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Student Solutions Manual for

Mathematics for Physical Chemistry


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Student 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 e57


Mathematicse1
11 Functional Series and Integral
2 Mathematical Functions e5 Transformse63

3 Problem Solving and Symbolic 12 Differential Equations e69


Mathematics: Algebra e11
13 Operators, Matrices, and
4 Vectors and Vector Algebra e15 Group Theory e79

5 Problem Solving and the Solution 14 The Solution of Simultaneous


of Algebraic Equations e19 Algebraic Equations with More
Than Two Unknownse89
6 Differential Calculus e27
15 Probability, Statistics, and
7 Integral Calculus e37 Experimental Errors e95

8 Differential Calculus with Several 16 Data Reduction and the


Independent Variables e43 Propagation of Errors e103

9 Integral Calculus with Several


Independent Variables e51

v
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Preface

This students solutions manual provides solutions to and their collaborators at Elsevier. It is also a pleasure to
nearlyallof the exercises and nearly all of the odd-numbered acknowledge the assistance of all those who helped with all
problems inMathematics for Physical Chemistry, Fourth editions of the book for which this is the solutions manual,
Edition, by Robert G. Mortimer. This edition is a revision of and especially to thank my wife, Ann, for her patience, love,
the third edition, published by Elsevier/Academic Press in and forbearance.
2005. Some oftheexercises and problems have been carried There are inevitably errors in the solutions in this man-
over from the third edition. Others have been modified, and ual, and I would appreciate learning of them through the
a number of new ones have been added. publisher.
I am pleased to acknowledge the cooperation and help
of Linda Versteeg-Buschman, Beth Campbell, Jill Cetel, 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 1018 J. of significant digits. Note that since you are dividing by
  V the smallest value of the quotient will correspond to the
1.6022 1019 J
a. (13.6 eV) = 2.17896 1019 J largest value of V.
1 eV
2.18 1018 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 K1 mol1 )(298.15 K)
= 3.890 104 m =
0.200 m3
   
5280 ft 12 in 0.0254 m = 12395 J m = 12395 N m2 1.24 104 Pa
3
c. (55 mi h1 )
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 K1 mol1 )(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 s1 n RT
Pmin =
Exercise 1.3. Convert the following numbers to scientific V
notation: (0.9995 mol)(8.3145 J K1 mol1 )(298.145 K)
=
0.2005 m3
a. 0.00000234 = 2,34 106 4
b. 32.150 = 3.2150 101 = 1.236 10 Pa

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00047-1


2013 Elsevier Inc. All rights reserved. e1
e2 Mathematics for Physical Chemistry

Exercise 1.6. Calculate the following to the proper   3


1 m3 1 in
numbers of significant digits. (22.414 l)
1000 l 0.0254 m3
 
a. 17.13 + 14.6751 + 3.123 + 7.654 8.123 = 34.359 1 gal
= 5.9212 gal
34.36 231.00 in3
b. ln (0.000123)   3
1 m3 1 in
(22.414 l)
1000 l 0.0254 m3
 3
ln (0.0001235) = 8.99927 1 ft
= 0.79154 ft3
ln (0.0001225) = 9.00740 12 in

The answer should have three significant digits: 9. Find the average length of a century in seconds and in
minutes. Use the rule that a year ending in 00 is not a
ln (0.000123) = 9.00 leap year unless the year is divisible by 400, in which
case it is a leap year. Therefore, in four centuries there
will be 97 leap years. Find the number of minutes in a
microcentury.
PROBLEMS
1. Find the number of inches in 1.000 meter. Number of days in 400 years
  = (365 d)(400 y) + 97 d = 146097 d
1 in
(1.000 m) = 39.37 in Average number of days in a century
0.0254 m
146097 d
= = 36524.25 d
3. Find the speed of light in miles per second. 4   
   24 h 60 min
1 in 1 ft 1 century = (36524.25 d)
(299792458 m s1 ) 1d 1h
0.0254 m 12 in
  = 5.259492 107 min
1 mi  
= 186282.397 mi s1 7 1 century
5280 ft (5.259492 10 min)
1 106 microcenturies
5. A furlong is exactly one-eighth of a mile and a = 52.59492 min
 
fortnight is exactly 2 weeks. Find the speed of light 60 s
in furlongs per fortnight, using the correct number of (52.59492 min) = 3155.695 s
1 min
significant digits.
   11. The Rankine temperature scale is defined so that the
1 1 in 1 ft Rankine degree is the same size as the Fahrenheit
(299792458 m s )
0.0254 m 12 in degree, and absolute zero is 0 R, the same as 0 K.
  
1 mi 8 furlongs
a. Find the Rankine temperature at 0.00 C.
5280 ft 1 mi
     
3600 s 24 h 14 d 9 F
0.00 C (273.15 K) = 491.67 R
1h 1d 1 fortnight 5K
= 1.80261750 1012 furlongs fortnight1
b. Find the Rankine temperature at 0.00 F.
7. A U. S. gallon is defined as 231.00 cubic inches.
273.15 K 18.00 K = 255.15 K
 
9 F
a. Find the number of liters in 1.000 gallon. (255.15 K) = 459.27 R
5K
  3  
231.00 in3 0.0254 m 1000 l
(1 gal) 13. The volume of a right circular cylinder is given by
1 gal 1 in 1 m3
= 3.785 l V = r 2 h,

b. The volume of 1.0000 mol of an ideal gas where r is the radius and h is the height. If a right
at 0.00 C (273.15 K) and 1.000 atm is circular cylinder has a radius given as 0.134 m and a
22.414 liters. Express this volume in gallons and height given as 0.318 m, find its volume, specifying
in cubic feet. it with the correct number of digits. Calculate the
CHAPTER | 1 Problem Solving and Numerical Mathematics e3

smallest and largest volumes that the cylinder might water is 4.18 J C1 g1 . Find the rise in temperature
have with the given information and check your first if 100.0 J of heat is transferred to 1.000 kg of water.
answer for the volume.  
100.0 J 1 kg
T =
V = (0.134 m)2 (0.318 m) = 0.0179 m3 (4.18 J C1 g1 )(1.000 kg) 1000 g
Vmin = (0.1335 m)2 (0.3175 m) = 0.01778 m3 = 0.0239 C
Vmax = (0.1345 m)2 (0.3185 m) = 0.0181 m3
19. The volume of a sphere is equal to 43 r 3 where r is the
15. Some elementary chemistry textbooks give radius of the sphere. Assume that the earth is spherical
the value of R, the ideal gas constant, as with a radius of 3958.89 miles. (This is the radius of
0.0821 l atm K1 mol1 . a sphere with the same volume as the earth, which
is flattened at the poles by about 30 miles.) Find the
a. Using the SI value, 8.3145 J K1 mol1 , obtain volume of the earth in cubic miles and in cubic meters.
the value in l atm K1 mol1 to five significant Use a value of with at least six digits and give the
digits. correct number of significant digits in your answer.
   4 3 4
1 1 1 Pa m3 1 atm V = r = (3958.89 mi)3
(8.3145 J K mol ) 3 3
1J 101325 Pa
 
1000 l = 2.59508 1011 mi3
= 0.082058 l atm K1 mol1    
1 m3 5280 ft 3 12 in 3
11 3
(2.59508 10 mi )
b. Calculate the pressure in atmospheres and in 1 mi 1 ft
N m2 (Pa) of a sample of an ideal gas with n =  3
0.0254 m
0.13678 mol, V = 10.000 l and T = 298.15 K. = 1.08168 1021 m3
1 in
n RT
P= 21. The hectare is a unit of land area defined to equal
V exactly 10,000 square meters, and the acre is a unit
(0.13678 mol)(0.082058 l atm K1 mol1 )(298.15 K) of land area defined so that 640 acres equals exactly
=
1.000 l one square mile. Find the number of square meters in
= 0.33464 atm 1.000 acre, and find the number of acres equivalent to
n RT 1.000 hectare.
P=
V   
(0.13678 mol)(8.3145 J K1 mol1 )(298.15 K) (5280 ft)2 12 in 2
= 1.000 acre =
10.000 103 m3 640 1 ft
4 3 4 2  2
= 3.3907 10 J m = 3.3907 10 N m 0.0254 m
4
= 4047 m2
= 3.3907 10 Pa 1 in
 
10000 m2
17. The specific heat capacity (specific heat) of a substance 1.000 hectare = (1.000 hectare)
1 hectare
is crudely defined as the amount of heat required to  
raise the temperature of unit mass of the substance by 1 acre
= 2.471 acre

1 degree Celsius (1 C). The specific heat capacity of 4047 m2
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Chapter 2
 

Mathematical Functions

EXERCISES 0.1 = 1/10


Exercise 2.1. Enter a formula into cell D2 that will log (0.1) = log (10) = 1
compute the mean of the numbers in cells A2,B2, and C2.
0.01 = 1/100
= (A2 + B2 + C2)/3
log (0.01) = log (100) = 2
Exercise 2.2. Construct a graph representing the function

y(x) = x 3 2x 2 + 3x + 4 (2.1) 0.001 = 1/1000

Use Excel or Mathematica or some other software to log (0.001) = log (1000) = 3
construct your graph.
Here is the graph, constructed with Excel: 0.0001 = 1/10000

log (0.001) = log (10000) = 4

Exercise 2.4. Using a calculator or a spreadsheet, evaluate


the quantity (1+ n1 )n for several integral values of n ranging
from 1 to 1,000,000. Notice how the value approaches the
value of e as n increases and determine the value of n needed
to provide four significant digits.
Here is a table of values
' $
x (1 + 1/n)n

1 2
Exercise 2.3. Generate the negative logarithms in the short
2 2.25
table of common logarithms.
5 2.48832
' $
10 2.59374246
x y = log10 (x) x y = log10 (x) 100 2.704813829
1 0 0.1 1 1000 2.716923932
10 1 0.01 2 10000 2.718145927
100 2 0.001 3 100000 2.718268237
1000 3 0.0001 4 1000000 2.718280469
& %& %
Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00048-3
2013 Elsevier Inc. All rights reserved. e5
e6 Mathematics for Physical Chemistry

To twelve significant digits, the value of e is There is no round-off error to 11 digits in the calculator
2.71828182846. The value for n = 1000000 is accurate that was used.
to six significant digits. Four significant digits are obtained
with n = 10000. Exercise 2.9. Using a calculator and displaying as many
digits as possible, find the values of the sine and cosine of
Exercise 2.5. Without using a calculator or a table of 49.500 . Square the two values and add the results. See if
logarithms, find the following: there is any round-off error in your calculator.

a. ln (100.000) = ln (10) log10 (100.000) sin (49.500 ) = 0.7604059656


= (2.30258509 )(2.0000) = 4.60517
cos (49.500 ) = 0.64944804833
b. ln (0.0010000) = ln (10) log10 (0.0010000)
= (2.30258509 )(3.0000) = 6.90776 (0.7604059656)2 + (0.64944804833)2 = 1.00000000000
ln (e) 1
c. log10 (e) = = = 0.43429 Exercise 2.10. Construct an accurate graph of sin (x) and
ln (10) 2.30258509
tan (x) on the same graph for values of x from 0 to 0.4 rad
Exercise 2.6. For a positive value of b find an expression and find the maximum value of x for which the two functions
in terms of b for the change in x required for the function differ by less than 1%.
ebx to double in size.
f (x + x) eb(x+x)
= 2= = ebx
f (x) ebx
ln (2) 0.69315
x = =
b b
Exercise 2.7. A reactant in a first-order chemical reaction
without back reaction has a concentration governed by the
same formula as radioactive decay,

[A]t = [A]0 ekt ,

where [A]0 is the concentration at time t = 0, [A]t is the The two functions differ by less than 1% at 0.14 rad.
concentration at time t, and k is a function of temperature Notice that at 0.4 rad, sin (x) x tan (x) and that the
called the rate constant. If k = 0.123 s1 find the time three quantities differ by less than 10%.
required for the concentration to drop to 21.0% of its initial
value. Exercise 2.11. For an angle that is nearly as large as /2,
        find an approximate equality similar to Eq. (2.36) involving
1 [A]0 1 100.0 (/2) , cos (), and cot ().
t = ln = ln
k [A]t 0.123 s1 21.0 Construct a right triangle with angle with the angle
= 12.7 s (/2) , where is small. The triangle is tall, with a
small value of x (the horizontal leg) and a larger value of y
Exercise 2.8. Using a calculator, find the value of the (the vertical leg). Let r be the hypotenuse, which is nearly
cosine of 15.5 and the value of the cosine of 375.5 . equal to y.
Display as many digits as your calculator is able to display. x
Check to see if your calculator produces any round-off error cos ((/2) ) =
r
in the last digit. Choose another pair of angles that differ by cot ((/2) ) = xy rx . The measure of the angle
360 and repeat the calculation. Set your calculator to use in radians is equal to the arc length subtending the angle
angles measured in radians. Find the value of sin (0.3000). divided by r and is very nearly equal to x/r . Therefore
Find the value of sin (0.3000 + 2 ). See if there is any
round-off error in the last digit. cos ((/2) )

cos (15.5 ) = 0.96363045321 cot ((/2) )



cos (375.5 ) = 0.96363045321 cos ((/2) ) cot ((/2) )
sin (0.3000) = 0.29552020666
Exercise 2.12. Sketch graphs of the arcsine function, the
sin (0.3000 + 2 ) = sin (6.58318530718) arccosine function, and the arctangent function. Include
= 0.29552020666 only the principal values.
CHAPTER | 2 Mathematical Functions e7

Here are accurate graphs: We calculate sin (95.45 ) and sin (95.45 ). Using a
calculator that displays 8 digits, we obtain

sin (95.45 ) = 0.99547946

sin (95.55 ) = 0.99531218


We report the sine of 95.5 as 0.9954, specifying four
significant digits, although the argument of the sine was
given with three significant digits. We have followed the
common policy of reporting a digit as significant if it might
be incorrect by one unit.

Exercise 2.15. Sketch rough graphs of the following


functions. Verify your graphs using Excel or Mathematica.

a. ex/5 sin (x). Following is a graph representing each


of the factors and their product:

b. sin2 (x) = [sin (x)]2

Following is a graph representing sin (x) and sin2 (x).

Exercise 2.13. Make a graph of tanh (x) and coth (x) on


the same graph for values of x ranging from 0.1 to 3.0.

PROBLEMS
1. The following is a set of data for the vapor pressure
of ethanol taken by a physical chemistry student.
Exercise 2.14. Determine the number of significant digits Plot these points by hand on graph paper, with the
in sin (95.5 ). temperature on the horizontal axis (the abscissa) and
e8 Mathematics for Physical Chemistry

the vapor pressure on the vertical axis (the ordinate). where [A]0 is the concentration at time t = 0, [A]t
Decide if there are any bad data points. Draw a smooth is the concentration at time t, and k is a function
curve nearly through the points, disregarding any bad of temperature called the rate constant. If k =
points. Use Excel to construct another graph and notice 0.232 s1 at 298.15 K find the time required for the
how much work the spreadsheet saves you. concentration to drop to 33.3% of its initial value at a
' $constant temperature of 298.15 K.
Temperature/ C Vapor pressure/torr  
ln [A]0 /[A]t ln (1/0.333)
t= = = 4.74 s
25.00 55.9 k 0.232 s1
30.00 70.0
5. Express the following with the correct number of
35.00 97.0 significant digits. Use the arguments in radians:
40.00 117.5
45.00 154.1 a. tan (0.600)
50.00 190.7
tan (0.600) = 0.684137
55.00 241.9
tan (0.5995) = 0.683403
& %
tan (0.60005) = 0.684210
Here is a graph constructed with Excel:
We report tan (0.600) = 0.684. If a digit is
probably incorrect by 1, we still treat it as
significant.
b. sin (0.100)

sin (0.100) = 0.099833


sin (0.1005) = 0.100331
sin (0.0995) = 0.099336

We report sin (0.100) = 0.100.


c. cosh (12.0)

cosh (12.0) = 81377


cosh (12.05) = 85550
The third data point might be suspect. Here is a cosh (11.95) = 77409
graph omitting that data point:
We report cosh (12.0) = 8 104 . There is only
one significant digit.
d. sinh (10.0)

sinh (10.0) = 11013


sinh (10.01) = 11578
sinh (9.995) = 10476

We report sinh (10.0) = 11000 = 1.1 104

7. Tell where each of the following functions is


discontinuous. Specify the type of discontinuity:

a. tan (x) Infinite discontinuities at x = /2,


x = 3/2, x = 5/2,
3. A reactant in a first-order chemical reaction without
b. csc (x) Infinite discontinuities at x = 0, x = ,
back reaction has a concentration governed by the
x = 2,
same formula as radioactive decay,
c. |x| Continuous everywhere, although there is a
[A]t = [A]0 ekt , sharp change of direction at x = 0.
CHAPTER | 2 Mathematical Functions e9

9. If the two ends of a completely flexible chain (one For this graph, we have plotted y 11.4538 such that
that requires no force to bend it) are suspended at the this quantity vanishes at the ends of the chain.
same height near the surface of the earth, the curve 11. Construct a graph of the two functions: 2 cosh (x) and
representing the shape of the chain is called a catenary. e x for values of x from 0 to 3. At what minimum value
It can be shown1 that the catenary is represented by of x do the two functions differ by less than 1%?
x 
y = a cosh
a
where
T
a=
g
and where is the mass per unit length, g is the
acceleration due to gravity, and T is the tension force
on the chain. The variable x is equal to zero at the center
of the chain. Construct a graph of this function such
that the distance between the two points of support is
10.0 m and the mass per unit length is 0.500 kg m1 ,
and the tension force is 50.0 N. By inspection in a column of values of the
T 50.0 kg m s2 difference, the two functions differ by less than 1%
a = = = 10.20 m at x = 2.4.
g (9.80 m s2 )(0.500 kg m1 )
2
13. Verify the trigonometric identity
y = (10.20 m) cosh (x/10.20 m)
cos (2x) = 1 2 sin2 (x)

for x = 0.50000 rad. Use as many digits as your


calculator will display and check for round-off error.

cos (1.00000) = 0.54030230587


1 2 sin2 (0.50000) = 1 0.45969769413
= 0.54030230587

There was no round-off error to 11 significant digits


in the calculator that was used.

1 G. Polya, Mathematical Methods in Science, The Mathematical Associa-


tion of America, 1977, pp. 178ff.
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Chapter 3
 

Problem Solving and Symbolic


Mathematics: Algebra

EXERCISES b. Find and if x = 5.00 and y = 10.00.



Exercise 3.1. Write the following expression in a simpler = x 2 + y 2 = 125.0 = 11.18
form:
= arctan (y/x) = arctan (2.00) = 1.107 rad
(x 2 + 2x)2 x 2 (x 2)2 + 12x 4
B= . = 63.43
6x 3 + 12x 4
Exercise 3.4. Find the spherical polar coordinates of the
x 2 (x 2 + 4x + 4) x 2 (x 2 4x + 4) + 12x 4 point whose Cartesian coordinates are (2.00, 3.00, 4.00).
B = 
6x 3 + 12x 4
r = (2.00)2 + (3.00)2 (4.00)2 = 29.00 = 5.39
 
x 4 + 4x 3 + 4x 2 x 4 + 4x 3 4x 2 + 12x 4 3.00
= = arctan = 0.98279 rad = 56.3
6x 3 + 12x 4 2.00
 
12x 4 + 8x 3 12x + 8 6x + 4 4.00
= = = = arccos = 0.733 rad = 42.0
6x 3 + 12x 4 12x + 6 6x + 3 5.39
Exercise 3.5. Find the Cartesian coordinates of the point
Exercise 3.2. Manipulate the van der Waals equation into whose cylindrical polar coordinates are = 25.00, =
an expression for P in terms of T and Vm . Since the pressure 60.0 , z = 17.50
is independent of the size of the system (it is an intensive
variable), thermodynamic theory implies that it can depend x = cos () = 25.00 cos (60.0 )
on only two independent intensive variables. = 25.00 0.500 = 12.50
 
a y = sin () = 25.00 sin (60.0 )
P + 2 (Vm b) = RT
Vm = 25.00 0.86603 = 21.65
a RT z = 17.50
P+ 2 =
Vm Vm b
RT a Exercise 3.6. Find the cylindrical polar coordinates of the
P = 2 point whose Cartesian coordinates are (2.000,2.000,
Vm b Vm
3.000).

Exercise 3.3. a. Find x and y if = 6.00 and = /6 = ( 2.00)2 + ( 2.00)2 = 2.828
radians  
2.00
= arctan = 0.7854 rad = 45.0
x = (6.00) cos (/6) = (6.00)(0.866025) = 5.20 2.00
y = sin () = (6.00)(0.500) = 3.00 z = 3.000

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00049-5


2013 Elsevier Inc. All rights reserved. e11
e12 Mathematics for Physical Chemistry

Exercise 3.7. Find the cylindrical polar coordinates of b. B = (3 + 7i)3 (7i)2 .


the point whose spherical polar coordinates are r = 3.00,
= 30.00 , = 45.00 . B = (3 7i)3 (7i)2 = (3 7i)3 (7)2

z = r cos ( ) = (3.00) cos (30.00 ) = 3.00 0.86603 Exercise 3.12. Write a complex number in the form x +i y
= 2.60 and show that the product of the number with its complex
conjugate is real and nonnegative
= r sin ( ) = (3.00) sin (30.00 ) = (3.00)(0.500)
= 1.50 (x + i y)(x i y) = x 2 + i x y i x y + y 2 = x 2 + y 2
= 45.00
The square of a real number is real and nonnegative, and x
Exercise 3.8. Simplify the expression and y are real.

(4 + 6i)(3 + 2i) + 4i Exercise 3.13. If z = (3.00 + 2.00i)2 , find R(z), I (z), r ,


and .
(4 + 6i)(3 + 2i) + 4i = 12 + 18i + 8i 12 + 4i = 30i
Exercise 3.9. Express the following complex numbers in z = 9.00 + 6.00i 4.00 = 5.00 + 6.00i
the form r ei :
a. z = 4.00 + 4.00i
R(z) = 5.00

r = 32.00 = 5.66 I (z) = 6.00
 
4.00 r = 25.00 + 36.00 = 7.781
= arctan = 0.785
4.00 = arctan (6.00/5.00) = 0.876 rad = 50.2
0.785i
z = 4.00 + 4.00i = 5.66e
Exercise 3.14. Find the square roots of z = 4.00 + 4.00i.
b. z = 1.00 Sketch an Argand diagram and locate the roots on it.
z = 1 = ei z = r ei

Exercise 3.10. Express the following complex numbers in r = 32.00 = 5.657
the form x + i y = arctan (1.00) = 0.785398 rad = 45.00
a. z = 3ei/2

x = r cos () = 3 cos (/2) = 3 0 = 0  5.657e0.3927i

z= 0.785398+2

y = r sin () = 3 sin (/2) = 3 1 = 3 5.657 exp 2 i = 5.657e3.534i
z = 3i
To sketch the Argand diagram, we require the real and
b. z = e3i/2 imaginary parts. For the first possibility

z = 5.657( cos (22.50 )) + i sin (22.50 )
x = r cos () = cos (3/2) = 0
= 5.657(0.92388 + i(0.38268)
y = r sin () = sin (3/2) = 1
= 2.1973 + 0.91019i
z = i
Exercise 3.11. Find the complex conjugates of For the second possibility

a. A = (x + i y)2 4ei x y z = 5.657( cos (202.50 )) + i sin (202.50 )

= 5.657(0.92388 + i(0.38268)
A = x 2 + 2i x y + y 2 4ei x y
= 2.1973 0.91019i
A = x 2 2i x y + y 2 4ei x y
= (x i y)2 4ei x y Exercise 3.15. Find the four fourth roots of 1.

Otherwise by changing the sign in front of every i: 1 = ei , e3i , e5i , e7i



4
A = (x i y)2 4ei x y ei = ei/4 , e3i/4 , e5i/4 , e7i/4
CHAPTER | 3 Problem Solving and Symbolic Mathematics: Algebra e13

Exercise 3.16. Estimate the number of house painters in 9. A surface is represented in cylindrical polar
Chicago. coordinates by the equation z = 2 . Describe the
The 2010 census lists a population of 2,695,598 for the shape of the surface. This equation represents a
city of Chicago, excluding surrounding areas. Assume that paraboloid of revolution, produced by revolving a
about 20% of Chicagoans live in single-family houses or parabola around the z axis.
duplexes that would need exterior painting. With an average 11. Find the complex conjugate of the quantity
family size of four persons for house-dwellers, this would e2.00i + 3ei
give about 135,000 houses. Each house would be painted
e2.00i + 3ei = e2.00i 3 = cos (2.00)
about once in six or eight years, giving roughly 20,000
house-painting jobs per year. A crew of two painters might + i sin (2.00) 3
2.00i i
paint a house in one week, so that a crew of two painters (e + 3e ) = cos (2.00) i sin (2.00) 3
could paint about 50 houses in a year. This gives about 400 = e2.00i 3
two-painter crews, or 800 house painters in Chicago.
13. Find the difference 3.00ei 2.00e2i .
3.00ei 2.00e2i = 3.00 2.00 = 5.00
PROBLEMS
15. Find the four fourth roots of 3.000i.
1. Manipulate the van der Waals equation into a cubic
i/2
equation in Vm . That is, make a polynomial with terms 3.000e

5i/2
proportional to powers of Vm up to Vm3 on one side of 3.000e
3.000i =
the equation. 3.000e9i/2



  3.000e13i/2
a
P + 2 (Vm b) = RT
Vm

4
3.000ei/8 = 1.316ei/8


4
4
3.000e5i/8 = 1.316e5i/8
Multiply by Vm2 3.000i =


4
3.000e9i/8 = 1.316e9i/8


(P Vm2 + a)(Vm b) = RT Vm2 4
3.000e13i/8 = 1.316e13i/8
P Vm3 + aVm b P Vm2 ab = RT Vm2  
3 + 2i 2
P Vm3 (b + RT )Vm2 + aVm ab = 0 17. If z = , find R(z), I (z), r, and .
4 + 5i
3. A Boy Scout finds a tall tree while hiking and wants to 4 5i 4 5i
estimate its height. He walks away from the tree and (4 + 5i)1 = =
16 + 25 41
finds that when he is 45 m from the tree, he must look  
3 + 2i 4 5i
upward at an angle of 32 to look at the top of the tree. = (3 + 2i)
4 + 5i 41
His eye is 1.40 m from the ground, which is perfectly  
level. How tall is the tree? 12 15 + 8 10
= + i+
41 41 41

h = (45 m) tan (32 ) + 1.40 m = 28.1 m + 1.40 m 22 7i
= 29.5 m 30 m =
41 41
 2  2
The zero in 30 m is significant, which we indicated 22 7i 22
=
with a bar over it. 41 41 41
   2
5. Express the equation y = b, where b is a constant, in 2 22 7 5
plane polar coordinates. i+
(41)2 41
y = sin () = b = 0.43378 0.18322i
b
= = b csc () R(z) = 0.43378
sin ()
I (z) = 0.18322
7. Find the values of the plane polar coordinates that
correspond to x = 3.00, y = 4.00. 
r = (0.43378)2 + (0.18322)2 = 0.47079
 
= 9.00 + 16.00 = 5.00 0.18322
  = arctan = arctan ( 0.42238)
4.00 0.43378
= arctan = 53.1 = 0.927 rad
3.00 = 0.39965
e14 Mathematics for Physical Chemistry

The principal value of the arctangent is in the fourth of 1.75 1010 m3 . Assume that the average grain of
quadrant, equal to 0.39965 rad. Since ranges from sane is roughly 0.3 mm in diameter, so that each cubic
0 to 2 , we subtract 0.39965 from 2 to get millimeter contains roughly 30 grains of sand. This is
equivalent to 3 1010 grains per cubic meter, so that
= 5.8835 rad we have roughly 5 1020 grains of sand. If we were to
include islands and inland bodies of water, we would
19. Estimate the number of grains of sand on the beaches likely have a number of grains of sand nearly equal to
of the major continents of the earth. Exclude islands Avogadros constant.
and inland bodies of water. 21. Estimate the number of blades of grass in a lawn with
Assume that the earth has seven continents with an an area of 1000 square meters.
average radius of 2000 km. Since the coastlines are Assume approximately 10 blades per square
somewhat irregular, assume that each continent has a centimeter.
coastline of roughly 10000 km = 1 107 m for a  
total coastline of 7 107 m. Assume that the average 100 cm 2
number = (10 cm2 ) (1000 m2 )
stretch of coastline has sand roughly 5 m deep and 1m
50 m wide. This gives a total volume of beach sand = 1 108
 

Chapter 4
 

Vectors and Vector Algebra

EXERCISES b. Find the components and the magnitude of 2.00A B.


Exercise 4.1. Draw vector diagrams and convince your- 2.00A B = i(4.00 + 1.00)+j(6.00 + 4.00)
self that the two schemes presented for the construction of
= i(5.00)+j(2.00)
D = A B give the same result.
|2.00A B| = 25.00 + 4.00 = 5.385
Exercise 4.2. Find A B if A = (2.50,1.50) and
c. Find A B.
B = (1.00,7.50)
A B = (2.00)(1.00) + (3.00)(4.00) = 14.00
A B = (1.50,9.00) = 1.50i + 9.00j
d. Find the angle between A and B.
Exercise 4.3. Let |A| = 4.00,|B| = 2.00, and let the angle
between them equal 45.0 . Find A B. AB 14.00
cos () = = = 0.94176
AB (3.606)(4.123)
A B = (4.00)(2.00) cos (45 ) = 8.00 0.70711 = 5.66. = arccos (0.94176) = 2.799 rad = 160.3

Exercise 4.4. If A = (3.00)i (4.00)j and B = Exercise 4.6. Find the magnitude of the vector
(1.00)i + (2.00)j. A = (3.00, 4.00, 5.00).

a. Draw a vector diagram of the two vectors. A = 9.00 + 16.00 + 25.00 = 50.00 = 7.07
b. Find A B and (2.00A) (3.00B).
Exercise 4.7. a. Find the Cartesian components of the
A B = 3.00 1.00 position vector whose spherical polar coordinates are
r = 2.00, = 90 , = 0 . Call this vector A.
+(4.00)(2.00) = 5.00
(2A) (3B) = 6(5.00) = 30.00 x = 2.00
y = 0.00
z = r cos ( ) = 0.00
Exercise 4.5. If A = 2.00i 3.00 j and B = 1.00i +
4.00 j A = (2.00)i

b. Find the scalar product of the vector A from part a


a. Find |A| and |B|.
and the vector B whose Cartesian components are
(1.00, 2.00, 3.00).
|A| = A = 4.00 + 9.00 = 3.606

|B| = B = 1.00 + 16.00 = 4.123 A B = 2.00 + 0 + 0 = 2.00

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00050-1


2013 Elsevier Inc. All rights reserved. e15
e16 Mathematics for Physical Chemistry

c. Find the angle between these two vectors. We must first By the right-hand rule, the angular momentum is vertically
find the magnitude of B. upward.

|B| = B = 1.00 + 4.00 + 9.00

= 14.00 = 3.742
2.00 PROBLEMS
cos () = = 0.26726
(2.00)(3.742)
1. Find A B if A = 2.00i + 3.00 j and B = 1.00i +
= arccos (0.26726) = 74.5 = 1.300 rad
3.00 j 1.00k.

Exercise 4.8. From the definition, show that


A B = 1.00i + 2.00k.

A B = (B A) . 3. Find A B if A = (0,2) and B = (2,0).

This result follows immediately from the screw-thread AB=0+0=0


rule or the right-hand rule, since reversing the order of the
factors reverses the roles of the thumb and the index finger.
5. Find A B if A = (1.00)i + (2.00) j + (3.00)k and
B = (1.00)i + (3.00) j (2.00)k.
Exercise 4.9. Show that the vector C is perpendicular to B.
We do this by showing that B C = 0. A B = 1.00 + 6.00 6.00 = 1.00

B C = B x C x + B y C y + Bz C z 7. Find A B if A = (0.00,1.00,2.00) and B =


= 1 + 2 1 = 0. (2.00,1.00,0.00).

