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Unit 3 - Properties of
Substances & Mixtures

3.1 Intermolecular & Interparticle Forces

3.2 Properties of Solids
3.3 Solids, Liquids & Gases
3.4 Ideal Gas Law
3.5 Kinetic Molecular Theory
3.6 Deviation from Ideal Gas Law
3.7 Solutions & Mixtures
3.8 Representations of Solutions
3.9 Separation of Solutions & Mixtures
3.10 Solubility
3.11 Spectroscopy & Electromagnetic Spectrum
3.12 Properties of Photons
3.13 Beer-Lambert Law
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3.1 Intermolecular Forces

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Coulombs Law
All bonding is based on the attractions (and repulsions) that exist between charged particles. The
strength of bonding is governed by Coulombs Law:
F = q1 q2

r2
Full charges found on ions such as
Na , Cl , Mg , O , Al , P etc. are + - 2+ 2- 3+ 3-

multiples of the charge of one electron

( 1.16 x 10-19 C ).
Partial charges δ+ and δ- as found in atoms
and molecules are harder to quantify but
will set up attractions (and repulsions) as
governed by Coulombs Law.
Depending on the nature of the charges and
how they arise, we have developed a system
for labelling these similar attractions as
different types of bonding.

Main Types of Bonding

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3.1 Intermolecular Forces (Van der Waal's Forces)

London Dispersion Forces - temporary dipole → induced dipole
These are usually the weakest of attractions and are present in all substances but are often ignored
if a stronger type of attraction, e.g. ionic or metallic, is present.

In all atoms, electrons are distributed in shells and orbitals but

are constantly changing position.
Normally, electrons will minimise repulsions and, as a result,
their charge will be evenly distributed throughout the relevant
shells and orbitals.

Sometimes, however, the electron cloud will 'wobble' and charge

can become unevenly distributed.
This creates a temporary dipole - regions of separated positive
and negative charge.
These will be partial charges, δ+ and δ-, and are usually
significantly less than the charges formed on ions.

Normally, the need to minimise repulsion within the shell will result in charge returning to a more
even distribution and the temporary dipole will disappear - until the next 'wobble'.
However, if another atom is close enough, then another dipole can be triggered in the
neighbouring atom - this is referred to as an induced dipole.

Weak attractions - London Dispersion Forces - can then be set up between neighbouring atoms.
The larger the partial charges ( q1 q2 ) and the shorter the distance ( r2 ) then the stronger the
London Dispersion Forces (LDF's) as shown by Coulombs Law.
F = q1 q2 / r2
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In larger atoms, the outer shells are further
from the nucleus so, when electron clouds
wobble, larger partial charges are created.
This results in stronger temporary-induced
dipoles leading to stronger LDF's.

Notice how close the MPt of Helium is to
absolute zero ( -273.15 °C ) - the LDF's are so
weak that they struggle to hold the He atoms
together in solid Helium.
Exactly the same wobbles can occur in
molecular orbitals which can, again, lead to
temporary dipoles within a molecule.
This can then cause an induced dipole in
a neighbouring molecule leading to the
creation of London Dispersion Forces.
With larger atoms, the outer shells are further
from the nucleus so, when electron clouds
wobble, larger partial charges are created.
This results in stronger temporary-induced
dipoles leading to stronger LDF's.
Alkanes have atoms of the same size so
identical partial charges will exist and equal
attractions.
However, larger molecules will have more
wobbles occurring along the chain so a larger
number of attractions exist.
So LDF's increase with molecular size.
Branched alkanes have smaller surface areas
compared to their chain isomer, so will have
less attractions leading to weaker LDF's.
The electrons in the π-bond can also
wobble more and increase LDF's.

Properties of single atoms and non-polar

molecules will be determined by
London Dispersion Forces.
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Permanent Dipoles
If there is significant difference in the
electronegativity of atoms within a
molecule and the shape of the molecule
is suitable, then permanent dipoles can
be set up.

These permanent dipole - permanent dipole (dipole - dipole) attractions are generally stronger
than the London Dispersion Forces in equivalent molecules.
Equivalent molecules should have (if possible) similar numbers of similar sized atoms with, as
close as possible, identical numbers of electrons.
For example,
butane and acetone have similar numbers of
similar sized atoms and both molecules have
similar number of electrons.
We can assume, therefore, that they would
have similar LDF's - resulting in a melting
point about 270° above absolute zero.
The 'extra' 55° elevation shown in the Bpt of
acetone will be due to the extra dipole-dipole
attractions due to the existence of permanent
dipoles.

Whilst a polar covalent bond will be formed

whenever there is a significant difference in
electronegativity values, this does not
guarantee a polar molecule.
The shape of the molecule must allow for a
dipole to be created.
If charge is symmetrically arranged then
there will be no dipole and the molecule will
be non-polar.

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Hydrogen Bonding
Under certain circumstances,
dipole-dipole attractions can be
enhanced to such a degree
that they are considered as a
different type of attraction.

Normally, to be considered a hydrogen bond, there must be a hydrogen atom bonded to either a
Nitrogen, Oxygen or Fluorine atom - the three smallest and most electronegative atoms. This will
produce a particularly strongly polar bond within the molecule.

The hydrogen bond can then form between molecules. Specifically, a δ+ hydrogen atom will be
'pinned' in a straight line between two δ- atoms, one within the same molecule and the other in a
neighbouring molecule.

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The extra strength of the hydrogen bond can be seen when comparing the boiling points of the
hydrides of various element.

Most of the molecules featured in the bar-graph are non-polar and rely on London Dispersion
Forces only.

Group 4 elements - As you go up the group (Sn → C) the number of electrons

decreases and the tendency to wobble is reduced. This reduces the sizes
of the temporary dipole / induced dipole so the strength of the London
Dispersion Forces decreases and the boiling points decrease.
Group 5 elements - Again, as you go up the group (Sb → P) the number of electrons
decreases and the tendency to wobble is reduced. However, NH3 is a
very polar molecule and can set up hydrogen bonding and it's boiling
point is about 75° higher than would be expected.
Group 6 elements - Again, as you go up the group (Te → S) the number of electrons
decreases and the tendency to wobble is reduced. However, H2O is a
very polar molecule and can set up hydrogen bonding and it's boiling
point is about 200° higher than would be expected.
Group 7 elements - Again, as you go up the group (I → Cl) the number of electrons
decreases and the tendency to wobble is reduced. However, HF is a
very polar molecule and can set up hydrogen bonding and it's boiling
point is about 100° higher than would be expected.

NB: H2S and HCl are polar so would benefit from extra dipole-dipole attractions, but this has a
small effect on their boiling points - much less than the effect of hydrogen bonding.

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The carbonyl group (C=O) found in molecules such as
aldehydes and ketones will make the molecules polar and
allow for dipole-dipole attractions.
However, there is not a hydrogen bonded to the oxygen so
no hydrogen bonding. Aldehydes and ketones are
volatile chemicals with relatively low boiling points.
The hydroxyl group (O—H) found in alcohols and water
will lead to a very polar molecule and the creation of very
strong hydrogen bonds. Alcohols have relatively high boil-
ing points.

However, hydrogen bonding can be set

up between two molecules even if one of
the molecules cannot do hydrogen
bonding on their own.
Methanol and methanal would mix
with (dissolve in) each other.
Hydrogen bonding can also exist within
a molecule.
Hydrogen bonding is responsible for the
helix structure found in many protein
strands.

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3.1 Practice Problems
1. The diagram opposite is a molecular model of a gaseous
diatomic element that is just above its boiling point.
Intermolecular forces between the gas molecules will cause
them to condense into the liquid phase if the temperature is
lowered.
Which of the following best describes how the model
is limited in its depiction of the phenomenon?

