EXPERIMENT IV

NITROGEN OXIDATION NUMBERS

31 March 2014
A. Objective
Studying the redox reaction of nitric acid and nitrate salts , nitric acid and redox reactions
redox reaction of ammonia
B. Basic Theory
Nitrogen contained in the free atmosphere and is the largest atmospheric constituent
gases (78% ) . Compound that formed from the combination of nitrogen with other
elements very much . Of the nitrogen compounds have varying oxidation number ( +5 , +3
, +2 , +1 , 0 , -1 , -2 , -3 ) . Nitrogen can combine with hydrogen to form a hydride
compounds , with oxygen to form oxides , with hydrogen and oxygen to form oxyacids
and can also form the oxy acid halide compounds . In addition, nitrogen can also form as
sodium nitrate and potassium nitrate . Examples of nitrogen compounds and oxidation
number are presented in the following .
Oxidation number
-3
-2
-1
0
+1
+2
+3
+4
+5
(Tim Dosen Kimia Anorganik, 2015)

Compound
NH3 (ammonia)
N2H4 (hydrazin)
NH2OH (hydroxilamin)
N2 (dinitrogen)
N2O (dinitrogen oxide)
NO (nitrogen oxide)
N2O3 (dinitrogen trioxide)
NO2 (nitrogen dioxide)
HNO3 (nitrate acid)

Most nitrogen is present in nature as N2 because this molecule is very stable . This gas is
colorless , odorless , ridak reactive , boils at -196 C and frozen at -210 C .
Ketidakreaktifan is caused by a triple bond strength .
:N N:
Bond energy is as high as 946 kJ/mol.
In the laboratory , the nitrogen can be made by heating a solution containing a salt of
ammonia and nitrite salts . The reaction is:
NH4+ (aq) + NO2- (aq)
N2 (g) + 2H2O (l)
Commercially nitrogen obtained by liquefaction of air . Mostly used to make ammonia, urea,
ammonium sulfate and nitric acid . Because nitrogen is not reactive , then nitrogen is used as
an inert gas blanket to eliminate oxygen in the manufacture of electronic devices . A large
number of liquid nitrogen is used in the food industry due to the low temperature ( -196 C )
so as to accelerate the cooling process .

Nitrogen can bind covalently with some non-metal elements , especially hydrogen and
oxygen . Nitrogen greater electronegativity than hydrogen but smaller than oxygen . As a
result , the oxidation number of nitrogen would be a negative sign if bound with hydrogen ,
while if it unites with oxygen is positive . For example : NH3 and NO2 .
Ammonia ( NH3 ) is a nitrogen compound that is very important because it is the raw
material for making other
Feimportant nitrogen compounds such as urea and nitrogen oxides .
Ammonia is commercially prepared by the Haber process , namely N2 and H2 gas mixing
with the iron catalyst .
H2(g) + 3H2(g)
2NH3
H = -92kJ mol-1
1000
atm
reversed

This reaction can be

so as to form an equilibrium .
In the laboratory , the ammonia is made from ammonium salts with strong bases or basic
oxide .
NaOH + NH4Cl NH3 + NaCl + H2O
CaO + 2NH4Cl 2NH3 + CaCl2 + H2O
Both of these reactions can be used for qualitative analysis of ammonium ion ( NH4 + ) with
ammonia odor that stimulate or tested with litmus . Ammonia is a colorless gas with a boiling
point of -33.35 C and -77.7 C freezing point .
Ammonia dissolved in water with a concentration of about 15m or 28 % by mass , because
the water and ammonia can form hydrogen bonds . Ammonia in water is alkaline due to the
equilibrium :
NH2 + H2O NH4+ + OH- Kb = 1,8.10-5
Ammonia is useful for producing these compounds by the reaction of ammonia and oxygen
( Ostwald process ) .
4NH3 (g) + 5O2 (g)
4NO (g) + 6H2O (g)
Then immediately oxidized to NO2
2NO (g) + O2 (g) 2NO2 (g)
3NO2 (g) + H2O (l) 2HNO3 + NO (g)
Nitrogen dioxide ( NO2 ) and nitrogen oxide ( NO ) is produced in the combustion of
ammonia to nitric acid .
NH3 (g)
NO (g)
NO2 (g)
HNO3 (g) + NO (g)
katali
s

Nitrogen oxide is a gas that is colorless and have unpaired electrons .

