PHOTOCHEMICAL REDUCTION OF ION IRON (III)

Semarang, 15th April 2016

A. Objective
Study the iron (III) reduction as a result of photochemical reaction and understand their
application in blueprints.
B. Basic Theory
Photochemical is part of the chemistry that studies the interactions between atoms,
small molecules and light (or electromagnetic radiation). As well as other disciplines,
photochemical system using SI or metric units. Units and constants are often used include
the meter, second, hertz, joules, moles, the gas constant R, and the constants Bolztmann. All
units and constants is also part of the field of physical chemistry.
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 transition. 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 metal most, and believed to be the chemical elements to the ten most
banya in nature. A large amount of iron in the earth thought to contribute to the Earth's
magnetic field. Its symbol Fe summary Ferrum Latin name for iron. Iron is a metal produced
from iron ore, and rare in the free state. In the industry, the iron produced from ore, mostly
hematite (Fe2O3), through reduction by carbon at a temperature of 20000C.
2 C + O2 2 CO
3 CO + Fe2O3 2 Fe + 3 CO2
Iron produced can be used in the synthesis of compounds containing Fe. Some of the
complex compounds with Fe central atom is

FeIII [(2,2-bipryridine) (HPO3) (H2PO4)]

Complex M [TCNQ]
Complex Fe (II) - Cr (III) Oxalate
(Petrucci, 1989)

FeO, Fe2O3, and Fe3O4 almost as if linked to its structure. Oxygen atoms in all of the
configuration structure c.c.p. in stoichiometric FeO shaped oktahidral all bound by the Fe
atom, which gives the effect of NaCl lattice of Fe 2+ da O2. Comparison of these two ions in
their compounds is approximately 48.56%. Removal of Fe3 + from Zink Aridear and
replacement with two to three of the number Fe 3+ gives FeO in reduced iron show more
accurate data than the addition of oxygen when the iron three-four aserrimeritan Fe 2+ is
replaced by Fe3+ ions will form compound Fe3O4, and a spinel structure.
(Heslop & Robinson, 1969)

Photochemical is the study of chemical reactions induced by light directly or indirectly.

Ordinary thermal reaction that takes place in the dark to obtain the activation energy of the
photon absorption of light by the molecules. Therefore this reaction provides the possibility of
high selectivity, which means that the energy of a quantum of light appropriate for the specific
reaction. The excited molecular electronic state and distribution of energy have different
electron from the ground state, so that the different chemical properties. Photochemical
reaction is a chemical reaction caused by light or ultraviolet radiation. Incoming photons are
absorbed by the reactant molecules generate excited molecules or molecules of free
radicals, which then react again. In photochemical there are two basic laws.
According to the first law of Grothus (1817) and Draper (1843), photochemical
change can only be brought about by the light absorbed. Radiation that is not absorbed but
can push excited molecules to emit light. The second law of photochemical proposed by
Stark and Einstein (1908-1912) stated that the molecule absorbs the incoming light quantum
becomes activated.
(Alberty, 1984)
Processing blueprint is still very rare, but the manufacturing process is usually very
easy blueprint blueprint paper, coated with ammonium iron citrate and potassium ferisianida
that are sensitive to light. The imaging process is done on a light translucent fabric or paper
that was placed on one sheet of paper blueprints and opened at a place illuminated by a
strong light. Light transform ammonium iron citrate salt into a compound of iron, then when
the paper soaked in water, salts of iron compounds react with potassium ferisianida to form a
deep blue solution which makes the paper become blue. Chemicals on paper protected from
light by a line of paper or dissolve 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 the change by light.
(Biddle, 1949)
According Syamsidar in his book Practical Inorganic Chemistry Introducing Washmolding is the process to process the film shooting results to be negative or positive film and
then printed. Wash print consists of two steps, namely the washing process uses a chemical
solution and printing process using light-sensitive paper that illuminated a light through the
film that has been washed. Wash-print or skills that are popular with the term blueprint can
be learned from the scientific aspects, namely from the point of electrochemical and
photochemical. If the iron (II) is reacted with hexacyanoferrat (III) then formed a blue solution.
The magnitude of the effect of light on the reduction of iron (III) to iron (II) seems to fit the
blue color density formed. From this case, then it was tested with the title of the
photochemical reduction of iron (III), which aims to study the reduction reaction of iron (III) in
photochemical and its utilization for studying blueprints.
(Syamsidar,2012)

C. Equipment and Material

Material :
1.
2.
3.
4.

