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Exercise Short Questions Notes

Chapter # 1 Stoichiometry

1. 58.5 amu are termed as formula mass and not molecular mass of

NaCl. Why?

Since NaCl is an ionic compound, therefore it cannot exist as individual,

neutral independent molecules. Therefore term formula mass is used to

express its mass instead of molecular mass.

2. Concept of limiting reactant is not applicable to the reversible

reactions. Explain.

The reactant that is consumed completely in a chemical reaction is called

limiting reactant. However, in reversible reactions reactants are not

completely converted into products. Hence, concept of limiting reactant is

not applicable to the reversible reactions.

3. How many covalent bonds are present in 9g of water?

Mass of water = 9g

Molar mass of water = 1g mole -1

Therefore

Number of molecules of water = Mass of water/ Molar mass of

water

No. of molecules of water = (9/18) x 6.02 x 10 23 = 3.01 x 1023

Thus

1 molecule of H 2 O contains covalent bonds = 2

3.1x 10 23 molecules of H 2 O contain covalent bonds = 2 x3.1x

10 23 = 6.2x 10 23 bonds

4.

Differentiate between limiting and non-limiting reactants.

a) The reactant that is consumed completely in a chemical reaction is called limiting reactant. The reactant left unused or unreacted after

the completion of reaction is called “Reactant in excess” or non- limiting reactant.

b) The limiting reactant controls the amount of product formed in a chemical reaction. The non-limiting reactant does not control the amount of product.

c) The amount of products formed depends upon the initial amount of limiting reactant. The amount of product formed is independent of the initial amount of non-limiting reactant.

 5. How many molecules are there in 12g of ice? Mass of ice (water) = 12 g Molar mass of water = 18 gmole -1 Thus Number of molecules of water = Mass of water / molar mass of water = (12/18) x 6.02x 10 23 = 4.01x 10 23 6. One mole of H 2 SO 4 should completely react with two moles of NaOH. How does Avogadro’s number help to explain it? The chemical reaction of H 2 SO 4 and NaOH is 2NaOH + H 2 SO 4 → Na 2 SO 4 + 2H 2 O 2 formula units molecules 1 molecule 1 formula unit 2 Or 2 moles 1 mole 1 mole 2

moles

Thus according to Avogadro’s, the above equation shows that 2 x 6.02 x 10 23 formula units of NaOH react with 6.02 x 10 23 molecules of H 2 SO 4 to produce 6.02 x 10 23 formula units of Na 2 SO 4 and 2 x 6.02 x 10 23 molecules of water.

7. Give reason that 1 mole of different compounds have different masses but have the same number of molecules.

One mole of different compound has different masses but same number of molecules. It is because individual molecules of different compounds have different masses, therefore, equal number of moles of different compounds will also have different masses although same number of molecules.

e.g.

1 mole of H 2 O = 6.02 x 10 23 molecules of H 2 O = 18 g of H 2 O

1 mole of CO 2 = 6.02 x 10 23 molecules of CO 2 = 44 g of CO 2

8. 23g of sodium and 238g of uranium have equal number of atoms in them. Since 1 mole of sodium (Na) = 23 g 1 mole of uranium (U) = 238 g As 1 mole of each element contains Avogadro’s number of atoms and there is 1 mole of each of Na and U. Hence 23 g of Na and 238 g of U contains equal number of atoms, i.e. 6.02 x 10 23 .

9. What is percentage composition? Calculate percentage composition of ' Glucose. The relative amount of each element present in a compound is called its percentage composition. The percentage of each element in glucose is

calculated as Molar mass of glucose (C 6 H 12 O 6 ) = 12x6+1x12+16x6=180 g mole -1

% of an e element = (Mass of the element in compound / Molar mass of

the compound) x 100

% of carbon = (72/180) x 100 = 40%

% of hydrogen = (12/180) x 100 = 6.67%

% of oxygen = (96/180) x 100 = 53.33%

10. Calculate the weight of oxygen gas evolved when 5.0 g of KClO 3 are completely decomposed thermally. Given mass of KClO 3 = 5g Formula mass of KClO 3 = 39 + 35.5 + 16 x 3 = 122.5 g mole -1 No. of moles of KClO 3 = 5/122.5 = 0.04 moles According to reaction, 2 KClO 3 → 2KCl + 3O 2 2 moles of KClO 3 = 3 moles of O 2

0.04 moles of KClO 3 = (3/2) x0.04 = 0.06 moles of O 2

Since 1 mole of O 2 = 32 g of O 2

0.06 moles = 0.06 x 32 g of O 2

= 0.361 g of O 2 11. What is limiting reactant? How will you determine it? The reactant that is consumed completely in a chemical reaction is called

limiting reactant.

The limiting reactant in a chemical reaction can be determined by following procedure.

i) Number of moles of each reactant is calculated.

ii) Using balanced chemical equation, amount of product from each reactant is calculated.

iii) The reactant which gives least amount of product is the limiting reactant.

12. Define Theoretical yield and actual yield.

Theoretical Yield The quantity of product calculated to be obtained from given quantities of initial reactants is called theoretical yield of a reaction Actual Yield The quantity of product that is actually produced in a chemical reaction is called the actual yield.

13. What is conversion factor? It is the ratio between the number of moles of reactants taking part and the number of moles of products formed during a chemical reaction. It is calculated by using balanced chemical equation as Conversion Factor = unit to determine/ unit available E.g. consider the reaction C 3 H 8 + 5O 2 → 3CO 2 + 4H 2 O If we want to determine the number of moles of CO 2 (unit to determine) from the given moles of C 3 H 8 (unit available), then conversion factor (in terms of moles) from above equation is Conversion Factor = 3 moles of CO 2 / 1 mole of C 3 H 8

14. What is the relationship between mass and volume of a gas at S.T.P.? The volume occupied by one mole of a gas at S.T.P. is called its molar volume. Its value is 22.414 dm 3 . Moreover, mass of 1 mole of a gas is called its molar mass. Hence, 22.414 dm 3 of a gas at S.T.P. equals its molar mass. e.g.

22.414

dm 3 of CO 2 at S.T.P. = 1 mole = 44 g. of CO 2

22.414 dm 3 of O 2 at S.T.P. = 1 mole = 32 g. of O 2

15. Identify the limiting reagent in a chemical reaction.

The limiting reactant in a chemical reaction can be identified by following procedure.

- Number of moles of each reactant is calculated.

- Using balanced chemical equation, amount of product from each reactant is calculated.

- The reactant which gives least amount of product is the limiting reactant.

16. The actual yield is lesser than the theoretical yield. Give reasons.

The actual yield may be lesser than the theoretical yield due to following reasons,

a) Formation of by-products due to side reactions.

b) Reversible reactions may not go to completion.

c) Mechanical loss due to filtration, distillation, and separation by separating funnel, washing and crystallization etc.

17. What are the representative particles in one mole of a gas at

S.T.P.? One mole of any gas at S. T. P occupies 22.414 dm 3 and contains 6.02 x

10 23 particles e.g.

 22.414 dm 3 of H 2 gas at S. T. P = 2g = 6.02 x 10 23 molecules 22.414 dm 3 of NH 3 gas at S. T. P = 17g= 6.02 x 10 23 molecules

18. Calculate the gram molecular mass of a gas when the density is

clearly known. The molecular mass of a gas is related to its density by the formula D = PM/RT

And M = dRT / P

Since S. T. P the volume occupied by 1 mole of a gas is 22.414 dm 3

therefore if density of a gas at S. T. P is clearly known then gram

molecular mass of a gas can be calculated. The STP is standard

temperature and pressure. Standard temperature is 273K (0C) and

standard pressure is 1 atm.

19. What is stoichiometry and stoichiometric amounts

d) The branch of chemistry which deals with the study of relative

amount of substance involved in a chemical reaction as given by a

balanced chemical equation is called stoichiometry.

e) The amounts of reactants according to balanced chemical equation

are called stoichiometric amounts

f) When reactants are used in stoichiometric amounts then all the

reactants are used up and there is no concept of limiting reactant.

Chapter #2 Atomic Structure

a) How does Mosley’s Law help in the production of X-rays?

The mathematical form of Moseley's law is √v = a (Z - b)

Where a and b are constants for a particular metal.

This law states,

The frequency of a spectral line in an X-ray spectrum varies as the

square of atomic number of the element emitting it.

Thus by proper selection of target material desired X -rays can be

produced.

b) Which quantum number is also called sub-shell quantum number?

Azimuthal quantum number tells about the shape of orbital or sub-shell

therefore, it is called sub-shell quantum number. It is denoted by “l”. It has

value from 0, 1, 2, 3

various subshells e.g. 0 stands for s-subshell

corresponds for

(n - 1). The numbers 0, 1, 2, 3

1 stands for p- subshell

2 stands for d- subshell

3 stands for f- subshell

c)

What is the difference between an orbit and orbital?

 Orbit Orbital It is the circular path on which electron revolves around nucleus. It is the region in space in which probability of finding electron is maximum (about 95%) This term is used in the Bohr s theory of atomic structure. This term is used in quantum mechanical model. It is three dimensional. It is two dimensional. In this exact position of electron indicated. Only probability of electron is given in an orbital. Number of electrons in an orbit is given by the formula, 2n 2 . Where ‘n’ is the number of orbit. Each orbital contains maximum two electrons.

d) What is the relationship between?

