2/28/17

Chemical Principles and Processes: Physical vs chemical properties

Properties of Gases
• Physical properties don’t depend on electron
behaviour: size, mass, velocity, density,
pressure, volume, temperature

• Chemical properties do depend on electron

behaviour: strength of intermolecular
interactions, reactivity, polarity
Dr Deborah Crittenden
[email protected]

(Partially) Separating gas mixtures (Partially) Separating gas mixtures

e.g. Carbon capture e.g. Carbon capture

Physical ➙ CO2
Mixture of separation
gases ➙
Chemical
separation ➙ Other
gases

Physical vs chemical separation Quiz time

Everyone on your feet!
• Physical separation: separates gas molecules
on the basis of their size or mass

• Chemical separation: separates gas

molecules based on the strength of their
interactions with each other or another type
of material

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Chemical properties of gases Chemical properties of gases

• What determines chemical properties of • Boiling points of gases determined by their

gases e.g. boiling points, reactivity, intermolecular interactions
greenhouse gas activity, ozone depleting • Reactivity determined by bond strengths /
nature? bond enthalpies
• Greenhouse gas activity determined by bond
polarities and molecular vibrations
• Ozone-depleting character due to presence
of bonds that photolyse to form halide
radicals

Determining intermolecular
Chemical properties of gases
interaction strength
• Boiling points of gases determined by their 1. Analyse atoms in molecules according to
intermolecular interactions electronegativies, assign charges and
– The stronger the intermolecular interactions, partial charges, bond polarities, molecular
the more kinetic energy required to overcome
them and get the molecules moving polarities
• Reactivity determined by bond strengths / 2. Analyse atoms in molecules according to
bond enthalpies polarizability – how easy it is to influence
– How hard is it to break bonds in the reactants? behaviour of valence electrons. The further
– How much energy can be gained from forming from the nucleus, the more polarizable the
bonds to make products? electrons generally (related to atomic radii)

Determining intermolecular
Examples
interaction strength
Molecule Molecular polarity Polarizability
In general:
CO moderate dipole moderate
• Electronegativity increases across periodic
table and decreases down CO2 moderate quadrupole moderate
• Polarizability decreases across periodic table CH4 non-polar moderate
and increases down Li non-polar high
• The larger a molecule and the more spread O2 non-polar moderate
out its electrons (aka delocalized, aka more
resonance structures), the higher its HF strong dipole low
polarizability HBr moderate dipole high

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Determining intermolecular
Reactivity
interaction strength
3. Categorize intermolecular interactions:
• Reactivity of gases determined by their
Type Interaction strength intramolecular interactions, ie. bond
dipole-dipole ++++++ strengths / bond enthalpies
dipole-quadrupole +++++ – How hard is it to break bonds in the reactants?
– How much energy can be gained from forming
quadrupole-quadrupole ++++
bonds to make products?
dipole-induced dipole +++/++++ • Can we predict molecular reactivities from
quadrupole-induced dipole ++/+++ bonding patterns?
induced dipole-induced dipole +/++

Case study – CO poisoning Properties

• O2 – essential for life • O2 and CO quite similar in many respects

Molar Mass Bond Boiling Point

Appearance
(g/mol) Length (Å) (°C)

Odorless,
• CO – highly toxic 32 1.21 -183
colourless

Odorless,
28 1.13 -192
colourless

Properties Properties
• Both bind to the transport protein hemoglobin • Both bind to the transport protein hemoglobin

heme

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Properties The importance of oxygen

• Both bind to the transport protein hemoglobin
• Cellular respiration: Glucose ➞ Energy

C6H12O6(aq) + 6O2(g) ➞ 6CO2(g) + 6H2O(l)

ΔG = -2880 kJ/mol

Chemical reactivity Bonding energies

C6H12O6(aq) + 6O2(g) ➞ 6CO2(g) + 6H2O(l)

Bond dissociation
energy (kJ/mol)
ΔG = -2880 kJ/mol
498

1070
C6H12O6(aq) + 6CO ➞ no reaction

Flammability The reactants side

• Single bonds are relatively easy to break

• A special type of reactivity – reactivity
towards O2 • Double and triple bonded molecules are
usually not combustible (acetylene is an
exception)
• Again, need to consider how much energy is
required to break bonds
• And how much energy can be recovered by
forming bonds in products

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The products side Recap

• Combustion products: • Boiling points determined by strength of

• almost always include the ultra-stable intermolecular interactions
H2O, CO2, or both • Reactivity determined by strength of
• occasionally NOx and SOx intramolecular bonding, and stability of
• Any molecule that can’t form these products products.
won’t be flammable

Practice

• Complete column 1 of tutorial problems

from lectures 4 & 5