Chng 1: CC DNG SAI S TRONG HA PHN TCH

1.1. Sai s v cch biu din 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 ( khng m bo o) ca s liu phn tch.
C hai loi sai s c biu din ch yu trong Ha phn tch l sai s tuyt i v sai
s tng i.
1.1.1.Sai s tuyt i (EA) (Absolute error)
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 phng php.
* 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;
b) gi tr c n nh hoc chng nhn trn c s th nghim ca mt s t chc
quc gia hoc quc t;
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 a), b) v c).
1.1.2. Sai s tng i (ER) (Relative error)
L t s gia sai s tuyt i v gi tr tht hay gi tr bit trc, c chp
nhn.
ER =

xi

hay ER % =

EA

. 100%

* Sai s tng i cng c th biu din di dng phn nghn (parts per
thousand-ppt)
ER =

. 1000 (ppt)

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

c dng biu din chnh xc ca phng php phn tch.

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

hnh 1.1. Hm lng ng ca aspirin trong mu chun l 200 mg. Nh vy, php
o mc sai s tuyt i t -4mg n +10mg v sai s tng i t -2% n +5% (hay
20ppt n 50ppt).
195

200

205

Sai s tuyt i (EA : mg)

-5

Sai s tng i (Er : % )

-2,5

2,5

210

10
5

Hnh 1.1: Sai s tuyt i v sai s tng i khi phn tch aspirin trong mu chun.

1.2. Phn loi sai s

1.2.1. Sai s h thng hay sai s xc nh (Systematic or determinate error):
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). Do , khi kch thc mu tng
th nh hng ca sai s ny hu nh khng ng k v c loi tr bng th nghim
vi mu trng (blank sample).
- 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.

Sai s h
thng bin
i

Sai s h
thng khng
i

Khi
lng
cht
phn
tch
(mg)

Gi tr ng

Khi lng mu (g)

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

Sai s h thng phn nh chnh xc ca phng php phn tch. 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) ...
* 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.
- Phn tch theo phng php thm chun loi tr nh hng ca cc cht cn
tr.
- Phn tch mu chun (hay mu chun c chng nhn- mu CRM: Mu chun
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.
- Thay i kch thc mu: pht hin sai s h thng khng i v bin i.
1.2.2. Sai s ngu nhin hay sai s khng xc nh (random error or
indeterminate):
L nhng sai s gy nn bi nhng nguyn nhn khng c nh, khng bit trc.
Sai s ngu nhin thng gy ra do:
-

Khch quan: nhit tng t ngt, thay i kh quyn, i lng o c

chnh xc gii hn

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.
1.2.3. Gi tr bt thng (outliers):
Gi tr bt thng l nhng gi tr thu c thng rt cao hoc rt thp so vi gi
tr trung bnh. Gi tr bt thng dn n nhng kt qu thu c sai khc nhiu so vi
tt c cc s liu lp li ca tp s liu.
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.
1.2.4. Sai s tch lu (accumulated error):
Trong mt phng php phn tch, sai s ca s liu phn tch thu c thng
bao gm sai s do cc giai on trong qu trnh phn tch ng gp nn. sai s
chung l nh th khi phn tch cn phi tm iu kin ti u theo nh lut lan truyn
sai s.
Sai s tch lu hay s lan truyn sai s h thng c x l tng t nh sai s h
thng. V sai s h thng c du (+) hay (-) nn s dn n s trit tiu sai s v trong
mt s trng hp sai s tch lu c th bng khng.
-

Khi ch c kt hp tuyn tnh ca php o ngu nhin ( 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.
Nu m= A+B +C th Em = EA +EB + EC

- Khi biu din nguyn nhn cc kt qu ( kt qu cui cng l php nhn hoc chia),
ngi ta dng sai s xc nh tng i ETR

ERm ERA ERB ERC

=
+
+
Nu m= A.B/C th
m
A
B
C
Th d 1.2:
4

a) Khi cn mu trn cn phn tch c chnh xc 0,0002 gam 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) Khi lng dung
(3,430,01).(5,660,01)=?

dch

tnh

theo

cng

thc

m=V.d=

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)
1.3. lp li, trng, hi t, phn tn
* lp li (repeatability): Trong phn tch, khi thc hin cc php th nghim
thc hin 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 khng th kim sot
c hon ton tt c cc yu t nh hng n u ra ca mt php o. Khi bo co
cc d liu o, cn xem xt n nguyn nhn v kt qu s thay i ny.
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 o, 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
S thay i gia cc php o do 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.
* trng (reproducibility): c trng cho mc gn nhau gia gi tr ring l
xi ca cng mt mu phn tch, 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,
thi gian) (between laboratory precision) .
Vi cng mt phng php phn tch, thng xt n lp li hn l
trng.
* 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.
5

* 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.
1.4. chm v chnh xc
* 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 .
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 lch ca s liu phn tch khi gi tr trung bnh: di = xi x
* ng (trurness): 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.
* chnh xc (accuracy): l mc gn nhau ca gi tr phn tch (thng l
gi tr trung bnh x ) vi gi tr thc hay gi tr c chp nhn xt hay .
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.
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 sau 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 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
nh.