Professional Documents
Culture Documents
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v tng ng gi tr ca t:
46 . 0
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l 2.3 vi bc t do l 8, nn khng c s khc nhau ng k no gia gi tr ca kt qu
thu c t 2 phng php. Do s khc nhau (0.64) c so vi thut ng lch chun
ca 1.4 trn. Gi tr 1.4 ny l lch chun lin quan vi s khc nhau v theo i din
cho phn b lin quan ti KB lin quan vi php o chch.
7.7.6. chch tng c th c c lng bng thc hin phn tch thm cc vt liu
nghin cu. Cng xem xt p dng nh nghin cu mu chun ( trn). Thm vo, s khc
nhau ca cc vt liu thm v vt liu t nhin vo mu c th c xem xt v to s tha
nhn. S tha nhn c th to nn trn c s ca:
- Cc nghin cu phn b chch c quan st cho mt khong cc mu v mc phn
tch thm.
- So snh kt qu quan st mu chun vi h s thu hi ca phn tch mu thm trong cng
mu chun.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 24
- L lun trn c s mu c th vi tc ng c bit bit. V d tht hu, l mt loi mu
tht bin c bit n c xu hng kt ta mt vi yu tt vi mui canxi trong khi tiu
ho v c th cung cp mt c lng sai v h s thu hi m c lng KB c th
da vo (v d trng hp sai nh la chn phn b tam gic hoc phn b hnh ch
nht).
- L lun trn c s nhng kinh nghim c
7.7.7. chch c th c c lng bi so snh cc phng php c th vi mt gi tr
xc nh ca mt phng php thm chun bit lng thm vo mu th phn tch v nng
phn tch chnh xc suy ra bng ngoi suy. KB lin quan vi chch thng nh
hng bi cc KB lin quan vi ngoi suy, tng hp (khi thch hp) vi bt k phn b
ng k ca KB no t khu chun b v thm dung dch chun.
Ch thch: c c lin quan trc tip vic thm vo cn to ti mu gc hn l mu
chit.
7.7.8. Yu cu chung trong ISO Guide l cc s hiu chnh cn c p dng cho tt c cc
nh hng h thng ng k bit. Khi mt s hiu chnh c p dng cho chch tng
ng k th KB lin quan vi chch c c lng nh phn 7.7.5. cp trng
hp chch ng k.
7.7.9. Khi chch l ng k nhng vn b qua v cc mc ch thc t, cn tin hnh thm
cc cng vic (xem phn 7.15.).
Thm cc tham s
7.7.10. Cc nh hng ca bt k tham s cn li cn c c lng ring khng theo
phng sai thc nghim hay chm thit lp theo l thuyt. KB lin quan vi cc tham
s cn c c lng, tng hp v lu h s vi cc thnh phn khc theo cch thng
thng.
7.7.11. Khi nh hng ca cc tham s cn li c chng minh l c th l i v so vi
chm ca nghin cu l (v d thng k l khng ng k) c th khuyn ngh rng phn b
KB tng ng lch chun lin quan vi php th lin quan vi tham s .
V d: nh hng ca vic chit trong thi gian 1 gi c nhn thy bng php th t trong 5
ln trn mi mu th vi thi gian chit thng thng v thi gian chit gim sau 1 gi.
Trung bnh v lch chun (tnh mg/L) vi thi gian chun l: TB: 1.8; lch chun 0.21;
thi gian gim: TB: 1.7 lch chun 0.17. th t s dng phng sai tng hp
037 . 0
) 1 5 ( ) 1 5 (
17 . 0 ) 1 5 ( 21 . 0 ) 1 5 (
2 2
+
+
thu c
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 25
82 . 0
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,
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khng ng k khi so snh vi t
crit
= 2.3. Nhng ch thch rng s khc nhau (0.1) c so
snh vi vic tnh lch chun . 12 . 0 ) 5 / 1 5 / 1 ( 037 . 0 + Gi tr ny l phn b ti
KB lin quan vi nh hng phng sai trong thi gian chit.
7.7.12. Khi mt nh hng c pht hin v c thng k ng k nhng nh v khng
ng k thc t c l i th p dng theo hng dn nu trong 7.15.
7.8. nh gi KB cho cc phng php kinh nghim
7.8.1. Phng php kinh nghim l phng php c tha nhn da vo mc ch ca php
o so snh p dng trong mt lnh vc c th khi thuc tnh i lng o ph thuc vo
phng php s dng. Phng php xc nh i lng o. V d bao gm cc phng php
kim loi c th lc trong gm s v si thc phm trong thc phm (xem phn 5.2 v v d
A.5).
7.8.2. Khi mt phng php s dng trong phm vi p dng c xc nh, chch
lin quan vi phng php c xc nh l = 0. Trong trng hp ny th c lng
chch ch cn c lin quan vi vic thc hin ti PTN v cn thm cc tnh ton bn cht
chch ca phng php. iu ny c tun theo cc hng dn.
7.8.3. Mu chun nghin cu, d chng minh chch c th l i hoc o chch
u cn tin hnh s dng mu chun c chng nhn s dng phng php c th hoc
thu c gi tr vi phng php c th c sn so snh.
7.8.4. Khi mu chun m cc thuc tnh khng c sn th kim sot chch tng lin quan
vi kim sot cc tham s ca phng php nh hng n kt qu; cc tham s nh thi
gian, nhit , khi lng, th tch KB lin quan vi cc tham s u vo phi c
nh gi theo v ch ra KB lin quan ti cc tham s c b qua hay tnh n (xem v
d A.6).
7.8.5. Phng php theo kinh nghim thng l i tng nghin cu lin phng v
KB c th c nh gi nh cp trong phn 7.6.
7.9. nh gi KB cho phng php ad-hoc
7.9.1. Phng phap ad-hoc l cc phng php c thit lp tin hnh nghin cu thm
d, th mu nhanh hoc trong thi gian ngn. Nh phng php c da vo chun hoc
phng php thit lp tt trong PTN nhng c sa li v c bn (v d nghin cu mt
php phn tch khc) v s khng chng minh chung cho cc nghin cu ph duyt cho vt
liu c th.
7.9.2. Gii hn kt qu s c sn thit lp cc phn b KB lin quan cn da vo s
hiu bit ca cc h thng lin quan hoc trong cc h thng. c lng KB cn da
theo vic thc hin bit trong h thng v cc h thng lin quan. Cc thng tin thc hin
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 26
cn c h tr bng cc nghin cu cn thit thit lp mi lin quan ca cc thng tin.
Theo khuyn ngh gi thit rng h thng lin quan l c sn v c nghin cu hiu qu
thu c c lng KB ng tin hoc bao gm cc thng tin t cc phng php khc
v KB trong khun kh c thit lp t trc.
7.9.3. Ti thiu, cn c lng chch tng v s ch ca chm c th ca phng
php. chch s c o l tng theo mu chun, nhng thc t thng thng c nh
gi bng h s thu hi ca mu thm. Nghin cu phn 7.7.4 sau p dng, tr cc h s
thu hi mu thm cn dc so snh vi cc quan st trn h thng lin quan thit lp s
lin quan vi cc nghin cu trc cho phng php ad-hoc. chch tng c quan st
cho phng php ad-hoc trn cc mu th cn c so snh t quan st cho h thng
lin quan trong cc yu cu nghin cu.
7.9.4. Nghin cu chm ti thiu bao gm phn tch lp li. Khuyn ngh l s ln th
nghim lp li bng vi s ln thc hin th nghim thc t. chm cn c so snh cho
h thng lin quan; lch chun cho phng php ad-hoc cn c so snh.
Ch thch: khuyn ngh rng s so snh c da vo kim tra. S lng th nghim thng
k ng k (v d th nghim F) ni chung s khng ng tin vi mt s lng lp li t v s
c xu hng kt lun mt cch d dng rng khng c s khc nhau ng k no do kh nng
thp ca php th.
7.9.5. Khi cc iu kin trn c p ng r rng, c lng KB cho h thng lin quan
c th c p dng trc tip t cc kt qu thu c bi phng php ad-hoc, khi iu chnh
bt c iu kin g nh nng v nhng thng s bit.
7.10. nh lng tng thnh phn
7.10.1. Thng cn cn nhc mt vi ngun KB ring l. Trong mt s trng hp iu
ny ch cn thit i vi mt s lng nh cc ngun, trong trng hp khc, c th thc t
khi c t hoc khng c cc d liu ca phng php, tt c cc ngun cn c nghin cu
ring (xem v d 1, 2, 3 trong ph lc A minh ho). C nhiu phng php chung c
lng cho tng thnh phn KB ring l.:
- Phng sai thc nghim khi cc i lng u vo khc nhau;
- T d liu c sn nh kt qu o v chng ch hiu chun;
- Bi m hnh t cc qui tc l thuyt;
- S dng l lun da vo kinh nghim hoc khng nh bng m hnh gi thit;
Cc phng php khc nhau c cp tm tt di y.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 27
7.11. c lng thc nghim ca tng phn b KB
7.11.1. C kh nng v thc nghim thu c c lng phn b KB t nghin cu th
nghim c th cho cc tham s ring l.
7.11.2. KB chun ny sinh t cc nh hng ngu nhin thng c tnh t cc lp
li thc nghim v nh lng di dng lch chun ca cc gi tr o. Thc t khng cn
thc hin qu 15 ln lp li nu khng yu cu chm cao.
7.11.3. Cc dng nghin cu thc nghim khc bao gm:
- Nghin cu nh hng ca phng sai ca mt tham s n kt qu. Thch hp c th
trong trng hp lin tc, cc tham s c th kim sot, c lp ca cc nh hng khc.
T l thay i ca kt qu khi thay i cc tham s c th thu c t cc d liu nghin
cu. S thay i ny thng c tng hp trc tip vi KB trong tham s thu
c phn b KB lin quan.
Ch thch: S thay i tham s c th thay i cn bn ng k kt qu so vi chm c sn
trong nghin cu (v d vi lch chun ca 5 ln o lp li).
- Cc nghin cu sai s th (Robustness), h thng th nghim l thay i c mc cc
tham s. Nghin cu ny thch hp cho vic xc nh nhanh cc nh hng ng k v
thng s dng cho vic ti u ho phng php. Phng php ny c th c p dng
trong trng hp cc nh hng ring bit nh thay i nhiu (matrix) hoc thay i nh
trong cu hnh thit b m c cc nh hng khng bit trc n kt qu. Khi mt thng
s c tm thy l c nh hng ng k th thng cn phi nh gi thm. Khi nh
hng ng k th KB (t nht l c lng ban u) thu c t nghin cu sai s th.
- Thit k th nghim vi h thng a thng s c lng cc nh hng thng s v
cc s tng tc. Cc nghin cu nh th c s dng c th khi c lit k cc thay i.
Mt lit k cc thay i m trong gi tr ca thay i l khng lin quan ti ln ca
nh hng; s lng PTN tham gia nghin cu, tn th nghim vin hoc dng mu l cc
v d cho vic lit k s thay i. V d nh hng ca vic thay i trong dng nhiu
(trong phm vi phng php ch ra) c th c c lng t nghin cu h s thu hi
tin hnh trong nghin cu a nhiu lp li. S phn tch phng sai cn cung cp trong
v gia cc thnh phn nhiu ca phng sai cho s quan st phn tch h s thu hi. Gia
thnh phn nhiu ca phng sai c th cung cp mt KB chun lin quan vi
phng sai nhiu.
7.12. c lng da vo cc kt qu hoc d liu khc
7.12.1. Vic ny thng c th c lng mt vi KB chun s dng cc thng tin lin
quan c sn v KB trn php nh lng lin quan. Cc phn di y s a ra cc gi
v mt vi ngun thng tin.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 28
7.12.2. H thng th nghim thnh tho (PT). Kt qu ca mt PTN t vic tham gia vo h
thng PT c th s dng nh kim tra nh gi KB, t KB cn so snh vi
khong cc kt qu m PTN thu c qua vic tham gia cc PT. Thm mt vi trng hp khi
- Thnh phn ca mu s dng trong h thng bao gm ton b phm vi phn tch thng
thng
- Cc gi tr ch ra trong mi ln lin kt chun ti cc gi tr tham chiu thch hp v
- KB trn gi tr n nh l nh so vi khong quan st c ca cc kt qu
sau s phn tn khc nhau gia cc gi tr c bo co v cc gi tr n nh thu c qua
cc ln lp li cung cp c bn mt c lng tt v KB ny sinh t cc phn ny ca
th tc o trong phm vi ca h thng. V d i vi mt h thng thc hin vi cc vt liu
n gin v cc mc phn tch, lch chun khc nhau c th cung cp KB chun. Tuy
nhin lch h thng t lin kt chun n nh gi tr v cc ngun KB khc (nh c
ghi ch trong 7.6.1) phi c tnh n.
7.12.3. D liu m bo cht lng (QA) Nh ch thch cn m bo rng ch tiu cht
lng t ra trong tiu chun thc hin cc th tc c thc hin v cc php o trn cc
mu m bo cht lng ch ra rng cc ch tiu tip tc c p ng. Khi cc cht chun
c s dng kim tra trong kim sot cht lng phn 7.5 ch ra cc d liu c th c
s dng nh gi KB. Khi s dng bt c vt liu n nh khc d liu m bo cht
lng cung cp mt c lng chm trung gian (mc 7.7.2). D liu m bo cht lng
cng to thnh mt s kim tra trn gi tr c ca KB. R hn KB tng hp ny
sinh t cc nh hng ngu nhin khng th t hn lch chun ca cc php o m bo
cht lng.
7.12.4. Thng tin ca nh cung cp. i vi nhiu ngun ca KB nh chng ch hiu
chun hoc catalo ca nh cung cp a ra cc thng tin. V d dung sai ca dng c o bng
thu tinh c th thu c t catalo ca nh cung cp hoc chng ch hiu chun lin quan ti
phm vi c th khi s dng.
7.13. M hnh t cc qui tc l thuyt
7.13.1. Trong nhiu trng hp l thuyt vt l c thit lp tt cung cp cc m hnh tt
v cc nh hng ln kt qu. V d, nh hng ca nhit ln dung tch v t trng c
bit n r rng. Trong cc trng hp cc KB c th c tnh hoc c lng t
dng mi lin quan s dng phng php ph bin ca KB cp trong phn 8.
7.13.2. Trong cc tnh hung khc c th cn s dng cc m hnh l thuyt tng ng kt
hp vi d liu thc nghim. V d khi mt php o phn tch ph thuc vo thi gian xy ra
phn ng c th cn nh gi KB lin quan vi thi gian. C th hon thnh bng
phng sai n theo thi gian. Do c th tt hn thit lp m hnh t l tng ng t
tm tt nghin cu thc nghim ca pht sinh phn ng gn cc nng lin quan v nh
gi KB t t l d on thay i ti thi gian ra.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 29
7.14. c lng da vo l lun
7.14.1. nh gi KB khng phi l cng vic hng ngy hay mt php ton no c; n
ph thuc vo kin thc cn k v i lng o v phng php o cng nh th tc s dng.
Cht lng v li ch ca KB a ra cho kt qu ca mt php o c bn ph thuc vo
s hiu bit, phn tch ti gii hn v tnh ton vn ca nhng phn b c qui cho gi tr
ca kt qu.
7.14.2. Hu ht cc phn b ca d liu c th c din gii theo ngha l t d liu quan st
nm gn bin ca phn b hn l trung tm. nh lng v lch chun lin quan ca
cc phn b t c qua cc php o lp li.
7.14.3. Do , cc nh gi khong cch khc c th yu cu trong trng hp khi cc php
o lp li khng thc hin c hoc khng cung cp ngha o lng cho thnh phn
KB
7.14.4. C mt s trng hp c bit trong phn tch ho hc thnh hnh mun v yu cu
phi c l lun. V d:
- Khng th nh gi h s thu hi v KB lin quan cho tng mu n. Thay vo
nh gi cho mt nhm cc mu (v d. nhm cc dng mu), v cc kt qu p dng cho
tt c cc mu v dng mu. Mc ging nhau l khng c bit, do s nhiu (t
dng ca cc mu ti mt mu c th) lin quan ti vic thm vo KB m thng
khng c gii thch.
- M hnh ca mt php o nh vic xc nh bng yu cu ca cc th tc phn tch c
s dng chuyn nh lng i lng o ti gi tr ca i lng (kt qu phn tch).
M hnh l - thng tt c m hnh trong khoa hc - i tng ca KB. Ch c gi
thit rng bn cht tun theo m hnh c th nhng c th khng bao gi c bit n
hon ton chc chn .
- Vic s dng cc mu chun c c bit khuyn khch nhng KB lin quan khng
ch gi tr thc nhng cng lin quan vi mu chun dng phn tch mt mu c th. Yu
cu nh gi m rng tuyn b bn cht chun tng ng tng i t nhin ca cc
mu trong cc tnh hung c th.
- Ngun khc ca KB ny sinh khi i lng o c xc nh khng y do th
tc o. Nghin cu s xc nh oxi ho pemanganat (thuc tm) khc nhau rt r rng khi
phn tch nc ngm hoc nc thi th. Khng ch cc thng s nh nhit oxi ha
cng nh cc nh hng khc nh nhiu v thnh phn hoc nn c th c nh hng ln
yu cu k thut ca phng php.
- Thng thng thc t trong phn tch ho hc c gi l thm mt n cht nh mt
cht c cu trc tng t hoc cht ng v t c h s thu hi ca cht t nhin tng
ng hoc nhm hp cht c nh gi. R hn, KB lin quan c nh gi thc
nghim cung cp phn tch c chun b cho nghin cu h s thu hi cho tt c cc mc
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 30
v t l nng ca i lng o thm vo v tt c cc nhiu lin quan. Nhng thng
thng mt thc nghim c ngn nga v thay th bi cc quyt nh v:
tnh ph thuc nng ca cc h s thu hi ca i lng
tnh ph thuc nng ca h s thu hi mu thm
tnh ph thuc ca h s thu hi trn cc dng nhiu
tnh ng nht ca cc phng thc lin kt ca cc cht t nhin v cht thm
7.14.5. nh gi ca dng ny khng da vo cc kt qu thc nghim trc tip nhng c
th do ch th (con ngi) din t y c th s dng ng ngha vi mc tin cy,
c th do trc gic v ng tin cy [H.11]. Gi s rng mc tin cy l khng da vo
nh gi nhanh nhng c cn nhc nh gi cn thn.
7.14.6. D c tha nhn l c tnh ch quan khc nhau t mt ngi n nhiu ngi
khc v d l mt ngi qua cc khong thi gian chng khng b b buc nh chng c
nh hng bi gic quan thng thng, kin thc ca chuyn gia v bng cc nghin cu thc
nghim v quan st sm hn.
