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Some Investigations on the corrosion of iron

I.

Introduction

Corrosion is a spontaneous chemical reaction wherein metals are oxidized when

they are exposed to the environment. Consequently, it results to the weakening of
structural strength of metals. This process has a great impact to the economy of
country since billions of money are funded to replace the rusted metals. The most
common example of this phenomenon is the rusting of iron. The hydrated iron (III)
oxide produces a red-brown rust. However, some metals such as aluminum develop
a thin oxide covering which protects their internal structures from further oxidation.
Anodic areas, where the oxidation of metal can occur, should be present for a
corrosion to happen. The general reaction is:
Anode reaction: M(s) -> Mn+ + neCathodic areas, where electrons are consumed, must also be present. There are
many possible half-reactions that can be act upon such as
Cathode reaction: 2H2O (l) + 2e- -> 2OH- (aq) + H2 (g)
O2 (g) + 2H2O(L) +4e - ->OHThe color of rust is affected by the degree of hydration of the iron oxide which
may vary from black to yellow and to the familiar reddish browns that is usually
seen in roofs or gates.
The objectives of these exercise were to state the effects of the following factors
like the acidity and basicity of the solution in contact with the metal, mechanical
stress applied on the metal, and contact with other metals in the corrosion of iron.
II.

Materials
Reagents
Nails
FeSO4
NaoH
agar

NaCl
Distilled H2O
copper strip
HCl
zinc strip

KO4

KNO3
HNO3

Na3PO4
NaSCN

H2SO4
O.1 K3Fe(CN)6

Apparatus
Test tubes
400 mL beaker phenolphthalein blue/Litmus paper
pliers dropper 10 ml pipet aspirator stirring rod

hot plate

III.

Procedures
Reactions of iron with various aqueous solutions
A clean bright nail was placed in each of the five test tubes. Each nail
was carefully slide down the side to avoid the breaking of the bottom of the
test tube. Each test tube was filled with the following solutions such that the
nails were completely immersed.
Set A
NaOH
NaCl
Hcl
Distilled H20

Set B
KOH
KNO3
hNO3
Distilled H20

Set C
Na3PO4
NaSCN
H2SO4
Distilled H20

The acidity of each solution was determined using litmus paper or

phenolphthalein blue. The results were simply recorded as basic, acidic, or neutral.
Afterwards, the nails were allowed to stand overnight in the solutions. The
observable changes that took place were recorded. Then, one to two drops of
potassium ferricyanide ( K3Fe(CN)6) were added. The reaction was observed and
recorded.1 ml of the ferrous sulfate solution was placed into a test tube then one
drop of 0.1 M K3Fe(CN)6 was added. Then, the visible observations were noted.

Preparation of agar medium

200 mL of distilled water was heated to a gentle boil. Then, it was removed
from the hot plate and was stirred in 4g of agar. The heating of the solution was
continued with stirring until the agar is dispersed. Afterwards, 10 drops of
K3Fe(CN)6 and 2 drops of phenolphthalein was added to the agar mxture. Then it
was stirred and allowed to cool until lukewarm temperature.

Reactions of iron as affected by mechanical stress

Two bright clean nails were selected. One nail was placed on one side of the
beaker. The other nail was bend sharply with a pair of pliers and was placed on the
other side of the beaker as shown in figure 12.1 (picture). When the agar mixture
has cooled, it was carefully poured into the beaker until the nails are covered to a
depth of about 0.5 cm. The nails were allowed to stand overnight in the solution.
After standing overnight, the results were observed and recorded.

Reactions involving Metal couples-Two Metals in contact

A clean piece of copper strip was winded around the clean iron nail. The nail
was removed and the copper coil was tighten so the nail will make a tight contact
with the coil when it is reinserted. The procedure was repeated using a zinc strip on
another nail. Then, the nails were placed in a beaker. The nails must not touch each
other. The lukewarm agar was poured into the beaker until the nails are covered to
a depth of about 0.5 cm. The nails were allowed to stand overnight in the solution.
After standing overnight, the results were observed and noted.
IV.
V.

