Solutions to Problems of Chapter 9

9-1.
a. A releasing agent is a cation that reacts preferentially with an anion to release the analyte. The
releasing agent should form a compound of higher stability than that formed by the analyte.

b. A protective agent is usually a ligand that reacts with the analyte forming a relatively volatile
comple.

c. An ioni!ation suppressor is a salt of an al"ali metal added to suppress ioni!ation of an analyte.
The al"ali metal is easily ioni!ed resulting in a flu of electrons which shift the ioni!ation
e#uilibrium of analyte towards formation of atoms.

d. Atomi!ation is the process whereby gaseous molecules will brea"down to form atoms.

e. Pressure broadening is a mechanism whereby atomic lines are broadened due to collisions$
especially at high pressures. %roadening ta"es place since atoms of analyte in the ground states
assume different energies due to collisions.

f. A hollow cathode lamp is the most common line source used in AAS. A &C' lamp is
composed of a glass envelope (with a #uart! window) encompassing a hollow cathode$ covered
with a layer of the metal of interest$ and a wire anode. The lamp contains an inert gas li"e argon
at low pressure.

g. Sputtering is a process whereby energetic argon ions rapidly stri"e the hollow cathode surface
thus releasing too many atoms from the cathode surface.

h. Self-absorption is a process observed when a &C' lamp is operated at high currents where
sputtering of a large number of atoms ta"es place. *ost atoms do not get enough ecitation
energy in this process and thus absorb emitted radiation from other ecited atoms within the
lamp. The result is a splitting of the atomic line where the center of the line would have a
minimum eactly at the wavelength of the original line.

i. The class of interferences related to spectral properties of components other than atomi!ed
analyte is referred to as spectral interferences. Three sources for spectral interferences can be
identified including spectral line interference$ scattering$ and broad band spectral interference.

+. Chemical interferences are those interferences that occur due to chemical processes which ta"e
place in flames. These include formation of compounds of low volatility$ dissociation e#uilibria$
and ioni!ation e#uilibria.

". A radiation buffer is a substance added to both sample and standards in such a concentration
that largely eceeds the concentration initially present in the sample. The reason for addition of a
radiation buffer is to ma"e the interference from the initial substance in the sample insignificant
since now a large ecess is added to both sample and standards.

'. ,oppler broadening is a manifestation of the ,oppler effect where a detector will see a higher
fre#uency for a fast moving atoms towards it and will see a lower fre#uency for atoms moving
away from it. ,oppler broadening is a ma+or reason for line broadening in atomic spectroscopy
and is largely increased at higher temperatures.

9--. The signal for silver increases as we move to higher temperatures away from the burner tip
where silver will not be easily oidi!ed. %est results for the analysis of chromium occur at lower
heights (fuel rich flames) since at higher heights oygen from atmosphere will force chromium
to convert to the oide which will not be atomi!ed at flame temperatures. .ncreasing the height
above tip will increase the signal for *g due to increased atomi!ation at higher temperatures.
&owever$ at higher distances the oide starts to form leading to a decrease in signal.

9-/. Three reasons for etra sensitivity of electrothermal methods can be identified0
a. 1sually$ higher temperatures are used in electrothermal methods.
b. The residence time of atoms inside the graphite furnace is much longer than that in flames
resulting in higher sensitivities due to longer eposure times.
c. 2lame sensitivities are usually limited by inconsistencies in flame composition and impurities
from fuel3 which is avoided in electrothermal methods.

9-4. .n this techni#ue$ radiation from a deuterium lamp and a &C' lamp alternately pass through
the graphite tube analy!er. .t is essential to "eep the slit width of the monochromator sufficiently
wide in order to pass a wide bandwidth of the deuterium lamp radiation. .n this case$ the
absorbance by analyte atoms is negligible and absorbance can be attributed to molecular species
in matri. The absorbance of the beam from the deuterium lamp is then subtracted from the
analyte beam (&C') and thus a bac"ground correction is obtained.



9-5. Source modulation is used in atomic absorption spectroscopy in order to overcome the
problems due to emission in flames resulting from impurities in fuel as well as burner head.

9-6. Two main reasons for the increased signal in presence of ethanol0
a. .ncreased nebuli!ation rate due to lower surface tension in presence of ethanol which
produces smaller droplets
b. 2aster evaporation of solvents in flame.

