Analysis of gaseous sulfur compounds by process gas chromatography
by Edward I-Sen Wan
A Thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of
MASTER OF SCIENCE in Chemical Engineering
Montana State University
© Copyright by Edward I-Sen Wan (1969)
Abstract:
A process gas chromatograph for the quantitative determination of gaseous sulfur compounds has been
developed and successfully tested on the prepared samples The instrument is an improved version of
the instrument reported by Applebury (4) The sensitivity and precision are increased by replacing the
column packing with PORAPAK Q-S material and increasing the titration solution concentration by
twenty percent.
A detailed study of the variation of peak size, with sample pumping time, cell adjustment and titrating
solution concentration is reported.
The calibration data of hydrogen sulfide, sulfur dioxide and methyl mercaptan are presented at different
operating conditions. The study of higher order sulfur compounds, as well as the effects of temperature,
carrier gas flow, and steam condensation is also reported.
The instrument can analyze wide concentration ranges of gaseous sulfur compounds (from 0.1 ppm to
1000 ppm by volume), and the analysis may be performed by remote-control at ten minute intervals. • ANALYSIS OF GASEOUS SULFUR COMPOUNDS
.
BX PROCESS C-AS 'CHROMATOGRAPHY '
'
' '•
.
" by
. ■
EDWARD I -S E S WAS
A t h e s i s s u b m i t t e d t o t h e G r a d u a te F a c u l t y i n p a r t i a l
f u l f i l l m e n t o f th e re q u ire m e n ts f o r th e degree
of
■MASTER OF SCIENCE
.
in
C h e m ic a l E n g i n e e r i n g
A p p ro v e d :
H e a d , M a jo r D e partm e
C h a irm a n ? E x a m in in g C om m ittee
G r a d u a t e ’ Dean
(7
■MONTANA STATE UNIVERSITY ■
Bozem an, M ontana. J u n e ,■ 1969 -
■
iii.
■
.
:
ACKNOWLEDGEMENTS
.
'•
- The a u t h o r w i s h e s t o t h a n k t h e ’ e n t i r e s t a f f o f t h e C h e m ic a l ,
E n g i n e e r i n g D e p a r tm e n t o f M o n ta n a S t a t e U n i v e r s i t y , a n d i n p a r t i c u l a r ,
D r. M i c h a e l J . S c h a e r who d i r e c t e d , t h i s r e s e a r c h , f o r t h e i r ' s u g g e s t i o n s
w h ic h . l e d t o t h e c o m p le tio n o f t h i s p r o j e c t .
•■ ■The a u t h o r a l s o w i s h e s t o a c k n o w le d g e t h e U n i t e d . S t a t e s 1 P u b l i c
H e a lth S e rv ic e f o r t h e i r f i n a n c i a l su p p o rt g iv en t h i s p r o j e c t .
iv
■•
. TABLE OF CONTENTS
Page
■ I.
I n t r o d u c t i o n .................................................. .
I
II.
E q u ip m e n t a n d E x p e r i m e n t a l P r o c e d u r e s
3
III.
I n s t r u m e n t s ....................■ ..................................
A. A n a l y z e r . .....................................................
B . C o n t r o l U n i t .................................................
C. D a t a P r o c e s s i n g S y stem
6
Reagent
....................................................................
6
P r o c e d u r e ............................. ' .............................
6
R e s u lts and D is c u s s io n
..................................
9
v a r i a t i o n o f p e a k s i z e ........................
P um ping Time .................................................
C e ll A d ju stm e n t
.......................................
T i t r a t e S o lu tio n C o n c e n tra tio n . .
9
9'
9
The
' A.
B.
C.
C a l i b r a t i o n D ata . . . .
Column T e m p e r a t u r e E f f e c t
V.
12
.............................
13
........................
22
. C a r r i e r Gas Flow E f f e c t .......................
26
• S te am C o n d e n s a t i o n T e s t
26
. . • ....................
H i g h e r O r d e r S u l f u r Compounds
. . . .
29
S u g g e ste d O p e ra tin g C o n d itio n s
. . . .
29
. . .
30
' C o n c l u s i o n ................................' .........................
31
' L i te r a t u r e C ited
.32
■ Recommended R e g u l a r M a in t e n a n c e
IV .
k
b
h
V
'
I.
LIST OF TABLES
• ' '
'
'
Page
S t a n d a r d C o n c e n t r a t i o n . . .............................................................................
8
L I.
S o l u t i o n C o n c e n t r a t i o n I n v e s t i g a t i o n ................... '................................
13
III.
C a l i b r a t i o n D a t a o f P r e p a r e d Sam ple a t Temp=90°C, C a r r i e r
G a s 'F l o v = 1 5 0 m l." /m in ........................................................' ..................... .... . .
l6
C a l i b r a t i o n D a t a o f P r e p a r e d Sam ple a t Temp=Sb0C, C a r r i e r
Gas Flow=SOO m l . / m i n .............................................. ■..............................................
IT
C a l i b r a t i o n D a t a o f P r e p a r e d Sam ple a t Temp=90°C, C a r r i e r
Gas Flow=SOO m l . / m i n .
...................................................
18
C a l i b r a t i o n D a t a o f P r e p a r e d Sam ple a t Temp=IOO0C 5 C a r r i e r
Gas Flow=SOO m l . / m i n .............................................................................................
19
C a l i b r a t i o n D a t a o f P r e p a r e d Sam ple a t Temp=OO0 C5 C a r r i e r
Gas Flow=S50 m l . / m i n .............................................................................................
20
Minimum D e t e c t a b l e C o n c e n t r a t i o n ..................................................... ....
SI
• IV .
V.
V I.
V II.
V III.
.
'
Ti
.•
LIST OF FIGURES'
. . .
- ' - . - " - - I '
.
....................................... ................................. , . .
Page^
1.
A n a ly z er
2.
P ro cessin g in t i t r a t i o n
3.
D a ta sy ste m
4.
V a r i a t i o n o f p eak s i z e d u rin g t h e c o n tin u o u s c o u rse o f
a n a l y s i s ..............................
; .........................................
10
C o m p a ris o n o f m i x t u r e an d p u r e c o m p o u n d s r e s p o n s e a f t e r
f o u r h o u r s a n a l y s i s ........................ ...................................................................
I^
5.
S e l l .....................................................
.......................................
6 .. D i r e c t c a l i b r a t i o n c u r v e o f H-^S5 SO ^, CH^SH
7.
•8.
5
7
..................................
.
2b
.......................
25
Column t e m p e r a t u r e a f f e c t s t h e c h r o m a t o g r a p h i c r e s p o n s e
Column t e m p e r a t u r e a f f e c t s t h e r e t e n t i o n t i m e
23
9.
C a r r i e r g as flo w a f f e c t s t h e c h ro m a to g ra p h ic re s p o n s e
10.
C a r r i e r g a s f l o w a f f e c t s r e t e n t i o n t i m e ............................
.
. . .
27
28
v ii
•
'
'
' •
.•
■
‘ ■ .'ABSTRACT '
.
'
A p r o c e s s g a s c h r o m a to g r a p h f o r t h e ' q u a n t i t a t i v e d e t e r m i n a t i o n ofg a s e o u s s u l f u r compounds, h a s b e e n ' d e v e l o p e d a n d s u c c e s s f u l l y t e s t e d on t h e '
p r e p a r e d s a m p le s
.
