Jan HALKIEWICZ, Janusz GRZYBOWSKI, Elżbieta

Jan HALKIEWICZ, Janusz GRZYBOWSKI, Elżbieta

Jan HALKIEWICZ, Janusz GRZYBOWSKI,
Elżbieta SACHARCZUK_________________
M edical A cadem y in G dańsk
In stitu te of C h em istry and A nalytics
GAS CHROMATOGRAPHIC DETERMINATION OF Zn, Cu
AND Ni IN ROTTOM SEDIMENTS IN THE FORM OF
DIETHYLDITHIOCARBAMATE COMPLEXES
Contents:
feren ces.
1. In trod u ction , 2. E x p erim en ta l, 3. C o n clu sion s; S treszczen ie;
R e­
1. IN TRODU CTIO N
G as-liquid c h ro m ato g rap h y (GLC) provides a v e rsa tile tech n iq u e for
q u a lita tiv e and q u a n tita tiv e analysis of m ix tu re s. T he tech n iq u e is u s u ­
ally em ployed for analysis of organic com pounds w hich m eet th e re ­
q u ire m en ts pcsed b y o p erativ e conditions of th e chrom atographic co­
lum n, i.e. th e y ex h ib it p ro p e r v o la tility and th e rm a l stab ility .
A p a rtic u la r section of GLC provides analysis of organic and in o r­
ganic com pounds of m etals. These com pounds a re u su a lly n o n v olatile
a t th e te m p e ra tu re of th e colum n due to th e ir ionic n a tu re e x h ib ited
in th e solid sta te and in solution, m oreover, th e y h av e an additional
p ro p e rty — a high re a c tiv ity in resp ect to colum n packings and th e co­
lum ns them selves. S tu d ies on th e application of GLC in th e analysis
of m etals and th e ir com pounds have been carrie d out in sev eral d ire c ­
tions. One of th em involves th e application of m eta l com plexes w ith or­
ganic ligands in th e ch ro m atographic analysis.
T he m etal com plexes used for ch ro m ato g rap h y should m eet th e fol­
low ing req u irem e n ts:
i) th e y should be n e u tra l;
(ii) th e y should ex h ib it p ro p er th e rm a l sta b ility d u rin g elution fro m
th e colum n;
(iii) th e y should not in te ra c t w ith th e colum n packing;
(iv) ligands should be slow ly released from th e com plex;
(v) th e re should be no exchange of th e ligands b etw een th e com ple­
xes fed onto th e colum n;
O c e a n o lo g y N o 13(1980)
(vi) th e y should be solvolytically stable;
(vii) th e y should possess p ro p er v o la tility u n d e r p rese rv atio n of
in te g rity of a m olecule in th e gas phase on a h o t and active packing
surface;
(viii) th e y should be av ailable on th e m arket.
Tl e GLC m ethod of d e te rm in in g m etals has th e follow ing a d v a n ­
tages over o th er an a ly tic a l m ethods:
(i) high detectio n selectiv ity of com plexes leaving th e colum n, owing
to th e use of a p ro p er d e te c to r (ECD, FID , etc.);
(ii) p o ssibility of using a re la tiv e ly inexpensive gas chrom atograph;
(ir) possibility of assaying of tra c e and u ltra tra c e am ounts of m e­
tals;
(iv) p o ssibility of sim u ltan eo u s q u a lita tiv e and q u a n tita tiv e d e te r­
m ination of sev eral m etals in one sam ple;
(v) p o ssib ility of lim itatio n of th e sam ple (liquid or solid) tak e n
fo r analysis;
(vi) possibility of m u ltip le analysis of m etal com plexes in th e sam ­
ple;
(vii) possibility of assaying m eta l levels in sam ples containing an
e le m en t at th e d etection lim its, b y o th er m ethods;
(viii) possibility of a se v e ra l-h u n d re d -fo ld c o n cen tratio n of m etal
com plexes e x tra c te d fro m a sam ple;
(ix) application onto a colum n of sm all p o rtio n s of th e an a ly te
(0.5— 2.0 nf).
