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Electrochemistry
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17. ELECTROCHEMISTRY
1. INTRODUCTION
Electrochemistry is a branch of chemistry which deals with interconversion of chemical energies and electrical
energy. We’ll discuss electrolytic reactions (reactions that occur when electricity passes through solutions) as well
as electromagnetic reaction (reactions that produce electric energy). Some examples of electrolytic reactions are
electrolysis, electroplating, electro refining of metals, etc. Some examples of electro genetic reactions are reactions
occurring in cells or batteries.
2. TERMINOLOGIES IN ELECTROCHEMISTY
Some important terms used in Electrochemistry are as follows:
(a) Electrical Conductors: Materials that allow flow of electrons are known as conductors. There are broadly two
types of conductorsElectronic/Metallic and Electrolytic/Solution.
Table 17.1: Difference between Electronic Conductor and Electrolytic Conductors
Electronic Conductors or Metallic Conductors Electrolytic Conductors or Solution Conductors
1. Passage of current by movement of electrons in the Passage of current by ions in molten state or in aqueous solution
metallic lattice, e.g., Cu, Ag, etc. of electrolytes, e.g., NaCl (aq) or NaCl (fused).
2. Passage of current brings in only physical changes. Passage of current brings in physical as well as chemical changes.
3. It generally shows no transfer of matter. It involves transfer of matter in the form of ions.
4. It generally shows an increase in resistance during the It generally shows a decrease in resistance due to decrease in
passage of current due to increase in temperature. viscosity of the medium and degree of hydration of ions with
Thermal motion of metal ions hindering the flow of increase in temperature.
electrons increases with increase in temperature.
5. The conducting power of metals is usually high. The conducting power of electrolytic conductors is relatively low.
(b) Insulators: Those materials which don’t allow the passage of electrons are known as Insulators. For e.g. wood,
wool, plastic, silk, etc.
(c) Electrolytes: The substance that in solution or in the molten state, conducts electric current and is
simultaneously decomposed is called an electrolyte.The extent or degree of dissociation of different electrolytes
in solution is different. Electrolytes can be broadly categorized into two: Strong and Weak Electrolytes.
(d) Strong Electrolytes: Substances which are largely dissociated and form a highly conducting liquid in water
are strong electrolytes, e.g., All salts (except CdBr2, HgCl2), mineral acids like HCl, H2SO4, HNO3, etc. and
bases like NaOH, KOH, etc. are strong electrolytes. The strong electrolytes are almost 100% ionized at
normal dilution.
1 7 . 2  Electrochemistr y
(e) Weak Electrolytes: Substances which dissociate only to a small extent in aqueous solution forming low
conducting liquid are weak electrolytes, e.g., All organic acids (except sulphonic acids), inorganic acids
like HCN, H3BO3, etc. and bases like NH3, amines, etc. are weak electrolytes.
(f) Electrodes: In order to pass the current through an electrolytic conductor, two rods or plates are always
needed which are connected with the terminals of a battery. These rods/plates are called Electrodes. The
electrode where oxidation reaction takes place is anode and electrode where reduction takes place is cathode.
3. ELECTROLYSIS
The phenomenon in which passage of current through an electrolyte (molten or solution) brings in chemical
changes involving electronation (reduction) as well as deelectronation (oxidation) of ions is known as electrolysis.
3.1 Preferential Discharge Theory
If an electrolytic solution consists of more than two ions and the electrolysis is done, it is observed that all the
ions are not discharged from the electrodes simultaneously but certain ions are liberated from the electrodes in
preference to others. This is explained by preferential discharge theory. It states that if more than one type of
ions are attracted towards a particular electrode, then the one discharged is the ion which requires least energy.
The potential at which the ion is discharged or deposited on the appropriate electrode is termed the discharge
potential or deposition potential. The values of discharge potential are different for different ions.
Table 17.2: Examples of preferential discharge theory
Electrolyte Electrode Cathodic reaction Anodic reaction
Aqueous acidified Pt 2Cl− → Cl2 + 2e−
CuCl2 solution
Cu2+ + 2e− → Cu
Molten PbBr2 Pt 2Br − → Br2 + 2e−
Pb2+ + 2e− → Pb
Sodium chloride Hg 2Cl− → Cl2 + 2e−
solution
2Na+ + 2e− → 2Na
Silver nitrate solution Pt
Ag+ + e− → Ag 1
2OH− → O2 + H2O + 2e−
2
Sodium nitrate Pt
2H+ + 2e− → H2 1
solution 2OH− → O2 + H2O + 2e−
2
Illustration 1: Find the charge in coulomb on 1 gion of N3− . (JEE MAIN)
Sol: First determine charge on one ions of this can be calculated as product of number of electron and charge of
electron. According to Avogadro’s law one g of ion contains 6.02 × 1023 ions. So, charge on one gion of N3− can be
calculated by multiplying charge.
Charge on one ions of N3− into Avogadro number.
3− −19
Charge on one ions of N =3 × 1.6 × 10 coulomb One gion = 6.02 × 1023 ions
Thus, charge on one gion of N3− =3 × 1.6 × 10 −19 × 6.02 × 1023 = 2.89 × 105 coulomb
Illustration 2: Explain the reaction: (a) 2KI + Cl2 → 2KCl + I2 , (b) 2KClO3 + I2 → 2KIO3 + Cl2
Sol: Compound which undergoes oxidation acts as a reducing agent and compound which undergoes reduction
acts as an oxidizing agent.
Chem i str y  17.3
(a) Cl2 acts as oxidizing agent: 2e− + Cl2 → 2Cl− ; 2I − → I2 + 2e−
(b) I2 acts as reducing agent: 2Cl5+ + 10e− → Cl ; I02 → 2I5+ + 10e−
2
PLANCESS CONCEPTS
Misconception: Electrolysis does not mean breaking up of an ionic compound into ions. An ionic
compound even on dissolution in water furnishes ions.
Note: During electrolysis, oxidationreduction occurs simultaneously. Oxidation occurs at anode whereas
reduction occurs at cathode.
Nikhil Khandelwal (JEE 2009 AIR 94)
3.2 Faraday’s Law of Electrolysis
The relationship between the quantity of electric charge passed through an electrolyte and the amount of the
substance deposited at the electrodes was presented as the ‘laws of electrolysis’ by Faraday in 1834.
3.2.1 Faraday’s First Law
When an electric current is passed through an electrolyte, the amount of substance deposited is proportional to
the quantity of electric charge passed through the electrolyte.
If W be the mass of the substance deposited by passing Q coulomb of charge, then according to the law, we have
the relation: W ∝ Q
Q = current in amperes × time in seconds = I × t
So, W ∝ I × t or W = Z×I×t
Where Z is a constant, known as electrochemical equivalent and is characteristic of the substance deposited.
When a current of one ampere is passed for one second, i.e., one coulomb (Q = 1), then W = Z.
Definition of electrochemical equivalent: Mass of the substance deposited by one coulomb of charge or one
ampere current for one second.
3.2.2 Faraday’s Second Law
When the same quantity of charge is passed through different electrolytes, then the masses of different substances
deposited at the respective electrodes will be in the ratio of their equivalent masses. Again according to first law,
W= Z × Q
When, Q = 96500 coulomb, W becomes gram equivalent mass (E).
E Z1 E1
Thus, E= Z × 96500 or Z = ; =
96500 Z 2 E2
3.2.3 Faraday’s Law for Gaseous Electrolytic Product
ItVe
For the gases, we use V =
96500
Where, V = Volume of gas evolved at STP at an electrode
Ve = Equivalent volume = Volume of gas evolved at an electrode at STP by 1 faraday charge
1 7 . 4  Electrochemistr y
Example: A 40.0 amp current flowed through molten iron (III) chloride for 10.0 hours (36,000 s). Determine the
mass of iron and the volume of chlorine gas (measured at 25ºC and 1 atm) that is produced during this time.
Sol:
1. Write the halfreaction that take place at the anode and at the cathode.
Anode (oxidation): 2Cl− → Cl2 (g) + 2e− Cathode (reduction): Fe3+ + 3e− → Fe(s)
2. Calculate the number of moles of electrons.
1.44 × 106 C
40.0amps × 36,000s =
1F 1mole e−
1.44 × 106 C × 14.9F ; 14.9F ×
= 14.9mole e−
=
96, 485C 1F
3. Calculate the moles of iron and of chlorine produced using the number of moles of electrons calculated and
the stoichiometry from the balanced halfreactions. According to the equations, three moles of electrons
produce one mole of iron and 2 moles of electrons produce 1 mole of chlorine gas.
1mole Fe 1mole Cl2
14.9mole
= e− × e− ×
4.97mole Fe; 14.9mole= 7.45mole Cl2
−
3mole e 2mole e−
4. Calculate the mass of iron using the molar mass and calculate the volume of chlorine gas using the ideal gas
law (PV = nRT).
55.847 gFe (7.45moleCl2 )(0.0821atm L / mole K)(298K)
=
4.97mole Fe × 278gFe; = 182L Cl2
1mole Fe 1atm
Calculating the Time required
To determine the quantity of time required to produce a known quantity of a substance given the amount of
current that flowed:
(i) Find the quantity of substance produced/consumed in moles.
(ii) Write the balanced halfreaction involved.
(iii) Calculate the number of moles of electrons required.
(iv) Convert the moles of electrons into coulombs.
(v) Calculate the time required.
Example: How long must a 20.0 amp current flow through a solution of ZnSO 4 in order to produce 25.00 g of Zn
metal?
Sol:
(i) Convert the mass of Zn produced into moles using the molar mass of Zn.
1mole Zn
25.00gZn × 0.3823mole Zn
=
65.39gZn
(ii) Write the halfreaction for the production of Zn at the cathode. Zn2+ (aq) + 2e− → Zn(s)
(iii) Calculate the moles of e required to produce the moles of Zn using the stoichiometry of the balanced half
reaction. According to the equation, 2 moles of electrons will produce one mole of zinc.
2mole e−
0.3823mole Zn × 0.7646mole e−
=
1mole Zn
Chem i str y  17.5
(iv) Convert the moles of electrons into coulombs of charge using Faraday’s constant.
1F 96, 485C
0.76mole e− × = 0.7646F; 0.7646F × = 73,770C
1molee − 1F
(v) Calculate the time using the current and the coulombs of charge.
20.0amps
= × t 73,770C;
= t 3,688s or 1.03h
Calculating the Current required
To determine the amount of current necessary to produce a known quantity of substance in a given amount of
time:
(i) Find the quantity of substance produced/or consumed in moles.
(ii) Write the equation for the halfreaction taking place.
(iii) Calculate the number of moles of electrons required.
(iv) Convert the moles of electrons into coulombs of charge.
(v) Calculate the current required.
Example: What amount of current is required to produce 400.0 L of hydrogen gas, measured at STP, from the
electrolysis of water in 1 hour (3600 s)?
Sol:
(i) Calculate the number of moles of H2. (Remember, at STP, 1 mole of any gas occupies 22.4 L)
1mole H2
400.0L H2 × = 17.9mole H2
22.4L H2
(ii) Write the equation for the halfreaction that takes place.
Hydrogen is produced during the reduction of water at the cathode. The equation for this halfreaction is:
4e− + 4H2O(I) → 2H2 (g) + 4OH− (aq)
(iii) Calculate the number of moles of electrons. According to the stoichiometry of the equation, 4 mole of e− are
required to produce 2 moles of hydrogen gas, or 2 moles of e− s for every one mole of hydrogen gas.
2mole e−
17.9mole H2 × 35.8mole e−
=
1mole H2
(iv) Convert the moles of electrons into coulombs of charge.
1F 96, 485C
35.8mole e− × 35.8F; 35.8F ×
= 3.45 106 C
=×
1mole e − 1F
(v) Calculate the current required. I × 3600s =3.45 × 106 C; I =958C / s =958amps
PLANCESS CONCEPTS
As one faraday (96500 coulombs) deposits one gram equivalent of the substance, hence electrochemical
equivalent can be calculated from the equivalent weight,
Eq. wt. of the substance
i.e., Z =
96500
Note: Knowing the weight of the substance deposited (W gram) on passing a definite quantity of electricity
W
(Q coulombs), the equivalent weight of the substance can be calculated, i.e., Eq. wt.
= × 96500
Q
1 7 . 6  Electrochemistr y
PLANCESS CONCEPTS
Tip: The quantity of electricity actually passed is calculated from the current and time as follows:
Quantity of electricity in columbs = Current amperes × time in seconds
Thus, knowing the quantity of electricity passed, the amount of substance deposited can be calculated.
Faraday’s first law and second law can be combined to give a mathematical relation as follows:
E Q Q M C×t M
W = ZQ = ×Q = ×E = × = ×
F F F z F z
z = Electrochemical equivalent; Q = Quantity of electricity passed, E = Eq. wt. of the metal,
F = 1 Faraday, M = Atomic mass of the metal; z = Valency of the metal; C = Current passed,
t = Time for which current is passed.
Saurabh Gupta (JEE 2010 AIR 443)
Illustration 3: Electric current of 100 ampere is passed through a molten liquid of sodium chloride for 5 hours.
Calculate the volume of chlorine gas liberated at the electrode at NTP. (JEE MAIN)
Sol: Here current and time is given so from this first calculate quantity of electricity passed (charge) and from this
calculate the amount of chlorine liberated. Volume of Cl2 liberated at NTP can be determined by multiplying the
amount of chlorine liberated by 22.4 L
The reaction taking place at anode is: 2Cl− → Cl2 + 2e− Q = I × t = 100 × 5 × 60 × 60 coulomb
71.0 g 71.0 g 2×96500 coulomb
1mole
The amount of chlorine liberated by passing 100 × 5 × 60 × 60 coulomb of electric charge
1
= × 100 × 5 × =
60 × 60 9.3264 mole Volume of Cl2 liberated at NTP= 9.3264 × 22.4= 201L
2 × 96500
Illustration 4: How much electric charge is required to oxidize (a) 1 mole of H2O toO2 and
(b) 1 mole of FeO to Fe2O3 ? (JEE MAIN)
Sol: Charge = No of electrons involved in the reaction x faradays constant
So first find out the no of electron reaction involved in the reaction by writing the chemical reaction, balancing it
and then calculate the charge.
1
(a) The oxidation reaction is: H2O → O2 + 2H+ + 2e− ; Q= 2 × F =
2 × 96500 =
193000 coulomb
1mole 2 2mole
1 1
(b) The oxidation reaction is: FeO + H2O → Fe2O3 + H+ + e− ; O= F= 96500 coulomb
2 2
Illustration 5: An aqueous solution of sodium chloride on electrolysis gives H2 (g),Cl2 (g) and NaOH according to
the reaction. 2Cl− (aq.) + 2H2O → 2OH− (aq.) + H2 (g) + Cl2 (g) .
A direct current of 25 ampere with a current efficiency 62% is passed through 20 L of NaCl solution (20% by mass).
Write down the reactions taking place at the anode and cathode. How long will it take to produce 1 kg of Cl2? What
will be the molarity of the solution with respect to hydroxide ion? Assume no loss due to evaporation.
(JEE ADVANCED)
Chem i str y  17.7
Sol: Time can be calculate by using charge and current relationship. Effective current is determined by using
current efficiency. Here it is given that we have to find out the molarity of the solution with respect to hydroxide
Ion. Volume is given. We have to find out the no of moles of oxygen.
This can be achieved by calculating the no of mole of Cl2 present in 1 kg.
Reactions at anode and cathode are: 2Cl− → Cl2 + 2e− (at anode)
1000
2H2O + 2e− → H2 + 2OH− ( at cathode) 1kg of=
Cl2 = 14.08 mole
71.0
Charge to produce one mole of Cl2=2 x 96500
Charge to produce 14.08 mole of Cl2=2x96500x14.08
62
Effective current = × 25.0 =
15.5 ampere
100
Charge 2 × 96500 × 14.08
Time
= = = 175318.7 second
= 48.699 hour
Current 15.5
OH ions produced = 2 × moles of Cl2 = 2x14.08 = 28.16
Mole 28.16
Molarity
= = = 1.408M
Volume 20
Illustration 6: An acidic solution of Cu2+ salt containing 0.4 g of Cu2+ is electrolyzed until all the copper is deposited.
The electrolysis is continued for seven more minutes with volume of solution kept at 100 mL and the current at 1.2
amp. Calculate the gases evolved at NTP during the entire electrolysis. (JEE ADVANCED)
0.4
Cu2+
Sol: 0.4 g of = = 0.0126g − equivalent
31.75
8
At the same time, the oxygen deposited at anode = × 0.0126g =
0.00315g − mole
32
After the complete deposition of copper, the electrolysis will discharge hydrogen at cathode and oxygen at anode.
The amount of charge passed = 1.2 × 7 × 60= 504 coulomb
1 8
So, Oxygen liberated= × 504= 0.00523g − equivalent = × 0.00523 =
0.001307g − mole
96500 32
1
0.00523g − equivalent =
Hydrogen liberated = × 0.00523 =0.00261g − mole
2
Total gases evolved =(0.00315 + 0.001307 + 0.00261)g
= − mole 0.007067g − mole
NTP 22400 × 0.007067mL = 158.3mL
Volume of gases evolved at=
4. ARRHENIUS THEORY OF ELECTROLYTIC DISSOCIATION
In order to explain the properties of electrolytic solutions, Arrhenius put forth a comprehensive theory. The main
postulates of the theory are:
(a) An electrolyte, when dissolved in water, breaks up into two types of charged particles, one carrying a positive
charge and the other a negative charge. These charged particles are called ions. Positively charged ions are
termed as cations and negatively charged as anions.
A +B− + aq. → A + (aq.) + B− (aq.)
1 7 . 8  Electrochemistr y
(b) The process of splitting of the molecules into ions of an electrolyte is called ionization. The fraction of
the total number of molecules present in solution as ions is known as degree of ionizations or degree of
dissociation. It is denoted by ‘ α ’
Number of molecules dissociated int o ions
(c) α =
Total number of molecules
(d) Ions present in solution constantly reunite to form neutral molecules and, thus, there is a state of dynamic
equilibrium between the ionized and nonionized molecules, i.e. AB A + + B−
[A + ][B− ]
(e) Applying the law of mass action to the above equilibrium = K . K is known as ionization constant. The
[AB]
electrolytes having high value of K are termed strong electrolytes and those having low value of K as weak
electrolytes.
(f) When an electric current is passed through the electrolytic solution, the positive ions (cations) move towards
cathode and the negative ions (anions) move towards anode and get discharged, i.e., electrolysis occurs. The
ions are discharged always in equivalent amounts, no matter what their relative speeds are.
(g) The electrolytic solution is always neutral in nature as the total charge on one set of ions is always equal to
the total charge on the other set of ions. However, it is not necessary that the number of two sets of ions must
be equal always.
AB A + + B− (Both ions are equal)
NaCl Na+ + Cl− (Both ions are equal)
AB2 A2+ + 2B− (Anions are double that of cations)
2+ −
BaCl2 Ba + 2Cl (Anions are double that of cations)
A2B 2A + + B2− (Cations are double that of anions)
Na2SO 4 2Na+ + SO24− (Cations are double that of anions)
(h) The properties of electrolytes in solution are the properties of ions present in solution. For example, acidic
solution always contains H+ ions while basic solution contains OH− ions and characteristic properties of
solutions are those of H+ ions and OH− ions respectively.
Limitations of Arrhenius Theory
(i) You cannot apply Ostwald’s dilutions law which is based on Arrhenius theory to strong electrolytes.
(ii) Strong electrolytes conduct electricity in a fused state, i.e., in the absence of water. This is in contradiction of
Arrhenius theory which states that the presence of solvent is imperative for ionization.
(iii) Arrhenius theory assumes independent existence of ions but fails to account for the factors which influence
the mobility of the ions.
4.1 Factors Affecting Degree of Ionization
(a) Nature of solute: When the ionizable parts of a molecule of a substance are held more by covalent bonding
than by electrovalent bonding, less ions are furnished in solution.
(b) Nature of solvent: The main function of the solvent is to weaken the electrostatic forces of attraction between
the two ions and separate them.
(c) Dilution: The extent of ionization of an electrolyte is inversely proportional to the concentration of its
solution. Thus, degree of ionization increases with the increase of dilution of the solution, i.e., decreasing the
concentration of the solution.
Chem i str y  17.9
(d) Temperature: The degree of ionization increases with the increase in temperature. This is due to the fact
that at higher temperatures molecular speed is greater than before which overcomes the forces of attraction
between the ions.
5. ELECTRICAL CONDUCTANCE
The conductance is the property of the conductor (metallic as well as electrolytic) which facilitates the flow of
electricity through it. It is equal to the reciprocal of resistance, i.e.
1 1
Conductance
= = ... (i)
Resistance R
It is expressed in the unit called reciprocal ohm ( ohm−1 or mho) or Siemens.
5.1 Specific Conductance or Conductivity
The resistance of any conductor varies directly with its length (l) and inversely with its crosssectional area (a),
l l
i.e. R ∝ or R = ρ …..... (ii)
a a
Where, ρ is called the specific resistance. If l = 1 cm and a = 1cm2 , then R = ρ ... (iii)
The specific resistance is, thus, defined as the resistance of one centimeter cube of a conductor.
The reciprocal of specific resistance is termed the specific conductance or it is the conductance of one centimeter
cube of a conductor. It is denoted by the symbol κ, Thus,
1
κ= , κ= kappa − The specific conductance ... (iv)
ρ
Specific conductance is also called conductivity.
a. 1 l .1 l l
From eq. (ii), we=
have ρ R or
= ; κ= × C = cell constant
l ρ a R a a
or Specific conductance = conductance × cell constant
5.2 Equivalent Conductance
Equivalent conductance is defined as the conductance of all the ions produced by one gramequivalent of an
electrolyte in a given solution. It is denoted by Λ .
In general Λ = κ × V ... (v)
Where, V is the volume in mL containing 1 gequivalent of the electrolyte.
In case the concentration of the solution is c gequivalent per liter, then the volume containing
1 gequivalent of the electrolyte will be 1000/c.
1000
So, equivalent conductance Λ = κ × ... (vi)
c
1000
Λ = κ× ; where, N = normality. The unit of equivalent conductance is ohm−1 cm2 eq−1 .
N
5.3 Molar Conductance
The molar conductance is defined as the conductance of all the ions produced by ionization of 1 gmole of an
electrolyte when present in V ml of solution. It is denoted by µ.
Molar conductance µ = κ × V ... (vii)
1 7 . 1 0  Electrochemistr y
Where, V is the volume in mL containing 1 gmole of the electrolyte. If c is the concentration of the solution in
1000
gmole per liter, then µ = κ × Its unit is ohm−1 cm2 mol−1 .
c
Molar conductance Molecular mass
Equivalent conductance = ; where, n =
n Equivalent mass
Illustration 7: 1.0 N solution of a salt surrounding two platinum electrodes 2.1 cm apart and 4.2 sq. cm in area was
found to offer a resistance of 50 ohm. Calculate the equivalent conductivity of the solution. (JEE MAIN)
Sol: As Equivalent conductivity = κ × V
In order to find equivalent conductivity we have to calculate specific conductance.
l 1
Specific conductance ( κ ) is given as κ = .
a R
l 1
Given, l = 2.1 cm, a = 4.2 sq. cm, R = 50 ohm. Specific conductance, κ = .
a R
2.1 1
Or =
κ × = 0.01 ohm−1 cm−1 ; Equivalent conductivity = κ × V
4.2 50
V = The volume containing 1 gequivalent = 1000 mL
= 0.01 × 1000 = 10 ohm−1 cm2 eq−1
So, Equivalent conductivity
Illustration 8: The specific conductivity of 0.02M KCl solution at 25ºC is 2.768 × 10−3 ohm−1 cm−1 . The resistance
of this solution at 25ºC when measured with a particular cell was 250.2 ohm. The resistance of 0.01 M CuSO 4
solution at 25ºC measured with the same cell was 8331 ohm. Calculate the molar conductivity of the copper
sulphate solution. (JEE ADVANCED)
1000
Sol: Molar conductivity is given
= by Sp. cond. × so first we have to calculate specific conductivity of the
C
solution. Sp.conductivity is given as a product of cell constant and conductance. Now cell constant is not provided;
we can calculate it from the conductance and Sp.conductivity of KCl solution.
Sp. cond. of KCl 2.768 × 10−3
Cell constant = = = 2.768 × 10−3 × 250.2
Conductance of KCl 1 / 250.2
For 0.01 M CuSO4 solution
1
Sp. Conductivity = Cell constant × Conductance = 2.768 × 10−3 × 250.2 ×
8331
1000 2.768 × 10−3 × 250.2 1000
= Sp. cond.
Molar conductance = × = × 8.312 ohm−1 cm2 mol−1
C 8331 1 / 100
6. KOHLRAUSCH’S LAW
At infinite dilution, when dissociation is complete, each ion makes a definite contribution towards molar conductance
of the electrolyte, irrespective of the nature of the ion with which it is associated and the value of molar conductions
of its constituent ions, i.e., Λ = λ + + λ − λC and λa are called the ionic conductance of cation and anion at infinite
dilution respectively. The ionic conductance are proportional to their ionic mobilities. Thus, at infinite dilution,
λC = kuC and λa = kua, where, uC and ua are ionic mobilities of cation and anion respectively at infinite dilution. The
value of k is equal to 96500 C, i.e., one Faraday.
Thus, assuming that increase in equivalent conductance with dilution is due to increase in the degree of dissociation
of the electrolyte, it is evident that the electrolyte achieves the degree of dissociation as unity when it is completely
ionized at infinite dilution. Therefore, at any other dilution, the equivalent conductance is proportional to the
degree of dissociation. Thus,
Chem i str y  17.11
Λ Equivalent conductance at a given concentration
Degree of dissociation =
α =
Λ∞ Equivalent conductance at inf inite dilution
Ionic Mobility, µ: It is the distance travelled by an ions per second under a potential gradient of 1 volt per meter.
1. For an, µ = λ º /F
2. Ionic mobility of an ion depends on its charge, size, viscosity of solvent, temperature, etc.
3. For aqueous solution, greater the charge or smaller the size of gaseous ion, greater will be the size of aqueous
ion. When such a big ion moves in solution, it experiences greater resistance by the size of solvent particles.
This results in a decrease in its conductance as well as ionic mobility. Following are the increasing order of
ionic mobilities of some ions:
Li+ < Na+ < K + < Rb+ < Cs+ ; F− < Cl− < Br − < I − ; Al3+ < Mg2+ < Na+
4. The size of gaseous H+ ion is smallest among all the ions and hence its ionic mobility should be minimum
but among all the ions, it is maximum. The ion with second highest ionic mobility is OH–. The very high ionic
mobilities of these ions are due to interchange of hydrogen bonds and covalent bonds, by which migration of
charge occurs without any large displacement in the ions (Grotthus mechanism).
Applications of Kohlrausch’s Law:
0 0
(a) Determining Λm of a weak electrolyte: In order to calculate Λm of a weak electrolyte say CH3COOH, we
0
determine experimentally Λm values of the following three strong electrolytes:
(i) A strong electrolyte containing same cation as in the test electrolyte, say HCl
(ii) A strong electrolyte containing same anion as in the test electrolyte, say CH3COONa
(iii) A strong electrolyte containing same anion of (a) and cation of (b) i.e. NaCl.
0 0 0 0 0
Λm of CH3COOH is then given as: Λm (CH3COOH) = Λm (HCl) + Λm (CH3COONa) − Λm (NaCl)
0
Proof: Λm (HCl) = λH0 + λ ... (i)
Cl−
0
Λm (CH3COONa) = λ0 +λ ... (ii)
CH3COO− Na+
0
Λm (NaCl) = λ0 + λ0 − ... (iii)
Na+ Cl
Adding equation (I) and equation (II) and subtracting (III) from them:
0 0 0
Λ(HCl) + Λ(CH − Λ(NaCl) = λ0 + + λ0 = Λ0(CH
3COONa) (H ) (CH3COO− ) 3COOH)
No. of molecules ionised Λm
(b) Determination
= of degree of dissociation (α): α =
Total number of molecules dissolved Λ0
m
0 1000 κ
(c) Determination of solubility of sparingly soluble salt: Λm = ,
C
Where C is the molarity of solution and hence the solubility.
0 0
(d) Determination of ionic product of water: From Kohlrausch’s law, we determine Λm of H2O where Λm is the
molar conductance of water at infinite dilution when one mole of water is completely ionized to give one mole
0
of H+ and one mole of OH− ions i.e. Λm (H2O) = λ0 + + λ0
H OH−
κ × 1000
Again using the following Λm = , where C=molar concentration i.e. mole L−1 or mole dm−3
C
1 7 . 1 2  Electrochemistr y
κ
⇒ Λm = , where C = concentration in mole m−3
C
0 0 κ κ
Assuming that Λm differs very little from Λm ; Λm = ⇒C=
C Λm0
Specific conductance ( κ ) of pure water is determined experimentally. Thereafter, molar concentration of
dissociated water is determined using the above equation. K w is then calculated as: K w = C2
7. THEORY OF WEAK ELECTROLYTES
(i) Electrolytes that are not completely ionized when dissolved in a polar medium like water are called weak
electrolytes. There exists equilibrium between ions and unionized molecules. AB A + + B−
(ii) The Concept of chemical equilibrium and law of mass action can be applied to ionic equilibrium also.
AB A⁺ + B⁻
t = 0 C 0 0
[A + ][B− ] Cα × Cα Cα 2
teq. C – Cα Cα; K
Cα = = ; K= ... (i)
[AB] C(1 − α ) 1−α
For weak electrolytes, α << 1 ∴ (1 − α ) ≈ 1
K
Thus, equation (i) can be written as: K= Cα2 ⇒ α = ... (ii)
C
From eq. (ii), it is clear that on dilution concentration decreases, as a result of which degree of ionization 'α'
increases. Both equivalent and molar conductance increase when at a high degree of ionization.
ΛCe Λm
C
(iii) Degree of ionization can be calculated as: =
α = ... (iii)
Λe∞ Λm
∞
ΛCe , Λm
C
= Equivalent and molar conductance at concentration ‘C’
Λe∞ , Λm
∞
= Equivalent and molar conductance at infinite dilution. 2
ΛC
C × ∞e
Λ C( ΛCe )2
Substituting the values of ' α ' from eq. (iii) in eq. (i),=
we get K = e ... (iv)
ΛCe Λe∞ ( Λe∞ − ΛeC )
C 2
C( Λm ) 1 −
Similarly K = Λe∞ ... (v)
∞ ∞ C
Λm ( Λm − Λm )
Equations (iv) and (v) are called Ostwald equation.
Illustration 9: A decinormal solution of NaCl has specific conductivity equal to 0.0092. If ionic conductance of Na+
and Cl− ions at the same temperature are 43.0 and 65.0 ohm−1 respectively, calculate the degree of dissociation of
NaCl solution. (JEE MAIN)
Sol: Degree of dissociation is calculated as equivalent conductance at a particular dilution divided by equivalent
conductance at infinite dilution.so first we have to calculate Λ ∞
Λ v . Λ ∞ is determined by summing up ionic conductance of each ion. Λ v is product of specific conductance and
dilution.
Equivalent conductance of N/10 NaCl solution
=Λ v Sp.conductivity × dilution = 0.0092 × 10,000 = 92 ohm−1 ;
Λ∞ = λ +λ = 43.0 + 65.0 = 108 ohm−1
Na+ Cl−
Chem i str y  17.13
Λv 92
Degree of dissociation, =
α = = 0.85
Λ ∞ 108
Illustration 10: At 18ºC, the conductivities at infinite dilution of NH4 Cl,NaOH and NaCl are 129.8, 217.4 and 108.9
mho respectively. If the equivalent conductivity of N/100 solution of NH4 OH is 9.93 mho, calculate the degree of
dissociation of NH4 OH at this dilution. (JEE ADVANCED)
Sol: Degree of dissociation is calculated as equivalent conductance at a particular dilution divided by equivalent
conductance at infinite dilution. Λ v is given. Λ ∞ is determined by summing up ionic conductance of each ion
Λ ∞NH =λ +λ = 129.8 ... (i)
4 Cl NH+
4 Cl−
Λ ∞NaOH = λ +λ = 217.4 ... (ii)
Na+ OH−
Adding eqs. (i) and (ii) and subtracting eq. (iii),
Λ +λ +λ +λ −λ −λ =λ +λ = 129.8 + 217.4 − 108.9
NH+
4 Cl− Na+ OH− Na+ Cl− NH+
4 OH−
Λv 9.93
Λ ∞NH 238.3 mho . Degree of dissociation, =
= α = = 0.04167 or 4.17% dissociated.
4 OH Λ ∞ 238.3
8. ELECTROCHEMICAL CELLS
8.1 Electrolytic Cells
Electrolytic cells are devices in which electrolysis (chemical reaction involving oxidation and reduction) is carried
out by using electricity or in which conversion of electrical energy into chemical energy is done.
8.2 Galvanic Cells
This is a device where a redox reaction is used to convert chemical energy into electrical energy, i.e., electricity is
obtained with the help of oxidation and reduction reaction. The chemical reaction responsible for production of
electricity takes place in two separate compartments. Each compartment consists of a suitable electrolyte solution
and a metallic conductor. The metallic conductor acts as an electrode and the compartments containing the
electrode and the electrolyte solution are called halfcells. When the two compartments are connected by a salt
bridge and electrodes are joined by a wire through the galvanometer, the electricity begins to flow. This is the
simple form of voltaic cell.
8.3 Daniel Cell
Figure 17.1: Representation of a daniel cell
1 7 . 1 4  Electrochemistr y
Oxidation half reaction, Zn(s) → Zn2+ (aq.) + 2e−
Reduction half reaction, Cu2+ (aq.) + 2e− → Cu(s)
Net reaction Zn(s) + Cu2+ (aq.) → Zn2+ (aq.) + Cu(s)
Salt Bridge: A Salt bridge is usually an inverted Utube filled with a concentrated solution of inert electrolytes. An
inert electrolyte is one whose ions are neither involved in any electrochemical change nor do they react chemically
with the electrolytes in the two halfcells.
Significance of salt bridge: The following are the functions of the salt bridge:
(i) It connects the solutions of two halfcells and completes the cell circuit.
(ii) It prevents transference or diffusion of the solutions from one halfcell to the other.
(iii) It keeps the solutions in two halfcells electrically neutral.
(iv) It prevents liquidliquid junctionpotential, i.e., the potential difference which arises between two solutions
when in contact with each other.
A broken vertical line or two parallel vertical lines in a cell reaction indicates the salt bridge.
Zn  Zn2+  Cu2+  Cu
Electrode Potential: A metal placed in a solution of its ions obtains either a positive or negative charge with respect
to the solution. On account of this, a definite potential is developed between the metal and the solution. This potential
difference is called electrode potential. It depends on the nature of electrode, concentration of ions and temperature.
Oxidation Potential: It is the tendency of an electrode to get oxidized, i.e., to lose electrons.
M → Mn+ + ne−
Reduction potential: It is the tendency of an electrode to get reduced, i.e., to accept electrons.
Mn+ + ne− → M
Standard Electrode Potential: The potential difference developed between metal electrode and the solution of its
ions of unit molarity (1 M) at 25ºC (278 K) is called standard electrode potential.
The magnitude of potential depends on the following factors:
(i) Nature of the electrode,
(ii) Concentration of the ions in solution,
(iii) Temperature.
Standard Electrode Potential: While dipping an electrode in a solution in order to compare the electrode
potentials of different electrodes, it is essential to first specify the ion concentration in the solution as well as the
temperature of the half cell. The potential difference developed between metal electrode and the solution of its
ions of unit molarity (1 M) at 25ºC (298 K) is called standard electrode potential. Standard oxidation potential =
Standard reduction potential
EMF of a cell: It is the difference in the potential across left and right electrodes due to which electrons flow from
anode to cathode.
Standard EMF: The EMF values of an electrode under standard conditions (1 atm, 298 K) and the unit concentrations
of its ions is called as standard EMF and is denoted by Ecell
º º º º º º
Ecell Ecathode
= − Eanode or Ecell Eright
= electrode − Eleft electrode
Chem i str y  17.15
8.4 Reference Electrode (Standard Hydrogen Electrode, SHE or NHE)
The potential of an individual halfcell cannot be measured but the difference in the potential of two halfcells
can be measured experimentally. It is therefore, necessary to couple the electrodes with another electrode whose
potential is known. This electrode is termed as reference electrode like standard hydrogen electrode (SHE). Which
is standard electrode potential considered zero.
H2(g)
(at 1 atm)
H3 O+(aq.) Pt black
(1 M) electrode
Figure 17.2: Representation of reference electrode
The hydrogen electrode thus obtained forms one of two halfcells of a voltaic cell. A voltaic cell is created when this
halfcell is connected with any other halfcell. The hydrogen electrode can act as cathode or anode with respect to
other electrode.
SHE half reaction Electrode potential
+ −
H2 → 2H + 2e 0.0 V (Anode)
2H+ + 2e− → H2 0.0 V (Cathode)
8.5 Some other Reference Electrodes
(i) Calomel Electrode: Pt wire
To salt
bridge
Saturated
KCl solution
Hg2Cl2 and
Hg paste
Mercury
Figure 17.3: Representation of calomel electrode
1
→ Hg + Cl
Reaction when electrode act as cathode: Hg2Cl2 + e− ←
2
(ii) Silversilver chloride electrode: This is another widely used reference electrode. It is reversible and stable
and can be combined with cells containing chlorides without inserting liquid junction.
Silver chloride is deposited electrolytically on a silver or platinum wire and it is then immersed in a solution
containing chloride ions. Its standard electrode potential with respect to the standard hydrogen electrode is
0.2224 V at 298 K. The electrode is represented as: Ag  AgCl  Cl–
The electrode reaction is: AgCl + e− → Ag + Cl−
1 7 . 1 6  Electrochemistr y
PLANCESS CONCEPTS
In MnO −4 + 8H+ + 5e → Mn2+ + 4H2O , oxidant should be taken as [MnO −4 ][H+ ]8 ,i.e., all ions
concentration present with oxidant should be reported accordingly in Nernst halfcell potential. Similarly
for reductant, all ions present with reductant should be considered.
Aman Gour (JEE 2012 AIR 230)
8.6 Nernst Equation
Nernst Equation: Suppose, for example, that we reduce the concentration of Zn2+ in the Zn/Cu cell from its unit
activity value of around 0.5 M to a much smaller value:
Zn(s) Zn2+ (0.001M)  Cu2+  Cu(s)
This will reduce the value of Q for the cell reaction Zn(s) + Cu2+ → Zn2+ + Cu(s)
The free energy change ∆G more negative than ∆G0, so than E would be more positive than Eº.
The relation between the actual cell potential E and the standard potential Eº is developed in the following way.
According to cell potential and Gibb’s free energy change: ∆G0 = –nEoF; ∆G = –nEF
These expressions can then be substituted into the relation ∆G = ∆G0 + RTIn Q
RT
Which gives –nEF = –nEoF + RTIn Q . Which can be rearranged to E= E − lnQ
nF
This is Nernst Equation, which relates the cell potential to the standard potential Eº. If Q is unity then at 25ºC
0.059
Nernst Equation will be E= Eº − logQ
n
And for a general electrochemical reaction of the type aA+bBcC+dD
RT RT [C]c [D]d
Nernst equation can be written as: Ecell =
E(cell) − lnQ =
E(cell) − ln
nF nF [A]a [B]b
PLANCESS CONCEPTS
• The overall reaction and ∆Gº for each cell is same.
º
• Ecell and 'n' values are different for each cell.
º
• Ecell × n is same for each cell.
º
• ∆Gº depends on cell reaction and Ecell depends upon making up of a cell.
B Rajiv Reddy (JEE 2010 AIR 11)
Chem i str y  17.17
8.7 Electrochemical Series
Characteristics of electrochemical series
(a) Negative sign of SRP (standard reduction potential) indicates that an electrode when joined with SHE acts as
anode and oxidation occurs on this electrode. Similarly positive sign of SRP indicates that an electrode when
joined with SHE acts as cathode and reduction occurs on this electrode.
(b) In the series, those substances that are stronger reducing agents than hydrogen are placed above it.
(c) The substances which are stronger oxidizing agents than H+ ion are placed below hydrogen in the series.
(d) The activity decreases from top to bottom and the metals on top are called active metals.
Application of electrochemical series
(i) Reactivity of metals
•• Alkali metals and alkaline earth metals having high –ve values of SRP which are chemically active react
with cold water, evolve hydrogen and readily dissolve in acids.
•• Metals like Fe, Pb, Sn, Ni, Co etc. do not react with cold water but react with steam to evolve hydrogen.
•• Metals Li, Be, Cu, Ag and Au which lie below hydrogen are less reactive and do not evolve hydrogen from
water.
(ii) Electropositive character of metals: Electropositive character of metals decreases from top to bottom.
(iii) Displacement reactions: The metal having low SRP will displace the metal from its salt’s solution which has
higher value of SRP.
(iv) Reducing power of metals: Reducing nature decreases from top to bottom in the electrochemical series.
(v) Oxidizing nature of nonmetals: Oxidizing nature increases from top to bottom in the electrochemical
series.
(vi) Thermal stability of metallic oxides: The thermal stability of the metal oxide decreases from top to bottom.
(vii) Products of electrolysis: The ion which is a stronger oxidizing agent is discharged first at cathode.
K + ,Ca2+ ,Na+ ,Mg+2 , Al+3 , Zn+2 ,Fe+2 ,H+ ,Cu+2 , Ag+ , Au+3 increasing order of deposition.
(viii) Corrosion of metals: Corrosion is defined as the deterioration of a substance because of its reaction with its
environment. The corrosion tendency decreases from top to bottom.
(ix) Extraction of metals: Ag and Au extracted by cyanide process.
1 7 . 1 8  Electrochemistr y
Table 17.3: Reduction potential of different ions

Reaction (Oxidized form + ne ) → Reduced form Eº/V
2.87
F2 (g) + 2e− → 2F−
1.81
Co3+ + e− → Co2+
→ 2H2O 1.78
H2O2 + 2H+ + 2e−
→ Mn2+ + 4H2O 1.51
MnO −4 + 8H+ + 5e−
1.40
Au3+ + 3e− → Au(s)
1.36
Cl2 (g) + 2e− → 2Cl−
→ 2Cr3+ + 7H2O 1.33
Cr2O27− + 14H+ + 6e−
→ 2H2O 1.23
O2 (g) + 4H+ + 4e−
2+
→ Mn + 2H2O 1.23
MnO2 (s) + 4H+ + 2e−
1.09
Br2 + 2e− → 2Br −
Increasing strength of oxidizing agent
Increasing strength of reducing agent
→ NO(g) + 2H2O 0.97
NO3− + 4H+ + 3e−
→ Hg22+ 0.92
2Hg2+ + 2e−
0.80
Ag+ + e− → Ag(s)
0.77
Fe3+ + e− → Fe2+
→ H2O2 0.68
O2 (g) + 2H+ 2e−
0.54
I2 + 2e− → 2I −
0.52
Cu+ + e− → Cu(s)
0.34
Cu2+ + 2e− → Cu(s)
0.22
AgCl(s) + e− → Ag(s) + Cl−
0.10
AgBr(s) + e− → Ag(s) + Br −
→ H2 (g) 0.00
2H+ + 2e
0.13
Pb2+ + 2e− → Pb(s)
0.14
Sn2+ + 2e− → Sn(s)
0.25
Ni2+ + 2e− → Ni(s)
Chem i str y  17.19

Reaction (Oxidized form + ne ) → Reduced form Eº/V
→ Fe(s) 0.44
Fe2+ + 2e−
→ Cr(s) 0.74
Cr3+ + 3e−
Increasing strength of oxidizing agent
Increasing strength of reducing agent
→ Zn(s) 0.76
Zn2+ + 2e−
2H2O + 2e− → H2 (g) + 2OH− (aq) 0.83
Al3+ + 3e− → Al(s) 1.66
Mg2+ + 2e− → Mg(s) 2.36
Na+ + e− → Na(s) 2.71
Ca2+ + 2e− → Ca(s) 2.87
K + + e− → K(s) 2.93
Li+ + e− → Li(s) 3.05
Two important parameters that can be determined from a cell potential are the equilibrium constant for the cell
reaction and the free energy change for the cell reaction.
º
1. Determining the equilibrium constant from Ecell
º
2. Determining the standard state free energy change from Ecell
3. Determining the nonstandard free energy change
º
Determining the Equilibrium Constant from Ecell
To calculate the equilibrium constant for an electrochemical cell we need to know:
1. The standard state potential for a cell
2. The halfreactions involved
º RT
The Nernst equation is used in calculating the equilibrium constant. Ecell = lnQ
nF
At equilibrium Q = K, Substituting in K for Q and the values for R, T and F we get:
º 0.0257 0.0592
=Ecell = lnK logK
n n
Example: Find the value of the equilibrium constant at 25ºC for the cell reaction for the following electrochemical
cell: Cu  Cu2+ (1M)  Ag+ (1M)  Ag
Sol: (i) Write the equations for the cell halfreactions, calculate the standard cell potential and determine the
number of electrons transferred.
º
2Ag+ (aq) + 2e− → 2Ag(s) Ereduction = +0.799 V
º
Cu(s) → Cu2+ (aq) + 2e− Eoxidation = −0.518 V
º
2Ag+ (aq) + Al(s) → 2Ag(s) + Cu2+ (aq) Ecell = +0.281 V
1 7 . 2 0  Electrochemistr y
n = 2 moles of electrons
(ii) Substitute into the above equations and solve for K.
0.0592 0.0592
º
Ecell = logK ; 0.281 = K 109.49
logK ; logK = 9.49 ; = = 3.1 × 109
n 2
Note: values for the equilibrium constant for electrochemical cell reactions are sometimes very large.
º
Determining the Standard State Free Energy Change from Ecell
To determine the standard state free energy change for a cell reaction
º
1. Determine the Ecell
2. Determine the number of moles of electrons transferred in the reaction.
º
3. Solve for ∆G using the equation ∆G =
−nFEcell
∆Gº =standard state free energy change ( joules); n = number of moles of electrons transferred
º
F = Faraday’s constant (96,485 C/mole e− ); Ecell = standard state cell potential (volts or joules/C)
Example: Find the value of the equilibrium constant at 25ºC for the cell reaction for the following electrochemical
cell: Cu  Cu2+ (1M)  Ag+ (1M)Ag
º
(The solution for the determination of the Ecell and the number of moles of electrons, n, are shown in the example
in the previous section.)
º º
1. Determine the Ecell . Ecell = +0.281 volts
2. Determine the number of moles of electrons transferred. n = 2 moles of e−
3. Substitute into the equation and solve.
∆G =−(2mole− )(96, 485C / mole− )0.281 J / C; ∆G =−54,200 J or − 54.2kJ
Determining the NonStandard State Free Energy Change
To determine the nonstandard state free energy change:
º
1. Calculate the standard cell potential, Ecell
2. Determine the number of moles of electrons transferred, n
3. Calculate the reaction quotient, Q
4. Calculate the nonstandard cell potential, Ecell, using the Nernst equation
5. Calculate the nonstandard free energy change using the equation: ∆G =−nFEcell
Example: Calculate the free energy change for the following electrochemical cell.
Zn(s)  Zn2+ (1.50M)  Cu2+ (0.25M)  Cu(s)
º
1. Calculate Ecell .
º
Zn(s) → Zn2+ (aq) + 2e− Eoxidiation = +0.762 volts
º
Cu2+ (aq) + 2e− → Cu(s) Ereduction = +0.339 volts
º
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Ecell = +1.101 volts
2. Determine “n”. n = 2 moles of electrons
∆G =−208. = Q = = 6. Calculate Q.9 Dry Cell In this cell.6 volt.101 volts − ln6 = 1.0257 4.078 volt 2 5. Calculate Ecell . This is also defined as the process by which metals have the tendency to go back to their combined state. 2MnO2 + H2 → 2MnO(OH) Ammonia produced at cathode combines with zinc ions to form complex ion.) Oxidation: Fe2O3 + xH2O → Fe2O3 .. the zinc is oxidized to Zn2+ .4 : Process of corrosion Oxidation: Fe(s) → Fe2+ (aq. 485C / mole e− )(1. Water drop O2 O2 OH. once the chemicals have been consumed.) + 4e− → 2H2O(l ) Atmospheric: 4Fe2+ + O2 + 4H2O(l ) → 2Fe2O3 (s) + 8H+ (aq. Chem i str y  17.078 volts) .8 Corrosion The weakening and deterioration of a substance because of its reaction with its environment is called as corrosion.25 0. . Calculate ∆G. i. ∆G =−nFEcell =−(2mole e− )(96.50 3. 2NH+4 + 2e− → 2NH3 + H2 (Cathode reaction) The cell reaction is Zn + 2NH+4 → Zn2+ + 2NH3 + H2 Hydrogen is oxidized by MnO2 in the cell.e. reverse of extraction of metals. 2+ OH Fe Rust Rust Cathode Anode Cathode Iron e. Zn → Zn2+ + 2e− (Anode reaction) The electrons are utilized at carbon rod (cathode) as the ammonium ions are reduced. Zn2+ + 4NH3 →[Zn(NH3 )4 ]2+ . xH2O Rust 8.) + 2e− Reduction: O2 + 4H+ (aq. Ecell = 1. It cannot be regenerated by reversing the current flow through the cell using an external direct current source of electrical energy. e Figure 17.000 joules or − 208kJ 8. further reaction is not possible. Ecell is 1. As the cell operates.21 [Zn2+ ] 1.0 [Cu2+ ] 0.
The overall cell reaction produces water. is independent of concentration of alkali because redox reaction does not involve [OH⁻]. Mredul Sharda JEE Advanced 2013 AIR 8. two amalgams of the same metal at two different concentrations are immersed in the same electrolytic solution. • In alkaline cells.H2 (Pr essure p1 ) H2 (Pressure p2 )Pt [H+ ] Anode Cathode If p1 > p2 . ∆G η= ∆H 8.) Overall: 2H2 (g) + O2 (g) → 2H2O(l ) These type of cells are used in spacecrafts. e. • Alkaline cells show more efficient ion transport because of alkaline electrolyte and thus give rise to more stable current and voltage. The main disadvantage of a primary cell is that it can deliver current for a short period only. 2 2  Electrochemistr y PLANCESS CONCEPTS • T hese are called dry cells but are not actually dry. Hydrogen is oxidized at anode and oxygen is reduced at cathode. 0.11 Concentration Cell (a) Electrode concentration cells: In these cells. • Alkaline cells retards corrosion as corrosion is favored more in H+ ions.) → 2H2O(l ) + 2e− ] × 2 Cathode: O2 (g) + 2H2O(l ) + 4e− → 4OH− (aq. Hydrogen gas is introduced into one compartment and oxygen gas is fed into another compartment. This is because the quantity of oxidizing agent and reducing agent is limited. The cell consists of three compartments separated by a porous electrode. Pt. oxidation occurs at LHS electrode and reduction occurs at RHS electrode. Fuel cells are efficient and pollution free.1 7 . These gases then diffuse slowly through the electrodes and react with electrodes that are made of porous carbon and the electrolyte is a resin containing concentrated aqueous sodium hydroxide solution.10 Fuel Cell Fuel cells are another means to convert chemical energy to electrical energy. Thermodynamic efficiency of fuel cells is the ratio of the electrical free energy to the enthalpy of the reaction. One of the examples is the hydrogenoxygen fuel cell. .f. These contain moist paste and operate only as long as the paste in it remains wet.0591 (p ) Ecell = log 1 at 25º C 2 (p2 ) In the amalgam cells. the potential difference is developed between two like electrodes at different concentrations dipped in the same solution of the electrolyte.m. two hydrogen electrodes at different gas pressures in the same solution of hydrogen ions constitute a cell of this type. For example. But energy can be obtained indefinitely from a fuel cell as long as the outside supply of fuel is maintained. The reactions which occur are: Anode: [H2 (g) + 2OH− (aq. M(HgC1 )  M n+  Zn(HgC2 ) .
Thus.10 M and the bromide ion concentration is 0. Such a cell is represented in the following manner: ( C2 is greater than C1 ). at the beginning.Eoxidation º of Zn = −( −0.50 atm. the two concentrations tend to become equal. (iii) Calculate the value for the reaction quotient. Cu2+ (aq) + 2e− → Cu(s) º (ii) Look up the standard potentials for the reduction halfreaction. º º Oxidation: Zn(s) → Zn2+ (aq) + 2e− Eoxidation = −Ereduction = −( −0. With the expiry of time.25 M.077 V) = −1. Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Sol: (i) Write the halfreactions for each process.762 V) = +0.762 V. the hydrogen ion concentration is 0.f of the cell is at its maximum and it gradually falls to zero.f of the cell is given by the expression Ecell = log 1 at 25º C n C2 (b) Electrolyte concentration cells: In these cells.0591 C The e.762 V (iv) Add the cell potentials together to get the overall standard cell potential. Ereduction of Cu2+ = +0.m. Zn  Zn2+ (C1 )  Zn2+ (C2 )  Zn M  Mn+ (C1 )  Mn+ (C2 )  M or Anode Cathode 0.229 V Overall: O2 (g) + 4H+ (aq) + 4Br − (aq) → 2H2O(l ) + 2Br2 (l ) Eº = +0. the e.) . Q.f of the cell is given by the following expression: Ecell = log 2(RHS) at 25ºC n C1(LHS) The concentration cells are used to determine the solubility of sparingly soluble salts.762 V º Reduction: Cu2+ (aq) + 2e− → Cu(s) Ereduction = +0. Chem i str y  17. Zn(s) → Zn2+ (aq) + 2e− .762 V) = +0.339 V (iii) Look up the standard reduction potential for the reverse of the oxidation reaction and change the sign. º Ereduction of Zn2+ = −0. electrodes are identical but these are immersed in a solution of the same electrolyte of different concentrations. O2 (g) + 4H+ (aq) + 4Br − (aq) → 2H2O(l ) + 2Br2 (l ) º Sol: (i) Calculate the standard cell potential for the reaction. (Note: We calculate Q using molar concentrations for solutions and pressures for gases.0591 C The e.m. The source of electrical energy in the cell is the tendency of the electrolyte to diffuse from a solution of higher concentration to that of lower concentration. valency of the cation of the electrolyte and transition point of the two allotropic forms of a metal used as electrodes.152 V cell (ii) Determine the new cell potential resulting from the changed conditions. Ecell.101 V Example: Predict the cell potential for the following reaction when the pressure of the oxygen gas is 2.m. Example: Find the standard cell potential for an electrochemical cell with the following cell reaction.077 V − − + − º Reduction: O2 (g) + 4H (aq) + 4e → 2H2O(l ) Ereduction = +1. therefore they are not included in the calculation of Q.23 0. etc. Water and bromine are both liquids.339 V º Overall: Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Ecell = +1. using the tabled values: º º Oxidation: 4Br (aq) → 2Br2 (l ) + 4e Eoxidation = −Ereduction = −( +1.
Standard potential E for the cell is given by standard potential of reducing electrode+ standard potential of oxidising electrode.20 volt Cd/Cd2 + Ag+ /Ag Illustration 12: The standard oxidation potential of zinc is 0.1M Sol: First calculate the standard potential for reaction which is calculated as º º º Ecell = Eoxidation − Ereduction º After calculating Ecell e.80 volt.m. (i) The half reactions are: 2Ag+ + 2e− → 2Ag Re duction (Cathode) Eº = 0.76 volt and of silver is − 0.0591 [Products] E= cell Ecell − log n [Reactants] º The cell reaction is Zn + 2Ag+ → 2Ag + Zn2+ .0413) volt = 1. n 0.= + 4 − 4 PO [H ] [Br ] (2.m. n = 4 moles of electrons (v) Substitute values into the Nernst equation and solve for the nonstandard cell potential. The electrode having less electrode potential act as negative electrode.02 × 106 .25 0.80 volt and −0. 1 7 .063V Illustration 11: Reaction → 2Ag + Cd2+ .Ecell = Ecell = 0.0591 = Ecell − log 1.f of the cell can be easily calculated using following equation º 0.50atm)(0.25M 0.76 + 0. Q Q 1.80 = 1.40 + 0.0591 0.56 − 0.3979 = (1.40 volt (Reduction potential) or Eº = +0.0591 [Products] We know that. Calculate the e. n.f of the cell: Zn  Zn(NO3 )2  AgNO3  Ag At 25ºC.56 − = × 1.1 2 .40 volt Cd2 + /Cd Cd/Cd2 + Eº = Eº + Eº = 0.80 volt (Reduction potential).10 M)4 (0.25M)4 2 (iv) Calculate the number of moles of electrons transferred in the balanced equation.56 volt º 0. The standard electrode potentials for Ag+ → Ag and Cd2+ → Cd couples are 0. (JEE MAIN) 0. Eoxidation of Zn = 0. E= cell Ecell − log n [Reactants] º 0.02 × 106 ). +0.5187 volt .40 volt respectively (i) What is the standard potential E for this reaction? (ii) For the electrochemical cell. in which this reaction takes place which electrode is negative electrode? (JEE MAIN) Sol: First write down the two halfcell.76 volt º º º º Ereduction of Ag = 0.0257 / 4)ln(1.152 V − (0.80 volt .80 = 1.1 × 0. 2 4  Electrochemistr y 1 1 Q = . Cd → Cd2+ + 2e− Ag+ /Ag Oxidation ( Anode ) Eº = −0. Ecell = Eoxidation of Zn + Ereduction of Ag = 0. Ecell .
42 + 0.80 volt.17 − 0.m.42 volt. 2 (1 × 10−3 )2 Illustrations 14: To find the standard potential of M3+ / M electrode. Mg(s)  Mg2+ (0.f is given we have to calculate standard potential of anode.37) = 3. Nernst equation º 0.064) =0. E= cell Ecell − log n [Ag+ ]2 0.1 M? (JEE MAIN) Sol: First calculate the standard potential for reaction which is calculated as º º º Ecell = Eoxidation − Ereduction º After calculating Ecell e.2 = 3.17 − 0.25 Illustration 13: Calculate the e.2M)  Ag+ (1 × 10 −3 )  Ag Eº +0. Eº = 0.f if concentration of Mg2+ ion is decreased to 0.f of the cell can be easily calculated using following equation º 0.01)3 º º Ecell = ECathode − EºAnode or = EºAnode ECathode º º − ECell =(0. Mg + 2Ag+ → 2Ag + Mg2+ .0591 [M3+ ] Applying Nernst equation. Standard potential of cell can be determined using following expression.1566 = = 2 [1 × 10−3 ]2 º 0.f of the cell.01mol−1L) Ag The e. Ecell =(0.80 − ( −2.37 volt = Ag+ /Ag Mg /Mg What will be the effect on e.0134 volt when Mg2+ = 0.80 − 0.0223 volt.1 E= cell Ecell − log = (3.17 − log 3. the following cell is constituted: Pt  M  M3+ (0. E= cell Ecell − log 3 [Ag+ ]3 º 0.484 volt 3 (0.0591 [M3+ ] E= cell Ecell − log 3 [Ag+ ]3 The cell reaction is M + 3Ag+ → 3Ag + M3+ º 0.0591 0. Chem i str y  17. So first we have to calculate standard potential of the cell and subtract it from the provided standard potential of cathode.f of this cell is found to be 0.0591 (0.484) =0.m.m.m.17 volt º 0.0018) º º 0.1477) volt = 3.064 . Eº 2+ = −2.m.8 volt. .32 volt .0591 0.0018mol−1L)  Ag+ (0.0591 Mg2+ Cell reaction. (JEE MAIN) Ag+ /Ag Sol: Here e. Calculate the standard potential of the half reaction M3+ + 3e− → M.1M 3.0591 [Products] E= cell Ecell − log n [Reactants] º º Ecell = ECathode − EºAnode = 0.42 = Ecell − log Ecell = − 0.
(iii) Determine Q. coulombs. the reaction quotient. (iv) Convert the moles of substance to desired units of measure. For the oxidation halfreaction.485 coulombs = 1 Faraday (iii) 1 Faraday = 1 mole of electrons The through process for interconverting amperes and moles of electrons is: Amps and time Coulombs Faradays Moles of electrons Use of these equations are illustrated in the following sections. (d) Determination of standard cell potentials: A cell’s standard state potential is the potential of the cell under standard state conditions. (c) To calculate the quantity of substance produced or consumed: To determine the quantity of substance either produced or consumed during electrolysis. (ii) Write the oxidation and reduction halfreactions for the cell. time. Ereduction. (ii) Calculate the number of moles of electrons that were transferred. for the reduction halfreaction in a table of reduction potentials. 2 6  Electrochemistr y PROBLEMSOLVING TACTICS (a) Related to electrolysis: Electrolysis comprises of passing an electric current through either a molten salt or an ionic solution. given the time a known current flowed: (i) Write the balanced halfreactions involved. Most electrolysis problems are really stoichiometry problems with the addition of some amount of electric current. (iii) Calculate the number of moles of substance that was produced/consumed at the electrode. º (iii) Look up the reduction potential. faradays and moles of electrons: Three equations related these quantities: (i) Amperes × time = Coulombs (ii) 96. º º º Ecell −Ereduction = + Eoxidation (e) For determining nonstandard state cell potentials: To determine the cell potential when the conditions are other than standard state (concentrations not 1 molar and/or pressures not 1 atmosphere): (i) Determine the standard state cell potential. The quantities of substances produced or consumed by the electrolysis process is dependent upon the following: (i) Electric current measured in amperes or amps (ii) Time measured in seconds (iii) The number of electrons required to produce or consume 1 mole of the substance (b) To calculate amps.1 7 . (ii) Determine the new cell potential resulting from the changed conditions. (i) To calculate the standard cell potential for a reaction. Eoxidation = −Ereduction . (v) Add the potentials of the halfcells to get the overall standard cell potential. (iv) Look up the reduction potential for the reverse of the oxidation halfreaction and reverse the sign to º º obtain the oxidation potential. . Thus the ions are “forced” to undergo either oxidation (at the anode) or reduction (at the cathode). and it is approximated with concentrations of 1 mole per liter (1 M) and pressures of 1 atmosphere at 25ºC.
etc.0257 / n)lnQ or in terms of log10 .0592 / n)logQ POINTS TO REMEMBER S. Utube containing inert electrolytic solution. Ecell = standard state cell potential R = constant (8. (v) Determine Ecell.27 (iv) Determine n. g. HCl.Solutions in which the substance dissolved (solute) is present Electrolytes entirely as ions.31 J/mole K). Description 1 Electrolyte Any substance which dissolves in water to form a solution that will conduct an electric current (ionic substances). 3 Dissociation The separation of ions that occurs when an ionic substance dissolves: CaCl2(s) + H2O → Ca+2(aq) + 2Cl(aq). E= cell Ecell − (0. of the tendency for a half reaction to occur as a reduction half reaction. CH3COOH. HF). paste. [C]c [D]d Q = Reaction quotient for the reaction. NH4NO3. h.Electrolytes may be classified as strong (NaCl. Salt bridge: A device (porous disk or bridge i. Electrode: An electrical conductor (metal strip) used to establish contact with a non Electrochemical cells metallic part of the circuit (usually an electrolyte).e. . KCl. NaOH) or weak (NH4OH. External circuit: The part of the cell where charge is conducted as a current of moving electrons. c. e. Solutions that do not conduct electricity at all are called nonelectrolytes. Electrolyte: A liquid. aA + bB → cC + dD.No. Q = [A]a [B]b If the temperature of the cell remains at 25ºC. Chem i str y  17. in volts. Standard Electrode Reduction Potential E : The measurement. the cell potential at the nonstandard state conditions using the Nernst equation. 2 Strong and Weak Strong electrolyte . or gel that serves to conduct charge by moving ions in the cell. f. d.A solute that yields a relatively low concentration of ions in solution. Anode: The electrode at which oxidation occurs. 4 Electrochemical Cells A system of electrodes and electrolytes in which a spontaneous or nonspontaneous redox reaction occurs. Cathode: The electrode at which reduction occurs. Weak electrolyte . 5 Components of a. b. T = absolute temperature (Kelvin scale) F = Faraday’s constant (96. º E= cell Ecell − (RT / nF)lnQ º Ecell = cell potential at nonstandard state conditions.485 C/mole e− ) n = Number of moles of electrons transferred in the balanced equation for the reaction occurring in the cell. the equation simplifies to: º º E= cell Ecell − (0. Halfcell: A single electrode immersed in a solution of its ions. the number of electrons transferred in the reaction “n”.) placed between the cells which maintains electrical neutrality by allowing ions to migrate between the cells.
electroplating.0 mole of electrons and it is equal to 96500 coulombs (approx. t I = Current strength in ampere T = time in seconds ⇒ W = ZQ = Zit Z is a constant called electrochemical equivalence (ECE) 10 Electrochemical It is the amount of an electrolyte discharged on passing one coulomb of electricity. The cell potential E is positive and the anode is the negative electrode. = I.). W1 and W2 are the weights of electrolytes discharged at two different electrodes in two different cells connected in series and E1 and E2 are their respective equivalent weights.e. Cu(s) Cu+2(1M) Cu+2(1M) Cu(s) anode cathode 8 Quick Comparison of Type of redox reaction cell Galvanic/Voltaic Electrolytic Electrolytic Cells potential (Eºcell) Electron Spontaneous Nonspontaneous flow (Eºcell is positive) (Eºcell is negative) Site of oxidation Creates one Requires one Site of reduction Anode Anode Positive electrode Cathode Cathode Negative electrode Cathode Anode Flow of electrons Anode Cathode Anode to cathode Anode to cathode (negative to positive) (positive to negative) Batteries Electrolysis. Q ⇒ W=E where.No. electroplating 9 Faraday’s First law of The amount of electrolyte discharged at an electrode is directly proportional to the Electrolysis quantity of electricity passed: W ∝ Q where. i. The cell potential (Eo) is negative and the anode is the positive electrode. electrolysis. same number of gram equivalent of electrolytes are discharged at each of the electrodes: W1 E1 ⇒ = W2 E2 Where. Equivalent 11 Faraday’s Constant It is the charge possessed by 1. batteries Zn(s) Zn+2(1M) Cu+2(1M) Cu(s) anode cathode 7 Electrolytic Cells Cell in which an external electric current is required to drive a nonspontaneous redox reaction. . In terms of faraday’s constant the number of gram equivalent of electrolyte discharged at an electrode is equal to the number of faraday’s passed. 2 8  Electrochemistr y S. etc. E = Equivalent weight 96500 12 Faraday’s Second Law Second Law: If same quantity of electricity is passed through different cells connected in series.e. i.1 7 . Description 6 Voltaic/Galvanic Cells Redox reactions are spontaneous and chemical energy is transformed into electrical energy.
