3.6 VECTOR ADDITION – ANALYTICAL then, a vector T = a + b – c has components : METHOD T x = a x + b x − c x Although the graphical method of adding vectors Ty = a y + b y − c y (3.23b) helps us in visualising the vectors and the T z = a z + b z − c z .resultant vector, it is sometimes tedious and has limited accuracy. It is much easier to add vectors ⊳ Example 3.2 Find the magnitude andby combining their respective components. direction of the resultant of two vectors AConsider two vectors A and B in x-y plane with and B in terms of their magnitudes and components Ax, Ay and Bx, By : angle θ between them. ɵ ɵ A = A x i + A y j (3.18) * Note that angles α, β, and γ are angles in space. They are between pairs of lines, which are not coplanar. Reprint 2025-26 34 PHYSICS ⊳ Example 3.3 A motorboat is racing towards north at 25 km/h and the water current in that region is 10 km/h in the direction of 60° east of south. Find the resultant velocity of the boat. Answer The vector vb representing the velocity of the motorboat and the vector vc representing Fig. 3.10 the water current are shown in Fig. 3.11 in Answer Let OP and OQ represent the two vectors directions specified by the problem. Using the A and B making an angle θ (Fig. 3.10). Then, parallelogram method of addition, the resultant using the parallelogram method of vector R is obtained in the direction shown in the addition, OS represents the resultant vector R : figure. R = A + B SN is normal to OP and PM is normal to OS. From the geometry of the figure, OS2 = ON2 + SN2 but ON = OP + PN = A + B cos θ SN = B sin θ OS2 = (A + B cos θ)2 + (B sin θ)2 or, R2 = A2 + B2 + 2AB cos θ R = A 2 + B 2 + 2AB cosθ (3.24a) In ∆ OSN, SN = OS sinα = R sinα, and in ∆ PSN, SN = PS sin θ = B sin θ Therefore, R sin α = B sin θ R B or, = (3.24b) sin θ sin α Fig. 3.11 Similarly, PM = A sin α = B sin β We can obtain the magnitude of R using the Law A B or, = (3.24c) of cosine : sin β sin α Combining Eqs. (3.24b) and (3.24c), we get R = v 2b + v c2 + 2v bv c cos120 o R A B = = (3.24d) = 25 2 + 10 2 + 2 × 25 × 10 ( -1/2 ) ≅ 22 km/h sin θ sin β sin α To obtain the direction, we apply the Law of sines Using Eq. (3.24d), we get: R vc v c B = sin θ or, sin φ = sin α = sin θ (3.24e) sin θ sin φ R R where R is given by Eq. (3.24a). 10 × sin120 10 3 = = ≅ 0.397 SN B sin θ 21.8 2 × 21.8or, tan α= = (3.24f) OP + PN A + B cos θ φ ≅ 23.4 ⊳ Equation (3.24a) gives the magnitude of the 3.7 MOTION IN A PLANEresultant and Eqs. (3.24e) and (3.24f) its direction. Equation (3.24a) is known as the Law of cosines In this section we shall see how to describe and Eq. (3.24d) as the Law of sines. ⊳ motion in two dimensions using vectors. Reprint 2025-26 MOTION IN A PLANE 35 3.7.1 Position Vector and Displacement Suppose a particle moves along the curve shown The position vector r of a particle P located in a by the thick line and is at P at time t and P′ at plane with reference to the origin of an x-y time t′ [Fig. 3.12(b)]. Then, the displacement is : reference frame (Fig. 3.12) is given by ∆r = r′ – r (3.25) ɵ ɵ and is directed from P to P′. r = x i + y j We can write Eq. (3.25) in a component form: where x and y are components of r along x-, and y- axes or simply they are the coordinates of ɵ ɵ ɵ ɵ ∆r = x' i + y' j − x i + y j ( ) ( )the object. ɵ ɵ = i ∆ x + j ∆ y where ∆x = x ′ – x, ∆y = y′ – y (3.26) Velocity v The average velocity ( ) of an object is the ratio of the displacement and the corresponding time interval : ɵ ɵ ∆ r ∆ x i + ∆y j ɵ ∆ x ɵ ∆ y v = = = i + j (3.27) ∆ t ∆ t ∆ t ∆ t Or, v = v x ˆi + v y j (a) ∆ r Since v = , the direction of the average velocity ∆t is the same as that of ∆r (Fig. 3.12). The velocity (instantaneous velocity) is given by the limiting value of the average velocity as the time interval approaches zero : ∆ r d r v = lim = (3.28) ∆ t → 0 ∆ t d t The meaning of the limiting process can be easily understood with the help of Fig 3.13(a) to (d). In these figures, the thick line represents the path of an object, which is at P at time t. P1, P2 and (b) P3 represent the positions of the object after Fig. 3.12 (a) Position vector r. (b) Displacement ∆r and times ∆t1,∆t2, and ∆t3. ∆r1, ∆r2, and ∆r3 are the average velocity v of a particle. displacements of the object in times ∆t1, ∆t2, and Fig. 3.13 As the time interval ∆t approaches zero, the average velocity approaches the velocity v. The direction of v is parallel to the line tangent to the path. Reprint 2025-26 36 PHYSICS ∆t3, respectively. The direction of the average velocity v is shown in figures (a), (b) and (c) for three decreasing values of ∆t, i.e. ∆t1,∆t2, and ∆t3, (∆t1 > ∆t2 > ∆t3). As ∆t → 0, ∆r → 0 and is along the tangent to the path [Fig. 3.13(d)]. Therefore, the direction of velocity at any point on the path of an object is tangential to the path at that point and is in the direction of motion. We can express v in a component form : Fig. 3.14 The components vx and vy of velocity v and the angle θ it makes with x-axis. Note that dr vx = v cos θ, vy = v sin θ. v = dt The acceleration (instantaneous acceleration)  ∆x ɵ ∆y ɵ  is the limiting value of the average acceleration = lim  i + j  (3.29) ∆t → 0 ∆t ∆t  as the time interval approaches zero : ∆ v ∆x ∆y ɵ ɵ a = lim (3. 32a) + = i lim j lim ∆t → 0 ∆t ∆t → 0 ∆t ∆ t → 0 ∆ t ɵ ɵ ɵ dx ɵ dy ɵ ɵ Since ∆ v = ∆ v x i + ∆ v y j, we have + jOr, v = i = v x i + v y j . dt dt ɵ ∆ v x ɵ ∆ v y dx dy a = i lim + j lim ∆ t → 0 ∆ t ∆ t → 0 ∆ twhere v x = dt , v y = dt (3.30a) ɵ ɵ So, if the expressions for the coordinates x and Or, a = a x i + a y j (3.32b) y are known as functions of time, we can use d v y d v xthese equations to find vx and vy. (3.32c)* where, a x = , a y = The magnitude of v is then d t d t 2 2 As in the case of velocity, we can understand v = v x + v y (3.30b) graphically the limiting process used in defining and the direction of v is given by the angle θ : acceleration on a graph showing the path of the object’s motion. This is shown in Figs. 3.15(a) to  v y  (d). P represents the position of the object at v y −1 tanθ = , θ = tan     (3.30c) time t and P1, P2, P3 positions after time ∆t1, ∆t2,  v x  v x ∆t3, respectively (∆t 1> ∆t2>∆t3). The velocity vectors vx, vy and angle θ are shown in Fig. 3.14 for a at points P, P1, P2, P3 are also shown in Figs. 3.15 velocity vector v at point p. (a), (b) and (c). In each case of ∆t, ∆v is obtained using the triangle law of vector addition. ByAcceleration definition, the direction of average acceleration The average acceleration a of an object for a is the same as that of ∆v. We see that as ∆t time interval ∆t moving in x-y plane is the change decreases, the direction