bn ngoi, t chc hot ng gim st cht
lng v cc hot ng h tr k thut m bo cht lng.
iu kin bo qun v lu hnh kt qu s dng phi c tin cy v c kh
nng so snh c vi nhau, cng nh trao i quc t.
7.1.3. Th tc tin hnh QA/QC
Mt chng trnh kim sot cht lng tt phi bao gm y cc yu t sau:
7.1.3.1.Thit lp k hoch ng: Khi thit lp k hoch phn tch cn xc nh ni
dung, nhim v ca cc php phn tch t c cc yu cu v ngun nhn lc, trang
thit b, phng php ly mu v phn tch, cc bin php phng tin m bo an
ton.
7.1.3.2.S cng nhn trnh th nghim vin: Trc khi th nghim vin c
php lm vic th phi chng minh c kh nng ca mnh trong qu trnh phn tch,
c th hin qua thao tc, tc phong v tnh n nh ca kt qu phn tch. V d c
th yu cu th nghim vin phn tch lp li 4 ln mu kim tra (c hm lng trong
khong 5 - 50 ln gii hn pht hin ca phng php- MDL) khi dng phng php
phn tch trong PTN .
7.1.3.3. thu hi lng thm chun: Thm lng bit trc dung dch chun vo
mu phn tch nh gi nh hng ca nn mu, kim tra cc yu t nh hng khi

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phn tch mt mu c nn mi, nh gi sai s ca PTN, cc sai s hiu chun, sai s
chun b mu.
7.1.3.4.Phn tch cc mu chun t ngun bn ngoi: Vic phn tch mu chun sn
c ( mu chun kim tra hoc mu kim chng CRM) cn tin hnh thng xuyn
hoc t nht phi tin hnh khi php phn tch lng thm chun trn khng mang li
hiu sut thu hi chp nhn c.
7.1.3.5.Php phn tch mu trng: Phn tch mu trng l rt cn thit nh gi
s nhim to ra trong ton b qui trnh phn tch, n c dng nh gi n
nh, nhiu ca thit b. Do , s mu trng cn phn tch t nht phi chim 5 o/o
tng s mu phn tch. i khi php phn tch mu trng c th tin hnh sau khi phn
tch mt mu hoc phn tch mu c nng ln hn mu c hm lng cao nht theo
ng chun.
7.1.3.6.Chun ha cc tiu chun: Khi tin hnh mt php phn tch, phi c t nht
ba t l pha long ca mt dung dch chun. Sau phn tch mt hay nhiu mc nng
dung dch chun trong phm vi tuyn tnh kim tra ng chun hng ngy. Cc
kt qu phn tch c th bo co c l nhng kt qu nm trong phm vi tuyn tnh
ca ng chun dng. Khng bo co cc gi tr cao hn nng cao nht trong
ng chun, tr khi m rng phm vi tuyn tnh. Khi s dng mt ng chun
phn tch, khng thay cc i thng s dng c. Gi tr thp nht c th bo co c
l gii hn pht hin ca phng php (MDL).
7.1.3.7. Php phn tch kp: Dng nh gi chnh xc ca php phn tch. S
mu cn phi phn tch kp t nht phi chim 5o/o s mu cn phn tch.
7.1.3.8.Cc th kim tra (control charts).
Hai loi th kim tra thng c dng trong PTN l th trung bnh cho mu QC
v th gii hn.

th trung bnh (mean chart): Cn gi l th kim tra ng ca phng

php. N c xy dng t gi tr trung bnh v lch chun cu mu QC. th
ny gm gii hn cnh bo trn v gii hn cnh bo di (UWL ; LWL), gii hn
kim sot trn v gii hn kim sot di (UCL ; LCL) ca nng trung bnh. Thng
thng, gii hn ny tng ng vi qui tc 2s v 3s (vi s l lch chun). Nu
nng thay i trong khong rng th c th biu th bng hiu sut thu hi.

171
 Hnh 7.1 : th trung bnh ca mu QC
Th d:
g/l)
ng (
N g/l)
ng (
N

Hnh : 7.2: th kim sot cc mu QC

172
 Trong qu trnh phn tch, nu hm lng trong mu QC vt ra ngoi khong
UWL v LWL th cc kt qu phn tich mu cha bit s khng c chp nhn.
th ny cng c dng nh gi hng nm loi tr im yu cu phng php v
c ci tin lin tc php phn tch.
* th gii hn (range chart): Cn gi l th kim tra chnh xc ca
phng php. N c xy dng t gi tr trung bnh v lch chun ca mu QC
nhng biu din lch ca php phn tch lp hoc phn tch p theo thi gian. Nu
cc kt qu phn tch p khng khc nhau th c th xem ng nn trn th l
zr. Do , ch gii hn cnh bo trn v gii hn kim sot trn l c ngha.
Nu lch chun bit trc th c th s dng h s qui i t lch
chun sang gii hn.

Gii hn trung bnh: R = D2.s (vi D2 l yu t qui i s sang gii hn;

D2=1,128 nu lm lp li 2 ln, D2 = 1,693 nu lm lp li 3 ln). s(R) lch chun
ca gii hn.

gii hn kim sot : CL = R 3s(R)

gii hn cnh bo : WL = R 2s(R)

*Cc gi thit:
1. Trung bnh c 1 trong s 20 im o vt qu gii hn cnh bo (WL) v mt
trong 300 im o vt qu gii hn kim sot (CL).
2. ng trung tm l x ln gii hn pht hin ca phng php (MDL) vi x ln
nht l 20.
3. Tiu chun v cc hnh ng x l p dng cho cc im o nm trn hai cn
ca tham s.
* Cch khc phc.

Tham s thng k Tiu chun Hnh ng

Gii hn 1. Mt im o vt qu CL. 1. Lp li php phn tch.

Kim sot(CL) 2a. Cc php phn tch lp li < CL 2.a. Tip tc phn tch
2b. Cc php phn tch lp li> CL 2b. Dng li v hiu chnh

Gii hn 1. Hai hoc ba im o vt qu 1. Phn tch mu khc

cnh bo (WL) WL. 2.a. Tip tc phn tch.

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 2.a. im o tip theo < WL. 2.b. Dng li v hiu
2.b. im o tip theo > WL chnh

lch chun (SD) 1.Bn hoc nm im o>1 SD 1.Phn tch mu khc

2.a. im o tip theo < 1SD 2.a. Tip tc phn tch
2.b. im o tip theo > 1SD 2.b. Dng li v hiu
chnh

ng trung tm 1. im o nm trn CTL 1. Phn tch mu khc

(CTL) 2.a. im o tip theo di CTL 2.a. Tip tc phn tch
2.b. im o tip theo trn CTL 2.b. Dng li v hiu
chnh

7.1.3.9. th hai mu (2 sample plots):

Dng th hai mu kim tra xem sai s h thng ca phng php c phi l
nguyn nhn gy ra s sai lch kt qu phn tch gia cc PTN hay khng. Cch kim
tra theo th ny cng tng t nh so snh hai phng php phn tch s dng
phng trnh hi qui.
Nguyn tc: Mi PTN tham gia trong chng trnh kim tra cht lng phi gi
kt qu phn tch hai mu tng t nh nhau (X,Y) v tr li cu hi xc nh cc mu
nh th no.
Nu k hiu cc mu l x, y, nh s cc PTN t 1... m ta s thu c m cp gi
tr x 1 y1 , x 2 y 2 , , x m y m . V cc im ny ln trc to 2 chiu x, y c cc vch
chia bng nhau 2 trc.
+ Mi im trn th i din cho mt cp cc kt qu ca mt PTN. ng
nm dc v ng nm ngang c v qua im chia th thnh bn gc phn t.
+Nu kt qu t cc PTN khc nhau b thay i v sai s ngu nhin th s xc
nh ca X v Y trong mi trng hp c th a ra kt qu nh sau: C hai u cao ;
c hai u thp; X thp, Y cao; Y thp, X cao.
+ Nu sai s h thng l nguyn nhn chnh ca sai lch th c th khng nh
mt iu chc chn l: mt PTN m t c gi tr X cao cng c xu hng t c
gi tr Y cao. iu dn n s vt tri ca cc im pha trn bn phi v bn
tri gc phn t ca th.

174
 + Gi thit o l tn ti sai s ngu nhin th tt c cc im s nm gc
nghing 450 ca th. Trong thc t sai s ngu nhin lun c mt, khi cc im
s ri vo hnh ellip c trc i xng ln l ng cho. di ca ng vung gc
ti mt im a ra sai s ngu nhin. V ng vung gc giao nhau vi ng
vung gc ti im (X,Y) to ra sai s h thng ca phng php .

mu Y

( X ,Y )

mu X

Hnh 7.3. th hai mu (Youden Plot) kim tra sai s h thng cc PTN
7.1.3.10. Chun b php th lin PTN
Mc ch ca php th ny l nh gi s dao ng ca phng php phn
tch ang nghin cu mt s PTN trong h thng PTN. Kt qu c dng nh
gi xem bn thn phng php c ph hp khng. Mi PTN tin hnh phn tch
cng mt mu vi cng phng php hai mc hm lng cao v thp. S dng phn
tch phng sai nh gi kt qu ca cc PTN xem c s khc nhau c ngha hay
khng.
Tm li, cc bc tin hnh QA/QC trong PTN c th c m t nh s hnh 2.

175
 Mc tiu s dng

Xy dng phng php

La chn phng php

Bin son phng php

Chp nhn phng php

- kim tra hiu qu
- nh gi hiuKhng
qu tt

Tt

Kim
Tt sot cht lng
Khngtt

(bao gm bo tr thit b)

176
 Sot xt/chp nhn li
- kim tra hiu qu
- nh gi hiu qu

Hnh 7.2 : Hot ng QA/QC trong PTN .

7.2. M hnh ha v ti u ha phng php phn tch

7.2.1.Ti u ha l g?
Ti u ha l qu trnh tm cc i hay cc tiu ca mt i lng o, thng
thng trong ha phn tch l tn hiu phn tch hoc hiu sut thu hi, nhiu ca
thit b, lp li ca php o.... Trong phn ny ch cp n vic ti u ha cc
iu kin phn tch sao cho tn hiu phn tch thu c l ln nht c th tng
nhy php phn tch, khng c sai s h thng v chnh xc ca php phn tch tt
nht ( chun nh nht).
S cc yu t nh hng n qu trnh phn tch ha hc c th m t tm nh
sau :
u vo Chuyn i tn hiu o u ra

Mu Qui trnh phn tch Kt qu phn tch

Yu t nh hng Thit b i lng o (hm)

Bin Qu trnh Sn phm

Cc tham s H thng Nng cht phn tch
Th nghim Tn hiu o

177
 Ci t ban u

ti u ha khi tin hnh th nghim c th so snh kt thu c khi thay i

mt s yu t vi cc gi tr c chp nhn, chm, gii hn pht hin, kt qu thu
c t u n cui qu trnh, lng thuc th tiu tn, thi gian phn tch v gi
thnh phn tch. Nhng yu t nh hng n cc i lng cn kim sot trn c th
khng d pht hin v cng khng phi yu t no cng nh hng ti tt c cc i
lng mong mun nu trn. Vy khi cn nghin cu iu kin ti u cn quan tm n
cc yu t no ?
- Yu t cn kho st : Khi tin hnh th nghim, trc tin cn kim tra xem yu
t no nh hng chnh v c th kim sot, yu t khng th kim sot v tm ra
khong gi tr cn nghin cu xem xt nh hng ca n n kt qa o. Gi s c
n yu t cn kho st v mt hm s biu th i lng o, khi kt qu s c biu
din trong khng gian n+1 chiu (hnh 7.3).

Hnh 7.3 : th biu din kt qu thc nghim ph thuc ng thi vo mt

(hnh a) hoc 2 yu t nh hng (hnh b).

Khi , iu kin ti u tm c l khong gi tr ca bin m cho kt qu o n

nh nht khi bin thin mt yu t trong khi c nh cc yu t khc ( hnh 7.4a) hoc
ti mt gi tr ca yu t 1 v thay i yu t 2 sau v th trong khng gian 3
chiu v tm khong gi tr 2 bin sao cho hm thu c vi gi tr cao nht (hnh

178
7.4b). Tuy nhin, ngi lm th nghim cn tm gi tr bin cho ph hp vi c iu
kin khc na nh cc c tnh ha l ca h o, chnh xc ca s liu thc nghim
v i khi iu kin c chn khng phi ti s cho gi tr o l ln nht.

Hnh 7.4. Th d v iu kin ti u

a- mt yu t nh hng (pH) v tn hiu o c cc tr nhng c th chn
vng ti u
b- hai yu t nh hng, kt qu o c cc tr v c vng cc tr

Vic kho st iu kin ti u theo phng php n bin thng n gin

nhng kt qu iu kin ti u thu c ch ng khi cc yu t khc c nh (hnh
7.5). Trong thc t khi mt trong cc yu t thay i thng dn n iu kin tm
c khng cn l iu kin ti u na m i hi phi kho st bin thin ng thi
ca cc yu t.

