Physical Chemistry
Physical Chemistry
2nd Edition
ISBN: 9781285969770
Author: Ball
Publisher: Cengage
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Chapter 10, Problem 10.71E

Mathematically, the uncertainty Δ A in some observable A is given by Δ A = A 2 A 2 . Use this formula to determine Δ x and Δ p x for Ψ = ( 2 / a ) sin ( π x / a ) and show that the uncertainty principle holds.

Expert Solution & Answer
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Interpretation Introduction

Interpretation:

The value of Δx and Δpx for Ψ is to be determined. The validation of uncertainty principle is to be shown.

Concept introduction:

The uncertainty principle deals only with the parameters that cannot be measured simultaneously. Such two parameters are momentum and position in same direction. The uncertainty principle is given by formula as follows.

ΔxΔpx2

Where,

Δx represents the uncertainty in the position of the object.

Δpx represents the uncertainty in the momentum of the object.

represents a constant.

Answer to Problem 10.71E

The uncertainty in the position of a particle is (a2ππ263).

The uncertainty in the momentum of a particle is πa.

The uncertainty principle has been validated.

Explanation of Solution

From Appendix 1,

xsin2(bx)dx=x24x4bsin(2bx)18b2cos(2bx) …(1)

The average value of x is calculated as,

x=0aΨx^Ψdx …(2)

Where,

x^ represents the position operator.

Ψ represents the wavefunction.

The given wavefunction Ψ is defined as 2asinπxa.

The position operator is defined as x().

Substitute the value of Ψ and x^ in the equation (2).

x=0a(2asinπxa)x(2asinπxa)dx=0ax(2asinπxa)2dx=2a0ax(sinπxa)2dx

Assume b=πa and expand the above expression similarly as equation (1).

x=2a[x24xa4(π)sin2πxaa38(π)3cos2πxa]0a=2a[(a24a24πsin2πaaa38(π)3cos2πaa)((0)24(0)a4(π)sin2π(0)aa38(π)3cos2π(0)a)]=2a[(a24a24πsin2πa38(π)3cos2π)((0)24(0)a4(π)sin2π(0)aa38(π)3cos2π(0)a)]

Substitute the value of sinπ=0 in the above expression.

x==2a[(a24a24π(0)a38(π)3cos2π)((0)24(0)a4(π)sin4π(0)aa38(π)3cos2π(0)a)]=(2a)(a24)=a2

Therefore, the average value of position, x, for Ψ1 of a particle-in-a-box is a2.

From Appendix 1,

sin(bx)cos(bx)dx=1bsin2(bx) …(3)

The average value of px is calculated as,

px=0aΨ1px^Ψ1dx …(4)

Where,

px^ represents an operator.

Ψ1 represents the wavefunction.

The given wavefunction Ψ1 is defined as 2asinπxa.

The operator px^ is defined as iddx().

Substitute the value of Ψ1 and x^ in the equation (4).

px=0a(2asinπxa)iddx(2asinπxa)dx=0a(2asinπxa)(i)(2a(πa)cosπxa)dx=2iπa20a(sinπxacos2πxa)dx

Assume b=πa and expand the above expression similarly as equation (3).

px=2iπa2[(1(π/a))sin2(πxa)]0a=2iπa2[(1(π/a))sin2(π(a)a)(1(π/a))sin2(π(0)a)]=2iπa2[(1(π/a))sin2(π)(1(π/a))(0)]

Substitute the value of sinπ=0 in the above expression.

px=2iπa2[(1(π/a))(0)(1(π/a))(0)]=0

Therefore, the value of px, for Ψ1 of a particle-in-a-box is 0.

From Appendix 1,

x2sin2(bx)dx=x36(x24b18b3)sin(2bx)x4b2cos(2bx) …(5)

The average value of x2 is calculated as,

x2=0aΨx2^Ψdx …(6)

Where,

x2^ represents an operator.

Ψ represents the wavefunction.

The wavefunction at n=1, Ψ1, is defined as 2asinπxa.

The wavefunction at n=2, Ψ2, is defined as 2asin2πxa.

The operator x2^ is defined as x2().

