Experiment 2: Elemental Analysis by Sodium Fusion

Jirov A. Advincula, Adriel Noel R. Andonaque, Czariss Dale Grace Bedoya

Group 1, Chemistry 33 – LB5A Date Performed: September 20, 2019
Sir Aaron Noel P. Genato Date Submitted: October 11, 2019

Abstract
The presence of nitrogen, sulfur, and halogen in different organic compounds can’t be attested
at their organic phase, but is possible if they were converted into their inorganic anions which
will bind with a cation. In this particular qualitative analysis, sodium was used to extrapolate these
elements from their covalence with carbon chains. Sodium fusion of p-chloroaniline, sulfanilic
acid, chlorobenzene and an unknown compound were separately conducted, and each extract
was subjected to sulfur, nitrogen, and halogen testing. Positive and negative results for each
sample were deduced after observation of changes in color of the solution and appearance of
precipitate. Thus, elemental analysis on p-chloroaniline, chlorobenzene, and sulfanilic acid
confirmed the presence of sulfur, nitrogen, and halogens while the composition of the sets of
unknown were partially revealed.

Keywords: qualitative analysis, sodium fusion, Lassaigne’s extract, sulfur, nitrogen, halogens

I. Introduction presence of nitrogen in several reactions through

The significance of elemental analysis in the field
of organic chemistry has played a vital role in
determining the composition of certain
compounds, whether it be confirmatory or
completely exploratory to of some of unknown
(Gabbai et al., 2016). It can be done in two ways:
qualitatively and quantitatively. Qualitative
approach ascertains the presence of particular
elements, but the percent amount (usually in
percent weight) is done quantitatively (Barron &
Raja, 2019). For instance, according to Borje and
Hall (2001), in determining the amount of carbon
and hydrogen in an organic compound, they are
converted to carbon dioxide and water through
combustion followed by a quantitative analysis of
the latter compound. In the field of a more
advanced technological analysis, most common
techniques used in laboratories today are X-ray
fluorescence (XRF), absorption atomic
spectroscopy (AAS), and inductively coupled
plasma (ICP) techniques (Bozic, 2019).
However, the experiment was only limited to
qualitative analysis, which was specifically done
through Lassaigne’s test, considered to be the
most efficient method in laboratories (Criddle and
Ellis, 1967). Also known as the sodium fusion
test, this particular experimental setup is named
after its developer, Jean Louis Lassaigne
(Henssonow et al., 2010). Lassaigne started this
discovery with the detection of nitrogen from
samples of small quantities. He has observed
that chemists before used to determine the
isolating the proper substances in the gaseous
state. By burning the gas, nitrogen is transformed
into ammonia, which is easily identified but not in
minimal amounts of the substance.
In Lassaigne's fusion experiment of nitrogen-
containing organic compound and potassium
produced potassium cyanide, he discovered that
in the presence of ferrous-ferric salt, the
precipitate was green blue or yellow and after a
few drops of HCl, the precipitate turned blue.
Thus, he continued his experiment with other
nitrogen-containing organic compounds in small
quantities. Using the same method of fusion and
the addition of ferrous-ferric sulfate followed by a
drop of HCl, the presence of nitrogen was
indicated by the formation of a deep blue solution
(Wisniak, 2014). However, it was Jacobsen in
1897 who replaced potassium with sodium as the
active reagent since sodium is a stronger
reducing agent than potassium (Gower &
Rhodes, 1969). This fusion method was then
developed by other scientists to detect other
elements such as halogens and sulfur (Wisniak,
2014). Other elements, aside from nitrogen,
sulfur and halogens, are usually only tested if
their presence is suspected from other evidence
(Gower & Rhodes, 1969).
The sodium-fusion test usually makes use of
color changes or precipitate formation in
solutions to indicate specific chemical reactions
(Co & Salindo, 2012). The test involves “fusing”
clean sodium metal with an organic compound

