AUSTRALIAN CHEMISTRY OLYMPIAD

(AChO)

2015
PREPARATORY
NOTES
0. INTRODUCTION
The AChO Summer School is a 2 week intensive program that aims to present new,
interesting and challenging chemistry to students who have shown a talent in the subject.
Each year, AChO students come from diverse backgrounds. In particular, the high school
curricula vary from state to state. The aim of these preparatory notes is to provide you with
some background information which will help you get into gear for the camp. It is important
that you read these notes and are familiar with the material before arriving in January.
We are also happy to provide guidance if you find any part of these notes unclear. Feel free to
contact us by email:

Sam Alsop

email: samuelalsop@bigpond.com

Audrey Lee

email: aud2005@gmail.com

We hope you will spend some time going through these notes and we look forward to seeing
you in the summer.
The Australian Chemistry Olympiad Team

1. MATHEMATICS
As with all branches of science, the accurate modelling of physical phenomena requires a
mathematical toolkit to aid and concrete the description. You will find that these
mathematical tools pop up frequently during the Summer School, particularly in the physical
chemistry and analytical chemistry topics. For this reason, it is important to read the
following section thoroughly and attempt the problems associated with each section. Along
with what is covered here, it is also expected that students:

are confident solving simple linear and quadratic equations and inequations
are able to solve a system of simultaneous equations using elimination and
substitution techniques
are comfortable with tabulating, graphing and interpreting data (particularly during
laboratory sessions)

1.1 Significant Figures

When you are doing any sort of scientific calculations you need to be aware of significant
figures, decimal places, and how accurately you can report your results.
Significant figures include every figure in the number except zeros that are used to place the
decimal point
Example. The following all have three significant figures
a. 0.465
b. 0.0465
c. 15.0 (this zero is not placing the decimal point but makes the number more accurate
than 15 so is significant)
When performing operations with numbers with different significant figures, one must be
aware of the accuracy with which the answer can be reported. The following table is a
summary of the rules to use:
Operation

Rule

Example

a+b=c

The answer should be given to the same

number of decimal places as the original
numbers (whichever of a or b has fewer)

53.06 52.1 = 1.0

ab = c
a b = c

The answer should be given to the same

number of significant figures as the original
numbers (whichever of a or b has fewer)

43 0.01 = 0.4

logb a = c

The answer should be given to the same

number of decimal places as significant figures
in the original number a.

log10 11.2 = 1.049

10a = c

The answer should be given to the same

number of significant figures as decimal places
in the original number a.

100.42 = 2.6

ab=c

Note that multiplication and division take priority over addition and subtraction so would be
reported to the correct number of significant figures.
Rounding of a number should not occur until the final answer. When rounding the following
rules apply for the first number excluded from the answer:
Less than 5 (0-4): nothing will change
Greater or equal to 5 (5-9): the last number that you have in your answer will be
increased by one
Example. Round the following to 2 significant figures:
a. 34.5 = 35
b. 0.09385 = 0.094
c. 1.34 = 1.3
Additional References:

www.chem.tamu.edu/class/fyp/mathrev/mr-sigfg.html
chemed.chem.purdue.edu/genchem/topicreview/bp/ch1/sigfigs.html
Problem Set 1.1:
1.1. Write the following to the correct number of significant figures or decimal places as
required.
a. 32.15-7.98
b. 0.253 0.04556
c. (34.5+12.45)-1.00
d. (10.00 9.00) 5.000
e. (12.32 + 9.11) 0.10

1.2 Logarithms
Logarithms are used to solve equations such as 10x = 100 by rearranging the equation to give
log10 100 = x allowing for the solving of x. It is the inverse (reverse action) function of an
exponential function (log10x is the inverse of 10x, log2x for 2x etc.). While it might seem
redundant for simple propositions like the one above, once x starts to change from a whole
integer it becomes much more important. For example, 10x = 567.
There are two common forms of logarithms, or logs, used in chemistry. The first is log to the
base 10 written as log10 or more simply as log. The other is the natural log, loge or more
simply as ln, where the base e is approximately equal to 2.71828.
For all purposes in chemistry the answer of a log can be produced using a calculator.
However manipulating an equation may become important for simplifying problems. The
following rules should be obeyed and apply to log and ln equally.

Logarithm Law
Equation

Rearranged equation

Example Calculation (Solve for x)

(associated logarithm law)

10y = x

Solve ex = 901

log x = y

x = ln 901 = 6.804
log x = y

10y = x

Solve log x = 1.69

x = 101.69 = 49

log (a b) = y

log (a) + log (b) = y

Solve log (10 x) = 2

(logarithm of a product of
two elements is the sum of
the logarithm of each
element)
log (a b) = y

log (a) log (b) = y

log (10) + log (x) = 2

1 + log (x) = 2
log (x) = 1
x = 10
Solve log (x 42) = -0.26
log (x) - log (42) = -0.26

(logarithm of a quotient of
two elements is the
difference of the logarithm
of each element)
log (ac) = y

log(x) = -0.26 + log (42)

x = 10 -0.26 + log (42)
x = 23
Solve ln (4x) = 19

c log (a) = y

x ln (4) = 19

(follows from the 3rd

property)

x = 19 ln (4)
x = 17.71

logx x = y

Solve ex = 901

y=1
(logarithm of a number to
the base of itself is 1)

ln(ex) = ln (901)
x ln(e) = ln (901)
x = ln (901) = 6.804

logx1 = y

y=0

Solve log (1 x ) = 2

(the logarithm of 1 is 0 in
any base y)

log (1) log (x) =2

log (x) = -2
x = 10-2 = 0.01

logb (x)

= loga (x) loga (b)

Find log3 (7) in terms of logarithms to the

base 10 only.

(changing the base of a

logarithm from a to b)

log3 (7) = log10 (7) log10 (3)

Additional References:
www.physics.uoguelph.ca/tutorials/LOG/
www.chem.tamu.edu/class/fyp/mathrev/mr-log.html
Problem Set 1.2.:
1.2 Find y remembering to use the correct number of significant figures.
a. log y = 0.20
b. 10y = 14
c. log y = -5.87
d. log (12 3.00) = y
e. log (y 3.00) = 0.60
f. log y-1 = 5.60

1.3 Calculus
1.3.1 Functions, Operators and Functionals
Functions are the working objects of basic calculus. A function of a variable, f, maps an input
x (usually a real number) to another number f (x) as determined by the function. It defines a
one-to-one relationship between one variable and another.

Figure 1.3.1: the action of a function

Many phenomena can be expressed as such relationships. Some examples include:
a) the position of a car on a road could be expressed as a function of time, i.e. x(t)
b) the population of whales in a given region of ocean might be expressible in terms
of a function of the average krill population in that region, i.e. wpop(kpop).
We are most familiar with functions in their graphical form: the set of points (x, f(x)) on two
axes. For instance, we have all probably seen graphs of y = f(x) = x2 (a parabola) and
y = f(x) = sin(x) (the sine wave function).
These functions are called analytic as the action of the function is expressible in some closed
algebraic form. Note that there is no restriction that states functions have to be analytic - we
could imagine a function which was still a one-to-one relationship but that we could not
express with any algebra known to us (consider a random scatter of points). In fact, it is
frequently the case that physical problems involving functions cannot be solved in any
closed/analytic form. In this case a lot more work is required to describe the function. Luckily
for us, most of the functions we'll deal with at the Summer School are smooth-looking
(continuous) and analytic!
We can also have functions of more than one variable. For instance, the population of whales
might depend on both the population of krill and the average temperature. So we write the
function as wpop(kpop, Tavg), in terms of variables kpop and Tavg.