7.14.7. C th pht hin ra cc iu bt li nhng khng hng dn trong thc t ti c
lng xu hn t cc php o lp li. C th iu ny p dng nu thc t khc nhau trong
iu kin thc nghim khng c m phng v d liu kt qu khc nhau khng a ra mt
bc tranh ng tin cy.
7.14.8. Mt dng vn ny sinh t nhin khi s khc nhau lu di cn c nh gi khi
khng c d liu nghin cu lin phng. Mt nh khoa hc ngi b qua s la chn kh
nng ch quan v vt thay th cho mt i lng o thc (khi m ln sau cng l khng c
sn) c l i cc phn b quan trng n KB tng hp nn sau cng t khch quan hn
l mt ngi da vo cc kh nng ch quan.
7.14.9. i vi mc ch c lng KB tng hp c hai c trng v mc c
lng tin cy l cn thit:
- Mc tin cy c lin quan nh khong gi tr m tuyn b mt khong gii hn
trn v di ti cc phn b c th c cung cp
- Cc cng c in ton tng t p dng trong vic tng hp phn b mc tin cy ca
KB ti KB tng hp nh cho cc lch chun thu c bi cc phng php
khc.
7.15. chch ng k
7.15.1. Mt yu cu chung ca ISO GUM l cc s hiu chnh cn c p dng cho tt c
cc nh hng h thng ng k v bit.
7.15.2. Trong vic quyt nh khi chch bit c th c b qua, cch tip cn c
khuyn ngh nh sau:
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 31
a. c lng KB tng hp khng cn nhc ti chch lin quan
b. So snh chch vi KB tng hp
c. Khi chch so vi KB l khng ng k th c th b qua
d. Khi chch so vi KB l ng k th yu cu phi c hnh ng gii quyt. C
th gii quyt bng cch:
- Loi tr hoc hiu chnh cho chch, a ra s tha nhn KB ca s hiu
chnh
- Bo co chch quan st c v thm KB ca chch vo kt qu
Ch thch: khi chch bit khng c hiu chnh theo qui nh, phng php cn c
cn nhc theo li kinh nghim (xem phn 7.8).
8. BC 4. TNH KHNG M BO TNG HP
8.1. Cc khng m bo chun
8.1.1. Trc khi tng hp tt c cc thnh phn KB phi c din t nh cc KB
chun hoc lch chun. Cc KB chun c th c chuyn t cc php o phn
tn. Theo cc qui tc nu trong hng dn chuyn mt thnh phn KB thnh mt
lch chun.
8.1.2. Khi thnh phn KB c nh gi thc nghim t s phn tn ca cc php o
lp li th c th c din t nh lch chun. phn b ti KB trong cc php o
n th KB chun c quan st chnh l lch chun; tnh trung bnh ca cc kt qu,
lch chun ca trung bnh [B.24] c s dng.
8.1.3. Khi c lng mt KB t cc kt qu v d liu c sn th vn c th din t
nh mt lch chun. Do khi c mt khong tin cy c a ra vi mt mc tin cy
(theo dng t a ti p%) th chia gi tr a cho im phn trm tng ng ca phn b thng
cho mc tin cy tnh lch chun.
V d:
Mt yu cu k thut cng b rng kh nng c ca cn l trong khong 0,2 mg vi mc
tin cy 95%. T bng chun ca im phn trm th phn b chun, mc tin cy 95%
th tnh ton lch chun s dng mt gi tr l 1.96. Theo cng thc th thu c KB
chun l 0.2/1.96 0.1.
8.1.4. Nu gii hn ca t a c a ra v khng km theo mc tin cy v c cc l do
cho rng s phn b cc gi tr l nh nhau th thng l d on theo phn b tng ng
l phn b hnh ch nht nn lch chun tnh theo cng thc a/ 3 . (Xem ph lc E).
V d:
Mt bnh nh mc cp A 10mL c chng nhn l 0.2 mL. KB chun l 0.2/ 3 0.12
mL.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 32
8.1.5. Nu gii hn ca t a c a ra v khng km theo mc tin cy nhng c l do
cho rng cc gi tr phn b khng nh nhau th thng d on theo phn b tng ng
l phn b hnh tam gic nn lch chun tnh theo cng thc a/ 6 (Xem ph lc E)
V d:
Mt dnh nh mc cp A 10mL c chng nhn l 0.2 mL nhng Kim tra ti PTN ch ra
rng cc gi tr him khi tp trung gn hai cc . KB chun l 0.2/ 6 0.08 mL.
8.1.6. Khi c lng c to nn t cc l lun c bn th c th c lng thnh phn trc
tip nh mt lch chun. Nu khng th th c lng c th t lch chun ln nht m
c th xut hin t thc tin (ngn chn/loi tr cc sai li). Nu mt gi tr nh hn c cn
nhc v c bn c nhiu kh nng hn th c lng ny nn coi nh m t ca mt phn b
hnh tam gic. Nu khng c v tr no tin rng nhiu kh nng c mt sai s nh hn l sai
s ln th c lng nn theo phn b hnh ch nht.
8.1.7. Cc thng s chuyn i thng thng nht s dng cc chc nng phn b c
cp trong ph lc E.1.
8.2. Tng hp khng m bo chun
8.2.1. Sau khi c lng tng thnh phn hoc nhm cc thnh phn KB v din t
chng nh nhng KB chun, bc tip theo l tnh ton KB chun tng hp s dng
mt trong cc th tc c m t di y.
8.2.2. Mi quan h chung gia KB chun tng hp u
c
(y) ca gi tr y v KB ca
cc tham s c lp x
1
, x
2
, x
n
m
y ph thuc l
n i
i
n i
i i c
x y u x u c x x y u
, 1
2
, 1
2 2
2 1
) , ( ) ( ,...)) , ( (
Trong y(x
1
, x
2
,) l mt hm ca mt s tham s t x
1
, x
2
, , ci l h s nhy c nh
gi bng cng thc c
i
= y/x
i
o hm tng phn ca y vi x
i
v u(y, x
i
) chng t KB ca
y ny sinh t KB ca x
i
. Mi phn b phng sai u(y, xi) l bnh phng KB lin
quan din t nh lch chun nhn vi h s nhy tng ng. Cc h s nhy ny m t
gi tr ca y thay i nh th no khi thay i cc thng s x
1
, x
2
Ch thch: H s nhy c th c nh gi trc tip t thc nghim, c gi tr c th khi
khng c m t ton hc ng tin ca cc mi lin quan.
8.2.3. Khi cc phng sai khng c lp th mi quan h phc tp hn
+
n i
k i
n k i
k i k i i
i
j i
x x u c c x u c x y u
, 1 , 1 ,
2 2
) , ( ) ( ...)) , ( (
Trong u(x
i
, x
k
) l hip phng sai gia x
i
v x
k
v c
i
v c
k
l h s nhy nh m t v
nh gi phn 8.2.2. Hip phng sai c quan h ti h s hip tng quan r
ik
theo cng
thc:
ik k i k i
r x u x u x x u ). ( ). ( ) , (
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 33
Khi -1 r
ik
1
8.2.4. Th tc chung p dng khi cc KB lin quan vi tng thng s, nhm cc thng
s hoc theo 1 phng php. Do khi phn b KB c lin quan vi ton b th tc th
thng c din t nh 1 nh hng n kt qu cui cng. Trong nhng trng hp
hoc khi KB ca 1 tham s c din t trc tip bng thut ng nh hng n y th h
s nhy y/x
i
thng bng 1.0
V d:
Mt kt qu 22mg/L ch ra lch chun l 4.1mg/L. KB chun u(y) lin quan vi
chm di cng iu kin l 4.1mg/L. M hnh n ca php o b qua nhng tham s khc
lm r l:
y = (kt qu c tnh ton) +
trong th hin nh hng ca phng sai ngu nhin di cc iu kin o y/ l
bng 1.0
8.2.5. Tr trng hp trn khi h s nhy bng 1 v cc trng hp c bit c nu
trong qui tc 1 v 2 di, th tc chung yu cu s pht sinh cc phn khc nhau hoc cc s
liu tng ng phi c tnh n. Ph lc E cp chi tit phng php s liu, do
Kragten khuyn co [H.12], to nn cc nh hng s dng bng tnh trong phn mm
cung cp KB tng hp t cc KB chun ca i lng u vo v m hnh o
bit. C mt khuyn ngh rng phng php ny hoc cc phng php khc da vo my
tnh c s dng nhng cho nhng trng hp n gin.
8.2.6. Trong mt vi trng hp, s din t KB tng hp theo dng c n gin
nhiu. Hai qui tc n gin tng hp KB chun c nu ra di y.
Qui tc 1
Cc m hnh ch bao gm mt tng hoc thng, v d y = (p + q + r +), KB chun
tng hp u
c
(y) c tnh theo cng thc
... ) ( ) ( ,...)) , ( (
2 2
+ + q u p u q p y u
c
Qui tc 2
Cc m hnh ch bao gm cc php nhn v chia, v d y = (p x q x r x) hoc
y = p/(q x r x ), KB chun tng hp u
c
(y) c tnh theo cng thc
...
) ( ) (
) (
2 2
+
,
_
,
_
q
q u
p
p u
y y u
c
Trong (u(p)/p) l KB ca tham s c din t nh lch chun tng quan.
Ch thch: Php tr trong m hnh ton cng tnh theo cng thc nh php cng v php chia
trong m hnh ton cng tnh theo cng thc nh php nhn.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 34
8.2.7. Vi mc ch tng hp cc thnh phn KB th c mt cch s to s thun tin
hn khi bin i s din t m hnh ton hc c th p dng mt trong cc qui tc trn. V
d bin i cng thc
(o + p) / (q + r)
thnh 2 thnh phn (o + p) v (q + r). KB chuyn cho tng thnh phn trn v c th
c tnh ton theo qui tc 1 trn, sau tng hp KB s dng qui tc 2 c
KB chun tng hp .
8.2.8. Cc v d di y minh ha cch s dng cc qui tc trn:
V d 1:
y = (p q + r) gi tr l p = 5.02, q = 6.45 v r = 9.04 vi cc KB chun u(p)=0.13,
u(q)=0.05 v u(r)=0.22.
y = 5.02 6.45 + 9.04 = 7.61
26 . 0 22 . 0 05 . 0 13 . 0 ) (
2 2 2
+ + y u
V d 2:
y = (op/qr). Cc gi tr l o = 2.46, p = 4.32, q = 6.38 v r = 2.99 vi cc KB chun l
u(o) = 0.02, u(p) = 0.13, u(q) = 0.11 v u(r) = 0.07.
y = (2.46 x 4.32) / (6.38 x 2.99) = 0.56
024 . 0 043 . 0 56 . 0 ) (
99 . 2
07 . 0
38 . 6
11 . 0
32 . 4
13 . 0
46 . 2
02 . 0
56 . 0 ) (
2 2 2 2
,
_
+
,
_
+
,
_
+
,
_
y u
y u
8.2.9. C mt vi hng s trong ln ca cc thnh phn KB khc nhau vi cc mc
phn tch. V d KB trong s thu hi c th nh hn i vi vt liu cp cao hoc tn
hiu quang ph c th c cc khong khc nhau trn thc t l tng ng thi gian lu.
(hng s phng sai). Trong cc trng hp vic quan trng l tnh s thay i KB
chun vi cc mc phn tch. S tip cn bao gm:
- Gii hn c th ca th tc hoc c lng KB ti phm vi nh ca cc nng
phn tch.
- Cung cp KB c lng theo dng lch chun tng quan
- Tnh ton c lp r rng v tnh li KB cho kt qu
Ph lc E4 a thm thng tin v cc tip cn trn
8.3. khng m bo m rng
8.3.1. Bc cui cng l nhn KB chun tng hp vi h s ph c la chn thu
c KB m rng. KB m rng c yu cu cung cp mt khong m c th
hy vng bao gm phn ln s phn b ca cc gi tr m c th qui cho i lng o mt cch
hp l.
8.3.2. Trong vic chn mt gi tr cho h s ph k, mt s cch c th cn nhc, bao gm;
- Yu cu v mc tin cy
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 35
- Bt c kin thc no da vo phn b
- Bt c kin thc v s lng cc gi tr s dng c lng cc nh hng ngu nhin
(xem 8.3.3 di).
8.3.3. i vi hu ht cc mc ch th u c mt khuyn ngh l s dng h s ph k =2.
Do gi tr ny ca k c th t hiu qu khi KB chun tng hp c tnh da vo cc
quan trc thng k vi mt vi bc t do lin quan (t hn 6). Khi chn k th ph thuc vo s
bc t do nh hng.
8.3.4. Khi KB chun tng hp c chi phi bng mt phn b n vi bc t do nhiu
hn 6, c khuyn ngh l k c thit lp bng cch tnh s bc t do v tra bng student
tm c gi tr ca k v mc tin cy theo yu cu (thng l 95%). Bng 1 a ra mt
danh mc cc gi tr ca t.
V d:
KB chun tng hp cho vic cn c to thnh t cc phn b u
cal
= 0.01 mg ny sinh
t KB hiu chun v s
obs
= 0.08mg da vo lch chun ca 5 ln quan st lp li.
KB chun tng hp uc tng ng l
2 2
08 . 0 01 . 0 + =0.081mg. y l nh hng do
phn b lp li s
obs
qua 5 ln quan trc lp li cho bc t do l 5 - 1 = 4, k tra trong bng
student t gi tr ca t vi bc t do l 4 v mc tin cy 95% c k = 2.8; k c t l
2.8 th KB m rng U = 2.8 x 0.081 = 0.23 mg.
8.3.5. Hng dn [H.2] cp thm hng dn la chn k khi thc hin s ln o t
c lng nh hng ngu nhin v cn c tham chiu khi c lng s bc t do cho cc
phn b ng k.
8.3.6. Khi cc phn b ln quan ti phn b chun, h s ph k = 2 (hoc la chn theo mc
8.3.3 8.3.5 s dng mc tin cy 95%) cho mt khong tin cy xp x 95% trong phn b
ca cc gi tr. C mt khuyn ngh rng khng p dng khong tin cy 95% nu khng c
kin thc g v phn b lin quan.
Bng 1: Bng student vi mc tin cy 95%
Bc t do
t
1
2
3
4
5
6
12.7
4.3
3.2
2.8
2.6
2.5
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 36
9. BO CO KHNG M BO O
9.1. Gii thiu chung
9.1.1. Thng tin cn thit bo co kt qu ca mt php o ph thuc vo mc ch s
dng ca kt qu. Cc qui tc hng dn l:
- a ra cc thng tin hu hiu qua kt qu c th c nh gi li khi thng tin mi
hoc c sn d liu
- D c li khi cung cp qu nhiu thng tin hn l t thng tin
9.1.2. Khi cc chi tit ca mt php o bao gm KB c xc nh nh th no, ph
thuc vo cc ti lieu tham chiu, i hi ti liu phi cn hiu lc v cc phng php s
dng phi sn c.
9.2. Thng tin yu cu
9.2.1. Bo co hon chnh ca mt kt qu o cn bao gm hoc tham chiu ti cc ti liu,
- M t phng php s dng tnh kt qu o v KB t cc quan st thc nghim v
d liu u vo.
- Cc gi tr v cc ngun ca tt c cc s hiu chnh v hng s s dng trong tnh ton v
phn tch KB
- Danh mc tt c cc thnh phn KB vi cc ti liu ch ra rng mi thnh phn
c nh gi nh th no
9.2.2. D liu v ngi phn tch cn c sn trong trng hp cn thit cc bc quan trng
c th tnh ton li kt qu.
9.2.3. Khi mt bo co chi tit bao gm yu cu din gii cho cc gi tr u vo th bo co
cn
- a ra gi tr ca mi gi tr u vo, KB chun ca cc gi tr u vo v m t cch
thc thu c i lng u vo
- a ra mi lin quan gia kt qu v cc gi tr u vo v bt c thnh phn dn xut,
hip phng sai hoc h s hiu chnh s dng tnh ton cc nh hng hip tng
quan.
- Tuyn b c lng s bc t do cho KB chun ca mi i lng u vo (cc
phng php c lng bc t do c a ra trong ISO Guide [H.2]).
Ch thch: Khi mi lin quan ca hm s (cng thc ton hc tnh kt qu) l phc tp hoc
khng r rng (v d c th ch tn ti di dng chng trnh my tnh) mi lin quan c th
c m t bng cc thut ng chung hoc bng cch trch dn tham chiu thch hp. Trong
cc trng hp phi nu tht r rng cch t c kt qu v KB.
9.2.4. Khi bo co kt qu cc php phn tch thng thng c th c hiu qu khi ch tuyn
b gi tr ca o KB m rng v gi tr ca k.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 37
9.3. Bo co KB chun
9.3.1. Khi KB c din t nh KB chun tng hp u
c
(coi nh mt lch
chun) mt dng bo co c khuyn ngh nh sau:
(Kt qu): x (n v) [vi a] KB chun ca uc
(n v) [khi KB chun c nh
ngha trong thut ng v nh ngha o lng c bn VIM, 2
nd
edition.., ISO 1993 v tng
ng vi mt lch chun].
Ch thch: Khng khuyn khch s dng biu tng khi tuyn b KB chun v biu
tng ny thng lin quan vi phm vi tng ng vi mc tin cy cao.
Thut ng trong du [ ] c th b b qua hoc vit tt mt cch thch hp
V d:
Tng nit : 3.52 % w/w
KB chun : 0.07 % w/w
*
* KB tng ng vi 1 lch chun
9.4. Bo co KB m rng
9.4.1. Nu khng c yu cu g khc kt qu x nn c tuyn b cng vi KB m rng
U tnh bng cch s dng h s ph k = 2 (hoc theo cch m t trong phn 8.3.3). Khuyn
ngh cng b kt qu theo dng:
(Kt qu) : (x t U) (n v)
Trong du [ ] c ghi l [ KB m rng c xc nh theo nh ngha ca VIM, 2
nd
ed.,
ISO 1993] c tnh ton s dng h s ph k = 2, [vi mc tin cy xp x 95%]
Thut ng trong du [ ] c th b qua hoc vit tt li mt cch thch hp. H s ph nn iu
chnh ch ra gi tr s dng thc s
V d:
Tng Nit : (3.52 0.14) %w/w
*
* Bo co KB l KB m rng c tnh bng cch s dng h s ph k=2 vi mc
tin cy xp x 95%.
