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Hannah A.

Mercado
A-14L
Group3

Date Submitted:
Date Performed:
Some Investigations on the Corrosion of Iron

I. Introduction
Corrosion is a spontaneous chemical reaction that occurs when metal ions come in
contact with dissolved oxygen and produce rust (Zumdahl, 1998). Some metals continuously
corrode until theres no more left. Due to this, it is an inconvenience that can cost industries
millions in maintenance and replacement of costly equipment. To properly manipulate the
inevitable chemical occurrence of corrosion, its process must be understood to keep it from
damaging metallic equipment and appliances.
The development of rust comes in two parts in a reduction-oxidation (redox) reaction. It
is an electrochemical process wherein different parts of the metals electrochemical cells act as
sites for oxidation and reduction. The following are the half-reactions involved in rusting:
(cathodic reaction) O2(g) + 2H2O(l) + 4e- 4OH-(aq)
(anodic reaction) Fe(s) Fe2+(aq) + 2e-

E= -0.44V
E= -0.40V

Iron must first be oxidized and the resulting electrons would drive the cathodic reaction
to occur and produce OH- from the reduced atmospheric oxygen. A requirement for this to
happen is that both cathode and anode sites are immersed in the same electrolyte for the
corrosion circuit to be complete (Chang, 2011). The resulting hydroxides and Fe ions would
bond and oxidize to form reddish-brown rust (Fe(OH)3) as shown (Whitten et al., 2007):
Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)
Fe(OH)2(s) Fe2O3 . xH2O
This corrosion process could be stopped or hasted by inhibiting or facilitating the anodic
reaction and/or the cathodic reaction as investigated in this experiment (Burton,2000).
The process or presence of iron corrosion could be tracked by knowing if the system has
the presence of Fe2+ ions. This could be confirmed by using an indicator called ferroxyl
(K3Fe(CN)6) where in the Fe2+ ions would react with the indicator and produce a Prussian blue
ion complex (FeFe(CN)6 -) that can be easily seen in the solution. Ferroxyl is continually used in
various experiments for confirmation of iron cations due to its capability to detect the slightest
amounts of Fe2+ ions.
With the use of aqueous solutions, ferroxyl, and agar, conditions that affect the rate of
iron corrosion were studied. Factors such as acidity of solution, mechanical stress on the metal,
and contact with other metals were studied in control environments with appropriate indicators
for observation. The study was conducted at room A-127 Laboratory of Physical Sciences
Building of University of the Philippines Los Baos, Laguna on March 24, 2015.

II. Materials
A. Reagents
B. ApparatusKNO
and 3Equipment
NaOH
NaCl test tubesHNO3
heat plateNa3PO4
HCl
aspirator
KOH pipet andNaSCN
litmus paper

H2SO4
agar
FeSO4 250mL glass beakerCopper strips
pliers
Phenolphthalein
Zinc strips
0.1M K3Fe(CN)6 ferroxyl Iron nails

III. Procedure
A. Effect of Acidity or Basicity of Solution
Clean 2cm iron nails were each carefully placed in 12 prepared test tubes. Each
test tube were filled with various solutions such that the nails were completely
submerged. Three sets of 4 solutions were made. Each set comprised test tubes
with a salt solution, a strong acid, a strong base, and distilled water set as control as
shown in Table 1.
Table 1. Solutions used during test of effect of acidity on iron corrosion.
Chracteristic
Set A
Set B
Set C
strong base
NaOH
KOH
Na3PO4
ionic solution
NaCl
KNO3
NaSCN
strong acid
HCl
HNO3
H2SO4
control
distilled H2O
distilled H2O
distilled H2O
Before the solutions were placed in each test tube, its acidity or basicity was
confirmed using red and blue litmus paper. All the test tubes were then allowed to
stand overnight before observation approximately 48 hours later. Any signs of rusting
were observed and noted in Table 2.
After observations of presence of rusting, two drops of 0.1M ferroxyl (K3Fe(CN)6)
were added into each test tube to confirm for a presence of Fe 2+ ions. Any signs of
color change was observed and recorded. Two drops ferroxyl was also added into a
separate test tube containing ferrous sulfate solution (FeSO 4) to make a control
setup in comparison to the color changes in the experimental solutions. All
observations color change were noted and tabulated in Table 2 and 3.
B. Effect of Mechanical Stress
Agar was prepared by gently boiling 200mL of distilled water. The beaker was
removed from the heat plate and 4g of agar were stirred into the water. The mixture
was then continually heated and stirred until the agar completely dispersed in the
liquid. Ten drops of ferroxyl and 2 drops of phenolphthalein was added and stirred
into the agar mixture. The agar was then cooled to lukewarm.
Two nails are placed at the bottom of a glass beaker. One is bent using a pair of
pliers the other remains unbent. The nails are then submerged in the prepared agar
and cooled until lukewarm. The setup was left to stand overnight before observation
48 hours later. Presence, site, and color of the rust and agar were observed and
tabulated in Table 4.

