(국립환경연구원고시 제2005-4호, 2005.02.17)
TRANSCRIPT
-
- 1 -
2005-4(2005. 2)
2005. 2
-
- 2 -
1 1
2 3
1 4
2 10
3 22
4 36
5 40
6 46
3 54
4 69
1 70
2 , ,
77
3 99
4 , , ,
n- iso- 114
5 130
5 144
1 / 145
2 153
3 158
4
163
5 172
6 178
: (QA/QC) ------------------------- 187
------------------------------------------------- 196
-
- 1 -
1
1.
5
.
2.
( ) ,
, (QA/QC) .
3.
.
.
4.
. ,
.
.
5.
(
) .
.
6. .
7. , , ( ) .
-
- 2 -
8.
.
9. , , ,
. ,
,
.
10. ,
,
.
11.
KSA 3251-1( -1 : ) .
12.
,
.
-
- 3 -
2
-
- 4 -
1
1.
.
2.
1961 .
3.
1 , KSA 0105
(SI) .
4.
4.1 % .
4.1 100 mL 100 mL (g) W/V%
.
4.2 100 mL 100 mL (mL) V/V%
.
4.3 (Parts Per Million) ppm
mol/mol (V/V),
mol/mol (W/W), (W/V) .
4.4 10 (Parts Per Billion) ppb ppm
.
-
- 5 -
1.
()()
m
()nm(m)
ggng
kLL
mLL
atmHgH2O
5.
5.1 (Celcius) .
K 0 K -273 .
5.2 1525 , 135 , ()
015 .
5.3 () 15 , () 6070 , () 100 .
6.
.
7.
() .
-
- 6 -
8.
8.1 (1+2), (1+5), (1+5+10) 1
2 , 1 5 1 5 10
, (1 : 2), (1 : 5), (1 : 5 : 10) . ,
(1+2) (1 : 2) 1 2 .
8.2 (12), (15)
1 g , 1 mL 2 mL 5 mL
.
9. , ,
9.1 1 ,
. , , ,
2 .
2.
(%) ()
HC1
HNO3
H2SO4
CH3COOH
H3PO4
NH4OH
35.037.0
60.062.0
95%
99.0%
85.0%
28.030.0 %(NH3)
1.18
1.38
1.84
1.05
1.69
0.90
9.2
(-4 ) .
10 ()
-
- 7 -
20 20 1 mL
.
11. ()
11.1 KSL 2302(
)
.
11.2 , , , ,
.
11.3 KSM
7602 5 .
12. ()
12.1 ,
.
12.2 () ()
.
12.3 ()
.
12.4 ()
.
12.5 ()
.
13. ()
-
- 8 -
.
14.
14.1 1
g 0.3 .
14.2 30 .
14.3 15 Hg .
14.4 ()
() () ,
. ab" a b
.
14.5 () ,
.
14.6 , ,
(Lot) .
14.7 ()
, ()
()
.
14.8 () pH
.
15.
-
- 9 -
15.1 25 , 1
.
15.2
.
15.3 KSA
3251-1( -1 : ) .
15.4 ,
, , .
-
- 10 -
2 ( Absorptiometric Analysis )
1.
()
200900 nm
.
2.
() (Monochrometer)
(Filter) ()
()
. Io 1 C, L
.
Pt Po - (Lambert-Beer)
.
1.
-
- 11 -
Pt = Po10-cL ( 1)
, - Po :
- Pt :
- C :
- L :
- : () ,
C = 1 , L = 0 K .
Pt Po PtPo = t (), ,
t 100 = T () loglt =
A () . -
Io, It
. ()
. -
A = cL
()
.
.
3.
3.1
2 (), (
), () () ()
.
-
- 12 -
2.
3.2
() ()
() . () ()
()
. .
3.3
(Monochrometer) (Filter) .
,
(Slit) . , , .
3.4
(Cell, ) ()
(Cell Holder) () ()
.
3.5
(), (),
() () (),
.
-
- 13 -
, ( )
, () .
, , .
, , .
3.6
()
() .
(), 2(). ()
.
3.7
.
3.
-
- 14 -
3.8 ( Cell )
3 4 .
3 (a) 1 mL () 10 mm , (b)
, (c)
, (d) 50 mm
.
, , . ()
() , ,
.
3.9
3.9.1
(Line Spectrum)
4
m . m ( ) t
0(Zero) .
4.
3.9.2 (Holmium)
. ()
() .
.
-
- 15 -
3.9.3
110 3 (1 ) N/20
. K2Cr2O7
0.0303 g/L . 10.0 mm 25
1 nm .
2 2
.
2. () (25 )
() () () ()220230240250260270280290300310320330
0.4460.1710.2950.4960.6330.7450.7120.4280.1490.0480.0630.049
35.867.450.731.923.318.019.437.370.989.586.471.0
340350360370380390400420440460480500
0.3160.5590.8300.9870.9320.6950.3960.1240.0540.0180.0040.000
48.3 27.6 14.8 10.3 11.7 20.2 40.2 75.1 88.2 96.0 99.1100
3.9.4 (, Stray Light)
() 3
(, Stray Light) 6
(Cut Filter) .
3.
( ) 200220300330700800
,
-
- 16 -
4.
4.1
.
4.1.1
4.1.2
4.1.3
4.1.4
4.1.5
4.2
.
4.2.1 370 nm
370 nm .
4.2.2 (L) 10 mm .
4.2.3 , .
( 8 )
. ( )
() .
-
- 17 -
4.2.4 .
.
(2 W/V ) ( : )
4050 10 .
(1 + 5) 30
.
.
(Dryer) .
.
1
.
()
.
.
4.3
.
4.3.1 .
4.3.2 (Zero) .
4.3.3 .
4.4
.
4.4.1 .
4.4.2 () ()
.
.
-
- 18 -
4.4.3 100 .
4.4.4 () ()
. .
4.4.5 100 .
4.4.6 2,3,4
.
4.5 ( )
. 10 nm
() , ()
. (Peak)
15 nm .
.
() .
() .
4.6
.
4.6.1
4.6.2 ,
4.6.3
4.6.4 ,
4.6.5
4.6.6
4.6.7
4.6.8
4.6.9
4.6.10
-
- 19 -
5.
.
( )
.
5.1
,
. .
. ,
()
.
5.1.1
()
.
.
5.1.2
.
5.2
.
5.2.1
5.2.1.1
5.2.1.2
-
- 20 -
5.2.1.3
5.2.1.4 pH
5.2.1.5
5.2.1.6 ,
5.2.1.7
5.2.1.8
5.2.1.9
5.2.1.10 ()
5.2.1.11
5.2.2
5.2.2.1
. , , ()
.
5.2.2.2 , .
5.2.2.3 0.20.8
.
5.2.2.1 0.1
.
5.3
.
5.3.1 () .
5.3.2 , , , , ,
.
5.3.3 .
5.3.4 .
5.3.5 , ,
.
5.3.6 4.4 .
5.3.7 5.1
.
-
- 21 -
:
.
-
- 22 -
3 (Gas Chromatography)
1.
2.
2.1 -
(GSC) , (solid support)
- (GLC) .
2.2 (carrier gas)
. , ,
, , .
2.3 , , ,
.
2.4
(PC )
(peak) (chromatogram) .
2.5 ,
(retention time)
(retention volume) .
-
- 23 -
,
.
3.
( ),
.
3.1
.
3.1.1 ,
.
3.1.2 , , .
.
3.2
3.2.1
, , .
3.2.2 , ,
.
,
.
3.3 (column oven)
-
- 24 -
.
(), ,
. , .
0.5 , 10 %
0.5 .
3.4 GC
.
3.4.1 (Flame Ionization Detector, FID)
(nozzle), (ion collector)
, , .
3.4.2
(Electron Capture Detector, ECD),
(Flame Photometric Detector, FPD), (Nitrogen Phosphorus
Detector, NPD) . ,
, .
3.5 (Mass Selective Detector)
, , ,
.
3.5.1
.
-
- 25 -
,
.
3.5.2 (Eelectron Impact ionization, EI)
,
(, M+) .
(M) (M+) (ionization
energy, IE), 812 eV (8001200 kJmol-1)
.
M + e- M+ + 2 e-
(fragment ion)
.
M+ M1
+, M2
+, etc.
(-)
10-5 torr .
70 eV
. (m/z)
. (Library)
, .
1.
3.5.3 (Mass Analyzer)
(m/z)
-
- 26 -
. (Analyzer) ,
, , .
3.5.3.1 (Quadrupole Analyzer)
,
. x y
, x2-y2 = ro
2 .
z (U) (V cos t)
(Potential Pulse) .
3.5.3.2 (Ion Trap Analyzer)
(Ring) (End cap)
. U+V cos (t) ,
. m/z
.
.
.
.
.
3.5.3.3
(Electron Multiplier, EM) Cu-Be
(Dynode) . 12 20
.
.
4.
99.999 % .
5. ,
-
- 27 -
5.1
.
GSC(Gas-Solid Chromatography) GLC(Gas-Liquid
Chromatography) , .
, ,
.
.
5.2
5.2.1
.
3060(mesh), 6080, 80100 .
,
. ,
, (Molecular Sieve), .
.
5.2.2
-
.
,
.
5.2.2.1 (Support)
. , , , ,
, , (silane finishing) .
5.2.2.2 (Stationary Liquid)
.
.
-
- 28 -
.
.
, .
.
.
