Analyfica Chmrca Ada

Blsev~cr Publrshing Company, Amsterdam

381
Prmtcd m The Ncthcrlnnds ’

INTERFERENCES OF ACIDS IN ATOMIC ABSORPTION

SPECTROPHOTOMETRY

TOSHIl-IlSA i\IAICUT.-1,hlhS.UII SGZUKI hSi> TSUGIO ThKI<I~Cl-II

Drpartrtted uf .!Tyrt/ltcltc Citeirrtstry. I:itctdty of Bttgtrtl~er rrtg. ix-$l,WYiL U1ttvzrstty, Clttktrsa-frtr.
Nttgoycr f Ja fian)
(I<ccc~wxl hIarch pd. 1970)

Many papers have describccl the interferences of acids m atomic absorption

spectrophotometry. RAILIAKIIISHNR et al.1 reported the depressing effect of hydro-
chloric. sulfuric and perchloric acids on copper in oxy-hydrogen flames. S-lul~AIi2
described the serious effect of nitric acid on copper and of nitric and perchloric acids
on n-on by a long absorption-cell technque, and concluded that the effect of oxidizmg
acids on copper and u-on resulted from a greatly increased rate of oxide formation.
1x1~4 ANXJ I%JwR" pointed out the enhancing effect of perchloric acid on clu-omium.
However, the mechamsm of acid mterferenccs has not been fully elucidated. In tllis
work tile interferences of various acids were compared rn an attempt to elucidate
the mechamsm of acid interferences for copper, n-on and chromium.

A Nippon Jarrell-Ash AA-IE atomic absorption spectrophotometer was used

with Hitachi burner-atomizer systems The hght sources were hollow-cathode lamps
from Westmghousc Electric Corp. for copper, Hitachi Ltd. for iron, and Hatnamatsu
TV Co., Ltd., for chromium.
The light beam through the air-acetylene flame was controlled by an aperture
for measuring absorbance in a small region of the flame. Nitrous oxide-acetylene
flames were also used for comparison.

Reagents
Copper solution, moo pg d- 1. D~ssolvc 0.250 g of copper metal in hydrochloric
and nitric acids, boil to remove all oxides of mtrogen, add enough hydrochloric acid
to make the final acidity about 0.1 M, and dilute to 250 ml. Prepare weaker solutions
by dilution with water just before use.
Iron solution, IO00 pg nd- 1. Dissolve 0.250 g of electrolytic iron in hydrochloric
and nitric acids, boil to remove all oxides of nitrogen, add enough hydrochloric acid
to make the final acidity about 0.1 iI4 and dilute to 250 ml. Prepare weaker solutions
lust before use.
~kromauna solz4tion, 1000 pg wtz -1. Dissolve 0.707 ,g of potassium dichromate
in water and dilute to 250 ml. Prepare weaker solutions by heatmg a suitable alquot
of stock solution with hydrochloric acid to reduce chromium, followed by dihrtlon.
All acids were of analytical grade.

Anal. Chum Ada, 51 (1970) 781-385

382 T. MAIZUTA, >I. SUZUKI, T. TAKEUCHX

The solution (IO ,~g ml-l) of copper, n-on or chrorrnum containing hyclrochloric,
perchloric, nitric or phosphoric acid was prepared to give an acidity of 0.1 M. Each
solution was also 0.01 M in hydrochloric acid. These solutions were sprayed into the
flame and the absorbances of the metals were mcastrrecl m various flame condltlons
and m various regions of the flame.

I<@SULT5 ANI) I~ISCUSSION

The mtcrfcrencesof l~ydroclllorlcaclcl on copper, n-on and cllromium absorbances

are shown m Fig. I. This acid had a dcprcssmg effect on copper absorbance Irrespective
of flame conclltlons and beam llcights. The dcpressmg effect may be attributed to the
mcomplete dissociation of CuCl molecules in the flame. The appearance of CuCl
bands at 4281, 4333 and 4354 A confirmed this mcchamsm of mterference. Sodium
chlortcle solution (0.x M) had little effect on copper absorbance, hence it is assumed
that the free acid IS responsible for the clcpressing effect Moreover, ltttle effect was
observed when a copper solution 0.1 k? in hydrochloric acid was made ammoniacal
before spraying. No interference from chlonde was observed in the nitrous oxide-
acetylene flame although the size of the copper absorbance was small.