Ksp = 8.4 × 1022 electrons ∴ [Ag+] = (K sp=) (8. Ag.0591log [Reduced form] n [Oxidised form] Solved Examples JEE Main/Boards Pt(H2 ) H+ Ag+ Ag Eo cell = 0. Why? Sol: Since platinum electrode has zero reduction Sol: Both Zn and iron have more EOP than Cu. of electron lost or gained during electrolysis of 2 g Cl– from NaCl (aq) to give Cl2 Sol: Here solubility product is given from this calculate at anode. EI/AgI/Ag can find out by Ag+ /Ag ∵ 2Cl– → Cl2 + 2e⁻ using the value of solubility product. Na. Also calculate the standard reduction potential of I– / AgI/Ag electrode. (i).5) eq.No. a saturated solution of AgI. whereas potential the standard electrode potential will be equal Pt and Au have less EOP to the standard electrode potential of the cell.5 35.7991 V 1bar = a 1= a 1 Example 1: Zn and iron can replace Cu in a solution but Pt and Au cannot.799 V.29 S.32 × 10–19 … (ii) Ag /Ag Zn /Zn given values: ∴ By Eq. of Cl– used = 2/35. of an element involves 1 faraday charge or N E = E +(0. Given that for AgI.used during the value in Nernst equation determine E + Ag /Ag reaction and on multiplying it with avogadro number will give us the no of electron lost during the reaction As we have found out E .5 = 3. Cu. the Nernst equation can be written as. Ehalf–cell = E half–cell – 0. Now substituting this Sol: First calculate the equivalent of Cl.7991 V Ag+ /Ag Ag+ /Ag Al. the concentration of silver ions. Example 5: Standard reduction potential of the Ag+/Ag Sol: Al and Na cannot be obtained because they have electrode at 298 K is 0. Eq.5 ∵ 1 eq.023 × 1023 × 2 ∵ [Ag]+ = [I–] (for a saturated solution) = electrons = 35. of an element involves Also.059/1) log [Ag+] … (i) Ag+ /Ag Ag+ /Ag electrons ∴ (2/35. Description 13 Nernst Equation 2.303 RT [Reduced form] Ehalf–cell = E half–cell – log nF [Oxidised form] At 298 K.7 higher EOP than H and thus. Chem i str y  17. reduction of Cu2+ and Ag+ × 10–17. K sp = [Ag+ ][I – ] AgI N× 2 6.7991=0 + ERP ∴ ERP = 0. .7 × 10 –17 ) AgI Example 4: Evaluate the E + and E 2+ from the = 9. evaluate the potential of the Ag+/Ag electrode in will give Cu and Ag. Ecell = EOP + ERP Example 2: Which of the following metals cannot H/H+ Ag+ /Ag be obtained by the electrolysis of their aqueous salt solution and why? Or 0. Example 3: Calculate the no.
From the Ag+ /Ag = 0.5) −∆G1 = 1 × E1 × F .149 V ∴ ECell = EOP + ERP = 0.799 + (0. (i) Sol: Find out current in ampere and from the calculated Cu+ + e⁻ → Cu ..2% Example 7: The standard oxidation potential of Ni/Ni 2+ electrode is 0.15 × F + 1 × 0.15 V + +0.m. – ( ∆G1 + ∆G2 ) .059/1) log (9. If 0. of Cu = 63. 3 0  Electrochemistr y E calculate the concentration of hydrogen ion. (i) and (ii) Cu2+ + 2e⁻ → Cu . −∆G2 = 1 × E2 × F … (ii) Current efficiency = Cu + 2e⁻ → Cu .50 V Cu Cu Cu 0.236V = 0. determine the current efficiency.059 [H+ ]2 ∴ Ecell = Ecell + log10 2 [Ni2+ ] 2+ +0. Does Cu+ disproportionate in solution? Example 8: A current of 3 ampere was passed for 2 Sol: Given.236 V.236 + 0.m. 2+ E3 =? Current passed actually × 100 −∆G3 = 2 × E3 × F Total current passed experimentally … (iii) ∵ wCu = E. i.059/1) log K sp pH= –logH+ Ag+ /Ag AgI Ni → Ni2+ + 2e⁻. E2 = 0.799 – 0.. time and other term calculate the actual zero so first the standard electrode potential of the cell current flow. If this is combined with a hydrogen Example 9: An ammeter and copper voltmeter are electrode in acid solution. E1 = 0. Calculate current efficiency.948 = – 0.32 V Also. hour through a solution of CuSO4. at what pH of the solution connected in series in an electric circuit through which a will the measured e.5 × F] Current passed actually = × 100 ∴ E3 = 0.e.32 × 10–9) concentration one can easily find out the pH as using the following expression = 0.059/1) log [8. As we are asked it we are also with e. The ammeter shows 0.7 × 10 ] –17 2H+ + 2e⁻ → H2.474 = 0. be zero at 25ºC? constant direct current flows.799 – 0.325V Total current passed experimentally = (1. ERP =0 = 0. −∆G3 = −( ∆G1 + ∆G2 ) Current efficiency 2× E3 × F = [1 × 0.236 V Ni H Example 6: The reduction potential diagram for Cu in acid solution is: 0..6354 g of Cu is deposited in one hour. t / 96500 Adding Eqs.5 V current passed. (iv) 63.f of the cell (zero) so substitute to calculate percentage error divide the error by actual the values of different term in Nernst equation and current flow . EI/AgI/Ag = E + (0. Wt.0 = 0..f.5 × i × 2 × 60 × 60 ∴3= or i = 1.266 ampere 2 × 96500 i.236 + log10 [H+]2 o 2 E = X volt or –logH+ = 4 ∴ pH = 4 Calculate X.1 7 . of Cu = 63.799 + (0.3g of Cu2+ ions were Cu2+ + e⁻ → Cu+ . what is percentage error of ammeter? (At.54) Sol: Here we are provided with standard oxidation potential of nickel electrode and we all know that Sol: In order to find out the error first from the given reduction potential of hydrogen electrode is always Weight. Here us the error shown by the ammeter.15V discharged at cathode.266/3)×100 = 42.525 (Assume [Ni2+] = 1 M) ampere. (At wt.059 0 = 0. EOP = 0.. The difference between the two will give is equal the oxidation potential of nickel electrode.
93 × 106 coulomb of CuSO4 in the other cell. Find out the conc.3 liter (∵ t = 60 × 60 sec) (63. of Cu2+ lost = Equivalent of H+ formed ∴ n = 4 (an integer).4) = 50 × 0.011 × 100 ∴ % error in ammeter = = 2.977 3 × 1 × 60 × 60 2H2O → 4H + O2 + 4e + (at anode) or = 106.012 M H+ E×i× t [SO24− ] = 0. i. 0.094 M Sol: Quantity of electricity can be calculated using 2 × 50 Simple relationship [H+]= (N / 1) = (0.m.m. What weight of NaOH and what N Meq.t/96500 And Eq. t.4 / n 96500 ∵ w/E = i.6354 × 96500 = [20 × 0. value is 0.4 conc.6/50) = 0. if current is passed using Example 10: 3 ampere current was passed through Cu electrodes? an aqueous solution of unknown salt of Pd for 1 hour 2. (At. of one cell is ∴ Q= × 96500 = × 96500 E 71 / 2 0.6 Example 1: Calculate the quantity of electricity that will ∴ Meq.536 ampere Example 2: 50 mL 0. of CuSO4 left in solution be required to liberate 710g of Cl2 gas by electrolyzing a = 10 – 0. Of CuSO4 in solution = Meq.1 × 2 = 10 (∵ Meq.977 g of Pdn+ was deposited at cathode.011 using Pt electrodes with a current of 0.5 M.0821 × 300] / [2 × 1] = 246.965 ampere for a period of 1 minute.05% does not change during electrolysis. Cu2+ ions are discharged 2 at cathode and Cu2+ are formed at anode and thus ∵ 2Cl– → Cl2 + 2e. Anode Cu → Cu2+ + 2e ∴ Eq.f.1 M CuSO4 solution is electrolyzed Thus.4 = = 0. 0. What will be the concentration of each species. The redox changes are: Eq. wt. solution of NaCl.03 V higher than the other. of CuSO4 in the cell with higher e.6 = 9.525 = 0. error in (I) = 0. calculate [Cu2+]. of Pd or (w/E) = (I × t)/96500 Cu2+ + 2e → Cu (at cathode) 2. of H+ discharged= Eq. The conc.536 – 0. Also Eq. = 1. The e.536 [H+] and [SO24− ] after electrolysis. Of Cu2+ Wt. Find n. Sol: Meq. of Pd = 106. of Cu2+ or Meq. Wt.f. Chem i str y  17.54 / 2) × 60 × 60 ∴ i = 0.303RT = Eq. if Cu electrodes are used.. Also. Assuming that volume of solution 0. of Cu2+ volume of H2 at 27ºC and 1 atm pressure is obtained ∴[Cu2+]= Cu2 + = during this process? 2 2 × Volume of solution (in mL) 9. of NaOH formed 2. Of N× V in mL) Sol: For the reduction: Pd n+ + ne → Pd .31 Current flown = 0.06 F ./2 Cathode Cu2+ + 2e → Cu E×i× t E×Q Now w = = (∵ Q = i × t) 96500 96500 Example 3: Two students use same stock solution w 710 ZnSO4 and a solution of CuSO4. of Cl2 = M.965 × 1 × 60 = = = 6 × 10–4 96500 96500 JEE Advanced/Boards Or Meq.525 ampere as shown by ammeter ∴ wNaOH = {710[71/2]} × 40 = 800 g Actual current flown And wH = {710/[71/2]} × 1 = 20g w 2 (I) = × 96500 E×t ∴ VH = wRT / mp 2 0. Of Cu2+ lost = 0. of Cl2 formed = 0.1M W= (∵ Q = i × t) 96500 (∵ SO2– 4 is not involved in redox changes) Similarly calculate wNaOH and wH from the value of 2 wH volume can be calculated using ideal gas equation. 2H+ + 2e → H2 no changes in molarity of CuSO4 solution.
059 At R.= pK a − log C Cell I: Zn  ZnSO4  CuSO4  Cu 2 2 2 0.m.059 pK a − pK a = Eocell + log 2 . .701 = 0. E= cell Ecell + log 2 [Zn2+ ](PH ) 2 Consider the cell Pt H2(1 atm)  HA2  HA1  (H2 ) (1atm) Pt 0.760 + log10 2 [Zn2+ ](PH ) 2 0.S. As an acid undergoes dissociation.265 g For acid HA1 HA1 + − H + Al After addition of NaOH to cathode solution [H+] becomes 10–7 since both acid and base are neutralized [H+] = C α = Ka . (i) and (ii) Ecell − E'cell = log 2 Zn Zn HCl Pt(H2 ) E 2+ 2 [C' ] 2 + = +0.059 [H+ ]2 0. 1 1 pH2 Similarly. e.1] × 1 [H+] = 0.. by H+ /H 2 (PH ) substituting pH in terms of degree of dissociation and 2 concentration in nernst equation. (i) and (ii).060 [C ] = EOP + ERP + 0. 0.059 = EOP − log10 [Zn2+ ] Sol: First write down the nernst equation for two half. (i) H/H H/H+ Since. Thus. Zn/Zn2 + 2 cell as both solutions are acid we have to find out the concentration of hydrogen ion we can express it in 0. Find e.0316 × 1000 (∵ V = 1 liter) E + = ERP − 0. of cell after addition of NaOH.m. (ii) H /H H+ /H ∴ w = 1.059 volt Cell II: Zn  ZnSO 4  CuSO 4  Cu C1 C'2 Example 5: Calculate the minimum weight of NaOH required to added in RHS to consume all the H+ present ' 0.f.f.. +0.06 [C'2 ] E= cell Ecell + log .760V 2 0. Ecell (C2 = 0.059 [H+ ]2 0. (ii) in RHS of cell of e.059 [H+ ]2 + ERP + log10 the form of pH.060 [Cu2+ ] (∵ C are same) By Eqs.H.m.f. (i) H/H+ H/H+ 2 2 2 1 2 [C1 ] = 0 + 0.06 [C ] By Eqs.5 M).059 [H+ ]2 be easily determined.m.5 0.S. new e.06 0.05M 2 C' 2 Sol: For given cell ∵ EOP > EOP Zn/Zn2 + H/H+ Example 4: Two weak acid solutions HA1 and HA2 each ∴ Redox changes will be: Zn → Zn2+ + 2e with the same concentration and having pKa values 3 and 5 are placed in contact with hydrogen electrode 2H+ + 2e → = H2. value of C2 can be calculated..H.03 = log or C'2 = 0. 0.0316 mole liter–1 E + EOP ∴ = + 0.059 × 5[5 – 3]/2 = + 0..f of the cell can 0.059 At L. By comparing both the ∴ pH1 = pK a − log C 2 1 2 equation.059(pH)1 .1M 1 litre 1 atm ZnZn 0. 3 2  Electrochemistr y Sol: First write down the halfcell reaction and nernst 1 1 equation for both the half cell..701 = 0.059(pH)2 …. of cell. of [H+] H /H H+ /H 1 (w/40) × 1000 = 0. 2 [C1 ] Also report the e. C completely. Ecell EOP + ERP (1 atm at 25ºC)) and are interconnected through a salt Zn/Zn2 + H+ /H bridge.1 7 .701 V at 25ºC before its use. H+ must be used by NaOH 0. of NaOH = Meq.= E + EOP − log[H+ ]2 H/H H/H+ 1 0. Ecell = Ecell + log 2 [Zn2+ ] 1 1 0.m. of cell.f...760 + log10 ∵ –log H+ = pH 2 [0.= E + ERP + log[H+ ]1 ∴ Meq.
001 = 3.404 × F = – 2. o Thus.001 M Sol: Standard free energy can be calculated using the equation Calculate the e.S.1 (a) Design and point out the number of cells showing the overall reaction Fe + 2Fe3+→ 3Fe2+ Example 6: For the galvanic cell: (b) Also calculate Ecell and ∆G values for each cell.m.13V .H.059 [H+ ]2 Example 7: Ecell values for E= cell E= cell log10 2 (0.→ 2Fe2+ 2. ∆G = –6 ×0. Ksp of AgCl = 2. FeFe2 + Fe3+ Fe Ag 1 0.036] × F (n = 1) out the concentration of silver ion in each solution.760 + log10 Ecell = 0.H.8 × 10–10 2Fe3+ + 2e.036 0.4 × 10−9 Acid: Cr2O27− + 14H+ + 6e⁻ → 2Cr3+ + 7H2O .H.404V + ERP + log[Ag+ ]R.H.059 [Ag+ ]R.059 3.H.8 × 10−10 Redox Fe + 2Fe3+ → 3Fe2+ or [Ag+] = = =1.3765 V 2 0.1) Fe → Fe2+ + 2e.4×10–9 M [Cl ] − 0. Also comment on the result. L.3 × 10–13 Fe/Fe2+ Fe3+ /Fe2 + or [Ag+][Br–] = 3.H.424 F Ecell = log …. – ∆G3 = – ( ∆G2 + ∆G1 ) Here we are provided with solubility product of the two solution.059 = EOP – log [Ag+]L.3 × 10−10 medium. Chem i str y  17. – ∆G2 = – 0.→ Fe .036 × 3 × F Sol: Write down the halfcell equation for both the cell.036=0.33 0. ∴ Fe3+ + e.m. Cell no.S. From the value of solubility product first find −n EF = [2 × 0.059 (10−7 )2 V respectively: = 0.S.440 – 3 × 0. ∴ By Eq. AgCl(s) KCl KBr AgBr(s) Ag Ag 0.2 M 0.and Fe → Fe3+ + 3e.440–0. Fe2+  Pt L.S.e.are 0.H.3 × 10–13) / 0.3 × 10–13 Example 8: Oxidizing power of Cr2O27− is more in acidic or [Ag+] = (3.→ Fe2+ . (i) 1 [Ag+ ] Cell no. Ag 1 Redox Fe + 2Fe3+ → 3Fe2+ 0.H. Ksp of AgBr = 3.772 V the e. Ecell. Sol: ERP o in acidic medium is more than ERP in alkaline 0.8 × 10−10 2. II: Fe  Fe2+  Fe3+. Now substitute this value in Nernst equation and calculate Eº = + 0.f.. (i).8 × 10 . K sp = 3.3 × 10 ] AgCl AgBr Fe3+ + 3e.2 = Ecell EOP + ERP For R.f generated and assign correct polarity to each electrode for a spontaneous process ∆G =−n EF after taking an account of cell reaction at 25ºC. Ecell = log = –0.S. ERP = −0. For L. R.3 × 10–10 M medium than in alkaline medium.S.059 Ecell = EOP +ERP =0. Also. I: Fe  Fe+2  Fe3+  Fe Ecell EOP = + ERP .037V 1 1. Fe → Fe2+ + 2e.33V of cell Alkali: Cr2O27− + H2O → 2CrO24− + 2H+ CrO24− + 4H2O + 3e− → Cr(OH)3 + 5OH− .440 × 2 × F −10 −13 [Give.S. K sp = 2.8 × 10–10 Fe → Fe2+ + 2e or [Ag+][Cl–] = 2. 3Fe → 3Fe2+ + 6e⁻ Ag Ag 2Fe3+ + 6e⁻ → 2Fe 0. to get cell reaction (i.S.440 and 0. Ecell = +ve) polarity ERP = +1. – ∆G1 = +0.
8 volt.3 Write the Nernst equation and e. (i) 20.2 Electrolytic conductivity of 0. ECell ECathode = − EAnode = 0. (i) Which of the electrode is negatively charged? Q.050 M)H (0. The I2 so formed gets absorbed in starch to give blue color.020 M)H2(g)(1 bar)Pt(s) 2+ + (ii) 1 mole of FeO to Fe2O3? (iv) Pt(s)Br2(l)Br–(0.0591 [Products] º series having lesser EOP than iodine and thus.20 M solution of KCl at 298 K (ii) Individual reaction at each electrode.001M)H+(1M)H2(g)(1bar)Pt(s) (i) 1 mole of H2O to O2? (iii) Sn(s)Sn (0.f of the cell can be easily blue when Cl2 water is added.1 Depict the galvanic cell in which the reaction Zn(s) Zn(s) +Ag2O(s) + H2O(l) → Zn2+(aq) + 2Ag(s) + 2OH–(aq) + 2Ag+ (aq) → Zn2+ (aq) + 2Ag(s) takes place. is 0.2 = 3.0001 M)Cu(s) oxidation of: (ii) Fe(s)Fe2+(0. Explain.17 volt 2I– → I2 + 2e Cell reaction.1 What will be the effect on e.m. Further show: Determine ∆rG’ and E’ for the reaction.0 g of Ca from molten CaCl2? Q.f if concentration of Mg2+ E= cell Ecell − log ion is decreased to 0.030 M)H2(g) (1 bar)Pt(s) . Calculate its molar to produce conductivity.0134 volt Eo = + 0.7 How much electricity is required in coulomb for the (i) Mg(s)Mg2+ (0.1 M? 2 (1 × 10−3 )2 = (3.0223 volt Sol: First calculate the standard potential for reaction º º º which is calculated =as Ecell Eoxidation − Ereduction JEE Main/Boards Exercise 1 Q.37 volt When Mg2+ = 0.f of the following (ii) 40.0591 Mg2+ E= cell Ecell − log Cl2 + 2I– → I2 + 2Cl– n [Ag+ ]2 0.1 M Ag+ Ag Mg2 + /Mg 0.17 – log Example 10: Calculate the e.17 – 0.5 The conductivity of 0.1566 = 3.4 In the button cells widely used in watches and other devices the following reaction takes place: Q.001M)Cu2+(0. shows E= cell Ecell − log n [Reactants] reduction whereas I– undergoes oxidation.37)= 3.48 × 10–2 ohm–1cm–1.m. Q.80–(–2.17 – 0.1477) volt= 3. 2 [1 × 10−3 ]2 Mg(s)  Mg2+(0.010 M)  H+(0. 3 4  Electrochemistr y Example 9: Color of KI solution containing starch turns º After calculating Ecell e.0248 S cm–1. Eo = – 2.20 mole L–1 solution of Q.0591 0.0 g of Al from molten Al2O3? cells at 298K: Q. Calculate it molar conductivity.f of the cell.6 How much electricity in terms of faraday is required KCl at 298 K is 2.m.m. Mg + 2Ag+ → 2Ag + Mg2+ Cl2 + 2e. calculated using following equation Sol: Chlorine placed below iodine in electrochemical 0.1 7 .→ 2Cl– 0.0591 0.2 M)  Ag+ (1 × 10–3)  Ag = 3.
E = –1.74 × 10–5.146 × 10–3 S cm–1? the following: (i) Which of the following is strongest oxidizing agent: Q.45 g of silver deposited at the electrodes at 25ºC: cathode of cell B. Q.15 55. Calculate the standard potential of Cu2+ Cu electrode. = –0.5 S cm2 mole–1.80 V.5 amperes was passed Q.5 atm)  Cl– (0. O3. respectively are connected in series.896 × 10–5 S cm–1. Cl–.80V. Ka for CH3COOH = Given: E = –0.001 M)  Cu . o If Λ ∞ for acetic acid is 390. Find the values of Λ ∞ conditions? Given: E = + 0. (i) Fe3+(aq) and I– (aq) (ii) Ag+(aq) and Cu(s) (iv) Pt  Cl2 (0.19 Calculate the electrode potential of the following through them until 1. Ksp of Ag  Ag the following is feasible: AgCl = 2 × 10–10. Calculate its molar conductivity. respectively.20 Calculate the reduction potential at 25ºC for Fe3+/ Q. C containing solution of ZnSO4. what is its (ii) Which of the following is the strongest oxidizing dissociation constant? agent: Ag.66 V 1. Eº = + 0.001 M KCl solution at 298 K is 1500 Ω.36 V Cl 2 Cl– (iii) Fe (aq) an Br (aq) 3+ – (iv) Ag(s) and Fe (aq) 3+ (v) HCl (pH = 4.100 IO3− + 3H2O + 6e− → I – + 6OH− . predict if the reaction between (iii) AgCl (stand.13 Using the standard electrode potentials of electrochemical series. Q.00241 M acetic acid is Ag+.09 V Fe3+ Fe2 + Br2  Br − Q.07 V.237 11.50 V. Eº = + 0.14 The standard electrode potentials of Cu2+Cu+ an Fe2+ electrode if the concentration of Fe2+ ion is five Cu+Cu electrodes are +0. E = + 1. E = 0.15 Arrange Zn. O3.010 0. and O2 Q. Ag+.020 0. E = 1.260 V 102 × k/S m–1 [Acid Medium] 1. and O3? 7. and O2 platinum electrodes using a current of 5 amperes for 20 minutes.02 M).22 The standard reduction potential for Cu2+ Cu is + .907 V 0. sol)  Ag . AgNO3 and CuSO4. E = + 0.74 Calculate Λ ∞ for all concentrations and draw a plot Q.02 M) .76 V Zn2 +  Zn Q. How long did the current flow? What (i) Cu2+ (0. answer K is 0. respectively. Fe3+  Fe2 + Q.357M – CH3COOH. +1. E = –0.8 The resistance of a conductivity cell containing Q. Concentration M IO3− + 6H+ + 6e− → I – + 3H2O .10 A solution of Ni(NO3)2 is electrolyzed between agent: Ag.77 V. A steady current of 1.050 0. and O2? (iii) Which of the following is the strongest reducing Q. Ag+. What mass of Ni deposited at the cathode? (iv) Which of the following is the strongest reducing agent: Ag.16 The standard electrode potentials of Ag+Ag.11 The conductivity of sodium chloride at 298 K has been determined at different concentrations and the Q. Chem i str y  17.4)  H2(2 atm)  Pt (iv) Br2(aq) and Fe2+(aq).35 Q.12 Three electrolytic cells A.76 V.18 Can Fe3+ oxidize Br– to Br under standard o between Λ ∞ and S. Pb and Al in the increasing order of their reducing power under standard conditions.9 Conductivity of 0. E + = +0.13 V. Cl2. Using these information.34 V mass of copper and zinc were deposited? Cu3+  Cu (ii) Zn  Zn2+ (0.001 0.21 Calculate electrode potential for the halfcell PtH2 (1 atm)  0.18 V and +0. times that of Fe3+ ion.85 23. What is the cell Cl2Cl– and O3O2 electrodes are +0.001 M KCl solution at 298 +2.36V and constant if conductivity of 0. B. Zn2 + Zn Al2 + Al] Q.77 volt.53 106.17 The following reactions represent the reduction of results are given below: IO– ion into I–ion in acidic and basic medium. 0.
2 One mole of electron passes through each of the the above couple.8 If the pressure of H2 gas is increased from 1 atm to Q.130 M) + 2Ag(s) calculate its Ecell if Eºcell = 3.29 Calculate the equivalent conductivity of 1M H2SO4 (A) Hydrogen is easier to oxidize solution. if its conductivity is 26 × 10–2 ohm–1 cm–1. B (atomic weight = Cl– (0. pH of the solution around the cathode remains constant (b) Pt2 H2 (1 atm)  HCl (0.25 The molar conductivity of 0.05 V (C) 3. Ksp of AgCl = 2 × 10–10 Cl +  AgCl  Ag Ag+  Ag (ii) E . Single Correct Choice Type Q.80 V. 2 (C) 40758 (D) 20348 C Q.1 g of A was deposited.004M)AgCl  Ag Ag+  Ag 27) and C (atomic weight = 48) were electrolyzed under Ksp of AgCl = 2 × 10–10 identical conditions using the same quantity of electricity. The quantity of Q.4 The density of Cu is 8.81 × 1022 electrons.m.1 7 . 3 6  Electrochemistr y 0. sodium sulphate. 1 and 3 (D) 2.025 mole methanoic electricity needed to plate an area 10 cm × 10 cm to acid is 46.26 Suggest a list of metals that are extracted Q.4 L (C) 2.23 Calculate and Al deposited are: (A) 1: 1: 1 (B) 6: 3: 2 (C) 6: 3: 1 (D) 1: 3: 6 (i) E .1 One gm.3 Salts of A (atomic weight = 7). pH of the solution around the (c) Calculate the potential of hydrogen electrode in cathode decreases.1 S cm2 mole–1.35 (B) 133. the weights of B and C deposited were 2.8 L Mg(s) + 2Ag+ (0. E = 0.0 × 10–10.7 (D) 55 (A) 0. 3 and 2 Q. Ksp of Cu(OH)2 is 1.f of the cell in which the valencies of A.94 g cm–3. 1 and 2 (B) 1.7 A standard hydrogen electrons has zero electrode potential because Q.160 M) + 2Ag(s) (A) 3.6 When an aqueous solution of lithium chloride is electrolyzed using graphite electrodes Q.0295 V (D) 0.6 S cm mol/L.2 L (B) 2.7 and 7.24 Calculate the e. Q.34 V. Q.59 V (C) 0. E = + 0.5 During electrolysis of an aqueous solution of electrolytically. the 1.4L of oxygen at STP was liberated at anode. B and C respectively are: following reaction takes place: Ni(s) + 2Ag+(0.059 V (B) 0. CuSO4 and AlCl3 when Ag. The volume of hydrogen at STP. It was found that when 2. metal M+2 was discharged by the passage of 100 atm keeping H+ concentration constant at 1 M. Cu Q.6 S cm2 mol/L and (A) 13586 C (B) 27172 C λ°(HCOO⁻) = 54.4 (C) 66. (B) This electrode potential is assumed to be zero (C) Hydrogen atom has only one electron Exercise 2 (D) Hydrogen is the lightest element. Calculate its degree of a thickness of 10–2 cm using CuSO4 solution would be dissociation and dissociation constant. What is the atomic weight of metal? change in reduction potential of hydrogen halfcell at 25ºC will be (A) 33. The molar ratio of Ag. 2.6 L (D) 4.17V. liberated at Q.2 g. contact with a solution whose (i) pH = 5 (ii) pOH = 4 Q.002 M) → Ni2+ (0.28 Calculate the reduction potential of the following (A) Cl2 is liberated at the anode electrodes: (B) Li is deposited at the cathode (a) Pt2 H2 (4 atm)  H2SO4 (0. The Q.80 V. solution of AgNO3. 3 and 2 Given that E cell = 1. Given Λ0 (H+) = 349.2 M) (D) As the current flows.27 Represent the cell in which following reaction cathode would be takes place: (A) 1. Calculate the reduction potential at pH = 13 for Q.118 V . Cu and Al are deposited at cathode.01 M) (C) As the current flows.0001 M) → Mg2+(0.
635kJ/K (C) 3.2 (B) 0.3667 V (B) 0.5 g of mass takes place voltmeter Q. then at anode (A) –RT ln X + 1. Chem i str y  17.18 Consider the following Galvanic cell (D) A decrease of 2.)+ 1 O2(g)+ 1 H2O→Au (CN)2 + OH– − E = –0.95 × 10–11 (B) 5.1 V (B) –0.95 × 10–11 O2 + 2H2O + 4e– → 4OH– .1 M HCl solution its ore saturated with AgCl develop a potential of –0.7346 V (C) 1.0591 (C) –0.1349 V Q.11 During electrolysis of an aqueous solution Au3+ + 3e– → Au .15 If x is specific resistance of the electrolyte solution Q.5 M solution of an electrolyte in a cell was found to be 50Ω.13 The resistance of 0. then Λm is given by y 2H2 (g) + O2 (g) → 2H2O (l).95 × 10–11 (D) 1.5 KJ/mole 1000x (A) (B) 1000 y x What is ∆S298 for the given fuel cell reaction? 1000 xy Given O2 (g) + 4H+ (aq) + 4e– → 2H2O (l) E = 1.19 For the cell solution is 10 S cm2 equivalent–1 and that at infinite dilution is 200 S cm2 equivalent–1 Hence pH of HA PtH2 (0. If Au+2CN–(aq. if 2.3 (D) 3. If the electrodes in the By what value the voltage change when concentration cell are 2.1836 V (D) 0.51 kJ/K (D) –0. E° = + 1. ∆ fH298 (H2O. Kf{Au(CN)2} = X (C) 3.6 × 10–5 and the molar conductivity at infinite dilution is 380 × 10–4 S m2 mol–1.3 (B) 1.(l)= –285.16 The dissociation constant of nbutyric acid is Mg+2 (aq) → Sr+2 (aq) + Mg(s) is 2.322 kJ/K .4 cm2 then of ions in anodic and cathodic compartments both the molar conductivity (in S m2 mole–1) of the solution is increases by factor of 10 at 298 K (A) 0.12 The cost at 5 paise / KWH of operating an electric H2(g) Cl2(g) motor for 8 hours which takes 15 amp at 110 V is KNO3 (A) Rs 66 (B) 66 paise HCl HCl Pt(s) (C) 37 paise (D) Rs.14 Equivalent conductance of 0. The specific conductance of The E for a cell made up of the Sr/Sr+2 and Mg+2/Mg the 0.17 Consider the reaction of extraction of gold from Q.01 M acid solution is halfcells (A) 1.52 × 10–3 S m–1 (D) None of these (C) 0.11 F (D) –RTln X –1.25 V. E° = + 0.02 (C) 0.7 (C) 2.52 × 10 S m–1 (B) 1.799 V. the Ksp of AgCl in pure water will be: Ag/ Ag+ 4 2 (A) 2.7 (A) –0.041 (D) None of these Q.5 (C) –0.41 volt Q.29 F X (C) 2.1182 (D) 0 Q.60 Anode Cathode Q. E°= + 1.1 × 10–11 Use the following data to calculate ∆Gº for the reaction.4 atm)  H+ (pH=1)  H+ (pH =2)  H2 (0.1 atm)  Pt solution is The measured potential at 25ºC is (A) 1.5 g of Cu is Au + 2e → Au .5 g of copper is deposited Q.10 A silver wire dipped in 0.23 V (C) (D) xy 1000 (A) –0.9 The equilibrium constant for the reaction Sr(s) + Q.1 M HA (weak acid) Q.0591 (B) –0.69 × 1012 at 25ºC 1.20 For the fuel cell reaction: and y is the molarity of the solution.322 J/K (B) –0.5 volt of CuSO4 using copper electrodes.52 × 10–2 S m–1 (A) 0.2 cm apart and have an area of 4.29 F (B) –RTln X –2.37 Q.11 F (A) 890 ml of Cl2 at STP is liberated (B) 445 ml of O2 at STP is liberated (C) –RTln 1 + 2.002 (D) None of these (A) 0.4 volt 3+ – + deposited at cathode. 6.
2 M of the same solution is 520 Ω.490 V (C) 0.4 During the process of electrolytic refining of copper.827 V (B) 0. the mass of silver deposited in the cathode will Q. To calculate λHOAc .3 During the electrolysis of a solution of AgNO3.153 V respectively.10 Saturated solution of KNO3 is used to make ‘salt to area of the vessel and the concentration of the bridge’ because (2002) solution in it and is inversely proportional to the length of the vessel then the unit of the constant of (A) Velocity of K+ is greater than that of NO3– proportionality is (2002) (B) Velocity of NO3– is greater than that of K+ (A) S m mole –1 (B) S m mole 2 –1 (C) Velocities of both K+ and NO3– are nearly the same (C) S–2 m2 mole (D) S2 m2 mole–2 (D) KNO3 is highly soluble in water . the electrolyte will be (2006) some metals present as impurity settle as ‘anode mud.8 The molar conductivities λNaOAc and λHCl at infinity (B) Cathode to anode through external supply dilution in water at 25ºC are 91.1 M acetic acid (A) 0.24 × 10–4 S m2 mol–1 (C) Ag and Au (D) Fe and Ni (D) 1.1 M fluoroacetic acid (D) 0.9 Resistance of a conductivity cell filled with a solution be (2003) of an electrolyte of concentration 0. flow of electrons is from (2003) (D) Λ of chloroacetic acid (Cl/CH2COOH) (A) Cathode to anode in solution Q.8 g (C) 21. 3 8  Electrochemistr y Q.184 V (B) 0.1 M is 100 Ω.7 The equivalent conductance’s of two strong electrolytes at infinite dilution in H2O (where ions move Q.5 Conductivity (unit Siemen’s) is directly proportional Q.1 When the sample of copper with zinc impurity is to freely through a solution) at 25ºC are given below: A t be purified by electrolysis.2 S cm2/equivalent What additional information/quantity one needs to (b) Impure sample Pure copper calculate Λ° of an aqueous solution of acetic acid (c) Impure zinc Impure sample (A) Λ° of NaCl (d) Pure copper Impure sample (B) Λ° of CH3COOK o + (C) The limiting equivalent conductance of H+ ( Λ H ) Q.0 S cm2 / equivalent Cathode Anode 3COONa (a) Pure zinc Pure copper ΛHCl = 426. The conductivity of this solution is 1. the additional value (D) Anode to cathode through internal supply required is (2006) (A) λH (B) λKCl (C) λNaOH (D) λNaCl Q.1 7 .21 The standard reduction potentials of Cu2+/Cu Q.02 M solution of Q.1 M difluoroacetic acid Previous Years' Questions Q. the appropriate electrodes 25ºC are given below: (2007) are (2002) Λ CH = 91.29 S m–1. Resistance of (A) 1.4 × 10–4 S m2 mole–1 These are (2005) (B) 1240 × 10–4 S m2 mole–1 (A) Sn and Ag (B) Pb and Zn (C) 1.2 S cm2/mole (C) Cathode to anode through internal supply respectively.6 The highest electrical conductivity of the following and Cu2+/Cu+ are 0.’ (A) 12.08 g (B) 10.6 g (D) 108 g the same cell when filled with 0.1 M chloroacetic acid (C) 0. The aqueous solution is of (2005) standard electrode potential of Cu+/Cu halfcell is: (A) 0. 9650 2O coulombs of charge pass through the electroplating both.0 and 426. The molar conductivity of 0.337 and 0.2 In the electrolytic cell.24 × 10–4 Sm2 mole–1 Q.521 V (D) 0.
ZnZn (1M) Cu (1M) Cu ( Ecell = 1. Y = Ni Q. Ecell is 1.036V. The reaction is . concentration C and at infinite dilution are λC and λ∞.16 Given E Cr 3 + /Cr = −0.19 The reduction potential of hydrogen halfcell will be negative if: (2011) Q.385 V spontaneous when: (2012) (C) 0.13 The standard reduction potential for Fe2+/ Fe and (A) p(H2 ) = 1 atm and [H+ ] =1.14 Given E −0.072 V (B) 0.270 (A) Antilog (24.26 V (B) 0.58 V (D) –0.0 M standard Gibb’s energies of formation for CH3OH(l). For the given cell reaction Fe2+ + Sn → Fe + Sn2+.1M) → Zn2+ (1M) + Cu(2) taking place in Q.30 V (B) –0.303 = 0. Y = Zn (D) X = Zn.80 volt − (C) 1. Chem i str y  17. The reaction X + Y2+ X2+ + Y will be (A) –0.270 V (A) X = Ni. E° − 1. EFe 2+ /Fe = −0.17.18 Given: EFe = −0.21 Given: E°Cr3+ /Cr3+ = −0. The correct relationship between λC and λ∞. 237. E 2+ = −0.0 M methanol is 726kJ mol1. E° − MnO /Mn2 + 1.08) (B) 37.(B)C Q.44 V change.39 Q.10 volt.0 M standard EMF is (1990) (C) p (H2) = 2 atm and [H+ ] = 2. In a fuel cell methanol is used as fuel and oxygen (C) λC = λ∞ .1M)Fe2+(0.399 v (C) 0. 2 (B) P(H ) = 1 atm and [H+] = 1.439V .2.15 For the redox reaction: Zn(s) + Cu2+ (0.0591 (2003) Based on the data given above.26 V (A) λC = λ∞ + (B)C (B) λC = λ∞ . efficiency of the fuel cell will 2 (D) P(H ) = 2 atm and [H+] = 2.770 V (D) –0.30 V (D) p (H2) =1 atm and [H+ ] = 2.3 (D) 9.01M)Fe is (2008) respectively. –0.58 V (C) +0.07 volt (D) 0. Fe3(aq) + e− → Fe2+ (aq) will be → + respectively. strongest oxidising F agent will be: (2013) (A) 2.82 volt (A) Cl (B) Cr3+ (C) Mn2+ (D) MnO 4 Q.10 2+ 2+ V) was allowed to be completely discharged at 298 K.0 M Sn2+/Sn electrodes are –0.42V . Y = Fe (B) X = Ni.36 V Cr2 O7 /Cr Cl/Cl RT 2.44 and –0.74V.0 M H2O(ll) and CO2 (g) are 166.76. 3+ 2+ The relative concentration of Zn2+ to /Fe /Fe The value of standard electron potential for the change.14 volt (B) 1.33 = V.14 volt respectively.0 M be (2009) 2 (A) 80 % (B) 87% (C) 90% (D) 97% Q.339 V (D) 0. Ecell for the cell will be E° 2 − 3+ = 1.11 The reduction potential of hydrogen halfcell will 3 be negative if (2011) CH3OH( ) + O2 (g) → CO2 (g) + 2H2O( ) at 298K 2 (A) P(H ) = 1 atm and [H+] = 2.(B) C (D) λC = λ∞ + (B) C gas is used as an oxidizer.072 V (B) 0. Y = Zn (C) X = Fe.385 V (C) 0.2 and 394.4 kJ mol1 2 respectively.23 and –0. If standard enthalpy of combustion of (C) P(H ) = 2 atm and [H+] = 1.0 M (A) +0. the (B) p (H2) =2 atm and [H+ ] =1.0 M Q. The potential for the cell CrCr3+ (0.3 (C) 1037.65 × 104 Q.770 V (D) 0. Zn2+ 3+ Cu is (2007) + e − →Fe 2+ (aq) will be: 2+ 2+ Fe(aq) (2009) [Cu ] (A) 0. The value of standard electrode potential for the Ni2+/ Ni. and Fe2+/ Fe are –0.20 The standard reduction potentials for Zn2+/ Zn.51 V = 4 a cell.22 The equivalent conductance of NaCl at Q. EFe = −0.12 The cell.439V = Fe3+ /Fe Fe /Fe Q. Q.72V. is given as (Where the constant B is positive) (2014) (A) 0.036V.
23 Given below are the halfcell reactions Q. the reaction will occur JEE Advanced/Boards Exercise 1 Q. the above couple.f of the cell Ag  AgI  KI (0. H2 (1 atm)  H+ (pH = x)  Normal calomel (i) What is the cell reaction? electrode has an EMF of 0.1 M)  NH3 (aq.8 M) Ag(s) is 0.33 V.9 V.8 M)Ag is 0.40 V concentration each is electrolyzed at 25ºC.f. Calculate the reduction potential at pH = 14 for Ag+ + e → Ag(s) = 0.8 × 10–5. of AgI.33 V.3 × 10–3 that can be obtained from one mole of Ni2O3? M) Ag+ (0. E° = –0.05 M NaOH is added. value can [Cu2+] be brought down before bismuth starts to deposit.51 V Q.51 V 3+ – 2+ (A) 0 g (B) 63.5 g (C) 2 g (D) 127 g The E° for 3 Mn → Mn + 2Mn will be 2+ 3+ (A) –2. The oxidation potential of the calomel concentration of KOH? electrode on hydrogen scale is –0. E° (Bi3+Bi) Ni2O3(s) + H2O (i) + 2e– l 2NiO(s) + 2OH–.05 M)  AgNO3 H2 (1. Calculate the pH (ii) What is the cell e.982 V. Kb (NH3) = 1.24 Two Faraday of electricity is passed through a (2014) solution of CuSO4. 4 0  Electrochemistr y Q.344 V respectively. (iii) What is the maximum amount of electrical energy Q. H2 (1 atm) HOCN (1.2 The cell Pt.5 Calculate the e.226 V and 0.1 M MnO4– and 0.18 V (2015) (Mn + e → Mn ). Calculate the Ka for HOCN. Q.m.8 V.0 atm)  CH3COOH (0.f of the cell. Ecell = –0.1 7 .8 M H+ and salt at 298 K from the following cell data at 298 K.01M)  Q.8 × 10–5.69 V. A mixture of salts of bismuth and copper at unit E° = +0. Ksp of Cu (OH) 2 is 1 × 10–19. Q.  H+ (0. mass of Cu = 63.67 V at 25°C.8 Determine the degree of hydrolysis and hydrolysis versus the standard hydrogen electrode. E° = + 1. which was treated with 90% of the Fe2+ necessary to reduce all the MnO4– to Mn+2. H2 (1. and E° (Cu2+Cu) are 0.m.6 The Edison storage cell is represented as Fe(s)  FeO(s)  KOH (aq)  Ni2O3(s) Ni(s) the halfcell reaction are Q. Calculate the solubility product Ka (CH3COOH) = 1.188 V MnO4– + 8H+ + 5e → Mn2+ + 4H2O.3 Voltage of the cell Pt. 0.? How does it depend on the of the solution.10 The e.34 V. The mass of copper deposited at the cathode is: (at. E° = 1.28 V. Pt (0.f when 40 ml Q.1 M.f of the cell of 0.4 Calculate the potential of an indicator electrode Q. the reaction will not occur (D) –0.m.87 V Q.1 The standard reduction potential values. PtH2 (1 atm)  H+ (1M) M/32 C6H5NH3ClH2 (1 atm)  Pt.788 V. the reaction will not occur (B) –2.69 V. the reaction will occur (C) –0.5 amu) Mn2+ + 2e– → Mn. Pt. Calculate the e.05 M)  Ag is 0.m. PtH2(1 atm). .7 The standard reduction potential for Cu2+/Cu is 0. 30 ml)  Ag+(0. To what FeO(s) + H2O (l) + 2e– l Fe(s) + 2OH–. Neglect [H+] because of oxidation of H2 (g).m. in electrolysis.0 atm). E° = — 1.9 The e. which constant of aniline hydrochloride in M/32 solution of originally contained 0.
× 1012. of the cell Ag(NH3)2+ + e– → Ag + 2NH3 Ag(s)  AgIO3(s)  Ag+(x M).126 V E° for Sn/Sn2+ = 0.84 × 10–4M)  Zn(s) is E = + 0.41 Q. Given Q. Zn displaces Cu2+ till Q. The solubility NH3 has been added to the cathode compartment product constants of AgBr & AgCl are respectively 5 × to make NH3 concentration 2M. E° = 1. Eº = 0. E.25 V.33 V Zn(s)  Zn(CN)42–(0. Q.00 mL of 0.17 The voltage of the cell Kins [Ag(NH3)2+] = 6. Calculate the EMF generated ions at equilibrium? and assign correct polarity to each electrode for a spontaneous process after taking into account the cell Q.82 V (OH) 2(s) E (Mn2+/Mn) = –1. Br– and Cl– ions would the e. Examine The mass of x deposited is 0. E° = –0. Ti.124 M sodium find E° for this disproportionation.22 Kd for complete dissociation of [Ag(NH3)2]+ into reaction at 25ºC.600 M)  Pb2+ (2.356) E° (Pb2+/ 3Sn(s) + 2Cr2O72– + 28H+ → 3Sn4+ + 4Cr3+ + 14H2O Pb) = –0.15 Calculate the voltage. of the cell at 25ºC [Co(CN]6]3– e– → Co(CN)64– is –0. Calculate E for the following [Ksp (AgCl)] –2.11 Consider the cell Q. If the E° value for Ag+Ag is 0.00 × 10–4M)  formation constant of [Co(CN)6]3– Given Co3++ e– → Cu2+ (0.617 g and the iodine is the spontaneity of the reaction.136 V E° for Sn2+/Sn4+ = – 0.18 V Q.23 The overall formation constant for the reaction of PbCl2 a 25ºC? 6 mole of CN– with cobalt (II) is 1 × 1019. When excess of Zn is added to CuSO4. What is the ratio of Zn2+ to Cu2+ (0. E° (Co3+/Co2+) = 1.26 Calculate the equilibrium concentration of all ions constant Kf for in an ideal solution prepared by mixing 25. Ag+ and 2NH3 is 6 × 10–8. Find the equivalent mass of x.154 V Q. Given: E – 0. E. determine Ksp for Q.7991 V.799 V Q.f of the cell be zero? Zn + Cu2+ → Zn2+ + Cu is 1.84 V complexation reaction of importance.02 × 10–8 and Pb(s)  PbSO4(s)  NaHSO4 (0. E° for the reaction.13 For the galvanic cell: Ag AgCl(s)  KCl (0.100 M Ti+ with 25.061 V.450M). CN–(2.2 M)  KBr equilibrium is reached. For what ratio of the concentration of = 1.001 M) AgBr(s)  Ag.76 and that of Cu is –0. the only Zn2+ + CN⁻ E° (Ti+/Ti3+) =–1.12 The pKsp of Agl is 16. Kf for [Cu (NH3)4]2+ 10–13 & 1 × 10–10.25 Calculate the equilibrium constant for the reaction: Pb(s) + SO42–(aq) → PbSO4(s) + 2e– (E° = 0.83 V. Ksp (AgBr) – 3. Also completely reduced by 46.175 M)  Zn(s) if Ksp = 3. Chem i str y  17.00 mL of 0.162 for HIO3.300 M)  Zn2+ Ag(CN)2– e– → Ag + 2CN– (0.19 Given the standard reduction potentials Ti+ + e– → liberate iodine (at anode) and a metal x (cathode).m. Q.24 Calculate E° for the following reactions at 298 K.268 V for the Cl–PbCl2Pb couple and –0.200M Co3+.65 × 10–3M)  Zn2+ (3. 3Ti+ → 2Ti + Ti3+. Find the E° for the halfcell reaction AgI (s) Q. Q. thiosulphate. Ag+ Ag Q.14 Given. Zn2+ + 4CN– → Zn(CN)42–. The standard reduction potential for the reaction Q. the dissociation constant for HSO4–.1 V.8 × 10–10.16 Calculate the voltage. Calculate K2 = [H+] [SO42– ]/ [HSO4–]. E° =1.07.20 Estimate the cell potential of a daniel cell having 1 M Zn++ & originally having 1 M Cu++ after sufficient Ag  AgBr(s) Br–  AgCl(s).34 V at 25ºC.9 × 10–13 for Mn Co2+ . HIO3 (0.675 M)  Cu(s) given that Ksp = 1.34 V and Ti3+ + 2e– →Ti+.25 V.50 × Kins[Ag(CN)2–] = 1.27 Same quantity of electricity is being used to Q.18 The voltage of the cell E° for Cr2O72–/Cr3+ = 1. E° = –0. Ag  Cl– at 25ºC. Ag(NH3)2+ + e– → Ag + 2NH3 Ag+ + e– → Ag. Calculate the Mn(s)  Mn (OH2) (s) Mn2+ (xM).02 × 10–8 for AgIO3(s) and Ka = 0.126 V for the Pb2+Pb couple.995 ×10–19 10–5M)  Pb(s) is E = +0.099 V.3 cc of 0.3 × 10–13] half reaction.21 The normal oxidation potential of Zn referred to + e– → Ag + I– SHE is 0.7991 V. . OH– (1. Calculate the Q.
Ag+ /Ag Q.699 Cu at cathode.39 At 25ºC.5 L of acid and the volume practically remains constant – 0.38 Determine at 298 for cell discharging reactions are: Pt  Q. Q.32 An acidic solution of Cu salt containing 0.0 PbO2 + 4H+ + SO42– + 2e– →PbSO4+ 2H2O (cathode) (b) The pH when Ecell = 0 Q.5 cm How many years would it take to electrolyze the lake? apart is filled with 0. l) = –56700 cal/mole and Q. Ag anode if For H2S: K1 = 10–8 and K2 = 1. battery. disulphuric acid. What Cu2+ is electrolyzed until all the copper is deposited.5 a solution of CuSO4.40 Calculate the cell potential of a cell having reaction: Ag2S + 2e– →2Ag + S2– in a solution buffered Q.1 × 10–13.5 × 106 coulomb per second at an appropriate voltage. In such (b) Initial concentration (M) of CuSO4.76 and + 0. Ksp (Ag2S) = 2 × 5 ampere current is passed for 2 hours? Purity of silver is 95% by weight.5 cm2 in surface area and 0. Calculate percentage current efficiency of the process.m.294 to 1.1 M H2S. Assuming no volume change during electrolysis. A cell with 1.37 An external current source giving a current of 0.m. QH2.139 g mL–1 is 20% by weight.f when pH = 5.8 .261 g ml–1 at 25ºC) to 27% Q.f increase by 0. How far would the . E = −0.28 In a fuel cell. H2 gas is oxidized at the anode & O2 at as H2SO4 is used up. H+  1M KCl  Hg2Cl2(s)  Hg (l)  Pt Pb + SO42– → PbSO4 + 2e– (anode) (a) Its e. H2S2O8.29 One of the methods of preparation of per 35 ml. Calculate the total charge released at anode of the a potential of 6 volt was applied.30 During the discharge of a lead storage battery Before passing the current the LHE and RHE contained the density of sulphuric acid fell from 1.35 L of O2 were generated at STP.34 V respectively. The solution after electrolysis Cathode: O2 + 2H2O + 4e– → 4OH– was neutralized.5 A was joined with Daniel cell and removed after 10 hrs. if at the volume of solution kept at 100 ml and the current 26ºC the e. treated with excess KI and titrated with 0. The Q.4 g of 2+ energy of ionization of H2O (l) = 19050 Cal/mol.10N solution A power reactor produces electricity at the rate of of MgCl2 is 97.04 M Na2S2O3.42 A dilute aqueous solution of KCl was placed by weight.31 A current of 3 amp was passed for 2 hour through (c) The positive electrode when pH = 7. 1L each of 1M Zn2+ and Cu2+ respectively. Overall reaction is the cathode. across which liter. If 67. at 1. The original volume of electrolyte is one between two electrodes 10 cm apart.35 A lead storage cell is discharged which causes the electrodes is 5 volt? H2SO4 electrolyte to change from a concentration of 34.6% by weight (density 1. Q.41The equivalent conductance of 0. Calculate the number of ampere hours for which the battery must have been used. Q. involve electrolytic oxidation calculate: of H2S O4 at anode (2H2S O4 → H2S2O8 + 2H+ + 2e–) (a) Duration of electrolysis if current efficiency is 80% with oxygen and hydrogen as byproducts.722 L of H2 and 2. 10–49. E of Zn2+/Zn and Cu2+/Cu at 25ºC is 3.34 Dal Lake has water 8. how many grams of Cu will be deposited? electrodes by passing 0.2 amp.28. Q. ∆Hf (H2O. Find the EMF mL–1 H2SO4 of density 1. Calculate the volume of gases evolved at NTP during the entire electrolysis. E° RP (LHS) = 0.2 × 1012 liter approximately.1 mho cm2 equi–1 at 25ºC.139 g. The will be the reversible EMF at 25ºC of the cell? electrolysis is continued for seven more minutes with Pt  H2 (g) (1 atm)  H+  OH–  O2 (g) (1 atm)  Pt.001158 V. 9. What is the weight of H2S2O8 formed? Q. The battery holds current source.33 In the refining of silver by electrolytic method at pH = 3 and which is also saturated with 0. an electrolysis. 3g of Cu2+ ions were deposited as Given E° RP (RHS) = 0. during the discharge.36 100ml CuSO4 (aq) was electrolyzed using inert (II) solution. electrode that are 1. 4 2  Electrochemistr y Q. How much current will flow when potential difference between the Q.1 N MgCl2 solution. Note that the water is produced by the reaction In the process.294 g mL–1 is 39% and that of supplied by the Daniel cell after removal of the external density 1. H2 & O2 react to produce electricity.2 liter of H2 at STP react in 15 minutes. Pb(s) + PbO2(s) + 2H2SO4 (l) → 2PbSO4(s) + 2H2O (l) what is the average current produced? If the entire current is used for electrode deposition of Cu from Cu Q.965 A till the pH of the Anode: H2 + 2OH– → 2H2O + 2 e– resulting solution was 1. what will be the weight of 100 gm. Volume of Na2S2O3 required was Q.1 7 .
46 A sample of water from a large swimming pool has is 9 × 10–6 S m–1 and its equivalent conductivity is a resistance of 9200 Ω at 25ºC when placed in a certain 1. Hg2(NO3)2.2 S cm2 mole–1 (D) 42 S cm2 mole–1 Single Correct Choice Type Multiple Correct Choice Type Q.5 Ω–1cm–1mol–1 and molar conductivity of KCl at conductivity of mixture if conductivity of CH3COONa is 0.1 An aqueous solution containing one mole per liter each of Cu(NO3)2 AgNO3.) E = +1.2 The charge required for the oxidation of one mole ion at infinite dilution at 25ºC is 73.46 and 79.02 M is 138 Ω–1 cm2 mole–1.34V and E −2. per liter of SrSO4 in water. Q. the pKa value of the acid can be data: Conductivity of a saturated solution of given as Co2[Fe(CN)6] is 2.015 M Given: Molar conductance of NaCl at that concentration NaOH are mixed together.02 M KCl solution.015 M CH3COOH & 0. Cu (D) Cu.3 A solution of sodium sulphate in water is separation of electrodes. Mg(NO3)2 is being Q.44 The specific conductance at 25ºC of a saturated solution of SrSO4 is 1. the sequence of deposition of I2(s) + 2e → 2I–(aq. standard of Co2 [Fe(CN)6] in water at 25ºC from the following hydrogen electrode. Calculate Q. 6. Mg (B) Mg. Hg. [Sr = 87.) E = + 1. The value of following from inspection of standard reduction standard potentials are potentials (Assume standard state conditions).09 volt Cu2+Cu Mg2+Mg Br2 /Br – With increasing voltage.) + 2e → 2Cl–(aq.50 × 10–4 S m–2 equivalent–1.118 0. Ag E = + 2. If reduction potential values for two cells Q. Area of electrodes is 1.7 Pick out the correct statements among the electrolyzed by using inert electrodes.80V. which was thoroughly (C) 8.45 Calculate the solubility and solubility product are found to be E1 and E2 respectively w.36 volt Ag+ Ag Hg22+ Hg Cl2 /Cl– E − 0.54 volt I 2 /l– metals on the cathode will be (A) Ag.8 × 10–9 NaCl were dissolved in the pool. O = 16] a buffer solution of sodium acetate and acetic acid in the ratio b: a. the resistance was found to be 170.06 × 10–6Ω–1cm–1 and that of water used 4.5 ohm.0 Ω–1cm–1 mole–1. The products at the cathode and anode are respectively. Q. A sample of this solution gave a resistance of 7600 Ω. E − 0. O2 (B) O2 .5 × 10–6 mho cm–1.The ionic molar conductivities E1 + E2 E2 − E1 E1 + E2 E1 − E2 (A) (B) (C) − (D) of Co2+ and Fe(CN)64– are 86.79V.43 When a solution of specific conductance 1.t.4 S cm2 mole–1 (B) 84 S cm2 mole–1 Exercise 2 (C) 4. Hg.00 volt S2O32− /SO24− .8 ohm–1 cm2 mole–1 a: b and another hydrogen electrode Y was placed in respectively. Q. the cell has a resistance of 85 Ω at 25ºC. Q.86×10–4m2. 500 gm. Hg. Cl2 (aq.118 444. Hg.4 A hydrogen electrode X was placed in a buffer Molar ionic conductance of Sr2+ and SO42– ions at solution of sodium acetate and acetic acid in the ratio infinite dilution are 59. Chem i str y  17.1 × 10–7Ω–1cm–1. E − 0. Na (D) None of water used is 1. H2 (C) O2.6.) + 2e → 2SO24− (aq.5 The conductivity of a saturated solution of Ag3PO4 Q.3V = Br2 (aq. Ag S2O28− (aq.32 × 10–18 (B) 1. Determine at 25ºC the solubility in gm. When filled with 0. The Ksp of Ag3PO4 is: conductance cell.118 0.) (C) Ag.43 K+ ion move in 2 hours at 25ºC? Ionic conductance of K+ Q.) + 2e → 2Br–(aq. Calculate the volume of water in the pool. of (A) 4.) E = + 0. Cu.0 Ω–1cm2 mole–1 and 0.64 × 10–13 (D) None of these stirred.342 ohm–1 meter–1 was placed in a conductivity cell (C) 10 × 96500 C (D) 2 × 96500 C with parallel electrodes.482 × 10–4 ohm–1 cm–1 while that (A) H2 .3 × 10–4 S cm–1? (A) 8. Cu.118 0. What would be molar is 126.52 ohm–1 cm2 mole–1? Mn3O4 into MnO42– in presence of alkaline medium is (A) 5 × 96500C (B) 96500 C Q. S =32.r.6 Equal volumes of 0. electrolyzed using inert electrodes.
in order to get electrode potential of net reaction.1 7 . 0. statementII is true and statementII is NOT the correct explanation for solution statementI. (C) Fused NaOH with inert electrodes.12 StatementI: The voltage of mercury cell remains oxygen at anode during electrolysis? constant for long period of time.22 volt. (A) H2SO4 is produced 585 gm. of NaCl were dissolved in the pool.10 During discharging of lead storage battery.17 Volume (in Liters) of water in the pool is: (A) 1.8 volt respectively.25 × 105 (B) 1250 (C) 12500 (D) None of these . Q.02 M is 200 Ω–1 cm2 mole–1. so oxidizing 273 K power of ions is C3+ > A+ > B2+.11 The EMF of the following cell is 0.9 If 270.16 Conductivity (Scm–1) of H2O is: (B) Increasing Cl concentration in Anodic compartment – (A) 4 × 10–2 (B) 4 × 10–3 (C) Increasing H concentration in cathodic compartment + (C) 4 × 10–5 (D) None of these (D) Decreasing KCl concentration in Anodic compartment.14 StatementI: The SRP of three metallic ions A+.3. the cell has a resistance of 100 Ω at 25ºC. statementII is true Q. –0. (B) Total 504 L gases will be produced at 1 atm & 273 K StatementII: Higher the SRP.] Q. (C) PbSO4 is formed at both electrodes [Given: Molar conductance of NaCl at that concentration (D) Density of electrolytic solution decreases is 125 Ω–1cm2 mole–1 and molar conductivity of KCl at 0. StatementII: Electrode potential is an intensive Q. higher the oxidizing power (C) 336 L of H2(g) will be evolved at anode at 1 atm & 273 K Comprehension type (D) 45 F electricity will be consumed Paragraph 1: A sample of water from a large swimming pool has a resistance of 10000 Ω at 25ºC when placed Q. statementII is false of Cl– (D) StatementI is false. experiment performed by Miss Abhilasha with 75% current efficiency then Q. (A) Dilute H2SO4 solution with Cu electrodes. 4 4  Electrochemistr y 2− Assertion Reasoning Type (A) Cl2 can oxidize SO 4 from solution (A) StatementI is true. A sample of this solution gave a resistance of 8000 Ω. Q.15 Cell constant (in cm–1) of conductance cell is: Ag(s)  AgCl(s) KCl (1M) H+ (1M) H2 (g) (1atm). Br– and I– from aqueous (B) StatementI is true. statement2 is true and (B) Cl2 can oxidize Br– and I– from aqueous solution statementII is correct explanation for statementI (C) S2O8 2− can oxidize Cl–. Q.8 Which of the following arrangement will produce Q. (A) 168 L of O2 (g) will be evolved at anode at 1 atm & B2+ C3+ are –0. which in a certain conductance cell. Pt(s) (A) 4 (B) 0.5. involve active species.4 (C) 4 × 10–2 (D) 4 × 10–5 Which of the following will decreases the EMF of cell (A) Increasing pressure of H2 (g) from 1 atm to 2 atm Q.0 of water is electrolyzed during an property. Br– can be reduce in presence (C) StatementI is true.02 M of the following is/are true? KCl solution. StatementII: It because net cell reaction does not (B) Dilute H2SO4 solution with inert electrodes. When filled with 0. 2− (D) S2O8 is added slowly.13 StatementI: We can add the electrode potential (D) Dilute NaCl solution with inert electrodes. which was (B) H2O is consumed thoroughly stirred.
flow of electrons is from (2003) At [Fe2+] = 10–3 M.32/0. Assuming 1 2H+ + 2e– + O → H2O (l). The plot of conductance (Λ) versus the copper is same? volume of AgNO3 is (2011) (A) 101.01 M)  Fe. Previous Years' Questions 2Fe(s) + O2 (g) + 4H+ (aq) → 2Fe2+ (aq) + 2H2O (l).61 (B) ~0.1 M2 and PNO = PNO = 10–3 atm and using 2 2 2 given data answer the following questions: Fe2+ + 2e– → Fe(s).6 × 104 s (A) ~0. Chem i str y  17.01 mole of H2 gas at the cathode is F (1 F = 96500 C mole–1) (2008) Q. E = 1.f of the above cell is 0. Equilibrium constant for the cell reaction is (2004) Fe3+ (aq) + 3e– → Fe E° = –0.19 At what HNO3 concentration thermodynamic solution gradually and the conductivity of the solution tendency for reduction of NO3– into NO and NO2 by was measured.47 V (B) 1.67 V Q.7 For the reduction of NO3– ion in an aqueous solution E° is + 0. The time required At 298 K (2. P (O2) = 0. E = –0.77 V (C) 1.303) = 0.1 M)  Fe2+ (a = 0.32/0.04 V (A) 100.2 ZnZn2+ (a = 0.71 (C) ~ 0.1 In the electrolytic cell.06 volt to liberate 0.18 ECell for reduction of NO3– → NO by Cu(s).0295 (D) 100.87 V (D) 1.96 volt (A) –76 (B) –322 (C) –122 (D) –176 NO3− /NO E − = +0.32/0.51 (D) ~0.26/0.56 M (C) 100.96 V.059 (B) 100. Of HNO3 in solution.3 The halfcell reaction for rusting of iron are: depending upon conc.4 Electrolysis of dilute aqueous NaCl solution was RT carried out by passing 10 mA current.12 M Match the Columns V V Q.34 volt Cu2 + /Cu ∆Gº (in kJ) for the reaction is (2005) E = + 0.1 atm and pH = 3.81 Q.6 Consider the following cell reaction.23 M (B) 100.2905 V.95 × 104 (D) 38.0295 Au3+ (aq) +3e– → Au E° = + 1. the cell (A) Cathode to anode is solution potential at 25ºC is (2011) (B) Cathode to anode through external supply (A) 1. E° = + 1.5 AgNO3 (aqueous) was added to an aqueous KCl Q.79 volt NO3 /NO2 Q.45 Paragraph 2: Copper reduces NO3– into NO and NO2 Q.66 M (D) 100. Values of E° for some metal ion are given below Q.44 V E = + 0.19 V The e.65 × 104 s (B) 19.20 Column I Column II Volume Volume (P) (Q) (Electrolysis product using inert electrode) V V (A) Dilute solution of HCl (p) O2 evolved at anode (B) Dilute solution of NaCl (q) H2 evolved at cathode (C) Concentrated Solution (r) Cl2 evolved at anode Volume Volume of NaCl (R) (S) (D) AgNO3 solution (s) Ag deposition at cathode (A) (P) (B) (Q) (C) (R) (D) (S) Q.295 .40 V (C) 100.m. V2+ (aq) + 2e– → V E° = –1. when (A) 9.23 V [Cu2+] = 0.57 V (C) Cathode to anode through internal supply (D) Anode to cathode through internal supply Q.3 × 104 s [HNO3] = 1 M is [At T = 298] (C) 28.