Chemistry 33: Elemental Analysis by Sodium Fusion Page 1 of 6

sample at very high temperature (Henssonow et
al., 2010). The main principle is that, since
elements to be tested are covalently bonded to
the hydrocarbons, their tendency is to break the
bond with the carbon chains, becoming in their
ionic form (which are anions in this case) to bond
with the cation metal Na+. These new ionic bonds
are extracted from the “fused” mass by boiling
and subsequent filtering. The extract, called a
sodium fusion extract or Lassaigne’s extract, is
subjected to different qualitative tests utilizing
different reagents to specifically identify if the
sample contains nitrogen, sulfur, and/or
halogens (vlab.amrita.edu, 2011).
The objectives of the experiment were to (1)
prepare a “complete” sodium fusion of p-
chloroaniline, sulfanilic acid, chlorobenzene, and
unknown samples; (2) distinguish a positive
result from a negative result in respective
analyses using compounds of known elemental
composition; and (3) determine whether the sets
of unknown compounds contain nitrogen, sulfur,
chlorine, bromine, and/or iodine.
II. Experimental
Sodium Fusion
In a fume hood, a 5 mm piece of sodium metal
was removed from a kerosene oil bath and then
placed on tissue paper and patted dry. A few
drops of hexane were used to remove excess
kerosene and to ensure sodium purity. The
sodium was then placed in a test tube and heated
over an alcohol lamp until the metal had
vaporized. The test tube was removed from the
flame and 30 mg of the organic sample was
added into the tube. The test tube was then again
heated for ten minutes. While still hot, the test
tube was dropped into a 150-mL beaker
containing approximately 20 mL of distilled water
allowing it to break and have the fusion mix with
the water. The solution in the beaker was again
heated for five minutes, after which it was filtered
into another beaker using filter paper in a glass
funnel. This procedure was separately done for
the preparation of sodium fusion with p-
chloroaniline, sulfanilic acid, chlorobenzene, and
an unknown substance respectively.
Sulfur Test
Five drops of the prepared fusion solution was
added into a 10-mL test tube containing three
Chemistry 33: Elemental Analysis by Sodium Fusion
drops of water. Two drops of 2% aqueous
Na2[Fe(C)5NO] was then added to the solution.
Development of a purple solution indicated a
positive result; absence of sulfur in the sample
was deduced otherwise.
Nitrogen Test
A pinch of FeSO4 was added to a test tube
containing 1 mL of the fusion solution. Five drops
of 10% KF was also added, and the solution was
boiled for 10 seconds. After boiling, two drops of
5% FeCl3 was added to the solution, and 6 M
H2SO4 was added to acidify the solution. A piece
of litmus paper was dropped into the solution to
confirm the acidity of the solution. Development
of a blue solution confirmed the presence of
nitrogen; similar to the previous test, absence of
nitrogen is indicated otherwise.
Halogen Test
In a fume hood, a test tube containing 10 drops
of the prepared fusion solution and a few drops
of 2M HNO3 was heated. After subjecting to heat
for five minutes, four drops of 0.1M AgNO3 was
added. The test tube was then centrifuged at
1000 rpm for one minute. The decantate was
discarded from the test tube, and 2 M NH3 was
added dropwise to the test tube to examine its
solubility. The properties of the formed precipitate
(if any) were observed to deduce the presence of
halogens.
III. Results
Since the experiment used a qualitative
approach in elemental analysis, the sets of
results are descriptive observations on the color
change, precipitation and the corresponding
appreciable solubility of these precipitates.
Sodium Fusion
Table 1. Color appearance of sodium fusion
extract after filtration.
Sample Color of Solution
p-chloroaniline slightly grayish
chlorobenzene slightly grayish
sulfanilic acid colorless
unknown 1 yellowish
As shown in Table 1, most of the sodium fusion
solutions appeared to be slightly grayish to