.
■
The i n s t r u m e n t i s an im p ro v e d v e r s i o n o f t h e i n s t r u m e n t r e p o r t e d
b y A p p leb u ry (A L
The s e n s i t i v i t y a n d p r e c i s i o n . a r e i n c r e a s e d b j r e p l a c i n g
t h e colum n p a c k i n g w i t h PORAPAK Q-S m a t e r i a l an d i n c r e a s i n g t h e t i t r a t i o n
s o l u t i o n c o n c e n t r a t io n by tw e n ty p e r c e n t .
A d e t a i l e d s t u d y o f t h e v a r i a t i o n o f p e a k s i z e , w i t h s a m p le pum ping
t i m e , c e l l a d ju s tm e n t and t i t r a t i n g s o l u t i o n c o n c e n tr a tio n i s r e p o r te d .
The c a l i b r a t i o n d a t a o f. h y d r o g e n s u l f i d e , s u l f u r d i o x i d e an d m e t h y l
m ercap tan a re p r e s e n te d a t d i f f e r e n t o p e ra tin g c o n d itio n s .
The .s t u d y o f
h i g h e r o r d e r s u l f u r com pounds, as w e l l as t h e e f f e c t s o f t e m p e r a t u r e ,
c a r r i e r g a s f l o w , a n d s te a m c o n d e n s a t i o n i s a l s o r e p o r t e d .
The i n s t r u m e n t c a n a n a l y z e w id e c o n c e n t r a t i o n r a n g e s o f g a s e o u s
s u l f u r compounds ( f r o m 0 . 1 ppm t o 1000 ppm b y v o l u m e ) , a n d t h e a n a l y s i s
may b e p e r f o r m e d by r e m o t e - c o n t r o l a t t e n m i n u t e i n t e r v a l s .
I.
IN TR O D U CTIO N .
The K r a f t p u l p m i l l h a s b e e n ' r e p o r t e d t o b e a s i g n i f i c a n t
c o n t r i b u t o r t o a i r p o l l u t i o n , and i n t e n s i v e s t u d i e s a r e i n p r o g r e s s t o
m in i m i z e p o l l u t a n t s fro m t h i s
so u rce.
These s tu d i e s have n e c e s s i t a t e d th e
d e v e lo p m e n t o f a n a l y t i c a l t e c h n i q u e s c a p a b l e o f o b t a i n i n g d e f i n i t i v e
i n f o r m a t i o n on t h e c o m p o s i t i o n s o f m i l l e x h a u s t .
Many g a s c h r o m a t o g r a p h i c m e th o d s f o r d e t e r m i n i n g g a s e o u s s u l f u r
compounds h a v e b e e n r e p o r t e d i n t h e l i t e r a t u r e
(l,
2 , 3 ) , b u t none o f
t h e s e m e th o d s h a v e t h e c a p a b i l i t y o f c o n t i n u o u s l y m o n i t o r i n g p o l l u t a n t s
fro m p u l p m i l l s .
The p r o c e s s g a s c h r o m a to g r a p h
u s e d i n t h i s w ork was o r i g i n a l l y
c o n s t r u c t e d b y A p p le b u r y ( U ) , a n d t h e i n s t r u m e n t d e s c r i b e d i n t h i s t h e s i s
i s a n im p r o v e d v e r s i o n o f t h a t i n s t r u m e n t .
The s e n s i t i v i t y a n d p r e c i s i o n
w e re I n c r e a s e d t e n f o l d b y s e v e r a l m o d i f i c a t i o n s .
(1)
These a r e :
r e p l a c i n g t h e colum n p a c k i n g s w i t h PORAPAK Q-S ( 1 0 0 /1 2 0 m e s h ) , fro m
Yan W a te rs A s s o c . I n c . ,
(2 )
r e p l a c i n g a l l tu b in g and c o n n e c tio n s w ith t e f l o n or s t a i n l e s s s t e e l
m a te ria ls,
(3)
r e p l a c i n g t h e s a m p le v a l v e w i t h a Wesco s o l e n o i d v a l v e , m o d el N o .A 9 7 3 ,
(U)
i m p r o v in g t h e ' s a m p l i n g c o n t r o l b o x and s a m p le i n j e c t o r ,
(5)
i n c r e a s i n g t h e KBr c o n c e n t r a t i o n i n t h e t i t r a t i n g
s o l u t i o n by tw e n ty
p e r c e n t , and
(6) .
i n c r e a s i n g t h e c a r r i e r g a s f l o w r a t e t o 200 m l . / m i n .
-2 -
These m o d i f i c a t i o n p r o v id e d t h e d e s i r e d i n c r e a s e d s e n s i t i v i t y
■without l o s s i n r e s o l u t i o n .
II-
EQUIPMENT AND EXPERIMENTAL PROCEDURES
•
-
INSTRUMENTS
The p r o c e s s gas- c h r o m a to g r a p h c o n s i s t s o f an a n a l y z e r , a c o n t r o l
u n i t , and a d a t a p r o c e s s in g sy stem .
A.
A nalyzer
The a n a l y z e r p r o v i d e s t h e a n a l y s i s o f t h e s a m p l e s .
I t has a
s e n s i t i v i t y o f 0 . 1 ppm t o I ppm d e p e n d in g on t h e i n d i v i d u a l s u l f u r compound
( f o r a d e ta i le d d e s c r ip tio n of th e a n a ly z e r s th e re a d e r i s r e f e r r e d to th e
t h e s i s o f A p p leb u ry ( 4 ) ] .
The s c h e m a t i c d i a g r a m o f t h e a n a l y z e r i s shown
in F ig u re I .
The d e t e c t o r was a t h r e e s e c t i o n b r o m in e c o u l o m e t r i c
m ic ro titra tio n c e ll.
The p o s i t i o n o f t h e s e n s o r e l e c t r o d e w a s ■c h a n g e d so
t h a t t h e c a p i l l a r y tu b e was p e r p e n d i c u l a r t o t h e p la tin u m p l a t e o f t h e
sensor e le c tro d e .
The new p o s i t i o n i s shown i n F i g u r e 2 .
The column
p a c k i n g w as r e p l a c e d w i t h PORAPAK Q-S ( 1 0 0 /1 2 0 m e s h ) .
B.
C o n tro l U n it
A c o n t r o l u n i t g o v e r n e d by a program m ed t i m e r m ec h a n ism
p r o v id e d rem o te c o n t r o l o f t h e a n a l y s i s .
The f u n c t i o n s w i t c h i n b o t h t h e
c o n t r o l p a n e l and th e m ic ro c o u lo jn e te r p e r m i t t e d e i t h e r m anual o r a u to m a tic
a n a l y s i s o f t h e s a m p le m i x t u r e .
d e s c r ib e d in A p p leb u ry ' s ' t h e s i s
A d e t a i l e d d i s c u s s i o n o f t h i s u n i t was
(4 ).
Mylor bag,;
.Compressed air
.Stack sample
Heated line
_Waste
VNa W/" Sample box
A
Solenoid
valve
L' / r!
