Question
A less obvious example of electron transfer is realised when hydrogen combines with oxygen to form water by the reaction:

$2\text{H}_2(\text{g}) + \text{O}_2 (\text{g}) → 2\text{H}_2\text{O} (\text{l})$

Though not simple in its approach, yet we can visualise the H atom as going from a Neutral (zero) state in H2 to a positive state in H2O, the O atom goes from a zero state in O2 To a dinegative state in H2O. It is assumed that There is an electron transfer from H to O and Consequently H2 is oxidised and O2 is reduced. However, as we shall see later, the charge Transfer is only partial and is perhaps better Described as an electron shift rather than a Complete loss of electron by H and gain by O. Two examples of this class Of the reactions are:

$\text{H}_2 (\text{s}) + \text{Cl}_2(\text{g}) → 2\text{HCl} (\text{g})$ And,

$\text{CH}_4 (\text{g}) + 4\text{Cl}_2 (\text{g}) → \text{CCl}_4(\text{l}) + 4\text{HCl (g)}$

In order to keep track of electron shifts in Chemical reactions involving formation of Covalent compounds, a more practical method Of using oxidation number has been Developed. In this method, it is always Assumed that there is a complete transfer of Electron from a less electronegative atom to a More electonegative atom. For example, we Rewrite equations to show Charge on each of the atoms forming part of The reaction:

It may be emphasised that the assumption Of electron transfer is made for book-keeping Purpose only and it will become obvious at a Later stage in this unit that it leads to the simple Description of redox reactions. Oxidation number denotes the Oxidation state of an element in a Compound ascertained according to a set Of rules formulated on the basis that electron pair in a covalent bond belongs Entirely to more electronegative element.  It is not always possible to remember or Make out easily in a compound/ ion, which Element is more electronegative than the other. Therefore, a set of rules has been formulated To determine the oxidation number of an Element in a compound/ ion. We may at this stage, state the rules for the Calculation of oxidation number. These rules are:

1.) In elements, in the free or the uncombined State, each atom bears an oxidation Number of zero. Evidently each atom in H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has the Oxidation number zero.

2.) For ions composed of only one atom, the Oxidation number is equal to the charge On the ion. Thus Na+ Ion has an oxidation Number of +1, Mg2+ ion +2 , Fe3+ ion, +3, Cl –  Ion, –1, O– ion, –2; and so on. In their Compounds all alkali metals have Oxidation number of +1, and all alkaline Earth metals have an oxidation number of +2. Aluminium is regarded to have an Oxidation number of +3 in all its Compounds.

3.) The oxidation number of oxygen in most Compounds is –2. However, we come across Two kinds of exceptions here. One arises In the case of peroxides and superoxides, The compounds of oxygen in which oxygen Atoms are directly linked to each other. While in peroxides (e.g., H2 O2, Na2 O2), each Oxygen atom is assigned an oxidation Number of –1, in superoxides (e.g., K O2, Rb O2) each oxygen atom is assigned an Oxidation number of –(½). The second Exception appears rarely, i.e. when oxygen Is bonded to fluorine. In such compounds e.g., oxygen difluoride (OF2) and dioxygen difluoride (O2F2), the oxygen is assigned an oxidation number of +2 and +1, respectively. The number assigned to oxygen will depend upon the bonding state of oxygen but this number would now be a positive figure only.

4.) The oxidation number of hydrogen is +1, Except when it is bonded to metals in binary Compounds (that is compounds containing Two elements). For example, in LiH, NaH, And Ca H2, its oxidation number is –1.

5.) In all its compounds, fluorine has an Oxidation number of –1. Other halogens (Cl, Br, and I) also have an oxidation number Of –1, when they occur as halide ions in Their compounds. Chlorine, bromine and Iodine when combined with oxygen, for Example in oxoacids and oxoanions, have Positive oxidation numbers.

6.) The algebraic sum of the oxidation number Of all the atoms in a compound must be Zero. In polyatomic ion, the algebraic sum Of all the oxidation numbers of atoms of The ion must equal the charge on the ion. Thus, the sum of oxidation number of three Oxygen atoms and one carbon atom in the Carbonate ion, (CO3) 2– must equal –2.

A term that is often used interchangeably With the oxidation number is the oxidation State. Thus in CO2, the oxidation state of Carbon is +4, that is also its oxidation number And similarly the oxidation state as well as Oxidation number of oxygen is – 2. This implies That the oxidation number denotes the Oxidation state of an element in a compound.

The oxidation number/state of a metal in a Compound is sometimes presented according To the notation given by German chemist, Alfred Stock. It is popularly known as Stock Notation. According to this, the oxidation Number is expressed by putting a Roman Numeral representing the oxidation number In parenthesis after the symbol of the metal in The molecular formula. Thus aurous chloride And auric chloride are written as Au(I)Cl and Au(III)Cl3. Similarly, stannous chloride and Stannic chloride are written as Sn(II) Cl2 and Sn(IV)Cl4. This change in oxidation number Implies change in oxidation state, which in Turn helps to identify whether the species is Present in oxidised form or reduced form. Thus, Hg2(I) Cl2 is the reduced form of Hg(II) Cl2.

  1. H atom goes from a … state in H2 to a positive state in H2O in water formation.
  1. Neutral
  2. Positive
  3. Negative
  4. All the above
  1. In oxidation number method, there is a complete transfer of electron from a …. electronegative atom to a … electonegative atom.
  1. more, less
  2. less, more
  3. non, more
  4. non, less
  1. Oxidation number of Mg+ ion is:
  1. -2
  2. -1
  3. +2
  4. +1
  1. In Na2O2 each oxygen atom is assigned an oxidation number of …
  1. +1
  2. -2
  3. +2
  4. -1
  1. The algebraic sum of the oxidation number of all the atoms in a compound must be…
  1. 0
  2. 1
  3. 2
  4. -2

 

Answer

  1. (a) Neutral
  2. (b) less , more
  3. (c) +2
  4. (d) -1
  5. (a) 0

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IUPAC (International Union of Pure and Applied Chemistry) system of nomenclature. Common names are useful and in many cases indispensable, particularly when the alternative systematic names are lengthy and complicated. A systematic name of an organic compound is generally derived by identifying the parent hydrocarbon and the functional group(s) attached to it. By using prefixes and suffixes, the parent name can be modified to obtain the actual name. In a branched-chain compound, small chains of carbon atoms are attached at one or more carbon atoms of the parent chain. The small carbon chains (branches) are called alkyl groups. An alkyl group is derived from a saturated hydrocarbon by removing a hydrogen atom from carbon. Abbreviations are used for some alkyl groups. For example, methyl is abbreviated as Me, ethyl as Et, propyl as Pr and butyl as Bu.

