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H tn
Bin son
Xem xt
Ph duyt
V Xun Thy
TS.H Tt Thng
K tn
THEO DI SA I TI LIU
TT
V tr
Ni dung sa i
Ngy sa i
II.
III.
AGL 18
Trang : 1
I.
1.
2.
3.
4.
5.
6.
7.
AGL 18
Trang : 2
8.
AGL 18
Trang : 3
Tnh
2 x 3 x 1 x 10-3 = 0.006 mL
Sau chuyn thnh lch chun bng cch chia cho 2 nn khng m bo do nh
hng ca nhit l:
0.006/2 = 0.0030 mL
Tng hp 3 thnh phn khng m bo trn s cho khng m bo ca th tch
dung mi chuyn qua pipet l:
10.
mL
khng m bo cn
Mt phng php yu cu cn mt chun ni b 100mg trn cn 4 s. Tnh khng
m bo chun ca vic cn?
- Chng ch hiu chun ca cn c nu khng m bo o l 0.0004g vi mc
tin cy khng di 95%
- Cn lp li qu cn 100mg trn cn 4 s c lch chun l 0.000041g
Tnh
khng m bo t vic hiu chun cn c tnh ton t chng ch hiu chun.
khng m bo c trch dn l 0.0004g vi mc tin cy l 95%. Bin i
thnh lch chun bng cch chia khng m bo cho 2. khng m bo
hiu chun l:
0.0004/2= 0.0002g = 0.200mg
Trang : 4
11.
W P
1000
V
Trong :
W:
P:
V:
100 ,5 99 ,9
1000 = 1004 , 0 mg / L
100
u p uv
+ +
P V
2
Trang : 5
AGL 18
Trang : 6
II.
1.
CN
1.1
Mc ch
32,5829
32,0822
Wt Cu, g
0,5007
Tuyn tnh
nhy
lp li
Khi lng m
Hiu chun
0 , 0001 / 3 = 0 , 000058
1.3.2 Qui trnh cn
1.3.2.1. Hiu chun tuyn tnh
Hiu chun bn ngoi ca cn c s dng tuyn b rng s khc nhau gia trng
lng tht trn a cn v s (trng lng) c trn thc chia trong khong
0,05mg vi tin cy 95%.
AGL 18
Trang : 7
Tng kt cc gi tr ca khng m bo
M t
1.5
Gi tr x
u(x)
u (x)/x
0,9999
0,000058
0,000058
500,7
0,07
0,00014
0 , 000058
+ 0 , 00014
khng m bo m rng vi h s ph k = 2 l:
U (WCu) = 0.07 x 2 = 0.14
khi lng ng 500.7mg bo co khng m bo l:
500,7 0,14 mg vi h s ph k=2 [mc tin cy xp x 95%]
Ghi ch phn b khng m bo ca tinh khit ca ng l rt nh c th
khng tnh n.
AGL 18
Trang : 8
2.
S CHUN B TH TCH
2.1
Mc ch
2.1.1 chun b mt axt ng ho dung dch chun nitrat Cu t 500.7mg Cu pha trong bnh
nh mc 500mL
2.1.2 Cc bc tin hnh l:
a)
b)
c) Khi phn ng ngng v Cu ho tan hon ton trong dung dch axit. Chuyn
dung dch ny vo bnh nh mc 500mL. Thm nc ct n vch nh mc.
2.2
Xc nh ngun khng m bo
2.3
AGL 18
Trang : 9
u (V) =
2.4
2.5
Gi tr X
U (x)
U (x)/x
500,7
0,07
0,00014
Th tch V, mg
500
0,26
0,0005
[u (W ) / W ]2 + [u (V ) / V ]2
= 0,00052
Cng nh nng ca dung dch Cu l 500,7mg/500mL = 1001,4mg/L
U(conc) = 0,00052 x1.001,4mg/L = 0,52mg/L
khng m bo m rng ca vic chun b 500,7 mg Cu trong 500ml dung dch hay
nng 1001,4 mg/L l 0,52 x 2 = 1,04mg/L vi h s ph k=2
Bi th, nng ca dung dch Cu l 1001,4 1,0mg/L vi h s ph k=2
2.6
Nhn xt
AGL 18
Trang : 10
3.
3.1
Mc ch
chun b 1 mol hoc dung dch thng, trng lng phn t ca dung dch cn bit
v khng m bo trong nh gi khi lng phn t. VD, chng ti yu cu tnh
khng m bo bng cch tnh khi lng phn t KMnO4
3.2
khng m bo
chun u (e)/3
Nguyn t
39,0983
0,0001
0,000058
Mn
54,938049
0,000009
0,0000052
15,9994
0,0003
0,00017
Ch :
3.4
AGL 18
Trang : 11
Nguyn t
H2
C
N2
O2
F
Na
Mg
Al
P
S
Cl2
K
Ca
Cr
Mn
Fe
Co
Ni
Cu
Zn
as
Br
Ag
Cd
Ti
Sb
I
Ba
Hg
Pb
AGL 18
KB lin quan
0.00007
0.0008
0.00007
0.0003
0.0000005
0.000002
0.0006
0.000002
0.000002
0.006
0.0009
0.0001
0.004
0.0006
0.000009
0.002
0.000009
0.0002
0.003
0.02
0.00002
0.001
0.0002
0.008
0.007
0.001
0.00003
0.007
0.02
0.1
Trang : 12
4.
4.1
4.2
Ngun khng m bo
C 4 ngun khng m bo chnh ng quan tm khi nh gi khng m bo ca
xobs
a. S thay i ngu nhin ca php o y (gm yi v yobs)
b. nh hng ngu nhin qui cho nhng gi tr ca xi
c. Hng s khng bit gia xi v yi
d. Gi nh khng c gi tr tuyn tnh
Trong 4 ngun trn th mt ngun c ngha nht l (a). Phng php nh gi (a)
thng qua s thay i cn li S, S c th tnh bng cng thc:
S2 = (yi - yc)2/(n-2)
Trong :
yi: l s c im hiu chun th i
yc: l s c tnh t y = a+bx
n: s im hiu chun
v u (xobs,y)= var(x) vi var (x)=S2/b2
4.3
V d
Trong v d ny c 3 chun s dng hiu chun
tp trung, xi
Thu c, yi
125
50
1,197
200
4,754
Trang : 13
xi+yi+ - nx y
b=
a = y - bx
xi - nx
2
Trong v d ny
x
x2
xy
125
625
25
50
1197
59850
2500
200
4754
950800
40000
Tng
255
6076
1011275
42525
Trung bnh
85
2025,333
Trong :
xiyi+ - nxy
1011275 - 3 x 85 x 2025,333
b=
= 23,732
xi2 - nx2
42525 - 3 x 852
5
50
200
125
1197
4754
yc c tnh
126,76259
1194,7086
4754,5288
(y - yc)
3,10672
5,25036
0,27961
V th
S2 = (yi - yc)2/(n-2)
= (3,10672 + 5,25036 + 0,27961)/(3 - 2)
= 8,63669
var(x)
= S2/b 2
= 8,63669 / 23,73213432
= 0,0153346
u(xobs,y) =
AGL 18
var(x) =
0.0153346= 0,124
Trang : 14
5.
5.1
Mc ch
V d di ch ra khng m bo o trong k kh khi ph GC- MS
(gas chromatographic - mass spectrometric).
5.2
Tinh khit
Ho tan
Cn
chm
chm
Cspl
A0
chm
A50
chm
Aspl
chm
Bc 3: Xc nh khng m bo tng hp
C50:
- Dung dch chun c chun b t cht rn biphenyl, u tin cn v sau ho tan
v pha long trong benzen.