179
 iu kin ti u

Hnh 7.5 : Thay i mt yu t kho st ti mt thi im khng cho ng iu

kin ti u
a- bt u t gi nguyn yu t 1 v thay i yu t 2, sau gi yu t 2 iu
kin ti u tm c v thay i yu t 1
b- cch lm tng t nh cch (a) nhng khng tm c iu kin ti u

Trong phm vi gio trnh ny ch xt nghin cu nh hng ca cc yu t theo

phng php n bin (kho st nh hng ca tng yu t trong khi c nh cc yu
t khc) v xt nh hng ca c hai yu t theo phng php t l cn cc nh hng
ng thi ca c hai yu t theo m hnh th nghim bc mt hay bc hai s xt trong
gio trnh nng cao khc.

7.3. c lng khng m bo o

Nh bit mi giai on qu trnh o u c cha khng m bo o v theo
tch ly thnh khng m bao o cui cng. Mc d kt qu phn tch m khch
hng nhn c di dng (gi tr khng m bo o m rng) nhng khi cng
nhn cht lng PTN thc hin theo ISO/IEC 17025, yu cu PTN phi cng b bng
vn bn v cch c lng khng m bo o.
7.3.1. Ngun gc v phn loi khng m bo o
* khng m bo o loi A (do sai s ngu nhin): Khi qu trnh phn tch ch
mc sai s ngu nhin th KB c th thu c t x l thng k s liu phn tch

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lp li. N c tnh t lch chun kt hp vi vic c tnh t khng m bo
thnh phn khc tnh ra c khng m bo ca php o.
* KB loi B (sai s h thng) : Khi mt bc trong qu trnh phn tch c
xut hin sai s h thng th KB ca kt qu cui cng c tnh theo lan truyn
khng m bo o ( xt chng 1).
7.3.2. Phm vi p dng KB o
- p ng yu cu ca cng nhn cht lng: theo yu cu ca ISO/IEC 2005.
- p ng nhu cu ca khch hng
- c lng K o nh sc xut xut hin, vi tin cy 95% th khng
m bo o m rng l 2.U
7.3.3. Cc cch tip cn c lng KB o
Theo Horwitz(2003) ngi i u trong cch tip cn t trn xung th c 4 cch
tnh KB o nh sau :
+ Tnh khong tin cy t lch chun ca cc php o lp li.
+ Tip cn theo cch di ln ( bottom-up). Horwitz (2003) m t cch tip cn
ny di dng p t/n nh cho KB do 9 t cc quc t qui nh (ISO 1993b)
hay GUM)
+Cch tip cn t trn xung (top- down) dng lch chun ti lp v lp li
t cc nghin cu trong lin phng th nghim theo ch dn ca IUPAC/AOAC
protocol (Horwitz 1995) or ISO 5725 (ISO ) ( 1994)
+ ng dng mt trong cc cng thc c Horwitz pht trin, lin quan vi
lch chun tng i v nng biu din di dng h s khi.
Trong phn ny chng ti trnh by cch c lng KB o ph bin theo
ISO GUM v EURACHEM

7.3.4. c lng KB o theo nguyn tc ca ISO GUM v EURACHEM.

Theo cch ny KB o c tnh ton theo cc bc c th sau:

181
Bc 1: Cn lit k y v i lng no cn xc nh bao gm c mi lin

182
quan gia i lng v cc i lng c nh lng trc tip m i lng o ph
thuc, nu c th bao gm c s hiu chnh ca cc nh hng h thng bit. Thng
tin v yu cu k thut cn c nu trong qui trnh tin hnh chun (SOP) hoc cc
miu t phng php khc.
Bc 2: Xc nh cc ngun KB o gm cc ngun c lin quan n KB
thnh phn ( gi l KB chun) trong cc thng s lin quan vi i lng o xc
nh bc 1 nhng cng c th bao gm cc ngun khc v cc ngun ny sinh trong
qu trnh phn tch ho hc.
Mt s ngun chnh gy ra KB l:
Ly mu
Trong phng php th ni b hoc trong qui trnh phn tch tiu chun, Kb
o gy ra do vic ly mu chu nh hng ca phng sai ngu nhin gia cc
mu khc nhau do ly mu khng ng nht, i din v phng sai c sn khi
ly mu.
iu kin bo qun mu
Khi cc mu th c lu gi mt thi gian trc khi tin hnh phn tch th cc
iu kin lu mu c th nh hng ti kt qu phn tch. Do vy, thi gian lu
cng nh iu kin trong qu trnh lu mu cn c xem xt n nh cc ngun
KB.
nh hng ca thit b
nh hng ca thit b c th bao gm nhiu yu t nh gii hn v chnh xc
trong hiu chun ca cn phn tch; ngi kim sot nhit do c th duy tr
nhit trung bnh khc s ch ca im t; thit b t ng c th l nguyn
nhn gy ra cc nh hng.
tinh khit ca thuc th
Nng ca dung dch chun khng chnh xc do tnh khit ca cht chun
khng phi 100%, cng thc ha khng ng ng vi thnh phn ha hc. Do
vy tinh khit ca cht chun cng l yu t gy ra KB.
Phn ng ha hc
Khi qui trnh phn tch c gi thit l tun theo mt phn ng ho hc v dng
n tnh ton th cn kim tra xem phn ng c xy ra theo h s t lng nht
nh hoc phn ng c xy hon ton khng hoc c hay khng c cc phn ng
ph.

183
 Cc iu kin o
iu kin do c bit l nhit c nh hng ln n dng c thu tinh do iu
kin s dng khc vi nhit khi dng c c hiu chun hoc m rt quan
trng khi vt liu nhy cm vi s thay i m.
nh hng ca nn mu
H s thu hi ca php phn tch c dng nh gi nh hng ca nn mu
vi cc mu c thnh phn nn phc tp hoc thit b c th nh hng bi thnh
phn ca mu. Mt khc, s n nh ca mu phn tch c th thay i qua cc
ln phn tch v s thay i ca iu kin bo qun mu nn khi s dng phng
php thm chun vo nn mu thc cn tnh n KB ca h s thu hi.
nh hng ca m hnh tnh ton
Vic la chn m hnh ton hc cho ng chun c KB o cho bn thn
cc h s trong phng trnh hi qui.
Hiu chnh mu trng
C th cn tnh KB trong c gi tr o v hiu chnh mu trng thch hp.
iu ny c bit quan trng l trong cc php phn tch vt.
nh hng ca nhn vin th nghim (tay ngh)
Kh nng c trn thc v thang o c th cao hoc thp; Kh nng thc hin
chnh xc cc th nghim ha h.
nh hng ngu nhin
Cc nh hng ngu nhin phn b ti KB trong tt c cc giai on cu qui
trnh phn tch. Do vy cn lit k cc ngun u vo tm ra ht cc nguyn
nhn gy ras KB.
Ch thch: Cc ngun trn khng nht thit c lp
Mt s ch dn c th v cc ngun gy ra KB thnh phn c cho trong ph
lctrch t ti liu AGL 18 hng dn v cch tnh KB trong phn tch ha hc
ca Vn phng Cng nhn cht lng.
Bc 3: nh lng cc thnh phn KB c th da trn d liu hiu chun
thit b (dng phn b chun), dung sai thit b o (phn b tam gic hoc phn b ch
nht), gi tr hiu chnhSau y l mt s cch c lng KB thnh phn:
- Cch 1: nh gi KB t cc ngun n l v sau tng hp li

184
- Cch 2: xc nh trc tip thnh phn KB ca kt qu t mt vi hoc ton b
cc ngun s dng d liu thc hin phng php.
thc hin vic tnh KB thnh phn cn tun theo cc bc sau:
+ lit k cc ngun KB cn c kim tra xem cc ngun no ca KB
thu c t cc d liu sn c, hoc c th thng qua nghin cu cc thnh
phn c th hoc thng qua thay i mt s tham s tnh thc nghim ca
phng php.
+ vi cc ngun ca KB khng c th hin qua cc d liu c sn v cng
khng tm thy thng tin no khc t cc d liu trong cc ti liu nh chng
ch, yu cu k thut ca thit b th phi tin hnh cc nghin cu thc
nghim tm phn b ca KB hoc tin hnh nghin cu phng php
m bo thu c phng sai i din cho cc thng s quan trng.

+ thnh phn KB no nh hn 1/3 gi tr KB ln nht th khng cn nh gi

chi tit
+ c lng KB s dng phng php so snh lin phng v d liu ph
duyt phng php
- Kt qu nghin cu trong so snh lin phng dng ph duyt phng php,
theo AOAC/IUPAC hoc tiu chun ISO 5725 l ngun d liu c gi tr h tr cho
c lng KB. D liu bao gm c lng lch chun ti lp s nhiu mc
R

hm lng v c lng tnh tuyn tnh ph thuc ca s vi tng mc hm lng v

R

c th bao gm c lng chch da vo nghin cu mu chun c chng nhn

(CRM). Cc ngun c th cn xem xt c th l:
- Ly mu. Cc nghin cu so snh lin phng him khi bao gm bc ly mu. Nu
phng php th ni b bao gm c chia nh mu v c lng thuc tnh ca
mu ln t mu nh th cc nh hng ca ly mu cn c nghin cu.
- Tin x l. Trong hu ht cc nghin cu, mu c ng nht v c th thm cht
n nh trc khi phn tch. C th cn nghin cu v thm cc nh hng ca qu
trnh thc hin th tc tin x l mu p dng trong ni b PTN.
- chch ca phng php. chch ca phng php thng nghin cu trc
hoc qua so snh lin phng, khi c th bng cch so snh vi phng php gc
hoc mu chun. Khi bn thn chch c KB lin quan vi cc gi tr tham
chiu c s dng v chm lin quan vi kim tra chch c so snh ti
s th khng cn thm KB ca chch. Nu khng s cn tnh thm.
R

185
- Cc iu kin thay i. Cc PTN tham gia vo nghin cu c th hng theo hng
c tnh n phm vi iu kin thc nghim, kt qu l khng c lng c phm
vi m kt qu c th nm trong theo nh ngha ca phng php. Khi cc nh
hng c xem xt v ch ra khng ng k so vi phm vi cho php th khng
cn tnh n thm na.
- Thay i cc loi mu. KB ny sinh t thnh phn mu hoc mc nhim bn
bn ngoi phm vi cn cn nhc nghin cu thm
Mi ngun KB ng k khng thu c qua d liu so snh lin phng cn c
nh gi theo dng KB chun v tng hp vi lch chun ti lp s theo cch
R

thng thng
* c lng KB qua nghin cu xy dng v ph duyt ni b
c lng KB t cc tham s s dng:
- c lng c sn tt nht ca chm ton phn
- c lng c sn tt nht cc chch ton phn v KB ca chch.
- nh lng ca bt k KB lin quan vi nh hng cha tnh n trong cc
nghin cu trn.
-T cc nghin cu chm: Cn nh gi c phng sai ca tt c cc thng s
nh hng n kt qu. Cc phng sai c th thu c t:
- lch chun ca cc kt qu cho mt dng mu c phn tch lp li nhiu ln
trong mt khong thi gian s dng nhng ngi phn tch v thit b khc nhau. Nu
c th (cc kt qu o ca cc mu kim tra cht lng QC c th cung cp thng tin).
- lch chun thu c t phn tch lp li thc hin nhiu ln trn mt mu.
Ch thch: Lp li cn c thc hin cc thi im khc nhau thu c c lng
chm trung gian; vic phn tch lp li trong mt l ch cung cp c lng lp
li.
- Tnh c lng phng sai cho tng tham s t nghin cu thc nghim a tham s
c phn tch bi ANOVA
- T cc nghin cu chch: chch tng c c lng tt nht bng phn
tch lp li mu chun c chng nhn qua tt c cc bc trong qui trnh phn tch,
s dng th tc o hon chnh. Khi chch khng ng k th KB lin quan vi
chch l tng hp KB ca mu chun c chng nhn vi lch chun lin
quan vi chch.

186
 chch ca 1 phng php nghin cu c th cng c xc nh bng so snh
cc kt qu t c bi phng php nghin cu vi phng php tham chiu. Nu
cc kt qu ch ra rng chch thng k l khng ng k, KB chun l KB
ca phng php gc, tng hp vi KB lin quan vi i lng o khc trong
phng php .

