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SOME INVESTIGATIONS ON THE CORROSION OF IRON
I.

Introduction

Electricity is one important product of the reactions in voltaic cells or batteries.

However, this reactions also leads to unfavorable outcomes. The electrochemical
basis of this reaction underlies the process of corrosion (Petrucci et al, 2011).
The process of corrosion is one view of returning metals to its natural state from
which they were originally obtained in ores (Zumdahl et al, 2010). Corrosion is
defined as the deterioration of metals due to the electrochemical process it
undergoes. In our surroundings, many manifestations of corrosion is taking
place. Some of these are the formation of green patina on copper and brass,
tarnishing of silver, and the most common is the rusting of iron. Corrosion is
responsible in the immense damages in cars, buildings, bridges, ships, and other
metal-involved infrastructures and equipment. (Chang et al, 2013). It involves
oxidation or conversion of uncombined metals into oxides or other compounds
(Torio et al, 2012). The corrosion of metals except gold is so because their
standard reduction potentials is less positive compared to that of oxygen gas.
Thus, when their half-reactions is reversed and combined with the half-reaction
of oxygen, the total charge (Ecello) would be positive, which says that the reaction
is spontaneous. However, the positive value does not tell how fast the oxidation
of metals by oxygen will occur (Zumdahl et al, 2010).
Since our experiment focuses mainly to rusting of iron, lets take it first into
consideration. The reactions involved in corrosion of iron is held quite complex
and is not completely understood yet. However, main steps are believed to be as
what really occurs in the reaction. In order for rust to form, oxygen gas and
water must be present on iron. Oxidation occurs at a certain region of the
metals surface which serves as anode:
Fe(s)

Fe2+(aq)

2e-

+0.44 V

The charge of the reaction is positive since we reverse the reaction. In another
region of the same metals surface, this electron product reduces atmospheric
oxygen forming water at the cathode.
O2 (g)

4H+(aq)

4e-

2H2O(l)

+1.23 V

The overall redox reaction is

2Fe(s)

O2 (g)

4H+(aq)

2Fe2+(aq)

Computing for the standard electromotive force (E ocell):

Eocell

Eocathode

Eoanode

2H2O(l)

= 1.23 V

(-0.44 V)

=1.67 V
By convention, the Eoanode would still be in negative sign since the reaction in the
anode is oxidation but the formula has already factored the negative sign.
Since H+ ions is supplied in part due to the reaction of atmospheric CO 2 with
water forming H2CO3, this reaction occurs in an acidic medium.
Further oxidation of Fe2+ by oxygen occurs again in the anode through the
reaction:
4Fe2+(aq)

O2 (g)

(4+2x)H2O (l)

2Fe2O3 xH2O (s)

+8H+(aq)

Rust
A product of the reaction which is a hydrated form of Iron (III) oxides is the one
known as the rust. We represent the formula as Fe 2O3 xH2O since the amount
of H2O associated with the Iron (III) oxide varies. Through migration of electrons
and ions, electrical circuit is completed (Chang et al, 2013). Varying color of the
rust from black to yellow to the familiar reddish brown is affected by the degree
of hydration of the iron oxide (Zumdahl et al, 2010).
Other than iron, other metals also undergo corrosion. Like for example
aluminum, a metal used in building airplanes and making beverage cans. Since it
has a more negative standard reduction potential compared to Fe, it has a
greater tendency to oxidize than iron does. However, we do not see airplanes
dissolving and corroding in rainstorms. This is so because the layer of insoluble
Al2O3 that forms on its surface after it has been exposed to air shields the
aluminum underneath from further corrosion. In the case of iron, rust is too
porous to protect the iron underneath. Metals like copper and silver also corrode
much more slowly. After being exposed in atmosphere, copper forms a verdigris
which is basic Copper carbonate (CuCO 3), a green substance also called as
patina, which protects metal underneath from further corrosion. Similarly,
silverwares, after coming to contact with foods, develop a film of black silver
sulfide (Ag2S) layer.
In this particular experiment, the class stated the effects of three factors on the
corrosion of iron. These factors are; the acidity or basicity of the solution in
contact with the metal, mechanical stress applied on the metal and lastly, its
contact with other metals.
Objectives
II.