Vi cc ln cn khc nhau tnh c khng m bo chun l 0.000206g i vi
0,052g biphenyl
AGL 18
Trang : 15
Gi tr
0.052
99.5%
1000.22
KB
0.000206
0.289%
0.857
0.052
0.052206
0.052
0.052
99.5%
99.5%
99.789%
99.5%
1000.22
1000.22
1000.22
1001.077
C50
51.72862
51.9335
51.8789
51.6843
0.20492
0.15025
-0.04428
0.04199
0.02257
0.00196
0.066529
u (C50)
AGL 18
0.257933
Trang : 16
A0 , A50 , Aspl
o lp li a ra kt qu sau:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Trung bnh
lch chun
lch chun trung bnh
Vng phn ng ca GC - MS
A0
A50
2
390
0
397
0
395
1
394
0
398
2
396
2
391
1
392
0
396
1
395
0.9
394.4
0.876
2.633
0.277
0.833
Aspl
265
260
269
266
263
268
265
262
267
265
265
2.749
0.869
AGL 18
(0 , 222
+ 0 , 577
) = 0 , 618 ug
/ mL
Gi tr
KB
C50
51.72862
0.257933
A0
0.9
0.277
A50
394.4
0.833
Aspl
265
0.869
C50
A0
A50
Aspl
51.72862
0.9
394.4
265
51.98655
0.9
394.4
265
51.72862
1.177
394.4
264
51.72862
0.9
395.233
265
51.72862
0.9
394.4
265.869
Cspl
34.8363
34.861
0.0245
0.0006
34.7627
-0.07359
0.00542
34.9505
0.11424
0.01305
u(Cspl)
0.04924
0.2219
35.01
0.173703
0.030173
Trang : 17
A0
A50
Aspl
Gi tr
0.052
99.5%
1000.22
0.9
394.4
265
KB
0.000206 0.289%
0.857
0.277
0.833
0.869
0.052
0.052206 0.052
0.052
0.052
0.052
0.052
99.5%
99.5%
99.789%
99.5%
99.5%
99.5%
99.5%
1000.22
1000.22
1000.22
1001.077 1000.22
1000.22
1000.22
A0
0.9
0.9
0.9
0.9
1.177
0.9
0.9
A50
394.4
394.4
394.4
394.4
394.4
395.233
394.4
Aspl
265
265
265
265
265
265
265.869
Cspl
34.8363
34.9743
34.9375
34.8065
34.8608
34.7627
34.9505
0.13801
0.10118
-0.0298
0.02454
-0.0736
0.11424
0.01905
0.01024
0.00089
0.0006
0.00542
0.01305
0.04924
u(Cspl)
0.221902
Bng ny a ra kt qu tng t nh bng kt qu trc
AGL 18
Trang : 18
6.
6.1
Gii thiu
6.1.1 khng m bo ca c tnh cht liu ca vt cht nh trng lng v khi lng
ca dung dch chun b c mi lin h n gin v khng phc tp xc nh. Cc
c tnh phn tch ca vt cht m gi tr thc v bn cht ca thnh phn c xc
nh l phc tp bi v trong tin trnh phn tch chng ta tin hnh khng ch php
phn tch cui cng nhng hu ht cc trng hp mt th tc tin phn tch m c th
t bn thn n l ngun gy sai khc ln hn l s sai khc c tm thy trong bn
thn php phn tch.
6.1.2 Cc th tc phn tch thng da vo cc c tnh ho hc ca vt cht v d dng ca
hp cht cho php phn tch ngay hay tch ra qua tnh cht cht liu c s dng
tch v d tnh tan, tnh bay hi/d bay hi...Cc tnh cht s dng cho cc th tc
phn tch khng l cc tng chng l cc ch s mt hn ch nh hng n
chnh xc v cp chnh xc ca cc kt qu phn tch bi nguyn nhn sai s c th
ca khng m bo a ra trong phng php. V d: cc kt ta khng tan thng
tan trong mt chng mc no , qui trnh khng tch c th lin quan nh s hon
ho v ...v.v.
6.1.3 Khng th tho lun tt c cc nguyn nhn c th m c th ch dn cc sai s trong
cc qui trnh phn tch ring v nh phn tch phi bit trc cc sai s h thng v
hiu chnh chng khi khng m bo phn tch c tnh n. Hn na bt c
phng php phn tch v bt c s thay i no trong phng php l i tng ca
cc sai s c th ca bn thn phng php . y chng ta phi cp duy nht
cc ngun chung ca sai s c th m tnh cht quan trng ca sai s c th c din
t bng s.
6.2
6.2.1 Ngun c th ca sai s trong php phn tch trng lng qua s kt ta l ho tan ca
cc kt ta.
S cn bng
ABn A + Bn
M c thit lp trong s khng ho tan ca mt tnh cht c th ho tan ca ABn. l
cc c im bi sn phm ho tan
Ksp = [A][B] n
tp trung [A] v [B] s dng trong sn phm pha long phi thng c din t
nh nng phn t gam. Cc gi tr Ksp ca mt vi vt cht quan trng c a ra
bng di:
AGL 18
Trang : 19
Ksp
1.56 x 10 -10 (25)
7.7 x 10-13 (25)
1.5 x 10-16 (25)
1.1 x 10-36 (18)
1.1 x 10-15 (18)
1.6 x 10-14 (18)
2.45 x 10-5 (25)
1.08 x 10-10 (25)
1.5 x 10 -8 (18)
0.87 x 10-8 (25)
2.6 x 10 -5 (12)
7.0 x 10 -9 (16)
6.2.2 V d 1
tnh mi quan h sai s, nguyn nhn do ho tan ca phn ca cht kt ta trong qu
trnh ra bng cch gn/cht: 0.1g ca AgCl c ra vi 250ml nc ti 250C
y
Ksp = [Ag+][Cl-] = 1.56 x 10-10 mol2.L-2
Nu mt mol ca AgCl ho tan trong mt lt nc th: [Ag+] = [Cl -] = a
T vic ho tan ca mt mol AgCl, mt mol ion Ag v mt mol ion Cl c sinh ra
Thay th vo s din t cho Ksp chng ta c: Ksp = a2 = 1.56 x 10-10 mol2.L-2
v do : a = 1.25 x 10-5 mol.L-1
Nng ca AgCl g/L l a ra bi cng thc nhn trng lng gram ca AgCl
1.25 x 10 -5 mol.L-1 x 143.3g.mol-1 = 1.8 x 10-3 g/L
Bi vy ch 4.5 x 10 -4 g ca AgCl s ho tan trong 250ml nc ra s dng
Sai s i km l:
4.5 x 10 -4 x 100
% = 0.45%
0.1
Ch thch: Sai s ny khng nh nn khng th b qua c. Sai s ny phi c hiu
chnh trong vic c lng khng m bo.
6.2.3 V d 2
tnh nguyn nhn sai s trong phn tch trng lng ca 0.1g AgCl bng ra cht kt
ta vi 250ml dung dch HCl 0.01M
Trong trng hp ny, [Cl-] = 0.01M hoc 10-2mol.L-1
AGL 18
Trang : 20
6.3.1 Sn phm tan c cng c s dng tnh ton trong chun cht kt ta m
im cn bng c th c ch ra bi s to thnh ca ho tan t t cht kt ta qu
mc chun v trong s phc tp chun m mt cht kt ta c ho tan li.
6.3.2 V d 3
Trong chun Mohr dung dch nitrat bc vo dung dch NaCl m thm cromat kali.
AgCl kt ta hon ton trong khi chun nhng rt nhanh chng nng Cl t mt
gi tr hin ti, dng clo bc nu ch ra mc cn bng hoc im kt thc. Tng cc
ion Cl khng c chun tng ng ti nng ion bc dng clo bc.
Tng s khng chun ny c th c xc nh t sn phm
K(Ag2CrO4) = [Ag+]2[CrO42-] = 2 x10-12mol3.L-3
Bng tnh nng ion trong dung dch v thay th gi tr ny vo cng thc ton.
Nu chng ta cn nhc trng hp m 1mL ca 5% w/v dung dch clo kali c thm
vo ho 25mL ca 0.1M dung dch Clo v 0.1 nitrat bc, nng ion Clo l:
0.05
1000
[CrO4 ] = ---------- x -------- mol.L-1 = 5.15 x 10-3 mol.L-1
194.2 50
2-
2 x10 12
1
mol.L = 2 x 10 -5mol.L-1
3
5.15 x10
AGL 18
Trang : 21
50
--------- x 2 x 10 -5 mol = 10-6 mol
1000
Nh tng tnh l
25
-------- x 0.1mol
1000
V th sai s km theo l:
10 -6 x 100
--------------- %, hoc 0.04%
2.5 x 10-3
C th thy t tnh ton trn trong trng hp ny sai s chun ph thuc vo nng
ca cht ch th thm vo; iu ny c din t s cn nhc rng cht ch th
vn chuyn vai tr ca cht lm kt ta. Nu cho qu nhiu clo vo dung dch, clo bc
c nh dng trc khi t c im kt thc; mt khc nu nng clo l qu nh,
thm nitrat bc thm vo dung dch vt qu v bi vy m mu clo bc s kh nhn
thy hn. V th sai s c th lm nh i bi vic gi iu kin chun (nh tng
cht ch th nng v dung tch ca dung dch...) gn nh ging nhau qua s tiu
chun ho ca chun bng chun ca clorua natri tinh khit s dng sau khi
chun trong xc nh mu.