Z72ZZZZZZZZZZZZZZZ7/;
V/aste
Titration
cell
F ig u re I .
A n aly zer
Chromatographic oven
-5-
Carrier gas in
Solution in_
Sensor____
—Solution and
carrier gas out
------ Anodo
I
Ii
H
-:-v"""•
a%
-tzirn n . K = -X tr:
Ca p i l l a r y t ube.
F ig u re 2.
T i t r a t i o n C e ll
-Glass frits
Platinum plate
-6C.
D a t a P r o c e s s i n g S y stem .
;
'
The o u t p u t s i g n a l was r e c o r d e d b y . a c o n v e n t i o n a l . s t r i p
reco rd er.
■
'
ch art
The r e s u l t s w e r e f o u n d b y t h e c u t a n d w e ig h m e th o d a n d t h e n
c o m p a r e d .w i t h t h e c a l i b r a t i o n d a t a ' fro m a known s a m p le .
d ia g r a m o f t h i s
A sc h em a tic
s y s te m i s shown i n F i g u r e 3.
KSAGEMT
G aseous h y d r o g e n s u l f i d e , s u l f u r d i o x i d e , an d m e t h y l m e r c a p t a n ,
( M a th e s o n C om pany), w e r e u s e d f o r t h e p r e p a r a t i o n o f t h e s a m p l e s .
n itro g e n
Pure
(99•9%) , was u s e d f o r t h e p r e p a r a t i o n o f t h e g a s s t a n d a r d s and
fo r th e c a r r ie r g a s .
The. t i t r a t i o n
C o m p resse d a i r was u s e d t o f l u s h o u t t h e s a m p le b a g .
I
s o l u t i o n was made o f r e a g e n t g r a d e p o t a s s i u m b r o m id e (M a th e son
Coleman a n d B e l l ) , 9 8 % c o n c e n t r a t e d s u l f u r i c a c i d (M athe s o n C om pany), and
d is tille d w a te r.
PROCEDURE
T h e - s t a n d a r d g a s m i x t u r e s w e re p r e p a r e d b y v o l u m e t r i c t e c h n i q u e s
w h ic h i n v o l v e d t h e u s e o f a w e t t e s t m e t e r t o m e a s u r e n i t r o g e n and a
g a s - t i g h t s y rin g e to m easure th e p u re g a s e s .
i n c o n c e n t r a t i o n s a s shown i n T a b l e I .
s t o r e d i n M ylar b a g s .
The s t a n d a r d s w e r e p r e p a r e d
A l l s t a n d a r d g a s m i x t u r e s w e re
Sepam iicn
/ Column
S c rn p ie
v
r
Sample valve
: D efection
I
|— ^
/ C
-
i I
Ccrrier
gas
Recorder
❖
Strip Chart
Data
F ig u r e 3.
D a t a P r o c e s s i n g S y stem
e l i
■-.8TABLE I .
-STANDARD CONCENTRATION .
C o n c e n t r a t i o n (ppm b y v o l . )' .
P u r e Gas
. .
. .D ilu te N itro g e n
#5
2 m l.
*10
4 m l.
If
25
10 m l.
Il
50
20 m l.
M
75
’ 30 m l.
It
100
• 'to m l.
M.
("20
I . IkU CU. f t .
* The f i r s t d i l u t i o n
ppm t o 100 ppm) was made i n a s a m p le h a g .
t h i s r a n g e , t h e c o n c e n t r a t i o n was o b t a i n e d by m u l t i p l e d i l u t i o n .
Below
The i n s t r u m e n t a u t o m a t i c a l l y s a m p le s a n d a n a l y s e s t h e s t a n d a r d
m i x t u r e s , a n d r e c o r d s t h e r e s p o n s e on a s t r i p
c h a r t a s a c h r o m a to g r a m .
The q u a n t i t a t i v e m e a s u r e m e n t o f t h e e l u t i o n t i m e and p e a k a r e a i d e n t i f y t h e
compound a n d i t s
c o n c e n tra tio n .
The c u t a n d w e ig h m e th o d was u s e d f o r q u a n t i t a t i v e m e a s u re m e n t
of th e peak a rea.
The a c c u r a c y was 5$.
III.
RESULTS AND DISCUSSION
VARIATION OF PEAK. SIZE
E a r l y e x p e r i m e n t a l r e s u l t s i n d i c a t e d ' an i r r e g u l a r i t y o f t h e
r e s p o n s e a n d i t was d i f f i c u l t t o o b t a i n r e p r o d u c i b l e ' d a t a .
F ig u re 4
i s an ex a m p le o f an e a r l y r e s u l t ..
The s i z e o f t h e f i r s t p e a k was s m a l l e r t h a n t h e r e s t , an d t h e
f ro m t h e s e c o n d t o t h e s i x t h , t h e r e s p o n s e g r a d u a l l y i n c r e a s e d .
t h a t , t h e r e s p o n s e was s t a b l e .
A fter
T h i s a b n o rm a l b e h a v i o r h a s b e e n s t u d i e d
and s e v e r a l p a ra m e te rs w ere fou n d t h a t d i r e c t l y a f f e c t t h e peak s i z e .
The p a r a m e t e r s w e r e :
s a m p le t i m e , c e l l a d j u s t m e n t , an d t i t r a t i o n
s o lu tio n
c o n c en tra tio n .
A.
Pum ping Time
Because th e p r e p a r e d m ix tu re i s n o t d i r e c t l y i n j e c t e d i n t o th e
c h r o m a t o g r a p h i c c o lu m n , t h e ’ q u a n t i t y o f sa m p le pumped was s o m e tim e s
i n s u f f i c i e n t to have a f u l l resp o n se .
F i g u r e 4 shows t h a t t h e s m a l l r e s p o n s e o f t h e f i r s t r u n o f
t h e a n a l y s i s was due t o i n s u f f i c i e n t s a m p l i n g t i m e .
T h is has been
im p r o v e d b y i n c r e a s i n g t h e pum ping t i m e t o one m i n u t e .
The d o t t e d l i n e
i n F i g u r e 4 shows t h e i m p r o v e d r e s p o n s e .
B.
C e l l A d j u s tm e n t
The m i c r o t i t r a t i o n c e l l i s d e s i g n e d t o o p e r a t e a t a c o n s t a n t
titra tio n
i o n c o n c e n t r a t i o n w h ic h i s . d e t e r m i n e d by t h e b i a s s e t c o n t r o l
-1 0 -
F ig u re ^ .
V a r i a t i o n o f peak s i z e d u rin g th e c o n tin u o u s
course o f a n a ly s is .
—H r
of th e m fcro co u lo m eter.
T h e ' t i t r a t i o n i o n s a r e B r -/B r . . A s h i f t i n
t i t r a n t io n c o n c e n tra tio n w ith in th e t i t r a t i o n
refe re n c e sensor e le c tro d e s .
c e l l is d e te c te d by th e
The EMF b e tw e e n t h e s e e l e c t r o d e s i s a
d i r e c t f u n c t i o n o f t h e t i t r a n t i o n c o n c e n t r a t i o n ( a c t i v i t y ) upon t h e
s u rfa c e o f th e p la tin u m e le c tr o d e .