Tabelle 1. C om p arison o f th e d eten tion limiit<s in th e GŁC and cither m eth od s
for sam e e le m e n ts
T a b ela 1. Porów,nan'ie w a r to śc i g ra n ic y w y k r y w a ln o śc i o trzy m a n y ch dla n ie ­
k tó r y c h p ie r w ia s tk ó w m e to d ą GŁC oraz in n y m i m etodam i.
M etal -to
b e assayed:
O znaczan y
metlal
AAS
GLC
A SA
N eu tro n a c ti­
v a tio n analysils
A k ty w a c y jn a
an aliza n e u tr o ­
now a
E m issio n
■spectrograp h y
S p e k tr o ­
g ra fia
e m isy jn a
Sp ark ^souiree
imiass sp ectro grap h y
Isk row a sp ek tro ­
g ra fia m as
8 X 10-12
io-6
1 X 10-»
5 X
2 X io-8
5 X io-11
2 X IO-»
9 X 10-n
7 X 10-11
1 X 10-«
1 X io-»
3 X 10-»
2 X 10-“
Co
1 X 10-“
2 X 10-»
5 X lO-io
1 X 10-6
5 X 10-n
Pd
1 X 10-10
3 X io-8
5 X io-»
1 X
10-'
5 X lO-io
Ni
1 X 10-11
2 X 10-»
5 X io-»
8 X 10-»
7 X 10-u
4 X ,10-«
1 X 10-»
Cr
2 X 10-1«
2 X 10-»
1 X
Rh
2 X 10-“
Al
o1
2 X lO-io
Be
T able 1 lists th e absolute d etection lim its (in gram s) obtained in
th e d e te rm in a tio n of m etals by various an aly tical tec h n iq u es [15]. H igh
d eten tio n lim its of GLC a re associated w ith an im p o rta n t fe a tu re of
th e m ethod, n a m e ly w ith th e sep aratio n of im p u ritie s fro m a com plex
leaving th e colum n and w ith th e possibility of em ploying a d e te c to r
of p ro p er q u ality .
Of th e ligands stu d ied h ith e rto , dialk y ld ith io carb am ates, and p a rti­
c u la rly d ieth y ld ith io c a rb a m ate s of c e rta in m etals, c o n stitu te a little
studied and p rospective group. B efore using th e m in GLC, th e ir v o la ti­
lity w as studied. R esu lts of th e in v estig atio n s of d ieth y ld ith io c a rb a m ate s
of Co(Il), Ni(II), Zn(II), Cd(II), Hg(II), Fe(III) and Ag (I), c a rrie d out by
D’Ascenzo [3, 4] co nfirm ed th e possibility of using some o-' ’h em in
chro m ato g rap h ic studies. D espite sceptical view s [6, 12, 17] on th e
u sefulness of th e com plexes of this ligand in GLC, successful a tte m ts
[7, 8] have been re p o rte d on th e sep aratio n of a m ix tu re of som e d ithio carb am ates [2, 9, 18]. T hese papers, w ith th e exception of [5], w ere
confined to a tte m ts to se p ara te som e com plexes on ran d o m ly chosen
packing only. T h e re are no re p o rts on optim ization ,of e ith e r q u a lita tiv e
or q u a n tita tiv e elu tio n of m ix tu re s of m eta l com plexes.
In th is p ap er th e p a ra m e te rs of q u a lita tiv e and q u a n tita tiv e sepa­
ratio n of zinc, copper and nickel com plexes have been established and
applied to assaying m eta ls in m arin e b ottom sedim ent.
2. EXPERIMENTAL
GLC sep aratio n w as c a rrie d out on a P y e U nicam M odel 104 gas c h ro ­
m ato g rap h equipped w ith a flam e ionization d e te c to r (FID). A rgon w as
used as c a rrie r gas.
