l4

Flame Photometry

14.1.,- Introduction ./
".-.-Flame photrrmetry is based o" th. *"mrrd-"nt of rntensrt
T oli ttrtnr
110 prnl r^rhpn a rnf|fel le rnt rntn a
colorrr
tntgnstty tetts us how m i
Flame photometry is also named as @sp€cl.t'
ltaltr'tt

Flame photometry, couplecl with simple read.out devices, |)rr,

vides high sensitivity and high reliability for the determinafiev1 r,l
elements in the first two gf the periodic table. Ary"g tlr, r',
iunn, potassium, h-tm:-, c um, strr,rr
tium, and barium. T ese elemeirts is v,',1
useful in medicine, agriculture and plant science. Flame photon)r'tr v
is also successful in-determining c-ertain transition elements, srrr l,
as copperr iron and rnanganese. By making a wavelength scan ,,1
it is also p t| 1", : ,

I
plame photometry is a sample, rapid method for the rr)ut'r,
deterrfination of elements that cqrl. be easily excited.
' Principle
^._r_ /
14.-w- ./
When a Uquid samplg_-re&ining a metallic salt soltrl i,r,
introduced into a Jl-ame, the processes-iruyofv -------
ffipliotonrrrr
a gisasimplified version oTlEe c-v t't I t ',

(a)r''lhe solvent is vaporised, leaving particles cif the solirl 1 ,l

(b>l-he salt is vaporised or converted into the gaseous st:rr r

rt or all of the are Dro

tsso_1;lgjed to siveffial at Thest:
,atoms are excitcd bv the th:rmal ener.gv of ths flame.) 'fht:
 \r-'--

---'
nbme Pltotortetry 365

atotns, which are unstablg er

llyreachingtheunexcitedstate.The[l€?SUfG. r'i

ment of the enritted photons, d.e., radiation forms the basis of flame,

adiation emitted during the jt'*P

may be defined by equation 14.l ,
Ez- Er:Dv w/ ... (l 4.ll
where h is the Plancks' constant, and v the frequency of emitted light
which is defined as follows

v- cl ... (l 4.2)

On combining equations (14.1) and (14.2), we get

Er-B, : A^ -'
or 7:A-
E,
- ...(14.3)
-Er
From equation (14.3) one can calulate the wavelength of the

r ontaining liquid droplets droplets resulting

r.fr.ment aspirated - in the formation of
lrrlo a flame residue
t-./ €
I
+
W,rvelength and +-Formation of excited <-Decomposition of
irtcnsitybf atoms and emission residuiinto
nrrritted radi?rtion of radiation from neutral atoms
rttr.nrured by atoms /,'
ll,rme photometry ,r'
(
l|rry
ul th
lurrc
llilor
The &egtior of free atoms th.at are1,[-e19ga[11_e5.qi1ed_ is go:qp-
llhy a BoltffiFiCh-ii?i-folioil t"-
N* : A o-LEtkT
'rv ... ( 1 4,4')
No ./
 .1 tt J

Ulr"t.: N* is the nunrbcr ol'r.xcit,.rl atonrx, Nu tlrr. lgm[r.rr ot'.rt.nrr

a partit:ul:tl' , i,
rk tltr: ll,,lt ,
,levels,

TABLE I4.I
Flame temperature
Fuel Oxidant Flame Temp. (o('l

Propane air 19m

Propane oxygen 2800
Hr alr zrw
Hs oxygen 2800
Acetylene alr 22W
Acetylene oxygen 3000

When the temperature of {lame is increased, the intensity

'l
emitted radiation generally increases. _But this is not tnre in casc,'l
sgl or pota *ily
elementsffi
Iese elements
When-ttr-ese are Fe eratures in flames, llrr y

[qnised instead of excitcd. "Therefore, for such elemr r rtr

moderate temperd eS7re r€qurred whr 6-ilrrfrt
excrfed atoms.-

t4.d$tt1-:ntation _/,
ffitockdiagramoftheequipmentusedinfl,a6ephotonrrtry

Sanpb

Fig. l.l.l. Block diagram of a flasle photometcr.

