ch8-9
ch8-9
ch8-9
Assign oxidation numbers to the underlined elements in each of the following species:
Answer :
(a)
We know that,
Oxidation number of Na = +1
Oxidation number of H = +1
Then, we have
(b)
Then, we have
(c)
Then, we have
(d)
Then, we have
(e)
Then, we have
(f)
Then, we have
(g)
Then, we have
(h)
Then, we have
Or,
We can ignore the water molecule as it is a neutral molecule. Then, the sum of the oxidation numbers of all atoms of
the water molecule may be taken as zero. Therefore, after ignoring the water molecule, we have
Q2 :
What are the oxidation numbers of the underlined elements in each of the following and how do you
rationalise your results?
(a) KI3 (b) H2S4O6 (c) Fe3O4 (d) CH3CH2OH (e) CH3COOH
Answer :
(a) KI3
In KI3, the oxidation number (O.N.) of K is +1. Hence, the average oxidation number of I is . However, O.N.
cannot be fractional. Therefore, we will have to consider the structure of KI3to find the oxidation states.
In a KI3molecule, an atom of iodine forms a coordinate covalent bond with an iodine molecule.
Hence, in a KI3molecule, the O.N. of the two I atoms forming the I2molecule is 0, whereas the O.N. of the I atom
forming the coordinate bond is –1.
(b) H2S4O6
However, O.N. cannot be fractional. Hence, S must be present in different oxidation states in the molecule.
The O.N. of two of the four S atoms is +5 and the O.N. of the other two S atoms is 0.
(c)
On taking the O.N. of O as –2, the O.N. of Fe is found to be . However, O.N. cannot be fractional.
Here, one of the three Fe atoms exhibits the O.N. of +2 and the other two Fe atoms exhibit the O.N. of +3.
(d)
or, 2x + 4 = 0
or, x = -2
(e)
2 (x) + 4 (+1) + 2 (-2) = 0
or, 2x = 0
or, x = 0
However, 0 is average O.N. of C. The two carbon atoms present in this molecule are present in different
environments. Hence, they cannot have the same oxidation number. Thus, C exhibits the oxidation states of +2 and
–2 in CH3COOH.
Q3 :
Answer :
(a)
Let us write the oxidation number of each element involved in the given reaction as:
Here, the oxidation number of Cu decreases from +2 in CuO to 0 in Cu i.e., CuO is reduced to Cu. Also, the oxidation
number of H increases from 0 in H2 to +1 in H2O i.e., H2 is oxidized to H2O. Hence, this reaction is a redox reaction.
(b)
Let us write the oxidation number of each element in the given reaction as:
Here, the oxidation number of Fe decreases from +3 in Fe2O3 to 0 in Fe i.e., Fe2O3 is reduced to Fe. On the other
hand, the oxidation number of C increases from +2 in CO to +4 in CO2 i.e., CO is oxidized to CO2. Hence, the given
reaction is a redox reaction.
(c)
The oxidation number of each element in the given reaction can be represented as:
In this reaction, the oxidation number of B decreases from +3 in BCl3 to –3 in B2H6. i.e., BCl3 is reduced to B2H6.
Also, the oxidation number of H increases from –1 in LiAlH4 to +1 in B2H6 i.e., LiAlH4 is oxidized to B2H6. Hence, the
given reaction is a redox reaction.
(d)
The oxidation number of each element in the given reaction can be represented as:
In this reaction, the oxidation number of K increases from 0 in K to +1 in KF i.e., K is oxidized to KF. On the other
hand, the oxidation number of F decreases from 0 in F2 to –1 in KF i.e., F2 is reduced to KF.
(e)
The oxidation number of each element in the given reaction can be represented as:
Here, the oxidation number of N increases from –3 in NH3 to +2 in NO. On the other hand, the oxidation number of
O2decreases from 0 in O2 to –2 in NO and H2O i.e., O2 is reduced. Hence, the given reaction is a redox reaction.