1M oxalic acid
0,1M diammonium hidrofosfat
Solution of iron (III) chloride 0,1M
HVS paper and tracing paper

5.
6.
7.
8.

0,1M hydrochloric acid solution

Solution of K3Fe(CN)6 0,1M
Solution og 0,03 M K2Cr2O7
Filter paper

9.
10. Equipment :
1. 1 pieces beaker glass 250ml
2. Pipette

3. Tweezers
4. Chips of glass

5.
D. Procedure
6.
1.

2.

Solution made from mixture

of 10 mL of irom (III) chloride
0,5 M in 10 mL diammonium
7. hidrofosfat 0,5 M in glass
beaker 250 ml.
8.

Solution being kept in a dark

room (cupboard).

Solution being added by 10

9. mL of oxalic acid 1 M to a
solution of iron (III) chloride is
10.
in the cupboard.

Solution being stirred well in

dark room

11.
Cupboard being closed and
opened only when necessary.

12.
13.
14.

3.

15. 4 sheets of HVS paper taken

and dipped into the solution
in the cupboard.

all the papers immersed

solutionbeing kept but does
not damage the paper.

16.
17.
18.
4.

paper removed and placed

between two filter paper.

This step being done in the

cupboard

19.
20.
21.
A sharper will be produced,so
22. the paper must be dried for
one night.
23.
24.
25.
26.
27.

5.

After it was dry, the paper was used as a

sensitive paper.

Make the object on tracing

28. paper with the black ink or
make object with black
paper, for

Paper being left between the

two filter paper for 10-15
minutes so that the paper
become dry.

29.
30.
6.

The objects was placed on

sensitized paper and nip with
two pieces of glass, then hitted
31.
the sunlight for 4-5 minutes.
32.

7.

Sensitized paper that has been

irradiate with light then dipped
33.
into a solution of
heksasianoferrat ion (III) 0,1 M.
34.
35. 8.
the paper was removed and dip
it in a dilute solution of
36.
potassium dichromate (0,03 M).
37.

all the papers immersed was

kept in the solution.

Then the paper was washed

with 100 ml of 0,1 M HCl

38.
39.

Followed by tap water and

let it dry in atmosphere.

40.
41.
E. Observation Data
42. Result of Observation :
1.
2.
3.
4.
5.
6.

Color of iron (II) chloride solution at first

Color of diammonium hidrofosfat solution first
Color of mixed solution
Color of the solution plus a mixture of oxalic acid
Color of paper after being immersed in the solution
Printouts :

43.
44.
45.

: orange or yellow-brownish
: colorless solution
: yellow
: yellow
: light yellow

7. Reactions :
46.
47. FeCl3 (aq) + (NH4)2HPO4

48.
(aq)

(aq)

FePO4 (aq) + 2NH4Cl (aq) + HCl (aq)

2FePO4 (aq) + 3H2C2O4 (aq)

2FeC2O4 (aq) + 2H3PO4

+ 2CO2 (aq)
49.

Fe2+ (aq) +

K3[Fe(CN)6] (aq)

[Fe(CN)3]

2K3[Fe(CN)6]

(aq)

Fe4[Fe (CN)6]3 (s)

50.

3 K2Cr2O7 (aq) +

2[Fe(CN)6]3- (aq)

(aq)

3Cr2O72- (aq)
51.