of ∆v changes and in velocity divided by the time interval : consequently, the direction of the acceleration ɵ ɵ changes. Finally, in the limit ∆t g0 [Fig. 3.15(d)], j v x i + v y ∆ v ∆ ( ∆ v y ɵ ) ∆ v x ɵ a = = = i + j (3.31a) the average acceleration becomes the ∆ t ∆ t ∆ t ∆ t instantaneous acceleration and has the direction ɵ ɵ as shown. Or, a = a x i + a y j . (3.31b) * In terms of x and y, ax and ay can be expressed as Reprint 2025-26 MOTION IN A PLANE 37 x (m) Fig. 3.15 The average acceleration for three time intervals (a) ∆t1, (b) ∆t2, and (c) ∆t3, (∆t1> ∆t2> ∆t3). (d) In the limit ∆t g0, the average acceleration becomes the acceleration. Note that in one dimension, the velocity and the acceleration of an object are always along -1  v y  − 1  4  ° θ = tan   = tan   ≅ 53 with x-axis. the same straight line (either in the same  v x   3  direction or in the opposite direction). ⊳ However, for motion in two or three dimensions, velocity and acceleration vectors may have any angle between 0° and 180° 3.8 MOTION IN A PLANE WITH CONSTANT between them. ACCELERATION ⊳ Suppose that an object is moving in x-y plane Example 3.4 The position of a particle is and its acceleration a is constant. Over an given by interval of time, the average acceleration will r = 3.0t ˆi + 2 .0t 2 ˆj + 5 .0 kˆ equal this constant value. Now, let the velocity where t is in seconds and the of the object be v0 at time t = 0 and v at time t. coefficients have the proper units for r to Then, by definition be in metres. (a) Find v(t) and a(t) of the v − v 0 v − v 0 particle. (b) Find the magnitude and a = = t − 0 t direction of v(t) at t = 1.0 s. Or, v = v 0 + a t (3.33a) Answer In terms of components : v x = v ox + a x t dr d ɵ ɵ ɵ v ( t ) = = 3.0 t i + 2.0t2 j + 5.0 k ( ) v y = v oy + a y t (3.33b) d t dt ɵ ɵ = 3.0 i + 4.0t j Let us now find how the position r changes with d v time. We follow the method used in the one- a ( t ) = = +4.0ɵj dt dimensional case. Let ro and r be the position a = 4.0 m s–2 along y- direction vectors of the particle at time 0 and t and let the velocities at these instants be vo and v. Then,At t = 1.0 s, v = 3.0ˆi + 4.0 ˆj over this time interval t, the average velocity is 2 2 -1 (vo + v)/2. The displacement is the average It’s magnitude is v = 3 + 4 = 5.0 m s velocity multiplied by the time interval : and direction is Reprint 2025-26 38 PHYSICS ˆ  v + v 0   ( v 0 + at ) + v 0  = 5.0 t + 1.5 t 2 i + 1.0 t 2 ˆj ( ) t t = r − r0 = 2  2    2 Therefore, x (t ) = 5.0 t + 1.5 t 1 2 y (t ) = +1.0 t 2 at = v 0 t + 2 Given x (t) = 84 m, t = ? 1 2 5.0 t + 1.5 t 2 = 84 ⇒ t = 6 s Or, r = r0 + v 0t + at (3.34a) At t = 6 s, y = 1.0 (6)2 = 36.0 m 2 d r 2.0 t ˆjIt can be easily verified that the derivative of Now, the velocity v = = ( 5.0 + 3.0 t ) ˆi + d t d r ɵ ɵEq. (3.34a), i.e. gives Eq.(3.33a) and it also At t = 6 s, v = 23.0 i + 12.0 j d t satisfies the condition that at t=0, r = ro. speed = v = 232 + 122 ≅ 26 m s−1 . ⊳Equation (3.34a) can be written in component form as 3.9 PROJECTILE MOTION 1 2 x = x 0 + v ox t + a x t As an application of the ideas developed in the 2 previous sections, we consider the motion of a 1 2 projectile. An object that is in flight after being y = y 0 + v oy t + a y t (3.34b) thrown or projected is called a projectile. Such 2 a projectile might be a football, a cricket ball, a One immediate interpretation of Eq.(3.34b) is that baseball or any other object. The motion of a the motions in x- and y-directions can be treated projectile may be thought of as the result of two independently of each other. That is, motion in separate, simultaneously occurring components a plane (two-dimensions) can be treated as two of motions. One component is along a horizontal separate simultaneous one-dimensional direction without any acceleration and the other motions with constant acceleration along two along the vertical direction with constant perpendicular directions. This is an important acceleration due to the force of gravity. It was result and is useful in analysing motion of objects Galileo who first stated this independency of the in two dimensions. A similar result holds for three horizontal and the vertical components ofdimensions. The choice of perpendicular projectile motion in his Dialogue on the greatdirections is convenient in many physical world systems (1632).situations, as we shall see in section 3.9 for In our discussion, we shall assume that theprojectile motion. air resistance has negligible effect on the motion ⊳ Example 3.5 A particle starts from origin of the projectile. Suppose that the projectile is launched with velocity vo that makes an angle at t = 0 with a velocity 5.0 î m/s and moves in x-y plane under action of a force which θo with the x-axis as shown in Fig. 3.16. produces a constant acceleration of (3.0iɵ+2.0jɵ) m/s 2. (a) What is the After the object has been projected, the acceleration acting on it is that due to gravity y-coordinate of the particle at the instant which is directed vertically downward: its x-coordinate is 84 m ? (b) What is the ɵ speed of the particle at this time ? a = −g j Or, ax = 0, ay = – g (3.35) Answer From Eq. (3.34a) for r0 = 0, the position The components of initial velocity vo are : of the particle is given by 1 at 2 vox = vo cos θo r (t ) = v 0 t + 2 2 voy= vo sin θo (3.36) t 3.0ˆi + 2.0 ˆj = 5.0 ˆi t + (1/2 )( ) Reprint 2025-26 MOTION IN A PLANE 39 Now, since g, θo and vo are constants, Eq. (3.39) is of the form y = a x + b x2, in which a and b are constants. This is the equation of a parabola, i.e. the path of the projectile is a parabola (Fig. 3.17). Fig 3.16 Motion of an object projected with velocity vo at angle θ0. If we take the initial position to be the origin of the reference frame as shown in Fig. 3.16, we have : xo = 0, yo = 0 Then, Eq.(3.34b) becomes : x = vox t = (vo cos θo ) t and y = (vo sin θo ) t – ( ½ )g t2 (3.37) Fig. 3.17 The path of a projectile is a parabola. The components of velocity at time t can be Time of maximum height obtained using Eq.