The energy of radiation is inversely proportional to its wavelength E=hc/λ

Where

 λ = wavelength of any light radiation h = Planck’s constant = 6.625 x 10- 34 Js

b) frequency and wavelength Frequency is related to wavelength as

c=v/ λ

or

v=c/ λ

Where

c = velocity of light = 3 x 10 8 ms -1

λ = wavelength of any light radiation

e) What species are formed by the decay of neutron?

Free neutron decays into proton with the emission of electron and neutrino.

f) Hydrogen atom and He+ are mono electronic system, but the size of He + is much smaller than H, why? Both, hydrogen atom and He+ ion have one electron in their outermost shell. However the nucleus of He+ has greater positive charge (due to two protons) than that of hydrogen atom (due to one proton). Therefore, nucleus of He+ attracts its electron more powerfully as compared to hydrogen. Hence, size of He becomes smaller than hydrogen.

g) How the wavelength of moving particles is inversely proportional to its momentum? The wavelength of particles is inversely proportional to its momentum. λ =h / mv = h/p

 Where p = mv = momentum of particle λ = wavelength of any light radiation h = Planck’s constant = 6.625 x 10 -34 Js

h) State Heisenberg’s uncertainty principle. It is impossible to determine simultaneously and precisely, both position and momentum of a small fast moving particle e.g. electron.

i) Why is4s orbital lower in energy than 3d orbital? According to Wiswesser’s rule, the Energy of orbital is determined from the (n+l) value. Lower the (n+l) value lower will be the energy of orbital & vice versa. Thus

 Orbital (n + C) n Remarks value value 4s 4+0=4 4 4s is of 3d 3+2=5 3 lower energy

j) Write electronic configuration of 25 Mn 2+ , 30 Zn 2+ , 24 Cd 3+ , 13 Al 3+ .

 25 Mn 2 Is2 2s2 2p6 3s2 3p6 4s0 3d5 30 Zn 2 Is2 2s2 2p6 3s2 3p6 4s0 3d10 24 Cd 3 1s2 2s2 2p6 3s2 3p6 4s0 3d4 13 Al 3+ Is2 2s2 2p6 3s0 3p0

k) What is (n+ l) rule? The energy of the orbital can be decided by Wiswesser’s rule also called 9 is s :( n+l) rule. The energy of orbital is determined from the (n+l) value.

Lower the (n+ l) value lower will be the energy of orbital & vice versa. If two orbital have same (n+ l) value then lower the value of n lower will be the energy of orbital & vice versa.

Examples

 Orbital (n+ l) n Remarks value value 4s 4+0=4 4 4s is of lower 3d 3+2=5 3 energy 4p 4+1=5 4 3d is of lower 3d 3+2=5 3 energy

l) Point of the defects in Bohr’s Model. How these defects are partially covered by dual nature of electron and Heisenberg’s uncertainty principle. Following are the defects of Bohr’s atomic model.

g) It cannot explain the spectrum of multi-electron or poly-electron systems like He, Li, Be etc.

h) Powerful spectrometer shows that individual lines in line spectrum of an atom actually consist of several lines, e.g. H a -line in Balmer series consists of five component lines. This is called fine structure or multiple lines. Bohr’s theory cannot explain this fine structure.

i) Bohr suggested circular orbits for electrons. However, researches have shown that the motion of electron around the nucleus takes place in three dimensional space. Thus atomic model is not flat

j) When the spectrum of excited hydrogen is taken in a strong magnetic field, spectral lines further split up into closely spaced lines. This is called Zeeman Effect, e.g. when Na spectrum is taken in a weak magnetic field, its single line is split up into two component

lines.

Similarly, when emission spectrum of excited H-atom is taken in a strong electrical field, lines are split up into component lines. This is called stark effect. Bohr’s theory cannot explain Zeeman Effect and Stark’s effect.

'Heisenberg’s uncertainty Principle pointed out that both position and momentum of a small fast moving particle cannot be determined simultaneously. However with the idea of wave nature of electron Schrodinger showed that the probability of finding an electron can be determined. Schrodinger derives an equation which explained the behavior of electron in three dimensional space in an atom.

m)Differences

 Continuous spectrum Line Spectrum In this colors are diffused into each other and they are not separated. It consists of dark or bright lines separated by bright or dark bands. Each color in the band has a range of frequencies. Each line in the spectrum has its own characteristic color and frequency. There is not sharp boundary There is distance between the between colors. lines. It is characteristic of the molecules. It is characteristic of atoms. It is obtained by passing It is obtained by heating a polychromatic triangular prism. light through a substance or by passing polychromatic light through a substance and then passing emitted radiations through a prism. It has only one type. It is of two types (line emission spectrum, line absorption spectrum) Example: rainbow. Example: Balmer series of hydrogen spectrum Line Emission Spectrum Or Line Absorption Spectrum Or Atomic Spectrum Atomic Absorption Spectrum Bright line separated by dark bands. Dark line separated by bright bands. Formed when the substance is in excited state. Formed when substance is in unexcited state.
 Formed when the substance is Formed by transparent gases, excited to vapor state. transparent liquids, and solids. Electron jumps from higher energy For its formation electron jumps level to lower and emits energy as from lower energy level to higher by light for its formation. The emitted absorbing energy. The absorbed radiations are indicated by colored radiations are indicated by dark lines. lines. Emission spectrum of sodium has Absorption spectrum of sodium has two yellow lines separated by dark two dark lines separated by bright bands. bands.

Chapter #3 Theories of Covalent and Shapes of Molecules

a) Give reason for the difference in calculated values and observed

values

In HX, the electronegativity of X is greater than that of H. So, X attracts

electron more towards itself and gets 5 charge while H gets 5 charge.

Thus, ionic character is developed in HX bond. This increases the

attraction between H and X. So, bond energy also increases. Hence, the

observed values of bond energies are higher than the calculated values.

b) Effect of high bond energy on bond length with reason

Generally, shorter the bond, higher the bond energy. It is because, shorter

bonds have effective overlap of orbitals. So, they are difficult to break. In

HX, ionic character is present due to electronegativity difference between

H and X. Therefore, the observed bond energy is greater than the

calculated bond energy. As a result, bond length becomes short.

c) Ionic character on the basis of bond energies, with reason

In HX, the electronegativity of X is greater than that of H. So, X attracts

electron more towards itself and gets δ- charge while H gets δ + charge.

The ionic character is developed in HX bond. Generally, greater the

electronegativity difference between the two bonded atoms, greater is the

ionic character and stronger is the bond. Since, electronegativity

difference in HCl is greater than in HI, therefore, HCl has more ionic

character than HI.

Chapter #4

Gases

a) What is Absolute zero and Absolute Scale of temperature?

Absolute zero: the temperature at which the given amount of volume of

a gas reduces to zero

a) On Celsius scale Absolute zero is equal to -273.15°C.

b) It is considered as the lowest possible temperature.

Absolute Scale of temperature: Lord Kelvin developed the Absolute

temperature scale or the Kelvin temperature scale. On this scale, -

273.15°C is the starting point of the scale. I.e. - 273.15°C = Zero Kelvin.

It is related to the Celsius scale as K = °C + 273

b) Give any four applications of Plasma Slate.

Plasma has many uses

a) It is used for processing of semiconductors, sterilization of some

products, lamps, lasers, etc.

b) It is used to derive particle accelerators.

c) It is used to make fluorescent tubes, neon signs etc.

d)

It helps to clean up the environment, pasteurize food, used to make

corrosion resistant tools.

c) What are the different units of gas constant (R.)? The value of gas constant R depends upon the units of pressure and volume of a gas. Following are the common units and value of R

R = 62.4 dm 3 mm of Hg mole -1 K -1 (pressure in mm of Hg and volume

in dm 3

R

= 62.4 dm 3 torr mole -1 K -1 (pressure in torr and volume in

dm3)

R = 62400 cm 3 torr mole -1 K -1

in cm3)

R = 8.3143 J mole -1 K -1

(pressure in torr and volume

(SI unit)

d) Define the Translational, Rotational and Vibration Energies. Translational energy The motion of gaseous molecules in a straight line in all possible directions is called translational motion and energy due to this motion. The kinetic energy of this motion is called translation kinetic energy. Rotational energy The motion of gas molecules due to net angular momentum about their center of is called rotational motion. The kinetic energy of this motion is called Rotational kinetic energy. Vibrational energy

The motion of gas molecules due to oscillations is called vibrational

of this motion is called vibrational kinetic

motion. The kinetic energy energy.

e) Define Pressure. How will you explain it in different units? Pressure is defined as the force per unit area, i.e.

P=F/A

Units of Pressure:

a) SI units The SI unit of pressure is Pascal (symbol: Pa).

A Pascal is defined as the force of one newton (N) spread over an area

of 1m 2 Thus 1 Pa = 1 Nm -2

b) CGS system

In CGS system, the unit of pressure is barye (symbol: Ba)

A barye is defined as the force of one dyne spread over an area of

1cm 2 . Thus 1 Ba = 1 dyne cm -2

c) Other units Other units commonly used are atmosphere, torr, mm of Hg, Pounds per square inch (psi).

An atmosphere (atm) is defined as

One atmosphere is the force exerted by 76 cm long column of mercury on area of 1 cm 2 at 0°C.