DATA AND RESULTS

DISCUSSION
In determining the reactions of iron with various aqueous solutions, a
clean bright nail was placed in five different test tubes. Each test tube was
filled with assign solutions such that the nails were completely immersed.
The acidity of each solution was determined using phenolphthalein blue or
a litmus paper. The results showed that for set A, NaOH was basic, NaCl
was neutral, and HCl was acidic. In set B, KOH was basic, KNO3 was
neutral, and HNO3 was acidic. For Set C, Na3PO4 was basic, NaSCN was
neutral, and H2SO4 was acidic. All three sets have distilled H20 which was
a neutral solution.
The nails were allowed to stand overnight in the solutions. After
standing overnight, the results showed that for set A, NaOH and HCl with
the iron nail showed no changes. The solution is still clear and colorless
and nothing happened with the Iron nail . Iron nail and NaCl reacted
producing a clear orange solution with an orange precipitate and the tip of
the nail became dark brown. The iron nail also reacted with distilled H2O
producing a clear orange solution with an orange precipitate and rust
surrounded the nail. For Set B, the color of the solution of nail with KOH
and KNO3 is still clear and colorless and no precipitate was formed, but
some parts of the iron nail became brown in color. HNO3 and distilled
H2O also reacted with the iron nail producing a clear orange solution with
some parts of the nail colored brown and no formation of precipitate was
observed. In set C, Na3PO4 and NaSCN a clear yellow solution was
observed, no precipitate was formed, and also no changes was observed
on the iron nail. H2SO4a clear yellow solution was observed with orange
precipitate and no changes was observed in the iron nail. For distilled H2O
with the iron nail, a clear light yellow solution was observed with brown
precipitate and no changes was observed in the iron nail.
After observing the solution, one to two drops of potassium
ferricyanide ( K3Fe(CN)6) was added to the solution. The results showed
that for set A, NaOH, NaCl, and distilled H2O with iron nail produced a
yellow solution. The solution with the HCl and the iron nail became blue in
color. For set B, KOH, KNO3, and distilled H2O with the iron nail also
produced a yellow solution. HNO3 and the iron nail solution became a
color blue solution. In set C, Na3PO4, NaSCN, and distilled water with the

iron nail became a yellow solution. H2So4 with the iron nail produced a
color blue solution.
Potaasium ferricyanide is a clear blue solution while ferrous sulfate is a
clear yellow solution. A drop of 0.1 m ferricyanide was added to the
solution of 1 ml ferrous sulfate. The produced solution was colored blue.
.The solutions showing no indication of corrosions are the solutions of iron
nail with NaOH, NaCl, distilled H2O,KOH, KNO3, Na3PO4, and NaSCN
wherein the solution turn became color yeelow upon addition of
ferricyanide. Solutions showing indications of corrosions are the solutions
of iron nail with HCl, HNO3, and H2SO4 where in the solutions turn blue
upon addition of ferricyanide. Adding potassium ferricyanide to ferrous
sulfate produces a blue solution while ferricyanide added to various
solutions containing nails produces a yellow and blue solution depending
on the acidity of the solution present. The blue color indicates that Fe 2+
was produced upon reaction of potassium ferricyanide with the solution of
HCl, HNO3, and H2SO4 (Birk, 1994).
Ferrous ions react with ferricyanide forming a blue colored solution with
the chemical reaction:
K3Fe(CN)6(aq) + Fe2+(aq)
KFe[Fe(CN)6](s) + 2 K+(aq)
In determining the reactions of iron as affected by mechanical stress,
two bright clean nails was placed inside a beaker. One nail on the other
side and the other one was bent and placed on the other side of the
beaker. A white agar mixture was prepared. After it has cooled down, it
was carefully poured into the beaker until the nails was covered to a depth
of about 0.5 cm and it was allowed to stand overnight. After standing
overnight, the results showed that blue agar color was evident near the
tips of the straight nail and some light pink agar color could also be seen.
Also, blue agar color was evident near the bent part of the bent nail and
also along its tips and some light pink agar was seen. Adding mechanical
stress to the nail increases the rate of corrosion (Kotz et al., 1994).
The blue color in the agar set-up undergoes Oxidation reaction while
the pink color on the agar set-up (Zumdahl, 1986). The chemical reactions
for these set-ups were:
Equation
he anodic oxidation will be: Fe Fe2+ + 2eand the cathodic reduction: 2H2O + 2e- H2 + 2OHi.e. overall: Fe + 2H2O H2 + Fe2+ + 2OHi.e Fe(OH)2 and this precipitates to form a coating that slows further
corrosion.
If both water and air are present, then the corrosion can be severe with
oxygen now as the oxidant
the anodic oxidations: 2Fe 2Fe2+ + 4eand the cathodic reduction: O2 + 2H2O + 4e- 4OH-