9.5. Din t kt qu bng s
9.5.1. Cc gi tr bng s ca kt qu v KB ca n khng nn a ra vi s cc ch s
qu nhiu. Khi cng b KB m rng U hoc KB chun u thng thng him khi cn
cng b KB nhiu hn 2 ch s. Cc kt qu cn c lm trn thng nht vi KB
ca kt qu.
9.6. Cng b ph hp gii hn
9.6.1. Qui nh ph hp thng yu cu mt i lng o nh nng cht c ch ra
trong gii hn c th. KB o r rng c p dng din gii cc kt qu phn tch
trong phm vi cho php. C th:
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 38
- KB trong kt qu phn tch c th cn tnh n khi nh gi s ph hp
- Gii hn c th c thit lp vi mt vi KB tha nhn.
Cn nhc cn c a ra cho c 2 nhn t trong bt k s nh gi no. Cc phn di y
a ra cc v d thc nghim thng thng.
9.6.2. Cc gii hn khng c KB, 4 tnh hung c trnh by cho trng hp ph hp
vi gii hn trn (xem hnh 2):
a. Kt qu bao gm KB m rng vt qu gii hn trn
b. Kt qu vt qu gii hn trn nhng KB khng vt qu gii hn trn
c. Kt qu nm di gii hn trn nhng KB vt qu gii hn trn
d. Kt qu v KB khng vt qu gii hn trn
Trng hp a. thng c din gii r l khng ph hp. trng hp d. c din gii l
ph hp. Trng hp b. v c. s yu cu phi cn nhc hn v tho thun vi ngi s dng
kt qu. lp lun tng t p dng trong trng hp cng b ph hp gii hn di.
9.6.3. Khi c bit hoc tin rng gii hn thit lp vi mt vi tun th vi KB, s phn
quyt ph hp theo tuyn b ca phng php xc nh cho tng tnh hung. Tim n trong
yu cu c d on KB hoc t nht l ti lp ca phng php tuyn b l nh
l i cho cc mc ch c th. Trong cc trng hp cn cung cp cc chng trnh
kim sot cht lng thch hp, s ph hp c bo co thng thng ch c gi tr ca kt
qu c th. Thng c tuyn b trong bt c mt chun tip cn.
Gii hn
kim sot trn
a - kt qu v
KB nm pha
trn gii hn trn
b - kt qu nm
trn gii hn
trn nhng
KB nm di
gii hn trn
c kt qu di
gii hn nhng
KB nm
trn gii hn
trn
d - kt qu v
KB nm di
gii hn trn
Hnh 2 : Gii hn ph hp v khng m bo
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 39
PHN B:
C LNG KHNG M BO O T D LIU PH DUYT PHNG PHP
1. GII THIU:
Phn ny hng dn c lng KB c th thu c t thc nghim nghin cu ph
duyt phng php (xc nhn hiu lc phng php). Hng dn ny khng a ra cc yu
cu ca vic xc nhn hiu lc phng php. Hng dn ny ch tha nhn mc ch ca vic
xc nhn hiu lc phng php l nghin cu chm v ng v cc th nghim sai s
th (ruggedness). Qua cc d liu thu c t qu trnh nghin cu chm, ng hoc
cc th nghim sai s th c lng KB o. S 1 minh ha cc bc trong qui
trnh c lng KB. Mc ch ca phn ny a ra hng dn chi tit vic lp k hoch
thch hp nghin cu thc nghim sao cho tho mn hai mc ch l xc nhn hiu lc
phng php v c lng KB o.
S 1: qui trnh tm tt c lng KB
(cc s trong du ngoc lin quan ti cc mc trong phn B ca hng dn)
Xc nh cng thc ton hc
tnh kt qu v cc ngun
khng m bo (2)
K hoch v thc hin
nghin cu chm (3.1)
K hoch v thc hin nghin
cu ng (3.2)
Xc nh thm cc ngun khc gy
KB v nh gi (3.3)
Tng hp cc c lng KB thnh phn tnh KB
tng hp v m rng cho phng php (4)
Bo co v lu ti liu KB (5)
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 40
S 2: Minh ho qui trnh c lng KB
(cc s trong du ngoc lin quan ti cc mc ca hng dn)
Tnh KB qua
nghin cu chm
(3.1.1)
Tnh Rm t phn tch lp li 10
ln trn cc mu thm ca cng
cc mu t mt l mu (3.2.2)
hoc bng phng php khc
(3.2.3, 3.2.4)
Vit cng thc y tnh ton
kt qu ca phng php (2)
Lit k cc ngun c th gy ra
KB (2)
Gii quyt cc ngun c th gy ra
KB bng vic nhm, xo b (2)
Lp k hoch nghin cu chm (3.1)
Tin hnh phn tch lp li
cc mu i din cho cc
nng v/hoc cc dng
mu nu trong phm vi ca
phng php (3.1.2)
Tin hnh phn tch lp
li 10 ln cc mu i
din c ly t cc l
khc nhau (3.1.1)
Tp hp tt c cc KB thu c qua
nghin cu chm vo mt danh mc
Tnh KB qua
nghin cu chm
(3.1.2)
Lp k hoch nghin cu ng (3.2)
C mu chun
c chng
nhn khng ?
Tnh Rm t phn tch lp
li 10 ln trn cc mu t
mt l mu (3.2.1)
Kim tra nu Rm c khc 1 nhiu
khng (3.2.5)
Tnh u(Rm) (3.2.5)
Khng
C
C Khng
Phm vi ca phng
php c bao gm
nhiu khong nng
hay nhiu dng
mu hay khng ?
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 41
S dng d liu t
nghin cu sai s
th/ tin hnh thm
cc nghin cu thc
nghim (3.3.3.3)
Phm vi ca phng
php c bao gm
nhiu khong nng
hay nhiu dng mu
hay khng
Tnh Rs
v u(Rs)
(3.2.6)
Nghin cu mu
thm c
lng Rm
Tng hp KB thu hi a
ra R
v u(R) (3.2.8)
Tp hp tt c cc KB thu c qua nghin
cu chm vo mt danh mc (3.3)
Cc d
liu c sn
Tnh KB
(3.3.1, 3.3.2)
Thc hin cc th
nghim ruggedness
(3.3.3.1)
Cc thng s c
nh hng ng
k n kt qu
(3.3.3.1)
c lng KB t kt
qu cc th nghim
ruggedness (3.3.3.2)
Tnh KB tng hp t cc
KB qua nghin cu chm, thu
hi, KB nghin cu thm (4.1)
Tnh KB m rng (4.2)
Bo co v lu ti liu v KB
(5)
C
Khng
c
Tnh Rrep
v u(Rrep)
(3.2.7)
c
Khng
Tnh KB
(3.3.3.3)
Ch thch:
Ruggedness: sai s th
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 42
2. XC NH CNG THC TON HC TNH KT QU V CC NGUN
KHNG M BO
Mc 5 phn A trnh by chi tit cch thc a ra cng thc ton hc v cc ngun KB o. Cc
bc c bn xc nh cc ngun KB nh sau:
- Vit y cng thc tnh kt qu, bao gm c cc php o trung gian. Lit k cc tham s lin
quan ca phng php
- Nghin cu cc bc ca phng php v xc nh cc thng s khc nh hng n kt qu
- Cn nhc cc tham s m s nh hng n xc nh tham s
- Lit k cc phn b KB ca tng tham s u vo phn tch cc ngun trng lp.
3 qui tc:
- Loi b cc nh hng
- T hp cc nh hng ging nhau hoc ng thi
- Gi li cc nh hng tng t
Tm li cui cng mc ch ca phn ny l a ra mt danh mc cc ngun gy ra KB v c
th th hin qua s xng c
Mc ch ca phn ny lit k tt c cc ngun c th gy ra KB cho phng php. Bc ny
khng nht thit lin quan n vic nh lng cc thnh phn KB m ch nhm a ra cc ngun
KB. Theo EURACHEM th qui trnh xc nh cc ngun KB v mt s dng ngun KB
gm:
- Ly mu
- chch ca thit b
- iu kin o
- Cc nh hng ca mu
- Cc nh hng ca thit b tnh ton in t
- Cc nh hng ngu nhin...
3. NH LNG CC THNH PHN KB
Phn ny gm vic lp k hoch nghin cu thc nghim thu thp thng tin v d liu cho vic c
lng KB tng hp ca phng php. Hai phn nghin cu thc nghim c cp n l
nghin cu chm v ng. Cc nghin cu thc nghim phi c lp k hoch tt c cc
ngun KB lit k trong phn 2 c xc nh thch hp. Cc tham s lin quan khc c nh
gi t nhng nghin cu thc nghim ph hp. Phn ny tho lun v dng nghin cu thc nghim
v cc d liu thu c bng cch no tnh KB. Tuy nhin nghin cu thc nghim nu ra
phn ny ca hng dn cha chc l mt qui trnh xc nhn hiu lc phng php y m cn
c thm cc nghin cu khc v d nh nghin cu v tuyn tnh v gii hn pht hin.
Cc bc trong qu trnh nh lng KB bao gm:
3.1 Nghin cu chm
3.2 Nghin cu ng
3.3 Xc nh cc thnh phn KB khc m khng bao gm trong nghin cu chm v
ng. nh gi cc thnh phn KB khc
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 43
Cc bc c cp chi tit di y. Trng hp n gin nht l c lng chm t phn tch
lp li trn mt l mu v c lng ng t phn tch i din mt cht chun c chng nhn
(CRM). Cc nghin cu ny c nu trong 3.1.1 v 3.2.1. Tuy nhin nhiu phng php s phc tp
hn v cc phng php gii quyt v mt s tnh hung thng thng c nu trong 3.1, 3.2 v
3.3.
Tm li nghin cu thc nghim phi lun tp trung vo hai vn l xc nhn hiu lc ca
phng php v c lng KB. Nghin cu phi bao gm ton b phm vi ca phng php.
3.1 Nghin cu chm
Yu cu nghin cu chm ca phng php ph thuc vo phm vi ca phng php. Trng hp
n gin nht l khi phng php s dng phn tch mt dng mu vi mt nng phn tch
(xem 3.1.1) . Trng hp phc tp hn khi phm vi ca phng php bao gm nhiu dng mu
v/hoc nhiu nng phn tch (3.1.2).
3.1.1 Dng mu n
Nu phm vi ca phng php ch bao gm mt dng mu hoc mt nng phn tch th chm c
th c c lng t phn tch lp li trn cng mt dng mu. Thc hin t nht 10 ln phn tch
mu. Mi mt ln phn tch phi p dng y cc bc trong phng php bao gm c cc bc
chun b mu. Khng nn thc hin 10 ln phn tch trn 10 mu ca mt l vt liu. Nn ly 10 mu
trn cc l vt liu khc nhau v thay i mt s tham s.
Cc tham s la chn c th l:
- Hiu chun: nghin cu nn bao gm vic chun b chun hiu chun khc nhau vi cc dung dch
chun hiu chun t cc l khc nhau (Bao gm c dung dch s dng chun b dung dch hiu
chun);
- Thuc th: cc thuc th nn chun b t cc l khc nhau
- Ngi phn tch: thc hin nghin cu chm vi nhiu nhn vin hn l ch mt nhn vin
PTN.
KB qua nghin cu chm ca phng php, u(P) l lch chun s ca cc kt qu qua
nghin cu chm. Chuyn thnh lch chun tng i v d: u(P)/P l chia lch chun ca
cc kt qu mu cho trung bnh ca cc kt qu nghin cu chm.
3.1.2 Phm vi ca phng php bao gm cc dng mu
Trong mt s trng hp phm vi ca phng php bao gm cc di nng phn tch mt s khong
nng cho mt s dng mu. Trong nhng trng hp ny nghin cu chm phi c cn nhc
n i din ca cc dng mu trong phm vi ca phng php. C th s dng vic c lng
KB m bao ph cho tt c cc dng mu nu trong phm vi ca phng php nu c bng chng
rng cc KB l c th so snh c . Tuy nhin c th c trng hp nhiu dng mu v/hoc
nng phn tch cn phi c lng KB ring cho tng i tng, tng dng mu.
3.1.2. Trng hp mt nng phn tch, nhiu dng mu
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 44
Xc nh cc mu i din cho mi dng mu trong phm vi ca phng php. Nu phng
php c phm vi rng th c th khng nghin cu thc t nh th c m nghin cu lp
li bng ly mi dng mu mt mu i din. Trong nhiu trng hp ngi phn tch s
quyt nh s lng dng mu cn nghin cu, phn tch. Phn tch lp li i vi mi mu.
Cn phi thc hin phn tch lp li 10 ln cho mi dng mu. Tuy nhin nu i tng mu
a dng th vic nghin cu thc nghim nh vy l khng thc t. Ph thuc vo phng
php, t nht phi thc hin th nghim lp li 4 ln cho mt i tng mu. Th nghim lp
li cho mi mu nn tin hnh i vi cc mu cc l khc nhau (phn 3.1.1).
Tnh ton lch chun ca cc kt qu thu c cho mi mu. Nu lch chun khng
khc nhau ng k th c th dng cng thc tnh lch chun pool (ct.3.1) c lng
mt chm m c th p dng cho cc dng mu qua nghin cu chm. Nhng nu mt
trong s cc lch chun nghin cu c gi tr khc so vi cc lch chun khc th cn
phi tnh KB ring cho tng i tng mu.
Tu thuc vo s khc nhau gia cc lch chun quyt nh s dng lch chun pool
hay nghin cu th nghim thng k (F-tests)
ct.3.1
Trong :
s1: lch chun tnh cho dng mu 1
n1: s ln th lp li cho dng mu 1
3.1.2.2 Trng hp mt dng mu, nhiu khong nng phn tch
chm phi c nghin cu ti cc nng m c th bao ph ton b cc khong nng
trong phm vi ca phng php. Nu khng c mu i din cho cc khong nng thch
hp nghin cu phn tch th s dng cc mu thm nghin cu. Ch l t nht phi c
3 khong nng c nghin cu (v d nh khong nng thp, trung bnh v cao). vi t
nht 4 ln th nghim lp li cho mi khong nng .
Tnh ton lch chun v lch chun tng i ca cc kt qu ca tng mu. Nu khng
c s khc nhau ng k gia cc lch chun tng i ca tng mu th c ngha l
chm l tng ng cho nng phn tch. Trong trng hp cc lch chun tng i c
th c tnh bng pool a ra mt c lng n m c th p dng cho khong nng
khi nghin cu chm (ct.3.2). Do thng khng tm thy chm l khng t l vi
nng ca cc khong nng trong phm vi ca phng php k c khi phm vi nng
l rng. C th c trng hp cn tnh KB ring cho mt khong nng v d nh khi
khong nng thp th c th tnh t l khng cn.
Nh cp trong 3.1.2.1 th chm khi c s khc nhau gia cc lch tng i c
tnh cho cc khong nng . t nht cn phn tch nghin cu 5 khong nng v cc
lch chun ca cc kt qu nghin cu l i din cho tng khong nng s cho chng ta
thy mi lin quan gia chm v nng . Nu cc kt qu tuyn tnh th c ngha l
( )
,
_
+ +
+ +
... ) 1 ( ) 1 (
... ) 1 ( 1
2 1
2
2 2
2
1 1
n n
xs n xs n
s
pool
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 45
chm t l cho cc mc nng v c th dng cng thc pool. Nu nghin cu 5 mc nng
v ngi phn tch cn xc nh khi no th s khc nhau gia cc lch chun tng i
l ng k. Thng s c cn nhc khi to ra chm c tho lun trong mc 3.1.2.1
c lng lch chun tng i bng pool theo cng thc sau:
ct.3.2
Trong RSD
1
l lch chun tng i tnh cho cc mu nng 1, n
1
l s ln th lp
li i vi mu
3.1.2.3 Phn tch nhiu dng mu v nhiu khong nng
Nu phng php s dng phn tch c phm vi bao gm nhiu dng mu v nhiu khong
nng th c th khng thc hin vic c lng n v KB qua nghin cu chm.
cho cc dng mu trong phm vi ca phng php. chm c th khng t l cho cc mc
phn tch cc khong nng v ln ca chm c th khc nhau gia cc dng mu.
Hng dn nh gi mi quan h gia chm, dng mu v khong nng phn tch
c cp trong 3.1.2.1 v 3.1.2.2. Nghin cu thc nghim c m t 2 mc trn cng
thch hp nghin cu cho trng hp ny.V d nu mt dng mu m phn tch nhiu
khong nng tin hnh nghin cu nh m t trong 3.1.2.2. Nghin cu ny s a ra mi
lin h chm v khong nng phn tch. nu khong nng l tng ng cho cc
dng mu th nghin cu c trnh by trong 3.1.2.1 xc nh nh hng ca mu ln
chm
Cn tin hnh nghin cu bng th nghim lp li cho tng mu cc l khc nhau
i vi cc phng php m phm vi ca phng php bao gm nhiu dng mu v nhiu
khong nng th cn thit phi thit lp mt chng trnh nghin cu c th v thch hp
c th m bo tnh ton c KB cho php th mt cch y v chnh xc.
Sau y l mt s trng hp c th xy ra khi nghin cu phng php v cch gii quyt
- chm l t l qua mc phn tch theo phm vi nng v c lp vi mi dng mu.
Trong trng hp ny chm c c lng cho tng mu nghin cu v c chuyn
thnh lch chun tng i s dng cng thc 3.2. chnh l c lng KB
bng nghin cu chm qua lch chun tng i (v d, u(P)/P c th p dng cho
tt c cc mu trong phm vi ca phng php.
- chm t l gia cc nng phn tch nhng khc nhau ln gia cc dng mu. Trong
trng hp ny lch chun tng i tnh ti cc nng khc nhau cc mu c lp
c th s dng cng thc 3.2 c lng cc chm ring cho tng dng mu. iu
ny c ngha l cn c lng KB tng hp cho tng loi mu.
- chm l khng t l i vi cc mc nng . Nghin cu thc nghim c th ch ra
rng chm l t l ti khong nng ch mt gii hn mt khong nng hoc
khng khong no. Thm vo c th khc nhau gia cc loi mu. Trong trng hp
ny c th dng cng thc pool cho c lng mt vi chm c u(P) cho tng nhm
( )
,
_
+ +
+ +
... ) 1 ( ) 1 (
... ) 1 ( 1
2 1
2
2 2
2
1 1
n n
xRSD n xRSD n
RSD
pool
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 46
mu v hoc cho tng khong nng . V d mt phng php c th quan st c cc
nng thp th lch chun tng t cho cc dng mu v gi nguyn khong gii hn
nh ca nng . iu ny ch ra rng chm l c lp cho c mu v khong nng
phn tch. Trong trng hp ny cc lch chun quan st c cho tng mu c th s
dng cng thc pool ct.3.1 c lng chm n m c th p dng cho cc nhm
mu c th.