6.4
6.4.1 Trong m hnh phn tch ho hc cc phng php chit l thng c s dng
phn chia cc cht. Qui tc ca cc phng php l s phn b mt cht trong hai dung
mi. Th tc thc hin bao gm vic lc dung dch, thng mt dung dch m vic
lc khng ho trn c m cht c chit d ho tan hn theo s phn chia
c hc ca hai gia on.
6.4.2 Trong phn tch ho hc hu c dung dch - s chit dung dch c s dng cho thi
gian di; trong phn tch ho hc v c, hp cht phc tp (thnh thong mu) ca cc
kim loi khc nhau c chit trong dung mi phn cc thp. S phc tp ca mu c
th o c ngay lp tc bi my o mu. Hoc dung mi c th c bay hi sau khi
chia, v thnh phn chit c a tr li dung dch nc v xc nh c im chia.
6.4.3 Kh nng trng hp khc trong vch v d thc hin chit li vo dung dch nc ca
mt thnh phn khc (thng pH khc nhau) t dung dch/ho tan khi s chit bc
u kt thc. Trong cc phn tch vt s chit l thng bao gm quang ph hc hoc
trc quang s ht v pht ra nguyn t.
6.4.4 Nng ca cht trong dung dch gim i bi s chit t nng nguyn C0 ti nng
C1 l:
VA
C1 = C0 ---------------DVB + VA
Nu D l h s phn b v VA, VB l dung tch ca giai on A v B s dng trong chit.
Trong hot ng chit tip theo nng ca cht c chit gim so vi nng ban u l
AGL 18
Trang : 22
VA
------------------DVB + VA
C2 = C0
100
------------------85 x 50 + 100
= 0.0046 g
C2 0.2
100
------------------85 x 50 + 100
2
= 0.0001057 g
v gy ra khng m bo l:
2
0.0001057 x 100
------------------0.2
Do khi thc hin chit CCl2 l chit hon ton iot t dung dch nc.
AGL 18
Trang : 23
7.
Gii thiu: V d ny tho lun v vic chun b mt dung dch chun cho thit b quang ph
hp ph nguyn t (AAS), t kim loi c tinh khit cao (trong v d ny l 1000mg/L Cd
pha trong HNO3). D v d ny khng i din cho mt php phn tch nhng vic s dng
chun hiu chun l mt phn ca hu ht cc php phn tch v php phn tch thng thng
l cc php o m c lin quan ti cc chun cung cp vic lin kt chun ti h n v SI.
Bc 1: Yu cu k thut
Mc tiu ca bc 1 l vit ra tuyn b r rng l i lng no c o. Yu cu k thut
v d ny l m t vic chun b chun hiu chun v php ton th hin mi lin quan ca i
lng o v cc thng s m i lng o ph thuc.
Qui trnh/th tc
Chun b chun hiu chun bao gm cc bc sau:
Chun b chun cadmi (Cd)
Lm sch b mt kim
loi
Cn kim loi
Ho tan v pha
long
Kt qu
Cc bc tin hnh l:
B mt ca kim loi c tinh khit cao c x l vi hn hp axit loi b cc oxit
kim loi. Phng php lm sch c nh cung cp kim loi a ra v cn c th thu
c kim loi tinh khit nh cng b trong chng ch.
Bnh nh mc (100mL) c cn theo 2 cch l khng c kim loi tinh khit v c kim
loi tinh khit bn trong. Cn s dng c phn gii 0.01mg.
Tnh ton
i lng o trong v d ny l nng ca dung dch hiu chun v ph thuc vo khi
lng tinh khit ca kim loi c tinh khit cao (Cd), Dung tch ca dung dch c pha
long. Nng ca dung dch c th hin theo cng thc:
AGL 18
Trang : 24
C Cd =
Trong :
CCd:
1000.m.P
mg / L
V
1000:
m :
P
V
:
:
AGL 18
Trang : 25
V
Nhit
Hiu chun
lp li
c(Cd)
phn gii
phn gii
m(b)
Tuyn tnh
nhy
m(tng)
Tuyn tnh
lp li
lp li
Hiu chun
nhy
Hiu chun
m
3
u ( P) =
0.0001
3
= 0.000058
Khi lng m
KB lin quan vi khi lng ca Cd c c lng s dng d liu t chng ch hiu
chun cn v khuyn co ca nh sn xut v vic c lng KB l 0.05mg. Vic c
lng ny l t 3 ngun KB c nu trong bc 2.
Th tch V
Chun b th tch c 3 ngun nh hng chnh: hiu chun, lp li v nhit .
- Hiu chun: nh sn xut cung cp s liu cho bnh nh mc l 100mL 0.1mL ti iu
kin 20 0C. Gi tr KB c cung cp khng c mc tin cy hoc thng tin v phn
b, do d on phn b theo hnh tam gic v KB c tnh theo cng thc:
0.1mL
6
= 0.04mL
Trang : 26
= 0.05mL
C Cd =
1000.m.P
mg / L
V
S dng cc gi tr thu c th hin trong bng trn tnh c nng ca chun hiu chun
CCd nh sau:
C Cd =
Gi tr x
u(x)
u(x)/x
0.9999
0.000058
0.000058
100.28
0.05 mg
0.0005
100.00
0.07 mL
0.0007
Da vo cng thc tnh KB tng hp vi trng hp cng thc tnh i lng o l php
nhn v chia ta thu c KB tng hp:
2
u c (Cd )
u (V )
u( P)
u (m)
2
2
2
=
+
+
= 0.000058 + 0.0005 + 0.0007 = 0.0009
C Cd
P
m
V
u(cCd) = CCd x 0.0009 = 1002.7mg/L x 0.0009 = 0.9 mg/L
KB m rng U(cCd) c tnh bng cch nhn KB tng hp vi h s ph k = 2:
U(cCd) = 2 x 0.9mg/L = 1.8 mg/L
Qua phn tnh KB tng hp chng ta nhn thy KB chun do nh hng ca vic
chun b dung tch bnh nh mc l ln nht sau n nh hng do cn kim loi. nh
hng do tinh khit ca kim loi gy ra KB rt nh, khng ng k.
AGL 18
Trang : 27
* Vic tnh ton KB tng hp c th c tnh theo cch s dng bng tnh di
y:
A
Gi tr
0.9999
100.28
100.00
KB
0.000058
0.05
0.07
4
5
0.9999
0.999958
0.9999
0.9999
100.28
100.28
100.33
100.28
100.00
100.00
100.00
100.07
c(Cd)
1002.69972
1002.75788
1003.19966
1001.99832
10
u(y,xi)
0.05816
0.49995
-0.7014
0.00338
0.24995
0.49196
11
u(y) ,u(y,xi)
0.74529
12
13
u(c(Cd))
0.9
AGL 18
Trang : 28
1.
Phng php.
Xc nh dung dch NaOH 0,1 M bng chun trn c s dung dch KHP 0,1 M
1.2
1.3
Th tc.
-
Bc 1: Cn 5 g KHP
Bc 2: Ho tan KHP trong nc v nh mc ti 250 ml th tch
Th tch (KHP)
1.4
Bc 1: Cn KHP
Cng vic
Hp ng + KHP
33,5895 g
Hp rng
28,5130 g
AGL 18
5,0765 g
Trang : 29
Cc ngun khng m bo
Khi lng (KHP)
Hiu chun
Hiu chun
nhy
tinh khit (KHP)
nhy
lp li
tuyn tnh
lp li
tuyn tnh
Hiu chun
Hiu chun
lp li
nhy
Tuyn tnh
Tuyn tnh
Cn (tng)
Cn (b)
c (NaOH)
lp li
Hiu chun
Nhit
AGL 18
chch
lp li
im kt thc
Trang : 30
a.
b.
c.
S khc nhau gia nhit dung dch v nhit hiu chun ca bnh nh mc.
Coi nh ch h s gin n th tch ca dung dch bi v n l con s ng k ln hn
dung tch gin n ca bnh nh mc thu tinh, cho mc ch thc hin.
Ly h s gin n i vi nc l 2.1 * 10-4 trn mt C v nu s khc nhau v nhit
gia dung dch v nhit hiu chun l 5 .. i vi dung tch 250 ml c s
dng s a ra mt khong tin cy 95% ca:
250 x 5 x 2.1 x 10-4 mL = 0.263 mL
Do s khc nhau lch chun ca nhit l:
0.263/ 2 = 0.132 ml
khng m bo o phi hp ca th tch chun KHP u (Vk) l:
u (Vk) =
3 , v ta c.
3 = 0,0012
AGL 18
Trang : 31
Cng thc phn t ca KHP l C8 H5O4K . Xem bng trng lng nguyn t ca cc nguyn
t, C, H, O, K bao gm cc c lng khng m bo c ban hnh bi IUPAC tp ch
Ho hc tinh khit v ng dng, s 66.
