Chemistry Module I Physical I Ranveer Singh

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About the Author
Ranveer Singh has an M.Sc. in Chemistry and has been mentoring and teaching Chemistry to JEE aspirants for more than 15
years. He aims for perfection and has an enormous passion when it comes to applying new methods to create solutions. These
are the qualities that make him stand out from the crowd as a teacher and instructor.
Ranveer Singh
McGraw Hill Education (India) Private Limited

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Physical Chemistry for JEE (Main & Advanced) Module-I
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Dedicated
to
Shri Amar Chand Ji Maharaj
Preface
Chemistry forms an important part of all entrance tests. In my teaching career, spanning over a decade and half, I have felt that a
chemistry book based on the changing perceptions, needs, feedback and the experiences of the students and educators is needed
by the engineering aspirants. It is with this vision that the present book has been written.
This book is not a textbook. It is a refresher text to help students revise their lessons in the quickest possible way and in the
most effective manner. It does not over emphasise theories, as has been done in several other competitive books available in the
market. However, every care has been taken to ensure that no important theory is left out. This book has several new features:
coverage of the syllabus of JEE (Main + Advanced); a great number of solved numerical examples to acquaint students with
the application of several theories, solution at the end of each exercise and two levels of questions at the end of the chapters to
give readers an opportunity to assess their understanding of the chapters. The use of easily understandable language is at the
core of the author’s efforts.
The exercises given at the end of every chapter is further categorised into three difficulty level of questions and their patterns
asked in JEE along with the previous year questions with solutions.
l Level-I has the questions mainly suitable for JEE Main exam.
l Level-II contains slightly difficult questions suitable for JEE Advanced.
l Level-III has the highest questions of various patterns asked in JEEAdvanced (such as more than one correct answer,
comprehension, match the column and single digit integer).
I hope this book will help in motivating and encouraging the students towards the preparation forthe Chemistry portion of
the examinations. Every care has been taken to make the book error-free. However, some mistakes may have been crept in inad-
vertently. Constructive suggestions and comments from students and teachers would encourage me to make the book more au-
thentic and acceptable in the next edition. We wish our young readers a great success at the engineering entrance examinations.
Ranveer Singh
Acknowledgements
I express my gratitude towards the publisher and the members of the editorial team. I would be failing in my duty if I don’t
express my thankfulness to Mr. Sanjay Agrawal for encouraging me to start writing this book and helping me step by step while
preparing the manuscript.
Contents
Preface vii
Acknowledgements ix
1. Mole Concepts 1.1–1.45
● Key Concepts 1.1
● Solved Examples 1.7
● Exercise 1.12
■ Level I 1.12
■ Level II 1.17
■ Level III 1.20
● Previous Years’ Questions of JEE (Main & Advanced) 1.24
● Answer Key 1.25
● Hints and Solutions 1.26
2. Atomic Structure 2.1–2.49

● Exercise 2.12
■ Level I 2.12
■ Level II 2.19
■ Level III 2.21
● Answer Key 2.30
3. Gaseous State 3.1–3.63

● Exercise 3.28
■ Level I 3.28
■ Level II 3.33
■ Level III 3.35
● Answer Key 3.42

xii Physical Chemistry-I for JEE (Main & Advanced)
4. Chemical Equilibrium 4.1–4.32

l Key Concepts 4.1
l Solved Examples 4.6
l Exercise 4.9
■ Level I 4.9
■ Level II 4.12
■ Level III 4.14
l Previous Years’ Questions of JEE (Main & Advanced) 4.18
l Answer Key 4.19
l Hints and Solutions 4.20
5. Ionic Equilibrium 5.1–5.52
l Key Concepts 5.1
l Solved Examples 5.13
l Exercise 5.18
■ Level I 5.18
■ Level II 5.20
■ Level III 5.22
l Previous Years’ Questions of JEE (Main & Advanced) 5.27
l Answer Key 5.29
l Hints and Solutions 5.30
Chapter
1
Mole Concept
Key Concepts
Mole in Latin means ‘heap’ or ‘mass’ or ‘pile’. A mole of at- 1 Liter = 10–3 m3
oms is a collection of atoms whose total weight is the number T = Temperature in Kelvin
of grams equal to the atomic weight. R = Universal gas constant
The mole is defined as the amount of a substance con- = 0.0821 L atom K–1 mol–1
taining as many atoms, molecules, ions, electrons or other = 8.314 J K–1 mol–1
elementary entities as there are carbon atoms in exactly 12 g = 1.987 cal K–1 mol–1
of C12. Hence, 1 mole is a collection of 6.022 ¥ 1023 particles STP or NTP fi Temperature 273 k and P = 1 atm but in
which is known as the Avogadro Number thermodynamics, T = 298 k.
1 NA = 6.022 ¥ 1023 fi Volume of 1 mole of gas at STP is 22.4 L
fi Volume of 1 mole of gas at 300 k is 24.63 L
fi Number of moles of solute = Molarity ¥ Volume
Method of Calculation of solution in Liter
of Mole
(i) If the number of species is given then Average Atomic Mass
Number of atom
Number of moles =
6.022 ¥ 1023 It is defined as the mass of all atoms divided by number of
(ii) If the weight of an element is given then atoms.
Weight in gram
Number of moles =
Atomic weight Average Molecular Mass
(iii) If the weight of a molecule is given
Weight in gram
Number of moles = It is defined as the total mass of molecules divided by number
Molecular weight of molecules
(iv) Calculation of moles for ideal gases. We know xM +x M +x M º
PV = nRT Average molecular mass = 1 1 2 2 3 3
x1 + x2 + x3 + º
Patm ¥ Vliter
\ n= where M1, M2, M3 are the molecular masses of compound
0.0821 ¥ TKelvin whose abundance x1, x2, x3 ….
P = Pressure exerted by gas (no force of attraction be- fi It is in terms of number of moles or in terms of
tween them) molecules
1 atm = 760 mm Hg or 76 cm Hg fi If x1 + x2 + x3 + …. = 100 then it is called percentage
V = Volume of gas (free volume available for the mo- abundance
tion of gas molecule
1.2 Physical Chemistry-I for JEE (Main & Advanced)
N2 + 3H2 Æ 2 NH3
MoleCular forMulae and Nitrogen Hydrogen Ammonia
eMPiriCal forMulae 1 mole 3 mole 2 mole
28 gram 6 gram 34 gram
Molecular formulae: The actual number of atoms of various NA molecules 3 NA 2 NA
elements present in the compound, e.g., C6H12O6. 22.4 litre 3 ¥ 22.4 litre 2 ¥ 22.4 litre
Empirical formulae: The simplest whole number ratio of
atom in element present in compound, e.g., E.F. of glucose Steps for Using Mole Method in Problem _____
(C6H12O6) is CH2O which shows that carbon, hydrogen and (i) Write down a balanced chemical reaction.
oxygen combined in simple ratio 1 : 2 : 1. (ii) Calculate the number of moles known substance.
Relation between M.F. and E.F. (iii) Write down the number of moles of known substance
under the chemical reaction and relate them.
Molecular Formula = n[Empirical formula]
n = 1, 2, 3, …..
Molecular weight solution and
n= ConCentration terM
Empirical formula weight
Step for Determination of Empirical Formulae Solution is defined at a homogenous mixture of more than
(i) Divide % of atom by its atomic mass. It gives relative one substance in which one is solvent and rest solute.
number of moles of various elements present in the Which substance is solute or solvent is controversial and
can be concluded in the following cases:
compound.
(ii) Divide relative number of moles obtained in Step (i) by Case I: When substances forming solution are in different
the smallest mole so as to get simple ratio of moles of states, the final state of solution will be solvent irrespective
various elements present in compound. of substances.
(iii) If simple ratio of mole is a fractional value, then the Case II: When substances forming solution are in the same
value of simple ratio of moles of each element is mul- state, then the solvent is one which is present in large amount.
tiplied by smallest integer so as to get simplest whole Amounts compared should be in mass and mole.
number ratio of each element present in the compound. Some hints are given in the question like A in B. Then A is
solute and B is solvent.
Determination of Molecular Formulae _______ All the concentrated terms defined are applicable only for
(i) When the molecular mass is given homogenous mixture and not for heterogeneous mixture.
Suppose Empirical formula = C3H6O and Weight of solute
1. Density =
Molecular mass = 174 Volume of solution
174 Unit is either in g/mL or g/litre
n= =3 Temperature is dependent because Mass µ / T but vol-
58
ume is depend upon temperature (T µ V).
then M.M. = 3[C3H6O] = C9H18O3
\ T inversily proportional to
(ii) When number of any atom is given
Suppose EF is C3H6O and given that number of oxygen Weight of solute
(density) except water
atom is 2. Volume of solution W
then MF = [C3H6O] ¥ 2 = C6H12O6 2. Mass percentage or percentage mass %
W
(iii) When the vapour density is given W Weight of Solute
%= ¥ 100
(only for gas and vapour) W Weight of solution
2 ¥ VD Temperature independent
n=
Molecular weight For example, 20% mass of NaOH solution means 100 g
of solution contains 20 g of NaOH and mass of solvent
is 80 g.
stoiChioMetrY W
3. % weight by volume or % or % by volume.
V
It deals with the calculation of quantities of various reactants W Weight of Solute
and products in a chemical reaction. %= ¥ 100
V Volume of solution
The numerical used to balance a chemical reaction is V
known as stoichiometric coefficient. 4. % volume by volume or % or % by volume.
V
Balanced equations gives the qualitative and quantitative
V Volume of Solute
information. %= ¥ 100
V Volume of solution
Mole Concept 1.3
Molarity For gases

Moles of solute Volume of solute
M= PPM = ¥ 106
Volume in liter Volume of solution
Temperature dependent Moles of solute
PPB = ¥ 109
For example, 2 M NaCl solution means 1 L solution contains Moles of solution
2 moles of NaCl. Æ For gases parts = volume = moles
Æ For solid/liquid parts = weight
For solid/liquid
MolaritY of Pure
weight of solute
suBstanCe PPM = ¥ 106
weight of solution
1 mL = 1 g weight of solute
1000 mL = 1000 g = 55.56 moles PPB = ¥ 109
weight of solution
\ moles in 1 L pure solution Æ For dilute solution
weight (Weight of Solute  Weight of Solution)
Molar mass 55.56 mole weight of solute
= = = Molarity = 55.56 M PPM = ¥ 106
Volume in liter 1 liter weight of solvent
MolalitY [m] tYPiCal ConCentration

terMs
Number of moles of solute in 1 kg solvent.
These concentrated terms are typical because they are de-
So temperature is independent.
fined exclusively for the substance concerned depending on
For example, 2 m solution of NaCl means 2 moles of NaCl
what purpose those substances are used.
present in 1000 g of solvent.
Concentration of H2O2: H2O2 is used as a source of oxygen
gas and hence the typical concentration of H2O2 gives the
Mole fraCtion value of oxygen obtained from the given solution. Since it
decomposes according to following reaction:
Ratio of moles of one component to the total number of 2H2O2 Æ 2H2O + O2
moles of solution. Definition of concentration term of H2O2: “x volume
A B C H2O2” means 1 L of H2O2 gives x L of O2 gas at STP.
nA nB nC Number of moles For example, 20 volume H2O2 means 1 L of H2O2 gives
XA XB XC mole fraction 20 L of O2 at STP. It can be converted to normal concentration.
nA
XA=
n A + nB + nC ConCentration of oleuM
and Sx = 1
or xA + xB + xC = 1 Oleum is considered as a solution of SO3 gas dissolved in
H2SO4. H2S2O7 is a type of oleum and 1 mole of SO3 and 1
For binary solution xA + xB = 1 mole of H2SO4.
XB = 1 – xA H2SO4 SO3 H2S2O7
Log10[xA + xB + xC] = log101 = 0 Liquid Gas
If Sn = 1 Solvent solute solution
Concentration of oleum is defined in such a way that it
XA = nA gives an idea of amount of H2SO4 it can give.
It means MF of A = mole of A. Concentration of oleum is given by x % oleum. It means
100 g of oleum sample can maxima give x g of H2SO4 by the
PPM and PPB (Parts per million and addition of (x – 100) g of water.
For example, 109 % oleum means 100 g oleum is capable
Parts per billion) _________________________
of giving 109 g H2SO4 by adding 9 g of H2O in 100 g of
Parts of solute oleum.
PPM = ¥ 106 An oleum sample labelled as x % implies the (x – 100) g of
Parts of solution
H2O will be required to react with all the SO3 present in 100
Parts of solute
PPB = ¥ 109 g of oleum according to the following reaction:
Parts of solution
H2O + SO3 Æ H2SO4 in 100 g oleum
So, number of mole of water required = number of moles of

SO3 gas present in Oleum
analYsis of gaseous
suBstanCes in
x % Max. wH2O nH2O wSO3 wH2SO4 eudioMetriC tuBes
Oleum H2SO4 = nSO3
Gaseous reactions are studied in this tube. After the comple-
104.5 % 104.5 4.5 0.25 0.25 ¥ 80 = 20 100 – 20 = 80 tion of reaction, the reaction is brought back to original tem-
109 % 109 9 0.5 0.5 ¥ 80 = 40 60 perature.
118 % 118 18 1 1 ¥ 80 = 80 20 1 atm
Pt
Filament to 1 atm
spark mixture Reactant can
be added
analYsis of gaseous
Hg
reaCtion [eudioMetrY]
This method is used to determine the composition of gaseous
mixture or to find out the M.F. of an unknown compound.
It is based on ‘Gay Lussac Law of combining volume’.
This law states that gaseous reaction volume of reactant
Eudiometric Tube
consumed and volume of product obtained [at fixed T and P]
are in a simple whole number ratio [which is same as the ratio Fig. 1.1
of Stoichiometric coefficient of balanced reaction].
To estimate the volume of each gas, certain solvents are
For example, from experiment it was found that 10 L of N2 used.
require 30 L of H2 to produce 20 L NH3.
Solvent Gases absorbed
\ volume ratio = 1 : 3 : 2 [Stoichiometric coefficient] 1. KOH CO2, SO2, Cl2
Since the reaction is carried out at constant T and P, then, 2. CuSO4/CaCl2 H2O (g)
volume of gaseous mixture is directly proportional to number 3. H2O NH3, HCl
of moles of gases and change in volume is proportional to 4. Terpentine oil O3
change in number of moles of gases. 5. Alk. Pyrogallol O2
Vµn 6. Ammonical Cu2Cl2 CO
\ DV µ Dn We will consider only the volume of gases and not of solid
This expression can be used if pressure of individual spe- and liquid as they have very less volume compared to gas.
cies used [at constant T and V] Hence, the volume of solids and liquids is neglected with re-
Pµn spect to gases.
Whenever water is formed inside the eudiometric tube, it
DP µ Dn is always assumed to be liquid until a minimum temperature
Hence, for N2 + 3H2 Æ 2NH3 of 100°C.
1 mole 3 mole 2 mole It is used in the following combinations:
1 atm of N2 3 atm of N2 2 atm of NH3 (i) Combustion of all organic compound.
So V µ n [at constant T and P] (ii) Reaction of H2 with O2.
P µ n [at constant T and V] (iii) Dissociation or formation of NH3.
(iv) Reaction between N2 and O2 never occur inside the
Example: 10 mL of alkane on complete combustion gives 30 eudiometric tube as it requires very high temperature.
mL of CO2. Calculate molecular formula? (v) H2 when reacts with certain oxide gives H2O.
È y˘ y (vi) Whenever a substance is added in eudiometric tube for
CxHy + Í x + ˙ O2 Æ xCO2 + H2O
Î 4˚ 2 a particular reaction, it is always assumed to be taken
1 mole gives x mole in excess.
1 mL give x mL
10 mL 10 ¥ x mL = 30 mL given eXPeriMental Methods
and x=3 for deterMination of
È y˘ y eleMents in organiC
10 mL 10 Í x + ˙ ml 10x mL 10 ¥ mL CoMPound
Î 2 ˚ 2
Since, molecular formula of alkane CxH2x + 2 = Cx Hy A sample of organic compound on qualitative analysis (with
So, y = 8 elements present) was found to contain C S H N P O X. The
following experiment were performed. Calculate % composi-
Therefore, molecular formula = C3H8
tion of each element.
Mole Concept 1.5
A w g sample was burned in the presence of CuO to cause

[P – P ¢]V ml ¥10-3
oxidation of C, H and N only (CO2, H2O, N2). The gaseous and nN2 =
mixture was passed through a solution of KOH weighing RT
w1 g. The final weight after passing the gases was w2. The -3 28
\ % N = ÈÍ(P - P ¢)V ml ¥10 ˘˙ ¥ ¥ 100
remaining gases on passing through white CuSO4 crystal to W
Î RT ˚
convert into blue crystal (hydrated CuSO4) caused a weight
rise of w3 g.
The remaining gas was collected over H2O at T Kelvin. estiMation of n2 inforM
[Any gas collected over H2O is present with some water va- of nh3 in solution
pour]. Total pressure observed was ‘P atm’. Value of displaced KJeldohl’s Method
liquid was V mL and T. If aq. tension of H2O at T is P1 atm [aq.
tension at any temperature is defined as maximum pressure W g sample was reacted with concentrated H2SO4 to cause
which can be exerted by water vapour in equilibrium with wa- conversion of all N2 present in the compound. Ammonium
ter in liquid form], calculate the composition of each element. sulphate (NH4)2SO4 solution was then added with excess of
From first experiment NaOH and all NH3 librated was reacted with H2SO4 solution
[Liebig Method] having molarity M1 and volume V1 liter. The residual acid
Organic Compound
CuO
CO2 + H2O + N2 was reacted with NaOH solution and it was observed that V2
liter of NaOH molarity M2 was required to complete natural-
Wgram
Absorbed Absorbed ization of residual acid. Calculate % composition of N2 from
by by above data?
KOH w2 (after) con H SO
W1 CuSO4 Sol. Organic Compound æææææ
2
MV
4
Æ (NH 4 ) 2SO 4
1 1
before w3 gm W gram
Weight rise in KOH = w2 – w1 = wCO2 NaOH (for neutralisation of excess H SO )

æææææææææææææ
2 4
Æ NH3
M V 2 2
Since all CO2 obtain from Organic Compound
2NH3 + H2SO4 Æ (NH4)2 SO4
w - w1
\ nC = nCO2 fi 2 and
44
\ % of Carbon in Organic Compound H2SO4 + 2 NaOH Æ Na2SO4 + 2H2O
1 w2 - w1 1
= ¥ 12 ¥ 100 MV MV
44 W 2 2 2 2 2
w M V
Moles of H2O = 3 = nH2O = nH2 (i) nH2SO4 = 2 2
18 2
w3 (react with NaOH)
\ moles of H2 = È M V ˘
18 (ii) nH2SO4 = Í M1V1 - 2 2 ˙
w react with NH3 Î 2 ˚
\ weight of H2 = 3 ¥ 2
18 È M V ˘
w 2 (iii) \ nNH3 = 2 Í M1V1 - 2 2 ˙
\ % of H in Organic Compound = 3 ¥ ¥ 100 Î 2 ˚
18 W
From second experiment : [Duma Method] È1 ¥ nNH3 ¥ 14 ˘
(iv) % N in OC = Í ˙ ¥ 100
Organic Compound æææ
CuO
Æ H2O + CO2 + N2 Î W ˚
P¢ + PN2 P Ï È M 2V2 ˘ ¸
Ì2 Í M1V1 - ˙ ¥ 14 ˝
Î 2 ˚
= Ó ˛ ¥ 100
aq. tension
N2
W
Barometric
pressure P \ PN2 P P¢
Carius Method
[identifiCation of
Fig. 1.2 halogen eXCePt fluorine]
PN2 ◊ VN2 Organic Compound Wgram æææ
3
Æ X-
HNO
n N2 = but % N in Organic Compound
R ◊ TN2 AgNO
ion in solution ææææ
3
Æ AgX
wN2
= ¥ 100 W Gram ________________________________
W
W g of Organic Compound is reacted with concentrated
nN2 ¥ 28 ¥ 100
\ %N = HNO3, then AgNO3 solution is added in the remaining solu-
W
tion (containing halide ion solution which is obtained by re-

action between Organic Compound and concentrated HNO3).
eXPeriMental Methods
Weight of residue will be formed if w1 g white precipitate, w2
for deterMination of
g of AgBr (pale yellow precipitate) and w3 g of AgI (bright atoMiC Mass of Metals
yellow precipitate) are formed. Then calculate % composi- Dulong Petit’s law
tion of Cl, Br and iodine. Atomic weight ¥ Specific heat of compound ≥ 6.4
wCl (i) This is experimental law.
% WCl in Organic Compound = ¥ 100
W (ii) Specific heat should be measured in calorie/gram.
1 ¥ n[AgCl] ¥ 35.5 ¥ 100 (iii) The above expression given is approximately Atomic
= (using POAC)
W weight.
1 ¥ w1 ¥ 35.5
% WCl in Organic Compound = ¥ 100 1 g of metal at 30º was immersed in 10 g of water at 19.886
143.5 ¥ W ºC. If the final temperature is 20ºC then predict that metal
as same
could be iron (Specific heat of H2O = 1 cal/g).
1 ¥ w2 80
% WBr in Organic Compound = ¥ ¥ 100 1 gm metal at 10 gm water at
188 W 30°C 19.866°C
1 ¥ w3
% WI in Organic Compound = ¥ 127 ¥ 100
235 ¥ W
20°C
estiMation of sulPhur Heat lost by metal = Heat gained by water
m1C1Dt1 = m2C2 Dt2
W g sample of Organic Compound was reacted with concen-
trated HNO3. The remaining solution containing H2SO4 (ob- 1 ¥ C1 ¥ [30 – 20] = 10 ¥ 1[20 – 19.886]
tained after all the sulphure gets oxidised to SO3 and then to \ C1 = 0.114
H2SO4) was reacted with excess of BaCl2 solution and w1 g 6.4
of white ppt of BaSO4 was obtained. Calculate % composi- \ Atomic mass = = 56.2
0.114
tion of sulphur.
w 1 ¥ w1 ¥ 32
% S = S ¥ 100 = ¥ 100
W W ¥ 233 deterMination of
MoleCular Mass
estiMation of PhosPhorus [viCtor MaYer Method]
Weight
Organic Compound æææ
3 HNO
Æ H3PO4 æææææææ
Magnesia mixture
Æ PV = nRT = ¥ RT
[MgSO + NH Cl] 4 4 Molar Mass
D
Mg(NH4)PO4 ææ
Æ Mg2P2O7 (white ppt) W RT
M Mass =
( P – P ¢)V
W g sample of Organic Compound was reacted with
HNO3. All phosphorous after being oxidised to H3PO4 was Vair displaced = Vvapour
reacted with magnesia mixture and a yellow precipitate was and Pair displaced = Pvapour
obtained, which on heating gives w1 g of white precipitate of
Mg2P2O7. Calculate % of P in Organic Compound. w ( P – P¢)V
and =
w Molar mass RT
% of P in Organic Compound = P ¥ 100
W
2 ¥ w1 31 P = P + Pdisplaced air
= ¥ ¥ 100
222 W
From
2[nMg 2 P2O7 ]
¥ 31 ¥ 100
W
W gram Water
estiMation of oXYgen
Weight of oxygen in Organic Compound Fig. 1.3

= Weight of organic compound – W ¢
[sum of weight of all element] \ Pdisplaced air = (P – P¢)
Mole Concept 1.7
Vapour of volatile substance are collected over water and and Molar Mass of AgX = Atomic Mass of Ag + Molecular
measured by the method as Duma’s method. Mass of X
w1
deterMination of ¥ 108 = 108 + Molecular Mass of X
w2
MoleCular Mass of
organiC aCid silver salt Èw ˘
Molecular mass of X = Í 1 ¥ 108 - 108˙
Method Î w2 ˚
Hydrogen connected to a more electronegative atom is acidic. Molecular mass of HX = Atomic Mass of H + Molecu-
Basicity is defined as the number moles of hydrogen ion
lar Mass of X
in 1 mole of given acid.
AgNO3 soluton D = 1 + M.M. of X
Organic Acid ææææææ Æ Silver salt ææ Æ Ag
For monobasic Acid (CH3COOH) Molecular mass of HX or Organic Acid = 1 + Molar Mass
AgNO D of X
HX ææææ 3
Æ AgX ææ
Æ Ag
CH3COOH w1 w2 For dibasic Acid H2X
Applying POAC on Ag Atom ÔÏ È w ˘ Ô¸

Molecular mass of H2X = 2 + Ì Í 1 ¥ 108 - 108˙ ˝ ¥ 2
w1 w2 w
ÓÔ Î 2 ˚ ˛Ô
=
Molar Mass of AgX Atomic Mass of Ag
ÏÔ È w1 ˘ ¸Ô
w For tribasic Acid H3X = 3 + Ì Í ¥ 108 - 108˙ ˝ ¥ 3
\ Molar Mass of AgX = 1 ¥ Atomic Mass of Ag ÓÔ Î w2 ˚ ˛Ô
w2
w1 Èw ˘
= ¥ 108 = Í ¥ 108 - 107 ˙ ¥ 3
w2 w
Î 2 ˚
Solved Examples
1. Calculate the volume of 1 mole gas exerting pressure Sol. 1 mole of S8 = NA molecules of S8 = 8 ¥ 32 g
of 1 atm at a temperature of 273 K. 64 N
nRT \ number of molecules = = A
Sol. V = = 0.0821 ¥ 273 = 22.4 L 8 ¥ 32 4
P NA
2. Calculate the volume of 1 mole of gas exerting pres- \ number of atom of sulphur = 8 ¥ = 2 NA
4
sure of 1 atm at a temperature of 300 K. 6. Calculate the number of molecules in
Sol. PV = nRT (i) 34.2 g of cone sugar (C12H22O11)
nRT (ii) 1 L of water assuming density 1 g
\ V= = 1 ¥ 0.0821 ¥ 300 = 24.3 L (iii) 1 drop of water having mass 0.05 g
P
3. 44.8 L of oxygen contains how many moles of O2? 34.2 N
Sol. (i) ¥ NA = A
Sol. Since T and P are not given, so number of mole cannot 342 10
be calculated. (ii) 1 mL = 1 g
4. 22.4 L of aq.{H2O] at STP contains how many moles? 1000 g
Sol. 1 mL = 1 g \ 1000 mL = NA
18
1000 0.05 N
1 litre = 1000 g = moles (iii) ¥ NA = A
18 18 360
Calculation of number of atoms and molecules in a given 7. Elemental analysis of an organic compound containing
mass of substance. C, H, N and O and weighing 7.3 g was found to contain
5. How many atoms and molecules of sulphur are present 3.6 g of carbon, 0.7 g of H and 1.4 g of nitrogen. Cal-
in 64 g of S8? culate Empirical formula.
0.7 \ number of moles of O2 obtained

Sol. H 0.7 = 0.7 7
1 3 3 È 1.49 ˘
3.6 = [n] = ¥ Í ˙
C 3.6 = 0.3 3 2 2 Î 74.5 ˚
12 3 È 1.49 ˘
1.4 \ mass of O2 = ¥ 32
N 1.4 = 0.1 1 2 ÍÎ 74.5 ˙˚
14
\ volume of oxygen at STP
1.6
O 1.6 = 0.1 1 3 1.49
1.6 = ¥ ¥ 22.4 L = 0.672 L
\ Empirical formula = C3H7NO 2 74.5
11. When 4 g of CaCO3 and sand mixture is treated with
OR
excess of HCl, 0.88 g of CO2 is produced. Calculate %
weight weight weight of CaCO3.
C H
Atomic weight Atomic weight
Sol. CaCO3 + 2HCl Æ CO2 + H2O + CaCl2
weight weight
N O Sand + HCl Æ No reaction
Atomic weight Atomic weight 0.88
C 3 6 H 0 7 N 1 4 O1 6 = C3H 7 NO Number of moles of CO2 = = 0.02 mole
44
12 1 14 16
\ number of moles of CaCO3 = 0.02 moles
8. Calculate the Empirical formula of the following min-
erals that have the following composition: ZnSO4 = 0.02 ¥ 100
\ % mass of CaCO3 = ¥ 100
56.14 H2O = 43.86. Weight of mixture
56.14 0.35 0.02 ¥ 100
Sol. ZnSO4 56.14 = 0.35 =1 = ¥ 100 = 50%
161.4 0.35 4
43.86 2.44
H 2O 43.86 = 2.44 =7 12. A sample of 5 g of natural gas consisting of methane
18 0.35 and ethylene was burnt in excess of O2 yielding 14.5 g
ZnSO4.7H2O of CO2. Calculate the weight % of ethylene.
9. Calculate Empirical formula of hydrocarbon if 1.4 g of Sol. CH4 = x g
this compound is on complete combustion. Gives 4.4 g C2H4 = 5 – x g
of CO2 and 1.8 g of H2O. Number of Moles of CH4 = x/16
y Number of Moles of C2H4 = 5 – x/28
Sol. CxHy + O2 Æ xCO2 + H2O CH4 + O2 Æ CO2 + 2 H2O
2
 1 mole of CO2 contains 1 mole of C C2H4 + O2 Æ 2 CO2 + 2 H2O
\ 44 g of CO2 contains 12 gram of C 14.5
\ 4.4 g of CO2 contain 1.2 g of C Number of Moles of CO2 =
44
1 mole H2O contains 2 mole of H. [from methane and ethylene]
18 gram H2O contains 2 mole = 2 g
14.5 È5 - x ˘ Èx ˘
\ 1.8 gram H2O contains 2 mole = 0.2 g = Í ¥ 2˙ + Í ¥ 1˙
44 Î 28 ˚ Î16 ˚
1.2
C 1.2 0.1 1 5- x
1.2 \ % weight of ethylene = ¥ 100
0.2 5
H 0.2 0.2 2 13. In a rocket motor filled with butane, how many kg of
1
CH2 = EF liquid oxygen should be provided for each kg of butane
for its complete combustion?
10. Calculate the weight of KClO3 required and the weight
13
of oxygen in product. If 1.49 g of KCl is obtained on Sol. C4H10 + O2 Æ 4CO2 + 5 H2O
heating, calculate the volume of oxygen at STP. 2
Sol. 2KClO3 Æ 2 KCl + 3O2 [1 ¥ 103 g]
1.49 1000
Number of moles of KCl = \ number of moles of C4H10 =
74.5 58
2 moles of KCl produced from 2 moles of KClO3.
\ mass of KClO3 = n ¥ molecular weight È1000 ˘ 13
\ number of moles of O2 = Í ¥
1.49 Î 58 ˙˚ 2
= ¥ 122.5
74.5 È1000 ˘ 13
\ Mass of O2 = Í ¥ ¥ 32 gram = 3.586 Kg
and 2 moles of KClO3 is required for 3 moles of O2. Î 58 ˙˚ 2
Mole Concept 1.9
14. In a sample of NaCl and KCl weight of mixture is 20.75 2.76 È Weight ˘
g. This was dissolved in water and heated with excess
138
= 12 Í ˙ \ Weight = 1.163 gram
Î 698.2 ˚
of AgNO3. If weight of white precipitate of AgNO3 is
43.05 g, calculate the weight of each component. 17. For preparation of H2SO4 from iron pyrite [FeS2] in-
volves following set of reaction:
Sol. Weight of NaCl = x g FeS2 + O2 æÆ Fe2O3 + SO2
\ weight of KCl = 20.75 – x g SO2 + O2 æÆ SO3
AgNO SO3 + H2O æÆ H2SO4
NaCl ææææ 3
Æ AgCl
H 2O Calculate the weight of H2SO4 which can be obtained
x
= (a mole) when 240 kg of FeS2 is used.
58.5 Sol. Applied POAC of S
AgNO3
KCl ææææ Æ AgCl 2 moles of FeS2 = 1 ¥ moles of H2SO4
H O 2
20.75 - x È Weight of FeS2 ˘ È Weight of H 2SO 4 ˘
= (b mole) 2Í ˙ = 1¥ Í ˙
143.5 Î MM of FeS2 ˚ Î MM of H 2SO 4 ˚
43.05 x 20.75 - x È 240 ¥ 103 ˘
a+b= = + È weight ˘
143.5 58.5 74.5 2Í ˙ = 1¥ Í
Î MM of FeS 2˚ Î 98 ˙˚
If chemical reaction are not balanced [Principle of Atomic Weight of H2SO4 = 392 kg
conservation] [POAC]
v w w
According to this theory, if atoms are conserved, then moles 18. If 20 % is given then convert into % and % .
of atoms shall also be conserved [POAC]. V W V
This concept is used when chemical reaction is not bal- If d is the density of solution.
anced and atleast one of the atoms is such that it is present Sol. 100 mL of solution contains 20 mL of NaOH and 80
only in one given compound and required compound. mL of H2O.
KClO3 Æ KCl + O2 w Mass of solution - Mass of solvent
% = ¥ 100
Applied POAC on K atom W Mass of solution
Weight of KClO3 Weight of KCl È100d - 80 ¥ 1˘ È100d - 80 ˘
= Í ¥ 100 = Í ˙˚ %
Molar Mass of KClO3 = Molar Mass of KCl Î 100 d ˙
˚ Î d
Applied POAC on oxygen atom
w È 100d - 80 ¥1 ˘
3 ¥ moles of KClO3 = 2 ¥ moles of O2 %= Í ˙ ¥ 100 = [100d – 80]%
V Î100(Volumeof solution) ˚
Weight of KClO3 Weight of O 2
3¥ =2¥ w
MM of KClO3 MM of O 2 19. Given 20 % of aq. NaOH. Then find its molarity.
V
15. CaCO3 æÆ CaO + CO2
Sol. 100 mL solution contains 20 g NaOH.
1000 g weight of CO2 = ?
\ 1000 mL solution contains 200 g NaOH
POAC on C atom 200
1 ¥ mole of CaCO3 = 1 mole of CO2 \ number of moles = = 5 moles
40
Weight of CaCO3 Weight of CO 2 and 1000 mL = 1 L
=
MM of CaCO3 MM of CO 2 5
1000 weight of CO 2 \ molarity = = 5 M.
= 1
100 44 w
Weight of CO2 = 440 g 20. Convert 40 % NaOH solution into molarity. If
W
16. Calculate the mass of compound [K2Zn3[Fe(CN)6]2 density of solution is d g/mL.
when 2.76 g of K2CO3 undergoes series of reaction Sol. 100 g solution contains 40 g NaOH.
such that all carbons convert into this complex. Given 40 g of NaOH = 1 mole
Molar Mass of complex compound (C.C) = 698.2 and
100 1
MM of K2CO3 = 138. Volume of solution = = L
d ¥ 1000 10 d
Sol. K2CO3 Æ K2Zn3[Fe(CN)6]2
È Mass ˘
Applied POAC on carbon ÍSince V = density ˙
1 mole of K2CO3 = 12 ¥ moles of complex Î ˚
Weight of K 2 CO3 È Weight of C.C ˘ 1
= 12 Í  L solution contains 1 mole of NaOH
˙ 10 d
MM of K 2 CO3 Î MM of C.C ˚
\ 1 L solution contains 1 mole of NaOH \ molarity after ionisation

1 0.1 ¥ 80
= = 10 dM 0.1 – aa 2aa
1 100
10 d 0.1 ¥ 80 2 ¥ 0.1 ¥ 80
=
\ Molarity = 10 dM 100 100
M Be+2 = 0.08 M
21. Calculate molality of 20% by mass NaOH solution. and M Cl- = 0.16 M
Sol. 20 % by mass means 20 g NaOH present in 80 g of
solvent. pH = – log[H+]
20/40 20 1000 [H+] Æ [1] 10–7 10–14
\ Molality m = = ¥
80/1000 40 80 Acidic
Neutral
Basic
PH O ¨æææ 7 æææ
Æ 14
22. A solution of I2 in benzene has a mole fraction of
I2 = 0.2. If density of solute is 1.2 g/mL, calculate 25. Calculate the degree of dissociation of pure water at
(i) Molality (ii) Molarity 298 K if it is known that pH = 7.
Sol. I2 in benzene means I2 solute and benzene solvent Sol. H2O æÆ H+ + OH–
nI 55.55 M 0 0
and X I 2 = 2 [55.55 – 55.55a] 55.55a 55.55a
Sn
nI 2 = X I 2 ¥ Sn but [H+] = 55.55a = 1 ¥ 10–7
1 ¥ 10-7 1
\ nC6H6 = xC6H6 ¥ Sn \ a= = = 1.8 ¥ 10–9
55.55 55.55 ¥ 107
X I 2 = 0.2 \ X C6H6 = 1 – 0.2 = 0.8 Hence, out of 55.55 ¥ 107 molecule of water, only one
x I 2 ¥ Sn molecule dissociate.
m= ¥ 1000 concentration of any ion
xC6H6 ¥ Sn ¥ 78 Note: a =
concentration of that ion (theoritically)
È x I 2 ¥ Sn ˘ (complete ionisation)
M= Í ˙ ¥ 1000
[(
Í I2 x ¥ S n ) ¥ 254] + ( xC6 H 6 ◊ S n ) ¥ 78 ˙ 26. If Molarity of Na3PO4 is 1 molar and concentration of
ÍÎ 1.2 gram/ml ˙˚ Na ion is 0.2 M. Calculate % dissociation of Na3PO4.
23. Calculate molality of all ions present in 1 molar Sol. Na3PO4 æÆ 3Na+ + PO -4 - -
Al2(SO4)3 solution. Given that density of solution = 1 0 0
2.34 g/mL. 1–x 3x x
1 If complete ionisation actually
Sol. mAl2 (SO4 )3 = ¥ 1000 ---
1000 ¥ 2.342 - 1 ¥ 342 1 mole gives 3 mole Na+ and 1 mole PO 4
2 Given that 3x = 0.2
mAl+3 = ¥ 1000 = 1 m
2000 0.2 20
\ a= ¥ 100 = = 6.6 %
3 3 3
m - - = 3 ¥ 100 = m
SO4
2000 2 27. (i) 200 mL of 1 M HCl solution is mixed with 800 mL
of 2 M HCl solution. Calculate the molarity of final
Case II: Degree of Dissociation solution.
Moles dissociated (x) Number of moles of solute
= Sol. Molarity =
Total number of moles before dissociation Total volume(V1 + V2 )
x
a= È ˘
a Í 1 ¥ 200 2 ¥ 800 ˙
\ x = aa Í 1000 + 1000 ˙
For A æÆ 3B + C = Í ˙ ¥ 1000
Î 800 + 200 ˚
a 0 0
a–x 3x x = 1.8 M
(a – aa) (3aa) (aa) (ii) If density of solution is 1.2 g/mL, calculate molal-
24. Find the molarity of each ion in 0.1 M BaCl2 consider- ity.
ing degree of dissociation = 80 % 1000 M
Sol. m =
BeCl2 æÆ Be+2 + 2Cl– 1000d - Molar Mass of solute
0.1 0 0 1.8 ¥ 1000
0.1 – x x 2x = m
1000 ¥ 1.2 - 1.8 ¥ 36.5
Mole Concept 1.11
(iii) If sample of H2SO4 in 1.8 g/mL is 98% wt. What 30. Calculate [H+] concentration if 0.2 M of H2SO4 solu-
is the volume of acid that has to be taken to tion having volume 100 mL is mixed with 0.1 M of 300
form 1 L of 0.2 M H2SO4 solution? mL of NaOH.
Sol. 2NaOH + H2SO4 Æ Na2SO4 + 2 H2O
98 % wt. diluted 1L of 0.2 M before reaction
Sol. æææÆ
1.8 g/mL H 2SO 4 solvent No. of moles of NaOH = 0.1 ¥ 0.300
No. of moles of H2SO4 = 0.2 ¥ 0.100
Number of mole of solute before dilution = Number of No. of moles of H2SO4 after reaction
mole of solute after dilution
0.003
È 98/98 ˘ = 0.02 – = .005
V ¥ M = 1 ¥ 0.2 = Í ¥ 1000 2
100 ˙
Í ˙ \ [H+] = 2 ¥ 0.005 Mole = 0.01 mole
Î 1.8 ˚
È 0.01˘
28. 10 mL of H2O[d = 1 g/mL] and 4 mL of CH3OH \ molarity = Í ¥ 1000 = 0.025 M
[d = 0.8 g/mL) is mixed to form a solution. If the den- Î 400 ˙˚
sity of final solution is 1.1 g/mL, calculate the molarity 31. 200 mL of 0.1 M NaCl is mixed with 100 mL of 0.2 M
of final solution. AgNO3 solution. Calculate molarity of all the ions in
Sol. WH2O = 10 ¥ 1 = 10 g final solution.
Sol. NaCl + AgNO3 Æ AgClØ + NaNO3
WCH3OH = 4 ¥ 0.8 = 3.2 g
0.2 ¥ 0.1 0.1 ¥ 0.2 ppt
Total weight of solution = 10 + 3.2 = 13.2 g 0.02 0.02 \ if no ion is formed
13.2 0 0 0.02 0.02
\ volume of solution = = 12 mL
1.1 0.02
\ M Na + = ¥ 1000 and
È 3.2/32 ˘ 300
\ molarity of solution = Í ˙ ¥ 100
Î 12 ˚ 0.02
M NO- = ¥ 1000
3 300
Note:
32. 10 L mixture of C2H6 and C3H8 at STP on complete
1. If during mixing of solution, mass of final solu-
combustion gives 22 L of CO2 at STP. Find the molar
tion and density of final solution is given then
concentration of the mixture in molar ratio.
volume of solution should be calculated by
Total mass 7
V= Sol. C2H6 + O2 Æ 2CO2 + 3H2O
Density of solution 2
2. If any one data of the following is not given: C3H8 + 5O2 Æ 3CO2 + 4H2O
(a) mass of any mixing substance (b) density Since V µ Number of moles of gas
of resultant solution, then it has to be assumed
and VCO2 = 22 L = [VCO2 ]C2H6 + [VCO2 ]C3H8
that there is no volume contraction or expan-
sion taking place and V = V1 + V2 + …… = 2V + 3(10 – V) = 22
\ –V = –8
29. 100 mL of 0.1 M of Al2(SO4)3 is mixed with 100 mL V=8L
of 0.1 M AlCl3. Calculate molarity of Al+3 ion if final VC2H6 nC H 8
solution has density of 1.2 g/mL. \ = 2 6 = =4:1
VC3H8 nC3H8 2
100 ¥ 0.1
Sol. nAl2 (SO4 )3 = = 0.01 mole 33. If volume of CO2 is 24 L at 1 atm and 300 K in Q32,
1000
then calculate the molar composition of initial mixture.
nAlCl3 = 100 ¥ 0.1 = 0.01 mole PV PV
1000 1 1
= 2 2
\ n of Al+3 T1 T2
0.02 mole + 0.01 mole = 0.03 mole PV T 1 ¥ 24 ¥ 273
\ V2 = 1 1 2 =
From Al2(SO4)3 and AlCl3 P2T1 1 ¥ 300
\ molarity of Al+3 V2 = 2V + 3[10 – V]
nAl+3
= Note:
Total volume If in a question [volume or pressure] is given in dif-
È 0.03 ˘ ferent conditions then it is better to convert at STP
= Í ¥ 1000
Î 200 ˙˚ PV
condition by using 1 1 = 2 2
PV
= 1.5 ¥ 10–1 M T1 T2
34. A mixture of C2H6 and C3H8 at 200 mm of Hg on com- 37. The vapour of W g sample of Organic Compound oc-
plete combustion gives CO2 at 450 mm Hg. Calculate cupy V mL at STP in Victor mayer process. Calculate
molar ratio of initial mixture. Molar mass of compound?
Sol. Since P µ Number of moles of gas Sol. From V mL = W gram at STP
450 mm = (PCO2 )C2H6 + (PCO2 )C3H8 W
\ 22400 mL = ¥ 22400 = Molar mass
7 V
C2H6 + O2 Æ 2CO 2 + 3H2O
2 (2x )
38. 0.41 g of silver salt is obtained after reaction between
dibasic acid and silver nitrate solution, which on heat-
C3H8 + 5O2 Æ 3CO 2 + 4 H2O
3[200 - x ] ing gives 0.216 g of residue. Calculate MM of acid.
Sol. w1 = 0.41 g, w2 = 0.216 g
\ 450 = 2x + 3[200 – x]
Acid fi dibasic then
X = 150 = PC2H6
\ PC3H8 = 200 – 150 = 50 Ïw ¸
MM = Ì 1 ¥ 108 - 107 ˝ ¥ 2
nC2H6 3 Ó w2 ˛
\ = Ï 0.410 ¸
nC3H8 1 = Ì ¥ 108 - 107 ˝ ¥ 2 = 196
Ó 0.216 ˛
35. 1 g of metal at 30º was immersed in 10 g of water at
19.886 ºC. If the final temperature is 20ºC then predict 39. Estimation of Molar Mass
that metal could be iron (Specific heat of H2O = 1 cal/g). of silver salt, acid graph of
Sol. 1 gm metal at 10 gm water at the residue obtained and the
30°C 19.866°C weight of silver salt was
plotted as shown in fol- Ag
q 30°
lowing graph. If the acid (w2)
20°C is known to be monobasic, Silver salt
(w1)
Heat lost by metal = Heat gained by water calculate Molar Mass of
Fig. 1.4
salt and Molar Mass of acid.
m1C1Dt1 = m2C2 Dt2
1 ¥ C1 ¥ [30 – 20] = 10 ¥ 1[20 – 19.886] w1 w2
Sol. We know =
\ C1 = 0.114 Molar Mass of AgX Molar Mass of Ag
6.4 w1 1
\ atomic mass = = 56.2 Slope = tan 30° = =
0.114 w2 3
36. A sample of Organic Compound weight 10 g in Victor
w2 1 Molar Mass of Ag
mayer process was found to displace 2.463 mL at 1 atm \ = =
and 300 K. Calculate Molar Mass of volatile substance. w1 3 Molar Mass of AgX
Weight 10 Patm ¥ VLiter 1 108
Sol. n = = = =
Molar Mass Molar Mass 0.0821 ¥ TKelvin 3 Molar Mass of AgX
10 g Æ 2.463 mL [At P = 1 atm and T = 300 K]
Molar Mass of AgX = 108 3
10 1 ¥ 2.463 ¥ 10-3
= \ Molar Mass of HX = [108 3 - 107]
Molar mass 0.0821 ¥ 300
\ molar mass = 105 g
Exercise
(c) Ratio of number of nitrogen atom to number of
level i oxygen atom is 3 : 4.
(d) Total number of atoms in one mole of (NH4)3PO4
1. Select the correct statement(s) for (NH4)3PO4. is 20.
(a) Ratio of number of oxygen atom to number of (a) ab (b) abc (c) bc (d) All
hydrogen atom is 1 : 3. 2. What volume (in mL) of liquid H2O2 has same number
(b) Ratio of number of cation to number of anion is of atoms as there are number of atoms in 22.4 mL H2O
3 : 1. gas at 2 atm and 546 K?
Mole Concept 1.13
[Given: Density of liquid H2O2 = 5.1 ¥ 10–3 g/mL; 14. X is molecular substance containing 21 atoms of car-
Density of liquid H2O = 1 g / mL] bon per molecule. The weight % of C in X is 50.4%.
(a) 2 (b) 5 (c) 3.5 (d) 4.2 What is the molecular weight of X in amu?
3. A sample of Mg3(PO4)2 contains 72 g Mg in the sam- (a) 500 (b) 200 (c) 300 (d) 400
ple. Calculate the number of g molecule of oxygen in 15. Calculate pressure (in atm) exerted by gas at 27°C,
the sample. which is produced by the complete decomposition of
(a) 2 (b) 3 (c) 3.5 (d) 4 162.5 g of FeCl3 in 0.0821 L container according to the
4. What mass (in gram) of Na2SO4 would contain the same following reaction: (Assume volume occupied by the
number of total ions as present in 930 g of Ca3(PO4)2? solid substances is negligible.)
(a) 710 (b) 800 (c) 200 (d) 500 FeCl3(s) æÆ FeCl2 (s) + Cl2 (g)
5. A sample of Cl contains 80% Cl35 and 20% Cl37 iso- (a) 250 (b) 150 (c) 15 (d) 300
topes. The average number of neutrons per atom is 16. A term ‘P’ is defined as
(a) 18.4 (b) 19.4 (c) 35.4 (d) 20.4 P = 294 ¥ (Ratio of masses of Al2 (SO4)3 and H2SO4 in
6. A sample of K2SO4. Al2(SO4)3. 24 H2O contains 6.4 kg g each containing 96 g of sulphur).
oxygen. Calculate mass of sulphur (in gram) in same Calculate P.
sample. (a) 342 (b) 294 (c) 684 (d) 171
(a) 1280 (b) 1000 (c) 128 (d) 12.8 17. Calculate molality(m) of pure water if its density is
7. A 448 L vessel contains O2(g) and CO2 (g) in 2 : 3 ratio 0.936 g/mL.
at 1 atm and 0°C. Calculate the number of moles of (a) 50 (b) 55.56 (c) 57.56 (d) 56.56
CO2 (g) present in the vessel. 18. The volume (in mL) of 0.5 M NaOH required for the
(a) 12 (b) 1.1 (c) 1.2 (d) 120 complete reaction with 150 mL of 1.5M H3PO3 solu-
8. Find the value of ‘x’, if hydrated salt A2SO4 . xH2O tion is
undergoes 45% loss in mass on heating and becomes (a) 1350 (b) 900 (c) 1250 (d) 1150
anhydrous (where atomic weight of ‘A’ is 7). 19. For the reaction,
(a) 8 (b) 9 (c) 10 (d) 5 AlCl3 + NaOH æÆ Al(OH)3 + NaCl
9. Calculate the volume of Cl2 gas (in mL) liberated at 1 if initially, 1 mole of each reactant is taken, then the
atm and 273 K when 1.74 g MnO2 reacts with 2.19 g number of moles of AlCl3 remaining after the comple-
HCl according to the following reaction with % yield tion of reaction is
40: 1
(a) 1 (b)
MnO2 + HCl æÆ MnCl2 + Cl2 + H2O 3
(a) 336 mL (b) 112 mL (c) 134.4 mL(d) 44.8 mL 2
(c) (d) None of these
10. Calculate the mass % of CaCO3 in the 103 g mixture 3
containing CaCO3 and Na2CO3, which produces 24 L 20. A mixture of CaCO3 and CaO on heating gives off
of CO2 at 1 atm and 300 K with excess of HCl. 22.4 L of CO2 gas at 273 K and 1 atm. If the same mass
[Given : R = 0.08 atm. lit / mol/ K] of mixture when treated with HCl required 219 g of
(a) 50 % (b) 48.5 % (c) 53 % (d) 40 % HCl for complete reaction, then the mole % of CaCO3
11. Calculate the mass of HCl (in g) produced if 2 g H2 is in the mixture is
mixed with 71 g Cl2. (a) 50% (b) 33.33%
H2 + Cl2 æÆ 2HCl (c) 25% (d) None of these
(a) 35.5 (b) 72 (c) 36.5 (d) 73 21. The relative density of a mixture of CO2 (g) and H2O (g)
12. Select the correct statement(s): w r.t. gaseous hydrogen atoms is 30. The molecular %
(a) Number of oxygen atoms are same in 1 g O2 and of the CO2 is
1 g O3. 600 2400
(a) (b) %
(b) 1 g molecule of any substance contains equal 13 13
number of atoms. 1200
(c) Reactant having minimum number of moles, acts (c) (d) None of these
13
as limiting reagent. 22. Molar mass of electron is nearly (NA = 6 ¥ 1023)
(d) During a chemical reaction total number of moles (a) 9.1 ¥ 10–31 kg mol–1 (b) 9.1 ¥ 10–31 g mol–1
may increase or constant. (c) 54.6 ¥ 10–8 g mol–1 (d) 54.6 ¥ 10–8 kg mol–1
13. Calculate the volume (in mL) of NO2 at 1 atm and 273 23. Calculate the number of moles of compound (KH-
K obtained by treating 12.7 g of Cu with excess of con- C2O4)0 95· H2C2O4 in its pure sample if sample contains
centrated nitric acid from the following reaction: 4 moles of oxygen atoms.
Cu(s) + HNO3 (aq) æÆ Cu(NO3)2 (aq) + H2O (l) + NO2
(a) 0.5 (b) 0.5 ¥ 0.95
(a) 8960 (b) 896 (c) 89.3 (d) 6900 4 4
(c) (d)
(4 + 0.95 ¥ 4) 0.95
24. What is the relationship between mole fraction of of a 32. One of the major uses of H2O2 is for artificial respira-
solute (XA) and its molality (m). If molar mass of sol- tion. It is stored in cylinder of 3 L capacity completely
vent is 100. (g/mol). filled with H2O2 solution of ‘44.8 V’. In a hospital, pa-
(X A) (X A) tient under artificial respiration takes 200 mL O2 per
(a) (b) min at 1 atm at 273 K for 2.8 hours from cylinder.
10 (1 - X A ) 100 (1 - X A )
[Assume volume of solution and rate of decomposition
10 (1 - X A ) 10 ( X A ) remain constant.]
(c) (d) Then which of the following statements is incorrect?
(X A) (1 - X A )
(a) Initial moles of H2O2 in a cylinder are 12.
25. 100 mL of 0.1 M ammonium phosphite solution is (b) Volume of oxygen used for respiration is 33.6 L.
mixed with 200 mL of 0.2 M sodium pyrophosphate (c) Volume strength of H2O2 left in solution is 11.2 V.
solution. Assuming complete dissociation of each salt (d) Volume strength of H2O2 left in solution is 33.6 V.
and no reaction occurs between the ions produced, cal- 33. Two gases N2 and H2 are allowed to react completely to
culate the concentration of total positive ions in mil- form mixture of N2H2(l) and N2H4 (g) leaving no reac-
limoles per litre.
tants. Formation of N2H2 (l) does not create any energy
(a) 600 (b) 200 (c) 500 (d) 60
change whereas formation of 1 mL N2H4 (g) absorbs 2 J
26. A mixture of C2H4, CO and N2 gases having total pres-
energy. Ratio of volume contraction to energy change
sure 250 mm of Hg in which 250 mm Hg of O2 is added
(in mL / Joule) when 30 mL N2 and 40 mL H2 react
at 27°C and then sparked. After the system is brought
to the original temperature, the total pressure becomes under similar conditions of temperature and pressure.
370 mm of Hg. If the partial pressure of CO2 is 200 mm (a) 3mL /J (b) 5mL /J
of Hg, then calculate the sum of initial pressure of CO (c) 6mL /J (d) None of these
and O2 in mm of Hg before the sparking 34. 150 mL mixture of CO and CO2 is passed through a
Given : At 27°C aqueous tension is 20 mm of Hg. tube containing excess of red hot charcoal. The volume
(a) 100 (b) 200 (c) 300 (d) 350 becomes 200 mL due to reaction.
27. Human lungs can absorb 8 g O2 per hour by respira- CO2 (g) + C(s) æÆ 2CO (g)
tion. If all oxygen atoms are converted to carbohy- Select the correct statement(s).
drates (C6H12O6), how long will it take to produce 180 (a) Mole percent of CO2 in the original mixture is 50.
g C6H12O6? (b) Mole fraction of CO in the original mixture is 0.56.
(a) 8 hr (b) 12 hr (c) 10 hr (d) 6 hr (c) Original mixture contains 50 mL of CO2.
28. If in a sample of oleum, mole fraction of SO3 is 0.5, (d) Original mixture contain 50 mL of CO.
label the oleum sample. 35. A mixture of formic acid and oxalic acid is heated in
(a) 109 % (b) 110.11 % the presence of H2SO4.
(c) 104.5 % (d) 114.22 HCOOH æÆ H2O + CO
29. Manganese oxide (MnO2) is heated in a stream of hy- H2C2O4 æÆ H2O + CO2 + CO
drogen to give water and new oxide MnxOy. If 17.4 g of
MnO2 produces 12.6 g of MnxOy then y : x will be The produced gaseous mixture is collected and cooled.
On its treatment with KOH solution, the volume of
1 3 5
(a) 1 (b) (c) (d) gaseous mixture decreases by one-tenth. Calculate the
2 2 2 molar ratio of the two acid in original mixture. [If the
30. A pure sample of an element ‘E’ is cut by knife into
simplest ratio is a : b then find a + b.]
perfect cubes. If 7.5 ¥ 1022 atoms are present in one
(a) 6 (b) 9 (c) 2 (d) 5
such cube and ‘a’ is edge length of cube in cm, then
36. In a tyre of a ‘ferrari’ car, a tube having a volume of
what will be the value of a6 (in cm6)?
12.3 L is filled with air at a pressure of 4 atm at 300
[Given : Atomic mass of E = 32, NA = 6 ¥ 1023, Density
K. Due to travelling, the temperature of the tube and
of element = 4/3 g/cm3 ]
air inside it is raised to 360 K. The porosity (number
(a) 9 (b) 4 (c) 16 (d) 25
of pores per unit area) of the tube material is 5 ¥ 105
31. Which of the following option(s) is incorrect?
pores/cm2 and each pore can transfer air from inside to
[Take H2O to be solvent in every case and solute is
outside of tube at the rate of 6.023 ¥ 108 molecules per
completely soluble]
minute. Due to above factors, pressure reduces to 3.6
(a) If mass fraction of CaBr2 and H2O are same then
atm in 20 min. Calculate the total surface area (m2) of
molality of CaBr2 is 5 m.
the tube, assuming volume of tube to be constant. (R =
(b) If equal moles of NaCl and H2O are taken then
0.082 lit-atm/mole-K)
molality of NaCl is 55.55 m.
(a) 5000 (b) 500 (c) 4000 (d) 400
(c) If in place of NaCl we use NaBr as solute in op-
37. Calculate the number of milligrams of SO2 in a sample
tion (2) then molality of NaCl changes.
of air, if in the following reaction 9 mL of 0.008 M
(d) If mole fraction of NaCl is same as that of H2O
KMnO4 solution is required for titration.
then molality of NaCl will be 55.55 m.
Mole Concept 1.15
SO2 + MnO4– æÆ SO4 –2 + Mn+2 47. Calculate the number of Na+ ion present in 142 amu of
(a) 11.52 mg (b) 0.18 mg Na2SO4 in aqueous solution.
(c) 0.072 mg (d) None of these (a) 5 (b) 2 (c) 1 (d) 4
38. Two acids H2SO4 and H3PO4 are neutralised separately 48. 1 mole of diatomic gas A2 contains 32 and 36 moles
by the same amount of base, producing sulphate and of electrons and neutrons respectively. Find the mass
dihydrogen phosphates respectively. The ratio of mass number of element A.
of H2SO4 and H3PO4 reacted with base respectively is (a) 32 (b) 68 (c) 40 (d) 34
(a) 1 : 1 (b) 2 : 1 49. Find the number of moles of Na3PO4 which contain as
(c) 1 : 2 (d) Data insufficient many ions as present in 6840 g of Al2(SO4)3.
39. Calculate mass % of oxygen in water (a) 20 (b) 25 (c) 30 (d) 60
(a) 88.88% (b) 73.68 % 19 39
50. An equimolar mixture of 9 F, 19 K and 32XA have
(c) 20.61% (d) 25.63 % average number of neutron of 25. Find average mass
40. 100 g ‘118% oleum’ sample is mixed with 9 g of H2O. number of mixture.
The final solution has (a) 22.5 (b) 21.5 (c) 45 (d) None
(a) mass % of H2SO4 is 2.7. 51. Find the correct option for 36 g C6H12O6.
(b) Mass % of combined SO3 is 16.3. (a) 4.8 NA molecules of C6H12O6
(c) New labelling as 108.25% oleum. (b) 19.2 NA electrons
(d) Mass % of free SO3 is 80. (c) 0.8 moles
M (d) 0.6 g molecules of oxygen
41. The two solutions of NaOH having molarity and 52. To obtain maximum mass of NO2 from a given mass of
M 10
are mixed to prepare 1 L of NaOH solution in such a mixture of NH3 and O2, the ratio of mass of NH3 to
30 O2 should be
a way that 300 mL of final solution is completely neu- 7
tralised by 10 mL of 0.5 M H3PO4 solution. Calculate 2NH3 + O2 æÆ 2NO2 + 3H2O
2
M 17 4
the volume (in mL) of NaOH solution used.
10 (a) (b)
40 7
[Assuming 100% dissociation]
17
(a) 250 mL (b) 350 mL (c) (d) None of these
(c) 50 mL (d) 500 mL 56
42. 1 mole of ammonium phosphite will contain 53. Find the mass (in g) of P4O10 produced if 31 g of phos-
(a) 2 moles of nitrogen atoms. phorus (P4) is mixed with 32 g of O2.
(b) 8 moles of hydrogen atoms. (a) 26.8 (b) 56.8 (c) 568 (d) 5.68
(c) 12 moles of hydrogen atoms. 54. If 200 mL of 0.1 M Na2SO4 is mixed with 100 mL of 0.2
(d) 6 moles of hydrogen atoms. M Na3PO4 solution, what is the molarity of Na+ in the
43. In a container 6 L N2 and 30 L H2 are taken which react final solution, if final solution has a density of 1.2 g/mL.
according to the following reactions and N2H2 reacts (a) 0.196 M (b) 0.33 M
with H2 to give N2H4. (c) 1.5 M (d) 0 .66 M
55. Mark the option containing temperature-independent
N2(g) + H2(g) æÆ N2H2(g)
concentration terms.
N2H2(g) + H2(g) æÆ N2H4(l)
(I) ppm
Find percentage of volume contracted. (II) %w/w
(a) 50 (b) 40 (c) 30 (d) 60 (III) Volume strength of H2O2
44. Find the total number of carbon atom present in one (IV) % labelling (V) %w/v
molecule, if 0.078 g hydrocarbon having simplest for- (a) All except V (b) I, II, IV
mula unit CH, occupy 22.4 mL of volume at 1 atm and (c) I, II only (d) Only II
0°C.
56. Total number of electrons present in 818O–2 is 1.2 ¥ 1022
(a) 5 (b) 4 (c) 2 (d) 6
then the number of moles of oxide ion present is
45. Find the % mass of Ca in 10 g of pure CaCO3. (a) 2 ¥ 10–3 mole (b) 10–3 mole
(a) 40 (b) 30 (c) 60 (d) 50 (c) 10 mole (d) 0.02 mole
46. Find volume occupied by 1 molecule of CH3CH2OCH3 57. Ratio of number of protons to neutrons in 3.011 ¥ 1022
having density of 0.8 g/cm3. molecules of D3O+ is
[Given : NA = 6 ¥ 1023] (a) 2 (b) 1 (c) 4 (d) 3
(a) 1.25 ¥ 10–22 cm3 (b) 2.25 ¥ 10–22 cm3 58. 80 g of SOx gas occupies 14 L at 2 atm and 273 K. The
(c) 3.25 ¥ 10–22 cm3 (d) 1.00 ¥ 10–22 cm3 value of x is
(Use R = 0.0821L-atm/K-mole)
(a) 3 (b) 2 (c) 1 (d) None
59. Haemoglobin contains 0.25% iron by mass. The mo- 71. If one million atoms of silver weight is 1.79 ¥ 10–16 g,
lecular mass of haemoglobin is 89600 then the number the gram atomic mass of silver is
of iron atoms per molecule of haemoglobin (Atomic (a) 107 g (b) 107.2 g
mass of Fe = 56) is (c) 107.8 g (d) 108.2 g
(a) 8 (b) 4 (c) 12 (d) 160 72. How many g-atoms are present in 1.4 g of Nitrogen?
60. 12 g of mg was burnt in a closed vessel containing 32 g (a) 1 (b) 0.1 (c) 0.01 (d) 0.5
oxygen. Which of the following statements is not cor- 73. On heating a given mass of blue vitrol 95.7 g, anhy-
rect? drous copper sulphate is obtained. The number of water
(a) 2 g of mg will be left unburnt. molecules lost are
(b) 0.75 gram-molecule of O2 will be left unreacted. (a) 3 (b) 5
(c) 20 g of MgO will be formed. (c) 18.06 ¥ 1023 (d) 30.10 ¥ 1023
(d) The mixture at the end will weight 44 g. 74. The amount of zinc needed to produce 112 mL of H2 at
61. Calculate maximum mass of CaCl2 produced when STP on reaction with dil H2SO4 will be
2.4 ¥ 1024 atoms of calcium is taken with 96 L of Cl2 (a) 0.65 g (b) 0.325 g
gas at 380 mm pressure and at 27ºC. (c) 6.5 g (d) 3.25 g
[R : 0.08 atm L/mole-K and NA = 6 ¥ 1023] 75. Calculate the number of electrons present in 18 mL of
(a) 111 g (b) 444 g H2O at 25ºC.
(c) 61 g (d) 222 g
(a) 6.023 ¥ 1023
62. A mixture containing 3 moles each of C4H8 and C6H6
(b) 6.023 ¥ 1024
undergoes complete combustion with O2 to form CO2
180
and H2O. Calculate the total mass of CO2 produced. (c) ¥ 6.023 ¥ 1023
(a) 1320 g (b) 610 g 22400
(c) 528 g (d) 792 g 180
(d) ¥ 6.023 ¥ 1023
63. An impure sample of KClO3 of 50% purity on decom- 22.4
position produces 67.2 L of oxygen at 0ºC and 1 atm. 76. Experimentally it is found that a metal oxide has for-
The other product of decomposition is KCl. The initial mula M0 98O1. Metal M is present as M+2 and M+3 in its
mass of impure original sample (in gram) taken is oxide. Fraction of metal which exist as M+3 would be
(a) 245 (b) 122.5 (a) 7.01% (b) 4.08%
(c) 490 (d) None of these (c) 6.05% (d) 5.08%
64. A cylinder of compressed gas contains nitrogen and 77. The ratio of masses of O2 and N2 in a particular gaseous
oxygen gas in the mole ratio 3 : 1. If the cylinder is mixture is 1 : 4. The ratio of number of their molecules
known to contain 2.40 g of oxygen, what is the total is
mass of gas mixture? (a) 1 : 8 (b) 3 : 16 (c) 1 : 4 (d) 7 : 32
(a) 8.7 g (b) 7.2 g (c) 6.8 g (d) 6.3 g 78. A solution of H2O2 is labelled as 11.2 V. If the density of
65. If in urea [CO(NH2)2] there are 20 g – atoms of nitro- solution is 1.034 g/mL then identity the correct option.
gen present then the mass of urea will be (a) Molarity of solution = 2M
(a) 600 g (b) 60 g 1
(c) 6 g (d) 120 g (b) Molality of solution =
1.034
66. The weight of 2.8 liter of gas at NTP is 3.50 g. Its va- w 3400
pour density is (c) % =
w 1034
(a) 14 (b) 28 (c) 32 (d) 20
w 34
67. If nickel oxide has the formula Ni0 98 O1 00, then what (d) % =
fraction of nickel exist as Ni+3? v 1000
(a) 96% (b) 4% (c) 98% (d) 2% 79. A gaseous mixture of CO and CO2 having total volume
68. Find the number of iodine atoms present in 40 mL of its 150 mL is passed through a tube containing excess of
0.1 M solution. red hot charcoal to cause the following reaction:
(a) 48.1 ¥ 1020 (b) 4.81 ¥ 1020 CO2(g) + C(s) æÆ 2CO(g)
23
(c) 6.02 ¥ 10 (d) None of these The volume increases to 250 mL. Identify the correct
69. Assuming complete ionisation, the pH of 0.1 M HCl is statement.
1. The molarity of H2SO4 with same pH is (a) Original mixture contains 50% by moles CO.
(a) 0.1 (b) 0.2 (c) 0.05 (d) 2 (b) Original mixture contains 33.33% by moles CO.
70. The mole fraction of solute in one molal aqueous solu- (c) Original mixture contains 33.33% by moles CO2.
tion is (d) Mole fraction of CO2 in the original mixture is 0.4.
(a) 0.009 (b) 0.018 (c) 0.027 (d) 0
Mole Concept 1.17
80. Hydrogen gas is prepared in the laboratory by reacting 6. An ore of iron contains FeS and some non-volatile im-
dilute HCl granulated zinc. Following reaction takes purity. On roasting this ore converts all FeS into Fe2O3
place: and 8% loss in weight was observed. Calculate mass
Zn + 2HCl æÆ ZnCl2 + H2 percentage of FeS in ore?
Calculate the volume of H2 evolved at STP when 130.6 FeS + O2 Æ Fe2O3 + SO2
g of zinc reacts with HCl. (a) 20 (b) 60 (c) 88 (d) 44
[Atomic mass of Zn = 65.3] 7. For the reaction,
(a) 22.4 L (b) 44.8 L 7 A + 13 B + 15 C Æ 17 P
(c) 11.35 L (d) 68.1 L if 15 moles of A, 26 moles of B and 30.5 moles of C are
81. For a mixture of KCl and KNO3 which of the following taken initially then limiting reactant is
is possible percentage of K by mass? (a) A (b) B
(a) 10% (b) 45% (c) 70% (d) 90% (c) C (d) None of these
82. In 200 mL of aqueous HCl solution, excess of MnO2 is 8. The number of moles of KOH required for complete
added. If the liberated gas occupies 164.2 mL at 127ºC neutralisation of H2SO4 produced from dissolution of
and 38 cm-Hg, then the molarity of HCl solution is 500 g of 118% oleum in water is nearly
(R = 0.0821 L atm/K mol) (a) 12 (b) 10 (c) 13 (d) 15
90%
MnO2(s) + 4HCl(aq) æÆ 9. Zn + O2 æææ Æ ZnO ... (i)
MnCl2(aq) + Cl2(g) + 2H2O(l) ZnO + H2O Æ Zn(OH)2 ... (ii)
(a) 0.1 M (b) 0.2 M If on taking 130 g of Zn with 100 g of O2 and 50 g of
(c) 0.4 M (d) 0.05 M H2O afterwards 178.2 g Zn(OH)2 is obtained, calculate
the % yield of second reaction.
[Take Zn = 65]
level ii (a) 100 (b) 75 (c) 10 (d) 80
10. A mixture of C2H4, CO and N2 gases having total pres-
1. Select the correct option for increasing order of number sure 250 mm of Hg in which 250 mm Hg of O2 is added
of atoms. at 27°C and then sparked. After the system was brought
(I) 2 g of hydrogen (II) 16 g of sulphur to the original temperature, the total pressure becomes
(III) 4 g of oxygen (IV) 31 g of phosphorus 370 mm of Hg. If the partial pressure of CO2 is 200 mm
(a) II > III > IV > I (b) IV > II > III > I of Hg, then calculate the initial partial pressure of C2H4
(c) I > IV > II > III (d) I = IV > II > III (in mm of Hg)
2. Two elements C and D combine to form two com- [Given : At 27°C aqueous tension is 20 mm of Hg.]
pounds; CxDy and CyDx. 0.5 mole of CyDx weigh 40 g (a) 40 (b) 50 (c) 60 (d) 75
and 1 molecule of CxDy weigh 1.66 ¥ 10–25 kg. The 11. A mixture of C2H4, CO and N2 gases having total pres-
atomic weight of C and D are 20 and 40 respectively. sure 250 mm of Hg in which 250 mm Hg of O2 is added
What are ‘x’ and ‘y’? at 27°C and then sparked. After the system was brought
(a) 3, 2 (b) 1, 3 (c) 1, 2 (d) 2, 2 to the original temperature the total pressure becomes
3. To form one molecule of Mg3N2, the total number of 370 mm of Hg. If the partial pressure of CO2 is 200 mm
electron transferred from metal to non–metal is of Hg, then calculate total O2 consumed in mm of Hg.
(a) 6 NA (b) 3 NA (c) 3 (d) 6 [Given: At 27°C aqueous tension is 20 mm of Hg.]
4. A gaseous mixture contains SO3 (g) and CH4(g) in 5 : 1 (a) 150 (b) 170 (c) 200 (d) 220
ratio by mass. Calculate Q 12. To a 100 g an oleum sample labelled as ‘118% oleum’,
where Q = 200 ¥ ratio of total number of atoms present 9 g of water is added. Select the correct option(s).
in SO3(g) to total number of atoms present in CH4(g). (a) It contains only H2SO4 , SO3 and SO2.
(a) 160 (b) 16 (c) 320 (d) 32 (b) It contains H2SO4, SO3 and H2O.
5. Select the correct statement(s) for the following reac- (c) New solution will have labelling 109 %.
tion: (d) % w/w of SO3 is nearly 36.7 %.
2 A(s) + B(g) Æ 3 C (g) + 4 D (l) 13. Acid sample is prepared using HCl, H2SO4, H2SO3 and
(a) 2 moles of A always produce 3 moles of C and 4 H3PO4 separately or as a mixture of any two or more.
moles of D Calculate the minimum volume of 4% w/v NaOH add-
(b) 22.4 l of B (g) produces 3 moles of C at 1 atm and ed (in mL) to 294 g sample, in order to ensure complete
273 K in excess of A. neutralisation in every possible case.
(c) B will always remain in excess because volume of (a) 9000 (b) 6000 (c) 4000 (d) 900
gas is very high than solid. 14. 30 mL gaseous mixture of methane and ethylene in vol-
(d) Moles of D produced is always less than C be- ume ratio X : Y requires 350 mL air, containing 20%
cause volume of liquid is less than gas. of O2 by volume for complete combustion. If ratio of
methane and ethylene is changed to Y : X, what will be mL of 0.2 M KMnO4 solution under acidic conditions.
the volume of air (in mL) required for complete reac- Calculate the volume strength of the diluted H2O2 solu-
tion under similar condition of temperature and pres- tion.
sure? (a) 28 V (b) 14 V (c) 32 V (d) 16.8 V
(a) 400 (b) 200 (c) 300 (d) 800 20. The number of oxygen atoms present in 24.5 g of
15. The Haber’s process for preparing ammonia involves H3PO4 is equal to
direct conversion of hydrogen and nitrogen gases into (a) Number of electrons present in 1.6 g methane
NH3 at high temperature and pressure using a catalyst (CH4).
N2(g) + 3H2(g) Æ 2NH3(g) (b) Number of molecule of CO2 present in 11.2 L at 1
atm and 546 K.
If air [consider it to contain 80% N2, 20% O2 by vol-
(c) Number of moles of proton present in NA gram-at-
ume] is used as source for nitrogen, O2 present in the air
om of Hydrogen.
will oxidise NH3 to NO as per the following reaction:
(d) Number of total atoms present in 4/3 mol of CO2.
4NH3 (g) + 5O2 (g) Æ 4NO (g) + 6H2O (g) (a) a, c and d (b) a and c
Air and H2 are taken in equal volumes in the begin- (c) Only c (d) a and b
ning. Assume that both above reactions get completed 21. 25 mL of a solution containing HCl and H2SO4 re-
and no other reaction is taking place. Select the correct quired 10 mL of 1M NaOH solution for complete neu-
statement(s). tralisation. 20 mL of the same acid mixture on being
(a) O2 is completely exhausted. treated with excess of AgNO3 gives 0.1435 g of AgCl.
(b) H2 is not completely exhausted. If molarity of HCl is ‘x’ and that of H2SO4 is ‘y’
(c) N2 is completely exhausted. (x + y) will be
(a) 0.225 (b) 0 .125 (c) 1.25 (d) 0.05
(d) NH3 is completely exhausted.
22. Consider the given reaction.
16. Calcium phosphide Ca3P2 formed by reacting magne- H4P2O7 + 2NaOH Æ Na2H2P2O7 + 2H2O
sium with excess calcium orthophosphate Ca3(PO4)2, If 534 g of H4P2O7 is reacted with 30 ¥ 1023 molecules
was hydrolysed by excess water. The evolved phos- of NaOH then total number of molecules produced in
phine PH3 was burnt in air to yield phosphrous pentox- the product is
ide (P2O5). How many grams of magnesium metaphos- (a) 2.5 ¥ NA (b) 5 ¥ NA
phate would be obtained if 192 gram Mg were used? (c) 7.5 ¥ NA (d) 75 ¥ NA
(Atomic weight of Mg = 24, P = 31) 23. The phosphorus pentaoxide used to produce phos-
Ca3(PO4)2 + Mg Æ Ca3P2 + MgO phoric acid for cola soft drinks is prepared by burning
Ca3P2 + H2O Æ Ca(OH)2 + PH3 phosphorus in oxygen. What is the % yield if 10 g of
PH3 + O2 Æ P2O5 + H2O P4O10 is isolated from the reaction P4 + 5O2 Æ P4O10.
MgO + P2O5 Æ Mg(PO3)2 Initially 0.2 mole of each P4 and O2 each are taken.
(a) 11.52 g (b) 182 g (a) 88.13 % (b) 98.1 %
(c) 18.2 g (d) 24 (c) 68.1 % (d) 95. 1%
17. A solution contains substances A and B in H2O (sol- 24. Automotive air bags are inflated when a sample of so-
vent). The mole fraction of ‘A’ is 0.05 and molarity of dium azide (NaN3) is rapidly decomposed [2NaN3(s)
‘B’ is 7 M. The solution has a density of 1.14 g/mL. Æ 2Na(s) + 3N2(g)]. What mass of sodium azide is
Calculate molarity of ‘A’. required to produce 368 L of N2(g) with density 1.12
[Molecular weight of A = 10 g/mol; molecular weight g/L?
of B = 30 g/mol] (a) 0.638 kg (b) 1.2 kg
(a) 2 M (b) 3 M (c) 1.5 kg (d) 5 kg
(c) 0.5 M (d) None of these 25. A mixture of AgCl and AgBr undergoes a loss in weight
18. If 200 mL of 0.1 M Na2SO4 is mixed with 100 mL of by 8.9% when exposed to excess chlorination. The %
0.2 M Na3PO4 solution. Find molarity of Na+ in the by mass of AgCl in the original mixture is
final solution, if final solution has density 1.2 g/mL. (a) 37.6% (b) 17.8%
(a) 0.196 M (b) 0.33 M (c) 62.4% (d) 82.2%
(c) 0.5 M (d) None of these 26. Which of the following options does not represent con-
19. A solution of H2O2, labelled as ‘32V’, was left open. centration of semi-molal aqueous solution of NaOH
Due to this, some H2O2 decomposed and the volume having dsolution = 1.02 g/mL?
strength of the solution decreased. To determine the 1 9
(a) Molarity = M (b) XNaOH =
volume strength of the remaining H2O2 solution, 10 mL 2 1009
of this solution was taken and it was diluted to 100 mL. (c) % w/w = 10% (d) % w/v = 2%
10 mL of this diluted solution was titrated against 25
Mole Concept 1.19
27. Statement 1: During the reaction: N2(g) + 2H2(g) Æ The volume change is given by
N2H4(l) volume contraction takes place. (a) 0 mL (b) 30 mL (c) 5 mL (d) 10 mL
Statement 2: Volume contraction always takes place 34. 112.0 mL of gaseous NO2 at 1 atm and 273 K was liq-
when one of the product is in liquid state. uefied, the density of the liquid being 1.15 g/mL. Cal-
(a) Statements 1 and 2 are true. Statement 2 is the culate the volume of and the number of molecules in
correct explanation for statement 1. the liquid NO2.
(b) Statements 1 and 2 are true. Statement 2 is NOT (a) 0.10 mL and 3.01 ¥ 1022
the correct explanation for statement 1. (b) 0.20 mL and 3.01 ¥ 1021
(c) Statement 1 is true, statement 2 is false. (c) 0.20 mL and 6.02 ¥ 1023
(d) Statement 1 is false, statement 2 is true. (d) 0.40 mL and 6.02 ¥ 1021
28. Statement 1: For a very dilute solution, molality and 35. Adipic acid HOOC–(CH2)4 COOH is used in making
molarity are always approximately equal nylon. Calculate the weight of hydrogen atom present
Statement 2: Mass of solution is always approximate- in 58.4 g of adipic acid.
ly equal to mass of solvent for a very dilute solution. (a) 4 g (b) 8 g (c) 40 g (d) 0.4 g
(a) Statements 1 and 2 are true. Statement 2 is the 36. A gaseous mixture contains SO3 (g) and C2H6 (g) in
correct explanation for statement 1. a 16 : 15 ratio by mass. The ratio of total number of
(b) Statements 1 and 2 are true. Statement 2 is NOT atoms present in C2H6(g) and SO3 (g) is
the correct explanation for statement 1. (a) 2 : 5 (b) 1 : 5 (c) 5 : 1 (d) 5 : 2
(c) Statement 1 is false, statement 2 is true. 37. What amount of heat (in kJ) is released during forma-
(d) Statement 1 is true, statement 2 is false. tion of 31.2 g AsH3 by the following reaction?
29. Statement 1: As temperature increases, molality of so- [Given: Atomic weight As = 75, H = 1
lution decreases. 2As (s) + 3H2 (g) Æ 2 AsH3; DH = –770 kJ]
Statement 2: Molality of a solution is dependent on (a) 250 (b) 350 (c) 154 (d) 35
the mass of solute and solvent. 38. 5 mole of N2 gas is added in a vessel at 1 atm and 300 K.
(a) Statements 1 and 2 are true. Statement 2 is the Find the change in volume (in litre) of gas when 2 mole
correct explanation for statement 1. of He gas is added in it at same temperature and new
(b) Statements 1 and 2 are true. Statement 2 is NOT pressure of 1.05 atm.
the correct explanation for statement 1. [Given: R = 0.08 atm L]
(c) Statement 1 is true, statement 2 is false. (a) 240 L (b) 40 L
(d) Statement 1 is false, statement 2 is true. (c) 100 L (d) 54 L
30. SO3 can be produced by the following two reactions: 39. 1 atom of X, 2 atoms of Y and 3 atoms of Z combine
S8 + O2(g) Æ SO2(g) together to give a molecule XY2Z3. Now we take 10 g
SO2(g) + O2(g) Æ SO3(g) of X and 2 ¥ 1023 atoms of Y and 0.06 moles of Z in a
How many moles of S8 are required to produce 20 mole container, to give 5.6 g of XY2Z3. What is the molar
of SO3? mass of Z.
[Given: MX = 60 g/mol MY = 80 g/mol]
5 5
(a) mole (b) mole (a) 25 (b) 24 (c) 32 (d) 20
2 4 40. Hydrogen sulphide reacts with chloric acid in an aqueous
(c) 10 mole (d) 5 mole solution liberating chlorine by the following reaction:
31. When CH4(g) is burnt in oxygen, it forms carbon H2S + HClO3 Æ Cl2 + H2SO4 + H2O
dioxide and water. If 16 g of methane is mixed with In an experiment, 40 mL of solution of chloric acid was
6.022 ¥ 1024 molecules of oxygen at 1 atm, 300 K allowed to react with sufficient amount of H2S.
maximum volume of water that can be produced can be Cl2 formed were reduced by 20 mL H2O2 by the fol-
[Given : R = 0.0821 L-atm/mole K, d H2O(l ) = 1 g/mL] lowing reaction:
(a) 49.26 L (b) 44.8 L (c) 90 mL (d) 36 mL H2O2 + Cl2 Æ HCl + O2≠
32. Percentage loss in mass heating mixture of Na2CO3 In the above reaction, 896 mL of O2 was evolved at 1
and CaCO3 containing equal masses of Na2CO3 and atm and 273 K.
CaCO3 is Which of the following option is incorrect for afore-
(a) 44% (b) 25% (c) 22% (d) 50% mentioned experiment?
33. To an Eudiometry tube 10 mL of P, 30 mL of Q, 20 mL (a) Normality of H2O2 solution used is 4 N.
of R and 15 mL of S are added and subjected to spark- (b) Molarity of original HClO3 solution used is 2 M.
ing to cause the following reactions: (c) Equivalents of H2S reacted with HClO3 is 0.05.
2P(g) + 3Q(g) Æ 2A(g) + B(l) (d) Moles of Cl2 produced is 0.04.
R(g) + 2S(g) Æ 3A(g) + 2C(g)
Stage 1: The water sample is treated with excess of Mn2+ (aq)

level iii solution along with a base to cause the following reaction:
Mn2+ (aq) + 2OH– (aq) Æ Mn(OH)2 (s) …(i)
Paragraph for Q. Nos. 1 to 3
24 g pure sample of magnesium is burned in air to form mag- The precipitate then reacts with dissolved oxygen as shown
nesium oxide and magnesium nitride. When products are below.
treated with excess of H2O, 3.4 g of gaseous NH3 is generated 1
according to given reactions. 2Mn(OH)2 (s) + O2(aq) + H2O(l) Æ 2Mn(OH)3 (s) …(ii)
2
Mg + O2 Æ MgO
Mg + N2 Æ Mg3N2 Stage 2: The solution is added with excess of acidified solu-
tion of KI to cause the following reaction:
Mg3N2 + 6H2O Æ 3Mg (OH)2 + 2NH3
1. Calculate the amount of magnesium oxide (in g) in 2Mn(OH)3 (s) + 2KI + 3H2SO4
products. Æ 2MnSO4 + K2SO4 + I2(aq) + 6H2O …(iii)
(a) 28 (b) 20 (c) 16.8 (d) 32 Stage 3: The I2 produced is calculated by the following reac-
2. Calculate the amount of Mg(OH)2 (in g) produced in tion by calculating the amount of Na2S2O3 consumed.
the above reaction.
(a) 11.6 (b) 17.4 (c) 23.2 (d) 15.8 I2 + 2Na2S2O3 Æ 2NaI + Na2S4O6 …(iv)
3. Calculate the mass % of Mg converted into Mg3N2. Using the above information answer the following questions:
(a) 20 (b) 30 (c) 35 (d) 40 8. If 1 L of water sample is taken then calculate the maxi-
mum volume of 0.01 M Na2S2O3 solution required if
Paragraph for Q. Nos. 4 to 5
the sample is considered ‘heavily polluted’.
12 mL gaseous mixture of an alkane and an alkene (contain-
ing same number of carbon atoms) require exactly 285 mL of (a) 80 mL (b) 80 L (c) 120 mL (d) 120 L
air (containing 20% v/v O2 and rest N2) for complete com- 9. If 1 L of water sample is taken then calculate maxi-
bustion at 200 K. After combustion when gaseous mixture is mum volume of 0.1 M Na2S2O3 solution required if the
passed through KOH solution it shows volume contraction sample is considered ‘optimum fit’ for aquatic life.
of 36 mL. (a) 8 mL (b) 80 mL (c) 12 mL (d) 120 mL
4. Formula of alkane is 10. Which of the following statements is correct w.r.t.
(a) C5H12 (b) C3H8 above method?
(c) C2H6 (d) C4H10 (a) Greater the amount of dissolved oxygen, lesser
5. Mole fraction of CO2 in final gaseous sample is will be moles of Na2S2O3 required.
6 6 6 6 (b) Excess solution in Stage 1 ensure all dissolved
(a) (b) (c) (d) oxygen reacts.
51 44 45 13 (c) Moles of Mn(OH)2(s) reacted and moles of
Paragraph for Q. Nos. 6 to 7 Mn(OH)3 formed will be different.
1292.5 g of aquesous solution of ‘5 m’ NaCl is kept in a (d) 1 mole of dissolved oxygen will require 2 moles
large bucket. The bucket is placed under a tap from which of Na2S2O3 for estimation.
‘2 m’ aqueous solution of NaCl is flowing. Rate of flow of
solution from tap is 0.5 g/sec. (One or more than one correct type)
6. The total amount of solution (in g) finally present in 11. Which of the following solutions will be definitely
bucket when solution present in bucket have concentra- basic?
tion of NaCl 4 m is (a) 400 mL of 0.1 M NaOH is mixed with 100 mL of
(a) 558.5 (b) 1851 0.4 M CH3COOH.
(c) 1351 (d) 1938.75 (b) Equal volumes of same % w/v of NaOH and
7. The time (in seconds) after which the bucket will have H2SO4 solutions are mixed.
‘4m’ concentration of NaCl. (c) Different volumes of 0.2 M NaOH and 0.1 M HCl
(a) 117 (b) 2000 (c) 1117 (d) 1292.5 solutions are mixed.
Paragraph for Q. Nos. 8 to 10 (d) Equal masses of same % w/w NaOH and HCl so-
Analysis of dissolved oxygen in river water is very essential lutions are mixed.
to ensure that aquatic life is safe. As per European standards, 12. In the formation reaction of NH3 from N2 and H2, 140
dissolved oxygen should never be less than 6.4 mg/L and g of N2 and 40 g H2 were mixed. Select the option(s)
preferably should be greater than 9.6 mg/lit. A water body which is are not correct.
having value less than 6.4 mg/L is considered ‘heavily pol- (a) Maximum mass of NH3 which can be formed is
luted’ and a water body having value greater than 9.6 mg/L 180 g.
is considered optimum fit for aquatic life. One method to (b) If % yield of reaction is 80%, then H2 consumed
measure dissolved oxygen is through Winkler titration. The will be 32 g.
method involves three stages:
Mole Concept 1.21
(c) Some N2 (g) will be left after the reaction. 18. For the following reactions:
(d) If NH3 formed is 85 g then % yield will be 50%. I. (NH4)2SO4+2NaOH æææ
40 %
Æ Na2SO4+2H2O+
13. 500 g of 109% labelled oleum is taken. Which of the 2NH3
following statement(s) is/are correct regarding this ole- 80%
II. NH3 + HCl æææ Æ NH4Cl
um sample?
If 4 g of NaOH is taken then
(a) The maximum mass of H2SO4 which may be ob-
(a) produced moles of NH4Cl (in IInd reaction) are 1.6
tained from the sample is 509 g.
times of produced moles of Na2SO4 (in reaction I).
(b) When 100 g water is added in it, the sample fi- (b) reacting moles of HCl (in reaction II) is 20 %
nally contains 545 g H2SO4 and 55 g water. lesser than original (NH4)2SO4 moles.
(c) When 100 L water is added in it, the approxi-
(c) reacting moles of HCl (in reaction II) is lesser
mate molarity of H2SO4 solution obtained will be
than reacting moles NaOH (in reaction I).
0.056M.
(d) produced mass of NH4Cl is 2.71 g.
(d) When 20 g water is added to it, the sample finally
contains 520 g pure H2SO4. 19. Choose incorrect options.
(a) 2 25 ¥ 10–22g of Ca(OH)2 containing 32 amu of O.
14. When taken in an Eudiometer tube operating at room
(b) If one atom of an element weighs 1.8 ¥ 10–22 g,
temperature and pressure and subjected to complete
then its atomic mass is 108.36.
reaction, in which of the following options the contrac- (c) 10 g of CaCO3 contains 0.3 g atom of oxygen.
tion in volume is greater than or equal to 30% of origi- (d) Number of atoms in 2 moles of S8 is greater than
nal volume. 5.5 moles of SO2.
(a) CO(g) and O2(g) taken in a molar ratio of 2 : 1. 20. Which of the following is/are correct?
(b) 10 mL of CH4(g) and 30 mL of O2(g). (a) The density of a gas depends upon pressure and
(c) N2(g) and H2(g) taken in a molar ratio of 3 : 1. temperature.
(d) N2 and H2 taken in a molar ratio of 1 : 3 (b) The relative density of a gas depends upon pres-
15. Which of the following is/are correct statement(s)? sure and temperature.
(a) For the production of equimolar mixture of CO (c) The vapour density of a gas depends upon pres-
and CO2 gases, 12 g carbon must be burnt with sure and temperature.
24 g oxygen (assuming 100% yield of reactions). (d) The relative density of SO3 with respect to oxy-
(b) Molarity of any aqueous solution will be equal to gen is 2.5 at 1 atm and 273 K.
21. A mixture of H2 and O2 having total volume 55 mL is
its molality if the volume of solution (in mL) and
sparked in an eudiometry tube and contraction of 45
the mass of solvent (in gram) are numerically same.
mL is observed after cooling. What can be the compo-
(c) Gases behave ideally in the conditions of their
sition of reacting mixture?
very low molar volumes and force of attraction (a) 30 mL H2 and 25 mL O2
between them. (b) 10 mL H2 and 45 mL O2
(d) all of the above. (c) 40 mL H2 and 15 mL O2
16. A gaseous organic compound CxH2yOy (M = 150) was (d) 35 mL H2 and 20 mL O2
burnt with four times the amount of O2 gas as required 22. Which of the following is/are incorrect statement(s)?
for complete combustion. The resulting gases when (a) Vapour density of gaseous mixture decreases
cooled to 1 atm pressure and 300 K were found to oc- during the progress of
cupy (4.926) L along with 0.9 g of water. Identify the H2(g) + Cl2(g) Æ 2HCl(g) reaction.
correct option(s). (b) 22.4 L of H2O at 1 atm and 273 K contains
(a) If 10 mL of organic compounds is taken then oxy- 6.02 ¥ 1023 molecules of H2O.
gen taken should be 200 mL. (c) 10 g of 104.5 % labelling oleum sample contains
2 2 g of free SO3.
(b) Fraction of O by number in the compound is .
(c) The compound should be C4H6O3. 3 (d) Volume of solution is always equal to the sum of
(d) Percent of H by mass in the compound will be volume of solute and solvent.
100 23. Choose the correct statement(s).
%. (a) The mole is the amount of substance containing
15
the same number of chemical units as there are
17. The sample(s) containing same number of ‘Na’ atom as atoms in exactly 12 g of 12C.
there are ‘Na’ atoms in 5.3 g of Na2CO3, is/are (b) Avoggadro’s number is the number of units in a
(a) 4 g of NaOH mole.
(b) 5.85 g of NaCl (c) The weight of one gram-atom of an element
(c) 0.25 mole of Na2SO4 means its atomic weight in g.
(d) 5.6 g of Na3PO4 (d) One g-atom of each element contains the same
number of atoms.
24. Select the incorrect statement(s). Column I Column II

(a) Mass of 6.022 ¥ 1025 molecule of SO3 is 8 kg.
(A) 1 mole of O2 (P) occupies 22.4 L at 1 atm
(b) Number of oxygen atoms in 4.8 g of O3 are 18.06
and 0°C
¥ 1023.
(c) Mass of 22.7 mL of C2H6 at 1 bar pressure and (B) 1 mole of SO2 (Q) weighs 32 g
273 K is 30 g. (C) 4 g of He (R) collection of NA smallest
(d) Volume of 51 mg of NH3 at 1 bar pressure and existing independent spe-
273 K is 68.1 l. cies
25. Choose the incorrect option(s). (D) 1 g of H2 (S) occupies 12.3 L at 1 atm
(a) 2.25 ¥ 10-22 g of Ca(OH)2 containing 32 amu of O. and 300 k
(b) One atom of an element weighs 1.8 ¥ 10–22 g, then
its atomic mass is 108.36. 29. Match the expressions/statements Column–I with ex-
(c) 10 g of CaCO3 contains 1 g atom of C. pressions/Statements in Column–II.
(d) Number of atoms in 2 moles of S8 is greater than Column I Column II
5.5 moles of SO2. Atomic masses % composition of
26. Identify the incorrect statement(s). Isotope-I, Isotope-II, heavier isotope
(a) Molarity of very dilute solution with CCl4 as Avg
solvent is greater than its molality if density of (A) (z – 1), (z + 2), z (P) 33.33 % by moles
CCl4 is 1.6 g/cm3. (B) (z + 1), (z + 3), (z + 2) (Q) 50 % by moles
196 (C) z, 3z, 2z (R) % by mass depen-
(b) An oleum with labelling ¥ 100 will have
178 dent on z
160
mass % combined SO3 equal to ¥ 100% . (D) (z –1), (z + 1), z (S) 75 % by mass
178
(c) The value of universal gas constant is (0.0821 ¥ 30. Match the expressions/statements in Column I with
0.76) in mm of Hg – m3/mole Kelvin. expressions/Statements in Column II.
(d) For an all gaseous reaction if volume changes
Column I Column II
during reaction at constant temperature and pres-
sure then vapour density may remain constant. (A) 1.0 g-ion of Na+ (P) 6.02 ¥ 1024 electron
(B) 23.0 g of Na (Q) 7.224 ¥ 1024 neutron
(Column matching)
(C) 1.0 g-ion of Mg+2 (R) 6.02 ¥ 1023 ¥ 2 ¥ 1.6 ¥
27. A2 reacts with B2 in either of the following ways 10–19 columb charge
depending upon supply of B2: (D) 24 g of Mg (S) 7.224 ¥ 1024 proton
A2 + B2 Æ 2AB
A2 + 3B2 Æ 2AB3 31. Match the expressions/statements in Column I with
Also, the products formed may also react with appro- expressions/Statements in Column II.
priate reactant remaining to form other product. Using
Column I Column II
this information, match composition of the final mix-
ture for initial amount of reactants. (A) 0.5 mol of CO2(g) (P) Occupy 11.2 L at 1 atm
and 273 K
Column I Column II
(B) 2 g of helium (g) (Q) mass = 24 g
(Initial reactants) (Final Products)
(C) 0.5 g molecule of (R) total number of atoms
(A) 4 moles of A2 are (P) None of the reactant
O3(g) = 1.5 ¥ 6.02 ¥ 1023
mixed with 8 moles is left
of B2 (D) 4.515 ¥ 1023 mol- (S) mass = 22 g of oxygen
ecules O2 (g)
(B) 2 moles of A2 are (Q) Product contains
mixed with 5 moles both AB and AB3 (T) 3.01 ¥ 1023 molecules
of B2
32. Match the expressions/statements in Column I with
(C) 2 moles of A2 are (R) One of the reactant expressions/Statements in Column II.
mixed with 1 moles is left
of B2 Column I Column II
(No. of moles)
(D) (S) Equal moles of AB
and AB3 are formed (A) Oxygen atoms in 0.5 mol (P) 8
Ca3(PO4)2
28. Match the expressions/statements in Column I with
expressions/Statements in Column II. (B) Carbon atoms in 89.6 L (Q) 4
CH3 at 1 atm and 273 K.
Mole Concept 1.23
(C) Sulphur atoms in 192 g of (R) 5 37. 10.48 g of chloroplatinate salt of diacidic organic base
SO2 was subjected to heating to obtain 3.9 g of white shining
residue. Molar mass of the organic base is given by
(D) ‘Cl’ in 15 ¥ 1023 molecules (S) 3 (a) 1048 (b) 228 (c) 114 (d) 72
Cl2O [Take NA = 6 ¥ 1023] 38. Different acid samples are prepared by using H2SO4,
(T) 6 HCl, HNO3, H3PO2 and HClO4 separately or as a mix-
ture. Calculate minimum volume of 20% w/v NaOH
33. Match the expressions/statements in Column I with solution required (in mL) to completely neutralise any
expressions/Statements in Column II. sample which can be prepared if mass of the sample
Column I Column II cannot exceed 292 g.
(No. of moles) [Round-off answer to nearest integer if required]
39. Calculate a four-digit number “abcd” from the
(A) 1 mole of O2 (P) Occupies 22.4 L at 1
following information.
atm and 0°C
ab = Volume of water (in L) required to obtain 3 L
(B) 1 mole of SO2 (Q) Weighs 32 g of 17% w/v AgNO3 solution from a stock solution of
(C) 4 g of He (R) Collection of NA units AgNO3 having molarity 3 M.
of given substance cd = Mole percentage of ethane in a mixture of ethane
(D) 1 g of H2 (S) Occupies 12.3 L at 1 4
and argon having mass fraction of Argon equal to .
atm and 300 K 7
(T) Contains 2 g-atom of [if your answers are 6 and 25 fill 0625]
oxygen 40. 10 mL of a gaseous organic compound CxHyOzNp (mo-
lar mass = 61) is taken in an eudiometry tube and mixed
with sufficient oxygen gas such that volume becomes
(Integer type) 42.5 mL. On sparking, some contraction was observed.
34. KClO4 can be prepared by Cl2 and KOH by a series of On passing the residual gas through alcoholic KOH,
reactions as given below: a contraction of 20 mL was observed. The volume of
Cl2 + 2KOH Æ KCl + KClO + H2O the residual gas is 5 mL. All volumes are measured at
3KClO Æ 2KCl + KClO3 room temperature and pressure. Calculate the value of
4KClO3 Æ 3KClO4 + KCl the four digit number ‘xyzp’.
If 10 moles of Cl2 are mixed with 22 moles of KOH, 41. 10 mL of a mixture of CO (g) and CH4(g) was mixed
calculate total moles of all the substance at the end of with 22 mL of O2 gas and subjected to sparking. The
reaction. (Assuming 100% yield of all the reactions.) contraction observed when the residual gases are
35. Four identical bottles numbered from 1 to 4 are arbi- passed through alc. KOH is given by x mL. Find x?
trarily filled with four substances : C6H12O6 (Glucose), [All volumes are measured at same temperature
CH3COOH (Acetic acid), CH3–COCH3 (Acetone) and and pressure]
HCHO (Formaldehyde) (No specific order). Based on 42. Compositions Solution codes
following information given, identify the substances (a) 100 g SO3 and 200 g H2SO4 8
filled. (b) 80 g SO3 and 80 g H2SO4 6
Information-I : Percentage of C is same in compounds (c) 5 moles SO3 and 5 moles H2SO4 4
filled in bottles 1, 3, 4 but different in 2. (d) 6 moles SO3 and 5 moles H2SO4 2
Information-II : Vapour density of compound filled Calculate a four-digit number ‘abcd’ which is obtained
in bottle 4 = 3 ¥ vapour density of compound filled in by writing solution codes of above compositions in the
bottle 1. increasing order of % labelling of above oleum.
After identifying the substances filled in different bot- 43. Three substances A, B and C can react to form C and D
tles, arrange them in decreasing order of their molecu- as shown below.
lar masses. 2A + 3B + C Æ 4D + 2E
[For example, If molecular mass order is 4 > 3 > 2 > If molar masses of A, B, C and D are 40, 30, 20 and
1 then answer is 4321] 15 respectively and 570 g of mixture of A, B, and C is
[Assuming normal behaviour of all the substances.] reacted then calculate maximum mass of E which can
36. 1000 g of a mixture of Na2CO3, Na2SO4 and NaOH be obtained (in gram).
for complete neutralisation requires 511 g of HCl. The 44. If 246 g of a triatomic ideal gas having only one type
same mixture when reacted with excess of BaCl2 so- of atoms is found to occupy 44.8 L at 2 atm and 546 K
lution, produced 466 g of white precipitate of BaSO4. then what will be the atomic weight of the element?
Calculate mass % of NaOH in mixture. 45. 100 mL of 0.2M H2SO4 solution is mixed with 400 mL
of 0.05M Ba3(PO4)2. The concentration of [Ba+2] ion in
resulting solution is xM. Find the value of 100 ¥ x?
46. Acrylonitrile, C3H3N, is the starting material for the 4. The density (in g mL–1) of a 3.6 M sulphuric acid solu-
production of a kind of synthetic fibre (acrylies). It can tion that is 29 % H2SO4 (molar mass = 98 g mol–1) by
be made from propylene, C3H6, by reaction with nitric mass will be [AIEEE 2007]
oxide, NO as (a) 1.64 (b) 1.88 (c) 1.22 (d) 1.45
C3H6(g) + NO(g) Æ C3H3N(g) + H2O(g) + N2(g) (Un- 5. Amount of oxalic acid present in a solution can be de-
balanced) termined by its titration with KMnO4 solution in the
How many kilograms acrylonitrile are obtained from presence of H2SO4. The titration gives unsatisfactory
420 kg of propylene and excess NO? result when carried out in the presence of HCl because
47. 10 mL gaseous C4Hx requires exactly 55 mL O2 for HCl [AIEEE 2008]
complete combustion. What is the value of ‘x’. (a) gets oxidised by oxalic acid to chlorine.
48. In 1200 g solution, 12 g urea (NH2CONH2) is present. (b) furnishes H+ ions in addition to those from oxalic
If density of the solution is 1.2 g/mL, then the molarity acid.
of the solution is xM. Find 10x? (c) reduces permanganate to Mn2+.
49. In the following reactions if initially 100 moles of A (d) oxidises oxalic acid to carbon dioxide and water.
were taken then calculate sum of moles of D and C 6. The mass of potassium dichromate crystals required to
after the reaction. oxidise 750 cm3 of 0.6 M. Mohr’s salt solution is (mo-
40%
Æ 3B + D
A æææ lar mass = 392) [AIEEE 2011]
(a) 0.49 g (b) 0.45 g
50%
2B æææ
Æ 4C (c) 22.05 g (d) 2.2 g
50. Calculate the sum of molality and molarity of a pure 7. The molality of a urea solution in which 0.0100 g of
liquid (molar mass M = 50) having density d = 2 g/mL. urea, [(NH2)2CO] is added to 0.3000 dm3 of water at
51. What would be the maximum volume (in mL) of 3 M STP is [AIEEE 2011]
HCl solution that can be prepared by using 2 M, 1 L (a) 5.55 ¥ 10–4 m (b) 33.3 m
HCl and 5 M, 2 L HCl kept in separate vessels. (c) 3.33 ¥ 10–2 m (d) 0.555 m
52. 20 mL of a mixture of C2H6 and C3H8 gases in X : Y 8. The density of a solution prepared by dissolving 120 g
mole ratio, is burnt completely by which 52 mL CO2 of urea (mol. mass = 60 u) in 1000 g of water is 1.15 g/
gas is evolved. If 20 mL of a mixture of CH4 and C4H10 mL. The molarity if this solution is [AIEEE 2012]
gases in Y : X mole ratio is burnt completely, then what (a) 0.50 M (b) 1.78 M
is the volume (in mL) of CO2 gas evolved? (c) 1.02 M (d) 2.05 M
9. The molarity of a solution obtained by mixing 750 mL
of 0.5 M HCl with 250 mL of 2 M HCl will be
Previous Years’ Questions [JEE Main 2013]
of Jee (Main & advanCed) (a) 0.875 M (b) 1.00 M
(c) 1.75 M (d) 0.0975 M
JEE Main 10. A gaseous hydrocarbon gives 0.72 g of water and 3.08
g of CO2 upon combustion. The empirical formula of
1. How many moles magnesium phosphate, Mg3(PO4)2,
hydrocarbon is [JEE Main 2013]
will contain 0.25 mole of oxygen atoms?
(a) C2H4 (b) C3H4
[AIEEE 2006]
(c) C6H5 (d) C7H8
(a) 2.5 ¥ 10–2 (b) 0.02
11. The ratio of masses of oxygen and nitrogen in a par-
(c) 3.125 ¥ 10–2 (d) 1.25 ¥ 10–2
ticular gaseous mixture is 1 : 4. The ratio of number of
2. Density of a 2.05 M solution of acetic acid in water is
their molecule is [JEE Main 2014]
1.02 g/mL. The molality of the solution is
(a) 1 : 4 (b) 1 : 8 (c) 7 : 32 (d) 3 : 16
[AIEEE 2006]
(a) 0.44 mol kg–1 (b) 1.14 mol kg–1 JEE Advanced
(c) 3.28 mol kg–1 (d) 2.28 mol kg–1
3. In the reaction : 2Al(s) + 6HCl (aq) Æ 2 Al3+ (aq) + Single Correct Answer Type
6Cl–(aq) + 3H2 (g) [AIEEE 2007] 12. Consider a titration of potassium dichromate solution
(a) 6 L HCl(aq) is consumed for every 3 L H2(g) pro- with acidified Mohr’s salt solution using diphenyl-
duced. amine as indicator. The number of moles of Mohr’s salt
(b) 33.6 L H2(g) produced regardless of temperature required per mole of dichromate is [IIT JEE 2007]
and pressure for every mole Al that reacts. (a) 3 (b) 4 (c) 5 (d) 6
(c) 67.2 L H2(g) at STP is produced for every mole Al 13. Given that the abundance of isotopes 54Fe, 56Fe and
that reacts. 57
Fe is 5%, 90% and 5% respectively. The atomic mass
(d) 11.2 L H2(g) at STP is produced for every mole of Fe is [IIT JEE 2009]
HCl(aq) consumed.
Mole Concept 1.25
(a) 55.85 (b) 55.95 Find the volume of (mL) of stock solution required to
(c) 55.75 (d) 55.05 prepare a 200 mL solution of 0.4 M HCl.
14. Dissolving 120 g of urea [Mw = 60) in 1000 g of water [IIT JEE 2012]
gave a solution of density 1.15 g mL–1. The molarity of 20. If the value of Avogadro number is 6.023 ¥ 1023 mol–1
solution is [IIT JEE 2011] and the value of Boltzmann constant is 1.380 ¥ 1028 J
(a) 1.78 M (b) 2.00 M K–1, then find the number of significant digits in the
(c) 2.05 M (d) 2.22 M calculated value of the universal gas constant.
[JEE Advanced 2014]
Integer Answer Type 21. The molecular formula of a commercial resin used for
15. A student performs a titration with different burettes exchanging ions in water softening is C8H7SO3Na (mo-
and finds titre values of 25.2 mL, 25.25 mL and 25.0 lecular weight = 206). What would be the maximum
mL. Find the number of significant figures in the aver- uptake of Ca2+ ions by the resin when expressed in
age titre value. [IIT JEE 2010] mole per gram resin? [2015 JEE Main]
16. Silver (atomic weight = 108 g mol–1) has a density of 1 1
10.5 g cm–3. The number of silver atoms on a surface (a) (b)
103 206
of area 10–12 m2 can be expressed in scientific notation 2 1
as y ¥ 10x. Find the value of x. [IIT JEE 2010] (c) (d)
309 412
17. Find the value of n in the molecular formula BenAl-
22. 3g of activated charcoal was added to 50 mL of acetic
2Si6O18. [IIT JEE 2010]
acid solution (0.06 N) in a flask. After an hour it was
18. Among the following, what is the number of elements filtered and the strength of the filtrate was found to be
showing only one non-zero oxidation state ? O, Cl, F, 0.042 N. The amount of acetic acid adsorbed (per gram
N, P, Sn, Tl, Na, Ti [IIT JEE 2010] of charcoal) is [2015 JEE Main]
19. 29.2 % (w/w) HCl stock solution has a density of 1.25 (a) 18 mg (b) 36 mg
g mL–1. The molecular weight of HCl is 36.5 g mol–1. (c) 42 mg (d) 54 mg
Answer Key
level i
1. (b) 2. (b) 3. (d) 4. (a) 5. (a) 6. (a) 7. (a) 8. (d) 9. (c) 10. (b)
11. (d) 12. (a) 13. (a) 14. (a) 15. (b) 16. (a) 17. (b) 18. (b) 19. (c) 20. (b)
21. (a) 22. (d) 23. (c) 24. (d) 25. (a) 26. (d) 27. (b) 28. (b) 29. (b) 30. (a)
31. (c) 32. (c) 33. (a) 34. (c) 35. (b) 36. (a) 37. (a) 38. (c) 39. (a) 40. (c)
41. (a) 42. (a) 43. (a) 44. (d) 45. (a) 46. (a) 47. (b) 48. (d) 49. (b) 50. (c)
51. (b) 52. (c) 53. (b) 54. (b) 55. (b) 56. (a) 57. (b) 58. (b) 59. (b) 60. (a)
61. (d) 62. (a) 63. (c) 64. (a) 65. (a) 66. (a) 67. (b) 68. (a) 69. (c) 70. (b)
71. (c) 72. (b) 73. (c) 74. (b) 75. (b) 76. (b) 77. (d) 78. (c) 79. (b) 80. (b)
81. (b) 82. (d)
level ii
1. (c) 2. (c) 3. (d) 4. (a) 5. (b) 6. (c) 7. (b) 8. (a) 9. (a) 10. (b)
11. (c) 12. (d) 13. (a) 14. (a) 15. (a) 16. (b) 17. (b) 18. (b) 19. (b) 20. (b)
21. (a) 22. (c) 23. (a) 24. (a) 25. (c) 26. (c) 27. (c) 28. (c) 29. (d) 30. (a)
31. (d) 32. (c) 33. (a) 34. (b) 35. (a) 36. (c) 37. (c) 38. (b) 39. (d) 40. (c)
level iii
1. (a) 2. (b) 3. (b) 4. (b) 5. (b) 6. (b) 7. (c) 8. (a) 9. (c) 10. (b)
11. (a, b) 12. (a, b, c) 13. (b, c) 14. (a, b, d) 15. (a, b) 16. (a, d) 17. (a, b, d)
18. (a, b) 19. (a, d) 20. (a, d) 21. (a, c) 22. (a, b, d) 23. (a, b, c, d) 24. (b, c, d)
25. (a, c, d) 26. (b, d) 27. (A) Æ P, Q, S; (B) Æ P, Q; (C) Æ R
28. (A) Æ P, Q, R; (B) Æ P, R; (C) Æ P, R; (D) Æ S 29. (A) Æ P, R; (B) Æ Q, R; (C) Æ Q, S; (D) Æ Q, R
30. (A) Æ P, Q; (B) Æ Q; (C) Æ P, Q, R, S; (D) Æ Q, S 31. (A) Æ P, R, S, T; (B) Æ P; (C) Æ P, Q, T; (D) Æ Q, R
32. (A) Æ Q; (B) Æ Q; (C) Æ S; (D) Æ R 33. (A) Æ P, Q, R, T; (B) Æ P, R, T; (C) Æ P, R; (D) Æ S
34. (32) 35. (4123) 36. (8) 37. (114) 38. (1600) 39. (0251) 40. (2711) 41. (10) 42. (8426) 43. (390)
44. (41) 45. (8) 46. (530) 47. (6) 48. (2) 49. (160) 50. (60) 51. (1500) 52. (44)
Previous Years’ Questions of Jee (Main & advanCed)
1. (c) 2. (d) 3. (d) 4. (c) 5. (c) 6. (c) 7. (a) 8. (d) 9. (a) 10. (d)
11. (c) 12. (d) 13. (b) 14. (c) 15. (3) 16. (7) 17. (2) 18. (2) 19. (8) 20. (4)
21. (d) 22. (d)
Hints and Solutions

Average number of neutrons
level 1
18 ¥ 80 + 20 ¥ 20
= = 18.4
100
1. (a) (1) Oxygen atom : Hydrogen atom
6. (a) K2SO4. Al2(SO4)3 ◊ 24 H2O
4 : 12 [1 : 3]
6.4 kg oxygen
(2) 3NH +4 : 1 PO34- [3 : 1] [moles of substance ¥ 40] = number of mole of oxygen
(3) N atom : Oxygen atom [3 : 4] 40 ¥ x ¥ 16 = 6400 g= wt of oxygen
(4) (NH4)3PO4 | 3N + 12 H + P + 4 O x = 10 moles
1 mole number of moles of S = 4 ¥ 10 moles = 40 moles
1 mole of (NH4)3PO4 having 20-Mole of atoms and weight of sulphur = 40 ¥ 32 = 1280 g
or (20 ¥ NA) atoms. 7. (a) 448 l O2 and CO2(g) 2 : 3
2. (b) PV = nRT
3
= 1 ¥ 10–3 number of moles Volume of CO2 = ¥ 448 = 268.8 l
\ No of moles of of atom = 3 ¥ 10–3 5
Let volume of H2O2 is V mL 268.8L
Number of moles of CO2 = = 12 mole
Mass of H2O2 = V ¥ d = V ¥ 5.1 ¥ 10–3 22.4L
8. (d) A2SO4 ◊ xH2O
V ¥ 5.1 ¥ 10-3 A2SO4 ◊ xH2O h A2SO4 + xH2O
Moles of H2O2 =
34 x ¥ 18
% of H2O = ¥ 100 = 45
V ¥ 5.1 ¥ 10-3 110 + x ¥ 18
Number of moles of atoms = ¥4
34 1800 x = 4950 + 810 x
= 3 ¥ 10–3 1800 x – 810 x = 4950
V of H2O2 = 5 mL 990 x = 4950
3. (d) 72 g Mg is present in x=5
1 mole Mg3(PO4)2 9. (c) MnO2 + 4HCl h MnCl2 + Cl2 + 2H2O
\ 8 moles of O atoms
4 moles of O2 molecules 1.74
nMnO2 = = 0.02
4 gm molecules of O2 are present 87
4. (a) 930 gm of Ca3(PO4)2 = 3 mole of Ca3(PO4)2 2.19
nHCl = = 0.06
= 15 moles of ions 36.5
5 moles of Na2SO4 = 15 mole of ions No of moles /stoichiometric cofficient least for HCl
weight of Na2SO4 = 5 ¥ 142 \ HCl is limiting reagent
= 710 g 4 mole of HCl gives 1 mole of Cl2
5. (a) Average atomic weight = SXiMi 1 mole of HCl gives 1/4 mole of Cl2
= 35 ¥ 0.8 + 37 ¥ 0.2 0.06 mole of HCl gives 1/4 ¥ 0.06 mole of Cl2 = 0.015
= 35.4 Mole
Mole Concept 1.27
Actual product formed Ê 936 ˆ