(3.33b) : How much time does the projectile take to reach the vx = vox = vo cos θo maximum height ? Let this time be denoted by tm. Since at this point, vy= 0, we have from Eq. (3.38): vy = vo sin θo – g t (3.38) vy = vo sinθo – g tm = 0 Equation (3.37) gives the x-, and y-coordinates Or, tm = vo sinθo /g (3.40a) of the position of a projectile at time t in terms of The total time Tf during which the projectile is two parameters — initial speed vo and projection in flight can be obtained by putting y = 0 in angle θo. Notice that the choice of mutually Eq. (3.37). We get : perpendicular x-, and y-directions for the analysis of the projectile motion has resulted in Tf = 2 (vo sin θo )/g (3.40b) a simplification. One of the components of Tf is known as the time of flight of the projectile. velocity, i.e. x-component remains constant We note that Tf = 2 tm , which is expected throughout the motion and only the because of the symmetry of the parabolic path. y- component changes, like an object in free fall Maximum height of a projectile in vertical direction. This is shown graphically The maximum height hm reached by theat few instants in Fig. 3.17. Note that at the point projectile can be calculated by substituting of maximum height, vy= 0 and therefore, t = tm in Eq. (3.37) : -1 v y 2 = oθ = tan    g  v 0 sinθ0 v 0 sinθ0 v x y = h m = ( v 0 sinθ0 )  −   Equation of path of a projectile  g  2  g  What is the shape of the path followed by the ( v 0 sinθ0 ) 2 projectile? This can be seen by eliminating the Or, h m = (3.41) 2gtime between the expressions for x and y as given in Eq. (3.37). We obtain: Horizontal range of a projectile g 2 The horizontal distance travelled by a projectile from x y = ( tan θo ) x − (3.39) its initial position (x = y = 0) to the position where it 2 (v o cosθo )2 passes y = 0 during its fall is called the horizontal Reprint 2025-26 40 PHYSICS range, R. It is the distance travelled during the time y (t) = yo + voy t +(1/2) ay t2 of flight Tf . Therefore, the range R is Here, xo = yo = 0, voy = 0, ay = –g = –9.8 m s-2, R = (vo cos θo) (Tf ) vox = 15 m s-1. The stone hits the ground when y(t) = – 490 m. =(vo cos θo) (2 vo sin θo)/g – 490 m = –(1/2)(9.8) t2. 2 sin 2θ0 This gives t =10 s. v 0 Or, R = (3.42a) The velocity components are vx = vox and g vy = voy – g t Equation (3.42a) shows that for a given so that when the stone hits the ground : projection velocity vo , R is maximum when sin vox = 15 m s–1 2θ0 is maximum, i.e., when θ0 = 450. voy = 0 – 9.8 × 10 = – 98 m s–1 The maximum horizontal range is, therefore, Therefore, the speed of the stone is 2 v 0 v 2x + v y2 = 15 2 + 98 2 = 99 m s −1 ⊳ R m = (3.42b) g ⊳ ⊳ Example 3.6 Galileo, in his book Two new Example 3.8 A cricket ball is thrown at a sciences, stated that “for elevations which speed of 28 m s–1 in a direction 30° above exceed or fall short of 45° by equal amounts, the horizontal. Calculate (a) the maximum the ranges are equal”. Prove this statement. height, (b) the time taken by the ball to return to the same level, and (c) the distance from the thrower to the point Answer For a projectile launched with velocity where the ball returns to the same level. vo at an angle θo , the range is given by v 02 sin2θ0 R = Answer (a) The maximum height is given by g 2 2 sin sin 30 ( 28 ( v 0 θo ) ° ) m = m =Now, for angles, (45° + α) and ( 45° – α), 2θo is h 2 2 g ( 9.8 )(90° + 2α) and ( 90° – 2α) , respectively. The values of sin (90° + 2α) and sin (90° – 2α) are 14 × 14 = = 10.0 mthe same, equal to that of cos 2α. Therefore, 2 × 9.8 ranges are equal for elevations which exceed or fall short of 45° by equal amounts α. ⊳ (b) The time taken to return to the same level is Tf = (2 vo sin θo )/g = (2× 28 × sin 30° )/9.8 ⊳ = 28/9.8 s = 2.9 s Example 3.7 A hiker stands on the edge (c) The distance from the thrower to the point of a cliff 490 m above the ground and where the ball returns to the same level is throws a stone horizontally with an initial speed 2 of 15 m s-1. Neglecting air resistance, v o sin2θo 28 × 28 × sin60o ( ) = = 69 m ⊳ find the time taken by the stone to reach R = g 9.8 the ground, and the speed with which it hits the ground. (Take g = 9.8 m s-2 ). 3.10 UNIFORM CIRCULAR MOTION Answer We choose the origin of the x-,and y- When an object follows a circular path at a axis at the edge of the cliff and t = 0 s at the constant speed, the motion of the object is called instant the stone is thrown. Choose the positive uniform circular motion. The word “uniform” direction of x-axis to be along the initial velocity refers to the speed, which is uniform (constant) and the positive direction of y-axis to be the throughout the motion. Suppose an object is vertically upward direction. The x-, and y- moving with uniform speed v in a circle of radius components of the motion can be treated R as shown in Fig. 3.18. Since the velocity of the independently. The equations of motion are : object is changing continuously in direction, the x (t) = xo + vox t object undergoes acceleration. Let us find the magnitude and the direction of this acceleration. Reprint 2025-26 MOTION IN A PLANE 41 Fig. 3.18 Velocity and acceleration of an object in uniform circular motion. The time interval ∆t decreases from (a) to (c) where it is zero. The acceleration is directed, at each point of the path, towards the centre of the circle. Let r and r′ be the position vectors and v and r′ be ∆θ. Since the velocity vectors v and v′ are v′ the velocities of the object when it is at point P always perpendicular to the position vectors, the and P′ as shown in Fig. 3.18(a). By definition, angle between them is also ∆θ . Therefore, the velocity at a point is along the tangent at that triangle CPP′ formed by the position vectors and point in the direction of motion. The velocity the triangle GHI formed by the velocity vectors vectors v and v′ are as shown in Fig. 3.18(a1). v, v′ and ∆v are similar (Fig. 3.18a). Therefore, ∆v is obtained in Fig. 3.18 (a2) using the triangle the ratio of the base-length to side-length for law of vector addition. Since the path is circular, one of the triangles is equal to that of the other v is perpendicular to r and so is v′ to r′. triangle. That is : Therefore, ∆v is perpendicular to ∆r. Since  ∆v  ∆ v ∆ r average acceleration is along ∆v  a =  , the =  ∆t  v R average acceleration a is perpendicular to ∆r. If we place ∆v on the line that bisects the angle ∆ r Or, ∆ v = v between r and r′, we see that it is directed towards R the centre of the circle. Figure 3.18(b) shows the Therefore, same quantities for smaller time interval. ∆v and ∆ v v ∆ r v ∆r hence a is again directed towards the centre. a = lim = lim = lim t ∆ t → 0 R ∆ t R ∆ t → 0 ∆ tIn Fig. 3.18(c), ∆tŽ 0 and the average ∆ t → 0 ∆ acceleration becomes the instantaneous If ∆t is small, ∆θ will also be small and then arc acceleration. It is directed towards the centre*. PP′ can be approximately taken to be|∆r|: Thus, we find that the acceleration of an object ∆ r ≅v∆ t in uniform circular motion is always directed ∆r towards the centre of the circle. Let us now find ≅ v the magnitude of the acceleration. ∆ t The magnitude of a is, by definition, given by ∆ r lim = v ∆v Or, ∆ t → 0 ∆ t a = lim ∆ t → 0 ∆t Let the angle between position vectors r and Therefore, the