A f te r each a n a ly s is » th e g e n e ra to r
p a i r r e - e s t a b l i s h e s t h e t i t r a n t t o i t s o r i g i n a l c o n c e n t r a t i o n and t h e
s y s te m i s a g a i n i n e q u i l i b r i u m .
The t i t r a t i o n
s o l u t i o n i s r e p l a c e d by
p e r i o d i c a l l y pum ping a s m a l l amount o f e l e c t r o l y t e
e le c tr o ly te in th e t i t r a t i o n
c e llJ
(i.e .
20$ o f t o t a l
i n to th e c e l l a f t e r each a n a l y s i s .
I t was f o u n d t h a t t h e e q u i l i b r i u m t i m e f o r t h e f r e s h e l e c t r o l y t e
s o l u t i o n was on t h e o r d e r o f t h r e e t o t e n m i n u t e s .
p a r a m e t e r s w h ic h a f f e c t t h i s
of th e sensor e le c tro d e ,
e q u ilib riu m tim e.
There a r e t h r e e
They a r e :
( l) th e lo c a tio n
( 2 ) t h e s a m p le r e s i d e n c e t i m e i n t h e s o l u t i o n ,
and ( 3 ). t h e r e g e n e r a t i o n s o l u t i o n r a t e .
The e l e c t r o d e s w e r e p l a c e d s o t h a t . t h e
d i r e c t l y i n f r o n t o f th e gas i n l e t c a p i l l a r y .
s e n s o r e l e c t r o d e was
The m ore p e r p e n d i c u l a r t h e
p o s i t i o n of. t h e s e n s o r e l e c t r o d e t o t h e c a p i l l a r y , t h e l e s s tim e r e q u i r e d
fo r e q u ilib riu m .
e le c tro d e t o
A l s o , t h e m o re p e r p e n d i c u l a r th e - p o s i t i o n o f t h e s e n s o r
t h e c a p i l l a r y , t h e l e s s t a i l i n g o f t h e sa m p le p e a k .
The g a s s a m p le was e m i t t e d fro m t h e c a p i l l a r y t u b e a n d r e a c t e d i n
th e t i t r a t i o n
so lu tio n .
r e a c t i o n t i m e , w h ic h
The e q u i l i b r i u m t i m e d e p e n d e d u p o n t h e s o l u t i o n
in tu rn
was a f u n c t i o n o f g a s f l o w r a t e .
The
g r e a t e r t h e g a s f l o w r a t e , t h e s m a l l e r t h e s a m p le r e s i d e n c e t i m e ' an d h e n c e .
-12I e s s r e a c t i o n t i m e was n e e d e d .
The r e g e n e r a t i o n r a t e n o t o n l y d e t e r m i n e d
t h e e q u i l i b r i u m tim e ,, b u t a l s o e f f e c t e d t h e s h a p e o f t h e p e a k an d t h e
lo c a tio n o f th e b a s e lin e .
Xf t h e ' r e g e n e r a t i o n ' r a t e was n o t p r o p e r l y
a d j u s t e d , t h e r e was a n e x c e s s o r d e f i c i e n c y o f t i t r a t i o n i o n i n t h e c e l l .
An e x c e s s o f B r - i o n p r o d u c e d a s h a l l o w o v e r s h o o t a n d a d e f i c i e n c y
p roduced a l e n g t h ly t a i l as th e c e l l e q u i l i b r a t e d .
F o r p r o p e r o p e r a t i o n i t was n e c e s s a r y t h a t t h e s e n s o r e l e c t r o d e ,
t h e c a r r i e r g a s f l o w , a n d t h e r e g e n e r a t i o n r a t e b e a d j u s t e d so t h a t t h e
p e a k h a d no o v e r s h o o t o r t a i l i n g .
E x p e r i e n c e showed t h a t t h e f o l l o w i n g c o n d i t i o n s p r o d u c e s a t i s f a c t o r y
r e s u l t s : ( l ) th e c a p i l l a r y tu b e p e r p e n d ic u la r to th e s e n so r e le c tr o d e ,
(2)
t h e c a r r i e r ’ g a s f l o w r a t e a t 200 m l . / m i n . , an d (3 ) t h e r e g e n e r a t i o n r a t e
a t 3 c c /c y c le .
C.
T itr a te s o lu tio n c o n c e n tra tio n
S e v e r a l c o n c e n t r a t i o n s w e re - i n v e s t i g a t e d s i n c e a c h a n g e i n t h e
titra tio n
s o lu tio n c o n c e n tra tio n e ffe c te d th e c e ll o p e ra tio n .
shows t h e c a s e s i n v e s t i g a t e d a n d t h e r e s u l t s .
T ab le I I
-13TABLE I ! ..
SQLUTION CONCENTRATION INVESTIGATION
C o m p o s it io n
R esp o n se /C o n ce n tra tio n
. EgS
CE SE
S02
Case I
7 . 2 g KBr + 6 m l.EgSO,
+ I l i t e r KgO
0.51
. " 0 .2 0
0 .7 0
Case 2
• 8 . SltgKBr 4- 6 m l.IC SO ,
+ I l i t e r KgO
0.60
" 0.26
0.85
Case 3
7 *Sg KBr + 7 .2ml.EgSO,+ I l i t e r EgO
0 .6 3
0.28
0.90
Case k
8. SltgKBr +
0.69
• 0 .3 1
1 .0 0
7.2ml.H SO1^+ I
l i t e r KgO
The above d a t a i n d i c a t e s t h a t t h e h i g h e r c o n c e n t r a t i o n l e v e l gave
th e h ig h er s e n s i t i v i t i e s .
T h e r e f o r e , we o p e r a t e d t h e t i t r a t i o n
c e l l w ith
t h e c o n c e n t r a t i o n l e v e l o f Case It.
CALIBRATION DATA
.
.
.
A f te r th e s te a d y s t a t e resp o n se had been fo u n d , r e p l i c a t e d bags o f
s t a n d a r d s a m p l e s w e r e p r e p a r e d and a n a l y z e d .
A c a l i b r a t i o n c u r v e was
o b t a i n e d , f o r s t a n d a r d s o f p u r e H gS5 S O ^, a n d CH^SH, and a l i n e a r r e s p o n s e
was shown.
Then a m i x t u r e o f HgS5 SOg, a n d CH^SH was p r e p a r e d t o i n v e s t i ­
g a t e t h e p o s s i b l e r e a c t i o n s b e tw e e n t h e c o m p o u n d s.
re su lts
The e x p e r i m e n t a l
i n d i c a t e d t h a t , i n t h e f i r s t f o u r h o u r s , t h e m i x t u r e h a d t h e same
r e s p o n s e a s e a c h compound p r e p a r e d s e p a r a t e l y .
H o w e v e r, a f t e r f o u r h o u r s ,
t h e r e s u l t s showed t h a t t h e SOg and HgS r e a c t e d s l o w l y w i t h e a c h o t h e r .
T h e r e f o r e t h e r e s p o n s e o f t h e s e tw o was s l i g h t l y d e c r e a s e d , a s s h o w n 'i n '
F i g u r e 5*
I n a d d i t i o n , a random c o n c e n t r a t i o n s a m p le was p r e p a r e d and
u s e d t o com pare w i t h t h e p u r e c o m p o u n d 's r e s p o n s e .
