Professional Documents
Culture Documents
0.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
0.1.1 Quantitative methods in chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1 Numbers 2
1.1 Number theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.1 Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.2 Partial fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.3 Polynomial division . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.4 Substitutions and expansions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.1 Functions as tools in chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Units and dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.1 Units, multipliers and prexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.2 Conversion factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.3 Greek alphabet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.4 Unit labels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.5 An aside on scaling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.6 Making tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4 Statistics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4.1 Denition of errors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4.2 Combination of uncertainties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5 Plotting Graphs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5.1 The properties of graphs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.6 Complex numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.6.1 Introduction to complex numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 Trigonometry, matrices 8
2.1 Trigonometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.1 Free Web Based Material from UK HEFCE . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.2 Trigonometry - the sin and cosine rules . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.3 Trigonometric identities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.4 Identities and equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.5 Some observations on triangles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.6 The interior angles of a polygon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
i
ii CONTENTS
2.2 Vectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2.1 Free Web Based Material from HEFCE . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2.2 Vectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2.3 A summary of vectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3 Matrices and determinants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.1 Simultaneous linear equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.2 Practice simultaneous equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3.3 Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.4 Matrix multiply practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.5 Finding the inverse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.6 Determinants and the Eigenvalue problem . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.3.7 Matrices with complex numbers in them . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3 Calculus 14
3.1 Dierentiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1.1 Free web-based material from HEFCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1.2 The basic polynomial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1.3 The chain rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1.4 Dierentiating a product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1.5 Dierentiating a quotient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.1.6 Using dierentiation to check turning points . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2 Integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.1 Free Web Based Material from HEFCE . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.2 Logarithms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2.3 Integrating 1/x . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2.4 Integrating 1/x like things . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2.5 Some observations on innity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2.6 Denite integrals (limits) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.7 Integration by substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.8 Simple integration of trigonometric and exponential Functions . . . . . . . . . . . . . . . . 17
3.2.9 Integration by parts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.10 Integration Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2.11 Dierential equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.12 The calculus of trigonometric functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.13 Integration by rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.14 The Maclaurin series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.15 Calculus revision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.3 Some useful aspects of calculus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.3.1 Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.3.2 Numerical dierentiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3.3 Numerical integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
CONTENTS iii
5 Further reading 26
5.1 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.1.1 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
0.1 Introduction
This book was initially derived from a set of notes used
in a university chemistry course. It is hoped it will evolve
into something useful and develop a set of open access
problems as well as pedagogical material.
For many universities the days when admission to a
Chemistry, Chemical Engineering, Materials Science or
even Physics course could require the equivalent of A-
levels in Chemistry, Physics and Mathematics are prob-
ably over for ever. The broadening out of school curric-
ula has had several eects, including student entry with
a more diverse educational background and has also re-
sulted in the subject areas Chemistry, Physics and Mathe-
matics becoming disjoint so that there is no co-requisite
material between them. This means that, for instance,
physics cannot have any advanced, or even any very sig-
nicant mathematics in it. This is to allow the subject to
be studied without any of the maths which might be rst
studied by the A-level maths group at the ages of 17 and
18. Thus physics at school has become considerably more
descriptive and visual than it was 20 years ago. The same
applies to a lesser extent to chemistry.
This means there must be an essentially remedial com-
ponent of university chemistry to teach just the Mathe-
matics and Physics which is needed and not too much, if
any more, as it is time consuming and perhaps not what
the student of Chemistry is most focused on. There is
therefore also a need for a book Physics for Chemistry.
Numbers
1.1 Number theory metrical angles, e.g. sin 60 = 23 and so they appear fre-
quently in mathematical expressions regarding 3 dimen-
1.1.1 Numbers sional space.
Notation
Real numbers come in several varieties and forms;
The notation used for recording numbers in chemistry is
the same as for other scientic disciplines, and appropri-
Integers are whole numbers used for counting in- ately called scientic notation, or standard form. It is a
divisible objects, together with negative equivalents way of writing both very large and very small numbers
and zero, e.g. 42, 7, 0 in a shortened form compared to decimal notation. An
example of a number written in scientic notation is
Rational numbers can always be expressed as frac-
tions, e.g. 4.673 = 4673/1000. 4.65 106
Irrational numbers, unlike rational numbers, cannot with 4.65 being a coecient termed the signicand or the
be expressed mantissa, and 6 being an integer exponent. When written
as a fraction or as a denite decimal, in decimal notation, the number becomes
e.g. and 2
4650000 .
Natural numbers are integers that are greater than or
equal to zero. Numbers written in scientic notation are usually nor-
malised, such that only one digit precedes the decimal
point. This is to make order of magnitude comparisons
It is also worth noting that the imaginary unit and there-
easier, by simply comparing the exponents of two num-
fore complex numbers are used in chemistry, especially
bers written in scientic notation, but also to minimise
when dealing with equations concerning waves.
transcription errors, as the decimal point has an assumed
position after the rst digit. In computing and on calcu-
Surds lators, it is common for the 10 (times ten to the power
of) to be replaced with E (capital e). It is important
The origin of surds goes back to the Greek philosophers. not to confuse this E with the mathematical constant e.