Tm li, khi phm vi ca phng php bao gm mt phm vi cc loi mu v cc khong
nng th mc tiu c lng chm nn s dng cng thc pool. Nu chm l t l
vi nng phn tch th c lng chm nn s dng cng thc pool nh lch chun
tng i s dng cng thc 3.2. Nu chm c nhn thy l c lp ca nng phn
tch th c lng nn dng dng cng thc lch chun theo cng thc 3.2. Nh tho
lun trong mc 3.1.2.1 v 3.1.2.2, quyt nh p dng c lng chm bng cng thc no
l do ngi phn tch. Cc thng s c cn nhc s dng cc th nghim thng k thch
hp c nu trong cc phn trn.
3.2 Nghin cu ng
Trong hng dn ny th nghin cu ng chnh l nghin cu thu hi ca phng php
v d t l gia gi tr thu c qua phn tch vi gi tr qui c (gi tr mong i). T l
cng gn ti 1 th tc l t c chch nh nht trong phng php. thu hi c th
c nh gi theo mt s cch v d phn tch da vo mu chun c chng nhn (CRMs)
hoc mu thm (spike). Nghin cu thc nghim yu cu nh gi thu hi v KB
ph thuc vo phm vi ca phng php, kh nng thc hin v mu chun c chng nhn.
thu hi cho mt mu c th R c th c tnh ton nh tng hp ca 3 thnh phn:
- m R l c lng thu hi trung bnh ca phng php v d nh phn tch mu CRM hoc
mu thm. KB ca m R l tng hp KB trong cc gi tr lin quan (nh KB
ca gi tr ca CRM trong giy chng nhn) v KB ca cc gi tr th nghim (nh
lch chun ca trung bnh cc ln th nghim lp li). Phn b ca m R ti KB tng
ca phng php ph thuc vo mc khc vi 1 v s hiu chnh p dng.
- R
s
l s hiu chnh c tnh t s khc nhau trong thu hi ca mu thc vi thu hi
ca vt liu (mu CRM, mu thm) dng c lng m R
- R
rep
l s hiu chnh c tnh th hin s khc nhau gia mu thm v mu thc khi phn
tch.
C 3 yu t c tng hp a ra thu hi cho mu c th l R = m R x R
s
x R
rep
.
KB ca R l u(R) c phn b t 3 ngun u( m R ), u(R
s
), u(R
rep
). Tnh ton tng thnh phn
v KB ca tng thnh phn trn ph thuc vo phm vi ca phng php v CRM. Cc
bc tin hnh nghin cu c tm tt trong hnh 3
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 47
Bn cnh vic nghin cu mu thm cn c cc
phng php khc nh gi Rm
c cp trong 3.2.3 v 3.2.4
Bt u
C mu chun
c chng
nhn khng?
Tin hnh phn tch
lp li trn 10 mu
(3.2.1)
Phn tch mu
thm vi 1 loi
mu ai din vi
mt nng i
din (3.2.2)
Tin hnh phn tch
lp li trn 10 mu
c lng Rrep v
u(Rrep)
Tnh ton Rm
v u(Rm)
(3.2.1, 3.2.2)
Kim tra nu Rm
c khc 1 nhiu
khng (3.2.5)
C hiu
chnh kt qu
thu hi?
Tnh ton u(Rm)'
trng hp 2 (3.2.5)
C
Khng
C C
Tnh ton u(R
m
)'
trng hp 3 (3.2.5)
Tnh ton u(R
m
)'
trng hp 1 (3.2.5)
Phm vi phng php
bao gm cc khong
nng v/hoc loi
mu
c lng Rs v
u(Rs) (3.2.6)
Tng hp u(Rm)',
u(Rs) v u(Rrep)
c u(R) (3.2.8)
Kt thc
Khng
Khng
C
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 48
3.2.1 c lng m R v u( m R ) s dng CRM
Xc nh mt mu chun c chng nhn (CRM) vi mt dng mu v phn tch i din
mt nng ca mu m s tr thnh phm vi nng th nghim thng thng trong phm
vi qui nh ca phng php. Phn tch t nht 10 ln trn mu chun ca mt l mu (trng
hp kh thc hin 10 mu trn cng mt l th c th cc l khc nhau nhng nn thc hin
trong cng khong thi gian). Mi mu phi tin hnh y cc bc phn tch. Tnh ton
thu hi trung bnh m R theo cng thc:
CRM
obs
m
C
C
R ct.3.3
trong obs C l trung bnh ca th nghim lp li ca CRM v C
CRM
l gi tr c chng
nhn ca CRM
Tnh ton KB ca thu hi u( m R ) theo cng thc:
( )
2
CRM
2
2
) (
,
_
,
_
CRM obs
obs
m m
C
C u
C n
s
R R u ct.3.4
trong s
obs
l d lch ca cc kt qu t phn tch lp li CRM, n l s ln th lp li v
u(C
CRM
) l KB chun ca gi tr c chng nhn ca CRM.
Cc tnh ton trn cung cp mt c lng thu hi trung bnh v KB ca thu hi.
Phn b ca thu hi v KB ca n ti KB tng hp ca phng php ph thuc
vo mc chnh lch so vi 1 v c p dng h s hiu chnh hay khng. Mc 3.2.5 s
hng dn cch c lng phn b ca thu hi ti KB tng.
3.2.2 c lng m R v u( m R ) s dng nghin cu mu thm ti mt nng trn mt
dng mu
Nu khng c mu chun c chng nhn (CRM) th m R v u( m R ) c th c lng t
nghin cu mu thm v d nh phn tch vt liu c nghin cu t trc. Mu thm c
th c chun b theo cch lm sao c th cng i din cho mu thc cng tt. C mt s
cch tip cn cho trng hp ny, ph thuc vo i tng mu th l mu trng tc l khi
mu th khng cha hm lng cht phn tch.
3.2.2.1 Thm vo mu trng mt lng mu nht nh
Tim mt lng mu vi nng cht cn phn tch thch hp vo i tng mu th bit
l khng cha hm lng cht phn tch. Thc hin th nghim trn 10 mu c tim.
m R c tnh nh sau:
spike
obs
m
C
C
R ct.3.5
trong trong obs C l trung bnh ca th nghim lp li ca mu thm v C
spike
l nng
ca mu thm.
Tnh ton KB ca thu hi u( m R ) theo cng thc:
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 49
( )
2
spike
2
2
) (
,
_
,
_
spike obs
obs
m m
C
C u
C n
s
R R u ct.3.6
3.2.2.2 Thm vo mu c cha nng cht phn tch mt lng cht phn tch
Nu khng c mu trng th chun b mu thm v tim vo mu c cha nng cht phn
tch. Phn tch mu thm lp li v m R c tnh nh sau:
spike
native obs
m
C
C C
R
ct.3.7
trong native C l nng phn tch trong mu khi cha thm mt lng cht phn tch. Ch
rng chng ta khng quan tm ti s khc nhau gia nng ca mu thm v mu khng
thm, native C khng i din cho gi tr thc ca nng phn tch cho mu khi cha thm.
KB c tnh nh sau:
2
2
2 2
) (
) (
/
) (
,
_
+
spike
spike
native obs
native obs
m m
C
C u
C C
s n s
R R u ct.3.8
trong s
native
l lch chun ca trung bnh ca cc kt qu phn tch lp li ca cc mu
cha thm
3.2.2.3 Thm vo mu trng (mu bit l khng cha hm lng cht phn tch) mt lng
mu
Nu thc t chun b phn mu thm ng nht cho cc mu nh l khng thc hin c th
cc mu thm c lp c chun b. Chun b cc mu thm vi khi lng tng t nhau
v thm vo mu th khng cha hm lng (mu trng). Khuyn ngh l nn phn tch t
nht l trn 10 mu. thu hi tnh bi cng thc
spike
obs
m
m
m
R ct.3.9
trong obs m l khi lng trung bnh thm thu c t cc mu phn tch v m
spike
l
trng lng ca phn thm vo mi mu. ) ( m R u c tnh theo cng thc:
2
2
2
) (
) (
,
_
,
_
spike
spike
obs
m
m m
m
m u
m n
s
R R u
obs
ct.3.10
trong Sm
obs
l lch chun ca cc kt qu thu c t cc mu thm, n l s lng cc
mu phn tch thm v u(m
spike
) l KB trong tng lng thm vo mi mu.
3.2.2.4 Thm cc phn mu vo mu c cha hm lng cht phn tch
Nu cc mu thm c chun b t mu thc vi cc nng phn tch th tnh hung l
phc tp hn. thu hi cho mi mu R
m(i)
c tnh theo cng thc:
) (
) (
) (
i spike
native i obs
i m
C
C C
R
ct.3.11
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 50
trong C
obs(i)
l nng phn tch quan st c t mu i v C
spike(i)
l nng mu thm
c thm vo mu i
thu hi trung bnh m R c tnh theo cng thc:
n
i i spike
native i obs
m
C
C C
n
R
1 ) (
) ( 1
ct.3.12
KB ) ( m R u c tnh theo cng thc:
1
1
]
1
1
1
]
1
+
1
1
]
1
n
i
i spike
i spike
native i obs
native
n
i i spike
i obs
i spike
m
C u
C
C C
n
C u
C n
C u
C n
R u
1
2
) (
2
) (
) (
2
2
1 ) (
2
) (
) (
2
) (
) (
1
) (
1 1
) (
1 1
) (
ct.3.13
Do nu cc iu kin c p ng th cng thc 3.13 v 3.14 c th c s dng:
- u(C
spike(i)
) phi nh hn u(C
obs(i)
) v u(C
native
). Thng trng hp ny do vic thm t
c c s ca mt dung dch hoc khi lng phn tch bit. Cc KB lin quan
vi hot ng thng nh hn so vi KB lin quan vi quan st ca tng phn tch
trn mt mu.
- lch chun ca cc gi tr C
spike(i)
l nh so vi trung bnh ca cc gi tr C
spike(i)
. Nu
iu kin ny c p ng th trung bnh ca cc gi tr C
spike(i)
, spike C s dng trong tnh
ton. Thng trong trng hp ny nghin cu thu hi ti mc n s dng nh
lng thng thng ca mu trong s so snh vi mu thm
- c lng ca u(C
obs(i)
) l ng dng. Trong trng hp trung bnh ) (
) (i obs
C u c th s
dng. Trng hp nu mi mu c thm vo cng nng th tt c cc gi tr ca
C
obs(i)
l ng dng th t ln
2
2
) (
) (
) (
1
) (
native
i obs
spike
m C u
n
C u
C
R u + ct.3.14
3.2.3 c lng m R v ) ( m R u bng so snh vi phng php chun
m R c th c nh gi bng phn tch mt dng mu s dng phng php c nh
gi v k thut v tnh KB. Ch l cn thc hin th nghim vi mi phng php t
nht l 5 ln. m R c tnh bi:
dard s
method
m
C
C
R
tan
ct.3.15
trong method C l trung bnh cc kt qu s dng phng php ang nghin cu cn dard s C tan
l trung bnh ca cc kt qu s dng phng php chun. KB ca thu hi ) ( m R u
theo cng thc:
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 51
2
tan
tan
2
2
) (
) (
,
_
,
_
dard s
dard s
method
method
m m
C
C u
C n
s
R R u ct.3.16
trong s
method
l lch chun ca cc kt qu thu c s dng phng php ang nghin
cu, n l s th nghim lp li cn u(C
standard
) l KB lin quan vi phng php chun.
3.2.4 Cc phng php c lng m R v ) ( m R u khc
Trong trng hp khng c sn CRMs hoc cc phng php chun v mu thm khng
chun b c th c th chn cc phng php khc nghin cu thu hi. K thut yu
cu chung cho yu t nh gi trong phn ny ca phn tch v c th ch s dng mt ch s
ca KB lin quan ti KB lin quan ti thu hi. Nu cc kt qu ch ra rng
KB lin quan ti thu hi ca phng php l mt phn b ng k ti tng KB ca
php th th cn phi c cc nghin cu thm c th a ra c c lng tt hn. K
thut ny bao gm:
3.2.4.1 Nghin cu hot ng chit
Mt k thut l ti chit cc mu di cng iu kin nghin cu hoc vi cc h thng chit
mnh hn (v d dung dch chit mnh hn). So snh tng phn tch chit di iu kin
thng ca phng php v di iu kin thay i (tng chit ban u cng tng chit bi
ti chit). m R l t l ca hai phn chit. Nu ti chit t c s dng cng cc iu kin
nh ln chit ban u th s khc nhau gia thu hi thc v gi tr gi nh l 1 c bit
n t nht l 1 - m R . S khc nhau c th ln nh chit lp li di cng cc iu kin c th
khng nh lng thu hi tng cho mu th. Ch l KB ) ( m R u lin quan vi gi tr
gi nh ca m R =1 c lng nh (1 - m R ). Nu chit lp li c tin hnh s dng mt h
thng chit mnh hn, tin cy v s khc nhau gia m R v gi nh gi tr ln hn 1 tt
hn l chit lp li s nh lng c thu hi ca php phn tch. Trong trng hp ny
) ( m R u c c lng nh (1 - m R )/k, trong k l h s ph m c th s dng tnh
ton KB m rng.
Trong cc trng hp trn th gi nh rng m R tng ng 1 v KB c c lng
theo . Do liu c cn thit phi theo cc bc trong phn 3.2.5.
Cc k thut khc kim sot qu trnh chit vi thi gian v s dng cc thng tin lm
mnh l bao nhiu hm lng c chit.
3.2.4.2 Phn tch CRM "worst case"
Trng hp mu CRM c sn cho mt mu bit nhng kh chit v phn tch so vi
mu thc, thu hi thu c t CRM c th cung cp c lng khng c tt lm "worst
case" m da vo thu hi ca mu thc. Nu mu c bit r rng so vi mu th th l
do gi nh rng thu hi cho mu th l gn 1 hn l R
CRM
thu hi ca CRM. iu
ny tng t nh ly R
CRM
nh i din gii hn thp nht ca phn b hnh tam gic. Nh
c lng ban u, m R gi nh l tng ng 1 vi KB ) ( m R u
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 52
6
1
) (
CRM
m
R
R u
ct.3.17
Ch thch l khng c bng chng ch ra l khi khong 1 - R
CRM
thu hi cho cc mu th l
nm trn mt ng c th c gi nh phn b hnh ch nht. ) ( m R u = 3 / 1
m
R
Nu gi nh l m R v ) ( m R u c tnh giai on ny th khng cn theo cc bc trong
3.2.5.
3.2.5 c lng phn b ca m R ti u(R)
Gi nh c lng thu hi m R v KB ) ( m R u c a ra s dng mt phng php
nu trong 3.2.1 ti 3.2.4 c 3 trng hp ny sinh:
- T m R tnh ) ( m R u khng khc ng k so vi 1 nn cc kt qu khng cn hiu chnh cho
thu hi
- T m R tnh ) ( m R u khc 1 ng k nn cc kt qu c hiu chnh cho thu hi
- T m R tnh ) ( m R u khc 1 nhng khng hiu chnh cho thu hi
Tnh ton th nghim thng k t s dng cng thc sau:
) (
1
m
m
R u
R
t
ct.4.18
Nu bc t do lin quan vi ) ( m R u c bit so snh t vi 2 gi tr bin, t
crit
tng ng
s bc t do ti mc tin cy l 95%. Nu t t hn gi tr ti hn th m R khng khc 1 ng k
Nu bc t do lin quan vi ) ( m R u khng bit n v d nu c mt phn b t KB ca
gi tr oc chng nhn ca mu chun, so snh t vi k h s ph c s dng tnh
KB m rng
Nu k R u R m m < ) ( / 1 thu hi khng khc 1 ng k
Nu k R u R m m > ) ( / 1 thu hi khc 1 ng k
Trng hp 1
Cc s ch th nghim ch ra rng KB l khng khc 1 ng k nn khng c l do
hiu chnh cc kt qu phn tch cho thu hi. Do c mt KB lin quan vi c
lng m R nh th nghim khng th phn bit cc khong gi tr vi 1.0. Nu th nghim
thng k c so snh vi t
crit
khong 1 t t
crit
x ) ( m R u . KB lin quan vi thu hi
trong trng hp ny l )' ( m R u c tnh bng cng thc:
96 . 1
) (
) (
' m crit
m
R u t
R u
ct.3.19
Nu th nghim thng k c so snh vi h s ph k, khong l 1 t k x ) ( m R u .
i thnh lch chun tng i chia ) ( m R u cho )' ( m R u bng gi tr gi nh m R .
Trong trng hp ny m R = 1 nn lch chun tng ng vi lch chun tng i
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 53
Trng hp 2
Nh s hiu chnh c p dng, m R r rng bao gm trong tnh ton kt qu. ) ( m R u l bao
gm tnh ton KB tng hp di dng ) ( m R u / m R
Trng hp 3
Trong trng hp thu hi l khc ng k vi 1 v thng k nhng thng phng php l
khng p dng s hiu chnh. (v d m R c coi tng ng 1). KB phi c tng
ln tnh chnh xc thu hi l khng c hiu chnh. KB o tng ln v ' )' ( m R u
tnh theo cng thc:
2
2
' '
) (
1
) ( m
m
m R u
k
R
R u +
,
_
ct.3.20
trong k l h s ph m s c s dng tnh KB m rng.
' )' ( m R u c din t nh mt lch chun tng i bng cch chia cho gi tr gi nh
ca m R nh trng hp 1
3.2.6 c lng R
s
v u(R
s
) t nghin cu mu thm
Khi phm vi phng php bao gm nhiu dng mu v nng phn tch th thm vo thut
ng KB c yu cu thm cc tnh ton khc v thu hi ca mt mu c th/mu
thc so vi vt liu s dng c lng m R . C th nh gi bng th lp li mu thm vi
cc khong i din ca dng mu v nng phn tch. S lng ca dng mu v mc
th nghim v s cc th nghim lp li cho mi dng mu ph thuc vo phm vi ca
phng php. Cc hng dn p dng tng t nh nghin cu chm c tho lun trong
lc 3.1. Tnh ton thu hi trung bnh cho tng mu cng thc 3.12. R
s
gi thit l tng t
1.0 do KB cng c tnh n. iu ny ch ra cc thu hi trung bnh thu c t
cc mu thm khc nhau. KB u(R
s
) l lch chun ca trung bnh thu hi thu c
ca tng dng mu.
