1.

(a)
Strategy:

We are given the wavelength of an electromagnetic wave and asked to calculate

the frequency.

Rearranging Equation (1.2) of the text and replacing u with c (the speed of

light) gives:

Solution:

Because the speed of light is given in meters per second, it is convenient to first

convert wavelength to units of meters.

456 nm

Recall that 1 nm 1 109 m.

We write:

1 109 m
456 109 m 4.56 107 m
1 nm

Substituting in the wavelength and the speed of light ( 3.00 108 m s 1 ), the frequency is:

4.56 10

6.58 1014 s 1 or 6.58 1014 Hz

The answer shows that 6.58 1014 waves pass a fixed point every second.

Check:

This

very high frequency is in accordance with the very high speed of light.

(b)
Strategy:

We are given the frequency of an electromagnetic wave and asked to calculate

the wavelength.

Rearranging Equation (1.2) of the text and replacing u with c (the speed of

light) gives:

Solution:

Substituting in the frequency and the speed of light ( 3.00 108 m s 1 ) into the

above equation, the wavelength is:

2.45 109 s 1

0.122 m

The problem asks for the wavelength in units of nanometers.

Recall that 1 nm 1 109 m.

 0.122 m
1.6

1 nm
1 10

1.22 108 nm
m

(a)
Strategy:

We are given the frequency of an electromagnetic wave and asked to calculate

the wavelength.

Rearranging Equation (1.2) of the text and replacing u with c (the speed of

light) gives:

Substituting in the frequency and the speed of light (3.00 108 m s-1) into the

Solution:

above equation, the wavelength is:

7.5 1014 s 1

Check:

4.0 107 m 4.0 102 nm

The wavelength of 400 nm calculated is in the blue region of the visible spectrum

as expected.

(b)
Strategy:
energy.

We are given the frequency of an electromagnetic wave and asked to calculate its

Equation (1.3) of the text relates the energy and frequency of an electromagnetic

wave.
E h

Solution:

Substituting in the frequency and Planck's constant (6.63 1034 J s) into the

above equation, the energy of a single photon associated with this frequency is:

E h (6.63 1034 J s) 7.5 1014 s 1 5.0 1019 J

Check:

We expect the energy of a single photon to be a very small energy as calculated

above, 5.0 1019 J.

1.16

Because the same number of photons are being delivered by both lasers and because both
lasers produce photons with enough energy to eject electrons from the metal, each laser will
eject the same number of electrons.

The electrons ejected by the blue laser will have higher

kinetic energy because the photons from the blue laser have higher energy.

1.18

(a)

The maximum wavelength is obtained by solving Equation 1.4 when the kinetic energy

of the ejected electrons is equal to zero. In this case, Equation 1.4, together with the relation

c / , gives

hc

6.626 10

34

J s 3.00 10 8 m s 1

520 10 9 m

3.82 10 19 J

h (kinetic Energy)

(b)

(kinetic Energy)

hc

6.626 10
(kinetic Energy)

34

J s 3.00 10 8 m s 1

3.8227 10 19 J 5.9 10 20 J

450 10 9 m

Please remember to carry extra significant figures during the calculation and then round
at the

1.24

We use more accurate values of h and c for this problem.

1.28

very end to the appropriate number of significant figures.

hc

( 6.6256 10 34 J s )( 2.998 108 m s 1 )

Equation 1.14:

656.3 10

rn

3.027 10 19 J

0 h2n2
Z me e2

for n = 2:
(8.8542 10 12 C 2 J 1 m 1 )(6.626 10 34 J s)2 2
2.117x10 10 m = 211.7 pm
1 (9.109 10 31 kg)(1.602 10 19 C)2
2

r2

for n = 3:
(8.8542 10 12 C 2 J 1 m 1 )(6.626 10 34 J s)2 3
4.764x10 10 m = 476.4 pm
1 (9.109 10 31 kg)(1.602 10 19 C)2
2

r3

1.30

Z 2 RH

1
1
2
2
n1 n2

1 3.289832496 1015 s ?
2

1.36

1 11 3.289832496x10

15

s ? 3.289832496x10 15 ?Hz

From the Heisenberg uncertainty principle (Equation 1.22) we have

x p

h
2

For the minimum uncertainty we can change the greater than sign to an equal sign.

h
1.055 10 34 J s

1 10 ?
? 1
2 x
2 (4 10 m)

kg m s ?

Because p = m u, the uncertainty in the velocity is given by

p 1 10 24 kg m s 1

1 10 6 m s 1
m
9.1095 10 31 kg

The minimum uncertainty in the velocity is 1 106 m s1.

1.37

Below are the probability distributions for the first three energy levels for a one-dimensional
particle in a box, as shown in Figure 1.24.

The average value for x for all of the states for a

one-dimensional particle in a box is L/2 (the middle of the box).

This is true even for those

states (like the second state) that have no probability of being exactly in the middle of the box.

1.38

The difference between the energy levels n and (n + 1) for a one-dimensional particle in a box
is given by Equation 1.31:

Enn1

h2
(2n 1) .
8mL2

All we have to do is to plug the numbers into the equation remembering that 1 =10-10 m.

Enn1

(6.626 10 34 J s)2 [2(2) 1]

1.20 10 18 J
8(9.109 10 31 kg)[5.00 10 10 m]2

Energy is equal to Plancks constant times frequency.

We can rearrange this equation to

solve for frequency.

1.39

E
1.20 10 18 J

1.81 1015 s 1 1.81 1015 Hz

h 6.626 10 34 J s

From Equation 1.15 we can derive an equation for the change in energy going from the n=1 to
n=2 states for a hydrogen atom:

3Z 2 e 4 m e
.
32h 2 02

From Equation 1.31 we can derive an equation for the change in energy going from the n=1 to
n=2 states for a particle in a box:

3h 2
.
8mL2

We can combine the two equations and solve for L.

3Z 2 e 4 m e
3h 2

32h 2 02
8mL2

4h 4 02
2h 2 0 2(6.626 10 34 J s)2 (8.8542 10 12 C 2 J 1 m 1 )

3.326 10 10 m
Z 2 e 4 me2 Ze2 me
1(1.602 10 19 C)2 (9.109 10 31 kg)

The radius of the ground state of the hydrogen atom (the Bohr radius) is 5.29 10-11 m (see
Example 1.4).
calculated.

This leads to a diameter of 1.06 10-10 m, which is only a third the size of L that we

So, it seems

like a crude estimate.

1.40

The average value for x will be greater than L/2.

The larger the electric field, the larger the

average value of x.

1.42

(a)

2p: n 2, l 1, ml 1, 0, or 1

(b)

6s: n 6, l 0, ml 0 (only allowed value)

(c)

5d: n 5, l 2, ml 2, 1, 0, 1, or 2

An orbital in a subshell can have any of the allowed values of the magnetic quantum number
for that subshell.

All the orbitals in a subshell have exactly the same energy.

1.46

A 2s orbital is larger than a 1s orbital.

is lower in energy than the 2s.

1.50

The 1s orbital

The 1s orbital does not have a node while the 2s orbital does.

(a)

False.

n 2 is the first excited state.

(b)

False.

In the n 4 state, the electron is (on average) further from the nucleus and

hence easier to

(c)

True.

(d)

False.

a shorter

(e)
1.70

Both have the same spherical shape.

remove.

The n 4 to n 1 transition is a higher energy transition, which corresponds to

wavelength.

True.

The kinetic energy acquired by the electrons is equal to the voltage times the charge on the
electron.

After calculating the kinetic energy, we can calculate the velocity of the electrons

(KE 1/2mu2).

Finally, we can calculate the wavelength associated with the electrons using

the de Broglie equation.

KE (5.00 10 3 V)

1.602 10 19 J
8.01 10 16 J
1V

We can now calculate the velocity of the electrons.

KE

1
mu 2
2

8.01 1016 J

1
(9.1094 1031 kg)u 2
2

4.19 107 m s-1

Finally, we can calculate the wavelength associated with the electrons using the de Broglie
equation.

h
mu


1.72

(a)

(6.63 10 34 J s)
(9.1094 10 31 kg)(4.19 107 m s 1 )

1.74 10 11 m 17.4 pm

The average kinetic energy of 1 mole of an ideal gas is 3/2RT.

average kinetic energy

Converting to the

per atom, we have:

3
1 mol
(8.314 J mol 1 K 1 )(298 K )
6.171 10 21 J atom 1
2
6.022 10 23 atoms

(b)

To calculate the energy difference between the n 1 and n 2 levels in the hydrogen

atom, we modify

Equation 1.5 of the text.

1
1
1
1
E RH 2 2 (2.180 10 18 J) 2 2
1
nf

ni

(c)

1.635 1018 J

For a collision to excite an electron in a hydrogen atom from the n 1 to n 2 level,

KE E

3
RT
2
1.635 10 18 J
NA

2 (1.635 10 18 J)(6.022 10 23 mol1 )

7.90 10 4 K
3
(8.314 J mol1 K 1 )

This is an extremely high temperature. Other means of exciting H atoms must be used to
be practical.

1.75

Below are the solutions for the particle in a one dimensional box (Equation 1.35).

2
n (x)
L

1/2

n x
sin
L

n 1, 2, 3,....

The equation below yields the average value of x, for a particle in a one dimensional box.

x (x) dx
2

2 2 n x
2
x L sin L dx L
0
L

xsin

n x
L dx

We can use the following relation obtained from a table of integrals:

xsin ax dx
2

x 2 x sin(2ax) cos 2ax

4
4a
8a 2

2n x
2n x
2 x sin
cos
L
2
2
2 x
L

2 n x
f x (x) dx xsin

dx L 4
2
L
L

n
0
0

4
8

L
L

We now evaluate this for x equal to L and 0.

2 L
1
1
2
L

2
2
L 4
L

n
n 2

8
8

L
L

The result above shows us that for all states for a particle in a box, the average value of x is
L/2. This makes sense, because the squared wavefunctions are all symmetric about x = L/2.

The equation below yields the average value of x2, for a particle in a one dimensional box.

2
x (x) dx
2

2
2 2
2 n x
x L sin L dx L
0
L

x sin
2

n x
L dx

We can use the following relation obtained from a table of integrals:

2a 2 x 2 1 sin 2ax
x 3 x cos(2ax)
ax dx

6
4a 2
8a 3

x sin
2

2
2
2
x (x) dx L
0
L

x sin
2

n x

L dx

2n x

x cos
3

L
2 x

2
L 6
n
4

n 2

2n x

x 2 1 sin
2

n
8

We now evaluate this for x equal to L and 0.

2 L
L
1

2 1

f

L
2
3
L 6

n
2 n

for n = 1 the average value of x2 is 0.283 L2

for n = 2 the average value of x2 is 0.308 L2
for n = 3 the average value of x2 is 0.328 L2

1.76

The average value of r using Equation 1.41:

r rP r dr r 3 R(r) dr
0

3
2 Zr
Z 3/2 Zr
Z 3 a
ao
3
3

r r R10 (r ) dr r 2 e
dr 4 r e o dr
a0

a0 0
0
0

From an integral table:

x e

n ax

dx

n!
a n1

To use the above integral to solve our problem, n = 3, x = r, and a

Z
r 4
a0

r e
3

2 Zr
ao

Z
dr 4
a0

6ao4 3ao 3

ao .

4
16Z 2Z 2

2Z
,
ao

Hence, the average value for r for a 1s orbital is

3
a .
2 o

Remember that Z is the nuclear charge

and is equal to 1 for a hydrogen atom.

To calculate the most probable value of r, we set the derivative of the radial probability
function to zero and solve for r.

2
2 Zr
Z 3/2 Zr
Z 2 a
ao
2
2

P r r R r r 2 e
4 r e o
a0

a0

Z
Z
d
a
P r 4 r 2e o 4
dr
a
0
a0

When r

ao
Z

2Zr

2
2Zr
2Zr
2Zr 2Z

Z
Z 2 ao
ao
2
2re ao

r e
8 r r e
ao
ao
a0

ao the derivative is zero, which corresponds to the most likely value of r.

This is consistent with ao being the Bohr radius.

For the 2s orbital

r rP r dr r 3 R(r) dr

The average value of r:

0
2

Zr
2 Z 3/2
Zr 2 ao
dr
r r R10 (r ) dr r
2

e
ao
4 a0

0
0

3
Zr

1 Z
4Z
a
3
r 4 r e o dr
8 a0
ao

r e
4

Zr
ao

dr

Z2
ao2

r e
5

Zr
ao

dr

Using the same integral solution as above, we can solve for the three integrals in the square
brackets

4 r 3e
0

Zr
ao

dr 4

6ao4
Z4

24ao4
Z4

4Z
ao

Z2
ao2

r e

5
r e

Zr
ao

Zr
ao

dr

dr

5
4
4Z 24ao 96ao
5
ao Z
Z4

6
4
Z 2 120ao 120ao

ao2 Z 6
Z4

When we plug in the results for the integrals into the above equation we get that the average
distance from the nucleus for a 2s orbital is six times the Bohr radius.

Notice that this is four

times the average distance from the nucleus for a 1s orbital.

4
4
4
4
a
1 Z 24ao 96ao 120ao 1 Z 48ao

6 o 6ao

4
4
4
4
8 a0 Z
Z
Z
Z 8 a0 Z

To calculate the most probable value of r, we can set the derivative of the radial probability
function to zero and solve for r.

3
Zr
Zr
2 Z 3/2
Zr 2 ao
1 Z 2
4Zr Z 2 r 2 ao

P r r R r r
2 e
r 4
2 e
ao
8 a0
ao
4 a0

ao

P r

3
Zr
Zr
Zr
1 Z 2 ao 4Zr 3 ao Z 2 r 4 ao

4r
e

e
8 a0
ao
ao2

2
Zr
Zr
Zr
d
1 Z d 2 ao 4Zr 3 ao Z 2 r 4 ao
4r e
P r
e 2 e
dr
8 a0 dr
ao
ao

d
1 Z
Zr 2 4Z 2 Zr 3 Z 2 3 Zr 4 ao
P r 4 2r

3r

4r
e
dr
8 a0
ao ao
ao ao2
ao

Zr

d
1 Z
16Zr 2 8Z 2 r 3 Z 3 r 4 ao
P r 8r

3 e
dr
8 a0
ao
ao2
ao

Zr

3
a
16ao2 r ao r 2
d
1 Z rZ 3 8a
P r 3 3o

r3 e o
2
dr
8 a0 ao Z
Z
Z

Zr

The above polynomial can be solved computationally to determine three roots.

root, which corresponds to the most probable value is r

1.77

3 5 a
Z

The largest

3 5 ao .

1/2
1/2
L

n x
m x
n x
m x
2
2

sin
sin
dx

sin
sin
dx

L L
L

L0
L
L
0

Using a table of integrals, it can be shown that the last integral listed above is zero if n does
not equal m, and is L/2 if n equals m.

Hence, the wavefunctions for a one-dimensional

particle in a box are orthogonal.

1.78

The five lowest energy levels for a two-dimensional particle in a box correspond to the
following sets of quantum numbers: (nx=1, ny=1), (nx=1, ny=2), (nx=2, ny=1), (nx=2, ny=2),
(nx=3, ny=1) , (nx=1, ny=3) , (nx=3, ny=2) , (nx=2, ny=3). These wavefunctions are plotted
below with the lowest energy wavefunction at the bottom.

Notice that the states

ny=2) and (nx=2, ny=1) have the same energy as do the states
and the states (nx=3, ny=2) and (nx=2, ny=3).

(nx=1,

(nx=1, ny=3) and (nx=3, ny=1)