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Solutions Manual for Mathematics

for Physical Chemistry

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Full file at https://buklibry.com/download/solutions-manual-mathematics-for-physical-chemistry-4th-edition-by-robert-g-mortimer/

Solutions Manual
for Mathematics for
Physical Chemistry
Fourth Edition

Robert G. Mortimer
Professor Emeritus
Rhodes College
Memphis, Tennessee

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD • PARIS

SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

Academic Press is an Imprint of Elsevier

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Contents

Preface vii

1 Problem Solving and Numerical 10  Mathematical Series e79

Mathematicse1
11  Functional Series and Integral
2 Mathematical Functions e7 Transformse89

3 Problem Solving and Symbolic 12  Differential Equations e97

Mathematics: Algebra e13
13  Operators, Matrices, and
4 Vectors and Vector Algebra e19 Group Theory e113

5 Problem Solving and the Solution 14  The Solution of Simultaneous

of Algebraic Equations e23 Algebraic Equations with More
Than Two Unknownse125
6 Differential Calculus e35
15  Probability, Statistics, and
7 Integral Calculus e51 Experimental Errors e135

8 Differential Calculus with Several 16  Data Reduction and the

Independent Variables e59 Propagation of Errors e145

9 Integral Calculus with Several

Independent Variables e69

v
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This book provides solutions to nearly of the exercises and
problems in Mathematics for Physical Chemistry, fourth
edition, by Robert G. Mortimer. This edition is a revision
of a third edition published by Elsevier/Academic Press in
2005. Some of exercises and problems are carried over from
earlier editions, but some have been modified, and some
new ones have been added. I am pleased to acknowledge
the cooperation and help of Linda Versteeg-Buschman, Beth
Campbell, Jill Cetel, and their collaborators at Elsevier. It is
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Preface
also a pleasure to acknowledge the assistance of all those
who helped with all editions of the book for which this is
the solutions manual, and especially to thank my wife, Ann,
for her patience, love, and forbearance.
There are certain errors in the solutions in this manual, and
I would appreciate learning of them through the publisher.
Robert G. Mortimer
vii
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Chapter 1
 

Problem Solving and Numerical

Mathematics

EXERCISES Exercise 1.4. Round the following numbers to three

significant digits
Exercise 1.1. Take a few fractions, such as 23 , 49 or 37 and
represent them as decimal numbers, finding either all of the
a. 123456789123 ≈ 123,000,000,000
nonzero digits or the repeating pattern of digits.
b. 46.45 ≈ 46.4
2
= 0.66666666 · · ·
3 Exercise 1.5. Find the pressure P of a gas obeying the
4
= 0.4444444 · · · ideal gas equation
9
3 P V = n RT
= 0.428571428571 · · ·
7
if the volume V is 0.200 m3 , the temperature T is 298.15 K
Exercise 1.2. Express the following in terms of SI base and the amount of gas n is 1.000 mol. Take the smallest
units. The electron volt (eV), a unit of energy, equals and largest value of each variable and verify your number
1.6022 × 10−18 J. of significant digits. Note that since you are dividing by
  V the smallest value of the quotient will correspond to the
1.6022 × 10−19 J
a. (13.6 eV) = 2.17896 × 10−19 J largest value of V.
1 eV
≈ 2.18 × 10−18 J
    n RT
5280 ft 12 in 0.0254m P =
b. (24.17 mi) V
1 mi 1 ft 1 in (1.000 mol)(8.3145 J K−1 mol−1 )(298.15 K)
= 3.890 × 104 m =
0.200 m3
   
5280 ft 12 in 0.0254 m = 12395 J m = 12395 N m−2 ≈ 1.24 × 104 Pa
−3
c. (55 mi h−1 )
1 mi 1 ft 1 in n RT
  Pmax =
1h −1 −1 V
= 24.59 m s ≈ 25 m s
3600 s    12  (1.0005 mol)(8.3145 J K−1 mol−1 )(298.155 K)
1m 10 ps =
d. (7.53 nm ps )−1 0.1995 m3
109 nm 1s = 4
1.243 × 10 Pa
= 7.53 × 103 m s−1 n RT
Pmin =
Exercise 1.3. Convert the following numbers to scientific V
notation: (0.9995 mol)(8.3145 J K−1 mol−1 )(298.145 K)
=
0.2005 m3
a. 0.00000234 = 2,34 × 10−6 4
b. 32.150 = 3.2150 × 101 = 1.236 × 10 Pa