Thus

1 Atm

a) atm

1 atm=

101325 Pa =101325 N m -2 760 torr = 760mm of Hg 101325 Pa

=

=

1 101.325 kPa

1 14.7 Psi (pounds per square inch)

atm=

atm=

f) Define Charles Law. How will you derive Absolute Zero with its help?

g) Define Avogadro’s Law. What is its significance? This law states Equal volumes of all the gases at same temperature and pressure contain equal number of particles molecules Thus, volume of a gas is directly proportional to the number of moles

I.e.

V n

Avogadro s law can be applied to determine:

1. Mass

2. Volume

3. Number of molecules of a gas.

h) What is the difference between an Ideal gas and a real gas?

 Ideal Gas Non-ideal gas It obeys gas laws under all It does not obeys gas laws under all conditions of temperature and pressure. conditions of temperature and pressure. There are no attractive or repulsive forces among the gas particles. There are attractive or repulsive forces among the gas particles. Actual volume of gas particles is negligible as compared to the total volume of gas. Actual volume of gas particles is not negligible as compared to the total volume of gas, particularly at low ‘T’ and high ‘P’ values. PV/RT = constant PV/RT ≠ constant It is an imaginary gas and does not exist in nature. It is a real gas and exists in nature e.g., SO 2 , NH 3 etc.

i) Ice on a car windscreen will disappear as you drive along, even without the heater on. Explain. When the speed of wind increases rate of evaporation also increases. As a car moves with speed then wind hits the windscreen with high speed. Thus, rate of evaporation ice increases and it disappears after sometime.

j) When salt is placed on ice, the ice melts. Explain When salt is added to ice, it decreases its vapor pressure due to solute- solvent interactions. Thus, freezing point of ice is depressed and it melts.

k) When jar of coffee is opened, people in all parts of the room soon notice the smell. Use the Kinetic Theory to explain how this happened.

This is due to the diffusion process. According to kinetic molecular theory, the vapors of coffee show translational motion. Therefore, they move in a straight line in all possible-directions in the room. So people in all parts of the room notice the smell.

l) Why diffusion in gases is faster than in liquids? In gases the molecules have high translational kinetic energy and are widely separated. Thus, they can move freely in all direction. Therefore, they diffuse rapidly. In liquids, there are small empty spaces packed between molecules. Therefore the motion of molecules is limited. So the diffusion between closely packed molecules of liquids is slow due to less collision between them. m) A bubble of methane gas rises from the bottom of the North Sea. What will happen to the size of the bubble as it rises to the surface? When the bubble rises from the bottom of the North Sea, it will increase in size because there is high pressure of water at the bottom which compresses the bubble. So it is of small size. And when it rises the pressure decrease and the volume of the bubble increases.

n) Use Kinetic Theory to explain the following:

1. When you take a block of butter out of the fridge, it is quite hard. However after 15 minutes it is soft enough to spread.

At low temperature the kinetic energy of molecule is less, therefore they do not show much motion. So in the bridge a block of butter becomes hard due to limited movement of molecules. However when it is taken out of the bridge it absorbs heat which increases the kinetic energy of molecules. So it becomes soft enough to spread.

2. When you come home from college and open the door, you can smell the tea which is being made. This is due to the diffusion process. According to kinetic model theory, the vapors of tea show translational motion. Therefore, they move in a straight line in all possible directions. So, you can notice smell of tea.

3. A football is blown up until it is hard on a hot summer. In the evening the football feels softer. There are two reasons:

c) This is due to effusion process. In hot summer, temperature is high, due to which molecules of gas filled in football have high kinetic energy. Therefore, they effuse slowly. So, due to slight decrease in amount of gas in football it feels softer.

d) In the evening, the temperature decreases therefore the kinetic

energy of molecules also decreases and as a result the gas in football is slightly compressed and it feels softer.

4. A windy day is a good drying day The rate of evaporation increases with the increase in the speed of wind. It is because wind continuously carries away the water vapors e.g. water vapors evaporation from wet clothes are continuously taken away by the wind. Thus rate of evaporation increases from surface of clothes which dry quickly. So a windy day is a good drying day.

Chapter #5

Liquids

1. Give the general properties of liquids as to

a) Diffusion

Liquid molecules have kinetic energy. They can move from place to

place. The diffusion in liquids is due to movement of molecules from

one place to another. Due to limited movement of molecule, the rate of

diffusion decreases.

E.g. when a drop of ink is added to water it diffuses slowly, it is because

there are small empty spaces between the molecules. The diffusion

between closely packed molecules of liquids is slow due to less

collision between them.

b) Compression

In liquids molecules are in close contact, therefore, it cannot be

compressed significantly by applying pressure.

E.g. when pressure on water is increase from one to two atmospheres,

its volume is reduced to 0.0045 percent which is negligible. However

the same pressure reduces the volume of a gas up to 50 percent.

2. What are intermolecular forces?

The forces of attractions among the molecules of a substance are called

intermolecular forces.

E.g. water exists as a liquid due to inter molecular forces called Hydrogen

bonds.

- The forces of attraction among molecules of non-polar

substances are called Van der Waal’s forces.

- The physical properties of liquids depend upon the strength of these forces. Examples: Dipole-Dipole forces, London Dispersion forces, Hydrogen bonding etc.

3. What are the types of intermolecular forces, give examples? The intermolecular forces are of five types

- Dipole-dipole forces: e.g. between HCl molecule (polar)

- Ion-dipole forces: e.g. between H + ions and water molecules

- Dipole-induced dipole forces: e.g. between He gas (non-polar) and HCl gas (polar)

- London Dispersion forces: e.g. forces between He molecules (non-polar)

- Hydrogen bonding: e.g. forces between water molecules

4. What is hydrogen bonding? Give particular examples. A hydrogen bond is the attraction between the lone pair of electronegative atom and a hydrogen atom that is bonded to either N, O, or F.

Example: Hydrogen bonding is present among molecules of H 2 O, HF, and NH3 etc.

5. What are the applications of H-bonding Hydrogen bonding has many applications. It is responsible for

a) Thermodynamic properties of covalent hydrides

b) Solubilities of hydrogen bonded molecules

c) Cleansing action of soap and detergents

d) Adhesive nature of paints, dyes, glue, honey etc.

e) Rigidity and tensile strength of fibers for clothing

f) Properties of food materials

g) Stability of biological molecules, e.g., protein,

6. What are the different types of physical properties of liquids? Following are the types of physical properties of liquids Additive properties These properties depend upon the molecule E.g. molecular mass Constitutive properties These properties depend upon the arrangement of atoms in the molecules and not their number. E.g. optical activity. Colligative properties Number of ions and molecules present but do not depend upon the structure of molecules. E.g. Osmotic pressure, molar volume etc.

7. Define vapor pressure. What are the factors affecting the V.P? The pressure exerted by the vapors of a liquid in equilibrium with a liquid state at a given temperature is called vapor pressure of a liquid. Following factors affect the vapor pressure of a liquid. Intermolecular forces: stronger the intermolecular forces lower will be vapor pressure and vice versa. Temperature: increase in temperature increases the boiling point of a liquid and vice versa.

8. What is a) Viscosity Viscosity of a liquid is a measure of its internal resistance to flow. Larger the viscosity the more slowly the liquid flows. E.g. the water has less resistance to its flow than honey or glycerin SI unit of viscosity are kilogram per meter per second (kgms -1 )

b) Surface tension The forces in dynes acting at right angle on a unit length of surface of a liquid is called surface tension. The surface of liquids such has water as stretched membrane due to surface tension. SI unit of surface tension is joule per square meter. 9. Define molar heat of fusion and molar heat of vaporization.

Molar Heat of Fusion The amount of heat required to convert one mole of a solid into a liquid state at its melting point is called molar heat of fusion E.g. H 2 O (s) → H 2 O (l) Molar Heat of Vaporization The amount of heat required to convert one mole of a liquid into vapors state at its boiling point is called molar heat of vaporization e.g. H 2 O (l) → H 2 O (g)

10. Why distillation under reduced pressure is often used in the purification of chemicals? The separation of liquids on the basis of their boiling points by heating under reduced pressure is called vacuum distillation. Some high boiling liquids cannot be separated by distillation at normal pressure (i.e. 1atm). It is because they decompose before reaching their

boiling points e.g. boiling point of glycerin is 290C at 760mmHg. But it decomposes before reaching its boiling point. However when the external pressure is reduced to 50mmHg in a vacuum distillation apparatus, it boils at 210C. Hence it can be purified without decomposition.

11. You wish to have a “five minute” boiled egg for breakfast. For

each of the following location or situation, would you cook your egg

less than or more than five minutes to produce your “five minutes” boiled egg? Explain your answers of the following. The temperature at which the vapor pressure of a liquid becomes equal to the atmospheric pressure or some other external pressure is called boiling point of a liquid. Thus increase in external pressure increases the boiling point of a liquid and vice versa.

a) You are at top of Whittler Mountain in British Columbia At the top of the Whittler Mountain the external pressure is less than normal (760 torr) pressure. Therefore, water boils below 100C, so the cooking of the egg will require more than 5 minutes.

b) You have breakfast just before you start work 2000 meter underground in a gold Timmons, Ontario. In underground gold mine, the external pressure is more than normal (760 torr) pressure. Therefore, water boils above 100C. So the cooking of egg will require more than 5 minutes.

c) You have breakfast on a very clear bright sunny day at sea level. At sea level, the external pressure is normal i.e. 760 torr. Therefore water boils at 100C. So the cooking of egg will require 5 minutes. Explain.

a) What happens to the particles of a solid at its melting point? When a solid is heated, the particles present in it start vibrating at higher frequency. They transfer their kinetic energy throughout the solid. At the melting point, their vibrational energies become so high that they leave their fixed positions at once and become a liquid.

b) What happens during evaporation in a liquid?