Materials
A. Reagents
Part A
12 small bright nail
NaOH
NaCl

HCl
KOH
KNO3
HNO3
Na3PO4
NaSCN
H2SO4
dH2O
12 - 1 to 2 drops 0.1 M K3Fe(CN)6
1 mL FeSO4
Part B and C
1 drop of 0.1 M K3Fe(CN)6
200 mL dH2O
4g agar
10 drops K3Fe(CN)6
2 drops phenolphthalein
4 big and bright nails
Copper strip
Zinc strip

B. Apparatus/Other Materials
12 centrifuge
tubes
1 test tube
Phenolphthalein
Hot plate

3 -250 mL beaker
Stirring rod
Pliers
Sand paper

III.

Procedure
A. Reaction of Iron with various Aqueous Solutions
To carry out the experiment, small nails was polished first with
sandpaper in order to remove the rust it already has. Each nails was
putted in each of the five centrifuge tubes. They were carefully slid down
the bottom to avoid breaking of tubes. Each tubes was filled with solutions
categorized in three sets A, B, and C. Our group was assigned with Set A
containing NaOH, NaCl, HCl, and distilled H 2O solutions. The acidity of
each solution was determined using phenolphthalein. Then, the nails was
allowed to stand overnight in the solutions. Observations on changes that
took place was recorded on Table _____. After standing overnight, one to
two drops of 0.1 M potassium ferricyanide (K 3Fe(CN)6) solution was added
into each test tube. The potassium ferricyanide dissociated to form K + and
[Fe(CN)6]3-. Changes in the solution was observed and noted. In order to
give descriptions to K3Fe(CN)6 solution, together with FeSO4 solution, a
drop of 0.1 M K3Fe(CN)6 was added to 1mL FeSO4 solution placed in a test
tube. Visible observations of the reaction was noted in Table ______.

Preparation of Agar Medium

About 200 mL of distilled water was heated to a gentle boil to be used

in making agar medium. The heated water was removed from hot plate
and was added with 4 g agar. After addition, the mixture was stirred and
continued to be heated until the agar is spread all throughout. Then, 10
drops of K3Fe(CN)6 and 2 drops of phenolphthalein was added to the agar
mixture. The mixture was allowed to cool until lukewarm.
B. Reactions of Iron as affected by Mechanical Stress
Two large nails were refurbished to be used in the experiment. One nail
was placed in the beaker while the other was bent with a pair of pliers
before putted in the same beaker but not allowing the two nails to touch
each other. The cooled agar mixture was carefully poured into the beaker
until the nails were covered to a depth of about 0.5 cm. Then, the beaker
was allowed to stand overnight. Changes on the nails were observed and
recorded in Table ______.
C. Reactions Involving Metal Couples Two Metals in Contact
Same is done in having the large nails polished beforehand in this next
experiment. A clean piece of copper strip was winded around the clean
iron nail. Then the coil was allowed to be tightened by removing the nail
and tightening the copper coil. Thus, when the nail was reinserted it made
a tight contact with the coil. Same procedure was done using a zinc strip
instead of copper on another nail. These nails together with its
constricting coil were placed in the beaker. However, the nails was
ensured not to touch each other. Then, the lukewarm agar mixture was
poured into the beaker as what was done before in part B. The beaker was

allowed to stand overnight until changes is observable. Changes was

recorded in Table ____.
IV.

Data/Observations
Table 12.1 Observations of the reaction of Iron with various aqueous
soln after standing overnight and upon addition of K 3Fe(CN)6

tA

OH

Cl

Se

Cl

H 2O

tB

OH

Se

Na
Na

K
K

NO3

After
standing overnight

No corrosion
observed

Brown ppt
formed; nail
corroded

Brown ppt
formed; dull
texture; corroded
tip

Brown ppt
formed;
concentrated
rusting on the tip

After
standing overnight

No corrosion
observed
S
l
i
g
h
t

Upon addition of
K3Fe(CN)6

turned yellow
green

turned yellow

pH

Basic

Neutral

Turned blue

Acidic

turned yellow

neutral

pH

Basic

Neutral

Upon addition of
K3Fe(CN)6

turned Yellow
green

Turned yellow

c
o
r
r
o
s
i
o
n

NO3

H 2O

Red brown
ppt formed; dull
color of nail

Brown ppt
formed;

Turned blue

Acidic

Turned yellow

neutral

Se

tC

Na

PO4

SCN

H2

SO4

H 2O

Na

concentrated
rusting on the tip

After
standing overnight

White ppt
(error); cloudy
mixture

Brown ppt
formed

Gas evolved;

