SOLUTIONS MANUAL

toaccompany |

PHYSICAL
CHEMISTRY
| ROBERTA. ALBERTY

SEVENTH EDITION &

“FSOULITIONS mann, sei
: a re 268 = : oie
 SOLUTIONS MANUAL
to accompany

PHYSICAL
CHEMISTRY
SEVENTH EDITION

ROBERT A. ALBERTY
Professor of Chemistry
Massachusetts Institute of Technology

JOHN WILEY & SONS

New York Chichester Brisbane Sydney Toronto Singapore
Copyright
©) 1987 by John Wiley & Sons, Inc.

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ISBN O 471 82900 5

Printed in the United States of America

10 O88 756924
 PREFACE

This manual gives solutions of the problems in the first set of

the text R. A. Alberty, PHYSICAL CHEMISTRY, 7th ed., Wiley, New York,
1987, and it gives answers for the second set.

Working problems is an important part of learning physical

chemistry. Not all knowledge of physical chemistry is quantitative, but
muchO Lend beer si. Since physical chemistry utilizes physics and
mathematics to predict and interpret chemical phenomena, there are many
Opportunities to use quantitative methods.

The availability of hand-held electronic calculators has made it

much easier to work physical chemistry problems and has made it possible
to include more difficult problems.

The units of physical quantities are usually shown in solving

problems in this manual. It is important to develop the habit of using
units and cancelling them to obtain the units for the answer because
this helps prevent errors.

In this book, as in your handwritten lecture notes, there is no

distinction between italic (sloping) and roman (upright) type, but it is
important to note that in the printed literature italic type is used for
symbols for physical quantities and roman type is used for units.

I am indebted to many physical chemists who have recommended

problems and who have suggested improvements in this SOLUTIONS MANUAL.

Robert A. Alberty

Cambridge, Massachusetts
February 1986
 Digitized by the Internet Archive
in 2022 with funding from
Kahle/Austin Foundation

https://archive.org/details/solutionsmanualt0000albe
 ConOLeN ele Ns ole aS

Part I
THERMODYNAMICS

Zeroth Law of Thermodynamics and Equations of State

First Law of Thermodynamics

Second and Third Laws of Thermodynamics

Gibbs Energy and Helmholtz Energy .

Chentcon! shond
ab riom 65 2) sess

Phase Equilibrium: One-Component Systems and Ideal Solutions

Phase Equilibrium: Nonideal Solutions 108

Electrochemical Equilibria 27
F&F
WA
NK
Onn
NY
Wo Equilibria of Biochemical Reactions 146
ja Oo Surface Thermodynamics ...... 161

Parte.
QUANTUM CHEMISTRY

11 Quantum Theory 168

12 ATOMIC eSTTUCTULE Gos. 6 = « 188

a3 SVMMCT
TY. Batis s Be bey oe) fos ou’ tne Eis 204

14 Molecular Electronic Structure .... 208

ne Molecular Spectroscopy 223

16 Electronic Spectroscopy of Molecules 242

iby Magnetic Resonance Spectroscopy . 253

18 Statistical Mechanics « «64 « 5 < i, « 265

 Part III
CHEMICAL DYNAMICS

Kine ticelneO tym O laGdS CSmr meme mn cnn mmCmmCns 290

Experimental Gas Kinetics ..... . 308
Theoretical Gas Kinetics ... 341
Kinetics: Liquid Phase Psi eile Sears 348
Photochemistry 371
Irreversible Processes in Solution . 386

Part IV
STRUCTURES

25 Solid-State Chemistry . 402

 PART ONE
THERMODYNAMICS

CHAPTER 1: Zeroth Law of Thermodynamics and Equations of State

1.1 The perfect gas law also represents the behavior of mixtures of

gases at low pressures. The volume is then interpreted as the

molar volume of the mixture, that is the volume of a mole of the

mixture. The partial pressure of gas i in a mixture is defined as

y;P, where Yi is its mole fraction, and P is the total pressure.

Ten grams of Ny is mixed with 5 g of Oy and held at 25 °C at 0.750

bar. (a) What are the mole fractions of Ny and 05? (b) What are
the partial pressures of Ny and 0,? (c) What is the molar volume
assuming the molecules do not interact? (d) What is the actual
volume assuming the molecules do not interact?

SOLUTION
my = ——°8—_ = 0.357 mol
2) 28.013 g mol

ate Bae SE ee
2 32,000 g mol
P= (0.357/0.513)(0.750 bar) = 0.522 bar
2
Py = (0.156/0.513)(0.750 bar) = 0.228 bar
2
y = RE _ (8.3144 J KT* mot@*) (298.15 K)
P 0.750 x 10> Pa
0.0331 m> mol?
The gas contains 0.357 + Ee 0.513 mol and so the actual
volume is (0.513 mol) (0.0331 m> mol-+).
=u0-0170umoa or 17. Ga
i Calculate the second virial coefficient of hydrogen at 0 °C from

the fact that the molar volumes at 50.7, 101.3, 202.6, and 303.9

bar are 0.4634, 0.2386, 0.1271, and 0.09004 L mol, respectively.

SOLUTION
Ae Fee io ana oe A aera
RT V v2
P/bar 50.7 101.3 202.6 303.9

V/L moi2 0.4634 0.2386 0.1271 0.09004

PV/RT 1.035 1.064 1.134 1.205

(1/V)/mo1 L72 2.158 4.191 7.868 11.106

1
(0)

Slope =B
// 0.014 1 mo/-!
aly
qIS

LOW
eo) SF
WN
10

1. The second virial coefficient B of methyl isobutyl ketone is -1580

3 mol =
cm” at 120 itoe Compare its compressibility factor at this
temperature with that of a perfect gas at 1 bar.

SOLUTION PV B BP
Z —=1+-—-=1+—
RT V RT
 3

In the B/V term, V may be replaced by RT/P if Z%1, since the

approximation is made in a small correction term. At 1 bar

Jove odet all. 58 L moi@')(1 bar)

(0.08314 L bar K-- mo1~+) (393.15 K)
0.952
The compressibility factor for a perfect gas is of course unity.

1.4 Using Fig. 1.4 calculate the compressibility factor Z for NH3(g) at
400 K and 50 bar.

ae Bee 1 Oven onol

pric B = 71110 om? moi) (07 L cm >)
OFC Ail ber Kt mols
1).(400.E)
= 2231 101°. bara
Fe et BEP = 1 — (3231 x 10° bar”) (s0ubar)
0.835

Derive the expressions for van der Waals constants a and b in terms

of the critical temperature and pressure; that is, derive equations

1235 and 1.36 from 1-232 — 1734.

SOLUTION
Equations 1.32 and 1.33 may be written
RT

(Vi. =1t) v-

2RT
es = oe. (2)
Os =p) ve
Division of the first equation by the second yields
V. = 3b (3)
c
Substitution of this expression in equation 1 yields
(Ns, = 8a/27Rb (4)

Substitution of equations 3 and 4 in equation 1.34 yields

P= a/27b2 (5)
 Since there are three relations (equations 3 - 5) between the van

der Waals constants and the critical constants, a and b may be

expressed in terms of a and P, or Be and Nee Critical pressures

are generally known more accurately than critical volumes, and so a

and b are generally calculated using equations 1.35 and 1.36.

16 Calculate the second virial coefficient of methane at 400 K_ and

300 K from its van der Waals constants, and compare these results

with Fig. 1.4.

SOLUTION
For methane a = 2.283 L? bar mol” and b = 0.04278 L molt, From
equation 1.28, the virial coefficient at 400 K is

B = b — a/RT = 0.04278 — 2.283/(0.083144)

(400)
= -0.026 L moi!
compared with -—0.020 L mol! from Fig. 1.4. The calculated virial
coefficient at 300 K is -0.048 L mol, compared with 0.050 L mol}
in Fig. 1.4.
iL The critical temperature of carbon tetrachloride is 283.1 °C. The
densities in grams per cubic centimeter of the liquid Py and vapor
p,, at different temperatures are as follows:

tie 100 150 200 250 270 280

Py 1.4343 12.3215 1.1888 0.9980 0.8666 0.7634
Py 0.0103 0.0304 0.0742 0.1754 0.2710 0.3597

What is the critical molar volume of CC14? It is found that the

mean of the densities of the liquid and vapor does not vary rapidly
with temperature and can be represented by

Py + Py
Se eae AT + B where A and B are constants.
 5

The extrapolated value of the average density at the critical

temperature is the critical density. The molar volume Vig at the

critical pointis equal to the molar mass divided by the critical
density.

SOLUTION

0.7

a 0.6

Up
100 Z00 Te “4300

P, + Py ;
Extrapolating Gira are sO TS we obtain

pa ctUe a cn

v, = ISSe4e genrol = = Pe
0.557 g cm?
i Use the van der Waals constants for Hy, and O, in Table 1.3 to

calculate the initial slopes of the plots of the compressibility

factor Z versus P.

-———== 1 a
Z=1+ EF (b RT uP asa.

At 273.15-K, RT = (0.083144 L bar K! mo1*) (273.15 K)

= 22.71 L bar mol”
For Hy, Z=ud + (02:71) [010266 = (0.2476/22.
71). P tee
ak (62 O21 08 heen hee
For 05, Ze=) 1 522-174)ge LG, 0318 —aClasi6/ 22071) epee
= 1- (4.07 x 103 bar) P+...
See Fig. 1.2

il A mole of ethane is contained in a 200 ml-cylinder at 373 K. What

is the pressure according to (a) the perfect gas law and (b) the
van der Waals equation? The van der Waals constants are given in
Table 1.3.

SOLUTION
(a) P = RT/V = (.08314)(373)/0.200 = 155 bar
oy peer SET te ee ~(00834).13 73-5 S502
V ab, 9V- 0.200 - 0.0638 (0.200)2
= 88.6 bar

.10 What is the molar volume of n-hexane at 660 K and 91 bar according
to (a) the perfect gas law, (b) the van der Waals equation, and (c)
the Redlich-Kwong equation? T_ = 507.7 K P. = 30.3 bar
Cc c

SOLUTION
_ RT _ (0.08314 L bar K~! moi!) (660 K) =T
(a) V = > = ree = 0.603 L mol
 2. 2
(b) a = 8 = (27)(0.08314)? (507.7)?
Ze

64 PF. (64) (30.397 ~ * te

= 24.81 L2 bar mol2
RT
pees 0008324950727).
ore 8(30.3)
= 0.174 L mol~

V-b v2

(660 K) _ 24.81
91 bar = (0:08314)
V - 0.174 e
Rather than solving a cubic equation, substituting successive
values of V shows that
Vi=tO) 3081 pois
(c) a = 0.4275 R2 ead ae = 0.4275(.08314)2(507.7)2°>/30.3
= 566.4 L- bar ql/2 mol
b = 0.0866 RT 72 = (0.0866) (.08314) (507.7)/30.3

091247 L nol
RT a
a
v-p T/2 wy +b)
_ (08314) (660) _ 566.4
V - 0.121 (660)1/2 viv + 0.121)
Trying successive values of V shows that V = 0.40 L mol},

1.11 Derive equation 1.25 that gives the boundary of the physically

unrealizable region for a van der Waals gas and show that the

maximum pressure satisfying this equation is the critical pressure.

SOLUTION
 aV/y (V-»v)* vw?
Eliminating RT between these equations yields

The maximum pressure according to this equation is obtained by

differentiating with respect to V.
Vc RT c
aP = 2a + Gab so that b = = where equation 1.37
: ore has been used.

1.12 When pressure is applied to a liquid, its volume decreases.

Assuming that the isothermal compressibility =—- (39)

is independent of pressure, derive an expression for the volume as

a function of pressure.

SOLUTION
Vv2 dV P2
| as - k [ab
Py

_ i=} | i -K (Py - P,)

7,

< iH} v1 She, - P)

N

1.13 The coefficient of cubic expansion coefficient a is defined by

1 OV
a -(t = and the isothermal compressibility is defined by
P

Oly,
k -(2 a Calculate these quantities for a perfect gas.

SOLUTION

V = RT/P

(eg are
oT Pp P
 (g)-
oe Ss 17T

oP p2
Rie er ee iP
ve

1.14 Assuming that the atmosphere is isothermal at 0 °C and that the

average molar mass of air is 29 g mol ?, calculate the atmospheric

pressure at 20,000 ft above sea level.

SOLUTION
h (2-0¥x 40°) ft) (i2ein ft) 2064 ce in) 10 ot ee 8) = 6096 mn
|)
_ Poe
| .-gMh/RT
8

P (1.013 bar) ol
-(9.8 m s_7)(29 x 107° kg mol
+)(6096 m)
(8.314 J K~1 moi) (273 K)
0.472 bar

he) Calculate the pressure and composition of air on the top of Mt.
Everest assuming the atmosphere has a temperature of 0 oC

independent of altitude (h = 29,141 ft).

SOLUTION

h = (29,141 £t)(12 in ft~1)(2.54 cm in +)(0.01 m cm) = 8,882 m

For 0), P= (0.2 bar) exp (-9.8 x 32 x 10° x 8882/8.314 x 273)
= 0.059 bar

For Ny, P = (0.8 bar) exp (-9.8 x 28 x 10° x 8882/8.314 x 273)

= 0.274 bar

The total pressure is 0.333 bar, and Yo. 0.177 and ie 0.823.
2 2
B=-K,
21.7 cm
3 mol
ch
10

275.9 cm
3 mol =A

K = 0.28
= 435 K (actual 425 K)
0.261 L mol.) (actual 0.255 % mols)
ac) I 39 bar (actual 38.0 bar)
Cc

0.324 nm

14567) Oso | ands 07 60nx. 106° bare

(a) 1978 (b) 1621 (c) 2739 bar

(a) 100 (b) 152 bar

a 1/T(1 + bP/RT) K-= 1/P(1 + bP/RT)

Vor explo CL — 1s js)
ViozaVe (1 +. a(T = ro

0.843 bar

3.21 = 108? bat

CHAPTER 2: First Law of Thermodynamics

2.1 How much work is done when a person weighing 75 kg (165 lbs) climbs
the Washington monument, 555 ft high? How many kilojoules must be
supplied to do this muscular work, assuming that 25% of the energy

produced by the oxidation of food in the body can be converted into

muscular mechanical work?

SOLUTION
Ww = mgh

work = (mass) (acceleration of gravity) (height)

= (75 kg)(9.806 m s7)(555 £t)(12 in ft +)
(2.54 x 10°? m in +)
124.4 kJ
The energy needed is four times greater than the work done.

E 4(124.4 kJ)
497.6 kJ

The surface tension of water is 71.97 x 10-2 N nat or 71.97 x

10> Jom at 23 °C. Calculate the surface energy in joules of 1

mol of water dispersed as a mist containing droplets 1 pm C105" cm)

in radius. The density of water may be taken as 1.00 g cm >,

SOLUTION
The ratio of area to volume for a droplet is the same as the ratio

of area to volume for the whole 18 ome

V=eT
3 18 ee
EA n(10 -6 m) \3

A= 4 nx*,.= 4 n(10~° m)2

Total area =
4 n(10~©
ee EET
m)2 Total area = 54m
2}

182 10° «a x n(10°° m)?

12

Surface energy = (54 m7) (71.97ixsLObseamne )

3.89 J

26 A mole of sodium metal is added to water. How much work is done on

the atmosphere by the subsequent reaction if the temperature is

95 °C?

SOLUTION
Na(s) + H,0(1) = NaOH(soln) + 1/2 H,(g)
V = RT/P = (8.314 J K2 mot +) (298 K)/(101325 Pa)
= 0.0245 m> moi?
w = -PAV = -(101325 Pa) (0.0123 m> mol~)
= -1.24 kJ mol?
2.4 One mole of nitrogen at 25 °C and 1 bar is expanded reversibly and

isothermally to a pressure of 0.132 bar. (a) What is the value of

w? (b) What is the value of w if the nitrogen is expanded against
a constant pressure of 0.132 bar?

SOLUTION
(a) w = RT in(P,/P,)
= (8.314 J K? mol?) (298.15 K) 1n 0.132
= -5.03 kJ mol?
(b) Vy = RT/P, = (8.314) (298.15) /101325 = 0.0245 m°
V. = (8.314) (298.15) / (0.132) (101325) = 0.185 m?
w = -PAV = - (0.132 x 10°)(0.185 - 0.0245)
= -2.12 kJ moi!
os 5 Calculate the work done on the gas in the reversible isothermal

(298.15 K) expansion of a mole of Ny, from 1 L to 10 L assuming it

is (a) an ideal gas and (b) a van der Waals gas (See Table 1.3).
 13

SOLUTION

Vo
(a) w = -RT In Fe
—(8.314) (298.15) 1n 10
1
= =§.71 kJ mol
Ve"=
2 ">
OS lh ee Sr eae ne
1 Yi. “Yo
We can leave V in L mo1 in the first term because this unit
cancels, but we must convert a to SI base units and express

V, and V, in SI units in the second term.

a = (1.408 L? bar mol 7)(10° Pa bar !)(10°? m> L-)?
= 0.1408 m? Pa mol”
10°=— 0;0391 1 1
w = —(8.314)(298.15) In T~— 0.0391 + 0.1408 aes - —)

= -5,67 kJ mol
Are the following expressions exact differentials?

(a) 2 dy
xy“dx - x“y (b) Lae aaedy
yi y

SOLUTION
(a) Taking the cross derivatives

a(-x2y) a
—2xy
Ox

Since the cross derivatives are unequal, the expression is

not an exact differential.

OU) ye a(-x/y*) peas

(b) 0 y) a 0x
y2 y2

Since the cross derivatives are equal, the expression is an

exact differential.
14

Pare | Over narrow ranges of temperature and pressure, the differential

expression for the volume of a fluid as a function of temperature

and pressure can be integrated to obtain

v = Ke?! . KP
(a and Kare defined in Section 1.10). Show that V is a state
function.

The test of a state function is that it forms exact differentials.

For an exact differential the mixed second derivatives are equal.

ov =P aT
aT Ke e a

oe) = ett e KP (- Ka)

ov
=P ety= Ke.ol € uh Penis )
(-k

SR)
0
oP = etl eo KP (- ka)
Thus V for a substance that can be described in this way is a state
function.

A mole of liquid water is vaporized at 100 °C and 1.013 bar. The

heat of vaporization is 40.69 kJ mo1t, What are the values of

(2) we,
ev (b) q, (c) AU, and (d) AH?

SOLUTION
(a) Assuming that water vapor is a perfect gas and that the volume
of liquid water is negligible,
WwW -PAV = -RT

-(8.314 x 1079 ky Kt moi!) (373.15 K)

-3.10 kJ mot
(b) The heat of vaporization is 40.69 kJ molt, and, since heat is
absorbed, q has a positive sign.
 15

aq = 40.69 kJ moi2
(c) AU=qt+w
= (40.69 - 3.10) kJ molt
= 37.59 kJ molt
(d) AH = AU + A(PV) = AU + PAV
= AU + RT
= 37.59 kJ molt + (8.314 x 1072 kJ K-! mo1+) (373.15 K)
= 40.69 kJ mol
Calculate H°(2000 K) - B°(0 K) for H(g).
SOLUTION
Equation 2.50 may be integrated to obtain

T)
0 0 A 0
H°(T,) - H°(T,) = |Coan
Ty

2000
H°(2000 K) - H°(0 K) = oR aT = > R(2000) 28 402590") mols
0
Table A.2 yields 6.197 + 35.376 = 41.573 kJ mol
(Note that for O(g) a slightly higher value is obtained because
there is some absorption of heat by excitation to higher electronic
levels.)

2210 Considering H,O to be a rigid nonlinear molecule, what value of Cp

for the gas would be expected classically? If vibration is taken

into account, what value is expected? Compare these values of Cp

with the actual values of 298 and 3000 K in Table A.1.

SOLUTION
A rigid molecule has translational and rotational energy. The

translational contribution to Cy is
16

SR ali
acbel ay Kk mol
=A) ~. Since H,0 is a nonlinear molecule, it has

three rotational degrees of freedom, and so the rotational contri-

bution to Cy is = R = 12.471 J K+ mo17+. Thus Cp for the rigid

molecule is Cyletty Rosse cs iek a ole
Since H,0 is a nonlinear molecule, the number of vibrational

degrees of freedom is 3N —- 6 = 3. Since each vibrational degree of

freedom contributes R to the heat capacity, classical theory

predicts Cp 03362 58TaK samo te 3B

= 58.201 J K? moi?
The experimental value of Cp at 298 K is 33.577 J x! mo1?, which
is only slightly higher than the value expected for a rigid mole-

cule. The experimental value of Cp at 3000 K is 55.664 J x molt,

which is only slightly less than the classical expectation for a

vibrating water molecule.

5 Atal The heat capacities of a gas may be represented

by Cp = a + BT + yT?
For Ny a = 26.984, B = 5.910 x 10%, and y = -3.377 x 10°’, when
Cp is expressed in J x! mol!, How much heat is required to heat
a mole of No from 300 K to 1000 K?

SOLUTION
1000
2
" |(26.984 + 5.910 x 10-2 T - 3.377 x 10°” T2)aT
300
26.984(1000 - 300) + 5(5.910 x 1073) (10002 - 3002) -

$(3.377 x 10-7)(10002 — 3003)

21.468 kJ moi
 V7

2.12 One mole of methane (considered to be a perfect gas) initially at

25 °C and 1 bar pressure is heated at constant pressure until the
volume has doubled. The variation of the molar heat capacity with

absolute temperature is given by Cp = 22.34 + 48.1 x Lon at

where Cp is in J K-1 mo1-!. Calculate (a) AH, and (b) AU.

SOLUTION
596.2 K
Af | (22.34 + 48.1 x 1072 T)dT
298.1 K
= (22.34)(298.1) + [(48.1 x 1079)/2]1(596.22 - 298.12)
= 13.07 kJ moi?
AU = AH - PAV = 13.07 - P(RT/P)
= 13.07 - (8.314 x 10°> ky K-! mol
4)(298.1 K)
= 10.59 kJ moi!
One mole of perfect gas at 25 °C and 100 bar is allowed to expand

reversibly and isothermally to 5 bar. Calculate (a) the work done

on the gas in joules, (b) the heat absorbed in joules, (c) AU, and
(d) AH.

SOLUTION
(a) w = RT ln (P,/P,)

= (8.314)(298) 1n (5/100)

= -7.42 kJ mol
(b) q = -—w = 7.42 kJ mol
(c) AU = 0 since the gas is perfect
(d) AH = AU + A(PV) = 0

2.14 Calculate the temperature increase and final pressure of helium if

a mole is compressed adiabatically and reversibly from 44.8 L at
ONC 6122470.
18

SOLUTION
5 3 5
Y= Cp/Cy = > R)/ (> R) = 3

= Jl
tT (py
T) Mt
Ty (273.25 K)(44.8 L/22.4 L)2/3
433.6 K or 160.4 °C
Thus the temperature increase is 160.4 °c. The final pressure is
given by

Pre RT _ (0.08314 L bar K+ mol+) (433.6 K)

y ye Pei
1.609 bar

odlS A mole of argon is allowed to expand adiabatically from a pressure

of 10 bar and 298.15 K to 1 bar. What is the final temperature and

how much work can be done?

SOLUTION
y = Cp/Cy = (5 RY/( R) = 3 (y - W/y = 2/5

1, = (298-15 K)(1/10)7/° = 118.701 x

us)
atl Cy, dt = 2 R(T, - 7)
us
= 2
2 ° (3.314 y x mo1~4) (118.70 K - 298.15 K) e ° = 2238 J mo mol!
Thus the maximum work that can be done on the surroundings
ip 2238 J nolo.
 19

2.16 A tank contains 20 liters of compressed nitrogen at 10 bar and 25

°C. Calculate the maximum work (in joules) which can be obtained
when gas is allowed to expand to 1 bar pressure (a) isothermally

and (b) adiabatically.

SOLUTION
(a) For the isothermal expansion of 1 mol

Ie 2
Wreyv = RT In Py

= (8.314 JK? moi 1) (298.15 K) 1n (1/10)

= -5708 J mol
There are

(10 bar) (20 L)/(0.08314 L bar K+ moi 4)(298 K) = 8.07 mol.

Therefore the maximum work done on the surroundings is 46.1 kJ.

(b) For the adiabatic expansion we will assume that y = Cp/Cy has
the value it has at room temperature. From Table A.2

wire 29.12 5/429 125. —58.514) = 1,399

T p (y - 1)/y
1 1 T, <2) (298,15 K) (3/10), 0.285
° = 154.7 K
T, Po
T)
whbe= All ie~ ata= Co (Tyee)
Ty
(20.811 J K~+ moi 1) (154.7 - 298.15 K)
-2.99 kJ mol
For 8.07 moles the maximum work done on the surroundings is
24 4 EJ.<

2.17 In an adiabatic calorimeter, oxidation of 0.4362 gram of

naphthalene caused a temperature rise of 1.707 [C. The heat

20

capacity of the calorimeter and water was 10,290 J xl, If

corrections for oxidation of the wire and residual nitrogen are

neglected, what is the enthalpy of combustion of naphthalene per

mole?

SOLUTION
_ (10,290 J K71) (1.707 K) (128.19 g mol+)
(0.4362 g)(1000 J xJ~4)
=5163 kJ mol.
-18 The following reactions might be used to power rockets.

(1) Hy(g) + 509g) = Hy0(e)

(2) CH,0H(1) + 1507g) = CO)(g) + 2H,0(g)
(3) Hy (g) + Fo(g) = 2HF(g)
(a) Calculate the enthalpy changes at 25 °C for each of these
reactions per kilogram of reactants.

(b) Since the thrust is greater when the molar mass of the exhaust
gas is lower, divide the heat per kilogram by the molar mass of the

product (or the average molar mass in the case or reaction 2) and
arrange the above reactions in order of effectiveness on the basis
of thrust.

(a) (1) AH = -241.818 kJ moi

= (-241.818 kJ mol 4)(1000 g kg 1)/(18 g mo1~2)
= -13.4 MJ kgtt
(2) AH = -393.509 + 2(-241.818) + 238.66
= -638.49 kJ mol
= (-638.49 kJ mol +)(1000 g kg +)/(80 g moi~)
= -7.98 MJ kg
 21

(3) AH 2(-271.1) = -542.2 kJ mo11

(-542.2 kJ mol +)(1000 g kg~1)/(40 g mo1~1)
-13.6 MJ kg
Cb)” 6(2) o=1354/18 -0.744

(2) VE it a = -0.299
5(44 + 2x 18)

(3) —13..6/20 -0.680

bid > A392 > AZ)

2.19 Calculate the enthalpy of formation of PCls(cr), given the heats of

the following reactions at 25 oes
2P(cr) + 3C1y(g) = 2PC13(1) AH” -635.13 kJ mol~
PC13(1) + Cly(g) I= PCls(cr) AH” Ul 2437 28-41 wicla

Multiplying the second reaction by 2 and adding the two reactions

yields

1
2P(cr) + 5C1j(g) = 2PC1,(cr) AH® = -909.69 kJ mol
AH; [PC15(cr)] (-909.69 kJ mol *)/2
-454.85 kJ mol
PRAY) Calculate AH°for the dissociation O,(g) = 20(g) at 0, 298, and
3000 K. In Section 14.2 the enthalpy change for dissociation at 0

K will be found to be equal to the spectroscopic dissociation

energy Do-

SOLUTION
AH’ (0 K) = 2(246.785). = 493,570-kJ ‘mol7
AH® (298 K) 2(249.170) = 498.340 kJ mol
1
22

AH® (3000 K) = 2(256.722) = 513.444 kJ mol}

The spectroscopic dissociation energy of 0, is given as 5.115 eV in

Table 15.4. This can be converted to kJ mol? by multiplying by

96.485 kJ Vt moi! to obtain 493.521 kJ mol ?.

2.21 Compare the enthalpies of combustion of CH, (g) to CO,(g) and H,0(g)

at 298 and 2000 K.

CHy(g) + 205(g) = CO)(g) + 2H,0(g)

SOLUTION
AH® (298 K) 3997.52.20 48 2(—2
410. S27) 8 (748873)

-~802.303 kJ mol
AK® (2000 K) -396.639 + 2(-251.668) - (-92.462)

~807.5130kI_ mol
2.22 Calculate AH>9g for
Hy(g) + Fo(g) = 2HF(g)

Hy(g) + Cly(g) = 2HC1(g)

Hy(g) + Bro(g) = 2HBr(g)

Hy(g) + I5(g) = 2HI(g)

SOLUTION
(a) 2(-271.1) -542.2 kJ mol
(b) 2(-92.31) -184.62 kJ moi?
(c) 2(-36.40) = 30091 i} -103.71 kJ moi
(d) 2(26.48) - 62.44 -9.48 kJ mol?
2.23 Methane may be produced from coal in a process represented by the
following steps, where.coal is approximated by graphite:
 23

2C(cr) + 2H,0(g) 2CO(g) + 2H, (g)

CO(g) + H,O(g) i] CO, (g) + Hy (g)

CO(g) + 3H, (g) i} CHy(g) + H,0(g)

The sum of these three reactions is

2C(cr) + 2H,0(g) = CHy(g) + CO, (g)

What is AH® at 500 K for each of these reactions? Check that the
sum of the AH°’s of the first three reactions is equal to AH® for
the fourth reaction. From the standpoint of heat balance would it

be better to develop a process to carry out the overall reactions

in three separate reactors, or in a single reactor?

SOLUTION
AHSog = 2(-110.02) - 2(-243.83) = 267.62 kJ mol+
AHooq = -393.68 - (~110.02) - (-243.83) = -39.83 kJ mol?
AHSoq = ~80.82 - 243.83 - (-110.02) = -214.63 kJ mol™*
AHS99 = -80.82 - 393.68 - 2(-243.83) = 13.16 kJ mol*
Since the first reaction is very endothermic, there is an advantage

in carrying the subsequent reactions out in the same reactor so

that they can provide heat.

.24 Compare the enthalpy of combustion of CH, (g) to CO, (g) and H,0(1)

at 298 K with the sum of the enthalpies of combustion of graphite

and 2H, (g), from which CH, (g) can in principle be produced.

SOLUTION

AH° (298 K) = 393.51 + 2(-285.83) - (-74.81) = -890.36 kJ moi}

24
a
2H, (g) + O,(g) = 2H,0(1) AH® = -571.66 kJ mol
0 _—

= COy(g) AH® = -393.51 kJ mol 1

C(graphite) + O,(g)

The sum of the enthalpy changes for the last two reactions

(-965.17 EJ mol?) is more negative than the enthalpy change for

the first reaction by the enthalpy of formation of CHy(g).

Calculate the heat of hydration of NajSO,(s) from the integral

heats of solution of Na,SO,(s) and Na,S0,°10 H,0(s) in infinite
amounts of H,0, which are -2.34 kJ mol-! and 78.87 kJ moi?,
respectively. Enthalpies of hydration cannot be measured directly

because of the slowness of the phase transition.

SOLUTION
Na,S04(s) = Na,S0, (ai) AH® = -2.43 kJ mol?
Na,SO,(ai) = NajS04°10 H,0(s) AH? = -78.87 kJ mol?
NaySO4(s) + 10 H,0(1) = NayS04°10 H,0(s) AH® = -81,21 kJ mol +
2.20 Calculate the integral heat of solution of one mole of HCli(g) in
200 H,0(1).

HCL(g) + 200 H,0(1) = HC1 in 200 H,0

SOLUTION

AH}gg = AgH® [HC1 in 200 H,0] - A,H°[HC1(g)]

=16652720— 1(—924307)i = =73.965ekh mob ©
2.27 Calculate the enthalpies of reaction at 25 °C for the following
reactions in dilute aqueous solutions:

(a) HC1(ai) + NaBr(ai) HBr(ai) + NaCl1(ai)

(b) CaC1,(ai) + NajCO3(ai) = CaCO3,(s) + 2 NaC1(ai)
 25

SOLUTION
(a) AH® = O because all of the reactants and products are
completely ‘ionized.

Heer Ol S Noe eRe =H?) 4° Bs 74Na 4 Cin

(by) Ca’ (ai) + CO,*~(ai) = CaCO, (s)

Ae -7=e-1206,92°—1(-549°63) — (677,14) = 3 /05°k) mols.
2.28 Calculate AH’ (298.15 K) for the solution process

CaCl, °6 H,0(cr) = CaCl, in 400 H,0 + 6 H,0(1)

For CaCl,*H,0(cr), A,H? = -2607.9 kJ mo1+ and

for CaCl, in 400 H,0, A,H° = -874.982 kJ moi}.

SOLUTION
AH® = -874.982 + 6(-285.830) - (-2607.9) = 17.9 kJ mol72
Notice that the water of hydration is included explicitly in the
calculation, but the water of dilution is not.

What is the heat evolved in freezing water at -10 “c given that

HyO(1) = Hy0(cr) AH°(273 K) = -6004 J moi? and

C,(H)0,1) = 75.3 J K+ mol + and Cp(Hy0,s) = 36.8 J K-* mol”*
SOLUTION
AH 0 4263°K) cag
= Ho4273) K+ (pn oer) “3
p,n,oc1)! £10063 K == 273°)

SDE6004EF mai ' 19-5 (238 a5eF KE lp) (108k)

=: -§619. Jmol
2.30 What is the enthalpy change for the vaporization of water at 0 °C?
This value may be estimated from Table A.1 by assuming that the

heat capacities of H,0(1) and H,O(g) are independent of temperature

from 0 to 25 °C.
26

SOLUTION
H,0(1) = H,O(g)
AH’ (298 K) = -241.818 -— (-285.830) = 44.011 kJ mol 1
oO 0

AH®(273 K) = AH°(298 K) + [Cp(H,0,g) — Cp(H)0,1)1(273 - 298)

= 44,011 + (33.577 - 75.291)(-25) = 45,054 J mol?

Ae Calculate the enthalpy of dissociation of Hj(g) at 3000 K using

ApH (H, 298.15 K) = 217.999 kJ mol! and H° - H5 98 values in
Table A.2.

SOLUTION
2 (217.999)
Hy(g) = 2H(g)
298 K |

88.743 | 2 (56.162)

Hy (g) = 2H(g)
3000 K

AH’ (3000) = -88.743 + 2(217.999) + 2(56.162)

= 459.579 kJ mol! (4.74551 eV)
fan 32 Calculate the standard enthalpy of formation of methane at 1000 K

from the value at 298.15 K using the H° - Hjg9g data in Table A.2.
SOLUTION
1000 K C(graphite) + 2H, (g) = CH, (g)
0 0 0 0 0 0
(Hiooo ~ B298)¢ 2(Hi 000 ~ A298) Hn, (i000 ~ 298) cu,
298 K C(graphite) + 2H, (g) = CE, (g)

The change in state represented by the first reaction can be

accomplished by cooling one mole of graphite and two moles of

 2),

hydrogen to 298 K, converting them to methane, and then heating the

methane to 1000 K.

0 a ae Oris v= 0 = 0 0 0
AsHi000 = ~Hio00 ~ 2298)¢ ~ 2Hio90 ~ M298), + AgB (CHy, 298 K)
0 0
+ (Hy 990 - #298) cH,
-11.816 = 2(20.686) -— 74.873 + 38.179
-89.882 kJ mo1
2.33 Estimate the heat capacity at constant pressure at 298 K for ethane
using the Benson method. Compare this result with the value

calculated using values in Table 2.2.

UN Me
Cpi= 2(25590)" = 51-80 7°x* moi
Cp = 9.404 + (159.836 x 1079) (298.15) - (462.28 x 10°7)(298.15)?
52.95 J K-72 moi?
2.34 Estimate the enthalpies of formation of n-butane and iso-butane at
298.15 K using the Benson method.

SOLUTION
1
For n-butane, A pH® 2(-42.68) + 2(-20.63) -126.62 kJ mol
1
For iso-butane, AH 3(-42.68) - 7.95 -135.99 kJ mol

The values in R. A. Alberty and C. Gehrig, J. Phys. Chem. Ref.

Data, 13, 1173(1984) are -125.7 and -134.6 kJ mol1, respectively.
2.35 914.3 m

2.36 2.91 kWh 0.172 4.4 kg

0.37 (a) 172 (b) kJ mol

28

dCy/9d In V # 0(RT)/0T
dCy/9 In V = OR/d In T

(a) 1.99 (b)a-23730 (c P2500 (4) -21.31 “J mol2

-41 106.780 kJ mol2
.42 At 298 K HI is a rigid diatomic molecule. At 200 K its
vibration is almost completely excited. At 298 K I, is
almost completely vibrationally excited. At 2000 K it absorbs
more energy per degree because of electronic excitation.

-43 co CO, NH3 CH,

Cp(classical) 37.413 62.354 83.136 108.077

Cp (3000 K) YT] ey 62.229 719.496 101.391

Thesvalués are in J-Ki- mol -.

44 40.874 kJ mol+
45 (a) -5.70 (b) 5.70 (c) 0 (4) 0 kJ moi?
- 46 (a) 567K (b) 9.42 bar (c) 5527 J molt
-47 (a) 0.495 (b) 0.307 bar
-48 (a) 41.84 (b) 25.56 kJ
-49 C(cr) + 20(g) + 2H, (g)

CHy(g) + 209 (g)

CO, (g) + 2Hy(g) + 05(g)

CO, (g) at 2H,0(1)

-50 (a) -253.42 (b) -249.70 kJ mol +

 29

Mem | ASIST malas

22 12.01 kJ mo1~4
Ae! SSOkut Say ol. end. -=S86.4 2 kT mol)
-54 (a) -120.9 (b) -50.2 (c) -19.92 (ad) -45.2 kJ mol
eke 225.756 kJ mol* is absorbed.

-56 -214.627, —-800.521, -1015.148 kJ mo1

sol 432.074, 435.998, 459.578 kJ mol4
1
-58 2145627, 407892) 16, 710KS aol >: Single reactor.

1
oo (a) -94.1 (6)'235970 CT mol”
-60 (a) 0.038 (b) 10,03 KJ mol--
-61 -44.037 kJ mol2
562 2432.63 g 2
- 63 1640.558 kJ mol?
-64 -89.881 kJ mol
.65 2600 K
CHAPTER 3: Second and Third Laws of Thermodynamics

$. 1 Theoretically, how high could a_gallon of gasoline lift an

automobile weighing 2800 1b against the force of gravity, if it is

assumed that the cylinder temperature is 2200 K and the exit

temperature 1200 K? (Density of gasoline = 0.80 g om >; 1 lb =

453.6 g; 1 ft = 30.48 cm; 1 L = 0.2642 gal. Heat of combustion

of gasoline = 46.9 kJ gt.)

SOLUTION
q = (46.9 x 103 J got)(1gai)(10% ems L1) (0.80 g cm *)
0.2642 gal Lt
= 14,2 x 10’ 7
T=
1 . 1 20 :
er ,
ee ee
2
we Aa 20 S12 200 Bs 100 EP sy oye kee os
Ty (2200 K)

= mgh = (2800 1b) (0.4536 kg 1b-1)(9.8 ms ~) (0.3048 m ft “)h

h = 17,000 ft

3. (a) What is the maximum work that can be obtained from 1000 J of
heat supplied to a steam engine with a high-temperature reservoir
at 100 °C if the condenser is at 20 ° Cc? (b) If the boiler
temperature is raised to 150 *c by the use of superheated steam
under pressure, how much more work can be obtained?

SOLUTION
t T. - T
2 80 K
(a) Wose.G ee = (1000 J) 373.1 K = 214 J

130
(b) w=) (1000 2) see
423.1K
ee © SOTEE lee G8 nee
 31

3.3 A heat pump is to be used to maintain the temperature of a building

at 18 °C when the outside temperature is -5 °C. For a frictionless
heat pump how much work must be expended to obtain a joule of heat?

SOLUTION
lw] = lag }(ry - T))/7, = (2 3)(23 K)/(291 K)
= 0.079 J

ae What is the entropy change for the freezing of one mole of water at
0 °C? The heat of fusion is 333.5 J g .

SOLUTION
SANT A (os5 oe fe yO OlS nol) = = =f =]
AS = a 273.15 K = 22.00 J K mol

In the reversible isothermal expansion of a perfect gas at 300 K

from 1 to 10 liters, where the gas has an initial pressure of 20.27

bar, calculate (a) AS for the gas and (b) AS for all systems
involved in the expansion.

SOLUTION
tee ae (20.27 bar) (1 L) Be pe ae?
(0.08314. L bar. Ka++mol +) (300.K)
Vv2 1 7
AS = nR In = (0.812 mol)(8.314 J K Ve Rot +) dn Ao
1
="15356.J 1k ~
(b) AS = 0 since the process is carried out reversibly. The heat
gained by the gas is equal to the heat lost by the heat
reservoir, and both bodies are at the same temperature.

3. 6 Assuming the heat capacity of water is independent of temperature,

calculate the net change in entropy when 1 mol of water at 0 °C is

mixed with 1 mol of water at 100 °C. Assume the heat capacity is
32

(4.184 y K71 g-1)(18 g mot4) = 75.3 J K1 moi+, and the heat

capacity of the calorimeter is negligible.

SOLUTION

The entropy change for the cold water is

-1 -1
AS came (1553, INR Tae Ng 273.15
eee 126505 7K mol

The entropy change for the hot water is

ASy
Q= C153 030K
ee
mol ~) in
323.15
37345 ~10.83 J K+ moi
The net entropy change, 1.82 J ie mo1t, is positive, as expected
for an irreversible process.

A mole of propane gas is allowed to expand from 2 L to 10 L. What

is the change in entropy of the propane, assuming (a) it is a

perfect gas and (b) it is a van der Waals gas?

SOLUTION
Vo 10°L) no1= = eee eal
(a) AS = R In Te
8.3144 In ———————- ='—s6gW». 113.38 Ji K mol
i 2 L mol
Voth
ES: at UE ELWSe
(bv) AS “= R In Bea AO e084 13.67 J] K+ -1 mol -1

Calculate the increase in entropy of a mole of silver that is

heated at constant pressure from 0 to 30 °C if the value of Cp in

this temperature range is considered to be constant at 25.48 J x}

mol+,

SOLUTION T
A Pa pale2
p in re a ;
(25.48e 1 5kKeo
ig nole=
ay a in hs
303
73

= 2.657 J K7* noi7t

Sak) Calculate the change in entropy of a mole of aluminum which is

heated from 600 °C to 700 °C. The melting point of aluminum is

 33

660 °C;\ the heat of fusion is 393 J g 1, and the heat capacities of
the solid and liquid may be taken as 31.8 and 34.3 J K moi,
respectively.

SOLUTION

T T
f 2
Cc AH Cc
_ Pos f Pod
AS = r diet i + = dT
T, T}

Tr AH T
=C In — + +C In
Pes T Tr P51 Ty

-1 -1
= =i -1 933 K (C27 g mol )(393 J g )
(30-870 0K mol ~) In R73 K + 933 K +

= -l 973 K _ =| =]
(345 3,0—K ie moles ein EP 14.92 J K~ mol

ee A mole of steam is condensed at 100 °C and the water is cooled to

0 °C and frozen to ice. What is the entropy change of the water?
Consider that the average specific heat of liquid water is 4.2

yx ae The heat of vaporization at the boiling point and the

heat of fusion at the freezing point are 2258.1 and 333.5 J gt,
respectively.

SOLUTION

AS = - = vap aiar Cp
aterous

yap” 3373 K fus

_ _ (2258.1
= —)(18.016 g
J g mol
= ~) r
: 373.15 K
273 K = =]
=
(75 3798) Ki mol) |4
= in T
_ (332-55
(333.5 J ge 18.016
te
g ee
mol _)
o73 kK :
-154.4 3 kK! moi
34

ww .11 Calculate the increase in entropy of nitrogen when it is heated

from 25 to 1000 °C (a) at constant pressure, and (b) at constant

volume. Given: Cp = 26.9835 + 5.9622 x 10° T - 3.377 x 10°! 17

ones ke isola

SOLUTION
1273, 1273
Cayuse z= (28-9835 5.9622 x 10° - 3.377 x 10! T)daT
298 298

= 26.9835 In ue F 5. 9622"x 10 (1273 —2298)5—

(53.377 x 10-7(12732 - 2987) = 45.25 3 K+ moi

va Lares, UP. ies

(b) AS = —;— aT = —F aT - 8.314 In 35
298 298

= 45.25 - 8.314 In ie 2i'39eie jana lence:

3.12 One mole of ammonia (considered to be a perfect gas) initially at

25 °C and 1 bar pressure is heated at constant pressure until the

volume has trebled. Calculate (a) q, (b) w, (c) AH, (d) AU, and
(e) AS. Given: Cp = 25.895 + 32.999 x 109 T - 30.46 x 107 T? in
TK + mol
SOLUTION
(a) q I Q
a]
a lar

894
3 |
[25.895 + 32.999 x 10. T - 30.46 x 10. T]aT
298
 35

= (25.895) (596) + — 32.999 3 DOs

eye -~ 2982)-
30.46 x 10°
Bye - 2983)
3
-

= 26.4 kJ mol
(b) w = -PAV = -R(T, - T,) = -(8.314 J K+ moi
4) (596 K)
= -4.96 kJ moi
(c) AH = q, = 26.4 kJ mol
(dq) AU= gq + w= 26.4 — 5.0 = 21.4 kJ mol4
894
cP
(ie) Se 7 dT
298
894
= [ee $932.999 x 105 — 30746 4.105) Thal
298
-7
= 25.895 in soe 32.999 x 1073(894 - 298) - 30:48 3 20 — (8942 - 2982)

= 46.993 K mol?

3.13 A mole of perfect gas is expanded isotbermally and reversibly from

30 L to 100 L at 300 K. (a) What are the values of AU, AS, w and
q? (b) If the expansion is carried out irreversibly by allowing
the gas to expand into an evacuated container, what are the values

Of vAUGEAS. =wanda:

SOLUTION
(a) eAUS=20

KSueaa RT ya Owihtewiae
. els aie yah
30,L
= 10.01 J K~1 mo171
36

eo= =RT In Z = -~(8.314 J K7! moi!) (300 K) In ao =

= =3,.003 kJ’ mol-

¢ =©31003 9 mot2
(b) AU = 0 AS = 10.010 J K-'- mol)
w= 0 q = 0

The temperature of a mole of perfect monatomic gas is increased

from 300 K to 500 K. What is the change in entropy (a) if the

volume is held constant and (b) if the pressure is held constant?

SOLUTION
T
(a) AS =
Jone 3
Cy In hae 7 (8.314 IK
SER) ively
Aes|)) la
500 KK
300

= 6.371 J Kv! moi

(b) SAS-=ss Cy aia

1 ateme 2 g a 31481 Kulenolnl
sa lake*7300"K

= 10.618 J K7! moi

Saas A mole of argon undergoes the following change in state

P, = 20 bar, T, = 300 K > Py = 1 bar, T, = 200 K

What is the change in entropy, assuming it is a perfect gas?

SOLUTION

Since argon is monatomic, equation 3.55 yields

AS ges
= 5(8.314) In iTS = =
355 - 8.314 In5= 16.48 3 K~ ote!
mol

3.16 What is the change in entropy of a mole of liquid benzene at 25 :C

when the pressure is raised to 1000 bar? The coefficient of thermal

expansion a is 1.237 x 10.2 K-1, the density is 0.879 g cm >, and

the molar mass is 78.11 g mol?,
 37

SOLUTION
AS = -VaAP +

78.11 1 =I e E Piece
= east =| (1072 m cm +)3(1.237 x 1072 K~1) (1000 bar)
0.879 g cm

=10/99 J K7) moi~2

3.17 Ten moles of Hy and two moles of Ds are mixed at 25 ° C. What is

the value of AS°?

> wn |=-R(n, invy; + ny In yo)

—(8.314 J K-* mol*) [c20 mol) In at (2 mol) In Z|

44.95 J Kt
3.18 Section 3.13 showed that the entropy of mixing of 4 atoms of A and
4 atoms of B in an idealized crystal is k In 70. When Stirling's
approximation is used, equation 3.68 is obtained. Equation 3.68
will give only an approximate answer for the 8 atom system, but
calculate the result and see how good it is.

SOLUTION
ASa=-katn 70% 14.425) &

1 1
AS = -k[4 In ee 4 1n z! =ESk olny 2m 9555 0k

3.19 Calculate the molar entropy of liquid chlorine at its melting

point, 172.12 K, from the following data obtained by W. F. Giauque

and T. M. Powell.
38

T/K 15 20 Zz 30 35 40 50 60

Cp/J K+ mo14 Sele 7.74 12.09 16.69 20.79 23.97 q29525, (33.47

T/K 710 90 110 130 150 170 172.12

Cais Kl nol. 86.32 40263 43081 947704 p51804~ 55210 M.P.

The heat of fusion is 6406 J mol 2. Below 15 K it may be assumed

that Cp is proportional to T°.

SOLUTION
Ror T (45 k,C, = Cr’) C= ee
(15 K) 3
15 K
: || tO 3 dh 30 ER15) e e edee seaS
Sig pec Se SA
0 15
1.24 3K! moi4

The contributions from 15 K to the melting point are calculated

using CpAT/T, where Cp is the average for the range and T is the
average for the range.

K Taveg Cp avg AT
15-20 17.5 ols 5
20-25 2255) 9.92 5
25-30 MLS 14.39 5
30-35 S2o 18.74 5
35-40 3735 Pd Be 5
40-50 45 26.61 10
50-60 55 31.36 10
60-70 65 34.89 10
70-90 80 38.47 20
90-110 100 42.22 20
110-130 120 45.52 20
130-150 140 49.14 20
150-170 160 SSO, 20
LIO=LI212 171.06 ee hay AW PARWed
 39

CAT AH
P fus 6406
S
liquid, T,
? . =
1.24 >
+ Z \
7 + ——
T =
1.24 + 69.29 + 172.12
—_ ——

Sa
m

107075) K > mol

.20 Calculate the molar entropy of carbon disulfide at 25 °C from the
following heat-capacity data and the heat of fusion, 4389 J moi},
at the melting point (161.11 K).

T/K 15.05 20.15 29.76 42.22 57.52 75.54 89.37

Cp/J Knot 6.90 12.01 “20.75 29.16 35.56 40.04 43.14

T/K 99.00 108.93 119.91 131.54 156.83 161-298

Cp/J K-1 mo17! 45.94 48.49 50.50 52.63 56.62 75.48

SOLUTION
161.11 K 298.15
C(15.05 K) C AH C
ry eee ve. fus oe
S°" (298.15 K) = Fae ae ee T dT + id 7 dT

15.05 K 161.11

The first integral may be approximated by multiplying the average

value of Cp/T for each temperature interval by the width of the

interval. Thus the first contribution is

1 (6.90 , 12.01 ) (20.15 - 15.05) = 2.69 J K~ moist

2.15505. 20215
The first integral has the value 74.69 J K-! mo17!. Thus
é 6.90 4389 298.15
S; (298715 K) ——3 + 74.69 + a IEEE + 75.45 ln 161.11
161.11

i} 150.67 JK? moi

3 Pil Using molar entropies from Table A.1, calculate AS®° for the

following reactions at 25 6
40

(a) Hy(g) + 5 09 () = H,0(1)

(b) Hy(g) + C1y(g) = 2HC1(g)
(c) Methane(g) + = 05 (8) = Methanol(1)

1
(ay AS ver 6909 1)= 130.68 z (205.13) -163.34 J K7+ moi
il
(b) AS° = 2(186.908) - 130.684 -— 223.066 20.066 J K-- mol

°
~~ — > op) Se ll 126 ha 186064 > (205.138) = <162.0 J.Ki mote

3.22 What is AS° for H,(g) = 2H(g) at 298, 1000, and 3000 K?

1 al
AS° (298 K) i} 2(114.604) - 130.574 98.634 J K ~ mol

AS° (1000 K) 9(130.758) = 166.113 i} 113.403 J K-* moi2

AS° (3000 K) Wt 2(162.594) - 202.778 i] 122410 J K+ mol*
3.23 What is AS°® (298 K) for
H,0(1) = H*(ao) + OH (ao)

Why is this change negative and not positive?

SOLUTION
AS = -10.75 - 69.92 = -80.673 K} moi}
The ions polarize neighboring water molecules and attract them.
For this reason the product state is more ordered than the reactant
state.

3.24 From electromotive force measurements it has been found that AS°

for the reaction + Hy (s) + AgCl(cr) = HCl(aq) + Ag(cr)

1
is -62.4 J K+ moi? at 298.15 K. What is the value of S°[C1~(aq)]?
 41

SOLUTION
Since HCl is completely dissociated in aqueous solution
and S°[H‘(ao)] = 0,

AS® = $°[C1™(ao)] + S°[Ag(er)] - 5 S°[H)(g)] - S°[AgC1(cr)]

~62.4 = S°[C1 (ao)] + 42.55 - > (130.684) 90.2

SfC1=(a0)Jo"= 5636 JK) mot!

See Estimate the standard entropy of n-butane and iso-butane at

298.15 K using the Benson method.

SOLUTION
For n-butane, S° = 2(127.24) + 2(39.41) - 8.314 in (3% x 2)
i} 309.3 J K+ moi1
For iso-butane, rhe 31127 .24)) = 50.50 —-8.914 In 37
303.8 J K- mol4

3.26 The gas is not returned to its initial state.

eee | (a) 16.1% (b) 34.8% Ce). 37.1%

(d) 37.3% (e) 47.1% (f) 62.0%

3.28 9.96 JK moi

3.29 Since this quantity is always positive, the change is
spontaneous.

3.30 (a) 8.50 (b) 76.61 (eo) 5.00 J Kk molt

Seok 125.39 J K+ mo12
Soe 19.262 J K-! mo1~+
SAGE) AU = -2.252 kJ mo1~2 AS'= 0

q=9re Ww ll 2) 252 EI moi!

=0.0253 3 Kk mol
9.13 J K-* moi
For the system AS = 0.021 J k-1 mo1-1. Therefore the change
is spontaneous.

115-5 J K+ moi
288.7 3 K-2 mo1—2
(a) 80.479 (bh) 32-93 (c) -38.9 7 kK mol*
eSNG) 45.426 7 Ko ol
316.6 JK mol
20308 365200) Kat omol
CHAPTER 4: Gibbs Energy and Helmholtz Energy

4.1 Derive the expression for Cp - Cy for a gas with the following
equation of state.

(Py eRT
ue

SOLUTION
Combining equations 4.41 and 4.47

Cp
_ 7/22)
cy - 1(3) V (5),
fav
RT a
Pp SS ate Sa
V y2

(=) _R
aT, V

py2 = RIV - a
py - RIV + a = 0

2 we(34) - wv mal) = 0
Pp Pp
(2) EP. APRy ere
OU) tee2 PVs BE

2 PV DaaNe
cp - cy = RZ 2Y- 3] = nls - 3.8)

4.2 Show that Cp and Cy for a perfect gas are independent of volume and

pressure.

SOLUTION

cy - (37)
V
av
aT),

(2)
av
agouti -OVoT.
tee dlav.
Yee) ~ dT VovV
;
44

since (=) = 0. The value of (0V/dV) 7 can be obtained from

T Equation 4.42.

(2¢v)
oP T
coed
OdPO0T
feats
dTOP
geoTDey\ dPOlT SCY
oT \ OV T oP T
6
since (0V/dV)_ = 0 for a perfect gas. Since Cp = Cy + R,
(dCp/dV) 7 = 0 and (0Cp/ dP) > = 0.

4.3 (a) Integrate the Gibbs-Helmholtz equation to obtain an expression

for AG, at temperature Ty in terms of AG, at Tj, assuming AE is
independent of temperature. (b) Obtain an expression for AG, using
the more accurate approximation that AH = AH, + Ch T,)ACp where

Ty is an arbitrary reference temperature.

(a) Using equation 4.51

|acacrn —— |(AH/T*) aT

ia ces meee 6
Sar |
qT, a T, T,

AH, (T - T,)
(b) d(AG/T) = — dT + ac ——_~.— dT
2 P 2
T T

AG AG T
2 il te 2 ) 1
—— -— = - —-=) + ACp ln — + T,AC,/— - —
Ty Ty (7; 7;| P Ty bE olz, =

4.4 One mole of a perfect gas is allowed to expand reversibly and

isothermally (25 °C) from a pressure of 1 bar to a pressure of 0.1
 45

bar: (a) What is the change in Gibbs energy? (b) What would be
the change in Gibbs energy if the process occurred irreversibly?

SOLUTION
aG
(a) (3) = V=
RT
=
aP | P

Po
AG = RT Iny- = (8.314 5 £ * nol +)(o08$.15 Kk) In 001
1
= -5708 J mol
(b) AG = -5708 J mol? because G is a state function and
depends only on the initial state and the final state.

$5) Calculate the change in Gibbs energy for the process

H,0(1,-10 °C) = H,0(cr,-10 °C)
The vapor pressure of water at -10 °C is 286.5 Pa, and the vapor
pressure of ice at -10 °C is 260.0 Pa. The process may be carried

out by the following reversible steps:

ake A mole of water is transferred at -10 °C from liquid to

saturated vapor (P = 286.5 Pa). AG = 0, since the two phases

are in equilibrium.
Die The water vapor is allowed to expand from 286.5 to 260.0 Pa at

-10 °C.
3% A mole of water is transferred at -10 °C from vapor at

P = 260.0 Pa to ice at =-10 °C.