It is relatively simple to prove that the square root of 2 Engineering notation is a special restriction of scientic
cannot be a ratio of two integers, no matter how large notation where the exponent must be divisible by three.
the integers may become. In a rather Pythonesque inci- Therefore, engineering notation is not normalised, but
dent the inventor of this proof was put to death for heresy can easily use SI prexes for magnitude.
by the other philosophers because they could not believe
such a pure number as the root of 2 could have this impure Remember that in SI, numbers do not have commas
property. between the thousands, instead there are spaces, e.g.
18 617 132 , (an integer) or 1.861 713 2x107 . Com-
(The original use of quadratic equations is very old, Baby- mas are used as decimal points in many countries.
lon many centuries BC.) This was to allocate land to farm-
ers in the same quantity as traditionally held after the
great oods on the Tigris and Euphrates had reshaped the Exponents
elds. The mathematical technology became used for the
same purpose in the Nile delta. Consider a number xn , where x is the base and n is the
When you do trigonometry later you will see that surds exponent. This is generally read as x to the n or x to
are in the trigonometric functions of the important sym- the power of n . If n = 2 then it is common to say x
2
1.1. NUMBER THEORY 3
squared, and if n = 3 then x cubed. Comparing pow- We can reverse this process by use of a common denom-
ers (exponentiation) to multiplication for positive integer inator.
values of n (n = 1, 2, 3 . . . ) , it can be demonstrated that 3
1 = 3(x1)(x+1)
2(x+1) 2(x1) 2(x+1)(x1)
4x = x + x + x + x , i.e. four lots of x added together
The numerator is 2x 4 , so it becomes
x4 = xxxx , i.e. x multiplied by itself four times. (x2)
(x+1)(x1)
1 0
For x , the result is simply x . For x the result is 1 .
which is what we started from.
So we can generate a single term by multiplying by the
Order of operations denominators to create a common denominator and then
add up the numerator to simplify. A typical application
When an expression contains dierent operations, they might be to convert a term to partial fractions, do some
must be evaluated in a certain order. Exponents are evalu- calculus on the terms, and then regather into one quotient
ated rst. Then, multiplication and division are evaluated for display purposes. In a factorised single quotient it will
from left to right. Last, addition and subtraction are eval- be easier to see where numerators go to zero, giving so-
uated left to right. Parentheses or brackets take prece- lutions to f (x) = 0 , and where denominators go to zero
dence over all operations. Anything within parentheses giving innities.
must be calculated rst. A common acronym used to re- A typical example of a meaningful innity in chemistry
member the order of operations is PEMDAS, for Paren- might be an expression such as
theses, Exponents, Multiplication, Division, Addition,
A
Subtraction. Another way to remember this acronym is (EEa )2
Please Excuse My Dear Aunt Sally. The variable is the energy E, so this function is small ev-
Keep in mind that negation is usually considered multi- erywhere, except near Ea . Near Ea a resonance occurs
plication. So in the case of x2 , the exponent would be and the expression becomes innite when the two ener-
evaluated rst, then negated, resulting in a negative num- gies are precisely the same. A molecule which can be
ber. electronically excited by light has several of these reso-
nances.
Take note of this example:
Here is another example. If we had to integrate the fol-
3 + x 2 , let x=5.
lowing expression we would rst convert to partial frac-
If evaluated incorrectly (left-to-right, with no order of op- tions:
erations), the result would be 16. Three plus ve gives 3x 3x A B
= 2(x+1)(x2) = x+1 + x2
eight, times two is 16. The correct answer should be 13. 2x2 2x4
Five times two gives ten, plus three gives 13. This is be- so
cause multiplication is solved before addition. 3
x = A(x 2) + B(x 1)
2
let x = 2 then 3 = B
1.1.2 Partial fractions let x = 1 then 3
2 = A
therefore the expression becomes
Partial fractions are used in a few derivations in thermo-
dynamics and they are good for practicing algebra and x2 2(x+1)
3 3
(5) 3
2(x2) 2
2(x1) ax2 + bx + c = 0
there is a formula
b (b2 4ac)
1.1.3 Polynomial division x= 2a
(Notice the line over the square root has the same priority
This is related to partial fractions in that its principal use
as a bracket. Of
course
we all know by now that a+b
is to facilitate integration.
is not equal to a + b but errors of priority are among
Divide out the most common algebra errors in practice).
3x2 4x6
1+x There is a formula for a cubic equation but it is
like this rather complicated and unlikely to be required for
undergraduate-level study of chemistry. Cubic and higher
3x - 7 ----------------- x + 1 ) 3x2 4x 6 3x2 +3x ------ equations occur often in chemistry, but if they do not fac-
--- 0 7x 6 7x 7 -------- 1 torise they are usually solved by computer.
So our equation becomes 3x 7 + 1+x 1
Solve:
This can be easily dierentiated, and integrated. If this 2x2 14x + 9
is dierentiated with the quotient formula it is consider- 2
ably harder to reduce to the the same form. The same 1.56(x + 3.67x + 0.014)
procedure can be applied to partial fractions. Notice the scope or range of the bracket.