I I I I I I
20 24 20 24 20 24
Flow rate of acetylene (1 mln-‘1
l71.g I TnLcrfcrcnccs of hydrochloric ncxl on copper, Iroll and cht-omlum al~sorbnnccs (A) G mm
above burner Lip, (13) IO mm nbovc burtw tip, (C) 18 mm above hrncr tip, (I) To pg Cu ml-l,
0.01 M I-[Cl, (I) IO pg Cu 1111-1, 0 I I At.?HCl, (3) IO pg Cr ml-l, 0 or M I-ICI, (4) IO pg Cr ml-',
0 T t Ad I-fcl; (5) IO ,Ic~ k llll-1, 0 01 Af HCI. (6) 10 pg l?c ml-l, 0 II 111 I-ICI, flow rate of air
ii 2 1 111111-1

A small enhancmg effect on iron was found in the whole leg1011ot the flame,
but an enhancing effect on chromium was observed only in the lower region of the
flame. This effect may be derived from the chlormatmg action of hydrochloric acid
on iron and chromium; the chlorides of these elements have relatively low melting
and boiling points, which are some indication of the rate of vaporization. For chro-
mium, the high stability of chromium oxide seems to provide a reasonable explanation
for the slight enhancing effect in the higher region of the flame. More concentrated
acid (I JU) gave essentially the same effect as 0.1 M for iron and chromium.

AIlal. Clbrm. Ada, 51 (1970) 351-355

ACID INTERFERENCES IN A.A.S. 353

Perchlorzc acid
Figure 2 shows the interferences of perchlorlc acid on copper, iron and chro-
mium. Perchloric acid gave an enhancmg effect for chromium, but a depressing effect
for iron. The enhancing effect on chromium absorbance decreased with mcreasmg
height in the flame GIBSON et al .4 llave explained the enhancing effect of perchloric
acid on calcium emission, on the basis that calcium perchlorate dissociates to a
greater extent than calcium chloride. IIUA ANI) l?uw_4fi demonstrated that the en-
hancing effect on chromium absorbance could result from the oxidation of chromium
with perchloric acid The production of volatile compounds such as oxychloride
may also contribute to the enhancement of chromium.

20 24 20 2.4 20 24
Flow rate of acetylene
(I mm-‘)
IGg. 2 Tntcrfcrcnccs of perchloric awl on copper, Iron and chromium absorbanccs (A) G mm
above burner tip, (13) IO mm above burner tip, (C) IS mm above burner tip, (r) IO 116 Cu ml-l,
0 01 M I-ICI, (2) x0 cog Cu ml-l, 0 01 M HCl -t_ 0 10 M I-IClOd; (3) IO 116 Cr nil-l, 0 or M I-ICI;
(4) IO fog Cr ml-l, 0 01 M I-ICl + 0 IO M NCIO4, (5) 10 pg 17~ ml-l, 0 ox iVf I-ICI, (6) 10 ~16 1%
ml-l, o OI h2 I-ICI t_ o IO fif I-IClOd, flow rate of illr G 2 1 mm-1

The depressing effect on the iron absorbance might bc explained by a greatly

increased rate of oxide formation in the presence of perchloric acid. %~UPAR~ also
reported the marked depression on iron absorbance.
RAMAICRISHNA et al.1 noted the depressing effect on copper. In the present
work, a larger depressing effect at a higher concentration (I M) of perchloric acid
was observed for copper, but not for iron. No interferences were shown in the nitrous
oxide-acetylene flame ; the high temperature of the flame may be effective in the
dissociation of oxides.

Nitric acid
Nitric acid caused a depressing effect on both copper and chromrum in the
lower region of the flame, but little effect was observed with increasing height in the
flame (Fig. 3). ZIAMAI~RISHNA et aZ.1 reported no interference on copper from nitric
acid in an oxy-hydrogen flame, while $~UPAR~ found a depressing effect in the air-
hydrogen flame. From these facts it seems reasonable to consider that the tem-
perature of the flame is an important factor for interference of nitric acid on copper.
This was confirmed by the fact that no interference of nitric acid was found m
nitrous oxide-acetylene flames. However, the interEerence on chromium was not
reduced even in nitrous oxide-acetylene flames; chromium differed from the other
elements in this respect.

