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Group 7

Fita Candra

4301413046

Nurul Latifiyah

4301413083

Bunga Mahardhika 4301413105

OXIDATION NUMBER OF NITROGEN


May, 5th 2015
A. Objectives
Study the redox reaction of nitric acid and nitrate salts, the redox reaction of nitrous acid,
redox reaction of ammonia and ammonia ions
B. Theoretical Background
Most nitrogen is present in nature as N 2 because this molecule is very stable. This gas
is colorless, odorless, non-reactive, boils at -196C and frozen at -210C . The lack of late
is due to the reactive power of the triple bond. Bond energy is as high as 946 kJmol - 1.
:N N:
Nitrogen can bind covalently with some non-metal elements, especially hydrogen
and oxygen. Electronegativity of nitrogen is greater than hydrogen but smaller than
oxygen. As a result, the oxidation state of nitrogen will be marked negatively if bound
with hydrogen, while if it unites with oxygen is positive. For example : NH3 and NO2.
(Taher, 2012)
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)

heat

N2(g) + 2H2O(l)

Ammonia (NH3) is a nitrogen compound that is very important because it is the raw
material for making other important nitrogen compounds such as urea and nitrogen
oxides.
H2(g) + 3H2(g)

2NH3(g)

H = -92kJ mol-1

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 reducing the permanganate ion
(MnO4-)
2HNO2 + 2H+ + 2I- I2 + 2NO + 2H2O
5HNO2 + H+ + 2MnO4- Mn2+ + 5NO3- + 3H2O

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 (-196C) so as to accelerate the cooling process.
(Syukri, 1992)
Some nitrogen compounds
a. Ammonia
Ammonia is a compound of nitrogen which is quite important in the chemical industry.
Ammonia melts at 0C and boils at -77.7 -33.8C. Ammonia is made according to the
haber process, ie dihydrogen and dinitrogen reacted at a pressure of 1000 atm and a
temperature of 50000C with an iron catalyst.
N2(g) + 3H2(g)
2NH3(g)
b. Hydrazine
Hydrazine is a hybrid compound of nitrogen other than ammonia
with molecular formula N2H2. Hydrazine is a colorless compound with
a melting point of 20C and the boiling point of 114 0C, smelled like
ammonia.
c. Nitrogen oxides
Nitrogen can combine with oxygen to form oxides with various levels
of oxide , from +1 to +5. Nitrogen has six types of oxides, namely
nitrogen (I) oxide, nitrogen (II) oxide, nitrogen (II) oxide, nitrogen (III)
oxide, nitrogen (IV) oxide, nitrogen (V) oxide
d. Nitric acid and nitrate salts.
Nitric acid and nitrate compounds is one of the important chemical
industrial materials from nitrogen compounds. Nitric acid is made
through oswald process. This process was first proposed by Friedrich
Oswald in 1908 with raw material ammonia. Nitrogen can form
covalent compounds with many elements. Nitrogen can form a
covalent compound with a lot of non-metallic elements. Nitrogen has
an important compounds with hydrogen and oxygen which can be
found on the oxidation state of nitrogen 1-5.
(Achmad,1992)
Nitrogen contained in the free atmosphere and is the largest atmospheric constituent
gases ( 78 % ) . Compound 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. Example of nitrogen compounds and oxidation are
presented table 1.
Table 1. Oxidation number of nitrogen
Oxidation Number

Compounds

-3
-2
-1
0
+1
+2
+3
+4
+5
(Inorganic Chemistry Lecturer Team, 2015)

NH3
N2H4 (hidrazin)
NH2OH (hydroxylamine)
N2
N2O
NO
N2O3
NO2
HNO3

The electronic configuration of nitrogen atom in its ground state is 1s 2 2s2 2p3, with the
three 2p electrons distributed among the p x, py, and pz orbitals with spins parallel. Nitrogen
forms an exceedingly large number of compounds. Most of which are to be considered
organic rather than inorganic. It is one of the most electronegayive elements, only oxygen and
fluorine exceeding in this respect. The nitrogen atom may complete its octet in several ways :
Electron gain to form the nitride ion, N3 Formation of electron-pair bonds
Formation of electron-pair bonds with electron gain
Formation of electron-pair bonds with electron loss
(Cotton and Wilkinson. 1989)
C. Methode
Equipments
Test tube
250 ml beaker glass
100 ml erlenmeyar
Stirring bar
Spiritus burner
Tripod
Gauze
Clamp
Spatula
Materials
Litmus indicator
0,05 M NaOH
0,05 M sulfuric acid
2 M HNO3
Potassium nitrate solid
Copper nitrate solid
Concentrated nitric acid
KI
KMnO4
7 M HNO3
Aluminium metal