5.2.3
(Divinyl Benzene) (Bridge Intermediate)
.
6.
6.1
6.1.1 /(GC/MS)
85 % .
6.2.2
.
5.2.2.1 : ,
10 % .
5.2.2.2 : ,
.
5.2.2.3 : 10 .
6.2
6.2.1
6.2.1.1 : ,
.
-
- 29 -
.
6.2.1.2 : .
.
6.2.1.3
,
,
.
6.2.2
.
6.3
6.3.1
.
6.3.1.1
6.3.1.2 MS (transfer-line)
6.3.1.3 ( , ,
)
6.3.1.4
6.3.2
.
6.3.3
6.3.3.1 : ( )
( 0.55 mL) .
6.3.3.2 :
(micro syringe, 1100 L) , .
6.3.3.3 : 6.3.3.2
.
7.
-
- 30 -
.
7.1
(Theoretical Plate Number) (Height
Equivalent to a theoretical plate, HETP) ,
.
(N) = 16
t RW
2
( 1)
, - tR : ()
- W :
- HETP = LN
- L : (m)
7.2
.
(d ) = tR2tR1 (R) = 2( )tR2tR1W1 +W2
=2d
W1 +W2 ( 2)
, - tR1 : 1
- tR2 : 2
- W1 : 1
- W2 : 2
- d : (tR2-tR1)
-
- 31 -
dddd
2.
8.
.
, (library)
.
(retention time), (retention volume),
(relative retention), (retention ratio), (retention index)
. 3 .
530 3 %
. (dead volume)
.
9.
,
, .
.
9.1
-
- 32 -
.
9.1.1
(GC)
.
.
9.1.2
, 1)
.
Xi(% ) =
Aifi
i = 1
n Aifi
100 ( 3)
, - f i : i
- n :
9.1.3
(X) (S)2)
.
(MX) (MS) (MX/MS)
(AX) (AS) (AX/AS)
3 .
(M) (n)
,
.
(A X) (A S) (A X/A S) ,
(M X) (M S ) (M X/M S) ,
(X) .
1) : (, , )
. .
.
2) ,
.
-
- 33 -
X (% ) =
M XM S
n
M 100 ( 4)
, .
.
3.
9.1.4 : A B
a1 b1 . W A WA3)
A B a2 b2 K
.
WAWB
= Ka1b1
WA + WA
WB = K
a2 b2 ( 5)
, WA WB A B , K
A X(%) .
X (% ) = WA
a2b2
b1a1
1 W 100
( 6)
3) WA a2/b2 1.2~2.0 .
-
- 34 -
9.2
9.1 (mole) .
9.3
,
(noise) 3 (S/N >3)
9.4
,
20 % .
10.
.
10.1 :
10.2 : , ,
10.3
10.3.1 : , ,
10.3.2
, , , ,
10.3.2.1 :
( )
.
10.3.2.2 : .
-
- 35 -
10.3.2.3 :
.
.
10.3.2.4 , , , ,
.
,
. .
10.3.3
10.3.3.1 : ,
10.3.3.2 : ,
10.3.3.3 : , ()
10.3.4 : .
10.3.5
10.3.5.1 :
.
10.3.5.2 :
.
10.3.5.3 : , .
10.3.6
10.3.6.1 :
10.3.6.2 :
10.3.6.4 : SI mole .
-
- 36 -
4 (Ion Chromatography)
1.
(F-, Cl-, NO2-, NO3
-, PO4-, Br- SO4
2-) .
2.
1 , ,
, ,
(suppressor) .
1.
2.1
10
-
- 37 -
. 150350 /
() .
2.2
-
20100 L.
2.3
.
2.3.1 (suppressor)
(1015 )
35 mm, 530 mm .
2.3.2
( 1015 ),
( 1012.5 ) (6 )
46 mm, 510 cm .
2.4 ()
.
.
2.5
,
.
-
- 38 -
3.
3.1
0.45
(GF/C)
.
.
.
3.2
3.2.1 (1 mg/mL)
105
1 L .
1 .
C1-Br-NO3-NO2-PO4-SO42-F-
NaC1 NaBr NaNO3*NaNO2 KH2PO4 K2SO4 NaF
1.6485 1.2876 1.3707 1.4998 1.4330 1.8141 2.2100
*
3.2.2
.
3.2.3 1)
3.2.3.1 (0.003M NaHCO3 - 0.0024M Na2CO3)
0.252 g 0.2544 g 1 L .
3.2.3.2 (0.0013M - 0.0013M Na2B4O7)
-
- 39 -
1.02 g 1.0466 g 4 L .
3.2.4 ( 0.025N H2SO4 )
0.7 mL 1 L .
3.3
13 mL/
.
3
.
3.4 2)
(/L) .
1)
.
2)
.
-
- 40 -
5 (HPLC)
1.
,
.
2.
2.1
,
.
HPLC
,
. ,
.
2.2 HPLC
, ,
, , , , ,
, , .
3.
1 .
-
- 41 -
1. HPLC
3.1 HPLC
HPLC , PTFE, PEEK, ,
.
, . , ,
. ,
.
3.2 HPLC
,
.
HPLC HPLC ,
18 .
15 .
(v/v) .
.
HPLC () .
-
- 42 -
3.2.1 .
3.2.2 k ' 110 .
3.2.3 .
3.2.4 .
3.2.5
.
3.3 (Degassor)
HPLC
, .
1 He ,
,
.
3.4
,
, HPLC
. .
3.4.1 .
3.4.1 500 psi .
3.4.3 0.1 10 mL/ .
3.4.4 .
3.4.5 0.5 %
.
3.4.6 .
3.5
HPLC ,
. (Sample Loop)
-
- 43 -
HPLC . ,
2.0 L5.0 mL
, 20 L .
3.6
HPLC 5,000 psi
.
. 1030 cm
, 4.6 mm, 5 , 40,00060,000 plate/m,
(Analytical Column) (Guard Column)
. 510 cm ,
.
, .
, , ,
. HPLC
.
3.7
HPLC
, .
3.7.1 -(Ultraviolet-Visible detector)
HPLC , -
. -
,
.
, .
-
- 44 -
3.
-
-
-
- 10-610
-10 g .
- .
- .
.
4.
4.1
3
4.2
4.2.1
.
4.2.1
4.2.2
4.2.3
4.2.4
4.2.2
, .
4.2.3
12 mL/
.
.
.
-
- 45 -
.
4.2.4
.
4.2.5
.
4.2.5.1
4.2.5.2
4.2.5.3 (L mL)
4.2.5.4
4.2.5.5
4.2.5.6
4.2.5.7
4.2.5.8
-
- 46 -
6
(Differential Optical Absorption Spectroscopy)
1.
501,000m
( ) (Path)
, 1802,850 nm
(Xenon) , , , ,
.
2.
2.1
(Differential Optical Absorption Spectroscopy : DOAS)
Beer-Lambert .
It = Io 10 -CL
( 1)
, - Io :
- It :
- C :
- L :
- :
. (It/Io) ,
. 1
(nm) 1 .
(DOAS) .
() (DOAS) ()
-
- 47 -
.
(nm)n-1 n n+1
1.
(nm)
n-1 n n+1
2.
Y
, 1
. 1
, 2
.
. 2
( 1) .
Differential Optical Absorption
.
.
-
- 48 -
, ,
.
(Fitting) (, )
,
, .
2.2
Czerny-Turner Holographic .
.
(Photo Multiplier Tube) PDA
(Photo Diode Array) . (Detection Window)
.
A/D(Analog/Digital)
. , ,
.
.
3.
3.1
, ,
, , , .
-
- 49 -
Library
& S/W
/
Internet
3.
3.2.
/( ) ,
.
3.2.1 /
,
. 1802850 nm .
.
3.2.2
.
3.3
, .
,
.
3.3.1
-
- 50 -
Czerny-Turner Holographic ,
.
3.3.2
(Path)
.
3.3.3
PDA
.
3.3.4 (Library Data Base)
,
.
4.
4
4.
4.1
-
- 51 -
, .
3 , ,
.
4.2
24 .
.
5 % .
4.3
(24 )
2 .
.
. 4 .
4.4
. .
4.5
A . +10 %
10 B . -10 %
10 C . B-A, C-A (RANGE)
.
4.6
, ( )
AC 1000 V 1 .
-
- 52 -
4.7
, ( )
KSC1031 KSC1302 DC500V
.
4.8
01 V 15 V( 500 ) 420 mA
4.9
.
, 90 %
() .
4.10
, (2
030 ) 5
.
5.
5.1
.
5.1.1 .
5.1.2 .
5.1.3 , .
-
- 53 -
5.1.4 , .
5.1.5 .
5.2
5.2.1 .
5.2.2 .
5.2.3 2 .
5.2.4 .
5.2.5 .
5.3.
.
5.4.
5.4.1 (Path) .
5.4.2 6 1 .
5.4.2 .
-
- 54 -
3
-
- 55 -
1.
1.1
.
.
1.
()
()
1000 500 5001000 300500
20 15 1520 1015
1.2
.
2.
2.1
(3, 10, 30 )
.
2.2
-
- 56 -
2.2
( )
2.2.1
.
2.2.2
.
3.
3.1
3.1.1
1 , , ,
.
3.1.1.1 (Mass Flow Control)
1.
-
- 57 -
(Mass flow
controller) .
3.1.1.2
.
3.1.1.3 (Diaphragm Pump)
.
3.1.1.4
.
