CHU11E05 Chemistry

CHU11E05 – Chemistry

Part I – Introduction to Atomic Structure

& Bonding

Lecture 1

Prof. Dónall A. Mac Dónaill dmcdonll@tcd.ie

Course Director: Prof. Richard Hobbs hobbsr@tcd.ie

CHU11E05 Chemistry – Lecture 1

Why Study Chemistry?

• Chemistry is the study of

- Materials and their properties
- Changes in materials
- Effects of composition on properties and change

• Chemists make materials

• Chemists can provide solutions for problems

All of which are important to engineers

CHU11E05 Chemistry – Lecture 1

Why Study Chemistry?

CHU11E05 Chemistry – Lecture 1

Course Overview – Part 1

Introduction to Atomic Structure and

Bonding – Prof. Dónall A. Mac Dónaill

• Elements, compounds and mixtures

• Atoms
• Molecules - and “the mole”
• Chemical equations and stoichiometry
• Atomic structure
• Compounds and chemical Bonds - covalent and ionic
• Shapes of molecules
• Metals, insulators and semiconductors

CHU11E05 Chemistry – Lecture 1

Course Overview – Part 2

Introduction to Physical Chemistry – Profs.

Dónall A. Mac Dónaill and Richard Hobbs

• Chemical Thermodynamics • Chemical Equilibrium

– First law, internal energy,
enthalpy
– Introduction to entropy
– Criterion for chemical change
– Equilibrium constant, Gibbs free
energy
• States of matter
– Phase changes and phase
diagrams
– Ideal solutions, colligative
properties
– Law of mass action
– Factors influencing the position of
equilibrium
• Ionic Equilibria
– Ionic equilibria in aqueous solutions
– Strong and weak acids and bases
– Buffer solutions and indicators
• Chemical Kinetics
– Rates of reactions
– Factors influencing rates of reactions
– Heterogeneous and homogeneous
Catalysis

CHU11E05 Chemistry – Lecture 1

Recommended Texts

“Chemistry : The Molecular Nature of Matter and Change”, Silberberg,

Amateis (McGraw-Hill)

Currently on 9th edition but older versions also suitable

Online resources also useful:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemistry
_-_The_Molecular_Nature_of_Matter_and_Change_(Silberberg)

Other notable books

• Kotz, Treichel, Weaver “Chemistry and Chemical Reactivity”
• P. Atkins and L. Jones, 'Chemical Principles, The Quest for Insight‘
• P. W. Atkins, 'Elements of Physical Chemistry'

CHU11E05 Chemistry – Lecture 1

Physical Properties and Chemical Properties

Physical Properties: Characteristics that a substance shows by itself –

without changing into or interacting with another substance

e.g. melting point, boiling point, density, colour, smell

Chemical Properties: Characteristics of a substance as it interacts

with another substance or changes into another substance, or its
tendency to do so.

e.g. flammability, reactivity, toxicity

CHU11E05 Chemistry – Lecture 1

Physical Change and Chemical Change

Physical Change: When a substance alters its physical properties but

not its composition

e.g. Ice(solid) → water(liquid)

H2O(solid) → H2O(liquid)

Physical properties change, composition does not

Chemical Change: When a substance is converted into a different

substance or substances

e.g. water(liquid) → hydrogen(gas) + oxygen(gas)

H2O(liquid) → H2 (gas) + 1/2 O2 (gas)

The composition has changed – final sample is no longer water

CHU11E05 Chemistry – Lecture 1

Physical Change and Chemical Change

Consider the following, are they primarily physical or chemical

changes?