SOLUTION
Since the first and third steps are transfers at equilibrium, there
are no Gibbs energy changes associated with them.

P4 - a 286.5 Pa
AG, = -RT 1n Eee -(8.314 J K~ mol ~) (263.15 K) In 5-5-5

2240503. nol
46
4.6 A mole of perfect gas is compressed isothermally from 1 to 5 bar at

100 °C. (a) What is the Gibbs energy change? (b) What would have
been the Gibbs energy change if the compression had been carried

out at 0 Ge?

SOLUTION P
0 2 -1 -1
(a) AG = RT in moat (8.314 J K mol ~)(373.15 K) In 5
1
= 4993 J mol2
(b) AG = (8,314.7 K " mol —)(273.15.K) In 5 =) 3655 J mole”
What is the difference between the molar heat capacity of iron at

constant pressure and constant volume at 25 °C? ~Given:

a = 35.1 x 10° xt, ,K = 0.52_x 107° bart, and the density is

7.86 pcm.

=i. 3 =i1
Voss oct! Smell | 3 1 cm mol me i ecci0r® at mcta!
7.86 g cm? (107 cm m+)3

Gp Caer
(35,1 x 107° K74)2(298 K)(7.11 x 107° m> mot
1)(10° Pa bar!)
(0.52 x 10° bar+)
0.51 J K* moi4

4.8 When a liquid is compressed its Gibbs energy is increased. To a

first approximation the increase in Gibbs energy can be calculated
using (dG/dP), = V, assuming a constant molar volume. What is the
change in Gibbs energy for liquid water when it is compressed to
1000 bar?
 47

SOLUTION
2 ae
ac = | vaP
i Sn
>Q I VAP = (18 x 10°© m> mo1~1)(999 bar)(10° Pa bar~4)
1.8 kJ mol
Show that when a liquid is compressed, the change in Gibbs energy

is given by
1
AG = VAP - > RV(AP)? if K AP << 1. The isothermal compressibility
is represented by KG.

SOLUTION
2 Po Py
dGeese [swap eax Pday ex’ex io wap
G, P, Be

= 1]

[KAP - 2K 2(aP)? +... 1 = vaP - 5h V(AP)?

The entropy of 0j(g) at 1 bar is listed in Table A.2 in the

Appendix as 205.138 J x} mol! , and the Gibbs energy of formation

is listed as 0 kJ mol, Assuming 05 is a perfect gas, what will

the molar entropy and molar Gibbs energy of formation be at 100

bar?

SOLUTION iL =
S = S’o= Ro dn -* = 205.138 - 8.314 1n 100 = 166.849 J K” mol
Pp
48

A,G° = 0 + RT In (P/P°) = (8.314 x 1072) (298) 1n 100

11.41 EJ mol)
pola A mole of helium is compressed isothermally and reversibly at

100 °C from a pressure of 2 to 10 bar. Calculate (a) q,

(b) w, (c) AG, (d) AA, (e) AH, (f) AU, and (g) AS.

Po
de=— Wee hei ne
Pi
= -o(8 314 7 Ko) mol.
2)(373415 Koo laren
2 bar
sc 0s et mote

(b) w=-q = 4993 J mol?

PF P, F
(c) AG = VaP = RT In 5- = 4993 J mol
1
Py
(4) AA = who = 4993 J mol
(e) AR — AU + A(PV) = 0
CE) PAH E—30
= _AG_, _ 4933 J mol 1 ek -1 —
(g) AS = AH tT 0 e373 sks = 13.38 J K ~ mol

-12 (a) Calculate the work done against the atmosphere when 1 mol of
Ct)
toluene is vaporized at its boiling point, 111 .C. The heat of
vaporization at this temperature is 361.9 J gt. For the
vaporization of 1 mol, calculate (b) q, (c) AH, (d) AU, (e) AG, and
(f) AS.

SOLUTION
(a) Assuming that toluene vapor is a perfect gas and that the
volume of the liquid is negligible, the work done against the
 49

atmosphere is

w= PAV = RT = (8.314 J K- mo1~1)(384 K)

= 3193 J moi2
NOTE: The work done on the toluene is -3193 J mol.

(b) Gp = AHygy = (361.9 J g™1)(92.13 g moi?) = 33,342 J mot,

(c) AH = 33,342 J mol2
(d) AU = q + w = 33,342 - 3193 = 30,149 J moi
(e) AG = 0 because the evaporation is reversible at the boiling
point and 1 atm.

q -1
ieee Se 33,342 JJ mol = -1 -1
(f) T 384 K 86.8 J K mol

4.13 One mole of a perfect gas at 300 K has an initial pressure of 15

bar and is allowed to expand isothermally to a pressure of 1 bar.

Calculate (a) the maximum work that can be obtained from the

expansion, (b) AU, (c) AH, (d) AG, and (e) AS.

[ 1
Cajawee=iRL an = (8.314 J Kk mo1 +) (300 K) In is
Py 5

269954 47° mol

(b) AU = 0 because dU/0T = O for a perfect gas
(c) AH = AV + A(PV) = 0
P
(a) AG = RT In = = =6 2754 kF mola
j

(Ce) ASS =) RD in oe
i (8.314 J K~
iret
mol ~)(in 15)
2
199.54 J Ki mol
50

4.14 For H,(g) up to 100 bar the fugacity may be represented

approximately by f = pebP/RT where b = 0.01399 L moi, What is

the fugacity at 100 bar?

SOLUTION
(100 bar) = exp
(0.01399 L mol
+) (100 bar)
: =i! =i
(0.08206 L atm K mol ~)(298 K)
105.9 bar

Using the relation derived in Example 4.6, calculate the fugacity

of H,(g) at 100 bar at 298 K.

SOLUTION
f =2 P exp (b gERT RT
ag

= (100 bar) exp [0.02661 - 0.2476/(.08314)

(298) ]100/(.08314) (298)

106.9 bar

4.16 Show that if the compressibility factor is given by Z = 1 + B’P the

fugacity is given by f = Pel, If Z is not very different from
unity, e+=<1+ (Z- 1) +... &Z ‘so that £ = PZ. ‘Using this
approximation, what is the fugacity of Hy (g) at 50 bar and 298 K
using its van der Waals constants?

SOLUTION
Pp

19 | - nf + 2 ap
P Pp
0

Pp
= (= + B'dP = uf t') +2 Rp
Pp ; Pp
0
 |

a P
Th A say — RP ‘EP

a pe PIO ATE 50
1.034
PLUS omerELUM
ERTAY, (0.08314) (298)

f = (50 bar) e9°934 = 51.7 bar

4.17 As shown in Example 4.6, the fugacity of a van der Waals gas is

given by a fairly simple express ion if only the second virial

coefficient is used. To this degree of approximation derive the

expressions) Lom G, as, As) U, oH, and: Vi;

SOLUTION
G@ =.G> +27 19(—| a Me ee oT. nf) (b - ale
p° p°

a2 Eee = S°-R 1n(}* —

p°} rt2
A=6- p(28| =a Goud RT in | - RT
Ge p°

U=6 -
aG
(28) Pipl
dG) _ G
0 + TS
3 RT
aP
RT

0 aP zy Orr aP
aaa se DOCRT
Since the second term is small, we can use the perfect gas law to

obtain =U = va

Note that this agrees with the earlier result (Section 4.4)

that (QU/aV)_ = a/V?.

H=U+ ~ 7° 4+
PY =U° +2.2b + RT + bP -
_ ab
5
0 2a
=H + (b- RDP
52

4.18 Using experimental data from Fig. 4.4 calculate (08/01), and
(0U/d1), using only the data at 10 °c and 70 °C, assuming these
quantities are independent of temperature. These thermodynamic

quantities do depend on the elongation so calculate them for 200%

and 400% elongation. (For f and T simply use averages for this

temperature range.)

SOLUTION
At 200% elongation

(23) + (a _ _ (10.8 - 9.0)(10° Nm”)

a1), aT), (70 — 10)K
ee=3 Ors 10> NUKo mee
au E 2755
(7)
a1 T eee 1(3)
aT 1 = 9.5 x'107 Nm ~ = (319"K) (3.0 x 10° No keo eee

= OSL"N mn -
At 400% elongation
os EP (260 213) xe 207 5 Nee —2
= 3 ily eto)

oU = oa =
(27) = 23 x 10° Nm” — (313 K)(7.8 x 102 NK m2)
T

= -1.4N me*

2 3
R°T V
4.20
RIV = 2a(¥ > b)-
4.21 (aV/aV), = a/2Tt/2vv - »)
4.22 -108.3 J moi2
4.23 89.5 J moi+
4.24 1.756 «3 moi
 53

4.25 168-97. F Kiet moll4 6 0p = 11 42°49 Wor

4.26 (a) 6820 J mol (b) 6070 J mol
(ed) OF mol (d) 15.73 kK! moi?
4.27 (a) -5230 J mol (b) 5230 J mol
(c) OJ moi (d) -5230 J mol 4
(e) 19.142 3 K7! moi (f) 0 J mol?
Cg)y OF mol (h) 0 J mol2
(i) -5230 J molt (j) 19.142 J K+ moi
(x) o3 Ko moi! 1) 19.4940 7 Ko mole
4.28 3100, -40,670, -40,670, =37,570; 0,
3100 J mol
-108.8 J K+ moi+
4.29 0, 19.16 3K moi
4.32 60a 107°.) 5.8)x 10°" me
CHAPTER 5: Chemical Equilibrium

Dre J Calculate AG and AS for the formation of a quantity of air

containing 1 mol of gas by mixing nitrogen and oxygen at 298.15 K.

Air may be taken to be 80% nitrogen and 20% oxygen by volume.

(8.314 J K+ moi“) (298.15 K)(0.8 In 0.8 + 0.2 in 0.2)

iso aoe
ail mol =
I
In Yall + MG) In Yo) = 4,159 J K
AS nix = “Rlyy

af? A mole of gas A is mixed with a mole of gas B at 1 bar and 298 K.
How much work is required to separate these gases to produce a

container of each at 1 bar and 298 K?

SOLUTION
The mixture can be separated by diffusion through a perfect semi-
permeable membrane. The highest partial pressure of each that can
be reached is 1/2 bar. These gases then have to be compressed to 1
bar.

1 aL

= tl (2 mol) VdP = (2 mol) (RE/

DP) dee = 2s nol) eines
If. 1/92

= 2(8.314)(298) In 2
= 3.4 kJ
The actual process will require more work.

His) For the reaction Ny (g) ae 3H, (g) = 2NH3(g), K = 1.60 x 10-4 at
0
400 °C. Calculate (a) AG° and (b) AG when the pressures of No
and H, are maintained at 10 and 30 bar, respectively, and NE, is
 Bic

removed at a partial pressure of 3 bar. (c) Is the reaction

spontaneous under the latter conditions?

SOLUTION :
(a) AG° = -RT ink
ee
= (6.314 1 Eo Ah) ine,
mol- SK.
J4673 K) An 1.60) x10 -4

= 48.9 kJ mol +
2
PAH
(b). AG = AG® + RT In :
P. Pe
ae
3
= 48.9 + (8.314 x 10-°)(673) In --#--
10(30)
= 10.2 kT moi
(c) No

A 1:3 mixture of nitrogen and hydrogen was passed over a catalyst

at 450 °C. It was found that 2.04% by volume of ammonia was

formed when the total pressure was maintained at 10.13 bar [A. T.
Larson and R. L. Dodge, J. Am. Chem. Soc., 45, 2918 (1923)]. Cal-
culate the value of K for > Hy (g) + > Ny (e) = NH3,(g) at this tem-
perature.

SOLUTION
At equilibrium a8 a PN + "NE, = 10.13 bar

rg WW (10.13 bar) (0.0204) = 0.207 bar

ac) 24 rg = 10.13 bar - 0.207 bar = 9.923 bar

ro Ul w ac] because this initial ratio is not changed by reaction

 56

pe oe 9.923 bar _ 2.481 bar

N 2, 4
P = 39,923 bar) = 7.442 bar
H 4
Z
Ct)

(Pxn,/”')
K g Bre
—
(m/e)?

- 5281 ___, = 6.47 x 10°

7.442°/7 2,482
5.5 Water vapor is passed over coal (assumed to be pure graphite in

vay: this problem) at 1000 K. Assuming that the only reaction occurring

is the water gas reaction

C(graphite) + H,0(g) = CO(g) + H, (g) K = 2.52

calculate the equilibrium pressures of H,0, CO, and Ho at a total

pressure of 1 bar. (Actually the water gas shift reaction

CO(g) + H,0(g) = COy(g) + Hy (g)

occurs in addition, but it is considerably more complicated to take

this subsequent reaction into account.)

SOLUTION
(Pog / PV (Py /P°) 0 0
; ;
ko = Ee
(a an )
2
Oxy x* = 2.52 - 5.04x
Ke ot 5)04x5 — 2.02) —..0

P
Ss OAV 040
; cA = 0.458 = Poo = ‘Hy
 $7

P
I
R N al Il 0.084 = ——
+
P
a")H,0 i} 0.084 bar Poo = 0.458 bar ie = 0.458 bar

D6 An evacuated tube containing 5.96 x 10° mol L-! of solid iodine is

heated to 973 K. The experimentally determined pressure is 0.496
[M. L. Perlman and G. K. Rollefson, J. Chem. Phys., 9, 362 (1941)].
Assuming perfect-gas behavior, calculate Kp for In(g) = 21(g).

SOLUTION
P =——Vv RT

0.496 bar = (1 4°a)(5.96-2-107°. L*)(.08314 Lebar K mol“) (973 K)

0.496 bar
4 SO a as 1

(5-96: < 10° °0ms101) +) (,08314 Laban --K~*;mols) (9734K)

= 0.0287
402 (P/P°)
re ee ee 4(0.0287)2(0.496)
ee Ne eee 10 -3
1 - a2 1 - 0.02872
At 55 °C and 1 bar the average molar mass of partially dissociated
N,0, is 61.2 g molt. Calculate (a) a and (b) K for the
reaction Ny0,(g) = 2NO,(g). (c) Calculate a at 55 °C if the total
pressure is reduced to 0.1 bar.

SOLUTION
(a) es nie 2 9250-01222 ray:
et an My 2 61.2
i

(Sten. = 4H 2 ee p De Ue y)
eee
Ly — 1G; 1. 0,503
(c) a
oe
K 1.36

1 =<¢ 4(P/P°) 4(0.1)

a = 0.879

A liter reaction vessel containing 0.233 mol of Ny and 0.341 of

PC1; is heated to 250 °C. The total pressure at equilibrium is

29.33 bar. Assuming that all the gases are ideal, calculate K for

the only reaction that occurs.

PCi5(g) = PC13(g) + Clo (g)

SOLUTION
ee Vine (29.33 bar) 1) es
Et ok ete ae ee = 0.674 mol
(0.08314 L bar K- mol +) (523.15 K)

Moles of reactants = 0.674 - 0.233 = 0.441 = (0.341 - x) + 2x

x = moles of PC13 = moles of Cl, = 0.100

0 0 2
(P pci,/ P )(P C1, J” ) | a)
(G35 (29.33)
2
K = = =" 81!
0 oe)
Peci/” (0-20 (29.33)

What are the percentage dissociations of H)(g), O9(g), and In(g) at

2000 K and a total pressure of 1 bar?

SOLUTION
Hy(g) = 2H(g)

AG? = 2(106,653 J mol~2)

= -RT In K
= -(8.31441 J K-) mo1~!)(2000 K) in K

K WED CoO far

 59

1/2
a" 2 (: a ; a (2:82 x a) = 0.000819 or 0.0819%
P

0,(g) = 20(g) j

AG? = +2(121,448 J moi)

K = 4.53 x 10°! a 0.0337%

I,(g) = 21(g)

AG2T 7S 2 (29,637 J mol)

K =" 35432 a 94.8%

5.10 Hydrogen is produced on a large scale from methane. Calculate the

equilibrium constant K for the production of By from CH, at 1000 K

using the reaction CH,(g) + H,0(g) = CO(g) + 3Hy(g).

SOLUTION
AG° = -200.297 - 19.460 + 192.576 = -27.181 kJ mo1 1

= -(8.31441 x 107 kJ K-! moi~1)(1000 K) 1n K

K =ie263

Sead From the A,G° of Bro(g) at 25 °C, calculate the vapor pressure of
Bry(1). The pure liquid at 1 bar and 25 °C is taken as the
standard state.

SOLUTION
0
Br, (1) Br, (g) K = pr /?

0 x - 0
AG = RT in Bareih? )

P
ED 311007) sodas
Ee aa ead a ena eras Came | ,
P (8.314 J K mol ~)(298.15 K)
60

P = 0.258 bar
Br,

12 In order to produce more hydrogen from "synthesis gas'’ (CO + H,)

the water gas shift reaction is used.

CO(g) + H,O0(g) = CO(g) + Hy(g)
Calculate K at 1000 K and the equilibrium extent of reaction

starting with an equimolar mixture of CO and H,0.

SOLUTION
AG? = -395,924 — (-200,297) - (-192,576) = -3051 J mo1 1
= (8.314 J K+ moi !)(1000 K) in K
SH,ACO, 2
K = 1.44 = ery oe a
co H,0 (1 Ssx)

x = 0.545, fractional conversion of reactants to products

(Note that this reaction is exothermic so that there will be a
larger extent of reaction at lower temperatures. In practice
this reaction is usually carried out at about 700 K.)

ale Acetic acid is produced on a large scale by the carbonylation of

methanol at about 500 K and 25 bar using a rhodium catalyst. What

is Ky under these conditions? (A,G° for acetic acid gas at 500 K
is -335.28 kJ mol.)

SOLUTION
CO(g) + CHj0H(g) = CH3CO,H(g)
AG? “= <335-98 + 155-68 02193552) 046-001 EIo Role
VA ALY
Kos 1639. 100 = AA a2
*CO*CH 0H
 61

YAA 6
R= sp = G39 104) (25) 1.60 x 10
%CO*CH,0H

5.14 Calculate the degree of dissociation of H,0(g) into H,(g) and 0,(g)
at 2000 K and 1 bar. (Since the degree of dissociation is small,
the calculation may be simplified by assuming that Py Sec 1 bar.)
i

al
H,0(g) = H, (g) + z 0, (8)

AG? = 1347456 J soi.

= -(8.3144 J K+ mo1~+)(2000 K) in K
K = 3.079 x 10-4

(Pa,/* }(F0,/* }*

P,
(ia P, 1/2 P, 3/2
2 2 OE i 2
p° 2P° a et po

Py
+ - (v2 x)2/3 = 0.0058
P

Sede At 500 K CH30H, CH, and other hydrocarbons can be formed from CO

and H,. Until recently the main source of the CO mixture for the

synthesis of CH,0H was methane.

CH, (g) + H,0(g) = CO(g) + 3H, (g)
When coal is used as the source, the "synthesis gas” has a

different composition.
62

C(graphite) + H,O(g) = CO(g) + Hy(g)

Suppose we have a catalyst that catalyzes only the formation of

CH30H. (a) What pressure is required to convert 25% of the CO to

CH,0H at 500 K if the "synthesis gas’ comes from CH,? (b) If the
synthesis gas comes from coal?

SOLUTION
(a) CO +//2H, = CH,0H
Initial 1 3 0
Equil. fe 3-2 E Total = 4-2€

y
Pet Pabedan
2 2
toot ae
ay)

AG? = =133252 — (-155.68). 822 t16nk) aoto

Kies 418405 100
5 1/2
rere (4-24)
Kp (1-&) (3-26)
; 1/2
7 OHS) : me
4.842 x 10 -(0.75) (2.5)
(b) CO 4 2H) 80 -9 cH,on
Initial 1 1 0
Equil. ikea Va 2e E Total = 2-2€

K E( 2-2 2) p = |_(0. S05)

0.2 e 29 sores
(1-21-20) K(0.75) (0.5)
5.16 Show that in going from a standard-state pressure of 1 atm to 1
bar, thermodynamic quantities for reactions are corrected as
follows:
 63

ACp° (bar) = ACp° (atm)

AH°(bar) = AH° (atm)
AS°(bar) = AS(atm) + (0.109 J K+ moi?) 34),
AG°(bar) = AG°(atm) - (0.109 x 10°? kJ Kt mot 4)TI0,
K (bar) = K(atm)(1.013 25)2%i
where IV; is the difference between the stoichiometric co-
efficients of gaseous products and gaseous reactants in the
balanced chemical equation.

SOLUTION
For perfect gases the enthalpy and heat capacity are independent

of pressure, and so the choice of standard state does not affect

AH® or ACp for a reaction.

As explained in connection with equation 3.75 the entropy
decreases when a perfect gas is compressed from 1 bar to 1 atm.
AS® = -R In (101325 Pa/10° Pa) = -0.109 J K+ moi}
To apply this to a chemical reaction consider

A (1 atm) + B (1 atm) I C (1 atm)

A (1 bar) + | (1 bar) i C (1 bar)

AS° (bar) = -0.109 - 0.109 + AS°® (atm) + 0.109

= AS° (atm) - 0.109 J K? moi
Since eT = -1, we can generalize this to the expression given

above.
The expression for AG° (bar) can be derived from
AG° (bar) = AH®° (bar) - TAS® (bar)
but let us derive the expression for K first and use it.
vi Vi
K (bar) = nm{[P;/(1 bar) ] and K (atm) = n{P5/(1 atm]
i i
64

a7 =e sv
K (bar) (1 atm) a (1 atm) = 1.01325 i
K (atm) (1 bar) (1 bar) "

0 i
AG (bar) = -RT In n{P,/(1 bar) ]
i

Ue
= -RT ln n{P;/(1 atm)]
Vi [(1 atm)/(1 bar)]
i
baa.
1
= -RT In K(atm) = RT In 1.01325

= AG° (atm) - (0.109 x 10°? kJ K} mol })T3V,

Seka Calculate the total pressure that must be applied to a mixture of

three parts of hydrogen and one part nitrogen to give a mixture

0
containing 10% ammonia at equilibrium at 400 °c. At 400 Cc,
Ki= 1.60 <2107'Mfor theerenetion Ny (g) + 3H, (g) = 2NH3 (g).

SOLUTION
0.2
Ory )
K = - — =1.60x 107% OR
(P
4/2, P )C
/ P=)

2)
NH
Kee he 1960 1 0n aber
PP :
No Hy

, (0.1P)7 _ _¢0.01)44
(= 0.9P)( 0.9P)> 390.9) Pp?
P = 30.1 bar

meeiss In the synthesis of methanol by CO(g) + 2H, (g) = CH,0H(g) at 500 K,

calculate the total pressure required for a 90% conversion to
 65

methanol if CO and H, are initially in a 1:2 ratio. Given:

K = 6.09 x 10°.
>

SOLUTION
initial moles al 2 0
equil. moles 0.1 OZ 0.9 Totals

Bre: (0.9) (1.2)?

P (0.1) (0.04) (6.09 x 10

P = 231 bar = total pressure for 90% conversion to CH,0H

Doto At 1273 K and at a total pressure of 30.4 bar the equilibrium in

the reaction CO,(g) + C(s) = 2CO(g) is such that 17 mole % of the
gas is CO, . (a) What percentage would be CO, if the total pressure

were 20.3 bar? (b) What would be the effect on the equilibrium of
adding Ny to the reaction mixture in a closed vessel until the
partial pressure of N, is 10 bar? (c) At what pressure of the
reactants will 25% of the gas be CO,?

SOLUTON
Ca) »P = (30.4 bar)(0.17) = 5.2 bar
co,

P = (3054 bar) (0.835) = 2552 bar

co
66

Zz
K
SOS
= 5.2 = 122

Let x = mole fraction CO,

= [2055(1 Sex) 2 x oy
K =) = Ages
ta ee 122 x 0.127

Percentage CO, at equilibrium = 12.7%

(b) No effect for perfect gases because the partial pressures of

the reactants are not affected.

(c) K
[0.75(P/P°)17 = 622
0.25(P/P°)
ae) 54 bar

5.20 At 2000 °C water is 2% dissociated into oxygen and hydrogen at a

total pressure of 1 bar.
i!
(a) Calculate K for H, 0(g) = H, (g) + z 0, (8)

(b) Will the degree of dissociation increase or decrease if the

pressure is reduced? (c) Will the degree of dissociation increase
or decrease if argon gas is added, holding the total pressure equal
to 1 bar? (d) Will the degree of dissociation change if the
pressure is raised by addition of argon at constant volume to the

closed system containing partially dissociated water vapor?

(e) Will the degree of dissociation increase or decrease if oxygen

gas is added while holding the total pressure constant at 1 bar?

SOLUTION 1
(a) H,O(g) = H, (g) + x (8)

Initially 1 0 0
Equilibrium 1-é E £/2 Total = 1 + &/2

eel Ses 2: aCe Pe 2662

 67

rt. ghrp yy”

4 [1 EN a =)
1/2

3/2 1/2
ee ee a eo 05 fe LOTS
¥2 (1.01)1/? (0.98)
(b) If the total pressure is reduced, the degree of dissociation
will increase because the reaction will produce more molecules to
fill the volume.

(c) If argon is added at constant pressure, the degree of

dissociation will increase because the partial pressure due to the
reactants will decrease.

(d) If argon is added at constant volume, the degree of

dissociation will not be changed because the partial pressure due
to the reactants will not change.

If oxygen is added at constant total pressure, the degree of

dissociation of H,O will decrease because the reaction will be
pushed to the left.

Bis 2k At-250. C PC1s is 80% dissociated at a pressure of 1.013 bar, and

so K = 1.80. What is the percentage dissociation at equilibrium

after sufficient nitrogen has been added at constant pressure to

produce a nitrogen partial pressure of 0.9 bar? The total pressure

is maintained at 1 bar.

SOLUTION 2
K 0.8 (4.073) 1.80

1 - 0.8

K Pari:
a 9
1

a i} 0.973 or 97.3% dissociated.

68

5.22 The following data apply to the reaction Bro(g) = 2Br(g)

T/K i923 BLT 1223 1273
K/2002 0.408 1.42 3.32 ee
Determine by graphical means the enthalpy change when 1 mol of Bry

dissociates completely at 1200 K.

SOLUTION

0.75 0.80 Ogs 0.90

107
At T 1200 K (1/T = 0.833 x 10-2) the slope is -10.4 x 10° K
AH® = -2.303 R (slope)

= (2.303)(8.314 J K+ mo1~1)(10.4 x 103 x)

= 199.2 kJ moi
 69

5.23 The vapor pressure of water above mixtures of CuC1, +H,O0(cr) and

CuC1,°2H,O(cr) is given as a function of temperature in the

following table.

t/sC 17.9 39.8 60.0 80.0

P/bar 0.0049 0.0250 0.122 0.327
(a) Calculate AH°® for the reaction
CuC1,°2H,O(cr) = CuC1,°H,O(cr) + H,0(g)
(b) Calculate AG° for the reaction at 60 °C.
(c) Calculate AS° for the reaction at 60 °C.

SOLUTION
0

log K
=f.

25 30 35
3
l0/T
(a) K = Pio slope = -3060 K
2
Ano se) 25503 Rl slope) = 57.3-k) mol+

(b) AG? = -RT in K = (8.314) (333 K) 1n 0.122 = 5.82 kJ mol+

(ey AS? = AHS AGS Te 15407. 5-K mol

70

5.24 The following reaction is nonspontaneous at room temperature and

endothermic.

3C(graphite) + 2H,0(g) = CH4(g) + 2C0(g)

As the temperature is raised, the equilibrium constant will become
equal to unity at some point. Estimate this temperature using data
from Table A.2.

SOLUTION
At 1000 K
AG° = 19.460 + 2(-200.297) - 2(-192.576) = 4.018 kJ mol*
= -(8.314 x 109 kJ K-? moi !)(1000 K) 1n Kp
KS) 05617
AH® = -89.881 + 2(-112.010) - 2(-247.885) = 181.869 kJ mol+
K 0

Fee Ke etal
oR
let
(Ea Te

in 1 = _181,869 J mol -1 ( Lameies =)

0.617 ete els Or

1h @ a= SS
2 ilacs bap Bae Aly peeae ed
1000 K 181,869 ~" 0.617
aie 25 The measured density of an equilibrium mixture of Ny04 and NO, at
15 °C and 1.013 bar is 3.62 g L™, and the density at 75 °C and
1.013 bar is 1.84 g Lt, What is the enthalpy change of the
reaction Nj0,(g) = 2NO,(g)?

SOLUTION
At 15 °C
_ Rg (0.08314) (288) (3.62)
M = a Bir cae 85.57 g mol =f
 ys

M M
a
eeeMi,
2 eTitehe gerg7
OUI ten nT oe=—5 020753

K =
4a” P _
see
4(0.0753)7(1.013)
WE Fiieged St tity We = 0.0231
aS" ei = Wy Sys)

ACLTS TSC
M
_= (0.08314)
—
(348) (1.84)
{bie BA SIS) g mol
~1

pe
=)
9201 952.55).
TST
CT Tae 0.751 K =
Z 5.24

hee sa byeKy (8.314) (288) (348) es

Clot.) K 60 0231
2 1 il!

= 75 J mol?
5.26 (a) A mixture of one mole of hydrogen and one mole of nitrogen
reacts to form ammonia at equilibrium at 500 K and 1 bar. The

equilibrium extent of reaction is 0.0599. What is the effect of

adding a small amount of nitrogen at constant pressure, as

expressed by d&/an,°? (b) A mixture of one mole of hydrogen and

1.2 mole of nitrogen reacts to form ammonia at equilibrium at 500 K
and 1 bar. The equilibrium extent of reaction is 0.0597. What is

the effect of adding a small amount of nitrogen at constant

pressure, as expressed by a€/an,°?

SOLUTION
(a) For the reaction 3H,(g) + No(g) = 2NH3(g), the numerator of
equation 5.83 is equal to zero.

v a
v Lo: GE Oe eT,
n n5 (Ya 1-€

Thus the addition of a small amount of nitrogen at constant

72

pressure and temperature does not change the extent of

reaction. The volume will of course increase slightly. Note
that the mole fraction of nitrogen in the equilibrium mixture
ig? (11 =2€)/ (29-326) 430.5.

(b) The numerator of equation 5.83 is negative.

v Zee -2 1
ny, Spann | eae

= 1
+ 2 = 2110597) | aso ee ese
Thus adding a small amount of nitrogen at constant pressure
and temperature causes some ammonia to dissociate. This
effect can also be seen in the extents of reaction given
above. If the nitrogen addition is continued, the NH, will
completely dissociate at equilibrium. This effect is not
obtained when hydrogen is added to the equilibrium mixture at
constant pressure and temperature.

5.27 The preceding problem shows that under certain conditions the

addition of No to the No, Hy, NH3 equilibrium causes NH3 to

dissociate. (a) Why doesn't this happen with Ho? (b) Is NH3
present in the limit of indefinitely large additions of hydrogen?
(c) Nitrogen?

This doesn’t happen to Ho because its stoichiometric

coefficient is larger than that of No. Even when the ratio of

hydrogen to nitrogen goes to infinity, there will still be
some NHz if there is some Nj. As Ny, is added, however, all
NH, dissociates in the limit. These same considerations apply
to any gas reaction for which the reactants have different
stoichiometric coefficients.
 73

5.28 Mercuric oxide dissociates according to the reaction

2HgO(cr) = 2Hg(g) + 0,(g). At 420 °C the dissociation pressure is
5.16 x 10* Pa, and at 450 °C it is 10.8 x 104 Pa. Calculate (a)
the equilibrium constants, and (b) the enthalpy of dissociation per
mole of HgO.

SOLUTION
(i)0 P Be = 2, Po, Bie =
2=P
a Ps = _
1zP
2
2
‘ 2 eae (2 a 3
R420 rile "05 . (3) (3 ‘3
i i ( oe 4 = 3
et aaah
1.013 x 10° Pa
4 3
Kyso 7 ea 108 ax408 2 Baty Ag g
1.013 x 10° Pa
RT_T K
(bo) aH? = gS in
Bert) 1
_ (8.314 J K* mot?) (693 K)(723 K) | 0.1794
s 30 K ™ 0.0196
= 308 kJ mol + for the reaction as written
154 kJ mol + of HgO(cr)
5.29 Calculate (a) K and (b) AG° for the following reaction at 20 PC.
CuSO, + 4NH3 (cr) = CuSO4:2NH3(cr) + 2NH3 (g)
The equilibrium pressure of NH, is 8.27 kPa.

“ 2
sia 8270 Pa 2 23
(a) K = (Px, /? = (se - 6.66 x 10 -3
74

(b) AG® = -RT 1n kK

= -(8.314 1 kK) mol-4) (293.15 K) in 6.66 x 10°
= 9241 er more
5.30 The decomposition of silver oxide is represented by

2AgoO(cr) = 4Ag(cr) + Op (g)

Using data from Table A.1 and assuming ACp° = 0 calculate the
temperature at which the equilibrium pressure of O, is 0.2 bar.
This temperature is of interest because Ag,0 will decompose to
yield Ag at temperatures above this value if it is in contact with

air.

SOLUTION
AU? =e 231505) RetROQIALO) oT amta
AS® =. 4(42.55) 205.1362 20120 ek =) 132.7 0 Ko) mol
AG = AG° + RT In P
02

) = AH° — TAS® + RT In 0.2

ANG Meee DGAS- OR lnc 0.2)

emer AH® a 62,100 J moi}

ASSL OR tn 1012 (932 a= 8.304 Wn 082) K mol
= 425k
The dissociation of ammonium carbamate takes place according to the
reaction

(NH, )CO(ONH, ) (cr) = 2NH3 (g) * CO, (g)

When an excess of ammonium carbamate is placed in a previously
evacuated vessel, the partial pressure generated by NH, is twice
the partial pressure of the CO,, and the partial pressure of
(NH, ) CO(ONH, ) is negligible in comparison. Show that
 75

2
"xa, \ [Pco, een
K = ; 3 SEONG ire where P is the total pressure.
P P P

SOLUTION
P = P ar Le = 3P since P =2P
NE, co, co, NB, co,

Poo = P/3 PAH = =P

2, 3
2
P P
Bae Ee a Ne Z il ie 4 P
Shae Sx 1E
25 P
a4] F ntl Seagek
Pp
Pol!Sine
P
dt Gav DIA we
P

5.32 At 1000 K methane at 1 bar is in the presence of hydrogen. In the

presence of a sufficiently high partial pressure of hydrogen,

methane does not decompose to form graphite and hydrogen. What is

this partial pressure?

SOLUTION
CHy(g) = C(graphite) + 2H, (g)

AG? =. RD iuukie=. 10146 1 mot ¢

K 69s
Hy af)?P
CH,
the

Lp ~ P°[(10.39) (1) 12/2 = 3.2 bar

2

5.33 A gaseous system contains CO, CO,, Hy, H,0, and C6He in chemical

equilibrium. How many components are there? How many independent

reactions? How many degrees of freedom are there?

76

SOLUTION
co CO, Hy H,0 Cee

C 1 gs 0 0 6
0 i 2 0 1 0
H 0 0 2 2 6

Subtract the first row from the second and divide the third
row by 2 to obtain

1 1 0 0 6
0 1 0 1 -6
0 0 1 1 3

Subtract the second row from the first

1 0 0 -1 12
0 1 0 5k -6
0 0 1 al 3

The rank of this matrix is 3, and so there are 3 independent

components. The stoichiometric coefficients of 2 independent
reactions are given by the last 2 columns.

co, + Hy = H,0 + CO

If the species are arranged in a different order in the

matrix, a different pair of independent equations will be
obtained.

Pete fer ip raz

If the numbers of moles of 3 components and the temperature

are specified, the system is completely determined; that is,
the numbers of moles of the other two species and the pressure
can be calculated--given values of the equilibrium constant.
Alternatively, the mole fractions of 2 species and _ the
temperature and pressure may be specified. We then have two
mathematical expressions between 5 mole fractions, 4 of which
ae independent since 2Y; = 1. If 2 mole fractions are known,
 717

the other two can be calculated from the two simultaneous

equations.

5.34 Superheated steam is passed over coal, represented in these

calculations by graphite, at 1000 K to produce CO, CO,, Hy, and
CH,. Since there are 6 species and 3 element balance equations,
there are 3 independent chemical reactions which may be written as

follows:

3(graphite) + H,0(g) CO(g) + Hy(g)

3C(graphite) + 2H,0(g) CHy(g) + 2C0(g)
2C(graphite) + 2H,0(g) = CHy(g) + CO,(g)
What are the equilibrium constants for these reactions? If the

total pressure is raised to 100 bar, one of these reactions will

predominate. Neglecting the other two reactions, calculate the

equilibrium mole fractions of the gases present.

SOLUTION
Using Table A.2 the following equilibrium constants are calculated
for 1000 K

C(graphite) + H,O(g) = CO(g) + Hpy(g) K = 2.5

3C(graphite) + 2H,0(g) = CHy(g) + 2CO(g) K = 0.61

2C(graphite) + 2H,O(g) = CH4(g) + CO, (g) K = 0.35

At 100 bar the K.. values for these three reactions are 0.025,
0.0061, and 0.35, respectively. Thus the third reaction will
predominate.

"CH, "CO,
Se ea a eee 1 ed OC y
YHOO
2
= + =a
: Yoo” Hay TY cone teOle aa Yu,0 y
78

Substituting in K. and solving the quadratic equation for y yields

y
y
= 0.27, Yeo = Ome. Yao: ts 0.46.
CH, 2 Z

oe 35 Acetic acid and ethanol react to form ethyl acetate and water

according to
CH,CO,H(1) + C,H,OH(1) = CH3CO,CoHs (1) + H,O0(1)
Analytical data obtained by titrating the acetic acid remaining at

equilibrium at 298 K indicates that K = 40 when mole fractions are

used, and the solution is assumed to be ideal. The standard Gibbs

energies of formation of ethanol, acetic acid, and water are given

in Table A.1. Calculate the standard Gibbs energy of formation of

ethyl acetate.

SOLUTION
AG? -RT In K = -(8.314)(298) In 4.0 = -3.44 kJ mols
=
_—
AG 0
ae Ac _
228.9 4 + 389.9 + 174.078

A,G © Vek paic hs 339.6 kJ mol Al

ale 36 The equilibrium constant for the association of benzoic acid to a

dimer in dilute benzene solutions is as follows at 43.9 °C.

2C¢H5COOH ee
= (CgH5COCH) 5 K, 2= 2.7 x 10 22
Molar concentrations are used in expressing the equilibrium
constant. Calculate AG°, and state its meaning.

SOLUTION
AG? = -RBT in K, = -(8.314 3 K+ mo) (317.1 K) in (2.7 x 10?)
= -14.8 kJ moi
This is the decrease in Gibbs energy when 2 mol of
monomer at unit activity on the molar scale is converted
to 1 mol of dimer at unity activity on the molar scale.
 ye

DoT Amylene, C5Hi 9; and acetic acid react to give the ester according
to the reaction
CoHyQ(1) + CHZCOOH(1) = CH,CooC,H,,
(1)
What is the value of K. if 0.006 45 mol of amylene and 0.001 mol of
acetic acid, dissolved in a certain inert solvent to give a total

volume of 0.845 L, react to give 0.000 784 mol of ester? Use the
molar concentration scale.

SOLUTION
Ka (7.84 x 1074) /0.845
[((ce50s 10° — 7,84°x°10 3701845][10 x 10°" = 7084. x10 9) /0.645)
541
AS oye RR, Pe xy PY Xo Inixy * xg In -z5)

AG,iz = —TAS,i,

D392 ~4.73 kJ molt, 15.88 JK? moi?

5.40 AG) 17-2 &3 mol
3.41 0.696
1.87 x 104, ieeaex 1066) 90h TOs 0856410
As the pressure is increased, the gases behave more
imperfectly.

(a) 17.0 kJ mo1+ (b) 0.795 bar

(a) 9.63 g (b) 1.215, 0.032, 1.457 bar
x = 33/2;4K = 0.0164
0.351 bar
3.74 bar
5.48 (a) 2.48 (b) 0.54 mol
80

-49 —€ = 0.800 Kau=y 1380

.50 (a) 0.0788 (b) 0.0565
-o1 6.9
eo2 1.81 x 10-2
ahs} 2.99 x 10° 0.0273 0.0861
54 0.081 0.363
-o0 0.53
.56 (a) 1.20 x 102° 3.91 x 102
(vo) 8.25 x 102 0.352
ou 18.2 bar

58 (a) No (b) 0.285

59 (a) 5x 10° bar (b) 1.79% (c) 0.0221 bar

60 (ay t/°C 25 45 65
a 0.1852 0.3775 0.6284
K 0.1451 0.6737 2.644

(b) 60.7 kJ molt (c) 0.320 (d).0.371

-61 135°8)-C
.62 153 kJ mo14
-63 109405010722, bee

64 6.88 x 10°24 4.79 x 10°43

-65 452 kJ moi?
- 66 (a) 19.70 bar (b) 35.6 bar
 81

Da 67 (a) Nf 0.5000, 0.4363, and Yun. = 0.0637

No 2 8)

(b) Ws 0.5481, iH} 0.3946, and y = 0.0574

YN NH
2 2 3
Dissociation into atoms and solubility proportional to the
partial pressure of atoms.

Fe,0,

5.6 x 10> bar

2.66 x 10° bar

1-0 Dar

5.74 (a) 9.75 8 (pn 1907 Se6

Dold 3.31 x 102° bar of O, is required to oxidize Ni, but the
partial pressure of 0, from partially dissociation H,0 in the
presence of 3 mole percent hydrogen is only 9.7 x 10°18 bar.

5.76 3 components, 1 independent reaction, variance of 4. If C is

present, the answers are 3, 2, and 3.

5.77 16.06 &Jimol’=

CHAPTER 6: Phase Equilibrium: One-Component Systems and Ideal Solutions

yg! E What is the maximum number of phases that can be in equilibrium at

constant temperature and pressure in one-, two-, and three-

component systems?

SOLUTION
Rees ce peta

YS al oa
ae 5 a) =

Ona S25 pre 2h p =4

0) = 3" — p+ 25 =p =45

nz How many degrees of freedom are there for the following systems,

and how might they be chosen?

(a) CuSO, °5H,0(cr) in equilibrium with CuSO,(cr) and H,O(g).
(b) N,O, in equilibrium with NO, in the gas phase.
(c) CO, , Co, H,0O, and Hy in equilibrium in the gas phase.

(d) The system described in (c) is made up of specified amount of

CO and Hy.

SOLUTION
(ad) oC 2s" =n = 3 S01 a2
J 9S Coase ee = PS saa eS il
Only the temperature or pressure may be fixed.

(Cb) co @ (sa) 272 = =a

eS ee yar 7A ee Lk ee
Temperature and pressure may be fixed.

(ce) 6 = 4=1 = 3
Roe “era per 2 = 3 ea = A
Temperature, pressure, and two mole fractions may be fixed.
 83

(d)OgCIk=Tts sore=smncs Al> tes 2yyevad

|SE ay ice 2 iG. ee7 ee A ee ee ee
Only temperature and pressure may be fixed if the elemental
composition is fixed.

o.3 How many degrees of freedom do the following systems have?

(a) NH,Cl(cr) is allowed to dissociate to NH3(g) and HC1(g) until
equilibrium is reached.

(b) A solution of alcohol in equilibrium with its vapor.

SOLUTION
(a) NH,Cl(cr) = NH,(g) + HC1(g)

oo ase Pee ok ee ae Pd eh 1

The additional constraint is that only equal numbers of moles

of NH3z and HC1 can be formed.

es Ge hse BS GL a De SG,
Only temperature or pressure may be fixed.

Cho EF =. os pit? i= a = 2 = 2
Temperature and pressure may be fixed.

6.4 Ice has the unusual property of a melting point that is lowered by

increasing pressure. Thus, one can skate on ice provided that the
pressure exerted by one’s skates is great enough to liquefy the ice

under them. Would a 75-kg skater whose skates contact the ice with
Zz,
an area of 0.1 cm” be able to skate at -—3 oC?

SOLUTION
Bacnibvenplien6eai WAT. =ac(io5 1icl0y- ck: bara )AP

AT = -(1.5 x 107? K bar 4)(75 kg) (9.80 m s ”)

(0.1 cm2)(1072 m cm 4)2(10° Pa bar“)
-5.51 °C so the answer is yes.
84
6.5 The change in Gibbs energy for the conversion of aragonite to

calcite at 25 °C is -1046 J mola. The density of aragonite is

293 ¢ cm > at 25 °C and the density of calcite is 2.71 g ono s, wae

what pressure at 25 °C would these two forms of CaCO, be in

equilibrium?

SOLUTION
aragonite = calcite AG° = -1046 J mol?

hy eed 100209. mol+ — 100.09 g mol?

2.718 cm? 2al3s2g cm >

2.77 om? mol DF 1000 me mel

2 P
(338) SLAY, | diGe= | AVaP
T 1 1

AG, - AG; = AV(P - 1)

04.1046 J mol = (2.77% 10° m mol y(P - 1)
Po = des780 bar
6.6 n-Propyl alcohol has the following vapor pressures.

£/ 40 60 80 100
Poat/ kPa 6.69 19.6 50.1 112.3

Plot these data so as to obtain a nearly straight line, and

calculate (a) the heat of vaporization, and (b) the boiling point
at 1 bar.

log P is plotted versus 1/T

(Please see top of page 85)
 85

406

4.0

25
ee BE, oF
> Xd
AH
(ajikeelopeeme” =2534%7-107- kt ee
32303 (863149 Ke mole)
AH vap = 44.8 kJ mol

112.3 _ 44,800 1 1
(b) In 399° = 8.3144 T 373.15

ane. Pee see RSN ed 20888 OS) 24 7h S970

> Beet dd 119-3 it 7 : a ;
44,800)" 100 ~* 373.15
6.7 For uranium hexafluoride the vapor pressures (in Pa) for the solid
and liquid are given by
In P; = 29.411 - 5893.5/T
In Py = 22.254 - 3479.9/T
Calculate the temperature and pressure of the triple point.
86

SOLUTION
porate 12823:
T
58593 sg T
Te 33 1e2 K = 64.0 °C
pos ero Ail — $893 .5/337.2 152.2 kPa

If ACp = Cp val = Cp liq is independent of temperature, then

AH ap = AH, ,vap + TACp where AH, .vap is the hypothetical enthalpy

of vaporization at abolute zero. Since ACp is negative, AH ap

decreases as the temperature increases. Show that if the vapor is

a perfect gas, the vapor pressure is given as a function of

temperature by

~AH a AC
In P = Sst + >: In T + constant

SOLUTION
d inP ce O,vap WS es O,vap | nS
aT RT? RT” RT

Integrating

O,vap a
Tin) P = RT ee oF aon In T + constant

6.9 The heats of vaporization and of fusion of water are 2490 J Pe and
3393)..50 J) gt at 0 °C. The vapor pressure of water at 0 °C is 611

Pa. Calculate the sublimation pressure of ice at -15 “Cc; assuming

that the enthalpy changes are independent of temperature.

SOLUTION
AH =
sub i is oaap
liquid
ae = 333.5 + 2490
AH =4
vap = 2824 J ¢g
 87
Pp =
rr es if ae ee (T, T,)
Py RTT,

= (611) Pe.) exp Seen

(2824 Las
x 18 edJ amol i-)(-15 K) ee
(asl) AF Ax MOL el 7s KOC2
SSicilian Ko)

= 166 Pa

6.10 The vapor pressure of toluene is 8.00 kPa at 40.3 °C and 2.67 kPa
at 18.4 °C. Calculate (a) the heat of vaporization, and (b) the
vapor pressure at 25 rice

SOLUTION

Bees Pp
Ba
ae
RTT,

=f =4
ia _ (8.314 JK mol _)(291.6 K)(313.5 K) | 8.00
# aT 95K eh I
=< $8.1 kT mots
P af
2 (38,100 J mol )(6.6 K)
(b) In aya =1 =]
: (8.314 JK mol )(298.15 K) (291.6 K)
P, = 3.78 kPa

6.11 The sublimation pressures of solid Cly are 352 Pa at -112 °C and 35

Pa at. -126.5 °C... The vapor pressures of liquid Cl, are 1590 Pa at

-110 °C and 7830 Pa at -80 t?)

°C. Calculate (a) AH abe (a
(c) AHp,5, and (d) the triple point.
88

_ (8.314 J K7 moi?) (161.15 K) (146.65 K) | 352

Zz 145°K 35
¥= 31.4 kJ mol =4

fy Shey fe Lee DR el 5173) T199215 7820

Be apne 20 K 1590
BPS Bie OR:

(c)) Ais fus ee BARN. sub4 )= An vap = G14, P20, =u oesc Ie mo ls

(d) For the solid

In P = In 352 fe
31,400
8.314 (sas
1 1
z]
_= 29.300
shit
ery ie

For the liquid

In P = In 1590 +
22,100
2230 (a
f Beri-| ¥= Deo S
2658ae
mg

At the triple point

29.300 ST.
See _ ee
2658 TarEee
ge, = LTO Re

T “= 10703 K=)273,15 K =; 2103-0 °C

6.12 The boiling point of n-hexane at 1 bar is 68.6 °C. Estimate (a) its
molar heat of vaporization, and (b) its vapor pressure at 60 °C.

SOLUTION
(a) AHyg) = (88 I K+ mol*)(69 + 273)K = 30.1 kJ moi}
gaeecae
P, (2 Z 7
2Bears i

jideban 2301009 mol ( ick Catan =|

P S51 7 ee oie socal aee
P= 03S S5abar
 89

6.13 According to Trouton's rule the entropy of vaporization of a liquid

at its boiling point is 88 J K-1 moi. What is the change in
boiling point expected for a liquid with a boiling point of (a)
100 °C and (b) 200 °C at 101,325 Pa in going to a reference state
ofely bar?

SOLUTION
(a) AH) = (88 J Ko) mol*)(373 K) = 32,800 J moi”?
se P, c Mee ne l
Pe RTT,

10
5 325800 {T,2: — 1.)
it 0
lb = Tt. <a ns =0.46. °C
ag ets (8.314) (373)? aN ee
(b) AH, = (883 kK? moi!) (473 K) = 41,600 J moi?
ee ee Ess 4473) 10 oY eee
2 Ee 41,600 ™ 101,325 :

6.14 Calculate AG° for H,O(g, 25 Ch = H,O(1, 25 °C). The vapor

pressure of water at 25 °C is 3168 Pa.

SOLUTION

H,0(g, 101325 Pa, 25 °C) = H,0(g, 3168 Pa, 25 RC) =-H0(1; 025 ©©)
Since AG Ul 0 for the last step

AG = RT 1n(P,/P,) i] (8.314) (298.15) In (3168/101325)

=§,59 kT mole

6.15 From tables giving AG”, AH,” and Cp for H,0(1) and H,O(g) at

298 K, calculate (a) the vapor pressure of H,0(1) at 25 °c, and

(b) the boiling point at 1 atm.
90

SOLUTION
(a) H,0(1) = H,0(g)
AG? = £228,572 - (-237.129) = 86557 kJ mol2
AG° = -RT In (P/P°)
eT
p/P° = exp Ohh Sh
permet TE eee 3.168 x 1072
(8.314 J K~2 mo1~1) (298.15 K)
=> 5
Piles U34068% 10-1072 Pa) bee 300 7hxO 3 Pa
(b) AH? (298.15 K) = -241.818 - (-285.830) = 44.012 kJ moi}
In the absence of data on the dependence of Cp on T we will
calculate AH°(T) from
T
AH°(T) = 44,012 + (33.577 — 75.291)dT
273.15

= 44.012 - 41.714 (T - 273.15)

8 (AG°/T) J © ABCD)
ar 12

AG -44,012 41.714 (40114) (2957015)

Sinn ae So a ee Sr aaa
T 1 T

Ee Ce Cy
. T

where I is an integration constant which can be evaluated

from AG° (298.15 K).
8590 _ 44.012 (41.714) (298.15)
298.15 Dotgis tka ge oo ae ($98.15) ooo
ee ll -398.191

At the boiling point AG° = 0 and so we need to solve the

following equation by successive approximations.
 91

0 = Set 4 an.7ig ant + SSEATEA) 298-45) _ 596 191

Trying T = 373 K RHS = 0.163
Trying T = 374 K RHS = -0.130
Therefore the standard boiling point calculated in this way is
close to 373.5 K.

6.16 Calculate the partial molar volume of zine chloride in 1-molal

ZnCl, solution using the following data.

% by weight of
ZnCl, Z 6 10 14 18 20

Density/g cm > 1.0167 1.0532 1.0891 1.1275 1.1665 1.1866

EE EY,
Taking the first solution as an example, 1 g of solution contains
0.02 g of ZnCl, (M = 136.28 g mol+) and 0.98 g of H,0. The weight
of solution containing 1000 g of water is
1000
0.98
1020 ¢g

molality ZnCl,
(0.02) (1020 g) = 0.1497 m
136.28 g mol

Volume of solution containing 1000 g of H,0

See 2 1003 .2 com?

1.0167 g cm >

Volume Containing
Wt % Molality 1000 g of H,0
2 0.1497 m 1003 .2
6 0.4683 1010.1
10 0.8152 1020.2
14 1.194 1031.3
18 1.610 1045.5
20 1.834 1053 .4
92

1060

1OYO
Vie?
102.0

1000 | ar ee
0 | 2
m—
The slope of this plot at m= 1 molar is 29.3 cm
3 mo1 + and so this
is the partial molar volume of ZnCl,.

Cra For a solution of ethanol and water at 20 °C which has a mole

fraction of ethanol of 0.2, the partial molar volume of water is
17.9 cm> mol! and the partial molar volume of ethanol is 55.0 cm?
mo1?, What volumes of pure ethanol and water are required to make

a liter of this solution? At 20 °C the density of ethanol is

0.789 g cm? and the density of water is 0.998 g cm>,

SOLUTION
Component 1 is water, and component 2 is ethanol.

V = nyVy +t nyV> = 4n5Vy ar nyV> = no (4V, ts Vo )

1000 cm> = ny {(4) (17.9 em? moist) 4°55 00cm: mol~2]

n= 7.90 mol =
8
46.07 g mole
It 363.9 g
 93

Volume of pure ethanol = pise ar 461 cm :

0.789 g cm

ay = 4n, = 31.60 =
al
18.016 81 = 569.3 g

Volume of pure water = popes acy 570 cm 3

0.998 g cm
6.18 Use the Gibbs-Duhem equation to show that if one component of a

binary liquid solution follows Raoult'’s law, the other component

will too.

SOLUTION
xydu, + Xodup = 0

Tf.) = vy + BT ints,
du, = zt

x
sf RT
dp, =3 his. x5 dx,

Since X41 a x9 = di, dx5 = ~dx4

RT ye
dp, = = oni? = RT dI1n X»

Hy = CONS tate tae Lt Xy

0
If Xp ict iby const = Wy

Weal ey PoeRE in x,

b.19 Show that the effect of external hydrostatic pressure P on the

vapor pressure p of a liquid of partial molar volume Vi is given by

94

Rr “ at
provided the vapor behaves as a perfect gas. Hint: When the

pressure is changed at constant temperature, dG, = dG ap’ so that

V,daP = VeasdP- Integrate this equation to find an expression for

the vapor pressure p of the liquid at some higher applied pressure

P in terms of the vapor pressure p’.

SOLUTION
The vapor pressure is represented by a lower case p.

Vv Vv.
Gp. cay moles _lop dp _ 7 dinp
_ 7
dP OV ~ RT BP p soe Ree i
gas

p P

ul bak, V_dP
Pak RT 1
0 0
Pp Pp

Assuming the partial molar volume of the liquid is independent of

pressure,
Vantec)
leis cae p = p.
oO

exp [V (P - p°)/RT]
—

6.20 What is the difference in chemical potential of benzene (component

0
1) in toluene (component 2) at Xy = 0.5 and Xi = 0.1 at: 25: /CF
assuming ideal solutions?

SOLUTION
*

ae ey a Roe
Ap, = (8.314 J K1 mo1 1) (298 K) In ee

3988 J mol
 95

6.21 Ethanol and methanol form very nearly ideal solutions. The vapor
pressure of ethanol is 5.93 kPa, and that of methanol is 11.83 kPa,

at 20 °C. (a) Calculate the mole fraction of methanol and ethanol

in a solution obtained by mixing 100 g of each. (b) Calculate the
partial pressures and the total vapor pressure of the solution.

(c) Calculate the mole fraction of methanol in the vapor.

SOLUTION
7 100/146 7
(a) *c,HOH ~ 100/146 + 100/32 ~ 0.410
z 100/32 .
“cH,oH ~ 100/146 + 100/32 O20

(b) P =O
C,H,OH C,H,0H p°
© C,H,OH

= (0.410)(5930 Pa) = 2430 Pa

Pon OH 6OC®CH OH PCH OH

3 3 3
= (0.590)(11,830 Pa) = 6980 Pa
P = 2430 Pa + 6980 Pa = 9410 Pa
total

_ 6980 Pa _
Soy cH OH tyReOr Fa 9410 Pa 092! 4?
3

6.22 Ethylene dibromide and propylene dibromide form very nearly ideal

solutions. Plot the partial vapor pressure of ethylene dibromide

(psat = 22.9 kPa), the partial vapor pressure of propylene

dibromide (PS4t = 16.9 kPa), and the total vapor pressure of the
solution versus the mole fraction of ethylene dibromide at 80 CC.