Nguyn t
KB
KB chun
12.011
0.001
0.00058
1.00794
0.00007
0.00004
15.9994
0.0003
0.00017
39.0983
0.0001
0.000058
Trng lng c
tnh ton
Kt qu c
tnh
KB c
tp hp
C8
8 x 12.011
96.088
0.0046
H5
5 x 1.00794
5.0397
0.00020
O4
4 x 15.9994
63.9976
0.00068
1 x 39.0983
39.0983
0.000058
204.2236
Do khi lng phn t ca KHP l 204,2236 v khng m bo tng hp ca u(MW)
l cn bc 2 ca tng bnh phng ca cc khng m bo ring bit. V d
u(MW) =
Gi tr c s
dng, V
KB
Wk
5.0765 g
0.000104
2.05 * 10 -5
0.998
0.0012
1.202 * 10-3
Vk
250 ml
0.16
6,4 * 10-4
MW
204.2236
0.0047
2.3 * 10-5
Do khng m bo chun ca nng (Mk) trong dung dch chun KHP c biu
din nh sau:
u (Mk)/ Mk =
Nng dung dch KHP, Mk, c tnh theo cng thc (1) nh sau:
Mk = (5,0765 * 0,998 * 1000) / (250 * 204,2236) = 0,0992 mol L-1
AGL 18
Trang : 32
Bc 6: Chun dung dch NaOH trn c s dung dch KHP chun (Va)
25 dung dch NaOH c chun trn c s dung dch chun KHP t mt burette 50 mL.
Mt khc, chng ta cn lu cc ngun khng m bo t quan im ca cc 3 yu t tng
ng c tho lun trn:
a.
AGL 18
Trang : 33
Khi mong mun s dng khong 25 mL dung dch chun trong vic chun , vic cn v c
lp li ca th tch 25 mL t buret c kim tra v a ra mt lch chun 0,012 mL.
Chng ta phi s dng con s ny nh khng m bo chun ca th tch c s dng.
c.
hoc 0.034 ml
Gi tr c s
dng, V
khng m
bo
lch chun
lin quan
Mk
0.00014
1.41 x 10 -3
Vk
25.2 ml
0.034
1.35 x 10 -3
Va
25.0 ml
0.021
8,40 x 10 -4
khng m bo chun trong nng dung dch NaOH (Ms) c tnh nh sau:
u (Ms)/ Ms =
AGL 18
Trang : 34
Nng ca dung dch NaOH, Ms, c tnh theo cng thc (2) nh sau:
Ms = (25.20 x 0.992)/ 25.0 = 0.100 mol L-1
T , khng m bo chun u (Ms) trong nng dung dch NaOH l:
u (Ms) = 0.0021 x 0.1000 = 0.00021 mol L-1
Bc 8: Ly 25 ml dung dch NaOH chun HCL (Vb)
25 ml th tch dung dch NaOH chun c s dng cho chun , nhng lu tng t c
th c p dng nh trong bc 5, 25 ml dung dch vi khng m bo chun l u (Vb)
0.021 ml.
Bc 9: Chun NaOH trn c dung dch HCL (Vc)
Nh trong bc 6, dung dch HCL chun 25 ml NaOH t buret 50 ml. Do khng
m bo chun tng hp, u(Vc) l 0.034ml.
Bc 10: Tnh ton nng dung dch HCL (Mh)
Cng thc c s dng trong vic tnh ton dung dch NaOH l:
Mh = (Ms x Vb)/Vc
Mh: Nng dung dch HCL
Ms: Nng dung dch NaOH chun
Vb: Th tch dung dch NaOH chun c s dng
Vc: Th tch dung dch HCL c chun
Lu ton b nhng tp hp khng m bo trong bc 3 n bc 9, chng ta c th
tm tt chng nh di y:
Nhn t khng
m bo
Gi tr c s
dng, V
khng m
bo
lch chun
lin quan
Ms
0.00021
2.13 x 10 -3
Vb
25.00 ml
0.021
8.4 x 10-4
Va
25.10 ml
0.034
1,35 x 10 -3
khng m bo o chun lin quan trong nng dung dch HCL (Mh) c tnh nh
sau:
u( M h )
Mh
Nng ca dung dch HCL, Mh, c tnh theo cng thc (3) nh sau:
Ms = (25,00 * 0,100)/ 25,30 = 0,0988 mol L-1
T , khng m bo tng hp chun u (Mh) v nng dung dch HCL l:
u (Mh) = 0,0027 x 0,0988 = 0,00027 mol L-1
AGL 18
Trang : 35
Nhng lu :
nh hng nhit s khc nhau gia nhit phng v nhit hiu chun;
tinh khit ca ho cht c s dng trong chun ho;
AGL 18
Trang : 36
2.
2.1
a.
b.
Cn chnh xc 10g mu sa bt
Mu c chit di s c mt ca NH4OH vi ru cn, ete etilic v ete du.
c.
Cc este metyl axit bo ca vic chit cht bo c chun b bng s dng NaOCH3 v
este ho BF3CH3OH
d.
e.
f.
Xc nh ngun khng m bo
Nguyn nhn v kt qu c th c xy dng nh sau;
Fml
Fla
Cml
Cspl
AGL 18
Wspl
Trang : 37
2.3
chng c o v thu c kt qu
Phm vi phn
ng thc
0
133
278
558
1192
Tng
xy
x2
133
133
278
556
558
2232
16
10
1192
11920
100
17
2161
14841
121
Do
xiyi
= 14841/121 = 122.6528926 y = 122.6528926x. V th:
b=
x
AGL 18
(y - yc)2
Tnh yc
133
122.652893
107.06263
278
245.305785
1068.9117
558
490.61157
4541.2005
10
1192
1226.52893
1192.2467
Trang : 38
Do ,
S2 = (yi - yc)2/(n-2) = (107.06263 + 1068.9117 + 4541.2005 +1192.2467)/ (5-2)
= 2303.14
var(x)= S2/b2 = 2303.14/122.65289262 = 0.1531
u(xobs,y) = var(x) = 0.1531 = 0.391
Kt qu l u(Cml) = 0.391mg/mL
V: Bnh dung tch s dng y dung dch cui cng n 25mL c chng ch gi tr
25.040 0.015 mL ti 200C thu c t ti liu k thut ca nh cung cp. Trong nghin cu
ny phn b dng hnh ch nht c la chn. Bi vy khng m bo hiu chun l
0.0153 = 0.00866mL
Bnh thu tinh c s dng trong mi trng m nhit thay i 4.00C (mc tin cy
95%, nu khng nu mc tin cy th phn b hnh ch nht c tha nhn)
H s n ca heptan theo s thay i nhit l khng c bit n, c tha nhn n
khong gp hai nh h s n ca nc 2.1x10-4 mL/0C. Trong trng hp ny h s n ca
heptan c tha nhn l 4.2x10 -4 mL/0C. T kinh nghim ca chng ta chng ta bit rng s
tha nhn l trong c ln hn phm vi nhit ca PTN ni m tin hnh phn tch.
khng m bo theo s thay i nhit cho mt dung tch 25.04mL l t ti im ln nht
ca 25.04x(4.0/2)x4.2x10-4 = 0.0210mL
Bi vy, u (V) =
Fla: nh v d trc trng lng phn t (NW) ca axit linoleic (C18H32O2) v khng m
bo ca n c tnh nh sau:
Gi tr
12.0107
1.00794
15.9994
KB
0.00046
0.00004
0.00017
12.0107
12.01116
12.0107
12.0107
1.00794
1.00794
1.00798
1.00794
15.9994
15.9994
15.9994
15.99957
Fla
280.44548
280.454
280.447
280.446
0.00832
0.00128
0.00035
6.9E-05
1.6E-06
1.2E-07
7.091E-05
u (Fla)
AGL 18
0.008421
Trang : 39
Gi tr
12.0107
1.00794
15.9994
KB
0.00046
0.00004
0.00017
12.0107
12.01116
12.0107
12.0107
1.00794
1.00794
1.00798
1.00794
15.9994
15.9994
15.9994
15.99957
Fml
294.47206
294.481
294.473
294.472
0.00878
0.00136
0.00035
7.7E-05
1.8E-06
1.2E-07
7.902E-05
u (Fml)
0.0088895
AGL 18
Trang : 40
Cml
Fla
Fml
Wspl
Gi tr
7.15
25.04
280.44548
95.0%
294.47206
10.0232
KB
0.391
0.0227
0.008421
5.61%
0.00889
0.00033
Cml
7.15
7.541
7.15
7.15
7.15
7.15
7.15
25.04
25.04
25.0627
25.04
25.04
25.04
25.04
Fla
280.44548
280.445
280.445
280.4539
280.445
280.44548
280.445
95.0%
95.0%
95.0%
95.0%
100.61%
95.0%
95.0%
Fml
294.47206
294.472
294.472
294.47206
294.472
294.48095
294.472
Wspl
10.0232
10.0232
10.0232
10.0232
10.0232
10.0232
10.0235
Cspl
17.906665
18.8859
17.9229
17.907203
16.9082
17.906125
17.9061
0.97923
0.01623
0.0005376
-0.9985
-0.000541
-0.00058
0.95889
0.00026
2.89E-07
0.99695
2.922E-07
3.4E-07
1.9561078
u(Cspl)
1.3986092
AGL 18
Trang : 41
( )
( )]
u(x)/x =
{[u(x )/ x ] +[u(x )/ x ] }
2
KB chun
KB lin quan
Cml
7.15mg/g
0.391 mg/g
0.0547
25.04mL
0.0227 mL
0.0009
Fla
280.44548g/mol
0.00842 g/mol
0.00003
Fml
294.47206g/mol
0.00889 g/mol
0.00003
Wspl
10.0232
0.000327 g
0.00003
95.0 %
5.61 %
0.0591
r
Cspl
0.170
17.90667mg/g
3.35 mg/g
0.192
AGL 18
Trang : 42
3.