% yield = ¥ 100 ÁË ˜
theoritical product formed 18 ¯ (52 ¥ 1000)
17. (b) m = fi fi 55.56
x Ê 936 ˆ 936
40 = ¥ 100 ÁË ˜
0.015 1000 ¯
0.015 18. (b) H3PO4 + 2NaOH h Na2HPO3 + 2H2O
x = 40 ¥ = 0.006 moles Cl2 Number of moles of H3PO4 = ½ No of moles of NaOH
100
Volume of Cl2 at 1 atm, 273 K = 0.006 ¥ 22.4 (lit.) = 150 ¥ 1.5 1 V 0.5
= ¥ ¥
134.4 ml 1000 2 1000 1
10. (b) (CaCO3 + Na2CO3) mixture = 103 g V = 900 mL
Let moles of CaCO3 = x 19. (c) AlCl3 + 3NaOH h Al(OH)3 + 3NaCl
moles of Na2CO3 = y 1 1
x y 1 1 mole AlCl3 Require 3 mole NaOH for Completion of
CaCO3 + Na2CO3 + HCl h CO2 and other products. Reaction
CO2 produced have C atoms from Na2CO3 and CaCO3 \ No of moles of AlCl3 react with 1 mole
moles of CO2 produce = PV = nRT 1
NaOH = Mole
1 ¥ 24.63 = n ¥ 0.0821 ¥ 300 3 1 2
n=1 \ Moles of AlCl3 left = 1 – = Mole
3 3
Apply POAC on C atom
20. (b) a
mole CaCO3 + b mole CaO
1¥x+y¥1=1  
x+y=1 CaCO3 h CaO + CO2
100 x + 106 y = 103 = wt of mixture a mole CaCO3 give 22.4 litre or 1 mole CO2
6x = 3; x = 0.5; y = 0.5 CaCO3 + 2HCl h CaCl2 + CO2 + H2O
weight of CaCO3 = 50 g 1 ¥100 gram CaCO3 React with 2 ¥ 36.5 = 73 gram HCl
weight of Na2CO3 = 53 g CaO + 2HCl h CaCl2 + H2O
\ Wt of HCl react with CaO
50
% CaCO3 = ¥ 100 = 48.54 % = 219 – 73 = 146 gram
103 146
11. (d) H2 + Cl2 h 2HCl nHCl = = 2b = 4 mole
36.5
2g 71 g \ b = 2 mole
1 mole of H2 react with 1 mole Cl2 gives 2 mole HCl = 2 × 56 = 112 gram
\ No of moles of HCl produced Mole % of CaCO3
= 2 moles = 2 ¥ 36.5 g = 73 g
1
12. (a) Conceptual ¥ 100 = 33.33%
13. (a) Cu + 4 HNO3 h Cu(NO3)2 + 2H2O + 2NO2 3
1 mole Cu Provide 2 moles NO2 d gas M gas È PM ˘
21. (a) RD = = ÍÎ d = RT ˙˚
12.7 12.7 d ref gas M ref gas
Mole Cu provide = 2 ¥ Mole NO 2
63.5 63.5 M gas
nNO2 = 0.4 RD = fi Mgas = 30
1
\ Volume = 0.4 ¥ 22.4 ¥ 1000 mL = 8960 mL W
Mavg = T
14. (a) Mass of carbon in 1 molecule of X = 21 ¥ 12 = 252 amu nT
if % weight of carbon is 50.4 % in molecule then CO2 : H2O
252 ¥ 100 Mole a b
Molecular mass of X = = 500 amu
50.4 a ¥ 44 + b ¥ 18
30 = fi 30a + 30b = 44a + 10b
1 a+b
15. (b) FeCl3(s) h FeCl2(s) + Cl2(g)
2 a 6
14a = 12b fi =
1 mol FeCl3(s) given 0.5 mol Cl2(g) b 7
0.5 ¥ 0.0821 ¥ 300 a 6 600
P= = 150 atm Mole % of CO2 = ¥ 100 = ¥ 100 =
0.0821 a+b 13 13
–31
È 54 + 96 ¥ 3 ˘ È 342 ˘ 22. (d) Mass of 1 electron = 9.1 ¥ 10 kg
16. (a) P = 294 Í ˙ = 294 Í = 342 Molar mass of Electron mean mass of NAe–
Î 98 ¥ 3 ˚ Î 294 ˙˚
= 9.1 ¥ 10–31 ¥ 6.022 ¥ 1023 = 54.8 ¥ 10–8 kg/ mole From (i), (ii) and (iii)
23. (c) (KHC2O4)0 95 · HC2O4 x = 50, y = 100 and z = 100
[4 + 0.95 ¥ 4] mole oxygen atom present in 1 mole \ PCO + Po2 = 100 + 250 = 350 mmHg
compound 27. (b) 3O2 h C6H12O6
1 For 1 mole Glucose requires 3 mole O2
\ 1 mole oxygen atom present in
[4 + 0.95 ¥ 4] 8
Mole compound mole (O2) in 1 hour is taken
1 32
\ 4 mole oxygen atom present in 1 32
[4 + 0.95 ¥ 4] 1 mole (O2) in taken in hour = hour
Mole compound 8/32 8
No of moles of solute (WA ) 32 ¥ 3
24. (d) M = ¥ 1000 (i) \ 3 mole (O2) in taken in = 12 hours.
Wt of solvent (gm) 8
nA 28. (b) If total moles = 1
xA = moles of SO3 = mole of H2SO4 = 0.5
Sn
mass of SO3 + H2SO4 = 40 + 49 = 89 g
n A = x A Sn
SO3 + H2O h H2SO4
WA 0.5 0.5
= X A Sn
MA mass of H2O require = 0.5 ¥ 18 = 9 g
\ WA = XASn MA = wt of solute 89 g require 9 g H2O
100 g require = 10.11 g
\ WB = XBSn MB = wt of solute % Labelling = (100 + 10.11) = 110.11%
From equation (1) 29. (b) MnO2 + H2 h MnxOy + H2O
x SnM A 17.4 g 12.6 g
m= A ¥ 1000
xB SnM B 17.4 12.6
x A 1000 87 55 x + 16 y
= ¥
xB M B Applying POAC on Mn atom
xA 1000 10 X A 1 12.6 x
= ¥ = =
(1 - x A ) 100 1 - X A 5 55 x + 16 y
25. (a) 100 mL of 0.1 M (NH4)2HPO3 63x = 55x + 16y
10 mm of (NH4)2HPO4 8x = 16y
È y 1˘
ÍÎ x = 2 ˙˚
NH4+ HPO42
20 mm 10 mm ¥ 0.2 M 40 mm
7.5 ¥ 1022 1
30. (a) Moles of element in cube = =
Na4P2O7 h 200 mL + 0.2 M = 40 mm 6 ¥ 1023 8
1
Mass of element in cube = ¥ 32 g = 4 g
Na+ P2O74 8
4 ¥ 40 mm 40 mm
4 Mass
Volume of cube = = 3 cm3 =
Total millimoles of positive ions = 180 4/3 density
180 1800 a3 = 3 cm3 \ a6 = 9 cm6

Conc. (mm/litre) = = = 600 mass of CaBr2
0.3L 3 31. (c) (1) m = ¥ 1000
M.W. ¥ mass of H 2O
x C2H4 C2H4 H2O(l)
CO Sparking CO2 1000
26. (d) y CO N2 m= = 5m
N2
O2 200
z N2 O2 H2O(Vapour) 0.5
(2) m = ¥ 1000 = 55.5
x + y + z = 250 ...(i) 0.5 ¥ 18
C2H4 + 3O2 h 2CO2 + 2H2O (l) 0.5
(2x + y) + z + [(250 – (3x + y/2)] + 20 = 370 (3) m = ¥ 1000 = 55.5
0.5 ¥ 18
CO + O2 h CO2(g)
2x + y = 200 ...(ii) (4) As mole fraction of NaCl and H2O are same which
–x + y/2 + z = 100 ...(iii) means both have same moles hence m will be 55.5.
Mole Concept 1.29
32. (c) M = 44.8/11.2=4 A = 5000 m2

(1) moles of H2O2 in 3L = 3 ¥ 4 = 12 +4 +7 +6
(2) volume of H2O2 (used) = (60 ¥ 0.2 ¥ 2.8) = 33.6 L 37. (a) SO 2 + MnO 4- h SO 4-2 + Mn +2
nf = 2 nf = 5
33.6
Mole of O2 used = = 1.5 Let x mole of SO2
22.4
Mole of H2O2 used = 2 ¥ 1.5 = 3.0 (equivalent of SO2 = equivalent of KMnO4)
(3) 2H2O2 h H2O + O2 9 ¥ 0.008 ¥ 5
moles (H2O2) = 2 ¥ 1.5 = 3 moles x¥2=
1000
moles of H2O2 left = 12 – 3 = 9 9 ¥ 0.008 ¥ 5
M (H2O2) = 9 mole/3L = 3M x=
1000 ¥ 2
(4) V.S. = 3 ¥ 11.2 = 33.6 V
33. (a) N2 + H2 h N2H2(l) + N2H4(g) weight of SO2, = x ¥ 64
POAC on N a mole b mole
Ê 9 ¥ 0.008 ¥ 5 ¥ 1000 ¥ 64 ˆ
30 ¥ 2 = 2a + 2b fi a + b = 30 = Á ˜¯ mg = 11.52 mg
POAC on H 40 ¥ 2 = 2a + 4b fi a + 2b = 40 Ë 1000 ¥ 2
b = 10, a = 20 38. (c) 98 gram 80 gram
V.C. = (30 + 40) – 10 = 60 mL H2SO4 + 2NaOH h Na2SO4 + 2H2O
Energy change = 10 ¥ 2 = 20 H3PO4 + NaOH h NaH2PO4 + H2O
60/20 = 3 98 gram 40 gram
34. (c) When mixture is pass through hot graphite CO2 will 40 gram NaOH reacts with 49 gram H2SO4 and 98
be converted into CO as C is present in excess gram H3PO4 to form sulphate and dihydrogen phos-
CO2(g) + C(s) h 2CO (g) phate.wt. ratio
x mL 2x mL H2SO4 : H3PO4
Initial mixture 150 mL 49 98
Volume of CO2 = x mL 1 : 2 Ans.
Volume of CO = 150 – x 39. (a) Mol % of oxygen Present in
Which is already present in mixture 16
Total volume after reaction = 150 – x + 2x = 200 H2O = ¥ 100 = 88.88%
18
x = 50 mL Volume of CO2 in original mixture = 50
Volume of CO in original mixture = 100 118 % Oleum
100 40. (c) + 9 g H2O
Mole fraction of CO in original mixture = = 0.66 100 g
150
35. (b) HCOOH h H2O + CO
a mole gives a a 80 g SO3 20 g H2SO4
H2C2O4 h H2O + CO2 + CO
b mole gives b b b H2SO4 + SO3
Since H2O exist in liquid state.
volume of CO 2 b 1
= =
total volume (CO + CO 2 ) a + b + b 10 69 g 40 g
10b = a + 2b H2SO4
8b = a (1) % H2SO4 by wt. = 63.30 %
mole ratio 8 : 1 8+1=9 (2) Mass % of combined SO3 fi = 51.67%
4 ¥ 12.3 (3) with 109 g New oleum water can react = 9 g
36. (a) Initial moles of air = =2 \ with 100 g New oleum water can react = new
0.082 ¥ 300
labelling = 100 + 8.25 fi 108.25 %
3.6 ¥ 12.3 40
mole of air after 20 minutes = = 1.5 (4) Mass % of free SO3 = ¥ 100 fi 36.69%
0.082 ¥ 300 109
mole of air leaked in 20 min. 0.5 41. (a) 3NaOH + H3PO4 h Na3PO4 + 3H2O
molecule escape = 0.5 NA Total m moles of H3PO4 = (10 ¥ 0.5) = 5
Let surface area A cm2 \ Require NaOH = 15 m moles
Total molecule escape in 20 min. 15 1
0.5 ¥ 105 ¥ A ¥ 6.023 ¥ 108 ¥ 20 = 0.5 NA for Molarity of NaOH required = fi
300 20
A = 5 ¥ 107 cm2
Number of neutron in one molecule = 36

Ê 1ˆ Ê 1ˆ
V1 Á ˜ + V2 Á ˜ 36
Ë 10 ¯ Ë 30 ¯ 1 Number of neutron in one atom = = 18
= 2
V1 + V2 20
Mass number = number of proton + number of neutron
2 = 16 + 18 = 34
V + 2V1 = V1 + V2 49. (b) Mol. wt. of Al2(SO4)3 = 342
3 2
1 6840
V1 = V2 No. of moles of Al2(SO4)3 = = 20 moles
3 342
V no. of moles of ions in it = 20 ¥ 5 = 100 mole
V1 = 2  4 moles of ions are present in 1 mole Na3PO4
3
100
V2 = 3V1 \ 100 moles of ions are present in mole Na3PO4
4
V1 + V2 = 1000 mL 50. (c) 9F19 19K39 32XA
4V1 = 1000 mL fi V1 = 250 mL 1 : 1 : 1 Mole ratio
42. (a) (NH4)2HPO3 10 : 20 : (A – 32) Number of neutron
43. (a) N2(g) + H2(g) h N2H2(g) Average number of neutron
6 30 0
10 ¥ 1 + 20 ¥ 1 + ( A - 32)
LR = = 25
0 24 6 3
N2H2(g) + H2(g) h N2H4(l) A – 2 = 75 \ A = 77
6 24 0 1 ¥ 19 + 1 ¥ 39 + 1 ¥ 77
\ av. mass =
LR 3
0 18 6 Average Mass = 45
Volume contraction = (30 + 6) – 18 = 18 L 51. (b) Molecular weight of C6H12O6 = 180
18 36
% of volume contracted = ¥ 100 = 50% Number of mole of C6H12O6 = = 0.2 mole
36 180
44. (d) wt = 0.078 gram Number of electron in one molecule of C6H12O6
PV = nRT = 6 ¥ 6 + 12 ¥ 1 + 6 ¥ 8 = 96
22.4 Number of electron in 0.2 mole C6H12O6 = 0.2 ¥ 96 ¥
1¥ = n ¥ 0.0821 ¥ 273 NA = 19.2 NA
1000
0.078 7
= ¥ 0.0821 ¥ 273 52. (c) 2NH3 + O2 h 2NO2 + 3H2O
M mass 2
w1 w2
M Mass of hydrocarbon = 78
EF mass = 13 w1 w2
molecular formula = C6H6 17 = 32 ; w1 = 2 ¥ 2 ¥ 17; = 17 Ans.
45. (a) 10 gm CaCO3 contains 4 g Ca 2 7 w2 32 ¥ 7 56
4 2
% mass = ¥ 100 = 40%
10 M mass 53. (b) P4 + 5O2 h P4O10
46. (a) Volume of 1 mole of CH3CH2OCH3 31
density mole 32
60 mole
= = 75 cm 3 4 ¥ 31 32
0.8
 O2 is limiting reagent
75
Volume occupied by 1 molecule = 1
6 ¥ 1023 So, Number of mole of P4O10 formed = mole
5
= 1.25 ¥ 10–22 cm3 1
47. (b) Na2SO4 h 2Na + SO4+ 2– wt. of P4O10 formed = ¥ 284 = 56.8 gm
5
1 molecule gives 2 ions of Na+
54. (b) Moles of Na2SO4 = 200 ¥ 0.1 ¥ 10–3
48. (d) One mole A2 contain 32 mole electron and 36 mole
neutrons. Moles of Na+ = (200 ¥ 0.1 ¥ 10–3) ¥ 2 = (2 ¥ 10–2) ¥ 2
So, Number of electron in one molecule = 32 Moles of Na3PO4 = 100 ¥ 0.2 ¥ 10–3
32 Moles of Na+ = (100 ¥ 0.2 ¥ 10–3) ¥ 3 = 2 ¥ 10–2 ¥ 3
Number of electron in one atom = = 16 Total moles of Na+ = 5 ¥ 2 ¥ 10–2 = 10–1
2
Mole Concept 1.31
10-1 1 1
M Na + = ¥ 1000 = = 0.33 M Ans \ wt of MgO = ¥ 40 = 20 g
300 3 2
12 + 32 = 44 g (Mass conservation)
Parts of solute wt of solute
55. (b) PPM = ¥ 106 = ¥106
Part of solution wt of solution 2.4 ¥ 1024
61. (d) nC a = = 4 Mole
6 ¥ 1023
w wt of solute
%= ¥ 100
w wt of solution 380
¥ 96
Pv 0.5 ¥ 96 48
% Labeling of OLEUM = 100 + wt of water added for nCl 2 = = 760 = = = 2 Mole
obtaining maximum wt of H2SO4 in 100 gram Oleum. RT 0.0800 ¥ 300 24.00 24
Since V µ T So above concentration term independent Ca + Cl2 h CaCl2
of temperature or volume. 4 2 0
56. (a) No of e– in one O– – ion = 8 + 2 = 10e 2 0 2 Mole = 2 ¥ 111 = 222 g
10e– present in one O– – ion 62. (a) C4H8 + 6O2 h 4 CO2 + 4H2O
1 –– 3 mole C4H8 give h 3 ¥ 4 CO2= 12 Mole CO2
\ 1 e– present in one O ion
10 C6H6 + O2 h 6 CO2 + 3H2O
1 3 Mole C6H6 gives h 6 ¥ 3 CO2 = 18 Mole CO2
\ 1.2 ¥ 1022 present in one ¥ 1.2 ¥ 1022
10 12 + 18 = 30 Mole CO2 = 30 ¥ 44 = 1320 gram.
= 1.2 ¥ 1021 oxideion 50%
63. (c) 2KClO3 æææ Æ 2KCl + 3O 2
1.2 ¥ 1021
= mole 67.2
6 ¥ 1023 nO 2 = = 3 Mole
22.4
= 2 ¥ 10–3 Mole
57. (b) No of proton in one D3O+ = 3 + 8 = 11 3 Mole O2 produced from 50% impure KClO3
No of neutron in one D3O+ = 3 + 8 = 11 \ Moles of pure KClO3 in impure Sample
n 11 2
\ ratio of = = 1 : 1 any amount =2¥ ¥ 3 = 4 Mole
p 11 3
= 4 ¥ [39 + 35.5 + 48 ] = 490 gram.
Since Deuterium have 1P, ln and l e– 64. (a) No of moles of N2 = 3a
Oxygen atom have 8P, 8n and 8e– No of moles of O2 = a
PV wt 2.4
58. (b) n = = a=
RT Mwt 32
2 ¥ 14 80 2.4
= \ No of moles of N2 = 3 ¥
0.0821 ¥ 273 Mwt 32
28 80 2.4
= Wt of N2 = 3 ¥ ¥ 28 = 6.3 gram
22.4 Mwt 32
80 ¥ 22.4 \ Total Mass = 6.3 + 2.4 = 8.7 gram
Mwt = = 64
28 65. (a) Urea NH2 CONH2 have 2 atom of Nitrogen in one
64 = 32 + x [16] Molecule or 2 gram atom in 1 Mole
\ x=2 \ 20 gram atom in 10 Mole urea = 10 ¥ 60 = 600 gram
wt of iron 2.8 3.5
59. (b) ¥ 100 = 0.25 66. (a) =
M Mass 22.4 M Mass
x ¥ 56 0.25 22.4 ¥ 3.5
= = M Mass =
89600 100 2.8
89600 ¥ 0.25 M Mass
x= =4 \ VD = = 14
56 ¥ 100 2
1 67. (b) Ni0 98 O100 fi Ni98 O100
60. (a) Mg + O2 h MgO x [ + 3] + (98 – x) ¥ 2 + 100 (–2) = 0
2
1 3x + 196 – 2x = 200
Here Mg L.R. \ 12 g = mole Mg gives x=4
2
1 4
mole MgO ¥ 100  4%
2 98
40 \ number of M+3 = 0.04

68. (a) No of moles I2 = ¥ 0.1 0.04
1000
Percentage of M+3 = ¥ 100 = 4.08%
È 40 ˘ 0.98
\ No of atom = Í ¥ 0.1 ¥ 6.022 ¥ 1023 ˙ ¥ 2 1
Î1000 ˚ nO2 7
= 48.17 ¥ 1020 77. (d) = 32 =
nN2 4 32
+
69. (c) [H ] = 0.1 M 28
H2SO4 h 2H+ + SO -4 V 11.2
78. (c) M = = =1M
[H+] = 0.1 M 11.2 11.2
0.1 M w 10
\ MH2SO4 = = 0.05 M M= %
2 v MA
70. (b) 1 Molal aq solution means
1 Mole in 1000 gram = 55.5 mole water w 10
1= %¥
1 1 v 34
\ Mole fraction = = = 0.0179 = 0.018 w
1 + 55.5 56.5 % = 3.4%
v
71. (c) 1 Million = 106
Wt of 106 atom = 1.79 ¥ 10–16 g w 10d
M= %
w MA
1.79 ¥ 10-16
\ Wt of 1 atom = w 10 ¥ 1.034
106 1= %¥
w 34
1.79 ¥ 10-16 w 34 3400
\ wt of NA atom = ¥ 6.022 ¥ 1023 \ %= =
106 w 10.34 1034
= 17.9 ¥ 6.022 = 107.79 79. (b) CO(a mL) + CO2 (150-a mL) = 150 mL initially
72. (b) gram atom or Mole CO2 + C(s) Æ 2CO
(150 – a)mL CO2 gives 2 [150 – a] mL CO
1.4
= 0.1 gram atom Total volume after reaction
14 a + 2 [150 – a ] = 250
73. (c) CuSO4 ◊ 5H2O h CuSO4 + 5H2O 300 – a = 250
wt of CuSO4 = 95.7 a = 50 mL = VCO ˘
No of Moles of CuSO4 = No of moles of blue vitriol inoriginal mixture
Vco 2 = 100 ml ˙˚
95.7 95.7
= = 50
63.5 + 96 159.5 ¥ 100 = 33.33%
150
\ No of water Molecule 80. (b) Zn + 2HCl Æ ZnCl2 + H2
95.7
= ¥ 6.022 ¥ 1023 ¥ 5 = 18.06 ¥ 1023 130.6
159.5 = No of moles of Zn = No of mole of H2
65.3
74. (b) Zn + H2SO4 h ZnSO4 + H2
130.6
112 1 \ VH 2 = ¥ 22.4 = 44.8 L
No of moles of H2 = = moles 65.3
22400 200
39
no of moles of H2 = No of moles of Zn 81. (b) % wt of K in KCl = ¥ 100 = 52.34%
74.5
1
= Moles 39
200 % wt of K in KNO3 = ¥ 100 = 39%
1 101
= ¥ 65 = 0.325 g \ % of K vary between 39% to 52.34% in mixture of
200
KCl and KNO3
18 mL ¥ 1 g/mL 82. (d) MnO2 + 4HCl h MnCl2 (g) +Cl2 + 2H2O
75. (b) No of moles = = 1 mole
18 164.2 mL
No of e– in one molecule of H2O = 2 + 8 = 10 38 164.2
\ Total No of e– in 1 Mole = 10 ¥ 6.022 ¥ 1023 ¥
PV 1
= 6.022 ¥ 1024 nCl 2 = = 76 1000 = mole
RT 0.0821 ¥ 400 400
76. (b) n ¥ 2 + (0.98 – n) ¥ 3 = 1 ¥ (–2)
1
n = 0.94 \ nHCl = mole = M ¥ 0.2
100
Mole Concept 1.33
1 6. (b) Let the mass of sample is 100

Molarity = = 0.05 M Let the mass of FeS is x
20
\ Mass of impurities will be 100 – x
After reaction,
level ii Loss = 8 gm
Remaining mass of sample = 92 g
Since loss is due to FeS converting into Fe2O3
1. (c) (I) 2 g of hydrogen
\ Mass of impurities still remain same = 100 – x
2 \ Mass of Fe2O3 formed = x – 8
number of moles = = 2 ¥ NA number of at-
oms 1 7
2FeS + O2 h Fe2O3 + 2SO2
(II) 16 g of sulphur 2
number of moles Apply POAC on Fe atom
x x-8
16 1 = ¥2
= = ¥ NA number of atoms 88 160
32 2
(III) 4 g of oxygen \ x = 88 gram or 88%
7. (b) 7 A + 13 B + 15 C h 17 P
4 1
number of moles = = ¥ NA number of 15 26 30.5
16 4
atom 7 13 15
(IV) 31 g of phosphorus 2.1428 2 2.033
LR = B
31
number of moles = = 1 ¥ NA number of at- No of moles
31 If Least
oms Stoichimetric coefficient
I > IV > II > III behave as L.R.
2. (c) Weight of 1 molecule of CxDy = 1.66 ¥ 10–25 kg SO3
80 ¥ 5 = 400 g
weight of 1 mole CxDy = 100 g
x ¥ 20 + y ¥ 40 = 100 8. (a) 118%
weight of 1 mole CyDx = 80 g H2SO4
20 ¥ 5 = 100 g
20y + 40x = 80
or 100 OLEUM given = 118 g H2SO4
40y + 80x = 160 590
500 OLEUM given = 590 g =
40y + 20x = 100 98
60x = 60 Mole H2SO4 = 6 moles
\ x = 1 and y = 2 H2SO4 + 2KOH h K2SO4 + H2O
3. (d) In one molecule of Mg3N2 ◊ 3Mg+2 are present \ No. of moles of KOH required 6 ¥ 2 = 12 mole
\ total number of electron transferred = 3 ¥ 2 = 6 for complete neutralisation.
4. (a) Weight ratio = 5 : 1 9. (a) 2 Zn + O2 æææ
90%
Æ 2ZnO
5 1 130
\ Molar ratio = : No. of moles of Zn = = 2 moles
80 16 65
\ ratio of atoms
100
NA ¥ 4 : 5 ¥ NA number of atoms No. of moles of O2 = = 2 moles
32
5
200 ¥ ¥ NA ¥ 4 \ Zn (LR)
80
Q= 90
1 No. of moles of ZnO = ¥ nZn = 2 moles
¥ NA ¥ 5
16 100
2ZnO + H2O Æ 2Zn (OH)2
4 Since 1.8 mole ZnO Produced 1.8 mole Zn (OH)2
Q = 200 ¥ 1(SO3) : 1(CH4) mole ratio
5 \ % yield of reaction 100%
Q = 160
10. (b) x C2H4 C2H4 H2O(l)
5. (b) 2A(s) + B(g) h 3C(g) + 4D(l) Sparking CO2
CO
y CO N2
22.4 L N2
= 1 mole B gives 3 moles of C in excess of A O2
22.4 L z N2 O2 H2O(Vapour)
here B is L. R.
x + y + z = 250 ... (i) C2H4 + 3O2 h 2CO2 + 2H2O

C2H4 + 3O2 h 2CO2 + 2H2O (l) x
(2x + y) + z + [(250 – (3x + y/2)] + 20 = 370 Total O2 = 10 ¥ 2 + 20 ¥ 3 = 80 mL
CO + O2 h CO2(g) 20
Volume of O2 = ¥ volume of air = 80 mL
–x + y/2 + z = 100 ...(iii) 100
2x + y = 200 ...(ii) Volume of air = 400 mL.
From (i), (ii) and (iii) 15. (a) Let 100 mL of air and 100 mL of H2 is taken
x = 50, y = 100 and z = 100 100 mL air contain 80 mL N2 and 20 mL O2
Partial Pressure of C2H4 = 50 mmHg N2 (g) + 3H2 (g) h 2NH3 (g)
x C2H4 C2H4 H2O(l) 2
CO2
80 100 ¥ 100 = 66.67
CO Sparking 3
11. (c) y CO N2 L.R.
N2
O2
z N2 O2 H2O(Vapour)
4NH3 + 5O2 h 4NO + 6H2O
66.67 20 L.R.
x + y + z = 250 ...(i) H2 and O2 Limiting regent
C2H4 + 3O2 h 2CO2 + 2H2O (l) \ Completely exhausted.
(2x + y) + z + [(250 – (3x + y/2)] + 20 = 370 16. (b) Ca3(PO4)2 + 8Mg h Ca3P2 + 8MgO
CO + O2 h CO2(g) Excess 8 mole 1 mole 8 mole
–x + y/2 + z = 100 ...(iii) Ca3P2 + 6H2O h 3Ca(OH)2 + 2PH3
2x + y = 200 ...(ii) 1 mole Excess 3 mole 2 mole
From (i), (ii) and (iii) 2PH3 + 4O2 h P2O5 + 3H2O
x = 50, y = 100 and z = 100 2 mole Excess 1 mole 3 mole
\ Total Oxygen consume = 200 mmHg MgO + P2O5 h Mg(PO3)2
12. (d) 118% oleum means in 100 gram oleum by adding 8 mole 1 mole 1 mole
18 gram water it gives 118 gram H SO nH2O added =
2 4
LR wt = 182 gram.
nSO3 Present in 100 gram Oleum by adding 9 gram or 17. (b) In 1 Liter or 1000 mL
wsol = V ¥ d = 1140 gram
1 1 1 wB = 7 ¥ 30 = 210 gram
mole water mole SO3 change into H2SO4 and
2 2 2 wA + wsolvent = 930
mole SO3 = 40 gram SO3 present in 109 gram Oleum 10nA + wsolvent = 930
40 nA
\ % wt of SO3 = ¥ 100 = 36.7% x A = 0.05 =
109 WH2O
13. (a) HCl H2SO4 H2SO3 H3PO4 nA + 7 +
18
36.5 98 82 98
4% w/v fi 1 Molar NaOH 18. (b) Moles of Na2SO4 = 200 ¥ 0.1 ¥ 10–3
H3PO4 + 3NaOH h Na3PO4 + 3H2O Moles of Na+ = (200 ¥ 0.1 ¥ 10–3 ) ¥ 2 = (2 ¥ 10–2 ) ¥ 2
3 9 moles Moles of Na3PO4 = 100 ¥ 0.2 ¥ 10–3
Moles of NaOH required = 9 = M1V1 fi V1 = 9 litres Moles of Na+ = (100 ¥ 0.2 ¥ 10–3) ¥ 3 = 2 ¥ 10–2 ¥ 3
V1 = 9000 mL Total moles of Na+ = 5 ¥ 2 ¥ 10–2 = 10–1
14. (a) CH4 + 2O2 h CO2 + 2H2O 10-1 1
M Na + = ¥ 1000 = = 0.33 M Ans
x mL 300 3
C2H4 + 3O2 h 2CO2 + 2H2O 19. (b) Milli equivalent of H2O2 = Milli equivalent of
y mL KMnO4
Volume of hydrocarbon (x + y) 2 ¥ M ¥ 10 = 25 ¥ 0.2 ¥ 5
20 M = 1.25
Volume of O2 = ¥ 350 = 2x + 3y
100 Volume strength of H2O2 = 11.2 ¥ molarity
x + y = 30 ...(1) fi 11.2 ¥ 1.25 = 14 V
2x + 3y = 70 ...(2) 20. (b) Number of mole atoms of
2x + 2y = 60
24.5
y = 10 O= ¥ 4 = 1 mol atom = NA atoms
Thus volume of C2H4 = 10 mL 98
volume of CH4 = 20 mL 1.6
number of electrons = ¥ 10 ¥ NA electrons
If ratio changed y : x then 16
CH4 + 2O2 h CO2 + 2H2O = NA electrons
y
Mole Concept 1.35
Number of molecules 25. (c) During excess chlorination All Ag Br change into
AgCl.
PV 1 ¥ 11.2 ¥ N A N A
= ¥ NA = = 1 1
RT 0.0821 ¥ 546 4 26. (c) Semimolal = m means mole NaOH in 1000
2 2
NA moles of H = NA moles of P+ gram water
1
4 \ wt of solution = ¥ 40 + 1000 = 1020 gram
Total number of atoms = ¥ 3 ¥ NA = 4 NA atoms 2
3
21. (a) Let molarity of HCl is x and H2SO4 is y w 20
\ %= ¥ 100 = 1.96%
m mole m mole w 1020
27. (c) Volume contraction occur if No of moles of gaseous
x ¥ 25 + 2 y ¥ 25 = 10 ¥ 1
 product less than No of moles of gaseous reactant
m mole of [H + ]
1000 M
28. (c) m =
Applying POAC on Cl Atom 1000d - MM A
20 ¥ x 0.1435 w = wt of solute +wt of solvent
= = 10-3 for very dilute solution wt of solute + wt of solvent
1000 143.5
= wt of solvent.
1 29. (d) No of moles of solute in 1 Kg of solvent indepen-
x= = 0.05 M
20 dent of volume or temp.
8.75 30. (a) S8 h SO3
y= = 0.175 M Apply POAC on S atom
50
22. (c) H4P2O7 + 2 NaOH h Na2 H2 P2 O7 + 2H2O 8 ¥ nS8 = 1 ¥ 20
534 30 ¥ 1023 20 5
\ nS 8 = = moles
178 6 ¥ 1023 8 2
3 Mole 5 Mole 31. (d) CH4 + 2O2 Æ CO2 + 2H2O
(L.R.) 1 mole 10 mole 0 0
LR
5
No of moles of Na2H2P2O7 = moles = 2.5 \ nH 2 O Produced = 2 ¥ 1 = 2 moles
2
2 ¥ 18 g = 36 g = 36 mL.
no. of moles of H2O = 5 Mole
(at 27°C water exist in liquid state)
Total No. of Moles of product = 5 + 2.5 = 7.5
32. (c) Na2 CO3w gram Æ Melt (Do not decompose)
Total No. of molecules of product = 7.5 NA
CaCO3 Æ CaO + CO2
23. (a) P4 + 5 O2 Æ P4O10
0.2 0.2 w w
w gram CaCO3 or mole CaCO3 gives moles CO2
L.R. 100 100
0.2 w
expected No of moles P4O10 = = 0.04 mole nCO2 =
5 100
expected wt of P4O10 = 0.04 ¥ 284 = 11.36 w
actual wt wt of CO2 = ¥ 44 = 0.44 w
% yield = ¥ 100 100
exp ected wt
wt of CO 2
10 \ % loss in wt = ¥ 100
= ¥ 100 = 88.13% wt of reactant taken
11.36
0.44 w
24. (a) 2NaN3(s) h 2Na(s) + 3N2(g) = ¥ 100 = 22%
wt of N2 = Vxd = 368 ¥ 1.12 w+w
368 ¥ 1.12 33. (a) Conceptual
No. of moles of N2 = 112 1
28 34. (b) No of moles of NO2 = = mole
22400 200
2 Ê 368 ¥ 1.12 ˆ 1
\ No. of moles of NaN3 = ¥Á ˜¯ \ wt of NO2 = ¥ 46 g = 0.23
3 Ë 28 200
2 È 368 ¥ 1.12 ˘ wt 0.23
\ wt of NaN3 = ¥ ˙˚ ¥ (23 + 42) gram \ Volume = = = 0.2 mL
3 ÍÎ 28 density 1.15
= 0.638 Kg
No of molecules = n. NA 1 5.6
1 =
= ¥ 6.022 ¥ 1023 50 M mass
200
1 5.6
= 3.01 ¥ 1021 molecules =
50 60 + 160 + 3 z
35. (a) Mol. wt. of adipic acid = 146
220 + 3Z = 280
58.4 g
No. of mole of adipic acid = = 0.4 mole 3Z = 60
146 g Z = 20
 One molecule of adipic acid contains 10 H-atoms. V
\ No. of mole of H-atom in given adipic acid 40. (c) N H2O2 =
5.6
= 0.4 ¥ 10 mole = 4 mole. V = volume of O2 evolved at STP from 1 L H2O2 solu-
wt. of H-atom = 4 g = 4000 mg tion
36. (c) SO3 : C2H6 896
Moles of Cl2 = moles of O2 = = 0.04
16 15 22400
80 : 30 equivalent of H2S = equivalent of HClO3
1 1 = equivalent of Cl2 = nf ◊ N
5 2 = 10 ¥ 0.04 = 0.4
H2S + 8HClO3 h 4Cl2 + H2SO4 + H2O
Mole 2 : 5 1
Atom 8 : 40 No of moles of HClO3 = moles of Cl2
2
\ ratio of No atoms in C2H6 and SO3
40 : 8 fi 5 : 1 1
= ¥ 0.04 = 0.02 moles
37. (c) Given: 2As(s) + 3H2(g) h 2AsH3; DH = – 770 kJ 2
\ Heat of formation of AsH3 0.02 20 1
M= = = M = 0.5 M
- 770 40 ¥ 10 -3
40 2
= = – 385 kJ/mole.
2
31.2
no. of mole of AsH3 given = = 0.4 mole level iii
78
then heat released = 385 ¥ 0.4 = 154 kJ.
1. (a) 2 Mg + O2 h 2MgO
n1RT 5 ¥ R ¥ 300
38. (b) Initial volume = = = 1500 R L 3 Mg + N2 h Mg3N2
P1 1 Mg3N2 + 6H2O h 3Mg (OH)2 + 2NH3
(n1 + n2 ) RT (5 + 2) R ¥ 300 3.4 g
Final volume = =
P2 1.05 Wt of NH3 = 3.4 g
= 2000 R L È1 ˘ È 2 ˘
nNH3 = [nMg ] Í ˙ Í ˙
Change in volume = 2000 R – 1500 R Î3˚ Î 1 ˚
= 500 R 2
= 500 ¥ 0.08 nNH3 = ¥ nMg
3
= 40 L wMg 2 3.4
39. (d) X + 2y + 3z Æxy2z3 ¥ =
24 3 17
10 2 ¥ 1023 wMg = 7.2 gm which converted into 3.4 g NH3
0.6
60 6 ¥ 1023 wt. of Mg left = 24 – 7.2 = 16.8 g
1 1 6 2 mole Mg gives = 2 mole MgO
mole
6 3 100 16.8 16.8
mole Mg give mole MgO
Here Z(L R) because Number of moles/Stoichiometry 24 24
coefficient minimum 16.8
\ wt of MgO = ¥ 40 ¥ 28 g
1 24
\ Moles of XY2 Z3 = Moles of z 2. (b) Factor level method in
3
3 Mg + N2 h Mg3N2
1 6 1
= ¥ = mole Mg3N2 + 6H2O h 3Mg(OH)2 + 2NH3
3 100 50
Mole Concept 1.37
È1 ˘ È3˘ 8, 9, 10.
nMg(OH)2 = [nMg ] Í ˙ Í ˙ 1
Î3˚ Î1 ˚ 2 Mn (OH)2 + O2 + H2 O(l) Æ 2 Mn (OH)3
2
7.2 wMg(OH)2 2
= nMn(OH)3 = no 2
24 58 1/2
wMg(OH)2 2 Mn (OH)3 + 2 KI + 3H2SO4 Æ 2MnSO4 + K2SO4 +
= 17.4 g
7.2 I2 (aq) + 6H2O
3. (b) % Mg = ¥ 100 = 30 %
24 1
nI2 = n
3n + 1 2 Mn(OH )3
4. (b) Cn H 2n + 2 + O 2 h nCO2 + (n + 1) H2O
2 I2 + 2Na2 S2O3 Æ 2 NaI + Na2 S4 O6
x mL
nx mL CO2 gas
3n n 2
Na 2S2O3 = nI2
Cn H 2n + O2 h nCO2 + nH2O 1
12 - x 2
n(12 – x) mL CO2 gas 2 1 4
nNa 2 S2O3 = ¥ ¥ ¥ no 2
Ê 3n + 1ˆ 3n 285 1 2 1
ÁË ˜ x + (12 - x) = ¥ 20 nNa 2S2O3 = 4 ¥ no2
2 ¯ 2 100
Total volume of CO2 = nx + (12 – x)n = 36 In heavily polluted water = 6.4 mg / Liter O2 is present
fi nx + 12x – nx = 36 nNa 2S2O3 = 4 ¥ no2
12n = 36 \ n = 3
3nx + x + 36n – 3nx = 114 6.4
0.01 ¥ V L = 4 ¥
36n + x = 114 ...(1) 1000 ¥ 32
12n = 36 V = 0.08 L = 80 mL
n=3 ...(2) For optimum fit water = 9.6 mg/Liter O2 is present
x = 6 mL 9.6
\ Alkane is C3H8 0.1 ¥ V/L = 4 ¥
1000 ¥ 32
5. (b) C3H8(g) + 5 O2 (g) h 3 CO2 (g) + 4H2O (l) V = 0.012 L = 12 mL
6 mL 30 mL 18 mL 24 mL In order to react with O2 in Stage I solution of Mn+2
9 should be excess
C3H6 (g) + O2 (g) h 3 CO2 (g) + 3H2O (l)
2 11. (a, b)
6 mL 27 mL 18 mL 18 mL (i) NaOH + CH3COOH Æ CH3COONa + H2O
mole fraction of CO2 0.4 ¥ 0.1 0.100 ¥ 0.4
0.04 mole 0.04 mole 0 0
VCO2 36 36 6
= = fi = 0 0 0.04 mole 0.04 mole
VN2 + VCO2 228 + 36 264 44 Salt of weak acid and strong base formed \ basic
6. (b) 1292.5 gram solution of bucket contains W 10 x ¥ 10
(ii) M = % = for NaOH
5 mole NaCl in 1 kg water V MA 40
Let x moles of NaCl and y kg of water is added to buck-
x ¥ 10
et from tap M= for H 2SO 4
x 5+ x 98
= 2, =4 (n f MV) NaOH > (n f MV) H2SO4 \ basic
y 1+ y
fi x = 1 mol. Volume of HCl
(iii) If volume of NaOH < then basic
1 2
y= kg
2 (iv) 40 gram NaOH means 1 mole NaOH and 40 gram
amount of solution finally present 40
= 1292.5 + x ¥ 58.5 + y ¥ 1000 HCl means >1
36.5
= 1292.5 + 58.5 + 500
\ Solution acidic in nature
= 1851
12. (a, b, c)
7. (c) Total wt of NaCl and water added to bucket from
N2 + 3H2 Æ 2NH3
tap = 58.5 + 500 = 558.5 gram
558.5 140 40
Time taken = 1117 sec. 0
0.5 28 2
5 mole 20 mole 0 16. (a, d) Conceptual

0 5 mole 10 mole
17. (a, b, d) 5.3 ¥ 2 N A = 4 ¥ N A
10 ¥ 17 = 170 gram 106 40
Actual wt 5.85 5.6
fi % Yield = 80 = ¥ 100 = NA = ¥ 3 N A π 2 ¥ 0.25 N A
expeted wt 58.5 164
80 w 1 40 4 2
= 18. (a, b) nNa 2SO 4 = ¥ ¥ = = 2 ¥ 10-2
100 30 2 100 40 100
\ w = 24 gram. 1 40 4 40 4
nNH3 = ¥ ¥ ¥2= ¥
fi N2 (L. R) completely consumed in reaction 2 100 40 100 40
50 w 40 4 80
fi = nNH 4Cl = ¥ ¥ = 32 ¥ 10-3
100 170 100 40 100
\ w = 85 gram. 32 ¥ 10-3
13. (b, c) 109% OLEUM by adding 9 gram water in 100 = 1.6 times
2 ¥ 10-2
gram OLEUM it gives 109 gram H2SO4. SO in 500 fi nNaOH > nHCl always in above reaction
500 If % yield 100%
gram OLEUM of water required = ¥ 9 = 45
100 Then nNaOH = nHCl
\ Total wt = 545 gram
\ by adding 100 gram water 545 gram H2SO4 and 55 fi mass of NH4Cl = 32 ¥ 10–3 ¥ 53.5 = 1.712 g.
gram water present in solution 225 ¥ 10-22
19. (a, d) = 3 ¥ 10-22 mole
nH 2SO 4 545 74
M= = L = 0.056 M
VL 98 ¥ 100 = 3 ¥ 10–22 ¥ 6 ¥ 1023
14. (a, b, d) = 180 molecule
(i) 2 CO + O2 Æ 2 CO2 = 2 ¥ 180 Oxygen atom
2a a 0 = 2 ¥ 180 ¥ 16 amu
0 0 2a fi 1.8 ¥ 10–22 ¥ 6.022 ¥ 1023 = 108.396
Vi = 3a Vf = 2a 10
fi = 0.1 mole CaCO3
Dv = 3a – 2a = a 100
a 0.1 mole CaCO3 contains 0.3 gram atom of oxygen
¥ 100 = 33.3% fi 2 ¥ 8 ¥ NA < 5.5 ¥ 3 ¥ NA = 16 NA < 16.5 NA
3a
nRT
(ii) CH4(g) + 2O2(g) Æ CO2(g) + 2H2O(l) 20. (a, d) P =
10 30 V
0 10 10 w RT
P= ¥
Vi = 40 mL V M mass
Vf = 20 mL dRT
Dv 20 P=
\ ¥ 100 = ¥ 100 = 50% M mass
v 40
15. (a, b) C + O2 Æ CO + CO2 P ¥ M mass
=d
POAC on C atom RT
Æ relative density independent of P and T
12
1¥ = 1 ¥ nCO + 1 ¥ nCO2 = a + b (i) M
12 Æ V.D = mass which is independent of P or T
2
POAC on oxygen atom
M of SO3 80
24 Æ mass = = 2.5
2¥ = 1 ¥ a + 2b M mass of O 2 32
32
3 21. (a, c)
= a + 2b (ii) H2 + ½ O2 Æ H2O(l)
2
(ii) – (i) fi 30 25 —
0 10 —
1 1
b = mole and a = mole. Volume contraction = 55 – 10 = 45
2 2 H2 + ½ O2 Æ H2O(l)
fi If mass = Volume means
density = 1 m/mL fi 10 45 0
\ M=m 0 5 —
Mole Concept 1.39
\ volume contraction = 55 – 5 = 50 mL 26. (b, d)

H2 + ½ O2 Æ H2O(l) Mole
fi 40 15 0 (A) Molarity =
Liter
10 0 — In case of very dilute solution
\ Volume contraction 55 – 10 = 45 Volume of solution = Volume of solvent
H2 + ½ O2 Æ H2O(l) molality = mole/kg
fi 35 20 0 1 kg of solvent = 1000 gram
0 2.5 — as density of solvent CCl4 = 1.6 g/mL
55 –2.5 = 52.5 mL 1000
volume contraction 55 – 2.5 = 52.5 mL \ Volume of solvent = ml
1.6
22. (a, b, d) Since Dng = 0 \ V. Density constant.
\ molarity > molality
22400 ml ¥ 1 gm/ml
fi 22.4 L = ¥ 6.02 ¥ 1023 molecules 196
18 (B) ¥ 100% OLEUM
178
4.5 1 178 gm oleum means 80 g SO3 and 98 gm H2SO4
fi in 100 gram OLEUM = mole SO3 Perfect
18 4 80
¥ 100
1 1 1 98
\ in 10 gram OLEUM = ¥ = mole % of combine SO3 =
10 4 40 178
1 (C) 0.0821 L atm K–1 mol–1
= ¥ 80 = 2 gram SO3 0.0821 ¥ 10–3m3 ¥ 760 mm Hg K–1 mol–1
40
0.0821 ¥ 10–3 ¥ 760 Hg m3 mol–1 K–1
V1d1 + V2 d 2 0.0821 ¥ 0.76 Hg m3 mol–1 K–1
fi VSolution =
(d) solution (D) Volume change as Dng π O
\ Volume contraction and volume expansion possible. So vapour density will change
23. (a, b, c, d) A, C are correct
fi Both have NA particle and B D are incorrect
fi NA particle means 1 mole 27. (A - p, q, s); (B - p, q); (C - r)
fi 1 gram atom = Atomic wt in gram = 1 mole (A) A2 Æ B2 Æ 2 AB
fi 1 gm atom have NA atom 4 8 0
0 4 8
6.022 ¥ 1025
24. (b, c, d) ¥ 80 gm = 8 kg 2AB + 2B2 Æ 2AB3
6.022 ¥ 1023 8 4 0
4.8 4 0 4
fi = 0.1 mole
48 (B) A2 + B2 Æ 2AB
= 0.1 NA molecule 2 5 0
= 0.3 NA Oxygen atom 0 3 4
= 0.3 ¥ 6.02 ¥ 1023 = 1.806 ¥ 1023 2AB + 2B2 Æ 2AB3
22.7 4 3 0
fi ¥ 30 gram
22400 1 0 3
(C) A2 + B2 Æ 2AB
51 ¥ 10-3 V
fi = = 67.2 ¥ 10-3 L 2 1 0
17 22.4
1 0 2
2.25 ¥ 10-22 28. (A - p, q, r); (B - p, r); (C - p, r); (D - s)
25. (a, c, d) = 3 ¥ 10-24 mole
74 (A) 1 Mole O2 = 22. 4 Liter at STP
= 3 ¥ 10–22 ¥ 6 ¥ 1023 = 1 ¥ 32 gram
= 1.80 molecule = 1 ¥ NA O2 Molecules
= 2 ¥ 1.80 Oxygen atom (B) 1 Mole SO2 = 22.4 Liter at STP
= 2 ¥ 1.80 ¥ 16 amu = 1 ¥ 64 gram
fi 1.8 ¥ 10–22 ¥ 6.022 ¥ 1023 = 108.396
= 1 ¥ NA SO2 Molecules
10
fi = 0.1 mole CaCO3 contains 0.1 gram atom C (C) 4 gram He = 1 mole
100
= 22.4 Liter at STP
fi 2 ¥ 8 ¥ NA < 5.5 ¥ 3 ¥ NA = 16 NA < 16.5 NA
= NA atom
1 (C) 1 g ion Mg+2 = 1 Mole Mg+2 ion

(D) 1 gram H2 = Mole = 10 ¥ NA electron
2
= 12 ¥ NA Proton
1 = 12 ¥ NA Neutron
= ¥ 22.4 = 11.2 Liter at STP or 12.3
2 L at 1 atm and 300 K = 2 ¥ 1.6 ¥ 10–19 ¥ 6.022 ¥ 1023
1 Coulomb charge
= ¥ NA (H2 Molecule.) (D) 24 g Mg = 1 Mole Mg
2
= 12 NA electron
29. (A - p, r); (B - q, r); (C - p, s); (D - q, r) = 12 NA Proton
Isotope-I = M1 = 12 NA neutron
Isotope-II = M2 31. (A - p, r, s, t); (B - p); (C - p, q, t); (D - q, r)
M avg - M1 0.5 mole CO2 = 0.5 ¥ 22.4 = 11.2 L
% by mole = ¥ 100 = 0.5 ¥ 44 = 22 g
M 2 - M1
= 0.5 ¥ 3NA = 1.5 ¥ 6.022 ¥ 1023 atom
M2 = 0.5 ¥ NA = 3.01 ¥ 1023 Molecule
% by mass = % by mole ¥
M avg
1
( Z ) - ( Z - 1) 1 (B) 2 gram He = Mole = 11.2 Liter at STP
(A) ¥ 100 = ¥ 100 = 33.33% 2
( Z + 2) - ( Z - 1) 3 (C) 0.5 gm molecule O3 = 0.5 mole O3
( Z + 2) = 11.2 L at STP
% by mass = 33.33 ¥ = 0.5 NA Molecule
Z
= 0.5 NA ¥ 3 = 1.5 ¥ 6.02 ¥ 1023 atom
( Z + 2) - ( Z + 1) 1 = 0.5 ¥ 48 g
(B) ¥ 100 = ¥ 100 = 50%
( Z + 3) - ( Z + 1) 2 = 24 g
( Z + 3) 50 Z + 150 4.515 1023
50 ¥ = (D) ¥ = 0.75 mole
( Z + 2) Z +2 6.02 1023
2Z - Z = 0.75 ¥ 32 = 24 gram
(C) ¥ 100
3Z - Z = 0.75 ¥ N A ¥ 2 atom
Z 32. (A - q); (B - q); (C - s); (D - r)
= ¥ 100 = 50
2Z (A) No of oxygen atom = 0.5 ¥ 8 NA = 4 NA
3Z 89.6
= 50 ¥ = 75% (B) No of carbon atom in CH3 radical = = 4 NA
2Z 22.4
( Z ) - ( Z - 1) 192
(D) ¥ 100 (C) No of S atom in 192 gm of SO2 = = 3 NA
( Z + 1) - ( Z - 1) 64
1 (D) No of Cl atom in 15 ¥ 1023 Molecule =
=
¥ 100 = 50
2 15 ¥ 1023
50 ¥ ( Z + 1) ¥ 2 = 5 NA
= 6 ¥ 1023
Z
50 Z + 50 33. (A - p, q, r, t); (B - p, r, t); (C - p, r); (D - s)
=
Z (A) 1 mole of O2 :- Occupies 22.4 lit at 1 atm and 0°C
30. (A - p, q); (B - q); (C - p, q, r, s); (D - q, s) weighs 32 gm.
(A) 1 g ion Na+ = 1 Mole Na+ Contains 2 mole of (O), oxygen atom Collection of
= 10 ¥ NA electron NA units of given substance.
= 11 ¥ NA Proton (B) 1 mole of SO2 :- Weight 64 gm, occupies 22.4 lit at
= 1.6 ¥ 10–19 ¥ 6.022 ¥ 1023 1 atm and 0°C,
coulomb Charge Collection of NA units of given substance.
(C) 4 g of He :- Occupies 22.4 lit at 1 atm and 0°C.
= 12 ¥ NA neutron
Collection of NA units of given substance.
(B) 23 g Na = 1 Mole Na Atom (D) 1 g of H2 :- Occupies 12.3 lit at 1 atm and 300 K.
= 11 ¥ NA electron 34. [Cl2 + 2 KOH Æ KCl + KClO + H2O] ¥ 12
= 11 ¥ NA Proton [3KClO Æ 2KCl + KClO3] ¥ 4
= 12 ¥ NA Neutron 4 KClO3 Æ 3 KClO4 + KCl]
Mole Concept 1.41
12 Cl2 + 24 KOH Æ 3 KClO4 + 21 KCl + 12 H2O ÈÊ 10.48 ˆ ˘ 2

10 22 = ÍÁ ˜¯ ¥ 195 - 410˙ ¥ = 114
Ë
Î 3.9 ˚ 2
3 21
0 2 gives ¥ 10 ¥ 10 10 38. Molar mass of H2SO4 = 98 fi require 80 gram NaOH
12 12
After reaction KOH = 2 for neutralization
KClO4 = 2.5 Molar mass of HCl = 36.5 = require 40 gram Na OH for
KCl = 17.5 neutralisation
H2O = 10 Molar mass of HNO3 = 63 = require 40 gram Na OH
Total = 32.0 mole substance after for neutralisation
Molar mass of H3 PO2 = 3 + 31 + 32 = 66 = require 40
reaction gram Na OH for neutralisation
35. % of C same (40%) for C : H : O fi 1 : 2 : 1 Molar mass of HClO4 = 1 35.5 + 64 = 100.5 = require
O 40 gram NaOH neutralisation
||
C6H12O6 H − C − H and CH3 − C − OH \ minimum volume of NaOH neutralise by HClO4
|| 292
O No of moles of HClO4 = = No of moles of
100.5
V. D of C6H12 O6 = 6 ¥ V. D. of CH2O = 3 ¥ V. D. of NaOH = M.V
CH3CO2H Ê w 10 ˆ
\ in bottle 4 is C6H12O6 (M mass = 180) =Á % V
Ë v M A ˜¯
and in bottle 1 is CH3CO2H (M mass = 60)
292 10
in bottle (2) CH3 COCH3 (M mass = 58) = 20 ¥ ¥V
100.5 40
M mass C6H12O6 > CH3COOH > CH3 CO CH3 > HCHO
292
or V. D. (4) (1) (2) (3) \ V= = 581ml
502.5
M mass
Since V.D = Maximum value of NaOH required if only HCl present
2 in solution
36. If No of moles of Na2CO3 = a mole
292 10
No of moles of Na2SO4 = b mole = 20 ¥ ¥V
No of moles of NaOH = c mole 36.5 40
a ¥ 106 + b ¥ 142 + c ¥ 40 = 1000 gram. 292
V= = 1.6 L = 1600 ml
No of moles of HCl required for neutralisation of mix- 36.5 ¥ 5
511 \ To neatralise mixture or any separate solution VNaOH
ture 2a + c = = 14
36.5 used From 581 mL to 1600 mL
No of moles of BaCl2 = No of moles of BaSO4 \ Ans. 1600 mL
= No of moles of Na2SO4 (b) w
39. 17% means 17 gram AgNO3 in 100 mL
466 466 v
= = = 2 moles
137 + 96 233 in 100 mL solution weight of AgNO3 = 17 gram
106a + 40c = 1000 – 284 = 716 17
\ In 1 mL solution weight of AgNO3
80a + 40c = 14 ¥ 40 = 560 100
156 \ in 3000 mL solution weight of AgNO3
a= =6
26 17
= ¥ 3000 = 510 gram
c = 14 – 12 = 2 100
so wt of NaOH = 2 ¥ 40 = 80 gm 510
No of moles of AgNO3 = = 3 moles
80 170
% of NaOH = ¥ 100 = 8%
1000 3
\ M2 = = 1 M
2nH PtCl
37. B ææææ6 D
Æ nPt
Æ B2 [H 2 PtCl6 ]n ææ 3
w1 gram w2 gram M1V1 = M2V2
(10 48gm) (10 48)
3 ¥ V1 = 1 ¥ 3
POAC on Pt atom V1 = 1 Liter
Èw ˘ n \ VH2O = 3 – 1 = 2 Liter \ ab = 02
M mass of Í 1 ¥ 195 - 410˙ ¥
Î w2 ˚ 2 Mass of Ar = 4a
Mass of etnane = 7a
7a for obtaining maximum mass of E there should be no

reactant after reaction
Mole percentage of ethane 30 ¥ 100
7 a 4a \ 2a ¥ 40 + 3a ¥ 30 + a ¥ 20 = 570
+ 80a + 90a + 20a = 570
30 18
190a = 570
0.233
= ¥ 100 = 51% a=3
0.233 + 0.222 \ nA = 6 mole
Cd = 51 nB = 9 mole
\ abcd = 0251 nC = 3 mole
+ O2 y P gives 4 ¥ 3 mole of D and 2 ¥ 3 moles of E
40. C x H Y O Z N P ææææÆ
combution
xco 2 + H 2O + N 2 \ Mass of D = 12 ¥ 15 = 180 g
2 2
12x + y + 16z + 14P = 61 Mass of A + B + C = mass of (D) + (E) (mass conserva-
Compound (10 mL) on combustion gives 20 mL CO2 tion)
means 570 = 180 + mass of E
\ 10x = 20 mass of E = 390 g
x=2 PV
44. n =
Volume of residual gas N2 = 5 mL RT
P 2 ¥ 44.8 2 ¥ 22.4 ¥ 2
\ ¥ 10 = 5 = = = 2 moles
2 0.821 ¥ 546 0.0821 ¥ 273 ¥ 2
P=1 wt of 2 mole of triatomic gas = 246
Y and Z can not be – Ve or fraction
\ y = 7 and z = 1 246
\ Molar mass = = 123
\ 12 ¥ 2 + 7 + 16 + 14 = 61 M mass 2
\ correct and 2711 123
+O \ Atomic mass = = 41
41. CO æææ
2
Æ CO 2 3
+O 45. 3H2SO4 + Ba3 (PO4)2 Æ 3BaSO4Ø + 2H3PO4
CH 4 æææ 2
Æ CO 2 + H 2O(l) 0.2 ¥ 0.1 0.4 ¥ 0.05
volume of (CO + CH4) = 10 mL Since 1 mol CO gives 0.02 mole 0.02 mole
1 mol CO2 and 1 mol CH4 gives 1 mol CO2 Here H2SO4 L. R
\ Volume of CO2 released = 10 mL 0.02
\ Volume contraction = 10 mL \ remaing moles of Ba3 (PO4)2 = 0.02 –
3
(since all CO2 absorbed by KOH)
42. If No of moles of SO3 or (mass of SO3) Per 100 gram 0.04
= Mole
Oleum or (Per 100 gram H2SO4) high than % Labelling 3
of Oleum high 0.04
(1) In 200 gram H2SO4 wt of SO3 = 100 gram \ No of moles of Ba+2 ion = 3 ¥ = 0.04 Mole
3
\ in 100 gram H2SO4 wt of SO3 = 50 gram
(2) In 80 gram H2SO4 wt of SO3 = 80 gram Volume of solution = 0.1 + 0.4 = 0.5 L
\ In 100 gram H2SO4 wt of SO3 = 100 gram 0.04
\ M= = 0.08M = x
(3) In 5 ¥ 98 = 490 gram H2SO4 wt of SO3 = 5 ¥ 80 = 0.5
400 gram \ 100x = 0.08 ¥ 100 = 8
400 46. C3H6 + NO Æ C3H3N + H2O + N2
\ In 100 gram H2SO4 wt of SO3 = ¥ 100
490 POAC on C atom
= 81.6
(4) In 5 ¥ 98 = 490 gram H2SO4 wt of SO3 = 6 ¥ 80 420 ¥ 103 wt
3¥ =3¥
= 480 42 53
480 \ wt of C3H3N = 530 Kg
In 100 gram H2SO4 wt of SO3 = ¥ 100
490
Ê xˆ x
= 98 gram 47. C4 Hx + ÁË 4 + ˜ O2 Æ 4CO 2 + H 2O
100 > 98 > 81.6 > 50 4¯ 2
Solution code 6 > 2 > 4 > 8 \ correct Ans 8426 Ê xˆ
43. 2A + 3B + CÆ 4D + 2 E
10 ml ÁË 4 + ˜¯ ¥ 10
4
2a moles 3a moles a moles
Mole Concept 1.43
Ê xˆ Previous Years’ Questions

ÁË 4 + ˜ ¥ 10 = 55
4¯ of Jee (Main & advanCed)
x
4+ = 5.5 1. (c) 8 mol O atom present in 1 mol Mg3 (PO4)2.
4
1
x \ 25 mol of ‘O’ atoms are in ¥ 0.25 = 3.125 ¥
= 1.5 –2 8
4 10 mole
x=6 moles of the solute
48. Wt of solution = 1200 g 2. (d) Molality =
mass of the solvent in kg
wt of solute = 12 g Weight of acetic acid = 2.05 ¥ 60 = 123
density solution = 1.2 g/ mL
Weight of solution = 1000 ¥ 1.02 = 1020
1200 \ Weight of water = (1020 – 123) = 897 g
\ Volume of solution = = 1000 mL
1.2 2.05 ¥ 1000
\ Molality = = 2.28 m
No of moles of solute 12/60 897
M= =
volume of solution 1L 3. (d) 2Al(s) + 6HCl (aq) Æ 2Al3+(aq) + 6Cl–(aq) +
1 3H2(g)
x=  6 moles of HCl produces = 3 moles of H2
5
1 = 3 ¥ 22.4 L of H2 at STP
\ 10 x = ¥ 10 = 2
5 3 ¥ 22.4
\ 1 mole of HCl produces = L of H2 at STP
40%
6
49. A æææ
Æ 3B + D = 11.2 L of H2 at STP
100 3 ¥100 ¥ 0 4 1¥100 ¥ 0 4 = 40
WA 100
50% 4. (c) M = ¥
2 B æææ
Æ 4C MA V
4 WA 10
120 ¥ 120 ¥ 0.5 M= ¥ 100 ¥
2 V MA
120 + 40 = 160 W 10 w 10d
%¥ = %
d ¥ 1000 2 ¥ 1000 V MA w MA
50. M = = = 40
50 50 29 ¥ 10 ¥ d
3.6 =
40 Mole in 1 Liter or in 2 kg 98
\ No of moles in 1 kg = 20 mole = m d = 1.21 gm/mL
40 + 20 = 60 5. (c) Titration of oxalic acid by KMnO4 in the presence
51. 5 ¥ x + 2 ¥ 1 = 3 (1 + x) of HCl gives unsatisfactory result because HCl is a bet-
5x – 3x = 1 ter reducing agent than oxalic acid and HCl reduces
1 preferably MnO4– to Mn2+.
x= L
2 6. (c) Mohr’s salt is FeSO4 ◊ (NH4)2SO4 ◊ 6H2O
\ Total volume = 1000 mL + 500 mL = 1500 mL. Only oxidizable part Fe2+ is
52. C2H6 + O2 Æ 2 CO2 + 3H2O [Fe2+ Æ Fe3+ + e–] ¥ 6
x mL C2H6 gives 2x ml CO2 Cr2O72– + 14H+ + 6e– Æ 2Cr3+ + 7H2O
6Fe2+ + Cr2O72– + 14H+ Æ 6Fe3+ + 2Cr3+ + 7H2O
C3H8 + O2 Æ 3CO2 + 4 H2O Millimoles of Fe2+ = 750 ¥ 0.6 = 450
(20 – x) mL C3H8 gives 3(20 – x) mL CO2 450
2x + 60 – 3x = 52 Moles of Fe2+ = = 0.450 mol
1000
x = 8, y = 12 6 mol of Fe react with 1 mol Cr2O72–
2+
8 : 12 = 2: 3 0.450
\ 0.450 mol Fe2+ = = 0.075 mol Cr2O72–
CH4 Æ CO2 + H2O 6
12 mL CH4 gives 12 mL CO2 = 0.075 ¥ 294 g = 22.05 g
C4H10 Æ 4CO2 moles of the solute
7. (a) Molality =
8 mL C4H10 gives 4 ¥ 8 mL CO2 mass of the solvent in kg
\ Vco2 Total = 12 + 32 = 44 mL WB = WH2 = V ◊ d = 0.3 L ¥ 1 = 300 mL ¥ 1 = 300 gram
WA 1000 0.01 1000 14. (c) Total mass of solution = 1000 + 120 = 1120 g
m= ¥ = ¥
M A WB 60 60 1120
Total volume of solution in (L) = ¥ 103
= 5.55 ¥ 10-4 mol kg -1 1.15
8. (d) Total mass of solution = 1000 g water + 120 g urea W 1 120 1.15 ¥ 103
M= ¥ = ¥ = 2.05 M
= 1120 g M V (in L) 60 1120
Density of solution = 1.15 g/mL 15. (c) The least significant figure in titre values is 3.
mass 1120g 25.2 + 25.25 + 25 75.4
Thus, volume of solution = = Average titre value = = = 25.1
density 1.15g/mL 3 3
= 973.91 mL = 0.974 L The number of significant in average titre value will
120 also be 3.
Moles of solute = = 2 mol
60 mass
moles of solute 16. (7) d = fi 10.5 g/cc means in 1 cc
Molarity = V
volume (L) of solution fi 10.5 g of Ag is present
2 mol 10.5
= = 2.05 mol L–1 Number of atoms of Ag in 1 cc fi ¥ NA
0.974 L 108
9. (a) The molarity of a resulting solution is given by 10.5 ¥ N A
In 1 cm number of Ag atom = 3
108
M1V1 + M 2V2
M= 2/3
V1 + V2 Ê 10.5 ˆ
2
In 1 cm , number of atoms of Ag = Á N
750 ¥ 0.5 + 250 ¥ 2 875 Ë 108 A ˜¯
= = = 0.875 M
750 + 250 1000 In 10–12 m2 or 10–8 cm2, number of atoms of Ag
2/3
10. (d) 18 g H2O contains 2 gH Ê 10.5 ˆ
=Á N ¥ 10-8
\ 0.72 g H2O contains 0.08 g H. Ë 108 A ˜¯
44 g CO2 contains 12 g C. 2/3
\ 3.08 g CO2 contains 0.84 g C. Ê 10.5 ¥ 6.022 ¥ 1023 ˆ -8 7
=Á ˜¯ ¥ 10 = 1.5 ¥ 10
0.84 0.08 Ë 108
\C:H= : = 0.07 : 0.08 = 7 : 8 Hence x = 7.
12 1
\ Empirical formula = C7H8 17. (2) BenAl2Si6O18
11. (c) The number of moles is given by (2n) + (3 ¥ 2) + (4 ¥ 6) + (–2 ¥ 18) = 0
or 2n + 30 – 36 = 0
weight (W)
Number of moles = or 2n = 6
molecular weight (M)
or n=3
Thus, ratio of moles of O2 and N2 is given by 18. (2) Na shows only +1
Ê WO2 ˆ F shows only –1
nO2 Á M O2 ˜ Ê WO2 ˆ Ê M N2 ˆ 19. (8) Stock solution of HCl = 29.2 % (w/w)
=Á ˜=
nN2 Á WN2 ˜ ÁË WN ˜¯ ÁË M O ˜¯ M=
WA 1000
¥
2 2
Á ˜ MA V
Ë M N2 ¯
WA 10
Ê 1 ˆ Ê 28 ˆ 7 M= ¥ 100 ¥
= Á ˜ ¥Á ˜ = V MA
Ë 4 ¯ Ë 32 ¯ 32
W 10 w 10d
%¥ = %
Hence, ratio of nO2 and nN2 is 7 : 32 V MA w MA
12. (d) The following reaction occurs:
w 10d
6Fe2+ + Cr2O72– + 14H+ Æ 6Fe3+ + 2Cr3+ + 7H2O Molarity of stock solution of HCl = M = %
From the above equation, we find that Mohr’s salt w MA
(FeSO4 ◊ (NH4)2SO4 ◊ 6H2O) and dichromatic reacts in 29.2 ¥ 10 ¥ 1.25
= = 10
6 : 1 molar ratio. 36.5
13. (b) The atomic mass of iron is If volume of stock solution required = V mL then
(5 ¥ 54) + (90 ¥ 56) + (5 ¥ 57) 10 ¥ V = 0.4 ¥ 200
= = 55.95
100 V = 8 mL
Mole Concept 1.45
R 1
20. (4) = Boltznann constant \ mole of C8H7SO3Na will combine with
N 206
fi R = Boltzann constant ¥ N 1 1 1
6.023 ¥ 1023 ¥ 1.380 ¥ 10–23 = 8.312 ¥ mol Ca 2+ = Ca 2+
2 206 412
It has four significant figures. 22. (d) Given, initial strength of acetic acid = 0.06 N
21. (d) 2C8 H 7SO3 Na + Ca 2+ Æ (C8 H 7SO3 ) 2 Ca + 2Na + Final strength = 0.042 N; Volume given = 50 mL
 2 moles of C8H7SO3Na combines with 1 mol Ca2+ \ Initial millimoles of CH3COOH = 0.06 ¥ 50 = 3
1 Final millimoles of CH3COOH = 0.042 ¥ 50 = 2.1
\ 1 mole of C8H7SO3Na will combine with mol \ Millimoles of CH3COOH adsorbed = 3 – 2.1
Ca2+ 2
= 0.9 mmol
= 0.9 × 60 mg = 54 mg
Chapter
2
Atomic
Structure
Key Concepts
Rutherford Model ________________________
DALTON’S THEORY OF ATOM 1. The atom of an element consist of a small positively
charged nucleus which is situated at the centre of the
Atom was considered as a hard, dense and smallest indivis- atom and carries almost the entire mass of the atom.
ible particle of matter. It cannot be destroyed or created. 2. An electron rotates arround the nucleus. Since very few
a-particles (1 out of 20,000) are returned back it means
Drawbacks ______________________________ the size of the nucleus is very small and is very rigid.
3. The order of diameter of an atom is 10–10 m or 1 Å and
The discovery of various sub. atomic particle e, p, n, x-ray. of the nucleus is 10–15 m = 1 fm.
4. rn = (1.33 ¥ 10–15) A1/3 m. A = mass number rn =
MODELS OF ATOM radius of Nucleus of any element having mass number A.
Failure of Rutherford Model
Thomson’s Model ________________________ 1. According to electromagnetic theory, when a charged
Atom is electrically neutral. It contains positive as well as particle moves with acceleration, they emit energy in
negative charges. According to Thomson, atom is a uniform the form of electromagnetic radiation. According to
sphere of positive charge with electron embedded in it. This Rutherford model electrons are revolving around nu-
was known as plum pudding modle at that time. cleus and emit energy in the form of
electromagnetic radiation. As a re-
sult of which electron loses energy
Rutherford’s Scattering Experiments ________
continuously and should collapse
on nucleus following a spherical
path. Rutherford model failed to
ZnS explain the stability of atom.
2. If electrons loose energy continuously the observed
Au plate spectrum may be continuous but it will consist of well-
defined line of definite frequency. Hence the loss of
energy by the electron is not continuous in an atom.
Result
Calculation of distance between a particle and centre of
1. Most of the a-particle passed through the foil. nucleus:
2. Some of them were deflected through small angles. Total energy at initial point
3. Very few (1 in 20,000) were deflected at large angles
1
(180°). Ti = K.E. + P.E. = mv2 + 0 ...(i)
2
Total energy at final point Types of Spectrum________________________

K ◊ q1q2 1. Emmision spectrum: When any substance absorbs energy
Tf = 0 + ...(ii)
r or radiation, its atoms get excited to higher energy state. After
some time when they return to their original state, they emit
radiation and spectrum. This is called emission spectrum.
i f
M
fi fi Emission
r spectrum
E E
By energy conservation law tio
n
Ti = Tf dia
Ra
q2 = charge on Nucleus of an element
q1 = charge and particle = 2 ¥ 1.6 ¥ 10–19 C 2. Absorption spectrum: When radiation is passed through
m = mass of µ particle = 4 ¥ 1.6 ¥ 10–27 Kg a substance, certain wavelength absorbed and when this
1 2 K ◊ q1q2 outcoming radiation is analysed at the photographic plate we
mn = observe dark line at plane of observed wave length. This is
2 r
2 K ◊ q1q2 called absorption spectrum.
r= It may be continuous, band or line.
mn 2
2 ¥ 9 ¥ 109 ¥ (2 ¥ 1.6 ¥ 10-19 )( Z ¥ 1.6 ¥ 10-19 )
=
4 ¥ 1.6 ¥ 10-27 ◊ n 2 Continous Band Line
Wave: It is a disturbance in medium A A
through which transfer of energy takes
B B
C C
place from one place to other without a D
E
D
E
F
the transfer of matter.
F
G G
Spectrum H H
Parameters: before I I
(i) Wavelength: Distance covered l experiment Absorption spectrum B C E F Spectrum

by the wave in completion of one after
experiment
cycle. Radiation Emitted
(ii) Frequency (n): The number of cycles completed in E1 Vapour radiation
E2
1 sec.
(iii) Time period: Time taken by the wave in one cycle Quantum theory of radiation: According to Max Plank,
1 radiation emitted from hot bodies, radiant energy (light or
completion where T =
n heat) is not emitted continuously but discontinuously in the
1 form of small packets called Quanta. It means atoms or mol-
(iv) Wave No. n =
l ecules emit or absorb the energy in the form of Quanta [E =
Electromagnetic waves do Electric field hn]. They absorb or emit energy as hn, 2hn ... not in the form
not require any medium to of 1/2 hn, 3/2hn, etc., i.e., fraction of Quanta is not possible.
propagate from one place to Wave direction E = hn [h = Plank constant = 6.63 ¥ 10–34 J.S.]
another place. It has two com- and TE = n (hn) n is the number of Quanta of particular
ponents: (i) Electric field and Magnetic field frequency.
(ii) Magnetic field. They are l (in Å) 0.01 1.0 150 3800 7600 6 ¥ 106 3 ¥ 109
perpendicular to one another and to the direction of propaga- Cosmic
g rays x rays uv rays visible Infra Micro Radia
tion. Light is an electromagnetic wave. rays
light red wave wave
When white light is passed through prism it get dispersed
Frequence
into different colours. It is called spectrum of white light. in (Hz)
1017 1057 1014 1011 109
t Bohr’s atomic model

eligh
Whit
R
O
Y
B
G m Ze
I e–
e r
V
Atomic Structure 2.3
1. According to Bohr’s atomic model, e– rotate around

h2 n2 2 n2h2
the nucleus in a circular orbit. The required centripetal r= ¥ and n =
force is provided by electrostatic force of attraction be- 4p 2 mKe2 Z 4p 2 m 2 r 2
tween the electron and nucleus. [6.63 ¥ 10-34 ]2
=
mn 2 Ke ¥ Ze 4 ¥ (3.14) 2 ¥ 9.1 ¥ 10-31 ¥ 9 ¥ 109 ¥ (1.6 ¥ 10-19 ) 2
=
r r2 n2
¥ m/sec.
2. Electrons revolve in those orbit which have angular z
nh
momentum equal to (where n is an integer 1, 2, n2
3,...) 2p r = 0.529 Å
Z
nh Ê n 2 ˆ nh
mnr = mn r = mn ¥ Á 0.529 A∞˜ =
2p Ë z ¯ 2p
3. Each allowed orbit have definite energy. These are
Z
called stationary orbit. Electrons when revolve in v = 2.18 ¥ 106 m/sec.
stationary orbit do not radiate energy. The energy of n
stationary orbit increases as we move farther from the Total energy = K.E. + P.E.
nucleus. KZe 2 1
4. Electrons emits energy only when it transitions from P.E. = - and K.E. = mn 2
r 2
higher energy states to lower energy states.
mn 2 KZe 2
We know = 2
r r
1 2 1 È KZe 2 ˘
\ K.E. = mn = Í
2 2 Î r ˙˚
Humphry series 6
5 1 È KZe 2 ˘ È KZe 2 ˘
Pfund n1 6 \ T.E. = K.E. + P.E. = Í ˙ + Í- ˙
d n2 7, 8 … 2Î r ˚ Î r ˚
Bracket
r are 4
Inf 3
Paschan
Infra Red 1 KZe 2
Infra Red
n1 3 2 T.E. = -
2 r
Balmer
Visible n2 …
1
Lyman n1 2
U.V n2 3, 4 … 1 9 ¥ 109 ¥ (1.6 ¥ 10-19 ) 2 Z
n1 1 =-
n2 2, 3 … 2 n2
0.529 ¥ 10-10
Z
First line a Line [minimum energy line]
1 Ê z2 ˆ
È1 1˘ T.E. = -13.6 Á 2 ˜ ev/atom
= Rz 2 Í 2 - 2 ˙ R = 1.097 ¥ 107 Ën ¯
l n
Î 1 n2˚
Second line b line. Ê z2 ˆ

T.E. = - 313.6 Á 2 ˜ Kcal/mole
Calculation of radius, energy and velocity of e– in nth Ën ¯
Bohr atom
Electrostatic force of attraction provide required centrip- 1 eV = 1.6 ¥ 10–19 joule
etal force Result Species having only one electron system around nu-
cleus in any orbit
K ( Ze)e mn 2 ...(i)
F= = (i) Total Energy = –Kinetic Energy of electron
r2 r (ii) Potential Energy = 2 Total Energy
nh (iii) Ionisation Energy = Kinetic energy = –Total Energy
mn r = ...(ii)
2p
Drawbacks of Bohr’s Model________________
n2h2
\ m 2n 2 r 2 = 1. It explains the spectrum of species having only one
4p 2 electron H atom, He+ ion and Li++ ion. It does not ex-
È n2h2 ˘ plain the spectral of atoms having more than one elec-
\ r=Í 2 2˙ tron.
Î 4p m ¥ KZe ˚
2. When a resolving power spectroscope is used it was È 2p r ˘

observed that the spectral line in H spectrum is not a \ Time taken = Í second
single line but a collection of several lines which are Î V ˙˚
very close to one another. Bohr’s theory does not ex- De Broglie Equation ______________________
plain the fine spectrum of H atom.
According to this theory, small particles like electrons,
3. It does not explain the splitting of spectral lines into a
protons, neutron, a particle, etc., behave as particle nature as
group of finite lines under the influence of magnetic
well as wave nature. The wavelength of particle is given by
field [Zeman effect] and electric field [Stark effect].
Jusitification of quantisation angular momentum. h h
l= =
4. Spectrum of isotope of H was expected to be same by mn P(momentum)
Bohr’s theory but it is different by experiment.
Ionisation energy: Minimum amount of energy which is Proof of Bohr’s Theory by De broglie Relationship
required to eject the electron from the atom from its ground When electrons rotate around nucleus in any orbit, the
state. number of completed wave is equal to the number of orbit.
E• = 0 It means No. of waves = No. of oribtal
\ IE = E• – En = 0 – [En] È h ˘
From nl = 2p r or n Í ˙ = 2p r 1
IE = - En Î mn ˚ 2
n=1 1l = 2p r
Total number of spectral line that can be obtained when nh
electron in nth energy state gets transitioned. n=2 2l = 2p r mn r = 5
2p 3
( Dn)( Dn + 1) proved.
= 4
2 n=5 5l = 2p r
n Some relations:
4 1. Between Momentum (P) and Kinetic Energy (K.E.)
2. Between K.E. and Wave length (l)
3 h h h
l= = =
P 2 KE.m 2q ¥ V ¥ m
for Electron
2
6.625 ¥ 10-34 150
l= = Å
2 ¥ 1.6 ¥ 10 -19
¥ 9.1 ¥ 10 -31
¥V V
1 Since
1 2
K.E. = mn fi 2K.E. = mn2
hc z 2 È 13.6 z 2 ˘ hc 2
DE = En2 - En1 = = 13.6 2 - Í- ˙=
l n2 Î n12 ˚ l fi 2K.E. ◊ m = (mn)2 = (P)
È1 1 ˘ hc 1 13.6 È 1 1˘ \ P = 2KE ◊ m
= 13.6 en Z 2 Í 2 - 2 ˙ = fi = Í n 2 - n 2 ˙ en
n
Î 1 n2˚ l l hc Î 1 2˚ 3. Relation between K.E. and mass of particle for same
1 È1 1˘ value of de broglie wavelength.
= Rh Z 2 Í 2 - 2 ˙ RH = 1.097 ¥ 107 m -1
l n
Î 1 n 2˚
h h2
We know l = \ l2 =
Rh = Rydberg constant 2(KE).m 2KE.m
\ for same l (Wave length)
Frequency of revolution:
Distance travelled in 1 revolution = 2p r 1
r \ KE µ
meter. m
Distance travelled in 2p r meter h 1 mass of e– < Proton < Neutron < a particle
revolution \ for same de-Brogile Wave length order of kinetic
1 energy
\ Distance travelled in 1 metre h revolution e– > Proton > Neutron > a particle
2p r
V
\ Distance travelled in V meter h = Frequency
2p r
Heisenberg Uncertainity Principle __________ Note:

It is impossible to measure both the position and velocity (or 1. Current depends on intensity. i µ I (intensity)
momentum) of a microscopic particle simultaneously with 2. K.E. depends upon frequency and K.E. µ frequency.
absolute accuracy.
According to this theory, product of uncertainity in posi-
tion and uncertainity in momentum is always greater than or Stopping potential: It is the minimum required potential to
h stop moving electrons.
equal .
4p 1
h K.E. = mn2 = hn – W
(Dp) (Dx) ≥ 2
4p = Applied voltage ¥ charge [q ¥ V]
h
Dx ¥ m ◊ DV = V = stopping potential
4p
h I2
Dx ¥ DV =
4p m I1
I2 > I 1
Photoelectric effect: Hertz Light hv
(1887) discovered that when Current
a beam of light of suitable
wavelength falls on a clean e–
metal plate (such as cesium)
in vacuum, electrons are
Vaccum Voltage
emitted from the surface
of the metal plate. This Stopping potential is same.
phenomenon involving G
the emission of electrons
from the surface of a metal by the action of light is known QUANTUM NUMBER
as photoelectric effect. The electrons so emitted are called
photoelectrons. The set of four integers required to define an electron com-
Photon energy = K.E. of e– + threshold energy. pletely in an atom are called quantum number.
K.E. of e– = photon energy – threshold energy. 1. Principle quantum number: It was proposed by Bohr.
It is called orbit, shell or energy level.
1 2 È1 1 ˘ It is denoted by n. value of n is positive integer. It is
mn = hn - hn 0 = hc Í - ˙ = hn - f
2 Î l l0 ˚ denoted by KLMNOP.........
It shows the average distance from the nucleus
n0 = Threshold frequency or critical frequency.
n2
l0 = Threshold wavelength or critical wavelength. r = 0.529 Å.
z
It show the average energy of electron
Experimental Result
1. If n < n0 fi Photoelectric effect does not occur. What z2
E = –13.6 eV.
ever intensity is high. n2
2. If n > n0 fi Photoelectric effect. If intensity Increases num- Maximum number of electron in any orbit is given by
ber of ejected electron Increases and K.E. remain same. 2n2
3. If n Increases then K.E. of ejected e Increases since It has maximum number of subshell = n
K.E. = hn – hn0 Maximum number of orbital = n2.
We know K.E. = hn – hn0 ∫ y = mx – C. 2. Azimuthal quantum number:
It was proposed by Sommer Field.
It is donated by l.
It shows the shape of orbital.
KE Value of l for any value of n 0, 1, 2, 3 ...(n – 1)
l = 0 fi s subshell
tan q h slope l = 1 fi p subshell
v0 q l = 2 fi d subshell
l = 3 fi f subshell
v0
v It has maximum no. of electron In any subshell = 2(2l
hn0 + 1)
Maximum no. of orbital In any subshell = (2l + 1)

l Naming l subshell shape ELECTRONIC RULE
1 0 s 0 s spherical
2 0, 1 sp 1 p dumble Pauli rule: According to this rule, 2 electron in an atom cannot
3 0, 1, 2 spd 2 d double dumble have same set for all four quantum numbers. In other words,
we can say an orbital cannot have more than two electron.
4 0, 1, 2, 3 spdf 3 f complex
Hund’s rule of maximum multiplicity: Electrons are
The value of Azimuthal angular momentum distributed among the orbital of the subshell in such a way
h as to give the maximum number of unpaired electron with
= l (l + 1) = orbital angular moment a parallel spin. Pairing of electrons in the orbitals belonging
2p
3. Magnetic quantum number: to the same subshell does not take place until each orbital
It shows the orientation of electron around nucleus. belonging to that subshell has got one electron each.
It is represented by ‘m’. 3P4
The value of m for any value of l is [–l...0...+ l]
Total number of orbital in any subshell = (2l + 1) 3P3
n 4
Auf bau principle: The electrons are added progresively to
l 0 1 2 3 various subshell in the order of increasing energies starting
with the subshell of the lowest energy.
m 0 1 0 +1 2 1 0 +1+2 3 2 1 0 +1 +2 +3 Or
the order of ascending energy of subshell can be calculated
Spin quantum number:
from (n + l).
It shows the rotation of electron on its self axis.
Lower the value of (n + l) for an subshell having lower
1 1 energy. If two subshell have same the value of (n + l) then
It has value + and - where +ve sign shows a clockwise
2 2 the subshell which has low value of ‘n’ will have low energy.
and –ve sign shows anticlockwise rotation.
Orbital n l n+l
h
Spin angular moment = s ( s + 1)
2p 1s 1 0 1
2s 2 0 2
SHAPE OF ORBITAL
2p 2 1 3
3s 3 0 3
s-orbital
3p 3 1 4
py py 3d 3 2 5
4s 4 0 4
p-orbital px px
pz 4p 4 1 5
z 4d 4 2 6
y z
+
4f 4 3 7
x y x 5s 5 0 5
+
5p 5 1 6
dxy dxz
d-orbital dz2
z y Multiplicity: 2|S| + 1
S = total spin.
2 3
x x for ns np
1 1 1 3
d(x2 S= + + =
dxz y)2
2 2 2 2
3 Probability curve: It was found that wave function y can be

Multiplicity = 2 +1= 4 expressed as a product of two functions.
2
y[r ◊ qf] = R(r) ◊ f(qf)
1s Ø Ø
2s 2p radial angular
3s 3p 3d function function
4p wave function of different Hydrogen orbital
4s 4d 4f
2
5s 5p 4d 5f for 1s = R(r) = 3/2
e–s
a
6s 6p 6d
1
7s 7p for 2s = R(r) = (2 – s) e–s/2
2 2 a03/2
1
for 2p = R(r) = se–s/2
Exchange energy = It is the number of possible transition of 2 6 a03/2
electron in the same subshell.
e–x = Hyperbola curve
fi 4 h2
when a0 = = 0.529 Å
4p mke 2
2
r
fi 3 s=
a0
10
R = wave function
fi 2
r = distance from nucleus
R2 = intensity of wave function
fi 1 Angular node = l
Radial node = n – l – 1
Node and nodal plane: It is the space where probability of
finding electron is zero. The plane where probability of find- Total node in a shell
ing electron is zero is called nodal plane. (n – l – 1) + l = n – 1
Schrödinger Wave Equation _______________ Radial Probability Density _________________

This model is based on particle and wave nature of electrons The square of the radial wave function for an orbital gives the
known as wave mechanical model of an atom. radial probability density of finding an electron at a point at
distance ‘r’ per unit volume.
∂2 x ∂2 y ∂2 z 8p 2 m
+ + + 2 ( E - V )y = 0
∂x 2 ∂y 2 ∂z 2 h
Radial Probability Distributed
h = Plank constant, E = Potential electron Function (4p r2R2) ________________________
V = Potential energy, m = Mass of electron The radial probability density at a radial distance ‘r’ is R2.
y = Wave function Therefore, radial probability of finding the electron in a vol-
Significance of y: The wave function may be regarded as the ume dn will be R2dn.
amplitude of vibration expressed in terms of coordinate x, y, Radial probability is the probability of finding electron in
z. The wave function may have positive or negative values a radial shell between spheres of radius ‘r’ and ‘r + dr’ where
depending on the values of coordinate. dr is small radial distance volume (dn) of spherical shape of
Significance of y2: For electromagnetic radiation, the square thickness ‘dr’.
of amplitude is proportional to the intensity of light. y2 at any r + dr
point is proportional to the probability of finding of electron.
N r dr
Orbital: Region or space where probability of finding
electron is maximum (90 – 95%).
4 4 Total probability distribution = R2 ◊ dn = R2(4p r2dr)

dn = p (r + dr)3 – p r3
3 3 = (4p r2) dr = radical distribution function
4 Zeffective = Z – s
= p [(r + dr)3 – r3]
3 s can be calculated by Slater Rule
= p [(r3 + dr3 + 3r2dr + 3rdr2 – r3] (i) s for 1s or 1s2 = 0.30
Ø Ø (ii) s for ns and ns np electron = [Valance electron – 1] ¥
0.35 + [(n – 1) Shells electron] ¥ 0.85 + [Rest electron
neglect neglect from (n – 1) shell and nucleus] ¥ 1
4 (iii) s for d/f electron = [given d/f electron – 1] ¥ 0.35 +
dn = p [3r2dr], dn = 4p r2dr
3 [Rest electron from given d/f and nucleus] ¥ 1
R10 R2, 0 R3, 0 R2, 1
r r r
r
for (1s) (2s) (3s) (2p)
2 2
R1,0 2
R2,0 2
R3,0 R2,1
r r r r
2 2 2
4pr2R1,0 4pr2R2,0 4pr2R3,0
rmax rmax rmax
(1s) (2s) (3s)
2 2 2
4pr2R2,1 4pr2R3,1 4pr2R3,2
rmax rmax rmax

r
(2p) (3p) (3d)

Comparision between 3s, 3p and 3d.
2 2 2
4pr2R3,0 4pr2R3,1 4pr2R3,2
rmax rmax rmax

r
(3s) (3p) (3d)

Solved Examples
1. Find the ratio of frequencies of violet light (l = 4.10 ¥ 1242

10–5 cm) to that of red light (l = 6.56 ¥ 10–5 cm). Also DE (ev) = = DE (ev)
l (nm)
determine the ratio of energies carried by them.
hc 1242
Sol. We know E = = hn T.E. = eV = 24.84 eV and I.E. = 13.6 eV
l 50(nm)
hc K.E. = T.E. – I.E. = 24.84 – 13.6 = 11.24 eV
C = vl and E = = hn
l 6. Find the longest wavelength of the radiation which is
nv lR E n l required to pickout the electron from the first excited
= = 1:1.6 V = V = R = 1:1.6 = 0.625 : 1 state of Paschan series?
n R lv ER n R lV
Sol. First excited state of Paschan series means n = 4
2. A 100 W power source emits green light at a wave- È1˘ hc
length l = 5000 A. How many photons per minute are \ E4 = –13.6 Í 2 ˙ = –0.85 =
Î4 ˚ l
emitted by the source?
hc 1242
T.E. = P ¥ t = 100 ¥ 60 E• = 0 \ DE = 0.85 = \l= nm
Energy emitted by source (T.E.) = power ¥ time l 0.85
= Number of photon ¥ Energy of one photon 7. The frequency of series limit of Lyman series is n1 and
series, limit of Paschan series is n2, and frequency of
hc 6.63 ¥ 10-34 ¥ 3 ¥ 108 emission of electronic energy from 3 to 1 is n3. Find the
Energy of one photon = =
l 5 ¥ 103 ¥ 10-10 relation between n1, n2 and n3.
\ Number of photons emitted •
T.E. 100 ¥ 60 ¥ 5 ¥ 103 ¥ 10 –10
= =
Energy of one photon 6.63 ¥ 10 –34 ¥ 3 ¥ 108
= 1.5 ¥ 1022 n2
3. Find the ionisation energy of H, He+, Li++.
n1
ÈZ2 ˘ E3 Paschan
Sol. EH = –13.6 Í 2 ˙ ev/atom
În ˚ E2 Balmer
È1˘ n3
E1 = –13.6 Í ˙ = –13.6 eV
Î1˚ E1 Lyman
E• = 0
\ DE = E• – E1 = 13.6 eV for hydrogen atom Sol. E• – E1 = hn1 E• – E3 = hn2
E3 – E1 = hn3
È 13.6[2]2 ˘ + From the figure
= 0 – Í- ˙ = 13.6 ¥ 4 eV for He
Î 1 ˚ hn3 = hn1 – hn2
È13.6[3]2 ˘ n3 = n1 – n2
++ 8. Find the magnitude of the current flowing in fourth
=0– Í ˙ = 13.6 ¥ 9 eV for Li
Î 1 ˚ Bohr orbit in hydrogen atom in one revolution.
4. Find the wavelength of the radiation which is required q e eV
for the very first transition of H atom? Sol. i = = =
T 2p r 2p r
hc
Sol. E2 – E1 = very first transition means n(2) to n(1) V
l È1˘
1 È 13.6 ¥ 1˘ hc hc We know V = 2.18 ¥ 106 Í ˙ and r = 0.529 ¥ 10–10
-13.6 ¥ 2 - Í- = = 10.2 eV = În˚
2 Î 12 ˙
˚ l l [n 2 ]
,n=4
Z
10.2 ¥ 1.6 ¥ 10 -19 1˘
\ l= metre È
6.63 ¥ 10 -34 ¥ 3 ¥ 108 [1.6 ¥ 10-19 ] ¥ Í2.18 ¥ 106 ¥ ˙
\ i= Î 4 ˚ amp.
5. A radiation of wavelength 50 nm incident on H atom -10 È 1 ˘
0.529 ¥ 10 Í 2 ˙
in ground state. Find the kinetic energy of ejected elec- Î4 ˚
tron.
9. A particle having K.E. 5 eV collides with the atom at
hc 6.63 ¥ 10-34 ¥ 3 ¥ 108 ground state. Predict the collision: Elastic or non-elas-
Sol. DE ( joul) = =
l l (meter) tic?
Sol. We know minimum energy 13.6/4 eV For charge Particle

required would be 10.2 eV 10.2 eV KE = Charge ¥ Voltage
for the transition since it is 13.6 eV For electron
only 5 eV. So collission will
6.625 ¥ 10-34
be perfectly elastic. l=
10. A hydrogen-like species is observed to emit six radia- 2 ¥ V ¥ 1.6 ¥ 10-19 ¥ 9.1 ¥ 10-31
tion originating from all possible transition between a
12.27 ¥ 10-10
group of level. These levels have energy between –0.85 = meter
eV to –0.544 eV eV including both level. Find (a) V
Quantum numbers and (b) Atomic number. 12.27 150
= Åª Å
z 2 V V
Sol. En = –13.6 = – 0.85 eV
n2 14. Calculate de broglie wavelength of an electron acceler-
6 radiation means Dn = 3 ated through a potential difference of
z2 n+3 (a) 75 volt (b) 300 volt
E(n+3) = –13.6
(n + 3) 2 n+2
150
= –0.54 Sol. (a) l = Å = 1.414 Å
n+1 V
En (n + 3) 2
=
E( n + 3) ( n) 2 n 150
(b) l = Å = 0.7 Å
n+3 85 300
\ = = 1.25, n = 12
n 54 15. Calculate the uncertainity of position of electron if it is
equal to uncertainity of distance travelled by electron
Z2 in 1 sec.
\ En = –13.6 = – 0.85 Z can be calculated
n2 Sol. Dx = DV (Heisen berg)
11. Calculate the wavelength of photo electron which is h
ejected from ground state of hydrogen atom by absorb- \ (Dx) ◊ (Dx) =
4p m
ing 14 eV photon?
Sol. K.E. = T.E. – I.E. h
\ Dx =
here DE = K.E. = 14 – 13.6 = 0.4 eV 4p m
e– eject from atom if given Total Energy (T.E.) > Ioni- 16. If the velocity of electron in third orbit of He+ ion is ‘x’,
sation Energy (I.E.) calculate the velocity of electron in second orbit of Li+2
6.625 ¥ 10-34 ion.
\ l=
Z
2[0.4 ¥ 1.6 ¥ 10-19 ).9.1 ¥ 10-31 Sol. We know v = 2.18 ¥ 106 m/sec
n
12. Arrange in increasing order K.E. of electron, protons For He+ Z = 2 and n = 3
neutron and a particle.
2
Sol. When All have the same de broglie wavelength. 2.18 ¥ 106 ¥ =x …(i)
\ for same l (Wave length) 3
For He+ z = 2 and n = 3
1 3
\ KE µ 2.18 ¥ 106 ¥ =V …(ii)
m 2
1 Equation (ii)/(i)
K.E. µ for same wavelength
m V 3 3 9
\ = ¥ =
Since order of mass me < mp < mn < ma x 2 2 4
\ Order of Kinetic Energy a < n < P < e 9
v= x
13. Show that de broglie wavelength of electron accelera- 4
1 17. Calculate K.E. and P.E. of electron in third orbit of H
Ê 150 ˆ 2 atom.
tion through V volt is nearly given by l = Á A.
Ë V ˜¯ Sol. We know T.E. = –K.E. and P.E. = 2 ¥ Total Energy
h
Sol. We know for l =
p z 2 -13.6 ¥ 1 -13.6
and T.E. = –13.6 = = = –1.51 eV
h h n2 32 9
\ l= =
2(KE)m 2(q.V )m \ K.E. = 1.51 eV and P.E. = 2 ¥ 1.51 = –3.02 eV
18. Suppose the potential energy between electron and pro- (Electrostatic force of attraction) Provide centripetal
- Ke 2 force
ton at a particular distance r is given by . Use
3r 3 mn 2 K K
Bohr’s theory to obtain energy of such a hypothetical = \ v=
r r m
atom.
Sol. d(U) = F ¥ dr K = mn2
È - Ke 2 ˘ We know
dÍ 3 ˙
dU - Ke 2 È dr -3 ˘ Ke 2 nh
F= = Î 3r ˚ = Í ˙= ¥ 3r -4 mn r =
dr dr 3 Î dr ˚ 3 2p
F = Ke2r–4 = electrostatic force of attraction nh
n=
mn 2 2p mr
and we know F = (from Bohr’s theory)
r K nh
Ke 2 mn 2 =
= ...(i) m 2p mr
r4 r
nh m
1 2 r=
\ K.E. = mn 2p m K
2
1 Ke 2 nh
KE = r=
2 r3 2p Km
nh n2h2 T.E. = K.E. + P.E.

We know mnr = fi m2n2r2 =
2p 4p 2 1 2
2 2 = mn + K ln r
n h 2
fi m(mn2)r2 =
4p 2 1
From (1) = K + K ln r
2
È Ke 2 ˘ n 2 h 2 4p 2 Ke2 m
m Í 3 ˙ r2 = \ È1 ˘
Î r ˚ 4p 2 n2h2 = K Í + ln r ˙
Î2 ˚
1 Ke2 È Ke2 ˘ Ke2
T.E. = K.E. + P.E. = + Í ˙ T.E. = È1 nh ˘
2 r 3 Î 3r 3 ˚ 6r 3 T.E. = K Í + ln
Î 2 2p Km ˙˚
Ke2
= 3 1
È 4p 2 mKe2 ˘ 20. If the ratio of K.E. of ejected photoelectron is when
6Í ˙ K
Î n2 h2 ˚ photo frequency n1 and n2 given. The calculate thresh-
n6 h6 old frequency of metal?
T.E. =
384p 6 K 2e4 m3 We know K.E. = h(v – v0)
19. Suppose P.E. between electron and proton at a separa- Kinetic Energy (K.E.1) = h(v1 – v0) v2 – v0 = K[v1 – v0]
tion ‘r’ is given by u = K ln r. K is a constant. For such a Kinetic Energy (K.E.2) = h(v2 – v0) v2 – v0 = Kv1 – Kv0
hypothetical atom, calculate the radius of nth Bohr orbit
and energy. K.E.1 1 n - n0
= = 1 v0(K – 1) = Kv1 – v2
Sol. u = K ln r K.E.2 K n 2 - n 0
du d [ K ln r ]
F= =
dr dr [kn1 - n 2 ]
\ n0 =
d [ln r ] K (k - 1)
F= = =F
dr r
Exercise
LEVEL I 1 1
(a) 5, 0, 0, + (b) 5, 1, 0, +
2 2
1. The energy of hydrogen atom in its ground state is 1 1
(c) 5, 1, 1, + (d) 6, 0, 0, +
–13.6 eV. The energy of the level corresponding to 2 2
n=5 15. The orbital diagram in which the Aufbau’s principle is
(a) –0.54 eV (b) –5.40 eV violated is
(c) –0.85 eV (d) –2.72 eV 2 s 2 px 2 p y 2 p 2 s 2 px 2 px 2 px
2. The spectrum of He+ is expected to be similar to that (a) ≠Ø ≠Ø ≠ z
(b) ≠ ≠Ø ≠Ø ≠Ø
of -
2s 2 p 2 p 2 p 2s 2 p 2 p 2 p
(a) Li+ (b) He (c) H (d) Na (c) ≠Ø ≠x ≠x ≠x (d) ≠Ø x x z
≠Ø ≠Ø ≠
3. What possibly can be the ratio of the de Broglie wave-
length for two electrons having the same initial energy 16. The total number of neutrons in dipositive zinc ions
and accelerated through 50 volts and 200 volts? with mass number 70 is
(a) 3 : 10 (b) 10 : 3 (c) 1 : 2 (d) 2 : 1 (a) 34 (b) 40 (c) 36 (d) 38
4. The uncertainty in the momentum of an electron is 17. Which of the following sets of quantum numbers repre-
1.0 ¥ 10–5 kg m s–1. The uncertainty of its position will sents an impossible arrangement
be (h = 6.626 ¥ 10–34 kg m2 s–1) n l m s
(a) 1.05 ¥ 10–28 m (b) 1.05 ¥ 10–26 m 1
–30 (a) 3 2 –2
(c) 5.27 ¥ 10 m (d) 5.25 ¥ 10–28 m 2
5. The orbital with zero angular momentum is 1
(a) s (b) p (c) d (d) f (b) 4 0 0
2
6. The electronic configuration of the Mn4+ ion is
(a) 3d44s0 (b) 3d24s1 (c) 3d14s2 (d) 3d34s0 1
(c) 3 2 –3
7. Which of the following ions has the maximum number 2
of unpaired d-electrons? 1
(d) 5 3 0
(a) Zn2+ (b) Fe2+ (c) Ni3+ (d) Cu+ 2
7
8. The total spin resulting from a d configuration is 18. The explanation for the presence of three unpaired
(a) 1 (b) 2 (c) 5/2 (d) 3/2 electrons in the nitrogen atom can be given by
9. Given: K L M N (a) Pauli’s exclusions principle
2 8 11 2 (b) Hund’s rule
The number of electrons present in l = 2 is (c) Aufbau’s principle
(a) 3 (b) 6 (c) 5 (d) 4 (d) Uncertainty principle
10. The value l and m for the last electron in the Cl– ion are 19. The electronic configuration of an element is 1s2 2s2
(a) 1 and 2 (b) 2 and +1 2p6 3s2 3p6 3d5 4s1. This represents its
(c) 3 and –1 (d) 1 and –1 (a) Excited state
11. The maximum energy is present in any electron at (b) Ground state or cationic form
(a) Nucleus (c) Cationic form only
(b) Ground state (d) None of these
(c) First excited state 20. Which of the following has the maximum number of
(d) Infinite distance from the nucleus unpaired electron (atomic number of Fe 26)?
12. Which electronic level would allow the hydrogen atom (a) Fe (b) Fe (II) (c) Fe (III) (d) Fe (IV)
to absorb a photon but not to emit a photon? 21. Which quantum number is not related with Schroding-
(a) 3s (b) 2p (c) 2s (d) 1s er equation?
13. The third line in Balmer series corresponds to an (a) Principal (b) Azimuthal
electronic transition between which Bohr’s orbits in (c) Magnetic (d) Spin
hydrogen? 22. If l0 is the threshold wavelength for photoelectric
(a) 5 Æ 3 (b) 5 Æ 2 (c) 4 Æ 3 (d) 4 Æ 2 emission, l wavelength of light falling on the surface
14. Correct set of four quantum numbers for valence elec- of metal, and m mass of electron, then de Broglie wave-
tron of rubidium (Z = 37) is length of emitted electron is
1 1 influence of electric field (E), magnetic field (B)

È h(ll0 ) ˘ 2 È h ( l0 – l ) ˘ 2 and V is potential difference applied across elec-
(a) Í ˙ (b) Í ˙
Î 2mc(l0 – l ) ˚ Î 2mcll0 ) ˚ trodes.
1 1
31. The quantum numbers of four electrons (e1 to e4) are
È h ( l – l0 ) ˘ 2 hll0 ˘ 2 given below.
(c) Í ˙ (d) ÈÍ ˙
Î 2 mc ll )
0 ˚ Î 2mc ˚ n l m s
23. It is known that atoms contain protons, neutrons and e1 3 0 0 +1/2
electrons. If the mass of neutron is assumed to half of e2 4 0 1 1/2
its original value whereas that of proton is assumed to e3 3 2 2 –1/2
be twice of its original value then the atomic mass of e4 3 1 –1 1/2
14
6C will be
The correct order of decreasing energy of these elec-
(a) Same (b) 25 % more trons is
(c) 14.28 % more (d) 28.5 % less (a) e4 > e3 > e2 > e1 (b) e2 > e3 > e4 > e1
24. The shortest wavelength of He+ in Balmer series is x. (c) e3 > e2 > e4 > e1 (d) none
Then longest wavelength in the Paschene series of Li+2 32. If radius of second stationary orbit (in Bohr’s atom) is
is R. Then radius of third orbit will be
36 x 16 x 9x 5x (a) R/3 (b) 9R (c) R/9 (d) 2.25 R
(a) (b) (c) (d)
5 7 5 9 33. The wavelength associated with a gold weighing 200 g
25. An electron in a hydrogen atom in its ground state ab- and moving at a speed of 5 m/h is of the order
sorbs energy equal to ionisation energy of Li+2. The (a) 10–10 m (b) 10–20 m
wavelength of the emitted electron is (c) 10 m–30
(d) 10–40 m
(a) 3.32 ¥ 10–10 m (b) 1.17 Å 34. If the nitrogen atom had electronic configuration 1s7,
(c) 2.32 ¥ 10–9 nm (d) 3.33 pm it would have energy lower than that of normal ground
26. In compound FeCl2, the orbital angular momentum state configuration 1s2 2s2 2p3, because the electrons
of last electron in its cation and magnetic moment (in would be closer to the nucleus. Yet 1 s7 is not observed
Bohr Magneton) of this compound are
because it violates
(a) ( 6), 35 (b) ( 6), 24 (a) Heisenberg uncertainty principle
(c) 0 (d) None of these (b) Hunds rule
27. An electron, a proton and an alpha particle have kinetic (c) Pauli’s exclusion principle
energy of 16 E, 4E and E respectively. What is the qual- (d) Bohr postulate of stationary orbits
itative order of their de Broglie wavelengths? 35. The total number of electrons in ‘Cu’ atom having
(a) le > lp = la (b) lp = la > le
magnetic quantum number (m = 0) will be
(c) lp > le > la (d) la < le >> lp
(a) 13 (b) 8 (c) 10 (d) 12
28. Given DH for the process Li (g) h Li+3 (g) + 3e– is
19800 kJ/mole and IE1 for Li is 520 then IE2 and IE1 of 36. Find the number of electrons with the value of azi-
Li+ are respectively (approx value) muthal quantum number ‘l’ = 1 for Cd2+.
(a) 11775, 7505 (b) 19280, 520 (a) 18 (b) 20 (c) 22 (d) 24
(c) 11775, 19280 (d) Data insufficient 37. Two bulbs A and B are emitting monochromatic light of
29. The ratio of difference in wavelengths of first and sec- wavelength such that A can just ionise H atoms and B
ond lines of Lyman series in H-like atom to difference in can just ionise He+ ions. If the power of A and B are 30
wavelength for second and third lines of same series is W and 40 W respectively, calculate the ratio of number
(a) 2.5 : 1 (b) 3.5 : 1 (c) 4.5 : 1 (d) 5.5 : 1 of photons emitted per second by bulb A to bulb B.
30. Which of the following statements is INCORRECT? (a) 4 (b) 5 (c) 3 (d) 7
e 38. In a sample of hydrogen atoms, electrons jump from
(a) ratio for canal rays is maximum for hydrogen
m 10th excited state to ground state. If x is the number of
ion. different ultraviolet radiations, y is the number of dif-
e ferent visible radiations and z is the number of different
(b) ratio for cathode rays is independent of the gas
m infrared radiations. The value of z – (x + y) is
taken. [Assume all the Balmer lines lie within visible region.]
(c) The nature of canal rays is dependent on the elec- (a) 17 (b) 18 (c) 19 (d) 36
trode material. 39. A 4pr2 y2 (r) vs r plotted for a H-orbital curve contains
e E2 ‘3’ maxima. If orbital contains 2 angular node then or-
(d) The ratio for electron is expressed as ,
m 2 B 2V bital is
when the cathode rays go undeflected under the (a) 5d (b) 4d (c) 5p (d) 4p
40. In a hydrogen atom, in transition of electron, a photon (a) Angular momentum is an integral multiple of
of energy 2.55 eV is emitted. Then the change in wave- h
.
length of the electron is 2p
(a) 3.32 Å (b) 6.64 Å (b) The electron stationed in the orbit is stable.
(c) 9.97 Å (d) None of these (c) The path of an electron is circular.
41. The ratio of the wavelength of a proton and a-particle (d) The change in the energy levels of electron is con-
will be 1 : 2 if their tinuous.
(a) velocity of proton to velocity of a particle is in the 48. In which orbit of the hydrogen atom is the speed of the
ratio 1 : 8. electron maximum?
(b) velocity of proton to velocity of a particle is in the (a) n = 2 (b) n = 1 (c) n = 3 (d) n = 4
ratio 8 : 1. 49. For an electron, the product vn (velocity ¥ principal
(c) kinetic energy of proton to kinetic energy of a quantum number) will be independent of the
particle is in the ratio 64 : 1. (a) principal quantum number
(d) kinetic energy of proton to kinetic energy of a (b) velocity of the electron
particle is in the ratio 6 : 1. (c) energy of the electron
42. Choose the correct statement. (d) frequency of its revolution
(I) dyz orbital lies in the xz plane. 50. Assume that the potential energy of a hydrogen atom
(II) pz orbital lies along x-axis. in its ground state is zero. Then its energy in the first
(III) Lobes of Px orbital are at 90° with z-axis excited state will be
(IV) Lobes of dxy orbital are at 90° with z-axis. (a) 13.6 eV (b) 27.2 eV
(a) III, IV (b) II, III (c) 23.8 eV (d) 10.2 eV
(c) I, II (d) All of these 51. In an atom, two electrons move around the nucleus in
43. Choose the correct option regarding energy of empty circular orbits of radii R and 4R. The ratio of the time
orbitals. taken by them to complete one revolution is
n l m s (a) 1 : 4 (b) 4 : 1 (c) 1 : 8 (d) 8 : 7
1 52. The wavelength of a spectral line for an electronic tran-
(I) 4 0 0 +
2 sition is inversely related to
1 (a) the number of electrons undergoing the transition.
(II) 3 2 0 - (b) the nuclear charge of the atom.
2
(c) the difference in the energy of the energy levels
1
(III) 3 1 1 + involved in the transition.
2 (d) the velocity of electron undergoing the transition.
1 53. When the electron of a hydrogen atom jumps from
(IV) 3 0 0 -
2 n = 4 to n = 1 state, the number of spectral lines emit-
(a) I > IV (b) II > I ted is
(c) II > III (d) I = III (a) 15 (b) 6 (c) 3 (d) 4
(a) a, b, c (b) b, c 54. When the frequency of light incident on a metallic
(c) b, c, d (d) All of these plate is doubled, the K.E. of the emitted photoelectron
44. Find the product of multiplication of number of elec- will be
trons corresponding to (n + l) = 3 and l = 2 in Cu (29). (a) doubled
(a) 80 (b) 90 (c) 70 (d) 60 (b) halved
45. Which of the following may represent the possible (c) increased but more than doubled of the previous
quantum numbers for the last electron of Ga? K.E.
1 1 (d) Quantum number remains unchanged.
(I) 3, 1, +1, + (II) 4, 0, +1, + 55. The electrons, identified by quantum numbers n and l,
2 2
(i) n = 4, l = 1, (ii) n = 4, l = 0, (iii) n = 3, l = 2, and (iv)
1 1 n = 3, l = 1 can be placed in order of increasing energy,
(III) 4, 1, 0, – (IV) 4, 1, +1, +
2 2 from the lowest to highest, as
(a) III, IV (b) II, III (a) (iv) < (ii) < (iii) < (i) (b) (ii) < (iv) < (i) < (iii)
(c) III, IV (d) All of these (c) (i) < (iii) < (ii) < (iv) (d) (iii) < (i) < (iv) < (ii)
46. For which of the following species, Bohr’s theory is 56. The correct set of four quantum number for the outer-
not applicable? most electrons of rubidium (z = 37) is
(a) Be+3 (b) Li+2 (c) He+2 (d) H 1 1
47. Which of the following postulates does not belong to (a) 5, 0, 0, + (b) 5, 1, 0, +
2 2
Bohr’s model of the atom?
1 1 69. Of the following transitions in hydrogen atom, the one

(c) 5, 1, 1, + (d) 6, 0, 0, + which gives an absorption line of maximum wave-
2 2
length is
57. The number of electrons in sulphur atom having n + l
(a) n = 1 to n = 2 (b) n = 3 to n = 8
= 3 is
(c) n = 2 to n = 1 (d) n = 8 to n = 3
(a) 2 (b) 4 (c) 6 (d) 8
70. Electromagnetic radiation with maximum wavelength
58. The orbital angular momentum of an electron in 2s-
is
orbital is
(a) ultraviolet (b) radiowave
(a) h/4p (b) zero
(c) X-ray (d) infrared
(c) h/2p (d) 2h /2p 71. The wave number of the first line in the Balmer se-
59. Magnetic moments of V(Z = 23), Cr(Z = 24), Mn(Z = ries of hydrogen atom is 15200 cm–1. What is the wave
25) are x, y, z. Hence number of the first line in the Balmer series of Be3+?
(a) x = y = z (b) x < y < z (a) 2.432 ¥ 105 cm–1 (b) 15200 cm–1
–1
(c) x < z < y (d) z y < x (c) 415200 cm (d) 215200 cm–1
60. The radial distribution curve of the orbital with double 72. The wavelength associated with a golf ball weighing
dumbbell shape in the fourth principle shell consists of 200 g and moving at a speed of 5 m/h is of which order
‘n’ nodes, n is (a) 10–10 m (b) 10–20 m
–30
(a) 2 (b) 0 (c) 1 (d) 3 (c) 10 m (d) 10–40 m
61. The increasing order (lowest first) for the values of e/m 73. If the following matter waves travel with equal veloc-
(charge/mass) for electron (e), proton (p), neutron (n) ity, the longest wavelength is that of
and alpha particle (a) is (a) electron (b) proton
(a) e, p, n, a (b) n, p, e, a (c) neutron (d) alpha particle
(c) n, p, a, e (d) n, a, p, e 74. If the velocity of hydrogen molecule is 5 ¥ 104 cm sec–1,
62. The ratio of charge and mass would be greater for then its de Broglie wavelength is
(a) Proton (b) Electron (a) 2 Å (b) 4 Å (c) 8 Å (d) 100 Å
(c) Neutron (d) Alpha 75. Correct set of four quantum numbers for the valence
63. Calcium (Ca) has atomic number 20 and mass number (outermost) electron of Ca
40. Which of the following statements is not correct (a) 4, 0, 0, + 1/2 (b) 5, 1, 0, + 1/2
about Ca atom? (c) 4, 1, 1, + 1/2 (d) 6, 0, 0, + 1/2
(a) The number of protons is same as the number of 76. The quantum numbers of most energetic electron in Ar
neutrons. atom when it is in first excited state is
(b) The number of electrons is same as the number of (a) 2, 1, 0, 1/2 (b) 4, 1, 1, ½
neutrons. (c) 4, 0, 0, 1/2 (d) 4, 1, 0, 1/2
(c) The number of protons is half of the number of 77. The outermost electronic configuration of the most
neutrons. electronegative element is
(d) The number of nucleons is double the number of (a) ns2np3 (b) ns2np4 (c) ns2np5 (d) ns2np6
neutrons. 78. Which of the following orbitals is associated with the
64. The triad of nuclei that is isotonic is angular nodes?
(a) s-orbials (b) p-orbitals
(a) 14 15 17
6 C, 7 N, 9 F (b) 12 14 19
6 C, 7 N, 9 F
(c) d-orbitals (d) f-orbitals
(c) 14 14 17
6 C, 7 N, 9 F (d) 14 14 19
6 C, 7 N, 9 F 79. The energy of the second Bohr orbit in the hydrogen
65. Rutherford’s experiment on scattering of particles atom is –3.41 eV. The energy of the second Bohr orbit
showed for the first time that the atom has of He+ ion would be
(a) electrons (b) protons (a) –0.85 eV (b) –13.64 eV
(c) nucleus (d) neutrons (c) –1.70 eV (d) –6.82 eV
66. The value of Bohr radius of hydrogen atom is 80. The ratio of energy of the electron in ground state of
(a) 0.529 ¥ 10–8 cm (b) 0.529 ¥ 10–10 cm hydrogen to the electron in first excited state of Be+3 is
–12
(c) 0.529 ¥ 10 cm (d) 0.529 ¥ 10–6 cm (a) 4 : 1 (b) 1 : 4 (c) 1 : 8 (d) 8 : 1
67. Ratio of radii of second and first Bohr orbits of H-atom 81. The ratio of the difference in energy of electron be-
is tween the first and second Bohr’s orbit to that between
(a) 2 (b) 4 (c) 3 (d) 5 second and third Bohr’s orbit is
68. The radius of which of the following orbit is same as 1 27 9 4
(a) (b) (c) (d)
that of the first Bohr’s orbit of hydrogen atom 3 5 4 9
(a) He+ (n = 2) (b) Li+2 (n = 2) 82. The first emission line in the atomic spectrum of hy-
2+
(c) Li (n = 3) (d) Be3+ (n = 2) drogen in the Balmer series appears at
9 RH 7 RH 95. If uncertainty in position of an electron was zero, the