Substitute the value of Ψ1 and x2^ in the equation (6).

x2=0a(2asinπxa)x2(2asinπxa)dx=0ax2(2asinπxa)2dx=2a0ax2(sinπxa)2dx

Assume b=πa and expand the above expression similarly as equation (5).

x2 =(2a)[ x 36( x 2 4( π/a ) 1 8 ( π/a ) 3 )sin(2( π/a )x)x4 ( π/a ) 2cos(2( π/a )x) ]0a=(2a)[ ( ( a ) 3 6 ( ( a ) 2 4( π/a ) 1 8 ( π/a ) 3 )sin( 2( π/a )( a ) ) ( a ) 4 ( π/a ) 2 cos( 2( π/a )( a ) ))( ( 0 ) 3 6 ( ( 0 ) 2 4( π/a ) 1 8 ( π/a ) 3 )sin( 2( π/a )( 0 ) ) ( 0 ) 4 ( π/a ) 2 cos( 2( π/a )( 0 ) ))]=(2a)[ ( ( a ) 3 6( a 3 4 π 2 a 3 8 π 3 )sin( 2π) a 3 4 π 2 cos( 2π))0 ]

Substitute the value of sin2π=0 and cos2π=1 in the above expression.

x2=(2a)[((a)36(a34π2a38π3)(0)a34π2(1))0]=(2a)((a)36a34π2)=a23a22π2

Therefore, the value of x2 for a particle-in-a-box having n=1 is (a23a22π2).

From Appendix 1,

sin2(bx)dx=x214bsin(2bx) …(7)

The average value of px is calculated as,

px2=0aΨpx2^Ψdx …(8)

Where,

px2^ represents an operator.

Ψ represents the wavefunction.

The wavefunction at n=1, Ψ1, is defined as 2asinπxa.

The wavefunction at n=2, Ψ2, is defined as 2asin2πxa.

The operator px2^ is defined as 22x2().

Substitute the value of Ψ1 and px2^ in the equation (8)

px2=0a(2asinπxa)22x2(2asinπxa)dx=0a(2asinπxa)(2)(2a)(πa)(x(cosπxa))dx=0a(2asinπxa)(2)(2a)(πa)2(sinπxa)dx=2π22a30a(sin2πxa)dx

Assume b=πa and expand the above expression similarly as equation (7).

px2=(2π22a3)[x214(π/a)sin(2(π/a)x)]0a=(2π22a3)[(a214(π/a)sin(2(π/a)(a)))((0)214(π/a)sin(2(π/a)(0)))]=(2π22a3)[(a214(π/a)sin(2π))(0)]

Substitute the value of sin2π=0 in the above expression.

px2=(2π22a3)(a2)=π22a2

Therefore, the value of px2 for a particle-in-a-box having n=1 is (π22a2).

The given relation is represented as,

ΔA=A2A2…(9)

Where,

ΔA represents the uncertainty ΔA in an observable.

The equation (9) can be represented for the value of Δx as,

Δx=x2x2…(10)

Substitute the value of x2 and x in the equation (10).

Δx=(a23a22π2)(a2)2=a1312π214=a4π263π212π2=a2ππ263

Therefore, the uncertainty in the position of a particle is (a2ππ263).

The equation (9) can be represented for the value of Δpx as,

Δpx=px2px2…(11)

Substitute the value of px2 and px2 in the equation (11).

Δpx=(π22a2)0=πa

Therefore, the uncertainty in the momentum of a particle is πa.

The uncertainty principle is given by formula as follows.

ΔxΔpx2…(12)

Where,

Δx represents the uncertainty in the position of the object.

Δpx represents the uncertainty in the momentum of the object.

represents a constant.

Substitute the value of Δx and Δpx in the equation (12).

(a2ππ263)(πa)2(2π263)2

Substitute the value of π=3.14 in the above expression.

(2)((3.14)263)2(2)(3.85963)2(2)(1.2865)2(1.1342)(2)2

The value of left hand side in the above expression is greater than the value of right-hand side. Therefore, the above expression shows that the uncertainty principle is valid.

Conclusion

The uncertainty in the position of a particle is (a2ππ263).

The uncertainty in the momentum of a particle is πa.

The uncertainty principle has been validated.

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