3.1.1.5
.
3.1.1.6
.
3.2
2 .
2.
3.3
( ) ( )
,
-
- 58 -
(Teflon) , (Tedlar), (Polyester)
320 L . (silicone
rubber) (natural rubber) (seals and joints)
.
3.4
3.
3.5
3.5.1
110 L/ ()(: )
() .
3.5.2
4 .
3.3
. 110 L/
. 1
.
-
- 59 -
4. ( )
3.6 ()
(Glass)
1 mL (Gas Tight Syringe) .
.
.
4.
4.1
4) 2
.
2.
Acetic acid 1.0 wt %
Trimethlyamine 0.1 wt %
Methylcyclopentenolone 0.32 wt % ,
-Penylethylalcohol 1.0 wt %
4) Methylcyclopentenolone(C6H8O2), -Penylethylalcohol(C8H10O)
-
- 60 -
4.2 : 14 cm, 7 mm ,
5.
5.1
.
5.1.1
5.1.2
5.1.3 (, , , )
5.2
1 .
5.3
1
. 10
.
5.4
5.4.1
5.1
.
5.4.2
5.4.2.1
.
5.4.2.2 3 .
-
- 61 -
5.4.2.3 1
.
5.4.3 110 L/ 5 .
5.5
5.5.1
5 m
.
5.5.2
5.5.2.1
.
5.5.2.2 3 .
5.5.2.3 1 .
5.5.3
5 (glass wool) .
.
5.
5.6
(1525 )
(:, )
. .
-
- 62 -
5.7 48 .
6.
6.1
6.1.1 ( 14 cm, 7 mm)5 1 3
( ) 3 2
1 cm 5 .
23 .
6.1.2 5 1
3 3
3, 4 .
.
3.
6.1.3 5 (Panel)
. .
6.1.4 19 .
0 (None)
1 (Threshold)
2 (Moderate)
3 (Strong)
4
(Very Strong)
,
5
(Over Strong)
-
- 63 -
6.1.5 .
6.1.6
6.1.7
6.2
6.2.1 .
6.2.2 , , ,
.
6.2.3 30 .
6.2.4 .
6.3 DB
6.3.1 .
6.3.2 .
7.
7.1
.
7.1.1
7.1.1.1 3.3 320 L
.
7.1.1.2
.
7.1.1.3 6
-
- 64 -
.
6.
7.1.1.4 .
.
7.1.1.5 2 .
7.1.1.6 3
(10, 30, 100) . (300, 1000,
3000) .
.
.
7.1.2
7.1.2.1 .
7.1.2.2 ,
.
7.1.2.3 30
.
7.1.2.4 3
.
7.1.2.5 2 .
7.1.2.6 10 ()
.
7.1.2.7 1 (1 2 )
-
- 65 -
7.1.2.8 .
7.2
.
.
7.2.1
7.2.1.1 (,
, , ) .
7.2.1.2 .
.
7.2.1.3
.
7.2.2
7.2.2.1
5 .
7.2.2.2 ( 10, 300)
1
2 1 1 .
7.2.2.3 3
23 .
7.2.2.4
.
7.2.2.5 1
1 .
7.2.2.6
0.6 .
1.00, 0.00 .
7.2.2.7 2 0.60
.
2
-
- 66 -
. 1 2
1 .
1
7.2.3 5
.
8.
8.1
.
8.2
.
() :(2 0.8)
1 2 (30)
3 (100)1(10) 1(10)
a b ( )c d e
: , :
-
- 67 -
()
a a =
(3 10)= 5.477 ()
(5.4773010)=11.8
b b = 100 ()
c c =
(3 10)=5.477
d d = 30
e e = 10
(: 10 3 )
8.3
,
.
8.5
,
-
- 68 -
[ 1 ]
(1)() 200 . . . (: ~ )
(2)
(3)
(4)
(5)
(6)
(, m)
(7)
(8)
(, ,
)
(9)
,
.
, ( ) .
( )
( )
, .
.
( )
(10)
(11)
-
- 69 -
4
-
- 70 -
1
1.
1.1
.
-
.
1.2
, .
12 ppm 2 ppm,
1 ppm .
2.
2.1 :
2.2
2.2.1 ()5)
1 .
5) 20 mL 1
200 mL ,
-
- 71 -
A : ,
B :
C : )
()
1.
83
25
24/40
130
80
40
83
25
24/40
130
80
40
2.2.1.1 20 mL
, 1 .
20 mL 2
.
2.2.1.2 10 L/
.
2.2.1.3 115 L/ .
2.2.2
2 1020 L/
.
3.
-
- 72 -
.
3.1
3.1.1
5 g 1 L .
3.1.2 , ()
5 g, () 26) 25 mg
500 mL . 1
.
3.1.3
7)( 310 %) 60/CmL[ C
(NaOCl) ( %)] 10 g
12 35.8 g 1 L .
.
() .
() 10 mL 200 mL .
10 mL 300 mL 100 mL
. 12 g (1+1) 6 mL
5 50 mmol/L
(1W/V%) 1 mL ,
. 10mL
. 50 mmol/L "a"mL
factor .
(W/V%)= af(200/10)1/20(mL) 0.001773100 ( 1)
3.1.3
47 mm, 0.3 m 500 1
6) (sodium nitroprusside, Na2Fe(CN5)NO.2H2O, FW= 297.95)
7) () 10%
.
-
- 73 -
5 % 5
.
3.2 8)
3.2.1
130 [(NH4)2SO4] 0.295 g 1 L .
50 . 1 mL 2 L
(0, 1) .
3.2.2
040 mL 50 mL
, 10 mL .
.
4.
4.1
10 L/ 5
.
4.2
2 (polytetrafluoroethylene : PTFE)
1020 L/ 5 .
5. (QA/QC)
8) 1 . .
-
- 74 -
5.1
5.1.1
, 535 oC, 85 %
.
5.1.2
.
5.1.2.1 ,
10 % .
5.1.2.2 ,
.
5.1.2.3 10 .
5.2
5.2.1
5.2.2
.
5.3
5.3.1
0.01 ppm .
5.3.2
3.2.2
. r2 = 0.98 .
5.3.3
"6.2 " 3
.
-
- 75 -
5.3.4
3
(RSD %) . 10 .
5.3.5.
1
, .
5.3.6
(law data)
.
6.
6.1
6.1.1
2 50 mL ,
50 mL
. 10 mL .
6.1.2
20 mL 1
.
6.2
() 5 mL
, 5 mL 2530 1
, 640 nm . () 10 mL
.
-
- 76 -
7.
7.1 ()
3.2.2 (25 , 1)
.
C=5A
V298273 + t
P760 ( 2)
, - C : (ppm)
- A : (L)
- V : (L)
- t : ()
- P : (Hg)
7.2 ()
C 1=
(Ca - Cb)20
V298273 + t
P760 ( 3)
, - C1 : (ppm)
- Ca : (L)
- Cb : (L)
- 20 : (mL)
- V : (L)
- t : ()
- P : (Hg)
7.3
ppm
.( KSA 3251-1 )
-
- 77 -
2 , ,
1.
1.1
.
, -
- ( GC ) .
1 .
1.
(ppm)
(ppm)
0.004 0.002 0.0020.004
0.06 0.02 0.020.06
0.05 0.01 0.010.05
0.03 0.009 0.0090.03
1.2.
.
0.150 ppb(nmole/mole)
.
2.
2.1 (cold trap) (thermal desorption)
-
- 78 -
.
2.2 (capillary column)
,
1(R1)
.
2.3 (Conditioning)
230
10 99.999 % 50 mL/ 23
. .
3.
3.1.
3.1.1 ()
1 .
(Teflon), (Tedlar), (Polyester)
320 L
. . 110 L/
.
1 .
-
- 79 -
1. ( )
3.1.2 - GC
2 , .
(tubing)
sulfinert silico .
24 mm .
-180
( : ) . DMCS1)
( 0.21 mm)
. ( ) 150 oC
30 . 120 oC
10 . GC GC
(FPD), (PFPD), (AED),
(SCD), (MS) .
3.1.2.1 : (glass bead)
3.1.2.2 (30 L )
1) DMCS : dimethylchlorosilane silylation ( non-polar )
-
- 80 -
2. - GC
3.1.3 - GC
3.
3 .
34 mm .
10 N ,
2) ( ) 0.81.0 g
. 2 -180 oC 200
oC .
.
-180
2) 1,2,3-TCEP(25%) = 1,2,3-[tris-2-cyanoethoxy]propane 25%, coated on Shimalite(80/100mesh, acid
washed and treated with DMCS)(Max. Temp. 150), '- ODPN = -oxydipropionionitrile 25% coated
on Chromosorb W(60/80 mesh acid washed and treated with DMCS)(max. temp. 100)
-
- 81 -
3) .
( )
23 .
( 5 oC ) 2030
. GC 3.1.2 .
4. - GC
3.1.5 - GC
, , , , GC
. , GC
GC .
3)
,
, .
-
- 82 -
5. - GC
1600mL/ (Digital
Mass Flow Controller) 1 L/
. (tubing)
sulfinert (tubing)
silico (coating) .
() 4) .
130 mm 23 mm, 66.6 mm(1/4")
5) .
-30
Valve,
(60) .
(syringe pump)
5 (syringe) , loop
GC GC .
-30 (-10 )
4) : nafion dryer , .
