Question

The orbital wave function or $\psi$ for an electronin an atom has no physical meaning. It issimply a mathematical function of thecoordinates of the electron. However, fordifferent orbitals the plots of correspondingwave functions as a function of r (the distancefrom the nucleus) are different. According to the German physicist, MaxBorn, the square of the wave function(i.e.,$\psi^2$) at a point gives the probability densityof the electron at that point. Boundary surface diagrams of constantprobability density for different orbitals give afairly good representation of the shapes of theorbitals. In this representation, a boundarysurface or contour surface is drawn in spacefor an orbital on which the value of probabilitydensity $\mid\psi\mid2$ is constant. In principle manysuch boundary surfaces may be possible.However, for a given orbital, only thatboundary surface diagram of constantprobability density* is taken to be goodrepresentation of the shape of the orbital whichencloses a region or volume in which theprobability of finding the electron is very high,say, 90%.

In hydrogen atom, electron has the same energy when it is in the2s orbital as when it is present in 2p orbital.The orbitals having the same energy are calleddegenerate. The 1s orbital in a hydrogenatom, as said earlier, corresponds to the moststable condition and is called the ground stateand an electron residing in this orbital is moststrongly held by the nucleus.

An electron inthe 2s, 2p or higher orbitals in a hydrogen atomis in excited state.The filling of electrons into the orbitals ofdifferent atoms takes place according to theaufbau principle which is based on the Pauli’sexclusion principle, the Hund’s rule ofmaximum multiplicity and the relativeenergies of the orbitals. Theaufbausprinciple states : In the ground state of theatoms, the orbitals are filled in order oftheir increasing energies. In other words,electrons first occupy the lowest energy orbitalavailable to them and enter into higher energyorbitals only after the lower energy orbitals arefilled.The number of electrons to be filled in variousorbitals is restricted by the exclusion principle,given by the Austrian scientist Wolfgang Pauli(1926). According to this principle : No twoelectrons in an atom can have the sameset of four quantum numbers. Pauliexclusion principle can also be stated as : “Onlytwo electrons may exist in the same orbitaland these electrons must have oppositespin.” This means that the two electrons canhave the same value of three quantum numbersn, l and ml, but must have the opposite spinquantum number.Hund’s Rule of Maximum Multiplicity rule deals with the filling of electrons into the orbitals belonging to the same subshell. It states : pairing ofelectrons in the orbitals belonging to thesame subshell (p, d or f) does not take placeuntil each orbital belonging to thatsubshell has got one electron each i.e., itis singly occupied.

The distribution of electrons into orbitals of anatom is called its electronic configuration.If one keeps in mind the basic rules whichgovern the filling of different atomic orbitals,the electronic configurations of different atomscan be written very easily.The electronic configuration of differentatoms can be represented in two ways. Forexample :

  1. sa pbdc…… notation
  2. Orbital diagram

  1. …at a point gives the probability density of the electron at that point.
  1. $\psi\times2$

  2. $-\psi^2$

  3. $\psi$

  4. $\psi^2$

  1. Only …. electrons may exist in the same orbital and these electrons must have opposite spin.
  1. One
  2. Two
  3. Three
  4. Four
  1. …deals with the filling of electrons into the orbitals belonging to the same subshell.
  1. Hund’s Rule of Maximum Multiplicity rule
  2. Pauli’s exclusion principle
  3. Aufbau principle
  4. Werner Heisenberg
  1. Electrons first occupy the …. energy orbital available to them and enter into … energy orbitals.
  1. Lowest, Higher
  2. Higher, Lowest
  3. Middle, Higher
  4. Higher, Middle

Answer

  1. (d) $\psi^2$
  1. (b) Two
  1. (a) Hund’s Rule of Maximum Multiplicity rule
  1. (a)Lowest, Higher

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When anions and cations approach each other, the valence shell of anions are pulled towards the cation nucleus and thus, the shape of the anion is deformed. The phenomenon of deformation of anion by a cation is known as polarization and the ability of the cation to polarize the anion is called as polarizing power of cation. Due to polarization, sharing of electrons occurs between two ions to some extent and the bond shows some covalent character.
The magnitude of polarization depends upon a number of factors.

1. Out of $AlCl _3$ and $AlI _3$ which halides show maximum polarization?
2. Out of $AlCl _3$ and $CaCl _2$ which one is more covalent in nature?
3. The non-aqueous solvent like ether is added to the mixture of $LiCl , NaCl$ and KCl . Which will be extracted into the ether?
OR
Out of $CaF _2$ and $CaI _2$ which one has a minimum melting point?

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 (i) to (v).

The first concreteexplanation for the phenomenon of the blackbody radiation was given byMax Planck in 1900.An ideal body, which emits and absorbs radiations of allfrequencies uniformly, is called a black bodyand the radiation emitted by such a body is called black body radiation. Max Planck arrived at a satisfactory relationshipbymaking an assumption that absorption andemmission of radiation arises from oscillatori.e., atoms in the wall of black body.He suggested that atoms andmolecules could emit or absorb energy onlyin discrete quantities and not in a continuousmanner. He gave the name quantum to thesmallest quantity of energy that can be emitted or absorbed in the form of electromagnetic radiation. The energy (E) of aquantum of radiation is proportionalto its frequency (ν) and is expressed byequation .