Exercise 4.10. The magnitude of the earths magnetic A B = A B = i(A y Bz A z B y )


field ranges from 0.25 to 0.65 G (gauss). Assume that the + j(A z Bx A x Bz ) + k(A x B y A y Bx )
average magnitude is equal to 0.45 G, which is equivalent to
= i(0.00 2.00) + j(4.00 0.00)
0.000045 T. Find the magnitude of the force on the electron
in the previous example due to the earths magnetic field, + k(0.00 2.00)
assuming that the velocity is perpendicular to the magnetic = 2.00i + 4.00j 2.00k
field.
9. Find the angle between A and B if A = 1.00i +2.00 j +
|F| = F = (1.602 1019 C) 1.00k and B = 1.00i 1.00k.
(1.000 105 m s1 )(0.000045 T)
= 7.210 1019 A s m s1 kg s2 A1 A B = 1.00 + 0 2.00 = 1.00


19 2 19 A = 1.00 + 4.00 + 1.00 = 6.00 = 2.4495
= 7.210 10 kg m s = 7.210 10 N

B = 1.00 + 1.00 = 2.00 = 1.4142
Exercise 4.11. A boy is swinging a weight around his 1.00
cos () = = 0.28868
head on a rope. Assume that the weight has a mass of (2.4495)(1.4142)
0.650 kg, that the rope plus the effective length of the boys = arccos (0.28868) = 107 = 1.86 rad
arm has a length of 1.45 m and that the weight makes
a complete circuit in 1.34 s. Find the magnitude of the 11. A spherical object falling in a fluid has three forces
angular momentum, excluding the mass of the rope and that acting on it: (1) The gravitational force, whose
of the boys arm. If the mass is moving counterclockwise magnitude is Fg = mg, where m is the mass of the
in a horizontal circle, what is the direction of the angular object and g is the acceleration due to gravity, equal to
momentum? 9.80 m s2 ; (2) The buoyant force, whose magnitude
is Fb = m f g, where m f is the mass of the displaced
2(1.45 m)
v = = 6.80 m s1 fluid, and whose direction is upward; (3) The frictional
1.34 s force, which is given by Ff = 6 r v, where r
L = mvr = (0.650 kg)(6.80 m s1 ) is the radius of the object, v its velocity, and the
(1.45 m) = 6.41 kg m2 s1 coefficient of viscosity of the fluid. This formula for
CHAPTER | 4 Vectors and Vector Algebra e17

the frictional forces applies only if the flow around The angle between this vector and the negative z axis is
the object is laminar (flow in layers). The object is  
falling at a constant speed in glycerol, which has a 0.240
= arctan = 0.117 = 0.00294 rad
viscosity of 1490 kg m1 s1 . The object has a mass 117.6
of 0.00381 kg, has a radius of 0.00432 m, a mass of
15. According to the Bohr theory of the hydrogen atom,
0.00381 kg, and displaces a mass of fluid equal to
the electron in the atom moves around the nucleus
0.000337 kg. Find the speed of the object. Assume
in one of various circular orbits with radius r = a0 n 2
that the object has attained a steady speed, so that the
where a0 is a distance equal to 0.5291010 m, called
net force vanishes.
the Bohr radius and n is a positive integer. The mass
of the electron is 9.109 1031 kg. According to the
Fz,total = 0 = (0.00381 kg)(9.80 m s2 ) theory, L = nh/2 , where h is Plancks constant,
+ (0.000337 kg)(9.80 m s2 ) equal to 6.626 1034 J s. Find the speed of the
+ 6(1490 kg m1 s1 )(0.00432 m)v electron for n = 1 and for n = 2.
 
(0.00381 kg)(9.80 m s2 )+(0.000337 kg)(9.80 m s2 )
 
v=  Since the orbit is circular, the position vector and the
 6(1490 kg m1 s1 )(0.00432 m) 
velocity are perpendicular to each other, and L = mvr .
= 0.18 m s1
For n = 1:

13. An object of mass 12.000 kg is moving in the x L (6.626 1034 J s)


v = =
direction. It has a gravitational force acting on it equal mr 2(9.109 1031 kg)(0.529 1010 m)
to mgk, where m is the mass of the object and g is = 2.188 106 m s1
the acceleration due to gravity, equal to 9.80 m s1 .
There is a frictional force equal to (0.240 N)i. What For n = 2
is the magnitude and direction of the resultant force
(the vector sum of the forces on the object)? L 2(6.626 1034 Js)
v = =
mr 2(9.109 1031 kg)22 (0.529 1010 m)
Ftotal = (12.000 kg)(9.80 m s1 )k + (0.240 N)i = 1.094 106 m s1
= (117.60 N)k + (0.240 N)i
 Notice that the speed for n = 1 is nearly 1% of the
Ftotal = (117.6 N)2 + (0.240 N)2 = 118 N speed of light.
This page is intentionally left blank
 

Chapter 5
 

Problem Solving and the Solution


of Algebraic Equations

EXERCISES Exercise 5.3. Carry out the algebraic manipulations to


obtain the cubic equation in Eq. (5.9).
Exercise 5.1. Show by substitution that the quadratic
formula provides the roots to a quadratic equation. Ka = x y
For simplicity. we assume that a = 1. Ka
y =
 2   x
b b2 4c b b2 4c
+b +c where we let y = [A ]/c . Since the ionization of water
2 2
and the ionization of the acid both produce hydrogen ions,

b2 b b2 4c b2 4c b2 [HA] c  
= + = xy
4 2 4 4 c c  
Kw
b b2 4c x x
+c =0 x
2 Ka =
c Kw

x+
  c x
Exercise 5.2. For hydrocyanic acid (HCN), K a = 4.9 c Kw
Ka x + = x 2 Kw
1010 at 25 C. Find [H+ ] if 0.1000 mol of hydrocyanic c x
acid is dissolved in enough water to make 1.000 l. Assume
that activity coefficients are equal to unity and neglect Multiply this equation by x and collect the terms:
hydrogen ions from water.

cK a

x 3 + Ka x 2 + K w x Ka Kw = 0
c
K a K a2 + 0.4000K a
x =
2 Exercise 5.4. Solve for the hydrogen ion concentration
 2   in a solution of acetic acid with stoichiometric molarity
4.9 1010 4.9 1010 + (0.4000) 4.9 1010 equal to 0.00100 mol l1 . Use the method of successive
=
2 approximations.
= 7.00 106 or 7.00 106
For the first approximation
[H+ ] = [A ] = 7.00 106 mol l1 .
x 2 = 1.754 105 (0.00100 x)
The neglect of hydrogen ions from water is acceptable, since
(1.754 105 )(0.00100) = 1.754 108
neutral water provides 1 107 mol l1 of hydrogen ions,
and will provide even less in the presence of the acid. x 1.754 108 = 1.324 104
Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00051-3
2013 Elsevier Inc. All rights reserved. e19
e20 Mathematics for Physical Chemistry

For the next approximation Since tan (x) is larger than x in the entire range from x = 0
to x = , we look at the range from x = to x = 2 .
x 2 = 1.754 105 (0.00100 1.324 104 ) By trial and error we find that the root is near 4.49. The
following graph of tan (x) x shows that the root is near
1.754 105 (8.676 104 ) x = 4.491.
1.5217 108
=
x 1.5217 108 = 1.236 104

For the third approximation

x 2 = (1.754 105 )(0.00100 1.236 104 )


(1.754 105 )(8.7664 104 )
1.5376 108
=
x 1.5376 108 = 1.24 104
[H+ ] = 1.24 104 mol l1

Since the second and third approximations yielded nearly Exercise 5.8. Using a graphical procedure, find the most
the same answer, we stop at this point. positive real root of the quartic equation:
Exercise 5.5. Verify the prediction of the ideal gas x 4 4.500x 3 3.800x 2 17.100x + 20.000 = 0
equation of state given in the previous example.

V RT The curve representing this function crosses the x axis in


Vm = = only two places. This indicates that two of the four roots
n
 P  are complex numbers. Chemists are not usually interested
8.3145 J K1 mol1 (298.15 K)
= in complex roots to equations.
1.01325 106 Pa A preliminary graph indicates a root near x = 0.9 and
= 2.447 103 m3 mol1 one near x = 5.5. The following graph indicates that the
root is near x = 5.608. To five significant digits, the correct
Exercise 5.6. Substitute the value of the molar volume answer is x = 5.6079.
obtained in the previous example and the given temperature
into the Dieterici equation of state to calculate the pressure.
Compare the calculated pressure with 10.00 atm =
1.01325 106 Pa, to check the validity of the linearization
approximation used in the example.

Pea/Vm RT (Vm b) = RT
RT ea/Vm RT
P =
(Vm b)

0.468 Pa m6 mol2
ea/Vm RT = exp  
2.30 103 m3 mol1 8.3145 J K1 mol1 298.15 K
2
= e8.20810 = 0.9212
RT e a/V m RT
P =
(Vm b)
  
8.3145 J K1 mol1 298.15 K 0.9212 Exercise 5.9. Use the method of trial and error to find the
=
2.30 10 3 3
m mol 1 4.63 10 5 m mol1
3 two positive roots of the equation
= 1.013328 106 Pa
e x 3.000x = 0
which compares with 1.01325 106 Pa.
to five significant digits. Begin by making a graph of the
Exercise 5.7. Find approximately the smallest positive function to find the approximate locations of the roots.
root of the equation A rough graph indicates a root near x = 0.6 and a root
x = 1.5. By trial and error, values of 0.61906 and 1.5123
tan (x) x = 0. were found.
CHAPTER | 5 Problem Solving and the Solution of Algebraic Equations e21

Exercise 5.10. Use Excel to find the real root of the Use the Find Root statement to find the real root of the same
equation equation.
x 3 + 5.000x 42.00 = 0 The result is
The result is that x = 3.9529. x = 3.00

Exercise 5.11. Write Mathematica expressions for the Exercise 5.15. Solve the simultaneous equations by the
following: method of substitution:
a. The complex conjugate of (10)e2.657i x 2 2x y x = 0
10 Exp[2.635 I] x+y = 0
b. ln (100!) (100 ln (100) 100)
We replace y in the first equation by x:
Log[100!] (100 Log[100] 100]
x 2 + 2x 2 x = 3x 2 x = 0
c. The complex conjugate of (1 + 2i)2.5
(1+2I)2.5 This equation can be factored

Exercise 5.12. In the study of the rate of the chemical x(3x 1) = 0


reaction:
aA + bB products This has the two solutions:

the quotient occurs: 0
1 x= 1

([A]0 ax)([B]0 bx) 3
where [A]0 and [B]0 are the initial concentrations of A The first solution set is
and B, a and b are the stoichiometric coefficients of these
reactants, and x is a variable specifying the extent to which x = 0, y = 0
the reaction has occurred. Write a Mathematica statement
to decompose the denominator into partial fractions. The second solution set is

In[1] : = Clear[x] 1 1
    x= , y=
Apart 1/ A a x B b x 3 3

Exercise 5.13. Verify the real solutions in the preceding Exercise 5.16. Solve the set of equations
example by substituting them into the equation.
3x + 2y = 40
The equation is
2x y = 10
f (x) = x 4 5x 3 + 4x 2 3x + 2 = 0
We multiply the second equation by 2 and add it to the
By calculation first equation
f (0.802307) = 8.3 107
7x = 60
f (4.18885) = 0.000182 60
x =
By trial and error, these roots are correct to the number of 7
significant digits given. We substitute this into the second equation
Exercise 5.14. Use the NSolve statement in Mathematica 120
to find the numerical values of the roots of the equation y = 10
7
x 3 + 5.000x 42.00 = 0 120 50
y = 10 =
7 7
The result is
Substitute these values into the second equation to check

3.00 our work;
x = 1.500 + 3.4278i 120 50 70

= = 10
1.500 3.4278i 7 7 7
e22 Mathematics for Physical Chemistry

Exercise 5.17. Determine whether the set of equations has


x1 + x2 (x1 + x2 )2 4x1 x2
a nontrivial solution, and find the solution if it exists: x =
 2
5x + 12y = 0 x1 + x2 x12 + 2x12 x + x22 4x1 x2
15x + 36y = 0. =
 2
We multiply the first equation by 3, which makes it x1 + x2 x12 2x12 x + x22
identical with the second equation. There is a nontrivial =
solution that gives y as a function of x. From the first 2 
equation x1 + x2 (x1 x2 ) x1 if + is chosen
= =
2 x2 if is chosen
5x
y= = 0.4167x
12 5. The acid ionization constant of chloroacetic acid is
Exercise 5.18. Use Mathematica to solve the simultane- equal to 1.40 103 at 25 C. Assume that activity
ous equations coefficients are equal to unity and find the hydrogen
ion concentration at the following stoichiometric
2x + 3y = 13 molarities.
x 4y = 10
a. 0.100 mol l1
The result is
x2 x2
x = 2 1.40 103 =
0.100 x 0.100
y = 3  3
 1/2
x 1.40 10 (0.100)
= 0.0118
  1/2
PROBLEMS x 1.40 103 0.100 0.0118
= 0.0111
1. Solve the quadratic equations:   1/2
x 1.40 103 (0.100 0.0111)
a. = 0.0112
2
x 3x + 2 = 0 [H ] = 0.011 mol l1
+

(x 2)(x 1) = 0

1 b. 0.0100 mol l1
x=
2
x2 x2
b. 1.40 103 =
0.0100 x 0.0100
x2 1 = 0 x [(1.40 103 )(0.0100)]1/2
(x 1)(x + 1) = 0 = 0.00374
 x [(1.40 103 )(0.0100
1
x= 0.00374)]1/2
1
= 0.00296
c.
x [(1.40 103 )(0.0100
2
x +x +2 = 0 0.00296)]1/2

1 1 8 1 7i = 0.00314
x = =
2 2 2 x [(1.40 103 )(0.0100
= 0.500 1.323i
0.00314)]1/2
3. Rewrite the factored quadratic equation = 0.00310
(x x1 )(x x2 ) = 0 in the form [H ] = 0.0031 mol l1
+

x 2 (x1 + x2 )x + x1 x2 = 0. Apply the quadratic


formula to this version and show that the roots are 7. Make a properly labeled graph of the function y(x) =
x = x1 and x = x2 . ln (x) + cos (x) for values of x from 0 to 2
CHAPTER | 5 Problem Solving and the Solution of Algebraic Equations e23

a. 13. An approximate equation for the ionization of a weak


acid, including consideration of the hydrogen ions
from water is

[H+ ]/co = K a c/co + K w ,
where c is the gross acid concentration. This
equation is based on the assumption that the con-
centration of unionized acid is approximately equal
to the gross acid concentration. Consider a solution
of HCN (hydrocyanic acid) with stoichiometric acid
concentration equal to 1.00 105 mol l1 . K a =
4.0 1010 for HCN. At this temperature, K w =
1.00 1014 .
b. Repeat part a using Mathematica. a. Calculate [H+ ] using this equation.
9. Using a graphical method, find the two positive roots [H+ ]/co
of the following equation.
= (4.0 1010 )(1.00 105 ) + 1.00 1014
e x 3.000x = 0. = 1.18 107 1.2 107

The following graph indicates a root near x = 0. 6 and Roughly 20% greater than the value in pure water.
one near x = 1.5. b. Calculate [H+ ]/co using Eq. (5.9).
 
x 3 + 4.0 1010 x 2
  
1.00 105 4.0 1010 + 1.00
   
1014 x 4.0 1010 1.00 1014 = 0

x 3 + 4.0 1015 x 2
 
1.00 1014 x 4.0 1025 = 0

The solution is


4.0 10
11

x = 9.9980 108


1.0002 107
By trial and error, the roots are at x = 0.61906 and
x = 1.5123 We reject the negative roots and take [H+ ]/co =
11. Write an Excel worksheet that will convert a list of 1.0002 107 , barely more than the value in pure
distance measurements in meters to miles, feet, and water.
inches. If the length in meters is typed into a cell in
15. Solve the cubic equation by trial and error, factoring,
column A, let the corresponding length in miles appear
or by using Mathematica or Excel:
on the same line in column B, the length in feet in
column C, and the length in inches in column C. Here x 3 + x 2 4x 4 = 0
is the result:
This equation can be factored:
' $
(x + 1)(x 2)(x + 2) = 0
meters miles feet inches
The solution is:
1 0.000621371 3.28084 39.37007874

2
2 0.001242742 6.56168 78.74015748
x = 1
5 0.003106855 16.4042 196.8503937

2
10 00.00621371 32.8084 393.7007874
17. Find the root of the equation
100 0.0621371 328.084 3937.007874
& % x 2.00 sin (x) = 0
e24 Mathematics for Physical Chemistry

By trial and error, the solution is 23. The Dieterici equation of state is
x = 1.8955 Pea/Vm RT (Vm b) = RT ,
19. Find the real roots of the equation where P is the pressure, T is the temperature, Vm is
2 the molar volume, and R is the ideal gas constant.
x 2.00 cos (x) = 0
The constant parameters a and b have different
A graph indicates roots near x = 1.4. By trial and values for different gases. For carbon dioxide, a =
error, the roots are 0.468 Pa m6 mol2 , b = 4.63 105 m3 mol1 .
Without linearization, find the molar volume of carbon
x = 1.4546 dioxide if T = 298.15 K and P = 10.000 atm =
21. Solve the simultaneous equations by hand, using the 1.01325 106 Pa. Use Mathematica, Excel, or trial
method of substitution: and error.

x 2 + x + 3y = 15 (1.01325 106 Pa)


3x + 4y = 18 0.468 Pa m6 mol2
exp
Vm (8.3145 J K1 mol1 )(298.15 K)
Use Mathematica to check your result. Since the first
(Vm 4.63 105 m3 mol1 )
equation is a quadratic equation, there will be two
solution sets. = (8.3145 J K1 mol1 )(298.15 K)

18 3x Divide this equation by (1.01325 106 Pa) and


y= ignore the units
4
Substitute this into the first equation

0.468 Pa m6 mol2

exp
18 3x Vm (8.3145 J K1 mol1 )(298.15 K
x2 + x + 3 = 15 (Vm 4.63 105 m3 mol1 )
4

(8.3145J K1 mol1 )(298.15 K)
9 54 =
x2 + 1 x+ = 15 (1.01325 106 Pa)
4 4

0.00018879
exp (Vm 4.63 105 ) 0.00244655 = 0
x 2 1.25x + 13.5 = 15 Vm
x 2 1.25x 1.50 = 0
4x 2 5x 6 = 0 Using trial and error with various values of Vm we seek
a value so that this quantity vanishes. The result was
5 25 + 96
x =
8 Vm = 0.0023001 m3 mol1
5 121
= Compare this with the ideal gas value:
8
5 11 2 RT (8.3145J K1 mol1 )(298.15 K)
x = = 3 Vm = =
8 P (1.01325 106 Pa)
4 = 0.002447 m mol1
3

Check the x = 3/4 value:




25. Solve the set of equations using Mathematica or by
9 3 hand with the method of substitution:
4 5 6=
16 4
x 2 2x y + y 2 = 0
For x = 2
18 6 2x + 3y = 5
y= =3
4 To solve by hand we first solve the quadratic equation
For x = 3/4 for y in terms of x. The equation can be factored into
18 + 9/4 18 + 2.25 two identical factors:
y= = = 5.0625  2
4 4 x 2 2x y + y 2 = x y = 0
Check this
Both roots of the equation are equal:
9 3
+ 3(5.0625) = 15
16 4 y=x
CHAPTER | 5 Problem Solving and the Solution of Algebraic Equations e25

We substitute this into the second equation 10x 4x 2 25 20x 4x 2


x2 + + + =0
3 3 9 9 9
2x + 3y = 5x = 5 25 2 50 25
x x+ =0
x = 1 9 9 9

The final solution is Multiply by 9/25

x = 1 x 2 2x + 1 = 0
y = 1 This equation can be factored to give two identical
factors, leading to two equal roots:
Since the two roots of the quadratic equal were equal
to each other, this is the only solution. (x 1)2 = 0
Alternate solution: Solve the second equation for y
x = 1
5 2x
y= This gives
3

2 5 2x 5 2x 2 2 + 3y = 5
x 2x + =0
3 3 3 y = 1
This page is intentionally left blank
 

Chapter 6
 

Differential Calculus

EXERCISES c.
y = tan (x)
Exercise 6.1. Using graph paper plot the curve represent-
ing y = sin (x) for values of x lying between 0 and /2 This function is differentiable except at x = /2, 3/2,
radians. Using a ruler, draw the tangent line at x = /4. 5/2, . . .
By drawing a right triangle on your graph and measuring
its sides, find the slope of the tangent line. Exercise 6.3. The exponential function can be represented
by the following power series
Your graph should look like this:
1 2 2 1 1
ebx = 1 + bx + b x + b3 x 3 + + bn x n
2! 3! n!
where the ellipsis ( ) indicates that additional terms
follow. The notation n! stands for n factorial, which is
defined to equal n(n 1)(n 2) (3)(2)(1) for any
positive integral value of n and to equal 1 for n = 0. Derive
the expression for the derivative of ebx from this series.
 
d 1 1 1
1 + bx + b2 x 2 + b3 x 3 + + bn x n
dx 2! 3! n!
     
1 2 1 3 1 n n1
=b+2 b x +3 b x2 + + n b x
2! 3! n!
 
2 1 1 1
The slope of the tangent line should be equal to 2 = = b 1 + bx + b2 x 2 + b3 x 3 + + bn x n
2! 3! n!
0.70717
= bebx
Exercise 6.2. Decide where the following functions are
differentiable. Exercise 6.4. Draw rough graphs of several functions from
a. Table 6.1. Below each graph, on the same sheet of paper,
1 make a rough graph of the derivative of the same function.
y=
1x
Solution not given here.
This function has an infinite discontinuity at x = 1 and
is not differentiable at that point. It is differentiable Exercise 6.5. Assume that y = 3.00x 2 4.00x + 10.00.
everywhere else. If x = 4.000 and x = 0.500, Find the value of y using
b. Eq. (6.2). Find the correct value of y
y = x +2 x  
This function has a term, dy
x, that is differentiable y x = (6.00x 4.00)(0.500)
everywhere, and a term 2 x, that is differentiable only dx
for x 0. (24.00 4.00)(0.500) = 10.00
Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00052-5
2013 Elsevier Inc. All rights reserved. e27
e28 Mathematics for Physical Chemistry

Now we compute the correct value of y: f (0.208696) = 0.043554 (5.000)(0.208696)


y(4.500) = (3.00)(4.5002 ) (4.00)(4.500) + 10.00 + 1.000 = 0.000074
(1)
= 52.75 f (0.208696) = 2(0.208696) 5.000 = 4.58261
2
y(4.000) = (3.00)(4.000 ) (4.00)(4.000) + 10.00 0.000074
x2 = 0.208696 + = 0.20871
= 42.00 4.58261
y = y(4.500) y(4.00) = 52.75 42.00 We discontinue iteration at the point, since the second
approximation does not differ significantly from the first
= 10.75
approximation. This is the correct value of the root to five
Our approximation was wrong by about 7.5%. significant digits.

Exercise 6.6. Find the following derivatives. All letters Exercise 6.8. Find the second and third derivatives of
stand for constants except for the dependent and the following functions. Treat all symbols except for the
independent variables indicated. specified independent variable as constants.

dy a. y = y(x) = ax n
a. , where y = (ax 2 + bx + c)3/2
dx dy
  = anx n1
d 2 3/2 3 2ax + b dx
(ax +bx+c) =
dx 2 (ax 2 + bx + c)5/2 d2 y
= an(n 1)x n2
dx 2
d ln (P)
b. , where P = keQ/T d3 y
dT = an(n 1)(n 2)x n3
dx 3
Q
ln (P) = ln (k) b. y = y(x) = aebx
T
d ln (P) d(Q/T ) Q dy
= = 2 = abebx
dT dT T dx
dy d2 y
c. , where y = a cos (bx 3 ) = ab2 ebx a
dx dx 2
d3 y
d = ab3 ebx
a cos (bx 3 ) = a sin (bx 3 )(3bx 2 ) dx 3
dx
= 3abx 2 sin (bx 3 ) Exercise 6.9. Find the curvature of the function y =
cos (x) at x = 0 and at x = /2.
Exercise 6.7. Carry out Newtons method by hand to find
the smallest positive root of the equation dy
= sin (x)
dx
1.000x 2 5.000x + 1.000 = 0 d2 y
df = cos (x)
= 2.000x 5.000 dx 2
dx
d2 y/dx 2 cos (x)
A graph indicates a root near x = 0.200. we take x0 = K =  2 3/2 =  3/2
0.2000. dy 1 + ( sin (x))2
f (x0 ) 1+
x1 = x0 (1) dx
f (x0 )
at x = 0
1
f (0.2000) = 0.04000 (5.000)(0.200) + 1.000 K = = 1
13/2
= 0.04000
at x = /2.
(1)
f (0.2000) = (2.000)(0.2000) 5.000 = 4.600 0
K = =0
0.04000 23/2
x1 = 0.2000 = 0.2000+0.008696 = 0.208696
4.600 Exercise 6.10. For the interval 10 < x < 10, find the
maximum and minimum values of
f (x1 )
x2 = x1 (1)
f (x1 ) y = 1.000x 3 + 3.000x 2 3.000x + 8.000
CHAPTER | 6 Differential Calculus e29

We take the first derivative: Exercise 6.14. Investigate the limit


dy lim (x n e x )
= 3.000x 2 + 6.000x 3.000 x
dx
= 3.000(x 2 2.000x + 1.000) for any finite value of n.
= 3.000(x 1.000) = 0 if x = 1 2  x  x 
e e
lim (x n e x ) = lim n
= lim
x x x x nx n1
We test the second derivative to see if we have a relative
maximum, a relative minimum, or an inflection point: Additional applications of lHpitals rule give decreasing
powers of x in the denominator times n(n 1)(n 2) ,
d2 y until we reach a denominator equal to the derivative of a
= 6.000x + 6.000 constant, which is equal to zero. The limit does not exist.
dx 2
= 0 if x = 1.000
Exercise 6.15. Find the limit
The point x = 1.000 is an inflection point. The possible 
ln (x)
maximum and minimum values are at the ends of the lim .
x x
interval
We apply lHpitals rule.
ymax = y(10.000) = 1538  
ln (x) 1/x
ymin = y(10.000) = 522 lim = lim
x x x x 1/2
 1/2 
The maximum is at x = 10 and the minimum is at x = 10. x 1
= lim = lim =0
x x x x
Exercise 6.11. Find the inflection points for the function
y = sin (x). The inflection points occur at points where the Exercise 6.16. Find the limit
second derivative vanishes.  
N h
lim
dy e h/kB T 1
= cos (x)
dx We apply Hpitals rule
d2 y  
= sin (x) N h
dx 2 lim
e h/kB T 1
d2 y

= 0 when x = 0, , 2, 3, . . .  
dx 2 Nh N kB T
= lim lim =0
h h/kB T e h/kB T
Exercise 6.12. Decide which of the following limits exist kB T e
and find the values of those that do exist. Notice that this is the same as the limit taken as T 0.

a. lim x/2 [x tan (x)] This limit does not exist, since
tan (x) diverges at x = /2. PROBLEMS
b. lim x0 [ln (x)]. This limit does not exist, since ln (x)
diverges at x = 0. 1. The sine and cosine functions are represented by the
two series
Exercise 6.13. Find the value of the limit: x3 x5 x7
sin (x) = x + +
 3! 5! 7!
tan (x)
lim x2 x4 x6
x0 x cos (x) = 1 + +
2! 4! 6!
We apply lHpitals rule. Differentiate each series to show that
   2 d sin (x)
tan (x) d tan (x)dx sec (x) = cos (x)
lim = lim = lim dx
x0 x x0 dx/dx x0 1
 and
1 d cos (x)
= lim =1 = sin (x)
x0 cos2 (x) dx
e30 Mathematics for Physical Chemistry

The derivative of the first series is c. y = y(x) = a ln (x 1/3 )


d sin (x) 2x 2 5x 4 yx 6   
= 1 + + dy a 1 a
dx 3! 5! 7! = 1/3 x 2/3 =
dx x 3 3x
x2 x4 x6
= 1 + +
2! 4! 6! 7. Find the first and second derivatives of the following
The derivative of the second series is functions.
  
d cos (x) 2x 4x 3 6x 5 1 1
= + + a. y =
dx 2! 4! 6! x 1+x
 
x2 x4 x6      
= 1 + + . dy 1 1 1 1
2! 4! 6! =
dx x2 1+x x (1 + x)2
     
3. Use the definition of the derivative to derive the 1 1 1 1
formula = 2 +
x3 1+x x2 (1 + x)2
d(yz) dz dy      
=y +z 1 1 1 1
dx dx dx + + 2
x2 (1 + x)2 x (1 + x)3
where y and z are both functions of x.   
1 1
= 2
d(yz) y(x2 )z(x2 ) y(x1 )z(x1 ) x3 1+x
= lim      
dx x2 x1 x2 x1 1 1 1 1
+2 + 2
x2 (1 + x)2 x (1 + x)3
Work backwards from the desired result:
2 /(2kT )
dz dy z(x2 ) z(x1 ) b. f = f (v) = cemv where m, c, k, and T
y +z = lim y are constants
dx dx x 2 x 1 x2 x1
y(x2 ) y(x1 ) 

+ lim z df 2 2mv
x2 x1 x2 x1 = cemv /(2kT )
dv 2kT
y(x2 )z(x2 ) y(x2 )z(x1 )  
= lim mv 2 /(2kT ) mv
x2 x1 x2 x1 = ce
kT
y(x2 )z(x1 ) y(x1 )z(x1 )  mv 2
+ lim z d2 f 2
x2 x1 x2 x1 = cemv /(2kT )
dv 2 kT
 
Two terms cancel: mv 2 /(2kT ) m
ce
kT
dz dy y(x2 )z(x2 ) y(x1 )z(x1 )
y +z = lim
dx dx x2 x1 x2 x1 9. Find the second and third derivatives of the following
functions. Treat all symbols except for the specified
5. Find the first and second derivatives of the following independent variable as constants.
functions

a. P = P(Vm ) = RT 1/Vm + B/Vm2 + C/Vm3 a. vrms = vrms (T ) = 3RT
M
where R, B, and C are constants
    
dP dvrms 1 3RT 1/2
= RT 1/Vm2 2B/Vm3 3C/Vm4 =
dVm dT 2 M
     
d2 P d2 vrms 1 1 3RT 3/2
2
= RT 2/Vm3 + 6B/Vm4 + 12C/Vm5 =
dVm dT 2 2 2 M
  3/2
b. G = G(x) = G + RT x ln (x) + RT (1 x) ln 1 3RT
=
(1 x), where G , R, and T are constants 4 M
   
dG d3 vrms 1 3 3RT 5/2
= RT [1 + ln (x)] + RT [1 ln (1 x)] =
dx dT 3 4 2 M
    5/2
d2 G 1 1 3 3RT
= RT + RT =
dx 2 x 1x 8 M
CHAPTER | 6 Differential Calculus e31

n RT an 2 15. Draw a rough graph of the function


b. P = P(V ) = 2
(V nb) V
y = y(x) = e|x|
dP n RT an 2
= + 2
dV (V nb)2 V3
Your graph of the function should look like this:
d2 P n RT an 2
2
= 2 3
6 4
dV (V nb) V
3
d P n RT an 2
3
= 6 4
+ 24 5
dV (V nb) V

11. Find the following derivatives and evaluate them at the


points indicated.

a. (dy/dx)x=1 , if y = (ax 3 + bx 2 + cx + 1)1/2 ,


where a, b, and c are constants
 
dy 1
= (ax 3 + bx 2 + cx + 1)3/2
dx 2
Is the function differentiable at x = 0? Draw a rough
(3ax 2 + 2bx + c)
    graph of the derivative of the function.
dy 1
= (a + b + c + 1)3/2
dx x=1 2 
(3a + 2b + c) dy ex if x  0
=
dx ex if x  0
b. (d2 y/dx 2 )x=0 , if y = aebx , where a and b are
constants.
The function is not differentiable at x = 0. Your graph
dy of the derivative should look like this:
= abebx
dx
d2 y
= ab2 ebx
dx 2
 2 
d y
= ab2
dx 2 x=0

13. Find a formula for the curvature of the function

n RT an 2
P(V ) = 2.
V nb V

where n, R, a, b, and T are constants


17. Draw a rough graph of the function
d2 y/dx 2
K =
[1 + (dy/dx)2 ]3/2
dP n RT an 2 y = y(x) = cos (|x|)
= + 2
dV (V nb)2 V3
2
d P n RT an 2 Is the function differentiable at x = 0? Since the
= 2 6 cosine function is an even function
dV 2 (V nb)3 V4
n RT an 2
2 3
6 4 cos (|x|) = cos (x)
(V nb) V
K =   2 3/2
n RT an 2
1+ +2 3 The function is differentiable at all points. Draw a
(V nb)2 V
rough graph of the derivative of the function, your
e32 Mathematics for Physical Chemistry

graph of the function should look like a graph of the endpoints of the interval:
cosine function:
G m (0) = G m + RT lim [x ln (x)]
x0

Apply lHpitals rule


ln (x) 1/x
lim 1
= lim = lim (x) = 0
x0 x x0 1/x 2 x0

The same value occurs at x = 1, since 1 x plays


the same role in the function as does x. The maximum
value of the function is

G m (0) = G m (1) = G m

23. The sum of two nonnegative numbers is 100. Find their


19. Show that the function (x) = cos (kx) satisfies the values if their product plus twice the square of the first
equation is to be a maximum. We denote the first number by x
d2 and let
= k 2
dx 2 f = x(100 x) + 2x 2
if A and k are constants. df
= 100 2x + 4x = 100 + 2x
d dx
= k sin (kx)
dx At an extremum
d2
= k 2 cos (kx) = k 2 0 = 100 + 2x
dx 2
21. The mean molar Gibbs energy of a mixture of two This corresponds to x = 50. Since we specified that
enantiomorphs (optical isomers of the same substance) the numbers are nonzero, we inspect the ends of the
is given at a constant temperature T by region.