S nguyn nhn v kt qu
CKOH
W (du)
MW (KOH)
Gi tr ca axit
Chun (V)
3.3 Xc nh cc khng m bo
3.3.1 Dung dch chun KOH 0.1M vi HCl 0.5M
A
(0 .23
+ 0 . 32
)/ 1000
= 0.00039
AGL 18
Trang : 43
khng m bo chun ca trng lng phn t HCL, theo khi lng nguyn t
IUPAC v phn b hnh ch nht, l:
u(mHCL) = 0.000043
Cn lu rng u(MHCL)/ MHCL l khng ng k khi so snh vi u(V)/V v
u(mHCL)/ mHCL , khng m bo chun lin quan l:
u(Cst)/ Cst =
B.
2
2
(0.00039 + 0.00022 ) = 0.00045.
Xc nh CKOH
Nng chnh xc ca dung dch KOH c thit lp trc khi s dng bng chun
trn c s dung dch HCL chun.
Do , CKOH = Cst * Vst/ VKOH
Ni, Vst l th tch (ml) dung dch HCL chun c s dng cho chun th tch
VKOH (ml) ca dung dch KOH.
Nh c trnh by trn, u(Cst)/ Cst = 0.00045
i vi vic chuyn dung dch KOH n bnh tam gic, mt pipet thu tinh dung tch 5
0.01 ml c s dng. Ly s bin i nhit c th l 30C vi tin cy 95%,
v lp li ca pipet ( lch chun) 0.0033 mL, n c th tnh u(VKOH)/VKOH =
0.0015
Vic chun c hon thnh s dng mt buret vi lng 5 ml c vch chia 0.01
ml ( chnh xc hiu chun ca nh sn xut l 0.01 ml)
S sai khc nhit c th l tng t nh nu trn, lch chun ca vic ong l
0.0033 mL v lch chun ca im ch cui cng tng ng vi c ca buret
(0.017mL) l 0.0098mL
V th gi tr ln nht ca u(Vst)/Vst = 0.013 nu CKOH = 0.1 mol/L v tng ng Vst
= 1 mL
khng m bo u(Cst)/Cst v u(VKOH)/VKOH l khng ng k trong so snh ti
u(Vst)/Vst
V vy u(CKOH)/CKOH = u(Vst)/Vst = 0.013
3.3.2 Xc nh gi tr ca axit
Gi tr ca axit l:
AV = MKOHVKOHCKOH / m
Lu phng php th s dng v khi lng phn t KOH l 56.1 thay th hon ton
gi tr MKOH = 56.10564; bi th trong trng hp ny
u(MKOH)/MKOH = 0.00564/(56.1 x 3 ) = 0.00006
chit axit bo t do bng dung dch KOH chng ta s dng buret 5mL ni trc
u(Vst)/Vst = u(Cst)/Cst = u(Vst)/Vst = 0.013
AGL 18
Trang : 44
u( Av) / Av =
khng m bo m rng vi h s ph k 2 l
U(AV)/AV = 2 x 0.018 hoc 0.04
Ghi ch: s ch ca im kt thc ca chun l ngun nh hng khng m bo ln. Nu
buret v d c c l 0.043mL khng m bo m rng c th tng n 0.07
Hn na mu ca du v s thay i c th trong cht ch th chy ti gn im kt thc trong
dung dch du ho tan l khng c tnh ti. Tng t mi lin quan ti nh hng ca CO2
khng kh trong CKOH
AGL 18
Trang : 45
4.
4.1
Tm tt
4.1.1 Mc ch
Xc nh d lng thuc tr su phospho hu c trong bnh m dng phng php chit v
sc k kh (GC)
4.1.2 Qu trnh o
Qu trnh xc nh d lng thuc tr su phospho hu c trong bnh m c th hin
hnh 4.a
Hnh 4.a. Phn tch thuc tr su phospho hu c
ng nht
Tch chit
Lm sch
C c
Chun b chun
hiu chun
Xc nh GC
Hiu chun GC
Kt qu
4.1.3 i lng o
D lng thuc tr su phospho hu c trong bnh m c tnh theo cng thc sau:
Pop =
I op .cref .Vop
I ref . Re c.msample
Trong :
Pop: hm lng thuc tr su c trong mu (mg.kg-1)
Iop : Cng ti a ca phn chit ca mu
Cref : Nng khi lng ca cht chun (g.ml-1)
Vop : Th tch cui cng ca dch chit
106 : chuyn t g.g-1 sang mg.kg-1
Iref : Cng ti a ca cht chun
AGL 18
Trang : 46
c(ref) tinh
khit (ref)
V(op)
m(ref)
I(op)
I(ref)
m(ref)
V(ref)
pha long
tuyn
tnh
hiu chun
I (op)
nhit
hiu chun
nhit
V(ref)
hiu chun
hiu chun
V(op)
hiu chun
Pha long
m (sample)
P(op)
m(gross)
m(tare)
tuyn
tnh
hiu chun
tuyn
tnh
hiu chun
hiu chun
F(hom)
I(ref)
thu hi
m mu
KB
chun u(x)
j KB chun
tng i u(x)/x
lp li
1.0
0.27
0.27
Da trn 2 ln th ca 2
mu khc nhau
chch
0.9
0.043
0.048
mu thm
Cc ngun gc khc
( ng nht...)
1.0
0.2
0.2
nh gi trn c s
phng php s dng
u(Pop)/Pop
--
--
0.34
KB chun tng i
M t cc ngun
AGL 18
Ghi ch
Trang : 47
0.1
0.2
0.3
0.4
ii)
iii)
iv)
v)
Axeton nitril/hexane lng, ra axeton nitril bng hexane, sy hexane qua ct natri
sulphate
vi)
AGL 18
Trang : 48
vii) Pha long n th tch tiu chun Vop (khong 2ml) trong ng nghim chia vch 10ml
viii) o : Tim 5l dch chit v o GC c c cng mi (peak) Iop
Chun b dung dch chun 5l .ml-1 (nng khi lng Cref)
Hiu chun GC s dng 5l dung dch chun, tim v o GC c cng mi
ix)
x)
chun Iref
Hnh 4.a. Phn tch thuc tr su phospho hu c
ng nht
Tch chit
Lm sch
Bulk up
Chun b chun
hiu chun
Xc nh GC
Hiu chun GC
Kt qu
Tnh ton kt qu
Nng khi lng Cop ca mu cui cng c tnh nh sau
C op = c ref .
I op
I ref
g.ml-1
cop .Vop
Re c.msample
. 106
mg.kg-1
I op .c ref .Vop
I ref . Re c.m sample
.10 6 mg.kg-1
Trong :
Pop: Mc thuc tr su trong mu (mg.kg-1)
Iop: Cng mi ca mu chit
Cref: Nng khi lng ca mu chun (g.ml-1)
AGL 18
Trang : 49
hiu chun
c(ref) tinh
khit (ref)
tuyn tnh
I (op)
V(op)
m(ref)
chm
nhit
nhit
V(ref)
hiu chun
hiu chun
hiu
chm
chm
Pha long
P(op)
m(khng b)
m(b)
chm
tuyn
tnh
hiu chun
nhy
nhy
F(hom)
AGL 18
thu hi
I(ref)
hiu chun
tuyn
tnh
chm
hiu chun
m mu
Trang : 50
Pop =
I ref . Re c.msample
Trong F(hom) l mt s hiu chnh gi thit cho tnh thng nht trong php tnh gc. iu
ch r rng khng m bo o trong h s hiu chnh phi c bao gm trong s nh
gi khng m bo o tng. Cng thc trn cng ch ra khng m bo o s c p
dng.