2x2 4x + 2
1.1.4 Substitutions and expansions 45.1(1.2[A]2 57.9[A] + 4.193)
Notice here that the variable is a concentration, not the
You can see the value of changing the variable by simpli-
ubiquitous x .
fying
3 2
( J(J+1) ) +2( J(J+1) )+1 ( J(J+1) ) 2( J(J+1) )+1
J(J+1) 2
( ) 9 J(J+1) 2
( ) +9 1.3 Units and dimensions
to
x3 +2x+1 x2 2x+1
x2 9 x2 +9
1.3.1 Units, multipliers and prexes
where
It is usually necessary in chemistry to be familiar with
J(J+1)
x= at least three systems of units, Le Systme International
This is an example of simplication. It would actually be d'Units (SI), atomic units as used in theoretical calcula-
possible to dierentiate this with respect to either J or tions and the unit system used by the experimentalists.
using only the techniques you have been shown. The alge- Thus if we are dealing with the ionization energy, the
braic manipulation involves dierentiation of a quotient units involved will be the Joule (J), the Hartree (E , the
and the chain rule. atomic unit of energy), and the electron volt (eV).
Evaluating dy
gives These units all have their own advantages;
dx
+ 2 (x(x2x+1)x
3 2
3x2 +2
2 (x(x+2x+1)x 2x2 The SI unit should be understood by all scientists
x2 9 2 9)2 x2 +9 2 +9)2
regardless of their eld.
Expanding this out to the J s and s would look ridicu-
lous. The atomic unit system is the natural unit for theory
as most of the fundamental constants are unity and
Substitutions like this are continually made for the pur-
equations can be cast in dimensionless forms.
pose of having new, simpler expressions, to which the
rules of calculus or identities are applied. The electron volt comes from the operation of the
ionization apparatus where individual electrons are
accelerated between plates which have a potential
1.2 Functions dierence in Volts.
the output of a large power station (gigaJoules), or the in- Magnetic Susceptibility
teraction of two inert gas atoms, (a few kJ per mole or
a very small number of Joules per molecule when it has 1 cm3 mol1 = 16.60540984 JT2 x 1030 (joule tesla2 )
been divided by Avogadros number).
In SI the symbols for units are lower case unless derived
from a persons name, e.g. ampere is A and kelvin is K.
Note the use of capitals and lower case and the increment Old units
on the exponent being factors of 3. Notice also centi and
deci are supposed to disappear with time leaving only the Occasionally, knowledge of older units may be required.
powers of 1000. Imperial units, or convert energies from BTUs in a ther-
modynamics project, etc.
In university laboratory classes you would probably be
1.3.2 Conversion factors
given material on the Quantity Calculus notation and
methodology which is to be highly recommended for sci-
The, (sometimes call caret or hat), sign is another nota-
entic work.
tion for to the power of. E means times 10 to the power
of, and is used a great deal in computer program output. A good reference for units, quantity calculus and SI is:
I. Mills, T. Cuitas, K. Homann, N. Kallay, K. Kuchitsu,
Quantities, units and symbols in physical chemistry, 2nd
Energy edition, (Oxford:Blackwell Scientic Publications,1993).
An approximation of how much of a chemical bond each
energy corresponds to is placed next to each one. This
indicates that light of energy 4 eV can break chemical
bonds and possibly be dangerous to life, whereas infrared 1.3.3 Greek alphabet
radiation of a few cm1 is harmless.
1.3.4 Unit labels
1 eV = 96.48530891 kJ mol1 (Near infrared), ap-
proximately 0.26 chemical bonds
The labelling of tables and axes of graphs should be done
1 1
1 kcal mol = 4.184000000 kJ mol (Near in- so that the numbers are dimensionless, e.g. temperature
frared), approximately 0.01 chemical bonds is T /K ,
1 MHz = 0.399031E-06 kJ mol1 (Radio waves), ln(k/k0 ) and energy mol / kJ etc.
approximately 0.00 chemical bonds This can look a little strange at rst. Examine good text
1 cm = 0.01196265819 kJ mol (Far infrared), books like Atkins Physical Chemistry which follow SI
1 1
The technique of adding unit labels to numbers is espe- In an experimental situation, values with errors are often
cially useful, in that analysis of the units in an equation combined to give a resultant value. Therefore, it is nec-
can be used to double-check the answer. essary to understand how to combine the errors at each
stage of the calculation.
Practice
The absolute error is x, 0.05 cm3
Plot x2 1 between 3 and +2 in units of 1.
The fractional error is x
x , 50 = 0.001
0.05
1.6 Complex numbers Eulers equation is obvious from looking at the Maclaurin
expansion of ei .
1.6.1 Introduction to complex numbers To nd the square root of i we use de Moivres theorem.
ei 2 = 0 + 1i
The equation:
2
so de Moivres theorem gives ei 2 = cos 2.2 + i sin 2.2
x + 6x + 13 = 0
= 12 + 12 i
Does not factorise
Check this by squaring up to give i .
x = 3 9 13
The other root comes from:
4 without complex
numbers does not exist. However
the number i = 1 behaves exactly like any other num- 4 + i sin 4 = 2 2 i
5 5 1 1
Trigonometry, matrices
cos2 + sin2 = 1
2.1.1 Free Web Based Material from UK
HEFCE Remember this is a consequence of Pythagoras theorem
where the length of the hypotenuse is 1.