* Cc cch tnh khng m bo tng hp

- Khi c lng KB t cc kt qu v d liu c sn th khng m bo c

tnh nh lch chun. Do khi c mt khong tin cy c a ra vi mt mc
tin cy (theo dng a ti P%) th chia gi tr a cho h s ca phn b mc tin cy
tnh lch chun.
V d:Mt yu cu k thut cng b rng kh nng c ca cn l trong khong
0,2 mg vi mc tin cy 95% . T bng phn b chun Gauss, mc tin
cy 95% th tnh ton khng m bo m rng s dng gi tr Z=1.96.
Nn KB chun l 0,2/1,96 0.1.
- Nu gii hn ca a (dung sai ) c cng b v khng km theo mc tin cy v
c cc l do cho rng s phn b cc gi tr l nh nhau trn ton khong chia th
c th qui v phn b hnh ch nht nn lch chun tnh theo cng thc a/3.
V d: Mt buret cp A 25 mL c chng nhn l 0,2 mL. KB chun l
0,2/ 3 0,12 mL.

- Nu gii hn ca a (dung sai ) c cng b v khng km theo mc tin

cy nhng c l do cho rng cc gi tr phn b khng nh nhau trn ton khong
chia th c th qui v phn b phn b hnh tam gic nn lch chun tnh theo cng
thc a/ 6

V d: Mt bnh nh mc cp A 10mL c chng nhn l 0.2 mL nhng Kim

tra ti PTN ch ra rng cc gi tr him khi tp trung gn hai cc. KB
chun l 0,2/6 0.08 mL.
Bc 4:
- Vi kt qu o y, KB tng, thut ng chnh xc l khng m bo chun
tng hp v c vit di dng u (y) c c lng t lch theo cch tnh lan
c

truyn khng m bo o khi c sai s ngu nhin.

187
- Tnh KB o m rng U l khong tn ti m trong cc gi tr ca i lng o
c tin rng s nm trong vi tin cy cao. U t c bng cch nhn KB
tng hp u (y) vi h s ph k. Vic la chn h s k l da vo mc tin cy mong
c

mun. i vi mc tin cy xp x 95% th h s k=2. Do U= 2uc(y)

V d: KB chun tng hp cho vic cn c to thnh t cc phn b u

cal

= 0,01 mg ny sinh t KB hiu chun v s = 0,08mg da vo lch

obs

chun ca 5 ln quan st lp li. KB chun tng hp uc tng ng l

0,012 0,08 2 =0,081mg. y l nh hng do phn b lp li s qua 5 ln
obs

quan trc lp li cho bc t do l 5 - 1 = 4, kim tra trong bng student t gi tr

ca t vi bc t do l 4 v mc tin cy 95% c k = 2,8; th KB m
rng U = 2,8 x 0,081 = 0,23 mg.

* Bo co kt qu :
- KB chun : (Kt qu): x (n v) [vi a] KB chun ca uc (n v)
Trong du [ ] c ghi l [ KB chun tng ng vi lch chun ; c nh
nd
ngha trong thut ng v nh ngha o lng c bn VIM, 2 edition.., ISO 1993)].
Ch thch: Khng khuyn khch s dng biu tng khi tuyn b KB chun v
biu tng ny thng lin quan vi phm vi tng ng vi mc tin cy cao.
V d: Tng hm lng nit : 3,52 % w/w ; KB chun ( chnh l lch
chun):0,07 % w/w.
- khng m bo m rng: (Kt qu) : (x U) (n v)
Trong du [ ] c ghi l [ KB m rng c xc nh theo nh ngha ca VIM,
nd
2 ed., ISO 1993] c tnh ton s dng h s ph k = 2, [vi mc tin cy xp x
95%]
*
V d: Tng hm lng Nit : (3,52 0,14) %w/w
* Bo co KB l KB m rng c tnh bng cch s dng h s ph k=2
vi mc tin cy xp x 95%

7.3.5. Mt s th d

188
 Th d 1: Qui nh k thut ca nh sn xut vi mt s dng c thy tinh bnh nh
mc 100mL loi A l 0,08mL, ca pipet chia vch 2 ml l 0,01 ml. Khi khng
m bo chun ca th tch bnh v th tch pipet c tnh da trn phn b ch nht
nn gi tr ny tng ng l 0,08/ 3 = 0,046 mL v 0,01/ 3 = 0,0058 mL.

Th d 2: Chng ch hiu chun cho cn 4 s trong mt PTN cho bit khng m

bo o l 0,0004g vi tin cy khng t hn 95%. Khi KB chun bng
KB m rng chia 2 tc l 0,0004/2 = 0,0002 g.
Th d 3: Mt dung dch chun ni b PTN c chun b bng ho tan khong
100mg vt liu (cn trn cn phn tch 4 s), ha tan trong dung mi hu c thch hp
v nh mc n vch trong bnh nh mc 100mL bng dung mi ny. Tnh nng
ca dung dch (mg/L). Tnh khng m bo chun v khng m bo m rng
ca nng dung dch ?
Gii: - Cc ngun khng m bo gp phn vo ton b khng m bo ca nng
dung dch l:
Vic cn vt liu chun b dung dch;
tinh khit ca cht chun;
Th tch cui cng ca dung dch.
*Cc khng m bo thnh phn c lin quan l:
- Cn vt liu (uw): Nu cn ang s dng c chng ch hiu chun ca cn vi
khng m bo o l 0,0004g, tin cy khng di 95% th KB hiu chun l:
0,0004/2= 0.0002g = 0,200mg. Php cn c cn lp li vi qu cn 100mg trn cn
4 s c lch chun l 0,000041g th khng m bo do s bin thin ca cc ln
c cn l lch chun ca cc php cn lp li: 0,000041g = 0,041mg
Tng hp khng m bo trn s cho khng m bo ca khi lng vt liu

l: uw = 0,200 2 0,0412 = 0,208 gam

- Nu tinh khit ca cht chun theo nh sn xut l (99,9 0,1)% th KB ca

tinh khit ca cht chun up= 0,1/ 3 = 0,00058%
- khng m bo chun ca th tch cht lng trong bnh nh mc 100mL gm
dung sai ca bnh nh mc, h s n ca th tch dung mi, s khc nhau gia nhit
hiu chun v nhit PTN Gi s tng hp cc KB chun ny theo php
cng phng sai l uV= 0,16 mL.

189
Khi , vi cng thc tnh nng C(mg/l) theo cng thc:

th nng dung dch l

Tnh KB chun tng hp theo cng thc ta c:

Cc th d trn ch l th d n gin nht v tnh KB ca i lng cn tm.

Nu th nghim cng tin hnh qua nhiu giai on th vic tnh ton cng phc tp.
Vn ny s c xt chi tit trong mt ti liu tham kho cho lnh vc cng nhn
PTN Ha phn tch.

7.4. Xc nhn ga tr s dng ca phng php phn tch (validation and

verification of analytycal method)
Khng c bt c phng php phn tch no em s dng m khng cn xc
nhn gi tr ca phng php. ISO/IEC 17025 khuyn khch s dng cc phng php
c cng b l phng php chun quc gia (nh TCVN), chun khu vc hoc chun
quc t hoc cc hip hi khoa hc quc t cng b nh ASTM, APHA, AOAC,
EPA.. nhng cng khng c ngha l khng cn xc nhn li gi tr s dng ca
phng php v khi thc nghim c s thay i v a im tin hnh th nghim,
thit b s dng, dung dch chun i chng, iu kin mi trng tin hnh phn tch.
i vi cc phng php phn tch khng phi l phng php tiu chun nh phng
php do PTN t xy dng, phng php tham kho t cc kt qu nghin cu khoa
hc cng b trn tp ch trong v ngoi nc, phng php theo hng dn ca nh
sn xut gi l cc php th ni b cng cn c cc d liu khng nh phng
php th l ng n v c tin cy cao trc khi a vo s dng.
Xc nhn gi tr s dng ca phng php phn tch (trc y gi l ph duyt
phng php) l thut ng dng ch s ph hp ca qui trnh xy dng c vi bt
k i tng phn tch khi cung cp c cc bng chng khng nh rng phng
php l ng. Trc khi tin hnh QA /QC ti PTN, chng ta cn xc nhn gi tr s

190
dng ca phng php phn tch trong hai trng hp. Mt l nghin cu, tham kho
v xy dng phng php sau bin n thnh phng php tiu chun s dng trong
PTN (validation of analytical method) v hai l p dng phng php tiu chun vo
iu kin c th ca PTN (verification analytical method). Cc thng s cn tin hnh
trong hai trng hp ny c th t c qua nghin cu xy dng phng php v so
snh lin p h n g h o c th eo q u i tc x c n h n h iu l c c a p h n g p h p p h n tch .
IS O /IE C 1 7 0 2 5 ch ra rn g x c n h n g i tr s d n g p h n g p h p l k h n g n h
b n g cch k i m tra v cu n g c p cc b n g ch n g p n g c yu cu s dng
phng php c hiu qu, n bao gm cc qui nh phi tin hnh xc nhn phng
php phn tch c th s dng c. Do vy, kt qu phi c bo co y di
dng phng php l g, cc thng s kho st, kt qu nghin cu v kt lun g rt
ra.
Mi quan h gia xc nhn gi tr s dng (XNGTSD) ca phng php phn
tch, pht trin phng php phn tch v p ng nhu cu khch hng c th hin
qua s sau:

191
 Nhu cu phn tch Vn cn phn tch
ca khch hng

Chn phng php phn

tch vi cc thng s chnh
p ng c yu cu

Cha
Phng php hin c
c xc nhn gi tr s
Pht trin phng php dng cha?

Tin hnh cc th
nghim cn thit Ri
XNGTSD
ca phng php

Phng t
Phng
php c Khng
php tha Phn tch v
th bin
mn c bo co kt qu
son li?
XNGTSD?

Khng

a ra li khuyn Kt thc
cho khch hng

Khi nghin cu xc nhn hiu lc cho phng php phn tch nh lng cn xc
nh c trng mt vi hoc tt c cc thng s sau:
* chm (Precision): bao gm lch chun lp li sr, lch chun ti lp sR
(ISO 3534-1) v chm trung gian i khi c biu th l szi vi i biu th s nhn t
khc nhau (ISO 5725-3:1994). chm trung gian lin quan ti phng sai trong cc
192
kt qu quan st khi mt hoc nhiu nhn t thay i trong mt PTN nh thi gian,
thit b v nhn vin th nghim; cc kt qu thu c khc nhau ph thuc vo nhn
t no c gi khng i. c lng chm trung gian thng c xc nh
trong PTN nhng cng c th c xc nh bng nghin cu so snh lin phng.

lch chun trong trng hp mt mc nng cht phn tch, nhiu

thnh phn nn mu khc nhau
Nu phng php c phm vi ng dng rng i vi nhiu loi i tng phn
tch khc nhau, cn phn tch lp li t nht 4 ln cho mt i tng mu, ly
cc l mu khc nhau. Bng cch tnh ton lch chun ca cc kt qu thu
c cho mi loi mu. Nu lch chun khng khc nhau ng k th c th
dng cng thc tnh lch chun gp (Spool)

f1 .S 21 f 2 .S 2 2 ...
S pool
(n1 1 (n2 1) ...

lch chun trong trng hp mt loi mu, nhiu khong nng phn
tch
chm phi c xc nh ti cc gi tr nng nm trong khong nng
tuyn tnh ca phng php phn tch. Nu khng c mu i din cho cc
khong nng thch hp phn tch th s dng cc mu thm chun
nghin cu. Ch l t nht phi c 3 khong nng c nghin cu (v d
nh khong nng thp, trung bnh v cao) vi t nht 4 ln th nghim lp li
cho mi khong nng .
T kt qu phn tch lp li, tnh ton lch chun v lch chun tng i
ca cc kt qu ca tng mu. Nu khng c s khc nhau ng k gia cc
lch chun tng i ca tng mu th c ngha l chm l tng ng cho
nng phn tch v c th dng cng thc tnh lch chun gp (Spool)
Nu c s khc nhau gia cc lch tng i ca cc khong nng th cn
lm t nht 5 khong nng v cc lch chun ca cc kt qu nghin cu l
i din cho tng khong nng s cho chng ta thy mi lin quan gia
chm v nng . Nu cc kt qu tuyn tnh th c ngha l c s khc nhau
gia cc lch tng i c tnh cho cc khong nng . t nht cn phn
tch nghin cu 5 khong nng v cc lch chun ca cc kt qu nghin
cu l i din cho tng khong nng s cho chng ta thy mi lin quan gia
chm v nng . Nu cc kt qu tuyn tnh th c ngha l chm t l cho
cc mc nng v c th dng cng thc tnh lch chun gp

193
 lch chun trong trng hp nhiu dng mu v nhiu khong nng
Vi mt phng php phn tch, cn tin hnh nghin cu bng th nghim lp
li cho tng loi mu cc l khc nhau ( thay i nng kho st). C mt
s trng hp sau :
-Nu lch chun t l vi nng cht phn tch v c lp vi mi dng mu
th chm c c lng cho tng mu nghin cu v c chuyn thnh
lch chun tng i s dng cng thc RSDpool.
- Nu lch chun t l gia cc nng phn tch nhng khc nhau ln gia
cc dng mu th lch chun tng i tnh ti cc nng khc nhau cc
mu c lp c th s dng cng thc tnh RSDpool c lng cc chm
ring cho tng dng mu.
- Nu lch chun khng t l i vi cc mc nng v khc nhau gia cc
loi mu th c th dng cng thc tnh Spool cho c lng mt vi chm.

ng (nh gi qua chch (Bias) hoc hiu sut thu hi (recovery)):

- chch ca phng php phn tch thng c xc nh bng cch th
nghim vi c c m u ch u n i ch n g (C R M ) h o c c c m u th m ch u n
(sp ik e).
chch c th c din t theo cch tnh h s thu hi trong phn tch (gi tr thu
c thc t c chia cho gi tr c chp nhn).
thu hi cho mt mu c th R c th c tnh ton nh tng hp ca 3 thnh
phn theo cng thc : R = Rm . R . R .
s rep

trong :

Rm l c lng thu hi trung bnh ca phng php v d nh phn tch mu

CRM hoc mu thm chun.
R l s hiu chnh c tnh t s khc nhau trong thu hi ca mu thc vi
s

thu hi ca vt liu (mu CRM, mu thm) dng c lng Rm

-R l s hiu chnh c tnh th hin s khc nhau gia mu thm v mu thc

rep

khi phn tch.