S olutions of m etal com plexes w e re p re p a re d im m ed iately before
GLC sep aratio n . T he com plexes w ere p re p a re d b y using p ro ced u res
re p o rte d in [2, 3, 7], C hloroform ic solutions of th e com plexes contained
2000 ¡ig of each of th e m etals in 1 cm 3. T hey w ere p ro p e rly d ilu ted , if
needed, to c o n cen tratio n s of 400, 100 and 40 ¡ig /c m 3.
2.1. Chromatographic separation
A tte m p ts to se p ara te both in d iv id u al m eta l com plexes and th e ir m ix ­
tu re s w e re m ade by using conditions and packings specified in T able 2.
R e su lts of p re lim in a ry tests rev e a le d th e possibility of se p ara tin g th e
zinc, copper and nickel com plexes on 3%> SE-30 coated on C hrom osorb
W -H P (item 1, T able 2). T he re te n tio n tim es conform ed w ith those
obtained fo r single com plexes. These conditions did not, how ever, en 11 — O ceanologia
%
1.5 .m/2>mm
1.5 ,m/2mm
5°/o QF-1 on (na)
Gas Chrom Q
Mixed
packing
W ypełnienie m ie ­
szan e
7
1.5 m/2mm
1.5 im/2mm
5
4
3
2
240
240
240
10 °/m in
200—290
250
250
250
320
17.6
20
20
20
866
702
299
554
com plex :es — nie r óżnicuje
does n ot d ifferen tia te the
iróżnicuje
355
6018
m/2mm
45
30
1.8
330
320
1
I
3.03
6.0
3.2
3.05
2.96
5.2
5.68
5.8
5.39
6.57
korn p lek sów
ko ipleksów
1.87
4.6
8.0
9.12
7.57
7.3
4.0
6 .0
2.93
0.46
Zn
5.58
0.83
Cu
8.77
1.17
Ni
Rett, réten tio n
tim es
Wagi. cza sy
x aten cji
DM hyW ithiocartbamates
No. of th e -'
■
R eten tion
oretüicäl
Itimets
L iczba
gas pólek te o - Czasy renltencji
(m in)
U
. 'Cli.
Ni
Cu
Zn
rate of
Flow
deltector
T em p .
detektora |c:anrier
Temsp. f o
....
comple: tes — nie
280
10 °/rmn
240—290
Temp. of
th erm ostat
Temp. te r ­
mo sit atu
(°C)
1
does n ot d ifferen tiate : the
1
F'ig.
Kyis.
1
.
ch rom atograficzn ej
m/2mm
1
analizy
3.0
1.5 m/2imm
1.5 m /2m m
ri.u'iuaiiui
1--------------------
Column d i­
mensions
Wymiary
6
h)
a)
5% OV-lOl on
(na) Gas
Chrom
5
O
2.5°/o BM BT
4
GC
(na)
3°/o OV-7 on
C h ro m osoib
W -H P
Tenex
(na)
3°/o SE-30 on
Chrom os or b
W -H P
Column packing
W yp ełn ien ie
1
3
2
1
No.
Nr
i
Table 2. Column packings and conditions of GLC analyses in this paper
Tab. 2. Zestawienie
użytych
do badań
wypełnień
oraz warunków
sure rep ro d u c ib le ch rom atogram s of a m ix tu re fed onto th e colum n,
sim ilarly as w ith packing consisting of th e OV-7 phase (3®/») coated on
C hrom osorb W -H P (Figs. 1A and IB, item 2, T able 2). B y using th e
O V -lO l (5°/o) phase on Gas C hrom Q, th e sep aratio n of a m ix tu re of
' 0 1 2 3 4 - 5
0
1
2
3
4
5
(min)
F ig. 1A and IB. A chrom aitogram o f a m ix tu r e of th e Zn, Ciu and N i c o m p le ­
x e s ob tained b y u sin g a colu m n packed w ith 3% of OV-7 on C hrom osorb W -H P
d uring tw o su cce ssiv e injeationis.