i.e. overall: 2Fe + O2 + 2H2O 2Fe(OH)2 with limited O2, magnetite is

formed (Fe3O4), otherwise the familiar red-brown
Fe2O3 H2O rust is found (www. chem.uwimona.edu.jm).
To determine the effect of contact with other metals on the corrosion of
iron, a clean piece of copper was winded to a clean iron nail. The copper
coil was tightened so that the iron nail will make a tight contact with the
coil. The same was done using a zinc strip. The nails was a placed in a
beaker in a way that they dont touch the other to be able to get the best
results. The cooled agar mixture was poured into the beaker where in the
nails were not submerged completely and was allowed to stand overnight.
After standing overnight, the results showed that blue agar near the nail
and a light pink agar was observed around the nail with copper strip coiled
around it. The nail coiled with zinc strip around it showed no changes in
the color of the agar but a white precipitate was seen on the zinc strip.
The iron nail coiled with copper showed an indication of corrosion.
Therefore, the rate of corrosion may increase or decrease depending on
the metal to which the iron is in contact.
Corrosion could of iron could be slowed down by coating it with grease
or oil, or by the formation of a metal oxide as you coat the iron by a
specific metal strip. A good example of this is iron coated with zinc. Zinc is
being oxidized first before any of the iron part. Furthermore, as zinc was
corroded, Zn(OH)2 forms a film that is insoluble and slowed the corrosion
(Chang and Overby, 2008).
During the experiment errors committed may affect the results.
Possible sources of errors are the presence of impurities and human error.
So it is recommended to always use clean apparatuses and materials to
avoid impurities and be careful in labelling the test tubes because the
reagents might be interchange which can affect the results of the
experiment.
VI.

Conclusion
Corrosion is a spontaneous process wherein the metals
deteriorate due to their interaction with the components in the
surroundings. It is evidently seen in metals reacting with acids. For
acidic solution like HNO3, HCl, and H2SO4 with iron nail showed an
indication of corrosion by producing a color blue solution upon addition
of potassium ferricyanide.. Adding mechanical stress to the mtal
increases the rate of corrosion. Also, contact with other metal may
increase or decrease the rate of corrosion of a certain metal. Errors
committed during the experiment may possibly be human error and
the presence of impurities. These may greatly affect the results of the
experiment so it is recommended to always use clean apparatuses and

materials to avoid impurities and be careful in labelling the test tubes

because the reagents might be interchange.

ron forms many intensely colored compounds, and as a fairly reactive metal, it can
displace hydrogen gas from acids and undergoes many exothermic redox reactions.
Here are a few of the more common reactions involving iron and its compounds that
meet your criteria.
Common compounds and reactions of iron. Formulas in italics are actually
nonstoichiometric compounds!
Compound

Appearance

Reactions

Fe2O3 (hematite,
rouge)

rust red to brown

4 Fe(s) + 3 O2(g)
(exothermic)

2 Fe2O3(s)

FeO (wstite)

jet black powder

FeOFe2O3(magnetit black to brown

e)

3 Fe(s) + 2 O2(g)
(exothermic)

FeOFe2O3(s)

FeS (iron sulfuret)

gray to gray brown

Fe(s) + S(s)
FeS(s) (exothermic)
FeS(s) + 2 HCl(aq)
H2S(g) + FeCl2(aq)

FeS2 (pyrite, fool's

gold)

shiny gold or brassy

crystals

4 FeS2(s) + 11 O2
Fe2O3(s)

8 SO2(g) + 2

FeSO47H2O (green
vitriol)

blue-green crystals

Fe(s) + H2SO4(aq)

FeSO4(aq) + H2(g)

Fe2(SO4)3

gray powder

Fe2O3(s) + 3 H2SO4(aq)
Fe2(SO4)3(aq)
+ 3 H2O( )
Fe2(SO4)3(s)
Fe2O3(s) + 3 SO3(g)

FeCl24H2O

blue-green crystals

Fe(s) + 2 HCl(aq)

FeCl36H2O

orange-yellow
crystals

2 FeCl2(aq) + Cl2(g)

FeCl2(aq) + H2(g)
2 FeCl3(aq)