12.

The molecules of liquids have kinetic energy. The molecules on the surface have kinetic energies higher than the average kinetic energies. Thus they overcome the intermolecular forces and enter the gas phase. This is called evaporation.

c) Why a given gas occupies all the available space? In gases, molecules are widely separated from one another. They have very weak intermolecular forces and have high kinetic energy. Therefore when a gas is added to a container, molecules of gas occupy all the available space by random motion.

d) The latent heat of fusion? The amount of heat required to convert solid into liquid at its melting point is latent heat of fusion. Since temperature becomes constant at melting point therefore latent heat is used to break the intermolecular forces. Explain.

a) How liquids mix? Liquids mix by the process of diffusion. Liquid molecules have kinetic energy. They can move from place to place. The diffusion in liquids is due to movement of molecules from one place to another. However diffusion is slow in liquids. The molecules of two diffusing liquids develop different types of intermolecular attractions for each other and form a solution. E.g. water and ethanol form H-bonds with each other so they mix together.

13.

b) Why temperature of a boiling liquid does not raise at its boiling

point?

When a liquid is heated, its temperature goes on increasing until its

boiling point is reached. At boiling point the temperature becomes

constant. It is because the heat supplied at boiling point is used to

convert the liquid into vapors by breaking intermolecular forces. The

amount of heat required to convert one mole of a liquid into vapors at

its boiling point is called molar heat of vaporization.

Chapter #6

Solids

1. Indicate the effect of pressure and temperature on solids.

There are little affected by changes in temperature and pressure. In

solids, molecules are tightly packed, therefore, pressure has no effect on

them. However increase in temperature increases their volume to some

extent. It is because of decrease in intermolecular forces.

2. What do you know about hexagonal closest packing?

When two layers of spheres are placed over each other than the second

layer has two types of holes in it, tetrahedral holes and octahedral holes.

If third layer of spheres is placed directly above the tetrahedral holes then

this third layer is identical to bottom layer. This is called hexagonal close

packing (hcp) arrangement. It is usually written as ABAB or 1212 pattern.

3. Write a note on Dispersion effect.

The distortion of electronic cloud of a substance is known as dispersion

effect. This produces polarizability in the molecule.

The polarizability of an atom or molecule is a measure of the ease with which electron charge density is distorted. Bigger atoms have more electrons and bigger electron cloud than small atoms. In bigger atoms, the outer electrons are more loosely bound. They can shift towards another atom more readily. Thus polarizability increases with increased atomic and molecular size.

4. There are some changes in matter. Which of the changes require us to provide energy and which gives out energy?

a) Solids -> Liquids This is melting process. This change requires energy called heat of fusion. It is because intermolecular forces of solids should be broken to convert them into liquid.

b) Liquid -> Gas This is vaporization process. This change requires energy called heat of vaporization. It is because intermolecular forces of liquids should be broken to convert them into gas.

c) Gas -> Liquid This is condensation process. This change releases energy since gas is at higher energy state than liquid so it is cooled to convert into liquid state.

d) Liquid -> Solid This is freezing process. This change releases energy since liquid is at higher energy state than solid so it is cooled to convert it into solid state.

5. Explain each of the statements below.

a) You can smell a fish from across the road.

This is due to the diffusion process. The vapors from the fish diffuse into air and reach you. So you can smell the fish.

b) Sugar dissolves faster in hot water than in cold water. The solubility of sugar in water is an endothermic process. Therefore when temperature is increased, the intermolecular forces among sugar molecules break faster. Thus sugar dissolves faster in hot water than in cold water.

c) Why is the temperature and pressure important when giving the

density of oxygen and nitrogen? According to the equation, d=PM/RT, the density of a gas is directly proportional to the pressure and inversely proportional to the temperature. Thus temperature and pressure should be mentioned for densities of gases.

6. Explain why the particles in solid ice stick together and those of steam not even when they get very close (collision)? In solid ice particles have strong intermolecular forces therefore they stick

together. They only show vibrational motion. In steam, particles have weak intermolecular forces and have high translational kinetic energy. Therefore even when they collide they do not stick together.

7. When long bridges are constructed, the roadbed is made in sections with spaces between the sections. Why must be done so? It is because the roadbed section may expand due to increase in temperature during summer. Therefore spaces are made between the sections to provide some space for expansion. This avoids any damage due to expansion.

8. Explain each of the following situations in terms of energy produced

or used.

a) You feel cold immediately after getting out of a swimming pool,

but you feel comfortably warm when you have dried yourself.

After getting out of swimming pool, a thin layer of water is present on

the body. This water evaporates by taking heat from the body,

therefore you feel cold immediately. When the body is dried up, then it

equals its temperature to the surrounding there you feel warm.

b) Skin exposed for just a short time to steam can suffer severe

burns whereas, skin exposed to hot water for the same length of

time suffers only a mild burn or none at all.

Since steam is produced by supplying heat of vaporization to the

boiling water, therefore steam molecules contain more energy than hot

water molecules. Thus steam causes severer burns than hot water.

Chapter #7

20. Write the equation of K c and K P for the following processes.

d) Blue vitriol is deep blue solid copper (II) sulphate pentahydrate is heated to drive off water vapors to form white solid copper (II) sulphate. The chemical reaction is CuSO 4 .5H 2 O CuSO 4 + 5H 2 O Since solids are not included in equilibrium constant expression, therefore K c = [H 2 O] 5 And

K p = P 5 H2O

e) The decomposition of solid phosphorus pentachloride to gaseous phosphorus trichloride and chlorine gas The chemical reaction is

PCl 5 PCl 3 + Cl 2 Since solids are not included in equilibrium constant expression, therefore K c = [PCl 3 ] [Cl 2 ] And

K p = P PCl3 x P Cl2

21. Predict the shift in equilibrium position that will occur for each of the following processes when the volume is reduced.

o) PCl 3 + 2NH 3 P (NH 2 ) 3 + 3HCl According to Le-Chatlier’s principle, when volume is reduced then the equilibrium will shift in a direction in which number of molecules are reduced. In the given reaction, three molecules are present on reactant side and four one the products side. So when volume is reduced, the equilibrium will shift in backward direction to reduce the number of molecules.

p) 2NO + O 2 2NO 2 According to Le-Chatlier’s principle, when volume is reduced then the equilibrium will shift in a direction in which number of molecules are reduced. In the given reaction, three molecules are present on reactant side and two on the product side. So when volume is reduced, the equilibrium will shift in forward direction to reduce the number of molecules.

q) 4NH 3 + 5O 2 4NO + 6H 2 O According to Le-Chatlier’s principle, when volume is reduced then the equilibrium will shift in a direction in which number of molecules are reduced. In the given reaction, seven molecules are present on reactant side and eight on the product side. So when volume is reduced, the equilibrium will shift in backward direction to reduce the number of molecules.

22. For each of the following reactions, predict how the value

of K c changes as the temperature is increased.

e) 2NO + O 2 2NO 2

ΔH°=180kJ

Since the reaction is endothermic, heat is written as reactant 2NO + O 2 +heat 2NO 2 According to Le-Chatlier’s principle, when temperature is increased this reaction will shift in forward direction in order to

absorb the added heat. Therefore, concentration of NO will increase and that of N 2 and O 2 will decrease. i.e. Thus, the value of K c will increase with increase in temperature and vice versa.

f) 2SO 2 +O 2 2SO 3

ΔH°=-598kJ

Since the reaction is exothermic therefore heat is written as product, 2SO 2 +O 2 2SO 3 +heat According to Le-Chatlier’s principle, when temperature is increased this reaction will shift in backward direction in order to absorb the added heat. Therefore, concentration of SO 2 and O 2 will increase and that of SO 3 will decrease. i.e. Thus, the value of K c will decrease with increase in temperature and vice versa.

g) N 2 O 4 2NO 2 ΔH°=58kJ Since the reaction is endothermic therefore heat is written as reactant, N 2 O 4 +heat 2NO 2 According to Le-Chatlier’s principle, when temperature is increased this reaction will shift in forward direction in order to absorb the added heat. Therefore, concentration of NO 2 will increase and that of and N 2 O 4 will decrease. i.e. Thus, the value of K c will increase with increase in temperature and vice versa.

h) CH 4 + H 2 O CO+3H 2 ΔH°=256kJ Since the reaction is endothermic therefore heat is written as reactant, CH 4 + H 2 O +heat CO+3H 2 According to Le-Chatlier’s principle, when temperature is increased this reaction will shift in forward direction in order to absorb the added heat. Therefore, concentration of CO and H 2 will increase and that of and CH 4 and H 2 O will decrease. i.e.

Thus, the value of K c will increase with increase in temperature and vice versa.

23. What is the difference between an equilibrium with a K c value larger than one compared with an equilibrium that a K c value smaller than one. For a general reaction

Reactants Products The K c is given as K c = [Products] / [Reactants] The numerical value of the equilibrium constant, K c can be used to determine the extent of the chemical reaction

- If K c < 1, the equilibrium mixture contains more products than reactants. Thus forward reaction occurs to greater extent.