There is a DVD on trigonometry at Math Tutor. sin( + ) = sin cos + cos sin
cos( + ) = cos cos sin sin
The dierence of two angles can easily be generated by
2.1.2 Trigonometry - the sin and cosine putting = and remembering sin = sin
rules and cos = cos . Similarly, the double angle for-
mulae are generated by induction. tan( + ) is a little
more complicated but can be generated if you can handle
B the fractions! The proofs are in many textbooks but as a
chemist it is not necessary to know them, only the results.
8
2.2. VECTORS 9
coceles triangle you can always dispense with the sin and the 3 dimensions:
cosine rules, drop a perpendicular down to the base and i + j + k
use trig directly. Remember that the bisector of a side or
an angle to a vertex cuts the triangle in two by area, an- so that
gle and length. This can be demonstrated by drawing an v = Axi + Ayj + Az k
obtuse triangle and seeing that the areas are 12 12 .R.h .
The hat on the i, j, k signies that it is a unit vector. This
is usually omitted.
2.1.6 The interior angles of a polygon Our geographical analogy allows us to see the meaning of
vector addition and subtraction. Vector products are less
Remember that the interior angles of a n -sided polygon obvious and there are two denitions the scalar product
are n * 180 360, and the vector product. These are dierent kinds of math-
( n 2 ). ematical animal and have very dierent applications. A
scalar product is an area and is therefore an ordinary num-
For benzene there are six equilateral triangles if the centre
ber, a scalar. This has many useful trigonometrical fea-
of the ring is used as a vertex, each of which having an
tures.
interior angle of 120 degrees. Work out the the angles in
azulene, (a hydrocarbon with a ve and a seven membered The vector product seems at rst to be dened rather
ring), assuming all the C-C bond lengths are equal, (this strangely but this denition maps onto nature as a very
is only approximately true). elegant way of describing angular momentum. The struc-
ture of Maxwells Equations is such that this deni-
tion simplies all kinds of mathematical descriptions of
2.2 Vectors atomic / molecular structure and electricity and mag-
netism.
4.20 = 2x + 4y x + 4y = 8
and and
6.30 = 4x + y x + 5y = 10
i.e. y = 4.20
24 x and y = 6.30 4x 7x 4y = 10
4
If you plot these equations they will be simultaneously Notice that you can solve:
true at x = 1.5 and y = 0.30 . 3x + 4y + 9z = 4
Notice that if the two rounds of drinks are 2 pints and 3x + 2y 4z = 1
2 packets of crisps and 3 pints and 3 packets of crisps
we cannot solve for the prices! This corresponds to two 0x + 0y 2z = 1
parallel straight lines which never intersect. because it breaks down into a (2x2) and is not truly a
2.3. MATRICES AND DETERMINANTS 11
(3x3). (In the case of the benzene molecular orbitals, As discussed earlier the solving of simultaneous equa-
which are (6x6), this same scheme applies. It becomes tions is equivalent in some deeper sense to rotation in n
two direct solutions and two (2x2) problems which can -dimensions.
be solved as above.)
This is if we rotate by +45 degrees. For = 45o Here Adj A is the adjoint matrix, the transposed matrix
cos(45) = cos 45 and sin(45) = sin 45 . So the of cofactors. These strange objects are best described by
rotation ips over to give (01) . The minus sign is nec- example.....
essary for the correct mathematics of rotation and is in 1 1 2
the lower left element to give a right handed sense to the 2 1 1
rotational sign convention. 3 1 1
12 CHAPTER 2. TRIGONOMETRY, MATRICES
This determinant is equal to: 1 ( 1 x 1 - 1 x (1)) - (1) ( 2.3.6 Determinants and the Eigenvalue
2 x 1 - 1 x 3) + 2 ( 2 x (1) - ( 1 x 3) each of these terms problem
is called a cofactor.
a11 a12 a13 In 2nd year
quantum chemistry you will come across this
E
a21 a22 a23 0 0
a31 a32 a33 E 0
object: =0
0 E
a11 (a22 a33 a23 a32 ) 0 0 E
DetA = 1i+j1 + 1i+j1 a12 (a21 a33 a23 a31 )
+ 1i+j1 a13 (a21 a32 a22 a31 ) You divide by and set ( E)/ to equal x to get:
This 1i+j1 thing gives the sign alternation in a form x 1 0 0
1 x 1 0
mathematicians like even though it is incomprehensible.
0 1 x 1 = 0
Use the determinant 0 0 1 x
1 1 2
Expand this out and factorise it into two quadratic equa-
2 1 1
tions to give:
3 1 1
(x2 + x 1)(x2 x 1) = 0
to solve the simultaneous equations on page 47 by the
matrix inverse method. The matrix corresponding to the which can be solved using x = b etc.
equations on p47.2 is:
1 1 2 6 2 1 1 = 3 3 1 1 6 The cofactors are 2 1 5 Simultaneous equations as linear algebra
1 5 2 3 3 3 You may nd these 9 copies of the
matrix useful for striking out rows and columns to form The above determinant is a special case of simultaneous
this inverse.... 1 1 2 1 1 2 1 1 2 2 1 1 2 1 1 2 1 1 equations which occurs all the time in chemistry, physics
3 1 1 3 1 1 3 1 1 1 1 2 1 1 2 1 1 2 2 1 1 2 1 and engineering which looks like this:
1 2 1 1 3 1 1 3 1 1 3 1 1 1 1 2 1 1 2 1 1 2
2 1 1 2 1 1 2 1 1 3 1 1 3 1 1 3 1 1 These are the (a11 )x1 + a12 x2 + a13 x3 ..... + a1n xn = 0
a21 x2 + (a22 )x1 + a23 x3 ..... + a2n xn = 0
little determinants with the 1 to the (n-1) factors and the
.....
value of the determinant is 9. The transposed matrix of
.....
cofactors is 2 1 3 1 5 3 5 2 3 So the inverse is 2
1 3 1/9 X 1 5 3 5 2 3 Giving a solution 2 1 a1n xn + a2n xn + an3 x3 ..... + (a11 )x1 = 0
3 6 1 1/9 X 1 5 3 X 3 = 1 5 2 3 6 2 This equation in matrix form is (A 1)x = 0 and the
This takes a long time to get all the signs right. Elimi- solution is Det(A 1) = 0 .
nation by subtracting equations is MUCH easier. How- This is a polynomial equation like the quartic above. As
ever as the computer cannot make sign mistakes it is not you know polynomial equations have as many solutions as
a problem when done by computer program. the highest power of x i.e. in this case n . These solutions
The following determinant corresponds to an equation can be degenerate for example the orbitals in benzene
which is repeated three times giving an unsolvable set of are
6
a degenerate pair because of the factorisation of the
simultaneous equations. x polynomial from the 6 Carbon-pz orbitals. In the 2nd
year you may do a lab exercise where you make the ben-
1 2 3
zene determinant and see that the polynomial is
1 2 3
2 4 6 (x2 4)(x2 1)(x2 1) = 0
Matrix multiplication is not necessarily commutative, from which the 6 solutions and the orbital picture are im-
which in English means AB does not equal BA all the mediately obvious.
time. Multiplication may not even be possible in the case The use of matrix equations to solve arbitrarily large
of rectangular rather than square matrices. problems leads to a eld of mathematics called linear al-
I will put a list of the properties and denitions of matrices gebra.
in an appendix for reference through the later years of the
course.
2.3.7 Matrices with complex numbers in
them
Calculus
dx v = v2
1. The derivative of a function times a constant is just
the same constant times the derivative.
Problems
2. The derivative of a sum of functions is just the sum
of the two derivatives. Dierentiate with respect to x
3x2 x(1 + x)(1 x)
To get higher derivatives such as the second derivative Notice we have (a2 b2 ) . 4x7 3x2
keep applying the same rules.
(3x + 2)2 + ex
One of the big uses of dierentiation is to nd the station-
8x6 12 x
ary points of functions, the maxima and minima. If the
function is smooth, (unlike a saw-tooth), these are easily x(x + 3)2
located by solving equations where the rst derivative is x2 (3x (2 + x)(2 x))
zero.
Evaluate the inner brackets rst.
Evaluate
( )
3.1.3 The chain rule d
e z
z9
3
dz 18 z 2
dy dy dw ( )
dx = dw . dx
d
c5
dc
This is best illustrated by example: nd dy
given y = d ( 1 )
d 2 3
dx 1 1
9
(x4 + 1) ( ( ))
d
Let y = u9 and u = x4 + 1 . d e
1
2 + 3 2
2
d
( ( ))
Now dy
du = 9u8 and du
dx = 4x3 dr e
5r
ra3 + rb6 + rc9
So using the chain rule we have 9(x4 + 1) .4x3 = a, b and c are constants. Dierentiate with respect to r .
8
8
36x3 (x4 + 1) 3re3r
14
3.2. INTEGRATION 15
d
( ) dy d y 2
dx x6 ex y = f (x) dx = f (x) dx2 = f (x)
5e5r + 3a
+ 6b
+ 9c 2x 6
r4 r7 r 10
e3r (3 9r) Solutions are 1/3( 19 1) and 1/3( 19 + 1) , i.e.
1.7863 and 1.1196.
x5 ex (x + 6) d2 y
dx2 = f (x) = 6x + 2
d2 y
There are 3 coincident solutions at x = 0 , dx2 = 0 , at
Harder dierentiation problems
0 so this is an inection point.
Dierentiate with respect to x : The roots are 0, 1 and 1.
4 5
x (x + 9)
5
5x2 (x2 7x + 9)
Dierentiate with respect to r
3.2 Integration
3
(r2 + 3r 1) e4r
3.2.1 Free Web Based Material from
Dierentiate with respect to HEFCE
( 2 )
4 3 19
1
Remember how we do a denite integral This is done in many textbooks and Wikipedia. Their
3 3 notation might be dierent to the one used here, which
0
(f (x)) = [F (x)]0 = F (3) F (0) hopefully is the most clear. You derive the expression
where F is the indenite integral of f . by taking the product rule and integrating it. You then
make one of the U V into a product itself to produce the
Here is an example where limits are used to calculate the
expression.
3 areas cut out by a quartic equation:
( )
x 2x x + 2x .
4 3 2 U V = U V U V
We see that x = 1 is a solution so we can do a polynomial (all integration with respect to x . Remember by
division:
U V = U [int] [diff][int]
x3 -x2 2x ------------------- x-1 ) x4 2x3 -x2 +2x x4 ( U gets dierentiated.)
-x3 -------- -x3 -x2 -x3 +x2 ------- 2x2 +2x 2x2 +2x
-------- 0 The important thing is that you have to integrate one ex-
pression of the product and dierentiate the other. In
So the equation is x(x x 2)(x 1) which factorises the basic scheme you integrate the most complicated ex-
2
4e2x dx
sin 2d
Integrate the following by parts with respect to x .
sin2 + cos2 d
xex
cos d
x2 sin x
x cos x
Answers x2 ex
x2 ln x
2e2x + c
ex sin x
3e3x + c
e2x cos x
21 cos 2 + c 7
x(1 + x)
+c
Actually this one can be done quite elegantly by parts, to
i.e. the integral of 1d . give a two term expression. Work this one out. Expand-
sin + c ing the original integrand by Pascals Triangle gives:
18 CHAPTER 3. CALCULUS
3x sin x
2x2 cos 2x 3.2.12 The calculus of trigonometric func-
tions
If you integrate x7 sin x you will have to apply parts 7
times to get x to become 1 thereby generating 8 terms:
There are many dierent ways of expressing the same
7 6 5 4 3 -x cos(x) + 7 x sin(x) + 42 x cos(x) - 210 x sin(x) thing in trig functions and very often successful integra-
- 840 x cos(x) + 2 2520 x sin(x) + 5040 x cos(x) - 5040 tion depends on recognising a trig identity.
sin(x) + c (Output from Maple.)
sin 2xdx = 12 cos 2x + c
Though it looks nasty there is quite a pattern to this, 7,
but could also be
7x6,7x6x5 -----7! and sin, cos, -sin, -cos, sin, cos etc
so it can easily be done by hand. sin2 x or cos2 x
(each with an integration constant!).
When applying calculus to these functions it is necessary
3.2.11 Dierential equations to spot which is the simplest form for the current manip-
ulation. For integration it often contains a product of a
First order dierential equations are covered in many function with its derivative like 2 sin x cos x where inte-
textbooks. They are solved by integration. (First order gration by substitution is possible.
dy dy
equations have dx , second order equations have dx and
Where a derivative can be spotted on the numerator and
d2 y
dx2 .) its integral below we will get a ln function. This is how
The arbitrary constant means another piece of informa- we integrate tan .
sin x
tion is needed for complete solution, as with the Newtons tan xdx = cos x dx = ln (cos x) + c
Law of Cooling and Half Life examples.
We can see this function goes to innity at /2 as it should
Provided all the x s can be got to one side and the y s to do.
another the equation is separable.
dy
2y dx = 6x2
3.2.13 Integration by rearrangement
2ydy = 6x2 dx
y 2 = 2x3 + c Take for example:
This is the general solution. cos2 xdx
Typical examples are: Here there is no sin function producted in with the cos
dy
dy
dx
powers so we cannot use substitution. However there are
y = x dx y = x the two trig identities
ln y = ln x + ln A (constant) i.e. y = Ax cos2 + sin2 = 1
by denition of logs. and
dy
dx = ky (1) cos2 sin2 = cos 2
dy
kxy = dx Using these we have
dy
y = kxdx (2) cos2 xdx = 21 (1 + cos 2x)dx
ln y = 1 2
(3) so we have two simple terms which we can integrate.
2 kx +A
This corresponds to:
y = Be 2 kx
1 2 3.2.14 The Maclaurin series
The Schrdinger equation is a 2nd order dierential We begin by making the assumption that a function can
equation e.g. for the particle in a box be approximated by an innite power series in x :
2 d2
2m dx2 + E = 0 f (x) = a0 + a1 x + a2 x2 + a3 x3 + a4 x4 + . . .
3.3. SOME USEFUL ASPECTS OF CALCULUS 19
ln(1 + x) converges extremely slowly. ex is much faster As sin x = x for small x this expression is cos x .
because the Similarly for cos
20 CHAPTER 3. CALCULUS
dy cos(+)cos
d =
cos cos sin sin cos
=
cos sin cos
=
This is equal to sin .
4.1 Some mathematical examples a very natural description mathematically and maps
ideally onto the physical reality. Here we are inte-
applied to chemistry grating with respect to t and , the operating fre-
quency if it is a laser experiment is a constant, there-
4.1.1 Variable names fore it appears on the denominator in the integration.
2
cos(t) sin(t)dt = cos()2 + c In this case
The ubiquitous x is not always the variable as you will all we can see a physical interpretation for the integra-
know by now. One problem dealing with real applications tion constant. It will be a phase factor. If we were
is sorting out which symbols are the variables and which dealing with sunlight we might well be integrating
are constants. (If you look very carefully at professionally a dierent function over in order to calculate all
set equations in text books you should nd that there are of the phenomenon which has dierent strengths at
rules that constants are set in Roman type, i.e. straight the dierent light frequencies. Our integration lim-
letters and variables in italics. Do not rely on this as it is its would either be from zero to innity or perhaps
often ignored.) over the range of energies which correspond to vis-
Here are some examples where the variable is conven- ible light.
tionally something other than x .
21
22 CHAPTER 4. TESTS AND EXAMPLES
4.1.2 van der Waals Energy to give the shape of the potential and hence the infra-red
spectrum. E is usually modelled by a very complicated
The van der Waals energy between two inert gas atoms function whose dierentiation is not entered into lightly.
can be written simply as a function of r
A B
Evdw =
r 12 r6 4.1.4 A one-dimensional metal
12
Notice that the r term is positive corresponding to re-
pulsion. The r6 term is the attractive term and is negative A one-dimensional metal is modelled by an innite chain
corresponding to a reduction in energy. A and B are con- of atoms 150 picometres apart. If the metal is lithium
stants tted to experimental numbers. each nucleus has charge 3 and its electrons are modelled
This function is very easy to both dierentiate and inte- by the{ function}
grate. Work these out. In a gas simulation you would cos2 2 150 r
In a diatomic molecule the energy is expanded as the bond 4.1.6 Newtons law of cooling
stretches in a polynomial. We set x = (r r0 ) . At r0
the function is a minimum so there is no dE/dx term. is the excess temperature of a cooling body over room
2 3 temperature (20o C say). The rate of cooling is propor-
E = 12 kharm. ddxE2 + 16 kanharm. ddxE3 tional to the excess temperature.
Whatever function is chosen to provide the energy setting d = k
dt
the 1st derivative to zero will be required to calculate r0 .
dx 1
The 2nd and 3rd derivatives will then need to be evaluated using dy = dy
dx
4.2. TESTS AND EXAMS 23
dt
d = k
1
4.1.8 Partial fractions for the 2nd order
This is a dierential equation which we integrate with re- rate equation
spect to to get
In chemistry work you will probably be doing the 2nd or-
t = k1 ln + c
der rate equation which requires partial fractions in order
The water is heated to 80o C and room temperature is 20o to do the integrals.
C. At the beginning t = 0 and = 60 , so
If you remember we have something like
0 = k1 ln 60 + c 1 A B
(2x)(3x) = (2x) + (3x)
therefore
Put the right-hand side over a common denominator
ln 60
c= k 1 A(3x)+B(2x)
(2x)(3x) = (2x)(3x)
t= k1 ln + 1
k ln 60
This gives 1 = 3A Ax + 2B Bx
but ln 60 ln = ln 60
By setting x to 3 we get 1 = -B (B=1). Setting x = 0 and
so ln 60 = kt B = 1
After 5 minutes the water has cooled to 70o C. 1 = 3A 2 (A=+1) Check 1 = 3 -x 2 +x true...
so ln = 5k so k =
50
60 ln 15 5
6 = 1
5 ln 6
5 < math > Therefore
.So < math > k = 0.0365
1
(2x)(3x) dx = 1
(2x) 1
(3x) dx = ln(2 x) +
ln
60 = 0.0365t ln(3 x) + c
Half life calculations are similar but the exponent is neg- (4) What is
1
ative. log2 64
24 CHAPTER 4. TESTS AND EXAMPLES
(10) x3 (x (2x + 3)(2x 3)) (20) What is 2ei4 cos 4 in terms of sin and cos
Expand out the dierence of 2 squares rst.....collect and This is just Eulers equation..... 2e
i4
= 2 cos 4
multiply....then just dierentiate term by term giving: 2i sin 4
20x4 4x3 + 27x2 so one cos 4 disappears to give ... cos 4 2i sin 4 .
3
(11) 3x cos 3x
This needs the product rule.... Factor out the 9x2 .... 50 Minute Test II
9x2 (cos 3x x sin 3x)
(1) Simplify 2 ln(1/x3 ) + 5 ln x
(12) ln(1 x)2
1
(2)What is log10
This could be a chain rule problem....... 10 000
1
(1x) 2 .2.(1).(1 x) (3) Solve the following equation for t
or you could take the power 2 out of the log and go straight t 3t 4 = 0
2
to the same answer with a shorter version of the chain rule (4) Solve the following equation for w
to: (1x)
2
.
w2 + 4w 12 = 0
(13) Perform the following integrations:
( ) (5) Multiply the two complex numbers
2 cos2 + 2 d (4, 3) and (5, 2)
cos2 must be converted to a double angle form as shown (6) Multiply the two complex numbers 3+2i and 3
many times.... then all 3 bits are integrated giving ....... 2i
cos sin + + 2 (7) The Maclaurin series for which function begins with
( 3 4 )
(14) 8x + 3 dx 8 these terms?
x x
, which goes to ln , this is straightforward x x /6 + x /120 + . . .
3 5
Apart from x4
polynomial integration. Also there is a nasty trap in that (8) Dierentiate with respect to x :
two terms can be telescoped to x163 .
x3 (2 3x)2
( x82 + 4 ln x)
(9) 2x 23x
(15) What is the equation corresponding to the determi-
nant: (10) x4 3x2 + k
b 1 0 where k is a constant.
1 2
b 1 = 0
2 (11) 3x2 4 Ax4
0 1 b
where A is a constant.
4.2. TESTS AND EXAMS 25
(12) 3x3 e3x (17) What is the equation corresponding to the determi-
(13) ln(2 x) 3 nant:
x 1 0
(14) Perform the following integrations:
1 x 0 = 0
( 4 )
3w 2w2 + 5w6 2 dw 0 0 x
x1
(15) (3 cos + ) d (18) Express (x+3)(x4) as partial fractions.
(16) What is the equation belonging to the determinant (19)What is the general solution of the following dier-
\begin{vmatrix} x & 0 & 0\\ 0 & x & i \\ 0 & i & x \\ ential equation:
\end{vmatrix} = 0</math> d r
dr = A
(17) What is the general solution of the following dier-
ential equation: (20) What is ei2 2i sin 2 in terms of sin and cos.
dy
dx = ky
(18) Integrate by any appropriate method:
( )
ln x + x4 dx
x+1
(19) Express (x2)(x+2)
as partial fractions.