5) : () Carbopack C Silica-gel 2 Guard
Carbopack C , Silica-gel 1 : 6
-
- 83 -
GC
.
. GC 3.1.2 .
3.2
3.2.1 (1 L) 10 L , ,
(bag)
3.2.2 (Gas tight Syringe : 1 mL, 5 mL)
3.2.3 (10 L)
3.2.4 (5 L , )
3.2.5 : GS-Q, DB-1
3.2.6
3 mm , 35 m 10 N
. 6080 mesh
(dimethyldichlorosilane)
.-oxydipropyonitrile 25 % ( )
.6) (TCEP )
4,
4.1.
6) '-ODPN = ' -Oxydipropionitrile 25%, coated on Chromosorb w, AW-DMCS. (Max. Temp. 100) 1,2,3-TCEP = 1,2,3-Tris-[2-Cyanoethoxy]-Propane 25%, coated on Shimalite(80/100mesh) AW-DMCS,
Max. Temp. 150). 1,2,3-TCEP DMS SO2 ,
. '-ODPN COS, CS2, SO2 , . , , , 4
4
. , H2S COS, MeSH CS2, DMS SO2
.
-
- 84 -
4.1.1 : 99 %
4.1.2 : 99 %
4.1.3 : 99 %
4.1.4 : 99 %
4.1.5 , , ,
(ppm)
4.2
4.2.1 :
4.2.2
4.2.3 : , ,
4.2.4 99.999 %
4.3
4.3.1
ppm
, 10 L .
7) 10 N ,
. 99 %
1 mL , (
) , 1 . 99%
1 mL , 1
. 3 L (micro-syringe)
, 1 , 4 L
1 , 10
. ppm
ppb .
7) () 0.05N-H3PO4 50 mL
.
-
- 85 -
1
( 100 ppm) , 100
ppm, 110 ppm .
.
C(ppm)= (g/mL)(uL)V(L)(g/mole)(mL) ( 1)
, - V(L) = ,
) 25 oC, 1001 mbar ,
C(ppm)=0.845g/mL3uL24.45L62.14g/mole10,000mL
1,000,000= 101 ( 2)
C(ppm)=1.05g/mL4uL24.45L94.20g/mole10,000mL
1,000,000= 110 ( 3)
4.3.2
ppb ( )
.
4.3.3
ppm ppb .
()
( : MFC : Mass Flow Controller)
.
. (saturation)
.
.
5.
-
- 86 -
5.1
. ,
(shelter) .
5.2
.
.
, ,
. , 5
.
. 1
5 L . , (, ,
) .
6. (QA/QC)
6.1
6.1.1
, 535 oC, 85 %
.
6.1.2
.
6.1.2.1 ,
10% .
6.1.2.2 ,
-
- 87 -
.
6.1.2.3 10 .
6.2
6.2.1
6.2.1.1 ,
.
.
6.2.1.2 .
.
6.2.2
,
, 8)
.
6.2.3
.
6.3
6.3.1
6.3.1.1
6.3.1.2
6.3.1.3
6.3.2
6.3.2.1 : , ,
6.3.2.2 :
6.3.2.3 , .
6.3.2.4 GC . , , , ,
, split .
8) .
-
- 88 -
6.3.2.5 .
6.3.2
6.3.2.1 :
.
6.3.2.2 .
.
6.3.2.3 .
6.4.5 ,
.
6.5
6.5.1
(minimum detection limit, MDL) , , ,
0.2 ppb .
7
3.149) .
6.5.2
3
(peak) (RT: Retention Time) .
3 10 ppb
10 % . 520 ppb r2 = 0.98 .
6.5.3
6.5.3.1
5 L 10 %() 80 %()
. 10 %()
80 %() 50 mL/ 5
(Dynamic Flow)
(Gas Tight Syringe) .
.
9) 7 99%
-
- 89 -
6.
6.5.3.2 10)
2. (mmHg)
()()
0.0 0.2 0.4 0.6 0.8
10 9.209 9.33 9.458 9.585 9.714
11 9.844 9.976 10.109 10.244 10.380
12 10.518 10.658 10.799 10.941 11.085
13 11.231 11.379 11.528 11.680 11.833
14 11.987 12.144 12.302 12.462 12.624
15 12.788 12.953 13.121 13.290 13.461
16 13.634 13.809 13.987 14.166 14.347
17 14.530 14.715 14.903 15.092 15.284
18 15.477 15.673 15.871 16.071 16.272
19 16.477 16.685 16.894 17.105 17.319
20 17.535 17.753 17.974 18.197 18.422
21 18.650 18.880 19.113 19.349 19.587
22 19.827 20.070 20.316 20.565 20.815
23 21.068 21.234 21.583 21.845 22.110
24 22.377 22.648 22.922 23.198 23.476
25 23.756 24.039 24.326 24.617 24.912
26 25.209 25.509 25.812 26.117 26.426
27 26.739 27.055 27.374 27.696 28.021
28 28.349 28.680 29.015 29.354 29.697
29 30.043 30.392 30.745 31.102 31.461
30 31.824 32.191 32.561 32.934 33.312
31 33.695 34.082 34.471 34.864 35.261
32 35.663 36.068 36.477 36.891 37.308
33 37.729 38.155 38.584 39.018 39.457
34 39.898 40.344 40.796 41.251 41.710
35 42.175 42.644 43.117 43.595 44.078
36 44.563 45.054 45.549 46.050 46.556
37 47.067 47.582 48.102 48.627 49.157
38 49.692 50.231 50.774 51.323 51.879
39 52.442 53.009 53.580 54.156 54.737
10) : EPA, TECHNICAL ASSISTANCE DOCUMENT FOR SAMPLING AND ANALYSIS OF OZONE
PRECURSORS, EPA/600-R-98/161, September 1998
-
- 90 -
.
.
. , 21 (mmHg) 18.650mmHg
(atm) .
18.650mmHg
760 (mmHgatm
) = 0.02454atm ( 4)
.
, .
PV = nRT
n = PVRT
( 5)
, - n : H2O
- V :
- P : (atm)
- T : ( 273 + ())
- R : (0.08205 Latm / K mole)
21 , H2O
.
n = (0.02454 atm) (6L)
0.08205 (L atm/K mole ) (297K )
= 0.00610 mole s of H2O required for 100% RH in the canister
( 6)
H2O (n) 21 %
.
0.00610moles RH (20% 0.01 ) 18g
mole 1000
mgg
1.0L1.0mg
= 22.0L ( 7)
-
- 91 -
6.5.4
6.5.3
ppm GC
. 10 %()
80 %, 80%()
60 % .
6.5.5
1
, , .
6.5.6
(law data)
.
7.
7.1 - GC
7.1.1
( -183
) GC . , ,
,
, (FPD),
(PFPD), (AED), (SCD), (MS)
.
7.1.2
GC .
.
(blank) .
-183 11) 100 mL
.
11) , ,
. .
-
- 92 -
GC (injecting)
, 8090 oC
GC . 3 (cold
trap desorb) GC
150 oC .
.
7.1.3
(Tee)
GC (septum) .
5 L (: )12) 60 % (
) .
50 mL/ 5
(Dynamic Flow) (Gas Tight Syringe)
. .
7.1.4
( ).
, -180
1 GC .
3. -GC ()
, - 180 , 80
GC
CP-SIL, 5CB (50 m x 0.53 mm x 5)
5.0 mL/
-40 (4 ), 7 / to 80 , 20
/ to 190
200 mL (100 mL/ x 2 )
FPD 100 mL/, 75 mL/
() 250
12) : GC zero air gas , GC no peak
-
- 93 -
7. -GC ()
7.1.5
ppm (Tee)
7.1.3 , 7.1.4
. FPD PFPD
()
.13)
7.1.6
ppm
, , , (25 ,
1 (g) (umole/mole,
ppm) .
C 1=AV=
A
V '298273+ t
P '760
C = C 124.46(L/mole)MW(g/mole)
( 4)
C : (ppm, umole/mole)
C1 : (/L)(25, 1)
13) () .
I = a x C2 square-root I = a x C
-
- 94 -
A : ()
V' : (L)
V : (L)(25, 1)
t : ()
P' : (mmHg)
MW : (g/mole)
7.1.7
.
3. ( : ppm)
0.000 0.0000
KSA 3251-1
0.00 0.000
0.00 0.000
0.000 0.0000
7.2 - GC
7.2.1 : 7.1.1
7.2.2
GC .
.
(blank) .
110 oC
. 8
-183
100 mL
.14) ,
8090 oC
14)
, .
.
-
- 95 -
GC . 3 (cold trap desorb)
GC 150 oC
.
.
8.
7.2.3
7.1.3
7.2.4
( )
, -183
1 GC .
4. - GC ()
FPD, 200
3 x 2 m,
25% , -ODPN
130
80
, 30mL/
-
- 96 -
T im e ( R T )T im e ( R T )
9. - GC
7.2.5 : 7.1.5
7.2.6 : 7.1.6
7.2.6 : 7.1.6
7.4 - GC
7.4.1
(Syringe
Pump) .
(100) . (Syringe pump)
GC ,
. GC .
7.4.2
GC .
.
(blank) . -30
100 mL/min MFC
.
(Syringe Pump)
,
-
- 97 -
(). (loop) GC GC . GC (Conditioning) ( )
.
/ .
.