1. Draw the structure of 3-Ethyl-4,4-dimethylheptane. (1)
2. How is the numbering in branched chain hydrocarbon done? (1)
3. Derive the structure of 2-Chlorohexane. (2)
OR
Why $CH _4$ after becoming- $CH _3$ called a methyl group? (2)
Read the passage given below and answer the following questions from (i) to (v).
When a liquid evaporates in a closed container, molecules with relatively higher kinetic energy escape the liquid surface into the vapour phase and number of liquid molecules from the vapour phase strike the liquid surface and are retained in the liquid phase. It gives rise to a constant vapour pressure because of an equilibrium in which the number of molecules leaving the liquid equals the number returning to liquid from the vapour. We say that the system has reached equilibrium state at this stage. However, this is not static equilibrium and there is a lot of activity at the boundary between the liquid and the vapour. Thus, at equilibrium, the rate of evaporation is equal to the rate of condensation. It may be represented by
$\text{H}_2\text{O}_{(\text{l})}\rightleftharpoons\text{H}_2\text{O}_{(\text{vap})}$
The double half arrows indicate that the processes in both the directions are going on simultaneously. The mixture of reactants and products in the equilibrium state is called an equilibrium mixture.
Equilibrium can be established for both physical processes and chemical reactions. The reaction may be fast or slow depending on the experimental conditions and the nature of the reactants. When the reactants in a closed vessel at a particular temperature react to give products, the concentrations of the reactants keep on decreasing, while those of products keep on increasing for some time after which there is no change in the concentrations of either of the reactants or products. This stage of the system is the dynamic equilibrium
The chemical equilibrium may be classified in three groups.
  1. The reactions that proceed nearly to completion and only negligible concentrations of the reactants are left. In some cases, it may not be even possible to detect these experimentally.
  2. The reactions in which only small amounts of products are formed and most of the reactants remain unchanged at equilibrium stage.
  3. The reactions in which the concentrations of the reactants and products are comparable, when the system is in equilibrium.
The equilibrium involving ions in aqueous solutions which is called as ionic equilibrium.
Solid-Liquid Equilibrium Ice and water kept in a perfectly insulated thermos flask (no exchange of heat between its contents and the surroundings) at 273K and the atmospheric pressure are in equilibrium state and the system shows interesting characteristic features. We observe that the mass of ice and water do not change with time and the temperature remains constant. However, the equilibrium is not static. The intense activity can be noticed at the boundary between ice and water. Molecules from the liquid water collide against ice and adhere to it and some molecules of ice escape into liquid phase. There is no change of mass of ice and water, as the rates of transfer of molecules from ice into water and of reverse transfer from water into ice are equal at atmospheric pressure and 273 K. It is obvious that ice and water are in equilibrium only at particular temperature and pressure. For any pure substance at atmospheric pressure, the temperature at which the solid and liquid phases are at equilibrium is called the normal melting point or normal freezing point of the substance. The system here is in dynamic equilibrium and we can infer the following:
  1. Both the opposing processes occur simultaneously.
  2. Both the processes occur at the same rate so that the amount of ice and water remains constant.
Solid – Vapour Equilibrium Let us now consider the systems where solids sublime to vapour phase. If we place solid iodine in a closed vessel, after sometime the vessel gets filled up with violet vapour and the intensity of colour increases with time. After certain time the intensity of colour becomes constant and at this stage equilibrium is attained. Hence solid iodine sublimes to give iodine vapour and the iodine vapour condenses to give solid iodine. The equilibrium can be represented as,
$\text{l}_2(\text{solid})\rightleftharpoons\text{l}_2(\text{vapour})$
Other examples showing this kind of equilibrium are,
$\text{Camphor}_{(\text{solid})}\rightleftharpoons\text{Camphor}_{(\text{vapour})}$
$\text{NH}_4\text{CI}_{(\text{solid})}\rightleftharpoons\text{NH}_4\text{CI}_{(\text{vapour})}$
The equilibrium Involving Dissolution of Solid in Liquids Only a limited amount of salt or sugar can dissolves in a given amount of water at room temperature. If we make a thick sugar syrup solution by dissolving sugar at a higher temperature, sugar crystals separate out if we cool the syrup to the room temperature. We call it a saturated solution when no more of solute can be dissolved in it at a given temperature. The concentration of the solute in a saturated solution depends upon the temperature. In a saturated solution, a dynamic equilibrium exits between the solute molecules in the solid state and in the solution: Sugar (solution) Sugar (solid), and the rate of dissolution of sugar = rate of crystallisation of sugar. Equality of the two rates and dynamic nature of equilibrium has been confirmed with the help of radioactive sugar. If we drop some radioactive sugar into saturated solution of non-radioactive sugar, then after some time radioactivity is observed both in the solution and in the solid sugar. Initially there were no radioactive sugar molecules in the solution but due to dynamic nature of equilibrium, there is exchange between the radioactive and non-radioactive sugar molecules between the two phases. The ratio of the radioactive to non- radioactive molecules in the solution increases till it attains a constant value.
  1. Which of the following symbol represents equilibrium.
  1. $\rightleftharpoons$
  2. $\leftrightarrows$
  3. $\nLeftrightarrow$
  4. $\uparrow\downarrow$
  1. When there is no change in the concentrations of either of the reactants or products, this stage of the system is the …
  1. Static equilibrium
  2. Dynamic equilibrium
  3. Physical equilibrium
  4. Chemical equilibrium
  1. A … solution means no more of solute can be dissolved in it at a given temperature.
  1. Unsaturated
  2. Supersaturated
  3. Saturated
  4. None of these.
  1. The equilibrium involving ions in aqueous solutions which is called as …
  1. Static equilibrium
  2. Dynamic equilibrium
  3. Physical equilibrium
  4. Ionic equilibrium
  1. The concentration of the solute in a saturated solution depends upon the …
  1. Solvent
  2. Pressure
  3. Temperature
  4. System

Read the passage given below and answer the following questions from 1 to 5.