(a) cm –1 (b) cm –1 uncertainty in its momentum will be
400 144
h h
3RH 5 RH (a) zero (b) (c) (d) Infinity
(c) cm –1 (d) cm –1 2p 4p
4 36
83. What element has a H-like spectrum and whose lines 96. Which of the following represents the correct set of the
have wavelengths four times shorter than those of four quantum numbers of 4d-electrons?
atomic hydrogen? 1
(a) 4, 3, 2, + (b) 4, 2, 1, 0
(a) He (b) He+ (c) H (d) Li+2 2
84. The second line of Lyman series of H coincides with 1 1
(c) 4, 3, –2, (d) 4, 2, 1, -
the sixth line of Paschen series of an ionic species X. 2 2
Find X assuming R to be same for both H and X? 97. The first emission line in the atomic spectrum of hy-
(a) He+ (b) Li+2 (c) Li+ (d) H drogen in the Balmer Series appears at
85. The work function for a metal is 4 eV. To emit a photo 9 RH 7 RH
electron of zero velocity from the surface of the metal, (a) cm –1 (b) cm –1
400 144
the wavelength of incident light will be
(a) 2700 Å (b) 1700 Å 3RH 5 RH
(c) cm –1 (d) cm –1
(c) 5900 Å (d) 3100 Å 4 36
86. If l1 and l2 denote the de Broglie wavelength of two 98. The fourth line of the Balmer series corresponds to
particles with same masses but charges in the ratio of electron transition between which energy levels
1 : 2 after they are accelerated from rest through the (a) 6 and 2 (b) 5 and 2
same potential difference, then (c) 4 and 1 (d) 5 and 1
(a) l1 = l2 (b) l1 < l2 99. The ionisation potential of hydrogen atom is 13.6 eV.
(c) l1 > l2 (d) None of these The ionisation potential of Be3+ ion is
87. The velocity of electron of H-atom in its ground state is (a) 217.6 eV (b) 109.8 eV
2.2 ¥ 106 m/s. The de Broglie wavelength of this elec- (c) 54.4 eV (d) 136.0 eV
tron will be 100. If 10–17 J of light energy is needed by the interior of
(a) 0.33 nm (b) 23.3 nm human eye to see an object, the photons of green light
(c) 45.6 nm (d) 100 nm (l = 550 nm) needed to see the object are
88. The wavelength associated with a golf ball weighing (a) 27 (b) 28 (c) 29 (d) 30
0.200 g and moving at a speed of 5 m/h is of the order 101. The energy of a photon having wavelength 700 nm is
(a) 10–10 m (b) 10–27 m (a) 1.77 eV (b) 2.47 eV
–30 (c) 700 eV (d) 3.57 eV
(c) 10 m (d) 10–40 m
102. A 1-kW radio transmitter operates at a frequency of
89. An electron in a H-like atom is in an excited state. It
880 Hz. How many photons per second does it emit?
has a total energy of –3.4 eV. Calculate the de Broglie’s
(a) 1.71 ¥ 1021 (b) 1.71 ¥ 1030
wavelength? 23
(c) 6.02 ¥ 10 (d) 2.85 ¥ 1026
(a) 66.5 Å (b) 6.66 Å
103. The ratio of the e/m values of a proton and an a-particle
(c) 60.6 Å (d) 6.06 Å
is
90. Non-directional orbital is
(a) 2 : 1 (b) 1 : 1 (c) 1 : 2 (d) 1 : 4
(a) 3s (b) 4f (c) 4d (d) 4p
104. Which particle among the following will have the
91. The ionisation energy of a hydrogen atom in terms of
smallest de Broglie wavelength, assuming that they
Rydberg constant (RH) is given by the expression have the same velocity?
(a) RHhc (b) RHc (a) A positron (b) A photon
(c) 2RHhc (d) RHhcNA (c) An a-particle (d) A neutron
92. The ratio of the energies of photons of 2000 Å to that of 105. The energy needed to excite a hydrogen atom from its
4000 Å is ground state to its third excited state is
1 1 (a) 12.1 eV (b) 10.2 eV
(a) 2 (b) 4 (c) (d)
2 4 (c) 0.85 eV (d) 12.75 eV
93. For a ‘d’ electron, the orbital angular momentum is 106. The wavelength of the third line of the Balmer series
(a) 6 (b) 2 (c)  (d) 2 for a hydrogen atom is
94. The energy of an electron in the first Bohr orbit of H- 21 100
(a) (b)
atom is –13.6 eV. The possible energy value of the ex- 100R• 21R •
cited state in the Bohr orbit of H-atom is 21R• 100 R•
(a) –4.2 eV (b) –3.4 eV (c) (d)
100 21
(c) –6.8 eV (d) +6.8 eV
107. When the value of the azimuthal quantum number is 119. The energy for an electron is an orbit of hydrogen atom
3, the maximum and the minimum values of the spin 13.6
is given by, En = - 2 Z 2 eV . Calculate the energy of
multiplicities are n
(a) 4, 3 (b) 8, 1 (c) 1, 3 (d) 8, 2 the orbit having a radius 9r1 where r1 is the radius of
108. The energy of an electron in the first Bohr orbit of H- the first orbit?
atom is –13.6 eV. The possible energy value of the 3rd (a) –1.51 eV (b) 10.2 eV
excited state for electron in Bohr orbit of hydrogen is (c) 13.6 eV (d) 1.36 eV
(a) –3.4 eV (b) – 0.85 eV 120. An electron in a Bohr orbit of hydrogen atom with the
(c) – 6.8 eV (d) + 6.8 eV quantum number n2 has an angular momentum 4.2176
109. For the hydrogen atom, the energy of the electron is ¥ 10–34 kg m2 s–1. If electron drops from this level to
defined by the factor En = –13.58/n2 eV. Here n is posi- the next lower level, find the wavelength of this line.
tive integer. The minimum quantity of energy which it
(a) 18.75 ¥ 10–7 m (b) 1.87 ¥ 10–7 m
can absorb in its primitive stage is –7
(c) 187.5 ¥ 10 m (d) 0.187 ¥ 10–7 m
(a) 1.00 eV (b) 3.39 eV
121. The maximum wavelength of light that can excite an
(c) 6.79 eV (d) 10.19 eV
110. The radius of Bohr’s first orbit in hydrogen atom is electron from first to third orbit of hydrogen atom is
0.053 nm. The radius of second orbit in He+ can be (a) 487 nm (b) 170 nm
(a) 0.0265 nm (b) 0.0530 nm (c) 103 nm (d) 17 nm
(c) 0.106 nm (d) 0.2120 nm 122. The work function for a metal is 4 eV. To emit a photo
111. The ratio of the radii of the first three Bohr orbits is electron of zero velocity from the surface of the metal,
(a) 1 : 0.5 : 0.33 (b) 1 : 2 : 3 the wavelength of incident light should be (nearly)
(c) 1 : 4 : 9 (d) 1 : 8 : 27 (a) 2700 Å (b) 1700 Å
112. An electron has wavelength 1 Å. The potential by (c) 5900 Å (d) 3100 Å
which the electron is accelerated will be 123. The total energy of the electron in the hydrogen atom in
(a) 0.0926 V (b) 0.0502 V the ground state is –13.6 eV. The K.E. of this electron is
(c) 0.0826 V (d) 150 V (a) 13.6 eV (b) Zero
113. Atomic number of chromium is 24, then Cr3+ will be (c) –13.6 eV (d) 6.8 eV
(a) diamagnetic (b) paramagnetic 124. Which of the following sets of quantum numbers repre-
(c) ferromagnetic (d) None of these sents the highest energy of an atom?
114. Which of the following arrangement of two electrons 1
in two degenerated orbitals is not possible at all? (a) n = 4, l = 0, m = 0, s = +
2
(a) (b) 1
(b) n = 3, l = 0, m = 0, s = +
2
(c) (d) All 1
(c) n = 3, l = 1, m = 1, s = +
2
115. A compound of vanadium possesses a magnetic mo- 1
ment of 1.73 BM. The oxidation state of vanadium in (d) n = 3, l = 2, m = 1, s = +
2
this compounds is
125. Which option gives the values of the quantum numbers
(a) 1 (b) 2
for the 21st electron of scandium (Z = 21)?
(c) 4 (d) Cannot be predicted
116. Uncertainty in position and momentum are equal. Un- 1 1
(a) 3, 1, 1, + (b) 3, 2, 2, +
certainty in velocity is 2 2
(a) h / p (b) h /2p 1 1
(c) 3, 2, –3, – (d) 3, 1, 2, –
(c) 1/2m h / p (d) None of these 2 2
117. The second line of Lyman series of H coincides with 126. The number of unpaired electrons in Mn4+ (Z = 25) is
the sixth line of Paschen series of an ionic species X. (a) four (b) two (c) five (d) three
Find X assuming Rydberg constant to be same for both 127. The value of the magnetic moment of a particular ion is
H and X? 2.83 Bohr magneton. The ion is
(a) Li+2-ion (b) Li+-ion (a) Fe2+ (b) Ni2+ (c) Mn2+ (d) Co3+
+
(c) He -ion (d) None of these 128. The number of spherical nodes in 3p orbitals is
118. Two particles A and B are in motion. If the wavelengths
(a) one (b) three (c) two (d) zero
associated with particle A is 5 ¥ 10–8 m, calculate the
129. Which of the following electronic configurations have
wavelength of particle B if momentum of B is half of A.
zero spin multiplicity?
(a) 10–8 m (b) 10–7 m (c) 10–5 m (d) 10–3m
140. From the following observations, predict the type of

(a) (b) orbital.
Observation 1: x y plane acts as nodal plane.
Observation 2: The angular function of the orbital in-
(c) (d) none of these
tersect the three axis at origin only.
130. The fraction of volume occupied by the nucleus with Observation 3: R2(r)v/s r curve obtained for the orbital
respect to the total volume of an atom is is
(a) 10–15 (b) 10–5 (c) 10–30 (d) 10–10 R2(r)
131. Which of the following is iso-electronic with neon-
(a) O2– (b) F+ (c) Mg (d) Na
132. The MRI (magnetic resonance imaging) body scanners
used in hospitals operate with 400 MHz radio frequen-
cy energy. The wavelength corresponding to this radio
r
frequency is
(a) 5pz (b) 6dxy (c) 6dx2 – y2 (d) 6 dyz
(a) 0.75 m (b) 0.75 cm (c) 1.5 m (d) 2 cm
133. Radius of Nucleus of atom having Atomic mass = 64 141. Consider the following nuclear reactions involving X
will be and Y:
(a) 5 fm (b) 9 fm X h Y + 42 He
(c) 10 fm (d) 85 fm
Y h 8O18 + 1H1
134. What is likely to be principal quantum number for a
If both neutrons as well as protons in both sides are
circular orbit of diameter 20 nm of the hydrogen atom
conserved in nuclear reaction then identify period num-
if we assume Bohr orbit be the same as that represented
ber of X and moles of neutrons in 4.6 g of X.
by the principal quantum number?
(a) 3, 2.4 NA (b) 3, 2.4
(a) 10 (b) 14 (c) 12 (d) 16
(c) 2, 4.6 (d) 3, 0.2 NA
135. Choose the correct relationship.
142. Electromagnetic radiations having l = 310 Å are sub-
(a) E1 of H = 1/2 E2 of He+ = 1/3 E3 of Li2+ = 1/4 E4
jected to a metal sheet having work function = 12.8
of Be3+
eV. What will be the velocity of photoelectrons with
(b) E1(H) = E2(He+) = E3(Li2+) = E4(Be3+)
maximum kinetic energy.
(c) E1(H) = 2E2(He+) = 3E3(Li2+) = 4E4(Be3+)
(a) 0, no emission will occur
(d) No relation
(b) 2.18 ¥ 106 m/s
136. If the value of E = – 78.4 kcal/mole, the order of the
orbit in hydrogen atom is (c) 2.18 2 ¥ 106 m/s
(a) 4 (b) 3 (c) 2 (d) 1 (d) 8.72 ¥ 106 m/s
137. If velocity of an electron in first orbit of H atom is V, 143. If in Bohr’s model, for unielectronic atom, time period
what will be the velocity of 3rd orbit of Li+2? of revolution is represented as Tn, z where n represents
(a) V (b) V/3 (c) 3 V (d) 9 V shell number and z represents atomic number then the
138. In a certain electronic transition in the hydrogen atoms value of T1, 2 : T2, 1 will be
from an initial state (A) to a final state (B), the differ- (a) 8 : 1 (b) 1 : 8
ence in the orbit radius |r1 – r2| is 624 times the first (c) 1 : 1 (d) None of these
Bohr radius. Identify the transition. 144. Which of the following orbital is non-directional?
(a) 5 Æ 1 (b) 25 Æ 1 (c) 8 Æ 3 (d) 7 Æ 5 (a) s (b) p
139. Match the following: (c) d (d) All of these
(a) Energy of ground state of (i) –6.04 eV 145. Uncertainty in position is twice the uncertainty in mo-
He+ mentum Uncertainty in velocity is
(b) Potential energy of I orbit (ii) –27.2 eV h 1 h
(a) (b)
of H-atom p 2m p
(c) Kinetic energy of II excit- (iii) 8.7 ¥ 10–18 J 1 h
ed state of He+ (c)  (d)
2m 4p
(d) Ionisation potential of He+ (iv) –54.4 eV 146. For which orbital angular probability distribution is
(a) A – (i), B – (ii), C – (iii), D – (iv) maximum at an angle of 45° to the axial direction?
(b) A – (iv), B – (iii), C – (ii), D – (i) (a) dx2 – y2 (b) dz2
(c) A – (iv), B – (ii), C – (i), D – (iii) (c) dxy (d) Px
(d) A – (ii), B – (iii), C – (i), D – (iv) 147. Which orbit will be the first to have ‘g’ subshell?
(a) 3rd (b) 4th (c) 5th (d) 6th
148. Frequency of revolution of e– in shell (II) Ti3+, Cr+, Sc2+ ions are diamagnetic.
4 3 (III) Value of (n + l + m) for last electron of Mg is 3.
pr (IV) The value of Zeff for 3s electron of Cl is 10.9.
2p r
(a) (b) 3 (a) I, IV (b) I, III
V V
(c) III, IV (d) All of these
V qV 6. An element has mass number of 23 and its unipositive
(c) (d)
2p r 2p r ion has electronic configuration 1s2 2s2 2p6. Select the
149. The decreasing order of energy of the 3d, 4s, 3p, 3s correct statement(s).
orbitals is (I) It is isotonic with Mg24.
(a) 3d > 3s > 4s > 3p (b) 3s > 4s > 3p > 3d (II) The ratio of n to l for last electron in atom of above
(c) 3d > 4s > 3p > 3s (d) 4s > 3d > 3s > 3p element is 2.
150. If n and l are respectively the principle and azimuthal (III) Atom of the above element is isoelectronic with
quantum numbers, then the expression for calculating H2O.
the total number of electrons in any orbit is (IV) Atom of the above element is paramagnetic.
l=n l = n -1 (a) I, IV (b) II, III (c) III, IV (d) All
(a) Â 2(2l + 1) (b) Â 2(2l + 1) 7. If the Aufbau principle is not followed and subshells
l =1 l =1 of a shell are progressively filled according to their en-
l = n +1 l = n -1
ergy, which of the following elements is paramagnetic?
(a) Mg (b) Ca (c) Ni (d) Zn
(c) Â 2(2l + 1) (d) Â 2(2l + 1)
8. Find the total number of species having magnetic mo-
l =0 l =0
ment value of 2.84 B.M. from following species:
Fe+2, Cr, Cr3+, Ti2+, Mn2+, V3+
LEVEL II (a) 2 (b) 3 (c) 4 (d) 5
9. Select the correct statement(s).
1. Select the correct statement for Ne. 1
(I) Maximum number of electrons having s = + in
(a) It is not isoelectronic with H2O. 2
sulphur is 9.
(b) Last electron enters in s-orbital.
(II) If electron has zero magnetic quantum number
(c) The value of ‘m’ must be zero for last electron.
then it must be present in s-orbital.
(d) The value of ‘l’ must be ‘1’ for last electron.
(III) All isoelectronic ions have same value of Zeff.
2. Give the correct order of initials True (T) or False (F)
(IV) Number of subshell present in a nth shell is equal to
for the following statements:
‘n’.
(I) Number of electrons having ‘l = 0’ is 10 in Pd.
(a) I, IV (b) II, III
(II) The value of Zeff for 3d electron of Cr and 3d elec-
(c) III, IV (d) All of these
tron of Mn is same as the number of electron in ‘d’
10. Total number of electrons having l = 2 in Fe+2 accord-
subshell of Cr and Mn are same.
ing to Aufbau principle (n + l rule) is
(III) Multiplicity of Fe is equal to Ni+2.
(a) 5 (b) 4 (c) 3 (d) 6
Ê lˆ 11. Similar to quantum number n, l, m a set of new quan-
(IV) Value of ÁË ˜¯ for last electron of element having
n tum numbers was introduced with similar logic but dif-
atomic number 57 is 0.4. ferent values defined as
(a) T T T T (b) F T T T x = 1, 2, 3... all (+ve) integral values
(c) T F T F (d) F F F T y = (x – 1) (x – 2)(x – 3)... No (–ve) value
3. ‘A+2’ is isoelectronic with ‘CO2’ and has (Z+2) neu- z = +(y + 1/2) to – (y + 1/2) in integral steps
tron (Z is atomic number of A), then select the correct For each value of (z), there will be two electrons, if (x + y)
option(s). rule is followed similar to (n + l) rule then number of
(I) Mass number of A+2 is 50. electron in third shell for Zn (Atomic number = 30) is
(II) Last electron enters in ‘s’ orbital in element ‘A’. (a) 12 (b) 13 (c) 14 (d) 15
(III) Number of unpaired electron in ‘A’ is 4. 12. Select the incorrect statement(s) (According to Bohr
(IV) During formation of A+2, electron(s) are removed model).
from ‘s’ as well as ‘d’ subshell. -2p 2 K 2 Z 2e 4 m
(a) I, IV (b) II, III (c) III, IV (d) All (a) Total energy =
n2h2
4. Calculate ‘Q’ for last electron of Ga
where Q = n + l + maximum possible value of ‘m’. n2h2
(b) Radius of orbit =
(a) 6 (b) 8 (c) 7 (d) 5 4p 2 KZe 2 m
5. Which of the following is / are true? 2p KZe 2
(I) Multiplicity in Fe3+ is greater than that in Co3+. (c) Velocity of electron in an orbit =
nh
(d) Frequency of revolution of an electron in an orbit to stop photocurrent completely is 0.24 V. The kinetic
n3 h3 energy of ejected electron is
= (I) 0.24 eV (II) 0.20 eV
4p K 2 Z 2e 4 m
(III) 0.10 eV (IV) 2.4 eV
13. The electrons in a sample of gaseous Li2+ ions which
(a) I, II, III (b) II, III, IV
are initially present in a particular excited state makes
(c) I, III, IV (d) All of these
a transition to a lower level. The emitted photons are
19. The distance of spherical nodes from nucleus for the
absorbed by a sample of H-atoms which are present given orbital are
in their ground state. This sample of H-atoms on de- 3/2
excitation gives maximum 6 different types of spectral 1 ÊZˆ
Y radial = [(s 2 - 4s + 3)] exp(- s /2)
lines. Find the quantum number of initial excited state 9 2 ÁË a0 ˜¯
of Li2+ ions. 2Zr
where a0 and Z are the constants and s = .
(a) 11 (b) 12 (c) 13 (d) 14 a0
14. The radial wave function for 1s electron in H-atom is a0 1 a0
(a) Zero, infinity (b)
,
2 Z 2 Z
R = 3/2 e - r / a0 where a0 = radius of first orbit of H-at-
a0 3 a0 1 a0 a 3 a0
(c) , (d) 0 ,
om. The ratio of probability of 1s electron in hydrogen 2 Z 2 Z Z 2 Z
a 20. The difference in angular momentum associated with
atom at distance a0 from nucleus to that at distance 0 the electron in two successive orbits of hydrogen atoms
from nucleus is 2
is
1 h h h (n - 1)h
(a) equal (b) times (a) (b) (c) (d)
e p 2p 2 2p
4 e 21. The shortest l for the Lyman series of hydrogen atom
(c) times (d) times is … (Given: RH = 109678 cm–1)
e 4
(a) 911.7 Å (b) 700 Å
15. Which of the following has correct the matching of (c) 600 Å (d) 811 Å
curve and orbital? 22. The velocity of an electron in the first Bohr orbit of a
I II III
hydrogen atom is 2.19 ¥ 106 ms–1. Its velocity in the
4pr2Ry2
4pr2Ry2
4pr2Ry2
second orbit would be

(a) 1.10 ¥ 106 ms–1 (b) 4.38 ¥ 106 ms–1
5 –1
r r r (c) 5.5 ¥ 10 ms (d) 8.76 ¥ 106 ms–1
(I) I (2p) II (1s) III (4p) 23. The atomic spectrum of Li+2 – ion arises due to the
(II) I (3p) II (3d) III (3s) transition of an electron from n2 to n1. If n1 + n2 = 4 and
(III) I (4d) II (2p) III (5d) (n2 – n1) = 2, find the wavelength of the third line of
(IV) I (2s) II (4f) III (3d) this series in Li+2-ion.
(a) II, III (b) I, III (c) III, IV (d) All (a) 1.08 nm (b) 10.8 nm
16. If the position of an electron can be determined within (c) 108 nm (d) 1080 nm
±0.0001 Å precision when momentum of electron is 24. If the wavelength is equal to the distance travelled by
h the electron in one second, then
, where a0 is 0.529 Å, find the ratio of minimum h h
2p a0 (a) l = (b) l =
uncertainty in momentum to given momentum. p p
[h = 6.626 ¥ 10–34] h h
(a) 2423 (b) 2645 (c) 2768 (d) 2357 (c) l = (d) l =
p m
17. An unknown particle having double charge as proton
25. According to the Schrodinger model, nature of electron
moves with wavelength l. It is accelerated from the
in an atom is
V (a) Particles only
rest through a potential difference of volts, while
8 (b) Wave only
proton itself moves with same wavelength l when ac- (c) Both simultaneously
celerated from rest through a potential difference ‘V’ (d) Sometimes waves and sometimes particle
volts. The particle is 26. Which of the following describes orbital?
(a) He+ (b) Li2+ ion (c) He2+ (d) Be2+ (a) y (b) y2
18. When photons of wavelength l = 253.7 nm is subjected 2
(c) |y |y (d) All of these
on Cu plate (work function = 4.65 eV) then photoelec- 27. In order to have the same wavelength for the electron
trons are emitted. The magnitude of potential required (mass me) and the neutron (mass mn), their velocities
should be in the ratio (electron velocity/neutron veloc- (a) l1 + l2 + l3 = 0 (b) l3 = l1 + l22

ity) ll
(a) mn/me (b) mn ¥ me (c) me/mn (d) one (c) l3 = l1 + l2 (d) l3 = 1 2
l1 + l2
28. Which of the following is true about y
39. The wavelengths of photons emitted by electron transi-
(a) y represents the probability of finding an electron
tion between two similar levels in H and He+ are l1 and
around the nucleus.
l2 respectively. Then
(b) y represent the amplitude of the electron wave.
(a) l2 = l1 (b) l2 = 2l1
(c) Both A and B
(c) l2 = l1/2 (d) l2 = l1/4
(d) None of these
40. If first ionisation potential of an atom is 16 V, then the
29. Consider an electron in the nth orbit of a hydrogen atom
first excitation potential will be
in the Bohr model. The circumference of the orbit can
(a) 10.2 V (b) 12 V (c) 14 V (d) 16 V
be expressed in terms of the de Broglie wavelength l of
41. In which transition minimum energy is emitted?
the electron as
(a) • Æ 1 (b) 2 Æ 1
(a) (0.529) nl (b) nl (c) 3 Æ 2 (d) n Æ (n – 1) (n ≥ 4)
(c) (13.6) l (d) nl 42. Number of visible lines when an electron returns from
30. A particle X moving with a certain velocity has a de fifth orbit to ground state in H spectrum is
Broglie wavelength of 1A°. If particle Y has a mass of (a) 5 (b) 4 (c) 3 (d) 10
25% that of X and velocity 75% that of X, de Broglie’s
wavelength of Y will be
(a) 3 A° (b) 5.33 A° (c) 6.88 A° (d) 48 A° LEVEL III
31. What are the values of the orbital angular momentum
of an electron in the orbitals 1s, 3s, 3d and 2p? 1.
(a) 0, 0, 6, 2 (b) 1, 1, 4, 2 Column-I Column-II
(c) 0, 1, 6, 3 (d) 0, 0, 20, 6 (A) (p) s-orbital
32. If m = magnetic quantum number and l = azimuthal
y2r
quantum number, then

(a) m = l + 2 (b) m = 2l2 + 1
r
m –1
(c) l = (d) l = 2m + 1
2
33. The number of unpaired electrons in Mn4+ (Z = 25) is (B) (q) p-orbital
(a) Four (b) Two (c) Five (d) Three
r
4pr2y 2
34. After np orbitals are filled, the next orbital filled will be
(a) (n + 1) s (b) (n + 2) p
(c) (n + 1) d (d) (n + 2) s
35. The value of the magnetic moment of a particular ion is r–
2.83 Bohr magneton. The ion is
(a) Fe2+ (b) Ti (c) Mn2+ (d) Co3+ (C) (r) d-orbital
36. In Bohr’s model of the hydrogen atom, the ratio be-
y2 r
tween the period of revolution of an electron in the or-

bit of n = 1 to the period of the revolution of the elec-
tron in the orbit n = 2 is
(a) 1 : 2 (b) 2 : 1 (c) 1 : 4 (d) 1 : 8 r
37. Let u1 be the frequency of the series limit of the Lyman
(D) (s) f-orbital
series, u2 be the frequency of the first line of the Lyman
y2 r
series, and u3 be the frequency of the series limit of the

Balmer series.
(a) u1 – u2 = u3 (b) u2 – u1 = u3
r
(c) u3 = 1/2 (u1 – u3) (d) u1 + u2 = u3
38. The energies of energy levels A, B and C for a given (t) Radial
atom are in the sequence EA < EB < EC. If the radia- probability
tions of wavelengths l1, l2 and l3 are emitted due to distribution
the atomic transitions C to B, B to A and C to A respec- function.
tively then which of the following relations is correct?
(a) (I) P (II) P, Q, R, S, T (III) Q, R, S (IV) P 6.

(b) (I) Q (II) Q, R, S, T (III) P, Q, R, S (IV) P Column-I Column-II
(c) (I) P, R (II) P, Q, R, S (III) Q, R (IV) S (A) Aufbau principle (p) Line spectrum in
(d) (I) P, Q, R (II) Q, S, T (III) P, Q, S (IV) R visible region
2. Matrix matching
(B) de Broglie (q) Orientation of an
Column-I Column-II electron in an orbital
(C) Angular (r) Photon
(A) Lyman series (p) Visible region momentum
(B) Balmer series (q) Infrared region (D) Hund’s rule (s) l = h/mn
(E) Balmer series (t) Electronic
(C) Paschen series (r) Utraviolet region
configuration
(D) Brackett series (s) n2 = 4 to n2 = 3 (F) Planck’s law (u) mvr
(t) n2 = 5 to n2 = 1 7.
Column-I Column-II
3. Matrix matching
(A) Cathode rays (p) Helium nuclei
Column-I Column-II
(B) dumb bell (q) Uncertainty principle
(A) 2p orbital (p) Number of spherical nodes (C) Alpha particles (r) Electromagnetic radiation
=0
(D) Moseley (s) p-orbital
(B) 3d orbital (q) Number of nodal plane = 0
(E) Heisenberg (t) Atomic number
(C) 2s orbital (r) Orbital angular momentum (F) X-ray (u) Electrons
number = 0
8. Frequency = f, Time period = T, Energy of nth orbit =
(D) 4f orbital (s) Azimuthal quantum num-
En, radius of nth orbit = rn, Atomic number = Z, Orbit
ber = 0
number = n:
4. Matrix matching Column-I Column-II
Column-I Column-II (A) f (p) n3
(A) Radius of nth orbit (p) Inversely propor- (B) T (q) Z2
tional to z 1
(C) En (r)
(B) Energy of nth orbit (q) Integral multiple n2
h 1
of (D) (s) Z
2p rn
(C) Velocity of electron (r) Proportional to n2
9.
in the nth orbit
Column-I Column-II
(D) Angular momentum (s) Inversely propor-
of electron tional to n (A) Lyman series (p) Maximum number
of spectral line ob-
(t) Proportional to Z2 served = 6
5. Matrix matching (B) Balmer series (q) Maximum number
of spectral line ob-
Column-I Column-II served = 2
(A) H (p) Radius of 4th orbit 0.53 ¥ 4 Å (C) In a sample 5 Æ 2 (r) Second line has
(B) He+ (q) Energy of second orbit = –13.6 eV 8R
wave number
(C) Be3+ (r) Radius of second orbit = 0.53 ¥ > 9
4Å (D) In a single isolat- (s) Second line has
(D) Li2+ (s) Velocity of electron in the third ed H-atom for 3 3R
wave number
orbit Æ 1 transition 4
(t) Energy of fourth orbit = –13.6 eV (t) Total number of
spectral line is 10
10. Column I and Column II contain data on Schrodinger 15. When electrons make transition to ground state, the
Wave-Mechanical model, where symbols have their largest wavelength (in nm) in the emitted radiations is
usual meanings. Match the columns. [Given : “E” represents energy level in eV]
Column-I Column-II 1240 1240
(a) (b)
(A) (p) 4s | E6 - E5 | | E2 - E1 |
yr
1240 1240
(c) (d)
r | E6 - E1 | | E5 - E4 |
(B) yr24pr2 (q) 5px Passage 3
The magnetic quantum number is denoted by letter m, and for
a given value of l, it can have all the values ranging from –l to
+l including zero of l, m has 2l + 1 values. For example, if l =
(C) Y(q, f ) = K (independent of (r) 3s 2, m can values, i.e., m = –2, –1, 0, +1, +2. This implies that
q and f ) there are five different orientations of the d-subshell. In other
words, d-subshell has five d-orbitals.
(D) atleast one angular node is (s) 6dxy
16. How many electrons can fit into the orbitals that com-
present
prise the third quantum shell n = 3?
(a) 2 (b) 8 (c) 18 (d) 32
Passage 1
17. The maximum number of electron that can be accom-
In an atom, when an electron jumps from higher energy level
modated in f-shell is
to lower energy level, it emits energy in the form of electro-
(a) 2 (b) 8 (c) 18 (d) 14
magnetic radiations. When these electromagnetic radiations
18. Which of the following is correct for 2p-orbitals?
are passed through a prism and received on a photographic
(a) n = 1, l = 2 (b) n = 1, l = 0
film, some lines are observed and those lines are called spec-
(c) n = 2, l = 0 (d) n = 2, l = 1
tral lines.
For hydrogen-like species when jump takes from any ex- Passage 4
cited state to ground state (n = 1), line produced in that case A German physicist gave a principle about the uncertainties
is called a Lyman series line. in simultaneous measurement of position and momentum of
If transition occurs from third or above levels to second small particles. According to that physicist, it is impossible to
level, then corresponding lines produced are called Balmer measure simultaneously the position and momentum of small
lines. particle simultaneously with absolute accuracy or certainty. If
Similarly for next level, it is called Paschen series line. an attempt is made to measure any one of these two quantities
11. In a gaseous sample 3 atoms of a Hydrogen-like spe- with higher accuracy, the other becomes less accurate. The
cies are present and all atoms are in fourth excited state product of the uncertainty in position (Dx) and uncertainty
then calculate the maximum number of different spec- momentum (Dp) is always constant and is equal to or greater
tral lines that can be produced. h
than , where h is Plank’s constant, i.e.,
(a) 10 (b) 7 (c) 12 (d) 8 4p
h
12. If there are 3 atoms of a Hydrogen like specie in second, ( Dx)( Dp ) ≥
third and fourth excited state respectively, then how 4p
many maximum total different Balmer and Paschen 19. Uncertainty in position is twice the uncertainty in mo-
lines can be produced? mentum. Uncertainty velocity is
(a) 2 (b) 3 (c) 4 (d) 5 h 1 h
Passage 2 (a) (b)
p 2m p
Alpha particles capture free moving electrons having wave-
length 0.25 nm and form excited H-like species. In this excit- 1 1 h
(c) h (d)
ed state, electron has circumference 6 times the wavelength 2m 2 2m p
of electron. Bohr’s quantisation rule is applicable. 20. The uncertainty in position of an electron (m = 9.1 ¥
13. The energy of photon emitted in this process will be 10–28 gm) moving with a velocity 3 ¥ 104 cm/s accurate
(a) 20.49 eV (b) 22.49 eV up to 0.001% will be
(c) 25.51 eV (d) 27.51 eV (a) 3.84 cm (b) 1.92 cm
14. What is the number of maximum possible spectral lines (c) 7.68 cm (d) 5.76 cm
obtained in Balmer series, when electron makes transi- 21. If uncertainty in the position of an electron is zero, the
tion to ground state? uncertainty in its momentum would be
(a) 15 (b) 4 (c) 6 (d) 10 (a) zero (b) < h/4p
(c) > h/4p (d) Infinite
Passage 5 1 Ê 1 1ˆ
It is tempting to think that all possible transitions are permis- n= = RH ◊ z 2 Á 2 - 2 ˜ …(i)
l Ë n1 n2 ¯
sible, and that an atomic spectrum arises from the transition
of an electron from any initial orbital to any other orbital. 2p 2 m k 2e 4
where RH = = Rydberg constant for H-atom
However, this is not so, because a photon has an intrinsic h 3c
h where the terms have their usual meanings.
spin angular momentum of 2 corresponding to S =
2p Considering the nuclear motion, the most accurate would
1 although it has no charge and no rest mass. On the other have been to replace mass of electron (m) by the reduced
mass (m) in the above expression, defined as
hand, an electron has two types of angular momentum: or-
m¢ ◊ m
h m=
bital angular momentum, L = l (l + 1) and spin angular m¢ + m
2p
hˆ where mf = mass of nucleus.
Ê
momentum, Ls Á = s ( s + 1) ˜ arising from orbital mo- For Lyman series: n1 = 1 (fixed for all the lines) while n2
Ë 2p ¯
= 2, 3, 4, … infinite for successive lines, i.e., first, second,
tion and spin motion of electron, respecitvely. The change
third … infinite lines, respectively. For Balmer series: n1 = 2
in angular momentum of the electron during any electronic
(fixed for all the lines) while n2 = 3, 4, 5 … infinite for suc-
transition must compensate for the angular momentum car-
cessive lines.
ried away by the photon. To satisfy this condition, the differ-
25. The ratio of the wave numbers for the highest energy
ence between the azimuthal quantum numbers of the orbitals
transition of e– in Lyman and Balmer series of H-atom
within which transition takes place must differ by one. Thus,
is
an electron in a d-orbital (l = 2) cannot make a transition into
(a) 4 : 1 (b) 6 : 1 (c) 9 : 1 (d) 3 : 1
an s-orbital (l = 0) because the photon cannot carry away
26. If proton in H-nucleus be replaced by positron having
enough angular momentum. An electron as is well known,
the same mass as that of proton but same charge as that
possesses four quantum numbers n, l, m and s. Out of these
of proton, then considering the nuclear motion, the
four, l determines the magnitude of orbital angular momen-
wave number of the lowest energy transition of He+ ion
tum (mentioned above) while m determines its Z-component
in Lyman series will be equal to
Ê hˆ (a) 2 RH (b) 3 RH (c) 4 RH (d) RH
as m Á ˜ . The permissible values of only integers from –l
Ë 2p ¯
Passage 7
to +l. While those for l are also integers starting from 0 to (n
The sum of spins of all electrons is the total spin(S) and
– 1). The values of l denotes the subshell. For l = 0, 1, 2, 3,
2S + 1 and is called spin multiplicity of the electronic config-
4… the sub-shells are denoted by the symbols s, p, d, f, g….
uration. Hund’s rule defines the ground state configuration of
respectively.
electrons in degenerate orbitals, i.e., orbitals within the same
22. The maximum orbital angular momentum of an elec-
subshell which have the same values of n and l, states that in
tron with n = 5 is
degenerate orbitals pairing of electrons does not occur unless
h h and until all such orbitals are filled singly with their paral-
(a) 6 (b) 12
2p 2p lel spin. However, degeneracy of orbitals of a given subshell
h h may be destroyed in an inhomogeneous magnetic field like
(c) 42 (d) 20 Octahedral field, tetrahedral field, etc. For example, d-orbital
2p 2p
23. The orbital angular momentum of an electron in p- is five-fold degenerate and degeneracy is destroyed in an ap-
orbital makes an angle of 45° from Z-axis. Hence Z- plied magnetic field provided that it is in homogenous condi-
component of orbital angular momentum of electron is tion. This is called splitting of d-orbital. In an octahedral field
(Oh), splitting of d-orbital takes place such that dxy, and dxz
h Ê hˆ h Ê hˆ
(a) (b) ÁË ˜¯ (c) - (d) - ÁË ˜¯ orbitals (triply degenerate) have lower energy than d x2 - y 2
p 2p p 2p
24. The spin-only magnetic moment of a free ion is 8 and (doubly degenerate) d z 2 which may again split into two
B.M. The spin angular momentum of electron will be levels: d x2 - y 2 and the former having higher energy than the
h h h 3 h latter. The pairing of electron in lower energy may occur if
(a) 2 (b) 8 (c) 6 (d)
2p 2p 2p 4 2p the energy difference between the two level called splitting
Passage 6 energy (D.E.) is greater than the pairing energy, Ep, i.e., the
For a single electron atom or ion, the wave number of radia- increase in energy resulting from interelectronic repulsion
tion emitted during the transition of electron from a higher during pairing so as to yield an electronic configuration of the
energy state (n = n2) to a lower energy state (n = n1) is given lowest possible energy state, i.e., the ground state. This con-
by the expression: dition is met only in the strong magnetic field. In tetrahedral
field (Td), the splitting is just the reverse of the Oh field. A
spinning electron behaves as though it were a tiny bar magnet (a) Statement I is true, Statement II is true; Statement II is
with poles lying on the axis of spin. The magnetic moment of the correct explanation for Statement I.
any atom, ion or molecule due to spin called spin-only mag- (b) Statement I is true, Statement II is true; Statement II is
netic moment (ms) is given by the formula: NOT a correct explanation for statement-I
m s = n(n + 2) B.M where n = number of unpaired (c) Statement I is true, Statement II is false.
electron(s). (d) Statement I is false, Statement II is true.
27. The spin-only magnetic moment of Cr3+ (EC [Ar] 3d3) 35. Statement I: Nodal plane of px atomic orbital in yz
in strong Oh magnetic field is equal to plane.
Statement II: In px, atomic orbital electron density is
(a) 3 B.M (b) 8 B.M zero in the yz plane.
(c) 15 B.M (d) Zero 36. Statement I: No two electrons in an atom can have the
28. The spin-multiplicity of Fe3+ (Ec[Ar]3d5) in its ground same values of four quantum numbers.
state but placed in a strong Oh magnetic field is Statement II: No two electrons in an atom can be si-
(a) 6 (b) 2 (c) 3 (d) 4 multaneously in the same shell, same subshell, same
29. Statement 1: The kinetic energy of an electron is orbitals and have the same spin.
greater than a-particle having same momentum. 37. Statement I: p-orbital has dumb-bell shape.
Statement 2: Mass of a-particle is greater than the Because
mass of electron. Statement II: Electrons present in p-orbital can have
(a) Statements 1 and 2 are true. Statement 2 is the one of three values for ‘m’, i.e., 0, +1, –1
correct explanation for statement 1. 38. Statement I: The ground state configuration of Cr is
(b) Statements 1 and 2 are true. Statement 2 is NOT 3d5 4s1.
the correct explanation for Statement 1. Statement II: A set of exactly half-filled orbitals con-
(c) Statement 1 is true, Statement 2 is false. taining parallel spin arrangement provide extra stabil-
(d) Statement 1 is false, Statement 2 is true. ity.
30. Statement 1: For hydrogen orbital energy increases as 39. Statement I: Mass numbers of the elements may be-
1s < 2s < 2p < 3s < 3p < 3d < 4s < 4p … fractional.
Statement 2: The orbital with lower (n + l) value has Statement II: Mass numbers are obtained by the sum
lesser energy and hence filled up first. of mass of electron and neutron.
31. Statement 1: When two or more empty orbitals of 40. Statement I: Limiting line in the Balmer series has a
equal energy are available. One electron must be placed wavelength of 36.4 mm.
in each until they are all half-filled. Statement II: Limiting lines is obtained for a jump of
Statement 2: The pairing of electron is an unfavour- electron from n = • to n = 2 for Balmer series.
able phenomenon. 41. Statement I: The electronic configuration of nitrogen
32. Statement 1: The Paschen series in the spectrum of atom is represented as
hydrogen lies in the infra-red region.
Statement 2: The Paschen series is born of transition
not as
of electrons onto the second orbit from higher orbits.
33. Statement 1: The principal quantum number, n, can
have whole number values 1, 2, 3, … etc. Statement II: The configuration of ground state of an
Statement 2: The angular momentum quantum num- atom is the one which has the greatest multiplicity.
ber can never be equal to n. 42. Statement I: The configuration of B atom cannot be
34. Question: Is the specie paramagnetic? 1s2 2s3.
Statement 1: The atomic number of specie is 29. Statement II: Hund’s rule demands that the configura-
Statement 2: The charge on the specie is +1. tion should display maximum multiplicity.
(a) Statement (1) alone is sufficient but statement (2) 43. Statement I: 2p orbitals do not have spherical nodes.
is not sufficient. Statement II: The number of spherical nodes in p-or-
(b) Statement (2) alone is sufficient but statement (1) bitals is given by (n – 2).
is not sufficient. 44. Statement I: In Rutherford’s gold foil experiment,
(c) Both statements together are sufficient but neither very few a-particles are deflected back.
statement alone is sufficient. Statement II: Nucleus present inside the atom is
(d) Statements (1) and (2) together are not sufficient. heavy.
45. Statement I: Each electron in an atom either +½ or –½
(Assersion and Reason)
spin quantum number
These questions contains, Statement I (assertion) and State- Statement II: Spin quantum numbers are obtained by
ment II (reason). Bohr’s Theory.
46. Statement I: There are two spherical nodes in 3s-orbit- 58. What is the number of waves made by a Bohr electron
al. in Hydrogen atom in one complete revolution in the
Statement II: There is no angular node in 3s-orbital. third orbit?
47. Choose the correct relation on the basis of Bohr’s 59. The number of nodal plane in dxy orbital.
theory. 60. What is the number of nodes in the radial distribution
1 curve of 2s orbital?
(a) Velocity of electron µ
n 61. Magnetic moment of Mx+ is 24 BM . What is the
Z2 number of unpaired electrons in Mx+?
(b) Frequency of revolution µ 3
n 62. The wave function of an orbital is represented as y420.
(c) Radius of orbit µ n2Z What is the azimuthal quantum number of that orbital?
Z3 63. The number of concentric spherical surfaces for 3s
(d) Force on electron µ 4 orbital at which the probability of finding electron is
n
zero, are
48. A hydrogen - like atom has ground state binding energy
64. What is the number of electrons with l = 2 in the ground
122.4 eV. Then
state of Chromium atom?
(a) its atomic number is 3.
65. What is the value of ‘n’ of the highest excited state that
(b) an electron of 90 eV can excite it to a higher state.
an electron of hydrogen atom in the ground state can
(c) an 80 eV electron cannot excite it to a higher state.
reach when 12.09 eV energy is given to the hydrogen
(d) an electron of 8.2 eV and a photon of 91.8 eV are
atom?
emitted when a 100 eV electron interacts with it.
66. A transition metal cation M+3 has magnetic moment
49. Energy equivalent of 10.00 cm–1 is –
(a) 2 ¥ 10–22 J per photon 35 BM . What is the number of unpaired electrons in
(b) 2.9 ¥ 10–2 kcal mol–1 photon ns orbital of M+3?
(c) 1.2 ¥ 10–1 kJ mol–1 photon (Note: Transition metal exhibit ferromagnetic proper-
(d) 2 ¥ 10–15 ergs per photon ty)
50. Radiation of wavelength 200 Å falls on a platinum sur- 67. The circumference of the second, orbit of electron in
face. If the work function of the metal is 5 eV, which of hydrogen atom is 400 nm, the de Broglie wavelength
the following results are correct about experiment? of electron corresponding to the circumference of same
(a) The velocity of photoelectrons increases with in- orbit is 200 nm. What is the number of waves made by
crease in intensity of radiation. an electron?
(b) Photo-emission of electrons takes place. 68. What is the number of waves made by a Bohr electron
(c) The threshold frequency of the metal is 1.21 ¥ in an orbit of maximum magnetic quantum 3?
1015 sec–1. 69. How many elements does the last electron have the
(d) The velocity of the photo-electrons is 4.48 ¥ quantum numbers of n = 4 and l = 1?
106 m/sec. 70. What is the orbital angular momentum of an electron in
51. Which of the following statement (s) is/are correct? 3s – orbital?
(a) Fe3+ and Mn2+ have equal paramagnetic character. 71. How many d – electrons in Cu+(At.No = 29) can have
(b) Cu2Cl2 and CuCl2 are coloured. Ê 1ˆ
the spin quantum Á - ˜ ?
(c) MnO -4 is purple in colour because of unpair d Ë 2¯
electrons. 72. What is the maximum number of electrons in an atom
(d) The magnetic moment of Fe2+ and Co3+ is equal to that can have the quantum numbers n = 4, me = ±1?
2 6 B.M. 73. What is the number of radial nodes for 3P – orbital?
52. What is the number of waves made by an elelctron 74. How long would it take a radio wave of frequency
moving in an orbit having maximum magnetic quan- 6 ¥ 103 sec–1 to travel from Mars to Earth, a distance
tum number +3? of 8 ¥ 107 km?
53. What is the number of spectral lines produced when an 75. The energy levels of hypothetical one electron atom are
electron jumps from fifth orbit to second orbit in the shown below.
hydrogen atom? 0 eV —— n = •
54. What is the orbital angular momentum of 2s electron? –0.50 eV —— n = 5
h –1.45 eV —— n = 4
55. The angular momentum of an electron is . The –3.08 eV —— n = 3
p
–5.3 eV —— n = 2
Bohr’s orbit in which the electron is revolving is.
–15.6 eV —— n = 1
56. What is the the number of radial nodes of 2p orbital?
(a) Find the ionisation potential of atom?
57. An oil drop has –6.39 ¥ 10–19 Coulomb charge. What is
(b) Find the short wavelength limit of the series ter-
the number of electrons in the oil drop?
minating at n = 2?
(c) Find the wave number of photon emitted for the 89. Estimate the difference in energy between I and II Bohr
transition made by the electron from third orbit to orbit for a hydrogen atom. At what minimum atomic
first orbit? number a transition from n = 2 to n = 1 energy level
(d) Find the minimum energy that an electron will would result in the emission of X-rays with l = 3.0 ¥
have after interacting with this atom in the ground 10–8 m? Which hydrogen-like species does this atomic
state, if the initial kinetic energy of the electron is number correspond to?
(i) 6 eV and (ii) 11 eV? 90. 1.8 g atoms of hydrogen are excited to radiations. The
76. Suppose 10–17 J of light energy is needed by the interior study of spectra indicates that 27% of the atoms are in
of the human eye to see an object. How many photons third energy level and 15% of atoms in second energy
of green light (l = 550 nm) are needed to generate this level and the rest in ground state. If I.P. of H is 21.7 ¥
minimum amount of energy? 10–12 erg. Calculate
77. Find the number of photons of radiation of frequency (i) number of atoms present in third and second en-
5 ¥ 1013 s–1 that must be absorbed in order to melt one ergy level.
g ice when the latent heat of fusion of ice is 330 J/g. (ii) total energy evolved when all the atoms return to
78. The eyes of certain member of the reptile family pass ground state.
a single visual signal to the brain when the visual re- 91. One mole He+ ions are excited. Spectral analysis
ceptors are struck by photons of wavelength 850 nm. showed existence of 50% ions in 3rd orbit, 25% in 2nd
If the total energy of 3.15 ¥ 10–14 J is required to trip and rest in ground state. Calculate total energy evolved
the signal, what is the minimum number of photons when all the ions return to the ground state in terms of
that must strike the receptor? NA and DE.
79. The wavelength of a certain line in the Paschen series 92. The energy of an excited H-atom is –3.4 eV. Calculate
is 1093.6 nm. What is the value of nhigh for this line angular momentum of e–.
[RH = 1.0973 ¥ 10+7 m–1]? 93. The vapours of Hg absorb some electrons accelerated
80. Wavelength of the Balmer Ha line (first line) is 6565 Å. by a potential difference of 4.5 volt. As a result of it,
Calculate the wavelength of Hb (second line). light is emitted. If the full energy of single incident e– is
81. Calculate the Rydberg constant R if He+ ions are known to be converted into light emitted by single Hg atom,
to have the wavelength difference between the first (of find the wave number of the light.
the longest wavelength) lines of Balmer and Lyman se- 94. The hydrogen atom in the ground state is excited by
ries equal to 133.7 nm. means of monochromatic radiation of wavelength x A0.
82. Calculate the energy emitted when electrons of 1.0 g The resulting spectrum consists of 15 different lines.
atom of hydrogen undergo transition giving the spec- Calculate the value of x.
tral line of lowest energy in the visible region of its 95. A plot of P(r) of 1s electron of H-atom versus distance
atomic spectrum. from the nucleus (r) is shown in the figure given below.
83. A photon having l = 854 Å causes ionisation of a nitro- Find the value of r corresponding to the maximum in
gen atom. Give the I.E. per mole of nitrogen in KJ. terms of a0 where the maximum occurs.
84. Calculate energy of electron which is moving in the or- Given:
bit that has its radius, 16 times the radius of first Bohr Ê 1 ˆ
1/2
orbit for H-atom. P(r ) = 4p r 2y 2 y 1s (for H-atom) = Á 3 ˜ e – r / a0

Ë p a0 ¯
85. The electron energy in hydrogen atom is given by
– 21.7 ¥ 10 –12
En = ergs. Calculate the energy required
n2 P(r)
–
to remove an e completely from n = 2 orbit. What is r
the largest wavelength in cm of light that can be used
96. Absorption of energy by an atom of hydrogen in the
to cause this transition?
ground state results in the ejection of electron with
86. Calculate the wavelength in angstrom of photon that
de-Broglie wavelength l = 4.7 ¥ 10–10 m. Given that
is emitted when an e– in Bohr orbit n = 2 returns to the
the ionisation energy is 13.6 eV, calculate the energy of
orbit n = 1. The ionisation potential of the ground state
photon which caused the ejection of electron.
of hydrogen atom is 2.17 ¥ 10–11 erg/atom.
97. Photo-chemical dissociation of oxygen results in the
87. The velocity of e– in a certain Bohr orbit of the hydro-
production of two oxygen atoms, one in the ground
gen atom bears the ratio of 1 : 275 to the velocity of
state and one in the excited state.
light. What is the quantum number “n” of the orbit.
hn
88. A doubly ionised lithium atom is hydrogen like with O 2 ææÆ O + O *
atomic number Z = 3. Find the wavelength of the radia- The maximum wavelength needed for this is 174 nm.
tion required to excite the electron in Li2+ from the first If the excitation energy O Æ O* is 3.15 ¥ 10–19J. How
to the third Bohr orbit.
much energy in kJ/mole is needed for the dissociation weight of natural boron is 10.81. Calculate the percent-
of one mole of oxygen into normal atoms in ground age of each isotope in natural boron. [IIT-JEE 1978]
state? 8. The energy of the electron in the second and the third
98. If the average lifetime of an excited state of H atom Bohr’s orbits of the hydrogen atom is –5.42 ¥ 10–12 erg
is of order 10–8 sec, estimate how many orbits an e– and –2.41 ¥ 10–12 erg respectively. Calculate the wave-
makes when it is in the state n = 2 and before it suffers length of the emitted radiation when the electron drops
a transition to n = 1 state. from the third to the second orbit. [IIT-JEE 1981]
99. Calculate the frequency of e– in the first Bohr orbit in a 9. Calculate the wavelength in Angstroms of the pho-
H-atom. ton that is emitted when an electron in the Bohr orbit,
100. A single electron orbits around a stationary nucleus of n = 2 returns to the orbit, n = 1 in the hydrogen atom.
charge +Ze where Z is a constant from the nucleus and The ionisation potential of the ground state hydrogen
atom is 2.17 ¥ 10–11 erg per atom. [IIT-JEE 1982]
e is the magnitude of the electric charge. The hydro-
10. The electron energy in hydrogen atom is given by
gen like species required 47.2 eV to excite the electron
E = (–21.7 ¥ 10–12)/n2 ergs. (a) Calculate the energy
from the second Bohr orbit to the third Bohr orbit. Find
required to remove an electron completely from the
the value of Z give the hydrogen like species formed.
n = 2 orbit. What is the longest wavelength (in cm) of
101. A stationary He+ ion emitted a photon corresponding to light that can be used to cause this transition?
a first line of the Lyman series. The photon liberated a [IIT-JEE 1984]
photoelectron from a stationary H atom in ground state. 11. What is the maximum number of electrons that my be
What is the velocity of photoelectron ? present in all the atomic orbitals with principle quan-
102. Calculate the threshold frequency of metal if the bind- tum number 3 and azimuthal quantum number 2?
ing energy is 180.69 kJ mol–1 of electron. [IIT-JEE 1985]
103. Calculate the binding energy per mole when threshold 12. According to Bohr’s theory, the electronic energy
wavelength of photon is 240 nm. of hydrogen atom in the nth Bohr’s orbit is given by
– 21.76 ¥ 10 –19
En = J . Calculate the longest wave-
PREVIOUS YEARS’ QUESTIONS n2
OF JEE (MAIN & ADVANCED) length of light that will be needed to remove an elec-
1. The increasing order (lowest first) for the values of e/m tron from the third Bohr orbit of the He+ ion.
(charge/mass) for electron (e), proton (p), neutron (n) [IIT-JEE 1990]
and alpha particle (a) is [IIT-JEE 1984] 13. A ball of mass 100 g is moving with 100 ms–1. Find its
(a) e, p, n,a (b) n, p, e,a wavelength. [IIT-JEE 2004]
(c) n, p,a, e (d) n, a, p, e 14. Find the velocity (ms–1) of electron in first Bohr’s orbit
2. The triad of nuclei that is isotonic is [IIT-JEE 1988] of radius a0. Also find the de Broglie’s wavelength (in
14 15 17 12 14 19
m). Find the orbital angular momentum of 2p orbital of
(a) 6 C, 7 N, 9 F (b) 6 C, 7 N, 9 F hydrogen atom in units of h/2p. [IIT-JEE 2005]
(c) 14 14 17
(d) 14 14 19 15. Estimate the difference in energy between first and sec-
6 C, 7 N, 9 F 6 C, 7 N, 9 F
ond Bohr orbit for a hydrogen atom. At what minimum
3. Rutherford’s experiment on scattering of particles
atomic number, a transition from n = 2 to n = 1 energy
showed for the first time that the atom has
level would result in the emission of X-rays with = 3.0
[IIT-JEE 1981]
¥ 10–8 m? Which hydrogen atom-like species does this
(a) electrons (b) protons
atomic number correspond to? [IIT-JEE 1993]
(c) nucleus (d) neutrons
16. What transition in the hydrogen spectrum would have
4. The wavelength associated with a golf ball weighing
the same wavelength as the Balmer transition n = 4 to n
200 g and moving at a speed of 5 m/h is of the order
= 2 of He+ spectrum? [IIT-JEE 1993]
[IIT-JEE 2000]
17. Find out the number of waves made by a Bohr electron
(a) 10–10m (b) 10–20 m (c) 10–30m (d) 10–40m
in one complete revolution in its third orbit.
5. Correct set of four quantum numbers for the valence
[IIT-JEE 1994]
(outermost) electron of rubidium (Z = 37) is
18. Iodine molecule dissociates into after absorbing light
[IIT-JEE 1984]
of 4500 Å. If one quantum of radiation is absorbed by
(a) 5, 0, 0, + ½ (b) 5, 1, 0, + ½
each molecule, calculate the kinetic energy of iodine
(c) 5, 1, 1, + ½ (d) 6, 0, 0, + ½
atoms. (Bond energy of I2 = 240 kJ mol–1.)
6. The outermost electronic configuration of the most
[IIT-JEE 1995]
electronegative element is [IIT-JEE 1988]
19. Calculate the wave number for the shortest wavelength
(a) ns2np3 (b) ns2np4 (c) ns2np5 (d) ns2np6
transition in the Balmer series of atomic hydrogen.
7. Naturally occurring boron consists of two isotopes
[IIT-JEE 1996]
whose atomic weights are 10.01 and 11.01. The atomic
20. With what velocity should an a-particle travel towards (D) Probability density (s) Electron spin
the nucleus of a copper atom so as to arrive at a dis- of electron at the quantum number
tance 10–13 metre from the nucleus of a copper atom? nucleus in hydro-
[IIT-JEE 1997] gen – like atom
21. An electron beam can undergo diffraction by crystals.
Through what potential should a beam of electrons be
accelerated so that its wavelength becomes equal to Comprehension-Based Questions
1.54 Å? [IIT-JEE 1997] The hydrogen- like species Li2+ is in a spherically symmetric
22. Calculate the energy required to excite one litre of hy- state S1 with one radial node. Upon absorbing light, the ion
drogen gas at 1 atm and 298 K to the first excited state undergoes transition to a state S2. The state S2 has one radial
of atomic hydrogen. The energy for the dissociation of node and its energy is equal to the ground state energy of the
H-H bond is 436 kJ mol–1. [IIT-JEE 2000] hydrogen atom.
23. Wavelength of high energy transition of H-atoms is 27. The state S1 is (2010)
91.2 nm. Calculate the corresponding wavelength of (a) 1s (b) 2s (c) 2p (d) 3s
He atoms. [IIT-JEE 2003] 28. Energy of the state S1 in units of the hydrogen atom
24. The Schrodinger wave equation for hydrogen atom is ground state energy is (2010)
[IIT-JEE 2004] (a) 0.75 (b) 1.50 (c) 2.25 (d) 4.50
1 Ê 1ˆ
3/2
Ê r0 ˆ – r0 / a0 29. The orbital angular momentum quantum number of the
Y2s =
4 2p ÁË a0 ˜¯ ÁË 2 – a ˜¯ e state S2 is (2010)
0
(a) 0 (b) 1 (c) 2 (d) 3
where a0 is Bohr’s radius. If the radial node in 2s be at
r0, find r0 in terms of a0. Integer-Type Questions
25. Match the columns according the Boh’s theory. 30. The maximum number of electrons that can have prin-
En = Total energy cipal quantum number, n = 3 and spin quantum num-
Kn = Kinetic energy 1
ber, ms = - , is (2011)
Vn = Potential energy 2
rn = Radius of nth orbit (2006, 6M) 31. Which of the following is the energy of a possible ex-
cited state of hydrogen? [2015 Main]
Column I Column II (a) +13.6 eV (b) –6.8 eV
(A) Vn/Kn = ? (p) 0 (c) –3.4 eV (d) +6.8 eV
(B) x (q) –1 32. The correct set of four quantum numbers for the va-
If radius of nth orbit µ En , x = ? lence electrons of rubidium atm (Z = 37) is
(C) Angular momentum in lowest or- (r) –2 [2013 Main]
bital 1 1
(a) 5, 0, 0, + (b) 5, 1, 0, +
1 2 2
(D) µ zy, y = ? (s) 1 1 1
rn (c) 5, 1, 1, + (d) 5, 0, 1, +
2 2
26. Match the entries in column I with the related quantum 33. Energy of an electron is given by E = –2.78 ¥ 10–18 J
number(s) in Column II. (2008, 6M) Ê Z2ˆ
Column I Column II ÁË 2 ˜¯ . Wavelength of light required to excite an elec-
n
(A) Orbital angular (p) Principal quantum tron in an hydrogen atom from level n = 1 to n = 2 will
momentum of the number be [2013 Main]
electron in a hy- (h = 6.62 ¥ 10–34 Js and c = 3.0 ¥ 108 ms–1)
drogen- like atomic (a) 1.214 ¥ 10–7 m (b) 2.816 ¥ 10–7 m
–7
orbital (c) 6.500 ¥ 10 m (d) 8.500 ¥ 10–7 m
34. The kinetic energy of an electron in the second Bohr
(B) A hydrogen – like (q) Azimuthal quan-
orbit of a hydrogen atom is [a0 is Bohr radius]
one electron wave tum number
[2012]
function obeying 2 2
Pauli’s principle h h
(a) (b)
(C) Shape, size and (r) Magnetic quantum 4p 2 ma02 16p 2 ma02
orientation of hy- number h2 h2
drogen- like atomic (c) (d)
orbitals 32p 2 ma02 64p 2 ma02
35. In an atom, the total number of electrons having quan- 36. The atomic masses of He and Ne are 4 and 20 amu,
1 respectively. The value of the de-Broglie wavelength
tum numbers n = 4, |m| = 1 and m2 = - is of He gas at –73°C is ‘M’ times that of the de-Broglie
2
[2014 Adv.] wavelength of Ne at 727°C M is [2013 Adv.]
Answer Key
LEVEL I
1. (a) 2. (c) 3. (d) 4. (c) 5. (a) 6. (d) 7. (b) 8. (d) 9. (a) 10. (d)
11. (d) 12. (d) 13. (b) 14. (a) 15. (b) 16. (b) 17. (c) 18. (b) 19. (b) 20. (c)
21. (d) 22. (a) 23. (c) 24. (b) 25. (b) 26. (b) 27. (a) 28. (a) 29. (b) 30. (c)
31. (c) 32. (d) 33. (c) 34. (c) 35. (a) 36. (a) 37. (c) 38. (a) 39. (a) 40. (b)
41. (b) 42. (a) 43. (a) 44. (a) 45. (c) 46. (c) 47. (d) 48. (b) 49. (a) 50. (c)
51. (c) 52. (c) 53. (b) 54. (c) 55. (a) 56. (a) 57. (d) 58. (b) 59. (c) 60. (c)
61. (d) 62. (b) 63. (c) 64. (a) 65. (c) 66. (a) 67. (b) 68. (d) 69. (b) 70. (b)
71. (a) 72. (c) 73. (a) 74. (b) 75. (a) 76. (c) 77. (c) 78. (a) 79. (b) 80. (b)
81. (b) 82. (d) 83. (b) 84. (b) 85. (d) 86. (c) 87. (a) 88. (b) 89. (b) 90. (a)
91. (a) 92. (a) 93. (a) 94. (b) 95. (d) 96. (d) 97. (d) 98. (a) 99. (a) 100. (b)
101. (a) 102. (b) 103. (a) 104. (c) 105. (d) 106. (b) 107. (d) 108. (b) 109. (d) 110. (c)
111. (c) 112. (d) 113. (b) 114. (b) 115. (c) 116. (c) 117. (a) 118. (b) 119. (a) 120. (a)
121. (c) 122. (d) 123. (a) 124. (d) 125. (b) 126. (d) 127. (b) 128. (a) 129. (d) 130. (a)
131. (a) 132. (a) 133. (a) 134. (b) 135. (b) 136. (c) 137. (a) 138. (b) 139. (c) 140. (d)
141. (b) 142. (c) 143. (d) 144. (a) 145. (c) 146. (c) 147. (c) 148. (c) 149. (c) 150. (d)
LEVEL II
1. (d) 2. (d) 3. (a) 4. (a) 5. (b) 6. (a) 7. (b) 8. (a) 9. (a) 10. (d)
11. (a) 12. (d) 13. (b) 14. (c) 15. (a) 16. (b) 17. (c) 18. (a) 19. (c) 20. (b)
21. (a) 22. (a) 23. (d) 24. (d) 25. (b) 26. (b) 27. (a) 28. (b) 29. (d) 30. (b)
31. (a) 32. (c) 33. (d) 34. (a) 35. (b) 36. (d) 37. (a) 38. (d) 39. (d) 40. (b)
41. (d) 42. (c)
LEVEL III
1. (A) Æ P; (B) Æ P, Q, R, S, T; (C) Æ Q, R, S; (D) Æ P 2. A Æ r, t; B Æ p; C Æ q, s; D Æ q

3. A Æ p; B Æ p; C Æ p, q, r, s; D Æ p 4. A Æ r, p; B Æ r, t; C Æ s; D Æ q
5. A Æ r; B Æ q; C Æ p, t; D Æ s 6. (A) Æ t; (B) Æ s ; (C) Æ u ; (D) Æ q ; (E) Æ p; (F) Æ r
7. (A) Æ u ; (B) Æ s ; (C) Æ p ; (D) Æ t ; (E) Æ q ; (F) Æ r
8. (A) Æ q ; (B) Æ p ; (C) Æ q, r ; (D) Æ r, s
9. (A) Æ r ; (B) Æ s; (C) Æ p; (D) Æ q
10. A Æ P, BÆp, q, s, CÆp, r, D Æ q, s
11. (b) 12. (b) 13. (c) 14. (b) 15. (a) 16. (c) 17. (d) 18. (d) 19. (d) 20. (b)
21. (d) 22. (d) 23. (b) 24. (a) 25. (a) 26. (b) 27. (c) 28. (b) 29. (a) 30. (d)
31. (c) 32. (c) 33. (b) 34. (c) 35. (a) 36. (a) 37. (b) 38. (a) 39. (e) 40. (a)
41. (a) 42. (b) 43. (a) 44. (b) 45. (e)
46. (b) 47. (a, b, d) 48. (a, c, d) 49. (a, b, c, d) 50. (b, c, d)
51. (a, d) 52. (4) 53. (6) 54. (0) 55. (2) 56. (0) 57. (4) 58. (3) 59. (2) 60. (1)
61. (4) 62. (2) 63. (2) 64. (5) 65. (3) 66. (0) 67. (2) 68. (4) 69. (6) 70. (0)
71. (5) 72. (12) 73. (1) 74. (2.66 ¥ 102 sec.)
75. (a) [15.6] (b) [233.9 nm] (c) [1.808 ¥ 107 m–1] (d) [–9.6 eV and –4.6 eV] 76. [28] 77. [1022]
5
78. [1.35 ¥ 10 ] 79. [6] 80. [4863 Å] 81. [1.096 ¥ 10 m ] 82. [1.827 ¥ 105J/m]
7 –1
83. [1400 KJ/mole] 84. [–0.85 eV] 85. [5.425 ¥ 10–12 ergs. 3.66 ¥ 10–5cm] 86. [1220 Å]
87. [2] 88. [108.8 eV] 89. [10.2 eV, He] 90. [0.486 NA, 0.27 NA, 56.65 ¥ 1011 erg]
h
91. [0.5 NA (E2 – E1) + 0.25 NA(E2 – E1)] 92. 93. [0.0036 nm–1] 94. 932 Å 95. r = a0
p
96. [3.271 ¥ 10–18 J] 97. [498.3 KJ/mole] 98. [8 ¥ 106] 99. [2.3 ¥ 1013Hz] 100. [5]
6 –34
101. [3.09 ¥ 10 m/sec.] 102. [v0 = 6.626 ¥ 10 ] 103. 318.9 Kj/mole]
PREVIOUS YEARS’ QUESTIONS OF JEE (MAIN & ADVANCED)
1. (d) 2. (a) 3. (c) 4. (c) 5. (a) 6. (c) 7. [B – 11.01 80%, 20% and B 10.01]
8. [6603 Å] 9. [12220 Å] 10. [3.67 ¥ 10–5 cm] 11. (10) 12. [2055 Å]
h
13. [6.62 ¥ 10–25 Å] 14. [2.18 ¥ 106 m sec–1, 3.3 Å, 2 ] 15. [He+] 16. [n Æ 2 to n Æ 1] 17. [3]
p
18. [2.16 ¥ 10–20J] 19. 27419.25 cm–1] 20. [6.3 ¥ 106m sec–1] 21. [63.3 volt] 22. [98.18 KJ]
23. [22.8 nm] 24. [r0 = 2a0] 25. A Æ r; B Æ q, C Æ p, D Æ s
26. A Æ q; B Æ p, q, r, s; C Æ p, q, r ; D Æ p, q, r 27. (b) 28. (c) 29. (b) 30. (9) 31. (c)
32. (a) 33. (a) 34. (c) 35. (6) 36. (5)
Hints and Solutions
LEVEL I 8. (d) d7
1 1 1 3
1 Total spin = + + + =
2 2 2 2
1. (a) E5 = –13.6 ¥ = – 0.54 eV
(5) 2 9. (a) K = 2e– = 1s2
2. (c) Li+2 and He+ both have same number of electron so L = 8e– = 2s2 2p4
spectrum pattern will be similar. M = 11e– = 3s2 3p6 3d3
h 1 N = 2e– = 4s2
3. (d) l = lµ l = 2 for d \ e– = 3
2mqV V
10. (d) Cl– = 1s2 2s2 2p6 3s2 3p6
l1 V 200 2 For last e– n = 3, l = 1, m = ±1 or 0 or –1
= 2 = =
l2 V1 50 1
13.6 z 2
h 11. (d) En = - eV
4. (c) Dx ◊ Dp = n2
4p as move away from the nucleus, the energy increases,
put value Dp = 1.0 ¥ 10–5 kg ms–1 hence, energy is maximum at infinite distance from the
5. (a) Orbital angular momentum nucleus.
h 12. (d) When an electron jump from higher level to lower
= l(l + 1) ◊ for l = 0 level, it emits the photon and lower level to higher lev-
2p
el. It absorbs photon. Hence, ‘1s’ only absorbs photon
6. (d) 25Mn = 1s2, 2s2 2p6, 3s2 3p6 3d5, 4s2 because it is lowest energy level.
Mn+4 = 1s2, 2s2 2p6, 3s2 3p6 3d3, 4s0 1 È1 1˘
7. (b) 30Zn2+ = 1s2, 2s2 2p6, 3s2 3p6 3d10 13. (b) = RH Í 2 – 2 ˙
l Î n1 n2 ˚
(unpaired de– = 0)
2+ 2 2 6 2 6 6 – In Balmer series, electron jumps from higher energy
26Fe = 1s 2s 2p 3s 3p 3d (unpaired de = 4)
3+ 2 2 6 2 6 7 –
level to second energy level. Hence third line form
28Ni = 1s 2s 2p 3s 3p 3d (unpaired de = 3) when electrons jump from fifth energy level to 2
+ 2 2 6 2 6 9 –
29Cu = 1s 2s 2p 3s 3p 3d (unpaired de = 1) energy level. 5 Æ 2
14. (a) 37Rb = 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 5s1 1 È1 1 ˘ 1 È 7 ˘
n l m s = RH z 2 Í – ˙ = RH 32 Í ˙
l Î 9 16 ˚ l Î 9 ¥ 16 ˚
5 0 0 + 1/2
15. (b) Aufbau’s principle : electron fills in orbital increas- 9 ¥ 16 1 16
l= ¥ fi l = x
ing order of energy level. 9 ¥ 7 RH 7
70 2+
16. (b) 30 Zn = n = A – Z = 70 – 30 = 40 25. (b) (IE) Li2+ = (IE) H ¥ Z 2
17. (c) n > l, m = –l to + l
= 21.8 ¥ 10–19 ¥ 9 J/atom
n l s
\ Kinetic energy of ejected electron
3 2 ½
= 8 ¥ 21.8 ¥ 10–19 J atom
The value of (m) is wrong h h
l = 2, m = –2, –1, 0, +1, +2 l= =
2KE ◊ m 2qV ◊ m
18. (b) Hund’s rule
19. (b) Cr = 1s2 2s2 2p6 3s2 3p6 3d5 4s1 ; Mn+ = 1s2 2s2 2p6 6.62 ¥ 10 –34
l=
3s2 3p6 3d5 4s1 2 ¥ 9.1 ¥ 10 –31 ¥ 2.18 ¥ 10 –19 ¥ 8
i.e., it represents both ground state and cationic form.
l =1.17 Å
20. (c) Fe3+ = 1s2 2s2 2p6 3s2 3p6 3d5 26. (b) Fe2+ = 1s2 2s2 2p6 3s2 3p6 3d6
21. (d) Schrödinger’s equation gives only n, l and m quan-
tum number. Spin quantum number is not related to
Schrodinger equation. Unpaired electron (n) = 4
1 Magnatic moment
22. (a) hn = hn0 + mn2
2 = n(n + 2) BM = 4(6) = 24 BM
hc hc 1 2 Orbital angular momentum
= + mn
l l0 2 = l ¥ (l + 1)  = 2(3)  fi 6 
Ê l – lˆ 1 2
K.E. = hc Á 0 = mn h 1
Ë l l0 ˜¯ 2 27. (a) l = lµ
2 KE ◊ m 2qV ◊ m
Ê h2 ˆ Ê l0 – l ˆ Ê h ˆ 1 1
Á ˜ = hc ÁË ll ˜¯ ÁË
\l = le µ ; l p+ =
Ë 2mle2 ¯ 0 2mK ◊ E ˜¯ M e ¥ 16 E M p ¥ 4E
l l0 h
le2 = la µ
1
; hence le > l p + = lµ
[l0 – l ]2mc
4 p ¥ 4E
M
1
È h l l0 ˘ 2 28. (a) Li (g) h Li+ + e– ; DH = 520
le = Í ˙
Î 2mc [l0 – l ] ˚ Li+ (g) h Li+2 + e ; DH = a KJ/mol
23. (c) mn = mass of neutron; mp = mass of proton Li2+ (g) h Li2+ + e ; DH = b KJ/mol
mn b = ( IE2 ) Li+ and (IE) Li2+ = (IE)n ¥ z2 = 1313 ¥ 9
2mp
2 b = ( IE2 ) Li+ = 11817 KJ/mol
atomic mass fi (mn + mp) [mn ~ mp] 520 + a + 11817 = 19800
fi (8 + 6) = 14 mp ( IE2 ) Li+ = a = 7463 KJ/mol
new atomic mass fi (4 + 12) = 16 mp
1 Ê 1 1ˆ Ê n2 – n2 ˆ
16 – 14 29. (b) = RH Á 2 – 2 ˜ fi RH Á 2 2 21 ˜
% increase = ¥ 100 = 14.28 % l
14 Ë n1 n2 ¯ Ë n1 n2 ¯
1 È1 1˘ (n22 n12 ) 1
24. (b) = RH Z 2 Í 2 – 2 ˙ l= 2 2
¥
l Î n1 n2 ˚ (n2 – n1 ) RH
for shortest wavelength n2 = •, n1 = 2 First line of Lymen series n2= 2, n1= 1
Second line of Lymen series n2 = 3, n1= 1
1 È1 1 ˘ 4 1
= RH 22 Í – ˙ l = = =x Third line of Lymen series n2= 4, n1 = 1
l Î4 •˚ 4 RH RH 30. (c) The anode ray/canal ray is independent to the elec-
for longest wavelength of Parchan series n2 = 4, n1 = 3 trode material.
31. (c) Energy order decide from (n + l) rule; (n + l) is mP 1 1 4 v

minimum, energy is minimum. If (n + l) value is equal, = ; or = ◊ a
ma 4 2 1 vp
lower the value of ‘n’, lower the energy.
e3 > e2 > e4 > e1 vp 8 h h
= ; or l = =
r r va 1 p 2mKE
32. (d) r1 = 22 r1 = ; r3 = r1 ¥ n2
n 4 Now,
r3 = r/4 ¥ 9 r3 = 2.25R h
h 6.62 ¥ 10 –34 ¥ 3600 lp 1 2m p ◊ KE p Ê 1ˆ
2
2m ◊ KEa 1
33. (c) l = = = = ; or Á ˜ = a =
mv 0.2 ¥ 5 la 2 h Ë 2¯ 2m p ◊ KE p 4
l = 2.38 ¥ 10–30 metre 2ma ◊ KEa
34. (c) According to Paulis, an orbital can accomdate max-
imum two electrons. Hence Paulis exclusion principle 4 K.E.a 1 K.E. p 16
or, ◊ = ; \ =
violates. 1 K.E. p 4 K.E.a 1
35. Cu(29) = 1s2 2s2 2p6 3s2 3p6 4s1 3d10
44. 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Form (m = 0) = 2 + 2 + 2 + 2 + 2 + 1 + 2 (n + l) = 3 means
= 13 electron 2p6 and 3S2
+2
36. Cd [z = 48] l = 2 means 3d10
Azimuthal l = 1 only for p-orbital n + l = 3 fi 8 electron
upto 48 Æ 2p6 3p6 4p6 = 18e l = 2 fi 10 electron
37. A h 30 W EA (photon) = 13.6 eV 8 ¥ 10 = 80
B h 40 W EB (photon) = 13.6 ¥ 22 = 4 ¥ 13.6 eV 45. Ga last e–1 in 4P1
For A(13.6 ¥ 1.6 ¥ 10–19) ¥ nA = 30 \ n = 4, l = 1
m = –1 or O or +1
For B (4 ¥ 13.6 ¥ 1.6 ¥ 10–19) ¥ nB = 40
S = +½ or –½
nA 3 or single e– system.
=
4 nB 4 46. Bohr’s theory is applicable to H and H-like species.
nA 3 47. Conceptual
fi = Z
nB 1 48. Vn = 2.18 ¥ 108 ¥ cms -1
38. n2 = 11 higher state n
n1 = 1 lowest state for Vn to be maximum; for hydrogen atom
U.V. = 11 – 1 = 10 Z = 1, n = 1 \ V = 2.18 ¥ 108 cms–1
Visible = 11 – 2 = 9 1
11 ¥ 10 49. We know that v µ and n = principal quantum num-
Remaining = – 19 = 55 – 19 n
2 ber. Therefore, vn will be independent of the principal
(z) I.R. = 36 quantum number.
Hence, z – (x + y) = 36 – (9 +10) = 17 50. –P.E. = 2K.E. = 2 ¥ (+13.6) = 27.2 eV.
39. Number of angular nodes = l = 2 (d-orbitals) \ P.E. = –27.2 eV
and number of maxima = n – l = 3 fi n = 5 P.E. with respect to ground state = 27.2 eV, which we
40. 2prn = nl assume to be zero.
4h2 13.6
2p r4 2p r2 K.E. = - 2 eV
l4 = l2 = n
4 2 For the first excited state, n = 2.
È 0.529(4) 2 0.529(2) 2 ˘ 13.6
l4 - l2 = 2p Í - ˙Å \ K.E. = - 2 eV = - 3.4 eV
Î 1¥ 4 2 ˚ 2
= 2p (0.529) ¥ 2 Total energy = (27.2 –3.4)eV = 23.8eV.
= 4pr1 = 6.64 Å 2p rn 2p r1 ¥ n 2
51. T = = or T µ n3; n = 2 here
h un u1 / n
l Ê 1 ˆ mp ◊ vp m v
41. P = Á ˜ = = a a 1
la Ë 2 ¯ h mp ◊ vp 52. DE = E2 - E1; E2 - E1 or l µ
( E2 - E1 )
ma va
53. N = number of lines emitted 74. According to de Broglie

diff. ¥ (diff. + 1) 3(3 + 1) 12 h 6.62 ¥ 10-27 erg sec
= = = =6 l= =
2 2 2 mv 2
¥ 5 ¥ 104 cm/sec
54. hn1 = hn0 + K.E.1 6.023 ¥ 1023
2hn1 = hn0 + K.E.1
K.E. = hn1 – hn0 = 4 ¥ 10-8 cm = 4Å
The value of K.E. will increase but more than double of 75. Z = 20, so electronic configuration is
the previous K.E. 1s2 2s2 2p6 3s2 3p6 4s2
55. Aufbau’s principle
56. For outermost electron of Rb, the configuration is 5s1. \ for outer most electron 4s electron n = 4, l = 0, m =
57. The electronic configuration of sulphur atoms 1s2s22p- 1
6 2 4
0, s = +
3s 3p , the orbitals with (n + l) = 3 are 2p and 3s, 2
therefore 8 electrons in sulphur atom have (n + l) = 3. 76. The electronic configuration of Ar atom is 1s2 2s2 2p6
58. Orbital angular momentum 3s2 3p6. In its first excitation state, the electron from 3p
h h will unpair and shift to 4s where its quantum numbers
= l (l + 1) = 0(0 + 1) =0
2p 2p will be 4, 0, 0, ± ½.
59. Number of unpaired electrons in V, Cr and Mn is 3, 6 77. Most electro-negative element is F.
and 5. \ electronic configuration: ns2np5
60. Double dumb bell shaped in 4th principle quantum 78. Angular nodes are only associated with directional or-
number means 4d
bital.
n–l–1=4–2–1=1
E 22 4
2 1 1 79. E2(He+ ) = 21 = -13.6 ¥ 2 = -13.6 ¥ = -13.6 eV
61. Charge/mass for n = 0, a = , p = , e = n n 4
4 1 1/1837
So, order is n, a, p, e. Z2
80. En = -13.6 ¥
62. Charge/mass for n2
1 En (H)
n = 0, a = 2/4, p = 1/1 and e = 1 1
1/1837 = = = 1: 4
En (Be+3 ) 42 4
63. Number of p, n and e are 20, 20 and 20.
64. Isotonic : same number of neutrons 4
65. Conceptual 3 5 27
81. Ratio = E2 – E1/E3 – E2 = =
4 36 5
n2
66. r = r0 = 0.529 ¥ 10-8 cm
Z 1 È1 1˘
82. = RH Z 2 Í 2 - 2 ˙ for Balmer series
Radius of second Bohr orbit 0.529 22 l Î n1 n2 ˚
67. = ¥ =4
Radius of first Bohr orbit 0.529 1 1 È1 1˘ R 5
= RH ¥ 12 Í 2 - 2 ˙ = H cm -1
3+ 0.529 ¥ (2) 2 l Î2 3 ˚ 36
68. rBe = = 0.529
4 1 È1 1˘
69. Absorption line in the spectra arise when energy is ab- 83. = RH ¥ 12 Í 2 - 2 ˙ …(A)
lH n
Î 1 n2˚
sorbed, i.e., electron shifts from lower to higher orbit.
Maximum wavelength means minimum energy so, the 1 È1 1˘
transition involving minimum energy is the right op- = RH ¥ Z 2 Í 2 - 2 ˙ …(B)
lX Î n1 n2 ˚
tion.
70. Conceptual Dividing (A) by (B), we get
lX 1
È1 1˘ = 2
71. VH = RH Í 2 – 2 ˙ ; Z =1 for H-atom lH Z
Î2 3 ˚
1 1
È1 1˘ =
VBe3+ = RH ¥ 16 Í 2 – 2 ˙ ; Z = 4 for Be3+ 4 Z2
Î2 3 ˚
Z = 2 (He+)
Thus, V Be3+ = 16V H = 16 ¥ 15200 cm
84. for hydrogen
= 2.432 ¥ 105 cm–1.
h 6.6 ¥ 10-34 Ê1 1 ˆ Ê 1 1ˆ
72. l = = = 2.37 ¥ 10-30 m Z H2 ¥ Á - 2 ˜ = Z X2ÁË 2 - 2 ˜¯
mv (0.2) ¥ 5/(60 ¥ 60) Ë1 3 ¯ 3 9
h sixth line of Paschen series = 9
73. l = l will be large if m is small.
mv
8 Ê1 1 ˆ hc
= Z X2 Á - ˜ 92. E =
9 Ë 9 81¯ l
8 8 1
= Z2 fi lµ
9 81 E
Z2 = 9 l1 E2 4000 Å
\ = =
Z = 3 (Li+2) l2 E1 2000 Å
85. hn = hn0 zero velocity K.E. = 0 \ l1 :l2 = 2 : 1
hn = hn0 93. For a ‘d’ electron, l = 2
hn = 4 eV Orbital angular momentum
hc h h
= 4 eV = l (l + 1) = 6 or 6
l 2p 2p
h ¥ c 6.626 ¥ 10-34 ¥ 3 ¥ 108 12
l= = = 3100 Å 94. E = -13.6 eV ¥ = - 3.4 eV
4 eV 4 ¥ 1.6 ¥ 10-19 22
h h
86. l = K.E. = eV K.E. = eV = qV 95. DP ◊ Dx ≥
2mKE 4p
same mass 96. n = 4
l=2
l1 KE 2 2
= = m = –2, –1, 0, +1, +2
l2 KE1 1 1
s=±
\ l1 = 2 l2 2
h 6.626 ¥ 10-34 1 Ê 1 1ˆ
87. l = = 97. = RH (1) 2 Á 2 - 2 ˜
mV 9.1 ¥ 10-31 ¥ 2.2 ¥ 106 l Ë 2 3 ¯
= 0.33 ¥ 10–9 Ê 5ˆ Ê 5R ˆ
= RH ◊ Á ˜ cm -1 or n = Á H ˜ cm -1
= 0.33 nm Ë 36 ¯ Ë 36 ¯
h 6.626 ¥ 10-34 98. For Balmer series n2 = 2
88. l = =
mV 0.200 ¥ 10-3 ¥ 5/3600 Fourth line is 6 to 2
22 -13.6 ¥ 42
= 2.3853 ¥ 10-27 m 99. I.P. = –E1 = –13.6 ¥ 2 = - (for I.P., n
always = 1) n 12
e2 E = 217.6 eV
89. Total energy = - = - 3.4 eV = 21
2rn n hc
100. Required energy = 10–17 J = n ¥
-13.6 l
\ n2 = =4 6.625 ¥ 10-34 ¥ 3 ¥ 108
- 3.4 fi n¥ J = 10-17 J
n=2 550 ¥ 10-9
\ n = 28
The velocity in second orbit hc 1242 1242
101. E (eV) = = = = 1.77 eV
U1 2.18 ¥ 108 l l (nm) 700 nm
= = (cm sec -1 )
2 2 102. E = hn
= (6.62 ¥ 10–34 Js) (880 s–1)
h 6.626 ¥ 10-27 ¥ 2 = 5.831 ¥ 10–31 J.
l= =
mu 9.1 ¥ 10-28 ¥ 2.18 ¥ 108 1
Number of photons emitted = ¥ 10+31 = 1.71 ¥
= 6.6 ¥ 10–10 = 6.6 Å 30 5.831
10 per second.
90. Shape of s-orbital is spherical, so it is non–directional e 1
orbital. 103. For a proton (11 H), =
m 1
1 Ê 1 1ˆ e 2 1
91. = RH Z 2 Á 2 - ˜ 4
For an a-particle ( 2 He), = =
l Ë1 •¯ m 4 2
hc RH hcZ 2 (e / m) p 1/1
E= = = = 2 :1
l 1 (e / m)a 1/2
h h h
104. The de Broglie equation is l = = l=
p mv mv
1 h
Here h and v are constant. So l µ . l= ; l =1Å
m 2eVm
Since the a-particle has the highest mass among the
150
given entities, it has the smallest de Broglie wave- On solving l = Å for electron
lengths. V
13.6 150
105. En = - 2 Z 2 , where n = 1 for ground state, 2 for first l=1Å= \ V = 150 Volt
n V
excited state, and so on. Z = 1 for hydrogen. 113. Number of unpaired electrons in Cr3+ = 3
1 Ê 1 1ˆ 114. Violates Hund’s law
106. = R• Á 2 - 2 ˜ for H atom.
l Ë n1 n2 ¯ 115. 1.73 = n(n + 2) V = 3d3 4S2
For the Balmer series, n=1
n1 = 2 and n2 = 5 (for the third line). Oxidation state = 4
1 Ê 1 1 ˆ 21 h
= R• Á 2 - 2 ˜ = R• 116. Dp ◊ Dx ≥
l Ë2 5 ¯ 100 4p
100 Given Dp = Dx
l=
21R• h
(mDv) 2 ≥
107. l = 3 mean f subshell have 7 orbital. 4p
Maximum multiplicity for the f orbitals (7 electrons) 1 h
= 2s + 1 = 2 ¥ 7/2 + 1 = 8 Dv ≥
2m p
Minimum multiplicity for the f orbital (1 electron) 117. For the second line of Lyman series of H,
= 2s + 1 = 2 ¥ 1/2 + 1 = 2 n1 = 1, n2 = 3
Z2 1 È1 1 ˘ 8R
108. En = -13.6 ¥ eV = R ¥ 12 Í 2 - 2 ˙ =
n2 lH Î1 3 ˚ 9
For the 3rd excited Bohr’s orbit of H atom 9
fi Z = 1, n = 4 \ lH = …(i)
8R
E1 = –13.6 eV
For 3rd excited state of hydrogen For the sixth line of Paschen series,
n1 = 3, n2 = •
12
E2 = -13.6 ¥ = - 0.85 eV 1 È1 1 ˘ È 1 1 ˘ RZ
2
42 = RZ 2 Í 2 - 2 ˙ = RZ 2 Í - ˙ =
lx Î3 • ˚ Î9 0 ˚ 9
-13.58
109. En = 9
n2 \ lx = …(ii)
RZ 2
at n = 1, E1 = –13.58 eV
(In primitive stage) n = 2, E2 = –3.395 eV But, lH = lX
Energy absorbed = –3.395+13.58 = 10.19 eV 9 9
i.e.; = \ Z2 = 8
2
n 8R RZ 2
110. rn = r1 ¥
Z Z = 83
42 i.e., Li+2 – ion.
r2 = r1 ¥ = 0.106 nm
2 118. According to the question
n2 h
111. rn = r0 ¥ , here Z = 1 l=
Z p
rn µ n2 h
lA = …(i)
So r1 : r2 : r3 … = n12 : n22 : n32 … pA
= 12 : 22 : 32 h
= 1:4:9 lB = …(ii)
pB
112. If electron is accelerated by V volt
1 l A pB
K.E. = eV = mv 2 = l B = 10-7 m
2 lB pA
119. We know that  1 fm = 10–15 m ª 5 fm

rn = r1 ¥ n2 134. (b) d = 20 nm
9r1 = r1 ¥ n2 20
\ n2 = 9 r= = 10 nm =100 A°
2
\ n=3 n2
 r = 0.529 ¥ A° For H atom Z = 1
13.6 Z
\ E3 = - 2 = -1.51 eV
3 100 = 0.529 ¥ n2 n = 14
120. According to Bohr’s atomic model Z2
mvr = nh/2p 135. (b) En = –13.6 ¥
n2
6.62 ¥ 10-34 1
4.2176 ¥ 10–34 = n2 ¥ E1(H) = – 13.6 ¥ = –13.6 eV
2 ¥ 3.14 1
\ n2 = 4 4
1 È1 1˘ E2(He+) = – 13.6 ¥ = –13.6 eV
= R ¥ 12 Í 2 - 2 ˙ 4
l Î3 4 ˚ 32
E3(Li2+) = – 13.6 ¥ = 2 –13.6 eV
\ l = 18.75 ¥ 10–7 m 3
hc 42
121. E3 – E1 = DE = E4(Be3+) = – 13.6 ¥ = –13.6 eV
l 42
hc 1242 1242 \ B is the answer.
l= or l (nm) = =
DE DE (rev) 12.4 ev 136. (c) E = –78.4 kcal/mol
l = 1030 Å = 103 nm Z2
En = –313.6 ¥ kcal/mol
122. hn = work function + K.E.; n2
Given K.E. = 0; 1
for H atom Z = 1 –78.4 = 313.6 ¥
1242 n2
Thus, hn = 4 eV or 4 = 313.6
l (nm) n2 = n=2
78.4
1 Ze 2 Ze 2 137. (a) Vn = 2.188 ¥ 106 ¥ m/sec.
123. K.E. = mu 2 = , T.E. = - \ (A)
2 2r 2r
V3 (Li 2+ ) Z 3 / n3 3/3
124. The state corresponds to the 3d atomic orbitals. = = V(Li2+) = V
125. The 21st electron corresponds to 3d1. For this orbital, V1 (H) Z1 / n1 1/1
1 138. (a) Let state (A) = n1
n = 3, l = 2, m = 2, s = + . State (B) = n2
2
126. Mn4+ (21 electrons) = [Ar]3d3 contains three unpaired r1 – r2 = 624 r0
electrons. n12 0.529n22 0.529 ¥ 1
127. The spin-only formula is given by mspin only 0.529 ¥ - = 624 ¥
Z Z Z
= n(n + 2) BM n12 - n22 = 624
n = No of unpaired e– n1 = 25
The value of m = 2.83 BM corresponds to the presence n2 = 1
of two unpaired electrons. So the ion is Ni2+ (3d8). 25 Æ 1
128. For the 3p orbital, n = 3, l = 1. 139. (c)
The number of spherical nodes = n – l – 1 = 3 – 1 – 1 = 1 (a) Energy of ground state
129. Spin multiplicity = (2S + 1). He+ = –13.6 ¥ 4 eV = –54.4 eV
rA 0.529 ¥ 1
130. (a) = 105 (b) P.E. of first orbit of H-atom = 2T.E. =
rN Z
–2 ¥ 13.6 eV = –27.2 eV
3
VA Ê rA ˆ (c) Energy of second excited state
= = (105 )3 = 10-15
VN ÁË rN ˜¯ Z2 (2) 2
= -13.6 ¥ = - 13.6 ¥
131. (a) neon and O– 2 have 10 electron n2 (3) 2
C 3×108 4
132. (a) l = = = 0.75 m = -13.6 ¥ = - 6.03 eV
n 400×106 9
133. (a) R = R0 A1/3 = 1.33 ¥ 10–13 ¥ (64)1/3 cm (d) I.E.= –E1 = 21.8 ¥ 10–19 ¥ 4J = 8.7 ¥ 10–18 J
= 5.32 ¥ 10–13 ª 5 fm
140. (d) For dyz, xy and xz are nodal palne

node = (n – l – 1) = 6 – 2 – 1fi 3 LEVEL II
141. (b) x h y + 42 He
1. (d) last e– enter in 2P subshell
y h 8O18 + 1H1
\ l=1
y = 9y19 2. (d)
x = 11x23 Pd 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s0 4d10
Hence x = Na (I) l 0
Na present in third period 2 2 2 2 0 8 electrons
Number of neutron = 23 – 11 fi 12
(II) Z is different, therefore, Zeff will be different.
4.6 (III) Configuration of 26Fe Æ [Ar] 4s2 3d5
Mole of Na = fi 0.2
23 Configuration of Ni+2 Æ [Ar] 3d8 4s0
Mole of neutron fi 0.2 ¥ 12 fi 2.4 Number of unpaired electrons are different.
hc 1240 1240 (IV) 57 electron (La ) 5d1
142. (c) E = fi eV E = fi 40 eV
l lnm 31 n=5
40 = 12.8 + K.E. Êlˆ
l=2 ÁË ˜¯ = 0.4
K.E. = 40 – 12.8 = 27.2 eV n
+2
K.E. = 27.2 ¥ 1.6 ¥ 10–19 3. (a) A have 22 electron
1 A has 24 electron / 24 p+
27.2 ¥ 1.6 ¥ 10–19 = ¥ 9.1 ¥ 10–31 ¥ v2 n0 = 26
2
(i) Mass number of A = 50
v = 2.18 ¥ 2 ¥ 106 m/s Atomic number is 24
1 v z /n 3d54s1
143. (d) Frequency = µ µ 2 +2
T r n/z (iv) A 1 electron is removed from s and 1 from d.
4. (a) Ga (31) 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p1
1 z2 n3 1/4 1
Frequency = µ 3 Tµ 2 = fi n=4
T n z 8/1 32 l=1 n+l+m=6
144. (a) s-orbital is spherical hence it is non-directional. m=1
h 5. (b)
145. (c) Dx = 2Dp Dx ◊ 2Dp =
4p (a) Fe+3 [Ar]3d5
h h Co+3 [Ar] 3d6
2 (Dp)2 = (Dv)2 = More the number of unpaired electron, more will be
4p 8p m 2
multiplicity.
1 h 1
Dv = Dv = h Ti +3[Ar]3d1 ¸
2m 2p 2m ÔÔ
(b) Cr + [Ar]3d 5 ˝ are paramagnetic
Ô
Sc +2 [Ar]ed1 Ô˛
45° (c) Mg [Ne] 3s2

146. (c)
n = 3, l = 0, m = 0
\ n+l+m=3
(d) Cl (1s2) (2s2 2p6) (3s2 3p5)
s = 6 ¥ 0.35 + 8 ¥ 0.85 + 2 ¥ 1 = 10.9
147. (c) n = 5 Zeff = 17 – 10.9 = 7.1
l = 0, 1, 2, 3, 4, 6. (a) Element is Na
s, p, d, f, g \ number of neutron = 12
148. (Theory Based) \ number of proton and electron = 11
149. (c) From (n + l) rule (a) Mg24 also has 12 neutrons
150. (d) The value of l = 0 to (n – 1) (b) 3s1 is last electron
Number of electron for given value of l = 2 (2l + 1) (c) H2O has 10 electrons
l = ( n –1) (d) Since atoms have 1 unpaired electron \ it is para-
Hence Â 2(2l + 1) magnetic.
l=0
7. (b) 4 - a0 / a0
(a) 12Mg 1s2 2s2 2p6 3s2 (Diamagnetic) 4p a02 ¥ e
p1 a03
(b) 20Ca 1s2 2s2 2p6 3s2 3p6 3d2 (Paramagnetic) =
p2 a02 4
(c) 28Ni 1s2 2s2 2p6 3s2 3p6 3d10 (Diamagnetic) 4p ¥ 3 e -2 a0 /2 a0
(d) 30Zn 1s2 2s2 2p6 3s2 3p6 3d10 4s2 (Diamagnetic) 4 a0
8. (a) For 2.84 B.M., 2 unpaired electrons are required. p1 e -2 4
= =
Fe2+ [Ar] 3d5 p2 1
e -1 e
Cr [Ar] 3d5·4s1 4
Cr+3 [Ar] 3d3 15. (a) See graph in theory
Ti +2
[Ar] 3d2 16. (b) Dx = 0.0001 Å
Mn +2
[Ar] 3d5 DP = ?
+3 h h
V [Ar] 3d2 Dx ¥ Dp ≥ ; DP =
9. (a) S 1s22s22p63s2 3p2 4p 4p ¥ 0.0001 Å
a0 = 0.529 Å
h
1 1 1 1 1 1 1 1 1 P=
2p ¥ 0.529 Å
S = +1/2
minimum (7) e– h
S = +1/2 [16 – 7] = 9 DP 4p ¥ 0.0001 Å
=
Maximum (9e–) P h
(b) e with m = 0 present in s-orbital is not compulsory 2p ¥ 0.529 Å
as the value of n increases m also be 0. DP 2 ¥ 0.529
= = 2645
(c) Na+1 Mg+2 all isoelectronic species have same P 4 ¥ 0.0001
s but different Zeff
h
(d) Number of subshell nth shell is equal to n. 17. (c) l =
10. (d) l = 2 2m ¥ e ¥ V
Fe (26) = 1s2 2s2 2p6 3s2 3p6 3d6 4s2 h
l=
Fe2+ (24) = 1s2 2s2 2p6 3s2 3p6 3d6 V
2 ¥ m¢ ¥ 2e ¥
l = 2 fi d 8
Electron present in (l = 2) d-orbitals = 6 V
11. (a) 1s4 2s4 2p8 3s4 3p8 4s2 m¢ ¥ 2e ¥ = m ¥ e ¥V
8
v m¢ = 4 m
12. (d) Hint Use
2p r 1242
13. (b) DE +2 = DEH 18. (a) Maximum KE of Ejected e– = – 4.65
Li 253.7
= 0.245 ev
È1 1˘ È1 1˘
13.6 ¥ 32 Í 2 - 2 ˙ = 13.6 ¥ 12 Í 2 - 2 ˙ 19. (c) Spherical node : Y2 = 0
Î n1 n2 ˚ Î1 4 ˚ s2 – 4s + 3 = 0; s2 – 3s – s + 3 = 0
È 1 ˘ È1 1˘ s (s – 3) – 1 (s – 3) = 0; (s – 1) (s – 3) = 0
Í 2 2˙
=Í 2 - 2˙ 2 Zr
Í Ê n1 ˆ - Ê n2 ˆ ˙ Î1 4 ˚ s = 1, 3; s= = 1, 3
a0
ÍÎ ÁË 3 ˜¯ ÁË 3 ˜¯ ˙
˚ 3 a0 1 a0
r= ,
fi n1 = 3 2 Z 2 Z
n2 = 12 nh
14. (c) Probability of finding and electron at a particular 20. (b) Let the orbits are n and (n + 1) mn1r1 = …(i)
2p
distance = 4pr2R2 (n + 1)h
4 mn 2 r2 = …(ii)
P1 = 4pr2R2 = 4pr2 ¥ 3 e -2 r / a0 2p
a0 The difference in angular momentum will be (ii) – (i)
4 -2 a0 / a0 (n + 1)h nh Ê h ˆ
at r = a0 p1 = 4p a02 ¥ e or (mv2 r2 - mv1r1 ) = - =Á ˜
a03 2p 2p Ë 2p ¯
a02 4
-2 a
0 1 Ê 1 1ˆ
at r = a0/2 p2 = 4p ¥ 3 e 2 a0 21. (a) = R ¥ (1) 2 ¥ Á 2 ¥ ˜ ; lmin = 911.7 Å
4 a0 lmin Ë1 •¯
35. (b) Ti = 1s2 2s2 2p6 3s2 3p6 3d2

2.19 ¥ 106 ¥ Zm/sec.
22. (a) n n =
n
For n = 2 of hydrogen atom n=2
6
2.19 ¥ 10 ¥ m/sec Magnetic moment = n(n + 2) fi 2(4) = 8 = 2.83 BM
n2 = = 1.09 ¥ 106 m/sec.
2 n3 T1 n13
23. (d) n1 + n2 = 4 36. (d) T µ = = 1/8
z2 T2 n23
n2 - n1 = 2
37. (a) E• – E1 = hn1, fi E1 fi hn1
2n2 = 6 E2 – E1 = hn2
\ n2 = 3 E• – E2 = hn3, fi E2 fi hn3
For the third line of the same series; –hn3 + hn1 = hn2
n1 = 1 and n2 = 4
v2 = v1 – v3
4
v3 = v1 – v2
3
2 hc
3rd Line 38. (d) EC – EB = ...(i)
1 l1
1 hc
È1 1˘ È1 1˘ EB – EA = ...(ii)
= RZ 2 Í 2 - 2 ˙ = R ¥ 9 Í 2 - 2 ˙ l2
l n
Î 1 n2˚ Î1 4 ˚
hc
l = 1080 nm EC – EA = ...(iii)
l3
h
24. (d) l = v l = add equations (i) and (ii)
mv
Ê1 1ˆ
EC – EA = hc Á + ˜
h Ë l1 l2 ¯
l 2 = fi l =
m put in equation (iii)
25. (b) According to Schrodinger’s model e– behave as Ê1 1 ˆ hc
hc Á + ˜ =
wave only. l
Ë 1 l 2¯ l3
26. (b) The maximum probability of finding an electron is
described by the orbital, which is denoted by Y2. 1 l1 + l2 ll
= fi l3 = 1 2
h l3 l1l2 l1 + l2
27. (a) lm = le l=
mv hc
h h ve mn 39. (d) DE =
= = l
mc vc mn vn vn mc hc
DE = (for H atom)
28. (b) (Y) is the solution of Schrodinger wave equation. l1
29. (d) 2pr = nl [as per de Broglie theory] hc
DE ¥ z2 = (for He+ ion)
30. (b) my = 0.25 mx, vy = 0.75 vx l2
h h h hc hc l
l= lx = , ly = ¥4= fi l2 = 1
mv m v
x x m yvy l1 l2 4
h 40. (b) First excitation potential
ly = ly = 5.33 A
0.25M x ¥ 0.75vx = E2 – E1 fi – 4 + 16 fi 12 eV
41. (d) n2= 4, n1 =3; n •
31. (a) Orbital angular momentum = l (l + 1) 
s p d f n2 = 5 n1 = 4; E/4
l=0 1 2 3 n2 = 6 n1 = 5; E
n Æ (n – 1) (n ≥ 4) 3E/4
m –1
32. (c) m = (2l +1) fi l = 42. (c) n2 = 5, n1 = 1
2 Dn( Dn + 1)
33. (d) Mn4+ = 1s2 2s2 2p6 3s2 3p6 3d3 Total number of spectrum line are
OR S (5 – 1) fi S4 2
OR S4 fi 4 +3 + 2 + 1
lyman Balmer Paschen brackett
34. (a) According to (n + l) rule, after np, (n + l) s always
Three line in visible reigon.
filled.
LEVEL III 1 h
Dp =
2¥2 p
(Match the Column) 1 h

Dv =
2 2m p
1. [(A) P (B) P, Q, R, S, T (C) Q, R, S (D) P ]
2. A – r.t B-p C-q, s D – q 20. (b) Dv = 0.3
3. A – p B- p C-p, q, r, s D – p h 6.6 ¥ 10-27
4. A – r, p B – r, t C – s D – q Conceptual Dx = = = 1.92 cm
4p mDv 4 ¥ 3.14 ¥ 9.1 ¥ 10-28 ¥ 0.3
5. A – r B - q C – p, t D - s
(A) for H , radius of second orbit 21. (d) When Dx = 0, Dp = •
22 Passage 5
= 0.53 ¥ = 0.53 ¥ 4 Å
1 h
22. (d) Orbital angular momentum (O.A.M) = l (l + 1)
6. (A) Æ t; (B) Æ s ; (C) Æ u ; (D) Æ q ; (E) Æ p; (F) Æ r 2p
7. (A) Æ u ; (B) Æ s ; (C) Æ p ; (D) Æ t ; (E) Æ q ; (F) Æ r n = 5, So l = 1,2,3,4. For maximum
8. (A) Æ q ; (B) Æ p ; (C) Æ q, r ; (D) Æ r, s h h
9. (A) Æ r ; (B) Æ s; (C) Æ p; (D) Æ q O.A.M = 4(5) = 20
2p 2p
10. A Æ P, BÆp, q, s, CÆp, r, D Æ q, s
Radial node = (n – l – 1) h
23. (b) m = l (l + 1) cos q ¥
Angular node = l 2p
4s, 5px, 6dxy having 3 radial node. l = 1 for p-orbital
angular node in all ‘s’ orbital in zero. h
m = 1(2) cos 45∞ ¥
Passage-1 2p
h
11. (b) 1st atom 2nd 3rd atom Z - component of O.A.M =
2p
24. (a) 8 = n(n + 2); n = 2
Number of unpaired electrons = 2
1 1
12. (b) s= + =1
2 2
150 h h
13. (c) l = Ls = s ( s + 1) = 2
V 2p 2p
V = 24 volt \ energy of free electron = 24 eV, 25. (a) Lyman series
È1 1˘ 1 È1 1˘
DE = 13.6 ¥ (Z)2 Í 2 - ˙ = n1 = RH ◊ 12 Í 2 - 2 ˙
Î6 •˚ l1 Î1 n2 ˚
= 1.51 eV
Total energy released = 24 – (–1.51) = 25.51 Balmer series
14. (b) (n – 2) 1 È1 1˘
6–2=4 = n 2 = RH ◊ 12 Í 2 - 2 ˙
l2 Î2 n2 ˚
15. (a) Minimum energy transition for 6 Æ 5
For highest energy transition
Passage 3 For Lyman series n2 = •
16. (c) Maximum number of electrons in an orbit is = 2n2 = 2 For Balmer series n2 = •
¥ 32 = 18
17. (d) Maximum number of electrons in a subshell = 2[2l n1 4
\ =
+ 1] = 4l + 2 = 4 ¥ 3 + 2 = 14 n2 1
18. (d) For 2p orbital n = 2, l = 1
1 È1 1˘
Passage 4 26. (b) = n = RH Z 2 Í 2 - 2 ˙
l
19. (d) Dx = 2Dp ÎÍ n1 n2 ˙˚
h For lowest energy transition of ion in Lyman series
Dx ¥ Dp =
4p È1 1˘
n = RH 22 Í 2 - 2 ˙ = 3RH
h Î1 2 ˚
2( Dp ) 2 =
4p
Passage 7 39. (c) mass number is the sum of n + p

27. (c) Cr3+ = 3d3 (Valance shell). 1242
n = 3 (Unpaired electrons) 40. (a) nm = 365.3 nm
3.4
m s = 15 BM 41. (a) Hund’s Rule
42. (b) (n + l) Rule and Hund’s Rule
43. (a) Spherical nodes = n – l – 1
28. (b) 2 –1 – 1 = 0
for p orbital l = 1
\ Spherical node for p orbital = n – 2
Fe3+ = 3d5 (Valance shell) 44. (b) Ruther ford’s experiment
45. (e) concept
1
s= in strong Oh magnetic field 46. (b) Spherical nodes = n – l – 1
2 angular node = l
Spin multiplicity = 2(s) +1 = 2 47. (a, b, d)
29. (a) Momentum = 2mK .E. Z Z 1
(a) v = 2.18 ¥ 106 ¥ fi v µ or v µ
Pe = Pa n n n
2me ◊ K.E.e = 2ma ◊ K.E.a v v Z /n Z2
(b) f = or f = µ 2 f µ 3
meK.E.e = maK.E.a 2p r r n /Z n
K.E.e ma È n3 ˘
= (c) r µ n 2 / Z ÍT µ 2 ˙
K.E a me Î Z ˚
Mass of a particle is more than mass of electron. mn 2 n 2 (Z 2 / n2 ) Z3
m K.E.e (d) F = \F µ µ 2 Fµ 4
Thus, a > 1; thus >1 r r n /Z n
me K.E a
So ans (A, B, D)
Thus statement 1 is true.
48. (a, c, d) B.E. = I.E.
Statement 2 is also true.
(I.E.)any atom = (I.E.)H ¥ z2
30. (d) Aufbau principle
31. (c) Pairing is favourable when all orbitals are half 122.4
= z2
filled. 13.6
32. (c) The Balmer series is born of transition of electron z2 = 9 z = 3
into the second orbit from higher orbits. E2 – E1= 122.4 – 30.6 = 91.8 eV
33. (b) Both statements are independently true. 49. [a, b, c, d] 10 cm–1 = 1000 m–1
34. (c) Cu+ = 1s2 2s2 2p6 3s2 3p6 3d10 hc
\ E = hn = = hc
í
All the electrons are paried; hence it is paramagnatic. l
(b) For energy of second orbit = 6.66 ¥ 10–34 (Js) ¥ 3 ¥ 108 (ms–1) ¥ 1000 (m–1)
22 = 2 ¥ 10–22 J per photon
= -13.6 ¥ 2 = -13.6 eV
2 = 2 ¥ 10–15 ergs per photon
42 = 2 ¥ 10–22 ¥ 6.02 ¥ 1023 J mol–1
(c) For radius of fourth orbit = 0.53 ¥ = 0.53 ¥ 4 Å
4 = 1.2 ¥ 10–1 kJ mol–1
Also, energy of fourth orbit
= 2.9 ¥ 10–2 kcal mol–1
42 50. [b, c, d] According to emission photoelectric effect
= -13.6 ¥ = -13.6 eV 1
42 hn = hn0 + mV2
(d) For, velocity of electron in third orbit = 2
hc
3 E of incident radiation =
2.18 ¥ 108 ¥ = 2.18 ¥ 108 Å l
3 6.626 ¥ 10 –34 ¥ 3 ¥ 108
Assertion and Reason =
200 ¥ 10 –10
Nodal plane in yz plane
35. (a) Px = 9.94 ¥ 10-18 J
5 ¥ 1.6 ¥ 10 –19
36. (a) Pauli rule n0 = = 1.2 ¥ 1015 sec–1
37. (b) Lobes = 2l 6.626 ¥ 10 –34
38. (a) Conceptual 1 2
mv = 9.94 ¥ 10–18 – 8 ¥ 10–19 = 9.14 ¥ 10–18
2
69. (6) Hint: n = 4, l = 1 represents 4P – subshell contain-

2 ¥ 9.14 ¥ 10 –18 ing six electrons. Thus, three will be six elements hav-
v= = 4.47 ¥ 106 m/sec
9.1 ¥ 10 –31 ing 4P1 to 4P6 electronic configuration.
51. (A, D) Both Fe3+ and Mn2+ have 5 unpair electrons. h
70. (0) Hint: ml = l (l + 1) (l = 0 for s -orbital)
Cu2Cl2 is colourless because Cu+ has no unpair elec- 2p
trons. 71. (5) Hint: Cu+ = [Ar]3d104s0
MnO -4 has no unpair electrons in Mn+7, due to charge 1
Five d – electrons have + spin
transfer spectra it is coloured. 2
m = n(n + 2) BM and n = 4 1
Five d – electrons have – spin
2
for Fe+2 and CO+3
72. (12) Hint: n = 4 l = 0 me = 0
52. (4) If m = + 3 (maximum), then l = 3 and n = 4
l = 1 me = –1, 0, +1
Number of waves in an orbit = n
l = 2 me = –2, –1, 0, +1, +2
53. (6) Number of spherical lines produced
l = 3 me = –3, –2, –1, 0, +1, +2, +3
(n – n )(n – n + 1) (5 – 2)(5 – 2 + 1)
= 2 1 2 1 = =6 There are three orbitals having me = +1, and three orbit-
2 2 als having me = –1,
54. (0) Orbital angular momentum Thus maximum number of electrons in them will be 12.
h h 73. (1) Hint: Number of radial nodes
= l (l + 1) = 0(0 + 1) =0
2p 2p = n – l – 1 = 3 – 1 – 1 (for 3P, n = 3, l = 1).
h 74. Distance to be travelled from Mars to Earth
55. (2) mvr = n = 8 ¥ 107 km
2p
h h = 8 ¥ 1010 m
=n ,n=2  velocity = 3 ¥ 108 m/sec
p 2p
8 ¥ 1010
56. (0) Number of radial modes = n – l – 1 \ Time = Distance/Velocity =
2–l–1=0 3 ¥ 108
-6.39 ¥ 10-19 = 2.66 ¥ 102 sec.
57. (4) Number of electron = =4
-1.60 ¥ 10-19 75. (a) I.P. = DE = E• – E1 = 0 –(–15.6) = 15.6 l.v.
58. (3) Number of waves = n 1= •
60. (1) Number of radial nodes = n – l – 1 = 2 – 0 – 1 = 1 (b) n = • n = 2

DE = [0 – (–5.3)] = 5.3 l.v.
61. (4) n(n + 2) = 24
1240 1240
n(n + 2) = 24, n = 4 DE = l= = 233.9 nm
l (nm) 5.3
62. (2) y420 is 4d orbital l = 2
63. (2) n – l – 1 = 3 – 0 – 1 = 2 (c) |DE3 Æ 1| = |–3.08 – (–15.6)|
64. (5) l = 2 = 15.6 – 3.08 = 12.52 e.v.
Number of d-electrons = 5 1240 12.52 1
= = = (n m)
65. (3) En = –13.6 + 12.09 = –1.51 l 1240 l
E -13.6 l = 1.808 ¥ 107 m–1
En = 21 \ n 2 = = 9, n = 3
n -1.51 (d) (i) E = –15.6 – (–6) = –15.6 + 6 = –9.6
66. (0) Hint: m = n(n + 2) = 35 BM (ii) E = –15.6 – (–11) = –15.6 + 11 = –4.6
n=5 n hc
76. E =
i.e., 5 unpaired ee are present in (n – 1)d l
shell of M+3 transition metal cation n ¥ 6.625 ¥ 10-34 ¥ 3 ¥ 108
so it is Fe+3 10–17 =
6 2 550 ¥ 10-9
26Fe Æ [Ar]3d 4s
5 0 n = 27.67 \ 28
Fe Æ [Ar]3d 4s
Circumference 77. 330 J = n(hn)
67. (2) Hint: Number of waves n = 330 J = n [6.62 ¥ 10–34 ¥ 5 ¥ 1013]
Wavelength
400 330
n= = 2 (or) nl = 2p r = n = 1022
200 6.62 ¥ 10-34 ¥ 5 ¥ 1013
n ¥ 200 = 400 nhC 3.15 ¥ 10 –14 ¥ 850 ¥ 10 –9
n=2 78. E = n=
68. (4) Hint: m = 3, l = 3, n=4
l 6.62 ¥ 10 –34 ¥ 3 ¥ 108
For n = 4 number of waves will be 4. n = 134.8 ¥ 103 n = 1.35 ¥ 105
1 È1 1˘ = 5.425 ¥ 10–12 ergs

79. = Rh Z 2 Í 2 - 2 ˙
l Î n1 n2 ˚ 6.625 ¥ 10 –34 ¥ 3 ¥ 108
(b) l =
n1 = 3 for paschan 5.425 ¥ 10-19
80. n2 = 3 n1 = 2 [first line] = 3.66 ¥ 10–7 meter = 3.7 ¥ 10–5 cm
n2 = 4 n1 = 2 [second line] È 1 1˘
1 86. DE = I.E. Í – ˙
È1 1˘ 2 Æ1 Î 4 1˚
= RH Í – ˙
l Î4 9˚ È 1 1˘ hc
1 2.17 ¥ 10–11 erg/atom Í – ˙ =
È1 1˘ Î 4 1 ˚ l ( m)
Å = RH Í – ˙ (i)
6565 Î4 9˚ –34 8
È 1 1˘ 6.626 ¥ 10 ¥ 3 ¥ 10
1 È1 1 ˘ 2.17 ¥ 10–11 ¥ 10–7 J Í – ˙ =
= RH (ii) Î 4 1˚ l
l ÍÎ 4 – 16 ˙˚
6.626 ¥ 1034 ¥ 3 ¥ 108 ¥ 4 6.626 ¥ 4 ¥ 108
5 l= =
2.17 ¥ 10 –18 ¥ 3 2.17
l 36 5 ¥ 16
= = l = 4863 Å = 12.20 ¥ 10–8 m = 1220 Å
6565 3 36 ¥ 3
16 Z 2.18 ¥ 106
81. 3 Æ 2 87. Vn = 2.18 ¥ 106 ¥ =
n n
1 È1 1˘ È1 1˘
= RH ¥ Z 2 Í 2 – 2 ˙ = RH ¥ Í – ˙ ...(i) 2.18 ¥ 10 6
1 v
l1 Î n1 n 2 ˚ Î4 9˚ = =
n 275 3 ¥ 108
1 È1 1 ˘
2 Æ1 = RH ¥ 4 Í – ˙ ...(ii) 2.18 ¥ 106 3 ¥ 108
l2 Î1 4 ˚ =
n 275
(l1 – l2) = 133.7 nm ...(iii) n = 1.99  2
We solve the three equations and we get
88. Z = 3, n1 = 1, n2 = 3
R = 1.096 ¥ 107 m–1
È1 1˘ È1 1 ˘
È1 1 ˘ En = 13.6 ¥ (Z2) Í 2 – 2 ˙ = 13.6 ¥ 9 Í – ˙
82. DE = 13.6 Í – ˙ ¥ 96.3368 kJ/mole n
Î 1 n2˚ Î1 9 ˚
Î9 4 ˚
8
È4 – 9˘ = 13.6 ¥ 9 ¥ = 108.8 eV
= 13.6 Í ¥ 96.368 = 182.074 9
Î 36 ˙˚
È1 1˘ È1 1 ˘
= 1.827 ¥ 105 J/mole 89. (i) En2 Æ n1 = 13.6 ¥ Z 2 Í 2 – 2 ˙ = 13.6[1]2 Í – ˙
Î n1 n2 ˚ Î1 4 ˚
hc
83. IE per mole = N A ¥ 3
l = 13.6 ¥ 1 ¥ = 10.2 eV
4
6.022 ¥ 1023 ¥ 6.625 ¥ 10-34 ¥ 3 ¥ 108
= J 1 È1 1˘
854 ¥ 10-10 (ii) = RH Z 2 Í 2 – 2 ˙
l Î n1 n2 ˚
= 0.14 ¥ 107 = 14 ¥ 105 J = 1400 KJ/Mole
1 7 2 3
84. Radius = 16 ¥ radius of H in ground state = 16 ¥ 0.529 –8 = 1.09 ¥ 10 ¥ Z ¥
3 ¥ 10 4
n2
16 ¥ 0529 = 0.0529 ¥ \ Z=2
Z 90. 1.8 mole = (1.8 NA) atoms
n2 27% = IIIrd energy level = 1.8 ¥ NA ¥ 0.27 = 0.486 NA
16 = n=4
1 15% = IInd energy level = 1.8 ¥ NA ¥ 0.15 = 0.27 NA
Z2
T.E. = –13.6 ¥ 2 e.v. = –0.85 e.v. DE = DE1 + DE2
n 3Æ1 2 Æ1
–12
– 21.7 ¥ 10 È 1 1˘
85. En = 1 erg = 10–7 Joule = 1.8 ¥ NA ¥ 0.27 ¥ IE + Í – ˙
n2 Î 9 1˚
– 21.7 ¥ 10 –12 È 1 1˘
En = + 1.8 ¥ NA ¥ 0.15 ¥ IE Í – ˙
4
Î 4 1˚
È – 21.7 ¥ 10 –12 ˘ 21.7 ¥ 10 –12 = (0.432 NA + 0.20 NA) ¥ IE = 56.65 ¥ 1011 erg.
J.E. = 0 - Í ˙=
Î 4 ˚ 4
91. Number of atom in third orbit = 0.5 NA The energy of photon which can cause ejection of elec-
Number of atom in second orbit = 0.25 NA tron
Total energy evolve = 0.5 NA(E3 – E1) + 0.25NA(E2 – E1) = 2.179 ¥ 1018 + 1.092 ¥ 10–18
Ê hˆ = 3.271¥ 10–18J
92. Angular momentum = n Á ˜
Ë 2p ¯ 97. Energy required per molecule in the following process
is given as
Ê hc ˆ (1) 2
ÁË ˜¯ = – 3.4 eV –3.4 = –13.6 ¥ hn
O 2 ææÆ O + O *
l n2
– 3.4 1 13.6 h ¥ c 6.626 ¥ 10 –34 ¥ 3 ¥ 108
= 2 2
n = =4 E= =
–13.6 n 3.4 l 174 ¥ 10 –9
n2 = 4 fi n = 2 = 11.424 ¥ 10–19 J/molecule

