2.5 POTENTIAL DUE TO A SYSTEM OF CHARGES Consider a system of charges q1, q2,…, qn with position vectors r1, r2,…, rn relative to some origin (Fig. 2.6). The potential V1 at P due to the charge q1 is 1 q1 V1 = 4 πε0 r1P where r1P is the distance between q1 and P. Similarly, the potential V2 at P due to q2 and V3 due to q3 are given by 1 q 2 1 q 3 V 2 = , V 3 = 4 πε0 r2P 4 πε0 r3P where r2P and r3P are the distances of P from charges q2 and q3, respectively; and so on for the potential due to other charges. By the FIGURE 2.6 Potential at a point due to a superposition principle, the potential V at P due system of charges is the sum of potentials to the total charge configuration is the algebraic due to individual charges. sum of the potentials due to the individual charges V = V1 + V2 + ... + Vn (2.17) 51 Reprint 2025-26 Physics 1  q1 q 2 q n  = + + ...... + (2.18) 4 πε0  r1P r2 P rnP  If we have a continuous charge distribution characterised by a charge density r (r), we divide it, as before, into small volume elements each of size Dv and carrying a charge rDv. We then determine the potential due to each volume element and sum (strictly speaking , integrate) over all such contributions, and thus determine the potential due to the entire distribution. We have seen in Chapter 1 that for a uniformly charged spherical shell, the electric field outside the shell is as if the entire charge is concentrated at the centre. Thus, the potential outside the shell is given by 1 q V = (r ≥ R ) [2.19(a)] 4 πε0 r where q is the total charge on the shell and R its radius. The electric field inside the shell is zero. This implies (Section 2.6) that potential is constant inside the shell (as no work is done in moving a charge inside the shell), and, therefore, equals its value at the surface, which is 1 q V = [2.19(b)] 4 πε0 R Example 2.2 Two charges 3 × 10–8 C and –2 × 10–8 C are located 15 cm apart. At what point on the line joining the two charges is the electric potential zero? Take the potential at infinity to be zero. Solution Let us take the origin O at the location of the positive charge. The line joining the two charges is taken to be the x-axis; the negative charge is taken to be on the right side of the origin (Fig. 2.7). FIGURE 2.7 Let P be the required point on the x-axis where the potential is zero. If x is the x-coordinate of P, obviously x must be positive. (There is no possibility of potentials due to the two charges adding up to zero for x < 0.) If x lies between O and A, we have 1  3 × 10 – 8 2 × 10 –8  − x × 10 –2 4 πε0  (15 − x ) × 10 –2  = 0 where x is in cm. That is, 3 2 − = 0 2.2 x 15 − x which gives x = 9 cm. If x lies on the extended line OA, the required condition is 3 2 − = 0 EXAMPLE x x − 15 Reprint 2025-26 Electrostatic Potential and Capacitance which gives x = 45 cm Thus, electric potential is zero at 9 cm and 45 cm away from the positive charge on the side of the negative charge. Note that the EXAMPLE formula for potential used in the calculation required choosing potential to be zero at infinity. 2.2 Example 2.3 Figures 2.8 (a) and (b) show the field lines of a positive and negative point charge respectively. Electric potential, equipotential-sufaces-12584/ FIGURE 2.8 equipotential (a) Give the signs of the potential difference VP – VQ; VB – VA. (b) Give the sign of the potential energy difference of a small negative charge between the points Q and P; A and B. surfaces: (c) Give the sign of the work done by the field in moving a small positive charge from Q to P. (d) Give the sign of the work done by the external agency in moving a small negative charge from B to A. (e) Does the kinetic energy of a small negative charge increase or decrease in going from B to A? Solution 1 (a) As V ∝ , VP > VQ. Thus, (VP – VQ) is positive. Also VB is less negative r than VA . Thus, VB > VA or (VB – VA) is positive. (b) A small negative charge will be attracted towards positive charge. The negative charge moves from