We have just defined a function as a relationship that maps one real number to another real
number. There are other kinds of relationships, such as:

An operator maps a function to another function - that is, if you take a function, and
apply an operator, you'll get another function. Lots of operators have a special

. Examples are the differential and

notation, a circumflex or 'hat' above them: O
indefinite integral operators, as explained in the following sections.

A functional maps a function to real number - that is, if you take a function and
apply a functional, you'll end up with a real number. The simplest example of a
functional is a definite integral, as defined below.

1.3.2 Differentiation
KEY IDEA:
Differentiation is about finding the rate of change of one variable compared to another, or
the rate of change of a (continuous) function f(x) with respect to the variable x.
If we have a graph comparing two variables (e.g. y, x), where y = f(x), then differentiation is
equivalent to finding the gradient of the curve.
The gradient of a straight line function is given by Rise over Run. We can express the

y
, where y is the change in y and x the change in x between two
x
2
points (see Fig 1). For a graph/function that is curved (for instance for the graph y = x ) the
gradient as m =

gradient is no longer constant, but is different at each point. We get closer to the true value of
the gradient at a certain point by decreasing the size of x and y (see Fig 2).

Differentiation finds the true value of the gradient by allowing x and y to approach (or
get infinitely close to) zero.

Notation:
An infinitely small value of x is expressed as dx, and y as dy
The true value of the gradient for any function (at a given point) is given by:

m=

dy

lim x = dx

y,x 0

In terms of the function defining the y variable, this equivalently becomes:

dy df ( x)
f ( x + x) f ( x)
=
= lim
dx
dx
x
x 0
This object, df /dx, is referred to as the derivative (rate of change) of the function f
with respect to the variable x.
Differentiation changes one function into another.
As we said, the value of the gradient (the derivative) can vary from point to point (like in a
parabolic function). For this reason, we expect the action of taking the derivative
(differentiating) of a function to return another function (an operator relationship). For
instance, to find the derivative of the function f ( x) = x 2 , we start with:

df
( x + x) 2 x 2
=
dx lim
x
x 0

(1)

Expanding gives:

df
x 2 + 2 xx + (x) 2 x 2
= lim
dx x 0
x
(2 x + x)x
= lim
x
x 0
= lim (2 x + x)
x 0

= 2x
where the last line follows from the fact that x is approaching 0.
Therefore

df
= 2 x , where f(x) = x2.
dx

Table of Derivatives
Luckily for us, it is unnecessary to apply the formal definition of differentiation every time
we want to find a derivative. In fact, in practical use - no-one does. We use short-cuts. Below
is a tabulated list of common derivatives and how to find them. It is very important to learn
these.

d
(C ) = 0
dx

Differentiating a constant gives zero

(i.e. a horizontal line has zero
gradient)

d
(ax + b ) = a
dx

Differentiating a linear equation gives

a constant (i.e. the gradient of a
straight line is constant)

d n
(
x )= nx n 1
dx

Differentiating a polynomial lowers its

power by 1, but multiplies the result
by the original power (recall the
2
derivative of y = x )

d x
(
e )= e x
dx

Differentiating the exponential of

Eulers constant e (e = 2.71828)
gives itself

d
(ln x) = 1
dx
x

Differentiating the natural logarithm

gives 1/x

d
(sin x) = cos x, d (cos x) = sin x
dx
dx

Differentiating sine gives cosine, and

differentiating cosine gives the
negative of sine

The linearity property:

d
(kf ( x) + lg( x)) = k d ( f ( x)) + l d (g ( x)) - the derivative of a scalar multiple of
dx
dx
dx
a function is just the scalar times the
derivative of the function.
- the derivative of the sum of two
functions is the sum of the two
derivatives

where k, l are constants.

Product Rule (by illustration):

Suppose that two functions x(t) and y(t) change
with time t in Fig 3, e.g. the side lengths of a
rectangle.
Note that

Area(t ) = x(t ) y(t ) .

Then the change in area:
d ( Area) = xdy + ydx
dy dx is infinitely small compared with
either of dy , dx and is thus negligible.
Hence:

d ( Area)
dy
dx
=x +y
dt
dt
dt
In general:

d ( fg )
dg
df
=f
+g
dx
dx
dx
where f and g are arbitrary functions. This result is called the product rule and allows one to
calculate more complicated derivatives.
Chain Rule:
When there is a function within a function (e.g. when z ( x) = ln(sin x) , which is equivalent
to stating two functional relationships: y ( x) = sin x and z ( y ) = ln y ), then

dz dz dy
=

dx dy dx
In the given example,

dz dz dy 1
1
1
=

= cos x =
cos x =
dx dy dx y
sin x
tan x

Problem Set 1.3.2:

1.3.1. Evaluate

dy
, using the appropriate rules:
dx

Differential Rules
2
a. y = 4 x + 5 x 1
b.

y = ln x + cos x 5e x

Product Rule
c. y = x ln x
d. y = sin x cos x

)(

e. y = x 1 x + 4

NB: k is a constant.

Chain Rule
f. y = sin (kx)

g.

y = sin (x 2 )

h.

y = x3 + 1

1.3.3 Integration
KEY IDEAS:
1. Integration is the opposite operation of differentiation. It computes an antiderivative.
It takes you from a rate of change function to an explicit relationship between the two
quantities. This means if you have a rate of change of a quantity expressible in functional
form f(x) and want to calculate a direct relationship between the quantity and the
variable, you would integrate the rate of change f(x) with respect to x. Since this action
takes a function to a function, it is an operator. We call this taking an indefinite integral.
For example, if you knew the rate of change of position with respect to time (the
velocity), as v(t) = dx(t)/dt, you would integrate the function v(t) to find the function x(t).
2. Integration can also find the area under the curve (x, f(x)) between two points. If you
take the indefinite integral function, F(x), found from Key Idea #1 and compute the
difference in F(x) between two points you will obtain the area (bounded by the axis)
under the original function f(x). Since this takes a function to a number (an area), it is a
functional. We call this taking a definite integral.
How can both these ideas be true? It turns out they're equivalent. This is proved below for
your reference. This is not essential knowledge, however, and may be skipped at your
discretion.
Proof:
Suppose you are trying to estimate the area under a curve y = f ( x) by drawing rectangles
under the curve and calculating its area (Fig 4). By decreasing the width ( x ) of the
rectangles, you arrive at a better estimate (Fig 5). Obviously, the best estimate is when x is
infinitely small (i.e. x approaches zero).

Note: if the curve is in below the horizontal axis, the area between the zero line and the
curve is negative in value.
Now, let us define y = F ( x) which we can use to find the area under the curve of y = f ( x) .
Here is how the function works (see Fig 6):
An area bordered on the left by x = A, on the right by x = B, above by y = f ( x) , and below
by y = 0 is given by
AREA = F ( B) F ( A)
(This is AREA (2) in Fig 6)
NB: If the curve y = f ( x) lies below y = 0 (i.e. is negative), then the value of this area is
also negative

10

Using these rules, we can see that AREA (1) is expressed as

AREA (1) = F(A) F(0),
and the sum of AREA (1) and AREA (2) is given by
AREA (1) + AREA (2) = F(B) F(0)

Then the area bounded by the infinitely small rectangles we were exploring in Figure 4 and 5
is given by:

AREA= F ( x + x) F ( x) = f ( x)x
As x approaches zero, this becomes:

AREA= F ( x + dx) F ( x) = f ( x)dx

Note that F ( x + dx) F ( x) is simply another way of writing change in y (or dy ) or
dF ( x) !
Rearranging:

F ( x + dx) F ( x) dF ( x)
=
= f ( x)
dx
dx
Thus, the differential of our area under the curve function is the original function.