T his s tu d y r e v e a le d
t h a t t h e r e s p o n s e s w e re a l m o s t t h e same d u r i n g t h e f i r s t f o u r h o u r s o f
-Ilt-
—
pure compound
mixtures after 4
hours analysis
—r
20
30
60
70
90
IOO
Concentration ( ppm)
F i g u r e 5>
C o m p a ris o n o f m i x t u r e a n d p u r e c o m p o n e n t’ s r e s p o n s e a f t e r
It h o u r s a n a l y s i s a t colum n t e m p e r a t u r e = 9C°C.
C a rrie r
g a s f l o w = 200 m l / m i n . B i a s s e t = 725 mv. Range 2.
I / V x 6 ' PO'RAPAIC Q-S c olum n.
■■
a n a ly s is..
’
“15- •
■
‘
C o n se q u e n tly , th e ' c a l i b r a t i o n d a ta can o n ly be ta k e n d u rin g t h e ’
f i r s t four h o u rs.
•
'
.
•
.
T h e ’ c a l i b r a t i o n d a t a f o r . a l l t h r e e compounds a t d i f f e r e n t o p e r a t i n g
c o n d i t i o n s a r e l i s t e d on T a b l e X I I , T a b l e I V 5 T a b l e V, T a b l e X7I and T a b l e . V I I ,
T a b l e V I I I shows t h e minimum d e t e c t a b l e c o n c e n t r a t i o n .
T h e o r e t i c a l l y , t h e r e s p o n s e o f e i t h e r H^S or.. Ch^SH s h o u ld , b e f o u r
t i m e s g r e a t e r t h a n SO , b e c a u s e o f t h e d i f f e r e n c e i n e l e c t r o n r e q u i r e m e n t ■
f o r th e e le c tro c h e m ic a l r e a c tio n s .
T his i s
shown i n t h e f o l l o w i n g
e q u a tio n s.
A. H2S
O x i d a t i o n : _ IiHgO +
R e d u c tio n :
SO,
IiBr2 + Ge"
C ell r e a c t i o n :
+ IOH+ + Be
B B r'
^HgO + ^ B r2 + HgS
8Br
+ SO^
+ IOH
B. SO2
O x id a tio n :
ZHgO + SO
R e d u c tio n :
B r 2 + 2e
C e ll re a c tio n :.
. SOjjT + t o + + 2 e “
2Br
ZHgO + Br
+ SOg
2Br
+ SO^. + UH
S i m i l a r l y , t h e m e t h y l m e r c a p t a n h a s t h e same e l e c t r o n c h a n g e
r e q u i r e d a s i n t h e HgS r e a c t i o n .
The c a l i b r a t i o n c u r v e o f t h e m i x t u r e
•.
p r e p a r e d f o r 5 ppm , 10 ppm , 25 ppm, 50 ppm , 75 ppm a n d 100 ppm i s shown i n
~ i6 "
TABLE III.
A.
CALIBRATION DATA OF PREPARED MIXTURE AT TEMPERATURE=9Q°C,
CARRIER GAS ,ELO¥=150 ml/min BIAS SET=725 mv. AND RANGE=Z.
H yd ro g e n s u l f i d e
C o n c e n tra t.io n C p p m l
R e s p o n s e (peak, a r e a i n mg)__________ . Avg. R e s p o n s e
5
5 .4
10
9 .8
25
2 4 :1
50
48.2
73.0
99.4
75
100
■
'
5:2
' 5.3
5 .5
' 5 .1 .
10.0 . 9 . 7
9.9 . 10.2
24.3 23.8 ■ 24.2 23.6
49.2 . 4 9 . 9
50.3 48.9
73.9 ' 7 5 . 4
74.9 75.9
98.6 99.3 99.7 1 0 0 .3
5 -3
. 9.9
23,9
4:9.3
74.3
99.4
S u lfu r d io x id e
5
2.5
2.6
2.7
2 .3
2 .5
'10
5-7
5 .8
5 .4
5 .5
5 .4
2.5
- 5.6
25
9-5
9 .4
9-7
19-4
2 0 .0
75
28.0
4 0 .9
29.8
39.3
'
9.9
20.8
29.0
9-7
50
9.8
20.7
29.7
4 i.4
4 i.i
9-1
9.3
9/8
15.9
8.4
8.7
16.5 ■ 17.0
35.2 34.4
66.8 66.4
96.0 95.4
100
M e th y l m e r c a p t a n
5
10
25
50
75.
100
16.9
35-9
64.6
95.2
126.2
l6 .6
34.0
66.3
98.5
122.5
3 5 -7
64.9
97.1
120.5
1 2 1 .7
20.5
28.9
4o.6
125.6
-
20.3
29.0
40.7
8.9
16.6
35.0
65.8
96.4
1 2 3 .3
•
TABLE IV.
' . - I T 1'
.
CALIBRATION DATA O F P R E P A R E D MIXTURE AT TEMPERATURE=80oC s
GAS FLOW=20Q. ml/mi.n5 BIAS SET=725 mv A N D RANGE=R. '
C A RRIER
A.
H yd ro g en s u l f i d e
• .
C o n c e n tra tio n (p p m )
R e s p o n s e ( p e a k a r e a i n mg)_______
6 .7
.T-O
1 3 .1
1 3 .5
1 3 .2
27.3
52.7
7 7 .1
27.9
53.0
76.3
95.7
96.6
99.8
27.8
52.2
76.6
97.9
2.2
2 .3
2.3
5.0
8,3
4 .8
5 -0
7 .2
7 .4
7.0
10
.1 3 .2
12.6
25
28.5
13.4
28.3
50
5 1 .3
' 75
76.2
100
100.2
27.0
52.6
78.2
.97.3
A vg. R e s p o n s e
6.9
5
5 1 .5
7 5 .5
S u lfu r d io x id e
5
2 .3
2 .4
2 .5
10
5-0
5.2
4 .9
25
8.2
8 .4
75
8.3
16.5
23.6
100
50
■
8.3
16.9
24.5
34.0-
- 8.3
"
17.5
17.1
1 7 .7
1 7 .1
25.1
24.6
3%.2
25.2
32.9
3 4 .7
3 4 .5
5
9 .2
8.7
9 .1
10
16.6
16.4
15.6
16.1
16.7
1 6 .3
25
3 4 .2
34.4
3 4 .0
32.9
50
59-5
61.0
75
8 7 .4
89.9
59.8
88.6
33.8
60.5
88.1
100
1 1 4 .3
118.8
33.5
61.5
88.2
109.9
2 4 .6
3 4 .1
M e th y l m e r c a p t a n
1 0 8 .4
8.9 '
8.6
6 l.l
86.8
1 1 3 .8
8.9
1 1 1 .4
-18TABLE v.
A.
CALIBRATION DATA QF PREPARED MIXTURE AT TEMPERATURE-8Q°C,
. CARRIER 'GAS FL0W=2Q0 ml/min, BIAS. SET=725 mv AND R A N G E = Z .
