Title

:

FLAME ATOMIC SPECTROSCOPY
section 1: section 2: section 3: section 4: Instrumental settings Wavelength scan, atomic emission and absorption Chemical interferences Detection limit, external standard vs. standard addition

Full name: Student no.: Sections:

NAUMAN MITHANI
301016320 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 subspecies’ 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 after nebulisation difference Ca (aq) utilised

! ! ! !

10 ppm Ca (aq): 94.51 g ; 10 ppm Ca (aq): 70.34 g ;

water: 55.03 g water: 76.70 g

10 ppm Ca (aq): (-)24.17 g ; water: (+) 21.67 g 24.17 g – 21.67 g = 2.5 g density of water " 1 g/mL

10 ppm Ca (aq) burner height mean signal 2 0.963 2.5 1.308 2.75 1.018 3 0.504 3.25 0.384 3.5 0.318 4 0.254

# {noise} 0.001 0.001 0.002 0.004 0.002 0.002 0.001

blank mean signal # {noise} 1.109 0.001 1.237 0.001 0.856 0.001 0.307 0.001 0.144 0.001 0.133 0.001 0.087 0.001

"

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

24.17 mL of 10 ppm Ca (aq) " 24.17 mL #10 = 3.63 #1018 atoms delivered in 5 minutes = 1.21#1016 atoms /s

mg g ÷ 40.08 # NA L mol

!

!

'! 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 2 2.5 2.75 3 3.25 3.5 4

signal:noise 963 1308 509 126 192 159 254

signal:background 0.868349865 1.057396928 1.189252336 1.641693811 2.666666667 2.390977444 2.91954023

!

(!

!

!

)!

FAS section 2: CaI emission intensity $ (nm) 421.5 421.6 421.7 421.8 421.9 422 422.1 422.2 422.3 422.4 422.5 422.6 422.7 422.8 422.9 423 423.1 423.2 423.3 signal -0.05 -0.048 -0.046 -0.045 -0.039 -0.036 -0.015 0.094 0.212 0.317 0.471 0.578 0.698 0.728 0.649 0.517 0.409 0.293 0.197 MgI emission intensity $ (nm) 284.2 284.3 284.4 284.5 284.6 284.7 284.8 284.9 285 285.1 285.2 285.3 285.4 285.5 285.6 285.7 285.8 285.9 286 286.1 286.2 signal 0.17 0.163 0.166 0.163 0.165 0.165 0.165 0.17 0.173 0.182 0.182 0.183 0.177 0.174 0.171 0.163 0.155 0.151 0.146 0.147 0.151 CaOH emission intensity $ (nm) 552 552.1 552.2 552.3 552.4 552.5 552.6 552.7 552.8 552.9 553 553.1 553.2 553.3 553.4 553.5 553.6 553.7 553.8 553.9 554 signal 0.154 0.147 0.156 0.156 0.162 0.165 0.183 0.193 0.213 0.246 0.272 0.303 0.347 0.379 0.39 0.408 0.414 0.438 0.43 0.422 0.402

! "

*+! Q1:

!

**!

max emission intensity: average emission intensity:

atomic Ca > ionic Ca > atomic Mg ionic Ca > atomic Ca > atomic Mg

table of net emission signal strength net signal error CaI (422.5 nm) 0.001 0.000000 CaII (393.3 nm) -0.060 0.002236 MgI (285.2 nm) -0.310 0.002828 MgII (279.5 nm) -0.290 0.002236

error % 0.000 3.727 0.912 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 no K (aq) 0.001 0 10 ppm K (aq) 0.529 0.004 100 ppm K (aq) 0.312 0.002 net absorption signal strength for 10 ppm Mg (aq) no K (aq) 0.31 0.002 10 ppm K (aq) 0.415 0.001 100 ppm K (aq) -0.021 0.001

with

error % 0 0.756 0.641 0.645 0.241 4.762

with

"

low volatility compounds: net emission signal strength for 10 ppm Ca (aq) net signal no additives 0.001 0.01 mol/L H3PO4 (aq) 0.312

error 0 0.002 0.003 0.001

error % 0 0.641 1.456 0.1265

with

0.01 mol/L H3PO4 + 1000 ppm Sr2+ 0.01 mol/L H3PO4 + 0.05 mol/L EDTA

0.206 0.79

!

!

*#!

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: -

limit of detection =

mean signal - lowest signal 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 0.226 = 0.059 • concentration + 0.140 concentration = 1.457 ppm

of the unknown

!

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

=

0.005 • 0.059

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

2

= 0.084 •

4 ("0.048) 2 + 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 0.8 0.403 0.003 0.6 0.416 0.002 0.4 0.535 0.002 0.2 0.481 0.004 0 0.226 0.001

error % 0.744 0.481 0.374 0.832 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 CaI (422.5 nm) 0.001 0.000000 CaII (393.3 nm) -0.060 0.002236 MgI (285.2 nm) -0.310 0.002828 MgII (279.5 nm) -0.290 0.002236

error % 0.000 3.727 0.912 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 no K (aq) 0.001 0 10 ppm K (aq) 0.529 0.004 100 ppm K (aq) 0.312 0.002 net absorption signal strength for 10 ppm Mg (aq) no K (aq) 0.31 0.002 10 ppm K (aq) 0.415 0.001 100 ppm K (aq) -0.021 0.001

with

error % 0 0.756 0.641 0.645 0.241 4.762

with

low volatility compounds: net emission signal strength for 10 ppm Ca (aq) net signal no additives 0.001 0.01 mol/L H3PO4 (aq) 0.312 with 0.01 mol/L H3PO4 + 1000 ppm Sr2+ 0.01 mol/L H3PO4 + 0.05 mol/L EDTA 0.206 0.79

error 0 0.002 0.003 0.001

error % 0 0.641 1.456 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.

!

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.

2-

*(!

"

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 %).