194
 *Tnh tuyn tnh (Linearity): hu ht cc php phn tch cng c u c
thc da trn vic xy dng phng trnh hi qui n bin tuyn tnh biu din s ph
thuc tuyn tnh gia tn hiu phn tch v nng cht phn tch (gi l xy dng
ng chun). Tnh tuyn tnh th hin h s tng quan tuyn tnh R (thng
thng R>0,99). Hn ch ti a vic s dng phng trnh hi qui n bin bc hai,
bc 3 .. nh lng. Cc mi quan h khc nh hm m cn tm cch chuyn v
hm tuyn tnh n bin bng cch ly logarit...
*Gii hn pht hin v gii hn nh lng (LOD, LOQ): hai i lng ny
cn c xc nh thit lp gi tr nh nht ca nng cht phn tch m phng
php phn tch cn c th pht hin c hoc c th nh lng c.
*Khong tuyn tnh : Khi xc nh c mi quan h tuyn tnh gia tnh hiu
phn tch v nng cht nh phn cn xc nh gii hn tuyn tnh (LOL) ( bng
cch ni rng im trn ca ng chun cho n khi h s tng quan R ln hn
0,99). Khi khong tuyn tnh c nh ngha l t LOQ n LOL.
* nhy : gm hai khi nim nhy theo nhy ca ng chun v
nhy ca phng php phn tch ( xem chng 6).
* Tnh n nh ca ph ng php (Robustness or ruggedness ): y c tn h
c a p h n g p h p p h n tch k h n g b n h h n g b i n h n g th ay i n h c c h n h
c a c c th n g s c a p h n g p h p v c h ra c tin c y c a p h n g p h p tro n g
q u trn h s d n g . Vic nh gi ny thng c thc hin bng cch thay i mt
hoc nhiu thng s v nh gi chch v chm. Nu c thay i ng k th
phi tin hnh nghin cu chi tit xc nh c mc nh hng v a ra cc
khong gi tr n nh cho php.
Bng 7.... l mt v d v cc bc cn tin hnh trong nghin cu tnh n nh
ca phng php

Bng7... : V d v nghin cu tnh n nh ca phng php

Thao tc tin hnh V d

Lit k c cc tham s cn nghin cu Nhit , thuc th, thit b, tui th ct

tch, loi ct, pH, pha ng, loi etecto

Chn m hnh nghin cu Qui hoch ha thc nghim theo nhn t

195
 hoc phn tch phng sai

Chn khong bin thin cho cc yu t T= 10-300C ; pH=5-8 ; ct mi v ct s

dng c 1 thng, t l metanol : nc
trong pha ng thay i 2%

Lm th nghim ngu nhin theo m hnh Trn c s ma trn thc nghim lm ngu
nhin cc th nghim

Tnh ton nh hng ca cc yu t v nh hng l : pH=,.. T=...

kim tra tnh c ngha ca m hnh xy
dng c

* chn lc/tnh c hiu (Selectivity/specificity):

chn lc khi phn tch cht A c trng cho mc nh hng ca cc thnh
phn i cng trong nn mu n php phn tch cht A. Do phi nh gi nh hng
ca cc cht i cng ny ti c mu trng v mu thm chun. Phng php c kt
lun c chn lc tt nu cc nh hng ca cht i km trong nn mu l khng ng
k.
* khng m bo o: cn xc nh KB o trong hai trng hp c sai s
ngu nhin v c c sai s h thng ( KB o loi A v loi B). Trong trng hp c
cc d kin v xc nhn gi tr s dng ca phng php th khng m bo c th
c tnh nh s hnh 7:

196
197
 Hnh 7 : S minh ha v qui trnh c lng KB theo cc i lng thu
c trong xc nhn gi tr s dng ca phng php phn tch
(Cc s trong du ngoc l phn lin quan trong ti liu AGL 18- Vn phng cng
nhn cht lng)
198
 Tnh lin kt chun: c nh ngha l T n h ch t c a k t q u o h o c g i
tr c a m t ch u n m n h c th lin h t i n h n g ch u n n h , th n g l
ch u n q u c g ia h ay ch u n q u c t, th n g q u a m t ch u i so sn h k h n g g in o n
v i n h n g k h n g m b o n h .
T h it lp tn h li n k t ch u n nhm so snh cc kt qu gia cc PTN khc nhau
hoc cng mt PTN ti nhng thi im khc nhau vi mc tin cy nht nh. Do vy,
cn m bo rng tt c cc PTN s dng cng mt phng php xc nh hoc cng
cc mu phn tch chun i chng. Trong nhiu trng hp vic t c bi thit
lp mt chui hiu chun ti chun quc gia hoc quc t, l thuyt l mt chui thng
nht ti h n v o quc t SI. Mt v d thng thng nht l cn phn tch; mi
c n c h i u c h u n s d n g q u c n c h u n m c c q u c n ch u n c k i m
tra v i chun quc gia hoc chun u kg. Chui so snh khng gin on ti cc gi
tr chun cung cp lin kt chun ti mt im chun m bo rng ngi thc hin
khc nhau s dng cng mt n v o. Trong php o thng thng s thng nht ca
cc php o gia mt PTN (hoc thi gian) v nhng iu khc l nhm thit lp lin
kt cho cc php o trung gian lin quan s dng thu c hoc kim sot kt qu
ca mt php o. Lin kt chun l thut ng quan trng trong tt c cc nhnh ca o
lng.
Tnh lin kt chun ca kt qu trong mt qui trnh phn tch c th c thit lp
bng cc cch sau:
- S dng cc chun c th lin kt hiu chun thit b o (thng theo h n v
SI).
- S dng hoc so snh cc kt qu ca mt phng php gc. Phng php gc
ca mt php o l mt phng php c cht lng v o lng hc cao nht m vic
thc hin c m t mt cch y v c hiu trong thut ng ca h n v S I
v c c k t q u c c h p n h n k h n g c n li n k t t i m t c h u n c c n g n h
l n g .
- S dng mu chun tinh khit: Tnh lin kt chun c th c chng minh
thng qua php o mt mu t to cha mt lng mu chun bit hoc bng mu
thm chun.
- S dng mu chun c chng nhn thch hp (CRM): Tnh lin kt chun c th
c chng minh qua so snh cc kt qu o trn cht chun c chng nhn vi cc gi
tr c chng nhn.
- S dng qui trnh c xc nh v c chp nhn.

199
 Nh vy c th a mt phng php vo ng dng trong PTN cn bt u t
nghin cu chn cc iu kin ti u sau phi tin hnh cc bc xc nhn gi tr s
dng ca phng php. C th tm tt cc bc cn tin hnh trong xc nhn gi tr s
dng ca phng php khi phn tch c s dng ng chun theo s chung
sau:

200
 Xy dng cc ni dung
cn th nghim nh gi

Chn khong hm lng cht

n b
Chu cn nh lng
Ci tin qui trnh
Chun b dy mu chun phn tch, thu hp
xy dng ng chun khong nng
(nu cn)

Dng ng chun

Tm phng trnh hi qui

tuyn tnh v lch chun
ca phng trnh hi qui Sy

V th chun

Khng Nghi ng ng
m tra tnh tuyn tnh

chun khng tuyn

tnh?

Tm phng trnh ng chun bc hai

v lch chun Sy2
Ki

Khng Qui trnh C

Kim tra tnh phn tch c
tuyn tnh theo tr thay i c
s goodness-of- tuyn khng?
test tnh
Tuyn tnh Khng

Tip tc v s
dng phng
trnh phi tuyn

201
 Phn tch lp li 10 mu chun nng
thp nht v cao nht.
Xc nh gi tr o trung bnh ca hai
kt qu ny v lch chun ca n
Ging
nhau Qui trnh C
So snh hai gi tr phn tch
phng sai
sai
c th
( chun F)

ng sai
tra ph hiu chnh?

ng nht
ng nha
phng

Khng
m
Ki

Khng Tip tc
v dng
phng
trnh hi
qui khi
m tra gi

Kim tra gi tr bt thng,

sai s th Pht hin c gi
t th

tr bt thng
ng
Ki
b
tr

S liu khng
c gi tr bt thng

Nng thp nht Khng

khc khng c ngha
( chun t)
m tra chm nng

chm nng khng

thp c thay
i ng k?
Ki

p
th

202
 Lu ti liu s liu ng chun
cui cng Ci tin qu
trnh phn tch

Xy dng li ng chun khi c thay

i v ha cht, thit b, iu kin..
Xc nh hiu sut thu hi

Kim tra lch chun Lu ti

cc b

ng bi

ca qu trnh phn tch chm liu

c ri

(chun F) km
t
T

Kim tra sai s h thng

khng i C sai s
v bin i h thng

ng chun c s
m tra cc yu t nh h

dng nn mu
ng n qu tr

nh phn tch

Kim tra lch

chun ca qu trnh
chm
( chun F) km
Ki

ng ca nn mu

Kim tra sai s h

thng khng i v
C sai s
nh h

bin i h thng
T

203
 Chn mu kim tra

Phn tch kp mu kim tra cc

ngy khc nhau

Ci tin qui trnh phn

Tnh lch chun lp li, ti lp v
tch , hiu chnh thit
lch chun gp
b hng ngy v dng
li ng chun
( nu cn)
c
Kim tra s khc nhau
gia lch chun lp
li v ti lp

Khng

Chp nhn lch c

nhng nh h

chun gp
ng tm thi
m tra cc yu t nh h

Spool

Khng
ng n qu tr

nh phn tch
T

Qu trnh phn tch

Ki

c th hiu chun

khng?

Khng

Lu ti liu

204
 Thc t, ty thuc vo vic s dng phng php tiu chun hay t xy dng
phng php lm php th ni bi m cc yu cu c bn cn phi lm xc nhn
gi tr s dng ca phng php phn tch trong hai trng hp s dng phng php tiu
chun hoc phng php do PTN t xy dng c khc nhau:

7.4.1. Xc nhn gi tr s dng ca phng php tiu chun (Verification of

analytical method)
Hu ht cc ni dung cng vic phi lm v xc nhn gi tr s dng ca phng
php phn tch (t y tr i gi tt l nh gi phng php phn tch) c cng b
bi cc t chc quc t pht hnh tiu chun . Khi chnh xc v chm c
cng b t cc s liu ca cc php th lin phng th c th tin c rng phng php
c kim tra k lng. Tuy nhin, khi PTN ln u dng phng php tiu chun
trong iu kin phn tch khng ging nh cc PTN ca t chc quc t s dng
(nhn vin khc, thit b khc, thuc th khc, iu kin khc ) th p dng c cho
phn tch cn kho st li cc thng s v nh gi phng php trn cc mu chun
m bo rng phng php c th cho kt qu ng khi phn tch cc mu thc t.
Bng 7... trnh by s lng ti thiu cc th nghim cn tin hnh nh gi
phng php tiu chun khi ln u tin s dng n trong PTN.

Bng 7: Cc th nghim cn tin hnh nh gi phng php tiu chun

Thng s cn kim tra Cc th nghim cn lm nh gi

chch/ Hiu sut thu Phn tch mu chun i chng c thnh phn nn ph hp
hi hoc mu thm chun trn nn mu c trng hoc mu
c trng c gi tr bit km theo khng m bo o
c thit lp bi phng php khc

chm Xc nh lch chun ca 10 php xc nh c lp ca

mt mu phn tch c trng

205
c lng KB o Xem xt cc yu t ng gp vo KB o t cc ngun
trong PTN ang s dng; son li cc i lng B o
thnh phn

M hnh ng chun Khi chun ha phng php ln u, cn kim tra xem

phng trnh hi qui ca ng chun c tha mn iu
kin phng trnh tuyn tnh khng.