Ch thch: Cc h s hiu chnh: cch tip cn ny kh l khi qut v c th rt c gi tr. V mt
nguyn l, mi php th u phi c cc h s hiu chnh thng nht. V d: khng m bo o Cop
c th c din t bng khng m bo o chun i vi Cop hoc khng m bo o chun
i din cho khng m bo o trong cho h s hiu chnh. Trong trng hp sau, gi tr xc nh
khng m bo o Cop c din t bi lch tiu chun tng i.
ti lp(1)
I (op)
V(op)
c(ref) tinh
khit (ref)
V(op)
m(ref)
I(op)
I(ref)
m(ref)
V(ref)
pha long
tuyn
tnh
nhit (2)
V(ref)
hiu chun(2)
hiu
hiu chun(2)
pha long
m (sample)
P(op)
m(c mu v b)
m(b)
tuyn
tnh
hiu chun(3)
tuyn
tnh
hiu chun(2)
hiu chun(2)
F(hom) (3)
AGL 18
thu hi (2)
I(ref)
m mu
Trang : 51
Ch thch: Thng thng mu c chy tng l mu nh, mi l mu chy u phi hiu chun thit
b, mu kim tra thu hi kim sot chch v mu p ngu nhin kim tra chm. S phi
thc hin hnh ng khc phc nu trong trng hp cc ln th ny c du hiu cho cc kt qu lch
nhau ng k. Kim sot cht lng c bn ny p ng c cc yu cu chnh ca vic nh gi
KB t d liu ph duyt phng php.
Vic chn thm mt yu t nh hng lp li trong s cho ta cng thc tnh Pop nh
sau:
Pop =
I op .c ref .Vop
I ref . Re c.m sample
mg.kg-1
cng thc *
D2
[mg.kg-1]
Malathion
1.30
1.30
Malathion
1.30
Malathion
Trung bnh
[mg.kg-1]
D1 D2
D1-D2/
trung bnh
1.30
0.00
0.000
0.09
1.10
0.40
0.364
0.57
0.53
0.55
0.04
0.073
Malathion
0.16
0.26
0.21
-0.10
-0.476
Malathion
0.65
0.58
0.62
0.07
0.114
Pirimiphos Methyl
0.04
0.04
0.04
0.00
0.000
Chlorpyrifos Methyl
0.08
0.09
0.085
-0.01
-0.118
Pirimiphos Methyl
0.02
0.02
0.02
0.00
0.000
Chlorpyrifos Methyl
0.01
0.02
0.015
-0.01
-0.667
Pirimiphos Methyl
0.02
0.01
0.015
0.01
0.667
Chlorpyrifos Methyl
0.03
0.02
0.025
0.01
0.400
Chlorpyrifos Methyl
0.04
0.06
0.05
-0.02
-0.400
Pirimiphos Methyl
0.07
0.08
0.75
-0.10
-0.133
Chlorpyrifos Methyl
0.01
0.01
0.10
0.00
0.000
Pirimiphos Methyl
0.06
0.03
0.045
0.03
0.667
D lng
AGL 18
Trang : 52
Cc d liu thu c khc nhau (khc so vi trung bnh) cung cp mt kt qu cho phng sai
tng ca qu trnh th nghim lp li. a ra s c lng KB chun tng i cho
tng th nghim n l, lch chun phi chia cho 2 thnh lch chun cho KB
chun cho cc gi tri n. T suy ra gi tr ca KB chun t phng sai ca qu trnh
th nghim lp li tun theo ton b cc bc trong qu trnh phn tch nhng loi tr nh
hng ng nht 0.382/ 2 = 0.27.
Ch thch: Ban u c th cc php th p ny khng a ra bc t do. Nhng n khng c mc
ch l a ra s lng chnh xc i v chm ca qu trnh phn tch i vi mt loi thuc tr
su c bit trong mt loi bnh m c bit no . iu quan trng hn trong qu trnh phn tch
php th l nghin cu th nghim c trn nhiu loi mu th v mc nng d lng trong
mu a ra s la chn i din ca cc loi thuc tr su phospho hu c. Cch thc c hiu qu
nht l th nghim lp li trn cc loi mu bnh khc nhau nghin cu bc t do cho mi loi
mu nghin cu.
Nghin cu v chch
chch ca phng php phn tch c nghin cu ni b trong phng th nghim bng
cch nghin cu cc mu thm (ng nht mu v chia mu thnh cc mu nh v thm mt
hm lng vo mi mu nh) bng 4.h a ra cc kt qu ca mt qu trnh nghin cu cc
mu thm trong mt thi gian di trn cc dng khc nhau.
Bng 4.h. Kt qu nghin cu thu hi thuc tr su
Loi d
lng
PCB
Nng
[mg.kg-1]
10.0
OC
s2) (%)
Trung bnh
2)
(%)
84
0.65
33
109
12
OC
0.325
100
90
Du thc vt v ng vt
OC
0.33
34
102
24
OC
0.32
32
104
18
Bnh m
OP
0.13
42
90
28
Bnh biscot
OP
0.325
30
84
27
OC
0.325
95
12
Gluten ng
OC
0.325
92
ci du
OC
0.325
11
89
13
La m
OC
0.325
25
88
tng
OC
0.325
13
85
19
La mch
OC
0.325
84
22
C cht
Du thi
N1)
Trang : 53
1 Re c
u (Re c)
(1 0.9)
= 2.315
0.0432
crit
th Rec l khc ng
lp li (1)
tuyn tnh
I (op)
V(op)
m(ref)
I(op)
I(ref)
m(ref)
V(ref)
pha long
V(op)
c(ref) tinh
khit (ref)
nhit (2)
V(ref)
hiu chun(2)
hiu chun(3)
hiu chun(2)
pha long
m (sample)
P(op)
m(gross)
m(tare)
tuyn tnh
hiu
chun(3)
F(hom) (3)
AGL 18
thu hi (2)
hiu chun(2)
tuyn
tnh
hiu chun(2)
I(ref)
m mu
Trang : 54
AGL 18
Trang : 55
KB
chun u(x)
j KB chun
tng i u(x)/x
lp li
1.0
0.27
0.27
Da trn 2 ln th ca 2
mu khc nhau
chch
0.9
0.043
0.048
Mu thm
Cc ngun gc khc
( ng nht...)
1.0
0.2
0.2
nh gi trn c s
phng php s dng
u(Pop)/Pop
--
--
0.34
KB chun tng i
M t cc ngun
Ghi ch
u(y,xi) (mg/kg)
ng nht
chch
lp li
P(op)
0
0.1
0.2
0.3
0.4
AGL 18
Trang : 56
B
Gi tr
KB o
C
lp li
1.0
0.27
D
chch
0.9
0.043
E
ng nht
1.0
0.2
ti lp
chch
ng nht
1.0
0.9
1.0
1.27
0.9
1.0
1.0
0.943
1.0
1.0
0.9
1.2
Pop
u(y, xi)
u(y)2, u(y, xi)2
1.1111
1.4111
0.30
0.09
1.0604
- 0.0507
0.00257
1.333
0.222
0.04938
u(Pop)
0.377
0.1420
AGL 18
Trang : 57
Trong l1 v l2 l lng c cht trong cc phn bng nhau thu c t mu L1 & L2 , tng
trng lng l X. p1 , p2 l kh nng xy ra ca cc phn chia c chn t mu (n phi
nh khi i chiu vi tng s cc phn chia c chn)
Coi rng kch thc ca mu l 12 x 12 x 24 cm, chia thnh 432 phn bng nhau c kch
thc 2 x 2 x 2cm v ly 15 phn bng nhau ngu nhin v ng nht trong s . Cng thc
trn c tnh nh sau:
Trng hp (a)
Vt liu c xc nh l n v c b mt rng trn nh ca mu. V th L2 = 0 ging nh l2
v L1 = 1. Mi phn chia bao gm mt phn ca b mt s nhn c mt lng l1 ca vt
liu. Vi kch thc ni trn bng 1/6 ca kch thc mu v th, p1 = 1/6 hoc 0.167 v l1 l
X/72 (v c 72 phn chia)
Ta c:
= 15 x 0.167 x l1 = 2.5 l1
2 = 15 x 0.167 x (1-0.17) x l12 = 2.08 l12
= 1.44l1
RSD = / = 0.58
Ch thch : tnh ton lng X trong ton b mu, gi tr trung bnh ca 432/15 v th X s l:
Trng hp (b):
Vt liu c phn phi trn ton b b mt. Lp lun tng t nh trn, v coi trn ton b
b mt cc phn chia cha cng mt lng l1 ca vt liu, l2 = 0 v p1 c kch thc c tnh
bi:
p 1 = ((12 x 12 x 24) (8 x 8 x 20)) / (12 x 12 x 24) = 0.63
p1 l phn chia ca mu ngoi 2 cm. l1 = X / 272
Ch thch: c s thay i gi tr so vi trng hp (a)
Ta c:
=15 x 0.63 x l1 = 9.5 l1
= 15 x 0.63 x (l1-0.63) x l12 = 3.5 l12
= 1.87 l1
RSD = / = 0.2
Trng hp (c)
Lng vt liu gn b mt gim xung gn n 0 do c s bay hi hoc cc tht thot khc.