A It does not show how hydrogen bonds are constantly forming, breaking, and
reforming, which results in a net force of attraction between the molecules.
B It does not show how the interactions between ions and the induced molecular
dipoles result in a net force of attraction between the molecules.
C It does not show how the interacting permanent dipoles of the molecules result in a
net force of attraction between the molecules.

O
D It does not show how the temporary fluctuating dipoles of the molecular electron
clouds result in a net force of attraction between the molecules.

2.

The electron cloud of HF is smaller than that of F2 , however, HF has a much higher
boiling point than has F2 . Which of the following explains how the dispersion-force model
of intermolecular attraction does not account for the unusually high boiling point of HF ?

A F2 is soluble in water, whereas HF is insoluble in water.

B The F2 molecule has a greater mass than the HF molecule has.
C Liquid F2 has weak dispersion force attractions between its molecules, whereas l
iquid HF has strong ionic interactions between H+ and F- ions.

O
D Liquid F2 has weak dispersion force attractions between its molecules, whereas
liquid HF has both weak dispersion force attractions and hydrogen bonding
interactions between its molecules.

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3.

Four different liquid compounds in flasks at are represented above. The table below
identifies the compounds. Flask C shows the most particles in the vapor phase.

Which of the following is not shown in the model but best helps to explain why flask C
must contain pentane?
A The random motion of the particles within the liquids.
B The relative speeds of the vapor particles in each flask.

O
C The strength of the intermolecular forces between the particles in the liquids.
D The structural formula of the molecules of the liquid and vapor in each flask.

4. In the diagram below, which of the labeled arrows identifies hydrogen bonding in water?

A A
B B
C C
D O D

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5. In which of the following liquids do the intermolecular forces include dipole-dipole
forces?
A F2 (l) B CH4 (l) C CF4 (l) O
D CH2F2 (l)

6. The London (dispersion) forces are weakest for which of the following gases under the
same conditions of temperature and pressure?

O
A H2 B O2 C Xe D F2 E N2

7. Thymine and adenine form a base pair in the DNA molecule. These two bases can form a
connection between two strands of DNA via two hydrogen bonds.
Which of the following diagrams shows the correct representation of the hydrogen
bonding (denoted by dashed lines) between thymine and adenine base pairs?
(In each diagram, thymine is shown at the left and adenine is shown at the right. The bases
are attached to the backbone portion of the DNA strands.)
A B

C D O

8. Which of the following is the strongest type of interaction that occurs between the atoms
within the circled areas of the two molecules represented below?
A polar covalent bond
B non-polar covalent bond
C O hydrogen bond
D london dispersion force
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Quick Check - AP FRQ Questions
1.

The boiling point of liquid propene (226 K) is lower than the boiling point of liquid
vinyl chloride (260 K). Account for this difference in terms of the types and strengths of
intermolecular forces present in each liquid.
1 point is earned for a discussion of intermolecular forces and for a comparison of their
relative strengths.
Both substances have dipole-dipole interactions and London dispersion forces (or propene
is essentially nonpolar with only LDFs while vinyl chloride has both LDFs and
dipole-dipole forces). Propene contains a CH3 group, but vinyl chloride contains a Cl atom.
Vinyl chloride thus has a larger electron cloud, is more polarizable, and has a larger dipole
moment. Thus intermolecular attractions are stronger in vinyl chloride, which results in it
having a higher boiling point.

2.

a) At 1 atm and 298 K, pentane is a liquid whereas propane is a gas. Explain.

1 point is earned for recognizing that pentane and propane both have only LDF’s.
1 point is earned for recognizing that pentane has a larger electron cloud with greater
IMF’s and higher BP (reference to state of matter).
Both molecules are nonpolar, and the only intermolecular forces in each are London
dispersion forces. However, pentane is larger than propane and has a more extensive
electron cloud that can be involved in a greater number of London interactions, leading to
stronger intermolecular attractions overall. Thus it takes a higher temperature for
pentane molecules to have enough kinetic energy (on average) to overcome their stronger
intermolecular attractions, thus pentane has the higher boiling point.
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Q2 continued
b) At 1 atm and 298 K, methanol is a liquid whereas propane is a gas. Explain.
1 point is earned for recognizing that methanol has hydrogen-bonding IMF’s and propane
has LDF’s.
1 point is earned for recognizing that hydrogen-bonding results in a greater IMF causing
methanol to be a liquid.

Propane molecules are nonpolar and only interact with one another via London dispersion
forces. Methanol molecules are polar and hydrogen bonds (as well as London forces) can
form among them. Because hydrogen bonds are stronger than London forces, methanol
has greater intermolecular attractions. Thus it takes a higher temperature for
methanol molecules to have enough kinetic energy (on average) to overcome their stronger

intermolecular attractions, thus methanol has the higher boiling point.

3.

Two types of intermolecular forces present in liquid H2S are London (dispersion) forces
and dipole-dipole forces.
a) Compare the strength of the London (dispersion) forces in liquid H2S to the
strength of the London (dispersion) forces in liquid H2O. Explain.
1 point is earned for the correct answer with a correct explanation.
The strength of the London forces in liquid H2S is greater than that of the London forces in
liquid H2O. The electron cloud of H2S has more electrons and is thus more polarizable than
the electron cloud of the H2O molecule.

b) Compare the strength of the dipole-dipole forces in liquid H2S to the strength of the
dipole-dipole forces in liquid H2O. Explain.
.
1 point is earned for the correct answer with a correct explanation.
The strength of the dipole-dipole forces in liquid H2S is weaker than that of the
dipole-dipole forces in liquid H2O. The net dipole moment of the H2S molecule is less than
that of the H2O molecule. This results from the lesser polarity of the H–S bond compared
with that of the H–O bond (S is less electronegative than O).

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4. Propanoic acid, C2H5COOH has a lower boiling point than butanoic acid, C3H7COOH.

a) Identify all the types of intermolecular forces present among the molecules in
propanoic acid.
1 point is earned for identifying both London dispersion forces and hydrogen

bonding.

London dispersion forces, dipole-dipole forces, and hydrogen bonding. (Identifying
dipole-dipole forces is not required to earn the point.)

b) Which of the types of intermolecular forces that you identified in part a) is most
responsible for the difference in boiling points of the two acids?

1 point is earned for the correct answer. London dispersion forces.

5.
Br2 + Cl2 → 2 BrCl
Br2 and Cl2 can react to form the compound BrCl .
The boiling point of Br2 is 332K, whereas the boiling point of BrCl is 278K. Explain this
difference in boiling point in terms of all the intermolecular forces present
between molecules of each substance.

The response meets both of the following criteria.

The response indicates that the only intermolecular attractions in Br2(l) are London forces,
while those in BrCl(l) include both London forces and dipole-dipole forces.
The response indicates that due to the greater polarizability of the electron cloud of Br2(l)
compared to that of BrCl(l) , the London forces in Br2(l) are stronger than the
combined intermolecular forces in BrCl(l) and thus the boiling point of Br2(l) is greater than
that of BrCl(l) .

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6. Answer the following questions by using principles of molecular structure and
intermolecular forces.
a) Structures of the pyridine molecule and the benzene molecule are shown below.

Pyridine is soluble in water, whereas benzene is not soluble in water. Account for the
difference in solubility. You must discuss both of the substances in your answer.
1 point is earned for identifying a relevant structural difference between pyridine and
benzene.
1 point is earned for indicating that pyridine is soluble in water because pyridine can form
strong dipole-dipole interactions (or hydrogen bonds) with water, while benzene cannot.