colorless in color, except for the fusion using
sulfanilic acid which turned out to be completely
Page 2 of 6
colorless. Among the unknown samples, majority Halogen Test
had similar appearance (grayish) with the
previous fusion solutions, except for unknowns 5, Table 4. Color of the precipitate formed after the
6, and 7. Unknown 5 was similarly yellowish to addition of AgNO3 and their solubility in NH3.
unknown 1 while the solutions for both Unknowns Color of Solubility
Sample
Precipitate in NH3
6 and 7 were colorless.
slightly
p-chloroaniline white
soluble
Sulfur Test chlorobenzene none N/A
sulfanilic acid black* N/A
Table 2. Color appearance of the solution after unknown 1 none N/A
sulfur test. *black precipitate is a nonhypothetical result,
Color of thus no need to check its solubility
Sample Indication
Solution
p-chloroaniline deep yellow - Upon addition of AgNO3, only the p-chloroaniline
chlorobenzene deep yellow -
precipitated and is slightly soluble in NH3.
deep blue-
sulfanilic acid + Chlorobenzene, however, appeared to have a
violet
unknown 1 deep yellow - cloudy yellow solution, which can be an indication
of incomplete precipitation. On the other hand,
As table 2 suggests, p-chloroaniline, sulfanilic acid accumulated black precipitate,
chlorobenzene, and unknown 1 responded which is different from the expected outcomes
negatively in the sulfur test, indicated by deep (which could either be white or yellow
yellow coloration. However, sulfanilic acid fusion precipitate), so the solubility of this precipitate
solution turned blue violet, which is a positive
was not tested anymore. Among the unknown,
indication of sulfur. Among the remaining
unknowns, unknown 5 exhibited a similar result unknown 6 exhibited yellow precipitation and is
with sulfanilic acid, suggesting a positive result as slightly soluble as well.
well.
IV. Discussion
Nitrogen Test
The paradigm of Jean Louis Lassaigne on
Table 3. Color appearance of the solution after sodium fusion has a goal of breaking the organic
nitrogen test. covalent bonds between hydrocarbons and
Color of functional groups which contain the elements to
Sample Indication
Solution be tested to form new inorganic compounds
p-chloroaniline light blue + which display color changes during reactions.
chlorobenzene cloudy yellow -
Sulfur-containing groups are usually bonded with
sulfanilic acid blue* +
unknown 1 dirty yellow - carbon chains as sulfonic acids, thioaldehydes,
*after a period of time, dark blue precipitate was thioketones, thiols, and sulfides. Nitrogen is
formed and the solution turned colorless mostly contained in amide, nitrile, amine, and
nitro compounds. Lastly, halogens such as
Nitrogen is present in p-chloroaniline and chlorine, bromine, and iodine are bonded to
sulfanilic acid due to blue coloration of their carbons as halides or acyl halides. These organic
solution after the addition of FeCl3. However, the molecules bind these specific elements or groups
solution in containing sulfanilic acid turned into covalently. However, these bonds are easily
colorless as dark blue precipitate formed and broken by sodium, which is a very strong
settled at the bottom of the tube. P-chloroaniline reducing agent and can break the organic
contrastingly didn’t exhibit this aftermath and compound chain (Kokv, 2011). When these
remained blue the entire time. On the other hand, elements separate from their respective organic
chlorobenzene and unknown 1 exhibited compounds, the tendency is to exist in their
yellowish coloration of the solution, a negative stable ionic form, such as S2-, CN-, Cl-, Br-, and I-
response to nitrogen testing. Unknown 1 was , by which the elements may ionically bind with
described as “dirty” due to the presence of black Na+ during fusion. There must be an excess of
precipitate-like particles. None of the unknowns sodium metal in order for the reaction to proceed
responded positively to nitrogen testing, since towards the formation of ionic compounds. The
none has turned blue.