9-7. This phenomenon is attributed to self-absorption. Self-absorption is a process observed
when a &C' lamp is operated at high currents where sputtering of a large number of atoms ta"es
place. *ost atoms do not get enough ecitation energy in this process and thus absorb emitted
radiation from other ecited atoms within the lamp. The result is a splitting of the atomic line
where the center of the line would have a minimum eactly at the wavelength of the original line.

9-8. 9e are limited to the temperature of the acetylene:nitrous oide flame but can perform one
of the following0
1. The reason for a lower sensitivity can be attributed to several reasons$ therefore try using a
releasing agent.
-. Try using a protective agent.
/. Try using an organic solvent to improve nebuli!ation and thus sensitivity.
4. .f you have enough sample$ try to etract Sr into an immiscible solvent containing a suitable
ligand.

9-9. Atomic emission is the techni#ue that will be severely affected by fluctuations in
temperature since signal is dependent on the number of atoms in the ecited state. This number is
significantly affected by fluctuations in temperature as derived from the %olt!mann e#uation.
&owever$ in the case of atomic absorption$ the signal depends on the number of atoms in ground
state that will absorb energy. Always the number of atoms in ground state is very high as related
to the number of ecited atoms0

;+:;o < 1.7-1=
-4

or
17- ecited atoms for each 1=
6
atoms in ground state

This suggests a very high population of the ground state even at high temperatures. Therefore$
atomic absorption will not be affected to any significant etent by fluctuations in temperature$ if
compared to atomic emission spectroscopy. &owever$ there are some indirect effects of
temperature on atomic absorption spectroscopy.

9-1=. .nitially$ nebuli!ation of the *gCl- will ta"e place resulting in the formation of a spray of
small si!ed droplets containing *gCl-. ,esolvation of the droplets in flame will render the spray
into a solid aerosol of *gCl- particles. These particles will be converted to gaseous molecules of
*gCl-. The gaseous molecules will then be atomi!ed giving *g and Cl atoms. *g atoms will
then absorb energy from a &C' or A,' lamp where absorbance can be measured.

9-11.
> < :
> < 5==: =.==- < -.51=
5

> < n;
-.51=
5
< 1 ? ;
; < -.51=
5
bla!es

Si!e of @rating < -.51=
5
bla!e:-.41=
/
bla!e:mm< 1=4 mm

9-1-. 2rom my observations (you may have slightly different values)0

&eight (cm) T (
o
C) T (A)
- 17== 197/
/ 186/ -1/6
4 18/= -1=/
5 175= -=-/

The intensity of the emission lines is proportional to the number of atoms in ecited state3 which
is best obtained from the %olt!mann relation0

B+ < hc:
B+ < (6.6-561=
-/4
C s

-.9981=
1=
cm s
-1
):D(766.5 nm (cm:

1=
7
nm)E
B+ < -.591=
-19
C

The ratio at 197/ A can be calculated from %olt!mann e#uation0

;+:;o < (P+:Po) ep (- B+:AT)
;+:;o < (6:-) ep D(--.591=
-19
C:(1./81=
--/
C A
-1
197/ A)E
;+:;o < -.-11=
-4

.n the same manner we can calculate the ratio at other temperatures$ we get0

&eight (cm) T (
o
C) T (A) ;+:;o .:.- cm
- 17== 197/ -.-11=
-4
1.=
/ 186/ -1/6 4.591=
-4
-.1
4 18/= -1=/ /.991=
-4
1.8
5 175= -=-/ -.81=
-4
1.-6

9-1/.
a. .ron forms a compound with low volatility with the sulfate ions resulting in a decrease in
signal.
b. 1. The easiest way is to add a releasing agent li"e 'a or Sr which prefer to react with sulfate
-. Addition of a protective agent li"e B,TA.
/. .ncreasing temperature to brea"down the compound.