Q4 :
Answer :
Let us write the oxidation number of each atom involved in the given reaction above its symbol as:
Here, we have observed that the oxidation number of F increases from 0 in F2 to +1 in HOF. Also, the oxidation
number decreases from 0 in F2 to –1 in HF. Thus, in the above reaction, F is both oxidized and reduced. Hence, the
given reaction is a redox reaction.
Q5 :
Calculate the oxidation number of sulphur, chromium and nitrogen in H2SO5, –. Suggest
structure of these compounds. Count for the fallacy.
Answer :
(i)
However,the O.N. of S cannot be +8. S has six valence electrons. Therefore, the O.N. of S cannot be more than +6.
(ii)
(iii)
Here, there is no fallacy about the O.N. of N in .
Q6 :
Answer :
HgCl2
NiSO4
SnO2
Tl2SO4
Fe2(SO4)3
Cr2O3
Q7 :
Suggest a list of the substances where carbon can exhibit oxidation states from -4 to +4 and nitrogen from -3
to +5.
Answer :
The substances where carbon can exhibit oxidation states from –4 to +4 are listed in the following table.
Q8 :
While sulphur dioxide and hydrogen peroxide can act as oxidising as well as reducing agents in their
reactions, ozone and nitric acid act only as oxidants. Why?
Answer :
In sulphur dioxide (SO2), the oxidation number (O.N.) of S is +4 and the range of the O.N. that S can have is from +6
to -2.
In hydrogen peroxide (H2O2), the O.N. of O is -1 and the range of the O.N. that O can have is from 0 to -2. O can
sometimes also attain the oxidation numbers +1 and +2. Hence, H2O2can act as an oxidising as well as a reducing
agent.
In ozone (O3), the O.N. of O is zero and the range of the O.N. that O can have is from 0 to -2. Therefore, the O.N. of
O can only decrease in this case. Hence, O3acts only as an oxidant.
In nitric acid (HNO3), the O.N. of N is +5 and the range of the O.N. that N can have is from +5 to -3. Therefore, the
O.N. of N can only decrease in this case. Hence, HNO3acts only as an oxidant.
Q9 :
Also suggest a technique to investigate the path of the above (a) and (b) redox
reactions.
Answer :
Step 1:
Step 2:
The H2produced in step 1reduces CO2, thereby producing glucose (C6H12O6) and H2O.
The path of this reaction can be investigated by using radioactive H2O18in place of H2O.
(b) O2is produced from each of the two reactants O3and H2O2. For this reason, O2is written twice.
The given reaction involves two steps. First, O3decomposes to form O2and O. In the second step, H2O2reacts with the
O produced in the first step, thereby producing H2O and O2.
Q10 :
The compound AgF2 is an unstable compound. However, if formed, the compound acts as a very strong
oxidizing agent. Why?
Answer :
The oxidation state of Ag in AgF2 is +2. But, +2 is an unstable oxidation state of Ag. Therefore, whenever AgF2 is
formed, silver readily accepts an electron to form Ag+. This helps to bring the oxidation state of Ag down from +2 to a
more stable state of +1. As a result, AgF2 acts as a very strong oxidizing agent.
Q11 :
Whenever a reaction between an oxidising agent and a reducing agent is carried out, a compound of lower
oxidation state is formed if the reducing agent is in excess and a compound of higher oxidation state is
formed if the oxidising agent is in excess. Justify this statement giving three illustrations.
Answer :
Whenever a reaction between an oxidising agent and a reducing agent is carried out, a compound of lower oxidation
state is formed if the reducing agent is in excess and a compound of higher oxidation state is formed if the oxidising
agent is in excess. This can be illustrated as follows:
If an excess of P4is treated with F2, then PF3will be produced, wherein the oxidation number (O.N.) of P is +3.
However, if P4is treated with an excess of F2, then PF5will be produced, wherein the O.N. of P is +5.
(ii)K acts as a reducing agent, whereas O2is an oxidising agent.
If an excess of K reacts with O2, then K2O will be formed, wherein the O.N. of O is –2.
However, if K reacts with an excess of O2, then K2O2will be formed, wherein the O.N. of O is –1.
If an excess of C is burnt in the presence of insufficient amount of O2, then CO will be produced, wherein the O.N. of
C is +2.