Trng hp ny c th tnh ton mt cch n gin nht l coi n nh mt trng hp ngc
li vi trng hp (b), vi p 1 = 0.37 v l1 = X/160
AGL 18
Trang : 58
Ta c:
=15 x 0.37 x l1 = 5.6 l1
2 = 15 x 0.37 x (1-0.37) x l12 = 3.5 l12
= 1.87 l1
RSD = / = 0.33
Tuy nhin, s tht thot ny t n mt su nh hn kch thc ca phn chia, mi phn
s cha mt t lng vt liu l1 v l2 v th, c hai s khng bng 0. Ta ly trng hp m
phn ngoi l 50% v phn trung tm mu l 50%.
Ta c:
l1 = 2 x l2 l1 = X / 296
= 15 x 0.37 x (l1 - l2) + 15 x l2
= 20.6l2
2 =15 x 0.37 x (1 - 0.37) x (l1 - l2) 2 = 3.5 l22
RSD = 1.87/20.6 = 0.09
Trong dng ny, tng ng vi su 1cm m vt liu b mt. Kim tra cc mu bnh m c
v dy 1cm hoc nh hn v s dng. Trong cc dng hin nay th tng ng vi su 1cm
ci m vt liu b mt. Kim tra cc dng mu bnh m c v dy 1 cm hoc nh hn v to
ra su cho vt liu v quan tm n s mt (v cng bn thn n l b ngn cn s mt
di chiu su ny). do phng sai thc trong trng hp (c) s a ra gi tr ca ,
khng nh gi tr 0.09 trn
Ch thch: Trong trng hp trn s gim cc ny sinh KB trong vic mu khng ng nht l
thng s nh hn l ng nht. Ni chung s u mnh vic gim phn b KB. Cn thm vo m
hnh nghin cu cc trng hp s lng ln hn l s lng nh ( ging nh s kt hp cht ch ca
cc ht trong cc khi ln) cha ng gi tr khng t l vi vt liu quan tm. Cung cp rng kh
nng tng hp tr nn khng kt hp vo cc phn mu ng nht l ln, phn b KB s
khng vt qu bt c tnh ton no trong cc trng hp trn.
AGL 18
Trang : 59
5.
XC NH VITAMIN A V E TRONG SA BT
5.1
As V f C STD
ASTD Ws
Trong :
AS : l din tch mi (nh) ca dung dch mu
ASTD : l din tch mi ca dung dch chun
VF : l lng mu bm (ml)
WF : l trng lng mu dng phn tch (g)
CSTD : l nng ca dung dch chun (gml-1)
Mt s dng chy minh ha cc giai on trong phng php c trnh by hnh 5.1
5.2 Nghin cu chm
Mt nghin cu v nhn hiu thc phm ca cc sa bt sn c trn th trng ch ra rng tt
c u c cc thnh phn c th so snh v cht bo, protein, cacbonhyrat v cha nhng
nng vitamin A v vitamin E tng t. Ba mu c chn kim tra bao ph ht khong
nng c th ca vitamin trong mu. Mi mu c phn tch 4 ln, trong 4 ln chit v
chy sc k lng hiu nng cao (HPLC) khc nhau. Vi mi ln chy HPLC u dng ng
hiu chun mi v dung mi pha ng. Thm vo phn tch mt cht chun c chng
nhn (SRM 1846) c lng Rm . Nhng kt qu ny c tng kt trong nghin cu
chm. Kt qu c trnh by bng 5.1
AGL 18
Trang : 60
Butylat hydroxytoluen
*
Lng thch hp ca
mi dung dch chy
HPLC nn la chn
da theo nng ca
mi vitamin gn vi
chun hiu chun
tng ng.
Thm 1g pyrolgalol vo
150ml dung dch etanolic
KOH
X phng ho trong vng
30 pht bng h hi lu
Ct n kh ti 40 C
nh lng alltrans retinol bng
HPLC pha ngc
Ho tan vi mt lng
thch hp metanol*
Ct n kh bng my ct quay
Thm 2 ml
dung dch
BHT
nh lng
-tocopherol bng
HPLC pha thng
AGL 18
Trang : 61
Trung
bnh
(mg kg-1)
lch
chun
(mg kg-1)
lch
chun
tng i
Trung
bnh (mg
kg-1)
lch
chun
(mg kg-1)
lch
chun
tng i
Sa bt A
9.67
0.146
0.0151
64.08
2.411
0.0376
Sa bt B
10.04
0.247
0.0238
69.05
2.156
0.0312
Sa bt C
6.67
0.217
0.0325
171.93
7.959
0.0463
SRM 1846
5.32
0.285
0.0536
278.51
10.663
0.0383
Nghin cu ng
Tnh Rm v u ( Rm)
Trong trng hp s dng mu chun c chng nhn SRM 1846 do vin Quc Gia v tiu
chun v cng ngh ca Nht (NIST) sn xut. CRM l mu sa bt chun c chng nhn
v s lng vitamin, bao gm vitamin A v vitamin E. Su mu CRM c phn tch. Kt
qu, cng vi nhng gi tr c chng nhn ca mu chun c tng kt bng 5.2
AGL 18
Trang : 62
Ch tiu phn
tch
Gi tr c cng nhn
khng m
Nng
khngm
bo chun
CCRM
bo CRM
u(CCRM)
(mgkg-1)
(mgkg-1)2
(mgkg-1)1
Gi tr quan st c
Trung bnh
C obs
(mgkg-1)
lch
chun sobs
(mgkg-1)
VitaminA
5.84
0.68
0.35
5.32
0.285
vitaminE
271
25
12.8
278.51
10.663
Tnh Rm v u ( Rm)
i vi vitamin A (all-trans retinol): Rm = 5.32/5.84 = 0.911
0.2852 0.35
+
u ( R m ) = 0.911
= 0.0581
2
6 5.32 5.84
2
1 Rm
u(R m )
1 0.911
= 1.53
0.0581
1 n C obs ( i ) C native
C
n i 1
spike( i )
AGL 18
Trang : 63
Nng
tng ng
(mgkg-1)
Trung bnh
thu hi
14.0
2
3
Vitamin E
n
Nng
tng ng
(mgkg-1)
Trung
bnh
thu hi
0.981
84.0
1.028
18.0
0.991
99.0
1.103
22.0
0.996
114.0
1.167
0.00767
u(Rs)
u(Rs)
0.0696
u ( R m ) u ( Rs ) u ( Rref )
= 0.05812 + 0.00767 2 = 0.0586
+
+
u ( R) = Rx
R
R
m s ref
2
Nghin cu sai s th
C mt s tham s ca phng php m khng i din cho s khc nhau qua nghin cu
chm v ng. Nhng nghin cu ny s dng nghin cu sai s th. Cc bc chit
chit v cc giai on chy sc k lng hiu nng cao (HPLC) ca phng php. Ch c
nghin cu sai s th i vi vitamin A c thc hin. Mt nghin cu tng t cng c
yu cu i vi vitamin E hon thnh c tt c cc ngun gy ra khng m bo.
Nhng tham s c nghin cu v la chn c tng kt trong bng 5.4 v bng 5.5 di
y. Nghin cu c thc hin trn CRM.
Giai on chit v ra sch
Nhng kt qu thu c t kim tra khng thun nht ca qu trnh chit i vi vitaminA
c trnh by bng 5.6. S khc nhau i vi mi tham s, t DxA n DxG, c tnh ton
nh miu t phn B mc 3.3.3.1 Ti liu hng dn c lng KB cho phn tch
ha hc nh lng.