higher potential energy to lower potential energy. Therefore the sign of potential energy difference of a small negative charge between Q and P is positive. Similarly, (P.E.)A > (P.E.)B and hence sign of potential energy differences is positive. http://video.mit.edu/watch/4-electrostatic-potential-elctric-energy-ev-conservative-field- (c) In moving a small positive charge from Q to P, work has to be done by an external agency against the electric field. Therefore, work done by the field is negative. (d) In moving a small negative charge from B to A work has to be done by the external agency. It is positive. EXAMPLE (e) Due to force of repulsion on the negative charge, velocity decreases and hence the kinetic energy decreases in going from B to A. 2.3 53 Reprint 2025-26 Physics 2.6 EQUIPOTENTIAL SURFACES An equipotential surface is a surface with a constant value of potential at all points on the surface. For a single charge q, the potential is given by Eq. (2.8): 1 q V = 4 πεo r This shows that V is a constant if r is constant. Thus, equipotential surfaces of a single point charge are concentric spherical surfaces centred at the charge. Now the electric field lines for a single charge q are radial lines starting from or ending at the charge, depending on whether q is positive or negative. Clearly, the electric field at every point is normal to the equipotential surface passing through that point. This is true in general: for any charge configuration, equipotential surface through a point is normal to the electric field at that point. The proof of this statement is simple. If the field were not normal to the equipotential surface, it would have non-zero component along the surface. To move a unit test charge against the direction of the component of the field, work would have to be done. But this is in contradiction to the definition of an equipotential FIGURE 2.9 For a surface: there is no potential difference between any two points on the single charge q surface and no work is required to move a test charge on the surface. (a) equipotential The electric field must, therefore, be normal to the equipotential surface surfaces are at every point. Equipotential surfaces offer an alternative visual picture spherical surfaces in addition to the picture of electric field lines around a charge centred at the configuration. charge, and (b) electric field lines are radial, starting from the charge if q > 0. FIGURE 2.10 Equipotential surfaces for a uniform electric field. For a uniform electric field E, say, along the x-axis, the equipotential surfaces are planes normal to the x-axis, i.e., planes parallel to the y-z plane (Fig. 2.10). Equipotential surfaces for (a) a dipole and (b) two identical positive charges are shown in Fig. 2.11. FIGURE 2.11 Some equipotential surfaces for (a) a dipole, 54 (b) two identical positive charges. Reprint 2025-26 Electrostatic Potential and Capacitance 2.6.1 Relation between field and potential Consider two closely spaced equipotential surfaces A and B (Fig. 2.12) with potential values V and V + dV, where dV is the change in V in the direction of the electric field E. Let P be a point on the surface B. d l is the perpendicular distance of the surface A from P. Imagine that a unit positive charge is moved along this perpendicular from the surface B to surface A against the electric field. The work done in this process is |E|dl. This work equals the potential difference VA–VB. Thus, |E|d l = V – (V + dV)= – dV V i.e., |E|= −δ (2.20) δl Since dV is negative, dV = – |dV|. we can rewrite FIGURE 2.12 From the Eq (2.20) as potential to the field. δV δV E = − = + (2.21) δl δl We thus arrive at two important conclusions concerning the relation between electric field and potential: (i) Electric field is in the direction in which the potential decreases steepest. (ii) Its magnitude is given by the change in the magnitude of potential per unit displacement normal to the equipotential surface at the point.