On the other hand, if C is burnt in an excess of O2, then CO2will be produced, wherein the O.N. of C is +4.
Q12 :
(a) Though alkaline potassium permanganate and acidic potassium permanganate both are used as oxidants,
yet in the manufacture of benzoic acid from toluene we use alcoholic potassium permanganate as an
oxidant. Why? Write a balanced redox equation for the reaction.
(b) When concentrated sulphuric acid is added to an inorganic mixture containing chloride, we get
colourless pungent smelling gas HCl, but if the mixture contains bromide then we get red vapour of bromine.
Why?
Answer :
(a) In the manufacture of benzoic acid from toluene, alcoholic potassium permanganate is used as an oxidant
because of the following reasons.
(i) In a neutral medium, OH– ions are produced in the reaction itself. As a result, the cost of adding an acid or a base
can be reduced.
(ii) KMnO4 and alcohol are homogeneous to each other since both are polar. Toluene and alcohol are also
homogeneous to each other because both are organic compounds. Reactions can proceed at a faster rate in a
homogeneous medium than in a heterogeneous medium. Hence, in alcohol, KMnO4 and toluene can react at a faster
rate.
The balanced redox equation for the reaction in a neutral medium is give as below:
(b) When conc. H2SO4 is added to an inorganic mixture containing bromide, initially HBr is produced. HBr, being a
strong reducing agent reduces H2SO4 to SO2 with the evolution of red vapour of bromine.
But, when conc. H2SO4 is added to an inorganic mixture containing chloride, a pungent smelling gas (HCl) is evolved.
HCl, being a weak reducing agent, cannot reduce H2SO4 to SO2.
Q13 :
Identify the substance oxidised, reduced, oxidising agent and reducing agent for each of the following
reactions:
Answer :
Q14 :
Why does the same reductant, thiosulphate react differently with iodine and bromine?
Answer :
The average oxidation number (O.N.) of S in is +2. Being a stronger oxidising agent than I2,
Br2oxidises to , in which the O.N. of S is +6. However, I2is a weak oxidising agent. Therefore, it
oxidises to , in which the average O.N. of S is only +2.5. As a result, reacts differently with
iodine and bromine.
Q15 :
Justify giving reactions that among halogens, fluorine is the best oxidant and among hydrohalic compounds,
hydroiodic acid is the best reductant.
Answer :
HI and HBr can reduce H2SO4 to SO2, but HCl and HF cannot. Therefore, HI and HBr are stronger reductants than
HCl and HF.
Thus, the reducing power of hydrohalic acids increases in the order of HF < HCl < HBr < HI.
Q16 :
What conclusion about the compound Na4XeO6(of which is a part) can be drawn from the reaction.
Answer :
In this reaction, the oxidation number (O.N.) of Xe decreases from +8 in to +6 in XeO3and the O.N. of F
increases from –1 in F– to O in F2.
Q17 :
What inference do you draw about the behaviour of Ag+and Cu2+from these reactions?
Answer :
Ag+ and Cu2+ act as oxidising agents in reactions (a) and (b) respectively.
In reaction (c), Ag+ oxidises C6H5CHO to C6H5COO-, but in reaction (d), Cu2+ cannot oxidise C6H5CHO.
Hence, we can say that Ag+ is a stronger oxidising agent than Cu2+.
Q18 :
(c) H2O2(aq) + Fe2+(aq) → Fe3+(aq) + H2O (l) (in acidic solution)
Answer :
(a) Step 1: The two half reactions involved in the given reaction are:
Step 2:
Now, to balance the charge, we add 2 e–to the RHS of the reaction.
Step 3:
In the reduction half reaction, the oxidation state of Mn has reduced from +7 to +4. Thus, 3 electrons are added to the
LHS of the reaction.
Now, to balance the charge, we add 4 OH–ions to the RHS of the reaction as the reaction is taking place in a basic
medium.
Step 4:
In this equation, there are 6 O atoms on the RHS and 4 O atoms on the LHS. Therefore, two water molecules are
added to the LHS.