(a) What will be the composition of the vapor in equilibrium with a

solution containing 0.75 mole fraction of ethylene dibromide? (b)

What will be the composition of the liquid phase in equilibrium

96

with ethylene dibromide-propylene dibromide vapor containing 0.50

mole fraction of each?

SOLUTION
(a)

O |
mole fraction ethylene dibromide

(0.75) (2259)
= ee ee 0.802
YEtBr, (0.75) (22.9) + (0.25) (16.9)

= (0.25) (16.9) -
[TTB ~ (0.75) (22.9) + (0.25) (16.9) OnA28

*EtBr,*?

(b) y. = 0.5 = =
EtBr, "Hepes, 72>? + (1 7 EB es agar

*EtBr, = 0.425

6.23 The vapor pressure of a solution containing 13 g of a nonvolatile

solute in 100 g of water at 28 °C is 3.6492 kPa. Calculate the
molar mass of the solute, assuming that the solution is ideal. The

vapor pressure of water at this temperature is 3.7417 kPa.

SOLUTION 0
e n
2 ales pom 741 weingcagie ae
2 ee ee 3741.7 = b0.024)
 97

wv = 0.0247 =
13/M
n <a n
2 (100718) + (13/m)
>

M = 92.4 g mol2

6.24 One mole of benzene (component 1) is mixed with two moles of

toluene (component 2). At 60 °C the vapor pressures of benzene and

toluene are 51.3 and 18.5 kPa, respectively. (a) As the pressure
is reduced at what pressure will boiling begin? (b) What will be

the composition of the first bubble of vapor?

SOLUTION
(a) P= P.SPts 4. (poet op eet)5,
me AS. SikPa ft, (5125 kPa sect8:5. kPa) (04333)

= 29.4 kPa

: psat

(b> fs Wie sat ; oe sat

P, + (P, P, )x,

a (075353)'(51.3) KRa)
18.5 kPa + (32.8 kPa)(0.333)

= 0.581 kPa

S25 The vapor pressures of benzene and toluene have the following

values in the temperature range between their boiling points at 1

bar:

t/°C 19.4 88 94 100 110.0

he /bax 1.000 1.285 1.526 1.801

Aes

pee ee setae 0.508 0.616 0.742 1.000

CoH,
98

(a) Calculate the compositions of the vapor and liquid phases at

each temperature and plot the boiling point diagram. (b) If a

solution containing 0.5 mole fraction benzene and 0.5 mole fraction

toluene is heated, at what temperature will the first bubble of

vapor appear and what will be its composition?

SOLUTION

(ay At “88 “c xnil.285) + (1 — x5) 0.508 = 1

Xp = 0.633

Yp = (0.633)(1.285)/1 = 0.814

At 94 °C xp(1.526) + (1 - xp) 0.616 = 1

xR = 0.422

Yp = (0.4222)(1.526)/1 = 0.644

At 100 °C xp(1.801) + (1 - xp) 0.742 = 1

XR = 0.244

Yp = (0.244)(1.801)/1 = 0.439

(b) Please see diagram at the top of page 99.

 99

1/0

100

90

t/*¢

80

75

Bubble point
100

6.26 The following table gives mole % acetic acid in aqueous solutions

and in the equilibrium vapor at the boiling point of the solution

at 1.013 bar.

0
B.P., C 118.1 a MicSe 107.5 104.4 102.1 100.0

Mole % of acetic acid

In liquid 100 90.0 70.0 50.0 30.0 0
In vapor 100 + SoS 37.4 18.5 0

Calculate the minimum number of theoretical plates for the column

required to produce an initial distillate of 28 mole % acetic acid

from a solution of 80 mole % acetic acid.

SOLUTION

IOO

On©

Vapor
Fercent
Mole
yr

O 50 JOO
Mole Fercént + Liguid

Since there are four steps, three theoretical plates are required
in the column. The distilling pot counts as one plate.
 101

6.27 If two liquids (1 and 2) are completely immiscible, the mixture

will boil when the sum of the two partial pressures exceeds the
applied pressure:
sat sat
P = PL + P,

In the vapor phase the ratio of the mole fractions of the two

components is equal to the ratio of their vapor pressures.

sat

isege tinny Stee)

ay 7) 85M,
where 8; and gy are the masses of components 1 and 2 in the vapor
phase, and M, and My are their molar masses. The boiling point of

the immiscible liquid system naphthalene-water is 98 °C under a

pressure of 97.7 kPa. The vapor pressure of water at 98 °C is 94.3

kPa. Calculate the weight percent of naphthalene in _ the

distillate.

SOLUTION 0

Be tp ON ATI Ogg A pe ee
85 Pp °M (94.3)(18) :
2 2

Weight percent naphthalene = 1-28 = 0.207 or 20.7%

6.28 Calculate the solubility of p-dibromobenzene in benzene at 20 °c

and 40 °C assuming ideal solutions are formed. The enthalpy of
fusion of p-dibromobenzene is 13.22 kJ mo1 1 at its melting point

(86.9 °C).

SOLUTION
At 20 °C in x, =
102

(13,220 J mol") (-66.9 K) _

(8.3143 kK mol’) (36001 K)(20302 KD
x» = On S05

rte str ye ea (13 220 3 nol-1 )(-46.9 K)

, . -46.

(8.314 JK mol ~)(360.1 K)(313.2 K)

x, = 0.546

Calculate the solubility of naphthalene at 25 °C in any solvent in

which it forms an ideal solution. The melting point of naphthalene

is 80 °C, and the heat of fusion is 19.29 kJ mol 2s The actual

measured solubility of naphthalene in benzene is x, = 0.296.

SOLUTION
fags > age cau OMe.
A On
: ~(19,290 J mol +)(353 K - 298 K)
eon ed
(8.314 J K | mol at+) (353 K) (298 K)
=f

x, = 0.297

6.30 If 68.4 g of sucrose (M = 342 g mol +) is dissolved in 1000 g of

water: (a) What is the vapor pressure at 20 °C? (b) What is the
freezing point? The vapor pressure of water at 20 °C is 2.3149
kPa.

SOLUTION
68.4
(a) xX, SOE
=68.4 AN1000
I et
= 3.59 x 10 -3
342° ~«S
 103

Pp ; ibs aarp 2.3149 - = P, me =

mainstand 02 2.3149 cae eve
ies

P, = 2.3149(1 - 3.59 x 107") = 9.3066-LPa

(b) AT, = Kym = 1.86(0.2) = -0.372
1 = ie =
0N3T Ie oO

6.31 The protein human plasma albumin has a molar mass of 69,000

g mo1 2 - Calculate the osmotic pressure of a solution of this

protein containing 2 g per 100 cm Sat. 25°C tn (a) pascals, and (b)
millimeters of water. The experiment is carried out using a salt

solution for solvent and a membrane permeable to salt.

SOLUTION
y= ORT _ (20 x 1079 kg £71) (103 L m3) (8.314 J Ko tmo1*) (298.15 KY
in 69 keemol
= 719 Pa
ne (So 719 Pa

CE (1 g Gm?) (10° ky g 1) (10% cm m1) (9.8 m sv)

= 7.34 x10 2 m = 73.4 mm of water

6.32 The following osmotic pressures were measured for solutions of a

sample of polyisobutylene in benzene at 25 aC;

c/10-2 g cm? 0.500 1.00 1.50 2.00

n/g cm2 0.505 1.03 1.58 2.15
Calculate the number average molar mass from the value of n/c

extrapolated to zero concentration of the polymer.

SOLUTION
rT |RTM ri ey
O|A
104

The ratio n/c is plotted versus c and extrapolated to c = 0.

c/g/100 cm? 0.50 1.0 1.50 2.00

m(100) /atm one
- 1028 - 0.0982 0.1002 0.1025 0.1046

l (9.60 x 10-2 atm cm? g 4+)(101325 Pa atm) x

a
e o|A
~~
o

(103 g kg 4) (10-2 m cm 1)3

= 9.73 Pa(mol m>)~4
(2) . Rr
. c=0 4 - 1
M = - RT . 8.314
‘é I K~ - mol “4 ~)(298 K) _ 255 "ke mol nS 1
(=| 9.73 Pa (mol ar) s
c
c=0

105

nw
II

ae
 105

6.33 A sample of polymer contains 0.50 mole fraction with molar mass
100,000 g mol and 0.50 mole fraction with molar mass 200,000 ¢
mo1-!, Calculate (a) M,, and (b) M,.

SOLUTION
nM,
(a) M = -=— = %3x.M. where x. is mole fraction of the ith
n in, deni i
component

= 5 5 Al
=O. a0) i+) Oso? £4105) 9-= 15075000 2 mol

Bn M,”
(b) Mi = a i
es
Dividing numerator and denominator by 2n;
2
Ba
ee Sel fie
Pe) 050
= Meee.
8) 0s 4 ur
08S)
ae = 167,000 g mol
-1
ed OFS (TOs eet TORGI( 2x) 10m)

6.34 Calculate the osmotic pressure of a 1 mol Lot sucrose solution in

water from the fact that at 30 °C the vapor pressure of the

solution is 4.1606 kPa. The vapor pressure of water at 30 °C is

4.2429 kPa. The density of pure water at this temperature (0.99564

g cm?) may be used to estimate Vi for a dilute solution. To do

this problem, Raoult's law is introduced into equation 6.88.

SOLUTION
Vit = -RT In xy
Substituting Raoult’s law Py, = x4P,°

1b Sees a In
‘| ie

Ee 3 -1 -1
vY,= poeta gam = «61810 cm mol 5 = 0.01810 L mol
0.99564 g cm~
106

(0.08314 L bar Kt mol +) (303.15 K) in 422429 kPa

A Ga 4.1606 kPa

27.3 bar

6.37 (ay 38281: (hye-16c6 «ec

6.38 4.9K

6.39 1.67 kPa

0.167 kPa

6.40 96 °C

6.41 (a) 2.82 kJ (b). 50.1 Pa, Kee (c) 360 Pa 387 Pa

6.42 (a) 1623 kPa (b) 1428 kPa

6.43 0.076 Pa
6.44 27.57 kJ mol
6.45 (a)o58-C) 53. 28skPa (b) 9.90 kJ molt
6.46 94 °C
6.47 0.79 cm? ie

6.48 (a) 0.204 cm? s- (b) 19.4 cm> mol

6.49 D601 en?

5.293 J K+ moi! -1577 J mol?
(a) x 0.653 x = 0.365
CHC1,

(b) 20.92 kPa

 107

(a) 3.1615 kPa (b) 3.1615 kPa

(c) 3.1557 kPa (d) 3.1615 kPa
(a) xp = 0.72 xp = 0.28 3.162 kPa
(b) xp = 0.537
6.54 0.194 24.67 kPa
(igs) AGS 5 = RT (x4 In x, + x9 In xy) + wx4x9

AS ice -R(xy In x, + xy In xy)

AH nix PA EES:

AVinix wa

(a) At -31.2 °C Dror ane = 0.560

At. -16.3 °C Leagan = 02196
(6) At. "-31.2 °C Saeopane wap Ooh
At -16.3 °C x nop eiete ap Meebo”
Gco7 xp = 0.240 yp = 0.434
6.58 562 g
On09. 0.108
6.60 Xin 0. BAA ore 7474 g/100 g of solution

6.61 ast C

6.62 12.7 kJ mol

6.63 122,000 g mol
6.64 1810 Pa
6.65 (a) 36,800 ¢ mol (b) 48,500 g mol
CHAPTER 7: Phase Equilibrium: Nonideal Solutions

7.1 For a solution of n-propanol and water, the following partial

pressures in kPa are measured at 25 °c. Draw a complete pressure-

composition diagram, including the total pressure. What is the

composition of the vapor in equilibrium with a solution containing

0.5 mole fraction of n-propanol?

P
*n-propanol Pa 0 Teaconenol *n-propanol Py 0 n-propanol
yD 2

0 3.168 0.00 0.600 2.65 2.07

0.020 3.13 0.67 0.800 1579 2) era
0.050 3.09 1.44 0.900 1.08 2.59
0.100 3.03 1.76 0.950 0.56 PIG |
0.200 2.91 1281 1.000 0.00 2.901
0.400 2.89 189

SOLUTION

P/KRa

x
N= propanol

1.95 kPa
x = ——— = (0.406
 109

toe Using the Henry law constants in Table 7.1, calculate the
percentage (by’ volume) of oxygen and nitrogen in air dissolved in
water at 25 °C. The air in equilibrium with the water at 1 bar
pressure may be considered to be 20% oxygen and 80% nitrogen by
volume.

SOLUTION

P
N B)
zs Fe = 2 a 0.80 x Pa a. 3% 10°°

2 N, 8.68 x 10 Pa

P
1) 5
% - = 2. = OFZ 0Fx a Pa aWaess -y 107°

22 0, 4.40 x 10 Pa

The percentage of oxygen in this dissolved air is given by

x
(0) —-4
2 x 100-= At = 33.0%
*o 2 *N 2 (4.55 + 9.22) x 10

The percentage of nitrogen is 100 - 33.0 = 67.0%

TS The following data on ethanol-chloroform solutions at 35 °C were

obtained by G. Scatchard and C. L. Raymond [J. Am. Chem. Soc., 60,
1278 (1938)]:

*EtOH, liq f Ont: oe: 0.6 0.8 1.0

*EtOH, vap 0.0000 0.1382 0.1864 0.2554 0.4246 1.0000

Total pres-—
sure, kPa 39.345 40.559 38.690 34.387 Za. so 13.703

Calculate the activity coefficients of both in these solutions

according to Convention I.
110

SOLUTION
Yetou
*EtOH Oe: YEtoH — psat
=F tOH EtOH

(0.1382) (40.559) 2 045

(O83). 13703)
(0.1864) (38.690) =o
*EtOH 0.4 YEtou (0.4) (13.703)

(0.2554) (34.287) .065

*BtOH 0.6 YEtOH (0.6) (13.703)

(0.4246) (25.357)
- 982
*EtOH O78 YEtOR (0.8) (13.703)

(1.000) (13.703)
.000
*FtOH el YEtOH (1.000) (13.703)

y P
cuc1,
s sat
CHC1, “CHC1,

(1) (39.345)
1 Y cHC1, (1) (39.345)

(0.8618) (40.559)
a
one Ycuc1 (0.8) (39.345)
3

(0.8136) (38.690)
eae YCHC1 -ao2
3 (0.6) (39.345)

0. (0.7446) (34.387)
: YCHC1 -627
3 (0.4) (39.345)

On? (0.5754) (25.357)

YCHC1 854
(0.2) (39.345)
 afta

7.4 Using the data of the following table, which gives vapor pressures

att 35:2) BC; calculate the activity coefficients of acetone and

chloroform at 35.2 °C, following Convention I, for mole fractions
of chloroform of 0.20, 0.40, 0.60, and 0.80.

*CHCI, 0 Om2 0.4 0.6 0.8 1.00

ois Ch cas 0 4.5 10.9 19.7 30.0 39.1

Pp /kPa 45.9 36.0 24.4 1376 5.6 O

acetone

SOLUTION

Component 1 is chloroform. Component 2 is acetone.

1D,
ty = 4
: x be
al iB

455
ie he Vi = onpaohin. a ee
10.9
se Oe UCTa aust
ee Py
of age 1 01.0 .669.a1) oe
30.0
soe Ute ORS (GSAT) y,Bi
36.0
Sl ge os v2, = Oreaptone
24.4
Ay seme 14 SPM lleLACTIL)
13.6
oles ions 75 “Otesse)
5.6
Si Oerst* Paced ORI
CLEAL Tals
ate

Using the data in Problem 7.1, calculate the activity coefficients

of water and n-propanol at 0.20, 0.40, 0.60, and 0.80 mole fraction

n-propanol, using Convention II and considering n-propanol to be

the solvent. 2

[ION
SOLUTION
Bete Yo,
1.81
Qo \(osgonme = eet
Sao. 1.89
wi"= Wayans _

x,
7 2507 -
= 0.6 Fe ASTORUe mee es

x, * 2037 2
= 0.8 1 = (osgyea.o01) 4 779?
To obtain the Henry law constant for H,O (Component 2) plot
P,/x, versus X,. :

Pp
a ~2.-_ 0.56 9+
At xp = 0.05, "il ware see

P
AG@ieMiee
2 0.10,
Feo
x 2 me 1288)
0.1 Eee

Thus as xy —> 0,P, =e xy

x <= "0)..2
2 2179 We
x, = 0.8 Oo oO aoe

f II
re ee er nang Ae
x, = 0.6 Ub wemariey (Oba aS
10

a
reme0.4 9/2)
nT
Oo
6(a
ee
Carake 0 0. 02
 113

2 ; = 2.91
Oye pte wretiiceyo

1.6 Show that the equations for the bubble-point line and dew-point
line for nonideal solutions are given by

sat
Seren
a Se sat sat
Mary Woks

sat sat ,sat

=e Stasi ViVori= *o
1 sat sat
Py Py PyoPo
SOLUTION
= sat sat
F te sd Ftp St a oP 5
ei sat sat _ sat
= YoPp + X41Py YP?
sat
3 Y2Py
ot = sat sat
%4Py P <%5t5
sat
ie fa . itt
it P. +P sat sat sat
1 2 Y>P, + x1 (74P) Y>P, )

Substituting the expression for x, yields the desired expression

i
for Yy°

A regular binary solution is defined as one for which

ig = by + RT in x, + wx?

Wy = Wg + RT In Kat + wx?

(a) Calculate AG ;,, AS;,, AH,;,, and AV,,, for the mixing of
Xq moles of Component 1 with Xo moles of Component 2. Assume the
114

coefficient w is independent of temperature and pressure. (b)

Derive the expressions for the activity coefficients y, and yy in

terms of w.

SOLUTION

(a) AG ax = X44 SP X9N9 = RT (xy In Xq ste x9 In Xo)

= xqny’ + xpiig’ + weyxo” + way’

x9
= qty’ + xQHg” + wxyxe
cage 0 0
oe (==) pe hfe eb)
G = Xqhy 55 XoHo = X4Hy" oF XoUo” oF RT (x, In x1 or

X_ In Xo) + WX4X5
0 0
ee ee

LN weit
Six 7 scree = Re ae ety
AH ix = AG ix + TAS ix = WX4X5

\ mix
(De oPSa )n ar

ry
(b) My = My ot: RT In Y1*1

Hy = By ° + RI In Xy + WX9 2
 115

Therefore 2 2
; he RT WX [re
ee ae VOenGur <&

The expressions for the activity coefficients of the components of

a regular binary solution were derived in the preceding problem.

Derive the expression for Y; in terms of the experimentally

measured total pressure P, the vapor pressures of the _ two

components, and the composition of the solution for the case that

the deviations from ideality are small.

SOLUTION
Ya) = (ezD (wxy7/RT) 15 “= "exp (wx,7/RT)
= ss sat sat

If the exponentials are not far from unity, the exponentials may be
expanded to obtain
Z
wx wx
a sat 2 sat il
P = x,P, il gp RT + x,P, (+ RT )

sat sat
wie ei XoPo )
RT sat sat sat
FS SNe Fs )
Thus from a measurement of the total pressure of a mixture of the

two components, the activity coefficients of the components can be

calculated over the entire concentration range using the first two

equations given above. This is a particular example of the general

situation that yy, and yy) can be calculated from the total pressure

as a function of X4-
116

Using the data in Problem 7.1, calculate the activity coefficients

of water and n-propanol at 0.20, 0.40, 0.60, and 0.80 mole fraction

of n-propanol, using Convention II and considering water to be the

solvent.

SOLUTION
The data at the lowest mole fractions of n-propanol are used to
calculate the Henry law constant for n-propanol in water.

xX, 1 el= P,/x,

Ky

0.02 33.5
0.05 28.8 40
0.10 176

Y = 2
x, & 30
a Fe 7 Tikly 2 0.24 K2
2 ; Yo 0.2(37)

os is 1:39 0.13 20
eee Ce NCEE Tf)
2.07
a)
= 0.
6 INE
S
0637)
a 0.093
10
. n 2.37% 0 0 40
ae Yo = Nona 0.080 2 08
K2
Y, 1 = asat ig Pe
Dia 1 = (0.8) @.17)
mi ey
eee
Be Yee
2.89
m2 . %1 - (0.6)@.17)
= 0.

yee bee %1 = (0.47.17)

7= 008 Pepe 1.79
SE ein
-2 %1 ~ (0.2)(.17)
 ae i,

7.10 The Gibbs—Duhem equation in the form

oe
oT
dpaspree oe
oP
dpeet ) (x ees
dM.) Ul oS
P,x. sex.

applies to any molar thermodynamic property M in a homogeneous

phase. If this is applied to ree it may be shown” that if the

*
J. M. Smith and H. C. Van Ness, Introduction to Chemical Engineer—
ing Thermodynamics, McGraw-Hill, New York, 1975, p. 346.

vapor is an ideal gas

d in (y,P) d in (y,P)
x, CO Ft SOX. ———_ =_ *OO':«“(constant T)
ul dx, 2 dx,

Show that this can be rearranged to the coexistence equation

ap. ¥. Ply, - x,)

dy, y,(1 - y,)

Thus if P versus y; is measured, there is no need for measurements

of X1°-

SOLUTION
xzd In yy + x,d In P + x9d In yo + xod InP = 0
x x x x
1 2
doin. Py = -— ay, < — ay, = (- 3 + =?Jay,
71 , A 0)
Lee cs ee eae he iar ae ag
¥49> 1 y,@ - y,) 1

7.11 From the data given in the following table construct a complete
temperature-composition diagram for the system ethanol-ethyl

acetate for 1.013 bar. A solution containing 0.8 mole fraction of

ethanol, EtOH, is distilled completely at 1.013 bar. (a) What is
118

the composition of the first vapor to come off? (b) That of the
last drop of liquid to evaporate? (c) What would be the values of
these quantities if the distillation were carried out in a cylinder

provided with a piston so that none of the vapor could escape?

0 t)

XEtOH YEtOH B.P., C XEtOH YEtOH B.P., C

0 0 17.15 0.563 0.507 72.0
0.025 0.070 16.7 0.710 0.600 72.8
0.100 0.164 75.0 0.833 0.735 14.2
0.240 0.295 712.6 0.942 0.880 7684
0.360 0.398 711.8 0.982 0.965 17.7
0.462 0.462 71.6 1.000 1.000 718.3

SOLUTION

16

74

12
Temperature
>

Mole Fraction ethanol >

(a) The liquid *will start’ to boil at’ "73-7" C. eee The vapor in
equilibrium with it is 0.69 mole fraction in ethanol (point
A)
 119

(b) As the boiling continues, more and more of the EtAc will be
removed. As the mole fraction of EtOH increases, the boiling
point will also increase. Finally, the very last vapors will
be pure EtOH, as indicated by point B.

(c) The first vapor to come off will be the same as in part (a).
However, when all of the mixture is in vapor state, the mole
fraction of the vapor state will be .800, simply because that
is the total mole fraction of EtOEK in the entire mixture.
Thus, to find the composition of the last drop to evaporate
into the cylinder, simply note what liquid is in equilibrium
with vapor which has .800 EtOH in it. This is given by point
Cs

7.12 The following table gives the mole percent of n-propanol (M = 60.1
g mol) in aqueous solutions and in the vapor at the boiling point

of the solution at 1.013 bar pressure.

B.P.5 £ 1005029272057 8953 MSS.) Si8 oSsd ee90eS Sis

Mole % of n-propanol
In liquid 0 20) 6.0 20.0 43.2 60.0 80.0 100.0
In vapor 0 21.6 3553, 139.2) 43.2. 40.2 © 6471 100.0

With the aid of a graph of these data, calculate the mole fraction
of n-propanol in the first drop of distillate when the following

solutions are distilled with a simple distilling flask that gives

one theoretical plate: (a) 87 g of n-propanol and 211 g of water;

(b) 50 g of n-propanol and 5.02 g of water.
lOO
SOLUTION
ee oe,
eps T6050
90
271 |
co Oe. mone! |
|
r 1544 one oeph eee :
“Pr (9440+ 11.9 : Oe OU 4506 Oa 0
Mole/n- Propanol
From graph Yoo > ORs
120

50 _
(b) pe Se 60.1. = 0.831

Sn 020
ny 0 = “ae” = 0.279
2
0.831
Xp, = 0.831 + 00279 Or
Ypr 0.59 from graph

7.13 The NBS Tables of Chemical Thermodynamic Properties list A,G’ for
I, in CgHg:x as 7.1 kJ mol. The x indicates that the standard
state for I, in CoH is on the mole fraction scale. What is the
solubility of I, in CgH¢ at 298 K on the mole fraction scale? A
chemical handbook lists the solubility as 16.46 g I, in 100 cm of
Cog. Are these solubilities consistent?

SOLUTION

AG. wei RTs 1 nex

qoqe Eat (gts a9 )(298) tas

bd i} 0.0569 where x is the equilibrium mole fraction of I,

The mole fraction calculated from the chemical handbook is

16.46
253.8
16.46, (100)(.8787) One>
253.8 78.12

so the values are consistent.

7.14 The following cooling curves have been found for the system
antimony-—cadmium.
 121

Cd, Wt. % Oni? Oded) iS ond Sak eGie 8 70 93 100

First break in curve, °C —- 550 461 — 419 — 400 -- --
Continuing constant .
temperature, °c 630 410 410 410 410 439 29599295 321

Construct a phase diagram, assuming that no breaks other than these

actually occur in any cooling curve. Label the diagram completely

and give the formula of any compound formed. How many degrees of
freedom are there for each area and at each eutectic point?

SOLUTION

tf

Weight fraction Cd
122

7.15 The phase diagram for magnesium-copper at constant pressure shows

that two compounds are formed: MgCuy which melts at 800 °C, and

Mg,Cu which melts at 580 °C. Copper melts at 1085 °C, and Mg at

648 °C. The three eutectics are at 9.4% by weight Mg (680 °C), 34%
by weight Mg (560 °C), and 65% by weight Mg (380 °C). Construct the
phase diagram. How many degrees of freedom are there for each area

and at each eutectic point?

SOLUTION
1100 ligvid
F=2

Biee:
O MgC, MNg2Cu 50 IDO
CU Ne mg
Weight lo m4

Uh Se ga) es Al In the liquid region F = 2; in the two-phase

regions F 1; and at the eutectic point F = 0.

7.16 For the ternary system benzene-isobutanol-water at 25 °C and 1 bar

the following compositions have been obtained for the two phases in
 123

equilibrium.

Water-—Rich Phase Benzene-Rich Phase

Isobutanol, wt.% Water, wt.% Isobutanol, wt.% Benzene, wt.%

2533 Oi 39 3.61 96.20
4.30 95.44 19.87 19.07
523 94.59 39.57 57.09
6.04 93.83 59.48 33.98
oS? 92.64 76.51 11.39

Plot these data on a triangular graph, indicating the tie lines.

(a) Estimate the compositions of the phases that will be produced
from a mixture of 20% isobutanol, 55% water, and 25% benzene. (b)
What will be the composition of the principal phase when the first
drop of the second phase separates when water is added to a
solution of 80% isobutyl alcohol in benezene?

SOLUTION Water
(a) H,O layer:
fp

5.23% isobutanol
94.5% H,0

Benzene layer:
39.57% isobutanol
57.09% benzene

(b) 10% H,0

72% isobutanol
18% benzene

Tsobutano) Benzene
124

7.17 The following data are available from the system nickel sulfate-
sulfuric acid-water at 25 °C. Sketch the phase diagram on
triangular coordinate paper, and draw appropriate tie lines.

Liquid Phase Solid Phase

NiSO,, wt .% H,S0,, wt .%

PMS Als 0 NiSO,°7H,0

2134 1.79 NiSO * 7H,0
IMF! ILS) 3.86 NiSO *7H50
26.15 4.92 NiSO, -6H,0
15.64 19.34 NiSO,°6H,0
10.56 44.68 NiSO,°6H,0
9.65 48.46 NiSO,° H,0
ZiT 63.73 NiSO, ° H,0
0.12 91.38 NiSO,- H,0
0.11 93.74 NiSO,
0.08 96.80 NiSO,

Wt. %

Nisa, *H20
NiSO,- H,0 89.6
NiSO,°6H,0 58.8
NiSO,*7H,0 54.9
NNSA, 640
NPS0y°7H,O

H.50y
 125
-18 2 .361x110-> K
19
Yacetone ~~ 1.67 Yes

-20 (a) 19.9 kPa (bd): 2.00; 1415) 1.375 1565, 1.88; °1.96

22 0.125, 0.186, 0.182, 0.166, 0.120

223 ee ann wae 0.55 Pure CoH may be obtained by distillation

6 6 .
provided Xo H » SSE
6 6

.24 11.17 kJ mol

025

LIQUID

ihe

WEIGHT FRACTION AV
126

a2 6)

Methyle yclohexane

40, Waniline
>Clneth yleyele =
36.5 4methyle yclohexane
Bane
73iN-heotane 55.2% heptane
B5% antl ne

Aniline — > n-heptane

Wee

2.0
Saturated Solution

Na,S0y ‘Al, (50,), I4HO

No SO Al, (Sy)
CHAPTER 8: Electrochemical Equilibria

8.1 How much work is required to bring two protons from an infinite
distance of separation to 0.1 nm? Calculate the answer in joules
using the protonic charge 1.602 x 10 19 C. What is the work in kJ
mol! for a mole of proton pairs?

SOLUTION
Q,
P otential
i ¢ = Tce
fe)

_ (1.602 x 10 7? c) (0.89875 x 107° N mc”)

107. "a
= 147396-Jac—4
Orden (1,602 <x 10+”) (14.3987 0.4)
2.307 x 104° 7
(2.307 x 10-28 3)(6.022 x 107? moi)
i) 1389.3 kJ mol
8.2 What is the electric field strength 0.5 nm from a proton?

SOLUTION
E = a
4ne r
fo)
1.602 x 10°19 ¢
4n(8.854 x 10712 c2 no! m2) (0.5 x 107? m)2
ll 5.759 x 10° Vm
A small dry battery of zinc and ammonium chloride weighing 85 g
will operate continuously through a 4-Q resistance for 450 min

before its voltage falls below 0.75 V. The initial voltage is

1.60, and the effective voltage over the whole life of the battery
128

is taken to be 1.00. Theoretically, how many kilometers above the

earth could this battery be raised by the energy delivered under

these conditions?

SOLUTION
T= 5 = ie = 0.254
Powersc= I7R = (0905 A)*(4.9) = 10.256
Work = (0.25 W)(450.4°60 s) = .6.75-26100 9
= (0.085 kg)(9.80 ms ~)h
UF hy RRO 15 eet nei Ope a
(0.085 kg) (9.80 m s 2)
z (8103 x 10° 5 cm) Lean
(2¥54 om in+)(12 im ft ~)(5280-ft mile
7)
8.4 What is the expression for the activity of Na,SO, in terms of the

mean ionic activity coefficient and the molality.

SOLUTION
Na, SO, Na+ S0,= YNat 2m

“$0 ,=
= (2myy 4+) (Yo m) ¥g9 = =
4 4
i 4m s4e3
y+ Where y+ 7 (Yy,* 2 ¥so,-) 1/3

8.5 A solution of NaCl has an ionic strength of 0.24 mol kee (a)
What is its molality? (b) What molality of Na,SO, would have the
same ionic strength? (c) What molality of MgSO4?

SOLunion
(a) T= + (m Zz + m,z,)
 129

0.24 = 51 (1°2 + 17) m =

m = 0.24 mol kg}
i
(b) 0.24 = 7 (2m x ie + m2”) m = 0.08 mol kg

1
(c) 0.24 = = (27 + 27) m m = 0.06 mol kg

8.6 For 0.002 mol kg CaCl, at 25 °C use the Debye-Hickel limiting law
to calculate the activity coefficients of Ca** and Cl”. What is
the mean ionic activity coefficient for the electrolyte?

SOLUTION
I = +(0.002 x 27 + 0.004 x17) = 0.006
log ¥; =, -0.509°z,7) 11/2
log Yo,2+ = -0.509(27)(0.006)1/2
Yca2t = 0.695
log yeq-_— = -0..509(17) (0.006) 4/2
Yoi- = «0-913
1+ = (y, 7_7)2/3 = (0.695 x 0.913)2/3
= 0.834
8.7 The cell PtlH,(1 bar) |HBr(m)|AgBrlAg has been studied by H. S.
Harned, A. S. Keston, and J. G. Donelson [J. Am. Chem. Soc., 58,
989 (1936)]. The following table gives the electromotive forces
obtained at 25 °C.

m/mol kg 2 0.01 0.01 0.05 0.10

E/V Or5127 0.2786 0.2340 0.2005

Calculate (a) E° and (b) the activity coefficient for a 0.10 mol
kg solution of hydrogen bromide.
130

(a) Plot E + 0.1183 log m — 0.0602 Nn versus Db.

The intercept at m = 0 is E° = 0.0710 V.

(b) E = 0.0710 V - (0.05915 V) log y+? m?

0.2005 V = 0.0710 V - (0.1183 V) log y+ - (0.1183 V) log 0.1
‘ _ _ 0.2005 - 0.1183 - 0.0710
gee an 0.1183
y+ = 0.804

According to Table A.1 what is the value of the equilibrium

constant for the reaction

> Hy (e) + AgCl(cr) = Ag(cr) + H” (ao) + Cl (ao)

at 25 °C and how it is defined?

SOLUTION
AG? = -131 298 — (-109-789) = -21-329 kJ mols
0

K epee Ss 701 10"

a(H*)a(C1_) _a(HC1)

Ce ite oa
In writing the equilibrium constant expression the activities of
the pure crystalline phases are taken equal to unity. Strictly
speaking the pressure of hydrogen should be replaced by its
fugacity.

8. 9 The electromotive force of the cell

Pb (cr) |PbSO, (cr) |Na,S0,°10H,0(sa

[Hgt)
80, (cr) [Hg (1)
is 0.9647 V at 25 °C. The temperature coefficient is 1.74 x 1074
VE -, (a)i What as the coll reaction? (b) What are the values of
AG, AS, and AR?
 131

SOLUTION
Ca)" Potcr)” + “HgoSOg(cr) = PbSO,(cr) + 2Hg(1)

(b) AG = -nFE = -(2)(96,485 C mol!) (0.9647 V) = -186.16 kJ mo1~?

AS = oF (ir) = (2)(96,485 C mol t)(1.74 x 104 v K-4)

= 983) Seer Ke mol¢

AH = -nFE + nFT (=)

= -2(96,485 C mol +)(0.9647 V) + 2(96,485 C mo1~-)

(298.15 K)(1.74 x 10°* vy K-4)
= -176.15 kJ mol
8.10 (a) Write the reaction that occurs when the cell
Zn|ZnC1, (0,555 mol kg) |AgcilAg delivers current and calculate
(b) AG, (c) AS, and (d) AH at 25 °C for this reaction. At 25 °C,
E = 1.015 V and (9E/8T)p = 4.02 x10 *vK?.
SOLUTION
(a) R ZAgC] + Je = 2Ag “+ 2C1~

L Ine Jem = Ifo

2AgCl + Zn = 2Ag + ZnC1,(0.555 mol kg +)

(6) SAG) = =nRE = =2(965485 C mol
+) (1,015 V)-=--195.9 kJ. mol>

(ce) "AS? =) “nk (22) 527156 485 Comolf-)(-4.02.% 10°" V.K"*)

Pp
35 -=7 75haTakiconol+
(4) AH’ = AG + TAS’ = 195,900 + (298) (-7716) = —219.0 kJ moi+
8.11 In problem 4.3 two equations were derived for calculating AG at

another temperature if it is known at one. Compare the values of

132

AG° (323 K) ‘and K, calculated with these equations for

H,0(1) = H’(a0) + OH (ao)

SOLUTION
Pate a ApG° (298 K) AH® (298 K) Cp’ (298 K)
H,0(1) =237.129 -285.830 75.291
H* (ao) 0 0 0
OH (a0) -157.244 -229.994 -148.5
AG? = -157.244 + 237.129 = 79.885 kJ moi}
AH? = -229.994 + 285.830 = 55.836 kJ mol}
ACh = -148.5 -— 75.291 = ~-223.8 J Ki! mo +
(a) AG,° = AG,° T/T, + AH(1 - T,/T,)
AG° (323) = (79.885) (323.15)/298.15 + 55.836 (1 - 323.15/298.15)
81.902 kJ molt
K, &= 6.94 x 10 -14

T>-ACp in (1, /7,)

(79.885) (323.15)/298.15 + [55.836 -— (298.15) (-0.2238) ]

(1 ="323,15/298.15)° + (323.15) (-0.2238) In (323.15/298-15)

I 70.483 kJ mol2
K Ww 4.046 x 10-12
ACp® is rather large for this reaction and so the simpler
equation yields a misleading result.

8.12 For the electrochemical cell

Zn(s)|Zn0, (aq) 1 1Cu0, (aq) 1Cu(s)

 133

what are (a) the half cell reactions, (b) cell reaction, (c) the

standard electromotive force, (d) the equilibrium constant for the

cell reaction, and (e) equilibrium constant expression?

SOLUTION
(Ca) tRCpel (aghe batt 26ape—cdCu ter) B® o6 on039370V
1 Zn7* (aq) + 2e = Zn(cr) E° = -0.763 V

(bo) Zn(s) + Cu**(aq) = Zn**(aq) + Culs)

(e) EB? = =93370 (0l963) et +1.100-V
Baye oe cot (96 $85) (201) 7 (85314) (298) oy 6 201937
3 3
a7 nCl 4 Mm ACl ¥4(ZnC1, )
2 2
(e) K eee 3 3
CuCl, 4 "CuCl, 7+(CuCl1, )

If the CuCl, solution and ZnCl, solution have the same

concentration, the activity coefficients will be approxi-

mately the same so that

"ZnCl, 1/3
z (1.62 : 10°7)
"CuCl,

8.13 Calculate the standard electromotive force of the cell

LilLiC1(ai)1C1,(g),Pt at 25 °C using (a) electrode potentials and

(b) standard Gibbs energies of formation.

SOLUTION
R Clj(g) + 2e° = 2 C1 (ao) 1.360 V
Led Libre err eye bi -3.045 V
C1, (g) + 2 Li = 2 LiC1(ai) 4.405 V
134

Using AgG° values

AG? = 2(-298.31 - 131.228) = ~849.076 kJ mol

Sit resiAG 849,076 J 4.400 V
nF
2(96,485 C mol-)

8.14 According to Table 8.1 what are the equilibrium constants for the

following reactions at 25 EC?

(a) H’ (ao) + Li(cer) = Li (a0) ot > H, (8)

(b) 2H’ (ao) + Pb(cr) = Pb" Cae) + H, (g)

3
(c) 3H’ (ao) + Au(cr) = Rae(ae) + > H, (8)

SOLUTION
+ = 1
(a) R + e = 7 A, E° = 0

edo ae ak Pr Peg ee CoE yes 045.0

fp eee > 4, oa 3 7045.V

x = enE°/RT 0

(96.485 C mol
1) (3.045 V)/(8.314 J K~2 mo1~1) (298 K)
= 3.1 x 10°4
ov
(b)) Rize Gee2eeee = sens E* 0 sa 6
Lipbe!
. 4 See 2 py eenewste Dipte panSee 0 LORY
T5689
+

On. ee ePh ee = Pp-* ea, E° = 0.126

2(96,485) (0.126) /(8.314) (298 K

K = e¢ )¢ ) meReat Os
(c) R OY + et Sle¥ = det:>3 Hy wee
Eons 0
L Rue foe Ce e= Ae E° = 1.50 V
ah ee Aa eee <n, Eo = 1280 Vi
 135

ee al (96,485)
3 ’ ae (-1.50)/(8.314) (298
. . K) a ay SUG Uysi

The striking resistance of gold to corrosion by acid is

evident.

S15 Devise a cell for which the cell reaction is

H,0(1) = H*(ao) + OH (ao)

Calculate AG® at 25 °C from electrode potentials. What is the
value of the equilibrium constant at this temperature?

SOLUTION
PtlH,(g) 1H" (ao) | JOH (ao) IH, (g) [Pt

R HO + e ee = |54H, + O8 7 E° Beng= oe -0.8281 V

+ - = A: One
1B OU + e aS H, E = 0O

H,0(1) =H (40) .39 OH (a0) R= 076281 ¥

AG’ =. =nFE® = (96,485 C mol) (-0.8281 VY), = 79.899 kJ mol +

eu a gcAGS RT o
Lie"-79,899/ (8.314)
(298) nieces —_—

(a,+) (age) i) 2 2
aie: beeen
H,0 a LE

The activity of water is taken to be unity since, in contrast

with the ions, its activity is measured on the mole fraction
scale (Section 5.17).

8.16 Devise an electromotive force cell for which the cell reaction is

AgBr(cr) = Ag* + Br . Calculate the equilibrium constant

(usually called the solubility product) for this reaction at 25 °C.

SOLUTION

AglAg* |IBr |AgBrlAg

136

R AgBr + e = Ag + Br E° = 0.095 V

LviAg Stale yle ty owipolt) LIV) We soleeeeIE a enO V1991e

AgBr = Ag’ + Br E° = -0.701 V
_ E° ~ OO.
log K = 9795916 ~ 0.05916 V eae
pet — 5211: 8Sieg signs

8.17 We found in Section 8.8 that for PtlH,|HCilAgCilAg E° = 0.2224 V

at 25 °C. Using the value of A,G°[C1 (ao)] obtained in Example
8.6, what is the value of AgG° [AgC1(cr)]?

SOLUTION
(a) R AgCl + e = Ag + Cl E° = 0.2224 V
Coyote oa +H, E° = 0
Agcl + +H, = Ag+ +C1 E° = 0.2224 V
AG? = -(96,485 C mol~1)(0.2224 V) = -21,458 J mol
= A,G°[C1-(a0)] - A,G°LAgC1(cr)]
A,G°[AgCl(cr)] = 21,458 - 131.263 = -109.805 kJ mo1 4
8.18 From standard electrode potentials in Table 8.1 what are the stand-

ard Gibbs energies of formation at 25 °C for Cl (ao) and Na’(ao)?

SOLUTION
For Hy (g) |HC1(ai)1C1,
(g)

R + Cl, wetchine ter Fadi Hellsac0any

Cen + ae = -p a$4, EY i} =es 0

agg + —

5 Clout Gg Boe 1H (aalech Cli (ag) E° = 1.3604 V

 E31

AG? = -nFE° = -(96,485 C mol t)(1.3604 V) = -131.258 kJ moi!

This is ApG° [C1 (ao) ] since AG° for reaction 1 is zero by
convention. Table A.1 gives -131.228 kJ mol.

For Hy (g) |H* (a0) | [OH (a0) 10, (g)

R L70, 1
+5 4H,0(1) +e oe= OH : (ao) E° a =fs 0.401 V
Lich (ao) ich & = + 4, E° = 0

ee
4 0, +
ear
5 H,
ae
+ 3 H,0
Mie
= H (ao)
pate earn ees Eee ROeN
+ OH (ao) =
AEE EN,
0.401

AG” = £2(96,485: Cémol”-)10.4010 V)e.= —38269 kJ mol:

SUeAVG f 10H eo (a0). Cee A 3 1.0)
2

A,G° [0H (a0)] = -38.69 + > (-237.129) ay 159. 06cer mola”

Table A.1 gives -157.244 kJ mol2.

For Na(cr) INa’ (ao) | 1H" (ao) IH, (g)

+ - 1
Rae ae 7 H, E ote= 70

+ - 0
Nar Oe be Gate Ne) 8 ie) =} om, LS OTE Ss)2.704 V
Na(cr) + H' (ao) = Na (ao) + > Hy (e) E° = 2.714 V

AG? = -(96,485 C mol +)(2.714 V) = -261.86 kJ mol* = A,G°[Na*(a0)]

Table A.1 gives -261.905 kJ mol-.
8.19 Using data from Table A.1 calculate the solubility of AgCl(cr) in
water at 298.15 K. The salt is completely dissociated in the

aqueous phase.

SOLUTION
AgCl(cr) = Ag*(ao) + Cl (ao)
138

AG? = 77.107 - 131.228 + 109.789 = 55.668 kJ mol2

K = exp(-55,668/8.21449e 298;15)ui= Halogexd10 4c
= (aq,+) (acy) = mw v4
5= m

m 1.33 x 10> mol kg!

8.20 Calculate standard electrode potentials at 25 °C for the following

electrodes using Table A.1.

(a) Li* (ao) ILi(er)
(b) F (ao) IF, (g)
(c) Pb**(a0)
[PbO, (cr) IPb
SOLUTION
bic es ea

AG? = —(-293.31) = 293731 kJamola-

E° “= =AG°/nF = -(293-310 J mol 1)/(96,485 C mol.) = =3.0400V

1 on =

> F, ( gz ) t e = F

AG? f= <2 78279 kT nol”

E° = (278,790 J mol 1)/(96,485 C mol) = 2.889 V

1
paeDO ee 2H) + tee = O62 010"
nab 2+
THRO

AG? 6) =ome -237.129 + 51 (-24.43) - 51 (-217.33) = -140.68 kJ mol

=

E° = (140,680 J mol~1)/(96,485 C mol) = 1.458 V

8.21 Using Table A.1 calculate the values of AG°, AH°, AS°, and ACp’
for the electrode reaction for the Na*|Na electrode.
 139

SOLUTION

The shorthand notation for the electrode reaction is Nat +e = Na,

but we must remember that we are really talking about the cell for
which the cell reaction is

Nat + > Hy (8) = Na(cr) + H*

AG° = -(-261.905) = 261.905 kJ mol?

AH®. = -(-240.12) = 240.12 kJ mol2
AS® @° Siepise-sus900 — > (130.684) 2 73137 5 Ko We

AC,® oS= 28,24 2 aGea ors ih

> (28.824) ah= -32.572 J K+ se mol oer

According to Table 8.1

AG? = -nFE° = -(96,485 C mol~1)(-2.714 V) = 261.860 kJ mol!
8.22 Calculate the standard Gibbs energy of formation of NO3 (ao) from

its A,H° and S° using data from Table A.2.

SOLUTION
il 3 il. a = +
z No(s) a 7 0, (8) + > H, (8) = NO, (ao) + 4H (ao)

WG SAHxf
Sobein
= TIS’ (NO)
3
= AS
2 2
(Ne Ses O00.)2
y)
Ae Sac)
2 2
= 1 3
= -205.0 - (298.15 x 10 ~)[146.4 - 5(191.61) - > (205.138)

1
rol (130.684) ]

= 108.86 EJ mol 2
The tepiiated velue sie -108 75 KI mol,8

8.23 What are the differences between the standard electrode potentials

for a standard-state pressure of 1 bar and 1 atm for the following

140

electrodes:

E°(1 atm)
C1 |AgC1(cr) lAg 0.2224 V
C111, (g) IPt 1.3604

SOLUTION
The change in potential with pressure should be calculated for the
balanced reaction that includes the hydrogen electrode.

ROH’) 44) 0) -a0e , Age CL.

L AgCl +
8 Gat, e tie= ae
o>
Bo ae ike ei et ae aed
> 4, + AgC1 = Ag + HC1(ao) 20; ses

Bo 0 -E* sl = -(A,6 @ 2
a,6*)/nk
*
=ae ks
<= [RT in (P*/P°)
* 0
159,
= (0.338 2V,/n) mV at 298.15 K = -0.338/2 = -0.17 mV

ei
Dec? (g) + e = Cl

1 a + -
> Ay = &f + €

Wa
Dua? 2eyoi = neha* SHEi SG
E° -E* = -0.34 mV
8.24 (a) When one mole of methane is oxidized completely to CO,(g) and
H,0(1) how much electrical energy can be produced using a fuel
cell, assuming no electrical losses? What is the electromotive

force of the fuel cell? (b) When one mole of methane is oxidized
completely in a Carnot engine that operates between 500 K and 300
K, how much electrical energy can be produced, assuming that the
mechanical energy can be converted completely into electrical
energy?
 141

SOLUTION
(a) B20, Sie: + 8 HY = 4 H,0
+ =
1G CO, ar 8 H + 8 e = CH, st: 2 H,0

AG° = -394.359 + 2(-237.129) - (50.72) = -817.90 kJ mol2

= -nFE°
Vibe ce 817.90°x
ee, 10° J mo1-2 A OSOGCV
8(96,485 C mol-)

(b) AH® = -393.509 + 2(-285.830) - (-74.81)

= -890.4 kJ mol
Iw! == lal (rT, * T0t, =z 200
8390407, _ 356 kJ mol -1

Thus the fuel cell would produce over twice as much electrical
energy.

8.25 Calculate the electromotive force of Li(1) [LiC1(1) 11, (g) at 900 K
for Poy = 1 bar. This high-temperature battery is attractive
2
because of its high electromotive force and low atomic masses.
Lithium chloride melts at 883 K and lithium at 453.69 K. [The A,G°
for LiC1(1) at 900 K in JANAF Thermochemical Tables is —335.140 kJ

mol?,]

SOLUTION
Li) 1
oe CLag)e = Stich)
AG? = -335,140 J mol > = -FE
142

pe ore 335,140,T mole -1 Ty aan,

-96,485 C nots

8.26 Ammonia may be used as the anodic reactant in a fuel cell. The

reactions occurring at the electrodes are

NH,(g) + 3 OH (a0) = Note) 3,80) e

S|R

0, (8) ro. te H,0(1) + fe 4 OH (ao)

What is the electromotive force of this fuel cell at 25 °c?

SOLUTION
Rimsm0, 9 86°10. (4 eei2 6 = 12° 0H

EL 2N, £1280 + “126 = 4 NH, + 12 08

3:0, ef g4uNion ROR2 INR ant 0

Using Table A.1

AG’ = 6(-237.129) — 4(-16.45) "= +1356.97 kJ mol.» = -nFE
=I
Ross 1,356,970 J mol . = 1.1720 V

(12) (96,485 C mol ~)

§.27 When a hydrogen electrode and a normal calomel electrode are

immersed in a solution at 25 °C a potential of 0.664 V is obtained.

Calculate (a) the pH, and (b) the hydrogen-ion activity.

SOLUTION
are RT 0
(a) E = E - oF 2 ayt+ = E + 0.0591 pH

_ E-E° _ 0.664 - 0.2802 _

D005 91a an 0.0591 = | 8-8?

(bien to Sl OIn Perso eee nee

 143

8.28 Calculate the equilibrium constant at 25 °C for the reaction

2H* + Do(g) = Hy(g) + 2D

from the electrode potential for D* |p, 1Pt, which is -3.4 mV
at, 2545¢?

ae SUN Ae
Pt|D,, DI 1H", HA [Pt
E = 0 - (-0.0034) = 0.0034 V
* gnFE°/RT
iu

= ie hoe oe -1 ors VP 20
(8.314 JK mol ~)(298 K)
8129 A membrane permeable only by Na’ is used to separate the following
two solutions:
a 0.10 mol kg+ NaCl 0.05 mol kg? KC1
B 0.05 mol kg- NaCl 0.10 mol kg? KC1
What is the membrane potential at 25 °C and which solution has the

highest positive potential?

SOLUTION a B
¢ p= ¢ wo = BT7 ln 3=
De j

eee Coes tA meee Ks

-1_.-1
mol )(298 K) ren ‘2 Ss 0.018 V

96,485 C i

The 6 phase is more positive because of the diffusion of Na* from a

to BP. Since the ionic strengths of the two solutions are the
same, the activity coefficients of Na in a and B are very nearly
the same.
277.8 kJ mol 4
AGInL 46.11, 5.77 kJ mol 2
0.905

(a) ((a,)(a_)]4/?/m (by (Ca, ) (a_)2 17! S739 08 a

(etal (an) (acdh iain
(a) 0. 1 (b) 0.3 (c) 0.4 (d) 0.4

(a) aa)
tee ks
ete i5) eels 2\8
Cg) H (ao) + Cl (ao)

-131.260, NO reel 2 Ons -120.3 J K+ mo12

(6) -=1325260, —L67s127*ks > 56 50t Kiet
(a) The electrode with the higher percent thallium is
negative.

(hy) =1456m0o males (c) 0.030462 V

-130.318 kJ mol4 -125 J K~mo1 + ~167.580 kJ mol

(a) NalNaOH(m)|H,, Pt
At 25 °C B = E° - 0.0591 log (m” ys? P, 1/2)
2
(b) PtH, 1H,SO,(m) 1AgS0, lAg
KGl05) Ce Eee: a ty)
a 0.0296 log (4m? v9 P, ~4)
z

pK = 1.018 VI + log 5
sia (B.=.E FE
2.303 kr «*} «1°8 ™ 3
The equilibrium constants are 5.79 x 1 0895) ef9 s56ee 1080)
2.01) & 105s" 3.200, 20% Andee oeo Se

0.828 V
=O nlo2
 145

8.43 79.885) 055. 835k) mola uel -801668 Jake wmiolss,

1.008 x 10714
38268 EIemolee, -0.4009 V

6139, 91034 x*107° mols

-261.92 kJ moi
-744.49 kJ mol?
1.239 V
(a) 1.229 'V (bh), 15229 V

0.60

ib) 2040x107
CHAPTER 9: Equilibria of Biochemical Reactions

0
al According to Table A.1, what are the values of AG°, AH®, and AS® at

298 K for
H,0(1) = H*(ao) + OH (ao)
Show that the same value of AS° is obtained from AG°® and AK® as by

using AS° = X-,S,°

SOLUTION
AG? = -157.244 + 237.129 = 79.885 kJ mol
AH? = 290.904 4 2859830 = 55.836 kJ mol
AS?) = =10- 75 9-69-01 = —60n66 Kk mele” or
5 ABS OAC: (55,836 - 79,885) J mol
T 298.15 K

= 80.66 Ji ko motes
ne Using Table A.1 calculate AH’, AG°, and AS° for
Ch,CO,H(aq) = H’(ao) + CH,CO, (ao)
and compare the values in Table 9.1 for 298.15 K.

SOLUTION
AH® = -486.01 + 485.76 = -0.25 kJ mol
AG? = -369.31 + 396.46 = 27.15 kJ moi2
AS? “et 186,602 4178.7 @= 0s O2hd0 eK anole
oS For the acid dissociation of acetic acid AR is approximately zero

at room temperature in H,0. For the acidic form of aniline, which

is approximately as strong an acid as acetic acid, AR’ is

approximately 21 kJ mol -, Calculate AS° for each of the following
reactions.
 147
+
MN X
ee. + =

How do you interpret these entropy changes? What compensates for

the increase in entropy expected from the increase in number of

molecules in the reaction?

SOLUTION
For acetic acid

AG® = -RT in K
= RT 2.303 pK
= (8.314 J K} moi?) (298 K) (2.303) (4.75)
= 27.1 kJ moi
AS° = (AH —.AG°)/T- = -(27.1 x 10° J mol *)/ (298K)
= —9f 9 K+ mol
This increase in order is due to the hydration of the ions
that are formed.

For aniline

AG? = (8.314 J K+ moi

1) (298 K) (2.303) (4.63)
= 26.4 kJ mol4
AG? te 191 = 26 4) 00° J) wo 1/298 x)
=8 21g897K-*1a017"
The entropy change is much smaller than for acetic acid
because there is no change in the number of ions.

9.4 Estimate pK, and pK> for H3P0, at 25 °C and 0.1 mol ee ionic

strength. The values at zero ionic strength are pK = 2.148

pK, = 7.198.
148

SOLUTION
K pK (2n + 1)art/2
I I=0 fog
p. = vas Nn a TIPS

A = 0.509 at 25 °C
- + ~(n+1
n is defined by HA” = H +A ea)
For pK, of HPO), n = O

pK, = 2.148
(0.509) eed.
ee
(0.1) 2/2 2.148 — 0.122 2.026
1 + (0.1)

For pK, of H,PO,, n = 1

pK, = 7.198
(3) (0.509)ern
aaa
(0.1)W025
2/2 hy
1 + (0.1)
= 7,198 - 0;369 = 6.891

9.5 At what pH is the average net charge on a lysine molecule zero?

That is, what is its isoelectric point?

pK, = 2.16(-CO,H)
pK, = 9.18(a - NH”)
pK, = 10.79(e - NH3”)
(Simply set up the equation for calculating [H*], but do not

attempt to calculate [H*] because the equation is cubic.)