LOD Phn tch mt mu th gn LOD kim tra kh nng pht

hin ti gi tr LOD cng b.

7.4.2. Xc nhn gi tr s dng ca phng php do PTN t thit lp (Validation of

analytical method).
Khi khng th p dng hoc khng c sn phng php tiu chun th PTN c th
t xy dng phng php phn tch nh lng da trn cc nghin cu cng b, xy
dng cc phng php dng cho phn tch hin trng, phng php sng lc (nh tnh
v bn nh lng)... i vi mt phng php PTN t tham kho v xy dng th cc
thng s trong bng 7... cho bit PTN cn kho st cc i lng no.
Bng 7...: Cc thng s cn kho st khi xc nhn gi tr s dng ca phng php do
PTN t xy dng

Cc thng s Gi v m t cch tin hnh

c trng chn lc v Nghin cu nh hng ca cc cht cn tr, bng

ca phng tnh c hiu cch tin hnh vi cc nn mu khc nhau ch ra
php c phm vi ng dng ca phng php nghin cu
(cho i tng no, ngng nh hng ca cc yu
t i km...)

LOD Cng b ga tr nh nht ca i lng o hoc nng

Gii hn ca nh nht ca cht phn tch m cn pht hin/
phng php nh lng c

LOQ Ga tr nh nht t c vi khng m bo o

c n nh trc

Cc tham s Phng trnh hi qui y ca dng chun; Cc

trong m hnh tham s trong phng trnh ng chun c km theo
ng chun KB o

206
 ( nhy)
Hiu chun Khong tuyn Khong ga tr ca i lng o dng xc nhn ga
(Tnh tuyn tnh tr s dng ca phng php
tnh)
chch/ Hiu Chng minh phng php khng mc sai s h thng
sut thu hi ( c ngha sau khi hiu chnh
ng)

c lng nh hng loi KB o c tnh t x l thng k cc kt qu

KB o A ca php o lp li
( chm trong
iu kin lp
li v ti lp)

nh hng loi c lng da trn cc phng php phi thng k

B gm nhng s liu c, kinh nghim ca ngi
phn tch ...

Tnh n nh Kh nng phng php khng b nh hng bi s

thay i cc tham s ca phng php/iu kin phn
tch

Tuy nhin, khng phi tt c cc i lng nu u phi tin hnh nh gi

phng php phn tch. V d, i vi cc php phn tch th tch hay phn tch trng
lng khng xc nh theo ng chun th khng th nh gi tnh tuyn tnh. Ty
tng phng php phn tch m chn cc yu cu c th ( xem bng 7...)
Bng 7...: Cc yu cu cn lm xc nhn gi tr s dng ca cc phng php khc
nhau

Yu cu phn tch Cc thng s chnh Cc thng s khc nh

nh gi phng gi phng php
php

Ch phn tch nh lng chn lc v LOD Tnh c hiu

Nhn dng v phn tch dng cc chn lc ng chun, KBBD

cht (nh trng thi oxi ha, ng o, tnh n nh,

207
phn,...)

Xc nh cht trong nn mu bt chn lc , ng chun, tnh n

k KB o nh, ( LOD)

Phn tch lng vt chn lc , ng chun, tnh n nh

KB o, LOD

Kt qu dng so snh vi kt KB o ng chun, tnh n

qu ca PTN khc nh, (LOD)

Kt qu dng so snh vi gii KB o Tnh n nh, ( chn lc,

hn hoc s liu ch nh LOD)

Phng php c thc hin bi KB o, tnh n ng chun, (LOD,

cc KTV khc nhau trn cc thit nh chn lc)
b khc nhau

Yu cu phn tch cn t KB o, tnh n ng chun, tnh n nh

KB o t trc nh (LOD)

Mt s mu phn tch thuc cc ng chun, Tnh n nh, (LOD)

khong nng khc nhau KB o

Cc i lng trong ngoc ( ) ch cn nghin cu khi c yu cu.

7.5. Cng nhn cht lng PTN
Hot ng cng nhn PTN l nhng th tc m theo PTN phi trnh ra c,
p ng c mt lot cc php th, php o c n nh bi tiu chun quc gia
hoc quc t. Lnh vc cng nhn bao ph ton b cc i tng th, cc qui trnh hay
phng php s dng, cc thit b hay nhn s s dng trong qui trnh v tt c cc h
thng c lin quan n PTN. Mt khi c cng nhn, PTN c quyn xc nhn
cc kt qu php th i km vi chng nhn l PTN c cng nhn. iu c
ngha l kt qu a ra c xc nhn l c cht lng v c th chuyn cho khch
hng vi tin cy cao. Do vy, cng nhn cht lng em li li ch cho PTN, v cho
php PTN c th th hin c kh nng ca mnh i vi cc php th c bit, n
cng em li li ch cho khch hng nh cung cp cho khch hng la chn cc PTN
c cng nhn.

208
 Cng nhn l mt phn trong hot ng thng mi quc t. Mi quan h gia
cng nhn v mc tiu v s ph hp trong thng mi c th hin trong s sau
(hnh 7...):

T chc thng
H thng o lng mi th gii WTO)
quc t SI (CCGM)

Kh nng o Qui nh
lng ph hp

S ph hp thng mi

Cng nhn Chun ha

T chc cng T chc tiu
nhn (ILAC) chun (ISO)

Hnh : Quan h gia s ph hp quc t trong h thng thng mi v h thng

cht lng
Hin nay, Vn phng cng nhn cht lng (thuc B Khoa hc v Cng ngh t
02/10/2009) l thnh vin Vit Nam duy nht tham gia vo ILAC v l c quan t
chc iu hnh h thng cng nhn phng th nghim Vit Nam (VILAS) (vi hn
400 PTN, n v hoc t chc trong v ngoi nc c cng nhn).
Nhng ni dung cng nhn PTN sau y c trch dn vn tt ch yu t ti
liu AGL03- Vn Phng cng nhn cht lng.
PTN c cng nhn cht lng th PTN phi p ng c "Yu cu chung
v nng lc ca phng th nghim v hiu chun" c nu trong ISO/IEC 17025:2005.
Hin ti cc PTN mun c cng nhn phi np h s v xin cng nhn ti Vn Phng
cng nhn cht lng (BoA) xin cng nhn PTN thuc h thng cng nhn PTN
(VILAS).
Cc yu cu cng nhn cho cc PTN ho hc khng ph thuc vo qui m ln
hay nh, s lng cc php th nghim/hiu chun m PTN thc hin hoc s lng
nhn vin.

7.5.1.Chun mc cng nhn

209
 Chun mc cng nhn phng th nghim lnh vc ha hc ca VILAS bao gm:
ISO/IEC 17025 : 2005 - "Yu cu chung v nng lc ca cc phng
th nghim v hiu chun".
Yu cu b sung cng nhn cho phng th nghim lnh vc ho hc.
Cc chnh sch ca VILAS lin quan cng nhn phng th nghim
Cc vn bn php qui lin quan n hot ng th nghim trong lnh vc ha hc
.
PTN ch cn np n xin cng nhn v chun b y h s, iu kin p ng
c th tc cng nhn phng th nghim.

7.5.2. Cc yu cu b sung cng nhn cho phng th nghim thuc lnh vc ha

PTN phi p ng c cc yu cu sau
7.5.2.1. Cc yu cu v qun l
- T chc
- H thng qun l
- Hp ng ph v th nghim v hiu chun
- Hnh ng phng nga
- Kim sot h s: H s k thut (h s th nghim) cn bao gm cc thng tin
sau:
- nhn mu;
- phng php th nghim;
- ngy th nghim;
- ngy kt thc th nghim;
- thit b th nghim;
- ti liu ghi chp v tnh ton cho php th nghim lm bng chng (lu
dng s ghi chp trong PTN);
- nhn vin thc hin th nghim;
- bng chng chng minh vic tnh ton v truyn d liu c kim
tra;
- cc thng tin khc ghi r trong phng php th, cc vn bn hp
ng khc hoc cc qui nh do php lut yu cu lin quan.
210
 - nh gi ni b
- Xem xt cu lnh o:
7.5.2.2. Cc yu cu k thut
- Nhn vin
- Tin nghi v mi trng
- Phng php th nghim, hiu chun v ph duyt phng php
-Thit b
- Lin kt chun o lng
- Ly mu
- Qun l mu th nghim
- m bo cht lng kt qu th nghim
- Bo co kt qu
Chi tit cc ni dung trn nm trong mc 7.1 cp hoc c th tham kho
thm trong ti liu AGL03 ca vn phng cng nhn cht lng.

PH LC

Bng 1 : Tch phn Gauss (phn din tch gia 0 v z)

211
 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09

0.000 0.004 0.008 0.012 0.016 0.019 0.023 0.027 0.031 0.035
0.0
0 0 0 0 0 9 9 9 9 9

0.039 0.043 0.047 0.051 0.055 0.059 0.063 0.067 0.071 0.075
0.1
8 8 8 7 7 6 6 5 4 3

0.079 0.083 0.087 0.091 0.094 0.098 0.102 0.106 0.110 0.114
0.2
3 2 1 0 8 7 6 4 3 1

0.117 0.121 0.125 0.129 0.133 0.136 0.140 0.144 0.148 0.151
0.3
9 7 5 3 1 8 6 3 0 7

0.155 0.159 0.162 0.166 0.170 0.173 0.177 0.180 0.184 0.187
0.4
4 1 8 4 0 6 2 8 4 9

0.191 0.195 0.198 0.201 0.205 0.208 0.212 0.215 0.219 0.222
0.5
5 0 5 9 4 8 3 7 0 4

0.225 0.229 0.232 0.235 0.238 0.242 0.245 0.248 0.251 0.254
0.6
7 1 4 7 9 2 4 6 7 9

0.258 0.261 0.264 0.267 0.270 0.273 0.276 0.279 0.282 0.285
0.7
0 1 2 3 4 4 4 4 3 2

0.288 0.291 0.293 0.296 0.299 0.302 0.305 0.307 0.310 0.313
0.8
1 0 9 7 5 3 1 8 6 3

0.315 0.318 0.321 0.323 0.326 0.328 0.331 0.334 0.336 0.338
0.9
9 6 2 8 4 9 5 0 5 9

0.341 0.343 0.346 0.348 0.350 0.353 0.355 0.357 0.359 0.362
1.0
3 8 1 5 8 1 4 7 9 1

212
 0.364 0.366 0.368 0.370 0.372 0.374 0.377 0.379 0.381 0.383
1.1
3 5 6 8 9 9 0 0 0 0

0.384 0.386 0.388 0.390 0.392 0.394 0.396 0.398 0.399 0.401
1.2
9 9 8 7 5 4 2 0 7 5

0.403 0.404 0.406 0.408 0.409 0.411 0.413 0.414 0.416 0.417
1.3
2 9 6 2 9 5 1 7 2 7

0.419 0.420 0.422 0.423 0.425 0.426 0.427 0.429 0.430 0.431
1.4
2 7 2 6 1 5 9 2 6 9

0.433 0.434 0.435 0.437 0.438 0.439 0.440 0.441 0.442 0.444
1.5
2 5 7 0 2 4 6 8 9 1

0.445 0.446 0.447 0.448 0.449 0.450 0.451 0.452 0.453 0.454
1.6
2 3 4 4 5 5 5 5 5 5

0.455 0.456 0.457 0.458 0.459 0.459 0.460 0.461 0.462 0.463
1.7
4 4 3 2 1 9 8 6 5 3

0.464 0.464 0.465 0.466 0.467 0.467 0.468 0.469 0.469 0.470
1.8
1 9 6 4 1 8 6 3 9 6

0.471 0.471 0.472 0.473 0.473 0.474 0.475 0.475 0.476 0.476
1.9
3 9 6 2 8 4 0 6 1 7

0.477 0.477 0.478 0.478 0.479 0.479 0.480 0.480 0.481 0.481
2.0
2 8 3 8 3 8 3 8 2 7

0.482 0.482 0.483 0.483 0.483 0.484 0.484 0.485 0.485 0.485
2.1
1 6 0 4 8 2 6 0 4 7

0.486 0.486 0.486 0.487 0.487 0.487 0.488 0.488 0.488 0.489
2.2
1 4 8 1 5 8 1 4 7 0

0.489 0.489 0.489 0.490 0.490 0.490 0.490 0.491 0.491 0.491
2.3
3 6 8 1 4 6 9 1 3 6

0.491 0.492 0.492 0.492 0.492 0.492 0.493 0.493 0.493 0.493
2.4
8 0 2 5 7 9 1 2 4 6

213
 0.493 0.494 0.494 0.494 0.494 0.494 0.494 0.494 0.495 0.495
2.5
8 0 1 3 5 6 8 9 1 2