Definite and Indefinite Integrals:

An indefinite integral in the above example is simply y = F ( x) , a reverse of differentiation.
F(x) is called the anti-derivative.
Notation:

F ( x) = f ( x)dx

A definite integral is an expression that finds the area bound by the curve, horizontal axis,
and two horizontal axis values (the vertical lines x = a and x = b).
b

Notation: F ( B) F ( A) =

f ( x)dx
a

11

Note: In this way (expressed in Figure 5 above), the integral notation is actually a continuous
sum! It sums the product f(x)dx (product of the graphical height of the function f(x) and the
width of each rectangle) continuously between the bounds a and b. This can be expressed
mathematically as:
b

f ( x)dx = lim f ( xn )xn

n

n=a

(where xn is the midpoint of the one of the rectangles, n is the number of rectangles, and xn is
the width of the each rectangle (which decreases as the number of rectangles increases)).
2

Example. To find the area under the curve y = x between x = 1 and x = 4 , we find the
indefinite integral, which is

x dx = 3 x

+ C (see the table below), and then turn it into a

definite integral by substituting the lower and upper bounds (i.e. the A and B):
B

x3
4 3 13 63
AREA= f ( x)dx = x dx = =
=
= 21
3 3
3
3 1
A
1
2

12

Table of Indefinite Integrals

Luckily, once again, we do not have to use the formal definition of integration to compute
integrals - we have rules. These rules for computing anti-derivatives are summarised in the
table below. You'll notice that they are simply the reverse of differentiating.
Note that indefinite integrals always contain an integration constant, C. This is because
differentiating a constant gives 0 (previous section), so we are free to choose an arbitrary
constant in the reverse process. The constant is often determined after the integration by using
a physical condition given to us (for instance, the value of the new function at a particular
value of x). This integration constant will always cancel out in definite integrals.

0dx = C

Integrating anything gives an infinite

number of similar functions, all varying
by a constant number C.

adx = ax + C

Integrating a constant gives a linear

equation
(a curve with a constant gradient is
obviously any straight line with that
gradient)

nx

n 1

From the derivative law!

dx = x n + C OR

x n +1
x dx = n + 1 + C
n

e dx = e

From the derivative law!

+C

dx
x

x dx = ln x + C

x dx is sometimes written as

sin dx = cos x + C; cos dx = sin x + C

Simple reversals of the differentiation

rules

[af ( x) + bg ( x)]dx = a f ( x)dx + b g ( x)dx + C

Integrals, like derivatives, are linear.

Problem Set 1.3.3:

1.4. Integrate
2

x + 5 x + 3dx
b. cos x + sin xdx
kdx
c.
where k is a constant
x
a.

d.

kdx
where k, n are constants and n > 1
xn

13

1.3.4 Representation as Operators

We've talked about the fact that both differentiating (finding the derivative) and integrating
(finding the indefinite integral) are operations, so now it's time to make some important
distinctions.
d
If we write
before a function, it means we take that function and return its
dx
derivative.

Similarly, if we write dx after a function and place the integration (

front of it, it means we take that function and return its integral.

e.g.

) sign in

d 2
( x ) = 2 x , 2 xdx = x 2
dx

This idea of representing a differential operator as

the derivative itself,

d
is not to be confused with the idea of
dx

df
, which is a well-defined quantity (a ratio of two changes) and is no
dx

longer an operator. The derivative can be manipulated in a normal way, for instance if

df
=1
dx
df = dx
is implied.
We can take the derivative of a function more than once. For example, the second derivative
of a function f is defined as

d df
d2 f
. For examples, the second derivative of
( )=
dx dx
dx 2

position with respect to time is acceleration in mechanics. Higher derivatives are defined
similarly.

Note: at no point can you cancel the d letters. Remember that df and dx represent
changes in a particular variable and can be manipulated in the normal algebraic way,
and that the d by itself is meaningful only as an operator.

1.3.5 Separable Differential Equations

These calculus ideas actually underpin most of physics (and hence physical chemistry). The
most common form in which one finds calculus is differential equations. Differential
equations involve relationships between derivatives and functions, and are often incredibly
complicated to solve. They are often unsolvable in terms of analytic functions.
The reason they are so common in physics is because physics describes dynamics, or rates of
change (derivatives). The most obvious exam is Newton's law of motion, which translates
into a simple differential equation.
ma = F,
where F is force, m is mass and a is acceleration
14

In differential equation language, this translates to:

d 2 x(t )
= F(x , t )
dt 2

These differential equations also have more obvious chemical applications, particularly in
thermodynamics and chemical kinetics.
At Summer School, you will only have to solve a special class of differential equations called
separable differential equations. This means that all variables of one type can be collected
on one side of the equation by algebraic manipulation, and all variables of the other type can
be collected on the other side. Since both sides (infinitesimal changes) are equal everywhere,
both sides can be easily integrated (summed) to give the explicit relationship desired. This
technique is demonstrated in the example below.

dA
= kA (where k is a constant)
dt

Solve
Solution:

(1) We separate the two variables, A and t, to either side:

kdt =

1
dA
A

(2) We integrate both sides:

kdt = A dA

(3) The desired relationship is reached:

kt = ln A + C where C is the constant of integration
(4) The constant of integration is either left arbitrary, or determined by some given
condition (e.g. the value of A when t = 0)
Problem Set 1.3.5:
1.5.1. The concentration of a reagent A (denoted [A]) is found to decrease as a function of
kt
time t via the following relationship: [ A] = [ A]0 e (where k is a constant and

[ A]0 is the initial concentration of reagent A). Show that the rate of change of [A]
d [ A]
(i.e.
) is proportional to the concentration of [A].
dt
1.5.2. The rate of a reaction is found to vary according to the following relation:

d [ A]
= k[ A] 2 . The initial concentration (i.e. t = 0) of the reagent is [A]0
dt
1
+ C = kt
a. By separating variables, prove that
[ A]
1
1

= 3k
b. At t = 3 sec, prove using a definite integral that
[ A]3 [ A]0

15

1.4 Complex Numbers

If you were asked to solve the equation ! = 1, what would your response be? If your
answer is anything along the lines of you cant take the square root of a negative number,
then boy, is this the section for you! Read on, brave Summer Scholar, to discover the world of
complex numbers.

1.4.1 The in the sky

Im going to go out on a limb here, and define a number called , which stands for imaginary.
This number is defined by this simple equation:
= 1
itself is called the imaginary unit.
You cant do that! I hear you say.
Why not? Just as all numbers are inventions, so too is this new one. As long as it fits neatly
into our current system of numbers, why cant we use it alongside what we already know? In
fact, lets see what happens when we apply some simple maths and see where that leads us:
!