G m = G m (x) f (0) = 0
= G m + RT x ln (x) + RT (1 x) ln (1 x) f (100) = 20000

where x is the mole fraction of one of them. G m is The maximum corresponds to x = 100.
a constant, R is the ideal gas constant, and T is the 25. Find the following limits.
constant temperature. What is the concentration of
each enantiomorph when G has its minimum value? a. lim x [ln (x)/x 2 ] Apply lHpitals rule:
What is the maximum value of G in the interval 
2 1/x
0  x  1? lim [ln (x)/x ] = lim =0
x x 2x
dG m
= RT [1 + ln (x)] + RT [1 ln (1 x)] b. lim x3 [(x 3 27)/(x 2 9)] Apply lHpitals
dx rule:
This derivative vanishes when  3  2
(x 27) 3x
lim = lim
1 + ln (x) 1 ln (1 x) = 0 x3 (x 2 9) x3 2x

ln (x) ln (1 x) = 0 3x 9
  = lim =
x x3 2 2
ln = 0   
1x 1
x c. lim x x ln
= 1 1+x
1x
= 1x  
x    1
ln 1+x
1 1
x = lim x ln = lim
2 x 1+x x 1/x

The minimum occurs at x = 1/2. There is no ln (1 + x)
relative maximum. To find the maximum, consider the = lim
x 1/x
CHAPTER | 6 Differential Calculus e33

Apply lHpitals rule: At the relative extremum


 
ln (1 + x) 1/(1 + x) r = 4a0
lim = lim
x 1/x x 1/x 2
 2 This is a relative minimum, since the function is
x negative at this point. The function approaches
= lim
x 1 + x zero as r becomes large, so the maximum is
This diverges and the limit does not exist. at r = 0.
b. Draw a rough graph of 2s . For a rough graph,
27. Find the following limits we omit the constant factor and let r /a0 = u. We
graph the function
2
a. lim x (ex /ex ).

f = (2 u)eu/2
2
ex 2
lim x
= lim (ex +x ) = 0 your graph should look like this:
x e x

b. lim x0 [x 2 /(1cos (2x))]. Apply lHpitals rule


twice:
 
x2
lim
x0 1 cos (2x)
 
2x 2 1
= lim = lim =
x0 2 sin (2x) x0 4 cos (2x) 2

c. lim x [sin (x)/ sin (3x/2)]. Apply lHpitals


rule
 
sin (x) cos (x) 2
lim lim = 2 .
c. Locate the maxima and minima of 2s
x sin (3x/2) x 3 cos 3x)/2 3
    
29. If a hydrogen atom is in a 2s state, the probability of 2 = 1 1 1 3 r 2 r /a0
2s 2 e ,
finding the electron at a distance r from the nucleus 4 2 32 a0 a0
2 where represents the
is proportional to 4r 2 2s
orbital (wave function): To locate the extrema, we omit the constant factor
  
 3/2   d r 2 r /a0
1 1 r 2
2s = 2 er /2a0 , dr a0
e
4 2 a0 a0


where a0 is a constant known as the Bohr radius, equal d 4r r2 r /a0
= 4 + 2 e
to 0.529 1010 m. dr a0 a0


a. Locate the maxima and minima of 2s . To find the 4 2r
= + 2 er /a0
extrema, we omit the constant factor: a0 a0

 
  r2
d 4r r /a0 1
2
r
er /2a0 + 4 + 2 e =0
dr a0 a0 a0 a0
     
1 r /2a0 r 1
= e + 2 er /2a0 =0 Cancel the exponential term:
a0 a0 2a0


4 2r 4 4r r2
We cancel the exponential factor, which is the + 2 2+ 3 = 0
same in all terms: a0 a0 a0 a0 a0
     4 2r 4 4r r2
1 r 1 + 2 + 2 3 = 0
+ 2 = 0 a0 a0 a0 a0 a0
a0 a0 2a0
2 r 8 6r r2
+ 2 = 0 + 2 3 = 0
a0 2a0 a0 a0 a0
e34 Mathematics for Physical Chemistry

Let u = r /a0: and multiply by a0 One root is u = 0. The roots from the cubic factor
are
u 2 6u + 8 = (x 2)(x 4) = 0
0.763 93
u= 2
The relative extrema occur at x = 3 and x = 4.

The first is a relative minimum, where f = 0, 5. 236 1
and the second is a relative maximum. The two minima are at r = 0 and at r = 2a0 , and
d. Draw a rough graph of 2s 2 . For a rough graph, the maximum is at r = 5. 236 1a0
2 . For our rough
f. Draw a rough graph of 4r 2 2s
we plot
f (u) = (2 u)2 eu graph, we plot

f = (2u u 2 )2 eu

2 .
e. Locate the maxima and minima of 4r 2 2s
  3  
4 1 1 r 2 r /a0
4r 2 2s
2 = r2 2 e
4 232 a0 a0 31. According to the Planck theory of black-body
 3

1 1 r2
2 radiation, the radiant spectral emittance is given by
= 2r er /a0 the formula
32 2 a0 a0
2 hc2
To locate the relative extrema, we omit the = () = ,
5 (ehc/kB T 1)
constant factor
 2 where is the wavelength of the radiation, h is Plancks
df d r2 constant, kB is Boltzmanns constant, c is the speed of
= 2r er /a0
dr dr a0 light, and T is the temperature on the Kelvin scale.
   Treat T as a constant and find an equation that gives
r2 2r
= 2 2r 2 er /a0 the wavelength of maximum emittance.
a0 a0
 2   
r2 1 d 5
+ 2r er /a0 =0 = (2 hc2 ) 6 hc/k T
a0 a0 d (e B 1)
 
1 hc
We cancel the exponential factor 5 hc/k T e hc/kB T
(e B 1)2 2 k B T
    2  
2r 2 2r r2 1 At the maximum, this derivative vanishes. We place
4r 2 2r = 0 both terms in the square brackets over a common
a0 a0 a0 a0


denominator and set this factor equal to zero.
12r 2 4r 3 4r 2 4r 3 r4
8r + 2 2 + 3 = 0 5(ehc/kB T 1) + ehc/kT (hc/kB T )
a0 a0 a0 a0 a0 =0
6 (ehc/kB T 1)2
Divide by a0 , replace r /a0 by u and collect terms:
We set the numerator equal to zero
2 3 4
8u 16u + 8u u = 0 5(ehc/kT 1) + ehc/kB T (hc/kB T ) = 0
We multiply by 1 We let x = hc/kB T so that

u(8 + 16u 8u 2 + u 3 ) = 0 5(e x 1) + e x x = 0


CHAPTER | 6 Differential Calculus e35

We divide by e x Solve Eq. (6.1) for Tc :


x
5(1 e )+x =0 2n 2 a(Vc nb)2
Tc = (6.3)
This equation is solved numerically to give x = 4.965 n RVc3
hc hc Substitute this expression into Eq. (6.2):
max = =
kB T x 4.965kB T   2 
2n R 2n a(V nb)2 6n 2 a
33. Draw a rough graph of the function 0 = +
(V nb)3 n RV 3 V4
tan (x) 4n 2 a 6n 2 a
y= 0 = +
x (V nb) V
in the interval < x < . Use lHpitals rule to 2 3
evaluate the function at x = 0. Here is an accurate 0 = + when V = Vc
(V nb) V
graph. The function diverges at x = /2 and x = Vc = 3nb
/2 so we plot only from 1.5 to 1.5. At x = 0
Substitute this into Eq. (6.3)
tan (x) sec2 (x) sec2 (0)
lim = lim = =1
x0 x x0 1 1 2n 2 a(2nb)2 8a
Tc = 3 3
=
n R(27n b ) 27Rb

n RTc n2a 8n Ra n2a


Pc = 2 = 2 2
Vc nb Vc 27Rb(2nb) 9n b
4a a a
= 2 =
27b2 9b 27b2
37. Solve the following equations by hand, using
Newtons method. Verify your results using Excel or
Mathematica:

a. ex 0.3000x = 0. A rough graph indicates a


root near x = 1. We take x0 = 1.000
35. The van der Waals equation of state is
  f = ex 0.3000x
n2a
P + 2 (V nb) = n RT f = ex 0.3000
V
f (x0 )
When the temperature of a given gas is equal to x1 = x0
its critical temperature, the gas has a state at which f (x0 )
the pressure as a function of V at constant T and n f (1.000) = e1.000 0.3000 = 0.06788
exhibits an inflection point at which dP/dV = 0 and f (1.000) = e1.000 0.3000 = 1.205
d2 P/dV 2 = 0. This inflection point corresponds to the 0.06788
critical point of the gas. Write P as a function of T, V, x1 = 1.000
1.205
and nand write expressions for dP/dV and d2 P/dV 2 , = 1.000 + 0.0563 = 1.0563
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 (1.0563) = e1.0563 (0.3000)(1.0563)
n RT n2a
P = 2 = 0.3477 0.3169 = 0.03082
V nb V
f (1.0563) = e1.0563 (0.3000)(1.0563)

dP n RT 2n 2 a
= 2
+ = 0.3477 0.3169 = 0.6646
dV (V nb) V3
0.03082
= 0 at the critical point (6.1) x2 = 1.0563
2
0.6646
d P 2n RT 6n 2 a = 1.0563 + 0.0464 = 1.10271
= +
dV 2 (V nb)3 V4 f (x2 )
= 0 at the critical point (6.2) x3 = x2
f (x2 )
e36 Mathematics for Physical Chemistry

f (1.10271) = e1.10271 (0.3000)(1.10271) cos (x) sin (x)


f (1.25) =
= 0.33197 0.33081 = 0.001155 x x2
= 0.25226 0.60735 = 0.35509
f (1.10271) = e1.0563 (0.3000)(1.0563) 0.009188
x1 = 1.25
= 0.33197 0.33081 = 0.66278 0.35509
= 1.25 + 0.02587 = 1.2759
0.001155
x3 = 1.10271 = 1.1045 f (x1 )
0.66278 x2 = x1
f (x1 )
To five significant digits, this is the correct answer. sin (1.2759)
f (1.2759) = 0.7500
b. sin (x)/x 0.7500 = 0. A graph indicates a root 1.2759
= 0.00006335
near x = 1.25. We take x0 = 1.25.
cos (x) sin (x)
f (1.2759) =
sin (x)/x 0.7500 x x2
cos (x) sin (x) = 0.2278 0.58878 = 0.35997
f = 0.00006335
x x2 x1 = 1.2759
0.35997
f (x0 )
x1 = x0 = 1.2759 0.000259 = 1.2756
f (x0 )
sin (1.25) We stop iterating at this point. The correct answer
f (1.25) = 0.7500 = 0.009188 to five significant digits is x = 1.2757
1.25
 

Chapter 7
 

Integral Calculus

EXERCISES integral is
Exercise 7.1. Find the maximum height for the particle in  1
the preceding example. e x dx = e x |10 = e1 e0 = 2.71828 1
We find the time of the maximum height by setting the 0
first derivative of z(t) equal to zero: = 1.71828

dz
= 0.00 m s1 = 10.00 m s1 (9.80 m s2 )t = 0 Exercise 7.4. Find the area bounded by the curve
dt
representing y = x 3 , the positive x axis, and the line
The time at which the maximum height is reached is x = 3.000.
10.00 m s1  
t= = 1.020 s 3.000 1 2 3.000 1
9.80 m s2 area = x 3 dx = x  = (9.000 0.000)
0.000 2 0.000 2
The position at this time is

(9.80 m s2 )(1.020 s)2 = 4.500


z(t) = (10.00 m s1 )(1.020 s)
2
= 5.204 m Exercise 7.5. Find the approximate value of the integral

Exercise 7.2. Find the function whose derivative is  1


(10.00)e5.00x and whose value at x = 0.00 is 10.00. 2
ex dx
The antiderivative of the given function is 0

F(x) = (2.00)e5.00x + C by making a graph of the integrand function and measuring


an area.
where C is a constant.
We do not display the graph, but the correct value of the
F(0.00) = 10.00 = (2.00)e0.00 + C integral is 0.74682.
C = 10.00 2.00 = 8.00
F(x) = (2.00)e5.00x + 8.00 Exercise 7.6. Draw a rough graph of f (x) = xex and
2

satisfy yourself that this is an odd function. Identify the


Exercise 7.3. Evaluate the definite integral area in this graph that is equal to the following integral and
 1 satisfy yourself that the integral vanishes:
e x dx.
0  4 2
The antiderivative function is F = ex so that the definite xex dx = 0.
4
Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00053-7
2013 Elsevier Inc. All rights reserved. e37
e38 Mathematics for Physical Chemistry

Here is a graph for 2 :


The area to the right of the origin is positive, and the area
to the left of the origin is negative, and the two areas have
the same magnitude.

2
Exercise 7.7. Draw a rough graph of f (x) = ex . Satisfy
yourself that this is an even function. Identify the area in
the graph that is equal to the definite integral

 3 2
I1 = ex dx
3

and satisfy yourself that this integral is equal to twice the


integral b. Draw a rough graph of the product 1 2 and satisfy
 3 yourself that the integral of this product from x = 0
I2 =
2
ex dx. to x = a vanishes. Here is graph of the two functions
0 and their product:

Here is the graph. The area to the left of the origin is


equal to the area to the right of the origin. The value of the
integrals areI1 = 1.4936 and I2 = 0.7468.

Exercise 7.9. Using a table of indefinite integrals, find the


definite integral.
 3.000
cosh (2x)dx
0.000
Exercise 7.8. a. By drawing rough graphs, satisfy
 3.000  6.000
yourself that 1 is even about the center of the box. 1
That is, 1 (x) = 1 (a x). Satisfy yourself that 2 cosh (2x)dx = cosh (y)dy
0.000 2 0.000
is odd about the center of box. 6.000
1  1
For the purpose of the graphs, we let a = 1. Here = sinh (y) = [sinh (6.000) sinh (0.000)]
is a graph for 1 2 0.000 2
CHAPTER | 7 Integral Calculus e39

 
1 1
= sinh (6.000) = [e6.000 e6.000 ] = 100.8 x cos (x)dx = x sin (x)|0 sin (x)dx
2 4 0 0
= 0 + cos (x)|0 = 2
Exercise 7.10. Determine whether each of the following
improper integrals converges, and if so, determine its value: 
 1 1 x 2 sin (x)dx = x 2 cos (x)|0 + 2 ( 2)
a. dx 0
0 x
= 2 4
 1 1
dx = lim ln (x)|1b = 0 + Exercise 7.13. Solve the simultaneous equations to obtain
0 x b0 the result of the previous example.
This integral diverges since the integrand tends strongly A1 + A2 = 6
toward infinity as x approaches x = 0. A1 + 2 A2 = 30
 1

b. 0 1+x dx
Subtract the first equation from the second equation:
  1

A2 = 36
dx = lim ln (1 + x)|b0 =
0 1+x b Substitute this into the first equation
This integral diverges since the integrand approaches A1 36 = 6
zero too slowly as x becomes large. A1 = 42

Exercise 7.11. Evaluate the integral


Exercise 7.14. Use Mathematica to verify the partial
 /2 fractions in the above example.
esin ( ) cos ( )d
0 Solution not given.
without using a table of integrals. We let
Exercise 7.15. Show that the expressions for G and H
y = sin ( ) are correct. Verify your result using Mathematica if it is
dy = cos ( )d available. Substitute the expressions for G and H into the
equation
 /2  =/2  y=1
1
esin ( ) cos ( )d = e y dy = e y dy
0 0 0 ([A]0 ax)([B]0 bx)
  
= e y |10 = e 1 = 1.7183 1 1
=
[A]0 ax [B]0 b[A]0 /a
Exercise 7.12. Evaluate the integral   
1 1
 + .
[B]0 bx [A]0 a[B]0 /b
x 2 sin (x)dx    
1 ([B]0 bx) a
0 =
[A]0 ax [B]0 bx a[B]0 b[A]0
without using a table. You will have to apply partial    
[A]0 ax 1 b
integration twice. For the first integration, we let u(x) = x 2 + .
and sin (x)dx = dv [B]0 bx [A]0 ax b[A]0 a[B]0
   
1 ([B]0 bx) a
=
du = 2x dx [A]0 ax [B]0 bx a[B]0 b[A]0
   
v = cos (x) [A]0 ax 1 b
 
[B]0 bx [A]0 ax (a[B]0 b[A]0 )
x sin (x)dx = x 2 cos (x)|0 + 2
2
x cos (x)dx
0 0 a([B]0 bx) b([A]0 ax)
=
([B]0 bx)([A]0 ax)(a[B]0 b[A]0 )
For the second integration, we let u(x) = x and
cos (x)dx = dv a[B]0 abx b[A]0 + abx
=
([B]0 bx)([A]0 ax)(a[B]0 b[A]0 )
du = dx 1
=
v = sin (x) ([B]0 bx)([A]0 ax)
e40 Mathematics for Physical Chemistry


Exercise 7.16. Using the trapezoidal approximation, eval- a. cos3 (x)dx
 2 5x 2
uate the following integral, using five panels. b. 1 e dx
 2.00
The correct values are
cosh (x)dx
1.00
a. 
We apply the definition of the hyperbolic cosine 3 1
cos3 (x)dx = sin x + sin 3x
4 12
1 x
cosh (x) = (e + ex ) b. 
2 2 2
e5x dx = 2.4917 107
1
 2.00 
e1.00
e x dx + e1.20 + e1.400
1.00 2
 PROBLEMS
e2.00
+e1.600 + e1.800 + 1. Find the indefinite integral without using a table:
2
(0.200) = 4.686 
 2.00  1.00 a. x ln (x)dx
e
ex dx + e1.20 + e1.400
1.00 2 u(x) = x

e2.00 du/dx = 1
+e1.600 + e1.800 +
2 ln (x) = dv/dx
(0.200) = 0.2333 v = x ln (x) x

 2.00 4.6866 + 0.2333 x ln (x)dx = x(x ln (x) x)
cosh (x)dx = 2.460
1.00 2 
The correct value is 2.4517 (x ln (x) x)dx + C
 
Exercise 7.17. Apply Simpsons rule to the integral 2 x ln (x)dx = x(x ln (x) x) + x dx + C
 20.00
x2
x 2 dx = x 2 ln (x) x 2 +
10.00 2
x2
using two panels. Since the integrand curve is a parabola, = x 2 ln (x)
your result should be exactly correct. 2
  
1 x2
 20.00 x ln (x)dx = x 2 ln (x)
( f 0 + 4 f 1 + f n )x 2 4
x 2 dx
10.00 3 
1 b. x sin2 (x)dx
= (10.00 + 4(15.00)2 + 20.002 )(5.00) = 2333.3
2
 
3 1
x sin2 (x)dx = x[1 cos (2x)]dx
This is correct to five significant digits. 2
 
1 1
Exercise 7.18. Using Simpsons rule, calculate the integral = x dx x cos (2x)dx
2 2
from x = 0.00 to x = 1.20 for the following values of the 
1
integrand. x cos (2x)dx = x sin (2x)
2
x 0.00 0.20 0.40 0.60 0.80 1.00 1.20 
1
f (x) 1.000 1.041 1.174 1.433 1.896 2.718 4.220 sin (2x)dx
2
 1.20 1 1
1 = x sin (2x) + sin (2x)
[1.000 + 4(1.041) + 2(1.174 + 4(1.433)
f (x)dx 2 4
0.00 3 
2 1 2 1
+2(1.896) + 4(2.718) + 4.200)](0.20) 2.142 x sin (x)dx = x x sin (2x)
4 4
Exercise 7.19. Write Mathematica entries to obtain the 1
cos (2x)
following integrals: 8
CHAPTER | 7 Integral Calculus e41

3. Evaluate the definite integrals, using a table of y = 2x + 3, the x axis, the line x = 1, and the line
indefinite integrals x = 4.
 2.000  4
ln (3x)
a. 1.000 x dx area = (2x + 3)dx = (x 2 + 3x)|41
1
 2 = 16 + 12 1 3 = 24
2.00 ln (3x) 1 
2
dx = [ln (3x)] 
1.00 x 2 1 13. Determine whether each of the following improper
1 integrals converges, and if so, determine its value:
= {[ln (6.000)]2 [ln (3.000)]}2 = 1.0017
2
 1
 5.000 a. 0 x3
dx
b. 0.000 4x dx.
 
 5.000
1 1 
5.000  4x dx = 2  = 0 + (diverges)
4 dx =
x  0 x3 2x 0
0.000 ln (4) 0.000
0
1 5.000

b. x dx
= 4 40.000 e
ln (4)
 0
1
= (1024.0 1.000) e x dx = e x |0 = 1 (converges)
1.38629
= 737.9
4 15. Determine whether the following improper integrals
5. Evaluate the definite integral: 2 x ln1(x) dx converge. Evaluate the convergent integrals
1 1
 4 a. 0 dx =
1 xln (x)

dx = ln ( ln (|(x)|)|42 = ln ( ln (4)))  1
2 x ln (x) b. 1 dx =
ln ( ln 2)) x
= ln (1.38629) ln (0.69315)
17. Determine whether the following improper integrals
= 0.32663 + 0.36651 = 0.69314 converge. Evaluate the convergent integrals.
 10 
7. Evaluate the definite integral: 1 x ln (x)dx a. 0 sin (x)dx diverges, The integrand continues to
 10 oscillate
 /2 as x increases,
 10 x2 x 2  b. /2 tan (x)dx
x ln (x)dx = ln (x)
1 2 4 1  u
100 1
/2 
= 50 ln (10) + tan (x)dx = lim ln (| cos (u)|)
4 4 /2 u/2 u
99 = lim [ln ( cos (u)) ln ( cos (u))] = 0
= 50 ln (10) = 90.38 u/2
4
 /2 Since the cosine is an even function, the two terms
9. Evaluate the definite integral: x sin (x 2 )
 0 are canceled before taking the limit, so that the
dx = 21 21 cos 41 2 . x sin (x 2 )dx = 21 cos x 2 . result vanishes.
 /2  2
2 1 /4 19. Using Simpsons rule, evaluate erf(2):
x sin (x )dx = sin (u)du
0 2 0  2.000
 2 /4 2 2
1  erf(2) = et dt
= cos (u) 0
2 0
1 2 1 1 1 Compare your answer with the correct value from a
= cos ( /4) + = ( 0.78121) + more extended table than the table in Appendix G,
2 2 2 2
= 0.89061 er f (2.000) = 0.995322265. With x = 0.0500, the
result from Simpsons rule was 0.997100808. With
11. Find the following area by computing the values of a x = 0.100, the result from Simpsons rule was
definite integral: The area bounded by the straight line 0.99541241.
e42 Mathematics for Physical Chemistry

21. Find the integral: We divide the integral into two parts, one from t = 0 K
  to T = 30 K, and one from 30 K to 270 K.
1
x ln (x 2 )dx = ln (u)du
2 4.77 J K1 mol1
a= = 1.77 104
1 1 1 (30 K)3
= [u ln (u) u] = x 2 ln (x 2 ) x 2
2 2 2
23. The entropy change to bring a sample from 0 K  30 K  30 K
C P,m a
(absolute zero) to a given state is called the absolute Sm (30 K) = dT = 4
dT
0 T 0 T
entropy of the sample in that state.
1 a 1
 = = C P.m (30 K)
T C P,m 3 T3 3
Sm (T  ) = dT = 1.59 J K1 mol1
0 T
Sm (270 K) = 1.59 J K1 mol1
where Sm (T  )
is the absolute molar entropy at  270 K
C P,m
temperature T  ,C P,m is the molar heat capacity at + dT
constant pressure, and T is the absolute temperature. 30 K T
Using Simpsons rule, calculate the absolute entropy The second integral is evaluated using Simpsons rule.
of 1.000 mol of solid silver at 270 K. For the region The result is of this integration is 38.397 J K1 mol1
0 K to 30 K, use the approximate relation so that
C P = aT 3 , Sm (270 K) = 1.59 J K1 mol1 + 38.40 J K1 mol1
where a is a constant that you can evaluate from the = 39.99 J K1 mol1
value of C P at 30 K. For the region 30 K to 270 K,
25. Use Simpsons rule with at least 4 panels to evaluate
use the following data:1
the following definite integral. Use Mathematica to
' $check your results.
T/K CP /J K1 mol1 T/K CP /J K1 mol1  3 2
e x dx
30 4.77 170 23.61 1
50 11.65 190 24.09
With 20 panels, the result was 1444.2. The correct
70 16.33 210 24.42 value is 1443.1.
90 19.13 230 24.73
110 20.96 250 25.03
130 22.13 270 25.31
150 22.97
& %

1 Meads. Forsythe, and Giaque, J. Am. Chem. Soc. 63, 1902 (1941).
 

Chapter 8
 

Differential Calculus with Several


Independent Variables

   
EXERCISES z z
b. = +?
u x,y u x,w
Exercise 8.1. The volume of a right circular cylinder is
       
given by z z z w
V = r 2 h, = +
u x,y u x,w w x,u u x,y
where r is the radius and h the height. Calculate the c. Apply the equation of part b if z = z(x,y,u) =
percentage error in the volume if the radius and the cos (x) + y/u and w = y/u.
height are measured and a 1.00% error is made in each  
measurement in the same direction. Use the formula for the z y
= 2
differential, and also direct substitution into the formula for u x,y u
the volume, and compare the two answers.
   
V V z(x,u,w) = cos (x) + w
V r + h  
r h h r z
= 1
2r hr + r 2 h w x,u
V 2r hr r 2 h 2r h w(x,y,u) = cos (x) + z
+ = +    
V 2
r h 2
r h r h w z y
= = 2
= 2(0.0100) + 0.0100 = 0.0300 u x,y u x,y u
     y   z 
The estimated percent error is 3%. We find the actual z w
=1 2 =
percent error: w x,u u x,y u u x,y
V2 V1 r 2 (1.0100)2 h(1.0100) r 2 h Exercise 8.3. Show that the reciprocal identity is satisfied
=
V1 r 2 h r 2 h by (z/ x) and (z/z) y if
3
= (1.0100) 1 = 1.03030 1 = .03030  
x
percent error = 3.03% z = sin and x = y sin1 (z) = y arcsin (z).
y
Exercise 8.2. Complete the following equations. From the table of derivatives
   
    z 1 x
H H = cos
a. = +? x y y y
T P, n T V, n  
        x 1 y y
H H H V = y =   =  
= + z y 1z 2
2 cos x
T P, n T V, n V t,n T P, n 1 sin y x y

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00054-9


2013 Elsevier Inc. All rights reserved. e43
e44 Mathematics for Physical Chemistry

where we have used the identity z(u,v,y) = a(uvy)2 + bu sin (y)


 
z
sin2 () + cos2 () = 1 = 2au 2 v 2 y + bu cos (y)
y u,v
 x 
Exercise 8.4. Show by differentiation that ( 2 z/ y x) = z(u,v,x) = ax 2 + bu sin
uv
( 2 z/ x y) if    x 
z bu
z = e x y sin (x). = 2ax + cos
x u,v uv uv
 
x
2z = uv
= [ye x y sin (x) + e x y cos (x)] y u,v
y x y       x 
z x bu
xy = 2ax + cos uv
= {e [y sin (x) + cos (x)]} x u,v y u,v uv uv
y
= 2auvx + bu cos (y)
= e x y [x y sin (x) + x cos (x)] + e x y sin (x)]
= 2au 2 v 2 y + bu cos (y)

2z Exercise 8.8. Determine whether the following differen-


= xe x y sin (x) tial is exact:
x y x
= e x y sin (x) + x ye x y sin (x) + xe x y cos (x) du = (2ax + by 2 )dx + (bx y)dy
= e [x y sin (x) + x cos (x)] + e
xy xy
sin (x)]

Exercise 8.5. Using the mnemonic device, write three  


(2ax + by 2 )
additional Maxwell relations. = 2by
y
     x
T V (bx y)
= = by
P S,n S V, n x y
   
S V
= The differential is not exact.
P T, n T P, n
   
S P Exercise 8.9. Show that the following is not an exact
= differential du = (2y)dx + (x)dy + cos (z)dz.
V T, n T V, n
 
(2y)
Exercise 8.6. For the function y = x 2 /z, show that the = 2
y
cycle rule is valid.  x
x
  = 1
y 2x x y
=
x z z
    There is no need to test the other two relations.
x [(yz)1/2 ] 1
= = y 1/2 z 1/2
z y z y 2 Exercise 8.10. The thermodynamic energy of a mona-
  2 tomic ideal gas is given by
z x
= 2
y x y 3n RT
U=
2
         Find the partial derivatives and write the expression for dU
y x z 2x 1 1/2 1/2
= y z using T, V, and n as independent variables. Show that your
x z y z 2
z y x
 2 differential is exact.
x x3  
2 = 3/2 3/2 U 3n R
y z y =
T V, n 2
z 3/2 y 3/2  
= = 1 U
z 3/2 y 3/2 = 0
V T, n
 
Exercise 8.7. Show that if z = ax 2 + bu sin (y) and x = U 3RT
=
uvy then the chain rule is valid. n V, n 2
CHAPTER | 8 Differential Calculus with Several Independent Variables e45

   
3n R 3RT = (4y 2 2)ex
2 y 2
dU = dT + (0)dV + dn  
2 2 2 f
  = 2yex
2 y 2
( 2x) = 4x yex
2 y 2
2U x y
= 0
V T n
  At (0,0)
2U
= 0
T V D = ( 2)( 2) 0 = 4
 
n  
2U 2 f
= 0 = 2
V n x2 y
T
 
2U
= 0 Since D  0 and ( 2 f / x 2 ) y 0, we have a local
n V T maximum.
 
