1

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 (E
A
) (Absolute error)
L s sai khc gia gi tr o c (x
i
) vi gi tr tht hay gi tr qui chiu c
chp nhn (k hiu l ).
E
A
= x
i
-
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 (E
R
) (Relative error)
L t s gia sai s tuyt i v gi tr tht hay gi tr bit trc, c chp
nhn.
E
R
=

i
x
hay E
R
% =

A
E
. 100%
* Sai s tng i cng c th biu din di dng phn nghn (parts per
thousand-ppt)
E
R
=

A
E
. 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.




2
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).
195 200 205 210

Sai s tuyt i (E
A
: mg) -5 0 5 10
Sai s tng i (E
r
: % ) -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.
1.2. 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.
3


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

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

4
- 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 E
T
l tng cc sai s tuyt i ca php
o ring r.
Nu m= A+B +C th E
m
= E
A
+E
B
+ E
C

- 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 E
TR

Nu m= A.B/C th
C
E
B
E
A
E
m
E
C B A
R R R
Rm
+ + =

Th d 1.2:
5
a) Khi cn mu trn cn phn tch c chnh xc 0,0002 gam c kt qu nh
sau:
m
chn +mu
= (21,1184 0,0002) gam ; m
chn
= (15,8465 0,0002) gam
vy khi lng mu s l
m
mu
= (21,1184 0,002) - (15,8465 0,002) = (5,2719 0,004) gam
b) Khi lng dung dch c tnh theo cng thc m=V.d=
(3,430,01).(5,660,01)=?
Ta c:
E
RV
= 0,01/3,43 ; E
Rd
= 0,01/5,66; E
Rm
= (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
x
i
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.
6
* 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 x
i

ca cc php o lp li. Ni cch khc, chm c dng ch s sai khc gia cc
gi tr x
i
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: d
i
= x x
i

* 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 x
t
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.











7
Chng 2 CC I LNG THNG K
(Descriptive statistics)
2.1. Cc i lng trung bnh
* 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 x
1
, x
2
,, x
N
th gi tr trung bnh s hc
ca tp s liu gm N th nghim lp li l:
x =
N
x x x
n
+ + + ...
2 1
=
N
x
N
i
i
=1
(2.1)
Gi tr trung bnh c tnh cht sau:
- Tng lch gia cc gi tr ring r v gi tr trung bnh bng khng.

= 0 ) ( x x
i

- 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.

2
) ( x x
i
<

2
) ( a x
i
( vi a x )
* Trung bnh bnh phng ( x
bp
): vi tp s liu gm N s liu lp li x
1
,
x
2
,,x
n
ta c:
x
bp
=
N
x x x
n
2 2
2
2
1
... + + +
(2.2)
* Trung bnh hnh hc hay trung bnh nhn (geometric average) vi cc php
o c hm lng cn tm di dng logarit th:
lg x
hh
= ) lg ... lg (lg
1
2 1 Nn
x x x
N
+ + +
Do x
hh
=
N
N
x x x .... .
2 1
( 2.3)
* Trung v (median) : Nu sp xp N gi tr lp li trong tp s liu theo th t
tng n hoc gim dn t x
1
, x
2
, , x
N
th s nm gia tp s liu c gi l trung
v.
- Nu N l th trung v chnh l s gia dy s.
- Nu N 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
8
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.
2.2. Cc i lng c trng cho 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 = x
max
- x
min
(2.4)
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 S
2
): 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 th
( )
N
x x
N
i
i
=

=
1
2
2

Nu tp s liu nh th
( )
1
1
2
2

=
N
x x
S
N
i
i
=
|
|
|
|
|

\
|
|

\
|

=
=
N
i
N
i
i
i
N
x
x
N
1
2
1 2
1
1
(2.5)
vi N-1=f l s bc t do.
Khi c m tp s liu, mi tp s liu lm k th nghim lp li i vi cng mt
mu nh:
x
11
, x
12
, x
13
,, x
1k


x
21
, x
22
, x
23
,, x
2k


x
j1
, x
j2
, x
j3
,, x
jk

x
m1
, x
m2
, x
m3
,., x
mk

9
th
( )
k N
x x
S
m
j
k
i
i ij

= = 1 1
2
2
(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 km.
* lch chun (Standard deviation)
- 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 php o
cc mu phn tch ring r) 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 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 tng th .
+ Trung bnh mu ( sampling fluctuation) ( x ) l gi tr trung bnh ca mt mu
thng k gii hn c rt ra t tp hp cc s liu v c xc nh theo cng thc:
N
x
x
N
i
i
=
=
1
.
+ Trung bnh tng th (population average) () l gi tr trung bnh ca tp hp
cc s liu, 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 tng th cng l gi tr tht ca php
o.

N
x
N
i
i
=
=
1
khi N . Thng thng khi N > 30 c th xem nh x
- lch chun tng th (Population standard deviation): () c trng cho
phn tn cc s liu trong tp hp vi gi tr trung bnh v c xc nh theo phng
trnh:

( )
N
x x
N
i
i
=

=
1
2
hay
2
= (2.6)
vi N l s th nghim lp li ca tp hp, thc t thng xem cc tp s liu c
N>30 l tp hp.
- lch chun mu c on (Sample estimate standard deviation): (S)

10

( )
1
1
2

=
N
x x
S
N
i
i
hay
2
S S = (2.7)
vi N l s th nghim trong mu thng k c rt ra t tp hp. S bc t do
trong trng hp ny l f =N-1.
(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 kch thc mu tr i 1
bc t do cho mi trung bnh. Thut ng bc t do cn c dng ch s lch
( ) x x
i
) c lp dng trong php tnh lch chun)
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.
Khi tnh ton ch khng lm trn s liu ca lch chun cho n khi kt
thc php tnh ton v ch ghi gi tr cui cng di dng s c ngha.
Nu trng hp c m mu thng k, mi mu lm n th nghim song song th:
( )
m n m
x x
S
m n
ij

.
1 1
2

bc t do f=m(n-1) (gi thit S
j
khc nhau khng ng k).
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).
S
R
=R.K
R
Gi tr K
R
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)
( ) ( ) ( )
5 3 2 1
1 1 1
2
3 3
2
2
2
2
1 1
...
1 2 3
N N N N
x x x x x x
S
N
i
N
j
N
k
k j i
pooled
+ + +
+ +
=

= = =

Vi N
1
l s cc s liu trong tp s liu th nht, N
2
l s cc s liu trong tp
s liu th hai, N
*
l s cc tp s liu c hp nht.
* sai chun ( lch chun trung bnh) (standard deviation of a mean
standard error):
11
Nu c nhiu dy s liu lp li (nhiu mu thng k), mi dy c N s liu
c ly ngu nhin t tp hp s liu th s phn tn ca trung bnh mu 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

Dng sai chun
m
c trng cho sai s ngu nhin cu phng php
phn tch. Tuy nhin, i vi tp s liu hu hn (N<30) ch thu c s c lng
x
S
thay cho
m
.
( )
( ) 1
2
1
2

= = =

=
N N
x x
N
S
N
S
S
N
i
i
x

sai chun thng c dng c trng cho bt n ca gi tr trung bnh.
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).
+ Dng kt qu phn tch khng lm trn (vi 1 ch s cui cng l s khng c
ngha).
+ S ph thuc tr s gi tr o v thnh phn mu.
* lch chun tng i (Relative standard devition) (RSD) v h s bin
thin (coefficient variation) (CV).
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 phn trm (nhn vi 100%).
RSD(%)= 100 .
x
S
% hay RSD= 1000 .
x
S
ppt
RSD(%) cn c gi l h s bin thin (CV). i lng ny c dng o
chnh xc tng i 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.
* 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.
12
Th d 2.1 :Cho kt qu phn tch lp li 35 ln hm lng nitrat (g/ml) 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
Sv t tnh cc i lng thng k theo cng thc v so snh vi kt qu tnh theo phn
mm MINITAB di y, gii thch ngha cc kt qu .
hamluong nitrat ( micogam/ml)
0.53 0.52 0.51 0.50 0.49 0.48 0.47 0.46
Phanbo cac gia tri thuc nghiemtheo tan suat

h
a
m

l
u
o
n
g

n
i
t
r
a
t

(

m
i
c
r
o
g
a
m
/
m
l
)
0.53
0.52
0.51
0.50
0.49
0.48
0.47
0.46
Do thi khoi cac gia tri thuc nghiem

2.3. Bo co kt qu phn tch
2.3.1. 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 cn phi ghi r tin cy ca s liu
v cc s liu cn c lm trn ch mc khng chc chn ca n (uncertanty).
Ni cch khc, s liu ch c cha cc s c ngha.
2.3.1.1. 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 2.2 : Khi c th tch dung dch ng trong buret 50 ml, chng ta c th
thy vch cht lng v tr ln hn 30,2 ml v nh hn 30,3 ml. Nu c th c on
v tr vch cht lng cp chia khong + 0,02 ml th c th bo co th tch l
Descriptive Statistics for nitrate
concentration
Total Count : 35
Mean: 0.50413
SE Mean: 0.00260
StDev : 0.01537
Variance : 0.000236
CoefVar : 3.06
Sum of Squares: 8.80810
Minimum: 0.46
Q1: 0.49
Median : 0.50
Q3 : 0.51
Maximum : 0.53
Range: 0.07
Skewness : -0.20
Kurtosis: 0.50
hamluongnitrat ( microgam/ml)
t
a
n

x
u
a
t
0.53 0.52 0.51 0.50 0.49 0.48 0.47 0.46
10
8
6
4
2
0
Bieu do phan bo tan xuat ham luong nitrat

13
30,24 ml (4 s c ngha).
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 khng 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 khng nm gia cc s khc l s c ngha.
- Nu s khng nm cui dy s th ch l s c ngha nu ng sau du
phy.
- Nu s khng nm trc du thp phn th khng phi l s c ngha.
* Lm trn s: l loi b cc s khng c ngha trong kt qu. 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. V d: 2,25 lm trn thnh 2,2; 2,35 thnh 2,4.
Th d 2.3 : 25,24 c 4 s c ngha 0,15 c 2 s c ngha
15,00 c 4 s c ngha 1,36 c 3 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. (Nh vy
c th ghi gi tr nng l 0,0215; 2,15.10
-2
hoc 21,5.10
-3
hoc 215.10
-4
M)
Nu ghi th tch bnh l V= 2,0 lit th khi chuyn sang n v ml khng th ghi l
2000 ml (v y ch ghi 1 s c ngha) m phi ghi l 2,0.10
3
ml.
2.3.1.2. Cch ly gi tr gn ng
* i lng o trc tip: gi tr o c phi 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.
* i lng o gin tip.
- Php tnh cng v tr : lm trn s thnh s chnh xc v ghi s c ngha theo g
tr no c t s c ngha nht.
- 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. (Khi tnh bt n tuyt i
khgn tnh n du thp phn)
- Php tnh logrit v ngc logrit:
+ logrit: ly cc ch s sau du phy bng tng cc s c ngha trong s ban u
+ ngc logarit: ly cc s c ngha bng s cc ch s sau du phy.
Th d 2.4: 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.
14
b) % 5470578 , 88 % 100 .
1689 , 1
05300 . 0 . 5481 , 0 . 63 , 35
=
Trong dy s trn, khng chc chn ca mi s l 1/3563; 1/5481; 1/5300 v
111689/ Nh vy khng chc chn ca s th nht ln hn so vi khng
chc chn ca s th hai v th ba. Do , gi tr c t s c ngha nht l 35,63
nn kt qu cui cng phi c ghi l 88,55%
c) log(9,57.10
4
)=4- log 9,57= 4,981 (gi tr 4 c 1 s c ngha; gi tr9,57 c 3
s c ngha )
log(4,000.10
-5
)=5- log4,000=-4,397940=-4,3479
Antilog(12,5)=3,162277.10
12
=3.10
12

2.4. Quy lut lan truyn sai s ngu nhin - lch chun ca i lng o gin tip
Tt c cc kt qu phn tch nh lng thu c t thc nghim u c cha sai
s ngu nhin. V vy, cc gi tr c bo co thng l gi tr trung bnh vit ng
s c ngha km theo sai s ngu nhin ca gi tr . Thng thng chng c vit
l S x , vi S l lch chun.
Th 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 S x = 10,10+0,01 (vi N=5 th nghim lp li).
Ngoi ra, khi s th nghim lp li ln, kt qu phn tch cn c trnh by
di dng
N
S t
x
.
v s c xt n trong chng 3.
Tuy nhin, 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. Mt khc, mi s liu thu c trong cc php tnh u c lch
chun ring, v vy phi xt n lan truyn sai s gy ra cho kt qu cui cng.
Gi s cc kt qu thc nghim a, b, c, .. l cc s liu thu c t cc php o
trc tip M
1
, M
2
, M
3
. Gi x l gi tr cui cng tnh ton c t cc kt qu ring
r a, b, cKhi x l hm ph thuc vo cc tham s a, b, c
Gi
c b a
, , l lch chun ca cc php o trc tip 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 / 1 2
2
2
2
...] [ +
|
|