 'l'lr,'vilriorl'i c()nllx)tt('nls
ol'lltr. in.rlrunlr.nl :tr'(. de.tcribed as
! ll,,rvrr

I Burnor. 'l'ltc fl:rmc use(l in the flame photometer must

; ee,irllrr. lrrllowiagfunctions,
..-,,,
( ) 'l'ltt: llame should
' poss ess tloe-dbifity to evaporate t5e liquid
Itrrf tlr':l'r lrom the sample solution, reaulting in the formation of ;lid
=ir lilr'.
(r r ) 1'he flame should decompose thq compounds in the sotid
' ="lrr. li,rnred in step (d), ---
flglting-in the formatiott of atoms.
(rrr.) The flame must have the capability to.excite the atorns
I rrrrrl irrstep F_or-
.,,', )
| ,.i1 ., I pur nsity
r,..'lrI lxr steady_g@ p
'l'ltc temPeratur_e of
the flame, which is primarily responsible
I r t lrr' ()(:currtnce of the above mentioned processes, isrruttrottgd-
! , r'r'r'irl factors which are summarisedjls follews
-
(r) Typ" of fuel and oxidant and fuel-to.oxidant ratio;
(r
) Typ" of solvent for preparing the sample solution;
d

(r u ) Amount of solvent which is entering into the flame;

r'), Typ. of burner employed in flame photometer ; and
(r

(r,) itt* particular region in flame whictr rs to be focussgd-iglo,

, ,, r'l l rirn
f r tiOn u
ln flame photometrlr several burners and fuel.oxidant combi.
" ,r r 'u ut have been used to produce the ar.ralytical flame. Some of
rl,, rr .u'o discussed as below :

(r) Medcer btrner. This burner was used earlier and employed
,,<trll,tl g4q .As r roduced relatively lonq
a

!,'r1,,,;,',tt tion ene t used

l,.r rlri.stud

,'L'lys'flame produced by Mecker burner is not homogeneous

nlie;rlly. ft means that there arr different regions in the flarne,
f ,,
i ,. ,r n "o&disixg" region and a "reducing" region appear in the
lletrrr'
,l,ll, t ll
. rr t r .r I i

'l'hese days Mecker burner is not used.

(i}fi5tal oonaumption bu,,nner. A ryp6 total consumption
I is shown in Fig. 14.?.. In this br^rner, the fuel and oxidant
',','r
r,, l,yrlrogen aq{- 9_Iygeq_g?ses respectively. In this type of burner,
tl, lrrlrrid sampfe ii drawn intb the RdmE. From thc-sicle tum[q
h1,11'g€o
I tlrr. I
and oxygen are entering and both are burning at the toP 3Wt
td'
,ll,t\v 1
f'lume Photortretn' und Flume Infi'ured Entissiorl (FIRE) l.i? l

particular region in flame which is to be focussed into the entrance slit of the spectral isolatiorr
-$=.Ttre
unrt.
In flame photometry, several burners and fuel-oxidant combinations have been used to produce the
lytical flame. Some of these are.discussed as below :
Mecker burner. This burner was used earliet 4d employe{ natural gas and oxygen. As this burner
produced relat and low exiifation en. ruis_g#ully used for the
study of aikali m6tals only.
The flamilioclfic6d by Mecker bumer is pot homogeneous chemically. It means that there are
different regions in the flame, r.e., ah "oxidisinlftEioil;;Al "reducing" rggion appeai i4 th6 flarire.
As the.processep leadinglo itornic eiciation in the flame differ in the oxidising and reducing regions
in flame, -different. concdniratidns oT excited atbms are'obfained iri ese regions.

r , gr" used. 't- C>t\- <+ lff^>

Ql1{}6tal altotal own in Fig. 14.3. In this burner,
"{the fu and ox In
th_is type.of bumerl the liquid
t Lampl om the nd oxygeri are'entering and both
are buming at the top of the burner to produce a'flame. As soon as the liquid sannple_ls'drawn
into the baie of llame, the oxygen aspirates sample solution leaving a solid residue. Atomi-iition
and excitation of the sarrrple then follow. ' - ^,

The name "total consumption burner" is used because all the sample that enters the capillary tube
will entqr the flame regardless of droplet size.
hrbulent but can be adiusted to'
rau-o.ffira
nufE-er" 6lT€ers-5-rit-fis use has been stopped and rephced by other types of burners.

Base of Flame

3- fiz (Fuel)
p,
Sample lnlet

Fig. 14.3 : Totel consumptlon burnsr.

ix of laminar-flow burner. A typical premix or laminar- flow bumer is shown in Fig. 14./k In
a b energy type of burner. asoirated sanrdle. fuel and oxidant are thorourhly_4qixed before reaching
-the
burirer openiir!' s move in non-turbulent
fashion, i.€., in lafrinar flow.
An important feature of laminar-flow burner is that only a small portion (about 57o) of the sample
in the iorm of small droplets reaches the flame and is e?sily decomposed. By the easy deconrposition
in means that an effrcient a6lnization of the sample in the flame will ake place. l:rger droplets from
the aspirator impinge on the side of the spray chamber and are drained off. Thus, in this burner 95%
2.372 Flame Photometry and Flame Infrared Emission (FIPJ

However, this loss must -r:

- in a loss of sensitivity.
of the sample may be wasted, thereby, resulting
inr"n""a against the loss of iarger iioplets.
advantage :
The flame produced by premix burner is non-hrrbulent, no-iseless and stable. Another
that in this burner ...y d".o*position of the sample takes place which results in an efficter--
handle solutions up to several perce:'
atomization of the sample in the flame. Premix bumers can
without clogging.