E = hυ.

The proportionality constant, ‘h’ is knownas Planck’s constant and has the value6.626×10–34 Js.In 1887, H. Hertz performed a very interestingexperiment in which electrons (or electriccurrent) were ejected when certain metals (forexample potassium, rubidium, caesium etc.)were exposed to a beam of light. The phenomenon is calledPhotoelectric effect. The results observed inthis experiment were:

  1. The electrons are ejected from the metalsurface as soon as the beam of light strikesthe surface, i.e., there is no time lagbetween the striking of light beam and theejection of electrons from the metal surface.
  2. The number of electrons ejected is proportional to the intensity or brightness of light.
  3. For each metal, there is a characteristicminimum frequency,ν0(also known asthreshold frequency) below which photoelectric effect is not observed. At afrequency ν >ν0, the ejected electrons comeout with certain kinetic energy. The kineticenergies of these electrons increase withthe increase of frequency of the light used.
The particle nature of light posed a dilemmafor scientists. Theonly way to resolve the dilemma was to acceptthe idea that light possesses both particle andwave-like properties, i.e., light has dualbehaviour. Depending on the experiment, wefind that light behaves either as a wave or as astream of particles. Whenever radiationinteracts with matter, it displays particle likeproperties in contrast to the wavelike properties (interference and diffraction), whichit exhibits when it propagates. This conceptwas totally alien to the way the scientiststhought about matter and radiation and it tookthem a long time to become convincedof itsvalidity.

The study of emission or absorption spectra is referred to as spectroscopy.The emission spectra of atoms inthe gas phase, on the other hand, do not showa continuous spread of wavelength from redto violet, rather they emit light only at specificwavelengths with dark spaces between them.Such spectra are called line spectra or atomicspectra.The Swedishspectroscopist, Johannes Rydberg, noted that

all series of lines in the hydrogen spectrumcould be described by the following expression:

$\bar{\text{v}}=109,677\big(\frac{1}{\text{n}^2_1}-\frac{1}{\text{n}^2_2}\big)\text{cm}^{-1}$

The value 109,677 cm–1 is called theRydberg constant for hydrogen. The first fiveseries of lines that correspond to n1= 1, 2, 3,4, 5 are known as Lyman, Balmer, Paschen,Bracket and Pfund series, respectively.Neils Bohr (1913) was the first to explainquantitatively the general features of thestructure of hydrogen atom and its spectrum.He used Planck’s concept of quantisation ofenergy. Though the theory is not the modernquantum mechanics, it can still be used to rationalize many points in the atomic structureand spectra. Bohr’s model for hydrogen atomis based on the following postulates:

  1. The electron in the hydrogen atom canmove around the nucleus in a circular pathof fixed radius and energy. These paths arecalled orbits, stationary states or allowedenergy states. These orbits are arrangedconcentrically around the nucleus.
  2. The energy of an electron in the orbit doesnot change with time. However, theelectron will move from a lower stationarystate to a higher stationary state whenrequired amount of energy is absorbedby the electron or energy is emitted when electron moves from higher stationarystate to lower stationary state. The energychange does not takeplace in a continuous manner.
  3. The frequency of radiation absorbed oremitted when transition occurs between two stationary states that differ in energyby $\triangle\text{E},$ is given by:

$\text{v}=\frac{\triangle\text{E}}{\text{h}}=\frac{\text{E}_2-\text{E}_1}{\text{h}}$

Where E1 and E2 are the energies of the lower and higher allowed energy statesrespectively. This expression is commonly known as Bohr’s frequency rule.

  1. The angular momentum of an electron isquantised. In a given stationary state itcan be expressed as in equation

$\text{m}_{\text{e}}\text{vr}=\text{n}.\frac{\text{h}}{2\pi}\text{n}=1,2,3.....$

  1. The first concrete explanation for the phenomenon of the black body radiation was given by ….in 1900.
  1. Max Planck
  2. De Broglie
  3. Albert Einstein,
  4. Niels Bohr
  1. Which of the following equation is Planck’s equation?
  1. E= mc2
  2. E = hυ
  3. E= hc2
  4. E= vc2.
  1. What is nature of light?
  1. Wave
  2. Particle
  3. Wave and Particle
  4. None of above
  1. The value …. is called theRydberg constant for hydrogen.
  1. 109,674cm–1
  2. 109,675cm–1
  3. 109,676cm–1
  4. 109,677cm–1
  1.  …was the first to explain quantitatively the general features of the structure of hydrogen atom and its spectrum.
  1. Max Planck
  2. De Broglie
  3. Albert Einstein,
  4. Niels Bohr
The molecular orbital theory is based on the principle of a linear combination of atomic orbitals. According to this approach when atomic orbitals of the atoms come closer, they undergo constructive interference as well as destructive interference giving molecular orbitals, i.e., two atomic orbitals overlap to form two molecular orbitals, one of which lies at a lower energy level (bonding molecular orbital). Each molecular orbital can hold one or two electrons in accordance with Pauli's exclusion principle and Hund's rule of maximum multiplicity.
For molecules up to $N _2$, the order of filling of orbitals is:
Image
Bond order $=\frac{1}{2}$ [bonding electrons - antibonding electrons]
Bond order gives the following information:
I. If bond order is greater than zero, the molecule/ion exists otherwise not.
II. Higher the bond order, higher is the bond dissociation energy.
III. Higher the bond order, greater is the bond stability.
IV. Higher the bond order, shorter is the bond length.