Energy for O Æ O* is 3.15 ¥ 10–19 Joule
Ê 6.626 ¥ 10 –34 ¥ 7 ˆ h 6.62 ¥ 10 –39 ¥ 7 Thus, energy O2 Æ 2O will be
= 2Á ˜ = or
Ë 2 ¥ 22 ¯ p 2 = 11.424 ¥ 10–19 – 3.1 ¥ 10–19
= 8.274 ¥ 10–19 J/molecule
1240 1 4.5
93. 4.5 eV = = = 0.0036 nm–1 = 8.274 ¥ 10–19 ¥ 6.023 ¥ 1023 ¥ 10–3 kJ/mole
l (nm) l 1240 = 498.3 kJ/mole
Dn( Dn + 1)
94. = 15 1 V0
2 98. V2 = V0 ¥ =
2 2
Dn (Dn + 1) = 30 = 5 ¥ 6 x=v¥t
\ n1 = 1 and n2 = 6
1 È1 1 ˘ V0 Ê V ¥ 10 –8 ˆ
= RH ¥ Í – ˙ x= ¥ 10 –8 sec = Á 0 ˜¯ m
lÅ Î1 36 ˚ 2 Ë 2
1 1 35 35 ¥ 2496 2pr distance covered in 1 round
= ¥ =
x 912 36 32832 V0 ¥ 10 –8 V ¥ 10 –8 1
\ distance covered in 0 ¥
l = 932 Å 2 2 2p r
r2 = r0 ¥ n2 = 4r0
95. The condition can be met by taking first derivative P(r)
w r.t r and setting the same equal to zero, i.e., V0 /2 ¥ 10 –8 V0 ¥ 10 –8 ¥ 1
so, number of revolutions = =
v
dP(r ) 1 ÈÊ 1 ˆ 2 – r / a0 ˘ 2p ¥ 4r0 2 ¥ 2p ¥ 4r0
= ÍÁ 3 ˜ e ˙=0
dr dr ÍÎË p a0 ¯ ˚˙ 2.18 ¥ 106 ¥ 10 –18
=
2 ¥ 2 ¥ 3.14 ¥ 4 ¥ 0.529
\ r = a0 ( e -2 r / a0 π 0)
96. The energy of photon which can cause ejection of elec- 2.18 ¥ 10 –12
= = 0.838 ¥ 1019 = 8 ¥ 106
tron = kinetic energy of ejected electron + ionisation 2.6 ¥ 10 –21
energy …(i)
Ionisation energy = 13.6 eV V
99. n =
13.6 l
= J = 2.179 ¥ 10–18 J …(ii)
6.24 ¥ 1018 E of Ist Bohr orbit = –13.6
Here 6.24 ¥ 1018 eV = 1 J
h 6.626 ¥ 10 –34 ¥ 3 ¥ 108
de Broglie wavelength = l = -13.6 =
mv l
1240
h 6.626 ¥ 10 –34 or -13.6 =
\ v= = l (in nm)
ml 9.1 ¥ 10 –31 ¥ 4.7 ¥ 10 –10
= 0.15492 ¥ 107 m/sec 1240
l= ¥ 10
1 136
K.E. = mv 2
2 l = 91.17 (nm) = 912 Å
1
= ¥ 9.1 ¥ 10–31 ¥ (0.15492 ¥ 107)2 1
2 2.18 ¥ 106 ¥
n= 1 = 2.3 ¥ 1013 Hz
= 1.092 ¥ 10–18J …(iii)
Now from Eq. (i) 912 ¥ 10-10
Ê 1 1ˆ hc
100. DE = 47.2 eV = 13.6 Z2 Á - ˜ 8. DE = E3 – E2 =
Ë 4 9¯ l
hc
47.2 5 2 = –2.41 ¥ 10–12 – (5.42 ¥ 10–12) =
= Z l
13.6 36
6.626 ¥ 10 –34 ¥ 3 ¥ 108
Z2 = 25 = 3.01 ¥ 10–12 ¥ 10–7 =
\ Z=5 l
–26 –7
101. DE = Z2 ¥ 10.2 eV = 4 ¥ 10.2 eV 6.626 ¥ 10 ¥ 3 6.626 ¥ 10 ¥ 3
l= =
3.01 ¥ 10 –19 3.01
1 –7
K.E. = mV 2 = 4 ¥ 10.2 - 13.6 eV = 6603 Å = 6.603 ¥ 10 m
2
È1 1˘
2 ¥ 27.2 ¥ 1.6 ¥ 10-19 9. DE = 2.17 ¥ 10–18 Í 2 – 2 ˙
\ V= -31
= 3.09 ¥ 106 m/sec. Î n1 n2 ˚
9.1 ¥ 10
hc È 1˘
= 2.17 ¥ 10 –18 Í1 – ˙
102. B.E. = 180.69 kJ/mole fi w = hv0 l Î 4˚
180.69 6.62 ¥ 10 –34 ¥ 3 ¥ 108 3
eV/atom = hv0 = 2.17 ¥ 10 –18 ¥
96.368 l 4
180.69
¥ 1.6 ¥ 10-19 = 6.6 ¥ 10-34 ¥ v0 4 ¥ 6.62 ¥ 3 ¥ 10 –26
96.368 l= = 12.20 ¥ 10 –8 m = 1220 Å
6.51 ¥ 10 –18
v0 = 6.626 ¥ 10-34
2.17 ¥ 10 –18 2.17 ¥ 10 –18
103. hn1 = hn0 + 2E1 and hn2 = hn0 + E1 10. DE = 2
¥ Z2 = = 5.42 ¥ 10-19
n 4
hn1 – hn0 = 2E1 and hn2 – w0 = E1 or 5.42 ¥ 10–12 erg
hn - w0 hc
2= 1 \ 2hn 2 - 2 w0 = hn1 - w0  DE =
hn 2 - w0 l
h[2n2 – n1] = w0 6.626 ¥ 10 –34 ¥ 3 ¥ 108
l= = 3.67 ¥ 10-7 meter
w0 = 6.62 ¥ 10–34 (4 ¥ 1015 – 3.2 ¥ 1015) 5.42 ¥ 10 –19
w0 = 6.62 ¥ 10–34 ¥ 0.8 ¥ 1015 or 3.67 ¥ 10–5 cm
w0 = 5.29 ¥ 10–19 w0 = 318.9 kJ/mol 11. For n = 3 and l = 2 (i.e., 3d orbital), the values of m
varies from –2 to +2, i.e., –2, –1, 0, +2 and for each ‘m’
there are 2 values of ‘s’, i.e., +1/2 and –1/2.
PREVIOUS YEARS’ QUESTIONS Maximum number of electrons in all the five d-orbitals
OF JEE (MAIN & ADVANCED) is 10.
2 1 1 – 21.76 ¥ 10 –19 ¥ 4
1. (d) Charge/mass for n = 0, a = , p = , e = 12. E rd = J
4 1 1/1837 3 9
So, order is n, a, p, e 87.04
2. (a) Isotonic : same number of neutrons = ¥ 10 –19 = 9.67 ¥ 10 –19 J
9
3. (c) Conceptual
hc
h 6.6 ¥ 10-34 \ DE =
4. (c) l = = = 2.37 ¥ 10-30 m l
mv (0.2) ¥ 5/(60 ¥ 60)
6.626 ¥ 10 –34 ¥ 3 ¥ 108
5. (a) Z = 37, so electronic configuration is 1s2 2s2 2p 3s2 l=
3p6 4s2 3s10 4p6 5s1 9.67 ¥ 10 –19
\ for outermost electron = 2.0556 ¥ 10–7 M = 2055 Å
6. (c) Most electro-negative element is F. h 6.62 ¥ 10 –34
\ electronic configuration: ns2np5 13. l = =
mu 0.1 ¥ 100
7. Average mass = Mass of isotopes ¥ Mole fraction +
Mass of isotopes ¥ Mole fraction or l = 6.62 ¥ 10–35 m = 6.62 ¥ 10–25 Å
10.81 = 11.01 ¥ x + 10.01 (1 – x) 14. For hydrogen atom, Z = 1, n = 1
10.81 = 11.01 x + 10.01 – 10.01 x Z
V = 2.18 ¥ 106 ¥ ms –1 = 2.18 ¥ 106 ms–1
x = 10.81 – 10.01 = 0.80 n
% = 0.80 ¥ 100 = 80% de Broglie wavelength,
Kinetic energy = Absorbed energy – Bond energy

h 6.26 ¥ 10-34
l= = \ kinetic energy = 4.417 ¥ 10–19 – 3.984 ¥ 10–19 J
mv 9.1 ¥ 10 –31 ¥ 2.18 ¥ 106
= 3.34 ¥ 10–10 m = 3.3 Å = 4.33 ¥ 10–20 J
\ kinetic energy of each atom
For 2p, l = 1
h 4.33 ¥ 10 –20
\ Orbital angular momentum 2 = = 2.165 ¥ 10–20 J
hc 2p 2
15. From DE = Ef – Ei = 19. The shortest wavelength transition in the Balmer series
l
corresponds to the transition
È 1 1 ˘
2.18 ¥ 10–18 ¥ Z2 Í 2 – n = 2 Æ n = •. Hence, n1 = 2, n2 = •
Î (1) (2) 2 ˙˚
Ê 1 1ˆ Ê 1 1 ˆ
6.626 ¥ 10 –34 ¥ 3 ¥ 108 n = RH Á 2 – 2 ˜ = (109677 cm –1 ) ¥ Á 2 – 2 ˜
= Ë n1 n2 ¯ Ë 2 • ¯
3 ¥ 10 –8
= 27419.25 cm -1
3
or –2.18 ¥ 10–18 ¥ Z2 ¥ = 6.626 ¥ 10–18 20. As the a particle travelling with velocity, ‘u’ stops at a
4
6.626 ¥ 10 –18 ¥ 4 distance 10–13 m, its K.E. becomes zero and gets con-
Z2 = ª4 verted in to P.E.
2.18 ¥ 10 –18 ¥ 3
Z=2 1 2 1 2 Ze 2 Ze 2
mu = ¥ or u 2 =
for He+ Z = 2 2 4pe 0 r pe 0 ◊ m.r
16. DEHe+ = DEH
Here, Z = 29 for Cu atom
È1 1 ˘ 29 ¥ (1.6 ¥ 10 –19 ) 2
or -2.18 ¥ 10-18 ¥ Z 2 Í – ˙ fi u2 =
Î 4 16 ˚
3.14 ¥ 8.85 ¥ 10 –12
È1 1˘
= – 2.18 ¥ 10 –18 Í 2 – 2 ˙ ¥ (4 ¥ 1.672 ¥ 10 –27 ) ¥ 10 –13
Î n1 n2 ˚
\ u = 6.3 ¥ 106 m sec–1
È1 1 ˘ È 1 1˘
4Í - ˙ = Í 2 - 2 ˙ 1 2 h
Î 4 16 ˚ Î n1 n2 ˚ 21. mu = eV; also l =
2 mu
\ n1 = 1 and n2 = 2
17. rn for H = r1 ¥ n2 1 h2 1 h2
\ m 2 2 eV or V =
R3 for H = 0.529 ¥ 9 ¥ 10–8 cm = 529 ¥ 9 ¥ 10–10 m 2 m l 2 ml 2e
( r1 = 0.529 A°)
1 ¥ (6.62 ¥ 10 –34 ) 2
u V=
Also un = Z 1 2 ¥ 9.108 ¥ 10 –31 ¥ (1.54 ¥ 10 –10 ) 2 ¥ 1.602 ¥ 10 –19
n
= 63.3 volt
2.19 ¥ 108 2.19 ¥ 106
\ u3 = cm sec –1 msec –1 22. Determination of number of moles of hydrogen gas,
3 3
( u1 = 2.19 ¥ 108 cm sec–1) PV 1¥1
n= = = 0.0409
\ Number of waves in one round RT 0.082 ¥ 298
2p r3 2p r3 2p r3 ¥ u3 ¥ m The concerned reaction is H2 Æ 2H; DH = 436 kJ mol–1.
= = = Energy required to bring 0.0409 moles of hydrogen gas
l h /mu3 h
to atomic state = 436 ¥ 0.0409 = 17.83 kJ.
2 ¥ 22 ¥ 0.529 ¥ 9 ¥ 10 –10 ¥ 2.19 Calculation of total number of hydrogen atoms in
¥ 106 ¥ 9.108 ¥ 10 –31 0.0409 mole of H2 gas.
= =3 1 mole of H2 gas has 6.02 ¥ 1023 molecules
7 ¥ 3 ¥ 6.62 ¥ 10 –34
6.02 ¥ 1023
18. Bond energy of I2 =240 kJ mol–1 = 240 ¥103 J mol–1 0.0409 mole of H2 gas = ¥ 0.0409
1
240 ¥ 103
= J mol –1 = 3.984 ¥ 10–19 J mol–1 Since 1 molecule of H2 gas has 2 hydrogen atoms, 6.02
6.023 ¥ 1023 ¥ 1023 ¥ 0.0409 molecules of H2 gas = 2 ¥ 6.02 ¥ 1023
hc 6.626 ¥ 10 –34 Js ¥ 3 ¥ 108 ms –1 ¥ 0.0409 = 4.92 ¥ 1022 atoms.
Energy absorbed = =
l 4500 ¥ 10 –10 m Energy required to excited an electron from the ground
= 4.417 ¥ 10–19 J state to the next excited state
Ê 1 (b) To describe a one electron wave function, three

1ˆ Ê1 1ˆ
= 13.6 Á 2 – 2 ˜ eV = 13.6 ¥ Á – ˜ quantum numbers n, l and m are needed. Further
Ë n1 n2 ¯ Ë 1 4¯
to abide by Pauli exclusion principle, spin quan-
3 1.6 ¥ 10-19 tum number (s) is also needed.
= 13.6 ¥
= 10.2 eV = 10.2 ¥ KJ
4 1000 (c) For shape, size and orientation, only n, l and m are
Therefore, energy required to excite 4.92 ¥ 1022 elec- needed.
trons (d) Probability density (y2) can be determined if n, l
= 1.632 ¥ 10–21 4.92 ¥ 1022 kJ and m are known.
= 8.03 ¥ 10 = 80.3 kJ
Therefore, total energy required = 17.83 + 80.3 Comprehension-Based Questions
= 98.17 kJ 27. fi n = 2, i.e., S1 = 2s orbital.
23. For maximum energy, n1 = 1 and n2 = • 28. Ground state energy of electron in H –atom.(EH)
1 Ê 1 1ˆ
= RH Z 2 Á 2 – 2 ˜ [3]2
l Ë n1 n2 ¯ -13.6 ev
( ELi+2 ) S1 [2]2 9
= = = 2.25
Since RH is a constant and transition remains the same EH [1] 2
4
-13.6 ¥ 2 ev
1 l Z2 1 [1]
µ Z 2 ; He = 2H =
l lH Z He 4
29. In S2 state, E (Li2+) = k (given)
1
Hence, lHe = ¥ 91.2 = 22.8 nm (3) 2 (1) 2
4 ELi+2 = -13.6 ev = 13.6 ¥ ev
2 n22 (1) 2
24. y 2s = Probability of finding electron within 2s sphere
2 \ n2 = 3 = S2
y 2s = 0 (at node)
( probability of finding an electron is zero at node) Integer-Type Questions
2 2
È 1 1 Ê 1 ˆ 3/2 Ê r0 ˆ ˘ 30. When n = 3, l = 0, 1, 2, i.e., there are 3s, 3p and 3d
\ 0=Í Á ˜ Á 2 - ˜ ¥ e – r0 / a0 ˙ orbitals. If all these orbitals are completely occupied as
ÍÎ 4 2p Ë a0 ¯ Ë a0 ¯ ˙˚
È r0 ˘ r0
fi Í2 – a ˙ = 0; \ 2 = a ; 2a0 = r0
Î 0˚ 0 1
25. A Æ r; B Æ q, C Æ p, D Æ s Total 18 electrons, 9 electrons with s = + and 9 with
2
1
(a) Potential Energy s=- .
2
1 Ê Ze 2 ˆ z2
= - ÁË ˜¯ = -13.6 ¥ 2 2 ev 13.6
4pe 0 r n 31. \ En = - eV where, n = 1, 2, 3..........
n2
z2 -13.6
Kinetic energy = +13.6 ev In excited states, E2 = = - 3.4 eV
n2 4
32. (a) Given, atomic number of Rb, Z = 37
1 Ê Ze 2 ˆ Vn
Kn = ÁË ˜¯ fi = - 2( R ) Thus, its electronic configuration is [Kr]5s1. Since, the
8pe 0 r Kn last electron or valence electron enter is 5s subshell.
Ze 2 Z2 So, the quantum numbers, are n = 5, l = 0, (for s-orbit-
(b) En = - = -13.6 2 ev µ r -1 fi x = -1 al) m = 0  m = + l to – l, s = +1/2 or –1/2.
8pe 0 r n
h ÈZ2 ˘
(c) Angular momentum = l (l + 1) 33. (a) Given, in the question E = - 2.178 ¥ 10-18 J Í 2 ˙
2p În ˚
= 0 in S orbital For hydrogen Z = 1,
2 2
an n È1˘
(d) rn = 0 = 0.529 Å So, E1 = - 2.178 ¥ 10-18 J Í 2 ˙
z z În ˚
26. A Æ q; B Æ p, q, r, s; C Æ p, q, r ; D Æ p, q, r
È1˘
h E2 = - 2.178 ¥ 10-18 J Í 2 ˙
(a) Orbital angular momentum (L) = l + (l + 1) Î2 ˚
2p
i.e., depends on azimuthal quantum number only. Now, E1 – E2 i.e.
1 ˆ hc 4s 4p 4d 4d
Ê1
DE = 2.178 ¥ 10-18 Á 2 - 2 ˜ = 0 –1 0 +1 –2 –1 0 +1 +2 –3 –2 –1 0 +1 +2 +3
Ë1 2 ¯ l
1 ˆ 6.62 ¥ 10-34 ¥ 3.0 ¥ 108 According to question |m1| = 1, i.e. there are two pos-
Ê1
2.178 ¥ 10-18 Á 2 - 2 ˜ = sible values of m1, i.e. +1 and –1 and one orbital can
Ë1 2 ¯ l
1
\ l = 1.21 ¥ 10–7 m contain maximum two electrons one having s = +
and other having s = –1/2. 2
34. (c) According to Bohr’s model,
So, total number of orbitals having {|m1| = 1} = 6
nh n2h2 Total number of electrons having
mvr = fi (mv) 2 = 2 2
2p 4p r 1¸
Ï
1 2 n2h2 Ì| m1 | = 1 and m2 = ˝ = 6
fi Kinetc Energy = mv = 2 2 Ó 2˛
2 8p r m 1 3
Also, Bohr’s radius for H-atom is, r = n2a0 36. (5) Hint: K.E. = MV 2 = RT
2 2
Substituting ‘r’ in Eq. (i) gives
\ m 2v 2 = 2mKE \ mv = 2mKE
h2 h2
K.E. = 2 2 2 when n = 2, K.E. = h h h
8p n a0 m 32p 2 a02 m l(wavelength) = = µ
mv
2mKE 2m(T )
35. (6) Hint: This problem is based on correct of quantum
number. Follow the following steps to solve this prob- Where, T = Temperature in Kelvin
lem. Write all possible orbital's having combination of h
l (He at – 73°C = 200 K) =
same principal, azimuthal, magnetic and spin quantum 2 ¥ 20 ¥ 1000
number. Then count the all possible electrons having
given set of quantum numbers. For n = 4, the total num- l (He) 2 ¥ 20 ¥ 1000
\ =M = =5
ber of possible orbitals are l (Ne) 2 ¥ 4 ¥ 200
Thus, M = 5
Chapter
3
Gaseous
State
Key Concepts
In this chapter, we will study about physical classification 3. Pressure of gas P
of matter. State in which a matter exists depends upon two 4. Temperature of gas T
factors: Temperature determines the direction of heat flow.
1. Intermolecular force: This gives an idea of binding There are three scales for temperature measurement.
force between constituents particles.
(i) Celcius scale (°C)
2. Kinetic energy or thermal or heat: It gives the idea of
(ii) Kelvin scale (K)
velocity of constituent particles.
These two factors at a given temperature decide the (iii) Fahrenheit scale (°F)
state of aggregate matter. Tanyscale - F.P.(water)
Property Solid Liquid Gas = constant
(BP - FP) water
1. Shape Fixed Not fixed Not fixed
2. Intermolecular High Lower Least
BP = Boiling Point
force of attraction than solid
3. Volume Fixed Fixed Not fixed FP = Freezing Point
4. Density High Intermediate Low This equation is used to convert temperature from 1 scale
5. Kinetic energy Least Higher than High to another scale.
solid
(BP)water °C100 K373 F212
6. Diffusibility Less Medium High
7. Compressibility Low
Gas
Medium High | | |
Ideal Real (FP)water 0 273 32
1. No intermolecular force Exist
of attraction or repulsion t °C - 0 t - 273 T - 32
= k = F
2. The volume of gaseous Molecular 100 - 0 373 - 273 212 - 32
molecules is negligable volume exist
in comparison to the 5
volume of container eg. 1. t°C = [tf – 32]
9
It is a theoretical concept, For example, all gases
there is no ideal gas around us. 5
2. Tk = t( f ) + 255.2
Measurable properties of gases: 9
1. Number of moles of gases or amount of gas (n) 3. Tk = 273 + °C
2. Volume of gas V
F mg Vaccum
Pressure : P = =
A A A
(No gas particle)
It is the force exerted by the gas per unit area on the walls of
a container. Pressure exerted because of collision and caus- h
ing change in momentum assuming no intermolecular force B
of attraction.
Device:
1. Baromater (Atmospheric pressure)
2. Monometer (Other than atmospheric pressure)
Unit:
Hg is preferred in barometer because density is high, length
1 atm = 76 cm of Hg = 760 mm Hg = 760 torr
of tube small and non volatile.
= 1.013 ¥ 105 N/m2 or pascal
For other liquid
Other liquid Hg
EXPERIMENTAL METHOD FOR h1d1g h2d2g
PRESSURE CALCULATION
h1d1 = h2 d 2
PB = PA + DP
or hd = constant
= PA + Pressure due to ‘h’ column (liq)
Hg H2O
Ê Fˆ mg 0.76 ¥ 13.6 ¥ 103 = h2 ¥ 1 ¥ 103
PB = PA + Á ˜ = PA +
Ë A¯ A 0.76 ¥ 13.6
h1 = = 10.33 meter
V ¥d ¥g 1
= PA +
A It means d≠ then hØ
A◊ h ◊ d ◊ g Case II
= PA +
A
Gas
PB = PA + hdg
A
Patm h
A B
h Patm
B C
d
Patm = PA + hdg
This formula is applicable only when d is constant Ø Ø
throughout vertical height. Pressure Pressure
PB = PC because h is same. of gas due to column
Q.1 (i) An open tank is filled with Hg upto a height of 76
Barometer: cm. Find pressure at the bottom and middle of the
Case I tank. If atmospheric pressure is 1 atm.
\ PA = 0 (ii) Find the height of water up to which water must be
PB = PA + DP filled to create same pressure at the bottom.
PB = 0 + hdg Q.2 What will be the pressure
d = 13.6 gm/cm3 = 13.6 ¥ 9.8 (i) at the bottom of the Patm
g = 9.8 m/sec2 and h = 76 cm tank?
\ PB = hdg (ii) at middle of the bottom d2 h2
= 0.76 ¥ 13.6 ¥ 103 ¥ 9.8 layer? If two immis-
cible liquids are filled
= 1.01325 ¥ 105 pascal d1 C h1
as shown in the above
PB = 1 atm
figure. B
Gaseous State 3.3
Q.3 What will be the pressure (ii) y = mx

(i) at the bottom of the tank? y
(ii) at h1/2 height from bot-
tom if two completely
miscible liquids densi- d2 h2
ties are d1 and d2 are m tan q slope
filled as shown in the q
following diagram as- d1 C h1 x
suming cross-section
area is same. B (iii) yx = constant
constant
(Discussed in Solved Examples) y=
x
MONOMETER Hyberbola
(Rectangular)
Closed end y
Vaccum
Gas P=0 x
P = hdg 2
h Pgas = PA + hdg (iv) y = kx
Hg Pgas = 0 + hdg Parabolic
equation
Pgas = hdg
K > 0 or +ve
Open end
There are three posibility K < 0 or ve
(v) x = Ky2
If K < 0 or –ve
Gas Gas Gas If K > 0 or +ve
h h
Hg
x
If level of Hg is Pgas > Patm Pgas < Patm
same in both limb. Pgas = Patm + hdg Pgas = Patm hdg
Pgas = Patm Pgas = 1 + h(cm)/76 atm Pgas = 1 h(cm)/
76 atm
Q4. Find pressure of the gas inside the container if manom- Gas Laws _______________________________
eter attached to the container show a difference of 60 Assumption
mm as shown in figure? 1. All gases are assumed to have no molecular attraction
and volume of gas molecule is negligible.
Gas
2. In any gas law, relation between any two parameter are
studied and other two are kept constant.
60 mm Hg
3. All gas laws are based on experiment.
Boyle’s Law Gas
P (1) (2)
60 6 This law states that for a fixed amount
P = Patm += 1 + atm of gas kept at fixed temperature
760 76
Common equation for graph the pressure exerted by gaseous P2 (P2V)
(i) y = mx + C molecule is inversaly proportional to
the volume of the gas. (P1V) n2
y P1
1 n1
Pµ [n and T constant]
q V V V
tan q m slope K
P=
C V
x
PV = K (1)
P=y È nR ˘
3. Gaylussac law: P µ T and Í K =
V=x Î V ˙˚
yx = K constant. È RT ˘
K 4. Avogadro’s law: V µ n and Í K =
PV = nRT = K \P= P2 > P1 Î P ˙˚
V
Ê Kˆ Ê Kˆ
(nRT)2 > (nRT)1 ÁË ˜¯ > ÁË ˜¯
V 2 V 1 Graph’s for Boyl’s law ____________________
(i) If T1 = T2 \ n2 > n1
(ii) If n1 = n2 \ T 2 > T1 1
1. P VS
V
Charle’s Law (2)
K P
This law states that for a fixed amount of gas at constant P=
V P2 (1)
pressure, volume occupied by two gases is directly 1
proportional to absolute temperature. P=K◊
V µ T [n and p constant] V P1
y = mx
V nR P (2) Gas P2 > P1
=K= 1/V
T P
or V2
(V2T) (1) Gas Ê Kˆ Ê Kˆ
ÁË ˜¯ > ÁË ˜¯
V 2 V 1 { 1
V
is same }
V = KT V1 (V1T) K2 > K1
= y = mx
(i) If n1 = n2 V2 > V1
T (nRT)2 > (nRT)1
P1 > P2 (KT)2 > (KT)1 (i) If n1 = n2 \ T 2 > T1
Ê nR ˆ Ê nR ˆ (ii) If T1 = T2 \ n2 > n1
(ii) If P1 = P2 K2 > K1 or ÁË ˜¯ > ÁË ˜¯
P 2 P 1 2. PV VS P
\ n2 > n1 y = PV
At constant pressure, the volume of a given amount of a
x=P
1
gas increases or decreases by th of volume at 0°C per From Boyl’s law
273.15
degree rise or fall of temperature PV = K = y
P≠ then VØ
V
V0 K2 > K1
m tan q
275.15 (nRT)2 > (nRT)1
(2)
273.15°C t°C
(nRT)2 K2 (1)
If V0 is the volume of gas at 0°C then at t°C nRT1 K1
{
Vt°C = V0 +
V0
273.15
t } 3. log P VS log V
fi y = C + mx y = log P
x = log V
Note:
Temperature lower than –273.15°C is not possible because
volume of gas cannot be negative.
1 Slope 1
1. Boyle’s law: P µ and [K = nRT] log P
V
C log K log (nRT)
È nR ˘
2. Charle’s law: V µ T and Í K =
Î P ˙˚
log V
Gaseous State 3.5
But from Boyl’s law

PV = K
log(PV) = logK = log(nRT)
logP + logV = logK Slope
logP = –logV + logK q
log P
= y = –mx + C
log nRT
P 1
4. VS 2
V V log 1/V
P 1
y = and x = 2 P
V V 8. vs V2
V
But PV = K P/V
PV K From Boyl’s law
\ 2
= 2 PV = constant = K
V V
P 1 1/V2 PV K
= ¥K 2
= 2
V V2 V V
∫ y = mx P K
= P/V
P 1 V V2
5. VS
V V P
= y and V2 = x
P 1 V
y = and x = V2
V V
K
But PV = K y=
x
PV K
= yx = K
V2 V2
P 1
=K 2 (1) (2) Special Case for Charle’s Law ______________
V V P (i) V µ T
∫ y = Kx2 V nR
Since P =K=
P V T P
Ê Pˆ Ê Pˆ
1
>
ÁË ˜¯ ÁË ˜¯
V P V = KT
V 1 V 2 V 2 ∫ y = mx
V
slope
Ê Kˆ Ê Kˆ 1/V (ii) V = KT K
ÁË 2 ˜¯ > ÁË 2 ˜¯ = K[t°C + 273] q
V 1 V 2 T
V = Kt°C + 273 K
1
6. VS P
V
K
1 q
V
V
273 K
t°C
P
(iii) V = KT
1
7. log P vs log
V È5 ˘
V = K Í T f + 255.2˙
1 Î9 ˚
y = log P and x = log
V È5 ˘
PV = K = nRT V = Í K ˙ T f + 255.2 K
Î9 ˚ 5K
log P + log V = log(nRT) 9
log P = –log V + log(nRT) ∫ y = mx + C
V
hence slope of kelvin and °C
Ê 1ˆ scale will be same but in foren-
255.2 K
log P = log ÁË ˜¯ + log(nRT)
V heit scale it will be lesser. T°
f
Combining Law or Ideal Gas Equation ______ Graham’s Law of Diffusion and Effusion _____
Ideal gas equation According to this law, rate of diffusion and effusion of any
1 gas is inversaly proportional to the square root of molecular
Vµ Boyle’s Law (1) mass of gas.
P
VµT Charle’s Law (2) 1
Rµ [T.P. and n are constant]
Vµn Avogadro’s Law (3) M mass
Combining (i), (ii) and (iii)
RA MB
nT = [T.P. n are constant]
Vµ RB MA
P
PV µ nT
RA PA MB
= [Dfferent partial pressure]
PV = nRT RB PB MA
R = universal gas constant. Since mole µ Partial pressure
R = 8.314 JK–1 mol–1 when P sin Pa or N/m2 RA n A M B
and V in m3 =
RB nB M A
R = 0.0821 atm lit mol–1 K–1
P in atm and V in litre Ê DV ˆ Ê DL ˆ
ÁË ˜¯ ÁË A ◊ ˜
R = 1.987 cal/mol K–1 RA Dt A DT ¯ A
= =
We know RB Ê DV ˆ Ê DL ˆ
PV = nRT ÁË ˜¯ ÁË A ◊ ˜
Dt A Dt ¯ B
wt
PV = RT Enrichment of a lighter gas in given gaseous mixture
Mwt
(i) For single diffusion system
wt
P Mwt = RT
V A Æ nA n¢A
PMwt = dRT B Æ nB n¢B
or PM = dRT
n ¢A n A MB
Dalton’s Law of Partial Pressure ____________ =
nB¢ nB MA
A B A+B (ii) Double diffusion system

+
nA nB nA nB nA n¢A n≤A
nB n¢B n≤B
n RT n RT n RT nB RT
PA = A PB = B PT = A +
V V V V
Partial pressure of gas A = PA and partial pressure of gas n ¢A n A MB
for 1st = (i)
B = PB. nB¢ nB MA
PT = PA + PB n ¢¢ n¢ MB
for 2nd A
= A (ii)
nB¢¢ nB¢ MA
PA = XAPT and PB = XBPT
This law states that total pressure exerted by the mixture Èn MB ˘ MB
of gas is equal to the sum of partial pressure of each gas. =Í A ˙◊
Î nB MA ˚ MA
PT = PA + PB 2
n ¢¢
A È n ˘ ÏÔ M B ¸Ô
Partial pressure of any gas is defined as pressure exerted = Í A ˙Ì ˝
nB¢¢ Î nB ˚ ÓÔ M A ˛Ô
by moles of that particular gas only in same condition of tem-
perature and volume. (iii) For multiple diffusion
The above law is applied only for non-reacting gas at giv-
nA n¢A nA final
en condition.
nB n¢B nB final
Gaseous State 3.7
n
È nA ˘ Èn ˘ ÔÏ M B Ô¸
Ín ˙ = Í A˙ Ì ˝ Patm
Î B ˚ final Î nB ˚initial ÔÓ M A Ô˛
n is also known as isotopic separation factor or number PHg
of diffusion step.
Air or gas Pgas
Application of Concept of Gaseous State _____
Pgas = Patm + PHg
Connected Container = Patm + hdg
PA PA PA¢ PB¢ È h 13.6 ¥ 103 ¥ 9.8 ˘
=1+ Í ¥ ˙ atm
1.01 ¥ 105 ˚
VB¢ if
VA VA
fi
VA
VA VB V Î1000
TA TA TA TB¢
nA nA nA¢ nB¢ h
Pgas = 1 + atm
Result: 760
(i) PA¢ = PB¢ (ii) n A + nB = n ¢A = nB¢ h = height of Hg column in mm Hg.
(2) This type of problem obeys Boyle’s law
(iii) VA = VA¢ (iv) VB¢ = VB
PV
1 1 = P2V2
Cylinder- and Balloon-Type Problem ________ Case I:
Pgas = Patm + PHg
h
P1 Pfinal 1 atm Pgas = 1 + atm
V1 760
T1
n1
Rules Patm
1. Pfinal = 1atm
2. Vinitial = Vcylinder PHg
[Because volume of balloon initially = 0] Air or gas Pgas
3. Vfinal = Vcylinder + Vballoons
= Vcylinder + n [volume of 1 balloon]
Case II:
Note: Pgas = Patm – PHg
1. In this type of problem, volume of system increases. h
2. Number of moles of gas present in cylinder at initial Pgas = 1 - atm
760
position is equal to moles of cylinder and moles of
balloon finally.
ninitial = ncylinder + nballoon Patm
PV
1 cylinder [Vcylinder + Vballoon ]
=1¥ PHg
T1 T2
Air or gas Pgas
Capillary Tube-Type Problem ______________ Case III:

Pgas = Patm = 1 tm
Rules
1. In this type of problem, we assume all the forces are bal-
anced at equilibrium position. In other words, we can
say total downward force is equal to total upward force.
Hg always applies force in downward direction
whereas atmospheric pressure and pressure of gas is
applied on surface of mercury (Hg)
Total upward directive force = Total downward direc-
Pgas PHg Patm
tive force
Case IV: 2. Temperature remains constant through the vertical

height.
3. If molar temperature is constant.
a tm
P q P1V1 = P2V2
s
ga
q)
P
(90 P0V0 = PhVh

PHg P0 Vh mgh
sin q = = e RT
PHg
q q Ph V0
Pgas = Patm + PHg sin q mgh
\ Vh = V0 e RT
h V
Pgas = 1 + sin q Mgh
760 log h =
V0 2.303RT
Borometic distribution: To calculate the pressure difference
for a vertical height ‘h’ for any fluid where density is depen- 4. Since P µ d (density)
dent on pressure. Ph d h -
mgh
–dp = dh(rg) (i) = = e RT

P0 d 0
Negative sign shows that decrease in pressure with increase mgh
- RT
in height. d h = d0e
dP (Pf Pi)
dh hf > hi 5. Mdis air = Mpay load + Mballoon
\ MPayload = V ¥ dh – Mballoon
h mgh
- RT
h h0 0 M Payload = Vd 0e - M balloon
P P0
Pay load: It is defined as the maximum weight that can
PV = nRT be lifted by a gas filled balloon.
or PM = dRT = rRT FBuoyancy = Mg + mballoong
m = M = molar mass of air
Mdisplaced air ¥ g = WPay load + Wballoon
PM [Mdisplaced air ¥ g]
r=
RT (ii) = [Mpayload ¥ g] + [Mgas ¥ g + Mballoon ◊ g]
From Eqs. (i) and (ii)
PMg \ [Vballoon ◊ dair ◊ g ] =
- dp = dh
RT [ M payload ◊ g ] + [Vballoon ◊ dgas ◊ g + M balloon ◊ g ]
dp mg
=- dh
P RT
Ph h Buoyancy force
dP mg
Ú P
=-
RT Ú0
dh
Balloon
P0
Ph mgh
ln =-
P0 RT
M For max force
P mgh that can be lifted.
2.303log 0 = (iii)
Ph RT
From Eq. (iii) Problems Related with Piston ______________
Ph -
mgh
P1 P1
= e RT
P0 Mass P1 P2 Mass
-
mgh
P2 less P2 PP full
Ph = P0e RT
P1 P2
mgh
- 2 303 RT P1 P2
or Ph = P010 P1 + P P P2
Assumption: Final pressure is equal at both sides of movable massless

1. Composition of air does not change with increase in piston.
height.
Gaseous State 3.9
Semi-permeable membrane (SPM) Assumptions:

S.P.M. 1. Gas consists of small particles (molecules or atoms)
identical in size, shape and mass.
2. The volume of molecules itself is considered negligible
(i) H2 O2 w r.t. to the total volume of the gas (total volume of
container).
3. There is no force of interaction (attraction or repulsion)
S.P.M. in between the gas particles, i.e., each molecule can
H2 move independently.
S.P.M. allows the movement of some particular molecules 4. The gaseous molecules move in rapid motion and col-
through itself. lide randomly with each other as well as the walls of
(ii) Partial pressure of diffusable gas is same in non-mov- container. (The pressure of gas is due to the collision of
able or fixed S.P.M. molecules with the walls of container.)
5. The collisions are perfectly elastic in nature (no energy
loss). Hence there is no net loss of kinetic energy. Ki-
HUMIDITY netic energy is transferred from one molecule to anoth-
er but it is not converted into any other form of energy
At equilibrium such as heat.
Vapour Pressure A. Tension 6. At any instant, given molecules can have energy range
from small to large but the average kinetic energy of
the molecules is directly proportional to absolute tem-
Ê3 ˆ
perature Á RT ˜ .
Ë2 ¯
7. The law of classical mechan-
3 V
ics (Newton’s law of motion)
are applicable to the mol-
H2O(l)  H2O(vap) ecules.
Consider there are total ‘N’ par-
K = equilibrium constant. It depends only on temperature. It ticles in a cubic container having y v
does not depend on quantity of water, volume or any other volume ‘V’ and side length ‘l’.
gaseous pressure. Consider a particle having ve- x
At equilibrium position quantity of water in air is maxi- locity ‘v’ moves on X-direction z
mum. So we can say equilibrium is a saturation point. then momentum of that particle be-
At equilibrium (saturation) point, partial pressure of water fore collision = mvx.
is called aqueous tension. Momentum of particle after collision = –mvx.
È nH O RT ˘ Therefore, change in momentum mvx – (–mvx) = 2mvx.
P.P. of H 2O vapour at saturation = Í 2 ˙ The molecules collide with opposite wall as the time
Î V ˚
l È l˘
P.P. of H 2O vapour =  vx = ˙
Relative humidity = ¥ 100 vx ÍÎ t˚
A.T as same temp. It is the time of one collision.
and 1 v
Total collisions are per unit time = = x
Ptotal = Pdry air + PH O vapour T l
2
R.H. relative humidity Change in momentum per unit time in x-direction by a
single particles is
P.P.H2O in air
¥ 100 vx 2mvx2
A.T. = V.P. = P.P.H2O (at equi.) = 2mvx ¥ =
l l
if (P.P.H2O )air > A.T. (condensation) Similarly in y-direction and z-direction
2mv 2y
y=
KINETIC THEORY OF GASES l
2m2vz2
(Microscopic model) z=
l
KTG is a theoretical model which can correlate the experi-
mental facts.
Total rate of change of momentum by single particle in all PV = RT

direction: Data in MKS
2m 2 2 P = N/m2
(vx + v y + y z2 ) M = kg/mol
l
R = 8.314
v = vxiˆ + v y ˆj + vz kˆ
v 2 = vx2 + v 2y + vz2 Proof of Various Gas Laws _________________
Boyle’s law
2m 2
= v 1 2
l PV = m Crms
3
There are ‘N’ particles present in a container. Therefore,
force exerted by them is equal to if T in Kelvin (Constant)
2m 3RT
= ( N1v12 + N 2v22 + ......... + N N vN2 ) C=
l M
2m 2 1
= [ Nurms ] Pµ
l V
2m 2 2 1
[ Nurms ]
l PV = ◊ MC 2
\ Applied pressure = 3 2
6l 2
2 3
1 = ¥ ◊ RT
P= 2
m[ Nurms ] 3 2
3l 3
PV = RT
l3 = V
PV = nRT
1 2
P= m[ Nurms ]
3V Maxwell’s distribution of velocities.
for 1 mole m. N. = M mass According to the kinetic theory of gases velocity of a
1 2 molecule continuously change as a result of collision with
PV = M MassU rms
3 other molecules as well as the walls of container.
1 3 Net result cannot comment about the velocity of ‘a’ single
K.E. = mu 2 = PV . molecule but we consider that the average of velocity of all
2 2
3 molecules remains constant at constant temperatures.
= nRT Since the observed properties such as volume pressure
2
and temperature of an isolated gaseous sample do not change
3 with time, so it is expected that the same is also true for the
for 1 mole KE = RT
2 distribution of molecular velocities, i.e., the fraction of the
3 total number of molecules having velocity in between any
for 1 molecule KE = KT definite range must be constant.
2
Maxwell gave the expression by the theory of probability:
R
K= = 1.38 ¥ 10-23 3/2 2
NA Ê M ˆ - 2Mv
d Nu = 4p N Á U 2e RT ◊ du
Boltzmann constant Ë 2p RT ˜¯
Calculation of Root, Mean, square velocity Represented as
dNu Æ total nmber of molecules in velocity range
Vrms or Urms and Crms
from u to (u + du)
N1v12 + N 2v22 + N 2v32 + N n vN2 N Æ total number of particles in collection
Vrms = M Æ molar mass of gas (kg/mole)
N
1 T Æ temperature in kelvin
2
PV = MU rms u Æ starting speed
3
du Æ difference of speed
3PV
U RMS = R Æ gas constant
M
3/2 2
3RT d Nu Ê M ˆ - Mu
U RMS = fi for mole gas = 4p Á ˜ u 2e 2 RT ◊ du (i)
M N Ë 2p RT ¯
Gaseous State 3.11
d Nu d Ê 1 dN ˆ È - Mv2 2 -
Mv 2 2mv ˘
Æ fraction of molecules having velocity is be- ÁË ˜¯ = k Í2ue 2 RT + u e 2 RT ¥ (-) ˙
N tween u to (u + du) du N du Î 2 RT ˚
3/2
Ê M ˆ
Note: K = 4p Á
Ë 2p RT ˜¯
According to Eq. (1)
È Mv 2 ˘
2
d Nu - Mv
(fraction of molecules) depends only on temperature = K ¥ ue RT
Í2 - ˙
N Î RT ˚
for a given gas (having molecular mass M)
Characteristics of Maxwell’s distribution d Ê 1 dN ˆ
For maximisation, put Á ˜ =0
du Ë N du ¯
Curve Mv 2
The parameter which were selected by Maxwell such that the fi 2=
RT
area under the graph (curve) give the value of fraction of mol-
ecules between two speeds.
2RT
3/2 2 vmp =
1 d Nu Ê M ˆ 2 - Mu M
◊ = 4p Á ◊U ◊ e 2 RT
N du Ë 2p RT ˜¯
OR
It can be derived by condition of maxima.
È 1 dNu ˘
Area dÍ
Î N du ˙˚ = 0
dN dN Area represent
represent N
dN ¥ d u dN ¥ du du
N
3/2
d È È M ˘ Mu 2 ˘
2 - 2 RT
U U (u + du) = Í4p Í u e ˙=0
u du Î Î 2p RT ˙˚ ˚
3 È - mu ˘ 2
Finally, È M ˘ 2 d Í u 2 e 2 RT ˙
2 = 4p Í =0
y = x 2 ◊ e- x Î 2p RT ˙˚ du Í
(i )(ii ) ˙
ÎÍ ˚˙
3 È mu 2 ˘
2
È M ˘ 2 Í - 2muRT -
2 2 RT 2mu ˙
d = 4p Í 2ue + u e ¥ ( - )
1 d d
Î 2p RT ˚˙ ÎÍ 2 RT ˚˙
¥ N 1 dN
Area ¥ N ¥ du 3
N du N du N mu 2
represent È M ˘ 2 - 2 RT È mu 2 ˘
= 4p Í ue Í2 - ˙=0
u u+ Î 2p RT ˙˚ Î RT ˚
y x2 ◊ e–x2 MV 2
2- =0
RT
Mu 2
=2
e–u2 RT
u2 u 0
2 RT
e–0 1 ump =
U
M
1. Most probable speed M = molecular mass in kg

1 dN T = Temperature in Kelvin
The values of speed for which is maximum is
N du R = 8.314 J K–1 mol–1
called most probable speed, i.e., the speed possessed by 2. Average molecular speed
maximum number of molecule or maximum fraction of
molecules is called the most probable speed. (Uamp or vmp) N1V1 + N 2V2 + N 3V3 + - -
uav =
3/2
N1 + N 2 + N3 + - -
2
Ê 1 ˆ Ê dN ˆ Ê M ˆ - 2Mv
ÁË ˜¯ ÁË ˜¯ = 4p ÁË ˜ u 2e RT
We can also derive this by Maxwell distribution theory.
N du 2p RT ¯
3
2
We can say that for a particular gas at constant temprature
Ê dNu ˆ Ê M ˆ 2 3 - mu d
uÁ = 4p Á u e RT du.
Ë N ˜¯ Ë 2p RT ˜¯ for fraction, N is constant. So the average kinetic energy of
N
3 •
2 gas is only and only the function of temperature.
Ê M ˆ 2 3 - mu
Ë 2p RT ˜¯ Ú
= 4p Á u e RT du.
0
Conclusions _____________________________
3
È Ê RT ˆ 2˘ 1. The fraction of molecules having very low or very high
Ê M ˆ2
uav = 4p Á Í2 ˙ speed are small in number.
Ë 2p RT ¯ Í ÁË M ˜¯ ˙
˜
Î ˚ 2. Majority of molecules have speed near the most prob-
M ˘ È Ê RT ˆ ˘
2 able speed.
Ê M ˆÈ
uav = 4p Á Í ˙ Í 2 ˙ 3. Total area under the curve is the major of total number
Ë 2p RT ˜¯ Î 2p RT ˚ Î ÁË M ˜¯ ˚
of fraction of molecules (or total number of molecules
8 RT in collection).
uav =
pM 4. Since with increase in temperature kinetic energy of
molecules increases by which fraction of molecules
3. Root mean square velocity have low speed range decreases whereas the fraction of
molecules having high speed range increases.
M1V12 + M 2V12 + M 3V32
urms = T
M total f1
f2 T2
3RT
urms =
M
Note:
The relative ratio ump u ump
uav : Ump : urms
5. With the increase in temperature, Ump also increases
8RT 2RT but corresponding fraction of molecules will decrease.
: : 3
pM M 6. Speed distribution also depends on molar mass of gas
8 and the gas having high molar mass has higher fraction
: 2 : 3 (corresponding to Ump).
p
56 M2
: 2 : 3 f1
22 M1
f2
M2 > M 1
Consequence of Distribution of Speed _______
It is the average kinetic energy of gas at a given time that is
constant.
v1
dN1 (ump)m2 (ump)m1

dN2 v2
M
Hence the distribution depends on the value of . It
T
dN3 v3 means the distribution will be same for gas having ‘2M’
M
1 1 1 molecular mass at 2T temperature because ratio
K.E. = Mv12 ¥ d N1 + Mv22 d N 2 + ...... + Mvn2 d N T
2 2 2 remains same.
N
1 Ê d ˆ Example 1. The temperature at which Maxwell distribution
= M Â vi2 Á Ni ˜
2 i =1 Ë N ¯ (i) curve of SO2 will be same as O2 at 300 K.
d N1 + d N 2 + ...... + d Nn = N M O2 = 32 M SO2 = 64
Mass is double \ temperature is doubled
From Eq. (i)
fi T = 600 K.
Gaseous State 3.13
Ratio of speeds Collision cross-section area

8 It is the cross-sectional area of imaginary sphere surround-
ump : vav : vrms :: 2: :: 3 = 1.14 : 1.6 : 1.732 ing a molecule into which centre of another molecule cannot
p
penetrate.
s 2r
1 dN s ps2
N du
Vavg
ump umv urms
u
If the speeds are written in terms of pressure and volume then s
number of moles of gas are also required but if temperature is When the molecules arrive a circumference of 2r, then the
given then number of moles number is not required. molecules will collide.
1
PV = mNu 2rms Collision frequency
3
mass of gas = m ¥ N = total weight and M molar mass It is equal to the number of collision occuring in per unit vol-
ume per unit time under the specific conditions.
1
nRT = mNu 2rms Case 1: Consider only one particle is moving and others
3 are stationary
weight 1 (i) A molecule will collide if centre will lie inside the col-
RT = mNu 2rms
Molar Mass (M ) 3 lision cross has a section.
(ii) If a moving particle speed of uavg, then the imaginary
3RT
urms = volume swept by moving particle per unit time is equal
M to v¢ = ps2 Vavg.
v¢ = ps2 Vavg
3PV
= urms v¢ = A ¥ 
nM
3PV (iii) If N* is the number of molecules of gas per unit vol-
ume, then the total number of molecules within the
ÊW ˆ
ÁË ˜¯ M swept volume is equal to ps2vavg ¥ N* = Z = collision
M
frequency.
3P N
= urms N* =
d V
Molecular collision Total number of particles = N* ¥ V ¢
Assumptions 100 molecule
(i) Molecular are considered perfectly rigid and spherical
in shape.
(ii) All the particles are moving with uavg speed. 10 L
Collision Diameter (s) \ N* 10

It is the distance between centres of two-diameter colliding
particles, i.e. the distance between particles is 2R, the par-
ticles will collide.
Same gas Different gas Therefore, Z is the number of collisions made by a sin-
gle moving particle in per unit time, when all others are
considered to be stationary.
r r r1 r2
Case 2: Consider all molecules are moving.
(i) Two particles can collide at an- Vavg
gle anywhere 0 to 180°. It means
the chances of collision at each
s 2r s r1 + r2
angle are same. Therefore, aver- 2 Vavg Vavg
age angle of collision is 90° and
the relative velocity = 2 vavg
Z1 = 2ps 2vavg ¥ N * (ii) If N B* is the number of molecules of gas B per unit

volume, then the total number of molecules within the
Z1 is the number of collisions made by a single mol- swept volume = ps2 urelative ¥ N B*
ecule in per unit time when all particles are moving. (iii) Then the total number of collision made by gas A per
Bimolecular collision unit volume per unit time is equal to
Case I: N *A ¥ N B* ¥ ps 2vrelative = Z12
When molecular collision in between two molecules of same
gas (Z11). Mean free path (l):
1 It is defined as the average distance travelled by molecules
Bimolecular collision frequency = ¥ (number of par-
2 between two successive collissions.
ticle per unit volume) ¥ (number of collisions made by 1 par- Then distance travelled by 1 molecule in per unit time
ticle in per unit time) l
vavg =
1 t = 1 sec.
Z11 = ¥ (N*) ¥ (Z1)
2
Total collision made by a molecule in per unit time
1
= ¥ (N*) ¥ ( 2 ps2 vavg) ¥ N* Z1 = 2 ps2 uavg ◊ N*
2
l distance travelled in one collision.
1 1
Z11 = ps 2vavg ( N *) 2 \ 1unit distance travelled in collision.
2 l
1
Then, uavg distance travelled in ¥ uavg collision.
Note: l
Division by 2 is essential since the simple multiplication of
1
Z1 by N* would count every collision twice. ¥ uavg collission = Z1
l
Case 2: uavg
When collision occurs in between B l=
the molecules of two different gases Z1
A
(Z12). uavg
s12 = rA + rB =
rA rB 2ps 2uavg N *
sA sB
s= + 1
2 2 l=
\
2ps 2 N *
(uavg) A
Effect of temperature, pressure and volume on l, Z1, Z11
1
(uavg) B l=
urelative 2ps 2 N * (i)
Z1 = 2 ps2 u N*
avg
1
Ê8 ˆÊ 1 1 ˆ Z11 = ps2 (N*)2 uavg
urelative = Á RT ˜ Á + = (uavg ) 2A + (uavg ) 2B 2
Ëp ¯ Ë M A M B ˜¯
Ê N ˆ
PV = Á RT
8RT Ë N A ˜¯
urelative =
pM Ê NˆÊ R ˆ
P=Á ˜Á T
Ë V ¯ Ë N A ˜¯
1 1 1
{ = + P = N* KT
M MA MB
P
(i) The volume swept by moving molecule A per unit time = N*
KT
is equal to ps2 urelative.
Gaseous State 3.15
From Eq. (i)

T
lµ E
E
P dN e
RT
8 RT P N
Z1 µ ¥
p M kT
P
Z1 µ E
T
8 RT P2
Z11 µ ¥ 2 2
p M k T REAL GAS
P2
Z11 µ Gases which do not obey ideal gas law is called real gas. A
(T )3/2
real gas is different from ideal gas from 2 factor.
At constant (T) (i) According to K.T.G., the intermolecular attraction
T P P2 negligible for an ideal gas. However in reality, the at-
lµ Z1 µ Z11 µ traction are significant enough. Therefore, the pressure
P T T 3/2
observed will be less than pressure that would have
1
≠lµ ≠ Z1 µ P ≠ Z11 µ P 2 been obtained under similar condition by an ideal gas.
PØ Therefore a correction factor ‘PC F ’ is to be added.
1 1
At constant (P) l µ T Z1 µ Z11 µ 3/2 P = Pobs + PC F
T T
(ii) According to K.T.G., the volume occupied by particle
At constant (V)
is negligible hence total free volume for ideal gas is
T* T T2 same as volume of container. However for real gas
lµ =K Z1 µ = T Z11 µ
T T T 3/2 since size of molecule is significant, therefore, free
volume available for the moment is less than volume
≠ P µT ≠ Z11 = µ T
of container.
l = constant [when volume is constant] V = Vobs – VC F
P Gas equation for real gas
V = = constant
T (P + PC F ) (V – VC F ) = RT
Maxwell distribution in terms of kinetic energy
3/2 2
Calculation for correction factor
d Nu Ê M ˆ - MU
= 4p Á ˜ U 2e 2 RT ◊ du (1) Calculation of pressure correction:
N Ë 2p RT ¯
The pressure correction factor depends on 2 factor.
1
KE = E = mu 2 (i) Number of molecules attracting the striking molecules.
2 (ii) Number of molecules striking the wall of container.
2E
u=
M
1
dE = m ¥ 2Udu
2
dE
= = du
MU
dE dE
= du fi PC F µ [Attracting molecules] ¥ [String molecules]
2E 2 EM
M N
M PC.F. µ [N*] [N*] and N* = and N = nNA
dN E 2 E - E
V
= e RT
NdE p ( RT )3/2 ÈN ˘ÈN ˘
PC F µ Í ˙ Í ˙
ÎV ˚ ÎV ˚
y = xe - x
Èn ¥ NA ˘ Èn ¥ NA ˘
Ê dN ˆ PC F µ Í
dE = Á Î V ˙˚ ÍÎ V ˙˚
Ë N ˜¯
Q. One way of writing the equation of state for real gases

n2 is
PC F =a 2
V È B C D˘
PV = RT Í1 + + 2 + 3 ˙ where B is a constant.
PC F V 2 Î V V V ˚
a=
n2 Derive an expression for ‘B’ in terms of Van der wall
constant.
Unit = atm lit2 mol–2 Ans. We know that Van der wall gas equation for real gas is
a = Vanderwall const. a ˘
È
Correction Factor for Volume ÍÎ P + V 2 ˙˚ [V – b] = RT
È a ˘ RT
ÍÎ P + V 2 ˙˚ = V - b
RT a
P= - 2
R R V -b V
RTV a
PV = -
V -b V
È V a ˘
PV = RT Í - ˙
ÎV - b VRT ˚
È 1 a ˘
The shaded part show the excluded volume for the pair of PV = RT Í -
particle. b VRT ˙
Í1 - ˙
4 Î V ˚
Excluded volume for a pair of molecule = p [2R]3 -1
3 ÈÊ bˆ a ˘
PV = RT ÍÁ1 - ˜ - ˙
32 3 ÎË V ¯ VRT ˚
= pR
3 We know (1 – x)–1 = 1 + x + x2 + x3 + …
16 3 if x << 1
\ excluded volume for one molecule = pR b
3 x= << 1
È4 3˘ V
= 4 Í p r ˙ = 4 [volume of 1 molecule]
Î3 ˚ 2 3
È a ˘
\ excluded volume for 1 mole molecule PV = RT Í1 + b Ê bˆ Ê bˆ
+Á ˜ +Á ˜ +- ˙
= 4 [Volume of 1 molecule ] ¥ NA Î V ËV ¯ ËV ¯ VRT ˚
= 4 ◊ V1NA = b È b 2 3
È a ˘ Ê bˆ Ê bˆ ˘
\ for n mole molecule = n ¥ 4V1NA = nb PV = RT Í1 + ÍÎb - + Á ˜ + Á ˜ ˙
Î V RT ˙˚ Ë V ¯ Ë V ¯ ˚
È n2a ˘
\ Í P + 2 ˙ [V – nb] = nRT This equation is compared by the given equation then
Î V ˚ we can find the value of ‘B’.
This is called Van der wall equation for real gas for n mole.
È a ˘
Physical significance of a and b B = Íb - C = b2 D = b3
Î RT ˙˚
(i) a depends on force of at-
traction between mole- F2 He Note:
cules.
Cl2 Ne a increases A temperature above which real gases have a ideal gas na-
F.A. µ (i) At wt. or Mwt. Br2 Ar ture is called Boyle’s temperature.
I2
F.A. µ (ii) polarity of com-
pound Calculate the Value of Boyle’s Temperature
\ aNH3 > aN2 We find
È 2 3 ˘
Polar Nonpolar 1È a ˘ Ê bˆ Ê bˆ
PV = RT Í1 + Íb - ˙ + ÁË ˜¯ ÁË ˜¯ + .....˙
+
ÈHCl, NH3 ˘ È N 2 , Cl2 ˘ Î VÎ RT ˚ V V ˚
Í H O ˙ ÍH , O ˙
Î 2 ˚ Î 2 2˚ b
Since <<< 1
(ii) b depends on size of molecules V 2 3
b Ê bˆ Ê bˆ
b µ size of molecule So we can neglect the heigher value of for eq. ÁË ˜¯ , ÁË ˜¯
V V V
So bH2 < bCl2 … etc.
Gaseous State 3.17
For ideal nature

Æ z N2 < z NH3
a
b- =0
RT \ z N2 > z NH3
a (b) At high pressure
T= Boyle's temperature
Rb
Ê a ˆ
PV = RT ÁË P + 2 ˜¯ (V - b) = RT
V
Compressibility Factor The value can be neglected with respect to pressure but at
It is defined as the ratio of actual volume of gas and volume high pressure the volume of gas is low hence ‘b’ cannot be
occupied by ideal gas under similar condition of temperature neglected with respect to ‘V’.
pressure and mole. (V – b) = RT
È Vactual ˘ P[V – b] = RT
ÍZ = V ˙ Same condition of P, T and n. PV – Pb = RT
Î ideal ˚
PV Pb
nRT - =1
Videal = RT RT
P
PV Pb
Vact =1+
Z= RT RT
nRT
Pb
P Z =1+
RT
PVact
Z= Since size of N2 < size of NH3
nRT
\ bN2 < bNH3
PVact = Z ◊ nRT Z = 1 for ideal gas
ZN2 < NH3
For 1 mole
if b≠ z≠
PVact = ZRT For lighter gases like H2 and He having low value of Mo-
Z > 1 fi Less compressible than expected. lar Mass and both are non-polar gases so that attraction be-
tween molecule is much less compared to other gases.
PV
Z= It means we can assume that the value of a = 0. [Both for
RT high pressure and low pressure.]
Variation of Compressibility factor with È a ˘
Respect to Pressure So ÍÎ P + V 2 ˙˚ [V – b] = RT
(a) At low pressure
P(V – b) = RT
Ê a ˆ PV Pb
ÁË P + 2 ˜¯ (V - b) = RT - =1
V RT RT
At low P volume V≠ so V – b ª V PV Pb
a ˆ =1+
Ê RT RT
ÁË P + 2 ˜¯ V = RT
V Pb
Z =1+
a RT
PV + = RT
V \ Z>1
PV a We know b≠, z≠
+ =1 bH2 > bHe
RT RVT
PV a So [ Z H2 > Z He ]P of constant pressure.
=1-
RT RVT H2
a He
\ Z =1-
RVT
if a≠ zØ,
Æ aN2 < aCO2 Z 1 Ideal gas
N2
\ z N2 > zCO2 NH3
low pressure
Critical temperature (TC): Temperature above which gases

\ VC = 3b
cannot be liquified by any applied pressure of ‘p’ is called
critical temperature (TC) By Eq. (iv)
Critical pressure (PC): Minimum pressure which is required a
= 3VC2
to liquify the gas at critical temperature. PC
Critical volume (VC): Volume of 1 mole of gas at critical a
= 3[3b]2
temperature and pressure is called critical volume (VC) PC
Isotherms for gases a
\ PC =
27b 2
From Eq. (iii)
RTC
L b+ = 3VC
PC
P(atm) Tb
Tc RTC
b+ = 3VC
È a ˘
G+L ÍÎ 27b 2 ˙˚
Gas
RTC
b+ = 3[3b]
V È a ˘
ÍÎ 27b 2 ˙˚
We know Van der wall equation
a ˆ RTC
Ê = 8b
ÁË P + V 2 ˜¯ (Vm - b) = RT a
m
27b 2
( PVm2 + a ) (Vm - b) = RTVm2 8b a
\ TC = ¥
PVm3 - PbVm2 + aVm - ab = RTVm2 R 27b 2
PVm3 - Vm2 [Pb + RT] + aVm – ab = 0 8a
TC =
È RT ˘ a ab 27 Rb
Vm3 - Vm2 Íb + + Vm - =0
Î P ˙˚ P P The law of corresponding states
At critical conditions- Pr = Reduced pressure.
È RT ˘ aV ab P T Vm
Vm3 - Vm2 Íb + C ˙ + m - =0 (i) Pr = Tr = Vr =
PC ˚ PC PC PC TC VC
Î
Equation (i) should have only one value of volume and Ê a ˆ
should be ‘Vc’. ÁË P + V 2 ˜¯ (Vm - b) = RT
m
The roots of equation will be a ˘
È
(Vm – VC) (Vm – VC) (Vm – VC) = 0 Í Pr PC + (V V ) 2 ˙ [VrVC - b] = RTrTC
Î r C ˚
or Vm3 - 3Vm2VC + 3VmVC2 - VC3 = 0 (ii) a a ˘
È È 8a ˘
Equations (ii) and (i) are similar so we can compare their Í Pr 27b 2 + V 2 (3b) 2 ˙ [Vr (3b) - b] = RTr ÍÎ 27 Rb ˙˚
Î r ˚
coefficient.
a È Pr 3 ˘ È a ˘
RT + b[3Vr - 1] = 8Tr Í
\ b + C = 3VC (iii) 27b ÍÎ b Vr2b ˙˚ Î 27b ˙˚
PC
a È 3 ˘
= 3VC2 (iv) Í Pr + 2 ˙ [3Vr - 1] = 8Tr
PC Î Vr ˚
ab PVm ( Pr PC )(Vr VC )
= VC3 (v)
PC Z= =
RT R[Tr TC ]
(5) VC3 ab PC
= 2 = ¥ 3 È Pr Vr ˘
(4) 3VC PC a Z=
8 ÍÎ Tr ˙˚
VC
=b
3
Gaseous State 3.19
Molar Heat Capacity Degree of freedom:

Translational degree of freedom
It is the required heat to rise 1°C temperature of 1mole
Movement of molecules in all 3(x, y, z) directions.
substance. Value of translational degree (max.) is 3[for mono, di
1. In case of gaseous state molar heat capacity is a func- or triatomic]
tion of pressure and volume so that it has two different Degree of rotation is possible due to the rotation of at-
values CP and CV. oms in molecule and the value of rotation degree of
CP: molar heat capacity at constant pressure: freedom is
It is the required heat to rise 1°C temperature of 1 mole for linear molecules (L) = 2
of gas at constant pressure. for non linear molecules (NL) = 3
CV: Molar heat capicity at constant volume: Vibration degree of freedom:
It is the required heat to rise 1°C of temperature of It is possible due to the vibration in molecules
1mole of gas at constant volume.
2. For liquid and solid CP = CV
3. For ideal gas CP – CV = R and CP > CV H H S S
R = 2 cal mol–1K–1
(3N – 5) for linear molecule (L)
C (3N – 6) for non-linear molecule (NL).
and g = P = constant = poisson ratio
CV where N is number of atoms.
g>1 Degree of freedom Linear (L) Non-linear (NL)
4. Value of CP and CV for different gases. Translation 3 3
Rotational 2 3
CP Vibrational 3N – 5 3N – 6
Gas CV CP = CV + R r =
CV Q. Determine the various degree of freedom for CH4
3 5 5 Comp. Trans. Rot. Vib. Total
Monoatomic R R CH4 3 3 9 15
2 2 3
5 7 7 3tr 1
Diatomic R R 2 KT
2 R 5 1
2rot [L]
Triatomic 7 9 9 3¥N 2 KT
R R 1
linear (L) 2 2 7 3 rot [N.L] 2 KT
Triatomic 4 (3n 5) vib[L] KT
3R 4R
non linear (NL) 3 (3n 6) vib [N.L] KT
5. Normally CP and CV are constant and it does not de- For one molecule of benzene number of atom 12 (Non
pend on temperature. But in case of high temperature, linear) so total degree of freedom 3 ¥ 12 = 36 = 3 Rota-
it is a function of temperature and it varies with tem- tional + 3 Translation + 30 vibrational
perature. \ Energy of one molecule
CV = a + bt + ct2 3 3
where a, b and c are constant. KT + KT + 30 KT = 33 KT for C6H6
2 2
Solved Examples
1. (i) An open tank is filled with Hg up to a height of 76 h

cm. Find pressure at the bottom and middle of the PB = Patm +
76
tank, if atmospheric pressure is 1 atm.
76
(ii) Find the height of water up to which water must be =1+ = 2 atm
filled to create same pressure at the bottom. 76
h
Patm PA = Patm +
76
Sol. (i) 38
=1+ = 1.5 atm
A 76 cm Hg 76
B
(ii) (h1d1 g ) H2O = (h2 d 2 g ) Hg 1 1

tan q = nA =
3
h1 ¥ 1 ¥ 10 = 0.76 ¥ 13.6 ¥ 10 3 nRT RT tan q
h = 10.33 meter 1 1
2. What will the pressure nA = fi n A = mole
0.0821 ¥ 273 ¥ tan45° 22.4
Patm
1 1
nB = = mole
RT tan 60° 22.4 3
d2 h2
5. At constant P of 0.0821 atm log V vs log T graph was
plotted for three sample of ideal gases. Calculate the
d1 C h1 number of moles of each gas.
Sol. V µ T log V (1)
B V nR (2)
=K=
(i) at the bottom of the tank? T P (3)
(ii) at the middle of the bottom layer if two immis- log V = log T + log K
cible liquids are filled as shown in figure? y = mx + C 0.4771
Sol. PB = Patm + Pressure due to liquid (2) + Pressure due to nR
C = log K = log ÊÁ ˆ˜ 0.30 log T
liquid (1) Ë P¯
h2 d 2 g h1d1 g
PB = Patm + + È 0.0821˘
1.013 ¥ 105 1.013 ¥ 105 C = log Ín ¥
Î 0.0821˙˚
If h in metre d in kg/m3 and g in m/sec2] or in M.K.S. For (1) C = log n
1 atm = 1.013 ¥ 105 Pa 0.4771 = log n = log 3
h1 n=3
h2 d 2 g dg
PC = Patm + + 2 1 For gas (2) 0 = log n = log 1
1.013 ¥ 105 1.013 ¥ 105 n=1
For gas (3) – log x = 0.30
3. Find the pressure of gas inside the container if manom-
– log 2 = log n
eter attached to the container shows a difference of 60
–log 2–1 = log n
mm as shown in the figure?
È1˘
log Í ˙ = log n
Î2˚
1
n= mole
2
60 mm Hg
6. Radius of a bubble at the bottom of the tank shown be-
low was found to be 1 cm. Find the radius of the bubble
at the surface of water at same temperature.
60 6
Sol. P = Patm + = 1 + atm
760 76 10.336 10.336
1 metre
4. At a constant temperature of 273K, vs P is plotted metre
V
for two ideal gases A and B as shown in the figure. Find
out the number of moles of gases A and B. hdg
1 Pressure at bottom = Patm +
Sol. PV = nRT, P = nRT 1.013 ¥ 105
sB
V
ga
10.336 ¥ 1 ¥ 103 ¥ 9.8

sA
1 1 =1+ = 2 atm
ga
= P 1 1.013 ¥ 105
V nRT V
Comparing by above equation, 45° 60° Since temperature is constant and n constant
P
y = mx + C PV
1 1 PV
\ = 2 2
C=0 n1T1 n2T2
1
m= (m = tan q) \ P1V1 = P2V2
nRT
Gaseous State 3.21
4 4 P2 = 1440 = Pgas
2 ¥ p (1)3 = 1 ¥ p r 3 \ PT = Pg + Paq ten = 1440 + 20 = 1460 mm-Hg
3 3
(Aqueous tension change with temperature only)
r = 2 cm
3
(c) P1V1 = P2V2
(b) If the absolute temperature at surface is 4 times to 720 ¥ V = P2 ¥ 2V
that at the bottom. Find the radius of bubble at surface? P2 = 360
Sol. T2 = 4T PT = P2 + Paq ten
= 360 + 20 = 380 mm-Hg
PV PV
1 1
= 2 2 10. An iron tank contains helium at a pressure of 3.0 atm
T1 T2 at 27ºC. The tank can withstand a maximum pressure
4 4 of 10 atm. The building in which tank has been placed
2 ¥ p (1)3 1 ¥ p r 3
3 3 catches fire. Will the tank blow up first or melt. (Melt-
=
T 4T ing point of iron is 1535ºC.)
8 = r3 Sol. P1 = 3.0, T1 = 300 K
r = 2 cm P1 P2 3.0 P
= fi = 2
7. If 2 liter of gas A at 1.5 atm and 3 liter of gas B at 2 atm T1 T2 300 1808
are mixed in a 5 liter container find the final pressure.
3.0 ¥ 1808
Sol. n1 + n2 = n P2 = = 18.08 atm
300
PV
1 1 PV PV
+ 2 2 = Since at melting point, it is greater than the maximum
RT RT RT pressure, therefore it will blow up.
P1V1 + P2V2 = PV 11. An open vessel at 27°C is heated until 3/5th of the air in
1.5 ¥ 2 + 2 ¥ 3 = P ¥ 5 it has been expelled. Assuming that the volume of the
9 vessel remains constant, find
P = atm = 1.8 atm
5 (a) the temperature at which vessel was heated.
8. Two moles of NH3 and one mole of HCl gas are taken (b) the air that escaped if vessel is heated to 900 K.
in a container of capacity 8.21 L at 300 K to produce (c) temperature at which half of the air escaped out.
NH4Cl. Find total pressure after reaction. Sol. Note the fact that on heating a gas in a vessel, the num-
Sol. NH3 + HCl h NH4Cl ber of moles of gas which go out, the volume of vessel
(g) (g) (S) remains constant.
2 1 O Let initial moles of air at 300 K be ‘n’. On heating
1 O 1 3/5 moles of air are escaped out at temperature T.
ng = nNH3 = 1 mole (after reaction) Ê 3 ˆ 2n
\ moles of air left at temperature T = Á n – n˜ =
ng RT Ë 5 ¯ 5
1 ¥ 0.821 ¥ 300
P= = = 3 atm (a) Under simillar conditions of P and V
v 8.21
9. A closed container containing O2 and some liquid wa- n1T1 = n2T2
ter was found to exert 740 mm pressure at 27°C. 2n
(a) Calculate the pressure exerted by O2 if aqueous n ¥ 300 = ¥ T fi T = 750 K
5
tension at 27°C is 20 mm of Hg. (b) On heating vessel to 900 K, let n1 moles be left
(b) What will be the final pressure if volume is re- again n1T1 = n2T2
duced to half; assuming volume of liquid water is
1
negligible? n1 ¥ 900 = 300 ¥ n fi n1 = n
(c) What will be the final pressure when volume is 3
doubled? n 2
\ moles escaped out = n - = n moles
Sol. (a) PT = Pg + Paq tension 3 3
740 = Pgas + Paq tension (c) Assume n/2 moles are escaped at temperature T,
Paq tension = 20 mm Hg then
\ Pgas = 720 mm Hg n1T1 = n2T2
Gas law applicable for gas only n/2 ¥ T = n ¥ 300
(b) (Paq tension change with temp. only) T = 600 K
Gas law applicable for gas only 7
12. A balloon is inflated to of its maximum volume at
P1V1 = P2V2 27°C. 8
V
720 ¥ V = P2 ¥
2 (a) Will it burst at 30°C?
(b) Calculate the minimum temperature above which LNH3 MB 36.5

it will brust. Sol. = =
Sol. (a) Balloon will burst if V¢ ≥ maximum volume LHCl MA 17
Maximum volume = V x 6
=
7 100 - x 4.1
Initial volume of balloon = V
8 \ x = 60 cm
at 27°C or at 300 K 16. A container consist of H2 & O2 gas having same no
7 of moles. If the volume of H2 gas is collected after
V ¥ 300 = V 1 ¥ 303 half an-hour is 30 ml. Then calculate the volume of O2
8
collected under similar condition.
2100
V¢ = V RH2 MM of O 2 RH2 32 VH2 30
2424 Sol. = = = = = =4
RO2 MM of H 2 RO2 2 VO2 VO2
\ ballon will not burst.
V V 30
(b) 1 = 2 \ VO2 = = 7.5 ml
T1 T2 4
In 30 minute VO2 collected = 7.5 ml
7
V /300 = V /T2
8 Note:
7 1 In any diffusion and effusion process, the rate of dif-
=
9 ¥ 300 T2 fusion and effusion do not remain constant through-
out the given time interval. (Generally it decreases)
2400
T2 = = 342.85 K. However, for solving a problem, the rate is assumed
7 to be constant during specific interval of time and
13. An open flask contains air at 27°C. Calculate the tem- this constant rate of diffusion or effusion is taken as
perature at which it should be heated so that initial rate of diffusion or effusion.
1
(i) of air measured in the container at 27°C es- 17. A container consists of H2 and O2 gases having same
3
number of moles. If the volume of H2 gas is collected
capes out. after half an-hour is 30 ml. Then calculate the volume
1 of O2 collected in 15 minutes taking diffusion rate con-
(ii) of air measured in the container if final tem-
3 stant.
perature escapes out. RH2 MM of O 2 RH2 32 VH2 30
Sol. Hint: ni – nf = n expelled Sol. = = = = = =4
RO2 MM of H 2 RO2 2 VO2 VO2
PV PV 1 È PV ˘
(i) - =
R.300 RT 3 ÍÎ R.300 ˙˚ 30
\ VO2 = = 7.5 ml
PV PV 1 PV 4
(ii) and - =
R.300 RT 3 RT In 30 minutes VO2 collected = 7.5 mL
14. H2 15
N2 In 15 minutes VO2 collected = 7.5 ¥ = 3.75 mL
30
P P 18. A container consists of H2 and O2 in 2 : 1 molar ratio.
LN2 If the volume of H2 gas collected after 10 minutes is 15
Find = ? If P is same for both gases.
LH2 mL at same T and P. What will be the volume of O2 gas
collected at minute and 20 minute?
DV LN RA VA n A M B n A 32
A◊ 2 Sol. = = ¥ = = 16
MB 2
Sol. Dt = Dt = = RB VB nB M A nB 2
DV LH 2 MA 28
A◊ VH 2 2
Dt Dt = ¥4
VO2 1
xcm fumes of NH4 Cl
15
\ VO2 = at t = 10 minute
15. NH3 HCl 8
at t = 20 minute
1 metre 15 20 30
¥ = mL
Find x. 8 10 8
Gaseous State 3.23
1 1 n
19. A container consists of moles of D2 gas and 5 3 È 352 ˘
20 10 = Í ˙
3 5 Î 349 ˚
mole of H2 is collected through a nozzle to a large con-
n
tainer. After 10 minute 0.1 gm of D2 was collected in 25 È 352 ˘ 2
=
the second container, then calculate 9 ÍÎ 349 ˙˚
(i) initial rate of diffusion of both gases.
n
(ii) Moles of H2 obtained in second container after 10 log 25 - log 9 = log[1.0086]
minute. 2
n
RH2 nH2 4 1 20 1.397 - 0.954 = [0.0037]
Sol. (i) = = ¥ 2 2
RD2 nD2 2 10 1 n = 240
1 22. Given figure shows 2 Identical A and B with rigid walls
\ RH2 = 2 2 RD2 or RD2 = RH
2 2 2 containing ideal gas. The pressure, volume and tem-
perature in vessel A are TA, VA and PA whereas in second
nH¢ 2 nH2 4 1/10 container pressure is PB, volume is VB and temperature
(ii) = fi ¥ 2
nD¢ 2 nD2 2 1/20 is TB. Vessels second are now connected through a nar-
row tube. Show that the final ratio of ‘P’ and tempera-
nH¢ 2
=2 2 P 1 ÈP P ˘
nD¢ 2 ture T satisfy the equation = Í A + B ˙
T 2 Î TA TB ˚
nH¢ 2 = 2 2 nD¢ 2 PA PB P P
0.1 Sol. VA VB
fi
T T
WH2 = 2 2 ¥ ¥2 TA TB V
VA VB V
4 V
nA nB nA¢ nB¢
= 0.1414 gram
VA = VB = V (Same vessel)
20. A closed container having molar ratio H2 and N2 of 1 :
9. After n diffusion this ratio changed up to 9 : 1. Cal- PAV PV
nA = n ¢A =
culate what is the value of ‘n’? RTA RT
Ê nA ˆ 1 Ên ˆ 9 PBV PV
ÁË n ˜¯ = and Á A ˜ = nB = nB¢ =
Sol. B initial 9 Ë nB ¯ final 1 RTB RT
Ê MB ˆ
n (n ¢A + nB¢ ) = n A + nB
Ê nA ˆ Ên ˆ
ÁË n ˜¯ = Á A˜ Á ˜ PV PV È PAV PBV ˘
B final Ë nB ¯ initial Ë M B ¯ + = +
n
RT RT ÍÎ RTA RTB ˙˚
1 Ê 28 ˆ
9= Á ˜ 2 PV V È PA PB ˘
9Ë 2 ¯ = Í + ˙
n RT R Î TA TB ˚
81 = (14) 2
P 1 È PA PB ˘
n = +
log (9) 2 =log (14) T 2 ÍÎ TA TB ˙˚
2
n 23. Two flasks of equal volume connected by a narrow
2 ¥ 2[log 3] = [log 2 + log 7] tube are at 27°C and container has 0.7 moles of H2 and
2
0.5 atm. One of the flasks is then emerged into a bath
n
4[0.4771] = [0.3 + 0.85] kept at 127°C while the other remains at 27°C. Calcu-
2 late the final pressure and number of mole of H2 in each
1.9084 ¥ 2 flask.
n= = 3.31
1.15 nRT 0.35 ¥ 0.082 ¥ 300
Sol. V = = = 11.2 L
\ after 4 diffusion. P 0.5
21. A sample of 235UF6 and 238UF6 is present in ratio 3 : 5 Case I
motar ratio after n diffusion this ratio become 5 : 3 then
calculate value of n. n 0.35 n 0.35
È n 235 UF ˘
Sol. Í 238 6 ˙
È n 235 UF ˘
= Í 238 6 ˙ ¥Í
È M 238 UF ˘
235
6 ˙
P 5 atm
T 300
P 0.5
T 300
fi
ÍÎ n UF6 ˙˚ final ÍÎ n UF6 ˙˚initial ÍÎ M UF6 ˙˚ V 11.2 V 11.2
A B
Case II 10
= P2 +
x mole (0.7 x) 76
mole Psame and
for A PiVi = PfVf for B PiVi = PfVf
Vnew Vinitial
Pihi = Pfhf 1 ¥ 45 = P2[90 – l1] (i)
300 K 400 K
È 10 ˘
A B 1 ¥ 45 = Í P2 + ˙ L1 (ii)
Î 76 ˚
For A Pnew V = x ◊ R ¥ 300 (i)
For B Pnew V = (0.7 – x) ◊ R ¥ 400 (ii) Ê 10 ˆ
P + L
x ◊ R ◊ 300 = (.700 – x) ¥ R ¥ 400 (ii) ÁË 2 76 ˜¯ 1
= =1
300x = 280 – 400x (i) P2 [90 - L1 ]
700x = 280 L1 and L2 can be calculated.
x = 0.4 mole 27. Calculate L2.
24. A mixture of 0.5 moles of CO and 0.5 moles of CO2
is taken in a vessel and allowed to effuse in another Hg liquid d 10.2 gm/ml
container which has vacuum. If total ‘A’ moles have Patm
effused out in time ‘t’, show that M1A + M2 (1 – A) =
36 M1, M2 are mean molar masses of mixture that are Pliq
effused out and mixture still remaining. 1 atm PHg
Sol. Initial mass = 0.5 ¥ 28 + 0.5 ¥ 44 = 36
L2 Pgas
Final mass = (1 – A) M2 + AM1 = 36
= M2 – M2A + AM1 = 36 20 cm 2cm6 cm
or
Sol. P2 = Pgas = Patm + PHg + Pliq
M1A + M2 [1 – A] = 36
È 6 ˘
0.5 mole (1 A) A(mole) Í ¥ 10.2 ¥ 103 ¥ 9.8 ˙
2 100
CO No mole Pgas = Í1 + + ˙ atm
gas Î 76 1.01 ¥ 105 ˚
0.5 mole
M2 M1
CO2 P1 = 1 atm, V1 = A ¥ L1 = A ¥ 20
25. A 2 L cylinder has 10 mole at 300 K. This container is P2 = Pgas, V2 = A ¥ L2
connected to a 1 L vaccum container by a narrow tube. P1V1 = P2V2
If final temperature is remain same, then calculate the 1 ¥ 20 = Pgas ¥ l2
final pressure of the system. 20
Sol. P1V1 = n1RT1 l2 = CM
È 2 6 ˘
1 + +
ÍÎ 76 100 ˙˚
10 ¥ 0.0821 ¥ 300 PV
1 1 PV
P1 = and = 2 2
2 n1T1 n2T2 28. 10 cm column of air is trapped by a column of Hg 8 cm.
If capillary tube is fixed horizontally as shown in the
È10 ¥ 0.0821˘
ÍÎ 2 ˙˚ ¥ 2 P2 ¥ 3 figure at 1 atm, calculate the length of air column when
= the tube is fixed at same temperature.
nT n¥T (a) Vertically with open end up.
10 ¥ 0.0821 ¥ 300 (b) Vertically with opened down.
P2 = = 82.1 atm
3 (c) At 45° from horizontal with open end up.
45 cm 10 cm 45 cm Sol. (a) Pgas = Patm = 1 atm
Let the area be A
B P1V1 = P2V2
P2 L2
8
26. 1 atm 1 atm P2 = Pgas + PHg = 1 +
A B PHg 76
10 8
P1 L1
A
100 cm
Calculate L1 and L2 Pgas Patm
Sol. L1 + L2 = 90 cm (Hg does not expand)
and P1 = P2 + PHg
PHg
Gaseous State 3.25
È 8˘ Sol. (i) nT = nHe + nAr + nNe

1 ¥ 10 ¥ A = Í1 + ˙ ¥ h ¥ A
Î 76 ˚ 30 5
Pf V f ¥ A ¥ 35 ¥ A ¥ 40
h = 9.04 cm 10 ¥ 25 ¥ A 7
= + + 2
(b) P1 = 1 atm, V1 = 10 ¥ A RT RT RT RT
È h˘ È 8˘ 30
P2 = Í Pgas - ˙ = Í1 - ˙ Pf ¥ A ¥ 100 = 10 ¥ 25 ¥ A +
Î 76 ˚ Î 76 ˚ 7
5
V2 = h ¥ A ¥ A ¥ 35 +
¥ 40 ¥ A
2
P1V1 = P2V2
Pf ¥ 100 = 250 + 150 + 100
È 8˘ 500
1 ¥ 10 ¥ A = Í1 - ˙ ¥ h ¥ A Pf = = 5 atm
Î 76 ˚ 100
h = 11.18 cm
Pf = 5 atm
(c) P1 = 1 atm, V1 = 10 ¥ A
È h ˘ (ii) (a) P1V1 = P2V2 fi 10 ¥ 25 = 5 ¥ l2
P2 = Í1 + sin 45∞˙
Î 76 ˚ l2 = 50 m
V2 = h ¥ A
(b) P1V1 = P2V2
P1V1 = P2V2
h = 9.3 cm 30
¥ 35 = 5 ¥ l2
29. Mr. Gupta weights 72.15 kg and wants to fly in the sky 7
with balloon whose weight is 20 kg and each contain- l2 = 30 m
ing 50 moles of H2 gas at 0.05 atm and 27°C. Density
of air at given condition is 1.25 gm/ltr. How many such
types of balloon is needed to fly in the sky?
Sol. MPayload = Mdip air – MBalloon
N[Vballoon ¥ dair] – [dgas ◊ Vballoon + Mballoon] = Mpay load
È nRT ˘
NÍ ¥ 1.25 – N [20 ¥ 103 + 100] = 75.15 ¥ 103
Î P ˚˙ 50 30
80 m
75.15 ¥ 103 Final position = 80 meter
N= =7
È 50 ¥ 0.0821 ¥ 300 ¥ 1.25 ˘ 3
31. Few gases are filled as air in the container as shown in
ÍÎ ˙˚ - [20 ¥ 10 + 100]
0.05 the figure and allowed to attain equilibrium (assuming
\ N=7 temperature remains constant) throughout the process.
30. Figure below shows initial conditions of a uniform Select the correct option:
cylinder with frictionless piston A and B held in posi- (i) Total moles of gas in compartment III will be 12.
tion by mechanical stoppers. If the mechanical stoppers (ii) The moles of hydrogen in compartment II will
holding piston A and B are removed, (assume that tem- be 2.
perature remains constant) (iii) The length of compartment containing only hy-
(i) What will be the pressure developed in each com- drogen will be after equilibrium is attained?
partment in final state? (iv) Distance of movable piston from left end is 50 cm
(ii) What will be the final position of piston A with after equilibrium is attained.
respect to for left end of container?
(20 + y) (40 y)
(iii) What will be the final position of piston B with
respect to for left end of container?
A B 20 cm 40 cm 40 cm
He H2 O2
P = 10 atm P = 10 atm P = 10 atm
25 m 35 m 40 m P1 P2 PH
He (g) Ar (g) Ne (g) Fixed
I II III
P atm 10 P 30/7 atm P 5/2 atm S.P.M.
(allow only H2)
I II III
at equilibrium fl dNu
3/2 2
È M ˘ - 2mu
= 4p Í u 2e RT du
N Î 2p RT ˙˚
20 + y 40 y 40 cm 3
È 28 ¥ 10-3 ˘2
He H2 O2 PH2 = 4 ¥ 3.14 Í ˙
10 atm 10 atm 10 atm Î 2 ¥ 8.314 ¥ 300 ¥ 3.14 ˚
P1 P2 x (10 x)
È 2 RT ˘ - 2MRT ¥ 2MRT 2 RT
I II Fixed III ÍÎ M ˙˚ e ¥ 0.01
M
S.P.M. 3
È 28 ¥ 10-3 ˘2
Sol. At S.P.M. compartment II and III = 4 ¥ 3.14 Í ˙
Î 2 ¥ 8.314 ¥ 300 ¥ 3.14 ˚
PH2 = P2 = PH¢ 2
¥ [422]2 e -1 ¥ 0.01 ¥ 422
Let (x) moles of H2 are deffused from II Æ III (By
= 8.303 ¥ 10-3 Ans
S.P.M.)
P. Pressure of H2 in II = III 34. What is the ratio of the number of molecules having
speeds in the range of 2 ump and 2ump + du to the Num-
x (10 - x)
= ber of molecules having speed in the range of ump and
40 - y 40 ump +du.
P2 = PH¢ 2 Area of A
nRT Area of B
V
At Piston in compartment I and II
P1 = P2 ump + du
A
10 RT xRT
=
(20 + y ) R (40 - y ) A 1 Nu 2ump + du
N du
10 x
=
20 + y 40 - y
x=2 B A
y = 30 3
Ê dNu ˆ È M ˘ 2 2 - 2MRT u 2A
32. Calculate Vrms speed of oxygen at 300 K. Sol. Á ˜ = 4p Í uA e du
Ë N ¯A Î 2p RT ˙˚
3 ¥ 8.314 ¥ 300 3
Sol. Vrms = = 483.12 m/sec Ê dNu ˆ È M ˘ 2 2 - 2MRT uB2
32 ¥ 10-3 ÁË ˜¯ = 4p Í uB e du
N B Î 2p RT ˙˚
33. Calculate the fraction of N2 molecules at 1 atm pres-
Ê dNu ˆ Mv 2
sure and 300 K– whose speeds are in the range of ump ± ÁË ˜ - A
N ¯ A u A2 e 2 RT
0.005. = 2 ¥
Ê dNu ˆ uB Mv 2
- B
ÁË ˜¯ e 2 RT
N B
- M ¥ 4 ¥ 2 RT
2 RT M
4u 2 e
= 2mP ¥
Sol. umP - M ¥ 2 RT
e 2 RT M
e -4 4
= 4 ¥ -1 = 4e -3 = 3 = 0.199
e e
ump 0.05 ump +0.05 35. Calculate vrms speed of H2 molecule under the follow-
\ du = final velocity – Initial velocity ing conditions?
= [ump + 0.005] – [ump – 0.005] = 0.1 (i) 2 moles of H2 gas at 27°C.
du = 0.01 (ii) 3 moles of H2 gas in 5 l container at 105 Pa.
By Maxwell distribution theory (iii) 4 moles of H2 having density 1 g/mL at 105 Pa.
Gaseous State 3.27
Sol. We know Sol. Volume of balloon

3RT 4 3 4 Ê 22 ˆ 3
Vrms = = pr = Á ˜ (10) = 4190.47 m
3
Molar mass in kg 3 3Ë 7 ¯
3PV 3P = 4190.47 ¥ 103 L
= = Mass of dry air = d ¥ v = 1.2 ¥ 4190.47 = 5028.56 kg
Total mass in kg d
PV
P in Pascal, V in m3, molar mass in kg and density d or Mass of the helium = W = ¥ 4 ¥ 10-3 kg
RT
r in kg/m3
1.66 ¥ 4190.47 ¥ 103 ¥ 4 ¥ 10-3
3RT 3 ¥ 8.314 ¥ 300 = = 1117.45 kg
(i) vrms = = 0.083 ¥ 300
M 2 ¥ 10-3 Mass of balloon with helium
3 ¥ 83.14 ¥ 3 ¥ 104 = 1117.45 + 100 = 1217.45 kg
= = 19.34 ¥ 102 m/sec. Pay load = mass of air displaced – mass of filled bal-
2
loon = 5028.56 – 1217.45 = 3811 kg
3PV 3 ¥ 105 ¥ 5 ¥ 10-3 38. The compressibility factor for 1 mole of a Van der
(ii) = -3
= 25 ¥ 104 Walls gas at 0°C and 100 atm pressure is found to be
nM 3 ¥ 2 ¥ 10
0.5. Assuming that volume of a gas molecule is ‘negli-
= 500 m/sec gible’, calculate the Van der Walls constant ‘a’.
PV
3P 3 ¥ 105 Sol. For 1 mole of the gas Z =
(iii) = = 17.32 m/sec. RT
d 103
100 ¥ V
10-3 kg 0.5 =
1 g/ml = = 103 kg/m3 0.0821 ¥ 273
10-6 m3
V = 0.112 L
36. What is the density of moist air with 90% relative hu- Ê a ˆ
midity under the condition of 1 atm pressure and 21ºC. Neglecting b, the equation is Á P + 2 ˜ V = RT
Ë V ¯
The vapour pressure of water at 25ºC is 23.7 torr and a
dry air has 76% N2 and 24% O2. Also find the differ- or PV + = RT, a = 1.25L2 atm mol–2
V
ence in the density of dry air and moist air at the given
39. Calculate the pressure exerted by 22 g of carbon diox-
condition.
ide in 0.5 dm3 at 298 15 K using:
Sol. (V.P. of H2O at 25ºC is 23.7 mm of Hg)
(a) the ideal gas law and
(Mav)dry air = (0.76 ¥ 28) + (0.24 ¥ 32)
(b) Van der waals equation.
= 21.28 + 7.68 = 28.96 g/mol.
Given: [a = 363.76 kPa dm6 mol–2
Partial Pressure of H 2O and b = 42.67 cm3 mol–1]
{ R.H. = ¥ 100 ;
V.P. of H 2O Ê 22 ˆ 0.0821 ¥ 298.15
Sol. (a) P = Á ˜ ¥ atm = 2.479 ¥ 103 kPa
PM air Ë 44 ¯ 0.5
Density (r) =
RT Ê Ê 1ˆ
2 ˆ
Á Á ˜ ¥ 363.76 ˜
\ PH2O = 23.7 × 0.9 = 21.33 mmHg = 0.028 atm. Ë 2¯ Ê 1 42.67 ˆ
(b) Á P + ˜ ¥ Á 0.5 – ¥ ˜
(Now) Moist air = (28.96 ¥ 0.972) + (18 ¥ 0.028) Ë (0.5)2
¯ Ë 2 1000 ¯
= 28.147 + 0.504 = 28.65 gm/mol.
1
PM moist air 1 ¥ 28.65 = ¥ 8.3187 ¥ 298.15 kPa
= 2
rmoist air = = 1.17 gm/L
RT 0.0821 ¥ 298 P = 2225.55 kPa
Dr = rdry air – rmoist air 40. The Van der waals, constants for gases A, B and C are
as follows:
P Gas a/dm6 kPa mol–2 b/dm3 mol–1
= [ M dryair - M moist air ]
RT A 405.3 0.027
1 B 1215.9 0.030
= (28.96 - 28.65) = 0.1267
0.0821 ¥ 298 C 607.95 0.032
Which gas has
37. Calculate the payload when a balloon of radius 10
(i) the highest critical temperature,
meter mass 100 kg is filled with helium at 1.66 bar
(ii) the largest molecular volume, and
at 27°C. (Density of air 1.2 kgm–3 and R = 0.083 bar
(iii) most ideal behaviour around STP?
dm3k–1mol–1)
8a 3 2.2 ¥ 0.0821 ¥ 200

Sol. (i) find TC = \ gas B V= ¥ = 1.65 L
27 Rb 8 8.21
(ii) Large value of b a largest molecular volume. \ so volume of 0.5 mole N2 = 1.65 ¥ 0.5 = 0.825 L
gas C 43. The critical temperature and pressure of CO2 gas are
(iii) Least value of a and b \ gas A 304.2 K and 72.9 atm respectively. What is the radi-
41. A commercial cylinder contains 6.91 m3 of O2 at 15.18 us of CO2 molecule assuming it to behave as Van der
M Pa and 21°C. The critical constants for O2 are TC = Waal’s gas?
–118.4°C, PC = 50.1 atm. Determine the reduced pres- Sol. TC = 304.2 K PC = 72.9 atm
sure and reduced temperature for O2 under these condi- 8a a
tions. TC = PC =
27 Rb 27b 2
P
Sol. Reduced pressure. Pr = = 2.99 8a
PC
TC 27 Rb 8a 27b 2 8b
\ = = ¥ =
T PC a 27 Rb a R
Reduced temperature Tr = = 1.90 2
TC 27b
42. Calculate the volume occupied by 14.0 g N2 at 200 K RTC 1 0.082 ¥ 304.2
PV 3 PV or b= = ¥
and 8.21 atm pressure if C C = and r r =2.2. 8 PC 8 72.9
RTC 8 Tr
= 0.04277 lit mol–1 = 42.77 cm3/mole
Sol. 14 g N2 Æ 0.5 mole 4
T = 200 k, P = 8.21 atm b = 4 NA ¥ p r 3 = 42.77 cm3
3
PCVC 3 PrVr
= , = 2.2 4 3
RTC 8 Tr \ 4 ¥ NA ¥ p r = 42.77
3
P V
Pr = , Vr = , Tr = T/Tc so, 3 ¥ 42.77 ¥ 10 –23
Pc Vc or r3 = r 3 =
16 ¥ 6.023 ¥ 3.14
( Pc Pr ) (VcVr ) 3 PV 3 or r3 = 0.424 ¥ –23 = 4.24 ¥ –24
= ¥ 2.2 fi = ¥ 2.2
R (TcTr ) 8 RT 2 or r = (4.24)1/3 ¥ –8 cm = 1.62 ¥ –8 cm
\ radius of CO2 molecule = 1.62 Å
Exercise
5. 380 mL of a gas at 27°C, 800 mm of Hg weights 0.455
LEVEL I g. The molecular weight of gas is
(a) 27 (b) 28 (c) 29 (d) 30
1. Pressure of 1g of an ideal gas A at 27° C is found to be 6. At what temperature will be the rate of effusion of N2
2 bar. When 2 g of another ideal gas B is introduced in be 1.625 times the rate of effusion of SO2 at 500°C?
the same flask at the same temperature, the pressure (a) 273 K (b) 830 K (c) 110 K (d) 173 K
becomes 3 bar. Find the relationship between their mo- 7. What is the ratio of the rate of diffusion of O2 and H2 at
lecular masses. same P and T?
(a) MA = 4MB (b) MB = 4MA (a) 1 : 4 (b) 1 : 8 (c) 1 : 16 (d) 4 : 1
(c) MA = 2MB (d) MB = 2MA 8. Equal weights of methane and oxygen are mixed in an
2. Density of a gas is found to be 5.46 g/dm3 at 27°C at 2 empty container at 25°C. What is the fraction of the
bar pressure. What will be its density at STP? total pressure exerted by oxygen?
(a) 6 gm/l (b) 8 gm/l (c) 3 gm/l (d) 1.5 gm/l 1 1 2 1 273
3. Calculate the temperature of 4.0 mole of a gas occupy- (a) (b) (c) (d) ¥
3 2 3 3 298
ing 5 dm3 at 3.32 bar. (R = 0.83 bar dm3 K–1 mol–1).
9. What will be the pressure of the gaseous mixture when
(a) 100 K (b) 50 K (c) 150 K (d) 200 K
0.5 L of H2 at 0.8 bar and 2.0 L of dioxygen at 0.7 bar
4. Calculate the volume occupied by 8.8 g of CO2 at
are introduced in a 1 L vessel at 27°C?
31.1°C and 1 bar pressure. R = 0.083 bar LK–1mol–1.
(a) 4 bar (b) 1.8 bar
(a) 10.1 ltr (b) 8.0 ltr
(c) 0.9 bar (d) 3.6 bar
(c) 2.0 ltr (d) 5.05 ltr
Gaseous State 3.29
10. Calculate the total pressure in a mixture of 8 g of (a) 2 atm (b) 0.5 atm (c) 1.5 atm (d) 1 atm
dioxygen and 4 g of dihydrogen confined in a vessel of 20. The density of CO2 at 100°C and 800 mm Hg pressure
1 dm3 at 27°C. R = 0.083 bar dm3 K–1 mol–1. would be
(a) 28.5 bar (b) 56.025 bar (a) 1.212 g ltr–1 (b) 1.5124 g ltr–1
(c) 112.5 bar (d) 14.25 bar (c) 2.1124 g ltr –1
(d) 1.012 g ltr–1
11. 2.9 g of gas at 95°C occupied the same volume as 0.184 21. Pressure remaining the same, the volume of given mass
g of dihydrogen at 17°C, at the same pressure. What is of an ideal gas increases for every degree centigrade
the molar mass of the gas? rise in temperature by definite fraction of its volume at
(a) 120 g mol–1 (b) 20 g mol–1 (a) 0°C (b) its critical temperature
–1
(c) 80 g mol (d) 40 g mol–1 (c) absolute zero (d) its Boyle temperature
12. The average velocity of an ideal gas molecule at 27°C 22. If 20 cm3 gas at 1 atm is expanded to 50 cm3 at constant
is 0.3 m/sec. What will be the average velocity at T, then what is the final pressure?
927°C?
(a) 0.6 m/sec (b) 0.3 m/sec 1 1
(a) 20 ¥ (b) 50 ¥
(c) 0.9 m/sec (d) 3.0 m/sec 50 200
13. The root mean square velocity of one mole of a monoa-
1
tomic gas having molar mass M is Ur.m.s. What is the (c) 1 ¥ ¥ 50 (d) None of these
relation between the average kinetic energy (E) of the 20
gas and Ur m.s.? 23. The volume of 1 g each of methane (CH4), ethane
(C2H6), propane (C3H8) and butane (C4H10) was mea-
3E 2E
(a) ur m s = (b) ur m s = sured at 350K and 1 atm. What is the volume of bu-
2M 3M tane?
2E E (a) 495 cm3 (b) 600 cm3
(c) ur m s = (d) ur m s = (c) 900 cm3 (d) 1700 cm3
M 3M
24. A sample of gas occupies 100 mL at 27°C and 740 mm
14. The compressibility of a gas is less than unity at STP.
pressure. When its volume is changed to 80 mL at 740
Therefore,
mm pressure, what will be the temperature of gas?
(a) Vm > 22.4 ltr (b) Vm < 22.4 ltr
(c) Vm = 22.4 ltr (d) Vm = 44.8 ltr (a) 21.6°C (b) 240°C
15. In Van der Waals equation of state for a non-ideal gas, (c) –33°C (d) 89.5°C
what is the term that accounts for intermolecular forc- 25. At S.T.P., the density of nitrogen monoxide is?
es? (a) 3.0 gL–1 (b) 30 gL–1
–1
(a) (V – b) (b) RT (c) 1.34 gL (d) 2.68 gL–1
26. The rate of effusion of a gas is proportional to?
Ê a ˆ
(c) Á P + 2 ˜ (d) (RT)–1
Ë V ¯ P P
(a) (b)
16. 4.0 g of argon has pressure P at temperature T K in a d d
vessel. On keeping the sample at 50° higher tempera-
ture, 0.8 g gas was given out to maintain the pressure P. P P
(c) (d)
What was the original temperature? d d
(a) 73 K (b) 100 K (c) 200 K (d) 510 K 27. If 4 g of oxygen diffuse through a very narrow hole,
17. The temperature of an ideal gas is increased from 140 how much hydrogen would have diffused under identi-
K to 560 K. If at 140 K the root mean square velocity cal conditions?
of the gas molecules is u, at 560 K it becomes (a) 16 g (b) 1 g (c) 1/4 g (d) 64 g
(a) 5u (b) 2u (c) u/2 (d) u/4 28. The rate of diffusion of SO2 and O2 are in the ratio
18. 40 mL of mixture of H2 and O2 was placed in a gas bu- (a) 1 : 2 (b) 1 : 32 (c) 1 : 2 (d) 1 : 4
rette at 18°C and 1 atm. A spark was produced so that 29. A cylinder is filled with a gaseous mixture containing
the formation of water was complete. The remaining
equal masses of CO and N2. The partial pressure ratio
pure gas had a volume of 10 mL at 18°C and 1 atm. If
is
the remaining gas was H2, what was the initial mole %
(a) PN2 = PCO (b) PCO = 0.875 PN2
of H2 in mixture?
(a) 75% (b) 25% (c) 60% (d) 45% (c) PCO = 2 PN2 (d) PCO = 1/2 PN2
19. A flask of capacity of 1 ltr contains NH3 at 1 atm and
25°C. A spark is passed through until all the NH3 is 30. Which of the following is correct relation for root mean
decomposed into N2 and H2. Calculate the pressure of square velocity?
gases left at 25°C.
42. A gas occupies 1.5 ltr, volume at 75 cm Hg pressure. At

8 RT 3RT
(a) Vrms = (b) Vrms = the same temperature, what will be the volume of gas
pMw Mw at 50 cm, Hg pressure?
(a) 1.25 ltr (b) 3.25 ltr
2 RT 3RT (c) 4.25 ltr (d) 2.25 ltr
(c) Vrms = (d) Vrms =
Mw Mw 43. A mixture of gases at 760 mm Hg contains 65% N2,
31. The average velocity of gas molecules is equal to 15% O2 and 20% CO2 by volume, then partial pressure
1 1 of each gas in mm is
Ê 8 RT ˆ 2 Ê 3RT ˆ 2 (a) 494, 114, 252 (b) 494, 224, 152
(a) Á (b) Á
Ë M ˜¯
w Ë M ˜¯
w
(c) 494, 114, 152 (d) None of these
44. 0.45 g of a gas having mole weight is 60 and 0.22 g
1
Ê 8 RT ˆ 2 Ê 8 RT ˆ of another gas has 44 mole weight. The total pressure
(c) Á (d) Á on these gases is 75 cm Hg, then partial pressure of
Ë p M w ˜¯ Ë p M w ˜¯ another gas is
32. A gas occupies 300 mL volume at 27°C temperature (a) 30 cm of Hg (b) 20 cm of Hg
and 730 mm pressure. Its volume at STP is (c) 10 cm of Hg (d) 40 cm of Hg
(a) 162.2 mL (b) 262.2 mL 45. If the density of a gas A is 1.5 times that of B then the
(c) 362.2 mL (d) 462.2 mL molecular mass of A is M. The molecular mass of B
33. A truck having oxygen cylinders is coming from Shri- will be
nagar. The gas in cylinder is at –23°C temperature and M
(a) 1.5 M (b)
3 atm pressure when truck passes from Madras. What 1.5
will be the pressure of oxygen gas when temperature is M
30°C? (c) 3M (d)
3
(a) 2.64 atm (b) 1.64 atm 46. A certain mass of a gas occupies a volume of 2 ltr at
(c) 1 atm (d) 3.64 atm STP. Keeping the pressure constant at what tempera-
34. Find out the density of CO2 at 100°C temperature and ture would the gas occupy a volume of 4 ltr?
400 mm Hg pressure. (a) 546°C (b) 273°C
(a) 0.75 g L–1 (b) 2.5 g L–1 (c) 100°C (d) 50°C
–1
(c) 0.5 g L (d) 0.2 g L–1 47. 8.2 L of an ideal gas weighs 9.0 g at 300 K and 1 atm
35. The density of a gas at –23°C temperature and 780 torr pressure. The molecular mass of gas is
pressure is 1.40 g L–1. Identify the gas. (a) 9 (b) 27 (c) 54 (d) 81
(a) CO2 (b) SO2 (c) Cl2 (d) N2 48. One litre of an unknown gas weighs 1.25 g at N.T.P.
36. Calculate the weight of CH4 gas when the applied pres- Which of the following gas pertains to the above data?
sure is 16 atm, temperature is 27°C and its volume is 9 (a) CO2 (b) NO2 (c) N2 (d) O2
litre (R = 0.08 L atm K–1). 49. If pressure of a gas contained in a closed vessel is in-
(a) 96 g (b) 86 g (c) 80 g (d) 90 g creased by 0.4% when heated by 1°C, what is its initial
37. The density of SO2 at STP is temperature?
(a) 2.86 g L–1 (b) 1.76 g L–1 (a) 250 K (b) 250°C
(c) 1.86 g L –1
(d) None of these (c) 2500 K (d) 25°C
38. The volume occupied by 7 g N2 gas at 27°C tempera- 50. A football bladder contains equimolar proportions of
ture and 750 mm Hg pressure is H2 and O2. The composition by mass of the mixture
(a) 6.3 ltr (b) 7.3 ltr effusing out of punctured football is in which ratio (H2
(c) 6.8 ltr (d) 5.3 ltr : O2)?
39. 5 g XeF4 gas is filled in a 6 ltr vessel at 80°C tempera- (a) 1 : 4 (b) 2 2 :1 (c) 1: 2 2 (d) 4 : 1
ture, the applied pressure on gas is 51. At low pressure compressibility factor is equal to:
(a) 0.21 atm (b) 0.31 atm
Ê a ˆ Ê RTV ˆ
(c) 0.11 atm (d) 0.41 atm (a) Á1 - ˜ (b) Á1 - ˜
Ë RTV ¯ Ë a ¯
40. 5.75 g of gas at 55°C temperature and 0.940 atm pres-
sure occupies 3.5 ltr volume. Identify the molecular Ê a ˆ Ê RTV ˆ
weight of gas. (c) Á1 + ˜ (d) Á1 + ˜
Ë RTV ¯ Ë a ¯
(a) 45 (b) 47 (c) 49 (d) 51
52. If a mixture containing 3 moles of hydrogen and 1 mole
41. 28 g of a N2 gas occupies 10 ltr volume at 2.46 atm
of nitrogen is converted completely into ammonia,
pressure. Identify the temperature.
what will be the ratio of initial and final volume under
(a) 300 K (b) 320 K
the same temperature and pressure?
(c) 340 K (d) 280 K
(a) 3 : 1 (b) 1 : 3 (c) 2 : 1 (d) 1 : 2
Gaseous State 3.31
53. SO2 at STP contained in a flask was replaced by O2 62. The weight of 350 mL of a diatomic gas at 0°C and 2
under identical conditions of pressure, temperature and atm pressure is 1 g. The weight in g of one atom at NTP
volume. Then the weight of O2 will be ______ of SO2? is
(a) half (b) one fourth (a) 2.64 ¥ 10–23 g (b) 2.64 ¥ 10–22 g
–23
(c) twice (d) four times (c) 5.28 ¥ 10 g (D) 0.82 ¥ 10–22 g
54. According to Charle’s law, 63. Oxygen is present in a litre flask at a pressure of 7.6 ¥
Ê dV ˆ Ê dV ˆ 10–10 mm of Hg. The number of oxygen molecules in
(a) Á = k (constant) (b) Á =P
Ë dT ˜¯ P Ë dT ˜¯ P the flask at 0°C is
(a) 2.7 ¥ 109 molecules (b) 2.7 ¥ 1010 molecules
Ê dV ˆ Ê dV ˆ (c) 2.7 ¥ 1011 molecules (d) 2.7 ¥ 1012 molecules
(c) Á =V (d) Á =T
Ë dT ˜¯ P Ë dT ˜¯ 64 The r m.s. velocity of hydrogen at 27°C, R = 8.314 J
55. A sample of gas at 35°C and 1 atm pressure occupies a mol–1 K–1 is
volume of 3.75 ltr. At what temperature should the gas (a) 1.934 m/s (b) 19.34 m/s
be kept if it is required to reduce the volume to 3 ltr at (c) 193.4 m/s (d) 1934 m/s
the same pressure? 65. Temperature at which R.M.S. speed of O2 is equal to
(a) –26.6°C (b) 0°C that of neon at 300 K is
(c) 3.98°C (d) 28°C (a) 280 K (b) 480 K
56. Equal weights of methane and hydrogen are mixed in (c) 680 K (d) 180 K
an empty container at 25°C. The fraction of total pres- 66. The most probable velocity of a neutron at 20°C is
sure exerted by hydrogen is nearby
(a) 1/2 (b) 8/9 (c) 16/19 (d) 1/9 (a) 220 m/s (b) 2200 m/s
57. The best vaccum so far attained in laboratory is 10–10 (c) 22200 m/s (d) 22 m/s
mm of Hg. The number of molecules of gas remain per 67. The R.M.S. speed of the molecules of a gas of density
cm3 at 20°C in this vaccum is 4 kg m–3 and pressure 1.2 ¥ 105 N m–2 is
(a) 3.29 ¥ 104 molecules (a) 120 m s–1 (b) 300 m s–1
–1
(b) 3.29 ¥ 105 molecules (c) 600 m s (d) 900 m s–1
(c) 3.29 ¥ 106 molecules 68. The R.M.S. velocity of a gas whose each molecule
(d) 3.29 ¥ 107 molecules weighs 10–12 g and at temperature 27°C is
58. A hydrocarbon contains 10.5 g of carbon per gm of H. (a) 0.70 cm/s (b) 0.35 cm/s
One litre vapours of hydrocarbon at 127°C and 1 atm (c) 0.35 m/s (d) 0.70 m/s
pressure weighs 2.8 g. The molecular formula of hy- 69. The average speed of an ideal gas molecule at 27°C is
drocarbon is 0.3 m sec–1. The average speed at 927°C is
(a) C6H8 (b) C7H8 (c) C5H12 (d) C8H4 (a) 0.15 m sec–1 (b) 0.6 m sec–1
59. A 0.5 dm3 flask contains gas A and 1 dm3 flask contains (c) 1.2 m sec –1
(d) 0.6 cm sec–1
gas B at the same temperature. If density of A = 3 g/dm3 70. The temperature at which CO2 has the same R.M.S.
and that of B = 1.5 g/dm3 and the molar mass of A = 1/2 speed to that of O2 at S.T.P. is/are
of B, the ratio of pressure exerted by gases is (a) 375.38 K (b) 102.38 °C
PA PA (c) 275.38 K (d) 202.38 °C
(a) =2 (b) =1 71. The temperature at which the most probable speed of
PB PB
CO2 molecules be twice as that of 50°C is
PA PA (a) 200°C (b) 1292 K
(c) =4 (d) =3
PB PB (c) 100°C (d) 646 K
72. What is the total translational and rotational energy of
60. 120 g of an ideal gas of molecular weight 40 are con-
1 mole of oxygen at 300 K?
fined to a volume of 20 ltr at 400 K. What is the pres-
R = 8.314 J mol–1 K–1:
sure of gas is?
(a) 6235.5 J (b) 623.25 J
(a) 490 atm (b) 4.92 atm
(c) 62.325 J (d) 6.2325 J
(c) 2236 atm (d) 22.4 atm
73. The kinetic energy of N molecules of O2 is x Joule at
61. A cylinder contains acetylene gas at 27°C and 4.05 M
Pa. The pressure in the cylinder after half the mass of –123°C. Another sample of O2 at 27°C has a kinetic
gas is used up and the temperature that has fallen to energy of 2 x. The later sample contains ________ mol-
12°C will be ecules of O2.
(a) 4.05 M Pa (b) 2.025 M Pa (a) N (b) N/2 (c) 2 N (d) 3 N
(c) 3.84 M Pa (d) 1.92 M Pa 74. The average kinetic energy in joules of molecules in
8.0 gm of methan at 27°C is
(a) 6.21 ¥ 10–20 J/molecule (a) Vm > 22.4 L (b) Vm < 22.4 L
(b) 6.21 ¥ 10–21 J/molecule (c) Vm = 22.4 L (d) Vm ≥ 44.8 L
(c) 6.21 ¥ 10–22 J/molecule 86. If two moles of an ideal gas at 546 K occupies a volume
(d) 3.1 ¥ 10–22 J/molecule of 44.8 ltr, the pressure must be
75. The ratio of rates of diffusion of CO2 and SO2 at the (a) 2 atm (b) 3 atm (c) 4 atm (d) 1 atm
same pressure and temperature is 87. At STP, the order of root mean square velocity of mol-
(a) 4 : 11 (b) 11 : 4 ecules of H2, N2, O2 and HBr is:
(c) 1 : 4 (d) 1 : 6 (a) H2 > N2 > O2 > HBr (b) HBr > O2 > N2 > H2
76. 20 L of SO2 diffuses through a porous partition in 60 (c) HBr > H2 > O2 > N2 (d) N2 > O2 > H2 > HBr
seconds. Volume of O2 diffuse under similar conditions 88. The density of a gas at 27°C and 1 atm is d. Pressure
in 30 seconds will be remaining constant at which of the following tempera-
(a) 12.14 L (b) 14.14 L tures will its density become 0.75 d?
(c) 18.14 L (d) 28.14 L (a) 20°C (b) 30°C (c) 400 K (d) 300 K
77. Three footballs are respectively filled with nitrogen, 89. At 27°C the ratio of R.M.S velocities of ozone to oxy-
hydrogen and helium. If the leaking of the gas occurs gen is
with time from the filling hole, then the ratio of the rate (a) 3/5 (b) 4/3
of leaking of gases (rN2 : rH2 : rHe ) from three footballs
(in equal time interval) is (c) 2/3 (d) 0.25
(a) (1: 14 : 7) (b) ( 14 : 7 :1) 90. A real gas most closely approaches the behaviour of an
ideal gas at
(c) ( 7 :1: 14) (d) (1: 7 : 14) (a) 15 atm and 200 K (b) 1 atm and 273 K
78. NH3 and SO2 gases are being prepared in two corners (c) 0.5 atm and 500 K (d) 15 atm and 500 K
of a laboratory. The gas that will be detected first in the 91. At STP, 2.8 ltr of hydrogen sulphide were mixed with
middle of the laboratory is 1.6 ltr of sulphur dioxide and the reaction occurred ac-
(a) NH3 (b) SO2 cording to the equation,
(c) Both at the same time(d) Cannot determine 2H2S (g) + SO2 (g) h 2H2O (l) + 3S (s)
79. 10 mL of gaseous hydrocarbon on combustion gives 40 Which of the following shows the volume of the gas
mL of CO2 and 50 mL of H2O. The hydrocarbon is remaining after the reaction?
(a) C4H6 (b) C4H8 (c) C8H10 (d) C4H10 (a) 0.2 ltr of SO2 (g) (b) 0.4 ltr of H2 (g)
80. The volume of oxygen required for complete oxidation (c) 1.2 ltr of H2S (g) (d) 1.2 ltr of SO2 (g)
of 2 ltr of methane at NTP is 92. The rates of diffusion of SO3, CO2, PCl3 and SO2 are in
(a) 12.25 L (b) 4 L the following order:
(c) 1 L (d) 3 L (a) PCl3 > SO3 > SO2 > CO2
81. LPG is a mixture of n-butane and iso-butane. The vol- (b) CO2 > SO2 > PCl3 > SO3
ume of oxygen needed to burn 1 kg of LPG at NTP (c) SO2 > SO3 > PCl3 > CO2
would be (d) CO2 > SO2 > SO3 > PCl3
(a) 2240 L (b) 2510 L 93. A closed vessel contains equal number of nitrogen and
(c) 1000 L (d) 500 L oxygen molecules at pressure of P mm. If nitrogen is
82. The viscosity of a which liquid is the maximum? removed from the system, then the pressure will be
(a) Water (b) Glycol (a) P (b) 2P (c) P/2 (d) P2
(c) Acetone (d) Ethanol 94. The rate of diffusion of methane at a given temperature
83. Equal masses of methane and oxygen are mixed in an is twice that of gas X. The molecule weight of X is
empty container at 25°C. The fraction of the total pres- (a) 64.0 (b) 32.0 (c) 4.0 (d) 8.0
sure exerted by methane is R.M.S velocity of SO 2
(a) 1/3 (b) 1/2 95. The ratio, , of sulphur dioxide
R.M.S velocity of He
(c) 2/3 (d) (1/3) (273/298)
84. Helium atom is two times heavier than a hydrogen and helium gases at 30°C is equal to
molecule. At 298 K, the average kinetic energy of a (a) 4 (b) 0.25 (c) 0.10 (d) 8
helium atom is 96. A certain volume of argon gas (Mol. Wt. 40) requires
(a) Two times that of a hydrogen molecules 45 s to effuse through a hole at a certain pressure and
(b) Same as that of a hydrogen molecules temperature. The same volume of another gas of un-
(c) Four times that of a hydrogen molecules known molecular weight requires 60 s to pass through
(d) Half that of a hydrogen molecules the same hole under the same conditions of tempera-
85. The compressibility of a gas is more than unity at STP. ture and pressure. The molecular weight of the gas is
Therefore, (a) 53 (b) 35 (c) 71 (d) 120
Gaseous State 3.33
97. A chemist has synthesised a greenish yellow gaseous 7. The circulation of blood in human body supplies O2
compound of chlorine and oxygen and finds that its and releases CO2. The concentration of O2 and CO2
density is 7.71 g/L at 36°C and 2.88 atm. Then the mo- is variable but on the average, 100 mL blood contains
lecular formula of the compound will be 0.02 g of O2 and 0.08 g of CO2. The volume of O2 and
(a) ClO3 (b) ClO2 (c) ClO (d) Cl2O2 CO2 at 1 atm and at body temperature of 37°C, assum-
98. When a gas is expanded at constant temperature, ing 10 ltr blood in human body, would be
(a) the pressure decreases. (a) 2 ltr, 4 ltr (b) 1.5 ltr, 4.5 ltr
(b) the kinetic energy of the molecules remains the (c) 1.59 ltr, 4.62 ltr (d) 3.82 ltr, 4.62 ltr
same. 8. When 2 g of a gas ‘A’ is introduced into an evacuated
(c) the kinetic energy of the molecules decreases. flask kept at 25°C, the pressure is found to be 1 atm. If
(d) the number of molecules of the gas decreases. 3 g of another gas ‘B’ is then added to the same flask,
99. At what temperature will the total K.E. of 0.3 mol of the total pressure becomes 1.5 atm. Assuming ideal gas
He be the same as the total K.E. of 0.40 mol of Ar at behaviour, calculate the ratio of molar masses MA : MB
400 K (a) 1 : 3 (b) 1 : 4 (c) 4 : 1 (d) 3 : 1
(a) 533 K (b) 400 K (c) 346 K (d) 300 K 9. 5 mL of a gaseous hydrocarbon was exposed to 30 mL
100. If molecules of the gas are spherical of radius 1 Å, the of O2. The resultant gas, on cooling is found to mea-
volume occupied by the molecules in 1 mol of a gas is: sure 25 mL, of which 10 mL was absorbed by NaOH
(a) 22400 mL (b) 22.4 L and the remainder by pyrogallol. All measurements are
(c) 2.52 mL (d) 4.22 mL made at constant pressure and temperature. The mo-
lecular formula of the hydrocarbon is
LEVEL II (a) C2H2 (b) C3H8 (c) C2H4 (d) C2H6
10. A gaseous compound X contained 44.4% C, 51.9% N
and 3.7% H. Under like conditions 30 cm3 of X dif-
1. The drain cleaner, Drainex contains small bits of alu-
fused through a pinhole in 25 sec and the same volume
minum which react with caustic soda to produce dihy-
drogen. What volume of dihydrogen at 20°C and one of H2 diffused in 4.81 sec. The molecular formula of X
bar will be released when 0.15g aluminum reacts? is
(a) 200.4 mL (b) 102.5 mL (a) C2H2N (b) C2H4N2
(c) 101.25 mL (d) 405.0 mL (c) C2H2N2 (d) C4H2N212.
2. A mixture of dihydrogen and dioxygen at one bar pres- 11. The density of the gaseous mixture (He and N2) is
sure contains 20% by weight of dihydrogen. Calculate 10
g/ltr at NTP. What is the percentage composition
the partial pressure of dihydrogen. 22.4
(a) 0.8 bar (b) 0.4 bar (c) 1.6 bar (d) 3.2 bar of He and N2 by volume in this mixture respectively?
3. How much time would it take to distribute one Avoga- (a) 75%, 25% (b) 25%, 75%
dro number of wheat grains, if 1010grains are distrib- (c) 30%, 70% (d) 40%, 60%
uted in each second? 12. A gas bulb containing air is connected to an open limb
(a) 4 ¥ 102 year (b) 9 ¥ 106 year manometer at 27°C and at 750 mm Hg. Assuming that
4
(c) 6 ¥ 10 year (d) 2 ¥ 106 year initially the level of Hg in the both limbs were same.
4. What will be the pressure exerted by a mixture of 3.2 g The bulb was heated to 77°C, what will be difference in
of methane and 4.4 g of carbon dioxide contained in a the levels of Hg in two limbs? (Assuming the volume
9 dm3 flask at 27°C? difference of the gas produced is negligible at higher
(a) 8.314 Pa (b) 8.314 ¥ 102 Pa temperature).
2
(c) 2 ¥ 10 Pa (d) 8.314 ¥ 104 Pa (a) 7.5 cm Hg (b) 8 cm Hg
5. 34.05 mL of phosphorus vapour weighs 0.0625 g at (c) 6 cm Hg (d) 12.5 cm Hg
546 °C and 0.1 bar pressure. What is the molar mass of 13. In the following graph of Maxwell-Boltzmann distri-
phosphorus? bution of molecular velocities
(a) 1247.7 g (b) 1147.0 g T1
(c) 1047 g (d) None of these T2
6. A student forgot to add the reaction mixture to the
round bottom flask at 27°C but instead he/she placed
Fraction of
T3
molecules
the flask on the flame. After a lapse of time, he realised

his mistake and using a pyrometer he found the tem-
perature of the flask was 477°C. What fraction of air
would have been expelled out? Velocity
(a) 5/3 (b) 5/6 (c) 3/5 (d) 6/5
Which of the following is the correct order of tempera- (c) 0.55, CO2 is more compressible than ideal gas.
ture? (d) 0.62, CO2 is more compressible than ideal gas.
(a) T1 < T2 < T3 (b) T3 < T2 < T1 24. On the surface of the Earth at 1 atm pressure, a balloon
(c) T2 < T1 < T3 (d) None of these filled with H2 gas occupies 500 mL. This volume 5/6 of
14. CH4 gas is collected over water vapour having total its maximum capacity. The balloon is left in air. It starts
pressure = 735 torr and temperature = 29°C. If the pres- rising. The height above which the balloon will burst
sure of water vapour is 30 at 29°C temperature, the ap- if temperature of the atmosphere remains constant and
plied pressure of dry methane gas is the pressure decreases 1 mm for every 100 cm rise of
(a) 605 torr (b) 205 torr height is
(c) 405 torr (d) 705 torr (a) 120 m (b) 136.67 m
15. What is the density of oxygen gas at 1.0 atm. pressure (c) 126.67 m (d) 100 m
and 27°C temperature? 25. 11 moles N2 and 12 moles of H2 mixture reacted in 20
(a) 0.8 g L–1 (b) 1.3 g L–1 litre vessel at 800 K. After equilibrium was reached,
(c) 1.8 g L –1
(d) 2.3 g L–1 6 mole of H2 was present. 3.58 ltr of liquid water is
injected in equilibrium mixture and resultant gaseous
16. The van der Waal’s constant ‘b’ of a gas is 4p ¥ 10–4
mixture suddenly cooled to 300 K. What is the final
L/mol. How near can the centres of the two molecules
pressure of gaseous mixture? Negative vapour pressure
approach each other?
of liquid solution. Assume (i) all NH3 dissolved in wa-
[Use : NA = 6 ¥ 1023]
ter, (ii) no change in volume of liquid and (iii) no reac-
(a) 10–7 m (b) 10–10 m tion of N2 and H2 at 300 K.
–11
(c) 10 m (d) 10–9 m
17. A box of 1L capacity is divided into two equal com- N2 : 11 moles T 800 K N2H2 T 300 K; P ?
partments by a thin partition which are filled with H2 : 12 moles V 20 L NH3(aq) solution
2 g H2 and 16g CH4 respectively. The pressure in each
compartment is recorded as P atm. The total pressure Initial conditiion
when partition is removed will be (a) 18.47 atm (b) 60 atm
(a) P (b) 2P (c) P/2 (d) P/4 (c) 22.5 atm (d) 45 atm
18. A 2.24 L cylinder of oxygen at N.T.P. is found to devel- 26. Two closed vessel A and B of equal volume contain-
op a leakage. When the leakage was plugged, the pres- ing air at pressure P1 and temperature T1 are connected
sure dropped to 570 mm of Hg. The number of moles to each other through a narrow open tube. If the tem-
of gas that escaped will be perature of one is now maintained at T1 and other at T2
(a) 0.025 (b) 0.050 (where T1 > T2) then what will be the final pressure?
(c) 0.075 (d) 0.09
T1 2PT
1 2
19. An open vessel containing air is heated from 27°C to (a) (b)
127°C. The fraction of air originally present which 2 PT
1 2 T1 T2
+
goes out of it is 2PT
1 2 2P1
(a) 3/4 (b) 1/4 (c) 2/3 (d) 1/8 (c) (d)
T1 - T2 T1 + T2
20. At a constant pressure, what should be the percent-
27. A balloon containing 1 mole air at 1 atm initially is
age increase in the temperature in Kelvin for a 10%
filled further with air till pressure increases to 4 atm.
increase in volume The initial diameter of the balloon is 1 m and the pres-
(a) 10% (b) 20% (c) 5% (d) 50% sure at each stage is proportion to diameter of the
21. Assuming that O2 molecule is spherical in shape with balloon. How many number of moles of air added to
radius 2Å, the percentage of the volume of O2 mol- change the pressure from 1 atm to 4 atm?
ecules to the total volume of gas at S.T.P. is (a) 80 (b) 257 (c) 255 (d) 256
(a) 0.09% (b) 0.9% (c) 0.009% (d) 0.045% 28. What is the density of wet air with 75% relative humid-
22. The mass of molecule A is twice that of molecule B. ity at 1 atm and 300 K? Given : vapour pressure of H2O
The root mean square velocity of molecule A is twice is 30 torr and average molar mass of air is 29 g mol–1.
that of molecule B. If two containers of equal volume (a) 1.614 g/L (b) 0.96 g/L
have same number of molecules, the ratio of pressure (c) 1.06 g/L (d) 1.164 g/L
PA/PB will be 29. Calculate minimum number of balloons each of vol-
(a) 8 : 1 (b) 1 : 8 (c) 4 : 1 (d) 1 : 4 ume 82.1 L required to lift a mass of 1 kg to a height
23. Calculate the compressibility factor for CO2, if one of 831 m. Given : molar mass of air = 29 g/mol, tem-
mole of it occupies 0.4 ltr at 300 K and 40 atm. Com- perature is constant at 290 K and mass of each balloons
ment on the result. is 40 g. [Use e–0 1 = 0.9, pressure at sea level = 1 atm,
(a) 0.40, CO2 is more compressible than ideal gas. acceleration due to gravity (g) = 10 m/s2].
(b) 0.65, CO2 is more compressible than ideal gas. (a) 10 (b) 20 (c) 25 (d) 50
Gaseous State 3.35
LEVEL III (C) CO2 (R) Highest value of CP/CV

at temperature T
1. Match the columns: (D) SO2 (S) Vibrational energies
equal to 4RT per mole
Column I Column II at temperature T
(A) Tc/Pc (P) Z
(B) Tc/Vc (Q) a/Rb Comprehension
(C) TB (R) 8b/R Passage # 1 (Ques. 5 to 7)
(D) Ti/TB (S) 8a/81Rb2 Measuring the molar mass of gases is an important applica-
tion of the ideal gas law. Before the development of mass
2. Four different gases and their Van der Waal's constant spectroscopy, the molar mass of many substances were de-
are given below. termined using the ideal gas law. The ideal gas law is used
Gas a in atm L2mol–2 b in L/mol to calculate the number of moles in a sample of known mass
then molar mass can be found.
A2 1.5 0.05 5. What is the molar mass of a gas if 0.495 g sample of
B2 2.0 0.08 the gas occupies 127 mL at 754 torr pressure and 98°C
C2 4.2 0.025 temperature?
D2 5.0 0.1 (a) 120 (b) 160 (c) 190 (d) 200
6. Calculate the molar mass of the gas that has a density
of 0.714 g/L at STP
Column I Column II (a) 12 (b) 16 (c) 20 (d) 26
(A) Gas having highest intermolecular (P) A2 7. A 3 ltr container is rated to hold a gas at a pressure not
force of attraction. higher than 100 atm. What is the maximum number of
(B) Gas having smallest size of mol- (Q) B2 moles of the gas that container can hold at 27°C?
ecules. (a) 13.6 (b) 11.4 (c) 12.2 (d) 15.8
(C) Gas that can’t be liquefied at 90 K. (R) C2 Passage # 2 (Qus. 8 to 10)
(D) Gas resembles with ideal gas at the (S) D2 Real gas obey the equation of state PV = nRT under condi-
boiling point of water tions of low pressure and high temperature. In general, the
most easily liquefiable gases, like CO2, SO2 and ammonia
3. show much longer deviations from ideal behaviour than gas-
Column I Column II es like H2, N2, Or, O2. This can be seen from the compress-
ibility factor (Z) – pressure diagram for various gases. The
(A) At definite volume and (P) Changes with deviation from ideal behaviour is attributed to two factors:
temperature total pres- the change in (i) The volume occupied by gas molecules is not negligible
sure of gas. temperature. in comparison to the total volume of gas and (ii) The inter-
(B) The ratio of densities (Q) Changes with molecular forces between gas molecules are significant. To
of moist air to the den- change in num- account for these deviation, the Van der Waals equation has
sity of dry air at the ber of moles. been proposed.
definite temperature 8. The Van der Waals constant "a" for SO2, ethylene, HCl
and pressure. and CO2 are 6.71, 4.47, 13.67 and (3.59) L2 atm mol–2
pH2O (R) Ideal gases respectively. The order of liquefaction of the gases in
(C) The value of . increasing order will be:
p∞H2O (a) CO2 < HCl < C2H4 < SO2
(D) Dalton’s law of partial (S) Lesser than one. (b) SO2 < C2H4 < HCl < CO2
pressures. (c) C2H2 < SO2 < CO2 < HCl
(d) HCl > SO2 > C2H4 > CO2
4. 9. The critical compressibility factor ZC for O2 is 0.308
and its critical pressure and critical volume are 50.1
Column I Column II
atm and 7.8 ¥ 10–2 ltr mol–1 respectively. The Boyle
(A) He (P) Greatest urms at temper- temperature of O2 is (in deg K)
ature T (a) 348.6 (b) 215.4 (c) 154.5 (d) 521.4
(B) H2 (Q) Lowest urms at tempera- 10. At extremely low pressures, the Van der Waals equa-
ture T tion for one mole of a gas may be expressed as
a 20. Two moles of a gas are confined to a 5 ltr flask at 27°C.