(20) What is 2ei2 + 2i sin 2 in terms of sin and cos.
Further reading
5.1 Further reading Maths for Chemistry is an online resource providing in-
teractive context-based resources which explain how var-
ious aspects of maths can be applied to chemistry. There
5.1.1 Further reading
are quizzes and downloadable les to check understand-
ing.
Books
Online resources
26
Chapter 6
6.1 Text
Mathematics for Chemistry/Introduction Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Introduction?oldid=
1938631 Contributors: Amigadave and Adrignola
Mathematics for Chemistry/Number theory Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Number_theory?
oldid=2097024 Contributors: Whiteknight, Jguk, MartinY, Mikes bot account, Amigadave, NipplesMeCool, Adrignola and Anonymous:
2
Mathematics for Chemistry/Functions Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Functions?oldid=1612124
Contributors: Amigadave and Adrignola
Mathematics for Chemistry/Units and dimensions Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Units_and_
dimensions?oldid=2587155 Contributors: Whiteknight, Jomegat, Jguk, MartinY, Mikes bot account, QuiteUnusual, Amigadave, Adrignola
and Anonymous: 8
Mathematics for Chemistry/Statistics Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Statistics?oldid=1612175
Contributors: Whiteknight, MartinY, Mikes bot account, Amigadave and Adrignola
Mathematics for Chemistry/Plotting graphs Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Plotting_graphs?
oldid=1612136 Contributors: Amigadave and Adrignola
Mathematics for Chemistry/Complex Numbers Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Complex_
Numbers?oldid=2514602 Contributors: Whiteknight, Jguk, MartinY, Mikes bot account, Amigadave, Adrignola and Anonymous: 1
Mathematics for Chemistry/Trigonometry Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Trigonometry?oldid=
2174342 Contributors: Whiteknight, MartinY, Mikes bot account, Amigadave, Adrignola and HethrirBot
Mathematics for Chemistry/Vectors Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Vectors?oldid=2358133 Con-
tributors: Whiteknight, MartinY, Recent Runes, Mikes bot account, Amigadave, Adrignola and Anonymous: 2
Mathematics for Chemistry/Matrices and Determinants Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/
Matrices_and_Determinants?oldid=2563875 Contributors: Whiteknight, Jguk, MartinY, Mikes bot account, Amigadave, Adrignola, Lla-
maAl and Anonymous: 4
Mathematics for Chemistry/Dierentiation Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Differentiation?oldid=
2168593 Contributors: Whiteknight, Jguk, MartinY, Mikes bot account, Amigadave, Adrignola, Frigotoni and Anonymous: 1
Mathematics for Chemistry/Integration Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Integration?oldid=
2680267 Contributors: Whiteknight, Jomegat, Jguk, MartinY, Xania, Mikes bot account, Jake Wasdin~enwikibooks, Amigadave,
Adrignola and Anonymous: 5
Mathematics for Chemistry/Some Useful Aspects of Calculus Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/
Some_Useful_Aspects_of_Calculus?oldid=1612173 Contributors: Whiteknight, Jguk, MartinY, Mikes bot account, Amigadave and
Adrignola
Mathematics for Chemistry/Some Mathematical Examples applied to Chemistry Source: https://en.wikibooks.org/wiki/
Mathematics_for_Chemistry/Some_Mathematical_Examples_applied_to_Chemistry?oldid=1612172 Contributors: Whiteknight, Jguk,
MartinY, Mikes bot account, Amigadave, Adrignola and Anonymous: 1
Mathematics for Chemistry/Tests and Exams Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Tests_and_Exams?
oldid=1612176 Contributors: Whiteknight, MartinY, Mikes bot account, Amigadave and Adrignola
Mathematics for Chemistry/Further reading Source: https://en.wikibooks.org/wiki/Mathematics_for_Chemistry/Further_reading?
oldid=1731273 Contributors: Thenub314, Amigadave, Adrignola, Msuxg~enwikibooks and Gibbs~enwikibooks
27
28 CHAPTER 6. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES
6.2 Images
File:Argon_dimer_potential.png Source: https://upload.wikimedia.org/wikipedia/commons/0/04/Argon_dimer_potential.png License:
CC-BY-SA-3.0 Contributors: Self-made with Gnuplot. Converted to PNG with GIMP Original artist: Poszwa
File:Book_important2.svg Source: https://upload.wikimedia.org/wikipedia/commons/9/91/Book_important2.svg License: CC BY-SA
3.0 Contributors: Own work Original artist: darklama
File:Trigonometric_Triangle.svg Source: https://upload.wikimedia.org/wikipedia/commons/4/48/Trigonometric_Triangle.svg License:
CC-BY-SA-3.0 Contributors: en:Image:Trigonometric Triangle.PNG/Image:Trigonometry triangle.svg Original artist: Traced by User:
Stannered
File:Wikipedia-logo.png Source: https://upload.wikimedia.org/wikipedia/commons/6/63/Wikipedia-logo.png License: GFDL Contrib-
utors: based on the rst version of the Wikipedia logo, by Nohat. Original artist: version 1 by Nohat (concept by Paullusmagnus);