- If K c > 1, the equilibrium mixture contains more reactants than products. Thus backward reaction occurs to greater extent.

- If K c = 1, the equilibrium mixture contains almost same amount of products and reactants.

24. Describe the behavior of the following equilibria with the stated changes.

d) Increasing pressure on: C 3 H 8 + 5O 2 3CO 2 + 4H 2 O According to the Le-Chatlier’s principle, if pressure is increased on an equilibrium system, then it will reduce its volume by reducing the number of molecules present. In the given reaction, six molecules are present on reactant side and seven on the product side. So when pressure is increased, the equilibrium will shift in backward direction to reduce the number of molecules.

e) Adding I 2 to 2HI I 2 + H 2 According to the Le-Chatlier’s principle, when a product (e.g. I 2 ) is added to equilibrium mixture then concentration of products increased and equilibrium is disturbed. Therefore, to regain the constant value of K c , the reaction will proceed in reverse direction until new equilibrium is established.

f) Removing heat from CO 2 CO + ½ O 2

ΔH°=284kJ

Since the reaction is endothermic, therefore heat is written as

reactant, CO 2 +heat CO + ½ O 2

According to the Le-Chatlier’s principle, when temperature is decreased this reaction will shift in backward direction. Therefore concentration of CO 2 will increase and that of CO and O 2 will decrease. i.e. Thus the value of K c will decrease with decrease in temperature and vice versa.

g) Decreasing pressure on:

C 2 H 6 H 2 + C 2 H 4

According to the Le-Chatlier’s principle, if pressure is decreased on an equilibrium system then it will increase its volume by increasing the number of molecules present. In the given reaction, one molecule is present on reactant side and two molecules are present on product side. So when pressure is decreased, the equilibrium will shift in forward direction to increase the number of molecules.

25. Consider the following gas phase reaction

SO 2 +Cl 2 SO 2 Cl 2 + Heat Describe the four changes that would derive the equilibrium to left. The four changes can be made according to Le-Chatlier’s principle.

a) High temperature The forward reaction is exothermic. Therefore high temperature

will drive the reaction in backward direction.

b) Low pressure In the given reaction, two molecules are present on reactant side and one on the product side. So when pressure is decreased, the equilibrium will shift to the left.

c) Continual removal of reactants When reactants are removed continuously then the equilibrium will shift in backward direction from right to left.

d) Continual addition of products When products are added continuously then the equilibrium will shift to the left.

26. How would you change the volume of the following

reactions to increase the yield of products?

a) Cl 2 + I 2 2ICl 2 According to Le-Chatlier’s principle, when volume is reduced then the equilibrium will shift in a direction in which number of

molecules are reduced. In the given reaction two molecules are present on reactant side and two molecules are present on product side. So when volume is changed there will be no effect on the equilibrium position. b) 2NO 2 N 2 O 4 According to Le-Chatlier’s principle, when volume is reduced then the equilibrium will shift in a direction in which number of molecules are reduced. In the given reaction two molecules are present on reactant side and one molecule are present on product side. So when volume is reduced, the equilibrium will shift in forward direction and the yield of product is increased.

Chapter #8

27. What are acidic, basic and amphoteric substances? Give

one example of each substance. Acidic substance: According to Lowry-Bronsted concept, an acid is a proton donor. Example: CO 2 . It is a non-metal oxide which dissolves in water to form acid.

CO 2 (g) + H 2 O (l) → H 2 CO 3 (aq)

Basic substance: According to Lowry-Bronsted concept, a base is a proton acceptor. Example: Na 2 O (s) +H 2 O (l) → 2NaOH (aq) Amphoteric substance: These show properties of both acids and bases. Example: Aluminum oxide (Al 2 O 3 ) is an amphoteric substance as it reacts with both acidic and basic solutions:

(Basic) Al 2 O 3 (s) +6HCl (aq) → 2AlCl 3 (aq) +3H 2 O (l) (Acidic) Al 2 O 3 (s) +2NaOH (aq) → 2NaAlO 2 (aq) +H 2 O (l)

28. Elaborate with equations two compounds which are

amphoteric in nature. Amphoteric substances show properties of both acids and bases. Example 1: Aluminum oxide (Al 2 O 3 ) is amphoteric and it reacts with

both acidic and basic solutions (Basic) Al 2 O 3 (s) +6HCl (aq) → 2AlCl 3 (aq) +3H 2 O (l) (Acidic) Al 2 O 3 (s) +2NaOH (aq) → 2NaAlO 2 (aq) +H 2 O (l)

Example 2: Chromium trioxide is amphoteric since it reacts with both acids and bases (Basic) Cr 2 O 3 (s) +6HNO 3 (aq) → 2Cr (NO 3 ) 3 (aq) +3H 2 O (l) (Acidic) Cr 2 O 3 (s) +2KOH (aq) → 2K 3 CrO 3 (aq) +3H 2 O (l)

29. What is Bronsted – Lowry acid-base theory? Give

examples. J. Bronsted and T. Lowry independently define acids and bases as:

Acid: A Bronsted acid is a proton donor. Base: A Bronsted base is a proton acceptor. Examples:

- HCl donates a proton to water. So, HCl is Bronsted acid and water is a Bronsted base.

HCl (g) +H 2 O (l) → H 3 O + (aq) + Cl - (aq)

Acid Base Since water accepts a proton, it is a Bronsted base.

- NH 3 accepts a proton from water. Therefore, NH 3 is a Bronsted base and water is a Bronsted acid.

NH 3 (g) +H 2 O (l) → NH 4 + (aq) + OH - (aq)

Base Acid

30. What are conjugate acid-base pairs? Explain with

examples. Conjugate acid: It is a species which is formed as a result of acceptance of proton by a base. Conjugate base: It is a species which is left behind after donation of a proton from the acid. Every Bronsted acid has a conjugate base and vice versa. Example:

Ionization of HCl in water HCl (g) +H 2 O (l) → H 3 O + (aq) + Cl - (aq)
Acid
Conjugate
Base
Conjugate
Base
Acid

31. How preservatives are used in food products and allergic reactions in people?

 - A preservative is a substance that is added to products such as foods, to prevent decomposition by microbial growth or by chemical changes. - Most commonly used preservatives are Benzoates in bakery products Nitrates in meat products Sulphites in drinks etc. - The preservatives can cause severe allergic reactions in people. For example, sulphites can cause wheezing, chest tightness and coughing. Benzoates may cause urticarial, asthma etc.

32. Define Lewis acid and Lewis base. Give one example in

each case. G.N. Lewis, in 1932, defined acid-base as following. Base: A base is a substance that donates a pair of electrons Acid: And acid is a substance that can accept a pair of electrons Example 1: The hydroxide ion (OH - ) is a Lewis base because it donates a pair of electrons and the proton (H + ) is a Lewis acid because it accepts a pair of electrons. Example 2: Ammonia is a Lewis-base and boron tri-fluoride is a Lewis

acid 33. Classify each of the following as Bronsted acid or Bronsted base.

n) HCO 3 -1 It is a Bronsted base because it accepts a proton when dissolved in water. HCO 3 -1 +H 2 O → H 2 CO 3 + OH -

o) H Br It is a Bronsted acid because it donates a proton when dissolved in water.

H Br +H 2 O → H 3 O + + Br -

p) CH 3 COO -

It is a Bronsted base because it accepts a proton when dissolved in water. CH 3 COO - +H 2 O → CH 3 COOH + OH -

34. Explain gastric acidity and use of anti-acid drug.

The human stomach has naturally produced acidic liquid. It helps in digestion. However, excess stomach acid can cause severe problems. The most common is heartburn which causes a burning sensation near the heart. This excess acid is generally produced by eating spicy food. The excess acid is neutralized by anti-acid (antacid) drugs. Most commonly antacids are Al (OH) 3 and Mg (OH) 2 . These are insoluble bases and neutralize acid in the stomach. These are generally present in a single medicinal preparation.

35. Write briefly about the ionization of water.

Water undergoes self-ionization to a small extent. This reaction is called as auto-ionization of water. H 2 O + H 2 O → H 3 O + + OH - The equilibrium constant (K) for this equilibrium can be expressed by the following equation:

- Since water is a solvent, the concentration of water is in large excess therefore it remains constant. K [H 2 O] 2 = K w = [H 3 O + ] [OH - ] K w = [H + ] [OH - ]

- In pure water at 25°C, the concentration of H + and OH - are equal and found to be 1.0 x 10 -7 M each. Thus:

K = [1.0 x 10 -7 ] [1.0 x 10 -7 ] =1.0 x 10 -14

36. Define pH. What are the values for acidic, basic and neutral

solutions? The negative logarithm of H + ions concentration in (mold dm -3 ) is called pH. pH = - log [H + ] According to the pH concept the different types of solutions will show the following behaviors at 25°C. Acidic Solution: [H + ] > 1.0 x 10 -7 M, pH < 7.00 Basic Solution: [H + ] < 1.0 x 10 -7 M, pH < 7.00 Acidic Solution: [H + ] = 1.0 x 10 -7 M, pH = 7.00

37.

Define K a and pK a and its applications. K a : it is measure of the extent to which an acid is ionized or

dissociated at the equilibrium state. For any acid HX, it is given as

H X +H 2 O → H 3 O + + X -

pK a : It is negative logarithm of K a . PKa = - log (K a ) Applications:

- The K a values of different acids are used to compare their strengths. The greater the value of K a , the stronger the acid.