Chemistry 33: Elemental Analysis by Sodium Fusion Page 3 of 6

newly formed inorganic compounds are then
suspended in the aqueous solution and are
subjected to different reactions during qualitative
testing. Combination reactions such as in ionic
bonding are illustrated below (Shriner, Hermann,
Morrill, Curtin, and Fuson, 2004).
[Eq’n 1] Na+(s) + S2- → Na2S(aq)
[Eq’n 2] Na+(s) + CN- → NaCN(aq)
[Eq’n 3] Na+(s) + X- *→ NaX*(aq)
*where X is any halide i.e.
chloride, bromide, or iodide
During sodium fusion reaction, heating is an
important process and is vital in order to push the
reaction forward as shown in Eq’ns 1, 2, and 3.
Additionally, heating volatilizes any unreacted
organic material from the sample compound in
order to avoid disturbances in the results. When
the ignition tube was red-hot, it was plunged into
a beaker containing distilled water and covered
with wire gauze in order to secure the products in
the aqueous solution. Reheating is an optional
process, although it has been found that higher-
temperature solutions are easier to filter than cold
ones. The filtrate at this point, which is supposed
to be colorless (otherwise indicating an
incomplete fusion reaction), is the sodium fusion
extract, or Lassaigne’s extract, which contains
the inorganic compounds if present and will be
subjected to different qualitative testing to detect
the presence of sulfur, nitrogen, and halogens
(Gower & Rhodes, 1969).
Sulfur Test
[Eq’n 4] NasS(aq) + Na2[Fe(CN)5NO](aq) →
Na4[Fe(CN)5NOS](aq)
As illustrated in Eq’n 1, sulfur exists in the
solution as sodium sulfide. During sulfur testing,
the addition of 2% sodium nitroprusside results to
a combination reaction forming sodium
pentacyanonitrosylferrate (II) (as shown in Eq’n
4). Sodium pentacyanonitrosylferrate (II) appears
in the solution as deep blue-violet in color
(Shriner et al., 2004).
Of the three known compounds, only sulfanilic
acid responded positively to the test, while p-
chloroaniline and chlorobenzene exhibited a
deep yellow coloration. Theoretically, the results
are correct since sulfanilic acid contains sulfonic
acid functional groups (-SO3H), whilst the other
Chemistry 33: Elemental Analysis by Sodium Fusion
two compounds do not contain sulfur. Among the
unknown, unknown 5 has also a positive result,
which suggests that it contains sulfur.
Nitrogen Test
[Eq’n 5] 2 NaCN(aq) + FeSO4 (s) →
Fe(CN)2 (aq) + Na2SO4
[Eq’n 6] Fe(CN)2 (aq) + 4 NaCN(aq) →
Na4Fe(CN)6 (aq)
[Eq’n 7] Na4Fe(CN)6 (aq) + 4 KF(aq) →
K4Fe(CN)6 (aq) + 4 NaF
[Eq’n 8] 3 Na4Fe(CN)6 (aq) + 4 FeCl3 →
Fe4[Fe(CN)6]3 (aq) + 12 NaCl
[Eq’n 9] K4Fe(CN)6 (aq) + FeCl3 (aq) →
KFe[Fe(CN)6](s) + 3 KCl
Eq’n 2 illustrates that nitrogen group in a sodium
fusion exist as sodium cyanide. Upon addition of
ferrous sulfide, sodium will be displaced from the
compound to form ferrous cyanide (Eq’n 5).
Ferrous cyanide will further react and combine
with the remaining sodium cyanide in the solution
to form sodium ferrocyanide (Eq’n 6). Addition of
potassium fluoride in the solution complexes with
sodium ferrocyanide, forming potassium
ferrocyanide (Eq’n 7). Upon the addition of ferric
chloride, both the remaining sodium ferrocyanide
(Eq’n 8) and potassium ferrocyanide (Eq’n 9) will
react and form ferric ferrocyanide and potassium
diiron (III) hexacyanoferrate, respectively
(Haynes, 1966). Early practice in nitrogen testing
did not include the addition of KF, which is why
earlier studies did not always acquire the most
accurate qualitative results in this particular test.
However, the presence of potassium diiron (III)
hexacyannoferrate is confirmed by dark blue
precipitate, specifically Prussian blue (Brainly,
2018). Thus, collectively, the products formed
after addition of ferric chloride provide a
qualitative amount upon determination of
nitrogen presence, which is deduced if Prussian
blue precipitate settles at the bottom of the tube
after the blue coloration of the solution vanishes.
In the experiment, p-chloroaniline and sulfanilic
acid tested positive since the organic structures
of both compounds contain amine groups.
Meanwhile, chlorobenzene exhibited a cloudy
yellow color. Unknown 1 exhibited a dark yellow
coloration as well, which suggests a negative
response for nitrogen testing. One of the
Page 4 of 6
unknowns, unknown 7, encountered a greenish
precipitate. This indicates that the sodium wasn’t
heated enough during fusion, that’s why there
was only a very minute amount of cyanide that