Pyridine is polar (and capable of forming hydrogen bonds with water), while the nonpolar
benzene is not capable of forming hydrogen bonds. Pyridine will dissolve in water because
of the strong hydrogen bonds (or dipole-dipole intermolecular interactions) that exist
between the lone pair of electrons on pyridine’s nitrogen atom and the solvent water
molecules. No such strong intermolecular interaction can exist between benzene and
water, so benzene is insoluble in water.

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Q6 continued
b) Structures of the dimethyl ether molecule and the ethanol molecule are shown
below.

The normal boiling point of dimethyl ether is 250 K, whereas the normal boiling
point of ethanol is 351 K. Account for the difference in boiling points. You
must discuss both of the substances in your answer.
1 point is earned for recognizing that ethanol molecules can form intermolecular hydrogen
bonds, whereas dimethyl ether molecules do not form intermolecular hydrogen bonds.
1 point is earned for recognizing that, compared to the energy required to overcome the
weaker intermolecular forces in liquid dimethyl ether, more energy is required to
overcome the stronger hydrogen bonds in liquid ethanol, leading to a higher boiling point.

The intermolecular forces of attraction among molecules of dimethyl ether consist of

London (dispersion) forces and weak dipole-dipole interactions. In addition to London
forces and dipole-dipole interactions that are comparable in strength to those in dimethyl
ether, ethanol can form hydrogen bonds between the H of one molecule and the O
of a nearby ethanol molecule. Hydrogen bonds are particularly strong intermolecular
forces, so they require more energy to overcome during the boiling process. As a result, a
higher temperature is needed to boil ethanol than is needed to boil dimethyl ether.

c) The normal boiling point of Cl2 (l) (238 K) is higher than the normal boiling point
of HCl(l) (188 K). Account for the difference in normal boiling points based on the
types of intermolecular forces in the substances. You must discuss both of the
substances in your answer.
1 point is earned for recognizing that the London forces among Cl2 molecules must be
larger than the intermolecular forces (London and dipole-dipole) among HCl molecules.
1 point is earned for recognizing that the strength of the London forces among molecules
is proportional to the total number of electrons in each molecule.
The intermolecular forces in liquid Cl2 are London (dispersion) forces, whereas the
intermolecular forces in liquid HCl consist of London forces and dipole-dipole
interactions. Since the boiling point of Cl2 is higher than the boiling point of HCl, the
London forces among Cl2 molecules must be greater than the London and dipole-dipole
forces among HCl molecules. The greater strength of the London forces between Cl2
molecules occurs because Cl2 has more electrons than HCl, and the strength of the London
interaction is proportional to the total number of electrons.
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3.2 Properties of Solids

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3.2 Properties of Solids

Just about all substances can be found in the solid, liquid or gas phase, depending on temperature
and pressure. Those with the strongest Intermolecular Forces are most likely to be found in the
solid phase at s.t.p. (standard temperature & pressure - 25° C and 1 atm pressure)

Typically, Ionic bonding - all ionic compounds are solids at s.t.p.

Metallic bonding - all metals except Mercury are solids at s.t.p.
Covalent bonding - all covalent networks are solids at s.t.p.
covalent molecules depend on strength of
van der waals forces.
CO2 and I2 are both non-polar molecules and
rely on London Dispersion Forces.
CO2 is a gas at s.t.p. so LDF's are relatively
weak. LDF's in I2 are stronger and iodine is a
solid at s.t.p.
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Ionic Lattices
Ionic compounds benefit from many strong
interactions at short distances.
F = q1 q2 / r2
Melting points and lattice enthalpies can be
used to compare the strengths of ionic bonds.

From the table, it can be deduced that the charge on the ions (q1 q2) has the biggest influence on
the force of attraction but, when comparing compounds with same charges, the distance (r2) will
explain differences. Distance can be considered to be the sum of the two ionic radii.

The same pattern is seen when considering lattice

enthalpies. In general, ionic compounds will have
high melting and boiling points. There will be
very little tendency to produce gas so vapour
pressures will be extremely low.
Though they can be considered hard solids, ionic
compounds are very brittle as any distortion in the
ionic lattice can produce strong repulsion forces
that will break the crystal apart.
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The best definitions of an electric current describe it in terms of the movement of charge. Charge
carriers can include electrons, protons, ions and even 'positive holes'.

Ionic compounds can be considered as

conductors - more often referred to as
electrolytes - but only when their ions
are free to move.
This can be achieved by melting the
ionic compound or (usually easier) by
dissolving it in water or some other
suitable solvent.
It must be stressed that electrons do not flow
through ionic compounds. They do not conduct
like metals.
Instead, reactions at the electrodes will produce a
flow of electrons in the external circuit - allowing
bulbs to light, buzzers to ring etc.
The ionic compound is broken down as a result -
Electrolysis.
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3.2 Practice Problems - Part 1
1.

The ionic compounds NaCl and MgS are represented by the diagrams above. Which
statement correctly identifies diagram 1 and identifies the compound with the lower
melting point, explaining why?

A Diagram 1 represents NaCl ; it has a lower melting point than MgS has because the
coulombic attractions between the singly charged Na+ ions and the Cl- ions in NaCl
are stronger than those between the ions in MgS.

O
B Diagram 1 represents NaCl ; it has a lower melting point than MgS because the
coulombic attractions between its singly charged Na+ ions and the Cl- ions are weaker
than those between the ions in MgS.
C Diagram 1 represents MgS ; it has a lower melting point than NaCl because the
coulombic attractions between its doubly charged Mg2+ ions and the S2- ions are
stronger than those between the ions in NaCl.
D Diagram 1 represents MgS ; it has a lower melting point than NaCl because the
coulombic attractions between the doubly charged Mg2+ ions and the S2_ ions are
weaker than those between the ions in NaCl.

2. A sample of a hard, solid binary compound at room temperature did not conduct
electricity as a pure solid but became highly conductive when dissolved in water.
Which of the following types of interactions is most likely found between the particles in
the substance?

O
A ionic bonds B metallic bonds
C covalent bonds D hydrogen bonds

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3. A student is given a sample of a pure, white crystalline substance.
Which of the following would be most useful in providing data to determine if the
substance is an ionic compound?
A Examining the crystals of the substance under a microscope
B Determining the density of the substance
C Testing the electrical conductivity of the crystals

O
D Testing the electrical conductivity of an aqueous solution of the substance

4.

Based on the diagram above, which of the following best helps to explain why MgO(s) is
not able to conduct electricity, but MgO(l) is a good conductor of electricity?
A MgO(s) does not contain free electrons, but MgO(l) contains free electrons that can
flow.
B MgO(s) contains no water, but MgO(l) contains water that can conduct electricity.
C MgO(s) consists of separate Mg2+ ions and O2− ions, but MgO(l) contains MgO
molecules that can conduct electricity.

O
D MgO
MgO
(s)
consists of separate Mg2+ ions and O2− ions held in a fixed lattice, but in
the ions are free to move and conduct electricity.
(l)

5. Which of the following could be the identity of a white crystalline solid that exhibits the
following properties?
• It melts at 320°C.
• It does not conduct electricity as a solid.
• It conducts electricity in an aqueous solution.
A C6H12O6(s)

O
B NaOH(s)
C SiO2(s)
D Cu(s)
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Covalent Networks
Covalent networls also benefit from many
strong interactions at short distances.
F = q1 q2 / r2
Melting points can be used to compare the
strengths of covalent networks.