The term ‘hydrocarbon’ is self-explanatory which means compounds of carbon and hydrogen only. Hydrocarbons play a key role in our daily life. You must be familiar with the terms ‘LPG’ and ‘CNG’ used as fuels. LPG is the abbreviated form of liquified petroleum gas whereas CNG stands for compressed natural gas. Another term ‘LNG’ (liquified natural gas) is also in news these days. This is also a fuel and is obtained by liquifaction of natural gas. Petrol, diesel and kerosene oil are obtained by the fractional distillation of petroleum found under the earth’s crust. Coal gas is obtained by the destructive distillation of coal. Natural gas is found in upper strata during drilling of oil wells. The gas after compression is known as compressed natural gas. LPG is used as a domestic fuel with the least pollution. Kerosene oil is also used as a domestic fuel but it causes some pollution. Automobiles need fuels like petrol, diesel and CNG. Petrol and CNG operated automobiles cause less pollution. All these fuels contain mixture of hydrocarbons, which are sources of energy. Hydrocarbons are also used for the manufacture of polymers like polythene, polypropene, polystyrene etc. Higher hydrocarbons are used as solvents for paints. They are also used as the starting materials for manufacture of many dyes and drugs. Thus, you can well understand the importance of hydrocarbons in your daily life. In this unit, you will learn more about hydrocarbons.

Classification Hydrocarbons are of different types. Depending upon the types of carbon-carbon bonds present, they can be classified into three main categories – (i) saturated

(ii) unsaturated and

(iii) aromatic hydrocarbons. Saturated hydrocarbons contain carbon-carbon and carbon-hydrogen single bonds. If different carbon atoms are joined together to form open chain of carbon atoms with single bonds, they are termed as alkanes. On the other hand, if carbon atoms form a closed chain or a ring, they are termed as cycloalkanes. Unsaturated hydrocarbons contain carbon-carbon multiple bonds – double bonds, triple bonds or both. Aromatic hydrocarbons are a special type of cyclic compounds. You can construct a large number of models of such molecules of both types (open chain and close chain) keeping in mind that carbon is tetravalent and hydrogen is monovalent. For making models of alkanes, you can use toothpicks for bonds and plasticine balls for atoms. For alkenes, alkynes and aromatic hydrocarbons, spring models can be constructed.

Alkanes As already mentioned, alkanes are saturated open chain hydrocarbons containing carbon – carbon single bonds. Methane (CH4) is the first member of this family. Methane is a gas found in coal mines and marshy places. If  replace one hydrogen atom of methane by carbon and join the required number of hydrogens to satisfy the tetravalence of the other carbon atom,it get C2H6. This hydrocarbon with molecular formula C2H6 is known as ethane. Thus it can consider C2H6 as derived from CH4 by replacing one hydrogen atom by -CH3 group. Go on constructing alkanes by doing this theoretical exercise i.e., replacing hydrogen atom by –CH3 group. The next molecules will be C3H8, C4H10 …

These hydrocarbons are inert under normal conditions as they do not react with acids, bases and other reagents. Hence, they were earlier known as paraffins (latin: parum, little; affinis, affinity). the general formula for alkanes is CHn + 2. It represents any particular homologue when n is given appropriate value. methane has a tetrahedral structure, in which carbon atom lies at the centre and the four hydrogen atoms lie at the four corners of a regular tetrahedron. All H-C-H bond angles are of 109.5°.

In alkanes, tetrahedra are joined together in which C-C and C-H bond lengths are 154 pm and 112 pm respectively. We have already read that C–C and C–H $\sigma$ bonds are formed by head-on overlapping of sp 3 hybrid orbitals of carbon and 1s orbitals of hydrogen atoms.

Difference in properties is due to difference in their structures, they are known as structural isomers. structural isomers which differ in chain of carbon atoms are known as chain isomers.

Preparation- Petroleum and natural gas are the main sources of alkanes. However, alkanes can be prepared by following methods:

1) From unsaturated hydrocarbons Dihydrogen gas adds to alkenes and alkynes in the presence of finely divided catalysts like platinum, palladium or nickel to form alkanes. This process is called hydrogenation. These metals adsorb dihydrogen gas on their surfaces and activate the hydrogen – hydrogen bond. Platinum and palladium catalyse the reaction at room temperature but relatively higher temperature and pressure are required with nickel catalysts.

2) From alkyl halides

i) Alkyl halides (except fluorides) on reduction with zinc and dilute hydrochloric acid give alkanes.

ii) Alkyl halides on treatment with sodium metal in dry ethereal (free from moisture) solution give higher alkanes. This reaction is known as Wurtz reaction and is used for the preparation of higher alkanes containing even number of carbon atoms.

  1. Which of the following catalyst is used for hydrogenation…
  1. platinum
  2. palladium
  3. nickel
  4. All the above
  1. LPG stands for ….
  1. Liquid Pressure Gas
  2. Liquefied Petroleum Gas
  3. Liquid Platinum Gas
  4. Liquid Processed Gas
  1. Difference in properties is due to difference in their structures, they are known as …. isomers.
  1. Functional
  2. Positional
  3. Structural
  4. Chain
  1. Structural isomers which differ in chain of carbon atoms are known as…  isomers.
  1. Functional
  2. Positional
  3. Structural
  4. Chain
  1. CNG Stands for ..
  1. Compressed Natural Gas
  2. Condensed Natural Gas
  3. Compressed Neutral Gas
  4. Compressed Neutral Gallium
Read the passage given below and answer the following questions from (i) to (v).