SOLUTION
The three acid dissociation constants are represented by

LH ese) Le ctjeHt K, = ([L](H*)/(1H]

ay
[LH] (H"1/{LH,*)
+
LH, i] cs==) ae: = A i]
No

etter LH ae K, = ([LH.*I(H*)/(LH32*1
 149

The net charge z is given by

ae + a+
(Lal +; (LH, ] + 2{LH, ]
Ed
2+
[L, Ot? +4 e[Lejod+ [LH] + (LH 3 1

-K,ULBI/H] + (LHI(H*]/K, + 2(LH](H"]7/K,K,

denominator

The net charge is zero when the numerator is zero so that

al (HE) Ǥ22gnia?
[H"] Ky KOK,
Multiplying each term by K,K,(H ] yields

+2 +3
“K,KAK, + K,[H ] ae eth) = 0

At pH 7 and pMg 4 what value of pCa is required to put half the ATP
in the form CaATP-2? At 0.2 mol L7! ionic strength and 25 °C the
following constants are known.

HATP?- = H* + aTP* pK = 6.95

MgATP2- = Mg2* + aTp4- pK = 4.00
CaATP?7 = Catt + arp4- pK = 3.60
SOLUTION
[CaATP” ] eee
[ATP*”] + [HATP®] + [MgATP”] + [CaATP”] 7
[CaATP?]/L[ATP* ] oor
[HATP> ] [MgATP~] [CaATP” ] :
WS Corey
[ATP” a]ca Seals eeaaycomb
[ATP* ] e d as naycca]
[ATP*
Peail 05> 1
Teco ee ie we ECan 1/10"
150

[Ca I) = A725 5x TOM nROIe ET pCa = 3.14

9.7 Show how the partition function method yields the ~4

number of A

bound per P and the number -tp of B are bound at the same site so

that
PA = P + A K, = (PI{Al/(PA]
PBo= P + B Kp = (PJ[BI/(PB]
Show that

i
din [B] @ in [A]

for these linked bindings.

SOLUTION
ZT te EB

bey Fy Soe 1OE ee oes

UO hed Shedkiee GkZOIAl 2 tele & [A]/K, + [B]/K,

[K]/K,
2 ee
B 1 + [A]/K, + [B]/K,

ee . [B]0 <4 [A] [B]/K,K,

2 1n ([B] — d{B] 2
(1 + [Al/K, + [B1/K,)
Bend 7 [Ald <4, y [AJ[BI/K,K,,
@ in [A] atA]
(1 + (Al, + [B1/K, ) x
9.8 Will 0.01 mol yt creatine phosphate react with 0.01 mol Lt
adenosine diphosphate to produce 0.04 mol pl creatine and 0.02 mol
Lt? adenosine triphosphate at 25 =ce pH7, pMg4? What concentration
of ATP can be formed if the other reactants are maintained at the
indicated concentration?
 ital

SOLUTION

Creatine P + H,0 = Creatine + Pp AG? ' = -43.5 kJ mol =

ADP + P = ATP + H,0 AGS ao S0RsiETewoLs!

Céeatine (PY p22 ADP. =) (Creatine + ATP AGU Ue S47: ET ole

RG Ae ee [Creatine] [ATP]
[Creatine P] [ADP]

=3 100 =" (8.314) (298) ein (0.04) (0.02)

(0.01) (0.01)
1340 J mo14
Therefore the answer to the first question is no.

K
e AG /RT _ .1340/ (8.314) (298) 4.5
[Creatine] [ATP]
[Creatine P] [ADP]

If the reactants are maintained at the indicated

concentrations,

4.5 [Creatine PJ[ATP] _ 4.5 (0.01) (0.01)

[ATP] i}
[Creatine] 0.04
1
jedi dese hlal:

9.9 In a series of biochemical reactions the product in one reaction is

aeereactant jin the = next. This has the effect that spontaneous

reactions drive nonspontaneous reactions. For example, reaction 2

follows reaction ll].

iL
1. L-malate = fumarate + H,0 AG°! 2.9 kJ mol
1
2. fumarate + ammonia = aspartate AG?’ = -15.6 kJ mol
The AG°' values are for pH 7 and 37 °C, and the state of ionization

of the reactants is ignored. In reaction 1, the activity of H,0 is

to be taken as 1. If the ammonia concentration is 10% mol Lo;
calculate [aspartate]/[L-malate] at equilibrium.
152

SOLUTION
L-malate + ammonia = aspartate + H,0 AG?’ = -15.6 kJ mo12

A 0 [aspartate]
BGa ne SOR eet [L-malate] [ammonia]
t
Oo aeentssc00 eid (80314)(298) tn eee el
[L-malate](10 ~)
[aspartate] _ 1.3
[L-malate]

9.10 Biochemistry textbooks give AG°! =e 2 Oaks) mol? for the

hydrolysis of ethyl acetate at pH 7 and 25 cc. Experiments in acid

solution show that

[CH CH, OH] [CH,CO,H]

= 14
[CH,CO, CH, CH, ]

where concentrations are in moles per liter. What is the value of

AG ° ,
obtained from this equilibrium quotient? The pK of acetic

acid = 4.60 at 25 °C.

SOLUTION
Of [CH CH, OH] (tcH,co, + [CH,CO, 1)
[CH,CO,
CH, CH,]

: [CH,CH, 0B] [CH,CO,H] ( ; [CH,CO, ]

[CH,CO, CH, CR] [CH CO, H]

a “cH ,CO,B
= 14 mol L oo ee
[HT]
At pH 7
-4.6
Ke = 14 [1 + = 3530
 153

AG?” = -RT in Ki = <(8.314:7 x 1 nol 1) (298.15 K) In 3540

25078 Kh looie

9.11 The cleavage of fructose 1,6-diphosphate (FDP) to dihydroxyacetone

phosphate (DHP) and glyceraldehyde 3-phosphate (GAP) is one of a
series of reactions most organisms use to obtain energy. At 37 C
and pH 7, AG°’ for the reaction FDP = DHP + GAP is 23.97 kJ mol -.
What is AG’ in an erythrocyte in which [FDP] = 3 x 10-© moi L7!,
[DHP] ¥38 52101° moll, sad. fGAPli= 18.5 x 10° moist 2?

FDP - a0 0S DEP ty GaP

0 o, [DHP] [GAP]
AG Uy
AG + RT In [FDP]

, ae
23,970 + (8.314)(310) In Oss x 10 DOR Sz M
(35x 108=)

i 5770 J mol

9.12 Fumarase catalyzes the reaction fumarate + H,0 = L-malate

At 25 °C and pH 7 K' = 4.4 = [L-malate]/[fumarate]. What is
the value of K’' at pH 4? Given:
For fumaric acid Ky
1074 ous
For L-malic acid Ky

(Migje + CB 1/K5y)
[L-malate] _ [M] + _ [BM]
[fumarate] [F] + [HF] FF 1 (tsa: [H1/K jp]

474974: 73y 6.37

4.4 [er 100 414974°18;
= * 25h
5
[1 + 16
154

Oli suGavensAG) =p 4Ot4i ki gota. for

ATES 4- oa Ho “Oo AME 2- SEO 7 ee cr iy

calculate AG°’ at pH 7 and 25 °C and 0.2 mol ies ionic strength.

See Table 9.4

SOLUTION
4- ois 4- at
i + 10> T PO: + On

107595 1975 °45 | Hates

HATP> HAMP!~ HP.O,” |

| eee
og,

2-

H,P,9,

(caneFs 1 + tum"): 4- + [HP,0,37]

(tP,0,471 S + [,P,0, ae 1)
(tare*") + trate?)|

[AMP
2- I[P,0, 4~ J \1 +

[ATP* ]

TS KOGe mie a

2]
~
(+ PL) 6 wo. tm
K
+ te

K
+_2

K
24 1PP 1PP 2PP
nit +

[ATP ] eae 1+ fa]

KATP
 155

7 a 132
-
baad
pceae US \
are
kOe NP
es lO) eee 10.
ere weer
co haa
(2077)? gas
10°."
= 1.53 x 107
AG’? = -RTtin K’ = -(8,314-3 K-! mof7+)(298'K) "in (1.53 x 10’)
Sar0 47 nor
9.14 The hydrolysis of adenosine triphosphate ATP to adenosine

diphosphate ADP and inorganic phosphate at pH 8 and 25 e

has a standard enthalpy change of -13 kJ mo1}, The standard

enthalpy changes of acid dissociation of KATP’ °, HADP~2, and

HPO, + aren-o.) O,) ands to oko) mol !, respectively. Calculate the

standard enthalpy change for the reaction

73 x =? 2
KATP + HO. = HADP + H,PO,

SOLUTION
ate* + a0 ADP? + HPO, eed Ag AHO = =13. kIomolee

HATP? = HY + ATP’ a8
ne tages 2) RAD? 0
+ 2- a oe!
H: +2 38ROR H,PO, - 8

HATP> + H,0. = HADP= + HPO,” AW (=: 229 kJ wola-

Ethyl acetate is hydrolyzed in an aqueous buffer at pH 7 in a

calorimeter. The enthalpy of hydrolysis as measured in the

calorimeter does not correspond with what is calculated from the

156

following standard enthalpies of formation from a chemical

thermodynamic table.

AH? (298 K)/kJ mo1 1

acetic acid (1) -484.5
ethanol (1) -277.0
ethyl acetate (1) -479.0
H,0 (1) -285.8
Please explain why. What additional information would you need to

calculate the heat absorbed in this experiment?

SOLUTION
ethyl acetate (1) + H,O(1) = ethanol (1) + acetic acid (1)

AE. 5 3236) mot

This heat absorption would be obtained in acidic solution (where
the acetic acid is undissociated) if the reactants and products
form ideal solutions. At pH 7 HH is produced and reacts with
the buffer. Therefore, it is necessary to know the heat of acid
dissociation of the buffer. To calculate an accurate value for the
heat absorbed, AgH® is needed for

acetic acid dissolved in water

ethanol dissolved in water
ethyl acetate dissolved in water

9.16 If n molecules of a ligand A combine with a molecule of protein to

form PAL, without intermediate steps, derive the relation between
the fractional saturation Y and the concentration of A.

SOLUTION
P+ nA = PAL

K =Ny [PALA
[PA] LE .
oo Eee Lene
 ES7

(cP1 fe)
iy n
1) tay” n Pa
n

iPxdrare
wan
Sek [PJ] TA) = Fe [PA] (x + (al")

Y = eon a | ae
[P] | 1 + K/{Al2 ioe he

This equilibrium represents a cooperative effect in that as soon as

one ligand molecule is bound, the other (n - 1) ligand molecules
are also bound.

9.17 The percent saturation of a sample of human hemoglobin was measured

at a series of oxygen partial pressures at 20 ce pH 7.1, 0.3 mol

Lt} phosphate buffer, and 3 x 10-4 mo1 L7! heme.

P /Pe Percent Saturation

0
2.

393 4.8
7187 20
1183 45
2510 78
2990 90

Calculate the values of h and Ky in the Hill equation. (See

problem 9.19.)

SOLUTION 4
log P log (;-—y)

2.594 cgae
2.896 -0.602
3.074 -0.087
3.400 +0.550
3.476 +0.954

(Please see graph, top of page 158)

y.
log ([—y = -log KL + n log P

n = slope = 2.4 K = 4x 10
158

t/ 2)

log(5)
Al

Ht

-3 | eee ore eee eee. ae

O- te2> 3.0 35 4.0
log ie

9.18 When myoglobin is in contact with air how many parts per million of

CO are required to tie up 10% of the myoglobin? The partial

pressure of oxygen required to half saturate myoglobin at 25 °C is

3.7 kPa. The partial pressure of CO required to half saturate

myoglobin in the absence of oxygen is 0.009 kPa.

SOLUTION
seeerie
co'Ecos. ae
sion *o,
afm / Ko2 + Poo/Koo
Ko, ues eae Pa Koo = 0-009 kPa

Py = (0.2)(101.325 kPa) = 20.3 kPa

 So

Pag /0-009 kPa

L7 #4 (20.3)kPa/3i7 "kPa + Pag/0-009 kPa ote

P = 0 6
Poeee —
CO 00005" kEa 101.3 kPa eas
9.19 Since it is difficult to determine the values of the four
dissociation constants in equation 9.67, the empirical Hill
equation

is frequently used to characterize binding. Show that the Hill

coefficient h may be obtained by plotting log [Y/(1 - Y)] versus
Poe
0,

SOLUTION

Be
i‘s Speers Lotte
°S ps y= ae eetio oe,
Tk Mh lo °8 ee0,

For a variety of binding systems relatively linear Hill plots are

obtained for values of Y in the range 0.1 to 0.9, but deviations
usually occur at the extremes unless h = 1. At the extremes the
plot usually approaches a slope of unity.

9.20 Kl Se 884g 10 pKye eb et0 pH = 6.615

9.21 The pH cf a solution of monosodium aspartate is

(pK, + pKy)/2 = 6.9. The pH of a solution of disodium

aspartate is greater than 10.

9.23 4.710
 4.35
+ +_2 De 2+ +
a: 3 Wie tu 1 * . [H J : (Wg nts Ug ie ]
1PP 1PP “2PP MgPP MgPP “1PP
+ +_2 2+ +

sO (=
1PP ae
1PP “2PP ie 1PP an
“MgPP We

sigg = (qth
6
«pune)7 MgPP
2+

ipp ‘vepp
0.063
AG = 9.2 kJ molt No
USE) (3

3.88 x 10 2 mol L
=423 kT omols
=30.33 kJ mol-
2.93 x 10!
pH 8, pMg 4 pH 8, pMg 8

AH®! 296.57 kiemol2 -19,7 kJ mols.

AG°' -42.7 kJ mol -44.4 kJ mol

9735 Cl ’
Ge s
-.
Aetean enw +
py el > KS TE 1)

0.158 mol L2 3 25.6%

=10)75.5 x71 “moi74
CHAPTER 10: Surface Thermodynamics

10.1 The surface tension of toluene at 20 °C is 0.0284 N meee and its

density at this temperature is 0.866 g cm >, What is the radius
of the largest capillary that will permit the liquid to rise 2 cm?

SOLUTION
1
Y = 3 best

peas 25% 2(0.284 N m4)

eiit piiheal oie
PE (0.866 x 10° kgtee
ahad
m~)(9.80akm sbo ~)(0.02
OES
m)

Sees eae eo 2es35 5.107 cn

10.2 Mercury does not wet a glass surface. Calculate the capillary
depression if the diameter of the capillary is (a) 0.1 mm. The
density of mercury is 13.5 g cm >, The surface tension of mercury
at 25 °C is 0.520N m2.
SOLUTION
r = hgpr/2 h = 2y/gpr
he al =2 3 =3 es
faye h = 02) Oss 20ON m7 19.80 wt s* 113.5 x 107 Kg°m ~)(0.05"x°107~ m)

=e 50) acm

(b) h = (2)(0.520)/(9.80)
(13.5 x 109 kg m°)(10°2 m) = 7.86 mm
10.3 If the surface tension of a soap solution is 0.050 N nv, what is

the pressure difference inside and outside for (a) a soap bubble 2
mm in diameter and (b) a bubble 2 cm in diameter.

SOLUTION
The effective surface tension is 2y because the soap film has 2
surfaces.
162

AP = 2y =, 4(0.050 NEea) Se
ae 0 P
(2) oR 0.002 m 2 £

4(0.050 N a) Pa
(b) AP = 7 * onooeneae
: a 10 P

0
10.4 Calculate the vapor pressure of a water droplet at 25 C that has

a radius of 2 nm. The vapor pressure of a flat surface of water

is 3167 Pa at 25 °C.

SOLUTION
ves
p° he~ ovat
> RT

P 2(18.016 x 10 -3 --kg mol = (0.07197, Nm)et

In (3767 Pa? = =9 a ae
(22 10s mn) (8 chan ko mol ok as
eee ees
(10° kg oe
P= 05350) Pa
10. 5 A solution of palmitic acid (M = 256 g mol1) in benzene contains
4.24 g of acid per liter. When this solution is dropped on a

water surface, the benzene evaporates and the palmitic acid forms

a monomolecular film of the solid type. If we wish to cover an

area of 500 om with a monolayer, what volume of solution should

be used? The area occupied by one palmitic acid molecule may be

takenutathea?lix 107° mc.
SOLUTION
The number of molecules in a cubic centimeter of solution is

(de2deg La (6L0220s
a
104TS]
melee) = 9S] ex. Or
18 cm -3
(256 g mol )(1000 cm L ~)
 163

The number of molecules required to cover 500 cm? is

(500 em")(10- +m Om) 17

2Z1%x 10 m

be ee Ge
——————————— = 0.0239 cm
3
OT TEx fo"° sane

20; 6 A protein with a molar mass of 60,000 g moi forms a perfect

gaseous film on water. What area of film per milligram of protein

will produce a pressure of 0.005 N mt at 25 °C?

SOLUTION
RT (si5i4 3K mol) (298 ©) 5 2 |
A = — = Sea erie ae meneomr ee er eee E = 94.596 x9105 sm moll
: = 0.005 Nm

n = eet Ee = 1.67 x 10 8 mol

60 kg mol

Area per milligram

nA = (1.67 x hi Se SEO ei ee eee ea

=» 82.8 mak

a0. 7 The acid CH, (CH, ) 4 3C05H forms a nearly perfect gaseous monolayer

on water at 25 °C. Calculate the mass of acid per 100 om?

required to produce a film pressure of 102° Nm.

SOLUTION
=I =4 7a
nee EL iB alae a mous hs Secor a ern
. Z 10° Nm

=|. 72
(100 pat 0201 m cm _
=|8
2.48 x tO etalne
164

- ‘i (244
-
x 10 ; kg mol
-1 __)
~ _ (200 pm N00. 01 m cm
2.48 x 10° m mol.
- betes
9.85 S07. Oeesess ION on ame
10.8 What volume of oxygen, measured at 25 °C and 1 bar, is required to

film on 1 m
2 of a metal with atoms in a square array
form an oxide

0.1 nm apart?

SOLUTION
Assuming one oxygen atom combines with each metal atom, the
number of moles of 0, adsorbed per m is

(1 an)
(J)t0sde 10 = no
The volume of oxygen is given by

(i a- (813141 Ko mol) (298) k)

(2)(0.1 x 10> m)7(6.022 x 102% mol) (101 325 Pa)
a2 4s 10k oe ate kes

10.9 The following table gives the number of milliliters (v) of

nitrogen (reduced to 0 °C and 1 bar) adsorbed per gram of active
carbon at 0 °C at a series of pressures.
P/Pa 524 1731 3058 4534 7497
v/cm 3.1 0.987 3.04 5.08 7.04 10.31
Plot the data according to the Langmuir isotherm, and determine
the constants.

SOLUTION
1 1 1 -
[ieee eer Intercept = 0.025 g cm q

v = 1/(0.025 g cme) = 40 Be a.
 165

eiepe pate awe os -3 igh een al i

Se} se ao) Pa

ee re ee
es (40 oo aK

K = [(513
-
g cm : Pa) (40 ene g ae oe
ats 4810
a2 Pa
|

10
at
V

Os

(©)

O
O | Z.
107>
Pa
166

10.10 Hydrogen gas is adsorbed on a metal surface as atoms. Show that

the fractional saturation 9 of the surface is given by

KP 1/2
H
@o=— :
1+ KP ee
2

SOLUTION
2
P
ke A - 1/2
B, (g) = 2H(g) Ky “iaprse Pu = (KOP Ey )
H 2
2

1/2 2,
K.(K_P.. ) KP
PR ve
1 + KPa
ag1+Kee(KP ayi/2 1+
|Os
KP. 172
H' P i, H,

10.11 Calculate the surface area of a catalyst that adsorbs 103 com? of

nitrogen (calculated at 1.013 bar and 0 °C) per gram in order to

form a monolayer. The adsorption is measured at -195 °C, and the
effective area occupied by a nitrogen molecule on the surface is
16.2 x 10°29 m* at this temperature.

The surface area is equal to the number of molecules times the

effective area per molecule. The number of molecules is PYN,/RT.

a = (1.013 bar) (0.103 L)(6.022 x 10° mol") (16.2 x 107? m”)

(0.083 L bark mol -)(2737K)
=e
10.12 The pressures of nitrogen required to cause the adsorption of 1.0
cm? oa. (25 °C, 1.013 bar) of gas on P-33 graphitized carbon black
are 24 Pa at 77.5 K and 290 Pa at 90.1 K. Calculate the enthalpy
 167

of adsorption at this fraction of surface coverage using the

Clausius-—Clapeyron equation.

SOLUTION
RET, in (P3/8)
ak = |
2 Rgnacay k1

_ (8.314 JK? mol *)(77.5 K)(90.1 K) 1m (290/24)

(00a Kk =" 7755 Kk)
=e Omk Jamo.)
2]

LOS13 0.0233 Nm
10.14 (a) 1.00288 (b) 1.0288 bar
10.15 (a) 15.2 x 10-29 m (b) 97
10.16 4.04 x 1076 mol m2

£0.17 244 m

10.18 20.3 L at 25 °C and 1 bar

10.19 (a) v, = 38.2 mm K = 1,22 4/100? Par?

(b) 30.4 mm?
10.20 39.6 L

710.21
Yared auen
A'A : une
BB

cAvadsm, Op arte, xpky > xk

10.22 AG) Leif mol?

10.23 29.5 kJ moi}

 PART TWO
QUANTUM CHEMISTRY

CHAPTER 11: Quantum Theory

11.1 A hollow box with an opening of 1 cm area is heated electrically.

(a) What is the total energy emitted per second at 800 K? (b) How
much energy is emitted per second if the temperature is 1600 K?

(c) How long would it take the radiant energy emitted from the box
at this temperature, 1600 K, to melt 1000 g of ice?

SOLUTION
(a) I = of* = (5.67 x 10°83 51 m2 x~4)(800 K)4
= 2.32 x 1043 m2 sl
(b) I = of = (5.67 x 10-8 5 s~1 m2 x~4)(1600 K)4
= 37.2\x 10° Jn grt
(c) AH = (333 J g 1)(1000 g kg 1) = 3.33 x 10° J
a SES ee Reeeer hie
Siiecedees

ik At what temperature does M, for cavity radiation have a maximum at

(a) 800 nm and (b) 400 nm? (c) What is Amax £0 cavity radiation
at. 25 7?

SOLUTION
(a) T . 2.898 x 10°” -3 K w/h,,,

_ 2,898 x10" -3 Km
600°: 10"
 169

-3
2°
ip) T = ee ee = 7245 K
400 x 10 nm

eyes 5 2URDBe eA eK ake Bis ageine Ae

max 298 K
This wavelength is in the middle of the near infrared range.

:Wa
AK Derive the value of the constant in the Wien displacement law

(equation 11.7).

SOLUTION
M, 2_ Onhe~
SO OY a
ve obe/AkT sae

xe he
Setting dM, /dd = 0 yields aea ee 5 where x = kn
e = eee:

Substituting successive values of x shows that x = 4.965. Thus

x rece he _ (6.626 x 10°" J s)(2.998 x 10° m oo)

max 4.965 k —23 1
(4.965) (1.3807 x 10 ike)

See eee eed ae

11.4 Calculate the wavelengths (in micrometers) of the first three

lines of the Paschen series for atomic hydrogen.

SOLUTION
oEac2 ee
‘et il Dn, Ny Cart h vty 2
sft 2 2 we SA9 BR 2
(n, = ig ) (n, 9)

For na, = 4 i = =o) 1S) ae = 1.8756 um

(109677.58 cm) (7)
For n, = 5 fy Pe cans ee ors
(109677.58 cm +) (16)
170

(9) (36)
For es 6 a =
(109677.58 cm ) (27)

iil, In the Balmer series for atomic hydrogen what is the wavelength of

the series limit?

SOLUTION
1 R
lim ae lim yes = or nA
ny =) CO n,—? © 2 ny

4
a= = ee a a 364.7054 nm
1.0967758 x 10° m
ik Calculate the wavelength of light emitted when an electron falls

from the n = 100 orbit to the n = 99 orbit of the hydrogen atom.

Such species are known as high Rydberg atoms. They are detected

in astronomy and are more and more studied in the laboratory.

SOLUTION
~(1-0967 x NOkea) Oko om") (> z 43
Ei00 ~ FEo9 =
100 99
= 0.2227 cm!
a = 4.49 cm
GL In the photoelectric effect an electron is emitted from a metal as

the result of the absorption of a photon of light. Part of the

energy of the photon is required to release the electron from the
metal; this energy ¢ is called the work function. The kinetic
energy of the ejected electron is given by

=—my “= hk 4A- ¢

where m and v are the mass and velocity of the electron. For the
 17All

100 face (see Section 25.7) of silver the work function is 4.64
eV. What is v,if the wavelength of the light is 300 nm?

SOLUTION
61626 x ay See
hv = £62626 x 1020 J s)(2.998 x 10 ms) = 9.93 x10 ~ 19 3
206510 a
fo eG 6eeV1e602e 10 CC) = 045 OS
fines
savy = hy Hg =. 9.93 210° e ° J - “f 5
743x409
Sm eex 10. iS
pa, ONL12
ey) Meteat2 2 ee = 7.42 110° ms”
Geider aes teks
BA. What potential difference is required to accelerate a singly

charged gas ion in a vacuum so that it has (a) a kinetic energy

0
equal to that of an average gas molecule at 25 C; (b) an energy
equivalent to 83.7 kJ mo1 1?

SOLUTION
(a) It has been shown earlier that the kinetic energy of an aver-—
age gas molecule is (3/2)kT.

Ee = > eT

2S ih

2(1.602 x 10 CO)

—]
83,700 J mol 1.3896 x 10
19
(b) Ee " J

Tg sho6nxtl0n ead 0.867 V

12602 x 10°
172.

Electrons are accelerated by a 1000 V potential drop. (a)

Calculate the de Broglie wavelength. (b) Calculate the wavelength

of the x-rays that could be produced when these electrons strike a

solid.

SOLUTION
2
(a) Ee = > mv
1/2
—19
Vv =
cS Ne =>
2(1000 V)(1.602 x 10
ane ais em A 24 eae
C)
ae

Qut10)x0 10) Maes

= 5875 HO ss >
h CHE OES
Mee ys Eon Cibolo Ei ee ee ae Tena
(9. 110~x 10 kg)(1.875 x 10 ms” )
= 0.0387 nm

(b) Ee = he/a eeeEe

N = (6,626 x 10° Js) (2.998% 10° m sr) -19

Om
= 1.24 nm

(1000 V)(1.602 x 10 C)

11.10 An ultraviolet photon (A = 58.4 nm) from a helium gas discharge

tube is absorbed by a hydrogen molecule which is at rest. Since

momentum is conserved, what is the velocity of the hydrogen

molecule after absorbing the photon? What is the kinetic energy

of the hydrogen molecule in J mol/?

SOLUTION

Poi hhte = Osea

6leoe wenot oT
as oe Letsox 10
-26 kg ms
41 = mv
58.4 x 10° m

2(1.0079 x 10> kg nC lee) .

6.0225 10-> mols
 26 23 =i!
(1.135 x 10. kg m se) 16.022 x 10 mol ~ ) ; ms =
, = | = 3.39
2(1.0079 x 10 kg mol )

1 2 -
E = z mv Ny = 0.012 J mol -

11.11 What is the de Broglie wavelength of an oxygen molecule at room

temperature? What is the average distance between oxygen

molecules at 1 bar at room temperature?

SOLUTION
slg ames? e 3kT 1/2 _ oh
7) mv a kT v= (2#*) aes

seam VAR
a8aes
p 6.63 x10 "Js
[(3) (5.31 x 10 2° kg) (1.38 x 1029 5 x )(298 x)}t/?
= 0.0259 nm

Sincere ees (3))< 10E kg mode (6102 20x010-° mol.)

5y31 x 107° kg

To calculate the average distance between molecules we calculate

the length of the side of a cube containing one molecule.

V = RI/P = (8.314 3 K mol

+)(298 K)/(10> Pa)

=P prOrig a Gel.

is Re tOMODATER? mol )/(6.022e% Nie es

t= 3246) nm

Since the de Broglie wavelength is much shorter than the average

distance between molecules, translational motion can be treated
classically.

11.12 What is the wavelength of a thermal neutron at 300 K?

174

SOLUTION
Died rheeresMa 5
3 EAL 2s Tee p
as oe oo ey 2m
n

p = VV 3kT Mm

/ = = -27
= 3)(ro Sexe 23 5 K 1) (300 Ky) G67 Sexe 1/0 kg)

= 4.563 x 10 a kg ms

pe ae ~$:820_ 3 27 2 8 Sh i452 s 108. tn

P “SIGS x6 IU kg ms

= .1452 nm

11.13 Calculate the approximate quantum number corresponding with the

translational energy of a 1-g bullet fired with a velocity of 300

ms at a target 100 m away. What is the de Broglie wavelength?

SOLUTION
Ear 1G + (0? kg )\(200 mistake A B4520007

oe
es 2
8ma

n = (¢) (8mE) 1/2ae (Geer 100 MO 2 We cune hie

61626 x40 Js
Og Sase TO..

PR 28Geen
WOOO S10 -34
lege ee eS Ae ee I ™33
(10 ~ kg)(300 ms ~)

11.14 A molecule exists in a certain electronic state for only 10 1° S.

What is the uncertainty in energy of the molecule? What is the
uncertainty in the energy of a mole of these molecules?
 SOLUTION
ABAC ROO veo Wa Que 8 hat et ets) ews 27-200"? AF
4n(10 s)
2 23 it
Sesto ahxehore> 5)(6.020%5) 105" ono <2) Eee G18 F BOL

as For a particle in a one-dimensional box, the wave function is

sae =
2 iLife
sin(nx/a)

(a) What is the probability that the particle is in the right half
of the box? (b) What is the probability that the particle is in
the middle third of the box?

SOLUTION
(a) 1/2, by symmetry

2a/3 2a/3
ete 2) + 2
(b) probability = qrdxte=") = sin (nx/a)dx

a/3 a/3

2 1 , EYE:
oe A)eee Ps sin(2nx/a)
os 2 a/3

2 a a a 2n2a a 2na
a a ee 3a Ang eS

ai lteeie gestartsay eas]

1 1 Bea x 1 mente
= 3 = ae sin 3 ot: De sin 3
176

11.16 Show that the function p =

Beo*
is an eigenfunction of the

operator d/dx. What is the eigenvalue?

SOLUTION
oY = ‘: Be = 40 e 5% = S» Thus the eigenvalue is 5.
x x

11.17 What are the results of operating on the following functions with

the operator d/dx?

(a) eae (b) cos x (c) ets

SOLUTION
Aeesce eee dcosx
(a) —=—- = -2axe (b) = -sinx
dx dx

(c)
dees
“a qpeee ike
ikx An eigenvalue, ik, is obtained only
with the last function.

11.18 Show that the operators for the x coordinate and for the momentum
p, in the x-direction do not commute.

SOLUTION
z =" xe and 2 = 4 LE
Px i Ox

$b f(x) = x° B er(x) where f'(x) is Of(x)/@éx.

® 2£(x) = 2 <— (xf(x)) = e Ef(z)? tear tl xh

Since these operators do not commute, we cannot specify precise

values of both x and Py: The relationship between the uncertain-—
ties in these two variables is given by the Heisenberg uncertainty
principle.
 177

Pi 19 (a) Calculate the energy levels for ny —serand on = Ay ate Ea)

electron in a’ potential well of width 0.5 nm with infinite
barriers on either side. The energies should be expressed in kJ
mol?, (b) If an electron makes a transition from n = 2 to n = 1,
what will be the wavelength of the radiation emitted?

SOLUTION

che (6.626 ¢-10-° aie

ee fe ho 2 29] BOURD. ROME SIOS TOO:
8ma 8(9.110 x 10 Kg)(5 x 10 m)

Selosacce s-1012 7

SeaG2A0bG or e1en 17) 6N022eE 10-° nog)

taser is nol for n=1

For «n®<=" *2

=4 26)
E = 4(145.1 kJ mol) = 580.4 kJ mol

(b) AE = (2.4096 x (on J)(4 - 1)

= he
a r
—34 8 =A
2.4096 x 10 - 1? 3)(4 - 1) = (6-626
:
x 20 "J J s)i22.998
208 x21010 ms) )
» = 274.7 nm

41.20 For a hydrogen atom in a one-dimensional box calculate the value

of the quantum number of the energy level for which the energy is

equal to(3/2)kT at 25 °C (a) for a box 1 nm long, and (b) for a

box 1 cm long.

SOLUTION
(a) E = kT = 3 (1,38 x 10. 23 JK 1)(298 K) = 6.47 2 100" 21 al
Nw
178

Wp
n = = (8mE) /
=6
ss -3 -1 —vHA|
1/2
10° m 8(1.008 x 10 Kee mot ©) (06.17 xo J)
r - 23 -1
6.63 x 10 Je Jers 6.02 x 10 mol

= 13.7 or approximately 14

(by) ee eee 10°

11.21 Show that the wave functions for a particle in a one-dimensional

box are orthogonal using

il
sina sinfBp = F cos (of Bar z cos (ao + B)

SOLUTION
2 we nmx
9, =) = cS Nie i = Pees

a a a
- +
2 sin “* sin “ax = + cos Same ES d ie cos ERE d
a a a a a
) o ra)

= 0 ifm#n

because n -~ m and n + m are both integers. The integrals are over

(integer)
nx
complete cycles of cos ; which are equal to zero.

11.22 Calculate the degeneracies of the first three levels for a

particle in a cubical box.

SOLUTION
2.
Ea eeipy An + n s +n a ios th) fn fey tl, 9), <8)
8ma
x Zz
 Ta.

2
n n n E/ LS
x y _ x Sma

ib il 1 3 Degeneracy = 1

z i |
2 1 6 Degeneracy = 3
1 1 2

2 z 1
2 1 2 9 Degeneracy = 3
1 2 2,

11.23 Later in Table 15.4 we will find that the following molecules have
the indicated fundamental vibration frequencies.

Br, (325 om 4) A Er (2640 cane) *H, (4401 emec)

What are the force constants for these molecules?

SOLUTION
k = ul(2nc e = p(2nc is

79
Bay) BS 30 460r
Bee 1D ee
2k ee
ee UIE 2a 8 Re =] rerey Ate hey i)
6.022 x 10°” mol

= 45 SiN a
81 Ly ae nee i
Rete (a2 998 x 10 8 -4(2,649 x 10" Baka cul) le
6.022 x 10°” mol

SoResuiicuNen x
1 0.5039 x 10> k we
ee ye tie 998 0 8 4.40 x10 CS mecat
mY
6.022 x 10 mol

i} 575.1 N m2
180

11.24 Check the normalization of Vo and V4 for the harmonic oscillator

and show they are orthogonal.

SOLUTION
2 : uy pee ore ; 1/2 ni! 2

ioe ae () S teen i. 2:

; saree 1 1/2
since e dx = aa 7
a

fo)

fee}

Sly 2 Srl 2 ~
9,
il
ax = 2(£)
Tt
reuton -4(2)
Tt
7eoGee dx
—co —o 10)

See /2 ni!/2 niet 1/2

-4(s ) > 3/2 1 since | x e dx = 3/2
I 4a
fo)

To check orthogonality

2
9 14x as ni/2 (2) Af? De ee a ae,

—c —o

ed
since x is an odd function and e Sy is an even function.

11.25 For the harmonic oscillator substitute the wave function for the
ground state into the Schrodinger equation and obtain the
expression for the ground state energy.
 181

SOLUTION
“ye
ee Ce “ where a = , Vkm

Shdo ts ay, ON as 2 Lax?

ave = 2axCe See = 4a x Ce = oo 2aCe a

Substituting in the Schrodinger equation

1 2
ree + z kx y = Ey

yields Eye 5) a(es ve x) she)

= h~/

11.26 In the vibrational motion of HI, the iodine atom essentially

remains stationary because of its large mass. Assuming that the

hydrogen atom undergoes harmonic motion and that the force

eonstant? kiicis 11327 oN m?, what is the fundamental vibration

frequency ~~) ,?

SOLUTION
1.0078 x 10> k Tes -27
m = ee ee = 1.674 x 10 kg
6.022 x 10°” mol

ae1 fe = 1 | 317ktes 5.7____ =

sti 6.93 x 10" 137-1
s
x = S 1.674 x 10 kg
TG

2
<x”> for a quantum
27 What are the expectation values for <x> and

mechanioal harmonic oscillator in the v = 0. state? What is the

standard deviation Ax?

SOLUTION

As shown in Example 11.10, for w= 0, <x> = 0 and

ee +
soe
(uk) 42

2 1/2
. ( 2. ar 1 h /
x : Ax = <xy ON minesyey 7
; 2 1/2
(nk)

What are the reduced mass and moment of inertia of 23ya Fei? The

equilibrium internuclear distance R, is 236 pm. What are the

values of L, L,» and E for the state with J = 1?

SOLUTION
oct eae: me Gye ee
i + _i my + Ty

“; =
> aQ|gorr _~3 ‘ -1 -3 ah
= ——_(22.98977_ x 10" kg mol" )(34.96885 x 10 " kg mol ~) _
[(22.98977 + 34.96885) x 10> kg mol 1(6.022045 x 102° mol)
-
= 2.30332 x 10 7° x,
 183

= ph.” = 26
(2.303 x 10 ~° a2
kg)(236 x 107s) Z
>

= 1.783 = 100” kg “

Pn wItssi) A a2 (Ginie 210° 8's) = ee Bi” 5s

Lo = or) se =~ (6.626 x 10 34 Js) = 0 tov / 2512054 x 10 24 Is

OE 3Nae pe an C2 Siete IS 63
A ia

21 2
4n°(1.283 x 10.
=45 kg m’‘)
2

= 42734 5 40° 4

11.29 Show that the first two spherical harmonics in Table 11.2 give the
same values of the energy and angular momentum as eguations 11.123
and sal 535.

SOLUTION

° 5
Y = —7;
ro) (an)t/?

Substituting in equation 11.121,

h?
- az (f° Yo
° =
°
EY |

so that E = 0, in agreement with equation 11.123.

: : : : 2 O
Substituting in equation 11.134, -4 (0)¥, = [| Y¥

so that a = 0, in agreement with equation 11.135.

y° = (=) cos 86
184

Substituting in equation 11.121,

1/2\.
ea Pi jin @ Oe
ia? o(2)yt atte? 4n 1

a
es ae, ) = : fa)
FY) (sin 6 2 sin 6 cos

Zz 1/2 NY ie
A
ee uh eee 3 ) @| = Eo otan
((—3) )
Si ET: ae 2 sin ® cos cos

45 AL 7) is cos 6 = E° 7) <n cos 6

I Ge 1 \4n

0
E, = weF 2
as expected.

Substituting in equation 11.134

2 1 a 0 il a7 fo) 2 20)
20 PS Cra) MOS nSe
6 0¢
ne a
a2 1/2
= he = (2 2 cos 9 = ies (=) cos 6
4n 4n

ig = nie as expected from i = 1(1 + 1)87

11.30 A diatomic molecule is in the J = 2 rotational state. What is the

value of the angular momentum? What are the values of the angular
momentum in a particular direction?

SOLUTION
L = Ai a1), Goes ¢ Veo on) (67606 e 10) sete)

9883 x 10 Te
 185

Possible values of L are

Z
POMNe(6h26 2108 Wis) /2n 1. .=20109 Sor <
-1 " " " SF 10s 0°
0 " " a a
1 " " ra oss Jos
3 " " " $63 4093410 J

Tha Bes fat 857.7 watts

re 32 290 nm
11.33 1397 J min}
11.34 6.62 x 10°" J 3, 2238 x 10°27? sx
11.35 2.74 x 1014 5-1, 1094 nom
11.36 4052, 2626 nm
11.37 Lie ® 20! Ay st
11.38 1.325 x 1027 kg ms 4, 0.0113 ms 2
11.39 5.93 x 10° ms 2
11.40 0.130 nm

11.41 0.00549 nm
11.42 5.28 x 10 °° J 1.6 x10 %
11.44 (a) - 6a (bin 1k

11.45 E = n?h?/8m12
11.46 146.9 582, 1305 kJ mol2
186

Wh A 4/ nnyn, i 2

E(8ma*/h”) 3 6

Degeneracy 1

£1549

11.50 E

ISIES §
 187

11.52

EZ
Lz=24
L2:%
£220

11.53 15438-x.10.7° kgs 1.454 x10 7° ky mw”, D558e¥r 10-455 5,

1.442 x 10-21 5
CHAPTER 12: Atomic Structure

IZ. 1 How much energy is required to remove a 4p electron from a

hydrogen atom in eV and in kJ mol 1?

SOLUTION
E ~(13.605 80 V)/n2 = -(13.605 80 V)/16 = -0.850 36 V
(-0.850 36 V)(96,485 C molt) = -82,047 J mol
2 «2 What are the wavelengths of the first line in the Balmer series
for H (relative atomic mass 1.007 825) and D (relative atomic mass

2.014 10)?

SOLUTION
The mass of the proton is given in the Appendix, but let us
calculate it from the relative atomic mass since we are going to
need to do this to obtain the mass of the deuteron.

no (My/Na) aa

= (1.007 825 x 10°? kg mol 4)/(16.027 045 x 1022 mo1-2)

~ 9.110 x 10°?! kg
= 1.627 648 5x 102! kg
Re Re) Cl m,/m,)

_ 1.097 373 177

x 10’ m?
1 + 9.109 53 x 10791 kg/1.672 649 x 10°27 kp
= 1.096 776 x 10’ m+

tCa)
A = 7.2/R, = 656.469 5 nm
 189

=o
(M)/N,) it ee 3.343 634 x 10 kg

"1.097 373 177 x 10’ m2

(124995109-5322 10 7/3 9438634 210” kg)
= 1.097 707 4x 10' mw"

Noe =) 7 6211.097-907 4x 10th t= 656.290.9 ne

12.3 Calculate the ionization potentials for He’, Li2*, Be>*, Bw and
cot
SOLUTION
E = (13.61 V)Z2
Z E/V Zz E/V
Hen 2 54.44 The 5 340.25
Liz 3 122.49 cot 6 489.96
Be? 4 217.76

12.4 Calculate the energies of ionization of H and D using the appro-

priate reduced masses.

SOLUTION
—_ #8 ae = ue teu, ps4

a 1/m, + 1/m, m + m

_ (9,109 534 x hes kg) (1.672 648 5 x 1007! kg)

(1.672 648 5 x 10°’ kg + 9.109 534 x 10°° kg)
BOO G4 15x10 ea kg

ari ~ &, Hy/m,

7
(150976373) 1717710 m +) (9.104 Sia x 10 te kg)
9.109 534 x 10 > kg
190

yi
= 1.096 775 8 x010. mee
Using the mass of the deuteron from problem 10.2

(9,109 534 x 10 >* kg) (3.343 634 x to ty)

line |Sa tat an g Bag LDy Riga) ME e-
(3.343 634 x 10 kg + 9.109 534 x 10 =31 kg)
= 9,107 052 x 10>¢ kg
7-1 -31
R= (1.097, 373 177 x 10 mm’ )(95107 052-x 10 kg)
9.109 534 x 10-4 kg

S04 Co7s074"2°S010) Ae
The ionization energy from the ground state is

Eee fl -
neR( +5 1
+) os= heR
| ey
The ionization energy of a hydrogen atom is
-34 8 -1
E, = (6.626 176 x 10 J s)(2.997 924 58 x 10 ms)
e 15096 TTSs xO) mee
=624178h7200xt10000| Jan=ew13%598e397=6V
The ionization energy of a deuterium atom is

E, = (6.626 176 x 407°) Js) (22997 924058 x 10> meee)

$097 (074.255 10 Rt
= 2.179 313 x 10 "y+ = 13.602 097 eV

12.5 Using data from Table A.2 at 0 K what is the ionization energy of
H(g)?
H(g) = H'(g) +hle.

For H(g) at OK Agi” i} 216.037 kJ mol>

H*(g) at OK A,H® 1528.085 kJ mol
 191
e (g) at OK A,H” = 0

E 1312,048 J molt
1312,048 J mol
(1.602 189 2 x 10 1° c)(6.022 045 x 107% nol)
i} 13.598 53 eV

12.6 Calculate the Bohr radius with the reduced mass of the hydrogen
atom.

SOLUTION

i -
ek deg imil
m m
e p
=n Ef e:1 aoleig
1 1
anh pe
9.109 534 x 10 kg eee Pee
Bea
1.672 648 5x10 207%kg

=i nl04 $75 102 ike

hae ) i €
pees Sel Ie °
Ouse 2. m HWAe
ae
He

_ (6.626 176 x RN eT VCR RS 4018 T0820 Co INT ee)

z 31
n(9.104 575 x 10 ~ kg)(1.602 189 2 x 10
=19 c)”

ll 0.052 946 5 nm

12.7 For a ls level in a hydrogenlike atom the Schrodinger equation

reduces to

8n“m 2
cy (Pees ee og awe e = 0
2 or or 2 4ne or
192

Using the functional form for Y1s obtain the expression for the

energy of the ground state.

SOLUTION
1 Z, a SLEVa) _ =Zr/a
V1s = aa e o = Ce fo)
x 0
oie
ee
ZC e
-Zr/a oO
or a
10]

a
a
ZCr- are
Sta)
oO
Mare
= ee
2ZCr | -Zr/a )
Or a 2,
a a
re) Oo

Substituting in the Schrodinger equation and eliminating ay by

ie ) anim 1Z
use Of a0 = —————— yields eee
2 anne” n’ (4ne,)”

12.8 What are the degeneracies of the following orbitals for

hydrogenlike atoms? (a) n=1, (b) n = 2, and Coe ne= 3.

SOLUTION
(a) n=1 f=0 m=0 a ie
degeneracy = 2 y

(by n= 2 f= 0 m = 0 m= ft 1
s 2

b= 1 m=-1,0,41 m= £5
degeneracy = 8 :

(c) n = 3 f= 0 m= 0 i = + i
s 2

f= A me ety0;e. mee
s
ee2,
f= 2 = m = -2,-1,0,+1,+2 as = 7
degeneracy = 18

[Note that the degeneracy is on?

.]
 193

£229 Show that for a 1s orbital of a hydrogenlike atom the most

probable distance from proton to electron is a,/Z.

SOLUTION -Zr/a
1, re ry)
ee e 2et/a,
Probability density of p(r) a r? Vis.

Setting the derivative of the probability density equal to zero,

2 eg
2ztla, ( 22) eae ecient eo. rt fe se
a
oO

12.10 What is the average distance from an orbital electron to the

nucleus for a 2s and 2p electron in (a) H and (b) Li2*

SOLUTION ;
na
(a) Cry =2 z° 1 + 15 E erCl
5 )
n

spdor aie1 2.0

Die Saie telCL)
iim cite
e 2
ae eee-9 pm

27 (52 92 pm) 1 2
Sead wa araitaer
ool ile 7 = 7 = 264.6 pm

(b) For Li2*

in 3 27 (52.92 pm) eS 105.8 vp

$020 8) 3 2 bine

iG
on 3
eee 2 ee 4 ee ap
i Aap le| Use equation 12.19 to derive the expression for the average

distance between the electron and proton in a hydrogenlike atom in

the 1s level.
194

SOLUTION

12.12 The wave function for the ground state of the hydrogen atom may be

represented by
t/a)
y = Ce

Where ay is a constant. Determine the normalization constant c.

SOLUTION

*
»" y dz = y gr dr sin O0d6d ¢

< Tt 2n

= | dr +2 d © sin 6 delice em etal = ona,”

fo) oO oO

3 YD
Therefore c = (1/na,.)

a
pasthe Calculate the expectation value of the distance between the
nucleus and the electron of a hydrogenlike atom in the 2p, state

using equation 11.54. Show that the same result is obtained using
equation 12.20.

SOLUTION

{r>
r == Po ° re Po 14t = 9041 4 rdt

3/2 Zr
(= cos © exp(-Zr/2a )
a O
 93

2n T
il
eTaer LNG
(fe) 3
<r> 3 exp(-Zr/a_)cos 0 + eind d0dgdr

o o Yo

The element of volume in spherical polar coordinates is

dt = r2sin © d@dgdr
and the ranges of the coordinates are

0< 6 on OoXt¢atd2n Os<rro< le

as may be seen in Figure 11.8.

When the integration is carried out using

- +
iw as dx = n!/b™ a we obtain Coy = 5a /Z
°
Equation 12.20 yields
4a
<r) =er7 1 + i
5} 1 _i7} Z= 5a/Z

12.14 It can be shown that a linear combination of two eigenfunctions

belonging to the same degenerate level is also an eigenfunction of

the hamiltonian with the same energy. In terms of mathematical

formulas, if Hy, = E,p, and Hyy = Eypo, then H(cyp y + Cop.) =
E, (cy 44 1 CoP). The wave function cy, + Coy. still needs to be
normalized. Equation 12.5 yields the following expressions for

the 2p eigenfunctions

%> 2 be 2t/2a r sin 0 ae

Pay

» = pea r sin 9 ane

2p -1

¥2p5 ce eta r cos 8

196

Use this information to find the real functions for the 2p

orbitals that are given in Table 12.1. Given:

e
ig = cos g + i sin ¢g
-ig
e = cos ¢ - i sin ¢

SOLUTION
As indicated in the footnote in Section 12.2, we define 2p and
x

op as the following linear combinations:

Y2p Car 20, )/ Ne

vo,2p, ~(%,2P 44 - 9 2P_4 iW oe
Substituting in these expressions we obtain

5 = bere ee sin Sle + 210) Wa

Py

= ape 27/28 r sin 8 cos 0/2

op = bee r sin Ble.” = 01%) /i ff

= ae r sin 6 sin ¢/v2

12.15 For a 2p electron in a hydrogenlike atom what is the magnitude of

the orbital angular momentum and what are the possible values of
L,?
SOLUTION
n = 2 L=1 m=-1,
0, +1
YO = 2 tae ea 1/2 Sh
V2 (6.626 x 10°" J s)/2n = 1.49102 10724 3 ¢
 197

Lore es imhee= (6.626 x07? 3 <s)/2n

+ 1.054 x 10°" 5 s
0
Shas tai ae ee a
12.16 What is the magnitude of the angular momentum for electrons in 3s,
3p and 3d orbitals? How many radial and angular modes are there
for each of these orbitals?

SOLUTION 3s 3p 3d

IL] = (i) 1) 2s 0 (2 [64

Radial modes 22 1 0
Angular modes 0 1 2

a2.17 Derive iy = mi (equation 12.23) using ie = -iff8/dg (11.132c) and

hs=e img .

SOLUTION
4% q = -iff 9 , img = mhe1™? = mi?
zZ ng
12.18 For the wave function
g,61) yy (2)
» =

9p il) Pp (2)

show that (a) the interchange of two columns changes the sign of

the wave function, (b) the interchange of two rows changes the
sign of the wave function, and (c) the two electrons cannot have

the same spin orbital.

SOLUTION
(a) The interchange of two columns yields
198

= pa (2) pp (1) a pa (1) pp(2)

This is the wave function for the atom with the two electrons
interchanged, and it is the negative of the function given in
the problem, as required by the anti-symmetrization
principle.

(b) The interchange of two rows yields

a pa (2) ppt) aad pall) gp?)

pa (1) pa (2)

which is the negative of the wave function given in the

problem. Thus the interchange of two columns or two rows is
equivalent to the interchange of two electrons between
orbitals.

(c) If two electrons are represented by the same spin orbitals,

the determinant

wa (1) pa (2)

pa (1) pa (2)

is in accord with the principle that two electrons in an atom

cannot have four identical quantum numbers.

12.19 What are the electron configurations for H, Li’, o-" F; Nae
and Mg2*?

SOLUTION
1s’, list; 1s72s72p°, 1s72s72p®, 1s72s*2p°, 1s72s72p°,

12.20 How many electrons can enter the following sets of atomic
orbitals: (ls; 2sD-2p; 385) 3p,. 367%

SOLUTION
There are 2t + 1 values of m for n given 2 and each of these
 199

orbitals may be occupied by 2 electrons so 2.24 + 1) electrons

can enter a set of orbitals.
>

Hist f=0, 2(28 +1) = 2

ZS P=.) 22 1) = 2
fell 210° f 4°71) eo 6
feo, 2(24+1) = 2
(Se 422 fae) 6
3d: lesz, 22000471) t= 10
12.21 Since the outer electron for Li is quite a bit further out than

the two ls electrons, this atom is something like a hydrogen atom

in the 2s state. The first ionization potential of Li is 5.39 V.

What ionization potential would be expected from this simple model

of a Li atom? What effective nuclear charge Z' seen by the outer

electron would give the correct first ionization potential?

SOLUTION
E 13.61ae V i} 13.61 V/4 = 3.40 V
n

5.39 V (z')2 (13.61 V)/4

Zz!
12259

12.22 The ionization potential of atomic hydrogen is 13.60 V. Calculate

the wavelength of the light produced when a free electron without

kinetic energy returns to the inner orbit.

SOLUTION
mole et bole “StrEe
SP ead Rote
a y we Oz oux 0 ay B148) 2.908 10
AeA eee ee)
eels Fyad 91678 am
Ee -19
(13.60 V)(1.602 x 10 C)
200

12.23 What is the electronic energy in hartrees of He, Li, and Be with

respect to the nuclei and free electrons? Ionization energies are

given in Table 12.4.

SOLUTION
The sums of the ionization energies are

He 79.003 V
Li 203.481 V
Be 399,139 V

The ionization energies expressed in eV are given by the same

numbers. The energies of the neutral atoms with respect to the

nucleus and free electrons are the ionization energies with a

negative sign. The energies of the neutral atoms are expressed in

hartrees (E,) by dividing by 27.211 608 eV By

He —2.903 Ey

Li -7.478 En
Be -14.668 Ey

12.24 Why is the ionization energy of boron less than beryllium and the
ionization energy of oxygen less than nitrogen?

SOLUTION

The first ionization energy of beryllium is due to the removal of

one of the two 2s electrons, and the first ionization energy of
boron is due to the removal of the electron from the singly
occupied 2p subshell. The 2p electron is on the average further
from the nucleus and is more easily removed.

The first ionization energy of nitrogen is due to the removal of

one of the three 2p electrons, and the first ionization energy of
oxygen is due to the removal of, one of the four 2p electrons.
Since the fourth electron in 2p° in the oxygen atom has to join
a ,half-filled orbital, it is not bound as strongly as the
2p electrons of nitrogen.
 201

12.525 The enthalpy of formation of H (g) at 0 K is given as 143.264 kJ

Hol ini TabierAc?. What.is the electron affinity of H(g)?

SOLUTION
The electron affinity is the energy released in the reaction

H(g) + e = H(g)

= 143.264 -— 216.037. = -72.773 kJ mol

=
Sonate T7 mol — ) 55 = = 00,7542 46V
C6022 2-10 CyCG0225%. 104 mol >)

Thus the electron affinity of H(g) is 0.7542 eV.

12.26 For a carbon atom in the configuration [He]2s22p

2 the following

term symbols are all possible, 183 0”

According to Hund's rules, which is the most stable state?

SOLUTION

According to Hund'’s first rule the most stable states are abe

See, and "Px, In using the third rule we have case (a).

; 3
According to this rule the most stable is Po:

12.27 Which of the following transitions are allowed in the electronic

spectrum of a hydrogenlike atom: (a) 2s > 1s, (b) 2p % Is,

(c) 34 > 1s, (d) 3d > 3p?

SOLUTION
(a) A = 0, not allowed (b) A 2 = -1, allowed

(c) Af = -2, not allowed (4) A 2 = -1, allowed

202

12;.268 1.153 x 1018 3 7.197 eV 694.3 kJ mol!

12.29 983 kJ mol+ 265
12.30 656.172 12, 656.163 58 nm
2 .o 1 0.198 um.
12.32 {r> = 6a,

PAR (a) 243 nm (b) 6.80 V

12.34 (0, 0, 106 pm) and (0, 0, -106 pm)

1230

<915|%25> = (const.) ro: = = e oO € Cun dc

3
->x
= (const.) (a = =) e : dx where x = r/a
re)
Oo

oe S25 32 if,
= (const.) (a7 77) = 0

1230
4 2 -2r/a
A. igs = 3 re o dr
na
rey re)

12.38 17.639 pm

12.39 0.7144, 0.6615, 0.5557 nm

12.40 0. 0, Vo ae eee
 203

12.41
4s 4p 4d 4f

inl = VaC2
+ 1) £ 0 N24 V6 4h V12A
Radial modes 3 2 1 0
Angular modes 0 i Zz 3

12.42 @ = il1sa(1) i1sp(2) - I1sa(2) 1sf(1)

Interchanging coordinates gives
Isa(2) 1spB(1) - 1sa(1) 1sB(2)" = wp

12.43 The inner electrons (1s) screen the nucleus, but since the
probability density of the 2s orbital is greater near the
nucleus than that of the 2p, the 2s electrons are not
screened as much as the 2p electrons, and therefore are bound
more tightly (have a lower energy).

12.44 Those with outer electrons in s orbitals are spherically

symmetrical: H, He, Li, Be, Na, and Mg.