\
|
+
|
|

\
|
=
b
b
x
a
a
x
x

(theo nh lut lan truyn sai s, biu thc

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.
* lch chun ca tng v hiu:
x = a
1.
a( S
a
) + b
1
.b( S
b
) c
1
.c( S
c
) vi a
1
,b
1
, c
1
l cc hng s th
lch chun ca x l
15
... . . .
2 2
1
2 2
1
2 2
1
+ + + =
c b a x
S c S b S a S
* lch chun ca php nhn v chia:
x =
1
1 1
.
c
b a
c
b a
th ... . . .
2
2
1
2
2
1
2
2
1
+ |

\
|
+ |

\
|
+ |

\
|
=
c
S
c
b
Sb
b
a
S
a
x
S
c a x

Khi , kt qu s c biu din di dng x =
1
1 1
.
c
b a
c
b a
S
x
.
* lch chun ca php tnh logarit:
x= k.lna th S
x
= |

\
|
a
S
k
a
.
x= k.loga th S
x
= |

\
|
a
S k
a
.
30 , 2

Cc gi tr lch chun trong php o trn c gi l sai s tuyt i ca php
o. i lng |

\
|
a
S
a
gi l sai s tng i.
Th d 2.5: a) Tnh gi tr biu thc:
(65,060,07) +(16,130,01)-(22,680,02)= 58,51?
ta c
x
S 073 , 0 02 , 0 01 , 0 07 , 0
2 2 2
= + + = V biu din x = 58,51 0,07
lch chun tng i ca php o l % 1 , 0 % 100 .
51 , 58
07 , 0
=

b) ? 0 , 356
006 , 0 623 , 4
) 2 , 0 4 , 120 ).( 02 , 0 67 , 13 (
.
=

= =
c b
a
x
ta c
2 2 2
623 , 4
006 , 0
4 , 120
2 , 0
67 , 13
02 , 0
|

\
|
+ |

\
|
+ |

\
|
=
x
S
x
=0,0026 do vy
S
x
=356,0.0,0026=0,93
kt qu cui cng s l x = 356,00,9
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 AgNO
3
c nng
( 0,11670,0002) M. Th tch dung dch AgNO
3
tiu tn sau 3 ln o lp li l 36,78;
36,82 v 36,75 ml.
HD gii : - th tch dung dch chun AgNO
3
trung bnh l: 36,78 ml
- p dng cng thc tnh lch chun th tch chun ta c S= 0,035
- Vy 04 , 0 78 , 36
3
=
AgNO
V (ml)
- S mmol Cl
-

c chun trong 250 ml mu :
X= (0,11670,0002).((36,780,04).10= 42,92 ?
16
Ta c : 019 , 0 10 .
78 , 36
04 , 0
1167 , 0
0002 , 0
2
2 2
= |

\
|
+ |

\
|
=
x
S
x

Do S
x
= 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.





























17
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 dng biu thng gp l biu
ct hay biu hnh ch nht (bar chart), biu hnh qut (pie chart), biu tn
sut (historgram) hay biu ng gp khc (pylogon). Nu cn biu din gi tr
thc nghim ca cc tp s liu khc nhau, th s dng ln ca cc s liu. Trong
trng hp cn biu din cc s liu trong cng tp s liu th thng dng tn sut
ca gi tr trong tp s liu.
Trong phn trnh by di y ch xt n biu biu din tn s xut hin ca
gi tr trong tp s liu di hai dng biu tn sut v biu ng gp khc .
Cch tin hnh: Cc gi tr trong tp s liu 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: Ngi ta xc nh ng thi Al trong mt mu thp 12 phng th nghim
(PTN). Mi PTN cho 5 gi tr phn tch thu c 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 (%)
trong mu thp
STT PTN X
1
X
2
X
3
X
4
X
5
1 A 0,016 0,015 0,017 0,016 0,019
2 B 0,017 0,016 0,016 0,016 0,018
3 C 0,015 0,014 0,014 0,014 0,015
4 D 0,011 0,007 0,008 0,010 0,009
5 E 0,011 0,011 0,013 0,012 0,012
6 F 0,012 0,014 0,013 0,013 0,015
7 G 0,011 0,009 0,012 0,010 0,012
8 H 0,011 0,011 0,012 0,014 0,013
9 I 0,012 0,014 0,015 0,013 0,014
10 K 0,015 0,018 0,016 0,017 0,016
11 L 0,015 0,014 0,013 0,014 0,014
12 M 0,012 0,014 0,012 0,013 0,012


Gii hn 8 10 12 14 16 18 20 .10
-3
%
trn ca cp
ca
Hnh 3.1: Phn phi tn sut khi xc nh ng
thi hm lng Al trong mu thp ti 12 PTN.
M
M
M L
M L
M L L
I L K
H I K
H I K
H I I
G H F
G H C
G F C
F F B
E F B K
G E E B K
G E C A B
D D E C A B
D D D C A A A
18
Nh vy c tt c N=60 gi tr. Gi tr thp nht l ca PTN D c
2
D
X =0,007%.
Gi tr cao nht ca PTN A l
5
A
X
= 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 phn b tn
sut thc nghim c trnh by hnh 3.1 v biu tn sut phn trm hnh 3.2.
T
a
n

x
u
a
t

(
%
)
20 18 16 14 12 10 8
35
30
25
20
15
10
5
0

Hnh 3.2. Biu phn trm tn sut hm lng Al trong kt qu phn tch cc PTN
T dng phn b tn sut c th thy c nh tnh v s xut hin sai s ngu
nhin. Khi sai s ngu nhin ln th phn b rng, sai s ngu nhin nh th phn b
hp v nhn, nhng trong trng hp ny khng cho bit v sai s h thng v sai s
h thng khng lm thay i dng phn b.
3.2. 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)
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 rng ca lp nh (d 0) th phn b tn sut c biu din bng hm
mt xc sut sau:
2
) (
2
1
2
1
) (

=
x
e x y
(3.1)
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
19
tht hoc gi tr trung bnh, c trng cho php o v tr phn b (measure of location) ;
x l to hoc gi tr trn trc honh; Y: tung d, chiu cao ca ng biu din
tung ng vi gi tr x.
V tr v dng ng cong c xc nh bi v . Cc i ca ng cong
ti y' = 0, tc l im x= . Cc im un l x
1
= - v x
2
= + . 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 .

Hnh 3.5: Phn b chun vi cc gi tr
trung bnh cng khc nhau.
Hnh 3.6 : Biu din hnh hc ca lch
chun
Nu k hiu

=
x
Z th Z l mt bin ngu nhin v hm phn b c dng
2
.
2
1
2
1
) (
Z
e z Y

=

(3.2) khi
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).
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 gi tr x
i
. Gi tr xc sut
ny 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 x
i
trong khong tch phn.
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. Xc sut gi tr o nm ngoi gii hn trn ca tch phn l =1-P. Phn
din tch P cng c biu din theo % so vi tng din tch v gi l tin cy thng
k.
Trong khong th mt xc sut chim 68 % din tch ca ng cong.
Trong khong 2 th mt xc sut chim 95 % din tch ng cong. C
ngha l c 95 % gi tr trung bnh mu nm trong khong:
m

c

s
u

t

lch chun
20
- 1,96(
n

)< x < +1,96 (

n

). Do khong bin thin gi tr thc l:

x - 1,96(
n

)< < x +1,96 (

n

) (y l khong tin cy c on ca gi tr trung

bnh).
Trong khong 3 th mt xc sut chim 99,7 % din tch ca ng cong.
Tc l x - 2,97(
n

)< < x +2,97 (

n

)
a s cc kt qu o 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.
Nu k hiu tin cy thng k xut hin ga tr x
i
nm trong vng (-, x
i)
l
P(x
i
). T hm phn b chun, khi cho gi tr u
i
(x) ta tnh c tin cy thng k P
i

(ng vi din tch P
i
v ngc li. Thay cho tnh ton, ngi ta lp sn bng s tra
gi tr u khi bit P hoc ngc li (xem ph lc 1 )
Ch : -Trong thc nghim c nhng tp s liu 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 ri tnh gi tr trung bnh v lch chun .
Phn phi ny gi l phn b log-chun (log-normal distribution).
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
x

=
vi x= 0,1, 2, 3 v l trung bnh ca s cc s kin
trong khong thi gian xt.
Phn b ny c gi l phn b Poisson, cc i lng c trng thng k l:
- Gi tr trung bnh = .
21
- Phng sai
2
=
- Gia v c quan h: =
1/2
vi l s thc v >0

Hnh 3.6. Phn b Poisson vi cc gi tr khc nhau ca trung bnh cng.
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. Cc phn b c bit.
3.2.3.1. Phn b Student (t)
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:

2
1 2
) 1 ( ) , (
+

+ =
f
f
t
B f t Y vi B l hng s v f l bc t do.
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 (hnh
3.7).

22

Hnh 3.7: 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. Hai loi bng tra gi tr t tng ng vi phn b t mt pha hoc
hai pha (hnh 3.8).
Chun t (Student-test) c dng tnh khong tin cy ca s liu thc nghim,
so snh gi tr trung bnh thc nghim v gi tr tht, so snh 2 gi tr trung bnh hoc
tnh khng m bo o ca lch chun mu khi s mu nh.




3.2.3.2. Phn b Fisher (F)
Gi s c 2 tp s liu vi kch thc mu N
1
v N
2
, phng sai tng ng l S
1
2

v S
2
2
vi cc bc t do f
1
= N
1
-1 v f
2
= N
2
-1 v lp t s :
PP chun
Phn phi chun

/2 /2
Hnh 3.8 : Phn b Student 1 pha (1 sided) v hai pha (2 sided).

xc sut P
23

2
2
2
1
S
S
F =
(F>1)
Th hm mt xc sut c dng:
2
2
1
2
2
) , , (
2 1
1
2 1
) 1 (
f f
f
f f x
f
f
x
A Y
+

+
=

trong , x l bin ngu nhin v A l hng s ph thuc f
1
v f
2
; 0 x +.
ng cong thu c mang c tnh ca mt pha, c v trong gc phn t th
nht gia x=0 v x= (hnh 3.9).

Hnh 3.9. Phn b F vi hai bc t do f
1
v f
2.
Nu ly tch phn hm phn b trong gii hn 0...F
p
( F
p
<) ta c P phn ca
tng din tch di ng cong, n biu th xc sut gi tr tm c
2
2
2
1
s
s
F =
nm gia 0 v F
p
. Cc gii hn ca php tch phn F(P, f
1
, f
2
) vi P = 0,95 v P = 0,99
theo f
1
, f
2
c cho ph lc.
3.2.4. Phn b
2
( chi - square distribution)
Cho i lng ngu nhin x
1
, x
2
...x
n
. Nu c phn b chun th c th thu c
i lng ngu nhin vi s bc do f=n-1

2
2
2
2
1
) 1 ( ) (

= =

s
n
x x
n
i

Hm phn b
2
c dng:
2
2
) ( ) , (
2
2
2

=

f
Ce f Y

0< <+
1 2 3 4

24
Hm phn b vi
2
nm trong gc phn t th nht trong min t
2
=0

n

2
=
c dng ph thuc vo bc t do f (hnh 3.10).


Nu f nh, ng cong bt i xng, nu f tng s bt i xng gim v f
ta c ng cong Gauss vi >0. Ly tch phn hm phn b trong gii hn t 0 n

2
P
(
2
P
<) ta c phn tng din tch di ng cong ng vi xc sut gi tr
2

= thu c t f quan st c lp, ri vo khong (0,1...
2
P
). Cc gii hn ly tch phn
hm
2
(, f) vi =0,95 v =0,99 c cho trong phn ph lc. Hm phn b vi
2
c
dng kim tra phng sai.
3.3. Quan h gia cc phn b ring


















Phn phi F
Bc t do f
1
v f
2

f
1
=1; f
2
= f
F= t
2

f
1
=f;

f
2
=
F=
2
/f
Phn phi t
Bc t do f
Phn phi
2

Bc t do f
f=
t=z
f=

2
=z
Phn phi chun
=
2

x>15
Phn phi Poisson
F=S
1
2
/S
2
2

N s
x
t
/

=
2 /
2 2
fS =

=
x
Z



! / x e P
x

=
f=2
f=10
Hnh 3.10: Phn b
2
vi f bc t do.
25
3.4. Khong tin cy, gii hn tin cy v khng m bo ca i lng o
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 n 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, 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

N
Z x

<

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

=

y Z l yu t thng k, lin quan ti mc ngha 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 ngha thng k l 95% th gi tr thc tn ti trong khong :
) 96 , 1 ; 96 , 1 (
N
x
N
x

+

Thc t c th p dng chun Z cho tp s liu c s th nghim N>30 v tun
theo phn b chun.
i vi cc tp s liu nh (tc l cc mu thng k c N<30), ngi ta s dng S
( lch chun c on) thay cho ( lch chun) v gi tr chun student (t) thay
cho chun Gauss Z .
Khi , gii hn tin cy c tnh l :
N
S
t x CL = ) (

Gi tr t c tra trong bng phn b t hai pha (phn ph lc) vi tin cy thng
k 95% (hay 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 .
- Mc ngha cng cao th khong tin cy cng ln v c Z v t u tng. Vi
mc xc sut l 100 % th khong tin cy l .
Ch : Vi tp s liu rt nh N<10 nh ch phn tch lp li 2-3 ln th gii hn
tin cy c tnh t khong bin thin R nh sau:
26