• Milk turns sour

• Frost forms on a metal bar on a cold winter night

• Clouds form in the sky

• Sweat evaporates from a professional athlete

• Rust forms on an old car

• A slice of bread is toasted

CHU11E05 Chemistry – Lecture 1

Elements, Compounds & Mixtures

Any sample of material will be

either or

A mixture A pure substance

e.g. air, whiskey, cheese which in turn will be

either
or

An element
A compound e.g. Helium, Gold, Chlorine
e.g. water, salt, ethanol

Mixtures contain two or more elements or compounds. The composition of a

mixture is variable and the chemical properties of the mixture are those of
the components.
CHU11E05 Chemistry – Lecture 1
Elements, Compounds & Mixtures (ii)

No further
Compound Separable into Elements chemical
(pure breakdown
substance) (re)combine into

e.g.
Separable into
H2O H + O
Water Hydrogen + Oxygen
(re)combine into

• Elements are substances that cannot be broken down into simpler

materials by chemical means
• Compounds are chemical combinations of two or more elements
in definite ratio by mass
• Any pure substance will have its own characteristic physical and
chemical properties; for a compound these are generally different
from those of the constituent elements.
CHU11E05 Chemistry – Lecture 1
Elements, Compounds & Mixtures (iii)

NaCl
Melting Point: 801 oC
Boiling point: 1413 oC
Colour: colourless (white)
Density: 2.16 g/cm3
Behaviour in water: Dissolves freely

Na
Cl2

Na
Melting Point: 97.8 oC
Boiling point: 881.4 oC
Colour: silvery
Density: 0.97 g/cm3
Behaviour in water: Reacts
Cl2
Melting Point: -101 oC
Boiling point: -34 oC
Colour: yellow-green
Density: 0.0032 g/cm3
Behaviour in water: Dissolves slightly
Na: https://commons.wikimedia.org/w/index.php?curid=3831512
Cl: https://commons.wikimedia.org/w/index.php?curid=15356384

CHU11E05 Chemistry – Lecture 1

Elements, Compounds & Mixtures (iv)

Decomposition of water

H2O H + O

18g 2g 16g

• Proportions of H and O obtained from splitting up water always in the ratio

2:16 or 1:8 by mass
• Law of Constant Composition: A given pure compound always contains the
same elements in the same proportions of mass (compare mixtures)
• So elements can only react in these proportions to form a given compound
and any excess will be left unchanged e.g.

(a) 2g Hydrogen + 16g Oxygen → 18g Water

(b) 3g Hydrogen + 16g Oxygen → 18g Water + 1g Hydrogen
(c) 1g Hydrogen + 9 g Oxygen → 9 g Water + 1g Oxygen

• Similarly :
1g Hydrogen + 35.5g Chlorine → 36.5g Hydrogen chloride

CHU11E05 Chemistry – Lecture 1

Limiting Reagent

This leads to the important concept of the limiting reagent

The Limiting Reagent is the reagent present in the lowest

(molar) amount relative to the products of the reaction and
which therefore determines (i.e. limits) the yield of product.

e.g. (from last slides)

(i) 1g Hydrogen and 9g Oxygen yield 9g Water and 1g Oxygen –

the Hydrogen is the limiting reagent [not enough H some O
left unreacted]

(ii) 3g Hydrogen and 16g Oxygen yield 18g Water and 1g

Hydrogen – the Oxygen is the limiting reagent [not enough O
and some H left unreacted]

CHU11E05 Chemistry – Lecture 1

Law of Constant Composition

Law of Constant Composition: A given pure compound always contains the same
elements in the same proportions of mass

The source of the pure compound does not matter – its elements will always occur
in the same proportion by mass.

mass of element in a compound = mass of compound x mass fraction of element

Q: Sodium chloride, which contains only sodium and chlorine, is 60.66% chlorine by
mass. What mass of sodium would there be in 1 kg of sodium chloride.

Mass fraction of sodium = 39.34%

Mass of sodium in sample = 1 kg x 39.34% = 393.4 g

CHU11E05 Chemistry – Lecture 1

Dalton’s Atomic Theory

• All matter consists of atoms

• An atom is the smallest particle of an element

that retains the characteristic chemical
properties of that element.

• Atoms of one element cannot be converted

to another element (transmutation is not
possible!)

• All atoms of the same element have the same

mass and chemical properties; atoms of
different elements have different masses and
chemical properties.

• During chemical reactions atoms are

conserved. They cannot be created or
destroyed, or converted to another type.

https://commons.wikimedia.org/w/index.php?curid=6204781

CHU11E05 Chemistry – Lecture 1

Historical Digression - Dalton

In addition to atomic theory, John Dalton worked

on

• Meteorology and measuring mountains

• Colour blindness

• Gas laws

• Atomic weights

• Optics

CHU11E05 Chemistry – Lecture 1

Atoms

• Following from the law of constant composition –

compounds result from the chemical combination of a
specific ratio of atoms of different elements.

*Atoms can be imaged using modern research techniques

such as electron microscopy and scanning tunnelling
microscopy – available in research groups in TCD

*Image by Prof. Jani Kotakoski, University of Vienna

CHU11E05 Chemistry – Lecture 1

Atomic Structure

• Dalton established that matter was made of indivisible atoms and

that the masses of elements could be explained in terms of atoms

• However, Dalton’s model did not explain how atoms bonded with
each other

• Furthermore, Dalton’s model treated atoms like “billiard-balls”

- Did not predict existence of subatomic particles

CHU11E05 Chemistry – Lecture 1

Discovery of the Electron - Background

• In the aftermath of Dalton’s postulates,

scientists knew that matter and electric
charge were related

• Rubbing amber or plastic with cloth leads

to the formation of positive and negative
charges

• Scientists knew that the passing of electric

current could decompose certain
compounds – but the nature of this
current was unknown

CHU11E05 Chemistry – Lecture 1

Discovery of the Electron – Cathode Ray Tube

https://commons.wikimedia.org/w/index.php?curid=100143

• To better understand this, scientists tried passing current through nearly evacuated
gas tubes fitted with metal electrodes

• With the power on, a “ray” was seen striking the phosphor-coated end of the tube
which emitted a spot of light

• These rays were called cathode rays because they originated at the negative
electrode (cathode) and moved to the positive electrode (anode)
CHU11E05 Chemistry – Lecture 1
Discovery of the Electron – Cathode Ray Tube (ii)

Observation 1: Ray bends in magnetic field

Conclusion: Consists of charged particles

Observation 2: Ray bends towards positive plate

Conclusion: Consists of negative particles

Observation 3: Ray is identical for any cathode

Conclusion: Particles found in all matter

In 1874/1891/1894 Stoney suggested the name

electron for the fundamental electrical particle

[Born: Dún Laoghaire, Prof. Queen's College Galway]

“Of the "Electron," or Atom of Electricity”, Philosophical

Magazine, Series 5, Volume 38, p. 418-420, October 1894
https://www.chemteam.info/Chem-History/Stoney-1894.html
https://royalsocietypublishing.org/doi/abs/10.1098/rsnr.1975.0018

CHU11E05 Chemistry – Lecture 1

Discovery of the Electron – Mass and Charge

1897, J. J. Thompson measured the ratio of the mass of the

cathode ray particle to its charge

• Obtained mass to charge ratio (m/e) of -5.6 x 10-12 kg/C

• Estimated that the cathode ray particle weighed less than

1/1000 as much as a hydrogen atom

• Was met with disbelief from his scientific peers!

* Note C stands for Coulomb, the SI derived unit of charge

https://commons.wikimedia.org/w/index.php?curid=2969861

CHU11E05 Chemistry – Lecture 1

Discovery of the Electron – Mass and Charge (ii)

https://commons.wikimedia.org/w/index.php?curid=14695366

Robert Millikan & Harvey Fletcher measured the charge of the electron in 1909

• X-rays used to knock electrons from gas molecules

• Electrons stuck to tiny oil droplets

• Adjusting the applied electric field the drop could be slowed and suspended

• This allowed the total charge to be measured: gravity balanced by force from electric
field

• Total charge was always an integer multiple of a minimum charge – the electron – very
close to today’s accepted value of -1.602 x 10-19 C

CHU11E05 Chemistry – Lecture 1

Discovery of the Electron – Mass and Charge (iii)

Know mass/charge ratio from Thompson: -5.686 x 10-12 kg/C

Know charge from Millikan & Fletcher: -1.602 x 10-19C

Can now calculate the mass:

= × ℎ
ℎ

= (-5.686 x 10-12 kg/C) x (-1.602 x 10-19C)

= 9.109 x 10-31 kg or 9.109 x 10-28 g

~1/1840 the mass of a H atom

CHU11E05 Chemistry – Lecture 1

Structure of Atoms: Plum Pudding Model

While electrons are negatively charged, atoms are neutral

• What positive charges balance them?

Electrons have a tiny mass

• What accounts for an atom’s larger mass?

Thompson proposed a “plum pudding” model

• A spherical atom of diffuse positively charged matter with electrons
embedded in it

CHU11E05 Chemistry – Lecture 1

Discovery of Atomic Nucleus

Plum pudding model tested by Ernest Rutherford in 1910

Positive alpha particles fired at thin gold foil

Expected minimal deflection – should go straight through “plum pudding”

But In reality observed some particles coming backwards

CHU11E05 Chemistry – Lecture 1

Discovery of Atomic Nucleus

Rutherford concluded that these few alpha particles were

being repelled by something small, dense and positive
within the Au atoms

Calculations showed that

• An atom is space mostly occupied by electrons

• In the centre is a tiny region, named the nucleus by Rutherford, which

contains all of the positive charge and the vast majority of the mass of the
atom.

Rutherford proposed that positive particles, called protons, were in the nucleus

Neutrons:

*Rutherford’s observations did not account for all of the mass of atoms

In 1932 Chadwick discovered the neutron, an uncharged particle that also lies
in the nucleus

CHU11E05 Chemistry – Lecture 1

Structure of the Atom
Neutron, n0 e-
(no charge) (neg. charge)

Electron:
< 10 x 10-18 m

Nucleus:
~ 5 x 10-15 m
Atom: ~ 1 x 10-10 m

http://www.nuclear-power.net/
Proton, p+
(positive charge)

CHU11E05 Chemistry – Lecture 1

Atomic Number

The atomic number (Z) of an element equals the number of protons in

the nucleus. For a neutral atom it is also the number of electrons.

• All atoms of an element have the same atomic number

• Each element has a different atomic number

e.g. All carbon atoms have Z = 6, so 6 protons

All fluorine atoms have Z = 9, so 9 protons

CHU11E05 Chemistry – Lecture 1

Mass Number

The mass number (A) of an element equals the total number of

protons and neutrons in the nucleus.

• Each proton and each neutron contribute one unit to the mass number
• While all atoms of an element have the same atomic number, they can
have different mass numbers due to different numbers of neutrons

Number of neutrons = mass number – atomic number

e.g. All carbon atoms have Z = 6, so 6 protons

But carbon can have A = 12 or A = 13
(or in very rare cases A = 14)

This corresponds to 6, 7 (or 8) neutrons

CHU11E05 Chemistry – Lecture 1

Periodic Table

An arrangement of
elements in order of
increasing atomic number

Atomic number
Atomic symbol

Atomic Mass
CHU11E05 Chemistry – Lecture 1
Atomic Masses of the Elements

The masses of atoms are measured relative to the mass of an atomic

standard

The standard used is the 12C atom whose mass is defined as exactly 12
atomic mass units

The atomic mass unit (amu), or Dalton, is 1/12 the mass of a 12C atom

This is typically used as a unit of relative mass

e.g. 1H has a mass of 1.008 amu

1 amu has an absolute mass of 1.66054 x 10-27 kg

CHU11E05 Chemistry – Lecture 1

Isotopes and Atomic Mass

Isotopes of an element are atoms that have different numbers of

neutrons and therefore different mass numbers

Carbons isotopes labelled 12C, 13C and 14C

The chemical properties of elements are primarily dependent on the

number of electrons – so isotopes will have near identical chemical
behaviour albeit with different masses

*Note: The atomic mass (or atomic weight) reported in the periodic
table is averaged over all the stable isotopes and weighted
according to their relative abundance.

CHU11E05 Chemistry – Lecture 1

Isotopes and Atomic Mass (ii)

Q: How many neutrons are present in Uranium’s 3 most common

isotopes, 238U, 236U, 235U

Atomic no. for U = 92

No. of neutrons in 238U = (238 – 92) = 146

No. of neutrons in 236U = (236 – 92) = 144

No. of neutrons in 235U = (235 – 92) = 143

CHU11E05 Chemistry – Lecture 1