5. -GC ()
GC PFPD (TD)
VP1,50m0.325
. 250 50 mL/
1.6 mL/ ( m L /)
=10.7 -30 . 40 H2=10.0 . 90 . 200 He(13.8psi) 2 5 5 mL/ 5 15 /
10. -GC ()
-
- 98 -
-10 GC
6.5
.
6. ()-GC ()
Carbopack B/Silica gel , - 10 , 250 , 5
GC VF-1 MS, (60 m x 0.25 mm x 1.0)
2.0 mL/ 60 (5 ), 10 / to 200
100 mL (25 mL/min x 4 min)
PFPD 1 : 17 mL/, 2 : 10mL/min : 14 mL/
() 200 (S )
7.4.3 : 7.1.3
7.4.5 : 7.1.5
7.4.6 : 7.1.6
7.4.6 : 7.1.6
-
- 99 -
3
1.
1.1
. , -
( GC), -
.
0.02 ppm , 0.005 ppm ,
0.0050.02 ppm .
1.2
0.125 ppb
. .
2.
2.1 (thermal desorption)
.
2.2 (capillary column)
,
1(R1)
.
.
-
- 100 -
3.
3.1
3.1.1
20mL 2
110 L/ 5 % .
.
3.1.2
47 mm, 0.3 m
210 L/, 215/
. 5 %
.
1.
3.2 - GC
3.2.1
.
. 2
. 5 mm .
10 %
.
.
-
- 101 -
. .
,
. ,
.
3.2.2
3 .
(FID : Flame Ionization Detector) (NPD :
Nitrogen Phosphorus Detector)15) . 3 mm,
35 mm 10 % .
6080 mesh 15 %,
15 %, 2 % .
15) (NPD) : (base line)
-
- 102 -
3.3 - GC
(headspace gas) GC
(SPME : Solid Phase Micro Extraction)(fiber)
GC .
3.3.1 :
3.3.2 : 1001,500 rpm .
3.3.3 (headspace vial)
(teflon) .
.
G = G = (Headspace)(Headspace)
S = S =
G = G = (Headspace)(Headspace)
S = S =
4. .
-
- 103 -
A B
C
D
E
F
G
GC HS sampler
A B
C
D
E
F
G
GC HS sampler
A: Headspace vial, B: Heating block, C: Needle, D: Transfer lineE: GC Injector, F: Analytical column, G: Detector
5. - GC
3.3.4 (Solid Phase Micro-Extraction, SPME)
SPME 6 ,
. SPME carboxen/polydimethyl-
siloxane (CAR/PDMS) 7585 m .
GC 250 oC 1 .
6. SPME
3.3.5
.
-
- 104 -
(FID : Flame Ionization Detector) (NPD : Nitrogen
Phosphorus Detector)16) .
4.
4.1 -GC
4.1.1
(KOH) 500 g 1 L .
4.1.2
4.1.2.1
(2040 %)
1020 . 10 mL (
) , 0.1 M
. .
(%) =V Cl N f M D
V 1000 ( 1)
, - VCl : 0.1M HCl (mL)
- N : 0.1M (mole/L)
- f : 0.1M (factor)
- V :
(mL)
- M : (g/mole)
- D :
4.1.2.1
.
1 M 1 (:1904 mg/L) ,
1 M 2 (:1952 g/L) .
16) (NPD) : (base line)
-
- 105 -
2 3
. 3 .
4.1.3
.
4.1.4
0.1 %( 100 mg 100 mL
) 0.1 %( 100 mg 100 mL
) 5 : 1 .
4.1.6
359 mL , 1 mL
.
4.1.7
() 47 mm, 0.3 m
500 1
1 N 1 mL
1 N 1 mL
. .
4.3.5
2 ,
.
5.
. ,
(shelter) .
.
5.1
,
-
- 106 -
. 20 mL
, 2
.
20 mL 2
10 L/ 5 .
5.2
(holder) 10 L/
5 %
. 110 L/ .
10 L/ 5 .
6. (QA/QC)
6.1
6.1.1
, 5 35 oC, 85 %
.
6.1.2
.
6.1.2.1 ,
10 % .
6.1.2.2 ,
.
6.1.2.3 10 .
6.2
-
- 107 -
6.2.1
6.2.1.1 ,
.
.
6.2.1.2 .
.
6.2.2
,
, 17)
.
6.2.3
.
6.3
6.3.1
6.3.1.1
6.3.1.2
6.3.1.3
6.3.2
6.3.2.1 : , ,
6.3.2.2 :
6.3.2.3 , .
6.3.2.4 GC . , , , ,
, split .
6.3.2.5 .
6.3.2
6.3.2.1 :
.
6.3.2.2 .
17) .
-
- 108 -
.
6.3.2.3 .
6.4.5 : ,
.
6.5
6.5.1
(Minimum Detection Limit, MDL)
7 3.1418)
. 0.5 ppb .
6.5.2
, 3 (peak)
(RT: Retention Time) .
3 5 ug/L
(RSD%) 10 % . 120 ug/L
r2 = 0.98 .
6.5.3
1
, .
6.5.4
(law data)
.
7.
7.1 -GC
18) 7 99%
-
- 109 -
7.1.1
GC GC
(FID) (NPD)
.
7.1.2
7.1.2.1
10 ml 20 ml
7.1.2.3
50 mL 20 mL
5 , .
"2.3 "
250300 mL/
23 L -180
. 70
.
7.1.3
19)
.
70 2
.
7.1.4
(,: 120 ug/L)
-
.
7.1.5
.
19) , ,
. .
-
- 110 -
C =24.46A
59,000V298273+ t
P760 ( 1)
A=20Vam
, C : (ppm)
A : (ng)
V : (L)
t : ()
P : (Hg)
m : (ng)
Va : (mL)
7.1.6
ppm
.
KSA 3251-1 .
7.2 - GC
7.2.1
(Headspace) .
.
GC .
7.2.2
7.2.2.1
4 mL PTFE/Silicone , 50 %
KOH 5 mL . KOH
20 , GC
.
7.2.2.2
24 PTFE/silicone
-
- 111 -
, 50 %KOH 9 mL . KOH
5 ( 5 )
,
GC .
7.2.3
(Gas Tight
Syringe) .
UA-Carbowax KOH treated (30 m 0.53 mm 1 um)
. (FID : Flame Ionization
Detector) (NPD : Nitrogen Phosphorus Detector) .
200 GC .
1. - GC/FID ()
UA-Carbowax KOH treated
(30 m 0.53 mm 1 ) (5 mL/) . 75 40 (4)20 /120 FID . 230
30 mL/
300 mL/
(Headspace Auto Sampler). 70
75 oven 50
0.1 4.0 withdrawal 0.1 10 GC cycle time 15
, SPME
GC .
-
- 112 -
(headspace) SPME (Fiber) 15 .
SPME ,
250 GC . GC 3 GC .
SPME
2. (SPME)-GC ()
GC-NPD
20)
5.0 mL/
140 oC (12 )
250 oC (split ratio 5:1)
NPD 320 oC
SPME
SPME 85 Carboxen/PDMS
15
3
7.2.4
(:120 g/L)
7.2.3 .
.
7.2.5
(g/L)
.
C=mV s24.46M ( 2)
C : (ppm : mole/mole)
m : (ng)
Vs : (25 , 1) (L)
M : (g/mole)
20) CP 7594(25 m x 0.53 mm x 20)
-
- 113 -
V s=Q t 298
273+TP760 (3)
, Vs : (L)
Q : (L/)
t : ()
T : ()
P : (mmHg)
m= C x V x (4)
, m : (ng)
Cx : (g/L)
Vx : (mL)
7.2.6 : 7.1.6
-
- 114 -
4 , ,
, n- iso-
1.
1.1
, , ,
n- iso-
2,4-( DNPH )
(High Performance Liquid Chromatography,
HPLC) (Gas Chromatography, GC) .
1.
((ppm)
(ppm)
0.1 0.05 0.050.1
0.1 0.05 0.050.1
0.1 0.029 0.0290.1
n- 0.02 0.009 0.0090.02
I- 0.006 0.003 0.0030.006
1.2
1.2.1 DNPH (HPLC/UV)
2,4-Dinitrophenylhydrazine(DNPH)
DNPH (acetonitrile)
(HPLC) (UV) 360 nm . 1
DNPH DNPH
.
-
- 115 -
1. DNPH
1.2.2 DNPH
2,4-Dinitrophenylhydrazine(DNPH)
DNPH (Acetonitrile)
(Gas Chromatograph) .
2.
(capillary column)
,
1(R1)
.
3.
3.1
3.1.1 DNPH
DNPH-
. DNPH
(braekthrough)
-
- 116 -
. DNPH
.
2. DNPH
75 225 640 6400 150~250 DNPH 1 3 mg 8.6 mg 86 mg(Bed) 350 1 g 10 g 0.1
3.1.2
1.5 g KI DNPH .
,
.
3.1.3
(
:) 110 L/
.
3.1.4
5 % .
3.1.5
.
3.1.6
, , (1 mL), (1 mL), , (5 mL),
(10 mL), Luer type (10 mL), (10 mL)
3.1.7
3.1.8
,
-
- 117 -
(Teflon) , (Tedlar), (Polyester)
320 L .
3.1.8
2,4-DNPH . DNPH
2,4-DNPH
GC (NPD)
2,4-DNPH
. 40 100
.
3.2
3.2.1 (HPLC)
HPLC .
, , ( ) .
(ODS )
. (injector) (loop)
20100 uL .
3.2.1.1 , () : .