was detected (Kokv, 2011). This result is
commonly encountered in early practices, that’s
why, as discussed, the convention of adding KF
to the solution yields a more desirable data upon
completion.
Halogen Test
[Eq’n 10] NaCN + Na2S + HNO3 →
HCN + H2S + NaNO3 (unbalanced)
[Eq’n 11] NaX + AgNO3 (aq) →
AgX(s) + NaNO3
[Eq’n 12] AgX(s) + NH3 → solubility
In a halogen test, the goal is to precipitate the
halogen with silver (as shown in Eq’n 11) in case
there are any present. However, other organic
compounds may contain other elements or
groups that can complex with silver and form a
precipitate (in this case, nitrogen and sulfur). The
addition of nitric acid to the solution favors the
reaction involving sulfides and cyanides of
forming hydrogen sulfide and hydrogen cyanide,
respectively and as shown in Eq’n 10. The two
aforementioned acids are weak acids that
volatilize upon heating. It is possible that this
mechanism may involve formation of HCl, HBr,
and HI. However, these are strong acids in
comparison with the weak acids which will
evaporate first. Upon the addition of silver nitrate,
the halogens present will complex and form a
precipitate. To distinguish which halogen is
present, the color and solubility in NH3 of
precipitate are observed and tested (Table 4).
This elemental analysis is only limited to chlorine,
bromine, and iodine because of their Ksp
(solubility constant) with silver (review of General
Chemistry principles on acids and solubility). In
order to detect if there are any halogens present
aside from those within the limitations, other tests
must be conducted using other reagents.
Table 5. Color of halide precipitate their solubility
in NH3.
Color of Solubility in
Halogen
Precipitate NH3
chlorine white soluble
bromine yellow slightly soluble
iodine yellow insoluble
Chemistry 33: Elemental Analysis by Sodium Fusion
Silver chloride is a white precipitate and is soluble
in NH3. On the other hand, silver bromide
appears to be yellow and slightly soluble in NH3
as well. Silver iodide is also yellow in color, but is
insoluble in solubility testing (Shriner et al.,
2004). Centrifugation prior to solubility testing
separates the precipitate from the solution and
allows for easy decantation.
During halogen testing in the experiment, p-
chloroaniline and chlorobenzene both produced
a white, soluble precipitate, while, sulfanilic acid
produced black precipitate. This is an undesired
result because upon precipitate formation, the
presence of nitrogen and sulfur in the solution
might affect the results afterwards. Silver cyanide
can be mistakenly observed as silver chloride,
because it also appears as white precipitate.
However, silver sulfide appears to be black. This
is observed in sulfanilic acid, which suggests that
the nitric acid added and the process of heating
did not expel the sulfide in the solution
completely. Among the unknown, the yellow
precipitation on unknown 6 is a false positive
result since it is expected not to exhibit any
precipitation. One possible source of
precipitation is the incomplete expulsion of non-
halogen elements (which was previously
discussed). Unknown 3 must have contained
positive result indicating presence of chlorine, but
possible mishandling of the procedures might
have further expelled them as well.
V. Conclusion and Recommendations
Elemental analysis confirmed the presence of
expected elements in the known compounds.
Sulfanilic acid tested positive for both sulfur and
nitrogen. P-chloroaniline produced a positive
result for both nitrogen and halogen tests, and
the halogen was then identified as chlorine.
Lastly, chlorobenzene tested positive for
halogens, of which chlorine was identified.
Of seven unknown samples subjected to the
three elemental analysis tests, only unknown 5
tested positive for sulfur, while only unknown 6
tested positive for halogens. The halogen was
identified to be bromine. However, some
discrepancies were identified between the
expected results and the obtained data. First,
unknown 3 was expected to test positive for
halogens, specifically chlorine. This is an
indication that the halogen did not completely
Page 5 of 6
react with sodium during fusion. The same case
was found for unknown 7, where nitrogen was
expected to be present. The halogen test result
for unknown 6 was a false positive, as it did not
contain any of the testable elements within the
scope of the study.
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