12.45 Sc 1s72s72p°3s23p° 3d4s2

Sc* {argon core] 3d4s

Sc2* [argon core] 3d

Sc3t [argon core]

12.46 230A, 16.40 nm

12.47 54.4 V 164.0 nm 121.0 nm

CHAPTER 13: Symmetry

ie el E, Cy(z), oy (xz), o,,' (yz)

NS} 2? E, C3, 30,

Cy (z), S4(z), C, (x), Cy (y), 2C, ’ iv Op

13.3 Dy Cy(z),

o,(xz), o,(yz), 204

13.4 E, 4Cz, 4S¢, Cy(x), Cyly), Cy(z), 384, Cy (x), Co (y),

Co (z), Cone, 5Us 36}; 604

AIS is) E, C,

13.6 E, C3(z), S3(z), 3Cy, op, 36,

NASs 1 E

13.8 Ey, CpeehCase 20ee. 29,

13.9 Bre @ayn dC34 andaas
13.10 E, Cy(z), Cy ly), Cy(x), i, o(xy), o(xz), olyz)

13011 RCo. Soret ie? (ae ee

1312 E, Cy(z), Cyly), Cy(x), i, o(xy), o(xz), olyz)

13.13 EMS A(z) Ca (2h etConn) Cy yan 2a,

13.14 E, Cy(z), o(xz), o, (yz)
13205 E, Cy(z), Coly), Cylx), i, olxy), of(xz), olyz)

13.16 E, 4C3, Sy(x), Syly), Sglz), Cyolx), Cyly), Cy(z), 604

alten Le) E, Cg(z), S3(z), 3C€y, oo, 30,

13.18 E, i

i3515 E, Cz, 3Cy, i, 3604

 205

13.20 Construct the operator multiplication table for the point group
Con: ;

SOLUTION
E c* op i

E E Orn Sh i
al 1
C, C, E i oy

o o i E (¢ i
h h 2)
: : 1
i i oF Cy R

3.21 List the operators associated with the 56 elements and their
equivalents, if any. How many distinct operations are produced.

Thus an S¢ axis implies the existence of both a C3 axis coincident

with the S¢ axis and a center of symmetry (i) Only the se and
ee operations are distinct operations characteristic of only the

S¢6 axis.

13.22 The C; point group has only the symmetry elements E and i. Write
the matrices for these two symmetry elements and show that they

follow the same multiplication table as E and i.

SOLUTION
1
E =| 0 1 0 i= Os2 -1 0
0
206

1 0 0 0 0

EE = 0 1 0 = £ ii = 0 1 0

0 0 1 0 1

ie <0, MO ais a0" 0

iE = 0 -1 0 = i Ei = 0 -1

0 0 -1 0 0 -1

The multiplication table is E i

E E i

i i E

13.23 01, Es 4C3, 4S¢, 3C,, 384; 3Cy, 6C, s ds 36}; 604

13.24 Doq E, S4> Cy, 2C, > 264

a Se?4) C,; E, op

13.26 Dey E, Cs, Ss, SCy, Op So,

t3327 Coy E, Cy; Gy2, Cy

13.28 Den E, Ce, C3, S6> $3, C,; 3Cy , 3Cy ’ 1, Oy?

30, 304

US Sea? Dag E, Sg, Cy; C,, 4C, é 404

137530 01 See 13.23

13 331 D3y E, C3, $3, 3C,, Op? 30,

tsa Ty E, 4C3, 384; 3C,, 604

13.33 Coy See 13.27

13.34 Ce See 13.25

ie Baer) Den See 13.31

 207

13236

ETE | *See 13 rea |

13.38

13.39

13.40

13.41

13.42

13.45
CHAPTER 14: Molecular Electronic Structure

14,2 The internuclear repulsion ZZge"/4ne Rag is omitted from the

hamiltonian operator Hey of a diatomic molecule. If Yo, is an

A .

a
eigenfunction of Bey with eigenvalue Ee. what is the eigenvalue
aA
of the operator Hey + ZZge"/4ne Rag?

SOLUTION
i. Beet ;

et i. 4ne R Te cans Pel

o af
2 2:
A
Z Ze Lie Lene ,

H + 2 y = E ae Pe » = Ey
eltel 4ne R el el 4ne R el el
o af o af

E. = “E + ZZ Blan R
ent a a af

14.2 Given the equilibrium dissociation energy Dd; for No in Table 14.2

and the fundamental vibration frequency 2331 cm 2, calculate the

spectroscopic dissociation energy Be in kJ mo1 2,

SOLUTION
1 pe) = (6.626 x 1074 5 s)(2.998 x 10° m 5 )(2.331 x 10° m -)
aa 2(1000 J kJ) oe ae
SC
(6.022 21100)
—
mmoles}
= 13.93 kJ mol
D) SDs e 1 ehogr
2 0
ee= moss avian ianGs
941.4943 nol >
This is the thermodynamic dissociation energy at absolute zero.
The standard change in enthalpy for dissociation at 0 K calculated
from fable: As? ae. 941.57 ET malo.
 209

14.3 Derive the values of the normalization constants given in

equations 14.27 and 14.28.

SOLUTION
she = C(1s, + 1s.)

%,
2 ake
Pa
= {¢ (1s,
2 + 21s,1s, +
2
1s, )dt

2
iC E sa) 1s,1spdt + 1

¢ = : — where § = 1s s,1s
1isidt
(2 + 28)2/2 AB

| es Cc (1s, - 1s,)

at
r
= (Gy
2 (1s,
ae 21s,1s, + 1s, )dt
2

Boe \eslo os]

/ il
Ce
(2 - 28)2/2
14.4 Plot Pp and ~y versus distance along the internuclear axis for Hy

in the ground state without worrying about normalization (R,

106 pm).

SOLUTION
The values of these wavefunctions along the line through the two
nuclei are given by
rae oe Ue a ae
&
» (ou (eo IZl/a, a o (2 = R,)/a,]
u
where Z is the distance measured from nucleus A toward nucleus B,
and C and C’ are the normalization constants that we are going to
ignore. These plots are given in Fig. 14.5.
210

14. b} Plot % and %y- versus distance along the internuclear axis for

Hy in the ground state without worrying about normalization (R, =

106 nm).

SOLUTION

See Fig. 14.5.

14. 6 What are the normalization constants for P, and Yu for the

hydrogen molecule ion? It can be shown that the overlap integral

S is given by S = [1 + (R/a,) + (R?/3a*) lexp(-R/a,).

SOLUTION
Since R/a, = 106 pm/52.91 pm = 2.003

S = (1 + 2.003 + 2.0037/3) exp(-2.003) = 0.5856

According to Table 12.1 the normalization constant for a 1s
wave function for H,~ is

e378 = Wena pw 2 61466.5,100 tpn

For %s the normalization constant is

-3 =3/2
1.466 x 10 pm
Pe eee: tee!
/2
2a + si)
For Vu the normalization constant is

3 —3/2
1.466 x 10. pm
= 16610 e410 en.
iLfa
[21 — <8)

14. 7 Express the four VB wave functions for Hy as Slater determinants.

SOLUTION
: 1s, (1)a(1) 1s, (2)a(2) : 1s, (1) (1) 1s ,(2)B(2)

hfha ily] ae ey
1s, (1)B(1) 18, (2)B(2) 2 Isp(1a(1) 1s, (2)a(2)
 Paalal

Is, (1)a(1) 1s .(2)a(2)

1s, (1)a(1) 1s),(2)0(2)

pz is the same as > with B replacing a. Y4 is obtained from y,

by replacing the minus sign with a plus sign.

14.8 Show that the hybrid orbitals for tetravalent carbon given by
equations 14.53 to 14.56 are orthogonal.

SOLUTION
Ste Kl, As
ee (i) ee (Cia) ed:

= 24 ee s ee px et
Py PING
pz cS
tot px 1g py
2 gn)
pz
dk

cross terms do not contribute since atomic orbitals are orthogonal

=
1 2 +
2 -
2 c=
2 d
>| (v Pox Poy Voz )>

= + (1 7 = 119 — 2) = 0

since orbitals are normalized.

14.9 Show that the normalizing factor for an sp hybrid wave function is

Ay ALA

SOLUTION
eae AS aaa, Fy

D 2 2
N (g i gODodv = d= N y Fo dents 2 , ¥, dr tildgngtde

1
1 = n? {1+2x0+1] = Nn?(2) v2 = ; N = —_—
Peilp,

14.10 Discuss the structure of the methyl radical and the location of

the unpaired electron.

SOLUTION

The CH3 radical is planar with the 3-two-electron bonds due to the

overlapping of the sp2 orbitals of C with the s orbitals of H.

The odd electron is in the remaining unhybridized p orbital which

is perpendicular to the plane.

14.11 How many electrons are involved in sigma and pi bonding orbitals

in the following substances: (a) ethylene, (b) ethane,

(c) butadiene, (d) benzene?

SOLUTION
(a) 106, 2n (b) 140, On (c) 186, 4n (d) 2460, 6n

[o electron pairs not labeled]

(a) H é rau (b)

b CemiGe ¢ Hy ose 0” a) Ce eee
H wil H

(c) Tt (d)
H- ee edhe
& Cr co © Cr
Hite Ope Co. OH any oot
= i H * ie —H

14,12 The heat of hydrogenation of cyclohexene is -121 kJ mol and the

heat of hydrogenation of benzene is -209 kJ mol, What is the
reduction of energy due to the formation of the n bond system in
benzene?
 213

SOLUTION
If the molecule hexatriene existed, its heat of hydrogenation
would be expected to be 3(-121 kJ molt) = -362 kJ mol,

is I eS
hexatriene benzene

The resonance stabilization is equal to the difference in heats of

hydrogenation.
=362 kT mol* = {(-209 ki mol‘) = —1'53 ET mols?
14.13 Using data in Table A.1, calculate the electronegativities of Cl,
Br, and I. The electronegativity of H is taken to be 2.1.

SOLUTION
ne A prer B 10407 LE(Meee B phe oul
2:
El AgS-A)) eae B(Re=aB) lean
For HCl

Xo47 Xp 0.0497 < 92.307 + 217.965 + 121.679 —- 4 [2(217.965)

+ 2(121.679)] MC

Xoy ee = 1.0 Xo} eR bed |

For HBr
Xp = x,,| = 0.0497 «(36.401 + 217.965 + 111.884 —- : [2(217.965)
2

+ 2 x (111.884) - 30.907] He

Br 221 Ss “0.7 er 2.8

 For HI

by = x, = 0.0497 <-26.49 + 217.965 + 106.838 —- 5 (2(217.965)

+ 2(106.838) - 62.438] we

xr 7 2) ee Xy = 2.3

14.14 Explain the relative enthalpies of formation (Table A.1) of

HCl(g), HBr(g), and HI(g) in terms of electronegativity concept.

SOLUTION
Cy Br 7

Electronegativity of halogen atom 3.0 Ziad oS

A,H® (298 K) of hydride in kJ mol+ -92 336 +26

According to the electronegativity concept, the bond in HCl should
be stronger than in HBr, and the bond in HBr should be stronger
than in HI. This is in accord with the fact that more heat is
evolved when HCl is formed from its elements than HBr, and more
heat is evolved in forming HBr than EI.

14.15 For KF(g) the dissociation constant D, is 5.18 eV and the dipole
moment is 28.7 x 10730 C m. Estimate these values assuming that

the bonding is entirely ionic. The ionization potential K(g) is

4.34 eV, and the electron affinity of F(g) is 3.40 eV. The
equilibrium internuclear distance in KF(g) is 0.217 nm.

SOLUTION
The work required to separate K* F from the equilibrium inter-—
nuclear distance to infinity is

get 1°) =. 0a, 602 = 100PEC)e (ONRDER et IORCON mo Lca)

erat 217 x10” »
-18
Sods 10? ye gates Ue ee = 6.64 eV
1,602 2 100. eve”
 PANS)

Since KF actually dissociates into neutral atoms, the ionization

potential of the metal has to be subtracted and the electron
affinity of the nonmetal has to be added to calculate D,:

Da. = 6 -64.— 4.34 493.40 = 5270. oV

This is higher than the experimental value (5.18 eV) because there
is some repulsion of K* and F. due to inner electron clouds.

The dipole moment expected for the oversimplified structure K- be

is

(1. 600ix 100° €) (217% 10°22 oo) = 34.7% 10-8? Ce

14.16 The equilibrium internuclear distance for NaCl(g) is 236.1 pm.

What dipole moment is expected? The actual value is 3.003 x 10°29

Cm. How do you explain the difference?

SOLUTION
\ (1.602 x 10-29 c)(0.2361 x 109 m)
3-783 x 10°22 C m
The actual value is less because the ions polarize each other.
The positive ion attracts the electrons of the negative ion toward
itself, and the negative ion repels the electrons of the positive
ion. The more polarizable the ions the larger the effect is.

14.17 Show that the SI units are the same on the two sides of equation

14.84.

SOLUTION
N 2
Kea LS CG a + x) nh = Ch
K+ 2 p 3é 3kT e v

2 ee
coe dipole moment 2 Cia Cm 2, &
~ electric field strength Vv as J cl e m- 3

€ = c? wae Ae
216

Left side: Si Sy mapmols

=e
kg m

os Oo nt We PSges Pret s -1
Right side: Eee tes ee es at a = m mol
CaN kg m_ s kg m s

14.18 The molar polarization p of ammonia varies with temperature as

follows:

t/-¢ yA ee 35.9 She it3;9 139.9 ize

edt’ mol? RAEN | 55.01 51.22 44.99 42.51 39.59

Calculate the dipole moment of ammonia.

SOLUTION
N Z
PP £ A ie 4
rouse (, i Os i ox)

The slope of a plot seu versus 1/T is

m 7 3 =i =
ag yg O25)
OR MOLE dao hs io toate mol gaa
cee duct 1s Kae
ig:
52 See lOBabne inole wk

(esos P10 in nota K)9ke |

h = a

Ne

(5255100 2.3
-m mol 2K) (9)(1.381x10
2°J K 1) (8.854x10 ~12,.2,-1,,-2
22C2N )
69022"% 10-° “mole

SO 8sxIOi On

(Solution to 14.18 continued top of page 217)

 217

60

20

0 | ie = (oie “al
10° kK/T

14.19 At 1 bar the relative permittivity of NH, gas is 007 220 eat
292.2 K and 1.003 24 at 446.0 K. Calculate the dipole moment up
and the polarizability a.

SOLUTION
er 2rage aS
CTR pe or + a0C
re)

Assuming NH3 is a perfect gas P = pRT/M

Atay = 29 2h Kas

M/p = RT/P = (8.324 J K 2 mol

+)(292.2 K)/(101,325 Pa)
ST A ee any es
218

=3, 3 at
(K- 1) M/p = (1.007 20 - 1)(23.98 x 10 ~ m mol ")

Mis707 100° a ol

At T = 446.0 K
M/p = (8.314 J x: mo1
+) (446.0 K)/(101,325 Pa)

S236 cre On ol
- =1
(i— 1) Hip = (100031241) 36.602 100° wt Bot)
Ske 10 a mole

We have the following two simultaneous equations

2 (ee

LTTae 0 ee ee ee ce) eee ¢ page

é g pases ~ 39 Oo1k(292.2 K) -
0)

D) (an

PETER es ear ee ke eS * alse

: * ro tee 36.k(446.0
0)
k) é (@)

Taking the difference

N He
-4 3 =i A bowl 4 1
eee tk Pits Che ‘sos K 446.0 K
2
Nip
A 4 3 al
Car as 0.0458 m mol K
Oo

(0.0458m°mol 2K) (3)(8.854x10 -°C°N tm ~)(1.3807x10 2°93 Ky 1 )

6.0220 H0ceee le

SeoR, 10, Ce

Solving the first equation forq@

& wae
a OP ge to nol tt» Se ee
Na = ee 3¢ (292.2 K)
 219

a ee te se AN) ae PT ae
6.022 x 10 mol

(6022 510. mol 5.28 x 10 Cw) oa

B(eles4 x 10,°- C°.N” m-)(1.3807 x 107° 1K 1) (292.2 K)

= 2.36% 10 9 C m/v wm
14.20 The dipole moments of HCl, HBr, and HI are given in Table 14.4.
Explain the relative magnitudes of these moments in terms of
electronegativity.

SOLUTION
30 Electronegativity
n7.087 >) Com of halogen atom

HC1 3.44 3.0

HBr 2.64 ADeots:
HI 1.00 2.4

The electronegativities increase in going from I to Cl and so the

negative charge on the halogen is greater in HCl] than in BI and
the dipole moment is larger.

14.21 Calculate the dipole moment HCl would have if it consisted of a

proton and a chloride ion (considered to be a point charge)

separated by 127 pm (the internuclear distance obtained from the

infrared spectrum). The experimental value is 3.44 x 103° C nm.

How do you explain the difference?

SOLUTION

= = 19 -9
ph = QR = (1.602 x 10 C) CO 71277--x 10 m)

=000.45010>) Cm
Treat So Adae 105 0
The charges are not completely separated in HCl.
220

14.22 A beam of sodium D light (589 nm) is passed through 100 cm of an

aqueous solution of sucrose containing 10 g sucrose per 100 cm>.

Calculate I/I), where I, is the intensity that would have been

obtained with pure water, given that M = 342.30 g mol? and

dn/dc = 0.15 g com? for sucrose. The refractive index of water

at 20 °C is 1.333 for the sodium D line.

32mm, (dn/de) Me

3N 4

32n° (1.333) (0.15 g | cm?)”(342.30 g mol -)(0.1 gcm)

B(GNOOMET10-° wot
a).U58on10) cn)”

65h 0) oa
I = —(6. = Sue T
i =e tLe, (6.25 x 10 cm § )(100 cm) 0.9938
(0)

14.23 The Lennard-Jones parameters for nitrogen are e/k = 95.1 K and
o = 0.37 nm. Plot the potential energy (expressed as V/k in K)
for the interaction of two molecules of nitrogen.
 224

14.24 For Ne the parameters of the Lennard-Jones 6-12 potential are

e/k = 35.6 K and.o = 275 pm. Plot V in J mol7! versus r and

calculate the distance r, Where dV/dr = 0.

SOLUTION
r, = 22/6 g = 21/6 (9.275 nm) = 0.309 nm
e = (8.314 J K-? mo1~1)(35.6 K) = 296.0 J mo1~1

<4 if] 46 (2)”

V/T
~!mol

a. 6
V = 4(296.
J mol
0) eat - au
14.25 494 kJ mol= 493.570 kJ mol from Table A.2

14.29 0.899 976 Ey

222

14.30 0.375 Ey,

14.31 E = 4.7483 + 2(13.5984) = 31.9451 eV
14.35
14.36 787.38 kJ mol
14.37 6.408 x 10729 Cm
14.39 Because of the higher electronegativity of Cl, the Cl atom in
CH3zCl is more negative than the Br atom in CH3Br.

14.40 4.0 x10°9 Cm 0.88 x 1049 ¢ m/v mt

14.41 5.29 x 10°9 Cm
14.42 19,500 g mo1+ 0.9980
14.43

Kain

14.44 0.429 nm
CHAPTER 15: Molecular Spectroscopy

15 ol Since the energy of a molecular quantum state is divided by kT in

the Boltzmann distribution, it is of interest to calculate the

temperature at which kT is equal to the energy of photons of

different wavelength. Calculate the temperature at which kT is

equal to the energy of photons of wavelength 10° cn, 10-1 cm,
10°? cm, 10-> cm.
SOLUTION
Tae So eeey/N

te Be _ (6.626 x 10 ** F s)(2.998 x 10° ms)

2p ae
(eset 10 =23 7K) =F 10 a)
Seater 0s ks ioe 2h 210° on

Pin eenoe a (ae ds4 Kk

oe cm, T = 1440 K
Forest f08 te. T = 144,000 K
Note that conversion factors between temperature and various forms
energy are given in the back cover.

cS Most chemical reactions require activation energies ranging

between 40 and 400 kJ molt, What are the equivalents of 40 and

400 kJ mot + in terms of (a) nm, (b) wave numbers, and (c)
electron volts?

SOLUTION
Ror 40:1 anole
(ax = <

Uu6.6260r 10° = J 2)(2.998 x 40° wre) E (610222 10° 2 mol)

-1
(ae to yenoles)
6
= 2.991 x 10. m = 2991 nm
224

(hb) cer = a = ~- 4 - =) 93345 agi

d 2.991 x 10 cm

4 4
Ee G2 20 tml 2 = 0.415 ev
(6.022 x 10 mol ~)(1.602 x 10 TeV )

For 400-kJ. mol~

yk
(aligh *4) (29925nm) 2s -aaseescee in geet?dyam
4x 10° J mol

(bo) = : = ~------F aye iaausnrens

29 D1 xO cm

5 =
(c) (0.415 eV) fa 10 i nel — ow raed smay
4S 10 7 Penele

15.3 (a) What vibrational frequency in wave numbers corresponds to a

thermal energy of kT at 25 °C? (b) What is the wavelength of this

radiation?

SOLUTION
hese = kT

mo. ET (1,381 x 108s > 72h e+) (29881 5eK) (108 Pn tcaee)
Beda boos ea, eg ee
(6.626 x 10 JK )(2.998 x 10° ms)
= 207 cm

r = = = A839 x10 > on

eo

15.4 What are the SI units for the Einstein coefficients when the

energy densities are expressed in terms of frequencies?

SOLUTION
dN /dt 5) Sil
A = - — = aaa oe Ss
mn N rs 55)
n m
 Z25

dN /dt ao peal 33 3
B Sr See eer eee Se = m - a
mn ‘ 2 -2 -1 -3 i Oy
£5 1 kg Ss s : kg s 2 J
=i
a eee = ny Ug
La fae ca Rs * i en 3
m

15.5 Calculate the reduced mass and the moment of inertia of pci,
given that R, = 127.5 pm.

SOLUTION
a ees
Phe Cd
____ (2.014 10 x 10 ~*kg mot —}(34. 968 85 x 10° kg mol _-)
fia DiAe ion eg eO5se85)arel0=--f,on1= 106,022 O4sex 10 tomoll)
eT yy Peel a kg
Petes = 01h 1604 si0e eke) (i. 37583. 10°
Reval x 10 kg a
15.6 Calculate the frequency in wave numbers and the wavelength in cm
of the first rotational transition (J = 0 —) 1) for p?°c1.

SOLUTION
= 2B ; since J = 1
4n cl

The moment of inertia was calculated in the preceding problem,

34
nas : ae x a es) — = = 1089 iD
4n/ (2.998 x 10 ms ~)(5.141 x 10 kg m )

a aos 1) OER ahem +) 2 10-899em.

ene 10 80 em et 009183" on
226

15.7 The internuclear distance of 12¢16 is 112.83 pm. Calculate the

frequencies in wave numbers for the first four lines in the pure

rotational spectrum.

SOLUTION
: 1/6.022 045 x 107° mol-
rae 1 1
ea DS ea
12 x 10° kg 15.99491 x 10 ~ kg
= sels2e10 7° kg

Y = “Gsees2 x 10-° kg) (110-8393 100)- om)

Seeieyodes 10 | keene
~ 2h 2h6262 60s Ome Te) (10a secon:I
ga 2 5; 2 —46 2 8 =1
8n° Ic 8n (1.4494 x 10 kg m)(2.998 x 10 ms)
(3.863 ces
—~
J Sey)

0 1 3.863 cm?
1 2 7.725 cmt
2 3 11.588 cm
3 4 15.450 cm+
15.8 The far infrared spectrum of BI consists of a series of equally
~_ =
spaced lines with A-<J = 12.8 cm 1 What» is (a) the moment of
inertia, and (b) the internuclear distance?

2p = 8n
—2h cl

hee J (6.63) 10°" Js)

rock 8n- (2.998 x 10° m Ge Cane lone “a
 227

are Sric ule Rg?

Absa 1B
os = A 1/2

pn = |h4:37 x 104" kg m?)(128 x 10? kg)(6.02 x 107? mot?)

e€
@272 10" kg) (1 x 16°" kg)
i 163 pm

Gy Show that for a rotational spectrum of a diatomic molecule the

rotational quantum numer (to the nearest integer value) for the
maximum populated level is given by

J = kT £0
max 2hcB 2

SOLUTION
aN —BheJ (J_+ 1) -BhcJ(J + 1)
J) kT Bhc kT
a =- 2e at (23 + 1) iT e

At the maximum value of Ny this derivative is equal to zero so

that the above expression is obtained. For H>C1 at 300 K

(1.3806 x 10 73) (300)

ee 2(6.626 x 10°4)(2.998 x 10°) (1044)

i 2.7, which rounds to 3

228

15.10 What are the relative populations of the first five rotational

levels for B5¢1 and 12¢169 at room temperature?

SOLUTION
N, = K(2F +1) a thes(I + 1)B]/kT

For HCl, Pe PhaheccRanet

hcB = (6.626 x 10 P) Ses) (2099 79.0x 10° m s4)(1059 ney

22
210416 10a
—-22 =23
-—(2.104 x 10 ““)J(J + 1)/(1.3806 x 10 “~) (300)
N,/K =—(23et) Iie

Soke 1) ¢@ 005080 J(J + 1)

For occ.Oo, fl 179310 can

cba =B)
wT? 3 9.26 x 10

=3

J Pcl 12,16,

0 1 1
i! Bdol 2.95
2 3.69 4.73
3 3.81 6.26
4 3.26 7.48

15.11 The moment of inertia of 169120165 1S Yeilsg? se 10746 kg m2, (a)

Calculate the CO bond length, Rog, in CO,. (b) Assuming that

isotopic substitution does not alter Rog: calculate the moments
of inertia of (1) 18912185 and (2) 16913166

SOLUTION
(a) Since the co, molecule is symmetrical, the carbon atom is on
 229

the axis of rotation and does not contribute to the moment of

inertia.

I .
= 2mRoo yl

Rog
-= (J/2m)
1/2
= E 12
(7iv bien 10 igiaks m2 )(610229045 x410-° mot -)
Seis 5oa°9) x 16 ee omol-
= (0.1162 nm

Cv yas rates
2
I = 2mRog

2(17,999 16 x 10° kg mol *)(0.1162 x 10° m)”

6.022 045 x. 10-° mol.”
='h3.011 x 01" ‘yuck
For 16513,.16) the moment of inertia is the same as for 16 512,169 |

15.12 Derive the expression for the moment of inertia of a symmetrical

tetrahedral molecule like CH, in terms of the bond length R and

the masses of the four tetrahedral atoms. The easiest way to

derive the expression is to consider an axis along one CH bond.

Show that the same result is obtained if the axis is taken
perpendicular to the plane defined by one group of three atoms

HCH.

SOLUTION

wie’

SH sin 70.529° = h/R where h is

the perpendicular distance
E to the axis
230

8 mR
eee Teii eG (GI ena3

If the axis is taken perpendicular to the page through C

tt)

I = 2mk” + 2[R@sin7(90° 109. ty) = § mR”

15.13 What are the rotational energies for the symmetric top NH, for

J =1 and J = 2? Given: Ip = 4.41 x 10°47 kg m? and I, =

2.81 x tase kg m~,

SOLUTION
Be ot fee eas eee TS AEK1005 150 die gO
ancllas |auto 007 0° cmis +) (281 1G gem)
= 9.96 cm

cam th a 15054: x10 hs Jes

~ 4ncIp a Se 10 -1
| 4n(2.997 x 10 cms )(4.41 x 10° = kg m’)
—Onis ae

Rieane = (9.96 ene eh Ge til) =o E (S35 261 Caee) K-

Tie =i ok ONE = omOGt en oy) ee ot mene

Ko=ooel B== 719.92 — 3/01) = 163 1 cm au

= 4, = AL =j)
Tf J=2, K =O, E = (9.96 cm )(6) = 59.76 cm

Kieu Ee somICecnme ons oltcn as = 56n1 5Scnie

Kim 2:2, WE 59076hom> = (3, 60tem SCA) M=ndSea2 ome
The fundamental vibration frequency of H5¢1 is 8.667 x 1033 ney

What would be the separation between the infrared absorption lines

for W5¢1 and H37¢1 if the force constants of the bonds are
assumed to be the same?
 231

SOLUTION
pi ua CL
a Gy
For HCl
-3 24 -3 -1
He (1.007 825 x 10 ~ kg mol —)(34.968 85 x 10 ~ kg mol ~)
7 = a a 3p =
(250076166 < 108 tyueol) .) (600200045 x 10-24mol, 4)
= 162668 x 1057" kg
Por he et
-3 ~1 —3 -1
_ (1.007 825 x 10 ~ kg mol —)(36.947 x 10 ~ kg mol _)
eS =3 1 Me 1
(272959 xP 10" Kgrmolims(6.022 045. x°10 “mol ~)

=e e1e62911 = 108” ee
1/2
eg
Seoginoe ag
abe =
Se ee =
7) oo
Wy)
B 2 By 1
et (249979 4810° 1mn sa)
ame oe LO -9 om
8.667 x 10 s
1/2 1/2
Moe a Bo 1.629 11 x 10 7’ &
=9(3459-0 nm) |ee 34616 on
wal 1.626 68 x 10 ~' kg
Ay = Ay = 2.6 nm

eran Calculate the force constants k for fENS in the ground state and

in the 31, state. (See Table 15.4)

SOLUTION —3 all
i= z 2 14.0067 x 10 st fel = 1.162 952 x 10 26 ke

216.022 045. x 10% s01 ~)

1/2
~J)= = (|
T
e os ee
Pe (reyes 12035 857 m (2,997 924 x Niet Ce lon
232

= 2295.41 Nm
1 for
iv”
)
g
=) 8 sit yew
Ek = (2nCl73 339m )(2.997 924x910 ms len

= 4959 $61 Niwa Pore oon

&

15.16 (a) What fractions of H°°C1 molecules are in the v = 1, 2, and 3

states at 1000 K and (b) 2000 K?

SOLUTION
Cast at ated ~ ‘ eS
heme
it tneSe (67, 6262x210 oh J s)(2.998
a x 107° cm s 1) (2990.95 ) cm)
See ee

= 4302 K

(a) At 1000 K, equation 15.70 yields

eo 4-302 -4.302
fh =, (L- Vie = 0.0133
re Sete @ 4-302) -(2) (4.302) = 0.0018

i sari 9 4-302) .-(3) (4.302) = 0.000002

(b) At 2000 K

f= Ue e 7isl Je ee are ey! = 0.1028

7 aane pote lel (2 (2 15 L) Ne ener
perskcrs eg 151, (3) (28ST eae HUIS

15.17 Given the following fundamental vibration frequencies:

H?>¢1 2989 cm4 H2D 3817 om+

202° C1 2144 cm} pp 2990 cm}
Calculate AH® for the reaction

Hci (2 = 0) + 2p2p(-w=0) = 2p35c1(-e7= 0) + H2D(~/= 0)

 233

SOLUTION
Ane Ee Be Ee E = ho~/2 for v = 0
2
Aoceee cat 4d 2 R11 2980n Se S990 =. 1S cn
AH® = - + hea

= - +(6.63 BROS Sire) (55x10 ahaa (ene cm 4)100 eae)

=$sisg9 Gitoe a
SS {inyo s7i0) 6022 = 10 mol) ee pot
a5 .18 Calculate De for H,~ using the information that Do = 2.650 78 eV,
0, == PRAOEP Vein =! ae Pe = OG 2 eCMl 1 a aaand be aPaes 0.6 cm”.
=i

SOLUTION
Dern ei eels) a pte e424 Ww18

(2.650 78 eV) (8065.47 cm+) + (2321.7 cm-+)/2

- (66.2 cm *)/4 + (0.6 cm-)/8
22,540 cm
The value in Chapter 14 is 22,527 cm,

nS 19 Using the values for w, and WoXe in Table 15.4 for 1435 ¢4

estimate the dissociation energy assuming the Morse potential is

applicable.

SOLUTION
wo, = 2990.95 om wx, = 52.819 om x, = 0.01766
The zero point energy lies at
1 a il = 1 -1
G(0) =
7 e
= -_ _
Z exe =
5) (2991
_
cm ~) _
ii (52.8
—— oD .
cm ~ )

|
Ul ay BS le)i) is) B
234

W -1
- S a 2990595 ,cm 5 =il
Os dz, ~ 4(0.017 66) terete
DD ee G(0) = 42,341 - 1482 = 40,859 Bre

= (407859cm) (102399 x 10°" eV cn) wees sO Tey

The actual value is 4.434 eV

15.20 (a) What fraction of Hj(g) molecules are in the v = 1 state at

room temperature? (b) What fractions of Brj(g) molecules are in
the v = 1, 2, and 3 states at room temperature?

SOLUTION
SESS a
(a) Using equation me (1 =<e . oy Ne NL

he hee?_ (6.626 x 10° 34 J _s)(2.998 x 10° 0 om s_') (4401 cm)

ou tt (1.381 x 102° 3 K2)(298 K)

=) 2d? fk ee eae ae 108e

(b) For Br,, w, = 325.321 car’

heciee HOSE (61626ex 10> «Ts )2098 eee 10> emia Ga shotcnaa)
IS eas (1.381 x 102° 3 x4)(298 K)
= 1.570
f= a cyte Gun ae A = 0.165
bares. ees 10, ) (2) 0) neers
eee a 1510,
(2) 00)

15.21 The first three lines in the R branch of the fundamental

vibration-rotation band of H29C1 have the following frequencies in
cm+; 2906.25(0), 2925.78(1), 2944.89(2), where the numbers in
parentheses are the J values for the initial level. What are the
’
values of Wo» By 5 | Bs B,> and a?
 Pa

According to equation 15.75

= w (By + By, ym + (By _ BL )m”

=a + bm - + cm where m = a + 1

29062255 =) a. te bo + cc

2925.18 <= a. +e2b" + 4¢

2944.89 = a + 3b + 9c

a v=. 2886/30 ¢ = ®6
b =) 2033:6) = By + BL

c = -0.21 = BL - BY

B = 9.98 cm
-1 = 8B —-
3
—'a
Vv e 2

OMeVv IOL Overt) cB e Hs 2

a
B =. 40,30 a6
e€

a L wrgtsieu*

15.22 In Table 14.1 D, for Hy, is given as 4.7483 eV or 458.135 kJ mol,

Given the vibrational parameters for H, in Table 15.4 calculate

the value you would expect for A,H® for H(g) at OK.

SOLUTION
1 1
a ~ ae ba Me if 4 veae

-1 .-1 - 1
5(4400.39) 1
+ 3(120.815)
= (4.7483 eV)(8065.478 cm eV)
362127 toms 018 2432/9175 49 “mol
H, (g) 2E(g)
A
An 2A A (H) = 432 /175°h mol
(0)
236

AH (H) = 516. Osstktinol

Table A.2 gives 216.037 kJ nota.

15.23 Calculate the wavelengths in (a) wave numbers, and (b) micrometers

of the center two lines in the vibration-rotation spectrum of HBr

for the fundamental vibration. The necessary data are to be found

in Table 15.4.

SOLUTION
The reduced mass of 78%p, is given in Table 15.4 as

0.995 2858 x 10 -3a

aone? kg mol -1 _= 1.653 23 x 10° -27 kg
6.022 045 x 10 ~~ mol
Thee Rae ends G53 24x TOS a
Cs Se 10) teh
m3 3040500410 | keen
B= —
8n cl

¥
Ren EE
(60626 x SCS
105 *RG
ils) (LOR a
oman)
ay 8.47 cm
-1
8n (2.998 x 10 ms )(3.3045 x 10 kg m )
~ wv
(a) ey = 29, - 2BI" where J" = 1,2,3,....
=a 2649.67 cm =1 - =1
2(8.47 cm’) = 2632.72 cm -1
re oe Z, POR + 2980" nwhere.J!) =< 0, lsat 4
== 2649.67 cm ~1 + -1
2(8.47 cm) = 2666.61 cm -1
(b) A, = 1/2 = 3.798 34 x UY ore cays ee
dp = tices = 3.750 08 x 10. ~4 cm = 3.750 08 um

15.24 How many normal modes of vibration are there for (a) SO, (bent),
(b) H,0, (bent), (c) HC=CH(linear), and (d) Cele?
 237

SOLUTION
The number of normal modes of vibration is 3N-6 for a non-linear
molecule and 3N-5 for a linear molecule.

(a) 3N-6 | ig NAN = 3 (c) 3N-5 iH} ic 7)

ray " ~
(b) 3N-6 12-6) = 6 (d) 3N-6 = 36-6 = 30

15.25 List the numbers of translational, rotational, and vibrational

degrees of freedom for (a) Ne, (b) Ny, (c) CO,, and (d) CH,0.

SOLUTION
Molecule Trans. Rot. Vib. Total = 3N
(a) Ne 3 0 0 3
(b) No 3 2 1 6
(c) C0, 3 2 4” 9
(4) CH, 0 3 3 és 12
*For linear molecules 3N-5 **For nonlinear molecules 3N-6

a5 .26 Acetylene is a symmetrical linear molecule. It has seven normal

modes of vibration, two of which are doubly degenerate. These

normal modes may be represented as follows:

>< t t
€H—— c2Ct ——— > H———
c=C ——E
na ‘ 4 Si
oud = 3374 cm 4 = 612 cm

>< t t
H—— c=Cc—<— H H—— C=C ———-H
Al ~ Mies =il
7), =| 1074 om 2 = 729 om

H >< C=C H>

ee) =) 8287 a
238

(a) Which are doubly

the degenerate vibrations?
(b) Which vibrations are infrared active?
(c) Which vibrations are Raman active?

(a) ca and po since they can also take place in a plane perpen-

dicular to the plane of the paper

(bo) and <<. because the dipole moment changes during the
3 5
vibration
“~~. aw, —_/
(c) wu) <I, and aes because the polarizability of the mole-
cule changes during these vibrations

When CCl, is irradiated with the 435.8 nm mercury line, Raman

lines are obtained at 439.9, 444.6, and 450.7 nm. Calculate the
Raman frequencies of CCl, (expressed in wave numbers). Also

calculate the wavelengths (expressed in pm) in the infrared at

which absorption might be expected.

SOLUTION
an = —--- S95 2513.
ae incid Ne catt

at 1 -
= ee eee oe = 214 cm
435.8 x 10 cm 439.9 x 10 cm

ail 1 =6
7 = ie i meer ee 46.7 x 10 m
Ww 214 cm

For the remaining lines

i Rael ee -1 312 454 759
A/pm 32.0 22.0 13.2
15.28 The first several Raman frequencies of Lane ane 19 S90 8h m2 Soule
35581250 435762, 51,721, ‘and “59 6620¢messeeThose. Ih nee car oree
to pure rotational transitions with J = 1,2,3,4,5, and 6. The
 Za

spacing between the lines is 4B, . What is the internuclear

distance? \

SOLUTION

(14,003 07 x 107° Epc

eS = =
(28.006 14 x 10 2 kg) (6.022 045 x 07 mol sf

i162 65tx 0) kg
The average spacing between lines is 7.951 cae” and so
Bo =g201.951 om)*)(102 cm m4)/4 = 198.78 m! since AJ = 2.

i oe, aah
e 2 2
8n cur.

n> ( h
1/2

8 cuB

6626176 2100 Ts
26 it
8n-(2.997 924 58 x 10° m s *)(1.162 651 x 10 kg) (198.78 m ~)
110 pm

a) .29 What Raman shifts are expected for the first four Stokes lines for

CO,?

SOLUTION
T= ene] x 19.0” kg AG (Problem 15.11)
ay iene eS teiciete10s Jos) (10 meen)
: brie Sh (7ib7 3 100” kg By 1220918) au10 ae)
Sues o0Geeat Aw, = 2B (2J + 3)
= ~~

jy" Ay

2.3436 cm
w ‘oOi=)nN jo)

oo
wWwdrF
240

15.30 (a) 3.10 nm (b) 414 nm

15.31 11,604 K
15,32 (aq) 1.138 52 x 10,-° ke (b) 1.4492 x 10°46 kg m2
15:33 24.1, 4222, 6323)) 189-9 cm +
474, 29) we | oe Bn

15.34 (iyearal 2107- (by 6 15"s 10-48

(c) 6292 x 10-48% <(4)'9.22 2h1000° (kg m2
15.35 0.4515 kJ G02 65cm
15.36 113 pm

15.37 ~~) = Jhi4n-t

15.38

G27} - stokes 7 hare

Litid fF Pe We: Z O j 2 oe:

final T= 5 ee / O Z 5) 44 Sy G

ed axe ’TCNCG £ SIM GE

15.40 OS ne) 40s Sils O GEES OFS OS GEM Cc

15.41 9.10, 14.39 K

15.42 Oa, Wsalysyy ey

15.43 Bist «10-0 J 52.59 kJ 0.5449 eV

 241

15.44 (a) 26.288 (b) 3.381 kJ mol

15.45 6.216 x 1039 st = 4.83 wm

15.46 4.09 x 108° Nm?
15.47 8.9 x 10! 0.358
15.48 3.025 eV
15.49 87,510 cm? 10.85 eV
z.50 4592.8 4605.9 4632.1 4645.2 cmt
21973 2.1054" 29,1588 2.1528 pm
zS.51 1870 cm 8.45 cmt
PS «52 BL = 5.29 BL = 5.42 B, = 5.49 a = 0.13 cm

R, = 127.0 pm compared with 127.455 pm in Table 15.4.

= .53 Molecule Translational Rotational Vibrational

C1, 3 2 SN-- Se=e1

H, 0 3 3 3N =-6° =. 3
HC=CH 3 3 SNe

15.54 Molecule Translational Rotational Vibrational

NNO 3 2. 3N- 5 = 4

NH 3 3 3N - 6 = 6

£5.55 0.075 19 nm
BS .56 109.7 pm

ZS. 7 655 J mol

CHAPTER 16: Electronic Spectroscopy of Molecules

16: The spectroscopic dissociation energy of H, (g) is 4.4763 eV, and

the fundamental vibrational frequency is 4395.24 om, What is
the spectroscopic dissociation energy of D,(g) if it has the same

force constant?

SOLUTION
Since deuterium atoms are more massive, the fundamental vibration

frequency will be lower in Do than Hy. Therefore the zero point

energy for Dy) is lower, and its dissociation energy is higher.

For Hy

: (1.007 825 x 10 a © kg mol)Bie

eae OS are”
2(1.007 825 x 10 ~ee errs I—)(6.022 045 x 10°”03m. mol)
kg mol wate

ey 88367 197 x 10e.. ke

For Dy 2

a= (2.014 10 x 10° kg mol‘)

2(2.014 10 x 10> kg mol
~)(6.022 045 x 100° %mo1)
16.722 725'x°107-° kg
According to equation
11.95
®» ee ILfz
& 8. 5670797xa10 28 kg
mH, 160122) 1250 100- ke
7 4 =
w = 4395.24 cm so w, = 3109.10 cm
H D
2) 2

Aw = 1286.1 Oe

ie = 4.4763 eV + heAw/2
2
eer EOS 34 J_s)(2.9979x10
° ms ')(1.o86s10> eam
(1.602 = 10m ayeey 2)
 243

= 4.4763 eV + 0.0797 eV = 4.5560 eV

26.2 According to the hypothesis of Franck, the molecules of the

halogens dissociate into one normal atom and one excited atom.

The wavelength of the convergence limit in the spectrum of fodine

is 499.5 nm. (a) What is the energy of dissociation of icdine
into one normal and one excited atom? (b) The lowest excitation
energy of the iodine atom is 0.94 eV. What is the energy
corresponding to this excitation? (c) Compute the heat of
dissociation of the iodine molecule into two normal atoms, and
compare it with the value obtained from thermochemical data,

144.4 kJ mol.

SOLUTION
(a) E = heN,/2
= 8 i 23 51
Pu(G 62603r10) oF0s) (2.998 2105 gs 2) 6,022 0x 102" moles)
(200stee10 mw) (10° ee
Se 40sec enol.
PATE OtOarey 1o6 48S Clmelye 20 9007 13 moll
* =

ee a AMI ae holes
* -1
ee
a i et oe oe et ed SOL
7 “a ¥9y ie
hee Sp ee

a6. 2g The ultraviolet absorption of 0, includes a series of lines (the

3
Schumann-Runge bands) due to transitions from the oa ground

state to the excited electronic state ‘A which are shown in

Fig. 16.1. These lines converge to 175.9 nm, which corresponds to

dissociation to one O atom in its ground state 3p and one O atom

in an excited state 1p, What is Do for 05? EKow does this conpare

with the enthalpy of formation at 0 K? Given: The 1p state of O

is 1.970 eV above the ground state 3p,

244
SOLUTION
The dissociation energy Dg for oy) = o(3P) +. O('D) is

i 23
ee heN, (6 626x10 °* J_s)(2.998x10° ms )(6.022 x 10° mol_)
~ tisko 10; oe
Reread
Se MINE nol. Si =,
:
G0 (C680 2UkTi mol =r=) 006, 465. bom rc View)
= 7.050 eV
Since. 0(°P) = O('D) AE = 1.970 eV
The dissociation energy of 0G) into 20(3P) is

Do = 7.050 - 1.970 = 5,080 eV or 490.14 kJ mo11,

From Table A.2 AgH® (0K) = 2(246.785) = 493.57 kJ mol
16.4 The spectroscopic dissociation energy of sci is 1.542 38 eV

according to Table 15.4. What wavelength of light would you use

to dissociate ground state molecules to ground state atoms if you
wanted the atoms to fly away with velocities of 103 mi s 19

Ee) (15420381 6y) (96n4asuT cmole veViale ee 2

2(> 126.904 = As kpemdll ) C10; pee
= (1488 2 10° 21269 2 10°) mol
wa OT Sia 107 mole oe Nhe/2
, = (6.022
x 107% mot”) (6.626 x 10°" J s)(2.998 x 10° ms“)
2,157 x 10° J mol
= 413500y 10 em, = 7499 9onm
16. § A solution of a dye containing 0.1 mol Ll transmits 80% of the
light at 435.6 nm in a glass cell 1 cm thick. (a) What percent of
light will be absorbed by a solution containing 2 mol Lit in a
cell 1 cm thick? (b) What concentration will be required to
 245

absorb 50% of the light? (c) What percent of the light will be
transmitted by a solution of the dye containing 0.1 mol i> in a
cell 5 cm thick? (d) What thickness should the cell be in order
to absorb 90% of the light with solution of this concentration?

SOLUTION
nog ATT) ec]

log (100/80) e(0.1 mol L~1)(1 cm)

=" 0.969 1 nol ent
(a) I = I e 2-303 ecl
O°

(100)exp [-(2.303) (0.969 L mo1~! cm 4)(2 mot L71)(1 cm)]

= 1.2%
(b) log (100/50) = (0.969 L mol? cm+)(1 em)c
c -= 0.311 mol Lt
(c) I = (100)exp[-(2.303)
(0.969 L mol tem +)(0.1 moi L74)(5 cm)]
= 32.8%
(d) log (100/10) = (0.969 L molt cm )(0.1 mol L>4)1
1 = 10.3 cm

16.6 The absorption coefficient a for a solid is defined by I = I,e ™,

where x is the thickness of the _ sample. The absorption

coefficients for NaCl and KBr at a wavelength of 28 um are 14 and

On25 om), Calculate the percentage of this infrared radiation

transmitted by 0.5 cm thicknesses of these crystals.

SOLUTION
-1
aot l4 cm )(0.5 cm) 0.091%
For NaCl I = Te = 100
246

MGs cnt) (OnShem) 88.2%

Fox KBr I = 100 e

16.7 The following absorption data are obtained for solutions of

oxyhemoglobin in pH 7 buffer at 575 nm in a 1-cm cell:

g/cm Transmission, &

aoe 53.5
BW e0r4 35.1
10 =ail0ed 12.3
The molar mass of hemoglobin is 64.0 kg molt, (a) Is Beer's law
obeyed? What is the molar absorption coefficient? (b) Calculate
the percent transmission for a solution containing 105 g/cm.

SOLUTION
Ane
grams per cm 3 mol L zy 1/1, log(I/I,) e/L mol eS~ cm

3x10 °. 4.69% 10° 05535 =0.272 5.80 x 104

SE xt £0) (1282) 20102 eae or ss -0.455 5.82 x 104
140x104 15.64x10° 0,123 -0.910 5.82 x 104
Beer's law is obeyed and the molar absorption coefficient is
5.81 x 104 L mol! cm},
(db) Slog(l/T)e =) sec!
= =[5.81 x 10* 1 mot? om “100.564 x 10° nolL 4) om)
= -0.091

I/t = 0.81 or 81% transmission

16.8 The protein metmyoglobin and imidazole form a complex in solution.

The molar absorption coefficients in L molt cm of the
metmyoglobin (Mb) and the complex (C) are as follows:
 247

' = “Mb Pe ote Ula ke

5 10° L eoite ie 10° L Es al te

500 nm 9.42 6.88

630 nm 3.58 1.30

An equilibrium mixture in a cell of 1-cm path length has an

absorbance of 0.435 at 500 nm and 0.121 at 630 nm. What are the
concentrations of metmyoglobin and complex?

SOLUTION
log (12/4) = A (ec, “up EC) 1

At 500 nm 0.435. = -«9.42x10%c, + 6.88x10%c,

At 630 nm 0.121 = =3.58x10%c, + 1.30x10%c,
Solving these equations simultaneously

Fil 2.17 x 10-> mol L>! metmyoglobin

do) 3.48-x. 10; moter complex

16. The absorption spectrum for benzene in Fig. 16.6 shows maxima at
about 180, 200, and 250 nm. Estimate the integrated absorption co-

efficients using Emax? 1/2 and assuming that the width at

half maximum is 5000
1
cm ~ in each case. What are the three

oscillator strengths?

SOLUTION
At 180 nm
saaxh
sg = (50.1 x 109 L moi”? cm) (5000 om *)
= 2.50 x 10° L mol * cm~
f = (4.33 x 10° moi tL cm2) (2.50 esi ere mol Cnet) = 1.08

At 200 nm

ehEmA 445 = (7000 L note om) (5000 cm)

248

= 3.5 x 10. L ole” ome

¢ 2 (3 5 o2b10! Lemole cms)

CNST S100) mol Le om?) Seca

At 250nm
Emax 4g = (100 L moi? em™4) (5000 om™*)
= 95 x 10° L nore cnre

fp 2° %cangs 107 mar Lee? Cs 0 not ome" 92" 08 0022

16.10 An absorption band has a riaximum molar absorbancy index of 2 x 104

L mol? cm + and a width at half-height of 4000 cm), Assuming

the band has a triangular shape when plotted against wavenumber,

what is the integrated absorption coefficient for the band?

SOLUTION
a ow
ed J 1.06 Emaxe <4 19

(1,66)\(2e5. 101 mol ven14000 ch =>)

S48 107 L mol on *

Lert What is the oscillator strength f for the transition in the

preceding problem?

SOLUTION
time C4 132 2si0@ LO monben:) |ed -e/

= (4/32'x 10-7 L+ mol, cm?) (8.48 x 10’ mol! cm>) SoemOeee

16.12 (a) Calculate the energy levels for n = 1 and n = 2 for an
electron in a potential well of width 0.5 nm with infinite
barriers on either side. The energies should be expressed in J
and in kJ mol!. (b) If an electron makes a transition from n = 2
to n = 1, what will be the wavelength of the radiation emitted?
 249

SOLUTION
pete tng A
22
7g di oop ~ ae he 9
2 == =
8m a 8(9.110 x 10 e- kg)(5 x 10 19 in

2 - a
= n 2.410 x 10 4 J 2.410 x 10 wo J forn=1

9.640 x 107” J for n = 2

n?(2.410 x 1029 3)(6.022 x 107° aeiee)

(10° 3 xy”
4)
i
= (ns
Ae 145.14 kie mol
-1 145.14 kJ mol
-1 for n=1

580.57 kJ oe for n = 2

(b) E, E, _= he
he
A= =o
i 1
OO ea, ONO eee
Sp Sn loon
(9.640 - 2.410) x 10 J

16.13 The electronic spectrum of a molecule

R—(CH=CH),—R’
can be described by considering the transitions of 2kn electrons

among the levels in a one-dimensional box of length kl, where 1 is

the length of the unit ——CH=CH—. (a) Ignore electron-electron
interactions and assign electrons to orbitals in accord with the

Pauli principle. Obtain an expression for the lowest energy

transition as a function of k. (b) If 1 = 0.28 nm, what is the
wavelength of the lowest energy transition for k = 2, 5, and 10?

SOLUTION
(a) E =
8mk71
250

According to the Pauli principle assign 2 electrons per energy

level. We assign 2k electrons to the k lowest levels. The
transition of lowest energy is k >k+1.
(2k + Lhe he
Sea _ eae
8mk 1
Ier, Veen
=] 2
A=, (2. 59S 100” mm)ka/ (2kes 1)
(b) For 1 = 0.28 nm, i = ez: X» = 207 nm
ko = Sp A = 589 nn
k = 10, ’ = 1230 nm

16.14 The life times of vibrationally excited states of molecules of a

liquid are limited by the collision rates in the liquid. If one

in ten collisions deactivates a vibrationally excited state, what

is the broadening of vibrational lines if a molecule undergoes

1013 collisions per second?

SOLUTION
AE = hcA® YD h/2ndt
Aw y (2ncAt)? = [2n(3 x 1029 em s-4)(10-22 5)}71
AS > 5.3 om?
16.15 A sample cf oxygen gas is irradiated with Mek | . radiation of
sling
0.99 nm (1253.6 eV). A strong emission of electrons with
velocities of 1.57 x 10’ ms! is found. What is the binding
energy of these electrons?

SOLUTION
; ae = hw —- J

I = ho - > ov
-31 - 2
= 1253.6 ey - 5 0-100 x 10 )(1.57
x10) ms *)
(1i602 50108 eave)
Soo 6V
 251

16.16 The ionization potential of an atom may be determined by exposing

it to high energy monochromatic radiation and measuring the speed

of ejected electrons. When krypton is radiated with 584 pm light

from a helium discharge lamp, ejected electrons have a velocity of

1e50cpe10° wees. What. de the ionization potential?

SOLUTION
h -~ “ ia es + —E.
2 me i

(6.626 Posie: J s)(2.998 x 108 nm oP.)

E. =
i
(582412 7107° mi ti 602 < 10- y ever)
(95110 %x>10 aes ke) (1959ex 10° m ae)
N|R
(1.602 x 10 mor J Bveey
E. 21.23 €V — 7.19 eV = 14.04 eV
i
1 eV i} erdiy) oe en

16.17 When a-D-mannose (tal0° = +29.3°) is dissolved in water, the

optical rotation decreases as B-D-mannose is formed until at
equilibrium [a]o° = +14.2°). This process is referred to
mutarotation. As expected, when B-D-mannose (talo° = -17.2°)
is dissolved in water, the optical rotation increases until
20
lal, = +414.2° is obtained. Calculate the percentage of a form

in the equilibrium mixture.

SOLUTION
[a] = 29.3° fol = =1720¢
a. B
0," ee 0 = 0
[ile i tls2 e293 te 17.0 fe

= 129039". fera =. 1750" AS a

=) =17.0° + 36.3-¢
0 a

f = one = 0.67 = fraction of a form

252

16.18 What is the difference in refractive index for left (n;) and right
(n,) circularly polarized radiation if the measured rotation ¢ for
a one decimeter path length is nGeE degrees at a wavelength of

600 nm.

SOLUTION -3 =i -6
gx _ (10° deg dm )(6 x 10 dm)
n
1 = n
r =
1800 =
1800 deg
eae eae a

Be Vipes
16.19 -17.8 kJ mol
16.20 (a) 15,885 cm 2 (b) 1.9695 eV
16.21 4120/7 sain
16.22 25.2%
16.23 (ede teO00T ex 100° “ghemes
16.24 2.6 pg cm?
16.25 (ala3e24ax010sceenol bir 512 x 10m? molauee
(pb), 2895's: 10° "(aol ft)
16.26 Br ge eye (10 ee ee oat)
16.27 16 x 104 L mot! cm2 7x 10-4
16.28 0.522 nm

16.29 0.0053 cmt

16.30 5.20 eV
16n3t 0.418
16.32 0.636
CHAPTER 17: Magnetic Resonance Spectroscopy

>

7.1 Calculate the magnetic flux density to give a _ precessional

frequency for fluorine of 60 MHz.

SOLUTION

B = ad
ects

= (Giese
A SE 10s Fie 10 = 1.4973 T
(5.257) (5.0508 x 10 Jat)
17.2 Frequencies used in nuclear magnetic resonance spectrometers are

of the order of 60 to 300 MHz. Calculate the corresponding

energies in kilojoules per mole.

SOLUTION
aoe ne £61626 x 10°47 5) (6 x 107 5 *)(6.022 x107% mot ©)
(1000 5 xy)
Besos ee ET mel.
EB = (2.394 x 10> kJ mol +)(300 MHz)/(60 MEz)
11.970 x 10 ~ kJ mol
5 =f

27.3 What magnetic flux density is required for proton magnetic

resonance at 220 MHz?

SOLUTION
220 MHz
$0 MHz 1.4902 T 5.1670 T

17.4 (a) What are the energy levels for a 23Na nucleus in a magnetic

field of 2 T? (b) What is the absorption frequency?

SOLUTION -27 IT ya
E = leylaymB = (1.478) (5.0508 x 10 T)m,
254

= Wi4os%e 108 J)m,

=
3
_2’ = -
3
—
1
-_ —
1
—
3
oe d
i
Since I | 2’ 2’ 7 2’ a 2 an

- - -26
E = -2.240 x 10 cael -0.7465 x 10 2c 0.7465 x 10 F and

2.240 x 10-°
-26
ayo ae zs 1D aT = 22.53 MHz
6.6262 x 10 Jos

17.5 The magnetogyric ratio yy for a nucleus is defined by

My = yal What is the value of yy for H?