3.2.1.2 (1 L), (1 L, 4 L) : .
3.2.1.3 (25 uL, 250 uL), (25 uL, 250 uL) :
.
3.2.1.4 (100 uL) : .
3.2.1.5 (4 L) : .
3.2.1.6 (350 mL) : .
3.2.1.7 : .
3.2.2 (GC)
(FID :
Flame Ionization Detector), (NPD) (mass spectrometer)
.
-
- 118 -
4.
4.1
DNPH ( )
. , , , n-
iso- 2,4-
. GC
0.1mg/mL .
4.2
4.2.1 (Acetonitrile : HPLC , HPLC )
4.2.2 (HPLC , HPLC )
4.2.3 (Tetrahydrofuran : HPLC , HPLC )
HPLC .
4.2.4 (Ethylacetate)
(1 uL )
2-4-
.
5.
DNPH
5.1
5.1.1 5 .
DNPH 12 L/ .
5.1.2 DNPH 12 L/
5 .
5.1.3 1.0
cm 4 cm KI 3
DNPH .
-
- 119 -
5.1.4
(: ) , , (10 )
(4 ) .
.
2. DNPH
Air Pump
Ozone Scrubber
DNPH Cartridge
Air Pump
Ozone Scrubber
DNPH Cartridge
6. (QA/QC)
6.1
6.1.1
, 535 oC, 85 %
.
6.1.2
.
6.1.2.1 ,
10 % .
6.1.2.2 ,
.
6.1.2.3 10 .
6.2
6.2.1
-
- 120 -
6.2.1.1 ,
.
.
6.2.1.2 .
.
6.2.2
,
, 21)
.
6.2.3
.
6.3
6.3.1
6.3.1.1
6.3.1.2
6.3.1.3
6.3.2
6.3.2.1 : , ,
6.3.2.2 :
6.3.2.3 , .
6.3.2.4 GC/HPLC . , , , ,
, split .
6.3.2.5 .
6.3.3
6.3.2.1 :
.
6.3.2.2 .
.
6.3.2.3 .
21) .
-
- 121 -
6.3.4 ,
.
6.4
6.4.1
(Minimum Detection Limit, MDL) i-
1 ppb .
7
3.1422) .
6.4.2 (Field Blank)
.
6.4.3
3
(peak) (RT: Retention Time) .
3
1 mg/L 10 % . 0.110 mg/L r2 = 0.98
.
6.4.4
1
, .
6.4.5
(law data)
.
7.
7.1 DNPH (HPLC/UV)
22) 7 99%
-
- 122 -
7.1.1
7.1.1.1 60
.
7.1.1.2 10 mL (Luer type) ,
( ) .
7.1.1.3 DNPH .
7.1.1.4 (10 mL) 35 mL
. .
7.1.1.5 1 DNPH
( ) .
7.1.1.6 5 mL
.
7.1.1.7 ( ) DNPH
.
7.1.1.8 DNPH
.
7.1.1.9 ,
2 .
7.1.2
7.1.2.1 0.110 mg/L 35
.
7.1.2.2 DNPH
.
(mg/L)= (g)DNPH(g) DNPH(mg/L)
-
- 123 -
3. DNPH
(g) DNPH
(g)
DNPH 1 mg/L
(mg/L)
44.1 224.2 0.196
58.1 238.2 0.244
72.1 252.4 0.286
86.1 266.2 0.324
7.1.3 HPLC
7.1.3.1 DNPH 350380 nm
360 nm .
7.1.3.2 C18 (4.6 mm 150 mm) (peak)
.
7.1.3.3 1 mL ( A) ,
, (50:45:5, B) .
7.1.3.4 B .
7.1.3.5 HPLC 3 .
-
- 124 -
4. HPLC ()
20 uL (sample loop)
ODS (C18) 4.6 mm 250 mm ( )
A : 100 (V %)
B : // 50/45/5 (V %)
02 : B 100%, 225 : A
(0 % 50 % ), B (100 % 50 % )
2530 : A (100%)
1.0 mL/
20 uL
360 nm
3. HPLC ().
-
- 125 -
5.
1 Formaldehyde CH2O
2 Acetaldehyde CH3CHO
3 Acrolein CH2CH2CHO
4 Acetone CH3COCH3
5 Propionaldehyde C2H5CHO
6 Crotonaldehyde CH3CHCHCHO
7 Butyraldehyde CH3CH2CH2CHO
8 Benzaldehyde C6H5CHO
9 iso-Valeraldehyde (CH3)2CHCH2CHO
10 n-Valeraldehyde CH3(CH2)3CHO
11 o-Tolualdehyde CH3C6H4CHO
12 m-Tolualdehyde CH3C6H4CHO
p-Tolualdehyde CH3C6H4CHO
13 Hexaldehyde CH3(CH2)4CHO
14 2,5-Dimethylbenzaldehyde (CH3)2C6H3CHO
7.1.4
7.1.4.1 0.110 mg/L 35
.
7.1.4.2 x , y
(ug/mL) . ,
. , "7.1" DNPH
.
7.1.5
7.1.5.1 (25, 1 ).
( )ug/m 3 = Aa AbVm
Pa760
298273 + Ta
( 3)
, Aa = (ng)
Ab = (ng)
-
- 126 -
Vm = (L)
Pa = (mmHg)
Ta = ()
7.1.5.2 (ppb) (25 , 1 ).
(ppb)=(/) 24.46 L(g) ( 4) 7.1.6
6.
0.00 0.000
KSA 3251-1
0.00 0.000
0.000 0.0000
n- 0.000 0.0000
I- 0.000 0.0000
7.2 DNPH (GC)
7.2.1
7.2.1.1 60
.
7.2.1.2 10 mL (Luer type) ,
( ) .
7.2.1.3 DNPH DNPH
.
7.2.1.4 (10 mL) 35 mL
.
7.2.1.5 1/min
DNPH .
7.2.1.6
-
- 127 -
50L( 1) . 1 mL
.
7.2.1.7 ( ) DNPH
80L 5 mL ..
7.2.1.8 ( ) DNPH
.
7.2.1.8 DNPH
.
7.2.1.9 ,
2 .
7.2.2
-2,4-DNPH 0.1 mg/mL .
7.2.2.1
0.1mg/mL -
-2.4-DNPH 1mL 80 L
1 L GC .
7.2.2.2 .
7.2.3
7.2.3.1 12 uL (micro syringe)
.
7.2.3.2
1 mL .(
.)
.
7.2.3.3 (FID),
NPD), (mass spectrometer) .
7.2.3.4 (DB-5)
7.2.3.5 250 .
7.2.3.6 200 220 .
7.2.3.7 1.5 mL/ .
7.2.3.8 6 3 .
-
- 128 -
6. ()
HP-5 (Cross linked 5% PhMe Silicone, 0.2mm0.33, 25m)
. 250
. 250
100(1 )20/160(40 )3/200
1 L
3. Aldehyde-DNPH ()
7.2.4
(Mx) (Ms)
(Mx/Ms) -2,4-DNPH (Ax)
(As) (Ax/As)
. -2,4-DNPH
,
-
- 129 -
-2,4-DNPH .
-2,4-DNPH .
Aldehyde = AldehydeAldehydeDNPH AldehydeDNPH ( 5)
7.2.5
.
C = 24.46 (Aa Ab )
Mw V298
273 + t
P760
( 6)
, - C : (ppm)
- Aa : (ng)
- Ab : (ng)
- V : (L)
- t : ()
- Mw : (ng)
- P : (mmHg)
7.2.6 7.1.6 .
-
- 130 -
5
1.
1.1
. .
0.8 ppm , 0.4 ppm, 0.40.8 ppm
1.2
.
, ,
-( GC ) (
SPME )-
2.
2.1 (thermal desorption)
.
2.2 2 (2nd thermal desorption)
,
.
2.3 (breakthrough volume)
-
- 131 -
,
.
, 5 %
.
2.4 (Safe sample volume, SSV)
. 2/3 .
2.5 (Retention volume)
.
2.6 (Conditioning)
350 (
) 99.999 % 50 mL/
2 .
.
2.7
,
1(R1)
.
.
3.
-
- 132 -
3.1
3.1.1
1
, .
1.
3.1.1.1
(breakthrough volume) .
.
,
(conditioning) ,
PTFE (ferrules) . 24
4 .
3.1.1.2
50200 mL
5 .
3.1.1.3
. .
3.1.2
3.1.2.1
,
.
,
.
-
- 133 -
3.1.2.2 (cleaning)
.
6
, .
.
(oil vapor) .
, (trap)
,
(back stream) . ,
,
. ,
.
3.1.3
3.1.3.1
110 L/ ()
.
3.1.3.2
,
(Teflon) , (Tedlar), (Polyester)
320 L .
3.2
3.2.1
. 350
.
10500 mL
(6L) 2 L .
(Glass Bead) 23) -180
23) , ,
-
- 134 -
. ( ; Tenax)
-10 ( ) .
3.2.1.1
.
GC , ,
. , .
3.2.1.2 (Purge Gas)
.
. 99.999 % .
3.2.1.3 (Splitting)
(Splitting) .
10 : 1 .
3.2.1.4 (Desorb)
,
. ,
.
,
.
(thermal desorb). GC
(split) .
.
..
2.
. .
-
- 135 -
3.2.1.5
(Nafion Dryer)
.
3.2.2 (column)
, ,
3060 m 0.25
0.53 mm .
3.2.3 (detector)
(FID),(mass) .