$\frac{1}{2}\text{N}_2(\text{g})+\frac{3}{2}\text{H}_2(\text{g})=\text{NH}_3(\text{g});\triangle_\text{r}\text{H}^\ominus=-46.1\text{kJ}\text{mol}^{-1}$

$\frac{1}{2}\text{H}_2(\text{g})+\frac{1}{2}\text{Cl}_2(\text{g})=\text{HCl}(\text{g});\triangle_\text{r}\text{H}^\ominus=-92.32\text{kJ}\text{mol}^{-1}$

$\text{H}_2(\text{g})+\frac{1}{2}\text{O}_2(\text{g})\rightarrow\text{H}_2\text{O}(\text{l});\triangle_\text{r}\text{H}^\ominus=-285.8\text{kJ}\text{mol}^{-1}$

A spontaneous process is an irreversible process and may only be reversed by some external agency.

If we examine the phenomenon like flow of Water down hill or fall of a stone on to the Ground, we find that there is a net decrease in Potential energy in the direction of change. By Analogy, we may be tempted to state that a Chemical reaction is spontaneous in a given Direction, because decrease in energy has Taken place, as in the case of exothermic Reactions. For example:

The decrease in enthalpy in passing from Reactants to products may be shown for any Exothermic reaction on an enthalpy diagram. Thus, the postulate that driving force for a Chemical reaction may be due to decrease in Energy sounds ‘reasonable’ as the basis of Evidence so far ! Now let us examine the following reactions:

$\frac{1}{2}\text{N}_2(\text{g})+\text{O}_2(\text{g})\rightarrow\text{NO}_2(\text{g});\triangle_\text{r}\text{H}^\ominus=+33.2\text{kJ}\text{mol}^{-1}$

$\text{C}(\text{graphite,s})+2\text{s}(\text{l})\rightarrow\text{CS}_2(\text{l});\triangle_\text{r}\text{H}^\ominus=+128.5\text{kJ}\text{mol}^{-1}$

Therefore, it becomes obvious that while decrease in enthalpy may be a contributory factor for spontaneity, but it is not true for all cases .

Whenever heat is added to the system, it increases molecular motions causing increased randomness in the system. Thus heat (q) has randomising influence on the system. Temperature is the measure of average chaotic motion of particles in the system. The entropy change is inversely proportional to the temperature. $\triangle\text{S}$ is related with q and T for a reversible reaction as:

$\triangle\text{S}=\frac{\text{q}_\text{rev}}{\text{T}}$

The total entropy change $(\triangle\text{S}_\text{total})$ for the system and surrounding of a spontaneous process is given by $\triangle\text{S}_\text{total}=\triangle\text{S}_\text{system}+\triangle\text{S}_\text{surr}.0$

When a system is in equilibrium, the entropy is maximum, and the change in entropy,$\triangle\text{S}=0.$ We can say that entropy for a spontaneous process increases till it reaches maximum and at equilibrium the change in entropy is zero. Since entropy is a state property, we can calculate the change in entropy of a reversible process by

$\triangle\text{S}_{\text{sys}}=\frac{\text{q}_\text{rev,rew}}{\text{T}}$

G = H – TS

Gibbs function, G is an extensive property and a state function. The change in Gibbs energy for the system, $\triangle\text{G}_{\text{sys}}$can be written as

$\therefore\triangle\text{G}_{\text{sys}}=\triangle\text{H}_{\text{sys}}-\text{T}\triangle\text{S}_{\text{sys}}-\text{S}_\text{sys}\triangle\text{T}$

At constant temperature, $\triangle\text{T}=0$

$\triangle\text{G}_{\text{sys}}=\triangle\text{H}_{\text{sys}}-\text{T}\triangle\text{S}_{\text{sys}}$

Usually the subscript ‘system’ is dropped and we simply write this equation as

$\triangle\text{G}=\triangle\text{H}–\text{T}\triangle\text{S}$

Thus, Gibbs energy change = enthalpy change – temperature × entropy change,

and is referred to as the Gibbs equation, one of the most important equations in chemistry. Here, we have considered both terms together for spontaneity: energy (in terms of $\triangle\text{H}$) and entropy ($\triangle\text{s},$ a measure of disorder) as indicated earlier. Dimensionally if we analyse, we find that $\triangle\text{G}$ has units of energy because, both $\triangle\text{H}$ and the $\text{T}\triangle\text{S}$ are energy terms, since $\text{T}\triangle\text{S}=(\text{K}) (\text{J/K}) = \text{J}.$ Now let us consider how $\triangle\text{G}$ is related to reaction spontaneity. We know, $\triangle\text{S}_\text{systeam}+\triangle\text{S}_\text{surrounding}$ If the system is in thermal equilibrium with The surrounding, then the temperature of the Surrounding is same as that of the system. Also, increase in enthalpy of the surrounding Is equal to decrease in the enthalpy of the System. Therefore, entropy change of Surroundings,

$\triangle\text{S}_\text{surr}=\frac{\triangle\text{H}_\text{surr}}{\text{T}}-\frac{\triangle\text{H}_\text{sys}}{\text{T}}$

$\triangle\text{S}_\text{total}=\text{S}_\text{sys}+\Big(-\frac{\triangle\text{H}_\text{sys}}{\text{T}}\Big)$

Rearrangine the above equation:

$\text{T}\triangle\text{S}_{\text{total}}=\text{T}\triangle\text{S}_{\text{sys}}-\triangle\text{H}_{\text{sys}}$

For spontaneous process,

$\triangle\text{S}_\text{total}>0,$ so

$\text{T}\triangle\text{S}_{\text{sys}}-\triangle\text{H}_{\text{sys}}>\text{O}$

$\Rightarrow-(\triangle\text{H}_{\text{sys}}-\text{T}\triangle\text{S}_{\text{sys}})$

Using equation, the above equation can Be written as:

$-\triangle\text{G}>\text{O}$

$\triangle\text{G}=\triangle\text{H}-\text{T}\triangle\text{S},0$

$\triangle\text{H}_\text{sys}$

Is the enthalpy change of a reaction, $\text{T}\triangle\text{S}_\text{sys}$ Is the energy which is not available to Do useful work. So $\triangle\text{G}$ is the net energy Available to do useful work and is thus a Measure of the ‘free energy. For this reason, it Is also known as the free energy of the reaction. $\triangle\text{G}$ gives a criteria for spontaneity at Constant pressure and temperature.