- The K a values are also used to determine the percentage ionization of an acid.

- PKa also measures the strength of acid.

- Smaller the value of pK a , stronger will be the acid. It is because smaller pK a means greater K a value.

38. Explain curdling of milk with lemon juice. Milk is composed of several components mainly proteins, fats and water. One specific milk protein is casein. The casein molecules float

in milk. Since they carry negative charges, therefore, they repel each other. However, when lemon juice is added to the milk the pH decreases and the casein molecules become neutralized. Now they don’t repel each other. Rather they start clumping together and milk becomes curdle. This occurs fast at warmer temperatures than at cold ones.

39. Define K b and pK b and its applications. K b : it is measure of the extent to which a base is ionized or dissociated at the equilibrium state. For any base B, it is given as

B +H 2 O → BH + + OH -

PK b : It is negative logarithm of K b . pK b = - log (K b ) Applications:

- The K b values of different bases are used to compare their strengths. The greater the value of K b , the stronger the base.

- The K b values are also used to determine the percentage ionization of a base.

- pK b also measures the strength of a base.

- Smaller the value of pK b , stronger will be the base. It is because smaller pK b means greater K b value.

40. What is an iodized salt? What is its use in practical life? Iodine is added as Nail or KI to table salt. Such salt is called iodized salt. This is done to provide iodine to the body for the proper function of thyroid gland. The diet with insufficient iodine leads to enlargement of the glad. This disease is called goiter.

41. What is the relationship between K a and K b ?

They are inversely proportional to each other. K a = K w /K b

Where,

K b = ionization constant of a base K w = ionization constant of water Hence for an acid and its conjugate base or for a base and its conjugate acid,

K a = ionization constant of an acid

- Stronger the acid, weaker is its conjugate base and vice versa

- Strong a base, weaker is its conjugate acid and vice versa

42. Calculate concentrations of ions of slightly soluble salts.

There are different methods to calculate the concentration of ions of slightly soluble salts in aqueous solutions. Titration is one of these methods. Example: Li 2 CO 3 is sparingly soluble salt. Its concentration in solution can be determined by titration with strong acid (e.g., HCl) using methyl orange as indicator. Li 2 CO 3 ionizes in aqueous solution as

Li 2 CO 3 2Li + + CO 3 2- This equation shows that concentration of CO 3 2- will be equal to that of Li 2 CO 3 while the concentration of 2Li + will be twice of it.

43. Give two examples of butter solution.

- A buffer solution may contain a weak acid and the salt of that acid with a strong base

e.g.

Such solutions give acidic buffers with pH less than 7

CH 3 COOH + CH 3 COONa

- A buffer solution may contain a weak base and its salt with a strong acid

e.g.

Such solutions will give basic buffers with pH more than 7

NH 4 OH +NH 4 Cl

- Acidic Salts: These are salts of strong acids and weak bases. They hydrolyze producing acidic solutions (pH < 7) Examples: CuSO 4 , NH 4 Cl, NH 4 NO 3 etc.

- Basic Salts: These are salts of weak acids and strong bases. They hydrolyze producing basic solutions (pH > 7) Examples: CH 3 COONa, NaCN, Na 2 S etc.

45. Use the concept of hydrolysis to explain why aqueous solutions of some salts are acidic or basic.

- Acidic Salts: These are salts of strong acids and weak bases. According to Bronsted-Lowery concept, cat-ions of weak bases are strong conjugate acids. They hydrolyze producing acidic solutions. CuSO 4 + H 2 O → Cu (OH) 2 +H 2 SO 4

(Weak base)

(Strong Acid)

- Basic Salts: These are salts of weak acids and strong bases. According to Bronsted-Lowery concept, an-ions of weak acids are strong conjugate bases .They hydrolyze producing basic solutions. CH 3 COONa + H 2 O → CH 3 COOH + NaOH (Weak Acid)(Strong base)

46. What is hydrolysis? Discuss in details, the behavior of each of the following salts in the aqueous solutions. The reaction of cat-ions and an-ions of salts with water is called hydrolysis. Explanation:

When a salt (MX) is dissolved in water, it splits up into its M + and X - ions. These ions may react with water and give following reactions. M + + H – OH MOH + H +

X - + H – OH HX + OH -

Thus,

- When a cat-ion reacts with water, then H + ions are produced and the solution becomes acidic

- When an an-ion reacts with water, then OH - ions are produced and the solution becomes basic Hydrolysis of some salts:

d)

K 2 CO 3 is a salt of strong base and weak acid. In water K 2 CO 3 ionizes to give carbonate anion. K 2 CO 3 2K + + CO 3 2- CO 3 2- is a strong conjugate base of a weak acid H 2 CO 3 . According to Bronsted-Lowery concept, such anions react with water producing basic solutions. Thus, CO 3 2- + 2H 2 O H 2 CO 3 + 2OH - Overall reactions is K 2 CO 3 + 2H 2 O 2KOH + 2 H 2 CO 3 Hence aqueous solution of K 2 CO 3 is basic in nature.

NH 4 Cl

NH 4 Cl is a salt of strong acid and a weak base. In water, it ionizes to give ammonium cat-ion. NH 4 Cl NH 4 + +H + NH 4 + is a strong conjugate acid of a weak base NH 4 OH. According to Bronsted-Lowery concept, such cat-ions react with water producing acidic solutions. Thus,

NH 4 + + H 2 O NH 4 OH + H + Overall reaction is NH 4 Cl + H 2 O NH 4 OH + HCl Hence aqueous solution of NH 4 Cl is acidic in nature.

e) NaNO NaNO 3 is a salt of a strong base and a strong acid. In water NaNO 3 ionizes as

3

NaNO 3 Na + + NO 3 - Since, both cat-ions and an-ions are derived from strong base and strong acid respectively. Therefore, according to Bronsted-Lowery concept, they do not hydrolyze with water. Hence aqueous solution of NaNO 3 is neutral in nature.

47. Write a unique property of a buffer solution. What types of acids are required to prepare buffer solutions? Name two such acids.

- The unique property of a buffer solution is that its pH does not change significantly when a small amount of acid or base is added to it.

It is because the buffer solution has the ability to neutralize either added acid or a base. E.g. consider a CH 3 COOH/ CH 3 COONa buffer If a base is added to the buffer solution, the hydroxide ions (OH - ) will be neutralized by the acid (acetic acid) in the buffer. CH 3 COOH + OH - → CH 3 COO - + H 2 O If an acid is added (say HCl), the protons (H + ions) produced will be consumed by the base (acetate ions) present in the buffer:

CH 3 COO - + H + → CH 3 COOH

- Weak acids are used to prepare buffer solutions Examples: CH 3 COOH, H 2 CO 3 , H 3 PO 4 etc.

Chapter #9

5. Explain the cooling effect experienced when few drops of

ethanol are poured on palm, given that:

C2H5OH(I) -> C2H5OH(g)

The given equation shows that the conversion of liquid ethanol to gaseous ethane is an endothermic process. When few drops of ethanol are put on a palm, the molecule ethanol absorb energy from the palm and evaporate. Due to hydrogen bonding, ethane has high heat of vaporization (42.2 kJ/mole). Therefore, its molecules absorb heat from body to evaporate. Thus, temperature of palm decreases and it cause cooling effect.

ΔH0 = 42.2kJmole-1

6. Explain the significance of the rate determining step on the overall rate of multi-step reaction. The slowest step of a reaction mechanism which determines the overall rate of reaction is called as rate determining step. Significance:

The rate of the slowest step determines the overall rate of reaction. The activation energy is highest for the rate-determining step. In a multi-step reaction, no reaction can proceed faster than the determining step. The number of molecules participating in the rate determining step giving order of reaction.

The rate determining step help us to determine the mechanism of a chain reaction. Example For reaction N02 (g) + CO (g) -> NO (g) + C02 (g)

The rate equation is Rate =k [NO 2 ] 2

The rate equation gives us following information. The reaction is second order with respect to N02 and zero with respective CO. Therefore it is independent of the concentration of CO. Two molecules of N02 are involved in the rate-determining step give order of reaction. Reaction must proceed in more than one step. The proposed mechanism for the reaction is as follows. Slow NO3 (g) + NO (g) NO(g) + CO2(g) Fast

.

,

 Step I N02 (g) + .NO2 (g) Step II NO3 (g) + CO (g)

The first step is the rate determining step. Species NO:, that does not

appear in the overall reaction is called reaction intermediate. This example proves a balanced chemical equation may not give any information about the reaction mechanism.

48. What is the effect of a catalyst on the following?

a) The rate of reaction

A catalyst provides a new mechanism for the reaction with low energy activation. Thus catalyst increases the rate of reaction by decreasing its energy activation.

b) The energy of activation The catalyst provides a new mechanism for the reaction with low energy activation. Thus catalyst increases the rate of reaction by decreasing its energy activation.

49. The reaction of alkyl halide, R-X with water is as follows

R-X+H 2 O →R-OH+HX

If the reaction were a single step process, what would you predict the rate law to be? Solution:

Since the reaction is single step process therefore the single step is the rate determining step. In this step, one molecule of R-X and one molecule H 2 O are reacting together, so the reaction is first order in both R-X and H 2 O. Thus the rate equation is Rate = k[R-X] [H 2 O] So the order of the reaction will be 1+1=2 (second order) However in such reactions water is generally taken as solvent and therefore, it is present in large excess. So the rate will not depend upon its concentration. Thus the rate equation will become Rate=k[R-X] Now the reaction becomes first order. However such reactions in which two molecules are involved but rate depends upon only molecule are generally called pseudo first order reactions.