Basic
Unit

Structure

Name
Bond length 142
(pm)
154 165 186 (335 between layers)

Bond Strength 825

(kJ mol-1)
607 408 451 (~13 between layers)

Melting Point
( °C )
3500* 1700 2730 3500*

* Under normal atmospheric pressures, diamonds would convert to graphite at about 1000 °C
and then sublime to vapour at about 3500 °C.
Most covalent networks have a
tetrahedral structure based on
sp3 hybrid orbitals.
All electrons will be held in
strong covalent bonds which
result in high melting points.
The electrons have no freedom to move so covalent networks are
non-conductors. They will be hard but brittle:- bonds cannot
reform if atoms are moved.
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The exception amongst covalent networks
is graphite.
Each carbon is only bonded to 3 other
carbon atoms so only does sp2 hybridisation.
The remaining p-orbitals overlap to form π
bonding molecular orbitals that extend over
all the carbon atoms within a layer - this results
in delocalised electrons.

The delocalised electrons can be made

to flow in any direction so graphite is a
good conductor of electricity.
The extra bonding (bond order = 1.5)
ensures a strong C—C bond, which
contributes to the high melting point.
The delocalised electrons can also
'wobble' creating temporary dipoles
within a layer.
This can then induce dipoles in nearby
layers and will lead to weak London
Dispersion Forces between the layers.
As a result graphite is relatively soft
(pencils) while the ease with which
layers can slide over each other makes
graphite a good lubricant.

Metallic Lattices
Metallic lattices (elements and alloys) benefit
from many strong interactions at short
distances.
F = q1 q2 / r2
Melting points can be used to compare the
strengths of metallic bonds.
For example, mercury is a liquid at room
temperature, and caesium melts at 28.4°C,
whereas tungsten melts at 3680°C.
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F = q1 q2 / r2

There is a similar range in hardness of metals with caesium being a very soft metal and chromium
being the hardest pure metal, though many alloys, such as chromium steel are even harder.
The delocalised electrons mean that metals and alloys
of metals are all good conductors.
Metals are also malleable and ductile. Both malleability and
ductility refer to the ability of metals to be deformed (reshaped)
without any loss in structural strength.
Malleable refers to the ability to be beaten or rolled into sheet
metal - gold is the most malleable metal and can form sheets
that are only a few atoms thick.
Ductility is the ability of a substance to be pulled or stretched, in this case into a thin wire,
without breaking. The most ductile metal is platinum. A single gram of platinum can be drawn
into a wire more than 2.5 km long without breaking.

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Metals can form alloys so easily because replacing one
metal atom with another metal atom rarely disrupts the
strength of the metallic bonding too much.
For example, an alloy of sodium and potsssium can be
made, but the alloy formed is a liquid at room
temperature so the metallic bond is slightly weaker.

Brass is an example of a substitutional alloy. Zinc and

copper atoms are of very similar size so the original
structure is maintained, though strengthened.
This alloy retains properties such as malleability and
ductility as metallic bonding is easily re-established.

Steel is an interstitial alloy with much smaller carbon

atoms in the spaces between the iron atoms.
The presence of the carbon atoms enhances the
structure so steel is harder than the original iron, but it
will also be less malleable and less ductile as a result.

The wide variety of alloys makes it difficult to make accurate predictions about properties, but, in
general, alloys will be poorer conductors, less malleable, less ductile but stronger/harder.
Also, in general, smaller atoms that are able to form interstitial alloys will have a more disruptive
effect on metallic bonding, making it harder to displace atoms resulting in stronger alloys.

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3.2 Practice Problems - Part 2
7.

The table above provides some information about two types of steel, both of which are
alloys of iron and carbon. Which of the following best helps to explain why high-carbon
steel is more rigid than low-carbon steel?
A Elemental carbon is harder than elemental iron.
B The additional carbon atoms within the alloy make the high-carbon steel less dense.
C The additional carbon atoms within the alloy increase the thermal conductivity of
the high-carbon steel.

O
D The additional carbon atoms within the alloy make it more difficult for the iron
atoms to slide past one another.

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Covalent Molecular Solids
Covalent molecules only have the weaker
Van der Waals Forces operating between
molecules so most are liquids or even gases
at s.t.p.
However, some have strong enough
intermolecular forces to be solids at s.t.p,
though they will usually have low
Mpt = -78 °C Mpt = 113.5 °C melting points.

Molecular Elements

Elements will have non-polar covalent bonds so have to rely on London Dispersion Forces
(temporary dipole - induced dipole).
Only iodine, with electons in the 5th shell, wobbles enough to produce large enough partial
charges (δ+ and δ-) to be solid at room teperature.
F = q1 q2 / r2

Phosphorus and sulfur, with electons

in the 3rd shell, wobble less and have
smaller partial charges (δ+ and δ-).
However, being polyatomic molecules,
they can set up multiple LDF's.
Mpt of S = 112.8 °C
Mpt of P = 44.1 °C
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Molecular Compounds
Can either be
non-polar - London Dispersion Forces
or polar - permanent dipole - dipole
- hydrogen bonds
This depends on electronegativity differences.

In general, we can assume that polar molecules are more likely to form solds at s.t.p, but, in
reality many of our covalent molecular solids are non-polar due to the presence of large atoms
(bigger wobbles, greater partical charges) or due to the large number of atoms per molecule (more
wobbles).

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Summary of Main Attractions

Attractions between
Ionic positive ion (Cation) and
Negative ion (Anion)

Attractions between both

Covalent nuclei (+ve) for same pair of
shared electrons (-ve)

Attractions between positive

Metallic core (temporary cations) and
delocalised electrons (-ve)

Van Der Waal's Forces

Attractions between an ion

Ion - Dipole and the oppositively charged
end of a polar molecule

Attractions between the

Dipole - Dipole oppositively charged ends of
(Hydrogen Bonding) nearby polar molecules with
H—O or H—N

Attractions between the

Dipole - Dipole oppositively charged ends of
nearby polar molecules

Attraction between an ion

Ion - Non-Polar and the induced dipole of a
normally non-polar molecule

Attraction between a polar

molecule and the induced
Dipole - Non Polar
dipole of a normally
non-polar molecule

Attraction between the

Non Polar - Non Polar
temporary dipole and
(London Dispersion)
induced dipole
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3.2 Practice Problems - Part 3

8. Which statement best helps to explain the observation that NH3 (l) boils at -28°C ,
whereas PH3 (l) boils at -126 °C ?

A The dispersion forces in NH3 are weaker than the dispersion forces in PH3.
B The dispersion forces in NH3 are stronger than the dipole-dipole forces in PH3.

O
C NH3 has hydrogen bonding that is stronger than the dipole-dipole forces in PH3.
D NH3 has hydrogen bonding that is weaker than the dipole-dipole forces in PH3.

9. A certain crystalline substance that has a low melting point does not conduct electricity in
solution or when melted. This substance is likely to be

A a covalent network solid B a metallic solid

C a polymer D an ionic solid OE a molecular solid

10. At room temperature I2(s) is a molecular solid. Which of the following provides a
characteristic of I2(s) with a correct explanation?

A It has a high melting point because it has weak intermolecular forces.

B It is hard because it forms a three dimensional covalent network.

O
C It is not a good conductor of electricity because its valence electrons are localized
in bonding and nonbonding pairs.
D It is very soluble in water because its molecules are polar.
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11.

The structure of one form of boron nitride is represented above.

This form of boron nitride is one of the hardest substances known. Which of the following
best helps explain why boron nitride is so hard?
A Boron ions and nitrogen ions are held together by ionic bonds.

O
B Boron nitride is a network solid of atoms connected by covalent bonds with fixed
bond angles.
C Boron nitride is an alloy, and alloys are typically harder than the elements used to
make them.
D Boron nitride is a polymer made of long chains of boron atoms and nitrogen atoms
held together by london dispersion forces.

