DAY ONE SOME BASIC CONCEPTS OF CHEMISTRY 9

8 0.376 g Al = 0.468 L H 2 In 1 atom of water 10 electrons are present. Number of H-atoms in 0.0747 mole of sucrose
0.376 ∴ electrons in 1 mole H 2O = 22 × 6.023 × 10 23 × 0.0747
equivalent of Al = 0.468 L H 2
9 = (2 + 8) × 6.023 × 10 23 electrons = 9.9 × 10 23
∴1 equivalent of Al = 11.2 L H 2 = 10 × 6.02 × 10 23 21 Given, abundance of elements by mass
9 0.20 g oxygen ≡ 317
. g halogen = 6.02 × 10 24 electrons oxygen = 614. %, carbon = 22.9%,
∴Equivalent mass halogen hydrogen = 10%
15 Q6.02 × 10 molecules ofCuSO 4 ⋅ 5H 2O
23
317
. Total weight of person = 75 kg
≡ − 127 g
× 8 = 126.8 g ~ = 63.5 + 32 + 64 + 90 = 249.5 g 75 × 10 × 1
020
. Mass due to 1H = = 7.5 kg
∴ 1 × 10 22 molecules of CuSO 4 ⋅ 5H 2O 100
10 Mass of the given amount of a substance 249.5 1
H atoms are replaced by 2H atoms.
is a constant quantity. = × 10 22 = 415
. g
6.02 × 10 23 Mass due to 2H = (7.5 × 2) kg
11 In Mg 3(PO 4 )2; 1 moles of O-atoms are ∴Mass gain by person = 7.5 kg
16 Number of moles of Fe
present in 1 mole of Mg 3(PO 4 )2.
22 18 g H 2O contains 2 g of H
= 10 −4 mol
0.0056
Hence, 0.25 mole of O-atom are =
56 ∴ 0.72 g H 2O contains 0.08 g of H.
contained 2 moles of Fe is present in 1 mole of
1 44 g CO 2 contains 12 g of C
= × 0.25 (NH 4 )2 SO 4 Fe 2(SO 4 )3.
8 Therefore, 10 −4 mole of Fe is present in ∴ 3.08 gCO 2 contains 0.84 g of C
= 3.125 × 10 −2 10 −4 × 1 0.84 0.08
= mol ∴ C : H= : = 0.07 : 0.08 = 7 : 8
32 2 12 1
12 I. 1 molecule of O 2 =
6.022 × 10 23 g = 0.5 × 10 −4 mol ∴ Empirical formula = C 7 H 8
= 5.3 × 10 −23 g
17. 200 mg CO 2 = 0.2 g = 0.2 mol 23 Weight of oxygen in sample
14 44
II. 1 atom of N = = 0 .2075 − 01475
. = 0.06 g
6.022 × 10 g 23
= 0.00454 mol = 4.54 × 10 −3mol
01475
.
= 2.3 × 10 −23 g 10 21 Moles of cobalt = = 0.0025
10 21 molecules of CO 2 = 59
III. 10 −10 g mol. wt. of oxygen 6.02 × 10 23 0.06
Moles of oxygen = = 0.0037
= 10 −10 × 32 = 3.2 × 10 −9g = 1.66 × 10 −3 mol 16
∴ Number of moles left
IV. 10 −10g atomic weight of copper
0.0025
Simplest ratio of Co = = 10
.
= (4.54 − 1.66) 10 −3 0.0025
= 10 −10 × 63.5 = 6.35 × 10 −9 g
= 2.88 × 10 −3 Simplest ratio of O =
0.0037
= 1.48 ≈ 15
∴ Order of increasing mass is 0.0025
.
II < I < III < IV. 18 0.1 L = 100 mL has Pb = 30 mg Ratio of Co:O = 1 :15. = 2 :3
13 Number of atoms = 30 × 10 −6 g So, the formula is Co 2O 3.
weight 30 × 10 −6
= × NA × species = mole of Pb 24 C xH y + ( x + y)4 O 2 → xCO 2( g ) + y2H 2O( l )
atomic weight 207 15 15 ( x + y )4 15x

∴ In 4 g of hydrogen, 30 × 10 −6
= × 6.02 × 10 23 Pb atoms Before Combustion
4 207 O 2 used = 20% of 375 = 75 mL
Number of atoms = × NA × 2 = 4 NA
2 Number of atoms per cm3 blood After Combustion
[Here, species = 2, because hydrogen is 30 × 10 −6 × 6.02 × 10 23 Inert part of air = 80% of 375 = 300 mL
= = 8.72 × 1014
present as H 2 ] 207 × 100 Total volume of gases = CO 2 + Inert part of air
In 71 g of chlorine, 330 = 15x + 300 ⇒ x = 2
19 16 g of O 2 = 16 = 0.5 mol x + ( y / 4) 75 y
Number of atoms =
71
× NA × 2 = 2 NA 32 = ⇒ x+ =5
71 1 15 4
NA
In 127 g of iodine, = molecules ⇒ x = 2, y = 12 ⇒ C 2H12 or C 3H 6.
127 2
Number of atoms = × NA × 2 14
Thus empirical formula of compound is C 3H 6
127 14 g of N 2 = = 0.5 mol
= 2 NA 28 25 We can calculate the simplest whole number
NA ratio for C and H from the data given as:
In 48 g of magnesium, = molecules
2 Simplest
48
Number of atoms = × NA × 1 = 2 NA Relative Molar Relative whole
24 20 Moles of sucrose [C 12 H 22 O11 ] Element
mass mass mole number
[Here, Mg is present as Mg so species 25.6 ratio
= 1] Thus, the number of atoms are = = 0.0747
342.3 6 0.5
largest in 4 g of hydrogen. C 6 12 = 0.5 =1
Number of H-atoms in 1 mole of sucrose 12 0.5
14 18 mL H 2O = 18 g H 2O = 1 mol = 22 × 6.023 × 10 23 1
=1
1
=2
H 1 1
1 0.5
= 6.02 × 10 23
molecules/atoms