2U 3R
= Exercise 8.13. a. Find the local minimum in the
n T 2
 
V function
2U 3R f (x,y) = x 2 + y 2 + 2x
=
T n 2
V At a relative extremum
Exercise 8.11. Show that the differential  
f
= 2x + 2
  x y
x ln (x) x 2  2 
(1 + x)dx + + dy f
y y = 2
x2 y
is inexact, and that y/x is an integrating factor.  
f
= 2y
(1 + x) = 0 y x
y  2 
  f
x ln (x) x 2 ln (x) 1 2x = 2
+ = + + = 0 y2 x
x y y y y y  2 
f
The new differential is = 0
x y
y(1 + x)
dx + [ln (x) + x]dy At the extremum
y x 
+ y dx + [ln (x) + x]dy 2x + 2 = 0
x
2y = 0
y  1 This corresponds to x = 1,y = 0.
+1 = +1
y x x     2 2
1 2 f 2 f f
[ln (x) + x] = + 1 D= = (2)(2)0 = 4
x x x2 y2 x y

Exercise 8.12. Evaluate D at the point (0,0) for the This point, ( 1,0), corresponds to a local minimum.
function of the previous example and establish that the point The value of the function at this point is
is a local maximum.
  f ( 1,0) = ( 1)2 + 2( 1) = 1
f 2 2
= 2xex y b. Find the constrained minimum subject to the
x y
 2  constraint
f 2 2 2 2
x + y = 0.
= 2ex y 2xex y ( 2x)
x2 y
2 y 2
On the constraint, x = y. Substitute the con-
= (4x 2 2)ex straint into the function. Call the constrained function
 
f 2 y 2 g(x,y).
= 2yex =0
y
 
x g(x,y) = x 2 + ( x)2 + 2x = 2x 2 + 2x
2 f 2 y 2 2 y 2 g
= 2ex 2yex ( 2y) = 4x + 2
y2 x x
e46 Mathematics for Physical Chemistry

At the constrained relative minimum Exercise 8.15. Find the gradient of the function

x = 1/2, y = 1/2 g(x,y,z) = ax 3 + yebz ,

The value of the function at this point is where a and b are constants.
     
1 1 1 g g g
f ( 1/2,1/2) = + 2(1/2) = g = i +j +k = i3ax 2 +jebz +kbyebz
4 4 2 y y z
c. Find the constrained minimum using the method of Exercise 8.16. The average distance from the center of the
Lagrange. sun to the center of the earth is 1.495 1011 m. The mass
The constraint can be written of the earth is 5.983 1024 kg, and the mass of the sun
is greater than the mass of the earth by a factor of 332958.
g(x,y) = x + y = 0 Find the magnitude of the force exerted on the earth by the
so that sun and the magnitude of the force exerted on the sun by
the earth.
u(x,y) = x 2 + y 2 + 2x + (x + y)
The magnitude of the force on the earth due to the sun
The equations to be solved are is the same as the magnitude of the force on the sun due to
  the earth:
u |r| 1
= 2x + 2 + = 0 F = Gm s m e 3 = Gm s m e 2
x y r r
  (6.6731011 m3 s2 kg1 )(5.9831024 kg)2 (332958)
u =
= 2y + = 0 (1.495 1011 m)2
y x
= 3.558 1022 kg m2 s2 = 3.558 1022 J
Solve the second equation for :

= 2y
Exercise 8.17. Find r if
Substitute this into the first equation:
r = ix + jy + kz.
     
2x + 2 2y = 0 x y z
r = + + =3
x y z
We know from the constraint that y = x so that
Exercise 8.18. Find r where
4x + 2 = 0
1 r = ix + jy + kz.
x =
2
1 Explain your result.
y =      
2 z y x z y x
r = i +j +k
The value of the function is y z z x x y
  = 0
1 1 1 1 1
f , = + 1=
2 2 4 4 2 The interpretation of this result is that the vector r has no
rotational component.
Exercise 8.14. Find the minimum of the previous example
without using the method of Lagrange. We eliminate y and Exercise 8.19. Find the Laplacian of the function
2 2 2
z from the equation by using the constraints: f = exp (x 2 + y 2 + z 2 ) = e x e y e z .
   
f = x2 + 1 + 4 = x2 + 5 2 2 2 2 2 2
2 f = 2xe x e y e z + 2ye y e x e z
x y
The minimum is found by differentiating:  
2 2 2
f + 2ze z e x e y
= 2x = 0 z
x 2 2 2 2 2 2 2 2
= (2e x + 4x 2 e x )e y e z + (2e y + 4y 2 e y )e x e z
The solution is 2 2 2 2
+ (2e z + 4z 2 e z )e x e y
2 2 2
x = 0, y = 1, z = 2 = [6 + 4(x 2 + y 2 + z 2 )]e x e y e z
CHAPTER | 8 Differential Calculus with Several Independent Variables e47

Exercise 8.20. Show that f = 0 if f is a differ- 2 2


= [r er ]
entiable scalar function of x,y, and z. r 2 r
2 2 2 2 2
f f f = 2 (er 2r 2 er ) = 2 (2r 2 1)er
+j
f = i +k r
  r
x y z 1 2
 2 2   2  = 2 2 2 er
f f f 2 f r
f = i +j
yz zz z x xz
 2 2 
f f
+k =0 PROBLEMS
x y y x
1. A certain nonideal gas is described by the equation of
This vanishes because each term vanishes by the Euler
state
reciprocity relation. P Vm B2
=1+
Exercise 8.21. a. Find the h factors for cylindrical polar RT Vm
coordinates. where T is the temperature on the Kelvin scale, Vm is
the molar volume, P is the pressure, and R is the gas
hr = 1 constant. For this gas, the second virial coefficient B2
h = is given as a function of T by
hz = 1 B2 = [1.00 104 (2.148 106 )
e(1956 K)/T ]m3 mol1 ,
b. Find the expression for the gradient of a function of
cylindrical polar coordinates, f = f (,,z). Find ( P/ Vm )T and ( P/ T )Vm and an expression
f 1f f for dP.
f = e + e +k RT RT B2
r z P= +
Vm Vm2
c. Find the gradient of the function  
P RT 2RT B2
2 +z 2 )/a 2 = 2
f = e( sin (). Vm T Vm Vm3
   
P R R B2 RT d B2
  = + 2 + 2
2 ( 2 +z 2 )/a 2 T Vm Vm Vm Vm dT
( 2 +z 2 )/a 2
e sin () = e e sin () R R B2
a2 = + 2 + need term here
1 Vm Vm
2 2 2
+ e e( +z )/a cos ()   
RT 2RT B2 RT d B2
  dP = 2 + dT
2z 2 2 2 Vm Vm3 Vm2 dT
+ k 2 e( +z )/a sin ()  
a R R B2
  + + 2 dVm
2 1 Vm Vm
= e 2
sin () + e cos ()

a

r 3. Find ( f / x) y , and ( f / y)x for each of the
2z 2 2 2 following functions, where a, b, and c are constants.
+ k 2 sin () e( +z )/a
a
a. f = ax y ln (y)
Exercise 8.22. Write the formula for the divergence of a  
f
vector function F expressed in terms of cylindrical polar = ay ln (y)
x y
coordinates. Note that ez is the same as k.  
  f
1 = ax ln (y) + ax
F= (F ) + (F ) + (Fz ) y x
z
b. f = c sin (x 2 y)
Exercise 8.23. Write the expression for the Laplacian of  
f
the function er
2
= c cos (x 2 y)(2x y)
x y

   
2 1 e r 2 1 1 r 2 f
2 r
e = 2 r 2
= 2 2
r ( 2r ) 2 e = c cos (x 2 y)(x 2 )
r r r r r r y x
e48 Mathematics for Physical Chemistry

5. Find ( f / x) y , and ( f / y)x for each of the 1


= (2c)
following functions, where a, b, and c are constants. (bx 2 + cy 2 )
1
a. f = a cos2 (bx y) (2cy)2
(bx + cy 2 )2
2
   2 
f f 1
= 2a cos (bx y)a sin (bx y)(by) = (2bx)(2cy)
x y x y (bx 2 + cy 2 )2
 
f 9. Test each of the following differentials for exactness.
= 2a cos (bx y)a sin (bx y)(bx)
y x
a. du = sec2 (x y)dx + tan (x y)dy
b. f = a exp b(x 2 + y 2 )
[sec2 (x y)] = 2 sec (x y) sec (x y) tan (x y)(x)
  dy
f
= a exp ( b(x 2 + y 2 )( 2bx) = 2x sec2 (x y) tan (x y)
x y
 
f [tan (x y)] = sec2 (x y)(y)
= a exp ( b(x 2 + y 2 )( 2by) dx
y x
The differential is not exact.
b. du = y sin (x y)dx + x sin (x y)dy
7. Find ( 2 f / x 2 ) y ,( 2 f / x y),( 2 f / y x), and
( 2 f / y 2 ), for each of the following functions, where
[y sin (x y)] = sin (x y) + x y cos (x y)
a, b, and c are constants. dy
2 2
a. f = e(ax +by ) [x sin (x y)] = sin (x y) + x y cos (x y)
dx
 
f 2 2 The differential is exact.
= e(ax +by ) (2ax)
x y 11. Test each of the following differentials for exactness.
 2 
f 2 2 2 2
2
= e(ax +by ) (2a) + e(ax +by ) (2ax)2 a. du = x y dx + x y dy
x y
 2  (x y)
f 2 2 = x
= e(ax +by ) (2ax)(2by) dy
y x (x y)
 
f 2 2 = y
= e(ax +by ) (2by) dx
y x
 2  The differential is not exact.
f 2 2 2 2 b. du = yeax y dx + xeax y dy.
= e(ax +by ) (2b) + e(ax +by ) (2by)2
y2 x
 2  (yeax y ) = eax y + ax yeax y
f 2 2 dy
= e(ax +by ) (2ax)(2by)
x y
(xeax y ) = eax y + ax yeax y
dx
b. f = ln (bx 2 + cy 2 )
The differential is exact.
 
f 1
= (2bx) 13. Complete the formula
x y (bx + cy 2 )
2
   
 2  S S
f 1 = +?
= (2b) V P, n V T, n
x2 y (bx 2 + cy 2 )    
S S
1 dS = dV + dT
(2bx)2 V T, n T V, n
(bx + cy 2 )2
2
     
 2  S S V
f 1 =
= (2bx)(2cy) V P, n V T, n V P, n
y x (bx + cy 2 )2
2
   
  S T
f 1 +
= (2cy) T V, n V P, n
y x (bx + cy 2 )
2
     
 2  S S T
f 2 2 = +
= 2 (2x)2 2 V T, n T V, n V P, n
y2 x (x + y 2 )3 (x + y 2 )2
CHAPTER | 8 Differential Calculus with Several Independent Variables e49

15. Find the minimum in the function of the previous We replace y by 2 x:


problem subject to the constraint x + y = 2. Do this
by substitution and by the method of undetermined f (x) = x 2 6x 8(2 x) + (2 x)2
multipliers. On the constraint = x 2 6x 16 + 8x + 2 2x + x 2 = 2x 2 14

y = 2x df
= 4x
f = x 2 x (2 x) + (2 x)2 dx
= x 2 2 + 4 4x + x 2 This vanishes at x = 0, corresponding to (0,2), which
= 2x 2 4x + 2 is on the boundary of our region. This constrained
maximum must be at (0,2) or at (2,0). The value of
the function at (0,2) is 20 and the value at (0,2) is 20.
df This is the same as the unconstrained maximum.
= 4x 4 = 0 at the minimum
dx 19. Find an expression for the gradient of the function
x = 1 at the minimum
y = 2 x = 1 at the minimum f (x,y,z) = cos (x y) sin (z)
f = i y sin (x y) sin (z) + j x sin (x y) sin (z)
Now use Lagranges method. The constraint can be + k cos (x y) cos (z)
written
21. Find an expression for the Laplacian of the function
g(x,y) = x + y 2 = 0
u(x,y) = x 2 x y + y 2 + (x + y 2) f = r 2 sin ( ) cos ()

The equations to be solved are  


2 1 2 2
  f = = 2 r r sin ( ) cos ()
u r r r
= 2x 1 + = 0  
x y 1 2
  + 2 sin ( ) r sin ( ) cos ()
u r sin ( )
= 1 + 2y + = 0 1 2 2
y x + r sin ( ) cos ()
r 2 sin2 ( ) 2
Solve the second equation for : 2 sin ( ) cos () 3
= (r )
r2 r
= 1 2y
r 2 cos ()
+ 2 [sin ( ) cos ( )]
Substitute this into the first equation: r sin ( )
r2
2x 1 + 1 2y = 0 2 2 sin ( ) cos ()
r sin ( )
= 6( sin ( ) cos ())
We know from the constraint that y = 2 x so that
cos ()
+ [cos2 ( ) sin2 ( )]
2x 1 + 1 2(2 x) = 0 sin ( )
1
4x 4 = 0 2 sin ( ) cos ()
sin ( )
x = 1
cos2 ( ) cos ()
y = 1 = 6 sin ( ) cos () +
sin ( )
17. Find the maximum in the function of the previous cos ()
sin ( ) cos ()
problem subject to the constraint x + y = 2. sin ( )
 
cos2 ( ) 1
f (x,y) = x 2 6x + 8y + y 2 = 6 sin ( ) + cos ()
sin ( ) sin ( )
This page is intentionally left blank
 

Chapter 9
 

Integral Calculus with Several


Independent Variables

EXERCISES We let u = x 2 ; du = 2x dx
 2  4
Exercise 9.1. Show that the differential in the preceding 2
2 (xe x )dx = (eu )du = e4 e0 = e4 1
example is exact. 0 0
The differential is 
c. Calculate the line integral c dz on the path going from
dF = (2x + 3y)dx + (3x + 4y)dy (0,0) to (0,2) and then to (2,2) (a rectangular path).

On the first leg:


We apply the test based on the Euler reciprocity theorem:
  2
dz = ((0)e0 )dx + 0 = 0
(2x + 3y) = 3 c 0
y
On the second leg

(3x + 4y) = 3   2
x
dz = 0 + (2)e2y dy
c 0
Exercise 9.2. a. Show that the following differential is
exact: We let w = 2y; dw = 2 dy
dz = (ye x y )dx + (xe x y )dy  2  4
2y
(2)e dy = ew dw = e4 1
0 0

(ye x y ) = e x y + x ye x y Exercise 9.3. Carry out the two line integral of du = dx +
y
x dy from (0,0) to (x1 ,y1 ):

(xe x y ) = e x y + x ye x y
x a. On the rectangular path from (0,0) to (0,y1 ) and then
 to (x1 ,y1 );
b. Calculate the line integral c dz on the line segment
from (0,0) to (2,2). On this line segment, y = x and On the first leg
x = y.   y1
   dz = 0 + 0 dy = 0
2 2 c 0
x2 y2
dz = (xe )dx + (ye )dy
c 0 0 On the second leg:
 2   x1
2
= 2 (xe x )dx dz = dx + 0 = x1
0 c 0

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00055-0


2013 Elsevier Inc. All rights reserved. e51
e52 Mathematics for Physical Chemistry

The line integral is Exercise 9.5. A two-phase system contains both liquid
 and gaseous water, so its equilibrium pressure is determined
(dx + x dy) = x1 by the temperature. Calculate the cyclic integral of dwrev
c for the following process: The volume of the system is
changed from 10.00 l to 20.00 l at a constant temperature of
b. On the rectangular path from (0,0) to (x1 ,0) and then
25.00 C, at which the pressure is 24.756 torr. The system
to (x1 ,y1 ).
is then heated to a temperature of 100.0 C at constant
On the first leg volume of 20.00 l. The system is then compressed to a
  volume of 10.00 l at a temperature of 100.0 C, at which
x1
the pressure is 760.0 torr. The system is then cooled from
dz = dx + 0 = x1
c 0 100.0 C to a temperature of 25.00 C at a constant volume
of 10.00 l. Remember to use consistent units.
On the second leg:
On the first leg
  y1
dz = 0 + x1 dy = x1 y1   
c 0 dwrev = P dV = P dV = PV
C C
The line integral is  C 
101325 Pa
 = (23.756 torr)
760 torr
(dx + x dy) = x1 + x1 y1  
1m 3
c
(10.00 l) = 31.76 J
The two line integrals do not agree, because the differential 1000 l
is not exact.
On the second leg

Exercise 9.4. Carry out the line integral of the previous
dwrev = 0
example, du = yz dx + x z dy + x y dz, on the path from C
(0,0,0) to (3,0,0) and then from (3,0,0) to (3,3,0) and then
from (3,3,0) to (3,3,3). On the third leg
On the first leg
 
y = 0, z = 0 dwrev = P dV = PV
C C
  3    
101325 Pa 1 m3
du = (0)dx + 0 + 0 (760.0 torr) ( 10.00 l)
c 0 760.0 torr 1000 l
On the second leg = 1013 J

x = 3, z = 0 On the fourth leg


  3
du = (0)dy + 0 
c 0
dwrev = 0
On the third leg C

wrev = dwrev = 31.76 J + 1013 J = 981 J
x = 3, y = 3
  3
du = (9)dz = 27
c 0 The cyclic integral does not vanish because the differential
is not exact.
The line integral on the specified path is

(yz dx + x z dy + x y dz) = 0 + 0 + 27 = 27 Exercise 9.6. The thermodynamic energy of a monatomic
c ideal gas is temperature-independent, so that dU = 0 in an
The function with this exact differential is u = x yz + C isothermal process (one in which the temperature does not
where C is a constant, and the line integral is equal to change). Evaluate wrev and qrev for the isothermal reversible
expansion of 1.000 mol of a monatomic ideal gas from a
z(3,3,3) z(0,0,0) = 27 + C 0 C = 27 volume of 15.50 l to a volume of 24.40 l at a constant
CHAPTER | 9 Integral Calculus with Several Independent Variables e53

temperature of 298.15 K. 25.00 10.00x + x 2


= 5.00(5.00 x) 5.00x
2
U = q + w x2
  V2 = 12.50 5.00x +
1 2
wrev = P dV = n RT dV  3.00  
x2
C V1 V V = 12.50 5.00x + dx = 12.50x
  0 2
V2
= n RT ln 3.00
V1 5.00x 2 x3 
+ 
= (1.000 mol)(8.3145 J K1 mol1 ) 2 6 0
  27.00
24.40 l = 37.5 22.50 + = 19.5
(298.15 K) ln 6
15.50 l
= 1125 J Exercise 9.9. Find the value of the constant A so that the
qr ev = 1125 J following integral equals unity.
 
2 2
A ex y dy dx.
The negative sign of w indicates that the system did work
on its surroundings, and the positive sign of q indicates that
heat was transferred to the system. The integral can be factored
 
2 2
A ex y dy dx

Exercise 9.7. Evaluate the double integral  
2 2
=A ex dx ey dy
 4
x sin2 (y)dy dx. The integrals can be looked up in a table of definite integrals
2 0
 
2 2
ex dx = 2 ex dx =
We integrate the dy integral and then the dx integral. We 0
use the formula for the indefinite integral over y:  
2 2
A ex y dy dx = A = 1
 4

x sin (y)dy dx 2 1
A=
2 0

 4   4
y sin (2y)  Exercise 9.10. Use a double integral to find the volume of
= x  dx = x dx
2 2 4 0 2 2 a cone of height h and radius a at the base. If the cone is
 4   standing with its point upward and with its base centered at
x 2  16 4
=  = = 3 the origin, the equation giving the height of the surface of
2 2 2 2 2 2
the cone as a function of is


Exercise 9.8. Find the volume of the solid object shown in f =h 1 .
a
Fig. 9.3. The top of the object corresponds to f = 5.00x
y, the bottom of the object is the x-y plane, the trapezoidal  

a 2
face is the x-f plane, and the large triangular face is the y-f V = h d d
1
plane. The small triangular face corresponds to x = 3.00. 0 0 a
 a 
2
 = 2 h d
3.00  5.00x 0 a
V = (5.00 x y)dy dx  2 a  2 
0 0 3  a a2 ha 2
= 2 h = 2 h =
2 3a 0 2 3 3
The first integration is
Exercise 9.11. Find the Jacobian for the transformation
 5.00x
from Cartesian to cylindrical polar coordinates. Without
(5.00 x y)dy resorting to a determinant, we find the expression for the
0 element of volume in cylindrical polar coordinates:
5.00x

= (5.00y x y y 2 /2) dV = element of volume = d d dz.
0
e54 Mathematics for Physical Chemistry

The Jacobian is 3. Perform the line integral


(x,y,z)
=    
(,,z) 1 1
du = dx + dy
Exercise 9.12. Evaluate the triple integral in cylindrical C C x y
polar coordinates:
on the curve represented by
 3.00  4.00  2
I = z 3 cos2 ()d d dz y=x
0 0 0
The integral can be factored: From (1,1) to (2,2).
 2  4.00  3.00
  
I = cos2 ()d 3 d z dz 2 1 2 1
0 0 0 du = dx + dy
C 1 x 1 y
The integral can be looked up in a table of indefinite
= [ln (x)]21 + [ln (y)]21
integrals:
 2   = 2[ln (2) ln (1)] = 2 ln (2)
sin (2) 2
cos2 ()d =  =
0 2 4 0
Note that du is exact, so that
 4.00 
4 4.00
 u = ln (x y)
3 d = = 64.0
0 4 0
 3.00 3 the line integral is equal to
z 2  9.00
z dz =  = = 4.50
0 2 0 2 u(2,2) u(1,1) = ln (22 ) 2 ln (2) = 1.38629
I = 4.50 64.0 = 288 = 905
5. Find the function f (x,y) whose differential is

PROBLEMS d f = (x + y)1 dx + (x + y)1 dy


1. Perform the line integral and which has the value f (1,1) = 0. Do this by
 
performing a line integral on a rectangular path from
du = (x 2 y dx + x y 2 dy), (1,1) to (x1 ,y1 ) where x1 > 0 and y1 > 0. Since the
C C
differential is exact,
a. on the line segment from (0,0) to (2,2). On this
path, x = y, so f (x1 ,y1 ) f (1,1)
  2  2 2 2 

3 3 x 4  y 4  = (x + y)1 dx + (x + y)1 dy
du x dx + y dy = +
C 0 0 4 0 4 0 C
16 16 We choose the path from (1,1) to (1,x1 ) and from
= + =8
4 4 (1,x1 ) to (x1 ,y1 ). On the first leg, x = 1 and dy = 0.
b. on the path from (0,0) to (2,0) and then from (2,0) On the second leg, x = x1 and dx = 0
to (2,2). On the first leg of this path, y = 0 and 

dy = 0, so both terms of the integral vanish on (x + y)1 dx + (x + y)1 dy
this leg. On the second leg, x = 2 and dx = 0. C
 x1  y1
  2 2 1 1
y 3  16 = dx + dy
du = 0 + 2
2y dy = 2 + 1 1+y
 = 3 1 x 1 x
0 3 y
C 0 = ln (x + 1)|1x1 + ln (x1 + y)|11
The two results do not agree, so the differential is = ln (x1 + 1) ln (2) + ln (x1 + y1 ) ln (x1 + 1)
not exact. Test for exactness:
 f (x1 ,y1 ) f (1,1) = ln (x1 + y1 ) ln (2)
2
(x y) = x 2
y Since f (1,1) = 0 the function is
 x

(x y ) = y 2
2
f (x,y) = ln (x + y) ln (2)
x y

The differential is not exact. where we drop the subscripts on x and y.


CHAPTER | 9 Integral Calculus with Several Independent Variables e55

7. Find the moment of inertia of a uniform disk of radius (a + a)5 = a 5 + 5a 4 a + 10a 3 a 2 + 10a 2 a 3
0.500m and a mass per unit area of 25.00 g m2 . The
+5aa 4 + a 5
moment of inertia, is defined by
  R  2 If a is small, so that we can ignore a 2 compare
I = m() 2 dA = m() 2 d d with a,
0 0

where m() is the mass per unit area and R is the radius (a + a)5 a 5 5a 4 a
of the disk. I 4 ma 4 a
 
2 1 kg
I = (25.00 g m ) We apply this approximation
1000 g
 0.500 m  2
I 4(3515 kg m3 )(0.500 m)4 (0.112 mm)
2 d d  
0 0 1m
 0.500 m = 0.309 kg m2
1000 mm
= (0.02500 kg m2 )(2 ) 3 d
0
  11. Derive the formula for the volume of a right circular
(0.500 m)4 cylinder of radius a and height h.
= (0.15708 kg m2 )
4
   2
= 0.002454 kg m2
h a
V = d d dz
0 0 0
The mass of the disk is  h  a
  R 2 = 2 d dz
0 0
M = m()dA = m() d d  h  a
0 0
 = 2 d dz
R R2 0 0
= 2 m() d = 2 m()  h  2
0 2 a
 2 = 2 dz = a 2 h
2 (0.500 m) 0 2
= 2(0.02500 kg m )
2
= 0.01963 kg 13. Find the volume of a right circular cylinder of radius
a = 4.00 with a paraboloid of revolution scooped out
The standard formula from an elementary physics of the top of it such that the top surface is given by
book is
z = 10.00 + 1.00 2
1 1
I = M R 2 = (0.01963 kg)(0.500 m)2
2 2 and the bottom surface is given by z = 0.00.
= 0.002454 kg m2
 2.00  10.00+1.00 2  2
9. Find an expression for the moment of inertia of a V = d dz d
hollow sphere of radius a, a thickness a, and a 0 0.00 0
uniform mass per unit volume of m. Evaluate your The limit on is obtained from the fact that = 2.00
expression if a = 0.500 m, a = 0.112 mm, when the parabola intersects with the cylinder.
m = 3515 kg m3 .
 a+a   2  2.00  10.00+1.00 2
I = mr 2 r 2 sin ( )d d d V = 2 dz d
0 0.00
a

0

0  2.00
a+a
r = 2 2 2
mr r sin ( )d dr = 2 d[10.00 + 1.00 2 ]
0
a 0    
 a+a 4.00 8
= 20.00 + 2.00
= (2)2 mr 4 dr 2 3
a
16.00
(a + a)5 a5 = 40.00 + = 142.4
= 4 m 3
5 5
15. Find the volume of a solid produced by scooping out
Expanding the polynomial the interior of a circular cylinder of radius 10.00 cm
e56 Mathematics for Physical Chemistry

 0.200 m
and height 12.00 cm so that the inner surface conforms
= (0.500 m) mx 2 dx
to z = 2.00 cm + (0.01000 cm2 ) 3 . 0.200 m
 10.00 cm  2  0.250 m
V = +(0.400 m) my 2 dy
0 0 0.250 m
 
2.00 cm + (0.01000 cm2 ) 3 d d 1
 2 = (0.500 m) m[x 3 ]0.200 m
0.200 m
3
= d
0 1  0.250 m
   10.00 cm +(0.400 m) m y 3
2.00 cm 2 0.01000 cm2 3 0.250 m
+ 5
2 5 0.00 2
 = (0.500 m) m(0.200 m)3
3 2
= (2 ) 100.0 cm + (0.00200 cm ) 3

(1.00 105 cm5 ) 2
+(0.400 m) m(0.250 m)3
3
= 1885 cm3
2
= (0.500 m) (10.00 kg m2 )(0.00800 m3 )
17. Find the moment of inertia of a flat rectangular plate 3
with dimensions 0.500 m by 0.400 m around an axis
2
through the center of the plate and perpendicular to it. +(0.400 m) (10.00 kg m2 )(0.015625 m3 )
Assume that the plate has a mass M = 2.000 kg and 3
that the mass is uniformly distributed. = 0.02667 kg m2 + 0.04167 kg m2
 0.250 m  0.200 m
I = m(x 2 + y 2 )dx dy = 0.06833 kg m2
0.250 m 0.200 m
From an elementary physics textbook
where we let m be the mass per unit area.
1
2.000 kg I = M(a 2 + b2 )
m= = 10.00 kg m2 12
0.200 m2
where a and b are the dimensions of the plate. From
 0.250 m  0.200 m this formula
I = mx 2 dx dy + I  
0.250 m 0.200 m 1  
  I = (2.000 kg) (0.400 m)2 + (0.500 m)2
0.250 m 0.200 m 12
= my 2 dx dy
0.250 m 0.200 m
= 0.06833 kg m2
 

Chapter 10
 

Mathematical Series

EXERCISES b. 0.001%.
0.001% of 1.64993 is equal to 0.00016449. The
Exercise 10.1. Show that in the series of Eq. (10.4) any n = 79 term is equal to 0.0001602, so we need the
term of the series is equal to the sum of all the terms partial sum S79 . However, this partial sum is equal to
following it. ( Hint: Factor a factor out of all of the following 1.6324, so again this approximation does not work very
terms so that they will equal this factor times the original well.
series, whose value is now known.)
Let the given term be denoted by
Exercise 10.3. Find the value of the infinite series
1
term =
2n


The following terms are [ln (2)]n
n=0
1 1 1 1
+ n+2 + n+3 + n+4 +
2n+1 2 2 2 Determine how well this series is approximated by S2 ,S5 ,
 
1 1 1 1 1 and S10 .
= n+1 1 + + + + + n +
2 2 4 8 2 This is a geometric series, so the sum is
2 1
= n+1 = n
2 2 1
s= = 3.25889
1 ln (2)
Exercise 10.2. Consider the series
The partial sums are
1 1 1 1
s =1+ + 2 + 2 + + 2 +
22 3 4 n
S2 = 1 + ln (2) = 1.693
which is known to be convergent and to equal
2 6/ = 1.64993 . Using Eq. (10.5) as an approximation, S5 = 1 + ln (2) + ln (2)2 + ln (2)3 + ln (2)4
determine which partial sum approximates the series to = 2.73746
S10 = 3.175461
a. 1%
1% of 1.64993 is equal to 0.016449. The n = 8 term is S20 = 3.256755
equal to 0.015625, so we need the partial sum S8 , which
is equal to 1.2574 . The series is slowly convergent
and S8 is equal to 1.5274, so this approximation does Exercise 10.4. Evaluate the first 20 partial sums of the
not work very well. harmonic series.
Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00056-2
2013 Elsevier Inc. All rights reserved. e57
e58 Mathematics for Physical Chemistry

Here are the first 20 partial sums, obtained with Excel: Exercise 10.7. Show that the Maclaurin series for e x is
' $ 1 1 1 1
ex = 1 + x + x2 + x3 + x4 +
1 1! 2! 3! 4!
1.5 Every derivative of e x is equal to e x
1.833333333  
1 dn f 1
2.083333333 an = =
n! dx n x=0 n!
2.283333333
2.45 Exercise 10.8. Find the Maclaurin series for ln (1 + x).
2.592857143 You can save some work by using the result of the previous
example.
2.717857143
The series is
2.828968254
2.928968254 ln (1 + x) = a0 + a1 x + a2 x 2 +
3.019877345
3.103210678 a0 = ln (1) = 0
 
3.180133755 d f  1 
= =1
3.251562327 dx  x=0 1 + x x=0
3.318228993 The second derivative is
 
3.380728993
d2 f    1 

3.439552523  = 1   2 
= 1
dx 2 x=0 1 + x x=0
3.495108078
3.547739657 The derivatives follow a pattern:
3.597739657  n  
d f 
n1 (n 1)! 
 n1
& % = ( 1)  = 1 (n 1)!
dx x=1
n (1 + x) x=0
n
 
1 dn f ( 1)n1
=
Exercise 10.5. Show that the geometric series converges n! dx n x=1 n
if r 2 1.
If r is positive, we apply the ratio test: The series is
       
an+1 1 1 1 1
lim =r ln (1+x) = x x 2+ x 3 x 4+ x 5 +
n an 2 3 4 5

If r 2 1 and if r is positive, then r 1, so the series Exercise 10.9. Find the Taylor series for ln (x), expanding
converges. If r is negative, apply the alternating series test. about x = 2, and show that the radius of convergence for
Each term is smaller than the previous term and approaches this series is equal to 2, so that the series can represent the
zero as you go further into the series, so the series converges. function in the region 0 x  4.
The first term is determined by letting x = 2 in which
Exercise 10.6. Test the following series for convergence. case all of the terms except for a0 vanish:

 1 a0 = ln (2)
n2
n=1 The first derivative of ln (x) is 1/x, which equals 1/2 at
Apply the ratio test: x = 2. The second derivative is 1/x 2 , which equals 1/4
  at x = 2. The third derivative is 2!/x 3 , which equals 1/4 at
1/(n + 1)2 n2 x = 1. The derivatives follow a regular pattern,
r = lim = lim =1
n 1/n 2 n (n + 1)2
 n  
d f n1 (n 1)! 
 (n 1)!
The ratio test fails. We apply the integral text: = (1) = ( 1)n1
  dx n x=2 x n x=2 2n

1 1 
dx = =1 so that  
1 x 2 x 1 1 dn f (1)n1
=
The integral converges, so the series converges. n! dx n x=1 n2n
CHAPTER | 10 Mathematical Series e59

and We use the expression for the square of a power series from
1 1 Eq. (5) of Appendix C, part 2:
ln (x) = ln (2) + (x 2) (x 2)2 + (x 2)3  2
8 24 RT RT B2 RT B3
1 + + +
(x 2)4 + Vm Vm2 Vm3
64       4
RT 2 RT RT B2 1
The function is not analytic at x = 0, so the series is = +2 + O
Vm Vm Vm2 Vm
not valid at x = 0. For positive values of x the series is    2 2   4
RT 2 R T B2 1
alternating, so we apply the alternating series test: = +2 +O
Vm Vm3 Vm
(x 2)n ( 1)n1  
tn = an (x 2)n = RT A2 RT RT B2 RT B3
n2n P = + + + +
Vm Vm Vm Vm2 Vm3
0 if|x 2| 2 or 0 x  4
   2 2   4
lim |tn | =
n if|x 2| > 2 or x > 4. A3 RT 2 R T B2 1
+ +2 3
+O
Vm Vm Vm Vm
Exercise 10.10. Find the series for 1/(1 x), expanding  
about x = 0. What is the interval of convergence? RT RT A2 RT A2 B2 A3 RT 2
+ = + + +
Vm Vm2 Vm3 Vm Vm
1
= a0 + a1 x + a2 x 2 + RT RT B2 RT B22 A3 R 2 T 2
1+x = + 2
+ 3
+
Vm Vm Vm Vm3
where we have replaced A2 by B2 . We now equation
 2
a0 = 1 coefficients of equal powers of 1/Vm in the two series
  
d 1  1  for P:
a1 =  =  = 1

dx 1 + x x=0 (1 + x) x=0
2
   RT B3 = RT B22 + A3 R 2 T 2
1 d 1  2 1 
a2 =  =  =1 A3 = B3 RT B22
2! dx (1 + x)2  2! (1 + x) x=0
3
x=0
Exercise 10.12. Determine how large X 2 can be before
The pattern continues: the truncation of Eq. (10.28) that was used in Eq. (10.16)
is inaccurate by more than 1%.
an = (1)n
1 2
1 ln (X 1 ) = ln (1 X 2 ) = X 2
X +
= 1 x + x2 x3 + x4 x5 + 2 2
1+x
If the second term is smaller than 1% of the first term
Since the function is not analytic at x = 1, the interval of (which was the only one used in the approximation) the
convergence is 1 x 1 approximation should be adequate. By trial and error, we
find that if X 2 = 0.019, the second term is equal to
Exercise 10.11. Find the relationship between the 0.0095 = 0.95% of the first term.
coefficients A3 and B3 .
We begin with the virial equation of state Exercise 10.13. From the Maclaurin series for ln (1 + x)
RT RT B2 RT B3 1 1
P= + 2
+ + ln (1 + x) = x x 2 + x 3 +
Vm Vm Vm3 2 3
We write the pressure virial equation of state: find the Taylor series for 1/(1 + x), using the fact that
d[ln (1 + x)] 1
RT A2 P A3 P 2 = .
P= + + + dx 1+x
Vm Vm Vm For what values of x is your series valid?
 
