Flame Emission Spectroscopy

Tutorial Solution
Question 1
FES is used in the determination of alkali metals and occasionally Calcium. This is because
alkali metals are excited at relatively low temperatures of the flame to give a spectra that is
simple and remarkably free of interference from other metallic species. Alkali-metal spectra
generally consists of a few intense lines, many of which are in the visible region and are well
suited to quantitative emission measurements.
Question 2
1. The temperature of the flame
2. The presence of interfering chemicals (hydroxide etc.)
3. The type of gas used for the flame (acetylene, oxygen etc).
4. Background interference (sample matrix).
5. Ionisation potentials of sample (high/low).
Question 3
Part 3A (Approach 1)
First calculate 4s→ 3p and then 3p→ 3s, following which multiply the two values together.
Consider the formula:
N ∗ 𝑔∗ −∆𝐸⁄
= 𝑒 𝑘𝑇
𝑁0 𝑔0

Since ∆E = hc/λ [h = planks constant (6.63 x 10-34) and c = speed of light (3 x 108)], substitute
hc/λ in place of ∆E to get the final equation;
ℎ𝑐
N∗ 𝑔∗
−( )⁄
𝜆 𝐍∗ 𝒈∗ −(𝒉𝒄)⁄
= 𝑔0 𝑒 𝑘𝑇 → = 𝒆 𝝀𝒌𝑻
𝑁0 𝑵𝟎 𝒈𝟎

Step 1
4s→ 3p
We have;

λ = 1139 𝑥 10−9 , g*=1, g0 = 3, k= 1.381 x 10-23, h= 6.63x10-34, c= 3x108, T= 2100 K

and N4s/N3p = ?
−34 )(3𝑥108 ))
𝑁4𝑠 𝑔∗ −(ℎ𝑐)⁄ 1 −((6.63𝑥10 ⁄
((1139𝑥10−9 )(1.381 𝑥10−23 )(2100𝐾))
= 0 𝑒 𝜆𝑘𝑇 = 𝑒 = 𝟖. 𝟎𝟖𝟖 𝒙 𝟏𝟎−𝟒
𝑁3𝑝 𝑔 3
Step 2
3p→ 3s
We have;

λ = 589.3 𝑥 10−9 , g*=1, g0 = 3, k= 1.381 x 10-23, h= 6.63x10-34, c= 3x108, T= 2100 K

and N4s/N3p = ?
−34 )(3𝑥108 ))
𝑁4𝑠 𝑔∗ −(ℎ𝑐)⁄ 1 −((6.63𝑥10 ⁄
((589.3𝑥10−9 )(1.381 𝑥10−23 )(2100𝐾))
= 0 𝑒 𝜆𝑘𝑇 = 𝑒 = 𝟐. 𝟔𝟒𝟕 𝒙 𝟏𝟎−𝟓
𝑁3𝑝 𝑔 3

Step 3
Calculating 4s→ 3s
Consider:
𝑁4𝑠 𝑁3𝑝 𝑁4𝑠 Hence; we multiply to get; 𝑁4𝑠
𝑥 = = (8.088𝑥10−4 )(2.6471𝑥10−5 )
𝑁3𝑝 𝑁4𝑠 𝑁3𝑠 𝑁3𝑠
= 𝟐. 𝟏𝟒𝒙𝟏𝟎−𝟖

Part 3B (Approach 2)
Alternatively, the ∆E can be calculated first and then substituted in the original formula. First
calculate 4s→ 3p. Here, 4s is the excited state and the degeneracy of 4s is 1(g*) and 3p is the
ground state with a degeneracy of 3(g0). First compute the ∆E and use that to determine the
ratio of excited atoms in 4s to number of atoms in the ground state in 3p. In a similar manner,
than compute 3p→ 3s, and finally multiply the ratios to obtain the ratio of 4s→ 3s.
Note: The λ = 589.3 nm for 3p→ 3s.
Step 1
4s→ 3p

ℎ𝑐 (6.63 𝑥10−34 )(3 𝑥 108 )

∆𝐸 = = = 1.746 𝑥 10−19
𝜆 (1139 𝑥10−9 )
Now, we have;

∆E = 1.746 𝑥 10−9 , g*=1, g0 = 3, k= 1.381 x 10-23, T= 3273 K and N4s/N3p = ?