R
t R x CL . + =
Gi tr t
R
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

t
R 0,95
6,4 1,3 0,72 0,51 0,40 0,33 0,29 0,26 0,23 0,00
t
R 0,99
31,83 3,01 1,32 0,84 0,63 0,51 0,43 0,37 0,33 0,00
3.5. Mt s bi ton lin quan n khong tin cy
3.5.1. X l s liu thc nghim tm khong tin cy ca gi tr thc
- Khi cha bit lch chun S hay khong bin thin CV
Gi s c tp s liu thc nghim : x
1
, x
2
, ...x
N
. T dy s ny ta tm c gi tr trung
bnh, phng sai S
2
v lch chun S.
Nh vy, vi tin cy P=0,95, tra bng ta c t(P,f) v xc nh c gi tr cn tm
nm trong khong
N
S
t x = ) (
Th d 3.2: Kt qu phn tch hm lng it trong mt mu nc bin Thanh Ho
theo phng php ng hc xc tc -trc quang ln lt l: 24,75; 25,12; 24,76;
26,28; 25,15 g/l. Tm khong xc nh ca hm lng thc it trong mu nc ny.
(SV t gii)
- Khi bit lch chun S hay khong bin thin CV
Gi s c tp s liu thc nghim : x
1
, x
2
, ...x
N
.
* Nu N<30, t dy s liu trn tnh c gi tr trung bnh, khi bit S
( hoc nu bit CV th tnh S theo cng thc % 100 . (%)
x
S
CV = ). Tra bng tm t(P,f)
v tnh c
N
S
t x = ) (

Th d 3.3: 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. 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.
(SV t gii)
* Nu N>30: 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:
N
S
x 96 , 1 ) ( =
27
3.5.2. Xc nh s th nghim cn tin hnh thu c chnh xc
mong mun:
Theo cng thc:
N
S
t x = ) (

Gi tr - x =
N
S
t c gi l khng chc chn, hay khng m
bo 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 . mt mc hm lng cht cn
phn tch c th, gi tr - x v lch chun S c cho trc (theo ISO), t
ta s tnh c i lng
N
S
t . Tra bng vi t
(P=0,95; n )
=1,96 s tm c N
kt qu thc nghim c tin cy cho trc.
3.5.3. Chn phng php phn tch thch hp c sai s nh hn gii
hn cho trc .
Mi phng php bit u mc sai s tng i cho trc. Bi ton t
ra l cn chn phng php no sau N ln th nghim th t chnh xc
CV(%) mong mun.
Theo cng thc =
N
S
t nu bit v N, s tnh c S sau , thay
vo cng thc trn xem c tho mn iu kin CV a % cho trc hay khng.
Theo ISO, vi cc mu c nn phc tp, quan h gia CV(%) v nng
cht phn tch c cho bng 3.3.
Bng 3.3: Quan h gia nng cht phn tch v CV cho php
Hm
lng
100
g/kg
10
g/kg
1
g/kg
100
mg/kg
10
mg/kg
1
mg/kg
100
g/kg
10
g/kg
1
g/kg
0,1
g/kg
CV(%) 2 3 4 5 7 11 15 21 30 43
Cng theo ISO, sai s tng i c nh gi qua chnh xc ca
phng php l :
1 ppb sai s tng i cho php t -50 % n +30 %
> 1 ppb n 10 ppb, sai s tng i cho php -30% n +10%
> 10 ppb, sai s tng i cho php -20% n +10%.





28
Chng 4: CC PHNG PHP KIM TRA THNG K

4.1. Nguyn tc php kim tra thng k (significant tests)
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
cng tp hp 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 v gi thit . Ni cch khc ta gi thit l ng (gi thit
o- null hypothesis) v tnh ra xc sut l gi thit ng.
Cch tin hnh: T kt qu cn kim tra ca mu, tnh gi tr ca mt i lng
cn kim tra , xc nh min trong tn ti vi xc sut P nh trc. Nu
nm ngoi min th gi thit chn (hai i lng ging nhau) b bc b v s
khc nhau gia cc i lng thu c gi l s khc nhau c ngha.
Khi kt lun ngi ta tun theo 3 qui tc sau:
- Gi thit cn kim tra b bc b nu sai lm loi mt (b ci ng) xut hin t
hn 100 (1% tng trng hp) (P 0,99 hay tr s P tc l P
value
<0,01), th s khc
nhau c ngha thng k mc tin cy 1%.
- Gi thit cn kim tra c chp nhn nu sai lm loi mt ln hn 100 (5%
tng trng hp) (P 0,95 hay P
value
> 0,05) th kt lun s khc nhau khng c ngha,
tc l c xem nh ging nhau mc tin cy 5%.
- Nu sai lm loi mt nm trong khong 5% v 1% (0,95 < P < 0,99 hay
0,01<P
value
<0,05) th xem l ang nghi vn. Khi phi lm thm php o.
Tuy nhin trong thc t phn tch, ch cn xt kt lun thng k tin cy 95%.
4.2. Xc nh gi tr bt thng
C 3 cch loi b gi tr bt thng:
Cch 1: Quan st mt cch khch quan tm nguyn nhn gy gi tr bt thng
v loi gi tr bt thng.
Cch 2: Gi li 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.
Cch 3: S dng chun thng k 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).
Tuy nhin, trong a s trng hp chng ta khng pht hin ra iu bt thng v vn
tin hnh o,v vn thu c kt qu. Do , cch khc quan l x l thng k theo ba
tiu chun thng k sau y.
* Tiu chun 1: chun Dixon ( Q-test)
29
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 theo biu thc (1) v so snh vi gi tr Q chun trong bng 4.1:
Q
tnh
=
min max
x x
x x
can lan ngo nghi

So snh Q
tnh
v Q
chun
(P=0,90; N). Gi tr nghi ng s chnh l gi tr bt thng
nu Q
tnh
> Q
chun
(P,N).
Bng 4.1 : Gi tr chun Q dng loi b gi tr bt thng.
N Mc tin cy
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 CaCO
3
(%) 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 gn nht ca 54,99 l 54,44.
Ta c: Q= 8 , 0
31 , 54 99 , 54
44 , 54 99 , 54
=

Vi 5 lVi 5 ln th nghim v P=0,90 tra bng chun Q ta c Q
chun
=0,56. vy Q
thc nghim
>Q
chun
hay ga tr 54,59 l gi tr bt thng.
* Tiu chun 2: (p dng cho tp s liu c N>10)
Da trn khong gii hn tin cy: x 2 cha 95 % s liu o c vi x l gi
tr trung bnh ca tp s liu ( loi b s liu nghi ng) v l lch chun tp hp.
Nhng gi tr no ngoi khong trn s c loi b.
*Tiu chun 3: Gi s tp s liu thc nghim c sp xp theo th t tng dn
x
L
, x
2
, , x
H
. Tnh gi tr trung bnh x v lch chun S v kim tra cc gi tr nghi
ng theo cch sau:
Trc tin tnh
S
x x
T
H

= i vi gi tr cao nghi ng.
30
V
S
x x
T
L

= vi cc gi tr thp nghi ng.

Sau so snh gi tr T tnh dc vi gi tr T
chun
(s php o: N) trong bng 4.2
mc ngha 5% v 1%:
Nu T
tnh
>T
chun
th x
L
v x
H
l sai s th cn loi b mc ngha thng k
cho.
Bng 4.2: Gi tr T chun 5% v 1 % ca s khng ph hp vi gi tr bt thng trong mu
chun.
Gi tr chun Gi tr chun S php o (N)
5% 1%
S php o (N)
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
Ngoi ra, cc gi tr bt thng c th c nhn bit bng cch dng th
boxplot trong phn mm thng k MINITAB.
4.3. S dng chun thng k trong cc php so snh
4.3.1. So snh trong 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.
31
Th d 4.2. Kt qu phn tch hm lng Ni( mg/kg) trong mu t 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.Kkt 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
Biu tn sut xut hin cc gi tr trong tp s liu c dng:
Ni
F
r
e
q
u
e
n
c
y
60 48 36 24 12 0
25
20
15
10
5
0
Mean 18.99
StDev 9.907
N 80
Histogram (with Normal Curve) of 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. Ttr 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 trong tp hp 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 H
0
: =
0
, nu khng tho mn th >
0
hay
<
0
mc tin cy thng k cho trc.
- Quyt nh mc ngha , thay i bc b nu n ng.
32
- Quyt nh da trn mc tin cy thng k s dng trong trng hp phn
phi chun: N
x
z

) (
0

=
-Tm phn phi mu ca gi tr thng k nu khng nh n ng.
y phi gi nh rng N
x
z

) (
0

= c phn phi chun vi gi tr trung

bnh bng "khng" v phng sai bng "mt".
- Tnh gi tr Z v so snh vi g tr Z
chun
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
Nu Z <-1,96 hoc Z >1,96 th loi b gi thit o (vi =0,05). Nu chn =
0,01 th xt khong -2,58 n +2,58.
Phng php ny ch p dng cho tp s liu tun theo phn phi chun. Nu Z<
Z
bng
th chp nhn gi thit o hay ni cch khc v
o
khc nhau khng c ngha
thng k. Nu s dng phn mm thng k th gi thit o c chp nhn nu P
value

P

( thng chn l 0,05 tc l khi gi thit ng m loi b th s mc sai lm loi
mt vi xc sut l ).
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). Trung 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 nu gi tr P
value
=0,027 th c ngha l ch c 2,7% c hi
o
. Do
vy, cn kt lun l
o
.
4.3.1.3. So snh gi rt trung bnh mu v gi tr c chp nhn (chun t).
Chun student c dng so snh xem c s khc nhau c ngha gia gi tr
thc nghim x v gi tr thc hay khng. Phng php ny cng c dng so
snh kt qu thc nghim vi gi tr chun trong mu kim tra cht lng (quality
control standard) v mu chun so snh (standard reference materials- SRM).
Php so snh ny da trn khong tin cy ca gi tr trung bnh. Nu s khc
nhau gia gi tr tm c v gi tr thc 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
d cho.
Vi tp s liu c N >20 hoc khi bit lch chun tp hp th
N
Z
x

.

Vi tp s liu c N <20 th
N
S t
x
.

Nh vy nu
N
S t
x
.
th xem nh x ( chp nhn gi thit o vi
P=0,95%)
33
Mt cch khc, so snh v x ngi ta tnh gi tr t
thcnghim
= . x N /S
sau so snh vi gi tr t
chun
(P,f) (tra chun Student 2 ui.
Nu t
thcnghim
> t
chun
hoc P
value
P

th gi thit o b bc b tc l khng c s
khc nhau c ngha thng k gia gi tr trung bnh v gi tr thc.
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 hoc gi tr c chp nhn ) v nh gi s sai khc gia gi tr x vi gi tr
thc .
Tnh gi tr t theo biu thc N
S
x
t

= v so snh vi t(P,f) vi f=N-1
Nu t
tnh
< t
bng
c th kt lun x khng khc hay phng php ch mc sai s
ngu nhin tc l phng php c ng chp nhn c.
Nu t
tnh
> t
bng
th phng php phn tch mc sai s h thng.
Cch so snh ny cn c p dng :
- So snh phng php nghin cu vi phng php chun bng cch so snh gi
tr trung bnh ca tp s liu trong phng php nghin cu vi kt qu c phn tch
bng phng php chun.
- 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 4.3: Khi nghin cu phng php trc quang xc nh As(III) bng vi
thuc th bc ietyl ithio cacbamat 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)
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
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?
Ngun: M.H. Arbab-Zavar, M. Hashemi :Talanta 52 (2000) 10071014.
4.3.2. So snh hai tp s liu (2 samples)
4.3.2.1. So snh phng sai ca hai tp s liu (chun Fisher : 2
2
)
Chun Fisher c dng so snh chm (precision) ca hai tp s liu hoc
hai phng php khc nhau. Gi s c hai tp hp kt qu phn tch thu c t hai
34
ngi phn tch, hai PTN phn tch hoc hai phng php vi hai gi tr phng sai
l
2
1
v
2
2
, bc t do tng ng f
1
v f
2
. Nh vy, cn gii p cu hi
2
1
v
2
2

c phi l phng sai ca cng tp hp khng?
Vy gi thit thng k trong trng hp ny l
2 2
2
2
1
= = .
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
2
1
S v
2
2
S .
Nu "gi thit o" tho mn th t s
2
2
2
1
S
S
phi tun theo phn phi chun Fisher
vi cc bc t do l f
1
v f
2
v gi tr F dc tnh theo cng thc:
F
tnh
=
2
2
2
1
S
S
>1
Khi , s bc b gi thit kim tra nu F
tnh
> F
bng
(P, f
1
, f
2
) (chun 2 ui: 2-
tailed-test) hoc P > P

. Ni cch khc, hai phng sai

2
1
S v
2
2
S c s khc nhau c
ngha hay chnh xc cc s liu thc nghim gia hai mu thng k (hoc hai
phng php) l khc nhau.
Nu lp li hai phng php khc nhau th c th kim tra xem phng php
A chnh xc hn hay km chnh xc hn phng php B (kim tra chun 1 ui: one-
tailed-test). Nu F
thc nghim
> F
chun
(P,f
1
, f
2
) th c th kt lun phng php A km
chnh xc hn phng php B.
Th d 4.5: nghin cu phng php, cn so snh lp li ca hai php o
khi xc nh Na theo phng php quang ph pht x ngn la. Cc ga tr lch
chun thu c ( tnh theo phn trm tng i) nh sau:
Phng php 1: S
1
= 3%; f
1
= 12
Phng php 2: S
2
=2,1%; f
2
=12
Ta c F= 19 , 4
1 , 2
3 , 4
2
2
2
2
2
1
= =
S
S