77 (A) NH3 combines with Ag to form a complex + O2 + 4H+ + 4e– → 2H2O E = 1.15 While Fe3+ is stable.38 (C) 28. the maximum weight (in gram) of amalgam formed this solution is Ag+ + e– → Ag. Q.5 (B) 1.65 from Ered explanations to (D) Ered will decrease by a factor of 0.92 at 298 K] F RT (2006) Q.36 Q.1 7 .9 When ammonia is added to the solution.0592 and = 38.0 (C) 2. Which Mn3+ + e– → Mn2+ E = 1. 1 F = 96500C). A simple example is a Daniel cell in which zinc and by how much? goes into solution and copper gets deposited.86 V A 4. The following (B) O2 oxidizes both Mn2+ to Mn3+ and Fe2+ to Fe3+ example illustrates a typical case. which requires a clear (D) Mn3+ oxidizes H2O to O2 understanding of the mole concept. identify the correct formed statement (D) NH3 has no effect on the standard reduction (A) Chloride ion is oxidized by O2 potential of glucose/gluconic acid electrode (B) Fe2+ is oxidized by iodine Paragraph 2: Chemical reactions involve interaction (C) Iodide ion is oxidized by chlorine of atoms and molecules. (2007) (A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V Q. Given (A) Eoxi will increase by a factor of 0. Mn3+ is not stable in acid large numbers conveniently.14 Among the following. E red = 0.8 2Ag+ + C6H12O6 + H2O → 2Ag(s) C6H12O7 + 2H+ (A) 24125 (B) 48250 (C) 96500 (D) 193000 Find in K of this reaction. the mole concept was solution because introduced.10 Ammonia is always added in this reaction. This concept has implications in diverse (A) O2 oxidizes Mn2+ to Mn3+.11 The total number of moles of chlorine gas evolved is (A) 0. Paragraph 3: Redox reaction play a pivotal role in (A) 66. pH is Reactions decide which way the reaction is expected to raised to 11.30 (D) 46.50 of the following must be incorrect? Fe3+ + e– → Fe2+ E = 0. electrochemistry and radiochemistry. . involving chemical/ (C) Fe3+ oxidizes H2O to O2 electrochemical reaction.0 Paragraph 1: Tollen’s reagent is used for the detection of aldehydes. To handle such Q. Hg = 200.0 M aqueous solution of NaCl is prepared and 500 mL of this solution is electrolyzed.13 The total charge (coulombs) required for complete electrolysis is Q. biochemistry.0 (D) 3.303 × = 0.65 from Ered I2 + 2e– → 2I– E = 0.65 from Eoxi below are a set of halfcell reaction (acidic medium) along with their Eº (V with respect to normal hydrogen (B) Eoxi will decrease by a factor of 0.80 V (A) 200 (B) 255 (C) 400 (D) 446 RT F [Use 2. 4 6  Electrochemistr y Hg2+ (aq) +2e– → Hg E° = + 0.13 (B) 58.29 chemistry and biology.023 × 1023) are present in a few grams of any chemical compound varying with their atomic/molecular masses. Using this data obtain the correct (C) Ered will increase by a factor of 0.65 from Eoxi electrode) values.12 If the cathode is a Hg electrode.23 (2007) (B) Ag (NH3)2 is a stronger oxidizing reagent than Ag + + (C) In absence of NH3 silver salt of gluconic acid is Q. This lead to the The pair (s) of metals that is (are) oxidized by NO3– in evolution of chlorine gas at one of the electrodes aqueous solution is (are) (2009) (Atomic mass: Na = 23. A large number of atoms/ (D) Mn2+ is oxidized by chlorine molecules (approximately 6. The values of standard redox potential ( E ) of two halfcell Q.54 Cl2 + 2e– → 2Cl– E = 1. areas such as analytical chemistry. When a solution of AgNO3 is added to glucose with NH4OH then gluconic acid is formed. Which halfcell reaction is affected by pH proceed.
The blue color is [F = 96500 C mol/L] (2015) due to the formation of (A) Fe4 [Fe (CN) 6]3 (B) Fe3 [Fe (CN) 6]2 Q. . potential  Ecell  = 70 mV. (A) 35 mV (B) 70 mV (C) 140 mV (D) 700 mV (B) Stops the diffusion of ions from one electrode to another.22 In a galvanic cell. the difference in their pKa values. then the magnitude of the cell potential would be (A) Does not participate chemically in the cell reaction. 1 bar)  H+ (aq.pKa (HY).303 0. M2+ (aq)  Pt(s) M(s)  M+ (aq. ∆Gº > 0 (D) Ecell > 0 . 1 molar)  M (s) M2+ (aq) For the above electrolytic cell the magnitude of the cell Ecell = 0. ∆G > 0 (B) Ecell > 0 . obtained from aniline.05 molar)  M+ (aq.10 M). (2010) M (aq) Given: E° 4 + 2 + 0. balance.01 M) is 10 times smaller than the molar conductivity of a solution of a weak acid HY (0.20 The molar conductivity of a solution of a weak (C) Fe4 [Fe (CN) 6]2 (D) Fe3 [Fe (CN) 6]3 acid HX (0.47 Q.25V. the number of moles of M+ treatment with iron (II) sulphate and H2SO4 in presence oxidized when one mole of X is converted to Y is of air gives a Prussian blue precipitate. The resulting potential difference acids to be << 1) (2015) across the cell is important in several processes such as transmission of nerve impulses and maintaining the ion Q. If λ ≈ λ 0Y − . 2.151 RT Q. on Under standard conditions. a pKa 0 Paragraph 4: The concentration of potassium ions X− inside a biological cell is at least twenty times higher (HX) . A simple model for such a concentration cell involving a metal M is: Pt(s)  H2(g.092 V when 4+ = 10 x . ∆G < 0 The value of x is (2016) (C) Ecell < 0 . Q.  E° = 0.21 For the following electrochemical cell at 298 K. is consider degree of ionization of both than the outside. ∆ G° = 193 kJ mol/L r (D) Ensures mixing of the two electrolytic solutions. 0. X → Y.16 Sodium fusion extract.0025 molar M+ solution. the salt bridge (2014) 0.05 molar solution of M+ is replaced by a Q. is used for oxidizing M as M → M + + 3+ + 2e . 1M) M4+(aq).18 If the 0.059 V M /M F (A) Ecell < 0 .19 All the energy released from the reaction 0 –1 (C) Is necessary for the occurrence of the cell reaction. Chem i str y  17.17 For the above cell = = V. ∆Gº < 0 (A) 2 (B) 1 (C) 1 (D) 2 Q.
6 Q.16 Q.22 –0.59 V Q.5 λm = 124 Ω1cm2mol1 Q.104 V V Q.45 Exercise 2 Exercise 2 Q. 2 × 10–4 Q.30 Q.17 Q.19 (i) 0.5 Q.96 V Q.8101 V (iii) 0.10 3.5 Q.9 ∧m = 32. (b) –0. 34 V Q. 66 gm (ii) –0.20 Previous Years' Questions Previous Years' Questions Q. 4 8  Electrochemistr y PlancEssential Questions JEE Main/Boards JEE Advanced /Boards Exercise 1 Exercise 1 Q.451 V.4 Q.3 Q. (v) –0.268 V Q.3 Q. Ca.67 × 10–4 Q.3 Q.27 2.20 0.28 (a) –0.226 V (iv) 1.12 Q.26 Na.219cm 1 Q.04 kJ. E°cell ==++1.8 0. (ii) 0.23 (i) 0.1615 V Exercise 1 Q.91 V Q.8 Q.21 0.0295 V Q. (ii) 0.42 Q.19 Q.1 7 .2 124 ohm cm mole –1 2 –1 Q.30 Q.22 Q.9 Q. Q.7 Q.3692 Q. ka = 2.7288 V .9 Q.118 V.2278 V .12 Q.25 3.1 Q. (c) (i) –0.18 Q.8 Answer Key JEE Main/Boards Q.16 Q.104 1.4 ∆rG° = 213.2515 V.29 1.15 Q.1536 V Q.18 Q.23 Q.3 × 102 ohm–1 cm2 equi–1 Q. Mg and Al.35 Q.4 Q. 765 cm2 mol–1 .0413 V.14 E° = 0.24 0.7 Q.12 Q.
74 × 10 4 Q. Kh = 1.16 –1.6 D Q.19 C Q.3 Q.1 (c) calomel electrode Q.12 Eº = –0.32 V (O2) = 99.27 Eq.29 43.7 Eº = – 0.42 3. = 158.037 V Q.33 amp.40 –0.41 0.456 g Q.24 0. 190.35 2.1 C Q.227 × 1063 Q.11 [Br–]: [Cl–] = 1: 200 Q.71 V Q.10 Ksp = 1.16 A Q.8 D Q.39 V Q.6 D Q.43 × 10–5 M Q.46 V Q.4 C Q.9 0.36 1250 s.21 C Previous Years Questions Q.1 D Q. (b) 7.188V Q.31 42.17 D Q.59 V.5 – 0.18 C Q.124 V.24 × 1016 Q.536 × 10–5 M3 Q.20 Eº = 0.7 A Q.39 0.167 V Q.21 D Q.13 –0. V (H2) = 58. 0.34 1.22 C Q.8 h =2.12 B Q.22 0.13 C Q.20 D Q.5 D Q.15 C Q.1 mL Q. wt. = 107.9 A Q.14 C Q.15 1.25 K = 10268 Q.3 Ka = 6.10 B Q.16 B Q.2 D Q.4 1.307 V Q.37 1.2 pH = 6.2 B Q. Q.23 A Q.14 C Q. non–spontaneous Q.941 × 10 2+ 2+ 37 Q.20 D Q.12 × 10–2.19 Eº = 1.24 A JEE Advanced/Boards Exercise 1 Q.373 V Q.46 mL.17 A Q.14 1.4 B Q.49 Exercise 2 Single Correct Choice Type Q.28 643.68 mL.29 cm . Q.12 C Q. Co3+ = 10–8 Q. Total vol.1511 V Q. Hr.30 265 Amp.1456 ampere Q.19 B Q.064 M Q. –0.3 B Q.10 C Q.6 (ii) 1.11 B Q. Chem i str y  17.8 A Q.23 Kf = 8.13 D Q.15 C Q.143 V Q.9 million year Q.18 5.4 × 105 coulomb Q.26 Ta+ = 5x10–9 .27V (ii) 245.33 57.3 B Q.5894 gm.1 kJ Q.1 × 10–16 Q.1 [Cu2+] = 10–4 M Q.21 [Zn ]/[Cu ] = 1.66 V Q.11 C Q.22 V Q.95 V Q.17 10 –2 Q.9 A Q.2 % Q.7 B Q.5 B Q.38 (a) –0.18 C Q.5 g Q.4414 V Q.61 Q.372 V.
46 2 × 105dm3 Exercise 2 Single Correct Choice Type Q.17 A Paragraph .1 C Q. q.2 Q.20 A → p.16 C Q. B → p.8 B.2 C Q.4 B Q.22 A .18 B Q.17 B Q. B.19 C Match the Columns Q. q.25 × 10–2 meter Q.1 Q.45 Ksp = 7.10 D Q.3 B Q.7 A. /liter Q.15 D Q.2 B Q. 5 0  Electrochemistr y Q. C.43 4.9 A. D → p.11 B Q. D Q.13 D Q. D Q.9 C Q. C Q.14 A Comprehension Type Paragraph .5 D Q.1 7 .15 B Q.16 A Q.1934 gm. r. B Q.6 B Multiple Correct Choice Type Q. C → q.11 D.6 D Q.682 × 10–17 Q.21 D Q.4 C Q.5 A Q.8 B Q.10 C.1 C Q.7 B. D Q.12 D Q.12 A Q. s Previous Years' Questions Q.13 D Q.18 C Q.44 0.14 C Q.3 A Q. C Assertion Reasoning Type Q.
09 = −212304 CV mol−1 ⇒ E = 0. 208 Sol 3: (i) Reaction: E = 1. 14 – 0.0001 ° E= cell 0. 02 0.104 V = 2.PH 2 [H+ ]2 2 (i) Zinc electrode is negatively charged 0. 1371 V Ag+(aq) + e– → Ag(s) (iv) Br2 + H2 → 2Br– + 2H+ k × 1000 2. ) → Cu ( s ) + Mg2+ ( aq. 298 V 0. 0001 M 0. 70 – 0. 53 V = −212304 mol−1 .344 + 0.001 E°cell = +1.076 V = E = E – 0. =−2 × 96500 C mol−1 × 1. ) E = 1. 02955 E°cell 0.04 2+ E = E° – 0.05 E = E° – 0.51 Solutions JEE Main/Boards (iii) Sn + 2H+ → Sn2+ + H2 0. 03)2 E = E° + 0. 09 = 0.104 V n=2 Use formula 0. 03 log 1 Then.001 E = E – log 2 0. 02955 log (0. 05 Exercise 1 n=2 −0. F=96500 C mol1 1 0.0591 0.0591 Sol 2: ∧m = = E = E° – log [H+] 2[Br] 2 M 0. 03 In balanced reaction there are 2 electron are transferring = 2. Chem i str y  17. 01)2(0.303 RT [Cu2+ ] E = E – log E°cell Eright = ° ° − Eleft nF [Mg2+ ] Use this link to get all values 0.104 V E = E° + 0.344 − ( −0. 208 Mg ( s ) + Cu2+ ( aq. 0029 At cathode ⇒ E = 0. 0029 Zn(s) → Zn(aq) + 2e– E = 0. 03 E°cell = +1.76 ) E = E – 0.2 2 ∧m = 124 Ω1 cm2 mol–1 = E° – 0. 001 M Sol 4: The formula of standard cell potential is −1 2. 03 log (ii) At anode: 0.0591 [Sn2+ ] Sol 1: Zn(s)  2+ Zn(aq)  + Ag(aq)  Ag(s) E = E° – log . 09 + 0. 67 V so that n = 2 (ii) Fe + 2H+ → Fe2+ + H2 Faraday constant.48 × 10−2 × 1000 0. 44 + 0.001 × 1 Plug the value we get E = E° – 0.0591 [Fe2+ ]PH E= E – log 2 − n FE°cell ∆r G = 2 + 2 [H ] 0.
76 q= = 0. 0134 6000 108 Moles of Ni deposited = 96500 Charge. 219 cm–1 At C = 0. 0134 × 96500 C 6000 Mass of Ni deposited = × 59 = 3. 53 106.2 102×k/sm–1 12. 31 Charge needed = (3nAl) × 96500C ∧m vs C 40 =3× × 96500 C = 4.674 1 1 (ii) Fe2O + H2O → Fe2O3 + H++e– 0. 5375 cm2 mol–1 ka = .45 nAg = = 0. 084 Cα 2 ∧ºm = 12. 05 0. H2O → O + 2H+ + 2e⁻ 2 2 11. 28 × 105 C 27 Sol 7: (i) H2O → O2 12.304 kJ mol−1 = 213.1 0.674 20 S cm2/mol Charge needed = 2 × nF = 2 × F = 1 F = 96500 C 40 (ii) Al + 3e⁻ → Al 3+ C 0.6 t= = I 1.0248 × 1000 C/M 0.575 11.85 11.05 0.37 1 11. 875 α = 0.74 Sol 6: (i) Ca2+ + 2e⁻ → Ca ∧ ºm 12. 03 0.896 × 10−5 Sol 9: ∧m = 1000 × = ∧m = 11.001 0. 02 k 1000 × 7.1 7 . 5 2  Electrochemistr y Sol 11: We use the formula = −212.575 11. 735 s Zn2+ + 2e⁻ → Zn . R = 1500 Ω ∧m = 11.105 Charge required = 2 F = 1. 275 ∧ ºm 390. 01.85 We have.1 2 2 Charge needed for 1 mole FeO = 1 F = 96500 C We have ∧m = ∧ º m – A C Sol 8: k = 0. 15 55.106 10. 14 0. 14 …(ii) C 0. A×0.02 0. 100 ∧m = = 124 Ω–1cm2mol–1 0. 765 cm2 mol–1 Subtracting ∧m 32.001 0. 146 × 10 s cm –3 –1 At C = 0. 6 C 96500 Q 1295. 2 × 10–4 1−α a (putting A in (i)) Sol 10: Ni2+ + 2e⁻ → Ni Sol 12: Ag+ + e⁻ → Ag Charge supplied = 5 × 20 × 60 C = 6000 C 1. 1 …(i) G* = Rk = 0.k = 2.37 11. 02 0. A×0. Q = nAg. F = 0.010 0. 1 0.04 kJ k × 1000 ∧m = 1000 C Sol 5: ∧m =k× C 0.5 A = 6. 01 A = 0. 22 0. 93 × 105 C 10.00241 ∧m = 32.37 11. 575 = ∧ºm . 66 gm Q = 1295. 85 = ∧ºm .5 t = 863.85 23.
18 F Q Moles of Zn. 09 = – 0. 03. still not feasible. 09) = –0. of Zn = nZn × 65 = × × 65 E° = 0. of copper = nCu × 63. 77 – 1. 2515 V E° = +0. 76 V.53 nAg ∆E1 = –nFEº = –0. nZn = = 2F 2 Cu+ + e → Cu. 5 F E° = 0. w Ag 1 Wt. then. 036 Fe3+ /Fe negative oxidation potential. n = 1 mAg 2 Wt. Adding Cu2+ + 2e⁻ → Cu Cu2+ + 2e → Cu. it is the strongest º º oxidising agent. 32 > 0 Br2 /Br + Fe2 + /Fe3+ Sol 19: (i) Cu2+ + 2e⁻ → Cu This reaction is feasible.0591 1 1 E =E° – log = 0. Chem i str y  17. 32 < 0 Fe3+ /Fe2 + Br2 /Br − (ii) As Ag cannot get reduced. 5 F For Cu. 34 – 0. 426 gm –2F E°= –0. of Zn = 0. 836.001 Sol 14: Cu2+ + e → Cu+ E = 0. 32 < 0 (v) Br2(aq)+Fe2+(aq)→ Br–(aq)+Fe3+(aq) 2 ∴ Fe3+ cannot oxidise Br– to Br2. 77 = 0. 66 V Ag+ /Ag Cu/Cu+ Al/Al This is feasible. E = –0. n = 1 . 09 – 0. Eº = E –E = 0. (iii) Ag is the strongest reducing agent as it has the least If Fe3+ → Fe. this is not feasible oxidised agent. 52 = 0. 77 – (1. Q nCu = = nZn ∆G = ∆G1 + ∆G2. 43 gm ∆G2 = –nF E° = –0. E° = Eº + Eº Fe3+ /Fe2 + Br − /Br2 1 = 0. 34 V 1 Sol 13: (i) Fe3(aq) + − + I(aq) 2+ → Fe(aq) + I (g) 2 2 Sol 15: Element with maximum oxidation potential will E = Eº− + Eº = –0. Eº = –0. 77 = +0. Sol 18: Fe3+ + Br– → Br + Fe2+ Fe3+ /Fe 2 2 E° = –0. 18 F – 0. 2870 Eº 2 + = 1. n = 2 2F Wt. still not feasible. So. \Reducing order: Pb < Zn < Al 1 1 (iii) Fe3(aq) + − + Br(aq) → Br2(g) + Fe2+(g) 2 2 Sol 16: (i) Since O3 has the highest SRP. 23 > 0 I /I2 Fe3+ /Fe2 + have highest reduction potential. 5 = 0. 54 + 0. 50 V. Zn/Zn2 + + (ii) + Ag(aq) + Cu(s) → Ag(s) + Cu(aq) Eº = 0. (iv) Ag(s)+Fe3+(aq) → Fe2+(aq) + Ag+(aq) Sol 17: IO3– will act as better oxidising agent in acidic E = Eº + Eº = –0. and E° = –1. This is feasible. this is not feasible 1 if Fe3+ → Fe. 77 = –0. 13 V Pb/Pb2 + º º E =E +E = 0. Eº = 0. E° = Eº + Eº = 1. O3 is still the strongest So. 18 V. 8 – 0. (iv) Ag is still the strongest reducing agent. 8 + 0. 0295 log 2 2 [Cu ]+ 0. 0. 126. 03 < 0 medium due to its larger SRP in acidic medium then Ag+ /Ag+ Fe3+ /Fe2 + basic medium. Now.
34 V. n = 1 Sol 21: CH3COOH CH3COO– + H+ ∆G1 = – nF E1 Cα 2 ka = = Ca2 ∆G1 = –0. 76 – 0.02 Ksp = [Cu2+] [OH–] 2 = 1. 492 × 10–3) E° = 0. 8 – 0. 0591 log = 0. 303RT log (2×10 ) –10 2 2 E° = 0 2. 0591(–1. ka α= K s = 2 × 10–10 C 1 ∆G2 = –RT ln Ksp [H+] = Cα = Ck a Adding [H+] = 0. 57 E = 0.0591 E = 0. 5015 [H+ ] 10−17 = –0. 34 – 0. 15 + 4. 0295 log (0. 0591(0. 0591 log Cu(OH)2 Cu + 2OH– 2+ (PCl )1/2 2 0.357 × 1.5)1/2 K sp 1 × 10−19 [Cu2+] = = E = 1. 77 – 0. 36 – 0. 1536 V E° = 0. 4 2 [Cu2+ ] PH21/2 1 E = 0.74 × 10−5 AgCl + e → Ag + Cl– [H+] = 2. 226 V Sol 22: pH = –log[H+] 1 (iv) Cl2 + e⁻ → Cl– 2 13 = –log[H+] ⇒ [H+] = 10–13 Eº = 1. 8101 V E = 0. n = 2 pH = – log[H+] 0. 492 × 10–3 ∆G = ∆G1 + ∆G2. 7287 V (iii) AgCl + e⁻ → Ag + Cl– Ag+ + e⁻ → Ag. n = 1 1 H → H+ + e –F E° = –0.303RT E° = 0. 548) (0. 36 V kw 10 −14 1 Cl2 /Cl− [OH–] = = = + [H ] 10 −13 10 [Cl− ] E = E° – 0. 268 V . 0591 log = –0. 0591 log [Fe3+ ] 0. 34 – 0. E1 = 0. 0591 log[H+] = –0. 76 [Fe2+ ] Zn/Zn2 + Zn/Zn2 + E = E – 0. 4) E = –0.1 7 . 451 V [OH− ]2 10−2 [Cu2+] = 10–17 M 1 (v) H + e⁻ → H2 + 2 Cu2+ + 2e → Cu E° = 0 E° = 0. 8 F – 2. 0295 log (2. 02) 2 ( [Fe2+] = 5 × [Fe3+] ) E = 0. 77 V Fe3+ /Fe2 + Eº = – Eº = 0.0591 1 E = E°– log [H+] = 10–4. 1615 V E = –0. 02 Eº = 0. 0591 log = 1. 5 4  Electrochemistr y (ii) Zn → Zn2+ + 2e⁻ Sol 20: Fe3+ + e⁻ → Fe2+ 0. 8. 0591(log 2 –log[H+] ) = 0. 8 + log (2 × 10–10) F E = –0. 0591 log 5 E = E – log[Zn2+ ] = 0. 8 F 1−α AgCl Ag+ + Cl–. 36 – 0.
91 V E° = 0. 22 – 0. 1182 0. 2 S cm mol2 –1 −0. 8F n = 2. n = 1 0. 0591 × 10 = 0. 05 – 0. 2955 V 2 2 Cα 0. 591 V (ii) Sodium Er = –E = –0. 22 V 1 (ii) E = E° – 0. 8 F – 2. 0591 log[Cl–] = 0.0591 [Ni2+ ] ∴E = E1 – log (b) HCl → H+ + Cl– 2 [Ag+ ]2 [H+] = [HCl] = 0. 0591 log (4 × 10–3) H → H+ + e⁻ 2 2 E = 0. E1 = 0. 17 – 0. Chem i str y  17. 0591 V (iii) Calcium Sol 29: n for H2SO4 = 2 (iv) Magnesium Normality = Molarity × n = 2M (v) Aluminium k × 1000 26 × 1000 × 10−2 ∧e = = = 130 Scm2 equiv–1 N 2 . (0.55 Sol 27: Mg(s)Mg2+(aq)Ag+(aq)Ag(s) Sol 23: (i) Ag+ + e → Ag . Er = –0. 160 M) + 2 Ag(s) E = –0. n = 1 Mg(s) + 2Ag+ → Mg2+ + 2Ag ∆G1 = –nF E1 = –0.303RT Sol 28: (a) H2SO4 → 2H+ + SO42– E° = 0. 02 M E° = 0.1 1 α= = 0 ∧m 404. 80 V. 303 RT log(2×10–10) 2. 209 (10−4 )2 ∆G = –nF E° = ∆G1 + ∆G2. Er = –0. 1182 . 0295 log = 1.2 Sol 25 HCOOH H+ + HCOO– E = E – log = 0 – 0.0591 log 1 P 1/2 1 0 0 0 H2 ∧m (HCOOH)= ∧m (HCOO–) + ∧m (H+) E = 0. 303 RT log(2×10–10) E = E° – log 2 [Ag+ ]2 Adding. E° = 3. 002 M) E = E° – 0. 135 1 (2 × 10−3 )2 H → H+ + e⁻ 2 2 E = 0. n = 1 [H+ ] 0.02 Sol 24: Ni(s) + 2Ag+(0.0591 E° = log[H+ ] = 0.13) AgCl + e⁻ → Ag + Cl– = 3.2 (i) pH = 5 α = 0. 05 – 0. 67 × 10–4 pH = 14 – pOH = 10 Sol 26: (i) Potassium E = 0. 17 V AgCl → Ag+ + Cl– 0. 0413 V = 349. 0591 log = –0.0591 [Mg2+ ] ∆G2 = –RT ln ksp = –2. 2955 V ka = = 1−α 1 − 0. 0591 p[H] ∧m 46.025(0. 0591 log 1/2 PH 4 2 → Ni2+(0. 8 + log (2 × 10–10) F [H+] = 2[H2SO4] = 0. 6 + 54. n = 1 0 ∧m = 404. 36 V E° = 0. 01) n=2 E = +0. 2 0. 17 – 0. n = 1 E = 2. 0413 V. 96 V –F E° = –0. 0591 × 5 = 0. 0295 log = 3. 6 (c) E = 0.16 = 1.114) Er = –0. 0591 log(0.0591 [H+ ] 0.114 (ii) pOH = 4 ka = 3. 114 E = 0.
0591 log 10 = –0. 0591 V Then.4 × 10 −2 0. For 1 gm. 3: 0.2 1 2 2 = . 81 × 1022 × 1.7 7. 799 + 0. water will be reduced.2 Molar ratio = : : = 0.1 7 . 2 kWh 1 Cost = 13.0591 Sol 2: (B) Moles of Ag = 1 E° = log(2.1 2. 94 g 8.0591 (PH )1/2 E= log 2 = –0. . Sol 13: (C) ∧m = . 059 log [Ag+] 1: : = 6: 3: 2 2 3 [Ag+] = 5. 2F charge 2F Sol 9: (A) We have. 2H2O + 2e⁻ → H2 + 2OH– (aq) ∧m 10 Sol 14: (C) α = = = 0. 8 L 1 2. for M gm. 0591 log 3 [Ag+ ] 1 1 0. charge = = 1. × = 0. 6 × 10–19 M 0. 13 × 10–10 2. 002 Sm2 mol–1 50 4. 3667 V 2 1 Moles of Cu = 2 Sol 10: (B) Ag+ + e⁻ → Ag 1 1 Moles of Al = E = E°– 0. 5 At anode = 6: 2: 3 1 1 2H2O → O2 + 4H+ + 4e⁻ = 1: : 3 2 1 Moles nO = nC \ Valency = 1. charge required = 2F −0. 0591 V If atomic weight is M.1 Sol 3: (B) Moles of A = ksp = [Ag+] [Cl–] = 5.5 ≈ 445 mL O2 is liberated Mass = 8.5 VO = 22400 nO = 22400 × × = 441 mL Sol 4: (B) Volume of plate = 10×10×10 cm = 1 cm –2 3 3 2 2 2 63. 69 × 1012) = 0. 1 [H+ ] ∆E = 0. 5 6  Electrochemistr y Exercise 2 Sol 7: (B) This is a convention. Single Correct Choice Type 1 Sol 8: (A) H+ + e– → H 2 2 Sol 1: (C) M+2 + 2e → M E° = 0 For one mole.94 P = 1. 25 = 0. 65 × 8 kWh = 13. 05 0 ∧m 200 pH of the solution around cathode will decrease.5 8. 1 × 10–11 7 2.5 Sol 6: (D) At cathode.0591 ⇒ M = 66.5 q = 1. 65 kW Quantity of electricity = × 2F = 27172 C 63. 15 Sol 11: (B) At cathode 7 27 78 Cu2+ + 2e⁻ → Cu = 3: 1: 1.94 Moles = Sol 12: (B) P = VI 63. 1: 0. 3 and 2 2 2 2 1 2. R a C VH = 2 × VO = 4. . 7 gm E° = log kC 2 0. 2 × 5 paise = 66 paise Sol 5: (D) H2O → H2 + O 2 2 2H2O → 2H2 + O2 1 1000 Only water will be oxidised and reduced.
9650C will liberate silver = 10. E° = 0. 005 Sol 19: (C) At cathode. 674 F ∆G1 = 4 2 ∆G4 = –1F(Eº) = –0.4)1/2 ⇒ ∧m = 380 × 10–4 × 0. cathode acts as source of [H+ ]2 [Cl– ]2 electrons. 674 F + 0. 1182 [H+ ]1 [Cl– ]1 + e– Sol 3: (B) Ag+ → Ag. 41F Cu2+ + e Cu+ .1)1/2 0 ∧m E = –0. 153 F –nFE i=1 Adding. 153 4 Cu+ → Cu2+ + e⁻. → 10–1 α= 10−1.(0. ) = –2 × 285. C = y) C xy x 1 H → H+ + e⁻ 2 2 ka 1. 5 kJ = –571 kJ Au + 2e → Au 3+ – + ∆G = ∆H – T∆S ∆G2 = –nFEº = –2. 410–20. 0591 log = 0. E1–E2 = 0. 0591 × 2 = 0. Chem i str y  17. 041 V 1000 × k ∧m = C × 1000 Sol 20: (D) O2(g) + 4H+(aq) + 4e– → 2H2O() k = 1. 1182 silver = 108 gm. 23 V ∆G° = –nFE = –474. 96500 C will liberate ∴E2 – E1 = –0.8 . 337 1 1 O2 + H2O + e– → OH– –nFE = –0.01 2 2 ∧m 0.(0.6 × 10−5 1 1 Sol 16: (B) α = = = 0. E° = –0. Eº = 0. 3 1 H+ + e⁻ → H 2 2 1000 1000 1 At anode Sol 15: (C) ∧m = k × = (k = .57 [H+] = Cα = 0. 04 = 1. 78 kJ Sol 17: (A) Au+ + 2CN– = Au(CN)2– ∆Hf (O2) = 0 ∆G1 = –RT ln X ∆Hr = 2∆Hf(H2O. 153 F At cathode E° = 0. 0591 log 1/2 1/2 PH . Sol 18: (C) At anode Cu+ + e⁻ → Cu 1 ∆G = ∆G1 +∆G2 H → H+ + e⁻ 2 2 –F E° = –0. 52 × 10–2 S m–1 E° = 1. 04 H2 + H+ → H2 + H+ C 0. 521 V 1 Cl + e⁻ → Cl– 2 2 1 1 Previous Years’ Questions H2 + Cl2 → H+ + Cl– 2 2 Sol 1: (D) Impure metal made anode while pure metal [H+ ][Cl– ] made cathode. ∆G = ∑ ∆G1 = –RT ln X + 1.PCl 2 2 Sol 2: (D) In electrolytic cell. E = Eº – 0. pH = –log[H+] = log[200] = 2. 0591 log 10−2. 52 × 10–3 E = –0. 5F Sol 21: (C) Cu2+ + 2e⁻ → Cu. 322 kJ/k Au → Au + 3e⁻ 3+ T ∆G3 = –nF(–Eº) = 4. 153 Summing. 8F ∆H − ∆G ∆S = = –0. 29 F ∆G2 = = + 0.
Hence.2 M solution Fe+2 + 2e– → Fe.1 Sol 10: (C) Velocities of both K+ and NO3– are nearly the = 1.036 variation of molar conductivity with concentration we (Fe3+ /Fe+2 ) can say that = 0. [Zn2+ ] Where.02M solution 0.02 M solution exactly. = = Conduc tance(l) Conduc tance(II) 129 Sol 14: (C) Fe3+ + 3e– → Fe.0295 log 10 = 1.1 7 . 0. ∧NaCl is also needed.0591 [Zn2+ ] o o o So.878 – 0.the 2 [Cu2+ ] o conductivity value of NaCl i. it = – 1 × E ×F (Fe3+ /Fe+2 ) is sure that its molar conductivity will be slightly greater than 12. 2 –1 2 (1)2 0.14) =−0.0591 P(H ) E= red Ered − log 2 Sm n (H+ )2 K[A]A C×l Sol 5 (B) C = .30V Sol 9: (A) Cell constant The negative EMF suggests that the reaction goes Conductivity(l) Conductivity(II) spontaneously in reverse direction.439 − 3 × 0. the molar For complete discharge. 0. [Zn ] 2 + ⇒ 2+ = 1037. Q = [Cu2+ ] Sol 8: (D) According to Kohlrausch’s law. (A) is the correct answer.24 × 10–3 × 10 Sol 15: (C) E = E – log n [Cu++ ] = 124 × 10–4 S m2mol–1. .44 − ( −0.e.07 volt. Ecell = log ∧HOAc from the conductivity of ∧NaOAc & ∧HCl . 5 8  Electrochemistr y Sol 4: (C) Gold (Au) and Silver(Ag) are present in the Sol 11: (C) 2H(aq) + + 2e− → H2(g) anode mud. Λ o + Λo + Λ o+ + Λo – − (Λo + Λo – ) Sol 13: (D) For the cell reaction. Conductivity (II) = Sm−1 520 ∆G1 = –3 × F × E Fe3+ /Fe 0. same in KNO3 so it is used to make saltbridge. ∴ Ered is found to be negative for (c) option Sol 7: (A) From Kohlraush’s law 0.2 M = 200 mol m–3.0591 Sol 6: (D) 0.439 × F Note: From given data it is not possible to calculate molar conductivity of 0. ∆G = ∆G1 –∆G2 200 ∆G = 3 × 0. Fe acts as cathode and Na+ OAc – H Cl Na+ Cl = Λ o + Λ o+ = ΛHOAc o Sn as anode.108 = 0.0591 Λ oCH = Λ oCH o + ΛHCl o − ΛNaCl Sol 12: (C) E= cell Ecell − logQ 3COOH 3COONa n Hence.036G – 2 × 0.0591 2 Ered= 0 − log = S m mol . Assuming linear inverse E = 2 × 0. Therefore to obtain 0. Molar conductivity of 0. ∆G2 = –2 × F × E Fe2 + /Fe 129 / 520 = = 12.10 – 0.3. Fe3+ + e– → Fe2+ . o o o o [Cu ] ΛNaOAc + ΛHCl − ΛNaCl = ΛHOAc i. OAc− H Ecell =Ecathode − Eanode =−0.059 [Zn++ ] = 1. Ecell = 0 conductivity of an electrolyte at infinite dilution is the sum of conductivities of its ions.059 1 = 1.10 – log 2 0.K= = 1 [A]A mol m3m2 0.1 M difluoroacetic acid has highest electrical Ered = log2 2 conductivity among the given solutions.4 × 10–4 Sm2 mol–1.4 × 10–4 S m2 mol–1. However.770 V ∴ Molar conductivity of 0.e.
30 − = log 0.59 Sol 16: (A) Sol 19: (B) 2H+ + 2e− → H2 ( g) As E −0.72) − = log 0. ∴ ∆G1 = −nFE = −3F( −0.3010 = negative value 2 1 2 0. E° = –1.2606 V Fe + Ni+2 → Fe2+ + Ni Zn + Ni2+ → Zn+2 + Ni Sol 17: (D) 3 All these are spontaneous CH3OH( ) + O2 (g) → CO2 (g) + 2H2O( ) ∆H = −726kJ mol−1 2 H2O( ) ∆H = −726kJ mol−1 Sol 21: (D) Higher the SRP.36 + 3.878F 3Mn2+ → Mn + 2Mn3+.439) = 0.059 log (here E is − ve when PH > H+ ) 2Cr + 3Fe2+ → 3Fe + 2Cr3+ 2 2 H+ 0.30 − = log 6 (0.4 kJ mol−1 ∆Gf CO2 ( ) = Sol 22: (C) ∆G = Σ∆Gf products − Σ∆Gf reac tants According to Debye Huckle onsager equation.18V.36F Fe3+ + 3e− → Fe.30 − = log10 4 Zn + Fe+2 → Zn+2 + Fe 6 10 −6 6 Ecell=0.0591 2 −0.36 – 2(–1.38 F ∴ − FE = +0.51) =−1.878F But ∆G3 = 12FE ∴ E= 0.42V = Cr3+ /Cr Fe /Fe PH2 2 E= o E − 0.036 V (2) Mn3+ + e⁻ → Mn2+. E = −0. MnO −4 is strongest oxidising agent.1)2 ( −0.6 kJ mol1 Here A = B ∆G ∴ λC = λ ∞ + (B) C now Efficiency of fuel cell = × 100 ∆H 702. Sol 18: (C) ∆G1 =−2F( −1.2 kJ mol−1 Also ∆Gf CH3OH( ) = Hence.108F − 0. To find Eo for Fe3(aq) + + e− → Fe2+ (aq) ∆G3 =∆G1 − 2∆G2 ∆G1 =−nFE =−1FE = [2. =394.0591 (0.2 λC = λ ∞ + (A) C =702.18) =2.878F = 5.439 V (1) .1)2 0.77v − 2FE ⇒ 5.878 − 0.036) = +0.38F = .51 V.42(237.51)] F G= G1 − G2 = (2.01) 3 6 (0.0591 (Cr3+ )2 E= cell Ecell − log −0.6 Sol 23: (A) = × 100= 97% 726 (1) Mn2+ + 2e⁻ → Mn.108F0. −166. Chem i str y  17. better is oxidising agent.02) F ∴ G =0.2 kJ mol = −394.108F ∆G1 =−F( −1.0591 0.0591 6 (Fe2+ )3 = log10 = × 0.72V and E 2+ = −0.2 × (2) ∴ ∆G1 = −nFE = −2F( −0. E° = +1. −1 ∆Gf H3O( ) −237.42 + 0. E = −0.108= 0.0591 (0.2) + 166.0591 10−2 0.51F Also Fe2+ + 2e− → Fe(aq).01)3 Sol 20: (D) 0.
059 E = 0 – 0.0591 1 E = E – log = 0. 170 V pH = 6. 226 5 [H+ ]8 [MnO − ] 4 2 [Cu2+ ] MnO4 + 8H + 5e → Mn + 4H2O – + . Sol 3: Ag+ + e⁻ → Ag 0. 61 H2 /H+ At cathode.8 × 10−5 1 α= = = 0. 0591 log C 0. 059 log[H+] JEE Advanced/Boards [H+] = 6. E = 0.0591 1 NH3 + H2O NH4+ + OH– º E =E – log Ag+ /Ag Ag+ /Ag 1 [Ag+ ] kb 1.8 × 10−5 1 α= = = 0. 28 – Eº + H /H2 º Sol 5: CH3COOH CH3COO– + H+ E = –0. 226. 01182 log = 1.1 7 .01 0.08)8 (0. 059 log [H+ ] [H+ ] E = Eº – 0. 34 × 10–3 + 1 E = E – 0.039 = log[H+] 2 0. 0591 log 1. 0295 log [Cu2+] = –0. Bi will also start to deposit 0. 08 0. 982 H2 /H+ Ag+ /Ag As E° value is negative reaction is nonspontaneous. 344 Cα 2 ka = 1−α 0. 2+ 0.3 × 10−3 E = 0.8 α = 0. 6 × 10–4 Exercise 1 6.0591 [Mn2+ ] 0. 67 = 0. 188 H2 /H+ − Sol 24: (A) Cu2+ + 2e → Cu 1 2F 1mole H → H+ + e⁻ = 63. 01 0. 059 log 1 [H+ ] H → H+ + e⁻ 2 2 1 –0. 34 × 10–3 H2 /H+ pH = –log[H+] E = 0. 344 – log = 0. 09 0. 1 0.01) 0. 0134 H+ + e → H2 C 0.1 2 [H ] = Cα = 1. 5 Sol 1: Cu + 2e → Cu 2+ 1. 39 H+ /H2 ka 1. 118 log [Cu2+] = –4 t = 0 0. 188 = 0 – 0. 28 V (0. 0591 log H2 /H+ H2 /H+ PH 1/2 −0. 8 – 0. 39 = – 0.5g 2 2 0.6 × 10−4 ⇒α= = 0.09 E = 1. 042 E = 0. 51 – 0. 39 V Sol 2: Reduction potential of calomel electrode = 0. 6 0  Electrochemistr y ⇒ E = −2.69 V E +E = 0. 226 2 [Cu2+ ] ka = 6. 794 Ag+ /Ag .0591 1 Sol 4: E = E – log 0. 74 × 10–4 As after E < 0. 6 × 10–4 Cα = 6. 8 [Cu2+] = 10–4 M t=t 0.
1 E = E°– 0. 24 × 10–4.05 . 4 = 1. 5 × 1. 0591 log [Ag+ ] Sol 7: Cu(OH)2 Cu2+ + 2OH– [H+ ]1 [Ag+ ]2 ∴ E2 – E1 = 0. equivalents of H+ remaining = 1 meq. 05 [Cu ] [OH ] = Ksp 2+ – 2 E2 = 0. 628 = 0. 05 = 2 meq. 87 + 0. 628 V Ch = [H+] −11 2. 27 V ∴ m.35 × 10 6. 0591 log Sol 8: H2 + H+ → H2 + H+ 0. equivalents of H+ = MV = 30 × 0. 2 = 245. 170 – 0.1 −14 E2 – 0. 0295 log [Ag+] c = 0. We have pH = –log[H+] = 14 [H+ ]2 [Ag+ ]1 [H+] = 10–14 0.61 [OH–] = Cα = 4.0591 1 1 E = E° – log = 0. 59 × 10–4 1 E = Eº – 0. 0591 log = –0. 95 V [Cu2+] = 1 × 10–19 Sol 10: E° = 0 Cu2+ + 2e⁻ → Cu Ag+ + Ag → Ag+ + Ag 0. 1 It does not depend on [KOH] [H+] = = 0. 34 – 0. equivalents of OH– added = MV (i) Cell reaction = 40 × 0. 87 V kh = 1. 1 = 3meq. 0591 log + 10 −14 [H ]cathode [H+] = = 2. 0591 log . 4 V Sol 9: m. 34 – 0. 9 = 0.05 2 2 [Ag+ ]a All conditions are standard except [H+] anode log = –13. 014 40 + 30 (iii) Maximum amount of electrical energy 1 H + Ag+ → H+ + Ag = –n F E°  2 2 = –2 × 96. Fe(s) + Ni2O3(s) → FeO(s) + 2NiO(s) m. 458 V (1 / 32) H2 /H+ H+ /H2 Cα 2 Sol 6: Fe(s) + 2OH → FeO(s) + H2O()+2e – Θ kh = 1. Chem i str y  17.014 [OH–] = =1 [H+ ] E2 – 0. 0591 log 1 [H+ ] H+ + e– → H 2 2 log [H+] = 6. 788 = –0. 56 = – 0. 0591 log H+ /H2 H2 /H+ [H+ ] C6H5NH3Cl C6H5NH2 + H+ + Cl– 1 = 0.0591 [Ag+ ]a E= log = 0. 0591 log . 35 × 10–11 − [OH ] 1 –0. (ii) E° = 0. 22 V 1 [Ag+ ] c [Ag+ ]a 1 1 0. 12 × 10–2 Ecell = E +E = 0. 1 kJ [H+ ] ∴ E = E° – 0. 43 × 10–5 Ni2O3(s)+H2O + 2e⁻ → 2NiO(s)+2OH– E° = +0. 27 kJ PH = 1 atm.59 × 10−4 h= = 2. 9 = 0. 188 = 0 – 0. 05 M 2 2 [Cu ]+ 10−19 −0.1 10 0.α E° = 0. 3 0.
1 7 . 9 × 10–5 Eº = –0. 037 V E = –0. 0591 log [Ag+ ]c 3.303RT (10−4 )2 E = E1 – pk sp nF [Mn2+] = 1. 3 × 10–10 [Ag+] a = 10−3 [Br − ] Ag + Ag+ + Ag + Ag+ (k sp )AgCl Similarly. 05 Ag → Ag+ + e⁻ ∴ ksp = 1. 4 × 10–9 [I–] = [KI] = 0. 536 × 10–5 AgI + e⁻ → Ag+ + I– Sol 15: Mn(OH)2 Mn2+ + 2OH– ∆n = –nF E = –nF E1 – RT ln k Ksp = [Mn2+] [OH–] 2 RT E =E + lnk nF 1. 32 × 10–15 ksp = [Ag+] a[Cl–] AgI Ag+ + I– 2. 142 V [Br − ] 1 = 5 × 10–3 = − [Cl ] 200 ∆G = –Fn E = –RT ln k nF Sol 12: AgI Ag+ + I ln k = E RT ∆G = –nFE1 nF log k = E RT × 2. 126 V = [Br − ] [Cl− ] Pb → Pb2+ + 2e⁻ E = 0. 268 = − −10 [Cl ] 1 × 10 PbCl2 → Pb2+ + 2Cl– E = –0. [Br] – 3.3 × 10−13 (k sp )AgBr [Ag+] c = = 3. 591 log = 0. 8n = 2 ∆G = –nFE1 k = 1.9 × 10−13 [Mn2+] = 2. 15 Cell reaction: Sol 13: At anode Mn + Cu2 → Mn2+ + Cu AgCl Ag+ + Cl– E = –1. electrodes should be [Ag ] a = [Ag ] c + + reversed. 16 × 10–16 At cathode AgBr Ag+ + Br– Sol 11: AgBr Ag + Br + – ksp = [Ag+] c [Br–] ksp = [Ag+] a.3 × 10−10 E° = 0 [Ag+ ]a E = –0. [Ag+] c = Cathode anode [Cl− ] Ag+ + Ag → Ag+ + Ag E = 0 [Ag+ ]a 1. 8 × 10–10 = [Ag+] a × 0. (k sp )AgBr (k sp )AgCl Sol 14: Pb2+ + 2e⁻ → Pb E = –0. 2 ksp = [Ag+] [I–] [Ag+] a = 1.303 Ag+ + e⁻ → Ag log k = –4.4 × 10−9 cathode anode E = –0. 0591 log =0 [Ag+ ]c For a spontaneous process. 126 V [Br − ] 5 × 10−13 PbCl2 + 2e⁻ → Pb + 2Cl– E = –0. 6 2  Electrochemistr y [Ag+] = 2. 18 V Mn2 + /Mn .
0591 [Ag+ ]2 E = E – log Sol 18: Cell reaction 2 [Zn2+ ] Zn + Zn2+ → Zn + Zn2+ (1. 0295 log Cathode anode 0.9 × 10−5 Pb2+ + SO42– → PbSO4 E° = 0. 69 × 10–7 = log 2 2. 37 × 10 + –7 HSO4– H+ + SO42– 2Ag + Zn → 2Ag + Zn 2+ + 0. 52 V 0. 075 0. 075 Eº = –0.0591 [Pb2+ ]a [Zn2+ ] E=0– log +0.5 × 10−5 Eºcell = Eº – Eº Cu2 + /Cu Mn2 + /Mn [Pb2+] a = 2. 22 M – 2. 52 – 0. 56 – 0. 18) At anode. 525 0. 14) 6. 56 V ka ≈ 10–2 0. 188 V −0. 230 = 1. 34 – (–1. 46 × 10–3 º º E cell = EAg/Ag+ + EZn2+ /Zn = –1.0591 [Zn2+ ]a E= log 2 [Zn2+ ] c Sol 17: Pb + Pb2+ → Pb + Pb2+ −0.6 × 10–8 = [Pb2+] [SO4–2] ksp = [Ag+] [IO3–] 1.60 × 10–8 AgIO3 Ag+ + IO3– ksp = 1. 0295 log = 1.5 × 10−3 At anode . 126 V 1. 356 2 [Pb2+ ] 3. 80 V Ag/Ag+ [H+ ][SO24− ] ka = Eº = –0. 76 V [HSO −4 ] Zn2 + /Zn ka = 9.63 Eº = 0. 061 log a = –3. Eº = 1.175 E = –1. 34 V [Pb2+ ]a Cu2 + /Cu log = –2.0591 [Pb ]a [Zn2+] a = 1.0591 [Zn2+ ]a 0.75 × 10−2 PbSO4 → Pb2+ + SO42– E° = –0. 099 = log E = 0 2 3. 50 × 10–2 [Ag ] = 1. 06 2.13 × 10−7 0.22 [SO42–] = 7. 52 – (–0. Chem i str y  17. 230 E = 1.6 × 10−8 3.303RT k = 1.37 × 10−7 )2 E = –1. 56 + 0.0591 [Mn2+ ] Pb + SO42– → PbSO4 + 2e⁻ E° = 0. 13 × 10–7 Eº = 0.84 × 10−4 0. 356 E = Eº – log 2 [Cu2+ ] Pb2+ + 2e⁻ → Pb. 372 E° = 0 E = –1. 66 V ∆G = –nF E° = –RT ln k Sol 16: HIO3 H + IO3 + nF ln k = E° ka RT [IO3–] = Cα = C = Ck a C nF log k = E [IO3 ] = 0.08 × 10−8 [SO42–] = [Ag+] = 2.84 × 10−4 c 2+ 0. E° = –0.
303 × RT 2Ti+ + 2e–→ 2Ti [Zn2+ ] k= ∆G2 = –2nF E° = –2F(–0. 799 = log(6 × 10–8) + 0. 6 4  Electrochemistr y Zn2+ + 4CN– → Zn(CN)42– Now for Zn + Cu2 → Cu + Zn2+ [Zn(CN)24− ] 0. it is non spontaneous reaction.0591 [Zn2+ ] kf = E = E – log [Zn2+ ][CN– ]4 2 [Cu2+ ] 0.x). E° < 0. 799 F (1.450 0. 25×10–14 −14 1 + 6. 799 V Sol 20: Cu + 4NH3 → [Cu(NH3)4] 2+ 2+ ∆G2 = –nF E = –F × 0. 25 × 10–14 Eº = ln k0 + 0. 76 – (–0. ∆G1 = –RT ln k0 Ag+ + e– → Ag E = 0. E° = 0. 1 V ∆G = –nF E° = –RT ln k Ti+ → Ti3+ + 2e– E° = –1. 25 Sol 22: Ag(NH3)2 Ag+ + 2NH3 Eº = –1. 1 = 37. 34) [Cu2+ ] 3Ti+ → 2Ti + Ti3+ [Zn2+ ] 2 log = × 1. [Cu(NH3 )4 ]2+ Ag(NH3)2 + e– → Ag + 2NH3 Kf = [Cu2+ ][NH3 ]4 ∆G = –nF E° = ∆G1+∆G2 x 1 × 10 = 12 –n E° = –RT ln k0 – 0. 1 – log 1. 1 – 0.65 × 10 )) −3 4 2 1−x 1 kf = 5. 59 V k0 = 6 × 10–8 Since. 34) = 1.0591 1 = E = 1. 25) log k = E 2. 0295 log 6. 25 × 10–14 x 1 Sol 23: We have. 24 × 1016 = 1. 25 V nF ∆G1 = –nF E° = –2F(–1.0591 ∆G = ∆G1 + ∆G2 ⇒ –2FEº = –2FEº1 – 2FEº2 [Zn2+ ] = 1.69 × 10 −7 × (2.25 × 10 .25 × 10 (i) Co2+ + 6CN– → [Co(CN)6] 4– 6. A – 4x = 2 Adding.25 × 10−14 E = 0. 941 × 1037 [Cu2+ ] Eº = E 1 + E 2 Eº = –0. 373 V – 1 = 6. x= −14 1 + 6. 799 x F F 1 E° = 0. 28 2+ [Cu ] 0.25 × 10−14 kf = 1 × 1014 1–x= ≈ 6. 71 V Sol 19: Ti+ + e– → Ti E° = –0. 34 V ∆G = –nF E° Sol 21: Zn + Cu2+ → Zn2+ + Cu Ti3+ + 2e– → Ti+ E° = 1. 25 V we have.1 7 .24 1−x RT 2. 34 – 1.303 RT = 6. 799 t=0 1 A t=t 1 – x A – 4x x (n = 1) We have.
924 F –15. n=1 ∆G2 = –nF E° = –2 × F × (–0. (i) + (ii) + (iii) gives kf = 8. if Ti+ = 0.303 RT 0. 154) = 0. 816 F + 0. (ii) gives. 3Sn → 3Sn2+ + 6e⁻ E° = –0. n = 2 . 59 V Similarly for [Ag (CN)2–] ∆G = –nF E° = –RT ln k. 757 RT ∆G'1 = –nF E° = –2F × 0. 995×10–19) 2F 0. ∆G = –RT ln k = ∆G1 + ∆G2 + ∆G3 (i)Ag + e → Ag E = 0. 0591 log (1. 84 V 2. 83 F ∆G'3 = –nFE° = –6F(1. F = 0. 308 F ∆G3 = –nF E° = –1. 154V. 5 = 25 Sn → Sn2+ + 2e. 33 V. 7991 + 0. Now. Chem i str y  17. (iii) + (i). 82 V. E°= 0. 83 V. 15. 83 RT RT ∆G3 = 2∆G'3 1. 83 F Sn2+ → Sn4+ + 2e⁻.852 kins = 6. 0591 log (6. 7991 V.65 ∆G1 = –RT ln kf = – 43.83 log kf = + 19 ∆G3 = –15. 33) = –7. 272 F (ii) [Co(CN)6] 3– + e– → [Co(CN)6] 4– For. 82 F For. n = 6 ∆G = –RT ln kf = –1. 7991 F F ln k = × 15. 757 + 0. 96 F 0. 7991 + log kins Adding.0295 E° = –0. 2Cr2O72+28H+ + 12e⁻ → HCr3+ 14H2O ⇒ln kf = × 1. 816 F ∆G2 = –nF E° = 0. 307 V k = 1020 Sol 25: We have. 372 V E° = 0. 82F – 43. 136 V. n = 1 Sol 26: Ti+ → Ti3+ + 2e⁻. 136 = –0.59 log k = E = = 20 2. 7991 + 0. Eº = –1. E° =–0. 98 F F F For. 82 + 43. 924 F Co3+ + 6CN– → [Co(CN)6] 3– Cr2O72– + 14H+ + 6e⁻ → 2Cr3+ + 7H2O ∆G = ∆G3 + ∆G1 – ∆G2 Eº = 1.0591 ∆G2 = –RT ln kins log k = 268 Adding (i) and (ii). 96F ∆G 1 = –nF E = –0. n=1 + – –RT ln k=–0. 7991 F – RT ln kins 2Co3+ + 2e⁻ → 2Co2+ Eº = 1. n=1 ∆G1 = 3∆G'1 = –0. 27 × 1063 3Sn(s) + 2Cr2O78– +28H+ → 3Sn4+ + 4Cr+3 + 14H2O Sol 24: we have.82 + 0. 02 × 10–8 log k = 0. 1 × 2.059 Now.Eº = 1. k = 10268 [Ag(NH3)2+] + e– → Ag + 2NH3. 852 RT (ii) [Ag(NH3)2+] → Ag+ + 2NH3. 02×10–8) Ti+ + 2Co3+ → Ti3+ + 2Co2+ E° = 0.303RT E° = 0. n = 2 E° = 0. ∆G2 = 3∆G'2 = 0. 25 V ∆G = ∆G1 + ∆G2 Co3+ + e⁻ → Co2+ –F E° = –0. 3Sn2+ → 3Sn4+ + 6e⁻. n = 2 (iii) Co3+ + e– → Co2+. 757RT – 0.
4 SO24− Charge produced by 1 mole H2=2F 2F charge consumes 2 moles of [SO42–] . 105 (2.x [Ti+] = = 5 × 10–9 = Q.2 Moles of H2 reacted = =3 ∴ ∆n = 9.4x2 . 5 – x)3 = = 1. 3 × 0. 5 × 1000 gm = 4.5 − x)(2.4824 × 10−3 = M 2 = 3.(50)2 (2. 33 A t = t 2.1 7 . 434 = 0. for oxidation of water x ≈ 2. 5 g x. 124 × 2 × 10–9 = 11. 3 gm 20 Mass of H2SO4 = × 3. eq.35 Moles of O2 produced. 136 H2 +2OH → 2H2O + 2e – – [H2SO4] = 2.5 − x) charge utilised [Co3+] = = 10–8 Moles of H2S2O8 = = 0. Moles of H2SO4 = 8.4 (2. M. 868 (2. 294 × 3.5 − x)2 9. 5 kg 0. 5 as k >>>1 2H2O → O2(g) + 4H+ + 4e– Putting x = 2. = 3 × 63. 4824 m. 224 50 2 Weight of H2S2O8 = 0. q = 4 × nO = 0. of S2O32– 2 2 Moles of H2SO4 = 18. 9865 kg M = 107. = 1. 76631 kg 1 100 eq. 5 5 0 0 I = 643. q = 0. 998 50 2(2.4824 × 10−3 [H2SO4] = 5. Q = 2 × 0.5. n = 2 2– Number of equivalent = n. 5 g Vfinal = 50 ml wt. 884 22. of H2SO4 = ×4. 529 kg Equivalents of x = eq. 2 = 5 Charge produced by 3 mole H2=6F Ti+ + 2Co3+ → Ti3+ + 2Co2+ 6F 6 × 96500 Current. 5 – x 5–2x x 2x Cu2+ + 2e → Cu 3+ 2+ 2 [Ti ][Co ] number of moles of Cu produced = 3 k= = 1020 [Co3+ ]2 [Ti+ ] wt. Sol 30: Initially. = 190. of x = 2 Finally.617 11. =1× of I2 = × eq. 456 gm Sol 27: For thiosulphate (S2O3 ). nO = = 0. I = = t 15 × 60 t=0 2. of I– 39 Wt. 7973 kg 100 Sol 28: At anode. 02 11. V.(50) = 1020 Sol 29: At cathode.5 – x)(5 – 2x)2 2H2O + 2e⁻ → H2(g) + 2OH–(aq) x3 = 1020 (2.4 x3 = 1020 Charge needed.722 Moles of H2 produced = =0. 224 × 194 = 43.5) 3 2 22. mass of H2SO4 solution = 46. 5 × 10 –7 Charge utilised for production of H2S2O8 2. 529 = 1. 420 2 2. 5 – x = 2. 324 M 67. 139 × 3. 434 22. 5 2. 9865 kg = 0.5 − x)3 At anode. 5625 × 10–3 1020 Charge needed. 15 M Eq. Mass H2SO4 solution = 1.(50)2 . only reduction of water takes place (50). 6 6  Electrochemistr y Initial milimoles of Co3+ = 25 × 0.
we have. 2 × 7 × 60 34. 2 % 15. 3 × 10–3 F = 1215. 258 F = 2. 22 × 10–3 F 100 5.45 − x)98 Q ∴ = 0. 58 g Sol 31: Cu2+ + 2e⁻ → Cu Sol 34: Charge supplied per second 3 Moles of Cu deposited = = 0. 422 Charge supplied 21600 4 F charges electrolysed 2 moles of H2O. 3600 Mass of electrode = 100 – 42. 74 C = 1. 41 = 57. 45 2H2O → O2 + 4H + 4e + – t=t 4.67 According to net reaction 0. 6x 76.54 \ Moles of water electrolysed per second = 2 Sol 32: At cathode.5 Time required in years = × 86400 × 365 18 × 7. 78 × 10–2 F (4. 392 Charge required = 9.606 + (4. 4x = 96.5 × 106 63. 77 8. if charge will oxidise 0. 14 mL 463. Chem i str y  17.2 × 1012 × 103 Cu2+ + 2e⁻ → Cu Total moles of water = 18 0. 61 × 10–3 Moles of H2SO4 = = 4. ∴ Efficiency = 42. 9 million years After deposition of copper. 4 × 105 C . 258 moles SO42– = 2 × 1. t=0 4. = 7. 258 Total charge supplied = = 0. 3×10–3 8. 54 F 96500 Charge utilised = 2 × 0.306 Moles of H2 evolved = = 2. 27(1261 – 80x) Total volume = 158. 45 × 10–3 × 22400 = 99. 306 = 504 C = 5.4 Moles of Cu deposited = = 6. 27 Moles of O2 evolved = = 4. hr. of H2SO4 = × 1261 = 436.6 Wt. 22 × 10–2 F = 1.5 = = 15.61 × 436. 094 F = 9071 C Electrolysis: Charge supplied = 3 × 2 × 3600 = 21600 C 2H2O → 2H2 + O2 Charge utilised 9071 2H2O → O2 + 4H+ + 4e⁻ ∴ Efficiency = = = 0. 95 moles of Ag.95 9.22 × 10−3 436. 46 mL Pb(s)+PbO2(s)+2H2SO4() → 2PbSO4(s)+2H2O() At anode. 392 × 108 = 42. 047 × F = 0. rather than 1 mole Charge produced by 1. since purity of electrode is 95% Charge produced by 1 mole SO42– = 2F Here. 68 mL ⇒ 436. 138 Sol 33: Ag → Ag + e + – x = 1. 3×10–3 × F + 5.373 \ Moles of Ag oxidised = = 0. 258 5 × 2 × 3600 Change in moles of SO42– = x = 1.45 − x)98 + x. 47 –21. 41 g Ampere hours = = 265 Amp.2 × 1015 63.18 4 Volume of O2 evolved = 4. wt. 45 2 98 Volume of H2 evolved = 2.884 × 96500 Mass of Ag oxidised = 0. 608 – 98x = 340.77 Charge supplied = 2 × 6. 884 F 0. of H2SO4 = 27 Q = 2 × 6. 1 Sol 35: Initial mass of electrolyte H+ + e → H+ (as solution is acidic) 2 = 1. 373 F 96500 Pb + SO42– → PbSO4 + 2e Now. 261 × 1000 = 1261 g Extra charge supplied = 1. 047 1. 608 – 98x = 0. 61 × 10–3 × 22400 = 58. 45 × 10–3 12. 45–x x Total charge.
0591 pH ∴ Moles of copper reduced = = 5 × 10–3 2 Ecell = –0. [H+] = 0. [Cu2+] = 1 + 0. [Zn2+] = 1 – 0. 067 E° = 0 E = –0. 699 + 0.419 pH = = 7. cell reaction. Q 96. 1 × 10–1 = 10–2 E° = 1. 04 × 35 × 10–3 0. actual time = s = 1250 s 4 (EºOP = – EºRP) Now. 4 × 10 –3 0. 1 – (0. 9326 = 0.1 7 . 1 – 0.0591 [Zn2+ ] 0. 064 M 100 × 10 −3 direction and cathode (Calomel electrode) is positive electrode. n = 2 H+ [H+] i = 10–7 0. = 2 × 0.5 × 10 QH2 → Q + 2H+ + 2e⁻ Theoretical time = = = 1000 s I 0. = 2 equivalents of S2O3– Ecell = –0. reaction takes place in the given Molarity = = 0. 1 Moles of copper = 31. 0591) × (5) = –0.9326 n = 10–7 × 10–1 = 10–8 H+ = 1. Cu2+(aq) + 2e– → Cu(s) E = E = 0. 0. At cathode. at anode At anode 1 Zn2+ + 2e⁻ → Zn H → H+ + e– Q 2 2 Moles of Zn2+ reduced = = 0. 28 – 0. 124 V Equivalents of copper (b) When Ecell = 0. 0295)(–1. 0295 log 2 2 [Cu ]+ 1.0591 E = E – log[H+] 2 Current efficiency = 80% 2 1000 × 5 Eº + 0.067 E = E° – log = 1. 6 8  Electrochemistr y Sol 36: At anode. 5 \ Total moles of Cu2+ = 6. 0235 V 64 × 10−3 Since. 861 F 96500 Sol 39: We have. 9326 log[H+] = 1 Now. 5 × 10 × 3600 Sol 37: Current passed = F = 1. 1 V. 45) Moles of H+ produced = 10–2 – 10–8 E = 1. 419 + 0. 0591 log [H+] . Ecell is positive. 9326 2 2H2 → 4H+ + 4e⁻ Final. 0591 pH After passing of current. 699 + 0. 9326 = 1. Equivalents of copper = equivalents of I2 (a) At pH = 5. 2H2O → O2 + 4H+ + 4e Cu → Cu2+ + 2e⁻ pH = 1 Final. 28 Current passed = 10 F –2 10−2 ∴Ecell = 0. 419 + (0. 0591 pH = –0. at cathode At cathode. 143 V ≈ 10–2 Charge needed = 10–2 F = 965 C Sol 38: At anode. for quinhydrone electrode. 4 × 10–3 Ecell = 0. 0591 pH Therefore.0591 ( n = 2 for Cu2+) (c) At pH = 7.965 0. 1 Zn + Cu2+ → Zn2+ + Cu n = [H+] × v = 0.
29 cm 2. 6 V/cm ∆G2 = –2FEº L 10 / 100 ∧0 Ionic mobility (drift speed) = ∞ ×E Ag2S + 2e⁻ → 2Ag + S2– F 73. k2 = 1. 1 × 10–13 ∆H = 4 × 19. 64 – 0. 2 kJ [S2− ]. 001058 E = –0.0591 E = –0. Chem i str y  17. ∆G2 = –FEº.5 R= = Sol 40: Ag2S + 2e⁻ → 2Ag + S2– ka 9. 1 × 10–16 M 2H2 + O2 + 2H2O → 4H+ + 4OH– E = –0. 0295(–15. 167 V ∆T P ∆S = 408.71 × 10−3 × 1. 2 kJ = –0.10−3 = 1. 05 kJ = 76. H2S H+ + HS– . 38 1000 Sol 41: ∧eq = k × N ∆G = –nFEº = ∆H – T∆S 97. 64 V = k R a = 1.303 RT E' = E + log ksp 1 nF Sol 43: R = k a E' = –0.∆H = –56. 1 2H2 + O2 + 2H2O → 4H+ + 4OH– \[HS–] = 10–6M 1 HS– H+ + S2– we have.[H]+ H2O → H + OH . 71 × 10–3 Ω–1 cm–1 ∆E ∆H 1000 E° = T − ∆T P ∆F 1 and.69 At cathode [H+ ]. 7 kJ 2 2 10–6 10–3 2H2 + O2 → 2H2O. 4414 V Ra 0.1 × 0. 342 × 170. 10 −6 [S2–] = 1.∆H = 19. 86 × 10–4 = 0. 7 kJ = –113. 95) ∆E ∆S = nF = 4 × 96500×0. 1456 A 2Ag+ + 2e⁻ → 2Ag 6 V Sol 42: E = = = 60 V/m = 0.52 ∆G = ∆G1 + ∆G2 = –2FEº – RT ln ksp = ×0. [H2S] = 0. 57 × 10–4 × 2 × 3600 = 3.1 k= = 9. [H+] = 10–3. 32 Ω V 5 ∆G1 = –RT lnksp I= = Z R 34. 1 × 10–13 Adding. 0295 log (1. 25 cm We have. H + H2O2 → H2O. 6 cm/s = 4.∆H= –2 × 56.[HS – ] = k1 O2 + 2H2O + 4e → 4OH– [H2S] Overall cell reaction k1 = 10–8. 1 × 10–16) ∆H = –37.5 Ag2S 2Ag2 + S2– R = 34. 4 kJ [S2− ]. n = 1 I = 0. 0425 m 0. 5 × 1. 64 – 0. 05 kJ + – = k2 [HS – ] 4H2O → 4H+ + 4OH– [H+] = 10–3. 64 – log[S2–] 2 = 4. 57 × 10–4 cm/s 96500 –nFEº = –2FEº – RT ln ksp Distance in 2 hours = 4.32 Ag+ × e⁻ → Ag. k = E° = 0. [HS–] = 10–6.