Upon addition of
K3Fe(CN)6

Turned Yellow
green

pH

basic

Turned Yellow

neutral

Turned blue

Acidic

Brown ppt

Turned yellow

neutral
formed;
concentrated
rusting on the tip
Table 12.2 Observations of the reaction of K3Fe(CN)6 with FeSO4

KFeSO4
Reaction b/w K3Fe(CN)6

Fe(CN)
and
FeSO
3
6
4

Light

Rusty

Bluish green with blue

bright yellow
colored, orange ,
precipitate
green soln
with rust
Table 12.3 Observations of the reaction of Iron after standing overnight
in agar set-ups

V.

Agar Set-ups
Straight nail

Bent nail

Nail coiled with Cu strips

Nail coiled with Zn strips

Changes overnight

Rusting is spreaded; pink color

body of nail; dark blue tip and head

Prominent rust on bent part;

dark blue on tip, head, and bent
portion; pink is the rest of the nail

Rusting on the nail; pink color

following traces on Cu strip, dark blue
rust on nail

Rusting on the Zn strips; pink

nail; faint white color on Zinc

Discussion

Based on our three objectives, the results were derive from the
experiment. The tables tell the factors that could affect the corrosion of
iron.

The first factor to be tested in the experiment is the acidity and

basicity of the solution in contact with the metal which is iron. From the
results of the experiment found in Table ___, it shows that basic solutions
have induced no observable sign of corrosion on the nail. These solutions
are NaOH and KOH. Since the dissociation of base has a product OH -,
O2 (g)
+
2H2O (l)
+ 4e
4OH-(aq)

 increasing its concentration hinders the reduction reaction above of the

oxygen (explained by Le Chateliers Principle) thus, blocking the corrosion.

However, in the acidic solutions, the results from Table ___ shows
that the nail corroded varying on the acid used. The HCl reacted to form
brown rust while the HNO3 reacted to form red brown rust, and lastly,
H2SO4 producing orange brown rust. The acids dissociation forms H + ions
and it is a reactant in the overall redox reaction below.
2Fe(s)
+
O2 (g)
+
4H+(aq)
2Fe2+(aq)
+
2H2O(l)
Thus, we increase the concentration of H+ ions shifting the redox forward to
form Fe2+ ions and water. The concentration of H + in the reaction:

4Fe2+(aq)

O2 (g)

(4+2x)H2O (l)

2Fe2O3 xH2O (s)

+8H+(aq)

is not increased since the this reaction occurs in the anode and the overall
redox is in the cathode.

In condition wherein salt solution is used, the reactions according to

Table ___, shows that the iron nail generally corroded except Na 3PO4 which
happen to be a basic salt. These salt solutions are NaCl, KNO 3, and NaSCN. This
salts dissociates readily into its ions. This ions helps facilitate the corrosion
process by providing electrons with a means of transportation between the
anodic and cathodic regions of the iron nail. Thus, salts serves somehow as
catalyst of the reaction.

Water is a requisite in rusting, thus it serves as the control to show

which reactions corroded most and which did not.

Upon addition of K3Fe(CN)6 to each mixture with nail Table ___ suggest;
basic mixtures just retained the color of the K 3Fe(CN)6 which is yellow green,
acidic mixtures produces blue precipitate, and salt and water turned yellow. The
reaction of K3Fe(CN)6 and FeSO4 produces a blue green colored mixture with a
blue precipitate in it. This blue precipitate is an iron blue called Turnbulls blue. It
signifies the reaction when Fe 2+ is treated with K3Fe(CN)6 (Petrucci et al, 2011).
The FeSO4 dissociate into Fe2+ and SO42-, and the Fe2+ reacts with K3Fe(CN)6 to
produce the blue precipitate. Thus, acidic mixtures that turned blue has evidence
of having Fe2+ ion in the solution showing oxidation.