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10 40 DAYS ~ JEE MAIN CHEMISTRY DAY ONE

Now, after calculating this ratio look for contain 0.01 mole of Br − and 0.01 SO 2− 4 ∴ 2 moles of C 8H 7 SO 3 Na combines with
condition 2 given in the question, i.e. ions. With excess of AgNO 3, 0.01 moles of 1 mole of Ca 2 + .
quantity of oxygen is half of the quantity AgBr, i.e. Y is formed and with excess of ∴1 mole of C 8H 7 SO 3 Na combines with
required to burn one molecule of BaCl 2, 0.01 moles ofBaSO 4 , i.e. Z is formed. 1
mole of Ca 2 + .
compound C xH y completely to CO 2 and 2
H 2O. We can calculate number of oxygen
29 200 mL of 5 N HCl 1
∴ mole of C 8H 7 SO 3 Na will combine with
atoms from this as consider the equation. = 200 × 5 milliequivalents 206
= 1000 millimoles = 1 mol HCl
C xH y +  x +  O 2 → xCO 2 + H 2O
y y
mole of Ca 2 +
1 1
×
 4  2 1.7g of AgNO 3 = 0.01 mol 2 206
mole of Ca 2 +
1
Number of oxygen atoms required AgNO 3 + HCl → AgCl + HNO 3 =
= 2 ×  x +  = 2 x + 
y y 1 mol 1 mol 1 mol
412
 4   2  0.01 mol 1 mol 0.01 mol
34 Mohr’s salt is FeSO 4 ⋅ (NH 4 )2SO 4 ⋅ 6H 2O
Now given, z = 2 x +  = 2 x + 
y AgNO 3 is the limiting reagent.
Only oxidisable part is Fe 2 + .
1 2
2  2   4  Thus, AgCl formed = 0.01 mol
[Fe 2 + → Fe 3 + + e − ] × 6
= 0.01 × 143.5 = 1.435 g
Here, we consider x and y as simplest Cr2O 72− + 14H + + 6 e − → 2Cr 3 + + 7H 2O
ratios for C and H so, now putting the 30 3BaCl 2 + 2Na 3 PO 4 → Ba 3(PO 4 )2 6Fe 2 + + Cr2O 27− + 14H + → 6Fe 3 +
values of x and y in the above equation.
+ 6NaCl + 2Cr 3 + + 7H 2O
z =  x +  = 1 +  = 15
y 2+
2
. Millimoles of Fe = 750 × 0.6
 Here, limiting reactant is Na 3PO 4 .
4   4  = 450 mmol
0.2 mole of Na 3PO 4 will give Ba 3(PO 4 )2
Thus, the simplest ratio figures for x, y 450
1 Moles of Fe 2 + = = 0.450 mol
and z are x = 1, y = 2 and z = 15 . . = × 0.2 = 0.1 mol 1000
2
Now, put these values in the formula 6 moles of Fe 2 + ≡ 1 mole of Cr2O 27−
C xH yO z = C 1H 2O1.5 31 2 y → 2 y3+ + 6e − [y → y3+ + 3e − ] 0.450
∴0.450 mole of Fe 2 + ≡
given, i.e.
So,empirical formula will be 6 H + + 6e − → 3 H 2 [2H+ + 2e − → H 2 ] 6
[C 1H 2O1.5 ] × 2 = C 2H 4O 3 = 0.0075 mole of Cr2O 72−
2 y + 6H+ → 2 y3+ + 3 H 2
Mass of K 2Cr2O 7 required
26 Let wt. of FeO = a g and wt. ofFe 3O 4 = b g The above individual equations suggest
= 0.075 × 294 g = 22.05 g
that,
1
2FeO + O 2 → Fe 2O 3 1 eq. of y = 1 eq. of H 2
2 (n = 3) (n = 2) 35 Normality equation is,
1 1 1 N1V1 + N2V2 + N3V3 = N4 ( V1 + V2 + V3 )
2Fe 3O 4 + O 2 → 3Fe 2O 3 ⇒ mol y = mol H 2
2 1 1
2 3 or 1 × 5 +20 × + 30 × = N4 (5 +20 +30)
Thus, H 2 : y = 2 : 3 2 3
Q 144 g of FeO gives 160 g Fe 2O 3. 25
∴Resulting normality ( N4 ) = = 0.45 N
160 × a 32 Initial strength of acetic acid = 0.06 N 55
∴ a g FeO will give = g Fe 2O 3 Final strength = 0.042 N
144
Given volume = 50 mL 36 For I solution : millimoles
Similarly, weight of Fe 2O 3 formed by b g = MV = 480 × 1.5 = 720
∴Initial millimoles of CH 3COOH
160 × 3 × b
Fe 3O 4 = = 0.06 × 50 = 3 For II solution : millimoles
464
Final millimoles of CH 3COOH = MV = 520 × 1.2 = 624
Now, if a + b = 100 …(i)
= 0.042 × 50 = 2.1 Total millimoles = 720 + 624 = 1344
160 × a 160 × 3 × b
Then, + = 105 …(ii) ∴Millimoles of CH 3COOH adsorbed Moles of solute
144 464 ∴ Molarity =
= 3 − 2.1 = 0.9 mmol Total volume of solution (L)
From Eqs. (i) and (ii), a = 20.25 g
Hence, mass of CH 3COOH adsorbed per 1344
and b = 79.75 g =
∴ Percentage of Fe 3O 4 = 79.75% gram of charcoal = 0.9 × 60 [molar mass 480 + 520
3 = 1.344 M
27 The reaction is of CH 3COOH = 60 gmol −1]
=
54
= 18 mg 37 Assertion and Reason both are false. As
2Ag+ + CrO 24− → Ag 2CrO 4 .
3 volume of solution changes by 20%, so it
Using the limiting reagent concept, 20
33 Molecular weight of C 8H 7SO 3Na becomes = 1 + = 1. 2 L
number of moles of Ag 2CrO 4 100
= 0.5 × 10 −3 = (12 × 8) + (1 × 7 ) + 32 + ( 3 × 16) + 23 ∴Molarity of resulting solution
= 206u Moles of solute
Amount of Ag 2CrO 4 formed =
Total volume of solution (L )
= 0.5 × 10 −3 × 331.73
Number of moles in 206 g of C 8H 7SO 3 Na
1
= 0.166 g resin = mol = 0.8 M
206
and change in molarity = 1 − 0.8 = 0.2 M
28 Mixture X will contain 0.02 mole of Now, reaction would be
∴ % change in molarity
Br − ions and 0.02 mole of SO 2−
4 ions in 2C 8 H 7SO 3Na + Ca 2 + →
0.2
2 L solution. Hence, 1 L of mixture X will (C 8H 7SO 3 )2Ca + 2Na + = × 100 = 16.66%
1.2