5 n 0 Sol 45: ∧m (Co2[Fe(CN)6] ) C= V 0 0 = 2 ∧m (Co2+) + ∧m ([Fe(CN)6] +) n 8. 26 ohm–1 cm2 mole–1 0. 0591 log [H+] = –0. 41 × 10–6 Exercise 2 = 1.5 = 59. kH −4 2O 2O 1000 × 1. 7 0  Electrochemistr y 0 0 0 500 Sol 44: ∧m SrSO4 = ∧m Sr2+ + ∧m SO42– nNaCl = = 8. 65 × 10 Ω cm –6 –1 –1 Single Correct Choice Type = 1. 6 gm/L 5. 76 × 10–3 × 85 = 0.064 × 10–3 × 183. Co2[Fe(CN)6] 2Co2+ + [Fe(CN)6] 4– ksp = (2s)2. 8 = 139.3 × 10−6 × 1000 S = 0.482 × 10 C= = (3. 682 × 10–17 [A + ] a pH = pka + log = pka + log [HA ] b 0 Sol 46: For KCl. 55 × 10–5 Ω–1 cm–1 0.19 × 10−5 = 2 × 86 + 444 = 616 Ω–1 cm–1 mol–1 V ≈ 2 × 105 dm3. 190 × 10–5 mole/L 126.1 7 .65 × 10−6 × 1000 C= = 0 ∧m 616 ∴ Charge required = 10 F C = 2. ∧m = 138 Ω–1 cm2 mol–1 1 H+ + e⁻ + H 2 2 1000 E1 = 0 + 0. k Co [Fe(CN)6] = ksolution – kwater 2 = 2.2346 k SrSO kNaCl+H = = 3. 76 × 10–3 Ω–1 cm–1 0. 08 – 2. 08 × 10–5 0 2O 7600 ∧m SrSO4 = 1000 × 4 C kNaCl = kNaCl+H . 65 × 10–6 Ω–1 cm–1 Sol 1: (C) As E > EHg > E 0 1000 Ag+ /Ag 2 /Hg Cu2 + /Cu ∧m =k× C Sol 2: (C) Mn3O4 + 16OH– → 3MnO42– + 8H2O + 10e⁻ k × 1000 1. 55) × 10–5 139. 3 × 10–6 Ω–1 cm–1 C = S = 1.26 C = 1. 59 × 10–6 mol/L anode and cathode respectively because SRP of SO42– is very high (magnitude). 064 × 10–3 mole/L kNaCl × 1000 CNaCl = ∧m = 1. S = 4S3 Sol 4: (C) At X ksp = 7.0591 a b . 59 × 10–6 mol/L Sol 3: (A) Only water will be oxidised and reduced at S = C = 2.547 V= = (1 L = 1 dm3) C 4. 064 × 10–3 = 5. 1953 gm/L = = 4. 06 × 10–6 – 0.2346 E2 = –0. 547 58. 46 + 79.02 = –pka – log k= = 2. 0591 pH ∴ ∧m = k × C E1 a 138 × 0. 0591 pH kwater = = R 9200 E2 b a = –pka – log = –pka + log kwater = 2.0591 b 1000 At Y G* = Rk b = 2. 2346 cm–1 pH = pka + log a G* 0.
Chem i str y  17.4 Sol 9: (A. 0591 log pka = – [Cl− ][PH ]1/2 0.71 E1 + E2 1 = –2pka H + Ag + Cl– → AgCl = H+ 0. 8 × 10–4 M Sol 13: (D) E° = E°left – E°right [PO43–] = 6 × 10–5 M E° is intensive. D) In all case H2O will oxidise at anode to 585 give O2. 4 S2O2 /SO2 4 − Cl2 /Cl− Br2 /Br − 2 /I1 G* 0. C. Sol 17: (A) nNaCl = = 10 58.0075 1000 1000 k = 4 × 10–3 Multiple Correct Choice Type G* = Rk = 100 × 4 × 10–3 Sol 7: (B. 1 = 33.8 1 G* 0. D) Refer text CNaCl = V 10 Sol 11: (D. ksp = [Ag+] 3 [PO43–] Sol 14: (A) These are facts. + Sol 5: (A) ∧eq = C 9 × 10−6 Assertion Reasoning Type C= × 10−3 = 6 × 10–5 M 1.5 × 10−4 Sol 12: (A) Cell Reaction: Ag3PO4 3Ag+ + PO43– Zn(Hg) + HgO(s) → ZnO(s) + Hg() [Ag+] = 3C = 1.3 × 10 × 1000 C ∧m 0.015 Paragraph 1 [CH3COONa] = = 0. ksp = 4. E will decrease. B) H2O → H2 + O kNaCl+H = = = 5 × 10–5 2 2 2O R 8000 270 nH = = 15 kNaCl = kNaCl+H – kH = 10–5 2O 18 2O 2O VH = 15 × 22.118 2 k×t on increasing [H ] or decreasing [Cl–] . 25 × 105 L 8 × 10−5 Cell reaction . 32 × 10–18 Sol 6: (B) CH3COOH + NaOH → CH3COONa + H2O Comprehension Type 0.02 × 200 = = 84 S cm2 mol–1 k= = 0. C) Ag + Cl– → AgCl + e V= = 1. 6 L kNaCl × 1000 2 ∴CNaCl = VO = 168 L. Sol 16: (C) kwater = = = 4 × 10–5 R 10 4 Sol 8: (B.0591 2 2 E1 + E2 [H+ ] E = Eº – 0.4 species with higher E° can oxidise a species with lower E°. C) Eº > Eº > Eº > EºI G* = 0. ∧m = 200 S cm2 mol–1 −4 6. evolved at anode ∧m 2 −5 10 × 1000 VT = 504 L = = 8 × 10–5 125 10 Sol 10: (C. 0075 2 Sol 15: (B) R = ρG* 1000 ∧m = k × C for KCl.
625 ≈ 100. 71 – 0. r 0. PNO (C) → q.67 V [HNO3] = 100.06 ER = 0.059 0. 06 log [H+ ]2 [NO3− ] 0. 66 = 0. q 0. 7 2  Electrochemistr y Paragraph 2 1 – Cl → Cl2 + e– 2 Sol 18: (B) NO3– + 4H+ → NO + 2H2O+ 3e(a) PCl NO3– + 2H+ + e → NO2 + H2O (b) E = E – 0. 71 V Therefore.0295 = 0.06 2 E = E° – log Cl– will be oxidised as concentrated solution 1 [H+ ]2 [NO − ] 3 (D) → p.2905 + log = 0. (B) → p. . 34 – 0.0295 0. Ecell = 0.1 ⇒ E = 0. 02 log Sol 2: (B) The cell reaction is : [H+ ][NO3− ] 10−3 n + Fe2+ → Zn+ + Fe .059 = 0. 96 – log10−3 = 1. q = –322.059 [Zn2+ ] ⇒ E = E – log 2 [Fe2+ ] Sol 19: (C) E1 = E2 0. 65 + 0.67 × 96500 = kJ 1000 Sol 20 (A) → p. PNO = 10–3 SEP of Ag+ < SEP of H2O 0. E = log K n 0. 66 2 2 ∆G = –n E F Match the Columns 2 × 1. 03 log 10–1 At cathode : Mn+ + ne → M (electron gone in solution) = –0. 06(–3 – 3log[HNO3] ) Also.2905 V E2 = 0. E for NO3 → NO.1 7 . 08 log[HNO3] = 0. 18 + 0.32 ⇒ log K = = 0.059 0.01 0. 65 – 0. 34 – 0. [NO3–] =[H+] = 1M. s For (a). 3 Cu → Cu2+ + 2e EL = –0. electron is moving from cathode to anode via internal circuit. 10−3 E1 = 0. 05 5 Sol 3: (B) The net reaction is log[HNO3] = 8 1 2H+ + O + Fe → H2O + Fe2+ + E = 1.32/0. 06 log 2 [Cl− ]1/2 For (a). 65 – 0. 03 log[Cu2+] Sol 1: (C) In electrolytic cell.32 V 0. 34 + 0.31 kJ Cl– will not oxidise at low concentration. 1 log[HNO3] 2E 0. 31 At anode : Xn− → X + ne– (electron supplied to anode) E = ER + EL ≈ 0. 48 – 0. electrolysis occur at the cost of electricity : EL = –0. 18 log[HNO3] ⇒ K = (10)0. 48 – 0. 02(–3 – 5log[HNO3] ) 2 0. 02 ∴ Ag+ will be reduced to deposit Ag at cathode. 48 + 0. 06 + 0.06 PNO E=– log SEP of Na+ < SEP of H2O 3 [H ]4 [NO − ] + 3 \ Water will get reduced to H2 at cathode For (b).06 log[Cu2+ ] Previous Years’ Questions 2 = –0.
e. i. one mole amalgam of KNO3 comes in solution resulting in almost constant Two moles of Na formed during electrolysis would conductivity. Hg(E° = 0. Ered increases by 0. As the end point is reached. Fe(E° =–0. Sol 9: (C) On increasing concentration of NH3. 2 0.27 V Also.0 moles of NaCl. metals E° = 1. Sol 8: (B) E for 2Ag+ + C6H12O6 + H2O → 2Ag(s) + E = – 0.35 However. therefore.059 (10−3 )2 E =E – log = 1. they are non solution.33 0. B.04 V).02 g equivalent Sol 10: (D) NH3 has no effect on the E° of glucose/ gluconic acid electrode.3 ×104s Sol 11: (B) Moles of NaCl electrolysed = 4 × = 2.0592 E° = + 0.54 = 0.75V (ii) 4Mn3+ + 2H2O → 4Mn2+ + 4H+ + O2.303 log K = 58.e.19 V).40V) cannot reduce NO3– in aqueous Sol 15: (D) In other cases Ecell < 0 . reaction (i) is non ⇒ log K = = 25. ⇒ ln K = 2. 0.65 V 2 Pr ussian blue i.65 V.1) Sol 14: (C) For spontaneous redox reaction: Ecell > 0 For 2I– + Cl2 → 2Cl– + I2 Sol 7: (A.82 V > 0 V (E°= –1. spontaneous. the Sodium fusion extract from aniline produces NaCN concentration of H+ ion decreases. reaction (ii) is spontaneous Mn3+ oxidises H2O to O2 and itself reduced to Mn2+ in acidic medium. . KCl will be 2Cl– → + 2e– displaced according to following reaction AgNO3(aq) + KCl (aq) → AgCl(s) + KNO3(aq) Hg Sol 12: (D) At cathode : Na+ + e– → Na(Hg) For every mole of KCl displaced from solution.57 V 4 (10 −3 )4 (0. Fe3+ is stable in acid solution. Therefore.01 mol H2 = 0.0592 Fe3+ + [Fe(CN)64– → Fe4 [Fe(CN)6 ]3 =0– × 2log 10 –11 = 0.0 Sol 5: (D) As AgNO3 is added to solution. Sol 13: (D) Two Faraday of electric charge would be Sol 6: (D) The half reactions are required for electrolysis of 2.96 V will able to reduce NO3– in aqueous solution. The complex ion then reacts with Fe3+ give blue precipitate of 0. Chem i str y  17.73 Sol 4: (B) 0. hence ⇒ Mass of amalgam =2 × (23 + 200) = 446g conductivity increases.0 10 × 10 −3 1000 ⇒ Moles of Cl2 produced = 1.36 – 0. added AgNO3 produce two moles of Na(Hg) amalgam.0592 spontaneous. D) Metals with Eº value less than 0.02 × 96500 = 1930 C ⇒ Q = It = 1930 C Paragraph 2 1930 500 ⇒t= = 19. For the reaction: Paragraph 1 (i) 4Fe3+ + 2H2O → 4Fe2+ + 4H+ + O2. ⇒ Coulombs required = 0. Fe(s) → Fe2+ (aq) + 2e– × 2 ⇒ total coulombs = 2 × 96500 = 193000 C O2(g) + 4H+ → 2Fe2+ (aq) + 2H2O(l) Paragraph 3 0. Cl2 will spontaneously oxidize I–. E = log K 2 2Eº Sol 16: (A) As evidenced above.46 V C6H12O7+ 2H+ is 0. therefore. remain in solution increasing ionic concentration. which reacts with Fe2+ to form [Fe(CN)6 ]4 − .86 V) will all reduce NO3– but Au (E° = 1.0592 E= red Ered − log[H+ ]2 Prussian blue.
139 V Mn+4 + 2e− → Mn+2 1 Cathode: = 139 V Mn+4 + H2 → Mn+2 + 2H+ +2 + 2 Sol 19: X → Y.151 − 0. the salt bridge does not participate chemically in the cell reaction.01 1 Sol 17: (B) M(s) + M+ (aq. 1 M) → M+ (aq. 0.303 RT 0. 7 4  Electrochemistr y Paragraph 4 2 C Λm 2 Ka1 0.1 10 m2 2.001 Ka2 C2 Λ 0 0. ∆rG0 = 193 kJ mol1 0.059 0.0025 = 0.092 = 0.  Ecell  = Ecell = 0.059 2 ( ) log10 10X 48.151 − X So the number of moles of M+ oxidized using X → 2 Y will be ⇒ X= 2 193 = = 4moles 48.059 Mn H E= E − log10 M+ → M3+ + 2e− E0 = −0. Sol 20: HK + H + X − H+ X − Ka = HX + − HY H +Y H+ X − Ka = HX Λm for HX = Λm 1 Λm for HX = Λm 2 1 Λm = Λ 1 10 m2 Ka= C ∝2 2 Λ Ka= C × m1 1 1 0 Λ m1 2 Λ Ka= C × m2 2 2 0 Λ m2 .05 Ecell = 0 – log >0 F 1 pKa1 − pKa2 = 3 Hence. Sol 21: (D) Anode: H2 (s) → 2H+ + 2e− 0.25 kJ / mole 0.05M) + M(s) =1 × 2 = × = 0.70 V and ∆G < 0 for spontaneity of reaction.25 ) × 96500 =48250 J / mol 0. 1 7 .25 Sol 22: (A) In a galvanic cell.092 = 0.25V 2 Mn PH +4 2 ∆G0 for the this reaction is ∆G0 =−nFE0 =−2 × ( −0.0538 Sol 18: (C) Ecell = E – log 0.
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Notes. S fP r es o titut Ins CHEMISTRY FOR JEE MAIN & ADVANCED SECOND EDITION Exhaustive Theory (Now Revised) Formula Sheet 9000+ Problems based on latest JEE pattern 2500 + 1000 (New) Problems of previous 35 years of AIEEE (JEE Main) and IITJEE (JEE Adv) 5000+Illustrations and Solved Examples Detailed Solutions of all problems available Plancess Concepts Topic Covered Tips & Tricks. Misconceptions. Facts. Problem Solving Tactics Chemical Kinetics PlancEssential Questions recommended for revision . Key Take Aways. 201718 100 & op kers Class 12 T By E ran culty JE Fa r IIT enior emie .
CHEMICAL KINETICS 1. then Change in the concentration of reactants or(Products) ∆C C − C1 Average rate = = ± ± 2 = Time ∆t t2 − t1 The graph shows the progress of reaction with respect to time. physical state of substance. concentration. Change in the concentration of reactants or(Products) Rate of reaction = Time 2.1: Concentration vs Time Unit of concentration gram mole / Litre Unit of average rate of reaction = = = g mol L–1 sec–1 Unit of time second . If ∆C is the change in the concentration of reactants and products in Dt time. RATE OF REACTIONS The rate of reaction is expressed in mol L–1 s–1. temperature.1 Average Rate of Reaction Average rate of reaction is defined as change in the concentration of reactants (or products) during large interval of time. presence of catalyst. Rate of reaction is defined as change in concentration of reactants or products per unit time. etc. It is influenced by various factors such as nature of substance. 18. Concentration Product Reactant Time Concentration vs Time Figure 18. INTRODUCTION Chemical kinetics deals with the study of rate of chemical reactions. 2.
rate of reaction is equal to the rate of change of concentration of a reactant (or a product) divided by the corresponding stoichiometric coefficient. The shorter the life time. Half life period is defined as either the time taken to complete half of the reaction or during which the concentration of the reactant is reduced to one half of its initial value. AIR 22) 2. except when stoichiometric coefficient involved is unity. pressure is replaced by concentration. Thus. unit will be atm sec–1 n PV = nRT or P = RT or P = CRT V ∆[P] ∆[C] = ⋅ RT or Rate in [atm/sec] = Rate in [molarity/sec] ×RT ∆t ∆t Vaibhav Krishnan (JEE 2009. 2  Chemical Kinetics PLANCESS CONCEPTS For gases. ∆c dc Instantaneous rate = ± Lim Concentration = ∆t →0 ∆t dt B Note: For the reaction n1A + n2B → m1C + m2D 1 d[A] 1 d[B] 1 d[C] 1 d[D] Instantaneous rate of reaction = – – = = + = + n1 dT n2 dT m1 dT m2 dT Time Figure 18. the faster the reaction. Nikhil Khandelwal (JEE 2009.4 Reaction Life Time It is defined as the time taken to complete 98% of the reaction. It is denoted by t1/2.1 8 . AIR 94) 2.3 Instantaneous Rate of Reaction Instantaneous rate of reaction is defined as the average reaction rate during a very short interval of time or rate of reaction at a particular time.2 Expression of Rate of Reaction For the following reaction n1A + n2B → m1C + m2D 1 ∆[A] 1 ∆[B] 1 ∆[C] 1 ∆[D] rate of reaction = – – = = + = + n1 ∆t n2 ∆t m1 ∆t m2 ∆t For the reaction 2H2O2 → 2H2O + O2 ∆[O2 ] 1 ∆[H2O2 ] The rate of reaction = =– ∆t 2 ∆t 2.2: Instantaneous Plot PLANCESS CONCEPTS Rate of reaction and rate of change of concentration of a reactant (or product) are two different terms. On the other. .
the rate law equation = K1 [A] + K2 [A] [B]. Calculate the average rate of reaction using units of time both in minutes and seconds. (JEE MAIN) ∆[R ] [R] – [R]1 0. RATE CONSTANT Consider a simple reaction A → B dx dx At a particular instant. dx At a fixed temperature. 3. rate constant can be defined as rate of reaction at unit concentration of the reactants. the rate of reaction in the remaining mixture is not affected. if CA = 1. called velocity constant or rate constant or specific reaction rate.02M – 0. then rate = = k …(i) dt Thus. then ∝ CA or = kCA dt dt where k is a proportionality constant.3 Illustration 1: For the reaction R → P. i.e.8 × 10–3 = 9× 10–4 mol L–1 min–1 ∆t 2 ∆t 2 ∆[N2O5 ] (Rate is always positive and hence – is taken positive. Illustration 4: For the reaction A + B → C + D. Also.8 × 10–3 = 3. Calculate the rates of –3 –1 formation of NO2 and O2 during the same interval. (JEE MAIN) Sol: Decomposition of N2O5 has the following rate expression: ∆[N2O5 ] 1 ∆[NO2 ] ∆[O2 ] –= = 2 ∆t 2 ∆t ∆t ∆[NO2 ] ∆[N2O5 ] So.01M = 4 × 10–4 mol L–1 min–1 = = 6.02 M in 25 min.) ∆t Illustration 3: During the analysis of the products. during a certain time interval. Explain. Chem i str y  18. the concentration of a reactant changes from 0. it involves rate of formation of product from A as well as product from A and B. amount of substance is independent of the concentration and hence remains unaffected. (JEE ADVANCED) Sol: The rate of reaction depends on concentration. Let us consider a general reaction aA + bB Product dx Rate = ∝ [A]a [B]b =k [A]a [B]b when [A] = [B] = 1 mol/L. which remains constant even if a portion of the mixture is removed. then rate = k dt . Different magnitude reflects only the rate of reaction of the one which is faster among the two mechanisms. 25 × 60s 1 Illustration 2: Decomposition of N2O5 is expressed by the equation. =2 = 2 × 1.03 M to 0.030M –0.01M Sol: Average rate = – =– 2 =– =– ∆t t2 – t1 25minutes 25minutes 0.6 × 10–3 mol L–1 min–1 ∆t ∆t ∆[O2 ] 1 ∆[N2O5 ] 1 and = = × 1.8 × 10 mol L min–1. the rate of decomposition of N2O5 is 1. where K1 and K2 represent two different constants and the products are formed by two different mechanisms. Explain the relative magnitudes of the rates of two individual mechanisms? (JEE ADVANCED) Sol: The rate of formation of products for both the reaction mechanisms must be of the same order of magnitude.66 × 10–6 mol L–1 sec–1. if CA is the molar concentration or acitve mass of A. even when a portion of the mixture is removed. N2O5 → 2NO2 + O2 2 If.
2. AIR 21) 3. rate constant is independent of the concentration of the reactants and dependent only on temperature.1 8 . mol / litre mol PLANCESS CONCEPTS When order of reaction is not mentioned explicitly.1 Units of Rate Constant For reactions of different order. Proportionality constant. decreases the volume and simultaneously increases the concentration. Temperature coefficient of reaction rate. if the unit of rate constant is M1sec1.2 Rate of Reaction and Reaction Rate Constant Table 18. unit for rate constant is as follows: n−1 1 Unit of rate constant = × time–1 unit of concentration n−1 n−1 1 litre = × sec = –1 × sec–1 where. the more rapidly the reaction proceeds. Therefore the rate of reaction increases. Neeraj Toshniwal (JEE 2009. Independent of the initial concentration of the reactants and has a constant value at fixed temperature.1: Difference between rate of reaction and reaction rate constant S. products with time. then it can be determined using the unit of rate constant. For example.3 Factors Affecting Rate of Reaction (a) Concentration: According to the law of mass action the greater the concentration of the reactants. then order = 1(1)=2. Aman Gour (JEE 2012. (b) Pressure (Gaseous reaction): Increasing the pressure.No. . 3. It has been observed that rate either k doubles or triples for every 10°C rise in temperature. 3. AIR 230) 3. 4  Chemical Kinetics PLANCESS CONCEPTS For a particular reaction. Depends upon the initial concentration of reactants. Speed at which reactants converts into products. n = order of reaction. T +10 ≈ 2 or 3. kT where k T +10 and kT are rate constants at two temperature. (d) Nature of the reactants: The rate depends upon specific bonds of the reactants involved in the reaction and hence on the nature of reactants. (c) Temperature: Increase in temperature increases the reaction rate. differing by 10°C. Measured as the rate of decrease in concentration of Equal to the rate of reaction when the concentration of reactants or the rate of increase in concentration of each of the reactants is unity. Rate of reaction Reaction rate constant 1.
5 (e) Surface area of the reactants: In heterogeneous reactions. (f) Catalyst: It has an immense effect on the rate of reaction. (b) Rate of chemical reaction is directly proportional to the concentration of reactants. (c) The rate law represents the experimentally observed rate of reaction. then what will be the change in rate of reaction? (JEE MAIN) Sol: For. if the reactants are in more powdered form. Illustration 5: The rate law of a chemical reaction 2NO + O2 → 2NO2 is K[NO]2 [O2 ]. (d) Rate law cannot be deduced from the equation for a given reaction. = K2 [N2O5] and = 2 = K3 [N2O5] 2 dt dt dt Derive a relation between K1.then the rate for same number of NO and O2 moles. 2NO + O2 → 2NO2 Rate = K[NO]2 [O2] Let us take a moles of NO and b moles of O2 to start a reaction at any time in a vessel with a capacity of V L. which do not appear in the equation for the overall reaction. (g) Intensity of radiation: The rate of photochemical reactions generally increases with increase in intensity of radiation.4 Rate Law (a) It may not depend upon the concentration of each reactant or product of the reaction. 2 a b r1 = K …(i) V V V if volume of vessel is reduced to . Sol: For the given reaction d[N2O5 ] 1 d[NO2 ] d[O2 ] = =2 Putting given values dt 2 dt dt 1 or K1[N2O5] = K [N O ] = 2K3[N2O5] or 2K1 = K2 = 4K3 2 2 2 5 3. Positive catalyst increases the rate of reaction by decreasing the activation energy. 2 = 64 i. Catalyst mainly affects the activation energy of reaction and hence the rate constant and rate of reaction changes. . It can be found out by experiments only. (f) It may not depend upon the concentration of species. 4 2 2 a b a b r2 = K = 64K …(ii) V / 4 V / 4 V V r Dividing equation (ii) by (i). then velocity is greater [as more active centres are available]. while negative catalyst decreases the rate of reaction by increasing the activation energy. m n Suppose. K2 and K3.If the volume of reaction vessel is reduced to 1/4th of its original value. Chem i str y  18. r2 is 64 times of r1 r1 Ilustration 6: Dinitrogen pentoxide decomposes as follows: (JEE ADVANCED) 1 −d[N2O5 ] d[NO2 ] d[O2 ] N2O5 → 2NO2 + O2 If = K1[N2O5]. mA + nB → Product R ∝ A B .e. (e) The rate law may not bear a simple relationship for the stoichiometric equation. which depends upon the slowest step of the reaction.
Reactions having order equal to 1. No.1 8 . It is the total number of reacting molecules It is the sum of powers of molar concentrations of the (atoms or ions) leading to chemical change. •• Misconception: Order and molecularity are one and the same. Participating molecules Molecularity One molecule unimolecular. bimocelular. 6  Chemical Kinetics 4. Rohit Kumar (JEE 2012. then the order with respect to A = p and the order with respect to B = q and the total order of the reaction = p + q. AIR 79) Table 18. 2 Three molecule trimolecular. It is always a whole number. zero. positive or negative. reacting molecules in the rate equation of the reaction. AIR 11) 5. For the reaction: mA+nB → product The experimental data suggests that Rate =k[A]p[B]q. . ORDER OF REACTION The order of any reaction may be defined as the sum of the powers to which the concentration terms are raised in order to determine the rate of reaction. fractional or integer. Reactions having order equal to 3 are IIIrd order reactions PLANCESS CONCEPTS •• Order can be zero. the reaction can be unimolecular. Reactions having order equal to 0 are zeroorder reactions. 3 PLANCESS CONCEPTS •• Molecularity of a reaction is moslty between 1 to 3. It may be a whole number. Depending on the number of participating molecules. atom or radicals that participate in the reaction. •• Stoichiometric coefficients m and n of the reactants are always not equal to orders p and q. trimolecular. 2. Reactions having order equal to 2 are IInd order reactions. MOLECULARITY OF A REACTION It is defined as the number of molecules. fractional. Molecularity Order of reaction 1. 1 Two molecule bimolecular. etc.2: Differences between order and molecularity S. B Rajiv Reddy (JEE 2012. But order may or may not be equal to molecularity of the reaction. but never zero. are Ist order reactions. It is rare that molecularity exceeds 3.
(3).2 × 10–4 =k [0.2 × 10–4 2.010]y ….020]y ….020]x Dividing Equation (iii) by Equation (ii). It is experimentally determined.4 × 10−4 [0. Order H2 + Cl2 → 2HCl r = k[H2]0[Cl2]0 0 H2 + Br2 → 2HBr r = k[H2][Br2]1/2 3/2 H2 + I2 → 2HI r = k[H2][I2] 2 Illustration 8: For the reaction 2NO + Cl2 → 2NOCl At 300 K.010]x Order of reaction = x + y = 2 + 1 = 3 Rate law for the reaction is Rate = k[NO]2 [Cl2] .4 × 10–4 = k [0.010]x [0. following data are obtained: (JEE ADVANCED) Initial Concentration Expt. 9. Initial Rate [NO] [Cl2] 1.(ii) Dividing Equation (ii) by Equation (i).010]x [0.010 1.010 0.020]y = or 2 = (2)y y = 1 −4 y 1. Reaction Exp. (2).6 × 10–4 What is the rate law for the reaction and the order of the reaction? Also calculate the specific rate constant.4 × 10−4 [0.010]x [0.(i) From expt. (2). Chem i str y  18. 1. Sol: Let the rate law for the reaction be Rate = k [NO]x [Cl2]y From expt. It is meaningless for overall complex reaction.6 × 10−4 [0. (1).010] From expt.020 2. It is meaningful only for simple reactions or It is meant for the reaction and not for its individual steps.4 × 10–4 =k [0. Illustration 7: Write the order of the following reactions? (JEE MAIN) Reaction Exp. 0.020]x [0.020]y From expt.2 × 10 [0.6 × 10–4 =k [0. 2. No.020 0. 0.010 0. rate equ. H2 + Cl2 → 2HCl r = k[H2]0[Cl2]0 H2 + Br2 → 2HBr r = k[H2][Br2]1/2 H2 + I2 → 2HI r = k[H2][I2] Sol: Order is the number to which the concentration of the reactants/products are raised corresponding mostly to the coefficients. individual steps of a complex reaction. It is a theoretical concept.7 3. x = 2 2. 0.4 × 10–4 3. rate equ. 2. 4.020]y 9. 2.020 9. = or 4 = 2x.
. we get the rate constant k = k = 0 .(iii) t Zeroorder reactions occur only under special conditions and hence they are uncommon... 8  Chemical Kinetics Considering Equation (i) again. We get a straight line with slope = –k and intercept equal to [R]0. where [R]0 is initial concentration of the reactant. R= t1/2 = or t1/2 ∝ R0 2 2K It is directly proportional to the initial concentration of the reactant. Some enzyme catalyzed reactions and reactions which occur on metal surfaces are a few examples of zeroorder reactions.. y = mx + c. Rate = k[NH3]0 = k Here. when [R] is plotted against t.1 ZeroOrder Reactions Rate of the reaction proportional to zero power of the concentration of reactants is known as zeroorder reaction. d[R] = – k dt dt Integrating on both sides [R] = – k t + I . Figure 18.1 8 .010] 1. the concentration of the reactant R = [R]0.(i) O Time(t) where I is the constant of integration. The thermal decomposition of HI on gold surface is another example of zeroorder reaction..2 × 102 mol–2 L2 s–1 [0. The metal surface reacting with gas molecules under high pressure gets saturated. platinum acts as a catalyst. . a further change in reaction conditions does not alter the amount of ammonia on the surface of the catalyst making rate of the reaction independent of its concentration. [R ] – [R] Simplifying equation (ii). REACTION OF VARIOUS ORDERS 6.2 × 10−4 k= = 1.(ii) Equation of a straight line. R0 R0 At t = t1/2 . Another example of zeroorder reaction is decomposition of gaseous ammonia on a hot platinum surface at high pressure. Consider the reaction d[R] Concentration of R K =Slope R → P Rate = =k[R]0 dt As any quantity raised to power zero is unity d[R] Rate = = k × 1 .010]3 6.2 × 10–4 = k[0. 1. 1130K 2NH3(g) Pt catalyst → N2(g) + 3H2(g) . (B) Halflife period (t1/2): It is the time taken to complete half of the reaction. Substituting in equation (i) [R]0 =– k × 0 + I [Rl0]=I Substituting the value of I in the equation (i) [R] = – kt + [R]0 .3: Zero order plot At t = 0. [R]0 [R] (A) Unit of rate constant: k = k mol L−1 sec−1 t Unit of rate of reaction and unit of rate constant are the same.. So..010]2[0.
we get ln [R] = – kt +I .(iv) I is the integration constant .. Chem i str y  18. In[R] log ([R]0/[R]) K = Slope In[R] Slope = k/2. Therefore...303 [R] k= log 0 . the slope = k/2.303 Hydrogenation of ethene is an example of firstorder reaction. For example.(v) [R] 1 [R] Rearranging this equation ln = – kt or k = ln 0 .303 O t O Time Fig. Subtracting (viii) from (vii) [R] ln[R]1 – ln[R]2 = – kt1 – (–kt2) ln 1 = k(t2 – t1) [R]2 1 [R]1 k= ln …(ix) (t2 − t1 ) [R]2 [R] Equation (v) can also be written as ln 1 = –kt [R]2 Taking antilog on both sides [R] = [R]0 e–kt When ln [R] is plotted against t .. equation (iv) can be written as ln [R]0 = – k × 0 + I = I Substituting I in equation (iv) ln [R] = – kt + ln[R]0 .9 6.. R= [R]0.(vi) [R]0 t [R] At time t1. R → P d[R] d[R] Rate = – = k [R] or – = –kdt dt [R] Integrating the above equation.. When t = 0. ln[R]2 = – kt2 + ln[R]0 .(x) t [R] [R]0 kt log = [R] 2.2 FirstOrder Reactions Rate of the reaction is proportional to the first power of the concentration of the reactant.. C2H4(g) + H2(g) → C2 H6(g) Rate = k [C2H4] All natural and artificial radioactive decay of unstable nuclei takes place by firstorder kinetics.: Plot of log [R]0/[R] vs time for a firstorder reaction for a firstorder reaction Figure 18.303 If we plot a graph between log [R]0/[R] and t.: A plot between In[R] and t Fig. where [R]0 is the initial concentration of the reactant.4: First order plot . from equation (iv) ln[R]1 = – kt1 + ln[R]0 …(vii) At time t2. hence its value can be determined easily..we obtain a straight line with slope = –k and intercept equal to ln [R]0...(viii) where [R]1 and [R]2 are the concentrations of the reactants at time t1 and t2 respectively. The firstorder rate equation (vi) can also be written in the form 2.
.303 R0 2. 1 0  Chemical Kinetics Examples: 226 (a) 88 Ra →24 He + 86 222 Rn . K= log = × log 2 = 2 t1/2 R0 / 2 t1/2 t1/2 0.g RCl + H2O → ROH + HCl Expected rate law: Rate = k [RCl][H2O]. pB and pC are the partial pressures of A. Pt = (pi – x) + x + x = pi + x x = (pt – pi).693 t1/2 = K 6. expected order = 1+1 = 2 Actual rate law: Rate = k’ [RCl] Actual order = 1 Water is taken in excess. therefore. B and C. therefore. RCOOR’ + H2O → RCOOH + R’OH follows first order kinetics: Rate = k [RCOOR’] It is also a pseudo firstorder reaction.4 Some Examples of FirstOrder Reactions and Their Rate Constants (a) For Gas Phase Reaction Let us consider a typical firstorder gas phase reaction A(g) → B(g) + C(g) Let pi be the initial pressure of A and pt the total pressure at time ‘t’.303 [R] (i) Unit of rate constant: K = log 0 = sec–1 t [R] (ii) Halflife period (t1/2): R0 2.693 At t = t1/2. e. respectively Decreasing x atm pressure of A at time t to form one mole of B and C each.303 0. where pA= pi – x = pi – (pt – p i ) = 2pi – pt . pseudo first order. Rate = k[Ra] (b) Decomposition of N2O5 and N2O are few more examples of firstorder reactions. its concentration may be taken constant. t = 0 pi atm 0 atm 0 atm At time t (pi – x) atm x atm x atm Where pi is the initial pressure at time t = 0.. The increase in pressure of B and C will also be x atm each. Integrated rate equation is as follows: Total pressure pt = pA + pB + pC (pressure units) pA. R = .3 PseudoOrder Reactions Reactions whose actual order is different from that expected using rate law expression are called pseudoorder reactions. 2. A(g) → B(g) + C(g) At time. 6.1 8 . the acid catalyzed hydrolysis of ester. Similarly. The reaction is. viz..
qt is polarimetric reading after time t and θ∞ is polarimetric reading after infinite time.303 V − V0 Hence.Vt and V∞ are volumes of standard alkali needed to neutralize a definite amount of x. will be proportional to V∞ – V0 2. If V0 . 2. K = log ∞ t V∞ − Vt (e) Oxide Layer Formation 1 τmax K= ln where tmax is the thickness of oxide layer after ∞ times and τ is the thickness of oxide layer at t τmax − τ time ‘t’.11 2. Chem i str y  18. Then.. (1)Volume of oxygen gas at different intervals of times is measured and or (2) definite amount of reaction mixture is titrated with standard KMnO4 at different intervals of time.303 pi = log t 2pi – pt (b) PseudoUnimolecular Reaction: Inversion of cane sugar H + C12 H22O11 + H2O → C6 H12O6 + C6 H12O6 Sucrose Glucose Fructose The progress of the reaction can be studied using a polarimeter.303 pi k= log . Let q0 is polarimetric reading at t = 0. R0 ∝ V0 .(xi) t pA 2.R ∝ Vt 2. If V0 represent the initial volume of KMnO4 and Vt final volume of KMnO4 at any time t Then. will be proportional to Vt – V0 and a. 1 a+x (f) Bacterial Growth: K = ln t a .303 V∞ K= log t V∞ − Vt (d) Hydrolysis of Ethyl Acetate (Ester) H + CH3COOC2H5 + H2O → CH3COOH + C2H5OH Kinetics of this reaction is studied by titrating a definite volume of the reaction mixture with standard alkali solution. K =– log 0 t Vt (ii) Decomposition of Ammonium Nitrite NH4NO2 → N2 + 2H2O If Vt is the volume of N2 evolved at any time t and V∞ is the volume of N2 evolved when the decomposition is complete.303 V Therefore. 2..303 θ − θ∞ k= log 0 t θt − θ∞ (c) (i) Decomposition of H2O2 Pt 1 H2O2 → H2O + O 2 2 The progress of the reaction can be studied by two methods. Cane sugar and glucose are dextrorotatory while fructose is laevorotatory.
5 SecondOrder Reaction A reaction is said to be of second order if its reaction rate involves two different concentrations. (c) Secondorder reaction confirms to the first order when one of the reactants is present in large excess. (b) When the initial concentrations of the two reactants are different. t = . where ‘k’ can be evaluated. respectively.303 b Hence.303 b(a − x) Consider. = k(a – x)2. 2O3 → 3O2 (d) Thermal decomposition of chlorine monoxide. Characteristics of the secondorder reactions (a) The value of k (velocity constant) depends on the unit of concentration. Thus. 2. i. 1 When ‘t’ is plotted against the resultant slope is a straight line.x) are the concentrations of A and B.1 8 . then (a – x) ≈ a and (a – b) ≈ a t(a − b) 10 a(b − x) 2. If a >>> b. Time − k(a − x) ka 1 The slope of the line is . t. 2NO2 → 2NO + O2 (c) Conversion of ozone into oxygen at 100°C.5 Second order plot k a × 0.303 b(a − x) = k(a – x)(b – x) . i.5a 1 (b) Halflife period (t1/2) = ⋅ = Figure 18. a b dx 2. k 1/(ax) 1 0. after time interval. (a − x) 1 1 Rearranging equation for k. Examples of secondorder reactions (a) Hydrolysis of ester by an alkali (saponification). the reaction follows firstorder kinetics with respect to the reactant taken relatively in small amount. The unit of k is expressed as (mol/litre)–1 time–1 or litre mol–1 time–1. log10 dt t(a − b) a(b − x) (a . 2Cl2O → 2Cl2 + O2 .e. dx A + B → Products or 2A → Products. A + B → Products Initial conc.x)and (b . 1 2  Chemical Kinetics 6. dt 1 x k= ⋅ t a(a − x) Where a is the initial concentration of the reactant or reactants and x is the concentration of the reactant changed in time t.e.5a ka Thus.. k = log . halflife period is inversely proportional to initial concentration.303 ba 2. CH3COOC2H5 + NaOH → CH3COONa + C2H5OH (b) The decomposition of NO2 into NO and O2. k= log10 or ka = k’ = log10 ta a(b − x) t (b − x) here since ‘a’ being very large is a constant after the change. The kinetics of secondorder reactions are given as follows: (a) When concentrations of both reactants are same or two molecules of the same reactant are involved in the change.
20 150 2.00 5. A + B + C → Products.00 5.5a) 2 k 2a × 0.20 2.5a(2a − 0.6 ThirdOrder Reaction Reaction is said to be of third order if its reaction rate involves three different concentrations.0 L 1 [A] 0. the rate expression is given as: dx 3A → Products. Other graphs are curved for a firstorder reaction. •• The unit of k is expressed in (mol/litre)–2 time–1 or L2 mol–2 sec–1. the plot of the logarithm of [A] versus time is a straight line with k = .15 In[A] 100 [A] k = . Time sec Time sec. = k(a – x)3 dt 1 x(2a − x) Therefore k= ⋅ t 2a2 (a − x)2 Characteristics of thirdorder reactions 1 0. as shown in the following figure.13 6.slope 3.0 1 mol A L 4. the plot of [A] versus time is a straight line with k = ve slope. [A] vs time In[A] vs time 1/[A] vs time 0. halflife is inversely proportional to the square of initial concentration. 2NO + Cl2 → 2NOCl Examples For a zeroorder reaction.7: Plot of the logarithm of [A] versus time .0 50 0. Other graphs are curved for a zeroorder reaction. Examples of thirdorder reactions •• Reaction between nitric oxide and oxygen.5a × 0. Chem i str y  18. as shown in the following figure.slope of the line.0 20 0.slope 60 0.05 0.15 In[A] [A] 40 mol 3.5a) 1 0. •• The change in the unit of concentration changes the numerical value of k. Figure 18.5a 3 •• Halflife period = ⋅ = = k 2 2a (0.0 0 20 40 60 0 20 40 60 20 40 60 Time (sec) Time (sec) Time (sec) Figure 18. When the concentration of all the three reactants is same or three molecules of the same reactant are involved.05 4. 2NO + O2 → 2NO2 •• Reaction between nitric oxide and chlorine.0 0.0 0 5 10 15 20 0 5 10 15 20 5 10 15 20 Time sec. [A] vs time In [A] vs time 1/[A] vs time 0.5a × 1.6: Plot of [A] versus time For a firstorder reaction.0 k = .5a 2a2k 2 Thus.
8 Consecutive Reactions k k A → B 1 2→ C k1 [A]0 −k1t – e 2 −k1t −k t [A]t = [A0] e .0 0 100 200 300 0 100 200 300 100 200 300 Time sec.0 10 0. HNO3 OH A k2 Time (Side) NO2 Figure 18. the plot of 1/[A] versus time is a straight line with k =ve slope of the line.00 5. 1 k2 1 K tmax = ln 1 K1 − K 2 K 2 . [A] vs time In[A] vs time 1/[A] vs time 0.9: Parallel reactions 6. as shown in the following figure. [B]t = e [k 2 − k1 ] k2 k k2 −k1 [C]t = [A0] – ([A]t + [B]t) .8: Plot of 1/[A] versus time 6.7 Parallel Reactions k1 B [A]0 [B] k1 A ln = (k1 + k2)t = [A]t [A] k 2 k2 C k1 [A]0 k 2 [A]0 [A] = [A0] e–kt [B] = (1 – e–kt) [C] = (1 – e–kt) k1 + k 2 k1 + k 2 Variation of concentration A.0 0. B and C with time may be graphically represented as. 1 4  Chemical Kinetics For a secondorder reaction.20 50 2. Examples: OH NO2 B k1 OH (Main) C Conc.0 1 L [A] 0.1 8 . Figure 18.slope [A] mol 3.15 40 In[A] k = . Other graphs are curved for a secondorder reaction.05 4. [B]max = [A0] . Time sec Time sec.
Chem i str y  18.303 For.693 0.303 [A] Sol: For a firstorder reaction k = log 0 k [A]t We have.4 5 5 2.303 × 0.6 2.1 × 10–2 min–1 5min 0.303 x xeq K Equilibrium conc.303 0.6 2.925 × 10−4 s–1 t1/2 60 minutes 60 × 60 seconds Illustration 10: Consider a firstorder reactions.1761 So.4 mol L–1 Then how long will it take for the initial concentration to become 0. [A]t = 0.1 × 10−2 Illustration 11: The following were obtained during the first order thermal decomposition of N2O5 (g) at constant volume: 2N2O5(g) → 2N2O4(g) + O2(g) .15 Conc.6 mol L–1 to become 0. k1 + k2 = log10 e = f t x e − x a − x eq K b Illustration 9: If the time required to decompose SO2Cl2 to half of its initial amount is 60 minutes and the decomposition is a firstorder reaction.3 8.693 Sol: For a firstorder reaction. (JEE MAIN) 0.3 mol L–1? (JEE MAIN) 2.693 0. [C] [B] [A] Time Figure 18. (a – xe) xe . [A]0 = 0. t = log 0 = log = log 2 = 8. at time (t) a – x x 2.5min.303 [A] 2.1 × 10 −2 0.3 mol L–1 .303 0. k = × log =log 1. if it takes 5 minutes for the initial concentration of 0.9 Reversible Reactions 1 k A ← →B k 2 Initial state (t = 0) a 0 Conc.303 2. k = t1/2 0. then calculate the rate constant of the reaction. k [A]t 8.6 mol L–1 [A]t = 0.10: Consecutive reactions Examples: (i) Decomposition of ethylene oxide: k (CH2)2O → CH3CHO 1 k CH3CHO 2→ CO + CH4 6.4 mol L–1 t = 5 min 2.5 min–1 = min–1 = 8.693 = = = 1.
x = 60. Therefore pressure of N2O4(g) increases by 2x atm and that of O2(g) increases by x atm. (a) In these types of reactions. 0 0.5 – 2pt At t = 100 s.5atm 2. What is the time required for 60% completion? (JEE ADVANCED) Sol: The equation for second order with both the reactants having same concentration is 1 x k= ⋅ If a = 100 . 100 0.512 atm PN2O5 = 1.303 Using equation (11) k = log i = log = × 0. k = × When a = 100.303 P 2. In another words.98 × 10–4 s–1 t PA 100s 0.5)= 1.5 × 2x) + 2x + x = 0.512 = 0. (JEE ADVANCED) Sol: Let the pressure of N2O5(g) decrease by 2x atm when two moles of N2O5 decompose to give two moles of N2O4 (g) and one mole of O2(g). x = 20.476 atm 2. consider 20% of the reaction is completed in 500 sec. intermediates are formed during the reaction which is different from the reactants and the products formed. Time (sec) Total Pressure (atm) 1.2 Complex Reactions These are multistep reactions in which order and molecularity may or may not be same.512 Calculate the rate constant.5 – 2 x 0. t = ? 500 100 × (100 – 20) 1 60 t= ⋅ k 100 × 40 Substituting the value of k. 1 6  Chemical Kinetics S.5 = 0. (b) Each step involved in this reaction is an elementary reaction. THE REACTION MECHANISM 7.5 atm 0 atm 0 atm At time t (0.5 × 2x) atm 2x atm x atm Pt = PN2O5 + PN2O4 + PO2 = (0.1 8 .1 Elementary Reactions Elementary reaction are single step reactions in which order and molecularity are always the same.5 + x x = pt – 0.476 atm 100s Illustration 12: In a secondorder reaction.0216 = 4.5 – 2(pt – 0. 500 × 100 × 80 60 t= × or t = 3000 sec 20 100 × 40 7. pt = 0.303 0.No. rate law and the law of mass action have the same expression. 2N2O5(g) → 2N2O4(g) + O2(g) At t = 0 0. t = 500 sec. t a(a − x) 1 20 So.5 2. in which both the reactants have same concentration. . 7.
order is not equal to molecularity. The concentration of I can be related with the concentrations of A and B with the help of first equilibrium.. 7. For e. DETERMINATION OF RATE LAW FOR A COMPLEX REACTION 8. (e) The order of reaction and the overall order of reaction may not be the same.. If it is not overall order. the overall rate of reaction is 1 + 2 = 3 . r = k2 k1 [A][B]. it has no significance. A series of steps (known as elementary processes) leading to the formation of products or by which the overall chemical reaction occurs is called the reaction mechanism.[B] = k[A][B]2. The reaction between H2 and I2 to form hydrogen iodide was originally postulated as a simple onestep reaction. Chem i str y  18. It depends on the concentrations involved in the rate law expression of RDS. However..3 Reaction Mechanism The steps involved in a reaction and determining which step is the slowest or rate determining is called mechanism. H2 + I2 = 2HI Rate = k[H2][I2] But.g. let the mechanism of reaction A + 2B → C + D is 1 k Step I: A + B ← → I k 2 k Step II: I + B 2→ C+D Overall rate of reaction. the formation of HI has been explained on the basis of the following mechanism: I2 → 2I (fast) …. r = rate of step II = k2[I][B] . equilibrium constant. A reaction can have more than one RDS. (d) The overall molecularity of reaction and the molecularity of the RDS are the same .(i) H2 + I → H2I (fast) .17 (c) The overall rate of reaction will be equal to the rate of slowest step. k1 [I] k1 For step I.... For example.(iii) Overall reaction: H2 + I2 → 2HI 8.1 Equilibrium Approach The concentration of intermediate can be determined from equilibrium constant of the reaction involved. it may be determined by equilibrium approach or by steady state approximation.. where.(i) But this cannot be considerd as correct because the overall rate of reaction should be in terms of concentrations of A and B (reactants).(ii) H2I + I → 2HI (slow) . For a complex reaction. k = 1 k −1 k −1 Hence. Keq = = \ [I] = [A][B] k −1 [A][B] k −1 k Putting this value in equation (i). Hence the slowest step is called the rate determining step (RDS) of reaction.
step I is faster than step II. we assume that the intermediates formed are so reactive that after some time from initiation of reaction (called induction period). •• When conditions of equilibrium approach are applied on the result obtained from steady state approximation. the concentration of intermediate at any time remains nearly equal to its equilibrium concentration. AIR 839) Illustration 13: The reaction 2NO + Br2 → 2NOBr obeys the following mechanism: fast Step I: NO + Br2 ← → NOBr 2 Slow Step II: NOBr2 → 2NOBr Suggest the rate expression. better results are obtained by steady state approximation.2 Steady State Approach In this method. r1 = r–1 >> r2 or. As step I is at equilibrium. from steady state approximation on the intermediate. For the above reaction. let the mechanism of reaction A +2B → C + D is 1 k Step I: A + B ← → I k 2 k Step II: I + B 2→ C+D d[C] The rate of reaction may be given as r = + = k2 [I] [B] …(ii) dt d[I] Now.1 8 . the same rate law expression is obtained. (JEE MAIN) Sol: The slowest step is the Rate determining step. better results are obtained by eqilibrium approach. Aishwarya Karnawat (JEE 2012. 1 8  Chemical Kinetics 8. the net rate of their formation becomes zero. k–1+k2[B] ≈ k–1 Now. They react with the same rate of their formation. [I] = k −1 + k 2 [B] k1 [A][B] k1k 2 [A][B]2 Substituting this value in equation (ii). . k–1>>k2[B] therefore.the rate expression obtained from steady state is k 2k1 [A][B]2 r= ≈ [A][B]2 k −1 + k 2 [B] Which is exactly same expression obtained from equilibrium approach. when the intermediate is more stable. More stable intermediate reacts very less and hence. For example.k–1[I]>>k2[I][B] or. I – =0 dt k1 [A][B] or k1 [A][B] – k–1[I] – k2[I][B] = 0 or. r = k2 · ·[B] = k −1 + k 2 [B] k −1 + k 2 [B] PLANCESS CONCEPTS •• When the intermediate is less stable.
The value of collision frequency is very high (of the order of 1025 to 1028) in case of binary collisions. r = rate of step II = k[N2O4][CO]2 . 9.(i) [N2O 4 ] Now. NOBr2 is an intermediate and thus its concentration is determined step I. molecules just collide and disperse in different directions with different velocities.11: Threshold Plot . but it is not the given rate law Hence. from step I: keq = or. the mechanism is not consistent with the rate law. r = k[NOBr2][NO] …(i) However. Collisions that do not form a product are ineffective elastic collisions. keq Illustration 14: The following mechanisms are proposed for the reaction CO + NO2 → CO2 + NO at low temperature: (a) 2NO2 → N2O4 (fast) N2O4 + 2CO → 2CO2 + 3NO (slow) (b) 2NO2 → NO3 + NO (slow) NO3 + CO → NO2 + CO2 (fast) d[CO2 ] Which of the above mechanism are consistent with the observed rate law: + = k[NO2]2 (JEE ADVANCED) dt Sol: For mechanism (a). For mechanism (b). r = k’[NO]2 [Br2] where k’ = k. i. The effective collisions are less when compared to the total number of collisions.. The number of collisions taking place per unit time per unit volume of the reaction mixture is known as collision frequency (Z).keq [NO2]2 [CO]2. [NOBr2 ] For step I. I = k[NO2]2. by equations (i) and (ii). r = k. 9. COLLISION THEORY OF REACTION RATE/ARRHENIUS THEORY Postulates: •• Collision of reactant molecules leads to chemical reaction. Chem i str y  18.1 Energy Barrier The minimum energy required by colliding molecules for the chemical reaction to take place is known as threshold energy. the following two barriers are to be cleared. which is the given rate law. Fraction of molecules Fraction of molecules capable of bringing effective collisions Energy E Figure 18. •• Not every collision brings a chemical change. For effective collision. r = k. r = rate of step. [N2O4] = keq[NO2]2 2 [NO2 ] Hence from (i). equilibrium constant keq = \ [NOBr2] = keq[NO] [Br2] …(ii) [NO][Br2 ] Thus..19 Step II is the step that determines the rate of the reaction and hence. keq[NO]2[Br2] or.e. Only effective collisions bring about a chemical change to form products..
12: Energy profile diagram for exothermic and endothermic reaction (a) Every reaction. (ii) When Ea. Its life span is very less. whether exothermic or endothermic. Activation energy = threshold energy – average kinetic energy of reacting molecules. Activated Activated Complex Complex Ea Ea E C + D Products Energy Energy Reactants Reactants A+B E A+B Products C+D Progress of the reaction Progress of the reaction (Exothermic) (Endothermic) Figure 18. when the activation energy for the forward reaction is less than that for the backward reaction. Collision of high energy molecules that overcomes the forces of repulsion and forms an unstable molecule cluster is called an activated complex. ∆H = + ve Thus.f > Ea.b . ∆E = + ve and. Thus.e.f < Ea. products. i. 2 0  Chemical Kinetics The minimum amount of energy required by reactant molecules to participate in a reaction is called activation energy.1 8 . (b) Lower the activation energy.2 Orientation Factor •• To form products reactants should have a proper orientation in addition to sufficient energy. The activation energy (Ea) depends upon the nature of chemical bonds undergoing rupture and is independent of enthalpies of reactants and products. ∆E = –v and. •• Rate of reaction is directly proportional to the number of effective collisions. ∆H = –ve Thus. higher will be the fraction of effective collisions leading to faster reaction and vice versa. The following graphs show the energy changes during exothermic and endothermic reactions versus the progress of the reaction. the activated complex breaks to either form reactants again or form new substances. needs to overcome an energy barrier for reactants to get converted to products. Threshold energy = initial potential energy of reactant molecules + activation energy. (c) Activation energy Ea = E(activated complex) – E(ground state) ∆H = activation energy of forward reaction – activation energy of backward reaction. (i) When Ea.b . energy is released. dx Rate = – = collision frequency × fraction of effective collisions dt = Z × f . energy is absorbed. when the activation energy for the forward reaction is more than that for the backward reaction. 9.
the factor e–Ea/RT corresponds to the fraction of molecules with kinetic energy greater than Ea. R Ea At temperature T1. for most reactions. k=Arrhenius factor. Ea=activation energy.3 Temperature Dependance of Rate Constant The temperature dependence of the rate of a chemical reaction can be accuratly explained by Arrhenius Equation k = AeEa/RT .(i) where.... we get ln k = ln A – . it has been found from Arrhenius equation (i) that increase in temperature or decrease in activation energy results in an increase in the rate of the reaction and an exponential increase in the rate constant. T=temperature According to the Arrhenius equation. T In the Arrhenius equation (i).(ii) RT The plot of ln k versus 1/T gives a straight line according to the equation (ii) as shown in the below figure.14: Plot of ln k versus 1/T Thus.21 A A A A A A B B B B B B Reactants Products Figure 18. Chem i str y  18. equation (ii) becomes ln k1 = – + ln A …. ln = – . Subtracting equation (iii) from (iv). log = – RT1 RT2 k1 R T1 T2 k1 2. R=gas constant.(iii) RT1 Ea At temperature T2. we obtain Ea Ea k2 Ea 1 1 k2 Ea 1 1 ln k2 – ln k1 = – .303R T1 T2 . Ea In the plot. slope = – and intercept = ln A. Ea Taking natural logarithm of both sides of equation (i). Value of Ea is determined 1 from the graph for and ln k is determined experimentally. Intercept = ln In k Slope = Ea/R A A log log R R 0 1/T 1 T A plot between In k vs 1/T T Figure 18. : The parameters A and Ea for a given reaction are collectively called Arrhenius parameters. Value of A inturn is calculated once Ea is known.. the rate constant increases with increase in temperature. equation (ii) becomes ln k2 = – + ln A …..13: Collision theory 9. So we can calculate Ea and A using these values.(iv) RT2 (since A is constant for a given reaction) k1 and k2 are the values of rate constants at temperatures T1 and T2 respectively.
9. When the temperature is raised. the area showing the fraction of molecules having energy equal to or greater than activation energy gets doubled leading to doubling the rate of a reaction. 2 2  Chemical Kinetics Maxwell’s–Boltzmann Distribution Curve: The peak of the curve corresponds to the most probable kinetic energy. spreads to the right such that there is a greater proportion of molecules with much higher energies. i.15: Distribution curve showing temperature dependence of rate of a reaction Increase in the temperature of the substance increases the fraction of molecules. the faster will be the rate of a reaction. MnO2 catalyses the following reaction so as to increase its rate considerably 2KClO3 MnO 2 → 2KCl + 3O 2 Reaction path without catalyst Energy of activation Energy of Potential Energy without activation Reaction catalyst with Reactants path with catalyst catalyst Products Reaction coordinate Figure 18. −Ea /RT According to Arrhenius equation. It is clear from the diagram that in the curve at (T +10). .e.1 8 . According to this theory a catalyst reacts with the reactant to form temporary bonds resulting in an intermediate complex.16: Effect of catalyst on activation energy Catalytic Mechanism: The mechanism of the catalyst can be explained by intermediate complex theory. k = Ae . the maximum of the molecules moves to the higher energy value (figure) and the curve broadens out. We can mark the position of Ea on Maxwell Boltzmann distribution curve. the lower the value of activation energy. The area under the curve must be constant since total probability should always be unity at any given time.e. It is believed that the catalyst provides an alternate pathway or reaction mechanism by reducing the activation energy between reactants and products and hence lowering the potential energy barrier. i. This has a transitory existence and decomposes to yield products and the catalyst. kinetic energy of maximum fraction of molecules. For example.4 Effect of Catalyst A catalyst is a substance which alters the rate of a reaction without undergoing any permanent chemical change. which collide with molecules with energies greater than Ea. t Fraction of molecules (t + 10) Energy of activation This area shows fractional This area shows of additional molecules fraction of which react at (t + 10) molecules reacting at t Kinetic energy Figure 18. Number of molecules decreases with energies higher or lower than this value.
•• Catalyst does not change the equilibrium constant of a reaction. the probability or steric factor (P) is introduced. It helps the molecules for a −E /RT proper oriented i. Rate = PZAB e a Illustration 15: What will be the effect of temperature on rate constant? (JEE MAIN) Sol: Rate constant of a reaction is nearly doubled with rise in temperature by 10°C.e. AIR) Note: In the following reaction formation of methanol from bromoethane depends upon the orientation of reactant molecules.e. •• Comparing the equation (vi) with Arrhenius equation. it catalyses the forward as well as the backward reaction to the same extent so that the equilibrium state remains same and is reached earlier. Saurabh Chaterjee (JEE Advanced 2013. •• Gibbs energy. where A is called frequency factor and Ea is the activation energy of the reaction. i. CH3 +OH– → CH3OH + Br – H +  Improper  H C Br OH Products Orientation H +  H  H C Br OH H H H Proper  +   Orientation HO C Br OH C H + Br H H H Intermediate Steric Factor: For effective collisions. we can say that A is related to collision frequency. •• It has an effect on spontaneous reactions but does not catalyse nonspontaneous reactions. rather it helps to attain equilibrium faster. else it simply bounce back and no products are formed. of a reaction is independent of the catalyst. Only proper orientation of reactant molecules lead to bond formation.303R T ..23 PLANCESS CONCEPTS For catalysts •• Even a small amount of the catalyst has the ability to catalyze a large amount of reactants. (JEE MAIN) Ea 1 Sol: We know that Arrhenius equation can be written as log k = log A – 2. Illustration 16: How is the value of activation energy calculated from the rate constants at two different temperatures. For collision theory •• Activation energy and proper orientation of the molecules together determine the criteria for an effective collision and hence the rate of a chemical reaction. k = Ae . ∆G. If the value of activation energy is 50 kJ/mol then show that by increasing the temperature from 300 K to 310 K. rate constant becomes nearly double. The dependence of the rate −Ea /RT constant on temperature is given by Arrhenius equation. Chem i str y  18. •• It considers atoms/molecules to be hard spheres and ignores their structural aspect.
we get log k2 – log k1 = − or =log 2 − 2. 0. log 2 − = k1 2.0693 min–1. E = ? a 0. Given T1 = 300K. T1 = 27 + 273 = 300 K.314 300 310 2. Illustration 18: A firstorder reaction is 50% complete in 30 min at 27°C and in 10 min at 47°C. T2 = 47 + 273 = 320 K. log k2 = log A – 2.303 × 8. burning of carbon is highly exothermic process.0231 2. 2 4  Chemical Kinetics If k1 and k2 are the rate constants at two different temperature T1 and T2 then Arrhenius equation at both the temperatures can written as Ea 1 Ea 1 log k1 = log A – .303R T2 Ea 1 1 k Ea 1 1 Subtracting equation (i) from (ii).693 0.1 8 .85 kJ mol –1 –1 20 . yet it does not start of its own.0231 min–1(at 27°C) and k = = 0.303R T1 T2 k1 2. Why? (JEE ADVANCED) Sol: A reaction can either be endothermic or exothermic.314 300 × 320 0.000 J k 50000 1 1 50000 310 − 300 Put these values = in eq.303R T1 T2 k2 = 0.303R T1 2. the reaction starts only when flame is applied to the heap of carbon contents.49 J mol = 43.2808 = 1.91 ≈ 2 k1 It is clear that by increasing the temperature from 300 K to 310 K doubles the rate constant.303 × 8.303 × 8.693 We know that k = or k= = 0. (iii). (JEE ADVANCED) Sol: Time for the completion of 50% reaction means t1/2.303 × 8. Ea = 50 kJ or 50.303 × 8.303 × 8. Ea can be calculated. and the energy of activation of the reaction in kJ/mol.4771 = 2. The activation energy of combustion of carbon is quite high and thus. but it possesses a minimum energy level for the molecules to cross the energy barrier for the reaction to take place. R = 8.314 × 300 × 320 or Ea = = 43848.4771 × 2.314 310 × 300 k2 or log = 0.314 300 × 320 Ea 20 0. k1 = 0.0693 min–1(at 47°C) t1/2 30 10 k Ea 1 1 We know that = log 2 − k1 2.2808 = Antilog 0.303R T1 T2 From the values of k1 and k2 at temperature T1 and T2. in spite of exothermic nature. Illustration 17: Even an exothermic reaction has activation energy. Also Threshold energy = ΣER + Ea and ∆H = ΣEP – ΣER (∆H may be + ve or – ve) For example.693 0.314 300 320 Ea 320 − 300 or log 3 = 2. It means t1/2 of the reaction at 27°C is 30 min and at 47°C is 10 min.0693 Ea 1 1 log = – 0.0231 min–1. T2 = 310 K.314 JK–1 mol–1. Calculate the rate constants.
for thirdorder reactions. 10.4 Van’t Hoff Differential Method Relationship between velocity V of nth order reaction and concentration of reactants C is given by log(V1 / V2 ) Van’t Hoff. 2t (a − x)2 a2 10.2 Graphical Method A graphical method based on the respective rate laws can also be used to determine the order of reaction. .3 HalfLife Method 1 A general expression for the halflife. for secondorder reactions.17: Plots of halflives versus concentration (t1/2 ∝ a ) This relation can be used to determine order of reaction ‘n’. Chem i str y  18. Conc. The equation which gives the most constant value for the specific rate constant (k) for a series of time intervals is the one corresponding to the order of reaction. METHODS OF DETERMINATION OF ORDER OF REACTION 10.1 Method of Integration (Hit and Trial Method) The most simple method is the one in which the quantities a. the reaction follows second order. is given by t1/2 ∝ n−1 a Zero order 1st order 2nd order 3rd order t1/2 t1/2 t1/2 t1/2 2 Conc. 1/a 1/a 1 −n Figure 18. the reaction follows first order. C1 and C2 are two different concentrations.303 a k= log10 . the kinetic equations are: 2. If all the reactants are at the same molar concentrations. for firstorder reactions. If the plot of log (a – x) versus ‘ t’ is a straight line. t (a − x) 1 1 1 k= − . (t1/2 ). (a − x)n−1 10. (a − x)2 1 In general. the reaction follows third order. x and t are determined and substituted in the kinetic equations of various orders. 1 If the plot of versus ‘ t’ is a straight line. n = log(C1 / C2 ) Where. (a − x) 1 If the plot of versus ‘t’ is a straight line.25 10. a graph of versus ‘t ‘ must be a straight line. for a reaction of nth order. while V1 and V2 are their velocities. t (a − x) a 1 1 1 k= − .
. 2 6  Chemical Kinetics 10. order with respect to B = m. [reactant at t2 ]–[reactant at t1 ] Rate = – t2 –t1 Square brackets denote concentration. then nA + nB + nC will be the order of reaction: When B and C are in excess. If nA. . 1 0. respectively are present in a reaction. PROBLEMSOLVING TACTICS (a) To determine the average rate for change in concentration over a time period. •• The overall order of the reaction. Average rate of reaction is the change in concentration of reactants (or products) during large interval of time.18: Plot of concentration (d) To determining the order of a reaction from its rate law versus time Rate law of a reaction is used to determine: •• The order of the reaction with respect to one or more reactants. the order of reaction will be nB.10 (ii) Calculate the slope of the curve between concentration of a product and time at t. ∆[reactant ] ∆[product ] Rate = – or rate= ∆t ∆t 0. when t = 0).15 Rate = Slope = 2 1.05 of concentration versus time: The initial rate of a reaction is the instantaneous rate at the start of the reaction (i. Figure 18. the order of reaction will be nC. rate = k[A]n[B]m[c]p For the rate law: Order with respect to A = n. When A and C are in excess.06 x 10 M/sec (i) Calculate the negative slope of the curve between concentration mol of a reactant and time at t.00 Initial rate is equal to the negative slope of the curve between 5 10 15 20 25 reactant concentration and time at t = 0. Negative sign in the above equation is used to make the rate of reaction positive. B and C. Minus sign can be ignored when calculating average rates from products.e. When A and B are in excess. Time. (c) Problemsolving tactics to determine the initial rate from a plot 0. 0. order with respect to C = p Reaction or overall order = n + m + p Note: The stoichiometric coefficient in the balanced equation for a chemical reaction is usually different from the order. nB and nC molecules of substance A. sec.5 Ostwald Isolation Method This method is used to find out the order of complex reactions. the order of reaction will be nA.20 (b) To determine instantaneous rate from a plot of concentration versus time: Instantaneous rate at time t is determined as follows: 0.1 8 .