Tra bng chun F ta c F(0,95; 12;12)=2,79
F(0,95; 12;12)=4,16
Vy F= 4,19 > 4,16 nn c th kt lun rng lp li ca hai php o khc
nhau c ngha, hay lp li ca hai phng php khng ging nhau.
Khi cn so snh chnh xc ca phng php nghin cu c ln hn c
ngha so vi phng php tiu chun khng?
Th d 4.6: nh gi mt phng php mi c xut xc nh SO
4
2-

trong nc thi cng nghip, ngi ta so snh ca phng php ny vi phng
php tiu chun qua th nghim sau:
Phng php

Gi tr
trung bnh
S th nghim
lp li
Bc t do lch
chun (mg/)l
Phng php tiu chun 72 8 7 3,38
35
Phng php xut 70 8 7 1,50
Hi c s khc nhau v ng ca hai phng php hay khng.
( SV t gii)
4.3.2 2. So snh 2 gi tr trung bnh thc nghim (Chun Student: 2t).
Gi s c hai gi tr trung bnh
A
x v
B
x thu c t hai dy php o vi s th
nghim lp li l n
A
v n
B
c lp nhau. Gi thit o cn kim tra l
A
x v
B
x ging
nhau hay s khc nhau gia
A
x v
B
x c phi do sai s ngu nhin hay khng? iu
c ngha l cn kim tra xem c s khc nhau c ngha gia hiu (
A
x -
B
x ) v gi tr 0
hay khng.
Cch lm:
Bc 1: Kim tra xem lp li ca hai tp s liu (qua phng sai
2
A
S v
2
B
S )
c ng nht khng hay c khc nhau c ngha thng k hay khng? (chun F).
- Nu
2
A
S v
2
B
S ng nht ( khc nhau khng c ngha) th tnh S
pooled
theo bc
2.
-Nu hai phng sai khng ng nht th tin hnh bc 3, s dng phng sai
ca A v B.
Bc 2: Nu
2
A
S v
2
B
S ng nht
Tnh lch chun hp nht S
pooled
ca hiu 2 gi tr trung bnh
A
x v
B
x vi s th
nghim n
A
v n
B
<30.

2
) 1 ( ) 1 (
2
) ( ) (
2 2
1
2
1
2
1
+
+
=
+
+
= =

= =

B A
B B A A
B A
n
B Bi
n
i
A Ai
pooled
x x
n n
S n S n
n n
x x x x
S S
B A
B A
( 4.4)
Khi s php o nh th hiu
B A
x x l i lng ngu nhin theo phn phi t.
Do ,
B A
B A
pooled
B A
thucnghiem
n n
n n
S
x x
t
+

=
.
v so snh vi t
chun
(P,f); bc t do l f=(n
A
-
1) + (n
B
-1)= n
A
+n
B
-2 ( v c 2 tp s liu ( n
A
v n
B
v gi tr trung bnh c tnh cho
mi tp s liu)
Nu t
thcnghim
> t
chun
(P,f) (tra chun t 2-pha) th s khc nhau gia
A
x v
B
x l c
ngha thng k.
Nu t
thcnghim
> t
chun
(P,f) (tra chun t 1-pha) th s khc nhau gia
A
x >
B
x l c
ngha thng k. Hoc P
value
<0,05 th s khc nhau gia
A
x v
B
x l c ngha thng
k.
Bc 3: Nu
2
A
S v
2
B
S khng ng nht
Tnh gi tr t
thc nghim
theo cng thc sau:
36

2
2
2
1
2
1
2 1
n
s
n
s
x x
t
calc
+

=

So snh vi ga tr t
chun
tra bng vi P=0,95 v bc t do f tnh theo cng thc
2
1 1
2
2
2
2
2
1
2
1
2
1
2
2
2
2
1
2
1

+
|

\
|
+
+
|

\
|
|

\
|
+
=
n
n
s
n
n
s
n
s
n
s
f
Trong mt s trng hp, phng php trn khng thch hp so snh hai gi tr
trung bnh thc nghim v s mu hn ch, mi phng php so snh ch phn tch mt
mc hm lng, lm lp li n ln, do khng thch hp cho ton b vng nng
kho st. Vic so snh nh gi phng php phn tch s c trnh by trong phn
4.4.
Th d 4.6: 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 vi 10 th nghim ca mi phng php. 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= 0,23 mg/kg. Hi gi tr trung bnh ca hai
phng php c khc nhau c ngha hay khng?.
( Sv t gii)
4.3.2.4. H s tng quan (coefficient of corelation:
COR)
Cng thc tnh h s tng quan tuyn tnh Pearson s c trnh by trong
chng 6.
Trong a s trng hp, h s tng quan Pearson (R) gia tng cp bin thng
c dng. i lng ny c trng cho mc quan h tuyn tnh gia hai bin.
R nm trong khong t -1 n +1. Nu R>0 th hai bin c tng quan ng bin
cn R<o th hai bin c tng quan nghch bin. Gi tr R cng ln th mc tng
quan tuyn tnh cng cao.
Gi thit thng k cn kim tra l hai bin khng c tng quan, =0.
Nu tnh c gi tr P
v alue
th c th so snh vi P

(thng l 0,01 hoc 0,05).

Nu P
valuie
< P

th mc tng quan ca hai bin l khc khng c ngha tc l c

bng chng kt lun chng c tng quan tuyn tnh.
4.3.2.5. ng phng sai (hip phng sai ) (coefficient of variance:COV)
y l thut ton gip tnh ng phng sai gia cc tp s liu, l bc trung
gian trong qu trnh phn tch a bin v s xt trong gio trnh khc.
37
4.4. So snh 2 phng php
Gi s chng ta nghin cu phng php A phn tch cht cha bit no .
Sau khi tm c cc iu kin ti u cho 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 s khng thch hp v kt qu ph thuc vo nh hng ca lng cht
nn khc nhau c trong mu phn tch. Khi , cn tin hnh th nghim theo tng cp.
Vi mi mu phn tch cn lm ng thi hai phng php: Phng php ang nghin
cu v phng php tiu chun v tin hnh vi cc kch thc mu khc nhau . Cc
gi tr thu c ln lt l x
1A
, x
1B
; x
2A
, x
2B
..x
iA
v x
iB.
. Cc kt qu thu c c th
so snh theo phng php tng cp hoc phng php th.
4.4.1. So snh tng cp
nh gi phng php phn tch ang nghin cu vi phng php chun, cn
phi so snh tng cp kt qu (mi kt qu ca mi phng php mt mc nng
nht nh) v s dng chun t so snh 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 khng c ngha
hay khng.
Gi tr t c tnh theo cng thc: t=
N
S x
d d
.
; Vi B A
B A
d
x x
N
x x
x
i i
=

=
)
(

d
x l trung bnh s sai khc gia cc cp gi tr.
V S
d
lch chun c on ca s sai khc.
gi tr t
chun
c tra trong bng chun vi mc ngha P=0,95 v (n -1 ) bc t do.
Nu t
tinh
<t
chun
hay gi tr P
value
>P

=0,05 th gi thit "khng" c chp nhn, c ngha

l hai phng php khng c s khc nhau c ngha. Phng php ny cn gi l
phng php hiu s.
4.4.2. Phng php th
V s liu trn th hai chiu mt trc l phng php phn tch (gi s l
phng php M) v mt trc l phng php chun (gi s phng php N)










Phng php N
Gi s theo phng php M s sai khc l
M
v sai s tuyt i l
M
cn theo
phng php N s sai khc l
N
, sai s tuyt i l
N
.
Phng
php
M
A
B
M

N

38
Mun so snh hai phng php ngi ta so snh hai t s
M
M

v
N
N

bng cch
ly t s hai i lng ny (hay chnh l dc cu ng biu din).
N M N M
N M
N N
M M
tg

/ /
/
/
/
=

=

Kt qu ny cng ln (cng gn 1) th s chnh xc ca phng php M ang
nghin cu cng cao. ng biu din khi s tin ti ng thng. Chng ta s xt
gi tr ny di dng h s tng quan ca phng trnh hi qui tuyn tnh bc mt
(R 1) chng 6.

Th d 4.8: Kt qa phn tch 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: 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?
( Sinh vin t gii)

(Cho kt qu tnh theo phn mm MINITAB 14.0 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
Hy nh ga kt qu trn v a ra kt lun v s ging hay khc nhau ga hai
phng php.



39

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 trong 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 nu. Tuy nhin, nu cn so snh nhiu
hn hai gi tr trung bnh th chun t khng cn ph hp. Do vy cn xt n nh
hng ca yu t trong nhm v giu cc nhm qua nh gi phng sai. Phng
php ny thng c gi l phn tch phng sai (analysis of variance- ANOVA)
hn l thut ng phn tch trung bnh a nhm (multi-group means analysis).
Nh vy, c th ni, phn tch phng sai l phn tch tc ng ca mt hay
nhiu yu t 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).
- 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 ,
1
x ,
2
x ,
3
x ,
k
x trong cng tp hp. Cc trung bnh mu ny
thu c t n th nghim trong mi mu thng k.
Mu thng k 1: x
11
, x
12
, ., x
1n
v c gi tr trung bnh l
1
x
Mu thng k 2: x
21
, x
22
, ., x
2n
v c ga tr trung bnh l
2
x

Mu thng k th i : x
i1
, x
i2
,., x
ij
v c ga tr trung bnh l
i
x
40
Mu thng k k : x
k1
, x
k2
, , x
kn
v c ga tr trung bnh l
k
x
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
=
1
x =
2
x ==
k
x . Khi cc mu thng k thuc cng tp hp th phng sai trong
m 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:
1
) (
1
2
1 1
2
1

=
n
x x
S
n
j
j

1
) (
1
2
2

=
n
x x
S
n
j
k kj
k

1
) (
1
2
2
1

=
n
x x
S
n
j
i ij
i

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 f
0
=k(n-1).
Do vy, phng sai trong cng mu (within-sample estimation of variance/
within-sample mean square) s l:
) 1 (
) (
1 1
2
1
2

= =

= =
=
n k
x x
k
S
MS
k
i
n
j
i
ij
k
i
i
within

*Phng sai gia cc mu: (between-sample estimation of variance)
Trung bnh tp hp :
k
x
X
k
i
i
=
=
1

phng sai gia cc mu:
1
) (
1
2

=
k
X x k
MS
k
i
i
between
bc t do f
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:
wwithin
between
calculate
MS
MS
F =
v so snh vi ga tr F
bng
(P=0,95; f
1
=k-1; f
0
=k(n-1)
Nh vy nu F
tnh
>F
bng
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
41
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.
i lng A c tnh theo cng thc sau:
) , (
.
2
f p
t
k
S A =
Vi S l lch chun c on trong cc mu
within
MS S=

t l gi t chun student tra bng vi tin cy thng k P=0,95 v bc t do f=
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 A v B l 5 >3,26. Vy nguyn nhn
cc gi tr trung bnh mu ny khc nhau l do hai mu A v B 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 nh (mu thng k). Tin hnh phn tch hm lng Al (tnh theo
phn trm Al
2
O
3
) trong mi, lm lp li 6 ln. Kt qu thu c nh sau:
Hy dng phng php ANOVA 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 ng nht khng.
PTN/M
laps
1 2 3 4 5 6
1 4,5 3,9 4,9 5,3 5,1 4,9
2 5,3 5,1 4,8 5,0 4,6 4,9
3 5,5 5,2 5,0 4,7 4,6 5,2
4 4,9 5,2 5,2 4,7 4,3 4,5
5 5,3 5,6 5,7 5,1 4,9 5,1
6 4,9 4,6 5,1 5,3 4,8 5,0
7 5,2 4,7 4,9 5,1 5,7 5,3
42
8 4,9 5,0 5,2 5,4 5,6 5,7
Gii: Nhp s liu vo phn mm MINITAB 14 di dng ct l % Al
2
O
3
v yu
t l cc mu t 1 n 8 .
Vo Stat->ANOVA-> Analysis of Means, nhp response l %Al
2
O
3
. Trong
Distribution of data chn Normal, factor 1 l ct cha Mu, alpha-level l 0.05, v
tick vo OK. Kt qu thu c nh sau:
mau
M
e
a
n
8 7 6 5 4 3 2 1
5.50
5.25
5.00
4.75
4.50
4.657
5.393
5.025
One-Way ANOM for Al2O3(%) by mau
Alpha = 0.05