SOLUTION
by ylyl Therefore, sa Bayly / hb

2n(5.585) (5.0508 x—3410.7) J T+) =a ZO Sax LO

8 s
-1,-1
T
(6.6262 x 10 ts)

: : 31 : :
17.6 What is the ratio of the number of P spins in the lower state to

the number in the upper state in a magnetic field of 1.724 T at

room temperature? (Given: Bn = 2-263)

SOLUTION
N kT
B

Dae e022 2630S

0A 08ers ORs UR a) Cero 4eT)
(1.3807 x 102° J x +) (298.15 K)

16 ytnudT9exel On”

17.7 In a magnetic field of 2 T, what fraction of the protons have

their spin lined up with the field at room temperature?
 255

SOLUTION
N
Ye.4 BytyB
Nase
h
ee
=2h1/ =i
- 1+ (35565) (5..05
SE10 Jel
Ee 1.000 013 72
Cis Cee ro. J K )(298 K)
N
Pe ee ee ee
N, 1 + N kK 1 + N,/Ny i i) gs 1/(N,/N,)

ge
der elyaDPO00RO13
ey
=72, °° 0.500 003 43

7.8 Using information from Tables 17.2 and 17.3, sketch the spectrum
you would expect for ethyl acetate (CH, CO, CH, CH; ).

SOLUTION
Ci, 3 = i= 0 = CH, = CH,
t “ t t
822 8%3.6 81

CHs of
acery/ group
CHz of thy! group hy!
CHofgroup Ts

3 2, L S)

17 <9 Chemical shifts & are generally expressed in ppm, but it is also

convenient to express them in Hz because coupling constants are

expressed in Hz. What shifts in frequency correspond with a

chemical shift of 8& = 1 for protons in a spectrometer with

(a) 0B ge11541 <Tacend»y (b). 7200 sT?

256

SOLUTION
COED = Te Fares _ o,)B/h

IN, Ae: le, luyo,B/b

(5.585) (5.051 x 1027 5 rT

4)(10
©)(1.41 T) BES 6
6.626 x 10
=34 Is z

(b) Ax = (60 Hz)(7.00 T)/(1.41 T) = 298 Bz

17.10 (a) What is the separation of the methyl and methylene proton
resonances in ethanol at 60 MHz? (b) At 300 MHz? (See Table
hg pe

SOLUTION

See 2 ety 10 -6 pe = 3.59 x 10 -6

3 y)

(a)~75 = (60 x 10° Hz) (2.42 x 10°) = 14.52 Hz

(b) 78 = (300 x 10° Hz)(2.42 x 10°) = 726 Hz

17.11 At a magnetic flux density of 1.41 T, the frequency separation

between protons in benzene and protons in tetramethylsilane is

436.2 Hz. What is the chemical shift?

SOLUTION
(1.41 T) (5.585) (5.0508 x 102" 3 TA)
w= Beyny/h = = Sak Fe
6.6262 2210,
= 60.0 MHz
& = 436,2 Hz/60 Miz = 7,270 x 10°
which is usually given as 7.270.

bby en 2 Calculate the factor for converting a chemical shift in terms of

magnetic flux density to frequency, for proton magnetic resonance.
 257

SOLUTION
wa = By hyB/h :

Bayh 5 a) =al
NUN 5.585(5.0508
ree ie S8h to O20 xA10 = 4257.2 -
x 10° Bz T?
626262_x 10°" J.s

7.13 Are protons a and b magnetically equivalent in

They are not magnetically equivalent (although they are chemically

equivalent) because the coupling H, _ H, is different from the
coupling HS — Hj.

17.14 Sketch the proton resonance spectrum of D,CHCOCD, (deuteroacetone

containing a little hydrogen). Indicate the relative intensities

of the lines.

SOLUTION

The deuteron has a spin of I = 1. Some of the methyl groups

will be CD, H- groups, so that the proton sees two equivalent

deuterons. The first deuteron will split the proton resonance

into a triplet, and the second deuteron will further split these
lines with the same spin-spin coupling constant.

(Please see figure, p. 258)

258

17.15 The proton resonance pattern of 2,3-dibromothiophene shows an AB-

type spectrum with lines at 405.22, 410.85, 425.07, and 430.84 Hz
measured from tetramethylsilane at 1.41 T [K. F. Kuhlmann and C.
L. Braun, J. Chem. Ed., 46, 750 (1969)]. (a) What is the coupling
constant J? (b) What is the difference in the chemical shifts of
the A and B hydrogens? (c) At what frequencies would the lines be
found at 2 T?

pornON
(a) The average spacing of the two doublets is J = 5.70 + 0.07 Hz.

(b) 23 = Wea - d)(b - e)|1 2a [(25.62) (14.229] 2/?

= 19.09 Hz
8 = (1940982) /60)x 10° Hz = 0.418 a0 ements ppm
' 2 6
(c) At 2 T ao = 7 Ane” xan Oe H 7s So eeex 10° Hz

The center of the spectrum shifts by ~2/ ~

6
418.00 Hest BL = 592.86
60 x 10
[6 es? 1 hci
Distance of b and c from center = ———————
2
 259

= $4 (85.1 x 0.318)” + 5.707J*4/? - 5.40 \ = 10.98

do = + 5920860 '-« 10.98 = (5.7008) 576218-Hz
b = 592.86 - 10.98 =) 581.88 Bz
c = 592.86 + 10.98 = 603.84 Hz
te 590 er on ( SP7G PS cote ane
17.16 At room temperature the chemical shift of cyclohexane protons is

an average of the chemical shifts of the axial and equatorial

protons. Explain.

SOLUTION
At room temperature the rate of conversion of cyclohexane from
boat to chair forms is so fast that the protons are at the average
local magnetic field.

a7 .17 As shown in Fig. 17.14, the two lines in the proton magnetic

resonance spectrum for the two methyl groups connected to nitrogen

in N,N-dimethylacetamide coalesce when the temperature is raised.
What is the rate constant for the cis-trans isomerization when the

multiplet structure is just lost at 331 K? The difference in

chemical shifts between the two peaks is 10.85 Hz.

SOLUTION
nA -
ee o WE nm(10.85 Hz) _ SA. a -
vay v2
17.18 Calculate the precessional frequency of electrons in a 1.5-T

field.

SOLUTION
Beste (1.512.023) (902742 x10 FT)
_ 6.6262 x 10°" J s
4.2037 x 1029 s+ = 42,037 MHz
260

17.19 Line separations in ESR may be expressed in G or MHz. Show how

the conversion factor 1 T = 2.80 x 104 MHz is obtained.

SOLUTION
The resonance frequency for electrons in a 1 gauss field is given
by

raed Beri WY ea
(200) Taex 10s Te ele)
My Fob9 ape Ce aes ae
J 3.80 57102" go = 980 x 10° Mz

17.20 Sketch the ESR spectrum expected for p-benzosemiquinone radical

ion.
Om

O
The four hydrogens are magnetically equivalent.

SOLUTION
1 i 1H
1 2 1 2H
il 3 3 1 3H
1 4 6 4 1 4H

Thus there will be five equally spaced lines with relative

intensities of 1, 4, 6, 4, 1.

17.21 An unpaired electron in the presence of two protons gives the

following four-line ESR spectrum: AB/104T = 0, 1, 3, 4. What
are the two coupling constants in T and in MHz?
 261

SOLUTION
a, = 3 x 10° T
a aye eee 10
F 1
0

‘os 34
Multiplying by the factor in problem 17.19

a, = (3 x 1074 1T)(2.80 x 104 MHz T+) = 8.40 MHz

ap = (1 x 104 7)(2.80 x 104 MHz T+) = 2.80 MRz
17.22 Sketch the ESR spectrum for an unpaired electron in the presence
of three protons for the following cases: (a) the protons are not
equivalent, (b) the protons are equivalent, and (c) two protons
are equivalent and the third is different.

SOLUTION

(a)

ee ene
alee fae
262

17.23 Sketch the ESR spectrum of CH.

SOLUTION

! !
ek oe
One

17.24 1.410 x 10°27 3 r1

17.25 (a) 0.4669 T (b) 0.1248 T
17.26 498 MHz
17.27 0.4991 T
17.28 10.706 MHz
17.29 0.500 001 71
 26

17.30

SPECTRUM
Rae Assuming rapid exchange of OH proton

OH CH, CH» CH3

1 2 2 3

relative
area

H
OH CH 2CH3 |
1 1 6 HO —C — CH3
|
CH3

CH
OH 3CH3 |
1 9 HO — C — CH3

CH3

ihe Sey? The proton resonance would be split into three lines by th
deuteron and would occur at 42.6 MHz at 1 T. The deutero:
resonance would be split into two lines by the proton an
would occur at 6.5 MHz at 1 T.

7) SSI The Hy resonance will be split into a triplet with a couplin;

constant of 0.5 - 4 Hz. The Hs resonance will be split int
264

a triplet with a coupling constant of 6 - 9 Hz. The Hy = He

resonance will produce an AB-type spectrum.

17.34 9230 MHz

38G
fe es) The deuteron has a spin of +1, 0, or -1. Therefore the
following combinations of spins are possible:

Spin comb. Total spin No. of ways Spectrum

ail + +3 1
2+, 10 +2 3
2+, 1- +1 3
6
ZO Rec +1 3
Py =9 Eyal © 0 3! = 6
a
all 0 0 1
Yi Sbsr =I 3
6
207.1 —1 3
2-, 10 =2 3
ait =3 1

17.36

Ceres eee i" hae

See M. Bersohn and J. C. Baird, An Introducction to _Electron
Paramagnetic Resonance, Benjamin, New York, 1966, p. 93.

aDYSe i |

sels totesa wil sienait|thiesome

CHAPTER 18: Statistical Mechanics

va

18.1 Using the Boltzmann distribution calculate the ratio of

populations at 25 oh ogy2 energy levels separated by (a) 1000 om”!,
and “(b). 10 °&7 mol.
SOLUTION "ee
~ 34
(a) exp | - pee exp |-
(6.626x10_ Tey 2co ose sm es20 ews
Ss (1.380 x 10 5 K +) (298.15 K)
0.0080
4 1
py) ees Se ee = 0.0177
(8.314 J K™ mol -).(298 XK)
18.2 Calculate the ratio of populations at 25 “Cor energy levels
separated by (a) 1 eV and (b) 10 eV. (c) Calculate the ratios
at 1000 °C.

SOLUTION
N ~ E,/RT 438) =01B Sy/RT
(eet es eee NS, B
Ne —E,/RT
e

1eV = (1.602 x 10 1° 3) (6.022 x He oes

oe <genagsekibs déeoln
N,/N, = exp(- 9.647 x 104/8.314 x 298.15)
= 1.2530a4101--

(b) N,/N, = exp(- 9.647 x 10°/8.314 x 298.15)

= Maaco”
(c) At 1000 K N,/Nz = 1.100 x 1074
Zz, — Zz i} a So6tx 10 7°
266

18.3 Calculate the translational partition function for Hy (g) at 1000 K

and 1 bar.

SOLUTION
yen aon
ye BE {Gswoi)(8,314 7k -1 moll-1 ).(100008) | oka: aa 3
‘“ 10 No
= = 23 all
m = 2(1.0078 x 10 kg mol 1) 7 (6.022 x 10° molt.)
mea s47 x flO ee
2nmkT 3/2
Gey z rae %
h

2
on(3.347 x20 — kg) (1.3806 x 10-2 s x 1)(1000 K)
(6-6 6estd ieee ae
30 x (0.083 14 a
1.414 x 10

18.4 A helium atom is in a volume of 107? n>, What are the values of

its translational partition function at 298 K, 1000 K, and 5000 K?

SOLUTION
At 298 K
2 BY) 22
q, = 2nmkT/h V

_ |ax(4.0026 x 10.” 3 kg mol’ -1 )(1-38 x 10 =93-u

7° J £4)54 (098 K) 3/2 -9 3
23 mr 234 2 10" a")
(6.022 x 10 mol )(6.626 x 10 Js)

PC Gh eaniede
At 1000 K
aq, = 7.74 x 10° 21 (1000 K/298 x)?’ = 4.76 x 1072
At 5000 K
a, = 7-74 x 10°? 21 (5000 K/298 Ky3/2 5 32 x 1023
 267

18.5 The thermal de Broglie wavelength defined in connection with

equation 18.70 is a little different from the de Broglie
wavelength. (a) What is the de Broglie wavelength for hydrogen
atoms at 3000 K? (b) How does it compare with the thermal de
Broglie wavelength calculated in Example 18.1? (c) How does this
thermal de Broglie wavelength compare with the mean distance
between hydrogen atoms in a gas of hydrogen atoms at 3000 K and 1
bar?

SOLUTION
9)
(a) 2 hyfe aoe kT(equ. 15.73) SeBM ra Vy 22 mt ae

1.0079 x 10> ke mol 27

m = ann) cena aa = 1.674 x 10 kg
6.022 x 10 mol

en a” (seer tl?
= =)3 1/2
= (3)(2.674 x 10 kg) (1.38 x 10 J s) (3000 K)

Wie Aso re108 ok, use

h 666260 x 100, -11

1, at= = Sage = 4.596 x 10 m
P 1.442 x 10 kg ms
(b) This is a little larger than the thermal de Broglie
wavelength of 3.175 x 101! m.
(Cc) Va Nl

63404 ae =) (67020 2) t0semol 11°

ae ashi 0a va
Thus both the de Broglie wavelength and the thermal de
Broglie wavelength are small compared with the mean
distance between atoms.
268

18.6 Calculate the entropy of one mole of H-atom gas at 1000 K and (a)
1 bar, and (b) 1000 bar.

SOLUTION
3/2 5/2 CARD
SP re eee (2nmkT) Ve
ON
A

1.0079 x 10> k je
m= EE COF:«C*1«673 85 x 10" -27 kg
6.022 045 x 10° mol

wees RE ee csnsias K+ mol ~)(1000 K)

r 102° Nass
3 =4
= 0.083 14 m mol at 1 bar

Pee werere ery s

(tis eT at 1000 bar

(a) At 1000 K and 1 bar 6°. = jooca7] Tes mole

1 =A,
(b) At 1000 K and 1000 bar’ 8° 82.437 J]K~ mol

18.7 Calculate the entropy of neon at 25 °C and 1 bar.

SOLUTION
205179720 ke-nole- 26
m = a ank aan = 3.350 86 x 10 kg
6.022 045 x 10°” mol
Si @ET (8691409 Kicemole
1(298. 158K)
E 10° N moo
mie 470 0x 108 on emo

5 2nmkT 3/2 V
s° = R ee (xs) ce =" 146°328 3k) = -
motes
h A

0
18.8 Calculate S and Cp for argon (M = 39.948 g mol) at 25 °C and
1 bar.
 269

SOLUTION
mY a0t39%948 £910 =3 kg a ~1
39. = 39° By 102° 1,
6302290454%°105° imo
oe ET ees AK ol) (298 15k)
é 10° oN me
= 2.478 94 x 1072 m? mo1~4

0 5 2nmkT 3/2 Vv
2 at aha lanGes a|ne
h te lo TeA
= 154.844 3 kK! moi
ER
Cp aS
5 ehh R TS 2OR TSO JDK elec)
mol

5.9 What are the translational partition functions of hydrogen atoms

and hydrogen molecules at 500 K in a volume of 4.157 x 102 m>?

(This is the molar volume of a perfect gas at this temperature and

a pressure of 1 bar.)

SOLUTION

q, =| 2m(2.008 x 10> xg mol 1)(1.3806 x 10 °° J K ')(500 XK)

(e022 804ses 100” mol 167626 x 10007 8)
x (4.157 x 10°72 m°)
8.84 x 1078
For Hy, my = 2my
270

18.10 Calculate the translational partition functions for H, H, and H3

at 1000 K and 1 bar. What are the rotational partition functions

of Hy and H3 (linear) at 1000 K? The internuclear distances in H3

are 94 pm.

SOLUTION
y = RE _ (8.314 41 J x7) mo1”*) (1000 K)
B LOD en ma?
= 0.083 1441 m? moi
a. (OymeT een
qt h
3
[2n(1.0079x107> kg/6.022x102? moi) (1.38x10-29 J K~1) (10? K)13/? Vv
6:62 x-10°°* J s)°
= 6.026 x 10°" V = 5.00 x 107°

For H a, = 6.026 x 10°99 y 29/2 = 1.42 x 1099

For H, a, = 6.026 x 10°9 y 39/2 = 2.60 x 10°97
8n7IkT
2 coer
2h
For Hy

_ 8n2(4.6054x1048 kg m*)(1.38066x10~2> J K~1) (1000 K) Fete

: 2(6.62618 x 10734 J s)2
For H3

Leek
I = ————R
mn,m

ih pa
_ __(1.0079 x 1079 kg mo1t)?(1.88 x 1071 m)?
2(1.0078 x 10°? kg mol‘) (6.02205 x 1023 mo1~1)
= 2.96 x 10°47 kg m2
(Note that my is on the axis of rotation, and does not
 274

contribute to the moment of inertia.)

-48 2
tee Gea) 29.
ee Ga!) Tae 36.8
: “wg (he siege yas
18.11 What is the rotational contribution to C i and s° of CH, at
. 4
290,05 Ke

SOLUTION

(CajpeerrowRe
Piet: 2
=” =2 (ey314041 ip) 49,470 Ke” nol”

Th RF i
SF de = sh ig ee
r oO 6 6,86
aepec

1/2
ees 8haiaedin’ ie 298.15° x 2.7183"
sod hitsDs 435.6
Ae 6bI Kae pol
18.012 What are the symmetry numbers of the following organic molecules,
assuming free rotation of methyl groups? (a) ethane, (b)
propane, (c) 2-methylpropane, (d) 2,2-dimethylpropane.

SOLUTION
ae S = 42a S

| 3
|
CH

(4) CH, — C — CH,

eS o= 12x34 = 972
|
CH
272

1
eS Derive the expression for the vibrational contribution to the

internal energy U = a REZ where x = h~/kT.

e~ - 1

SOLUTION

a 1
qy nae rs
—-h ~/kT
eo Seer
oT
Ing = -In(1 eas
din q, eh o/kT (h ) ul
Soe eae ag Ihe ie ce eee Sey PS = —————_ where x = h-~/kT.
oT atoms h~/kT KT T(ex -~ 1)

U = RTx

eve t

: 0G : ; : :
18.14 Using (32) = -§S and the contribution of vibration to the
P
Gibbs energy for a diatomic molecule in a perfect gas
G = RT in(1-e%*) derive the expression for the corresponding

contribution to the entropy.

SOLUTION
ae h~ ds) 20 he
kT dT kT

ae R in(l -e%*) + ee eee (6a)

oT se. (Calle
(1 )

= Rin(1-e*) + se -x cx)
(1 -e *)
=x

= ORV In(l —le ~)) —— Rxe =

Gla eon)

— xX Rx x -x
S =aS aad
-Rin(1-e%*) + = R = iiGl = q >)
 273

18.15 By use of series expansions show the vibrational contribution to

0
Cy for a diatomic molecule approaches R as T —> ».,

SOLUTION
; e 2 Pecks

() : (+ wie.
( =h1))

Bee ase2! a am a
T

o a

(y) = R (4)

Scar ac (cy)
Vv

18.16 Calculate the entropy of nitrogen gas at 25 °C and 1 bar pressure.

The equilibrium separation of atoms is 109.5 pm and_ the

vibrational wave number is 2330.7 om,

SOLUTION =3 “4
6.022 045 x 1023 mo1~2
—23 =1
kT _ (1.380 662 x 10 donk “A298. 15K) A116 44 uy 10726 m3
Pp 10°
N m2
3/2
5° Ul
: 1a |
(2Eon) ts
t

3/2
=93
in |(2n(4265181x10“© kg)(1.380662x10 “J K+) (298.15 ©)
(6.626 176 x 1094 5 s)?
x (4016844 x 10228 mo) =2 15.593 36
274

S° = (8.314 41 J Kv mol) (2 + 15.591 36)

= 150.419 3 K mol
2
@ =>
ig 8n IK

Dene, Nee taougiee 1073 kg mol =|

amy Z 265022 045 x410-° mole)
= "1.16295 x 10°° ks
I = aR 2 a ie2sosen, 108-* kg) (1.095 x 10, ae
= 1.394 41 x 104° ky m*
Hees (6.626 176 x 10% 1 J is)=
8n2(1.394 41 x 104° kg m*) (1.380 662 x 1022 J K})
= 2.888 41 K
Os. eT
S. = R in(21)
r

= (8.314 41 JK} moi?) in (ae

= 41.104 3 K-! moi!
no = he eg
kT kT
34
(6.626176x10 ~* J s)(2.997925x10° m s+) (2.3307x10° m-)
(1.380662 x 10°23 J K~+) (298.15 K)
= eeele. 407)

s° soles = iie ace)

v x
a = al

Fa
= (8,31
(8.314 41 J K
-1
mol
-1
') 14.247a
11.247
In(1 - e
-11.247
)

1.21 x10 2 eK” Hole

oO
ee st A s° 2 s” = 150.419 + 41.104 +0 = 191.524 7 Kv! moi72
 2 fhe)

L&e17 Calculate Cp for co, at 1000 K. Compare the actual contributions

to Cp from the various normal modes with the classical
expectations.

SOLUTION
SOLUTION a
3 F 4 Rx2 el
G-=
Iv
2h)
2
43k 4 :
) :
x.
i=l 6 : re 1)2
he 7, cy
Eeeite seq ane (2-438 x 10,9) 7
~ Jn 1.3512 x810° 6.722 x 10° 6.722 x 10° 2.3964%x 10°
x. 1.943 0.967 0.967 3.446

Q i} 7 (8.314 a1) + 56.927 Et a2) 095). +4 3.344

53.974 JK moi2
2 One 0 0 Oe 5
Classically Cp = Cot a Che + Coy =i Ry +e) Riot Sc4R

- R = 62.3553 K 1 moi}
18.18 Calculate the ratio of the number of HBr molecules in state v = 2,

J = 5 to the number in state v = 1, J = 2 at 1000 K. Assume that

all of the molecules are in their electronic ground states.

(0, =-5700 Keped f= fiz) K)

SOLUTION
Ovib = Srot
eel , ET
N(v=2,J=5) _ ®avib ®5rot
eee ~ "avib ~ §2rot
kT a
Bivib® eorot

g SS) Ab aeGye UE Sy
276

Brot OL = pete 82 rot

= 11 for Bs rot
z =
efvib ve
Given e. = hw~/k = 3700 K for HBr

ae eit ee ; _ Js + 1)n*
eV ibe Be ny kT T rot ee

Given 9 = ; = 1251 K for HBr

x 8n~ Ik
ene J(J + 1)@.
= AN@l ¢ 1)0 k iT = aaa ae ae
Se ot

3
Nevad Josie to SMe Das 11 se 0s Ee eee
_ abe. + 5

MS e
-3.7 x 5xe
-2(2 + 1)(12.1)/10°

18.19 The ground state of Cl(g) is twofold degenerate. The first

excited state is 875.4 cm higher in energy and is twofold
degenerate. What is the value of the electronic partition
function at 25 °C? At 1000 kK?

~e,/kT os
a = £6¢ i 4° Lah ge he Y/kT

i} N +
2 exp -(6.626 x 10°" J_s)(2.9979 x 10° m s_*)(8.754 x 10° m*)
(1.3806 x 10 2° 3 x4) (298.15 kK)
—-4,224
=" 92> = 92 e 2.029
=1.299
At 1000 K qi 22ek2.04 2e = 2.568

18.20 What is the partition function for oxygen atoms at 1000 K

according to the date in Table 18.1? What are the relative
populations of these levels at equilibrium?
 A

SOLUTION
ie je 228-1/1000 , ,-325.9/1000 nace

P, = 5/a, = 0.617

P, = Per Ue Yee

P, = Saas me teens

18.21 Derive the expression for the electronic internal energy of an

atom or molecule. What is the electronic energy per mole for a

chlorine atom at 298 K and 1000 K? (See Problem 18.19)

SOLUTION

~e,/kT

cry, tae ~e,/kT

ae
2e,e

Date

where €, is taken as zero and e, = 875.4 cmt

g, = (875.4 emei)(10439' Roch) = 4, 260k

Ne, = Nhe A (6022 0x 1073 mol (6626 x 10° 343 s)

_1 (2-998 x 10° m s-*) (875.4 cm” )(100 cm m”)
=| O47 koe mod

-1, - 8
U 2 Ri Oedieer noi) pee = 0.150 kJ Ps a
298 01 i -1260/298 ‘
1 + e

- - 1000

1000 an 1260/1000 ;
278

18.22 Calculate the temperature at which 10% of the molecules in a

system will be in the first excited electronic state if this state

is 400 kJ mol? above the ground state.

SOLUTION
-E, /RT -E, /RT
ig
Nig
e h ies
en
—-E,/RT
aoe
N
ke
0/RT -E_/RT
i 1
De e + e

il
wo BE,/RT ry
e ae db

ee = 0.9 = 9 Fu = In 9
Y i RT
E -1
a 1 ~ (22400; 00003 mols) 22,000 K
R in 9
(8.314 J kK! moi 4)in 9

18.23 Calculate the fraction of hydrogen atoms that at equilibrium at

1000 °C would have n = 2.

SOLUTION
Since the fraction will be very small, it is given by the ratio of
the number with N = 2 to the number N = 1.

WE, /ED S(Pe EET

Fraction 2 e 4 "
-E,/kT
e€

From Example 12.1 E

~20179Ts 7 907ie= 1015 J
or
n

Fraction = exp _ (2.179 907 x 10718 3) (-0.75)

(1.380 662 x 10723 3 K~1)(1273 K)
4x10.
41
 279

18.24 Calculate the values of Do in Table 18.1 from data in Table A.2

for Hy (g), 04 (g), C1, (g), HCl(g), and CO(g).

SOLUTION
Hy(g) = 2H(g)
An’ = 2(216.037) = 432.074 kJ molt = 4.4781 eV

An’ = 2(246.785) = 493.570 kJ molt = 5.1155 eV

Cl, (ig) dex 201 (g)

AH’ =!-2(119.608) = 239.216 kJ mol = 2.479 eV

HCite)) =) H(z)) + L1G)

AH’ = 216.037 + 119.608 + 92.127 = 427.772 kJ mo1 +
=
4,4336 eV
CO(g) = Clg) + O(g)
Au’ = 709.506 + 246.785 + 113.805 = 1070.096 kJ mol!
= 11.0909 eV

18.25 Calculate the statistical mechanical values of cs S: 5 How and

G° for H(g) at 3000 K.

SOLUTION
(<) = > (8.314 FC molLN = 20 Tee Ke mol
Lc

Ht 4 5 (g.314 41 J K > mol -)(3000 K) = 62.358 kJ mol?

280

3/2
2n(1.0080x10> kg mol) (1.380662x10_ 23 5 x) (3000 K)
(6.626176 x 107324 3 s)2(6.022045 x 1022 moi)
(1.380662 x 10 -23
~~ J K =] )(3000 K) Aig ees
10° Nm
0 -1 -1 7
S, = (8.314 41 JK” mol “)(2.5 + 1n 1,294 43 x 10°)
= 156,944 3 K! moi
0 -1 -1 7
Gi = -(8.314 41 J K~ mol ~)(3000 K)(in 1.294 43 x 10°)
= -408.474 kJ mol?
For the purposes of this calculation (cs) = 0 and E. = 0.
e

s° = s . s" E (1560900) ee eA la 2) ke ele

= 162.707 J K +~mol*
Go= G+ G = [-408.474 + (8.314 x 10°°)(3000) In 2]kJ mol
0 oO 0 -3 -1

= =—425.763 kT mol
18.26 Calculate the statistical mechanical values of ce S43 Hae Sand
P
G° for Hy(g) at 3000 K.
SOLUTION
(cp)
caeeo BR 2 820-786 fiketdmot

Het Re COURT
2 = 620358 Ktomolee
3/2
(2) E = 3.661 20 x 107
h P
si = R(2.5 + 1n°35661.200% 10!) = $165. 580) ta Ket cise
o
G = -(8.314 41 JK”-1 mol -1
~)(3000 K) In 3.661 20 x 10 7
= -434,409 kJ moi
 281

e., ll R = 8.314 3 Ko! mo17

Ti
ge wes

= (RT = 24,943 kT mol2

O57 eT
2 a R in iS ;
r
(2.7183) (3000 K) -1 -1
= (8.314 41) In
(2) (87.547 K)
=
= 31.936 J K~ mol
0 ae -1
= -RT In { —)= -70.865 kJ mol
i o§
I

8 Sp bewns
Vv Kk

(6 .626176x10°* J _s)(2.997925x10® m s+) (4405.3 cm +) (107 cm m?)

1.380 662 x 1029 yx 1
= 9338 3"K
e (6 /T) “i
ee Slee AS ET eel
e = al

0. 2 oe 2 oe
(cp) = n(-*) 575 a 5.806 21K ool
‘4 (e - 1)

2 (8/7) -0 /T ay oes
s. = R coe
0 7T In (1 2 e ) =3) 3.487
3.487 J KT mo ie
di = 4

Spur ,
G° = RTeia (1 \ Sek GS DIANE mol -
V

Since g Oo = fas e =" 0 He sceeuG.e = =432073¢eIru01*

0 0 (0 0 0 z =A 5)
Pp (ch) ts ce) + (ce) +P (%) 34.907 J K ~~ mol

ee By Tislany te SEEM peat E -337.524 kJ mol >

282

g° = eo 455° Gs° 9°.) Sey SOIT ONGeTEK 2 meine

t r Vv e

Ge. @- we eG HIG =e noo selecioncins

ie r Vv e

0
18.27 What are the values of Nig AH®, AS°, and AG° for By (g) =

2H(g) at 3000 K calculated in the preceding two problems? What is

the value of Kp? What is the degree of dissociation at 1 bar?

SOLUTION
AC.Pp =0C (CH)
p Va uCp "2 (H.) = [2(205786)
° = 3409071) ke- mole
212665 JOKEo mol
AH? =) 2H° (HY = “HU(HS)) =~ (2(62-358)0) = (337.524) 1k note
= 462.240 kJ mol.”
AS” = 028° (B) = SOC, =. [2.162 .707) 901, 015 4 kien ike
= 124.401 3 kK mo1~2
AG? = 26°(H) - G°(H)) = [2(-425.763) - (-940.561)] kJ moi}
=. 89.035 kJ mola
gS AG°/RT _ -89.035/(8.314)
(3000)
0
seine

2 0 K
1/2
Ky,
e4cr(P/P°)
= ce es OF a
3= SS
p r= 0.084
1 - @ P

tY)
18.28 Calculate the entropy for chlorine gas at 25 C and 1 bar
pressure.

SOLUTION
0 5 2nmkT at kT dt
2 h P 2

+ R 2 - in(1 - e *) where x = 0 /T
x v
 283

Table 18.1 gives Js = 0.3456 K, 0, = 807.3 K, and o = 2.

S° = 161.889,+ 58.752 4°°9.218 = °2297859°7'

Kt hor
18.29 Calculate the equilibrium constant for the isotope exchange

reaction D+ H, = H + DH at 25 °C. Assume that the equilib-

rium distance and force constants of Hy and DH are the same.

SOLUTION
Since the force constants are the same

Lf2> 1/2
ED B, “4, /ap? = ~h, C(m,, + my) /2m)]

The change in energy for the reaction is due to the difference in

zero point energies for Hy and HD.

Ac, oO = B(w - %,)

=Y2 wH, (32) ee

>
(etiGaxr alos besadeldod
wel
os Sime eas 5 ueSax
207

id le sh ; Sytyy ~Ae,/*T
16at i,/*") “DH,

3/2 3/2
Sete
qi
(=)
"DE,
rae) = less
tD nd tH,

1 oa @ FEED2:
dup
es
Myy Ty, 2(2/mg) 42
ayon sae ee
ci ese
oe 23 ie
oa)
my
Gon yy my
w

~21 -23 -1
of : 85 x 10 J WyAa 1538 x 10 J K )(298 K)
K = (0.650) (2.66)

= 18
284

18.30 Express the equilibrium constant for the reaction Hy Ur I, = 2HI

in terms of molecular properties.

SOLUTION
22
ze 47 /V
q V Q ’)
( H, | ) ( oT)

= = T
2, - 46 Il er VE, ( ies )
- (2) coed 1 - ite onde
e m 2 6 kT
“Hy 7) OT HI (; var / )
= ( 2D - D - D
( oHI oH, ol,
X exp RT =

18.31 Calculate the equilibrium constant at 25 °C for the reaction

H, + D, = 2HD. It may be assumed that the equilibrium distance

and force constant k are the same for all three molecular species,

so that the additional vibrational frequencies required may be

calculated from 2n ww = (k/p)2/2, Because of the zero point
vibration, Ae, for this reaction is given by

Ae - $na(2~ - ~ icin)
fo) 2 2

SOLUTION
Since the force constants are the same

- 1/2... 1/2
poe be (“n, /") = “e (m, + m))/2m)

~p
,
= an (m,)/m))
1/2
2

my + m) se om.
|
>%
) a pee V2 : < = neo
2 ™) ED
 285

h -~
H, 3 Lf 2: 1 Lf 2
Pre 42 (>) = (5) = ed

(6.626 x 10°" J s)(1,319 x 1074 5 4)(0.0249)

2

EF si. 05211055”
2.
0 2,
on (tm, /P°) yp ~AU,/RT
f /?*) (4D, /? ) dy
(H,
0
%p
here?
0

2 2
P qd, ep qd. ED ean /RT
q q gq
tH tD, rH, q rD

The vibrational partition functions are essentially equal to

unity.
» 3 3
foe
Gente
ies Sanat
B72
tel
3/2
agar 3/2
mis Soke
43/2
epee : hey
tH, “tD, a "D5

The following is obtained by use of equation 18.91 with the

symmetry number in the denominator.

2 (2+ 2) (2+ 2) :
eS Ve ete Sala VA a ee eeae
"rH, “xD, es + 2)" (= my)

M1611 9(2))
———— 3555
32

rea 119) 585) 6 Seer tien apyha 5 meri ites28

-79/298
4.22 e Sees
286

18.32 Given the Lennard-Jones parameters for argon in Table 14.5, what
values of the second virial coefficient do you expect at 200 K and
500 K? Do these values agree with the experimental values in Fig.

1.4?

SOLUTION
For argon e/k = 120 K o = 341 x 1012 m
* 500 K
At 500 K it = > ADOGE nt 4.17

BY = 0
a 2s 3..*
B = 3 No B 0

2 ANTS
At 200 K T sey i Sees 1.67

| as a)
B = 7% (6,022 x 10°> mol ")(341 x 10°” m)°(-1.0)
= 50cm’ mol
These values are in agreement with Fig. 1.4.

18.33 Use the law of corresponding states to estimate the Lennard-Jones

parameters for methane from te = 191 K and ve = 100 com? molt,

The values obtained from second virial coefficient data are

o = 0.378 nm, and e/k = 148.9 K.

SOLUTION
1/3
ae Ye ) = 1 ecl0g cm? mol!)(1072 m cm 1)3
OHI (2.7) (6.022 x 1023 mo1~-)
= 0.395 nm

elk = (TL
c
/183 a) 3
ee ae
 287

18.34 Plot the probability density W(r) for random walk in three
dimensions after 1000 steps with a step length of unity. Indicate
the root-mean-square end-to-end distance on this plot.

SOLUTION
3 \3 es ie 342
W(r) = (
ane ont”

Si 271000
gia exp
Pros
2000

wr)
105
x

18.35 In polyethene H(CH, — CH,) ,H the bond length 1 is 0.15 nm. What

is the root-mean-square end-to-end distance for a molecule with

universal joints with a molar mass of 10° g mol? Taking into

account the fact that carbon forms tetrahedral bonds, what is

2 1/2,
Cra)
288

SOLUTION
10° g mol +
14 g mol
5 ily/?

21/2 = ni/2 b = ace 0.15 nm

14

= lh9) satin

D NYD 11//22 1+ cos 0 1/2

ln > = N oo ———
1 - cos 9

ONL /2
= 12.7 nm Gant = 17.8 nm
1—COS pe

18.36 (a) e85ex 1000° (b) 2.47 x 10°77

18.38 1.998 x 10°%compared with 1.414 x 10°°
18.39 (a) 1.23 (bh) 2-83. x 10714
18.40 108.96, 141.78, 139.85 J K? moi2
18.41 126.156 J K+ moi
18.42 2.86
18.43 12.472, 47.822 JK mol~
3.718, -10.540 kJ mol
18.44 (a) 4 (b) 3 (c) 18 (d)27 (e) 324

18.45

18.46 2-475 x 10°

18.47

18.48 3.369 8.144

18.49 11.526 J K7+ mo1-1 —3.437 ki mol=
11.634 J K-* mo171 34.902 kJ mol
 289

<10°99, 1.49 x 10723

251.800 J K+ moi}
29.100, 32.926 3 K7- mo1™

3.20 x 10>
4.41 x 104
0.211
111.770 kJ moi? 1.13 x 10°
-46, 7 om? mol

E 0 Zo 50

1000 steps of 1 W(é) x 104 126 92 36

500 steps of 2 W(E) x 104 89.2 76.3 47.

18.61 (a) 1100 nm (b) 13 nm (c) 18.4 nm

18.62 The maximum in the plot is at r = 10 nm.

 PART THREE
CHEMICAL DYNAMICS

CHAPTER 19: Kinetic Theory of Gases

19.1 If the diameter of a gas molecule is 0.4 nm and each is imagined

to be in a separate cube, what is the length of the side of the
cube in molecular diameters at 0 °C and pressures of (a) 1 bar,

and (>). 1 Pa,

SCLUTION Lis
|| eae mola O0tten sLe UG onmcenn)
6.02 x 1073 moi}
= 3.338 nm fe EEE 2 8.3 molecular diameters
0.4 nm

1/3
(b) (22.4 L atm mol Seley ae L 1) (101,325 Pa atm -)/(1 Pa)
6.02 x 1073 moi
= 155.6 nm = deb ol) = 389 molecular diameters
0.4 nm

19.2 Plot the probability density f(v) of various molecular speeds

versus speed for oxygen at 25 cc.

SOLUTION
f(v) = Aare Se en
2nRT é “My” /2R0

3/2 (Q2sc108 Egimola\y-

= 3 -1 = =
e. 4nve Sexo kg mol 2 28.3143 kK : mol 1) (298 K)
2n(8.314 J K moi +) (298 K)
= ey) ~ =j
Sy Was 104taut O"- com sje) se dee ew
 291

Where v is in ms

v/107 ms f(v)/104 s = 4
il 3.47
3 18.64
5 18.42
U 7.67
10 0.58

20
si

WwW
.
S

So
>
iS

O
5 10
292

19.3 What is the ratio of the probability that gas molecules have five

times the mean speed to the probability that they have the mean

speed?

SOLUTION
qe eee 2

i <v>“m
£i(<y>)CK meee kT
nur EEX
f(5<v>) &@ 25<v> e 2kT

22
LOXv)) 25e7 ore =
f (<v>)

Since Sie = cEy

nm

£(5<v>)
£(<v)) = 25e
=96/7 0=42 1.24x10
-12

19.4 Calculate the root-mean-square speed of oxygen molecules having a

kinetic energy of 10 kJ mol ?, At what temperature would this be
the root-mean-square speed?

SOLUTION
E = Nmdv>/2 = SRD

ee (2B/Nm)*/? = (2E/m)*/?
1/2
Dey2
<v > =)
ae.
——— =e
on\l/2
m M

1/2
2(10x 10° J moi)
32.0 x 10> kg mol1
=) 7 Og Oo
tee 2Es
a
21107 se 102s
ee
Tmo ee
ee
3(8.314 JK mol)
 293

19.5 Derive equations for calculating U and Cy for any monatomic gas

from kinetic theory.

SOLUTION
U = Ay oe F(v)dv
0

= as <v2> = 4. (2) = 3 RT

Sie GI % ao

19.6 Calculate the mean speed and the root-mean-square speed for the

following set of molecules: 10 molecules moving 5 x 102 m sl,

20 molecules moving 10 x 102 m svi, and 5 molecules moving 15 x
10% ms.

SOLUTION

ae DN _ 10(500) + 20(1000) + _5(1500)

dN, 1
35

= 928 ms

a a a 4 , yt/2
fezely2
Vv = —_—_——__
ivi _
=
|10(500)*
—_—————
+ 20(1000)~
ee
+ 5(1500)
eee Oe

) N. 1
35
= 982 ms

19.7 Calculate the velocity of sound in nitrogen gas at 25 °c. (See

Section 19.4.)
294

SOLUTION
1/2
: CpRT
‘ Cit
4 at =4 =f 1/2
(295125 3 K. mol” )(8.3144 I K ~ mols. (298-15 0K)
(20.811 J K~? mo1~1)
(2) (14.0067 x 10-9 kg mol+)
= 352 m ast

(352 m SW tee cm Sear s min +) (60 min re)

(2.54 om in-1)(12 in £t71)(5280 ft mile4)

787] miles here

19.8 (a) How many molecules of H, strike the wall per unit area per

unit time at one bar at 298 K? 1000 K? (b) How many molecules of
0, strike the wall per unit area per unit time at one bar at 298
K? 1000 K?

SOLUTION
(a) For H, at 1 bar and 298 K

M — 2.016 x 10°
=3 kg mol
=r S aang ges te
2 6.022 x 1023 mo1—1
Noe eye ea ica kg mol- 5.314 x 10°26 kg
2 6.022 x 102° moi

eeeRes
(anmkT) 2/2
2
10° Nome
a5
[(2n) (3.348 x 10 Gn S8ibxe lop 23 J x 1)(298 K)]2 /2
ke)
28 922. a—-1
1.075 x2 10 m s
 295

At 1000 K, J (075: x1d07° m2 os02)(298/1000)2 /2

r Se866 x 100 me ere
(b) For 0, at 1 bar and 298 K

10° Nm
[(2n) (5.314 x 10726 cg) (1.381 x 10°23 3 x71) (298)]? Up
2.698 x 10
oT m 2 Ss 1

At 1000 K, JN (2.698 x 107! m2 s *)(298/1000)2 /2

a tae I
1 $4932 110 m s

19.9 The Langmuir is a unit of gas exposure that is defined as

ik 5% 10-6 Torr s. If a surface with 1015 atoms per square

centimeter is exposed to a gas at 1 x 107-6 Torr for 1 s, what

fraction of a monolayer will be formed? Assume the gas has a

molar mass of 28 g mo1 1 and 27 t= 3008K. O(1 wlorr -=1133:.3 Pa.)

SOLUTION
boat Pe 0.028 kg mol -1 2h és age ows
6.022 x 1077 moi
J. = P
——;
Wyner (onaeny ee
2 133.3 x 107° Pa
[2RCAebslzs10cc” kg) (1.381 x iDECa Jak oy)(00K
So Bilge Se 107° ee ro

The number of binding sites is

10? ae
(107° om 2)(100 cu m+)” =
Thus exposure for 1 s will fill 0.383 of the sites if each gas
molecule incident on the surface is trapped by the attractive
surface potential (Section 21.8).
296

19.10 Calculate the number of collisions per square centimeter per

second of oxygen molecules with a wall at a pressure of 1 bar and

25 uae

SOLUTION
eee ayi arte (10° Nm £ *)(6.022 x 107° mol ae ~)
ae (8.3144 J K71 mo1~1) (298.15 K)
So ainsi
1/2
eh igars _ |(8)(8.3144 JK? moi") (298.15 K)
oe n(32 x 107° kg mol 2)
= 444.2 m at

FatN te PERSE?
4 LT4 G42 e107) mea) ada ease)
Ca n? 2667478 Onc iek sms
2B l(a. GSTS A10-) Bmbcen
a) C10 keen ene4
= 2.697 x 1072 Sais are

19.11 A fresh metal surface with 1015 atoms per square centimeter is

prepared. This surface is exposed to oxygen at 10-2 Pa. If every

oxygen molecule that strikes the surface reacts so that there is

one oxygen atom per metal atom in the surface, how long will it

take for half of the surface to become oxidized at 25 °C?

SOLUTION
-3 -1
mn = oeexe
ie ehprnel es 5.31 x 10-26 kg
6.022 x 10272 moi
P
Tes eee ne
an (2nmkT) 2/2
10-2 Nm?
[2n(5.31 x 10°26 xg)(1.38 x 10723 y x71) (298 xy q2/2
 297

Pie ils ee eee

In the surface there are (1015 cm 2)(100 cm m+)? = 1019 atoms

mm, Oxidizing half of the surface will require 0.25 x 1019
oxygen molecules

Bde Uyes
80 ORert LO ee ees aa Ie = aco
281 spa0ees ae het
£9.12 A Knudsen cell containing crystalline benzoic acid

(M = 122 g mol!) is carefully weighed and placed in an evacuated

chamber thermostated at 70°C for 1 hr. The circular hole through
which effusion occurs is 0.60 mm in diameter. Calculate the
sublimation pressure of benzoic acid at 70 °C in Pa from the fact

that the weight loss is 56.7 mg.

SOLUTION
Pee oy, (252)
M Pee 1/2
ee es6et x 10 Cus 2n(8.314 JK mol ~)(343 K)
(60x60 2)x(0,3x10°2)m)- 122 x 10° kg mol
=) 21 auNint
= 21.3 Pa x
29743 R. B. Holden, R. Speiser, and H. L. Johnston [J. Am. Chem. Soc.,
70, 3897(1948)] found the rate of loss of weight of a Knudsen
effusion cell containing finely divided beryllium to be 19.8 x
10°! “gcom-- a! St 1320 K-and1210-x.0” g,cm.- s - at 1537 K.-
Calculate AB cub for this temperature range.

SOLUTION

According to equations 19.29 and 19.30 the two vapor pressures are

proportional to AgT2/2
298

AH® =
142 In —
2
os ie
1/2
_ (8.314)
(1320) (1537) , 1210(1537)
(217) 19.8(1320)1/2
326 kJ hols

19.14 A 5 mL container with a hole 10 pm in diameter is filled with

hydrogen. This container is placed in an evacuated chamber at 0

°c. How long will it take for 90% of the hydrogen to effuse out?

SOLUTION
p_<v? , Op lGdNe) oasNasw
Jy = MEY De Veeterom A At aay fe

<v> = 1.69 x 10° ms! from Example 19.3

aN = x(Sux 10° m) (1.69 x 10° ms _/)N

a (5 x 10° m?)(4)
= NG a
NY C

= -(6.64x10° 87) | at
N fe)
fe)
N 4
In = = -(6.64x10~ aye
fC)

t
¥ In 0.1 ae
‘aa 347 s
-6.64 x10” 5s

ro S15 (a) Calculate the number of collisions per second undergone by a

single nitrogen molecule in nitrogen at 1 bar pressure and 25 “ee
(b) What is the number of collisions per cubic centimeter per
second? What is the effect on the number of collisions (c) of
 299

doubling the absolute temperature at constant pressure, and (d) of

doubling the pressure at constant temperature?

>

SOLUTION
(a) Z4(1)
Ae
=, 2
PiMed
pnd
oe: <v>

ome a ef (10° N m7) (6.022 x 1077 moi‘)

a (8.314 J Kt mo1~+) (298.15 K)
Se et ee
grt
Goamidage \!/2 Sog y 8(8.314)
aE (298.15)
an etal |t/% = 475 ms -1
moe x 100”)
“Seay 21/2 (9.429 x 107°) (0.375 x 10°) 7(475)

ee gaa 1 Onis Bo

lees Yo)
(b) 244 ee Ae p md <v>

= 2 1/2 (2.428. x 10-1 (083 75.5 10.°)7(475)

=] $nnor a? oe
= (3.7) re 10°4 op 57) 10F- mn Bart te
ee Ee Sg ae

(clip te oe go ain 7
1/2 15
eee pe we re pla T
12
Z, (27) aes i :

11
Gijta seas
OT
81
Syst
se” 924
2
(d) 241% Pp

7. 11 W2P) aie,
300

19.16 Methyl radicals appear to combine without activation energy

2CH ==> CoH¢ c The second order rate

constant at 300 K is 1010-5 L mo1 1 st, Assuming the collision

diameter is 0.40 nm, what rate constant is expected from the rate

of collisions?

SOLUTION
3
- —— = 2k (CH3)”

The rate constant is equal to 1/2 the rate of disappearance of

CH, when (CH3) = 1 mol yl,

p = 6.02 x Niece

es grt \t/2
a ee (8.314)
eRe SUAS(300)] 2/2 & Gala Fs -1
nit Sax 100s)
244 = 2
21/29p md
23 <v>

a-1/2 (6.02 x 1079)2n(0.4 x 10-9)7(651)

z= 68-39 x10") nm bene

(8.39 10° os 0 we
(6.02 f10e° cin)

suclet0sy 105) polsleens

d(CH.)d =f) ke
-— = 2.78 x ies FNL ee pte PG ST abe Ne
k =).1839 984007 Temotters ecto SL mores et
19 47 What is the average time between collisions of an oxygen molecule
in oxygen at 298 K and (a) 1 bar, (b) 107° bar, and (c) 10°22
bar? (d = 0.36 x 109 m)
 301
SOLUTION
At 1 bar an oxygen molecule is involved in 6.24 x 109 collisions
per second, according to Example 19.5. Since the number of
collisions is proportional to the pressure, a single oxygen

molecule is involved in 6.24 x 10° collisions s-! at 10-° bar, and

6.24 x 10°" collisions s %-st 1072 bar. The average times
between collisions are therefore

P/bar t/s
1 1.60 x 10 1°
10-6 1.60 x 104
1012 160
19.18 What is the mean free path of nitrogen at 1 bar and 25 °C? What
is the average time between collisions?

SOLUTION
Pare PNa _ (10° Nm ~)(6.02 x 107° mol-)
ae (8.314 J K7 mo1~+) (298 K)
= hep dan otiaeas
1 = [2t/2 SS
Bie 95043 5 10°" mo n(0.375%x 10° 7)
= 65).9) am

Gp) el hayste te From Problen 19,15

=
t es 65.9
x 107° m _ 1.4 x 10710 ;
475 ms 2
29,19 (a) Calculate the mean free path for hydrogen gas (o = 0.247 nm)
at 1 bar and 0.1 Pa at 25 °C. (b) Repeat the calculation for

chlorine gas (o = 0.496 nm).

302

SOLUTION
At 1 bar

N,P 23 % 1) (10° a2
ak (65022 x 10 yO mol
NeNm) = 2a 10
Poel eR
(8.314 J K7 mo1~+) (298 K)
At 0.1 Pa

(6.022 x 107° 2} mol )(0.1 Nm 2

)
(S23 14Miek se gol (298 &)
1
(a) 1
1/2 1g?
1
gl/2 (0.247 x 1079 m)7(2.44 x 1025 m3)
Laps oe ate at 1 bar

f
gt!2"= (0.247x 10-9 m)- x43. x0102° mee)
0.152 m at 0.1 Pa

1
(b) 1
23/2 (0.496 x 1079 m)2(2.44 x 1025 m3)
077 F100 “mvatsll bar
to See
1/
nce SUEY Aoo eM ERI el ee
0.037 m at 0.1 Pa

19.20 Large vacuum chambers have been built for testing space vehicles
at 10° Pa. Calculate (a) the mean-free path of nitrogen at this
pressure, and (b) the number of molecular impacts per square meter
of wall per second at 25 °C. o = 0.375 nm.
Ny
 303

SOLUTION
PN a
2 kK) S (Ones) (6.022 xaA
1029 moi 2) 14 23
ay or i Watt. = 2.430 x0 LO m
(8.314 J K mol ~)(298 K)

(a) 1 = :
V2 Tmo n

eA ee OE 6590 m
i on(3s7eet0 e146 10)

(b) Z = ey
P\OnM
i stwebe 1/2
=b (see: 1024 3) (8.314 J K mol —)(298 K)
2n 28 x 10° kg mo12
oeRe cr lO em 6
19.21 The pressure in interplanetary space is estimated to be of the

order of 10-44 pa. Calculate (a) the average number of molecules

per cubic centimeter, (b) the number of collisions per second per

molecule, and (c) the mean free path in miles . Assume that
only hydrogen atoms are present and that the temperature is 1000

K. Assume o = 0.2 nm.

SOLUTION
is (6.022 x 10° mol. )000 Ne)
ea ee (323140 Sake
Zeon
emolice) (10 K)

30.404 7e0d0 wl”. = ON704 om”

grt \t/2 (8.314 J Kk! mol

ak ie
2)(102K) |’
eee TAPER Rs ae ©
(b) <v> — 7M

e n(1 x 10°” kg mol -)

= 4600 nm aes

74, = git tes <v>

304

- 91/2 (9.724 x 105 m-3)(0.2 x 107° m)2(4600 ms?)

2s syooeh 10m: see

Ee
1 eee
1ue pe eed
(c) 1
gflt 21/2(0.2 x 1079 m)2(0.724 x 10°)
aS IM O« ‘eee m

(Jaiiewetolsen) (one a)
(oe sakeniae oan et 1) (5280 ft poe

4.83 x 10° miles

19.22 Consider an atomic beam of potassium passing through a scattering

gas of Ar contained in a cell of 1 cm length at 0 ce Assuming a

collision cross section of 6 x 1028 2 for potassium-argon
collisions, calculate the pressure of argon required to produce an

attenuation of the beam of 25%.

SOLUTION
Eases,
y\ A » ABNBY

og intr ASAD ere) © 225303 _iogh (00s)

E Qapl (600uea10L- aeClOn a)
Eeaae ers 10sn ese TOR Sate? bes

bi) SEERT |. 4s 802z 1007 1 E (8St Deke aemol S)(208K)

N 2
Nn (6.022 x 1072 moi?)
12811 10 Pa

ton 23 The viscosity of helium is 1.88 x 10> Pa s at °C. Calculate

(a) the collision diameter, and (b) the diffusion coefficient at
iebarns
 305

SOLUTION
(a) d =

m =
4.0026 x 10° kg molt 6.647 x 10 ef | kg
6.022 x 1073 moi
2 - 1/2
d =
E (6.647 x 107! x 1.38 x 10.7 x a]
_ n(1.88 x 107°)
0.217 nm

(b) p =
ay . (10° Pa m )(6.022
x 107° mol+)
RT ir ES ee
(8.314 J K-? moi~1) (273 K)
ye oar geces

Dice 3 (nmkr)*/?
: aes

3 [n(6.647 x 1G. ekg C1 abr On K+) (273 rape

8 2 (0.217x1079 m)2(2.65x102> m3) (6.647x10727 kg)
Teo as Cer aeie
19.24 What is the self-diffusion coefficient of radioactive CO, in

ordinary CO, at 1 bar and 25 °C? The collision diameter is

0.40 nn.

SOLUTION
ge
ee 1 OT Or kg
6.022 x 1073 moi?
> = N 2 TMA _ (1bar)(6.022
x10°* mol?)
(10° Lwot")
Vy al (0.083 14 L bar K? moi
+) (298 K)
— Da Sex 107° ate
306

5 eer
SG

3[n(7.307 x 102° 2 26 kg)(1.38 x 10 = ZS2° J K+). (298 K)] 1 {Z

n(0.4 x 1079 m)2(2.43 x 1025 m-2)(7.307 x 10°26 xg)
16m OP) eee

19% 25 3.89 2 10 eV
19. 26 0.1991
Ve) Pat | 418, 400, and 440 ms 2
19 .28 281 ms 4
19 oe) 4,18 x 107, 4.00 x 10%, 4.40 x 107 mst
UW). 30 481, 445, and 394 ms 2
ie) on (a) 1020 m st (b) 352 ms 2

Lo: 32 3.7 x 107 5s

19. 33 Caen) 36 <x 1022 molecules cm s 4

(b) 0.0629 g cm? min4

IME 34 0.0713 ¢
1 35 8.1x101%, 22101% xg,
iV) 36 78 g mol
19. oa (a) 4275 = 4042 mo ote

(b) 2.86 x 10> m

19. 38 5.8 x 1028 m1} 5-1
19; 39 1.58 x 10719 s 7489 vibrations
 307

19.40 (a) 2.65 x 10° cm3 (b) 6.52 x 10° m

ee : <v4?
19.41
2} : pynd,<v> a Pymd, 5 {V4 9?

; <v,>

fee p md, <v? + pynd,,~<v45?

19.42 28 m m (b) 14 nm2

(c) The cis compound has a large dipole moment while the trans
compound has no permanent dipole moment. Since CsCl is a
dipolar molecule, it interacts more strongly with the
polar isomer of dichloroethylene.

19.43 646 Pa

19.44 1.66 S010 Tera ts

19.45 1.302 x 10° Pa s

CHAPTER 20: Experimental Gas Kinetics

20.1 The half-life of a first-order chemical reaction A ——> B is 10

min. What percent of A remains after 1 hr?