20 Half life decreases Length of half life Length of half life with decreasing is constant increases with decreasing 0. halflife increases with decreasing concentration.15 concentration mol mol [A].19: Plot of concentration versus change in time For a firstorder reaction: For a secondorder reaction: A → products. rate = k[A]. Chem i str y  18.10 half 3 nd half life nd life 2 2 0.M L st st L st 1 half life 1 1 0.20 0. rate = k . (ii) For a 1st order reaction. rate = k[A]2 .693 / k For a secondorder reaction 2A → products or A + B → products (when [A] = [B]). Rate = k (k = ve slope of line) For a first order reaction. Then.05 rd 3 half life half life 0.10 rd 0.05 half life 0. Change in time changes the concentration of a reactant to half.27 Reaction Experimental Rate Law Order NO2 + CO → NO+ CO2 rate = k[NO2]2 2nd order reaction 2nd order in NO2 0 order in CO CH3CHO → CH4+ CO rate = k[CH3CHO]2 2nd order reaction 2nd order in CH3CHO (e) To determining rate laws from graphs of concentration versus time (integrated rate laws). t½ = 1 / k [A0] Graphical Relations and halflives: Differences in halflives for reactions of different orders (0.20 0. Time (sec) Time (sec) Figure 18. 1st. rate = k[A] (k = ve slope of line) For a second order reaction.00 20 40 60 80 0 5 10 15 20 25 100 200 300 400 Time sec.15 concentration 0. To determine the rate law for a reaction for different concentration (or the values of some function of concentration) versus time. (iii) For a secondorder reaction. or 2nd) are determined by plotting graphs between reactant [A] and time (t). t½ = 0. halflife decreases with decreasing concentration.00 0. [A] vs time for a [A] vs time for a [A] vs time for a Zero order reaction First order reaction Second order reaction 0. [A] versus t (linear for a zeroorder reaction) ln [A] versus t (linear for a 1st order reaction) 1 / [A] versus t (linear for a 2nd order reaction) The graph that is linear indicates the order of the reaction with respect to A.05 half life 3rd 0. make three graphs.00 0. rate = k[A] 2A → products/A + B → products (when [A] = [B]. halflife is constant.15 0. rate = k[A]2 . rate = k A → products. you can choose the correct rate equation: For a zeroorder reaction. rate = k[A]2 (k = slope of line) (f) Regarding questions of half lives: For a zeroorder reaction A → products. (i) For a zeroorder reaction. t½ = [A0] / 2k For a firstorder reaction A → products.10 half life 0.
dx When [A] = [B] = 1 mol/L. then =k dt Unit of rate n−1 constant litre Unit of rate constant = × sec–1 mol When n = order of reaction.1 8 . Various types of Type of Integrated rate equation Unite of rate t1/2 Halflife t3/4 period reactions reaction constant period Zeroorder Concentration d[A] A0 reaction – = k0[A]0 time–1 dt 2k dx Differential form =k dt . aA + bB → product rate = ∝ [A] [B] . 2 8  Chemical Kinetics POINTS TO REMEMBER Topic Formula Average rate of reaction Change in the concentration of reactants or(Products) ∆C C − C1 Average rate = = ± ± 2 = Time ∆t t2 − t1 Instantaneous ∆C dC rate of reaction Instantaneous rate = L im = ∆t → 0 ∆t dt For the reaction n1A + n2B → m1C + m2D 1 d[A] 1 d[B] 1 d[C] = – = + n1 dT n2 dT m1 dT 1 d[A] 1 d[B] 1 d[C] 1 d[D] Instantaneous Rate of reaction = – = – = + = = + n1 dT n2 dT m1 dT m2 dT 1 d[D] = + m2 dT Factors affecting •• Nature of reactants and products rate of reaction •• Effect of temperature •• Concentration of Reactants •• Presence of catalyst •• Effect of Sunlight Law of mass The rate at which a substance is directly proportional to its active mass and the rate at which a reaction action and rate proceeds is proportional to the product of the active masses of the reacting substances constant dx dx For a reaction. = k[A] [B] a b a b dt dt where k is rate constant or velocity constant.
x) 2 (conc) log[A] 1/(a x) t t t t t1/2 t1/2 t1/2 t1/2 0 1 (conc) (conc) 1/a 1/a HalfLife 1 t1/2 ∝ where n = order of reaction n−1 a Arrhenius k Ea 1 1 theory log 2 = − k1 2.303 a 0.693 0.303 b(a − x) reaction k2 = log time–1 t(a − b) a(b − x) 1 3 dx K 2a K 2a Differential form dt = k(a – x)2 Thirdorder Litre2 mole–2 _____ 1(2a − x) 1 3 reaction k3 = time–1 t2a2 (a − x)2 2 K 2a dx Differential form dt = k(a – x)3 Relationship Zero Order First Order Second Order Third Order between Rate of reaction and rate constant r r r r 0 1 2 3 (conc) (conc) (conc) (conc) 1/(a .693 1.x) Secondorder Mole–1 litre 2.303R T1 T2 −Ea /RT k = Ae where k1 and k2 are rate constant at temperatures T1 and T2. respectively (T2 > T1).382 log10 2× = t (a − x) K1 K1 k1 dx Differential form dt = k(a .29 Firstorder Time–1 reaction k1= 2. Chem i str y  18. .
k2 and k3 related? Initial concentration a Sol: The rate law reaction is rate = Concentration after (a – x) x 1 d[N2O5 ] 1 d[NO2 ] d[O2 ] 70 min − = = = k N2O5 2 dt 4 dt dt ∴ Fraction of the reaction remained unreacted d[N2O5 ] (a − x) 2. k1 = log or 0. m = 3 – 1 = 2.7021 dt a−x 2.036 k k a−x ∴ k 2 = 4k or k = 1 = 2 = k k = k 2 4 a−x 1 3 ∴ = ≈ 0.0231 × 70 = k [N2O5] = k3[N2O5] log = = 0. What is the order of the reaction with respect to NO and Cl2? (b) What is the rate of change of [N2O5] at this time? (c) What is the rate of reaction at this time ? Sol: Rate = k [NO]m [Cl2]n Let the concentrations of NO and Cl2 be x and y.6932 0. dt R3 = k xmyn. R3 = k(x)m (2y)n =0. Calulate the specific reaction rate of the (i) – = k1[N2O5] dt reaction. What fraction of the reactant remains after 70 d[NO2 ] min? (ii) = k2[N2O5] dt 0.6932 Sol: k1 = = = 0. 3 0  Chemical Kinetics Solved Examples JEE Main/Boards Example 3: In a reaction 2N2O5 → 4NO2 + O2. Example 2: For the reaction 2NO + Cl2 → 2NOCl.036 or 2k1 = k2 = 4k3. (given) R1 d[NO2 ] ∴ m + n = 3 Again.303 a = 4k[N2O5] = k2[N2O5] = log dt 70 a−x d[O2 ] a 0. d[O2 ] t1 30 (iii) = k3[N2O5] dt 2 Let the reaction be A → Product How are k1. R2 = k (2x)m (2y)n 2 dt 4 dt dt R2 and given that ∴ = 2m + n = 8 = 23. Sol: The rate of the reaction is expressed as respectively.1 8 .303 a k1 = 2k Taking antilog. 2n. we get = 5.0231 min–1. but when only the NO2 at the rate of 0. when the concentration of both reactants is doubled Example 4: The reaction 2N2O5 → 4NO2 + O2 forms the rate increased by a factor of 8.0231 dt a . the rate (a) What is the rate of change of [O2] at this time? doubles.0072 molL1s1. ∴ = 2n = 2 (given) (a) Rate of appearance of R1 ∴ n = 1.0072 mol L1s1 after a certain time. concentration of Cl2 concentration is doubled. 1 O2 = × rate of appearance of NO2 4 . 1 d[N2O5 ] 1 d[NO2 ] d[O2 ] rate = – = + = + R1 = kxm yn and. the rate can be expressed as Example 1: The halflife period of a firstorder reaction d[N2O5 ] is 30 min. t a−x d[NO2 ] 2.303 a ∴– = 2k[N2O5] = k1[N2O5] = Now.2 a 5.
of alkali (mL)used d[N2O5 ] 1 d[NO2 ] 1 : 19. a Find the stability constant for the complex. Thus we have dt 4 dt 4 1 Time(min) : 0 20 119 ∞ (b) Rate of disappearance of N2O5 = × rate of appearance of NO2 2 Vol.24 20.22 × 10–4 [Fe (dipy)32+ ] . no CH3COOH is formed. at zero time is only for HCl.79 k1= log =0.0036 mole /L/s.45 × 1013) [Fe2+][dipy]3and rate HCl CH3COOCH3 + H2O [H] → CH3COOH + CH3OH (reverse) = (1. Chem i str y  18.24 1 d[NO2 ] (c) Rate of reaction = × = 0= 1. Example 5: The activation energy for the reaction 2. kJ/mole.0018 (mole/L)s1. The amount of alkali 1.303 22. Conc.76 × 10−3 – log5.79 – 1. after t (ax) x Sol: At dynamic equilibrium.76 × 10–3 s–1 and k2 = 5. Example 7: For the reaction k k [Cr[H 2 O] 4 Cl 2 ] + (aq) → [Cr(H 2 O) 5 Cl 2 ] 2+ (aq) 1 2→ 9.6 42.6kJ E [Cr(H2O)6]3+(aq) k1 = 1. Fe2+ + 3 dipy → Fe (dipy)32+ Sol: Rate (forward) = (1.6 42.0072 = 0.79 4 dt (x) (x) (a) 1 = × 0.6 kJ.8 × 10–5 s–1 for the initial Energy 200kJ concentration of [Cr(H2O)5Cl2]+ is 0. Establish that the reaction is of first order. Reaction coordinate 2.303 22.0032 min–1 119 22.6 kJ/mol.6 + 200 kJ = 209.0072 = 0. titrated with a solution of alkali. Prepare 20 22. The alkali used against HCl is complex = Rate of its decomposition subtracted from the total alkali used (given in the data) to get the volume of alkali used only against CH3COOH.8 × 10 −5 needed for titration at various intervals is given below: Time: 0 20 119 ∞ (min) Example.03 (mL) forward and reverse directions.36 = 22.36 Sol: Energy of activation for reverse reaction The constancy of k1 shows that the reaction is of first = 9. order.73 26.22 × 10–4 [Fe (dipy)32+ ].0033 min–1 O3 (g) + NO (g) → NO2 (g) + O2 (g) is 9.0174 mol/L at 0°C.49 = 7.5 N HCl and 2mL of the mixture was withdrawn from time tc during the progress of hydrolysis of the ester and 2. 4 For t – 20. 8: The complexation of Fe2+ with the chelating agent dipyridyl has been studied kinetically in both Alkali used: 19.303(log1.76 × 10 −3 − 5.8 × 10−5 ) = = 2005 seconds. Calculate the value of t at which the concentration of [Cr(H2O)5Cl2]2+ is maximum. (1.alkali used = × = × 0.24 −19.24 −19.79 – 7.0018 mole/L/s. Hence.73 26.24 −19.24 20.0072 against dt 2 dt 2 CH3COOH = – 0.03 – = × = × 0. −19.49 an activation energy plot it ∆H° for this reaction is 200 For t = 119 . t = Example 6: 1 mL of methyl acetate was added to 20 mL k1 – k 2 of 0.45 × 1013) [Fe2+][dipy]3 = (1. What is the energy of activation for the reverse 2. Ini.Conc.79 reaction? k 1= log =0.31 d[O2 ] 1 d[NO2 ] 1 At zero time. Rate of formation of HCl acts as a catalyst.303(logk1 – logk 2 ) Sol: We have.
60 M. 2.84 kcal mol–1 [Fe(dipy)32+ ] 1.1 8 . concentration after 60 s for 10 g of its reactant to be reduced to 2. R1 = R2 = R3 . [A]t = 2. the first 0.34 – 10–5sec–1. [A] = 1.(ii) [A] < 1. k2 Methylcyclopentane Sol: For a firstorder reaction: k1 Percentage of cyclohexene = × 100 Rate of a reaction = k × molar concentration of the k1 + k 2 1. Sol: Rate constant. the unit of t = 2.8 × 0. and (b) rate after 60 sec.26 × 10−4 + 3.34 – [(1. Which reaction should be the fastest and is this true for all ranges of concentrations ? JEE Advanced/Boards Sol: Suppose R1.26 × 10 −4 reactant.02 × 2 = 0. concentration being in moles per litre.987 × 10–3 kcal mol–1 = 24. (b) ln K = 14.26 × 10–4 sec1.45 × 1013 ka = = = 1. respectively.25 × 104)/T] ….02 × 0. = × 100 = 77% 1.02 sec–1. Calculate (a) initial rate. R1 > R2 > R3 .25 × 104)/500] [Fe2+ ][dipy]3 1. R1< R2 < R3.34 – [(1.6020s = 138.25 × 104R Example 4: For a reaction at 800°C .. [A] > 1.303 × 102log 4s = 230. What is the percentage distribution of the 256 × 60 T rearrangement products? ∴ T = 513 K Sol: Example 2: The specific reaction rate of a firstorder k1 Cyclohexene reaction is 0.25 × 104 ∴ Ea = 1.5 g = 0.6s.25 × 104 × 1.04 mol/L–1sec–1. and (a) Comparing equations (i) and (ii). How much time will it take log = 0.35 × 10–5 sec–1 parallel first order rearrangements. ln K = 14. The initial concentration of the Bicyclohexane reactant is 2 molL–1. R2 and R3 are the rates of reactions of Example 1: The rate constant of a reaction is given by: ln first. 3 2  Chemical Kinetics = 1. k = 10–2 sec–1 ∴ Rate after 60 sec = k × concentration of the reactant Initial reactant conc. for first.8 × 10−5 (a) ∴ Initial rate = k × initial concentration ∴ Percentage of methyl cyclopentane = 23%. of activation and (b) the rate constant at 500 K. second and third order reaction.5 g? ∴ Concentration of the reactant after 60 sec = 0. ln K = ln A–(Ea/RT).02.(i) Now if.22 × 10−4 (∵ T = 500 K) Example 9: Bicyclohexane was found to undergo two ∴ K = 2. Calculate (a) the energy rate constant. R3 = k[A]3 what temperature will its halflife period be 256 min? [A] being the concentration of the reactant A in moles Sol: Given: per litre. At 730 K.012 molL–1sec–1 Time required. and for the formation of methyl cyclopentane the rate constant was 3.25 × 104)/T. which is the same for the three reactions.693 order rate constant for the formation of cyclohexene (c) K = (for first order) 256 × 60 was measured as 1. second and third order. Arrhenius equation.303 (b) Concentration of the reactant after 60 sec k = Example 10: A firstorder reaction has a specific 2 60 reaction rate of 10–2 sec–1.25 × 10 4 ∴ log = 14. (c) At ∴ R1 = k[A]1 . [A]0= 10 g after 60 sec.34 – (1.60 = 0. and k is the K(sec–1) = 14. R2 = k[A]2 . Final reactant conc. t = ? Example 3: The rate constant is numerically the same For a firstorder reaction.693 1. = 0.19 × 1017.3 × 0. (Ea/R) = 1.
4 of firstorder reaction.4771 m or m = = 2.5 2.5 7.9622 = 0. the whole obtained: of C6H5N2Cl converts into N2.24 (0. Hence volume of N2 at ∞ time corresponds to the initial concentration ‘a’ while [NO]×10–4 mole/L [H2]×10–3 mole/L d[NO]/dt×10–4 volumes of N2 at different time intervals correspond to x mole/L min as shown above.0032 min–1 70 162 − 33 The rate law of the above reaction is The consistency of k1 shows that the decomposition of 1 d[NO] C6H5N2Cl is a firstorder reaction. we get k (3) B + C →E + D 3 2.5 × 10 )m. m is the order with respect to NO the rate law for the disappearance of A. (2 × 10–3) …(ii) Sol.303 162 k1 = log = 0.4324 – 1. 0.5 × 10–4)m. show that the Half life period in hours: 3. log 220 – log 24 = m log 3 dt 2.33 2NO + 2H2 → N2 + 2H2O. the following data were At ∞ time. = After time t (a – x) x 1. (2 × 10 ) –4 –4 –3 .5 2..(i) 0.9622 Or 0.of N2 10 25 33 162 (mL) Sol: = 2 (t1/2 )2 a1 Sol: C6H5N2Cl → C6H5Cl + N2 where. we get the following results. the half change Hence the reaction is of second and first order with period for the catalytic decomposition of ammonia respect to NO and H. d[NO] k Or – = 2k[NO]m[H2] (1) A + B →C + D 1 dt k (2) C + D 2→A + B Substituting data (ii) and (iii). k1 = log = 0.2 (1. Hence the reaction is of 50 162 − 25 first order with respect to H2 Let us now consider the For t = 70 min..92 6667 (a ∝ initial pressure) = (2)n –1 . substituting the given data in equation (i) 1.5 × 10−4 )m 24 d[B] – = k1[A][B] + k3[B][C] – k2[C][D] and Taking log.2 × 10 = 2k(1.303 162 k1 = log = 0.24 For t = 20 min What is the order of this reaction with respect to NO 2. Sol: From the data (i) and (ii).24 × 10–4 = 2k(0. respectively. n is order of reaction Initial concentration a n−1 3.0 4. (ii) 1. rate = – × = k[NO]m[H2]1 2 dt Example 6: From the following reaction scheme. when the reaction is complete.5 3.52 1. were found as follows: Pressure (Pascals): 6667 13333 26666 Example 5: From the following data for the de composition of diazobenzene chloride.2 (iii) 1.0032 min–1 and H2 ? 20 162 − 10 For t = 50 min. Time 20 50 70 ∞ (min) n−1 (t1/2 )1 a Vol. i.3802 = m × 0. the rate is also halved at 2.0 0. Chem i str y  18. we see that when the concentration of H2 is halved.4771 Example 7: At a certain temperature.0033 min–1 constant concentration of NO.e. write where.303 162 NO as [H2] is constant.92 1.5 × 10−4 )m 220 ∴– = k1[A] [B] – k2[C][D] Similarly = = 3m or = 3m dt 0.0 reaction is of first order Calculate the order of reaction.4771 d[C] – = k2[C][D] + k3[B][C] – k1[A][B]. dt 0.: The reaction A is removed in step 1 and produced in step 2 Dividing (i) by (ii). data (ii) and (iii) to determine the order with respect to 2. B and C. d[A] 2.52 13333 From the given data.
11 ×106 form. Sol: 2.5×103 − 11 – 3.79 × 10–3 min–1 at 237°C and 12. initially containing is of first order .52 The rate constant and activation energy for reaction log = (n – 1) log 2 = 0.79 × 10−3 By equation (i) A1 = = Lactic acid – 12×103 7. Find out Similar calculations are made between first and third the temperature at which equimolar quantities of H2O.5 The values of k are fairly constant and so the reaction mol of B in the equilibrium mixture.303 45. −Ea /RT Sol: For reaction (a) K1 = A1e Example 8: The optical rotation of can sugar in 0. n = 1. The values of K and K are 2 × 10–3 mol L–1 k1 = log = 5.11 × 106 (a – x) = = 1. 103 12.77) (–10.50 – 31.27 A ← 1 → B. n comes equal to 1.79 × 10−3 2. CO.77) (–10. CO2 and H2 are formed (R = 2 cal).50° 31.7 × 10 Since in this reaction dextro form clianges to laevo e 2×510 = 4.75 =0 4.3010 × (n – 1) . i. If we add 0.87 ≈ 2 min–1 at 237°C and 24.908 (≈ 2).58 ×10 2 Sucrose (excess) Dextro Laevo 1.10° 13. 3 4  Chemical Kinetics 3.87 =24.87 2 sec–1 and 3 × 10–3 mol L–1 sec–1 respectively.77) (10. We now have.58 × 102 Substituting the data in equation.5 kcal mol–1 respectively.27 =41.52 × 10−4 1.5 −12.98 – – 10. Thus change in rotation is proportional If rate constants of two reactions are same.8 × 10−6 C12H22O11 → C6H12O6 + C6H12O6 e 2×510 + H2O Glucose Fructose = 3. −Ea /RT −Ea /RT Time 0 1435 11360 ∞ A1e 1 = A2e 2 (min) Ea −Ea [24.87 and for t = 1136 min Example 10: For the reversible reaction in equilibrium: k 2.1 8 . The volume of mixture is 1 L and may take place in two ways: remains constant.92 respectively. 2 mol of A. (i) HCOOH → H2O + CO 1 → B k Sol: A ← k (ii) HCOOH → H2 + CO2 2 t=0 2 mol L –1 0 .27 ∴ T = 668 K = 395°C k1 = log = 5.e.77– ∴ e RT = or e RT = rotation(°) (–10.5 = = 668 K for t = 1435 min RT 9. These values for reaction (ii) are 1.35 \T = × 12.5×103 Rotation(°): 34.35 × 2 2.5 N 12×103 – acid at 25°C at various time intervals are given below: or 2. the reaction is of second order. the reactions to the amount of sugar remaind after different time will give equimolar mixture of products.0]×103 2 1 A2 A2 Change in 34.98° – 10.303 45.52 × 10–4 0. same at temperature T.5 × 103 Or 9.10 – 13.0 kcal mol–1 1.79 × 10–3 = A1e RT ……(i) −Ea /RT Time (min): 0 1435 11360 ∞ For reaction (b): K2 = A2e 24. the optical rotation decreases with the progress of the reaction. Calculate the time taken for concentration of B to become equal to 3/4 of the concentration of A Example 9: The catalytic decomposition of formic acid at initial equilibrium.3010 × (n – 1) (i) are 2. Thus.52 × 10–4 = A2e RT …(ii) Show that the reaction is of first order. Let these be intervals. observations.311 × 10–5 k 1 2 1435 41.15 × 104 (a) (a – x) 3.77° – 1.77) A1 A1 = 45.442 × 10–5 1435 41.52 × 10−4 By equation (ii) A2 = = rotatory rotatory 24.2632 = 0.
∴ = K2 .66 dX ∴ K2 .66 – X) JEE Main/Boards Exercise 1 Q.16 – X) = 1.1 A solution of A is mixed with an equal volume of 2P(g) → 4Q(g) + R(g) + S(l) a solution of B containing the same number of moles.93 × 10–3 min–1 Moles added 1.34 0. at time t (1.66 mol L–1 = Kc (b) k × 100 = ln 400 A ←→B k × 100 =ln 2 Initial eq.303 log (0. dt (0.24 sec At equilibrium =0 3 × 10−3 0. \[X]eq = = min.16 –X) = 2 × halflife = 200 min (The reaction will obey back ward direction on addition (d) 2X(g) → 3Y(g) + 2Z(g) of B) 3 800 – x x 3 3 2 ∵ [B] = [A]eq = × 1. How much of A will be left unreacted pressure developed is found to be 317 mm Hg and at the end of 2h if the reaction is (a) first order in A and after a long period of time the total pressure observed zero order in B.4 A certain reactant Bn+ is getting converted to pseudo first order rate constant? B(n + 4)+ in solution.66 – X dt 2.34 0. t = 2.303 0. ∴ X = 0. Calculate the total pressure of the zero order in both A and B? vessel after 75 minute.34 +X) (1.3 The decomposition of a compound P at temperature T according to the equation Q.16 (c) For 75% reaction. At the end of 1h.66 K2 = 3 × 10 –3sec–1 (Ist order) 0. = K1 – K2[X] = 0. 1. start of decomposition in a closed vessel the total A is 75% reacted. t + C K1 = 2 × 10–3 mole L–1 sec–1 (zero order) at t = 0. The rate constant of this reaction is measured by titrating a volume of the solution with a .66 – 0. After 30 minutes from the and the reaction A + B → C occurs. K2 3 × 10−3 800 = 0.34 = 1. Chem i str y  18. What is the Q.66 – X) = K2 .66K2 –K2 X dt dX = K2[0.005.5= 1.005 3 4 4 Total pressure = 800 + x 2 (1. (b) first order in both A and B. (2 – X) mol L–1 X or – 2. Q. order = 1. is the first order reaction.66+0.2 The reaction CH3–CH2–NO2+ OH– → CH3–CH–NO2 +H2O obeys the rate law for pseudo first order kinetic Given: Vapor pressure of S () at temperature T = 32.5 in the presence of a large excess of hydroxide ion .also calculate the tiny fraction t1/8.155 dt (a) Partial pressure becomes half of initial in every 100 K1 2 × 10−3 ∴ 0=K1–K2[X]eq . if volume of liquid S is supposed to be negligible . time required At eq. 1% of nitro ethane undergoes reaction in half minute when the reaction concentration is 0. and (c) to be 617 mm Hg.303 log = K1[A]0 – K2[B]1 0.35 At eq. If mm Hg.66 ⇒ k = 6.303 log 0. X = 0 ∴ C = – 2. therefore.66 – X] .002 M.155 Also 800 – x = 700 ⇒ x = 100 3 ⇒ Total pressure = 800 + × 100 = 950 mm dX 2 Now.66 dX ∴t= log = 89.
some H2O2 decomposed. is 2. Estimate (a) the activation energy of the reaction that Show that equilibrium constant causes the spoiling of juice (b) How long should it take [B] K= = 5. calculate the rate constant of the new volume strength after 6 hours 10 mL of this the reaction (ii) at 300 K solution was diluted to 100 mL .10mL of this diluted solution was titrated against 25mL of 0. how much longer will it be before it If k1: k2 = 1: 9 and k1 = 1.14 For a reversible firstorder reaction k1 k1 decomposition is 4. Dimethyl ether decomposes as CH3OCH3(g) → CH4(g) + CO(g) + H2(g). if an order kinetics. Calculate Er and Eb at this Q.16 and the rate constant reaction. what will be the concentration of B after 30 s? Q.281 thou.15 For the system A ( g) → B ( g) .13 The reaction cis – Cr(en)2 (OH)2 ← 1 → trans– by pseudo first order kinetics. Calculate the rate constant of the conversion of Bn+ to follow first order kinetics.? The rate of film formation follows first Calculate the concentration ratio of C to A.956 k2 C thousand times of an inch. The rate constant of Q. (ii) B → products. how long would it take for half the Q. B & C are 60°. Calculate halflife of the the equilibrium constant is 0. 25% decomposition took place.572 × 105 at 300 K. The observed rotation of k 2 the mixture after 20 min was 5° while after completion Cr(en)2 (OH)+ is first order in both directions. Calculate the rate two parallel first order mechanism constant for decomposition of H2O2. If optical rotation per mole 2 of A.9 At room temperature (20°C) orange juice gets Q.10 A first order reaction.11 Two reactions In this process. At the same temperature B decomposes twice solution of H2O2 labelled as 20 volumes was left open as fast as A. If the film thickness is 1. The rate of the reaction (i) B(n + 4)+ assuming it to be a first order reaction.8 A vessel contains dimethyl ether at a pressure of equilibrium amount of the Trans isomer to be formed? 0.78 × 10–3 min–1. it converts Bn+ to B(n – 2)+ and B(n +4)+ to (i) A → products B(n – 1)+.16 The complex [Co(NH3)5F]2+ reacts with water same time in a 30% solution maintained at 40°C ? according to the equation Assume that activation energy remains constant in this range of temperature.7 An optically active compound A upon acid catalyzed k hydrolysis yield two optically active compound B and C + Q.6 A metal slowly forms an oxide film which completely A protects the metal when the film thickness is 3. ∆H for the forward spoilt in about 64 hours.4atm. the volume used up is 32 ml. What will be the percent decomposition in the Q. At 25°C of the reaction it was – 20°. Q. In a refrigerator at 3°C juice reaction is –33kJ/mol (Note. In an experiment starting with the pure cis form.3 × 10–5s–1. If the energy of activation for the reaction due to this. [B]0 = 0.When a 20% solution of A was the same for the forward and backward reactions kept at 25°C for 20 minutes. Calculate the ratio k2 of initial rate of diffusion to rate of diffusion after 4. requires activation temperature .01 mole L–1 and hours of initiation of decomposition. If [A]0 = 0.025 M KMnO4 Q. A minutes. can be stored three times as long before it gets spoilt. is doubled when the temperature is raised from 300 K to 310 K.Assume that the preexponential factor is energy of 70 kJ mol–1.12 A certain organic compound A decomposes by solution under acidic conditions. At t = 0 the volume of the reagent consumed is 25 ml and at t = 10 min. [Co(NH3)5F]2+ + H2O → [Co(NH3)5(H2O)]3+ + F– . To determine is half of that of reaction.1 8 . A → B. 3 6  Chemical Kinetics reducing reagent which only reacts with Bn+ and B(n+4)+.5 = 10–2 s–1 and [B]eq /[A]eq = 4.3 × 10–4 s–1.481 thou. in 6 weeks. k1 B Q.40° & – 80°. The halflife for this reaction at 310 K is 30 Q. Q. If the activation energies for juice to get spoilt at 40°C? [A] Er and Eb are in the ratio 20: 31. k1 is 3. experiment is started with only A and allowed to run for one hour.5 Decomposition of H2O2 is a first order reaction. ∆H = ∆E in this case).
show that the activation energy E’ for the disappearance of A is given in terms of activation Q. at 27°C and in 10 minutes at 47°C.26 t1/2 of a reaction is halved as the initial concentration k −2 of the reaction is doubled.25 The optical rotation of sucrose in 0.28 A substance reacts according to the law of first Where K = k 3 ⋅ 2 1 . Show that the above mechanism leads to the following Q. .29 What will be initial rate of a reaction if its rate k2 C(g) constant is 10–3 min–1 and concentration of reactant is 0. Find the activation energy for the reaction k 2 A → C .4 atm and after during the reaction. The initial pressure in a container of capacity V litres is The reaction is acid catalysed i. Evaluate the rate law = K[CO][Cl2]3/2. dt Arrhenius parameters A and Ea. How much of reactant will be converted into products in 200 minutes. Q. find out the order of the (iii) COCl + Cl2 k3 → COCl2 +Cl (slow) reaction. C →D A. of the substance is 1.19 The reaction of formation of phosgene from CO the reaction follows first order kinetics and Cl2 is CO + Cl2 → COCl2 Time (min) 0 10 20 30 40 ∞ The proposed mechanism is Rotation +32.of activation of the factor A and Ea for the apparent second order rate reaction in kJ per mole constant in terms of A1. Thus rate = k[Complex]a where k’ = k[H+]b calculate ‘a’ and ‘b’ given the following data at 25°C.22 The specific rate constant for a reaction increases k by a factor 4 of the temperature is changed from 27°C Q.27 The rate constant of a reaction is 1. 1/2 k k Q. x[complex]a x[H+]b. 2B(g A(g) Q.4 +19.e.0 M Q. Find the rate constant k1 and k2 for the appropriate reaction. Ea and Ea 1 2 3 for the three steps.37 The rate of the reaction = rate const.0 × 10–2 sec–1. Pressure at time t = 10 sec is 1.5 × 10–7 sec–1 at 100°C.5 × 10–7 sec–1 d[COCl2 ] at 50°C and 4.24 A first order reaction is 50% completed in 30 min approximation to eliminate the concentration of C.5 atmosphere.17 For the two parallel reactions A → B and 1 to 47°C.6 –11.18 For the mechanism (ii) What will be the effect of doubling concentration of k A + B ← 1 k3 → C .5 1 Q. A2 and A3 and Ea .21 A first order reaction takes 69. How much time will be needed for 80% 0.23 The reaction 2A+ B + C → D + 2 E is of first order k E + k 2E2 with respect to A and of second order with respect to B energies E1 and E2 for the two paths by E’ = 1 1 and is of zero order with respect to C k1 + k 2 (i) Write down the rate law for the reaction Q.5 +22.4 +28.8 +25. If initial conc. Calculate the rate (b) Assuming that k3 << k2. Chem i str y  18. Show that Q. express the preexponential constant at 27°C and the energy. k 2 (a) Derive the rate law using the steadystate Q.20 For the following first order gaseous reaction (a) Find out the initial rate k1 (b) Find out the rate after 1 min.5 M HCl at 35° C at different time intervals are given below.02 0. Q.2 mol dm–3. k − 2k −1 order reaction the velocity constant of the reaction is 1. [H+] does not change 1 atm.1 k1 (degrees) (i) Cl2 ← → 2Cl (fast equilibrium) k −1 k (ii) Cl + CO ← 2 → COCl (fast equilibrium) Q.1 0.3 minutes for 50% [Complex]M [H+ ]M T1/2hr T3/ 4hr completion.2 0. B and C.01 1 2 completion? 0. infinite time it becomes 1.
1 M.02 M (D) 0.09 M (B) 0.8 to 0. initial rate of reaction (A) Double (B) Remain unchanged were determined graphically in four experiments.65 (D) Value of k is independent of the initial concentration of A and B . Find the rate of reaction when reaction will be as concentration of A is 0.215 (3) 1.9 The initial rate of zeroorder reaction of the to 0. 1 1.25 B.30 A first order reaction is 20% complete in 10 Q. What would be the (A) 30 minutes (B) 15 minutes concentration of B after 60 sec? (C) 7.002 M 2A + B → C is found to be: rate=k [A] [B] The correct Q. (C) Triple (D) Increase by a factor of 4 S.75/k (C) 0.06 (B) 0.1 (D) 4. 3 8  Chemical Kinetics Q.2×10–3 10–1 8×10–3 If these reactions are carried simultaneously in a reactor such that temperature is not changing. Calculate concentration of a reactant to drop to 3/4 of its value. If rate of Rate law for reaction from above data is disappearance of B is y M sec–1 then rate of formation (A) r = k[A]2W2 (B) r = k[A]2[B] (in M sec–1) of Q is: (C) r = k[ A] [B]2 (D) r = k[A][B] 2 3 4 3 (A) y (B) y (C) y (D) y 3 2 3 4 Q. No. the t3/4 (a) Specific rate constant of the reaction and can be written as (b) Time taken for the reaction to go to 75 % completion (A) 0.025 M is gaseous reaction A(g) → 2B(g) is 10–2 M min–1.2 The rate law for a reaction between the substances A and B is given by rate = k [A]n [B]m On doubling the Q.8 Gaseous reaction A → B + C follows first order concentration of A and halving the concentration of kinetics.29/k Exercise 2 Q.1M.01 M Q. the rate of reaction will Q.6 A reaction was found to be second order with respect to the concentration of carbon monoxide. starting with different initial concentration of A and B. If Single Correct Choice Type the concentration of carbon monoxide is doubled.1 8 .1 For the reaction A + B → C.6×10–3 10–1 2×10–3 and M → 2Q + R ∆H = –x kJ/mole of M 4 3.2×10–3 5×10–2 4×10–3 3 1. with everything else kept the same. (A) 2(n – m) (B) 1/2m + n (C) (m + n) (D) (n – m) (A) 2 × 10–3M min–1 (B) 10–3M min–1 (C) 10–4M min–1 (D) 5 × 10–4M min–1 Q. [A]0/M (Initial [B]0/M (Initial rate/ (M sec ) –1 conc. If the initial concentration of A is 0. The time taken for the concentration to change from 0.10 Consider the following first order competing statement in relation to this reaction is reactions: (A) Unit of k must be s–1 k k X → A + B and Y 1 → C + D if 50% of the reaction 2 (B) t1/2 is a constant of X was completed when 96% of the reaction of Y was (C) Rate of formation of C is twice the rate of completed the ratio of their rate constants (k2/k1) is disappearance of A (A) 4. Concentration of A changes from 1M to 0. the concentration of the reactant.6×10–3 5×10–2 10–3 A + 3B → P ∆H = –2x kJ/mole of A 2 3. If the rate constant for a first order reaction is k.1 M Q. the ratio of the new rate to the earlier rate of the M in 138.7 For a hypothetical reaction.5 minutes (D) 60 minutes (A) 0.69/k (B) 0.6 minutes.) conc.5 t1/4 can be taken as the time taken for the minutes.4 M in 15 minutes.4 The rate equation for the reaction (C) 0.3 In a first order reaction.) Q. decreases from 0.10/k (D) 0.
log 2 = 0. (B) 600 sec. (C) 900 sec.21 For the first order reaction A → B + C.37. 20 minutes time is required for completion of 20% reaction.50 × 104L mol–1 s–1 (B) 1.11 At certain temperature.4kJ/mole (A) 300sec. (C) 100 kJ/mole (D) 88. when the reaction is allowed to take place at constant pressure and temperature P(mm Hg) 500 250 t1/2(in min) 235 950 (A) 0.0125 M (D) None of these [Given log(23. the halflife period for Q.25 M.20 A first order reaction is 50% completed in 20 then rate constant for the backward reaction at this minutes at 27°C and in 5 min at 47°C. of 1 M of A at 27°C if 3. 104.5 × 1011L mol–1 s–1 (A) 43.5) = 1. (C) A is adsorption factor d[B] (D) Ea is the energy of activation If =k[A].57kJ/mole .303 × 10–3 sec–1 (A) 12 kJ/mole (B) 831.65kJ/mol Q.30] Q.0 × 10–18s–1 (B) 6. then half life (t1/2) is dt (A) 55.17 In respect of the equation k = A exp (– Ea / RT). E represents (A) The fraction of molecules with energy greater than Q.58] Given: k = 2. what is the time taken for concentration of in the activated state.14kJ/mol (C) 1.8 × 10–16 % of the reaction molecules exists and B each. the activation energy and the Arrhenius parameter (A) of a chemical reaction at 25°C are 3.16 The reaction A (g) → B(g) + 2C (g) is a first order the thermal decomposition of a gaseous substance reaction with rate constant 3. (A) 1 (B) 2 (C) 2.0 × 10–4 s–1.44 min (B) 50 min Q. reaction is [log 3.5 × 10–3 s–1 at 100 K. Starting with initial conc.0 × 1014s–1 (C) Infinity (D) 3.465 × 10–6s–1. Chem i str y  18.15 Reaction A + B → C + D follows following rate law: Q.85kJ/mol (B) 55.025 M Find the order of reaction (C) 0.18 Rate of a reaction can be expressed by Arrhenius (C) 62.4 kJmol–1 and 6.13 If decomposition reaction A(g) → B (g) follows the activation energy of the reaction first order kinetics then the graph of rate of formation (B) The energy above which all the colliding molecules (R) of B against time t will be will react (A) R (B) R (C) The energy below which colliding molecules will not react (D) The total energy of the reacting molecules at a temperature T. (D) 1200 sec. find the concentration of as follows A after 200 sec.5 × 10–11L mol–1 s–1 (C) 11.19 The rate constant.97kJ/mol (D) 6. The value of the rare constant at T → ∞ t (A) 2.5 × 1010L mol–1 s–1 (D) 1. The energy of temperature is activation of the reaction is (A) 1. the Ea(activation energy) of the A to become 0.97.13 min (D) None of these equation as k = Ae–E/RT In this equation.6 × 1030s–1 Q.Starting with depends on the initial partial pressure of the substance 0. If 10–5 moles of A and 100 moles of B are present in a 10 litre vessel at equilibrium Q. carried out rate = k[A]1/2[B]1/2.05 M (B) 0.39 Q.12 Consider the reaction: A → B + C (B) k is equilibrium constant Initial concentration of A is 1M.5 (D) 3 which one of the following statements is correct? (A) R is Rydberg’s constant Q. log (95)= 1. t t (C) R (D) R Q.1 mole of A in 2 litre vessel.8 = 0.0 × 104 S–1 t respectively.14 The rate constant for the forward reaction A(g) → 2B(g) is 1.
04 (D) 0 (C) Both A and B (D) Neither A nor B . 2 A + B → Products When concentration of B alone was doubled.3 minutes (B) 23.1 8 . When the concentration of A alone was + 2Cl–(aq) The rate equation for this reaction is rate = doubled.03 minutes (C) 9. If the temperature is raised (A) Remain unchanged (B) Triple by 50° C.10The following mechanism has been proposed for in 2 × 102 sec. the rate increased by two times. the rate of the reaction increases by about (C) Increase by a factor of 4 (D) Double (2011) (A) 10 times (B) 24 times Q. The rate constant of reaction in sec–1 is the reaction of NO with Br2 to from NOBr: NO(g) + (2003) Br2 (g) ← → NOBr (g) NOBr (g) + NO(g) → 2NOBr 2 2 (A) 2 × 104 (B) 3. 0.0001% of the Q.3 In a first order reaction the concentration of reactant decreases from 800 mol/dm3 to 50 mol/dm3 Q. The energy of is 6.37k cal/mol (A) 230.9 For the reaction A + 2B → C. Then the concentration of N2O5 (in mol litre–1) is(2001) (A) A only (B) B only (A) 1.386 × 10–2 (D) 2 ×10–4 (A) 1 (B) 0 (C) 3 (D) 2 Q. rate of disappearance 2 (B) Can never be a unimolecular reaction of ‘A’ is related to the rate of appearance of B’ by the (C) Can never be a bimolecular reaction expression (2008) (D) Can never be a first order reaction d[A] 1 d[B] d[A] d[B] (A) – = (B) – = dt 4 dt dt dt Q.6 minutes Previous Years’ Questions Q.301) (2009) (A) Zero (B) 7. If (C) – =4 (D) – = dt dt dt 2 dt the concentration of carbon monoxide is doubled with everything else kept the same. B.11 Consider the reaction Cl2(aq) + H2S(aq) → S(s) + 2H+(aq) not change. rate is given by R = [A] [B]2 then the order of the reaction is (2002) (C) 32 times (D) 64 times (A) 3 (B) 6 (C) 5 (D) 7 Q.212 k cal/mol (D) 11.8 A reaction was found to be second order with d[A] d[B] d[A] 1 d[B] respect to the concentration of carbon monoxide.7 A reaction involving two different reactants (2005) 1 (A) Can never be a second order reaction Q.5 The rate constant for the reaction. the halflife did Q. The unit of k[Cl2][H2S] Which of these mechanisms is/are consistent rate constant for this reaction is (2007) with this rate equation (A) L mol–1 s–1 (B) No unit A. H2S ←→ H+ + HS– (fast equilibrium) 2N2O5 → 4NO2 + O2 is 3 ×10–5 sec–1. Cl2 + H2S → H+ +Cl– + Cl– + HS– (slow) (C) mol L s –1 –1 (D) s–1 Cl++ HS– → H+ + Cl– + S (fast) Q.45 × 10–5 (g) If the second step is the rate determining step.6 The halflife period of a first order chemical reaction total number of collisions are effective.93 minutes.06 minutes (D) 460.1 For a reaction A → 2B.05k cal/mol (C) 46.4 Consider the reaction.40 × 10–5mol litre–1 sec–1. the rate of reaction will Q. The time required for the completion of activation of the reaction is 99% of the chemical reaction will be (log 2 = 0. If the rate is Cl2 + HS– → 2Cl– + H+ + S (slow) (2010) 2.22 In a reaction carried out at 400 K .2 The rate of a chemical reaction doubles for every (2006) 10° C rise of temperature.2 (C) 0.4 (B) 1. the order of the reaction with respect to NO(g) is (2006) (C) 1. 4 0  Chemical Kinetics Q.
22 The rate of a reaction doubles when its temperature d[A] d[B] d[A] d[B] changes from 300 K to 310 K.47 x 10–5 M/min (D) 1.50 to L–1 if it is a zero order reaction (2010) 0. all at 298 K.314 JK1 mol1 and log dt dt dt dt 2 = 0.03 minutes + D.25 mol/L if it is a zero order reaction? (2010) (A) 1 h (B) 4h (C) 0.41 Q. the rate of the reaction increases by about: (2011) Q.20 The rate of a chemical reaction doubles for every (C) Eb =Ef 10oC rise of temperature. rate of disappearance A is 0.73 x 10–5 M/ min (B) 3.73 x 10–4 M/min d[A] 1 d[B] d[A] 1 d[B] (A) − = (B) − = dt 2 dt dt 4 dt Q.19 Consider the reaction: Cl2(aq) + H2S(aq) → reactions for A2 + B2 → 2AB are 180kJ mol–1 and S(s) + 2H+(aq) + 2Cl– (aq) The rate equation for this 200kJ mol–1 respectively. The presence of catalyst lowers reaction is rate = k [Cl2] [H2S] the activation energy of both (forward and reverse) Which of these mechanisms is/are consistent with this reactions by 100 kJ mol–1.3 minutes (B) 23.6 minutes separate experiments.17 The halflife period of a first order chemical (A) 53.25 h (A) 4 h (B) 0.0 mol/L.5 kJ mol1 completion of 99% of the chemical reaction will be (log 2 = 0.301) (2009) Q. The time required for the (C) 58.23 . in general (2005) (A) B only (B) Both A and B (A) Eb < Ef (C) Neither A nor B (D) A only (B) Eb >Ef Q.I concentration of A changes from 0. If the temperature is raised by (D) There is no definite relation between Eb and Ef 50oC. the (A) C (B) I (C) I2 (D) C. (A) → products.5 h (C) 0. is 2. For the nonstoichiometry reaction 2A + B → C (A) 230.06 minutes (D) 460.6 kJ mol1 (B) 48. how much time does it of the reactant ‘A’.1 M to 0.025 M in 40 minutes.21 For a first order reaction. Activation energy of (C) − = (D) − 4 = such a reaction will be : (R = 8. the rate of formation of AB* is directly proportional to (2001) Q. how much time does take for its concentration to come for 0.12 The time for half life period of a certain reaction Q.25 h (D) 1 h Q.16 For a reaction A → 2B .18 The time for halflife period of a certain reaction A A → Products is 1 hour.5h (D) 0. respectively. The rate of reaction when the concentration of 1 Q.15 If ‘I’ is the intensity of absorbed light and C is the (A) 24 times (B) 32 times concentration of AB for the photochemical process (C) 64 times (D) 10 times AB + hυ → AB*. When the initial concentration → products is 1 hour. (2014) .25 mol it take for its concentration to come from 0.6 kJ mol1 reaction is 6. The enthalpy change of the rate equation? (2010) reaction (A2 + B2 → 2AB) in the presence of catalyst will be (in kJ mol–1) (2007) (A) Cl2 + H2 → H+ + Cl– + Cl+ + HS–(slow) (A) 300 (B) 120 (C) 280 (D). Chem i str y  18. When the initial Concentration of the reactant ‘A’ is 2.14 Consider an endothermic reaction X → Y with Cl2 + HS– → 2Cl– + H+ + S (slow) the activation energies Eb and Ef for the backward and forward reactions.5 kJ mol1 (D) 60.93 minutes.20 Cl+ + HS– → H+ + Cl– + S (fast) (B) H2S ⇔ H+ + HS– (fast equilibrium) Q. the following kinetic data were obtained in three (C) 46.01 M is: (2012) 2 of ‘A’ is related to the rate of appearance of ‘B’ by the (A) 1.47 x 10–4 M/min expression (2008) (C) 3.0 mol L–1.13 The energies of activation for forward and reverse Q.50 to 0.301) (2013) Q.
4 × 103 (A) 6. Calculate the rate of reaction (in M sec–1) and rate of reaction in term of pressure.66 L min–1at STP The rate law for the formation of C is (C) 1. 4 2  Chemical Kinetics Initial Initial Initial rate of Q.3 In a catalytic experiment involving the Haber rate constant when the rate law is written for process N2 + 3H2 → 2NH3.6 For the elementary reaction 2A + B2 → 2AB.2 M 0.1 M 2.7 For the reaction 3BrO– → BrO–3 +2Br– in an alkaline (i) What is rate of formation of H2O? aqueous solution the value of the second order (in BrO–) rate constant at 80°C in the rate law for (ii) What is rate of disappearance of H2O2? ∆[BrO − ] – was found to be 0.2 In the following reaction 2H2O2 → 2H2O + O rate of formation of O2 is 3.05 M. the concentration of NO increases by 1. and C two times? .08 × 10–2 mol litre–1 in 3 seconds. (b) H2? 2 Given that – d [N2O5]/dt = k1[N2O5] Q.056L mol–1 s–1.1 Ammonia and oxygen reacts at higher temperatures decreases from 2 atmosphere to 1. the rate of formation of O2 will be: 0.5 to 0.8 Dinitropentoxide decomposes as follows: If there were no side reactions. Calculate Q. of A.1 M 0. In fifty minutes the concentration of (mol L1s1) H2O2 decreases from 0. What is the ∆t Q.2 × 103 (2016) 0. what was the rate of 1 N2O5(g) → 2NO2(g) + O2(g) reaction expressed in terms of (a) N2.1 M 0.6 M min–1 Q. When the concentration of H2O2 0. (i) Rate of reaction (ii) Rate of disappearance of Calculate how much the rate of reaction will change if ammonia (iii) Rate of formation of water the volume of the vessel is reduced to one third of its original volume? Q. (1) What is the relation between k1. the rate of reaction was ∆[BrO3− ] ∆[Br − ] measured as (a) (b) ? ∆t ∆t ∆[NH3 ] Rate = = 2 × 10 mol L s . k2 and k3? Give the rate law for the reaction in the form of differential equation. d[O2]/dt = k3[N2O5] first order in A second order in B and zero order in C.4 The reaction 2A + B + C → D + E is found to be d[NO2]/dt = k2[N2O5] .1 M 1.34 × 10–2 mol min–1 (D) 6.9 Suppose that the Sun consist entirely of hydrogen (ii) What is the effect in rate of increasing concentrations atom and releases the energy by the nuclear reaction. –4 –1 –1 ∆t Q. Q.2 × 103 reaches 0.5 At 27°C it was observed during a reaction of hydrogenation that the pressure of hydrogen gas Q.1 8 .93 × 10–2 mol min–1 dC dC (A) = k[A][B] (B) = k[A]2 [B] dt dt dC dC (C) = k[A][B]2 (D) = k[A] dt dt JEE Advanced/Boards Exercise 1 Q.24 Decomposition of H2O2 follows a first order Concentration (A) Concentration (A) formation (C) reaction.2 M 1. B. In an experiment.1 atmosphere in 75 as 4NH3(g) + 5O2(g)→ 4NO(g) + 6H2O(g) minutes.93 × 10–4 mol min–1 (B) 2.125 M in one such decomposition.
How long would it take concentration of both the substance will be equal.22 If a reaction A → Products. the concentrations of Time(min) [A] reactant A are C0. (ii) the time taken for the reactions to go to 75% completion. for H+ in drop to disappear? Q.... Q..5×10–4 2 × 10–3 2. Q.5 × 1–3 M and [NO] = 1. Q..15 A certain substance A is mixed with an equimolar quantity of substance B.11 In the given reaction. How long will 5. a2C0. what will the ratio of rate of reaction relative to initial rate when be the expiry time of the drug? PC becomes 0.5 × 10–3 sec–1.. if the rate constant of disappearance initially [A]= 4 [B].0 0. Calculate the value of k. The inactivation process was found to be first 10–2 M s–1.2 × 10–5 sec–1 at 320°C. Q.1 × 1–3M? .25 At 800° C the rate of reaction Q.8 × 10–4 Calculate (i) the specific rate constant.13 The rate constant for a zero order reaction is What % of SO2Cl2 is decomposed on heating this gas 2 × 10–2 mol/L sec–1. Chem i str y  18.8 atm.. Changes with the concentration of NO and H2 are (Given: order of reaction is zero) [NO] in M [H2] in M 1 d[NO] − in M sec–1 Q. (ii) 1. 2 dt How much time will it take for (i) 50% completion (i) 1. [H2] = 1.5% completion..after time interval 0. Also calculate 1.7 × 1030 kg.12 For the following data for the zero order reaction A → products. 2. A → B rate constant is 1. aC0.5×10–4 4 × 10–3 4. the initial partial later.0% of the virus was found to be inactivated per minute.10 The reaction A(g) + 2B(g) → C(g) + D(g) is an sample was 500 units/ml.. At the beginning of the min. 3t.18 Show that in case of unimolecular reaction. a3C0 .2 atm. if we start with 10 M of A. the concentration was found to be 420units/ml.6 and PB = 0. calculate the initial concentration. Calculate the time after which the of H+ is 1 × 107 mole liter–1 sec–1.25 g? constant at 3. Q..10 ml) contains follow first order kinetics are taken in such a way that 6 × 10–6 mole of H+..43 4 Q.24 Two substances A(t1/2 = 5 mins) and B(t1/2 = 15 mins) Q.0 g of this reactant take total output power of the Sun is assumed to remain to reduce to 1.25 M.08 M Q. experiment 2. Q. Take the mass of the Sun as 1.. 0.16 A first order reaction is 75% completed in 72 min.21 A viral preparation was inactivated in a chemical Q. if the concentration of the reactant for 90 min? after 25 sec is 0.0 0.2 × bath. 2t.2 × 10–4 Q. When analyzed 20 months elementary process. (iii) 3.19 A first order reaction has a rate constant is 411 H →2 He with 26 MeV of energy released.9% of the reaction to take place in ten times that required for half of the reaction.09 M the relation between k. Evaluate k for inactivation process.17 A first order reaction is 20% complete in 10 min.14 A drop of solution (volume 0. What is concentration of B after 10 and 20 order in virus concentration.23 The reaction SO2Cl2(g) → SO2(g) + Cl2(g) is a first order gas reaction with k = 2..10 M Show that the reaction is of first order. In an experiment.20 A drug is known to be ineffective after it has decomposed 30%.0×10–4 2 × 10–3 8..a and t..9 × 1026 W find the time it will take to burn all the hydrogen.. The original concentration of a Q. Calculate Assuming that decomposition is of first order. pressure of A & B are PA = 0.. Given 0 < a < 1. t. At the end of an hour A is 75% 2NO + H2 → N2 + H2O reacted Calculate the time when A is 10% unreacted. (a) What is the order of this reaction? (b) What is the rate equation for the reaction? Q.4 × 10–4 (ii) 87.. the (c) What is the rate when time required for 99. If the 1.. where a is a constant.0 0.
8 13.) 390 1195 3155 ∞ Pressure increase 96 250 467 619 Q. of KMnO4) 22. Find k. B and C.28 The pressure of a gas decomposing at the surface the gas pressure at intervals.05 1×10–3 0.37 From the following data show that decomposition Q. and the results are given below Time (in hrs) 0 5 7. its rate constant. What is the order of reaction? Time (sec. Q.34 S → G + F °C and at an initial pressure of 200 mm is 50% complete Time t ∞ in 53 minutes and 73% complete in 100 minutes Rotation of Glucose & Fructose r1 r∞ (i) What is the order of the reaction? (ii) Calculate the velocity constant Find k.26 The data below are for the reaction if NO and Cl2 Q.27 The catalytic decomposition of N2O by gold at 900 Q. Q.15 0.15 9×10–3 Q. 4 4  Chemical Kinetics Q.t.33 A → 2B + 3C (a) What is the order w. Time t ∞ (b) Write the rate expression Volume of reagent V2 V3 (c) Calculate the rate constant The reagent reacts with A. the half life period is reduced to 25 minutes.32 A → B + C to form NOCl at 295 K Time 0 t Concentration of Concentration Initial Rate Volume of reagent V1 V2 Cl2 [M] of NO (M s–1) The reagent reacts with A. Write the rate equation for this reaction and determine the rate Total pressure of A + B +C P2 P3 constant. at the 3 same temperature but at initial pressure of 600 mm? Q.5×103 Determine the order of reaction.5 10 t (sec) 0 100 200 300 Total pressure (in min) 758 827 856 882 Pa(Pascal) 4×103 3.3 8.05 0.1 8 .29 The half life period of decomposition of a reaction. B and C.31 A → B + C of H2O2 in aqueous media is first order. Find k.25 Find k. Find k. compound is 50 minutes.36 The thermal decomposition of dimethyl ether as measured by finding the increase in pressure of the Q. . Time t ∞ Time in (minutes) 0 10 20 Total pressure of ( B +C) P2 P3 Volume (in c.2 M & 0. Show from the following of a solid catalyst has been measured at different times figures that reaction is of first order. NO and Cl2 in the reaction.4 M respectively.30 In this case we have A → B + C (mm Hg) Time t ∞ The initial pressure of ether was 312 mm Hg. r.35 The reaction AsH3(g) → As(s) + H (g) was 2 2 followed at constant volume at 310°C by measuring Q.c. [Assuming nfactor of A B & C are same] Q. (d) D etermine the reaction rate when concentration of Cl2 and NO are 0.05 3×10–3 [Assuming nfactor of A B & C are same] 0. (iii) How much of H2O will decompose in 100 min.05 0. 0. If the initial concentration is (CH3)2O(g) → CH4(g)+H2(g)+CO(g) at 500°C is as follow: halved.5×103 3×103 2.
43 The reaction A(aq) → B (aq) + C (aq) is monitored on inversion of cane sugar by measuring optical rotation of reaction mixture as different time interval . k1 B (c) Calculate the fraction of H2O2 decomposed after A 25 minutes. Find the rate (degree) constant for first order conversion of A into B and C. On complete decomposition. Calculate after one hour [A] equation 2N2O5 (g) → 4 NO2(g) + O2(g) is a first order reaction. From these data find (a) initial pressure of A (b) the pressure of A at the end of 10 minutes B k1 (c) the specific rate of reaction(d) the halflife period of Q. Show that the reaction is of first order. k2 C Q.5° after 6. k1: k2 = 1: 10. H2O and O react bimolecularly solution gave 10.41 A definite volume of H2O2 undergoing spontaneous 2 → C.25 c.39 At 100°C the gaseous reaction A → 2B + C was k2 zt observed to be of first order. ∆H for This reaction is 72 kJ 273 K) after 5. at any given instant.00 ml oxygen occurs bimolecular recombination of 2OH radicals to form (per 100 ml solution) under similar storage conditions H2O and O at 500 K.c. It was found.34 mL oxygen.5 mm Hg.8 rotation was found to be 2. Find how long the peroxide can at 500 K and Ea = 77 kJ mol–1.2 +9. Chem i str y  18. be 284. After 10 and 20 4 2 2 minutes respectively the volumes of permanganate required were 13. pressure of system is 176 mm Hg and after a long time [y] + [z] 270 mm Hg. however.46 How much time would be required for B to reach the reaction.0 +5.314 kJ/ mol respectively find the temperature at (b) Calculate the time required for the decomposition which B and C will be obtained in molar ratio of 2:1.93 minutes and rotation optical rotation was –5° after infinite time. k maximum concentration for the reaction A →B 1 k Q.5 mm Hg. How may the result be 2 min–1 respectively at 300 K.40 The decomposition of N2O5 according to the k1 = x hr–1.An experiment with 100 ml of a the upper atmosphere. then calculate Ea for the be stored before the loss of 20. Calculate the rate constant of Q. . if complete decomposition of the H2O2sample gave 46. After 30 min.38 The following data were obtained in experiment Q. of standard ln2 ln2 Given k1 = k = permanganate solution for titration.8 and 8. that the hydrogen peroxide decomposed on the wall of the vessel Q. After what time would you expect a zero reading in polarimeter? Q.48 In gaseous reactions important for understanding (a first order reaction) . Q.The species A.42 Hydrogen peroxide solution was stored in a mild [Given: ln4 = 1.45 A the reaction? k2 C [C] Q.31 ml oxygen (corrected to 1 atm & to form two OH radicals. 30° and – 40° (minute) respectively.6 +10. the total pressure is 584. to be half completed. decomposition required 22.1 days.1 +11.44 For a reaction k1 y x Q. On starting with pure A it is found that at the end of 10 minutes the total [x]t Calculate value of ratio. Assuming only A was closed vessel the total pressure developed is found to present in the beginning. B and C are Time 0 60 120 1805 360 ∞ optically active with specific rotations 20°. Starting with pure A if the value of optical Angle of +13.87 –3.c.45 Q.47 For first order parallel reaction k1 and k2 are 8 and (a) Find order of reaction. from start of decomposition in a from the start of the reaction.4] steel vessel.8 c. If the activation energies explained? for the formation of B and C are respectively 20 and 28.
the Q.57 Reaction between NO and O2 to form NO2 is 2NO + O2 → 2NO2 follows the following mechanism (C) Diminish to oneeight of its initial value K (D) Increase to eight times of its initial value NO + NO N2O2 (in rapid equilibrium) 1 k −1 N2O2 + O2 Q.52 A catalyst lowers the activation energy for a certain reaction from 75 kJ to 25 kJ mol–1.56 For the reaction 2H2 + 2NO → N2 + 2H2O. What will be (e) If it is known that ultraviolet light causes the reaction the effect on the rate of reaction at 25°C after things of H2 and I2 to proceed at 200°C with the same rate law being equal? expression. 4 6  Chemical Kinetics Q. The presence of catalyst lower –1 Show that the rate of reaction is given by = K [NO]2[O2] 2 dt the activation energy of both (forward and reverse) .1 The rate of a reaction is expressed in different ways decomposition of H2O2 is 360 min.53 Given that the temperature coefficient for the saponification of ethyl acetate by NaOH is 1. is supposed to The reaction is: follow the following mechanism fast (A) 4A + B → 2C + 3D (i) NO + Br2 NOBr2 (B) B + 3D → 4A + 2C slow (ii) NOBr2 + NO → 2NOBr (C) A + B → C + D Suggest the rate law expression. will the reaction following mechanisms: have a halflife of 1 minute? (a) H2 + I2 → 2HI (one step) Q. (A) Increase to four times of its initial value (B) Diminish to onefourth of its initial value Q.75. (c) I2 → 2I Q. Single Correct Choice Type Q.58 Deduce rate law expressions for the conversion of is 104.5 kJ mole–1 and pre . which of these mechanisms becomes most improbable? Q.2 For the reaction system following mechanism has been suggested 2NO → N2O2 equilibrium constant K1 (fast) 2NO (g) + O2 (g) → 2NO2(g) volume is suddenly k2 reduced to half of its value by increasing the pressure N2O2 + H2 → N2O + H2O (slow) k on it.54 At 380°C the halflife period for the first order Q. (d) Can the observed rate law expression rate = k[H2][I2] distinguish among these mechanisms? Q. Calculate activation energy for the saponification of Exercise 2 ethyl acetate. If the reaction is first order with respect to O2 and N2O + H2 → H2 + H2O (fast) 3 second order with respect to NO the reaction rate will Establish the rate law for given reaction.50 The specific rate constant for a reaction increases (b) I2 → 2I by a factor of 4. If the temperature is changed from 27°C 2I + H2 → 2HI (slow) to 47°C. Calculate the time required for 75% decomposition at 450°C. At what temperature.1 8 . Determine the temperature at which half life of the reaction is 2 hours. Find the activation energy for the reaction. (D) B + D → A +C Q. 1 d[C] 1 d[D] 1 d[A] d[B] + =– = + =– 2 dt 3 dt 4 dt dt Q.3 The energies of activation for forward and reverse → 2NO2 (slow) k2 reactions for A2 + B2 2AB are 180 kJ mol–1 and 1 d[NO2 ] 200 kJmol respectively.exponential factor (A) is H2 and I2 to HI at 400°C corresponding to each of the 5 × 1011 sec–1.49 The energy of activation of a first order reaction Q.51 The energy of activation and specific rate I + H2 → IH2 constant for a first order reaction at 25°C are 100 kJ/ IH2 + I → 2HI (slow) mole and 3.55 The reaction 2NO + Br2 → 2NOBr.46 × 10–3 sec–1 respectively. The energy of as follows: activation of the reaction is 200 kJ mol–1.
graph between solution was titrated against 37.7 For the first order decomposition of SO2Cl2(g).x) [A(g) → B(g)] 2 (A) (B) d[B] 3 [B] dt (A) 0.036 M min–1 Q. 25 mL of this diluted Q.3 a Q. t1/2 t1/4 A solution of H2O2 labelled as “16.5 mL of 0.5 Consider the reaction A → B.60 (D) 1.6 The reactions of higher order are rare because (C) 0.303 hours. some H2O2 decomposed.6 Experiment2 dt dt 5 10 15 20 time (min) t t (A) 0.30 (C) 0.8 V” was left open due to this. The most suitable (D) Many body collisions can take place only in the qualitative plot of potential energy (PE. The Hence graph between – and time will be dt reaction is represented as A (aq) → B(aq). coordinate for the above reaction.6 × 10–1 t t (C) 7. (B) Many body collisions have a very low probability fast k k A+B IAB → AB+I 1 2→ P+A (C)Many body collisions are not energetically favoured If k1 is much smaller than k2.8 Experiment1 d[A] d[A] 0.8 M? d[A] d[A] dt dt Concentration (M) 1. 0) 2 4 6 8 10 Q. What is the rate constant (sec–1)? (A) 300 (B) 120 (C) 20 (D) –20 Time (min) (0.5 t 1. shown in figure.10 The following mechanism has been proposed for energy the exothermic catalyzed complex reaction.2 (B) 4. The magnitude of enthalpy Q. What is the rate of reaction (M/min) when concentration (A) (B) of A in aqueous solution was 1.2 1 (C) (D) 0.13 M min–1 (D) 1 M min–1 (A) Many body collisions involve very high activation Q.8 Decomposition of H2O2 is a first order reaction.15 × 10–2 (C) (D) Q.) versus reaction gaseous phase. .4 Which graph represents zero order reaction 1 log(a0 . change of the reaction (A2 + B2 → 2AB) in the presence SO2Cl2(g) → SO2(g) + Cl2(g) a graph of log (a0 – x) vs t is of catalyst will be (in kJ mol–1). To determine the [A]0 [A]0 new volume strength after 2.47 reactions by 100 kJ mol–1. The rate constant (in hr–1) for decomposition of H2O2 is: t1/2 (A) 0.02 M KMnO4 halflife (t1/2) and initial concentration (a) of the reaction is solution under acidic conditions [Given: STP is 1 atm and 273 K].9 The variation of concentration of A with time in two experiments starting with two different initial d[A] concentration of A is given in the following graph. 20 mL of this solution was diluted to 100 mL.7 × 10–3 (D) 1. Chem i str y  18.15 (B) 0.08 M min–1 (B) 0.