centripetal acceleration ac is : * In the limit ∆tŽ0, ∆r becomes perpendicular to r. In this limit ∆v→ 0 and is consequently also perpendicular to V. Therefore, the acceleration is directed towards the centre, at each point of the circular path. Reprint 2025-26 42 PHYSICS 2 2 2  v  v R ω 2  R ac = = = ω a c =  R v = v2/R (3.43) R R Thus, the acceleration of an object moving with 2 a c = ω R (3.46) speed v in a circle of radius R has a magnitude v 2/R and is always directed towards the centre. The time taken by an object to make one revolution This is why this acceleration is called centripetal is known as its time period T and the number ofacceleration (a term proposed by Newton). A revolution made in one second is called itsthorough analysis of centripetal acceleration was frequency ν (=1/T). However, during this timefirst published in 1673 by the Dutch scientist the distance moved by the object is s = 2πR.Christiaan Huygens (1629-1695) but it was probably known to Newton also some years earlier. Therefore, v = 2πR/T =2πRν (3.47) “Centripetal” comes from a Greek term which means In terms of frequency ν, we have ‘centre-seeking’. Since v and R are constant, the ω = 2πν magnitude of the centripetal acceleration is also v = 2πRν constant. However, the direction changes — ac = 4π2 ν2R (3.48)pointing always towards the centre. Therefore, a ⊳centripetal acceleration is not a constant vector. Example 3.9 An insect trapped in a We have another way of describing the circular groove of radius 12 cm moves along velocity and the acceleration of an object in the groove steadily and completes 7 uniform circular motion. As the object moves revolutions in 100 s. (a) What is the from P to P′ in time ∆t (= t′ – t), the line CP angular speed, and the linear speed of the (Fig. 3.18) turns through an angle ∆θ as shown motion? (b) Is the acceleration vector a in the figure. ∆θ is called angular distance. We constant vector ? What is its magnitude ? define the angular speed ω (Greek letter omega) as the time rate of change of angular Answer This is an example of uniform circular displacement : motion. Here R = 12 cm. The angular speed ω is ∆θ given by ω = ∆t (3.44) ω = 2π/T = 2π × 7/100 = 0.44 rad/s The linear speed v is :Now, if the distance travelled by the object during the time ∆t is ∆s, i.e. PP′ is ∆s, then : v =ω R = 0.44 s-1 × 12 cm = 5.3 cm s-1 ∆ s The direction of velocity v is along the tangent v = ∆t to the circle at every point. The acceleration is directed towards the centre of the circle. Sincebut ∆s = R ∆θ. Therefore : this direction changes continuously, ∆θ v = R = R ω acceleration here is not a constant vector. ∆ t However, the magnitude of acceleration is v = R ω (3.45) constant: a = ω2 R = (0.44 s–1)2 (12 cm)We can express centripetal acceleration ac in terms of angular speed : = 2.3 cm s-2 ⊳ Reprint 2025-26 MOTION IN A PLANE 43 SUMMARY 1. Scalar quantities are quantities with magnitudes only. Examples are distance, speed, mass and temperature. 2. Vector quantities are quantities with magnitude and direction both. Examples are displacement, velocity and acceleration. They obey special rules of vector algebra. 3. A vector A multiplied by a real number λ is also a vector, whose magnitude is λ times the magnitude of the vector A and whose direction is the same or opposite depending upon whether λ is positive or negative. 4. Two vectors A and B may be added graphically using head-to-tail method or parallelogram method. 5. Vector addition is commutative : A + B = B + A It also obeys the associative law : (A + B) + C = A + (B + C) 6. A null or zero vector is a vector with zero magnitude. Since the magnitude is zero, we don’t have to specify its direction. It has the properties : A + 0 = A λ0 = 0 0 A = 0 7. The subtraction of vector B from A is defined as the sum of A and –B : A – B = A+ (–B) 8. A vector A can be resolved into component along two given vectors a and b lying in the same plane : A = λ a + µ b where λ and µ are real numbers. 9. A unit vector associated with a vector A has magnitude 1 and is along the vector A: A ˆn = A ɵ ɵ ɵ The unit vectors i, j, k are vectors of unit magnitude and point in the direction of the x-, y-, and z-axes, respectively in a right-handed coordinate system. 10. A vector A can be expressed as ɵ ɵ A = A x i + Ay j where Ax, Ay are its components along x-, and y -axes. If vector A makes an angle θ A y 2 2 with the x-axis, then Ax = A cos θ, Ay=A sin θ and A = A = A x + A y , tanθ = . A x 11. Vectors can be conveniently added using analytical method. If sum of two vectors A and B, that lie in x-y plane, is R, then : ɵ R = R x i + Ry ɵ,j where, Rx = Ax + Bx, and Ry = Ay + By ɵ ɵ 12. The position vector of an object in x-y plane is given by r = x i + y j and the displacement from position r to position r’ is given by ∆r = r′− r ɵ ɵ = ( x ′ − x ) i + (y ′ − y ) j ɵ ɵ = ∆x i + ∆y j 13. If an object undergoes a displacement ∆r in time ∆t, its average velocity is given by ∆ r v = . The velocity of an object at time t is the limiting value of the average velocity ∆t as ∆t tends to zero : Reprint 2025-26 44 PHYSICS ∆ r d r v = lim = . It can be written in unit vector notation as : ∆ t →0 ∆ t dt ɵ ɵ ɵ dx dy dz = y v = v x i + v y j + v z k where v x = dt , v dt , v z = dt When position of an object is plotted on a coordinate system, v is always tangent to the curve representing the path of the object. 14. If the velocity of an object changes from v to v′in time ∆t, then its average acceleration v − v' ∆ v is given by: a = = ∆ t ∆t The acceleration a at any time t is the limiting value of a as ∆t Ž0 : ∆ v dv a = lim = ∆ t → 0 ∆ t dt ɵ ɵ ɵ In component form, we have : a = a x i + a y j + a z k dvy dv x dv z where, a x = , a y = , a z = dt dt dt 15. If an object is moving in a plane with constant acceleration a = a = a x2 + a y2 and its position vector at time t = 0 is ro, then at any other time t, it will be at a point given by: 1 2 r = ro + v o t + at 2 and its velocity is given by : v = vo + a t where vo is the velocity at time t = 0 In component form : 1 2 x = x o + v ox t + a x t 2 1 2 y = yo + v oy t + a y t 2 v x = v ox + a x t v y = v oy + a y t Motion in a plane can be treated as superposition of two separate simultaneous one- dimensional motions along two perpendicular directions 16. An object that is in flight after being projected is called a projectile. If an object is projected with initial velocity vo making an angle θo with x-axis and if we assume its initial position to coincide with the origin of the coordinate system, then the position and velocity of the projectile at time t are given by : x = (vo cos θo) t y = (vo sin θo) t − (1/2) g