9.4 Alkynes 1 2 3 4 5 Like alkenes, alkynes are also unsaturated II. H3C–C≡ C– CH2– CH3 Pent–2-yne hydrocarbons. They contain at least one triple 4 3 2 1 bond between two carbon atoms. The number III. H3C–CH–C≡ CH 3-Methyl but–1-yne |of hydrogen atoms is still less in alkynes as CH3compared to alkenes or alkanes. Their general Structures I and II are position isomers formula is CnH2n–2. and structures I and III or II and III are chain The first stable member of alkyne series isomers. is ethyne which is popularly known as acetylene. Acetylene is used for arc welding Problem 9.13 purposes in the form of oxyacetylene flame Write structures of different isomers obtained by mixing acetylene with oxygen corresponding to the 5 th member of gas. Alkynes are starting materials for a large alkyne series. Also write IUPAC names of number of organic compounds. Hence, it all the isomers. What type of isomerism is interesting to study this class of organic is exhibited by different pairs of isomers? compounds. Solution 9.4.1 Nomenclature and Isomerism th 5 member of alkyne has the molecular In common system, alkynes are named as formula C6H10. The possible isomers are: derivatives of acetylene. In IUPAC system, they Table 9.2 Common and IUPAC Names of Alkynes (CnH2n–2) Value of n Formula Structure Common name IUPAC name 2 C2H2 H-C≡CH Acetylene Ethyne 3 C3H4 CH3-C≡CH Methylacetylene Propyne 4 C4H6 CH3CH2-C≡CH Ethylacetylene But-1-yne 4 C4H6 CH3-C≡C-CH3 Dimethylacetylene But-2-yne Reprint 2025-26 Hydrocarbons 315 (a) HC ≡ C – CH2 – CH2 – CH2 – CH3 Hex-1-yne (b) CH3 – C ≡ C – CH2 – CH2 – CH3 Hex-2-yne (c) CH3 – CH2 – C ≡ C – CH2– CH3 Hex-3-yne 3-Methylpent-1-yne 4-Methylpent-1-yne 4-Methylpent-2-yne Fig. 9.6 Orbital picture of ethyne showing (a) sigma overlaps (b) pi overlaps. orbitals of the other carbon atom, which undergo lateral or sideways overlapping to 3,3-Dimethylbut-1-yne form two pi (π) bonds between two carbon atoms. Thus ethyne molecule consists of one Position and chain isomerism shown by C–C σ bond, two C–H σ bonds and two C–C different pairs. π bonds. The strength of C≡C bond (bond enthalpy 823 kJ mol -1) is more than those 9.4.2 Structure of Triple Bond of C=C bond (bond enthalpy 681 kJ mol –1) Ethyne is the simplest molecule of alkyne and C–C bond (bond enthalpy 348 kJ mol–1). series. Structure of ethyne is shown in The C≡C bond length is shorter (120 pm) Fig. 9.6. than those of C=C (133 pm) and C–C (154 pm). Electron cloud between two carbon Each carbon atom of ethyne has two sp atoms is cylindrically symmetrical about thehybridised orbitals. Carbon-carbon sigma (σ) internuclear axis. Thus, ethyne is a linear bond is obtained by the head-on overlapping molecule. of the two sp hybridised orbitals of the two carbon atoms. The remaining sp hybridised 9.4.3 Preparation orbital of each carbon atom undergoes 1. From calcium carbide: On industrial overlapping along the internuclear axis with scale, ethyne is prepared by treating the 1s orbital of each of the two hydrogen calcium carbide with water. Calcium atoms forming two C-H sigma bonds. carbide is prepared by heating quick lime H-C-C bond angle is of 180°. Each carbon with coke. Quick lime can be obtained byhas two unhybridised p orbitals which are heating limestone as shown in the followingperpendicular to each other as well as to the reactions:plane of the C-C sigma bond. The 2p orbitals of one carbon atom are parallel to the 2p CaCO3 ∆ CaO + O2 (9.55) Reprint 2025-26 316 chemistry CaO + 3C CaC2 + CO (9.56) the sp hybridised carbon2 atoms whereas they are attached to sp hybridised carbon Calcium 3 atoms in ethene and sp hybridised carbons carbide in ethane. Due to the maximum percentage of CaC2 + 2H2O Ca(OH)2 + C2H2 (9.57) s character (50%), the sp