April 14th 2015

EXPERIMENT VI
PHOTOCHEMICAL REDUCTION OF ION IRON (III)
A. Objectives
Study the iron (III) reduction as a result of photochemical reaction and understand their
application in blueprints.
B. Theoritical Basic
Photochemistry is part of chemistry that studies the interaction between atoms, small
molecules and light (or electromagnetic radiation). As with other disciplines, photochemical
use SI units or metric system. Units and constants are often used include the meter, second,
hertz, joules, moles, R the gas constant, and constants Bolztmann. All units and constants is
also part of the field of physical chemistry.
Concentrated nitric acid, cold, iron ions are formed into a passive, in these circumstances,
it does not react with dilute nitric acid nor creak copper and a copper salt water solution. (G.
Svehla, 1985: 257)
Photochemistry is the study of chemical reactions induced by light directly or indirectly.
Ordinary thermal reaction which takes place in the dark obtain the activation energy of the
photon absorption of light by molecules. Therefore this reaction gives the possibility high
selectivity, which means that the energy of a quantum of light appropriate for a particular
reaction. The excited electronic state of the molecule and the energy distribution of electrons
having different from the ground state, so that the properties of different kimianyapun.
(Alberty, 1984)
Photochemical reaction is a chemical reaction caused by light or ultraviolet radiation.
Incoming photon is absorbed by molecules excited reactant molecules or molecules produce
free radicals, which then reacts again. (Alberty, 1984)
In photochemical there are two basic laws. According to the first law of Grothus (1817)
and Draper (1843), photochemical changes can only be brought about by light absorbed.
Radiation is not absorbed but can push the excited molecules to emit light. The second law of
photochemical proposed by Stark and Einstein (1908-1912) states that the molecule that
absorbs the incoming light quantum becomes activated. (Alberty, 1984)
Photosynthesis is a chemical reaction that requires light to allow the formation of sugars
from cellulose may occur from CO2 and H2O. The sunlight helps the formation of vitamin D in
the body. Bleaching cloth and straw material usually using sunlight. The blueprint was
developed by emitting light on iron compounds. In the world of photography silver and halogen
compounds undergo changes by light. (Biddle, 1949)
Blue print processing is still very rare, but the manufacturing process is usually very easy
blueprint blueprint paper, coated with iron ammonium citrate and potassium ferisianida are
sensitive to light. The imaging process is done on a translucent fabric or paper placed on top of
a sheet of blueprint paper and opened the place irradiated by intense light. Light turn iron
ammonium citrate salt of a compound of iron, then when the paper soaked in water, salts of
iron reacts with potassium ferisianida to form a dark blue solution which makes the paper
becomes blue. Chemicals on paper protected from light by a line of paper or dissolving the

image and result in paper or image to white. The blueprint was developed by emitting light on
iron compounds. In the world of photography silver and halogen compounds undergo change of
the light. (Biddle, 1949)
Absorption of electromagnetic radiation by ionic species in solution requires electrons in
the ion can move from one energy level to another. Absorbed light must have energy equal to
the difference and the energy levels in transisisi. If the transition energy lies at wavelengths of
visible light, then the light component is absorbed and transmitted light will be colored.
Transmitted light color is the complementary color and the color is absorbed. The rise of an
electron from a low energy level to a higher level of lead absorption components of white light
and the light that is passed colors.
Iron is the second metal that abundance in nature after the firt of aluminium. Most of the
iron is in the form of hematite, Fe2O3, magnetite, Fe3O4, lemonit, FeO(OH) and siderite, FeCO3.
Ferrous metals easily soluble in dilute mineral acids. With non-oxidizing acids and free air, the
iron ions will dissolve into the iron (II), whereas if there is aair or oxidizing acids will be
produced ions o iron (III).
Ions of iron (III) in solution easily reduced to iron (II) with a weak reducing agent, such
as I-ion.
Fe3+ + I
Fe2+ + I2
Ion solution, ions of iron (III) form complexes with water molecules as a ligand. This complex
ion has a tendency to undergo hydrolysis.
2[Fe(H2O)6]3+ [Fe(H2O)4(OH)2 Fe(H2O)4]4+ + 2H+
[Fe(H2O)6]3+ [Fe(H2O)5(OH)]2+ + H+
(Team of lectureship inorganic chemistry, 2015)
C. Equipment and Material
Equipment :
1. 1 piece glass 400 ml beaker
2. The dark room (cupboard)
3. Chips of glass
4. Tweezers
Material :
1. 1 M oxalic acid
2. 0.1 M diammonium hydrophosphate
3. Solution of iron (III) chloride 0.1 M
4. HVS paper and tracing paper
5. 0.1M hydrochloric acid solution
6. Solution of K3Fe(CN)6 0.1M
7. Solution of 0.03M K2Cr2O7
8. Filter paper