SOLUTION
a -0.693 t/t
[A] = TAsdece’
0)
JEORTAI @)
ete 212
fale a
rie =0,693 (60 m)
exp ey =7 0.0156

Thus 1.56% remains after one hour.

20.2 The following data were obtained on the rate of hydrolysis of 17h

sucrose in 0.099 mol ie HC1 aqueous solutions at 35 Cc;

t/min 9.82 59.60 93.18 142.9 294.8 589.4

Sucrose re-
maining, % 96.5 80.3 71.0 59.1 32.8 ia h wat

What is the order of the reaction with respect to sucrose and the
value of the rate constant k?

SOLUTION

Toe bes 2SKC

8 TA] 0)
2.303

slo = =1 “k
bed 612 m 2.303

=§ tai SU Stee =oee-t

Sel crapvain corks’ Sg

3
= (3.76 x 10. mo) (am Pls )

SOT ope es ie
(Solution concluded on page 309)
 309

100 200 300 400 500

4/min

20. 3 Methyl acetate is hydrolyzed in approximately 1 mol Lt HCI ate

sce Aliquots of equal volume are removed at intervals and

titrated with a solution of NaOH. Calculate the first-order rate

constant from the following experimental data.

i/s 339 1231 2745 4546 ©

v/en> 26.34 27.80 29.70 31.81 39.81

SOLUTION
Any quantity proportional to the concentration of reactant A that
remains may be used in equation
-kt
log([A] = 02303 + log[A] |
310

In this case the concentration of A remaining is proportional to

V-39 61 com>. Therefore log(V-3$.81 cm?) is plotted versus t.

12

09

0 | 2 3 4 5
10s
-0.247 i —k
slope = aeee ge
4.65 x 10 s 2.303

pe ee es) es ee ae
4.65 x 10° s
20.4 Prove that in a first-order reaction, where dn/dt = -kn, the

average life, that is the average life expectancy of the

molecules, is equal to 1/k.

» ndt

Average life

Average life
20.5 Since radioactive decay is a first-order process, the decay rate

for a particular nuclide is commonly given as the half life.

Given that potassium contains 0.0118% 405 which has a half life of
Ws eadp- 9.8 109 years, how many disintegrations per second are there in
a gram of KCl?

SOLUTION
tivo CIS Tet ee Sh Sedna) 4nd) COdbmdc (ks))GOney mine)
= 4.01 x 10! 5
a t See *
172

(0.6930) [(39.1/76.6)g1(6.02 x 107? mol +)(1.18 x 10°)

(4.01 x 102® 5)(40.0 g moi?)
ie Bee
20.6 The decomposition of HI to Hy, + I, at 508 °C has a half-life of
135 min when the initial pressure of HI is 0.1 atm and 13.5 min
when the pressure is 1 atm. (a) Show that this proves that the
reaction is second order. (b) What is the value of the rate
constant in L mol! s 12? (c) What is the value of the rate
constant in bar 2 s 4? (d) What is the value of the rate constant
in om? s§ 1?

(a) For a second order reaction t4/2 = 1/k[A], where [A], is

the initial concentration or pressure of the reactant. This

SW

is in agreement with the fact that the half-life is reduced

by a factor of 10 when the pressure is increased by a factor

of 10.

jig SP ie (8.314
a chee aS UG

JK? mo1~+) (781.15 K)

See Ie

mg a ed ctor ba

1 J
[A] (ty 72 (ics6 e410 * motel) (1g) ses 60s
ay Wot 2-10 wate ae

(eye op exe nng pE ge hag ieee 1Bae

* 7. thea
VO
A (19 sage 6One hl Olsaban)

= 22x 10° eee me

Ce pe lee ie 10GetLemote say) Cs cme 3)

(6.022 x 1023 moi~+)
GE ee RNa ny Seahva

.7 The reaction between propionaldehyde and hydrocyanic acid has been

studied at 25 °C by W. J. Svirbely and J. F. Roth (J. Am. Chem.

0
Soc., 75, 3106 (1953)]. In a certain aqueous solution at 25 C
the concentrations at various times were as follows.

t/min 2.78 S233 8.17 NSin23 19.80 co

[HCN] /mol ue 0.0990 0.0906 0.0830 0.0706 0.0653 0.0424

[C,H CHO]/ _
mol L 0.0566 0.0482 0.0406 0.0282 0.0229 0.0000

What is the order of the reaction and the value of the rate con-
stant K?
 313

The data does not give a linear log versus t plot, and so the data
are tested in the integrated equation for a second order reaction.
Equation 20.27 is

[A] [B] °
(kia (0)
:
1b)oO
In
TA lee
(0)
ak
In order to get [A], and [B], for t = 0, the clock is started at
the first experimental point. This yields the following data to be

plotted.

t/min Goru ss 5.39 12.45 17.02

i [A] [B],
IAT, - (BI.) In TAT (BI 0 1.695 3.677 8.458 11.523

= =il
The slope of this plot, 0.675 L mol : min , is the second order
rate constant.

ro

0,
1-9
ss 10

aes)
ra

[-8)
— |
“I
eS t~)

ye 0
0 |
t/min, ae
314

The second order rate constant for the reaction of C10 and NO is

6.2 x 107-12 cm? 5-1. What is its value in L molt 519

SOLUTION
Eve s(GRD OF Somers se lomae im cma (68022102 enolase)
=) 3293 x10 1 mol pec
20.9 The reaction CH,CH,NO, + OH —> H,O + CH,CHNO, © is of

secondeondet) andr ks atel © “Cov isigS9s itlomolicesinipaye An aqueous

solution is 0.004 molar in nitroethane and 0.005 molar in NaOH.

How long will it take for 90% of the nitroethane to react?

a(b - x)

= A 1 (0.004) (0.005 - 0.0036)

(39.51. lewol tmin?)
(0,00i nol ta) (0.005) (0.004 - 0.0036)

26.3 min

20.10 Hydrogen peroxide reacts with thiosulfate ion in slightly acidic

solution as follows
2- + 5
H,0, + 28,0, + 2H —) 2H,0 a 84%

This reaction rate is independent of the hydrogen-ion

concentration in the pH range 4 to 6. The following data were
obtained at 25 °C and pH 5.0.
Initial concentrations: 1
[H,0,] 0.036 80 mol L ~;

—
i} 0.020 40 mol Lt
 315

t/min 16 36 43 52
2- = =

[S,0, 1/10 Ee ee 10.30 5.18 4.16 3215

(a) What is the order of reaction? (b) What is the rate

constant?

SOLUTION
(a) In the first 16 minutes, [S05 1 is approximately halved.

In the next 20 minutes, [S05] is approximately halved. In the

next 16 minutes, [8,07 ] is considerably less than halved.

Therefore, the order is higher than one. The next section shows

that the reaction is first order in H,9, » first order in OR,

and second order overall.

(b) Let A=H,0, and B= ues Equation 20.26 becomes

: [A] [B]
kt bin =
(2[A] — [B] ) [A] [B]
(@) 0)

In TB] In [BT + (2[A], = [B] ,) kt

t/min 0 16 36 43 52
[B]/10 > os iaee 20.40 10.30 5.18 4.16 313
(Ai /40 deme) Ue 36.80 31.75 29.19 28.68 28.17
In as 0.590 1.126 1. 729 1.931 2.197

(Solution continued on page 316)

316

L5

20

CA)

1.0

0.5
0 10 20 30 40 50
t/min.

slope = aed = 0.0312 min

= (2[A] - [B] ) k
(0) (0)

en 0.0312 min+
2(36.80 x 1072 mol L-4) - 20.40 x 107° mol L-1
i} 0.59 L Bole niga

20.11 The pre-exponential factor for the ttrimolecular reaction

2NO + 0, -——> 2NO, isi 10° om) mol * 5° °. What is the value

in L? mol~2 s+ and om? st?

SOLUTION
6
(102 cm Bola a) (0° dw oe)1)6 EO 3 de 6 mole cae
 317

= ALOS-L 7 tind te=4

2
Setl07 U4 mol. 65-3010 cn)
(6.02 x 1073 mo1~1)?
= 2.76 x 10.
39 cm 6 s -1
20.12 A solution of A is mixed with an equal volume of a solution of B

containing the same number of moles, and the reaction A+B = C

occurs. At the end of 1 hr A is 75% reacted. How much of A will
be left unreacted at the end of 2 hr if the reaction is (a) first
order in A and zero order in B; (b) first order in both A and B;
and (c) zero order in both A and B?

SOLUTION
(a) If the reaction is first order in A and zero order in B, the
half time is 1/2 hour, and the following table may be
constructed doing calculations in your head.

t/hours 0 1/2 1 1-1/2 2

% Unreacted 100 50 25 125. 6.25

% Reacted 0 50 75 8.75 93.75

(b) If the reaction is first order in both A and B, and the

initial concentrations are equal, and the stoichiometry is
1:1, the concentration of A will follow

eowee:
alt[A] ote
[A] | t{A] |
Wf[A]oy
[A]
1 Ce) Ԥon1 100i0 - as -1
cA = (an? z= ) hon he |25 : 3 hr
After 2 hr Ai Eom 100 _ F
F aytg ied bed6,
(A) ee ening oe
318

(c) If the reaction is zero order in both A and B, both will be

completely gone in 1-1/3 hr.

20.13 Derive the integrated rate equation for a reaction of 1/2 order.
Derive the expression for the half-life of such a reaction.

SOLUTION
Cale = 1/2

[A] t [A]
SLU ER Ue ge Payee< sol ZuTAlS(out n ea
[A]
fete )
[A] oO 2

[Ales dA? Me cere

At tyyo) [A] = [A] 9/2

1/2
[A]
: 2a ° 2 Ge 2 1 1/2
Site Ad ( =) aS é (3 ; ra ere
be ee os
eee ee 1/2

20.14 Show that for a_ reaction following the rate law

-d{Al/dt = k[A]°, the half life is given by
. 7 ao L 1

Te) utga Stee

1¢)

where a is an integer not equal to unity.

SOLUTION
.. 7 =O, + ol
[A]
Se
[A]?
ee hh iN = 1Al a
ar.
 319

[A]®
. _
al [A 1%
(eat
1 =
( a Ss
1)kt
fa)

If [Al]
[A = —
1 [A ;
Tine —_—__—___
it
ee ayud = 1) = Cie = 1) kt
[A]
oO

20.15 Show that for a first order reaction R —) P_ the concentration

of product can be represented as a function of time by

[Pjca= att bt 2 ot ok and express a, b, and c in terms

of [R], and k.

SOLUTION
[Pl = [kK]. ° = {kl = [Re(rt—
o
15)
: Kt F ‘
Expanding e as a power series gives

[P] = ce (ke -
(kt)? A (xt)? i
2! 3!
chose asl —_ 0) be [R] k, and c= [R] k°/2.

20.16 For a reaction A —>) X, the following concentrations of A were

found in a single kinetics experiment

[A]/mol lee 1.000 0.952 0.909 0.870 0.833 0.800

t/hours 0 0.05 0.10 0.15 0.20 0.25

What is the rate v of this reaction at [A] = 1.000 mol Ll,

SOLUTION
as SlA)
‘! dt
C =i =Al
As a first approximation v = — = 0.960 mol L hr

A better value may be obtained by using

[Pit = ib + ct
for the first 10% of the reaction.
320

(xivaelt Ie 048 091 .130 167 .200

tiie 05 “10 “15 "10 25

O08
~05 FE To CG. 05) e e 02 960
0.091
p-vot _= b> + © (0.10) i 0.910

Taking the difference between these equations

03:050, &=, «-0205g¢
¢ =. 71.00; b = 1.010 = v

More experimental points can be included by least squaring.

Least squaring through 13% reaction yields

vy = 1.005 mot L? hr
Least squaring through 16.7% reaction yields

v = 0.998 mol ian ea

Least squaring through 20% reaction yields
v = 0.993 mol i ee
As the extent of reaction increases, this truncated series expan-
sion becomes less adequate, and so the initial velocity is

1,000 4104005 mol fo hei > | aeathowt han 0-06 molNle ent
obtained as a first approximation.

20.17 The following table gives kinetic data [Y. T. Chia and R. E.

Connick, J. Phys. Chem., 63, 1518 (1959)] for the following

reaction at 25 C.

OC] 7) Gila et Ol eee Cl

[0c17] (tr [OH] ats Thor
mol Lo mol he ae

0.0017 0.0017 1.00 17S

0.0034 0.0017 1.00 3.50
0.0017 0.0034 1.00 3.50
0.0017 0.0017 O5 3.50
 321

What is the rate law for the reaction and what is the value of the
rate constant?

SOLUTION
When other concentrations are held constant, doubling [0C1]
doubles the rate, doubling [I ] doubles the rate, and halving
[OH ] doubles the rate. Therefore the rate law is
d[OI ] as k{0C1 J[I ]
[oH]
Substituting the values for the first experiment
-1 -1
1.75 x 104 oa pt aot ~ k(0.0017 mol L )(0.0017 mol L )

(1 mo1 L7+)

20.18 When an optically active substance is isomerized, the optical

rotation decreases from that of the original isomer to zero in a

first-order manner. In a given case the half-time for this

process is found to be 10 min. Calculate the rate constant for

the conversion of one isomer to another.

SOLUTION
0.693
t = --—--__ = 600 s
1/2 ke ES,

Since K = 1, k) = ky

0.693 _
Ty eee. 1
es,

k,
be= eu0S693
s(e00ae,
4 ry Sine xe10
-4 s
-1

238
20.19 The first three steps in the decay of U are

2385 a y 2347, B y 234), B y234y

9 24.1 d 1.14 m
4.5 x 10° y
322

234
If we start with pure aac Ue what fraction will be Th after

10, 20, 40, and 80 days?

SOLUTION
Ene ~-—.----9:882 _________ spud Soa Ogen des
(4.5 x 10° y)(365 dy

ee _ 0.693
Grcer 0.0288 d -1
ren (234,41 : k, at : Se
Psy] Eo eke

t/d 10 20 40 80

Tie $03565:G510 (ce eek 398 BOM ea emoroRiaitoc > as aeeromes

20.20 For the reaction 2A = B + C the rate law for the forward

reaction is

ata]
ag
_=. k[A]

Give two possible rate laws for the reverse reaction.

SOLUTION
eas tec
[A]
Ateoquitibriva "2 oA
dt
70, =) eorRf I> Sea I IB IC
0 = k,fA] - xk (BI[CI/IA]
Ir

Possible rate law for the reverse reaction k [B](C]/{A]

- reat ene
[A]

At equilibrium - ala) 2% 0 = kK [A] - k [Bl]?! *[cy?/?

dt f I
 323

Possible rate law for the reverse reaction Elpio/ tcion

“ [B17 [e]7
4
[A]

At equilibrium ee Geared Als wear ed: (Cie

dt f I

Sey
0 = k,[A] - Hie
eo Al

Possible rate law for the reverse reaction x (B]7[c]7/ta]°

20.21 Suppose the transformation of A to B occurs by both a reversible

first-order reaction and a reversible second-order reaction

involving hydrogen ion.

1 3 -
A == B A + H == B+ E
k, k,

What is the relationship between these four rate constants?

SOLUTION
ae
alee
a eee
k,

PElecln | ‘ [B] k
Gee re yi, LE Neee
A k
fAl q
Lg eq
aA ary 4

Therefore
ky
ee = =
ky or kk, = kk,
324

el
20.22 The hydrolysis of (CHS) 6CN in 80% ethanol follows the first-—
CH,

order rate equation. The values of the specific reaction-rate

constants, as determined by H. C. Brown and M. Borkowski [J. Am.

Chem. Soc., 74, 1896 (1952)], are as follows.

tfc 0 25 35 45
k/s t 1.06x10> 3.19x10% 9.86x104 2.92 x 10°
(a) Plot log k against 1/T; (b) calculate the activation energy;
(c) calculate the pre-exponential factor.

SOLUTION
 325

-E a
(b) slope 7.303 R -4600 K

E, = (4600 K)(2.303)(8.314 K > mol+)

Set by mol

(c) Taking the 35 °C point and E, = 88.1 kJ ola

-E.

log k = 27303 RT + log A

32006 © pa -88,100
re J moi
ee2 ee ioe x
2.303(8.314 K~+ mo1~1) (308.15 K)
Kee ee 0 ee
20.23 (a) The viscosity of water changes about 2% per degree at room
temperature. What is the activation energy for this process? (b)
The activation energy for a reaction is 62.8 kJ molt, Calculate

SOLUTION
- -E/RT
(a) — = Ae
nN
E.
SR ees eeTe RT

E
ont on Siu
n RT

i RT AT

=f = 2
= - (8.314 J K~ mol ~)(300 K)“(-0.02)/(1 K)
=. stiees well
jee k35 : ALT TACT,
as ‘i RT.T
326

= —
(62,800 J moi +)(10 K)
(8.314 J ae edi) (298-15 K) (308.15 K)
k
oo = 2.27
Z5

20.24 If a first-order reaction has an activation energy of 104,600

1 ~E/RT
J mol and, in the equation k = Ae » A has a value of
Sex 10°? a at what temperature will the reaction have a half-

life of (a) 1 min, and (b) 30 days?

SOLUTION -E /RT
k = wate = Ae *
fz
Fs

sie R ln
0.693
At
172
Bae -104,600 J moi
(88914-79k > Smoleae |e
(5 x 1023 s-1)(60 s)
= 349K or 76 °C
-104,600 J mol
sb ts (8.314 J
1-1
K ~ mol ©) ln
0.693
|——-—-—-——-——_——_
(5S x 1023)
(60)? (24) (30)
= 270K .orca C

20.25 Isopropenyl allyl ether in the vapor state isomerizes to allyl

acetone according to a first-order rate equation. The following

equation gives the influence of temperature on the rate constant
-1)
(in s

where the activation energy is expressed in J mol.

ul
At 150 °C,
 327

how long will it take to build up a partial pressure of 0.395 bar

of allyl acetone, starting with 1 bar of isopropenyl allyl ether

[L. Stein and G.’W. Murphy, J. Am. Chem. Soc., 74, 1041 (1952)]?

SAL
ay eel LU
k = (5.4 x 102 71), (8-314) (423.15)
ee erat ae oc

ee 1 ee jpg 1 bar
eee
; PY
— =
0.605 bar
t = ae In

; 32535-1654, st
= 1420 s
20.26 For the mechanism
1 3
A+ Be ¢ CSD
ky
(a) Derive the rate law using the steady-state approximation to

eliminate the concentration of C. (b) Assuming that kz << ky,

express the pre-exponential factor A and Ea for the apparent

second-order rate constant in terms of A,, A), and Ag and

Ea.’ E,2° and E,3 for the three steps.

SOLUTION
atch. a =
(a) mae k, [Al [B] (k, + k,)1C] 0

aD} _ se 2 k, k, [AIL B ]
dt 3 k, + k,

(b) For k, >> k,,

-E/RT -E,,/RT
: k, k, 7 A,e A,e

app k, E 2 /RT
Ave
328

A, A, “(Ey + E.3 = Ei.) /kT

A, A
e573 = sat
anon i A, Pano i oral : 3 aa

k k
20.27 For the two parallel reactions A SS B and A pasa: (WF
show that the activation energy E for the disappearance of A is

given in terms of the activation energies E, and E, for the two

paths by
; KE, +r k,E,
k a k,

SOLUTION
The rate equation for A is

-d{A] _ ass a=
ae = k, [Al + k, [A] = (ky + k,) [A] k ¥ [A]

where t = k + k = Ae = /RT
1 2
rove ,
vag eee ¢
d in(k, + k,) ¥ Mae Coie) A dk, ; =
d ae dT (kp ker ~ (kh, 4k, wo vdiion dT
ed baa -_—-_-_o-oOoo- eee: oO SS eee
See ee ee - = ----_---—— —— ——

meee pe eh tere
(ara ur cke 2” dT

. 1 k,E, k,E,
(k, + k,) RT? RT”

ae ee ae
to ek
 329

20.28 The reaction 2NO + 0, —) 2NO, is third order. Assuming

that a small amount of NO, exists in rapid reversible equilibrium
with NO and 0, and that the rate-determining step is the slow

bimolecular reaction NO, ao NM) 2NO, , derive the rate

equation for this mechanism.

SOLUTION
= [NO,]
= eee
+ O,
2 == NO
3 * = TNOIIO;]
7)
NO, + NO ———> 2NO, (rate determining)

d{NO, ] 2
at = 2k, [NO,] [NO] = 2k, K [NO] [0,]

’ 2
k [NO]"[0,]

20.29 Set up the rate expressions for the following mechanism

ait ky
Ao B Boge (@ sees Sa SID

Ky
If the concentration of B is small compared with’ the

concentrations of A, C, and D, the steady-state approximation may

be used to derive the rate law. Show that this reaction may

follow the first-order equation at high pressures and the second-

order equation at low pressures.

Since the concentration of B is small, it is assumed to be in a

steady state.

Sage ekLAT) = AE ees k,(C]) (BI = 0

330

k, [A]
[B] Peore shearae
k, + k,[C]
kek:
d{D1 *«. ry Fei SPA LEI
ea es ee EO tet [C)
? d([D] _
At high pressures, k,[C] are aa k, [A]

ke k
d[D] _ ie)
At low pressures, k, »> k,(C], eee E, [A] [C]

20.30 The reaction NO, C1 = NO, + + Cl, is first order and appears to

follow the mechanism

Ki a)
NO, C1 —————) NO, + Cl NO, C1 ar (Cil ===> NO, + Cl,

(a) Assuming a steady state for the chlorine atom concentration,

show that the empirical first-order rate constant can be

identified with 2k,. (b) The following data were obtained by H.
F. Cordes and H. S. Johnston [J. Am. Chem. Soc., 76, 4264 (1954)]
at 180) -C. In. a single experiment the reaction is first order,
and the empirical rate constant is represented by k. Show that

the reaction is second order at these low gas pressures and

calculate the second-order rate constant.

6/105°*mols cnte 5 10 15 20
K/i0it 6 7 ae 5.2 6.9

SOLUTION
d [OD es ze
(3) =aaee 7 B, INO,C1)) = SRINO CITI CI) oa0

Therefore [Cl] =
ky
—
7)
 331

-d[NO,C1]
dt k, (NO, C1] + k, [NO,C1] [C1]

k, (NO, C1] = k, (NO, C1]k, /k,

i] 2k, [NO,C1]

(b) At low pressures the rate determining step is the first step,
and the reaction becomes second order.
,

k
1
N 10)701 + NO, C1 > NO, C1 — NO, ap (01)

-d[NO,C1]
ay parr ee ky [NO, C11? assuming [NO,C1] is approximately
constant

Loree = ky [NO, C1]

is U c
A eexen © 2 = k, (Se2010 )

, — -_

k = 63 .4°xz 10° cme mol s A

20.31 The apparent activation energy for the recombination of iodine

atoms in argon is -5.9 kJ mol, This negative temperature

coefficient may result from the following mechanism.

k
Ute = eB K = one il ae Uf an is ap Ju
CI] (M] k 2
i
Assuming that the first step remains at equilibrium, derive the

rate equation that includes both the forward and _ reverse

reactions. Show that the reverse reaction is bimolecular and the

equilibrium constant expression for the dissociation of iodine is

independent of the concentration of the third body.

332

SOLUTION
d{I,]
ae a LET s k_, (1,1)

Since [IM] = KI[I]I[M]

d{I,] 3
Poa cas ae Ibe k, (1, 1M]

Thus the rate law for the reverse reaction is k_, (1,1 (M1.

At equilibrium d{I,}/dt = 0 and = kK

[rie

20.32 What is the rate constant for the following reaction at 500 k?
Boot) HC) Ci eb
The data required are to be found in Tables 20.3 and A.2.

SOLUTION

The rate constant for the backward reaction is given by

k
b
= (Gaus cloreatmes ene) 9 23-000/8.314 x 500

aceon wore ee
0 0 0
AG = AG (C1) A ,G (H) AG (HC1)

94.191 - 192.955 + 97.169

87595 ‘ty Pdot

-1595/8.314
3 x 500 _ 4 3g,

8 1 =)
2° x10 L mol Ss
 333

20.33 What are the Arrhenius parameters for the following elementary
reaction?
H + HC1 —)> Cl + H,
The data required are to be found in Tables 20.3 and A.2.

SOLUTION
At 500 K
AH? = AgH°(1) - AgH°(H) - AgH° (HC1)
= 122.261 - 219.254 + 92.914 = -4.079 kJ moi
ASe® SUAS (CI)PRSesS"(H) SP*s (H) t= 8" (Cr)
= 176.749 + 145.737 - 125.462 - 201.995
= -4.971 J K? mo17}
Sep ee (1)
ae 0
wh
P c

4079/8314 T .-4.971/8.314 _ 9 seq ,490.6/T

= (1029-9 £ moi! e721) 5723 000/8-314 T

el NS
k= KK, = (1029°9 1 mort p72) 07232 000/BT (9.550) 04079/RT
f c

= (4.4 x 102° ib, age Saye ee RE

k
20.34 For the gas reaction O + 0, +i 0, + M
,

k
When M = 0,: Benson and Axworthy [J. Chem. Phys., 26, 1718 (1957)]
=) oe .5/RT
Rhee MEME 60a ey AO Le aotse as tee
where the activation energy is in kJ mol. Calculate the values
334

of the parameters in the Arrhenius equation for the reverse

reaction assuming AH® and AS are independent of temperature.

SOLUTION
AH’ =" 242.7 = 2497170 “= “="10675 &I asi:
AS° = 238.82 - 160.946 - 205.029 = - 127.16 J pee eee
=A{RE ASUR
K, e e

_ ,106,500/RT |-127.16/R

0
bey) i 1
K ae - x, (saa) not

C P\ co RT . k

ee ' 6k
24.46 Ky,

ae 6 eg ectoRE
24.46 ¢106+500/RT |-127.16/R

u
6 x 10’ 127.16R| 2500 - 106,500)/RT
24.46 ° £

(4.1 x 1022 a3 L molt gt) ) 9 1042000/RT

20.35 Derive the steady-state rate equation for the following mechanism
for a trimolecular reaction.

a * * k,
A+ A = A A. + M—)
A. + M
23 2 z
k
=

SOLUTION
d[A,]2a ee 2
yeahs lay’ (k_, + k,(M])[A,]* = 0
 aon

2
ir giet: ey aay es ee

20.36 For the mechanism

k) k,

+ X= 2HX ye es 9 HX + &E
H
: k : k
al =)

cs s
X, —— 2x Jel ar X, = Xe

Ks 4
show that the steady-state rate law is

a(HX) _ a 2
de 2 2k, TH, 1! (: KTH, 10%]

SOLUTION
There are five species, but there are two conservation equations.

fHi=s [HX}i. + 2[H,] = const.

xy & [HR] & 2X, ] const.

Therefore there are only three independent rate equations.

fy) SURES petra, Pe p kf MMT HT ee MCC ~— Lid

- k_,(HKI(H] - &_, CHK) (x)

py US = 2k) + E_{(exI[e) + Kalix.) = ¥_, fxr”

- k,(X][H,] - &_,UHKI[X] = 0

(3) MBL - gsrxiy] + &_,fexIEx] - & {TeKILH] - &,{HI(X)1 - 0

336

Adding 2k,
equations 2 and 3 [Xx] = eee
=—— [X,]

Substituting in equation 3 yields

k,[H,] + ky ay suas
tH] as
Tim as
‘ E,
as a
Substituting in equation 1
4 [BX]
ae rar 2k, [H, 1[X,] = k_, HX]
2 (k, 1%] f k, [HX])

2k,
oe ]
Bee =k_
tt)4 LHXI)
: : nie Rey
Se aa
ie

2k, [Xp] 3 (HX] + k,[x,]

eS My fea aT
, tT >FET
i) i
THX]
d(HX]
=_ ok, (H,IK,]
:
-
vf
2k, 08K)?
2
+ (eye, THI 1X5]
+ kjk ,UX,](HK] ; kyk g(HX](H,] -
- b kjk (HK) 2
+ kak ,(H,J(HX] + k,k,CH,J(X,] - k_k_, (0X) 2
2k» [Ky ]
i)
“Ugh egEE, ae inl eet
¥
= 2k, [H,J[X,] as 2k_, [EX]
2 + (2k,k,[H, J[X,] = S2KS 3k_ 40x17)

2k, [X5]
x ae
ki (HX) -+ “ke [X,]
 x, (xd?
= 2k, (H,11K,1 (1 - Perr
Sanit)
apy ee a 4 Se cenche fe. a Uf(ie |
ce es eahege kk, [B,1(X,]

2k, [X,]

x a2
k, [HX] + k,[X)]

2k, [X, ]

ren
dt
acer5 ee reid
ete
toe wells
K(H, J[X,]
Slaaliasy stat 2 Vee
k,5s k_,{HX] + k,[X,]

aS 2k,

2
Soe hoc 2 Be a ae es
ta 3 2 KIH, ][X, ] k_, [BX]
+
k,[X,]

20.37 The mechanism of the pyrolysis of acetaldehyde at 520 °C and 0.2

bar is
Si
CH, CHO ———) CH, + CHO

Ky
CH, + CH, CHO > CH, + CH,CO

CH,CO
3
————— 1CO) + CH,

CE. + CH,
KA
ao) C,H.

What is the rate law for the reaction of acetaldehyde, using the

usual assumptions? (As a simplification further reactions of the

radical CHO have been omitted and its rate equation may be

ignored.)
338

d (CH, CHO]
Ce ee 1 + ,{CH,1)[CH,CHO] = 0
dt

a [CH, ] .
Oe ae k, (CH,CHO] - k, (CH,][CH,CHO] + k,[CH,CO]

= Sai=
2k, [CH 1, 90

a [CH,CO]
(3) oe reas ae k, [CH] [CH ,CHO] = k,(CH,CO] = 0

Equation 3 yields [CH CO] = k, (CH, ][CH,CHO]/k,

Substituting this in equation 2 yields

2
k, (CH, CHO]
[CH,] = 2k,

Substituting this in equation 1 yields

LZ
a [CH,CHO] k,
a . em i
aaa Ss k, + = i) [CH CHO] ’? |(cH, cio}
If k, is small,

d [CH CHO]
1/
oor ae
>
ae k, (k,/2k,) [cH ,cHol® /2

20.38 Cr: ey iH 0.0348 mint

at 60 min k 0.0347 mint
(6). 20.0 min
20.39 0.25 min 4 2.77 min 4.00 min
20.40 (a) first (b)3959) x 108 eee (c) 0.354
20.41 4-038 Gel On emin
 339

20. 42 14.6%
20 43 (a) 4.97 x 10.7% (b) 6950 g
20 -44 (a) 0.107 L mot72 gt (b) 2850 s
20. 45 (a) 221 s (b) 82.5 s
20. 46 40.4 bar s 1

20 47 (a) 80% (b) 67.2% (c) 61.7%

20. 48 (a) 3.5% (b) 9%

20 -49 (a) 39506 (b) 32,900 ft?

20. 50 t = 2( 42 Es we)
1/2 r72

20 rey S 3.3-5-107 2
d[H, SeO. ]
20. 52 Ai SS ee +,277-73
aera rae ett k[H,Se0,][H [ee

20. 53 0.00750 mo1 L~2

20. 35 [B] =< KIA) te**

[c] = [A](1 wae (ia ke)
d({Bro0.
a J =RT =k’ 180,”
sg ERR EE URL, Co 1°1H
1° (80,7 a 1 Br)Ss
20. 56

20. | (a) 97.1 kJ mol? (vb) 9.3 x 1013 ,-1

(ey1.7 s

20. 58 CUE Cu ea (b) 388 °C

20. 59 (a) 5.3 x 10° s (b) 2740 s
20. 60 550 s
340

20.61 (a) 1091 K (b) 2180 K (co) 727-K

(d) The rate of the reaction with the higher activation

energy increases more rapidly with increasing
temperature than the rate of the reaction with the lower
activation energy.

20.62 A = 3x 10° L7 mol 2 s * E, = 57305 mo1~4

20.63 (a) 1.07 bar? 5-2 3.06 = 101° bar = -
(b) 0.013 s 0.62 s

20.64 K = [AB]/[(A][B] = exp ( exe(- 9

dtDia2
agers k(C][AB]
A= kI{C][A][B] exp ist)
aexp
AnH®
a)

E ° A
Ss exp (-Z) [C] [A] [B] exp (4s) exp ¢ an)

aBA + AH® AS°

k = A exp we Gre where A = §S exp (45°)

dO, ]
20.66 Page = 2k, [NO][0,]

20.67 $.0 5110-0 1 moles aot

2
20.68 2 ofA)”
a 3le eG 1 sfu,? © 84hty/k, [A]
CHAPTER 21: Theoretical Gas Kinetics

21 a | Use equation 20.68 to derive the expression for the activation

energy for a reaction following simple collision theory.

SOLUTION
Es =
od
RT
ink
aT

—S 07 ke.
ae 2 1 ote. 8
k.,'= Nat yp (8k, T/ mh) e

AR nal 2 1/2 1
E. = RT aT In Dorcas + z In (We ee @/k,T

q WS 97/4 *o
B

1
= Nx & 6 + > RT

21. Use the pre-exponential factor A = 3x 1013 cm? mo1-! 5! for

the reaction Br + Hy —> HBr + H to calculate the cross section

and collision diameter for this reaction at 400 K.

SOLUTION
1
ae wperoeeaoe 4 ee
2
719.904 x 10> kg 2.0158 x 10° kg
<1, 9660510— kg moins
1/2
( Lye _ | 8(8.314 JK" mol”) (400 K)
ae n(1.966 x 107° kg moi)
Oise

Pmt ec Maks wie

mse) TN ,
342

A 1/2
#2 ; SRT 72.
TUN 4

iL
= (CGix 1023 Pe mole a 1010 ‘ m cm ye “ ear 4vod
n(6.02 x 1023 mo1~1)(2075 m s~2)

The cross section is nd >” = 2.40 x 100" ace

Zits The thermal decomposition of gaseous acetaldehyde is a second-

order reaction. The value of E, is 190,400 J molt, and the
molecular diameter of the acetaldehyde molecule is 5 x 1078 cm.

(a) Calculate the number of molecules colliding per cm 3 per second

at 800 K and 1 bar pressure. (b) Calculate k in L mol! 5},

SOLUTION
ere SAS BACs Nome 16207 1022 motes)
RY (8.314 J K+ mo1~+) (800 K)
ero OSes 1058 mee
1/2
<v> = TRY =. sone
M
= OO)
Z44 = 2 p nd <v>

_ (9.05 x 1074 my? (5 x 101° my? (689)

31/2

= 9,139 a9 0 eee ae

1/63. 13ear 10° ee ea oe Caeaie \

= B53 t0- Nene ee

 343

a
(10° dim °)Ny AS Zo, 0-B/RY
0
(b) k = ——————~—— ee
2
p

Mella a lb 0g2er 10, mole (3,15 200 mn 5)

(9:17 2107 m3
_ __190,400
; (8.314) (800)

= 0.083 L mol 5 ¢
21.4 The pre-exponential factor for the reaction Ho zt: I, = 2eHL as

1011 1 moi! s-1 and the activation energy is 165 kJ mol? in the
range 300 - 500 °c. If the collision diameter is 320 pm, what
value of the pre-exponential factor is expected from collision

theory at 600 K and what is the value of the steric factor p? (At
higher temperatures this reaction goes by the unbranched chain

mechanism described in Section 20.15.)

SOLUTION
1
uN,
A = 1 a a
2(1.0079 x 10° kg) 2(126.9045 x 10> kg)
=3
= 1.999 x 10° kg

Ga 2 8RT te
eintet? mUN 4

| 2
ei 820x10 mn) 8(8.314 J K mo} tooo) (6.02x1073 moi)
n(1.999 x 10 ~~ kg)
x (10° ib >
= 4.87 x 197 L Tosh ati
PS ii gs 1 =1 1
= 10-7 L mol : s ies (4.87 x 10+ L mol s )p
exp
= 0.21
344

72es Show that the activated complex theory yields the simple collision

theory result when it is applied to the reaction of two rigid

spherical molecules.

SOLUTION
Assuming that the molecules react on their first collision (that
is, the activation energy is zero), activated complex theory
yields
of +

Po ae (1)
h ay" 4
where qy' and dp’ are molecular partition functions without
oo

the volume factor, and q wet is the molecular partition function

for the activated complex without the volume factor and without

the vibrational factor.

2nm kT aie 2mm kT S12

ewe
A
(n (2) qn’B = (=)
2
(3)
i We 2 2)
nee 2n(my + mp) kT 8n w(Ry + R,) kr mK
AB 2 2

mn, Mm

Substituting equations 2, 3, 4 and 5 in equation 1 yields

1/2
7 8nkT 2
k = Ny ( i (Ry + R,)

which may be compared with equation 21.2

: 2 / 8RT 1/2 _ (8nkt 1/2 2

k md15 ea z ( i ) (R, + Rp)
The difference between these expressions of a factor of Na is
simply a matter of units.
 345

21.6 What is the expression for the pre-exponential factor of a second

order gas reaction according to the thermodynamic formulation of
transition-state theory? What is the value of the pre-exponential
factor at 500 K if the entropy of activation is zero? When this
value is compared with values in Table 20.3, what do you conclude
about the sign of ast?

SOLUTION
ig caer! Les (2.718)" (8.314 J Kt mo1 )(500 K)
o°N,h (1 mol L7+) (6.022 x 1027 mo1~1)(6.63 x 10°24 J s)

= 7.70 x 10. L fol: <5

log (A/L rahe — = 13.9

ast is negative for all of these reactions, and is more negative

for metathesis reactions not involving atoms. This means that the
transition state has a lower entropy than the reactants.

21.7 F, W. Schuler and G. W. Murphy [J. Am. Chem. Soc., 72, 3155
(1950)] studied the thermal rearrangement of vinyl allyl ether to

allyl acetaldehyde in the range 150 to 200 °C and found that

ay 1011 e128, 000/RT

where k is in s ! and the activation energy is in J mol,

Calculate (a) the enthalpy of activation, and (b) the entropy of
activation, and (c) give an interpretation of the latter.

SOLUTION
The values of ant and ast are calculated for the mean temperature
of the range 273 + 175 = 448 k.

(a) aut IE RT

SDR I0UkT mol. = (8.314 410 > kJoK * mol) (448K)

346

124.3 kJ mol4
: N,bA
(b) AS = R In “RT = 1

23 =f =34
Wy Rides pata ee Oa ee mel ——— Tues) Noy
(8.314 J K7 mo1~1) (448 K)
iio Kael

A eee ne

(c) The activated complex may be an improbable ring structure

which is formed with a decrease in entropy.

PA The vapor-phase decomposition of di-t-butyl peroxide is first

order in the range 110 to 280 °C and follows the equation

k = 3 2) x 1016 e163, 600/RT

where k is in si and E, is in J mol !, Calculate (a) ABT , and

(b) Ast,
SOLUTION
(a) AHF = ED - RT
= bel63,600IT amolits sauu(8.304 0) Koesomobeo(443.ae)
= 159,900 J mol
N, bA
(b) AS e R in ed
RT

= (8.314 JK mol) |1a (6.02x107° moll )(6.626xh0me

6 : J_s)A
(2.718)(8.314 JK mol) (448 K)
!
WW A ‘© > ay A B° —_

Pad i] mw NO > = So
 347

21.9 (a2 0x 1011 1 moi? 574

(b) 3.2 x 10°29

(ej Dod tls
PALO Tee OL ere a feat laa?

21.12 -598, -544 and -523 J K+ mol + when the standard

concentration is taken as 1 mol L~. The activated complex
is more organized (lower entropy) than the reactants. This
is especially true for the first reaction.

21.13 Tg Oo le (ine 0ees 1One eas

21.14 (a) 224 kJ mol (bo) 18.0 3 K moi?
CHAPTER 22: Kinetics: Liquid Phase

22 sil Show that if A and B can be represented by spheres of the same

radius that react when they touch, the second-order rate constant

is given by

3
5 vey CSOT FF nsiaeuee
a 3H

where R is in J K moi?. To obtain this result the diffusion

coefficient is expressed in terms of the radius of a spherical

particle by use of equation 22.45. For water at 25 aC)

n = 8.95 x10 4 kg mts !, Calculate k at 25 °C.
SOLUTION
The diffusion coefficient for a spherical particle of radius r is
given by

eee eeRT
N,6nnx

Substituting in equation 22.4

k= . 4x(207 3 Lom)" <3 )N,(D, + DDR,,

2RT
= 4n(10° iF aa ( a )(az)
6mnr

8 x 10° RT =r
— —— I. mol ~ §
3n
where RT is expressed in J mol! and n is expressed in kg mt sl,

For water at 25 °C

8(10° Lm °)(8.314a, J Kt mol

5 +)(298 K) = 7.4 x 10? L moi? 5-1
3(8.95 x 104 kg mt 5-1)
 349

22.2 The diffusion coefficient D of an ion is related to its ionic

mobility u by

The ionic mobilities of H* and OH are

S263ex 10 a cee and
i ew al Gaal o :
2.05 x 10 m” V at 25 C. What is the rate constant
for the reaction H* + OH ——») H,0? The reaction radius is
0.75 nm, because once the proton is this close the reaction can
proceed very rapidly by quantum mechanical tunneling. The

electrostatic factor f is 1.70.

SOLUTION

Fe ELLE 10.’ m” v_* s_-)(8.314 J K mol) (298 K)

1 96,500 C mol
= 89539 Fat0n ems 20"

Foe 82208 x 10°) m? V" s°7)(8.314 J K- mol

1)(298°K)
2 96,500 C moi!
S86 x 10° ee

Peete 0 ee
a AY ND ot cide 2° Ra
"42
9° 2 =i
Eran 0 Lee 116.022 x 10 des iocsWeh cures he ee
x (0.75 x 10? m)1.7
ial sil
Tae ton seme ce

22.3 What is the reaction radius for the reaction

11 -1 -1
H’ ar |): _1.4 x10 Lmol ss y H,0
350

at? 259°C given that the diffusion coefficients of H* and OW at

this temperature are 9.1 x 10-9 ms) and 5.2 010° yaw ts =i

SOLUTION
k = 4nN,(D, + D,)R,>f

a
12 4nN (D5 + DD)
2
3 3
pe (leas 1014 L rites A eng: m ee)
4n(6.02-x 107° mol) (14-3) x 10 > m-*se
9
i] 1.29 x10° m

To calculate the electrostatic factor f, we have to know Ri2-

Successiv e approximations have to be made. Let us begin by

estimating Ry = 0.9 nm.

Lag toe
-(1.602 x 10729 c)2(8.988 x 109
N C7? m2)
(78.3) (1538 x 10-> ka 6298 K) (0.0 x 10am)
2091960 ¢= x

506° R181) #320 ciaae ee

1.45
1929's 1074 +e
Thus R aoe a Seer ye = 0.89 nm
12

22.4 Derive the relation between the relaxation time r and the rate

constants for the reaction

B, which is subjected to a small displacement

from equilibrium.
 351

age Ey La my > &, 1B)

At equilibrium

d{B] _ 2 s
Satan 0: c= Sy Sah

Let [A] = [A] - A{B]

eq
EB ise CB] + A[B]
eq

d{B] — dA[B] _ 4 "

oe af iscach Bales A[B]) Me ea + A[B])

= hs = ae = (k, + k,)A[B]

=are. (k, - k, ) ALB] Bee

= Ate!)
.

Z -1
ct = (k, + k,)

ae) For acetic acid in dilute aqueous solution at 25 ce K =

ih[sh se 1075, ends the aselaxation time is 85sxu10— seconds for oe
0.1 M solution. Calculate k, and Ky in

7 - +
CH,CO,H = cH,CO, + H
a

SOLUTION
Sele eee: ] : 2 ws Hicilt Beak et
+ =

[CH CO, H] 0.10 K

x) = (1.73 10° °)3 17 Or & [H] = [CH,CO, ]

1
+ _—

ky + k ((H let [CH CO, 1)

352

Pe rate Pee Tee

1.73 x 10°> k + &(2.64 x 10°°)

by i} AON enol ess

k i} (1.73 x 10°>)k, Bs ees 0 Gk

d

225 Calculate the first-order rate constants for the dissociation of

the following weak acids: acetic acid, acid form of imidazole

+ +
The corresponding acid dissociation constants are

We iSe e105) le OL endaes oie 910, respectively. The

second-order rate constants for the formation of the acid forms

from a proton plus the base are 4.5 x 101°, and 4.3 x 1019 L

mol! st, respectively.

SOLUTION
s ; ;
Eor, HA -——= H + A

ky

age RANCH aek,

+ -

[HA]

For acetic acid k, = kK

= (4.5% 10" -Eomold s°CTS 10 l enomema

LaeTowetG> ae
For imidazole k, = kK
1 — as — =
= (1.5 x 10 o L mol : s 14.2 x 10 q mol L y
aes 0) ee
For NH 3 k, = kK
4 te a2
= (4,9 2010 10 Slemole ioeear Seyi = :
10 +o moter at)
-1
= 25 5s
 353

a a The mutarotation of glucose is first order in _ glucose

concentration and is catalyzed by acids (A) and bases (B). The
first-order rate constant may be expressed by an equation of the
type that is encountered in reactions with parallel paths.

k = ky + kgt(H’] + k,fA] + kp(B]

where k, is the first-order rate constant in the absence of acids
and bases other than water. The following data were obtained by
J. N. Bronsted and E. A. Guggenheim [J. Am. Chem. Soc., 49, 2554
(1927)] at 18 °C in a medium containing 0.02 mol L + sodium
acetate and various concentrations of acetic acid.
[CH,CO,H] /mol uit 0.020 0.105 0,199
k/107* mint 1.36 1.40 1.46
Calculate Ky and K,. The term involving kpt+ is negligible under
these conditions.

SOLUTION

01 0
CCHsCOHI/mol L
354

Intercept = k. fe) = 1.35 x 107-4 min

4
Slope = (12465
1 35)o3 10 5.5 x 10> L mol 1 min Ai k
0.2 mol Lt

IP ¢ The mutarotation of glucose is catalyzed by acids and bases and is

first order in the concentration of glucose. When perchloric acid

is used as a catalyst, the concentration of hydrogen ions may be

taken to be equal to the concentration of perchloric acid, and the

catalysis by perchlorate ion may be ignored since it is such a

weak base. The following first-order constants were obtained by

J. N. Bronsted and E. A. Guggenheim [J. Am. Chem. Soc., 49, 2554
(1927) lat 18, £C;
[HC10,]/mol1 ba 0.0010 0.0048 0.0099 0.0192 0.0300 0.0400
k/10-4min 1525 1.38 deer) 1.90 e415 PIL)
Calculate the values of the constants in the equation
fe ke) ek Hd
SOLUTION

y ee a
CHCl 0.10%mol L*
 355

Intercept = k. = 1.21 x 10-4 min!

Slope = kypt = 3.4 x 107° L mol! min7+

-

Adipic acid and 1,10-decamethylene glycol were mixed in equimolar

amounts and polymerized at 161 °C and 191 °C [S. D. Hamann, D. H.
Solomon, and J. D. Swift, J. Macromol. Sci. Chem., A2, 153
(1968) ]. The extents of reaction, as determined by acid
titration, are as follows:

t/min 0 200 400 600 800

p(161 °C) 0.820 0.900 0.927 0.940 0.947
p(191 °C) 0.820 0.937 0.955 0.963 0.968
Time was measured from the point at which there was 85%

esterification. Taking [CO,E]5 = 1.25 mol kg at both

temperatures, what are the two values of k and the activation

energy?

SOLUTION
aaa 5 SS SF
(1 2p) (deed) 821)

At 161 °C
Qa) eee OTe
2
2[CO, #1, 3

0.111, 0.125, 0.132, 0.130 for the 4 successive times

= ONS ae A ie aes

At 191 °C
k =" 0756 ne" hy be ine?

phere Al
Cee 3? 288182314) (459) (489) 50.36
a Priest] Ey 30 0.13

= {68} Fell pole.

356

22.10 Adipic acid and diethylene glycol were polymerized at 109 He using

p-toluene sulfuric acid as a catalyst [P. J. Flory, J. Am. Chem.

Soc., 61, 3334 (1939)]. The extents of reaction at various times

are as follows:
t/min 0 40 80 120
P 0.800 0.909 0.944 0.960
Note that the time is taken as zero at p = 0.80. At what time
will the number average molar mass reach 10,000 g mol 1 for this
concentration of reactants and catalyst?

SOLUTION
1
= 1.4 k,[CO,H] \t
1i=ep
ads Piles” 1 + k, [CO,H] (0
1 — 0.800

1 - p 1- 0.800 _ k, (CO,H]|
|
re oQ i=) io ey i} o = nN 8 fete6
N i) °

M
p= 1-2 = 1-8eRol_ _ 6.9784
n 104 g mol
i) 1! et
1 — 0.9784 i= 02800 (0.16 min “)t
t = 258 min

22.11 For a condensation polymerization of a hydroxyacid in which 99% of

the acid groups are used up, calculate (a) the average number of
monomer units in the polymer molecules, (b) the probability that
a given molecule will have the number of residues given by this
value, and (c) the weight fraction having this particular number
of monomer units.
 357

SOLUTION

(a) The number-average degree of polymerization is given by

xX 1 1
n Lcapivescd — 0:99 er ae

(b) The probability that a given molecule will have 100 residues
is given by
hae |
t, = p (i= p)

200 s=- 1
© = 0.99 (ta09)) = 340ix 10°

(c) The weight fraction having this number of residues is given

by
WSq¢ > ips 1 eee

Wing Ls
= (100)(0.99) 100-—-1 (1 - 0.99) 2

3.70 x 10>
22.12 In the condensation polymerization of a hydroxyacid with a residue
mass of 200 it is found that 99% of the acid groups are used up.
Calculate (a) the number-average molar mass, and (b) the mass-—
average molar mass.

SOLUTION
(a)
=XO repay
1 ee SOTO
1 - 100

=1 =]
MM = (100)(200 g mol ) = 20,000 g mol

ae
(b) i > Betup. =..1:.99
n
=
M = 39,800 g mol
358

22.13 A hydroxyacid HO-(CH,)5-COH is polymerized and it is found that

the product has a number average molar mass of 20,000 g molt,

(a) What is the extent of reaction p? (b) What is the degree of

polymerization eae (c) What is the mass-average molar mass?

SOLUTION
The molar mass of a monomer unit is 114 g molt = M,

(a) M. = M /(1 — p)
n Oo

p = 1 Mi/M = 1 —- 114/20,000 = 0.9943

1 1 2
Oe ATE pico. t > 0.9943. pics

y L+p _ 1.9943
bein ho Dope te 1 09945
= 39,900 g ip
1
22.14 Suppose an enzyme has a turnover number of 104 win ~ and a molar

mass of 60,000 g molt. How many moles of substrate can be turned

over per hour per gram of enzyme if the substrate concentration is

twice the Michaelis constant? It is assumed that the substrate

concentration is maintained constant by a preceding enzymatic

reaction and that products do not accumulate and inhibit the

reaction.

SOLUTION
: V re
(104 min?) [E] fo)
1 + K/[S] 1+ 0.5

» (104 nines) g/60,000 g mol) (60 min hee)

owleholehe.
 359

22.15 The kinetics of the fumarase reaction fumarate + H,0 = L-malate

is studied at 25 °C using an 0.01 ionic strength buffer of pH 7.

The rate of reaction is obtained using a recording ultraviolet
spectrometer to measure the fumarate concentration. The following

rates of the forward reaction are obtained using a fumarase

concentration of 5 x 10-29 moi L7!.

[F1/10 ° mol oes vp/10 mol Las ne

2 22,
40 5.9

The following rates of the reverse reaction are obtained using a

fumarase concentration of 5 x 10710 mol ee

[M]/10 ° mol i Vy/10 mol ee ae

5 1.3
100 3.6

(a) Calculate the Michaelis constants and turnover numbers for the

two substrates. In practice many more concentrations would be

studied. (b) Calculate the four rate constants in the mechanism

A ky
eee OX et
Ky a2
where E represents the catalytic site. There are four catalytic

sites per fumarase molecule. (c) Calculate Keg for the reaction
catalyzed. The concentration of H,0 is omitted in the expression

for the equilibrium constant because its concentration cannot be

varied in dilute aqueous solutions.

360

SOLUTION

ee
287. ar
seat fer
dete Keo (BA F
Vv
Yr + F j Ky,
TF] == Ve

Teles 107 Oto Rk. ey

; : F F

5.9: 10. Eee. OCOLAS

: LeF way F

-3.7 x10) + 0.0952 K, = 0

3.7 x107 -6 =1
K., = 9.0952 cy iat)
se ah) mol L

Ye = 2.22 OMe (OH1110) (3695x4050) = 6655410) ewcieLn en

PS M hind
widats
1 + K,/ UM]

Vv.
De | a
‘wo Tl ue OR

1edbxcd0a | Gat OhO26Or

: KV
M M

BG ss'0k ake AOKO0S6

: Raabe
M RYM

oov3uxe10 4 on1050224 Ky, = 0

Kee
M et Ome Sk
0.0224 103.4010?!
Se ae moleLat

< Hl 1.3) x10. =$ 02026(1203 0x 100) ww deen On re tee

 361

The rate constants should be expressed in terms of the concentra-

tion of enzymatic sites and so
a

625. x 8107) mol L2 ote

[E] Boss 10> ¢ =

° A(Ste 1077 hao whe)

o-0ts 10g nol yi ot

2.0 x 10% 5-2
A(5 10719 oi Lt)

(3.3. + 2,0 ) x 102 Pea

Boa 100° moll.

(3.3 ) x 102 gis

+ 2.0
1.03 x10 mol_L*

Sei ae

Ve Ew
uF
10>)
(450 x 107") (3. ots. 40°)

(1.4 x 10°) (3.3 x

a)
(25 Olex. 107) (5.1 x
362

PAPE SAK At pH 7 the measured Michaelis constant and maximum velocity for

the enzymatic conversion of fumarate to L-malate

fumarate + H,0 = L-malate

are 4.0 x 10° mol Lt and (1.3 x 10° s-/){EJ,, where [E], is
the total molar concentration of the enzyme. The Michaelis

constant and maximum velocity for the reverse reaction are

10) x 10°° moll Let vand "(0080 x02 1) (E] Bs Whats demthe
equilibrium constant for this hydration reaction? (The activity

of water is set equal to unity since it is in excess.)

SOLUTION
K = eq _

(1.3 x 10° s *)[E] (10 B40 el Le)

(0.8 x 10° s*)[E] (4.0 x 10n motels.)

Pp PANG Derive the steady-state rate equation for the mechanism

“i k, K4
E + = x — E+ P E + EET
k, k,

for the case that [S] >> [E], and [I] >> [E] |.

SOLUTION
[E] | = [E] + [EIT +8 [x]

= EO e+ [I]/K,) + [X] (1)

k
.
since Ky
_= LEVER
“TET.
saes5
hadLe
4
 363

Assuming that X is in a steady state

aixl)
dt = k, (EJ(S) = (k, + k,)(X] = 0 XZ)

Solving equation 1 for [E] and substituting this expression in

equation 2 yields

k, [S][E] k,[S]
moe
1 + [1]/K,
= KN |e
INTER (I1/K,
etl 2
tk 3

d(P]
——
_= «,X)] = —_————
ee
dt 3 koe re kk
rts (: A =
k, [8] Ky

y,
= s
K
s [1]
BER eee PL Be
[S] ( a

22.18 The following initial velocities were determined

spectrophotometrically for solutions of sodium succinate to which

a constant amount of succinoxidase was added. The velocities are

given as the change in absorbancy at 250 nm in 10 x. Calculate V,

Kea nd Ky for malonate.

s

Ax 103
10 s

[Succinate] No 15 2 10 “moi §
10° mol L Inhibitor ____malonate
10 16.7 14.9
2 14.2 10.0
1 11.3 1.7
0.5 8.8 4.9
0.33 7.1 =
 02 15x10 *mol L”
malonate

No inhibitor

0
0 | 3
VCS]
Vv
er atF} = ——,--4 --- (22.85)
: — ar S n|
[S] K,

i 1
Ks {I]
bog s
pal
Ss
ns
I

=
Vv
e066?
:
Vi.s sis .