t2 vx = vox = vo cos θo vy = vo sin θo − g t The path of a projectile is parabolic and is given by : 2 gx y = ( tanθ0 ) x – 2 2 (v o cosθo ) The maximum height that a projectile attains is : Reprint 2025-26 MOTION IN A PLANE 45 (v o sinq o )2 h m = 2g The time taken to reach this height is : v o sinθo t m = g The horizontal distance travelled by a projectile from its initial position to the position it passes y = 0 during its fall is called the range, R of the projectile. It is : v o2 R = sin2θo g 17. When an object follows a circular path at constant speed, the motion of the object is called uniform circular motion. The magnitude of its acceleration is ac = v2 /R. The direction of ac is always towards the centre of the circle. The angular speed ω, is the rate of change of angular distance. It is related to velocity v by v = ω R. The acceleration is ac = ω 2R. If T is the time period of revolution of the object in circular motion and ν is its frequency, we have ω = 2π ν, v = 2πνR, ac = 4π2ν2R Reprint 2025-26 46 PHYSICS POINTS TO PONDER 1. The path length traversed by an object between two points is, in general, not the same as the magnitude of displacement. The displacement depends only on the end points; the path length (as the name implies) depends on the actual path. The two quantities are equal only if the object does not change its direction during the course of motion. In all other cases, the path length is greater than the magnitude of displacement. 2. In view of point 1 above, the average speed of an object is greater than or equal to the magnitude of the average velocity over a given time interval. The two are equal only if the path length is equal to the magnitude of displacement. 3. The vector equations (3.33a) and (3.34a) do not involve any choice of axes. Of course, you can always resolve them along any two independent axes. 4. The kinematic equations for uniform acceleration do not apply to the case of uniform circular motion since in this case the magnitude of acceleration is constant but its direction is changing. 5. An object subjected to two velocities v1 and v2 has a resultant velocity v = v1 + v2. Take care to distinguish it from velocity of object 1 relative to velocity of object 2 : v12= v1 − v2. Here v1 and v2 are velocities with reference to some common reference frame. 6. The resultant acceleration of an object in circular motion is towards the centre only if the speed is constant. 7. The shape of the trajectory of the motion of an object is not determined by the acceleration alone but also depends on the initial conditions of motion ( initial position and initial velocity). For example, the trajectory of an object moving under the same acceleration due to gravity can be a straight line or a parabola depending on the initial conditions. EXERCISES 3.1 State, for each of the following physical quantities, if it is a scalar or a vector : volume, mass, speed, acceleration, density, number of moles, velocity, angular frequency, displacement, angular velocity. 3.2 Pick out the two scalar quantities in the following list : force, angular momentum, work, current, linear momentum, electric field, average velocity, magnetic moment, relative velocity. 3.3 Pick out the only vector quantity in the following list : Temperature, pressure, impulse, time, power, total path length, energy, gravitational potential, coefficient of friction, charge. 3.4 State with reasons, whether the following algebraic operations with scalar and vector physical quantities are meaningful : (a) adding any two scalars, (b) adding a scalar to a vector of the same dimensions , (c) multiplying any vector by any scalar, (d) multiplying any two scalars, (e) adding any two vectors, (f) adding a component of a vector to the same vector. 3.5 Read each statement below carefully and state with reasons, if it is true or false : (a) The magnitude of a vector is always a scalar, (b) each component of a vector is always a scalar, (c) the total path length is always equal to the magnitude of the displacement vector of a particle. (d) the average speed of a particle (defined as total path length divided by the time taken to cover the path) is either greater or equal to the magnitude of average velocity of the particle over the same interval of time, (e) Three vectors not lying in a plane can never add up to give a null vector. 3.6 Establish the following vector inequalities geometrically or otherwise : (a) |a+b| < |a| + |b| (b) |a+b| > ||a| −|b|| Reprint 2025-26 MOTION IN A PLANE 47 (c) |a−b| < |a| + |b| (d) |a−b| > ||a| − |b|| When does the equality sign above apply? 3.7 Given a + b + c + d = 0, which of the following statements are correct : Q (a) a, b, c, and d must each be a null vector, (b) The magnitude of (a + c) equals the magnitude of ( b + d), (c) The magnitude of a can never be greater than the sum of the magnitudes of b, c, and d, (d) b + c must lie in the plane of a and d if a and d are not collinear, and in the line of a and d, if they are collinear ? 3.8 Three girls skating on a circular ice ground of radius 200 m start from a point P on the edge of the ground and reach a point Q diametrically opposite to P following different paths as shown in Fig. 3.19. What is the magnitude of the displacement vector for each ? For Fig. 3.19 which girl is this equal to the actual length of path skate ? 3.9 A cyclist starts from the centre O of a circular park of radius 1 km, reaches the edge P of the park, then cycles along the circumference, and returns to the centre along QO as shown in Fig. 3.20. If the round trip takes 10 min, what is the (a) net displacement, (b) average velocity, and (c) average speed of the cyclist ? Fig. 3.20 3.10 On an open ground, a motorist follows a track that turns to his left by an angle of 600 after every 500 m. Starting from a given turn, specify the displacement of the motorist at the third, sixth and eighth turn. Compare the magnitude of the displacement with the total path length covered by the motorist in each case. 3.11 A passenger arriving in a new town wishes to go from the station to a hotel located 10 km away on a straight road from the station. A dishonest cabman takes him along a circuitous path 23 km long and reaches the hotel in 28 min. What is (a) the average speed of the taxi, (b) the magnitude of average velocity ? Are the two equal ? 3.12 The ceiling of a long hall is 25 m high. What is the maximum horizontal distance that a ball thrown with a speed of 40 m s-1 can go without hitting the ceiling of the hall ? 