Based on above information select the true statement (s). If initial concentration of [A] is [A]0. AB+I A+P A+B IAB (E) ∆E for ∆Eoverall ∆E for Eafor E+S→ES for S®P EP→E+P EP→E+P reaction coordinate (C) Multiple Correct Choice Type Q. E. The rate law expression is (A) 2 (B) 1 (C) 0 (D) 3 d[A] – = k[A]1/2.12 Choose the correct set of indentifications. If the second step is the rate determining step. 15 ml is required to reach end point Q.E. then dt Q. 2 (A) The integrated rate expression is k= (A1/2 − A1/2 ) t 0 Potential energy (B) The graph of A vs t will be K (4) (C) The halflife period t1/2 = (1) (2) (3) 2[A]1/2 0 (D) The time taken for 75% completion of reaction reaction coordinate [A]0 t3/4 = k t1/2 a .1 8 . E+S→ES ES→EP for S®P EP→E+P A+B A+P IAB (B) Ea for ∆E for Ea for ∆Eoverall AB+I E+S→ES E+S→ES ES→EP for S®P reaction coordinate (B) (C) Ea for Ea for ∆Eoverall ∆E for ES→EP EP→E+P for S®P EP→E+P (D) Ea for Ea for Ea for ∆Eoverall E+S→ES ES→EP EP→E+P for S®P P.11 The following mechanism has been proposed for (C) An industry is manufacturing H2SO4 at the rate of the reaction of NO with Br2 to form NOBr 980 kg per day with the use of SO3 in air it should use NO(g) + Br2(g) NOBr2(g) 8 × 105 litre air/day NOBr2(g) + NO(g) → 2NOBr(g) (D) If SO3 emission is stopped then after 1000 days its concentrations will reduce to ≈ 1.13 SO3 gas is entering the environment at a constant P. (D) (A) Concentration of SO3 in Kota is 1.2 × 10–3 M.25 × 10–5 M (Assume SO3 present in air reaches steady state) P. A+B AB+I (B) If 103 L of air is passed through 1L pure water IAB A+P (assuming all SO3 to be dissolved in it) & resulting reaction coordinate solution is titrated against 1 N NaOH solution.93 × 10–5 gm/L/day due to the emission of A+B AB+I A+P polluting gases from thermal power plant but at the IAB same time it is decomposing & following first order reaction coordinate kinetics with halflife of 100 days. the order of the reaction with respect to NO(g) is Q. 4 8  Chemical Kinetics (A) (1) (2) (3) (4) (A) ∆E for Ea for ∆Eoverall Ea for P. rate of 6.E.E.14 For the reaction A → B.
B increase with (A) Increase in temperature Q. order with respect to a reactant decreases with the increase in concentration of the reactant. Q. then the (C) Molecularity is defined only for RDS in a complex increase in the rate of backward reaction is more than reaction that of forward reaction on increasing the temperature (D) Decay constant (λ) of radioactive substance is affected by temperature Q.20 StatementI: A fractional order reaction must be (B) The order of reaction with respect to one reactant a complex reaction.93 x 10 min 1 B Q. 1 Q.16 Which of the following statement is incorrect? (D) StatementI is false. statementII is true and (D) After 75% conversion of A in to B and C angle of statementII is NOT the correct explanation for rotation of solution will be 36° statementI (C) StatementI is true.18 In a consecutive reaction system A → B E StatementII: The threshold energy of forward reaction → 2 C when E1 is much greater than E2. Q. k2=13.24 StatementI: The time of completion of reaction of type A → product (B) Decreases in temperature (order < 1) may be determined. statementII is false. 42° and initial concentration of A is 2 M then than concentration of reactants.19 Which of the following is/are correct statement? Q. Q.22 StatementI: The overall rate of a reversible reaction is mol L–1 s–1 reaction may decrease with the increase in temperature. B and C all are optically active compound. Chem i str y  18. statementII is true.17 Select incorrect statement(s) (A) Unit of preexponential factor (A) for second order Q. If optical are identical rotation per unit concentration of A. the yield of is more than that of backward reaction. (C) A zeroorder reaction is controlled by factors other –72°. Q. rate and the rate constant A.49 2 k1=6. is the ratio of the change of logarithm of the rate of the reaction to the change in the logarithm of the StatementII: Fractional order of RDS equals to overall concentration of the particular reactant.23 StatementI: In a reversible endothermic reaction Ea of forward reaction is higher than that of backward E reaction. step reaction may be negative (D) The order of a reaction can only be determined StatementII: The rate of reaction having negative from the stoichiometric equation for the reaction.21 StatementI: Temperature coefficient of a one (C) Orders of reactions cannot be fractional. A (A) Stoichiometry of a reaction tells about the order of C the elementary reaction. concentrations of all other reactants constant.85 x 10 min1 (B) For a zeroorder reaction.15 Consider the reaction. keeping the order of a complex reaction. select write statements(s). (D) A zeroorder reaction is always elementary reaction (A) Solution will be optically active and dextro after very long time Assertion Reasoning Type (B) Solution will be optically active and laevo after very long time (A) S tatementI is true. B and C are 60°. statementII is true and statementII is correct explanation for statementI (C) Half life of reaction is 15 min (B) StatementI is true. (C) Increase in initial concentration of A StatementII: Reactions with order ≥ 1 are either too (D) Decrease in initial concentration of A slow or too fast and hence the time of completion cannot be determined . (A) The order of reaction is the sum of powers of all the concentration terms in the rate equation. (B) A zeroorder reaction must be a complex reaction StatementII: When the activation energy of forward reaction is less than that of backward reaction.
[B]1 = [e −e ] k2 2 (k 2 – k1 ) [C]1 = [A0] – ([A]1 + [B]1) Q. t? time time −n1kt (A) a ⋅ ekt (B) a ⋅ e (C) [C]1 (D) [C]1 −n2kt −n2kt (C) a ⋅ e (D) a(1 − e ) Conc. e–kt) per unit of time.25 StatementI: A catalyst provides an alternative Q. B & C at the end of 50% reaction are Q.28 How many moles of A are present at time. Conc.31 The time at which concentration of B is maximum is (A) 2 (B) 3 (C) 4 (D) 5 k1 k 1 (A) (B) ln 1 k 2 − k1 k 2 − k1 k 2 Q. B & C at anytime ‘t’ is given by k2 C k1 1 k1 [A]0 −k1t −k 2t where = .33 1 k k2 (C) ln 1 (D) k1 − k 2 k 2 k 2 − k1 Paragraph 2 The gaseous reaction: n1 A(g) → n2B (g) is first order Q.32 Select the correct option if k1 = 1000s–1 and with respect to A. Conc.e–kt (B) [A0 ] StatementII: The catalyst forms an activated complex 2 − e−kt of lower potential energy with the reactants by which e−kt more number of molecules are able to cross the barrier (C) [A0 ] (D) [A0](1 – 2 . the moles of A were ‘a’ and no B (A) [C]1 (B) [C]1 were present.666 (D) 0. k. A particular type of oxidation n involve overall first order kinetics with respect to fraction n −n kt (C) v 0 2 + 1 − 2 ⋅ e 1 of unoxidised metal (1 – ƒ) surface thickness relative to n1 n1 maximum thickness (T) of oxidised surface.30 What will be the concentration of A at time t. when metal surface is exposed to air for considerable period of time n n −n kt (D) v 0 2 + 2 – 1 ⋅ e 2 Rate law: = k(1 – ƒ). The true rate constant of reaction is k2 = 20s–1. if path to the reaction in which conversion of reaction n1 = 1 and n2 = 2 ? into products takes place quickly e−kt (A) [A0] . [A]1 = [A]0e–kt . where f = x/T. These steps involve n1 electron transfer reactions. 1 − e−kt Paragraph 3 Comprehension Type For the reaction sequential reaction Paragraph 1 k k k1 B A → B 1 2→ C For a hypothetical elementary reaction A the concentration of A. The reaction is studied at a constant pressure and temperature.26 The total number of moles of A.27 Number of moles of B are (A) 2 (B) 1 (C) 0.29 If the initial volume of system were v 0° then the [B]1 [A]1 [A]1 volume of system after time t will be time time n1 v 0 (A) n2 Paragraph 4 n2 v 0 Oxidation of metals is generally a slow electrochemical (B) reaction involving many steps.1 8 . Initially. [B]1 [A]1 [B]1 [A]1 Q. n1 n1 . Initially only 2 moles of A is present. Conc. 5 0  Chemical Kinetics Q. [B]1 Q.
5 litre vessel initially.34 The exponential variation of ‘f' with t(hrs) is given by (A) [1 – e–3t/200] (B) e–3t/200–1 (B) [A] vs t for first (q) (C) e–3t/200 (D) e3t/200 order Paragraph 5 A reaction is said to be first order if it's rate is proportional to the concentration of reactant. Q.66 min columnII and vice versa.66 min (D) 156.04 M (B) 0. Entry of column I are to be matched with A graph of ln( 1 – ƒ) vs t is 3 only one entry of column II shown inthe adjacent figure.38 ColumnI and columnII. Chem i str y  18. Entry of columnI are decompose? Given: log 2 = 0. t(xaxis) Q.1 hrs (B) 46. if reaction is allowed to takes place at constant pressure & at 298 K then find the concentration of B after 100 min. In(1) Column I Column II Q.09 M (D) None of these . How long will it take for 90% of the compound to Q.36 M (C) 0.If 75% of X is decomposed in 100 min.2hrs (A) vs dt dt (C) 100 hrs (D) 92.66 min ColumnI (Graphs ColumnII (Coordinates) reaction A → Products) (A) (p) ln [A] (yaxis).30 to be matched with one or more than one entries of (A) 190 min (B) 176.37 For the reaction of type A(g) → 2B(g) T = thickness of oxide film at Column I contains four entries and column II contains t=∞ four entries. Let us consider a reaction A(g) B(g) + C(g) (C) [B] vs t for first (r) order At t = 0 a 0 0 At time t ax x x dx The rate of reaction is govern by the expression dt = k(a – x) and integrated rate equation for a given reaction is represented as (D) [A] vs t for zero (s) a order 1 k= ln a − x where a = initial concentration and t (a – x) = concentration of A after time t. Starting with 2 moles of A in 12. (A) 0.35 Thermal decomposition of compound X is a first order reaction .386 × 10–2 min–1.36 Consider a reaction A(g) 3B(g) + 2C(g) with (order = 1) rate constant 1. (C) 166.33 The time taken for thickness to grow 50% of T is (p) d[B] −d[A] (A) 23.51 x = thickness of oxide film at 200 hrs Match the Columns 0 t time ‘t' and Q.4 hrs for first order Q.
3 If I is the intensity of absorbed light and C is the 0. (Q. 5 2  Chemical Kinetics Q. 7). The plot that follows Arrhenius equation is (2010) (A) (B) (D) (s) r(yaxis).4 Which one of the following statements is incorrect (B) (q) t1/2(yaxis). [A](xaxis)(order = 1) Previous Years’ Questions T T Comprehension (Q. ceases to be accurate over periods longer than 30. t(xaxis)(order = 0) (t) t 1/2(yaxis).5 Plots showing the variation of the rate constant (k) with temperature (T) are given below. falls due to the decay which C–14 14 14 (B) Changes the equilibrium constant of the reaction undergoes 6 C →7 N + β– (C) Shortens the time to reach equilibrium The halflife period of 14C is 5770 yr. (Q.1 8 .6). (2006) . [A0] (xaxis) (order K K > 1) 1 T T (u) (yaxis). the uptake (A) Increases the equilibrium concentration of the of carbon dioxide by it ceases and the level of 14C in product the dead being. (B) Initial concentration of the reactants 14 14 (C) Time of reaction 7 N +0 n1 →6 C +1 p1 (D) Extent of reaction 14 C is absorbed by living organisms during photosynthesis.2 A catalyst is a substance which (1983) organism once the plant or animal dies.I material from the living cycle. The 14C content is constant in living Q. t(xaxis)(order > 0) the reactants (D) Order cannot be fractional Q.8) Q. t(xaxis) [A] (C) (D) (order = 2) K K (v) r (yaxis).1 The rate constant of a reaction depends on(1981) Carbon14 is used to determine the age of organic (A) Temperature material. The procedure is based on the formation of 14 C by neutron capture in the upper atmosphere.000 yr. t1/2 AB + hv → AB*. The proportion of 14C to 12C in living matter is 1: 1012. (D) Supplies energy to the reaction The decay constant (λ) can be calculated by using the following formula Q. the rate of formation of AB* is directly The comparison of the β– activity of the dead matter proportional to (2001) with that of the carbon still in circulation enables measurement of the period of the isolation of the (A) C (B) I (C) I2 (D) C. [A0] (xaxis) about order of reaction? (2005) (order = 1) (A) Order of reaction is determined experimentally (B) Order of reaction is equal to sum of the power of concentration terms in differential rate law (C) It is not affected with stoichiometric coefficient of (C) (r) r(yaxis). The method however.693 λ= concentration of AB for the photochemical process.
75 0. equal to the rate of radioactive decay. Evaluate the Arrhenius concentration is C1 in nearby areas and C2 in areas far parameters A and Ea. Calculate (2005) (A) Order of reaction Q. when concentration of G is doubled keeping the Q.40 0.909 h. circulation of 14C from h. (B) The age of fossil will decrease at the place where 1 C Q.53 Q. What is the total pressure of the system after (D) It can be used to calculate any age 12 min? Assume ideal gas behaviour. Radioactive concentration of H fixed.6 Which of the following option is correct? Q.8 A nuclear explosion has taken place leading to Q. Find the minimum amount of 42Mo99 required to carry out the experiment in 6.5 × 107 s–1 at increase in concentration of C14 in nearby areas. However. hence the The halflife period of 42Mo99 which is a beta emitter is carbon content remains constant in living organisms 66.5 × 10–6 per second at 200° C. the rate is doubled.15 2X(g) → 3Y(g) + 2Z(g) explosion has taken place and T1 – T2 = ln 1 λ C2 Time (in min) 0 100 200 (C) The age of fossil will be determined to be the same Partial pressure of X (in mm of Hg) 800 400 200 T1 C1 (D) = T2 C2 Assuming ideal gas condition. the rate increases by eight times. C14 50° C and 4.9 The concentration of R in the reaction (B) Rate constant R → P was measured as a function of time and the (C) Time taken for 75% completion of reaction.05 0. The carbon in wood sample decays with a halflife of 5770 yr.6 h. When concentration of both the reactants G and H is The order of the reaction is (2010) doubled.14 (a) The rate constant of a reaction is 1.40 atm. Chem i str y  18. (1989) (D) Carbon dating cannot be used to determine concentration of 14C in dead beings. what percentage of the initial concentration would atmosphere is high so the carbon content is have change in the product? What is the halflife of this constant in organism reaction? (1987) (B) Carbon dating can be used to find out the age of earth crust and rocks Q.16 Consider a reaction aG + bH → Products. (1998) 1 away. Q. following data obtained: (D) Total pressure when px = 700 mm [R] (molar) 1.000 yr 0. If the age of the fossil is determined to be T1 and (b) For the reaction. if the initial pressure 1 C is 600 mm Hg and the pressure at any time is 960 mm explosion has taken place and T1 – T2 = ln 1 λ C2 Hg.10 t (min) 0. If the reaction is allowed to run for 10 (A) In living organisms.5 min. Assume ideal gas behaviour.7 What should be the age of fossil for meaningful determination of its age? CH3–O–CH3(g) → CH4(g)+ H2(g)+CO(g) (A) 6 yr The reaction is carried out in a constant volume container at 500°C and has a halflife of 14.12 An experiment requires minimum beta activity (C) Radioactive absorption due to cosmic radiation is produced at the rate of 346 beta particles per minute.0 0.0 0.13 The gas phase decomposition of dimethyl ether follows first order kinetics Q.12 0. (B) 6000 yr Initially only dimethyl ether is present at a pressure of (C) 60. (1993) Q. overall order of the reaction is (2007) What is the rate constant (in yr–1) for the decay? What fraction would remain after 11540 yr? (1984) (A) 0 (B) 1 (C) 2 (D) 3 .10 Radioactive decay is a first order process. N2O5 (g) → 2NO2 (g) + O2 (g) T2 at the places respectively then 2 calculate the mole fraction N2O5(g) decomposed at a (A) The age of fossil will increase at the place where constant volume and temperature.11 A first order gas reaction has A’ = 1.18 Q.5 × 107 s–1 at 100°C.
1 8 .3) (2013) Q.36 Q. 50% reaction of P. initial concentration of 1.5 mol1 dm3 (B) 1.34 Q.19 Q.20 For the elementary reaction M → N. stronger is the temperature dependence of the rate constant (D) The preexponential factor is a measure of the rate at which collisions occur. The time taken for its decomposition reaction with respect to M is (2014) to 1/8 and 1/10 of its initial concentration are t1/8 and [t ] (A) 4 (B) 3 (C) 2 (D) 1 t1/10 respectively. The concentration of Q varies with This is due to a greater number of collisions whose reaction time as shown in the figure. The overall order energy exceeds the activation energy of the reaction is (2013) (C) Higher the magnitude of activation energy.12 Q.15 Q.386 mol dm3 of a substance [Q]0 becomes half in 40 seconds and 20 seconds through [Q] first order and zero order kinetics.12 Q. the rate of disappearance of M increases by a factor of 8 upon Q.9 Q.9 Q.8 Q.20 Q.33 Q.37 Previous Years’ Questions Previous Years’ Questions Q. P + Q → R + S the time reaction taken for 75% reaction of P is twice the time taken for (B) Rate constant increases with increase in temperature.10 Q. What is the value of 1/8 × 10? (take [t1/10 ] log102=0.12 Q. irrespective of their energy.18 An organic compound undergoes firstorder doubling the concentration of M.0 mol dm3 (A) 2 (B) 3 (C) 0 (D) 1 (C) 1.2 Q.15 . (2015) (A) A high activation energy usually implies a fast Q.9 Q.14 Q.21 According to the Arrhenius equation.19 In the reaction.28 Q.17 Under the same reaction conditions. respectively.24 Q.0 mol1 dm3 Q.5 mol dm3 (D) 2. PlancEssential Questions JEE Main/Boards JEE Advanced/Boards Exercise 1 Exercise 1 Q.58(e) Exercise 2 Exercise 2 Q.4 Q.29 Q.7 Q.16 Q. The order of the decomposition.43 Q. Ratio 1 k1 of the rate constants for first order (k1) and zero k0 order (k0) of the reactions is (2008) Time (A) 0.1 Q.7 Q. 5 4  Chemical Kinetics Q.
495 × 10–3 mol–1 l–1 s–1 Q.4 D Q.6 C Q.21 C Q.10 D Q.0025 m Q.11 A Q.29 Rate = 2 × 10–4 mol dm–3 min–1 x = 18.7 C Q.1 (a) 6.17 C Q.3 P1 = 379.3 A Q.13 4.22 D Previous Years' Questions Q.21 161 minutes Q.13 C Q.0805 Q.537 Q.55 Answer Key JEE Main/Boards d(D) k1k 3 (A)(B) Q.30 k = 0.18 C Q.2 C Q.55 × 10–4 sec–1.15 Er=6 × 104 J.33 kJ mole–1 Q.022 hr–1 Q.96 min Q.12% E1k1 + E2k 2 Q.13 week Q.26: 1 E = 43.17 E= k1 + k 2 Exercise 2 Single Correct Choice Type Q.26 2 Q.3 × 104 J (b) = 5.1 A Q.15 B Q.8 C Q.13 D Q.2 A Q.21 % k = 8.83 mins A = 5.46 kJ mol–1 (b) 20.17 D Q.5 D Q.16 A Q.07 min Q.3.7 20 min K47 = 11.20 B Q.78 kJ/mol Q.11 D Q.27 Ea = 2.9 A Q. (b) 14.55 mmHg.22 A Q.18 (a) = dt k 2 + k3 Exercise 1 A1 A3 (b) Ea = Ea1 + Ea3 – Ea2 A = Q.12 C Q.24 K27 = 3.85 × 10–4 sec–1 Q.23 Rate = K(A][13]2 rate will became 8 times Q.12 D Q.6 15.5 k = 0.21 B Q.25 .11 k = 0 0327 min–1 Q.20 0.2 × 104 Q.15 B Q.42 × 1010 Q.1 B Q. (c) 0 % A2 Q.5 D Q.47 hour Q.14 0.12 0.24 A .14 A Q.28 (a) = 1 × 10–2 mol l–1 s–1 Q. t7/n = 399.14 D Q. Q.0207 min–1 Q.16 B Q.64 × 10–1 Q. Chem i str y  18.22 55.18 C Q.20 B Q.4 0.25 It is first order kinetics with Q.19 B Q.10 D Q.6 D Q.16 a = b= 1 Q.9 C Q.8 B Q. Eb = 9.23 D Q.9 (a) 43.4 A Q.7 B Q.3 C Q.10 % decomposition = 67.2 2 × 10–2 min–1 Q.02231 min–1 t = 62.19 D Q.8 0.
r.29 Zero order (ii) Rate increases by 8 times 1 P3 Q.2 (i) 7. (ii) 10 M Q. Exercise 1 (c) 8.19 924.677 min.362 sec Q.39 (a) 90 mm.019 mol L s .40 k1 =2. (b) 47 mm. (iii) 54 × 10–4 mol litre–1 sec–1 (d) Rate = 0.2 mol litre–1 min–1 (ii) k = 1.21 3. Q.012 atm min–1 Q.3 (a) 1 × 10–4 mol L–1 s–1.9 2.45 days Q.037 mol L–1 s–1 1 V1 Q.23 × 10–6 Ms–1. –1 –1 t (P3 − P2 ) (b) 0.2% Q.6 Rate increases by 27 times 1 P3 Q.5 7.33 k = ln Q.22 k = log t a Q.r.75 minutes.23 11. Q.8 2k1= k2 = 4k3 1 4V3 Q.7 (a) 0.256 mole L–1 s–1 Q.1 min–1 .3 × 10–4 s–1 (c) 0. (ii) 36 × 10–4 mol litre–1 sec–1 (c) K = 8 L2 mol–2s–1.303 1 Q. 0.75 M Q.24 15 min Q.308 × 10–2 min–1 Q. Q. NO = 2 and w.t. (b) 13.30 k = ln t 2(P3 − P2 ) Q.25 (a) Third order.36 (i) r = K[(CH3)2O]2 0.15 1.2 M.27 (i) First order (ii) 7.01 M min –1 Q.49 × 10–2 per minutes.11 (i) 7. 47.605 × 10–3 min–1 Q.35 First order Q.12 K= 0.10 1/6 1 r Q.41 (a) first order. (ii) 62.1 (i) r= = 9 × 10–4 mol litre–1 sec–1 Q.2 hr Q.716 0. 5 6  Chemical Kinetics JEE Advanced/Boards Q.85 ×10–3 M sec–1 1 d[NO] Q.32 k = ln t (2V1 − V2 ) Q.28 (i) Zero order.4 (i) = k [A][B]2 dt Q.0223 min .42 11. Cl2 = 1.37 First order Q.180 atm.26 (a) Order w. 4 dt (b) r = K[NO]2[Cl2].20 Expiry time = 41 months Q. (ii) K = 5 Pa/s Q.34 k = ln ∞ t (r∞ − r1 ) Q.72 × 10 sec 18 t 5(V3 − V2 ) Q. (iii) 73% (b) 3 × 10 mol L s –4 –1 –1 dx Q.13 0.43 0. (b) r = k[NO]2[H2].17 min –1 (d) 10.t.000428 sec–1 Q.1 8 .2 mol litre min .38 966 min Q. Q.17 (i) 0.31 k = ln Q.69 sec 2.16 (i) 36 min (ii) 108 min (c) 6. –1 –1 Q.14 6 × 10–9 sec Q.
81 × 108 times [C] 10 11x Q.23 C Q.25 A Q.57 r = K[NO]2 [H2].25 Q.37 A → s.52 Rate of reaction increases 5.B.2 D Q.38 A → p.54 t=20. D Q. D → v Previous Years’ Questions Q.46 t = 4 min Q.757 k cal mol–1 Q. s.17 A Q.30 B Q.4 D Q.D Q. 0.8 A Q.16 C.12 3.36 B Match the Columns Q. C → r.9 A Q.57 1 Q.31 C Q.53 10. D Q. C Q. D Q.27 C Q.24 C Q. C.1 K Q. B → r.2 C Q.51 306 K Q. C.29 D Q.20 C Q. (e) mechanism (a) is incorrect Q. Chem i str y  18.34 A Q. D . C → p.55 r = K’ [NO]2 [Br2] Q.1 A Q.14 A.44 e (K1 +K2 ) t −1 Q.35 C Q.10 0.5 A Q.18 A.13 A. B. D → q Q.16 D Q.45 = (e – 1) [A] 11 Q. t.5 C Q.33h Q.20 C Q.33 B Q.17 A.10 A Q.33 kJ mole –1 Exercise 2 Single Correct Choice Type Q.47 0379. where K=k2 × K1/k1 Q.7 B Q.1 B Q.12 B Multiple Correct Choice Type Q. C Comprehension Type Q.50 55.375 Q.4 minutes 56.8 C Q.26 B Q.49 349.28 B Q.75 atm Q.13 0.56x10–16 Q.3 D Q.56 k = k'2 Q.18 9 Q.7 C Q.15 (a) 1 (b) 693x103 min1 (c) 200 min (d) 950 mm Q.32 C Q.22 A Q. D Q.19 A.6 B Q.6 A Q. 2000 K Q.48 5 kJ mol–1 Q.58 (d) No.15x103 s–1.19 D Q.15 A.14 4.4 D Q.21 D Q.11 128. B → q.21 B.3 C Q.75 K Q.11 A Q.9 0 Q.
we know 100 A left is % or 14. 1/2 . [A] = [A] = 0. 4 [A0 ] – [A0] = –k (b) Here. at time t = 1 hour [A] = 6. 99[A0] = [A0] e–k. Sol 1: (a) A + B → C −1 1 3 −6 + = –2 × = We have. ⇒ [A] – [A0] = –kt [A] 1 = e–2×ln 4 = ⇒ [A] = [A0]kt [A0 ] 16 Now. 2 [A0 ] At time t = 1 hour. if t or [A] = 0 Since the initial concentration of A and B is the same and they have the same coefficient. k 3 −d[A] The reactions will be finished before 2 hours and 6 % of = k[A] 2 A will be left after 2 hours. their concentration [A0 ] 4 t= = hours < 2 hours will remain same at any time. first order in A and 0 order in B. 75. 25% of A will be left unreacted. reaction is first order in both A and B 4 3 d[A] ⇒k= [A ] ∴Rate = = k[A] [B] 4 0 dt We see that. 5 8  Chemical Kinetics Solutions JEE Main/Boards 3 ⇒k= [A0 ] Exercise 1 Now. 25 % of A0 [A0 ] [A] = ∴6. 99[A0] 4 4 1 (1 % of nitroethane reacted) ∴− + = –k [A0 ] [A0 ] ∴0. at t = 1 hour (c) If the reaction is 0 order 75% of A reacted d[A] 1 Rate = =k [A] = A0 – 0. at time t = 2 hours. dt [A] t − d[A] ⇒ ∫ = ∫ −kdt Sol 2: CH3CH2NO2 + OH– → CH3 CHNO2 + H2O 2 [A0 ] [A] 0 (A) Since this is a first order reaction 1 1 [A] = [A0] e–kt ⇒− + = –k(t – 0) = kt [A] [A0 ] 1 Now.1 8 . A = A0 dt 4 [A] t 1 ⇒ ∫ d[A] = ∫ k dt [A ] = [A0] e–kt ⇒ k = ln 4 4 0 [A0 ] 0 Now t = 2 hour. [A] [A0 ] [A0 ] [A0 ] −d[A] −d[A] 1 7 [A] 1 Rate = = k[A] 1[B] 0 = = – k[A] ⇒ = ⇒ = dt dt [A] [A0 ] [A0 ] 7 For first order reaction. 3 % [A] = [A0] e–kt 7 We have. we have at time t = minute.
for volume V of Bn+ + B(n+4). the reaction as. for titration we have At time. For titration of B(n–1)+. let initial pressure 8 P of P(g) be P0 mm Hg.(i) Now. 55 mm Hg as the liquid begins to form. P∆ = 0 8 P0 2. 22 ⇒ −k = loge(0.303 2P(g) → 4Q(g) + R(g) + S() Using rate law. 5 …….2×10 –3 ×75 2. 5P0 at time t = 0.8 x = 16. Chem i str y  18.303 233. 02 min–1 Pt = P0 + 3x + 32. Now. we have ⇒3x = 32 – 25 2. 99) 2 233. at t = 75 min. at t = 30 min a = 233. since the volume of liquid is negligible and Pt = 379. 8 + (3 × 37. 5 2 ⇒ 2V0 = 25 mL ⇒ P0 = 233. 5 k = 2 × 10–2 min–1 = 233. 303 Now. 8 mm Hg ⇒ V0 =12. total time ∴P0 – 2x + 4x + x + 32. 8 B(n+4)+ + 5e → B(n–1) ⇒ x = 16.8 − (2 × 16. 9 i.303 12. 5V volume of titrant is Now. ie. 5 = 617 2 of titrant is used. 5 mm Hg. since this is first order reaction. = P0e –kt ⇒ t = log 8 8 R at time t = 399. rate law is –5. pressure due to liquid will 7 Time fraction. 78) + 32. 5 – 233. Pt = 317 mm Hg at t=30 min. 78 ⇒ = 0. t = ∞ (very long time).303 P 2.8 Volume of titrant used = 32 mL k= log 0 = log t Pp 30 233. we get. 8 × 10 2. we have used. 2 2 Now.5 = 233. then according to stoichiometry completed. 2V volume ∴2P0 + + 32. total pressure at t = 75 min ⇒ k = 0. t7/8 is time at which th of reaction gets always be equal to 32. since this is a first order reaction. 5 At time t = 0 V0 0 2 Now. 96 min.9 ∴ At time t = 10 min.303 k= log 0 = log t V n+ 10 12.9) ⇒ 2(V0 – x) + 5x = 32 ⇒ k = 5. 5 Bn+ → B(n2)+ + 4e t = ∞ 0 2P0 P0 32. we see that for volume V0 of Bn+. 01 min.22 −k ⇒x= = 37. 5 = 317 t = 10 min V0 – x x ⇒ P0 + 3x = 284.8 − 158.59 ⇒ P0 – 2x = 158. t = 0 min P0 0 0 0 Sol 4: We have. we are given. 5 Sol 3: Here.2 × 10–3 min–1 ⇒ 2V0 + 3x = 32 Now. 22 m Hg . 5 mL Putting this in (i).5 − x B Pt = 158. we have 3x = 284.303 P k= log 0 7 t Pp ⇒x= 3 ⇒ Pt = P0 × 10–kt/2.e.303 V 2. 2. Pt = 617 mm Hg Bn+ + 2e → B(n–2)+ P0 From this. t = 30 min P0 – 2x 4x x 32. volume of titrant used = 25 mL ⇒ = 584.
0207 min–1 k= log 10 7 6 3.303 12. 10 mL of solution be diluted to 100 mL.956 = log . ⇒ x = 0. law. t = 6 hours.693 20 t1/2 = + τ = thickness at time t 2. 1 N 100 ⇒ 60 × 0. 022 hr–1 t N 6 3. as N is proportional to number of moles of H2O2 2. 75 N total optical rotation 5.956 – 2.303 N t θt − θ∞ k= log 0 = 2. 13 weeks Now.303 log 3. 13 weeks weight Then.481 Now.693 0.303 θ0 − θ∞ 2. τ = inch. Eq. k = 0. 5 = 30º Now.125 q0 = initial optical rotation Sol 6: We have for oxide film formation. 13 weeks Let normality of H2O2 = N longer = 9. when.303 (30 − 1 − 20) log (5 − 1 − 20) We are given since θ = 5º 3. we have According to reaction 1000 2.57 . optical rotation at t = 0 N. 065= log H2O2 → H2O + O t 3.1 8 .2 × 17N A →B + C \ 17 N g of H2O2 gives of O2 34 At t = 0 x 0 0 11. 20 ⇒ N0 = = 3. 6 0  Chemical Kinetics 2. 21 of O2 Let initially x moles of A be present H + 11.5 2.281 t1/2 = 20 min τ= inch. initially volume strength = 20 respectively at completion. at t = 6 weeks 1000 . volume strength is the volume of O2 given by unit volume of H2O2 t = 15. let normality be N. according to rate Using first order rate law.303 θ − θ∞ k= log 0 2.2 × 17N At t = ∞ 0 x x Volume strength = = 5.281 12.956 tmax = inch 0.10 Now normality = = 0.693 1 or t1/2 = = + k 2. since this is first order reaction. 11.065 t = 15.303 τ log k= log max θt − θ∞ 6 τmax − τ Putting values Where. k = 0.303 3. N = Sol 7: We have.49 at STP 2 0.3 × 20 1000 at t = 20 min = log2 1. 6 N 34 We know optical rotation of B and C are 40º and –80º Now.303 1 mole (34g) of H2O2 gives moles of O2 i. 065 Sol 5: We have initially. 21 ⇒t= × 0. 34 g of H2O2 gives 11. tmax = maximum thickness of oxide film (at t → ∞) 0.6 ⇒ 40x – 80x = 10 At time.303 3. e. weight H + ⇒ Weight = 17 N (equivalent weight = 17) A →B + C Now.956 – 1. volume strength = 20 2. Now.5 − 3 k = 0.481 2 2 1 2. 5 Since. 0.956 1 0.
= 4 2 P+x+x+x+x EA = 70 ks mol–1 0. Chem i str y  18. mean molecular mass. 055 min–1 k1 [A] = [A0] e–0. 4–x x x x k1 303 × 8. 0.29 + 0. 11 ⇒ x = 0. 3279 [A0] ∴ 67.20 ∴ = e 1 k2 EA 1 1 4 log = − k1 2.303 T1 T2 ⇒ k1 = 0.77 0.4 According to rate law = = × Dt Pt M1 46 0.11 + 0. T2 = (273 + 3)K = 276 K k = 0. t = 20 min. at t = 4. 014 min–1 Here.314 293 313 We are given k = 4.29 + 0. we have ∴ k2 = 3.314 298 313 According to Graham’s law ⇒ k2 = 3.29 × 2 = = 18. 26 Dt 3[A0 ] [A] = 4 Sol 9: (a) According to Arrhenius equation.303 × 8. It is a first order reaction and 1 Further. … t = 20 min. according to Arrhenius equation Now. 21 % of A got decomposed. equation Rate of diffusion ∝ M A→B D0 P0 M2 18.12 ⇒ PA = 0. t=0 0. 98 k1 2.4 = 0. 46 kJ/mol at (b) When T2 = (273 + 40) K = 313K.303 × 8. at T = 313 K.61 Sol 8: Since. M2 k2 EA 1 1 log = − k1 2. 47 hours 0. 77 t1 = (273 + 25) K = 298 K 0. = 0.303 × 8.314 293 276 . we have 3 −k . 4 – x + 3x = 0.303R t1 t2 (P0 − x)MCH + x. volume and temperature is constant. 5 × 60) ∴ = ⇒ t2 = t1 k2 3. 1 EA 1 1 log = − 3 2. 055 × 20 k2 = 3 Putting values [A] = 0. 87 k1 P Now.MCH + MCO + x + M0 + xMH 3OCH3 Here.4 × e(–4. as k ∝ t PA = P0e–kt t2 k1 6.98 [A] = [A0] e–kt D0 At T = 298 K.29 t2 = (273 + 40) K = 313 K at t = 0. 4 – x = 0. molecular mass Putting values M1 = MCH = 46 k2 3OCH3 70000 1 1 log = − Pt = 0.11 t2 = 20. we +(log3 × 2.314 × 293 × 276) ∴ EA = take P ∝ n 17 CH3OCH3(g)→CH4(g)+CO(g)+H2(g) EA = 43. 4 × 2x = 0.29 × 16 + 0. k = k1. 87 k1 = 0.5hr. 055 min–1 T1 = (273 + 20)K = 293 K Now. 78 × 10 –3 × 4. 78 × 10 . 5hr. 29 Sol 10: We have.11 × 46 × 0. 4 0 0 0 k2 43.460 1 1 We have. since unit is –3 ⇒ k2 = 3312 k1 min–1. log = − t = 4.29 × 28 + 0.
A xeq k2 C ln = (kf + kb) t xeq . ⇒ kb = = 2. k 268.303 × 8. = k2[A] k2 EA 1 1 dt log = − k1 2. 537 [A] Further. using Arrhenius equation. k at 300 K is 2 k 2 [A0 ] −(k1 +k 2 )t [C] = (1 − e ) Putting this in equation. according to Arrhenius equation d[C] We have.303R T1 T2 d[C] −(k +k )t ⇒ = k2[A0] e 1 2 dt For. 0625 × 10–4 s–1 0. 3 × 10–1 s–1 kt Sol 12: We are given.693 Time. 71 s ⇒ t = 4. 3 × 10–4 + 2. t1/2 = 30 min k2 = 9k1 = 1.16 k1 B Now using formula for eq. 0327 min–1 and kf = k1 = 3. t = 289. constant = = 0. Now. 0625 × 10–3)t xeq d[A] xeq − ∴ = –(k1 + k2)[A] 2 dt ln 2 ⇒ [A] = [A0] e −(k1 +k 2 )t ⇒t= s 2.02 1 1 kf log = − 0. At 310 K. xeq We have to find t for which x = k1 1 q = .303 × 8.303 × 8. we get We have. 67 kJ/mol Now we are also given at T = 310 K. reactions. 17 × 10–7 s–1 0. for (ii) (EA ) f k EA = = 26. 0231 min–1 t1/2 Putting values. k = 1. 83 min . A → products [C] t If k at 310 K is taken to be k −(k1 +k 2 )t ⇒ ∫ d[C] = k 2 [A0 ]∫ e dt k 0 0 Then. 16 kb k = 0. t = 1 hour = 3600 s ∴ k at 310 K = = 0. both are first order reactions ln = (3. 6 2  Chemical Kinetics Sol 11: We have.0769 2.314 310 300 Eq.[A0 ]e 1 2 log2 × 2. 3 × 10–5 s–1 k2 9 x eq Now. for (ii) B → products [C] 9 1.314 300 310 = 2 0 [A] −(k +k )t (k1 + k 2 ).x Here. we have k1 = 1. 0462 min–1 [C] = 0.1 8 .3×10−4 ×3600 = (e − 1) k = 211 for (i) [A] 10 = 0. for A → C.314 × 310 × 300 ⇒ EA = k2 (k1 +k 2 )t 10 = (e − 1) k1 + k 2 EA = 53.3925 × 10−5 Now. 3 × 10–5 s–1. 802 k J/mol Sol 13: As Cis(en)2(OH)2+ k b 2 transCr(en)2(OH)2+ Therefore. we get k1 + k 2 EA 1 1 k [A ](1 − e 1 2 ) −(k +k )t log 2 = − [C] 2.
008 − x We note that. ∆H = 33 kJ/mol ∴ Taking a = b = 1. 01 mole L–1 31 31 ⇒ Eb = 63 kJ/mol xeq =1 Ef = Eb – 33 0. 57 × 105 ∴a=b=1 Now. k = 5. k for disappearance of A. k′ 1. we are given Ef 20 k = Sol 17: A 1 →B Eb 31 2k Now. RT with T = 300 K. 01)b = k′ + b k[H ] k For forward reaction. 0025 mole L–1 which is true for given data also Sol 15: We have. 5 × 10–3 s–1 4 We see that Now at eq. we have t1/2 = . k′ = k[H+] b xeq Let’s assume that this is Pseudo first order reaction. that is ln = (k1 + k2)t a=1 xeq − x 0. t1/2 x = 0. we have ∆H = ∆E = –33 kJ/mol When [H+] = 0.386 We know. 07 Ef = 30 kJ/mol xeq = 0. 5 × 10 ) × 30 = – 0. [H+] = 0.693 1. At t = 30 s. 02 0. k1 = 10–2 s–1 k2 A B ∆H 10−2 Reaction coordinate → ⇒ k2 = = 2. 02)b = = k. .693 Then. 01 B(g) A(g) 0.693 t1/2 = 1 = = ⇒ (0.386 0. when.t1/2 k −∆Hº ln k = (since ∆S ≈ 0) These both will be satisfied for b = 1. [A] = [A0] – xeq Eb = Ef + ∆H [B] = xeq 20Eb ⇒ But Ef = xeq 31 Then. Now. =4 − xeq [A]e 20Eb 11Eb ∴Eb = + 33 ⇒ = 33 We are given [A] 0 = 0. using equilibrium first order formula. Chem i str y  18.693 0. here t3/4 = 2. we have for this transformation A →C −d[A] We have. (0. = (k1 + k2)t dt ∴ k = k1 + k2 . keq = = Ef Eb k2 [A]eq k1 ⇒ = 4. we know. 008 mole L–1 Now. Sol 16: We have rate k′[complex] a.693 0.008 t3/4 = ln = (12. all the given data can be verified and there are no contradictions we get. 375 –3 k′ 0. A B k 2 k1 [B]eq Energy → Also.01 xeq 5xeq = 0 + 60.63 1 k Sol 14: We have.
k2 k 2 Rate = k 3 [CO] 1 ([Cl2 ])1/2 [Cl] k k −2 k −1 1 A + B C k 2 k1 d[COCl2 ] k 2 k1 C → D = k3 [CO][Cl2 ]3/2 = k[CO] [Cl2] 3/2 dt k −2 k −1 Since second step is RDS. = –k3[C] + k2[A] [B] – k2[C] dt d[C] k [A][B] k1 Now. from equilibrium of (ii). 5 atm Ea = Ea + Ea − Ea Putting values and taking t = ∞. k1 + k 2 we get 1 + Sol 18: (a) We have. Rate = [A] [B] k2 [A] = [A]0 e–kt . 6 4  Chemical Kinetics Using Arrhenius equation. (b) If k2 >> k3.1 8 . then k2 + k3 ~ _ k2 −d[A] Rate = = –(k1 + k2)[A] k1k 3 dt Then. at steady state. R R R k1 [Cl]2 ⇒ Ek = E1k1 + E2k2 = k −1 [Cl2 ] E1k1 + E2k 2 k 1/2 ⇒E= [Cl] = 1 ([Cl2 ])1/2 k k −1 E1k1 + E2k 2 ⇒E= Putting these values back in rate formula. Rate = = k1[A] −EA 2 dt k = A e RT Putting value of [A] and integrating Ea Ea 1 3 −(Ea +Ea −Ea ) A1 e RT A3 e RT 1 3 2 2k1 [A1 ] A1 A3 k= = e RT [B] = (1 − e−kt ) Ea 2 A2 k1 + k 2 A2 e RT k 2 [A]0 −Ea Similarly. 1/2 Rate = k3[C] k 2 k1 k = k3 . k = k1 + k2 Using Arrhenius equation. R = k3[COCl] [Cl2] Ae RT = A1e RT + A2e RT (∵ (iii) is slowest step (RDS)) A = Pre exponential constant Also. we are given [A]0 = 1 atm A= A2 At t → ∞. 1 d[B] Further. −E1 −E2 −E Rate. [C] = (1 − e−kt ) Comparing with k = Ae RT k1 + k 2 A1 A3 Now. we get = T k −2 [CO][Cl] −E −E −E −AE RT −A1E1 RT1 −A2E2 RT2 e = e + e And from equilibrium of (i). d[C] k −2 k 2 Also. 1 k2 [COCl] Differentiating with respect to . = 0 ⇒ [C] = 1 2B(g) dt k3 + k 2 Sol 20: A(g) k1k 3 [A][B] k2 ∴ Rate = C(g) k3 + k 2 We have. we get 1 3 2 . Pt = 1. Sol 19 We have.
Pt = 1. taken at t = 10s. 4 atm (ii) Now rate.303 × 8. t. from Arrhenius equation.R = k[A] [B]2 2 Now. and 0 order w. 0693 min–1 = 11. 10 = (1 − e−k. 5[A]0 ⇒ e–10R = 0.0693 EA 1 1 Sol 22: We have. ⇒ 2k1 + k2 = 1.1) ⇒ EA = k= log 20 t 28. Sol 21: For 50% completion.303 θ − θ∞ k= log 0 EA 1 1 t θt − θ∞ log 4 = − 2. r. second order w. we assume that reaction is first order and k1 see if the data is consistent. 2 2. R′ = k[2A] [2B]2 = 8k[A] [B]2 = 8k k[A]0 ∴ Rate becomes 8 times ∴ [A]0e–k.314 2. 2log2 × 320 × 300 × 2. k = 0. we have Putting values.303R T1 T2 k2 Now.693 10 t1/2 = k k = 0. 5 k1 + k 2 k1 + k 2 (i) Since. log = − 0. 30 [A]t 1 e−10k At T = 27ºC = 300 K.10 ) k k[A]0 Sol 24: We know.55 × 10–4 s–1 0. r.303 ∴k= log2 0. t = 20 min . [A] = 0. 33 kJ mol–1 k = 8.01 T = 320 K. 2[A0] ln = − k1 2. 01 min–1 69. 0231 min–1 ⇒t= 0. 5k2 Rate law = k[A] [B]2[C]0 k ⇒ k1 = k2 = Rate. e. 50% of reaction gets ∴ e–10R + 1 – e–10R + – = 1.85 × 10–4 s–1 k ⇒ k 1 = k2 = = 0.4 − ( −11.65 2k1 k2 Sol 23: 2A + B + C → D + 2E + = 1. time taken 2. 78 kJ/mol k1 2. time taken for 50% completion is 10 min. we find 2. for 80%.10 ) = 1.303 [A] k= log 0 [A]0 = 1. i. B. 14 × 10–3 min–1 At time. C. 16 30 k = 0. t.303 32. 4 2 2 completed.693 Now. t = 10 min. r.314 300 320 k2 Ea 1 1 log = − EA = 43. 5 k1 + 1.1) EA = 55. T2 = 47ºC = 320 K For first order reaction. 08 2 At T = 47ºC=320 K.303 × 8. T1 = 27ºC = 300 K Sol 25: Firstly.0231 2. [A] t = 0. for first order reaction (1 − e−k.303 × 8.314 300 320 At time. A.8 − ( −11. 7 2k 2.303 T1 T2 Using [A] = [A]0e–RT ⇒ 0. Chem i str y  18. at t = 30 min. 0231 min–1 = 3. 0693 min–1 t = 161 min Putting values 0. 2 = e–RT ln5 At T = 300 K. k = 0. t. this is first order w.303 k= log2 ⇒ k = 0. = 4.3 k2 EA 1 1 Now. by Arrhenius equation ⇒k= = 0.
1 ∴ t1/2 ∝ [A]0 Sol 30: (i) At time. t = 30 min = 1 × 10–3 mol sec–1 L–1 2. at t = 50ºC = 323 K. keeping (B) constant Filling the data. we see that when (A) is doubled. 8 × 10–2 × 0. 8 [A]0 Or n – 1 = 1 ∴ 0.5 − ( −11) (i) Initial rate = k[A] 0 k = 8.314 323 373 −Ea Rate becomes 2 times Ea = A e RT ∴ Rate ∝ (B) ∴ Rate = k(A)2 (B) Ea = 2. ∴ Rate ∝ (A) 2 Ea 1 1 log 3 = − Also. it is first order reaction. by Arrhenius equation 1 [A] = [A]0. 8187[A] 0 Here as [A]0 is doubled. [A] = 0. (ii) When 75% reaction is completed. 5 × 10+7 sec–1.1 8 . given data. 2.4 − (11. 2 = 2×10–4 mol min–1 dm–3 1 After 200 minutes.1) We see that all values of k are pretty close to each other. 12 % of reactant converted into product.303 32. Initial rate = k [A]0 = 10–3 × 0. 64 × 10–3 min–1 = 1. Exercise 2 at T = 100ºC = 373 K. Sol 27: We have.214 ×323 rf = 1. 4 k2 Ea 1 1 log = − 1 k1 2.303 (32. k= log = 8. when (B) is doubled. 1 At time. ∴ 18. ⇒ t = 63. 022 min–1 Hence.1) = 5. 71 × 10–3 min–1 40 19. ∴ The reaction is first order. k = 4. 495 × 10–3 mol sec–1 L–1 k= log = 8. 6 6  Chemical Kinetics 2. 01 min. ri = k(A) n[B] m m +Ea B k 2n ⇒ A = ke RT rf = k[2A] n = [A] n [B] m 2. keeping (A) doubled.303 32. Sol 26: We know. t = 10 min.1) (ii) After 60 sec (1 min). second order reaction. 5 × 107 sec–1 Sol 1: (B) From the table. 022t 4 Now. for nth order reaction t1/2 ∝ [A]n0−1 −3 ×200 [A] = [A] 0 e−10 = 0.303k T1 T2 ∴ [A]0 = [A]0 e–0. 8[A]0 = [A]0 e–10k ⇒n=2 ⇒ k = 0.6 − ( −11. unit of rate constant is min–1. rate get becomes 4 times. 2 × 107 J mol–1 −Ea Now. t1/2 gets halved.2×107 2 2 m 7e 8.4 − ( −11) Rate = k[A] 1 At t = 40 min. 42 × 1010 s–1 . 70 × 10–3 min–1 t 22.4 − (11.1) Sol 28: Rate = k[A] k= log t 25.k = A e RT Sol 2: (A) Rate. k = 1.4 + 11.303 × 8. Sol 29: Since. 5 × 10 = 2(n – m) ri A = 5. = k[A]0 e–k×60 2.
2t1/2 = 138. Chem i str y  18. 6 = 950 500 n−1 k = t t 235 250 (1 1/2 → 0. rate becomes 4 times. i. = 0. 2 × 0. rate = 10–2 M min–1 (A) and (B) are correct for first order reaction. ⇒ n = 3 log2 When [A] = 0. 1. for nth order reaction 3 dt 3 1 2y 1 d[Q] d[Q] 4 ∝ Rate of second reaction= = ⇒ = y P0n−1 3 2 dt dt 3 n−1 (t1/2 )2 P0 ⇒ = 1 Sol 8: (B) We have t = 138. 25) log 4. 02 t [A] = [A]0e–kt At t = 60 sec = 1 minute 3 When. if these reactions are carried simultaneously k2 = t energy released from (i) and energy absorbed is (ii) counter each other further. 8 M → 0. M → 2Q + R ∴ 0. 1–x 2x = − not 2 dt 2 dt dt 1 d[B] = 10–2 2 dt Sol 5: (D) For a first order reaction. rate of second k2 ln25 = = 4.29 Then.02 M 3 −k. 04[Y] 0 = [Y] −k 2 t e ∆H = x kJ/mole of M …(ii) 0 ln25 We see that. 1 1/2 → 0. 01 ⇒n–1= = 2. for X →A + B 1 k ⇒ t3/4 = k 50% reaction gets completed at time t Sol 6: (D) rate ∝ [O] 2 1 −k t ⇒ [X]0 = [X]0 e 1 2 ∴ When [(O)] is doubled.67 Sol 3: (A) We have t1/2 = 15 min (0. 1 d[C] 1 d[A] d[A] t=1 0. 1 M to 0. 65 reaction will be double of that of (i) k1 ln2 −1 d[B] y Now. 5 1/2 → 0. rate of first reaction= = Sol 11: (D) We know.693 i. . for 0. [B] = 0. rate is always constant. t = t3/4 4 [B] = 0. 6 min for (t1/2 )1 P0 2 1M → 0. (C) is A(g) → 2B(g) wrong as t=0 0. 5 1/2 → 0. Sol 4: (D) Only statement (D) is correct as k is constant at a given temperature. 1 M min–1 t = 2 × t1/2 = 30 min = 10–3 M min–1 t t (0. ∆H = 2OH. 025) Sol 9: (C) For zero order reaction. e.t ⇒ = e 3/ 4 4 Sol 10: (D) Let time be t 0. 025 M. 25 M Putting values. [A] = [A]0 . ln2 k1 = t Sol 7: (C) A + 3B → P k For Y 2→C + D ∆H = 2x kJ/mole of A …(i) 96 % of reaction gets completed at time t..04 ⇒ k = 0. 4M) Rate = k[A] Now.e. 01 × 0.
As T → ∞. 25(A)0 Ea = RT loge N0 = 8. −d[A] EA 1 1 ⇒ = k(1 – x)1/2 (1 – x)1/2 log 4 = − dt 2.303log2 N0 t= = k 2. 2 −E0 /RT B V 10 4 1 k = A = 6 × 1014 s–1(∵ e → 1) We have.693 t1/2 = = 62. 27ºC = 300 K. t = 200 s (Since 20% reaction completed) −6 ×200 (A) = 0.303 [A] (A) = (A) 0e–kt k= log 0 t [A]t 0. 05 M 20 4 k = 1. 11 × 10–2 min–1 Sol 17: (D) R is universal gas constant 0. 314 × 300 loge N 2 n2 2 × 2. 3. Sol 14: (D) A(g) → 2B(g) −E0 /RT 100 2 Sol 19 (B) k = A e .303 × 8. 5 × 10–11 L mol–1 s–1 Here. 2.314 300 320 −d[A] ⇒EA = 55.5 × 10 −3 k2 EA 1 1 108 = f = log = − kb kb k1 2. e. = k(A) dt i.8 × 10−16 N0 t = 600 s Ea = 100 kJ/mol . Sol 21: (C) We have. N = N0 e−Ea /RT when (A) = 0. 8 × 10–16 of −d[A] reactant molecules exist in the activated region.693 k1 = min–1 20 t=0 1 1 0 0 t=1 1x 1–x x x At T2 = 47ºC = 320 K We have.465×10 2. 465 × 10–6 s–1. at T1 = 27ºC = 300 K Sol 15: (B) A + B → C + D 0. 0. 05 mol L–1 at t = 20 min. = 108 [A] 10 −5 10 −5 10 V Sol 20: (B) We have.303R T1 T2 ⇒ kb = 1. N = 3. 6 8  Chemical Kinetics Sol 12: (C) We have first order reaction Sol 16: (A) We have for first order. 05 e−3.1 (A)0 = mol L–1 = 0.8(A)0 2 k = 3.1 8 . from Arrhenius equation k 1.303 5 ⇒k= log ≈ 0. (A) t = 0.693 k2 = min–1 −d[A] 5 Rate = = k(A) 1/2(B) 1/2 dt Putting these values. 13 minutes k is rate constant k A is pre exponential factor Sol 13: (C) Rate = k(A) = k(A) 0e–kt Ea is activation energy It follows an exponential decay. keq = = = .303 × 10−3 3. 8 × 10–16 N0 ⇒ (A) = (A) 0e–kt Now. 14 kJ/mol ⇒ = k(1 – x) dt This can be written as. Sol 18: (C) This is the correct definition.
4 × 10–5 Rate = k[Cl2] [H+ ] = 3. Kc = 2. t = 46. hence reaction is of first order w.38 × 10 s –2 –1 dt 2 × 102 2 × 102 ∴The order of the reaction with respect to NO(g) is 2.06 min. reaction rate is doubled. a – x = 50 [NOBr2 ] We have. A.t. Previous Years’ Questions Sol 8: (C) Since – dx ∝ [CO]2 so on doubling the dt 1 d[A] 1 d[B] d[A] 1 d[B] concentration of CO. over all order of reaction is 1 +1 = 2 [H+ ][HS − ] keq = So. the halflife did not Rate = k[Cl2][H2S] (By slow step) change.693 2.303 [NO][Br2 ] k= log10 = log10 16 2 × 10 2 50 2 × 102 Provided the first reaction attains equilibrium rapidly.303 4 2. at 400 K. the rate of reaction will increase Sol 1: (A) A → 2B . Chem i str y  18. 314 × 400 log So. Rate = k[Cl2][HS–] Hence.303 100 are effective only 10–4% of molecules have their energy = log t1/2 t 100 – 99 above activation energy.303 800 2. a = 800. unit of rate constant mol lit s .303 × 2 Ea = 2. dc 2. For B hence reaction is of first order w. 0. of B is doubled.693 2.keq[Cl2] [H+ ] Sol 6 (C) In first order reaction for x% completion a Sol 12: (D) t1/2 = (for zero order reaction) 2. 10−6 N0 = 45. 944 k J/mol = 11.303 a Sol 3: (C) k = log10 . 0001% (10–4%) of collisions 0. NO + Br2 → NOBr2 would be 2. When concentration of A is doubled. N0 0.0 × 10 (N2O5) or (N2O5) –5 = 0.– = by 4 times. 303 RT log = N 6.r.r. – 2 = .69 Sol 22: (D) Since.t.93 t N0 = 2. Sol 4: (A) 2A + B → Product Sol 11: (A) For A When conc. 2 dt 2 dt dt 4 dt ∆T 50 Sol 9: (A) R = k(A)(B)2 order of reaction =2+1= 3 Rate at 50°C T Sol 2: (C) = (2) 1 = (2)10 = 25 = 32 times Rate atT1 °C Sol 10: (D) The differential rate law for. –1 –1 [H2S] (According to equilibrium) Sol 5: (D) Rate= k(N2O5) k eq [H2S] hence 2.303 ∴– = k × kc × [NO]2[Br2] = k[NO]2[Br2] = log10 2 = × 4 × 0. 05 k cal/mol Sol 7: (B) Because two molecules are taking part in elementary reaction. B. t a−x dc – =k[NOBr2][NO] dt t = 2 × 102.301 = 1.303 100 2k 0 k= log t 100 – x% a 2 k0 = = =1 2 × t1/2 2 × 1 . 303 × 8.8 mol l–1 [H2S] Rate = k.
25 Sol 19: (D) Rate equation is to be derived w. t1/2 = 1hr.t slow k0 = ⇒ k0 = =1 t t Step ∴ from mechanism (A) t = 0..06 minutes 0. EB. 20 d[A] 1 d[B] − = dt 4 dt K −Ea 1 1 Sol 22: (A) = log 2 − Sol 17: (C) K1 2.93 100 ∴ t= log = 46. (ii) 2t1/2 Dividing equation (i) by (ii) Since [A0]=2M. 7 0  Chemical Kinetics A0 – [A]t 0.1 Sol 21: (B) k = log .r..1]x [0.2]y . k = zero order rate constant 1.693 dt 2dt For a F.6 = J / mol 53. 1 40 0.2 × 10−3 k[0.50 – 0.303 × 8...O..93 −E 1 1 [A ] ⇒ log2 = − 2.2 × 10–3 = k [0.= T2 310K T1 300K = = λ = min−1 K1 t1/2 6.. Therefore 32k1 = k2 Sol 16: (B) 2.2 × 10−3 k[0.1]x[0.R – EaB..2]x[0. k=1 1.2]y 0..303 0.030R T2 T1 K2 0.(i) for a zero order reaction 1.. k1 50 k2 Sol 15: (B) In photochemical reaction.. (i) Or.303 2. = k[A]x [B]y t dt Where x = amount decomposed Now from table.6932 = 2. 1 8 .1]y .R .R.1]x[0.6 KJ / mol [A ] = initial concentration (amount) [A] = final concentration (amount) Sol 23: (D) 2. ∆HReaction = Ef – Eb = 80 – 100 = –20.(iii) k= …. rate = × 10−2 = 3..303 × 6. µ 10 =2 .47 × 10−4 M / min.(ii) [A]0 2.2 × 10–3 = k [0.25 hr 1 1 ⇒ 1= 2 . Sol 20: (B) Temperature coefficient µ =2. Sol 14: (A) For endothermic reaction ∆H = +ve ∆T k Then from equation ∆H = EaF.R ..6932 0.4 × 10–3 = k [0. the rate of µ 10 = 25 = 32 = k1 formation of product is directly proportional to the intensity of absorbed light.025 A → 2B 0. Rate = k[Cl2] [H2S] Sol 13: (D) So..1]x [0.134 310 300 Also t= log λ [A] =⇒ Ea 53598.1]y ⇒ = ∴ from equation (i) 1.25 y =t = 0.6932 1 −1 d[A] d[B] d[C] d[D] Rate of Reaction = = − = = 2 dt dt dt dt Sol 18: (C) Let rate of Reaction = k(A)x(B)y x d[C] For a zero order reaction k = ….25 hr.1]y .693 2 k= 20 d[A] d[B] − = + 0.R < EF.
second order in B JEE Advanced/Boards and 0 order w.93 × 10−4 mol / minute × litre rO = 2 2 Sol 4: (i) Reaction of first order in A.693 ⇒ K= per minutes 25 d[N2 ] −1 d[H2 ] 1 d[NH3 ] (a) = = 0. t.1]y 3 1.08 = × 10 −2 = 3. dx = k [A] 1[B] 2[C] 0. C.2 × 10 k[0.71 ⇒ y=0 +1.693 dt 3 dt 2 dt rH = × 0. 6 M min–1 dt dt Sol 24: (A) In 50 minutes.693 × 10−3 2 3 = ×2 × 10–4 mol L–1 s–1 = 3 × 10–4 mol L–1 s–1 6. by ideal gas equation (i) Rate of reaction = = 4 dt 4 3 n PV = nRT ⇒ P = RT = 9 × 10–4 mol L–1 V P = CRT −d[NH3 ] (ii) = +4 d[NO] P dt 4 dt C= RT . 2 M min–1 1 dt becomes of initial. Chem i str y  18.386 × 10−3 2O2 25 −d[N2 ] 1 d[NH3 ] = dt 2 dt 2H2O2 → 2H2O + O2 1 = × 2 × 10–4 mol L–1s–1 = 10–4 mol L–1 s–1 1 2 rO = ×r 2 2 H2O2 −d[H2 ] 3 d[NH3 ] (b) = × dt 2 dt rO = 0. 4 −d[H2O2 ] 2 d[H2O] −d[H2O2 ] ⇒ 2 × t1/2 = 50 minutes (b) = = = 7.2 × 10 k[0.08 × 10 −2 = × = 5. Rate of reaction = = = 4 dt 5 dt rf = k[2A] [2B] 2 = 8k[A] [B] 2 = 8r 1 d[NO] 1 d[H2O] Rate becomes 8 times = 4 dt 6 dt 1 d[NO] 1 1. k = [D]t Exercise 1 dt dx ⇒ = k[A] [B] 2 Sol 1: 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) dt −1 d[NH3 ] −1 d[O2 ] (ii) If [A]. [B].08 × 10−2 Sol 5: We have. r.2]x [0.05 = 1. 4 × 10–3 mol L–1 1 y 2 3 1 1 ⇒ = 2 2 Sol 2: (a) 2H2O2 → 2H2O + O2 ⇒ xx== 1 −1 d[H2O2 ] −1 d[H2O] d[O2 ] We know. concentration of H2O2 d[H2O] = 7. 6 × 10–3 mol L–1 3 Now dividing equation (i) by (iii) d[H2O] 6 d[NO] −3 x y (iii) = 1.1] [0. = = 2 dt 2 dt dt d[C] Hence = k[A]1 [B]0 dt d[H2O] d[O2 ] =2 = 2 × 3.1] dt 4 dt ⇒ = −3 1. [C] are all doubled. 2 M min–1 dt 2 dt dt ⇒ t1/2 = 25 minutes Sol 3: N2 + 3H2 → 2NH3 0.
ΔT = 75 × 605 = 4500 s Energy released by 1 mole of 1 0.384 6 Hence rate constant = 0.0186 mol–1 s–1 rf = k(0.9 × 1026 = = 6. 0186[BrO–] 2 ∆t ri 0. 037[BrO–] 2 k = 1. t = 0 0. 4)2 = 0. k2 = 2k. ri = k[A] 2[B2] 1. [A] and [B2] 6. 4 atm 2 ∆t ∆t We have. 0186 L mol–1s–1 Sol 11: A → B ∆[Br − ] (b) = 2k[BrO–] 2 = 0. 8 – 2x = 0. 23 × 1014 6. 1) atm = 0.26 × 1011 Sol 6: 2A + B2 → 2AB 1. k1 = k. 7 2  Chemical Kinetics ∆C 1 ∆P k2 Rate of reaction = = ⇒ k1 = = 2k3 ⇒ 2k1 = k2 = 4k3 ∆t RT ∆T 2 We have. 4)(0. 3k = 0. 2 atm 1 ∆[Br] −∆[BrO − ] = = k[BrO–] +2= = 3k[BrO–] 2 PA = 0. eject 26 MeV energy. 2 × 10–2 Ms–1 ∆t Rate constant = 0. 2 × 10–2 × 10 × 60 M 1 d[O2 ] [B] = 7.012 atm min–1 ∆t 75 3.7 × 1033 Time taken = = 2. 9 × 1026 J in one second. Total moles of H on sun = = 1.e.ri = k(0. 8 – 0. k3 = [B] = 1. 6 MeV ΔP = (2 – 1. 8)2 = 0.056 PB = 0. 9 atm It means 4 atoms of H. 8–2x x x Sol 7: 3BrO → BrO3 + 2Br –  Since this is elementary reaction We have. 6)(0.9 NA Rate of reaction = × Ms–1 H= = 26 × 106 × 1. 8 0 0 t 0.23 × 1014 becomes 3 times each. 0921 L atm/mol. N2O5(g) → 2NO2(g) + O2(g) Rate law [B] = kt 2 −d[N2O5 ] 1 d[NO ] At t = 10 min ⇒ = 2 dt 2 dt [B] = 1. 23 × 10–6 Ms–1 Power output of sun = 3. 381 k Rate = = 3 ∆t ∆t WhenPi = x – 0.064 1 ∆[BrO3− ] = = (a) = k[BrO–] 2 = 0. ∆H = 2.0921 × 300 75 × 60 4 = 7. ∆P 0. k 1 4 T = 27ºC = 300 K Sol 9: 4 1 H → 2 He . 4 M 2 .7 × 1030 Since. 9×1026 W = 3. rate becomes 27 times. r = k(B) 2(A) −1 ∆[BrO] ∆[BrO3− ] Now. 9 × 1026 J/s Rate of reaction in terms of pressure i. this is an elementary reaction.064 k rf 0. 6 – x = 0. 7 × 1033 10 −3 rate. it radiates 3. 2 M = = +k[N2O5] 1 dt At t = 20 min 2 k Hence.9 Number of moles of H required per second = = atm min–1 = 0. 72 × 1018 s If volume of vessel reduced to onethird. 6–x 0. 6 × 10–14 J = 6.1 8 . ∴ rf = k[3A] 2[3B2] = 27k (A) 2[B2] = 27ri Sol 10: A(g) + 2B(g) → C(g) + D(g) Hence. 4 atm k = 0. 4 = 0. Rate. 6 0. it is zero order reaction 1 Sol 8: We have. R = 0. 26 × 1011 J 0. 2 × 10–2 × 20 × 60 M = 14. 037 Lmol–1s–1 Since unit of rate constant is Ms–1.