50. The reaction of a compound A and B to give C and D was found to be second order in A and second order overall. Write rate expression for the reaction. The rate expression will be:

Rate=k [A] 2 [B] 0 =k [A] 2 The overall order of reaction =2+0=2. So reaction is second order. The rate equation shows that rate depends upon concentration of only and it is independent of concentration of B.

51. Explain why?

k) A very small amount of catalyst may prove sufficient to carry out a reaction. A catalyst is not consumed during a reaction. It is recycled again and again. Thus only a small amount of catalyst is sufficient to carry out a reaction.

l) The reaction rate decreases every moment. According to the law of mass action, rate of a chemical reaction is disproportional to the concentration of reactants. When the reaction starts the concentration of reactants is high, therefore, rate of reaction is fast. As the concentration of reactants is decreases with time, the rate of reaction is also decreased. Thus

the reaction rate decreases every moment and becomes very slow at the end of reaction. m)The unit of rate constant of a second order reaction is dm 3 mole -1 s -1 For a second order reaction, the rate of reaction is directly

proportional to the concentration of two reactants e.g., A and B

I.e.

Rate=k [A] [B] Where ‘k’ is the rate constant.

Or Since the units of rate =mold dm -3 sec -1 , and concentration of A and B are expressed in mold m -3 , therefore units of k will be

52. From the equation proposed for the gas phase reaction of NO 2 with CO, predict the rate law for the reaction. What is stoichiometric equation for the reaction? Identify reaction intermediate and write rate law for the reaction

 NO 2 +NO 2 →NO 3 +NO NO 3 +CO→NO 2 +CO 2

The slow step is rate determining step. Since two molecules of NO 2 are involved in the rate determining step, therefore rate equation is

Rate=k [NO 2 ] 2 Stoichiometric Equation:

The stoichiometric equation can be obtained by adding the two steps of the reaction. The resulting equation is overall reaction.

 NO 2 +NO 2 →NO +CO→NO 2 3 +NO (slow) NO 3 +CO 2 (fast)

NO 2 +CO→ NO+CO 2

(overall

reaction)

53. Predict the rate law for the oxidation of the iodide ion by hypo chloride I - (aq) +ClO - (aq) → If the reaction proceeds by the following mechanism ClO - +H 2 O→HOCl+OH - (slow step)

I - +HOCl→HOI+Cl HOI+OH - →IO - +H 2

-

O

(fast step)

(fast step)

The rate law depends upon the slow step. In slow step, one ClO -1 ion and one H 2 O molecule are participating, therefore the rate law is Rate=k [ClO -1 ] [H 2 O] The overall order of reaction=1+1=2. Hence it is a second order reaction.

Chapter #10

54. When cooking, what effect does adding salt to water have

on the time required to boil food? By adding salt the vapor pressure of water is decreased. As a result

its boiling point is increased. Hence, the water boiling at temperature will have more heat and thus boiling food will take less time.

55. Define the term water of hydration.

Water of hydration: the water molecules that combine with compounds as they are crystallized from aqueous solution are called water of crystallization or water of hydration.

Hydrate: A crystalline substance which has associated with each formula unit a definite content of water molecules is called a hydrate.

Examples: i) CuSO 4 .5H 2 O

ii) BaCl 2 .2H 2 O

56. Define the term colligative.

iii) (COOH) 2 .2H 2 O

The properties of solutions depend only on number of solute particles

and not on their nature. These properties are called as colligative properties. Examples:

- Lowering of vapor pressure

- Elevation of boiling point

- Depression of freezing point

- Osmotic pressure

57. Define hydrophilic and hydrophobic molecules Molecules that are miscible with water are known as hydrophilic molecules. Such molecules can form hydrogen bond with water molecules. Example: methanol, acetone, acetic acid etc. Molecules that do not dissolve in water are known as hydrophobic molecules. Example: organic fats and oils.

58.

Explain the phenomenon freezing in a mixture of ice and

salt. The temperature in which liquid and solid phases are in equilibrium and therefore have same vapor pressure is called the freezing point of the liquid. When salt is added to ice, the vapor pressure of solution is decreased. The solution will freeze at a temperature at which vapor pressure of both solution and solvent are the same. It means solution will freeze at lower temperature than that of the pure solvent. Thus freezing point of water is depressed and now temperature of the mixture of ice and salt goes below zero degrees. Thus addition of a non-volatile solute causes a depression in freezing point.

59. Explain how solute particles may alter the colligative properties.

- When non-volatile solute is dissolved in a solvent, the escaping tendency of solvent molecules from the surface of the solution decreases. Thus the vapor pressure is lowered.

- Since a solution boils at a temperature at which its vapor pressure becomes equal to the atmospheric pressure, the solution must be heated more than solvent to reach its boiling point. Hence the boiling point of solution is increased.

- Similarly, a solution freezes at a temperature at which vapor pressure of both solution and solid solvent are the same. It means solution will freeze at a lower temperature than that of pure solvent. Hence freezing point of solution is depressed.

- Moreover, the magnitude of colligative properties increases with increase in number of particles i.e. when concentration of solute is increased.

60. Compare molar and molal solutions.

- In one molal solution, one mole of solute is dissolved in 1kg of solvent. In one molar solution, one mole of solute is dissolved in 1dm 3 of solution.

- One molal solution of any substance is diluter than its one molar solution. Since one molal solution has greater quantity of solvent.

- The value of molality does not change with temperature but molarity changes. It is because molar solutions are based upon

volume, which changes with temperature, and hence molarity changes. But molal solution are based upon mass which is not changed with temperature.

61. Explain the following

b) Molality is independent of temperature but molarity depends on it. The value of molality does not change with temperature but molarity changes. It is because molar solutions are based upon volume, which changes with temperature, and hence molarity changes. But molal solution are based upon mass which is not changed with temperature.

c) One molal solution of glucose in water is dilute as compared to one molar solution of glucose, but the number of particles of solute is same. One molal aqueous solution of glucose is dilute as compared to its one molar solution because in one molal solution 1kg of water (i.e. 1dm 3 ) is present. In one molar solution, some volume is occupied by the solute particles. Since total volume is 1dm 3 , therefore amount of water will be less than 1dm 3 . However, both one molal and one molar solutions contain one mole of solvent particles. Thus both solutions contain same number of particles.

d) The total volume of solution by mixing 50 cm 3 of ethanol and 50 cm 3 of water may not be equal to 100 cm 3 . Why? During ideal solution formation volume is not changed since intermolecular forces remain same. However, alcohol and water develop forces of attraction for each other. These forces are stronger than water-water and ethanol-ethanol forces. So molecules of ethanol and water come closer together and volume of solution is decreased. Hence total volume of solution prepared will be less than 100cm 3 .

e) NaCl and NaNO 3 are used to lower the melting point of ice. When NaCl or NaNO 3 is added to H 2 O, its vapor pressure is lowered. Due to lowering of vapor pressure, solution freezes below the freezing point of H 2 O. Hence this mixture is used as freezing mixture e.g. in an ice-cream machine.

f) In summer the antifreeze solutions protect the radiator from boiling over. Antifreeze solution consists of solution of ethylene glycol in water. Since ethylene and glycol is less volatile, therefore vapor pressure of the solution is lowered and boiling point is increased. In summer due to large heat in engine, water may boil over in the radiator. However due to lower vapor pressure of solution, it required much greater heat to boil. Hence mixture prevents water from boiling over.

g) One molal and two molal solutions of urea boil at different temperatures. When a non-volatile solute is dissolved in a solvent, the vapor pressure of solution is decreased. So the boiling point is increased. Elevation of boiling point is colligative property which depends upon number of particles. Generally the magnitude of colligative properties increases with increase in number of particles. In molal urea solution, it contains one mole of urea particles while two molal urea solution contains two moles urea particles. Hence two molal urea solution boils at higher temperature than one molal urea solution.

h) Relative lowering of vapor pressure is independent of the temperature. According to Raoult’s law Relative lowering of vapor pressure is equal to the mole fraction of solute. I.e. ΔP/P 0 = x 2

62. Caffeine is about 10 times as soluble in hot water as in cold

water. Is ΔH soln of caffeine in water positive or negative? If ΔH o soln is positive, then the solubility of a solute increases with increase in temperature. Thus caffeine has positive ΔH o soln (endothermic). Explanation: according to Le-Chatlier’s principle, heat is taken as reactant in endothermic process. Therefore, an increase in

temperature will shift the solubility equilibrium in forward direction in order to absorb the added heat. Thus solubility of caffeine increases.

63. PCl 5 can react with itself in a reversible reaction to form a salt that contains the PCl 4 + and PCl 6 - ions

2PCL 5 PCl 4 + + PCl 6 - The extent to which this reaction occurs depends on the solvent in which it is run. Predict weather a nonpolar solvent such as

CCl 4 favors the product or the reactants of this reaction. Predict what would happen to this reaction if we use a polar solvent. Solubility principle is “like dissolves like”. PCl 5 is a nonpolar species, while PCl 4 + and PCl 6 - are polar ions. Thus a nonpolar solvent like CCl 4 will better dissolve PCl 5 than others. Since polar water molecules can attract the polar ionic species, therefore, it will better dissolve ionic species, PCL 4 + and PCl 6 - . So in a nonpolar solvent the equilibrium will be shifted towards reactants side. While in a polar solvent, the equilibrium will be shifted towards product side.