0.495 0.495 0.495 0.495 0.495 0.496 0.496 0.496 0.496 0.496
2.6
3 5 6 7 9 0 1 2 3 4

0.496 0.496 0.496 0.496 0.496 0.497 0.497 0.497 0.497 0.497
2.7
5 6 7 8 9 0 1 2 3 4

0.497 0.497 0.497 0.497 0.497 0.497 0.497 0.497 0.498 0.498
2.8
4 5 6 7 7 8 9 9 0 1

0.498 0.498 0.498 0.498 0.498 0.498 0.498 0.498 0.498 0.498
2.9
1 2 2 3 4 4 5 5 6 6

0.498 0.498 0.498 0.498 0.498 0.498 0.498 0.498 0.499 0.499
3.0
7 7 7 8 8 9 9 9 0 0

Bng 2a : Cn tch phn ca phn phi t mt pha (one-side) ph Bng 3: Cn

tch phn ca phn phi 2 (chi-thuc vo xc sut P , tin cy P, mc
ngha , bc t do f.

f\P 0.90 0.95 0.925 0.99 0.995 0.9995

1 3.077684 6.313752 12.70620 31.82052 63.65674 636.6192

214
2 1.885618 2.919986 4.30265 6.96456 9.92484 31.5991

3 1.637744 2.353363 3.18245 4.54070 5.84091 12.9240

4 1.533206 2.131847 2.77645 3.74695 4.60409 8.6103

5 1.475884 2.015048 2.57058 3.36493 4.03214 6.8688

6 1.439756 1.943180 2.44691 3.14267 3.70743 5.9588

7 1.414924 1.894579 2.36462 2.99795 3.49948 5.4079

8 1.396815 1.859548 2.30600 2.89646 3.35539 5.0413

9 1.383029 1.833113 2.26216 2.82144 3.24984 4.7809

10 1.372184 1.812461 2.22814 2.76377 3.16927 4.5869

11 1.363430 1.795885 2.20099 2.71808 3.10581 4.4370

12 1.356217 1.782288 2.17881 2.68100 3.05454 4.3178

13 1.350171 1.770933 2.16037 2.65031 3.01228 4.2208

14 1.345030 1.761310 2.14479 2.62449 2.97684 4.1405

15 1.340606 1.753050 2.13145 2.60248 2.94671 4.0728

16 1.336757 1.745884 2.11991 2.58349 2.92078 4.0150

17 1.333379 1.739607 2.10982 2.56693 2.89823 3.9651

18 1.330391 1.734064 2.10092 2.55238 2.87844 3.9216

19 1.327728 1.729133 2.09302 2.53948 2.86093 3.8834

20 1.325341 1.724718 2.08596 2.52798 2.84534 3.8495

215
 21 1.323188 1.720743 2.07961 2.51765 2.83136 3.8193

22 1.321237 1.717144 2.07387 2.50832 2.81876 3.7921

23 1.319460 1.713872 2.06866 2.49987 2.80734 3.7676

24 1.317836 1.710882 2.06390 2.49216 2.79694 3.7454

25 1.316345 1.708141 2.05954 2.48511 2.78744 3.7251

26 1.314972 1.705618 2.05553 2.47863 2.77871 3.7066

27 1.313703 1.703288 2.05183 2.47266 2.77068 3.6896

28 1.312527 1.701131 2.04841 2.46714 2.76326 3.6739

29 1.311434 1.699127 2.04523 2.46202 2.75639 3.6594

30 1.310415 1.697261 2.04227 2.45726 2.75000 3.6460

inf 1.281552 1.644854 1.95996 2.32635 2.57583 3.2905

Bng 2b : Cn tch phn ca phn phi t hai pha (two-side) ph thuc vo xc

sut P , tin cy P, mc ngha , bc t do f.

f\ P 0.90 0.95 0.99 0.995

216
1 6.314 12.706 63.657 127.32

2 2.920 4.303 9.925 14.089

3 2.353 3.182 5.841 7.453

4 2.132 2.776 4.604 5.598

5 2.015 2.571 4.032 4.773

6 1.943 2.447 3.707 4.371

7 1.595 2.365 3.500 4.029

8 1.860 2.306 3.355 3.832

9 1.833 2.262 3.250 3.690

10 1.812 2.228 3.169 3.581

15 1.753 2.131 2.947 3.252

20 1.725 2.086 2.845 3.153

25 1.708 2.060 2.787 3.078

inf 1.645 1.960 2.576 2.07

217
square distribution) ph thuc vo xc sut P v bc t do f.

f/ P 0.90 0.95 0.975 0.99 0.999

1 2.706 3.841 5.024 6.635 10.828

2 4.605 5.991 7.378 9.210 13.816
3 6.251 7.815 9.348 11.345 16.266
4 7.779 9.488 11.143 13.277 18.467
5 9.236 11.070 12.833 15.086 20.515
6 10.645 12.592 14.449 16.812 22.458
7 12.017 14.067 16.013 18.475 24.322
8 13.362 15.507 17.535 20.090 26.125
9 14.684 16.919 19.023 21.666 27.877
10 15.987 18.307 20.483 23.209 29.588
11 17.275 19.675 21.920 24.725 31.264
12 18.549 21.026 23.337 26.217 32.910
13 19.812 22.362 24.736 27.688 34.528
14 21.064 23.685 26.119 29.141 36.123
15 22.307 24.996 27.488 30.578 37.697
16 23.542 26.296 28.845 32.000 39.252
17 24.769 27.587 30.191 33.409 40.790
18 25.989 28.869 31.526 34.805 42.312
19 27.204 30.144 32.852 36.191 43.820
20 28.412 31.410 34.170 37.566 45.315
21 29.615 32.671 35.479 38.932 46.797
22 30.813 33.924 36.781 40.289 48.268
23 32.007 35.172 38.076 41.638 49.728

218
24 33.196 36.415 39.364 42.980 51.179
25 34.382 37.652 40.646 44.314 52.620
26 35.563 38.885 41.923 45.642 54.052
27 36.741 40.113 43.195 46.963 55.476
28 37.916 41.337 44.461 48.278 56.892
29 39.087 42.557 45.722 49.588 58.301
30 40.256 43.773 46.979 50.892 59.703
31 41.422 44.985 48.232 52.191 61.098
32 42.585 46.194 49.480 53.486 62.487
33 43.745 47.400 50.725 54.776 63.870
34 44.903 48.602 51.966 56.061 65.247
35 46.059 49.802 53.203 57.342 66.619
36 47.212 50.998 54.437 58.619 67.985
37 48.363 52.192 55.668 59.893 69.347
38 49.513 53.384 56.896 61.162 70.703
39 50.660 54.572 58.120 62.428 72.055
40 51.805 55.758 59.342 63.691 73.402
41 52.949 56.942 60.561 64.950 74.745
42 54.090 58.124 61.777 66.206 76.084
43 55.230 59.304 62.990 67.459 77.419
44 56.369 60.481 64.201 68.710 78.750
45 57.505 61.656 65.410 69.957 80.077
46 58.641 62.830 66.617 71.201 81.400
47 59.774 64.001 67.821 72.443 82.720
48 60.907 65.171 69.023 73.683 84.037
49 62.038 66.339 70.222 74.919 85.351
50 63.167 67.505 71.420 76.154 86.661
51 64.295 68.669 72.616 77.386 87.968
52 65.422 69.832 73.810 78.616 89.272
219
53 66.548 70.993 75.002 79.843 90.573
54 67.673 72.153 76.192 81.069 91.872
55 68.796 73.311 77.380 82.292 93.168
56 69.919 74.468 78.567 83.513 94.461
57 71.040 75.624 79.752 84.733 95.751
58 72.160 76.778 80.936 85.950 97.039
59 73.279 77.931 82.117 87.166 98.324
60 74.397 79.082 83.298 88.379 99.607
61 75.514 80.232 84.476 89.591 100.888
62 76.630 81.381 85.654 90.802 102.166
63 77.745 82.529 86.830 92.010 103.442
64 78.860 83.675 88.004 93.217 104.716
65 79.973 84.821 89.177 94.422 105.988
66 81.085 85.965 90.349 95.626 107.258
67 82.197 87.108 91.519 96.828 108.526
68 83.308 88.250 92.689 98.028 109.791
69 84.418 89.391 93.856 99.228 111.055
70 85.527 90.531 95.023 100.425 112.317
71 86.635 91.670 96.189 101.621 113.577
72 87.743 92.808 97.353 102.816 114.835
73 88.850 93.945 98.516 104.010 116.092
74 89.956 95.081 99.678 105.202 117.346
75 91.061 96.217 100.839 106.393 118.599
76 92.166 97.351 101.999 107.583 119.850
77 93.270 98.484 103.158 108.771 121.100
78 94.374 99.617 104.316 109.958 122.348
79 95.476 100.749 105.473 111.144 123.594
80 96.578 101.879 106.629 112.329 124.839
81 97.680 103.010 107.783 113.512 126.083
220
82 98.780 104.139 108.937 114.695 127.324
83 99.880 105.267 110.090 115.876 128.565
84 100.980 106.395 111.242 117.057 129.804
85 102.079 107.522 112.393 118.236 131.041
86 103.177 108.648 113.544 119.414 132.277
87 104.275 109.773 114.693 120.591 133.512
88 105.372 110.898 115.841 121.767 134.746
89 106.469 112.022 116.989 122.942 135.978
90 107.565 113.145 118.136 124.116 137.208
91 108.661 114.268 119.282 125.289 138.438
92 109.756 115.390 120.427 126.462 139.666
93 110.850 116.511 121.571 127.633 140.893
94 111.944 117.632 122.715 128.803 142.119
95 113.038 118.752 123.858 129.973 143.344
96 114.131 119.871 125.000 131.141 144.567
97 115.223 120.990 126.141 132.309 145.789
98 116.315 122.108 127.282 133.476 147.010
99 117.407 123.225 128.422 134.642 148.230
100 118.498 124.342 129.561 135.807 149.449
100 118.498 124.342 129.561 135.807 149.449

221
 Bng 4: Gii hn tch phn ca phn phi F ph thuc vo mc xc sut P
v bc t do f1 v f2.

1. Vi = 0,1 (P=0,90)

d
f
2 1
1 1 1 2 2 3 4 6
/ 1 2 3 4 5 6 7 8 9 2
0 2 5 0 4 0 0 0
d 0
f
1

3 4 5 5 5 5 5 5 5 6 6 6 6 6 6 6 6 6 6
9. 9. 3. 5. 7. 8. 8. 9. 9. 0. 0. 1. 1. 2. 2. 2. 2. 3. 3.
8 5 5 8 2 2 9 4 8 1 7 2 7 0 2 5 7 0 3
1 6 0 9 3 4 0 0 3 5 9 0 2 4 0 6 2 9 6 2
3 0 3 2 0 4 5 8 7 4 5 0 0 2 4 9 4 0 8
4 0 2 9 0 4 9 9 5 9 2 3 2 0 9 0 2 6 1
6 0 4 6 8 2 5 8 9 8 1 4 9 5 7 5 8 4 2

8. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9.
5 0 1 2 2 3 3 3 3 3 4 4 4 4 4 4 4 4 4
2 0 6 4 9 2 4 6 8 9 0 2 4 4 5 6 7 8 9
2
6 0 1 3 2 5 9 6 0 1 8 4 1 9 7 6 4 2 1
3 0 7 4 6 5 0 7 5 5 1 7 3 6 9 2 5 8 2
2 0 9 2 3 3 8 7 4 7 3 1 1 2 3 4 6 9 2

5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5.
5 4 3 3 3 2 2 2 2 2 2 2 1 1 1 1 1 1 1
3 6 9 4 0 8 6 5 4 3 1 0 8 7 6 5 5 4 3
3
8 2 0 2 9 4 6 1 0 0 5 0 4 6 8 9 1 2 3
3 3 7 6 1 7 1 6 0 4 6 3 4 3 1 7 1 5 7
2 8 7 4 6 3 9 7 0 1 2 1 8 6 1 2 9 1 0

222
 4. 4. 4. 4. 4. 4. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3.
5 3 1 1 0 0 9 9 9 9 8 8 8 8 8 8 7 7 7
4 2 9 0 5 0 7 5 3 1 9 7 4 3 1 0 8 7 6
4
4 4 0 7 0 9 8 4 5 9 5 0 4 0 7 3 9 5 0
7 5 8 2 5 7 9 9 6 8 5 3 3 9 4 6 5 2 7
7 6 6 5 8 5 7 4 7 8 3 6 4 9 2 1 7 7 3

4. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3.
0 7 6 5 4 4 3 3 3 2 2 2 2 1 1 1 1 1 1
6 7 1 2 5 0 6 3 1 9 6 3 0 9 7 5 4 2 0
5
0 9 9 0 2 4 7 9 6 7 8 8 6 0 4 7 0 2 5
4 7 4 2 9 5 9 2 2 4 2 0 6 5 0 3 2 7 0
2 2 8 0 8 1 0 8 8 0 4 1 5 2 8 2 3 9 0