12. In solid methane, the forces between neighboring CH4 molecules are best characterized as
A ionic bonds B covalent bonds C hydrogen bonds
D ion-dipole forces OE london (dispersion) forces

13. The best explanation for the fact that diamond is extremely hard is that diamond crystals
A are made up of atoms that are intrinsically hard because of their electronic structures
B consist of positive and negative ions that are strongly attracted to each other

O
C are giant molecules in which each atom forms strong covalent bonds with all of its
neighboring atoms
D are formed under extreme conditions of temperature and pressure
E contain orbitals or bands of delocalized electrons that belong not to single atoms
but to each crystal as a whole
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Biomolecules & Polymers
Very large molecules, such as polymers, will be
solids due to the large numbers of attractions,
even if only London Dispersion Forces, that can be
set up.
Polyethene -110 - 130 °C

Other polymers can have permanent

dipoles and will have stronger
attractions between the chains.

Polyvinylchloride -180 - 220 °C

The strongest polymers tend to mimic nature and

use the amide (peptide) links found in proteins.
One of the strongest polyamides is Kevlar and it
benefits from many strong hydrogen bonds at
regular intervals along the chain.

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Sugars (Saccharides, Carbohydrates)

The presence of so many hydroxyl

groups makes sugar molecules
very polar and produces hydrogen
bonding between molecules.
As a result of this hydrogen bonding, all sugars are solids at s.t.p. and most of them are soluble in
water - though polysaccharides such as starch are sparingly soluble.

Amino Acids

The presence of the carboxyl (COOH) and amine groups (NH2) again leads to hydrogen bonding.

However, hydrogen bonding alone

would not explain why amino acids are
crystalline solids at s.t.p.
In neutral conditions the hydrogen
from the carboxyl group migrates to
the amine group to produce two ionic
groups.
This produces attractions betwen
molecules that are much stronger than
expected.
Side chains can also contribute with a
variety of different types of attraction
possible.
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Proteins

The most significant attractions found in

protein molecules are the hydrogen bonds
formed between C = Oδ- and δ+H—N groups.
However, all forms of attraction will be
present in proteins.

As a result, complex and unique shaped sections are formed which can interact with specific
molecules with complementary groups that can form attractions to the protein. This allows the
protein to have a number of useful properties such as enzyme (catalyst) etc.

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Lipids (Fats & Oils)

Lipids are long term energy stores and are formed

from one glycerol molecule and 3 fatty acids.
They can also be referred to as triglycerides. Though
there are polar groups, the long non-polar carbon chains
mean that the main attractions are London Dispersion Forces.

The individual fatty acids typically have

between 13 and 18 Carbon atoms in the
chain.
Most fatty acids are described as saturated -
all the C to C bonds are single bonds.
Unsaturated fatty acids will have at
least on C to C double bond, which
will result in a permanent kink in the
chain.

Both Fats & Oils have a mixture of molecules

containing both saturated and unsaturated
fatty acids.
Saturated fatty acid molecules can
rotate around each bond to 'straighten'
the chain allowing them to maximise
the London Dispersion forces between
neighbouring molecules.
Unsaturated fatty acid molecules are
unable to rotate around the double
bond so London Dispersion forces are
reduced.
Therefore, in general, lipids made by
plants and marine animals, tend to be
more unsaturated and are likely to be
liquid oils at room temperature.

By contrast, most animals produce lipids that more saturated and tend to solid fats at room
temperature.
From Fats & Oils, our first soap molecules were made which are molecules with dual properties.
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Surfactants - Soaps & Detergents

Fatty acids have long enough carbon chains that

the 'head' can display polar properties (hydrophilic)
while the 'tail' is non-polar (hydrophobic).
The polarity of the 'head' can be greatly enhanced
if the acid is fully ionised by reacting with a base,
such as NaOH, to form a soluble salt of the acid.
Soaps were traditionally made by hydrolysing
(breaking down) fats or oils using a base.
The names of soaps often displayed this link -
Palmolive soap was made from palm oil and olive oil.
The glycerol formed would find its way into many
other cosmetic products such as hand creams and
lip balms.
Surfactants, such as soaps,
work at the interface of two
liquids that would normally
not mix - grease and water,
for example.
They can help disperse the
grease into tiny droplets so
that the grease appears to
dissolve into the water.
In reality, an unstable mixture
called an emulsion is formed.
Surfactants help mix oil paint
and water to form emulsion
paint suitable for covering large surfaces quickly.
Problems, particularly with 'hard' water - water
with Ca2+ and Mg2+ ions dissolved, led chemists
to develop more soluble artificial soaps -
called detergents.
Surfactants are widely used in the food
industry but are usually labelled as
emulsifiying agents.

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Surfactants - Phospholipids
In nature, a modified lipid is used as the
building block for cell membranes.

3.2 Quick Check - AP FRQ Questions

1. The structures for glucose, C6H12O6 , and
cyclohexane, C6H12 , are shown opposite.
a) Identify the type(s) of intermolecular
attractive forces in

i) pure glucose
1 point is earned for the correct answer.
Hydrogen bonding OR dipole-dipole interactions OR van der Waals interactions
(London dispersion forces may also be mentioned.)

ii) pure cyclohexane
1 point is earned for London dispersion forces.

b) Glucose is soluble in water but cyclohexane is not soluble in water. Explain.

1 point is earned for explaining the solubility of glucose in terms of hydrogen bonding or
dipole-dipole interactions with water.
1 point is earned for explaining the difference in the polarity of cyclohexane and water.

The hydroxyl groups in glucose molecules can form strong hydrogen bonds with the
solvent (water) molecules, so glucose is soluble in water. In contrast, cyclohexane is not
capable of forming strong intermolecular attractions with water (no hydrogen bonding), so
the water-cyclohexane interactions are not as energetically favorable as the interactions
that already exist among polar water molecules.
OR - see at end of next page
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2. The Lewis electron-dot diagrams for molecules of CH4 and CCl4 are shown
opposite.
Which compound has the higher boiling point? Justify your answer. The
type(s) of intermolecular force(s) in both substances should be included in

your answer.

The response meets both of the criteria below:

The response indicates that both compounds have London dispersion forces.
(If the response indicates that either of the compounds has any other type of
intermolecular force, the criterion is not met.)
The response indicates that has the higher boiling point and that it has greater
intermolecular forces.

Q1 b) answer continued
1 point is earned for any one of the three concepts; two points are earned for any two of the
three concepts.
• Glucose is polar and cyclohexane is nonpolar.
• Polar solutes (such as glucose) are generally soluble in polar solvents such as water.
• Nonpolar solutes (such as cyclohexane) are not soluble in the polar solvent.

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3.3 Solids, Liquids & Gases

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Solids
Solids can be crystalline, where the particles are arranged in a regular three-dimensional
structure, or they can be amorphous, where the particles do not have a regular, orderly
arrangement.

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In all solids, the motion of the
individual particles is limited,
and the particles cannot change
position with respect to each
other - motion is limited to
vibration.
The detailed structure of the solid
is influenced by interparticle
interactions and the ability of the
particles to pack together.

Liquids
The constituent particles in liquids are in close contact
with each other, and they are continually moving and
colliding.
The arrangement and movement of particles are influenced
by the nature and strength of the forces (e.g. polarity,
hydrogen bonding etc.) between the particles and, of
course, temperature.
The distance between particles of the same substance in the
solid and liquid are very similar.