I lluJr a smallegnumb<
olnlxrngnt. Th-us,
.on1p1r.g$ slll'uertuurru
-inGnslfigiving
;a incorlect resuts

Burner Head

Oxidant ---+>

Aspirating Mixin! batfles

alr
I
Drain

FIg. 14.4 : Premk ol lamlnar-flow burner.

(tu) Lundergarph burner.In the Lundegardh burner (Fig. 14.5), the sample must be in liquid fomr' It rs
aspirati into the spray chamber. Lirge droplets condense on the side and drain away; small dropler
and vaporised s,urr'rpl.-ur" swept into the bise of the flame in the form of a cloud. Various devices
have blen used to enhance the nebulization stage in this type of burner. These include the use oi
the impact bead (Perkin-Elmer), ultrasonic vibrators, and more recently thermospray heaters.

Oxygen

Fuel4 Sample Oxygen Mixture, <- Sample

Flg. 14.5 : Lundegardh burner. A rnodllled lorm ol thls burnel ls now commerclally used.

An important feature of this burner is that only about 5% of the sample reaches the flame. The rest
of the'droplets condense and are &ained away. This is a significant loss in atomization efficiencr'
and, therefore, sensitivity.
Difficulties may also arise if there is any selective evaporation of the solvent in the spray chamber'
In particular, ii there are two solvents, the more volatile will preferentially evaporate, leaving
the
 2.382 Flame Photometry and Flame Infrared Emission (FIRE

This type of interference can be overcome by either using very high tenrperature flames to dissociat:
that oxides producing free atoms for excitation or using oxygen{eficient environment to producs
excited atoms.

,\'/ ll.9 Factors thet Inlluence the Intensity of Emitted Rediation in e Flame Photometer
A number of facton will influence the intensity of light ernisSion from a given solution. Some of 0res<
ale as follows :

(a) Viscosity. The addition of a substance which increases the viscosity of the solution (e g
surco6e) decreases the intensity of light emission. This decrease results in due to a reduction in u:
efficiency of atomization.
l,b) Presence of Acids. When an acid is present in the sample solution, this decreases the lig:'
intefsity. This decrease arises due to the disturbance of the initial dissociation equilibrium.
(c). Presence of Other Metals. If other metals are present, these also alter the intensity of emine:
radiatidn. In order to remove this defect, special filters are used which will absorb radiation due to t:r
element which is to be estimated in the sample solution.

"-'M.lO Limitations of Flame Photometry

Although flame photometry is a mcans of determining the total metal cpntgnt present in a samp.:
\/' \D it does not provide information about the molecular form of'thc metal present in the origrci-
sample.
/ (ii') Flame photomebry cannot be used for the direct detection as well as for the determination of 'o*
inert gases.

€tr) Only liquid samples may be used. In some cases, lengthy steps are necessary to prepare liqu.:
$amples.
(Jyf Fhme photometry cannot be used for the direct determination of all metal atoms;,there is i
'/ limitation on the number of elements..that cai be anilysed by this method.

14.11 Determination of Norpmetals

The determination of nonmetals by flame photometry has two major handicaps. First, the atomic s-::
is usually not stable. For example, chlorine does not exist as CI but as CIr. Second, the resonance h:
are in the vacuum ultraviolet. High energy is necessary to cause electronic excitation-more en€rgy rL ':
is available in conventional flames. Atomic emission of non-mctals has not been exploited in flame phc':-
metry until recently, and even then only using research grade equipment.
However, molecular emission has been observed. These are band specta rather than line spectra r,:
are therefore less intense, analyically less sensitive, and more open to spechal interferences. Typical ,-:
are as follows :
l. Brr. Orange-Red System. These orange-red bands occur in the outer cones of flames contsir--,
bromine. The system consists of a very large nunrber of bands, which are degraded to red.
Wavelength (nm)

654, 647, 64t, 636, 634, 63t, 629, 626, 623, 622, 619,
617, 612, 607, 596, 594, 586, 583, 575, 572, 560, 559

In the inner cone of organic flames containing Br, was a sEong band near 290 nm.
2. BrO. Ethyl Bromide Flame Bonds. The bands are degraded to the red. The heads are slig:-.'
diffuse above the inner cone in flames containing ethyl bromide and in an oxygen-methyl bror--. :,'
flanre or an oxyhydrogen flame containing Brr.