H y d ro g e n s u l f i d e
C o n c e n tra tio n (p p m )
R e s p o n s e ( p e a k a r e a i n mg)_________
5
5-1
. 4 .8
5 .1
5*0
10
8 .9
9-1
9 .0
9 .1
25
2 1 .0
50
hi. 3
■ 75
6l.h
21.2
42.2
62.2
82.1
'
ioo-
82.8
20.7 ' 20.9
42.9
4 2 .7 '
63.8 63.5
8 2 .4
82.7
-
A vg. R e s p o n s e
4 .9
4 .9
9.2
20.9
'4 1 .9
63.1
83.6
9 .1
■
20.9
42.2
63.0
82.8
S u lfu r d io x id e
. 5
1 .9
' 2.0 •
1 .8
10
4 .4
4 .5
' 25
7 .4
50
'
2 .1
- 1.9
1.9
4 .3
4 .2
4 .2
4 .3
7-3
7-7
7 .6
7 .5
7 -5
1 5 .0
15-5
16.1
16.0
1 5 .5
15.6
75
2 1 .7
2 3 .1
22.5
2 2 .4
22.5
100
3 1 .7
32.1
31.9
23.0
32.1
3 1 .5
3 1 .5
6.7
13.5
27.3
52.7
M e th y l m e r c a p t a n
5
7-2
7 .4
7 .0
6.9
10
1 3 .4
1 3 .2
1 2 .6
1 3 .1
25
28.5
27.0
28.3
50
5 1 .3
52.6
51.5
75
76.0
7 8 .2
77.1
27.9
53.0
76.3
100
1 0 0 .2
97.3
95.7
9 6 . 6>
7 5 .5
99.8
7 .0
13.2
27.8
52.2
76.6
97.9
-19
TABLE VI.
A.
CALIBRATION DATA OF PREPARED MIXTURE AT TEMPERATURE=1Q0°C,
CARRIER GAS FLOW=POQ. ml/min, BIAS SET-725 W AND RANGE-2 .
H yd ro g e n s u l f i d e
C o n c e n tra tio n (p p m )
5
10
'
R esponse (peak a r e a
3 .1
3:0
5.9
6.0
■
i n mg)
Avg
.
R esponse
2.8
3 .0
3 .1
3 .0
5 .8
6:0
. G.2
6.0
25
15.2
1 5 .4
1 5 .1 '
15.1
1 4 .9
50
3 1 .7
32.4
32.9
75
^ 9 .2
49.8
5 1 .2
100.
67.8
67.4
67.5
33.1
50.9'
67.7
32.3
50.5
68.4
1 .6
1 .4
1 .5
3.6
6.6
3.8
6.6
15.1
32.5
50.3 . ' 67.7
S u lfu r d io x id e
5
'1 .5
10
3 ,7
1.6
3.8
' 25
6 .4
■ 6.5
50
13.7
i
75
1 9 .7
21.0
29.2
28.0
100
4 .q
3 .5 '
1 .5
■"3.7
6 .5
6 .5
1 4 .4
1 4 .1
i4 .i
20.9
29.5
2 0 .4
29.3
20.2
29.0
4 .9
4 .8
4 .7
9.6
22:6
9.9
22.3
10.3
4 3 .2
4 4 .5
4 4 .3
65.6
6 4 .4
6 4 .2
22.2
43.8
65.0
83.0
83.3
85.8
8 4 .3
1 4 .5
'
20.5
29.0
M e th y l m e r c a p t a n
5
5 .1
10
1 0 .2
25
22.8
50
75 .
100
•
5 .2 ■
10.0
21.6
- 44.2
4 3 .1
64.6 66.5
85.9 83.8
2 1 .7
4 .9 '
1 0 .0
'
"2 0 —
TABLE yiX.
A.
CALIBRATION DATA. OF PREPARED FIXTURE AT TERtPERATURE^Q0C 5
CARRIER
RLOW=R^Q
BIAS' SET=725 mv AZD RAlfGE=Z.
H yd ro g en s u l f i d e
C o n c e n t r a t i o n Cppm] . R e s p o n s e C p e a h ' a r e a •in mg),.
5'
2.8
10
’ 5-0
25
'1 3 . 1 '
1 3 .3
24.8
37.6
25.4
38.1
50.8
50
.
75.
'
‘5 1 . 2
100 .
2.&
2.9
2 .7
5-2
5 .1 .
Avg.- R e sp o n se .
• 2 .5
' 2 .7 '
5 ,2
5 .1
. 5-1
1 3 .0
12.8
1 3 .0
25.3
39.0
25.4
. 5 1 .3
5 1 .9
5 1 .4
25.3
38.5:
51.3
1 .4
1 .5
1 .3
1 .2
1 .3
3 .2 .
3 .0
3 .1
3 .0
3-1
5.8
..5 .2 '
5 .0
5-4
' 1 2 .9
25.0
39.1
'
38,7
S u lfu r d io x id e
1 .3
• 5 .
10
. 3 .1
25
5-3
5 .4
50
10.6 .
I L 10
1 1 .3
■11.5
1 1 .2
" 1 1 .3
75
1 5 .4
1 6 .4
22.5
21.7
16.0
22.7
15.9
100
16.9
22.8
2 2 .4 '
' ■16.1 '
22.3
• 5
5 .3
5 .5
5 .2
5 .1
5 -0
10
9-9
9.8
.
M e th y l m e r c a p t a n
9.3
9-7
20,9 " 20.0
3 8 .1 .
39.2
2 1 .1
2 0 .0
75 .
38.0
56.8
100 .
7 4 .2
38.9
57.9 5 7 . 1
73.1 . 70.9
25
50
■
56.6
9.9
20.2
39.0
55.6
7 1 . 6"
7 4 .0
5 .2
9-7 ■
20.5
3 8 .6
56.8
7 2 .7
21
TABLE V T I I . . ' '
MINIMUM DETECTABLE CONCENTRATIONS' '
H2S
SO2
CH SE
;
0 . 0 5 ppm
.
P.I
ppm
0 . 0 5 ppm
-22F i g u r e 6.
As s e e n i n t h i s
g r e a t e r t h a n SO^.
f i g u r e s't h e ' re s p o n s e o f
-was n o t f o u r t i m e s
I n s t e a d , i t was. 2 . 5 t i m e s g r e a t e r t h a n S O ..
The
s m a l l e r r e s p o n s e o f b o t h H S a n d CH SH. was t h r e e t i m e s g r e a t e r t h a n SO . ■
The s m a l l e r r e s p o n s e o f b o t h H.^S a n d CH SH i s due t o t h e i n c o m p l e t e
r e a c t i o n o f t h e s e compounds i n t h e t i t r a t i o n
show t h e l i n e a r r e s p o n s e .
so lu tio n .
A l l t h r e e compounds
I n t h e low c o n c e n t r a t i o n r a n g e , t h e a b s o r p t i o n
i n t h e colum n was . n o t i c e a b l e ; e s p e c i a l l y f o r t h e SO^.
T h e re fo re , th e
r e s p o n s e was l e s s t h a n e x p e c t e d f o r t h e . l o w c o n c e n t r a t i o n r e g i o n o f t h e
c a lib ra tio n
cu rv e.
The o r d e r o f e l u t i o n was HgS , SO^, a n d CH^SH.
COLUMH TEMPERATURE EFFECT
From q u a n t i t a t i v e s t u d i e s , t h e r e s u l t s show t h a t t h e h i g h e r t h e
colum n t e m p e r a t u r e , t h e l o w e r t h e r e s p o n s e .