If $\triangle\text{G}$ is negative (< 0), the process is

b) If $\triangle\text{G}$ is positive (> 0), the process is non

Entropy and Second Law of Thermodynamics – For an isolated system the change in energy remains constant. Therefore, increase in entropy in such systems is the natural direction of a spontaneous change. This, in fact is the second law of thermodynamics. Like first law of thermodynamics, second law can also be stated in several ways. The second law of thermodynamics explains why spontaneous exothermic reactions are so common. In exothermic reactions heat released by the reaction increases the disorder of the surroundings and overall entropy change is positive which makes the reaction spontaneous.

Absolute Entropy and Third Law of Thermodynamics Molecules of a substance may move in a straight line in any direction, they may spin like a top and the bonds in the molecules may stretch and compress. These motions of the molecule are called translational, rotational and vibrational motion respectively. When temperature of the system rises, these motions become more vigorous and entropy increases. On the other hand when temperature is lowered, the entropy decreases. The entropy of any pure crystalline substance approaches zero as the temperature approaches absolute zero. This is called third law of thermodynamics. This is so because there is perfect order in a crystal at absolute zero. The statement is confined to pure crystalline solids because theoretical arguments and practical evidences have shown that entropy of solutions and super cooled liquids is not zero at 0K. The importance of the third law lies in the fact that it permits the calculation of absolute values of entropy of pure substance from thermal data alone. For a pure substance, this can be done by summing q T rev increments from 0K to 298K. Standard entropies can be used to calculate standard entropy changes by a Hess’s law type of calculation.

$\text{A}+\text{B}\rightleftharpoons\text{C}+\text{D};$ is $\triangle_\text{r}\text{G}=0$

A knowledge of the sign and Magnitude of the free energy change of a Chemical reaction allows: Prediction of the spontaneity of the Chemical reaction. Prediction of the useful work that could Be extracted from it. So far we have considered free energy Changes in irreversible reactions. Let us now Examine the free energy changes in reversible Reactions.‘Reversible’ under strict thermodynamic Sense is a special way of carrying out a Process such that system is at all times in  Perfect equilibrium with its surroundings. When applied to a chemical reaction, the Term ‘reversible’ indicates that a given Reaction can proceed in either direction Simultaneously, so that a dynamic Equilibrium is set up. This means that the Reactions in both the directions should proceed with a decrease in free energy, which seems impossible. It is possible only if at equilibrium the free energy of the system is minimum. If it is not, the system would spontaneously change to configuration of lower free energy. So, the criterion for equilibrium

Gibbs energy for a reaction in which all reactants and products are in standard state, $\triangle_\text{r}\text{G}=0$ is related to the equilibrium constant of the reaction as follows:

$0=\triangle_\text{r}\text{G}^{\ominus}+\text{RT}\text{ln}\text{K}$

or $\triangle_\text{r}\text{G}^{\ominus}=-\text{RT}\text{ln}\text{K}$

or $\triangle_\text{r}\text{G}^{\ominus}=-2.303\text{RT}\log\text{K}$

We also know that

$\triangle_\text{r}\text{G}^{\ominus}=\triangle_\text{r}\text{H}^{\ominus}-\text{T}\triangle_\text{r}\text{S}^{\ominus}-\text{RT}\text{ln}\text{K}$

For strongly endothermic reactions, the value of $\triangle_\text{r}\text{H}^\phi$ may be large and positive. In such a case, value of K will be much smaller than 1 and the reaction is unlikely to form much product. In case of exothermic reactions, $\triangle_\text{r}\text{H}^\phi$  is large and negative, and $\triangle_\text{r}\text{G}^\phi$ is likely to be large and negative too. In such cases, K will be much larger than 1. We may expect strongly exothermic reactions to have a large K, and hence can go to near completion. $\triangle_\text{r}\text{G}^\phi$ also depends upon $\triangle_\text{r}\text{S}^\phi,$ if the changes in the entropy of reaction is also taken into account, the value of K or extent of chemical reaction will also be affected, depending upon whether $\triangle_\text{r}\text{S}^\phi$ Is positive or Negative, It is possible to obtain an estimate of $\triangle{\text{G}}^0$  From the measurement of $\triangle{\text{H}}^0$ And $\triangle{\text{S}}^0,$ And then calculate K at any temperature For economic yields of the products. If K is measured directly in the Laboratory, value of $\triangle{\text{G}}^0$ At any other Temperature can be calculated.

  1. A spontaneous process is an … process.
  1. Irreversible
  2. Reversible
  3. Partially irreversible
  4. Partially reversible
  1. $\triangle\text{S}_\text{systeam}+\triangle\text{S}_\text{surrounding}$
  1. < 0
  2. > 0
  3. = 0
  4. None of above
  1. When a system is in equilibrium, the entropy is maximum, and the change in entropy, $\triangle{\text{S}}.....0.$
  1. <
  2. >
  3. =
  4. None of above
  1. … does not discriminate between reversible and irreversible process:
  1. $\triangle\text{H}$

  2. $\triangle\text{S}$

  3. $\triangle\text{G}$

  4. $\triangle\text{U}$

  1. $\text{T}\triangle\text{S}=\ ...$
  1. Kg
  2. J
  3. M
  4. lit

Read the passage given below and answer the following questions from 1 to 5.

A reagent that brings an electron pair to the reactive site is called a nucleophile (Nu:) i.e., nucleus seeking and the reaction is then called nucleophilic. A reagent that takes away an electron pair from reactive site is called electrophile (E+) i.e., electron seeking and the reaction is called electrophilic.