Trong th trn, ng trung tm chnh l trung bnh chung (grand mean), hai
ng pha ngoi l gii hn quyt nh (decision limit). Nu cc im ch gi tr
trung bnh ca cc mu 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 tho mn tnh ng nht.
Sinh vin t kim tra bng cch tnh ton theo cng thc.
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) 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 khc nhau).
nghin cu nh hng ca yu t A, ngi ta tin hnh k mc th nghim,
mi mc nghin cu lp li n ln, kt qu th nghim l cc gi tr y
ij
( vi i=1k v
j= 1 n nh 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 a
1
a
2
a
3
... a
i
... a
k
43
S ln TN
1

y
11
y
21
y
31
y
i1
y
k1
2 y
12
y
22
y
32
y
i2
y
k2
3 y
13
y
23
y
33
y
i3
y
k3
...
j y
1j
y
2j
y
3j
y
ij
y
kj
...
N y
1n
y
2n
y
3n
y
in
y
kn
Tng ct







so snh s sai khc gia cc kt qu khi thay i cc mc ca A, ngi ta so
snh phng sai do s thay i cc mc nghin cu gy nn vi phng sai chung 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.
Vic so snh phng sai c thc hin qua chun F.
2
2
TN
A
tinh
S
S
F = >1 v so snh vi F
chun
(P, f
A,
f
TN
)
trong S
A
2
l phng sai ca th nghim khi thay i cc mc khc nhau ca
yu t A.
S
TN
2
: l phng sai chung ca th nghim v lm th nghim bao gi cng mc sai
s.
f
A
: bc t do ca cc mc nghin cu ca yu t A lm; f= k-1
f
TN
: bc t do ca s nghin cu tin hnh trong qui hoch nghin cu : f
2
=
k(n-1)
Gi thit thng k l: H
0
: S
A
2
S
TN
2
v H
a
: S
A
2
S
TN
2

V F>1 nn :
- Nu F
tinh
<F
bang
th F
tinh
khng ng tin cy v c th xem S
A
2
v S
TN
2
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 F
tnh
>F
bng
th F
tnh
ng tin cy, tc l S
A
2
v S
TN
2
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 (P
value
) so snh vi P

. nu
P
value
< 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

=
n
j
j
y
1
2
=
n
j
kj
y
1

=
n
j
ij
y
1

=
n
j
j
y
1
3
=
n
j
j
y
1
2
44
Trong qu trnh tnh ton trnh nhm ln, ngi ta lp bng cc cng on tnh
phng sai so snh cho bi ton mt yu t, k mc nghin cu v n ln lp li nh
sau:
Bng 5.2: Bng tnh phng sai khi nghin cu nh hng ca yu t A.
Ngun bin thin
(Source of
variation)
Bc t do
( Degree of
freedom) f
Tng cc bnh phng
( Sum of squares)

2
) ( x x
i

Trung bnh bnh
phng
( mean of square)
S
2
A k-1 SS
A
= SS
2
-SS
3

1
2

=
k
SS
S
A
A
Sai s th nghim
( residue error)
k(n-1) SS
TN
= SS
1
- SS
3

) 1 (
2

=
n k
SS
S
TN
TN
Total kn-1 SS
total
=SS
1
-SS
3

Cc k hiu trn c tnh nh sau:

=
=
1 j
ij i
y n A
(tng cc ga tr trong mt ct).
n
A
A
i
i

=
( trung bnh ct)

=
=
n
i
i
A
k
Y
1
1
(trung bnh chung) ( overall average)

=
=
k
i
i
A SS
1
2
2

=
=
k
i
i
A
n
SS
1
2
3
) (
1
( SS: Sum of squares);
( S
2
: mean of squares)

= =
=
k
i
n
j
ij
y SS
1 1
2
1
) (
vi
=
=
n
j
ij i
y A
1
( tng cc gi tr trong mt ct )
F
tinh
=
2
2
TN
A
S
S

So snh F
tinh
vi F
bang
(P,f
1
,f
2
) vi P=0,95; f
1
=k-1; f
2
=k(n-1).
Nu F
tinh
< F
bang
th kt lun rng yu t A gy nh hng khng ng k n kt
qu th nghim v ngc li.
45
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
Loi
1 2 3 4 5 6 7 8
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 (-------------*------------)
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%
46
Hy gii thch kt qu trn
5.3. Phn tch phng sai hai yu t (two-way ANOVA)
Gi s c hai yu t nh hng n kt qu th nghim A v B. Yu t A c k
mc nghin c, yu t B c m mc nghin cu, mi mc th nghim lp li n ln. 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
a
1
a
2
... a
i
... a
k

b
1
y
111
, y
112
, ..., y
11n
y
211
, y
212
, .. y
21n
y
i11
, y
i12
, .. y
i1n
y
k11
, y
k12
, .. y
k1n

b
2
y
121
, y
122
, .. y
12n
y
221
, y
222
, .. y
22n
y
i21
, y
i22
, .. y
i2n
y
k21
, y
k22
, .. y
k2n

B ...
b
j
y
1j1
, y
1j2
, .. y
1jn
y
2j1
, y
2j2
, .. y
2jn
y
j1
, y
ij2
, .. y
ijn
y
kj1
, y
kj2
, .. y
kjn

...
b
m
y
1m1
, y
1m2
, .. y
1mn
y
2m1
, y
2m2
, .. y
2mn
y
im1
, y
im2
, .. y
imn
y
km1
, y
km2
, .. y
kmn

Tng ct A
1
A
2
A
i
A
k
Cc bc tnh phng sai theo bng trn ln lt nh sau:

=
=
n
u
iju ij
y Y
1
(tng cc kt qu nghin cu trong 1 )

=
=
n
u
iju ij
y Y
1
2 2
) (

= = =
= =
m
j
ij
m
j
n
u
iju i
Y y A
1 1 1
(tng cc kt qu nghin cu trong 1 ct)

= = =
= =
n
i
ij
k
i
n
u
iju j
Y y B
1 1 1
(tng cc kt qu nghin cu trong mt hng)

= = = = =
= = =
k
i
m
j
j i
k
i
m
j
n
u
iju iju
B A y Y
1 1 1 1 1
(tng cc ct = tng cc hng)
47

= = =
=
k
i
m
j
n
u
iju
y SS
1 1 1
2
1
=
=
k
i
i
A
n m
SS
1
2
2
.
1

=
=
m
j
j
B
n k
SS
1
2
3
.
1

2
1 1 1 1
2
1
2
4
) (
. .
1
) (
. .
1
) (
. .
1

= = = = =
= = =
k
i
m
j
n
u
m
j
j
k
i
i iju
B
n m k
A
n m k
y
n m k
SS

Mu kt qu tnh ton ANOVA c trnh by trong bng 5.4
Bng 5.4: Bng phn tch phng sai hai yu t
Ngun bin thin
(Source of
variation)
Bc t do
(Degrees of
freedom)
f
Tng cc bnh phng
(Sum of squares)

2
) ( x x
i

Trung bnh bnh
phng
(Mean of square)
S
2

A k-1 SS
A
=SS
2
-SS
4

1
2

=
k
SS
S
A
A

B m-1 SS
B
= SS
3
-SS
4
1
2

=
m
SS
S
B
B
AB (k-1).(m-1) SS
AB
= SS
total
-SS
A
-SS
B
-SS
e
SS
AB
=SS
1
-SS
2
-SS
3
+SS
4

) 1 )( 1 (
2

=
m k
SS
S
AB
AB
Sai s th nghim
(Residue error)
mk(n-1) SS
e
=SS
total
-SS
A
-SS
B

SS
e
= SS
1
-

= =
k
i
m
j
ij
Y
n
1 1
2
1

) 1 (
2

=
n mk
SS
S
e
e

Tng mk(n-1) SS
total
= SS
1
-SS
4

Trong :
S
A
2
v S
B
2
: phng sai c trng cho nh hng ca yu t A v B n kt qu th
nghim.
2
2
2
2
2
2
; ;
e
AB
AB
e
B
B
e
A
A
S
S
F
S
S
F
S
S
F = = =

S
AB
2
: phng sai c trng cho nh hng tng h ca c hai yu t A v B n
kt qu th nghim.
S
e
2
: phng sai c trng cho sai s th nghim.
Bc t do:
f
A
=k-1: f
B
= m-1

; f
AB
= (k- 1).(m-1) ; f
e
= m.k.(n-1)
48
So snh F
A
, F
B
, F
AB
vi gi tr F
bang
vi P=0,95; f
1
= f
A
hoc f
B
hoc f
AB
v f
2
= f
e
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 Cu
2+
trong nc ca
nha vng cng (% Cu
2+
) 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
20,2
6,8
7,2
45,5
47,0
20,1
20,9
Ngy 2 28,1
29,6
22,6
23,5
15,5
16,0
7,5
8,6
3 8,7
9,0
38,7
38,2
6,7
7,1
52,7
53,0
4 30,4
30,9
50,6
51,1
18,9
17,6
60,4
61,2
5 50,7
50,5
18,8
18,5
30,5
30,9
67,6
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 ;
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
49
Loai 3 1922.9 640.962 2446.42 0.000
Interaction 12 8267.9 688.992 2629.74 0.000
Error (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
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.
50
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 a
1
, b
1
v c
1
.
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.
b
1
b
2
b
3
b
4
Tng
hng
a
1
c
1
y
1111
; y
1112
; y
1113

c
2
y
2121
; y
2122
; y
2123
c
3

y
3131
y
3132
; y
3133
;

c
4

y
4141
y
4132
; y
4143

A
1
a
2
c
2

y
1221
; y
1222
; y
1223

c
3

y
2231
; y
2232
; y
2233

c
4

y
3241
; y
3242
; y
3243

c
1

y
4211
; y
4212
; y
4213

A
2
a
3
c
3

y
1331
; y
1332
; y
1333

c
4

y
2341
; y
2342
; y
2343

c
1

y
3311
; y
3312
; y
3313

c
2

y
4321
; y
4322
; y
4323

A
3
a
4
c
4

y
1441
; y
1442
; y
1443

c
1

y
2411
; y
2412
; y
2413

c
2

y
3421
; y
3422
; y
3423

c
3

y
4431
; y
4432
; y
4433

A
4
Tng
ct
B
1
B
2
B
3
B
4
Y
*
Cch tnh cc gi tr trong bng trn nh sau:
A
1
= y
111
+y
122
+y
133
+y
144

A
1
: 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 a
1
( tc l tng trung bnh ca cc kt qu ca cc
trong hng a
1
).
Tng t ta c cc gi tr khc:
A
2
, A
3
, A
4
l tng cc kt qu c mc a
2
, a
3
, a
4
.
B
1
...B
4
l tng cc kt qu c mc b
1
, b
2
, b
3
, b
4
.
51
C
1
...C
4
l tng cc kt qu c mc c
1
, c
2
, c
3
, c
4
.
Y
*
= A
1
+A
2
+A
3
+A
4
= B
1
+B
2
+B
3
+B
4
= C
1
+C
2
+C
3
+C
4

= =
=
n
j
n
i
ij
y SS
1 1
2
1
(tng bnh phng cc ga tr c mt trong bng ).
2
1
2
2
1
2
2
1
2 5
1
2
4
1
2
3
1
2
2
) (
1
) (
1
) (
1
1
1
1

= = =
=
=
=
= = =
=
=
=
n
qi
q
n
j
j
n
i
i
n
q
q
n
j
j
n
i
i
C
n
B
n
A
n
SS
C
n
SS
B
n
SS
A
n
SS

2
2
2
2
2
2
e
C
C
e
B
B
e
A
A
S
S
F
S
S
F
S
S
F
=
=
=

Bng phn tch phng sai trong trng hp ny c dng sau:
Bng 5.5: Bng phn tch phng sai ba yu t
Ngun bin thin
(Source of variation)
Bc t do
(Degrees of
freedom) f
Tng cc bnh phng
(Sum of squares)

2
) ( x x
i

Trung bnh bnh phng
(Mean of square)
S
2

A n-1 SS
A
= SS
2
-SS
5

B n-1 SS
B
= SS
3
-SS
5

C n-1 SS
C
= SS
4
-SS
5

Sai s th nghim
(Residue error)
(n-1)(n-2) SS
e
=SS
total
-SS
A
-SS
B
-SS
c

) 2 )( 1 (
2

=
n n
SS
S
e
e

Tng n
2
-1 SS
total
= SS
1
-SS
5


So snh cc gi tr tnh ton vi gi tr tra bng F
bang
(P,f
1
,f
2
) vi P=0,95 ; f
1
=n-1

v f
2
=
(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
1
2

=
n
SS
S
A
A
1
2

=
n
SS
S
B
B
1
2

=
n
SS
S
C
C
52
sau:
b
1
b
2
b
3
b
4
a
1
c
1
0, 351


C
2
0,522

c
3
0,24 5

c
4
0,248
a
2
c
2
0,356


C
3
0,258


c
4
0,452


c
1
0,526


a
3
c
3
0,211


C
4
0,356


c
1
0,456


c
2
0,521


a
4
c
4
0,169


C
1
0,254


c
2
0,255


c
3
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 a
1
a
4
, 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
0.456 3 3 1
0.521 3 4 2
53
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).









54
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 v phn tch cng c.
- Phn tch ho hc 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 cht nh phn tm phng trnh h qui 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 bng phn phi 2 chiu. Ni
cch khc, cn phi tr li c cc cu hi sau:
- ng chun c tuyn tnh khng? Nu l ng cong th dng biu din l g?
- Mi im trn ng chun u mc sai s khi phn tch. Vy ng biu din
no s i qua tt c cc im thc nghim ny?
- Gi thit ng chun l thc s tuyn tnh th sai s v gii hn tin cy ca
nng xc nh c l bao nhiu?
-Gii hn pht hin ca phng php l bao nhiu?
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.
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 (cc bin) tun theo phn phi chun.
- Gi tr cc bin l c lp nhau.
- Phi loi b gi tr bt thng trc khi tnh h s tng quan.Trng hp nu
khng tun theo phn phi chun th nn s dng h s tng quan phn hng
Spearmen.