3. 3. 3. 3. 3. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
7 4 2 1 1 0 0 9 9 9 9 8 8 8 7 7 7 7 7
7 6 8 8 0 5 1 8 5 3 0 7 3 1 9 8 6 4 2
6
5 3 8 0 7 4 4 3 7 6 4 1 6 8 9 1 1 2 2
9 3 7 7 5 5 4 0 7 9 7 2 3 3 9 1 9 2 1
5 0 6 6 1 5 6 4 4 3 2 2 4 4 6 7 5 9 6

3. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
5 2 0 9 8 8 7 7 7 7 6 6 5 5 5 5 5 4 4
8 5 7 6 8 2 8 5 2 0 6 3 9 7 5 3 1 9 7
7
9 7 4 0 3 7 4 1 4 2 8 2 4 5 5 5 4 2 0
4 4 0 5 3 3 9 5 6 5 1 2 7 3 4 1 2 7 7
3 4 7 3 4 9 3 8 8 1 1 3 3 3 6 0 2 9 9

3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
4 1 9 8 7 6 6 5 5 5 5 4 4 4 3 3 3 3 2
5 1 2 0 2 6 2 8 6 3 0 6 2 0 8 6 3 1 9
8
7 3 3 6 6 8 4 9 1 8 1 4 4 4 3 1 9 6 2
9 1 8 4 4 3 1 3 2 0 9 2 6 1 0 3 1 1 5
2 2 0 3 5 3 3 5 4 4 6 2 4 0 2 6 0 8 7

223
 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
3 0 8 6 6 5 5 4 4 4 3 3 2 2 2 2 2 1 1
6 0 1 9 1 5 0 6 4 1 7 3 9 7 5 3 0 8 5
9
0 6 2 2 0 0 5 9 0 6 8 9 8 6 4 1 8 4 9
3 4 8 6 6 8 3 4 3 3 8 6 3 8 7 9 4 2 2
0 5 6 8 1 6 1 1 4 2 8 2 2 3 2 6 9 7 3

3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
2 9 7 6 5 4 4 3 3 3 2 2 2 1 1 1 1 0 0
1 8 2 2 0 2 6 1 7 4 2 8 4 0 7 5 3 0 8 5
0 5 4 7 5 1 0 3 7 7 2 4 3 0 8 5 1 7 1 5
0 4 6 3 6 5 9 1 3 6 0 5 7 4 4 6 1 7 4
2 7 7 4 4 8 7 5 1 0 5 1 4 3 3 9 6 6 2

3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1.
2 8 6 5 4 3 3 3 2 2 2 1 1 1 0 0 0 9 9
1 2 5 6 3 5 8 4 0 7 4 0 6 2 0 7 5 2 9 7
1 5 9 0 6 1 9 1 4 3 8 8 7 3 0 6 1 6 9 2
2 5 2 1 1 0 5 0 5 2 7 0 0 0 2 6 1 6 1
0 1 3 9 8 7 7 0 0 3 3 9 5 1 1 1 2 5 1

3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1.
1 8 6 4 3 3 2 2 2 1 1 1 0 0 0 9 9 9 9
1 7 0 0 8 9 3 8 4 1 8 4 0 5 3 1 8 5 3 0
2 6 6 5 0 4 1 2 4 3 7 7 4 9 5 1 6 9 2 3
5 8 5 1 0 0 7 5 5 7 4 8 6 9 4 1 7 2 6
5 0 2 0 2 2 8 7 2 6 4 5 8 9 9 0 3 8 1

3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1.
1 7 5 4 3 2 2 1 1 1 0 0 0 9 9 9 9 8 8
1 3 6 6 3 4 8 3 9 6 3 9 5 0 8 5 3 0 7 4
3 6 3 0 3 6 2 4 5 3 7 6 3 6 2 7 1 4 5 6
2 1 2 7 7 9 1 3 8 6 5 1 9 7 5 4 2 9 2
1 7 7 1 2 8 0 5 2 3 9 6 8 2 7 7 9 1 0

224
 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1.
1 7 5 3 3 2 1 1 1 0 0 0 9 9 9 8 8 8 7
1 0 2 2 9 0 4 9 5 2 9 5 0 6 3 1 8 5 2 9
4 2 6 2 4 6 2 3 3 1 5 3 9 2 7 1 5 7 8 7
2 4 2 6 9 5 1 9 9 4 7 5 4 6 9 1 2 0 2
1 7 2 9 4 6 3 0 5 0 1 3 5 6 3 6 3 0 8

3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1.
0 6 4 3 2 2 1 1 0 0 0 9 9 8 8 8 8 7 7
1 7 9 8 6 7 0 5 1 8 5 1 7 2 9 7 4 1 8 5
5 3 5 9 1 3 8 8 8 6 9 7 2 4 9 2 5 6 6 5
1 1 7 4 0 0 1 5 2 3 0 2 3 0 7 3 7 7 0
9 7 9 3 2 8 8 3 1 2 7 2 1 4 7 9 6 2 5

3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1.
0 6 4 3 2 1 1 0 0 0 9 9 8 8 8 8 7 7 7
1 4 6 6 3 4 7 2 8 5 2 8 3 9 6 3 1 8 5 1
6 8 8 1 2 3 8 8 7 5 8 5 9 1 5 8 0 1 0 8
1 1 8 7 7 3 0 9 3 1 3 9 2 5 7 8 5 7 1
1 7 1 4 6 3 0 8 3 5 9 2 7 6 9 4 6 5 7

3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1.
0 6 4 3 2 1 1 0 0 0 9 9 8 8 8 7 7 7 6
1 2 4 3 0 1 5 0 6 2 0 5 1 6 3 0 8 5 1 8
7 6 4 7 7 8 2 1 1 8 0 7 1 2 6 9 0 0 9 5
2 6 4 7 2 3 6 3 3 9 7 6 3 2 0 5 6 0 6
3 4 3 5 5 9 9 4 9 4 2 9 6 4 1 3 3 9 4

3. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
0 6 4 2 1 1 0 0 0 9 9 8 8 8 7 7 7 6 6
1 0 2 1 8 9 2 7 3 0 7 3 8 3 1 8 5 2 9 5
8 6 3 6 5 5 9 8 7 4 6 3 6 6 0 2 3 3 0 6
9 9 0 7 8 5 5 8 6 9 3 8 8 3 6 7 2 9 7
8 5 1 7 3 8 4 9 7 8 4 1 5 5 9 1 2 9 1

225
 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 6 3 2 1 1 0 0 9 9 9 8 8 7 7 7 6 6 6
1 8 0 9 6 7 0 5 1 8 5 1 6 1 8 5 2 9 6 3
9 9 5 7 6 5 9 8 7 3 5 1 4 4 7 9 9 8 5 0
9 6 0 3 9 3 0 1 6 7 7 7 1 3 2 7 7 8 7
0 1 2 0 6 6 2 0 4 3 0 1 6 1 4 9 6 7 7

2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 3 2 1 0 0 9 9 9 8 8 7 7 7 7 6 6 6
2 7 8 8 4 5 9 3 9 6 3 9 4 9 6 3 0 7 4 0
0 4 9 0 8 8 1 9 8 4 6 2 4 3 6 8 8 6 3 7
6 2 0 9 2 3 7 5 8 7 3 9 8 6 2 3 7 2 3
5 5 9 3 3 2 0 3 5 4 6 4 4 7 2 3 8 6 8

2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 3 2 1 0 0 9 9 9 8 8 7 7 7 6 6 6 5
2 6 7 6 3 4 7 2 8 4 1 7 2 7 4 1 8 5 2 8
1 0 4 4 3 2 5 3 1 7 9 4 7 5 8 9 8 6 2 6
9 5 8 3 3 1 2 8 9 6 9 1 5 0 2 9 9 7 1
6 7 9 4 1 2 5 6 7 7 7 5 5 7 7 6 1 8 5

2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 3 2 1 0 0 9 9 9 8 8 7 7 7 6 6 6 5
2 4 6 5 1 2 6 0 6 3 0 5 1 5 3 0 7 3 0 6
2 8 1 1 9 7 0 8 6 2 4 9 1 8 1 2 1 8 4 6
5 3 1 2 9 5 4 8 7 2 2 0 9 2 0 3 8 1 7
8 1 7 7 4 0 0 0 3 5 5 6 9 2 8 8 5 5 8

2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 3 2 1 0 9 9 9 8 8 7 7 7 6 6 6 5 5
2 3 4 3 0 1 4 9 5 1 9 4 9 4 1 8 5 2 8 4
3 7 9 8 6 4 7 4 3 8 0 4 6 3 5 6 5 2 7 9
3 2 7 5 9 2 9 1 8 2 9 4 9 8 4 3 3 1 0
6 9 3 1 1 3 2 2 8 5 7 3 2 8 3 5 7 1 3

226
 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 3 1 1 0 9 9 9 8 8 7 7 7 6 6 6 5 5
2 2 3 2 9 0 3 8 4 0 7 3 8 3 0 7 4 0 7 3
4 7 8 7 4 3 5 2 0 6 7 1 3 0 1 2 0 7 1 2
1 3 3 8 0 1 6 6 2 4 9 0 1 8 1 6 2 4 7
2 3 9 8 3 3 3 6 5 8 4 8 5 5 0 7 6 6 0

2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 3 1 0 0 9 9 8 8 8 7 7 6 6 6 5 5 5
2 1 2 1 8 9 2 7 2 9 6 2 7 1 8 5 2 9 5 1
5 7 8 7 4 2 4 1 9 4 5 0 0 7 8 8 7 3 7 7
7 3 0 2 1 0 3 2 6 7 0 8 5 9 9 1 3 0 6
4 1 2 4 6 6 8 5 9 8 0 3 2 8 5 8 5 3 0

2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 3 1 0 0 9 9 8 8 8 7 7 6 6 6 5 5 5
2 0 1 0 7 8 1 6 1 8 5 0 5 0 7 4 1 8 4 0
6 9 9 7 4 2 3 1 8 4 5 9 9 5 7 6 4 0 3 3
1 1 4 4 1 8 0 7 0 0 0 5 8 1 8 7 5 6 6
3 0 9 7 8 9 4 6 7 3 2 7 9 2 2 2 0 8 0

2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
9 5 2 1 0 0 9 9 8 8 7 7 6 6 6 6 5 5 4
2 0 1 9 6 7 0 5 0 7 4 9 4 9 6 3 0 6 3 9
7 1 0 8 5 2 4 1 9 4 5 8 9 5 6 5 3 8 1 0
1 6 7 4 9 5 5 0 2 1 8 1 1 1 6 2 5 2 5
9 1 1 6 8 2 1 9 7 1 9 7 4 6 0 0 9 9 7

2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
8 5 2 1 0 9 9 9 8 8 7 7 6 6 6 5 5 5 4
2 9 0 9 5 6 9 4 0 6 3 8 3 8 5 2 9 5 1 7
8 3 2 0 7 4 5 2 0 5 5 9 9 5 6 5 2 7 9 8
8 7 6 1 4 8 7 1 2 9 5 5 1 0 1 5 5 7 4
5 6 0 4 7 5 0 4 0 3 1 4 9 0 9 0 3 6 1

227
 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
8 4 2 1 0 9 9 8 8 8 7 7 6 6 6 5 5 5 4
2 8 9 8 4 5 8 3 9 5 2 8 3 7 4 1 8 4 0 6
9 7 5 3 9 6 7 4 1 6 7 0 0 5 6 5 2 7 8 7
0 4 0 4 5 8 5 8 7 4 8 6 9 5 5 5 2 9 0
3 8 7 1 8 1 2 4 9 1 1 0 3 5 1 3 1 9 4

2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
8 4 2 1 0 9 9 8 8 8 7 7 6 6 6 5 5 4 4
3 8 8 7 4 4 8 2 8 4 1 7 2 6 3 0 7 3 9 5
0 0 8 6 2 9 0 6 4 8 9 2 2 7 7 6 3 7 8 6
6 7 0 2 2 3 9 1 9 4 7 2 3 7 4 2 5 9 3
9 2 7 3 5 3 2 2 6 9 0 7 1 4 8 3 7 1 6

2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
8 4 2 0 9 9 8 8 7 7 7 6 6 5 5 5 4 4 3
4 3 4 2 9 9 2 7 2 9 6 1 6 0 7 4 0 6 2 7
0 5 0 6 0 6 6 2 8 2 2 4 2 5 4 1 5 7 4 6
3 3 0 9 8 8 5 8 9 6 5 4 1 1 0 6 1 7 9
5 7 9 5 2 8 2 6 0 9 6 1 5 1 8 2 6 6 1