Nitrogen dioxide is a reddish-brown gas , is toxic and has a resonance structure :
Nitric acid can not be isolated in pure liquid form because it is easily decomposed by
disproportionation reaction .
3HNO2 HNO3 + H2O + 2NO
HNO2 is oxidizing with iodine ions ( I- ) and as a reducing agent with the permanganate ion
(MnO4-).
2HNO2 + 2H+ + 2I- I2 + 2NO + 2H2O
5HNO2 + H+ + 2MnO4- Mn2+ + 5NO3- + 3H2O
In the laboratory , nitric acid is made through the following reaction :
KNO3 (s) + H2SO4 (l)
KHSO4 (s) + HNO3 (g)
Atoms formed can be separated by condensing because of its form in the form of gas .

Pure nitric acid is a colorless liquid , easily decomposes above 0 C to NO2, H2O dan O2.
4HNO3
4NO2 + O2 + 2H2O
Not reddish brown ( looks yellow when diluted )
HNO3 is a strong acid and a strong oxidizing . These compounds can dissolve most metals .
The results of the reaction depends on the concentration of HNO3 and dilute .
Cu + 2NO3- + 4H+ Cu2+ + 2NO2 + 2H2O (concentrate)
3Cu + 2NO3- + 8H+ 3Cu2+ + 2NO + 4H2O (aqueous)
(Achmad, 1992)
C. Equipment and Materials
Equipmet:
1. Test tube
2. 250ml beaker glass
3. 100ml Erlenmeyer
4. Stirring Bar
Materials:
1. Litmus indicator
2. Sulphuric acid 0,05 M
3. Kalium nitrat padat
4. Copper nitrate
5. Ammonium dichromate
6. Alumunium metal
7. Cu (keping logam)
8. NaOH 0,05 M
9. HNO3 concentrated
10. HNO3 7 M
11. HNO3 2 M
12. KI
13. KMnO4
14. Ice cube

D. Procedure
1. Redox reaction of nitric acid with nitrate salt
Experiment 1: The reaction of nitric acid with copper

Insert the copper metal into

a test tube.Add a few drops
of concentrated nitric
acid.Observe the reaction

Dilute 2 ml of nitric acid to

obtain a solution of nitric
acid 7 M.Add three pieces of
copper and note the gas
that is formed

Experiment 2: Heating of Nitrate Salts

Heat a solid KNO3 in a
test tube

In a different test
tube,heat the
Cu(NO3)2solid.Check
the gas and residual
solids generated in a
test tube

Observe the
changes that
occurred in both
tubes

Experiment 3: Nitrate reduction in alkaline solution

Insert into a test tube 2
ml of 2M HNO3 and 5 ml of
dilute NaOH solution

Add one piece of metal

AI,thenreheat.Check the gas
generated using litmus paper

2. Redox reaction of nitric acid

Experiment 4: Formation and Redox Reaction of nitric acid
Refrigerate 10 ml of dilute sulfuric acid in a test tube with ice for 5 minutes

Enter the sulfuric acid into the tube containing 1 gr of NaNO 3

Note the color of the solution,what compounds are formed

Divide the solution into 3 parts.Heat the tube first and then observe the

IntoInto
thethe
second
thirdtube,add
tube,addaKMnO
little 4KI.Observe
observe the
the
changes
changes