−9 )
𝑁4𝑠 𝑔∗ −∆𝐸⁄ 1 −(1.746 𝑥10 ⁄
(1.381 𝑥10−23 )(3273𝐾)
= 𝑒 𝑘𝑇 = 𝑒 = 𝟕 𝒙 𝟏𝟎−𝟑
𝑁3𝑝 𝑔0 3
Step 2
3p→ 3s

ℎ𝑐 (6.63 𝑥10−34 )(3 𝑥 108 )

∆𝐸 = = = 3.375 𝑥 10−19
𝜆 (589.3 𝑥10−9 )
Now, we have;

∆E = 3.375 𝑥 10−19 , g*=3, g0 = 1, k= 1.381 x 10-23, T= 3273 K and N3p/N3s = ?

−19 )
𝑁4𝑠 𝑔∗ −∆𝐸⁄ 3 −(3.375 𝑥10 ⁄
(1.381 𝑥10−23 )(3273𝐾)
= 0 𝑒 𝑘𝑇 = 𝑒 = 𝟏. 𝟕𝟏 𝒙 𝟏𝟎−𝟑
𝑁3𝑝 𝑔 1

Calculating 4s→ 3s
Consider:
𝑁4𝑠 𝑁3𝑝 𝑁4𝑠 Hence; we multiply to get; 𝑁4𝑠
𝑥 = = (7𝑥10−3 )(1.71𝑥10−3 ) = 𝟏. 𝟐𝒙𝟏𝟎−𝟓
𝑁3𝑝 𝑁4𝑠 𝑁3𝑠 𝑁3𝑠

Part 3C (Approach 1)
Step 1
4s→ 3p
We have;

λ = 1139 𝑥 10−9 , g*=1, g0 = 3, k= 1.381 x 10-23, h= 6.63x10-34, c= 3x108, T= 9273 K

and N4s/N3p = ?
−34 )(3𝑥108 ))
𝑁4𝑠 𝑔∗ −(ℎ𝑐)⁄ 1 −((6.63𝑥10 ⁄
((1139𝑥10−9 )(1.381 𝑥10−23 )(9273𝐾))
= 0 𝑒 𝜆𝑘𝑇 = 𝑒 = 𝟖. 𝟓𝟐𝟒 𝒙 𝟏𝟎−𝟐
𝑁3𝑝 𝑔 3

Step 2
3p→ 3s
We have;

λ = 589.3 𝑥 10−9 , g*=1, g0 = 3, k= 1.381 x 10-23, h= 6.63x10-34, c= 3x108, T= 9273 K

and N4s/N3p = ?
−34 )(3𝑥108 ))
𝑁4𝑠 𝑔∗ −(ℎ𝑐)⁄ 1 −((6.63𝑥10 ⁄
((589.3𝑥10−9 )(1.381 𝑥10−23 )(9273𝐾))
= 0 𝑒 𝜆𝑘𝑇 = 𝑒 = 𝟎. 𝟐𝟏𝟓
𝑁3𝑝 𝑔 3
Step 3
Calculating 4s→ 3s
Consider:
𝑁4𝑠 𝑁3𝑝 𝑁4𝑠 Hence; we multiply to get; 𝑁4𝑠
𝑥 = = (8.524𝑥10−2 )(0.215)
𝑁3𝑝 𝑁4𝑠 𝑁3𝑠 𝑁3𝑠
= 𝟏. 𝟖𝟑𝒙𝟏𝟎−𝟐 𝑜𝑟 𝟎. 𝟎𝟏𝟖𝟑

Question 4
First calculate the population of excited Na atoms at 2600K and then at 2610K. Following
this, find the percentage difference between the two values.
Step 1; (at 2600 K)
We have;

∆E = 3.371 𝑥 10−19 , g*=2, g0 = 1, k= 1.381 x 10-23, T= 2600 K and N*/N0 = ?