64. Water and carbon tetrachloride are not missile. When mixed they form two layers. If an aqueous solution of I 2 Iodine is shaken with CCl 4 , the iodine is extracted into the CCl 4 layer. Explain this behavior on the basis of your knowledge of intermolecular forces.

Solubility principle is “like dissolves like”. I 2 is nonpolar so it will better dissolve in nonpolar solvents like CCl 4 . It does not readily dissolves in polar solvents like water. Thus when an aqueous solution of I 2 is shaken with CCl 4 , it enters into the CCl 4 layer because it can better form intermolecular forces with the nonpolar CCl 4 molecules.

65. A cucumber placed in concentrated brine (concentrated NaCl solution in water) shrivels into a pickle. Explain. This is due to process of osmosis. In this process solvent molecules move a semi-permeable membrane from less concentrated to more concentrated solution. The skin of cucumber acts a semi-permeable membrane. The concentration of NaCl is less inside cucumber and more in brine solution. So when it is placed in concentrated solution

of brine, water flower out of its cell into the brine solution. Thus it shrinks into a pickle.

66. Two beakers are placed in a sealed bell jar. One beaker

contains water and the other contained concentrated glucose

solution. With time volume of water decreases and solution volume increases. Explain why.

A bell jar is sealed laboratory equipment which contain vacuum in it.

Let one beaker of water and other of glucose solution is placed in it. The vapor pressure of water (pure solvent) is greater than that of glucose solution. Therefore, the water vapors are transferred from high pressure are to the low pressure area. Thus volume of water decreases and that of solution increases.

67. Consider two aqueous solutions. One is sucrose and the

other of glucose. Both of these solutions boil at 101.52°C. List

some common properties of these solutions. Both these solutions have

- Same number of particles

- Same vapor pressure

- Same freezing point

- Same boiling point

- Same molality Chapter #12

68. Explain why?

iv) Reduction of 1 mole of each Zn +2 and Ag + require different Faradays of electricity. Faraday is the charge carried by 1 mole of elections. For reduction of Zn +2 ions two moles of electrons are needed i.e. Zn +2 +2e - →Zn. Thus it requires two Faradays charge of electricity. On the other hand, for the reduction of Ag + ions one mole of electrons is needed i.e. Ag + +1e - →Ag. Thus, it requires one Faraday charge of electricity.

v) It is not possible to measure the potential of an isolated half-cell. It is because one half-cell cannot occur without simultaneous reaction in another half-cell. However, relative half-cell potential (electrode potential) can be determined with reference to some standard e.g. standard hydrogen electrode.

vi) The life of a dry cell is shorter than that of an alkaline dry cell. In both cells, Zn acts as anode. However, in alkaline dry cell, a moist past of KOH is used as electrolyte. Therefore the alkaline

dry cell lasts longer because the zinc anode corrodes les rapidly in basic conditions.

69. Explain the following with reasons.

a) The oxidation potential of Zn is 0.76V and its reduction potential is -0.76V According to the law of conservation of energy, energy can neither be created no destroyed. Therefore, if standard oxidation potential of Zn is 0.76V, then its potential for reverse process, i.e. standard reduction potential will also be same but with positive sign. Thus Zn→Zn +2 +2e - E 0 ox =0.76 Zn +2 +2e - → Zn E 0 red =-0.76

b) A salt bridge maintains the electrical neutrality in the cell. In a Galvanic cell, the solutions are connected with a tube (salt bridge) filled with a solution of an electrolyte such as KCl, KNO 3 or Na 2 SO 4 . The salt bridge allows the movement of ions from one solution to the other without mixing of the two solutions. Thus it maintains electrical neutrality in each half-cell.

c) Na and K can display hydrogen from acids but Cu and Pt cannot. Greater the value of reduction potential. Lesser is the ability to loose electron to form positive ion. Hence weaker is its tendency to displace H 2 .

- Metals like Pt and Cu have high positive value of reduction potential. They are present below H 2 in activity series. Thus there do not displace H 2 .

- Metals like Na and K have negative values of reduction potential. They are present above H 2 in the activity series. Thus these can displace H 2 . 2Na+2HCl→2NaCl+H 2 2K+2HCl→2KCl+H 2

d) Lead storage battery is chargeable battery. During discharging of lead storage battery, H 2 SO 4 is used up, its density decreases and both the electrodes are completely covered with PbSO 4 . Thus the battery stops to deliver current. This battery can be recharged by connecting its anode to the negative terminal of direct current and the cathode to the positive terminal of the direct current.

Reverse chemical reactions occur at anode and cathode of the battery. Thus deposition of Pb on anode and PbO 2 on cathode takes place. The reactions of recharging of battery are as follows. At cathode

PbSO 4 (s) +2e - →Pb (s) +SO 4 -2 (aq)

At anode

PbSO 4 (s) +2H 2 O→PbO 2 (s) + SO 4 -2 (aq) +4H + (aq) +2e -

Net reaction

2 PbSO 4 (s) + 2H 2 O→ Pb (s) +PbO 2 (s) + 4H + (aq) +2SO 4 -2 (aq)

e) Zn plating saves Fe from corrosion. It is because Zn is more active metal than iron. Any oxidation that occurs dissolves Zn rather than Fe. Thus Zn acts sacrificial coating on Fe. This is also known as sacrificial corrosion. Fe +2 +2e - Fe E 0 =-0.44V Zn +2 +2e - Zn E 0 =-0.76V

70. What kind of reaction occurs at the negative terminal of the

galvanic cell? The species which has greater tendency to lose electron will form the negative terminal of the Galvanic cell. Thus, the negative terminal of cell will act as anode an oxidation reaction occurs at this terminal.

E.g., in Zn-Cu cell, Zn has greater tendency to lose electrons than Cu. Therefore, Zn electrode gets negative charge relative to Cu electrode and electrons flows from Zn electrode to Cu electrode. I.e. Zn (s) →Zn +2 (aq) +2e -

71. Corrosion is often accelerated where the coating on the body of a car has begun to crack. Explain. To prevent corrosion, the body of a car is painted. Thus it does not come in contact with oxygen and moisture and therefore, corrosion is greatly slowed down. However, if the coating is damaged then metal comes in contact with the atmospheric oxygen and other agents electrochemical reactions starts.

Reduction half reaction:

Oxidation half reaction:

Thus Fe is oxidized by oxygen to Fe +2 which is further oxidized Fe +3 . The Fe +3 form various insoluble hydrated oxides known as rut and

corrosion is accelerated.

O 2 (g) +H + (aq) +e - →2H 2 O (l) Fe→Fe +2 +e - (oxidation reaction)

72. If a chromium steel bicycle handlebar is scratched,

exposing steel, will chromium or steel corrode? Case I: Chromium Coating (Chrome coating): In this case a layer of chromium is coated on metal surface. Chromium is higher in activity series than iron. So when a handlebar is scratched exposing steel, it is the chromium which corrodes. Cr→Cr 3+ +3e - Case II: Stainless Steel: In this chromium is mixed with iron to produce an alloy. The chromium is higher in activity series than iron. So if iron and chromium are exposed to oxygen, it is the chromium that reacts with atmospheric oxygen to form a very thin layer of chromium (III) oxide. This layer protects further corrosion. The oxide layer is so thin that the metal can still shine through it. The protection is permanent. It is because even if the layer is scratched, the chromium in the steel immediately reacts with oxygen to reform the protective layer.

73. Justify the photosynthesis in plants as redox reaction.

Chlorophyll 6CO 2 +6H 2 O

C 6 H 12 O 6 +6O 2 The photosynthesis reaction:

 2(- - 6(- +4 2) 2(+1) 2 chlorophyll 6(0) 12(+1) 2) 0 6C O 2 +6H 2 O C 6 H 12 O 6 +6O 2

In this reaction

- The O atom changes its oxidation state from -2 in H 2 O to zero in O 2. This is due to loss of electrons. This is oxidation. Thus H 2 O is oxidized.

- The C atom changes its oxidation state from +4 in CO 2 to zero in C 6 H 12 O. This is due to gain of electrons. This is reduction. Thus CO 2 is reduced. Thus photosynthesis involves transfer of electrons. Hence, it is a redox reaction.

74. Standard electrode potentials of three electrodes are in the following order

Identify anode in the working cell, when

a) Electrodes A and C are joined in series

b) Electrodes B and C are joined in series

c) Electrodes A and B are joined in series

Standard electrode potentials are actually standard reduction potential. So, any electrode with higher standard electrode potential

will act as cathode and the other with relatively lower standard electrode potential will act as anode.

d) Electrodes A and C are joined in series

Since, It means standard electrode potential of electrode B is less than that of both A and C. therefore, electrode B can act as anode with

both electrodes A and C. however, the relationship between electrode potential of electrode A and C is not given, therefore anode and cathode cannot be identified.

e) Electrodes B and C are joined in series Since, Therefore, electrode B will act as anode and electrode C will act as cathode.

f) Electrodes A and B are joined in series Since, Therefore, electrode B will act as anode and electrode A will act as cathode.