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00025-2

© 2013 Elsevier Inc. All rights reserved. e1
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e48 Mathematics for Physical Chemistry

35. The van der Waals equation of state is Do the calculation by hand, and verify your result by
  use of Excel. A graph indicates a root near x = 0.300.
n2a we take x0 = 0.300.
P + 2 (V − nb) = n RT
V
f (x0 )
When the temperature of a given gas is equal to x1 = x0 −
f  (x0 )
its critical temperature, the gas has a state at which
the pressure as a function of V at constant T and n f (0.3) = 1.500 − e0.300 = 0.15014
exhibits an inflection point at which dP/dV = 0 and f  (0.300) = 5.000 − 1.34986 = 3.65014
d2 P/dV 2 = 0. This inflection point corresponds to the 0.15014
critical point of the gas. Write P as a function of T, V, x1 = 0.300 −
3.65014
and nand write expressions for dP/dV and d2 P/dV 2 , = 0.300 − 0.04113 = 0.2589
treating T and n as constants. Set these two expressions f (x1 )
equal to zero and solve the simultaneous equations to x2 = x1 − 
f (x1 )
find an expression for the pressure at the critical point.
f (0.2589) = 1.29434 − e0.0.2589
n RT n2a = 1.29434 − 1.29546 = −0.001130
P = − 2 
V − nb V f (0.2589) = 5.00 − e0.2589
dP n RT 2n 2 a = 5.000 − 1.2956 = 3.70454
= − +
dV (V − nb)2 V3 −0.001130
= 0 at the critical point (6.1) x2 = 0.2589 −
3.70454
2
d P 2n RT 6n 2 a = 0.2589 + 0.00359 = 0.26245
= + f (x2 )
dV 2 (V − nb)3 V4 x3 = x2 − 
= 0 at the critical point (6.2) f (x2 )
f (0.26245) = 1.31226 − e0.26245
Solve Eq. (6.1) for Tc :
= 1.31226 − 1.30011 = 0.01215
2n 2 a(Vc − nb)2 f  (0.26245) = 5.00 − e0.26245
Tc = (6.3)
n RVc3 = 5.000 − 1.30011 = 3.69989
0.01215
Substitute this expression into Eq. (6.2): x3 = 0.26245 −
3.69989
  2  = 0.2589 + 0.00359 = 0.25917
2n R 2n a(V − nb)2 6n 2 a
0 = − +
(V − nb)3 n RV 3 V4
We discontinue iteration at this point. The root is
4n 2 a 6n 2 a actually at x = 0.25917 to five significant digits.
0 = − +
(V − nb) V Notice that the approximations oscillate around the
2 3 correct value.
0 = − + when V = Vc
(V − nb) V 37. Solve the following equations by hand, using
Vc = 3nb Newton’s method. Verify your results using Excel or
Mathematica:
Substitute this into Eq. (6.3)
a. e−x − 0.3000x = 0. A rough graph indicates a
2n 2 a(2nb)2 8a
Tc = = root near x = 1. We take x0 = 1.000
n R(27n 3 b3 ) 27Rb
f = e−x − 0.3000x
n RTc n2a 8n Ra n2a f  = −e−x − 0.3000
Pc = − 2 = − 2 2 f (x0 )
Vc − nb Vc 27Rb(2nb) 9n b x1 = x0 − 
4a a a f (x0 )
= − 2 = f (1.000) = e−1.000 − 0.3000 = 0.06788
27b2 9b 27b2
f  (1.000) = −e−1.000 − 0.3000 = −1.205
36. Carry out Newton’s method to find the smallest
positive root of the equation 0.06788
x1 = 1.000 −
−1.205
5.000x − e x = 0 = 1.000 + 0.0563 = 1.0563

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CHAPTER | 13 Operators, Matrices, and Group Theory e123