3.2.7 c lng R
rep
v u(R
rep
) t nghin cu mu thm
R
rep
gi nh chung theo mt cng thc ch ra rng thu hi t mt mu thm i din cho
thu hi quan st c cho mu phn tch. KB u(R
rep
) l mt i lng o KB
lin quan vi s gi nh v d s khc nhau c th c gia R
rep
vi 1.
nh gi phc tp i din mu thm l i din cho cc mu th thc khc nhau t dng
mu ny ti dng mu khc vi phng php nghin cu c s dng. Trong nhiu trng
hp n c th gy tranh lun rng i din tht tt cho mu thc ly v d trong mu nc khi
phn tch thnh phn thng ho tan trong mu. Thm vo nu phng php bao gm tng
cc phn ho tan hoc b hu ca mu v d tro ho c th khng c l do tin rng mu
thm c th th hin s khc nhau t phn tch.. Do cc vn ny dinh lm cho cc mu
phc tp hn v khi phng php bao gm s chit hn l tng ph hu hoc ho tan. Cc
cch tip cn thch hp nh gi vic thc hin cc mu thm thay cho mu thc bao gm
s kim sot vic chit ca mu thm v cc phn tch t nhin vi cng thi gian v so snh
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 54
thu hi mu thm vi thu hi t i din mu CRM. Do c th khng thch hp trong
mi trng hp. Nu bng chng nghin cu thc nghim c tin hnh mt cch thch hp
trn mu thm khng th thc hin c th nghin cu v hoc gi nh l c th to c.
Theo l tng th R
rep
nn c nh gi bng phn tch mu chun (k c khi nu khng c
kh nng so snh trc tip vi mu thc) v so snh thu hi thu c vi cc kt qu
nghin cu mu thm. KB u(R
rep
) c c lng bng cng thc:
2 '
2
) ) ( (
1
) (
rep
rep
rep
R u
k
R
R u +
,
_
ct.3.21
Khi k l h s ph c s dng tnh KB m rng v u(R
rep
)' l KB lin quan vi
c lng Rrep. Cch tip cn tt nht v trc tip nht l s dng mu thm bng CRM. v
so vi thu hi thu c vi kt qu t phn tch mu chun khng thm. Trong trng hp
ny R
rep
c tnh theo cng thc:
) (
) ( ) (
CRM obs
CRM
spike
CRM obs spike obs
rep
C
C
C
C C
R
ct.3.22
trong ) (spike obs C l trung bnh nng thu c t phn tch lp li cc mu thm CRM,
obs(CRM) C l trung bnh nng thu c t phn tch lp li mu khng thm CRM, C
spike
l
nng phn mu thm v C
CRM
l nng mu chun c chng nhn. KB u(R
rep
)'
thu c s khc nhau theo cng thc sau:
2
2
) ( ) ( ) (
) ( ) (
2
) ( ) (
) (
'
) (
) (
) (
) ( ( (
) (
,
_
,
_
,
_
,
_
spike
spike
CRM
CRM
spike obs CRM obs CRM obs
spike obs CRM obs
CRM obs spike obs
spike obs
rep rep
C
C u
C
C u
C C C
C u C u
C C
C u
R R u ct.3.23
Trong trng hp ny chng ta ch c thng tin v s phn tn ca cc kt qu thu c cho
cc gi tr trung bnh C
obs(spike)
v obs(CRM) C . KB lin quan c a ra di dng lch
chun ca gi tr trung bnh ca cc nng quan st c trong tng trng hp. Ch thch
l cng thc trn nu nghin cu mu thm c da vo cch thc phn tch lp li ca mu
thm s dng CRM. Nu nghin cu da vo cc phn tch mt s lng cc phn mu c
lp ca CRM (vi khi lng tng t) tt c cc mu thm ti nng nht nh (xem phn
3.2.2.4) cng thc 3.22 v 3.23 c thay bng:
) (
) ( ) (
CRM obs
CRM
spoke
CRM obs spike obs
rep
C
C
C
C C
R
ct.3.24
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 55
2
2
2
) ( ) ( ) (
) ( ) (
2
) ( ) (
) (
'
) (
) (
(
) ( (
(
) (
,
_
,
_
,
_
,
_
spike
spike
CRM
CRM
spike obs CRM obs CRM obs
spike obs CRM obs
CRM obs spike obs
spike obs
rep rep
C
C u
C
C u
C C C
C u C u
C C
C u
R R u ct.3.25
trong ) (
) (spike obs
C u l trung bnh ca cc KB lin quan vi tng gi tr ca C
obs(spike)
bng cch cn bc hai ca bnh phng c gi tr ca C
obs(spike)
, spike C l trung bnh cc nng
phn mu thm thm vo tng mu th v ) (
spike
C u l trung bnh KB lin quan vi
tng gi tr ca C
spike
.
Nu khng c CRM th nghin cu s c da trn thng tin c sn v d nh cc nghin
cu c ban hnh.
3.2.8 Tnh ton R v u(R)
thu hi c th ca mt mu R c tnh bng
rep s
m R R R R . Do t R
s
v R
rep
l gi
nh chung tng ng vi 1, R= m R . Gi tr m R v ) ( m R u s dng ph thuc vo m R khc
1 mc no v mt s hiu chnh cho kt qu ca mt mu c th c p dng. iu ny
c th hin trong mc 3.2.5. KB lin quan vi R, u(R) tnh theo cng thc:
ct.3.26
Do nu Rs = Rrep = 1 cng thc 3.26 c chuyn thnh:
ct.3.27
3.3 nh gi cc ngun khc ca khng m bo
Cc ngun gy ra KB khng bao gm trong nghin cu chm v ng yu cu
phi c nh gi ring. V d, mt phng php yu cu rng mu c lm nng ti mt
nhit no . Phng php ny c th c th phm vi chp nhn v nhit lm nng v
d 100t0.5
0
C. Qua qu trnh nghin cu chm th nhit c th khng to ra sai khc
ng k ti ton b khong nhit chp nhn trong yu cu ca phng php. S la chn
ny c th khng c yu cu trong phng php cho mt thng s c th. Trong cc
trng hp ny th s nh hng ln kt qu phn tch t vic thay i trong thng s cn
c nh gi. Cc ngun khc ca KB m c th cn c nh gi bao gm:
- tinh khit ca chun v d nu mt l ca mu chun c s dng chun b cc
chun s dng nghin cu chm
- Hiu chun dng c thu tinh v d nu mt pipet c s dng trong sut qu trnh
nghin cu chm
2
2 2
) (
) ( ) (
) (
,
_
,
_
,
_
ref
ref
s
s
m
m
R
R u
R
R u
R
R u
Rx R u
2 2
2
) ( ) (
) (
) (
ref s
m
m
m R u R u
R
R u
x R R u + +
,
_
+ + +
Tnh ton cc s khc nhau cho tt c 7 tham s v lit k chng theo th t ln dn. Ch l
vic ch ra cc s khc nhau l khng quan trng. Nu phng sai trong 1 hoc 2 tham s l
nh hng ti php phn tch th s khc nhau ca chng v cn bn ln hn cc tham s
khc. xc nh phng sai trong cc tham s c nh hng ng k ti kt qu th nghim
c s dng nu tnh ton trn ra c kt qu khc vi 0. Cc bc tin hnh nh sau:
a ra chm ca mt t th nghim nh lch chun, t phn tch lp li ca mu i
din trong mt thi gian ngn
Tnh ton thng k t [12]
s
Dx n
t
i
2
Khi c lng chm ca phng php trong phn 1 trn th n l s ln th nghim thc
nghim c tin hnh ti mt mc ca tng tham s (n=4 theo thit k c trnh by
trn), v D
xi
tnh ton khc tham s x
i
So snh t vi 2 gi tr bin, t
crit
cho N - 1 bc t do ti 95% mc tin cy khi N l s cc th
nghim s dng c lng s.
Trng hp 1: nu t nh hn t
crit
v s khc nhau l khng ng k so vi 0. Vy cc phng
sai trong tham s khng c nh hng ti phng php
Trng hp 2: nu t ln hn t
crit
s khc nhau l ng k so vi 0. Vy cc phng sai
trongtham s c nh hng ti phng php
Trong c 2 trng hp u c KB lin quan ti tham s. Cc phng php c lng
KB c nu di y
3.3.3.2 Tnh ton KB cho cc tham s trng hp 1
Mc d nghin cu sai s th ch ra rng cc phng sai trong tham s khng nh hng
ti phng php (v d thay i cc kt qu khi thay i tham s l khng khc ng
k so vi 0). th nghim s nh hng c th khng phn bit gia cc gi tr trong
khong 0 t n s t
crit
/ ) 2 ( . KB lin quan vi kt qu cui cng y theo tham s x
i
tnh theo cng thc:
test
real crit
i
n
s t
x y u
96 . 1
2
)) ( (
trong
real
l s thay i trong tham s m c mong ch khi phng php thc hin di
s kim sot thng ngy v
real
l s thay i trong tham s c xc nh c th trong
nghin cu th nghim sai s th. thut ng ny yu cu c tnh vo thc t rng khi thay
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 59
i mt tham s s dng trong nghin cu sai s th c th ln hn nhng quan st thng
thng khi thc hin phng php.
Nu s nh hng l t l vi nng phn tch th KB nn c chuyn thnh lch
chun tng i bng cch chia c lng trung bnh t cc ln phn tch lp li ca mu s
dng phn b chun hoc nu khng c sn th ly trung bnh ca 8 kt qu nghin cu sai s
th. Do nu cc nng phn tch c lp th KB c din t nh lch chun.
3.3.3.3 Tnh ton KB cho cc tham s trng hp 2
tnh ton KB o cho i lng c th, x
i
c lng h s nhy c
i
vf KB ca i
lng u(x
i
) yu cu:
c lng u(x
i
): v d mt phng php tuyn b l mu phi c trng ct trong 120 pht.
Ngi phn tch c lng rng phng sai trong thi gian trng ct p dng trong phng
php l t 5 pht. KB trong thi gian trng ct l 2.9 pht. Gii hn kim sot c th
c thit lp cho i lng m bo rng phn b kt qu ti KB tng l c th chp
nhn. Nu mt i lng c kim sot theo yu cu k thut (nh yu cu v nhit nh
4 t 1
0
C), gii hn yu cu k thut i din KB lin quan vi i lng v c th chuyn
thnh lch chun.
c lng c
i
: nu th nghim sai s th ch ra rng i lng c nh hng ng k ti kt
qu, h s nhy c th c c lng t cc kt qu nghin cu:
parameter in Change
result in change Observed
c
i
= Quan st thay i kt qu/ thay i tham s
Nu i lng c tm thy l ngun ng k gy ra KB hoc nu yu cu c lng
tt hn nh hng ca i lng ti kt qu th cn thc hin cc nghin cu thc nghim.
nh gi t l thay i ca kt qu vi thay i trong i lng bi s lng cc thc nghim
vi i lng ti khong cc gi tr khc nhau. Biu kt qu chng li gi tr ca i lng.
Nu s quan h l tuyn tnh th h s nhy l tng ng vi dc ca ng gn nht
Tnh ton KB trong kt qu cui cng theo i lng xi, u(y(x
i
)) s dng cng thc
i i i
c x u x y u ) ( )) ( (
Nu nh hng l t l i KB thnh lch chun tng i bng cch chia u(y(x
i
)) cho y
trong y l kt qu thu c ca i lng ti gi tr c th trong phng php.
4. TP HP CC KB THNH PHN V TNH KB TNG HP,
KB M RNG
c trnh by trong mc 8 ca Phn A
5. BO CO KB
c trnh by trong mc 9 ca Phn A
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 60
PH LC B. NH NGHA
CC NH NGHA CHUNG/ GENERAL
B.1 chnh xc ca php o/ Accuracy of measurement
Mc gn nhau gia kt qu o v gi tr thc ca i lng o [H.4].
Ch thch:
1. chnh xc l mt khi nim nh tnh
2. Thut ng chm khng dng cho chnh xc
B.2 chm/ Precision
Mc gn nhau gia cc kt qu th nghim c lp nhn c trong iu kin qui
nh
Ch thch:
1. chm ch ph thuc vo phn b ca sai s ngu nhin v khng lin quan
ti gi tr thc hoc gi tr xc nh.
2. Thc o chm thng c th hin bng phn tn v c tnh ton
nh l lch chun ca cc kt qu th nghim. chm cng thp th
lch chun cng ln.
3. Cc kt qu th nghim c lp c ngha l nhng kt qu nhn c theo
cch khng b nh hng bi bt c kt qu no trc trn i tng th
nh nhau hoc tng t nh nhau. Thc o nh lng ca chm ph
thuc ch yu vo cc iu kin qui nh. iu kin lp li v iu kin ti lp
l nhng tp hp c th ca cc iu kin bt buc.
B.3 Gi tr thc/ True value
Gi tr ph hp vi nh ngha ca mt i lng ring bit cho [H.4].
Ch thch;
1. Gi tr thc l gi tr t c bng mt php o hon ho
2. Cc gi tr thc khng xc nh c trong thc t
B.4 Gi tr thc quy c/ Conventional true value
Gi tr quy cho mt i lng ring bit v c chp nhn, i khi bng tho c, c
khng m bo ph hp vi mc ch nh [H.4].
V d:
a Gi tr c th hin bng mt chun chnh mt a im xc nh c th
c ly lm gi tr thc qui c
b CODATA (1986) kin ngh gi tr hng s Avogadro NA l 6,022 1367 x
10
23
mol
-1
Ch thch:
1. Gi tr thc quy c i khi c gi l gi tr n nh, c lng tt nht
ca gi tr, gi tr quy c hoc gi tr tiu chun.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 61
2. Nhiu kt qu o ca mt i lng thng c dng thit lp gi tr thc
quy c.
B.5 i lng nh hng/ Influence quantity
i lng khng phi l i lng o nhng nh hng n kt qu o [H.4].
V d:
a Nhit ca micromt o di;
b Tn s trong php o bin hiu in th xoay chiu;
c Nng bilirubin trong php o nng haemoglobin ca mt mu huyt
tng trong mu ngi.
PHP O/MEASUREMENT
B.6 i lng o/ Measurand
i lng ring bit c o [H.4].
Ch thch - Bn k c im k thut ca i lng o c th a ra yu cu i vi
cc i lng nh thi gian, nhit v p sut.
B.7 Php o/ Measurement
Tp hp cc thao tc xc nh gi tr ca i lng [H.4].
Ch thch: cc thao tc c th c thc hin mt cch t ng
B.8 Th tc o/ Measurement procedure
Tp hp cc thao tc c m t chi tit thc hin php o c th theo mt phng
php cho [H.4].
Ch thch: th tc do thng c ghi trong mt ti liu, chnh ti liu ny i khi
c gi l th tc o (hoc phng php o) v thng l chi tit ngi
thao tc c th tin hnh php do khng cn thm thng tin khc.
B.9 Phng php o/ Method of measurement
Trnh t logic ca cc thao tc c m t mt cch tng qut thc hin php o
[H.4].
Ch thch: Cc phng php o c th phn loi theo nhng cch khc nhau nh:
Phng php th;
Phng php hiu;
Phng php ch khng
B.10 Kt qu ca php o/ Result of a measurement
Gi tr quy cho i lng o nhn c t php o [H.4].
Ch thch
1. Khi cho bit kt qu o phi lm r n c lin quan n:
S ch
Kt qu cha hiu chnh
Kt qu hiu chnh
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 62
v mt s gi tr c ly trung bnh hay khng
2. S trnh by y kt qu o bao gm thng tin v khng m bo ca
php o.
KHNG M BO O/ UNCERTAINTY
B.11 khng m bo (ca php o)/ Uncertainty (of measurement)
Thng s gn vi kt qu ca php o, c trng cho s phn tn ca cc gi tr c th
quy cho i lng o mt cch hp l.
Ch thch:
1. Thng s c th l lch chun (hoc bi ca n), hoc l ca khong vi
mc tin cy nh.
2. Ni chung, khng m bo o gm nhiu thnh phn. Mt s thnh phn c
th c nh gi bng phn b thng k cc kt qu ca mt dy php o v
c th c c trng bng lch chun thc nghim. Cc thnh phn khc,
cng c th c c trng bng lch chun, c nh gi t cc phn b
xc xut m phng trn c s thc nghim hoc cc thng tin khc.
3. Kt qu o c hiu l c lng tt nht v gi tr ca i lng o v tt c
cc thnh phn ca khng m bo o, bao gm c nhng thnh phn do cc
nh hng h thng nh cc thnh phn gn vi nhng s hiu chnh v gn vi
cc chun qui chiu gy ra, u gp phn vo phn tn.
B.12 Tnh lin kt chun/ Traceability
Tnh cht ca kt qu o hoc gi tr ca mt chun m nh c th lin h ti
nhng chun nh, thng l chun quc gia hay chun quc t, thng qua mt
chui so snh khng gin on vi nhng khng m bo nh.
Ch thch: chui so snh khng gin on c gi l chui lin kt chun.
B.13 khng m bo chun/ Standard uncertainty
) (
i
x u khng m bo ca kt qu ca mt php o c din t nh mt lch chun.
B.14 khng m bo chun tng hp/ Combined standard uncertainty
) ( y u
c
khng m bo chun ca kt qu ca mt php o khi kt qu nhn c t
cc gi tr ca mt s cc i lng khc nhau, bng dng cn bc hai ca tng cc
s hng, cc s hng l cc phng sai hoc l cc hip phng sai ca cc i lng
khc ny c trng s tu thuc theo kt qu o bin i nh th no so vi s thay i
ca cc i lng ny.
B.15 khng m bo m rng/ Expanded uncertainty
U i lng xc nh mt khong bao quanh kt qu ca mt php o m c th cho
rng n cha ng phn ln s phn b ca cc gi tr c th qui cho i lng o mt
cch hp l.
Ch thch
1. Phn s c th c xem nh xc sut ph hoc mc tin cy ca khong.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 63
2. lin kt mt mc tin cy c th vi khong c xc nh bi khng
m bo m rng i hi nhng gi thit r rng hoc tim n i vi phn b
xc sut c c trng bi kt qu o v khng m bo tng hp ca n.
Mc tin cy c th qui cho khong ny ch c th c bit ti phm vi m
nhng gi thit nh vy c coi l ng
3. khng m bo m rng U c tnh t khng m bo tng hp u
c
nhn vi h s ph k.
c
kxu U
B.16 H s ph/ Coverage factor
k Tha s bng s c s dng nh l bi ca khng m bo chun tng hp
nhn c mt khng m bo m rng.
B.17 nh gi loi A (ca KB)/ Type A evaluation (of uncertainty)
Phng php nh gi khng m bo bng phn tch thng k ca cc lot quan
trc.
B.18 nh gi loi B (ca KB)/ Type B evaluation (of uncertainty)
Phng php nh gi khng m bo bng cc phng php khc phng php
phn tch thng k ca cc lot quan trc.