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DAY ONE SOME BASIC CONCEPTS OF CHEMISTRY 11

38 Both Assertion and Reason are false. N 2 unreacted = 1 – 0.5 = 0.5 mol No. of moles of elemental boron
1 21.6
H 2 + O 2 → H 2O H 2 unreacted = 4 – 1.5 = 2.5 mol = = 2 mol
2 NH 3 formed = 1 mol 10.8
30 mL 15 mL ∴ No. of moles of H 2 consumed
Volume of O 2 left = 20 − 15 mL = 5 mL 3
But NH 3 gets dissolved in H 2O leaving N 2 = × 2 = 3 moles
Therefore, no H 2 left after the reaction and H 2 2
2 .5 5
hence, H 2 is the limiting reagent. ∴ xH 2 = = Volume of H 2 at NTP = (22.4 × 3) L
3. 0 6
= 67.2 L
SESSION 2 8 K 2SO 4 is isomorphous with K 2SeO 4 . 12 Molarity of acetic acid = 2.05 M
1 N 2 + 3H 2 → 2NH 3 The molar weight of K 2 SeO 4 is given by Mass of CH 3COOH in 1 L solution
2 × 17 g
6g (2 × 39) + x + ( 4 × 16)
450 g 34
× 450 = 2550 g = 2.05 × 60 = 123 g
6 [Q x = atomic wt. of Se]
Mass of 1 L solution = 1000 × 1.02 = 1020 g
Actual = 1575 g ⇒ (142 + x ) g
1575 × 100 (since density = 1.02 g/mL)
% yield = = 61.76% If (142 + x )g of K 2SeO 4 contains x g of
2550 Mass of water in solution
K 2SO 4 . So, therefore,
= 1020 − 123 = 897 g
x
2 (NH 4 )3PO 4 has 12 H atoms and 100 g of K 2 SeO 4 = × 100
= 2.28 mol kg −1
2.05
(142 + x ) ∴ Molality =
4 O atoms; H:O = 3:1 897 × 10 −3
Hence, O relative to 3.18 mol H But K 2 SeO 4 contains 50% of Se, thus
= 1.06 mol 50 =
x
× 100 13 Sn2+ → Sn4+ + 2e − 2 units
(142 + x ) Fe 2+ → Fe 3+ + e − 1 unit
3 2KClO 3 → 2KCl + 3O 2 −
or x = 142 g Cr2O 2–
7 + 6e → 2Cr 3 + 6 units
4Al + 3O 2 → 2Al 2O 3 Hence, the atomic wt. of Se is 142 g. Milliequivalent of Sn2+ = 15 × 0.04 × 2 = 1.2
2 mol of KClO 3 ≡ 2 mol Al 2O 3
9 KMnO 4 reacts with oxalic acid according Milliequivalent of Fe 2+ = 15 x × 1 = 15x
∴1 mol KClO 3 ≡ 1 mol Al 2O 3
to the following equation. 7 = 18 × 0.125 × 6
Milliequivalent of Cr2O 2–
4 106 g solution = 1 g Fe 2 + 2MnO −4 + 5 C 2O 24− + 16 H + → = 13.5
250 mL = 250 g solution 2Mn2 + + 10 CO 2 + 8 H 2O ∴ 1.2 + 15x = 13.5 ⇒ x = 0.82
= 6 × 250 g Fe 2 +
1 Equivalent mass of KMnO 4
10 molecular mass
14 KHC 2O 4 ≡ KOH
=
250 × 392 (7 − 2 )
100 mL of 0.01 M KOH
= g (A) ≡ 100 mL of 0.01 M KHC 2O 4
10 6 × 56 NKMnO 4 = 5 × molarity = 5 × 10 −4
= 1 millimol KHC 2O 4
= 1.75 × 10 −3
Equivalent mass of ∴ Na 2C 2O 4 = 1 millimol
5 Number of millimoles of Ca (OH)2 molecular mass
4 =
C 2O 2− Total C 2O 42– = 2 millimol
= 50 × 0.5 = 25 2(4 − 3)
= 4 milliequiv
molecular mass
Number of millimoles of CaCO 3 = 25 C 2O 4 =
2−
Let volume of KMnO 4 = V mL
2
Number of milliequivalents ofCaCO 3 = 50 (MnO –4 reduced to Mn2 + )
NC O 2− = 2 × molarity
∴ Volume of 0.1 N HCl 2 4 ∴ V × 0.01 × 5 = 4
50 = 2 × 10 −2
= = 500 cm3 ⇒ V = 80 mL
01
. According to normality equation,
N1V1 = N2V2
15 Let 100 m3 milk contains 4 m3 fat.
6 Required equation is given below: ∴ Weight of butter fat in 1 m3 milk
Zn + 2OH − → ZnO 22− + 2H + + 2 e − 5 × 10 −4 × V1 = 2 × 10 −2 × 0.5 4
2 × 10−2 × 05
. = × 865 = 35 kg
NO −3 + 8 H + + 8 e − → OH − + 2H 2O + NH 3 V1 = = 20 L 100
From the above equation, 5 × 10−4 Weight of 10 3 cm3 (1 L) milk = 1.032 kg
Q8 mole of electrons are absorbed by 10 100 g haemoglobin contains 0.33 g Fe. ∴ Wt. of 10 6 cm3 (1 m3 ) milk = 1032 kg
85 g of NaNO 3
∴67200 g haemoglobin contains ∴ Weight of skimmed milk = 1032 − 35
∴ 1 mole of electron will be absorbed by = 997 kg
0.33 × 67200
85
g of NaNO 3 = 10.625 g = g Fe and volume of skimmed milk = 1 − 0.04
8 100
= 221.76 g Fe = 0.96 m3
7 N 2 + 3H 2 → 2NH 3 221.76 ∴Density of fat free skimmed milk
∴Number of Fe-ato =
= 1038.5 kg m−3
1 mol 4 mol 997
56 =
NH 3 +HCl → NH 4 Cl = 3.96 ≈ 4
0.96
1 1
NH 3 formed = 1 mol 11 2BCl 3 + 3 H 2 → B + 3HCl
N 2 reacted = 0.5 mol 2
∴ H 2 reacted = 1.5 mol