We replace P and P 2 in this equation with the expression 1 d 1 2 1 3
= x x + x
from the virial equation of state: 1+x dx 2 3
  2x 3x 2 4x 3
RT A2 RT RT B2 RT B3 =1 +
P = + + + + 2 3 4
Vm Vm Vm Vm2 Vm3 = 1 x + x2 x3 + x4 x5 +
 2
A3 RT RT B2 RT B3 which is the series already obtained for 1/(1 + x) in an
+ + + + +
Vm Vm Vm2 Vm3 earlier example. The series is invalid if x  1.
e60 Mathematics for Physical Chemistry

Exercise 10.14. Find the formulas for the coefficients in a There is a pattern, with all even-numbered coefficients
Taylor series that expands the function f (x,y) around the vanishing and odd-numbered coefficients alternating
point x = a,y = b. between 1/n! and 1/n!.
f (x,y) = a00 + a10 (x a) + a01 (y b) + a11 (x a) 1 1
(y b) + a21 (x a)2 (y b) + a12 (x a) cos (x) = (x /2) + (x /2)3
1! 3!
(y b)2 + 1
a00 = f (a,b) (x /2)5 +
   5!
f 
a10 =
y x x=a,b=y 7. Find the coefficients of the first few terms of the Taylor
   series
f 
a01 =
y x a,b 2
 2  sin (x) = a0 + a1 x + a2 x +
f  4 4
a11 =
y x a,b
 n+m  where x is measured in radians. What is the radius of
1 f  convergence of the series?
amn =
n!m! y x 
m n
a,b
1
a0 = sin (/4) = = 0.717107
2

PROBLEMS 1  1
a1 = cos (x) =
1. Test the following series for convergence. 1! /4 2

1  1
 a2 = sin (x) =
(( 1)n (n 1)/n 2 ). 2! /4 2! 2

n=0 1  1
We apply the alternating series test: a3 = cos (x) =
3! /4 3! 2
  n
n1
limn |tn | = limn = lim n
  n2 n2 The coefficients form a regular pattern:
1
= limn =0
n 1
an = (1)n
The series is convergent. n! 2
3. Test the following series for convergence. 1 1 1 2
sin (x) = x + x

 2 2 4 2! 2 4
 
1/n! . 1 3  n 1 n
x + 1 x
n=0 3! 2 4 n! 2 4
Try the ratio test +
an+1 n! 1
r = lim = lim = lim =0 Since the function is analytic everywhere, the radius
n an n (n + 1)! n n + 1
of convergence is infinite.
The series converges.
9. The sine of /4 radians (45 ) is 2/2 =
5. Find the Taylor series for cos (x), expanding about
0.70710678 . . .. How many terms in the series
x = /2.
cos (x)= a0 + a1 (x /2) + a2 (x /2)2 + x3 x5 x7
  sin (x) = x + +
a0 = cos /2 = 0 3! 5! 7!
 
1 d  1 
a1 = 
[cos (x)] = sin (x) = 1 must be taken to achieve 1% accuracy at x = /4?
1! dx /2 2! /2
 
1 d  1 
a2 = [cos (x)] = cos (x) =0 = 0.785398
2! dx /2 2! /2 4
  x3
1 d  1  1
a3 = [cos (x)]  = sin (x) = x = 0.785398 0.080746 = 0.704653
3! dx 3! 3! 3!
/2 /2
CHAPTER | 10 Mathematical Series e61

This is accurate to about 0.4%, so only two terms are The function is not analytic at x = 0, so the interval
needed. of convergence is 0 x 2
11. Estimate the largest value of x that allows e x to be
1
approximated to 1% accuracy by the following partial = b0 + b1 (x 2) + b2 (x 2)2 +
sum x
e x 1 + x. 1 1
b0 = =
Here is a table of values: 2 2
' $ 1  1
b1 = 2  =
x 2 4
a. x difference 1 + x ex %  
1 2  1
b2 = =
2! x 3 2
0.20000 1.20000 1.221402758 1.78
8
0.19000 1.19000 1.209249598 1.62  
1 6  1
0.18000 1.18000 1.197217363 1.46 b3 = =
0.17000 1.17000 1.185304851 1.31 2! x 4 2 16
0.15000 1.15000 1.161834243 1.03 The coefficients follow a regular pattern so that
0.14000 1.14000 1.150273799 0.90
0.14500 1 an
1.14500 1.156039570 0.96
bn = ( 1)n = n
0.14777 1.14777 1.159246239 0.9999 2n 2
1 1 1 1
By trial and error, 1% accuracy is obtained = (x 1) + (x 1)2
with x 0.14777. x 2 4 8
& % 1 1
(x 1) + (x 1)4 +
3
16 32
13. Find two different Taylor series to represent the
function The function is not analytic at x = 0, so the interval
1 of convergence is 0 x 4. The second series must
f (x) =
x be used for x = 3, since this value of x is outside the
such that one series is region of convergence of the first series.
15. Using the Maclaurin series for e x , show that the
f (x) = a0 + a1 (x 1) + a2 (x 1)2 + derivative of e x is equal to e x .
and the other is
x2 x3 x4
2 ex = 1 + x + + + +
f (x) = b0 + b1 (x 2) + b3 (x 2) + 2! 3! 4!
d x 2x 3x 2 4x 3
Show that bn = an /2n for any value of n. Find the e = 0+1+ + + +
interval of convergence for each series (the ratio test dx 2! 3! 4!
may be used). Which series must you use in the vicinity x2 x3
= 1+x + + + = ex
of x = 3? Why? Find the Taylor series in powers of 2! 3!
(x 10) that represents the function ln (x). 17. Find the Taylor series for sin (x), expanding around
1 /2.
= a0 + a1 (x 1) + a2 (x 1)2 +
x
sin (x) = a0 + a1 (x /2) + a2 (x /2)2
1
a0 = = 1 +a3 (x /2)3 +
1   
1 a0 = sin /2 = 1
a1 = 2  = 1
x 1 
  1 dn 
1 2  an = sin (x)
a2 = =1 n! d x n 
2! x 3 1
/2
 
1 6  df
a3 = =1 = cos (x)
2! x 4 1 dx  
a1 = cos /2 = 0
The coefficients follow a regular pattern so that
d2 f
1 = sin (x)
an = ( 1) = 1 (x 1) + (x 1)2
n
dx 2
x 1   1
(x 1)3 + (x 1)4 + a2 = sin /2 =
2! 2!
e62 Mathematics for Physical Chemistry

d3 f 23. Find the first few terms of the two-variable Maclaurin


= cos (x)
dx 3 series representing the function
1  
a3 = cos /2 = 0 f (x,y) = sin (x + y)
3!
d4 f
= sin (x)
dx 4 f (0,0) = sin (0) = 0
1 1   
a4 = sin (/2) = f 
4! 4!  = cos (x + y)|0,0 = 1
x y
0,0
  
There is a pattern. Only even values of n occur,and f 
= cos (x + y)|0,0 = 1
signs alternate. y x 0,0
 2 
1 1 f 
sin (x) = 1 (x /2)2 + (x /2)4 = sin (x + y)|0,0 = 1
2! 4! y x 0,0
1  2 
(x /2)6 + f 
6! = sin (x + y)|0,0 = 0
x 2 0,0
19. Find the interval of convergence for the series for  2 
f 
cos (x). = sin (x + y)|0,0 = 0
y 2 0,0
x2 x4 x6  3 
cos (x) = 1 + + f   
= cos (x + y) 0,0 = 1
2! 4! 6! y x 2 0,0
 3 
Apply the alternating series test. Each term is smaller f   
= cos (x + y) 0,0 = 1
than the previous term if x is finite and if you go far y 2 x 0,0
enough into the series. The series converges for all  4 
f   
finite values of x.  = sin (x + y) 0,0 = 0
21. Using the Maclaurin series, show that y 2 x 2 0,0


 x1 5 f   
x 
es dx = e x 01 = e x1 1  = cos (x + y) 0,0 = 1
y2 x 3 
0 0,0
 x  x  
x2 x3 x4 There is a pattern. If n + m is even, the derivative
es dx = 1+x + + + + dx
0 0 2! 3! 4! vanishes. If n + m is odd, the derivative has magnitude
 x1 1 with alternating signs.
x 2 x 3 x 4 
= x+ + + + 
2 (3)2! (4)3! 0 1
sin (x + y) = x + y (x 2 y + x y 2 )
x2 x3 x4 1!2!
= 1+x + + + + 1 1 1
2! 3! 4! + (x 2 y 3 + x 3 y 2 ) (x 4 y 3 + x 3 y 4 ) +
= e 1
x1 3!2! 3!4!
 

Chapter 11
 

Functional Series and Integral Transforms

EXERCISES Exercise 11.2. Sketch a rough graph of the product


   
cos Lx sin Lx from 0 to 2 and convince yourself that
Exercise 11.1. Using trigonometric identities, show that its integral from L to L vanishes. For purposes of the
the basis functions in the series in Eq. (11.1) are periodic graph, we let u = x/L, so that we plot from to .
with period 2L.
Here is an accurate graph showing the sine, the cosine,
We need to show for arbitrary n that and the product. It is apparent that the negative area of the
product cancels the positive area.
   n x 
n(x + 2L)
sin = sin
L L
and    n x 
n(x + 2L)
cos = cos
L L
From a trigonometric identity
   
n(x + 2L) n(x)
sin = sin cos[2n ]
L L
 
n(x)
+ cos sin (2n )
L
 
n(x)
= sin
L
Exercise 11.3. Show that Eq. (11.15) is correct.
This result follows from the facts that
 L  m x 
 L  n x 
cos[2n ] = 1 f (x) sin dx = an cos
L L L L
sin (2n ) = 0 n=0
 m x 
sin dx
Similarly, L
   
 L  n x 
n(x + 2L) n(x) + bn sin
cos = cos cos[2n ] L L
L L n=0
   m x 
n(x) sin dx
+ sin sin (2n ) L
L
 
n(x) By orthogonality, all of the integrals vanish except the
= cos
L integral with two sines and m = n. This integral equals L.
Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00057-4
2013 Elsevier Inc. All rights reserved. e63
e64 Mathematics for Physical Chemistry

 L  n x 
L
f (x) sin dx = bn L = [n sin (n ) n
L L n
  n x 
1 L
L
 n x 

L
bn = f (x) sin dx sin (0)] + ( cos

L L L n L
0

Exercise 11.4. Show that the an coefficients for the series L
representing the function in the previous example all vanish. = 0+ [cos (n ) cos (0)]
n
 L
L
1 x 2

L
a0 = xdx = =0 = [( 1)n ) 1]
2L L 2
L n
  n x 
1 L L L
an = x cos dx |x| = + [( 1)n ) 1]
L L L 2 n
n1
Integrate by parts: Let u = x, du = dx, dv = (dv/dx)dx =  n x 
cos (n x/L)dx, v = (L/n ) sin (n x/L) cos
  L
udv = uv vdu
Exercise 11.6. Derive the orthogonality relation expressed
  n x 
L above.
L L

x cos dx = x sin (n x/L)

L L n L 
 L  n x 
L im x in x
L exp exp dx
sin dx L L L
n L  L 
m x   m x 
L

L = cos i sin
= [n sin (n ) L L L
n  n x   n x 
n sin ( n )] cos + i sin dx
L L

L  n x 

L  L  m x   n x 
+ ( cos
= cos cos dx
n L
L L L L
 L
L  m x   n x 
= 0+ [cos (n ) i sin cos dx
n L L L
cos ( n )] = 0  L  m x   n x 
+i cos sin dx
L L L
Exercise 11.5. Find the Fourier cosine series for the even  L  m x   n x 
function + sin sin dx
f (x) = |x| for L < x < L. L L L
= mn L i 0 + i 0 + mn L = 2mn L
Sketch a graph of the periodic function that is represented
by the series. This is an even function, so the b coefficients
vanish. We have looked up the integrals in the table of definite
 L 
L integrals.
1 1 L 1 x 2

L
a0 = |x|dx = xdx =
=
2L L L 0 L 2 0 2
For n  1, Exercise 11.7. Construct a graph with the function f from
  n x    n x  the previous example and c1 1 on the same graph. Let a =
1 L 2 L
an = |x| cos dx = x cos dx 1 for your graph. Comment on how well the partial sum
L L L L 0 L with one term approximates the function.
 L  n x 
L
L

x cos dx = x sin (n x/L)

0 L n 0 f = x 2 x 0.258012 sin ( x)
 L 
L n x 
sin dx
n 0 L Here is the graph, constructed with Excel:
CHAPTER | 11 Functional Series and Integral Transforms e65

If a s 0,

1 1
F(s) = (0 1) =
as sa

as shown in Table 11.1. If a s  0, the integral diverges


and the Laplace transform is not defined.

Exercise 11.11. Derive the version of Eq. (11.49) for


n = 2. Apply the derivative theorem to the first derivative

L{d2 f /dt 2 } = L{ f (2) } = s L{ f (1) } f (1) (0)


Exercise 11.8. Find the Fourier transform of the function = s[s L{ f } f  (0)] f (1) (0)
f (x) = e|x| . Since this is an even function, you can use = s 2 L{ f } s f  (0) f (1) (0)
the one-sided cosine transform.
 
2 x Exercise 11.12. Find the Laplace transform of the function
F(k) = e cos (kx)dx
0
f (t) = t n eat .
This integral is found in the table of definite integrals:
   where n is an integer.
2 x 2 1
F(k) = e cos (kx)dx =  
0 1 + k2
F(s) = t n e(as)t dt = t n ebt
Exercise 11.9. Repeat the calculation of the previous 0 0

1 n! n!
example with a = 0.500 s1 , b = 5.00 s1 Show that dt = n+1 u n eu du = n+1 =
a narrower line width occurs. b 0 b (s a)n+1
The Fourier transform is:
where b = s a and where u = bt and where we have
2 2ab used Eq. (1) of Appendix F.
F() =
[a 2 + (b )2 ][a 2 + (b + )2 ]
2 (5.00 s2 )
F() =
[0.250 s + (5.00 s )2 ][0.250 s2 + (5.00 s1 + )2 ]
2 1
Exercise 11.13. Find the inverse Laplace transform of
Here is the graph of the transform, ignoring a constant
factor: 1
.
s(s 2 + k2)

We recognize k/(s 2 + k 2 ) as the Laplace transform of


cos (kt), so that
 
1 cos (kt)
= L
s2 + k2 k

From the integral theorem


  t   
1 1
L cos (ku)du = L 2 sin (kt)
k 0 k
Exercise 11.10. Find the Laplace transform of the function  
1 cos (kt) 1
f (t) = eat where a is a constant. = L =
s k ks(s 2 + k 2 )
   
1 1
F(s) = eat est dt = e(as)t dt L sin (kt) =
0 0 k s(s + k 2 )
2

 
1 (as)t

1 1
= e
L1 2 2
= sin (kt)
as 0 s(s + k ) k
e66 Mathematics for Physical Chemistry

PROBLEMS 3. Find the Fourier series to represent the function


1. Find the Fourier series that represents the square wave 
e|x/L| L < t < L
 A(t) =
A0 T < t < 0 0 elsewhere
A(t) =
A0 0 < t < T ,
Your series will be periodic and will represent the
function only in the region L < t < L. Since the
where A0 is a constant and T is the period. Make graphs
function is even, the series will be a cosine series.
of the first two partial sums. This is an odd function,
so we will have a sine series:
 
1 L 1 L
a0 = f (x)dx = ex/L dx
an = 0 2L L L 0

L
x/L

bn =
1 T
f (t) sin
n t
dt =
A0 = e
= (e1 1) = (1 e1 )
0
T T T T
 0  T = 0.6321206
n t A0 n t   n x 
sin dt + sin dt 1 L
T T 0 T an = f (x) cos dx
T L L L
 0 
A0 T A0 T 2 L x/L  n x 
= sin (u)du + = e cos dx
T n n T n L 0 L
 n
sin (u)du n x Lu L
u = ; x= ; dx = du
0 L n n
A0 A0  n  u 
= [cos (0) cos ( n )] 2 L
n n an = exp cos (u)du
L n 0 n
[cos (n ) cos (0)] 
2 A0 2 A0 2 exp (u/n )
= [cos (0)cos (n )] = [1 (1)n ] =  1 2
n n n +1
n

2 A0 n t  

n
A(t) = [1 ( 1)n ] sin 1

n T cos (u) + sin (u)

n=1 n

0
4 A0 t 4 A0 3 t
= sin + sin +
T 3 T
where we have used Eq. (50) of Appendix E.

where we have let u = n t/T and dt = (T /n )du


 
and have used the fact that the cosine is an even 2 exp (1) 1
function. Here is a graph that shows the first term (the an =  1 2 cos (n )
n +1 n
first partial sum), the second term, and the sum of these n


two terms (the second partial sum):
+ sin (n )

 
2 exp (0) 1
 1 2 cos (0)
n +1 n
n

+ sin (0)

  
2 exp (1) 1
=  1 2 (1)n
n2 2 + 1 n
n
 
2 1 1
+  1 2
n +1 n
For the graph, we have let A0 equal unity. n
CHAPTER | 11 Functional Series and Integral Transforms e67

 
2 (1)n+1 e1 + 1 5. Find the one-sided Fourier sine transform of the
=  1 2 ax
function f (x) = e x .
n2 2 +1
n
 ax
 1  2 e
1 e +1 F(k) = sin (kx)
a1 = = 0.1258445
 2 0
1
x
2 +1
2 2  
dx = arctan ak
 1 
1 e + 1
a2 = 1
= 0.1115872
4 2 2 +1
where have used Eq. (33) of Appendix F.

7. Find the one-sided Fourier sine transform of the

function aebx
2
f (x) = (1 eL ) +  
n2 2 2
n=1 F(k) = a ebx sin (kx)dx
   0
(1)n+1 e1 1  n x  2 k2
 1 2 cos = a
+1 L b2 + k 2
n
 1 
x  where we have used Eq. (26) of Appendix F.
2 e 1 9. Find the one-sided Fourier sine transform of the
= 0.6321206 +   cos
2 1 2 L 2 2
function f (x) = xea x .
+1
   
2 e1 1 2 x 2 a 2 x 2
+  1 2 cos + F(k) = xe sin (kx)dx
2 L 0
2 + 1 
x  2 m k 2 /(4a 2 ) k 2 k 2 /(4a 2 )
= e = e
= 0.6321206 + 0.1258445 cos 4a 3 4a 3
L
where we have used Eq. (42) of Appendix F.
+ 0.1115872 cos (2 x) +
11. Find the Laplace transform of cos2 (at).

For purposes of a graph, we let L = 1. The following s 2 + 2a 2
est cos2 (ax)dx =
graph shows the function and the third partial sum. It 0 s(s 2 + 2a 2 )
appears that a larger partial sum would be needed for
adequate accuracy. where we have used Eq. (43) of Appendix F
13. Use the derivative theorem to derive the Laplace
transform of cos (at) from the Laplace transform of
sin (at).
d sin (ax)
= a cos (ax)
dx
 
d
L sin (at) = L{a cos (at)}
dt
= s L{sin (at)} sin (0)
as
= 2
s + a2
s
L{cos (at)} = 2
s + a2
This page is intentionally left blank
 

Chapter 12
 

Differential Equations

EXERCISES Division by ex gives the characteristic equation.


Exercise 12.1. An object falling in a vacuum near the 2 3 + 2 = 0
surface of the earth experiences a gravitational force in the This quadratic equation can be factored:
z direction given by
Fz = mg ( 1)( 2) = 0

where g is called the acceleration due to gravity, and is equal The solutions to this equation are
to 9.80 m s2 . This corresponds to a constant acceleration = 1, = 2.

az = g The general solution to the differential equation is


y(x) = c1 e x + c2 e2x
Find the expression for the position of the particle as a
function of time. Find the position of the particle at time Exercise 12.3. Show that the function of Eq. (12.21)
t = 1.00 s if its initial position is z(0) = 10.00 m and its satisfies Eq. (12.9).
initial velocity is vz (0) = 0.00 m s1 z = b1 cos (t) + b2 sin (t)
  z
t1 t1
= b1 sin (t) + b2 cos (t)
vz (t1 ) vz (0) = az (t)dt = gdt = gt1 t
0 0
2z
vz (t1 ) = gt1 = 2 b1 cos (t) 2 b2 sin (t)
 t2  t2 t 2
1
z z (t2 ) z(0) = vz (t1 )dt1 = gt1 dt1 = gt22 d2 z  
0 0 2 m 2 = 2 m b1 cos (t) + b2 sin (t)
dt
1 = kz
z(t2 ) = z(0) gt22
2  
1 Exercise 12.4. The frequency of vibration of the H2
z(10.00 s) = 10.00 m (9.80 m s2 )(1.00 s)2 molecule is 1.3194 1014 s1 . Find the value of the force
2
= 10.00 m 4.90 m = 5.10 m constant.
 
(1.0078 g mol1 )2 1 kg
N Av =
Exercise 12.2. Find the general solution to the differential 2(1.0078 g mol1 ) 1000 g
equation
= 5.039 104 kg mol1
d2 y dy
3 + 2y = 0 5.039 104 kg mol1
dx 2 dx = = 8.367 1028 kg
6.02214 1023 mol1
Substitution of the trial solution y = ex gives the  2
equation k = (2 )2 = 2(1.3194 1014 s1 )
2 ex 3ex + 2ex = 0 (8.367 1028 kg) = 575.1 N m1

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00058-6


2013 Elsevier Inc. All rights reserved. e69
e70 Mathematics for Physical Chemistry

Exercise 12.5. According to quantum mechanics, the Exercise 12.7. If z(0) = z 0 and if vz (0) = 0, express the
energy of a harmonic oscillator is quantized. That is, it can constants b1 and b2 in terms of z 0 .
take on only one of a certain set of values, given by  
  z(t) = b1 cos (t) + b2 sin (t) e t/2m
1
E = h v + z(0) = b1 = z 0
2  
 
where h is Plancks constant, equal to 6.62608 1034 J s, v(t) = b1 cos (t) + b2 sin (t) e t/2m
2m
is the frequency and v is a quantum number, which can  
+ b1 sin (t) + b2 cos (t) e t/2m
equal 0,1,2, . . . The frequency of oscillation of a hydrogen  
molecule is 1.319 1014 s1 . If a classical harmonic
v(0) = b1 + b2 = 0
oscillator having this frequency happens to have an energy 2m
equal to the v = 1 quantum energy, find this energy. What b1 z0
is the maximum value that its kinetic energy can have in this b2 = =
2m 2m
state? What is the maximum value that its potential energy
can have? What is the value of the kinetic energy when the Exercise 12.8. Substitute this trial solution into Eq.
potential energy has its maximum value? (12.39), using the condition of Eq. (12.40), and show that
  the equation is satisfied.
E = h 23 = 23 (6.626081034 J s)(1.3191014 s1 ) The trial solution is
= 1.311 1019 J
z(t) = tet
This is the maximum value of the kinetic energy and also the
maximum value of the potential energy. When the potential We substitute the trial solution into this equation and show
energy is equal to this value, the kinetic energy vanishes. that it is a valid equation.
Exercise 12.6. Show that e1 t does satisfy the differential  
equation. dz d2 z
kz = m
 2  dt dt 2
dz d z    
kz = m et + tet ktet = m et + et + 2 tet
dt dt 2
1 e1 t ke1 t = m21 e1 t
Divide by met
Divide by e 1 t and substitute the expression for 1 into the
equation   k
1 + t t = 2 + t2
 2 m m
/m 4k/m
+ k Replace k/m by ( /2m)2
2m 2
 2
 2 2
[1 + t] t = 2 + t2
/m 4k/m m 2m
= m +  2
2m 2
 [2 + 2t] t = 2 + t2
2 2m 2m
2 /m 4k/m
k Let /2m = u
2m  2 
2 ( /m)2 4k/m u 2 t + [2 + 2t]u + 2 + t2 = 0
=m
2m 2m t2 + (2tu + 2) + u 2 t + 2u = 0

1  2 
+ /m 4k/m Exercise 12.9. Locate the time at which z attains its
4
  maximum value and find the maximum value. The
2 2 m  2 
maximum occurs where dz/dt = 0.
k =m + /m 4k/m
2m 2m 4
2 2 c2 et + c2 tet = 0
= + k
4m 4m Divide by et
2
= k
2m 1.00 m s1 + (1.00 m s1 )(1.00 s1 )t = 0
CHAPTER | 12 Differential Equations e71

At the maximum Exercise 12.13. Solve the equation (4x +y)dx +x dy = 0.


t = 1.00 s Check for exactness
d
(4x + y) = 1
  dy
z(1.00 s) = (1.00 m s1 ) (1.00 s1 )(t = 1.00 s) d
  (x) = 1
dx
exp (1.00 s1 )(t = 1.00 s)
The Pfaffian form is the differential of a function f =
= (1.00 m)e1.00 = 0.3679 m
f (x,y)
Exercise 12.10. If z c (t) is a general solution to the  x1  y1
complementary equation and z p (t) is a particular solution to f (x1 ,y1 ) f (x0 ,y0 ) = (4x + y0 )dx + x1 dy
the inhomogeneous equation, show that z c +z p is a solution 
x0
x1
y0

to the inhomogeneous equation of Eq. (12.1). = 2x 2 + y0 x  + x1 y| y10
y

Since z c satisfies the complementary equation x0


2x12 + y0 x1 2x02 y0 x0 + x1 y1 x1 y0 = 0
d3 z c d2 z c dz c 2x12 2x02 y0 x0 + x1 y1 = 0
f 3 (t) 3
+ f 2 (t) 2
+ f 1 (t) =0
dt dt dt
We regard x0 and y0 as constants
Since z p satisfies the inhomogeneous equation
2x12 + x1 y1 + k = 0
d3 z p d2 z p dz p
f 3 (t) 3 + f 2 (t) 2 + f 1 (t) = g(t)
dt dt dt We drop the subscripts and solve for y as a function of x.
Add these two equations
x y = k 2x 2
d3 d2 k
y = 2x
f 3 (t) (z c + z p ) + f 2 (t) (z c + z p ) x
dt 3 dt 2
d
+ f 1 (t) (z c + z p ) = g(t) This is a solution, but an additional condition would be
dt
required to evaluate k. Verify that this is a solution:
Exercise 12.11. Find an expression for the initial velocity.
dy k
  = 2 2
dz d F0 dx x
vz (t) = = b2 sin (t) + sin (t)
dt dt m( 2 )
2
From the original equation
F0   
= b2 cos (t) + cos (t) dy 4x + y 1
m(2 2 ) =
y
= 4 = 4
k
2x
F0 dx x x x x
vz (0) = b2 +
m(2 2 ) k k
= 4 + 2 + 2 = 2 2
x x
Exercise 12.12. In a second-order chemical reaction
involving one reactant and having no back reaction, Exercise 12.14. Show that 1/y 2 is an integrating factors
for the equation in the previous example and show that it
dc leads to the same solution.
= kc2 .
dt After multiplication by 1/y 2 the Pfaffian form is
Solve this differential equation by separation of variables. 1 x
Do a definite integration from t = 0 to t = t1 . dx 2 dy = 0
y y
1
dc = k dt This is an exact differential of a function f = f (x,y), since
c2
 c(t1 )  t1  
1 1 1 (1/y) 1
2
dc = = k dt = kt1 = 2
c(0) c c(t1 ) c(t0 ) 0 y x y
1 1  
= + kt1 (x/y 2 ) 1
c(t1 ) c(t0 ) = 2
x y y
e72 Mathematics for Physical Chemistry

 x1  y1
1 x1 From the example in Chapter 11 we have the Laplace
f (x1 ,y1 ) f (x0 ,y0 ) = dx 2
dy = 0
x0 y0 y0 y transform
x1 x0 x1 x1
= + =0 z(0)(s + 2a) z (1) (0)
y0 y0 y1 y0 Z= +
y0 y1 (s + a)2 + 2 (s 2 + a)2 + 2
= + =0 z(0)(s + a) az(0) + z (1) (0)
x0 x1 = + .
(s + a)2 + 2 (s + a)2 + 2
We regard x0 and y0 as constants, so that
y y0 where
= =k k
x x0 a= and 2 = a2
2m m
where k is a constant. We solve for y in terms of x to obtain We now apply the critical damping condition
the same solution as in the example:
k
y = kx a2 =
m
Exercise 12.15. A certain violin string has a mass per unit so that
length of 20.00 mg cm1 and a length of 55.0 cm. Find the =0
tension force necessary to make it produce a fundamental
tone of A above middle C (440 oscillations per second =
440 s1 = 440 Hz). z(0)(s + a) z (1) (0) + az(0)
Z= +
nc  n   T 1/2 (s + a)2 (s + a)2
= = From Table 11.1 we have
2L 2L
 
1 1
 2 L = 1
2L s
T =  
1
n
   L1 2 = t
1 kg 100 cm s
= (20.00 mg cm1 )
106 mg 1m From the shifting theorem
 1 2
2(0.550 m)(440 s )  
= 468.5 kg m s2 L eat f (t) = F(s + a)
1
469 N
so that
Exercise 12.16. Find the speed of propagation of a
z (1) (0) + az(0) at
traveling wave in an infinite string with the same mass per z(t) = z(0)eat + te
unit length and the same tension force as the violin string (s + a)2
in the previous exercise.
Except for the symbols for the constants, this is the same
  1/2 as the solution in the text.
469 N mg 106
c = T
= 20.00 mg cm1 1 kg
= 4843 m s1 4840 m s1 Exercise 12.18. The differential equation for a second-
order chemical reaction without back reaction is
Exercise 12.17. Obtain the solution of Eq. (12.1) in the
case of critical damping, using Laplace transforms. dc
= kc2 ,
The equation is dt
 2  where c is the concentration of the single reactant and k
dz d z
kz = m is the rate constant. Set up an Excel spreadsheet to carry
dt dt 2
out Eulers method for this differential equation. Carry out
with the condition. the calculation for the initial concentration 1.000 mol l1 ,
 2 k = 1.000 l mol1 s1 for a time of 2.000 s and for
t =
k 0.100 s. Compare your result with the correct answer.
= .
2m m Here are the numbers from the spreadsheet
CHAPTER | 12 Differential Equations e73

' $
time/s concentration/mol l 1 Write the equation of motion of the object. Find the
general solution to this equation, and obtain the par-
0.0 1
ticular solution that applies if x(0) = 0 and vx (0) =
0.1 0.9 v0 = constant. Construct a graph of the position as a
0.2 0.819 function of time. The equation of motion is
0.3 0.7519239    
d2 x dx
0.4 0.695384945 =
dt 2 m dt
0.5 0.647028923
0.6 0.60516428 The trial solution is
0.7 0.568541899
0.8 0.53621791 x = et
0.9 0.507464946
1.0 0.481712878
t
1.1 0.458508149 2 et = e
m
1.2 0.437485176
The characteristic equation is
1.3 0.418345849
1.4 0.400844524
2 + =0
1.5 0.38477689 m
1.6 0.369971565
The solution is
1.7 0.356283669 
0
1.8 0.343589864 =
m
1.9 0.331784464
2.0 0.320776371 The general solution is
& %
 
t
The result of the spreadsheet calculation is x = c1 + c2 exp
m
c(t) 0.3208 mol l1
The velocity is
Solving the differential equation by separation of variables:    
t
v = c2 exp
dc m m
= k dt
c2

1 c(t) 1 1
 = + = kt  
c c(0) c(t) c(t)
v0 = c2
m
mv0
1 1   c2 =
= + 1.000 l mol 1 1
s (2.000 s)
c(t) 1.000 mol l1
= 3.000 l mol1 The initial position is
1
c(t) = 0.3333 mol l
x(0) = 0 = c1 + c2
mv0
c1 =

PROBLEMS
1. An object moves through a fluid in the x direction. The The particular solution is
only force acting on the object is a frictional force that   
is proportional to the negative of the velocity: mv0 t
x= 1 exp
  m
dx
Fx = x = . For the graph, we let mv0 / = 1, /m = 1.
dt
e74 Mathematics for Physical Chemistry

For a graph, we assume that


vo = 10.00 m s1 ; m = 1.000 kg; F0 = 5.00 N
 
mv0 (1.000 kg) 10.00 m s1
tstop = = = 2.00 s
F0 5.00 kg m s2
For this case
 
kg m s2
x = (10.00 m s1 )t 21 5.001.000 kg
 
t 2 = 10.00 m s1 t (2.500 m s2 )t 2

3. An object sliding on a solid surface experiences a


frictional force that is constant and in the opposite
direction to the velocity if the particle is moving, and is
zero it is not moving. Find the position of the particle as
a function of time if it moves only in the x direction and
the initial position is x(0) = 0 and the initial velocity
is vx (0) = v0 = constant. Proceed as though the
constant force were present at all times and then cut the
solution off at the point at which the velocity vanishes.
That is, just say that the particle is fixed after this time.
5. A less than critically damped harmonic oscillator
Construct a graph of x as a function of time for the case
has a mass m = 0.3000 kg, a force constant
that v0 = 10.00 m s1 . The equation of motion is
k = 98.00 N m1 and a friction constant
d2 x F0 = 1.000 kg s1 .
2
=
dt m a. Find the circular frequency of oscillation and
Except for the symbols used, this is the same as compare it with the frequency that would occur if
the equation of motion for a free-falling object. The there were no damping.
solution is 
 
t t   k 2
v(t1 ) v(0) = 01 az (t)dt = 01 Fm0 dt =
  m 2m
= Fm0 t1 !2 1/2
98.00 N m 1 1.000 kg s 1
 t2
=  
x(t2 ) x(0) = v(t1 )dt1 0.3000 kg 2 0.3000 kg
0
    
t2 F0 = 18.00 s1
= v(0) t1 dt1
0 m Without damping
 t2  
F0 $  1/2
= v(0)t2 t1 dt1 k 98.00 N m1
0 m = = = 18.07 s1
  m 0.3000 kg
1 F0
= v(0)t2 t22 b. Find the time required for the real exponential
2 m factor in the solution to drop to one-half of its
For the case that x(0) = 0, value at t = 0 .
  1
1 F0 e t/2m =
x(t) = t2 2
2 m t
= ln (0.5000) = ln (2.000)
The time at which the velocity vanishes is given by 2m
  2m ln (2.000)
F0 t =
0 = v0 tstop
m  
2 0.300 kg ln (2.000)
mv0 = = 0.4159 s
tstop = 1.000 kg s1
F0
CHAPTER | 12 Differential Equations e75

7. A forced harmonic oscillator with mass m = 0.200 kg 9. An nth-order chemical reaction with one reactant
and a circular frequency = 6.283 s1 (frequency obeys the differential equation
= 1.000 s1 ) is exposed to an external force dc
F0 exp (t) with = 0.7540 s1 . Find the solution = kcn
dt
to its equation of motion. Construct a graph of the
motion for several values of F0 . The solution to the where c is the concentration of the reactant and k
complementary equation is is a constant. Solve this differential equation by
separation of variables. If the initial concentration
z c = b1 cos (t) + b2 sin (t) is c0 moles per liter, find an expression for the time
required for half of the reactant to react.
Table 12.1 gives the trial particular solution  c(t1 )  t1
1
dc = k dt
z p = Aet c(0) c
n
0

1 1 c(t1 )
We need to substitute this into the differential equation = kt1
n 1 cn1 c(0)
d2 z k d2 z F0 exp (t) 1 1
2
+ z = 2 + 2 z = = kt
dt m dt m (n 1) c(t1 )n+1 (n 1) c(0)n+1
1 1
F0 et = + (n 1)kt
A 2 et + 2 Aet = c(t1 )n1 c(0)n1
m
For half of the original amount to react
Divide by et .
2n1 1
F0 n1
= (n 1)kt1/2
A 2 + 2 A = c(0) c(0)n1
m
2n1 1
Solve for A = (n 1)kt1/2
F0 c(0)n1
A=
m(a 2 + 2 )
2n1 1
The solution to the differential equation is t1/2 =
(n 1)kc(0)n+1
F0 et 11. Test the following equations for exactness, and solve
z = b1 cos (t) + b2 sin (t) + the exact equations:
m(a 2 + 2 )
For our first graph, we take the case that b1 = 1.000 m, a. (x 2 + x y + y 2 )dx + (4x 2 2x y + 3y 2 )dy = 0
b2 = 0, and F0 = 10.000 N d 2
(x + x y + y 2 ) = x + 2y
  dy
z = cos (6.283)t d
  (4x 2 2x y + 3y 2 ) = 8x y
(10.000 N) exp (0.7540 s1 )t dx
+  
(0.300 kg) (0.7540 s1 )2 + (6.283 s1 )2 Not exact
= cos[(6.283)t] + 0.8324 exp[(0.7540)t] b.
ye x dx + e x dy = 0
d x
ye = e x
dy
d x
e = ex
dx
This is exact. the Pfaffian form is the differential
of a function, f = f (x,y). Do a line integral as
in the example
  x2  y2
df =0= y1 e x dx + e x2 dy
c x1 y1
= y1 (e x2 e x1 ) + e x2 (y2 y1 ) = 0
Other graphs will be similar. = y1 (e x1 ) + e x2 (y2 )
e76 Mathematics for Physical Chemistry


We regard x1 and y1 as constants, and drop the 1.0
subscripts on x2 and y2 0.86215


1.2084
ye x = C
3.4735
y = Ce x
10.657


where C is a constant 15.653

9.2565
c.
4.1473
[2x y cos (x)]dx + (x 2 1)dy = 0

3.3463

dy 2x y cos (x) 6.6225
=
dx x2 1 18.952
Here is a graph of the values
d
[2x y cos (x)] = 2x
dy
d 2
(x 1) = 2x
dy

This is exact. the Pfaffian form is the differential


of a function, f = f (x,y). Do a line integral as in
the example
  x2  y2
df = 0= [2x y1 cos (x)]dx + (x22 1)dy
c x1 y1
= y1 (x22 x12 ) sin (x2 ) + sin (x1 ) + (x22 1)
(y2 y1 )
= y1 (x12 ) sin (x2 ) + sin (x1 ) + (x22 1)(y2 ) 15. Radioactive nuclei decay according to the same
differential equation that governs first-order chemical
We regard x1 and y1 as constants, and drop the reactions. In living matter, the isotope 14 C is
subscripts on x2 and y2 continually replaced as it decays, but it decays without
replacement beginning with the death of the organism.
y(x 2 1) sin (x) = C The half-life of the isotope (the time required for half
of an initial sample to decay) is 5730 years. If a sample
where C is a constant. of charcoal from an archaeological specimen exhibits
1.27 disintegrations of 14 C per gram of carbon per
C + sin (x) minute and wood recently taken from a living tree
y=
x2 1 exhibits 15.3 disintegrations of 14 C per gram of
carbon per minute, estimate the age of the charcoal.
13. Use Mathematica to obtain a numerical solution to
the differential equation in the previous problem for N (t) = N (0)ekt
the range 0 < x < 10 and for the initial condition 1
y(0) = 1. Evaluate the interpolating function for = ekt1/2
2
several values of x and make a plot of the interpolating kt1/2 = ln (1/2 = ln (2)
function for the range 0 < x < 10.
ln (2) ln (2)
k = = = 1.210 104 y1
dy t1/2 5739 y
+ y cos (x) = e sin (x)
dx The rate of disintegrations is proportional to the
d y + y cos (x) = e sin (x) number of atoms present:
dx
y(0) = 1 N (t) 1.27
= = 0.0830 = ekt
N (0) 15.3
Here are the values for integer values of x from x = 0
to x = 10 kt = ln (0.0830)
CHAPTER | 12 Differential Equations e77

ln (0.0830)
t = = 2.06 104 y
1.210 104 y1
= 20600 y

17. Use Mathematica to obtain a numerical solution to the


pendulum equation in the previous problem without
approximation for the case that L = 1.000 m with
the initial conditions (0) = 0.350 rad (about 20 )
and d/dt = 0. Evaluate the solution for t = 0.500 s,
1.000 s, and 1.500 s. Make a graph of your solution From the graph, the period appears to be about
for 0 < t < 4.00 s. Repeat your solution for (0) = 2.1 s. From the method of the pervious problem
0.050 rad (about 2.9 ) and d/dt = 0. Determine   
L 1.000 m 1/2
the period and the frequency from your graphs. = 2 = 2 = 2.007 s
How do they compare with the solution from the g 9.80 m s2
previous problem? For the second case
   = 9.80 sin ()
d2
L = g sin ()  (0) = 0
dt 2
(0) = 0.050
d2
= 9.80 sin () Here are the values for plotting:
dt 2

(0) = 0.350 0 0.05

0.25 3.5459 102

0.5 2.8968 104
 = 9.80 sin ()
0.75 3.5048 102

 (0) = 0
1.00 4.9997 102

(0) = 0.350 1.25 3.5865 102

1.50 8.6900 104


1.5 8.6900 104
0.5 6.1493 103 =
1.75 3.4632 10 2
1 = 0.34979
2.00 4.9987 102
1.5 0.01844

2.25 3.6266 102

2.50 1.4482 103

0 0.35 2.75 3.4212 102


0.25 0.24996 3.00 4.9970 102

0.5 6.1493 103 3.25 3.6662 102

0.75 0.24122 3.5 2.0272 103


1 0.34979

1.25 0.25839

1.5 0.01844


1.75 0.23219
=
2 0.34914

2.25 0.2665


2.5 3.0708 102

2.75 0.22286

3 0.34808


3.25 0.27429
2

3.5 4.2938 10
3.75 0.21326 The period appears again to be near 2.1 s.
e78 Mathematics for Physical Chemistry

  
19. An object of mass m is subjected to an oscillating t1 F0 F0
force in the x direction given by F0 sin (bt) where F0 x(t1 ) = x(0) + v(0) cos (bt) + dt
0 bm bm
and b are constants. Find the solution to the equation  t1
of motion of the particle. Find the particular solution F0  F0
= x(0) + v(0)t1 2 sin (bt) + t1
for the case that x(0) = 0 and dx/dt = 0 at t = 0. b m 0 bm

d2 x dv = x(0) + v(0)t1
F0
sin (bt1 ) +
F0
t1
m =m = F0 a sin (bt) 2
b m bm
dt 2 dt
 
F0 F0
dv F0 x(t) = x(0) + v(0) + t 2 sin (bt)
= sin (bt) bm b m
dt m
 For the case that x(0) = 0 and dx/dt = 0 at t = 0.
F0 t1  
v(t1 ) = v(0) + sin (bt)dt F0 F0 F0 1
m 0 x(t) = t 2 sin (bt) = t sin (bt)
F0 bm b m bm b
= v(0) cos (bt1 )|t01
bm
F0  
= v(0) cos (bt1 ) 1
bm
 

Chapter 13
 

Operators, Matrices, and Group Theory

d2
EXERCISES Exercise 13.3. Find the commutator [x 2 , ].
dx 2
Exercise 13.1. Find the eigenfunctions and eigenvalues of d2 2 d
2 d2 2
d [x 2 , ] f = x f (x f )
the operator i , where i = 1. dx 2 dx 2 dx 2
dx 2  
2d f d 2df
= x 2x f + x
df dx 2 dx dx
i = af d2 f df 2
dx 2d f
= x2 2 f 2x x
dx 2 dx dx 2
Separate the variables: df
= 2 f 2x
dx
df df a  2 
dx = = = ia d d
dx f i x 2 , 2 = 2 2x
dx dx
ln ( f ) = iax + C
f = eC eiax = Aeiax  = x + d , find A
Exercise 13.4. If A 3 .
dx
df    
= ia Aeiax = ia f
dx 3 = x + d
A x+
d
x+
d
dx dx dx
  
The single eigenfunction is Aeiax and the eigenvalue is d d d d2
= x+ x2 + x+x + 2
ia. Since no boundary conditions were specified, the dx dx dx dx
constants A and a can take on any values.
d d d2 d 2 d2
= x3 + x x + x2 +x 2 + x + 2x
dx dx dx dx dx
Exercise 13.2. Find the operator equal to the operator d d d 3
d2 + x + 3.
product 2 x. dx dx dx
dx
Exercise 13.5. Find an expression for  B 2 if 
B = x(d/dx)
  and find  2
B f if f = bx . 4
d2 d df d2 f df df
x f = x + f = x + +    
dx 2 dx dx dx 2 dx dx
 d 2 d df
B2 f = x f =x x
d2 f df dx dx dx
= x +2  2 
dx 2 dx df d f df d2 f
= x +x 2 =x + x2 2
dx dx dx dx
The operator equation is  
df 2
d f

B 2 (bx 4 ) = x + x 2 2 bx 4
d2 d2 d dx dx
x = x +2
dx 2 dx 2 dx = 4bx 4 + x 2 (4)(3)bx 2 = 16bx 4
Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00059-8
2013 Elsevier Inc. All rights reserved. e79
e80 Mathematics for Physical Chemistry

Exercise 13.6. Show that the solution in the previous 2(x) (1,2, 3).
Exercise 13.10. Find C
example satisfies the original equation.
2(z) (1,2, 3) = ( 1, 2, 3)
C
d2 y dy
3 + 2y = 0
dx 2 dx Exercise 13.11. Find 
S2(y) (3,4,5).
d2  2x  d  2x 
c 1 e + c 2 e x
3 c1 e + c2 e x 
S2(y) (3,4,5) = ( 3. 4, 5)
dx 2   dx
+2 c1 e2x + c2 e x Exercise 13.12. List the symmetry elements of a uniform
  cube centered at the origin with its faces perpendicular to
= 4c1 e2x + c2 e x 3 2c1 e2x + c2 e x the coordinate axes.
 
+ 2 c1 e2x + c2 e x = 0 The inversion center at the origin.
Three C4 axes coinciding with the coordinate axes.
Exercise 13.7. Find the eigenfunction of the Hamiltonian Four C3 axes passing through opposite corners of the cube.
operator for motion in the x direction if V (x) = E 0 = Four S6 axes coinciding with the C3 axes.
constant. Six C2 axes connecting the midpoints of opposite edges.
  Three mirror planes in the coordinate planes.
 2
+ E 0 = E Six mirror planes passing through opposite edges.
2m x 2
2 2m
Exercise 13.13. List the symmetry elements for
= E E 0 = 2
x2 
a. H2 O (bent)
where we let E,C2(z) ,x z , yz
2m
2 = (E E 0 ) b. CO2 (linear)

E,i,h ,C(z) ,C2 ,h ,v
If E  E 0 the real solution is
Exercise 13.14. Find  i2 px where  i is the inversion
real = c1 sin ( x) + c2 cos ( x)
operator. Show that 2 px is an eigenfunction of the
In order for real to be an eigenfunction, either c1 or c2 has inversion operator, and find its eigenvalue.
to vanish. Another version of the solution is  
 (x 2 + y 2 + z 2 )1/2
i2 px = i x exp
complex = b1 ei x + b2 ei x 2a0
 
In order for complex to be an eigenfunction, either b1 or b2 (x + y 2 + z 2 )1/2
2
= x exp = 2 px
has to vanish. 2a0
The eigenvalue is equal to 1.
Exercise 13.8. Show that the operator for the momentum
in Eq. (13.19) is hermitian. Exercise 13.15. The potential energy of two charges Q 1
We integrate by parts and Q 2 in a vacuum is

 d   d Q1 Q2
dx = dx V=
i dx i i dx 4 0 r12

 d
= dx where r12 is the distance between the charges and 0
i dx is a constant called the permittivity of a vacuum, equal
The other side of the equation is, after taking the complex to 8.854187817 1012 Fm1 = 8.854187817
conjugate of the operator 1012 C2 N1 m2 . The potential energy of a hydrogen
molecules is given by
 d
dx
i dx e2 e2 e2 e2
V =
4 0 r AB 4 0 r1A 4 0 r1B 4 0 r2 A
which is the same expression.
e2 e2
Exercise 13.9. Write an equation similar to Eq. (13.20) for +
4 0 r2B 4 0 r12
the v operator whose symmetry element is the y-z plane.
where A and B represent the nuclei and 1 and 2 represent
v(yz) (x1 ,y1 ,z 1 ) = ( x1 ,y1 ,z 1 ) the electrons, and where the two indexes indicate the
CHAPTER | 13 Operators, Matrices, and Group Theory e81


two particles whose interparticle distance is denoted. If a 1 2 3 0 2 2
hydrogen molecule is placed so that the origin is midway
A = 4 5 6 B = 3 1 2
between the two nuclei and the nuclei are on the z axis, show 7 8 9 1 2 3
that the inversion operator and the reflection operator h
do not change the potential energy if applied to the electrons 1 0 1
but not to the nuclei.
C = 0 3 2
We use the fact that the origin is midway between the 2 7 7
nuclei. Under the inversion operation, electron 1 is now the
0 2 2 1 0 1
same distance from nucleus A as it was originally from
BC = 3 1 2 0 3 2
nucleus B, and the same is true of electron 2. Under the h
operation, the same is true. The potential energy function 1 2 3 2 7 7
is unchanged under each of these operations.
4 20 18

= 1 17 19
Exercise 13.16. Find the product
5 27 26

1 2 3 4 20 18
1 0 2 0 2
A(BC) = 4 5 6 1 17 19

0 1 1 3 = 2 7 8 9 5 27 26
0 0 1 1 1
9 27 22

= 9 3 11
Exercise 13.17. Find the two matrix products 9 33 44

1 2 3 0 2 2 3 2 3

AB = 4 5 6 3 1 2 = 9 1 0
1 2 3 1 3 2 1 3 2
7 8 9 1 2 3 15 4 3
3 2 1 2 2 1 and 2 2 1
1 1 2 2 1 1 2 1 1 3 2 3 1 0 1

1 2 3 (AB)C = 9 1 0 0 3 2
15 4 3 2 7 7
3 2 1

1 1 2 9 27 22

= 9 3 11 .
The left factor in one product is equal to the right factor 9 33 44
in the other product, and vice versa. Are the two products
equal to each other?

1 2 3 0 2 2 1 0 1

1 2 3 1 3 2 1 10 3 4 5 6 3 1 2 + 0 3 2

3 2 1 2 2 1 = 5 14 3 7 8 9 1 2 3 2 7 7
1 1 2 2 1 1 5 3 1
4 25 27
1 3 2 1 2 3 12 6 10
= 7 58 48

2 2 1 3 2 1 = 7 9 6 . 10 91 69
2 1 1 1 1 2 6 5 9
1 2 3 0 2 2 1 2 3 1 0 1

4 5 6 3 1 2 + 4 5 6 0 3 2
The two products are not equal to each other. 7 8 9 1 2 3 7 8 9 2 7 7

3 2 3 7 27 24 4 25 27

= 9 1 0 + 16 57 48 = 7 58 48
Exercise 13.18. Show that the properties of Eqs. (13.45)
and (13.46) are obeyed by the particular matrices 15 4 3 25 87 72 10 91 69
e82 Mathematics for Physical Chemistry

Exercise 13.19. Show by explicit matrix multiplication Exercise 13.23. Expand the following determinant by
that minors:

1 0 0 0 a11 a12 a13 a14 a11 a12 a13 a14 3 2 0

0 1 0 0 a21 a22 a31 a41 a21 a21 a31 a41 1 5 7 5
= . 7 1 5 = 3 2
0 0 1 0 a31 a31 a31 a41 a31 a31 a31 a41 3 4 2 4
2 3 4
0 0 0 1 a41 a41 a31 a41 a41 a41 a31 a41
= 3( 4 15) 2(28 10) = 93
:Each element is produces as a single term since the other
terms in the same contain a factor zero. Exercise 13.24. a. Find the value of the determinant

Exercise 13.20. Show that AA1 = E and that A1 A = E 3 4 5

for the matrices of the preceding example.
2 1 6 = 47

Mathematica and other software packages can find a 3 5 10
matrix product with a single command. Using the Scientific
Work Place software b. Interchange the first and second columns and find the
value of the resulting determinant.
3 1 1

2 1 0 4 2 4 1 0 0 4 3 5

1 1
AA1 = 1 2 1 2 1 2 = 0 1 0 1 2 6 = 47

0 1 2 1 0 0 1 5 3 10
1 3

4 2 4 c. Replace the second column by the sum of the first
3 1 1
and second columns and find the value of the resulting
4 2 4
2 1 0 1 0 0 determinant.
1
1 7 4 5
A1 A = 2 1 2 1 2 1 = 0 1 0




3 1 6 = 47
0 1 2 0 0 1
1 1 3 2 5 10

4 2 4
d. Replace the second column by the first, thus making
Exercise 13.21. Use Mathematica or another software two identical columns, and find the value of the
package to verify the inverse found in the preceding resulting determinant.
example. Using the Scientific Work Place software

3 1 1 3 3 5

1 4
2 4 2 2 6 = 0
2 1 0
1 1 3 3 10
1 2 1 = 1
2 2
0 1 2 Exercise 13.25. Obtain the inverse of the following matrix
1 1 3
by hand. Then use Mathematica to verify your answer.
4 2 4
Exercise 13.22. Find the inverse of the matrix
  1
1 3 0 2 0 3
12
A=
3 4 3 0 4 = 1 0 1
3 1 9
1 2 0
Using the Scientific Work Place software, 2 4 4

 1 1 3 0 2 0 3 1 0 0
2 1 1 0 1
1 2
= 3 3 0 4 3 1 9 = 0 1 0
A1 = 1
3 4 1 2 0 0 0 1
2 2 2 4 4
Check this
   
2 1 Exercise 13.26. Obtain the multiplication table for the C2v
1 2 1 0
3 1= point group and show that it satisfies the conditions to be a
3 4 0 1
2 2 group.
CHAPTER | 13 Operators, Matrices, and Group Theory e83

Think of the H2 O molecule, which possesses all of the c. Find the matrix equivalent to h .
symmetry operators in this group. Place the molecule in
the y z plane with the rotation axis on the z axis. Note x = x
that in this group, each element is its own inverse. For the y = y
other operators, one inspects the action of the right-most z  = z
operator, followed by the action of the left-most operator.
If the result is ambiguous, you need to use the fact that a 1 0 0
reflection changes a right-handed system to a left-handed h 0 1 0
system while the rotation does not. For example,  v(yz) 0 0 1
followed by  v(x z) exchanges the hydrogens, but changes
the handedness of a coordinate system, so the result is the Exercise 13.28. By transcribing Table 13.1 with appropri-
same as  v(x z) . ate changes in symbols, generate the multiplication table for
the matrices in Eq. (13.65).
' $
E A B C D F

E 
C2 
v(yz) 
v(xz) E E A B C D F

E 
E 2
C 
v(yz) 
v(xz) A A B E F C D
2
C 2
C 
E 
v(xz) 
v(yz) B B E A D F C

v(yz) 
v(yz) 
v(xz) 
E 2
C C C D F E A B

v(xz) 
v(xz) 
v(xz) 2
C 
E D D D F C E A
& % F F C D A B E

These operators form a group because (1) each product Exercise 13.29. Verify several of the entries in the
is a member of the group; (2) the group does include the multiplication table by matrix multiplication of the matrices
identity operator; (3) because each of the members is its in Eq. (13.65).
own inverse; and (4) multiplication is associative.

1/2 3/2 0 1/2 3/2 0

Exercise 13.27. AB = 3/2 1/2 0 3/2 1/2 0
2 (z).
a. Find the matrix equivalent to C 0 0 1 0 0 1

1 0 0
x  = x
= 0 1 0 = E
y  = y 0 0 1
z = z
1/2 3/2 0 1/2 3/2 0
1 0 0
AD = 3/2 1/2 0 3/2 1/2 0
2 (z) 0 1 0
C
0 0 1 0 0 1
0 0 1 1 1
30
2 2
b. Find the matrix equivalent to 
S3 (z).

= 1 1
3 0 = C
1 2 2
x  = cos (2/3)x sin (2/3)y = x 00 1
  2

1 1/2 3/2 0 1/2 3/2 0
3 y
2 CD = 3/2 1/2 0 3/2 1/2 0
 
1 1 0 0 1 0 0 1
y  = sin (2/3)x + cos (2/3)y = 3 x y
2 2 1 1
z  = z. 3 0
2 2

1/2 3/2 0 = 1 1
 3 0 = A
S3 (z) 3/2 1/2 0 2 2
0 0 1 0 0 1
e84 Mathematics for Physical Chemistry

Exercise 13.30. Show by matrix multiplication that two df


= cos (x) f + sin (x)
matrices with a 2 by 2 block and two 1 by 1 blocks produce dx
another matrix with a 2 by 2 block and two 1 by 1 blocks df
sin (x) = cos (x) f
when multiplied together.  dx 
d
a b 0 0 0 0 a + b a + b 0 0 , sin (x) = cos (x)
dx
c d 0 0 0 0 c + d c + d 0 0
=
0 0 e 0 0 0 0 0 0 e 0  
d2
0 0 0 f 0 0 0 0 0 0 f b. ,x ;
dx 2
Exercise 13.31. Pick a few pairs of 2 by 2 submatrices
 
from Eq. (13.65) and show that they multiply in the same d2 d2 d2
way as the 3 by 3 matrices. ,x f = [x f ] x 2 f
dx 2 dx 2 dx
      
1/2 3/2 1/2 3/2 1 0 d df d2
= = x + f x 2 f
3/2 1/2 3/2 1/2 0 1 dx dx dx
1 1 df d2 df d2
   = +x 2 f + x 2 f
3
1/2 3/2 1/2 3/2 dx dx dx dx
= 2 2
df
3/2 1/2 3/2 1/2 1 1 = 2
3 dx
2 2  2 
1 1 d d
   
3 ,x = 2
1/2 3/2 1/2 3/2 2 2 dx 2 dx
= .
3/2 1/2 3/2 1/2 1 1
3 3. The components of the angular momentum correspond
2 2
Exercise 13.32. Show that the 1 by 1 matrices (scalars) in to the quantum mechanical operators:
Eq. (13.67) obey the same multiplication table as does the    
   
group of symmetry operators. Lx = y z , Ly = z x ,
i z y i x z
Since the elements E  1 C 3 1 C 2 1,  
3
 
the product of any two of these will yield +1. Since Lz = x y .
a 1 b 1 c 1, the product of any two of i y x
these will yield 1. The product of any of the first three with
These operators do  not commute with each other. Find
any of the second three will yield 1. the multiplication
the commutator  L x ,
Ly .
table is
' $

L x ,
Ly f

E 
C3 
C32 a b c    
 

E 1 1 1 1 1 1 = y z z x f
i z y i x z

C3 1 1 1 1 1 1    
 

C3 2 1 1 1 1 1 1 z x y z f
i x z i z y
a 1 1 1 1 1 1 
2 f f f
b 1 1 1 1 1 1 =  y z y x z z
z x z z y x
c 1 1 1 1 1 1 f f f
& % +z x z y +z z
y z x z x y

f f
x z +x y
z y z z
PROBLEMS  2
f f 2 f 2 f
= 2 yz +y x y 2 z2
1. Find the following commutators, where Dx = d/dx: z x z z y x
  2f 2f 2f
d
a. dx , sin (x) ;
+ zx zy + z2
  yz xz x y
d d df 2 2 
, sin (x) f = [sin (x) f ] sin (x) f f f
dx dx dx +zy x x z
z 2 y z y
CHAPTER | 13 Operators, Matrices, and Group Theory e85

 
We can now apply Eulers reciprocity relation to cancel c. The operator corresponding to px is i ddx .
all of the terms but two: Find the expectation value of px .
    a
 f f  2 x  d x 
  2
L x , L y f =  y x
z y  px = sin sin dx
  i a 0 a dx a
f f x  x 
2
=  x y = i Lz 2 a
y z = sin cos dx
ia a 0 a a

5. In quantum mechanics, the expectation value of a 2 a
= sin (u) cos (u)du
mechanical quantity is given by ia a 0

! 2 sin (u)
A dx = =0
A = ! , ia 2 0
dx
d. Find the expectation value of px2 .
where A  is the operator for the mechanical quantity a  x  d2 x 
and is the wave function for the state of the system. 2 22
 px =  sin sin dx
The integrals are over all permitted values of the a 0 a dx 2 a
a x  d x 
coordinates of the system. The expectation value is 2
=  sin cos dx
defined as the prediction of the mean of a large number aa 0 a dx a

of measurements of the mechanical quantity, given that 2  2 a 2  x 
the system is in the state corresponding to prior to = 2 sin dx
a a 0 a

each measurement. 2  2  a  2
For a particle moving in the x direction only and = 2 sin (u)du
a a 0
confined to a region on the x axis from x = 0 to x = a, 

the integrals are single integrals from 0 to a and px is 2 x sin 2x
= 2 2
given by (/i)/ x. The normalized wave function is a 2 4
0
"
2 x  2   2 2 h2
= sin = 2 2 = =
a a a 2 a2 4a 2
7. If x is an ordinary variable, the Maclaurin series for
Normalization means that the integral in the
1/(1 x) is
denominator of the expectation value expression is
equal to unity. 1
= 1 + x2 + x3 + x4 + .
1x
a. Show that this wave function is normalized. We
let u = x/a If 
X is some operator, show that the series
1+ 
X+
X2 + 
X3 + 
X4 +
2 a 2 x  2 a 2

sin dx = sin u du
a 0 a a 0 is the inverse of the operator 1 
X.


2 x sin 2x 2
 
= = =1 1 X 1+  X+ X2 +  X3 + 
X4 +
2 4 2
0 =1+ X+X2 + 
X3 + 
X4 +
 
b. Find the expectation value of x. X+X2 + 
X3 + 
X4 + = 1
x  x 
2 a 9. Find the result of each operation on the given point
x = sin x sin dx
a 0 a a (represented by Cartesian coordinates):
x   
2 a
= x sin2 dx 3(z) (1,1,1) = 1 , 1 3.1
a. C
a 0 a 2 2

2  a 2
b. 
S4(z) (1,1,1) = (1, 1, 1)
= u sin2 u du
a 0

 11. Find the result of each operation on the given point
2a x 2 x sin (2x) cos 2x (represented by Cartesian coordinates):
= 2
4 4 8 2(z) (1,1,1) = C2(z) ( 1, 1, 1)
0 a. C
 2 
2a 1 1 a = (1, 1, 1)
= 2 + = 2(z) (1,1,1) = ( 1, 1,1) = (1,1, 1)
4 8 8 2 b. C
e86 Mathematics for Physical Chemistry

13. Find the 3 by 3 matrix that is equivalent in its action 19. Show that A(B + C) = AB + AC for the example
to each of the symmetry operators: matrices in the previous problem.
8 (x): Let = /8 45
a. C 3 1 4 0 3 1

x = x B + C = 2 0 1 + 4 2 3
1 3 2 1 3 1 2
y  = cos ()y + sin ()z = (y + z)
2 3 4 5
1
z  = sin ()y + cos ()z = (y + z) = 6 2 4
2 6 3 1

1 0 0 0 1 2 3 4 5
1
A(B + C) = 3 1 4 6 2 4
8 (x) 0
C
0
2 2 3 1 6 3 1
1
0 0
2 6 8 2

b. 
S6 (x): Let = /3 60 = 21 2 23
6 17 21
 1 3
x = cos ()x sin ()y = x y 0 1 2 3 1 4
2
2
AB = 3 1 4 2 0 1
3 1
y  = sin ()x + cos ()y = x+ y 2 3 1 3 2 1
2 2
z  = z. 4 4 3

1 3 = 5 5 9
0 3 4 12
2 2
8 (x) 3 1
C
0 0 1 2 0 3 1
2 2
AC = 3 1 4 4 2 3
0 0 1
2 3 1 3 1 2
15. Give the function that results if the given symmetry
2 4 1
operator operates on the given function for each of the
following: = 16 7 14
9 13 9
a. (x + y + z 2 ) = ( x y + z 2 )
b. 
S4(x) (x + y + z) = x + z y 4 4 3

AB + AC = 5 5 9
17. Find the matrix products. Use Mathematica to check 3 4 12
your result.
2 4 1 6 8 2
1 2 3 1 2 3
+ 16 7 14 = 21 2 23
  0 3 4 0 3 4
9 13 9 6 17 21
a. 3 2 1 4 =
1 2 1 1 2 1
3 1 0 3 1 0 21. Test the following matrices for singularity. Find the

1 2 3 17 inverses of any that are nonsingular. Multiply the
2 original matrix by its inverse to check your work. Use
0 3 4 3
b. 3 = Mathematica to check your work.
1 2 1 1
3
3 1 0 9 3 2 1

  1 4 7 3
a. 4 6 3
6 3 1
c. 2 5 8 2 7 2 1
7 4 2
3 6 9 1
  3 2 1
9 33 9 11
=
9 36 1 11 4 6 3 = 48

7 2 1
CHAPTER | 13 Operators, Matrices, and Group Theory e87

Not singular
1 0 0

1 1
2
C 0 1 0

1 0
3 2 1 4 4 0 0 1

17 1 5
4 6 3
48 12 48 1 0 0
7 2 1 25 1 13
a 0 1 0
24 6 24 0 0 1

1 0 0
1 1
0 b 0 1 0
3 2 1 4 4 1 0 0

17 1 5 0 0 1
4 6 3 = 0 1 0.
48 12 48 b. Show that the matrices obtained in part (a)
7 2 1 25 1 13 0 0 1
have the same multiplication table as the
24 6 24 symmetry operators, and that they form a group.
The multiplication table for the group was to
0 2 3
be obtained in an exercise. The multiplication
b. 1 0 1 table is
2 0 1
0 2  2  v(yz) v(x z)
3
E C


E 
E 2 
C v(yz) v(x z)
1 0 1 = 2

C2 
C2 
E  v(x z) 
v(yz)
2 0 1

v(yz) v(yz) 
v(x z) E 2
C
Not singular  

v(x z) 
v(x z) 
v(yz) C2 E
1
0 2 3 0 1 1 where  v(yz) = a and 
v(x z) =b . We perform
1 3
1 0 1 = 2 3
a few of the multiplications.
2
2 0 1 0 2 1 1 0 0 1 0 0

a b 0 1 0 0 1 0
Check:
0 0 1 0 0 1

0 2 3 0 1 1 1 0 0
1
3 1 0 0

1 0 1 3 = 0 1 0. = 0 1 0 C 2
2 2
2 0 1 0 2 1 0 0 1 0 0 1

23. The H2 O molecule belongs to the point group C2v , 1 0 0 1 0 0

2
 C2 , a , 2
C

0 1 0 0 1 0

which contains the symmetry operators E,
and b , where the C2 axis passes through the oxygen 0 0 1 0 0 1
nucleus and midway between the two hydrogen nuclei,
1 0 0
and where the a mirror plane contains the three nuclei 
= 0 1 0 E
and the b mirror plane is perpendicular to the a
mirror plane. 0 0 1

1 0 0 1 0 0
a. Find the 3 by 3 matrix that is equivalent to each 2
C v(x z) 0 1 0 0 1 0
symmetry operator.
0 0 1 0 0 1

1 0 0 1 0 0

E 0 1 0

= 0 1 0  v(yz)
0 0 1 0 0 1
 

Chapter 14
 

The Solution of Simultaneous


Algebraic Equations with More
Than Two Unknowns

EXERCISES Exercise 14.3. Find the values of x2 and x3 for the previous
example.
Exercise 14.1. Use the rules of matrix multiplication to


2 21 1

show that Eq. (14.3) is identical with Eqs. (14.1) and (14.2).







1 4 1

4 1

1 1

1 4



2

21

+ 1


1 10 1

10 1

1 1

1 10

x2 =

=




   c1
2 4 1








1 1

4 ]

4 ]



2

1

+ 1

a11 a12 x1
=
1 1 1

1 1

1 1

1 1

a21 a22 x2
1 1 1

c2 2(4 10) 21(0) + 10 4 6


a11 x1 + a12 x2 = c1 = = =3
2( 1 1) (4 1) + (4 + 1) 2
a21 x1 + a22 x2 = c2


2 4 21


1 1 4

1 4

4 21

4 21



2

1

+ 1

Exercise 14.2. Use Cramers rule to solve the simultane-


1 1 10

1 10

1 10

1 4

x3 =

=




ous equations
2 4 1








1 1

4 ]

4 ]



2

1

+ 1


1 1 1

1 1

1 1

1 1

4x + 3y = 17
1 1 1

2x 3y = 5 2( 10 4) 1(40 21) + 1(16 + 21)




=


2( 1 1) (4 1) + (4 + 1)

17 3



10

5 3
51 + 15 36 = =5
x =

= = =2 2


12 6 18

4 3



Exercise 14.4. Find the value of x1 that satisfies the set of

2 3



equations




4 17



1 1 1 1 x1 10

2 5
20 34 54
y =

= = =3 1 1 1 1 x2 6


12 6 18 =

4 3
1 1 1 1 x3 4


2 3
1 1 1 1 x4 1

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00060-4


2013 Elsevier Inc. All rights reserved. e89
e90 Mathematics for Physical Chemistry



3

1 1 1 1

1 1

1


4 2 4

1 1 1 1
2 1 0


= 8 1 1

1 1 1 1

1 2 1 = 1

2

1 1 1 1
2
0 1 2


1 1 3

10 1 1 1



4 2 4


6 1 1 1
3


= 4 1 1

4 1 1 1

3

4 2 4

1 1 1 1
4
1
1
2
2 1 7 = 1
2
7
4 1 8
x1 = = 1 1 3 2
8 2
4 2 4
The complete solution is The solution is
1 3 7
x1 = , x2 = 1, x3 =
2 2
2
Exercise 14.7. Use GaussJordan elimination to solve the
2
set of simultaneous equations in the previous exercise. The
X=



3 same row operations will be required that were used in
Example 13.16.
9
2x1 + x2 = 1
2
x1 + 2x2 + x3 = 2
x2 + 2x3 = 3
Exercise 14.5. Determine whether the set of four
In matrix notation
equations in three unknowns can be solved:
AX = C

x1 + x2 + x3 = 12 2 1 0 x1 1
4x1 + 2x2 + 8x3 = 52
1 2 1 x2 = 2
3x1 + 3x2 + x3 = 25 0 1 2 x3 3
2x1 + x2 + 4x3 = 26 The augmented matrix is

..
We first disregard the first equation. The determinant of the 2 1 0 . 1

coefficients of the last three equations vanishes: .
1 2 1 .. 2




4 2 8
..


0 1 2 . 3


3 3 1
= 0


1

2 1 4
We multiply the first row by , obtaining
2

These three equations are apparently linearly dependent. 1 . 1.
21 0 .
We disregard the fourth equation and solve the first three 2
equations. The result is: .. .
1 2 1 . 2

.
5 11 0 1 2 .. 3
x1 = , x2 = 9, x3 =
2 2 We subtract the first row from the second and replace the
second row by this difference. The result is
Exercise 14.6. Solve the simultaneous equations by
matrix inversion 1 .. 1
1 2 0 . 2

2x1 + x2 = 4 3 . 3
0 .
1 . .

x1 + 2x2 + x3 = 7 2 2
.
x2 + 2x3 = 8 0 1 2 .. 3
CHAPTER | 14 The Solution of Simultaneous Algebraic Equations with More Than Two Unknowns e91

1 1
We multiply the second row by We now multiply the third row by ,
3 2

1 .. 1 1 .. 1
1 2 0 . 2 1 0 3 . 2

1 1 . 1 ..
.
0 . . 0 1 0 . 0

2 3 2

.. 1 .. 1
0 1 2 . 3 0 0 .
3 2
We replace the first row by the difference of the first row We add the third row to the first row, and replace the first
and the second to obtain row by the sum. The result is

1 .. .. 1
1 0 . 0

3
1 0 0 . 2
1 1 . 1
..
0 .
. .
2 3 0 1 0 . 0 .
2

.. 1 .. 1
0 1 2 . 3 0 0 .
3 2
We multiply the second row by 2,
We multiply of the third row by 3 to obtain

1 .. .. 1
1 0 . 0 1 0 0 .
3 2

2 .. ..
0 1 . 1.
0 1 0 . 0 .

3

.. .. 3
0 1 2 . 3 0 0 1 .
2
We subtract the second row from the third row, and replace
We now reconstitute the matrix equation. The left-hand side
the third row by the difference. The result is
of the equation is EX and the right-hand side of the equation

1 .. is equal to X.
1 0 3 . 0 AX = C


2 .. EX = C = X
0 1 . 1.
3 1
2
4 ..
0 0 . 2
3 EX = X =
0 .

1 3
We now multiply the third row by ,
2 2

1 .. The solution is
1 0 3 . 0 1 3
x1 = , x2 = 0, x3 =

2 .. 2 2
0 1 . 1.
3 Exercise 14.8. Find expressions for x and y in terms of z

2 .. for the set of equations
0 0 . 1
3 2x + 3y 12z = 0
We subtract the third row from the second and replace the xyz = 0
second row by the difference, obtaining
3x + 2y 13z = 0

1 ..
1 0 . 0 The determinant of the coefficients is
3

..
2 3 12

0 1 0 . 0.

2 ..
1 1 1
= 0
0 0 . 1


3 2 13

3
e92 Mathematics for Physical Chemistry

Since the determinant vanishes, this system of equations can PROBLEMS


have a nontrivial solution. We multiply the second equation
by 3 and add the first two equations: 1. Solve the set of simultaneous equations:

5x 15z = 0 3x + y + 2z = 17
x = 3z x 3y + z = 3
x + 2y 3z = 4
We multiply the second equation by 2 and subtract the
second equation from the first: Find the inverse matrix
1 1 1
5y 10z = 0
1 5 5 5
y = 2z 3 1 2
4 11 1
1 3 1 =
Exercise 14.9. Show that the second eigenvector in the
35 35 35
previous example is an eigenvector. 1 2 3
1 1 2

2 1 0 1/2 0 7 7 7

1 2 1 1/ 2 = 0 :
1
0 1 2 1/2 0 1 1
5 5 5
Exercise 14.10. Find the third eigenvector for the previous 17 2
4 11 1
example. 3
= 3
35 35 35

2x1 + x2 + 0 = 0 4 4
1 1 2
x1 2x2 + x3 = 0
7 7 7
0 + x2 2x3 = 0
x = 2, y = 3, z = 4
The solution is:
:
x1 = x3 , x2 = x3 2 3. Solve the set of equations, using Cramers rule:
With the normalization condition 3x1 + x2 + x3 = 19
x32 + 2x32 + x32 = 4x32 x1 2x2 + 3x3 = 13
x1 + 2x2 + 2x3 = 23

1
19 1 1

x1 = x3 =


13 2 3

2 1

x2 = =
23 2 2
75
2 2 x1 =

= =3

3 1 1
25

1/2


1 2 3

X = 1/ 2


1 2 2

1/2


3 19 1

Exercise 14.11. The Hckel secular equation for the



1 13 3

hydrogen molecule is




1 23 2
100


x2 =

= =4

W

3 1 1
25


=0


1 2 3

Determine the two orbital energies in terms of and .


1 2 2

x 1
3 1 19

= 0 = x2 1

1 x


1 2 13


1 2 23
150
x = 1 x3 =

= =6

3 1 1
25


1 2 3

W =

+
1 2 2

CHAPTER | 14 The Solution of Simultaneous Algebraic Equations with More Than Two Unknowns e93

Verify your result using Mathematica. The determinant of the coefficients is



2 1
3 4 1

1 0

5 5
4 3 2
= 0
3 1 1

1 1 8
7 7 3

1 2 3 =
25 5 25


A solution of x and y in terms of z is possible. Solve
1 2 2
4 1 7 the first two equations

25 5 25     
2 3 4 x 13 z
1 =
0 4 3 y 10 2z
5 5
19 3
1 1 8 Use Gauss-Jordan elimination. Construct the aug-
13

= 4
25 5 25 mented matrix

23 6
4 1 7 ..
3 4 . 13 z
25 5 25
..
5. Solve the equations: 4 3 . 10 2z
Multiply the first equation by 3 and the second
3x1 + 4x2 + 5x3 = 25
equation by 4:
4x1 + 3x2 6x3 = 7
x1 + x2 + x3 = 6 ..
9 12 . 39 3z
..
In matrix notation 16 12 . 40 8z

3 4 5 x1 25 Subtract the first line from the second line and replace
the first line by the difference
4 3 6 x2 = 7

1 1 1 x3 6 ..
7 0 . 1 5z
The inverse matrix is ..
16 12 . 40 8z
9 1 39

Multiply the first line by 16 and the second line by 7
1 8 8 8
3 4 5
5 1 19 ..
112 0 . 16 80z
4 3 6 =
4 4 4 ..
1 1 1 112 84 . 280 56z
1 1 7

8 8 8 Subtract the first line from the second line and replace
the second line by the difference
9 1 39
..
8 8 8

5 1
25 2 112 0 . 16 80z
19
.
4 4 7 = 1 0 84 .. 264 + 24z
4
6 3
1 1 7 Divide the first equation by 112 and the second

8 8 8 equation by 84:
The solution is
.. 16 80
1 0 . z
112 112
x1 = 2, x2 = 1, x3 = 3 .. 264 24
0 1 . + z
7. Decide whether the following set of equations has a 84 84
solution. Solve the equations if it does.
16 80 1 5
3x + 4y + z = 13 x = z= z
112 112 7 7
4x + 3y + 2z = 10 264 24 22 2
y = + z= + z
7x + 7y + 3z = 23 84 84 7 7
e94 Mathematics for Physical Chemistry

9. Find the eigenvalues and eigenvectors of the matrix 11. Find the eigenvalues and eigenvectors of the matrix

1 1 1 1 0 1

1 1 1 1 0 1
1 1 1 1 0 1

The eigenvalues are 0,3. The eigenvectors are, for Does this matrix have an inverse? The eigenvalues are
eigenvalue 0: 0 and 2. The eigenvectors are

1 1
0 1 1


0 and 1 1 , 0 0, 1 2





1 0 0 1 1

Check the first eigenvalue: Check the last case:



1 1 1 1 0 1 0 1 1 2

1 1 1 0 = 0 =
1 0 11 2 D
1 1 1 1 0 1 0 1 1 2

For the eigenvalue 3, the eigenvector is The determinant is




1 0 1

1
1 0 1
= 0


1 0 1

Check this There is no inverse matrix.



1 1 1 1 3

1 1 11 = 3
1 1 1 1 3

The eigenvalue is equal to 3.


 

Chapter 15
 

Probability, Statistics, and Experimental


Errors

EXERCISES d. The measurement of the time required for an


automobile to travel the distance between two highway
Exercise 15.1. List as many sources of error as you can for markers nominally 1 km apart, using a stopwatch.
some of the following measurements. Classify each one as
systematic or random and estimate the magnitude of each
source of error. Systematic : faulty calibration of the stopwatch 0.2 s
incorrect spacing of the markers 0.5 s
Random : reaction time difference in pressing the
a. The measurement of the diameter of a copper wire
start and stop buttons 0.3 s
using a micrometer caliper.

The reader should be able to find additional error


Systematic : faulty calibration of the caliper 0.1 mm
sources.
Random : parallax and other errors in reading the
caliper 0.1 mm
Exercise 15.2. Calculate the probability that heads will
b. The measurement of the mass of a silver chloride come up 60 times if an unbiased coin is tossed 100 times.
precipitate in a porcelain crucible using a digital
balance.  100
100! 1
probability =
Systematic : faulty calibration of the balance 1 mg 60!40! 2
Random : impurities in the sample 9.3326 10157
=
lack of proper drying of the sample (8.32099 1081 )(8.15915 1047 )
air currents 7.8886 1031 = 0.01084

c. The measurement of the resistance of an electrical


Exercise 15.3. Find the mean and the standard deviation
heater using an electronic meter.
for the distribution of heads coins in the case of 10 throws
of an unbiased coin. Find the probability that a single toss
Systematic : faulty calibration of the meter 2  will give a value within one standard deviation of the mean.
Random : parallax error and other error in
reading the meter 1  The probabilities are as follows:

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00061-6


2013 Elsevier Inc. All rights reserved. e95
e96 Mathematics for Physical Chemistry

' $
x2 = x 2  x2 = 60.0 (7.50)2 = 3.75
no. of heads binomial probability
=n coefficient = pn x = 3.75 = 1.94
0 1 0.0009766
1 10 0.009766 Exercise 15.5. Calculate the mean and standard deviation
2 45 0.043947 of the Gaussian distribution, showing that is the mean
3 120 0.117192 and that is the standard deviation.
4 210 0.205086 
1 2 2
5 252 0.2461032 x = xe(x) /2 dx
2
6 210 0.205086 
1 2 2
7 120 0.117192
= (y + )ey /2 dx
8 45 0.043947 2

9 10 0.009766 1 2 2
10 1 0.0009766 = yey /2 dx
2
& % 
1 2 2
+ ey /2 dy = 0 + =
2
10 
n = pn n = 5.000 1 2 2
2
x  = x 2 e(x) /2 dx
n=1 2

10 1 2 2
= (y + )2 ey /2 dy
n 2  = pn n 2 = 27.501 2

n=1 1 2 2
= (y 2 + 2y + 2 )ey /2 dy
2
n2 = n 2  n2 = 27.501 25.000 = 2.501 
1 2 2
n = 2.501 = 1.581 = y 2 ey /2 dy
2

The probability that n lies within one standard deviation of 2 2 2
+ yey /2 dy
the mean is 2

1 2 2
probability = 0.205086 + 0.2461032 + 0.205086 = 0.656 + 2 ey /2 dy
2
This is close to the rule of thumb that roughly two-thirds  
1 2 3/2
of the probability lies within one standard deviation of the = (2 ) + 0 + 2 = 2 + 2
2 2
mean.
x2 = x 2  = 2 = 2
Exercise 15.4. If x ranges from 0.00 to 10.00 and if f (x) =
x =
cx 2 , find the value of c so that f (x) is normalized. Find the
mean value of x, the root-mean-square value of x and the
standard deviation.
 10.00  Exercise 15.6. Show that the fraction of a population lying
2 1 3 10.00 c between 1.96 and + 1.96 is equal to 0.950 for the
1 = c x dx = c x  = (1000.0)
0.00 3 0.00 3 Gaussian distribution.
3  +1.96
c = = 0.003000 1 2 2
1000.0 fraction = e(x) /2 dx
2 1.96
 10.00 10.00  1.96
1  1
x 3 dx = c x 4 
2 2
x = c = ey /2 dy
0.00 4 0.00 2 1.96
0.003000  1.96
= (10000) = 7.50 1 2 2
4 = ey /2 dy
 10.00  2 0
2 4 1 5 10.00
x  = c x dx = c x 
0.00 5 0.00 Let u = y
2
0.003000
= (100000) = 60.0
5 1.96
2 1/2 1/2 y = 1.96 u = = 1.386
xrms = x  = (60.0) = 7.75 2
CHAPTER | 15 Probability, Statistics, and Experimental Errors e97

 1.386
2 2 h2
fraction = eu du p2x =  px2   px  =
2 0 4L 2
 1.386 h
1 2 px =
= eu du = erf(1.386) = 0.950 2L
0
Exercise 15.7. For the lowest-energy state of a particle in Exercise 15.9. Find the expression for vx2 1/2 , the root-
a box of length L, find the probability that the particle will mean-square value of vx , and the expression for the standard
be found between L/4 and 3L/4. The probability is deviation of vx .
  1/2   
2 0.7500L 2 m mvx2
(probability) = sin ( x/L)dx vx2  = 2
vx exp dvx
L 0.2500L 2 kB T 2kB T
     2.3562  1/2   
2 L m mvx2
= sin2 (y)dy = 2 vx2 exp dvx
L 0.7854 2 kB T 0 2kB T
   1/2   
2 y sin (y) cos (y) 2.3562 m 2kB T 3/2 2
= = 2 u
2 2 0.7854 2 kB T m 0

2 2.3562 sin (2.3562) cos (2.3562) exp ( u 2 ) du
=  1/2  
2 2 2kB T 3/2
 = 2
m
=
kB T
0.7854 sin (0.7854) cos (0.7854) 2 kB T 4
+ m m
2 2
2
= (1.1781 + 0.2500 0.39270 + 0.2500) kB T
v2x = vx2  0 = vx2  =
= 0.8183
m
kB T
v x =
Exercise 15.8. Find the expectation values for px and px2 m
for our particle in a box in its lowest-energy state. Find the
standard deviation. Exercise 15.10. Evaluate of v for N2 gas at 298.15 K.
  
2 L d  1/2
 px  = sin ( x/L) sin ( x/L) dx 8RT
i L 0 dx v =
 L M
2  1/2
= sin ( x/L) cos ( x/L)dx 8(8.3145 J K1 mol1 )(298.15 K)
i LL 0 =
 (0.028013 kg mol1 )
2 L
= sin (u) cos (u)du = 474.7 m s1
i LL 0

 2 sin2 (u) 
= =0 Exercise 15.11. Evaluate vrms for N2 gas at 298.15 K.
i L 2 0
 1/2
This vanishing value of the momentum corresponds to the 3RT
vrms =
fact that the particle might be traveling in either direction M
with the same probability. The expectation value of the  1/2
3(8.3145 J K1 mol1 )(298.15 K)
square of the momentum does not vanish: =
 (0.028013 kg mol1 )
2 L d2 = 515.2 m s1
 px2  = 2 sin ( x/L) 2 sin ( x/L)
L 0 dx

2 2  L Exercise 15.12. Evaluate the most probable speed for
= 2 sin2 ( x/L)dx nitrogen molecules at 298.15 K.
L L 0

2 2 L 
 1/2
= 2 sin2 (u)du 2RT
L L 0 vmp =

2 2 L  u 
sin (2u) 
M
= 2
 1/2
L L 2 4  2(8.3145 J K1 mol=1 )(298.15 K)
0 =

2 2L 2 2 h2 (0.028013 kg mol1 )
2
=  = =
L L 2 L2 4L 2 = 420.7 m s1
e98 Mathematics for Physical Chemistry

Exercise 15.13. Find the value of the z coordinate after There is one value smaller than 2.868, and one value
1.00 s and find the time-average value of the z coordinate greater than 2.884. Five of the seven values, or 71%, lie in
of the particle in the previous example for the first 1.00 s of the range between x sx and x + sx .
fall if the initial position is z = 0.00 m.
Exercise 15.16. Assume that the HOH bond angles
1 in various crystalline hydrates have been measured to be
z z (t) z(0) = vz (0)t gt 2
2 108 ,109 ,110 ,103 ,111 , and 107 . Give your estimate
1 of the correct bond angle and its 95% confidence interval.
= (9.80 m s2 )t 2 = 4.90 m
2
1
Bond angle =  = (108 + 109 + 110 + 103
 1.00 6

1 + 111 + 107 ) = 108
z = gt 2 dt
2(1.00 s) 0 s = 2.8
   3 1.00 (2.571)(2.8 )
(9.80 m s2 ) t = = 3.3
=
2(1.00 s) 3 0 6
 2  
9.80 m s (1.00 s)3
= Exercise 15.17. Apply the Q test to the 39.75 C data
2.00 s 3 point appended to the data set of the previous example.
= 1.633 m
|(outlying value) (value nearest the outlying value)|
Exercise 15.14. A sample of 7 individuals has the Q =
(highest value) (lowest value)
following set of annual incomes: $40000, $41,000, $41,000, 42.58 39.75 2.83
$62,000, $65,000, $125,000, and $650,000. Find the mean = = = 0.919
42.83 39.75 3.08
income, the median income, and the mode of this sample.

1 By interpolation in Table 15.2 for N = 11, the critical Q


mean = ($40,000 + $41,000 + $41,000 + $62,000
7 value is 0.46. Our value exceeds this, so the data point can
+ $65,000 + $125,000 + $650,000) safely be neglected.
= $146,300
median = $62,000
mode = $41,000 PROBLEMS
1. Assume the following discrete probability distribu-
Notice how the presence of two high-income members of tion:
the set cause the mean to exceed the median. Some persons ' $
might try to mislead you by announcing a number as an
x 0 1 2 3 4 5
average without specifying whether it is a median or a
mean. px 0.00193 0.01832 0.1054 0.3679 0.7788 1.0000

Exercise 15.15. Find the mean, x, and the sample 6 7 8 9 10


standard deviation, sx , for the following set of values: 0.7788 0.3679 0.1054 0.01832 0.00193
x = 2.876 m, 2.881 m, 2.864 m, 2.879 m, 2.872 m, & %
2.889 m, 2.869 m. Determine how many values lie below
x sx and how many lie above x + sx . Find the mean and the standard deviation. Find the
probability that x lies between x x and x x .
x = 2.876
1 10
sx2 = [(0.000)2 + ( 0.005)2 + ( 0.012)2 npn
6 n = n=0
10
+ (0.003)2 + ( 0.004)2 n=0 pn

+ (0.013)2 + ( 0.007)2 ] 10

= 0.0000687 pn = 2(0.00193) + 2(0.01832) + 2(0.1054)
n=0
sx = 0.0000687 = 0.008
+ 2(0.3679) + 2(0.7788) + 1.000
x sx = 2.868,x + sx = 2.884 = 3.5447
CHAPTER | 15 Probability, Statistics, and Experimental Errors e99

10
 The three values n = 4, n = 5, and n = 6 lie
npn = (0 + 10)2(0.00193) + (1 + 9)2(0.01832) within one standard deviation of the mean, so that the
n=0 probability that n lies within one standard deviation of
+ (2 + 8)2(0.1054) + (3 + 7)2(0.3679) the mean is equal to
+ (4 + 6)2(0.7788) + 1.000
= 17.723 probability = 0.196642 + 0.245602 + 0.213022
= 0.655266 = 65.53%
17.723
n = = 5.00 This is close to the rule of thumb value of 2/3.
3.5447
10 2 5. Assume that a random variable, x, is governed by the
n pn
n 2  = n=010
probability distribution
n=0 pn
10 c
 f (x) =
2
n pn = 95.697 x
n=0
95.697 where x ranges from 1.00 to 10.00.
n 2  = = 26.997
3.5447
a. Find the mean value of x and its variance and
n2 = n 2  n2 = 26.997 25.00 = 1.0799
standard deviation. We first find the value of c so
n = 1.0799 = 1.039 that the distribution is normalized:
 10.00 c
probability that x lies between x x and x x dx = c ln (x)|10.00
1.00
1.00 x
1.000 + 2(0.7788)
= = 0.722 = c[ln (10.00) ln (1.000)]
3.5447
= c ln (10.00)
3. Calculate the mean and the standard deviation of all of 1
the possible cases of ten throws for the biased coin in c = = 0.43429
ln (10.00)
the previous problem. Let n be the number of heads
in a given set of ten throws. Using Excel, we calculated
the following:  10.00 c
x = x dx
' $ 1.00 x
 10.00
n bin. (0.510)n
pn npn n2 p n
coeff. (0.490)10n = c dx = c(9.00)
1.00
0 1 0.000797923 0.000797923 0 0
9.00
1 10 0.000830491 0.008304909 0.008304909 0.008304909 = = 3.909
2 45 0.000864389 0.038897484 0.077794967 0.155589934 ln (10.00)
3 120 0.000899670 0.107960363 0.323881088 0.971643263  10.00
c
4 210 0.000936391 0.196642089 0.786568356 3.146273424 x 2  = x 2 dx
5 252 0.000974611 0.245601956 1.228009780 6.140048902 1.00 x
 10.00
c 10.00
6 210 0.001014391 0.213022105 1.278132629 7.668795772
7 120 0.001055795 0.126695363 0.886867538 6.208072768
= c x dx = x 2 
8 45 0.001098888 0.049449976 0.395599806 3.164798446
1.00 2 1.00
9 10 0.001143741 0.011437409 0.102936684 0.926430157
c
10 1 0.001190424 0.001190424 0.011904242 0.119042424 = (100.0 1.00)
& % 2
99.0
= = 21.50
2 ln (10.00)
10

n = npn = 5.100
x2 = x 2  x2 = 21.50 (3.909)2 = 6.220
n=0
10
n 2  = n 2 pn = 28.509
n=0 x = 6.220 = 2.494
n2 = n  n2 = 28.509 26.010 = 2.499
2
b. Find the probability that x lies between x x

n = 2.499 = 1.580 and x x .
e100 Mathematics for Physical Chemistry

 6.403 c where have used the fact that the integrand is an


probability = dx
1.415 x odd function.
= c ln (x)|6.403  10.00  10.00
1.415 x2 x2
1 x 2  = c 2
dx = 2c dx
= [ln (6.403) ln (1.415)] 10.00 x + 1 0 x2 + 1
ln (10.00)  
arctan (x/2) 10.000
ln (6.403/1.415) = 2c x 
= = 0.6556 2 0
ln (10.00)  
arctan (5.000)
= 2c 10.000 0
2
This close to the rule of thumb value of 2/3.
= 2(0.72812)[10.000 0.68670] = 13.5624

where we have used Eq. (13) of Appendix E.


7. Assume that a random variable, x, is governed by the
probability distribution (a version of the Lorentzian x2 = [x 2  0] = 13.562
function)
x = 13.562 = 3.6827
c
f (x) = b. Find the probability that x lies between x x
x2 +4 and x + x .
 3.6827
where x ranges from 10.000 to 10.000. Here is a 1
probability = c 2
dx
graph of the unnormalized function: 3.6827 x + 4
 3.6827
1
= 2c 2
dx
0 x +1

arctan (x/2) 3.6827
= 2c 
2 0
= c[1.07328]
= (0.72812)(1.07328) = 0.7815

9. The nth moment of a probability distribution is


defined by

Mn = (x )n f (x)dx.

a. Find the mean value of x and its variance The second moment is the variance, or square of
and standard deviation. We first normalize the the standard deviation. Show that for the Gaussian
distribution: distribution, M3 = 0, and find the value of M4 , the
fourth moment. Find the value of the fourth root of M4 .
 10.00 
1 1
1= c dx M3 = (x )3
2 2
e(x) /2 dx
10.00 x2 +4
 2
10.00
1 
= 2c dx 1 2 2
x 2+4 = y3 ey /2 dx = 0
0
 2
arctan (x/2) 10.00
= 2c  = c[1.3734] where we have let y = x, and where we set the inte-
2 0 gral equal to zero since its integrand is an odd function.
1 
c = = 0.72812 1
1.3734 M4 = (x )4
2 2
e(x) /2 dx
2

where we have used Eq. (11) of Appendix E. 1 2 2
= y4 ey /2 dx
2
 
10.00 2 2 2
x = c
x
dx = 0 = y 4 ey /2 dx
x2 + 1 2 0
10.00
CHAPTER | 15 Probability, Statistics, and Experimental Errors e101


where have recognized that the integrand is an even 1
sl = (0.03 in)2 + (0.01 in)2 + (0.02 in)2
function. From Eq. (23) of Appendix F, 9
 + (0.00 in)2 + (0.01 in)2 + (0.02 in)2
2 2 (1)(3)(5) (2n 1)
x 2n er x dx = + (0.02 in)2 + (0.04 in)2 + (0.03 in)2
0 2n+1r 2n+1
1/2
so that +(0.00 in)2 = 0.023 in
 (1)(3)
2x2
x 4 er dx = b. Give the expected error in the width and length
0 23 r 5 at the 95% confidence level.
2 3
M4 = (2 2 )5/2 = 3 4 (2.262)(0.019 in)
2 8 w = = 0.014 in
1/4 4 10
M4 = 3 = 1.316
(2.262)(0.023 in)
l = = 0.016 in
11. A sample of 10 sheets of paper has been selected 10
randomly from a ream (500 sheets) of paper. The
width and length of each sheet of the sample were
w = 8.50 in 0.02 in
measured, with the following results:
l = 11.01 in 0.02 in
' $
Sheet number Width/in Length/in c. Calculate the expected real mean area from the
width and length.
1 8.50 11.03
2 8.48 10.99 A = (8.499 in)(11.002 in) = 93.506 in2
3 8.51 10.98
4 8.49 11.00 d. Calculate the area of each sheet in the sample.
5 8.50 11.01 Calculate from these areas the sample mean area
6 8.48 11.02 and the standard deviation in the area.
7 8.52 10.98
' $
8 8.47 11.04
9 8.53 10.97 Sheet Width/in Length/in Area/in2
10 8.51 11.00 number
& % 1 8.50 11.03 93.755
2 8.48 10.99 93.1952
a. Calculate the sample mean width and its sample 3 8.51 10.98 93.4398
standard deviation, and the sample mean length 4 8.49 11.00 93.39
and its sample standard deviation. 5 8.50 11.01 93.585
1 6 8.48 11.02 93.4496
w = (8.50 in + 8.48 in + 8.51 in + 8.49 in 7 8.52 10.98 93.5496
10
+ 8.50 in + 8.48 in + 8.52 in + 8.47 in 8 8.47 11.04 93.5088
9 8.53 10.97 93.5741
+ 8.53 in + 8.51 in) = 8.499 in
 10 8.51 11.00 93.61
1 & %
sw = (0.00 in)2 + (0.02 in)2 + (0.01 in)2
9
+ (0.01 in)2 + (0.00 in)2 + (0.02 in)2
A = 93.506 in2
+ (0.02 in)2 + (0.03 in)2
1/2 s A = 0.150 in2
2 2
+(0.03 in) + (0.01 in)
e. Give the expected error in the area from the
= 0.019 in
results of part d.
1 (2.262)(0.159 in)
l = (11.03 in + 10.99 in + 10.98 in A = = 0.114 in2
10 10
+ 11.00 in + 11.01 in + 11.02 in
+ 10.98 in + 11.04 in 13. A certain harmonic oscillator has a position given by
+ 10.97 in + 11.00 in) = 11.002 in z = (0.150 m)[sin (t)]
e102 Mathematics for Physical Chemistry

where Let u = (0.915 s1 )t.


k  
= . 1 1
m K = (0.544 kg)(0.1372 m s1 )2
6.87 s 2
The value of the force constant k is 0.455 N m1    2
1
and the mass of the oscillator m is 0.544 kg. Find cos2 (u)dt
time average of the kinetic energy of the oscillator 0.915 s1 0
 
over 1.00 period of the oscillator. How does the time u sin (2u) 2
average compare with the maximum value of the = (0.0008143 kg m2 s2 ) + 
2 4 0
kinetic energy?A certain harmonic oscillator has a
= (0.0008143 kg m2 s2 ) = 0.00256 J
position given by
1
The time average is equal to of the maximum value
z = (0.150 m)[sin (t)] 2
of the kinetic energy:
where 1 2 1
k Vmax = kz max = (0.544 kg)(0.1372 m s1 )2
= . 2 2
m = 0.00512 J
The value of the force constant k is 0.455 N m1
and the mass of the oscillator m is 0.544 kg. Find 15. The following measurements of a given variable
time average of the kinetic energy of the oscillator have been obtained: 68.25, 68.36, 68.12, 68.40,
over 1.00 period of the oscillator. How does the time 69.20, 68.53, 68.18, 68.32. Apply the Q test to see if
average compare with the maximum value of the one of the data points can be disregarded.
kinetic energy? The suspect data point is equal to 69.20. The
closest value to it is equal to 68.53 and the range from
 
0.455 N m1 the highest to the lowest is equal to 1.08.
= = 0.915 s1
0.544 kg
0.67
Q= = 0.62
1.08
dz The critical value of Q for a set of 8 members is
v = = (0.150 m)[cos (t)]
dt equal to 0.53. The fifth value, 69.20, can safely be
= (0.150 m)(0.915 s1 )[cos (t)] disregarded. The mean of the remaining values is
= (0.1372 m s1 ) cos[(0.915 s1 )t]
1
mean = (68.25 + 68.36 + 68.12,68.40
7
1 2 + 68.53 + 68.18 + 68.32)
= = = 6.87 s
= 68.31
1
K = mv 2
2

 
1 1
K = (0.544 kg)(0.1372 m s1 )2
6.87 s 2
 6.87 s  
cos2 (0.915 s1 )t dt
0
 

Chapter 16
 

Data Reduction and the Propagation


of Errors

EXERCISES by which the freezing point of the solution is less than that of
the pure solvent, and K f and k f are constants characteristic
Exercise 16.1. Two time intervals have been clocked as of the solvent. Assume that in a given experiment, a sample
t1 = 6.57 s 0.13 s and t2 = 75.12 s 0.17 s. Find of an unknown substance was dissolved in benzene, for
the probable value of their sum and its probable error. Let which K f = 5.12 K kg mol1 and k f = 0.011 K1 . For
t = t1 + t2 . the following data, calculate M and its probable error:
t = 56.57 s + 75.12 s = 131.69 s
W = 13.185 0.003 g
t = [(0.13 s)2 + (0.17 s)2 ]1/2 = 0.21 s
w = 0.423 0.002 g
t = 131.69 s 0.21 s
Tf = 1.263 0.020 K.
Exercise 16.2. Assume that you estimate the total system- wK f
M = (1 k f Tf )
atic error in a melting temperature measurement as 0.20 C W Tf
at the 95% confidence level and that the random error has (0.423 g)(5.12 K kg mol1 )
been determined to be 0.06 C at the same confidence level. =
(13.185 g)(1.263 K)
Find the total expected error.
[1 (0.011 K1 )(1.263 K)]
t = [(0.06 C)2 + (0.20 C)2 ]1/2 = 0.21 C. = (0.13005 kg mol1 )[1 0.01389]
= 0.12825 kg mol1 = 128.25 g mol1
Notice that the random error, which is 30% as large as the
systematic error, makes only a 5% contribution to the total
We assume that errors in K f and k f are negligible.
error.

Exercise 16.3. In the cryoscopic determination of molar M Kf


= (1 k f Tf )
mass,1 the molar mass in kg mol1 is given by w W Tf
(5.12 K kg mol1 )
wK f =
M= (1 k f Tf ), (13.185 g)(1.263 K)
W Tf
[1 (0.011 K1 )(1.263 K)]
where W is the mass of the solvent in kilograms, w is the = 0.30319 kg mol1 g1
mass of the unknown solute in kilograms, Tf is the amount M wK f
= 2 (1 k f Tf )
W W Tf
1 Carl W. Garland, Joseph W. Nibler, and David P. Shoemaker, Experi-
(0.423 g)(5.12 K kg mol1 )
ments in Physical Chemistry, 7th ed., p. 182, McGraw-Hill, New York, =
(13.185 g)2 (1.263 K)
2003.

Mathematics for Physical Chemistry. http://dx.doi.org/10.1016/B978-0-12-415809-2.00062-8


2013 Elsevier Inc. All rights reserved. e103
e104 Mathematics for Physical Chemistry

' $
[1 (0.011 K1 )(1.263 K)]
= 0.00973 kg mol1 g1 1/(T/K) ln (P/torr)
M wK f wK f 0.003354 3.167835
= (1 k f Tf ) (k f )
Tf W (1Tf )2 W Tf 0.003411 2.864199
(0.423 g)(5.12 K kg mol1 ) 0.003470 2.548507
=
(13.185 g)(1.263 K)2 0.003532 2.220181
[1 (0.011 K1 )(1.263 K)] 0.003595 1.878396
(0.423 g)(5.12 K kg mol1 )(0.011 K1 ) 0.003661 1.521481

(13.185 g)(1.263 K) & %
1 1 1 1
= 0.10154 kg mol K 0.00143 kg mol K
1 1
= 0.10011 kg mol K Sx = 0.02102
M = [(0.30319 kg mol1 g1 )2 0.002 g)2 S y = 14.200
1 1 2 2
+(0.00973 kg mol g ) (0.003 g) Sx y = 0.04940
1 1 2 2 1/2
+(0.10011 kg mol K ) (0.020 K) ] Sx 2 = 7.373 105
= [3.68 107 kg2 mol2
+8.52 1010 kg2 mol2 D = N Sx 2 Sx2 = 6(7.373 105 ) (0.02102)2
+4.008 106 kg2 mol2 ]1/2 = 3.9575 107
= 0.00209 kg mol1 N Sx y Sx S y
m =
M = 0.128 kg mol1 0.002 kg mol1 D
[6(0.049404) (0.021024)(14.2006)]
= 128 g mol1 2 g mol1 = = 5362 K
3.95751 107
S 2 S y Sx Sx y
The principal source of error was in the measurement of b = x
Tf . D
(7.46607 105 )(14.2006) (0.021024)(0.049404)
=
3.95751 107
Exercise 16.4. The following data give the vapor pressure = 21.156
of water at various temperatures.2 Transform the data,
Our value for the molar enthalpy change of vaporization is
using ln (P) for the dependent variable and 1/T for the
independent variable. Carry out the least squares fit by hand, Hm = m R = (5362 K)(8.3145 J K1 mol1 )
calculating the four sums. Find the molar enthalpy change
= 44.6 103 J mol1 = 44.6 kJ mol1
of vaporization.
Exercise 16.5. Calculate the covariance for the following
' $ordered pairs:

Temperature/ C Vapor pressure/torr ' $

0 4.579 y x
5 6.543
1.00 0.00
10 9.209
0 1.00
15 12.788
1.00 0.00
20 17.535
0.00 1.00
25 23.756 & %
& %

x = 0.00
y = 0.00
2 R. Weast, Ed., Handbook of Chemistry and Physics, 51st ed., p. D-143, 1
sx,y = (0.00 + 0.00 + 0.00 + 0.00) = 0
CRC Press, Boca Raton, FL, 19711972. 3
CHAPTER | 16 Data Reduction and the Propagation of Errors e105

Exercise 16.6. Assume that the expected error in the the residuals, obtained by a least-squares fit in an Excel
logarithm of each concentration in Example 16.5 is equal to worksheet.
0.010. Find the expected error in the rate constant, assuming
the reaction to be first order. r1 = 0.00109 r6 = 0.00634
r2 = 0.00207 r7 = 0.00480
D = N Sx 2 Sx2 = 9(7125) (225)2 = 13500 min2
r3 = 0.00639 r8 = 0.01891
 1/2
9 r4 = 0.00994 r9 = 0.01859.
m = (0.010) = 2.6 104 min1
13500 min r5 = 0.01348

The standard deviation of the residuals is


m = 0.03504 min1 0.0003 min1
9
k = 0.0350 min1 0.0003 min1 1 2 1
sr2 = r1 = (0.001093)
7 7
i=1
Exercise 16.7. Sum the residuals in Example 16.5 and sr = 0.033064
show that this sum vanishes in each of the three least-square
fits. For the first-order fit D = N Sx 2 Sx2 = 9(7125) (225)2 = 13500 min2

r1 = 0.00109 r6 = 0.00634
 1/2
r2 = 0.00207 r7 = 0.00480 N
m = t(,0.05)sr
D
r3 = 0.00639 r8 = 0.01891  1/2
9
r4 = 0.00994 r9 = 0.01859. = (2.365)(0.033064)
13500 min2
r5 = 0.01348 = 0.0020 min1
sum = 0.00001 0
k = 0.0350 min1 0.002 min1
For the second-order fit
Exercise 16.9. The following is a set of data for the
r1 = 0.3882 r6 = 0.3062 following reaction at 25 C.3
r2 = 0.1249 r7 = 0.1492
(CH3 )3 CBr + H2 O (CH3 )3 COH + HBr
r3 = 0.0660 r8 = 0.0182
r4 = 0.2012 r9 = 0.5634. ' $
Time/h [(CH3 )3 CBr]/mol l1
r5 = 0.3359
sum = 0.00020 0 0 0.1051
5 0.0803
For the third-order fit
10 0.0614
r1 = 2.2589 r6 = 2.0285 15 0.0470
20 0.0359
r2 = 0.8876 r5 = 1.2927
25 0.0274
r3 = 0.2631 r8 = 0.2121 30 0.0210
r4 = 1.1901 r9 = 3.8031. 35 0.0160
40 0.0123
r5 = 1.9531
& %
sum = 0.0101 0
There is apparently some round-off error.
3 L. C. Bateman, E. D. Hughes, and C. K. Ingold, Mechanism
Exercise 16.8. Assuming that the reaction in Example of Substitution at a Saturated Carbon Atom. Pm XIX. A Kinetic
16.5 is first order, find the expected error in the rate constant, Demonstration of the Unimolecular Solvolysis of Alkyl Halides, J. Chem.
using the residuals as estimates of the errors. Here are Soc. 960 (1940).
e106 Mathematics for Physical Chemistry

Using linear least squares, determine whether the so that the rate constant is
reaction obeys first-order, second-order, or third-order
kinetics and find the value of the rate constant. k = 0.0537 h1
To test for first order, we create a spreadsheet with the time
in one column and the natural logarithm of the concentration which agrees with the result of the previous exercise.
in the next column. A linear fit on the graph gives the
Exercise 16.11. Change the data set of Table 16.1
following:
by adding a value of the vapor pressure at 70 C of
421 torr 40 torr. Find the least-squares line using both
the unweighted and weighted procedures. After the point
was added, the results were as follows: For the unweighted
procedure,

m = slope = 4752 K
b = intercept = 19.95;

For the weighted procedure,

m = slope = 4855 K
b = intercept = 20.28.
ln (conc) = (0.0537)t 2.2533
Compare these values with those obtained in the earlier
with a correlation coefficient equal to 1.00. The fit gives a
example: m = slope = 4854 K, and b = intercept =
value of the rate constant
20.28. The spurious data point has done less damage in the
k = 0.0537 h1 weighted procedure than in the unweighted procedure.
To test for second order, we create a spreadsheet with the Exercise 16.12. Carry out a linear least squares fit on the
time in one column and the reciprocal of the concentration following data, once with the intercept fixed at zero and one
in the next column. This yielded a set of points with an without specifying the intercept:
obvious curvature and a correlation coefficient squared
for the linear fit equal to 0.9198. The first order fit is  
better. To test for third order, we created a spreadsheet with x 0 1 2 3 4 5
the time in one column and the reciprocal of the square y 2.10 2.99 4.01 4.99 6.01 6.98
of the concentration in the next column. This yielded a  
set of points with an obvious curvature and a correlation
coefficient squared for the linear fit equal to 0.7647. The Compare your slopes and your correlation coefficients for
first order fit is the best fit. the two fits. With the intercept set equal to 2.00, the fit is

Exercise 16.10. Take the data from the previous exercise


and test for first order by carrying out an exponential fit
using Excel. Find the value of the rate constant. Here is the
graph

y = 0.9985x + 2.00
r 2 = 0.9994

Without specifying the intercept, the fit is


The function fit to the data is
y = 0.984x + 2.0533
c = (0.1051 mol l1 )e0.0537t
r 2 = 0.9997
CHAPTER | 16 Data Reduction and the Propagation of Errors e107

The intrinsic viscosity is defined as the limit4


  
1
lim ln
c0 c 0
where c is the concentration of the polymer measured
in grams per deciliter, is the viscosity of a solution
of concentration c, and 0 is the viscosity of the pure
solvent (water in this case). The intrinsic viscosity and
the viscosity-average molar mass are related by the
formula
 
Exercise 16.13. Fit the data of the previous example to a M 0.76
[] = (2.00 104 dl g1 )
quadratic function (polynomial of degree 2) and repeat the M0
calculation. Here is the fit to a graph, obtained with Excel
where M is the molar mass and M0 = 1 g mol1
(1 dalton). Find the molar mass if [] = 0.86 dl g1 .
Find the expected error in the molar mass if the
expected error in [] is 0.03 dl g1 .
 
[] M 0.76
=
(2.00 104 dl g1 ) M0

   1/0.76
M []
=
M0 (2.00 104 dl g1 )
 1.32
[]
=
(2.00 104 dl g1 )
 1.32
0.86 dl g1
P = 0.1627t 2 6.7771t + 126.82 1
M = (1 g mol )
(2.00 104 dl g1 )
where we omit the units. = 6.25 104 g mol1

dP  
= 0.3254t 6.7771  M 
dt M =   []
[] 

This gives a value of 7.8659 torr C1 for dP/dt at 45 C. = 1.32M0 (5.00 103 g dl1 )1.32 []0.32 []
= (1.32)(1 g mol1 )(5.00 103 g dl1 )1.32
 
dP (0.86 dl g1 )0.32 (0.03 dl g1 )
Hm = (T Vm ) = (318.15 K)(0.1287 m3 mol1 )
dT = 2.2 103 g mol1
 
101325 J m3
(7.8659 torr K1 ) Assume that the error in the constants M0 and 2.00
760 torr
104 dl g1 is negligible.
= 4.294 104 J mol1 = 42.94 kJ mol1 3. The van der Waals equation of state is
 
This is less accurate than the fit to a fourth-degree n2a
P + 2 (V nb) = n RT
polynomial in the example. V

For carbon dioxide, a = 0.3640 Pa m6 mol1 and


b = 4.267 105 m3 mol1 . Find the pressure of
PROBLEMS
4 Carl W. Garland, Joseph W. Nibler, and David P. Shoemaker,
1. In order to determine the intrinsic viscosity [] of a
solution of polyvinyl alcohol, the viscosities of several Experiments in Physical Chemistry, 7th ed., McGraw-Hill, New York,
2003, pp. 321323.
solutions with different concentrations are measured.
e108 Mathematics for Physical Chemistry

0.7500 mol of carbon dioxide if V = 0.0242 m3 state is


and T = 298.15 K. Find the uncertainty in the
pressure if the uncertainty in the volume is 0.00004 m3 difference = 7.657 104 Pa 7.681 104 Pa
and the uncertainty in the temperature is 0.4 K. = 2.4 102 Pa = 0.024 104 Pa
Assume that the uncertainty in n is negligible. Find
the pressure predicted by the ideal gas equation This is roughly the same magnitude as the estimated
of state. Compare the difference between the two error.
pressures you calculated and the expected error in the 5. The vibrational contribution to the molar heat capacity
pressure. of a gas of nonlinear molecules is given in statistical
mechanics by the formula
n RT n2 a
P= 2 3n6
V nb V  u i2 eu i
(0.7500 mol)(8.3145 J K1 mol1 )(298.1 K) Cm (vib) = R
= (1 eu i )2
0.0242 m3 (0.7500 mol)(4.267 105 m3 mol1 ) i=1

(0.7500 mol)2 (0.3640 Pa m6 mol1 ) where u i = hvi /kB T . Here i is the frequency of

(0.0242 m3 )2 the i th normal mode of vibration, of which there are
= 7.6916 104 Pa 3.496 102 Pa = 7.657 104 Pa 3n 6 if n is the number of nuclei in the molecule, h is
 
P n RT 2n 2 a Plancks constant, kB is Boltzmanns constant, R is the
= +
V n,T (V nb)2 V3 ideal gas constant, and T is the absolute temperature.
(0.7500 mol)(8.3145 J K1 mol1 )(298.1 K) The H2 O molecule has three normal modes. The
=
[0.0242 m3 (0.7500 mol)(4.267 105 m3 mol1 )]2 frequencies are given by
2(0.7500 mol)2 (0.3640 Pa m6 mol1 )
+ v1 = 4.78 1013 s1 0.02 1013 s1
(0.0242 m3 )3
v2 = 1.095 1014 s1 0.004 1014 s1
= 3.1836 106 Pa m3 + 2.889 104 Pa m3
v3 = 1.126 1014 s1 0.005 1014 s1
= 3.212 106 Pa m3
  Calculate the vibrational contribution to the heat
P nR
= capacity of H2 O vapor at 500.0 K and find the 95%
T n,V V nb
confidence interval. Assume the temperature to be
(0.7500 mol)(8.3145 J K1 mol1 ) fixed without error.
=
0.0242 m3 (0.7500 mol)(4.267 105 m3 mol1 ) h1
u1 =
= 2.580 102 Pa K1 kB T
    1/2 (6.6260755 1034 J s)(4.78 1013 s1 )
P 2 2 P 2 2 =
P = V + T (1.3806568 1023 J K1 )(500.0 K)
V T
= 4.588
 h2
= (3.212 106 Pa m3 )2 (0.00004 m3 )2 u2 =
kB T
1/2 (6.6260755 1034 J s)(1.095 1014 s1 )
+(2.580 102 Pa K1 )2 (0.4 K)2 =
(1.3806568 1023 J K1 )(500.0 K)
 1/2 = 10.510
= 1.651 104 Pa2 + 1.065 104 Pa2 = 1.65 102 Pa h3
u3 =
kB T
P = 7.657 104 Pa 1.65 102 Pa
(6.6260755 1034 J s)(1.126 1014 s1 )
= 7.66 104 Pa 0.02 104 Pa =
(1.3806568 1023 J K1 )(500.0 K)
From the ideal gas equation of state = 10.580

n RT
P = (4.588)2 e4.588
V Cm (mode 1) = (8.3145 J K1 mol1 )
(1 e4.588 )2
(0.7500 mol)(8.3145 J K1 mol1 )(298.1 K) = 1.817 J K1 mol1
=
0.0242 m3 (10.51)e10.51
Cm (mode 2) = (8.3145 J K1 mol1 )
= 7.681 10 Pa 4 (1 e10.51 )2
= 0.00238 J K1 mol1
The difference between the value from the van der (10.58)e10.58
Waals equation of state and the ideal gas equation of Cm (mode 3) = (8.3145 J K1 mol1 )
(1 e10.58 )2
CHAPTER | 16 Data Reduction and the Propagation of Errors e109

= 0.00224 J K1 mol1 +( 0.02026 J K1 mol1 )2 (3.84 102 )2


Cm (vib) = 1.1863 J K1 mol1 +( 0.01918 J K1 mol1 )2 (4.80 102 )2 ]1/2
= [3.87 104 J2 K2 mol2 + 6.05 107 J2 K2 mol2
h1 +8.48 107 J2 K2 mol2 ]1/2
1 =
kB T = 0.0197 J K1 mol1
(6.6260755 1034 J s)(0.02 1013 s1 ) Cm (vib) = 1.1863 J K1 mol1
=
(1.3806568 1023 J K1 )(500.0 K) 0.0197 J K1 mol1
= 1.92 102
h2
2 =
kB T 7. Vaughan obtained the following data for the
=
(6.6260755 1034 J s)(0.004 1014 s1 ) dimerization of butadiene at 326 C.
(1.3806568 1023 J K1 )(500.0 K)
' $
= 3.84 102
h3 (6.6260755 1034 J s)(0.005 1014 s1 ) Time/min Partial pressure of butadiene/ atm
3 = =
kB T (1.3806568 1023 J K1 )(500.0 K)
= 4.80 102 0 to be deduced
3.25 0.7961
Cm 8.02 0.7457
u 1
  12.18 0.7057
2u 1 eu1 u 21 eu 1 u 21 eu 1
= R 2 eu 1 17.30 0.6657
(1 eu 1 )2 (1 eu 1 )2 (1 eu 1 )3
24.55 0.6073
= (8.3145 J K1 mol1 )
  33.00 0.5573
2(4.588)e4.588 (4.588)2 e4.588 2(4.588)2 e2(4.588)
42.50 0.5087
(1 e4.588 )2 (1 e4.588 )2 (1 e4.588 )3
55.08 0.4585
= (8.3145 J K1 mol1 )
68.05 0.4173
[0.09528 0.21857 0.00449] = 1.025 J K1 mol1
90.05 0.3613
Cm 119.00 0.3073
u 2 259.50 0.1711
 
2u 2 eu i2 u i2 eu 2 u 22 eu 2
= R 2 eu 2 373.00 0.1081
(1 eu 2 )2 (1 eu 2 )2 (1 eu 2 )3 & %
= (8.3145 J K1 mol1 )
 
2(10.51)e10.51 (10.51)2 e10.51 2(10.51)2 e2(10.51) Determine whether the reaction is first, second, or third

(1 e10.51 )2 (1 e10.51 )2 (1 e10.51 )3 order. Find the rate constant and its 95% confidence
interval, ignoring systematic errors. Find the initial
= (8.3145 J K1 mol1 )
pressure of butadiene. A linear fit of the logarithm of
[0.000573 0.00301 0.000000164]
the partial pressure against time shows considerable
= 0.02026 J K1 mol1 ]
curvature, with a correlation coefficient squared equal
Cm
to 0.9609. This is a poor fit. Here is the fit of the
u 3
  reciprocal of the partial pressure against time:
2u 2 eu i3 u 23 eu 3 u 23 eu 3 u 3
=R 2 e
(1 eu 3 )2 (1 eu 3 )2 (1 eu 3 )3
= (8.3145 J K1 mol1 )
 
2(10.58)e10.58 (10.58)2 e10.58 2(10.58)2 e2(10.58)

(1 e10.58 )2 (1 e10.58 )2 (1 e10.58 )3
= (8.3145 J K1 mol1 )[0.0005379 0.0028455
0.000000145] = 0.01918 J K1 mol1

      1/2
Cm 2 2 Cm 2 2 Cm 2 2
Cm = 1 + 2 + 3
u 1 u 2 u 3

= [( 1.025 J K1 mol1 )2 (1.92 102 )2


e110 Mathematics for Physical Chemistry

This is a better fit than the first order fit. A fit of time showed a general curvature and a correlation
the reciprocal of the square of the partial pressure is coefficient squared equal to 0.977. A linear fit
significantly worse. The reaction is second order. The of the reciprocal of the concentration against the
rate constant is time gave the following fit:

k = slope = 0.0206 atm1 min1


1 1
P(0) = = = 0.938 atm
b 1.0664 atm1

The last two points do not lie close to the line. If one
or more of these points were deleted, the fit would be
better. If the last point is deleted, a closer fit is obtained,
with a correlation coefficient squared equal to 0.9997,
a slope equal to 0.0178, and an initial partial pressure
equal to 0.837 atm.

This close fit indicates that the reaction is second


order. The slope is equal to the rate constant, so
that
k = 0.0999 l mol1 min1

b. Find the expected error in the rate constant at the


95% confidence level. The sum of the squares of
the residuals is equal to 9.08 105 . The square
9. The following are (contrived) data for a chemical of the standard deviation of the residuals is
reaction of one substances.
1
' $ sr2 = (9.08 105 ) = 1.009 105
9
Time/min Concentration/mol l1
D = N Sx 2 Sx2 = 11(1540) (110)2
0 1.000
2 0.832 = 1.694 104 1.21 104 = 4.84 103
4 0.714
 1/2  1/2
6 0.626 N 11
m = t(,0.05)sr =
8 0.555 D 4.84 103
10 0.501
12 0.454 (2.262)(1.009 105 )
14 0.417
= 3.4 104 l mol1 min1
16 0.384
18 0.357
k = 0.0999 l mol1 min1
20 0.334
& %
0.0003 l mol1 min1

a. Assume that there is no appreciable back reaction


and determine the order of the reaction and c. Fit the raw data to a third-degree polynomial and
the value of the rate constant. A linear fit of the determine the value of the rate constant from the
natural logarithm of the concentrationagainst the slope at t = 10.00 min. Here is the fit:
CHAPTER | 16 Data Reduction and the Propagation of Errors e111

Using a linear least-squares fit with intercept set


equal to zero, find the value of the absorptivity a if b =
1.000 cm. For comparison, carry out the fit without
specifying zero intercept.
Here is the fit with zero intercept specified:

c = 8.86 105 t 3 + 4.32 103 t 2

8.41 102 t + 0.993


dc
= 2.66 104 t 2 + 8.64 103 t
dt A = abc
8.41 10 2 slope = m = ab = 1436.8 l mol1
m 1436.8
At time t = 10.00 min a = = = 1437 l mol1 cm1
b 1.000 cm
dc
= 0.0243 Here is the fit with no intercept value specified:
dt
dc
= kc2
dt
dc/dt 0.0243 mol l1 min1
k = =
c2 (0.501 mol l1 )2

= 0.0968 l mol1 min1


The value from the least-squares fit is probably
more reliable.
11. The BouguerBeer law (sometimes called the
LambertBeer law or Beers law) states that A =
abc, where A is the of a solution, defined as
log10 (I0 /I ) where I0 is the incident intensity of light m 1445.1
a= = = 1445 l mol1 cm1
at the appropriate wavelength and I is the transmitted b 1.000 cm
intensity; b is the length of the cell through which
the light passes; and c is the concentration of the The value from the fit with zero intercept specified is
absorbing substance. The coefficient a is called the probably more reliable.
molar absorptivity if the concentration is in moles per
a = 1437 l mol1 cm1
liter. The following is a set of data for the absorbance of
a set of solutions of disodium fumarate at a wavelength
of 250 nm.

' $

A 0.1425 0.2865 0.4280 0.5725 0.7160 0.8575


c (mol l1 ) 1.00 104 2.00 104 3.00 104 4.00 104 5.00 104 6.00 104
& %
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