SAI S/ ERROR
B.19 Sai s (ca php o)/ Error (of measurement)
Kt qu ca php o tr i gi tr thc ca i lng o.
Ch thch:
1. V gi tr thc l khng th xc nh c nn trong thc t dng gi tr thc
qui c (xem [VIM] 1.19, [B.2.3] v 1.20[B.2.4]).
2. i khi "sai s" c gi l sai s tuyt i ca php o phn bit vi "sai
s tng i". Khng c ln sai s tuyt i vi gi tr tuyt i ca sai s.
Gi tr tuyt i l modul ca sai s.
B.20 Sai s ngu nhin/ Random error
Kt qu ca mt php o tr i kt qu trung bnh t mt s v hn cc php o cng
mt i lng o trong iu kin lp li.
Ch thch:
1. Sai s ngu nhin bng sai s tr i sai s h thng.
2. V ch c th thc hin mt s hu hn cc php o, nn ch c th xc nh
mt c lng ca sai s ngu nhin.
B.21 Sai s h thng/ Systematic error
Kt qu trung bnh t mt s v hn cc php o cng mt i lng o trong iu
kin lp li tr i gi tr thc ca i lng o.
Ch thch:
1. Sai s h thng bng sai s tr i sai s ngu nhin
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 64
2. Ging nh gi tr thc, sai s h thng v nguyn nhn ca n khng th bit
c mt cch hon ton.
3. i vi phng tin o xem " sai s ng" ([VIM] 5.25).
THUT NG THNG K/ STATISTICAL TERMS
B.22 Gi tr trung bnh s hc/ Arithmetic mean
x Tng cc gi tr chia cho s lng cc gi tr
n
x
x
n i
i
, 1
B.23 lch chun ca mu/ Sample standard deviation
s c lng lch chun ca tp hp t n kt qu ca mt mu
( )
1
1
2
n
x x
s
n
i
i
B.24 lch chun ca gi tr trung bnh/ Standard deviation of the mean
x
s lch chun ca gi tr trung bnh x ca n gi tr t tp hp c tnh bng:
n
s
s
x
B.25 lch chun tng i (RSD)/ Relative standard deviation (RSD)
RSD c lng lch chun ca tp hp t n kt qu ca mt mu chia cho gi tr trung
bnh ca mu. Thng gi l h s hip phng sai (CV). Cng thng c tuyn b
nh h s phn trm
x
s
RSD
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 65
PH LC C. KHNG M BO TRONG CC QUI TRNH PHN TCH
C.1 Qui trnh thun tin nhn bit cc ngun c th gy KB trong th tc phn tch
l chia nh th tc phn tch thnh cc bc chung:
1. Ly mu
2. Chun b mu
3. S dng cht chun c chng nhn ti h thng o
4. Hiu chun thit b o
5. Phn tch (d liu thu c)
6. D liu qu trnh
7. Trnh by cc kt qu
8. Din gii kt qu
C.2 Cc bc trn c th chia nh hn theo KB ca tng phn b. Theo danh mc di
y, khng cn thit phi bao gm ton b nhng cung cp hng dn v cc nhn t cn cn
nhc.
1. Ly mu
ng nht
nh hng ca chin lc ly mu c th (v d ngu nhin, ngu nhin theo tng,
theo t l)
nh hng ca vic chuyn qua khi trung gian (mt la chn c th)
Tnh cht vt l ca khi (rn, lng, kh)
nh hng ca nhit v p sut
Qu trnh ly mu c nh hng n thnh phn? V d s hp ph khc nhau trong h
thng ly mu.
2. Chun b mu
ng nht v/hoc nh hng chia mu
Sy
Nghin
Ho tan
Chit
Nhim bn
Cht dn xut (nh hng ho hc)
Sai s pha long
Nng ban u
Kim sot nh hng thng s yu cu k thut
3. S dng cht chun c chng nhn (CRM) cho h thng o
KB ca CRM
CRM ph hp vi mu
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 66
4. Hiu chun thit b
Sai s hiu chun thit b s dng CRM
Cht chun v KB ca cht chun
Mu ph hp vi thit b hiu chun
chnh xc ca thit b
5. Phn tch
Chuyn vo my phn tch t ng
nh hng ca ngi phn tch v d m mu, th sai, cc sai s h thng khc
Nhim bn t mu, thuc th hoc ngi phn tch
tinh khit ca thuc th
t cc thng s thit b v d thng s tch phn
chnh xc qua nhng ln phn tch
6. D liu qu trnh
Ly trung bnh
Kim sot vic lm trn v rt gn
Phn tch thng k
Cc thut ton s hc (m hnh ph hp, v d bnh phng tuyn tnh ti thiu)
7. Trnh by kt qu
Kt qu cui cng
c lng KB
Mc tin cy
8. Din gii kt qu
Theo gii hn/ ng bin
Ph hp qui nh
Ph hp mc ch
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 67
PH LC D. CC NGUN KHNG M BO TRONG PHN TCH
D.1 Gii thiu
Thng thng cn xy dng vo lu h s danh mc cc ngun KB lin quan ti phng
php phn tch. Vic lu h s danh mc cc ngun KB l c li khi lp cu trc cho qu
trnh v m bo bao ph ht ton b cc ngun KB v trnh vic tnh ton qu nhiu.
Theo mt th tc (da vo phng php ban hnh trc [H.14]), cung cp mt kh
nng xy dng, cu trc phn tch thch hp cc phn b KB.
D.2. Qui tc tip cn
D.2.1 Ln k hoch gm hai giai on
- Xc nh cc nh hng ln kt qu
Thc nghim cn xc nh cu trc cc nh hng ca cc php phn tch s dng s
nguyn nhn v kt qu (i khi c th hin/bit n nh s Ishikawa hoc s
xng c) . [H.15].
- n gin ho v gii quyt/phn tch cc thnh phn xut hin lp li
Danh sch ban u c xc nh li trnh by n gin v m bo rng cc nh
hng khng cn thit khng b tnh lp li hai ln.
D.3. Phn tch cc nguyn nhn v kt qu
D.3.1 Cc qui tc ca vic xy dng s nguyn nhn v kt qu c m t y . Th
tc ny c thc hin nh sau:
1. Vit y cng thc tnh kt qu. Mi nhnh chnh ca s xng c l i din cho
mt i lng u vo trong cng thc tnh kt qu. Thng thm mt nhnh chnh tn l
hiu chnh cho ton b chch, thng gi l s thu hi v c th a ra khuyn ngh
giai on ny.
2. Cn nhc tng bc ca phng php v thm bt c nhn t nh hng chnh c tnh
ton bn ngoi vo s . V d cc nh hng v mi trng v nhiu.
3. i vi tng nhnh, thm cc nhn t ng gp vo cc nh hng cho ti khi chng nh
hng khng ng k v ti khi cc nh hng ln kt qu c th b qua c.
4. Phn tch cc thnh phn xut hin lp li v b tr li lm r cc phn b v nhm cc
nguyn nhn c lin quan. Vic ny thun tin nhm cc chm t cc nhnh c
chm khc nhau.
D.3.2 Giai on cui ca cc th tc xc nh nguyn nhn v kt qu yu cu lm r thm.
Cc nh hng ny sinh lp li t nhin trong chi tit cc phn b cho cc thng s u vo.
V d hin tng sai khc qua cc ln thc hin thng xut hin t nht l trn danh ngha
i vi tham s nh hng; cc nh hng ny phn b ti bt c phng sai tng thu c
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 68
t phng php v khng nn b sung thm mt phng sai nh hng ring nu tnh ton
k. Thng gp tnh hung l s dng cng thit b cn vt liu, s tnh lp li khng
m bo hiu chun ca cn. Cn cn nhc vic thit lp li s xng c theo mt s qui
tc sau ( l l do vic p dng s xng c c li hn cch thc lit k cc ngun khng
m bo).
- Xo b cc nh hng: Xo b trong trng hp cn hai ln vt liu s dng cng cn.
chch ca cn c th xo b ( chch trong s xng c).
- nh hng tng t, cng thi im, tng hp thnh mt ngun nh hng n. V d
phng sai lp li ca mt vi ngun u vo c th tng hp thnh mt nhnh chm.
Yu cu cn thn khi tng hp thnh nhnh chm t cc ngun u vo nh trn l
phng sai ca cc qu trnh thc hin c lp cho tt c cc s xc nh c th tng hp
c do phng sai trong qu trnh thc hin trn mt l mu (nh thit b hiu chun)
s c quan st chm gia cc l mu.
- V d khc: i tn. Thng thy cc nh hng c cng tn m thc t khc php o th
cn cn nhc v phn bit r.
D.3.3 Mu phn tch cc nguyn nhn v nh hng theo s ny khng u tin thay th
cho hnh thc lit k cc ngun. Trong v d m ti liu nu th nhit c th nh hng ti
khi lng vt liu c o v c khi lng dng c ng vt liu c o c th cng mt
cu trc. Trong thc nghim th khng nh hng n tnh thc t ca phng php. Cc nh
hng ng k c cp n trong danh sch cc ngun nh hng theo phng php lun
c gi li.
D.3.4 Mt phng php phn tch nguyn nhn v kt qu c thc hin bng cch i t cc
ngun u vo trong cng thc ton hc tnh kt qu sau thm cc ngun mi (nh nhit
).
D.4. V d
D.4.1 Mt v d minh ha theo ng cc bc ca phng php xy dng s xng c
nguyn nhn v kt qu l php o t trng Ethanol. Cn nhc trng hp xc nh trc tip
nng Ethanol bng cn khi lng bnh tam gic khi cha c ethanol v khi c ethanol.
Nng Ethanol c tnh bng cng thc:
d(EtOH) = (m
gross
- m
tare
)/V
Theo cng thc ton hc th ch c 3 ngun nh hng cn c cn nhc v xem xt: hiu
chun thit b, nhit v chm ca mi ln xc nh.. S D1-D3 minh ha r qu trnh
xc nh nguyn nhn v kt qu.
D.4.2 S nguyn nhn v kt qu bao gm cu trc theo th t ca tng ngun u ra. i
vi mc ch thc t th ngun u ra l kt qu phn tch t trng ethanol trong hnh D1. Cc
nhnh chnh ca ngun ra l cc nh hng chnh bao gm cc kt qu o trung gian v cc
thng s khc nh mi trng hoc nh hng nhiu khc. Mi nhnh c th c nhiu hn
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 69
cc phn b ca cc nh hng. Cc nh hng ny tng hp thnh cc thng s nh hng
n kt qu v cc cc phng sai v hng s; khng m bo ca bt k nh hng no s
ng gp vo khng m bo ca kt qu.
D.4.3 Hnh D1 ch ra s bao gm cc ngun nh hng p dng cho cc bc t 1-3. Cc
nhnh chnh l cc tham s trong cng thc ton hc v cc nh hng trn tng nhnh chnh
c th hin nh cc nhnh ph. Ch l c 2 ngun nh hng l nhit , 3 ngun
chm v 3 ngun nh hng hiu chun.
D.4.4 Hnh D2 ch ra l nh hng chm v nhit c nhm li theo qui tc 2 (cng
nh hng/cng thi gian); nhit c th c chuyn thnh mt nhnh nh hng n
trong vic xc nh t trng trong cc phng sai n ca mi xc nh phn b ti
phng sai quan st c trong o lp li ca phng php.
D.4.5 chch hiu chun trn 2 ln cn c trit tiu v c th chuyn thnh hnh D3 theo
qui tc 1 (hu b).
D.4.6 Cui cng gi li nhnh hiu chun v phn bit nh hai ngun phn b khc nhau ca
tuyn tnh ca cn cng khng m bo hiu chun lin quan ti vic xc nh dung
tch.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 70
Hnh D1: Danh mc ban u
m (tng) m (b)
tuyn tnh chch tuyn tnh chch
Nhit Nhit
chm Hiu chun chm Hiu chun
d(EtOH)
chm
Hiu chun
V (thtch)
Hnh D2: Tng h p c c nh hng tng t
Nhit m (tng) m (b)
tuyn tnh chch tuyn tnh chch
Nhit Nhit
chm Hiu chun chm Hiu chun
d(EtOH)
chm Hiu chun
V (thtch) chm
Hnh D3: Lo i b c c nh hng
C ng mt cn
chch lo i b
Nhit m (tng) m (b)
tuyn tnh chch tuyn tnh chch
Hiu chun Hiu chun
d(EtOH)
Hiu chun
V (thtch) chm
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 71
PH LC E. CC PHNG PHP THNG K THCH HP
E.1 Cc hm phn b
Theo cc bng ch dn di y th cch tnh ton khng m bo t cc tham s ca hai
hm phn b quan trng nht v a ra cc ch s trong cc tnh hung s dng nh th no
V d: c lng ho hc mt tham s phn b khng t hn 7 ti 10 nhng c th nhn thy
gi tr u trong m khng c thm nhn xt g v gi tr tp trung u nhiu hn.
y l m t ca phn b hnh tam gic vi rng 2a =3 (a=1.5). S dng hm di cho
phn b hnh ch nht, c lng khng m bo chun. S dng khong a=1.5 kt qu
khng m bo chun ca 1.5/ 3 =0.87
Phn b ch nht
Dng S dng khi KB
Chng ch - qui nh k thut
cho bit gii hn nhng
khng bit mc tin cy
(vd: 25mL t 0,05mL)
c lng u theo a cc i
nhng khng bit dng phn
b
Phn b hinh tam gic
Dng S dng khi KB
Thng tin v x nhiu hn i
vi phn b ch nht. Cc
gi tr gn x nhiu hn gn
vi bin.
c lng u theo a cc i
m t bng phn b i
xng.
1/2a
x
3
) (
a
x u
i
2a (= a)
1/a
x
2a (= a)
6
) (
a
x u
i
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 72
Phn b chun
Dng S dng khi KB
c lng u t nhng quan
trc lp li ca mt qu trnh
bin i ngu nhin.
Cho khng m bo o
theo:
+ lch chun s
+ lch chun tng i
s/x
+ h s phng sai CV%
nhng khng bit phn b
Cho KB vi mc tin cy
95% m khng bit phn b
u(x) = s
u(x) = s
u(x) = c/2
E.2 Tnh ton khng m bo bng phng php bng tnh
E.2.1 Bng tnh phn mm c th c s dng n gin ho s tnh ton trong phn 8.
Phng php ny mang li nhiu thun li so vi cc phng php s hc tng t v ch yu
cu kin thc v tnh ton s dng tnh ton kt qu cui cng (bao gm bt c h s hiu
chnh hoc nh hng cn thit no) v cc gi tr s ca cc tham s v khng m bo
ca cc tham s. M t di y theo Kragten [12]
E.2.2 Din t KB u(y(x
1
, x
2
,...,x
k
))
( )
,
_
,
_
n k i
k i
k i n i
i
i
x x u
x
y
x
y
x u
x
y
, 1 ,
2
, 1
, ) (
cung cp c y(x
1
, x
2
...x
n
) tuyn tnh ca x
i
hoc u(x
i
) l nh so vi x
i
, s khc nhau c th
c tnh theo cng thc:
) (
) ( )) ( (
i
i i i
x u
x y x u x y
xi
y +
KB u(y,x
i
) c tng hp t u(x
i
)ca y theo x
i
) .. ,... , ( ) )).. ( ,...( , ( ) , (
2 1 2 1 n i n i i i
x x x x y x x u x x x y x y u +
u(y,x
i
) l s khc nhau gia gi tr ca y tnh t [x
i
+u(x
i
)] so vi x
i
tng ng
E.2.3 Gi s c tuyn tnh hoc gi tr nh ca u(x
i
)/x
i
s khng ph hp trong mi trng
hp. D sao phng php cng cung cp chnh xc kh nng chp nhn cho mc ch c th
1 1
) / ( ) ( x s x x u
x
CV
x u
100
%
) (
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 73
khi cn nhc theo s cn thit tng ng trong vic c lng cc gi tr ca u(x
i
). Tham
kho H.12 tho lun v phng php thch hp kim tra v ph duyt cc gi thit.
E.2.4 Mt bng tnh c bn c thit lp di y, gi thit l kt qu y l mt hm gm
bn tham s p, q, r, s:
i. Vo cc gi tr ca p, q v cng thc tnh ton y trong ct A ca bng tnh. Copy t ct A
theo tng ct cho tt c cc phng sai trong y (xem bng E2.1). Thun tin cho cc v tr
ca cc gi tr KB u(p), u(q) v cc dng 1 nh trong bng.
ii. Thm u(p) vo p trong B3, u(q) vo q trong B4... nh trong bng E2.2. Tnh li trong
bng tnh th B8 thnh f(p+u(p), q, r...) biu th bng f(p, q, r,...) trong bng E2.2 v
E2.3, C8 tr thnh f(p, q+u(q), r,...)...
iii. Trong dng 9 vo dng 8 tr A8 (v d B9 l bng B8 A8). a ra cc gi tr ca
u(y,p) l
u(y, p) = f (p + u(p), q, r...) f(p, q, r...)...
iv. thu c lch chun ca y cc phn b n c bnh phng tng hp vi nhau
sau cn bc hai c u(y, p)
2
trong dng 10 (bng E2.3) v t cn ca bnh phng
vo ct A10. A10 c tnh theo cng thc:
SQRT (SUM(B10+C10+D10+E10)) vi KB chun theo ca y
E.2.5 Ni dung ca B10, C10 ch ra phn b bnh phng KB u(y,xi)
2
=(c
i
u(x
i
))
2
ca
phn b KB n l ti KB ca y v c th thy c thnh phn no l ng k.
E.2.6 Rt d hiu khi tnh ton theo cch ny tc l tng gi tr tham s KB thnh phn
thay i hoc KB c xc nh li. Trong cc bc i trn thay v copy ct A sang ct
B-E th copy gi tr ct p ti s, B3 ti E3 cho tt c cc lin quan A3, B4, E4 A4...Mi tn
ngang trong bng E2.1 ch ra s lin quan cho dng 3. Ch thch ct B8 ti E8 nn l cc gi
tr tham chiu trong cc ct B ti E nh ch ra trong ct B bi mi tn ngang trong E2.1.
Trong cc bc ii trn thm cc tham kho t dng 1 (nh ch ra mi tn trong hnh
E2.1). V d B3 tr thnh A3 + B1, C4 tr thnh A4 + C1...Thay i cc tham s hoc
KB s c phn nh ngay lp tc trong kt qu tng cng ti A8 v KB chun tng
hp trong A10.
E.2.7 Nu cc phng sai c hiu chnh th cn thm gii hn ti tng trong A10.