55
6.1.1. Cch tnh h s tng quan Pearson (the product-moment correlation
coefficient)
H s tng quan c tnh theo cng thc sau:
y x
XY
S S
COV
r =
vi COV l ng phng sai ca hai tp s liu X v Y v c tnh theo cng
thc:
n
y y x x
COV
i i
XY

=
) )( (
vi n l s ga tr trong tp s liu X v Y
Do vy

=
) ) ( )( ) ( (
) ).( (
) ) ( )( ) ( (
) (
2 2 2 2
2
y y x x
y y x x
y y x x
x y x n
r
i i
i i
i i
i i i
=

n
y
y
n
x
x
y x
n
y x
i
i
i
i
i i i i
2
2
2
2
) (
)(
) (
(
1

Khi r=1 th tp hp cc im (x
i
, y
i
) 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 cu x v y. Trong mt s
trng hp c th tnh h s xc nh ( r
2
) tc l phn phng sai ca mt bin c d
on bi bin kia theo tng phng sai. V d, r
2
=0,88 c ngha l x chim 88 %
phng sai ca x v y. Mt s th d v mc tng quan hai bin trong hnh 6.1:

Hnh 6.1: th biu din mc tng quan gia hai i lng o
56
Nhng yu t nh hng ln n h s tng quan l:
+ Khong bin i ca cc s liu trong tp s liu.
+ khng ng nht ca mu.
+ Sai s th.
Th d 6.1:
Phn tch hm lng gluco trong mu theo phng php ng chun. S ph thuc
gia hp th quang v nng gluco trong mu 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
SV hy vn dng cng thc nu trn tnh h s tng quan Pearson r v kt lun
mc tng quan tuyn tnh gia hai i lng nu trn.
tr li cu hi v 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.
) 1 (
2 .
2
r
n r
t

=
vi r l h s tng quan Pearson, n l s th nghim hay s s liu trong mi bin.
Sau , so snh ga tr t
tinh
vi t
chun
tra bng tin cy thng k mong mun (thng
chn P=0,95), s bc t do f=n-2.
Gi thit "khng" l gi thit gia X v Y khng c tng quan t c khi
t
tinh
< t
tra bang
. Nu t
tinh
>t
tra bang
th x v y c tng quan tuyn tnh.
Nu tnh ton bng cc phn mm thng k, c th s dng gi tr P ( P
value
) v so
snh vi khng tin cy . Thng thng nu P
value
<0,01 th kt lun rng hai bin c
tng quan tuyn tnh tin cy 99%. Kt lun tng t nu P
value
<0,05.
Th d 6.2: Khi so snh kt qu phn tch c lm bi hai phng php A v B ngi
ta tnh c r=0,65. S mc hm lng em phn tch l n=11.
Theo cng thc trn c th tnh c:
57 , 5
) 65 , 0 1 (
2 11 65 , 0
2
=

= t
tra bng gi tr t bc t do f=9 v tin cy thng k 95 % ta c t= 2,26
N h vy gi tr t tnh ton 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.
57
6.1.2. H s tng quan Spearmen (rs): H s ny cng c dng biu th mc
tng quan hai bin nhng khc vi h s tng quan Pearman, n xp th hng
mi bin thay v tnh gi tr.
1) - N( N
d
6
- 1 =
r
2
2
N
=1 i
s

y d l s khc nhau gia cc th hng trong hai phng php xp hng.
Khi N>=10 th r
s
c th c dng tnh gi tr t theo phng trnh trn.
6.1.3. H s tng quan Kendall :
H s ny phc tp hn Spearman v ch nn dng khi c nhiu hn 2 tp s liu
cn so snh v c tnh nh l hiu s ca cp ph hp tr i hiu s cp khng ph
hp.
Cp ph hp l khi (x
i
-x
j
)*(y
i
-y
j
)>0
Cp khng ph hp khi (x
i
-x
j
)*(y
i
-y
j
)<0.
6.1.4. Tng quan tng phn (r
p
): dng ch mc tng quan hai bin trong
cng mu v c dng trong cc trng hp sau:
+ Tng quan tng phn gia hai bin
+Tng quan tng phn gia nhiu bin trong tp s liu
+ Tng quan tng phn gia nhiu tp bin.
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 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
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 32.6 300.7 20503 57.2 207.7 667.8 56.5
7 972.2 45.1 639.6 34584 38.7 184.3 1257.0 104.9
8 * 73.8 524.6 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 29.2 378.5 810.4 64.0
11 614.4 49.7 295.1 24717 13.9 366.1 494.8 199.3
12 1145.0 50.7 369.9 37912 27.1 259.8 1179.0 283.5
58
13 905.8 128.9 451.3 52115 32.2 356.5 * 378.6
14 * 59.6 510.8 39931 38.0 131.3 706.5 312.3
15 898.0 74.7 377.7 26779 34.1 89.6 381.1 108.6
16 558.9 101.8 397.9 21001 24.5 235.9 439.6 183.9
17 1217.0 53.3 528.4 23656 23.8 139.0 990.5 83.6
18 1160.0 71.9 633.5 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 k hiu du * l nhng s liu th 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 thu c nh sau:
Ti Cr Mn Fe Ni Cu Zn
Cr 0.334
0.205
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
Cell Contents: Pearson correlation
P-Value
Gi tr trong mi gm h s tng quan Pearson v gi tr P. Hy kt lun v
chiu hng v mc tng quan gia hm lng cc kim loi nu trn.
6.2. Phng php bnh phng ti thiu
Gi s c 2 tp s liu : x: x
1
x
2
x
3
x
4
x
5
... (nng )
y: y
1
y
2
y
3
y
4
y
5
... (tn hiu phn tch)
59
ng chun s 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 biu din (ng chun) v b l dc ca ng chun. Trong
thc t 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 ( x
1
; y
1
) ( x
2
; y
2
)........ (x
n
; y
n
) ta s tm c im trng
tm (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 i qua tt c cc im trn ng chun (trong khi mi im thc nghim u
mc sai s)? Do , cn ti thiu ho lch (c gi tr dng hoc m) gia cc gi
tr thc nghim y
i
v gi tr
i
y tnh c theo phng trnh hi qui biu din quan h
tuyn tnh gia v x v y theo tng bnh phng s d (sum of square of the residuals).
V vy phng php ny cn gi l phng php bnh phng ti thiu.
Nu cc gi tr thc nghim c biu din bng phng trnh y=ax +b trong
a l im ct trc tung ca ng chun (intercept) v b l dc ca ng chun
(slope) th s sai khc gia gi tr thc nghim y
i
v gi tr tnh theo phng trnh l:
y
i
= y
i

i
y = y
i
a b.x
i
Bnh phng s sai khc ny c dng :
y
i
2
= (y
i
- a - b.x
i
)
2
= y
i
2
+ a
2
+ b
2
x
i
2
- 2ay
i
- 2bx
i
y
i
+ 2abx
i
2
.
Ly tng cc gi tr y
i
2
cho N im thc nghim trn ng chun th :

= = = = = =
+ + + =
n
i
i
n
i
i i
n
i
i
n
i
i
n
i
i
n
i
i
x ab y x b y a x b a n y y
1 1 1 1
2 2 2
1
2
1
2
2 ) ( 2 2 ) ( . ) ( ) (
s sai khc gia y
i
v y nh nht, ngi ta tm y
i
0, hay

= + + =

= + + =

= = =
=
= =
=
0 2 ) ( 2 ) . ( 2
) (
0 . 2 2 2
) (
1 1
2
1
1
2
1 1
1
2
n
i
i
n
i
i
n
i
i i
n
i
i
n
i
i
n
i
i
n
i
i
x a x b y x
b
y
a n x b y
a
y

Gii h hai phng trnh trn thu c

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



= =
= = = =

= =
n
i
n
i
i i
n
i
n
i
i i
n
i
i i
n
i
i
x x n
y x x x y
x b y a
1 1
2 2
1 1 1
2
1
) (
. . .
.
T cc ga tr thc nghim x
i
v y
i
s tm c phng trnh hi qui y=a+bx v h
s tng quan r.
60

Tnh sai s ca b v a trong phng trnh hi qui
lch chun ca a v b tu thuc vo mi im thc nghim sai khc bao nhiu
so vi im trn ng chun (d
i
). d
i
c gi l lch hay s d (residual)
d
i
= y
i
- y = y
i
- a - b.x
i

Trong : y
i
gi tr thu c t thc nghim
y gi tr tnh theo phng trnh hi quy.

Hnh 6.2: Phng php bnh phng ti thiu
V a, b l cc i lng o gin tip, do :
2 2 2
2
2
2
2
1
2
1
2
. ) ( ... . ) ( . ) (
n
n
Sy
y
a
Sy
y
a
Sy
y
a
Sa

+ +

=
2 2 2
2
2
2
2
1
2
1
2
. ) ( ... . ) ( . ) (
n
n
Sy
y
b
Sy
y
b
Sy
y
b
Sb

+ +

=
Xem
2
1
Sy =
2
2
Sy = ... =
2
n
Sy =
2
Sy (phng sai ca y).
S
y
c gi l lch chun ca m hnh (standard deviation of fit) (i khi k
hiu l S
y/x
)
Vi
2
) (
2
2

=

n
bx a y
Sy
i i
;

+ + + +
=
2 2
1 1 1
) (
) ... ( ) ... (
i i
n i n n
x x n
y y x y x y x n
b
Nh vy
2
2 2
1
2
2
2
1
2
1
2 ) ( ) (
) (
MS
x nx x x n
MS
x nx
y
b
i i i
+
=

vi

=
2 2
) (
i i
x x N MS
Tng t :
2
2
2 2
2
2
2
2
1 2
2
. 2 ) ( ) (
) (
MS
x nx x x n
MS
x nx
y
b
i i i
+
=

Do :
61
MS
n
MS
x n x n
MS
x n x n x n
y
b
y
b
i i i i i
n
=

=
+
=

+ +

2
2 2 2
2
2 2 2 2
2 2
1
) ( ) ( 2 ) (
) ( ... ) (
Vy


=

=
2
2
2 2
2 2
) ( ) (
.
x x
S
x x N
N
Sy Sb
i
y
i i

=
2
2
2
2 2
2
2 2
) ( ) (
.
x x
x
S
x x N
x N
Sy Sa
i
i
y
i i
i

T cc gi tr phng sai ca a v b c th tnh c lch chun S
a
, S
b

=
i
i
y
b
x x
S
S
2
) (

=
i
i
i
i y
a
x x
x S
S
2
2
) (

Khong tin cy cu a v b c tnh l : b t. S
b
v a t. S
a
Nh vy, phng trnh hi qui y c dng: y= (a t. S
a
) + (b t. S
b
) .x

Th d 6.4: kt qu phn tch hm lng Ca theo phng php FIA nh sau:
Nng
(ppm)
0 2 4 6 8 10 12 X
TB
=7
x
i
-x
TB
-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
TB
=12,8
Y
i-
YTB -9,9 -5,9 -2,3 2,4 6,1 9,8
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
Theo cc kt qu trn ta c: a=1,528 ; b= 1,930 ; S
a
=0,295; S
b
=0,041.
lch chun ca phng trnh l: S
y
=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.
Phng trnh hi qui ca ng chun trn s c dng:Y=(1,530,76)
+(1,930,11)x.