Copper metal

Work instructions
1. a. The reaction of HNO3 and Cu
Insert Cu metal into test tube. Add few drops of concentrated
HNO3. Observe the reaction
Dilute 2 ml of HNO3 to obtain solution of HNO3 7 M. Add
three pieces of Cu and note the gas that is formed
b. Heating of Nitrate salts
Heat a solid KNO3 in a test tube

In different tube, heat Cu(NO3)2 solid. Check the gas and


residual solid generated in test tube
Observe the changes in both tube
c. Nitrate reduction in alkaline solution
Insert into a test tube 2 ml of 2 M HNO3 and 5 ml of dilute
NaOH solution

Add one piece of Al metal then reheat. Check the gas


generated using litmus paper

2. Formation and redox reactions of HNO3


Refrigerate 10 ml of dilute H2SO4 in a test tube with ice for 5
minutes

Enter H2SO4 into the tube containing 1 g of NaNO3

Note the color of solution and the compounds that are formed

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

Add a little of KI into second tube. Observe the changes


Add KMnO4 into third tube. Observe the changes

D. Observation Data
N
o

Experiment
Observed
2 Copper metals +
few drops of
concentrated
HNO3

Reaction Occured

Observation Result

4HNO3(aq)p + Cu(s) Cu(NO3)2(aq)

+ 2NO2(g) + 2H2O(l)

3 copper metals +
HNO3 7M

2HNO3(aq) + Cu(s) Cu(NO3)2(aq) +

NO(g) + H2O(l)

Heating a solid
KNO3

2KNO3(s) KNO2(l) + 1/2 O2(g)

Heating a solid
Cu(NO3)2

Cu(NO3)2.3H2O(s) Cu(NO2)2(aq) +
3H2O(l) + O2(g)

2 ml HNO3 2M +
5ml NaOH
Adding of 1 piece
of Al metal
Heating

3NO3-(aq) + 8Al(s) + 5OH-(aq)


+ 18H2O(l)NH3(g) +
8[Al(OH)4]-(aq)

Blue solution
The color of gas is
brown
There are bubbles
The copper metal
is completely
dissolved
Colorless solution
There are bubbles
The copper metals
are dissolved
After some
minutes, the color
of solution
changed to light
blue
A solid KNO3 is
melted
There are bubbles
gas
pH of gas is acid
After some
minutes, crystal
KNO3 is formed
again
A solid Cu(NO3)2
is melted
There are bubbles
gas
pH of gas is acid

Yellow solution
Al metal is sink

Colorless solution

Diluted H2SO4
(cooled) + NaNO3
Dividing the
solution into 3
parts
Heating tube I
4

H2SO4(aq) + NaNO3(s)
NaHSO4(aq) + HNO2(aq) + 1/2O2(g)

There are bubbles


pH of gas is base
NaNO3 is dissolved,
colorless solution

3HNO2(aq) HNO3(aq) + 2NO (g)


+ H2O (l)

Tube II + KI

2NO2-(aq) + 4H+(aq) + 2I-(aq)


2NO(g) + 2H2O(l) + I2(aq)

Tube III +
KMnO4

5NO2-(aq)+2MnO4-(aq)+6H+(aq)
5NO3-(aq)+2Mn2+(aq) +3H2O(l)

Colorless solution
There are many
bubbles
pH of gas is acid
Pale yellow
solution
There are bubbles
pH of gas is acid
Purple solution
No bubbles and
gas formed

E. Discussion
Redox reaction of nitric acid with nitrate salt
Experiment 1 : The reaction of nitric acid with copper
The goal of this experiment is to identify 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 two pieces of copper metal. This experiment is carried out in a fume
because the solution used is a concentrated nitric acid.
Once we drop the concentrated nitric acid into test tube contained two pieces
of copper metal, the solution initially colorless turns to blue. There are also the
formation of bubbles. In the test tubes wall appears brownish yellow gas. Two pieces
of copper are completely dissolved. Reactions that occur :
4HNO3(l) + Cu (s) 2NO2(s) + Cu(NO3)2(aq) + 2H2O(l)
+
5