(a) PV = RT – (b) P(V – b) = RT Calculate its pressure using Van der Waals equation. For
V
ammonia a = 6.25 atm lit–2 mol–2 and b = 0.037 lit mol–1.
(c) (P + a) (V – b) = RT (d) PV = 1.2RT 21. What will be the temperature difference needed in a
Integer-Types Questions hot air balloon to lift 1.0 kg weight? Assume that the
volume of balloon is 100 m3, the temperature of atmo-
11. One mole of nitrogen gas at 0.8 atm takes 38 seconds sphere is 25°C and pressure is 1.0 atm. Average molar
to diffuse through a pinhole, whereas one mole of an mass of air is 29 amu.
unknown compound of xenon with fluorine XeFx at 22. 4 g of an ideal gas was introduced into a bulb of volume
1.6 atm takes 57 seconds to diffuse through the same of 0.821 dm3 at certain pressure, P and temperature T.
hole. Find out the value of x. The above bulb was placed in a thermostat maintained
12. 9 mL of a gaseous mixture consisting of a gaseous at temperature (T + 125) K of 0.8 gm of the gas was left
compound A and just sufficient amount of oxygen re- off to keep the original pressure. Calculate the pressure
quired for complete combustion, yielded on burning, 4 in atmospheres. [Molecular weight of the gas is 40 g
mL of CO2, 6 mL of water vapour and 2 mL of N2, all mole–1 and R value is 0.0821 lit-atm- K–1 mol.
volumes measured at the same temperature and pres- 23. Pressure in a bulb dropped from 2000 to 1500 mm in
sure. If compound A contained only C, H and N, how 47 minute when the oxygen leaked through a small
many volumes of oxygen are required for complete hole. The bulb was then completely evacuated. A mix-
combustion. ture of oxygen and another gas of molecular weight 79
13. 0.9 gm of an organic compound (Mol. wt. = 90) con- in molar ratio 1:1 at a total pressure of 4000 mm was
tains carbon, hydrogen and oxygen requires 224 mL introduced. Find the molar ratio of two gases remain-
of oxygen at STP for complete combustion. After the ing in the bulb after a period of 74 minute.
combustion, the gases occupy 556 mL at STP. On pass- 24. The composition of the equilibrium mixture, (Cl2
ing it through KOH solution, the volume reduced to m 2Cl) which is attained at 1200°C, is determined
112 mL. If the compound has formula CXHXO2X, then by measuring the rate of effusion through a pinhole.
find out the value of X. It is observed that at 1.80 mm Hg pressure, the mix-
14. At 400 K, the root mean square (rms) speed of a gas X ture effuses 1.16 times as fast a krypton effuses under
(Mol. wt. = 40) is equal to the most probable speed of the same conditions. Calculate the fraction of chlorine
gas Y at 60 K. What is the molecular weight of the gas molecules dissociated into atoms. (At. wt. of Kr = 84).
Y? 25. A mixture of ethane and ethene occupies 40 ltr at 1.00
15. Two flasks A and B have equal volumes. A is main- atm and at 400 K. The mixture reacts completely with
tained at 300 K and B at 600 K. While A contains H2 130 gm of O2 to produce CO2 and H2O. Assuming ideal
gas, B has an equal mass of CH4 gas. Assuming ideal behavior, calculate the mole fraction of C2H4 and C2H6
behaviour for the both gases, find the ratio of (uav)A : in the mixture?
(uav)B. 26. The total pressure of a mixture of H2 and O2 is 1.00 bar.
16. A flask of capacity of 1 L containing NH3 at 1atm and The mixture is allowed to react to form water which is
25°C. A spark is passed through until all the NH3 is de- completely removed to leave only pure at a pressure of
composed in N2 and H2. Calculate the pressure of gases 0.35 bar. Assuming ideal gas behavior and that all pres-
left at 25°C after the reaction. sure measurements we made under the same conditions
17. A compound exists in the gaseous phase both as mono- of temperature and volume, calculate the composition
mer (A) and dimer (A2). The atomic weight of A is 48. of the original mixture.
In an experiment 96 g of compound was confined in 27. The degree of dissociation is 0.4 at 400 K and 1.0 atm
vessel of volume 33.6 L and heated to 273°C. Calculate for the gaseous reaction PCl5(g) m PCl3(g) + Cl2(g).
the pressure developed if the compound exists as dimer Assuming ideal behavior of all gases, calculate the den-
to the extent of 50% by weight under these conditions. sity of equilibrium mixture at 400 K and 1.0 atm. (P =
18. The compressibility factor for nitrogen at 330 K and 31, Cl = 35.5)
800 atm is 1.90 and at 570 K and 200 atm is 1.10 A 28. The pressure exerted by 12 gm of an ideal gas at t°C
certain mass of N2 occupies a volume of 1 dm3 at 330 in a vessel of volume v ltr is one atm. When the tem-
K and 800 atm. Volume occupied by same quantity of perature is increased by 10°C at the same volume the
N2 gas at 750 K and 200 atm in litre is pressure increased by 10%. Calculate the temperature t
19. If the slope of Z (compressibility factor ) v/s p curve and volume v? (Mol. Wt. = 120)
is constant (slope = p/492.6 atm–1) at a particular tem- 29. The density of the vapour of a substance at 1 atm pres-
perature (300 k) and very high pressure, then calculate sure and 500 K is 0.36 kg m–3. The vapour effuses
diameter of the molecules in Å, (Given NA = 6.0 ¥ 1023, through a small hole at a rate of 1.33 times faster than
R = 0.0821 atm lit mol–1 K–1) oxygen under the same condition.
Gaseous State 3.37
Determine (i) molecular weight, (ii) molar volume, (iii) that all this O2 is used to produce energy by oxidis-
compression factor (Z) of the vapour and (iv) which ing glucose in the body. What is the mass of glucose
forces among the gas molecules are dominating: the at- required per hour by a resting male having mass 60 kg.
tractive or the repulsive? What volume, at STP of CO2 would be produced?
30. At 27°C, H2 gas is leaked through a tiny hole into a ves- 41. 12 g N2, 4 g H2 and 9 g O2 are put into a 1 ltr container
sel for 20 mts. Another unknown gas, at the same tem- at 27°C. What is the total pressure?
perature and pressure, as that of H2, is leaked through 42. 1.0 ¥ 10–2 kg of hydrogen and 6.4 ¥ 10–2 kg of oxygen
the same hole for 20 mts. After the effusion of the gas- are contained in a 10 ¥ 10–3 m3 flask at 473 K. Calcu-
es the mixture exerts a pressure of 6 atm. If H2 is 0.7 late the total pressure of the mixture. If a spark ignities
mol and volume of vessel is 3 ltr, calculate molecular the mixture, what will be the final pressure?
weight of the unknown gas. 43. At room temperature, NH3 gas at one atm and HCl gas
31. 1 ltr flask contains O2 at 0°C and 7.6 ¥ 10–10 mm Hg. at "P" atm are allowed to effuse through identical pin
Calculate the number of molecules of O2 present. holes to the opposite ends of a glass tube 1 m long and
32. Assuming that N2 molecules is spherical and its radius uniform cross section. A white deposit is observed at a
distance of 60 cm from the HCl end. What is P.
is 2 ¥ 10–10 metre, calculate the empty space in one
44. A gas mixture contains equal number of molecules of
mole of N2 gas at NTP.
N2 and SF6, some of it is passed through a gaseous ef-
33. A glass bulb of 1 ltr contains 2 ¥ 1021 molecules of
fusion apparatus. Calculate how many molecules of N2
nitrogen exerting pressure of 7.57 ¥ 103 Nm–2. Calcu-
are present in the product gas for every 100 molecules
late (a) the root mean square velocity and temperature
of SF6.
of the gas molecules and (b) Umpv of gas molecules at 45. Two gases NO and O2 were introduced at the two ends
this temperature. of a 1 mtr long tube simultaneously (tube of uniform
34. Two grams of gas A are introduced in an evacuated cross section). At what distance from NO gas end,
flask at 25°C. The pressure of the gas is 1 atm. Now 3 brown fumes will be seen?
g of another gas B is introduced in the same flask, the 46. At 20°C two balloons of equal volume and porosity are
total pressure becomes 1.5 atm. Calculate (a) the ratio filled to a pressure of 2 atm, one with 14 kg N2 and
of molecular mass MA and MB and (b) volume of the other with 1 kg H2. The N2 balloon leaks to a pressure
vessel, if A is O2.
35. 1 ltr O2 and 1 ltr H2 are taken in a vessel of 2 ltr at STP. of 1 atm in one hour. How long will it take for H2 bal-
These gases are made to react to form water. Calculate 2
(a) moles and weight of water formed (b) amount of loon to leak to a pressure of 1 atm?
2
gas left in the vessel and (c) total pressure of the gas at
47. Pure O2 diffuses through an aperture in 224 sec, where-
100°C.
as mixture of O2 and another gas containing 80% O2
36. A long rectangular box is filled with chlorine (at.wt.
diffuses from the same in 234 sec. What is molecular
35.45) which is known to contain only 35Cl and 37Cl.
weight of the gas?
If the box can be divided by a partition and the two
48. A space capsule is filled with neon gas 1.00 atm and
types of chlorine molecules put in the two comparti-
290 K. The gas effuses through a pin - hole into outer
ments respectively, calcualte where should the partition
space at such a rate that the pressure drops by 0.3 torr/
be made if the pressure on both side are to be equal.
sec.
37 3.6 g of an ideal gas was injected into a bulb of internal
(a) If the capsule were filled with ammonia at the
volume of 8 L at pressure P atm and temp T K. The
same temperature and pressure, what will be the
bulb was then placed in a thermostat maintained at (T
rate of pressure drop?
+ 15)K 0.6 g of the gas was let off to keep the original
(b) If the capsule were filled with 30.0 mol % heli-
pressure. Find P and T if molecular weight of is 44.
um, 20.0 mol% oxygen and 50.0 mol% nitrogen
38. A toy balloon originally held 1.0 g of He gas and had
at a total pressure of 1.00 atm and a temperature
a radius 10 cm. During the night, 0.25 g of the gas ef-
of 290 K, what will be the corresponding rate of
fused from the balloon. Assuming ideal gas behaviour,
pressure drop?
under these constant P and T conditions, what was the
49. Show that the height at which the atmospheric pressure
radius of the balloon the next morning?
0.693RT
39. If a scuba diver is to remain submerged for 1 hr, what is reduced to half its value is given by h = .
pressure must be applied to force sufficient air into the Mg
tank to be used. Assume 0.5 dm3 of air per breath at 50. Calculate the pressure of a barometer on an aeroplane
standard atmospheric pressure, a respiration rate of 38 which is at an altitude of 10 km. Assume the pressure to
breaths per minute, and a tank capacity of 30 dm3. be 101.325 kPa at sea level and the mean temperature
40. While resting, the average human male uses 0.2 dm3 of 243 K. Use the average molar mass of air (80% N2,
O2 per hour at STP for each kg of body mass. Assume 20% O2).
51. An iron cylinder contains helium at a pressure of 250 (i) the ideal gas equation
kPa and 27°C. The cylinder can withstand a pressure (ii) the Vander Waal’s equation
of 1 ¥ 106 Pa. The room in which cylinder is placed [a = 0.2107 atm L2 mol2, b = 0.0171 L mol–1]
catches fire. Predict whether the cylinder will blow 64. What will be the temperature difference needed in a hot
up before it metls or not. [Melting point of cylinder = air balloon to lift 1.0 kg of mass? Assume that the vol-
1800 K] ume of balloons is 100 m3, the temperature of ambient
52. Determine the molar mass of a gas if its pressure is to air is 25°C, the pressure is 1 bar, and air is an ideal gas
fall to one-half of its value in a vertical distance of one with an average molar mass of 29 g mol–1 (hot and cold
metre at 298 K. both).
53. The time taken for a given volume of gas E to effuse 65. One mole of a non-linear triatomic gas is heatted in a
through a hole is 75 sec. Under identical conditions, the closed rigid container from 500°C to 1500°C. Calcu-
same volume of a mix of CO and N2 (containing 40% late the amount of energy required if vibrational degree
of N2 by volume) is effused in 70 sec. Calculate of freedom become effective only above 1000°C.
66. The respiration of a suspension of yeast cells was mea-
(i) the relative molecular mass of E, and
sured by determining the decrease in pressure of the
(ii) the R.M.S velocity (in ms–1 units) of E at 0°C.
gas above the cell suspension. The apparatus was ar-
54. At what temperature in °C, the Urms of SO2 is equal to
ranged so that the gas was confined to a constant vol-
the average velocity of O2 at 27°C?
ume, 16 cm3 and the entire pressure change was caused
55. The density of CO at 273 K and 1 atm is 1.2504 kg m–3. by uptake of oxygen by the cells. The pressure was
Calculate (a) root mean square speed, (b) the average measured in a monometer, the fluid of which had den-
speed and (c) most probable speed. sity of 1.034 g/cm3. The entire apparatus was immersed
56. Calculate the temperature values at which the mol- in a thermostat at 37°C. In a 30 mts observation period,
ecules of the first two members of the homologous se- the fluid in the open side of the manometer dropped 37
ries CnH2n+2 will have the same R.M.S speed as CO2 mm. Neglecting the solubility of oxygen in the yeast
gas at 770 K. The normal b.p. of n-butane is 273 K. suspension, compute the rate oxygen consumption by
Assuming ideal gas behaviour of n-butane up to this the cells in mm3 of O2 (STP) per hour.
temperature, calculate the mean velocity and the most 67. In a basal metabolism measurement timed at 6 mts, a
probable velocity of its molecules at this temperature. patient exhaled 52.5 L of air measured over water at
57. Calculate the temperature at which the root mean 20°C. The vapour pressure of water at 20°C is 17.5 torr.
square velocity, average velocity and most probable The barometric pressure was 750 torr. The exhaled air
velocity of oxygen gas are all equal to 1500 ms–1. analysed 16.75 volume % oxygen and the inhald air
58. The compressibility factor for N2 at –50°C and 800 atm 20.32 volume % oxygen. Both on a dry basis neglect-
pressure is 1.95 and at 100°C and 200 atm, it is 1.10. ing any solubility of the gases in water and any differ-
A certain mass of nitrogen occupied 1 ltr at –50°C and ence in the total volumes of inhaled and exhaled air,
800 atm. Calculate the volume occupied by the same calculate the rate of oxygen consumption by the patient
quantity of N2 at 100°C and 200 atm. in mL (STP) per minute.
59. At 273.15 K and under a pressure of 10.1325 MPa, 68. The temperature and the relative humidity of air are
the compressibility factor of O2 is 0.927. Calculate the 20°C and 80% on a certain day. Find the fraction of the
mass of O2 necessary to fill a gas cylinder of 100 dm3 mass of water vapour that will condense if the tempera-
capacity under the given conditions. ture falls to 5°C. Saturation vapour pressures at 20°C
60. The Van der Waals constant for O2 are a = 1.36 atm L2 and 5°C are 17.5 mm and 6.5 mm of Hg respectively.
mol–2 and b = 0.0318 L mol–1. Calculate the tempera- 69. 6.0 g of He having average velocity 4 ¥ 102 ms–1 is
mixed with 12.0 g of Ne20 having the same average
ture at which O2 gas behaves, ideally for longer range
velocity. What is the average kinetic energy per mole
of pressure.
in the mixture?
61 Show that at low densities, the Van der Waals equation
70. Molar volume of He at 10.1325 MPa and 273 K is
Ê a ˆ
0.011075 times its molar volume at 101.325 kPa. Cal-
ÁË p + V 2 ˜¯ (Vm – b) = RT
m culate radius of He atom assuming negligible 'a'.
and the Dieterici's equation P(Vm – b) = RT exp 71. The viral equation for ethane gas is given by PV = RT
(–a/RTVm) given essential the same value of p. + BP. At 0°C, B = –0.1814 L/mol. Calculate volume of
62. Calculate from the Van der Waal's equation, the tem- one mole of ethane at 10 atm, and 'a'.
perature at which 192 g of SO2 will occupy a volume 72. Pressure of He gas confined in a steel chamber drops
of 10 dm3 at 15 atm pressure. [a = 6.7 atm L2 mol2, from 4.0 to 1.0 atmosphere in 4 hrs due to diffusion
b = 0.0564 L mol–1] through a pin hole in the steel chamber. If an equimolar
63. Calculate the pressure of 15 mol neon at 30°C in a mixture of He and methane gas at 20 atmosphere and
12 ltr container using the same temperature are confined in the same cham-
Gaseous State 3.39
ber, what will be the parital pressure of He and methane (b) Find the value of n to which the gas A is being
after 1 hr. Assume rate of diffusion to be linear function polymerised into.
of gas pressure and inverse function of square root of
3.2 atm
molar masses. 2.2875 atm
73. A 1 ltr flask containing NH3 (g) at 2.0 atmoshpere and atm (T + 10) atm (T + 10)
1.54 1.25
P(atm)
P(atm)
300 K is connected to another 800 mL flask containing (T) (T)
HCl (g) at 8.0 atmosphere and 300 K by means of a
narrow tube of negligible volume and gases were al-
T(°C) T(°C)
lowed to react quantitatively as (i) (ii)
NH3 (g) + HCl (g) h NH4Cl (s) ; DH = – 43 kJ/mol Expected Actual
If heat capacity of HCl (g) CV is 20 JK–1 mol–1, deter-
mine final pressure inside the flask assuming negligible 79. During one of his adventures, Chacha Chaudhary got
heat capacity of flask and negligible volume of solid trapped in an underground cave which was sealed 200
NH4Cl. yrs back. The air inside the cave was poisonous, hav-
74. Calculate the value of s, l, Z1 and Z11 for nitrogen mol- ing some amount of carbon monoxide in addition to
ecules at 25°C and at pressure of 10–3 mm Hg. Given O2 and N2. Sabu, being huge could not enter into the
that b for nitrogen is 39.1 cm3 mol–1. cave, so in order to save Chacha Choudhary he started
75. The mean free path of the molecule of a certain gas at sucking the poisonous air out of the cave by mouth.
300 K is 2.6 ¥ 10–5 m. The collision diameter of the Each time, he filled his lunge with cave air and exhaled
molecule is 0.26 nm. Calculate it out in the surroundings. In the mean time, fresh air
(a) pressure of the gas, and from surrounding effused into the cave till the pressure
(b) number of molecules per unit volume of the gas. was again one atmosphere. Each time Sabu sucked out
76. There are two vessels of same consisting same number some air, the pressure in the cave dropped to half of its
of moles of two different gases at same temperature. initial value of one atmosphere.
One of the gas is CH4 and the other is unknown X. As- If the initial sample of air from the cave contained 5%
suming that all the molecules of X are under random by volume CO. If the safe level of CO in the atmo-
motion whereas in CH4 except one all are stationary. sphere is less than 0.001% by volume, how many times
Calculate Z1 for X in terms of Z1 of CH4. Given that the does Sabu need to such out air in order to save Chacha
collision diameter for both gases are same and (Urms)x Choudhary.
1 80. A closed vertical cylinder is divided into two parts by a
(U av )CH4 frictionless piston, each part contains 1 mole of air. At
= 6 . 27°C, the volume of the upper part is four times than
77. A mixture of CH4 and O2 is used as an optimal fuel if that of the lower part. Calculate the temperature when
O2 is present in thrice the amount required theoretically volume of the upper part will be three times that of the
for combustion of CH4. Calculate number of effusion lower part.
steps required to convert a mixture containing one part 81. A water gas mixture has the composition by volume of
of CH4 in 193 parts mixture (parts by volume). If calo- 50% H2, 40% CO and 5% CO2.
rific value (heat evolved when 1 mole is burnt) of CH4 (i) Calculate the volume in litres at STP of the mix-
is 100 cal/mole and if after each effusion 90% of CH4 is ture which on treatment with excess steam will
collected, find out what initial mole of each gas in ini- contain 5 ltrs of H2. The stoichiometry for the wa-
tial mixture required for producing 1000 cal of energy ter gas shift reaction is
after processing? CO + H2O Æ CO2 + H2
[Given (0.9)5 = 0.6] (ii) Find the density of the water gas mixture in
78. A closed vessel of known volume containing known kg/m3.
amount of ideal gaseous substance 'A' was observed for (iii) Calculate the moles of the absorbants KOH,
variation of pressure with temperature. The expected Ca(OH)2 and ethanolamine.
graph was to be like (i) However actual observations HO – CH2 – CH2 – NH2 required respectively to
revealed the graph to be like. (ii) The deviation was collect the CO2 gas obtained.
attributed to polymerisation of gas molecules as 82. A gas present in a container connected to frictionless,
nA(g) m An(g). If it is known that the above reac- weightless piston operating always at one atmosphere
tion gave only 50% yield, pressure such that it permits flow of gas outside (with
nexperiment no adding of gas). The graph of n vs T (Kelvin) was
(a) calculate the ratio of (where nexp.=
ntheoritical plotted and was found to be a straight line with coordi-
Total number of gaseous mole actually present nates of extreme points as (300, 2) and (200, 3). Calcu-
ntheoritical = Total number of mole original taken) late:
(i) relationship between n and T 90. What is the difference in the density of dry air at 1 atm
(ii) relationship between V and T and 25ºC and moist air with 50% relative humidity un-
(iii) Maxima or minima value of 'V' der the same condition? The vapour pressure of wa-
83. Find the critical constant (Pc, Vc and Tc) in terms of A ter at 25ºC is 23.7 Torr and dry air has 75.5% N2 and
and B. Also find compressibility factor (z) for the fol- 24.5% O2.
lowing equation of state: 91. A sample of butane gas C4H10 of unknown mass is con-
tained in a vessel of unknown volume V at 25ºC and
A 2B a pressure of 760 mm-Hg. To this vessel, 8.6787 g of
PV = RT - +
V V2 neon gas is added in such a way that no butane is lost
where A and B are constant, P = pressure and V = molar from the vessel. The final pressure in the vessel is 1920
volume. mm-Hg at the same temperature. Calculate the volume
84. Calculate the mass of mercury in a uniform column of the vessel and the mass of butane.
760 mm high and 1.00 cm2 in cross-sectional area. Is 92. A mixture of CO and CO2 is found to have a density of
there any change in 1.50 g/ltr at 30ºC and 730 mm. Calculate the composi-
(a) mass and tion of mixture.
(b) pressure of column of same height but with 93. The pressure in a bulb dropped from 2000 to 1500 mm
2.00 cm2 cross-sectional area is taken? of mercury in 47 minutes when the contained oxygen
(Density of Hg = 13.6 g/cm3) leaked through a small hole. The bulb was then com-
85. The diameters of a bubble at the surface of a lake is pletely evacuated. A mixture of oxygen and another gas
of molecular weight 79 in the molar ratio of 1 : 1 at a
4 mm and at the bottom of the lake is 1 mm. If atmo-
total pressure of 4000 mm of mercury was introduced.
spheric pressure is 1 atm and the temperature of the
Find the molar ratio of the two gases remaining in the
lake water and the atmosphere are equal, what is the
bulb after a period of 74 minutes.
depth of the lake? (The density of lake water and Hg
94. 1 mole of CCl4 vapours at 77ºC occupies a volume of
are 1 gm/mL and 13.6 gm/mL respectively. Also ne- 35.0 L. If vander waal’s constants are a = 20.39 L2 atm
glect the contribution of pressure due to surface ten- mol–2 and b = 0.1383 L mol–1, calculate compressibil-
sion). ity factor Z under, (a) low pressure region and (b) high
86. At room temperature, following reaction goes to com- pressure region.
pletion: 94. One mole of nitrogen gas at 0.8 atm takes 38 sec to
2NO + O2 h 2NO2 h N2O4 diffuse through a pinhole, whereas one mole of an un-
Dimer N2O4 at 262 K is solid. A 250 mL flask and a known compound of xenon with fluorine at 1.6 atm
takes 57 sec to diffuse through the same hole. Deter-
100 mL flask are separated by a stop cock. At 300 K,
mine the molecular formula of the compound.
the nitric oxide in the large flask exerts a pressure of
95. Which of the following statements is correct?
1.053 atm and the smaller one contains O2 at 0.789
(a) He diffuses at a rate of 8.65 times as much as CO
atm. The gases are mixed by opening the stop cock and does
after the end of the reaction, the flasks are cooled to (b) He escapes at a rate of 2.65 times as fast as CO
220 K. Neglecting the vapour pressure of dimer. Find does
out the pressure and composition of gas remaining at (c) He escapes at a rate of 4 times as CO2 does
220 K (Assume gases behave ideally). (d) He escapes at a rate 4 times as fast as SO2 does
87. 1 mole of N2 and 3 moles of H2 are mixed in 8.21 ltr 96. The pressure of an ideal gas is increased isothermally
container at 300 K to form NH3. If equilibrium average at 298 K in a 5 L vessal from 1 bar to 2 bar. The correct
molecular mass was found to be 34/3 gram then find option (s) is /are
partial pressure of each component. (a) DG = 2.7 kJ/mol (b) DG = 1.7 kJ/mol
88. One litre flask contains air, water vapour and a small (c) DSgas < 0 (d) DSsurroundings = 0
amount of liquid water at a pressure of 200 mm-Hg. If 97. One mole triatomic vapours of an unknown substance
this is connected to another 1 ltr evacuated flask, what 4
effuses times faster than 1 mole O2 under same con-
will be the final pressure of the gas mixture at equi- 3
librium? Assume the temperature to be 50°C. Aqueous ditions. If the density of unknown vapours at pressure
tension at 50°C = 93 mm-Hg. P and temperature T is d, which of the following holds
89. A 500 mL bulb is filled with CH4 at a pressure of 1 atm true for the unknown substance?
and oxygen at a pressure of 4 atm at 27ºC. The mixture (a) dN T P = 0.8035 g/l
is then exploded, when the reaction CH4 + 2O2 h (b) Z(atomic number) = 6
CO2 + 2H2O (l) occurs. Calculate the pressure if the 18P
final temperature is 27ºC. Aqueous tension at 27ºC is (c) Z(compress ibility factor) =
dRT
26.7 mm. (d) Vapour density = 9
Gaseous State 3.41
1/2 1/2
PREVIOUS YEARS’ QUESTIONS P ÊM ˆ M A Ê PB ˆ
(c) A Á B ˜ (D)
OF JEE (MAIN & ADVANCED) PB Ë M A ¯ M B ÁË PA ˜¯
1. The number of moles per litre in the equation PV = nRT 10. An evacuated glass vessel weighs 50.0 g when empty,
is expressed by [AIEEE-02] 148.0 g when filled with a liquid of density 0.98 g /mL
P PV and 50.5 g when filled with an ideal gas at 760 mm Hg
(a) (b) at 300 K. Determine the molecular weight of the gas.
RT RT
11. Using Van der Waals equation, calculate the constant
RT "a" when 2 moles of a gas confined in a 4 ltr flask ex-
(c) (d) None of these
PV erts a pressure of 11.0 atm at a temperature of 300 K.
2. The correct value of R is [AIEEE-02] The value of "b" is 0.05 ltr mol–1. [JEE 1998]
(a) R = 0.082 litre atm 12. One mole of N2 gas at 0.8 atm takes 38 sec to diffuse
(b) R = 8.314 ¥ 107 erg –K–1 mol–1 through a pin hole, whereas one mole of an unknown
(c) R = 2K–1 mol–1 compound of Xenon with F at 1.6 atm takes 57 sec to
(d) None of the above diffuse through the same hole. Calculate the molecular
3. As the temperature is raised from 20°C to 40°C, the formula of the compound. [JEE 1999]
average kinetic energy of neon atoms changes by factor 13. A gas will approach ideal behaviour at [JEE 1999]
of which of the following ? [AIEEE-04] (a) low temperature and low pressure
(a) 1/2 (b) (313/293) (b) low temperature and high pressure
(c) 313/293 (d) 2 (c) low pressure and high temperature
4. In Van der Waal’s equation of state of the gas law, the (d) high temperature and high pressure
constant b is a measure of [AIEEE-04] 14. The compressibility of a gas is less than unity at STP.
(a) intermolecular repulsions Therefore [JEE 2000]
(b) intermolecular attraction (a) Vm > 22.4 L (b) Vm < 22.4 L
(c) volume occupied by the molecules (c) Vm = 22.4 L (d) Vm = 44.8 L
(d) intermolecular collisions per unit volume 15. The R.M.S. velocity of hydrogen is 7 times the
5. The ratio between the R.M.S. velocity of H2 at 50 K R.M.S. velocity of nitrogen. If T is the temperature of
and that of O2 at 800 K is [JEE 1996] the gas, [JEE 2000]
(a) 4 (b) 2 (a) T(H2) = T(N2) (B) T(H2) > T(N2)
(c) 1 (d) 1/4 (c) T(H2) < T(N2) (D) T(H2) = 7 T(N2)
6. X mL H2 gas effuses through a hole in a container in 5 16. Calculate the pressure exerted by one mole of CO2 gas
sec. The time taken for the effusion of the same volume at 273 K, if the Van der Waals constant a = 3.592 dm6
of the gas specified below under identical conditions is atm mol–2. Assume that the volume occupied by CO2
[JEE 1996] molecules is negligible. [JEE 2000]
(a) 10 sec, He (b) 20 sec, O2 17. The compression factor (compressibility factor) for
(c) 25 sec, CO (d) 55 sec, CO2 one mole of a Van der Waals gas at 0°C and 100 atmo-
7. One mole of N2O4 (g) at 300 K is kept in a closed con- sphere pressure is found to be 0.5. Assuming that the
tainer under 1 atm. It is heated to 600 K when 20% by volume of a gas molecule is negligible, calculate the
mass of N2O4 (g) decomposes to NO2 (g). The resultant Van der waals constant ‘a’. [JEE 2001]
pressure is [JEE 1996] 18. The density of the vapour of a substance at 1 atm pres-
(a) 1.2 atm (b) 2.4 atm sure and 500 K is 0.36 Kg m–3. The vapour effuse
(c) 2.0 atm (d) 1.0 atm through a small hole at a rate of 1.33 times faster than
8. One way of writing the equation for state for real gases oxygen under the same condition. [JEE 2002]
È B ˘ (a) Determine
is, PV = RT Í1 + + .........˙ where B is constant.
Î V ˚ [JEE 1997] (i) Molecular weight ; (ii) Molar volume ; (iii) com-
Derive an approximate expression for 'B' in terms of pressibility factor (z) of the vapour
Van der Waals constant 'a' and 'b'. (iv) Which forces among the gas molecules are domi-
9. According to Graham's law, at a given temperature the nating the attractive or the repulsive?
r (b) If the vapour behaves ideally at 1000 K, deter-
ratio of the rates of diffusion A of gases A and B is mine the average translational K.E. of a molecule.
rB
given by [JEE 1997] 19. The average velocity of gas molecules is 400 m/sec.
1/2 1/2 Calculate its (R.M.S) velocity at the same temperature.
PA Ê M A ˆ ÊM ˆÊP ˆ
(a) (b) Á A ˜ Á A ˜ [JEE 2003]
PB ÁË M B ˜¯ Ë M B ¯ Ë PB ¯
20. Positive deviation from ideal behaviour takes place be- C A

cause of [JEE 2003] z
(a) molecular interaction between atoms and PV
23. Ideal gas where Z = ,
PV nRT
>1
nRT
PV B
(b) molecular interaction between atoms and <1 P
nRT
PV a = Van der Waal's constant for pressure correction
(c) finite size of atoms and >1 b = Van der Waal's constant for volume correction
nRT
Pick the incorrect statement only. [JEE 2006]
PV (a) For gas A, if a = 0, the compressibility factor is
(d) finite size of atoms and <1
nRT directly proportional to pressure.
21. For a real gas obeying Van der Waal's equation a graph (b) For gas B, if b = 0, the compressibility factor is
is plotted between PVm (y-axis) and P(x-axis) where Vm directly proportional to pressure.
is molar volume. Find y-intercept of the graph. (c) For gas C, a π 0, b π 0, it can be used to calculate
[JEE 2005] a and b by giving lowest P value and its intercept
22. The ratio of the rate of diffusion of helium and methane with Z = 1.
under identical condition of pressure and temperature (d) Slope for all three gases at high pressure (not
will be [JEE 2005] shown in graph) is positive.
(a) 4 (b) 2 (c) 1 (d) 0.5
Answer Key
LEVEL I
1. (b) 2. (c) 3. (b) 4. (d) 5. (b) 6. (b) 7. (a) 8. (a) 9. (b) 10. (b)
11. (d) 12. (a) 13. (c) 14. (b) 15. (c) 16. (c) 17. (b) 18. (a) 19. (a) 20. (b)
21. (a) 22. (a) 23. (a) 24. (c) 25. (c) 26. (a) 27. (b) 28. (a) 29. (a) 30. (b)
31. (c) 32. (b) 33. (d) 34. (a) 35. (d) 36. (a) 37. (a) 38. (a) 39. (c) 40. (b)
41. (a) 42. (d) 43. (c) 44. (a) 45. (b) 46. (b) 47. (b) 48. (c) 49. (a) 50. (a)
51. (a) 52. (c) 53. (a) 54. (a) 55. (a) 56. (b) 57. (c) 58. (b) 59. (c) 60. (b)
61. (d) 62. (a) 63. (b) 64. (d) 65. (b) 66. (a) 67. (b) 68. (b) 69. (b) 70. (a)
71. (b) 72. (a) 73. (a) 74. (b) 75. (a) 76. (b) 77. (a) 78. (a) 79. (d) 80. (b)
81. (b) 82. (b) 83. (c) 84. (b) 85. (a) 86. (a) 87. (a) 88. (c) 89. (c) 90. (c)
91. (a) 92. (d) 93. (c) 94. (a) 95. (b) 96. (c) 97. (b) 98. (a) 99. (a) 100. (c)
LEVEL II
1. (a) 2. (a) 3. (d) 4. (d) 5. (a) 6. (c) 7. (c) 8. (a) 9. (c) 10. (c)
11. (a) 12. (d) 13. (a) 14. (d) 15. (b) 16. (b) 17. (a) 18. (a) 19. (b) 20. (a)
21. (a) 22. (a) 23. (b) 24. (c) 25. (c) 26. (b) 27. (c) 28. (d) 29. (b)
LEVEL III
1. (A) Æ r; (B) Æ s; (C) Æ q; (D) Æ p 2. (A) Æ s; (B) Æ r; (C) Æ p, q; (D) Æ p, q

3. (A) Æ q; (B) Æ s; (C) Æ p, s; (D) Æ p, q, r 4. (A) Æ r; (B) Æ p; (C) Æ s; (D) Æ q
5. (a) 6. (b) 7. (c) 8. (d) 9. (d) 10. (d) 11. (6) 12. (7 ml) 13. (2) 14. (4)
15. (2) 16. (2 atm) 17. (2 atm) 18. (4) 19. (5 Å) 20. (9) 21. (3) 22. (5 atm) 23. (1.236) 24. (0.138)
25. ( X C2H6 = 0.66) 26. ( X H2 = 0.78) 27. (4.46 g/L) 28. (100 K and 0.82 L)
29. (i) [M = 18.1], (ii) [50.27 ¥ 10–3 m3], (iii) [1.225], (iv) [Z > 1 repulsive] 30. (M = 1033 g Mol–1)
Gaseous State 3.43
31. (2.68 ¥ 1010) 32. (99.9%) 33. (494.2 m/sec. and 405.26 m/sec.) 34. (a) 1/3 (b) (1.53 lit.)
35. (a) [0.803 gram], (b) [0.71 gram], (c) [1.02 atm] 36. [3.44 : 1] 37. [0.062 atm, 75 K]
38. [r = 9.0856 cm] 39. [P = 38 atm] 40. [11.999 L] 41. [66.74 atm] 42. [19.66 ¥ 105 N/m2]
43. [P = 2.1979atm] 44. [x = 228] 45. [50.8 cm] 46. [16 min] 47. [46.6]
48. (a) [3.25 torr/sec.] (b) [0.3387 torr/sec.] 49. [Conceptual] 50. [25.027 kPa] 51. [Blow Up]
52. [M = 175.133 kg mole–1] 53. (i) [32.1428 gm/mole], (ii) [460.28 m/s] 54. [236.29°C]
55. (a) [493.03 m/s] (b) [454.259356] (c) [403 m/s] 56. [Conceptual]
57. [2886 K, 3399 K,4330 K for rms, average, most probable]
58. [3.77 L] 59. [15.40 kgm] 60. (Conceptual) 61. [Derivation] 62. T = 350.5°C
63. (i) [31.1 atm] (ii) [31.4 atm] 64. [Conceptual] 65. [4500 R] 66. [0.104 cm3/m]
67. [280 mL/min.] 68. [0.509] 69. [807.84 J] 70. [134 pm]
71. [a = 3.77 bar L2mol–2] 72. [8.4 atm] 73. [10.3 atmosphere]
74. [314 pm, 7.05 cm, 6739.4 sec–1, 1.09 ¥ 1017 cm–3 sec–1] 75. [530.3 Pa, 1.281 ¥ 1023 m–3]
76. (Z1(x) = Z1(CH4) 77. [5333.3 mole O2 and 28.78 mole CH4] 78. (a) [0.625] (b) [n = 4] 79. [n = 13]
80. [421.9 K] 81. (i) [V = 5.263 L], (ii) [r = 0.7 g/L], (iii) [0.2349 Mole]
È -T ˘ È RT 2 ˘
82. (i) Ín = + 5˙ (ii) ÍV = - + 5 RT ˙ , (iii) [51.3125 L]
Î 100 ˚ Î 100 ˚
È A3 6B A2 1˘
83. Í PC = 2
, VC = , TC = and Z = ˙
Î 108 B A 6 RB 3˚
84. (i) [2067.2 g] (ii) This mass would rest on twice the area and exert the same pressure.]
85. [65116.8 cm] 86. [PNO (left) = 0.221 atm] 87. [PN2 = 1.5 atm, PH2 = 4.5 atm]
88. [146.5 mm-Hg] 89. [3.0513 atm] 90. [0.007 kg m–3] 91. [6.85 L and 6.24 g]
92. [mole % of CO2 ,CO = 67.81%, 32.19%] 93. [1.236 : 1] 94. (a) [0.98], (b) [1.004]
95. (b,d) 96. (a, c, d) 97. (a, c, d)
PREVIOUS YEARS’ QUESTIONS OF JEE (MAIN & ADVANCED)
a
1. (a) 2. (b) 3. (c) 4. (c) 5. (c) 6. (b) 7. (b) 8. B = b - 9. (c)
RT
10. [123] 11. (6.46 atm ltr2 mol–2]) 12. [XeF6] 13. (c) 14. (b) 15. (c) 16. [0.9922 atm]
17. [1.253 atm L2 mol–2]
18. (a) (i) [18.09] (ii) [41.05 L] (iii) [1.224] (iv) [repulsive force] (b) [2.07 ¥ 10–20 J molecule–1]
19. [434 m/s] 20. (a) 21. [intercept = RT] 22. (b) 23. (b)
Hints and Solutions

2 1
LEVEL I =
5.46 ¥ 300 d 2 ¥ 273
1. (b) PA = 2 bar PTotal= PA + PB PV = nRT 5.46 ¥ 300
d2 = = 3 gm/dm3
PTotal = 3 bar PB = 3 – 2 = 1 bar PV = W/M RT 2 ¥ 273
PA M A PB M B 2 ¥ MA 1¥ MB M 1 3. (b) { PV = nRT
= or = or A =
WA WB 1 2 MB 4
PV 3.32 ¥ 5
or MB = 4MA T= = = 50 K
nR 4 ¥ 0.083
Ê w ˆ RT 4. (d) PV = nRT
2. (c) P = Á ˜
Ë v¯ M
nRT wRT 8.8 ¥ 0.083 ¥ 304.1
P1 M1 P2 M 2 V= = = = 5.05 ltr
= ( M1 = M 2 ) P MP 44 ¥ 1
d1T1 d 2 T2
w 800 380 0.455 14. (b) Z < 1 then Vm < 22.4

5. (b) From PV = RT = ¥ = ZRT
M 760 1000 M Since, PV = ZRT or V =
¥ 0.0821 ¥ 300 P
800 380 0.455 an 2 Ê an 2 ˆ
= ¥ = ¥ 0.0821 ¥ 300 15. (c) Pcorection = P = P +
760 1000 M ideal Á ˜
V2 Ë V2 ¯
rSO2 M N2 TSO2 x 28 773 Ê a ˆ
6. (b) = ¥ or = ¥ for 1 mole Pideal = Á P + 2 ˜
rN2 M SO2 TN2 1.625 x 64 TN2 Ë V ¯
responsible for intermolecular force.
28 16. (c) At constant P and V, n1T1 = n2T2
or TN2 = ¥ 773 ¥ 1.625
64 4 ¥ T1 = 3.2 ¥ (T1 + 50)
773 ¥ 1.625 On solving,
= 7¥ = 830 K
4 T1 = 200 K
rO2 M H2 2 1 17. (b) The ratio of Vrms of gas at two different tempera-
7. (a) = = = tures is given by
rH2 M O2 32 4
(Vrms ) 2 T
n wCH 4 M O2 32 = 2 ; (Vrms ) 2
8. (a) methane = ¥ = =2 (Vrms )1 T1
nO2 wO2 M CH 4 16
560
2 1 = ¥ V = 2V  (Vrms )1 = V
xCH4 = xO2 = 140
3 3
18. (a) Let the volume of O2 is the mixture be x mL
1
\ PO2 = xO2 ¥ Ptotal = Ptotal H2 + 1/2O2 h H2O (l)
3 Initial volume (40 – x) x
9. (b) For H2 Final volume (40 – 3x) 0
P1V1 = P2V2 Final volume of H2 = 10 mL (Given)
0.8 ¥ 0.5 = P3 ¥ 1 \ 40 – 3x = 10; x = 10 mL
\ P3 = 0.40 bar \ initial volume of H2 = 30 mL ; Initial mole % of
For O2 30
P1V1 = P4 ¥ 1 H2 = ¥ 100 = 75%
40
0.7 ¥ 2 = P4 ¥ 1 19. (a) Ammonia decomposes into N2 and H2 completely
P4 = 1.4 bar when a spark is passed through it.
\ PT = P3 + P4 = (0.4 + 1.4) bar = 1.8 bar 1 3
10. (b) PTV = nRT NH3 (g) h N 2g + H 2g
2 2
n RT 8 4
PT = T nT = nO2 + nH2 = + = 2.25 Initial 1 0 0
V 32 2
1 3
2.5 ¥ 0.083 ¥ 300 Final 0
= = 56.025 bar 2 2
1
The total pressure of N2 and H2 after complete decom-
nRT position is given by
11. (d) For gas Vgas = (i)
P PT = PN2 + PH2 = 0.5 + 1.5 = 2 atm
nH RTH2
For H2 VH2 = 2 (ii) 20. (b) Given: P = (800/760) atm
PH2
T = 100 + 273 = 373 K; mCO2 = 44
From Eqs. (i) and (ii) PV = (w/m) RT
2.9 ¥ 368 0.184 ¥ 290 w/V = d = (Pm/RT)
= (since volume and pressure
M gas 2 800 ¥ 44
d= = 1.5124 g litre–1
of both gases are same) 760 ¥ 0.0821 ¥ 373
Mgas = 40 g mol–1 V0
U1 T 300 1 21. (a) Vt ∞ = V0 + t
12. (a) U av µ T or = 1 = = 273.15
U2 T2 1200 2 For every 1°C increase in temperature, the volume of
U2 = 2 ¥ U1 = 2 ¥ 0.3 = 0.6 m/sec a given mass of an ideal gas increases by a definite
1
1 2 2E fraction of V0.
13. (c) Since K.E. = M urms \ urms = 273.15
2 M
Gaseous State 3.45
22. (a) P1V1 = P2V2 or 1 ¥ 20 = P2 ¥ 50

1 Ê 400 ˆ
or P2 = 20 ¥ atm 34. (a) Given: P = ÁË ˜ atm, T = 100 + 273 = 373 K
50 760 ¯
w
23. (a) PV = nRT = RT PM w 400 ¥ 44
Mw d= fi d = = 0.75 g L-1
RT 760 ¥ 0.0821 ¥ 373
wRT 1 ¥ 0.0821 ¥ 350
or V = = = 0.495 L = 495 mL 780
PM w 1 ¥ 58 ¥ Mw
PM w 760
35. (d) d = fi 1.40 =
PV
1 1 PV 740 ¥ 100 740 ¥ 80 RT 0.0821 ¥ 250
24. (c) = 2 2 or =
T1 T2 300 T2 fi Mw = 28 \ gas is N2
or T2 = 240 K = – 33°C 36. (a) Given: P = 16 atm, V = 9 ltr, T = 300 K, M wCH =
4
w P◊M 1 ¥ 30 16, R = 0.08 atm K–1
25. (c) d = = = = 1.34 gm/L
V RT .0821 ¥ 273 w
PV = ¥ R ¥T
1 Mw
26. (a) Rate of effusion µ µP
d w
16 ¥ 9 = ¥ 0.08 ¥ 300, w = 96 g
P 16
\ rate of effusion µ 37. (a) Molecular weight of SO2 = 64
d
rO2 VO2 Volume occupied by 1 mole SO2 gas = 22.4 ltr
27. (b) = 64
rH2 VH2 Density of SO2 = = 2.86 g L–1
22.4
nO2 MwH2 38. (a) Given : WN2 = 7 g,
=
nH2 MwO2 Ê 750 ˆ
P = ÁË ˜ atm. M wN = 28,
4/32 2 1 1 760 ¯ 2
or = or = or w = 1 g T = 300 K
w /2 32 4w 4
Ê w ˆ
rSO2 M w of O 2 32 1 1 { PV = Á RT fi
28. (a) = = = = Ë M w ˜¯
rO2 M w of SO 2 64 2 2
750 7
29. (a) Let weight of CO = Weight of N2 = w g, \ ¥V= ¥ 0.0821 ¥ 300
760 28
w w fi V = 6.29 ª 6.3 ltr
\ nCO = and nN2 = , Hence PN2 = PCO]
28 28 weight 5
39. (c) PV = RT or P ¥ 6 =
3RT Mw 207.3
30. (b) Vrms =
M ¥ 0.0821 ¥ (273 + 80)
8RT 5 ¥ 0.0821 ¥ 353
31. (c) Vavg = or P= = 0.11 atm
pM 6 ¥ 207.3
32. (b) Given: T1 = 300 K, T2 = 273 K (STP) 40. (b) Using gas equation
Ê 300 ˆ wRT 5.75 ¥ 0.0821 ¥ (273 + 55)
V1 = 300 mL = ÁË ˜ ltr, Mw = = = 47.0
1000 ¯ PV 0.940 ¥ 3.5
Ê 730 ˆ 41. (a) Given: wN2 = 28 g, P = 2.46 atm, M wN = 28,
P2 = 1 atm, P1 = Á atm, V2 = ? 2
Ë 760 ˜¯ V = 10 ltr
PV PV 730 ¥ 300 1 ¥ V2 Ê w ˆ
1 1
= 2 2◊ = { PV = Á RT
{
T1 T2 760 ¥ 1000 ¥ 300 273 Ë M w ˜¯
{ V2 = 0.2622 ltr = 262.2 mL Ê 28 ˆ
or 2.46 ¥ 10 = Á ˜ ¥ 0.0821 ¥ T
33. (d) P1 = 3 atm, P2 = ?, Ë 28 ¯
T1 = – 23 + 273 = 250 K, or T = 300 K
T2 = 273 + 30 = 303 K 42. (d) According to Boyle’s law
P1 P2 3 P 3 ¥ 303 P1V1 = P2V2 or 1.5 ¥ 75 = 50 ¥ V2
= fi = 2 fi P2 = = 3.64 atm.
T1 T2 250 303 250 1.5 ¥ 75
or V2 = = 2.25 ltr
50
65 T + 1 1.004 P
43. (c) PN¢ 2 = 760 ¥ = 494 mm, or = = 1.004 4
100 T P
15 or T = 250 K
PO¢ 2 = 760 ¥ = 114 mm,
100 rH M wO nH wH 2
50. (a) 2 = 2
= 2 =w 2
20 rO2 M wH nO2 O2
¢ 2 = 760 ¥
PCO = 152 mm, 2 32
100
w 0.45 32 wH 32
44. (a) Moles of first gas = n1 = 1 = = 0.0075 or =4= 2 ¥
m1 60 2 wO2 2
w2 0.22 wH2 4
Moles of second gas = n2 = = = 0.0050 or = = 1: 4
m2 44 wO2 16
So the total moles = n1 + n2 = 0.0075 + 0.0050 = 0.0125 51. (a) at low pressure
0.0050 Ê a ˆ
So partial pressure of second gas P2 = ¥ 75 ÁË P + 2 ˜¯ V = RT
0.0125 V
= 30 cm of Hg a
45. (b) dA = 1.5 dB PV + = RT
V
PM w a
d= Z+ =1
RT VRT
d A M wA M \
a
= = 1.5 = Z =1-
d B M wB M wB VRT
52. (c) N2 + 3H2 h 2NH3
M
or M wB = 1 3
1.5 0 0 2
V T Vinitial 4 2
46. (b) 2 = 2 = fi
V1 T1 Vfinal 2 1
4 T2 53. SO2 replaced by O2
or =
2 273 P, V, T fi same
or T2 = 2 ¥ 273 K n fi constant nO2 = nSO2
or T2 = 273°C wO2 wSO2 1
= wO2 = wSO2
wt. 32 64 2
47. (b) PV = RT 54. At constant pressure V µ T
Mw
9 V2 T2
1 ¥ 8.2 = 55. (a) V µ T \ =
¥ 0.0821 ¥ 300 V1 T1
Mw
or Mw = 27 3
T2 = ¥ 3.8 ¥ 3.8 fi 246.4 K T2 = –26.6°C
48. (c) N.T.P. means 3.75
T = 0°C = 273 K 56. (b) Pn2 µ nH2 Ptotal µ (nH2 + nCH4)
P = 1 atm. PH2 w /2 8
= fi
wt. Ptotal w /2 + w /16 9
PV = RT
Mw 10 –10 10 –3
RT 1.25 ¥ 0.0821 ¥ 273 57. PV = nRT n = ¥
or M w = wt. ¥ = 760 0.082 ¥ 293
PV 1¥1
Number of molecules
Mw = 28 gm mol–1
So gas is N2 10 –10 ¥ 10 –3
= ¥ 6.023 ¥ 1023 = 3.29 ¥ 106
49. (a) P1 = P 760 ¥ 0.082 ¥ 293
P2 = P + 0.004 P = (1.004)P w
T1 = T K 58. (b) PV = RT
Mw
T2 = (T + 1)K
wRT 2.8 ¥ 0.082 ¥ 400
T2 P2 Mw = fi
= PV 1¥1
T1 P1
Mw = 91.84 = 92 C7H8
Gaseous State 3.47
59. VA = 0.5 dm3, VB = 1 dm3 fi 0.352 cm/sec.

3
dA = 3 g/dm , dB = 1.5 g/dm3
8 RT U Avg 1200
1 d RT d RT 69. (b) UAvg = =
MA = MB PA = A , PB = B p M 0.3 300
2 MA MB UAvg = 0.6 m/sec.
PA d A M B 3
= ¥ fi ¥2=4
PB d B M A 1.5 3RT
70. Urms = TµM
M
3 ¥ 0.082 ¥ 400
60. (b) P = \ P = 4.92 atm ÊTˆ ÊTˆ
20 =Á ˜
ÁË ˜¯
w P M CO Ë M ¯ O
61. (d) PV = RT = constant 2 2
Mw wT T 273
= \ T = 375.37 K
P1 P 4.05 P2 44 32
= 2 =
w1T1 w2T2 w ¥ 300 w ¥ 285 2RT
2 71. Ump =
P2 = 1.92 MPa M
w u1 T
62 (a) PV = RT = 1
Mw u2 T2
wRT 1 ¥ 0.082 ¥ 273 1 273 + 50
Mw = fi = 32 =
PV 2 ¥ 0.350 (2) 2
T2
The mass of one atom
= 16 amu fi 2.64 ¥10–23 g T2 = 4 ¥ 323 = 1292 K
63. (b) PV = nRT 3
72. (a) ET = RT, ER = RT
PV 7.6 ¥ 10 –10 1 2
n= fi ¥
RT 760 0.082 ¥ 273 3 5 5
Etotal = RT + RT = RT = ¥ 300 ¥ 8.314
n fi 0.0446 ¥ 10–12 2 2 2
The no. of oxygen molecule = 0.0446 ¥ 10–12 ¥ NA = 6235.5 J
= 2.7 ¥ 1010 3 3 N
73. (a) K.E. = nRT x= ¥ ¥ 150 ¥ R
3RT 3 ¥ 8.314 ¥ 300 2 2 NA
64. (d) Urms = fi 3 N¢
Mw 2 ¥ 10 –3 2x = ¥ ¥ 300 ¥ R \ N¢ = N
2 NA
Urms = 1934 m/sec.
3
65. (b) (Vrms )O2 = (Vrms ) Ne 74. (b) K.E. = nRT
2
Ê 3RT ˆ Ê 3RT ˆ K.E 3 8 300 ¥ 8.314
ÁË ˜¯ = ÁË ˜ = ¥ ¥
M O2 M ¯ Ne Molecule 2 16 NA
T 300 = 6.21 ¥ 10–21 J/molecule
= \ T = 480 K
32 20 r1 M2 64 4
75. = = =
2 RT r2 M1 44 11
66. U mp =
M
V1 t2 M2
2 ¥ 8.314 ¥ 293 76. (b) ¥ =
= = 220 m/sec. V2 t1 M1
1.67 ¥ 10 –27 ¥ 6.023 ¥ 1023
20 30 32
3PV 3P ¥ =
67. (b) U rms = = V1 60 64
M d
V2 = 14.14 ltr
3×1.2×105 1
= = 300 m/sec. 77. (a) r µ
4 M
1 1 1 1 1 1
3RT 3 ¥ 8.314 ¥ 300 rN2 : rH2 : rHe :: : : :: : :
68. (b) U rms = = 28 2 4 14 1 2
M 10 –15 ¥ 6.023 ¥ 1023
rN2 : rH2 : rHe ::1: 14 : 7
3.52 3.52
U rms = m/sec. fi cm/sec.
103 10
1 rCH4 Mx M
78. Rate of diffusion µ = ◊4= x
molecular mass rx M CH4 16
79. (d)
CxHy + (x + y/4)O2 h xCO2+ y/2 H2O Mx fi 64
1.0 10x 5y (U rms )SO2 M He 4 1
10x = 40 5y = 50 95. (b) = = = = 0.25
x=4 y =10 (U rms ) He M SO2 64 4
C4H10 1 t2 M2
80. CH4 + 2O2 h CO2 + 2H2O 96. (c) r µ =
M t1 M1
13
81. (b) C4H10 + O h 4CO2 + 5H2O 60 X X 4 X 16
2 2 = fi = fi =
13 45 40 40 3 40 9
58 gm ¥ 32 x = 71.11
2
58 g CH4 required volume of O2 at dRT 7.71 ¥ 0.082 ¥ 309
97. (b) P = Mw =
13 Mw 2.88
NTP = ¥ 22.4 lit
2 Mw = 67.83 Molecular formula = ClO2
1000 g CH4 required volume of O2 at NTP 1
98. P µ
13 22.4 V
= ¥ ¥ 1000 = 2510 ltr if n and T constant.
2 58
82. Extent of intermolecular hydrogen bonding increasing 3
99. (a) K.E. = nRT nT = constant
the viscosity. 2
3W RT W RT PCH4 2 0.3 ¥ T = 0.4 ¥ 400 T = 533.33 K
83. (a) Ptotal = PCH4 = ◊ fi
32 V 16 V Ptotal 3 4
100. (C) V = p r 3
84. K.E. µ T 3
PVm Vm 4
85. (b) Z = ◊ > 1 Vm > 22.4 L Vm = ¥ p ¥ (10–10)3 ¥ 6.023 ¥ 1023
PV 22.4 3
Vm = 2.52 ¥ 10–6 m3
2 ¥ 0.82 ¥ 546
86. (a) PV = nRT P = P = 2 atm Vm 2.52 mL
44.8
3RT
87. Urms =
Mw LEVEL II
dRT
88. (c) P =
Mw 1. (a) 2Al + 2NaOH + 2H2O Æ 2NaAlO2 + 3H2 ≠
dT = const d1T1 = d2T2 According to the reaction
d ¥ 300 = 0.75 d ¥ T2 2 ¥ 27 g of Al releasing = 3 moles of H2
T2 = 100 ¥ 4 fi 400 K 3 ¥ 0.15
0.15 g of Al releasing = moles of H2
3RT (U rms )O3 32 2 2 ¥ 27
89. (c) U rms = ◊ = fi From PV = nRT
M w (U rms )O2 48 3
nRT 3 ¥ 0.15 ¥ 0.082 ¥ 293
90. Lowest pressure and highest temperature. V= =
P 2 ¥ 27
91. 2H2S (g) + SO2 (g) h 2H2O (l) + 3S (s)
V = 200.4 mL
2.8 1.6
2. (a) Let the weight of mixture = 100 g
H2S is limiting reagent
nH2
SO2 remaining = 1.6 – 1.4 fi 0.2 ltr PH2 = Ptotal ◊ X H2 = Ptotal ×
1 nH2 + nO2
92. Rates of diffusion µ
Molar Mass 20/2
=1¥ bar = 0.8 bar
n P 20 80
93. (c) PV = nRT P¢V = RT P¢ = +
2 2 2 32
1
94. (a) r µ rCH4 = 2rx
M
Gaseous State 3.49
3. (d) { time taken to be distributed the 1010 Wheat grains 1 2 ¥ M B M A 0.5 ¥ 2 1

= 1 sec \ = ; = =
0.5 M A ¥ 3 M B 3 3
\ time taken to distributed the 6.023 ¥ 1023
\ MA : MB = 1: 3
1 ¥ 6.022 ¥ 1023 9. (c) Let the formula of hydrocarbon be CxHy. Its com-
=
1010 bustion reaction is given as
= 6.022 ¥ 1013 sec. Ê yˆ y
CxHy(g) + Á x + ˜ O 2 (g) Æ xCO 2 (g) + H 2O(l)
6.022 ¥ 1013 Ë 4 ¯ 2
= years
60 ¥ 60 ¥ 24 ¥ 365 Initial 5 30 0 0
= 1.90956 ¥ 106 year Ê y ˆ
4. (d) { PV = nRT \ nT = n Methane + nCO2 Final 0 30 - Á x + ˜ 5 5x 0
Ë 4¯
\ n RT 3.2 4.4 Out of 25 mL of resultant gas, 10 mL was CO2 (ab-
P= T = + = 0.3
v 16 44 sorbed by NaOH) and the remaining 15 mL was oxy-
0.3 ¥ 8.314 ¥ 300 gen (absorbed by pyrogallol).
= = 8.2 ¥ 104 Pa \ 5x = 10 ; x = 2
9 ¥ 10-3
Ê yˆ
5. (a) { PV = nRT 30 - Á x + ˜ 5 = 15
Ë 4¯
n W
or P = RT = RT [M = Molar mass of P] On solving, y = 4
V M ¥V \ formula of gaseous hydrocarbon is C2H4.
WRT 0.0625 ¥ 0.082 ¥ 819 10. (c)
\ M= =
PV 0.1 ¥ 34.05 ¥ 10 –3 Element Mass % Mole % Relative molar
M = 1247.7 g ratio
6. (c) Let initially x moles are present at 27°C. C 44.4 3.7 1
P1V1= n1RT1 (Initially) (i) N 51.9 3.7 1
P2V2 = n2RT2 (Finally) (ii) H 3.7 3.7 1
from Eqs. (i) and (ii) \ empirical formula of X = CNH
Ratio of rate of diffusion of X and that of H2 is given by
T1 n2
= [{ V1 = V2, P1 = P2] rx 30 ¥ 4.81 2
T2 n1 = =
rH2 25 ¥ 30 M
300 n2
= On solving, M = 54
750 x
\ molecular formula of x is C2H2N2
2
\ n2 = x 10
5 11. (a) { Mmix = ¥ 22.4 = 0
22.4
\ fraction of air which have been expelled out
\ let the volume of He = V1 mL
Ê 2 ˆ 3
= Á x – x˜ / x = Let the volume of N2 = V2 mL
Ë 5 ¯ 5 \ V1 + V2 = 100  n µ V
7. (c) Number of moles of O2 in 10 L blood
Ê V ˆ V
0.02 ¥ 10 1 \ 10 = Á 1 ˜ ¥ 4 + 2 ¥ 28
= = Ë 100 ¯ 100
0.1 ¥ 32 16
0.08 ¥ 10 2 V1 Ê 100 - V1 ˆ
10 + ¥4+Á ¥ 28
Number of moles of CO2 in 10 L blood = = 100 Ë 100 ˜¯
0.1 ¥ 44 11
Solving, V1 = 75%
0.0821 ¥ 310
Volume of O2 at 1 atm and 37°C = = 1.59 L P1 P2
16 ¥ 1 12. (d) { =
Volume of CO2 at atm and 37°C T1 T2
2 ¥ 0.0821 ¥ 310 750 P2
= = 4.63 L =
11 ¥ 1 300 350
\ P2 = 875 mm Hg
8. (a) Partial pressure of gas A in the mixture = 1 atm
\ difference in height = 875 – 750 = 125 mm
Partial pressure of gas B in the mixture = 0.5 atm
Hg = 12.5 cm of Hg
We know that
13 (a) As the peak of the curve decreases, temperature in-
PA X A n A
= = creases.
PB X B nB
14. (D) Ptotal = Pdry + Pwater vapour Ê T – T ˆ Ê 1.1 – 1ˆ

% Á 2 1˜ = Á ˜ ¥ 100 = 10%
735 = Pdry + 30 Ë T1 ¯ Ë 1 ¯
so Pdry = 735 – 30 = 705 torr Volume of O 2 molecule
21. (A) ¥ 100
PM w Volume of O 2 molecule at STP
15. (B) d =
RT 4
1 ¥ 32 p ¥ 8 ¥ 10 –30 ¥ 103 ¥ N A ¥ 100
d= = 1.3 g L-1 fi 3 = 0.09%
0.0821 ¥ 300 22.4
4 22. (A) MA = 2MB, (Urms)A = (Urms)B
16. b = 4 ¥ ¥ p r3 ¥ N A;
3 3PV P
= 4 ¥ p ¥ 10-4 ¥ 1000 U rms = U rms µ
M M
4 (U rms ) A PA M B P 1
= 4 ¥ ¥ p ¥ r 3 ¥ 6 ¥ 1023 = ¥ ◊4= A ¥
3 (U rms ) B PB M A PB 2
r = 5 ¥ 10-9 cm PA
Distance of closest approach = 2r = 10–8 cm = 10–10 m = 8 :1
PB
17.
PV 40 ¥ 0.4
First Second 23. ( ) Z = fi
RT 300 ¥ 0.082
2 gmH2 16 gm CH4
P atm. P atm. Z = 0.65
0.5 lit. 0.5 lit. 24. (C) P1V1 = P2V2 1 ¥ 550 = P2 ¥ 600
2 5 5
nH2 =
= 1 mol P2 = atm P2 = ¥ 760 fi P2 = 633.33 mm
2 6 6
16 Pressure decrease fi 760 – 633.33 fi 126.67 mm
and nCH4 = = 1 mol 25. (C) N2 + 3H2 h 2NH3
16
11 12
nH2 = nCH4
9 6 4
Pmix Vmix = P1V1 + P2V2 Volume remaining after injected water
or Pmix (0.5 + 0.5) = P ¥ 0.5 + P ¥ 0.5 = 20 – 3.58 = 16.42
= P ¥ 0.5 ¥ 2 All NH3 dissolve in water PV = nRT
or Pmix ¥ 1 = P ¥ 1 P ¥ 16.42 = 15 ¥ 0.0821 ¥ 300
or Pmix = P P = 22.5 atm
18. (A) PV = nRT at NTP 26. (B) Let T1 > T2; final pressure will be same. Let x mole
1 ¥ 2.24 = ni ¥ 22.4 transfer from A to B vessel.
or ni = 0.1 mol \ PAV = (n – x) RT1 (A)
P2 n2 570/760 n2 and PAV = (n + x) RT2 (B)
= or =
P1 n1 1 0.1 n(T1 – T2 )
\ x=
T1 + T2
5.7
Remaining moles = n2 = mol nRT1
76 Finally P1 ¥ 2V = 2nRT1 ; V = put eq. (A)
5.7 P1
Escaped moles = n1 – n2 = 0.1 – = 0.025 mol.
76 nRT1 Ê n(T1 – T2 ) ˆ
\ PA ¥ = Án – RT1
19. (B) n1T1 = n2T2 P1 Ë (T1 + T2 ) ˜¯
or n1 ¥ 300 = n2 ¥ (400)
2 PT
1 2
n2 3 PA =
or = T1 + T2
n1 4
1 atm
n1 – n2 4 – 3 1 27. (D) P µ d; P = kd and k =
or = = 1 metre
n1 4 4
20. (A) Ê 4 Ê d ˆ 3ˆ
V1 = V PV = nRT ; kd ¥ Á p Á ˜ ˜ = nRT
Ë 3 Ë 2¯ ¯
V2 = V + 0.1 V = 1.1 V d14
n 1
T2 V2 1.1 V 1.1 4
= 1 ; 4 = n1/n2 ; n2 = 256
= = = d 2 n2 4
T1 V1 V 1
\ Number of moles of air added = 255 moles
Gaseous State 3.51
28. (D) % relative humidity 2. [A Æ S; B Æ R; C Æ P, Q, R, S ;D Æ P,Q]

Partial pressure of H 2O Gas Tc Tb
= ¥ 100 A2 108.4 K 365 K
Vapour pressure of H 2O
B2 90.33 K 304.8 K
PH2O C2 607 K 2048.6 K
75 = ¥ 100 fi PH2O = 22.5 torr ;
30 D2 180.67 K 607.7 K
(22.5) 3. PV = nRT
% of H2O vapour in air = ¥ 100 = 2.96 When V and T are constant then P µ n
760
29 ¥ 97.04 + 2.96 ¥ 18 (A) h (Q)
molar mass of wet air = PM d moist M moist
100 (B) d = \ = <1
2814.16 + 53.28 RT d dry M dry
= = 28.67
100 (B) h (S)
PM 1 ¥ 28.67 pH2O
Density of wet air = = = 1.164g/L (C) p∞H2O > pH2O , hence < 1 and
RT 0.0821 ¥ 300 p∞H2O
29. (B) Density of air at sea level, p∞H2O is also a function of temperature.
29 ¥ 1 1 (C) h (P, S)
d0 = = g/L
0.0821 ¥ 290 0.821 Dalton’s law of partial pressures are applicable for only
density at 831 m = d ideal gases.
-Á
Ê 29 ¥10-3 ¥10 ¥ 831ˆ (D) h (P, Q, R)
1 ˜
4. (A) h R
d 0e – Mgh / RT = ¥ e Ë 8 31¥ 290 ¯
0.821 Since He is monoatomic, therefore, CP/CV = 5/3 = 1.66
1 .9 (B) h (P)
fi ¥ e –0 1 = g/L
0.821 0.821 Since Molecular weight of H2 is least.
Let x be the number of balloons (C) h (S)
\ 103 ¥ g + x ¥ 40g = hdg Since CO2 is a linear triatomic molecule, therefore, vi-
0.9 brational energy = (3N – 5) RT = (9 – 5) RT = 4RT
= ¥ 8.21 ¥ g ¥ x = 20 balloons. (D) h (Q)
0.821
Since Molecular weight of SO2 is highest.
\ x = 20 balloons
Comprehension
LEVEL III Passage 1 (For Q. 5-7)

5. (a)
754
P = 754 torr = = 0.992 atm
(Match the Column) 760
PV = nRT
1. [A Æ R, B Æ S, C Æ Q, D Æ P] 0.992 ¥ 0.127 = n ¥ 0.0821 ¥ 371
A Æ R;
Weight
8a a n = 4.14 ¥ 10–3 mole fi n =
Tc = , Pc = Molar mass
27bR 27b 2
0.495
Tc 8a 27b 2 8b Molar mass = Weight/n = = 120 g/mol
= ¥ = 4.14 ¥ 10 –3
Pc 27bR a R
6. (b)
B Æ S; PV = nRT
Tc 8a 8a 1 ¥ 1 = n ¥ 0.0821 ¥ 273 fi n = 4.46 ¥ 10–2 mol
= =
Vc 27bR ¥ 3b 81Rb 2 Weight
Mole =
C Æ Q; Molar mass
a weight 0.714
TB = \ Molar mass = =
bR No. of mole 4.46 ¥ 10 –2
D Æ P; = 16 g/mole
Ti 2a bR 7. (c)
= ¥ = 2.
TB bR a PV = nRT
100 ¥ 3 = n ¥ 0.0821 ¥ 300

3RT 2 RT
n = 12.2 mol 14. U rms = U mp =
M M
Passage 2 (For Q. 8-10)
8. (d) 3R ¥ 400 2 R ¥ 60
\ from questions = = 4 gmol–1
Greater the 'a', more easily liquefiable is the gas. 40 M
9. (d) M=4
8 RTA 8 R(300 K)
PC VC P V 15. Since (uav)A = (uav ) A = =
ZC = \ TC = C C pMA p (0.002 kg mol –1 )
RTC ZC R
50.1 ¥ 0.078 8 RTB 8 R(600 K)
= = 154.5 K (uav ) B = =
0.308 ¥ 0.0821 pMB p (0.016 kg mol –1 )
Ê 27 ˆ 27 (uav ) A 300 16
TB = Á ˜ ◊ TC = ¥ 154.5 = 521.4 K Therefore, = ¥ =2
Ë 8¯ 8 (uav ) B 2 600
10. (d) 16. 2NH3 h N2 + 3H2
a Since number of moles after reaction (n2)
At very low pressure, will be very small in the term
V = 2 ¥ number of moles before reaction (n1)
È a ˘ at same T and V, P µ n
ÍÎ P + V 2 ˙˚ . Similarly b will be small compared to v in
P1 n1 1
\ = =
the term (V – b) P2 n2 2
\ Van der Waal equation reduce to PV = RT.
Hence pressure after reaction = 2 atm.
Integer-Types Questions 17. Since A and A2 are two states in gasoues phase having
their weight ratio 50%, i.e., 1 : 1
PN2 57 96 1 wˆ
11. = = 57/38 Ê
Pgas 38 \ mole of A = ¥ =1Án = ˜
2 48 Ë m¯
0.8 N gas 57 96 1 1
fi = mole of A2 = ¥ =
21.6 28 38 2 96 2
1 3
Ngas = 9 ¥ 28 = 252 \ total mole of A and A2 are = 1 + =
XeFx = 131 + 19x = 252 Thus, from PV = nRT 2 2
19x = 252 – 131 = 121 3
121 P ¥ 33.6 = ¥ 0.0821 ¥ 546
x= ª 6.5 x=6 2
19 P = 2 atm
XeF6 PV 1 ¥ 800
12. Suppose the compound A is CxHyNz. 18. z = , n330K = ,
nRT 1.90 ¥ R ¥ 330
(i) CxHyNz + O2 h CO2 + H2O + N2
(vapour) V ¥ 200
n570K = , by equalising the two, we get
(9 – v) mL.v. mL. 4 mL 6 mL 2 mL 1.10 ¥ R ¥ 570
or (9 – v) v moles 4 6 2 V=4
moles moles moles moles moles
pb b p
for O atoms. 19. z = 1 + at high pressure, slope = = ,
2 ¥ moles of O2 = 2 ¥ moles of CO2 + 1 ¥ moles of H2O RT RT 492.6
2v = 2 ¥ 4 + 1 ¥ 6 = 14 ; v = 7 mL p
b= ¥ 0.0821 ¥ 30 and
13. Let formula in CxHyOz. 492.6
4
1Ê y ˆ y b = p r3 ¥ 4N A
C x H y O z + Á 2x + – z ˜ O 2 ææ
Æ xCO 2 + H 2O 3
2Ë 2 ¯ 2
R = 2.5A0, d = 5A0
Volume of CO2 = 556 – 112 = 448 mL
nRT an 2
Moles = 0.02 20. P = – 2 = 10 –1 = 9
0.9 V – nb v
Moles of CxHyOz = = 0.01 21. Dm = mcold – mhot = (ncold – nhot)
90
x = 2 (1) PVM È 1 1˘
y = 2; z = 4 M= – , T2 – T1 = 3
R ÍÎ T2 T1 ˙˚
Formula C2H2O4
Gaseous State 3.53
4 X O2 = 0.217 » 22
22. Initial number of moles = = 0.1
40
X H2 = 0.78
3.2
Final number of moles = = 0.08 27. PCl5(g) m PCl3(g) + Cl2(g)
40
Since P and V are constant a 0 0
n1T1 = n2T2 teq. 0.6a 0.4a 0.4a
0.1T1 = 0.07T1 + 125 nT = 1.4a
T1 = 500 K 1.4a ¥ R ¥ 420
V=
From PV = nRT P
0.1 ¥ 0.082 ¥ 500 0.4a ¥ 137.5 + 0.4a ¥ 71
P= = 5 atm. Mass = 0.6a ¥
0.821 208.5
2000 - 1500 500 m 208.5a ¥ 208.5 g
23. RO2 = = mm min -1 d= = = 4.46 g/L
47 47 V a[1.4 ¥ 0.821 ¥ 420]
RO2 79
= = 1.57 Rgas = RO2 /1.57 28. Case – I P = 1 atm w = 12 gm T = (t + 273)K
Rgas 32 V = v ltr
500 74 10
Change in pressure of gas in 74 min = ¥ = Case – II T = (t + 283)K P=1+ = 1.1 atm
47 1.57 100
501.92 w = 12 gm V = v litre
500 ¥ 74 For case I – PV = nRT
Change in pressure of O2 = = 787.234
47 12
V= R(t + 273)
Vgas Pgas 2000 - 80/42 m
= = = 1.236 12
VO2 PO2 2000 - 787.234 for Case II 1.1 V = ¥ R(t + 283)
m
Rmix 84 for cases (I) and (II)
24. = 1.16 =
Rkr M mix 1.1 t + 283
Rmix = 62.43 =
1 t + 273
Cl2 m 2Cl
1.1t + 300.3 = t + 283
t=0 1 mole 0
t = –1730C = 100 K
1–x 2x
nT = 1 + x 12
Using case I V = ¥ 0.082 ¥ 100 = 0.82 ltr
M – M O 71 – 62.4 120
x= T = = 0.138 29. P = 1 atm. T = 500 K d = 0.36 kg/m3
MO 62.4
7 rO2 M gas M 1
25. C2H6 + O2 h 2CO2 + 3H2O = = =
2 rgas M O2 32 1.33
x 7/2x 2x 3x
32
C2H4 + 3O2 h 2CO2 + 2H2O (i) M =
40 – x 3x 2(40 – x) 2(40 – x) (1.33) 2
65 (ii) Molar volume
nO2 = mole Molecular weight 18.1 gm
16 = = = 50.27 ¥ 10 –3
2
65 Density 360 g/m
¥ 0.0821 ¥ 400
nRT 16 PV 1 atm ¥ 50.27
V= = L (iii) Z = = = 1.225
P 1 atm RT 0.0821 ¥ 500 K
7 65 ¥ 0.0821 ¥ 400 (iv) Z > 1 repulsive
x + 3x =
2 16 30. Mole of gaseous mixture,
Calculate x and find the ratio xC2H6 = 0.66. PV 6¥3
\ nH2 + unknown gas = = = 0.7308
26. 2H2 + O2 h 2H2O RT 0.0821 ¥ 300
mole
(1 – x) x 0
\ n(unknown gas) = 0.7308 – 0.7 = 0.0308 mole
–2x –x 1
1 – 3x 0 0
According to Dalton’s law of partial pressure

Mole of H 2 leaked M (unknown)
= P = PA + PB
Mole of unknown gas leaked M H2 1.5 = 1 + PB
0.7 M PB = 0.5 atm
=
0.0308 2 wRT
Now, PV =
M = 1033 g mol–1 m
31. PV = nRT For gas A : PA = 1 atm, m = MA, w = 2 g
–10
7.6 ¥ 10 2 ¥ RT
P= atmosphere 1¥V = (i)
760 MA
= 10–12 atmosphere for gas B : PB = 0.5 atm, m = MB, w = 3 g
V1 = 1 ltr n=?
3 ¥ RT
R = 0.082 ltr L atm K–1mol–1, T = 273 K 0.5 ¥ V = (ii)
\ 10–12 ¥ 1 = n ¥ 0.082 ¥ 273 MB
n = 4.46 ¥ 10–12 moles Dividing Eqs. (i) and (ii)
Molecules = 4.46 ¥ 10–14 ¥ 6.02 ¥ 1023 = 2.68 ¥ 1010 3¥ MA M 1
4 0.5 = or A =
32. Volume of one molecule of N 2 = p r 3 2 MB MB 3
3
–10 3 (B) If A is T = 298 K, V = ?
4 ¥ 3.14(2 ¥ 10 ) Put these values in Eq. (i)
=
3 2 ¥ 0.0821 ¥ 298
= 3.35 ¥ 10 m = 3.35 ¥ 10–23cm3
–29 3 V= = 1.53 litres
32
Volume of one mole molecules = 6.02 ¥ 1023 ¥ 3.35 ¥
10–23 cm3 = 20.167 cm3 35. 2H2 + O2 = 2H2O
Volume of one mole N2 at NTP = 22400 cc. Volume before reaction (L) 1 1 0
Hence empty space = 22400 – 22379.833 cm3 Volume after reaction (L) 0 0.5 1
(a) For : H2O PV = nRT
22379.833 ¥ 100
% empty space = = 99.9% At STP P = 1 atm, V = 1 litre,
22400 \ moles of H2O(n) = 4.46 ¥ 10–2
33. We will calculate the temperature of the gas from the Weight of H2O = 4.46 ¥ 10–2 ¥ 18 = 0.803 gram
given data. (b) Gas left in the vessel = 0.5 ltr of O2 at STP
PV = nRT 22.4 ltr at STP weigh 32 g
All values are to be taken in MKS system. 0.5 ltr at STP weigh = 0.71 g
P = 7.57 ¥ 103 N m-2 (c) Moles of H2O formed = 4.46 ¥ 10–2
V = 1 L = 1 ¥ 10–3 m3 Moles left = 0.5 ltr of O2 at STP = 2.23 ¥ 10–2
2 ¥ 1021 Total moles in the vessel = Moles of H2O + moles
n= moles , R = 8.31 JK–1 mol–1 of O2 left = 6.69 ¥ 10–2
6.02 ¥ 1023
PV = nRT
2 ¥ 1021 ¥ 8.31 ¥ T P = ?, V = 2 ltr,
7.57 ¥ 103 ¥ 10–3 =
T = 274.2 K 6.02 ¥ 1023 n = 6.69 ¥ 10–2 , T = 373 K
P ¥ 2 = 6.69 ¥ 10–2 ¥ 0.0821 ¥ 373
3RT P = 1.02 atm
Now, U rms =
M 35n1 + 37 n2
All the values are to be taken in MKS system, 36. = 35 - 45
n1 + n2
R = 8.31, M = 28 ¥ 10–3 kg for N2
35
T = 274.2 K where n1 and n2 are the number of moles of Cl and
37
Cl respectively.
3 ¥ 8.31 ¥ 274.2
U rms = = 494.2 metre/sec. n1
28 ¥ 10 –3 \ = 3.44 : n1 : n2 = 3.44 : 1
n2
Again, Ump = 0.82 ¥ Urms
= 494.2 ¥ 0.82 \ ratio of the lengths is 3.44 : 1.
= 405.26 metre/sec.
Ê 3.6 ˆ
34. For gas A : Its mass = 2 g; PA = 1 atm T = 298 K 37. P ¥ 8 = ÁË ˜ ¥R¥T (i)
M¯
For gas B : Its mass = 3 g, PB = 0.5 atm. T = 298 K
Gaseous State 3.55
From Eq. (i)/(ii)

0.3 17 dP
Ê 3.0 ˆ 48. (a) = fi = 3.25 torr/sec.
P ¥ 8 = ÁË ˜ ¥ R (T + 15) (ii) (dP / dt ) 20 dt
M¯
(b) Mavg = 0.30 ¥ 4 + 0.2 ¥ 32 + 0.5 ¥ 28 = 21.6
3.6 ¥ T = 3 (T + 15)
45 dP 21.6 dP
= 3T + 45 fi T = = 75 K = 0.3 fi = 0.3387 torr/sec.
0.6 dt 17 dt
3.6 0.0821 ¥ 75 49. Hint : P = P0e–Mgh/RT
fi P= ¥ = 0.062 atm
44 8 –
28 8 ¥10-3 ¥ 9 8 ¥10 ¥103
4 Ê 1ˆ 50. P = (101.325) e 8 314 ¥ 243

= 25.027 kPa
38. P ¥ p (10)3 = Á ˜ R ¥ T (i)
3 Ë 4¯ 51. If it melts then T > 1800 K
From Eq. (i)/(ii) 250 ¥ V P ¥V 250
n= = fi P = 1800 ¥
4 0.75 R ¥ 300 R ¥ 1800 300
P ¥ p r3 = ¥ RT (ii)
3 4 P = 1500 kPa
(10)3 1 4 3 1500 kPa > 106 Pa (or 103 kPa)
= = fi r = 3 ¥ 10
r3 0.75 3 4 so it will blow up before melting.
M ¥ 9 8 ¥1
r = 9.0856 cm P0 -
52. = P0e 8 314 ¥ 298
39. P ¥ 30 = 0.5 ¥ 38 ¥ 60 ¥ 1 P = 38 atm 2
40. C6H12O6 + 6O2 h 6CO2 + 6H2O M = 175.133 kg mole–1
Ê 0.2 ˆ
0.08928 mole Á ¥ 60 mole 0.53568 mole 75 M
Ë 22.4 ˜¯ 53. (i) = fi M = 32.1428 gm/mole.
= 16.071 gm = 11.999 lit 70 28
Ê 12 4 9 ˆ 3RT 3 ¥ 8.314 ¥ 273
41. P ¥ 1 = ÁË + + ˜¯ ¥ 0.0821 ¥ 300 = 66.74 atm (ii) v = = = 460.28 m/s
28 2 32 M 32.1428 ¥ 10 –3
P = 66.74 atm
Ê 10 64 ˆ 3RT 8 R ¥ 300
42. P ¥ 10 = ÁË + ˜¯ ¥ 0.0821 ¥ 473 54. –3
=
2 32 64 ¥ 10 p ¥ 32 ¥ 10 –3
fi P = 27.1833 atm 8 ¥ 300 ¥ 64
= 27.54 ¥ 105 N/m2 T= = 509.29 K = 236.29°C
3 ¥ 32 ¥ p
1
H2 + O2 h H2O(l) 3P 3 ¥ 1.01325 ¥ 105
2 55. (a) urms = = = 493.03 m/s
5 2 d 1.2504
(5–4) – 4
P ¥ 10 = 5 ¥ 0.0821 ¥ 473 8 1.01325 ¥ 105
(b) uavg = ¥ = 454.259356
P ¥ 19.4166 atm = 19.66 ¥ 105 N/m2 p 1.2504
(c) ump = 403 m/s
60 P 17
43. = fi P = 2.1979 atm 56. Use the results:
40 1 36.5
3RT1 8RT2 2 RT3
x (32 + 6 ¥ 19) 57. = = = 1500 m/s
44. = fi x  228 Ans. M pM M
100 28
Ï T1 = 2886 K rms
d NO 32 Ô
45. = fi d NO = 50.8 cm ÌT2 = 3399 K avg.
100 – d NO 30 ÔT = 4330 K
Ó 3 m.p.
t2 M2 2
46. = = fi t2 = 0.2672 hr  16 min 800 ¥ 1
t1 M1 28 58. 1.95 = (i)
nR ¥ 223
234 M mix 100 200 ¥ V
47. = fi M mix = 34.92 = 1.10 = (ii)
224 32 80 20 nR ¥ 373
+
32 M
1.95 800 1 373
M = 46.6 Ans. fi = ¥ ¥ V = 3.77 lit
1.10 200 V 223
10.1325 ¥ 105 ¥ 100 ¥ 10 –3 17.5 ¥ 0.8 ¥ V 6.5 ¥ V

59. 0.927 = n1 = fi n2 =
n ¥ 8.314 ¥ 273.15 R ¥ 293 R ¥ 277
w = n ¥ 32 = 15.40 ¥ 103 gm = 15.40 kgm n1
= 2.036
60. Hint : At critical temperature (TC) and critical pressure n2
(PC), O2 will behave ideally. n2
61. Hint : low density fi High molar volume (Vm) = 0.491
n1
Vm lim
 • So fraction of water vapour condensed
Ê 9 ¥ 6.7 ˆ n
62. Á15 + (10 – 3 ¥ 0.0564) = 3 ¥ 0.0821 ¥ T = 1 - 2 = 0.509
Ë (10) 2 ˜¯ n1
fi T = 623. K fi T = 350.5° 8RT
63. (i) P ¥ 12 = 15 ¥ 0.0821 ¥ (273 + 30)n 69. Average velocity = = 4 ¥ 102
pM
P = 31.1 atm RT
fi = 2 ¥ 104 fi RT = 2 2pM ¥ 104
Ê (15) 2 × 0.2107 ˆ pM
(ii) Á P + ˜ (12 – 15 ¥ 0.0171)
Ë (12) 2 ¯ Total K.E. of He
= 15 ¥ 0.0821 ¥ (273 + 30) P = 31.4 atm 6 3 9 9
= ¥ RT = RT = ◊ 2p ¥ 4 ¥ 10–3 ¥ 104 =180
Ê nRT2 nRT1 ˆ 4 2 4 4
64. 1000 ¥ g = e ÁË – ˜g pJ
P P ¯
Total K.E. of Ne
nR ¥ M
(T2 – T1 ) 12 3 9 9
RT1 = ¥ RT = RT = ¥ 2p ¥ 20 ¥ 10–3 ¥ 104
20 2 10 10
65. Q = CV1 (1000 – 500) + CV2 (1500 – 1000) = 360 pJ
Ê 3R 3R ˆ Ê 3R 3R ˆ (360 + 180)p
=Á + ˜ ¥ 500 + ÁË + + 3R˜ (500) Average K.E. per mol = = 807.84 J
Ë 2 2¯ 2 2 ¯ 1.5 + 0.5
= 1500 R + 3000 R = 4500 R 70. V – b = RT = 100 (0.011075 V – b) = 1.1075
66. r1h1 = r2h2, 99b
V – 100b fi V = = 921 b
In one hour h1 = 37 ¥ 2 = 74 mm 0.0175
1.034 ¥ 74 = 13.6 ¥ h2 fi 920 b = RT
h2 = 5.626 mm of Hg 4
fi b = 24.33 cm3 mol–1 = 4 ¥ p r 3 ¥ 6.023 ¥ 1023
5.626 3
P= atm/hr. PV = nRT fi r = 13.4 ¥ 10–9 cm = 134 pm
760
5.626 RT
¥ 0.016 = n ¥ 0.821 ¥ 310 71. V = + B = 2.058 L. Also, for the given equation
760 P
n = 4.653 ¥ 10–3 mole/hr. PB 10(– 0.1814)
Z=1+ =1+ = 0.918
Rate of O2 consumption = n ¥ 22400 cm3 = 0.104 RT 0.082 ¥ 273
cm3/m From Van der Waal's equation, for Z < 1, Z
O2 = 104 mm3/hr. a
67. P = 750 – 17.5 = 732.5 torr Z =1-
VRT
T = 20°C = 293 K a
Inhaled O2 = 52.5 ¥ 0.2032 fi = 0.082 fi a = 3.77 bar L2 mol–2
VRT
Exhaled O2 = 52.5 ¥ 0.1675 P t
PV PV – dP KP – dP K
fi Ú
M Ú0
72. = = dt
so at STP 1 1 = 2 2 dt M P
T1 T2 P 0
732.5 ¥ 52.5(0.2032 – 0.1675) 760 ¥ V ÊP ˆ Kt 4K

= fi ln Á 0 ˜ = fi ln 4 = = 2K
293 273 Ë P¯ M 4
fi V = 1.683 L for 6 min. 10 K
1.683 0.28 L ln = fi pHe = 7.07 atm
Oxygen consumption per min = = = 280 P 2
6 min
mL/min. ÊP ˆ Kt ÊP ˆ Kt
68. Let moles of water vapour initially = n1 Also, ln Á 0 ˜ = and ln Á 0 ˜ =
Ë P ¯ He 2 Ë P ¯ CH 4
4
Let moles of water vapour finally = n2
Gaseous State 3.57
2
Ê P0 ˆ Ê P0 ˆ 10 100
fi ÁË ˜¯ = ÁË ˜¯ fi = 2 3p
P He P CH4 7.07 PCH and vrms = (v ) so
4
8 avg
fi PCH4 = 8.4 atm
3p 1
73. NH3(g) + HCl(g) h NH4Cl(s) (vavg ) x = (vavg )CH 4
8 6
Moles 0.08 0.26 0
0 0.18 0.08 (vavg ) x 8 1 2
= ◊ =
fi Q = 0.08 ¥ 4300 = 3440 J (vavg )CH4 3p 6 3 p
3440
Also, Q = nCvDT fi DT = = 955.55 For X : Z1 = 2ps 2 (vavg )xN*
0.18 ¥ 20
Tfinal = 1255.55 K For CH4 : Z1 = ps2 (vavg )CH4 N*
Since T, P, v, n are same, N* will also be same.
0.18 ¥ 0.082 ¥ 1255.55
Pfinal = Z1 ( x) (vavg ) x 2
1.8 = 2 = 2◊
= 10.3 atmosphere Z1 (CH 4 ) (vavg )CH4 3 p
74. b = 39.1cm3mole–1 = 39.1 ¥ 10–6m3 mole–1 = 4V ¥ NA Z1(x) = Z1(CH4).
4 77. CH4 + 2O2 h CO2 + 2H2O
39.1 ¥ 10–1 = 4 ¥ p r 3 6.023 ¥ 1023
3 nCH4 1
r = 1.57 ¥ 10–10 m Initially =
nO2 192
s = 2r = 3.14 ¥ 10–10 m = 314 pm
8 RT 8 ¥ 8.314 ¥ 298 nCH4 1
mavg = = = 474.8 m/sec. Finally =
pM 3.14 ¥ 28 ¥ 10 –3 nO2 6
n
P 10 –3 ¥ 101325 1 1 Ê 32 ˆ
N*= = –23
= 3.24 ¥ 1019 = Á ˜
kT 760 ¥ 1.38 ¥ 10 ¥ 298 6 192 Ë 16 ¯
1 Z N* 32 = 2n/2
l1 = = 1
2ps 2 N * 2 5 = n/2 fi n = 10 steps
1 Let initial moles of CH4 Æ x so after 10 steps
= x (0.9)10 ¥ 100 = 1000
2 ¥ 3.14 ¥ (3.14 ¥ 10 –10 ) 2 ¥ 3.24 ¥ 1019
10
= 0.0705 m = 7.05 cm x= = 28.78 mole
0.36
Z1 = 2 ps2UN* 2 ¥ 3.14 ¥ (3.14 ¥ 10–10)2
Moles of O2 initially
¥ 474.8 ¥ 3.24 ¥ 1019 = 6739.4 sec–1
= 192 ¥ 27.78 = 5333.3 moles
1 Z N * 6739.4 ¥ 3.24 ¥ 1019
Z11 = ps 2UN * = 1 = nR
2 2 2 78. (a) Slope of P and T graph is
V
= 1.09 ¥ 1023m–3sec–1 = 1.09 ¥ 1017 cm–3 sec–1 nTh R
75. l = 2.6 ¥ 10–5 m, s = 0.26 nm = 2.6 ¥ 10–10 m so = 3.2 – 1.54 = 1.66
V
T = 300 K
1 nexp R
l= = 2.2875 – 1.25 = 1.0375
2ps 2 N * V
1 nexp 1.0375
2.6 ¥ 10–5 = so = = 0.625
2 ¥ 3.14 ¥ (2.6 ¥ 10 –10 ) 2 ¥ N * nTh 1.66
N* = 1.281 ¥ 1023 m–3 (b) nA m An with 50% yield
P Theoretical increase in pressure with temperature
N* =
KT should be 1.66 atm but actually it is 1.0375 only
P = 1.281 ¥ 1023 ¥ 1.38 ¥ 10–23 ¥ 300 so.
P = 530.3 Pa 1.66 ¥ 0.5
76. V, n, T Æ same so P Æ also same 1.66 – 1.66 ¥ 0.5 + = 1.0375
n
s Æ same
1 0.83
Given (vrms) x = (v ) 0.83 + = 1.0375 fi n = 4
6 avg CH4 n
79. Each time Sabu sucks air, volume of CO becomes half Moles of Ca(OH)2 required = 0.1174
so Moles of OH – CH2 – CH2 – NH2 required
Ê 1ˆ
n = 0.1174 ¥ 2 = 0.2349
5 Á ˜ < 0.001 5(0.5)n < 0.001 82. (i) Let n = mT + C
Ë 2¯
2 = 300 T + C and 3 = 200 T + C
log 5 + n log 0.5 < log 10–3 1
log 5 – 0.3 n < –3 0.3n > 3 + log 5 On solving m = – ,C=5
100
n > 12.3 n = 13
80. Plower = Pupper + Ppiston –T
So n= +5
Temp. 300 K 100
Ê –T ˆ
4V/5 (ii) PV = nRT fi 1 ¥ V = Á + 5˜ RT
1 mole Ë 100 ¯
V/5 1 mole RT 2
fi V =- + 5 RT
Initial 100
(iii) For Maximum volume
R ¥ 300 5 R ¥ 300
5¥ = + Ppiston dv – 2 RT
V 4 = 0 fi + 5 R = 0, T = 250
15 R ¥ 300 dT 100
¥ = Ppiston (i)
4 V – R(250) 2
V= + 5 ¥ 250 R = – 625 R + 1250
Plower = Pupper + Ppiston 100
4 RT 4 RT R = 625 R = 625 ¥ 0.0821 L = 51.3125 L
= + Ppiston A 2B
V 3 83. PV = RT - + 2
8 RT V V
= Ppiston (ii) 2
V RTV A 2B
V3- + V – =0
Temp. T
P P P
At critical point (V – Vc)3 = 0
3V/4 1 mole
V 3 - 3VcV 2 + 3Vc2V - Vc3 = 0
V/4 1 mole so on comparision
Final 3Vc2 = A/P (i)
From Eqs. (i) and (ii) 3Vc = RT/P (ii)
15 R ¥ 300 8 RT 4500 Vc3 = 2B/P (iii)
¥ = fi T = = 421.9 K
4 V V 32 (iii) Vc 2B
On fi =
81. (i) Let initial volume of mixture be V L, then (i) 3 A
H2 Æ 0.5 V, CO Æ 0.45 V, CO2 Æ 0.05 V
= Vc = 6B/A
On reaction with excess steam
from Eq. (i)
CO + H2O Æ CO2 + H2
2
0.045V – 0.05 V 0.95 V Ê 6B ˆ A3
3 Á ˜ = APc fi Pc =
– – 0.5 V 0.95 V Ë A¯ 108 B 2
0.95 V = 5
V = 5.263 L 3PcVc 3 Ê A3 ˆ Ê 6 B ˆ
From Eq. (ii) Tc = = Á ˜Á ˜
(ii) Molecular mass of initial mixture R 2 Ë 108 B 2 ¯ Ë A ¯
M = 0.5 ¥ 2 + 0.45 ¥ 28 + 0.05 ¥ 44 = 15.8 A3 6B
PM = rRT 2 ◊
A PcVc 108 B 2 A 1
1 ¥ 15.8 = r ¥ 0.0821 ¥ 273 Tc = fi Z = = =
6 RB RTc A2 3
r = 0.7 g/L R◊
6 RB
(iii) Volume of CO2 = 0.5 V = 0.5 ¥ 5.263 = 2.6315 L 84. 760 mm = 76 cm
2.6315 \ V = 76 ¥ 1 = 76 cm3
Moles of CO2 = = 0.1174 \ Mass = V ¥ d = 76 ¥ 13.6 = 1033.6 g
22.4
(a) If area of cross section is 2 cm2 (doubled) then vol-
Moles of KOH required = 0.1174 ¥ 2 = 0.2349 ume is also doubled hence,
Gaseous State 3.59
\ mass = 76 ¥ 2 ¥ 13.6 = 2067.2 g 88. The aqueous tension remains same in both the flask.
(b) This mass would rest on twice the area and exert Also flasks are at same temperature.
the same pressure. \ P1V1 = P2V2
85. The pressure on the bubble = 1 atm (when it is at the where P1 = 200 – 93 = 107 mm
surface.) V1 = 1 ltr
The pressure on the bubble = P atm (say) (when it is at V2 = 2 ltr
the bottom.) \ 107 ¥ 1 = P ¥ 2
1 P = 53.5 mm
The volume of the bubble = p(0.1)3
6 Since aqueous tension is also present in flask, it is
1 1 equivalent to 93 mm.
P¥ p ¥ (0.1)3 = 1 ¥ p (0.4)3 \ pressure of gaseous mixture = 93 + 53.5 = 146.5
6 6
mm-Hg.
or P = 64 atm. Thus the pressure due to water is 63
89. Partial pressure of CH4, ( pCH4 ) = 1 atm
atm (\ atmospheric pressure = 1 atm)
Now, consider the depth of lake is h cm Partial pressure of O2, ( pO2 ) = 4 atm
\ 63 ¥ 76 ¥ 13.6 ¥ g = h ¥ 1 ¥ g
or h = 63 ¥ 76 ¥ 13.6 cm = 65116.8 cm. 1 ¥ 0.5 0.5
\ moles of CH4 present, (nCH4 ) = =
86. For NO gas RT RT
PV 1.053 ¥ 250 4 ¥ 0.5 2
nNO = = = 1.069 ¥ 10–2 \ moles of O2 present (nO2 ) = =
RT 0.0821 ¥ 300 ¥ 1000 RT RT
CH4(g) + 2O2(g) = CO2(g) + 2H2O(l)
0.789 ¥ 100
For O2 gas :- nO2 = = 0.32 ¥ 10–2 0.5 2
0.0821 ¥ 300 ¥ 1000 Initially
Now, 2NO + O2 h N2 O4 RT RT
Mole before reaction: 1.069 ¥ 10–2 0.32 ¥ 10–2 0 1 0.5
Mole after reaction: 1.069 ¥ 10–2 – 2 ¥ 0.32 ¥ Finally –
RT RT
10–2 0 0.32 ¥ 10–2 After the reaction, moles of residual O2
= 0.429 ¥ 10–2
Moles of NO left = 4.29 ¥ 10–3 2 1 1
= – =
PNO ¥ V = nRT Given T = 220 K RT RT RT
0.5
250 + 100 350 After the reaction, moles of CO2 produced =
V= = litre RT
1000 1000
1.5
350 Hence total number of moles of O2 and CO2 =
PNO ¥ = 4.29 ¥ 10–3 ¥ 0.821 ¥ 220 RT
1000
1.5 RT
PNO (left) = 0.221 atm. \ total pressure due to O2 and CO2 = ¥ = 3 atm
87. N2 + 3H2 m 2NH3 RT 0.5
Initially 1 3 0 \ pressure exerted by the entire gaseous components
at equilibrium (1 – x) 3 (1 – x) 2x
26.7
Total moles = 1 – x + 3 – 3x + 2x = (4 – 2x) moles =3+ = 3 + 0.03513 = 3.0513 atm
760
34
Given Average molecular mass = 90. M (dry air)
3
34 28(1 – x) + 2(3 – 3 x) + 17(2 x) M1 (O 2 ) X1 (% of O 2 ) + M 2 ( N 2 ) X 2 (% of N 2 )
= =
3 (4 – 2 x) X1 + X 2
34
(4 - 2 x) = 34 fi 4 - 2 x = 3 fi x = 1/2 32 ¥ 24.5 + 28 ¥ 75.5
3 = = 28.98 g mol–1
100
So total number of moles = 3
PM (air) 1 ¥ 28.98
nRT 3 ¥ 0.821 ¥ 300 d (dry air) = =
PV = nRT fi = = 9 atm RT 0.0821 ¥ 298
V 8.21
1– x 0.5 = 1.184 g L–1 = 1.184 kg m–3
pN 2 = ¥P= ¥ 9 = 1.5 atm
3 3 Ê –3
–1 10 kg –3 ˆ
3 – 3x 1.5 ÁË1 g L = –3 3 = 1 kg m ˜¯
pH2 = ¥P= ¥ 9 = 4.5 atm 10 m
3 3
Relative humidity (50%) Let n1 moles of CO and (100 – n1) moles of CO2 be
Partial pressure of H 2O in air present in 100 moles.
= \ average molecular weight (M)
Vapour pressure of H 2O
\ P(H2O) = 0.50 ¥ 23.7 Torr n1 ¥ 28 + (100 ¥ n1 ) ¥ 44
= = 38.85 fi n1 = 32.19
11.85 100
= 11.85 torr = atm = 0.0156 atm
760 \ mole % of CO = 32.19, and mole % of CO2 = 67.81.
0.0156 ¥ 100 93. The molar ratio of oxygen and the other gas in the
% of H2O vapour in air = = 1.56% evacuated bulb is 1 : 1 and the total pressure of the gas
1
mixture is 4000 mm. Hence the partial pressure of each
% of N2 and O2 in air = 98.44%
gas is 2000 mm.
M (wet air)
The drop in the pressure of oxygen after 74 minutes,
28.98 ¥ 98.44(air) + 18 ¥ 1.56 (water vapour)
= (2000 – 1500) ¥ 74
100 = = 787.2 mm of Hg
–1 47
= 28.81 g mol
\ after 74 minutes, the pressure of oxygen = 2000 –
PM (wet air) 1 ¥ 28.81
d (wet air) = = 787.2 = 1212.8 mm of Hg.
RT 0.0821 ¥ 298 Let the rate of diffusion of other gas be rn, then
= 1.177 g L–1 = 1.177 kg m–3
rn 32
Difference = 1.184 – 1.177 = 0.007 kg m–3 =
91. Partial pressure of C4H10 (p1) = 760 mm Hg rO2 79
By Dalton's law of partial pressure, Ptotal = p1 + p2 32
\ drop in pressure for the other gas = 787.2 ¥ =
1920 = 760 + p2 or p2 = 1160 mm Hg 79
501.01 mm of Hg.
p2 = x2 ¥ ptotal
\ pressure of the other gas after 74 minutes = 2000
where x2 = mole fraction of Ne
– 501.01 mm = 1498.99 mm of Hg.
p2 1160
x2 = = = Moles of unknown gas 1498.99
Ptotal 1920 Molar ratio = =
0.60; Moles of O 2 1212.8
V 1 litre V 1 litre = 1.236 : 1
Moles of Ne =
8.6787 94. (a) Under low pressure region, V is high
= 0.43 \ (V – b) ª V
20.2
Ê a ˆ
n2 0.43 ÁË P + 2 ˜¯ V = RT
x2 = ; 0.60 = fi n1 = 0.28 V
n1 + n2 0.43 + n1
a
Molecular weight of C4H10 = 48 + 10 = 58. PV + = RT
V
So, amount of C4H10 = n1 ¥ 58 = 16.24 g
Again for C4H10 PV a
+ =1
PV = n1RT ; T = 273 + 25 = 298 K, RT RTV
PV Ê a ˆ 20.39
760 Z= = Á1 – ˜¯ = 1 - = 0.98
atm = 1 atm RT Ë RTV 0.0821 ¥ 350 ¥ 35
P=
760
(b) Under high pressure region, P is high,
n RT 0.28 ¥ 0.0821 ¥ 298
V= 1 = = 6.85 L Ê a ˆ
P 1 ÁË P + 2 ˜¯ ª P
V
92. For mixture, P = (730/760) atm,
\ P(V – b) = RT
T = 303 K, d = 150 g litre–1
PV – Pb = RT
\ PV = nRT = (w/M) RT fi P(w/VM) RT
d PV Pb
RT – =1
fi P = RT RT
M
PV Pb Ê PV P 1ˆ
730 1.50 \ Z= =1+ Á = 1, or = ˜
\ = ¥ 0.0821 ¥ 303 RT RT Ë RT RT V ¯
760 M
\ M = 38.85 b 0.1383
Z=1+ =1+ = 1 + 0.004 = 1.004
V 35
Gaseous State 3.61
95. (b, d) As rate of diffusion is also inversely proportional to

g He M CO 28 t M2
= = = 7 = 2.65 time, we will have, 2 =
g CO M He 4 t1 M1
g He 64 4
= = 16 = 4 (a) This, for He, t2 = (5s) = 5 2 s π 10 s
g SO2 4 2
96. (a, c, d) 32
P (b) For O2, t2 = (5s) = 20 s
DG = RT ln 2 2
P1
2 28
= 8.314 ¥ 298 ¥ 2.303 log (c) For CO, t2 = (5s) π 25 s
1 2
P
DS = – R ln 2 < 0 44
P1 (d) For CO2, t2 = (5s) π 55 s
97. (a, c, d) 2
rvap 2 7. N2O4 m 2NO2