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DAY TWO

States of Matter
Learning & Revision for the Day

u Classification of Matter u Liquid State u Bragg’s Law and Its

u Gaseous State u Solid State Applications
u Kinetic Theory of Gases u Unit Cell and Lattices

Classification of Matter
Anything which has mass and occupies space is called matter. Three states of matter are
as follows
1. Solids have definite volume, a definite shape and are rigid.
2. Liquids have definite volume, but not definite shape and are non-rigid.
3. Gases have neither definite shape, nor definite volume and are non-rigid. It is the
simplest state and shows great uniformity in behaviour.
l
Besides the three states of matter, two more states of matter have been found to exist.
These are plasma and Bose-Einstein condensate (predicted by Albert Einstein and
Indian physicist Satyendra Nath Bose).
l
If plasma are super-hot and super-excited atoms (a mixture of electrons and positively
charged ions formed by superheating, e.g. in the sun), the Bose-Einstein condensate are
total opposite, i.e. super-cold and super- unexcited atoms formed by super-cooling to
such an extent that the atoms lose their individual identity and condensate to form a
single super-atom.
Following two factors determine the physical state of matter: PREP
1. Thermal agitation due to kinetic energy of the particles, atoms [or molecules] of a
matter are in a state of continuous vibration and agitation. This increases with
MIRROR
Your Personal Preparation Indicator
increase in temperature due to increase in their kinetic energy.
u No. of Questions in Exercises (x)—
2. Cohesive forces (intermolecular forces) may be attractive or repulsive. Attractive
u No. of Questions Attempted (y)—
intermolecular forces are called van der Waals’ forces.
u No. of Correct Questions (z)—
The nature of intermolecular forces, molecular interactions and effect of thermal (Without referring Explanations)
energy on the motion of particles helps to determine the state of a substance.
Attractive intermolecular forces are known as van der Waals’ forces. The different u Accuracy Level (z / y × 100)—
types of van der Waals’ forces are as follows: u Prep Level (z / x × 100)—

(i) Dispersion or London forces are the forces that exists between non-polar
In order to expect good rank in JEE, your
molecules possessing temporary dipole moments. The interaction energy of these Accuracy Level should be above 85 & Prep
forces is proportional to 1 / r 6. [where, r is the distance between two particles]. Level should be above 75.

(ii) Dipole-dipole forces are forces that exists between dipole ends of polar
molecules and are strongest of all van der Waals’ forces.