Electron Displacement Effects in Covalent Bonds The electron displacement in an organic molecule may take place either in the ground state under the influence of an atom or a substituent group or in the presence of an appropriate attacking reagent. The electron displacements due to the influence of an atom or a substituent group present in the molecule cause permanent polarlisation of the bond. Inductive effect and resonance effects are examples of this type of electron displacements. Temporary electron displacement effects are seen in a molecule when a reagent approaches to attack it. This type of electron displacement is called electrometric effect or polarisability effect.

Inductive Effect When a covalent bond is formed between atoms of different electronegativity, the electron density is more towards the more electronegative atom of the bond. Such a shift of electron density results in a polar covalent bond. Bond polarity leads to various electronic effects in organic compounds. Let us consider cholorethane (CHCH2Cl) in which the C–Cl bond is a polar covalent bond. It is polarised in such a way that the carbon-1 gains some positive charge $(\delta+)$ and the chlorine some negative charge $(\delta-)$ The fractional electronic charges on the two atoms in a polar covalent bond are denoted by symbol (delta) and the shift of electron density is shown by an arrow that points from$(\delta+)$ to $(\delta-)$ end of the polar bond.

In turn carbon-1, which has developed partial positive charge $(\delta+)$draws some electron density towards it from the adjacent C-C bond. Consequently, some positive charge$(\delta\delta+)$develops on carbon-2 also, where $(\delta\delta+)$ symbolises relatively smaller positive charge as compared to that on carbon – 1. In other words, the polar C – Cl bond induces polarity in the adjacent bonds. Such polarisation of σ- bond caused by the polarisation of adjacent $σ-$bond is referred to as the inductive effect.

Resonance Structure There are many organic molecules whose behaviour cannot be explained by a single Lewis structure. An example is that of benzene. Its cyclic structure containing alternating C–C single and C=C double bonds shown is inadequate for explaining its characteristic properties.

As per the above representation, benzene should exhibit two different bond lengths, due to C–C single and C=C double bonds. However, as determined experimentally benzene has a uniform C–C bond distances of 139 pm, a value intermediate between the C–C single(154 pm) and C=C double (134 pm) bonds. Thus, the structure of benzene cannot be represented adequately by the above structure. Further, benzene can be represented equally well by the energetically identical structures I and II.

Therefore, according to the resonance theory the actual structure of benzene cannot be adequately represented by any of these structures, rather it is a hybrid of the two structures (I and II) called resonance structures. The resonance structures (canonical structures or contributing structures) are hypothetical and individually do not represent any real molecule. They contribute to the actual structure in proportion to their stability.

Resonance Effect The resonance effect is defined as ‘the polarity produced in the molecule by the interaction of two π-bonds or between a π-bond and lone pair of electrons present on an adjacent atom’. The effect is transmitted through the chain. There are two types of resonance or mesomeric effect designated as R or M effect. (i) Positive Resonance Effect (+R effect) In this effect, the transfer of electrons is away from an atom or substituent group attached to the conjugated system. This electron displacement makes certain positions in the molecule of high electron densities. This effect in aniline is shown as : (ii) Negative Resonance Effect (- R effect)  This effect is observed when the transfer of  Electrons is towards the atom or substituent  Group attached to the conjugated system. For  Example in nitrobenzene this electron  Displacement can be depicted as : The atoms or substituent groups, which represent +R or –R electron displacement effects are as follows: +R effect: – halogen, –OH, –OR, –OCOR, –NH2, –NHR, –NR2, –NHCOR, – R effect: – COOH, –CHO, > C = O, – CN, – NO2 The presence of alternate single and double bonds in an open chain or cyclic system is termed as a conjugated system. These systems often show abnormal behaviour. The examples are 1,3- butadiene, aniline and nitrobenzene etc. In such systems, the π-electrons are delocalised and the system develops polarity.

Electromeric Effect (E effect) It is a temporary effect. The organic compounds having a multiple bond (a double or triple bond) show this effect in the presence of an attacking reagent only. It is defined as the complete transfer of a shared pair of π-electrons to one of the atoms joined by a multiple bond on the demand of an attacking reagent. The effect is annulled as soon as the attacking reagent is removed from the domain of the reaction. It is represented by E and the shifting of the electrons is shown by a curved arrow ( ). There are two distinct types of electromeric effect.

a) Positive Electrometric Effect (+E effect)- In this effect the π−electrons of the multiple bond are transferred to that atom to which the reagent gets attached. For example

b) Negative Electromeric Effect (–E effect) -In this effect the $\pi-$ electrons of the multiple bond are transferred to that atom to which the attacking reagent does not get attached. For example: When inductive and electromeric effects operate in opposite directions, the electomeric  effect predominates.

  1. A reagent that brings an electron pair to the reactive site is called a …
  1. nucleophile
  2. electrophile
  3. amphoteric
  4. amphophillic
  1. A reagent that takes away an electron pair from reactive site is called ..
  1. nucleophile
  2. electrophile
  3. amphoteric
  4. amphophillic
  1. The … effect is defined as the polarity produced in the molecule by the interaction of two π-bonds or between a π-bond and lone pair of electrons present on an adjacent atom.
  1. hindrance
  2. inductive
  3. resonance
  4. hyperconjunction
  1. –OH group, represent … electron displacement effect.
  1. M+
  2. M-
  3. R-
  4. R+
  1. – COOH group, represent … electron displacement effect.
  1. M+
  2. M-
  3. R-
  4. R+
The phenomenon of the existence of two or more compounds possessing the same molecular formula but different properties is known as isomerism. Such compounds are called isomers. Compounds having the same molecular formula but different structures (manners in which atoms are linked) are classified as structural isomers. Structural isomers are classified as chain isomer, position isomer, functional group isomer. Meristematic arises due to different alkyl chains on either side of the functional group in the molecule and stereoisomerism and can be classified as geometrical and optical isomerism. Hyperconjugation is a general stabilising interaction. It involves delocalisation of $\sigma$ electrons of the C-H bond of an alkyl group directly attached to an atom of an unsaturated system or to an atom with an unshared p orbital. This type of overlap stabilises the carbocation because electron density from the adjacent $\sigma$ bond helps in dispersing the positive charge.