! = 1 = 1
! = ! = 1 =
!
= ! ! = 11 = 1
Thats pretty cool, so if we try multiplying by itself lots of times, we always end up going in
a circle of , 1, , 1, ,
9 = 91 = 9 1 = 3
And now, we can take square roots of any number!
Problem Set 1.4.1:
Evaluate the following:
a) !
b) !"
c) !""
d) 49
e)
50
f) 144
Solve the following equations:
g) ! = 16
h) ! = 40
i) ! + 5 + 10 = 0

1.4.2 Things are going to get more complex

So, things are about to get more complex. How so? Think a moment about the numbers you
use every day. In mathematical jargon, these are called real numbers.
What happens if we put both real numbers and imaginary numbers together?
1 + = ?
We cant actually combine the two into one single number they are fundamentally different
types of things. The best we can do is write it out just like we have above, with a real
component, and an imaginary component. This sum weve just created still represents one

16

number, its still one abstract quantity that appears to have two components, kind of like a
two-dimensional number. These sorts of numbers are called complex numbers.
Complex numbers have a real component and an imaginary component, and they can all be
represented in the form:
+
Where and are both real numbers. is called the real part and is called the imaginary
part.
Happily, we can do arithmetic with complex numbers, just by applying the normal rules we
have, and treating the real and imaginary components separately:
Addition
2 + 3 + 3 = 2 + 3 + 3 1 = 5 + 2
Subtraction
2 + 3 3 = 2 3 + 3 1 = 1 + 4
Multiplication
2 + 3 3 = 23 2 + 33 3
= 6 2 + 9 + 3
= 9 + 7
What happened to division? Well, it gets a bit messy. To do it, we have to introduce
something called the complex conjugate. As scary as this sounds, its really simple. If we
have a complex number = + , then the complex conjugate is defined as = .
Thats all there is. For example, the complex conjugate of 1 + is 1 .
We can use the complex conjugate to perform a neat little trick we can turn a complex
number into a real number! Take any complex number and multiply it by its complex
conjugate and watch what happens:
5 + 3 5 3 = 55 53 + 35 33
= 25 15 + 15 + 9
= 34
How awesome is that? In general:
+ = ! + !
Now, lets divide and conquer! Or we can conquer the divide. (Pick your pun)
Division (Gets a bit messy)
2 + 3 3 =

2 + 3
3

Now, multiply top and bottom by the conjugate of the denominator

=

2 + 3 3 +
6 3 + 2 + 9
=
3 3+
10

3 + 11
3
11
=
=
+

10
10 10

Problem Set 1.4.2:

Calculate the following, simplifying the answers as much as possible
a) 2 + + (8 5)
b) 3 7 + (2 + )

17

c) 1 + 4 2 + 3
d) 1 + 3 + 2
e) 4 + 3 3
f) ( 2 )( 8 + 2)
g) (1 + ) (2 )
h) 3 1 3
i) Challenge What is ?
Hint Write = + and solve ! = . Remember that and are real.

1.4.2 Egad! s gone crazy!

So, for Summer School, theres just one more important piece of info you need to know about
complex numbers. And its something called Eulers Formula.
Perhaps youve come across this wacky but devastatingly beautiful equation:
!" + 1 = 0
Five of the key numbers of mathematics united in one equation. It brings a tear to your eye,
doesnt it? This can easily be shown using Eulers Formula, which states:
!" = cos + sin
We must briefly touch on radians in order to use this formula.
What are radians you ask? So everybodys been familiar with dividing circles into 360 since
primary school. A radian is simply dividing the circle into 2 radians. Simple! As an
example, have a look at the following table:
Degrees
0
30
60
90
180
360

Radians
0
6
3
2

Degrees are probably the standard units for angles that you've come across so far. However, it
turns out that mathematically, there are very deep and fundamental reasons why radians are
used, as annoying as they may seem right now! So we'll be using radians when we apply
Euler's formula.
For example, lets prove our favourite equation by substituting = into Eulers Formula.
!" = cos + sin (= cos 180 + sin 180)
= 1 + 0 = 1
Problem Set 1.4.3:
Find exact expressions for the following:
a) !!"
b) !" !
c) !!" !
d) !"#!" !
18

2. ORGANIC NOMENCLATURE
The rules for naming organic compounds are set by an international body called the
International Union for Pure and Applied Chemistry (or IUPAC for short). The basics of
naming and drawing organic molecules will be covered here, to be expanded upon over
summer.

2.1 Basics:
There are three ways of writing formulae of organic compounds:
Structural Formulae: show all atoms, including hydrogen atoms which becomes difficult
when molecules become more complex
Example: 2-chloropropane

Cl

Condensed Structural Formulae: we just write out how many hydrogen atoms are present
without drawing those carbon to hydrogen bonds
Example: 2-chloropropane
Cl
H3C

CH

CH3

Skeletal Formulae there is a carbon at every vertex and the appropriate number of
hydrogen atoms is assumed to be bonded to each carbon atom. Hydrogen atoms are drawn
when bonded to non-carbon atoms.
Example: 2-chloropropane
Cl

Example: diethylamine
NH

Any organic molecule contains three main components:

the carbon backbone
the principal functional group, which influences the properties of the compound, is
referred to in the suffix of the name
substituents, which are secondary functional groups are named as prefixes

19

2.2 The carbon backbone:

The name of the backbone arises from how many carbon atoms are in the longest chain within
the molecule. For an example it is best to look at the alkanes, which are the simplest organic
compounds, containing only carbon and hydrogen with only single bonds between them. The
prefix (in bold) is used throughout molecule naming to describe a chain length with that many
carbon atoms in it.
H
H C H
H

CH4

methane

1 carbon

H3C CH3

C 2H 6

ethane

2 carbons

C 3H 8

propane

3 carbons

C4H10

butane

4 carbons

C5H12

pentane

5 carbons

C6H14

hexane

6 carbons

C7H16

heptane

7 carbons

C8H18

octane

8 carbons

We can then add any of a number of substituents to the chain and as you can see, when a
basic carbon chain is added the same prefix appears:
-CH3
-CH3CH2
-CH3CH2CH2

methylethylpropyl-

-F
-Cl
-Br

fluorochlorobromo-

isopropyl-

-I

iodo-

-CH2CH2CH2CH3

butyl-

-NO2

nitro-

CH3
-C-CH3
CH3

tert-butyl-

-NH2

amino-

-OCH3

methoxy-

-OCH2CH3

ethoxy-

-CH

CH3
CH3

At this point, there are a number of rules to introduce:

1. When there is more than one type of substituent, order prefixes in alphabetical
order.
Example: bromochloromethane not chlorobromomethane.
H
H

Cl

Br

20

2. When there is more than one of a substituent type, use prefixes di-, tri-, tetra- etc. to
signify the number. These prefixes do not contribute to the alphabetical order.
Example: dibromochloromethane not chlorodibromomethane
H
Br C

Cl

Br

3. To define where a substituent is attached, assign numbers to the carbon chain. Start
numbering from the end that will result in the lowest number for the substituent at
the first point of difference.
Example: 1-chloropropane not 3-chloropropane
Cl

4. Put a dash between all numbers and letters, a comma between numbers, and leave no
spaces between letters.
Example: 1,3-dichloropropane
Cl

Cl

5. Make sure that the backbone is the longest chain.

Examples of other Carbon Backbones:
Cycloalkanes: Are alkanes which have joined into a ring. These are named in exactly the
same way as alkanes, with a cyclo- prefix.
Example: 1-chloro-1-methylcyclohexane
Cl

Alkenes: Contain one or more double bonds. Similar rules to those applied to alkanes apply
here also. But you must number only the first carbon that has the double bond, and replace the
-ane of the alkane with -ene.
Example: 1-butene or but-1-ene

Example: 1,3-butadiene or buta-1,3-diene

21

The double bond takes priority over halo substituents so number from the end that will give
the lowest number to the alkene.
Example: 4-chloro-1-butene or 4-chlorobut-1-ene
Cl

Alkynes: Contain one or more triple bonds, and have the suffix -yne. The same rules as
alkenes apply, but if both are present then the alkene has higher priority than the alkyne.
Example: but-1-en-3-yne, not but-3-en-1-yne.