D. Work Instruction
10 ml of iron (III) chloride 0.5M in 10 ml
diammonium hydrophosphate 0.5M mixed

Kept the solution in a dark

room
Added 10 ml of oxalic acid 1M,
stired in dark room. Closed the
cupboard and opened only when
necessary

Taked 4 sheets of HVS paper and dip into the solution

in cupboard
The paper removed and olace it between 2 filter paper. Leave
paper in between the 2 filter paper for 10-15 minutes until
paper dry.
The paper must be dried for one night, the paper was used as a sensitive
paper

Object made on tracing paper with black ink/object with

black paper

Place the pbject on sensitized paper and nip with two pieces of glass,
hited in the sunlight for 4-5 minutes
Removed paper and dip it in a dilute solution of potassium
dichromate 0.03M, washed the paper with 100 ml of HCl,
followed by tap water and let it dry in atmosphere

Sensitive paper that has been irradiated with light then dipped
into a solution of hexacianoferrat ion (III) 0.1M (ketuker
langkah kerjanya)
E. Result of observation
1. Color of iron (III) chloride solution at first
: orange / yellow brownish
2. Color of diammonium hydrophosphate solution first: colorless

3.
4.
5.
6.

Color of mixed solution : yellow

Color of the solution plus a mixture of oxalic acid : yellow
Color of paper after being immersed in the solution : yellow - brownish
Printouts (result of printing) :
Object
Papper
Lighting (minutes)
Note
Write ITA
Tracing
5
Cant printout
Sign =
Carton
10
Object
can
printout, but only
a half part
Write FRIDA
Tracing
15
Cant printout
Sign
Carton
20
Object
can
printout,
but
indistinct

7. Reactions
:
Iron(III) chloride + Diammonium hydrophosphate
FeCl3(aq) + (NH4)2HPO4(aq) FePO4(aq) + 2NH4Cl(aq) + HCl(aq)
Mixture-1 + oxalic acid
2FePO4(aq) + 3H2C2O4(aq)
2 FeC2O4(aq) + 2 H3PO4(aq) + 2CO2(g)
Ion reaction :
Reduction : 2Fe3+ + 2e- 2Fe2+
Oxidaton : C2O42 2CO2 + 2eRedox : 2Fe3++ C2O42- 2Fe2+ + 2 CO2
Dip into hexacyanoferrat(III) ion
Fe2+(aq) + [Fe(CN)6]3-(aq)
Fe3+(aq) + [Fe(CN)6]4-(aq)
3+
4Fe (aq) + [Fe(CN)6] (aq)
Fe[Fe(CN)6]
Washed with potassium dichromate
3K2Cr2O7(aq) + 2 [Fe(CN)6]3-(aq) 2K3[Fe(CN)6](aq) + 3 Cr2O72-(aq)
Washed with HCl
K2Cr2O7(aq) + 2HCl(aq)
2KCl(aq) + H2Cr2O7(aq)
F. Discussion
Photochemical reduction of iron (III) experiment is to study that reduction of iron (III)
with sunlight used to aplication blue printout. Iron (III) reducted become iron (II), this
experiment need 2 condition there are nothing light (dark room) and light.
Practicant who has little body go into dark room, then mix iron (III) chloride solution and
diammonium hydrophosphate solution in dark room. Iron (III) chloride solution as oxidator
and contain Fe3+ ion, its has orange color. Diammonium hydrophosphate as solution to retard
reduction reaction, its has colorless. In this iron(III) still iron (III). Then add oxalic acid
solution for mixture-1. Oxalic acid as reductor, it has colorless. In this part iron (III) reducted
become iron(II). Stirr them and cover the dark room maximally, in order to not any light enter
into dark room. In dark room occurs reaction called antiphotochemical reaction. Look at this
reaction :
Iron(III) chloride + Diammonium hydrophosphate
FeCl3(aq) + (NH4)2HPO4(aq) FePO4(aq) + 2 NH4Cl(aq) + HCl(aq)
Mixture-1 + oxalic acid