K2Cr2O7 (aq) +

2HCl (aq)

2KCl (aq) +

H2Cr2O7 (aq)

52.
F. Discussion
53.
54. Practical photochemical reduction of iron ( III ) aims to study the reduction of iron
ions and the use of blueprints . The first thing to do is mix between iron ( III ) chloride
with diammonium hidrosulfat that the mixing is done in a dark place ( cupboard ) .
Because utilizing reduction reaction of iron ( III ) , the prepared solution should also
consist of iron ( III ) . Then mixed with oxalic acid . Oxalic acid here acts as a reducing
agent. Here Oxalic acid will reduce iron ( III ) be on the iron ( II ) and keep it in order
not oxidised back . The mixing is done in the dark because the light will affect the
reduction process, iron ( III ) to iron ( II ) .
55. The reaction that occrs in the mixing solution :
56. FeCl3 + (NH4)2HPO4
FePO4 + 2 NH4Cl + HCl
57. Based on the reaction seen that diammonium hidrofosfat can slow reduction
reaction Fe3+ because Fe3+ will react with the PO43- form FePO4 with stable bond that
requires great energy to reduce Fe3+ .
58. Furthermore, the mixed solution coupled with a solution of oxalic acid. This oxalic acid
solution serves as a reducing agent that will reduce iron (III) to iron ( II ).
59. Reaction that occur :
60. 2 FePO4 + 3 H2C2O4
2 FeC2O4 + 2 H3PO4 + 2 CO2
61. Ionic eaction that occur :
62. Reduction : Fe3+ + eFe2+
263. Oxidation : C2O4
2CO2 + 2e
3+
64.
2Fe + 2e
2Fe2+
265.
C2O4
2CO2 + 2e3+
22Fe + C2O4
2Fe2+ + 2CO2
66.
67. Energy derived from the sun will cause collisions between the particles with
the compound more quickly so that berlagsung reaction will be faster as well. If these
redox reactions take place quickly, it will be difficult to observe the reduction reaction
occurs. 4 sheets of paper HVS then dipped in a solution of + - 15 minutes. In this
dyeing should be done carefully so that the paper is not damaged.
68. After the dyeing is complete, HVS dried sandwiched between two filter paper.
The dried paper is used as a sensitive paper which is then clamped with a glass

object. The purpose of clamping the glass is that objects are not exposed to UV rays
directly and so the object printed clearly on the final result. With the arrangement of
glass objects, objects of paper, sensitized paper, and covered again with a glass
object. This is because the use of filter paper filter paper has a strong absorption so
that the drying process can take place quickly. The paper was dried for + - 30
minutes. Drying is also have function to ensure the solution has seeped into the
paper. This immersion is done in a dark room, so that sunlight does not enter. The
paper then removed and placed between two filter paper until the paper is left to dry
in a dark room. This meant that the iron reduction process can occur optimally. In
addition, the filter paper has a strong absorption so that the drying process can take
place quickly. Drying is done for 30 minutes, in order to produce sharper prints.
69.
While waiting for dry sensitive paper, made object creation. Our group
made two variations in creating objects, namely on tracing paper and paperboard.
Where the tracing paper written writing AKU and KAMU, the paperboard made
patterns (love). Variations irradiation was done by varying the time between 15 and
20 minutes (only with UV light). At the time of this experiment, only the irradiation
using UV light. Because of cloudy weather at the time, then irradiating with sunlight
can not do. The function of irradiation that mold removal between the paper pen and
paper objects can take place properly. And aims to oxidize iron (II) which has been
produced in the previous process into iron (III). But the part that has been covered
with markers on the object creation (writing and patterns) did not participate oxidized
to iron (III) for the part covered by the ink, and it is blocking the process of oxidation.
This stage is called photochemical stage which chemical reactions can take place
with the help of sunlight or UV rays. . At the time of the reaction process in the
darkroom aims to prevent the occurrence of photochemical process known as
reaction antifotokimia. Irradiation is conducted with variation within 15 minutes for
writing AKU and love pattern (rectangle with the love in the center) and within 20
minutes for writing KAMU and love cut pattern.
70.
71.
Sensitive paper is dipped in a solution of potassium heksasianoferrat
using tweezers, where the solution has a function as a conduit of blue color on
sensitized paper so that the object can be seen written. Blue color that appears is the
effect of oxidation reactions of iron (II) to iron (III) due to sun exposure. K2CrO7 then
dipped in a solution, which serves to remove impurities such as ions
heksasianoferrat. Then dipped in a solution of HCl which is used to remove dirt left
over from washing with K2CrO7 as well as to clean up the possibility of diammonium
excess in the event of a reaction.
72. Reaction that occur when dipped in potassium heksasianoferrat:
2+
3Fe3+(aq) + [Fe(CN)6]473. Fe (aq) + [Fe(CN)6] (aq)
74. Furthermore, these ions combine and produce a blue color Turnbull:
75. 4Fe3+(aq) + 3[Fe(CN)6]4Fe4[Fe(CN)6]3
76.
turnbull blue
77.
On the reaction seems that the reaction between Fe 2+ with [Fe (CN)
6] 3-produce blue Turnbull.
78. Reaction that occur when dipped into K2CrO7 and HCl :
79. 3 K2Cr2O7 + 2 [Fe(CN)6]32 K3[Fe(CN)6] + 3 Cr2O722 KCl + H2Cr2O7
80. K2Cr2O7 + 2 HCl