62


Hnh 6.3: ng chun biu th quan h tuyn tnh gia chiu cao pic v nng cht phn tch
Tnh nng cht nh phn:
T phng trnh hi qui tm c, khi mu nh phn c gi tr i lng cn o y
th c th tnh c nng cha bit x.
Nu ng chun c phng trnh y = a+ bx th sai s phng php phn tch
gm 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 x
0
c tnh nh sau:

+ + =
i
i
y
x
x x b
y y
n b
S
S
2 2
2
0
) (
) ( 1
1
0

y : S
x0
l lch chun c on hay sai s bnh phng trung bnh ca x
0

y
0
l gi tr thc nghim thu c khi phn tch x
0

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
0
y th :

+ + =
i
i
y
x
x x b
y y
n m b
S
S
2 2
2
0
) (
) ( 1 1
0

Kt qu phn tch mu cha bit s c vit di dng: x
0
t.S
x0
vi bc t do n-2.
Mt cch khc, tnh nng x
0
khi c gi tr thc nghim y
0
l tnh x
0
theo
cng thc
) (
) ( ) (
0
Sb b
Sa a Sy y
x
o

= v s dng quy lut lan truyn sai s tnh gi tr
x
0
.
Th d 6.5: Trong php phn tch trn nu c mt mu phn tch o c chiu
0 2 4 6 8 10 12
0
5
10
15
20
25
c
h
i

u

c
a
o

p
i
c

(
c
m
)
nng cht phn tch (ppm)
63
cao pic l y
0
=7,3.
S dng phng trnh hi qui s tnh c gi tr 98 , 2
93 , 1
53 , 1 3 , 7
0
0
=

=
b
a y
x
lch chun

+ + =
i
i
x y
x
x x b
y y
n b
S
S
2 2
2
0
/
) (
) ( 1
1
0

vi n=7 ; b= 1,93 S
y/x
= 0,433 1 , 13
7
7
1
= =

= i
i
y
y 9256 , 83 ) (
2
7
1
=

= i
i
x x
Thay s vo ta c: S
x0
= 0,25 vi t
(P=0,95,f=55)
=2,57
Vy khong xc nh ca x
0
l: x
0
= (2,980,64)
* Nu mu cn phn tch c xc nh lp li 3 ln v chiu cao pic trung bnh l
y
o
=7,3 th

+ + =
i
i
x y
x
x x b
y y
n m b
S
S
2 2
2
0
/
) (
) ( 1 1
0

vi m=3 thay s nh trn ta c S
x0
=0,28 v khong xc nh ca x
0
l
x
0
= (2,98 0,72)
nh hng ca s im th nghim khng 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 1/n ln, bc t do n-2
nh, nn t 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. Trong thc nghim
thng ch cn lm 6 th nghim xy dng ng chun v mun tng chnh xc
kt qu phn tch mu cn lm lp li nhiu th nghim xc nh x
0
.
6.3. Kim tra hng s trong phng trnh hi qui
Trong phng trnh hi qui y = a + bx, trng hp l tng xy ra khi a=0. 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 khng 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).
Nu xem a0 th phng trnh y=a+bx c vit thnh phng trnh y=b'x. Thay
cc gi tr y
i
v x
i
vo phng trnh y=b' x ta s c cc ga tr b'
I
v tnh
1
'

=

n
b
b
i
i trong n l s im trn ng chun, c tnh n im c nng
bng khng.
Phng sai ca hai phng trnh s c tnh nh sau:
2
) (
2
) (
2 2
2

=

n
bx a y
n
y y
S
i i i i
y

64
3
) (
3
) (
2 ' 2 '
2 '

=

n
x b y
n
y y
S
i i
i
i
y
S sai khc phng sai ca hai phng trnh ny c so snh theo chun F ( tnh
theo t s cu hai phng sai sao cho F>1 v so snh gi tr ny vi F
(P,f1,f2)
vi P=0,95
v f
1
= n-3, f
2
= n-2.
2
2 '
y
y
tinh
S
S
F =
Nu F
tinh
< 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:

) 2 ( ) 2 (
) ' ( ) (
1
2 2
2
+
+
=

m m
x b y bx a y
S
i i i i
g

Ta c phng sai ca hiu b-b
'

(
(
(
(

=

2
2
2
2
2
2
1
1
2
1
2 2
) (
1
1
) (
1
1
i i i i
g d
x
m
x x
m
x
S S
bc t do f = (m
1
-2)+(m
2
-2) vi m
1
v m
2
l s th nghim tin hnh ng chun
trong hai phng trnh.
kim tra ngha ca hiu b
1
-b
2
ta tnh
d
S
b b
t
2 1

= v so snh vi t(P,f) .
65
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
ppb 4 12 30 60 120 180 240 300 C
As
(.10-
7
M 0,53 1,6 4 8 16 24 32 40
A
1
0,0021 0,0065 0,0170 0,0330 0,0681 0,1004 0,1287 0,1656
A
2
0,0019 0,0067 0,1168 0,0333 0,0678 0,1007 0,1288 0,1660
A
3
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)C
As
Trong A l hp th quang v C
as
l nng As (III) (10
-7
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 . 10
7
, 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 0,00406 0,00423 0,00415 0,00425 0,00419 0,00402 0,00414
Cc gi tr lin quan n h s s l

Mean Trung bnh 0,004148771
0 10 20 30 40
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
Y = A + B * X
Parameter Value Error
------------------------------------------------------------
A 2.31211E-4 0.00124
B 0.00413 5.89054E-5
------------------------------------------------------------
R SD N P
------------------------------------------------------------
0.99939 0.00232 8 <0.0001
A
b
s
C
As
.10
7
M
66
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
Nu A 0 khng c ngha thng k mc tin cy 95%, phng trnh hi
quy c dng: ( )x S . t ' B y
' B
+ = .
Ta c: y =(0,00415 2,45.3,26.10
-5
)x
p dng cng thc: SS= ( )

2
i i
Bx A y v S
2
=
2 n
SS

ta c bng gi tr:
Hm Tng cc bnh phng Bc t do Phng sai
y = Bx SS=2,07.10
-5
5 S
2
= 4,14.10
-6
y = A + Bx SS = 1,83.10
-5
6 S
2
= 3,05.10
-6
C: F
tnh
=
2
2 '
S
S
= 4,14/3,05=1,35
Tra bng F(0,95;7;6)=4,3874 =>F
tnh
< F(0,95;5;6) c ngha l s sai khc
gia gi tr a v 0 khng c ngha thng k, phng php khng mc sai s h thng.
6.4. Gii hn pht hin, gii hn nh lng, nhy, chn lc
6.4.1. Gii hn pht hin (limit of detection- LOD)
LOD c xem l nng thp nht (x
L
) ca cht phn tch m h thng phn
tch cn cho tn hiu phn tch (y
L
) khc c ngha vi tn hiu ca mu trng hay tn
hiu nn (blank or background).
Tc l: y
L
=
B B
S k y . +
Vi
B
y l tn hiu trung bnh ca mu trng sau n
b
th nghim (ln hn 20 th
nghim). S
b
l lch chun tn hiu ca mu trng, k l i lng s hc c chn
theo tin cy mong mun.

=
=
b
n
j
bj
b
b
y
n
y
1
1

=
b
n
i
b
bi
b
b x x
n
S
1
2 2
) (
1
1

Nh vy
b
S k
x x
B
B
L
.
+ =
Mu trng c pha vi nng cht phn tch x
B
=0. Do gii hn pht hin
b
S k
LOD
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 php o c tin
hnh vi mu trng th a=0 )
67
Do IUPAC a ra phng trnh tnh LOD nh sau:
b
S S k
LOD
a
B ) ( .
2 2
+
= vi S
a
l lch chun ca h s a.
Trng hp khng phn tch mu trng th c th xem nh lch chun mu
trng S
B
ng bng sai s ca phng trnh hi qui, tc l S
B
=S
y
v tn hiu khi phn
tch mu nn y
B
= a. Khi tn hiu thu c ng vi nng pht hin Y
LOD
= a+ 3. S
y
.
Sau dng phng trnh hi qui c th tm c LOD.
LOD=
b
S
y
. 3

6.4.2.Gii hn nh lng ( limit of quantity- LOQ)
LOD c xem l nng thp nht (x
Q
) ca cht phn tch m h thng phn
tch nh lng c vi tn hiu phn tch (y
Q
) khc c ngha nh lng vi tn hiu
ca mu trng hay tn hiu nn (blank or background).
y
Q
=
B
y + K. S
B


Thng thng LOQ c tnh vi K=10 tc l C
Q
=10. S
B
/b
Tm li c 3 vng phn tch lin quan n nng cht phn tch
----------------------tn hiu phn tch ------------------>
X
L
X
Q
Khng pht hin c cht phn tch vng pht hin c vng nh lng
C
L
C
Q

--------------------------nng cht 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 ng
hc (dynamic range).
68

Hnh 6.4. Gii hn pht hin, gii hn nh lng v khong ng hc
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
ng chun. Do , nhy ng chun c tnh theo cng thc
dx
dy
m = .
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 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:
nng cht phn tch
tn
hi
u
ph
n
tc
h
69
b tg
x x
y y
m
bl
L
bl L
= =

=
vi x
L
l LOD
C
L
= ( x
L
-
bl
x )/m vi m l nhy php phn tch hay C
L
= K.S
bl
/m v x
bl
=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

.S
m
vi S
m
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:
C
L
= k.S
B
/( m t

.S
m
)

v dng gi tr t

.S
m
biu th LOD. Tuy nhin nu
t

.S
m
=0 hoc t

.S
m
<< m th C
L
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= b
A
.C
A
+ b
B
.C
B

+ b
C
.C
C
++ y
bl

y b
A
, b
B
, b
C
l cc h s nhy ca A, B, C.
C
A
, C
B
, C
C
l nng ca cht phn tch A v cc cht gy cn tr B, C
y
bl
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.
k
B,A
= b
B
/b
A
k
C,A
= b
C
/b
A
Phng trnh

hi qui xc nh A c th c vit thnh:
Y= b
A
( C
A
+ k
B,A
. C
B
+ k
C/A
.C
C
) + y
bl

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
A
bl
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
A
bl
0,0061 0,0063 0,056 0,0063 0,0060 0,0058 0,0059 0,0062 0,0055 0,0063
70
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

* Gii hn pht hin:
) 05 , 0 ( 10 . 2785 , 0
00413 , 0
00038 , 0 . 3 3
7
g M
b
S
LOD
B

= = =
S
B
: lch chun mu trng.
* Gii hn nh lng:
) 17 , 0 ( 10 . 9284 , 0
00413 , 0
00038 , 0 . 10 10
7
g M
b
S
LOQ
B

= = =
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 (S
y
=0,00232) th s thu c cc gi tr
sau:
LOD= 3S
y
/b = 1,68.10
-7
M
LOQ= 10S
y
/b=5,62.10
-7
M
nhy php o m= b/S
y
= 1,78.

6.5. Phng php thm chun (standard addition method) (spiking)
Trong nhiu trng hp cc cht khc i km vi cht phn tch cng cho tn hiu
gy nhiu n kt qu phn tch. Nu nh hng ca nn mu (matrix) 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, ngoi suy t th hoc tm phng trnh hi qui theo phng php bnh
phng ti thiu vi phng trnh hi qui c dng y=a+bx.
Gi s ly V
s
(ml) mu phn tch c nng C
x
vo cc bnh c th tch V ml.
Thm V
1
(ml), 2V
1
(ml), 3V
1
(ml)nV
1
dung dch chun c nng C
s
vo cc bnh
nh mc nyv nh mc n vch bng nc ct. o tn hiu phn tch ca cc dung
dch c cc i lng y
x
, y
x1
, y
x2
y
xn
.Khi nng cht phn tch C
x
c tnh
theo cc cch sau:
Cch 1: tnh theo cng thc
Ta c cc mi tng quan y
x
V
x
C
x
/V
Y
x1
(V
x
C
x
+V
1
C
s
)/V
71
Y
x2
( V
x
C
x
+2V
1
C
s
)/V
.
Nh vy c th lp cc t s:
s x x
x x
x
x
C V C V
C V
y
y
1 1
+
=
Do
x
s
x x
x
x
V
C V
y y
y
C
1
1
.

=

Tng t nh th s c
x
s
x x
x
x
V
C V
y y
y
C
1
2
2
.

x
s
x xn
x
x
V
C nV
y y
y
C
1
.

=

Ly gi tr trung bnh cc nng C
x
ny ta s c nng C
x
cn tm.
Cch 2: V ng thm chun v ngoi suy t th










Nng cht phn tch
Hnh 6.5 : Phng php thm chun

Cch 3: S dng phng trnh hi qui:
Gi thit phng trnh ng chun c dng y=a+bx. Theo cng thc tnh
tg=b=a/C
x
V
x
ta s c
x
x
V b
a
C
.
=

Khong tin cy ca nng cht phn tch trong mu x
E
l
C
x
tn
hiu
o
72
x
E
t. S
XE
vi

+ =
i
i
y
XE
x x b
y
n b
S
S
2 2
2
) (
1

Khi tng s th nghim n (s im thm trn ng chun) hoc tng bnh phng
hiu sai khc gia x
i
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
45
0
.
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
(g)
0 5 10 15 20 25 30
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:
6014 , 0 = y S
xE
=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 : =
XE
S t x . (17,3 1,9) g
* Nhc im phng php thm chun:
- Kh t ng ho
- Dng lng ln mu
- Phng php ngoi suy km chnh xc hn phng php ni suy.
6.6. Phng php ni chun
- 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 6.6). Phng php
ny rt cn khi phn tch nhng mu c nn phc tp hoc trong cc php o thay i
theo thi gian.