⎡ ⎤
21. Test the following matrices for singularity. Find the  −1 1 1
inverses of any that are nonsingular. Multiply the 2 3 ⎢− ⎥
X−1 = = ⎣ 22 21 ⎦
original matrix by its inverse to check your work. Use 4 3 −
Mathematica to check your work. 3 3
⎡ ⎤     
3 2 −1 1 2 2 3 10 9
⎢ ⎥ QX = =
a. ⎣ −4 6 3 ⎦ 2 1 4 3 8 9
7 2 −1
  ⎡ ⎤
 3 2 −1  1 1    
  −
  ⎢ 2 2 ⎥ 10 9 −1 0
 −4 6 3  = 48 −1
X QX = ⎣ 2
  1⎦ 8 9 = 4 3
 7 2 −1  −
3 3
Not singular
23. The H2 O molecule belongs to the point group C2v ,
⎡ ⎤  C2 , σ̂a ,
1 1 which contains the symmetry operators E,
⎡ ⎤−1 − 0
3 2 −1 ⎢ 4 4 ⎥ and σ̂b , where the C2 axis passes through the oxygen
⎢ ⎥
⎢ ⎥ ⎢ 17 1 5 ⎥ nucleus and midway between the two hydrogen nuclei,
⎣ −4 6 3 ⎦ ⎢ − ⎥
⎢ 48 12 48 ⎥ and where the σa mirror plane contains the three nuclei
7 2 −1 ⎣ 25 1 13 ⎦
and the σb mirror plane is perpendicular to the σa
−
24 6 24 mirror plane.
⎡ ⎤ a. Find the 3 by 3 matrix that is equivalent to each
1 1
⎡ ⎤ − 0 ⎡ ⎤ symmetry operator.
3 2 −1 ⎢ ⎢ 4 4 ⎥ 1 0 0
⎥
⎢ ⎥ ⎢ 17 1 5 ⎥ ⎢ ⎥ ⎡ ⎤
⎣ −4 6 3 ⎦ ⎢ − ⎥ = ⎣0 1 0⎦.
⎢ 48 12 48 ⎥ 1 0 0
7 2 −1 ⎣ 25 1 13 ⎦ 0 0 1 ↔ ⎢ ⎥
−
E ⎣0 1 0⎦
24 6 24 0 0 1
⎡ ⎤
0 2 3 ⎡ ⎤
⎢ ⎥ −1 0 0
b. ⎣ 1 0 1 ⎦
2 ↔ ⎢
C ⎣ 0 −1 0 ⎦
⎥
2 0 1  
0 2 3  0 0 1

  ⎡ ⎤
1 0 1 = 2
  1 0 0
2 0 1 ⎢ ⎥
σ̂a ↔ ⎣ 0 1 0⎦
Not singular
0 0 1
⎡ ⎤−1 ⎡ ⎤
0 2 3 0 −1 1 ⎡ ⎤
⎢ ⎥ ⎢ 1 3 ⎥ −1 0 0
⎣1 0 1⎦ = ⎢ ⎣ −3 ⎥ ⎢ ⎥
2 2 ⎦ σ̂b ↔ ⎣ 0 −1 0 ⎦
2 0 1 0 2 −1 0 0 1
Check: b. Show that the matrices obtained in part (a)
⎡ ⎤⎡ ⎤ ⎡ ⎤
0 −1 1 have the same multiplication table as the
0 2 3 ⎢ 1 0 0
⎢ ⎥ 1 3 ⎥
⎥ ⎢ ⎥ symmetry operators, and that they form a group.
⎣1 0 1⎦⎢ −3 = ⎣0 1 0⎦.
⎣ 2 2 ⎦ The multiplication table for the group was to
2 0 1 0 2 −1 0 0 1 be obtained in an exercise. The multiplication
table is
22. Find the matrix P that results from the similarity
transformation 
E 2 
C σv(yz) σv(x z)
P = X−1 QX, 
E 
E 2 
C σv(yz) σv(x z)
where     
C2 
C2 
E  σv(x z) 
σv(yz)
1 2 2 3 
σv(yz) σv(yz) 
σv(x z) E 2
C
Q= ,X= .
2 1 4 3 
σv(x z) 
σv(x z)  
σv(yz) C2 
E

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