R ys 1A i IB . C h rom atogram m ie sz a n in y k o m p le k só w Zn, Cu, N i o trzy m a n y
na k o lu m n ie w y p e łn io n e j 3% O V -7 na Chromosoirbie W-HiP w k o lejn y c h d w ó ch
nastrzyk ach .
zinc, copper and nick el com plexes w as m a rk e d ly im proved. A t th e sam e
tim e th e effect of th e com pactness of th e packing on th e q u a lity of
GLC sep aratio n of th e com plexes w as investigated. This w as accom ­
plished by using tw o colum ns of equal dim ensions filled w ith in d en tical packing of d iffe re n t com pactness. A m ix tu re of d ie th y ld ith io c a rb a m a-
F ig. 2. T h e sep aration o f th e d ie thyldithioeairbam ate c o m p le x e s on a
co lu m n loose'ly p a ck ed w ith 5% of
OV-101 on G as C hrom Q.
iRy.s. 2. R ozd ział m ie sza n in y k o m ­
p le k só w z DEiDTK u z y sk a n y n a w y ­
p ełn ien iu 5% O V -lO l na G as C hrom ie
Q (w y p ełn ien ie lu źn o u p ak ow an e).
F ig. 3. A ch rom atogram of the
zinc, copper and n ic k e l co m p lex e s, to ­
geth er wiith an in te rn a l stan d art, ob­
ta in ed b y ojisiing m ore co m p a ct p ac­
k in g (5% o f O V -lO l)
R ys. 3. C h rom atogram m iesza n in y
k o m p le k só w cy n k u , m ied zi i n ik lu
wiraż z wzo-rcem w e w n ę tr z n y m o trzy ­
m an y n a w y p e łn ie n iu 5% O V -lO l (w y ­
p e łn ie n ie b ard ziej u p a k o w a n e).
tes of zinc, copper and nickel could not be resolved on a loosely packed
colum n (the peaks of copper and nick el coalesced), a lth o u g h one-by-one
in je c te d com plexes se p ara te d w ell. A d eq u ate se p ara tio n of th e com p­
lexes w as achieved b y using p ro g ram m ab le h e a tin g of th e th e rm o sta t
(item 5a, T able 2, Fig. 2). W ith th e m ore com pact colum n, a good se­
p a ra tio n of in d iv id u al d ieth y ld ith io c a rb a m ate s and of th e ir m ix tu re w as
a tta in e d (item 5b, T able II, Fig. 3). U n d er th e speccified conditions,
th e peaks of th e zinc, copper and n ick el com plexes w e re sy m m etrical
and w ell sep arated . S im ila r re s u lts to th o se achieved on th e O V -lO l
packing w e re obtained w ith th e QF-1 (5% ) phase on G as C hrom Q.
T he re s u lts confirm th e u sefu ln ess of th e packing fo r th e se p ara tio n of
com ponents of a m ix tu re of zinc, copper and nick el com plexes. T he
peaks are sy m m etrical, w ell-sh ap ed and h av e p recisely d e te rm in e d p a ­
ra m e te rs (item 6, T able 2, Fig. 4).
F ig . 4 A ch rom atogram
o f a m ix tu r e o f th e zin c, c o ­
p er and n ic k e l d ie th y ld ith io cairfoamaites, to g eth er w ith an
in te r n a l sta n d a rd , o b ta in ed
on th e O F -1 p a ck in g .
R y s.
4.
C h rom atogram
m ie sz a n in y k o m p lek só w d w u ety lo d w u tio k a rb a m in ia n o w y ch
cyniku, m ie d z i i n ik lu w ra z z
w zo rcem w e w n ę tr z n y m o trzy ­
m a n y n a w y p e łn ie n iu
5%
O F -1.
In o rd er to use th e packings for q u a n tita tiv e analysis, th e b eh av io u r
of ce rtain organic com pounds w hich could be used as in te rn a l s ta n ­
dard s in th e p resen ce of m eta l com plexes w as in v estigated. T he organic
com pounds used w ere, am ong others, deh y d ro ep ian d ro stero n e, n -d o tria contane and benzo[ghi]perylene. Of these com pounds, n -d o tria c o n ta n e w as
th e m ost su ita b le for analy tical purposes (Fig. 3).