Step 5:
Equalising the number of electrons by multiplying the oxidation half reaction by 3 and the reduction half reaction by 2,
we have:
Step 6:
Adding the two half reactions, we have the net balanced redox reaction as:
(b)Following the steps as in part (a), we have the oxidation half reaction as:
Multiplying the oxidation half reaction by 5 and the reduction half reaction by 2, and then by adding them, we have the
net balanced redox reaction as:
(c) Following the steps as in part (a), we have the oxidation half reaction as:
Multiplying the oxidation half reaction by 2 and then adding it to the reduction half reaction, we have the net balanced
redox reaction as:
(d) Following the steps as in part (a), we have the oxidation half reaction as:
And the reduction half reaction as:
Multiplying the oxidation half reaction by 3 and then adding it to the reduction half reaction, we have the net balanced
redox reaction as:
Q19 :
Balance the following equations in basic medium by ion-electron method and oxidation number methods and
identify the oxidising agent and the reducing agent.
Answer :
(a)
The O.N. (oxidation number) of P decreases from 0 in P4 to – 3 in PH3 and increases from 0 in P4 to + 2 in .
Hence, P4 acts both as an oxidizing agent and a reducing agent in this reaction.
Ion–electron method:
By multiplying equation (i) with 3 and (ii) with 2 and then adding them, the balanced chemical equation can be
obtained as:
(b)
The oxidation number of N increases from – 2 in N2H4 to + 2 in NO and the oxidation number of Cl decreases from
+ 5 in to – 1 in Cl–. Hence, in this reaction, N2H4 is the reducing agent and is the oxidizing agent.
Ion–electron method:
The balanced equation can be obtained by multiplying equation (i) with 3 and equation (ii) with 4 and then adding
them as:
On multiplying N2H4 with 3 and with 4 to balance the increase and decrease in O.N., we get:
(c)
The oxidation number of Cl decreases from + 7 in Cl2O7 to + 3 in and the oxidation number of O increases
from – 1 in H2O2 to zero in O2. Hence, in this reaction, Cl2O7 is the oxidizing agent and H2O2 is the reducing agent.
Ion–electron method:
The balanced equation can be obtained by multiplying equation (i) with 4 and adding equation (ii) to it
as:
By multiplying H2O2 and O2 with 4 to balance the increase and decrease in the oxidation number, we get:
Q20 :
What sorts of informations can you draw from the following reaction ?
Answer :
The oxidation numbers of carbon in (CN)2, CN– and CNO– are +3, +2 and +4 respectively. These are obtained as
shown below:
(CN)2
2(x – 3) = 0
∴x = 3
CN–
x – 3 = –1
∴x = 2
CNO–
∴x = 4
It can be easily observed that the same compound is being reduced and oxidised simultaneously in the given
equation. Reactions in which the same compound is reduced and oxidised is known as disproportionation reactions.
Thus, it can be said that the alkaline decomposition of cyanogen is an example of disproportionation reaction.
Q21 :
The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+, MnO2, and H+ ion. Write a
balanced ionic equation for the reaction.
Answer :
The O atoms and H+ ions are balanced by adding 2H2O molecules as:
The balanced chemical equation can be obtained by adding equation (i) and (ii) as:
Q22 :
(a) Identify the element that exhibits only negative oxidation state.
(b) Identify the element that exhibits only postive oxidation state.
(c) Identify the element that exhibits both positive and negative oxidation states.
(d) Identify the element which exhibits neither the negative nor does the positive oxidation state.
Answer :
(c) I exhibits both positive and negative oxidation states. It exhibits oxidation states of - 1, + 1, + 3, + 5, and + 7.
(d) The oxidation state of Ne is zero. It exhibits neither negative nor positive oxidation states.
Q23 :
Chlorine is used to purify drinking water. Excess of chlorine is harmful. The excess of chlorine is removed by
treating with sulphur dioxide. Present a balanced equation for this redox change taking place in water.
Answer :
The O atoms and H+ ions are balanced by adding 2H2O molecules as:
The balanced chemical equation can be obtained by adding equation (i) and (ii) as:
Q24 :
Refer to the periodic table given in your book and now answer the following questions:
(a) Select the possible non metals that can show disproportionation reaction.