(Scan mode) ppb
, .
3.2.4 (carrier gas)
, (99.999 %)
.
3.2.5 SPME(Slid Phase micro Extractor)
SPME
. SPME carboxen/polydimethylsiloxane (CAR/PDMS) 75 ~
85 m . GC 250 oC
1 (conditioning) .
4.
4.1
.
(Tenax TA, Carbotrap 300 ) .
4.2
ppm(umole/mole)
-
- 136 -
nmole/mole(ppb) . ppm ppb (diluter)
. ppb .
5.
. ,
(shelter) .
5.1
, 150200 mL/
1 L .
10 % . 1
, , 4
.
250320 3060 (Thermal Cleaning) .
5.2
.
(0.05 mmHg)
.
. (Grap Sampling)
. ( 6L)
, (Positive Pressure)
(Air Pump) 2
2 .
-
- 137 -
5.3
110 L/ 5
.
6. (QA/QC)
6.1
6.1.1
, 535 oC, 85 %
.
6.1.2
.
6.1.2.1 ,
10% .
6.1.2.2 ,
.
6.1.2.3 10 .
6.2
6.2.1
6.2.1.1 ,
.
.
6.2.1.2 .
.
6.2.2
,
, 24)
24) .
-
- 138 -
.
6.2.3
.
6.3
6.3.1
6.3.1.1
6.3.1.2
6.3.1.3
6.3.2
6.3.2.1 : , ,
6.3.2.2 :
6.3.2.3 , .
6.3.2.4 GC . , , , ,
, split .
6.3.2.5 .
6.3.2
6.3.2.1 :
.
6.3.2.2 .
.
6.3.2.3 .
6.4.5 ,
.
6.5
6.5.1
(minimum detection limit, MDL)
7
-
- 139 -
3.1425) . 1 ppb
6.5.2
3
(peak) (RT: Retention Time) .
3 100 ppb
10 % . 10100 ppb r2 = 0.98
.
6.5.3
6.5.3.1
ppb 7.1.1
.
6.5.3.2 SPME
ppb 7.2.2 ,
7.2.3GC .
6.5.5
1
, .
6.3.4
(law data)
.
7.
7.1 -
7.1.1
.
.
200350 , 30100 mL/ 515
. 4001000 mL
25) 7 99%
-
- 140 -
.
.
7.1.2
. ( : tenax) -10 ,
(Glass Bead) 26) -180
.
7.1.3 2
250500 , 3100 mL/
115 2 . 2
.
7.1.4
GC GC
. GC/FID scan mode
GC . MS library
.
EI(extracted ion)
, SIM(selected ion monitoring) mode
.
26) , ,
. .
-
- 141 -
1. / ()
. 250
5
. -30
25 mL/
250
2
Tenax TA
GC . 200
GC/MSD
SPB-1,- 624, VOCOL(60m 0.32 mm 1m)
12 ml/
40 (4 ) 10 / 250
MS(Ion source) 190
(Transfer line) 200
35350 amu
EI (Electron ionization) mode
7.1.5
6.5.3 ( : 1 ppm)
( : 1100 ppb) .
. (ng)
.
7.1.6
(ng)
( : 25 , 1) .
C=mV s24.46M ( 1)
, C : (mole/mole)
m : (ng)
Vs : (L)
M : (g/mole)
-
- 142 -
V s=Q t 298
273+TP760 ( 2)
, Vs : (L)
Q : (L/)
t : ()
T : ()
P : (mmHg)
7.1.7
ppm
2
7.2 SPME-
7.2.1
SPME ,
GC .
(solid phase micro-extraction, SPME) .
(fused silica fiber) ,
GC , .
7.2.2
septum SPME
(needle) SPME (:15)
. SPME
.
7.2.3
SPME , 250
GC . GC 3 GC/FID GC/MS
.
7.2.4
-
- 143 -
7.1.6
7.2.5
7.1.7
-
- 144 -
5
-
- 145 -
1 /
1.
()
(Syringe Pump) . GC
, GC/FPD, PFPD(Pulsed Flame Photometric
Detector) .
2.
2.1 (Thermal desorption)
.
2.2 2 (2nd thermal desorption)
,
.
2.3 (Conditioning)
230 10 99.999 % 50 mL/ 2 3
.
.
2.4
-
- 146 -
,
1(R1)
.
.
3.
(TDU ),
(GC/PFPD) .
3.1 (GC/PFPD)
pg ,
PFPD .
3.2 (TDU : Thermal Desorption Unit)
Thermal Desorption Unit , , , ,
GC . ,
GC GC .
1.
-
- 147 -
3.2.1
3.2.1.1
(1 L/ ) MFC .
3.2.1.2 (Mass Flow Controller : MFC)
TDU 1650
1300 mL/ .
3.2.1.3 (Flow & Pressure Controller)
MFC Power , Set Point Voltage
(05 V DC) MFC .
3.2.1.4
Nafion Dryer .
3.2.1.5
.
3.2.2
3.2.1.1
( ) ,
-30 . .
2.
MFC
. (flow) TD
.
-
- 148 -
3.2.1.2
130, 2 3 mm, 6 6.6 mm(1/4")
.
3.2.3
: 6-port valve(24V CE certified Electrical valve),
2,3 way solenoid valve(Low Internal Volume)
3.2.3.1 6-port valve GC carrier gas
MFC .
3.2.3.2 2,3 way solenoid valve purge
.
3.2.3.3 carrier gas
purge . 6-port valve
syringe pump syringe .
3.2.3.4 (loop) GC GC
. GC
.
3.2.4
5 mL
, (loop) GC
GC .
4.
4..1
, , ,
4.1
5.
-
- 149 -
5.1
5.1.1
.
5.1.2
50mL/
.
6.
, , ,
6.5
7.
7.1
7.1.1 On-line
7.1.1.1
. , (H2S)
.
Nafion Dryer , (
) (Tube)
, Cryogenic 95 %
, . Nafion Dryer
, Dryer Air N2 2 (purge)
-
- 150 -
. ,
-30 1
. (Tube) ,
.
7.1.1.2
,
.
Glass Fiber Filter Silanized Glass Wool
. ,
.
.
7.2
7.2.1
7.2.1.1 (System Start)
,
MFC
(purge) .
7.2.1.2 (Sampling)
2,3-way valve , , cylinder,
MFC pump
.
7.2.1.3 (Purge vent)
2,3-way valve gas line
. 7.2.1.4 (Syringe Pump)
2, 3way solenoid valve , ,
-
- 151 -
syringe .
7.2.1.5 GC
6-port valve loop
GC GC . GC
7.2.1.6 (System Cleaning)
GC (Conditioning)
( )
.
/ .
.
7.2.3
H2S 15.2 pg, MM 11.3 pg, DMS 11.2 pg, DMDS 14.9 pg
.
1. ()
GC PFPD (TD)
VP1,
50m0.325
. 250 50mL/
1.6 mL/(mL/)
=10.7 -30
40 H2=10.0 90
200 He(13.8psi) 2
5 5mL/
5
15 /
-
- 152 -
3.
-
- 153 -
2
1.
(Differential Optical Absorption Spectroscopy : DOAS)
.
.
(It/Io), ,
. Beer-Lambert
.
It = Io 10 -CL
(1)
, - Io :
- It :
- : :
- L : ,
- C
2.
(DOAS)
Beer-Lambert
3.
3.1
, ,
, , , .
-
- 154 -
3.1.1
/( )
( 1 ) .
3.1.1.1 /
,
. 1802850 nm .
.
3.1.1.2
.
3.1.1.2
, .
Czerny-Turner Holographic ,
.
(Path)
.
PDA
.
(Library Data Base)
,
.
-
- 155 -
Library
& S/W
/
Internet
1.
3.2
2
.
2.
3.3
3.3.1 : 02000 ppb
-
- 156 -
3.3.2
, .
3 , ,
.
3.3.3
24 .
.
5 % .
3.3.4
(24 )
2 .
.
. 4 .
3.3.5
. .
3.3.6
A . + 10 %
10 B . - 10 %
10 C . B-A, C-A (RANGE)
.
3.3.7
, ( )
AC 1000 V 1 .
3.3.8
, ( )
KSC1031 KSC1302 DC500V
.
3.3.9
01V 15 V( 500 ) 420 mA .
3.3.10
. ,
-
- 157 -
90 % ()
.
4.
4.1
.
4.1.1
4.1.2 .
4.1.3 , .
4.1.4 , .
4.1.5 .
4.2
4.2.1 .
4.2.2 .
4.2.3 2 .
4.2.4 .
4.2.5 .
4.3.
.
4.4
4.4.1 (Path) .
4.4.2 6 1 .
4.4.3 .
-
- 158 -
3
1.
(Differential Optical Absorption Spectroscopy : DOAS)
.
(DOAS)
Beer-Lambert ,
.
(It/Io), ,
. ( , )
Beer-Lambert .
It = Io 10 -CL
( 1)
, - Io
- It
-
- L
- C
2.
(DOAS)
Beer-Lambert
3.
3.1.
, ,
-
- 159 -
, , , .
3.1.1
/( )
( 1 ) .
3.1.1.1 /
,
. 1802850 nm .
.
3.1.1.2
.
3.1.1.2
, .
Czerny-Turner Holographic ,
.
(Path)
.
PDA
.
(Library Data Base)
,
.
-
- 160 -
Library
& S/W
/
Internet
1.