A l s o , i t was f o u n d t h a t s a m p le s
a t lo w er c o n c e n t r a t io n s h ad l e s s te m p e ra tu re e f f e c t th a n th o s e a t h ig h e r
c o n c e n tra tio n s.
A c o m p a r is o n o f t h e t h r e e compounds shows t h a t SO
i s th e l e a s t
a f f e c t e d by t h e t e m p e r a t u r e , an d CH^SH i s t h e m o st a f f e c t e d . The t e m p e r a t u r e
e f f e c t .on a l l t h r e e compounds a t a c o n s t a n t c a r r i e r g a s f l o w (.200 m l . / m i n . )
i s shown i n F i g u r e 7•
A .c o lu m n t e m p e r a t u r e a l s o a f f e c t s t h e p e a k s h a p e a n d r e t e n t i o n
tim e.
The h i g h e r t h e t e m p e r a t u r e , t h e s h a r p e r .t h e p e a k a n d t h e s h o r t e r
th e r e t e n t i o n tim e.
i n F i g u r e 8.
A p l o t o f r e t e n t i o n t i m e v e r s u s t e m p e r a t u r e i s shown
.
-23-
OO
Concenh at ion ( ppm)
F ig u r e 6.
D i r e c t C a l i b r a t i o n C urve o f H^S, SO^, CHvSH.
90
IOO
~ 2 k~
o
^
O
Peak area
IOO PPM
7 5 PPM
5 0 PPM
5 0 PPM
IOO PPM
'C r — -
/s, —
—
O1
5 0 PPM
IO PPM
IOPPM
IO PPM
Column Temperature (0C)
Figure 7•
Column temperature affects the Chromatographic Response.
-25-
A
C A L :# /
o
%
Column Temperature (tTl)
F i g u r e 8.
C o l u m n 't e m p e r a t u r e a f f e c t s t h e r e t e n t i o n t i m e a t b a r r i e r
g a s f l o w = 200 m l . / m i n . B i a s s e t = 725 mv. E ange = 2 .
1/1+" x 6 ’ POMPAK Q-S colum n.
.-26 CAREIEE GAS FLOW EFFECT
The c h a n g e o f t h e ' c a r r i e r g a s 'flow; r a t e a f f e c t s t h e p e a k s h a p e ,
p e a k s i z e , an d e l u t i o n t i m e ,
. I t was n o t i c e d t h a t t h e h i g h e r t h e c a r r i e r
g a s f l o w , t h e g r e a t e r t h e random n o i s e .
The h i g h e s t c a r r i e r g a s f lo w
w i t h o u t n o t i c e a b l e n o i s e was 200 ml.; / m i n .
l e v e l was e s t i m a t e d t o b e 1% o f f u l l s c a l e .
At t h i s
c o n d itio n , th e n o ise
A diag ram r e l a t i n g th e
c a r r i e r g a s f l o w t o t h e r e s p o n s e o f e a c h compound a t c o n s t a n t t e m p e r a t u r e
i s shown i n F i g u r e 9•
The s l o p e shows t h a t t h e r e s p o n s e o f a l l t h r e e
compounds d e c r e a s e d w i t h i n c r e a s i n g f l o w r a t e .
A l s o ,b o t h th e response
o f SOg and CH^ SH show a l i n e a r d e c r e a s i n g r e l a t i o n s h i p , w h i l e HgS shows
a n o n lin e a r r e la tio n s h ip .
t i m e ' i s shown i n F i g u r e 1 0 .
The e f f e c t o f c a r r i e r g a s f l o w on r e t e n t i o n
I t shows: t h a t t h e r e t e n t i o n t i m e - a p p r o a c h e s a
d e f i n i t e v a lu e a t h i g h e r flo w r a t e s .
STEAM CONDENSATION TEST
'
'
The w a t e r - g a s s t r e a m s fro m p u l p i n g p r o c e s s e s a r e s a t u r a t e d w i t h
w a te r a t e le v a te d te m p e ra tu re s .
The c o n d e n s a t i o n .of t h i s w a t e r v a p o r
i n s i d e t h e sa m p le b o x a n d s a m p l i n g t u b e may c a u s e a c o r r o s i o n p r o b le m .
I n o rd e r to p r e v e n t c o n d e n sa tio n d u rin g th e a n a ly s i s p r o c e s s , b o th th e
s a m p l i n g t u b e and. t h e s a m p le b o x w e re i n s u l a t e d and m a i n t a i n e d a t a
t e m p e r a t u r e o f IOO0C ,
A t r i a l r u n u s i n g s te a m a s t h e sample- was s t u d i e d .
The r e s u l t s show ed no c h r o m a t o g r a p h i c p e a k a p p e a r e d on t h e s t r i p
ch art
r e c o r d e r and t h a t t h e in s tru e m e n t c o n tin u e d t o p erform s a t i s f a c t o r i l y
a f t e r th e t e s t .
A l t h o u g h t h e c o n d e n s a t i o n o f s te a m i n t h e c e l l c o u l d
-27-
O
IOO PPM
5 0 P PM
0- 3 0
5 0 PPM
IOO PPM
fb
200
Flow Rate (inVmin)
figure 9•
Carrier gas flow affects the chromatographic response.
-2 8 -
!7 5
200
2 25
Carrier gas flow (ml/min)
Figure 10.
Carrier gas flow affects retention time.
-29-
p o s s i b l y change th e t i t r a t i o n .s o l u t i o n , th e ' e x p e iim e n ta l r e s u l t s i n d ic a te d ’
t h a t th e' e f f e c t yas n e g lig ib le .
HIGHER ORDER SULFUR COMPOUNDS
. T h e ' h i g h e r o r d e r s u l f u r compounds i n c l u d i n g d i m e t h y l s u l f i d e and
d i m e t h y l d i s u l f i d e w e re s t u d i e d .
room t e m p e r a t u r e .
T h e s e two compounds e x i s t a s l i q u i d s a t
T h e r e f o r e , t h e s t a n d a r d s a m p le s w e re p r e p a r e d by
d i s s o l v i n g t h e compound i n a c e t o n e , an d t h e n i n j e c t i n g i t i n t o t h e M ylar
bag.
The s a m p le b a g was t h e n h e a t e d g r a d u a l l y b y a steam , h e a t e r .
The
q u a l i t a t i v e a n a l y s i s o f t h e s e compounds showed t h a t b o t h compounds h a v e
b ro a d c h ro m a to g ra p h ic p e a k s .
The r e t e n t i o n t i m e f o r d i m e t h y l s u l f i d e was
f o u r m i n u t e s a n d f o r d i m e t h y l d i s u l f i d e was 1 0 . 5 . m i n u t e s .
No c a l i b r a t i o n
c u r v e s w e re o b t a i n e d .
SUGGESTED OPERATING CONDITIONS
I t was f o u n d t h a t t h e f o l l o w i n g o p e r a t i n g c o n d i t i o n s p r o d u c e d
sa tisfa c to ry r e s u lts :
Column:
1 / 4 " x 6' PORAPAK Q-S 1 0 0 /1 2 0 m esh.