1. Why Isopentane, pentane and Neopentane are chain isomers?
2. The molecular formula $C _3 H _8 O$ represents which isomer?
3. What type of isomerism is shown by Methoxypropane and ethoxyethane?
OR
Why hyperconjugation is a permanent effect?
In order to explain the characteristic geometrical shapes of polyatomic molecules, Pauling introduced the concept of hybridisation. The orbitals undergoing hybridisation should have nearly the same energy. There are various type of hybridisations involving s, p and d-type of orbitals. The type of hybridisation gives the characteristic shape of the molecule or ion.

1. Why all the orbitals in a set of hybridised orbitals have the same shape and energy?
2. Out of $XeF _2$ and $SF _2$ which molecule has the same shape as $NO _2^{+}$ion?
3. Out of $XeF _4$ and $XeF _2$ which molecule doesn't have the same type of hybridisation as P (Phosphorus) has in $PF _5$ ?
OR
Unsaturated compounds undergo additional reactions. Why?

Read the passage given below and answer the following questions from 1 to 5.

Alkanes are generally inert towards acids, bases, oxidising and reducing agents. However, they undergo the following reactions under certain conditions.

1) Substitution reactions One or more hydrogen atoms of alkanes can be replaced by halogens, nitro group and sulphonic acid group. Halogenation takes place either at higher temperature (573-773K) or in the presence of diffused sunlight or ultraviolet light. Lower alkanes do not undergo nitration and sulphonation reactions. These reactions in which hydrogen atoms of alkanes are substituted are known as substitution reactions. As an example, chlorination of methane is given below: Halogenation

$\text{CH}_3-\text{CH}_3+\text{CL}_2\xrightarrow{\text{hv}}\text{CH}_3-\text{CH}_2\text{Cl}+\text{HCl}$

It is found that the rate of reaction of alkanes with halogens is F2 > Cl2 > Br2 > I2. Rate of replacement of hydrogens of alkanes is: 3° > 2° > 1°. Fluorination is too violent to be controlled. Iodination is very slow and a reversible reaction. It can be carried out in the presence of oxidizing agents like HIO3 or HNO3.

$\text{CH}_4+\text{I}_2\rightleftharpoons\text{CH}_3\text{I}+\text{HI}$

$\text{HIO}_3+5\text{HI}\rightarrow3\text{I}_2+3\text{H}_2\text{O}$

Halogenation is supposed to proceed via free radical chain mechanism involving three steps namely initiation, propagation and termination.

The General combustion equation for any alkane is:

$\text{C}_\text{n}\text{H}_{2\text{n}+2}+\Bigg(\frac{3\text{n}+1}{2}\Bigg)\text{O}_2\rightarrow\text{nCO}_2+(\text{n}+1)\text{H}_2\text{O}$

Combustion
Alkanes on heating in the presence of air or dioxygen are completely oxidized to carbon dioxide and water with the evolution of large amount of heat.

Due to the evolution of large amount of heat during combustion, alkanes are used as fuels. During incomplete combustion of alkanes with insufficient amount of air or dioxygen, carbon black is formed which is used in the manufacture of ink, printer ink, black pigments and as filters.

Controlled oxidation Alkanes on heating with a regulated supply of dioxygen or air at high pressure and in the presence of suitable catalysts give a variety of oxidation products.

Ordinarily alkanes resist oxidation but alkanes having tertiary H atom can be oxidized to corresponding alcohols by potassium permanganate .

Pyrolysis Higher alkanes on heating to higher temperature decompose into lower alkanes, alkenes etc. Such a decomposition reaction into smaller fragments by the application of heat is called pyrolysis or cracking.

Pyrolysis of alkanes is believed to be a free radical reaction. Preparation of oil gas or petrol gas from kerosene oil or petrol involves the principle of pyrolysis. For example, dodecane, a constituent of kerosene oil on heating to 973K in the presence of platinum, palladium or nickel gives a mixture of heptane and pentene.

Conformations- Alkanes contain carbon-carbon sigma $(\sigma)$bonds. Electron distribution of the sigma molecular orbital is symmetrical around the internuclear axis of the C–C bond which is not disturbed due to rotation about its axis. This permits free rotation about C–C single bond. This rotation results into different spatial arrangements of atoms in space which can change into one another. Such spatial arrangements of atoms which can be converted into one another by rotation around a C-C single bond are called conformations or conformers or rotamers. Alkanes can thus have infinite number of conformations by rotation around C-C single bonds. However, it may be remembered that rotation around a C-C single bond is not completely free. It is hindered by a small energy barrier of 1-20 kJ mol–1 due to weak repulsive interaction between the adjacent bonds. Such a type of repulsive interaction is called torsional strain. Conformations of ethane : Ethane molecule (C2H6) contains a carbon – carbon single bond with each carbon atom attached to three hydrogen atoms. Considering the ball and stick model of ethane, keep one carbon atom stationary and rotate the other carbon atom around the C-C axis. This rotation results into infinite number of spatial arrangements of hydrogen atoms attached to one carbon atom with respect to the hydrogen atoms attached to the other carbon atom. These are called conformational isomers (conformers). Thus there are infinite number of conformations of ethane. However, there are two extreme cases. One such conformation in which hydrogen atoms attached to two carbons are as closed together as possible is called eclipsed conformation and the other in which hydrogens are as far apart as possible is known as the staggered conformation. Any other intermediate conformation is called a skew conformation. It may be remembered that in all the conformations, the bond angles and the bond lengths remain the same. Eclipsed and the staggered conformations can be represented by Sawhorse and Newman projections.