2FePO4(aq) + 3H2C2O4(aq)
2 FeC2O4(aq) + 2 H3PO4(aq) + 2 CO2(g)
Redox : 2 Fe3++ C2O42- 2 Fe2+ + 2 CO2
Based on reaction iron (III) already reducted become iron (II). Characteristics also change, the
color of mixture solution is yellow.
We make sensitive paper use HVS paper, 4 pieces. We must make also model or object on
tracing and carton paper. In tracing paper, made word. In carton paper, made shape and cut it.
When mixture solution adsorb on HVS, dried HVS use filter paper in up and down. Filter
paper can adsorb liquid from HVS because has high adsorption capability. Set the sensitive
paper like as glass, object paper (tracing paper with word ITA), sensitiv papper and glass
again. Why must like that? Glass function is cover sensitive paper and object paper from
sunlight direct. Object paper in upper than sensitive paper, inorder to sensitive paper touch
sunlight. So sensitive paper adsorp color from sun, and choose color which suitable with wave
long from mixture solution.
Group 3 make variation of paper kinds, object, and time for lighting. The papers are
tracing and carton paper. On tracing paper created word (ITA and FRIDA), but on carton
prepare created shaped (= and
). Various of lighting time are 5, 10, 15, and 20 (in
minutes). For paper with word ITA lighted for 5 minutes, paper with shape = lighted for 10
minutes, paper with word FRIDA lighted for 15 minutes, and paper with shape
lighted
for 20 minutes.
Certainly lighting need good light, fortunatelly when practicum the weather is bright.
Function of light is remove printout from object paper to sensitive paper. This process called
photochemical, there are chemistry reaction using sunlight. Photochemical reaction can change
Fe2+ to Fe3+.
Every object papper dipped be spread evenly in potassiumhexacyanoferrat [K3Fe(CN)6].
[K3Fe(CN)6] produce blue color on object papper, so we can look object. After that dipped
object paper in potassium dichromate K2Cr2O7. Potassium dichromate solution clean up another
substance not any needed. Then dipped it into HCl, HCl solution can clean up another
substance which not succesed if only use K2Cr2O7. Look at this reaction :
Fe2+(aq) + [Fe(CN)6]3-(aq)
Fe3+(aq) + [Fe(CN)6]4-(aq)
Below iron (III) and complex of Fe gather together produce blue solution. Look at this reaction:
4Fe3+(aq) + 3[Fe(CN)6]4-(aq)

Fe4[Fe(CN)6]3(aq)
Blue trunbull

Based on reaction, sensitive paper can printed blue color if success.

Dip-2 use potassium dichromate solution. The function of potassium dichromate solution
is cleaner another substance needless. Dip-3 use HCl solution, the function of HCl is clean
residue which not bundle by K2Cr2O7. It can also clean diammonium excess. Dip-4 use flow
water from crane, water can remove HCl excess. So printing seen clearly.
Based on experiment, that not occurs for all object paper. For paper with word ITA
lighted for 5 minutes, it cant printout. For paper with shape = lighted for 10 minutes, it can

printout, but only a half part. For paper with word FRIDA lighted for 15 minutes, it cant
printout. The paper with shape lighted for 20 minutes, it printout but indistinct. Based on
theory, time lighting influence printout. As long time as, blue printout more clearly. But group
3, only carton paper which printout. But that still not enough perfect. It means occurs mistaken
from experiment. Maybe that occurs because :
a) Solution (FeCl3, diammonium hydrophosphate, and oxalic acid) already little
contaminated because touch light when mixed. Dark room not really dark room,
because there still a space.
b) Solution (FeCl3, diammonium hydrophosphate, and oxalic acid) not adsorb
maximally by HVS papper, because dipping not along 15 minutes but less from that.
c) Drying not enough, after diped into mixture solution (FeCl3, diammonium
hydrophosphate, and oxalic acid).

G. Conclusion
1. Reduction reaction iron (III) can use light, its called photochemical reaction.
2. In this experiment, we need 2 condition there are bright and dark.
3. If increasingly time of lighting, so increase too ion Fe(III) reducted and blue printout
more clearly.
4. Based on experiment there are mistaken cause printout not perfect.
H. Suggestion
1. We must keep dark room from light.
2. The sensitive paper must dried actually after diped into mixture solution (FeCl 3,
diammonium hydrophosphate, and oxalic acid).

I. Refference
Alberty, R.A. 1984. Thermodinamic of Biochemical Reaction. New Jersy: John Wiley and Sons
Inc.
Biddle,H.C. 1949. Chemistry Today. USA: Rand Mcalley and Company.
Inorganic Chemistry Lecturer Team. 2015. Manual Work of Inorganic Chemistry Practicum.
Semarang : UNNES.
Svehla, G. 1990. Vogel Buku Teks Analisis Anorganik Kualitatif Makro dan Semimikro.
Bagian 1 dan 2 Edisi kelima. Jakarta: PT. Kalman Media Pustaka.