∴ [B] = 14. (ii) When reaction is 87. 08 M. Chem i str y  18. which is the value given. 01 M min–1 k= 1 [A]0 ln t [A] At t = 2 min.01 M min–1 ∴k = ln 4 = 0. 10 0 1 [B] max = 10 M ∴ [A]0 = [A]0 – kt 10 [B] = 10 M 9 3 ⇒ [A] 0 = [A]0t Sol 12: For zero order reaction. [A] = 0.8[A]0 Time taken to disappear = k k = 0. [A] = [A]0 = 0. 10 4 [A] = [A]0 – kt ⇒ t = 1. 2 hr At t = 0. 1 – 0. 5% complete. k = 2 × 10–2 mol L–1sec–1 1 1 ∴t= ln and at t = 25 sec. 09 M Sol 16: (i) We know. 1 ∴ [A]0 = [A]0 – k Sol 18: Order will be equal to 1. [A] = 0. for first order reaction 0. reaction is 20% complete. e. 0223 min–1 6 × 10 −2 = sec = 6 × 10 sec –9 107 (ii) When reaction is 75% complete. 4 3 1 [A]0 ⇒ k = [A]0 M hr–1 t= ln 4 k [A]t . e.1 × 10−3 8[A]0 k = 107 mol L–1 sec–1 1 [A]0 k= ln [H+ ] 10 0. 17 min. 09 = 0. Sol 13: For zero order reaction ln2 [A] = [A]0 – kt t = t1/2 = = 36 min k We are given.1 – k [A] = [A]0e–kt ⇒ k = 0. [A] 0 = 10 M and [B] cannot be greater than [A0] [A]0. 019 min–1 72 When reaction is 50% complete. 1 Sol 15: Since it is a zero order reaction [A] = [A]0 4 [A] = [A]0 – kt 1 [A]0 1 [A]0 1 t= ln = ln When t = 1 hour. [H+]0 = = 6 × 10–2 M 0. (A) = 0. i. [A] = 0.125 [A]0 = [A] + kt t = 108 min = 0.4 M implies that reaction has reached 1 [A] = [A ] completion. [A] = [A]0 = 0. 75 M Sol 17: We have.0223 1 4 . 25 M k 0. 25 + 2 × 10–2 × 25 = 0. 01 × 2 1 At t = 72 min. i. [A] = 0. When A is 10% unreacted. 4 1 ∴ k = 0.73 But. i. [A] = [A]0 k [A]t 0. 75% reaction completed. for first order reaction Sol 14: It is a zero order reaction (∵ unit of rate constant 1 [A]0 k= ln is M sec–1) t [A]t 6 × 10−6 (i) At t = 10 min. 1 M At t = 1 min. e.[A]0 4 (∵ 75% reacted) t = 62. 125[A]0.
3 × 10–4 sec–1. ∴1.5[A]0 k k t = 0. N∝5 −1. α = C0e–k = aC0. Sol 24: For A. Initial concentration 1 [N]0 1 [N]0 ∴ t = log = log [A]0 a0 t [N]t 8. ln2 Using first order to rate law. 2 % of [SO2Cl2] decomposed. [SO2Cl2 ]0 [N]0 = 500 11. 5 × 10–3 sec–1 found the concentration of A to be of the form given in N ∝ 1. 717 × 10–3 month–1 Then. k = 0.1 8 . first order reaction t = 3t.5×10−3 t Sol 23: For first order reaction. we here. [A]t = 0. k1 = ln2 = t1/2 5 1 [N]0 Initial concentration = a0 k= ln t [N]t Let [A]t = a k = 8.5 decomposed 30%. . 98[A]0 4= e 1 2 (k −k )t 1 [A]0 k = log ln 4 1 0. α = C0e–3k = a3C0. 7 4  Chemical Kinetics When reaction is 99. the reaction is of first order.2×10−5 ∴ = e = 0. 25 = 5e 1 5 [SO2Cl2] = [SO2Cl2]0 e–kt ⇒t= ln 1. taking the reaction to be of first order. 2 × 10–5 sec–1. i. [N]t = 420. a = e–k Sol 19: We have. Therefore. k2 = ln2 = t1/2 1. t [A]t a0 −k 2 t We are given. t = 924. i. at t = 1 min. 9 % complete.693 ∴t2 = ln = = At time k 0. ∝ molar) question. e. α = C0 We see that t2 ≈ 10t1 t = t. 0 [A]0 then. 25 (wt. When reaction is 50% completed. a = e–k N = N0e–kt Therefore.25 k = 2.909 t1 = ln = ln10 = k 10−3 [A] k k Sol 22: If we assume the reaction to be of first order. [A]t = 2 a = C0e–kt 1 [A]0 ln2 0. α = C0e–2k = a2C0. e. let [A]t = α and [A]0 = C0. 02 min–1 [A]t = 10–3 [A] 0 k = 3. 2% of virus gets inactivated every minute a0 e−k1t = e 4 at the beginning. a = e–k t = 2t. b = e 4 1 [A]0 k = log When a = b. k = 1. 888 Sol 20: We have. 7 [N] 0.7[N]0 [B]0 = = 4 4 t ≈ 41 months [B]4 = b a0 −k 2 t Sol 21: For first order reaction Then. 3625 t = 90 min = 5400 sec [SO2Cl2 ] −5400×2. [N] = 0. a = e0 e−k1t ln2 The drug will be ineffective (will expire) when it has For B. 1 [A]0 3 6.5 × 10−3 1. At t = 20 months.98[A]0 ⇒t= k1 − k 2 .717 × 10−3 0.
[NO] = 0. r.05) 1 (d) If [Cl2] = 0.4 × 10−4 ∴k = (4 − 3) × 103 (1. [NO] = 0.2. [A] = [A]0e–kt. then our assumption is correct. –4 P0 − P (4 − 3. t. r. [A]n0−1 (a) Order w. t 100 k1 = 5 Pa/s Rate = 4. Cl2 is 1. At t = 53 min. so. 256 mol sec L –1 –1 ⇒n=0 Sol 27: Let us assume that this is first order reaction. keeping [H2] constant. e. P = 2 × 103 Pa 4. t. we will calculate k at both times. 4 M. this is first order reaction. [A]0 Rate = 10–3 50 2 1 ∴ = = 25 [A]0 2 −1 n rate 10−3 k= = = 8 M–2 sec–1 2 2 [NO] [Cl2 ] (0. e. 2 M. 05 M. When [NO] is doubled. 2= ⇒ 2n–1 = 2–1 n−1 2 Rate = k[NO] 2 [Cl2] = 8 × (0. Rate = k[NO]2 [H2] At t = 0 sec. r. Chem i str y  18. rate becomes 9 times.75 ln 4 2ln2 2 × 5 × 15 ln2 0. order w. 4 × 10–4 M sec–1 At t = 200 sec. i.5) × 103 k3 = = 5 Pa (c) Rate = 4. t = 15 min. P = 2. 013 min–1 ln2 ln2 1 1 10 t 53 − ln2 − 5 15 5 15 (i) We see that both values of k are same. ( t1/2 )2 = 25 min (b) Rate = k[NO] [Cl2] 2 2 n−1 (c) When [Cl2] = 0. If they are same. 85 × 10–3 M sec–1 We see that k1 = k2 = k3 = 5 Pa/s is same for all. 05 M. 5 × 10 M. so. for nth order reaction 1 When [NO] is tripled. rate becomes 3 times. Sol 29: We know. order w. when [H2] [N2O]0 is halved. NO is 2. [A] = 0. 88 × 106 × (1. P = 3. order t1/2 ∝ w. 1 × 10–3)2 × (1. 5 × 103 Pa (b) When. Using this. when [Cl2] is tripled. k1 = = Pa/s [H2] = 4 × 10–3 M. we assume order = 0 rate becomes 4 times so. 27 Sol 25: From the data. 1 × 10–3 M. 2) n – 1 = –1 Rate = 0. we observe that. r.05) (0. (t1/2)1 = t = 50 min Cl = 1 [A]0 at . 50% reaction completed. 5 × 10–3) 300 Rate = 8. reaction rate gets Thus 73% of N2O will decompose. 5 × 103 Pa [H2] = 1. reaction Sol 28: As in previous question. r.5) × 103 We have. [NO] = 1. t. So.693 = = = ∴k= = = 0. Hence this is zero order reaction. t [NO] is 2. 5[A]0 . P = P0 = 4 × 103 Pa (a) Order = 2 + 1 = 3 At t = 100 sec. At t = 300 sec. rate constant = 5 Pa/s Sol 26: From given data. order w. [N2O] −2 ×100 (ii) = e–kt = e−1. 4)2 (0. i.5 × 10−4 )2 × (4 × 10−3 )2 k = k2 = = 5 Pa/s 200 When [NO] = 1. halved. we observe that. and calculate k at different time. at [A]0. keeping [NO] constant.3×10 = 0. NO = 2 We have. 5 × 10 M –3 (4. t H2 is 1.
7 6  Chemical Kinetics Sol 30: (n0 − x)a + xa + xa (n0 + x)a Vn = V2 = = A → B+ C N N t=0 P0 0 0 NV2 ⇒ n0 + x = t P0 − x x x a t→∞ 0 P0 P0 NV0 N x= − n0 = (V − V1 ) a a 2 We have. PB + P0 = P3 = 2P0 NV2 P3 a + 4x = ⇒ P0 = n 2 at time. V2 = (a – x)n + 2xn + 3xn PB + PC = P2 = 2x ⇒ x = 2 NV2 = n(a + 4x) at time t → ∞. n + 3a. t → ∞. B. t NV N a 1 − (V2 − V1 ) Pt = P3 = 2P0 a a P3 1 V1 ⇒ P0 = k= ln 2 t 2V1 − V2 Taking first order reaction. t P2 N. t = t. B and C be n and normality of reagent Sol 31: Here. at time t = t1 1 n 1 n k = ln 0 = ln 0 P1 = Pt = P0 – x + x + x t nt t n0 − x P2 = P0 + x ⇒ x = P2 – P0 1 NV1 = ln At time. at time t = N then at time. 1 (PA )0 1 P 1 P0 Sol 33: A → 2B + 3C k= ln = ln 0 = ln t (PA )t t P0 − x t P0 − P2 + P0 Time. we have. Vr = V1 = t a−x t NV NV2 NV3 N 5n 3 − + 5n 4n 20n NV1 ⇒ n0 = V3 4V3 a 1 1 = ln = ln (nfactor of A.1 8 . . n t (PA )t t P3 P2 t P3 − P2 − ⇒ a = NV3 = 5an 2 2 NV3 a= 5n Sol 32: A → B + C NV2 NV3 Then 4x = – time n 5n t=0 n0 0 0 V3 N x= V2 − t n0 – x x x 4n 5 t→∞ 0 n0 n0 1 a 1 NV3 n0 − a k= ln = ln At time. t = 0. C = a) t 5 t 5(V3 − V2 ) V3 − V + 4V3 4 2 (using NV1 = n0a) 1 4 V3 Normality of reagent = N k= ln t 5 ( V3 − V2 ) At time. t = 0 a 1 P0 1 P3 Time. t → ∞ 1 (P ) 1 P3 1 P k = ln A 0 = ln = ln 3 NV3 = 2a. t a – x 2x 3x k= ln = ln t 2P0 − P2 3 2(P3 − P2 ) Time. t → ∞ 0 2a 3a Let nfactor of A.
Pt = 827 = P0 + 2 At t = 1195 s. 28 × 10–4 s 1195 312 − 125 1 758 k= ln 5 758 − 138 At t = 3155 s. Chem i str y  18. all 3 values of k are approximately the same. 039 hr–1 r∞ a= θ1 + θ2 Thus. at time t. hence first order reaction. t = 1P0 – x x 2 At t = 0. 3 x ∴ At time t. At t = 390 s. 039 hr–1 Then. 2. t P0 – x x x x θ1 + θ2 θ1 + θ2 t→∞ 0 P0 P0 P0 1 r∞ k= log t r∞ − r1 Total pressure. t → ∞ k= ln 10 758 − 248 aq1 + aq2 = r∞ k = 0.77 Sol 34: S→G+F x ⇒ = 856 – 758 Time t = 0 a 0 0 2 Time. pressure increases. 30 × 10–4 sec–1 t = 7.303 a 1 a k= log = log t a−x t a−x Sol 36 : (CH3)2O(g)→CH4(g)+H2(g)+CO(g) 1 r∞ Time t = 0 P0 0 0 0 k= log t r rt (θ1 + θ2 ) ∞ − Time. t a–x x x x = 196 mm Time t → ∞ 0 a a 1 758 k= ln 7. Pt = 856 = P0 + 3155 312 − 233. it won’t contribute to pressure. P0 = 312 mm Hg Since. Pt = 889 = P0 + 2 xq1 + xq2 = rt x = 2(883 – 758) rt x= x = 248 mm θ1 + θ2 1 758 At time. 04 hr–1 1 312 x k= ln = 4. 28 × 10–4 s x t = 5 hrs . DP = 467 = 2x x = 233. 5 hr. as a solid.5 2 . using k = ln 0 1 P 1 312 4 P0 − x ∴k= ln 0 = ln t P0 − x 390 312 − 48 t = 0 P0 = 758 = Pt k = 4. 5 mm Hg k = 0. at time t x t = 10 hr. DP = 250 = 2x x 827 = 758 + x = 125 mm Hg 2 1 312 ⇒ x = 138 mm k= ln = 4. Pt = P0 – x + x + x + x = P0 + 2x 3 Sol 35: As H3(g) → As(s) + H2(g) Increase in pressure = (P0 + 2x) – P0 = 2x 2 t = 0P0 We will assume that this is a first order reaction and 3 check the consistency of given data.5 758 − 196 Let specific rotation of Glucose and Fructose be q1 and q2 respectively k = 0. Pt = P0 – x + x = P0 + DP = 96 mm Hg = 2x 2 2 Let’s assume reaction is first order and calculate k at x = 48 mm Hg 1 P different times.
303 (13.87) − ( −3. this is first order reaction. this is a first order reaction Therefore. (i) (PA)I = 90 mm Hg 1 θ − θ∞ k= log 0 (ii) (PA)f = 47 mm Hg t θf − θ∞ (iii) k = 6.1) − ( −3. k1. k3 and k4 are all same within 20 8.8 k2 = log = 5. since. 7 8  Chemical Kinetics At t → ∞. 2º Here. t = 10 min. 57 × 10–3 min–1 120 (10. Pt = 584. t → ∞. 55 × 10–3 min–1 360 (5.8) 2.303 (13. 25 cc = Vt k4 = log = 1.25 experiment value. k = 6. 5 = P0 – 2x + 4x + x (PA)+ = P0 – x = 90 – 43 = 47 mm Hg ⇒ P0 + 3x = 284. t = t P0 – 2x 4x x Time.8) k3 = log = 1.8) t = 20. 3 cc = Vt 180 (9. 0.1) − ( −3. Therefore. 677 min k 6. 60 11. k2.Vr = 8. k 1 13. 49 × 10–2 min–1 At time. Therefore.303 (13. t = 120 min. t → ∞.8) k2 = log = 1. 67 min At time.DP = 2P0 = 624 mm Hg Now. 1 (iv) t1/2 = 10. 4 × 10–2 min–1 10 13.8) 2.8) 1 = 1. 54 × 10–3 min–1 t = 10. t P0 – x 2x x 2 Time. t→∞ 0 2P0 P0 P0 At t → ∞. 1 × 10–2 min–1 We see that. 8 At time.303 90 k= log A 0 = log Thus. qt = + 10. 6º Sol 40: 2N2O5(g)→4NO2(g)+O2(g) time.1 − ( −3. t = 0 P0 0 0 t→∞ 0 2 P0 P0 Time. θ+ = 11. qt = +9.θ = θ∞ = –3. Vr ∝ [H2O2] Assuming this is a first order reaction 2.49 × 10−2 Sol 38: For inversion of cane sugar.693 0.303 [H O ] 1 V k= log 2 2 0 = log 0 t [H2O2 ]t t Vt At time.2) − ( −3. 8 mm Hg 2x = 176 – 90 At t = 30 min. 5 . 5 2 At. Pt = P0 – x + 2x + x = P0 + 2x = 176 ⇒ P0 = 233. t = 0 P0 0 0 Sol 39: A(g) → 2B(g) + C(g) time. Vr 22. t = 0.303log .Pt = 3P0 = 270 mm Hg 2 5P0 P0 = 90 mm Hg = (PA) ⇒ = 584.8) = 4. qt = +5.6 − ( −3. ≈ 619 mm Hg 2.303 (P ) 2. x = 43 mm Hg Pt = 284.303 22.0) − ( −3. 28 × 10–4 sec–1 k1 = 2. 8 cc = V0 2. 55 × 10–3 min–1 Sol 37: H2O2(g) → H2O() + O (g) 2 2 At time.693 Halflife = = = 10. 49 × 10–2 min–1 So.Vr = 13.1) − ( −3. t = 180 min. 5 = 2P0 + At. 87º k1 = log = 5.3 2. θ = q0 = + 13.303 22. t = 360 min. k1 and k2 are equal within experimental error. 0º At time. t = 60. t = 0. we see that all 3 values of k are approximately the t (PA )+ 10 47 same. rate = k[(CH3)2O]. this is a first order reaction.8 At time.1 8 . first order reaction. assuming first order.8) 2.
43 min.93 × 10 −2 46. 5 – 233. 0.303 k= log 0 t Vt 2.34 − 10. 8 cc 4. 1 Sol 42: H2O2 → H2O + O −1 d[N2O5 ] 2 2 = k[N2O5] 2 dt We are given complete dissociation gives 46. 34 –20.8 = log k = 4. O2 lost.34 − 20 At t = 10 min. Chem i str y  18.303 22.693 (b) t1/2 = = = 13.303 46. 31) 2.303 V At time. θA = 20º. θB + n0θC Since.79 3x = 284.303 46. Vt = 8.25 At t → ∞.θ∞ = –5º = n0.1 46. [N2O5 ]t t Also VO ∝ [H2O2] d[N2O5 ] 2 ∫ = −2k ∫ dt [N2O5 ]0 ( VO is volume of O2 a given sample of H2O2 can give) [N2O5 ]0 0 2 ∴ [H2O2] 0 ∝ 46. 284 PN = P0 – 2x V0 2.31 2. 75 min θC = –40º k 5. 34 mL O2. 31 mL [N2O5 ]0 2 Then [H2O2] t ∝ (46. 605 × 10–3 min–1. 10 = 1 – 0. 45 days 2.05 × 10−2 = 1. 716 We have. k1 ≈ k2. 34 [N2O5 ]t ln = –2kt Also.8 t →∞ 0 n0 n0 k2 = log = 2 × 10–2 min–1 20 8. VO = 10. 2 × 30 200 When 20 mL. t = 6. Vt = 13. k = 2. 5 . 5 2. 02 × 10–2 min–1 Sol 43: A(aq) → B(aq) + C(aq) 10 13.V0 = 22.303 2O5 = 233. n0 = 0.34 = log We have.303 [H2O2 ]0 t= log V k [H2O2 ]0 − [H2O2 ]t 2.1 days.34 2t (PN O )t 2 5 k= log 2 5 5. 9 mm Hg Vt −25 × 5. 8 cc t = 11. 34 –10. 25 cc t = t n0 – x x x 2. at t = 5. 00) Sol 41: (a) Assuming first order reaction 2.303 [N O ] k= log 2 5 0 2t [N2O5 ]t 2. We have. 8 – 2 × 16. This is first order reaction.303 (PN O )0 k= log 2 5 (∵ PN O ∝ [N2O5]) 2.8 t = 0 n0 At t = 20 min.8 k1 = log = 5. k = log 2 2 0 t [H2O2 ]t 2. 8 Fraction decomposed x = 16. 93 × 10–2 days–1.693 0.05 × 10−2 ∴ 30n0 – 40n0 = –5 (c) At t = 25 min. k= log 0 25 Vt qt = (n0 – x)θA + x(θB + θC) = 2. [H2O2] t ∝ (46. 9 = 200 mm Hg Fraction decomposed = 0.303 22. θB = 30º.303 233.303 [H O ] So.
[x]t e−kt 1 ∴ = = 2. 25 k For first order conversion. k2 = 10 k1 = 10 × hr–1. k k ⇒[x] t = [x]0e–kt. 1 min–1 k [A]t = [A]0e–kt Sol 44: [C]t k2 (1 − e−kt ) 1 = = (e−kt − 1) k1 B [A]t k1 + k 2 e −kt k1 1+ x k2 k2 C We have.5 = log 6.93 0. 8 0  Chemical Kinetics 20n0 + x(30. d[B] ln2 ln2 Now. 5 – 2. 5 k k 30x = 7. 5 k + k2 (1 −e−kt ) [x]0 (1 − e ) = [x] 0 e −kt = 1 x = 0. k = k1 + k2 k = 0. k = k1 + k2 A → B 1 2→ C. t = 1 hr (B = y.303 n [y] + [2] 1−e −kt e + (k1 +k 2 )t −1 k= log 0 t n0 − x Sol 45: Using results of previous question 2. k1 = x hr–1.303 0. C = z) [C]t 1 We have.25 k 2 [A]0 [C]t = (1 − e−kt ) . we get .5 − 0. ∴ = (e(x +10x) − 1) [A]t 1 1+ d[x] 10 = –(k1 + k2)[x] [C]t dt 10 11x = (e – 1) [A]t 11 [x]t t d[x] ∫ = −(k1 + k 2 )∫ dt [x]0 [x] 0 Sol 46: We have. = k1[x] t k1 = . k1 + k 2 [B]t + [C]t = [y] + [x] Solving this.1 8 . 5 k1 [x]0 k 2 [x]0 = (1 − e−kt ) + (1 − e−kt ) 30x = 20 × 0. 40 – 20) = 2.k = dt ln1 2 2 d[B] For [A] = k1[x]0e–kt dt d[A] [B]t t = –k1[A] −kt dt ∫ d[B] = k1[x] 0 ∫e 0 0 ⇒ [A] = [A] 0 e−k1t −k1 [x]0 t d[B] [B]t = e−kt = k1[A] – k2[B] k 0 dt d[B] −k1 [x]0 = k1[A] 0 e−k1t – k2[B] [B] t = (1 − e −kt ) dt k1 + k 2 d[B] + k2[B] – k1[A]0 e−k1t = 0…(i) dt k 2 [x]0 Similarly [C] t = (1 − e−kt ) This is a linear differential equation.
63 × 10–3 1 ln2 −4 1 T t= ln = ln = 4 k1 − k 2 4. 7 = (k −k )t e 1 2 8. k1 = 8. we get ((Ea )1 − (Ea )2 ) 1 1 dt 4antilog − =2 2.5 × 10 ln 5 × 1013 2. 72) kJ mol–1 2 1 Ea = 5 kJ mol–1 k2 Ea 1 1 2 log = − k1 2. −k1t −k1t −k1t −k 2t k 2e .303R 300 T Ea = 104. k = 0.314 − 20) × 10 1 − 1 =0. Chem i str y  18. =0 =2 dt k2 d[B]t In (i). 1 K .314 300 T k2 1 1 logk1 − logk 2 − = 7 × 10–4 t = 300 T . 8314 kJ/mol 3 k1 ⇒ (28. Ea 1 k1 2OH– → H2O + O.ln2 ln2 2 T = 379. k = A e RT ⇒T= ln R k k1 (Ea )1 1 1 log = − A = 5 × 1013 sec–1 8 2. T2 = T Ea A −Ea Now. similarly. Ea = Ea – ∆H = (77. T1 = 300.303R 300 T d[B]t k1 Now. 75 K ∴ t = 4 min.303R T1 T2 Sol 49: For t1/2 = 1 min. = 0. =2= H2O+O [C] k2 Reaction coordinate → Let temperature be T. T = 349.81 k1 [A]0 −k1t −k 2t (Ea )2 1 1 [B] t = [e −e ] k2 = 2 antilog − k 2 − k1 2.155 × 10 −2 For A k2 → C.303R 300 T 8. at [B] max. Sol 48: H2O + O → 2OH–.303R 300 T k1[A]0 e−k1t = k2[B] (Ea )1 . putting = 0.134 1. 5 kJmol–1 (Ea )1 1 1 −1 k1 = 8 antilog − 3 T = 104.303 k1 − k 2 1 = 2. By Arrhenius equation.2.303R 300 T 2 k1[A]0 e−k1t = [e −e ] k 2 − k1 (Ea )1 = 20 kJ/mol.k 2e (Ea )2 = 2. 693 min = 1.(Ea )2 1 1 1 − = log k 2k1 [A]0 −k1t −k 2t 2.693 t1/2 For A k1 → B.k1e = k 2e . 155 × 10 s –1 –2 −1 Ea = 20 kJ/mol (E1). k2 = k1. Ea B 2 Sol 47: A Potential energy → k2 C E a2 [B] k1 = Ea1 [C] k2 2OH [B] k1 We need.
314 300 320 = 42.693 = = 1. Here. log = − −3 2. as equilibrium is Ea = 75 kJ mol–1 achieved fast 1 Ea = 25 kJ mol–1 Rate = k3[NOBr2] [NO] 2 T = 25ºC = 298 K For equilibrium of (i). 4 minutes 298 T T = 306 K Sol 55: We have.693 –1 0. k = 0.303 × 8. 625 × 10–5 sec–1 T2 = 450º C = 723 K. 757 kJ mol–1 20 Ea = 55.314 × 298 × 308 Ea 1 1 Ea = ∴ log 4 = − 10 2. k2 ∴ = 5. 8 × 108 k1 [NOBr2 ] k1 = k2 [NO][Br2 ] Therefore. 0.925 × 10 k2 Ea 1 1 log = − k k1 2.8 × 10−2 ⇒ − = 8. k1 = 3. . 625 × 10 sec –5 –1 By Arrhenius equation Ea = 100 kJ mol–1 k2 Ea 1 1 T1 = 25ºC = 298 K log = − k1 2. 8 × 108 times.925 × 10 −3 9. 5 × 10–5 Time = 20. 81 × 10–2 min–1 log = − −5 2.625 × 10 −5 100 × 103 1 1 k = 6. k2 = k So.303 × 8. 711 kJ mol–1 log 4 × 2. 925 × 10–3 min–1 t1/2 2 t1/2 360 = 9. Sol 52: By Arrhenius equation k1 (i) NO + Br2 NOBr2 k = A e−Ea /RT k2 k3 k2 (Ea −Ea )/RT (ii) NOBr2 + NO → 2NOBr = e 1 2 k1 This is RDS We have. we have. 33 kJ/mol Sol 54: At T1 = 380ºC = 653 K.693 Time required for 75 % reaction = 2t1/2 = 1 1 6.75 × 2.46 × 10 2 × 0. we use equilibrium approach. 8 2  Chemical Kinetics Sol 50: From Arrhenius equation k 308 k Sol 53: Temperature coefficient = = 1. 75 k2 Ea 1 1 k 298 k log = − k1 2.314 653 723 1.303 × 8.1 8 .303 × 8.314 298 T 3. 46 × 10–5 sec–1 Ea = 200 k J mol–1 k2 = 9.693 Sol 51: For t1/2 = 2 hr.303k 298 308 T2 = 47ºC = 320 K.693 = hr k1 = 0.303R T1 T2 T2 = T k 200 × 103 1 1 By Arrhenius equation.303 × 8. rate of reaction increases by 5.314 × 300 × 320 Ea = Ea = 10. 548 1.303R T1 T2 log = 1.303R T1 T2 By Arrhenius equation For T1 = 27ºC = 300 K and k 308 k Ea 1 1 log = − k2 k 298 k 2. =4 k1 log1.
rate = [NO] [Br] = k[NO] [Br2] 2 2 from (i) equilibrium. from (ii). RDS (iii) IH2 + I As equilibrium step is fast. k −1 1 Coefficient in rate law = stiochiometric coefficient Sol 58: (a) H2 + I2 → 2HI Given rate law since. this is one step. it cannot distinguish between the three mechanisms k1 as all the 3 molecules gives the same rate law. RDS k1k 3 [I]2 Hence. rate = k[H2] [I2] 1 d[C] −1 d[D] +1 d[A] d[B] + = = = − 2 dt 3 dt 3 dt dt (b) (i) I2 → 2I Reaction is 3D + B → 2C + 4A . k1 = k2 [I2 ] k1k 3 [I] 2 = k1[I2] k= k2 from (ii)Rate = k2[I] 2[H2] = k2k1[I2] [H2] Sol 56: (i) 2NO → N2O2 = k[H2] [I2] . = k1k2k3[I2] [H2] k1 [N2O2 ] = Rate = k[H2] [I2] k −1 [NO]2 (d) No. Chem i str y  18. 1 d[NO2 ] k 2k1 Rate = = k2[O2] [N2O2] = [NO] 2[O2] 2 dt k −1 1 d[NO2 ] Exercise 2 Rate = = k[NO]2[O2] . fast [NOBr2] = [NO] [Br] k2 (ii) 2I + H2 k2 → 2HI. Sol 57 (i) NO + NO N2O2 [fast] k −1 Rate = k3[IH2] [I] (ii) N2O2 + O2 → 2NO2 (RDS) k2 = k3k2[I] 2[H2] from equilibrium of (i). Rate = k2[N2O2] [H2] from equilibrium (ii). 2 dt Single Correct Choice Type k 2k1 k= Sol 1: (B) We know. fast [N2O2 ] from (i).83 k1 equilibrium constant = k1. [N2O2] = [NO] 2 k −1 (e) Mechanism (a) becomes most improbable as it just from (ii) involves one step and it is highly unlikely that I2 and H2 will combine directly at 200ºC without breaking into radicals. k=k2k1 equilibrium constant = k1 (fast) (c) (i) I2 → 2I (ii) N2O2 + H2 k2 → N2O + H2O equilibrium constant = k1. k1 = [I]2 [NO] 2 from equilibrium (i). fast RDS k3 (ii) I + H2 → HI2 (iii) N2O + H2 → N2 + H2O k 3 → 2HI. k1 = [I2 ] [N2O2] = k1[NO] 2 [I] 2 = k1[I2] Also. = k1k2[NO] [H2] 2 [IH2 ] k2 = [HI] 2 = k[NO] [H2] 2 [I][H2 ] k = k 2k 3 [IH2] = k2[I] [H2] 1 k since (iii) is RDS. we use equilibrium approach equilibrium constant = k2.
75 N d[B] rate. 1 × 37. [A] = [A]0 – kt 2.303 4. 02 M KMnO4. t O2 and second order −kt Slope of log (a0 – x) vs. t1/2 ∝ (A)0.303 a Sol 7: (C) We have k = log 0 t a0 − x −∆[A] 0. .303 16. 25 = 0. log(a0–x) = + log a0 2.8 k= log 2. Normality becomes Ef N. 6 = 0. V0 = 16.303 V 1 k= log 0 At time t = t3/4. 30 log(a0–x) For experiment 2. therefore.5M So. 8 4  Chemical Kinetics Sol 2: (D) If volume is reduced to half. 2 V Now. 8º Sol 3: (C) We have Now. t N2 2.2 Similarly. after 2. Reaction coordinate→ Under acidic conditions. let normality be N. 5 5 Sol 4: (D) For zero order reaction N = 0. rate of reaction will be independent of time. 303 log a0 – 2.303 rf = k[2O2] [2N2] 2 ⇒ k = 7. 6 N0 = 16. 303 hours. 7 × 10–3 rf = k[2O2] [2N2] 2 = 8ri Sol 8: (C) Volume strength = 5.1 8 . When 20 mL of this solution is diluted. r. reaction is first order w. 6 = 4. 3 × 10–3= 2. 8 V. =k Now volume strength dt [B] = kt V = N × 5. normality of KMnO4 = M × 5 ∴ ∆H = Eb – Ef = (200 – 180) kJ mol–1 = 0.55 Average rate = = = 0.95M little probability for more than 3 atoms to collide simultaneously. t1/2 ∝ [A0] k = 0. d[A] 1. 303 hours. using N1V1 = N2V2 N .303 −k \ Rate = k[O2] [N2] 2 Slope of given graph = –3.303 Now. 02 × 5 = 0. 75 × 5. Conc. r. t graph is w. 1 N ∆H = 20 kJ/mol Now. it is a zero order Sol 9: (A) For experiment 1. pressure will get −kt doubled.(M)→ dt Sol 6: (B) The given option is correct as there is very 0. 60 hr–1 Sol 5: (C) Here. 2 V ⇒t3/4 ∝ [A0] 2. 10min Time(min)→ 2. 3[A]0 ⇒t = 4k Vf = 4. 055 min–1 ∆t 10 kt = 2. reaction.20 N Energy → Eb = ∆Η 100 5 It is diluted against 0. [A] = [A0] t Vt 4 t = 2.
rate = [NO]2 [Br2 ] k2 Rate of H2SO4 production Order w. 5 × 10–2 N k1 [NOBr2 ] = N1V1 = N2V2 k2 [NO][Br2 ] 2. At steady state. r2 = ∆t This is the plot for enzyme catalysed reaction. emission rate of SO3 2 Hence the reaction is first order = 6. = 8. 93 × 10–6 gm/L/day When (A) = 1. 375 ≈ 1. R = –k3[NOBr2] [NO] [SO3] = 1.(M)→ Sol 12: (B) EP 1. t.8 = M min–1 = 0.6625 × 10−8 Sol 11: (A) NO(g) + Br2(g) NOBr2(g) ⇒ [SO3] = k2 6. Chem i str y  18.93 × 10−3 NOBr2(g) + NO(g) → 2NOBr(g) 3 k [SO3] = 1.693 0. 25×10–2 mol When dissolved in water (1 L). 6625 × 10–8 – 693×10–3[SO3] dt therefore the final energy of products should be less d[SO3 ] than the reactants plot which satisfies above 2 is (A). 0. 8 M 6. 5 × 10–2 × 1000 = 1 × V2 k1 ⇒ [NOBr2] = [NO] [Br2] V2 = 25 mL k2 k 3k1 SO3 + H2O → H2SO2 Therefore. 25 × 10–5 M We use equilibrium approach In 10–3 of air. Rate. NO = 2 980 × 103 = 980 kg/day = mol/day = 104 mol/day 98 SO3 required = H2SO4 manufactured = 104 mol/day . 0. r = 1. Normality of SO3 = 2M = 2. moles of SO3 = 1. 08 M min–1 For decomposition of SO3. 5 = 1 r2 1 / 25 [A]0 Sol 13: (A. 93 × 10–3 day–1 Sol 10: (A) Since k1 << k2 second reaction will have the t1/2 100 most activation energy d[SO3 ] Further.2 1 Correct option is (B).55 [A]0 ⇒ 1 = = 1. = M min–1 = M min–1 5 25 Multiple correct choice type r 0.693 k= = = 6. 8 × [x]2 = mol/L/day 80 1. since the overall reaction is exothermic. r. = 1.85 Conc. =0 dt k1 8. 6625 × 10–8 mol/L/day 25 ≈ 0. D) We have.8M S+E ES 5 Time(min)→ Reaction coordinate→ ∆A Average rate. 25 × 10–5×103 Since second step is RDS.93 × 10−6 Rate. 072 M min–1 = 8.5M P Energy → 0. 25 × 10–2 M From equilibrium of (i).
rest all are correct. C. D) = k(A) 1/2 dt If all concentration other than (A) are constant. 8 6  Chemical Kinetics number of moles [A]1/2 Now V = 2 [A]1/2 − 0 M 0 2 10 4 k = = 8 × 108 L/day 1. [A] t −d[A] d(logk) ∫ = ∫ k dt Then =m 1/2 [A]0 [A] 0 d(log[A]) [A] t (C) Order of reaction can be fractional 2[A]1/2 = kt [A]0 0 (D) Order of a reaction can only be determined kt experimentally (A) 1/2 = [A]1/2 0 = 2 −1 1/2 1/2) Sol 17: (A. 2 × 10–8 M Rate. C) With increase in [A]0.25 × 10−5 [A]0 If SO3 emission stopped. resulting in 2 [A0 ]1/2 1/2 0 2([2A]0 − 2 increase in yield of B.93×10−3 t dextro after very long time ⇒ [SO3] = [SO3]0 e [SO3] 0 = [SO3]0 e−6. 25 × 10–5 M t = 1000 days Sol 16: (C. C) = = 0 ( 2 − 1) ( 2 − 1)[A]0 k (D) A zero order reaction is always complex. 93 × 10–3[SO3] dt Sol 15: (A.A 2 0 (A) Unit of A = Unit of k ≠ mol L–1s–1 kt A = + A0 (B) Order of an elementary must atleast be 1 (atleast 1 2 molecule should be present) Straight line (C) Molecularity can be defined for any elementary [A]0 reaction. 1/2 which means it has lower k and thus with increase in [A] temperature k1 will increase more than k2. t3/4 = k d[SO]3 = –6. rate will increase. A → B has higher Ea. At t = t1/2. B. D) Solution will be optically active and −6. [A0 ]1/2 − 0 2 leading to increase in yield of B. D) k= (A . k 2 2k 2[A]1/2 Sol 19: (A. (A) = 2 (D) Decay constant (λ) of radioactive substance is independent of temperature. D) (A) is correct \[SO3]0 ≈ 1.93×10 −3 t After 75% conversion of A in to B and C angle of rotation of solution will be 36° [SO3] 0 = 1. 2 2k t1/2 = [A0 ]1/2 Sol 18: (A. R = k[A] m[B] n[C]0 −d[A] log R = log k + m log[A] + n log[B] Sol 14: (A. (A) = 4 2k \t3/4 = [A]1/2 [A]1/2 0 − 0 2 . B.1 8 . [A]0 At t = t3/4.
= 1 = = –(k1 + k2)[x] [C] k2 2 dt 1 [x]t t For every mole of A consumed.θ∞ = –5º = n0. C = z) k2 2C We have.303 0. A0 = 1 mole 1 2 d[B] Bn = ×2×1 = moles Now.25 [C]t k2 (1 − e−kt ) 1 = = (e−kt − 1) [A]t k1 + k 2 e −kt k1 k = 0.93 0.5 – 2. θB = 30º. mole used for forming d[x] 3 ∫ = −(k1 + k 2 )∫ dt B and rest for forming C. [A]t = [A]0e–kt 2. for every mole A. through the overall order of a reaction can x be fractional. = k1[x]t 3 3 dt 2 4 d[B] Cn = ×2×1 = moles = k1[x]0e–kt 3 3 dt [B]t [Since. k2 C k1 2B A (B = y. [x] [x]0 0 [A]0 = 2 moles ⇒[x]t = [x]0e–kt. = 1 −kt [x]0 (1 − e ) = [x]0 e k θt = (n0 – x)θA + x(θB + θC) = 2. θA = 20º.40 – 20) = 2.43 min. k1 + k 2 θC = –40º [B]t + [C]t = [y] + [x] \ 30n0 – 40n0 = –5 k1 [x]0 k 2 [x]0 = (1 − e−kt ) + (1 − e−kt ) n0 = 0.θB + n0θC k 2 [x]0 Similarly [C]t = (1 − e−kt ) We have. k = k1 + k2 k For first order conversion.303 n 2. Chem i str y  18.5 ∴ = = [y] + [2] 1−e −kt e + (k1 +k 2 )t −1 30x = 20 × 0.5 − 0.25 k 2 [A]0 [C]t = (1 − e−kt ) . k = k1 + k2 At end of 50% reaction.5 k k k + k2 (1 −e−kt ) At time.5 x = 0.87 Assertion Reasoning Type Sol 22: (A) Sol 20: (C) Order of an elementary reaction cannot be k1 B fractional.5 [x]t e−kt 1 20n0 + x(30.5 k= log 0 = log t n0 − x 6. 2 moles of B (or C) is produced] t −kt ∫ d[B] = k1[x]0 ∫e 0 0 Sol 21: (D) A(aq) → B(aq) + C(aq) −k1 [x]0 t t=0 n0 [B]t = e−kt k 0 t = t n0 – x x x −k1 [x]0 t →∞ 0 n0 n0 [B]t = (1 − e−kt ) k1 + k 2 At t → ∞.1 min–1 1+ k2 . t = 6.5 Sol 23: (C) Using results of previous question 30x = 7. [B] k 1 d[x] We have.
k2 = 10 k1 Paragraph 2 = 10 × hr–1. −n1kt at = a e Sol 25: (A) Sol 29: (D) n1A(g) → n2B(g) Without catalyst t = 0 a 0 −n1kt n2 −n1kt t=1 ae a(1 − e ) n1 Ea Total moles present Energy R −n kt n n −n kt = a e 1 + 2 − 2 e 1 P n1 n1 Reaction coordinate n n −n kt = a 2 − 2 − 1 e 1 n 1 n1 With catalyst Concentration is to remain same at time t.1 8 . Comprehension Type nA = ae–kt Paragraph 1 V = V0(2 – (2 – 1)e–kt) = V0(2 – e–kt) 2 4 Sol 26: (B) Total number of moles = 1+ + = 3 moles e−kt 3 3 nA ae−kt (A) = = = (A) 2 V V0 (2 − e−kt ) 0 2 − e−kt Sol 27: (C) Moles of B = = 0. 8 8  Chemical Kinetics We have. reaction never goes to 100 at n = –n1kt % completion and hence time of completion cannot be a determined. 666 moles. total moles present(n) a ∴ = 0 V V0 Ea n n −n kt Energy R V0 n ⇒V = = V0 2 − 2 − 1 e 1 a0 n1 n1 P Reaction coordinate Sol 30: (B) If n1 = 1. 3 . a dt 0 For reactions with order > 1. t = 1 hr Sol 28: (B) We have. n2 = 2 at time t. k1 = x hr–1. [C]t 1 n1A(g) → n2B(g) ∴ (e(x +10x) − 1) = [A]t 1 1+ time 0 a 0 10 [C]t 10 11x time t a – n1x n2x = (e – 1) [A]t 11 −1 d[A] \Rate = k[A] = = k[A] n1 dt Sol 24: (C) For reactions with order ≤ 1. time of at t completion can be determined as those reactions gets d[A] ⇒ ∫ = −n1k ∫ dt fully completed in specific amount of time.
=0 2 dt 1 d[B] = 1 – e–kt =0 2 dt n2 0. . 0. 1 a n2 \k = ln = min–1 100 3 50 [A]t = [A]0 e–1000t a− a 4 1000 When x = 0. k2 = 20 s–1. 04 –ln(1 – f) = kt x = 0.89 Paragraph 3 Sol 33: (B) Slope of ln(1 – f) vs f graph k1 [A]0 −3 –1 Sol 31: (C) (B) = [e −k1t −e −k 2t ] = –k = hr k 2 − k1 200 3 d[B] k [A] −k t −k t ⇒k = hr–1 = 1 0 ( −k1e 1 + k 2e 2 ) 200 dt k 2 − k1 1 d[B] When f = When (B) is maximum. 04 f −ln(1 − f)0f = k f 0 i.5 We have. tmax = n 1000 − 20 20 1 50ln10 50 50 t= ln10 = = = .9a ≈ [A]0e–20t. = 166. . 16–x 3x 2x Paragraph 4 d[A] df Also. x = a 4 Sol 32: (C) For k1 = 1000 s–1. 16 e1. 66 min [B]t will increase till tmax and then decay exponentially k ln2 ln2 0. 16 At time t 0. 9 a. 36. ⇒ −k1e + k 2e =0 k 3 −k1t −k 2t k1 e = k 2e Sol 34: (A) f = 1 – e–kt k1 f = [1 – e–3t/200] = k2 k1 1 k Paragraph 5 (k1 – k2)t = ln .386×10 0 0 = 0. = [A]0(1 – e –1000t –e –20t ) 1 d[B] = k[A] ≈ [A]0(1 – e ) –20t 3 dt A(g) → 3B(g) + 2C(g) [C]t will approach [A]0 asymptotically. Chem i str y  18. = –k[A] We have = k(1 – f) dt dt [A] = [A]0 e–kt f f df −2 ×100 ∫1−f = ∫ k dt = 0. 16 = [A]0 – [A0] e–1000t – [A]0e–20t 12. [B]t = [A] [e−1000t − e−20t ] 20 − 1000 0 1 a k= ln 1 1000 t a − 0. ⇒t = ln 1 k2 k1 − k 2 k 2 3 Sol 35: (C) For t = 100 min.693 × 200 −k1t −k 2t t= = = 46. 12 f = 1 – e–kt (B) = 3x = 0. At time 0 0. e.3 [C]t = [A]0 – ([A]t + [B]t) 2 Sol 36: (B) [A]0 = = 0. 2 hrs. 16 – x = 0.
Straight line with slope equal to 2.1 8 . A = Preexponential factor. 9 0  Chemical Kinetics Match the Columns We know. Ea = Activation energy. Straight line with positive slope and positive intercept. [A0 ] [A] = [A]0 – kt 1 1 ⇒ − = –kt Straight line with slope –k. Straight line with positive slope. 1 (U) vs t(order = 2) [A] (B) → r we have. [A] (D) → q −1 t ⇒ = −k t [A]0 0 For zero order. decreasing graph 1 d[B] −d[A] = 2 dt dt Matches (C). n > 0 Previous Years’ Questions for order > D. s It is independent of [A]0. (q) t1/2 vs (A)0 (order = 1) Matches (D) 0. (C) → r. (s) r vs t (order = 0) k = Ae–Ea /RT where. [A] = [A]0e–kt −d[A] −k exponential decay = dt [A]2 (C) → p [A] t d[A] (B) = 2([A]0 – [A]). straight line parallel to xaxis. r is constant of time. graph is straight line parallel to xaxis. For order. = 2[A]0 (1 – e–kt) ⇒ ∫ = −k ∫ dt [A]0 [A]2 0 Exponential graph will approach 2(A)0 asymptotically. [A] = [A]0e–kt (V)r vs [A] (order = 1) ln[A] = ln[A]0 – kt r = k[A] Straight line with negative slope matches (A). rate decreases with increasing t as (A) decreases with t Sol 1: (A) The rate constant (k) of all chemical reactions \decreasing graph (not straight line) matches (C). [A]0 [A] 1 1 Sol 38: We will draw all graphs given in ColumnII and ⇒ = kt + [A] [A]0 then match them with ColumnI. (t) t1/2 vs [A]0 (order > 1) Sol 2: (C) A catalyst increases the rate of reaction but by the same factor to both forward and backward . Sol 37: (A) → s 1 t1/2 ∝ [A0 ]n−1 We have. depends on temperature. We have.693 (A) → p t1/2 = k (B) → q. (p) ln (A) vs t (order 1) Matches no option in ColumnI. t Matches (B) (D) → v (r) r vs t (order > 0) r = k[A]n.
40 14. between the absorption of C14 (produced due to cosmic radiation) and the rate of decay of C14 present inside ⇒ Rate = kN the plant. 100 kt = ln 100 – x Sol 3: (D) Rate will be directly proportional to both concentration and intensity. λT1 = ln C Sol 13: CH3–O–CH3(g) → CH4(g)+ H2(g)+CO(g) C ln 2 λT2 = At 12 min :0.14 × 106 determined in normal area.40 – p ln2 Sol 9: Rate of reaction is constant with time. 100 ⇒ = 1. This will N increase N0 because living plants are still taking C–14 ⇒ N0 = 1.175 Sol 10: k = = yr–1 = 1.91 directions.4 + 2p 1 ln2 = 0. i.14 × 106 atoms of Mo ⇒ T (age) determined in the area where nuclear ⇒ Mass of Mo required explosion has occurred will be greater than the same 2.995 × 106 from atmosphere. but N will not change because fossil will not be doing photosynthesis.0715 N 66. N0 ⇒ kt = ln N N0 ln2 N Sol 8: (A) λT =ln ⇒ × 6.6 × 60 of carbon in a living plant.4 + 2 × 0.693 = 1.074 amount of C14 in the near by area increases.074 × 1.40 – p ln2 0.5 × 10–6 s–1 to reach the equilibrium. ⇒N= = k 0. = × 99 = 3.0054 Sol 4: (D) Order of a reaction can take any real value. This gives a constant amount of C14 per gram Rate 346 × 66.995 × 106 atoms Sol 7: (B) Fossil whose age is closest to halflife of C–14 (5770 yr) will yield the most accurate age by C–14 dating. 100 – x ⇒ x =5. during photosynthesis. fraction.56 × 10–16g 6.5 × 10 −6 Sol 12: The minimum rate of decay required after 6.75 atm. = 2.6 N where N0 = Number of C14 in the living matter and N = Number of C14 in fossil.693 ⇒ p = 0. = × 12 = ln 0. N0 ⇒ = 1. negative. = 128.909 = ln 0 = 0. rate of formation of AB 100 ⇒ ln * ∝ C.074 × N = 1.693 constant increases exponentially with temperature : Halflife = = = 462000 s.33 h k = Ae–Ea /RT k 1.e. integer. 1 ⇒f= = 0. a catalyst shorten the time required Sol 11: k = 1. Also k × 12 = ln 0. = 0. Due to nuclear explosion. rate ln2 0.25% reactant is converted into product Sol 5: (A) According to Arrhenius equation.4 + 2p ⇒ T1 – T2 = ln C2 0.5 0.175 Also kt = ln = × 11540 = ln 4 f 5770 = 0.5 × 10–6 s–1 ×10 × 60 × 60s.023 × 1023 C1 Also.2 × 10–4 yr–1 t1/2 5770 ⇒ Total pressure = 0.055 i.e. Hence. Chem i str y  18. etc. 100 – x = 1.40 C = Concentration of C–14 in fossil.909 Sol 6: (A) Living plants maintain an equilibrium h is 346 particles min–1. I.25 4 .40 – p p p p C C1 Total pressure = 0.
303 ⇒ Partial pressure of N2O5(g) k remaining = 600 – 240 Sol 19: (D) Overall order of reaction can be decided by = 360 mm the data given t75% = 2t50% 360 ∴ It is a first order reaction with respect to P. 800 (B) k × 100 = ln = ln 2 n 400 r1 1 M Sol 20: (C) = = ⇒n= 3 ⇒ k = 6.93 × 10–3 min–1 r2 8 2Mn (C) For 75% reaction.33 k0 40 1.386 Ea k0 = = Also ln k = ln A – 2t1/2 2 × 20 RT At 50°C : k1 0.303 600–p 2p =t1/10 = log10 2 k k 3 2. C.5 × 107 Ea 50 ⇒ ln = 7 8.386 8. D) A high activation energy usually = 2 × halflife implies a slow reaction.303 2. i.693 22 × 1000 = × = = 0.303 × 3log2 1 Sol= 18: t1/8 = (b) N2O5 (g) → 2NO2 (g) + O2 (g) k k 2 p 2. every 100 min.693 40 0. Hence (D) is correct. 9 2  Chemical Kinetics k2 Ea T2 – T1 Sol 16: (D) aG + bH → Product Sol 14: (A) ln = k1 R T1 T2 rate ∝ [G]a [H]b a = 1.5 mol−1 litre ln A = ln (1. order of reaction with respect to Q is zero and the rate Sol 15: (A) Partial pressure becomes half of initial in expression is r = k [P]1[Q]0. b = 2 4.693 1.15 × 103 s–1 2. therefore.386 1.314 323 × 373 0.693 0.1 8 .375 960 From graph [Q] is linearly decreasing with time. ⇒ Molefraction = = 0.314 × 323 ⇒ A = 4.5 × 10 ) –7 = 8.5 × 10 Sol 17: (A) = k1 = t1/2 40 ⇒ Ea = 22 kJ A0 1. = 200 min (D) 2X(g) → 3Y(g) + 2Z(g) 3 800–x x x 2 3 Total pressure = 800 + x 2 Also 800 – x = 700 ⇒ x = 100 ⇒ Total pressure 3 = 800 + × 100 = 950 mm 2 .e. order = 1.303 × 3log2 Total pressure = 690 = 600 + p 2 t1/8 k × 10 9 ⇒ p = 240 mm = × 10 = t1/10 2. time required Sol 21: (B.303log8 2.
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S fP r es o titut Ins CHEMISTRY FOR JEE MAIN & ADVANCED SECOND EDITION Exhaustive Theory (Now Revised) Formula Sheet 9000+ Problems based on latest JEE pattern 2500 + 1000 (New) Problems of previous 35 years of AIEEE (JEE Main) and IITJEE (JEE Adv) 5000+Illustrations and Solved Examples Detailed Solutions of all problems available Plancess Concepts Topic Covered Tips & Tricks. Notes. Facts. Key Take Aways. Problem Solving Tactics Solid State PlancEssential Questions recommended for revision . Misconceptions. 201718 100 & op kers Class 12 T By E ran culty JE Fa r IIT enior emie .
directions. 3. Isotropy and These are anisotropes i.p. properties such as refractive index. Symmetry These possess symmetry. INTRODUCTION We know that solids are substances which have a definite volume and a definite shape. rigidity and volume. their physical Anisotropy properties such as refractive index. conductivity etc. Geometry These have definite regular geometry These do not have definite orderly which extends throughout the crystals i.e. melting... arrangement.. CLASSIFICATION OF SOLIDS Solids can be broadly classified into two types: 1. their physical These are isotropic i. Interfacial angles Crystals are always guarded by planes so These do not possess interfacial angle.1: Difference between crystalline and amorphous solids S. 5. Melting Points These have sharp m. These do not possess any symmetry. 6. Property Crystalline solids Amorphous solids 1. have same value in all the different directions. Amorphous Table 19. 2. these solids have long range order. Volume change There is a sudden change in volume when There is no sudden change in volume on it melts. that a definite angle exists between two planes called interfacial angle.p. . These do not have definite heat of fusion. 7.e.e. Heat of Fusion These have definite heat of fusion. 2. have different values in conductivity etc. S O L I D S TAT E 1. 4. 19. Crystalline 2. A solid is a nearly incompressible state of matter with a welldefined shape.No. These do not have sharp m.
Cu. Units that occupy Atoms or molecules Atoms Positive ions in a ‘sea Positive and negative of electrons’ ions 2. (i) Very hard (i) Hard or soft (i) Quite hard and brittle (ii) Low melting points (ii) Very high melting (ii) Moderate high (ii) Fairly high melting points melting points points (iii) Non conductors (iii) Non conductors (iii) Good conductors 4. Solid NH3.1 9 . Diamond. 2  Solid State PLANCESS CONCEPTS Glass Transition Temperature An important property of amorphous polymer is glass transition temperature at which a glassy polymer transforms into flexible rubberlike mass capable of taking on shapes and forms. A more stable structure would require higher energy and hence melt at higher temperature. Fe. TYPES OF CRYSTALLINE SOLIDS On the basis of the nature of the constituent particles and the interparticle forces. KNO3. Example Solid Ne. dry ice Carborundum (SiC). Nikhil Khandelwal (JEE 2009 AIR 94) . (Solid CO2) quartz (SiO2) PLANCESS CONCEPTS Stability of a crystal is reflected in the value of its melting point. Vaibhav Krishnan (JEE 2009 AIR 22) 3. This property is used in the processing of polymers. Binding forces Vander Waal’s forces Covalent bonding Metallic bonding Ionic bonding (weak intermolecular (shared pair of (extreme delocalised (electrostatic attraction forces) of following electrons) bond) – positively between positive and two types charged atomic negative ions) cores surrounded by (i) London (dispersion) ‘sea’ of delocalised forces electrons (ii) Dipoledipole forces 3. crystalline solids may be divided into four classes.2: Characteristics of various types of solids Characteristics Molecular Solids Covalent Network Metallic Solids Ionic Solids 1. Table 19. Na2SO4 ice (Solid H2O). Ag NaCl. Physical Properties (i) Very soft.
Crystal System Axial Characteristics Examples 1. α = β = γ = 90º diamond 2. Cubic (Most symmetrical) a=b=c NaCl. Ag. c and their angles α. A line passing through the centre of a crystal in a direction parallel to the edge of zone is known as zone axis. These are known as unit cell parameters. Edges: The intersection of two adjacent faces forms an edge. Such unit cell are called nonprimitive unit cells. SnO2. Bravais (1848) showed from geometrical considerations that there can be only 14 different ways in which similar points (spheres) can be arranged.g. γ. when there are points only at the corner of the unit lattice. These fourteen types of lattice are known as Bravais lattices. Galena. CsCl. Crystal System: The unit cell in a 3dimension lattice is characterized by the length a. Interfacial Angle: The angle between the normals to the two intersecting faces is called interfacial angle. Tetragonal a=b≠c White tin. The planes which bind the crystal. Space Lattice z Lattice Point c a x b c Unit Cell a b Representation of y dimension of unit cell Figure 19. KCl. However. Cu. Faces: The surfaces are usually planar and arranged on a definite plane (as a result of internal geometry). TiO2 α = β = γ = 90º . b.. e. Chem i str y  19. Faces are of two types: (i) Like: A crystal having all faces alike. zinc blende. β.g. SALIENT FEATURES OF CYRSTALS A crystal possesses the following characteristic features: 1. certain unit cells have lattice points on other sides also in addition to the corners. (ii) Unlike: A crystal having all faces not alike. They can be divided into seven crystal systems as shown below: Table 19. are called faces. e. 2. Form: All the faces corresponding to a crystal are said to constitute a form.1: Representation of space lattice and unit cell Crystal Lattice: A space lattice is called a crystal lattice when the lattice points in the space are replaced by actual atoms or ions. 5. 4. Zone and Zone Axis: The faces of a crystal occur in sets called zones.3 4.3: Crystal system table S. which meet in parallel edges or would do so if the planes of the faces are extended. 3. Each zone forms a complete belt around the crystal. Fluorspar. Space Lattice: A three dimensional arrangement of points that shows how the atoms or ions are arranged in space is called a Space Lattice.No. Bravais Lattices: An arrangement of spheres as given above leads to simple or primitive unit cell. Each point is individually called a lattice point.
they are also referred to as mirror planes. There are two types of mirror planes (as shown below). Hexagonal a=b≠c Graphite α = β = 90º. β ≠ 90º Na2SO4. ICl α = β = γ ≠ 90º 6. Every Crystal Possesses Only One Centre of Symmetry (b) Plane of Symmetry: It is an imaginary plane passing through the crystal which can divide it into two equal parts in such a way that one part is an exact mirror image of the other. SYMMETRY IN A CRYSTAL (a) Centre of Symmetry: Centre of symmetry of a crystal may be defined as an imaginary point within a crystal such that any line passing through it.1 Laws of Crystallography The geometric crystallography (the outward spatial arrangement of crystal planes and shape of crystals) is based on the following three fundamental laws: (a) The Laws of Constancy of Interfacial Angles: The crystals of a substance can have different shapes depending upon the number and size of the faces but the angle at which the two adjacent faces intersect remains always constant. b. Thus. α = γ = 90º. the angle at which two adjacent faces intersect always remains constant. CuSO4. (b) Hauy’ s Law of Rationality of Indices: The intercepts of any face of plane of a crystal on suitable crystallographic axes can be expressed by small multiples of three unit distances a. 4  Solid State 3. As. PbCO3.e. (A) Rectangular mirror planes (B) Diagonal mirror plane . KNO3 α = β = γ = 90º 4. Sb.1 9 . intersects the crystal at equal distances in both directions e. n. i. γ = 120º PLANCESS CONCEPTS The relationship between the plane faces (F). straight edges (e) and interfacial angle (C) for a given crystal can be written as: F + C =e + 2 Saurabh Gupta (JEE 2010 AIR 443) 4. However.. staggered form of ethane possesses a centre of symmetry.5H2O α ≠ β ≠ γ ≠ 90º 7. H3BO3.g. Monoclinic a≠b≠c Monoclinic sulphur. quartz. NaNO3. ma: nb: pc or fraction of whole numbers. all crystals of the same substance possess the same elements of symmetry. Rhombohedral or trigonal a=b=c Calcite. PbSO4. p) of these unit distances. Triclinic(Most unsymmetrical) a≠b≠c K2Cr2O7.10H2O 5. the crystals of a substance can have different shapes. Orthorhombic a≠b≠c Rhombic sulphur.2H2O . 5. Depending on the number and size of the faces. (c) The Law of Constancy of Symmetry: According to this law. CaSO4. c or some simple integral multiple (m.
2: Representation of type of plane of symmetry present in a unit cell 5. after a rotation through 180º. I. passing through the crystal such that when the crystal is rotated about this line. ThreeFold Axis: If the original appearance occurs thrice. Neeraj Toshniwal (JEE 2009 AIR 21) . n TwoFold Axis: If a similar appearance occurs two times in one complete rotation i. on rotating through an angle of around an imaginary axis it is called nfold axis of symmetry where n– is known as order of axis.3: Representation of axis of symmetry present in a unit cell PLANCESS CONCEPTS A crystal may have a number of planes or axis of symmetry but it possesses only one centre of symmetry. then it is called three fold axis of symmetry.e. through 360º. it presents the same appearance more than once in one complete rotation. the axis is called two fold axis of symmetry or dyad axis. Four fold Axis Two fold axis of symmetry Three fold Axis (a) (b) (c) Six fold Axis of symmetry 1Rectangular Plane 2Rectangular 3Rectangular Plane Plane in a cube (d) (e) A B Diagonal plane 1 CBFB C Diagonal plane 2 ADHE D Diagonal plane 3 ABHG E F Diagonal plane 4 CDEF Diagonal plane 5 CAFH Diagonal plane 6 EGDB G H (f) Figure 19.1 Axis of Symmetry or Axis of Rotation An axis of symmetry or axis of rotation is an imaginary line. 360º When the same appearance of crystal is repeated.e. Chem i str y  19.5 Rectangular mirror plane Diagonal mirror plane Figure 19.
This classification depends on the position of constituent particles in a unit cell. a cube has 23 elements of symmetry. (iv) A bodycentred point belongs entirely to one unit cell since it is not shared by any other unit cell.4: Number of atoms in different type of unit cell Type of cell Number of atoms Number of atoms Number of atoms in Total at corners in faces the body of cube Simple or primitive 1 8× 1 = 0 0 1 cubic 8 Bodycentred cubic 1 8× 1 = 0 1×1=1 2 (bcc) 8 Facecentred cubic 1 1 8× 1 = 6× 3 = 0 4 (fcc) 8 2 . UNIT CELL The smallest repeating pattern in a space lattice is called a unit cell. Therefore onehalf (1/2) part lies in each unit cell. 6.2 Total Elements of Symmetry in a Cubical Crystal Total planes of symmetry =3+6=9 Axis of symmetry = 4 (3fold axis) 3 (Four fold axis) 6 (Six fold axis) = 13 Axes of symmetry Centre of symmetry =1 Hence. face centred and end centred. Simple or Body centred Face centred End centred Primitive (P) (I) (F) (E) Figure 19. 6  Solid State 5. (ii) A point present on an edge is distributed among the four unit cells. Therefore. body centred.1 Types of Unit Cell Unit cells are classified as simple or primitive. therefore only onefourth (1/4) of such a point belongs to the given unit cell. Table 19. only oneeighth (1/8) portion of each of such a point belongs to the given unit cell. its contribution to the unit cell is one. (iii) A facecentred point is shared between two unit cells.2 Number of Atoms in a Unit Cell (i) A point lying at the corner of a unit cell is shared equally by eight unit cells and therefore.4: Different types of unit cell 6. 6.1 9 .
Y atoms are at the cube centres and O atoms are at the edge centres. What is the formula of the compound? (JEE MAIN) Sol: Determine the number of atoms of A (Occupying Corner of a cube) present in one unit cell and no. Y and O present in a unit cell. Oneeighth of each corner atom (Au) and onehalf of each facecentred atom (Cu) are contained within the unit cell of the compound. of atoms of Ag (occupying Body center arrangement) present in one unit cell An atom at the corner of the cube is shared by 8 cubes and hence. . There are eight corners of a cube. thus contribution of Y towards unit cell = 1 x 1 = 1 O atom is present at each of the edge centre (number of edges of cube = 12) And each O atom present at edge centre will make 1/4 contribution towards the unit cell. 1 ∴ The number of A atoms in the unit cell = 8 × = 1 8 An atom at the body centre of cube belongs only to one unit cell. each atom of X at the corner makes 1/8 contribution towards the unit cell. Therefore. 1 Thus. y atom occupies body center and O occupies edge centre. therefore XYO3.7 Illustration 1: A solid has a cubic structure in which X atoms are located at the corners of the cube. (JEE MAIN) Sol: Determine the number of atoms of Au (Occupying simple primitive structure) present in one unit cell and no. 1 The number of O atoms per unit cell = 12 × =3 4 The formula of the compound is. formula is AB. ∴ Number of atoms of B in the unit cell = 1 × 1 = 1. Illustration 2: A cubic crystalline solid contains P atoms at the corners and Q atoms at the body centres. Illustration 4: A compound formed by elements A and B crystallizes in cubic structure where A atoms are at the corners of a cube and B atoms are at the body centre of the cube. Determine the formula of this compound. what will be the simplest formula of the resulting solid? (JEE MAIN) 1 7 Sol: ZP = 7 × = 8 8 ZQ = 1 ∴ The simplest formula is P7 Q = P7 Q8 . Atoms of X are present at all the eight corners of the cube. Thus. number of Au atoms per unit cell = 8 × =1 . lf one atom from the corner is missing. and 8 1 Number of Cu atoms per unit cell = 6 × = 3. Chem i str y  19. So calculate the no of atoms of X. What is the formula of the compound? (JEE MAIN) Sol: X atom is occupying simple cubic structure. contributes only 1/8 to a particular cube. 2 The formula of the compound is AuCu3. of atoms of Cu (occupying face center arrangement) present in one unit cell . 8 Illustration 3: A compound alloy of gold and copper crystallizes in a cube lattice in which the gold atoms occupy the lattice points at the corners of a cube and the copper atoms occupy the centres of each of the cube faces. 1 Number of atoms of X per unit cell = 8 × = 1 8 Y atom is present at the body centre.