Slope without inhibitor

3, nia 90 066 1 Se? Oe ag K
zs
3 = M10° “I-mol> s

A i} (25-< 108) (15.1)) a= ONS raion mol L~ 1

 365

Slope with inhibitor

4 = 0.069 = KSir +
= TOE H 02006
9 = 10° Lo mol . Ky

-6 =|

0.069 =- 55/1
0.38 + US gx LO : mol L
I

Ses =G SI
Ett
ke Ot ET
eee
fame ame Acie |
0.38

22.19 The maximum initial velocities for an enzymatic reaction are

determined at a series of pH values.

pH 6.0 Shes) ie 8.0 8.5 9.0

¥; i| 74 129 147 108 53
Calculate the values of the parameters v4 K K, in

UJ

Vv
1, foTR + 1 /K, + KTH+
Hint. A plot of V versus pH may be constructed and the hydrogen

ion concentration at the midpoint on the acid side referred to as

ol, and the hydrogen ion concentration at the midpoint on the

basic side is referred to as paral 2 Then

+ + + +
K. = [H Le + [H 1, - 4 UB ] {H ],

+ +
[H ] (H 1,

b K
a

SOLUTION

(Please see top of page 366)

366

150

100

50

0
6 7 3 g
ph

[#1 = 100! te O03 aN”

fe ce io) 8 = ae so

Ka See eee
a
org a b es ate a [EH] b

;
ONS xO
-9 + 1.74 x 10
-9 = 4a
PETS
(O13) exoel
eta
Ole) (lea 14x Ole)

Anaieertom nels Le
PK = 17.36

[ho Tete| (9.3 x 10,°) (94.2 10 4)

K bs pete oe
b K =8
a 4.41 x 10

CPiipre Woe eth ibs

or 8.45
 367
,

deeelh 1/K a
+ K-/{h
b
|
-

147 :
1 + {10 “(44d c0l07°)t+ (0.367 x 107°) 10°)
V= 234

22.20 Alcohol dehydrogenase catalyzes the reaction

alcohol + NADY = aldehyde + NADH + H*

where NAD* is nicotinamide adenine dinucleotide in the oxidized

form and NADE in the reduced form. For enzyme isolated from yeast

the maximum velocity for ethyl alcohol is given by

V(mol L>! min!) = 2.7 x 107 (Ele

where [E], is the molar concentration of enzyme of molar mass

150,000 ¢g mol ?, The reaction is conveniently followed

spectrophotometrically at 340 nm because NADH has a molar
absorbancy coefficient of 620 (mol L-1)71 ont,

a
Absorbancy = log To 6200[NADH]d

where d is the thickness of the spectrophotometer cuvette. How

many grams of enzyme must be placed in a 3-mL reaction mixture to

produce a rate of change of absorbancy of 0.001 per minute when a

1.0-cm cuvette is used?

SOLUTION
d [NADH] Verne 10 nine TEI
dt i
a i 1 d [NADH]
AG [6200(mol L ) cm ](1 cm) At
368

10
- ~ min = ~ = [6200(mol
ee
L S 1102.7 x 104 min
=| )TE],

= [6200(mol
-
L TOE x 104 min
~1 )
m

(0.003 L) (150,000 g mole)

9
m = 2.7 x 107 g of enzyme in 3 mL

22.21 What current density i will be obtained for the evolution of

hydrogen gas on (a) Pt, and (b) Fe from 1 mol Lu! nc1 at 25 °C

at an overpotential of 0.1 volt?

SOLUTION
E. /2.303a
(a) i = - e "

= (1072*© 4 om?) 90-2 (2-308) (0.028)

= 0.012 A cm
fey. Seago, 2 2 330.130)

= 1.4 x 10° A Ere

De. 122 0.6 nm

22. 22 2 nex 10-4 s

22 .24 Seoens

22 APB) E, = 1,8 x 40°° L mol 3°"

roy ead oxi0 er
22. 26 dit =m (CAY = Blea) ok (iGlee Gt Iba)
22. 27 Lich seit ky Kgp Sk eee, Re
2?) 29 H* production: k = 1.75 x 10°, 1.2 x 107, 5.71 st
OH production: k = 5.71, 0.83 x 103, 1.8 x 10> s~4
Imidazole can play both roles about equally well.
 369

22.30 Kj = [H0C1][0H~]/[0C17]

stat = k{I ][HOC1] = k(I 1K, [0C1 1/[0H ]

52731 0.57 kg mol mint

22.32 (a) 20 (b) 0.0189 (c) 0.0189
22.43 20M, 39.0 My
02°34 179 hr
22.35 Vo = 1.2 x 107° moi L! 571
Ko = "Or488x810 “emel Lt
22.36 (a) ky = Wes e yoo mor eet
eer? ole eee
£000.33 x 107%
kent) 553 x10) 0 mol 2 oe.
(b) 3.43 bJ mol
22.37 kjeeoPr 408s 10° oly 3.*
so 2.6 x 103 st

k» =O Oaex. 103 gui

a dex 10° Lemel apo

a a(P,] (ky Si ge e keke feeen.
dt k,(S] + k ,[P,] + k, + k_,[P,]

Peta
f
ee Gres
Seok ky
k, [S]
370

yead k_,(P,1LE],
r k k_,[P,]
Lo
2 7
k_, [P,] k_,[P,]

Thus all four rate constants can be determined.

Ph 39 V = kk, TE]\ |/ (ky ote k,) K. = k,/(k, + k,)

Since no enzyme-substrate complex is formed, this mechanism

does not account for the selectivity of enzyme-catalyzed
reactions.

Dye -40 The product completely inhibits the enzyme, putting it out of
action before all the S is used up. Since the binding of
product is reversible, the reaction can be restarted by
adding more substrate and displacing the product.

22 41 33%
BPD 42 V, = KklE],/[1 + [B"]/Kpyo]
Page Bit = [1 + bliss
1 [1 + [H 1/Kpyg]

ae k falcJ{E]
22. 43
fwg Stele].
k, [NAD“]
22. 44 (a) 0.045 (b) 1.31 V
272 45 (a) 78.2 kJ moi! (b) 73.6 kJ mo1
(co) da tect (4) 0.929 s 4
CHAPTER 23: Photochemistry

23 git A certain photochemical reaction requires an excitation energy of

126 kJ molt. To what values does this correspond in _ the

following units: (a) frequency of light, (b) wave number, (c)
wavelength in nanometers, and (d) electron volts?

SOLUTION

0) _ £E EE Ws £10 soeweT
(6.63 x 107°" J s)(6.02.x.102° mol-)
SGrie AoL

ee eet0 so cn)
. 2.998 x 108 ms
rio es00 an

Gs = ee re G45 ai 10 cee ae OOS Ae

10,500 cmt
-1
(d) _126
kJ mol _ 241 6V
96,485 C mol

Zo 2 How many moles of photons does a 560 nm laser with an intensity of

0.1 watt at this wavelength produce in one hour?

SOLUTION
= -9
EX (D1 Js 00 1X60 3s) (5605x2102) om) - —
ene ee ae na ee a ee gee a
ane (6 Doge” Goth, 3).(6.62625 10 3477 08) (0409815 10° aus.)

SET 10 gol
372

23.3 A sample of gaseous acetone is irradiated with monochromatic light

having a wavelength of 313 nm. Light of this wavelength

decomposed the acetone according to the equation

The reaction cell used has a volume of 59 com>, The acetone vapor
absorbs 91.5% of the incident energy. During the experiment the

following data are obtained.

Temperature of reaction = 56.7 =C

Initial pressure = 102.16 kPa
Final pressure = 104.42 kPa
Time of radiation = 7 hr
Incident energy = 48.1 x 107 od, oa

What is the quantum yield?

SOLUTION
Since PV = nRT, VAP = RTAn
=6 =3 3
cease var _ (59. x 10.) m, ) 1104.42, = (102216) x 10) Pal
(8.314 JK? mo1 +) (329.85 K)
Ea sScexel0er mol
= (4.86 x 10 -)(6.02 x 105° mol-)
19 A
= 2.93 x 10 molecules reacting

fatal ae! (etede e107" 7 tata 9ogO whet)

: 313) x 107m
=i 862360x/1000"
Number of quanta absorbed

(48.1 x 104 Js ')(7 x 60 x 60 s)(0.915) 20

-4 =

vie | ee en Ge ae eee aaa me 1 7S 2810

6.36 x 10 a
19
2to 3 10
go = “==> — = 0.167
1.75 x 1029
 373

23.4 A 100-cm? vessel containing hydrogen and chlorine was irradiated

with light of 400 nm. Measurements with a thermopile showed that
Des 10)| J of light energy was absorbed by the chlorine per
second. During an irradiation of 1 min the partial pressure of

chlorine, as determined by the absorption of light and the

application of Beer's law, decreased from 27.3 to 20.8 kPa

(corrected to 0 °C). What is the quantum yield?

SOLUTION
noe be _ (6.626 x 10°" J s)(2.998 x 10° ms)
x 400 x 10°? m
4.97 x 10°73
Number of =4/ =i
quanta absorbed = Ad ex 10* 38s F160" 3)’ = 15./3)39 x 1014

4.97 x 10°19 5
Since PV = nRT, VAP = RTAn

EVAR CL (Osdax, 100 3 m>) (27.3 - 20.8) x 10° Pa](6.02 x 10°

23 =a
mol ~ )
x (8.314 J K+ moi") (273 K)
= 47> x 10-7
Since H, + Cl, = 9h el

20
= 1.72 x 10 ee) = 2.6 x 106
1.33 10"%
23.0 Discuss the economic possibilities of using photochemical
reactions to produce valuable products with electricity at 5 cents

per kilowatt-hour. Assume that 5% of the electric energy consumed

by a quartz-mercury-vapor lamp goes into light, and 30% of this is

photochemically effective. (a) How much will it cost to produce

1 1b (453.6 g) of an organic compound having a molar mass of 100 g

374

mol, if the average effective wavelength is assumed to be 400 nm

and the reaction has a quantum yield of 0.8 molecule per photon?

(b) How much will it cost if the reaction involves a chain

reaction with a quantum yield of 100?

SOLUTION

(a) Numbex of quanta required

(453.6
9)(6.022 x 107° mol")
=al
= 34 tore
(100 g mol
+) (0.8)
ea he _ (6.26 x 10°45 s)(2.998 x 10°
ms ~)
: 4000 x 10729
Se Rp eee
Se eGo n0e \iarsg to ae a SO
4 (0.05) (0.3) ota

ee _ (1,13 x 10° 8 5)(0.5$/KW hr) ae.

36 x 10° J/KW hr
1kWhr = (10° 3 s1)(60 x 60s) = 36 x 10° J/KW hr
(b) $1.55 Aine
one wae s

236 The quantum yield is 2 for the photolysis of gaseous HI to Hy + I,

by light of 253.7 nm wavelength. Calculate the number of moles of

HI that will be decomposed if 300 J of light of this wavelength is
absorbed.

SOLUTION
he (6.626 10
-34 8 =
Pts res SB2000 5 30 __TAy s)(3-2
3 it:
10 ms) = 7egglse orl?
=
7
(QS 337] exad!0 m)

ye Ree AO)
(2) (300 J Deer
ad = 1027 2082!
= nol of HT
(7.84 x 10°19 3)(6.02 x 1023 mo1~1)
 375

23.7 Show that if a solute follows the Beer-Lambert law, the intensity
of absorbed radiation I. in moles of photons per unit volume per

second is given by

ae Sac
tie IN,b~ oa )

where 1 is the length of the cell in the direction of the

incident monochromatic radiation and I, is in energy per unit

area per unit time.

SOLUTION
Consider that monochromatic radiation of intensity Le is

perpendicular to the face of a reaction cell of area A and optical

path length 1. The rate that energy enters the cell is IA, and

the) rate) that energy leaves the cell is MIA, where

1s=GiX exp(—iicl)s aThearate ip of absorption of electromagnetic

radiation in moles of photons per unit volume per second is given

by
1 IA I
a= fe) -Kel
I = a e )
a VN,b IN, h

If the cell is thick enough that the radiation is essentially all

absorbed, 7 = I,/1N,h wv.

eos In the stratosphere molecular oxygen absorbs solar radiation in

the 185 -— 220 nm wavelength region.

Omer hice = O20

If the absorption cross section is 1.1 x1 cm’, what thickness

of a layer of O, at 298 K and 1 bar is required to absorb half of

the radiation.
376

SOLUTION
P = aa RT where N is the number of molecules per m?
A

EN, (10> Pa) (6.02 x 1023 moi?)

No teaRT? nea ee ee
(Sisi4nd K mol ~)(298 K)

=" 2543" x 10> <r

= = exp(-oNx)
Oo

0.50 = exp[-(1.1 x 10 a2
- Gan) (2443 x 10%
-
m 3) (0.01 m
See
cm) x]

= gvoint 30. we WOJ095 streweetesnen 309456 cove

(1.1 x 10727 m*)(2.34 x 102° m >)
23 39 The fluorescence quantum yield for benzene at 25 °C is 0.070. The
lifetime of the excited state is 26 ns. What is the radiative
lifetime t_?
Oo

SOLUTION

= *s = 26 x10” s = 370 ns
‘g or 0.070

23.10 The phosphorescence of butyrophenone in acetonitrile is quenched

by 1,3-pentadiene (P). The following quantum yields were measured

at 25 °C (see N. J. Turro, Modern Molecular Photochemistry, The

Benjamin/Cummings Publ. Co., Menlo Park, CA (1978), p. 248).
[P]/10°? moi L} 0 1.0 2.0
4/4. 1 0.61 0.43
Assuming that the quenching reaction is diffusion controlled and
the rate constant has a value of 10° 1 mo1 ent, what is the
lifetime of the triplet state?
 377

SOLUTION

0
1XxJo-3 2xlo->

CalVmo |BS
slope = kot 7. tee a 640 L mol
1 ex i0e> moll i

640 Leen
1 101° 1, mo171 574
23.11 For 900 s, light of 436 nm was passed into a carbon tetrachloride
solution containing bromine and cinnamic acid. The average power
absorbed was 19.2 x 104 J st. Some of the bromine reacted to
give cinnamic acid dibromide, and in this experiment the total
bromine content decreased by 3.83 x 1019 molecules. (a) What was
the quantum yield? (b) State whether or not a chain reaction was
involved. (c) If a chain mechanism was involved, suggest suitable

reactions that might explain the observed quantum yield.

SOLUTION

(a) E
homuemn (0, lex 10M 34 55) oon 10° ms‘)
r
(436 x 10° m)
rear Res it

og oe Sa = 4,21 x 1015 s =i rate quanta are absorbed

a56 10S” ST
378

(4.21 x 102> 5 4)(900 s) = 3.79 x 1028 quanta

Te pb 2250 19 ‘We Gost
3.79 x 1028

(b) Since ¢ > 1, a chain reaction is involved.

(c) gCH=CHCO,H + hw = gCH=CHCO,H”

gCH=CHCO, H” Oe gCHBrCHCO, H” Be”

gCHBrCHCO,H” + Br, = gCHBrCHBrCO,H + Br-

gCH=CHCO,H + Bre = CHErCHCO, H”

23.12 Ketone A dissolved in t-butyl alcohol is excited to a triplet

state a* by light of 320 - 380 nm. The triplet may then return to
the ground state A or rearrange to give the isomer B, thus

ee wef +Light =
Kp
A
The unimolecular rate constant k determines the rate of
deactivation of excited molecules and the unimolecular rate
constant k determines the rate of rearrangement. The symbol I
represents the number of moles of photons per second and it is

assumed that each photon absorbed produces one excited molecule of

Aaa EThe quantum yield ¢ for the formation of B is given by

jor ateItae wkel)

I
 379

Zimmerman, McCullough, Staiey, and Padwa measured the quenching

effect of dissolved napthalene and report the following data.

Moles napbtha-

lene re 0.0099 0.0330 0.0620 0.0680 0.0775 0.0960

¢ 0.0049 0.0023 0.0020 0.0017 0.0014 0.0012

The quenching rate by napthalene is controlled by the bimolecular

*
quenching constant of A , which is equal to the diffusion—

controlled constant kg = 1.2 x 10? L moi! s-}, Assuming a

steady state,
a{A"] _ 2 a es * =
*

erick oe k, [A ] k) [A ] k CA J(N] 0

where [N] is the concentration of naphthalene. Calculate kp and

ky by plotting 1/g versus [N] and determining the slope and
intercept of the line.

SOLUTION

: = k, + ky + KIN]
[A ]

k
ae ae ae tNGY Sat ED + = IN]
dean Steae R R

(Solution continued on page 380)

380

600
O

gan
(6)

200

0 005 0.10

cNi/mo/ L
-l

slope = SPs. ee 7.55 x 10° L moi!

9 =) ill
— 1.20 x 10° L mol s k ID sy 10> ah)
k R
R

intercept = 120 = 1 + * = 1) + “D
Kp 1.6 x 10° 5}
7 i
k, = 1.9
x 10 s

23.13 The following calculations are made on a uranyl oxalate

actinometer, on the assumption that the energy of all wavelengths

between 254 and 435 nm is completely absorbed. The actinometer

contains 20 cm’
3 of 0.05 mol L-* oxalic acid, which also is 0.01
mol pi with respect to uranyl sulfate. After 2 hr of exposure to

ultraviolet light, the solution required 34 com? of potassium

permanganate, KMn0,, solution to titrate the undecomposed oxalic
 381

acid. The same volume, 20 com>, of unilluminated solution required

40 cm? of the KMn0, solution. If the average energy of the quanta

in this range may’be taken as corresponding to a wavelength of 350
nm, how many joules were absorbed per second in this experiment?

(g = 0.57)

Moles of oxalic
acid decomposed (0.02 L) (0.05 mol L 2) Gare
= 1.5 x10 mol
Moles of photons Ee 104 ad!
2 3 -8 zy
Sheed - (x 60 x 60 s)(0.57) Ai SISSIES

n= be _ (6.626 x 10°45 s)(2.998 x 10° ms")

a Eee as (ae
ShB os Ole Cy
Energy
flux (3.65x10°. mol» s7+)(6.02x102° mol) x (5.68x10- J)

Vet sae pres

23.14 The quantum yield for the photolysis of acetone (CH) CO =
CyHe + CO at 300 nm is 0.2. How many moles per second of CO are
formed if the intensity of the 300-nm radiation absorbed is 1072 J

$a?

SOLUTION
po Be = {6.6262 OS SNe x210° yond) eG pg eg 19
300 x 1079 m
2
ee One)
Or ee Bag 105" mol. are
(6.02 x 102° mo1~4)(6.63 x 10729 3)
382

23nd A solution of a dye is irradiated with 400 nm light to produce a

steady concentration of triplet state molecules. If the triplet

state yield is 0.9, and the triplet state lifetime is 20 x 107° Si

what light intensity, expressed in watts, is required to maintain

a steady triplet concentration of 5 x 10°© mo1 Lt in a liter of

solution. Assume that all of the light is absorbed.

SOLUTION
d(T, ]
~3e- = 0.9 I ae Sent Sesteaes
—6 (T,] = 0
20 x 10

TC =
Cs
———
eos = 0.278 mol s
=f
(20 x 10°© s)(0.9)
= x
pe N,hHee 2pl6.0220x 10 molh )(6x62 10 Ts) (3ix 10° baat)
=

‘ 400 x 10° m
= s esi
= 2.99 x 10) J mol

I. -== (0.278 mol eal

s°”)(2.99 x 10 5 Jmol”)
=i
= 83 kW

23.16 The photochemical chlorination of chloroform

CHC1, + C1, = CCl, + HC)

is believed to proceed by the following mechanism.

I
Cl, + ha SS 21

ky
CY ie CHE) eee Cd ener

CC i + cl, eect
ky PCC a Cl

2CC1l. CL k,
ee Ce)
 383

Derive the steady state rate law for the production of carbon-
tetrachloride.

oor sneer 2
ae k, [CC1,][C1,] + 2k,[CC1,] [c1,]

-= k, [C1] [CHC1,] k,[CC1,](C1,] = 2k,[CC1,] 2 [C1,] =- 0

21, = k, [C1] [CHC1,1] - k,[CC1,][C1,] = 0

Adding the two steady state expressions yields

% 2
I. = k,[CC1,] (C1, ]

This makes it possible to eliminate [cci,] from the first equation

to obtain
GICCIz
Ay | t_5 fk 1
£72, [c1,]
1/2 TS 1/2 + 21
dt 2 a

23.17 Given that solar radiation at

noon at a certain place on the
Dt el
earth’s surface is 4.2 J] cm ~ min, what is the maximum power
output in W m2?

SOLUTION
at Pe es | il
(4.2° Jeom>s (mins 9) (100 ccm mie) Uy = 700 W m72
60 s min2
a
23.18 If a good agricultural crop yields about 2 tons acre of dry
organic material per year with a heat of combustion of about 16.7

kJ 1
g~, what fraction of a year's solar energy is stored in an

agricultural crop if the solar energy is about 4184 J min 2 ft?

and the sun shines about 500 min day 2 on the average: 1 acre =

43,560 ft~ 2 and 1 ton = 907,000 g.

384

SOLUTION
solar 2 -1 -1 -1
energy = (43,560 ft’ acre )(500 min day )(365 day year )

x (4184 J ft? min“)

= 3.33 % 10" J gx year
energy oF a 4 Ee
stored = (2 ton acre’ year )(907,000 g ton )()16,700 J g )

= 303 x 107° J yen year

10
fraction stored BREE: SC
3.33 x 10! J
23.19 Sunlight between 290 and 313 nm can produce sunburn (erythema) in
30 min. The intensity of radiation between these wavelengths in
summer and at 45° latitude is about 50 pW om -, Assuming that 1
photon produces chemical change in 1 molecule, how many molecules

in a square centimeter of human skin must be photochemically

affected to produce evidence of sunburn?

SOLUTION
—34 8
ee he < KO3 . 6305010
1 )(3 x 10 ) = 66a 6 we 19 J
3x10!
(50 x 100° Bs eecus 412012) COs ee MDGRIT Come
fo OM Ee. = 1.36 x 1027 molecules an
6.63 x 10 29
23.20 Calculate the longest wavelength of light that can theoretically
decompose water at 25 °C in a one~photon electrochemical process
to give H, (g) and + 0, (8) in their standard states. Given:

AG ome.= 237.2 kJ mol

al
for H,0(1) = H, (g) +
1
7 Oe).
 385

SOLUTION
AG? 0
=
—_—
N,he/d

, = ANS _ (6.022107* moi) (6.626x10 °4

N = «a

J s)(2.998x10°8 nm a)
AG° 237,200 J mol
504 nm

23.21 > 351 x OOS ok lee

23.22 (a)-052709 3s (b) 0.3988 J st
{c)-0.1709 watt (d) 0.3988 watt

23.23 2.18 x 10,19 5

23.24 7.84 x 104 s
23.25 10°!) mo1 Lot
23.26 OS et105 at 1

23.27 47.1 5s

23.28 0.0503 st
*
23.29 NO, + hea 5 NO,
*
NO, + NO, —— 2NO + 0,

Decreased concentration of NO, after long illumination makes

decomposing collisions less likely. Also reverse
reaction becomes more important as the concentrations of the
products build up.

3.94 tons

(a) 1074 (b) 4.53 x 10° g day4

617 g

24.4 tons

504 nm
CHAPTER 24: Irreversible Processes in Solution

24.1 Ten cubic centimeters of water at 25 °C is forced through 20 cm of

2-mm diameter capillary in 4 s. Calculate the pressure required

and the Reynolds number.

SCLUTION

sya peesSVl7 ame Pol) 1Onx 107° m°)(0.2 m)(8.95 x 10s egtm 2 sD)
mt n(10-> m)4(4 s)

= da eet ON ae
Reynolds number = ae

it ae volume of liquid per unit time

area of tube
=—Omeo
se eeNS 5) ey 0nac6 mee
n(10-2 m)2
4

Reynolds number
-3 =i 3 =3
(2x
Dix 10 m)(O.796
‘ ms )(0 kgm”) © 1780
(8.95 x 1074 kg mt ,-1)

24.2 A steel ball (p = 7.86 g cm?) 0.2 cm in diameter falls 10 om

through a viscous liquid (p, = 1.50 g emgs)ninh2oacoueWhat is) the
viscosity at this temperature?

SOLUTION
2
2r(p - pods

ois 1008 sm)2 186 ae Oe SHOR moe BS

0.10 m
: ( 25s
= 3.46 Pa s
 387

24.3 Estimate the rate of sedimentation of water droplets of 1-pm

t)
diameter in air at 20 Cr The viscosity of air at this
temperature is 1.808 x 107° Pa s.

SOLUTION
2
dx _ 2r(p -— pode
dt 9n

_ 20.5 x 10° m)7(0.998 x 10° kg m°)(9.8 ms 2)

9(1.808 x 10> Pa s)

BEOLe 10 oa

24.4 Using data in Table 24.1 and equation 24.6, estimate the
activation energy for water molecules to move into a vacancy at 25
i!)
c.

SOLUTION
Rit, ny
E. = T_T In —
2 1 uy)
4 a
(8.314, 0) Bic moll 14273 152K) (323015) K) 1793
(50 K)(10° 3 x«y71)
520

17, 4°43 hol

24.5 The relative viscosities of a series of solutions of a sample of

polystyrene in toluene were determined with an Ostwald viscometer

ste 25700.
c/10-2 g cm > 0.249 0.499 0.999 1.998
n/N i Sale: 1.782 Pest [i 6.090
The ratio Nsp/¢ is plotted against c and extrapolated to zero

concentration to obtain the intrinsic viscosity. If the

constants in equation 24.13 are K = 3.7 x 102 and a = 0.62 for

388
:
in
5!
g/cm,
this polymer, when concentrations are expressed

calculate the molar mass.

SOLUTION
10K g ee 0.249 0.499 0.999 1.998
n/n = il
2 142.6 156.7 188.1 254.8
Cc

aS

lee ce
a /Os |
ks

EO
| 2
COE cat

eee ee = 0.62 in M
3.7 x 1077

Mo= exp [oa In —~“® | = 500,000 g moi~?

; 3.7 x 10

24. 6 At 34 °C the intrinsic viscosity of a sample of polystyrene in

toluene is 84 om? gt. The empirical relation between the
intrinsic viscosity of polystyrene in toluene and molar mass is

[ni = 1715" x 10°~ Wo: 14." “Whatis the molar aise of this sample?
 389

SOLUTION

ee ee es 1M
1.15 x 102
1 i
M = exp 0.72 In —t_, = 230,000 g mol 1
: 1.15 x 10
24.7 Given that the intrinsic viscosity of myosin is 217 cm? gt,
approximately what concentration of myosin in water would have a

relative viscosity of 1.5?

SOLUTION
an -1
No = 217 cm
3-1
g
0.5
-— = 217 cm
3 g
-1
c Cc

6 aaa Seay tres a picwie

217 cm? gt

24.8 A conductance cell was calibrated by filling it with a 0.02 mol

L! solution of potassium chloride ( kK = 0.2768 oa) m1) ana
measuring the resistance at 25 ofeb which was found to be 457.3 Q.

The cell was then filled with a calcium chloride solution

containing 0.555 g of CaCl, per liter. The measured resistance
was 1050 @. Calculate (a) the cell constant for the cell, and
(b) the conductivity of the CaCl, solution.

SOLUTION
(a) From equation 24.15

K = kR = (0.2768 Opeeee 4ST 21D) = 1266

cell

K : -1 -1 -1
390

24.9 It is desired to use a conductance apparatus to measure the

concentration of dilute solutions of sodium chloride. If the

electrodes in the cell are each 1 cm 2 in area and are 0.2 cm

apart, calculate the resistance that will be obtained for 1, 10,

and 100 ppm NaCl at 25 Ce

=i
1 ppm = 1g NaCl in 10° g H,0 - g)/G8 C 4o_gmoh1
1m

Pali e102 nol we

Using electric mobilities at infinite dilution,

k= Fe(uy + U¢,-)

ee = = - a et
25(96.485 C mol +) (12121086 mot min) (Sssie2 497.913) anel0. mw Va ena
Su ORI 6x10) scone ae

1 0 ose
R= —5 = Sees eas = 9,24 5 10° 0
k (2-36 zbaloavitg’ twaeencoto1 ta)
For 10 ppmR = 9.25 x 10° o
For 100 ppm R iH 925 Q

24.10 A moving boundary experiment is carried out with a 0.1 mol Lt}

solution of hydrochloric acid at 25 °C (Cie = 4:24 Oo amen

Sodium ions are caused to follow the hydrogen ions. Three
milliamperes is passed through the tube of 0.3 cm“ 2 cross-sectional
area, and it is oberved that the boundary moves 3.08 cm in 1 hr.
Calculate (a) the hydrogen ion mobility, (b) the chloride ion
mobility, and (c) the electric field strength.

ae ee ee 3x 100" -3 A =|
Sse x ERG peeyh
(0.3 x 104 m2)(4.24 g-} go)
 391

ICC OA/ AVL. 3.08 x 10% m

E =
(60 x 60 s)(23.58 vy m4)
=o G50E 101 eo Viste
(b) k = Fe (uyt+ + Uos-)

Ae fb9 oit Pst 6 (45047 de embed

Clim ET Ce Pelt | acetate
(96,485 C mol
er ae es
~)(0.1 x 10° mol 7)

estes 0 ac ee
Beehs 10 be Vee

(c) See (a)

24.11 Calculate the conductivity of 0.001 mol Lo? HCI ato257°C. The
limiting ion mobilities may be used for this problem.

SOLUTION
k = Fe (uy,+ + Ua,-)

Pe ohTs SEC clsU1 mol mio) (36205 6 7,91) atl em Vio scl
= 0.042 612°
141

24.12 One hundred grams of sodium chloride is dissolved in 10,000 L of

water at 25 °C, giving a solution that may be regarded in these
calculations as infinitely dilute. (a) What is the conductivity
of the solution? (b) This dilute solution is placed in a glass
tube of 4-cm diameter provided with electrodes filling the tube

and placed 20 cm apart. How much current will flow if the

potential drop between the electrodes is 80 V?

SOLUTION -1

(107 cm?) (1072 m om72)3

392

k= (96,485 nol”-\(EogtxL0@p Holami 131 0ske AON anGavees)

2916 S10" "08 a
1 0.2 m

Pa 5 KA (2.16 eS 10t- a? mw4)(2 P AOMaERCH

= >74360x"10 sO
1-¢ at =i 1,09 xu Ob UA
7.36 x 104 9
24.13 Using Stokes’ law, calculate the effective radius of a nitrate ion

from its mobility (74.0 x 10°? m? vt 5-1 at 25 °C).

SOLUTION
IZ. le
f. = = = 6nnr
i

Iz.le
~~ i
u. 67H

fo ie B60 10 ew A See
(74 x 10-9 m2 vit 5~1)(6n) (8.95 x 1074 kg mt 5-1)
= 0.128 nm

24.14 It may be shown that the diffusion coefficient at infinite

dilution of an electrolyte with two univalent ions is given by
2u,u,RT
D = Se ae
(u, te u, )F

where u, and uy are the limiting values of the mobilities of the

two ions. What is the diffusion coefficient of potassium chloride
in water at 25 nO?
 393

SOLUTION
(1.617 if
x 10 me Vo ¥1)191913 2 10s 0 s +) (R) (298.15 K)
(15.53 x 10-8 m2 vy! 5~1)(96,485 C mo1~2)
1<99 4.40 ~ aces Be. =. 6.3145 Ko eole-

24.15 What is the self-diffusion coefficient of Nat in water at 25 °C?

SOLUTION

nae uRT
IzIF

(S002 x 105 ae V3 428 314 TK.

9.6485 x 104 C mol
13345 10° eee
24.16 Using a table of probability integral, calculate enough points on
a plot of c versus x (like Fig. 24.4c) to draw in the smooth curve
for diffusion of 0.1 mol pl sucrose into water at 25 °C after 4
hr and 29.83 min (D = 5.23 x 10729 2 s1),

SOLUTION
39
Noemaluprovability, fonction’ => =e (2° t8e. 6
por,
Vf2n
Equation 20.38
x/24/Dt
c ae
c. = = Es Z e B dp
vor
oO

In order to get this equation in the form of the normal probabil-

ity function let Be = AGH hp Thus Bp =t/ 2 and df =dt/ 2

f x/ V 2Dt 2
oO 2 -t'/2
C———— ih ge e dt
2 VV 2n
394

x/ V2DT

=
£
5 1 +
1 e
- ap dt

Von -x/ ¥2Dt

ee eee Eee
This area is obtainable from
tables of the normal probability
integral (N.P.I.)

lo = [1 + Area of N.P.I.]
NO

The + sign is used when x > 0, and the - sign is used when
x <0.

At x = 1 cm the Gaussian parameter is

x 102 m

N 2Dt
Ase ge 10). me 6 7269.83 x: 60 8)

Ix] x Area
ak Aa N.P.I. o(x) <0) c(x > 0)

0 0 0 On0 semi ta 0.05 mor ia

Ovi 0.243 0.1922 0.040 0.060
0.2 0.486 0.3732 0.031 0.069
0.3 0.729 0.5340 0.023 0.077
0.4 0.972 0.6690 0.016 0.084
0.6 1.458 0.8556 0.007 0.093
0.8 1.944 0.9480 0.003 0.097
1.0 2.43 0.9850 0.002 0.098
ue) 2.916 0.9964 0.001 0.099

(Solution continued on page 395)

 395

6) ,

O OD O./
C/70/ rgXs

24.17 A sharp boundary is formed between a dilute aqueous solution of

sucrose and water at 25 °C. After 5 hr the standard deviation of

the concentration gradient is 0.434 cm. (a) What is the diffusion
coefficient for sucrose under these conditions? (b) What will be
the standard deviation after 10 hr?

SOLUTION
OA Gs 2 Oe 1 AS34 4x 71065 -3 om) ,2 F08 -10 2 -1
eee (ek casa 60 3) CO |)

(b) o = Nope = 25.23 x 101° m? s-1)(10 x 60 x 60 s)

= 6.14 x10°
3 m

24.18 A sharp boundary is formed between a dilute buffered solution of

hemoglobin (D = 6.9 x 10°21 m? s-1) and the buffer at 20 °C. What
is the half width of the boundary after 1 hr and 4 hr?
396

SOLUTION
Giro “ope ee 31619 «108 = ae e606)
=) 7 05 20m nero ONO TOS UCR

(b) o = 26. Oies 40s chmomeen

cia 60muee

ey en ie ee BE ee

24.19 What is the root-mean-square displacement in the x direction of a

molecule of tobacco mosaic virus due to Brownian motion during one

minute in water at 20 °C? (See Table 24.5)

“n~ =~> ‘al ~~ 2, 1/2

Vv
ut opt. = 1(2)(0 253 SEO me e060 2) Io/2
0.0252 nm

24.20 The diffusion coefficient for serum globulin at 20 °C in a dilute

aqueous salt solution is 4.0 x 10721 m? sl, If the molecules are

assumed to be spherical, calculate their molar mass. Given:

n
H,0 = 0.001 005 Pas at 20°C and v= 0.75 cm? g! for the

protein.

SOLUTION
1/3 3
nee ERE
N,6nn
)
3Mv
Sere
oe
3v
ake
N,6nnD

4n(6.02x10"> mo12) © (83317 «7 m01

4)(293 kK)
3(0.75x10> m> kg -) \k(6.02 210°" mols Sy6n(dccsaec10. eke s)
3

(4.0 x 10-11 ,,2 st)

= 511 kg molt = 511,000 g mo1~4

 397

24.21 The diffusion coefficient of hemoglobin at 20 °C is 6.9 x 101! m2

=i) ; ‘
s ~. Assuming its molecules are spherical, what is the molar

mass? Given: vy = 0.749 s 10°? m9 kg and n = 0.001 005 J

Bes s.

SOLUTION
1/3
ae atts See)
N,6nm eee

3
ly Om
3v
on Tae
DN, Onn

yo = 4n(6.022x107* mol”) (8.314 JK? mol") (293 K)

BROt4G5100 om okots) 1116)
9x108- as f 45 (6.022710-° “mol
i)
3
rare
rs oO ee
6n(0.001 005 J m~ s)
—1 -1
= 100 kg mol = 100,000 g mol

24.22 Calculate the sedimentation coefficient of tobacco mosaic virus

from the fact that the boundary moves with a velocity of 0.454 cm
nr in an ultracentrifuge at a speed of 10,000 rpm at a distance

of 6.5 cm from the axis of the centrifuge rotor.

SOLUTION
0.454 cm wt
ar me i
dt 3600 s hr
wo © 10,000 x 2n ‘S15 Ga
60 s =

Pie Tieton
398

24.23 The sedimentation coefficient of myoglobin at 20°C is 2.06 x 1

s. What molar mass would it have if the molecules were spherical?

Given: v= 0.749 x 107°. m> kg! .0., pr= 0.9982, x 10° kgm, and
n = 0.001 005 Pa s.
SOLUTION
7 ee 1/3
én a Mi eave oe ey Mle aye (ae!)
Nyf N, 6x 3Mv

3/2 oe.
i Pree. 3v
= 1 - vp 4nN,

3/2
yw = | £62022 x 1073 moi 1) (6n(0.001 005)(2.06 x 10°)
1 - (0.749 x 10 °)(0.9982 x 10°)
Ee
(2x 0.749 x 10 }
4n6.022 x 1029
=o015 75 keemol
-1 = 15,500 g mol
-1

24.24 The sedimentation and diffusion coefficients for hemoglobin

corrected to 20 °C in water are 4.41 x 1 0 #5 and 6.3 x 100” m m-

sl, respectively. If v = 0.749 cm” 3 g_ ft and Pao = 0.998 g
2
cm > at this temperature, calculate the molar mass of the protein.
If there is 1 mol of iron per 17,000 g of protein, how many atoms
of iron are there per hemoglobin molecule?

SOLULTON

D(1 - vp)

: (B03) Tike moles) (003 Ky (anadeg 0)

(6.3x1011 m? s~1)[1 - (0.749x1079 m? kg~1) (0.998103 kg m3)]
 399

yh
= 67.6 kg mol
= = 67,600 g mol
=I

C1000 sarmal:
= 4 g-atom Fe oie
17,000 g g-atom Fe
= 4 Fe per molecule

24.25 Given the diffusion coefficient for sucrose at 20 °C in water (D =

45.5 x 19711 ae sl), calculate its sedimentation coefficient.

The partial specific volume v is 0.630 om? gf.

SOLUTION
Ss =

_ (342x10-> kg mol *)(45.5x107) m?_s 1)[1 - (0.630 om? g +)(A)]

(8.31 J Kt mol *)(293 K)
i: S
0.236 x10” 5s A = 1g cm

24.26 A sedimentation equilibrium experiment is to be carried out with

myoglobin (M = 16,000 g molt) in an ultracentrifuge operating

at 15,000 rpm. The bottom of the cell is 6.93 cm from the axis of
rotation and the meniscus is 6.67 cm from the axis of rotation.

What ratio of concentrations is expected at 20 °C if v = 0.75 x

10° mm ke and p= 1,00x 10° kp m >?

SOLUTION
2
a > M10 = vp)- (ry ie )
cy 2RT

_ (16 kg mol = +) (0.25) (2n250_s)

=
[(0.0693 m)” - (0.0667 m)~]2
2(8.314 J Kt mol
)(293.15 K)

0.716 — «= 2.05
400

24. 21 {els x 10° Pa m 2 The Reynolds number is 447, and so the

flow will be laminar.

24. 28 95.7 min

24 129 0.66 s

24. 30 0.001 41 Pa s
24. 31 8.39 x 10° g molt
24. 32 638,000 g molt
24. 33 520 nm

24. 34 (a) 4.2894 m1 (bv) 0.0768 m (c) 58.4 Vm

24. 35 0),1058,0.7) m +
24. 36 1.6x10- oa
24. 7 Sul6 x=l0a> m- Vo et
24. 38
 401

so9 0945x1107", 2.03 ealOr> est34 x 107° mm” 3

-40 Caton9 6 aha. (b) 56.4 hr.

41 643, 10 9 a ve 8
ec 2
.44 (b) cai DV c

45 (a) 104 min (b) 56.5 hr.

-46 7.09 x 10-22 »? 51

-48 5.41 x 104 cm
-49 27.6 x°10° g mol
.50 OpSsecm

ep! 64,000 g mol

 PART FOUR
STRUCTURES

CHAPTER 25: Solid-State Chemistry

Pa 531 What is the equation for the distances between planes 1, 1, O for

a crystal with mutually perpendicular axes?

SOLUTION
1 (2 1 i
i Poa
ae
D

a . : 3" : (= iy
Bre: : fa
ie 2 3 ai ad = 1/2
a b ab (.? - >”)

25.2 Calculate the angles at which the first-, second-, and third-order
reflections are obtained from planes 500 pm apart, using X rays
with a wavelength of 100 pm.

SOLUTION

GE he e e: eee
24d
ieeels
2(d/n)

, a 100 pm » o
sin ©) = 3(500 pm/1) ot ts ae
F 2 100 pm - ‘
ein eo > a0 s00s nas 2) sy iat ah
100 pm
nn aeB oO
3
ll
2(500 pm/3) ice)
w
i} 17.46°
 403

25.3 The only metal that crystallizes in a primitive cubic lattice is

polonium, which has unit cell side of 334.5 pm. What are the

perpendicular distances between planes with indices (110), (111),

(210) and (211)?

SOLUTION
d a See
a Gi +k eel)
1/2
diigo = 334-5 pm/2 = 236.5 pm
1/2
dia = 334.5 pm/3 = 193.1 pm

1/2
4,40 = 334.5 pm/5 = 149.6 pm

1/2
dy4, = 334.5 pm/6 = 136.6 pm

25.4 Calculate the structure factor for a cubic unit cell of AB in

which the B atoms occupy the body centered position. Which

reflections will be strong and which weak?

SOLUTION
5 2na (h/2>+ k/-25451/2)
F ikl = f, + fne

4 wath kee 1)
= fy ay fne

Jar Ve Grol
we ey £,(-1)

Di hot koe etisie vem, Fkl = fy ata fp » strong reflections.

Tifeeehe chek? tleeessivodds, Fil = fy = fp » weak reflections.

25 0 The crystal unit cell of magnesium oxide is a cube 420 pm on an

edge. The structure is interpenetrating face centered. What is

the density of crystalline MgO?

404

4(40.32 x 107° kg mol) 3.615 x 10° kg m>

(6.022 x 1023 mo1~1)(4.20 x 10719 m3
3,615 ¢ oe

A) Tungsten forms body-centered cubic crystals. From the fact that

the density of tungsten is 19.3 g cm, calculate (a) the length

of the side of this unit cell, and (b) dogo: d410° and doo2°

3 sil
= POSS 8S 410 kKg tol)
fe edosses 10 kee ear = 183.85 10 1)

(6.022 045 x 10 mol ~)a

4S EG i ye Siar
(b) d = fe SSE nas tae = 316 pm = 158 pm
200 fe Sen 2
2 sp) ge

a 316 pm
d = ———*—- = 223 pm
A10 aap Gap N 2

d = — ENS

2500 Copper forms cubic crystals. When an X-ray powder pattern of

crystalline copper is taken using X rays from a copper target (the
wavelength of the Ka line is 154.05 pm), reflections are found at
@ = 21.65°, 25.21°, 44.96°, 47.58°, and other larger angles.
(a) What type of lattice is formed by copper? (b) What is the
length of a side of the unit cell at this temperature? (c) What
is the density of copper?
 405

SOLUTION
d a r — 154.05 pm = a
hkl 2 sin 0» 2 sin 6 > > >
h +i k + 1

a) Ratio d... to
(3) d /pm
bk1 largest spacing

21.65° 208.77 1.0000

2531" 180.84 0.8662
37.06° 127.81 0.6122
44.96° 109.00 0.5221
47.58° 104.34 0.4998

Ratios expected for cubic crystals

d =
hkl
2 rh ms z 2

Primitive Body-—centered Face-centered

100 1.0000 __— —

110 0.7071 1.0000 —
still 0.5774 — 1.0000
200 0.5000 0.7071 0.8660
210 0.4472 — —
210 x 0.5774 —
220 x 0.5000 : 0.6124
310 xX 0.4472 -——
311 xX — 0.5222
222 xX xX 0.5000

— reflection absent

xX not needed for this problem

Thus copper forms face-centered cubic crystals.

a
(b) dia = =) 208277 pm
406

ee 4(63.546 x 100° ke mol —)

(6.022 05 x 1023 mo1~1) (361.6 x 10-12 m?)?
0.8927 x 10° kg ae

25% (a) Metallic iron at 20 °C is studied by the Bragg method, in

which the crystal is oriented so that a reflection is obtained
from the planes parallel to the sides of the cubic crystal, then

from planes cutting diagonally through opposite edges, and finally

from planes cutting diagonally through opposite corners.

Reflections are first obtained at © = 11° 36’, 8° 3', and 20%

26’, respectively. What type of cubic lattice does iron have at

26 °C? (b) Metallic iron also forms cubic crystals at 1100°C, but

the reflections determined as described in (a) occur at ® = 9°

Sie pl . 057 ands tate 55', respectively. What type of cubic

lattice does iron have at 1100 °C? (c) The density of iron at 20
°C is 7.86 g cm>. What is the length of a side of the unit cell

at 20 °C? (d) What is the wavelength of the X rays used? (e)

What is the density of iron at 1100 °C?

SOLUTION
(a)(b) The three orientations will give reflections from planes
a00, bbO, and ccc, respectively where a, b and c are_ small
integers. The smallest suitable integers are: primitive lattice:
a=b=c=1; body-centered lattice: b=1, a=c=2 (100 and 111
reflections are missing); face-centered lattice: c=1, a=b=2.

Since A/2a is constant for a particular experiment, the three

lattice types can be distinguished simply on the basis of the
relative magnitudes of the three @’s. Thus the crystal at 20° C
is body-centered since the second angle is smaller than the first
 407

and the third is the largest of all (ratio of sin ® is

22 AN2 83 A12 ). At 1100 °C the face-ceritered form is found
(ratio of sin @ is 2:18 :N3 ). Note that a primitive lattice

would give ratios of sin @ of 1:42 :¥V3 ).

a pa -3 -—1
Ce ace ee 3 _ 2(55.847 x 10 ~ kg mol |)
(6.022 045 x 1029 mo1-1)a>
% $¢ 1/3
a
7
= eS ee eC
(2)(55.847 x 10 ~ kg mol)
(6.022 045 x 1029 mo1~1)(7.86 x 10° kg m >)
eh o86.8 940 one 8b. 8 Gin

hk] 5 ; ;
hil <a WETRDS) 4
a1s.f ee sini” 36'>= 57.7 pa

aE ge sin 8° 3' = 56.8 pm

A 2

SH OEP To! 86) = 57-8 pn

A 12 Average = 57.4 pm
a
(ort Geet lee Qeaans ©

d Riese EISLe 180.8 pm; a = 4d 4 = 361.6 pm

200 ; 0 : 200
2 sin “9 8

d ee eee a eel onan SA NOS fe) 362.5 0pm

220 } Tee 220
Dasara Dae,

lee
111
iN
;
er
0 ;
Ry ar ee ae eee, pce
111
tie.
2°Sin” 7s 395

Average = 361.6 pm
408

ree 4(55.847 x 10> kg mol) —

(6.022 045 x 1023 mo1~1) (361.6 x 10-22 m)3
7846x810 kg gn

25. Cesium chloride, bromide, and iodide form interpenetrating simple

cubic crystals instead of interpenetrating face-centered cubic

crystals like the other alkali halides. The length of the side of
the unit cell of CsCl is 412.1 pm. (a) What is the density? (b)
Calculate the ion radius of Cs’, assuming that the ions touch

along a diagonal through the unit cell and that the ion radius of

Cl is 181 pm.

SOLUTION
ey at (168.36 x 10> kg mol)
(6.022 0450x010-> moti.) (412 Wier, 10saes ae
It 3.995 5 10° kg a

(b) The diagonal plane through the cubic unit cell is as follows:

2 2
a + (¥
(V2 a) = (2rq, + 2r0,)

Lf
La) Cs i} Le - (42 a7] —- 2(181 pm)

176 pm

25.10 The density of potassium chloride at 18 °C is 1.9893 g cm >, and

the length of a side of the unit cell is 629.082 pm, as determined
by X-ray diffraction. Calculate the Avogadro constant using the
 409

values of the relative atomic masses given in the front cover.

SOLUTION

1.9893 x 10° 3 kg m a3 = 4(7atSS1n 1010 etkeenol

<a ee+0
N, (629.082 x 10 m)

N, = 6.0213 x tGeancla-

25.11 Deslattes, et al., Phys. Rev. Lett., 33, 463 (1974) found the
following values for a single crystal of very pure silicon at 25

°C: p = 2.328199208 om °,)| a: 95431066 pm! Silicon has a face-

centered cubic lattice like diamond. The atomic mass is 28.085 41
g mol+. What value of Avogadro's constant is obtained from these
values?

SOLUTION
ee:
‘ N,a 3

Sy ee (8) (28.085 41 x 1072 kg moi?)

A pa 3 (2.328 992 x 10° 3 kg m -3 ~)(543.106 6 x 10 =12) m) (3

£°029093 = 10 mole

25.12 Insulin forms crystals of the orthohombic type with unit-cell

dimensions of 13.0 x 7.48 x 3.09 nm. If the density of the

g
3
cm ~ and there are six insulin molecules per
crystal is 1.315
unit cell, what is the molar mass of the protein insulin?

3 3 6M
AeeB le cS ex alOM ER ON
(6.022 045 x 107° mo1+)(13.0 x 7.48 x 3.09

x 10°! m?)
410

Ul = (1.315 10" kg mr 3561020 0458e 110 23) 5517 )(13.0°x° 7048) x 3.09
SS cal m?)
-1 -1
39.7 kg mol = 39,700 g mol

3 Yee i Molybdenum forms body-centered cubic crystals and, at 20 (by the

density is 10.3 g cm >, Calculate the distance between the

centers of the nearest molybdenum atoms.

SOLUTION

kg mol)
-3 =I

10.3 x 10? xg m2 = 2695-94 2 10”

(6.022 045 x 1023 mo14)a
a We Soh share 5phealt pmieab ee
Consider a plane bisecting the cube and cutting diagonally through
opposite faces.

length of diagonal = o) 22a) eens

Q fy
istance between a NB
= acces = 073 pm
atoms

avZ
25.14 Aluminum forms face-centered cubic crystals, and the length of the
0
side of the unit cell is 405 pm at 25 C. Calculate (a) the
density of aluminum at this temperature, and (b) the distances
between (200), (220), and (111) planes.

SOLUTION
Pho ee 4(26.981 54 x 10> kg mol‘)
(6.022 045 x 1023 mo1~1) (405.0 x 10712 m)3

2.698 x 10° kg m_ 5)
 411

@) dp hs 2 og og ee : PEee
Sie

50 Seon
hook it

d 220 en
irsch. Ps7 143.2dl he

d sp eee et £933 08 ee

25.15 Rutile (TiO, ) forms a primitive tetragonal lattice with a = 459.4

pm and c = 296.2 pm. There are two Ti atoms per unit cell, one at
(00C) and the other at (1/2 1/2 1/2). The four oxygen atoms are
located at = (nu0) and + (1/2 + vu, 1/2 - u, 1/2) with u =
0.305. What is the density of the crystal?

SOLUTION
=s0 7S
Vv (459.4 pm)” (296.2 pm) = 62.51 x 10 m

ioc 2047.90 + 2 x 15.99) x 10° kg mol

(6.022 045 x 1022 mo1~+) (62.51 x 107°9 m°)

4e245. x 407 kg ao

25.16 The diamond has a face-centered cubic crystal lattice, and there
are eight atoms in a unit cell. Its density is 3.51 g cm >,

Calculate the first six angles at which reflections would be

obtained using an X-ray beam of wavelength 71.2 pm.

a = $512 10° kgm? - 2022-011 x 107 -3 kg mol -1 >

(6.022 045 x 1023 mol~?)a®
ea Ones m = 357 pm
412

ww aX 2 2 2) Leer Fo ys 2 2 2
@ = sin 2a hie komen = sin (357) ji Sp yee sp il

For face-centered cubic the first six reflections are:

hk1 r)

td, 9.95°
200 11.50°
220 16.38°
311 19.3%"
222 20-21"
400 92.510

ZSoA7 Calculate the density of diamond from the fact that it has a face-
centered cubic structure with two atoms per lattice point and a

unit cell edge of 356.7 pm.

SOLUTION
foes (4) (12) (12.011 x 107° kg mol2)
(6.022 045 x 1072 mo1~1) (356.7 x 10722 m)3
3.516 x 10° kg are

25.18 Tungsten has a body-centered cubic structure at room temperature.

Since the density is 19.35 g cm” 3 at 20 °C, what is the atomic

radius?

SOLUTION
For a body-centered cubic crystal there are two atoms per unit
cell.
= =i
d
=
19.35 x 10? kg m7? = 2183.85 x 10" kg mol)
(6.022 045 x 107 mo1!)a

V3
ee, a eo pm) = 136.8 pm
 413

25.19 A close-packed structure of uniform spheres has a cubic unit cell

with a side of 800 pm. What is the radius of the spherical

molecule?

SOLUTION
Since the cubic close-packed structure is face-centered cubic, a
face diagonal is equal to four radii.

Length of m1
face diagonal = V128 x 10
800 pm
Radius of Ni 4
sphere: = ee oe = 282.8 pm

25.20 If spherical molecules of 500 pm radius are packed in cubic close

packing, and body-centered cubic, what are the lengths of the

sides of the cubic unit cells in the two cases?

SOLUTION

Cubic close packing (face-centered cubic)

Length of diagonal = 2,000 pm

Length of side
of unit cell — 1414.2 pm
2

Body-centered cubic

Consider a plane bisecting the cube and cutting diagonally through

opposite faces.

Length of diagonal = 2,000 pm

20007 = ae + (2 Se = Bao
2
a = A = 1154.7 pm
414

DeaI Titanium forms hexagonal close-packed crystals. Given the atomic

radius of 146 pm, what are the unit cell dimensions and what is

the density of the crystal?

SOLUTION
a = b = 2(156 pm) = 292 pm Cera rn 2 ay are 47 Tepe

Ve= Ae c(i) = ore aye = at c sin y

= (202npm)>
AY Tien) sins 120 eee uae does 105 ee

AP a) ee (47see
OR 90LTn eeI1OL ee
Ake MOLE»)
ee eee
(6.022 045 x 1023 mo1~1) (35.22 x 10°29 m)
3
esi ge s 10 ea
25.22 Metallic sodium forms a body-centered cubic unit cell with a =

424 pm. What is the sodium atom radius?

SOLUTION
Three atoms are in contact along the diagonal of the unit cell

(4B) Gama (424. pale ete ©pn) aero eee

R = ale. 424 pm = 184 pm

Alternatively,
1/2
1 z)
= : (x, ms 2 7 2 2
x,) + (y, y,? + (z, - z,) |

=‘ 424 pm 1 +
E 1
a +
1 L/2
i| ok cascae
3
424 pm = 367 pm

The sodium atom radius is half the distance.

367 pm
) = 184 pm
 415

25.23 What neutron energy in electronvolts is required for a wavelength

of 100 pm?

SOLUTION
2 2
Kinetic energy = ae then) since A = h/p
n 2m
n
2
Ee = = 5)
2X m

h2
E = 5)
2X me
n
(ABE34 oe
2(10729 m)2(1.675 x 10727 kg) (1.602 x 10729 c)
= 0.0818 V or 0.0818 eV

25.24 A solution of carbon in face-centered cubic iron has a density of

8.105 g cm > and a unit cell edge of 358.3 pm. Are the carbon
atoms interstitial, or do they substitute for iron atoms in the

lattice? What is the weight percent carbon?

SOLUTION
2 4(55.847 x 10° kg mol)
ae (6.022 045 x 1072 mo14) a (358.3 x 10 peas
1” m)
ty eee toe Voor ie
Since the experimental density is greater, the carbon atoms must
be interstitial.

$105 4910° ay = ©
-8.064 x 10°
0.041 x 10°
416

0.041 x 10°
100 = 0.51% by weight
8.105 x 10

25.25 At 50 °C the conductivity of solid NaCl is 20> et0mmece Sm

Since the sodium ions are smaller than the chloride ions (see
Table 25.1), they are responsible for most of the electric
conductivity. What is the ionic mobility of Na* under these

conditions?

SOLUTION
Since there are 4 Na~ per unit cell of a = 564 pm

(564 x 10-2 m)3

According to equation 25.38

u.= K/Na =
(2.23 x 1078 m-3)(1.60 x 10719 ¢)
S61 xi Ob uae Wor cae

25.26 What fraction of the lattice sites of a crystal are vacant at 300
K if the energy required to move an atom from a lattice site in
the crystal to a lattice site on the surface is 1 eV? At 100 K?

SOLUTION ; - E /kT
At 300 K N = e =

_ —__(1¥)
(1,602
090
x0a10°*e)
(1.38 x 10 7? 3 K+) 300 z
: Dll awe pi year
é (1V) (1.602
x 10! ¢)
-23 -1 Sy
ret een
At 1000 K ; (1.38 x 10 JK mol —)(1000 K)

9.08 x 10°
 n= 7

(a) 6 (b) 8 (c) 12

When h + k is odd, the structure factor F(hkl) is zero and

the reflection is extinguished.

(a) body-centered

(b) 314.8

(oe) 10,521 ¢ cm>

25. (a) 628 pm (b) 2.00 g cm>

25% 392.4 pm

714.69 g mo11

2826 kg m >
(a) 2 (b) 328
(c) 164 (d) 232
(e) 94.7 nm

287,124 pm
2.703 g cm>
aeLate cm?

8.836 x 10° kg m >

2.33 x 10° kg m >
ila)

152 pm

346 pm

(a) 8/3 a (67))-2 vee r (Co) 2:

418

25.46 0.524

25.47 0.414

25.48 145.8 pm

25.49 490 cm? v1 5-1

251.00 3.6 x 107° mole fraction

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