To d e te rm in e m u tu a l positions of p a rtic u la r com plexes in m ore
detail, re la tiv e re te n tio n s w ere calcu lated for each of th e m in resp ect
to n -d o tria c o n ta n e (Table 2, item s 5b and 6). D ue to a high p o la rity of
th e QF-1 s ta tio n a ry phase, th e p e a k of n -d o tria c o n ta n e in tro d u ced to ­
g e th e r w ith th e com plexes w as shifted. This disqualifies th e com pound
as an in te rn a l sta n d a rd . It leaves th e colum n to g o th er w ith volatile im ­
p u ritie s (Fig. 4). In view of th e fact th a t th e liquid phases possess diffe­
re n t acceptor-donor p ro p erties, th e packing w as m odified by m ixing
to g eth e r in th e 1:1 ratio by w e ig h t packings specified u n d e r 5 and 6.
T he v alues of re te n ttio n fractio n s calcu lated for p a rtic u la r packings by
F ig. 5. A ch ro m a to g ra m
of th e zinc, coipper and n i­
ckel
di ethyldiit h i ocarb am a tes
and o f n -d o tr ia co n ta n e ob ta­
in ed on a m ix ed p ack in g
R ys.
5.
C h rom atogram
m iesz a n in y
d w u e ty lo d w u tio k arbam i/nianów cyn k u , m ie d z i
i n ik lu oraz n -d o tria k o n ta n u
o trzy m a n y
na
w y p e łn ie n iu
m iesza n y m .
th e B row n m ethod [16] show ed th a t th e packing considered re ta in e d its
n o n p o larity sim ilar to th a t of th e O V -lO l phase and its acceptor-donor
p ro p ertie s w e re red u c e d as com pared w ith those of th e QF-1 phase,
th u s c o n trib u tin g to sep aratio n of th e com plexes. B y using th is packing,
a tte m p ts w ere m ade to se p ara te th e zinc, copper and nickel d ieth y ld ith io c arb am ates fro m b o th a sta n d a rd m ix tu re and fro m a b ottom sedim ent.
T he chro m ato g ram in Fig. 5 illu s tra te s e x c elle n t separation of th e Zn(II),
Cu(II) and Ni(II) com plexes and of n -d o triaco n tan e.
To assay zinc, copper and nickel, th e response of th e flam e ioni­
zation d etecto r w as d e te rm in e d on p ro g ressiv ely grow ing m asses of th e
m eta l com plexes applied onto th e colum n. C hom atographic peaks due
to p a rtic u la r m asses of th e com plexes are show n in Figs. 6— 8. A r e la ­
tionship b e tw e en p e a k area and th e m ass of a com plex (based on th e
m etal) is show n in Fig. 9. These data re v e a l a lin e a r rela tio n sh ip b e t­
ween the am ount of a com plex fed onto th e colum n (based on th e m e-
F ig. 6. A ch rom atogram sh o w in g th e resporase o f th e fla m e io n iz a tio n d etecto r
on a p ro g ressiv ely in crea sin g maiss o f th e zin c co m p lex .
Ry.s. 6. C h rom atogram o k reśla ją cy r ea k c ję detek tora płoimL&ni o w o -jo n iz a c y jn e g o
n a w p row ad zon ą m a sę k o m p le k su cyn k u .
ta l content) and p e a k a reas fo r copper and nickel over th e ran g e
10— 200 ng and for zinc over th e ran g e 30— 160 ng. A pplication onto th e
colum n of sm aller q u a n titie s of th e m etals th a n th e low er ones in d ica­
ted, b ro u g h t about a n o n p ro p o rtio n al d e te c to r response, p ro b ab ly due
to sorption of th e com plexes on th e packing.