3.13 A cricketer can throw a ball to a maximum horizontal distance of 100 m. How much high above the ground can the cricketer throw the same ball ? Reprint 2025-26 48 PHYSICS 3.14 A stone tied to the end of a string 80 cm long is whirled in a horizontal circle with a constant speed. If the stone makes 14 revolutions in 25 s, what is the magnitude and direction of acceleration of the stone ? 3.15 An aircraft executes a horizontal loop of radius 1.00 km with a steady speed of 900 km/h. Compare its centripetal acceleration with the acceleration due to gravity. 3.16 Read each statement below carefully and state, with reasons, if it is true or false : (a) The net acceleration of a particle in circular motion is always along the radius of the circle towards the centre (b) The velocity vector of a particle at a point is always along the tangent to the path of the particle at that point (c) The acceleration vector of a particle in uniform circular motion averaged over one cycle is a null vector 3.17 The position of a particle is given by r = 3.0t ˆi − 2.0t 2 ˆj + 4.0 kˆ m where t is in seconds and the coefficients have the proper units for r to be in metres. (a) Find the v and a of the particle? (b) What is the magnitude and direction of velocity of the particle at t = 2.0 s ? 3.18 A particle starts from the origin at t = 0 s with a velocity of 10.0 jɵ m/s and moves in ɵ ɵ the x-y plane with a constant acceleration of 8.0 i + 2.0 j m s-2. (a) At what time is ( ) the x- coordinate of the particle 16 m? What is the y-coordinate of the particle at that time? (b) What is the speed of the particle at the time ? 3.19 ɵi and ɵj are unit vectors along x- and y- axis respectively. What is the magnitude ɵ ɵ ɵ ɵ and direction of the vectors i + j , and i − j ? What are the components of a vector ɵ ɵ ɵ ɵ ɵ ɵ A= 2 i + 3 j along the directions of i + j and i −?j [You may use graphical method] 3.20 For any arbitrary motion in space, which of the following relations are true : (a) vaverage = (1/2) (v (t1) + v (t2)) (b) v average = [r(t2) - r(t1) ] /(t2 – t1) (c) v (t) = v (0) + a t (d) r (t) = r (0) + v (0) t + (1/2) a t2 (e) a average =[ v (t2) - v (t1 )] /( t2 – t1) (The ‘average’ stands for average of the quantity over the time interval t1 to t2) 3.21 Read each statement below carefully and state, with reasons and examples, if it is true or false : A scalar quantity is one that (a) is conserved in a process (b) can never take negative values (c) must be dimensionless (d) does not vary from one point to another in space (e) has the same value for observers with different orientations of axes. 3.22 An aircraft is flying at a height of 3400 m above the ground. If the angle subtended at a ground observation point by the aircraft positions 10.0 s a part is 30°, wat is the speed of the aircraft ? Reprint 2025-26 CHAPTER FOUR LAWS OF MOTION 4.1 INTRODUCTION In the preceding Chapter, our concern was to describe the motion of a particle in space quantitatively. We saw that 4.1 Introduction uniform motion needs the concept of velocity alone whereas 4.2 Aristotle’s fallacy non-uniform motion requires the concept of acceleration in 4.3 The law of inertia addition. So far, we have not asked the question as to what governs the motion of bodies. In this chapter, we turn to this4.4 Newton’s first law of motion basic question.4.5 Newton’s second law of Let us first guess the answer based on our common motion experience. To move a football at rest, someone must kick it.4.6 Newton’s third law of motion To throw a stone upwards, one has to give it an upward

9.3 Alkenes Alkenes are unsaturated hydrocarbons Fig. 9.4 Orbital picture of ethene depictingcontaining at least one double bond. What σ bonds only should be the general formula of alkenes? If there is one double bond between two carbon 9.3.2 Nomenclature atoms in alkenes, they must possess two For nomenclature of alkenes in IUPAC system, hydrogen atoms less than alkanes. Hence, the longest chain of carbon atoms containing general formula for alkenes is CnH2n. Alkenes the double bond is selected. Numbering of the are also known as olefins (oil forming) since chain is done from the end which is nearer to Reprint 2025-26 Hydrocarbons 307 Fig. 9.5 Orbital picture of ethene showing formation of (a) π-bond, (b) π-cloud and (c) bond angles and bond lengths the double bond. The suffix ‘ene’ replaces ‘ane’ Solutionof alkanes. It may be remembered that first member of alkene series is: CH2 (replacing (i) 2,8-Dimethyl-3, 6-decadiene; n by 1 in CnH2n) known as methene but has (ii) 1,3,5,7 Octatetraene; a very short life. As already mentioned, first (iii) 2-n-Propylpent-1-ene; stable member of alkene series is C2H4 known (iv) 4-Ethyl-2,6-dimethyl-dec-4-ene;as ethylene (common) or ethene (IUPAC). IUPAC names of a few members of alkenes Problem 9.8 are given below : Calculate number of sigma (σ) and pi (π) Structure IUPAC name bonds in the above structures (i-iv). CH3 – CH = CH2 Propene SolutionCH3 – CH2 – CH = CH2 But – l - ene σ bonds : 33, π bonds : 2CH3 – CH = CH–CH3 But-2-ene σ bonds : 17, π bonds : 4CH2 = CH – CH = CH2 Buta – 1,3 - diene σ bonds : 23, π bond : 1CH2 = C – CH3 2-Methylprop-1-ene | σ bonds : 41, π bond : 1 CH3 CH2 = CH – CH – CH3 3-Methylbut-1-ene 9.3.3 Isomerism | Alkenes show both structural isomerism and CH3 geometrical isomerism. Structural isomerism : As in alkanes, ethene Problem 9.7 (C2H4) and propene (C3H6) can have only one Write IUPAC names of the following structure but alkenes higher than propene compounds: have different structures. Alkenes possessing (i) (CH3)2CH – CH = CH – CH2 – CH C4H8 as molecular formula can be written in  the following three ways: CH3 – CH – CH | I. 1 2 3 4 C2H5 CH2 = CH – CH2 – CH3 (ii) But-1-ene (C4H8) (iii) CH2 = C (CH2CH2CH3)2 (iv) CH3 CH2 CH2 CH2 CH2CH3 II. 1 2 3 4 | | CH3 – CH = CH – CH3 CH3 – CHCH = C – CH2 – CHCH3 | But-2-ene CH3 (C4H8) Reprint 2025-26 308 chemistry III. 1 2 3 In (a), the two identical atoms i.e., both CH2 = C – CH3 the X or both the Y lie on the same side | of the double bond but in (b) the two X or CH3 two Y lie across the double bond or on the 2-Methylprop-1-ene opposite sides of the double bond. This (C4H8) results in different geometry of (a) and (b) i.e. disposition of atoms or groups in space in Structures I and III, and II and III are the two arrangements is different. Therefore,the examples of chain isomerism whereas they are stereoisomers. They would have thestructures I and II are position isomers. same geometry if atoms or groups around C=C bond can be rotated but rotation around Problem 9.9 C=C bond is not free. It is restricted. For Write structures and IUPAC names of understanding this concept, take two pieces different structural isomers of alkenes of strong cardboards and join them with the