73

Hnh 6.6: Phng php ni chun
Th d 6.9:Phng php ni chun trong sc k kh lng. Trch t:
http://zimmer.csufresno.edu/~davidz/Chem102/Sp98Web/Overhead/Separations/GLCI
ntStd/GLCIntStd.html
Gi s cn nh phn cht A khi c mt cht B v cht ni chun c thm vo
l IS. Cc thng s o v nng cc cht c cho trong bng sau:

Chun b cc dung dch chun c nng cht A thay i cn gi nguyn nng
th tch B v IS. Khi bm mu vo thit b o, th tch bm khng th ly chnh xc
1 l m cso 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:
74


Nu biu din s ph thuc chiu cao pic ca A theo nng th tch th c
dng khng phi tuyn tnh. Nhng nu chia chiu cao pic ca A cho chiu cao pic ca
cht ni chun v biu din s ph thuc t s ny vo nng th tch ca A th
ng biu din c dng tuyn tnh.

i vi cc mu cha bit , khi cn phn tch hai cht A v B th cn thm vo
mu lng cht ni chun nh khi thm vo dugn dch chun v ghi sc , t chiu
cao pic ca A v ca IS, tnh t s chiu cao pic v dng phng php ni suy t
th hay tnh theo phng trinh hi qui c th tm c nng A trong mu.
75


6.7. S dng ng hi qui trong phn tch so snh
Khi cn so snh hai phng php phn tch ngi ta c th s dng cc cch sau:
* 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 , sau biu din trn h to hai chiu. Mi im trn th (x,y)
i din cho 1 mu c phn tch bng 2 phng php c lp. Tnh cc h s a, b, r
theo phng php bnh phng ti thiu lp phng trnh hi qui dng y=a+bx
(a0 ; b=r 1). Trng hp l tng khi kt qu ca hai phng php nh nhau i
vi tt c cc mu th a= 0; b=1. 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.
Cc trng hp khng l tng c th gm:
+ b=1 nhng a 0: mt trong hai phng php phn tch c kt qu cao hn hoc
thp hn phng php kia (c th do tn hiu mu nn khng chnh xc) ( hnh a)
+ b>1 hoc b<1 c sai s h thng xy ra vi b mt trong 2 phng php (hnh
b v d)
+ dng ng cong ( khng tuyn tnh) do sai s h thng.
76


Hnh 6.7: So snh hai phng php
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
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 ca
nghin cu trc Y, dng phn mm Origin 6.0, kt qu cc h s ca phng trnh
hi qui htu c nh sau:
a=1,56 ; b= 0.98 ; r= 0,999
Cc i lng thng k tng ng l:
S
y/x
= 0,96236; sai chun SE
a
=0,89338 ; SE
b
=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
Phng
php A
a b
c d
e f
Phng php B
77
20 30 40 50 60 70 80 90 100
20
30
40
50
60
70
80
90
100
Y = A + B * X
Parameter Value Error
------------------------------------------------------------
A 1.56502 0.89338
B 0.98009 0.0136
------------------------------------------------------------
R SD N P
------------------------------------------------------------
0.99933 0.96236 9 <0.0001
p
h

n
g

p
h

p

F
I
A
phng php tiu chun

Kt qu ny cho thy cc ga tr a v b v r khng khc nhau
c ngha so vi ga tr 0 v 1. iu chng t khng c
bng chng v s khc nhau c ngha gia hai tp s liu.
SV t so snh hai phng php trn theo bi ton so snh hiu s dng chun Student
xem phng php ang nghin cu c mc sai s h thng khng.
6.8. ng hi qui khi (weightted 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. 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 ca gi tr 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. Mi nng cht phn
tch c lm lp li nhiu ln v tn hiu o c gi tr phng sai tng ng S
2
. Tuy
vy ngay c mi im ring bit c biu din bi to d (x
i
, y
i
) u c lch chun
tng ng s
i
. V vy gi tr khi ring phn c biu din l w
I
v c tnh nh sau:
w
i
=

i
i
i
S
n
S
2
2
1
.
1

Khi gi tr ca a , b trong phng trnh hi qui c tnh nh sau:

=
i
w
i i
w w
i
i i
x n x w
y x n y wx
b
2 2

78
v w
w
x b y a = trong
w
x v
w
y l to im trung tm khi (weighted
centroid) vi
w
x =
n
x w
i
i i
v
w
y =
n
y w
i
i i

Trong phng trnh hi qui khi, to im tm (
w
x
w
y ) 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 (S
xow)
ca nng cn tm
c a ra bi phng trnh
2
1
2 2 2
)
0
) / (
)
(
1 1
2

+ + =

i
w
i i
w o w x y
w x
x n x w b
y y
n w b
S
S
o

Trong phng trnh ny S
(y/x)w
c tnh nh sau:
2
1
2 2 2 2 2
) / (
2
) ( ) (

=

n
x n x w b y n y w
S
i i
w
i i w i i
w x y vi x
0
l xp x khi ca y
0
.
Phng trnh ny cho thy im gn u ng chun (gi tr khi ln nht) v
im gn im tm ti (y
0
- y
w
) nh s c gii hn tin cy nh nht.
S khc nhau gia hai phng trnh hi qui l gi tr 1/w
0
. V w
0
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
Cng hunh
quang

4
3
4
5
4
22
20
21
22
21
44
46
45
44
44
60
63
60
63
63
75
81
79
78
77
104
109
107
101
105
79
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.
0 10 20 30 40 50
0
20
40
60
80
100
120
Y = A + B * X
Parameter Value Error
------------------------------------------------------------
A 2.20952 2.01184
B 1.99029 0.06645
------------------------------------------------------------
R SD N P
------------------------------------------------------------
0.99778 2.77976 6 <0.0001
c

n
g

h
u

n
h

q
u
a
n
g

t
r
u
n
g

b

n
h
nng quinin (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
hunh quang trung bnh theo nng quinin c dng: y= 2,21+1,99 x.


80
0 10 20 30 40 50
0
20
40
60
80
100
120
Parameter Value Error
------------------------------------------------------------
A 3.22566 0.87159
B 1.92587 0.05081
------------------------------------------------------------
R SD N P
------------------------------------------------------------
0.99861 1.44252 6 <0.0001
------------------------------------------------------------
c

n
g

h
u

n
h

q
u
a
n
g
nng quinin ( ng/ml)

Hnh 6.9: ng hi qui khi
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.









81
Chng 7 M BO CHT LNG V KIM SOT
CHT LNG

7.1. Khi nim v m bo cht lng v kim sot cht lng (QA/QC)
Kt qu phn tch ca phng th nghim (PTN) 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 c chuyn
thnh mt tiu chun quc t mang tn ISO/IEC 17025: 1999 gm hai nhm yu cu
ln: yu cu v qun l v yu cu v k thut nh trong bng 7.1
Bng7.1 : Yu cu v qun l v k thut khi tin hnh QA/QC.
Yu cu v qun l:
1. T chc.
2. H thng cht lng.
3. Kim sot ti liu.
4. Xem xt yu cu, ngh v hp ng.
5. Hp ng ph v hiu chun v th
nghim.
6. Dch v mua sm v ngun cung cp.
7. Dch v khch hng.
8. Khiu ni.
9. Kim sot cng vic th nghim hoc
hiu chun khng ph hp.
10. Bin php khc phc.
11. Bin php phng nga.
12. Kim sot h s.
13. nh gi ni b.
14. Xem xt ca lnh o.

Yu cu v k thut
1. Yu cu chung
2. Nhn s.
3. Tin nghi v iu kin mi trng.
4. Phng php th nghim, hiu chun
v ph duyt phng php
5. Thit b.
6. Lin kt chun o lng.
7. Ly mu.
8. Qun l mu th nghim, hiu chun.
9. m bo cht lng kt qu th
nghim v hiu chun.
10. Bo co kt qu.
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
82
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.
7.2. 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.
7.2.1. 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.
7.2.2. 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
83
chun/phng php lun c s pht trin do PTN phi c s cp nht cc phng
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
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
84
*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.
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.
85
*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
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.
86
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.
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 kim chng 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
87
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 trongPTN, 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.
7.3. Th tc tin hnh QA/QC
Mt chng trnh kim sot cht lng tt phi bao gm y cc yu t sau:
7.3.1.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.
7.3.2.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 .
7.3.3. 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
phn tch mt mu c nn mi, nh gi sai s ca PTN, cc sai s hiu chun, sai s
chun b mu.
7.3.4.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.
7.3.5.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
88
mt mu hoc phn tch mu c nng ln hn mu c hm lng cao nht theo
ng chun.
7.3.6.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).
7.3.7. Php phn tch kp: Dng nh gi chnh xc ca php phn tch. S
mu cn phi phn tch kp t nht phi chim 5
o
/
o
s mu cn phn tch.
7.3.8.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.

UCL
UWL
x
LWL
LCL

Ngy phn tch

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.
Nng
,
mg/L
89
Gii hn trung bnh: R = D
2
.s (vi D
2
l yu t qui i s sang gii hn;
D
2
=1,128 nu lm lp li 2 ln, D
2
= 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 kim
sot(CL)
1. Mt im o vt qu CL.
2a. Cc php phn tch lp li < CL
2b. Cc php phn tch lp li> CL
1. Lp li php phn tch.
2.a. Tip tc phn tch
2b. Dng li v hiu chnh
Gii hn cnh bo
(WL)
1. Hai hoc ba im o vt qu
WL.
2.a. im o tip theo < WL.
2.b. im o tip theo > WL
1. Phn tch mu khc
2.a. Tip tc phn tch.
2.b. Dng li v hiu
chnh
lch chun (SD) 1.Bn hoc nm im o>1 SD
2.a. im o tip theo < 1SD
2.b. im o tip theo > 1SD
1.Phn tch mu khc
2.a. Tip tc phn tch
2.b. Dng li v hiu
chnh
ng trung tm
(CTL)
1. im o nm trn CTL
2.a. im o tip theo di CTL
2.b. im o tip theo trn CTL
1. Phn tch mu khc
2.a. Tip tc phn tch
2.b. Dng li v hiu
chnh
7.3.9. th hai mu (2 sample plots):
Dng th hai mu kim tra 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.
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.
90
Nu k hiu cc mu l x, y, nh s cc PTN t 1... m ta s thu c m cp gi
tr
m m 2 2 1 1
y x , , y x , y x . 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.
+ Gi thit o l tn ti sai s ngu nhin th tt c cc im s nm gc
nghing 45
0
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 X
Hnh 7.1 th hai mu kim tra sai s h thng cc PTN
7.3.10. 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. 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 cu cc PTN.
Tm li, cc bc tin hnh QA/QC trong PTN c th c m t nh s hnh 2.


( Y X, )
mu Y
91

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 hiu qu

Tt

Kim sot cht lng
(bao gm bo tr thit b)


Sot xt/chp nhn li
- kim tra hiu qu
- nh gi hiu qu



Hnh 7.2 : Hot ng QA/QC trong PTN .







Khngttt
t
Khngtt Tt
92
MC LC

Chng 1: CC DNG SAI S TRONG HA PHN TCH.............................. 1
1.1. Sai s v cch biu din sai s.................................................................................. 1
1.1.1.Sai s tuyt i (E
A
) (Absolute error) ....................................................................... 1
1.2. Phn loi sai s .......................................................................................................... 2
1.4. chm v chnh xc .......................................................................................... 6
Chng 2 CC I LNG THNG K............................ 7
2.1. Cc i lng trung bnh.......................................................................................... 7
2.2. Cc i lng c trng cho lp li..................................................................... 8
2.3. Bo co kt qu phn tch....................................................................................... 12
2.3.1. S c ngha v cch ly gi tr gn ng.............................................................. 12
2.4. Quy lut lan truyn sai s ngu nhin - lch chun ca i lng o gin tip14
Chng 3 HM PHN B V CHUN PHN B..................................... 17
3.1. Biu din s liu nh lng.................................................................................... 17
3.2. Phn b l thuyt..................................................................................................... 18
3.2.1. Phn b chun (Phn b Gauss) ...................................................................... 18
3.2.3. Cc phn b c bit. ....................................................................................... 21
3.2.4. Phn b
2
( chi - square distribution)................................................................. 23
3.3. Quan h gia cc phn b ring................................................................................. 24
3.4. Khong tin cy, gii hn tin cy v khng m bo ca i lng o.................... 25
3.5. Mt s bi ton lin quan n khong tin cy ............................................................ 26
Chng 4: CC PHNG PHP KIM TRA THNG K.............................. 28
4.2. Xc nh gi tr bt thng .............................................................................. 28
4.3. S dng chun thng k trong cc php so snh............................................. 30
4.3.1. So snh trong mt tp s liu (1 sample) ...................................................... 30
4.4. So snh 2 phng php .................................................................................... 37
4.4.1. So snh tng cp..................................................................................................... 37
4.4.2. Phng php th ................................................................................................. 37
Chng 5: PHN TCH PHNG SAI .................................................. 39
5.1. So snh mt s gi tr trung bnh............................................................................ 39
5.2. Phn tch phng sai mt yu t ( one-way ANOVA) .................................... 42
5.3. Phn tch phng sai hai yu t (two-way ANOVA)...................................... 46
5.4. Bi ton phn tch phng sai 3 yu t tr ln- phng
php vung Latinh.................................................................................... 50
Chng 6: PHN TCH TNG QUAN V HI QUI.............................. 54
6.2. Phng php bnh phng ti thiu........................................................................... 58
6.3. Kim tra hng s trong phng trnh hi qui ........................................................ 63
6.4. Gii hn pht hin, gii hn nh lng, nhy, chn lc........................................ 66
6.5. Phng php thm chun (standard addition method) (spiking) .................... 70
6.6. Phng php ni chun.................................................................................... 72
6.7. S dng ng hi qui trong phn tch so snh.............................................. 75
Chng 7 M BO CHT LNG V KIM SOT............................ 81
CHT LNG........................................................................................................ 81
7.1. Khi nim v m bo cht lng v kim sot cht lng (QA/QC) .................. 81
Yu cu v k thut.................................................................................................... 81
7.2. Cc iu kin tin hnh QA/QC............................................................................. 82
7.2.1. Nng lc qun l v thc thi cng vic ca phng th nghim ....................... 82
7.2.2. V c s vt cht. .............................................................................................. 82
7.3. Th tc tin hnh QA/QC.......................................................................................... 87
93