  1. Alkanes contain carbon-carbon … bonds.
  1. sigma $\sigma$
  2. pi bond$\pi$
  3. delta$\delta$
  4. eta $\eta$
  1. C-C single bond is hindered by a small energy barrier of…. kJ mol–1
  1. 10 - 200
  2. 1 - 20
  3. 100 - 427
  4. 342 - 786
  1. A decomposition reaction into smaller fragments by the application of heat is called as ….
  1. pyrolysis
  2. cracking
  3. both (a) & (b)
  4. combustion
  1. Which of the following steps are involving in free radical chain mechanism
  1. initiation
  2. propagation
  3. termination
  4. All the above
  1. The … reaction in which alkanes on heating in the presence of air or dioxygen are completely oxidized to carbon dioxide and water with the evolution of large amount of heat.
  1. pyrolysis
  2. cracking
  3. both (a) & (b)
  4. combustion
IUPAC (International Union of Pure and Applied Chemistry) system of nomenclature. Common names are useful and in many cases indispensable, particularly when the alternative systematic names are lengthy and complicated. A systematic name of an organic compound is generally derived by identifying the parent hydrocarbon and the functional group(s) attached to it. By using prefixes and suffixes, the parent name can be modified to obtain the actual name. In a branched-chain compound, small chains of carbon atoms are attached at one or more carbon atoms of the parent chain. The small carbon chains (branches) are called alkyl groups. An alkyl group is derived from a saturated hydrocarbon by removing a hydrogen atom from carbon. Abbreviations are used for some alkyl groups. For example, methyl is abbreviated as Me, ethyl as Et, propyl as Pr and butyl as Bu.

1. Draw the structure of 3-Ethyl-4,4-dimethylheptane. (1)
2. How is the numbering in branched chain hydrocarbon done?
3. Derive the structure of 2-Chlorohexane. (2)
OR
Why $CH _4$ after becoming- $CH _3$ called a methyl group? (2)

Read the passage given below and answer the following questions from 1 to 5.

Branched chain hydrocarbons: In a branched chain compound small chains of carbon atoms are attached at one or more carbon atoms of the parent chain. The small carbon chains (branches) are called alkyl groups. For example:

In order to name such compounds, the names of alkyl groups are prefixed to the name of parent alkane. An alkyl group is derived from a saturated hydrocarbon by removing a hydrogen atom from carbon. Thus, CH4 becomes – CH3 and is called methyl group. An alkyl group is named by substituting ‘yl’ for ‘ane’ in the corresponding alkane. Some alkyl groups are listed in Table

AlkaneAlkyl Group
Molecular formulaName of alkaneStructural formulaName of alkyl group
CH4Methane-CH3Methyl
C2H6Ethane-CH2CH3Ethyl
C3H8Propane-CH2CH2CH3Propyl
C4H10Butane-CH2CH2CH2CH3Butyl
C10H22Decane-CH2(CH2)8CH3Decyl

Abbreviations are used for some alkyl groups. For example, methyl is abbreviated as Me, ethyl as Et, propyl as Pr and butyl as Bu. The alkyl groups can be branched also. Thus, propyl and butyl groups can have branched structures as shown below .

Common branched groups have specific trivial names. For example, the propyl groups can either be n-propyl group or isopropyl group. The branched butyl groups are called sec- butyl, isobutyl and tert-butyl group. We also encounter the structural unit, – CH2C(CH3)3, which is called neopentyl group.

For Nomenclature of branched chain alkanes ,longest carbon chain in the molecule is identified. The numbering is done in such a way that the branched carbon atoms get the lowest possible numbers. lower number is given to the one coming first in the alphabetical listing. Carbon atom of  the branch that attaches to the root  alkane. in alphabetical order, the prefixes iso- and neo- are considered to be the part of the fundamental name of alkyl group. The prefixes sec- and tert- are not considered to be the part of the fundamental name.

Cyclic Compounds: A saturated monocyclic compound is named by prefixing ‘cyclo’ to the corresponding straight chain alkane. If side chains are present, then the rules given above are applied. Names of some cyclic compounds are given below.

The phenomenon of existence of two or more compounds possessing the same molecular formula but different properties is known as isomerism. Such compounds are called as isomers. The following flow chart shows different types of isomerism.

Structural Isomerism Compounds having the same molecular formula but different structures (manners in which atoms are linked) are classified as structural isomers. Some typical examples of different types of structural isomerism are given below:

(i) Chain isomerism: When two or more compounds have similar molecular formula but different carbon skeletons, these are referred to as chain isomers and the phenomenon is termed as chain isomerism. For example, C5H12 represents three compounds:

(ii) Position isomerism: When two or more compounds differ in the position of substituent atom or functional group on the carbon skeleton, they are called position isomers and this phenomenon is termed as position isomerism. For example, the molecular formula C3H8O represents two alcohols:

(iii) Functional group isomerism: Two or more compounds having the same molecular formula but different functional groups are called functional isomers and this phenomenon is termed as functional group isomerism. For example, the molecular formula C3H6O represents an aldehyde and a ketone:

(iv) Metamerism: It arises due to different alkyl chains on either side of the functional group in the molecule. For example, C4H10O represents methoxy propane (CH3OC3H7) and ethoxyethane (C2H5OC2H5).

Stereoisomerism The compounds that have the same constitution and sequence of covalent bonds but differ in relative positions of their atoms or groups in space are called stereoisomers. This special type of isomerism is called as stereoisomerism and can be classified as geometrical and optical isomerism.

Substrate and Reagent Ions are generally not formed in the reactions of organic compounds. Molecules as such participate in the reaction. It is convenient to name one reagent as substrate and other as reagent. In general, a molecule whose carbon is involved in new bond formation is called substrate and the other one is called reagent. When carbon-carbon bond is formed, the choice of naming the reactants as substrate and reagent is arbitrary and depends on molecule under observation. Example:

  1. CH4 becomes – CH3,  is called … group.
  1. methyl
  2. ethyl
  3. propyl
  4. butyl
  1. For the Nomenclature of branched chain alkanes  …. carbon chain in the molecule is identified.
  1. shortest
  2. longest
  3. smallest
  4. none of above
  1. when two or more compounds possessing the same molecular formula but different properties is known as ….
  1. Allotrops
  2. Isotops
  3. Isomers
  4. Isobars
  1. For the Nomenclature of branched chain alkanes, the numbering is done in such a way that the branched carbon atoms get the … possible numbers.
  1. biggest
  2. Lower
  3. Highest
  4. lowest
  1. Which of the following is not an example of isomerisim?
  1. Functional
  2. Positional
  3. Chain
  4. Preconditional