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Title: FLAME ATOMIC SPECTROSCOPY

section 1: Instrumental settings


section 2: Wavelength scan, atomic emission and absorption
section 3: Chemical interferences
section 4: Detection limit, external standard vs. standard addition

Full name: NAUMAN MITHANI


Student no.: 301016320

Sections: LA02: group C

Date of expt.: Feb. 7, 2008

ABSTRACT:

This atomic spectroscopy experiment employs a flame furnace-absorption

spectrophotometer in showing the following: the highest signal:noise ratio at a

different burner height than the highest signal:background; the spectroscopy runs

show strongest signals for atomic Ca absorption and ionic Mg absorption; the

chemical interference trials demonstrate the hindering effect of phosphoric acid and

the beneficial, preventative effect of strontium and EDTA in the Ca solutions destined

for spectral analysis; by the external standards method, the concentration of Ca (aq) in

the unknown was determined to be 1.457 ± 0.097 ppm (± 6.657 %). There is,

however, limited data in certain sections and so conclusions are not as binding.
! "!
INTRODUCTION:

In order to study the absorption/emission spectra (thus the related properties

and applications) of a substance, it must be excited; as the substance de-excites, it

releases energy, which is characteristic of the substance. This series of atomic

spectroscopy experiments employed the use of a flame furnace (coupled with an

atomic absorption spectrophotometer) to excite the analyte atoms and measure their

absorption/emission spectra.

The first section was the optimising the instrumentation setup; the second

section saw the main experiment where the analyte (Ca and Mg) was volatilised,

ionised and its spectra measured as per the sub-species (atomic or ionic Ca or Mg)

under study, this was done by adjusting the wavelengths corresponding to the sub-

species’ literature wavelengths. The practical scenario of interferences was measured

in the third section where the effect of additives such as K (aq), EDTA, phosphoric

acid and strontium were studied. The fourth section involved application of the

technique as a quantitative analytical tool.


! #!
EXPERIMENTAL:

Apparatus: Perkin-Elmer 1100 B Atomic absorption spectrophotometer,

Ca and Mg hollow cathode lamps.

FAS section 1: The experiment was commenced with the preparation of

250mL of a 10 ppm Ca (aq) solution from the stock solution of 1,000 ppm. This was

done by diluting 2.5 mL of the stock solution with de-ionised water to the mark in a

volumetric flask. 94.51 g of the Ca solution and 55.03 g of water were added to two

separate plastic bottles. The sample tube was inserted in the Ca solution bottle and the

drain tube in the water bottle. The flame was then lit. Aspiration and nebulisation

were conducted for five minutes (blue flame), at the end of which the flame was shut

off and the bottles were re-weighed at 70.34 g and 76.70 g for the Ca (aq) and water

respectively. The sample uptake rate was calculated at 0.5 mL/min and the experiment

was carried on.

The next section involved the process for selecting the optimum burner height.

The burner heights of 2, 2.5, 2.75, 3, 3.25, 3.5 and 4 were tried and for each height

value, the mean detector response was noted for the 10 ppm Ca solution and the

blank. The optimal burner height was deemed to be 3.25. During this aspiration, the

flame was seen to change to red-orange colour.

FAS section 2: The 1,000 ppm Ca and Mg stock solutions were used to

prepare 100 mL solutions of 10 ppm concentration. This was done by diluting 1 mL

extracts of the solutions with de-ionised water to the mark in separate volumetric

flasks.

The solutions were analysed and the emission intensities recorded; the

scanning wavelengths were set from 1 nm less to 1 nm beyond the literature emission
! $!
wavelength for the particular species to be analysed: 421.5 nm ! CaI ! 423.5 nm,

554.0 nm ! CaOH ! 556.0 nm and 284.2 nm ! MgI ! 286.2 nm; the scan rate was set

at 1 nm/min. The next step was measuring the signal intensities of the CaI, CaII, MgI

and the MgII species at their respective wavelengths of 422.5 nm, 393.3 nm, 285.2

nm and 279.5 nm respectively. The (H)ollow (C)athode (L)amp was turned on, set to

the suitable current and the signals were recorded for CaI and MgI at their respective

absorption line wavelengths.

FAS section 3: Three 100 mL solutions of Ca and Mg of 10 ppm

concentration each were prepared (as before). To one pair of Ca and Mg solutions,

0.1 mL of 10,000 ppm K (aq) were added to bring its K (aq) concentration to 10 ppm;

10 mL of the stock K (aq) solution were added to another pair to bring the K (aq)

concentration to 1,000 ppm and no K (aq) was added to the third pair. The emission

intensities of the Ca (CaI) solutions were measured and the absorption intensities of

the Mg (MgI) solutions were measured. Four more 100 mL Ca (aq) of 10 ppm were

prepared in the following manner. 10 mL of 0.01 mol/L H3PO4 was added to one 100

mL volumetric flask, bringing its concentration to 0.01 mol/L in that Ca (aq), 10 mL

of 0.01 mol/L H3PO4 + 10 mL of 10,000 ppm Sr2+ to have 0.01 mol/L concentration

of the acid and 1000 ppm of the Sr2+ (aq) was added to another, the same volume of

the acid (and thus concentration) + 50 mL of 0.05 mol/L EDTA were added to the

third flask, and nothing was added to the fourth flask; 1 mL of the stock Ca solution

was added to each flask and were all diluted to the mark with de-ionised water. Their

intensities were measured at the CaI line (422.5 nm). The presence of Sr (aq) caused

the colour of the flame to become red, orange with EDTA.

FAS section 4: The vessels used as the containers for the following are

volumetric flasks. Ca (aq) solutions of 10, 5, 1, 0.1 and 0.01 ppm were prepared. The

10 ppm solution was prepared as before; the 5 ppm one was prepared by diluting 0.5

mL of the 1,000 ppm Ca solution to the 100 mL mark; the 1 ppm solution was

prepared by diluting 10 mL of the 10 ppm solution to the mark; 0.1 ppm solution by
! %!
diluting 1 mL of the 1 ppm to the mark and so on and so forth for further lower

concentrations. The “unknown” solution was prepared by diluting 25 mL of

phosphoric acid + 2.5 mL of the 1,000 ppm Ca sol to the 250 mL mark with de-

ionised water. The HCL lamp was turned off and the emission intensities of CaI were

measured using the Ca solutions prepared. Multiple readings were taken for each

concentration and the averages recorded. The unknown was measured five times as

well.

25 mL aliquots of the unknown was made, to which 0, 0.2, 0.4, 0.6 and 0.8 mL

of the 1,000 ppm Ca stock solution was added then diluted to the 50 mL mark. Their

emission signals were also measured.


! &!
DATA AND RESULTS:

! FAS section 1: -

before nebulisation ! 10 ppm Ca (aq): 94.51 g ; water: 55.03 g

after nebulisation ! 10 ppm Ca (aq): 70.34 g ; water: 76.70 g

difference ! 10 ppm Ca (aq): (-)24.17 g ; water: (+) 21.67 g

Ca (aq) utilised ! 24.17 g – 21.67 g = 2.5 g

density of water " 1 g/mL

10 ppm Ca (aq) blank


burner height mean signal # {noise} mean signal # {noise}
2 0.963 0.001 1.109 0.001
2.5 1.308 0.001 1.237 0.001
2.75 1.018 0.002 0.856 0.001
3 0.504 0.004 0.307 0.001
3.25 0.384 0.002 0.144 0.001
3.5 0.318 0.002 0.133 0.001
4 0.254 0.001 0.087 0.001

" Q1: rate of delivery of Ca atoms to the flame:

mg g
24.17 mL of 10 ppm Ca (aq) " 24.17 mL #10 ÷ 40.08 # NA
L mol

= 3.63 #1018 atoms delivered in 5 minutes

= 1.21#1016 atoms /s

!
! '!

" Q2: Nebulisation efficiency:

calcium utilised 2.5g 2.5 mL


= "
duration (min) 5 5

= 0.5gmin#1 " 0.5mL min#1

" Q3, Q4: Signal:noise and signal:background ratios and graphs

CaI emission line


burner height signal:noise signal:background
2 963 0.868349865
2.5 1308 1.057396928
2.75 509 1.189252336
3 126 1.641693811
3.25 192 2.666666667
3.5 159 2.390977444
4 254 2.91954023
! (!
! )!
! FAS section 2: -

CaI emission intensity MgI emission intensity CaOH emission intensity


$ (nm) signal $ (nm) signal $ (nm) signal
421.5 -0.05 284.2 0.17 552 0.154
421.6 -0.048 284.3 0.163 552.1 0.147
421.7 -0.046 284.4 0.166 552.2 0.156
421.8 -0.045 284.5 0.163 552.3 0.156
421.9 -0.039 284.6 0.165 552.4 0.162
422 -0.036 284.7 0.165 552.5 0.165
422.1 -0.015 284.8 0.165 552.6 0.183
422.2 0.094 284.9 0.17 552.7 0.193
422.3 0.212 285 0.173 552.8 0.213
422.4 0.317 285.1 0.182 552.9 0.246
422.5 0.471 285.2 0.182 553 0.272
422.6 0.578 285.3 0.183 553.1 0.303
422.7 0.698 285.4 0.177 553.2 0.347
422.8 0.728 285.5 0.174 553.3 0.379
422.9 0.649 285.6 0.171 553.4 0.39
423 0.517 285.7 0.163 553.5 0.408
423.1 0.409 285.8 0.155 553.6 0.414
423.2 0.293 285.9 0.151 553.7 0.438
423.3 0.197 286 0.146 553.8 0.43
286.1 0.147 553.9 0.422
286.2 0.151 554 0.402
! *+!
" Q1:
! **!

max emission intensity: atomic Ca > ionic Ca > atomic Mg


average emission intensity: ionic Ca > atomic Ca > atomic Mg

table of net emission signal strength


net signal error error %
CaI (422.5 nm) 0.001 0.000000 0.000
CaII (393.3 nm) -0.060 0.002236 3.727
MgI (285.2 nm) -0.310 0.002828 0.912
MgII (279.5 nm) -0.290 0.002236 0.771

table of net absorption signal strength from HCL


net signal error error %
CaI (422.5 nm) 0.226 0.003162 1.399
MgII (285.2 nm) -0.022 0.001414 6.427
! *"!
! FAS section 3: -

" Ionisation equilibria: -

net emission signal strength for 10 ppm Ca (aq)


net signal error error %
no K (aq) 0.001 0 0
with 10 ppm K (aq) 0.529 0.004 0.756
100 ppm K (aq) 0.312 0.002 0.641
net absorption signal strength for 10 ppm Mg (aq)
no K (aq) 0.31 0.002 0.645
with 10 ppm K (aq) 0.415 0.001 0.241
100 ppm K (aq) -0.021 0.001 4.762

" low volatility compounds: -

net emission signal strength for 10 ppm Ca (aq)


net signal error error %
no additives 0.001 0 0
0.01 mol/L H3PO4 (aq) 0.312 0.002 0.641
with
0.01 mol/L H3PO4 + 1000 ppm Sr2+ 0.206 0.003 1.456

0.01 mol/L H3PO4 + 0.05 mol/L EDTA 0.79 0.001 0.1265


! *#!
! FAS section 4: -

" Q1: -

CaI emission intensity


concentration (ppm) mean net emission intensity error error %
10 0.693 0.003 0.433
5 0.538 0.003 0.558
1 0.145 0.002 1.379
0.1 -0.001 0 0.000
0.01 -0.001 0.001 -100.000
lowest concentration values aren’t considered due to apparent erroneous readings
! *$!
" Q2: -

mean signal - lowest signal


limit of detection =
gradient of calib. curve

0.3437 " 0.145


= = 3.367 ppm
0.059

! " Q3: -

emission signal = 0.069 • concentration + 0.065

0.226 is the unknown signal


of the unknown
0.226 = 0.059 • concentration + 0.140

concentration = 1.457 ppm

! error : "
2
s 1 1 ( yc " y)
sc = y + +
m M N m 2 Sxx

2
1 (0.226 " 2 (0.693 " 0.145))
1
0.005
= • 1+ +
0.059 4 0.059 2 # 40.67

4 ("0.048) 2
= 0.084 • +
3 0.145

= 0.084 • 1.35 = 0.084 #1.162 = 0.097 ppm

!
concentration of unknown: 1.457 ± 0.097 ppm
! *%!
" Q4, Q5: -

standard addition "unknown" emission intensity


concentration (ppm) mean net emission intensity error error %
0.8 0.403 0.003 0.744
0.6 0.416 0.002 0.481
0.4 0.535 0.002 0.374
0.2 0.481 0.004 0.832
0 0.226 0.001 0.442
! *&!
DISCUSSION:

" FAS 1:

in the calculation of the nebulisation efficiency, plastic bottles were used and

not glass. Plastic is lighter, easier to handle and wield and that it would still allow for

mass measurements on analytical balances without overloading them.

" FAS 1 Q5, Q6:

The best S/N ratio is found at a lower burner height than the for the best S/B

ratio. As the burner height is raised, the inter-zonal region is reached, which is the

most efficient region for atomisation and contains the highest concentration.

" FAS 2 Q6:

Mg: from the negative emission intensities, it can be seen that absorption is

more suited to Mg. The best signal is from the ionic emission since it has a higher net

signal and a lower error margin.

Ca: from the limited data, the absorption mode for atomic Ca provides the

best signal ! lowest error margin and a reasonable net signal strength.

table of net emission signal strength


net signal error error %
CaI (422.5 nm) 0.001 0.000000 0.000
CaII (393.3 nm) -0.060 0.002236 3.727
MgI (285.2 nm) -0.310 0.002828 0.912
MgII (279.5 nm) -0.290 0.002236 0.771

table of net absorption signal strength from HCL


net signal error error %
CaI (422.5 nm) 0.226 0.003162 1.399
MgI (285.2 nm) -0.022 0.001414 6.427
! *'!
" FAS 3 Q1 to Q5:

Ionisation equilibria: -

net emission signal strength for 10 ppm Ca (aq)


net signal error error %
no K (aq) 0.001 0 0
with 10 ppm K (aq) 0.529 0.004 0.756
100 ppm K (aq) 0.312 0.002 0.641
net absorption signal strength for 10 ppm Mg (aq)
no K (aq) 0.31 0.002 0.645
with 10 ppm K (aq) 0.415 0.001 0.241
100 ppm K (aq) -0.021 0.001 4.762

low volatility compounds: -

net emission signal strength for 10 ppm Ca (aq)


net signal error error %
no additives 0.001 0 0
0.01 mol/L H3PO4 (aq) 0.312 0.002 0.641
with
0.01 mol/L H3PO4 + 1000 ppm Sr2+ 0.206 0.003 1.456

0.01 mol/L H3PO4 + 0.05 mol/L EDTA 0.79 0.001 0.1265

K ionises more easily than Ca or Mg and so acts as an ionisation suppressor. It

consumes more energy of the system, so Ca or Mg has less and that by its own

ionisation, it releases electrons and inhibits the ionisation of Ca or Mg by Le

Chatilier’s principle. As the concentration rises even further, other factors such as

energy loss due to inter-atomic collisions come into play, since there exist more

particles to physically interact with each other.

A hotter flame would raise the rate of decomposition and volatilisation of the

analyte, and so artificially higher signal intensities may be observed.

The greater the concentration of H3PO4, the higher the concentration of the

compound CaHPO4 and consequently lesser the concentration of unbound Ca (the

analyte). This particular substance does not break apart as easily in the flame, nor

does it volatilise; hence the signal intensity is, in a way, doubly reduced.
! *(!
2-
Sr would react and bind with the HPO4 ion, thereby allowing for the Ca

analyte to remain free. In other words, it would block the interfering acid and prevent

a lesser signal intensity.

EDTA forms volatile complexes with Ca thereby saving it from forming the

non-volatile CaHPO4. Ca is eventually released.

" FAS 4 Q5 to Q7:

due to the non-linearity of the graph, further evaluation is not feasible.

Due to likely experimental errors and the more cumbersome calculations in the

evaluation of error margins with the standard addition method, the external standard

method is deemed more favourable.


! *)!
CONCLUSION:

It is proven that due to the inherent characteristics of a flame, the best S/N is

obtained at a different burner height than the best S/B. The subsequent data shows the

absorption mode for atomic Ca and ionic Mg as the most reliable signals, though the

data is limited and this cannot be satisfactorily proven. The interference section shows

the hindering effect of phosphoric acid and the beneficial, preventative effect of

strontium and EDTA in the Ca solutions destined for spectral analysis. Lastly, by the

external standards method, the concentration of Ca (aq) in the unknown was 1.457 ±

0.097 ppm (± 6.657 %).