V d nu p v q c hiu chnh vi h s hiu chnh r(p,q) sau thm gii hn
2 x r(p,q) x u(y,p) x u(y,q) c thm vo tnh tng trc khi cn bc hai. S hiu chnh c
th d dng bao gm bi vic thm gii hn thch hp trong bng tnh.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 74
Bng E 2.1
A B C D E
1 u(p) u(q) u(r) u(s)
2
3 p p p p p
4 q q q q q
5 r r r r r
6 s s s s s
7
8 y=f(p,q...) y=f(p,q...) y=f(p,q...) y=f(p,q...) y=f(p,q...)
9
10
11
Bng E 2.2
A B C D E
1 u(p) u(q) u(r) u(s)
2
3 p p + u(p) p p p
4 q q q + u(q) q q
5 r r r r + u(r) r
6 s s s s s + u(s)
7
8 y=f(p,q...) y=f(p
,...) y=f(...q
,...) y=f(...r
,...) y=f(...s
,...)
9 u(y,p) u(y,q) u(y,r) u(y,s)
10
11
Bng E 2.3
A B C D E
1 u(p) u(q) u(r) u(s)
2
3 p p + u(p) p p p
4 q q q + u(q) q q
5 r r r r + u(r) r
6 s s s s s + u(s)
7
8 y=f(p,q...) y=f(p
,...) y=f(...q
,...) y=f(...r
,...) y=f(...s
,...)
9 u(y,p) u(y,q) u(y,r) u(y,s)
10 u(y) u(y,p)
2
u(y,q)
2
u(y,r)
2
u(y,s)
2
11
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 75
E.3 khng m bo t hiu chun bnh phng tuyn tnh
E.3.1 Phng php phn tch hoc thit b thng c hiu chun bi s quan st kt qu y
t cc mc khc nhau ca phn tch gi tr x. Trong nhiu trng hp mi quan h ny
c th hin tuyn tnh bi hm:
y = b
o
+ b
1
x Ct.E.3.1
Hiu chun ng tuyn tnh ny thng s dng th hin nng x
pred
ca phn tch t
mt mu vi cc phng php quan st kt qu y
obs
t
x
pred
= (y
obs
b
0
)/b
1
Ct.E.3.2
Thng thng xc nh hng s b
1
v b
0
bng cn hoc khng cn ti thiu hi qui trong
mt tp cc cp n gi tr ca (x
i
,y
i
)
E.3.2 C 4 ngun chnh ca KB cn c cn nhc c ny sinh khi c lng nng
x
pred
;
- Phng sai ngu nhin trong o lng y nh hng ti c kt qu tng ng y v php o
y
obs
- Kt qu nh hng ngu nhin trong sai s ch trong gi tr tham chiu x
i
.
- Cc gi tr ca x
i
v y
i
c th ph thuc hng s khng bit b li v d ny sinh t cc gi
tr ca x thu c t cc ln pha long dung dch
- Gi thit tuyn tnh c th khng c gi tr
Trn y cc nh hng ng k thng gp trong thc nghim l cc phng sai ngu nhin
trong y v cc phng php c lng KB cho c ngun ny c nu chi tit trn.
Cc ngun c duy tr thng tm tt a ra cc ch s c sn cho cc phng php.
E.3.3 KB u(xpred, y) trong gi tr d on x
pred
theo phng sai trong y c th c c
lng theo mt s cch:
T tnh ton phng sai v hip phng sai
Nu cc gi tr ca b
1
v b
0
, phng sai var(b
1
), var(b
0
) v phng sai ca chng, hip
phng sai covar(b
1
, b
0
) c xc nh bi phng php bnh phng ti thiu, phng sai
trn x, var(x) thu c bng s dng cng thc trong chng 8 v mt cng thc khc nh
sau:
var (x
pred
) =
2
1
0 1 1
2
) var( ) , ( cov 2 ) var( ) var(
b
b b b ar x b x y
o pred pred obs
+ + +
Ct.E.3.3
v KB lin quan u(x
pred
, y) = ) var(
pred
x
T d liu hiu chun
T cng thc trn tnh var (x
pred
) c th c vit theo qui tc tp hp n im d liu,
(x
i
, y
i
) s dng xc nh hm hiu chun:
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 76
,
_
+ +
i i i i i
pred
i
obs
pred
w x w x w
x x
w b
S
b
y
x
/ ) ( ) ( (
) (
1 ) var(
) var(
2 2
2
2
1
2
2
1
Ct.E.3.4
Khi
( )
) ( ,
2
2
fi i
i
f i i
y y
n
y y w
S
l im d th i, n l s lng im d liu hiu chun, b
1
l c lng tt nht ca gradient,
w
i
l khi lng ch nh ca y
i
v l s khc nhau gia x
pred
v gi tr trung bnh ca n gi tr
x
i
, x
2
...
i vi cc d liu khng khi lng v nu var (y
obs
) c da vo php o p cng thc
E.3.4 tr thnh:
,
_
+ +
) / ) ( ) ( (
) (
1 1
) var(
2 2
2
2
1
2
n x x
x x
n p b
S
x
i i
pred
pred
Ct.E.3.5
y l cng thc m c s dng trong v d 5 vi
[ ]
2 2 2
) ( / ) ( ) ( x x n x x S
i i i xx
T thng tin trong phn mm s dng dng ng cong hiu chun
Mt vi phn mm a ra gi tr ca S, phng sai m t v d nh sai s RMS hoc sai s
chun cn li. C th c s dng trong cng thc E.3.4 hoc E.3.5. Do mt vi phn
mm c th a ra lch chun s(y
c
) trn gi tr tnh y so vi ng chun cho mt vi gi
tr ca x v c th s dng tnh var(x
pred
) vi p=1
) / ) ( ) ( (
) (
1
1 ) (
2 2
2
+ +
n x x
x x
n
y s
i i
pred
c
so vi cng thc E.3.5
var(x
pred
)=[s(y
c
)/b
1
]
2
Ct.E.3.6
E.3.4 Gi tr tham chiu x
i
c th c KB lin quan vi s ny sinh thng qua kt qu
cui cng. Thc t, KB trong cc gi tr ny thng nh so vi KB trong h thng
kt qu y
i
v c th b l i. c lng thch hp KB u(x
pred
, x
i
) trong mt gi tr d
on x
pred
theo KB ca gi tr tham chiu x
i
c th l:
u(x
pred
,x
i
) u(x
i
)/n
khi n l s gi tr x
i
s dng trong hiu chun. S din t c th s dng kim tra
u(x
pred
,x
i
) .
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 77
E.3.5 KB ny sinh t gi nh tuyn tnh quan h gia y v x thng khng ln
cn c yu cu c lng thm. Cung cp phn cn li ch ra rng khng c lch h thng
ng k no t vic gi nh tng quan, KB ny sinh t s gi nh ny (thm vo o
bi s tng kt qu phng sai y) c th c b qua. Nu phn cn li hc ra rng c xu
hng h thng th cn thit phi bao gm cc gii hn cao hn trong hm hiu chun. Cc
phng php tnh ton var(x) trong cc trng hp ny a ra cc vn bn chun. Nu c th
to ra iu chnh c bn trong c ca xu hng h thng.
E.3.6 Cc gi tr ca x v y c th l i tng cho hng s b khng bit (v d ny sinh khi
cc gi tr ca x thu c t nhiu ln pha long ca dng dch lm vic vi KB trong
chng ch gi tr). Nu KB chun trong y v x t cc nh hng ny l u(y,const) v
u(x,const) th KB trong gi tr ni suy x
pred
c a di dng:
u(x
pred
)
2
= u(x,const)
2
+ (u(y,const)/b
1
)
2
+ var(x) Ct.E.3.8
E.3.7 Bn thnh phn KB m t trong E.3.2 c th c tnh s dng cng thc E.3.3 ti
E.3.8. KB tng ny sinh t tnh ton t hiu chun tuyn tnh c th c tnh bi tng
hp bn thnh phn theo cch thng thng.
E.4 KB ph thuc vo mc phn tch
E.4.1 Gii thiu
E.4.1.1 Thng quan st c trong o lng ho hc, trn phm vi rng ca mc
phn tch, phn b u th KB tng s lng tng ng thch hp ti mc phn
tch l u(x) x. Trong nhiu trng hp thng KB nhn bit c nh lch
chun tng i hoc h s phng sai %CV
E.4.1.2 Khi KB khng b nh hng/thay i bi mc , v d cc mc thp
hoc khi khong gii hn tng i bao gm mc phn tch, thng c ch thch l gi
tr tuyt i ca KB.
E.4.1.3 Trong nhiu trng hp c hng s v cc s hng nh hng l quan trng. Phn
ny cp s tip cn chung ti h s thng tin KB khi phng sai ca KB vi mc
phn tch c cng b v bo co nh h s n ca phng sai khng tng ng.
E.4.2 C s tip cn
E.4.2.1 S hng ca KB v gi tr hng s cn thit vi mc m theo din t
chung theo cng thc:
2 1
2
0
) ( ) ( s x s x u + [1]
trong :
u(x) KB tng hp ca kt qu x (khi KB c din t nh lch chun)
s
0
phn b hng s ti KB
s
1
gi tr hng s
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 78
Din t da vo phng php thng thng tng hp hai phn b ti KB, gi nh mt
phn b (s
0
) l hng s v mt gi tr ti kt qu (xs
1
) bng E4.1 ch ra mt dng din t
Ch thch: Tip cn trn l thc nghim khi c th c tnh ton vi s lng ln cc gi tr. Khi
nghin cu thc nghim thng khng tin khi thit lp mi quan h theo ng parabon. Trong cc
trng hp mt s thch hp tng ng c th thu c bi ng tuyn tnh hi qui qua 4 hoc
nhiu KB tng hp thu c ti cc nng phn tch. Th tc ny l thng nht vi mi ngi
s dng trong nghin cu ti lp v lp li theo ISO5725. Din t lin quan l
1 0
' ' ) ( xs s x u +
E.4.2.2 th c th chia thnh hai khu vc (A v C trn th)
A KB l c nh hng bi gi tr s
0
v hng s thch hp v gn vi s
0
.
B C gi r phn b ng k; kt qu KB l ln ng k so vi c s
0
v xs
1
v cong
l c th nhn thy r
C Gi tr xs
1
c nh hn; KB ny sinh tuyn tnh thch hp vi tng x v gn xs
1
E.4.2.3 Ch thch rng trong mt vi trng hp thc nghim dng hon chnh ca ng
cong s khng c r rng. Thng bo co khong mc phn tch chp nhn bi phm
vi ca phng php ng dc gia khu vc biu n; kt qu l s trng hp c bit
lin kt vi cc chi tit di.
E.4.3.1 Ni chung, cc KB c th c ti liu ho di dng mt gi tr cho tng s
0
v s
1
. Cc gi tr c th c s dng cung cp c lng KB theo phm vi ca
phng php. Thi l gi tr c th khi tnh ton cho cc phng php thuc tnh tt c thc
hin bng h thng my tnh khi dng cng thc c th p dng thc hin c lp cc gi tr
ca tham s (mt trong s c th l 0 xem phn di). Ch chp nhn cc trng hp
c bit ch ra di hoc khi khng ph thuc mnh vo ng khng tuyn tnh*, KB
c ti liu ho di dng biu mu cc gi tr thng nht cc gi tr i din bi s
0
v gi
tr i din phng sai s
1
E.4.4 Cc trng hp c bit
E.4.4.1 KB khng ph thuc vo mc phn tch (s
0
c nh hng ln)
KB s c nh hng c lp khi quan st nng phn tch khi:
- Kt qu gn ti 0 (v d tuyn b gii hn pht hin ca phng php). Khu vc A trong
bng E.4.1
Mt v d quan trng ca ph thuc khng tuyn tnh l nh hng ca n ca thit b khi o hp
th ti im hp th cao gn gii hn trn ca kh nng thit b. iu ny c th khi tnh ton truyn
(nh quang ph hng ngoi). Di cc qui tc ng n c bn nguyn nhn rt ln gy ra KB
trong cc s hp th cao v KB ny sinh rt nhanh hn l c lng tuyn tnh n gin d on.
Tip cn thng thng l gim hp th, bng pha long a ra s hp th tt hn trong khu vc lm
vic; dng tuyn tnh s dng y s thng tng ng. Mt v d khc bao gm s tr li dng
xichma ca phng php phn tch min dch.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 79
- Phm vi ca cc kt qu (tuyn b trong phm vi phng php hoc trong tuyn b phm
vi c lng KB) l nh so vi mc quan st.
Di cc qui tc trn gi tr ca s
1
c th bo co bng 0. s
0
thng c tnh l KB
chun.
E.4.4.2 KB ton vn khng ph thuc vo phn tch (s
1
nh hng ln)
Khi kt qu cch xa im 0 (v d trn gii hn pht hin) v c bng chng r rng rng
KB thay i tng ng vi mc phn tch cho php trong phm vi ca phng php, nh
hng xs1 l ng k (xem khu vc C trong bng E.4.1). Di cc qui tc trn v khi phm vi
phng php khng bao gm cc mc phn tch gn 0 v s
1
thng din t KB nh
lch chun tng i.
E.4.4.3 Ph thuc trung gian
Trng hp trung gian v c th khi tnh hung ph hp vi khu vc B trong bng E.4.1 hai
cch tip cn c th p dng:
a. p dng phng sai ph thuc
Cng tip cn chung l xc nh, h s v s dng c s
0
v s
1
. c lng KB khi yu
cu c th thc hin trn c s cc bo co kt qu. Gi li cc khuyn ngh, ghi ch tip
cn khi p dng thc t.
Ch thch: xem ch thch E.4.2
b. p dng qui nh thch hp
La chn thay th m c th s dng trong th nghim chung v khi
- S ph thuc khng qu mnh (bng chng tng ng l yu) hoc
- Phm vi kt qu mong i l c mc / va phi/ hn ch
Hng dn trong c hai trng hp tnh KB m khng c gi tr nhiu hn 15% t c
lng KB trung bnh thng l l do tnh ton v ghi ch li gi tr KB s
dng da vo gi tr trung bnh ca kt qu mong i. l
cng
Gi tr trung bnh hoc gi tr dng x l c tnh ton c lng KB v c
s dng trong phm vi c lng ring l
hoc
lch chun n c cng b da vo nghin cu vt liu bao gm trn ton b
khong ca cc mc phn tch (trong phm vi ca c lng KB), v c t
bng chng chng minh s gi nh ca t l/tng ng. iu ny c th t c
nh trng hp ph thuc 0 v lch chun tng i bo co l s
0
E.4.5 Xc nh s
0
v s
1
E.4.5.1 Trong nhiu trng hp m mt gi tr nh hng, s khng hiu qu khi s dng
KB nh lch chun hoc lch chun tng i theo th t nh gi tr s
0
v s
1
. Khi
s ph thuc t r rng do c th cn xc nh s
0
v s
1
khng trc tip t hng lot c
lng KB ti cc mc phn tch khc nhau.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 80
E.4.5.2 a ra tnh ton KB tng hp t cc thnh phn khc nhau mt vi thnh
phn ph thuc vo mc phn tch trong cc thnh phn khc li khng ph thuc,
thng thng c th c nh gi ph thuc vo KB tng th ca c mc phn tch
bng m phng. Th tc c thc hin nh sau:
1. Tnh ton (hoc a ra KB thc nghim u(x
i
) cho t nht 10 mc phn tch ca
x
1
bao gm cho cc khong phn tch)
2. im u(x
i
)
2
theo x
i
2
3. Bi ng tuyn tnh hi qui, c lng thu c ca m v c cho ng u(x)
2
= mx
2
+ c
4. Tnh s
0
v s
1
t s
0
= c , s
1
= m
5. H s lu s
0
v s
1
E.4.6 Bo co
E.4.6.1 Tip cn c lng ca KB chun cho kt qu n. Trong qui tc khi thng
tin v KB c bo co, s dngj
[kt qu] t [ KB]
khi KB nh lch chun l tnh ton nh trn v nu cn th m rng (thng h s m
rng bng 2) tng mc tin cy. Khi s kt qu c bo co cng nhau th c th v
chp nhn chp nhn hon ho, a ra mt c lng KB p dng cho bo co tt c kt
qu.
E.4.6.2 Bng E.4.1 a ra cc v d. KB c cc ch s cho mt danh mc cc phn
tch khc nhau c th s dng lit k theo bng theo qui tc n gin
Ch thch: khi gii hn pht hin hoc bo co gii hn c s dng a ra kt qu
trong dng <x hoc nd , n thng a ra gii hn s dng thm KB p dng
cho kt qu trn bo co gii hn.
Bng E.4.1: Tng hp KB cho cc mu
Tnh hung Gii hn nh hng Bo co KB
KB cn thng nht qua
tt c cc kt qu
s
0
hoc c nh thch hp
(phn E.4.4.1 hoc E.4.4.3a)
lch chun: KB m
rng; 95% mc tin cy
KB tng ng chung
cho mc
xs
1
(xem phn E.4.4.2) KB chun tng i; h
s phng sai (%CV)
Trn tng ng v gi tr gii
h hp cho KB
Trng hp trung gian (xem
E.4.4.3)
Ch thch %CV hoc lch
chun tng i cng vi
gii hn di nh lch
chun
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 81
PH LC F. KHNG M BO O TI GII HN PHT HIN/
GII HN XC NH
F.1. Gii thiu
F.1.1. Ti cc nng thp, s tng thm trng thi khc nhau ca cc nh hng tr nn quan
trng v d bao gm:
- n hoc khng n nh ng nn
- Phn b ca cc nhiu ti tn hiu (tng)
- nh hng ca vic s dng phn tch mu trng v
- Mt i qua vic chit, tch hoc lm sch.
V cc nh hng nh dc ca cc nng phn tch nn KB tng i lin quan vi
kt qu c xu hng tng, u tin phn s quan trng ca kt qu v cui cng ti im m
khong KB i xng bao gm 0. Min ny thng lin quan vi gii hn pht hin thc
nghim ca phng php.
Ch thch: Thut ng v cc quy c lin quan vi o lng v bo co gii hn thp ca
php phn tch c tho lun rng ri cc ti liu khc (xem ti liu tham kho [H.16,
H.17, H.18] v v d v nh ngha). y thut ng gii hn pht hin ch p dng mt
mc ti s pht hin tr nn khng chc chn v khng lin quan vi bt k nh ngha c
th no.
F.1.2. Mt chp nhn rng ri l quan trng nht l s dng gii hn pht hin l ch ra khi
phng php thc hin tr nn khng thch hp c th chp nhn nh lng, do cn
tin hnh cc ci tin. Do ngha ca cc php o nh lng c th khng xc nh phm
vi ny. Tuy nhin nhiu i tng th nghim vic thc hin cc php o v bo co cc kt
qu nhng phm vi rt thp rt quan trng.