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DAY TWO STATES OF MATTER 13

Dipole-dipole interaction energy between stationary

polar molecules is proportional to 1 / r 3 and that
Measurable Properties of Gases
between rotating polar molecules is proportional to The characteristics of gases are described fully in terms of
1 / r 6. four parameters, i.e. pressure (p), volume (V), temperature (T )
and mass or mole, which are termed as measurable
(iii) Dipole-induced dipole forces are forces that exists
properties.
between the polar molecules having permanent
dipole and the molecules lacking permanent dipole. (i) Mass is expressed in gram or kilogram and is equal to
Permanent dipole of the polar molecule induces the difference in masses of empty vessel and vessel
dipole on the electrically neutral molecule by containing gas.
deforming its electron cloud. (ii) Volume is equal to the volume of the container and is
In dipole-induced dipole interactions, the interaction expressed in terms of litre (L), millilitre (mL), cubic
energy is proportional to 1 / r 6. centimetre (cm3 ), cubic metre (m3 ) or cubic decimetre
(iv) Ion-dipole and ion-Induced dipole forces are similar (dm3 ).
to dipole-dipole and induced-dipole interactions but 1 L = 1000 mL = 1000 cm3 = 1 dm3
involves only ions, instead of only polar and 1 m3 = 103 dm3 = 10 6cm3 = 10 6 mL = 103 L
non-polar molecules. These forces are stronger than
(iii) Pressure is defined as force per unit area. The greater
dipole-dipole interactions because the charge of any ion
is much greater than the charge of a dipole moment. the force acting on a given area, the greater is the
pressure. The origin of the force exerted by a gas is the
(v) Hydrogen bond it is a special case of dipole-dipole
continuous collisions of the molecules against the walls
interaction.
of the container.
(a) In a solid, the cohesive forces predominate the
The units of pressure are atm, mm Hg, torr etc.
effect of thermal agitation. Consequently, the
particles are held together in rigid, highly-oriented 1 atm = 76 cm of Hg = 760 mm of Hg = 760 torr
and close-packed structure. 1 atm = 101.325 kPa = 101325 Pa = 101.325 Nm–2
(b) In a liquid, the cohesive forces are no longer = 1.01325 bar
strong enough, however, these are still sufficient, 1 bar = 10 5 Pa = 0.987 atm
so that particles cannot escape each others
environment, they have sufficient mobility. (iv) Temperature is the measurement of hotness or coldness
(c) In a gas, the thermal agitation dominates the effect of an object. It is measured in Celsius scale or absolute
of cohesive forces, thus the gas molecules acquire scale (Kelvin scale). Celsius scale was earlier known as
the unrestricted and independent mobility of the the centigrade scale.
vapour state.
Gas Laws
Gaseous State Various types of gas laws are as follows:
It is the most disordered state of matter. In this state, matter
neither have fixed volume nor fixed shape. It takes the shape 1. Boyle’s Law (1662)
and volume of the container in which it is placed. At constant temperature, the pressure of a fixed amount of gas
Gases exhibit the following characteristic properties: varies inversely with its volume.
Gases expand indefinitely. 1
At constant temperature (T ), p ∝
l

l
Gases are highly compressible. V
pV = constant (for given moles and T )
l
Gases intermix freely with one another or move from one
place to other without any difficulty. This is known as or p1V1 = p2V2 = constant
diffusion. The two conventional ways of graphically representing
l
Pure gases or their mixtures are all homogeneous in Boyle’s law are as follows:
composition.
l
Gases possess very low density. The density of gas when
compared to that of hydrogen is termed as relative density. p p
l
Due to collision of molecules on the walls of container,
gases exert pressure which obviously increases due to
increase in temperature. 1/V
V
l
Gaseous molecules move very rapidly in all directions in a p vs V plot p vs 1/V plot
random manner, i.e. gases have highest kinetic energy.

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14 40 DAYS ~ JEE MAIN CHEMISTRY DAY TWO

2. Charles’ Law (1787) 4. Avogadro’s Law

At constant pressure, the volume of a fixed mass of a gas is It states that equal volumes of all gases at same pressure and
directly proportional to its absolute temperature. temperature contain equal number of molecules.
At constant pressure ( p), V ∝ T V ∝n (at given T and p)
V V1 V2
= constant (for given n and p) or =
T n1 n2
V1 V2
or =
T1 T2
Ideal Gas Equation
l
Charle’s found that for all gases at given pressure, graph
The Boyle’s law, Charle’s law and Avogadro’s law can be
of V vs T is a straight line.
combined together in a single equation known as ideal gas
equation.
p1 nT
p1<p2<p3<p4 V ∝
p2 p
w
p3 pV = nRT or pV = RT
Volume

M
p4  w
∴ number of moles n =
 M 
or pM = dRT
where, w = mass of gas,
–300 –200 –100 0 100 M = molecular weight of gas
Temperature (°C) d = density of gas,
V vs T graph at different constant pressures p = pressure of gas
l
Charles’ obtained experimentally that for 1°C change in T = temperature, V = volume
temperature of a gas, the volume get changed by a R = universal gas constant.
fraction of
1
. Hence, if V0 be the volume of a gas at 0°C Values of R = 0. 0821 L atm K −1 mol−1
273
= 8 . 314 J K −1 mol−1
and it is recorded to be V at t ° C then
1 = 1 . 987 cal K −1 mol−1
V = V0 + t V0
273.15 = 8 . 314 kPa dm3 K −1 mol−1
 t  V0 = 0 . 083 bar dm3 K −1 mol−1
= V0 1 + = T
 273.15 273.15 NOTE Standard temperature and pressure (STP or NTP) means 273.15 K
If temperature is lowered, the volume decreases at (0°C) temperature and 1 bar (i.e. exactly 105 pascal) pressure. At
constant pressure and become zero at − 273.15 ° C. STP, molar volume of an ideal gas is 22.71098 L mol −1 .