1. Arrange the following negative stabilities of $CN , CN ^{+}$and $CN ^{-}$in increasing order of bond. (1)
2. The molecular orbital theory is preferred over valence bond theory. Why? (1)
3. Ethyne is acidic in nature in comparison to ethene and ethane. Why is it so? (2)
OR
Bonding molecular orbital is lowered by a greater amount of energy than the amount by which antibonding molecular orbital is raised. Is this statement correct? (2)
The ionic character of metallic halides tends toward covalent nature as per Fajan's rule. Such covalent halides behave as non-metal in their higher oxidation states. The property to hydrolyse to give oxy-acids of the element and corresponding hydro halogen acid for most non-metallic elements proceeds exceptionally in the way, keeping oxidation number of element and halide sam in oxo-acids.
Non-polar halides are immiscible in water, as they do not show hydrolysis, but halides of some elements with empty d-orbital undergo hydrolysis. Stability of halides of the higher state is governed by the inert-pair effect.

1. How does halide undergo hydrolysis to give oxy-acids of underlined element $PCl _3$ ?
2. Out of $NCl _3$ and $BCl _3$ undergoes hydrolysis to form oxy-acids? Write the chemical reaction for the correct answer.
3. Out of $PbCl _4, PbF _4, PbI _4$ and $PbBr _4$ which one doesn't exist?
OR
Non-Polar halides are immiscible in water. Why?
The molecular orbital theory is based on the principle of a linear combination of atomic orbitals. According to this approach when atomic orbitals of the atoms come closer, they undergo constructive interference as well as destructive interference giving molecular orbitals, i.e., two atomic orbitals overlap to form two molecular orbitals, one of which lies at a lower energy level (bonding molecular orbital). Each molecular orbital can hold one or two electrons in accordance with Pauli's exclusion principle and Hund's rule of maximum multiplicity. For molecules up to $N _2$, the order of filling of orbitals is:
Image
Bond order $=\frac{1}{2}$ [bonding electrons - antibonding electrons]
Bond order gives the following information:
i. If bond order is greater than zero, the molecule/ion exists otherwise not.
ii. Higher the bond order, higher is the bond dissociation energy.
iii. Higher the bond order, greater is the bond stability.
iv. Higher the bond order, shorter is the bond length.

1. Arrange the following negative stabilities of $CN , CN ^{+}$and $CN ^{-}$in increasing order of bond.
2. The molecular orbital theory is preferred over valence bond theory. Why?
3. Ethyne is acidic in nature in comparison to ethene and ethane. Why is it so?
OR
Bonding molecular orbital is lowered by a greater amount of energy than the amount by which antibonding molecular orbital is raised. Is this statement correct?
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
Once an organic compound is extracted from a natural source or synthesised in the laboratory, it is essential to purify it. Various methods used for the purification of organic compounds are based on the nature of the compound and the impurity present in it. Finally, the purity of a compound is ascertained by determining its melting or boiling point. This is one of the most commonly used techniques for the purification of solid organic compounds. In crystallisation Impurities, which impart colour to the solution are removed by adsorbing over activated charcoal. In distillation Liquids having different boiling points vaporise at different temperatures. The vapours are cooled and the liquids so formed are collected separately. Steam Distillation is applied to separate substances which are steam volatile and are immiscible with water. Distillation under reduced pressure: This method is used to purify liquids having very high boiling points.

i. Which method can be used to separate two compounds with different solubilities in a solvent?
ii. Distillation method is used to separate which type of substance?
iii. Which technique is used to separate aniline from aniline water mixture?
OR
Why chloroform and aniline are easily separated by the technique of distillation?
When anions and cations approach each other, the valence shell of anions are pulled towards the cation nucleus and thus, the shape of the anion is deformed. The phenomenon of deformation of anion by a cation is known as polarization and the ability of the cation to polarize the anion is called as polarizing power of cation. Due to polarization, sharing of electrons occurs between two ions to some extent and the bond shows some covalent character.
The magnitude of polarization depends upon a number of factors.

1. Out of $AlCl _3$ and $AlI _3$ which halides show maximum polarization? (1)
2. Out of $AlCl _3$ and $CaCl _2$ which one is more covalent in nature? (1)
3. The non-aqueous solvent like ether is added to the mixture of $LiCl , NaCl$ and KCl . Which will be extracted into the ether? (2)
OR
Out of $CaF _2$ and $CaI _2$ which one has a minimum melting point? (2)