32 Ê 4ˆ 32
= fi Á ˜ = 1 – 0.2 2 ¥ 0.2
lO2 M vap Ë 3¯ M vap 0.8 mole 0.4 mole
Mvap = 18 nT = (0.8 + 0.4) mole = 1.2 mole
18 P1 P2
fi V.D = 9 fi Density = gram/ltr = at 300 K
22.4 T1 T2
= 0.8035 gram/ltr
Now, 1 P
= 2
300 600
PV P PM 18 P
Z= = = fi Z = \ P2 = 2 atm = PN2O4 at 600 K
nRT W
RT dRT dRT
or Pressure of 1 mole N2O4
MV
\ Pressure of 1.2 mole gas (N2O4 and NO2)
= 1.2 ¥ 2 = 2.4 atm
PREVIOUS YEARS’ QUESTIONS
a
OF JEE (MAIN & ADVANCED) 8. B = b -
RT
1. PV = nRT (number of moles = nV) Derivation of Boyles Temperature.
\ n/V = P/RT 9. According to Graham's law of diffusion, for two gases
2. Value of gas constant undergoing diffusion at different pressures throught
(R) = 0.0821 L atm K–1mol–1 same hole
= 8.314 ¥ 107 ergs K–1mol–1 rA M B PA
= 8.314 JK–1mol–1 = 1.987 cal K–1mol–1 = ¥
rB M A PB
3
K.E. of neon at 40°C 2 K ¥ 313 313 Ê 1 ˆ
3. = = ÁË r µ P ¥ At constant temperature˜
K.E. of neon at 20°C 3 K ¥ 293 293 M ¯
2 10. Weight of gas = 50.5 – 50
4. In van der waal’s equation, 'b' is for volume correction.
148 - 50
5. The expression of root mean square speed is \ V= = 100 ml
0.98
3RT w
U rms = Using, PV = nRT = RT
M m
Hence, 760 100 0.5 È 0.5 ˘
¥ = ¥ 0.082 ¥ 300 Ín =
U rms (H 2 ) È 3R(50 K)/(2g mol –1 ) ˘
1/2
760 1000 m Î m ˙˚
=Í ˙ =1
U rms (O 2 ) Î 3R(800 K)/(32g mol –1 ) ˚ \ molecular weight of gas (m) = 123
11. Van der Waal’s equation for n moles of gas is
r1 M2 È n2a ˘
6. Under identical condition, =
r2 M1 Í P + 2 ˙ [V - nb] = nRT
Î V ˚
Given: V = 4 ltr; P = 11.0 atm, T = 300 K; PV

b = 0.05 ltr mol–1, n = 2 17. We know that, compressibility factor, Z =
RT
È 22 a ˘ 100 ¥ V
Thus, Í11 + 2 ˙ [4 – 2 ¥ 0.5] = 2 ¥ 0.082 ¥ 300 0.5 =
Î 4 ˚ 0.082 ¥ 273
\ a = 6.46 atm ltr2 mol–2 \ V = 0.1119 L
12. We know that
Note: Further when volume of a gas molecule is neg-
r1 M 2 P1 n t M 2 P1
= ¥ or 1 ¥ 2 = ¥ ligible, Van der Waal's equation becomes
r2 M1 P2 t1 n2 M1 P2
Ê a ˆ
1 57 M 0.8 ÁË P + 2 ˜¯ (V - 0) = RT
or ¥ = ¥ V
38 1 28 1.6
a
\ M = 252 or PV = RT – or a = RTV – PV2
V
ÈXe + (F) x = 252 Substituting the values,
Í a = (0.082 ¥ 0.1119 ¥ 273)
Î131 + 19 x = 252; \ x = 6
Thus compound of xenon with fluorine is XeF6. – (100 ¥ 0.1119 ¥ 0.1119)
13. For an ideal gas behaviour, the molecules of a gas = 1.253 and L2 mol–2
should be far apart. The factors favouring this condi-
tion are high in temperature and low in pressure. 18. (a) d = 0.36 kgm–3 = 0.36 g/L
PV (i) From Graham's law of diffusion
14. Compressibility factor of ideal gas (Z) =
nRT rv M O2 32
For one mole of ideal gas at STP, = ;1.33 =
P ¥ 22.4 rO2 Mv Mv
Z=
RT 32
\ Mv = = 18.09
P ¥ Vm (1.33) 2
For given gases Z < 1 and Z =
RT
\ Vm < 22.4 ltr where Mv = MW of the vapour
Alternate solutions 0.36
(PV)Observed/(PV)Ideal < 1 (ii) Thus, 0.36 g = mol
18.09
fi Vobs < Videal, Vobs < 22.4 ltr 0.36
mol occupies 1 L volume, so 1 mole
15. We know 18.09
3RT occupies
U rms =
M 18.09
L = 40.25 L
3RTH2 3RTN2 0.36
= 7 Thus, molar volume of vapour = 50.25 L.
2 28
Assuming ideal behaviour the volume of the va-
\ TN2 = 2TH2 or TN2 > TH2
pour can be calculated by
16. Van der Waal’s equation for one mole of a gas is V1 V2 500
= fi V2 = 22.4 ¥ = 41.05 L
È a ˘ T1 T2 273
ÍÎ P + V 2 ˙˚ (V – b) = RT (i)
(iii) Compressibility factor (Z)
Given that volume occupied by CO2 molecules, ( PV )obs 1 ¥ 50.25
'b' = 0 = = = 1.224
( PV )ideal 1 ¥ 41.025
Hence, Eq. (i) becomes (iv) Z is greater than unity, hence it is the short range
È a ˘ RT a repulsive force that would dominate.
ÍÎ P + V 2 ˙˚ V = RT or P = V – V 2 ( actual density is less than given density.)
Using R = 0.082, T = 273 K, V = 22.4l for 1 mole of an 3 3 8.31
(b) E = KT = ¥ ¥ 1000
ideal gas at 1 atm pressure 2 2 6.02 ¥ 1023
0.082 ¥ 273 3.592 = 2.07 ¥ 10–20 J per molecule
\ P= - = 0.9922 atm
22.4 (22.4) 2 ( K, Boltzmann constant = R/NA)
Gaseous State 3.63
19. TIPS/Formulae: a ab
PVm - Pb + - = RT
3RT 8RT Vm Vm2
Vrms = , Cav =
M pM a ab
PVm = RT + Pb - + 2 (i)
Vrms 3RT pM 3p Vm Vm
= ¥ = = 1.085
Vav M 8RT 8
Note:
Vrms = 1.085 ¥ Cav = 1.085 ¥ 400 = 434 ms–1 To calculate the intercept P Æ 0, hence Vm Æ • due
to which the last two terms on the right side of the
20. For positive deviation : PV = nRT + nPb equation (I) can be neglected.
Pb \ PVm = RT + Pb
fi Z =1+ When P = 0, intercept = RT
RT
Thus, the factor nPb is responsible for increasing the 22. TIPS/Formulae:
PV value. Above ideal value, b is actually the effec- Using Grahms’ law of diffusion,
tive volume of molecule. So, it is the finite size of mol- M CH4
rHe 16
ecules that leads to the origin of b and hence positive = = =2
deviation at high pressure. rCH4 M He 4
21. The Van de Waal equation (for one mole) of a real gas Pb
23. For gas A, a = 0, Z = 1 + implies Z varies linearly
is RT
a ˆ with pressure.
Ê a
ÁË P + V 2 ˜¯ (Vm – b) = RT For gas B, b = 0, Z = 1 – . Hence, Z does not vary
m VRT
linearly with pressure.
Chapter
4
Chemical
Equilibrium
Key Concepts
Dependency of K eq = Ae
- DH ∞
RT ...(1)
Equilibrium Constant on
Temperature
DH ∞ 1
n K = nA - ◊ ...(2)
Eaf
R T
- RT
Kf Af e If DH° > 0
K eq = =
Kb Ab e - Eab / RT lnKeq
Arrhenius Equation �� Slope DH°/R
K = Ae–Ea/RT lnA
K =Rate constant or Velocity constant or Specific reac-
tion rate
1/T
A =Arrhenius constant or Frequency Factors or Preex-
ponential factor Ea = activation energy If DH° < 0
nKeq
Significance of A ��
A gives us number of reactant molecules colliding in unit
time in unit volume. Slope DH°
‘A’ for a particular reaction is constant and is independent R
of temperature. nA
For a particular reaction Ea is constant and is independent
of temperature. 1/T
K = f (T ) only Equation (2) is known as Van’t Hoff Equation (Integral)

Differentiate equation (2) with respect to temperature.
- 1 ( Eaf - Eab )
K eq = Ae RT
d (nK eq )
+DH ∞ 1
=◊ 2
dT R T
Eaf
Eab K 2 DH ∞ È 1 1˘
n = Í - ˙
K1 R Î T1 T2 ˚
PE DH Eaf Eab
Time
Thermodynamics of Equilibrium constant KP = KC(RT)1

DG = DH – TDS PCl5  PCl3 + Cl2
–nFE cell Initial Pressure P0 — —
= – W useful
At equilibrium P0(1 – a) P0a P0a
DG = DG∞ + RT n Q ...(1)
Pt = Peq = PPCl5 + PPCl3 + PCl2
DG < 0 fi Spontaneous or Irreversible
DG = 0 fi Reversible at equilibrium Pt = Peq = P0(1 + a)
DG > 0 fi Non-Spontaneous Peq
At equilibrium P0 =
(1 + a )
DG = 0
PPCl3 ¥ PCl2 P0a ◊ P0a a2
Qeq = Keq KP = = = ◊ P0
DG° = DH° – TDS° ...(2) PPCl5 P0 (1 - a ) (1 - a )
= –nFE°
a2
= –RT ln Keq ...(3) K P = Peq ◊
1- a2
If DG° > 0 fi ln Keq< 0 fi Keq< 1 fi Kf < Kb
DG° = 0 fi ln Keq = 0 fi Keq = 1 fi Kf = Kb PCl5(g)  PCl3(g) + Cl2(g)
DG° < 0 fi ln Keq> 0 fi Keq = 1 fi Kf > Kb Initial moles a – –
Equating Equations (2) and (3); At Equilibrium (a – x) x x
(a - x) x x
–RT ln Keq = DH° – TDS° Mole Fraction
a+x a+x a+x
DH ∞ DS ∞
n K eq = - + ...(4) (a - x) x x
RT R Partial Pressure ◊ PT ◊ PT ◊ PT
(a + x) (a + x) (a + x)
2
Calculation of Equilibrium Constant �� Ê x ˆ
PCl5(g)  PCl3(g) +Cl2(g) ÁË a + x PT ˜¯
KP =
Initial moles: a — — Ê a - xˆ
At Equilibrium (a – x) x x ÁË a + x ˜¯ PT
moles (a - x) x x
Equi.[Conc] = x2
v v v v = ◊ PT
a2 - x2
[PCl3 ][Cl2 ]
KC = a2
[PCl5 ] KP = ◊ PT
( x /v)( x /v) 1- a2
=
Ê a - xˆ
ÁË ˜ Degree of Dissociation (a) and Equilibrium
v ¯
Vapour Density (d) ��
x2 An(g)  nA(g)
KC =
v(a - x) Initial concentration C 0
PCl5(g)  PCl3(g) +Cl2(g) Equilibrium concentration C(1 – a) nCa
(b) Initial moles : a – – D0 = Initial vapour density, d = Equilibrium vapour density or
At Equilibrium a(1 – a) aa aa vapour density of mixture of An and A at equilibrium
a (1 - a ) aa aa 1
Concentration Vapour Density µ
v v v number of moles
a = degree of dissociation D0 neq c(1 - a + na )
\ = =
[PCl3 ][Cl2 ] d n0 c
KC =
[PCl5 ] D0
= 1 - a + na
Ê aa ˆ Ê aa ˆ d
ÁË ˜¯ ÁË ˜¯
v v D0
= -1
Ê a (1 - a ) ˆ a= d
ÁË ˜¯
v n -1
aa 2 * PCl5  PCl3 + Cl2
KC =
v(1 - a )
Chemical Equilibrium 4.3
Molar Mass of PCl5 208.5 Addition of inert substance or in active substance has no
D0 = = = 104.25 n = 2 effect on the equilibrium.
2 2
CaCO3(s)  CaO(s) + CO2(g) Keq = [CO2]
1
* SO3 m SO3 + O 2 CO2 Add – equilibrium shift in backward
2 CaCO3 add – no effect
Molar Mass of SO3 80 3 CaO add – no effect
D0 = = = 40; n =
2 2 2 He/N2 add – no effect
* 2NH3  N2 + 3H2 (at constant volume)
17 4 (ii) Effect of Pressure
D0 = ;n= =2
2 2 2R(g)  P(g)
RT
Degree of Association (a) and Equilibrium PT = nT
V
Vapour Density (d) �� For gaseous reaction having different gaseous moles on the
nA(g)  An(g)
Left Hand Side and Right Hand Side, if volume is decreased
Initial moles C —
at constant temperature or in other words, pressure is increas-
Ca
at Equilibrium C(1 – a) es then, equilibrium shift in a direction where total number of
n gaseous moles are less.
D0 C (1 - a + a /n) 2R(g)  P(g)
=
d C 2R(g) P(g)
concentration
a D0
a - =1- R R R
n d
R
Ê D0 ˆ
ÁË1 - ˜
a= d ¯ = D0 - d
P
Ê 1ˆ Ê1 ˆ
ÁË1 - ˜¯ ÁË - 1˜¯ d P
n n P
P
* PCl3 + Cl2  PCl5 (n = 2) Volume Volume Time
* N2 + 3H2  2NH3 (n = 2) decreases increase
* 2SO2 + O2  2SO3 (n = 3/2) equilibrium equilibrium
In forward In backward
direction direction
Le Chatelier’s Principle ��
According to Le Chatelier’s principle when any equilibrium (iii) Effect of Temperature
is subjected to change in pressure, temperature, concentration Case (i)
then, equilibrium shifts in a direction so as to nullify the effect. On decreasing temperature exothermic reaction proceed in
(i) Effect of Concentration Change forward direction
When reactant concentration is increased or product concen- Equilibrium
tration is decreased at equilibrium then, equilibrium always
move in the forward direction and vice versa. R P + heat
Equilibrium
R P
Equilibrium
Equilibrium On increasing temperature exothermic reaction proceed in
backward direction
con. equilibrium
R add Case (ii)
R On decreasing temperature endothermic reaction proceed in
backward direction
Equilibrium
R + heat P
P Premove Time
equilibrium
Equilibrium
On increasing temperature endothermic reaction proceed in

x2 - y 2
forward direction KP1 =
a-x
(iv) Addition of the Inert Gas at Equilibrium PO2 = x + y, PN2O3 = x - y
Case (i) Addition of the inert gas at equilibrium at constant
Example 4.
pressure:-
PCl5  PCl3 + Cl2 x(s)  A + C K P1 = x( x + y ) ...(i)
Initial mole 1 0 0 x x+y
at equilibrium (1-a) a a y(s)  B + C K P2 = y ( x + y ) ...(ii)
a2 y x+y
KC =
V (1 - a ) n A PA x
\ = =
where a is the degree of dissociation. nB PB y
Since V increases and thus to keep KC constant, a must in- and PT = PA + PB + PC
creases i.e., degree of dissociation of PCl5 increases or [PCl3]
= x + y + (x + y) = 2(x + y)
and [Cl2] increases at equilibrium and the [PCl5] decreases at
equilibrium Ex. When NO and NO2 are introduced in a container fol-
lowing equilibrium is simultaneously obtained.
Case (ii) Addition of the inert gas at equilibrium at constant
2NO2(g)  N2O4(g) KP = 6.8 atm–1
volume:-
PCl5  PCl3 + Cl2 NO(g) + NO2(g)  N2O3(g)
Initial mole 1 0 0 In an experiment NO and NO2 are mixed in the molar
at equilibrium (1-a) a a ratio. 1 : 2, the total final pressure was 5.05 atm and the
a2 partial pressure of N2O4 at equilibrium was 1.7 atm.
KC = Calculate the equilibrium PNO and Calculate KP for 2nd
V (1 - a ) reaction.
2
where a is the degree of dissociation. Sol. 2NO2(g)  N2O4(g)

Since Volume remains constant during the change and the 2P0 —
addition of inert gas at constant volume will also have no
x
influence on the equilibrium concentrations for this type of (2P0 – x – y) x/2 = 1.7 = x = 3.4
equilibria 2
NO + NO2  N2O3
(P0 – y) (2P0 – x – y) y
Simultaneous Equilibrium ��
When two or more than two equilibrium are established to- PN2O4
KP = 6.8 =
gether in the same container then, such equilibrium are re- ( PNO2 ) 2
ferred as simultaneous equilibrium provided they have atleast
one active component common. 1.7
fi ( PNO2 ) = = 0.5
Example 1. 6.8
(2P0 – 3.4 – y) = 0.5
CaCO3(s)  CaO(s) + CO2(g) KP1 = PCO2 = ( P1 + P2 )
fi 5.7 – 3.4 – y = 0.5 fi y = 1.8
MgCO3(s)  MgO(s) + CO2(g) KP2 = PCO2 = ( P1 + P2 )
PT + PNO2 + PNO + PN2O3 + PN2O4
Example 2. 5.05 = 0.5 + (Po – y) + y +1.7
N2 + 3H2  2NH3 P0 = 2.85
(P1) (P2) 0 y 1.8
P1 – x – y P2 – 3x – 2y 2x K P2 = = = 3.43 atm -1
PNO ¥ PNO2 1.05 ¥ 0.5
N2 + 2H2  N2H4
P1 – x – y P2 – 3x – 2y y Effect of Catalyst on the Equilibrium
1. Catalyst alters the reaction mechanism and in the new
Example 3.
path activation energy is lowest than the previous one.
N2O5  N2O3 + O2 2. Catalyst increases the rate of forward and back reaction
a 0 0 by same extent.
a–x x–y x+y 3. Since, catalyst increases the rate of forward as well
N2O3  N2O + O2 as backward reaction, it does not alter the equilibrium
x–y y x+y concentration of reactants and products.
4. Catalyst does not changes the DH for the reaction. rate of formation of B at equilibrium
5. Catalyst does not affect the equilibrium constant be- d [ B]
cause both Kf and Kb increases. =0
dt
6. Catalyst reduces the time taken in establishment of Kf[A] = Kb[B]
equilibrium.
Eaf E
tHree pHase DiaGram
af Eab
PE DH Eaf Eab dG = Vdp – SdT

for chemical reaction
Time d(DG) = DV ◊ dp – DS ◊ dT
at equilibrium: DG = 0
DV dp = DS dT
X
dP DS
Eaf = ææ Æ Claussius Claperpron Equation
Eaf
P dT DV
Eaf
H2O(R)  H2O(g)
R (1) H2O(l) + heat  H2O(g)
(a) On increasing temperature reaction proceed in forward
direction. On decreasing temperature reaction proceed
K = A- E0 / RT [K¢ > K] in back ward direction.
K¢ = Ae–(Ea – x)RT (b) On increasing pressure reaction proceed in backward
direction. On decreasing temperature reaction proceed
Rate in forward direction.
[P]
boilinG point
[A]
Time The temperature at which vapour pressure of any liquid is
equal to external pressure (surrounding pressure) is known
as boiling point.
rf
rf If external pressure is 1 atm then, boiling point is known
rb rb as normal boiling point. (See figs.)
Vapour Pressure
teqm teqm P2
P1
P1 1 atm
P3
Note: ………………………………
Line in above figure Represent change due to presnce of
catalyst.
Kinetic and Equilibrium constant

Kf T3 T 1 T 2 Time
 B
A 
Kb
- d [ A] 100°C/373 K
= rate of disappearance of A = Kf[A] – kb[B] Pressure µ Boiling Point
df
at equilibrium
- d [ A]
=0 fi Kf[A] = Kb[B] tHriple point
df
Kf [ B]
fi = = K eq dP DS (+Ve)
Kb [ A] =
dt DV (+Ve)
+ d [ B]
= K f [ A] - K b [ B] DG = DH – TDS
dt
DH DSm  10.5R
DS =  88 J/K-mole
T
ngRT DH m
DV = Vg – V1  Vg = DSm =
P TB
dP DS DH P DH m ◊ P 2. H2O(S) + heat  H2O(l)
= = ¥ =
dT DV T ng RT RT 2 On increasing pressure to a physical equilibrium, equi-
librium always shifts in a direction where density in-
Slope (+Ve)
creases.
P On increasing Pressure melting point of ice decreases
liquid dP DS (+ ve)
P
becaus slope = = = fi (– ve)
(latm) dT DV [Vl - Vs ]Æ(– ve)
solid
Triple 3. Na(S) + heat  Na(l)
(4.58 mm mg)
point gas dP DS (+ ve)

=
dT DV (+ ve)
On increasing pressure, melting point will increase.
T 4. H2O(S) + heat  H2O(g)
273.16 K 373 (K)
dP DS (+ ve)
=
On separting variables; dT DV (+ ve)
dP DH m T2 1
P2 5. KOH(S) + H2O(l)  KOH (aq.)
ÚP1 P
=
R ÚT1 T 2
◊ dT
+ Heat
P DHm È 1 1˘ on increasing temperature
n 2 = - Solubility of KOH decreases
P1 R ÍÎ T1 T2 ˙˚
6. NaCl(S) + H2O(l) + heat  NaCl(aq.)
on increasing temperature
trouton’s rule Solubility of NaCl increases
7. A(g) + Solvent  A(Solution) + heat
(DH < 0) or Exothermic on increasing temperature
1. For majority of the liquids, molar entropy change of
solubility of gas decreases on increasing pressure solu-
vapours.
bility of gas increases
Solved Examples
1. For the reaction H2 + I2  2HI at 300 K, equilibrium 5

constant is 100. If 2 moles of H2 and 2 moles of I2 are \ x=
3
taken in a 10 L vessel. Calculate the equilibrium con- 2- x 1
centration of each. [H 2 ] = [I 2 ] =
= M
10 30
Sol. H2 + I2  2HI
2x 1
Initial moles: 2 2 – [HI] = = M
Equ. moles: (2 – x) (2 – x) 2x 10 3
(2 - x) (2 - x) 2x 2. For the reaction N2O4(g)  2NO2(g) the equilibrium
Equ. [ ] :
10 10 10 moles of N2O4 and 2NO2 are 2 and 1 respectively, in a
10 L container at 300 K. Calculate KC, KP.
[HI]2
KC = or Sol. N2O4(g)  2NO2(g)
[H 2 ][I 2 ]
Equ. moles 2 1
(2 x /10) 2
100 = 2 1
(2 - x /10)(2 - x /10) Equ. [ ]
10 10
(2 x /10)
10 = [NO 2 ]2 (1/10) 2 1
(2 - x /10) KC = = = moles
[N 2O 4 ] (2/10) 20
20 - 10 x = 2 x
1 24.6 7. Calculate mole % of Cl at equilibrium for the reaction

K P = K C ( RT ) = ¥ (0.0821 ¥ 300)atm = atm PCl5  PCl3 + Cl2 KP = 0.2 under a total pressure of 2
20 20
atm.
3. For the equilibrium 2SO2(g) + O2(g)  2SO3(g) KC =
100 at any temperature (T). If at equilibrium on same Sol. PCl5  PCl3 + Cl2
temperature T equilibrium concentration of SO2 and P0 – –
SO3 are same in a 10 litre vessel. Calculate equilibrium P0(1 – a) P0a P0a
moles of O2.
P0a 2 a2
[SO3 ] 2 KP = = PT
Sol. KC = 1- a 1- a2
[SO 2 ]2 [O 2 ] PCl2 P0a a
1 1 X Cl2 = = =
[O 2 ] = = PT P0 (1 + a ) (1 + a )
KC 100
10 mole % of Cl = ( X Cl2 ¥ 100) = 23.07 %
Number of moles of O2 = = 0.1 mole
100 8. Calculate the equilibrium concentration of PCl3 in a 10 L
4. For the equilibrium PCl5  PCl3 + Cl2 at 400 K and rigid container if 1 mole of PCl5 is taken to be certain
1 atm; a = 0.4. Calculate the density of equilibrium. equilibrium according to the following reaction:
mixture under given condition in gram per litre. PCl5  PCl3 + Cl2
D0 KC = 10–5
-1
Sol. a = d Sol. PCl5  PCl3 + Cl2
n -1 Initial 1 – –
104.25 at eq. moles 1 – x x x
-1
104.25 1- x x x
a= d fi 0.4 = -1 active mass
2 -1 d 10 10 10
5. For the reaction : A(g) + B(g)  C(g) + D(g) KC = 25. 1
If we take 2 moles of each gases in a 40 litre L vessel. ª
10
What will be the equilibrium concentration of B.
Kc
Sol. A(g) + B(g)  C(g) + D(g) Since < 10-3 \1 - x = 1
2 2 2 2 Concentration
2–x 2–x 2+x 2+x ( x /10) 2 x2
2 K C = 10-5 = fi 10-5 =
Ê 2 + xˆ (1 - x /10) 10
ÁË ˜
25 = V ¯
2 x 2 = 10- 4 = x = 10- 2
Ê 2 - xˆ
ÁË ˜ x
V ¯ [PCl3 ] = = 10-3 M
2+ x 10
5=
2- x 9. Calculate the equilibrium concentration of PCl3 in a 10 L
rigid container if 1 mole of PCl5 is taken to be certain
10 – 5x = 2 + x
equilibrium according to the following reaction:
8 = 7x
8 PCl5  PCl3 + Cl2
x = mole
7 If Keqm = 10–2
8
2- Sol. PCl5  PCl3 + Cl2
[ B] = 7= 6 M
40 280 Initial 1 – –
at eq. moles 1 – x x x
6. Find Kp for N2O4(g)  2NO2(g) if initial pressure P0
and degree of dissociation for reaction is a. 1- x x x
active mass
Sol. N2O4(g)  2NO2(g) 10 10 10
P0 0 x2
P0(1 – a) 2P0a 10-2 =
10(1 - x)
PT = P0(1 + a) x = 0.96
(2 P0a ) 2 4 P0a 2 a2 x
KP = = = 4 PT [PCl3 ] = = 0.096 M
P0 (1 - a ) 1 - a 1- a2 10
10. 23 g of N2O4(g) was placed in a 1 L container at 400 K x = 0.21 M

and allowed to attain equilibrium N2O4(g)  2NO2(g). 13. A + 3B  2C + D
The total pressure at equilibrium was found to be 11.6
For this hypothetical reaction, initial moles of A is
bar, then what will be the partial pressure of NO2 at
twice that of B. If at equilibrium moles of B and C are
equilibrium?
equal then percent of B reacted is:
(a) 9.15 bar (b) 4.98 bar
(a) 10% (b) 20% (c) 40% (d) 60%
(c) 6.6 bar (d) 8.3 bar
Sol. (c) Sol. (d) A + 3B  2C + D
nRT 1 Initially 2a a 0 0
P= = ¥ 0.083 ¥ 400 = 8.3 bar m
V 4 At eq 2a – x a – 3x 2x x
\ N2O4(g)  2NO2(g) a
and a – 3x = 2x \ x=
8.3 – x 2x 5
8.3 + x = 11.6 3x 3
Moles of B reacted = ¥ 100 = ¥ 100 = 60%
\ x = 3.3 a 5
\ PNO2 = 2x = 6.6 bar 14. 2.0 mol of PCl5 were introduced in a vessel of 5.0 L ca-
11. What is the expression of KP for the following equilib- pacity at a particular temperature. At equilibrium, PCl5
rium 2NH3(g)  N2(g) + 3H2(g); if initially ‘a’ mole was found to be 35% dissociated into PCl3 and Cl2. The
of NH3 is present and at equilibrium ‘x’ mole of it de- value of Kc for the reaction is
composed and total equilibrium pressure is p? (a) 1.89 (b) 0.377
(c) 0.75 (d) 0.075.
27 p 2 x 4 9 px 2
(a) (b) Sol. (c)
16(a - x) 2 (a + x) 2 8(a - x)(a + x)
2 ¥ 35
Moles of PCl5 dissociated = = 0.7
3 px 2 3 p2 x2 100
(c) (d)
4(a - x) 2 8(a 2 - x 2 ) 2
Moles of PCl5 left undissociated = 2 – 0.7 = 1.3 mol
Sol. (a)
2NH3(g)  N2(g) + 3H2(g) 1.3 0.7 0.7
[PCl5] = M, [PCl3] = M, [Cl2] = M
Initially: a mole 0 0 5 5 5
x 3x
At equilibrium: (a – x) mole mole mole
2 2 Ê 0.7 ˆ Ê 0.7 ˆ
(a - x) x 3x [PCl3 ][Cl2 ] ÁË 5 ˜¯ ÁË 5 ˜¯
Partial pressure ¥P ¥P ¥P K= = = 0.75
(a + x) 2(a + x) 2(a + x) [PCl5 ] Ê 1.3 ˆ
ÁË ˜¯
5
( pN2 )1 ¥ ( PH2 )3 27 p 2 x 4
KP = 2
= 15. HI was heated in sealed tube at 400°C till the equilibri-
( pNH3 ) 16(a - x) 2 (a + x) 2 um was reached. HI was found to be 22% decomposed.
12. 2lCl(g)  l2(g) + Cl2(g) ; Kc = 0.14 The equilibrium constant for 2HI  H2 + I2 is
The initial concentration of lCl is 0.78 M. What will be (a) 1.99 (b) 0.0199
the equilibrium concentration of l2? (c) 0.0796 (d) 0.282
(a) 0.18 M (b) 0.21 M Sol. (b) 2HI Æ H2 + I2
(c) 0.39 M (d) 0.78 M
1 0 0
Sol. (b) 2lCl  l2 + Cl2
1–x
0.78 0 0
1 – 0.22 = 0.78 0.11 0.11
0.78 – 2x x x
22
x¥x x = 22% of 1 mole = ¥ 1 = 0.22
K= 100
(0.78 - 2 x) 2
x2 [H 2 ][I 2 ] 0.11 ¥ 0.11
0.14 = K= = = 0.0199
(0.78 - 2 x) 2 [HI]2 (0.78) 2
Exercise
equilibrium. The equilibrium constant for the reaction
leVel i of hydrolysis of ester will be
(a) 1 (b) 2 (c) 3 (d) 4
1. The equilibrium constant of a reaction is 20.0. At equi- 11. For the reaction, C(s) + CO2(g)  2CO(g), the partial
librium, the rate constant of forward reaction is 10.0. pressures of CO2 and CO are 2.0 and 4.0 atm respec-
The rate constant for backward reaction is tively at equlibrium. The KP for the reaction is
(a) 0.5 (b) 2.0 (a) 0.5 (b) 4.0 (c) 8.0 (d) 32.0
(c) 10.0 (d) 200.0 12. At 250°C the vapour density of PCl5 is 100 calculate
2. At a given temperature, the equilibrium constant for the the degree of dissociation at this temperature
reactions (a) 4 (b) .04 (c) .02 (d) 2
1 13. 6 gram hydrogen reacts with 9.023 ¥ 1023 chlorine
NO (g) + O2 (g) m NO2 (g) and 2 NO2 (g) m
2 molecules to form HCl. If total pressure of the reaction
2 NO (g) + O2 (g) are K1 and K2 respectively. If K1 is 4 is 800 mm then what will be the partial pressure of HCl?
¥ 10–3, then K2 will be (a) 400 mm (b) 533 mm
(a) 8 ¥ 10–3 (b) 16 ¥ 10–3 (c) 600 mm (d) 153.3 mm
(c) 6.25 ¥ 10 4
(d) 6.25 ¥ 106 14. 20% part of N2O4 is dissociated in NO2 at 1 atmospher-
3. Equilibrium constant for the reaction : 2NO(g) + Cl2(g) ic pressure. What is the value of Kp?
m 2NOCl (g); is correctly given by the expression (a) 0.29 (b) 16.0
(c) 1.60 (d) None of these
[2NOCl] [NOCl]2 15. In the reaction, A + B  C + D, the equilibrium con-
(a) K = (b) K =
[2NO] [Cl2 ] [NO]2 [Cl2 ] stant K is determined by taking 1 mole of A and 1 mole
of B as initial amounts. If 2 moles of A and three moles
[NO]2 [Cl]2 [NO]2 + [Cl]2
(c) K = (d) K = of B are taken, then the equilibrium constant will be
[NO]2 + [Cl2 ] [NOCl] (a) 2 times (b) 3 times
4. Molar concentration of 96 g of O2 contained in 2 L ves- (c) 6 times (d) Unchanged
sel is 16. Vaporisation of one mole of PCl5 is done in a 1 L con-
(a) 16 mol L–1 (b) 1.5 mol L–1 tainer. If 0.2 mole Cl2 is formed at equilibrium, then
(c) 4 mol L –1
(d) 24 mol L–1 what will be the value of equilibrium constant?
5. In which of the following reactions KP > KC? (a) 0.15 (b) 0.05 (c) 1.78 (d) 0.2
(a) N2(g) + 3H2(g) m 2NH3(g) 17. C(s) + H2O(g)  H2(g) + CO(g)
(b) H2(g) + I2(g) m 2HI(g) What will be the effect of pressure on the above equi-
(c) PCl3(g) + Cl2(g) m PCl5(g) librium process?
(d) 2SO3(g) m 2SO2(g) + O2(g) (a) Remains unaffected
6. At 1000 K, the value of KP for the reaction PCl5  (b) It will go in backward direction
PCl3 + Cl2 is 20R, then KC will be (c) It will go in forward direction
(a) 0.04 (b) 0.02 (c) 0.01 (d) 0.03 (d) Unpredictable
7. For the reaction N2O4  2NO, degree of dissociation 18. If pressure is increased in the following reaction: N2 + 3H2
is a. The number of moles at equilibirum will be m 2NH3, DH = – 22.4 kcal then the equilibrium will
(a) (1 – a)2 (b) (1 + a) (a) Be stable
(c) 3 (d) 1 (b) Shift towards left side
8. 4 mole of A are mixed with 4 mole of B, when 2 mole (c) Shift towards right side
of C are formed at equilibrium according to the reac- (d) Shift first towards left side, then right side
tion, A + B  C + D. The equilibrium constant is 19. In which case does the reaction go farthest to comple-
(a) 4 (b) 1 (c) ÷2 (d) ÷4 tion:
9. At a certain temperature, 2HI  H2 + I2 only 50% HI (a) K = 1 (b) K = 1010
–10
is dissociated at equilibrium. The equilibrium constant (c) K = 10 (d) 104
is 20. The equilibrium constant Kc for A(g) m B(g) is 1.1.
(a) 1.0 (b) 3.0 (c) 0.5 (d) 0.25 means
10. One mole of ethyl alcohol was treated with one mole of (a) [A]eq > [B]eq (b) [Aeq] < [B]eq
acetic acid at 25°C. 2/3 of the acid changes into ester at (c) [Aeq] = 1.1 M (d) [Beq] = 1.1 M
21. 0.1 mole of N2O4(g) was sealed in a tube under atmo- (a) I and III (b) II and IV
spheric conditions at 25°C. Calculate the number of (c) I and II (d) III and IV
mole of NO2(g) present, if the equilibrium N2O4(g)  30. In the reaction, N2(g) + 3H2(g)  2NH3(g)
2NO2(g), (Kp = 0.14) is reached after some time. the value of the equilibrium constant depends on
(a) 0.34 mole (b) 0.034 mole (a) volume of the reaction vessel
(c) 0.14 mole (d) 0.10 mole (b) total pressure of the system
22. What concentration of CO2 be in equilibrium with 2.5 (c) the initial concentration of nitrogen and hydrogen
¥ 10–2 mol L–1 of CO at 100°C for the reaction (d) the temperature
FeO(s) + CO(g)  Fe(s) + CO2(g) ; KC = 5.0 31. In the equilibrium reaction involving the dissociation
(a) 0.125 M (b) 12.5 M of CaCO3 CaCO3 (s)  CaO (s) + CO2 (g) the equilib-
(c) 0.125 mole (d) 2.5 M rium constant is given by
23. What is the % dissociation of H2S if 1 mole of H2S is PCO2
P ¥P
introduced into a 1.10 litre vessel at 1000 K? KC for the (a) CaO CO2 (b) CCaO ¥
reaction: 2H2S(g)  2H2(g) + S2(g) is 1 ¥ 10–6? PCaCO CCaCO3
3
(a) 1.3% (b) 5% PCaO
(c) (d) PCO2
(c) 10% (d) 0.1% PCaCO3
24. In the reaction, C(s) + CO2(g)  2CO(g), the equilib-
rium pressure is 12 atm. If 50% of CO2 reacts, calculate 32. Consider the reaction, PCl5 (g)  PCl3 (g) + Cl2(g) in
KP for reaction. a closed container at equilibrium at a fixed tempera-
(a) 12 atm (b) 8 atm ture. What will be the effect of adding more PCl5 on the
(c) 16 atm (d) 4 atm equilibrium concentration of Cl2(g)?
25. When a – D glucose is dissolved in water, it undergoes (a) It decreases
a partial conversion to b – D glucose to exhibit muta- (b) It increases
rotation. This conversion stops when 63.6% of glucose (c) It remains unaffected
is in b from. Assuming that equilibrium has been at- (d) It cannot be predicted without the value of Kp.
tained, calculate KC for mutarotation. 33. In which of the following options does the reaction go
(a) 1.747 (b) 2.4 almost to completion?
(c) 3.0 (d) 1.1 (a) K = 106 (b) K = 103
–6
26. For the reaction, A(g) + 2B(g)  2C(g), the rate constants (c) K = 10 (d) K = 10–12.
for the forward and the reverse reactions are 1 ¥ 10–4 34. XY2 dissociates as XY2(g)  XY(g) + Y(g). When the
and 2.5 ¥ 10–2 respectively. The value of equilibrium initial pressure is 600 mm of Hg, the total pressure at
constant, K for the reaction will be equilibrium developed is 800 mm of Hg. Therefore
(a) 1 ¥ 10–4 (b) 2.5 ¥ 10–2 pressure of Y at equilibrium is
–3
(c) 4 ¥ 10 (d) 2.5 ¥ 102 (a) 200 (b) 50 (c) 100 (d) 150
27. At a certain temperature, the equilibrium constant Kc 35. For the equilibrium 2SO2(g) + O2(g)  2SO3(g) the
is 16 for the reaction, SO2(g) + NO2(g)  SO3(g) + concentration of each substance is [SO2] = 0.60M, [O2]
NO(g). If 1.0 mol each of all the four gases is taken in = 0.82M and [SO3] = 1.90M, the Kc is
a 1 L container the concentration of NO2 at equilibrium (a) 1.2229 mol L–1 (b) 12.229 mol L–1
will be (c) 6.1145 mol L –1
(d) 18.22 mol L–1
(a) 1.6 mol L–1 (b) 0.8 mol L–1 36. Find out the value of KC for each of the following equi-
–1
(c) 0.4 mol L (d) 0.6 mol L–1 libria from the value of KP:
28. The following reactions are known to occur in the body: (i) 2NOCl (g)  2NO (g) + Cl2 (g); KP = 1.8 ¥ 10–2
CO2 + H2O  H2CO3  H+ + HCO3–1 at 500 K
If CO2 escapes from the system (ii) CaCO3 (s)  CaO(s) + CO2(g); Kp= 167 at
(a) pH will decrease 1073 K
(b) Hydrogen ion concentration will diminish The value of Kc are respectively
(c) H2CO3 concentration will remain unchanged (a) 4.4 ¥ 10–4 and 1.90 (b) 8.8 ¥10–4 and 3.8
(d) The forward reaction will be favoured (c) 4.4 ¥ 104 and 1.90 (d) 8.8 ¥104 and 3.8
29. For which of the following reactions, the degree of dis- 37. For the following equilibrium, KC = 6.3 ¥ 1014 at 1000 K
sociation cannot be calculated from the vapour density NO(g) + O3 (g)  NO2 (g) + O2(g)
data? Both the forward and reverse reactions in the equilib-
I. 2HI(g)  H2(g) + I2(g) rium are elementary bimolecular reactions. What is KC,
II. 2NH3(g)  N2(g) + 3H2(g) for the reverse reaction?
III. 2NO(g)  N2(g) + O2(g) (a) 15.9 ¥ 10–15 (b) 1.59 ¥ 10–15
–15
IV. PCl5(g)  PCl3(g) + Cl2(g) (c) 5 ¥ 10 (d) 9 ¥ 10–15
38. At 450 K, KP = 2.0 ¥1010/bar for the given reaction at for which K = 32 at 500 K. If initially pure BrCl is pres-
equilibrium. ent at a concentration of 3.3 ¥ 10–3 mol L–1, what is its
2SO2(g) + O2(g)  2SO3 (g) molar concentration in the mixture at equilibrium?
What is KC, at this temperature? (a) 3 ¥ 10–4 (b) 1 ¥ 10–4
–4
(a) 7.48 ¥ 1011 L mol–1 (b) 7.48 ¥ 10–11 L mol–1 (c) 1.5 ¥ 10 (d) 6 ¥ 10–4
(c) 3.78 ¥ 10–11 L mol–1 (d) 3.74 ¥ 1011 L mol–1 45. What are the values of DG0 and the equilibrium con-
stant for the formation of NO2 from NO and O2 at 298
39. A sample of HI(g) is placed in a flask at a pressure of
K
0.2 atm. At equilibrium, the partial pressure of HI(g) is
0.04 atm. What is Kp for the given equilibrium? 1
NO(g) + O2(g)  NO2(g)
2HI(g)  H2(g) + I2(g) 2
(a) 6 (b) 16 (c) 4 (d) 2 where DG 0f NO 2 = 52.0 kJ/mol
40. A mixture of 1.57 mol of N2, 1.92 mol of H2, and 8.13 DG 0f NO = 87.0 kJ/mol
mol of NH3 is introduced into a 20 L reaction vessel at
500 K. At this temperature, the equilibrium constant, DG 0f (O 2 ) = 0 kJ/mol
KC for the reaction N2 (g) + 3H2 (g)  2NH3(g) is 1.7 (a) 35 kJ mol–1 and 1.365 ¥ 106
¥ 102. Is the reaction mixture at equilibrium? (b) –35 kJ mol–1 and 1.365 ¥ 10–6
If not, what is the direction of the net reaction? (c) –350 kJ mol–1 and 1.3 ¥ 106
(a) Not at equilibrium, forward shift (d) –35 kJ mol–1 and 1.365 ¥ 106
(b) Not at equilibrium, backward shift 46. A reaction mixture containing H2, N2 and NH3 has par-
(c) Cannot be predicted tial pressures 2 atm, 1 atm and 3 atm, respectively at
(d) In equilibrium 725 K. If the value of Kp for the reaction, N2(g) + 3H2(g)
41. The equilibrium constant expression for a gas reaction  2NH3(g) is 4.28 ¥ 10–5 atm–2 at 725 K, in which
4 5 direction the net reaction will go?
is, KC = [NH3 ] [O 2 ] (a) Forward
[NO] [H 2O]6
4
(b) Backward
The balanced chemical equation corresponding to this (c) No net reaction
expression is (d) Direction of reaction cannot be predicted.
(a) 4NO(g) + 6H2O (g)  4NH3(g) + 5O2(g) 47. 2.0 mol of PCl5 were introduced in a vessel of 5.0 L ca-
(b) 4NH3(g) + 5O2(g)  4NO(g) + 6H2O (g) pacity at a particular temperature. At equilibrium, PCl5
(c) Both (a) and (b) was found to be 35% dissociated into PCl3 and Cl2. The
(d) None of these value of Kc for the reaction is
42. A sample of pure PCl5 was introduced into an evacu- (a) 1.89 (b) 0.377 (c) 0.75 (d) 0.075.
ated vessel at 473 K. After equilibrium was attained, 48. In the reversible reaction A + B  C + D, initially 1
concentration of PC15 was found to be 0.5 ¥ 10–10 mol M of A and B taken the concentration of each C and D
L–1. If value of KC is 8.3 ¥10–3, what are the concentra- at equilibrium was 0.8 mole/L–1, then the equilibrium
tions of PC13 and C12 at equilibrium? constant Kc will be
PCl5(g)  PCl3(g) + Cl2(g) (a) 6.4 (b) 0.64 (c) 1.6 (d) 16.0
(a) 0.08 M (b) 0.04M 49. 4 moles of A are mixed with 4 moles of B. At equilib-
(c) 0.2 M (d) 0.02 M rium for the reaction
43. Equilibrium constant, KC for the reaction A + B  C + D, 2 moles of C and D are formed. The
N2(g) + 3H2 (g)  2NH3 (g) at 500 K is 0.061 equilibrium constant for the reaction will be
At a particular time, the analysis shows that composi- (a) 1/4 (b) ½ (c) 1 (d) 4
tion of the reaction mixture is 3.0 mol L–1 N2, 2.0 mol 50. On a given condition, the equilibrium concentration of
L–1 H2 and 0.5 mol L–1 NH3. Is the reaction at equi- HI, H2, I2 are 0.80, 0.10 and 0.10 mole L–1. The equi-
librium and if not in which direction does the reaction librium constant for the reaction H2 + I2  2HI will be
tend to proceed to reach equilibrium? (a) 64 (b) 12 (c) 8 (d) 0.8
(a) At equilibrium 51. In which of the following, the reaction proceeds to-
(b) Not at equilibrium, backward shift wards completion?
(c) Not at equilibrium, forward shift (a) K = 103 (b) K = 10–2
(d) Can not be predicted (c) K = 10 (d) K = 1
44. Bromine monochloride, BrCl decomposes into bro- 52. A reversible chemical reaction having two reactants in
mine and chlorine and reaches the equilibrium, equilibrium. If the concentration of the reactants are
2BrCl (g)  Br2 (g) + Cl2(g) doubled, then the equilibrium constant will
(a) Also be doubled (b) Be halved (c) NO = 0.352 mol, Br2 = 0.178 mol
(c) Become one-fourth (d) Remain the same (d) NO = 0.0352 mol, Br2 = 0.0178 mol
53. The equilibrium constant in reversible reaction at a 5. At 450 K, KP= 2.0 ¥ 1010/bar for the given reaction at
given temperature equilibrium. 2SO2(g) + O2(g)  2SO3 (g) What is KC
(a) depends on the initial concentration of the reac- for 2SO3  2SO2 + O2
tants. 1 1
(a) (b)
(b) depends on the concentration of the products and 7.47 ¥ 1011 7.47 ¥ 1012
reactants at equilibrium.
1 1
(c) does not depend on the initial concentrations. (c) (d)
(d) it is not characteristic of the reaction. 7.47 ¥ 1014 7.47 ¥ 108
54. Pure ammonia is placed in a vessel at temperature 6. A sample of HI(g) is placed in flask at a pressure of
where its dissociation constant (A) is appreciable. At 0.2 atm. At equilibrium, the partial pressure of HI(g) is
equilibrium 0.04 atm. What is KC for the given equilibrium at 427°C
(a) Kp change with pressure. 2HI(g)  H2(g) + I2(g)
(b) Kp does not change with pressure. (a) 6 (b) 16 (c) 4 (d) 2
(c) Concentration of NH3 does not change with pres- 7. In equilibrium reaction, x moles of the reactant A de-
sure. compose to give 1 mole each of C and D. If the frac-
(d) Concentration of H2 is less than that of N2. tion of A decomposed at equilibrium is independent of
initial concentration, then the value of x will be
(a) 1 (b) 2 (c) 3 (d) 4
leVel ii 8. One mole of H2O and one mole of CO are taken in 10
L vessel and heated to 725 K. At equilibrium, 40% of
1. For the equilibrium 2SO2(g) + O2(g)  2SO3(g) the water (by mass) reacts with CO according to the equa-
concentration of each substance is [SO2] = 0.60M, [O2] tion,
1 H2O(g) + CO(g)  H2 (g) + CO2(g)
= 0.82M and [SO3] = 1.90 M, the KC is for SO2 + O 2
 SO 2 What is the value of equilibrium constant (Kc) for the
3
(a) 1.2229 (b) 3.5 reaction?
(c) 6.1145 (d) 18.22 (a) 44 (b) 4.4 (c) 0.44 (d) 2.22
2. For the reaction, CO(g) + 2H2 (g) m CH3OH (g) H2 9. A sample of pure PCl5 was introduced into an evacu-
is introduced into a five litre flask at 327°C, containing ated vessel at 473 K. After equilibrium was attained,
0.2 mole of CO (g) and a catalyst till the pressure is concentration of PC15 was found to be 0.5 ¥ 10–1 mol
4.92 atmosphere. At this point 0.1 mole of CH3OH(g) L–1. If value of KC is 8.3 ¥ 10–3, what are the concentra-
is formed. Calculate KP. tions of PC13 and C12 at equilibrium?
(a) 0.115 atm–2 (b) 1.15 atm–2 PCl5(g)  PCl3(g) + Cl2(g)
–2
(c) 2 atm (d) 3.15 atm–2 (a) 0.08 M (b) 0.04 M
3. If a mixture of 0.482 mol N2 and 0.933 mol of O2 is (c) 0.2 M (d) 0.02 M
placed in a 10 L reaction vessel and allowed to form 10. H2(g) + Br2(g)  2HBr(g) KC = 16 ¥ 10–6
N2O according to the reaction 2N2g + O2g  2N2Og at Find the equilibrium pressure of H2 gas if 10.0 bar of
a temperature for which KC = 2.0 ¥10–37 HBr is introduced into a sealed container at 1024 K.
The composition of equilibrium mixture are (a) 2.8 ¥ 103 (b) 5.2 ¥ 10–3
(a) N2 = 0.482 mol/L, O2 = 0.0933 mol/L, N2O = 6.6 (c) 2.5 ¥ 10 –3
(d) 2 ¥ 10–3
¥ 10–21 mol/L – –
11. X2 + X  X3 (x = iodine)
(b) N2 = 0.482 mol/L, O2 = 0.933 mol/L, N2O = 6.6 ¥ This reaction is set up in aqueous medium. We start
10–21 mol/L with 1 mol of X2 and 0.5 mol of X – in 1 L flask. After
(c) N2 = 0.0482 mol/L, O2 = 0.0933 mol/L, N2O = 6.6 equilibrium is reached, excess of AgNO3 gave 0.25 mol
¥ 10–21 mol/L of yellow ppt. equilibrium constant is
(d) N2 = 0.0482 mol/L, O2 = 0.0931 mol/L, N2O = 8.8 (a) 1.33 (b) 2.66 (c) 2.00 (d) 3.00
¥10–21 mol/L 12. 0.15 mole of CO taken in a 2.5 litre flask is maintained
4. When 0.087 mol of NO and 0.0437 mol of Br2 are at 750 K alongwith a catalyst so that the following re-
mixed in a closed container at constant temperature, action can take place.
0.0518 mol of NOBr is obtained at equilibrium. The CO(g) + 2H2 (g) m CH3OH(g)
equilibrium amount of NO and Br2 are: Hydrogen is introduced until the total pressure of the
(a) NO = 0.352 mol, Br2 = 0.0178 mol system is 8.5 atm at equilibrium and 0.08 mole of
(b) NO = 0.0352 mol, Br2 = 0.178 mol methanol is formed. Calculate Kp.
(a) 0.05 atm–2 (b) 2.15 atm–2 present at equilibrium at 700 K, what are the concen-
–2
(c) 2 atm (d) 0.005 atm–2 tration of H2(g) and I2(g), assuming that we initially
13. DG° for the dissociation of the dimer (A2  2A) in started with HI(g) and allowed it to reach equilibrium
benzene solution at 27°C is 6.909 kcal/mol. If 8 moles at 700 K?
of A is dissolved in 10 litre of benzene at 27°C, then (a) 0.068 M (b) 0.034 M
what is the equilibrium concentration of dimer (A2)? (c) 0.136 M (d) 0.68 M
(Given : R = 2 Cal/mol K)? 21. What is the equilibrium concentration of each of the
(a) 2 ¥ 10–3 (b) 0.4 substances of RHS in the equilibrium when the initial
(c) 0.04 (d) 0.02 concentration of ICl was 0.78 M?
14. When C2H5OH and CH3COOH are mixed in equivalent 2ICl(g)  I2 (g) + Cl2 (g); KC = 0.14
proportion, equilibrium is reached when 2/3 of acid and (a) 0.21 M (b) 0.42 M (c) 4.2 M (d) 2.1 M
alcohol are used. How much ester will be present when 22. KP = 0.04 atm at 899 K for the equilibrium shown be-
2g molecule of acid were to react with 2g molecule of low. What is the equilibrium concentration of C2H6
alcohol? when it is placed in a flask at 4.0 atm pressure and al-
(a) 1.33 g molecule (b) 1.5 g molecule lowed to come to equilibrium?
(c) 2 g molecule (d) 1.8 g molecule
C2H6 (g)  C2H4 (g) + H2 (g)
15. When sulphur in the form of S8 is heated at 900 K, the
initial pressure of one atm falls by 29% at equilibrium. (a) 7.24 atm (b) 3.62 atm
This is because of conversion of some S8 to S2. Find the (c) 1 atm (d) 1.5 atm
value of equilibrium constant for the reaction S8g  23. One of the reaction that takes place in producing steel
S2g. from iron ore is the reduction of iron(II) oxide by car-
(a) 1.16 atm3 (b) 0.71 atm3 bon monoxide to give iron metal and CO2. FeO (s) +
(c) 2.55 atm 3
(d) 5.1 atm3 CO (g)  Fe (s) + CO2 (g); KP = 0.265 atm at 1050K.
16. In a system, A(s)  2B(g) + 3C(g). If the concentration What are the equilibrium partial pressures of CO and
of C at equilibrium is increased by a factor 2, it will CO2 respectively at 1050 K if the initial partial pres-
cause the equilibrium concentration of B to change to sures are: pCO= 1.4 atm and PCO2 = 0.80 atm?
(a) two times of its original value. (a) [PCO] = 1.739 atm and PCO2 = 0.461 atm
(b) one-half of its original value.
(b) [PCO] = 17.39 atm and PCO2 = 0.461 atm
(c) 2 2 times of its original value.
(c) [PCO] = 4.79 atm and PCO2 = 0.46 atm
1
(d) times of its original value. (d) [PCO] = 2.739 atm and PCO2 = 1.461 atm
2 2
17. For the equilibrium: 24. The equilibrium constant for the following reaction is
25 at 1024 K
LiCl. 3NH3(s) m LiCl. NH3(s) + 2NH3(g)
H2(g) + Br2(g)  2HBr(g)
Kp = 9 atm2
Find the equilibrium pressure of H2 gas if 10.0 bar of
at 40°C. A 5 litre vessel contains 0.1 mole of LiCl. HBr is introduced into a sealed container at 1024 K.
NH3. How many mole of NH3 should be added to the (a) 10/7 (b) 4.9
flask at this temperature to derive the backward reac- (c) 7/10 (d) 5/16
tion for completion? 25. The heat of reaction for an endothermic reaction in
(a) 0.7837 mole (b) 1.7837 mole equilibrium is 1200 cal more than at constant pressure
(c) 3.2 mole (d) 2.00 mole at 300 K. Calculate the ratio of equilibrium constants
18. For the reaction Ag (CN)–2 m Ag+ + 2 CN–, the KC KP and KC.
at 25°C is 4 ¥ 10–19. Calculate [Ag+] in solution which (a) 1.648 ¥ 10–3 (b) 2.47 ¥ 10–8
was originally 0.1 M in KCN and 0.03 M in AgNO3. (c) 4.45 ¥ 10 –5
(d) 4.4 ¥ 10–3
(a) 0.75 ¥ 10–18 M (b) 0.50 ¥ 10–10 M 26. For the reaction,
–15
(c) 0.20 ¥ 10 M (d) 0.25 ¥ 10–20 M
–1 1 2HI(g)  H2(g) + I2(g)
19. DG° = 77.77 kJ mol at 1000 K for the reaction
1 2 The degree of dissociation (a) of HI(g) is related to
N2(g) + O2(g) m NO(g). What is the partial pres- equilibrium constant, Kp by the expression
2
sure of NO under equilibrium at 1000 K for air at 1 atm 1+ 2 Kp 1 + 2K p
pressure containing 80% N2 and 20% O2 by volume ? (a) (b)
2 2
(a) 3.47 ¥ 10–5 atm (b) 2.47 ¥ 10–8 atm
–15
(c) 4.45 ¥ 10 atm (d) 0.44 ¥ 10–20 atm 2K p 2 2K p
(c) (d)
20. At 700 K, equilibrium constant for the reaction: H2 (g) 1 + 2K p 1+ 2 Kp
+ I2(g)  2HI (g) is 54.8. If 0.5 mol L–1 of HI(g) is
27. At temperature T, a compound AB2(g) dissociates ac- 4. Match the chemical reaction in equilibrium (Column I)
cording to the reaction, 2AB2(g)  2AB(g) + B2(g) with the pressure dependent of degree of dissociation
with degree of dissociation a, which is small compared of the reaction (Column II):
with unity. The expression for KP, in terms of a and the
total pressure, PT is Column I Column II
PT a 3 2 3 P a2 (a) N2(g) + 3H2 (g)  2NH3 (g) (p) xµ P

(a) (b) PT a (c) PT a (d) T
2 3 3 2
1
28. The value of KP is 1 ¥ 10–3 atm–1 at 25°C for the reac- (b) 2SO2(g) +O2 (g)  2SO3(g) (q) x µ
P
tion: 2NO + Cl2 m 2NOCl. A flask contains NO at
0.02 atm and at 25°C. Calculate the mole of Cl2 that (c) PCl5(g)  PCl3 (g) + Cl2 (g) (r) xµP
must be added if 1% of the NO is to be converted to
NOCl at equilibrium. The volume of the flask is such (d) N2 + O2  2NO (s) x µ P0
that 0.2 mole gas Produce 1 atm pressure at 25°C. (Ig- (t) Kp = Kc
nore Probable association of NO to N2O2).
(a) 0.02042 (b) 2.01049 5. Match the following:
(c) 0.01021 (d) 0.04042
Column I Column II
(a) N2g + 3H2g  2NH3g (p) Dng > 0
leVel iii
(b) PCl5g  PCl3g + Cl2g (q) kp < kc
1. Match the reactions of Column I with the relations in (c) 2SO3g  2SO2g + O2g (r) kp not defined
Column II. (d) CH3COOC2H5 l (s) kp > kc
Column I Column II + H2O l  CH3COOHl
+ C2H5OHl
(a) H2(g) + I2(g)  2HI(g) (p) Kp = Kc(RT)
(Assume temperature = 25°C)
(b) N2(g) + 3H2(g)  2NH3(g) (q) Kp = Kc(RT)2
(c) PCl5(g)  PCl3(g) + Cl2(g) (r) Kp = Kc(RT)–2 Assertion and Reason
(d) NH4HS(s)  NH3(g) + (s) Kp = Kc Code:
H2S(g) (a) Statements 1 and 2 are True. Statement 2 is the correct
(t) Kp = Kc(RT)–1 explanation for Statement 1.
(b) Statement 1 and 2 are True. Statement 2 is NOT the
2. Match Column I with Column II. correct explanation for Statement 1.
Column I Column II (c) Statement 1 is True, Statement 2 is False.
(a) Q = K (p) Reaction is nearer to completion. (d) Statement 1 is False, Statement 2 is True.
6. Statement 1: A catalyst does not alter the equilibrium
(b) Q < K (q) Reaction is not at equilibrium.
constant of a reaction.
(c) Q > K (r) Reaction is fast in forward direction. Statement 2: The catalyst forms a complex with the
(d) K >> 1 (s) Reaction at equilibrium. reactants and provides an alternate path with lower en-
(t) Rate of forward reaction ergy of an activation for the reaction. The forward and
= rate of back ward reaction. reverse reaction are affected to the same extent.
7. Statement 1: Haber’s synthesis of NH3 is carried out
3. Match Column I with Column II and select the an- in the presence of catalyst.
swers from the given codes: Statement 2: The catalyst shifts the position of the
Column I (Mixture) Column II (pH) equilibrium of the reaction.
(a) Keq < 1 (p) Affected by temperature N2(g) + 3H2(g)  2NH3(g) to the product side.
(b) Degree of disso- (q) Affected by pressure 8. Statement 1: Addition of a non-reacting gas at con-
ciation stant volume and constant temperature to a container
containing gas (X), does not change the partial pressure
(c) Equilibrium (r) Kf < Kb
constant of gas (X).
Statement 2: Addition of non-reacting gas to a con-
(d) Melting of ice (s) Kf > Kb tainer at constant volume and constant temperature re-
(t) Kf /Kb sults in increase in total pressure of the container.
9. Statement 1: The graph between concentration and 1

time is as follows:  SO3(g) + heat
19. Statement 1: SO 2(g) + O 2(g) 
2
Forward reaction is favoured at high temperature and
Concentration low pressure.
Statement 2: Reaction is exothermic in forward direc-
tion.
Time
Comprehension I
Its graph shows a reversible reaction. For the reaction CaCO3(s)  CaO(s) + CO2(g), KP(1000 K)
Statement 2: In a reversible reaction the concentration = 0.059 and KP (1100 K) = 0.08. Exactly 10 g of CaCO3
of reactants and products becoming constant after a is placed in a 10 L container at 1000 K. The equilibrium is
certain time. reached. Assume that air contains 10% by volume of CO2.
10. Statement 1: Addition of an inert gas at constant pres- 20. The mass of CaCO3 which remains unreacted at 1000
sure to dissociation equilibrium of PCl5(g)  PCl3(g) K is
+ Cl2(g) favours forward reaction. (a) 1.485 g (b) 0.325 g (c) 9.282 g (d) 4.56 g
a 2V 21. The ratio of degree of dissociation of CaCO3 at 1100°K
Statement 2: K c = for dissociation equilibrium
1- a and 1000 K is
of PCl5, where a is degree of dissociation of PCl5 (a) 4.256 (b) 1.356 (c) 5.286 (d) 3.456
11. Statement 1: The reaction: 2NO(g) + O2(g)  22. The temperature at which CaCO3 dissociates freely in
2NO2(g) is favoured in the forward direction with in- air is
crease in pressure. (a) 415°C (b) 913.2°C
Statement 2: When pressure is increased then the equi- (c) 8, 05. 4°C (d) 43°C
librium shifts in those direction where V or number of 23. The value of DH is
moles decreases. (a) 6699 cal (b) 2399 cal
12. Statement 1: Addition or removal of solid reactant/ (c) 4599 cal (d) 2499 cal
products does not alter the existing equilibrium. Comprehension II
Statement 2: Concentration of solid substances re- Let DG° be the difference in free energy of the reaction when
mains constant. all the reactants and products are in the standard state (1 at-
13. Statement 1: A catalyst does not affect the equilibrium mospheric pressure and 298 K) and KC and KP be the ther-
constant. modynamic equilibrium constant of the reaction. Both are re-
Statement 2: Equilibrium constant depends on tem- lated to each other at temperature T by the following relation:
perature.
DG° = –2.303 RT log KC
14. Statement 1: The equilibrium constant for a reaction
having positive DH° increase with increase of tempera- and DG° = –2.303 RT log KP (incase of ideal gas)
ture. This equation represents one of the most important results
Statement 2: The temperature dependence of the equi- of thermodynamics and relates to the equilibrium constant of
librium constant is related to DH° and not DS° for the a reaction to a thermodynamic property.
reaction. It is sometimes easier to calculate the free energy in a re-
15. Statement 1: DG = DG° + 2.303 RT log10Q, where Q is action rather than to measure the equilibrium constant.
reaction quotient. Standard free energy change can be thermodynamically
Statement 2: Q may be greater or lesser than K or calculated as
equal to K if DG = 0. DG° = DH° – TDS°
16. Statement 1: A catalyst increased the equilibrium con- Here DH° = standard enthalpy change
stant at any fixed temperature. DS° = standard entropy change.
Statement 2: By the uses of catalyst, the rate of the 24. Which of the following statement is correct for a re-
reaction increases. versible process in state of equilibrium?
17. Statement 1: In the Haber process, (a) DG = –2.303 RT log K
N2 + 3H2  2NH3; DH = –ve (b) DG = 2.303 RT log K
Then concentration of NH3 increases by decreasing the (c) DG° = –2.303 RT log K
temperature and increasing the pressure. (d) DG° = 2.303 RT log K
Statement 2: For an exothermic reaction, equilibrium 25. At 490°C, the value of equilibrium constant; KP is 45.9
constant increases by increasing the temperature. the reaction
18. Statement 1: For the reaction 2NH3(g)  N2(g) + H2(g) + I2(g)  2HI(g)
3H2(g), the unit of Kp will be atm. Calculate the value of DG° for the reaction at that tem-
Statement 2: Unit of Kp is (atm)Dn perature?
(a) –3.5 kcal (b) 3.5 kcal 30. For the reaction,
(c) 5.79 kcal (d) –5.79 kcal NH2COONH4(s)  2 NH3(g) + CO2(g)
26. Calculate the equilibrium concentration ratio of C to The equilibrium constant KP = 2.9 ¥ 10–5 atm3. The
A if 2.0 mol each of A and B were allowed to come to total pressure of gases at equilibrium when 1 mole of
equilibrium at 300 K. reactant was heated will be
A+BC+D DG° = 460 Cal (a) 0.0194 atm (b) 0.0388 atm
(a) 1.0 (b) 0.5 (c) 0.8 (d) 0.679 (c) 0.0580 atm (d) 0.0667 atm
Comprehension III Comprehension IV
If the composition of the system does not change with time, A chemical reaction in the laboratory is carried out under the
the system is said to be in chemical equilibrium. It is the state condition of constant temperature and pressure. The condi-
in which net reaction of a system is zero. In other words, we tion of spontaneity in terms of enthalpy and entropy are, re-
can say that in reversible reactions, a stage is reached when spectively, DH < 0 and S > 0 whereas condition of equilib-
the rate of transformation of reactants into products equals rium are, respectively, DH = 0 and DS = 0. An endothermic
the rate of transformation of products into reactants. At this reaction is driven by increase in entropy, i.e., increase in dis-
stage, the composition of reactants and products does not orderness. The two criteria combined together, the condition
change with time. This does not mean that the reaction has of reversibility and irreversibility are as follows:
ceased, as both reverse and forward reactions are still tak- DGP, T = DH – TDS £ 0, where ‘equal to’ sign refers to
ing place but with equal place. Such equilibria are called dy- reversibility and ‘less than’ sign refers to irreversibility. Re-
namic equilibria. versibility is the condition of equilibrium whereas irrevers-
Let us consider a reaction of the type, ibility is the condition of spontaneity. A reversible reaction
A(g) + B(g)  C(g) + D(g) is characterised by equilibrium constant (K), the magnitude
[C ][ D] of which measures the position of equilibrium, i.e., how far a
KC = chemical reaction will go to completion before attainment of
[ A][ B]
equilibrium. The position of equilibrium constant of a reac-
where KC is equilibrium constant when the ratio of the con-
tion with temperature is given by Van Hoff equation of ther-
centrations of the product to reactants.
modynamics which is as follows:
PC ¥ PD This equation can be integrated assuming DH to be inde-
KP =
PA ¥ PB pendent of temperature. Within the short interval of tempera-
where KP is the equilibrium constant for the ratio of partial ture.
pressure and of products to reactants. The relation between For a gaseous equilibria k can be expressed Kc and Kp re-
KP and KC is as follows: lated as
KP = KC(RT)Dn where the symbols have their usual meanings. Dng of a re-
action can be found out from the unit of equilibrium, though
27. The mass ratio of steam and hydrogen is found to be
1 : 2 at equilibrium. it is not customary to write unit of equilibrium constant. An-
other way of finding Dng of a reaction is to use the equation,
3 Fe (s) + 4 H2O(g)  Fe3O4(s) + 4 H2(g)
DH = DE + Dng RT
The value of equilibrium constant (KC) for the above
reaction is where the terms have their usual meanings.
(a) 3.05 ¥ 103 (b) 1.05 ¥ 105 Knowing K and reaction quotient, it is possible to calcu-
(c) 0.75 ¥ 10 2
(d) 2.42 ¥ 107 late free energy change of a reaction using the equation:
1 1 1 DG = DG0 + RT ln Q
28. KC for the reaction N 2 (g) + O 2 (g) + Br2 (g) 
2 2 2 At equilibrium Q = K and DGP, T = 0
NOBr(g) from the following information at 298 K: So, DG0 = –RT ln K where DG0 is the free energy change
2NO(g)  N2(g) + O2(g) K1 = 2.4 ¥ 1030 of the reaction in the standard state.
1 The standard state of a substance is defined as the state of
NO(g) + Br2(g)  NOBr(g) K2 = 1.4 unit activity at 25°C. In the case of solution of a substance,
2
(a) 3.15 ¥ 10–9 (b) 6.35 ¥ 5 10–18 the activity is taken to be molar concentration while for a gas
(c) 9.03 ¥ 10–16
(d) 17 ¥ 10–17 it is pressure in atm. The standard free energy of an element
29. The equilibrium constant for the reaction 2SO2 + O2  is taken to be zero.
2 SO3 at 1000 K is 3.5. What will the partial pressure of 31. At 27°C the heat of reaction at constant pressure is 600
oxygen gas have to be to give equal moles of SO2 and cals more than that at constant volume. The ratio of Kp
SO3? to Kc of the reaction is
(a) 0.29 atm (b) 3.5 atm (a) 24.63 (b) (24.63)2
(c) 0.53 atm (d) 1.87 atm (c) 0.6 (d) 0.36
32. For the reaction, (i) find out the amount of each gas at equilibrium.
NH4HS(s)  NH3(g) + H2S(g) (ii) After equilibrium is reached, another 0.34 mole of
Kp and Kc are interrelated as CO2 and 0.34 mole of H2 are added to the reaction
Kc mixture. Find the composition of the mixture at
(a) Kp = KcRT (b) K p = the new equilibrium state.
( RT ) 2 41. The equilibrium constant for the reaction H2 + I2 
(c) Kp = Kc(RT)2 (d) Kp = Kc/RT 2HI; is found to be 64 at 450°C. If 6 mole of hydrogen
33. The Kp of a reaction is 10 atm–2 at a temperature T on are mixed with 3 mole of iodine in a litre vessel at this
Kelvin scale. Hence, temperature; what will be the concentration of each of
(a) Kp = Kc (b) Kp < Kc the three components, when equilibrium is attained? If
(c) Kp > Kc (d) Can’t be predicted the volume of reaction vessel is reduced to half; then
what will be the effect on equilibrium?
34. The Kc of a reaction is 4.0 mol2 L–2 at 27°C. Hence Kp 42. 5 gm of PCl5 were completely vaporised at 250°C in
of the reaction is a vessel of 1.9 L capacity. The mixture at equilibrium
(a) 4 (0.0821 ¥ 300)2 atm2 exerted a pressure of one atmosphere. Calculate the de-
(b) 4 (2 ¥ 300)2 atm2 gree of dissociation and KC.
4 43. If a mixture of N2 and H2 in the ratio 1 : 3 at 50 atmo-
(c)
(0.0821 ¥ 300) 2 atm -2 sphere and 650°C is allowed to react till equilibrium
is reached. Ammonia present at equilibrium was at 25
4
(d) atm pressure. Calculate the equilibrium constant for the
(2 ¥ 300) 2 atm 2 reaction,
Integer-Answer-Type Questions N2(g) + 3H2(g)  2NH3(g)
35. For the equilibrium N2O4  2NO2 44. A mixture of SO3, SO2 and O2 gases is maintained in
a 10.0 L flask at a temperature at which equilibrium
(GN0 2O4 ) 298K =100 kJ mol-1 and (GNO
0
)
2 298K
= 50 kJ mol-1. constant Kc for the reaction
When 5 mole/L of each in taken, calculate the value of 2SO2(g) + O2(g)  2SO3(g) is 100.
DG in KJ for the reaction at 298 K. (i) If the number of moles of SO2 and SO3 in the
36. When NO and NO2 are mixed, the following equilibria flask are equal, how many moles of O2 are pres-
are readily obtained; ent?
2NO2  N2O4 Kp = 6.8 atm–1 (ii) If the number of moles of SO3 in the flask is twice
and NO + NO2  N2O3 the number of mole of SO2, how many moles of
In an experiment when NO and NO2 are mixed in the O2 are present?
ratio of 1 : 2, the total pressure was 5.05 atm and the 45. The equilibrium constant Kp of the reaction 2SO2(g)
partial pressure of N2O4 was 1.7 atm. Calculate the + O2(g)  2SO3(g) is 900 atm–1 at 800 K. A mixture
equilibrium partial pressure of NO in atmospheres ¥ 10. containing SO3 and O2 having initial partial pressures
37. At 25°C and 1 atmospheric pressure, for the equilib- of 1 atm and 2 atm, respectively, is heated at constant
rium N2O4(g)  2NO2(g) the partial pressures in equi- volume to equilibrate. Calculate the partial pressure of
librium mixture of gaseous N2O4 and NO2 are 0.7 and each gas at 800 K.
0.3 atm respectively. Calculate the partial pressure of 46. H2S dissociates according to the equation 2H2S (g)
N2O4 in atm when they are in equilibrium at 25°C and  2H2(g) + S2(g). If a is the degree of dissocia-
the total pressure of 10 atm tion of H2S, show that Kp of the reaction is given as
38. For the reaction, CO2(g) + H2(g)  CO(g) + H2O(g), a3 p
Kp =
K is 0.63 at 700°C and 1.66 at 1000°C. What is the av- 2(1 - a ) 2 (1 + a /2)
erage H° in Kcal for the temperature range considered?
At 1125°C, the value of a is found to be 0.31 when
39. 16 moles of H2 and 4 moles of N2 are sealed in a 1 L
the equilibrium pressure is 1 atm. Determine the values
vessel. The vessel is heated at a constant temperature
of Kp and Kc.
until the equilibrium is established, it is found that the
47. COCl2 gas dissociates according to the equation COCl2
pressure in the vessel has fallen to 9/10 of its original
 CO + Cl2. When COCl2 is heated to 724 K at 1atm,
value. Calculate newly concentration of N2 in mol L–1
the density of gas mixture at equilibrium was found to
N2(g) + 3H2(g)  2NH3(g) be 1.162 g L–1. Calculate (a) the degree of dissociation
Subjective Questions and (b) Kp of the reaction.
48. The density of an equilibrium mixture of N2O and NO2
40. At 700 K, CO2 and H2 react to form CO and H2O. For at 1 atm and 348 K is 1.84 g dm–3. Calculate the equi-
this process, K is 0.11. If a mixture of 0.45 mole of CO2 librium constant of the reaction
and 0.45 mole of H2 is heated to 700 K, then
N2O4 (g)  2NO2 (g) (a) 1.8 atm (b) 3 atm

49. For the reaction, N2O5(g)  2NO2 (g) + 0.5O2 (g), (c) 0.3 atm (d) 0.18 atm
calculate the mole fraction of N2O5(g) decomposed at 6. The equilibrium constant (Kc) for the reaction
constant volume and temperature, if the initial pressure N2(g) + O2(g)  2NO(g) at temperature T is 4 ¥ 10–4.
is 600 mm-Hg and the pressure at any time is 960 mm The value of Kc for the reaction
Hg. Assuming ideal gas behaviour. 1 1
50. When 3.06 g of solid NH4HS is introduced into a 2 L NO(g)  N2(g) + O2(g) at the same temperature is
2 2 [AIEEE 2012]
evacuated flask at 270°C, 30% of the solid decomposes
into gaseous ammonia and hydrogen sulphide. (a) Cal- (a) 0.02 (b) 2.5 ¥ 102
culate Kc and Kp for the reaction at 27°C. (b) What will (c) 4 ¥ 10–4 (d) 50
happen to equilibrium when more solid NH4HS is in- 7. For the reaction,
troduced into the flask? 1
SO2(g) + O2(g)  SO3(g),
2
preVious years’ questions If KP = Kc(RT)x where the symbols have usual mean-
of Jee (main & aDVanceD) ings, then the value of x is (assuming ideality)
[AIEEE 2014]
1. Phosphorus pentachloride dissociates as follows, in a (a) –1 (b) –1/2 (c) 1/2 (d) 1
closed reaction vessel, PCl5(g)  PCl3(g) + Cl2(g). If to-
8. The standard Gibbs energy change at 300 K for the
tal pressure at equilibrium of the reaction mixture is P
reaction 2A Æ B + C is 2494.2 J. At a given time,
and degree of dissociation of PCl5 is x, the partial pres-
1
sure of PCl3 will be [AIEEE 2006] the composition of the reaction mixture is [A] = ,
2
Ê x ˆ Ê x ˆ 1
[B] = 2 and (C) = . The reaction proceeds in the
(a) Á P (b) Á P
Ë 1 - x ˜¯ Ë x + 1˜¯ 2
[R = 8.314 J/K/mol, e = 2.718] [JEE Main 2015]
Ê 2x ˆ Ê x ˆ
(c) Á P (d) Á P (a) Forward direction because Q > KC
Ë 1 - x ˜¯ Ë x - 1˜¯ (b) Reverse direction because Q > KC
2. The equilibrium constant for the reaction, (c) Forward direction because Q < KC
1 (d) Reverse direction because Q < KC
SO3(g)  SO2(g) + O2(g)
2
JEE Advanced
is Kc = 4.9 ¥ 10–2. The value of Kc for the reaction
2SO2(g) + O2(g)  2SO3(g) Single-Correct-Answer Type
will be [AIEEE 2006] 9. The Haber’s process for the formation of NH3 at 298 K
(a) 4.9 ¥ 10–2 (b) 416 is
(c) 2.40 ¥ 10–3 (d) 9.8 ¥ 10–2 N2 + 3H2  2NH3 ; DH = –46.0 kJ. Which of the fol-
3. The equilibrium constants KP1 and KP2 for the reactions lowing is the correct statement? [IIT JEE 2006]
X  2Y and Z  P + Q, respectively are in the ratio of (a) The condition for equilibrium is
1 : 9. If the degree of dissociation of X and Z be equal, GN2 + 3GH2 = 2GNH3 where G is Gibbs free en-
then the ratio of total pressures at these equilibria is ergy per mole of the gaseous species measured at
[AIEEE 2008] that partial pressure.
(a) 1 : 36 (b) 1 : 1 (c) 1 : 3 (d) 1 : 9 (b) On adding N2, the equilibrium will shift to for-
4. For the following three reactions 1, 2, and 3, equilib- ward direction because according to IIsecond law
rium constants are given of thermodynamics the entropy must increase in
(a) CO(g) + H2O(g)  CO2(g) + H2(g) ; K1 the direction of spontaneous reaction.
(b) CH4(g) + H2O(g)  CO(g) + 3H2(g) ; K2 (c) The catalyst will increase the rate of forward reac-
(c) CH4(g) + 2H2O(g)  CO2(g) + 4H2(g) ; K3 tion by two times and that of backward reaction
by 1.5 times.
Which of the following reactions is correct? (d) None of these.
[AIEEE 2008]
(a) K1 K 2 = K3 (b) K2K3 = K1 Multiple-Correct-Answer Type
(c) K3 = K1K2 (d) K3 ◊ K23 = K12 10. The equilibrium 2Cu1  Cu0 + CuII in aqueous me-
dium at 25ºC shift towards the left in the presence of
5. A vessel at 1000 K contains CO2 with a pressure of 0.5
[IIT JEE 2011]
atm. Some of the CO2 is converted into CO on the ad-
(a) NO 3 (b) Cl
dition of graphite. If the total pressure at equilibrium is
(c) SCN (d) CN
0.8 atm, the value of KP is [AIEEE 2011]
11. The thermal dissociation equilibrium of CaCO3 is stud- Assertion-Reasoning Type

ied under different conditions (A) Both Statements 1 and 2 are correct, but Statement 2 is
CaCO3(s)  CaO(s) + CO2(g). For this equilibrium, not the correct explanation of Statement 1.
the correct statement(s) is (are) (B) Both Statements 1 and 2 are correct, but Statement 2 is
[JEE Advanced 2014] not the correct explanation of Statement 1.
(a) DH is dependent on T. (C) Statement 1 is correct but Statement 2 is incorrect.
(b) K is independent of the initial amount of CaCO3. (D) Statement 1 is incorrect but Statement 2 is correct.
(c) K is dependent on the pressure of CO2 at a given T. 12. Statement 1: For every chemical reaction at tempera-
ture, standard Gibbs energy of reaction is zero.
(d) DH is independent of the catalyst, if any.
Statement 2: At constant temperature and pressure,
chemical reactions are spontaneous in the direction of
decreasing Gibbs energy. [IIT JEE 2008]
Answer Key
leVel i
1. (a) 2. (c) 3. (b) 4. (b) 5. (d) 6. (b) 7. (b) 8. (b) 9. (d) 10. (d)
11. (c) 12. (b) 13. (b) 14. (d) 15. (d) 16. (b) 17. (b) 18. (c) 19. (b) 20. (b)
21. (b) 22. (a) 23. (a) 24. (c) 25. (a) 26. (c) 27. (c) 28. (b) 29. (a) 30. (d)
31. (d) 32. (b) 33. (a) 34. (a) 35. (b) 36. (a) 37. (b) 38. (a) 39. (c) 40. (b)
41. (a) 42. (d) 43. (c) 44. (a) 45. (d) 46. (b) 47. (d) 48. (d) 49. (c) 50. (a)
51. (a) 52. (d) 53. (b) 54. (b)
leVel ii
1. (b) 2. (a) 3. (c) 4. (d) 5. (a) 6. (c) 7. (b) 8. (c) 9. (d) 10. (c)
11. (a) 12. (a) 13. (b) 14. (a) 15. (c) 16. (d) 17. (a) 18. (a) 19. (a) 20. (a)
21. (a) 22. (b) 23. (a) 24. (a) 25. (a) 26. (d) 27. (a) 28. (a)
leVel iii
1. (A) Æ s; (B) Æ r; (C) Æ p; (D) Æ q 2. (A) Æ s, t; (B) Æ q, r; (C) Æ q; (D) Æ p

3. (A) Æ r; (B) Æ p, q; (C) Æ p; (D) Æ p, q 4. (A) Æ r; (B) Æ p; (C) Æ q; (D) Æ s
5. (A) Æ q; (B) Æ p, s; (C) Æ p, s; (D) Æ s
6. (a) 7. (c) 8. (b) 9. (d) 10. (c) 11. (a) 12. (a) 13. (b) 14. (b) 15. (c)
16. (d) 17. (c) 18. (d) 19. (d) 20. (c) 21. (b) 22. (b) 23. (a) 24. (c) 25. (d)
26. (d) 27. (b) 28. (c) 29. (a) 30. (c) 31. (a) 32. (c) 33. (b) 34. (a) 35. (4)
36. (18) 37. (9) 38. (8) 39. (3)
40. (i) [CO2] = [H2] = 0.34 mole, [CO] = [H2O] = 0.112 mole (ii) [CO2] = [H2] = 0.594 mole, [CO] = [H2O] = 0.196 mole
41. [HI] = 5.68 M, [H2] = [I2] = 3.16 M. 42. a = 0.84, KC = 0.056 43. KP = 1.677 ¥ 10–3
44. (i) 0.1 mole (ii) 0.4 mole 45. Pso2 = 0.23 atm, Po2 = 2.0115 atm, Pso3 = 0.977 atm
46. KP = 2.71 ¥ 10–2 atm, KC = 2.39 ¥ 10–4 mole L–1 47. a = 0.433, Kp = 0.231 atm 48. KP = 5.206 atm
49. XN2O5 = 0.407 50. (i) KC = 8.1 ¥ 10–5 (mole L–1)2, Kp = 4.9 ¥ 10–2 atm2 (ii) no effect
preVious years’ questions of Jee (main & aDVanceD)
1. (b) 2. (b) 3. (a) 4. (c) 5. (a) 6. (d) 7. (b) 8. (b) 9. (a) 10. (b, c, d)
11. (a, b, d) 12. (d)
Hints and Solutions

[D] = x = 2 mole
leVel i
[C ][ D] 2 ¥ 2
Kc = = =1
[ A][ B] 2 ¥ 2
1. (a) Kc = 20 kf = 10 kb = ?
9. (d) 2HI  H2 + I2
kf 10 Initially 1 0 0
Kc = 20 =
kb kb Moles at equilibrium 1–a a/2 a/2
10 50% of HI is dissociated therefore a = .5
\ Kb = = 0.5 [HI] = 1 – .5 = .5
20
[H2] = .5/2
1 [I2] = .5/2
2. (c) NO(g) + O2(g)  NO2(g)
2 [H 2 ][I 2 ] .5/2 ¥ .5/2 1
[NO 2 ] Kc = = = = 0.25
K1 = = 4 ¥ 10- 3 [HI]2 [.5]2 4
[NO][O 2 ]1/2
10. (d)
Now for reaction 2NO2(g)  2NO(g) + O2(g) C2H5OH(l) + CH3COOH(l)  CH3COOC2H35(l) + H2O(l)
2
[NO] [O 2 ] 1 Initially(l) (1) 0 0
K2 = 2
= 2 Moles of equilibrium 1 – a 1–a a a
[NO 2 ] K1
Given a = 2/3
1 Therefore,
= = 6.25 ¥ 104
(4 ¥ 10-3 ) 2 C2H5OH = 1 – 2/3 = 1/3
CH3COOH = 1–2/3 = 1/3
3. (b) KC =
[ NOCl]2 CH3COOC2H5 = 2/3
[NO]2 [Cl2 ] H2O = 2/3
96
4. (b) Number of moles of O2 = = 3 mol [CH3COOC2 H5 ][H 2O] 2 /3 ¥ 2/3
32 Kc = = =4
Number of moles 3 [CH3COOH][C2 H5OH] 1/3 ¥ 1/3
Molar concentration = = = 1.5
Volume in litre 2 [ pco ]2 [4]2
mol/ltr 11. (c) Kp = =
5. Value of Kp is greater then Kc for those reaction in [ pco2 ] [2]
which Dn > 0. \ Kp = 8 atm
because = Kp = Kc (RT)Dn Molecular mass 208.5
12. (b) D for PCl5 = = = 104.25
Here for the reaction 2SO3(g)  2SO2(g) + O2(g); 2 2
Dn = 3 – 2 = 1 > 0 d for PCl5 = 100
Therefore Kp > Kc for this reaction D - d 104.25 - 100
6. (b) Kp = 20R (given) a= = = 0.0425
d 100
for the reaction Dn = (2 – 1) = 1
Kp = Kc (RT)Dn 13. (b) H2 + Cl2  2HCl
20R = Kc (RT)1 9.023 ¥ 1023
3 mole 0 Initial mole
20 R 6.023 ¥ 1023
\ Kc = = .02 mol L-1 3 – 1.5 mole 1.5–1.5 mole 3.0 mole at equilibrium
R ¥ 1000
Total mole at equilibrium = 1.5 + 3.0 = 4.5 mole
7. (b) N2O4  2NO2
Initially 1 0 3.0 1600
Partial pressure of HCl = ¥ 800 = = 533 mm
Moles at equilibrium 1–a 2a 4.5 3
14. (d) N2O4  2NO2
\ total number of moles at equilibrium = 1 – a + 2a
1–x 2x
=1+a
P = 1 atm. pressure. x = 20%, i.e., 0.2 mole
8. (b) A + B  C + D
Initially 4 4 0 0 4 x2 P
Kp =
At equilibrium 4 – x 4–x x x 1 - x2
Given at equilibrium mole of C = 2 (\ x = 2) 4 ¥ 0.2 ¥ 0.2 ¥ 1 0.16
\ [A] = 4 – 2 = 2 mole Kp = = = 0.17
[B] = 4 – 2 = 2 mole 1 - (0.2) 2 0.96
15. (d) Equilibrium constant (Kc) will remain unchanged. 24. C(s) + CO2(g)  2CO(g)
16. (b) PCl5  PCl3 + Cl2 Gaseous mole
Initial mole 1 0 0 before dissociation – 1 0
Mole at equilibrium 1 – 0.2 0.2 0.2 Gaseous mole
[PCl3 ][Cl2 ] 0.2 ¥ 0.2 1 Ê 50 ˆ 2 ¥ 50
Kp = = = = 0.5 atm after dissociation – ÁË1 - ˜
[PCl5 ] 0.8 20 100 ¯ 100
0.5 1
17. (b) Volume of gases is increasing in the forward reac- \ total mole = 1.5
tion. Therefore on increasing pressure, equilibrium will Total pressure given at equilibrium = 12 atm
shift towards backward direction.
18. (c) On increasing pressure in the reaction, equilibrium 1
Partial pressure of CO = ¥ 12 = 8
will shift towards the direction where volume gets de- 1.5
creased, i.e., towards forward (right) direction. .5
Partial pressure of CO2 = ¥ 12 = 4
[Product] 1.5
19. The ratio is maximum when K = 1010 and
[Reactant] P2 (8) 2
K p = CO = = 16 atm
thus reaction goes farthest to completion when K = 1010 PCO2 4
[ B]
20. For A(g)  B(g) ; Kc = = 1.1 fi [B] > [A]. 25. a – D glucose  b – D glucose
[ A] At equilibrium 36.4 63.6
If [B] = 1; [A] = 0.91
Case I 0.91 < [A] £ 1 Only [B] > 1 63.6
\ KC = = 1.747
Case II [A] > 1 Both [A] and [B] > 1 36.4
21. N2O4  2NO2
kf
1 ¥ 10- 4
0.1 0 26. (c) Apply the formula, K = = = 4 ¥ 10–3.
(0.1 – a) 2a kb 2.5 ¥ 10- 2
(2a ) 2 È P ˘
1 27. (c) SO2(g) + NO2(g)  SO3(g) + NO(g)
Kp = ¥Í 40a 2
˙
(0.1 - a ) Î 0.1 + a ˚ or K p = 1 1 1 1 Initial conc.
(0.1 - a ) 1–x 1–x 1 + x 1 + x At
40a 2 equilibrium
or = 0.14
(0.1 - a ) [SO3 ][NO] (1 + x)(1 + x)
K= =
\ a = 0.017 \ NO2 = 0.017 ¥ 2 = 0.034 mole [SO 2 ][NO 2 ] (1 - x)(1 - x)
[CO 2 ] (1 + x) 2 (1 + x)
22. K c = 16 = fi = 4 or x = 0.6
[CO] (1 - x) 2 (1 - x)
[CO 2 ]
\ 5= [NO2] = 1 – x = 1 – 0.6 = 0.4 mol L–1.
2.5 ¥ 10-2 28. (b) This is according to Le-Chatelier’s principle.
\ [CO2] at equilibrium = 2.5 ¥ 10–2 ¥ 5 = 12.5 ¥ 29. (a) The degree of dissociation cannot be calculated
10 mol L–1
–2
from the vapour density data. Because here the number
23. Reaction 2H2S  H2 + S2 of moles remains unchanged before and after reaching
Mole before dissociation 1 0 0 equilibrium.
a 30. (d) Equilibrium constant depends only on temperature
Mole after dissociation (1 – a) a
2 and stoichiometry of the reaction.
31. (d) K P = PCO2 and active mass of solid is constant
where a is degree of dissociation of H2S
Volume of container = 1.10 L 32. (b) On adding reactant, (PCl5) reaction proceed in for-
2
ward direction \ more Cl2 formed.
Èa ˘ È a ˘ 33. (a) Keq µ Stability of Pdt
[H 2 ]2 [S2 ] ÍÎ1.1˙˚ ÍÎ 2 ¥ 1.1˙˚ 34. (a)
\ KC = = = 1 ¥ 10 –6
[H 2S]2 È 1 - a ˘
2 Initial pressure xy2(g)  xy(g) + y(g)
Í 1.1 ˙ at equilibrium 600mm
Î ˚ 600 – p1 p1 p1
Assuming 1 – a = 1 since a is small because Kc = 10–6 Total pressure at equilibrium = 600 – p1 + p1 + p1
a3 = 600 + p1
\ = 10- 6 a = 1.3 ¥ 10–2 = 1.3% 1
600 + p = 800
2(1.1)
p1 = 800 – 600 = 200 mm
35. (b) 2SO2(g) + O2(g)  2SO3(g) t = teq (3.3 ¥ 10–3 – 2x) x x

2 2 2
[SO3 ] [1.9] x
KC = = M -1 = 12.237 mol L-1 KC = = 32
[SO 2 ]2 [O 2 ] [0.6]2 ¥ [0.82] (3.3 ¥ 10-3 - 2x) 2
36. (a) on solving, x = 1.5 ¥ 10–3
(i) KP = KC(RT)Dn [BrCl] = 33 ¥ 10–4 – 2x = 33 ¥ 10–4 – 30 ¥ 10–4
{ Dn = 1 = 3 ¥ 10–4
K 1.8 ¥ 10- 2 45. (d) DG 0 = DGNO0 0
- DGNO
\ KC = P = = 4.4 ¥ 10- 4 2
RT 0.0821 ¥ 500 = (52 – 87) kJ mol–1 = –35 kJ mol–1
(ii) \ Dn = 1 { DG0 = –2.303 RT log K
K 167 - 35 kJ mol-1
KC = P = = 1.90 log K =
RT 0.0821 ¥ 1073
- 8.301 Jk mol-1 ¥ 298 K ¥ 2.303
-1
1 1 On solving, K = 1.365 ¥ 106

37. (b) KC(reverse) = = = 1.59 ¥ 10-15
KC 6.3 ¥ 10-14
( PNH3 ) 2 (3) 2 9
38. (a) KP = KC(RT) Dn 46. (b) Qp = = = atm - 2
PN2 ¥ ( PH2 )3 (1)(2)3 8
Dn = –1
By putting the values and on solving = 1.125 atm–2.
KC = 7.47 ¥ 1011 M–1 Since value of Qp is larger than Kp (4.28 10–5 atm–2), it
39. (c) Reaction 2HI(g)  H2(g) + I2(g) indicates net reaction will proceed in backward direc-
t=0 0.2 atm 0 0 tion.
change –2x +x +x 2 ¥ 35
47. (d) Moles of PCl5 dissociated = = 0.7
t = teq (0.2 – 2x) x x 100
From question, 0.2 – 2x = 0.04 Moles of PCl5 left undissociated = 2 – 0.7 = 1.3 mol
2x = 0.2 – 0.04 = 0.16 1.3 0.7 0.7
x = 0.08 [PCl5 ] = M, [PCl3 ] = M, [Cl2 ] = M
5 5 5
0.08 ¥ 0.08 Ê 0.7 ˆ Ê 0.7 ˆ
KP = =4
[0.04]2 [PCl3 ][Cl2 ] ÁË 5 ˜¯ ÁË 5 ˜¯
K= = = 0.75
40. (b) N2 (g) + 3H2 (g)  2NH3(g) [PCl5 ] Ê 1.3 ˆ
ÁË ˜¯
2 5
Ê 8.13 ˆ
ÁË ˜ [8.13]2 ¥ [20]2 48. (d) Suppose 1 mole of A and B each taken then 0.8
Q= 20 ¯ =
3 mole L–1 of C and D each formed remaining concentra-
1.57 Ê 1.92 ˆ 1.57 ¥ [1.92]3
¥Á ˜ tion of A and B will be (1 – 0.8) = 0.2 mole L–1 each.
20 Ë 20 ¯
[C ][ D] 0.8 ¥ 0.8
= 2.38 ¥ 103 Q > KC, so reaction proceeds in backward Kc = = = 16.0
[ A][ B] 0.2 ¥ 0.2
direction.
41. (a) 4NO(g) + 6H2O (g)  4NH3(g) + 5O2(g) 49. (c) A + B  C + D
42. (d) PCl5(g)  PCl3(g) + Cl2(g) Initial concentration 4, 4 0 0
t = teq 0.5 ¥ 10–1 M x x After T time
concentration (4 – 2) (4 – 2) 2 2
x2
KC = 8.3 ¥ 10–3 = [C ][ D] 2 ¥ 2
0.5 ¥ 10-1 Equilibrium constant = = =1
2
x = 4.15 m ¥ 10 –4 [ A][ B ] 2 ¥ 2
x  0.02 M 50. (a) H2 + I2  2HI; [HI] = 0.80, [H2] = 0.10, [I2] = 0.10
43. (c) N2(g) + 3H2 (g)  2NH3 (g)
t = teq 3M 2M 0.5M [HI]2 0.80 ¥ 0.80
Kc = = = 64
0.5 ¥ 0.5 1 1 [H 2 ][I 2 ] 0.10 ¥ 0.10
Q= = =
3 ¥ 23 3 ¥ 8 ¥ 4 96 51. (a) Those reactions which have more value of K pro-
{ Q < K, system is not at equilibrium and equilibrium ceed towards completion.
will be reached by shifting in forward direction 52. (d) Kc is a characteristic constant for the given reaction.
44. (a) 2BrCl (g)  Br2 (g) + Cl2 (g) 53. Equilibrium constant is independent of original con-
t=0 3.3 ¥10–3 M 0 0 centration of reactant.
change –2x x x 54. Kp is constant and does not change with pressure.
Number of moles of Br2 = (0.043 – 0.0259) mol =

leVel ii 0.0178 mol
5. (a) KP = KC(RT) Dn
1. (b) 2SO2(g) + O2(g)  2SO3(g) Dn = –1
[SO3 ]2 1.92 By putting the values and on solving
KC = 2
= 2
M -1 = 12.237 mol L-1 KC = 7.47 ¥ 1011 M–1
[SO 2 ] [O 2 ] 0.6 ¥ 0.82
\ KC for
1 1
2SO3  2SO2 + O2
\ KC = SO 2 + O 2  SO3 (12.237) 2
2 1
2. (a) CO (g) + 2H2 (g) m CH3OH (g) 7.47 ¥ 1011
Initial mole 0.2 a 0 6. (c) 2HI(g)  H2(g) + I2(g)
Mole at (0.2 – 0.1) (a – 0.2) 0.1 t=0 0.2 atm 0 0
equilibrium change –2x +x +x
Now total mole at equilibrium are 0.1 + a – 0.2 + 0.1 =
t = teq (0.2 – 2x) x x
a
PV 4.92 ¥ 5 From question, 0.2 – 2x = 0.04
Also Mole (n) = = = 0.499 2x = 0.2 – 0.04 = 0.16
RT 0.0821 ¥ 600
x = 0.08
\ a = 0.499
0.08 ¥ 0.08
0.1 0.2 - 0.1 0.1 KP = =4
\ [CH3OH] = ; [CO] = = ; 0.042
5 5 5
0.499 - 0.20 0.299 KP = KC (RT)Dn
[H 2 ] = = Dn = 0
5 5
\ KP = KC
[CH3OH] 0.1/5 7. (b) The fraction of A decomposed at equilibrium is in-
 KC = =
[CO][H 2 ]2 0.1/5 ¥ (0.299/5) 2 dependent of initial concentration. In other words, the
equilibrium constant expression is free from concentra-
= 279.64 L2 mol-2
tion term. The equilibrium reaction is
KC = 279.64 litre2 mol–2 xA  C + D
KP = KC (RT)Dn Initial conc. c 0 0
= 279.64 ¥ (0.0821 ¥ 600)–2 Concentration
ca ca
at equilibrium c(1 – a)
KP = 0.115 atm–2 x x
3. (c) 2N2(g) + O2(g)  2N2O(g)
ca
Ê ˆ Ê ˆ ca
t=0 0.482 mol 0.933 mol 0 ¥
[C ][ D] ÁË x ˜¯ ÁË x ˜¯ (ca ) 2
Change –2x M –x M +2x M KC = = =
t = teq (0.0482 – 2x) (0.0933 – x) 2x [ A]x [c(1 - a )]x x 2 [c(1 – a )]x
Kc = 2 ¥ 10–37 = The expression of KC will be free from concentration
Since Kc has small value, x should be low term only when value of x is 2. Putting x = 2, gives
0.0482 – 2x = 0.0482 M c 2a 2 a2
0.0933 – x = 0.0933 M KC = 2
=
4[c(1 – a )] 4(1 – a ) 2
(2 x) 2 8. (c) H2O(g) + CO(g)  H2(g) + CO2(g)
2 ¥ 10–37 =
[0.0482]2 ¥ [0.0933] t = 0 1 mol 1 mol 0 0
On solving, x = 3.3 ¥ 10–21 M –0.4 mol –0.4 mol 0.4 mol 0.4 mol
[N2O] = 2x = 6.6 ¥ 10–21 M t = teq 0.6 0.6 0.4 0.4
[N2] = 0.0482 M ; [O2] = 0.0993 M 0.4 ¥ 0.4 4
4. (d) 2NO (g) + Br2(g)  2NOBr (g) KC = = = 0.44
0.6 ¥ 0.6 9
t = 0 0.087 mol 0.043 mol 0 9. (d) PCl5(g)  PCl3(g) + Cl2(g)
–2x –x 2x
t = teq 0.5 ¥ 10–1 M x x
t = teq 0.087 – 2x 0.0437 – x 2x 2
From equation, x
KC = 8.3 ¥ 10–3 =
2x = 0.0518 mol 0.5 ¥ 10-1
x = 0.0259 mol x2 = 4.15 ¥ 10–4
Number of moles of NO = (0.087 – 0.0518) mol = x = 0.02 M
0.0352 mol
10. (c) H2(g) + Br2(g)  2HBr(g) 14. (b) Case (i)

t=0 0 0 10 bar C2H5OH + CH3 COOH m CH3COOC2H5 + H2O
+x +x –2x Mole
t = teq x x 10 – 2x before 1 1 0 0
reaction
(10 - 2x) 2 Mole at 1–x 1–x x x
KC = 16 ¥ 10- 6 =
x2 equilibrium
10 - 2x 10 10 2
4 ¥ 10-3 =  ;x= = 2.5 ¥ 10- 3  x=
x x 4 ¥ 103 3
11. (a) X2 + X–  X 3- \ Mole at Ê 2ˆ Ê 2ˆ 2 2
ÁË1 - ˜¯ ÁË1 - ˜¯
1 0.5 0 equilibrium 3 3 3 3
(1 – x) (0.5 – x) x 2 2
– ¥
(0.5 – x) = unreacted X \ KC = 3 3 = 4
X– ∫ Ag + 0.25; x = 0.25 1 1
¥
[ X 3- ] 0.25 3 3
Kc = -
= = 1.33 Note: Volume terms are eliminated as Dn = 0
[ X 2 ][ X ] 0.75 ¥ 0.25 Case (ii)
12. (b) C2H5OH + CH3COOH m CH3COOC2H5 + H2O
CO(g) + 2H2(g) m CH3OH(g) Mole
M before reaction 0.15 a 0 before
M after reaction (0.15 – x) (a – 2x) x reaction 1 1 0 0
and x = 0.08 Mole at 2–x 2-x x x
Total mole at equilibrium = 0.15 – x + a – 2x + x equilibrium
= 0.15 + a – 2x x2 x
KC = 4 = \ =2
= 0.15 + a – 0.16 (2 - x) (2 - x)
= a – 0. 01 x = 1.33 g molecule
PV 15. (c) S8(g)  4S2(g)
Also total mole at equilibrium are obtained by n =
RT At start 1 0
P = 8.5 atm ¸ At eqbm 1 – 0.29 4 ¥ 0.29
8.5 ¥ 2.5 Ô
n=  V = 2.5 L ˝ at equilibrium = 0.71 atm = 1.16 atm
0.0821 ¥ 750
T = 750 K Ô˛ [ pS2 ]4 (1.16) 4
Kp = = = 2.55 atm3
\ n = 0.345 [ pS8 ] (0.71)
\ a – 0.01 = 0.345 16. A(s)  2 B(g) + 3C(g)
\ a = 0.355 1- x 2x 3x
At equilibrium : Kc = 4x2 ¥ 27x3

Mole of CO = 0.15 – 0.08 = 0.07 = 108x5
Mole of H2 = 0.355 – 0.16 = 0.195 A(s)  2 B(g) + 3C(g)
Mole of CH3OH = 0.08 2x ¥c 6x
[CH3OH] 0.08/2.5 108x5 = 4x2 ¥ c2 ¥ 216x3

\ KC = = 108 = c2 ¥ 216 ¥ 4
[H 2 ] [CO] Ê 0.07 ˆ Ê 0.195 ˆ 2
2
ÁË ˜Á ˜ 108
2.5 ¯ Ë 2.5 ¯ c2 =
4 ¥ 216
=187.85 mol–2 L
1
Also KP = KC (RT)Dn = 187.85 ¥ (0.0821 ¥ 750)–2 c=
= 0.05 atm 2 2
13. (b) 6.909 K cal/mol = –2.303 ¥ R ¥ 300 log K 17. LiCl. 3NH3 (s)  LiCl. NH3 (s) + 2NH3 (g) [KP =
1000 Ê 1ˆ 9atm2]
= log Á ˜  A2
2A  \ LiCl. NH3 (s) + 2NH3(g)  LiCl. 3NH3(s)
200 Ë K¯
È 1 -2 ˘
Ê 1ˆ –5 5 ÍÎ K P1 = 9 (atm) ˙˚
5 = log Á ˜ fi K = 10 K¢ = 10 fi [A2] = 0.4
Ë K¯
Inital mole 0.1 a 0 21. 2ICl(g)  I2(g) + Cl2 (g); KC = 0.14

at equilibrium 0 (a – 0.2) 0.1 t=0 0.78 M 0 0
Let initial mole of NH3 should be a to bring in comple- –2x x x
tion of reaction. t = teq (0.78 – 2x) x x
1
At eq. K P1 = x2
¢ 3 )2
( PNH 0.14 =
(0.78 - 2 x) 2
1 1
or = On solving, x = 0.21 M
¢ 3 )2
9 ( PNH
22. C2H6 (g)  C2H4(g) + H2(g)
\ PNH
¢ 3 = 3 atm t=0 4 atm 0 0
–x x x
 PV = nRT
t = teq 4–x x x
3 ¥ 5 = n ¥ 0.0821 ¥ 313
\ n = 0.5837 x2
0.04 =
i.e., (a – 0.2) = 0.5837 4- x
\ Initial mole of NH3 = a = 0.5837 + 0.2 = 0.7837 mole On solving, x = 0.38;
18. 2KCN + AgNO3 Æ Ag (CN)2– + KNO3 + K+
PC2H6 = 3.62 atm
0.1 0.03 0 0 0
(0.1-0.06) 0 0.03 0.03 0.03 23. FeO(s) + CO(g)  Fe (s) + CO2(g)
[Ag (CN)2–] = 0.03 M t=0 — 1.4 atm — 0.8 atm
Now use Ag (CN)2– m Ag+ + 2CN– — +x — –x
0.03 0 0.04 At equilibrium (1.4 + x) 0.8 – x
(0.03 – a) a 0.04 + 2a = 0.04
0.8 4
Since KC is too small and dissociation of Ag(CN)2– is Q= = = 0.55
1.4 7
very less and thus,
\ 0.04 + 2a = 0.04 and 0.03 – a = 0.03 { Q > K, system is not at equilibrium and to attain equi-
\ [Ag(CN)2–] = 0.03; [ Ag+] = a, [ CN–]= 0.04 librium it will shift in backward direction
[Ag + ][CN - ]2 a ¥ (0.04) 2 0.8 - x
Now KC = = K P = 0.265 =
[Ag(CN) 2- ] 0.3 1.4 + x
a = 0.75 ¥ 10 –18 On solving, x = 0.339
19. DG° = –2.303 ¥ RT log10 KC \ [PCO] = 1.739 atm and PCO2 = 0.461 atm
\ 77.77 ¥ 103 = –2.303 ¥ 8.314 ¥ 1000 log10 KC
KC = 8.67 ¥ 10–5 24. H2 + Br2  2HBr KP = 25
1 1 1
Reaction N2 + O 2 m NO \ KP for 2HBr  H2 + Br2 KP¢ =
2 2 25
10 – 2x x x
Initial pressure 0.8 0.2 0
Ê xˆ Ê xˆ 1 x2 1 x 10
Final pressure ÁË 0.8 - ˜¯ ÁË 0.2 - ˜¯ x K P¢ = = 2
fi = \ x = Bar
2 2 25 (10 - 2 x) 5 10 - 2 x 7
x 25. (a) Given that DE – DH = 1200 cal
\ 8.67 ¥ 10–5 =
Ê xˆ Ê
1/2
xˆ
1/2 Where DE is heat of reaction at constant volume and
ÁË 0.8 - ˜¯ ÁË 0.2 - ˜ DH is heat of reaction at constant pressure.
2 2¯
–5 Also we have DH = DE + DnRT
x = 3.47 ¥ 10 atm \ DnRT = –1200
20. H2(g) + I2(g)  2HI (g)
t = teq x x 0.5 M -1200
or Dn = = -2 ( R = 2 cal)
0.5 ¥ 0.5 2 ¥ 300
KC = 54.8 =
x2 Now KP = KC (RT)Dn
0.5 ¥ 0.5 KP
x2 = \ = (0.0821 ¥ 300) -2 = 1.648 ¥ 10-3
54.8 KC
On solving, x = 0.068 M
26. (d) 2HI(g)  H2(g) + I2(g)–

leVel iii
a a
1–a
2 2
Match the Columns
2
Êa ˆ 1. (a – s); (b – r); (c – p); (d – q)
ÁË PT ˜¯ a
Kp = 2 fi = 2 Kp KP = KC (RT)Dn
(1 - a ) 2 PT2 1- a (a) Dn = 0
2 Kp (b) Dn = 2 – 4 = – 2
a= (c) Dn = 2 – 1 = 1
1+ 2 Kp (d) Dn = 2 – 0 = 2
2. (a – s); (b – q, r); (c – q); (d – p)
27. (a) For the given equilibrium, the equilibrium concen-
Q = ratio of active masses of product to the active
tration are
masses of reactant.
2AB2(g)  2AB(g) + B2(g)
Q π K reaction is not at equilibrium
Equilibrium
Q = K Reaction at equilibrium (Rf = Rb)
ca
concentration c(1 – a) ca Q > K reaction proceed in back word direction
2 Q < K Reaction proceed in forward direction.
ca 3. (a – r), (b – p, q), (c – p), (d – p, q)
( PB2 )( PAB ) 2 ¥ (ca ) 2 ¥ PT
KP = = 2 ; Kf - DH
( PAB2 ) 2 2È Ê aˆ˘ K eq = = Ae RT
[c(1 – a )] Íc Á1 + ˜ ˙ Kb
Î Ë 2¯˚
If KF > Kb Keq > 1
a 3 ¥ PT
KP = If KF < Kb Keq < 1
Ê aˆ
2(1 - a ) 2 Á1 + ˜ 4. (a – r), (b – p), (c – q), (d – s)
Ë 2¯ Dn
Since, a is small compared to unity, so 1 – a = 1 and 1 È1˘ 2
degree of dissociation µ Í ˙
a a 3 ¥ PT ÎP˚
+  1 KP = 5. (a – q), (b – p, s), (c – p, s), (d – r)
2 2
28. (b) 2NO + Cl2 m 2NOCl Dng = (SnP)g – (SnR)g
Pressure at t = 0 0.02 Kp = Kc (RT)Dng
0.02 ¥ 99 0.02 ¥ 1 Dng > 0 fi Kp > Kc
at eq. P
100 100 Assertion and Reason
[ PNOCl ]2 (0.02 ¥ 0.01) 2 6. (a) Catalyst just helps to attain equilibrium fast.
 KP = = = 1 ¥ 10-3
[ PNO ]2 [ PCl2 ] (0.99 ¥ 0.02) 2 ¥ P 7. (c) Catalyst does not alter the constant of components
at equilibrium.
\ P = 0.102 atm
8. (b) No of moles µ Pressure
For Cl2 in vessel, using PV = nRT
9. (d) The graph shows irreversible reaction whereas in
0.102 ¥ V = n ¥ R ¥ T (i) reversible reaction, concentration of reactant and prod-
For a gas in vessel, 1 ¥ V = 0.2 ¥ R ¥ T (ii) uct become constant at equilibrium position.
By Eqs. (i) and (ii) nPCl3 ¥ nCl2 Ê p ˆ 1
\ mole of Cl2 (n) at equilibrium = 0.0204 10. (c) K p = ¥ Á ˜ with addition of more
nPCl Ë Sn ¯
2 atm of NO reacts with 1 atm of Cl2 (If V, T are con- 5
stant) and more inert gas Sn will increase that leads to de-
0.02 ¥ 1 atm 0.02 ¥ 1 P
NO react with = 0.0001 atm Cl2 crease in the value of and hence to keep KP con-
100 2 ¥ 100 Sn
stant moles of the product would increase, i.e., a in-
Thus, 0.0001 ¥ V = nCl2used ¥ RT (iii) creases.
By eqs. (ii) and (iii), 11. (a) Effect of pressure Le chatlier Principle.
\ which have reacted = 2 ¥ 10–5 12. (a) Active mass of solid remain constant.
\ Total Cl2 added = 0.0204 + 2 ¥ 10–5 = 0.02042 13. (b) A catalyst favours the forward and backward reac-
tion equally by lowering the corresponding energy of
activation by equal magnitude.
k2 DH È T2 - T1 ˘ Comprehension II
14. (b) log10 = = 24. (C*) DG° = –2.303 RT log K
k1 2.303R ÍÎ T1T2 ˙˚
25. DG0 = –2.303RT log KP = –5.79 k.cal
15 (b) Q < Kc forward reaction 26. DG0 = –2.303RT log k
Q = Kc equilibrium
log k = 1.665
Q > Kc backward direction
16. (d) By the use of catalyst, the reaction rate increases. K = Antilog of 1.665 = 0.4625
But equilibrium constant does not change until the tem- A + B ¤ C + D
perature is varying. Initial concentration 2 2 0 0
17. (c) In exothermic reaction, equilibrium constant in- Equilibrium
creases by decreasing the temperature. concentration 2–x 2–x x x
pH3 2 ¥ pN2 atm3atm x2