5b: Diagramatic representation face centred unit cell (c) Body Centred Cubic Structure (bcc): It is clear from the figure. e.g.5c: Diagramatic representation of body centred unit cell .3 Coordination Number The number of nearest neighbours that an atom has in a unit cell is called the coordination number. each atom say (A) has eight body centred atoms of 8 surrounding unit cells as neighbours in one plane. a body centred cubic structure reveals a coordination number of eight. CsCl. 3. In ionic crystal. Copper. A possesses 12 neighbour atoms and therefore. E F 2 A B 1 3 G 4 H D C Face centred cubic Figure19. that the nearest neighbour of a corner atom is body centred atom.. Thus. 8  Solid State 6. NaCl. The coordination number of a crystal depends upon its structure. Thus. in all. (a) Simple Cubic Structure: It is clear from the Figure that each atom say (A) has 4 nearest neighbours 2. it also possesses four face centred atoms in planes below and above it.1 9 . In addition. from the figure. 4 and the other is on its left side from another cell. each atom say (A) has 4 nearest neighbours 1. Thus... the number of oppositely charged ions surrounding each ion is called its coordination number.g.5a: Diagramatic representation of simple unit cell (b) Face Centred Cubic Structure (fcc): It is clear. 2 A 4 3 Simple cubic Figure 19.g. In addition. that the nearest neighbour of a corner atom is the face centred atom and thus. a simple cubic structure reveals a coordination number of six. e. it also possesses one atom vertically above of another unit cell. A possesses six neighbour atoms and therefore. in all. face centred cubic structure reveals a co ordination number of twelve. A 1 Body centred cubic Figure19. since A is surrounded by 8 surrounding unit cells. e. 2. 4 and one to the left of A of another unit cell in one plane. Thus.
wt. of Atoms × Mass of one of atom = n × Avog. •• High temperature decreases the coordination number. Calculate the atomic radius. no. Aman Gour (JEE 2012 AIR 230) 6.9 PLANCESS CONCEPTS Pressure and temperature changes the coordination number of a crystal.no. a3 × Av. No. . •• High pressure increases the coordination number. It is equal to a3 for cubic crystal systems. mass per unit cell Density of lattice matter = volume of unit cell Atomic mass Mass per unit cell = No. Now. Density of lattice matter = Av.99) (JEE MAIN) Sol: From the given value of edge length first determine the atomic radius for a bcc crystal lattice and density can be determined using the following formula.27 pm 4 4 n × at. no. n × at. (in cm) Where ‘n’ is number of atoms per unit cell. What would be the density of chromium in g/cm3? (At. Show how you can calculate its density. Density = = V × Av. volume of unit cell is to be derived for given crystal system. no. wt. The edge length of the unit cell is found to be 287 pm.4 Density of Lattice Matter It is defined as the ratio of mass per unit cell to the Volume of unit cells. n × at. no. a3 × Av. wt. × volume of unit cell n × atomic mass (or molar mass) ρ = NA × V n × atomic mass ρ = NA × a3 Where ‘a’ is edge length of cube. Density = = V × Av. wt. (JEE MAIN) Sol: The density of the unit cell is the same as the density of the substance. 3a 3 For bcc lattice. r = = × 287 =124. wt. Chem i str y  19. of Cr = 51. Illustration 5: The edge length of a cubic crystal of an element is found (by Xray diffraction) to be ‘a’ picometres. wt. n × at. n × at. Edge length of unit cell = a pm = a × 10–10 cm Volume of the unit cell = a3 × 10–30 cm3 n×M Density of the unit cell = gcm−3 3 −30 a × NA × 10 Illustration 6: Chromium metal crystallizes with a body centred cubic lattice.
5 Nearest Neighbouring Distance in Case of Identical Spheres Nearest neighbouring distance is the distance between the centres of any two touching spheres. (JEE ADVANCED) Sol: First determine the molecular mass of the element by using following equation.6a: Nearest neighbouring distance in case of SCC (b) Body Centred 2 (AB) = (AC)2 + (BC)2 ⇒ (Body Diagonal)2 = (Face Diagonal)2 + (edge)2 = 2(edge)2 + (edge)2 = 3(edge)2 .4 × 10–24 In a body centred cubic (bcc) structure n = 2.023 × 10 × 24.8 = 23 6.no.no.4 × 10−24 6. Let M be the molecular mass of the element. 1 0  Solid State n = 2 for bcc.1 9 . × a3 And from molecular mass determine the number of atoms present in 200 g of the element. Volume of the unit cell = a3 = (290 × 10–10 cm)3 = 24. (a) In case of SCC (Simple Cubic Lattice) In a simple cubic lattice the edge length (a) = Nearest neighbouring distance a = d = 2r a ⇒ r = 2 d a Figure19. n×M Density = Av. Calculate the number of atoms present in 200 g of the element.8 g cm–3) occurs in bcc structure with unit cell edge of 290 pm.023 × 1023 × 200 200 g of the element would contains = = 24.09 × 1023 atoms 50 6.023 × 1023 × 24. n×M Density = Av.99 ∴ ρ= = 7.31 g / cm3 −10 3 23 (287 × 10 ) × (6. × a3 2×M 6.023 × 10 ) Illustration 7: An element (density 6.4 × 10−24 M= = 50 g 2 ∴ 50 g of the element contain 6.8 × 6.023 × 1023 atoms 6. a = 287 pm = 287 × 10–10 cm 2 × 51.
z = number of sphere per unit cell .6b: Nearest neighbouring distance in case of BCC (c) Face Centred Cubic Lattice Here (Face diagonal)2 = (edge)2 + (edge)2 ∴ ( face diagonal) = a2 + a2 = 2a2 2 ∴ face diagonal = 2a ∴ 4r = 2a B r r r C r A d est ing ar r u ne bo ce g h an i t ne dis Figure 19.11 ⇒ (Body Diagonal)2 = 3(edge)2 = 3a2 ∴ body diagonal = 3 a Also Body Diagonal = r + 2r + r = 4r 3 ⇒ 24r = 3a ⇒ r = a 4 3 d = 2r ⇒ d= a = nearest neighbouring distance 2 A B r r r d r C D Figure19. Chem i str y  19.6 Packing Fraction Packing Fraction in Case of Identical Spheres Packing fraction is the ratio of volume occupied by sphere to the total volume of the cube 4 3 πr × z Volume occupied by sphere 3 = Packing Fraction = Total volume of cube a3 where a = edge of cube.6cNearest neighbouring distance in case of FCC 6.
e. 1 6 r= 6 NA × a3 × 10−30 cube (sc) 2 = 52. B Rajiv Reddy (JEE 2012 AIR 11) Table 19. more closely packed atoms are in FCC structure. No.6% Packing fraction for BCC 3 4 3 π a × 2 3 3 4 4 π×3 3 ×2 3π r= a .68 = 68% % Free space = 100 – 68 = 32% Packing Fraction for FCC 3 4 2 π a × 4 2 3 4 4 π×2 2 × 4 2π r= a . i.. z = 4 PF = = × = 0. FCC > BCC > SCC. Cubic Nuber of Coordi. = PF = = 2 a3 8×3 6 ' π ⇒ PF = =0. Atomic Packing Density (ρ) Nearest effective nation radius (r) efficiency neighbour (g cm )–3 atoms per Number distance unit cell (Zeff) (CN) (d) Z eff × Mw π ρ= a Simple a PE= × 100 1.524 6 π ⇒ % volume occupied by sphere = × 100 = 52. z = 1.1 9 .68 = 4 a3 3 64 8 ⇒ % volume occupied = 100 × 0.7407 = 4 a3 3 64 6 2π ⇒ PF = = 0.52.4% 6 ⇒ % Free space = 100 .4% 1 × Mw = NA × a3 × 10−30 .740 6 % volume occupied = 100 × 74 = 74 % % Free space = 100 – 74 = 26 % PLANCESS CONCEPTS The packing density data reveals that close packing of atoms in cubic structure follow the order.4 = 47. z = 2. 1 2  Solid State Packing fraction of SCC 3 4 a π × z a 3 2 4π π r= .5: Summary of Various Characteristics of Different Cubic Systems S. PF = = × = 0.
we can determine % empty space by subtracting the volume of solid Ar taken and volume occupied by Ar. This can be done in two different ways as shown in figures (a) and (b).65 Also. spheres are arranged in a row. Chem i str y  19. in a one dimensional close packed structure as shown below.65 g or one cm3 = × 6.65 g/mL at –233ºC. centred 2 8 r= 8 ρ= a cubic (bcc) 4 = 68% 3 NA × a × 10 −30 2 Face 2 4 × Mw 3.65 ∴ Total volume of all atoms of Ar in solid state = πr N = × × (1.7b: Close packing of spheres in two dimension .54 × 10−8 )3 × × 6. Figure 19. number of atoms in 1. What percentage of solid Argon is apparently empty space? (Ar = 40) (JEE ADVANCED) Sol: First determine the no.54 × 10–8 cm. touching each other. If the Argon atom is assumed to be sphere of radius 1.7a: Close Closepacking packingofofspheres in one dimension spheres in one dimension (b) Close Packing in Two Dimensions: Twodimensional close packed structure can be produced by stacking the rows of close packed spheres.380] ∴ % empty space = × 100 = 62% 1 7. CLOSED PACKING OF CONSTITUENTS (a) Close Packing in One Dimension: Here.023 × 1023 = N 40 4 3 4 22 1.380 cm3 3 3 7 40 As the volume of solid argon taken = 1 cm3 [1 − 0.13 Body 3 3a PE = π × 100 2 × Mw 3 2.65 g from this calculate the total volume occupied by all atoms of Ar. of atoms of Ar present in 1. (i) Square close packing (ii) Hexagonal close packing Figure 19.023 × 1023 = 0.04% Illustration 8: The density of solid Argon is 1. 4 Volume of one atom of Ar = πr3 3 1. centred 4 12 a PE = π × 100 ρ= a r= 6 cubic (fcc) 2 2 NA × a3 × 10−30 2 = 74.
half of these holes can be filled by these spheres. In every second row the particles occupy the depressions (also called voids) between the particles of the first row. 1 4  Solid State (c) Close Packing in Three Dimensions: (i) Hexagonal Close Packing (HCP):.. Presume that spheres in the third layer are arranged to cover octahedral holes. only 68% space is occupied and 32% remains unoccupied. G fold axis A B A B A (a) (b) (c) Figure 19.7c: Hexagonal close packing of spheres in three dimension (ii) Cubic Close Packing (CCP): If we start with hexagonal layer of spheres and second layer of spheres is arranged by placing the spheres over the voids of the first layer.While forming the first layer. A single unit cell has 4 atoms. but the fourth layer is similar to the first layer. In the third row. the particles are vertically aligned with those in the first row giving AB AB AB . minimum space is wasted by utilizing the maximum space possible.. fifth layer to second. 8 particles are present at the corners and 1 particle is present at the body centre. When organized this way. the third layer does not resemble either the first or second layer. .. The efficiency of this type of packing is less..P. . This arrangement has cubic symmetry and is known as cubic closed packed (CCP) arrangement.C. type of arrangement. the coordination number is 12 and only 26% space is free. C Three fold axis B A C B A (a) (b) (c) Figure 19.1 9 . sixth to third and so on giving pattern ABCABCABC . The coordination number of central sphere is 8.7d: Cubic close packing of spheres in three dimension (iii) Body Centred Close Packing (BCP): In B. In HCP. A single unit cell has 2 atoms. The free space available in this packing is 26% and coordination number is 12. This structure has hexagonal symmetry and is known as hexagonal close packing (HCP). This is also called facecentred cubic (FCC) arrangement. arrangement.
T T T T T T T o o o o o o T T T T T T T T T T T T o o o o o o T T T T T T T Figure 19.74. there is less free space between sphere than two dimensional square close packing. There is one octahedral void per atom in a crystal. and (c) Geometrical shape of the void . the fraction of the total volume occupied is 0. Explain. The two structures have the same coordination number of 12. •• In hexagonal close packing about 60. VOIDS OR HOLES The voids/holes are the empty spaces in between closed packed spheres.4% of the space by spheres.414. the spheres arrange themselves in hexagonal close packing.15 PLANCESS CONCEPTS •• In two dimensional hexagonal close packing. Thus. (JEE MAIN) Sol: In both the structures. Chem i str y  19. •• If only one layer of spheres is to be packed. 8.8b: Tetrahedral and Octahedral Voids (a) top view. Rohit Kumar (JEE 2012 AIR 79) Illustration 9: A hexagonal closepacked structure and a cubic closepacked structure for a given element would be expected to have the same density. Tetrahedral Tetrahedral hole hole Tetrahedron Octahedral hole Octahedral hole Octahedron (a) (b) (c) Figure 19. the coordination number of spheres remain twelve. (b) exploded side view. •• In both CCP and HCP.8a: Representation of a Void Types of Voids: (a) Octahedral Voids: This void is surrounded by six spheres and formed by a combination of two triangular voids of the first and second layer. The radius ratio (r void/rsphere) is 0. hexagonal close packing is denser than square close packing.4% of available space is occupied by spheres whereas square close packing occupies only 52.
There are 8 trigonal voids per atom in a crystal and the radius ratio is 0. + or vice versa.6: Summary of the Main Characteristics and Examples of Some Simple Ionic Solids Crystal Structure Brief description Examples Coordination Number of Coordination number formula unit/ number units cell Type AB: Rock salt It has fcc arrangement Halides of Li.8c: Trigonal void void Locating Tetrahedral and Octahedral Voids: Both octahedral and tetrahedral voids are present in all closed packed structures. Zn2+ are in vice versa. AgBr.155. Each Na+ is General 6: 6 (NaCl) type in which Cl– ion occupy Rb. 6 Cl–. NH4Br. CsI. TlBr. 1 6  Solid State (b) Tetrahedral Voids: These voids are surrounded by four spheres. CsBr. PLANCESS CONCEPTS The coordination number of a tetrahedral void is four. occupy all OVs at the body and edge centres. there is one octahedral void at the centre of body and 12 octahedral voids in each of the 12 edges of the cube. There are 2 tetrahedral voids per atom in a crystal and the radius ratio is 0. . Each void on the edge is shared by four other unit cells. Radius for fcc (r + ) a + r− = 2 Cesium Chloride It has bcc arrangement CsCl. Each Cl– is or AB centres of a cube while NH4I surrounded by 6 Zeff = 4 Na+ ions are present Na+. FigureTrigonal 19. TlCl. formula AB centre and Cl– ions at TlI and TlCN Each Cl– is Zeff = 1 the corners of a cube surrounded by 8 Cs . (c) Trigonal Voids: The void enclosed by three spheres in contact is called a trigonal void. AgF. Each Zn2+ is General 4: 4 (sphalerite) type in which S2– ions form AgI surrounded by formula A4B4 fcc and each Zn2+ 4 S2–. The coordination number of an octahedral void is six.1 9 . Each Cs+ is General 8: 8 (CsCl) type with Cs+ at the body CsCN. CuBr. surrounded by formula A4B4 the corners and face NH4Cl. AIR 199) Table 19. In a CCP pattern.225. Each S2– is or AB ion is surrounded surrounded by 4 Zeff = 4 tetrahedrally by S2– ion Zn2+. Krishan Mittal (JEE 2012. Radius for bcc type (r + + r− =) 3a 2 Zinc blende (ZnS) It has ccp arrangement CuCl. which lie at the vertices of a regular tetrahedron. CuI. surrounded by 8 Cl–. alternate TVs.
Chem i str y  19.17
Crystal Structure Brief description Examples Coordination Number of Coordination
number formula unit/ number
units cell
Type AB2 Fluorite It has ccp arrangement BaF2, BaCl2, SrF2, Each Ca2+ is General 8: 4
(CaF2) type in which Ca2+ ions form SrC2, CdF2, PbF2 surrounded by formula A4B4
fcc with each Ca2+ ions 8 F–. Each F– is or AB
surrounded by 8 F– ions surrounded by 4
Zeff = 4
and each F– by 4 Ca2+ Ca2+. F– ions occupy
ions all the 8 TVs.
Type A2B Here O2– form the Na2O, Li2O Each Na+ is General 4: 8
Antifluorite Type ccp arrangement so surrounded by 4 formula A4B4
that each Na+ ion is O2–. Each O2– is or AB
surrounded by four O2– surrounded by
Zeff = 4
ions and each O2– ion 8 Na+. Na+ ions
is surrounded by 8 Na+ occupy all the TVs
ions.
Illustration 10: In a cubic lattice, the closed packed structure of mixed oxides of the lattice is made up of oxide ion;
one eighth of the tetrahedral voids are occupied by divalent ions (A2+) while one half of the octahedral voids are
occupied by trivalent ions (B3+). What is the formula of the oxides? (JEE ADVANCED)
Sol: Let there be n no. of O2– in the crystal.
∴ Octahedral voids = n
Tetrahedral voids = 2n
1 n 3+ 1 n
A2+ ions = × 2n = , B ions = × n =
8 4 2 2
n n
A2+ : B3=
+
: O2 − =: :n 1:2: 4
4 2
∴ Formula is AB2O4.
9. RADIUS RATIO
The ratio of radius of cation to anion is known as radius ratio of ionic solids, i.e.,
Radius of cation (or r + )
Radius ratio =
Radius of anion (or r − )
Following important conclusions can be drawn from radius ratio of ionic solids.
(a) If the radius ratio (r+/r–) = 0.225, the cation would fit exactly into the tetrahedral voids and have coordination
number four.
(b) If the radius ratio (r+/r–) = 0.414, the cation would fit exactly into the octahedral voids and have coordination
number six.
Illustration 11: If the radius of the bromide ion is 0.182 nm, how large a cation can fit in each of the tetrahedral
hole? (JEE MAIN)
Radius of cation (or r + )
Sol: Radius ratio =
Radius of anion (or r − )
For tetrahedral voids (r+/r–) = 0.414
1 9 . 1 8  Solid State
From the given value of radius of the bromide ion determine the radius for cation. Depending upon the size of the
cation predict the answer.
For tetrahedral voids (r+/r–) = 0.414 (for maximum value of r+)
r+ = 0.414 × 0.182 = 7.53 × 10–2 nm
Thus, cation of 7.53 × 10–2 nm will fit exactly in tetrahedral voids.
Illustration 12: In the cubic crystal of CsCl (d = 3.97 g cm3) the eight corners are occupied by Cl– with a Cs+ at the
centre and vice versa. Calculate the distance between neighbouring Cs+ and Cl– ions. What is the radius ratio of the
two ions? (At. wt. of Cs = 132.91 and Cl = 35.45) (JEE ADVANCED)
Sol: In a unit cell, n = 1 for cubic crystal
n × mol.wt. n × mol.wt.
∴ =
density =
V × Av.No. a3 × Av.No.
1 × 168.36
∴ 3.97 =
a3 × 6.023 × 1023
a = 4.13 × 10–8 cm
a = 4.13 Å
For a cube of side length 4.13 Å.
Diagonal = 3 × 4.13 =
7.15 Å
As it is a bcc with Cs+ at centre (radius r+) and Cl– corners (radius r–) so,
2r+ + 2r– = 7.15 or r+ + r– = 3.57 Å
i.e., distance between neighbouring Cs+ and Cl– = 3.57 Å
Now assume two Cl– ions touching each other
So, Length of unit cell = 2r– = 4.13 Å
∴ r– = 2.06 Å
∴ r+ = 3.57 – 2.06 = 1.51
r+ 1.51
∴ = = 0.73
r − 2.06
10. DEFECTS
Atomic Imperfection: Atomic imperfections are the defects that arise due to irregularity in the arrangement of
atoms or ions. These are of following types:
Point Defects: These are caused by missing or misplaced atoms or ions. These involve:
(a) Vacancy defect: If an atom or ion is missing from the lattice site, the defect is known as vacancy defect.
(b) Impurity defect: If a foreign atom or ion occupies a lattice site as an impurity, the defect is called impurity
defect. If the foreign atom or ion occupies voids in the structure, the defect is called interstitial impurity.
Point Defects: These are caused by a departure from the periodic arrangement in the vicinity of an atom or a
group of atoms. Point defects in crystals may be classified as:
(a) Defects in stoichiometric solids, also called as stoichiometric defects.
(b) Defects in nonstoichiometric solids, also called as nonstoichiometric defects.
(c) Impurity defects.
Chem i str y  19.19
Defects in Stoichiometric Solids: Stoichiometric solids are those in which the number of positive and negative ions
are exactly in the ratio indicated by their chemical formulae. These are of 2 types (i) Schottky defect, (ii) Frenkel defect
(i) Schottky Defect: A pair of ‘holes’ or vacancies exists in the crystal lattice due to one cation and one anion
missing from the normal lattice sites. As the number of missing cations and anions remain the same, the crystal as
a whole remains the same. This sort of defect occurs in highly ionic compounds with a high coordination number
and where the ions (both cations and anions) are of similar size. Alkali metal halides such as NaCl, KCl, KBr, AgBr
and CsCl show this defect. In NaCl crystal, at room temperature, there will be one Schottky defect per 1016 ions.
Since the presence of large number of Schottky defects in a crystal leads to decrease in the number of ions in the
lattice, this results in lowering the density of the solid markedly.
A+ B+ A+ B+ A+
B+ B+ A+ B+
A+ B+ A+ A+
B+ A+ B+ A+ B+
Figure 19.9a: Schottky defect in a crystal
(ii) Frenkel Defect: When a ‘hole’ or ‘vacancy’ exists in the crystal lattice because an ion occupies an interstitial
lattice site, it gives rise to Frenkel defect. The crystal remains neutral. The defect occurs more frequently in solids
which have low coordination number and possess ions (cations and anions) of different sizes. Since cations are
generally smaller than anions, it is more common to find the cations occupying the interstitial sites. For example,
in AgBr and ZnS crystals. Ag+ ions and Zn2+ ions are missing from their normal lattice sites and are present in the
interstitial positions. AgBr, AgCl and AgI are special cases which show both Schottky and Frenkel defects.
However, the density of the solid remains the same as the presence of Frenkel defect does not change the number
of ions in the lattice. The defect causes increase in dielectric constant of the crystals as similar charges come closer.
A+ B+ A+ B+ A+
+
A
+
B B+ A+ B+
A+ B+ A+ B+ A+
B+ A+ B+ A+ B+
Figure 19.9b: Frenkel defect observed in a crystal
Illustration 13: Explain, why ZnO becomes yellow on heating? (JEE ADVANCED)
Sol: Due to Frenkel defect, when ZnO is heated, it loses oxygen reversibly and turns yellow in colour.
1
ZnO(s) → Zn2+ + O2 + 2e−
2
The Zn2+ ions formed enter the vacant voids in the crystal to form nonstoichiometric solid. The released electrons
are trapped in its neighbourhood. It is therefore, nonstoichiometric ZnO is yellow and shows increased conductivity.
Table 19.7: Difference between frenkel and schottky defects
S.No. Frenkel Defects Schottky Defects
1. The ion occupies an interstitial position than its Both cations and anions are missing from their lattice
actual lattice position. positions in the crystal (vacancy defect).
1 9 . 2 0  Solid State
2. There is no change in the density of the crystal. The defect decreases the density of the crystal.
3. It occurs in ionic compounds with low It occurs in compounds with high coordination number
coordination number and with a large difference and with ions of similar sizes.
in the size of cations and anions.
Illustration 14: Calculate the concentration of cation vacancies if NaCl is doped with 10–3 mole % of SrCl2.
(JEE ADVANCED)
Sol: Doping of SrCl2 to NaCl brings in replacement of two Na+ ion by each Sr2+ ion, but each Sr2+ occupies only one
lattice point. This produces one cation vacancy.
Thus, doping of 10–3 moles of SrCl2 in 100 mole NaCl will produce cation vacancies = 10–3 moles.
∴ 100 mole NaCl will have cation vacancies after doping = 10–3 moles.
10−3
∴ 1 mole of NaCl will have cation vacancies = = 10−5
100
∴ Total cationic vacancies = 10–5 × NA = 6.02 × 1018
11. MAGNETIC PROPERTIES OF SOLIDS
On the basis of their magnetic properties, substances can be classified into five categories.
Table 19.8: Magnetic properties of crystals
Sr. Properties Information Magnetic Example Application
No Alignment
1. Diamagnetic Repelled weakly in magnetic Benzene, Insulators
field. Such solids have only NaCl, TiO2,
paired electrons. V2O5, etc.
2. Paramagnetic Have unpaired electrons; O2, VO, CuO, Electronic devices
weakly attracted in magnetic TiO
field. They cannot be
permanently magnetised.
3. Ferromagnetic Also, have unpaired electrons. Fe, Ni, Co, CrO2 is used in audio,
Strongly attracted in magnetic CrO2 video tapes.
field. Such solids can be
permanently magnetised.
On heating to a temperature
called Curie Point, these solids
change to paramagnetic solid.
4. Antiferromagnetic In these solids changes Cr2O3, CoO, Used in the
electrons align themselves Co3O4, Fe2O3, instruments of
in such a way that resultant MnO, MnO2 magnetic susceptibility
magnetic moment is zero. measurement
5. Ferrimagnetic unpaired electrons align Fe3O4 –
themselves in such way
or
that there is a net magnetic
moment.
and so on
Chem i str y  19.21
Curie Temperature: The temperature at which a ferromagnetic substance loses its ferromagnetism and attains
paramagnetism only is called Curie temperature. For iron, the Curie temperature is 1033 K, for Ni it is 629 K and for
Fe3O4 it is 850 K. Below this temperature, paramagnetic substances behave as ferromagnetic substances.
12. ELECTRICAL PROPERTIES OF SOLIDS
Solids are classified into three groups on the basis of their electrical conductivities:
1. Conductors: These generally include metals. Their conductivity is of the order of 107 104 ohm–1 m–1.
2. Semiconductors: Those solids which have intermediate conductivities ranging from 10–6 to 104 ohm–2 m–1 are
classified as semiconductors. As the temperature rises there is a rise in conductivity because electrons from the
valence band jump to conduction band.
3. Insulators: These are solids which have very low conductivity values ranging from 10–10 to 10–20 ohm–1 m–1.
Causes of conductance in solids:
In most of the solids, conduction takes place due to migration of electrons under the influence of electric field.
However, in ionic compounds, the movement of the ion is responsible for their conducting behavior. In metals,
conductivity strongly depends upon the number of valence electrons available in an atom.
A band is formed due to closeness of molecular orbitals which are formed from atomic orbital.
If this band is partially filled or it overlaps the unoccupied higher energy conduction band, the electrons can flow
easily under an applied electric field and the solid behaves as conductor.
If the gap between valence band and next higher unoccupied conductions band is large, electrons cannot jump
into it and such a substance behaves as insulator.
Figure 19.10a: Distinction among metals, insulators and semiconductors
If the gap between the valence band and conduction band is small, some electrons may jump from valence band
to the conduction band. Such a substance show some conductivity and it behaves as a semiconductor [Fig(c)]. An
increase in temperature will increase the electrical conductivity of semiconductors as more electrons can jump
from valence to conduction band. Silicon and germanium show this type of behaviour and are called intrinsic
semiconductors.
Doping: The process of introducing an impurity into semiconductors to enhance their conductivity is called
doping.
1 9 . 2 2  Solid State
ntype semiconductor: When silicon or germanium crystal is doped with a group 15 element like P or As, the
dopant atom forms four covalent bonds like a Si or Ge atom but the fifth electron, not used in bonding, becomes
delocalised and contributes its share towards electrical conduction. Thus, silicon or germanium doped with P or As
is called ntype semiconductor, n indicative of negative since it is the electron that conducts electricity.
ptype semiconductor: When silicon or germanium is doped with a group 13 element like B or Al, the dopant
atom forms three covalent bonds like a B or Al atom, but in place of the fourth electron, a hole is created. This hole
moves through the crystal like a positive charge giving rise to electrical conductivity. Thus, Si or Ge doped with B
or Al is called ptype of semiconductor (p stands for positive hole), since it is the positive hole that is responsible
for conduction.
Silicon atom Mobile electron Positive hole
(no electrons)
As B
Perfect crystal ntype ptype
(a) (b)
Figure 19.10b: Distinction among perfect crytsal, ntype and ptype semiconductor
Diode: When ntype and ptype semiconductors are combined, what results, is known as a diode. These diodes
are used as rectifiers.
Transistors: These are used to detect or amplify radio or audio signals. They consist of pnp or npn Sandwich
semiconductors.
Photodiode: These are diodes which are capable of converting light energy into electrical energy and are used in
solar cells.
Table 19.9: Electrical properties of crystals
Properties Information Dipolar Example Application
Property
1. Piezoelectricity When a crystal of dielectrics is Development of Quartz and –
subjected to mechanical stress, charge in some Rochelle salt
then small magnitude current part of crystal
is produced. It is called direct
Piezoelectric effect.
2. Anti piezoelectricity In some solids, electric field Crystal –
develops mechanical effect. suffers elastic
deformation in
an electric field
3. Ferroelectricity Piezoelectric crystals having BaTiO3, Electromagnetic
permanent dipoles are said to KH2PO4, appliances
possess ferroelectricity Rochelle salt
4. Anti ferroelectricity Piezoelectric crystals with zero PbZrO3, Lead
dipole are said to posses anti zirconate
ferroelectricity.
5. Pyroelectricity Some polar crystals produce – Crystals of Used in fire alarms,
electric impulse on heating. tartaric acid thermostat
Chem i str y  19.23
13. TYPES OF IONIC STRUCTURES
(a) Rock Salt Structure: (NaCl) Larger atoms form ccp arrangement and smaller atoms fill all octahedral voids.
Na Cl
Na+
Cl
Rock salt structure
Figure 19.11a: Arrangement of atoms in rock salt type structure
(b) Zinc Blende (Sphalerite) Structure: (ZnS) Larger atoms form ccp arrangement and smaller atoms fill half of
alternate tetrahedral voids.
S
S
2
Zn
+2
Zn
Zinc blende structure
Figure 19.11b: Arrangement of atoms in Zinc blende type structure
(c) Cesium Halide Structure: (CsCl) Cl– at the corners of cube and Cs+ in the centre.
Cl
Cesium chloride structure
Figure 19.11c: Arrangement of atoms in cesium chloride type structure
(d) Fluorite Structure: (CaF2) Ca2+ form ccp arrangement and F– fill all tetrahedral voids.
Fluorite structure
Figure 19.11d: Arrangement of atoms in fluorite type structure
1 9 . 2 4  Solid State
(e) Antifluorite Structure: (Li2O) O2– ion form ccp and Li+ take all tetrahedral voids.
Figure 19.11e: Arrangement of atoms in antifluorite type structure
(f) Corundum Structrure: (Al2O3) O2– form hcp and Al3+ fill 2/3 octahedral voids.
(g) Rutile Structure: (TiO2) O2– form hcp while Ti4+ ions occupy half of the octahedral voids.
(h) Pervoskite Structure: (CaTiO3) Ca2+ in the corner of cube, O2– at the face centre and Ti4+ at the centre of cube.
Figure 19.11f: Arrangement of atoms in pervoskite type structure
Table 19.10: Summary of some characteristic of some closest and nonclosest packed structure
S. Formula Type of Type of Radius Packing factor (PF) TV occupied OV occupied Ligancy
Z eff
No. lattice structure
1. AB Rock salt fcc 4 None All by Na+ 6:6
4 2 4 2
(NaCl)* π 4 × 3 π rA ° 4 × 3 π rB° ions
(rA° + rB° ) = PF =
2
a2
2. ZnS (Zinc ccp 4 Half by Zn2+ None 4:4
4 2 4 2
blende) ions (Alternate
3 4 × 3 π rA ° 4 × 3 π rB°
(rA° + rB° ) = a PF = TV)
4 a2
3. CaCl hcp 1 None Only one by 8:8
4 2 4 2
2 (rA ° + rB° ) =3a 1× 3 π rA ° 1× 3 π rB° Cs+
PF =
2
a
4. AB2 CaF2 * ccp 4 All by Na+ ions None 8:4
4 2 4 2
3 4 × 3 π rA ° 8 × 3 π rB°
(rA° + rB° ) = a PF =
4 a2
Note: Here radius rule will change. Now r/r lies in 0.225 – 0.414 as anion lies in TV. 4:8
5. A2B Na2O ccp 4 All by Na+ ions None 4:8
4 2 4 2
(Antifuorite)
3 8 × 3 π rA ° 4 × 3 π rB°
(rA° + rB° ) = a PF =
4 a2
4 2
8× πr °
3
=
PF 3 A= =
π 0.34
a2 16
6. Diamond fcp 8 4 2 4 more C – None 4
Cubic (DC) 8× πr ° atoms are
3 3
r= a =
PF 3 A=
2
=
π 0.34 present in
a 16
8 alternate TVs
2
Height c = 4 r
3
Chem i str y  19.25
S. Formula Type of Type of Radius Packing factor (PF) TV occupied OV occupied Ligancy
Z eff
No. lattice structure
7. Hexagonal hcp 6 2r = 4   
4 3
closed 6 × πr
packed 3 π
=
PF = = 0.74
(AB AB … 2 3
Height (c) = 4r 24 2 r 3 2
packing) 3
1 9 . 2 6  Solid State
Base area, 4 3
6 × πr
3 π
=
PF = = 0.74
3
24 2 r 3 2
A = 6 3 r2
Volume = 24 2 r3
8. AB2O4 Spinel fcc 4 3 4 3 4 3 4 3 
Volume
= a= 16 2 r3 2−
O 2 × 3 πrAl3+ + 1× 3 πrZn2 + + 4 × 3 πrO2 − 1 1
PF = Zn2 + = TV Al3+ = OV
( ZnAl2O4 ) Al3+ = 2 For TV, 8 2
16 2 r 3 2 −
O
Zn3+ = 1 r
2− Zn2 + 3 2
Q =4 = 0.225 r Al3+ = OV
r =
π 1 rAl3+ + 1 Al3+ + 1 3
O2 − 4 r 2−
3 2 2 rO2 − O
For OV,
r π 1 3 1 3
Al3+ = ( 0.414 ) + =( 0.225) + 1 0.77
= 0.414 3 2 2 4
r
O2 −
9. A2O3 Correndum Hcp 6 4 3 4 3 6:4
Volume of hcp = 24 2 r 3
6 × 3 πrO2 − + 4 × 3 πrAl3+ 2
( Al2O3 ) r PF = Al3+ = OV
O2 − = 6 For OV, ⊕ = 0.414 3
rΘ 24 2 r 3 2 −
O
Al3+ = 4
3
π 2 rAl3+
= 1 +
3 2 3 rO2 −
3.1416 2 3
= 1 + ( 0.414 ) = 0.7756
3 × 1.414 3
Chem i str y  19.27
POINTS TO REMEMBER
Radius Ratio: In a given coordination number,
C.N r+/r
radius ratio has fixed value in the limiting case:
3 0.155
4(Td) 0.225
4(SP) 0.414
6 0.414
8 0.732
Packing fraction [φ] : It is the maximum fractional Typing of unit cells Packing fractions
volume of unit cell which can be occupied by Simple cubic 0.53
atoms or ions. In case of atomic solids of like
atoms, following are the values of packing Body centred cubic 0.68
fractions Fcc 0.74
Hcp 0.74
Relationship between radius and sides of
SC A=2r
unit cells in atomic solids (a = edge length,
r = atomic radius): Bcc
3a = 4r
Fcc
2a = 4r
Hcp a=2r
2
h = 4 r
3
Bravias lattices: Based on the arrangement of atoms or ions, the seven
crystal systems are further classified into 14 types known as
the bravias lattices.
Primitive cell: A primitive cell is a bravias lattice that homes only one atom
(effectively) in one unit cell.
Density of solid [ρ] : Massof atoms / ions in one unit cell
ρ=
volume of an unit cell
Cubic System : NM 1 −3
ρ= 3 gcm
NA a
N=number of atoms per unit cell,
M=molar mass,
NA =Avogadro’s number
a3=volume of unit cell in cm3
1 9 . 2 8  Solid State
Tetrahedral and Octahedral void (Holes) : (i) Number of tetrahedral voids=2 × effective number of
atoms/unit cell.
(ii) Number of octahedral voids =Number of atoms
(effectively) per unit cell.
A
x
B
The interstities below B
is tetrahedral void
x is the central of
octahedral void
Crystal defects : A) Point Defects\Stoichiometric defects
Two types:
(i) Schottky Defect –Atoms or ions absent from their
normal lattice sites. Observed in NaF, KCl etc.
(ii) Frenkel Defect Smaller cation leaves its normal lattice,
occupies the interstitial site. Observed in solids with smaller
cations like LiI.
+  +  +  +  +  + 
 + +  +  +  +  +
+
+   +  +  +  + 
 +  +  +  +  +  +
Schottky defect Frenkel defect
B) Fcenter defectAlkali metal vapours passed on an
ionic solid lets out electrons which substitute some anions
leading to trapped electrons.
Based on the geometry of unit cells, solids are divided into seven crystal systems as:
System Parameters Interaxial angle
Triclinic a≠b≠c α≠β≠γ
Monoclinic a≠b≠c α = γ = β ≠ 90ο
Orthorhombic a≠b≠c α = β = γ = 90ο
Tetragonal a= b ≠ c α = β = γ = 90ο
Cubic a=b=c α = β = γ = 90ο
Hexagonal a= b ≠ c α = β = 90ο ≠ γ = 120ο
Rhombohedral (or) (Trigonal) a=b=c α = β = γ ≠ 90ο
Chem i str y  19.29
Solved Examples
JEE Main/Boards = 400 × 10–12 m
(1 pm = 10–12 m)
Example 1: Both diamond and rhombic (solid) sulphur
= 400 × 10–10 cm
are covalent solids, however, the latter has very low
m.pt. in comparison to diamond. Explain. Volume of unit cell
= (400 × 10–10 cm)3
Sol: Value of Boiling point and melting point depends
on intermolecular force of attraction. By taking into = 64 × 10–24 cm3
consideration the forces that help the two structure
Number of atoms (n) in the fcc unit cell = 4
(diamond and sulphur) to hold together, answer the
question. 4 × 60
∴ Density =
Diamond has three dimensional covalent network and 6.023 × 1023 × 64 × 10−24
strong intermolecular forces whereas rhombic sulphur = 6.23 g cm–3
has one dimensional covalent network with puckered
eight membered ring held together by weak van der
Waals’ forces. Example 4: The figures given below show the location
of atoms is three crystallographic planes in a fcc lattice.
Draw the unit cell for the corresponding structure and
Example 2: Calculate the number (n) of atoms contained identify these planes in your diagram.
within (a) simple cubic cell (b) a body centred cubic cell
(c) a face centred cubic cell.
Sol: (a) The simple cubic unit cell has 8 atoms at eight
corners. Each atom is shared by 8 unit cells.
1 (i) (ii)
∴ n =8 × =1
8
(b) The body centred cubic cell consists of 8 atoms at
the corners and one atom at centre.
1 (iii)
∴ n = 8 × + 1 = 2
8
Sol: (i) Face plane,
(c) The face centred cubic unit cell consists of 8 atoms at
(ii) Face diagonal plane and
the eight corners and one atom at each of the six faces.
This atom at the face is shared by two unit cells. (iii) Diagonal plane
1 1
∴ n =8× + 6 × = 4
8 2 Example 5: Ferric oxide crystallizes in a hexagonal
closed packed array of oxide ions, with two out of every
Example 3: An element having atomic mass 60 has face three octahedral holes occupied by ferric ions. Derive
centred cubic unit cells. The edge length of the unit cell the formula of the ferric oxide.
is 400 pm. Find out density of the element.
Sol: Hexagonal close packing has an array of oxide ions,
Sol: From the edge length determine the volume of unit where two out of three octahedral holes occupied by Fe3+
cell as, Volume =a3 ions has one octahedral void or holes corresponding to
each atom constituting the close packing. In iron oxide
Density can be determined using the following
only 2/3 of octahedral holes are occupied by Fe3+ ions.
expression that relates density with edge length.
It means corresponding to each oxide ion, there are 2/3
4 × Mw
ρ= Fe3+ ions. Thus, molecular formula of iron oxide is Fe2O3.
NA × a3 × 10−30
Edge length of unit cell = 400 pm
1 9 . 3 0  Solid State
Example 6: The structure of CsCl is different from NaCl, Area (of base) of unit cell in hcp
though both have the similar formula. Explain.
= 6 3r 2 (Follow text)
Sol: CsCl has radius ratio ≥ 0.732 and shows cubic Height of unit cell in hcp
arrangement, whereas radius of NaCl is < 0.732 and has 2
octahedral arrangement. = 4r × (follow text)
3
6 × 4 πr 3
Example 7: Calculate the wavelength of Xrays, which ∴ Packing fraction =
2
produces a different angle 2θ equal to 16.80º for a 3 × 6 3r 2 × 4r ×
3
crystal. Assume first order diffraction with inter particle π
distance in crystal of 0.2 nm. = = 0.74 or 74%
3 2
Sol: using Bragg’s equation, =
nλ 2dsin θ Thus, empty space in hcp =
1 − 0.74 =
0.26 or 26%
Calculate the Wavelength.
Given, n = 1, d = 0.2 × 10–9 m,
JEE Advanced/Boards
16.80
=θ = 8.40º
2 Example 1: Metallic gold crystallizes in the face
2 × 0.2 × 10 −9 sin8.4 centred cubic lattice. The length of the cubic unit cell
Thus, λ= = 5.84 × 10–11 m is a = 4.070 Å.
1
(a) What is the closest distance between gold atoms?
Example 8: Explain, why solids with Fcentres are
(b) How many ‘nearest neighbours’ does each gold
paramagnetic?
atom have at the distance calculated in (a)?
Sol: Solids containing Fcentres are paramagnetic (c) What is the density of gold?
because the electrons occupying the holes are unpaired.
(d) Prove that the packing factor for gold, the fraction
of the total volume occupied by the atoms themselves,
Example 9: A fcc lattice cube is formed by atoms A and is 0.74.
B. If atom A is present at the corner of the cube and the
atom B at the faces of the cube. Find out the formula of Sol: (a) In fcc, a = 2 2 r
the compound. a
∴ 2r =
Sol: Contribution of atom ‘A’ at eight corners of the 2
cube 2r is closest distance between two atom.
1 4.070
= × 8 = 1 atom ∴ 2r
= = 2.878 Å.
8 1.414
1
Contribution of atom at each face = atom D
2
E
∴
The atom ‘B’ at six faces of the cube a G B
1 F
= × 6 = 3 atom
2 C A
∴ Formula of the compound = AB3
a
a
Example 10: A metallic element crystallizes into a lattice
containing a sequence of layers of ABABAB ............ Any (b) The problem is to find how many face centers are
packing of spheres leaves out voids in the lattice. What equidistant from a corner atom. Point A in figure may
percentage by volume of this lattice is empty space? be taken as the reference corner atom. In that same
4 3 figure, B is one of the facecenter points at the nearest
6× πr distance to A. In plane ABD in the figure, there are
Sol: Packing fraction in hcp = 3
Volume three other points equally close to A: the centers of the
6 × 4 πr 3 squares in the upper right, lower left, and lower right
=
3 × Area × Height quadrants of the plane, measured around A. Plane ACE,
Chem i str y  19.31
parallel to the plane of the paper, also has points in the Dividing dFCC and dBCC
centers of each of the squares in the four quadrants
around A. Also, plane ACF, perpendicular to the plane dFCC 4 (3)3
= × = 2 × 0.6297 = 1.259
of the paper, has points in the centers of each of the dBCC 2 (3.5)3
squares in the four quadrants around A. Thus there are
12 nearest neighbors in all, the number expected for a Example 3: You are given some marbles with a diameter
closepacked structure. of 10mm. They are to be placed such that their centres
The same result would have been obtained by counting are lying in a square bond by four lines each of length
the nearest neighbours around B, a facecentered point. 40 mm. What will be the arrangements of marbles in
a plane so that maximum number of marbles can be
(c) In fcc, n = 4, M = 197 g mol1 placed inside the area? Sketch the diagram and derive
a = 4.070 Å = 4.070 × 1010 cm expression for the number of molecules per unit area.
n×M 4 × 197 Sol: Area of square having spherical marbles in it
density = =
( )
3 3
NA .a 6.022 × 1023 × 4.07 × 10−10 40mm
A B
= 19.4 g cm3
(d) Since atoms at closest distance are in contact in a
closepacked structure, the closest distance between
a
centres calculated in (a), , must equal the sum of
2
the radii of the two spherical atoms, 2r. Thus, r = a/23/2. = 40 × 10−1 × 40 × 10−1 cm2
From (c), there are 4 gold atoms per unit cell. D
= 16 cm2 A B
4
mm
= 4 πr3
10
Then, Volume of 4 gold atoms
mm
3
10
∴ Volume of unit cell = a3 C
( ) 3
3
= 2 2 r CD 10 sin60º
= = 10 = 5 3
2
= 16 2 r 3 The maximum number of spheres of 10 mm diameter in
volume of 4 gold atoms hcp packing can be seen in figure.
∴ Packing fraction =
volume of unit cell Total length converted by spheres
16 = 5 + 4 × CD = 5 + 4 × 10sin60º
π r3
3 π
= = = 0.74
3
= 5 + 4 × 5 3 = 40mm = 4 cm
16 2 r 3 2
Maximum number of spheres (s)
Example 2: A metal crystalizes into two cubic phases, = 14 + 8
face centred cubic (FCC) and body centred cubic (BCC), (Full) (half)
whose unit cell lengths are 3.5 and 3.0 Å, respectively. = 14 + 4 = 18
Calculate the ratio of densities of FCC and BCC. 18
∴ Number of spheres per cm=
2
= 1.125
16
Sol: We know that
Example 4: Using the given data find out the type of
Z × Formula mass of substance
ρ= cubic lattice to which the crystal belong:
N0 × a3
Since for FCC, Z = 4 and for BCC, Z = 2 Fe V Pd Al
a in pm 286 301 388 405
4 × Formula mass of metal
dFCC = ρ in g cm–3 7.86 5.96 12.16 2.70
N0 × (3.5)3
At. mass in 55.85 50.94 106.4 26.98
4 × Formula mass of metal g mol–1
and dBCC =
N0 × (3)3
1 9 . 3 2  Solid State
n × At.mass Number of LiF molecules per mole
Sol: We know, ρ = 3
N0 × a (i.e., Avogadro constant)
3
ρ × N0 × a 1.201 × 1024
or n = = = 6.01 × 1023
At.mass 2
For Fe:
7.86 × 6.023 × 1023 × (286 × 10−10 )3 Example 6: Calculate the glancing angle on the
n= =2 cube (100) of a rock salt (a = 2.814 Å) corresponding
55.85
to second order diffraction maximum for Xrays of
(i.e., cubic lattice of Fe is body centred) wavelength 0.710 Å.
For V:
Sol: First determine the distance between lattice plane
5.96 × 6.023 × 1023 × (301 × 10−10 )3 a
n= =2 by using the following expression, dhkl =
50.94
h2 + k 2 + l2
(i.e., cubic lattice of V is body centred)
And then θ angle can be calculated using Bragg’s
For Pd: equation
12.16 × 6.023 × 1023 × (388 × 10−10 )3 2d sin θ = nλ ...(i)
n= =4
106.4
The distance between consecutive lattice planes is
(i.e., cubic lattice of Pd is face centred) defined by Miller indices (h, k, l) in a cubic lattice by
For Al: the relation
a
2.70 × 6.023 × 1023 × (405 × 10−10 )3 dhkl = = 2.814 Å, h=1, k=0, l=0
n= =4 h + k 2 + l2
2
26.98
2.814 Å
(i.e., cubic lattice of Al is face centred) ∴ d100
= = 2.814 Å = 2.814 × 10–8 cm
12 + 02 + 02
Example 5: The density of a particular crystal of LiF is From equation (i)
2.65 g/cc. Xray analysis shows that Li+ and F– ions are 2 × 2.814 × 10−8 sin θ = 2 × 0.710 × 10−8
arranged in a cubic array at a spacing of 2.01 Å. From
these data calculate the apparent Avogadro constant. 2 × 0.710 × 10−8
sin θ = = 0.2533
[Li = 6.939, F = 18.998 (1Å = 10–8 cm)] 2 × 2.814 × 10−8
sin θ =0.2533
Sol: In this problem, we have to calculate Avogadro
constant, i.e., the number of LiF molecules percent in 1 ∴ θ =sin−1 (0.2533)
mole of LiF weighs 25.937 g or θ =14º 36' 40"
(LiF = 6.939 + 18.998),
wt. of 1 mole Example 7: The edge length of unit cell of a metal
Volume of 1 mole =
wt. per cc (density) having molecular weight 75 g mol–1 is 5 Å which
25.937 crystallizes in body centred cubic lattice. If density is 2
= = 9.78 cc.
2.65 g cm–3, calculate radius of metal atom.
Since this volume is supposed to be a cube, the length n × Mol.wt.
of each edge of the cube Sol: Density =
V × NA
3
= 9.78 2.138 cm.
= 2 × 75
2=
Number of ions present in one edge a × 6.023 × 1023
3
2.138 (n = 2 for bcc)
= = 1.063 × 108
2.01 × 10−8 ∴ a= 5 × 10−8 cm3
Number of ions (Li + F ) present in cube
+ –
3 3
r= × a= × 5 × 10 −8
= (1.063 × 108 )3 = 1.201 × 1024 4 4
= 2.16 × 10–8 cm = 216 pm
Chem i str y  19.33
Example 8: A solid compound contains X, Y and Z = a 5.64 × 10−8 cm
atoms in a cubic lattice with X atoms occupying the
corners, Y atoms in the body centred position and Z Molar mass 58.8
Molar
= volume =
atom at the centre of the face of the unit cell. What is Density 2.165
the empirical formula of the compound? 1/3
58.8
Edge length
= (a) = 3 cm
(A) XY2Z3 (B) XYZ3 2.165
(C) X2Y2Z3 (D) X8YZ6 (E) XYZ
Example 11: In a solid AB having the NaCl structure, A
1 atoms occupy the corners of the cubic unit cell. If all the
Sol: (B) Number of atoms of X in a unit cell = × 8 = 1
8 face centred atoms along one of the axis are removed.
Number of atoms of Y in a unit cell = 1 what would be the resultant stoichiometry of solid?
1 Sol: AB has NaCl structure, i.e., 8 corner and 6 face
Number of atoms of Z in a unit cell = ×6 = 3
2 centred atoms. If we remove face centred atoms of one
Empirical formula of the compound = XYZ3 axis, two face centred atoms are removed. Thus, A is at
8 corners and B is at four faces.
Example 9: When an electron in an excited state of Mo 8
∴ Contribution of A = =1
atom falls from L to Kshell, an Xray is emitted. These 8
Xrays are diffracted at angle of 7.75º by planes with a 4
separation of 2.64 Å. What is the difference in energy Contribution of B = = 2
2
between Kshell and Lshell in Mo, assuming a first
order diffraction? (sin 7.75º = 0.1349) ∴ Stoichiometry of resultant solid is AB2.
Sol: Using Bragg’s equation first determine the
wavelength and then energy can be calculated as
hc
E=
λ
=nλ 2dsin θ
1 × λ = 2 × 2.64 sin7.75º
=
2 × 2.64 × 0.1349
λ =0.712 Å
Energy difference between K and Lshell of Mo
hc 6.626 × 10−34 × 3 × 108
= = = 2.791 × 10−15 J
λ −10
0.712 × 10
Example 10: The density of crystalline sodium chloride
is 2.165 g cm–3. What is the edge length of the unit cell?
What would be the dimensions of cube containing one
mole of NaCl?
N M
Sol: We know that, ρ = 3
a NA
Where, ρ = density = 2.165 g cm–3
M = molar mass = 58.5
NA = Avogadro’s number = 6.023 × 1023
N = number of formula unit
per unit cell = 4 (for bcc)
N M
a3 = = 4 58.5
= 1.794 × 10
–22
ρ NA 2.165 6.023 × 10
23
1 9 . 3 4  Solid State
JEE Main/Boards
Exercise 1 Q.10 An element crystallizes in fcc structure. 200 g of
this element has 4.12 × 1024 atoms. The density of A is
Q.1 Explain each of the following with a suitable 7.2 g cm–3. Calculate the edge length of the unit cell.
example:
Q.11 Lithium metal crystal has bodycentred cubic
(i) Paramagnetism. structure. Its density is 0.53 g cm–3 and its molecular
(ii) Frenkel defect in crystals. mass is 6.94 g mol–1. Calculate the volume of a unit cell
of lithium metal.=[NA 6.023 × 1023 mol−1 ]
Q.2 State the difference between Schottky and Frenkel
defects. Which of the two changes the density of the Q.12 If NaCl crystals are doped with 2 × 10−3 mol per
solid? cent of SrCl2, calculate the cation vacancies per mole.
Q.3 (a) What is meant by anisotropy? Q.13 An element exists in bcc structure with a cell
edge of 288 pm. If the density of the element is 7.2
(b) Give a sketch of arrangement of particles in a solid g cm–3, what is the atomic mass of the element?
which would show anisotropy. [NA 6.023 × 1023 mol−1 ]
=
Q.4 (a) Explain with the help of figure square close Q.14 An element A crystallises in fcc structure, 208 g
packing and hexagonal closepacking of particles in a of this element has 4.283 × 1024 atoms. If edge length
solid in two dimensions. of the unit cell of this element is 408 pm, calculate its
(b) What is the coordination number of a particle in the density.
two packings?
Q.15 Copper crystallises in facecentred cubic lattice
Q.5 Some crystal defects are shown in the figures and has a density of 8.930 g cm−3 at 239 K. Calculate
below: the radius of Copper atom. [At. mass of Cu = 63.55 u,
Avogadro’s constant =NA 6.02 × 1023 mol–1]
Q.16 Metallic gold crystallises in a fcc lattice and has a
density of 19.3 g cm–3. Calculate the radius of gold atom.
Indicate the types of defect shown by (a) and (b). [At. mass of gold = 197 u,= NA 6.023 × 1023 mol–1]
Q.6 A compound is formed by two elements M and Q.17 A substance forms facecentred cubic crystals. If
N. The element N forms ccp and atoms of M occupy the edge length of the unit cell is 630 pm and density of
1/3rd of tetrahedral voids. What is the formula of the the substance is 1.984 g cm–3, calculate the molar mass
compound? of substance.
Q.7 An element with molar mass 2.7 × 10−2 kg mol–1 Q.18 In a solid AB, having the NaCl structure, B atoms
forms a cubic unit cell with edge length 405 pm. If its occupy the corners of the cubic unit cell. If all the face
density is 2.7 × 103 kg m–3, what is the nature of the centred atoms along one of the axes are removed, then
cubic unit cell? what is the resulting stoichiometry of the solid?
Q.8 An element occurs in bcc structure with cell edge Q.19 Lithium boron hydride crystallizes in an
300 pm. The density of the element is 5.2 g cm–3. How orthorhombic system with 4 molecules per unit cell. The
many atoms of the element does 200 g of the element unit cell dimensions are a = 6.8 Å, b = 4.4 Å and c = 7.2
contain? Å. If the molar mass is 21.76, calculate density of crystal.
Q.9 The density of chromium metals is 7.2 g cm–3. If the Q.20 The simple cubic lattice consists of eight identical
unit cell has edge length of 289 pm, determine the type of spheres of radius R in contact, placed at the corners of
unit cell.[Atomic mass of Cr = 52 u; NA = 6.02 × 1023 mol–1] a cube, what is the volume of the cubical box that will
just enclose these eight spheres and what fraction of
this volume is actually occupied by the spheres?
Chem i str y  19.35
Q.21 In an ionic oxide, oxide ions are arranged in hcp Exercise 2
array and positive ion occupy two thirds of octahedral
void. Suggest the simplest formula assuming metal as M. Single Correct Choice Type
Q.22 A compound containing Zn, Al and S crystallises Q.1 A solid has a structure in which W atoms are located
with a closed packed array of sulphide ions. Zinc ions at the corners of a cubic lattice, O atom at the centre
are found in oneeighth of the tetrahedral holes and of the edges and Na atom at centre of the cubic. The
aluminium ions in one half of the octahedral holes. formula for the compound is:
What is the empirical formula of the compound? (A) NaWO2 (B) NaWO3 (C) Na2WO3 (D) NaWO4
Q.23 What is the percent by mass of titanium in rutile, a
Q.2 The coordination number of cation and anion in
mineral that contains Ti and oxygen? If structure can be
Fluorite CaF2 and CsCl are respectively
described as a closest packed array of oxide ions with
titanium ions in a onehalf of the octahedral holes? (A) 8: 4 and 6: 3 (B) 6: 3 and 4: 4
What is the oxidation number of titanium? (Ti = 48) (C) 8: 4 and 8: 8 (D) 4: 2 and 2: 4
Q.24 Calculate packing efficiency in ccp structure. How Q.3 The interstitial hole is called tetrahedral because
does it differ from packing efficiency in hcp structure?
(A) It is formed by four spheres.
Q.25 A strong current of trivalent gaseous boron passed (B) Partly same and partly different.
through a germanium crystal decreases the density (C) It is formed by four spheres the centres of which
of the crystal due to part replacement of germanium form a regular tetrahedron.
by boron and due to interstitial vacancies created by (D) None of the above three.
missing Ge atoms. In one such experiment, one gram
of germanium is taken and the boron atoms are found
to be 150 ppm by weight, when the density of the Ge Q.4 The mass of a unit cell of CsCl corresponds to
crystal decreases by 4%. Calculate the percentage of (A) 1 Cs+ and 1 Cl– (B) 1 Cs+ and 6 Cl–
missing vacancies due to germanium, which are filled
(C) 4 Cs+ and 4 Cl– (D) 8 Cs+ and 1 Cl–
up by boron atoms. [Atomic wt. Ge = 72.6, B = 11]
Q.26 What is a semiconductor? Describe two main Q.5 Which one of the following schemes of ordering
types of semiconductors and explain mechanism for closed packed sheets of equal sized spheres do not
their conduction. generates close packed lattice.
(A) ABCABC (B) ABACABAC
Q.27 (a) The electrical conductivity of a metal decreases
with rise in temperature while that of a semiconductor (C) ABBAABBA (D) ABCBCABCBC
increases. Explain.
Q.6 An ionic compound AB has ZnS type structure. If
(b) The ions of NaF and MgO have the same number of
the radius A+ is 22.5 pm, then the ideal radius of B–
electrons and internuclear distances are about the same
would be
[235 pm and 215 pm]. Why are then the melting points
of NaF and MgO so different [992ºC and 2642ºC]? (A) 54.35 pm (B) 100 pm
(c) Why does zinc oxide exhibit enhanced electrical (C) 145.16 pm (D) None of these
conductivity on heating?
Q.7 The tetrahedral voids formed by ccp arrangement
Q.28 Bring out with the help of a sketch the difference of Cl– ions in rock salt structure are
between metals insulators and semiconductors in terms of
energy gap between valence band and conduction band. (A) Occupied by Na+ ions
(B) Occupied by Cl– ions
Q.29 Explain with the help of a figure, how an electron (C) Occupied by either Na+ or Cl– ions
(i) moving in an orbital and (ii) spinning in an atom give
(D) Vacant
magnetic properties.
Q.30 How can you show with the help of a diagram that Q.8 The number of nearest neighbours around each
number of octahedral voids is equal to the number of particle in a facecentred cubic lattice is
atoms in cubic close packed structure? (A) 4 (B) 6 (C) 8 (D) 12
1 9 . 3 6  Solid State
Q.9 If the anions (A) from hexagonal closest packing Q.5 The packing efficiency of the twodimensional
and cations (C) occupy only 2/3 octahedral voids in it, square unit cell shown below is (2010)
then the general formula of the compound is
(A) CA (B) CA2 (C) C2A3 (D) C3A2
Q.10 A solid is formed and it has three types of atoms
X, Y, Z. X forms a FCC lattice with Y atoms occupying all l
the tetrahedral voids and Z atoms occupying half the
octahedral voids. The formula of the solid is (A) 39.27% (B) 68.02% (C) 74.05% (D) 78.54%
(A) X2Y4Z (B) XY2Z4 (C) X4Y2Z (D) X4YZ2
Q.6 StatementI: In any ionic solid (MX) with Schottky
Q.11 The intermetallic compound LiAg crystallizes defects, the number of positive and negative ions are
in cubic lattice in which both lithium and silver have same.
coordination number of eight. The crystal class is StatementII: Equal number of cation and anion
(A) Simple cubic (B) Body centred cubic vacancies are present. (2001)
(C) Face centred cubic (D) None of these (A) StatementI is true, statementII is true, statementII
is the correct explanation of statementI.
Q.12 NH4Cl cyrstallizes in a bodycentred cubic type (B) Statement I is true, statementII is true, statementII
lattice with a unit cell edge length of 387 pm. The distance is not the correct explanation of statementI.
between the oppositely charged ions in the lattice is (C) StatementI is true, statementII is false.
(A) 335.1 pm (B) 83.77 pm (D) StatementI is false, statementII is true.
(C) 274.46 pm (D) 137.33 pm
Q.7 Sodium crystallizes in a bcc cubic lattice with the
cell edge, a = 4.29 Å. What is the radius of sodium
Previous Years’ Questions atom? (1994)
Q.1 The coordination number of a metal crystallizing in Q.8 A metallic element crystallizes into a lattice containing
a hexagonal closepacked structure is (1999) a sequence of layers of ABABAB ......... Any packing of
(A) 12 (B) 4 (C) 8 (D) 6 layers leaves out voids in the lattice. What percentage by
volume of this lattice is empty space? (1996)
Q.2 In a solid ‘AB’ having the NaCl structure, ‘A’ atoms
occupy the corners of the cubic unit cell. If all the face Q.9 Chromium metal crystallizes with a body centred
centred atoms along one of the axes are removed, then cubic lattice. The length of the unit edge is found to be
the resultant stoichiometry of the solid is (2001) 287 pm. Calculate the atomic radius. What would be
(A) AB2 (B) A2B (C) A4B3 (D) A3B4 the density of chromium in g/cm3? (1997)
Q.3 A substance AxBy crystallizes in a face centred Q.10 A metal crystallizes into two cubic phases, face
cubic (fcc) lattice in which atoms ‘A’ occupy each corner centred cubic (fcc) and body centred cubic (bcc),
of the cube and atom ‘B’ occupy the centres of each whose unit cell lengths are 3.5 and 3.0 A⁰, respectively.
face of the cube. Identify the correct composition of the Calculate the ratio of densities of fcc and bcc. (1999)
substance AxBy. (2002)
(A) AB3 (B) A4B3 Q.11 The figures given below show the location of
atoms in three crystallographic planes in a fcc lattice.
(C) A3B (D) Composition cannot be specified
Draw the unit cell for the corresponding structures and
identify these planes in your diagram. (2000)
Q.4 Which of the following fcc structure contains
cations in alternate tetrahedral voids? (2005)
(A) NaCl (B) ZnS (C) Na2O (D) CaF2
Chem i str y  19.37
Q.12 In a compound atoms of element Y from ccp lattice Q.16 In a face centred cubic lattice, atom A occupies the
and those of element X occupy 2/3rd of tetrahedral corner positions and atom B occupies the face centre
voids. The formula of the compound will be (2008) positions. If one atom of B is missing from one of the face
centred points, the formula of the compound is: (2011)
(A) X 4 Y3 (B) X 2 Y3 (C) X 2Y (D) X 3 Y4
(A) AB2 (B) A 2B3 (C) A 2B5 (D) A 2B
Q.13 The edge length of a face centered cubic cell of an
ionic substance is 508 pm. If the radius of the cation is Q.17 Lithium forms body centred cubic structure. The
110 pm, the radius of the anion is (2010) length of the side of its unit cell is 351 pm. Atomic
radius of the lithium will be: (2012)
(A) 288 pm (B) 398 pm (C) 618 pm (D) 144 pm
(A) 75 pm (B) 300 pm (C) 240 pm (D) 152 pm
Q.14 Copper crystallizes in fcc with a unit cell length of
361 pm. What is the radius of copper atom (2009) Q.18 CsCl crystallises in body centred cubic lattice.
If ‘a’ is its edge length then which of the following
(A) 108 pm (B) 127pm (C) 157pm (D) 181pm expressions is correct? (2014)
3a
(A) rCs+ + rCl− =
3a (B) rCs+ + rCl− =
Q.15 Percentage of free space in cubic close packed 2
structure and in body centred packed structure are 3
respectively (2010) (C) rCs+ + rCl− = a (D) rCs+ + rCl− =3a
2
(A) 30% and 26% (B) 26% and 32%
(C) 32% and 48% (D) 48% and 26% Q.19 Sodium metal crystallizes in a body centred cubic
lattice with a unit cell edge of 4.29 Å. The radius of
sodium atom is approximately: (2015)
(A) 1.86 Å (B) 3.22 Å (C) 5.72 Å (D) 0.93 Å
JEE Advanced/Boards
Q.5 Spinel is a important class of oxides consisting of
Exercise 1
two types of metal ions with the oxide ions arranged
Q.1 A cubic solid is made up of two elements A and in ccp pattern. The normal spinel has oneeighth of
B. Atoms B are at the corners of the cube and A at the the tetrahedral holes occupied by one type of metal
body centre. What is the formula of compound? ion and one half of the octahedral hole occupied by
another type of metal ion. Such a spinel is formed by
Q.2 A compound alloy of gold and copper crystallizes Zn2+, Al3+ and O2–, with Zn2+ in the tetrahedral holes.
in a cubic lattice in which gold occupies the lattice Give the formulae of the spinel.
points at the corners of the cube and copper atom
occupies the centres of each of the cube faces. What is
Q.6 KF crystallizes in the NaCl type structure. If the
the formula of this compound? radius of K+ ions 132 pm and that of F– ion is 135 pm,
what is the shortest K F distance? What is the edge
Q.3 A cubic solid is made by atoms A forming close pack length of the unit cell? What is the closet KK distance?
arrangement, B occupying one fourth of tetrahedral
void and C occupying half of the octahedral voids. Q.7 A closed packed structure of uniform spheres has
What is the formula of compound? the edge length of 534 pm. Calculate the radius of
sphere, if it exist in
Q.4 What is the percent by mass of titanium in rutile, a (a) simple cubic lattice
mineral that contain Titanium and oxygen, if structure
can be described as a close packed array of oxide ions, (b) BCC lattice
with titanium in one half of the octahedral holes. What (c) FCC lattice
is the oxidation number of titanium?
27 Iron occurs as bcc as well as fcc unit cell.2 g cm–3. If the anion has a radius of 250 pm. one eighth percentage of sites that are unoccupied. O2– ion.11 AgCl has the same structure as that of NaCl. Show that KBr has face Q. Cs + ion.69 Å. 3 8  Solid State Q.42 Å.75 g cm–3. In this crystal the shortest distance between Pb+2 ion Q.023 × 1023 mol–1. Calculate of the unit cell in lead sulphide? Also calculate the unit the density of A and number of unit cells and number cell volume.13 The two ions A+ and B– have radii 88 and 200 pm having a radius of 180 pm be slipped into the tetrahedral respectively. It (a) The ratio of the sides of unit cell for KCl to that for has FCC structure.561 g cm–3. Calculate its density. Density of NaCl = 2. Q.25 Calculate the value of Avogadro’s number from Q. Given that Na = 0.65 Å. AB. 1.15 Gold crystallizes in a face centered cubic lattice. calculate the number What is the radius of an iron atom? of atoms present in 200 g of element.23 In a cubic closed packed structure of mixed pm and the density of AgCl is 5.18 The effective radius of the iron atom is 1.21 Iron has body centered cubic lattice structure. Q.19 A crystal of lead(II) sulphide has NaCl structure. Calculate the density. Calculate the radius of Cs+ ion. The edge length of unit cell of AgCl is found to be 555 Q. Calculate the interionic distance in CsCl. . Find the oxides the lattice is made up of oxide ions.12 Xenon crystallises in the facecentred cubic lattice ions (B3+). effective radius of an atom of iron is 124 pm. corners and Cs+ ions at the centre of the unit cells is 7 Å and the radius of the Cs+ ion is 1.29An element A(Atomic weight = 100) having bcc and S2– ion is 297 pm.9 An element crystallizes into a structure which may