In the second part of the experiment, the set up was putted in an agar
solution to retain the location of color and rust formation. K 3Fe(CN)6 and
phenolphthalein was added to detect the presence of Fe 2+ ion and basic region of
the nail respectively. The next factor which is the application of mechanical
stress was tested. After overnight, the straight nail appeared to have rust all
throughout it. The body of the nail is colored pink thus a basic region which is
the site of reduction (O2 (g)
+
2H2O (l)
+ 4e
4OH-(aq)) reaction due
to the presence of OH in the product side. The tip and head of the nail appeared
to be dark blue (presence of Turnbulls blue) which specifies the oxidation site.
Since the reduction occurs in the cathode and the oxidation at anode, the body
of the nail serves as the cathode while its head and tip as the anode. However,

upon application of mechanical stress by bending the nail, the nail appeared to
have a Turnbulls blue at the bent portion thus the oxidations sites were
increased to three (tip, head, and bent portion). Because the strained metal is
more active thus more anodic than unstrained metal, the nail preferentially
oxidized at portions like this. This is similar to the preferential rusting of a dented
automobile fender (Petrucci et al, 2011).

The third part of the experiment was about the effect of contact with
other metals on the rusting of iron. After overnight stand of nail coiled with Cu
strip, the nail was still rusted. It is so that iron can be electroplated with Cu and
be protected from rust, but once the coating is cracked, the underlying iron
starts to corrode. Since iron is more active than Cu, it undergoes oxidation and
copper plating undergoes reduction half-reactions. Thats why the copper strip is
pink whilst the iron is dark blue and rusted according to Table ___.

Reduction half reactions: Cu2+

2e-

Cu

Oxidation Half-reactions: Fe

Fe2+

2e-

Overall reaction:

Fe

Cu2+

Cu

Fe2+

While in the zinc strip coiled on iron, the zinc coats the iron which is
known as galvanized iron. Since zinc is more active compared to iron, the iron is
still protected from rusting even if the zinc plating is broken. Zinc is oxidized
instead of iron and corrosion of zinc protects it from further corrosion. The faint
white precipitate in the zinc strip mentioned in Table __ is characterized by zinc
ferricyanide as the reaction of K3Fe(CN)6 with Zn. The part of the nail uncovered
with zinc was colored pink thus a reduction site.

Reduction half reactions: Fe2+

2e-

Fe

Oxidation Half-reactions: Zn

Zn2+

2e-

Overall reaction:

Zn

Fe2+

Fe

Zn2+

The zinc serves as the anode and the oxidation site while the iron as
the cathode and reduction site (Petrucci et al, 2011).

The errors committed in the experiment may mainly concern to the

uncertain concentration of the reagents that affected the rate of corrosion. The
experiment may also be faulty due to the impure reagents like the white
substance in the Na3PO4. The colors also in the 2nd and 3rd part of the experiment
was not quite observable and this may be accounted in the insufficient amount
of indicating substance like phenolphthalein and K 3Fe(CN)6. I may suggest from
the experiment to add more time for the experiment in order to achieve most
favorable result and give points on certain highlights like why did KNO 3 did not
quite evidenced rusting.

VI.

Conclusion

Rusting of an iron is mainly affected by the three given factors. From

the experiment on acidity and basicity of solution in contact with the metal, we
could generalize that:

basic solutions induces unappreciable rusting on the metal

acidic solutions induces the metal to rust further
salt solutions catalyze the corrosion reaction of the metal
and water solution induces rust on the iron typically

On the second part of the experiment, mechanical stress on metal was

tested to affect rusting. It can be concluded that strained metal portion has
evidenced of the oxidation site and serves as the anode while the unstrained
portion serves as the cathode and the reduction site.

Lastly, contact with other metals affect the rusting of metal concerned.
The metal with the most active or most anodic (characterized by less
standard reduction potential) will be the one to be corroded and the other will
be the cathode of the reaction.
VII.

Literature Cited/Bibliography
-Chang, R., Goldsby, K. A, Chemistry 11th Edition, McGraw-Hill
Publishers, McGraw-Hill Companies, Inc., 1221 Avenue of the
Americas, New York, NY 10020, 2013
-Petrucci, R. H., Herring F.G., Madura, J. D., Bissonnette, C., General
Chemistry: Principles and Modern Applications 10 th Edition, Pearson
Prentice Hall, Pearson Canada Inc., Toronto, Ontario, 2011
-Torio, M.A. O., Revilleza, Ma. J. R., et al, Laboratory Instruction
Manual for CHEM 17.1: General Chemistry II Laboratory, General
Chemistry and Chemical Education Division, Institute of Chemistry,
CAS, UPLB, Los Baos, Laguna, 2012
-Zumdahl, S. S., Zumdahl S. A. et al, Chemistry, 8 th Edition, Brooks
Cole, Cengage Learning, 10 Davis Drive, Belmont, CA, USA, 2010