2.3 Functional groups:

Alcohols contain the OH group. Remember because the hydrogen is bonded to the oxygen it
is still drawn. If the alcohol is the principal functional group, the compound is named with an
-ol suffix, and numbering begins at the end which will give the lowest number for the carbon
attached to the OH.
Example: 1-propanol or propan-1-ol
OH

Example: 3-chloro-1-propanol or 3-chloropropan-1-ol

Cl

OH

If there is another group of higher priority, OH is named as a substituent, with the prefix
hydroxy- and is numbered accordingly. We will see the order of priority later.
O

R2
Carbonyl compounds contain the R1
group. Varying either R1 or R2 will then
change the type of carbonyl group. There are a number of different types of carbonyl
compounds:

Aldehyde - when one R group is a H and the other is a carbon atom bonded to anything else.
These are named with the suffix -al. An aldehyde will only be present at the end of a chain as
it cannot extend in both directions due to the requirement of the hydrogen.
Example: butanal
O

22

Ketone - when both R groups are a carbon atom bonded to anything else. These are named
with a suffix -one. Remember that because the C=O is in the middle of the chain, its position
will need to be shown by numbering.
Example
O

2-butanone or butan-2-one
Carboxylic acid: when one R group is an OH and the other is a carbon atom bonded to
anything else. These are named with the suffix -oic acid. Again this must be at the end of a
chain.
Example
O

OH

butanoic acid

increasing priority

We now come to priorities of functional groups. If a molecule is composed of more than

one functional group, the group of highest priority determines the root of the name (suffix)
and must be included in the longest chain. Any other functional groups are treated as
substituents and are described with the prefix.
functional group

suffix

carboxylic acid

-oic acid

aldehyde

-al

oxo-

ketone

-one

oxo-

alcohol

-ol

hydroxy-

alkene

-ene

-en-

alkyne

-yne

-yn-

alkane

-ane

-an-

Example: 2-hydroxypropanoic acid

HO

O
OH

Example: 2-oxopropanoic acid

O

O
OH

Example: but-3-enal
O

23

prefix

2.4 Aromatic compounds:

We now move to an entirely different area of organic chemistry, that of benzene.

Benzene consists of alternating double and single bonds, and can be represented as a
resonance of the above two forms. For simplicity, it is also represented by

A number of compounds of benzene have special names, listed here in order of

decreasing priority (as you read from left to right).
HO

OH

benzoic acid

phenol

NH2

aniline

CH3

anisole

toluene

If there are more than two groups attached, we need to define the positions:
ortho

ortho

meta

meta
para

Ortho, meta and para can be abbreviated to o, m and p.

Examples:
OH
Cl

Cl

Br

meta-dichlorobenzene

p-bromophenol

24

CH3

If there are more than 2 substituents, then we use numbering.

Example:
OH

Cl
Cl

3,4-dichlorophenol
If benzene is a substituent, it is known as the phenyl group, and can be abbreviated to Ph in
formulae.
Example:
O

OH

or

OH

Ph

3-phenylbutanoic acid
Additional References:
Brown and Poon, Introduction to Organic Chemistry, 3rd Ed, Wiley International
2005, Sections 3.1-3.6, 9.4, 13.3, 14.3 and pg 101-102.
Silberberg, Chemistry The Molecular Nature of Matter and Change, Sections 15.2:
The Structures and Classes of Hydrocarbons, 15.4: Properties and Reactivities of
Common Functional Groups
Problem Set 2:
2.1 Name the following compounds
O

a.

e.

b.
OH

f.
c.

g.
d.

25

Cl

NH2
Cl

OH

h.

i.
O

j.

O
OH

2.2. A compound has been named 3-chloro-2-ethyl-5-methyl-heptane. What should it

actually be called?

26

3. TRANSITION METAL CHEMISTRY

3.1 Introduction:
At Summer School, we will be talking about coordination compounds, also known as metal
complexes, which are known for all metals, but we will mostly be looking at the transition
metals. The molecules and ions which coordinate to the metal centre are called ligands. In
general, we can think of a coordinate bond formed between the metal and a ligand, in which
the ligand donates a pair of electrons to the metal centre. This bonding can quite drastically
change the reactivity of the metal and ligand.
For example, hexacyanidoferrate(III) (also called ferricyanide) comprises of six cyanide
ligands and an iron(III) centre. Usually the cyanide ion is very toxic, however
hexacyanidoferrate(III) has a very low toxicity, due to the strong iron-carbon bonds.

Another point to note is that hexacyanidoferrate(III) is an anion, so there is a positive counter

ion. The counter ion, frequently sodium or potassium for hexacyanidoferrate(III), is not
covalently bound to the metal or ligands and does not drastically change the reactivity.
One thing you may not have seen before is the wedged bonds. These are used to show that a
bond is not in the plane of the page. The solid wedged bonds come out of the page and the
dashed bonds go into the page. Here is another diagram of the hexacyanidoferrate(III) ion to
compare with the structure before.

27

3.2 How to draw a metal complex:

Metal complexes can have from one to twelve atoms attached to the metal centre so it is
important to be able to clearly show the geometry around the metal centre. The number of
atoms attached to the metal is called the coordination number, often abbreviated to CN.
Coordination numbers of 4 and 6 are the most common and there are multiple different
geometries around the metal centre that can be observed for the same coordination number.
CN = 6
Complexes with coordination numbers of six are usually octahedral, which puts the metal
centre at the centre of an octahedral formed by the atoms attached to it. The
hexacyanidoferrate(III) above is an example of an octahedral complex. This is the most
common way to draw octahedral complexes, however sometimes we draw them as shown
below.

3-

CN
NC

CN
Fe

NC

CN
CN

CN = 4
Complexes with a coordination number of four can be either square planar or tetrahedral and
we will discuss why at Summer School. For the purpose of getting you to practice drawing
them, you will be told if a complex is square planar or tetrahedral for the exercises.

2+

NH 3
H 3N

Br

NH 3

2-

Br
Ni

Pt
NH 3

H 3N

Br
Br

H 3N

Tetrahedral

Pt

NH 3

2+

NH 3
Square Planar (either is acceptable)

3.3 Naming:
There are a number of rules for naming coordination compounds.
1. The cation is names before the anion, as you've seen for naming simple ionic
compounds.
2. The ligands are named (in alphabetical order) before the metal.
3. If the ligand is anionic, replace the final -e with an -o.
4. If the ligand is neutral, use the full name. Do not abbreviate the name.
5. For multiples of the same ligand, use the prefixes below
28

If the ligand doesn't contain one of the

following prefixes e.g. chlorido

If the ligand does contain one of the following prefixes

e.g. 1,2-ethanediamine

di

Bis

tri

Tris

tetra

tetrakis

penta

pentakis

hexa

hexakis

6. If the complex is anionic, add -ate onto the end of the name of the metal. If it ends in -ium
or -um, replace it with -ate. Some metals also go back to their Latin roots.
Metal

Anionic Name

Metal

Anionic Name

Nickel

Nickelate

Palladium

Palladate

Copper

Cuprate

Iron

Ferrate

Lead

Plumbate

Gold

Aurate

Silver

Argentate

Tin

Stannate

Mercury

Mercurate

Manganese

Manganate

7. Write the oxidation number of the metal in Roman numerals after the metal. For example,
Fe(III).
For formulas, there are similar rules.
1. Cation before anion, as for ionic compounds.
2. The formula of the complex is in square brackets.
3. Inside the square brackets, the metal centre is first.
4. Ligands are written with the atom attached to the metal first or abbreviated and
ordered alphabetically. If there are multiples of the one ligand, follow with a
subscript. If the ligand comprises of multiple atoms, surround it with round
brackets.
Examples:

H2
N

H 2N
Co

N
H2

3+
NO 3NH 2

K+

NO 3-

Cu

NH 2
H 2N

2-

Cl

K+

NO 3-

tris(1,2-ethanediamine)cobalt(III) nitrate
[Co(en)3](NO3)3

Cl

Cl
Cl

potassium tetrachloridocuprate(II)
K2[CuCl4]

29

3.4 Common ligands:

There are a number of common ligands, which we will repeatedly see during Summer School.
The most important of these, namely water, ammonia, carbon monoxide and nitrogen
monoxide, are the exceptions to the rule for the names of neutral ligands are unchanged. The
differences are highlighted in the table below.
There are also ligands that can attach to the metal centre at two or more atoms, like
1,2-ethanediamine as before, through its two nitrogen atoms. These are called polydentate
ligands. Ligands which can only bind through one atom are called monodentate. Ligands with
two binding atoms are called bidentate; three tridentate, and so on. These can be contrasted
with ligands like the nitrite ion (NO2) and the thiocyanate ion (SCN), which have a lone pair
on more than one atom in the ion, so they can bind through either, but not both atoms. These
are called ambidentate ligands.
Molecule or ion

Ligand name ( - if neutral)

Formula (abbreviation)

Donor atoms

ammonia

ammine

NH3

water

aqua

H 2O

carbon monoxide

carbonyl

CO

nitrogen monoxide

nitrosyl

NO

acetonitrile

NCCH3

bromide

bromido

Br

Br
2-

carbonate

carbonato

CO3

chloride

chlorido

Cl-

Cl

cyanide

cyanido

CN-

iodide
nitrite

iodido

O or 2 O (can be
monodentate or
bidentate)

I
-

nitrito

NO2

nitride

nitrido

3-

N or O

oxide

oxido

O2-

O (doubly bonded
to the metal)

thiocyanate

thiocyanato

SCN-

S or N

pyridine

N (triply bonded to
the metal)

C5H5N (py)
1,2-ethanediamine
(ethylenediamine)

H2NCH2CH2NH2 (en)

2N

oxalate (ethanedioate)

oxalato

C2O42- (ox)

2O

2,2'-bipyridine

2N

30

C10H8N2 (bipy)
triphenylphosphine

P(C6H5)3, PPh3
glycinate

H2NCH2COO- (gly)

glycinato

ethylenediaminetetracetate ethylenediaminetetracetato
(EDTA)

1 N and 1 O
2 N and 4 O

O
O-

O
N

-O

O-

N
-O

O
O

C10H16N2O8 (EDTA)

Problem Set 3:
Note that some of these complexes have isomers, but we will discuss isomerism in detail at
Summer School.
1. Name and write the formula for each of the following complexes.
a)
b)

2-

OH2
H 3N

Cl
Cr

H 3N

Na +

NO 3-

CO
O
Mn

Cl

Na +

NH 3

2. Draw and write the formula for each of the following complexes.
a) diaquabis(2,2'-bipyridine)iron(II) chloride
b) diamminedichloridoplatinum(II) square planar
3. Draw and name each of the following complexes.
a) [RhCl(PPh3)3] square planar
b) [Zn(gly)2] tetrahedral

31

OH2
OH

OH

4. THEROETICAL CHEMISTRY / ELECTRONIC

STRUCTURE
In principle, all the chemical properties of matter can be derived from physical laws of
motion. For example, the simplest chemical system a hydrogen atom consists of a
positively charged nucleus accompanied by a negatively charged electron. The two particles
experience an attractive force and from this, the motion of the electron can be calculated.
From this, chemically important properties like the radius of a hydrogen atom, the ionization
energy and even the colour can be calculated.
As part of Summer School we will attempt to approach chemistry from this bottom-up
approach by considering what occurs at the microscopic level (electronic structure) but also
the physics behind chemical transformations. Both of these concepts originally had their roots
in simple classical physics.

4.1 Basic Mechanics

At Summer School, we will begin by considering the classical (pre-20th century) laws of
physics, particularly classical mechanics and classical wave theory. You should be familiar
with some of the very basic concepts before you arrive. This section will contain no examples
- it just aims to familiarise you with some of the vocabulary we will be using. Most of this is
covered in a standard year 11/12 physics course.
Particles
In classical mechanics, the state of a particle is described by quantities such as position (x),
velocity (v, directional speed, measured in ms-1), acceleration (a, measured in m s-2)
momentum (p, measured in kg m s-1), energy (E, measured in J) (kinetic (K) and potential
(V)), forces acting on (F, in N), mass (m, in kg), etc. The important terms are defined in the
table at the end of the section. In mechanics calculations, SI units should be used at all times.
Velocity and momentum describe the direction and magnitude of motion, while energy is a
number which describes the ability of a particle to push against forces (do 'work').
In classical mechanics, objects stay in constant motion (with a constant velocity and
momentum) unless they are acted upon by a force. Forces acting on a particle change the
momentum of a particle, and hence change its motion:

dp
=F
dt
Common forces include gravity, and electric forces.
! !! !!
Electrostatic: =
!
!!!! !

Gravitational: =

!! !!
!!

where r is the distance between the objects, qi is the charge of particle i and mi is the mass of
particle i.

32

In particular, classical motion obeys Newton's Law:

F = ma ,
Computation of the motion of a complicated system can be difficult, so often we can use the
more
general
conservation
laws
to
aid
us
in
our
calculations:

Conservation of energy (E): total energy in an isolated physical system is constant

over time.
Conservation of momentum (p): in a closed system of objects, with no external
forces, momentum is constant over time.

Waves
A wave is a form of energy which is spread out and transmitted through space - a disturbance
or oscillation which propagates through time. There are many different kinds of waves that
we are familiar with:
- Mechanical waves involve deformation or vibration of substances (water waves, sound
waves, etc.)
- Electromagnetic waves (light, X-rays, radio waves, etc.) are the oscillation of electric and
magnetic fields which can carry energy through a vacuum.
Waves are characterised by a frequency (f, number of cycles per unit time), a wavelength (,
the length from crest to crest), an amplitude (A, the height of the oscillations) and a speed (v =
f) which relate directly to their properties. Waves are subject to many special phenomena,
including diffraction, reflection, refraction and interference, all of which will be discussed at
the Summer School.

Particle
Mechanics

Forces cause
changes in
momentum, and
hence determine
the motion of
objects.

F ( x, t ) =

Properties
of waves

Potential Energy
is associated with
the location of a
particle (its
interaction with
forces).

dV
dx

Kinetic Energy
is associated
with the motion
of a particle.

K=

V (x)

1 2
mv
2

Momentum
measures how
much an object
is moving
(taking into
account mass).

p = mv

The speed of a wave, v,

is related to frequency
and wavelength.

Frequency counts the number

of oscillations of a wave per
unit time.

Wavelength is
the spatial
distance covered
by a wave in
one oscillation.

v =f

33

4.2 Electronic Structure

It is only since 1911 that chemists have known that atoms consist of electrons orbiting a tiny,
positively charged nucleus. The orbits of the electron are similar to planetary orbits, and can
be labeled by their average distance, angle of inclination etc. However, the laws of quantum
mechanics imply that only a handful of the infinite possible orbits are allowed. We call these
quantised orbits orbitals and label them with each of the following:
Shell Number:
which can be any of 1,2,3,4 in order of increasing distance from the nucleus.
Subshell Label:
which can be s, p, d, f, g, h The nth shell has n subshells, e.g. the second shell has
two subshells: 2s and 2p.
Direction Indicator:
The s subshell has no particular direction and contains only one orbital, whereas the
p subshell contains three orbitals (px, py, pz). The d subshell contains five
orbitals; the f subshell contains seven and so on.
Each orbital can hold two electrons, so long as they have opposite spin to each
other. However, it is slightly more energetically advantageous to have electrons
unpaired rather than paired.

Electrons fill the orbitals so as to minimise total energy: the electrons fill the lowest shells
first. We call this configuration the ground state.
The main contribution to the energy is the distance from the nucleus, so the shells are filled in
the order 1 < 2 < 3 < 4.
Next, the subshells are filled in the order: s < p < d < f, but there is a catch. The 4s subshell is
actually lower in energy than the 3d subshell! Likewise, the 5s subshell gets filled before the
4d, and the 5p and 6s subshells both get filled before the 4f.
Here is a helpful mnemonic for
remembering the order in which the
orbitals are filled. Write out all the
orbitals as shown, then read them
diagonally starting from the top right
and going to the bottom left.

Subshell
s

Shell

5

4

d xy d xz d yz d z2 d x2-y2

3
s

3d

px py pz

1s
2s 2p
3s 3p3d
4s 4p4d4f
5s 5p5d5f
6s 6p6d
7s 7p

1s
2s 2p
3s 3p3d
4s 4p4d4f
5s 5p5d5f
6s 6p6d
7s 7p

The order of filling orbitals is 1s, 2s,

2p, 3s, 3p, 4s and so on

34

Example The electron configuration of Nickel is 1s22s22p63s23p64s23d8

(as shown in the diagram above).
Problem Set 4:
3.1. Write the ground state electron configuration for
a. Fe
b. F
c. Hg.
3.2. Which neutral elements would have the following ground state electron
configurations
a. 1s22s22p4
b. 1s22s22p63s23p64s23d3
c. 1s22s22p63s23p64s23d104p1
3.3. Can you work out a formula (in terms of n) for the number of orbitals in the nth shell?
What about the maximum number of electrons allowed in the nth shell?

35

5. STOICHIOMETRY AND LABORATORY

CALCULATONS
At this stage, it is expected you would have a clear understanding of basic stoichiometry
including use of the formulae:
Mass (g)
Moles =
Molar Mass (g/mol)

Moles = Concentration (mol/L) Volume (L)

Students are also required to perform calculations with correct use of significant figures. (see
Section 1.1)
A recommended revision text is:
Silberberg, Chemistry The Molecular Nature of Matter and Change, Chapter 3:
Stoichiometry & Chapter 4: The Major Classes of Chemical Reactions.

5.1 Empirical Formula

The empirical formula is given as the simplest whole number ratio of elements in a
compound.
Examples:
Consider acetic acid: CH3COOH. Its empirical formula is C1H2O1 or CH2O.
The empirical formula of Methane CH4 is the same as its molecular formula.
Many ionic compounds can only be expressed in terms of its empirical formula, such as table
salt NaCl.
Determining Empirical Formula:
The composition of a compound of interest may be expressed in mass or as a percentage
mass. As we are only interested in the ratio of elements, both can be treated the same:
Example: Determine the empirical formula of Vitamin C, which has the following
composition: 40.91% Carbon, 4.59% Hydrogen and 54.50% Oxygen.
Step 1. Determine the number of moles per element:
Assume that 100g of the sample is present when percentages are given.
Divide the mass of each element by its molar mass to determine the mole ratio:
C:

40.91 g
4.59 g
=3.406 mol H:
=4.55 mol
1
12.01 g mol
1.008 g mol1

O:

54.50 g
=3.406 mol
16.00 g mol1
Our current preliminary formula is C3.406H4.59O3.406.

36

Step 2. Convert to integer ratio:

Divide each by the smallest number of moles present for an element, or by the smallest
subscript. Here, both C and O are present in the least amount.
C:

3.406
=1
3.406

H:

4.55
= 1.34
3.406

O:

3.406
=1
3.406

Often integer ratios appear at this step. If this is not the case, we multiply to obtain whole
numbers: here, we multiply by 3:
C: 1 3 = 3

H: 1.34 3 = 4.01 4

O: 1 3 = 3

Thus, the empirical formula of Vitamin C is C3H4O3.

Problem Set 5.1:
4.1.1. Determine the empirical formula of an oxide of nitrogen containing 30.45% N and
69.55% O by mass.
4.1.2. A sample contains 0.80 g C; 0.134 g H; 1.066 g O. Suggest a molecular formula if
its molecular weight is 180.16 g mol1
4.1.3. A 1.30 g sample of a unknown hydrocarbon undergoes complete combustion (in
oxygen) to produce 4.40 g of CO2 and 2.70 g of H2O. Suggest a molecular formula
if its molecular weight is 30.0 g mol1.

5.2 Laboratory Calculations

The aim of this section is to illustrate the expected layout when writing laboratory
calculations.

Standard Titrations:
In the standard titration, the concentration of a solution is determined by reaction with a set
volume of a solution with known concentration.
Example: The concentration of an unknown sodium hydroxide was determined by titration
with 20.00 mL of approximately 0.2 mol L1 hydrochloric acid which was standardised with
sodium carbonate.
a. The standard was made by dissolving 5.617 g in 500.0 mL. Determine its molarity.
Moles (Na2CO3) = Mass/ Molar Mass
n(Na2CO3) = 5.617 g / 105.99 g mol1
n(Na2CO3) = 0.05300mol
Concentration (Na2CO3) = n (Na2CO3)/ Volume
[Na2CO3] = 0.05300 mol /0.500 L
[Na2CO3] = 0.1060 mol L1

(Dont Round Off)

( [ ] indicates concentration)
(Four sig. figs)

b. Titration of 20.00 mL of Na2CO3 with HCl gave an average titre of 19.71 mL.
Determine the concentration of the acid.

37

2H+(aq) + CO32- (aq) CO2 (g) +H2O(l)

n(Na2CO3) = 0.1060 mol L1 0.02000 L
= 0.002120 mol L1
n(HCl) = 2 x n(Na2CO3)
= 0.004240 mol
[HCl] = 0.004240 mol / 0.01971 L
= 0.2151 mol L1

(Write a balanced equation)

(Again, 4 sig figs)

c. Below are burette readings in the titration with sodium hydroxide. Determine the
volumes of the NaOH titres and calculate its concentration.
V(NaOH)
(mL)
Initial Volume

Titre 1

Titre 2

Titre 3

Titre 4

0.34

0.23

0.45

0.34

Final Volume

27.69

27.57

27.59

27.70

Titre

27.35

27.34

27.14

27.36

Average
(27.14mL titre is an outlier and not included in the results)

27.35 mL

HCl + NaOH H2O + NaCl

n(HCl) = 0.02000 L 0.2151 mol L1
= 0.004302 mol
n(HCl) = n(NaOH)
[NaOH] = 0.004302 mol / 0.02735 L
= 0.1573 mol L1
Back Titration:
Sometimes a direct titration is not possible. In a Back Titration the sample is reacted with an
excess amount of reagent with volume and concentration known. The unreacted reagent is
then titrated with a known solution, allowing for compositional analysis of the initial sample.
Note that the limiting reagent runs out before the excess reagent does: i.e. The maximum
number of moles of product is equivalent to the number of moles of limiting reagent.
Example: The calcium carbonate content in rock was analysed by treating the sample with
15.00 mL of 0.912 mol L1 hydrochloric acid. The sample was back-titrated with
17.77 mL of 0.130 mol L1 NaOH. Determine the mass of calcium carbonate in the
sample.

Total Amount of HCl

Added:
Excess HCl reacted with NaOH

Amount of HCl used by

CaCO3

38

HCl XS + NaOH H2O + NaCl

(Equation for back titration)

n(NaOH) = 0.130 mol L1 0.01777 L

= 0.00231 mol
n(HCl XS) = 0.00231 mol
n(HCl total) = 0.9120 mol L1 0.01500 L
= 0.01368 mol
n(HCl used) = n(HCl total) n(HCl XS)
= 0.01368 mol 0.00231 mol
= 0.0114 mol
2HCl + CaCO3 CO2 + H2O + CaCl2
n(CaCO3) = n(HCl)
= 0.00569 mol
m(CaCO3) = 0.00569 mol x 100.07 g mol1
= 0.569 g

(Equation for HCl reaction with rock)

Yield:
The theoretical yield is the expected mass of a product in a reaction assuming 100%
conversion has occurred.
Example: a. Determine the theoretical yield of ethyl acetate in the following reaction, given
the following data
OH

Volume Used
(mL)
Density (g mL1)
Molecular
Weight (g mol1)

+ H2O

HO

Ethanol
5

Acetic Acid
5

Ethyl Acetate

0.789
46.07

1.044
60.05

0.897
88.105

Mass(ethanol) = Density x Volume

= 5 mL 0.789 g mL1
= 3.95 g
n (ethanol) = 3.945 / 46.07
= 0.0856 mol
Mass (acetic acid) = 5 mL x 1.044 g mL1
= 5.22 g
n (acetic acid) = 5.22 g / 60.05 g mol1
= 0.0869 mol
Ethanol is the limiting reagent and acetic acid is in excess.
Theoretical Yield = Masscalc (ethyl acetate)
= 0.0856 mol 88.105 g mol1
= 7.54 g

(Masscalc is the theoretical mass)

a. Determine the percentage yield if 5 mL of ethyl acetate was obtained.

39

The percentage yield is the obtained mass divided by the theoretical mass.
Massact (ethyl acetate) = 5 mL x 0.897 g mL1 (Massact is the actual or obtained mass)
= 4.49g
Massact (ethyl acetate )
Percentage Yield =
Masscalc (ethyl acetate )
=

4.49
100
7.54

= 59%
Problem Set 5.2:
5.2.1. A 25.00 mL solution of ammonia was reacted with 30.00 mL of 0.789 mol L1 HCl.
20.00 mL of the resultant solution was back-titrated with 0.098 mol L1 Na2CO3,
giving a titre of 15.65 mL. Determine the initial concentration of ammonia.
5.2.2. Fluorene can be oxidised to fluorenone using dichromate:
O

+ 2 Cr 2O72- + 16 H+

3
fluorene

+ 4Cr2+ + 11H2O

3
f luorenone

1.50 g of fluorene was added to 4.00 g of sodium dichromate dihydrate in 27 mL

glacial acetic acid (density 1.044 g mL1). If a 38% yield was obtained, calculate
the mass of fluorenone obtained.
5.2.3. The mass of 2-pentanone (C5H10O, FW:86.13 g mol1) in a sample can be
determined by reaction with basic iodine solution in the iodoform reaction:
C5H10O + 3 I2 + 4 OH CHI3 + C5H10O2 + 3 I
The iodoform (CHI3) was then treated with (excess) 25.00mL of
0.479 mol L1 silver nitrate in the following reaction:
CHI3 + 3 Ag+ + H2O 3 AgI(s) + 3 H+ + CO(g)
The solution of excess silver nitrate was then titrated with 5.23 mL of
0.138 mol L1 KSCN:
Ag+ + SCN AgSCN(s)
Determine the percentage mass of 2-pentanone in a 0.800 g sample

40

6. ANSWERS TO PROBLEMS
Section 1: Mathematics
1.1.1

a. 24.17
b. 0.0115 or 1.15 x 10-2
c. 46.0
d. 18.0
e. 2.1 x 102 or 210

1.2.1

a. y = 1.6
b. y = 1.15
c. y = 1.3 x 10-6
d. y = 1.56
e. y = 12
f. y = 2.5 x 10-6

1.3.2.

a.

d.

dy
dx
dy
dx
dy
dx
dy
dx

e.

dy
dx

= ( x 2 1) ( 2x ) + ( 2x ) ( x 2 + 4) = 2x ( 2x 2 + 3) = 4x 3 + 6x

f.

= k cos(kx)

g.

dy
dx
dy
dx

h.

dy
dx

b.
c.

1.3.3

= 8 x + 5
= 1x sin x 5e x
= x 1x + 1 ln x = 1 + ln x
= sin x sin x + cos x cos x = cos 2 x sin 2 x

( )
= (3 x ) 3(x + 1)

= 2 x cos x 2
2

x3 + 52 x 2 + 3 x + C
b. sin x cos x + C
c. k ln x + C
kdx
x1n
kx 1n
d. n = k x n dx = k
+C =
+C
(1 n)
(1 n)
x
a.

1
3

1.3.5. 1. Hint: Differentiate both sides with respect to t. The left hand side becomes

d [ A]
. Differentiate the right hand side, then re-substitute [A] into the equation.
dt
d [ A]
d [ A]
= k[ A] 2 becomes
= kdt
2. a. Rearrange
dt
[ A] 2
1
d [ A] = k dt
b.
[ A] 2
1
+ C = kt
Integrating:
[ A]

41

[ A]3

b. Using a direct integral instead:

1
d [ A] = k dt becomes:
2

[ A]0 [ A]
0

1
1

= k (3 0) which gives the answer.

[ A]3 [ A]0
1.4.1
a. -1
b. 1
c.
d. 7
e. 5 2
f. 12
g. 4
h. 2 10
!

!"

i.

1.4.2
a. 10 4
b. 1 6
c. 1 +
d. 3 2
e. 15 5
f. 2 + 4 2
!
!
g. +
!

h.
i.

!
!

!
!

1.4.3
a. 1
b.
c.

!
!

d.
!

!
!

Section 2: Organic Nomenclature

2.1 . The compounds are:
a. 2-methylpentane
b. 2-methylpent-1-ene or 2-methyl-1-pentene
c. 1,4-dimethylcyclohexane
d. 3-methylheptane
e. hexan-3-one or 3-hexanone
f. 4-hydroxypentan-2-one or 4-hydroxy-2-pentanone
g. hex-1-en-3-one
h. o-dichlorobenzene or 1,2-dichlorobenzene
i. o-aminophenol or 2-aminophenol
j. 3-oxobutanoic acid

42

2.2. 3,6-dimethyl-4-chlorooctane
Section 3: Transition Metal Chemistry
1.

a) triammineaquadichloridochromium(III) nitrate, [CrCl2(NH3)3(OH2)]NO3

b) sodium aquacarbonyldihydroxidooxalatomanaganate,
Na2[Mn(CO)(OH)2(OH2)(ox)]

2.

a) [Fe(bipy)2(OH2)2]Cl2

b) [PtCl2(NH3)2]
2+

N
N

ClFe

OH2

Cl-

Cl

NH 3
Pt

OH2

Cl

NH 3

3. a) chlorotris(triphenylphosphine)rhodium(I)

b) bis(glycinato)zinc(II)
O

PPh 3
Cl

Rh

PPh 3

N
H

PPh 3

Zn

NH

Section 4: Electronic Configuration

4.1 The electron configurations are
a. Fe
1s22s22p63s23p64s23d6
b. F1s22s22p6
(note the extra electron)
2 2
6 2
6 2
c. Hg
1s 2s 2p 3s 3p 4s 3d104p65s24d105p66s24f145d10
(or [Xe] 4f145d106s2)
4.2 The elements are (a, Oxygen) (b, Vanadium) (c, Gallium)
4.3 The number of orbitals in the nth shell is the sum of the first n odd numbers, 1 + 3 + 5
+ + (2n 1) = n2. The maximum number of electrons is therefore 2 n2.
Section 5: Stoichiometry and Laboratory Calculations
5.1.1. NO2
5.1.2. C6H12O6
5.1.3. C2H6
5.2.1. 0.609M
5.2.2. 0.618g
5.2.3. 40.4%

43

7. ACKOWLEDGEMENTS
These notes were written based on the previous notes compiled by Elizabeth New and
Anthony Phillips. The material in these notes has been collated by Alex Wong, Tristan
Reekie, Dustin Stuart, Anne Trinh, Shannon He, Nicholas Malouf, Trent Wallis and Sam
Salman. A special thanks is extended to William Jackson for his careful editing.

44