Further lowering is not possible thus, it is called the lowest

possible temperature or absolute zero of temperature. Scale Dalton’s Law of Partial Pressures
of temperature based on this choice of zero is called l
Total pressure exerted by the mixture of non-reacting gases is
absolute scale of temperature or thermodynamic scale of equal to the sum of the partial pressures of individual gases.
temperature. pTotal = p1 + p2 + p3 + p4 + K (at constant T, V)

T (K) = t (° C) + 273.15
l
Partial pressure of a gas (p) = mole fraction (χ) × total pressure
exerted by the mixture ( ptotal )
3. Gay-Lussac’s Law l
Percentage of a gas in the mixture
At constant volume, pressure of a fixed amount of a gas partial pressure of gas
= × 100
varies directly with the temperature. total pressure
At constant volume (V ), p ∝ T = mole fraction of that gas × 100
p
= constant l
When a gas is collected over the water, the pressure of the gas
T pobserved or moist = pressure of dry gas + aqueous tension or water
(for given n and V) vapour pressure.
p1 p2 Relative humidity (RH ) is given by RH = partial pressure of
=
l
or
T1 T2 water in air/vapour pressure of water.

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DAY TWO STATES OF MATTER 15

Different kind of velocities of molecules are as follows:

Graham’s Law of Diffusion
(i) Root mean square velocity
According to this law “if a gas is allowed to escape from its
container through a small hole into vacuum, the process is 3 RT 3p 3KT
(urms ) = = =
called effusion. On the other hand, diffusion is the passage of M d M
gas through a porous partition. For the same gas at two different temperatures, the ratio
1 of RMS velocities will be
l
Rate of diffusion or effusion ∝
molecular weight u1 T
= 1
[QMolecular weight = 2 × vapour density ⇒ M ∝ d] u2 T2
1 For two different gases, the ratio of the RMS velocities
Rate of diffusion or effusion ∝
density u1 M2
will be =
l
Rate of diffusion or effusion (r) u2 M1
volume diffused or effused 8 RT 8 KT
= (ii) Average velocity (uav ) = =
time taken πM πM
r1 t 2 d M2
Hence, = = 2 = 2RT 2 pV 2p
r2 t 1 d1 M1 (iii) Most probable velocity (ump) = = =
M M d
l
If p is not constant r ∝ p. Relation between different molecular velocities are as
r1 p1 M2 follows:
∴ =
r2 p2 M1 8
(i) ump : uav : urms : : 2 : : 3 =1 : 1.128 : 1.224
π
Kinetic Molecular Theory of Gases (ii) uav = urms × 0.9213
It is based on the following postulates: (iii) Kinetic energy of molecules
3
l
A gas consists of extremely small discrete molecules. These KE (per molecule) = K T
molecules are so small and so far apart that actual volume 2
of the molecules is negligible as compared to the total  R 
where, K = N  , K is Boltzmann constant
volume of the gas.  A 
R
l
Gas molecules are in constant random motion with high = 1.38 × 10 −23 J K −1 molecule
velocities that moves in a straight line and changes their N0
directions on collision with other molecules or walls of 3 3
KE (per mol) = pV = RT
container. 2 2
l
The intermolecular forces of attraction are negligible and At absolute zero, the kinetic energy of gas molecules
the effect of gravity on them is also negligible. become zero.
l
The collisions are perfectly elastic, therefore, there is no
loss of kinetic energy during collision. However, there may Real Gases
be redistribution of energy during such a collision. The gas which does not obey gas laws at all conditions of
l
The pressure of a gas is caused by the bombardment of temperature and pressure is called real gas. Real gases obey
moving molecules against the walls of container. the gas laws under moderate conditions of temperature and
pressure.
l
In a gas, different molecules have different kinetic energies
but the average kinetic energy of molecules is proportional Deviation from Ideal Behaviour
to absolute temperature of the gas.
At very low temperature and high pressure, real gases
l
On the basis of these assumptions, the following show deviation from the ideal gas behaviour.
mathematical expression for kinetic gas equation is derived.
The causes of deviation are:
1
pV = mNu2 (i) At low temperature and high pressure, volume of a
3
real gas is larger than that predicted for an ideal gas
1
or pV = Mu2 as the molecules of gas have their own volume.
3
(ii) Intermolecular forces are not negligible.
(QM = m × N , for one mole m = 1)
The deviations from ideal gas behaviour are expressed in
where, u = rms velocity. terms of compressibility factor (Z ).