C. Effect of Contact With Other Metals


A strip of copper metal was winded around a clean iron nail and a strip of zinc
metal winded another nail tightly. Both nails were placed and arranged at the bottom
of a 250mL glass beaker. It was made sure that the nails did not come in contact with
each other.
Agar was prepared and poured into the beaker containing both nails such that
the nails were completely submerged. The setup was left to stand overnight before
observation 48 hours later. Presence, site, and color of the rust were observed and
tabulated in Table 5.
IV. Data/Observations
Table 2. Observations of reactions of iron with various aqueous solutions.
Solution
Acidity
Observations
Presence of rusting
Color of solution after
after standing
adding K2Fe(CN)6
overnight
Set A
NaOH
basic
yellow
NaCl
neutral
dark
yellow
+
HCl
acidic
blue
dH2O
neutral
dark
yellow
+
Set B
KOH
basic
yellow
KNO3
neutral
dark yellow
HNO3
acidic
blue
+
dH2O
neutral
dark yellow
+
Set C
Na3PO4
basic
yellow
NaSCN
neutral
dark yellow
+
H2SO4
acidic
blue
+
dH2O
neutral
dark yellow
+
Table 3. Observation of the reaction between K3Fe(CN)6 and FeSO4 solution.
Reagent
Initial appearance
Appearance after mixing
K3Fe(CN)6 solution
yellow green clear solution
the resulting solution
FeSO4 solution
orange clear solution
change to a blue color due
to the presence of Fe2+
Table 4. Observation of the reaction of iron corrosion as affected by mechanical stress.
Nail (+agar w/ phenolphthalein
Observations
& K3Fe(CN)6)
Iron nail
Brown rusting indicated by a blue tint clings to the
head on the nail. Pink stains surround the nail.
Bent Iron nail
Brown rusting and blue tint is more abundant in the
sample and is seen both in the head of the nail and the
area that is bent. Pink stains surround the nail.

Table 5. Observation on the reactions between metal couples.


Metal couple (+agar)
Observations
Iron nail + Cu strip
Brown rusting is observed at the ends of the iron nail
where the Cu strip isnt coiled.
Iron nail + Zn strip
White rusting is observed at the middle of the iron nail
where the Zn strip is coiled.
V. Discussion
In order to investigate the effects of acidity of solution on the rate of iron corrosion,
several aqueous solutions of different acidic natures were used to submerge the iron nails.
After 48 hours, the entire sets of test tube samples were observed for rusting. According
to Table 2, most of the nails submerged in acidic and neutral solutions had signs of rusting. In
contrast, all the nails submerged in base did not show any signs of rusting. To further confirm,
ferroxyl was added into all the solutions to indicate whether ferrous ions were produced due to
oxidation. All samples with nails submerged in basic and neutral solution turned yellow in the
event of the addition of the indicator. Meanwhile, all the samples submerged in acid solution
turned blue.
When the solution turns blue, it indicates that there is an event of corrosion happening in
the system. The anion of the indicator (Fe(CN)6 3-) reacts with the Fe2+ ions from the oxidation of
Fe from the nail and produces in a Prussian blue ion complex as shown:
Fe2+ + Fe(CN)6 3- FeFe(CN)6Thus, oxidation of Fe occurred The only ones in which the solution turned blue are the
samples submerged in strong acid solutions. Theoretically, the strong acid would assist in the
oxidation of Fe2+ ions therefore it would fasten the corrosion of the metal and the ferroxyl would
indicate the significant concentrations of Fe2+ ions. Errors may have occurred in the samples of
HCl and KNO3 wherein rusting should have been observed but there was none. However, the
ferroxyl results still confirm that oxidation still occurred in HCl.
With the nails submerged in base, it is noticed that none of them had signs of corrosion
both in physical appearance and the ferroxyl test. It may have resulted due to the great
concentrations of OH- already present in the base hindering the reduction of O2 to produce OH-.
Thus, the circuit is temporarily hindered and rusting is delayed.
In the investigation of the effect of mechanical stress on iron corrosion, a bent and
unbent nail were observed for rusting. In Table 3, the data depicts that the head of the nails had
a blue tint and the surrounding agar was colored pink. An additional tint of blue is seen on the
bend of the bent nail. This suggests that an addition of mechanical stress would facilitate the
occurrence of corrosion.
Theoretically, the bending of the nail would increase the stress at the site where it is
bent. Regions within a metal subject to a high local stress will contain metal atoms at a higher
strain energy state. As a result, high-stress regions will be anodic to low-stress regions and can
corrode selectively. Therefore, rust would be produced at the sites of high-stress such as the
bend in the nail.

Experimentally, this is proved by the presence of the pink and blue regions around the
nail. Blue regions on end and bent areas of the nail would indicate the anodic sites wherein
there was high stress that drove the oxidation of iron and the production of iron ions. The Fe 2+
ions reaction with the ferroxyl in the agar created the blue regions. Pink regions on the agar are
the cathodic sites wherein O 2 was reduced to produce OH-. The hydroxides (base) reaction with
the phenolphthalein in the agar created the pink regions.
In the investigation of effect of metal coupling on the area of corrosion, iron nails coiled
with Cu or Zn strips were observed. For the nail coiled with copper, it is observed that the
rusting appeared at the regions where the copper isnt coiled. All the brown rust present is seen
only on the iron nail. Whereas for the nail coiled with zinc, white rusting is observed only on the
area where the zinc strip is coiled.
When reduction occurs, a metals standard reduction potential is considered first. A
metal that has a greater reduction potential would act as the cathode and its anodic reaction
would be preferred. The following are the standard cell potentials of the metals used.
Cu = 0.34V > Fe = -0.44V > Zn = -0.76V
For Cu, its reduction potential is greater than that of Fe (0.34V > -0.44V). Consequently,
the rusting would occur in the iron nail since the Fe metal would act as the anode where
oxidation would take place. Whereas for iron nail coiled with Zn, which has a lesser reduction
potential than Fe (-0.76V < -0.44V), white rusting would occur in the Zn strip as it acts as the
anode and site for oxidation.
VI. Conclusion
For iron to corrode, it must be exposed to oxygen and moisture. A redox reaction would
occur in a circuit and the resulting Fe(OH) 2 would oxidize and produce rust on the anode.
Factors that affect iron corrosion such as acidity of solution, mechanical stress, and metal
coupling were investigated in order to better manage iron corrosion.
Most samples submerged in acid and neutral solutions showed signs of rusting while all
those submerged in basic solution did not show any signs of rusting. Ferroxyl test indicates that
oxidation occurred in all the samples in acidic solution and there were none in the ones
submerged in basic solution. This is because the acid would assist in the oxidation of iron and
the base would hinder the reduction of oxygen thus the iron would respectively corrode faster or
slower.
Corrosion is observed at sites where there have been applications of mechanical stress.
The head and the bent area of the nail acted as anodes and the surrounding of the nail, the
cathode. Rusting occurs in the anodes resulting from the higher strain energy, given by
mechanical stress, that drives the oxidation.
Prevention of iron corrosion can also be done by pairing a desired metal with a metal
that has a lower standard reduction potential. In the experiment, zinc acted as the sacrificial
metal when it produced white rusting and the iron nail remained whole and clean. Copper
encouraged the rusting of the iron nail due to copper having a higher reduction potential and
thus the oxidation and rusting would occur on the iron.

Most of the data gathered were within what was theoretically sound aside from when the
sample with HCl solution did not show signs of rusting. Sources of error may come from
impurities of the nail or the solutions, and insufficient cleaning of glassware. It is recommended
that the experiment be done with double replicates and the sample be stored in a control
environment.
VII. Literature Cited/Bibliography
Burton, G. (2000). Chemical Storylines. United Kingdom, Heinemann.
Chang, R., Oversby, J. (2011). General Chemistry: The Essential Concepts (6 ed). New
th

York: McGraw-Hill.
Whitten, K.W., Davis, R.E., Peck M.L., & Stanley, G.G. (2007). Chemistry (8 ed.). USA:
th

Thomson Brooks/Cole.
Zumdahl, S.S. (1998). Chemical Principles. (3 ed). Houghton Mifflin Company.
rd