+
4

+
2

(reduction)
(oxidation)

Copper (Cu) undergoes oxidation becomes Cu2+ (Cu as a reducing agent) with
an increase in oxidation number from 0 to +2. While nitrogen (N) undergoes reduction
(nitrogen as an oxidizing agent) with a decrease in oxidation number from +5 to +4.
While the blue color is produced by the solution due to the Cu 2+ ions. In this reaction
produced NO2 because the solution thas used is a solution of concentrated nitric acid.
This is fit with the theory that if a metal reacted with concentrated nitric acid it will
produce NO2 gas.

Next, three pieces of copper metal is reacted with a solution of HNO 3 7M. This
reaction produced blue solution. There are bubbles. Copper metal is dissolved in
HNO3 solution. The reaction occured:
HNO3 (aq) + Cu (s) Cu(NO3)2 (aq) + 2NO (g) + 2H2O (l)
+
5

+
2
(oxidation)

+
2

(reduction)

The reaction produces NO gas. This different from the first reaction because
we used nitric acid solution 7M. This is fit with theory that if a metal reacted with
dilute nitric acid it will produced NO gas. In the reaction above, Cu as a reductant
because undergoes oxidation with the increase in oxidation number from 0 to +2.
While nitrogen as an oxidant because undergoes reduction with a decrease in the
oxidation number from +5 to +2.
The second reaction is slower than the first. It because we used the different
HNO3. The higher the concentration of HNO3, the ability to oxidize copper will be
greater. The gas produced is also different. The first experiment produces NO 2 gas,
while in second experiment produces NO gas.
Experiment 2 : Heating of nitrate salt
The purpose of this experiment is to identify the redox
reactions that occur in the heating of nitrate salts. First reaction is
heating spatula of white solid KNO 3 in a test tube. After heating,
KNO3 is melted and produces gas bubbles. When we test with red
litmus paper, the color of litmus does not changes. It means that the
pH of gas produced is acid. The reaction occured :
2KNO3 (s) KNO2 (l) + 1/2 O2 (g)
Second reaction is heating spatula of blue solid Cu(NO3)2 in a
test tube. After heating, Cu(NO3)2 is

melted and produces gas

bubbles. When we test with red litmus paper, the color of litmus
paper does not changes. It means that the pH of gas produced is
acid. The reaction occurs:
Cu(NO3)2.3H2O(s) Cu(NO2)2(aq) + 3H2O(l) + O2(g)

Experiment 3 : Nitrate reduction in alkaline solution


The goal of this experiment is to identify the reaction of nitrate reduction in
alkaline solution. This experiment was carried out by reacting a solution of nitric acid
2M with diluted NaOH solution and Al metal. After we reacting the material, the color
of solution is still the colorless and Al metal is sinking. Then, we will heat it. Before
heating, Al does not react directly. After heating, gas bubbles appear. This indicates

that the heating can quicken the reaction. This reaction produced ammonia gas. When
we test with red litmus paper, the color turns to blue. It means that the pH of gas that
produced is base. The reaction occured :
3NO3- (aq) + 8Al (s) + 5OH-(aq) + 18H2O (aq) NH
3 (aq) + 8[Al(OH)4]
+
-3
5
(reduction)

+
4

(oxidation)

From the reaction above, nitrogen undergoes a reduction with a decrease in


oxidation number from +5 to -3. It means that HNO 3 solution as an oxidizer for
aluminum. While the aluminum metal undergoes oxidation by increase in oxidation
number from 0 to +4. Alumunium metal as a reductor.