Spaces between particles in both solids and liquids are so small that it
is almost impossible to compress most normal solids and liquids.
Therefore, they typically have similar molar volumes because, in both phases, the constituent
particles are in close contact at all times.
The exception to this is water. As water
freezes, the strong hydrogen bonds
lock the water molecules into a
hexagonal structure.
This actually increases the spaces
between the water molecules, and
creates empty spaces in the centre of
the hexagons.

As a result, water expands as it freezes and solid water has a larger molar volume than liquid
water. This also means that water is just about the only substance where the solid floats (is less
dense) on top of its liquid.
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Gases
In the gas phase, the particles are in constant
motion.
Their frequencies of collision and the
average spacing between them are only dependent
on temperature, pressure, and volume - the particles
are too far apart to have intermolecular forces.
Becauseof this constant motion, and minimal
effects of forces between particles, a gas has neither a
definite volume nor a definite shape.
The much larger spaces between gas particles makes
it easy to compress a gas.

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Quick Check - AP FRQ Questions
1. The Lewis electron-dot diagrams for molecules of CH4 and CCl4 are shown
opposite.
CCl4(l) is placed in a previously evacuated container at 30°C, and some of the
CCl4(l) evaporates.
In the box below, draw a particulate diagram to show the species in the
container after some of the CCl4(l) has evaporated.
The phases of the species should be indicated by the spacing and distribution
of the particles in the diagram. Some of the species shown in the legend
will not be used.

The drawing meets all of the criteria below:

There are closely spaced undefined molecules near the bottom of the box.
There are more widely spaced undefined molecules in the box.
There are no separate undefined molecules, undefined atoms, or undefined atoms in the

box.

3.3 Practice Problems

1. Of the following, the best explanation for the fact that most gases are easily compressed is
that the molecules in a gas

A are in constant motion

O
B are relatively far apart
C have relatively small masses
D have a real, nonzero volume E move slower as temperature decreases
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3.4 Ideal Gas Law

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The Pressure –Volume Relationship: Boyle’s Law
British chemist Robert Boyle (1627–1691)
first investigated the relationship between
the pressure of a gas and its volume, using
a J-shaped tube like that shown in the
diagram opposite.
In the tube, a quantity of gas is trapped
above a column of mercury. Boyle then
changed the pressure on the gas by
adding mercury to the tube.
He found that the volume of the gas
decreased as the pressure increased.
For example, doubling the pressure caused
the gas volume to decrease to half its
original value.

Boyle’s law, which summarizes these observations, states that the volume of a fixed quantity of gas
maintained at constant temperature is inversely proportional to the pressure.

Mathematically, this can be expresed as: V = a constant x 1/P

Or, more usefully, it can be expressed as: PV = a constant
We apply Boyle’s law every time we breathe. The rib cage, which can expand and contract, and the diaphragm, a muscle
beneath the lungs, govern the volume of the lungs. Inhalation occurs when the rib cage expands and the diaphragm moves
downward.
Both actions increase the volume of the lungs, thus decreasing the gas pressure inside the lungs. Atmospheric pressure then
forces air into the lungs until the pressure in thelungs equals atmospheric pressure.
Exhalation reverses the process—the rib cage contracts and the diaphragm moves up,decreasing the volume of the lungs.
Air is forced out of the lungs by the resulting increase in pressure.
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The Temperature –Volume Relationship: Charles’s Law
The relationship between gas volume and
temperature— volume increases as
temperature increases —was discovered
in 1787 by French scientist Jacques Charles
(1746–1823).
Notice that the extrapolated (dashed) line
passes through -273 °C . Note also that the
gas is predicted to have zero volume at this
temperature.
This condition is never realized, however,
because all gases liquefy or solidify before
reaching this temperature.

In 1848 William Thomson (1824–1907), a Irish-Scottish physicist whose title was Lord Kelvin,
proposed an absolute-temperature scale, now known as the Kelvin scale. On this scale 0 K, called
absolute zero, equals -273.15 °C.
Charles’s law, which summarizes these observations, states that the volume of a fixed amount of
gas maintained at constant pressure is directly proportional to its absolute temperature..

Mathematically, this can be expresed as: V = a constant x T

Or, more usefully, it can be expressed as: V/T = a constant

The Quantity –Volume Relationship: Avogadro’s Law

The relationship between the

quantity of a gas and its volume
follows from the work of Joseph
Louis Gay-Lussac (1778–1823) and
Amedeo Avogadro (1776–1856).

Avogadro’s hypothesis: Equal volumes of gases at the same temperature and pressure contain
equal numbers of molecules.

For example, 22.4 L of any gas at and 1 atm contain 6.023 x 1023 gas molecules (that is, 1 mol).

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Avogadro’s Law: The volume of a gas maintained at constant temperature and pressure is directly
proportional to the number of moles of the gas.

V = a constant x n
Mathematically, this can be expresed as:
were n = number of moles
Thus, for instance, doubling the number of moles of gas causes the volume to double if T and P
remain constant.

THE IDEAL-GAS EQUATION

The previous three laws were obtained by holding two of the four variables P, V, T, and n
constant and seeing how the remaining two variables affect each other.
Boyle’s law: V ∝ 1/P (constant n, T)
Charles’s law: V ∝ T (constant n, P)
Avogadro’s law: V ∝ n (constant P, T)

Combined Law: V ∝ nT/P or better PV ∝ nT

As always, there is a constant of proportionality.
In this case it is called the Gas Constant, R so PV = nRT

'Unfortunately' there a wide variety of ways

of measuring or calculating these values and
many different units. Normally we would
expect to adopt SI units:
P in pascals (Pa) (1 Pa = 105 Nm-2)
V in m3 - m3 = 1000 L

However, it is easier to use pressures expressed as multiples of atmospheres, atm and volumes in
litres, so probably most likely to use the Gas Constant as:
R = 0.08206 L atm mol-1 K-1

'Fortunately'
T is always in Kelvin and n is always in moles
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Example 1 Sulfur hexafluoride (SF6 ) is a colorless, odorless, very unreactive gas.
Calculate the pressure (in atm) exerted by 1.82 moles of the gas in a
steel vessel of volume 5.43 L at 69.58 °C.
PV = nRT P = nRT/V
P = (1.82 mol) x (0.08206 L atm mol-1 K-1) x ( 342.5 K)
5.43 L
P = 9.42 atm

Example 2 Calculate the volume (in liters) occupied by 2.12 moles of nitric oxide (NO) at
6.54 atm and 768 °C.
PV = nRT V = nRT/P
V = (2.12 mol) x (0.08206 L atm mol-1 K-1) x ( 1041 K)
6.54 atm
V = 27.69 L

Strictly speaking, the ideal gas equation should only be

applied to “ideal gases,” that is, gases that conform to the
assumptions of the kinetic molecular theory.
Two of the assumptions of this theory are:-
that the molecules of a gas possess zero volume
and that there are no attractive forces between gases

In fact, the molecules of all gases do possess volume but it is very small - virtually all the volume of
a gas is empty space.
In fact, the molecules of all gases do exert attractive forces but they are very small - normally the
particles in a gas are too far apart to exert attractions but they will prevent collisions being elastic.

Elastic collisions conserve their kinetic energy, whereas

kinetic energy is lost during inelastic collisions.
In reality, as long as the pressure is not too high or the
temperature is too low, the Ideal-Gas Equation will
provide accurate calculations for almost all gases.