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16 40 DAYS ~ JEE MAIN CHEMISTRY DAY TWO

pV 3. When Temperature is High At high temperature, V is

Compressibility factor (Z ) = =1 (for ideal gas)
nRT a
very large, the terms 2 and b can be neglected thus,
Different conditions of compressibility factor (Z ) for real gases V
are as follows: pV = RT .
l
Z < 1 (as for CH4, NH3 , CO2 ) can be attributed to 4. When Temperature is Low At low temperature, both p
predominance of attractive forces among the molecules of and V are small thus, both pressure and volume
these gases at the temperature of experimentation. corrections are appreciable.
The values of van der Waals’ constant ‘a’ and ‘b’ do not
l
Z > 1 (for H2 , He) can be attributed to the dominance of
remain constant over the entire range of temperature
strong repulsive forces among the molecules. Boyle
and pressure. Hence, van der Waals’ equation is valid
temperature is the characteristic temperature of the gas at
only over specific range of temperature and pressure.
which it obeys ideal gas nature. Below this temperature, the
value of Z at first decreases, approaches a minimum and
then increases as the pressure increases continuously.
Liquefaction of Gases
and Critical Constants
van der Waals’ Equation l
The phenomenon of converting a gas into liquid is known
To rectify the errors caused by ignoring the intermolecular as liquefaction at particular temperature, pressure and
forces of attraction and the volume occupied by molecules,
volume. When a gas changes into liquid, these conditions
Johannes van der Waals’ proposed following equation, which
are known as critical conditions e.g. Tc , Vc , pc etc.
is valid for real gases upto a large range of temperature and
pressure. l
Critical Temperature (Tc ) is the maximum temperature at
 n a
2 which a gas can be liquefied. Critical pressure ( p c ) is the
 p + 2  (V − nb ) = nRT minimum pressure which is required to liquefy a gas.
 V 
Critical volume (Vc ) is the volume of one mole of a gas
where, n = number of moles, a = constant (measure of
which is occupied at critical temperature.
magnitude of attractive forces between the molecules)
8a
b = constant (due to occupied volume of gaseous molecules Critical temperature (Tc ) =
= co-volume or excluded volume). 27 Rb
a
Units of ‘a’ are atm L2 mol−2 or atm m6 mol−2 or Nm4 mol−2 and Critical pressure ( pc ) =
that of ‘b’ are L mol−1 or dm3 mol−1 . 27 b 2
Critical volume (Vc ) = 3 b
van der Waals’ equation get reduced at different conditions of
pressures and temperatures. These are shown below: 3
NOTE l Relation between critical p, V and T is pcVc = RTc
1. When Pressure is Low At low pressure, V is very large, 8
thus, (V − b ) ≈ V as b is neglected in comparison to V , pcVc 3
or = Z < 1 at critical point.
therefore equation becomes: RTc 8
 a a l At critical point, there is no distinction between gaseous
 p + 2  V = RT or pV + = RT state and liquid state as densities of a substance in gaseous
 V  V
and liquid states are same.
pV a pV a
⇒ =1− ⇒ Z= =1−
RT VRT RT VRT Liquid State
a
At extremely low pressures, is very small as V is very It is the state of matter in which the molecules are held close to
V each other and execute random motion through intervening
large. Thus, it can be neglected. spaces.
∴ pV = RT Liquids have definite volume. They can move past one
2. When Pressure is High At high pressure, V is quite another freely. They can flow, can be poured and can assume
small, thus, the term (V − b ) cannot be neglected while the shape of the container in which these are stored.
a
the term 2 is quite large but in comparison to high
V Physical Properties of Liquid
a
p, 2 can be neglected. 1 Vapour Pressure
V
l
Inside a closed vessel, the liquid and its vapours are in
∴ p(V − b ) = RT
dynamic equilibrium. The pressure exerted by the vapours
⇒ pV = RT + pb on the walls of the container increases. After sometime, it
pV pb pb becomes constant, an equilibrium is established between
=1+ or Z =1 +
RT RT RT liquid phase and vapour phase. Vapour pressure at this
stage is known as equilibrium vapour pressure.

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DAY TWO STATES OF MATTER 17

Since, the vapour pressure is a kinetic phenomena, it is

Bragg’s Law and Its Applications
l

independent of the amount of a liquid. It only depends on

the temperature. The fundamental relation among the wavelength of the
X-rays, the inter-planar distance in the crystal and the angle
l
When a liquid is heated in an open vessel, the liquid of reflection is known as the Bragg’s law.
vapourises from the surface. The temperature at which vapour
2d sin θ = nλ
pressure of the liquid becomes equal to the external pressure,
where,
vaporisation can occur throughout the bulk of the liquid is
called boiling point and the condition is called boiling. λ = wavelength of X-ray used
θ = angle between incident X-rays and the plane of the crystal
2 Viscosity d = distance between planes of the constituent particle in a
l
The ease with which a fluid can flow is determined by its crystal
property, called viscosity. It arises due to the internal n = an integer (1, 2, 3, 4, …) which represents the serial
friction between layers of fluids. order of diffracted beams.
l
Viscosity of liquid decreases with increase in temperature Various applications of Bragg’s law are as follows:
because rise in temperature increases the kinetic energy l
Structure of solids are determined by X-ray diffraction
of molecules, this results in decrease in inter-layer methods.
friction. l
Structures of complex substances such as proteins and
nucleic acids are also determined by this method.
3 Surface Tension
l
The force acting along the surface of a liquid at right angle
to any line per unit length is called surface tension. The unit of Unit Cell and Lattices
surface tension is Nm −1 . Surface tension decreases with An array of lattice points showing arrangement of
l