18. (d) K p = = = (atm) 2 KC = = 0.4625
pNH3 (atm) 2 (2 - x) 2
or Dn = 4 – 2 = 2 [C ] x
= = 0.68
Unit of Kp = (atm)2 [ A] 2 - x
19. (d) Reaction is exothermic, low temperature favours
Comprehension III
forward reaction. High press favours forward reac-
27. (b) Since Dn = 0, so Kc = Kp = Kx
tion as it is accompanied by decrease in the number of
moles. X H4 2 (2/2) 4
Comprehension I Kx = = = 184 = 1.05 ¥ 105
X H4 2O (1/18) 4
20. CaCO3(s) ¤ CaO(s) + CO2(g)
1/2
Initial moles 0.1 – – – 1 1 Ê 1 ˆ
28. (c) N 2 (g) + O 2 (g)  NO(g) K c = Á
Equilibrium moles 0.1 – x1 x1 x1 2 2 Ë 2.4 ¥1030 ˜¯
at 1000 K
1
1
n1CO2 RT1 NO(g) + Br2 (g)  NOBr (g) K2 = 1.4
K P1 = PCO = 2
2
V
1 1 1  NOBr(g)
x ¥ 0.0821 ¥ 1000 N 2 (g) + O 2 (g) + Br2 (g) 
= = 0.059 2 2 2
10
K = KC ¥ K2 = 9.03 ¥ 10–16
0.059
x= 2
PSO
8.21 29. (a) K p = 2 3
0.059 ˆ PSO ◊ PO2
unreacted CaCO3 = ÊÁ 0.1 - ˜ ¥ 100 = 9.282 . 2
Ë 8.21 ¯ 1 1
21. CaCO3(s) ¤ CaO(s) + CO2(g) \ PO2 = = atm = 0.29 atm
K P 3.5
Initial moles 0.1 – – –
Equilibrium moles 0.1 – x1 x1 x1 30. (c) K p = ( PNH ) 2 ◊ PCO = (2 p ) 2 ¥ P = 4 p 3
3 2
at 1000 K 1/3
ÊK ˆ
n1CO2 RT1 P=Á P˜ = 1.95 ¥ 10-2
1
K P1 = PCO = Ë 4 ¯
2
V
x \ PT = 3P = 3 ¥ 1.96 ¥ 10–2 = 0.058
Degree of dissociation, a1 = 1 = 10 x1
0.1 Comprehension IV
Equilibrium moles 0.1- x2 x2 x2 31. From question,
11
11
nCO2 RT2 DH – DE = 600 cals. = Dn ¥ 2 ¥ 300 cals.
at 1100 K K P2 = PCO =
2
V \ Dn = 1
x2 \ KP = KC (RT)Dn
a2 = = 10 x2
0.1 \ KP/KC = (RT)Dn = (0.821 ¥ 300)1 = 24.63
a 2 x2 K P2 T1 0.08 1000 32. KP = KC(RT)Dn, where Dn = total number of gaseous
= = ¥ = ¥ = 1.356
a1 x1 K P1 T2 0.059 1100 product molecules – total number of gaseous reactant
molecules
22. (b) 913.2°C Dn = (1 + 1 – 0) = 2
K P2 DH È T2 - T1 ˘ \ KP = KC(RT)2
23. log =
K P1 2.303R ÍÎ T1T2 ˙˚ 33. KP = 10 atm–2. from unit of KP, we can calculate
Dn = –2
DH = 6699 cal
KC (nNO2 ) 2 Ê Pˆ
Dn
(2 x) 2 È 10 ˘
1
KP = KC(RT)Dn = KC(RT)–2 = KP = ¥Á ˜ = ¥
(RT ) 2 nN2O4 Ë Sn ¯ (1 - x) ÍÎ (1 + x) ˙˚
\ KP < KC
34. The unit of KC is mol2 L–2, hence Dn = 2. x = 0.0565
\ KP = KC (RT)2 PNO
¢ 2 = 1.07 atm ª 1
4 ¥ [0.821 – 300]2 atm2
PN¢ 2O4 = 8.93 atm ª 9 atm
Subjective Questions
38. T1 = 700 + 273 = 973 K,
Integer-Answer-Type Questions T2 = 1000 + 273 = 1273 K
35. N2O4  2NO2 ; GN0 2O4 = 100 kJ mol-1 K1 = 0.63, K2 = 1.66
Using the Van’t Hoff equation
05 5
0
GNO = 50 kJ mol-1 K ÄH ∞ Ê T2 - T1 ˆ
2 log 2 =
0
K1 2.303R ÁË T1T2 ˜¯
DG0 for reaction = 2 ¥ G NO 2
- GN0 2O4 = 2 ¥ 50 - 100 = 0
Ê 1.66 ˆ DH ∞ Ê 1273 - 973 ˆ
DG = DG0 + 2.303RT log Q fi log Á = ;
Ë 0.63 ˜¯ 2.303 (1.99) ÁË 1273 ¥ 973 ˜¯
52 fi DH° = 8.0 ¥ 103 cal = 8.0 kcal
Now, DG = 0 + 2.303 ¥ 8.314 ¥ 10- 3 ¥ 298 log
5 Note: The units of R and DH must be same
= +3.99 kJ ª 4kJ 39. The given equilibrium is
36. For I equilibrium 2NO2  N2O4 N2(g) + 3H2(g)  2NH3(g)
At t = 0 4 16 0
PN¢ 2O4
KP = = 6.8 …(i) At equilibrium 4 – x 16 – 3x 2x
¢ 2 )2
( PNO Total gaseous moles at equilibrium = 4 – x + 16 – 3x +
2x = (20 – 2x).
P¢N2O4 = 1.7 atm \ by eq. (i) P¢NO2 = 0.5 atm
Since, pressure has fallen to 9/10 of its original value,
The equilibria are maintained using NO and NO2 in the hence number of moles will also fall up to the same
ratio 1 : 2 extent.
For II equilibria NO + NO2  N2O3
9
Initial pressures P 2P 0 (20 - 2x) = ¥ 20 = 18
Pressures at equi (p – x) (2P – x – 3.4) x 10
3.4 atm of NO2 are used for I equilibrium to have P¢N2O4 x=1
= 1.7 atm. 4 - x 4 -1
[N2] = = = 3 mole/L–1
At equilibrium (P – x) 0.5 x 1 1
({ P¢NO2 is same for both the equilbria since both reac- 2x
[NH3] = = 2 mole/L–1
tions are at equilibrium at a time) 1
Total pressure at equilibrium (Given 5.05 atm) 40. (i) The given equilibrium is
= PNO
¢ + PNO
¢ 2 + PN¢ 2O3 + PN¢ 2O4 CO2(g) + H2(g)  CO(g) + H2O(g)
= P – x + 0.5 + x + 1.7 At t = 0 0.45 0.45 0 0
5.05 = P + 2.20 At equilibrium (0.45 – x) (0.45 – x) x x
P = 2.85 atm x2
KC =
2P – x – 3.4 = 0.5 (0.45 - x) 2
2 ¥ 2.85 – x – 3.4 = 0.5
x2
x = 1.80 atm ª 2 atm 0.11 =
37. N2O4  2NO2 (0.45 - x) 2
Pressure at equilibrium 0.7 0.3 x = 0.112
\ [CO2] = [H2] = (0.45 – x) = (0.45 – 0.112)
( PNO2 ) 2 0.3 ¥ 0.3 = 0.3379 ª 0.34 mole each
\ KP = = = 0.1286 atm
PN2O4 0.7 [CO] = [H2O] = x = 0.112 mole each
Now assume decomposition at 10 atm pressure (ii) When 0.34 mole of CO2 and H2 are added in above
N2O4  2NO2 equilibrium then following case exists.
Initial mole 1 0 CO2(g) + H2(g)  CO(g)+ H2O(v)
Mole at equilibrium (1 – x) 2x At t = 0
(0.34 + 0.34) (0.34 + 0.34) 0.11 0.11
At eqbm 2
(0.68 – ) (0.68 – ) (0.11 +) (0.11 + ) È 0.0202 ˘
[PCl3 ][Cl2 ] ÍÎ 1.9 ˙˚ 4.08 ¥ 10- 4
[CO][H 2O] Kc = = =
KC = [PCl5 ] 0.0038 1.9 ¥ 0.0038
[CO 2 ][H 2 ]
1.9
(0.11 + a ) 2 = 0.0565 mole/L–1
0.11 = Kp = Kc (RT)Dn
(0.68 - a ) 2
where Kc = 0.0565
a = 0.086 Dn = 2 – 1 = 1
[CO2] = [H2] = (0.68 – 0.086) = 0.594 mole each 43. Equilibrium of formation of NH3 may be given as,
[CO] = [H2O] = 0.11 + = 0.11 + 0.086 = 0.196 mole each N2 + 3H2  2NH3
41. The given equilibrium reaction is At t = 0 1 3 2
H2 + I 2  2HI
At equilibrium (1 – x) 3(1 – x) 2x
At t = 0 6 3 0
Total moles at equilibrium = 1 – x + 3 (1 – x) + 2x =
At equilibrium (6 – x)/1 3 – x 2x
4 – 2x
Concentration at equilibrium
2x
(2 x) 2 Mole fraction of NH3 =
KC = (4 - 2 x)
(6 - x)(3 - x)
2x 2x
4 x2 Partial pressure of NH3 = ¥ p= ¥ 50
64 = (4 - 2 x) (4 - 2x)
x 2 + 18 - 9 x 2x ¥ 50
25 = \ x = 0.666
On solving x = 2.84 (4 - 2x)
2 x 2 ¥ 2.84 16x 2 (2 - x) 2 16 ¥ (0.666) 2 (2 - 0.666) 2
[HI] = = = 5.68; Kp = =
1 1 27p 2 (1 - x) 4 27 ¥ (50) 2 ¥ (0.334) 2
6 - x 6 - 2.84 = 1.677 ¥ 10 – 3
[H 2 ] = = = 3.16
1 1 44. The given equilibrium is
6 - x 6 - 2.84 2SO2(g) + O2(g)  2SO3(g)
[I 2 ] = = = 3.16
1 1
[SO3 ]2
In the present reaction Dn = 0 hence, volume change KC = …(i)
will not affect the equilibrium. [SO 2 ]2 [O 2 ]
42. Number of moles of PCl5 (i) If [SO3] = [SO2]
Weight 5 1
= = = 0.024 Then KC =
Molecular weight 208.5 [O 2 ]
The equilibrium for dissociation of PCl5 maybe repre- 1 1
[O 2 ] = = = 0.01 mole/L-1
sented as KC 100
PCl5  PCl3 + Cl2 Total moles of O2 present = 0.01 ¥ 10 = 0.1 mole
At t = 0 0.024 0 0 Volume of vessel is 10 L–1
At equilibrium (0.024 – x) x x (ii) When [SO3] = [SO2] ¥ 2
Total moles of gas components = 0.024 – x + x + x
= (0.024 + x) [SO 2 ]2 ¥ [2]2
Then KC = from Eq. (i)
We know, PV = nRT [SO 2 ]2 [O 2 ]
1 ¥ 1.9 = (0.024 + x) 0.0821 ¥ 523
4
1.9 100 =
(0.024 + x) = [O 2 ]
0.0821 ¥ 523
[O2] = 4/100 = 0.04 mole/L–1
x = 0.0202
Total moles of O2 in vessel at equilibrium = 0.04 ¥
0.0202 10 = 0.4 mole.
Degree of dissociation = = 0.843
0.024 45. If 2x is the partial pressure of SO3 that is decreased at
0.024 - a 0.024 - 0.0202 0.0038 equilibrium, we will have
[PCl5 ] = = =
1.9 1.9 1.9 2SO2(g) + O2(g)  2SO3(g)
a 0.0202 t=0 0 2 atm 1 atm
[PCl3 ] = [Cl2 ] = = teq 2x 2 atm + x 1 atm – 2x
V 1.9
The density of the mixture will be

(pSO3 ) 2 (1 atm - 2x) 2
Hence, K p = = nM COCl2 nM COCl2 p pM COCl2
(pSO2 ) 2 (pO 2 ) (2x) 2 (2 atm + x) or r= = =
V n(1 + a )RT (1 + a )RT
= 900 atm -1
pM COCl2
Assuming x << 2 atm, we get a= -1
r RT
(pSO3 ) 2 (1 atm - 2x) 2 Substituting the given values, we get
Kp = =
(pSO2 ) 2 (pO 2 ) (2x) 2 (2 atm + x) (1 atm)(99g mol –1)
a= –1
= 900 atm -1 (1.162g L ) (0.0821 L atm K –1 mol –1) (724 K)
–1
= 1.433 – 1 = 0.433
1 1 1
= 2
= 900, 2 = 7200 x = (b) The partial pressures of the species involved in the
4x ¥ 2 x 7200
reactions are
= 0.0115 1- a a a
Hence, p(SO2) = 2x = 0.023 atm; p(O2) = 2 atm + pCOCl2 = p; pCO = p; pCl2 = p;
1+a 1+ a 1+ a
x = 2.0115 atm
pCO pCl2 a2
and p(SO3) = 1 atm – 2x = 0.977 atm Hence, K p = = p
46. We have pCOCl2 1- a2
2H2S (g)  2H2 (g) + S2(g)
(0.433) 2
n(1 – a) na + n(a/2) Which gives K p = (1 atm) = 0.231
Total amount of gases = n(1 + a/2) 1 - (0.433) 2
48. Let n be the amount of N2O4 at t = 0 and let a be the
1-a a
Hence, pH2S = p; pH2 = p; degree of dissociation of N2O4 at equilibrium. Then
1 + a /2 1 + a /2
N2O4 (g) m 2NO2 (g)
a /2
pS2 = p t=0 n 0
1 + a /2 teq n(1 – a) n(2a)
Ê a
2
ˆ Ê a /2 ˆ Total amount at equilibrium = n(1 + a)
ÁË 1 + a /2 p˜ Á p˜ Using the ideal gas equation, we get
(pH 2 ) 2 (ps 2 ) ¯ Ë 1 + a /2 ¯
Thus, K p = = mass
(pH2S ) 2 Ê 1- a ˆ
2
PV = n(1 + a)RT = (1 + a )RT
ÁË 1 + a /2 p˜ M
¯ PM
(or) PM = r(1 + a)RT (or) a = -1
a3 p r RT
=
2(1 - a ) 2 (1 + a /2) Substituting the given data, we get
Substituting the given value of a, we get (1 atm)(92 g mol –1 )
a= –1
(1.84 g dm –3 )(0.082 dm3 atm K –1 mol –1 )(348 K)
(0.31)3 (1 atm)
Kp = = 2.71 ¥ 10-2 atm = 1.752 – 1 = 0.752
2(1 - 0.31) 2 (1 + 0.31/2)
Hence,
For the given reaction, Dng = +1
Hence, Kc = Kp(RT)–Dng p 2NO [2a p /(1 + a )]2 4a 2
= (2.71 ¥ 10–2 atm) Kp = 2
= = p
p N 2O 4 (1 - a )p /(1 + a ) 1 - a 2
{(0.0821 L atm K–1 mol–1) (1380 K)}–1
= 2.39 ¥ 10–4 mol L–1 4(0.752) 2
= ¥ 1 atm = 5.206 atm
47. (a) Let n be the initial amount of COCl2 and a be its 1 - 0.7522
degree of dissociation. We will have
COCl2  CO + Cl2 49. If p is the partial pressure of N2O5 that has decom-
t=0 n posed,
teq n(1 – a) na na 1
N2O5 (g)  2NO2(g) + O 2
Total amount of gases = n(1 – a) + na + na = n(1 + a) 2
Now, the volume of the flask will be 600 mm-Hg – p 2p p/2
n(1 + a )RT Pressure at any time = (600 mm-Hg – p) + 2p + p/2 =
V=
p 600 mm-Hg + (3/2)p
Equating this to 960 mm-Hg, we get 4 ¥ P1 1 P1 1

p = (2/3) (960 – 600) mm Hg = 244 mm-Hg = = =
P2 9 P2 36
The mole fraction of N2O5 decomposed would be
244 mm-Hg 4. (c)
x= = 0.407 (a) CO(g) + H2O(g)  CO2(g) + H2(g); K1
600 mm-Hg (A)
50. The reaction along with the given data is (b) CH4(g) + H2O(g)  CO(g) + 3H2(g); K2 (B)
NH4HS(s)  NH3(g) + H2S(g) (c) CH4(g) + 2H2O(g)  CO2(g) + 4H2(g); K3 (C)
t=0 3.06g 0 0 Equation (C) = Eq. (A) + Eq. (B)
(= 0.06 mol) Thus, K3 = K1 ◊ K2
teq 0.7 ¥ 0.06 0.3 ¥ 0.06 0.3 ¥ 0.06 mol
mol mol = 0.018 mol 5. (a) CO2(g) + C(s)  2CO(g)
= 0.018 mol Initial 0.5 atm –
(i) The equilibrium constant Kc is At equilibrium (0.5 – p) 2p atm
Total pressure of CO2 and CO gases
Ê 0.018 mol ˆ Ê 0.018 mol ˆ
K c = [NH3 ][H 2S] = Á ˜¯ ÁË ˜¯ PCO2 + PCO = Ptotal
Ë 2L 2L
= 8.1 ¥ 10-5 (mol/L) 2 0.5 – (p + 2p) = 0.8, p = 0.3 atm
The equilibrium constant Kp is \ pCO2 = 0.5 – 0.3 = 0.2 atm
Kp = Kc (RT)Dvg = (8.1 ¥ 10–5 mol2/L2)[(0.082 atm PCO = 2p = 0.6 atm
L mol–1K–1)(300 K)]2 = 4.90 ¥ 10–2 atm2 2
(ii) There will not be any effect on the equilibrium pCO 0.6 ¥ 0.6
KP = = = 1.8 atm
by introducing more of solid NH4HS as the equi- pCO2 0.2
librium constant is independent of the quantity of
6. (d) For the reaction
solid.
N2 + O2 Æ 2NO Kc = 4 ¥ 10–4
Hence for the reaction
preVious years’ questions 1 1
of Jee (main & aDVanceD) NO Æ N 2 + O 2
2 2
1. (b) PCl5(g)  PCl3(g) + Cl2(g) 1 1 100
K c¢ = = = = 50
1 0 0 Kc 4 ¥ 10 - 4 2
1–x x x
Peq ◊ x È x ˘ 7. (b) By using this formula, equilibrium constant,
Also PPCl
¢ 3= = P KP = Kc(RT)Dng
(1 + x) ÍÎ1 + x ˙˚
where Dng = (number of moles of products) – (number
[SO3 ]2
2. (b) KC¢ = of moles of reactants)
[SO 2 ]2 [O 2 ] For the given reaction,
[SO 2 ][O 2 ] 1
KC = 4.9 ¥ 10–2 = SO2(g) + O2(g)  SO3(g)
[SO3 ] 2
2 2 È1 ˘ È3˘ 1
È 1 ˘ È 1 ˘ Dng = 1 - Í + 1˙ = 1 - Í ˙ = -
\ KC¢ = Í ˙ =Í -2 ˙
= 416 Î2 ˚ Î2˚ 2
Î KC ˚ Î 4.9 ¥ 10 ˚ 8. (b) DG = DGº + RT ln Q
3. (a) X  2Y = 2494.2 + 8.1314 ¥ 300 ln 4
1 0 Q
(1–x) 2x = Positive DG = RT ln
K
1
fi (2 x) 2 Ê P1 ˆ Since, DG is positive so, Q > K, so reaction shifts in
K P1 =
(1 - x) ÁË 1 + x ˜¯ reverse direction.
Z  P + Q JEE Advanced
1 0 0
(1–x) x x Single-Correct-Answer Type
1 9. (a)In a reversible reaction, a catalyst speeds up both
(2 x) 2 Ê P1 ˆ
fi KP2 = forward and backward reactions to the same extent, so
(1 - x) ÁË 1 + x ˜¯ (C) is wrong. At equilibrium,
DG = Gproducts – Greactants = 0 (c) Keq depends only on temperature and not on pres-
fi 2GNH3 - (GN2 + 3GH2 ) = 0 or 2GNH3 = GN2 + 3GH2 sure.
(d) Enthalpy of reaction is independent of the cata-
Multiple-Correct-Answer Type lyst. A catalyst generally lowers activation energy
10. (b), (c), (d) Assertion-Reasoning Type
2Cu1  Cu0 + CuII
12. (d) We know that for every chemical reaction at equi-
Cl and CN both make precipitate with Cu1 and hence

librium. Gibb’s free energy (DG = 0) is zero. However
drive the reaction to the left.
standard Gibb’s free energy (DGº) may or may not be
Cupric thiocyanate Cu(SCN)2, black powder, insolu-
zero. Thus Statement 1 is false.
ble in water, readily turning into cuprous thiocyanate
For a spontaneous reaction, at constant temperature
Cu(SCN) a whitish yellow powder, hence it also drives
and pressure, the reaction proceed in the direction in
the equilibrium to the left.
which DG is < 0, i.e., in the direction of decreasing
11. (a), (b), (d)
Gibb’s energy (G) so Statement 2 is true.
(a) DH = CP(rxn) DT
Thus, the only such option is (D) which is the correct
Hence enthalpy depends on temperature
answer.
(b) CaCO3(g)  CaO(s) + CO2(g) KP = PCO2
Chapter
5
Ionic
Equilibrium
Key Concepts
Subtances - +
CH3COOH(aq.)  CH3COO (aq.) + H (aq.)
Electrolyte Non electrolyte Factors affecting degree of dissociation (a)
1. Nature of electrolyte: Strong or Weak
2. Nature of solvent: More is the polarity of solvent, more
Electrolytes
will be the a (degree of dissociation)
3. Temperature T µa (degree of dissociation)
These are the species which can dissociate into the ions in 4. Concentration: µ 1/a (degree of dissociation)
their aqueous solution or in the molten state. Dilution µ a
For example, NaCl, KCl 5. Common ion effect: Whenever common ion is added
to the aqueous solution of weak electrolyte a decreases
because of the increased concentration of common ion.
Non-electrolyte CH3COOH  CH3COO - + H +
These species cannot provide the ions in their molten state. HCl ææ Æ Cl- + H +
For example, sucrose, glucose. Here the common ion is H+. So dissociation of weak
electrolyte CH3COOH Ø (decreases)
Types of Electrolyte�� Ostwald’s law of dilution
1. Strong electrolytes: These electrolyte dissociate al- Applicable for weak electrolyte.
most completely, i.e., a  1 or 100%
1
For example, Strong Acid, Strong Base and salts ‘a ’ µ ‘a’ degree of dissociation of weak electrolyte
Strong Acid Æ HClO4, HCl, HBr, HI, H2SO4, HNO3 C
c = concentration
Strong Base Æ group I and group II, hydroxide (except
Li, Be) 1
‘a ’ µ V V = = dilution
C
HCl(aq.) Æ H+(aq.) + Cl–(aq.)
C 0 0 Ostwald’s law of dilution for monobasic acid
0 C C HA m H+ + A–
2.
Weak electrolytes: These electrolytes dissociate up to Initial Molarity C mole – –
the small extent, i.e., not complete dissociation. at equilibrium C(1 – a) Ca Ca
For example, Weak Acid, Weak Base.
Dissociation constant of Weak Acid (Ka) Ionic Product of Water (Kw) ��
Water is weak electrolyte and it self-ionises.
Ca ◊ Ca a 2C
Ka = = = a 2C H2O m H+ + OH–
C (1 - a ) (1 - a ) Dissociation constant (Kd) of water
If a << 1 fi 1 –a  1
[H + ][OH - ]
a will be neglected when less than equal to 0.05, i.e., 5% or Kd =
K [H 2O]
10–3 > a
C then, ionic product of water or self-ionisation constant.
Kw = kd[H2O]
Ka 1
a= fi ‘a ’ µ = [H+][OH–]
C C 1. Kw is constant at a given temperature.
[H + ] = C ◊ a = K a ◊ C Kw at 25°C is 10–14
Pkw at 25°C = 14
2. Variation of kw with temperature is given by:
For Monoacidic Base ��
BOH m B+ + OH– Kw2 DH È 1 1˘
ln = Í = ˙
C – – Kw1 R Î T1 T2 ˚
C(1 – a) Ca Ca DH Æ heat of ionisation of water.
Ca ◊ Ca a 2C as DH is +ve fi Kw ≠ fi Pkw Ø
Kb = =
C (1 - a ) (1 - a ) Kw = [H+] [OH–]
If a << 1 fi 1 – a  1 [H+] = [OH–] = Kw
a will be neglected when less than or equal to 0.05, i.e., 5% We know Kw µ temperature
Temperature Kw [H+] = [OH–] = Kw
2 Kb
Kb = a C fi a = 0°C 10–15 10 ¥ 10-16 = 3.16 ¥ 10–8
C
[OH - ] = Ca = K b ◊ C 25°C 10–14 10-14 = 10–7
60°C 10–13 10 ¥ 10-14 = 3.16 ¥ 10–7
Relative Strength of Weak Acid or Weak Base
For two Weak Acid 90°C 10–12 10-12 = 10–6
[H + ]1 Ka1 ◊ C Ph scale at different temperature
Relative strength = =
[H + ]2 Ka2 ◊ C 0
7.5
15 (At 0°C)
Ka1 Neutral
Relative strength =
Ka2 0
7.0
14 (At 25°C)
For weak bases: Neutral
6.5
Kb1 0 13 (At 60°C)
Relative strength =
Kb2 Neutral
6.0
K a ≠ fi P Ka Ø (P K a = - log K a ) fi acidic strength ≠ 0 12 (At 90°C)
Kb Neutral
K b≠ fi P Ø fi basic nature ≠
3. In neutral solution:
Dissociation of Polyproticacids [H + ] = [OH - ] = Kw = 10-7 mol/L (at T = 25∞C)
H3PO 4  H + + H 2 PO -4 ; Ka1 [H+][OH–] = Kw (for any solution)
at 25°C, neutral pH = 7
H 2 PO -4  H + + HPO 24- ; Ka2
HPO 24-  H + + PO34- ; Ka3 Relationship between Ka and Kb of conjugate
H3PO 4  3H + +
PO34- ; Ka = Ka1 ¥ Ka2 ¥ Ka3 acid base pair ��
For any polyprotic acid or any polyacidic base, successive HA(aq.) + H 2O(l)  H3O + (aq.) + A - (aq.)
dissociation constant will go on decreasing. [H3O + ][A - ]
Ka = ...(i)
[HA]
Ionic Equilibrium 5.3
For conjugate base:

x 2 + 10-7 x - 10-14 = 0
- -
A (aq.) + H 2 O(e)  HA(aq.) + OH (aq.)
x = 0.618 ¥ 10-7
-
[HA][OH ] ...(ii)
Kb(A - ) = [H + ] = 10-7 + 0.618 ¥ 10-7 = 1.618 ¥ 10-7
[A - ]
pH = 6.79
From Eqs (i) and (ii);
Ka(HA) ¥ Kb(A–) = [H3O+][OH–] 3. pH calculation for weak acids
Ka(HA) ¥ Kb(A–) = Kw [H+] = C ◊ a : C = Normality
a = degree of dissociation
pKa(HA) + pKb(A–) = pKw
For monoprotic Weak Acide:-
pH = - log(aH+ ) a Æ activity
[H + ] = C ◊ a = K a ◊ C
= - log[H + ]
-1 1
[H + ] = 10- pH pH = log K a - log C
2 2
p OH = - log[OH - ] 1 Ka
pH = [ p - log C ]
[OH - ] = 10- POH 2
[H+] [OH–] = Kw 4. pH calculation For weak base
fi –log[H+] – log[OH–] = –log Kw [OH–] = C ◊ a] C = Normality
fi pH + pOH = pKw = 14(at T = 25°C) a = degree of dissociation
pH scale: (at 25°C) For monoacidic base
acidic 7 basic
[OH - ] = Ca = Kb ◊ C
0 neutral point 14
1
P OH = [ P kb - log C ]
pH ≠ fi pOH Ø fi basic strength ≠ 2
Q. At 20°C, pH of a solution is 7, what will be its nature? 5. pH calculation of mixing of Strong Acid and Strong Base
Ans. Since temperature 20°C and less than 25°C Resultant normality of solution (NR)
\ [H+] Neutral less than 10–7. \ Solution acidic in nature.
| S (NV)acid - S (NV)base|
1. pH calculation for strong acids: NR =
V final
[H+] = Normality of acid = N
= M ¥ basicity = nf. M (i) If S(NV)acid > S(NV)base fi Acidic solution.
2. pH calculation for strong base: fi [H+] = NR
[OH–] = Normality of base = N (ii) If S(NV)acid < S(NV)base fi Basic solution.
= M ¥ acidity. = nf. M fi [OH–] = NR
Ph = 14 – POH (iii) If S(NV)acid = S(NV)base fi Neutral solution
Q. Find pH of 10–7 MHCl. = [H+] = [OH–] = 10–7
Ans. [H+] = 10–7 + {10–7} due to self-ionisation of H2O. fi pH = 7
= 2 ¥ 10–7 6. pH calculation of Mixture of Weak Acid and Strong Acid
pH = 7 – log 2 = 6.7
Weak acid Strong acid
OR
HA m H+ + A– HB Æ H+ + B–
Note: Initial C1 – – C2 – –
For very diluted solution, i.e., when [H+] or [OH–] is < Final C1 – x (x + C2) x – C2 C2
10–6M, while calculating the pH H+ or OH– due to self-ion-
isation of water are taken. (C2 + x) x
Ka =
C1 - x
If we consider, the common ion effect of water.
H2O m H+ + OH– Due to common ion effect of Strong Acid for Weak Acid
(x + 10–7) x x << C1
HCl h H+ + Cl– fi C1 - x  C1
(x + 10–7) 10–7
(C2 + x) ◊ x
Ka =
KW = [H + ][OH - ] = 10-14 C1
( x + 10-7 ) x = 10-14
If Strong Acid is highly concentrated H3PO4– m H+ + HPO42–; Ka2

C2 + x  C2 (x – y) (x + y + z) y–z
H3PO42– m H+ + PO43–; Ka3
C2 ◊ x (y – z) (x + z + y) z
Ka =
C1
( x + y + z )( x - y ) ( x + y + z) z
Ka1 = Ka3 =
7. pH for mixing of weak acids c-x ( y - z)
HA m H+ + A– HB m H+ + B– ( x + y + z )( y - z )
Ka2 =
C1 – – C2 – – x- y
C1 – x (x + y) x C2 – y (x + y) y
Ka1 >> Ka2 >> Ka3
( x + y) ◊ x ( x + y) ◊ y fi x >> y >> z
Ka1 = Ka2 =
C1 - x C2 - y fi x + y + z  x and x – y  x and y – z  y
Due to common ion effect, x, y will be negligible. x◊x x2
Ka1 = = as Ka1 is significant x is not negligible
C1 – x  C1 C2 – y  C2 c-x c-x
( x + y) ◊ x ( x + y) ◊ y Ka
Ka1 = ; Ka2 = or > 10-3 .
C1 C2 c
Ka2 = y
Ka1C1 = ( x + y ) ◊ x ...(i)
x◊z
Ka2C2 = ( x + y ) ◊ y ...(ii) Ka3 =
y
(i) + (ii); fi ( x + y ) 2 = Ka1C1 + Ka2C2
fi [H + ] = Ka1C1 + Ka2C2 tyPEs oF sAlt
8. pH for mixing of weak bases
[OH - ] = Kb1C1 + Kb2C2 +  (i) Complete salts or normal salts
9. pH of polyprotic acids: These are the salts which cannot provide H+ or OH–
For H2S if Ka1 = 10–7; Ka2 = 10–14 ions in their aqueous solution.
K2SO4, Na2HPO3 (salt of H3PO3 (Basicity-2), NaH2PO2
H2S m H+ + HS– ; Ka1
C – – (ii) Incomplete salts
C–x (x + y) x–y Salts which can provide H+ and OH– in their aqueous
HS– m H+ + S2– ; Ka2 solution.
(x – y) (x + y) y (a) Acidic salts: provides H+ in their aqueous solu-
tion.
( x + y )( x - y ) x2 x2
Ka1 = = = For example, NaHCO3, KHSO4, NaH2PO3
(c - x ) (c - x ) c (b) Basic salts: provide OH– in their aqueous solution.
( x + y ) y xy Ex. Ca(OH)Cl
Ka2 = = =y
( x - y) x
Ka1 >> Ka2 fi x >> y Salt Hydrolysis ��
x + y = x, x – y  x It is the reverse process of naturalisation in which ions of the
as Ka1 is very low fi c – x  c. salt react with water and form acid and base.
Salt + Water m Acid + Base
Note: H 2S  2H + + S2- ; Ka = Ka1 ¥ Ka2
Types of salt hydrolysis
The formula is used only when [H+] in the solution of H2S 1. Salt of Strong Acid and Strong Base.
is given and sulphide ion is asked or vice versa.
NaCl+ H2O m NaOH + HCl
[H + ]2 ¥ [S2- ] Na+ + Cl– + H2O m Na+ + OH– + H+ + Cl–
Ka1 ¥ Ka2 =
[H 2S] H2O m OH– + H+
fi Salt of strong acid and Strong Base are not hy-
Example 1: H3PO4; drolysed.
Ka1 = 7 ¥ 10–3 Ka2 = 6 ¥ 10–8 Ka3 = 8 ¥ 10–13 fi Their aqueous solution are neutral in nature.
H3PO4 m H+ + H2PO4–; Ka1 2. Salt of Strong Acid and Weak Base.
c – – NH 4Cl + H 2O  NH 4OH + HCl
(c – x) (x + y + z) x–y
Relation between Kh, Kw, Ka

NH +4 + Cl- + H 2O  NH 4OH + H + + Cl-
[CH3 COOH][OH - ]
NH +4 + H 2O  NH 4OH + H + Kh =
[CH3 COO - ]
fi Salt of Strong Acid and Weak Base show the cat-
ionic hydrolysis. Kw = [H + ][OH - ]
fi Their aqueous solution are acidic in nature. [CH3 COO - ][H + ]
Ka =
Relation between hydrolysis constant (Kh), Kw and Kb [CH3 COOH]
[NH 4 OH][H + ] Kw
Kh = ...(i) Kh =
[NH 4+ ] Ka
Degree of hydrolysis(h)
K w = [H + ][OH - ] ...(ii)
CH3COO– + H2O m CH3COOH + OH–
[NH +4 ][OH - ] C – –
Kb = ...(iii)
[NH 4OH] C(1 – h) Ch Ch
Ch ◊ Ch h 2C
K Kh = =
Kh = w C (1 - h) 1 - h
Kb
1–h=1
Degree of hydrolysis (h) Kh
fi Kh = h 2C fi h =
Moles hydrolysed C
h=
Moles taken initially Kw
h=
NH +4 + H 2O  NH 4OH + H + Ka ¥ C
C – – Calculation of Ph:
C(1 – h) Ch Ch
[OH - ] = Ch = Kh ◊ C
2
Ch ◊ Ch h C
Kh = = Kw ¥ C
C (1 - h) (1 - h) =
Ka
As h is negligible 1 – h  1. -1 1 1
2 P OH = log Kw + log Ka - log C
Kh = h C 2 2 2
Kh Kw OH 1 Ka 1
h= = P = 7 - P - log C
C Kb ¥ C 2 2
1 1
pH calculation pH = 7 + P Ka + log C
2 2
[H + ] = Ch = K h ◊ C 4. Salt of Weak Acid and Weak Base:
Kw CH3COONH 4 + H 2 O  CH3COOH + NH 4 OH
[H + ] = ¥C
Kb CH3COO - + NH 4+ + H 2 O  CH3COOH + NH 4 OH
-1 1 1 Salt of weak acid and Weak Base shows both anion as
pH = log K w + log K b - log C
2 2 2 well as cationic hydrolysis :
1 kw 1 Kb 1 Their aqueous solution are neutral (slightly acidic or
= P - P - log C
2 2 2 basic)
1 1 (i) If Ka = Kb fi PKa = PKb fi neutral solution
pH = 7 - P kb - log C (ii) If Ka > Kb fi PKa < PKb fi acidic solution
2 2
(iii) If Ka < Kb fi PKa > PKb fi basic solution
3. Salt of Weak Acid and Strong Base:-
For example, NH4CN fi basic nature
CH3COONa + H 2O  CH3COOH + NaOH
Relation between Kh, Kw, Ka and Kb
CH3COO - + Na + + H 2O  CH3COOH + Na + + OH -
[CH3COOH][NH 4 OH] (i)
CH3COO - + H 2O  CH3COOH + OH - Kh =
[CH3COO - ][NH +4 ]
fi Salt of W.A. and S.B. shows anionic hydrolysis. Kw = [H+][OH–] (ii)
fi Here, cation act as the spectator ion. - +
[CH3COO ][H ]
fi Aqueous solution of these salts are basic in nature. Ka = (iii)
[CH3COOH]
[NH -4 ][OH - ] Kw
Kb = (iv) Kh1 =
[NH 4OH] Ka2
( x - y )( x + y )
(ii) =
eq. = eq. (i) c-x
(iii) ¥ (iv)
Kw y ( x + y )
Kw Kh2 = =
\ Kh = Ka1 x- y
Ka ◊ Kb
Ka1 >> Ka2 fi Kh1 >> Kh2
Degree of hydrolysis (h)
fi x >> y
CH3COO - + NH 4+ + H 2 O  CH3COOH + NH 4 OH
Kw x2 Kw
C C – – = =y
Ka2 C - x Ka1
C (1 - h) C (1 - h) Ch Ch
[OH–]  x \ POH = – log[x]
Ch ◊ Ch Example 3: Na 3PO 4  3Na + + PO34(Hydrolyse)
-
Kh =
C (1 - h) ◊ C (1 - h)
h2 PO34- + H 2O  HPO 24- + OH - ; Kh1
= C-x ( x - y) ( x + y + z)
(1 - h) 2
h HPO 24- + H 2O  H 2 PO 4- + OH - ; Kh2
fi = Kh
1- h x- y y-z x+ y+z
Kw H 2 PO 4- + H 2O  H3PO 4 + OH - ; Kh3
h is negligible fi h = Kh = y–z z x+ y+z
Ka ¥ Kb
Hence, degree of hydrolysis ‘h’ is independent of concen- Kw ( x - y )( x + y + z ) x2
Kh1 = = =
tration or dilution for salt of Weak Acid and Weak Base Ka3 C-x C-x
pH calculation: Kw ( y - z )( x + y + z )
= Kh2 = =y
Ka2 ( x - y)
CH3COOH  CH3COO - + H +
Kw z ( x + y + z ) x ◊ z
[CH3COO - ][H + ] Kh3 = = =
Ka = Ka1 ( y - z) y
[CH3COOH]
Ka1 >> Ka2 >> Ka3 fi Kh1 >> Kh2 >> Kh3
+ [CH3COOH]
[H ] = Ka ¥ fi x >> y >> z
[CH3COO- ]
Hydrolysis of polyvalent cations
Ch h
[H + ] = Ka ¥ = Ka ¥
C (1 - h) 1- h Æ Fe +2 + 2NO3-
Fe(NO3 ) 2 ææ
Kw Fe +2 + H 2O  Fe(OH) + + H + ; Kh1
[H + ] = Ka ¥ Kh = ¥ Ka
Kb (C – x) x–y x+y
-1 1 1 Fe(OH) + H2O m Fe(OH)2 + H+; Kh2
+
pH = log Kw - log Ka + log Kb
2 2 2 (x – y) y x+y
Ka Kb
P P
pH = 7 + - Kw ( x - y )( x + y )
2 2 Kh1 = =
Kb2 C-x
fi pH of this solution is independent of dilution. Kw y ◊ ( x + y )
Kh2 = =
Hydrolysis of polyvalent anions Kb1 ( x - y)
Example 2: Na2S h 2Na+ + S2– (hydrolyse) Kb1 >> Kb2 fi Kh1 >> Kh2 fi x >> y
¥ 
S2– + H2O m HS– + OH–; Kh1 x2
Kh1 = Kh2 = y
C – – C-x
C–x x–y x+y Hydrolysis of salts containing amphiprotic anion
HS– + H2O m H2S + OH–; Kh2 Amphiprotic anions can provide as well as accept H+ i.e.,
(x – y) y y+x they can act as both acid as well as base.
For example, NaHS, KHCO3, NaH2PO4, Na2HPO4 Buffer solutions

Acidic nature These are the solution which resist pH change when small
HA– + H2O m H3O+ + A2–; Ka2 amount of acid or base is added.
These solutions can be kept for long time without chang-
[H3O + ][A 2- ] ing the pH.
Ka2 = ...(i)
[HA - ] Due to dilution, there is no appreciable change in their pH
value.
Basic nature
Types of buffer solutions
HA - + H 2O  H 2 A + OH - ; (a) Simple buffer solution:
Kw Salt of Weak Acid and Strong Base
Kh = ...(ii) e.g. CH3COONH4
Ka1
Acidic Buffer
Ka1 ¥ Ka2 [H3O + ][A 2- ] (b) Mixed buffer:
(i)/(ii); =
Kw [H 2 A][OH - ] Basic Buffer
1. Acidic buffer
Ka1 ¥ Ka2 [H O + ][A 2- ] Weak Acid + its conjugate base or salt.
= 3 (i) CH3OOH + CH3COONa
[H3O ][OH ] [H 2 A][OH - ]
+ -
(ii) HCN + KCN
[H 2 A] (iii) NaH2PO4 + Na2HPO4
[H3O + ]2 = Ka1 ¥ Ka2 ¥
[A 2- ] (iv) H2CO3 + NaHCO3
It is found in human blood which keeps the pH 7.35.
Assuming [H2A]  [A2–] when Ka2  Kh
2. Basic buffer
[H + ] = Ka1 ¥ Ka2 Weak Base + its conjugate acid or salt with strong acid.
(i) NH4OH + NH4Cl
P Ka1 + P Ka2
pH = (ii) RNH 2 + RNH3+ Cl-
2
Buffer action:
Note: It is a mechanism by which buffer solution resist the pH change.
[H 2 A] Buffer action for simple buffer solution:
fi If Kh > Ka2 fi >1 CH3COONH 4 ææ Æ CH3COO - + NH +4
[A 2- ]
fi [H+]≠ On adding H+
Ê P Ka1 + P Ka2 ˆ H + + CH3COO - ææ

Æ CH3COOH
H
\ p <Á ˜¯ (Almost unionises)
Ë 2
[H 2 A] On adding OH–
fi If Kh < Ka2 fi <1
[A 2- ] OH - + NH +4 ææ Æ NH 4OH (almost unionised)
fi [H+]Ø Buffer action for acidic buffer:
Ê P Ka1 + P Ka2 ˆ CH3COOH + CH3COONa

pH > Á ˜¯
Ë 2 CH3COOH  CH3COO - + H +
P Ka1 + P Ka2 Æ CH3COO - + Na +

CH3COONa ææ
(i) NaH 2 PO 4 fi H 2 PO 4-
ææ Æ Ka 2 fi pH =
2 On adding H+ or HCl
one –ve charge on –ve ion hence gives second H+ H + + CH3COO - ææ
Æ CH3COOH
P Ka2 + P Ka3 (Almost unionised)
(ii) Na 2 HPO 4 fi HPO 24 - ææ
Æ Ka3 fi pH =
2 On adding OH– or NaOH
- P Ka3 + P Ka4 OH - + CH3COOH ææ Æ CH3COO - + H 2O

Æ Ka4 fi pH =
(iii) Na 3 HA fi HA ææ
2 (No change in ph)
Buffer action for basic buffer:
P Ka1 + P Ka2
(iv) NaH3 A fi H3 A - ææ
Æ Ka2 fi pH = NH 4OH + NH 4Cl
2
NH 4OH  NH 4+ + OH -
Æ NH +4 + Cl-
NH 4Cl ææ
On adding H+ or HCl Buffer capacity in terms of buffer index

+
H + NH 4OH Æ NH +4
ææ + H 2O (No change in ph) Ê Db ˆ
ÁË DpH ˜¯
On adding OH–
OH - + NH +4 ææ
Æ NH 4OH (Almost unionised) Let an acidic buffer
pH calculation for acidic buffer s
pH1 = P Ka + log ...(i)
CH3COOH + CH3COONa a
CH3COOH  CH3COO - + H + On adding Db moles of base,
acid + base Æ salt
Æ CH3COO - + Na +
CH3COONa ææ a Db s
[CH3COO - ][H + ] a – Db 0 s + Db
Ka = s + Db
[CH3COOH] pH 2 = P Ka + log ...(ii)
[CH3COOH] a - Db
[H + ] = Ka ¥
[CH3COO- ] DpH = pH 2 - pH1
[Acid] s + Db
[H + ] = Ka ¥ = log - log s /a
[Salt of conjugate base] a - Db
[acid] Ê s + Db a ˆ
pH = - log Ka - log = log Á ¥
[salt] Ë a - Db s ˜¯
[Salt] Ê 1 + Db /s ˆ 1 Ê 1 + Db /s ˆ
pH = P Ka + log log Á = ln Á
[acid] Ë 1 - Db /a ¯ 2.303 Ë 1 - Db /a ˜¯
˜
Henderson equation or Henderson Hassel Baton equation,
x 2 x3 x 4
pH calculation for basic buffer ln(1 + x) = x - + - 
2 3 4
[Base] x 2 x3 x 4
[OH - ] = Kb ¥ ln(1 - x) = - x - - - 
[Salt or conjugate acid] 2 3 4
[Base]  x (when x is small)
P OH = - log kb - log
[Salt] 1 È Db Ê -Db ˆ ˘
DpH = -Á ˜
P OH = P Kb + log
[Salt] 2.303 ÍÎ s Ë a ¯ ˙˚
[Base] 1 È Db Db ˘
[Base] = +
pH = 14 - P kb + log 2.303 ÍÎ s a ˙˚
[Salt] Db Ê a + s ˆ
Calculate the concentration of NH3 and NH4Cl required to =
2.303 ÁË a ◊ s ˜¯
prepare 1 L solution of pH = 9. When total concentration of
buffering reagent is 0.6 mL. PKb (NH3) = 4.7 Ê Db ˆ Ê a◊s ˆ
Buffer index Á ˜ = 2.303 Á
Ph = 9 means basic buffer Ë DpH ¯ Ë a + s ˜¯
Buffer capacity
s a
Salt We know,
\ P OH = 5 = 4.7 + log
base a + s = const.(K )
log S /b = 0.3 = log 2 Db a ◊ ( K - a)
= 2.303
S DpH K
=2 Salt
b For maximum buffer capacity:
S + b = 0.6
d Ê Db ˆ
S = [NH 4Cl] = 0.4 M fi b = [NH3 ] = 0.2 M =0
da ÁË DpH ˜¯
Buffer capacity (f)
2.303 K K
It is the measurement of capability of buffer solution to resist fi 0= ( K - 2a ) fi a = fi s =
the pH change. K 2 2
Number of moles of acid or bases added to For maximum buffer action
a=s
1 litre buffer solution
f= At maximum buffer action
DpH For acidic buffer
f fi buffer action
[Salt] = [acid] pH of indicators

pH = PKa HIn m H+ + In– (coloured)
For basic buffer (colourless) (coloured)
[Salt] = [base] [H + ][In - ]
K In =
POH = PKb [HIn]
pH range of buffer solution [HIn]
It is the pH interval in which buffer solution works effective- [H + ] = K In ¥
ly and this pH range is PKa + 1 (for acidic buffer) any buffer [In - ]
[salt] pH of indicator
solution works effectively only when
[acid/base] [In - ]
1 pH = P KIn + log Hendorson equation
fi to 10. [HIn]
10
pH range of indicators
Note: It is the pH interval for indicator in which it shows transition
in colour (mixed colour).
More is the concentration of buffer solution, more will be
pH range = PKIn ± 1
its buffer action.
[In - ] 1
In Sol. (i) a = s = 0.1 M In the pH range is to 10.
[HIn] 10
If Db = 0.01
0.11 Example 1: Hph: pH range = 8.3 to 10
pH1 = P Ka ; pH 2 = P Ka + log
0.09 pH > 10 fi dark pink
11 pH < 8.3 fi colourless
DpH = log
9 8.3 to 10 fi transition colour
Example 2: MeOH: pH range = 3.1 to 4.4
In Sol. (ii) a = s = 0.2 M pH > 4.4 fi yellow
If Db = 0.01
pH < 3.1 fi Red
0.21
pH1 = P Ka ; pH 2 = P Ka + log 3.1 to 4.4 fi transition colour
0.13
Example 3: Bromothymol blue: (6 to 7.6)
21
DpH = log pH < 6 fi yellow
19
pH > 7.6 fi blue
Change in pH for solution I is more, so, buffer action is less. 6 to 7.6 fi transition colour
Example 4: Methyl Red (4.2 to 6.3)
INDIcAtors pH < 4.2 fi red
pH > 6.3 fi yellow
Indicators are the species which detect the end point in the In pH range
titration by colour change. [In - ]
Acid-base indicators are either weak organic acid or weak % ionised part = ¥ 100
[HIn] + [In - ]
organic base.
Indicators show the colour change because of their ionisa- [HIn]
% unionised part = ¥ 100
tion. [HIn] + [In - ]
Generally darker colour is associated with ionised part
where as lighter colour is associated with unionised part.
Example 1: Phenophthalene (Hph)
sElEctIoN oF INDIcAtor
Hph m H+ + Ph– (Pink)
For AcID-BAsE tItrAtIoN
(colourless) (pink) During the acid-base titration, there is a sudden change in pH
in, acidic medium h colourless nearby the equivalence point in certain limits called pH range
in basic medium h pink of titration.
Example 2: Methyl Orange (MeOH) Those indicators will be suitable for the given titration
MeOH m Me+ + OH– whose pH lie in pH range of titration ideally. For best indica-
(yellow) (red) tor, mid-point of the pH range is equal to the pH at equiva-
Red in acidic medium; yellow in basic medium lence point.
Titration of Strong Acid Vs Strong Base 2. VNaOH = 25 mL

CH3COOH + NaOH h CH3COONa + H2O
0.1 M NaOH 5 2.5 – –
2.5 – 2.5 –
After reaction both component present
0.1 M HCl 50 ml
\ buffer solution
HCl h 0.1 M, 50 mL [Salt]
pH = 4.74 from pH = PKa + log
NaOH h 0.1 M [Acid]
1. VNaOH = 0 mL 3. VNaOH = 40 mL
[H+] = 10–1 fi pH = 1 4
2. VNaOH = 20 mL pH = 4.74 + log = 5.34
1
5-2 3 4. VNaOH = 49 mL
[H + ] = =
50 + 20 70 4.9
pH = 4.74 + log fi 4.74 + 2 ¥ (0.85) = 6.44
Ê 3ˆ 0.1
pH = - log Á ˜ = 1.37
Ë 70 ¯ 5. VNaOH = 50 mL; (equivalence point)
3. VNaOH = 40 mL CH3COOH + NaOH h CH3COONa + H2O
5-4 1 5 5 –
[H + ] = = = pH = 1.95 – – 5
90 90
After reaction only salt present \ salt hydrolysis
4. VNaOH = 49 mL
1 1
+ 5 - 4.9 0.1 pH = 7 + pka + log C
[H ] = = fi pH = 3 2 2
99 99 1 1
5. VNaOH = 50 mL \ pH = 7 + ¥ 4.74 + log(5 ¥ 10-2 ) = 8.7
2 2
SNaVa = SNbVb 6. VNaOH = 51 mL
pH = 7 (equivalence point) CH3COOH + NaOH h CH3COONa + H2O
6. VNaOH = 51 mL 5 5.1 –
5.1 - 5 0.1 – 0.1 5
[OH - ] = =
101 101 0.1
[OH - ] =  10-3
OH
P = 3, pH = 11 101
POH = 3 pH = 11
11
11 Indicator used
Hph
PH range of titration
PH PH MeOH
3 6.5
Methyl red
Bromothymol blue
Base added
Base added
7. Titration of Strong Acid and Weak Base: as same as
equivalent pt
titration of Weak Acid and Strong Base
Indicator used
7 Indicator used
MeOH Æ 3.1 to 4.4 MeOH ✓
Boomothymol blue (6 to 7.6) Methylred
POH Methyl red
3.5
Titration of Weak Acid and Strong Base Hph
CH3COOH ææ
Æ 0.1 M, 50 ml Bromothymol blue ✓
NaOH ææ Æ 0.1 M Base added

1. VNaOH = 0 mL
Titration of Weak Acid and Weak Base
Since CH3COOH is a weak acid
Such type of titration is generally not carried out because no
1
pH = [4.74 - log10-1 ] = 2.87 sharp change in the pH is observed near equivalence point.
2
5 5
C= = = 2.5 ¥ 10- 2
150 + 50 200
PH (hydrolysis of polyvalent ion)
PKa2 + PKa1 Hydrolysis of

base added 2 polyvalent ion
Titration of polyprotic acid with Strong Base Ph
PKa2
H3PO 4 ææ
Æ 0.1 M, 50 ml PKa1 + PKa2
2
NaOH ææ Æ 0.1 M
PKa1
(i) VNaOH = 0 mL I II III
+ base added
H3PO 4  H + H 2 PO -4
(ii) VNaOH = 25 mL Solubility (S)
H3PO4 + NaOH Æ NaH2PO4 + H2O It is the maximum amount of the solute that can be dissolved
after reaction both component in one litre of the solution at saturation.
\ buffer Solubility product (KSP)
5 2.5 – A+B–(s) m AB(aqueous)
2.5 – 2.5 undissolved dissolved
pH = P Ka1 AB(s) m A+(aqueous) + B–(aqueous)
(iii) VNaOH = 40 mL Keq = KSP = [A+][B–] (at saturation)
4 Solubility product is the product of ionic concentration of the
pH = P Ka1 + log solute in its saturated solution.
1
(iv) VNaOH = 50 mL 1. AlCl3 (s)  Al+3 + 3Cl-
H3PO4 + NaOH h NaH2PO4 + H2O KSP = [Al+3 ][Cl- ]3
5 5 – –
– – 5 5 2. Ag 2CrO 4 (s)  2Ag + + CrO 24-
After reaction, amphiprotic salt formed.
KSP = [Ag + ]2 [CrO 42- ]
P Ka1 + P Ka2
pH = I equivalence Point +3 2-
2 3. Sb 2S3 (s)  2Sb + 3S
(v) VNaOH = 75 mL KSP = [Sb +3 ]2 [S2- ]3
pH = P Ka2 KSP is constant at a given temperature variation of KSP with
temperature is given by
(vi) VNaOH = 100 mL (second end point)
KSP2 DH È 1 1˘
P Ka2 + P Ka3 ln = -
pH = KSP1 R ÍÎ T1 T2 ˙˚
2
(vii) VNaOH = 110 mL DH = heat of solution
Na 2 HPO 4 + NaOH ææ
Æ Na 3PO 4 + H 2O Condition for precipitation
If Q = KSP fi Saturated solution
5 1 – –
Q = Reaction quotient as per KSP
4 – 1 1 If Q < KSP fi unsaturated solution more solute can be dis-
Ka3 1 solved
pH = P + log
4 If Q > KSP fi Precipitate forms super saturated solution
(viii) VNaOH = 125 mL
Q. Equal volume of 2 ¥ 10–8 M BaCl2 and 2 ¥ 10–2 M Na2SO4
Ka3
pH = P are mixed. Will there be any precipitate? KSP (BaSO4) = 10–10.
(ix) VNaOH = 150 mL Ans.
+2 2-
Q = [Ba ][SO 4 ]
Na 2 HPO 4 + NaOH ææ
Æ Na 3PO 4 + H 2O
= 10–8 ¥ 10–2
5 5 – = 10–10 KSP. \ No Precipitate form
– – 5
Note: Whenever two solutions having the concentration C1

2NO3-
and C2 respectively are mixed in the volume ratio V1 : V2 Pb(NO3)2 h Pb+2 +
then, new concentration in the final solution is given by 0.1 0.1 0.2
CV CV KSP = 7.1 ¥ 10–9 = 0.1 ¥ (2S¢)2
C1¢ = 1 1 C2¢ = 2 2
V1 + V2 V1 + V2 7.1 ¥ 10-9
S¢ =
Relationship between solubility product and solubility 0.1 ¥ 4
AxBy (s)  xA+ y + yB - x 7.1
S¢ = ¥ 10-4
Solubility: ‘S’ mol/L xS yS 4
KSP = [A+y]x[B–x]y
= (xS)x(yS)y sIMUltANEoUs solUBIlty
KSP = xx ◊ yy, sx+y
fi Al2(SO4)3; KSP = 22 ◊ 33 ◊ S5
If two sparingly soluble salt having common ions are pres-
Effect of common ion on solubility of sparingly soluble ent in a solution then, solubility of both the salts decreases
salts because of common ion effects.
On adding, common ion solubility decreases For example AgCl and AgBr
AgCl(s)  Ag + + Cl- ; KSP = S 2 AgCl(s) m Ag+ + Cl–;
Initials: ‘S’ mol/L S S x mol/L (x + y) x
On adding NaCl, Conc. ‘S’ decreased to ‘S¢’ mole/L. AgBr(s) m Ag+ + Br–;
AgCl(s) m Ag+ + Cl– y mol/L (x + y) y
if S¢ solubility S¢ S¢ + C KSP(AgCl) = (x + y)x ...(i)
NaCl h Na+ + Cl– KSP(AgBr) = (x + y)y ...(ii)
C gives C C + S¢ (i) + (ii) fi
KSP = [Ag+][Cl–] KSP (AgCl) + KSP (AgBr) = ( x + y ) 2
KSP = S¢(S¢ + C)
S¢ + C  C due to common ion effect for sparingly soluble [Ag + ] = ( x + y ) = KSP (AgCl) + KSP (AgBr)
salt. KSP (AgCl) x
S¢ << C =
KSP (AgBr) y
K
S ¢ = SP C = Concentration of common ion.
C
Above formula is applicable, for AB type Salt.
coMPlEX ForMAItoN
If solubility of AgCl in
H2O Æ S1, 0.1 M BaCl2 Æ S2, 0.5 M AgNO3 Æ S3 Ag + + 2NH3  [Ag(NH3 ) 2 ]+
then order of solubility S1 > S2 > S3 because Formation constant or stability constant for complex.
1 [Ag(NH3 ) 2 ]+
S¢ ¥ Kf = (i)
C
[Ag + ][NH3 ]2
Eg. Solubility of PbI2 = in
Generally, Kf is the large value, so, reaction for the formation
(i) 0.1 M KI
of complex proceeds almost completely.
(ii) 0.1 M Pb(NO3)2
KSP(PbI2) = 7.1 ¥ 10–9 Stability constant of complex
Sol. 1
Kinst =
(i) PbI 2  Pb +2 + 2I - Kf
S¢ S¢ (2 S ¢ + 0.1) = 0.1 Kf≠ fi Kinst Ø fi Stability of complex ≠
+ –
KI h K + I Complex formation in more than one-step process
0.1 M 0.1 M 0.1 M Ag + + NH3  [Ag(NH3 )]+ ; K f1
KSP = 7.1 ¥ 10–9 = S¢ ¥ (0.1)2
S¢ = 7.1 ¥ 10–7 M [Ag(NH3 )]+
K f1 = (ii)
(ii) PbI2 m Pb+2 + 2I– [Ag + ][NH3 ]
(S¢ + 0.1) 2S¢ [Ag(NH3 )]+ + NH3  [Ag(NH3 ) 2 ]+ ; K f 2
(i) Zn (OH)2(s) m Zn(OH)2(aqueous)

[Ag(NH3 ) 2 ]+
K f2 = (iii) K1 = [Zn(OH)2](aqueous)
[Ag(NH3 )]+ [NH3 ]
Basic nature
\ K f = K f1 ¥ K f 2 (ii) Zn(OH)2(aqueous) m Zn(OH)+ + OH–;
Effect of complex formation in solubility
[Zn(OH) + ][OH - ]
Due to complex formation, solubility increases. Kb1 = K 2 =
Solubility of AgCl in aqueous NH3 solution: [Zn(OH) 2 ]
AgCl(s)  Ag + + Cl- ; KSP = x( x - y ) (iii) Zn(OH) +  Zn +2 + OH -

x mol/e x- y x
[Zn +2 ][OH - ]
+ + x Kb2 = K3 =
Ag + 2NH3  [Ag(NH3 ) 2 ] ; K f = [Zn(OH) + ]
( x - y )(C - 2 x) 2
x C – Acidic nature
x – y C – 2y y=x - +
(iv) Zn(OH)2(aqueous) + H2O  Zn(OH)3 + H
||
C – 2x [Zn(OH)3- ][H + ]
as Kf is high, so x = y K4 =
[Zn(OH) 2 ]
On adding both equations
(v) Zn(OH)3- + H 2O  Zn(OH) 24- + H +
AgCl(s) + 2NH3 (aq.)  [Ag(NH3 ) 2 ]+ + Cl-
c - 2x x x [Zn(OH) 4 ]-2 [H + ]
K5 =
x2 [Zn(OH)3- ]
K f ¥ KSP =
(C - 2 x) 2 \ solubility of Zn(OH)2 = S
Amphoterism = [Zn(OH) 2 ]aq + [Zn(OH) + ] + [Zn +2 ]
Zn(OH)2, Cr(OH)3, Al(OH)3 shows amphoterism, show solu-
bility increases because of acidic and basic behaviour. + [Zn(OH)3- ] + [Zn(OH) 4 ]-2
For example, Zn(OH)2 K1K 2 K1K 2 K 3 K1K 4 K1K 4 K 5
= K1 + + + +
Solubility of Zn(OH)2 is because of five forms in the aqueous [OH - ] [OH - ]2 [H + ] [H + ]2
solution.
Solved Examples
1. Find the pH value: OR

M N Note:
(i) H 2SO 4 (ii) Ba(OH) 2
1000 100 For very diluted solution, i.e., when [H+] or [OH–] is
M < 10–6M, while calculating the pH H+ or OH– due to
(iii) Sr(OH) 2 self-ionisation of water are taken.
10
Sol. (i) [H+] = 2 ¥ 10–3 If we consider, the common ion effect of water.
pH = 3 – log 2 = 2.7
(ii) [OH–] = 10–2 H2O m H+ + OH–
POH = 2 x + 10–7 x
pH = 14 – 2 = 12 HCl h H+ + Cl–
(iii) [OH–] = 2 ¥ 10–1 x + 10–7 10–7
POH = 1 – log 2 = 1 – 0.3 = 0.7 KW = [H+][OH–] = 10–14
\ Ph = 14 – 0.7 = 13.3 (x + 10–7)x = 10–14
2. Find the pH of 10–7 MHCl. x2 + 10–7x – 10–14 = 0
Sol. [H+] = 10–7 + {10–7} due to self-ionisation of H2O. x = 0.618 ¥ 10–7
= 2 ¥ 10–7 [H+] = 10–7 + 0.618 ¥ 10–7 = 1.618 ¥ 10–7
pH = 7 – log 2 = 6.7 pH = 6.79
3. Find the pH of 10–8 M NaOH. FCH2COOH m FCH2COO– + H+

Sol. [OH–] = 10–8 + 10–7 C – –
= 1.1 ¥ 10–7 C–x x x = 4 ¥ 10– 4
POH = 7 – log 1.1
(4 ¥ 10- 4 ) 2
pH = 14 – 7 + log(1.1) K a = 4 ¥ 10- 4 =
7 + log(1.1) C - 4 ¥ 10- 4
4. Calculate the pH of C = 8 ¥ 10–4 M
–5
(i) 0.1 M CH3COOH solution Ka = 1.8 ¥ 10 9. How much water must be added to 1 L of 0.2 M solu-
(ii) 10–6 M CH3COOH solution pKa = 4.74 tion of HA, if a of acid is to be doubled, Ka = 1.8 ¥ 10–4
Ka Sol. ‘a ’ µ V
Sol. (i) a = 2
C Vi Ê a ˆ
V µ (a ) 2 \ =Á ˜
1 V f Ë 2a ¯
pH = [4.74 - log 10-1 ]
2 Vi = 1 L fi Vf = 4 ¥ 1 = 4L
= 2.87 \ water added = 3 L
(ii) [H + ] = C ◊ a 10. Calculate the pH of the following solutions:
(i) 200 mL 0.1 M of H2SO4 + 300 mL 0.1 M NaOH
a 2c (ii) 400 mL 0.05 N H2SO4 + 200 mL 0.1 M KOH
Ka =
1- a (iii) 100 mL 0.1 N HCl + 100 mL 0.1 M Ba(OH)2
0.1 ¥ 2 ¥ 200 - 0.1 ¥ 1 ¥ 300
10- 6 ¥ a 2 Sol. (i) [H + ] =
fi 1.8 ¥ 10-5 = 500
1- a
10
fi a = 0.95 = = 2 ¥ 10- 2
[H+] = 0.95 ¥ 10–6 500
pH = 6.022 pH = 2 – log 2 = 1.7
5. If a = 0.01 for centimolar solution of weak acid. Find (ii) pH = 7  SNaVa = SNbVb
the value of PKa. 0.1 ¥ 100 - 0.1 ¥ 2 ¥ 100
(iii) [OH - ] =
Sol. Ka = a2C 200
= (10–2)2 ¥ 10–2 10
= 10–6 = = 5 ¥ 10- 2
Ka
200
P =6
POH = 2 – log 5 = 14 – (2 – log 5) = 12 + log 5 =
6. Calculate the concentration of OH– in 10–4 M solution
12.7
if weak acid HA4% ionised.
11. Calculate the pH of the following solutions:
+ -4 4 (i) 50 mL (pH = 1) + 50 mL (pH = 2)
Sol. [H ] = 10 ¥ = 4 ¥ 10- 6
100 (ii) 50 mL (pH = 2) + 50 mL (pH = 12)
Sol. (i) [H+]1 = 10–1; 50 mL
10-14
[OH - ] = = 2.5 ¥ 10- 9 M [H+]2 = 10–2; 50 mL
4 ¥ 10- 6
10-1 ¥ 50 + 10-2 ¥ 50
[H + ] =
7. Calculate the molar concentration of NH4OH solution 100
that has pH = 12. Given Kb = 1.8 ¥ 10–5. = 5.5 ¥ 10 –2
Sol. pH = 12 fi pOH = 2 fi [OH–] = 10–2 pH = 2 – log 5.5 = 1.26
[OH - ] = 10-2 = 1.8 ¥ 10-5 ¥ C (ii) pH = 12 means basic solution
\ POH = 2 So [OH–] = 10–2 M
C = 5.55 and pH = 2 So [H+] = 10–2M
8. What concentration of FCH2COOH is needed so that Since S(NV) acid = S(NV) base fi Neutral solu-
[H+] is 4 ¥ 10–4. Ka = 4 ¥ 10–4? tion
Sol. [H + ] = 4 ¥ 10- 4 = 4 ¥ 10- 4 ¥ C = [H+] = [OH–] = 10–7
fi pH = 7
Ka 12. Ka for acid HA is 2.5 ¥ 10–8. Calculate for its decimolar
C = 4 ¥ 10- 4 fi a = =1 solution at 25°C.
C
(i) % dissociation
fi a is not negligible.
(ii) pH
If Ka/C > 10–3 or a > 5%
(iii) OH– ion concentration
Sol. HA m H+ + A– x x 2 + xy
C 0 0 Substitute for y = in K HA = =
2 c
C(1 – a) Ca Ca
2 x2 + x2
[H + ][A - ] Ca ◊ Ca Ca 2 1.6 ¥ 10-5 =
Ka = fi Ka = = ª Ca 2 2 ¥ 0.5
[HA] C (1 - a ) (1 - a ) 3x2 = 1.6 ¥ 10–5 fi x2 = 5.33 ¥ 10–6
x = 2.30 ¥ 10–3 M, y = 1.15 ¥ 10–3 M
Ka 2.5 ¥ 10- 8 [H+]Final = x + y = 2.30 ¥ 10–3 + 1.15 ¥ 10–3
(i) \ a = = (C = 1/10 M)
C 1/10 = 3.45 ¥ 10–3 M
= 5 ¥ 10–4 = 0.05% pH = –log10 (3.45 ¥ 10–3)
1 pH = 2.462
(ii) [H+] = Ca = ¥ 5 ¥ 10- 4 = 5 ¥ 10–5 mol/L 15. Calculate pH of [HS–], [S2–], [Cl–] in a solution which
10
fi So pH = 5 – log 5 = 4.30 is 0.1 M HCl and 0.1 M H2S given that K a1 (H2S) =
(iii) [H+] [OH–] = 1 ¥ 10–14 10–7, Ka2 (H2S) = 10–14. Also calculate a1 and a2.
Sol. HCl + H2S
10-14 0.1 0.1
\ [OH–] = = 2 ¥ 10–10 mol/L.
5 ¥ 10-5 C1 = C2 = 0.1
\ pH = 1 (most of [H+] comes from HCl]
13. Determine the degree of dissociation of 0.05 M NH3 at
H2S m H+ + HS–
25°C in a solution of pH = 10.
0.1(1 – a1) Ca1 Ca1 = 0.1 a1
Sol. NH4OH m NH4+ + OH–
C 0 0 Ca1 ¥ 10-1 10-7
Ka1 = = = a1
C – Ca Ca Ca C (1 - a1 ) 10-1
Given: pH = 10 fi a1 = 10–6
[H+] = 10–10 HS– m S2– + H+
[H+] [OH–] = 1 ¥ 10–14 Ca1(1 – a2) Ca1a2 0.1
1 ¥ 10-14 10–14 = 0.1 ¥ a2
\ [OH–] = = 10–4 = Ca fi a2 = 10–13
10-10 [S2–] = Ca1a2
[OH - ] 10- 4 = 10–6 ¥ 10–1 ¥ 10–13 = 10–20 M
\ a= = = 2 ¥ 10–3 or 0.2 %
C 0.05 16. Find out Kh at 363 K (90°C) of a salt of [strong acid
14. Two weak monobasic organic acids HA and HB have – weak base] if the value of Kb is 10–5 [At 90°C Kw =
dissociation constants as 1.6 ¥ 10–5 and 0.4 ¥ 10–5 re- 10–12].
spectively at 25° C. If 500 mL of 1 M solution of each K w 10-12
of these two acids are mixed to produce 1 L of mixed Sol. K h = = = 10-7
Kb 10-5
solution, what is the pH of the resulting solution ?
Sol. In such cases, we have to consider H+ from both HA 17. How many grams of NH4Cl should be dissolved per
and HB simultaneously. The concentration of HA and litre of solution to have a pH of 5.13 ? Kb for NH3 is
HB in the mixture = 0.5 M [equal volumes are mixed] 1.8 ¥ 10–5?
= say ‘c’ Sol. NH4Cl is a salt of strong acid and weak base for solu-
tions of such salts.
HA Æ H+ + A–
1
HB Æ H+ + B– pH = [pKW – log C – pKb]
Let, x = [H+] from HA and y = [H+] from HB 2
fi [H+]final= x + y fi 10.26 = 14 – log C – 4.74
fi log C = 9.26 – 10.26 = –1.0
( x + y) x ( x + y) y \ C = 10–1 M
K HA = and K HB =
c c [NH4Cl] = 10–1 M
+
[H ]HA x k ¥ C WNH4 NO3 = 10–1 ¥ 53.5 gL–1 = 5.35 gL–1
= = HA
[H + ]HB y kHB ¥ C
18. What is the pH of 0.4 M aqueous NaCN solution?
x 1.6 ¥ 10 -5 (Given: pKb of CN– = 4.70)
= =2 Sol. pKa for HCN = 14 – 4.7 = 9.30
y 0.4 ¥ 10-5
NaCN + H2O m NaOH + HCN
x C 0 0
x = 2y fi y =
2 C(1 – h) Ch Ch
22. What is the ratio of salt to acid when the buffering ac-
Kh K wC
\ [OH – ] = Ch = C = K hC = tion of a mixture of CH3COOH and CH3COONa is
C Ka maximum?
1 Sol. The buffer action of a buffer mixture is effective in the
pOH = [pKw – pKa – log C] pH range pKa ± 1. It is maximum when pH = pKa.
2
23. What amount of sodium propanoate should be added to
1 one litre of an aqueous solution containing 0.02 mole of
= [14 – 9.30 – log (0.4)] = 2.548
2 propanoic acid to obtain a buffer solution of pH 4.74?
\ pH = 14 – 2.5 = 11.45 What will be the pH if 0.01 mol HCl is dissolved in
19. The acid ionisation constant for the above buffer solution ? Compare the last pH value
Zn2+ + H2O m Zn(OH)+ + H+ with the pH of 0.01 molar HCl solution. Dissociation
is 1.0 ¥ 10–9. Calculate the pH of 0.10 M solution of constant of propanoic acid at 25°C is 1.34 ¥ 10–5.
ZnCl2. Also calculate the basic dissociation constant of Sol. Using Henderson’s expression
Zn(OH)+. [salt]
pH = pKa + log
Sol. Zn2+ + H2O m Zn(OH)+ + H+ [acid] [Salt]
K We get 4.74 = – log (1.34 ¥ 10–5) + log
+ h
\ [H ] = C ◊ h = C C = K hC 0.02
[Salt]
È where K b is the basic dissociation of ˘ which gives 4.74 = 4.87 + log
K wC Í + ˙ 0.02
= Í Zn(OH) ˙
Kb Í ˙ [Salt]
+ 
Zn 2+ + OH - or log = – 0.13 = log 0.74
Î i.e., Zn(OH)  ˚ 0.02
or [Salt] = 1.48 ¥ 10–2 M
We know Zn2+ and Zn(OH)+ are conjugate acid and
Hence, amount of sodium propanoate to be added =
base.
1.48 ¥ 10–2 ¥ 96 g = 1.42 g.
\ Ka ¥ Kb = 10–14
The addition of 0.01 mol of HCl converts the equiva-
10-14 lent amount of sodium propanoate into propanoic acid.
or Kb = = 10-5
10-9 Hence, we will have
(0.01482 - 0.01) mol L-1
10-14 ¥ 0.1 pH = 4.87 + log
Now, [H + ] = = 10- 6 = 10- 3 (0.02 + 0.01) mol L-1
10-9
pH = 4.87 + log (0.160) = 4.87 – 0.79 = 4.08
pH = 3 (The pH of 0.01 molar HCl solution will be
20. What is the pH of a mixture containing 0.2 M X– (base) pH = – log (0.01) = 2)
and 0.4 M HX with pKb (X–) = 4? 24. Equal volumes of 0.04 M CaCl2 and 0.0008 M Na2SO4
10-14 are mixed. Will we get a precipitate?
Sol. HX m H+ + X– , Ka = = 10–10 Ksp for CaSO4 = 2.4 ¥ 10–5
Kb
Sol. CaCl2 + Na2SO4 Æ CaSO4 + 2NaCl
[HX] 10-10 ¥ 0.4 Millimole 0.04 V 0.0008 ¥ V 0 0
[H + ] = K a =
[X - ] 0.2 added
Suppose V mL of both are mixed
or pH = 10 – log 2
21. The pH of a mixture of 1 M benzoic acid (pKa = 4.2) 0.04 V
\ [Ca2+] =
and 1 M sodium benzoate is 4.5, in 150 mL buffer, ben- 2V
zoic acid find volume of benzoic acid. 0.0008 V
[salt] [SO42–] =
Sol. pH = pKa + log 2V
[Acid]
0.04 V 0.0008 V
(150 - x) ˘ \ [Ca2+][SO42–] = ¥ = 8 ¥ 10–6
4.5 = 4.2 + log ÈÍ ˙˚ where x is the volume of
2V 2V
Î x
benzoic acid Thus, [Ca2+][SO42–] in solution < Ksp
8 ¥ 10–6 < 2.4 ¥ 10–5
È (150 - x) ˘ È (150 - x) ˘
0.3 = log Í ˙˚ or 2.0 = ÍÎ ˙˚ \ CaSO4 will not precipitate.
Î x x 25. Calculate the [OH–] of a solution after 50.0 mL of
or x = 50 mL 0.2 M MgCl2 is added to 50.0 mL of 0.4 M NaOH. Ksp
of Mg(OH)2 is 1.2 ¥ 10–11.
Sol. MgCl2 + 2NaOH Æ Mg(OH)2 + 2NaCl

AgBr(s) + 2S2O32-  Ag(S2O3 )32- + Br -
initially 10 mm 20 mm 0 0
final 0 0 10 mm 20 mm (0.1 – 2x) x x
Thus, 10 m mole of Mg(OH)2 are formed. The product x2
K f ¥ KSP = 5 ¥ 1013 ¥ 5 ¥ 10-13 =
10 ˘ È 20 ˘
2
(0.1 - 2 x) 2
of [Mg2+][OH–]2 is, therefore, ÈÍ ¥ =4¥
Î100 ˙˚ ÍÎ100 ˙˚ x
5= fi x = 0.045 M
–3
10 which is more than Ksp of Mg(OH)2. Now solubil- 0.1 - 2 x
ity (S) of Mg(OH)2 can be derived by Selective Precipitation
Ksp = 4S3
30. In a solution of 10–3 M Cl– and 10–2M CrO 24- , if sol-
\ S= 3 K sp = 3 1.2 ¥ 10-11 = 1.4 ¥ 10–4 M id AgNO3 is gradually added, which will precipitate
first AgCl, Ag2CrO4. Assuming no change in volume,
\ [OH–] = 2S = 2.8 ¥ 10–4 M what % of Cl– ion originally present remain in solution
26. Will a precipitate of Mg(OH)2 be formed in a 0.002 M when Ag2CrO4 begin to precipitate? Ksp(AgCl) = 10–10,
solution of Mg(NO3)2, if the pH of solution is adjusted Ksp(Ag2CrO4) = 10–12.
to 9? Ksp of Mg(OH)2 = 8.9 ¥ 10–12.
For ppt. of AgCl
Sol. pH = 9 Sol.
\ [H+] = 10–9 M 10-10 < [Ag + ][Cl- ]
or [OH–] = 10–5 M \ [Ag+] > 10–7M
Now if Mg(NO3)2 is present in a solution of [OH–] = For ppt. of Ag2CrO4
10–5 M, then,
Product of ionic conc. 10-12 < [Ag + ]2 [CrO 24- ]
= [Mg+2] [OH–]2 = [0.002] [[10–5]2 [Ag+] > 10–5M
= 2 ¥ 10–13 lesser than Ksp of Mg(OH)2, i.e., 8.9 ¥ 10–12 So AgCl Start Precipitate Before Ag2CrO4
\ Mg(OH)2 will not precipitate. To precipitate Ag2CrO4 before AgCl
27. You are given 10–5 M NaCl solution and 10–8 M AgNO3 10–10 = [Ag+][Cl–]
solution, they are mixed in 1:1 volume ratio. Predict = 10–5 ¥ [Cl–]
whether AgCl will be precipitated or not, if solubility [Cl ] = 10–5 M
–
product of AgCl in 10–2 M AgNO3 is = 10–10 mole L–1? % of Cl– ion originally present remain in solution when
Ag2CrO4 begin to precipitate
10-5 10-8
Sol. Ionic product = ¥ = 25 ¥ 10–15 < ksp
2 2 10-5
%[Cl- ] = ¥ 100 = 1%
Hence no precipitation will take place. 10-3
28. In the excess of NH3(aqueous), Cu+2 ion form a deep 31. What is the maximum volume of water required to dis-
blue complex ion [Cu(NH3)4]2+ which has Kf = 1011. If solve 1 g of calcium sulphate at 25°C. For calcium sul-
the concentration of Cu+2 ion in solution prepared by phate, Ksp= 9.0 ¥ 10–6.
adding 5 ¥ 10–3 mol. of CuSO4 to 0.5 L of 0.4 M NH3 Sol. CaSO4 (aq) m Ca2+ (aq) + SO42– (aq)
A If S is the solubility of CaSO4 in moles L–1
(aqueous) is . Then, what is the value of A?
(36) 4 Ksp= [Ca2+] ¥ [SO42–] = S2
Sol. Cu+2 + 4NH3 m [Cu(NH3)4]+2 \ S = Ksp = 9.0 ¥ 10- 6
Init. : 0.01 0.4 –
ion : [Cu+2] 0.4 – 4 ¥ 0.01 0.01 = 3 ¥ 10–3 mol L–1
= 0.36 = 3 ¥ 10–3 ¥ 136 g L–1 = 0.408 g L–1
For dissolving 0.408 g of CaSO4 water required
0.01 +2 10-5
1011 = fi [Cu ] = 1
[Cu +2 ][0.36]4 [36]4 L =1L
0.408
29 Calculate the molar solubility of AgBr in 0.1 M \ for dissolving 1g CaSO4 water required = 2.45 L.
Na2S2O3 (aqueous) solution. Ksp of AgBr = 5 ¥ 10–13 32. Calculate simultaneous solubility of AgCNS and AgBr
3-
and K f [Ag(S2O3 ) 2 ] = 5 ¥ 1013. in a solution of water. Ksp of AgBr = 25 ¥ 10–13 and Ksp
of AgCNS = 5 ¥ 10–12.
Sol. AgBr(s) m Ag+ + Br–
Sol. Let solubility of AgCNS and AgBr in a solution be a
x x
and b mol L–1 respectively.
Ag + + 2S2O32-  Ag(S2O3 )32- AgCNS (s) m Ag+ + CNS–
x–y 0.1 – 2x x a a
AgBr (s) m Ag+ + Br– Ksp = (CdS) = 8 ¥ 10–27

b b Ksp = (ZnS) = 1 ¥ 10–21
\ For AgCNS KspAgCNS = [Ag + ][CNS- ] Ka = (H2S) = 1.1 ¥ 10–21
Sol. In order to prevent precipitation of ZnS
5 ¥ 10–12 = (a + b)(a) ...(i)
[Zn2+][S2–] < Ksp(ZnS) = 1 ¥ 10–21
+ -
For AgBr KspAgBr = [Ag ][Br ] (ionic product)
25 ¥ 10–13 = (a + b)(b) ...(ii) or (0.1)[S2–] < 1 ¥ 10–21
By Eqs (i) and (ii), or [S2–] < 1 ¥ 10–20
a 5 ¥ 10-12 This is the maximum value of [S2–] before ZnS will
\ = =2 or a = 2b precipitate. Let [H+] to maintain this [S2–] be x. Thus
b 25 ¥ 10-13
for H2S m 2H+ + S2–
\ By Eq. (i), (2b + b)(2b) = 1 ¥ 10–12
[H + ]2 [S2- ] x 2 (1 ¥ 10- 20 )
6b2 = 5 ¥ 10–12 Ka = =
b = 0.912 ¥ 10–6 mol L–1 = 9.12 ¥ 10–5 M [H 2S] 0.1
By Eq. (i), (a + a/2) (a) = 5 ¥ 10–12 = 1.1 ¥ 10- 21
a = 1.82 ¥ 10–6 mol L–1
33. What [H+] must be maintained in saturated H2S(0.1 M) or x = [H+] = 0.1 M
to precipitate CdS but not ZnS, if [Cd2+] = [Zn2+] = 0.1 \ No ZnS will precipitate at a concentration of H+
initially ? greater than 0.1 M.
Exercise
(b) is decreased
lEVEl I (c) remain constant
(d) changes which cannot be predicted unless dis-
1. If KW for H2O at 90ºC is 10–12 M2, then what would be sociation constant of weak acid or weak base is
the dissociation constant of water at the same tempera- provided.
ture? [Assume d H2O = 1 g/mL] 8. 100 mL solution (I) of buffer containing 0.1(M) HA
(a) 10–14 (b) 1.8 ¥ 10–16 and 0.2 (M) A–, is mixed with another solution (II) of
(c) 1.8 ¥ 10 –14
(d) 10–12 100 mL containing 0.2(M) HA and 0.3(M) A–.
2. If 100 mL of 0.1 M CH3COOH is titrated against 50 After mixing, what is the pH of resulting solution?
mL of 0.1 M NaOH. Calculate pH of resulting solution [Given: pKa of HA = 5]
if pKa for CH3COOH = 4.76. (a) 5 – log 5/3 (b) 5 + log 5/3
(a) 4.76 (b) 4.46 (c) 5.06 (d) 2.76 (c) 5 + log 2/5 (d) 5 – log 5/2
3. What is the minimum pH required to prevent the pre- 9. Kb of an acid-base indicator H In is 10–9. The pH at
cipitation of ZnS in a solution that is 0.01 M ZnCl2 which its 10–3 (M) solution shows the colour change?
and saturated with 0.10 M H2S ? [Given Ksp = 10–21, (a) 9 (b) 7 (c) 5 (d) 3
K a1 ¥ K a2 = 10–20] 10. Ksp of SrF2 (s) in water is 3.2 ¥ 10–14. The solubility of
SrF2 (s) in 0.1 (M) NaCl solution is
(a) 0 (b) 1 (c) 2 (d) 4
(a) 3.2 ¥ 10–9 (M)
4. 4 mL of HCl solution of pH = 2 is mixed with 6 mL of
(b) 2 ¥ 10–5 (M)
NaOH solution of pH = 12. What will be the final pH
(c) 4 ¥ 10–4 (M)
of solution? log 2 = 0.3
(d) Slightly higher than 2 ¥ 10–5 (M)
(a) 10.3 (b) 11.3 (c) 11 (d) 4.3
11. What will be the value of Kw at 90ºC, if [H+] in pure
5. A solution of CuSO4 is
water is 10–6 gram ion per litre?
(a) acidic in nature (b) alkaline in nature
(a) 10–10 (b) 10–16
(c) neutral in nature (d) amphoteric in nature –12
(c) 1 ¥ 10 (d) 2 ¥ 10–6
6. The pH of 0.5 (M) Ba(CN)2 solution is +
12. Concentration of [H ] will decrease on mixing which
[Given: pKb of CN– = 9.3]
of the following salts with the solution of acetic acid?
(a) 8.35 (b) 3.35 (c) 9.35 (d) 9.5
(a) KCN (b) NaCl
7. On diluting a buffer solution, its pH
(c) NH4Cl (d) Al2(SO4)3
(a) is increased
13. Aqueous solution of FeCl3 (c) pH remains unchanged

(a) turns blue litmus solution red. (d) None of the above
(b) turns red litmus solution blue. 24. Which of the following indicators is appropriate in the
(c) decolourises litmus solution. titration of NH4OH and strong acid?
(d) does not affect litmus solution. (a) Phenolphthalein (b) Methyl orange
14. When HCl gas is passed in saturated solution of com- (c) Phenol red (d) Litmus
mon salt, then pure NaCl is precipitated, because 25. What will be the mole fraction of acetone in the so-
(a) Ionic product of Na+ and Cl– exceeds the solubil- lution formed by 1.8 gram of water and 2.9 gram of
ity product of NaCl. acetone?
(b) HCl is highly soluble in water. 2 1 2.9
(a) (b) 2.9 (c) (d)
(c) ionisation of NaCl is decreased due to chloride 3 3 4.7
ions of HCl.
26. Value of pKa for acetic acid at 25ºC is 4.75, then what
(d) HCl absorbs impurities.
will be the pH value of the solution in which ratio of
15. Which of the following has maximum value of solubil-
concentration of sodium acetate and acetic acid is 10?
ity product?
(a) 3.75 (b) 4.75 (c) 5.75 (d) 10.0
(a) Fe(OH)3 (b) Al(OH)3
27. Phenophthalein gives which of the following colours in
(c) Cr(OH)3 (d) Zn(OH)2
acidic medium?
16. Which of the following is true for aqueous solution of
(a) Pink (b) Red
CH3NH2 of 0.1 M concentration?
(c) No colour (d) Violet
(a) [OH–] = 0.1M (b) pH = 0
28. If pKa of acetic acid at 25ºC is 4.75, then determine the
(c) pH < 7 (d) pH > 7
pH of that solution in which 0.02 M sodium acetate and
17. If pH of 0.1M acetic acid is 3.0, then dissociation con-
acetic acid are present.
stant of this acid will be
(a) 4.75 (b) 3.75 (c) 5.75 (d) 2.75
(a) 1 ¥ 10–4 (b) 1 ¥ 10–5
–3 29. Which of the following ions are present in the solution
(c) 1 ¥ 10 (d) 1 ¥ 10–8
of the monosodium salt of orthophosphoric acid?
18. Solution of which of the following will have maximum
(a) Na+, PO4–3, H2PO4–2, HPO4–1
pH value?
(b) Na+, HPO4–2
(a) NaCl (b) Na2CO3
(c) Na+, H2PO4–, HPO4–2, PO4–3
(c) NH4Cl (d) NaHCO3
(d) Na+, HPO4–2, PO4–3
19. A precipitate will be obtained on mixing equal vol-
ume of which of the following solutions, if Ksp = 1.8 ¥ 30. What is the concentration of Ag+ ion in a 1L solution
10–10? containing 0.02 mol of AgNO3 and 0.14 mol of NH3.
(a) 10–4 M [Ag+] and 10–4M [Cl–] For Ag(NH3)2+, Kstab = 108.
(b) 10–5 M [Ag+] and 10–5M [Cl–] (a) 2 ¥ 10–7(M) (b) 10–8(M)
–8
(c) 10–6 M [Ag+] and 10–6M [Cl–] (c) 2 ¥ 10 (M) (d) 2 ¥ 10–9(M)
(d) 10–10 M [Ag+] and 10–4M [Cl–] 31. A 50 mL solution of pH = 1 is mixed with a 50 mL so-
20. Which of the following is present in an aqueous solu- lution of pH = 2. then pH of the mixture will be nearly
tion of Na2CO3? (a) 0.76 (b) 1.26 (c) 1.76 (d) 2.26
(a) H2CO3, Na+, OH– (b) H2CO3, OH– 32. The pH of a solution is 7.00. To this solution, sufficient
–2
(c) CO3 ion (d) Na+ and OH– ion base is added to increase the pH to 12.0. The increase
21. Why is NH4Cl added before NH4OH in qualitative in OH– ion concentration is-
analysis of third group ions? (a) 5 times (b) 1000 times
(a) To increase concentration of OH–. (c) 105 times (d) 4 times
(b) To decrease concentration of OH–. 33. The dissociation constants of two acids HA1 and HA2
(c) To make solution dilute. are 3.0 ¥ 10–4 and 1.8 ¥ 10–5 respectively. The relative
(d) For pure precipitation. strengths of the acids will be approximately
22. What is the volume of water needed to make normality (a) 1 : 4 (b) 4 : 1 (c) 1 : 16 (d) 16 : 1
of the solution 3N, prepared by mixing 250 mL 6 M
34. If 50 mL of 0.2 (M) KOH is added to 40 mL of 0.5(M)
HCl and 350 mL 8M HNO3?
HCOOH. The pH of the resulting solution is (K = 1.8 ¥
(a) 833.3 mL (b) 933.3 mL
10–4)
(c) 1000 mL (d) 500 mL
23. On dilution of a solution formed from CH3COONH4 (a) 3.75 (b) 5.6 (c) 7.5 (d) 3.4
(a) pH decreases 35. The sodium salt of a certain weak monobasic organic
(b) pH increases acid is hydrolysed to an extent of 3% in its 0.1 M solu-
tion at 25°C. Given that the ionic product of water is

10–14 at this temperature, what is the dissociation con- lEVEl II
stant of the acid ?
(a) ª 1 ¥ 10–10 (b) ª 1 ¥ 10–9 1. 100 mL of 0.02 M benzoic acid (pKa = 4.2) is titrated
–9
(c) 3.33 ¥ 10 (d) 3.33 ¥ 10–10 using 0.02 M NaOH. pH after 50 mL and 100 mL of
36. When 100 mL of 0.4 M CH3COOH are mixed with 100 NaOH have been added are
mL of 0.2 M NaOH, the [H3O+] in the solution is ap- (a) 3.50,7 (b) 4.2, 7
proximately : [Ka(CH3COOH) = 1.8 ¥ 10–5] (c) 4.2, 8.1 (d) 4.2, 8.25
(a) 1.8 ¥ 10–6 (b) 1.8 ¥ 10–5 2. What is the difference in pH for 1/3 and 2/3 stages of
(c) 9 ¥ 10 –6
(d) 9 ¥ 10–5 neutralisation of 0.1 M CH3COOH with 0.1 M NaOH?
37. What will be the pH at the equivalence point during the (a) – 2 log 3 (b) 2 log (1/4)
titration of a 100 mL 0.2 M solution of CH3COONa (c) 2 log (2/3) (d) –2 log 2
with 0.2 M solution of HCl ? Ka = 2 ¥ 10–5 3. The pH of 1.0 M NaHSO4 solution will be (given that
K1 and K2 for H2SO4 equal to • and 10–2 respectively)-
(a) 3 – log 2 (b) 3 + log 2 (a) nearly 1.0 (b) between 2 and 3
(c) 3 – log 2 (d) 3 + log 2 (c) between 1.2 and 1.8 (d) between 3 and 4
38. What % of the carbon in the H2CO3, HCO3–. Buffer 4. At 25 °C, the dissociation constant of HCN and HF are
should be in the form of HCO3– so as to have a neutral 4 ¥ 10–10 and 6.7 ¥ 10–4. The pH of a mixture of 0.1 M
solution ? (Ka = 4 ¥ 10–7) HF and 0.1 M HCN.
(a) 20 % (b) 40 % (c) 60 % (d) 80 % (a) 2.087 (b) 3.0 (c) 5.5 (d) 6.0
39. 50 mL of 0.1 M NaOH is added to 60 mL of 0.15 M 5. The pH of a solution prepared by mixing 50.0 mL of
H3PO4 solution (K1, K2 and K3 may be taken as 10–3, 0.200 M CH3CO2H and 50.0 mL of 0.100 M NaOH.
10–8 and 10–13 respectively). The pH of the mixture Ka = 1.8 ¥ 10–5.
would be about (a) 5 (b) 4.74 (c) 10.3 (d) 7
(a) 3.1 (b) 5.5 (c) 4.1 (d) 6.5 6. What fraction of an indicator Hln is in the basic form at
40. The concentration of Mg2+ in the solution made by a pH of 6 if pKa of the indicator is 5 ?
mixing 10 mL of 0.25 M Mg(NO3)2 and 25 mL of 0.2 1 1 10 1
M NaF will be (Ksp(MgF2 = 8 ¥ 10–8) (a) (b) (c) (d)
2 11 11 10
(a) 0.0027 M (b) 0.0714 M
7. An acid-base indicator which is a weak acid has a pKa
(c) 0.0030 M (d) 0.0060 M
value = 5.5. At what concentration ratio of sodium
41. The precipitate of CaF2(Ksp = 1.7 ¥ 10–10) is obtained
acetate to acetic acid will the indicator show a colour
when equal volumes of which of the following are
half-way between those of its acid and conjugate base
mixed?
(a) 10–4 M Ca2+ + 10–4 M F– forms ? pKa of acetic acid = 4.75.
(b) 10–2 M Ca2+ + 10–3 M F– (a) 4.93 : 1 (b) 6.3 : 1 (c) 5.62 : 1 (d) 2.37 : 1
(c) 10–5 M Ca2+ + 10–3 M F– 8. What is the percentage hydrolysis of NaCN in N/80
(d) 10–3 M Ca2+ + 10–5 M F– solution when the dissociation constant for HCN is
42. 1 CC of 0.1 N HCl is added to 99 CC solution of NaCl. 1.3 ¥ 10–9 and Kw = 1.0 ¥ 10–14.
The pH of the resulting solution will be (a) 2.48 (b) 5.26 (c) 8.2 (d) 9.6
(a) 7 (b) 3 (c) 4 (d) 1 9. The OH– concentration at the equivalent point when a
43. If pKb for fluoride ion at 25°C is 10.83, the ionisation solution of 0.1 M acetic acid is titrated with a solution
constant of hydrofluoric acid in water at this tempera- of 0.1 M NaOH. Ka for the acid = 1.9 ¥ 10–5.
ture is (a) 7 ¥ 10–7 (b) 5.2 ¥ 10–7
–6
(a) 1.74 ¥ 10–5 (b) 3.52 ¥ 10–3 (c) 5.2 ¥ 10 (d) 7.2 ¥ 10–7
–4
(c) 6.75 ¥ 10 (d) 5.38 ¥ 10–2 10. A solution contains HCl, Cl2HCCOOH and CH3COOH
–4
44. The pH of 2.0 ¥ 10 M H3X solution assuming first at concentrations 0.09 M in HCl, 0.09 M in Cl2HC-
dissociation to be 100%, second to be 50% and third to COOH and 0.1 M in CH3COOH, pH for the solution is
be negligible is 1. Ka CH3COOH = 10–5. What is the Ka for dichloro-
(a) 3.7 (b) 2.4 (c) 3.0 (d) 3.52 acetic acid?
M (a) 1.25 ¥ 10–4 (b) 1.25 ¥ 10–3
45. What is the pH of 10% dissociated H CO solu- –6
200 2 3 (c) 1.25 ¥ 10 (d) 1.25 ¥ 10–2
tion ?
11. A solution of ammonia bought for cleaning the win-
(a) 3 (b) 4 (c) 5 (d) 6
dows was found to be 10% ammonia by mass, having a
46. pH of 0.01 M solution of potassium propionate is 8.
density of 0.935 g.mL–1. What is the pH of the solution.
What is the pKa of propionic acid?
Take Kb for protonation of ammonia = 5.5 ¥ 10–6.
(a) 4 (b) 2
(a) 10.7 (b) 2.3 (c) 11.7 (d) 6.7
(c) 0 (d) None of these
12. The kw of water at two different temperature is:- (a) 1.3 ¥ 102, 1.7 ¥ 10–5 M
T 25°C 50°C (b) 1.7 ¥ 102, 1.308 ¥ 10–5 M
kw 1.08 ¥ 10–14 5.474 ¥ 10–14 (c) 1.3 ¥ 104, 1.308 ¥ 10–4 M
Assuming that DH of any reaction is independent of (d) 1.7 ¥ 103, 1.67 ¥ 10–6 M
temperature. The enthalpy of neutralization of a strong 22. If Ksp for HgSO4 is 6.4 ¥ 10–5, then solubility of this
acid and strong base. substance in mole per m3 is
(a) 51.95 J/mole (b) 51.95 kJ/mole (a) 8 ¥ 10–3 (b) 6.4 ¥ 10–5
(c) 5.195 kJ/mole (d) 519.5 kJ/mole (c) 8 ¥ 10 –6
(d) None of these
13. Calculate the pH of the following solution 40 mL of 23. How many moles NH3 must be added to 2.0 L of 0.80
0.050 M Na2CO3 + 50 mL of 0.040 M HCl Use H2CO3; M AgNO3 in order to reduce the Ag+ concentration to 5
For H2CO3 Æ k1 = 4.2 ¥ 10–7, k2 = 4.8 ¥ 10–11 ¥ 10–8 M. Kf of [Ag(NH3)2+] = 108
(a) 8.35 (b) 8.0 (c) 6.65 (d) 7.0 (a) 0.4 (b) 2 (c) 3.52 (d) 4
14. Calculate the pH of the following solution given for 24. Solubility of solid zinc hydroxide at a pH of 5
H3PO4Æk1 = 7.5¥ 10–3, k2 = 6.2¥ 10–8, k3 = 10–12 Zn(OH)2(s) m Zn(OH)2(aq) k1 = 10–6 M (i)
40 mL of 0.020 M Na3PO4 + 40 mL of 0.040 M HCl: Zn(OH)2(aq) m Zn(OH) + OH k2 = 10–7 M (ii)
+ –
(a) 4.66 (b) 12.66 (c) 8.64 (d) 2.66
Zn(OH)+ m Zn2+ + OH– k3 = 10–4 M (iii)
15. How many moles of HCl can be added to 1.00 L of a
solution 0.1 M in NH3 and 0.1 M in NH4Cl without
–
Zn(OH)2(aq) + OH m Zn(OH)3 k4 = 103 M–1 (iv)
–
changing the pOH by more than 1.00 unit ? Assume no Zn(OH)3– + OH–m Zn(OH)42– k5 = 10 M–1 (v)
change in volume. Kb(NH3) = 1.8 ¥ 10–5. (a) 0.1 M (b) 2 ¥ 10–2M
(a) 0.82 moles (b) 0.05 moles –6
(c) 2 ¥ 10 M (d) 10M
(c) 0.082 moles (d) 0.03 moles 25. Calculate the solubility of solid zinc hydroxide at a pH
16. Calculate the OH– concentration of a solution prepared of 13. Given:
by dissolving 0.1 mol of Na3PO4 in sufficient water to Zn(OH)2(s) m Zn(OH)2(aq) k1 = 10–6 M (i)
make 1 L of solution K1 = 7.1 ¥ 10–3, K2 = 6.3 ¥ 10–8,
Zn(OH)2(aq) m Zn(OH) + OH k2 = 10–7 M (ii)
+ –
K3 = 4.5 ¥ 10–13.
(a) 3.73 ¥ 10–2 M (b) 3.73 ¥ 10–4 M Zn(OH)+ m Zn2+ + OH– k3 = 10–4 M (iii)
(c) 3.73 ¥ 10 M–6
(d) 3.73 ¥ 10–10 M Zn(OH)2(aq) + OH m Zn(OH)3 k4 = 103 M–1 (iv)
– –
17. Calculate the H3PO4 concentration of a solution Zn(OH)3– + OH–m Zn(OH)42– k5 = 10 M–1 (v)
prepared by dissolving 0.1 mol of Na3PO4 in suffi- (a) 0.1 M (b) 2 ¥ 10–2 M
cient water to make 1 L of solution K1 = 7.1 ¥ 10–3, –4
(c) 2 ¥ 10 M (d) 1.0 M
K2 = 6.3 ¥ 10–8, K3 = 4.5 ¥ 10–13. 26. Salt mixture containing Cu3(AsO4)2 (Ksp = 8 ¥ 10–36)
(a) 3.93 ¥ 10–12 M (b) 5.93 ¥ 10–18 M
–13 and Pb3(AsO4)2 (Ksp = 4.096 ¥ 10–36) is shaken with
(c) 4.5 ¥ 10 M (d) 6. 3 ¥ 10–8 M
water. Find the concentration of Pb+2 cations in the so-
18. A solution of weak acid HA was titrated with base
lution at equilibrium. Neglect any hydrolysis of the dis-
NaOH. The equivalence point was reached when 36.12
solved ions.
mL of 0.1 M NaOH was added. Now 18.06 mL of 0.1
M HCl were added to titrated solution, the pH was (a) 7.1 ¥ 10–8 M (b) 2.875 ¥ 10–8 M
–8
found to be 4.92. What will be the pH of the solution (c) 8.825 ¥ 10 M (d) 2.3 ¥ 10–8 M
obtained by mixing 10 mL of 0.2 M NaOH and 10 mL 27. At what minimum pH will 1.0 ¥ 10–3 mol of Al(OH)3
of 0.2 M HA? go into 1 L solution as [Al(OH)4]–?
(a) 5 (b) 9 (c) 10 (d) 8 Given : Ksp [Al(OH)3] = 5.0 ¥ 10–33 and for
19. A weak base BOH was titrated against a strong acid. [Al(OH)4–] ¤ Al3+ + 4OH– .K = 1.3 ¥ 10–34.
The pH at 1/4th equivalence point was 9.24. Enough (a) 6.4 (b) 9.4 (c) 4.4 (D) 7.0
strong base was now added (6 m. eq.) to completely 28. What is the solubility of AgCl in 0.20 M NH3 ?
convert the salt. The total volume was 50 mL. Find the Given: Ksp(AgCl) = 1.7 ¥ 10–10 M2, K1 = [Ag(NH3)+]/
pH at this point. [Ag+][NH3] = 2.33 ¥ 103 M–1 and K2 = [Ag(NH3)2+] /
(a) 11.2 (b) 2.8 (c) 10 (d) 6.8 [Ag(NH3)+][NH3] = 7.14 ¥ 103 M–1 .
20. Calculate pH of 1M NaHCO3 is given (a) 9.6 ¥ 10–5 M (b) 9.6 ¥ 10–6 M
H2CO3 + H2O m HCO3– + H3O+, pK1 = 6.38 (c) 9.6 ¥ 10 M–1
(d) 9.6 ¥ 10–3 M
HCO3– + H2O m CO3–2 + H3O+, pK2 = 10.26 29. Predict whether or not AgCl will be precipitated from
(a) 8.32 (b) 6.38 (c) 5.32 (d) 10.26 a solution which is 0.02 M in NaCl and 0.05 M in
21. At 25 °C, the solubility product values of AgCl and KAg(CN)2. Given Kinst (Ag(CN)2–) = 4.0 ¥ 10–19 M2 and
AgCNS are 1.7 ¥ 10–10 and 1.0 ¥ 10–12 respectively. Ksp (AgCl) = 2.8 ¥ 10–10 M2.
When water is saturated with both solids, calculate the (a) Data insufficient
ratio [Cl– ]/[CNS– ] and also [Ag+] in the solution. (b) AgCl will precipitate
(c) AgCl will not precipitate 3. Ka and Kb are the dissociation constant of weak acid
(d) None of these and weak base and Kw is the ionic product of water.
30. Equal volumes of 0.02 M AgNO3 and 0.02 M HCN
Column I Column II
were mixed. Calculate [Ag+] at equilibrium. Take
Ka(HCN) = 9 ¥ 10–10, Ksp(AgCN) = 4 ¥ 10–16. (A) 0.1(M) KCN solu- (P) pH  7
(a) 6.67 ¥ 10–4 M (b) 6.00 ¥ 10–3 M tion
–5
(c) 6.7 ¥ 10 M (d) 4.5 ¥ 10–8 M (B) 0.1(M) C6H5NH3Cl (Q) 1
solution pH = 6.5 + pKa
2
lEVEl III (C) 0.1(M) KCl solution (R) 1
pH = 7.5 – pKb
2
Match the Columns
(D) 0.1(M) (S) 1
1. Match the Columns: CH3COONH4 pH = 7 + pKa –
2
Column I Column II solution
1
pKb
(A) Buffer capacity is (P) 1 2
maximum for an pH = pKa + log
3 4. Match the columns:
acid buffer is
Column I Column II
(B) 1 (Q) 1
At the th of the (pKa + log3) (A) NaHCO3 solution (P) Cationic hydrolysis
4 2
(B) CuSO4 solution (Q) Anionic hydrolysis
equivalence point
for the titration of (C) Potash alum (R) Acidic
weak acid HA solution
(C) (R) (D) NaCN solution (S) Alkaline
3 1
At the th of the pH = pKa – log 5. Match the columns:
4 3
equivalence point Column I Column II
for the titration of (A) pH of 0.1M HA (pKa = 5) and (P) 4
weak acid HA 0.01 M NaA
(D) 1 (S) pH = pKa (B) pH of 0.1 M BOH (pKb = 6) and (Q) 7
The pH of (M)
3 0.1 M BCl
solution of weak
(C) pH of 0.1 M salt of HA (pKa = 5) (R) 6
acid HA
and BOH (pKb = 7)
2. Match the columns:
(D) pH of 500 L of 0.2 M HNO3 and (S) 8
Column I Column II 500 L 0.2M NaOH
(A) CH3COOH (P) Acidic buffer at 6. Match the columns:
(pKa = 4.74;0.1 M) + its maximum ca- Column I Column II
CH3COONa (0.1 M) pacity
(A) Salt of weak acid (P) pH of solution at
(B) CH3COOH (0.1 M) + (Q) Buffer solution and weak base 25ºC is less than 7
HCl (0.1 M) (pKa = pKb)
(C) CH3COOH (R) pH < 7 at 25º C (B) Salt of weak acid (Q) pH of solution at
(pKa = 4.74 , and strong base 25ºC greater than 7
(0.1 M) + NH4OH
(pKa = 4.74, 0.1 M) (C) Salt of strong acid (R) pH of solution at
and strong base 25ºC equal to 7
(D) CH3COONa (S) pH = 7 at 25º C
(300 mL of 0.1 M) + (D) Salt of strong acid (S) pH can not be find
HCl (100 mL of 0.1 and weak base until the value of
M) Ka/Kb is given
7. Match the columns: (c) 0.01(M) aqueous solution of HNO3

Column I Column II (d) 1(M) aqueous solution of HD (Ka = 10–3)
– –6
13. 100 mL of 0.1 (M) HA and 100 mL of 1(M) HD
(A) pKb of X (Ka of HX = 10 ) (P) 6.9 (Ka = 10–3) solutions are mixed. What is the final ap-
–8
(B) pH of 10 M HCl (Q) 8 proximate pH of the solution neglecting the degree of
dissociation of HA and HD?
(C) pH of 10–2 M acetic acid solu- (R) 10.7
(a) 2.5
tion (Take Ka of acetic acid =
(b) 2.0
1.6 ¥ 10–5)
(c) 1.5
(D) pOH of a solution obtained by (S) 3.4 (d) Final pH cannot be determined
Mixing equal volumes of solu- Comprehension 3
tion with pH 3 and 5. 50 mL of 0.1(M) Na2CO3 solution is titrated with 0.1(M) HCl
8. Match the columns: solution
Column I Column II ææ
Æ HCO3-
Given: CO32- + H + ¨æ
æ K1 = 2.1 ¥ 1010
(A) The relation between (P)
[H + ][OH - ] ææ
HCO3- + H + ¨æ Æ H 2CO3 K2 = 2.2 ¥ 106
Ksp and the solubility of æ
Ag2CrO4 [H 2O]
Given: log 3 = 0.48
(B) Ionisation constant of (Q) Ksp = s2 14. The pH of solution at the start of titration is
water (a) 6.4 (b) 7.5 (c) 8.3 (d) 11.5
15. The pH of solution at the half-neutralisation point is
(C) The relation between Ksp (R) pH > 7 (a) 6.4 (b) 7.5 (c) 8.3 (d) 11.50
and solubility of BaCrO4 16. The pH of solution at the complete neutralisation point
(D) pH of aqueous solution of (S) Ksp = 4s3 is about
potassium carbonate (a) 4.0 (b) 6.0 (c) 7.0 (d) 8.0
Comprehension Comprehension 4
A solution of paranitrophenol indicator of concentration
Comprehension 1 6 ¥ 10–4 (M) was prepared and indicator solution was used
The pH of blood stream (7.4) is maintained by a proper bal- in the spectrophotometric measurement. The experimental
ance of H2CO3 and NaHCO3 concentration. results are tabulated as below.
9. What volume of 5 M NaHCO3 solution should be
mixed with a 10 mL sample of blood which is 2 M in Condition Form of Indicator Absorbance
H2CO3 in order to maintain its pH? : If PKa1 6.11 and Strongly Acidic H In 0.142
PKa2 10.2 Strongly Alkaline In– 0.943
(a) 40 mL (b) 38 mL (c) 50 mL (d) 78 mL
pH = 8 H In + In– 0.527
10. Following reaction occurs in the body :
CO2 + H2O m H2CO3 m H+ + HCO3– Given: log 2 = 0.3; log 3 = 0.48; log 5 = 0.7; log 7 = 0.85
If CO2 escapes from the system : 17. What is the molar concentration of In– at pH = 8?
(a) pH will decrease (a) 3.11 ¥ 10–4 (M) (b) 2.88 ¥ 10–4 (M)
–4
(b) pH will increase (c) 6 ¥ 10 (M) (d) None of these
(c) [H2CO3] remains unchanged 18. What is the Kin of the indicator ?
(d) forward reaction is promoted (a) 3.117 ¥ 10–4 (b) 6.12 ¥ 10–9
–10
(c) 9.25 ¥ 10 (d) 9.25 ¥ 10–9
Comprehension 2
19. What will be the pH of the solution if the total absor-
To the 100 mL of 10–2 (M) aqueous solution of HCl 0.1 (M)
bance is equal to 0.625 ?
HA (Ka = 10–2) is added in such a way so that the final pH of
(a) 8.00 (b) 10.22 (c) 11.23 (d) 8.215
the solution become 1.7.
Given log 2 = 0.3 Subjective
11. What volume of 0.1 (M) HA was required to add in
20. Calculate
aqueous HCl to reduced the final pH equal to 1.7?
(i) Ka for H2O (Kw = 10–14)
(a) 175 mL (b) 100 mL (c) 104 mL (d) 75 mL
(ii) Kb for B(OH)4–, Ka(B(OH)3) = 6 ¥ 10–10
12. Which of the following solution is isohydric with
(iii) Ka for HCN, Kb(CN–) = 2.5 ¥ 10–5
0.1(M) aqueous solution of HA?
21. Calculate the ratio of degree of dissociation (a2/a1)
(a) 0.01(M) aqueous solution of HB (Ka = 10–2)
1
(b) 0.01(M) aqueous solution of HC (Ka = 10–5) when 1 M acetic acid solution is diluted to times.
100
(Given: Ka = 1.8 ¥ 10–5)
22. Calculate the ratio of degree of dissociation of acetic a solution obtained by dissolving 0.1 mol Na4Y in 1 L.
acid and hydrocyanic acid (HCN) in 1 M their respective The acid dissociation constants of H4Y :
solution of acids (Given: Ka = 1.8 ¥ 10–5; = 6.2 ¥ 10–10] k1 = 1.02 ¥ 10–2, k2 = 2.13 ¥ 10–3, k3 = 6.92 ¥ 10–7,
23. Calculate: Ka for a monobasic acid whose 0.10 M solu- k4 = 5.50 ¥ 10–11:
tion has pH of 4.50. 39. Calculate the solubility of solid zinc hydroxide at a pH
24. Calculate pH of the following solution: of 9. Given:
(i) 0.1 M CH3COOH (Ka = 1.8 ¥ 10–5) Zn(OH)2(s) m Zn(OH)2(aq) k1 = 10–6 M (i)
(ii) 10–8 M HCl + –
Zn(OH)2(aq) m Zn(OH) + OH k2 = 10 M (ii) –7
(iii) 10–10 M NaOH Zn(OH)+ m Zn2+ + OH– k3 = 10–4 M (iii)