Aqaal CIGm. Acla, 51 (1970) 381-385

 I I I I I
20 2A
Flow rate of acetylene (I mln--‘I
171~ 3 Intcrfcic~iiccs of llllrlr+ :~citl on coppw, II-011 ;llld C~llOlllllllIl :l~JWI%~LllcC!~ (.\) G 111111 .llWVC

IllI WI tip. (I!) 10 111111 ;l~JCJVC hlrllcl~ tip, (c) 18 111111 ;l~JOVC ~JLllllC2r t,llJ, (I) 10 //fi cl1 Iill-1, o 0 1 fir

iI('i, (2) IO //g cl1 1111 ', 0 01 fir/ 1 ICI (- CJ IO I\f IINO.,. ( j) 10 11:: (:r ml-l, 0 OK A/ IiLl, (.I) 10 /cK
Lr nil- I, o 01 fib 1 I(,] -1 " IO IpI I1NO.r. (5) 10,//g I’C IllI ', 0 01 iv llt_l, (0) ICI #l/h' ITC ml-‘, 0 01 M
ll(‘1 -1 0 IO A/ IINO,, fl0w I-.I~L' of ;Llr Cj L I 1111111

20 24 20 24 20 24
Flow rate of acetylene (I min-I)
FIN Ink21 lcrcnccs
1, of pl~osplioi IC XICI on copper, iron ancl chromium absorbmws (A) 6 nlnl
.~~Io\L’ tip, (73) IO 111111.~Ixn~c buincr
bulncr iip, (C) 18 mm nbow burner tip, (I) 10 /cg Cu ml-I,
0 01 IW I-ICY, (2) 10 /cg cu ml-‘, 0 01 nd I-ICI -}- 0 10 M l-IJY.I~, (3) IO /ig Cr nil-*, 0 01 Al HCI,
(Jl) 10 ftg <‘r 1111-1, 0 or IVI I-ICI -I- 0 10 i%f l-131J0,;, (5) 10 pg 1% nil-L, 0 01 iIJ ZlCI, (6) I0 /tg I:c
ml-l, 0 01 A/l 11Cl + u 10 A4 II~jlY)~, flow r.rtc 0C ‘ur 6 2 1 n~iii-~

The effect of l~l~~spl~or~cacid on copper, iron and chromium is shown m Fig. 4.

I~hospllo~ic acid caused a marltccl dcprcssing cffcct on copper and chrommm, es-
pecially m the lower region of tile Clamc. This may be due to the formation of compounds
wlucl~ are stnblc m the cooler flame The size of the effect depends on the flame
temperature, and no mterference was found in nitrous oxxde-acetylene flames.
CUK~ISG noted ihat the cffcct of phosphoric acid on iron was most serious when the
flame bccamc lummous and that the interference was quite small with the light
beam passmg above the unburnt cone of gases under normal oxldlzmg conditions.
In the present work, the depressing effect of phosphoric acid on iron was founcl to
be not serious, u-respective of flame conditions and flame heights.
The acid effects are complex in nature and depend on various factors, and
the choice of acid is important m mlmmizmg their effect m atomic absorption spectro-
metry.
ACID INTEIIFEIIENCES IN A.A ‘5 355

The authors would hke to thank hlr IIf YASACTSAWA for asslstancc throughout
this work.

Hydrochloric, perchlorlc, nitric and pllosplioric acids were cxsamined to

elucidate tlie mechanism of tllcir interferences on the atomic absorption spcctro-
photometry of copper, iron and cllromiuni. The interferences were comples in
nature and varied for clrffcrcnt elements and for dlffcrent acids The mechanism of
the mterferenccs is chscussccl.

On cxamlne l’lnfluence des zlcides chlorhydrlc~ue, pcrchlorlclue, nltrlquc et

phosphorque sur la spectrophotom6trie par absorption atomlquc, du culvre, clu fcr
et du chrome. Ces interfdrcnces sont compleses ct varwnt suivant les dl&nents ct
les acldes. Unc dlscusslon cst pr&entdc sur le rn6chamsme dc ccs mterfdrenccs.

%1x-, Perclxlor-, Salpcter- und Phosplwrs,u.n-e wurclen zur Dcutung der

Ursaclwn der Storungcn dle5er Sauren bet der Aton~~~bsorptlonsflr~tnmenplloton~etr~c
von Kupfer, Eiscn uncl Chrom untersucht Die Storungcn warcn komplcxcr Natur
und varlierten hei verschledenen Elerncntcn und SLuren Dcr hIcchnnismus der
Storungen wird dlskutlert.