corresponding to C5H10. help of two nails. Hold one cardboard in your Solution one hand and try to rotate the other. Can (a) CH2 = CH – CH2 – CH2 – CH3 you really rotate the other cardboard ? The answer is no. The rotation is restricted. This Pent-1-ene illustrates that the restricted rotation of atoms (b) CH3 – CH=CH – CH2 – CH3 or groups around the doubly bonded carbon Pent-2-ene atoms gives rise to different geometries of such compounds. The stereoisomers of this (c) CH3 – C = CH – CH3 type are called geometrical isomers. The | isomer of the type (a), in which two identical CH3 atoms or groups lie on the same side of the 2-Methylbut-2-ene double bond is called cis isomer and the (d) CH3 – CH – CH = CH2 other isomer of the type (b), in which identical | atoms or groups lie on the opposite sides of CH3 the double bond is called trans isomer . Thus 3-Methylbut-1-ene cis and trans isomers have the same structure but have different configuration (arrangement (e) CH2 = C – CH2 – CH3 of atoms or groups in space). Due to different | arrangement of atoms or groups in space, CH3 these isomers differ in their properties like 2-Methylbut-1-ene melting point, boiling point, dipole moment, solubility etc. Geometrical or cis-trans isomersGeometrical isomerism: Doubly bonded of but-2-ene are represented below :carbon atoms have to satisfy the remaining two valences by joining with two atoms or groups. If the two atoms or groups attached to each carbon atom are different, they can be represented by YX C = C XY like structure. YX C = C XY can be represented in space in the following two ways : Cis form of alkene is found to be more polar than the trans form. For example, dipole moment of cis-but-2-ene is 0.33 Debye, whereas, dipole moment of the trans form is almost zero or it can be said that Reprint 2025-26 Hydrocarbons 309 trans-but-2-ene is non-polar. This can be (ii) CH2 = CBr2 understood by drawing geometries of the two (iii) C6H5CH = CH – CH3forms as given below from which it is clear that in the trans-but-2-ene, the two methyl (iv) CH3CH = CCl CH3 groups are in opposite directions, Threfore, dipole moments of C-CH3 bonds cancel, thus Solution making the trans form non-polar. (iii) and (iv). In structures (i) and (ii), two identical groups are attached to one of the doubly bonded carbon atom. 9.3.4 Preparation 1. From alkynes: Alkynes on partial reduction with calculated amount of cis-But-2-ene trans-But-2-ene dihydrogen in the presence of palladised (µ = 0.33D) (µ = 0) charcoal partially deactivated with poisons like sulphur compounds or quinoline give In the case of solids, it is observed that the alkenes. Partially deactivated palladisedtrans isomer has higher melting point than charcoal is known as Lindlar’s catalyst.the cis form. Alkenes thus obtained are having cis Geometrical or cis-trans isomerism geometry. However, alkynes on reductionis also shown by alkenes of the types with sodium in liquid ammonia form transXYC = CXZ and XYC = CZW alkenes. Problem 9.10 Draw cis and trans isomers of the following compounds. Also write their IUPAC names : (i) CHCl = CHCl (9.30) (ii) C2H5CCH3 = CCH3C2H5 Solution (9.31) iii) CH≡ CH+H2 Pd/C CH2 =CH2 (9.32) Ethyne Ethene CH3–C≡ CH+H2 Pd/C CH3–CH =CH2 iv) Propyne Propene (9.33) Will propene thus obtained show Problem 9.11 geometrical isomerism? Think for the reason in support of your answer. Which of the following compounds will show cis-trans isomerism? 2. From alkyl halides: Alkyl halides (R-X) on (i) (CH3)2C = CH – C2H5 heating with alcoholic potash (potassium hydroxide dissolved in alcohol, say, Reprint 2025-26 310 chemistry ethanol) eliminate one molecule of halogen takes out one hydrogen atom from the acid to form alkenes. This reaction is β-carbon atom. known as dehydrohalogenation i.e., removal of halogen acid. This is example of β-elimination reaction, since hydrogen atom is eliminated from the β carbon atom (carbon atom next to the carbon to which halogen is attached). (9.37) 9.3.5 Properties Physical properties Alkenes as a class resemble alkanes in physical properties, except in types of isomerism and difference in polar nature. (9.34) The first three members are gases, the next fourteen are liquids and the higher ones are Nature of halogen atom and the alkyl group solids. Ethene is a colourless gas with a faint determine rate of the reaction. It is observed sweet smell. All other alkenes are colourless that for halogens, the rate is: iodine > and odourless, insoluble in water but fairly bromine > chlorine, while for alkyl groups soluble in non-polar solvents like benzene, it is : tertiary > secondary > primary. petroleum ether. They show a regular increase 3. From vicinal dihalides: Dihalides in in boiling point with increase in size i.e., every which two halogen atoms are attached – CH2 group added increases boiling point by to two adjacent carbon atoms are known 20–30 K. Like alkanes, straight chain alkenes as vicinal dihalides. Vicinal dihalides on have higher boiling point than isomeric treatment with zinc metal lose a molecule branched chain compounds. of ZnX2 to form an alkene. This reaction Chemical properties is known as dehalogenation. Alkenes are the rich source of loosely held CH2Br–CH2Br + Zn CH2=CH2+ ZnBr2 pi (π) electrons, due to which they show (9.35) addition reactions in which the electrophiles add on to the carbon-carbon double bond toCH3CHBr–CH2Br + Zn CH3CH=CH2 form the addition products. Some reagents +ZnBr2 also add by free radical mechanism. There (9.36) are cases when under special conditions, alkenes also undergo free radical substitution4. From alcohols by acidic dehydration: reactions. Oxidation and ozonolysis reactions You have read during nomenclature of are also quite prominent in alkenes. A brief different homologous series in Unit 12 description of different reactions of alkenes that alcohols are the hydroxy derivatives is given below: of alkanes. They are represented by R–OH where, R is CnH2n+1. Alcohols on heating 1. Addition of dihydrogen: Alkenes add with concentrated sulphuric acid form up one molecule of dihydrogen gas in alkenes with the elimination of one water the presence of finely divided nickel, molecule. Since a water molecule is palladium or platinum to form alkanes eliminated from the alcohol molecule in (Section 9.2.2) the presence of an acid, this reaction is 2. Addition of halogens : Halogens like known as acidic dehydration of alcohols. bromine or chlorine add up to alkene to This reaction is also the example of form vicinal dihalides. However, iodine β-elimination reaction since –OH group does not show addition reaction under Reprint 2025-26 Hydrocarbons 311 normal conditions. The reddish orange colour of bromine solution in carbon tetrachloride is discharged when bromine adds up to an unsaturation site. This reaction is used as a test for unsaturation. Addition of halogens to alkenes is an example of electrophilic addition reaction involving cyclic halonium ion formation (9.42) which you will study in higher classes. Markovnikov, a Russian chemist made a generalisation in 1869 after studying such reactions in detail. These generalisations led Markovnikov to frame a rule called Markovnikov rule. The rule states that negative part of the addendum (adding (9.38) molecule) gets attached to that carbon atom which possesses lesser number of hydrogen atoms. Thus according to this rule, product I i.e., 2-bromopropane is expected. In actual practice, this is the principal product of the reaction. This generalisation of Markovnikov (9.39) rule can be better understood in terms of mechanism of the reaction. 