E. Observation Data
a. Changes in the experiment 1:
1. The color of solution change into tosca blue, appearance gas
2. The color of the solution change into tosca blue, appear gas, the copper was soluble
b. Reaction that occur in the experiment 1:
1. Cu (s) + 4HNO3pekat (aq) Cu(NO3)2 (aq) + 2NO2 (g) + 2H2O (l)
2. 3Cu (s) + 8HNO3 (aq) 3Cu(NO3)2 (aq) + 2NO (g) + 4H2O (l)
c. Changes in the experiment 2:
1. KNO3 melting and immediately to be solid again produce white solid
2. The color change as occurred to be dark blue, melting and tobe solid again
d. Reaction that occur in the experiment 2:
1. 2KNO3 (s) K2O (s) + 2NO2(g) + O2 (g)
2. Cu(NO3)2 . 3H2O (s) CuO (s) + 2NO2 (g) + O2 (g) + 3H2O
e. Changes in the experiment 3:
The color of the solution is colorless, produce gas, red litmus becomes blue litmus
f. Reaction that occur in the experiment 3:
1. NaOH (aq) + HNO3 (aq) NaNO3 (aq) + H2O (aq)
2. 3NO3- (aq) + Al (s) + 5OH- (aq) + 18 H2O(l) 3NH3 (g) + 8[Al(OH)4]-(aq)
g. Changes in the experiment 4:
Tube 1 : produce gases NO
Tube 2 : produce gas, the color of solution is yellow
Tube 3 : not produce gas, purple color
h. Reaction that occur in the experiment 3:
1. Tube I
H2SO4 (aq) + NaNO3 (s) NaHSO4 (aq) + HNO2 (aq) + O2(g)
3HNO2 (aq) 3HNO3 (aq) + 2NO (g) + H2O (l)
2. Tube II
2NO2- (aq) + 2I- (aq) + 4H+ (aq) 2NO (g) + I2 (aq) + 2H2O (l)
3. Tube III
5NO2- (aq) + 2MnO4- (aq) + 6H+ (aq) 5NO3- (aq) + 2Mn2+ (aq) + 3H2O (l)
F. Discussion
Redox Reaction of Nitric Acid with Salt Nitrate
Experiment 1 : Reaction of Nitric Acid with Copper

This experiment aims to identify and understand the redox reactions that occur
between concentrated nitric acid and dilute nitric acid when reacted with metallic copper. The
first experiments were conducted was reacting concentrated nitric acid solution with 1 piece
of copper metal. Once the puck drops of concentrated nitric acid copper , the solution initially
translucent color turns into green tosca and there are bubbles of gas and gas appears brownish
yellow. In invitro copper coins everything dissolves and the solution turns into blue.
Reaction occurs :
4HNO3 (l) + Cu (s) NO2 (s) + Cu2+ (aq) + 2OH- (aq)
+
5

+
4

0
-1
(reduksi)

+
2

+2

From the reaction

above showed that the resulting reaction NO2 is brownish yellow
(oksidasi)
seen in the walls of the reaction tube . In this case copper undergo oxidation reaction of Cu
into Cu2+ ( Cu acts as a reducing agent ) with an increase in oxidation number from 0 to +2 .
Then thr experienced a reduction reaction of nitrogen (nitrogen acts as an oxidizing agent)
with a decrease in the oxidation state of +5 to +4 . While the blue color produced by the
solution due to the presence of Cu 2+ ions . In this reaction produced NO2 gas is used as a
solution of concentrated nitric acid. This is consistent with the theory that if a metal is reacted
with concentrated nitric acid it will produce NO2 gas
In the next experiment, 3 pieces of copper reacted with 7M HNO 3 solution , resulting blue
solution and there are gas bubbles and dissolved copper pieces .
8HNO3(aq) + 3Cu (s) 3Cu(NO3)2 (aq) + 2NO (g) + 4H2O (l)
+
5

0
+2
(oksidasi)

+
2

+
2
-3
(reduksi)

From the above reaction showed that the reaction of NO gases produced. The
resulting gas is different from the first reaction as in the second experiment used solution is a
solution of nitric acid 7M. This is consistent with the theory that if a metal is reacted with
dilute nitric acid it will produce gas NO. In the above reaction of Cu acts as a reducing agent
because of an oxidation reaction of Cu into Cu (NO 3) 2 with an increase in oxidation state
from 0 to +2. While nitrogen acts as an oxidant due to the reduction reaction of NO with
HNO3 into decline becomes +2 oxidation state of +5.
In this experiment, the second reaction runs slower than the first reaction. This is
due to the use of different nitric acid solution. In the first experiment used a solution of
concentrated nitric acid while in the second experiment used 7M nitric acid solution. So it can
be said that the higher the concentration of nitric acid used, the ability to oxidize the copper
will be even greater. In addition, the resulting compound is different where the experiments
using concentrated nitric acid oxidizes into Cu2+ and Cu produced NO2 gas while in the
experiments using dilute nitric acid to form a compound of Cu (NO 3) 2 and NO gas is
produced.
Experiment 2. Heating Nitrate salts
This experiment aims to identify and understand the redox reactions that occur in
heating nitrate salts. The first experiment was heated spatula white solid KNO 3 in a test
tube. Solid KNO3 were heated to melt and there is a gas bubble. When tested with litmus
paper red, red litmus paper remains. Then after a few time idle, which has melted KNO 3
formed into a solid back .