hybridised orbitals of carbon atoms in ethyne molecules have2. From vicinal dihalides : Vicinal dihalides highest electronegativity; hence, these attract on treatment with alcoholic potassium the shared electron pair of the C-H bond of hydroxide undergo dehydrohalogenation. ethyne to a greater extent than that of the One molecule of hydrogen halide is 2 sp hybridised orbitals of carbon in ethene eliminated to form alkenyl halide which 3 and the sp hybridised orbital of carbon in on treatment with sodamide gives alkyne. ethane. Thus in ethyne, hydrogen atoms can be liberated as protons more easily as compared to ethene and ethane. Hence, hydrogen atoms of ethyne attached to triply bonded carbon atom are acidic in nature. You may note that the hydrogen atoms attached to the triply bonded carbons are acidic but not all the hydrogen atoms of alkynes. HC ≡ CH + Na → HC ≡ C–Na++ 1/2 H2 9.4.4 Properties Monosodium Physical properties ethynide Physical properties of alkynes follow the same (9.59) trend of alkenes and alkanes. First three HC ≡ C– Na + Na → Na+ C–Na+ ≡ C–Na++ 1/2 H2members are gases, the next eight are liquids and the higher ones are solids. All alkynes Disodium ethynide are colourless. Ethyene has characteristic (9.60)odour. Other members are odourless. Alkynes are weakly polar in nature. They are lighter CH3 – C ≡ C – H + Na+ NH–2 than water and immiscible with water but ↓ soluble in organic solvents like ethers, carbon CH3 – C ≡ C– Na+ + NH3 tetrachloride and benzene. Their melting Sodium propynide (9.61) point, boiling point and density increase with These reactions are not shown by alkenesincrease in molar mass. and alkanes, hence used for distinction Chemical properties between alkynes, alkenes and alkanes. What Alkynes show acidic nature, addition reactions about the above reactions with but-1-yne and and polymerisation reactions as follows : but-2-yne ? Alkanes, alkenes and alkynes A. Acidic character of alkyne: Sodium follow the following trend in their acidic metal and sodamide (NaNH2) are strong behaviour : bases. They react with ethyne to form sodium i) CH ≡ CH > H2C – CH2 > CH3 –CH3acetylide with the liberation of dihydrogen gas. These reactions have not been observed ii) HC ≡ CH > CH3 –C≡ CH >> CH3 –C≡C–CH3in case of ethene and ethane thus indicating that ethyne is acidic in nature in comparison B. Addition reactions: Alkynes contain a to ethene and ethane. Why is it so ? Has triple bond, so they add up, two molecules of it something to do with their structures dihydrogen, halogen, hydrogen halides etc. and the hybridisation ? You have read that Formation of the addition product takes place hydrogen atoms in ethyne are attached to according to the following steps. Reprint 2025-26 Hydrocarbons 317 The addition product formed depends upon stability of vinylic cation. Addition in unsymmetrical alkynes takes place according to Markovnikov rule. Majority of the reactions of alkynes are the examples of electrophilic addition reactions. A few addition reactions (9.66)are given below: (i) Addition of dihydrogen (iv) Addition of water Pt/Pd/Ni H2 Like alkanes and alkenes, alkynes are alsoHC≡CH+H2 [H2C = CH2] CH3–CH3 immiscible and do not react with water. (9.62) However, one molecule of water adds to alkynes on warming with mercuric sulphate CH3–C≡CH + H2 Pt/Pd/Ni [CH3–CH=CH2] and dilute sulphuric acid at 333 K to form Propyne Propene carbonyl compounds. ↓H2 CH3–CH2–CH3 Propane (9.63) (ii) Addition of halogens (9.67) (9.64) Reddish orange colour of the solution of bromine in carbon tetrachloride is decolourised. This is used as a test for unsaturation. (iii) Addition of hydrogen halides (9.68) Two molecules of hydrogen halides (HCl, HBr, (v) Polymerisation HI) add to alkynes to form gem dihalides (in (a) Linear polymerisation: Under suitable which two halogens are attached to the same conditions, linear polymerisation of ethyne carbon atom) takes place to produce polyacetylene or H–C≡C–H+H–Br [CH2 = CH–Br]→ CHBr2 polyethyne which is a high molecular Bromoethene weight polyene containing repeating units of CH3 (CH = CH – CH = CH ) and can be represented 1,1-Dibromoethane as —(CH = CH – CH = CH)n— Under special (9.65) conditions, this polymer conducts electricity. Reprint 2025-26 318 chemistry Thin film of polyacetylene can be used as but in a majority of reactions of aromatic electrodes in batteries. These films are good compounds, the unsaturation of benzene ring conductors, lighter and cheaper than the is retained. However, there are examples of metal conductors. aromatic hydrocarbons which do not contain a (b) Cyclic polymerisation: Ethyne on benzene ring but instead contain other highly unsaturated ring. Aromatic compoundspassing through red hot iron tube at 873K containing benzene ring are known asundergoes cyclic polymerization. Three benzenoids and those not containing amolecules polymerise to form benzene, which benzene ring are known as non-benzenoids.is the starting molecule for the preparation of Some examples of arenes are givenderivatives of benzene, dyes, drugs and large below:number of other organic compounds. This is the best route for entering from aliphatic to aromatic compounds as discussed below: Benzene Toluene Naphthalene (9.69) Biphenyl Problem 9.14 How will you convert ethanoic acid into 9.5.1 Nomenclature and Isomerism benzene? The nomenclature and isomerism of aromatic Solution hydrocarbons has already been discussed in Unit 8. All six hydrogen atoms in benzene are equivalent; so it forms one and only one type of monosubstituted product. When two hydrogen atoms in benzene are replaced by two similar or different monovalent atoms or groups, three different position isomers are possible. The 1, 2 or 1, 6 is known as the ortho (o–), the 1, 3 or 1, 5 as meta (m–) and the 1, 4 as para (p–) disubstituted compounds. A few examples of derivatives of benzene are given below:

3.10 In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial concentrations of A and B as given below: A/ mol L–1 0.20 0.20 0.40 B/ mol L–1 0.30 0.10 0.05 r0/mol L–1s–1 5.07 × 10–5 5.07 × 10–5 1.43 × 10–4 What is the order of the reaction with respect to A and B? 3.11 The following results have been obtained during the kinetic studies of the reaction: 2A + B ® C + D Experiment [A]/mol L–1 [B]/mol L–1 Initial rate of formation of D/mol L–1 min–1 I 0.1 0.1 6.0 × 10–3 II 0.3 0.2 7.2 × 10–2 III 0.3 0.4 2.88 × 10–1 IV 0.4 0.1 2.40 × 10–2 Determine the rate law and the rate constant for the reaction. 3.12 The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in the blanks in the following table: Experiment [A]/ mol L–1 [B]/ mol L–1 Initial rate/ mol L–1 min–1 I 0.1 0.1 2.0 × 10–2 II – 0.2 4.0 × 10–2 III 0.4 0.4 – IV – 0.2 2.0 × 10–2 3.13 Calculate the half-life of a first order reaction from their rate constants given below: (i) 200 s–1 (ii) 2 min–1 (iii) 4 years–1 3.14 The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood had only 80% of the 14C found in a living tree. Estimate the age of the sample. 3.15 The experimental data for decomposition of N2O5 [2N2O5 ® 4NO2 + O2] in gas phase at 318K are given below: t/s 0 400 800 1200 1600 2000 2400 2800 3200 102 × [N2O5]/ 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35 mol L–1 (i) Plot [N2O5] against t. (ii) Find the half-life period for the reaction. (iii) Draw a graph between log[N2O5] and t. (iv) What is the rate law ? Chemistry 86 Reprint 2025-26 (v) Calculate the rate constant. (vi) Calculate the half-life period from k and compare it with (ii).