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3.4 Quick Check - AP FRQ Questions 1
1. CaCO3(s) ⇌ CaO(s) + CO2(g)
When heated strongly, solid calcium carbonate decomposes to produce solid calcium oxide
and carbon dioxide gas, as represented by the equation above.
A 2.0mol sample of CaCO3(s) is placed in a rigid 100.L reaction vessel from which all the
air has been evacuated. The vessel is heated to 898°C at which time the pressure of CO2(g)
in the vessel is constant at 1.00atm, while some CaCO3(s) remains in the vessel.
a) Calculate the number of moles of CO2(g) present in the vessel at equilibrium.
The response includes both the following set up and calculation:

n = PV / RT = (1.00 atm)(100 L) / (0.0821 [Link]-1.K-1)(1171 K)


= 1.04 mol

b) The experiment was repeated, but this time starting with a 4.0mol sample of
CaCO3(s). On the following graph, draw a curve showing how the pressure of CO2(g)
would change over time as the vessel is heated to 898°C and equilibrium is
established.

The response shows a graph that starts at the origin, rises to right, and levels off
(slope = 0) at 1.00 atm
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2. CaCO3(s) ⇌ CaO(s) + CO2(g)
When heated, calcium carbonate decomposes
according to the equation above. In a study of
the decomposition of calcium carbonate, a
student added a 50.0 g sample of powdered
CaCO3(s) to a 1.00 L rigid container.
The student sealed the container, pumped out
all the gases, then heated the container in an
oven at 1100 K. As the container was heated,
the total pressure of the CO2(g) in the container
was measured over time. The data are plotted in
the graph opposite.
The student repeated the experiment, but this time the student used a 100.0 g sample of
powdered CaCO3(s). In this experiment, the final pressure in the container was
1.04 atm, which was the same final pressure as in the first experiment.
a) Calculate the number of moles of CO2(g) present in the container after 20 minutes
of heating.
1 point is earned for the proper setup using the ideal gas law and an answer that is
consistent with the setup. PV = nRT

n = PV / RT = (1.04 atm)(1.00 L) / (0.0821 [Link]-1.K-1)(1100 K)
= 0.0115 mol

b) The student claimed that the final pressure in the container in each experiment
became constant because all of the CaCO3(s) had decomposed. Based on the data in
. the experiments, do you agree with this claim? Explain.
1 point is earned for disagreement with the claim and for a correct justification using
stoichiometry or a discussion of the creation of an equilibrium condition.

3.4 Practice Problems - Part 1

1. The pressure, in atm, exerted by 1.85 mol of an ideal gas placed in a 3.00 L container at
35.0°C is given by which of the following expressions?

O
A B C

D E
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Molar Volume: Suppose we have 1.000 mol of an ideal gas at 1.000 atm and 0.000°C
(273.15 K).
According to the ideal-gas equation, the volume of the gas is
PV = nRT V = nRT/P
V = (1.000 mol) x (0.08206 L atm mol-1 K-1) x ( 273.15 K)
1.000 atm
V = 22.41 L

The conditions 0 °C and 1 atm are referred to as standard temperature and pressure (STP). The
volume occupied by 1 mol of ideal gas at STP, 22.41 L, is known as the molar volume of an ideal
gas at STP.
Experimentally determined molar volumes for individual gases will, of course, not be exactly the
same, as they are non-ideal gases. However, their behavior differs so little from ideal behavior
that we can ignore any deviations for all but the most accurate work.

Calculations that explicitely use the value of 22.41 L are not that commom in AP Chemistry - and
may involve conversions to allow for actual temperatures and actual pressures used (STP is not
'normal conditions').
Most questions seem to involve use of .......
Avogadro’s hypothesis: Equal volumes of gases at the same temperature and pressure contain
equal numbers of molecules.

..... combined with the ability

to juggle different volumes
and pressures .....

PV = nRT
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3.4 Practice Problems - Part 2
2. The table below contains information about samples of four different gases at 273 K. The
samples are in four identical rigid containers numbered 1 through 4.

On the basis of the data provided above, the gas in container 3 could be

O
A CH4 B O2 C Ar D CO2

3. This question refer to three gases in identical rigid containers under the conditions given
in the table below.

The density of the gas, in g/L, is

A greatest in container A O
B greatest in container B
C greatest in container C D the same for all 3 containers

4.

The figure above represents three sealed 1.0 L vessels, each containing a different inert
gas at 298 K. The pressure of Ar in the first vessel is 2.0 atm. The ratio of the numbers of
Ar, Ne, and He atoms in the vessels is 2 : 1 : 6, respectively.
After all the gases are combined in a previously evacuated 2.0 L vessel, what is the total
pressure of the gases at 298 K?
A 3.0 atm
ISPS Chemistry Oct 2025
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B 4.5 atm
page 58
C 9.0 atm D 18 atm
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Non STP conversions: Earlier we calculated the molar volume at STP
According to the ideal-gas equation, the volume of the gas is
PV = nRT V = nRT/P
V = (1.000 mol) x (0.08206 L atm mol-1 K-1) x ( 273.15 K)
1.000 atm
V = 22.41 L
However:
After elemental analysis the empirical formula of a compound was determined to be
CH2Br . It was also found to have a vapor density of 6.00 g L−1 at 375 K and 0.983 atm.

To solve questions related to this data, it might be necessary to know the molar volume under
these conditions. One way is to simply repeat the above calculation:
PV = nRT V = nRT/P
V = (1.000 mol) x (0.08206 L atm mol-1 K-1) x ( 375 K)
0.983 atm
V = 31.31 L

More generally, we can adapt the ideal-gas equation to calculate effect of different conditions
using the fact that R is a constant.
P1V1 P2V2 (where the subscripts 1 and 2
= R = represent the initial and final
n1T1 n2T2 states, respectively)

Quite
often number of moles P1V1 P2V2
is unknown but is remaining
=

constant so ..... T1 T2
Or rigid container with fixed
P1 P2 V1 V2
volume
or open system with = =

constant pressure so ..... T1 T2 T1 T2
Or we can even set things
up so that the temperature

P1V1 = P2V2
remains constant so .....

In reality, a lot of questions simply require you to use the ideal-gas equation to quickly establish
relationships such as:
doubling pressure will half the volume
doubling temperature will double the volume etc.
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3.4 Practice Problems - Part 3
5.

The reaction between NO(g) and O2(g) to produce NO2(g) in a rigid reaction vessel is
represented in the diagram above. The pressure inside the container is recorded using a
pressure gauge.
Which of the following statements correctly predicts the change in pressure as the reaction
goes to completion at constant temperature, and provides the correct explanation?
A The pressure will increase because the product molecules have a greater mass than
either of the reactant molecules.

O
B The pressure will decrease because there are fewer molecules of product than of
reactants.
C The pressure will decrease because the product molecules have a lower average
speed than the reactant molecules.
D The pressure will not change because the total mass of the product molecules is the
same as the total mass of the reactant molecules.

6. When a sample of oxygen gas in a closed con­tainer of constant volume is heated until its
abso­lute tem­pera­ture is doubled, which of the follow­ing is also dou­bled?

A The density of the gas

O
B The pressure of the gas
C The average velocity of the gas molecules
D The number of molecules per cm3
E The potential energy of the molecules

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Molar Mass and Density of a Gas:
The molar volumes of all gases are the same when
measured at the same temperature and pressure.
However, the molar masses of different gases will vary.
This means that different gases will have different densities
(different masses per unit volume).
If we know the molecular weight of a gas, we can calculate
its density and vice versa.
Though not a great exponent of dimensional analysis
(the Unit Factor Method), this is an example where starting by looking at units can help to link
various quantities quickly and easily without having to memorise a lot of new formulae.