81.
The last phase is washed with tap water sensitive paper by means
flowed slowly so sensitive paper does not tear. It aims to eliminate excess HCl ions
and salts.
82.
83.
84.
85.
86.
(a)
(b)
(a) It was dipped in potassium heksasianoferrat
(b) It was dipped in K2CrO7
(c) It was dipped in HCl

(c)

87.
In this experiment performed variations of the time is for 15 minutes
and 20 minutes, both were irradiated with UV light. Irradiation treatment 15 minutes
made for the object marked "AKU" and the pattern of love in the middle or can be
called the (a) picture below.. While the irradiation treatment for 20 minutes performed
for the object read "KAMU" and patterns of love (b picture below). Having compared
the results of irradiation for 15 minutes and 20 minutes has a difference in their prints.
Wherein the longer exposure time (20 minutes) the printed image more clearly than
the irradiation time of 15 minutes. The relationship between the length of exposure
time with the appearance of the object is created, ie the longer the exposure time, it is
possible the longer the time that is given to reduce Fe3 + to Fe2 +, so that the blue
color can be seen more clearly. The white color in the bottom part of product is
because when it wa irradiated with the UV light, one of the UV light is turn off. So the
light can not spread over all the paper.
88.
89.
90.
91.
92.
93.
94.
(a)

(b)
95.

96.
G. Conclusion
a. Fe3+ is reduced to Fe2+ with the help of sunlight where this reaction produces a blue
color

b. Knowing the influence of light on the process of photochemical reduction of iron (III) is
characterized by the formation of turnbull blue color after the addition of potassium
heksasianoferrat(III)
c. The longer the time given to reduce Fe3+ to Fe2+, blue look more apparent.
97.
H. References
98.
99.

Alberty, R.A. 1984. Thermodinamic of Biochemical Reaction. New Jersey: John

Wiley and Sons Inc. .

100.

Biddle,H.C. 1949. Chemistry Today. USA :Rand Mcalley and Company

101.
102.
Heslop,R.B. and Robinson P.L. 1960. Inorganic Chemistry:A Guide for
Advance Study, Elsever,Amsfer.
103.
104.
HS, Syamsidar. 2011. Penunutun Practical Inorganic Chemistry.
Makassar: UIN Press
105.
Erlangga
106.
107.

Petrucci, H.Rapl. 1989. Inorganic Chemistry. Volume 2. New York: