This action might not be possible to undo. Are you sure you want to continue?

Solutions to exercises

Discussion questions

E17.1(b) The Franck–Condon principle states that because electrons are so much lighter than nuclei an

electronic transition occurs so rapidly compared to vibrational motions that the internuclear distance

is relatively unchanged as a result of the transition. This implies that the most probable transitions

ν

f

←ν

i

are vertical. This vertical line will, however, intersect any number of vibrational levels ν

f

in

the upper electronic state. Hence transitions to many vibrational states of the excited state will occur

with transition probabilities proportional to the Frank–Condon factors which are in turn proportional

to the overlap integral of the wavefunctions of the initial and ﬁnal vibrational states. A vibrational

progression is observed, the shape of which is determined by the relative horizontal positions of the

two electronic potential energy curves. The most probable transitions are those to excited vibrational

states with wavefunctions having a large amplitude at the internuclear position R

e

.

Question. You might check the validity of the assumption that electronic transitions are so much

faster than vibrational transitions by calculating the time scale of the two kinds of transitions. How

much faster is the electronic transition, and is the assumption behind the Franck–Condon principle

justiﬁed?

E17.2(b) Color can arise by emission, absorption, or scattering of electromagnetic radiation by an object.

Many molecules have electronic transitions that have wavelengths in the visible portion of the elec-

tromagnetic spectrum. When a substance emits radiation the perceived color of the object will be

that of the emitted radiation and it may be an additive color resulting from the emission of more

than one wavelength of radiation. When a substance absorbs radiation its color is determined by the

subtraction of those wavelengths from white light. For example, absorption of red light results in the

object being perceived as green. Color may also be formed by scattering, including the diffraction

that occurs when light falls on a material with a grid of variation in texture of refractive index having

dimensions comparable to the wavelength of light, for example, a bird’s plumage.

E17.3(b) The characteristics of ﬂuorescence which are consistent with the accepted mechanism are: (1) it

ceases as soon as the source of illumination is removed; (2) the time scale of ﬂuorescence, ≈ 10

−9

s,

is typical of a process in which the rate determining step is a spontaneous radiative transition between

states of the same multiplicity; slower than a stimulated transition, but faster than phosphores-

cence; (3) it occurs at longer wavelength (higher frequency) than the inducing radiation; (4) its

vibrational structure is characteristic of that of a transition from the ground vibrational level of the

excited electronic state to the vibrational levels of the ground electronic state; and (5), the observed

shifting and in some instances quenching of the ﬂuorescence spectrum by interactions with the

solvent.

E17.4(b) See Table 17.4 for a summary of the characteristics of laser radiation that result in its many advantages

for chemical and biochemical investigations. Two important applications of lasers in chemistry have

been to Raman spectroscopy and to the development of time resolved spectroscopy. Prior to the

invention of lasers the source of intense monochromatic radiation required for Raman spectroscopy

was a large spiral discharge tube with liquid mercury electrodes. The intense heat generated by the

large current required to produce the radiation had to be dissipated by clumsy water cooled jackets

and exposures of several weeks were sometimes necessary to observe the weaker Raman lines.

These problems have been eliminated with the introduction of lasers as the source of the required

monochromatic radiation. As a consequence, Raman spectroscopy has been revitalized and is now

almost as routine as infrared spectroscopy. See Section 17.7(b). Time resolved laser spectroscopy can

SPECTROSCOPY 2: ELECTRONIC TRANSITIONS 279

be used to study the dynamics of chemical reactions. Laser pulses are used to obtain the absorption,

emission, and Raman spectrum of reactants, intermediates, products, and even transition states of

reactions. When we want to study the rates at which energy is transferred from one mode to another

in a molecule, we need femotosecond and picosecond pulses. These time scales are available from

mode-locked lasers and their development has opened up the possibility of examining the details of

chemical reactions at a level which would have been unimaginable before.

Numerical exercises

E17.5(b) To obtain the parities of Fig. 14.38 of the text we recognize that what is shown in the ﬁgure are the

signs (light = positive, dark = negative) of the upper (positive z-direction) lobe of the p

z

orbitals.

The lower lobes (not shown) have opposite signs. Inversion through the centre changes + to − for

the p

z

lobes of a

2

and e

2

, but the e

1

and b

2

lobes do not change sign. Therefore a

2

and e

2

are u, e

1

and b

2

are g.

E17.6(b) According to Hund’s rule, we expect one 1π

u

electron and one 2π

g

electron to be unpaired. Hence

S = 1 and the multiplicity of the spectroscopic term is 3 . The overall parity is u × g = u since

(apart from the complete core), one electron occupies a u orbital another occupies a g orbital.

E17.7(b) Use the Beer–Lambert law

log

I

I

0

= −ε[J]l = (−327 L mol

−1

cm

−1

) ×(2.22 ×10

−3

mol L

−1

) ×(0.15 cm)

= −0.10889

I

I

= 10

−0.10889

= 0.778

The reduction in intensity is 22.2 per cent

E17.8(b) ε = −

1

[J]l

log

I

I

0

[16.9, 16.10]

=

−1

(6.67 ×10

−4

mol L

−1

) ×(0.35 cm)

log 0.655 = 787 L mol

−1

cm

−1

= 787 dm

3

mol

−1

cm

−1

= 787 ×10

3

cm

3

mol

−1

cm

−1

[1 dm = 10 cm]

= 7.9 ×10

5

cm

2

mol

−1

E17.9(b) The Beer–Lambert law is

log

I

I

0

= −ε[J]l so [J] =

−1

εl

log

I

I

0

[J] =

−1

(323 L mol

−1

cm

−1

×(0.750 cm)

log(1 −0.523) = 1.33 ×10

−3

mol L

−1

E17.10(b) Note. A parabolic lineshape is symmetrical, extending an equal distance on either side of its peak.

The given data are not consistent with a parabolic lineshape when plotted as a function of either

wavelength or wavenumber, for the peak does not fall at the centre of either the wavelength or the

wavenumber range. The exercise will be solved with the given data assuming a triangular lineshape

as a function of wavenumber.

280 INSTRUCTOR’S MANUAL

The integrated absorption coefﬁcient is the area under an absorption peak

A =

ε d˜ ν

If the peak is triangular, this area is

A =

1

2

(base) ×(height)

=

1

2

[(199 ×10

−9

m)

−1

−(275 ×10

−9

m)

−1

] ×(2.25 ×10

4

L mol

−1

cm

−1

)

= 1.56 ×10

10

L m

−1

mol

−1

cm

−1

=

(1.56 ×10

9

L m

−1

mol

−1

cm

−1

) ×(100 cmm

−1

)

10

3

L m

−3

= 1.56 ×10

9

mmol

−1

= 1.56 ×10

8

L mol

−1

cm

−2

E17.11(b) Modelling the π electrons of 1,3,5-hexatriene as free electrons in a linear box yields non-degenerate

energy levels of

E

n

=

n

2

h

2

8m

e

L

2

The molecule has six π electrons, so the lowest-energy transition is from n = 3 to n = 4. The length

of the box is 5 times the C

––

C bond distance R. So

E

linear

=

(4

2

−3

3

)h

2

8m

e

(5R)

2

Modelling the π electrons of benzene as free electrons on a ring of radius R yields energy levels of

E

m

l

=

m

2

l

¯ h

2

2I

where I is the moment of inertia: I = m

e

R

2

. These energy levels are doubly degenerate, except for

the non-degenerate m

l

= 0. The six π electrons ﬁll the m

l

= 0 and 1 levels, so the lowest-energy

transition is from m

l

= 1 to m

l

= 2

E

ring

=

(2

2

−1

2

)¯ h

2

2m

e

R

2

=

(2

2

−1

2

)h

2

8π

2

m

e

R

2

Comparing the two shows

E

linear

=

7

25

h

2

8m

e

R

2

< E

ring

=

3

π

2

h

2

8m

e

R

2

**Therefore, the lowest-energy absorption will rise in energy.
**

E17.12(b) The Beer–Lambert law is

log

I

I

0

= −ε[J]l = log T

so a plot (Fig. 17.1) of log T versus [J] should give a straight line through the origin with a slope m

of −εl. So ε = −m/l.

SPECTROSCOPY 2: ELECTRONIC TRANSITIONS 281

The data follow

[dye]/(mol L

−1

) T log T

0.0010 0.73 −0.1367

0.0050 0.21 −0.6778

0.0100 0.042 −1.3768

0.0500 1.33 ×10

−7

−6.8761

0

2

4

8

6

0.00 0.01 0.02 0.03 0.04 0.05 0.06

Figure 17.1

The molar absorptivity is

ε = −

−138 L mol

−1

0.250 cm

= 552 L mol

−1

cm

−1

E17.13(b) The Beer–Lambert law is

log T = −ε[J]l so ε =

−1

[J]l

log T

ε =

−1

(0.0155 mol L

−1

) ×(0.250 cm)

log 0.32 = 12

¯

8 L mol

−1

cm

−1

Now that we have ε, we can compute T of this solution with any size of cell

T = 10

−ε[J]l

= 10

−{(128 L mol

−1

cm

−1

)×(0.0155 mol L

−1

)×(0.450 cm)}

= 0.13

E17.14(b) The Beer–Lambert law is

log

I

I

0

= −ε[J]l so l = −

1

ε[J]

log

I

I

0

(a) l = −

1

(30 L mol

−1

cm

−1

) ×(1.0 mol L

−1

)

×log

1

2

= 0.020 cm

(b) l = −

1

(30 L mol

−1

cm

−1

) ×(1.0 mol L

−1

)

×log 0.10 = 0.033 cm

282 INSTRUCTOR’S MANUAL

E17.15(b) The integrated absorption coefﬁcient is the area under an absorption peak

A =

ε d˜ ν

We are told that ε is a Gaussian function, i.e. a function of the form

ε = ε

max

exp

−x

2

a

2

where x = ˜ ν − ˜ ν

max

and a is a parameter related to the width of the peak. The integrated absorption

coefﬁcient, then, is

A =

∞

−∞

ε

max

exp

−x

2

a

2

dx = ε

max

a

√

π

We must relate a to the half-width at half-height, x

1/2

1

2

ε

max

= ε

max

exp

−x

2

1/2

a

2

so ln

1

2

=

−x

2

1/2

a

2

and a =

x

1/2

√

ln 2

So A = ε

max

x

1/2

π

ln 2

1/2

= (1.54 ×10

4

L mol

−1

cm

−1

) ×(4233 cm

−1

) ×

π

ln 2

1/2

= 1.39 ×10

8

L mol

−1

cm

−2

In SI base units

A =

(1.39 ×10

8

L mol

−1

cm

−2

) ×(1000 cm

3

L

−1

)

100 cmm

−1

= 1.39 ×10

9

mmol

−1

E17.16(b) F

+

2

is formed when F

2

loses an antibonding electron, so we would expect F

+

2

to have a shorter bond

than F

2

. The difference in equilibrium bond length between the ground state (F

2

) and excited state

(F

+

2

+ e

−

) of the photoionization experiment leads us to expect some vibrational excitation in the

upper state. The vertical transition of the photoionization will leave the molecular ion with a stretched

bond relative to its equilibriumbond length. Astretched bond means a vibrationally excited molecular

ion, hence a stronger transition to a vibrationally excited state than to the vibrational ground state

of the cation.

Solutions to problems

Solutions to numerical problems

P17.3 Initially we cannot decide whether the dissociation products are produced in their ground atomic

states or excited states. But we note that the two convergence limits are separated by an

amount of energy exactly equal to the excitation energy of the bromine atom: 18 345 cm

−1

−

14 660 cm

−1

= 3685 cm

−1

. Consequently, dissociation at 14 660 cm

−1

must yield bromine atoms

in their ground state. Therefore, the possibilities for the dissociation energy are 14 660 cm

−1

or

SPECTROSCOPY 2: ELECTRONIC TRANSITIONS 283

14 660 cm

−1

−7598 cm

−1

= 7062 cm

−1

depending upon whether the iodine atoms produced are in

their ground or excited electronic state.

In order to decide which of these two possibilities is correct we can set up the following Born–Haber

cycle

(1) IBr(g) →

1

2

I

2

(g) +

1

2

Br

2

(l) H

− −

1

= −

f

H

− −

(IBr, g)

(2)

1

2

I

2

(s) →

1

2

I

2

(g) H

− −

2

=

1

2

sub

H

− −

(I

2

, s)

(3)

1

2

Br

2

(l) →

1

2

Br

2

(g) H

− −

3

=

1

2

vap

H

− −

(Br

2,

l)

(4)

1

2

I

2

(g) → I(g) H

− −

4

=

1

2

H(I

––

I)

(5)

1

2

Br

2

(g) → Br(g) H

− −

5

=

1

2

H(Br

––

Br)

IBr(g) → I(g) +Br(g) H

− −

H

− −

= −

f

H

− −

(IBr, g) +

1

2

sub

H

− −

(I

2

, s) +

1

2

vap

H

− −

(Br

2

, l)

+

1

2

H(I

––

I) +

1

2

H(Br

––

Br)

=

¸

−40.79 +

1

2

×62.44 +

1

2

×30.907 +

1

2

×151.24 +

1

2

×192.85

¸

kJ mol

−1

[Table 2.6 and data provided]

= 177.93 kJ mol

−1

= 14 874 cm

−1

Comparison to the possibilities 14 660 cm

−1

and 7062 cm

−1

shows that it is the former that is the

correct dissociation energy.

P17.5 We write ε = ε

max

e

−x

2

= ε

max

e

−˜ ν

2

/2

the variable being ˜ ν and being a constant. ˜ ν is measured

from the band centre, at which ˜ ν = 0. ε =

1

2

ε

max

when ˜ ν

2

= 2 ln 2. Therefore, the width at

half-height is

˜ ν

1/2

= 2 ×(2 ln 2)

1/2

, implying that =

˜ ν

2

1/2

8 ln 2

Now we carry out the intregration

A =

ε d˜ ν = ε

max

∞

−∞

e

−˜ ν

2

/2

d˜ ν = ε

max

(2π)

1/2

¸

∞

−∞

e

−x

2

dx = π

1/2

¸

= ε

max

2π˜ ν

2

1/2

8 ln 2

1/2

=

π

4 ln 2

1/2

ε

max

˜ ν

1/2

= 1.0645ε

max

˜ ν

1/2

A = 1.0645ε

max

˜ ν

1/2

, with ˜ ν centred on ˜ ν

0

Since ˜ ν =

1

λ

, ˜ ν

1/2

≈

λ

1/2

λ

2

0

[λ ≈ λ

0

]

A = 1.0645ε

max

λ

1/2

λ

2

0

**From Fig. 17.52 of the text, we ﬁnd λ
**

1/2

= 38 nm with λ

0

= 290 nm and ε

max

≈

235 L mol

−1

cm

−1

; hence

284 INSTRUCTOR’S MANUAL

A =

1.0645 ×(235 L mol

−1

cm

−1

) ×(38 ×10

−7

cm)

(290 ×10

−7

cm)

2

= 1.1 ×10

6

L mol

−1

cm

−2

Since the dipole moment components transform as A

1

(z), B

1

(x), and B

2

(y), excitations from A

1

to

A

1

, B

1

, and B

2

terms are allowed.

P17.8 Draw up a table like the following:

Hydrocarbon hν

max

/eV E

HOMO

/eV

∗

Benzene 4.184 −9.7506

Biphenyl 3.654 −8.9169

Naphthalene 3.452 −8.8352

Phenanthrene 3.288 −8.7397

Pyrene 2.989 −8.2489

Anthracene 2.890 −8.2477

∗

Semi-empirical, PM3 level, PC Spartan Pro

TM

Figure 17.2 shows a good correlation: r

2

= 0.972.

–8.0

–8.5

–9.0

–9.5

–10.0

2.5 3.0 3.5 4.0 4.5

Figure 17.2

P17.11 Refer to Fig. 14.30 of the text. The lowest binding energy corresponds to the highest occupied orbital,

the next lowest to next highest orbital, and so on.

We draw up the following table

LineE

K

/eV Binding energy/eV Assignment

N

2

5.6 15.6 3σ

4.5 16.7 1π

2.4 18.8 2σ

∗

CO 7.2 14.0 3σ

4.9 16.3 1π

1.7 19.5 2σ

∗

The spacing of the 4.5 eV lines in N

2

is 0.24 eV, or about 1940 cm

−1

. The spacing of the 4.9 eV

lines in COis 0.23 eV, or about 1860 cm

−1

. These are estimates fromthe illustrations of the separation

of the vibrational levels of the N

+

2

and CO

+

ions in their excited states.

P17.13 0.125 eV corresponds to 1010 cm

−1

, markedly less than the 1596 cm

−1

of the bending mode. This

suggests that the ejected electron tended to bond between the two hydrogens of the water molecule.

SPECTROSCOPY 2: ELECTRONIC TRANSITIONS 285

Solutions to theoretical problems

P17.14 We need to establish whether the transition dipole moments

µ

ﬁ

=

∗

f

µ

i

dτ [16.20]

connecting the states 1 and 2 and the states 1 and 3 are zero or nonzero. The particle in a box

wavefunctions are

n

=

2

L

1/2

sin

nπx

L

[12.8]

Thus µ

2,1

∝

sin

2πx

L

x sin

πx

L

dx ∝

x

¸

cos

πx

L

−cos

3πx

L

¸

dx

and µ

3,1

∝

sin

3πx

L

x sin

πx

L

dx ∝

x

¸

cos

2πx

L

−cos

4πx

L

¸

dx

having used sin α sin β =

1

2

cos(α − β) −

1

2

cos(α + β). Both of these integrals can be evaluated

using the standard form

x(cos ax) dx =

1

a

2

cos ax +

x

a

sin ax

L

0

x cos

πx

L

dx =

1

π

L

2

cos

πx

L

L

0

+

x

π

L

sin

πx

L

L

0

= −2

L

π

2

= 0

0

L

x cos

3πx

L

dx =

1

3π

L

2

cos

3πx

L

L

0

+

x

3π

L

sin

3πx

L

L

0

= −2

L

3π

2

= 0

Thus µ

2,1

= 0.

In a similar manner µ

3,1

= 0.

Comment. A general formula for µ

ﬁ

applicable to all possible particle in a box transitions may be

derived. The result is (n = f, m = i)

µ

nm

= −

eL

π

2

¸

cos(n −m)π −1

(n −m)

2

−

cos(n +m)π −1

(n +m)

2

¸

For m and n both even or both odd numbers, µ

nm

= 0; if one is even and the other odd, µ

nm

= 0.

See also Problem 17.18.

Question. Can you establish the general relation for µ

nm

above?

P17.16 We need to determine how the oscillator strength (Problem 17.17) depends on the length of the chain.

We assume that wavefunctions of the conjugated electrons in the linear polyene can be approximated

by the wavefunctions of a particle in a one-dimensional box. Then

f =

8π

2

m

e

ν

3he

2

|µ

2

ﬁ

| [Problem 17.17]

µ

x

= −e

L

0

n

(x)x

n

(x) dx,

n

=

2

L

1/2

sin

nπx

L

= −

2e

L

L

0

x sin

n

πx

L

sin

nπx

L

dx

286 INSTRUCTOR’S MANUAL

=

¸

¸

0 if n

= n +2

+

8eL

π

2

n(n +1)

(2n +1)

2

if n

= n +1

The integral is standard, but may also be evaluated using 2 sin Asin B = cos(A−B) −cos(A+B)

as in Problem 17.14

hν = E

n+1

−E

n

= (2n +1)

h

2

8m

e

L

2

Therefore, for the transition n +1 ←n,

f =

8π

2

3

m

e

he

2

h

8m

e

L

2

(2n +1)

8eL

π

2

2

n

2

(n +1)

2

(2n +1)

4

=

64

3π

2

¸

n

2

(n +1)

2

(2n +1)

3

Therefore, f ∝

n

2

(n +1)

2

(2n +1)

3

The value of n depends on the number of bonds: each π bond supplies two π electrons and so n

increases by 1. For large n,

f ∝

n

4

8n

3

→

n

8

and f ∝ n

Therefore, for the longest wavelength transitions f increases as the chain length is increased. The

energy of the transition is proportional to

(2n +1)

L

2

; but as n ∝ L, this energy is proportional to

1

L

.

Since E

n

=

n

2

h

2

8m

e

L

2

, E =

(2n +1)h

2

8m

e

L

2

[n = +1]

but L = 2nd is the length of the chain (Exercise 17.11(a)), with d the carbon–carbon interatomic

distance. Hence

E =

L

2d

+1

h

2

8m

e

L

2

≈

h

2

16m

e

dL

∝

1

L

Therefore, the transition moves toward the red as L is increased and the apparent color of the dye

shifts towards blue .

P17.17 µ = −e

v

x

v

dx

From Problem 12.15, µ

10

= −e

1

x

0

dx = −e

¸

¯ h

2(m

e

k)

1/2

¸

1/2

Hence, f =

8π

2

m

e

ν

3he

2

×

e

2

¯ h

2(m

e

k)

1/2

=

1

3

¸

2πν =

k

m

e

1/2

**P17.19 (a) Vibrational energy spacings of the lower state are determined by the spacing of the peaks of
**

A. From the spectrum, ˜ ν ≈ 1800 cm

−1

.

(b) Nothing can be said about the spacing of the upper state levels (without a detailed analysis of the

intensities of the lines). For the second part of the question, we note that after some vibrational

SPECTROSCOPY 2: ELECTRONIC TRANSITIONS 287

decay the benzophenone (which does absorb near 360 nm) can transfer its energy to naphthalene.

The latter then emits the energy radiatively.

P17.21 (a) The Beer–Lambert Law is:

A = log

I

0

I

= ε[J]l.

The absorbed intensity is:

I

abs

= I

0

−I so I = I

0

−I

abs

.

Substitute this expression into the Beer–Lambert law and solve for I

abs

:

log

I

0

I

0

−I

abs

= ε[J]l so I

0

−I

abs

= I

0

×10

−ε[J]l

,

and I

abs

= I

0

×(1 −10

−ε[J]l

) .

(b) The problem states that I

f

(˜ ν

f

) is proportional to φ

f

and to I

abs

(˜ ν), so:

I

f

(˜ ν

f

) ∝ φ

f

I

0

(˜ ν) ×(1 −10

ε[J]l

).

If the exponent is small, we can expand 1 −10

−ε[J]l

in a power series:

10

−ε[J]l

= (e

ln 10

)

−ε[J]l

≈ 1 −ε[J]l ln 10 +· · · ,

and I

f

(˜ ν

f

) ∝ φ

f

I

0

(˜ ν)ε[J]l ln 10 .

P17.22 Use the Clebsch–Gordan series [Chapter 13] to compound the two resultant angular momenta, and

impose the conservation of angular momentum on the composite system.

(a) O

2

has S = 1 [it is a spin triplet]. The conﬁguration of an O atom is [He]2s

2

2p

4

, which is

equivalent to a Ne atom with two electron-like “holes”. The atom may therefore exist as a spin

singlet or as a spin triplet. Since S

1

= 1 and S

2

= 0 or S

1

= 1 and S

2

= 1 may each combine

to give a resultant with S = 1, both may be the products of the reaction. Hence multiplicities

3 +1 and 3 +3 may be expected.

(b) N

2

, S = 0. The conﬁguration of an N atom is [He] 2s

2

2p

3

. The atoms may have S =

3

2

or

1

2

.

Then we note that S

1

=

3

2

and S

1

=

3

2

can combine to give S = 0; S

1

=

1

2

and S

2

=

1

2

can

also combine to give S = 0 (but S

1

=

3

2

and S

2

=

1

2

cannot). Hence, the multiplicities 4 +4

and 2 +2 may be expected.

Solutions to applications

P17.24 The integrated absorption coefﬁcient is

A =

ε(˜ ν) d˜ ν [16.12]

If we can express ε as an analytical function of ˜ ν, we can carry out the integration analytically.

Following the hint in the problem, we seek to ﬁt ε to an exponential function, which means that a

288 INSTRUCTOR’S MANUAL

plot of ln ε versus ˜ ν ought to be a straight line (Fig. 17.3). So if

ln ε = m˜ ν +b then ε = exp(m˜ ν) exp(b)

and A =

e

b

m

exp(m˜ ν) (evaluated at the limits integration). We draw up the following table and ﬁnd

the best-ﬁt line

λ/nm ε/(L mol

−1

cm

−1

) ˜ ν/cm

−1

ln ε/(L mol

−1

cm

−1

)

292.0 1512 34248 4.69

296.3 865 33748 4.13

300.8 477 33248 3.54

305.4 257 32748 2.92

310.1 135.9 32248 2.28

315.0 69.5 31746 1.61

320.0 34.5 31250 0.912

5

4

3

2

1

0

31000 32000 33000 34000 35 000

Figure 17.3

So A =

e

−38.383

1.26 ×10

−3

cm

¸

exp

1.26 ×10

−3

cm

290 ×10

−7

cm

−exp

1.26 ×10

−3

cm

320 ×10

−7

cm

L mol

−1

cm

−1

= 1.24 ×10

5

L mol

−1

cm

−2

P17.25 The concentration of the hypothetical pure layer is

[O

3

] =

n

V

=

p

RT

=

1 atm

(0.08206 L atmmol

−1

K

−1

) ×(273 K)

= 4.46 ×10

−2

mol L

−1

So for 300 DU

A = εcl = (476 L mol

−1

cm

−1

) ×(0.300 cm) ×(4.46 ×10

−2

mol L

−1

) = 6.37

and for 100 DU

A = εcl = (476 L mol

−1

cm

−1

) ×(0.100 cm) ×(4.46 ×10

−2

mol L

−1

) = 2.12

SPECTROSCOPY 2: ELECTRONIC TRANSITIONS 289

P17.27 The reaction enthalpy for process (2) is

r

H

− −

=

f

H

− −

(Cl) +

f

H

− −

(OClO

+

) +

f

H

− −

(e

−

) −

f

H

− −

(Cl

2

O

2

)

so

f

H

− −

(Cl

2

O

2

) =

f

H

− −

(Cl) +

f

H

− −

(OClO

+

) +

f

H

− −

(e

−

) −

r

H

− −

f

H

− −

(Cl

2

O

2

) = (121.68 +1096 +0) kJ mol

−1

−(10.95 eV) ×(96.485 kJ eV

−1

)

= 161 kJ mol

−1

We see that the Cl

2

O

2

in process (2) is different from that in process (1), for its heat of formation

is 28 kJ mol

−1

greater. This is consistent with the computations, which say that ClOOCl is likely

to be the lowest-energy isomer. Experimentally we see that the Cl

2

O

2

of process (2), which is not

ClOOCl, is not very much greater in energy than the lowest-energy isomer.

- Handbook of Atmospheric sciences
- A Manual for Biochemistry Protocols
- Raman
- Optical Instrum (Net)
- Optical Instrum 1
- Mass Spectroscopy
- Mass Spect
- IR
- 13C NMR Spectroscopy
- 1H NMR Spectroscopy
- Bio Degradation of Pollutants
- Oxidative Stress
- Chap Ti
- ConcptsTxcityFigures
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed
- Atkins, Solution, 7th Ed

Sign up to vote on this title

UsefulNot usefulAtkins, 7th edition solutions manual

Atkins, 7th edition solutions manual

- Raman Lasers Important
- AtomsStarLight 01
- Chris D. Boone et al- Speed-dependent Voigt profile for water vapor in infrared remote sensing applications
- 7112256 Laser Therapy
- gems_EMC16_NEW-1.pdf
- A. Muntianu, B. Guo and P. F. Bernath- High-Resolution Infrared Emission Spectrum of NaF
- rotationalspectra
- Testing of Metals
- NMR Spectroscopy Lab
- dv8900 userGuide 5E6155
- Perkuliahan 7 Material Polimer Dan Komposit
- SERS of Pyridine adsorbed on rhodium electrodes
- Lbm
- Structural and Optical Characterization of Cdstio2 Nanocomposite (2)
- Physics Ip
- Manual Instr Analysette
- Documents_40 - PHYSICS
- Angel Wars Light vs Dark
- Numerical Investigation of Laser Drilling
- SPE-84844-MS
- Pullalign 2-Page-flyer Ali-9.690 20-01-12 g
- Forensic Analysis
- LASER WELDING
- Laser Types-lecture (Dr. M Fadhali)
- Toshiba Estudio 555-655-755-855 Service Manual
- Starek, Normalizing Lidar Intensities
- Artigo - 2011 - Investigation of Noise sdvSources in Radio-over-Fiber Systems for Wi-Fi Applications
- Chapter 10 - Laser Beam Welding
- A. Heisterkamp et al- Nanosurgery in live cells using ultrashort laser pulses
- fiber optics
- Atkins, Solution, 7th Ed