F ig 7. A ch rom atogram sh o w in g th e resp o n se of th e flaime io n iza tio n d etector
on a .p rogressively in crea sin g m ass o f th e cop p er co m p lex .
R ys. 7. C hrom atogram o k re śla ją c y re a k c ję d etek tora p ło m ie n io w o -jo n iza cy jn eg »
n a w p row ad zon ą m asę k o m p lek su m ied zi.
F ig . 8. A chrom atograim sh o w in g th e r e sp o n se o f the fla m e io n iza tio n detector
a p r o g r e ssiv e ly in c r e a sin g m a ss o f th e n ic k e l, co m p le x
R ys. 8. C h rom atogram o k reśla ją cy re a k c ję detektora, p ło m ien io w o -jo n iz a c y jn e ­
g o na w p row ad zo n ą m a sę k o m p le k su n ik lu .
on
F ig. 9. R ela tio n sh ip b e tw e e n p ea k area and th e m a ss o f a c o m p le x (based on
th e m eta l co n ten t).
R ys 9. K rzy w a z a leż n o ści p o w ier z c h n i p ik u od w p ro w a d zo n ej m a sy d a n e g o
k o m p lek su (w p rzeliczen iu n a metail).
2.2. Q ualitative and quantitative GLC assay of zinc, copper, and
nickel in marine bottom sedim ents
Sam ples of th e sedim ents (sands, loam s) w e re supplied by th e In s titu ­
te of M arine Geology, Sopot.
T he sam ples (ca 10 g) w ere dried a t 110°C for 2 hrs., g ro u n d in
a porcelain m o rta r and tem p e re d in a m u ffle fornace a t 500°C fo r 2
h rs. A fte r cooling th e sam ple, a 2-g p o rtio n w as ta k e n and m illed in
a v ib ratio n al ag ate m ill fo r 30 rnin. T he m a te ria l w as th e n w et digested
by using th e p ro ced u re described in [1, 10, 11, 13, 14].
A w eighed sam ple (0.2— 0.5 g) w as placed in a M odel 2 P e rk in
E lm er autoclave, m oistened w ith 1 cm 3 of d o u b le-d istilled w ater, follo­
w ed b y th e addition of 2 cm 3 of concd. H N 0 3 (sp. gr. 1.14) and 10 cm 3
of 40% H 2F 2 solution. T he c o n te n t of a teflo n in se rt w as m ixed and
autoclaved a t 150°C for 45 m in. A fte r cooling to room te m p e ra tu re , th e
F ig. 10. C h rom atogram s o f a m ix tu r e of th e zinc, coipper and n ic k e l co m p le x e s
obtained from m arin e sand and loam w ith the ad d itio n o f n -d o tr ia c o n ta n e (in ter­
n a l standard).
R ys. 10. C h rom atogram y m ie sz a n in y k o m p lek só w cy n k u , m ied zi i n ik lu o trzy ­
m an ej z próby p ia sk u m o rsk ieg o oraz ilu w r a z z d od atk iem w zo rca w e w n ę tr zn eg o
— n-dotiriakontanu.
c o n te n t w as tra n s fe rre d to a 100-cm 3 teflo n dish and tre a te d w ith 10 cm 3
of th e 40!°/oi H 2F 2 solution and 1 cm 3 of conc. HNO 3 . T he solution w as
ev ap o rated to d ry n ess on a sand b ath and th e p ro ced u re w as rep e a te d .
To th e d ry residue, 10 cm 3 of 8M .H C I w as added and th e c o n te n t w as
g e n tly h e a te d to dissolve th e solids. T he solution w as tra n s fe rre d to
a 250-cm 3 b eak er, 0.5 cm 3 of a L aC l3 solution (concentration 1000 ^g
cm -3) w as added, th e volum e w as m ade up to 100 cm 3 w ith d o u b le-d istilled w ater, th e solution w as placed on a boiling w a te r b a th for approx.
F ig 11. C h rom atogram of a m ix tu r e of c o m p le x e s from th e blank.
R ys. 11. C h rom atogram m iesza n in y k o m p lek só w u zy sk a n y ch z próby od n ośn ej.
5 m in, th e n 20 cm 3 of c o n c en tra te d am m onia solution and 1 cm 3 of 30%
H 2O 2 w ere added. U nder continuous stirrin g th e solution w as h e a te d fo r
5 m in, filte re d th ro u g h a sm all-p o re filte r p aper, th e p re c ip ita te was
w ashed tw ice w ith 10-cm 3 p o rtio n s of co n c en tra te d am m onia solution,
th e filtra te w as tra n s fe rre d to a 250-cm 3 se p ara tin g fu n n e l and 10 cm 3
of a 3% solution of sodium d ieth y ld ith io c a rb a m ate (previously p u rifie d
fro m m etallic im p u ritie s by e x tra ctio n w ith chloroform ) w as added.
A fte r 10 m in th e com plexes w e re e x tra c te d w ith chloroform , successive
e x tra c ts being collected in flasks w ith conical bottom . C hloroform w as
th e n co m pletely rem oved on a w a te r b a th at 80°C. To th e d ry residue,
a solution of n -d o tria c o n ta n e w as added and th e solution w as applied
w ith a m icrosyringe (0.6— 0.1-jxl portions) onto th e colum n filled w ith
th e m ixed packing (cf. item 7, T able 2). Illu s tra tiv e chrom atogram s of th e
zinc, copper and n ick el com plexes isolated fro m a sam ple of sand and
loam are show n in Figs. 10.
A b lan k w as p rep a re d , using p u re rea g e n ts only, by th e p ro ced u re
ju st described. A c h ro m ato g ram of th e b lan k is show n in Fig. 11. T he
accuracy and precision of th e m eth o d are now being d eterm in ed .
3. CONCLUSIONS
(i) To obtain a good separation of the zinc, copper and nickel diethydithiocarbam ates, a packing containing 5% of OV-lOl and 5%
of QF-1 coated on Gas Chrom Q should be employed. For quantitative
separation, a m ixed packing can be recom m ended cons:sting of a 1:1
(w /w ) m ixture of 5% of OV-lOl and 5% of QF-1 both coated on the
Gas Chrom Q carrier.
(ii) T he lin e a r ran g e of th e rela tio n sh ip b etw een th e signal in te n ­
sity of th e flam e ionization d e te c to r and th e m ass of a com plex fed onto
th e colum n ex ten d s fro m 30 to 160 ng fo r zinc and fro m 10 to 200 ng
fo r copper and nickel.
(iii) T he p ro ced u re used to isolate zinc, copper and nick el from
a sam ple in th e form of th e ir d ieth y ld ith io c a rb a m ate s affords w e ll-d e veloped ch rom atogram s in th e p resen ce n -d o tria c o n ta n e as an in te rn a l
stan d ard .
J a n M ALKIEW ICZ, Ja n u sz G R ZY B O W SK I, E lżbieta SA CHA RCZUK
A k ad em ia M ed yczn a w G dańsku
In sty tu t C h em ii i A n a lity k i
OZNA CZA N IE K O M PLEK SÓ W Zn, Cu i Ni Z D ED TK ZA PO M O CĄ
C H RO M A TO G RA FII G A ZO W EJ W PRÓ BA CH OSADÓW
DENNYCH
S treszczen ie
Z aletą sto so w a n ia ch ro m a to g ra fii g a zo w ej w a n a liz ie śla d o w e j m a terii je st m o ­
żliw o ść o zn aczan ia jed n o czesn eg o k ilk u m e ta li w tej sam ej próbie.
W a rty k u le opracow an o w a r u n k i a n a lizy ch rom atograficzn ej k o m p le k só w Zn,
Cu i N i z d w u ety io d w u tio k a rb a m in ia n em (DEDTK) d la m ie sza n in y w zo rcó w i dla
próby osad ów m orsk ich .