2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
7 3 1 0 9 8 8 7 7 7 6 6 5 5 4 4 3 3 2
6 9 9 7 4 4 7 1 7 3 0 5 0 4 1 7 3 9 4 9
0 1 3 7 0 5 4 9 4 8 7 7 3 3 0 5 7 5 7 1
0 2 4 9 7 7 3 8 0 0 4 3 4 7 5 3 2 5 4
7 5 1 9 1 2 9 3 2 1 3 7 9 2 4 4 0 7 6

2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
7 3 1 9 8 8 7 7 6 6 6 5 4 4 4 3 3 2 1
1
4 4 2 9 9 2 6 2 8 5 0 4 8 4 0 6 2 6 9
2
7 7 9 2 5 3 7 1 4 2 1 5 2 7 9 7 0 4 2
0
8 3 9 3 8 8 4 9 2 3 2 0 0 2 3 6 3 5 5
1 4 9 0 7 1 8 6 5 8 0 0 7 3 8 0 4 7 6

228
 2. 2. 2. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1.
7 3 0 9 8 7 7 6 6 5 5 4 4 3 3 2 2 1 0
0 0 8 4 4 7 1 7 3 9 4 8 2 8 4 9 3 6 0

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

2. Vi =0,05 (P=0,95).

f
2

1 1 1 2 12
1 2 3 4 5 6 7 8 9 24 30 40 60
/ 0 2 5 0 0
f
1

1 1 2 2 2 2 2 2 2 2 2 2 2
24 25 25 25 25 25
6 9 1 2 3 3 3 3 4 4 4 4 4
1 9. 0. 1. 2. 3. 4.
1. 9. 5. 4. 0. 3. 6. 8. 0. 1. 3. 5. 8.
05 09 14 19 25 31
4 5 7 5 1 9 7 8 5 8 9 9 0
18 51 32 57 29 44
4 0 0 8 6 8 6 8 4 8 0 4 1

1 1 1 1 1 1 1 1 1 1 1 1 1
19 19 19 19 19 19
8. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9. 9.
2 .4 .4 .4 .4 .4 .4
5 0 1 2 2 3 3 3 3 3 4 4 4
54 62 70 79 87 95
1 0 6 4 9 2 5 7 8 9 1 2 4
1 4 7 1 4 7
2 0 4 6 6 9 3 1 4 5 2 9 5

1 9. 9. 9. 9. 8. 8. 8. 8. 8. 8. 8. 8.
0. 5 2 1 0 9 8 8 8 7 7 7 6 8. 8. 8. 8. 8. 8.
3
1 5 7 1 1 4 8 4 1 8 4 0 6 63 61 59 57 54 52
2 2 6 7 3 0 6 5 2 5 4 2 0 85 66 44 20 94 64
8 1 6 2 5 6 7 2 3 5 6 9 2

4 7. 6. 6. 6. 6. 6. 6. 6. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5. 5.

229
 7 9 5 3 2 1 0 0 9 9 9 8 8 77 74 71 68 65 62
0 4 9 8 5 6 9 4 9 6 1 5 0 44 59 70 77 81 81
8 4 1 8 6 3 4 1 8 4 1 7 2
6 3 4 2 1 1 2 0 8 4 7 8 5

6. 5. 5. 5. 5. 4. 4. 4. 4. 4. 4. 4. 4.
6 7 4 1 0 9 8 8 7 7 6 6 5 4. 4. 4. 4. 4. 4.
5
0 8 0 9 5 5 7 1 7 3 7 1 5 52 49 46 43 39 36
7 6 9 2 0 0 5 8 2 5 7 8 8 72 57 38 14 85 50
9 1 5 2 3 3 9 3 5 1 7 8 1

5. 5. 4. 4. 4. 4. 4. 4. 4. 4. 3. 3. 3.
9 1 7 5 3 2 2 1 0 0 9 9 8 3. 3. 3. 3. 3. 3.
6
8 4 5 3 8 8 0 4 9 6 9 3 7 84 80 77 73 70 66
7 3 7 3 7 3 6 6 9 0 9 8 4 15 82 43 98 47 89
4 3 1 7 4 9 7 8 0 0 9 1 2

5. 4. 4. 4. 3. 3. 3. 3. 3. 3. 3. 3. 3.
5 7 3 1 9 8 7 7 6 6 5 5 4 3. 3. 3. 3. 3. 3.
7
9 3 4 2 7 6 8 2 7 3 7 1 4 41 37 34 30 26 22
1 7 6 0 1 6 7 5 6 6 4 0 4 05 58 04 43 74 98
4 4 8 3 5 0 0 7 7 5 7 7 5

5. 4. 4. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3.
3 4 0 8 6 5 5 4 3 3 2 2 1 3. 3. 3. 3. 2. 2.
8
1 5 6 3 8 8 0 3 8 4 8 1 5 11 07 04 00 96 92
7 9 6 7 7 0 0 8 8 7 3 8 0 52 94 28 53 69 76
7 0 2 9 5 6 5 1 1 2 9 4 3

5. 4. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 2.
1 2 8 6 4 3 2 2 1 1 0 0 9 2. 2. 2. 2. 2. 2.
9
1 5 6 3 8 7 9 2 7 3 7 0 3 90 86 82 78 74 70
7 6 2 3 1 3 2 9 8 7 2 6 6 05 37 59 72 75 67
4 5 5 1 7 8 7 6 9 3 9 1 5

230
 4. 4. 3. 3. 3. 3. 3. 3. 3. 2. 2. 2. 2.
1 9 1 7 4 3 2 1 0 0 9 9 8 7 2. 2. 2. 2. 2. 2.
0 6 0 0 7 2 1 3 7 2 7 1 4 7 73 69 66 62 58 53
4 2 8 8 5 7 5 1 0 8 3 5 4 72 96 09 11 01 79
6 8 3 0 8 2 5 7 4 2 0 0 0

4. 3. 3. 3. 3. 3. 3. 2. 2. 2. 2. 2. 2.
1 8 9 5 3 2 0 0 9 8 8 7 7 6 2. 2. 2. 2. 2. 2.
1 4 8 8 5 0 9 1 4 9 5 8 1 4 60 57 53 49 44 40
4 2 7 6 3 4 2 8 6 3 7 8 6 90 05 09 01 80 45
3 3 4 7 9 6 3 0 2 6 6 6 4

4. 3. 3. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2.
1 7 8 4 2 1 9 9 8 7 7 6 6 5 2. 2. 2. 2. 2. 2.
2 4 8 9 5 0 9 1 4 9 5 8 1 4 50 46 42 38 34 29
7 5 0 9 5 6 3 8 6 3 6 6 3 55 63 59 42 10 62
2 3 3 2 9 1 4 6 4 4 6 9 6

4. 3. 3. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2.
1 6 8 4 1 0 9 8 7 7 6 6 5 4 2. 2. 2. 2. 2. 2.
3 6 0 1 7 2 1 3 6 1 7 0 3 5 42 38 33 29 25 20
7 5 0 9 5 5 2 6 4 1 3 3 8 02 03 92 66 24 64
2 6 5 1 4 3 1 9 4 0 7 1 9

4. 3. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2.
1 6 7 3 1 9 8 7 6 6 6 5 4 3 2. 2. 2. 2. 2. 2.
4 0 3 4 1 5 4 6 9 4 0 3 6 8 34 30 26 22 17 13
0 8 3 2 8 7 4 8 5 2 4 3 7 87 82 64 29 78 07
1 9 9 2 2 7 2 7 8 2 2 0 9

4. 3. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2.
1 2. 2. 2. 2. 2. 2.
5 6 2 0 9 7 7 6 5 5 4 4 3
5 28 24 20 16 11 06
4 8 8 5 0 9 0 4 8 4 7 0 2
78 68 43 01 41 58
3 2 7 5 1 0 6 0 7 3 5 3 7

231
 1 3 4 6 3 5 6 8 6 7 3 4 5

4. 3. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2.
1 4 6 2 0 8 7 6 5 5 4 4 3 2 2. 2. 2. 2. 2. 2.
6 9 3 3 0 5 4 5 9 3 9 2 5 7 23 19 15 10 05 00
4 3 8 6 2 1 7 1 7 3 4 2 5 54 38 07 58 89 96
0 7 9 9 4 3 2 1 7 5 7 2 6

4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
1 4 5 1 9 8 6 6 5 4 4 3 3 2 2. 2. 2. 2. 2. 1.
7 5 9 9 6 1 9 1 4 9 4 8 0 3 18 14 10 05 01 96
1 1 6 4 0 8 4 8 4 9 0 7 0 98 77 40 84 07 04
3 5 8 7 0 7 3 0 3 9 7 7 4

4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
1 4 5 1 9 7 6 5 5 4 4 3 2 1 2. 2. 2. 2. 1. 1.
8 1 5 5 2 7 6 7 1 5 1 4 6 9 14 10 06 01 96 91
3 4 9 7 2 1 6 0 6 1 2 8 0 97 71 29 66 81 68
9 6 9 7 9 3 7 2 3 7 1 6 6

4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
1 3 5 1 8 7 6 5 4 4 3 3 2 1 2. 2. 2. 1. 1. 1.
9 8 2 2 9 4 2 4 7 2 7 0 3 5 11 07 02 97 93 87
0 1 7 5 0 8 3 6 2 7 8 4 5 41 12 64 95 02 80
7 9 4 1 1 3 5 8 7 9 0 1 5

4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
2 3 4 0 8 7 5 5 4 3 3 2 2 1 2. 2. 1. 1. 1. 1.
0 5 9 9 6 1 9 1 4 9 4 7 0 2 08 03 99 94 89 84
1 2 8 6 0 9 4 7 2 7 7 3 4 25 91 38 64 63 32
2 8 4 1 9 0 0 1 8 9 6 3 2

2 4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1.
1 3 4 0 8 6 5 4 4 3 3 2 1 0 05 01 96 91 86 81
2 6 7 4 8 7 8 2 6 2 5 7 9 40 02 45 65 57 17

232
 4 6 2 0 4 2 7 0 6 1 0 5 6
8 8 5 1 8 7 6 5 0 0 4 7 0

4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
2 3 4 0 8 6 5 4 3 3 2 2 1 0 2. 1. 1. 1. 1. 1.
2 0 4 4 1 6 4 6 9 4 9 2 5 7 02 98 93 88 83 78
0 3 9 6 1 9 3 6 1 6 5 0 0 83 42 80 94 80 31
9 4 1 7 3 1 8 5 9 7 8 8 7

4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
2 2 4 0 7 6 5 4 3 3 2 2 1 0 2. 1. 1. 1. 1. 1.
3 7 2 2 9 4 2 4 7 2 7 0 2 4 00 96 91 86 81 75
9 2 8 5 0 7 2 4 0 4 3 8 7 50 05 39 48 28 70
3 1 0 5 0 7 2 8 1 7 6 2 6

4. 3. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
2 2 4 0 7 6 5 4 3 3 2 1 1 0 1. 1. 1. 1. 1. 1.
4 5 0 0 7 2 0 2 5 0 5 8 0 2 98 93 89 84 78 73
9 2 8 6 0 8 2 5 0 4 3 7 6 38 90 20 24 96 30
7 8 8 3 7 2 6 1 2 7 4 7 7

4. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2.
2 2 3 9 7 6 4 4 3 2 2 1 0 0 1. 1. 1. 1. 1. 1.
5 4 8 9 5 0 9 0 3 8 3 6 8 0 96 91 87 82 76 71
1 5 1 8 3 0 4 7 2 6 4 8 7 43 92 18 17 84 10
7 2 2 7 0 4 7 1 1 5 9 9 5

4. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1.
2 2 3 9 7 5 4 3 3 2 2 1 0 9 1. 1. 1. 1. 1. 1.
6 2 6 7 4 8 7 8 2 6 1 4 7 8 94 90 85 80 74 69
5 9 5 2 6 4 8 0 5 9 7 1 9 64 10 33 27 88 06
2 0 2 6 8 1 3 5 5 7 9 6 8

2 4. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1. 1.
8 1 3 9 7 5 4 3 2 2 1 1 0 9 91 86 82 76 71 65

233
 9 4 4 1 5 4 5 9 3 9 1 4 5 47 87 03 89 38 41
6 0 6 4 8 5 9 1 6 0 7 1 8
0 4 7 1 1 3 3 3 0 0 9 1 6

3. 2. 2. 2. 2. 2. 2. 1. 1. 1. 1. 1. 1.
8 9 6 3 2 0 0 9 8 8 7 6 5 1. 1. 1. 1. 1. 1.
4 9 0 7 1 9 0 3 7 3 5 6 7 51 45 39 31 22 00
1 5 4 1 4 8 9 8 9 0 2 6 0 73 91 40 80 14 00
5 7 9 9 1 6 6 4 9 7 2 4 5

234
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237
238
CC NGUN C BN V CC GI TR CA KB

239
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