Reaction occurs :
2KNO3 (s) K2O (s) + 2NO2 (g) + O2 (g)
+
1

+
+
2
5
+1
(oksidasi)
-1

+
4

(reduksi)
From the above
reaction of nitrogen undergo reduction reaction of NO3 into NO 2
with a decrease in the oxidation state of +5 to +4 .
In the second experiment is heated spatula Cu ( NO3 ) 2 in blue into the reaction
tube . Cu ( NO3 ) 2 solid are heated to melt and there is a gas bubble . After Cu ( NO3 ) 2
melt , melts into dark blue . When tested with litmus paper red , red litmus paper remains .
Reaction occurs :
Cu(NO3)2 . H2O (s) CuO (s) + 2NO2 (g) + O2 (g) + 3H2O
+ -2
5

+
4
+2
(oksidasi)

-1
(reduksi)

From the above reaction of nitrogen undergo reduction reaction of NO 3 into NO2
with a decrease in the oxidation state of +5 to +4.
Of both the above reaction, it is known that heating nitrate salts produce NO 2 and
O2 gas. This is evidenced by the red litmus paper test. After testing the fixed red litmus paper
red. This suggests that both the gas mixture is acidic. Based on the existing theory, NO 2 gases
and O2 gas are acidic and alkaline. In this gas mixture, the acidic nature of NO 2 gas is
stronger than the alkaline nature of O2 gas. So the red litmus paper remains red. Heating
function in this experiment is to accelerate the reaction. In addition, NO 2 gas including toxic
gases and is highly soluble in water to form a mixture of nitric acid and nitrite. This is why
when the gas and the solution was tested with pH indicator paper produces acid.
In this case nitrogen acts as salt reduction reactions. Nitrate is reduced to nitrite that N acts
as an oxidant for the oxidation state of nitrogen decreased. In general, nitrate salts Pb (NO 3) 2
is used in the manufacture of NO 2 gas because it contains no water at the time of
crystallization, the oxygen produced can be separated by flow through the cooling mixture of
ice and salt, and NO2 will be condensed as a pale yellow solution. NO 2 is an odd number of
electrons molecules.
Experiment 3. Nitrate Reduction in Alkaline Solution
This experiment aims to identify and understand the nitrate reduction reaction in
alkaline solution. This experiment was carried out by reacting a solution of 2 M nitric acid
with aqueous NaOH solution and coupled with a coin al. These experiments resulted in clear
and colored solutions coin Al sink. Prior to heating, metal Al was not directly react with a
mixture of nitric acid solution with NaOH solution, but after warming gas bubbles appear.
This indicates that the warming may accelerate the reaction.
From the reaction of ammonia gas is produced. Heating is done also serves to evaporate the
ammonia gas. When tested with litmus paper red color is still red. The trial was supposed to
be blue litmus paper, because the gas produced is ammonia gas and alkaline and Al which are
amphoteric metals tend to base.
Reaction occurs:
3NO3- (aq) + 8Al (s) + 5OH-(aq) + 18H2O (aq) NH3 (aq) + 8[Al(OH)4]+
5

-3
-8
(reduksi)

+4
(oksidasi)

+
4

From the above reaction of nitrogen undergo reduction reaction with a decrease in
the oxidation state of +5 be -3. This means HNO3 solution acts as an oxidant for aluminum.
While the aluminum metal undergoes oxidation with an increase in oxidation of 0 to +4 .
Redox Reactions of Nitrous Acid
Experiment 4. Formation and Nitric Acid Redox Reactions
This experiment aims to identify and understand the formation of nitric acid and
redox reactions. This experiment was carried out by reacting a solution of dilute sulfuric acid
with NaNO3 solid. Before reacted , sulfuric acid solution was cooled in advance for 5
minutes. This is done in order for the gas that is formed from the decomposition NaNO 3 will
slow down a little and solubility. After reacting with dilute sulfuric acid solution, NaNO3 will
dissolve and clear colorless solution.
Reaction occurs :
H2SO4 (aq) + NaNO3 (s) NaHSO4 (aq) + HNO2 (aq) + 1/2 O2 (g)
Furthermore, the solution was divided into 3 parts :
Tube 1. Heating HNO2 solution
When the solution is heated HNO2 produced gas bubbles are NO gas and the
solution was translucent color. This reaction produces nitrate compounds.
Reaction occurs :
3 HNO2 (aq) HNO3 (aq) + 2NO (g) + H2O (l)
+
3