3.2
2
.
2.
3.3
3.3.1 : 02000 ppb
3.3.2
-
- 161 -
, .
3 , ,
.
3.3.3
24 .
.
5 % .
3.3.4
(24 )
2 .
.
. 4 .
3.3.5
. .
3.3.6
A . +10 %
10 B . -10 %
10 C . B-A, C-A (RANGE)
.
3.3.7
, ( )
AC 1000V 1 .
3.3.8
, ( )
KSC1031 KSC1302 DC500V
.
3.3.9
01V 15V( 500 ) 420mA .
3.3.10
. ,
90 % ()
-
- 162 -
.
4.
4.1
.
4.1.1
4.1.2 .
4.1.3 , .
4.1.4 , .
4.1.5 .
4.2
4.2.1 .
4.2.2 .
4.2.3 2 .
4.2.4 .
4.2.5 .
4.3.
.
4.4
4.4.1 (Path) .
4.4.2 6 1 .
4.4.3 .
-
- 163 -
4
1.
(Ammonia) (Amines)
.
. .
. .
, (Methyl Amine), (Dimethyl Amine),
(Trimethyl Amine).
2.
2.1
,
.
1030 .
(
1).
.
(loop) .
.
-
- 164 -
1.
2.2 ()
2 .
1: , 2: , 3: , 4: , 5:
, 6: , 7: , 8: , 9: ,10:
, 11: , 12: (eluent) ( ), 13:
2.
2.2.1
. 5 m
.
2.2.2
.
.
-
- 165 -
.
2.2.3 .
.
.
.
2.2.4 .
.
.
2.2.5
.
.
.
.
.
.
2.3
.
.
3 .
2.3.1 (suppressor) .
2.3.2
.(2.2.5 )
2.3.3
.
-
- 166 -
1: , 2: , 3: (suppressor), 4: , 5:
, 6: , 12: ( ), 13:
3.
3.
.
3.1
18 M .
3.2
98% (ammonium nitrate, NH4NO3),
(methylamine hydrochloride, CH5NHCl), (diethylamine
hydrochloride, C2H7NHCl), (trimethylamine hydrochloride, C3H9
NHCl) 1000 ppm
.
3..3
99 % (methanesulfonic acid, CH4O3S)
-
- 167 -
. .
4.
4.1
4.1.1
100200 L
.
.
.
.
4.1.2
10 L/
. 5 m
.
4.1.3
0.5 1.0 L/
.
(6.1 ).
.
0.95 .
4.1.4
50100 L/ .
.
.
1.
150 L
0.5 L/
70 L/
-
- 168 -
4.2
4.2.1 .
.
4.2.2
.
4.2.3 (suppressor)
. (background) 0.2 S
.
4.2.4 500 1500 L .
.
2.
-SO3H, 250mm4mm
40mM
1.0 mL/
Self Regenerating Suppressor
1000 L
5.
5.1
.
.
.
5.2
5.2.1
-
- 169 -
5.2.1.1 .
.
5.2.1.2 .
5.2.1.3
.
5.2.1.4
.
5.2.1.5
.
5.2.2
5.2.2.1 .
.
5.2.2.2 .
5.2.2.3
.
.
5.2.2.4 .
5.2.2.5
(2.2.4 ).
5.2.2.6
.
6. ()
6.1
.
. .
6.1.1 ()
.
6.1.2 (A, B)
.
6.1.3 .
-
- 170 -
.
(A) (B)
.
6.1.4
(IA, IB) .
6.1.5 .
B A .
(IA, IB) .
6.1.6 .
A=1-(I B/I'B)
AB : (0.0 1.0)
IB : B ( A B)
(mVmin)
IB : B ( B A)
(mVmin)
6.1.7 10 ppbv 0.9 .
6.2
6.2.1 4 .
.
0 5 ppm, 0
50 ppb 4 .
6.2.2 .
.
.
6.2.3
. 2
.
6.2.4 R2 = 0.98 .
6.3
-
- 171 -
.
.
CA =VA
V air
=mA(RT/P)
F airt res
=[C'
AEAV scr/FWA](RT/P)
F air(V scr/F abs)
=[C'
AEA/FWA](RT/P)
F air/F abs
CA : A (ppbv)
CA : A ( ) (ppb)
EA : A
VA : A (nL = 10-9 L)
Vair : (L)
tres : , ()
mA : A (nmol = 10-9 mol)
Vscr : (mL)
FWA : A (g/mol)
Fair : (L/)
Fabs : (mL/)
R : (0.0821 atmL/molK)
T : (K = + 273)
P : (atm)
6.4
6.4.1
7 .
6.1 .
3.14 .
.
6.4.2
6.4.1 .
5 % .
-
- 172 -
5
1.
, 2
(FID )
.
2.
2.1 (capillary column)
,
1(R1)
.
2.2 (Conditioning)
23010 99.999 % 50 mL/ 23
.
.
3.
Online Gas chromatograph 1
1
.
-
- 173 -
AmbientAir
CanisterAir
Dryer ATD
MFC andPump
TransferLine
BP-1Column
PLOTColumn
FID
ArchiveStorage
TurbochromPC
BufferedInterface
OptionalModem
V
FID
DcansSwitch
AmbientAir
CanisterAir
Dryer ATD
MFC andPump
TransferLine
BP-1Column
PLOTColumn
FID
ArchiveStorage
TurbochromPC
BufferedInterface
OptionalModem
V
FID
DcansSwitch
1. Online Gas chromatography system
3.1.
.
3.1.1
3.1.1.1
(semi-permeable membrane)
Nafion Dryer . stainless-steel tube
, .
3.1.1.2 (Automated Thermal Desorption)
GC
(graphite, carbon molecular sieve)
trap . trap 600 mL
trap
-10 . .
(carrier gas) GC .
3.1.1.3 SPT()
GC .
6-port switching , sampling loop
.
.
-
- 174 -
pyrex glass bead .
3.1.1.4 (MFC, Mass Flow Controller)
.
3.1.2
Glass, Steel Fused Silica
, 3060 m
0.250.32 mm 5
. 60
.
.
3.1.3
(GC/FID) .
GC .
3.1.4
, (99.9999%) , .
3.2
3.2.1
SRM(Standard Reference Material) ,
. (Online Gas chromatography)
100 ppb 1ppm
.
3.2.1.1
.
.
ppm ppb .
3.2.1.2
.
-
- 175 -
Cleaning
, line .
99.9999 %
.
, ,
, .
MFC
MFC 2 .
MFC .
,
.
3.3
4.
4.1
6.1 .
4.2
6.2 .
5.
5.1
-
- 176 -
TD(Thermal Desorbtion)
, MFC .
Nafion dryer ,
GC .
5.2
(ppb) .
5.3
()
.
2 .
2.
325 1 PLOT (0.32 mm, 50 m, 5 m)
-10 2 BP-1 (0.22 mm, 50 m, 1 m)
40/sec 15 psi (5 mL/)
1 250
1 44 for 12
15 mL/ 1 44120 (7/), 0
40 2 120168 (5/), 6
600 mL 3 168200 (20/), 6
5.4
.
,
-
- 177 -
1ppm
canister 1, 5,
10 ppb .
1, 5, 10 ppb 600 mL
.
5.5
(ppb) .
-
- 178 -
6
1.
.
( HPLC)
.
2,4-(2,4-dinitrophenylhydrazine, C6H6N4O4,
2,4-DNPH) .
HPLC . HPLC
. (formaldehyde),
(acetaldehyde), (acrolein), (acetone),
(propionadehyde), n-(n-butyraldehyde),iso-
(iso-butyraldehyde),n-(n-valeraldehyde), iso-
(iso-valeraldehyde) 9 .
2.
.
.
.
2.1
,
.
1030 (micron) .
( 1).
.
.
.
-
- 179 -
1.
2.2 ()
2 .
1: , 2: , 3: , 4: ,
5: , 6: , 7: , 8: , 9: , 10:
, 11: , 12: ( ), 13:
( )
1.
2.2.1
. 5 m
.
2.2.2
.
.
-
- 180 -
.
2.2.3 .
.
.
.
2.2.4 .
.
.
2.2.5
.
. .
.
.
.
2.3
2 .
2.3.1 9 -2,4- ..
2.3.2 .
2.3.3
.
-
- 181 -
1: , 2: , 3: UV-Vis , 4: , 5: ,
12: ( ), 13: ( )
2.
3.
.
3.1
(acetonitrile, C2H3N) (phosphoric acid, H3PO4)
3 % 2,4-DNPH 60 ppm .
2,4-DNPH
. .
3.2 -2,4-
-2,4-DNPH 3.1
9 1000 ppm .
. 99 % .
.
.
3.3
-
- 182 -
60 : 40 .
.
4.
4.1
4.1.1
100 200 L
.
.
.
.
4.1.2
10 L/
. 5 m
.
4.1.3
0.5 1.0 L/
.
(6.1 ).
.
0.95 .
4.1.4
50100 L/ .
.
.
-
- 183 -
3.
150 L
0.5 L/
50 uL/
4.2
4.2.1 .
4.2.2
.
4.2.3 UV 360 .
4.2.4 20 60 L .
.
4. ()
C18, 250 mm4.6 mm
: = 60 : 40
1.0 mL/
40 L
UV 360 nm
5.
5.1
.
.
.
-
- 184 -
5.2
5.2.1
5.2.1.1 .
1 , 1 .
5.2.1.2 .