rise in temperature. It is different for different liquids due constituent particles in different position in three
dimensional space, is known as space lattice or crystal
to different intermolecular forces.
lattice.
l
Due to surface tension, the small drops of liquids are l
Unit cell is the smallest group of lattice points which when
spherical as the liquid tends to have a minimum surface
repeated in all directions develop the entire lattice.
area. Due to surface tension, liquids rise or fall in capillary
tube.
l
A unit cell is characterised by its dimensions (a, b and c)
and angles (α, β, γ). These parameters of a typical unit cell
are tabulated as follows:
Solid State Seven crystal system and their unit cell parameters
It is defined as that form of matter which has rigidity and due
to which it possesses a definite volume and a definite shape. Crystal systems and Bravais lattices Unit cell parameters
These characteristics are due to the existence of very strong Cubic [primitive, face centred, body a = b = c , α = β = γ = 90°
forces of attraction among the constituent species of the solid. centred]
e.g. NaCl, KCl, diamond, copper, zinc
On the basis of the arrangement of their atoms or ions or blende etc.
molecules, solids are broadly classified into two groups:
Rhombohedral or trigonal [primitive] a = b = c , α = β = γ ≠ 90°
1. Crystalline Solids They have systematic and regular e.g. NaNO3 ,CaCO3 , HgS, etc.
arrangement of particles and sharp melting
Orthorhombic [primitive, face centred, a ≠ b ≠ c , α = β = γ = 90°
point.Crystalline solids are anisotropic, i.e. their body centred, end centred]
physical properties have different values in different e.g. Rhombic sulphur, BaSO 4 (baryta),
directions. On the basis of types of bond present, they PbCO3 etc.
are further divided into four groups. Triclinic (most asymmetric) [primitive] a ≠ b ≠ c , α ≠ β ≠ γ ≠ 90°
(a) Molecular crystals or van der Waals’ crystals, e.g. K2Cr2O7 , H3 BO3 ,CuSO 4 ⋅ 5H2O etc.
e.g. I2(s), H2O (s) etc. Monoclinic [primitive, end centred] a ≠ b ≠ c,
(b) Atomic crystals or (covalent crystals), e.g. graphite, e.g. Na 2SO 4 ⋅ 10H2O, Na 2 B2O7 ⋅ 10H2O, α = γ = 90° ,β ≠ 90°
diamond etc. monoclinic S etc.
(c) Metallic crystals, e.g. all metallic solids etc. Tetragonal [primitive, body centred] a = b ≠ c , α = β = γ = 90°
(d) Ionic crystals, e.g. NaCl, CsCl, ZnS etc. e.g. Cassiterite, white tin, rutile etc.

2. Amorphous Solids They are unsystematic and irregular Hexagonal [primitive] a = b ≠ c,

e.g. Mg, beryl, ZnO (zincite), PbI2 , α = β = 90° , γ = 120°
arrangement of particles. These are isotropic, i.e. their
physical properties have same values in different graphite etc.
directions.

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18 40 DAYS ~ JEE MAIN CHEMISTRY DAY TWO

Various types of unit cells are as follows: (ii) Hexagonal Close Packing (HCP) The particles in every
1. Simple unit cell or primitive unit cell in which particles next row are placed in the depression between the particles
are present only at corners. of the first row. The particles in the third row will be
1 vertically aligned with those in the first row.
∴ Number of atoms per unit cell = × 8 = 1
8
1 2
2. Face centred cell in which the particles are present at
the corners as well as at the centre of each face. 6 2 3
∴ Number of atoms per unit cell 5 4
1 1
= ×8+ ×6 = 4 Coordination number is 6 (HCP)
8 2 Hexagonal close packing
3. Body centred unit cell in which the particles are present
at the corners of the cube as well as one particle is 3. Three Dimensional Packing
present at the centre within the body.
It can be obtained by stacking two dimensional layers one
1
∴ Number of atoms per unit cell = × 8 + 1 = 2 above the other.
8
It is of two types:
Coordination Number (i) Hexagonal Closed Packing (HCP) The first layer as
The number of atoms in a crystal which surrounds particular
layer A and second layer as layer B, the arrangement is
atoms as its nearest atoms in its neighbour is called its called AB AB K pattern or hexagonal closed packing (hcp).
coordination number. Each coordination number corresponds to (ii) Cubic Close Packing (CCP) When the third layer is
a fixed radius ratio (the ratio of radius of cation to that of anion). placed over the second layer in such a way that spheres
cover the octahedral voids, a layer different from layers
r  Coordination
Radius ratio  +  Structure A and B is produced. Let us call it as layer C. This
 r–  number
pattern of stacking spheres is called ABC ABCK pattern
< 0.155 2 Linear or cubic close packing (ccp). It is similar to face centred
0.155 − 0.225 3 Planar triangle cubic (fcc) packing.
0.225 − 0.414 4 Tetrahedral
0.414 − 0.732 6 Octahedral Voids
0.732 − 1 8 Cubic In closely packed structures, the empty space is called
interstitial site or void. The void can be a simple triangular
space in the case of two dimensional packing and called the
Packing in Solids trigonal void.

The packing of spheres of equal size in solids takes place as

follows:

1. One Dimensional Packing

When the spheres are placed in horizontal row, touching each
other, an edge of the crystal is formed.

Close packing of spheres in one dimension Trigonal void

In three dimensional close packing patterns, the voids can be

2. Two Dimensional Packing of two types:
It is done in two different types:
1. Tetrahedral Void It is a simple triangular space
(i) Square Close Packing (SCP) The particles, when placed surrounded by four spheres.
in the adjacent rows show a horizontal as well as vertical
alignment and form squares.

1 Coordination number is 4
(SCP)
4 2

Square close packing Tetrahedral void

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