T itra tio n s o lu tio n :
8 . 6 4 m g.KBr added- t o t h e l 4 . 4 m l. c o n e .
s u l f u r i c a c id and I l i t e r o f d i s t i l l e d w a te r.
. Column t e m p e r a t u r e : 9 0 °C
S a m p lin g t u b e t e m p e r a t u r e :
S am ple b o x t e m p e r a t u r e :
C a r r i e r Gas f l o w :
IOO0 C
■
IOO0C
200 m l . / m i n .
-30B ias s e t ; .
725. w .
Range: 2
•
B ecpam iended' regular Jnaintenance:
1.
C le a n t h e t i t r a t i o n
c e l l once a m o n th .
2.
C le a n t h e ' Dyna pump e v e r y ' s i x m o n t h s . •
3.
Check t h e s o l e n o i d s a m p le v a l v e e v e r y s i x m o n th s t o s e e i f t h e
s i l i c o n ru b b e r O -rin g s a re b ro k en .
4.
Check t h e b a t t e r y i n t h e r e c o r d e r a n d c o n t r o l s y s t e m .
IV.
'CONCLUSION
R e s u l t s p r e s e n t e d ' shew t h a t t h e im p r o v e d i n s t r u m e n t g i v e s . . . r e l i a b l e
c a l i b r a t io n d a ta under sim u la te d p la n c o n d itio n s .
• The i n s t r u m e n t p e r f o r m e d s u c c e s s f u l l y w i t h o u t m a j o r m e c h a n i c a l
t r o u b l e s f o r a p e r io d o f t e n m o n th s.
w ith in f i f t e e n m in u te s.
An unknown s a m p le c a n b e a n a l y z e d
The r e t e n t i o n t i m e i d e n t i f y s t h e compound and
t h e r e s p o n s e i n d i c a t e s t h e c o n c e n t r a t i o n o f t h e com pound. •
The a v e r a g e d e v i a t i o n i s e s t i m a t e d a s 12%.
T h e •d e v i a t i o n s a re
c a u s e d by e r r o r s i n s a m p l i n g a n d i n t h e d a t a h a n d l i n g m e th o d .
■y.
LITERATURE CITED
(1 )
Adam s, D. F . , B a m e s b e r g e r 5 W, L.., R o b e r t s o n , T. J . , uA n a l y s i s o f
S u i f u r - - C o n t a i n i n g . G ases i n t h e A m b ien t A i r U s in g S e l e c t i v e P r e - F i l t e r s
and a M ic r o c o u lo m e tr ic D e t e c t o r " . A i r P o l l u t i o n C o n tr o l A s s o c ia t io n
M e e tin g , C l e v e l a n d , O h io .
Paper ^ 6 7 -1 0 7 , (J u n e , 1967).
(2)
Adams, D. F . , J e n s e n , G. A . , S t e a d m a n 5 J . P. , -Koppe5 R. K. , R o b e r t s o n 5
T . J . , " Im p ro v e d S u l f u r - R e a c t i n g M i c r o c o u l o m e t r i c C e l l f o r Gas
C h r o m a t o g r a p h y ." ' A n a l y t i c a l C h e m i s t r y ('V o l . 3 8 , Ho. 8 , J u l y 1 9 6 6 ) ,
1094-1096.
(3)
A dam s, D. F . , K o p p e , R. K . , "Gas C h r o m a t o g r a p h i s A n a l y s i s o f H ydrogen
S u l p h i d e , S u l f u r D i o x i d e , M e r c a p t a n s , an d A l k y l S u l f i d e s a n d D i s u l ­
p h i d e s . " .TAPPI OVol 4 2 , Ho. 7 , J u l y 1 9 59) 6 0 1 - 6 0 5 .
(4)
A p p l e b u r y , T. E . , " A i r P o l l u t i o n A b a te m e n t b y P r o c e s s Gas C hrom ato­
g r a p h y " , M a s t e r o f S c i e n c e t h e s i s , M a rc h , 1 9 6 8 , M ontana S t a t e U n i v e r ­
s i t y , B ozem an, M o n ta n a . .
(5)
"Dohrman M i c r o c c u l o m e t r i c T i t r a t i n g S y s te m O p e r a t i o n I n s t r u c t i o n s " ,
Dohrman I n s t r u m e n t s Company ( 1 9 6 7 ) .
(6)
F e l d s t e i n 5 M ., B l a e s t r i e r , S . , L e v a g g i , D. A . , " S t u d i e s on t h e Gas
C h ro m ato g rap h ic D e te rm in a tio n o f M e rc a p ta n s " , J o u r n a l o f A ir P o l l u t i o n
C o n t r o l A s s o c i a t i o n , ( V o l . 1 5 , Ho. 5 , May 1 9 6 5 ) 2 1 5 - 2 1 7 .
(7)
K o p p e 5 R. K . , Adam s, D . F . , " E v a l u a t i o n o f Gas C h r o m a to g r a p h ic
Columns f o r A n a l y s i s o f S u b p a r t s p e r M i l l i o n C o n c e n t r a t i o n s o f
G aseous S u l f u r Compounds" , E n v i r o n m e n t a l S c i e n c e a n d T e c h n o lo g y
• ( V o l ' I , Ho. 6 , J u n e 1 9 6 7 ) .
(8)
"A M anual f o r D i r e c t Gas C h r o m a t o g r a p h i c A n a l y s i s o f S u l f u r i n
P r o c e s s S tr e a m s '.', N a t i o n a l C o u n c i l f o r S t r e a m I m p r o v e m e n t , I n c . ,
R e p o r t No. 3 0 , 1 9 6 6 .
(9)
T hom as, E. W ., " D i r e c t D e t e r m i n a t i o n o f H y d r o c a r b o n S u l f i d e s i n K r a f t
G ases b y Gas .- L i q u i d C h r o m a t o g r a p h y " , TAPPI- ( V o l . 4 7 , N o . 9 , S e p t .
1964) 587-598.
( 1 0 ) B a l l , D.. L . , W. E . H a r r i s , . " E r r o r s i n M anual I n t e g r a t i o n T e c h n iq u e s
f o r C h r o m a t o g r a p h i c P e a k s " , J o u r n a l o f Gas C h r o m a t o g r a p h y , (V o l. J j 5
D e c . 1 9 6 7 ) 613-620.
( 1 1 ) J u n e t , R. S . , J . S . D a l N o r g r a r e 5 "Gas C h r o m a t o g r a p h y " , A n a l y t i c a l
C h e m i s t r y 5 ( V o l. 4 0 , No. 5 , , A p r i l , 1 9 6 8 ) 33R-44R.
0 - 2 ) S p a r k s , H. E . , "An Im p r o v e d I n j e c t i o n T e c h n iq u e f o r C a l i f b r a t i o n i n
Q u a n t i t a t i v e Gas C h r o m a to g ra p h y " J o u r n a l o f Gas C h r o m a t o g r a p h y , (V o l 6 ,
A u g 1968) 4 1 0 - 4 1 1 .
'
'
MONTANA STATE
3 1762 10020954
*378
Wl81
30P.2
Van, Edward I -S e n
A n a ly s is o f g a s e o u s
s u l f u r compounds by
p r o c e s s g a s chrom atog,rap h y______________ _____
W AMK A N O A O Q R g g g
U
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Co
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