+2
(oksidasi)

+
+
5
2
-1 (reduksi)

The above reaction is a disproportionation reaction (derived from the same species),
where the nitrogen oxidation reactions (in HNO3) with increase in oxidation state of +3 to +5
and experienced a reduction reaction (at NO) with a decrease in oxidation number of +3 be
+2 .
Tube 2. The solution HNO2 + KI solution
When the solution of KI was treated with a solution HNO 2 resulting yellow
solution. This reaction takes place under acidic conditions and the resulting NO gas is
colorless .
Reaction occurs :
2NO2 (aq) + 2KI (aq) 2KOH (g) + 2NO (aq) + I2 (aq)
+
3

-1

-1
(reduksi)

+
2

+1

(oksidasi)
From the above reaction of nitrogen undergo
reduction reaction with a decrease in
oxidation number of +3 be +2, where NO2 acts as an oxidant. While I undergo oxidation
reaction with the increase in oxidation number of -1 to 0 , where KI acts as a reducing agent.

Tube 3. Solution HNO2 + KMnO4 solution

When the solution of KMnO4was treated with a solution HNO2 resulting purple
solution. This reaction takes place in acidic conditions.
Reaction occurs :

5NO2- (aq) + 2MnO4- (aq) + 6H+ 5KNO3 + 2Mn2+ +3H2O

+
3

+
7

+2
(oksidasi)

+
5

+
2
-5

From the above reaction of nitrogen undergo

oxidation reaction with increase in
(reduksi)
oxidation state of +3 to +5, where nitrite acts as a reducing agent, whereas Mn experienced a
reduction reaction with a decrease in the oxidation state of +7 be +2, where MnO 4permanganate ions act as an oxidant .

G. Conclusion
1. Concentrated nitric acid when reacted with the metal will result in NO2 gas, whereas
dilute nitric acid when reacted with the metal will produce gas NO.
2. In the reaction of concentrated nitric acid, nitrogen experienced a reduction reaction
with a decrease in the oxidation state of +5 to +4. While the reaction of dilute nitric
acid, nitrogen experienced a reduction reaction with a decrease in the oxidation state
of +5 be +2.
3. Reaction heating nitrate salts KNO3 and Cu (NO3) 2 produce NO2 gas, which
experienced a reduction reaction of nitrogen with a reduced oxidation state of +5 to
+4.
4. Nitrate reduction reaction in alkaline solution produces ammonia gas, which
experienced a reduction reaction of nitrogen with a decrease in the oxidation state of
+5 be -3.
5. In the heating nitric acid, nitrogen oxidation reactions (in HNO3) with increase in
oxidation state of +3 to +5 and undergo reduction reaction (at NO) with a decrease in
oxidation number of +3 be +2.
6. In reaction to the tube 2, nitrogen undergo reduction reaction with a decrease in
oxidation number of +3 be +2.
7. In the reaction tube to 3, nitrogen undergo oxidation reaction by the increase in
oxidation state of +3 to +5
8. In this experiment nitrogen oxidation states have varied, ie -3, +2, +3, +4, and +5. In
addition, nitrogen can act as an oxidant, reductant, or both.
H. Suggestion
1.
2.
3.
4.

Practitioner should be more careful and meticulous during the practicum

Practitioner must understand the material before doing the lab
The tools that will used should be sterilized beforehand
Practitioner should work closely with members of the group

I. Refference
Achmad, Hiskia. 1992. Penuntun Belajar Kimia Dasar, Kimia Unsur Petrokimia.
Bandung: PT. Citra Aditya Bakti.
Cotton dan Wikinson. 1989. Kimia Anorganik Dasar. Jakarta: Universitas Indonesia.
S, Syukri. 1992. Kimia Dasar 2. Bandung: ITB.

Saadi, Parham dan Mahdian. 2008. Panduan Praktikum Kimia Anorganik. Banjarmasin:
FKIP UNLAM.
Tim Dosen Kimia Anorganik. 2015. Petunjuk Praktikum Kimia Anorganik. Semarang:
Unnes.