−19 )
𝑁4𝑠 𝑔∗ −∆𝐸⁄ 2 −(3.371 𝑥10 ⁄
(1.381 𝑥10−23 )(2600𝐾)
= 0 𝑒 𝑘𝑇 = 𝑒 = 𝟏. 𝟔𝟕 𝒙 𝟏𝟎−𝟒
𝑁3𝑝 𝑔 1

Step 2; (at 2610 K)

We have;

∆E = 3.371 𝑥 10−19 , g*=2, g0 = 1, k= 1.381 x 10-23, T= 2610 K and N*/N0 = ?

−19 )
𝑁4𝑠 𝑔∗ −∆𝐸⁄ 2 −(3.371 𝑥10 ⁄
(1.381 𝑥10−23 )(2610𝐾)
= 𝑒 𝑘𝑇 = 𝑒 = 𝟏. 𝟕𝟒 𝒙 𝟏𝟎−𝟒
𝑁3𝑝 𝑔0 1

Step 3; (Percentage difference)

1.74 𝑥10−4 − 1.67 𝑥10−4
𝑥 100 = 𝟒. 𝟎𝟐%
1.74 𝑥10−4

Question 5
Consider the relation and formula below;

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑖𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑆𝑖𝑔𝑛𝑎𝑙 𝑓𝑟𝑜𝑚 𝑖𝑛𝑖𝑡𝑖𝑎𝑙

=
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑝𝑙𝑢𝑠 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑖𝑛 𝑓𝑖𝑛𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑆𝑖𝑔𝑛𝑎𝑙 𝑓𝑟𝑜𝑚 𝑓𝑖𝑛𝑎𝑙
[𝑋]𝑖 𝐼𝑋
=
[𝑆]𝑓 + [𝑋]𝑓 𝐼𝑆+𝑋
Step 1
Compute [𝑆]𝑓 𝑎𝑛𝑑 [𝑋]𝑓 and make [𝑋]𝑖 the subject of the formula.

𝑉𝑠 5
[𝑆]𝑓 = [𝑆]𝑖 ∗ ( ) = [2.08 𝑀] ∗ ( ) = 𝟎. 𝟏𝟎𝟒
𝑉 100
𝑉0 95
[𝑋]𝑓 = [𝑋]𝑖 ∗ ( ) = [𝑋]𝑖 ∗ ( ) = 𝟎. 𝟗𝟓 [𝑿]𝒊
𝑉 100

Step 2
Substitute the variables in the original equation and solve for [𝑿]𝒊 .
[𝑋]𝑖 𝐼𝑋
=
[𝑆]𝑓 + [𝑋]𝑓 𝐼𝑆+𝑋
[𝑋]𝑖 4.27 𝑚𝑉
=
0.104 + 0.95 [𝑋]𝑖 6.50 𝑚𝑉
[𝑋]𝑖
= 0.65
0.104 + 0.95 [𝑋]𝑖
[𝑋]𝑖 = 0.068 + 0.62[𝑋]𝑖

0.38[𝑋]𝑖 = 0.068
[𝑿]𝒊 = 𝟎. 𝟏𝟖

Alternatively, use the formula:

Cs x Vs
[X]i = [R(Vs+Vo) − Vo]

Question 6
Explanation – Iron forms a compound with low volatility with the sulfate ions resulting in a
decrease in signal. (Iron sulfate has a much greater thermal stability)
3 Possible Methods:
1. Add a releasing agent like Sr which would react with the sulfate, leaving Iron free for
atomisation.
2. Add a protective agent like EDTA
3. Increase the flame temperature until the compound breaks down.