3. Addition of hydrogen halides: Hydrogen halides (HCl, HBr,HI) add up to alkenes Mechanism to form alkyl halides. The order of Hydrogen bromide provides an electrophile, reactivity of the hydrogen halides is H +, which attacks the double bond to form HI > HBr > HCl. Like addition of halogens carbocation as shown below : to alkenes, addition of hydrogen halides is also an example of electrophilic addition reaction. Let us illustrate this by taking addition of HBr to symmetrical and unsymmetrical alkenes Addition reaction of HBr to symmetrical alkenes (a) less stable (b) more stableAddition reactions of HBr to symmetrical primary carbocation secondary carbocationalkenes (similar groups attached to double bond) take place by electrophilic addition (i) The secondary carbocation (b) is more mechanism. stable than the primary carbocation (a), therefore, the former predominates CH2=CH2+H–Br CH3–CH2–Br (9.40) because it is formed at a faster rate. (ii) The carbocation (b) is attacked by Br– ionCH3–CH=CH–CH3+HBr CH3–CH–CHCH3 to form the product as follows : Br (9.41) Addition reaction of HBr to unsymmetrical alkenes (Markovnikov Rule) How will H – Br add to propene ? The two 2-Bromopropane possible products are I and II. (major product) Reprint 2025-26 312 chemistry Anti Markovnikov addition or peroxide effect or Kharash effect In the presence of peroxide, addition of HBr to unsymmetrical alkenes like propene takes place contrary to the Markovnikov rule. This happens only with HBr but not with HCl The secondary free radical obtained in the and Hl. This addition reaction was observed above mechanism (step iii) is more stable than by M.S. Kharash and F.R. Mayo in 1933 the primary. This explains the formation of at the University of Chicago. This reaction 1-bromopropane as the major product. It may is known as peroxide or Kharash effect be noted that the peroxide effect is not observed or addition reaction anti to Markovnikov in addition of HCl and HI. This may be due rule. to the fact that the H–Cl bond being (C6H5CO)2O2 stronger (430.5 kJ mol –1) than H–Br bond CH3 – CH=CH2+HBr CH3–CH2 (363.7 kJ mol –1), is not cleaved by the free radical, whereas the H–I bond is weaker CH2Br (296.8 kJ mol –1) and iodine free radicals 1–Bromopropane combine to form iodine molecules instead of adding to the double bond. (9.43) Mechanism : Peroxide effect proceeds via Problem 9.12 free radical chain mechanism as given below: Write IUPAC names of the products obtained by addition reactions of HBr to(i) hex-1-ene (i) in the absence of peroxide and (ii) in the presence of peroxide. Solution Homolysis C. 6H5+H–Br C6H3+ B. r(ii) 4. Addition of sulphuric acid : Cold concentrated sulphuric acid adds to alkenes in accordance with Markovnikov rule to form alkyl hydrogen sulphate by the electrophilic addition reaction. Reprint 2025-26 Hydrocarbons 313 ketones and/or acids depending upon the nature of the alkene and the experimental conditions (9.49) KMnO4/H+ CH3 – CH=CH–CH3 2CH3COOH (9.44) But-2-ene Ethanoic acid (9.50) 7. Ozonolysis : Ozonolysis of alkenes involves the addition of ozone molecule to alkene to form ozonide, and then cleavage of the ozonide by Zn-H2O to smaller molecules. This reaction is highly useful in detecting the position of the double (9.45) bond in alkenes or other unsaturated compounds.5. Addition of water : In the presence of a few drops of concentrated sulphuric acid alkenes react with water to form alcohols, in accordance with the Markovnikov rule. (9.51) (9.46) 6. Oxidation: Alkenes on reaction with cold, dilute, aqueous solution of potassium permanganate (Baeyer’s reagent) produce vicinal glycols. Decolorisation of KMnO4 solution is used as a test for unsaturation. (9.52) 8. Polymerisation: You are familiar with (9.47) polythene bags and polythene sheets. Polythene is obtained by the combination of large number of ethene molecules at high temperature, high pressure and in the presence of a catalyst. The large molecules thus obtained are called (9.48) polymers. This reaction is known as b) Acidic potassium permanganate or acidic polymerisation. The simple compounds potassium dichromate oxidises alkenes to from which polymers are made are called Reprint 2025-26 314 chemistry monomers. Other alkenes also undergo are named as derivatives of the corresponding polymerisation. alkanes replacing ‘ane’ by the suffix ‘yne’. n(CH2 =CH2) High temp./pressureCatalyst —( CH2–CH2 )— The position of the triple bond is indicated by the first triply bonded carbon. Common Polythene and IUPAC names of a few members of alkyne (9.53) series are given in Table 9.2. High temp./pressure You have already learnt that ethyne and n(CH3 –CH=CH2) Catalyst —( CH–CH2 )—n propyne have got only one structure but there are two possible structures for butyne – CH3 (i) but-1-yne and (ii) but-2-yne. Since these Polypropene two compounds differ in their structures (9.54) due to the position of the triple bond, they Polymers are used for the manufacture of plastic are known as position isomers. In how bags, squeeze bottles, refrigerator dishes, toys, many ways, you can construct the structure pipes, radio and T.V. cabinets etc. Polypropene for the next homologue i.e., the next alkyne is used for the manufacture of milk crates, with molecular formula C5H8? Let us try to plastic buckets and other moulded articles. arrange five carbon atoms with a continuous Though these materials have now become chain and with a side chain. Following are the common, excessive use of polythene and possible structures : polypropylene is a matter of great concern for Structure IUPAC name all of us. 1 2 3 4 5 I. HC≡ C– CH2– CH2– CH3 Pent–1-yne

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: