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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.
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