25. The value of Kw at the physiological temperature
Zn(OH)2(aq) + OH– m Zn(OH)3– k4 = 103 M–1 (iv)
(37° c) is 2.56 ¥ 10–14. What is the pH at the neutral
point of water at this temperature, where there are Zn(OH)3– + OH– m Zn(OH)42– k5 = 10 M–1 (v)
equal number of H+ and OH– ? 40. The standard free energy of formation for AgCl at
26. The pH of aqueous solution of ammonia is 11.5. Find 298 K is –109.7 kJ mole–1 .
molarity of solution. Kb(NH4OH) = 1.8 ¥ 10–5. DG° (Ag+) = 77.2 kJ/mole, DG° (Cl–) = – 131.2 kJ/
27. The solution of weak monoprotic acid which is 0.01 M mole. Find the solubility of AgCl in 0.05 M KCl. Ne-
has pH = 3. Calculate Ka of weak acid. glect any complication due to complexation.
28. Calculate [H+] and [CHCl2COO–] in a solution that 41. At what minimum pH will 1.0 ¥ 10–3 mol of Al(OH)3
is 0.01 M in HCl and 0.01 M in CHCl2COOH. Take go into 1 L solution as Al3+ ?
(Ka = 2.55 ¥ 10–2). Given: Ksp [Al(OH)3] = 5.0 ¥ 10–33 and for
29. Calculate [H+], [CH3COO–] and [C7H5O2–] in a solu- [Al(OH)4–] ¤ Al3+ + 4OH– . K = 1.3 ¥ 10–34.
tion that is 0.02 M in acetic acid and 0.01 M in benzoic 42. What is the pH of a 1.0 M solution of acetic acid ? To
acid. Ka(acetic) = 1.8 ¥ 10–5, Ka(benzoic) = 6.4 ¥ 10–5. what volume must 1 L of the solution be diluted so that
30. Determine the [S2–] in a saturated (0.1 M) H2S solution the pH of the resulting solution will be twice the origi-
to which enough HCl has been added to produce a [H+] nal value. Given Ka = 1.8 ¥ 10–5.
of 2 ¥ 10–4. K1 = 10–7, K2 = 10–14 43. A handbook states that the solubility of methylamine
31. Calculate [H+], [H2PO4–], [HPO42–] and [PO43–] in a 0.01 CH3NH2 (g) in water at 1 atm pressure at 25°C is
M solution of H3PO4. 959 volumes of CH3NH2 (g) per volume of water
Take K1 = 7.225 ¥ 10–3, K2 = 6.8 ¥ 10–8, K3 = 4.5 ¥ (pkb = 3.39):
10–13. (a) Estimate the maximum pH that can be attained by
32. Determine [OH–] of a 0.050 M solution of ammonia dissolving methylamine in water.
to which has been added sufficient NH4Cl to make the (b) What molarity NaOH (aqueous) would be re-
total [NH4+] equal to 0.100. [ = 1.8 ¥ 10–5]. quired to yield the same pH?
33. A buffer of pH 9.26 is made by dissolving x moles of 44. Mixture of solutions. Calculate the pH of the following
ammonium sulphate and 0.1 mole of ammonia into 100 solutions:
mL solution. If pKb of ammonia is 4.74, calculate value For H3PO4, k1 = 7.5 ¥ 10–3, k2 = 6.2 ¥ 10–8 , k3 = 10–12,
of x. (a) 50 mL of 0.12 M H3PO4 + 20 mL of 0.15 M
34. What is the OH– concentration of a 0.08 M solution of NaOH;
CH3COONa? [Ka(CH3COOH) = 1.8 ¥ 10–5] (b) 50 mL of 0.12 M H3PO4 + 40 mL of 0.15 M
35. 0.25 M solution of pyridinium chloride C5H6N+Cl– was NaOH;
found to have a pH of 2.699. What is Kb for pyridine, (c) 40 mL of 0.12 M H3PO4 + 40 mL of 0.18 M
C5H5N? NaOH;
36. What is the pH of 0.1 M NaHCO3? K1 = 4.5 ¥ 10–7, (d) 40 mL of 0.10 M H3PO4 + 40 mL of 0.25 M
K2 = 4.5 ¥ 10–11 for carbonic acids. NaOH.
37. A solution of volume V contains n1 moles of QCl and 45. Mixture of solutions. Calculate the pH of the following
n2 moles of RCl where QOH and ROH are two weak solution:
bases of dissociation constants k1 and k2 respectively. Use data of above question for H3PO4
Show that the pH of the solution is given by (i) 50 mL of 0.10 M Na3PO4 + 50 mL of 0.10 M
NaH2PO4;
1 ÈÊ k k ˆ V ˘
pH = log ÍÁ 1 2 ˜ ˙ (ii) 40 mL of 0.10 M H3PO4 + 40 mL of 0.10 M
2 k ( n k +
ÎË W ¯ 1 2 1 2 ˚ k n ) Na3PO4.
State assumptions, if any. 46. When a 40 mL of a 0.1 M weak base is titrated with
38. EDTA, often abbreviated as H4Y, forms very stable 0.16 M HCl, the pH of the solution at the end point is
complexes with almost all metal ions. Calculate the 5.23. What will be the pH if 15 mL of 0.12 M NaOH is
fraction of EDTA in the fully protonated form, H4Y in added to the resulting solution :-
47. A buffer solution was prepared by dissolving 0.05 mol (c) Lewis acid
formic acid and 0.06 mol sodium formate in enough (d) Lewis base
water to make 1.0 L of solution. Ka for formic acid is 58. What will be the resultant pH of the solution when
1.80 ¥ 10–4. 200 mL of an aqueous solution of HCl (pH = 2) is
(a) Calculate the pH of the solution. mixed with 300 mL of an aqueous solution of NaOH
(b) If this solution was diluted to 10 times its volume, (pH = 12.0) ?
what will be the pH? 59. Calculate the pH value at the equilibrium point when a
(c) If the solution in (b) was diluted to 10 times its solution of 0.1 M acetic acid is titrated with a solution
volume, what will be the pH? of 0.1 M NaOH. Ka for acetic acid is 1.9 ¥ 10–5.
48. If 0.00050 mol NaHCO3 is added to 1 L of a buffered 60. The pH of blood stream is maintained by a proper
solution at pH 8.00. How much material will exist in balance of H2CO3 and NaHCO3 concentrations. What
each of the three forms H2CO3, HCO3– and CO32–? For volume of 5 M NaHCO3 solution should be mixed with
H2CO3, K1 = 5 ¥ 10–7, K2 = 5 ¥ 10–13. 10 mL of blood which is 2 M in H2CO3 in order to
49. Equilibrium constant for the acid ionisation of Fe3+ to maintain pH of 7.4. Ka for H2CO3 in blood is 7.8 ¥
Fe(OH)+2 and H+ is 6.5 ¥ 10–3. What is the maximum 10–7?
pH, which can be used so that at least 95% of the total 61. What will be the pH of a solution obtained by mixing
Fe3+ in a dilute solution. exists as Fe3+. 800 mL of 0.05 N sodium hydroxide and 200 mL of
50. How much Na2HPO4 must be added to one litre of 0.1 N HCl, assuming complete ionisation of the acid
0.005 M solution of NaH2PO4 in order to make a 1 L and the base ?
of the solution of pH = 6.7? K1 = 7.1 ¥ 10–3, K2 = 6.3 ¥ 62. What is the pH of the solution when 0.2 mol of hydro-
10–8 , K3 = 4.5 ¥ 10–13 for H3PO4. chloric acid is added to 1 ltr of a solution containing
51. The indicator phenol red is half in the ionic form when 1 M acetic acid and acetate ion ? Assume that the total
pH is 7.2. If the ratio of the undissociated form to the volume is 1 ltr. Ka for CH3COOH = 1.8 ¥ 10–5.
ionic form is 1 : 5, find the pH of the solution. With the 63. Calculate the change in pH of one litre buffer solu-
same pH for solution, if indicator is altered such that tion containing 0.10 mol each of NH3 and NH4Cl upon
the ratio of undissociated form to dissociated form be- addition of (i) 0.02 mol of dissolved gaseous HCl, (ii)
comes 1 : 4, find the pH when 50% of the new indicator 0.02 mol of dissolved NaOH. Assume no change in
is in ionic form.
volume (Kb for NH3 = 1.8 ¥ 10–5).
52. A buffer solution, 0.080 M in Na2HPO4 and 0.020 M in
64. Calculate the composition of an acidic buffer solution
Na3PO4, is prepared. The electrolytic oxidation of 1.0
(HA + NaA) of total molarity 0.29 having pH = 4.4 and
m mol of the organic compound RNHOH is carried out
Ka = 1.8 ¥ 10–5.
in 100 mL of the buffer. The reaction is
65. Find the pH of a 2 L solution which is 0.1 M each with
RNHOH + H2O h RNO2 + 4H+ + 4e
respect to CH3COOH and (CH3COO)2Ba.
Calculate the approximate pH of the solution after the
66. A solution is found to contain 0.63 g of nitric acid per
oxidation is complete ?
100 mL of the solution. What is the pH of the solution
53. SO2 dissolves in water to form an acidic solution.
if the acid is completely dissociated ?
Explain.
67. 4.0 g of NaOH are dissolved per litre. Find (i) molarity
54. Explain the following:
of the solution, (ii) OH– ion concentration, and (iii) pH
CaC2O4 is insoluble in CH3COOH but soluble in dilute
HCl. value of the solution (Atomic weight: Na = 23, O = 16,
55. A solution of HCl has a pH = 5. If one mL of it is di- H = 1).
luted to 1 L, what will be the pH of resulting solution? N N N
68. If , 200 mL HNO3 and , 100 mL HCl and ,
56. Calculate the pH of a solution of given mixtures : 10 20 20
(a) (2g CH3COOH + 3g CH3COONa) in 100 mL of 100 mL H2SO4 were mixed in 1 L vessel. Calculate the
mixture; Ka = 1.8 ¥ 10–5 pH of resulting solution.
(b) 5 mL of 0.1 M NH4OH + 250 mL of 0.1 M 69. Determine the pH of a solution by mixing 2000 mL,
NH4Cl; Kb = 1.8 ¥ 10–5 N N
HCl and 1000 mL, NaOH.
(c) (0.25 mole of acid + 0.35 mole of salt) in 500 mL 10 10
mixture; Ka = 3.6 ¥ 10–4 70. The pOH of basic buffer [e.g., NH4OH/NH4Cl] is 5. If
57. Out of the following : the concentration of the salt is tripled whereas that of
H2PO4–, SO32- , ClO–, Fe3+, BCl3, NH +4 , base remains same, what is the value of new pOH?
select (Given log 3 = 0.48)
(a) Bronsted Lowry acid 71. Calculate the pH of a solution obtained by mixing 50 mL
(b) Bronsted Lowry base of 0.01 M Ba(OH)2 solution with 50 mL water.
72. How much water must be added to 300 mL of 0.2 M where K1 and K2 are the dissociation constant of acid
solution of CH3COOH for the degree of dissociation of H2A.Ksp is solubility product of MA.
the acid to double ? 85. The pH of a saturated aqueous solution of CO2 is 5; For
73. Find the concentration of H+, HCO3– and CO3–2 in a H2CO3 , Ka1 = 10–7 and Ka2 = 10–11. At the given pres-
0.01 M solution of carbonic acid if the pH of this is sure the solubility of CO2 in water is 10–2 (M). What is
4.18 Ka1 (H2CO3) = 4.45 ¥ 10–7, Ka2 (HCO3–) = 4.69 ¥ the value of –log [CO32–] in the nearest posssible inte-
10–11. gers ?
74. The self-ionisation constant for pure formic acid, K = 86. 200 mL of a saturated solution of CaC2O4(s) requires
[HCOOH2+][HCOO–] has been estimated as 10–6 at 8 mL of 5 ¥ 10–3 (N) KMnO4 solution for complete oxi-
room temperature. What percentage of formic acid dation in the presence of acid. Determine the –log Ksp
molecules in pure formic acid are converted to formate value of a saturated solution of CaC2O4(s) in nearest
ion? The density of formic acid is 1.22 gcm–3. possible integers.
75. Calculate the concentration of H3O+ ion in a mixture of 87. How much water in mL must be added to 300 mL of
0.02 M of acetic acid and 0.2 M sodium acetate. Given: 0.2 M solution of CH3COOH (Ka = 1.8 ¥ 10–5) for the
Ka for acetic acid is 1.8 ¥ 10–5. degree of ionisation (a) of the acid to Triple.
76. The ionization constant of phenol is 1.0 ¥ 10–10. What 88. You have given 100 mL of buffer solution containing
is the concentration of phenate ion in 0.05 M solution weak acid HA (Ka = 10–5) and its salt with strong base
of phenol? NaA at the concentration of 0.1(M) each.
77. Write the correctly balanced net ionic equation for the If 5 ¥ 10–3 moles of HCOOH (Ka = 10–4) is added
reaction whose equilibrium constant at 298 K is to this solution what will be value in the change in
(i) Ka(C6 H5 COOH) = 6.3 ¥ 10–5 pH ¥ 103 in nearest possible integers.
(ii) Ka(HSO3–) = 2.8 ¥ 10–7
(iii) Kb(CH3NH2) = 4.4 ¥ 10–5 Given: 76 = 8.71; log 2.34 = 0.369
(iv) Ka1(H2S) = 1.0 ¥ 10–7 89. What is the ratio of moles of Mg(OH)2 and Al(OH)3
78. The ionisation constant of dimethyl amine is 5.40 ¥ 10–4 in 1 L of their saturated solution. Ksp of Mg(OH)2 = 4 ¥
.Calculate the ionisation constant of its conjugate acid. 10–12 and Ksp of Al(OH)3 = 1 ¥ 10–33 (give your answer
79. How many grams of NaOH must be dissolved in 1 ltr by multiplying the ratio with 10–17).
of the solution to have a solution of pH = 12? 90. A given solution is saturated with both Ag2CrO4 and
80. What should be the ratio of concentrations of for- Ag2C2O4. The Ksp of
mate ion and formic acid in a buffer solution so that Ag2CrO4 = 9 ¥ 10–12 and Ksp of Ag2C2O4 = 6 ¥ 10–12
its pH should be 4? Around what pH will this buffer In the resulting solution determine [Ag+] ¥ 105 in the
have maximum buffer capacity? Ka for formic acid is nearest possible integers.
1.8 ¥ 10–4. Given: (240)1/3 = 6.214
81. Calculate the pH of a solution obtained by mixing of
Multiple Answer Type Question
100.0 mL of 0.1 M HCl with 100 mL of 0.2 M NH3 . Kb
for NH3 is 1.8 ¥ 10–5. 91. An acid-base indicator has a Ka of 3.0 ¥ 10–5. The acid
82. An organic monoprotic acid [0.1 M] is titrated against form of the indicator is red and the basic form is blue.
0.1 M NaOH. By how much does the pH change be- Then
tween 1/4 and 3/4 stages of neutralisation? If at one (a) pH is 4.05 when indicator is 75% red.
third stage of neutralisation, the pH is 4.45 what is the (b) pH is 5.00 when indicator is 75% blue.
dissociation constant of the acid ? Between what stages (c) pH is 5.00 when indicator is 75% red.
of neutralisation may the pH change by two units? (d) pH is 4.05 when indicator is 75% blue.
Integer Answer Type Question 92. pH of the following solution is not affected by dilution:
(a) 0.01 M CH3COONa
83. The salt Zn(OH)2 is involved in the following two (b) 0.01 M NaHCO3
equilibria: (c) Buffer of 0.01 M CH3COONa and 0.01 M
Zn(OH)2(s)  Zn2+(aq) + 2OH–(aq); Ksp = 1.2 ¥ 10–17 CH3COOH
Zn(OH)2(s) + 2OH–(aq)  [Zn(OH)4]2–(aq); Kc = 0.13 (d) 0.01 M CH3COONH4
Calculate the pH of solution at which solubility is mini- 93. Which of the following expression(s) is/are true?
mum.
84. Show that solubility of a sparingly soluble salt M2+A2– (a) [H+] = [OH–] = KW for a neutral solution
in which A2– ions undergoes hydrolysis is given by (b) [OH–] < KW for an acidic solution
Ê [H + ] [H + ]2 ˆ (c) pH + pOH = 14 at all temperature
S = Ksp Á1 + + (d) [OH–] = 10–7 M at 25°C for water
Ë K2 K1K 2 ˜¯
94. In the given question Ka values of five weak acids are (a) 1 ¥ 10–10 (b) 5
given. Ka for HA = 10–8, HB = 10–6, HC =2 ¥ 10–8, HD (c) 5 ¥ 10–8 (d) 1 ¥ 10–5
= 10–10, HE = 10–7. 6. Three reactions involving H 2 PO 4- are given below.
Select the correct statement (s) as per the information. [AIEEE 2010]
Given: log 2 = 0.3 I. H3PO4 + H2O Æ H3O+ + H 2 PO 4-
(a) Among NaA, NaB, NaC, NaD and NaE, the NaD
is most extensively hydrolysed. II. H 2 PO 4- + H2O Æ H 2 PO 4-2 + H3O+
(b) Among NaA, NaB, NaC, NaD and NaE, NaB is -
III. H 2 PO 4 + OH– Æ H3PO4 + O2+
most extensively hydrolysed.
(c) pH of 0.1 (M) aqueous solution of NaB is approx- In which of the above does H 2 PO 4- act as an acid ?
imately 9.5. (a) II only (b) I and II
(d) 0.1(M) solution of HE and 0.01(M) solution of (c) III only (d) I only
HB are isohydric to each other approximately. 7. In aqueous solution, the ionisation constants for car-
95. The solubility of AgCl in water, 0.01 M CaCl2, bonic acid are
0.02 M NaCl and 0.05 M AgNO3 are S1, S2, S3 and S4 K1 = 4.2 ¥ 10–7 and K2 = 4.8 ¥ 10–11 [AIEEE 2010]
respectively. Which of the following is true? (Neglect Select the correct statement for a saturated 0.034 M so-
any complex formation). lution of the carbonic acid.
(a) S2 > S1 (b) S2 > S3 (a) The concentration of CO32- is 0.034 M.
(c) S3 > S4 (d) S1 > S4
(b) The concentration of CO32- is greater than that of
96. Solubility of MnS(Ksp = 8 ¥ 10–37) is S1, of ZnS(Ksp =
7 ¥ 10–16) is S2, of Bi2S3(Ksp = 10–72) is S3, of Ag3PO4 HCO3- .
(Ksp = 1.8 ¥ 10–18) is S4 in water. Which of the follow- (c) The concentration of H+ and HCO3- are approxi-
ing is correct? mately equal.
(a) S4 > S2 (b) S4 > S3 (d) The concentration of H+ is double that of CO32- .
(c) S4 < S1 (d) S2 > S1 8. Solubility product of silver bromide is 5.0 ¥ 10–13. The
quantity of potassium bromide (molar mass taken as
PrEVIoUs yEArs’ QUEstIoNs 120 gm mol–1) to be added to 1 L of 0.05 M solution of
oF JEE (MAIN & ADVANcED) silver nitrate to start the precipitation of AgBr is
[AIEEE 2011]
JEE Main
(a) 1.2 ¥ 10–10 g (b) 1.2 ¥ 10–9 g
1. How many litres of water must be added to 1 L of an (c) 6.2 ¥ 10–5 g (d) 5.0 ¥ 10–8 g
aqueous solution of HCl with a pH of 1 to create an 9. At 25ºC, the solubility product of Mg(OH)2 is 1.0 ¥
aqueous solution with pH of 2? [AIEEE 2006] 10–11. At which pH, will Mg2+ ions start precipitating in
(a) 0.1 L (b) 0.9 L (c) 2.0 L (d) 9.0 L the form of Mg(OH)2 from a solution of 0.001 M Mg2+
2. The pH of a 0.1 molar solution of the acid HQ is 3. The ions ? [AIEEE 2012]
value of the ionisation constant, Ka of the acid is (a) 9 (b) 10 (c) 11 (d) 8
[AIEEE 2006]
10. Solid Ba(NO3)2 is gradually dissolved in a 1.0 ¥ 10–4 M
(a) 3 ¥ 10–1 (b) 1 ¥ 10–3
Na2CO3 solution. At what concentration of Ba2+, will it
(c) 1 ¥ 10–5 (d) 1 ¥ 10–7
begin to precipitate ? (Ksp for BaCO3 = 5.1 ¥ 10–9)
3. The first and second dissociation constant of an acid
H2A are 1.0 ¥ 10–5 and 5.0 ¥ 10–10 respectively. The [AIEEE 2012]
overall dissociation constant of the acid will be (a) 4.1 ¥ 10–5 M (b) 5.1 ¥ 10–5 M
[AIEEE 2007] (c) 8.1 ¥ 10–5 M (d) 8.1 ¥ 10–7 M
(a) 5.0 ¥ 10–5 (b) 5.0 ¥ 1015 11. Solubility product of silver bromide is 5.0 ¥ 10–13. The
(c) 5.0 ¥ 10–15 (d) 0.2 ¥ 105 quantity of potassium bromide (molar mass taken as
4. The Ksp for Cr(OH)3 is 1.6 ¥ 10–30. The molar solubil- 120 g mol–1) to be added to 1 L of 0.05 M solution of
ity of this compound in water is [AIEEE 2008] silver nitrate to start the precipitation of AgBr is
[AIEEE–2010]
(a) 2 1.6 ¥ 10-30 (b) 4 1.6 ¥ 10-30 –8
(a) 5.0 ¥ 10 g (b) 1.2 ¥ 10–10 g
–9
(c) 1.2 ¥ 10 g (d) 6.2 ¥ 10–5 g
(c) 4 1.6 ¥ 10-30 /27 (d) 1.6 ¥ 10–30/27
12. In aqueous solution the ionisation constants for car-
5. An acid HA ionises as HA m H+ + A–. The pH of 1.0 bonic acid are [AIEEE–2010]
M solution is 5. Its dissociation constant will be K1 = 4.2 ¥ 10–7 and K2 = 4.8 ¥ 10–11
[AIEEE 2009]
Select the correct statement for a saturated 0.034 M so- [AIEEE-2003]

lution of the carbonic acid: (a) 1 ¥ 10– 15 (b) 1 ¥ 10– 10
(a) The concentration of H+ is double that of CO32–. (c) 4 ¥ 10– 15 (d) 4 ¥ 10– 10
(b) The concentration of CO32– is 4.8 ¥ 10–11 M. JEE Advanced
(c) The concentration of CO32– is greater than that of
HCO3–. Single Correct Answer Type
(d) The concentrations of H+ less than HCO3– are ap- 22. Ag+ + NH3 m [Ag(NH3)]+ ; k1 = 3.5 ¥ 10–3
proximately equal. [Ag+ (NH3)]+ + NH3 m [Ag(NH3)2]+; k2 = 1.7 ¥ 10–3
13. At 25° C, the solubility product of Mg(OH)2 is 1.0 ¥ Then the formation constant of [Ag(NH3)2]+ is
10–11. At which pH, will Mg2+ ions start precipitating in [IIT JEE 2006]
the form of Mg(OH)2 from a solution of 0.001 M Mg2+ (a) 6.08 ¥ 10–6 (b) 6.08 ¥ 106
ions ? [AIEEE–2010] (c) 6.08 ¥ 10–9 (d) None of these
(a) 8 (b) 9 (c) 10 (d) 11 23. Solubility product constant (Ksp) of salts of types MX,
14. Solid Ba(NO3)2 is gradually dissolved in a 1.0 ¥ 10–4 M MX2 and MX3 at temperature T are 4.0 ¥ 10–8, 3.2 ¥
10–14 and 2.7 ¥ 10–15, respectively. Solubilities (mol
Na2CO3 solution. At what concentration of Ba2+ will it
dm–3) of the salts at temperature ‘T’ are in the order
begin to precipitate?
[IIT JEE 2008]
(KSP for Ba CO3 = 5.1 ¥ 10–9) [AIEEE-2009]
(a) MX > MX2 > M3X (b) M3X > MX2 > MX
(a) 8.1 ¥ 10–8 M (b) 8.1 ¥ 10–7 M
(c) MX2 > M3X > MX (d) MX > M3X > MX2
(c) 4.1 ¥ 10–5 M (d) 5.1 ¥ 10–5 M 24. Passing H2S gas into a mixture of Mn2+, Ni2+, Cu2+ and
15. The pKa of a weak acid, HA, is 4.80. The pKb of a weak Hg2+ ions in an acidified aqueous solution precipitates.
base, BOH, is 4.78. The pH of an aqueous solution of [IIT JEE 2011]
the corresponding salt. BA, will be [AIEEE-2008] (a) CuS and HgS (b) MnS and CuS
(a) 9.58 (b) 4.79 (c) 7.01 (d) 9.22 (c) MnS and NiS (d) NiS and HgS
16. In a saturated solution of the sparingly soluble strong 25. The initial rate of hydrolysis of methyl acetate (1M) by
electrolyte AglO3 (molecular mass = 283) the equilib- a weak acid (HA, 1 M) is 1/100th of that of a strong acid
rium which sets in is [AIEEE-2007] (HX, 1M), at 25ºC. The Ka of HA is
+ -
AglO3 m Ag (aq) + IO3(aq) [JEE Advanced 2013]
(a) 1 ¥ 10–4 (b) 1 ¥ 10–5
If the solubility product constant Ksp of AgIO3 at a giv- (c) 1 ¥ 10–6 (d) 1 ¥ 10–3
en temperature is 1.0 ¥ 10– 8, what is the mass of AgIO3 26. The Ksp of Ag2CrO4 is 1.1 ¥ 10–12 at 298 K. The solu-
contained in 100 mL of its saturated solution ? bility (in mol/L) of Ag2CrO4 in a 0.1 M AgNO3 solu-
(a) 28.3 ¥ 10– 2 g (b) 2.83 ¥ 10– 3 g tion is [JEE Advanced 2013]
–7
(c) 1.0 ¥ 10 g (d) 1.0 ¥ 10– 4 g (a) 1.1 ¥ 10–11 (b) 1.1 ¥ 10–10
17. The solubility product of a salt having general formula (c) 1.1 ¥ 10–12 (d) 1.1 ¥ 10–9
MX2, in water is : 4 ¥ 10– 12. The concentration of M2+
ions in the aqueous solution of the salt is Multiple Correct Answer Type
[AIEEE-2005] 27. Aqueous solutions of HNO3, KOH, CH3COOH and
(a) 1.0 ¥ 10– 4 M (b) 2.0 ¥ 10– 6 M CH3COONa of identical concentration are provided.
(c) 4.0 ¥ 10– 10 M (d) 1.6 ¥ 10– 4 M The pair(s) of solutions which form a buffer upon mix-
18. Hydrogen ion concentration in mol/L in a solution of ing is (are) [IIT JEE 2010]
pH = 5.4 will be [AIEEE-2005] (a) HNO3 and CH3COOH
(a) 3.88 ¥ 106 (b) 3.98 ¥ 108 (b) KOH and CH3COONa
(c) 3.98 ¥ 10– 6 (d) 3.68 ¥ 10– 6 (c) HNO3 and CH3COONa
19. The molar solubility in mol L–1 of a sparingly soluble (d) CH3COOH and CH3COONa
salt MX4 is ‘s’. The corresponding solubility product is
Ksp. ‘s’ is given in terms of Ksp by which relation? Linked Comprehension Type
[AIEEE-2004] When 100 mL of 1.0 M HCl was mixed 100 mL of 1.0 M
(a) s = (Ksp/128)1/4 (b) s = (128 Ksp)1/4 NaOH in an insulated beaker at constant pressure, a tempera-
(c) s = (256 Ksp)1/5 (d) s = (Ksp/256)1/5 ture increase of 5.7ºC was measured for the beaker and its
20. The solubility of Mg(OH)2 is x mole/lit. Then its solu- contents (Expt. 1). Because the enthalpy of neutralisation of
bility product is [AIEEE-2002] a strong acid with a strong base is a constant (–57.0 kJ mol–1),
(a) x3 (b) 5x3 (c) 4x3 (d) 2x2 this experiment can be used to measure the calorimeter con-
21. The solubility in water of a sparingly soluble salt AB2 stant. In a second experiment (Expt 2), 100 mL of 2.0 M ace-
is 1.0 ¥ 10– 5 mol L– 1. Its solubility product will be tic acid (Ka = 2.0 ¥ 10–5) was mixed with 100 mL of 1.0 M
NaOH (under identical conditions to Expt.1) where a tem- 31. Amongst the following, the total number of compounds
perature rise of 5.6ºC was measured.(Consider heat capacity whose aqueous solution turns red litmus paper blue is
of all solutions as 4.2 J g–1 K–1 and density of all solutions as KCN, K2SO4, (NH4)2C2O4, NaCl, Zn(NO3)2,
1.0 g mL–1) [JEE Advanced 2015] FeCl3, K2CO3, NH4NO3, LiCN [IIT JEE 2010]
28. Enthalpy of dissociation (in kJ mol–1) of acetic acid ob- 32. The total number of diprotic acids among the following
tained from Excerpt 2 is is
(a) 1.0 (b) 10.0 (c) 24.5 (d) 51.4 H3PO4 H2SO4 H3PO3 H2CO3 H2S2O7
29. The pH of the solution after Excerpt 2 is H3BO3 H3PO2 H2CrO4 H2SO3
(a) 2.8 (b) 4.7 (c) 5.0 (d) 7.0
33. In 1 L saturated solution of AgCl [Ksp(AgCl) = 1.6 ¥
Integer Answer Type 10–10], 0.1 mol of CuCl[Ksp(CuCl) = 1.0 ¥ 10–6] is add-
ed. The resultant concentration of Ag+ in the solution is
30. The dissociation constant of a substituted benzoic acid
1.6 ¥ 10–x. The value of ‘x’ is [IIT JEE 2011]
at 25ºC is 1.0 ¥ 10–4. The pH of a 0.01 M solution of its
sodium salt is [IIT JEE 2009]
Answer Key
lEVEl I
1. (c) 2. (a) 3. (b) 4. (b) 5. (a) 6. (c) 7. (c) 8. (b) 9. (c) 10. (d)
11. (c) 12. (a) 13. (a) 14. (a) 15. (d) 16. (d) 17. (b) 18. (b) 19. (a) 20. (a)
21. (b) 22. (a) 23. (c) 24. (b) 25. (c) 26. (c) 27. (c) 28. (a) 29. (b) 30. (c)
31. (b) 32. (c) 33. (b) 34. (a) 35. (a) 36. (b) 37. (a) 38. (d) 39. (a) 40. (b)
41. (b) 42. (b) 43. (c) 44. (d) 45. (a) 46. (a)
lEVEl II
1. (a) 2. (d) 3. (a) 4. (a) 5. (b) 6. (b) 7. (c) 8. (a) 9. (c) 10. (d)
11. (c) 12. (b) 13. (a) 14. (a) 15. (c) 16. (a) 17. (b) 18. (b) 19. (a) 20. (a)
21. (b) 22. (d) 23. (d) 24. (d) 25. (c) 26. (a) 27. (b) 28. (d) 29. (b) 30. (c)
lEVEl III
1. (A) Æ s; (B) Æ p; (C) Æ r; (D) Æ q 2. (A) Æ p, q, r; (B) Æ r; (C) Æ q, s; (D) Æ q, r

3. (A) Æ q; (B) Æ r; (C) Æ q, s; (D) Æ p, s 4. (A) Æ q, s; (B) Æ p, r; (C) Æ p, r; (D) Æ q, s
5. (A) Æ p; (B) Æ s; (C) Æ r; (D) Æ q 6. (A) Æ r; (B) Æ q, s; (C) Æ r; (D) Æ p, s
7. (A) Æ q; (B) Æ p; (C) Æ s; (D) Æ r 8. (A) Æ s; (B) Æ p; (C) Æ q; (D) Æ r
9. (d) 10. (b) 11. (d) 12. (d) 13. (c) 14. (d) 15. (c) 16. (a) 17. (b) 18. (d)
19. (d) 20. (i) [1.8 ¥ 10–16], (ii) [1.67 ¥ 10–5], (iii) [4 ¥ 10–10] 21. (10) 22. (170 : 1)
23. (Ka = 10–8) 24. (i) [2.38], (ii) [6.95], (iii) [7.0004] 25. (6.795) 26. (0.556M)
27. (1.1 ¥ 10–4) 28. (0.07, 6.126 ¥ 10–2) 29. (10–3, 3.6 ¥ 10–4, 6.4 ¥ 10–4) 30. (2.5 ¥ 10–15)
+ – –3 –2 –8 –3 –18
31. [H ] ≥ [H2 PO4 ] = 5.6 ¥ 10 M, [HPO4 ] = 6.8 ¥ 10 M [PO4 ] = 5.46 ¥ 10 M
32. (9 ¥ 10–6 M) 33. (0.05 mole) 34. (6.6 ¥ 10–6 M) 35. (10–9 8) 36. (8.34)
–26
37. (Solve by salt hydrolysis) 38. (3.82 ¥ 10 ) 39. (1.12 ¥ 10–6 M) 40. (3.4 ¥ 10–9 M)
41. [4.23] 42. (2.77 ¥ 104 L) 43. (i) [13.1] (b) [0.125 M] 44. (a) [2.12] (b) [4.66] (c) [7.2] (d) [12]
45. (i) [9.6] (ii) 7.2 46. (9.16) 47. (3.823, 3.846, 3.98)
48. (H2CO3) = 9.8 ¥ 10–6 M, (HCO3–) = 4.9 ¥ 10–4 M, (CO3– –)= 2.45 ¥ 10–8 M 49. (0.908)
50. (1.58 ¥ 10–3 mole) 51. [7.898, 7.3 and 7.3] 52. (7.8) 53. (Conceptual)
54. (SA+ SB  WA+ WB \ feasible) 55. (6.978) 56. (a) [4.78] (b) [7.55] (c) [3.58] 57. (Conceptual)
58. (11.3) 59. (8.71) 60. (78.36ml) 61. [12.3] 62. (4.5) 63. (0.176Ø, 0.176≠)
64. (salt = 0.087 M acid = 0.203 M) 65. (5.046) 66. (1) 67. (i) [0.1M] (ii) [0.1 M] (iii) [13]
68. (1.12) 69. (1.47) 70. (5.48) 71. [12] 72. (900 ml)
73. [H+] = 6.61 ¥ 10–5 M, [HCO3–] = 6.73 ¥ 10–5 M, [CO3– –] = 4.8 ¥ 10–11 M 74. (0.004%)
75. (1.8 ¥ 10–6 M) 76. (2.2 ¥ 10–6 M) 77. (SA + SB  WA + WB then feasible) 78. (1.23 ¥ 10–11)
Ê 10 1 ˆ
79. (0.4 g) 80. (1.8:1 & 3.74) 81. [9.26] 82. Á 0.9542, 4.751, th stage to th stage˜ 83. (10)
Ë 11 11 ¯
84. (conceptual) 85. (10) 86. (8) 87. (2400) 88. (369) 89. (8) 90. (31) 91. (a, b) 92. (b, c, d)
93. (a, b, d) 94. (a, c, d) 95. (c, d) 96. (a, b, d)
PrEVIoUs yEArs’ QUEstIoNs oF JEE (MAIN & ADVANcED)
1. (d) 2. (c) 3. (c) 4. (c) 5. (a) 6. (a) 7. (c) 8. (b) 9. (b) 10. (b)
11. (c) 12. (b) 13. (c) 14. (d) 15. (c) 16. (b) 17. (a) 18. (a) 19. (c) 20. (c)
21. (c) 22. (a) 23. (d) 24. (a) 25. (a) 26. (b) 27. (c, d) 28. (a) 29. (b) 30. (8)
31. (3) 32. (6) 33. (7)
Hints and Solutions
lEVEl I 1
pH = (pKw + pKa + log c)
2
1
[H + ][OH - ] 10-12 pH = (pKw + pKa) since c = 1(M)
1. (c) K H2O = = 2
[H 2O] 55.55
K H2O = 1.8 ¥ 10–14 1 1
\ pH = (2pKw – pKb) = (28 – 9.3)
2 2
[salt]
2. (a) pH = pKa + log 1
[weak acid] pH = (28 – 9.3) = 9.35
\ pH = pKa 2
3. (b) Ksp = [Zn2+] [S2–] 7. (c) On diluting a buffer solution, the ratio of salt to acid
(or base) does not change. Hence, its pH remains con-
10- 21
[S2- ] = = 10-19 stant.
0.01 8. (b) After mixing total moles of A–
[H + ]2 [S2- ] = 100 ¥ 0.2 ¥ 10–3 + 100 ¥ 0.3 ¥ 10–3
for K a1 ◊ K a2 =
[H 2S] = 100 ¥ 10–3 ¥ 0.5 moles
After mixing total moles of HA
[H + ]2 ¥ 10-19
10-20 = fi [H + ] = 0.1 = 100 ¥ 0.1 ¥ 10–3 + 100 ¥ 0.2 ¥ 10–3
0.1 = 100 ¥ 0.3 ¥ 10–3 moles
or pH = 1 5
4. (b) pH = 2, [HCl] = 10–2 (M) and pOH = 2 After mixing resulting pH = 5 + log
3
or [NaOH] = 10–2 (M)
9. (c) KaKb = 10–14
4 mL of 10–2 (M) HCl ∫ 4 ¥ 10–5 moles HCl.
or Ka = Kin = 10–5
6 mL of 10–2 (M) NaOH ∫ 6 ¥ 10–5 moles NaOH
\ [H+] = 10–5
After mixing excess moles of OH– = 2 ¥ 10–5
or pH = 5
2 ¥ 10- 5 10. (d)
[OH–] = ¥ 103 = 2 ¥ 10–3
10 SrF2 (s)  Sr2+ + 2F–
or pOH = 3 – log 2 = 3 – 0.3 = 2.7 s 2s
or pH = 11.3 where s is the solubility
5. (a) A solution of CuSO4 is acidic due to hydrolysis of \ 4s3 = 32 ¥ 10–15
strong conjugate acid Cu2+ ions, or s = 2 ¥ 10–5 (M)
Cu2+ + H2O m Cu (OH)+ + H+ But practically the solubility of SrF2 (s) in NaCl so-
6. (c) Ba2+ is not hydrolysed , CN– = 1 (M) lution is slightly greater than 2 ¥ 10–5 because NaCl
CN– + H2O m HCN + OH– increases ionic strength of the solution.
11. (c) Kw = [H+] [OH–] Total mole = 0.15 gram mole

[H+] in pure water = 10–6 0.05 1
[OH–] = 10–6 Mole fraction of acetone = =
0.15 3
Therefore, Kw = 10–12
12. (a) Solution of KCN is basic. Therefore, concentration [Salt]
26. (c) pH = pKa + log = 4.75 + log 10
of [H+] will decrease on mixing it with CH3COOH and [Acid]
thus pH will increase. pH = 5.75
13. (a) On dissolving FeCl3 in water, it will give Fe(OH)3, 27. (c) Henolphthalein is colourless in acid medium be-
H+ and Cl–. Ionisation of Fe(OH)3 will be low. There- cause concentration of Ph range 8.3 to 10.
fore, concentration of [H+] will be more than [OH–] in 28. (a) [Salt] = [Acid]
the solution, so the solution will be acidic and blue lit- [Salt]
mus solution will turn red. pH = pKa + log
[Acid]
14. (a) Ionic product of Na+ and Cl– becomes more than
0.02
the solubility product of NaCl. pH = 4.75 + log
15. (d) Fe Al and Cr are third group elements. Therefore, 0.02
pH = 4.75
their solubility product is low, whereas Zn is of fourth 29. (b) Na+ and undissociated H2PO4–, HPO42, PO4–3 ions
group and therefore its solubility product is high. will be there, because H3PO4 dissociates in three steps.
16. (d) CH3NH2 (an amine) is basic, therefore its pH will 30. (c)
be greater than 7. 8
K = 10
17. (b)  pH = 3, [H+] = 10–3 C = 10–1 Ag+ ææææ
+ 2NH3 ¨æææ Æ
æ Ag(NH3)2+
[H+] = C ◊ a 0.02 mol 0.14 mol
10–3 = 10–1 a — 0.1 mol 0.02 mol
10-3 [Ag(NH3 ) 2+] 0.02
a = -1 = 10–2, Ka = Ca2 108 = =
10 [Ag + ][NH3 ]2 [Ag + ] ¥ 0.01
Ka = Ca2 = 10–1 ¥ 10–2 ¥ 10–2 = 10–5 or [Ag+] = 2 ¥ 10–8 (M)
18. (b) among all Na2CO3 is most basic, therefore its pH 31. (b)
value will be highest. pH = 1 pH = 2
19. (a) Volume is increasing twice, therefore concentration [H+] = 0.1 [H+] = 0.01
will become half. V = 50 V = 50
Ksp = [Ag+][Cl–] N V + N 2V2 50(0.1 + 0.01)
Ionic product = 0.5 ¥ 10–4 ◊ 10–4 ¥ 0.5 = 10–8 ¥ 0.25 [H+] of mixture is[H+] = 1 1 fi
V1 + V2 100
Solubility product = 1.8 ¥ 10–10
Ionic product > Solubility product, therefore precipita- 0.11
tion will take place. [H + ] fi fi 0.055
2
20. (a) Na2+ CO3– + 2H2O m 2Na+ + 2OH– + H2CO3 pH = 1.26
CO3–2 + 2H2O m 2OH– + H2CO3 32. (c) pH = 7 \ [H+] = 10–7, [OH–] = 10–7
21. (b) To precipitate only the metal hydroxides of third New pH after addition of base
group, NH4Cl is added before NH4OH in qualitative pH = 12 \ [H+] = 10–12
analysis, because the concentration of OH– decreases and [OH–] = 10–2
due to common ion effect. [OH–] concentration increase 105 times.
22. (a) N1V1 + N2V2 = N3V3
250 ¥ 6M + 350 ¥ 8 = 3N ¥ V3 K a1 3 ¥ 10- 4
33. (b) Relative strength = = fi4:1
1500 + 280 = 3N ¥ V3 K a2 1.8 ¥ 10-5
V3 = 1433.3 mL 34. (a) HCOOH + KOH Æ HCOOK + H2O
Volume 1433.3 – (250 + 350) = 833.3 mL after reaction it forms Buffer solution
Therefore, 833.3 mL water has to be mixed.
10 10
23. (c) CH3COONH4 salt is made up of weak acid and [HCOOH] = [HCOOK] =
weak base. Therefore, pH remains unchanged on dilut- 90 90
ing it, because it acts as an amphiresistant solution. [salt]
pH = pKa + log pH = pKa
24. (b) In the titration of weak base and a strong acid, the [acid]
resulting solution will be acidic. Therefore, methyl or- pH = 4 – log (1.8) pH = 3.75
ange is an appropriate indicator. 35. (a) Let weak acid be HA and its sodium salt be NaA.
25. (c) 1.8 g water = 0.1 g mole K
2.9 Ka = w Kh = Ca2 fi 0.1 ¥ (0.03)2
2.9 g acetone = = 0.05 g mole Kh
58
10-14 0.1
Ka = K = ª 1 ¥ 10–10 [H+] = fi 0.001 pH = 3
9 ¥ 10-5 a 100
43. (c) HF + H2O m F– + H3O+
36. (b) CH3COOH + NaOH h CH3COONa + H2O
Ka ¥ Kb= Kw pKa + pKb= pKw
40 20 0 0
pKa = 14 – 10.83 \ pKa = 3.17
After reaction
and Ka = 6.75 ¥ 10–4
20 20
[CH3COOH] = , [CH3COONa] = 44. (d)
200 200 First dissociation : H3X h H2X– + H+
pH = pKa + log [salt] \ H+ ion concentration = 2 ¥ 10–4 M
[acid] Second dissociation : H2X– m HX– + H+
pH = pKa [H+] = Ka = 1.8 ¥ 10–5 \ H+ ion concentration = Ca = 2 ¥ 10–4 ¥ 0.5 = 10–4
37. (a) CH3COONa + HCl h CH3COOH + NaCl  Third dissociation is negligible
20 \ [H+] = 2 ¥ 10–4 + 10–4 = 3 ¥ 10–4
at equivalence the [CH3COOH] = fi 0.1 pH = 4 – log 3 = 3.52
200
1 1 1 10
pH = pK a - log C 45. (a) [H+] = 2Ca = 2 ¥ ¥ = 10-3 M
2 2 200 100
1 \ pH = 3
pH = [5 + log 2 - log 10-1 ] 46. (a)
2
1 1 1 1
pH = [6 - log 2] fi pH = 3 - log 2 Formula of pH is pH = pK w + pK a + log C
2 2 2 2
1 1
HCO3- 8=7+ pK a + log(10-2 )
38. (d) pH = pKa + log 2 2
H 2CO3
1
8 = 7 + pK a - 1
[HCO3- ] 2
7 = 7 – log 4 + log
[H 2CO3 ] 4 = pKa or pKa = 4
[HCO3- ]
4=
[H 2CO3 ] lEVEl II
4
[% HCO3–] = ¥ 100 fi 80 % 1. C6H5COOH + NaOH h C6H5COONa + H2O
5
39. (a) 2 1
NaOH + H3PO4 m NaH3 PO3 + H2O 1 0 1
5 mm 9 mm 0 0 [salt] 1
form buffer pH = pKa log + pH = 4.2 + log
[acid] 1
5 pH = 4.2
\ Ph = Pka1 + log
4 C6H5COOH + NaOH h C6H5COONa + H2O
= 3 + 0.7 - 0.6 = 3.1 2 2
40. Mg(NO3)2 + 2NaF h MgF2 + 2NaNO3 0 0 2
2.5 5 1 1
pH = 7 + pKa + log C
0 0 2.5 2 2
+2 2.5 1 2
(Mg ) = 0.0714 M pH = 7 + 2.1 + log
35 2 200
MgF2 h Mg+2 + 2 F pH = 9.1 – 1 pH = 8.1
Ionic product 2. (d)
41. IP > Ksp I.P. = [Ca+2][F–]2 CH3COOH + NaOH h CH3COONa + H2O
2 0.1 0.1 0 0
È10-2 ˘ È10-3 ˘ È10-8 ˘
I.P. fi Í ˙Í ˙ fiÍ ˙ At 1/3 neutralisation
Î 2 ˚Î 2 ˚ Î 4 ˚ 2/3 1/3 1/3 1/3
IP > Ksp (1.7 ¥ 10–10) (salt)
pH = pKa + log
42. (b) (acid)
HCl + NaCl
1 mL, 0.1 99 mL 1/3 1
pH1 = pKa + log = pKa + log ...(1)
2/3 2
at 2/3 neutralization 10. (d)

2/3 HCl Æ 0.09 M
pH2 = pKa + log = PKa + log 2 ...(2)
1/3 CH3COOH Æ C1 = 0.1 M, a1 K a1 = 10-5 ,
1 Cl2CHCOOH Æ C2 = 0.09 M, a2 , K a2 = ?
pH1 – pH2 = log – log 2
2 pH = 1, [H+] = 0.1
1 0.1 = 0.09 + C1a1 + C2a2
= log = –2 log 2
4 C1a1 + C2a2 = 0.01 ...(i)
3. HSO4– h H+ + SO42– CH3COOH m CH3COO– + H+
1 C1
(1– a) a a C1 – C1a1 C1a1 0.1
–2 a 2 Cl2HCCOOH m Cl2HCCOO– + H+
10 = \ a fi 0.09 pH = 1.02 C2
1- a
C2 – C2a2 C2a2 0.1
4. (a) HCN is a weak acid so H+ due to it can neglect.
As comparison to HF. (C a )(0.1)
K a1 = 1 1  a1 ¥ 0.1 = 10–5
C1 (1 - a1 )
[H + ] = KaC = 6.7 ¥ 10- 4 ¥ 0.1 = 67 ¥ 10- 6
a1 = 10–4
–3
= 8.18 ¥ 10 Putting this in equation (i)
pH = –log [8.18 ¥ 10–3] = 3 – log [8.18] 10–4 ¥ 0.1 + 0.09a2 = 0.01
pH = 2.087 a2 = 0.111
5. (b)
(C2a 2 )(0.1) (0.111)(0.1)
CH3CO2H + NaOH h CH3COONa + H2O K a2 = = = 1.25 ¥ 10-2
10m mol 5m mol C2 (1 - a 2 ) 1 - 0.111
pH = pKa = 5 – log 1.8 pH = 4.74 w 10d
11. (c) M = % =C
-
[In ] [In - ] w Molar Mass
6. (b) pH = pkin + log 6 = 5 + log
[HIn] [HIn] 10 ¥ 10 ¥ 0.935
= 5.5
In - [HIn] 1 17
= 10 \ -
= Kb = Ca2 fi 5.5 ¥ 10–6 = 5.5a2
HIn [HIn] + [In ] 11
a = 10–3
7. (c) At half way [HIn] = In– [OH–] = Ca = 5.5 ¥ 10–3
[salt] [salt] pOH = 2.26 , pH = 11.7
pH = 5.5 + log 5.5 = pKa + log
[acid] [acid] 12. (b)
[salt] [salt] k w2 DH Ê 1 1ˆ
log = 0.75 fi = 5.62 ln = Á - ˜
[acid] [acid] k w1 R Ë T1 T2 ¯
Kh Kw 5.474 ¥ 10-14 DH Ê 1 1 ˆ
8. (a) h = h= ln = Á - ˜
C Ka ¥ C 1.08 ¥ 10-14 8.314 Ë 298 323 ¯
DH = 51952.6 J = 51.95 kJ/mole
10-14 ¥ 80 13. (a)
h= h = 2.48%
1.3 ¥ 10- 9 ¥ 1 Na2CO3 + HCl h NaHCO3 + NaCl
9. (c) CH3COOH + NaOH Æ CH3COO + H2O – 2 2
(WASB) – – 2
1 pk1 + pk2
pH = [pKw + pKa + log C] pH = = 8.35
2 2
14. (a)
1 1 Na3PO4 + HCl h Na2HPO4 + NaCl
= [14 + 5 – log 1.9 + log ]
2 20 0.8 1.6
1 – 0.8 0.8
= [19 – log 1.9 – log 20] Na2HPO4 + HCl h NaH2PO4 + NaCl
2
0.8 0.8
1 – – 0.8
pH = [19 – log 20 ¥ 1.9] = 8.78
2 pk1 + pk2
pH = = 4.66
pOH = 5.28 [OH] = 5.24 ¥ 10–6 2
15. (c) Initial pOH = pKb =4.744 Na2HPO4 + NaOH h NaH2PO4 + NaOH
Let x mole of HCl has been added so x
[NH4+] = 0.1 + x, [NH3] = 0.1 – x x–y — y y+x
pOH = 5.744 x – y  x, y + x  x, so
0.1 + x ( y + x)
5.744 = 4.744 + log 1.58 ¥ 10–7 = y; y
0.1 - x ( x - y)
0.1 + x NaH2PO4 + H2O h H3PO4 + NaOH
1 = log
0.1 - x y
0.1 + x 0.9 y–z — z z+x
= 10 fi x = = 0.082 moles y – z  y, z + x  x
0.1 - x 11
z ( x + z ) z ¥ x z ¥ 3.73 ¥ 10-2
16. (a) Na3PO4 + H2O h Na2HPO4 + NaOH 1.4 ¥ 10-12 = = =
( y - z) y 1.58 ¥ 10-7
K
K = w = 0.0222 z = 5.93 ¥ 10–18
Ka3 [H3PO4] = z = 5.93 ¥ 10–18 M
Na2HPO4 + H2O h NaH2PO4 + NaOH 18. (b) At equivalence point
Kw meq. of HA = meq. of NaOH = 3.612
K= = 1.58 ¥ 10–7 NaA + HCl h HA + HCl + NaCl
Ka2
3.612 1.806
NaH2PO4 + H2O h H3PO4 + NaOH 1.806 – 1.806
K [S]
K = w = 1.4 ¥ 10–12 pH = pKa + log
Ka3 [A]
Since equilibrium constant of second and third reaction 1.806
is very less, [OH–] will mainly come from first reaction. 4.92 = pKa + log
1.806
Na3PO4 + H2O h Na2HPO4 + NaOH pKa = 4.92
0.1 Now NaOH + HA h NaA
0.1 – x x x 2 2
x2 – – 2
= 0.0222 fi 45x2 + x – 0.1 = 0 2
0.1 - x [NaA] = = 0.1
20
x = 3.73 ¥ 10–2
1 1 4.92 1
[OH–] = x = 3.73 ¥ 10–2 M pH = 7 + pK a + log C = 7 + + log 0.1
17. (b) Na3PO4 + H2O h Na2HPO4 + NaOH 2 2 2 2
pH = 9
Kw 19. (a) In the beginning, let x m mole of BOH are present.
K= = 0.0222
K3 BOH + HCl h BCl + H2O
Na2HPO4 + H2O h NaH2PO4 + NaOH x
x – –
Kw 4
K= = 1.58 ¥ 10-7 3x x
K2 0
4 4
NaH2PO4 + H2O h H3PO4 + NaOH
K pOH = pkb + log 1
K = w = 1.4 ¥ 10-12 3
K3 14 – 9.24 = pkb – log 3
Since equilibrium constant of second and third reaction pkb = 5.237
is very less, [OH–] will mainly come from first reaction. kb = 5.8 ¥ 10–6
Na3PO4 + H2O h Na2HPO4 + NaOH now BCl + NaOH h BOH
0.1 x
0.1 – x x x 6
4
– – x
x2
= 0.0222 fi 45x2 + x – 0.1 = 0 x
0.1 - x = 6, fi x = 24
4
x = 3.73 ¥ 10–2
24
[OH–] = x = 3.73 ¥ 10–2 M [BOH] = = 0.48
50
[OH–] = kb ¥ C = 1.668 ¥ 10–3 10-13 10-17

s = 10–6 + + +10–3[OH–]+10–2 [OH–]2
pOH = 2.77 [OH - ] [OH - ]2
pH = 11.22 pH = 5, pOH = 9, [OH–] = 10–9
20. (a) HCO3– is proton acceptor (a base) as well as proton s = 10–6 + 10–4 + 10 + 10–12 + 10–20 = 10 M
donor (an acid) and it is amphiprotic. For such a case 25. (c) s = [Zn(OH)2(aq)]+Zn(OH)++Zn+2+Zn(OH)3–+
[H+] = K1K 2 Zn(OH)4–2
Ê pK + pK 2 ˆ k1k2 kk k
or pH = Á 1 ˜¯ s = k1+ -
+ 1 2- 32 + k1k4[OH–] + k1k4k5 [OH–]2
Ë 2 [OH ] [OH ]
–
HCO3 is an amphiprotic ion. It can undergo hydrolysis
10-13 10-17
forming alkaline solution. s = 10–6 + + +10–3[OH–]+10–2 [OH–]2
HCO3– + H2O m H2 CO3 + OH– [OH - ] [OH - ]2
–
HCO3 can also ionise to form acidic solution, pH = 13, pOH = 1, [OH–] = 10–1
pH of this type of salt is – s = 10–6 + 10–12 + 10–15+10–4+10–4 = 2 ¥ 10–4 M
HCO3– + H2O H3O+ + CO3–2 26. (a) Let solubility of Cu3(AsO4)2 and Pb3(AsO4)2 is x
Ê pK + pK 2 ˆ 6.38 + 10.26 and y respectively.
pH = Á 1 ˜¯ = = 8.32 Cu3(AsO4)2 m 3Cu+2 + 2AsO4–3 Ksp = 8 ¥ 10–36
Ë 2 2
3x 2x + 2y
21. AgCNS m Ag+ + CNS–
Pb3(AsO4)2 m 3Pb+2 + 2AsO4–3 Ksp= 4.096 ¥ 10–36
solubility (1 – S1) (S1 + S2) S1
3y 2y + 2x
AgCl m Ag+ + Cl–
108 x3(x + y)2 = 8 ¥ 10–36 ...(i)
solubility (1 – S2) (S1 + S2) S2
108 y3(x + y)2 = 4.096 ¥ 10–36 ...(ii)
( Ksp ) AgCNS = ( S1 )( S1 + S2 ) ...(i)
(i) x3 8
fi 3= fi x = 1.25 y
( Ksp ) AgCl = ( S2 )( S1 + S2 ) ...(ii) (ii) y 4.096
Adding Eqs (i) and (ii) Putting this in Eq. (ii)
2 108y3 (2.25y)2 = 4.096 ¥ 10–36
( S1 + S2 ) = ( K sp ) AgCNS + ( Ksp ) AgCl y = 2.3 ¥ 10–8 x = 1.25y = 2.875 ¥ 10–8
( S1 + S2 ) = ( Ksp ) AgCNS + ( Ksp ) AgCl [Cu+2] = 3x = 8.825 ¥ 10–8
[Pb+2] = 3y = 7.1 ¥ 10–8
= 1.0 ¥ 10-12 + 1.7 ¥ 10-10 27. (b) Al(OH)3 m Al+3 + 3OH– Ksp
[Ag+] = (S1 + S2) =1.3 ¥ 10–5 Al(OH)4– m Al+3 + 4OH– K
Divide Eq. (ii) from Eq. (i) Al(OH)3 + OH– m Al(OH)4–
[Cl- ] S2 1.7 ¥ 10-10 Ksp
= = fi 1.7 ¥ 102 = 38.46
[CNS- ] S1 1.0 ¥ 10-12 K
È Al(OH - ) 4 ˘ 10-3
22. Ksp = s2 s = Ksp = 6.4 ¥ 10-5 38.46 = Í - ˙= -
Î [OH ] ˚ [OH ]
s = 8 ¥ 10–3 s = 8 mol/m3 [OH–] = 2.6 ¥ 10–5
23. AgNO3 + 2NH3 h [Ag(NH3)2+] pOH = 4.585
1.6 x pH = 9.415
5 ¥ 10–8 (x – 3.2) 0.8 28. (d) AgCl(s) m Ag+ + Cl– Ksp
[Ag(NH3 ) 2 ]+ Ag+ + 2NH3 m Ag(NH3)2+ K1 ¥ K2
Ks =
(AgNO3 )(NH3 ) +
AgCl(s)+2NH3 m Ag(NH3)2 + Cl–, K = Ksp K1K2
2 0.2
0.8/2 Ê x - 3.2 ˆ
108 = \Á ˜ = 0.16 0.2 – 2x x x
2 Ë 2 ¯
-8 Ê x - 3.2 ˆ
(5 ¥ 10 ) Á x2
Ë 2 ˜¯
K = KspK1K2 = = 0.002828
x=2M mole of NH3 = 4.0 (0.2 - 2 x) 2
24. (d) s = [Zn(OH)2(aq)] + Zn(OH)++Zn+2 + Zn(OH)3– + x
Zn(OH)4–2 = 0.05318
0.2 - 2 x
kk kk k
s = k1+ 1 2- + 1 2- 32 + k1k4[OH–] + k1k4k5 [OH–]2 x = 0.009613
[OH ] [OH ] Solubility = 9.6 ¥ 10–3 M
29. (b) 1
[Cl–] = 0.02 M (D) Æ Q = (pKa + log 3)
2
Ag(CN)2– m Ag++ 2CN– Kinst = 4 ¥ 10–19
0.05 2. [A Æ P,Q,R; B Æ R; C Æ Q,S; D Æ Q,R]
0.05–x  0.05 x 2x (A) CH3COOH + CH3COONa fi Buffer Solution
[S] = [A] \ acidic buffer at its maximum capacity
x ◊ (2 x) 2 pH = pKa = 4.74 \ [P, Q, R]
4 ¥ 10-19 =
0.05 (B) Mixture of S.A. and W.A.
4 x3 pH = –log [H+]SA \ pH < 7
= 4 ¥ 10–19 fi x = 1.7 ¥ 10–7 (C) CH3COOH + NH4OH Æ CH3COONH4
0.05
0.1 0.1 0
[Ag+][Cl–] = 1.7 ¥ 10–7 ¥ 0.02 = 3.4 ¥ 10–9 > Ksp
0 0 0.1
so AgCl will precipitate.
\ salt of WA and WB formed
30. (c) After mixing with equal volume
[Ag+] = 0.01 M, HCN = 0.01 M 1 1
\ pH = 7 + Pka - Pkb = 7
HCN m H+ + CN– Ka 2 2
1 Pka = Pkb
Ag+ + CN– m AgCN(s)
Ksp (CH3COONH4) also acts as simple buffer.
+ +
HCN + Ag m H + AgCN(s), (D) CH3 COONa + HCl Æ CH3COOH+ NaCl
300 ¥ 0.1 100 ¥ 0.1
Ka 30 10
K= = 2.25 ¥ 106
K sp 20 0 10 10
HCN + Ag+ m H+ + AgCN(s), means buffer
0.01 0.01 0 0 1
x x 0.01 – \ pH = 4.74 + log
2
since K value is very high, almost all of reactants will
pH < 7
convert into product.
3. [A Æ Q; B Æ R; C Æ P; D Æ P, S]
0.01 (A) 0.1 M KCN Salt of S.B. and W.A.
= 2.25 ¥ 106 x = 6.6 ¥ 10–5
x2 1 1
pH = 7 + Pka + log C
[Ag+] = 6.7 ¥ 10–5 M 2 2
1 1 1
= 7 + Pka + log[10-1 ] = 6.5 + Pka
lEVEl III 2 2 2
(B) 0.1 M C6H5 NH3Cl Salt of WB and SA
Match the Column 1 1
pH = 7 - Pkb - log C
2 2
1. [A Æ S; B Æ P; C Æ R; D Æ Q]
1 1
At maximum buffer capacity, [salt] = [acid] hence = 7 - Pkb - log[10-1 ]
pH = pKa 2 2
\ (A) Æ (S) 1
= 7.5 - Pkb
1 2
At the th equivalence point of titration of weak acid
4 (C) 0.1 MKCl salt of SA and SB \ pH = 7
1 (D) 0.1 MCH3COONH4
HA, pH = pKa + log
3 Salt of W.A. and W.B.
(B) Æ P 1 1
pH = 7 + Pka - Pkb
3 2 2
At the th equivalence point of titration of weak acid
4 if ka = kb
1 \ pH = 7
HA, pH = pKa + log 3 = pKa – log
3 4. [A Æ Q, S; B Æ P, R; C Æ P, R; D Æ Q, S]
(C) Æ R Only ion of W.A. or W.B. hydrolysis.
1 (A) NaHCO3 Æ Na+ + HCO3–
For C(M) solution of weak acid HA, pH = Ø
2
1Ê 1ˆ Anionic hydrolysis
(pKa – log c) = ÁË pK a - log ˜¯ \ solution basic
2 3
(B) CuSO4 Æ Cu+2 + SO4– – 10-3 V + 10-5 V

Ø And [H+] = = 5 ¥ 10–4
Cationic hydrolysis 2V
\ solution acidic in nature \ POH = 14 – 4.4 = 10.7
(C) K2SO4. Al2 (SO4)3. 24H2O 8. [A Æ S; B Æ P; C Æ Q; D Æ R]
\ Al+3 hydrolysis (A) Ag 2CrO 4  2Ag + + CrO -4
cationic hydrolysis
\ acidic solution. KsP = (2S ) 2 ( S ) = 4s 3
(D) NaCN Salt of SB and WA (B) H 2O  H + + OH -
NaCNÆ Na+ + CN–
Ø [H + ][OH - ]
Kd =
Aniomic Hydrolysis [H 2O]
\ anionic hydrolysis and solution basic in
nature. (C) BaCrO 4  Ba + 2 + CrO 4-
5. [A Æ P; B Æ S; C Æ R; D Æ Q] Ksp = S ¥ S
(A) If H.A. and NaA both present means buffer solution Æ 2K + + CO3-
(d) K 2CO3 ææ
0.01
Ph = Pka + log fi 5 -1= 4 CO3–2 anionic hydrolysis
0.1 \ Basic in nature Ph > 7
(B) BOH and BCl form basic buffer solution
0.1 Comprehension
POH = PKb + log fi6-0=6
0.1 Comprehension 1
\ Ph = 8 9. (d)
(C) HA + BOH m BA + H2O Suppose volume of HCO3– = V mL
Ø Millimoles of HCO3– = 5 V
Salt of W.A. and W.B. Millimoles of H2CO3 = 20
1 1 [HCO3- ]
\ Ph = 7 + pka - pkb
2 2 pH = pKa + log
[H 2CO3 ]
1 1
= 7 + (5) - (7) = 6 V
2 2 7.40 = 6.11 + log, V = 78 mL
(D) HNO3 + NaOH h NaO3 + H2O 4
500 ¥ 0.2 500 ¥ 0.2 10. (b) If CO2 escapes, [H+] decreases, hence pH increases.
– – 100 100
Comprehension 2
Salt of S.A. and S.B. formed \ Ph = 7
11. (d)
6. [A Æ R; B Æ Q,S; C Æ R; D Æ P,S]
Final pH = 1.7
1 1 or – log [H+] = 1.7
(A) pH = 7 + Pka - Pkb
2 2 or log [H+] = – 2 + 0.3
If Pka = Pkb or [H+] = 2 ¥ 10–2
pH = 7 Let V mL of 0.1 (M) HA solution is mixed with
1 1 100 mL of 10–2 (M) HCl. In the mixed solution, [HA]
(B) pH = 7 + Pka + log C V ¥ 10- 4
2 2 = ¥ 103
\ Ph > 7 (100 + V )
(C) No hydrolysis \ Ph = 7
0.1V 10- 3 ¥ 103
1 1 = ( M ) and [HCl] =
(D) pH = 7 - pkb - log C pH < 7 (100 + V ) (100 + V )
2 2
1
7. [A Æ Q; B Æ P; C Æ S; D Æ R] =
(A) PKa + Pkb = 14 (100 + V )
\ Pkb = 8 HA  H + + A–
(B) [H+] = 10–8 + x 0.1V 0.1V a 0.1V a 1
use x ª 10–7 (1 - a ) +
(100 + V ) (100 + V ) (100 + V ) (100 + V )
1
(C) Ph = [ Pka - log C ] (0.1V a + 1)
7 \ [H+] = = 2 ¥ 10–2
(B) Ph = –log [H+] = –log [5 ¥ 10–4] (100 + V )
or 0.1Va + 1 = 2 + 2 ¥ 10–2 ¥ V Comprehension 3

(0.1V a + 1) 0.1V a 14. (d)
¥
(100 + V ) (1.00 + V ) a 10-10
Ka = = ¥ 2 ¥ 10- 2 K a2 of HCO3- =
0.1V (1 - a ) (1 - a ) 2.1
(100 + V ) or pK a2 = 10 + log 2.1
a
\ ¥ 2 ¥ 10–2 = 10–2 1
(1 - a ) \ pH = 7 + (10 + log 2.1 ) – 1 = 11.161
2
a 1 15. (c)
or =
1- a 2 10- 6
or 2a = 1 – a K a1 of H 2CO3 =
2.2
1
or a= pK a1 = 6 + log 2.2
3
1
1 \at the half neutralisation point, pH = ( pK a1 + pK a2 )
\ 0.1V ¥ + 1 = 2 + 2 ¥ 10–2 ¥ V 2
3 1
V V = [10 + log 2.1 + 6 + log 2.2]
or - =1 2
30 50 1
20V = [16 + log ((2.1 ¥ 2.2)]
or =1 2
30 ¥ 50 1
150 = [16 + 0.665] = 8.33
or V= = 75 ml 2
2 16. (a)
12. (d) For isohydric solution, Ka1C1 = Ka2C2 At complete equivalence point, an aqueous solution of
13. (c) H2CO3 is produced.
HA  H+ + A– HD  H+ + D– 0.1
[H2CO3] = (M)
0.1 0.1 0.1 1 a2 a2 2
(1 - a1 ) a1 a1 (1 - a 2 )
2 2 2 2 2 2 [H + ] = K a1C
\
a 0.1
+ 2 + a1 1
2 2 or log [H+] = [log K a1 + log C]
+ 2
\ Total H in solution 0.1/2a1 + a2/2 for HA
\ Total H+ in solution 0.1/2a1 + a2/2 for HB 1
or pH = [ pK a1 - log C ]
a1 (0.1a1 + a 2 ) 2
10-2 = ¥ and
1 0.1˘
(1 - a1 ) 2 È
or pH = ÍÎ6 + log 2.2 - log 3 ˙˚
2
a2 (0.1a1 + a 2 )
10- 3 = ¥ 1
(1 - a 2 ) 2 or pH = [6 + 0.3424 + 1.48] = 3.91  4
2
Neglecting a1 and a2 with respect to 1 Comprehension 4
a1 17. (b)
= 10
a2 Let molar absorbance of H In = aH In and molar absor-
a2 bance of In– = a In -
2a 2
or 10–2  a1 ¥ = a1a2 = 1 \ 6 ¥ 10–4 ¥ aH In = 0.142
2 10
or a12 = 0.1 0.142
or a1 = 0.316 or aH In =
6 ¥ 10- 4
a2 = 0.0316
(0.0316 + 0.0316) and 6 ¥ 10–4 ¥ a In - = 0.943
+
\ final [H ] = = 0.0316
2 0.943
or final pH = 1.5 or a In - =
6 ¥ 10- 4
It is the approximate pH since practically a1 cannot be
neglected with respect to 1 At pH = 8, [In–] + [H In] = 6 ¥ 10–4
0.142 0.943 a2 C1 1
and -4
¥ [H In] + -4
[In - ] = 0.527 21. Ka = Ca 2 fi = = = 10
6 ¥ 10 6 ¥ 10 a1 C2 1/100
or 0.142[H In] + 0.943[In–] = 0.527 ¥ 6 ¥ 10–4 22. Ka = Ca2
and 0.142[H In] + 0.142[In–] = 6 ¥ 10–4 ¥ 0.142
\ 0.801[In–] = 0.385 ¥ 6 ¥ 10–4 a1 Ka1 1.8 ¥ 10-5 18
= = = ¥ 104 = 170 :1
0.385 a2 Ka2 6.2 ¥ 10 -10
6.2
or [In–] = ¥ 6 ¥ 10–4
0.801
= 0.48 ¥ 6 ¥ 10–4 = 2.88 ¥ 10–4 (M) 1 1
23. (a) pH = pK a - log C
18. (d) 2 2
[H In] = (6 – 2.88) ¥ 10–4 = 3.12 ¥ 10–4 4.50 ¥ 2 = pKa –log (0.1)
Kin
æææ
H In ¨ææ Æ H+ + In–
æ 9 – 1 = pKa pKa= 8 Ka= 10–8
[H + ][In – ] 10- 8 ¥ 2.88 ¥ 10- 4 24. (i) [H+] = Ka C = 18 ¥ 10- 6

K in = =
[H In] 3.12 ¥ 10- 4 1
\ pH = 3 – log [18] 2
2.88
= ¥ 10- 8 = 9.25 ¥ 10- 9 = 3 – 0.62 = 2.38
3.12
19. (d) (ii) [H+] = 10–8 + 10–7 = 10–7[0.1 + 1]
0.142 0.943 pH = 7 – log 1.1 = 6.95
0.625 = [H In] ¥ + [In - ] ¥
6 ¥ 10- 4 6 ¥ 10- 4 (iii) [OH–] = 10–10 + 10–7 = 10–7[1.001]
\ 0.625 ¥ 6 ¥ 10–4 = [H In] ¥ 0.142 + 0.943 ¥ [In–] POH = 7 – log 1.001 = 6.99
[H In] + [In–] = 6 ¥ 10–4 pH = 7.0004
\ 0.142 ¥ 6 ¥ 10–4 = [H In] ¥ 0.142 + 0.142[In–] 25. pKw = 14 – log 2.56 = 13.59 ª 13.6
or 0.801 [In–] = 0.483 ¥ 6 ¥ 10–4 pK w
pH = = 6.795
0.483 2
or [In–] = ¥ 6 ¥ 10–4 = 3.618 ¥ 10–4 (M)
0.801 26. pH = 11.5 [H+] = 10–11 5
\ [H In] = (6 – 3.618) ¥ 10–4 = 2.382 ¥ 10–4 [OH–] = 10–2 5
[H + ][In - ] bK
K in = NH4OH 
 NH4+ + OH–
[HIn]
10–2 5 10–2 5
[H + ] ¥ 3.618 ¥ 10- 4 10-5 1
or 9.5 ¥ 10- 9 = = 1.8 ¥ 10–5 C= =0.556 M
2.382 ¥ 10- 4 C 1.8
2.382 27. C = 10–2, [H+] = 10–3

or [H+] = ¥ 9.25 ¥ 10–9 = 6.09 ¥ 10–9 HA  H+ + A–
3.618 –2 –3
10 – 10 10–3 10–3
or pH = 9 – log 6.09 = 8.215
10- 3 ¥ 10- 3 10- 3
Subjective Ka = = = 1.1 ¥ 10- 4
10- 2 - 10- 3 9
Ka

20. (i) H2O  
 H+ + OH– 28. CHCl2COOH h H+ + CHCl2COO–
–7
10 10–7 0.01
[H ][OH ] 10 -7 ¥ 10 -7
+ - 0.01 – x (0.01 + x) x
Ka = =
[H 2O] 1000/8 x(0.01 + x)
= 2.55 ¥ 10- 2
0.01 - x
10 -14
= = 1.8 ¥ 10 -16 0.01 x + x2 = 2.55 ¥ 10–4 – 2.55 ¥ 10–2 x
55.5
x2 + 0.0355x – 0.000255 = 0
10 ¥ 10-15 CHCl2COO– = 6.126 ¥ 10–2 = x
(ii) K a = -10
= 1.67 ¥ 10-5
6 ¥ 10 29. For weak acid
10 ¥ 10-15 [H + ] = K1C1 + K 2C2 ... + K w
(iii) K a = = 4 ¥ 10-10
2.5 ¥ 10-5 = 1.8 ¥ 10- 5 ¥ 0.02 + 6.4 ¥ 10- 5 ¥ .01 + 10-14
= 100 ¥ 10- 8
[H + ][ACO - ] [NH 4OH] = [NH 4+ ]

[H+] = 10–3 Ka =
[ACOH]2 nNH4OH
– –4 \ number of moles of (NH4)2 SO4 =
[ACO ] = 3.6 ¥ 10 2
same [C7H5O2–] = 6.4 ¥ 10–4 0.1
= = 0.05 moles, x = 0.05 mole
30. H2S h 2H+ + S–2 2
[H+] = 2 ¥ 10–4, [H2S] = 0.1 M 34. CH3COO + H2O m CH3COOH + OH
K = K1¥ K2 K = 10–7 ¥ 10–14 0.08 – x x x
–21
K = 10
10-14
[2 ¥ 10- 4 ]2 [S-2 ] -21 4 ¥ 10-8 -2 Kh =
fi 10- 21 = 10 = [S ] 1.8 ¥ 10- 5
[0.1] 0.1
x2 10 0.8
1 Kh = = ¥ 10-10 x2 = ¥ 10-10
¥ 10-14 = [S–2] 2.5 ¥ 10–15 = [S–2] 0.08 1.8 1.8
4
31. (i) H3PO4  H+ + H2PO4– K1 = 7.225 ¥ 10–3 x2 = 0.44 ¥ 10–10 x = 0.66 ¥ 10–5
C(1 – a) Ca1 Ca1 35. C5H6N + H2O m C5H5NOH + H+
+
(ii) H2PO4–  HPO4–2 + H+ K2 = 6.8 ¥ 10–8 1

pH = [pKw – pKb – log C]
Ca1 (1 – a2) Ca1a2 [Ca1] 2
(iii) HPO4–2  H+ + PO4–3 K3 = 6.8 ¥ 10–8 1
a1a2C1(1 – a3) [Ca1] C(a1a2a3) 2.699 = [14 – pKb + 0.6]
2
Ca12 0.01 ¥ a12 5.398 = 14.6 – pKb
7.225 ¥ 10- 3 = = pKb = 14.6 – 5.398 = 9.802
(1 - a1 ) 1- a
Kb = 10–9 802
RxN. …(i) pK1 + pK 2
(1 – a) ¥ 0.7225 = a12 36. pH =
2
a12 + 0.7225 a – 0.7225 = 0
a1 = 0.562 11 + 7 - 2 log 4.5
pH = = 9 - log 4.5 = 8.34
fi [H+] = 0.01 ¥ 0.562 [H+] = 5.6 ¥ 10–3 2
[H2PO4] ª 5.6 ¥ 10–3 RxN. …(ii) n1
37. Q+ + H2O m QOH + H+ kw/k1 = n1¢
[HPO 4- 2 ][H + ]
–8 V
6.8 ¥ 10 = from [i] reaction. n¢1 – x x x+y
[H 2 PO 4- ]
n
fi [HPO4–2] = 6.8 ¥ 10–8 M RxN. …(iii) R+ + H2O m ROH + H+ 2 = n2¢
V
[PO 4-3 ][H + ] n¢2 – y y y+x
4.5 ¥ 10-13 =
[HPO 4-2 ] kw x( x + y ) x( x + y )
=  ...(i)
4.5 ¥ 10-13 ¥ 6.8 ¥ 10- 8 k1 n1¢ - x n1¢
= [PO 4-3 ]
5.6 ¥ 10- 3 kw y ( x + y ) y ( x + y )
=  ...(ii)
5.464 ¥ 10–18 = [PO4–3] k2 n2¢ - y n2¢
32. NH4Cl h NH4+ + Cl–
Assuming x << n1¢ and y << n2¢
NH4OH  NH4+ + OH–
from Eqs (i) and (ii)
[NH +4 ][OH - ] kw k
Kb = n1¢ and y(x + y) = w n2¢
[NH 4OH] x(x + y) =
k1 k2
[NH4+] = is due to salt because NH4OH ionises in less Adding both
amount due to common ions effect. È n ¢ n ¢ ˘ k (k n ¢ + k1n2¢)
( x + y )2 = kw Í 1 + 2 ˙ = w 2 1
0.1 ¥ [OH - ] Î k1 k2 ˚ k1k2
1.8 ¥ 10-5 = 9 ¥ 10-6 = [OH - ]
0.05 kw
33. POH = 14 – 9.26 = 4.74 [H + ] = ( x + y ) = (k2 n1 + k1n2)
k1k2V
[NH +4 ]
4.74 = 4.74 + log pH = - log[H + ]
[NH 4OH]
1 ÈÊ k k ˆ V ˘
[NH +4 ] pH = log ÍÁ 1 2 ˜ ˙
log 1 = log 2 Ë
Î w k ¯ ( k n
2 1 + k n )
1 2 ˚
[NH 4OH]
k s = 3.446 ¥ 10–9 M
38. Na4Y + H2O m Na3HY + NaOH w = 1.818 ¥ 10- 4 41. Ksp = [Al+3][OH–]3
k4
5 ¥ 10–33 = [1 ¥ 10–3][OH–]3
0.1
[OH–] = 1.7 ¥ 10–10
0.1 – x x x
pOH = 9.767
x2 pH = 4.23
= 1.818 ¥ 10–4 fi 5500.55x2 + x – 0.1 = 0
0.1 - x 42. In beginning [H+] = K a C
x = 4.17 ¥ 10–3
k [H+] = 1.8 ¥ 10-5 = 0.004242
Na3HY + H2O m Na2H2Y + NaOH w = 1.445 ¥ 10- 8
k3 pH = 2.372
x On doubling pH, new pH= 4.744
x–y y y+x [H+] = 1.8 ¥ 10–5
since y << x x – y  x, x + y  x
CH3COOH m CH3COO– + H+
y◊x C
1.445 ¥ 10–8 = =y
x C – Ca Ca Ca
k (Ca ) 2
Na2H2Y + H2O m NaH3Y+NaOH w = 4.7 ¥ 10-12 Ka = , Ca = [H+] = 1.8 ¥ 10–5
y k2 C (1 - a )
y–z z z+x (1.8 ¥ 10-5 ) 2
y – z  y, z + x  x 1.8 ¥ 10–5 =
C - Ca
z◊x
4.7 ¥ 10–12 = z = 1.628 ¥ 10–17 C – Ca = 1.8 ¥ 10–5
y C = 3.6 ¥ 10–5
kw 1
NaH3Y + H2O m H4Y + NaOH = 9.8 ¥ 10-13 V= = 2.77 ¥ 104 L
k1 C
z 43. (a) PV = nRT
z–t t t+x
1 ¥ 0.959 = n ¥ 0.0821 ¥ 298
z – t  z, t + x  x
n = 0.03919
t◊x 959 ml in 1 ml H2O
9.8 ¥ 10–13 = t = 3.82 ¥ 10–27
z Volume of H2O = 1 mL (per volume of H2O)
t n 0.03919
Fraction = = 3.82 ¥ 10–26 C= = = 39.19 M
0.1 V 10-3
39. s = [Zn(OH)2(aq.)] + Zn(OH)+ + Zn+2 + Zn(OH)3–
+ Zn(OH)4–2 pkb = 3.39 fi kb = 4 ¥ 10–4
kk kk k [OH - ] = KbC = 0.1252 M
s = k1 + 1 2- + 1 2- 32 + k1k4[OH–] + k1k4k5 [OH–]2
[OH ] [OH ] pOH = 0.9023 pH = 13.097
(b) M = 0.1252 for NaOH
10-13 10-17
s =10–6 + + +10–3[OH–]+10–2 [OH–]2 44. (a) H3PO4 + NaOH h NaH2PO4 + H2O
[OH - ] [OH - ]2 6 3
(b) pH = 9, pOH = 5, [OH–] = 10–5 3– 3
s = 10–6+10–8+10–7+10–8+10–12 = 1.12 ¥ 10–6 M pH = pk1 = 2.12
40. Given: (b) H3PO4 + NaOH h NaH2PO4 + H2O
1 6 6
Ag + Cl2 m AgCl DG°1=–109.7kJ/mole–1
2 – – 6
Ag h Ag+ + e– DG°2 = 77.2 kJ/mole–1 pk1 + pk2
pH = = 4.66
1 2
e– + Cl2 h Cl– DG°3 = –131.2 kJ/mole–1
2 (c) H3PO4 + NaOH h NaH2PO4 + H2O
so for reaction 4.8 7.2
AgCl m Ag+ + Cl– DG° = –DG°1 + DG°2 + DG°3 – 2.4 4.8
DG° = 55.7 kJ/mole NaH2PO4 + NaOH h Na2HPO4 + H2O
DG° = – RT ln Ksp 4.8 2.4
55.7 ¥ 10–3 = –8.314 ¥ 298 ln Ksp 2.4 – 2.4
Ksp = 1.723 ¥ 10–10
pH = pk2 = 7.2
1.723 ¥ 10–10 = [Ag+][Cl–] = s ¥ 0.05
(d) H3PO4 + NaOH h NaH2PO4 + H2O fi 27.77a2 + 34.33a – 1 = 0a = 0.0285

4 10 [H+] = 0.005a = 1.425 ¥ 10–4 pH = 3.846
– 6 4 (c) On further diluting solution by 10 times
NaH2PO4 + NaOH h Na2HPO4 + H2O [HCOOH] = 0.0005, [HCOONa] = 0.0006
4 6 HCOOH m H+ + HCOO–
– 2 4 0.0005
Na2HPO4 + NaOH h Na3PO4 + H2O 0.0005(1–a) 0.0005a 0.0005a + 0.0006
4 2
(0.0005a + 0.0006)(0.0005a )
2 – 2 K a = 1.8 ¥ 10- 4 =
pH = pk3 = 12 0.0005(1 - a )
45. H3PO4 Æ k1 = 7.5 ¥ 10–3, k2 = 6.2 ¥ 10–8, k3 = 10–12 0.0005a 2 + 0.0006a
(i) Na3PO4 + NaH2PO4 h 2Na2HPO4 = = 1.8 ¥ 10- 4
1- a
5 5
– – 10 2.77a2 + 4.33a – 1 = 0 fi a = 0.2047
[H+] = 0.0005a = 1.0235 ¥ 10–4
pk + pk3
pH = 2 = 9.6 pH = 3.9899
2 48. pH = 8, [H+] = 10–8, [OH–] = 10–6
(ii) H3PO4 + Na3PO4 h Na2HPO4 + NaH2PO4 HCO3– m H+ + CO3–2 K = 5 ¥ 10–13
4 4 0.0005
– – 4 4 0.0005–y–z 10–8 y
pH = pk2 = 7.2 K
46. BOH + HCl h BCl + H2O HCO3–+H2O m H2CO3 + OH– K = w =2 ¥ 10–8
K1
4 4 0.0005
–6
– – 4 0.0005 – y – z z 10
At end point, m moles of BOH = m moles of HCl since equilibrium constant for first reaction is very less
0.16 ¥ V = 4 V = 25 mL y << z
Total volume = 40 + 25 = 65 mL z (10- 6 )
4 2 ¥ 10-8 =
[BCl] = 0.0005 - z
65
51 z = 0.0005 fi z = 9.8 ¥ 10–6
Since BCl is salt of SAWB.
1 1 [H2CO3] = 9.8 ¥ 10–6 M
pH = 7 - pkb - log C [HCO3–] = 0.0005 – 9.8 ¥ 10–6 = 4.9 ¥ 10–4 M
2 2
1 1 4 10- 8 ¥ y
5.23 = 7 - pkb - log 5 ¥ 10-3 =
2 2 65 4.9 ¥ 10- 4
pkb = 4.75 [CO3–2] = y = 2.45 ¥ 10–8 M
Now on further adding NaOH 49. Fe + H2O h Fe(OH)+2 + H+ k = 6.5 ¥ 10–3
+3
BCl + NaOH h BOH + NaCl x
4 1.8
0.95x 0.05x 0.05x
2.2 – 1.8
2.2 (0.05) 2 x
pOH = pkb + log = 4.837 fi pH = 9.1628 6.5 ¥ 10–3 = x = 2.47
1.8 0.95
[H+] = 0.05x = 0.1235 pH = 0.908
0.06
47. (a) pH = pKa + log salt
0.05 50. pH = pK2 + log
acid
pH = 3.744 + log 1.2 = 3.823
(b) On diluting solution 10 times y
6.7 = 7.2 + log
[HCOOH] = 0.005, [HCOONa] = 0.006 0.005
HCOOH m H+ + HCOO– y = 1.58 ¥ 10–3 mole
0.005 51. When indicator is half in ionic form pH = pKa = 7.2
0.005 (1 – a) 0.005a 0.005a + 0.006 pH = 7.2 + log 5 = 7.898
(0.005a + 0.006) (0.005a ) Now with this pH
Ka = 1.8 ¥ 10–4 =
0.005(1 - a ) 7.898 = pKa1 + log 4 = pKa1 = 7.2959
Again when 50% of new indicator is in ionic form
0.005a 2 + 0.006a pH = pKa1 = 7.2959
= 1.8 ¥ 10- 4
1- a
52. 4 m mole of H+ ion will produce 25

4 ¥ 10-3 –5 255
[H + ] = = 0.04 \ pOH = – log 1.8 ¥ 10 + log
0.1 0.5
1 255
PO4–3 + H+ h HPO4–2 pOH = 6.4437
k3
0.02 0.04 0.08 pH = 14 – pOH = 7.5563
0.02 0.10 [salt]
1 (c) pH = – log Ka + log
HPO4–2 + H+ h H2PO4– [acid]
0.10 0.02 k 2
0.35
0.08 – 0.02
So now they form a buffer solution of HPO4–2 and = – log 3.6 ¥ 10 + log 500
–4
0.25
H2PO4–
500
0.08 pH = 3.5898
pH = pk2 + log (k2 = 6.3 ¥ 10–8)
0.02 57. (a) Bronsted Lowry acid : H2PO4–, NH4+
pH = 7.2 + log 4 = 7.8
(b) Bronsted Lowry base: SO32- , ClO–, H2PO4–
53. In terms of Lewis acid-base theory, the reaction of SO2
with water is very similar to the reaction of SO2 with (c) Lewis acid : Fe3+ , BCl3
pyridine. SO2 acts as an electron pair acceptor (Lewis (d) Lewis base : H2PO4– , SO32- , ClO–
acid) and water acts as the electron pair donor (Lewis
base). 58. pH of HCl solution = 2; [H3O+] in solution = 10–2 M
– Meq. of HCl solution (N1V1) = 10–2 ¥ 200 = 2
H
O H O O pH of NaOH solution = 12; [OH–] in solution = 10–2 M
O + S O S
–
+ H+ H O S Meq. of NaOH solution (N2V2) = 10–2 ¥ 300 = 3
H O O O H
Total volume Vnet of the solution after mixing =
54. CH3COOH being weaker acid than oxallic acid, does (200 + 300) = 500 mL
not decompose CaC2O4. On the other hand, HCl be- For heterogeneous mixtures
ing stronger acid forms Ca2+ and oxalate ion to pass N1V1 ~ N2V2 = NVnet
CaC2O4 in solution state. 2 ~ 3 = N (500)
CaC2O4 + 2HCl Æ CaCl2 + H2C2O4 N[OH–] = 1/500 = 2 ¥ 10–3
55. Meq. of HClI in 1 mL = 10–5 ¥ 1 Kw (10-14 M 2 )
Meq. of HClII in 1000 mL = N ¥ 1000 [H3O+] = = = 5 ¥ 10–12 M
[OH - ] (2.0 ¥ 10-3 M)
i.e., Meq. of HCl (conc.) = Meq. of HCl (dil.)
\ 10–5 ¥ 1 = N ¥ 1000 pH = – log [H3O+] = –log (5.0 ¥ 10–12)
\ N HClII = 10–8 = (12 – log 5) = (12 – 0.69897) = 11.30103
59. The reaction between an acid and base is
pH = 6.9788 CH3COOH + NaOH m CH3COONa + H2O
[salt] The concentration of CH3COONa at the equilibrium
56. (a) pH = –log Ka + log
[acid] 0.1
point = = 0.05 M
3 ¥ 1000 2 ¥ 1000 2
 [salt] = M and [acid] = M The formula for finding the pH of the salt solution is
82 ¥ 100 60 ¥ 100
3 ¥ 1000
1
82 ¥ 100 pH = – [log Kw + log Ka – log C]
\ pH = –log 1.8 ¥ 10–5 + log 2
2 ¥ 1000
1
60 ¥ 100 = – [log 10–14 + log (1.9 ¥ 10–5)
pH = 4.7851 2
[salt] –log (5.0 ¥ 10–2)]
(b) pOH = –log Kb + log
[base] 1
=– [–14 + (–5 + 0.2788) – (–2 + 0.6990)]
 total volume after mixing = 250 + 5 = 255 mL 2
Meq. of salt = 250 ¥ 0.1 = 25 1
Meq. of base = 5 ¥ 0.1 = 0.5 =– [–14 – 4.7217 + 1.301]
2
25 0.5
\ [salt] = M and [base] = M 1
255 255 =– [–17.420] = 8.71
2
60. Let the volume of NaHCO3 solution mixed = x mL [Salt]

Number of moles of NaHCO3 in x mL of 5M NaHCO3 pH = log – log Ka
[Acid]
5¥ x
solution = = 0.005x mol 0.8
1000 = log - log 1.8 ¥ 10- 5
Number of moles of H2CO3 in 10 mL of 2M H2CO3 1.2
2 ¥ 10 = log 2 – log 3 – log 1.8 ¥ 10–5
solution = = 0.02 mol = 4.5687
1000 63. pOH of NH3 and NH4Cl buffer
pH of the solution = 7.4, Ka for H2CO3 = 7.8 ¥ 10–7 [S ]
According to Henderson’s equation, = – log Kb + log
[ B]
[salt]
pH = –log Ka + log 0.1
[acid] = –log 1.8 ¥ 10–5 + log = 4.75
0.1
0.005 x ˆ pH = (14 – 4.75) = 9.25
7.4 = –log (7.8 ¥ 10–7) + log ÊÁ
Ë 0.02 ˜¯ First case
NH3 + HCl h NH4Cl
M1V1 [S] = (0.1+0.02) = 0.12 M
or pH = –log Ka + log
M 2V2 [B] = (0.1 – 0.02) = 0.08 M
0.005 x 0.12
7.4 = (7 – log 7.8) + log pOH = –log Kb + log
0.02 0.08
5¥ x = 4.75 + 0.176 = 4.926
pH = –log Ka + log pH = 14 – 4.926 = 9.074
2 ¥ 10
D pH = (9.25 – 9.074) = 0.176 pH unit
7.4 = (7 – 0.892) + log (0.25x)
Second case:
7.4 = 6.108 + log (0.25 x)
NH4Cl + NaOH m NH4OH + NaCl
log (0.25x) = 7.4 – 6.108 = 1.292
[S] = (0.1 – 0.02) = 0.08 M
0.25x = Antilog 1.292 = 19.59
[B] = (0.1 + 0.02) = 0.12 M
19.59
\ x= = 78.36 0.08
0.25 pOH = –log Kb + log
0.12
Thus, the volume of 5M NaHCO3 solution to be mixed = (4.75 – 0.176) = 4.576
= 78.36 mL pH = (14 – 4.574) = 9.426
61. Number of milli-equivalents of NaOH = 800 ¥ 0.05 = D pH = (9.426 – 9.25) = 0.176 pH unit
40 [S ] a
Number of milli-equivalents of HCl = 200 ¥ 0.1 = 20 64. pH = pKa + log = pKa + log
[ A] (0.29 - a )
Number of milli-equivalents of NaOH left after the ad-
dition of HCl = 40 – 20 = 20 a
4.4 = 4.76 + log
Total volume = (200 + 800) mL = 1000 mL = 1 L (0.29 - a )
20 milli-equivalents or 0.02 equivalent of NaOH are a
present in 1 L, i.e., - 0.36 = log
(0.29 - a )
0.02 N NaOH = 0.02 M NaOH and the base is com-
pletely ionised. 0.29 - a
log = 0.36 = log 2.3
[OH–] = 0.02 M = 2 ¥ 10–2 M a
pOH = – log (2 ¥ 10–2) = 1.7 2.3a = 0.29 – a
pH = 14 – 1.7 = 12.3 3.3a = 0.29
62. On adding HCl, the free hydrogen ions will combine
with CH3COO– ions to form CH3COOH. Thus, the a = 0.087 M = salt
concentration of acetic acid increases while that of acid = 0.29 – 0.087 = 0.203 M
CH3COO– ions decreases. [CH3COO - ]
[CH3COOH] = (0.2 +1) = 1.2 mol L–1 65. pH = pKa + log
[CH3COOH]
[Salt] = (1 – 0.2) = 0.8 mol L–1
pKa = –log (1.8 ¥ 10–5) = 4.7447
Applying Henderson’s equation,
[CH3COO–] = 2 ¥ [(CH3COO)2Ba] = 0.2 M
[salt]
Ph = PKa + log [CH3COOH] = 0.1 M
[Acid]
0.2
pH = 4.7447 + log = 5.046
0.1
66. Concentration of HNO3 solution = 0.63 g per 100 mL If the concentration of salt is increased three times,
(Given) then p’OH = 5 + log 3 = 5 + 0.48 = 5.48
6.3 71. Applying N1V1 = N2V2
= 6.3 g L–1 = mol L–1 = 0.1 M
63 Ba(OH)2 Mixture
( Mol. wt. of HNO3 = 63) (Normality of solution of Ba(OH)2 = 2 ¥ its molarity)
Now, HNO3 completely ionizes as We have, 0.01 ¥ 2 ¥ 50 = N2 ¥ (50 + 50) because it is
HNO3 + H2O m H3O+ + NO3– assumed as 100% ionised)
 [H3O+] = [HNO3] = 10–1M 0.01 ¥ 100
\ pH = –log [H3O+] = – log 10–1 = 1 N2 = = 0.01 N = [OH - ]
100
67. (i) Calculation of molarity:
pOH = –log [OH–] = –log 10–2 = 2 log 10 = 2
Weight of NaOH dissolved = 4.0 g L–1
pH + pOH = 14 or pH + 2 = 14 or pH = 12
Molecular weight of NaOH = 40
72. For acetic acid (weak acid)
\ molarity of the solution
a1 v
Strength in gL-1 4.0 = 1
= = = 0.1 M a2 v2
Molecular weight 40
2
(ii) Calculation of the OH– ion concentrated NaOH Ê 1ˆ 300
completely ionises as ÁË ˜¯ =
2 V2
NaOH m Na+ + OH– or V2 = 1200 mL
\ [OH–] = [NaOH] = 0.1 M = 10–1 M
So, 1200 – 300 = 900 mL water should be added.
(iii) Calculation of pH
73. We have,
We know that
pH = –log [H+]
[H3O+][OH–] = KW = 1.0 ¥ 10–14
4.18 = –log [H+]
KW 1.0 ¥ 10-14 or log [H+] = –4.18
 [H3O+] = = = 10–13 M
[OH - ] 10-1 Taking antilog,
[H+] = 6.61 ¥ 10–5 mol L–1
\ pH = –log [H3O+] = –log 10–13 = 13
Now, for equilibrium
68. N1V1 + N2V2 + N3V3 = NV
H2CO3 m HCO3– + H+
N N N [HCO3- ][H + ]
¥ 200 + ¥ 100 + ¥ 100 = N (400) K a1 =
10 20 20 [H 2CO3 ]
20 + 5 + 5 = N(400)
30 3 [HCO3- ](6.61 ¥ 10-5 )
N= = ¥ 10-1 or 4.45 ¥ 10-7 =
400 4 0.01
This is the normality of [H+] 4.45 ¥ 10-7 ¥ 0.01
 final solution is acidic \ [HCO3–] =
6.61 ¥ 10-5
\ pH = 1 + log 4 – log 3 = 1.12
= 6.73 ¥ 10–5 mol L–1
69. N1V1 ~ N2V2 = NV
Again for the dissociation of HCO3–, we have
N N HCO3– m CO3–2 + H+
¥ 2000 ~ ¥ 1000 = N (2000 + 1000)
10 10
[CO3-2 ][H + ]
200 – 100 = N (3000) K a2 =
100 1 [HCO3- ]
N= =
3000 30 K a2 ¥ [HCO3- ]
\ [CO3-2 ] =
N [H + ]
Hence, the resulting solution is HCl
30
4.69 ¥ 10-11 ¥ 6.73 ¥ 10-5
1 =
[H+] = = 0.033 mol L–1 6.61 ¥ 10-5
30
pH = – log [H+] = 4.8 ¥ 10-11 mol L-1
1 74. Given density of formic acid = 1.22 g cm–3
= -log = - log 1 + log 30 \ weight of formic acid in 1 L solution
30
= 0 + 1.4771 = 1.4771 = 1.22 ¥ 103 g
[Salt] [Salt] Thus,
70. pOH = pKb + log or 5 = pKb + log 1.22 ¥ 103
[Base] [Base] [HCOOH] = = 26.5 M
46
Since in case of auto-ionisation [Salt]

[HCOOH2+] ¥ [HCOO–] = 10–6. 80. We know, pH = pKa + log
[Acid]
\ [HCOO–] = 10–3
Now % dissociation of HCOOH [Formate]
4 = –log (1.8 ¥ 10–4 ) + log
- -3 [Formic acid]
[HCOO ] ¥ 100 Ca 10
= = ¥ 100 = 0.004%
[HCOOH] C (1 - a ) 26.5 [Formate]
4 = 3.74 + log
[Formic acid]
75. Acetic acid ionises partially while sodium acetate ion-
ises strongly in solution. Let x be the number of moles [Formate]
log = 4 – 3.74 = 0.26
of acetic acid ionised. The concentration can be formu- [Formic acid]
lated as follows :
[Formate]
CH3COOH(aq) + H2O m H3O+(aq) + CH3COO–(aq) = 1.8
(0.02 – x) x x [Formic acid]
CH3COONa h Na+(aq) + CH3COO–(aq) The buffer capacity of this solution would be maxi-
0.2 gives 0.2 0.2 mum near the pKa of the acid.
Because x is small as compared to 0.2, the total con- \ for maximum buffer capacity
centration of CH3COO– is approximately 0.2 mol L–1. pH = pKa = – log Ka = – log (1.8 ¥ 10–4 ) = 3.74.
Thus, 81. 100 mL of 0.1 M HCl = 10 m mol of HCl, 100 mL of
[CH3COO–] = 0.2 + x  0.2 mol L–1 0.2 M NH3 = 20 m mol of NH3
and [CH3COOH] = 0.2 – x  0.2 mol L–1 NH3 + HCl h NH4 Cl
[H3O + ][CH3COO - ] NH4 Cl formed = 10 m mol, NH3 left unreacted = 10 m
Ka = mol, Volume of solution = 200 mL
[CH3COOH]
10 10
[H3O + ] ¥ 0.2 [NH3] = M = 0.05 M; [NH4+] = M = 0.05 M
1.8 ¥ 10-5 = 200 200
0.02
[Salt]
1.8 ¥ 10-5 ¥ 0.02 pOH = pKb + log
[H3O+] = = 1.8 ¥ 10–6 mol L–1. [Base]
0.2
76. C6H5OH + H2O m C6H5O– + H3O+ 0.05
= –log (1.8 ¥ 10–5) + log = 4.74
(0.05 – x) x x 0.05
pH = 14 – pOH = 14 – 4.74 = 9.26
[H3O + ] = K a ¥ C = 1 ¥ 10-10 ¥ 0.05 = 5 ¥ 10-12 82. (a) pH at 1/4 neutralisation
= 2.2 ¥ 10- 6 M x /4 1
(pH)1 = pka + log = pka + log
[Phenate] = [H3O+] = 2.2 ¥ 10–6 M 3 x /4 3
77. (i) C6H5COOH + H2 O m C6H5COO– + H3O+ pH at 3/4 neutralisation
(pH)2 = pka + log = pka + log 3
(ii) HSO3– + H2O m SO32– + H3O+ DpH = (pH)2 – (pH)1 = 2 log 3 = 0.9542
(iii) CH3NH2 + H2O m CH3NH3+ +OH– x /3
(iv) H2S + H2O m HS– + H3O+ (b) 4.45 = pka + log = pka – log 2
2 x /3
78. Given: Kb = 5.4 ¥ 10–4 pka = 4.751
K a ¥ Kb = K w (c) DpH = 2, i.e.,
Kw 1 ¥ 10 -14 (pH)1 = pka + 1, (pH)2 = pka – 1
fi Ka = = = 1.23 ¥ 10 -11
Kb 5.40 ¥ 10 - 4 [S ]
For pka + 1 fi = 10
79. pH = –log[H3O ] = 12+ [ A]
log [H3O+] = –12 x
= 10 fi x = 10a – 10x
\ [H3O+] = 1 ¥ 10–12 mol L–1 a-x
Kw
We know that Kw = [H3 O+][OH–] \ [OH–] = 10a
[H3O + ] x=
11
Since NaOH is a strong base, it is completely ionised. th
\ [NaOH] = [OH– ] = 1 ¥ 10–2 mol L–1 i.e., 10 stage
Molecular mass of NaOH = 40 11
\ amount of NaOH in grams per litre [S ] 1
For pka – 1 fi =
= 1 ¥ 10–2 ¥ 40 = 0.4 g [ A] 10
x 1 s2
= ksp = [M+2][A–2] = s ◊ x =
a - x 10 [H + ] [H + ]2
1+ +
a k2 k1k2
x=
11
Ê [H + ] [H + ]2 ˆ
1 S = ksp Á1 + +
i.e.,
11
th stage Ë k2 k1k2 ˜¯
83. Zn(OH)2(s) m Zn+2(aq) + 2OH–(aq) Ksp [H + ][HCO3- ] [H + ][CO32- ]
Zn(OH)2(s) + 2OH– m [Zn(OH)4]–2(aq) KC 85. Ka1 = ; Ka2 =
[H 2CO3 ] [HCO3- ]
dissolved Zn(OH)2 is present in form of Zn+2 and
[Zn(OH)4–2] [H + ]2 [CO32- ]
so solubility S = [Zn+2] + [Zn(OH)4]–2 Ka1 ¥ Ka2 = = 10-18
[H 2CO3 ]
Ksp
S= + KC[OH–]2 10-10 ¥ [CO32- ]
[OH ] - 2 \ = 10-18
10-2
For minimum solubility
[CO32–] = 10–10
ds -2 Ksp \ – log [CO32] = 10
=0fi + 2KC [OH – ] = 0
-
d [OH ] [OH ]- 3 86. 8 mL of 5 ¥ 10–3 (N) KMnO4 ∫ 40 ¥ 10–6 equiv
1/4 KMnO4 ∫ 40 ¥ 10–6 equivalent C2O42– ∫ 20 ¥ 10–6 mole
Ê K sp ˆ C2O42–
[OH - ] = Á
Ë K C ˜¯ \ in the saturated solution of CaC2O4(s),
[OH–] = 9.8 ¥ 10–5 20 ¥ 10-6
[C2O42–] = s = ¥ 103 = 10–4(M)
pOH = 4.00869 200
pH = 9.9913 \ for CaC2O4 , Ksp = s2 =10–8
84. MA h M+2 + A–2 \ pKsp = 8
S S
Let solubility of MA is S mole L–1. a1 V
87. = 1
But some amount of A–2 will undergo hydrolysis. Let x a2 V2
is the amount of A–2 left in solution. 2
\ Ê 1ˆ 300
k ÁË ˜¯ =
A–2 + H2O m HA– + OH– w 3 V2
k2
V2 = 2700 mL
k
HA + H2O m H2A + OH w
– –
VH2O = 2700 - 300 = 2400 ml
k1
k w [HA - ][OH - ] - k w [A -2 ] 88. The initial pH of solution = 5
= fi [HA ] =
k2 [A -2 ] k2 [OH - ] eq K
A– + HCOOH ¨ææ æææ Æ HA
æ + HCOO–
k w [H 2 A][OH - ] k [HA - ] 10 –2
5 ¥ 10 –3
10 ¥ 10 –3 —
= -
fi [H 2 A] = w –3 –3 –3
k1 [HA ] k1[OH - ] (10 ¥ 10 – x) (5 ¥ 10 – x) (10 ¥ 10 + x) x
k 2 [A -2 ] [HA][HCOO - ] (KA) HCOOH
[H 2 A] = w K eq = =
k1k2 [OH - ]2 [A - ][HCOOH] (Ka) HA
From mass balance x(10- 2 + x)

\ = 10
k [A -2 ] k w2 [A -2 ] (10- 2 – x)(5 ¥ 10- 3 – x)
S=x+ w -
+
k2 [OH ] k1k2 [OH – ]2 or x2 + 10–2 ¥ x
[H + ]x [H + ]2 x = 10(5 ¥ 10–5 – 5 ¥ 10–3 ¥ x – 10 ¥ 10–3 ¥ x + x2)
S=x+ + or x + 10 ¥ 10–3 ¥ x
2
k2 k1k2
= 10(x2 – 15 ¥ 10–3 ¥ x + 5 ¥ 10–5)
S
x= or x + 10 ¥ 10–3 ¥ x
2
[H ] [H + ]2
+
= 10x2 – 150 ¥ 10–3 ¥ x + 5 ¥ 10–4
1+ +
k2 k1k2 or 9x – 160 ¥ 10–3 ¥ x + 5 ¥ 10–4 = 0
2
or s2 = (240)1/3 ¥ 10–5 = 6.214 ¥ 10–5 (M)

+160 ¥ 10-3 ± (16) 2 ¥ 10- 4 – 4 ¥ 9 ¥ 5 ¥ 10- 4
or x = 3
2¥9 s1 = 6.214 ¥ 10–5 ¥ = 9.321 ¥ 10–5 (M)
2
+16 ¥ 10- 2 ± (256 - 180) ¥ 10- 4 \ [Ag+] = 2(6.214 + 9.321) ¥ 10–5
or x = = 31.07 ¥ 10–5
2¥9
or [Ag ] ¥ 105 = 31.07  31
+
+16 ¥ 10-2 ± 8.71 ¥ 10-2 91. (a, b) HIn (Red)  H+ + In– (Blue)
=
2¥9 [In - ]
pH = pKIn + log
or x = 4.05 ¥ 10–3 [HIn]
\ in the final solution moles of HCOO– = 4.05 ¥ 10–3
Ê 25 ˆ
and moles of HCOOH = 0.95 ¥ 10–3 (a) pH = (5 – log 3) + log ÁË ˜¯ = 4.05
10 -4 75
\ æææ
HCOOH ¨ææ Æ H+ + HCOO–
æ Ê 75 ˆ
(b) pH = pKIn + log Á ˜ = 5 – log 3 + log 3 = 5
+
[H ][HCOO ] - Ë 25 ¯
\ 10- 4 = 92. (b, c, d)
[HCOOH]
pH of
10- 4 ¥ [HCOOH] 10- 4 ¥ 0.95 ¥ 10-3 [I] Salts of weak acid and weak base as RCOONH4.
or [H + ] = =
[HCOO - ] 4.05 ¥ 10-3 [II] Amphiprotic ions as HCO3- , HS–.
[III] Buffer solutions are not affected by dilution.
0.95 Thus (b), (c), (d) are the correct options.
or [H+] = ¥ 10–4 = 0.234 ¥ 10–4
4.05 93. (a, b, d) At 25°C Kw = [H+][OH–] = 10–14
= 2.34 ¥ 10–5 (M) for water
\ pH = 5 – log 2.34 = 5 – 0.369 = 4.631 94. (a, c, d)
\ DpH = 5 – 4.631 = 0.369
K 10-14 -6
\ D(pH) ¥ 103 = 369 For NaA, Kh = W = -8 = 10
89. Mg(OH)2 m Mg2+ + 2OH– K a 10
x 2x + 3y KW 10-14
Al(OH)3 m Al3+ + 3OH– For NaB, Kh = = = 10-8
K a 10-6
y 2x + 3y
Now x >> y because Ksp of Mg(OH)2 > > Ksp of Al(OH)3 KW 10-14 10-6
For NaC, Kh = = =
fi x ¥ (2x)2 = 4 ¥ 10–12 fi x = 10–4 ...(1) K a 2 ¥ 10-8 2
and y ¥ (2x)3 = 1 ¥ 10–33 KW 10-14
-33 -33 -21 For NaD, Kh = = = 10- 4
10 10 10 K a 10-10
y= 3
= -12
=
8x 8 ¥ 10 8
KW 10-14
-4 For NaE, Kh = = = 10-7
fi x 10 ...(2) K a 10-7
= ¥ 8 = 8 ¥ 1017
y 10- 21 Since Kh of NaD is the highest, therefore, NaD is
So answer 8 ¥ 10+17 ¥ 10–17 = 8 most extensively hydrolysed
90. Ag2CrO4(s)  2Ag+ + CrO42– 1
For NaB pH = (pKw+pKa+log C )
2s1 + 2s2 s1 2
+
Ag2C2O4(s)  2Ag + C2O42– 1Ê 1ˆ 1 1
2s2 + 2s1 s2 or pH = Á14 + 6 + log ˜ = (20 - 1) = ¥ 19
2Ë 10 ¯ 2 2
\ 4(s1 + s2)2 ¥ s1 = 9 ¥ 10–12
or pH = 9.5
4(s1 + s2)2 ¥ s2 = 6 ¥ 10–12
For isohydric solution, Ka1C1 = Ka2C2
s1  10–7 ¥ 0.1 = 10–6 ¥ 0.01 = 10–8
or = 3/2
s2 Hence, 0.1(M) HE is isohydric to 0.01(M) HB solution
or s1 = 3/2s2 95. (c, d) Solubility of sparing soluble salt decreases due to
2 presence to common ion effect.
Ê 5ˆ Ksp = S2 in water
\ 4 ¥ Á ˜ ¥ s23 = 6 ¥ 10–12
Ë 2¯
AgCl m Ag+ + Cl–
6 ¥ 10-12 NaCl Æ Na+ Cl–
or s23 = = 24 ¥ 10–14 = 240 ¥ 10–15 C C + S¢
25
KsP = S¢(S¢ + C) [H + ]2 [A 2- ]
KsP K= = K1 ¥ K2
S¢ = [H 2 A]
C
= (1.0 ¥ 10–5) ¥ (5 ¥ 10–10) = 5 ¥ 10–15
\ S1 > S2 = S3 > S4
4. (c) Let molar solubility of Cr(OH)3 = S mol L–1
96. (a, b, d)
3+ -
-37
Cr(OH) 3 (S) m Cr (aq) + 3OH (aq) lim
S1 = 8 ¥ 10 S 3S x Æ•
–30
Ksp = 1.6 ¥ 10
S2 = 7 ¥ 10-16
= [Cr3+][OH–]3 = (S)(3S)3 = 27 S4
S3 = 5 10-72 ¥ 108 1.6 ¥ 10-30
\ S4 =
S4 = 4 1.8 ¥ 10-18 ¥ 27 27
\ S4 > S2 = S3 > S1 1.6 ¥ 10-30

\ S= 4
27
5. (a) pH of a solution = 5
PrEVIoUs yEArs’ QUEstIoNs \ [H+] = 10–pH = 10–5
oF JEE (MAIN & ADVANcED) HA (a weak acid) ionises as
1. (d) pH = 1 HA m H+ + A–
\ [H+] = 10–1 = 0.1 M 1.0 0 0
pH = 2 (1–10–5) 10–5 10–5
\ [H+] = 10–2 = 0.01 M [H - ][A - ] 10-5 ¥ 10-5 10-10
Ka = = = [1 >>> 10–5]
For dilution of HCl, [HA] (1 - 10-5 ) 1
M1V1 = M2V2
6. (a) Only in reaction (II), H 2 PO 4- , gives H+ to H2O.
0.1 ¥ 1 = 0.01 ¥ V2
Thus, behaves as an acid.
V2 = 10 L
Volume of water to be added to 10 – 1 = 9 L 7. (c) H2CO3 m H+ + HCO3- ; K1 = 4.2 ¥ 10–7
2. (c) HQ  H+ + Q– HCO3- m H + + CO32- ; K2 = 4.8 ¥ 10–11
[H+] = K a C by Ostawald’s dilution law K1 >> K2
[H ] = 10–pH = 10–3 M
+ \ [H+] = [HCO3- ]
C = 0.1 M
[H + ][CO3–2 ]
–3 K a ¥ 0.1 K2 =
Thus, 10 = [HCO3- ]
10–6 = Ka ¥ 0.1
So, [CO32- ] = K2 = 4.8 ¥ 10–11
\ Ka = 10–5
Alternate method 8. (b) [AgNO3] = [Ag+] = 0.05 M
HQ m H+ + Q– Ksp[AgBr] = [Ag+][Br–]
Initial concentration 0.1 M 0 0 Ksp (AgBr)
fi [Br - ] =
Given, pH = 3. This suggests [H+] = 10–3 M at equilib- [Ag + ]
rium so [Q] = 10–3 m
5.0 ¥ 10-13
Hence, [HQ] = 0.1 M – 10–3 M = = 10-11 [mol L-1 ]
ª 0.1 M [10–3 M <<< 0.1 M] 0.05
Ka for the above reaction is given by Moles of KBr needed to precipitate AgBr
= [Br–] ¥ V = 10–11 mol L–1 ¥ 1 L = 10–11 mol
[H + ][Q - ] [10-3 ][10-3 ]
Ka = = Therefore, amount of KBr needed to precipitate AgBr
[HQ] [0.1] = 10–11 mol ¥ 120 g mol–1 ¥ 1 L = 1.2 ¥ 10–9 g
Ka = 1 ¥ 10–5 9. (b) Mg(OH)2 m Mg2+ + 2OH–
3. (c) H2A m HA– + H+ Ksp = [Mg2+] [OH–]2
[H + ][HA - ] K sp 1 ¥ 10-11
\ K1 = 1.0 ¥ 10–5 = (given) [OH–] = = = 10–4
[H 2 A] [Mg ]2+
0.001
HA–  H+ + A2– pOH = –log[OH–] = –log[10–4]
+
[H ][A ]2 pOH = 4
\ K2 = 5.0 ¥ 10–10 = (given) \ pH = 14 – pOH = 14 – 4 = 10
[HA - ]
10. (b) Na2CO3 m Na+ + CO32- 13. (c) Mg(OH)2 m Mg2+ + 2OH–
Ksp = [Mg2+] [OH–]2
2-
[Na2CO3] = [CO3 ] = 1 ¥ 10–4 M K sp1 ¥ 10-11
[OH - ] = = = 10-4
BaCO3 m Ba + 2+
CO32- [Mg 2+ ] 0.001
K sp(BaCO3 ) = [Ba 2+ ][CO32- ] pOH = –log[OH–] = –log[10–4]
pOH = 4
K sp [BaCO3 ] \ pH = 14 – pOH = 14 – 4 = 10
[Ba 2+ ] =
[CO32- ] 14. (d) Na2CO3 h 2Na+ + CO32–
5.1 ¥ 10-9 1 ¥ 10–4 M Na2CO3 gives 1 ¥ 10–4M Na+ and
[Ba 2+ ] = 1 ¥ 10–4M CO3– –
1 ¥ 10- 4
KSP(BaCO3) = [Ba2+][CO32–]
[Ba2+] = 5.1 ¥ 10–5 M
Hence, at 5.1 ¥ 10–5 concentration of Ba2+, a precipitate 5.1 ¥ 10- 9
[Ba2+] = = 5.1 ¥ 10–5 M
will begin to form. 1 ¥ 10- 4
11. AgBr m Ag+ + Br– 15. (c) It corresponds to choice (c) which is the correct an-
Ksp = [Ag+] [Br–] swer.
For precipitation to occur BA + H2O m BOH + HA
Ionic product > Solubility product Base Acid
K sp5 ¥ 10-13 Now pH is given by
[Br - ] = = = 10-11
[Ag ] +
0.05 1 1 1
pH = pK w + pK a - pK b
i.e., precipitation just starts when 10–11 moles of KBr is 2 2 2
added to 1 l AgNO3 solution Substituting given values, we get
\ number of moles of Br– needed from KBr = 10–11 1
\ mass of KBr = 10–11 ¥ 120 = 1.2 ¥ 10–9 g pH = (14 + 4.80 – 4.78) = 7.01
2
12. (b) 16. (b) Let s = solubility
H2CO3(aq) + H2O(l) m HCO3–(aq) + H3O+(aq) AgIO3 m Ag+ + IO3–
0.034–x x x S S
[HCO3- ][H3O + ] x¥x Ksp = [Ag+][IO3–] = S ¥ S = S2
K1 = =
[H 2CO3 ] 0.034 - x Given: Ksp = 1 ¥ 10–8
x2 \ S = Ksp = 1 ¥ 10- 8
fi 4.2 ¥ 10–7 fi x = 1.195 ¥ 10–4
0.034
As H2CO3 is a weak acid so the concentration of H2CO3 = 1.0 ¥ 10–4 mol/lit
will remain 0.034 as 0.034 >> x. = 1.0 ¥ 10–4 ¥ 283 g/lit
x = [H+] = [HCO3–] = 1.195 ¥ 10–4 ( molecular mass of AgIO3 = 283)
Now, HCO3– (aq) + H2O(l) m CO32–(aq) + H3O+(aq) 1.0 ¥ 10- 4 ¥ 283 ¥ 100
x–y y y = gm/100 ml
1000
As HCO–3 is again a weak acid (weaker than H2CO3) = 2.83 ¥ 10–3 gm/100 mL
with x >> y. 17. (a) MX2 m M+2 + 2X–
[CO32- ][H3O + ] y ¥ ( x + y ) S 2S
K2 = =
[HCO3- ] ( x - y) where s is the solubility of MX2
Note: [H3O+] = H+ from first step (x) and from second then Ksp = 4 ¥ 10–12 = 4S3 ; S = 1 ¥ 10–4
step (y) = (x + y) \ [M+2] = S = 1 [M+2] = 1 ¥ 10–4
[As x >> y so x + yx and x – yx] 1
y¥x 18. (c) pH = –log[H+] = log
So, K 2  =y [H + ]
x
fi K2 = 4.8 ¥ 10–11 = y = [CO32–] 1
5.4 = log
So the concentration of [H+]  [HCO3–] = concentra- [H + ]
tions obtained from the first step. As the first step. As On solving, [H+] = 3.98 ¥ 10–6
the dissociation will be very low in the second step so 19. (c) MX4 m M4+ + 4X–
there will be no change in these concentrations. S 4S
[H+] = [HCO3–] = 1.195 ¥ 10–4 and [CO32–] = 4.8 ¥ 10–11 KSP = [S][4S]4 = 256 S5
1/5 1/3
Ê K sp ˆ È 3.2 ¥ 10-14 ˘ È 32
1/3
˘
\ S =Á or Í ¥ 10-15 ˙
Ë 256 ˜¯ Solubility of MX2 = Í
Î 4
˙
˚ Î4 ˚
20. (c) Mg(OH)2 h [Mg2+] + 2[OH–] = [8 ¥ 10–15]1/3 or 2 ¥ 10–5
x 2x 1/4
Ksp = [Mg][OH] = [x][2x]2 = x.4x2 = 4x3.
2 È 2.7 ¥ 10-15 ˘
Solubility of M3X = Í ˙
21. (c) AB2 m A+2 + 2B– Î 27 ˚
[A] = 1.0 ¥ 10–5, [B] = [2.0 ¥ 10–5], = [10–16]1/4 or 10–4
Ksp = [B]2[A] = [2 ¥ 10–5]2[1.0 ¥ 10–5]
24. (a) In acidic solution [S2–] is low. So CuS and HgS
= 4 ¥ 10–15
(second group cations) will be precipitated more easily
JEE Advanced due to low Ksp value. NiS and MnS (IV group cation)
will precipitate if H2S is passed in basic medium.
Single Correct-Answer Type
1
22. (a) 25. (a) Rate in weak acid = (rate of strong acid)
100
i. Ag+ + NH3 m [Ag(NH3)]+; k1 = 3.5 ¥ 10–3
1
ii. [Ag+ (NH3)]+ + NH3 m [Ag(NH3)2]+; \ [H+]weak acid = [H+]strong acid
k2 = 1.7 ¥ 10–3 100
On the basis of above reaction 1
\ [H+]weak acid = M = 10–2 M
[Ag(NH3 )]+ 100
k1 = ….(i)
[Ag + ][NH3 ] \ Ca = 10–2
\ Ka = 10–4
[Ag(NH3 ) 2 ]+ Hence (a) is correct.
k2 = …(ii)
[Ag(NH3 )]+ [NH3 ] 26. (b) Ksp = 1.1 ¥ 10–12 = [Ag+]2[CrO4–2]
1.1 ¥ 10–12 = [0.1]2[S]
For the formation of [Ag(NH3)2]+
S = 1.1 ¥ 10–10
Ag+ + 2NH3 m [Ag(NH3)2]+
[Ag(NH3 ) 2 ]+ Multiple Correct-Answer Type
Formation constant (K) = …(iii)
[Ag + ][NH3 ]2 27. (c), (d)
When two equations are added their equilibrium 1. Not buffer since it is a mixture of strong acid and
constants are multiplied. weak acid.
2. Not buffer since it is a mixture of strong base and
From Eqs (i) and (ii), we get
salt of weak acid/strong base.
k = k1 ¥ k2
3. It is an acidic buffer since some of HNO3 will react
= 3.5 ¥ 10–3 ¥ 1.7 ¥ 10–3
with CH3COONa to produce weak acid and some
= 5.95 ¥ 10–6 = 6.08 ¥ 10–6
CH3COONa will be left. So buffer is formed
23. (d) MX Æ M+ + X– (where s is the solubility) HNO3 + CH3COONa Æ NaNO3 + CH3COOH
S S Initial x y 0 0
Then Ksp = S2 or S = Ksp Final — (y – x) (y – x) (y – x)
4. It is acidic buffer (mixture of weak acid and salt of
Similarly for MX2 Æ M2+ + 2X–
1/3
weak acid/strong base).
2
È Ksp ˘
3
Ksp = S ¥ (2S) = 4S or S = Í ˙ Linked Comprehension Type
Î 4 ˚
and for M3X Æ 3M+ + X–3 28. [A] Let the heat capacity of insulated beaker be C.
S S Mass of aqueous content in experiment
Then Ksp = S2 or S = Ksp 1 = (100 + 100) ¥ 1 = 200 g
1/4 fi \ Total heat capacity = (C + 200 ¥ 4.2) J/K
È K sp ˘ Mole of acid, base neutralized in Experiment 1
Ksp = (3S)3 ¥ S = 27S4 or S = Í ˙
Î 27 ˚ = 0.1 ¥ 1 = 0.1
From the given values of Ksp for MX, MX2 and M3X, fi Heat released in Expt. 1 = 0.1 ¥ 5.7 = 5.7 KJ
we can find the solubilities of those salts at tempera- = 5.7 ¥ 1000 J
ture, T fi 5.7 ¥ 1000 = (C + 200 ¥ 4.2) ¥ DT
5.7 ¥ 1000 = (C + 200 ¥ 4.2) ¥ 5.7
Solubility of MX = 4 ¥ 10-8 = 2 ¥ 10–4 fi (C + 200 ¥ 4.2) = 1000
In second experiment
K w 0.01h 2
N CH3COOH = 0.2, NNaOH = –0.1 Kh = =
Ka 1- h
Total mass of aqueous content = 200 g
fi Total heat capacity = (C + 200 ¥ 4.2) = 1000 10-14 10-2 h 2
= (1 - h ª 1)
fi Heat released = 1000 ¥ 5.6 = 5600 J 10- 4 1- h
Overall, only 0.1 mol of CH3COOH undergo neutrali-
[OH–] = 0.01 h = 0.01 ¥ 10–4 = 10–6
sation.
[H+] = 10–8
-5600 pH = 8
fi DHneutralisation of CH3COOH =
0.1 31. (c) KCN, K2CO3 and LiCN are the salts of weak acid
fi DHdissociation of CH3COOH = 57 – 56 = 1 kJ/mol. and strong base. So, their aqueous solution turns red
29. [B] Final solution contains 0.1 mole of CH3COOH and litmus paper blue.
CH3COONa each. 32. (6) Diprotic acids are H2SO4, H3PO3, H2CO3, H2S2O7,
Hence it is a buffer solution H2CrO4 and H2SO3.
È CH3COO - ˘ 33. (3) Let the solubility of AgCl is x mol L–1
pH = pKa + log Í ˙ + -
Î CH3COOH ˚ AgCl m Ag + Cl
x
x
0.1 +
and that of CuCl is y mol L–1 CuCl m Cu + Cl
-
= 5 – log 2 + log = 4.7 y y
0.1
\ Ksp of AgCl = [Ag+][Cl–]
Integer Answer Type 1.6 ¥ 10–10 = x(x + y) …(i)
30. (8) Ka(C6H5COOH) = 1 ¥ 10–4 Similarly Ksp of CuCl = [Cu+][Cl–]
pH of 0.01 M C6H5COONa 1.6 ¥ 10–6 = y(x + y) …(ii)
-
C6 H5COO + H 2O m C6 H5COO + OH - -1 On solving Eqs (i) and (ii)
0 01(1 - h ) 0 01h 0 01h [Ag+] = 1.6 ¥ 10–7
\ x=7

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McGraw Hill Education (India) Private Limited

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Published by McGraw Hill Education (India) Private Limited

Physical Chemistry for JEE (Main & Advanced) Module-I

Copyright © 2017, McGraw Hill Education (India) Private Limited.

This edition can be exported from India only by the publishers,

ISBN (13): 978-93-5260-528-6

Cover Designer: Creative Designer

visit us at: www mheducation.co.in

● Solved Examples 1.7

● Answer Key 1.25

● Hints and Solutions 1.26

2. Atomic Structure 2.1–2.49

● Solved Examples 2.9

● Answer Key 2.30

● Hints and Solutions 2.31

3. Gaseous State 3.1–3.63

● Solved Examples 3.19

● Answer Key 3.42

● Hints and Solutions 3.43

4. Chemical Equilibrium 4.1–4.32

Molarity For gases

MolalitY [m] tYPiCal ConCentration

So, number of mole of water required = number of moles of

A w g sample was burned in the presence of CuO to cause

Weight rise in KOH = w2 – w1 = wCO2 NaOH (for neutralisation of excess H SO )

tion (containing halide ion solution which is obtained by re-

Weight of oxygen in Organic Compound Fig. 1.3

Applying POAC on Ag Atom ÔÏ È w ˘ Ô¸

0.7 \ number of moles of O2 obtained

\ 1 L solution contains 1 mole of NaOH \ molarity after ionisation

Stage 1: The water sample is treated with excess of Mn2+ (aq)

24. Select the incorrect statement(s). Column I Column II

Previous Years’ Questions of Jee (Main & advanCed)

Hints and Solutions

Actual product formed Ê 936 ˆ

180 1800 a3 = 3 cm3 \ a6 = 9 cm6

32. (c) M = 44.8/11.2=4 A = 5000 m2

Number of neutron in one molecule = 36

40 \ number of M+3 = 0.04

1 6. (b) Let the mass of sample is 100

x + y + z = 250 ... (i) C2H4 + 3O2 h 2CO2 + 2H2O

5 mole 20 mole 0 16. (a, d) Conceptual

\ volume contraction = 55 – 5 = 50 mL 26. (b, d)

1 (C) 1 g ion Mg+2 = 1 Mole Mg+2 ion

12 Cl2 + 24 KOH Æ 3 KClO4 + 21 KCl + 12 H2O ÈÊ 10.48 ˆ ˘ 2

7a for obtaining maximum mass of E there should be no

Ê xˆ Previous Years’ Questions

Total energy at final point Types of Spectrum________________________

(i) Wavelength: Distance covered l experiment Absorption spectrum B C E F Spectrum

t Bohr’s atomic model

1. According to Bohr’s atomic model, e– rotate around

Second line b line. Ê z2 ˆ

2. When a resolving power spectroscope is used it was È 2p r ˘

Heisenberg Uncertainity Principle __________ Note:

Maximum no. of orbital In any subshell = (2l + 1)

3 Probability curve: It was found that wave function y can be

Schrödinger Wave Equation _______________ Radial Probability Density _________________

4 4 Total probability distribution = R2 ◊ dn = R2(4p r2dr)

R10 R2, 0 R3, 0 R2, 1

rmax rmax rmax

(1s) (2s) (3s)

2. Atomic Structure 2.1–2.49

3. Gaseous State 3.1–3.63

Schrödinger Wave Equation _ Radial Probability Density ___