9-14. ;+:;o < P+:Po ep
FB
+
:AT

B+ < hc:

Substitution in the above relation gives
;+:;o < P+:Po ep
F

hc:AT

a... 2or sodium at -1== A
;+:;o < 6:- ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(589/ A
o
? 1=
-1=
m:A
o
)(1./81=
--/
CA
-1
?
-1== A)E
;+:;o < -.61=
-5
a. ... 2or *g
G
we have the average resonance line at -8== A
o
;+:;o < 6:- ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(-8== A
o
? 1=
-1=
m:A
o
)(1./81=
--/
CA
-1
?
-1== A)E
;+:;o < 6.91=
-11

b... 2or ;a at -9== A
;+:;o < 6:- ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(589/ A
o
? 1=
-1=
m:A
o
)(1./81=
--/
CA
-1
?
-9== A)E
;+:;o < 6.61=
-4

b.... 2or *g
G
at -9== A
;+:;o < 6:- ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(-8== A
o
? 1=
-1=
m:A
o
)(1./81=
--/
CA
-1
?
-9== A)E
;+:;o < 6.11=
-8

c. .. 2or sodium at 6=== A
;+:;o < 6:- ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(589/ A
o
? 1=
-1=
m:A
o
)(1./81=
--/
CA
-1
?
6=== A)E
;+:;o < 5.11=
--

c. ... 2or *g
G
at 6=== A
;+:;o < -:6 ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(-8== A
o
? 1=
-1=
m:A
o
)(1./81=
--/
CA
-1
?
6=== A)E
;+:;o < 5.71=
-4

9-15. a. 2or acetylene:oygen flame at /===
o
C
.. 2irst calculate ratio between 4sto /p
The ecited state is the 4s (P+ < -) and ground state is /p (Po < 6)
;+:;o < P+:Po ep
F

hc:AT
Substitution gives0
;4s:;/p < -:6 ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(11/9 nm ? 1=
-9
m:nm)(1./81=
--/
CA
-1
?
/-7/ A)E
;4s:;/p < 71=
-/

... Calculate ratio from /p to /s (ground state)
;+:;o < 6:- ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(589./ nm ? 1=
-9
m:nm)(1./81=
--/
CA
-1
?
/-7/ A)E
;/p:;/s < 1.71=
-/

;4s:;/p ? ;/p:;/s < ;4s:;/s < 71=
-/
? 1.71=
-/
< 1.-1=
-5

b. 2or a plasma source at 9===
o
C
.. 2irst calculate ratio between 4sto /p
The ecited state is the 4s (P+ < -) and ground state is /p (Po < 6)
;+:;o < P+:Po ep
F

hc:AT
Substitution gives0
;4s:;/p < -:6 ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(11/9 nm ? 1=
-9
m:nm)(1./81=
--/
CA
-1
?
9-7/ A)E
;4s:;/p < 8.5/1=
--

... Calculate ratio from /p to /s (ground state)
;+:;o < 6:- ep F D(6.6-561=
-/4
C s ? -.9981=
8
m s
-1
):(589./ nm ? 1=
-9
m:nm)(1./81=
--/
CA
-1
?
9-7/ A)E
;/p:;/s < =.-15
;4s:;/p ? ;/p:;/s < ;4s:;/s < 8.5/1=
--
? =.-15 < 1.81=
--

9-16. Plot the three points as follows0
Concentration (ppm) Absorbance
=.=5 =.=9
=.1 =.17
=.- =./4
1n"nown =.1
2rom linear regression analysis of the data we have0

C < -=.==/ G =.598 S where S is the signal and C is the concentration
C < =.=595

9-17. The appearance of pea"s during drying and ashing processes could be attributed to
formation of particulates which result in scattering. Also$ volatile molecular species formed
during these processed obviously contribute to observed signals.

9-18. The etent of ioni!ation will definitely be more pronounced when the concentration of
uranium decreases since the vapor pressure of uranium atoms decreases. 2raction ioni!ed is
inversely proportional to partial pressure of atoms before ioni!ation.
9hen an al"ali metal is added electrons are introduced in the system$ thus decreasing ioni!ation
of uranium.

9-19. The purpose of an internal standard in flame emission spectroscopy is to correct for small
fluctuations in flame temperature as well as correction for fluctuations in sample aspiration rate.

9--=. 2or two points calibration we have0
Slope of the standard plot < (A- F A1):(C- F C1)
Slope < (=.599 F =./96):(=.45 F =.-5) < 1.=-

Therefore$ can calculate the intercept from the straight line e#uation0
A < mC G b
=.599 < 1.=-?=.45 G b
b < =.14=

;ow$ we can find the un"nown concentration0

=.444 < 1.=-C G =.14=
C < =.-98 ppm

Problems 9--1 and 9--- can be directly solved using any linear regression analysis program li"e
ecel or statview$ etc.