D o badań u ży to ch rom atografu g a zo w eg o P y c U n ica m m o d el 104, zaop atrzo­
n eg o v/ d etek tor p lc m ie n io w o -jo n iza c y jn y (FID). U ży to k o lu m n szk la n y ch o p rze­
k ro jach w ew n ętrzn y ch : 2 i 4 m m i d łu g o ści 1,5 m , 1,8 m , 3,0 m , sto su ją c n o śn ik i:
C hrom osorb W -H P oraz G as C hrom Q, p ok ryte ■» fa za m i stacjon arn ym i: SF-30,
OV-7, O V -lG l, QF-1, B B B T i T en ex o różn ych stop n iach p ok rycia.
R ozdziału m ie sz a n in y w zo rco w ej zaw iera ją cej k o m p lek sy d w u ety ło d w u tio k a r b a m in ia n o w e Zn, Cu i N i d ok on an o n a 5% OV-101 i sto su ją c w y p e łn ie n ie m ie sza n e
o sk ład zie 5%> OV -101 i 5°/o QF-1 w sto su n k u w a g o w y m 1:1. W y p ełn ien ie m ie sz a n e
zastosow an o ró w n ież do a n a lizy ilo śc io w ej k o m p lek só w . Z akres p r o sto lin io w o ści d la
zależn ości p o w ierzch n i piku od w p row ad zon ej m a sy k o m p lek su w p rzeliczen iu n a
m e ta l m ie śc ił się w za k resie dla Cu i Ni: 10— 200 ng i dla Zn: 30— 160 ng.
A n a lizy p róbki dokonano p ob ierając 0,5 g p o rcję osadu su szo n eg o a n a stę p n ie
w y p rażon ego w tem p era tu rze 500°C. R ozd rob n ion y m a te r ia ł poddano roztw arzan iu
w a u to k la w ie ciśn ie n io w y m fir m y P erk in E lm er w tem p era tu rze 150°C p rzez 40 m in.,
sto su ją c m iesza n in ę ro ztw arzającą o sk ła d zie p od an ym w załączonej p rzez firm ę
in stru k cji. P o roztw o rzen iu b ad an ego m a teria łu o ra z p o od p ęd zen iu k rzem u w p o ­
sta c i S il ' 4 su ch ą p o zo sta ło ść rozp u szczon o w 10“/o ro ztw o rze HC1. P o d od an iu do
roztw oru porcji 30°/o H 20 2 a n a stę p n ie 5 000 n g L a (III) w sp ó łstrą ca n o p rzeszk ad za­
ją c e w a n a lizie ch ro m a to g ra ficzn ej F e i M n. W sp ó łstrą ca n ie p rzep row ad zon o d od ając
do roztw oru b ad an ego 25°/o N H 3 • H ,0 . P o p rzesą czen iu p rzez tw a r d y sączek u z y sk a ­
n y osad p rzem yto ro ztw o rem N H 3 • H-O S w o d ą d o jo n izo w a n ą . D o p rzesą czu d od an o
3°/o N aD E D T K (oczyszczon ego w cz e śn ie j od za n ieczy szczeń organ iczn ych przez e k stra ­
k cję CHCl3/C H 3/;CO w sto su n k u o b jęto ścio w y m 5 : 2). P o w s ta łe k o m p lek sy ek stra h o ­
w a n o tą sam ą m iesza n in ą co c z y sty od czyn n ik . P o o d p arow an iu ro zp u szczaln ik a n a
łaźn i w od n ej w tem p. 80° do su ch ej p o zo sta ło ści d od aw an o CHC13 oraz roztw oru
w zorca w ew n ętrzn ego^ 'n -d otriak on tan u i a n a lizo w a n o n a ch rom atografie g a zo w y m
n astrzy k u ją c porcję 0,5— 1,0 ¡7! n a k o lu m n ę w y p ełn io n ą G as C hrom Q z n a n iesio n ą
m ieszan in ą fa z QF-1 i O Y -lO l.
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