Redox reaction of nitrous acid


Experiment 4 : Formation and redox reactions of nitric acid
The purpose of this experiment is to study the process of formation of nitric
acid and redox reactions of nitric acid. This experiment is carried out by reacting a
solution of dilute sulfuric acid with solid NaNO 3. Before reacted, H2SO4 is cooled in
ice bath for 5 minutes. This is done with the aims to minimize the gas that is formed
from the decomposition NaNO3. After reacting with dilute sulfuric acid solution,
NaNO3 will dissolve, and produced colorless solution. The reaction occured :
H2SO4 (aq) + NaNO3 (s) NaHSO4 (aq) + HNO2 (aq) + 1/2O2 (g)
Furthermore, the solution is divided into three solution.
Tube 1 (Heating the solution of H2SO4 + NaNO3)
When the solution of H2SO4 + NaNO3 is heated, bubbles gas are produced
which is NO gas. The solution is colorless. When we test with red litmus
paper, the color of litmus paper does not changes. It means that
the pH of gas produced is acid. This reaction produces nitrate. The reaction
occured :
3 HNO2 (aq) HNO3 (aq) + 2NO (g) + H2O (l)
+
5

+
3

(oxidation)

+
2

(reduction)

The reaction above is a disproportionation reaction (derived from the same species).
Nitrogen undergoes oxidation and reduction at the same time

Tube 2 (Solution of H2SO4 + NaNO3 + KI solution)


When the solution of H2SO4 and NaNO3 added with KI solution, the color of
solution become pale yellow. This reaction takes place under acidic conditions and
the produced NO gas. There are a little bubbles appeared. When we test with
red litmus paper, the color of litmus paper does not changes. It
means that the pH of gas produced is acid. The reaction occurs:

2NO2 (aq) + 4H+ (aq) + 2I- (aq) 2NO (g) + 2H2O (aq) + I2 (aq)
+
4

-1

+
2

(reduction)
(oxidation)

From the reaction above, nitrogen undergoes a reduction with a decreased of


oxidation number from +4 to +2, while NO2 as an oxidizer. KI undergoes oxidation
reactions with an increase in oxidation number from -1 to 0, so KI as a reductor.
Tube 3 (Solution of H2SO4 + NaNO3 + KMnO4 solution)
When the solution of H2SO4 + NaNO3 added KMnO4 solution, produced a
purple solution. This reaction takes place in acidic conditions.There is no gas and
bubbles in this reaction. The reaction occured :
5NO2- (aq) + 2MnO4- (aq) + 6H+ 5NO3- + 2Mn2+ +3H2O
+
3

+
7

+
5

+
2

(oxidation)
(reduction)

From the above reaction, nitrogen undergoes oxidation with an increase in


oxidation number from +3 to +5, where nitrite as a reductor. Mn undergoes
reduction with a decrease in the oxidation number from +7 to +2, where the ion
permanganate MnO4- as an oxidizer.
F. Conclusion
If we react metal with concentrated nitric acid, it will produce NO 2 gas. If we react
metal with dilute nitric acid, it will produce NO gas.
In reaction of concentrated nitric acid, nitrogen undergo reduction with a decrease in
the oxidation state of +5 to +4. While the reaction of dilute nitric acid, nitrogen
undergo reduction with a decrease in the oxidation state of +5 to +2.
Nitrate reduction in alkaline solution produces ammonia gas, which nitrogen
undergoes reduction with a decrease in the oxidation state of +5 be -3.
In the reaction tube 1, nitrogen undergoes oxidation (in HNO 3) with increase in
oxidation state of +3 to +5 and reduction (at NO) with a decrease in oxidation number
of +3 to +2.
In reaction to the tube 2, nitrogen undergoes reduction with a decrease in oxidation
number of +3 to +2.
In the reaction tube 3, nitrogen undergoes oxidation by the increase in oxidation state
+3 to +5.
In this experiment nitrogen has varied oxidation states, such as -3, +2, +3, +4, and +5.
Nitrogen can act as an oxidant, reductant, or both.
G. Suggestion
We should use the litmus paper in all experiments to observe the gas that formed
in the reaction.
H. References

Achmad, Hiskia. 1992. Penuntun Belajar Kimia Dasar, Kimia Unsur


Petrokimia. Bandung: PT. Citra Aditya Bakti.
Cotton, F.A and Wilkinson, G. 1962. Advance Inorganic Chemistry 3rd Edition. USA :
Interscience Publishers
Inorganic Chemistry Lecturer Team. 2015. Manual Work Of Inorganic
Chemistry Practicum. Semarang: Mathematics and Natural Science
Faculty Semarang State University
Syukri. 1992. Kimia Dasar 2. Bandung: ITB.
Taher. 2012. Bilangan Oksidasi Nitrogen. Accessed from
http://chemisttry.blogspot.com/2012/12/bilangan-oksidasi-nitrogen.html