AGL 18
Trang : 64
Gi tr
A
42g
21g
20 pht
40 pht
2 pht
1 pht
n trung tnh
n kh
Thm 5 pht
50oC
Lng nc ra
**
30 C
Gi tr
Tui ct
Mi
a'
Tc dng
0.8ml/pht
b'
1.2ml/pht
c'
T l pha ng
(Metanol/nc)
90/10
d'
95/5
Lng bm
15l
e'
25l
Bc sng
320nm
f'
330nm
Nhit ct
30 C
g'
5.25
3.98
4.22
4.43
5.51
4.78
4.35
4.96
DxB
DxC
DxD
DxE
DxF
DxG
-0.4329
0.3898
0.2948
-0.1009
0.2387
0.7036
0.03608
Trang : 65
Gi tr t
2.316
1.752
Khng
0.599
Khng
Lng nc ra
1.419
Khng
4.181
Nhit ct quay
0.214
Khng
2 t crit s real
=
n 1.96 test
= 0.184 real
test
test
4 1.96
Trang : 66
dng phng php ny hng ngy vic thm 3 ln nc ra cha chc c thc hin.
Nhng vic tng thm nc ra 1 ln c th xy ra. Nht l trong trng hp s trung tnh ch
va t ln ra trc . real v th c c lng ngang bng vi 1. v th khng m
bo u(y(xE) l 0.0613.
Nhit ct quay
Phng php ny thng dng vi nhit l 40oC. Ngi ta c lng rng nhit c th
dao ng l 2oC trong vic s dng thng thng. Trong th nghim sai s th nhit
c t ti 30oc v 50 oC, v gi tr ca rest l 20 oC v u(y(xG) l 0.0368mgkg-1.
i vi nhng thng s c xc nh th c khi c mt nh hng ng k i vi dch
chit.
Trng lng KOH s dng chun b dung dch etanolic KOH
Di iu kin vn hnh thng thng, s dng 42 0.1g KOH trong vic chun b dung
dch etanolic KOH theo yu cu cho phn ng x phng ho. Trong nghin cu sai s th,
lng KOH s dng gim xung l 21g. Kt qu thu c ny khc nhau, DxA l 0.4329mgkg-1. H s nhy c tnh nh sau:
cA =
0.4329
= 0.0206mgkg 1 g 1
21
AGL 18
Trang : 67
5.47
5.33
5.35
5.07
4.59
4.75
4.79
5.09
DxG'
0.06682
DxB'
Dx C'
DxD'
Dx E'
DxF'
0.4997
-0.04021
-0.01202
0.0091
0.2192
-0.000975
Tnh ton nhng khc nhau qua th nghim cho phng sai ng k so vi 0. lch chun
c s dng trong php th da vo cng thc pool gia cc l d liu chm t 3 dung
dch chun vitamin A, mi nng phn tch 4 ln. iu ny dn n mt lch chun
chung l 0.167mg/kh(v=9).Gi tr xp x tcrit vi tin cy 95% l 2.262
i vi nhng thng s c xc nh l khng c nh hng ng k, KB c c
lng l 0.136x(real /test).
Tc dng
Phng php s dng tc dng l 1ml/pht. Mt s thng tin t cc ti liu cho rng s
bin i c trng trong tc dng l .3%. Trong trng hp ny tng ng l
0.003ml/pht. real v th l 0.006ml/pht. Trong nghin cu sai s th tc dng thay i t
0.8-1.2ml/pht. test v th l 0.4ml/pht. khng m bo trong kt qu cui cng do s
bin i trong tc dng u(y(xB)) v th l 0.0024mg/kg
T l pha ng
Phng php ch ra rng mt pha ng t l l metanol: nc(90:10 v/v). T mt s ti liu
ngi ta d on rng bin i trong hn hp pha ng t khi vt qu 1% trong c hai
thnh phn. Trong nghin cu sai s th t l thay i l 95:5 (v/v) metanol: nc, c th
chp nhn mt t l thay i cao hn trong khi p dng hng ngy. Ln c lng u tin
ngi ta gi nh rng khi s dng thng thng, nh hng ca kt qu cui cng nh c s
bin thin trong hn hp pha ng bng 1/10 kt qu quan st c trong th nghim sai s
th.
AGL 18
Trang : 68
Lng bm
Thng tin t cc ti liu cho rng 1,5% l h s c trng cho bin ca lng bm i vi
mt mu bm t ng. Phng php s dng lng bm l 20l. test v th l 0,6l. Trong
nghin cu sai s th lng bm bin i 10l. khng m bo u(y(xE)) l 0.00816mg/kg
D bc sng
Trong nghin cu thun nht th d bc sng c thay i l 10nm. Da trn mt s
thng tin th chnh xc mt bc sng l 2nm. khng m bo u(y(xF)) v th l
0.00186mg/kg
Nhit ct
Nh phn nghin cu sai s th, iu tra nh hng ca ct khng c n nhit. Khi
nghin cu th nhit phng trung bnh l 22,2oC vi mt % Cv l 1%. Ct thng c
duy tr ti 30oC. Ngi ta c lng rng, n c m bo trong 1oC. real v test tng
ng l 2oC v 7.8oC. khng m bo u(y(xG)) l 0.0349mg/kg.
nh hng ca cc thng s trn coi nh t l vi nng phn tch. Nhng khng m
bo v th c tnh bng cch chia lch chun tng ng vi 5.32mg/kg
Ch c mt thng s c nh hng c ngha n phng php l tui ct. S dng ct c
cho kt qu thp hn khi s dng ct mi. nghin cu s liu cho thy din tch nh i vi
mu chun tng ct c trong khi din tch nh gim i vi mu, dn n gim nng
c tnh.
Nhng kt qu nghin cu sai s th ch ra rng: khi tui ct thay i th s thc hin phng
php thay i. Khi p dng hng ngy nn iu chnh bng vic s dng chun kim sot cht
lng HPLC. Vic thc hin kim sot thch hp sau khi chnh cc iu kin chy HPLC th
nhng phn chit ca mu s i din cho s phn tch. Do s vn hnh tng i ngn nn
dng nh nghin cu chm c thc hin nh mt phn ca ph duyt phng php s
bao gm phng sai ca phng php do tui ct. Tuy nhin khi dng phng php ny hng
ngy mt mu s c phn tch v d liu thu c s c thu thp trong tng khong thi
gian. Phng sai quan st c trong nhng kt qu ny s bao gm phng sai do s thay
i ct theo thi gian trong nhng gii hn c chp nhn bi chun kim sot cht lng
ca HPLC. Nu c lng chm trong mt thi hn di thu c t mu kim sot khc
c ngha vi c lng chm t nghin cu thc hin trc th n c th c
dng to ra mt c lng khng m bo th cho s liu ln sau. V nhng l do nh
trn m c lng KB do s thay i tui ct s khng bao gm trong KB hin thi.
Cc ngun khng m bo o khc
Nghin cu chm v ng c thit k bao gm cng nhiu KB o cng tt, v
d bng vic phn tch cc khong nng v bng so snh vi cc chun mi v HPLC pha
ng cho tng l th nghim. Cc tham s m khng thch hp s c sai khc th hin qua
nhng th nghim thc nghim nh vic chit v iu kin ca HPLC c nghin cu trong
AGL 18
Trang : 69
Bng 5.9 th hin cc KB thnh phn v ln ca tng thnh phn trong phng php
xc nh vitamin A trong sa bt.
Bng 5.9 : cc ngun KB trong phng php xc nh vitamin A trong sa bt
KB chun
Thng s
chm
u(P)
0.238 mgkg-1
thu hi
u(R)
0.0586
u(y(xA))
0.000224
u(y(xB))
0.0106
u(y(xD))
0.0346
S lng ln ra nc
u(y(xE))
0.0115
u(y(xF))
0.0382
Nhit ct quay
u(y(xG))
0.00692
Tc dng
u(y(xB'))
0.000383
T l pha ng
u(y(xD'))
0.00256
Lng bm
u(y(xE'))
0.00153
Bc sng
u(y(xF'))
0.0103
Nhit ct
u(y(xG'))
0.00656
AGL 18
Trang : 70
KB tng i
0.47
0.094
7.5
0.65
0.087
10
0.84
0084
KB m rng
(mg kg-1)
KB m rng
tng i
0.94
0.19
7.5
1.30
0.17
10
1.69
0.17
Trang : 71
Nhit ct
Bc sng
Lng bm
T l pha ng
Tham s
Tc dng
Nhit ct quay
Thi gian ct quay
S lng ln ra nc
Thi gian lc v chit
Thi gian x phng ha
Khi lng KOH
thu hi
chm
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
0.055
0.06
AGL 18
Trang : 72