F.1.3. ISO GUM [H.2] khng a ra cc ch dn r rng c lng KB khi cc kt qu
nh v KB l ln so vi kt qu. Thay vo dng c bn ca qui nh ph bin ca
KB cp trong chng 8 ca hng dn c th lin tc p dng chnh xc trong cc
phm vi ny; mt gi thit trong tnh ton c da vo l KB l nh so vi gi tr
ca i lng o. Thm vo kh tun theo t nh ngha KB a ra bi ISO GUM
qua cc quan st m tnh l c th v thng trong phm vi ny vic p dng s phn tn bao
gm cc gi tr di 0 khng th l ..l do quy cho gi tr ca i lng o khi i lng o
l mt nng v cc nng bn thn chng khng th l m tnh.
F.1.4. Cc kh khn ny khng loi tr s p dng cc phng php nm ngoi hng dn
ny nhng mt vi ch c yu cu din gii v bo co kt qu c lng KB trong
phm vi ny. Mc ch ca ph lc ny l cung cp hng dn c gii hn b sung cc
ngun c sn v KB.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 82
Ch thch: Nng thng thng c th p dng cho cc phm vi khc; v d khi lng
phn t hoc phn khi lng gn ti 100% c th gp nhng kh khn.
F.2. Cc quan st v c lng
F.2.1. Qui tc c bn ca khoa hc o lng l cc kt qu l c lng ca cc gi tr thc.
Cc kt qu phn tch v d c sn trong cc n vi ca du hiu quan st v d mV n v
hp ph. trao i ti lng khch hng ln hn c th l ti cc khch hng ca PTN hoc
ti cc c quan c thm quyn, d liu quan trc gc cn c cung cp cho ho hc nh
lng nh nng hoc tng lng cht. S chuyn i dng ny yu cu mt th tc hiu
chun (v d c th bao gm cc s hiu chnh quan st v cc thuc tnh tt b mt). Do
bt c s thay i no s quan st hoc du hiu c gi li. Nu thc nghim c tin
hnh mt cch thch hp, cc quan st c l c lng tt nht cho gi tr ca i lng o.
F.2.2. Quan st thng khng tp trung bi cng qui tc gii hn m p dng cho nng
thc. V d nhy hon hon bo co nng quan st c c lng di 0. S thch
hp khi nhy ti din tch ca phn tn ca quan st c vi khong m rng cng phm
vi. V d khi thc hin mt php o khng chch trn mt mu khng phn tch, th nht c
th xem mt na quan st di 0. Mt cch khc c bo co dng:
Nng quan st c = 2.4 t 8mg1
-1
Nng quan st c = -4.2 t 8mg1
-1
khng th s dng c; cn ly gi tr nh tuyn b
F.2.3. Phng php c lng KB c miu t trong hng dn p dng c lng
KB trong gi tr quan st. Tun theo cch khi bo co quan st v KB lin quan ti
s khng nh vi ngi s dng l khng c ro cn hoc s mu thun no trong bo co
c lng tt nht v KB lin quan vi kt qu p dng trong trng hp kh nng vt l
khng th xy ra. Thay vo mt vi trng hp (v d khi bo co gi tr cho mu phn
tch trng vi tn sut c s dng hiu chnh cc kt qu khc) n thng cn trong
trng hp vo co quan st v KB (mc ln).
F.2.4. Gi tr thc c gi li k c khi s dng kt qu c nghi ng. Ch khi kt qu quan st
c v KB lin quan c th c s dng trc tip (v d tnh ton tip tc theo xu
hng hoc din gii li).
F.2.5. ngha trong bo co l gi tr quan st c v KB lin quan ca cc gi tr.
F.3. Din gii cc kt qu ph hp vi cc tuyn b
F.3.1. Mc d cp n nhng phi chp nhn rng nhiu bo co phn tch v tuyn b
s ph hp trong vic din gii cho li ch ca ngi s dng cui cng. Thng thng nh
s din gii c th bao gm mt vi lin quan ni trn v mc ca s phn tch m c
th hp l vi sn phm c th. Nh s din gii v gii thch v v s thch hp trn ton
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 83
th gii v tn xut d nh (s dng bi ngi cui cng) xc nh gii hn thc. c
lng KB lin quan vi gi tr thc.
F.3.2. Trong nhiu trng hp khi ngi s dng cui cng hiu r v tt v khi ngowif s
dng cui cng thc t khng th thng bo cc gi tr o lng quan trc gc hng dn
chung cung cp cc thng tin lin quan (v d nh ti liu tham kho H.16, H.17, H.18) trong
bo co kt qu mc thp c th p dng.
F.3.3. Mt ch thm l thch hp. Cng nhiu thng tin v nng lc pht hin da vo mc
phn tch thng k lp li cc quan st. N c th c lm r cho ngi c nh hng
dn v phng sai quan st c ch l hng dn tt KB ca kt qu. Vi cc kt qu
trong cc vng khc s cn nhc cn thn cn theo tt c cc KB nh hng ti kt qu
a ra trc khi bo co kt qu.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 84
PH LC G. CC NGUN C BN V CC GI TR CA KB
Theo bng tng kt mt vi dng v d ca thnh phn KB. Bng tng kt cung cp cc
thng tin v:
- i lng o c th hoc th tc thc nghim (xc nh khi lng, dung tch)
- Cc thnh phn chnh v ngun khng m bo ca tng thnh phn
- xut phng php xc nh KB ny sinh t cc ngun
- V d cho tng dng
Bng tng kt nhm tm tt cc v d v ch ra cc phng php chung c lng KB
phn tch nhng khng nhm bao hm ton din v cng khng nn s dng cc gi tr trong
mt cch trc tip m khng thng qua chng minh c lp. Cc gi tr c th gip cho
vic quyt nh thnh phn ng k gy ra KB.
Dng gi tr Xc
nh
Ngun
KB
Nguyn nhn Phng php xc nh
V d Gi tr
KB ca
cn
Gii hn chnh
xc trong hiu
chun
Tuyn b trong chng
ch hiu chun, chuyn
thnh lch chun
Cn 4 s 0.5mg
Tnh tuyn tnh Nghin cu thc
nghim vi khong cn
c chng nhn
Yu cu k thut ca
nh sn xut
0.5 s c ngha
cui cng
Kh nng c Gii hn phn gii
trong hin th hoc
thc o
T s c ngha cui
cng
0.5 s c ngha
cui cng/ 3
tri hng
ngy
Phng sai, bao
gm c nhit
lch chun ca vic
kim tra khi lng.
Tnh ton nh lch
chun tng i
(RSD)nu cn
0.5 s c ngha
cui cng
Phng sai
gia cc ln s
dng
Phng sai lch chun ca mu
chun hoc kim tra
khi lng
0.5 s c ngha
cui cng
nh hng t
trng (c s
qui c) ch
thch 1
Hiu chun khi
lng/nguyn
nhn t t trng
mu khng tng
xng s khc nhau
trong nh hng
ca sc cng
khng kh (trng
trng)
Tnh ton t t trng
bit hoc gi nh v
iu kin ca dng
khng kh
Thp, nhm
Niken
Dung dch
hu c
Nc
Hyro
cacbon
1 ppm
20 ppm
50-100 ppm
65 ppm
90 ppm
Khi
lng
nh hng t
trng (c s
vacuo) ch
thch 1
Nh trn Tnh ton nh hng
trng trng v tr nh
hng trng trong
hiu chun khi lng
100g nc
10 g niken
+ 0.1 g
< 1 mg
(nh hng)
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 85
Dng gi tr Xc
nh
Ngun
KB
Nguyn nhn Phng php xc nh
V d Gi tr
KB hiu
chun
Gii hn chnh
xc trong hiu
chun
Tuyn b yu cu k
thut ca nh sn xut,
chuyn thnh lch
chun.
10ml (cp
A)
0.02/ 3 =0.01ml
phn b hnh ch
nht
Nhit Phng sai nhit
t hiu chun
nhit nguyn
nhn l s sai khc
trong dung tch ti
nhit chun
) 3 2 ( . T thu c
lch chun tng
i khi T l khong
nhit hp l v
h s nhy ca n
dung tch ca dung
dch gn bng
2.10
-4
K
-1
vi nc v
dung dch hu c l
1.10
-3
K
-1
100 ml
nc
0.03 ml hot
ng trong phm
vi 3
0
C ca nhi
hot ng
c cng b
Dung
tch
Phng sai
gia cc ln s
dng
Phng sai lch chun ca vic
kim tra ong dung
tch v chuyn (tnh
bng cch cn)
pipette
25ml
y v cn
lp li: s=0.0092
ml
tinh khit gim khng
tinh khit tng ca
mu chun hin
ti. Phn ng khi
dng mu khng
tinh khit c th
gy nhiu
Tuyn b ca nh sn
xut trong chng ch.
chng ch lin quan
thng khng a ra
gii hn
Mu chun
Potassium
hydrogen
phathalate
chng nhn
l
99.9t0.1%
0.1/ 3 =0.06%
Nng (c
chng nhn)
KB ca nng
mu chun
Tuyn b ca nh sn
xut trong chng ch.
Chng ch mu chun
thng khng a ra
gii hn cht lng nn
thng qui v phn b
hnh ch nht bng
chia cho 3
Cadmium
acetate
trong 4%
axit acetic.
Chng ch
l
(1000t2)
mgl
-1
2/ 3 =1.2 mgl
-1
(0.0012 nh
RSD) qui v
phn b hnh ch
nht
Nng
mu
chun
Nng (to
c t mu
chun chng
nhn)
Tng hp
khng m bo
trong cc gi tr
chun v cc bc
trung gian
Tng hp cc gi tr
cho cc bc n RSD
Cadmium
acetate sau
3 ln pha
long t
1000 mgl
-1
ti 0.5 mgl
-1 2
2
2
2
0017 . 0
0021 . 0
0017 . 0
0012 . 0
+
+
+
= 0.0034 nh
RSD
Hp
th
Hiu chun
thit b
ch thch:
thnh phn ny
lin quan ti
s hp th c
c chng li
hp th chun
khng hiu
Gii hn chnh
xc trong hiu
chun.
Tuyn b trong giy
chng nhn hiu chun
nh gii hn, chuyn
i thnh lch
chun.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 86
Dng gi tr Xc
nh
Ngun
KB
Nguyn nhn Phng php xc nh
V d Gi tr
chun ca
nng theo
hp th c
c
Hp
th
Phng sai
gia cc ln s
dng
Phng sai lch chun ca cc
xc nh lp li, hoc
thc hin m bo cht
lng (QA)
Trung bnh
ca 7 ln
c hp
th vi
s = 1.63
1.63/ 7 =0.62
Ly
mu
ng nht mu Cc mu chia t
vt liu khng
ng nht s
khng i din
chnh xc cho c
l mu
Ch thch: ly
mu ngu nhin
thng kt qu s
c chch l 0.
Cn kim tra vic
ly mu ngu
nhin
lch chun ca cc
kt qu mu chia (nu
mu khng ng nht
l tng i ln i vi
chnh xc phn tch)
lch chun c
lng t nhng tham
s cho tp hp bit
hoc d on.
Ly mu t
bnh m t
hai gi tr
d on
khng ng
nht (xem
v d A4)
Ly t 15 v tr
t 72 mu nhim
v 360 mu
khng nhim t
l hng: RSD:
0.58
Thu
hi
ca
chit
Thu hi trung
bnh
Chit it khi c
hon ton v c
th thm hoc bao
gm cc cht
nhiu
Thu hi tnh nh phn
trm h s thu hi t
mu chun hoc mu
thm (spike). KB
thu c t lch
chun ca trung bnh
cc nghin cu thu hi.
Ch thch: Thu hi c
th cng c tnh trc
tip t cc php o
thc hin.
H s thu
hi ca
thuc bo
v thc vt
(pesticide)
t bnh m;
42 nghin
cu, trung
bnh 90%,
s=28%
(xem v d
A4)
28/ 42 =4.3%
(0.048 nh RSD)
Phng sai
gia cc ln
chy thu hi
Phng sai lch chun ca
nghin cu
Thu hi ca
thuc bo
v thc vt
t bnh m
qua d liu
lp li (xem
v d A4)
0.31 nh RSD
Ch thch 1: Hng s c bn hoc nh ngha h n v SI, xc nh khi lng bng cn
thng hiu chnh ti khi lng trong chn khng. Trong hu ht cc tnh hung thc t,
khi lng c ch thch l qui c c bn nh nh ngha ca OIML [H.18]. Qui c l
khi ng ti t trng khng kh ca 1.2kg m
-3
v t trng ca mu ca 8000kg m
-3
hoc t
trng khng kh l 1.2kg m
-3
. Khi t trng khng kh l thng gn vi gi tr cui cng, s
hiu chnh ti khi lng qui c c th thng c b qua. Gi tr KB chun a ra
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 87
cho t trng lin quan nh hng ti khi lng qui c trong bng trn l hiu qu c
lng ban u v khi lng trong qui c c bn khng hiu chnh trng lc ti mc nc
bin. Khi lng xc nh ca qui c c bn c th khc khi lng thc 0.1% hoc nhiu
hn (xem cc nh hng trong phn cui ca bng)
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 88
PH LC H. TI LIU THAM KHO
H.1 ISO/IEC 17025:1999. Yu cu chung v nng lc ca phng th nghim v hiu
chun
H.2 Hng dn din t khng m bo trong o lng. ISO, Geneva (1993). (ISBN
92-67-10188-9)
H.3 EURACHEM, nh lng khng m bo trong o lng phn tch. Phng th
nghim ho ca chnh ph, London (1995). ISBN 0-948926-08-02
H.4 Thut ng chung v c bn v o lng quc t. ISO, Geneva, (1993). (ISBN 92-67-
10175-1)
H.5 ISO 3534:1993. Thut ng v n v thng k. ISO, Geneva, Thu S (1993).
H.6 Ban k thut cc phng php phn tch, Analyst (London).120 29-34 (1995)
H.7 EURACHEM, p ng mc ch cho cc phng php phn tch. (1998)
(ISBN 0-948926-12-0)
H.8 ISO/IEC Guide 33:1989. S dng cht chun c chng nhn, ISO, Geneva (1989).
H.9 Hip hi quc t v ho cht tinh khit v p dng. Pure Appl.Chem., 67,331-343,
(1995).
H.10 ISO 5725:1994 (phn 1-4 v 6). Cp chnh xc ( ng v chm) ca cc phng
php o v kt qu o. ISO, Geneva (1994). Xem trong ISO 5725-5:1998 v cc
phng php la chn c lng chm.
H.11 I.J.Good mc tin cy, trong cun kin thc chung ca khoa hc thng k,
quyn 2, Wiley, New York (1982).
H.12 J.Kragten, Analyst, 119, 2161-2166 (1994).
H.13 Tiu chun Anh BS 6748:1986. Gii hn ca kim loi cn li trong gm, dng c thu
tinh, gm thu tinh v gm men thu tinh.
H.14 S.L.R.Ellison, V.J.Barwick. Cng nhn.Cht lng. m bo. 3 101-105 (1998).
H.15 ISO 9004-4:1993, Qun l cht lng ton din. Phn 2. Hng dn ci tin cht
lng. ISO, Geneva (1993).
H.16 H.Kaiser, Phn tch ho hc. 42 24A (1970).
H.17 L.A.Currie, Phn tch ho hc 40 583 (1968).
H.18 IUPAC, Gii hn pht hin, spectrochim. Acta 33B 242 (1978).
H.19 OIML Khuyn ngh IR 33. Gi tr qui c ca kt qu khi lng trong khng kh.
Hng dn nh gi KB trong phn tch ho hc nh lng
AGL 18 Ln ban hnh : 1.04 Trang : 89
MT S TI LIU THAM KHO CHO PHN B CA HNG DN
1. Guide to the Expression of Uncertainty in Measurement,ISO,Geneva,Switzerland
1993. ISBN 92-67-10188-9
2. Eurachem: Quantifying Uncertainty in Anatical Measurement, Laboratory of the
Government Chemist, London, UK, 1995. ISBN 0-948926-08-2
3. The Fitness for Purpose of Analytical Methods, A Laboratory Guide to Method
Validation and Related Topics, Eurachem Guide, Edition 1,1998. ISBN 0-948926-12-
0
4. Preactical Statistics for the Analytical Scientist, A Bench Guide, T.J.Farrant, Royal
Society of Chemistry, Cambridge, UK, 1997. ISBN 0-85404 442 6.
5. V.J Barwick and S.L. Ellison, Evaluating uncertainties associated with recovery,
1998, VAM Technical Repot, LGC/VAM/1998/052.
6. V.J.Barwick and S.L. R. Ellison, Analyst, 1999,124,981.
7. K.D. Bartle, A.A. Clifford, S. B. Hawthorne, J.J. Langenfeld, D.J. Miller, R.Robinson.
Journal of Supercritical Fluids, 1990,3,143.
8. S.L. R. Ellison, Accred. Qual. Assur., 1998,3,95.
9. S.L.R. Ellison and A Williams in The use of recovery factors in trace analysis, M.
Parkany (Ed), Royal Society of Chemistry, Cambridge, UK, 1996. ISBN 0-85404-736-
0.
10. Statistical Manual of the Association of Official Analytical Chemists, W.J. Youden
and E. H. Steiner, Association of Official Analytical Chemist, Arlington. VA, 1975.
ISBN .0-935584-15-3
11. R. L. Plackett and J. P. Burnam, Biometrika, 33,305, 1946.
12. Y. Vander Heyden, K. Luypaert, C. Hartmann, D. L. Massart J. Hoogmartens, J. De
Beer, Anal. Chim. Acta, 1995,312,245.
13. ISO 9004-4:1993, Total Quality Management Part 2. Guidelines for quality
improvement.
14. S.L.R. Ellison, V.J. Barwick, Accred. Qual. Assur., 1998, 3. 101.
15. S.L.R. Ellison, V.J. Barwick, Analyst, 1998, 123, 1387.
16. ISO 3534-1:1993. Statistics- Vocabulary and Symbols- Part 1: Probability and general
statistical terms.
17. International Vocabulary of basic and general standard terms in Metrology, ISO,
Geneva, Switzerland 1993. ISBN 92-67-10175-1.
18. V.J. Barwick, S. L. R. Ellison, Anal Comm., 1998, 35,377.
19. ISO 5725: 1994 Accuracy (Trueness and Precision) of Measurement Methods and
Results. ISO, Geneva, Switzerland.