Answer :
In disproportionation reactions, one of the reacting substances always contains an element that can exist in at least
three oxidation states.
(a) P, Cl, and S can show disproportionation reactions as these elements can exist in three or more oxidation states.
(b) Mn, Cu, and Ga can show disproportionation reactions as these elements can exist in three or more oxidation
states.
Q25 :
In Ostwald's process for the manufacture of nitric acid, the first step involves the oxidation of ammonia gas
by oxygen gas to give nitric oxide gas and steam. What is the maximum weight of nitric oxide that can be
obtained starting only with 10.00 g. of ammonia and 20.00 g of oxygen?
Answer :
The balanced chemical equation for the given reaction is given as:
Therefore, O2 is the limiting reagent (we have considered the amount of O2 to calculate the weight of nitric oxide
obtained in the reaction).
Q26 :
Using the standard electrode potentials given in the Table 8.1, predict if the reaction between the following is
feasible:
(a) Fe3+(aq) and I-(aq)
Answer :
E° for the overall reaction is positive. Thus, the reaction between and is feasible.
E° positive for the overall reaction is positive. Hence, the reaction between and is feasible.
E° positive for the overall reaction is positive. Hence, the reaction between and is feasible.
Here, E° for the overall reaction is positive. Hence, the reaction between and is feasible.
Q27 :
Answer :
On electrolysis, either Ag+ ions or H2O molecules can be reduced at the cathode. But the reduction potential of
Ag+ ions is higher than that of H2O.
Hence, Ag+ ions are reduced at the cathode. Similarly, Ag metal or H2O molecules can be oxidized at the anode. But
the oxidation potential of Ag is higher than that of H2O molecules.
Therefore, Ag metal gets oxidized at the anode.
(ii) Pt cannot be oxidized easily. Hence, at the anode, oxidation of water occurs to liberate O2. At the cathode,
Ag+ ions are reduced and get deposited.
On electrolysis, either of H+ ions or H2O molecules can get reduced at the cathode. But the reduction potential of
H+ ions is higher than that of H2O molecules.
On the other hand, at the anode, either of ions or H2O molecules can get oxidized. But the oxidation of
involves breaking of more bonds than that of H2O molecules. Hence, ions have a lower oxidation potential
than H2O. Thus, H2O is oxidized at the anode to liberate O2 molecules.
(iv) In aqueous solutions, CuCl2 ionizes to give Cu2+ and Cl– ions as:
On electrolysis, either of Cu2+ ions or H2O molecules can get reduced at the cathode. But the reduction potential of
Cu2+is more than that of H2O molecules.
Hence, Cu2+ ions are reduced at the cathode and get deposited.
Similarly, at the anode, either of Cl– or H2O is oxidized. The oxidation potential of H2O is higher than that of Cl–.
But oxidation of H2O molecules occurs at a lower electrode potential than that of Cl– ions because of over-voltage
(extra voltage required to liberate gas). As a result, Cl– ions are oxidized at the anode to liberate Cl2 gas.
Q28 :
Arrange the following metals in the order in which they displace each other from the solution of their salts.
Al, Cu, Fe, Mg and Zn.
Answer :
A metal of stronger reducing power displaces another metal of weaker reducing power from its solution of salt.
The order of the increasing reducing power of the given metals is Cu < Fe < Zn < Al < Mg.
Hence, we can say that Mg can displace Al from its salt solution, but Al cannot displace Mg.
Thus, the order in which the given metals displace each other from the solution of their salts is given below:
Q29 :
Hg2+/Hg = 0.79V
Answer :
The lower the electrode potential, the stronger is the reducing agent. Therefore, the increasing order of the reducing
power of the given metals is Ag < Hg < Cr < Mg < K.
Q30 :
Depict the galvanic cell in which the reaction Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s) takes place, further show:
Answer :
The galvanic cell corresponding to the given redox reaction can be represented as:
(i) Zn electrode is negatively charged because at this electrode, Zn oxidizes to Zn2+ and the leaving electrons
accumulate on this electrode.