Iron oxides. The best known reaction of iron is rusting, in which iron reacts with
oxygen and water to form red hydrated Fe2O3. Wrapping a thermometer bulb in wet
steel wool results in a small but noticeable temperature rise; rusting is exothermic.
The color of dried Fe2O3 is intense, and it is used as a red pigment in pints, rubber,

ceramics, and glass. Burning the dry steel wool in air results in magnetite,
FeOFe2O3, a black addition compound that is weakly magnetic.
Iron sulfides. Heating iron filings with powdered sulfur results in a strongly
exothermic reaction that produces a charcoal-grey substance. While the substance
is commonly identified as iron(II) sulfide, FeS, it has a complex structure and is not a
stoichiometric compound (see Cotton and Wilkinson for details). FeS2 (pyrite) is a
brassy, shiny mineral sometimes mistaken for gold. It is not iron(IV) sulfide; the iron
is in a +2 oxidation state, combined with an S 22- ion (the sulfur analog of the
peroxide ion). Pyrite burns when heated to form sulfur dioxide and iron(III) oxide:
4 FeS2(s) + 11 O2

2 Fe2O3(s) + 8 SO2(g)

The reaction is sometimes used in industry as a source of sulfur dioxide for the
manufacture of sulfuric acid.
Iron sulfates. Iron is a fairly active metal and can easily displace hydrogen from
mineral acid solutions. It reacts vigorously and exothermically with sulfuric acid to
produce iron(II) sulfate:
Fe(s) + H2SO4(aq)

FeSO4(aq) + H2(g)

Drying the solution produces green vitriol: blue-green crystals of FeSO47 H2O. Air
oxidizes iron(II) salts to iron(III), and the crystals are soon crusted with brown
iron(III) hydroxides and sulfates. Iron(II) sulfate is used to make writing inks and
dyes by reaction with "tannic acid" (a complex mixture of organic acids extracted
from tree bark), followed by air oxidation to make intensely blue-black iron(III)
tannates.
Iron halides. Iron displaces hydrogen from hydrochloric acid to form pale green
iron(II) chloride:
Fe(s) + 2 HCl(aq)

FeCl2(aq) + H2(g)

The chloride crystallizes as FeCl24 H2O. Exposure to air gradually oxidizes the
iron(II) to FeCl3and Fe2O3. Oxidizing FeCl2 with Cl2 produces orange-yellow FeCl3,
which has metal-nonmetal bonds with covalent character.
Iron thiocyanates. When iron(III) ions are added to a solution containing
thiocyanate ions, a series of brilliantly red complexes form (Fe(SCN) 3, Fe(SCN)63-,
FeSCN+2...) Thiocyanate is a sensitive test for iron(III) only- iron(II) does not cause a
color change. This makes iron(II) thiocyanate useful as a quick test for the presence
of peroxides and oxygen, which rapidly oxidize pale green Fe(SCN) 23H2O crystals to
red iron(III) thiocyanate.
http://www.chemtopics.com/unit13/corros.pdf
http://antoine.frostburg.edu/chem/senese/101/inorganic/faq/iron-reactions.shtml
http://projects.icbse.com/chemistry-262

http://wwwchem.uwimona.edu.jm/courses/iron.html

Iron complex cyanides Both iron(II) and iron(III) ions form very stable complexes
with the cyanide ion (in fact, iron is used to complex waste cyanides to render them
less toxic.) Theferrocyanide (Fe(CN)64+) and ferricyanide ion (Fe(CN)63+) contain
covalent iron-carbon bonds arranged octahedrally around the central iron. An
intensely colored pigment can be made by combining these ions with iron in a
different oxidation state:
K4Fe(CN)6(aq) + Fe3+(aq)

KFe[Fe(CN)6](s) + 3 K+(aq)

The same pigment can be obtained from the reaction of iron(II) with ferricyanide:
K3Fe(CN)6(aq) + Fe2+(aq)

KFe[Fe(CN)6](s) + 2 K+(aq)

The product of the reaction is the blue color ingredient in many artist's pigments,
printing inks, and dyes (including Berlin blue, Chinese blue, mineral blue, Paris blue,
and Prussian blue). The reaction is also used in blueprinting. The undeveloped paper
is coated with iron(III), ferricyanide ion, and citrate. When the paper is exposed to
light, the citrate reduces the iron(III) to iron(II). Moistening the paper forms the deep
blue pigment.