Remember, though we often say the molar mass of CH4 is 16.04 g, it is really 16.04 g mol-1

For example 1: Uranium hexafluoride UF6 gas is used in the isotopic enrichment of natural
uranium. Calculate its density at STP.
Density = mass/volume so looking for something like g L-1
Knowing formula allows us to calculate molecular weight (352.02 amu) but
need g so better using molar mass = 352.02 g mol-1
STP so we also know molar volume = 22.4 L mol-1

From the units we can see:

* If non standard (more realistic) g mol-1 g molar mass
Temperature and Pressure is used
Density = = =

then P V /T = P V /T can be L mol-1 L molar volume
1 1 1 2 2 2
used to calculate an alternative
=
molar volume 352.02 / 22.4* = 15.72 g L-1

For example 2: Calculate the approximate molar mass of a gas whose measured density is
3.33 g/L at 30°C and 780 torr.
Ap Formula Sheet provides for conversion: 760 torr = 1 atm so 780 torr = 1.03 atm

Start by recalculating a value for P1V1 /T1 = P2V2 /T2 so V2 = P1V1T2 / T1P2
molar volume under these conditions.
V2 = 1.00 x 22.4 x 303.15 / 273.15 x 1.03 = 24.14 L mol-1

molar mass ( g mol-1 ) = Density ( g L-1 ) x molar volume ( L mol-1 ) = 3.33 x 24.14 = 80.37 * g mol-1
* Often this number can also be used to identify the identity of the gas - SO3 perhaps.
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3.4 Practice Problems - Part 4
7. Given that the density of Hg(l) at 0°C is about 14 g mL-­1, which of the following is closest to
the volume of one mole of Hg(l) at this temperature?

A 0.070 mL B 0.14 mL C 1.4 mL O

D 14 mL E 28 mL

8. A sample of an unknown gas from a cylinder

is collected over water in the apparatus
shown opposite.
After all the gas sample has been collected,
the water levels inside and outside the gas
collection tube are made the same.
Measurements that must be made to calculate
the molar mass of the gas include all of the
following except

A atmospheric pressure.
B temperature of the water
C volume of gas in the gas-collection tube
D initial and final mass of the gas cylinder

O
E mass of the water in the apparatus

The following two questions refer to the 1 L flasks shown below.

9. Which flask contains the sample with the greatest density?

A flask A B flask B O
C flask C D flask D E flask E

10. Which flask contains the smallest number of moles of gas?

A flask A
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B flask B C flask C
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D flask D E flask E
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3.4 Quick Check - AP FRQ Questions 2
3. A student was assigned the task of determining the molar mass of an unknown gas.
The student measured the mass of a sealed 843 mL rigid flask that contained dry air. The
student then flushed the flask with the unknown gas, resealed it, and measured the
mass again.
Both the air and the unknown gas were at 23.0°C and 750. torr. The data for the
experiment are shown in the table below.

a) Calculate the mass, in grams, of the dry air that was in the sealed flask.
(The density of dry air is 1.18 g L−1 at 23.0°C and 750. torr.)
1 point is earned for the correct setup and calculation of mass.


m = D x V = (1.18 g L−1)(0.843 L) = 0.995 g
b) Calculate the mass, in grams, of the sealed flask itself (i.e., if it had no air in it).
1 point is earned for subtracting the answer in part a) from 157.70 g.


157.70 g − 0.995 g = 156.71 g
c) Calculate the mass, in grams, of the unknown gas that was added to the sealed flask.
1 point is earned for subtracting the answer in part b) from 158.08 g.


158.08 g − 156.71 g = 1.37 g
d) Using the information above, calculate the value of the molar mass of the unknown
gas.

point is earned for the conversion of pressure (if necessary) and temperature and
1
the use of the appropriate R.
1 point is earned for the correct setup and calculation of moles of gas.
n = PV / RT

= (750/760 atm)(0.843 L) / (0.0821 [Link]-1.K-1)(296 K)
= 0.0342 mol
1 point is earned for the correct setup and calculation of molar mass.

OR - see next page

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Q3. d) continued

If calculation is done in a single step,
point is earned for the correct P and T,
1
1 point is earned for the correct density, and

1 point is earned for the correct answer.


molar mass = 1.37 g / 0.0342 mol = 40.1 g mol-1

OR

molar mass = DRT / P
= (1.37g / 0.843L).(0.0821 [Link]-1.K-1)(296K) / (750/760 atm)

= 40.0 g mol-1

Note: Significant figures were checked in this problem: parts a) and d) were scored

with ±1 significant figure needed, and parts b) and c) were scored with the

. correct number of significant figures needed for the subtraction.
e) After the experiment was completed, the instructor informed the student that the

unknown gas was carbon dioxide (44.0 g mol−1) .
Calculate the percent error in the value of the molar mass calculated in part d).

1 point is earned for the correct setup and answer.

percent error = ( |44.0 g mol-1 - 40.1 g mol-1| / 44.0 g mol-1 ) x 100 = 8.9 %

f) For each of the following two possible occurrences, indicate whether it by itself

could have been responsible for the error in the student’s experimental result.

You need not include any calculations with your answer. For each of the possible
occurrences, justify your answer.

Occurrence 1:
The flask was incompletely flushed with CO2(g) , resulting in
some dry air remaining in the flask.

1 point is earned for the correct reasoning and conclusion.

This occurrence could have been responsible.
The dry air left in the flask is less dense (or has a lower molar mass) than CO2

gas at the given T and P. This would result in a lower mass of gas in the flask
and a lower result for the molar mass of the unknown gas.

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Q3 contd
Occurrence 2: The temperature of the air was 23.0°C, but the temperature of the
CO
2(g)
was lower than the reported 23.0°C.
1 point is earned for the correct reasoning and conclusion.


This occurrence could not have been responsible.
The density of CO2 is greater at the lower temperature. A larger mass of CO2



would be in the flask than if the CO2 had been at 23.0°C, resulting in a higher

calculated molar mass for the unknown gas.
g) Describe
the steps of a laboratory method that the student could use to verify that
the volume of the rigid flask is 843 mL at 23.0°C. You need not include any
calculations with your answer.
1 point is earned for a valid method.


Valid methods include the following:
1.
Find the mass of the empty flask. Fill the flask 1. with a liquid of known

density (e.g., water at 23°C),and measure the mass of the liquid-filled

flask. Subtract to find the mass of the liquid. Using the known density

and mass, calculate the volume.
2.
Measure 843 mL of a liquid (e.g., water) in a 1,000 mL graduated

cylinder and transfer the liquid quantitatively into the flask to see if the

water fills the flask completely.

4. After elemental analysis the empirical formula of a compound was determined to be

CH2Br . It was also found to have a vapor density of 6.00 g L−1 at 375 K and 0.983 atm.
Using these data, determine the following.
a) The molar mass of the compound
1 point is earned for applying the gas law (PV = nRT) to calculate n.



n = PV / RT = (0.983 atm)(1.00 L) / (0.0821 [Link]-1.K-1)(375 K)
= 0.0319 mol
1 point is earned for calculating the molar mass, = 6.00 g / 0.0139 mol = 188 g mol-1

b) The molecular formula of the compound
point is earned for the molecular formula that is consistent with the molar mass
1
calculated in part a).
Each CH2Br unit has mass of 12.011 + 2(1.0079) + 79.90 = 93.9 g,
and 188 / 93.9 ≃ 2.00, so there must be two CH2Br units per molecule.
Therefore, the molecular formula of the compound is C2H4Br2 .

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Gas Mixtures - Partial Pressures:
The ideal-gas equation applies to
mixtures just as to pure gases.
It was in fact with a gas mixture,
ordinary air, that Boyle, Gay-Lussac
and Charles did their early experiments.
The only new concept we need in order to deal with gas mixtures is the partial pressure, a
concept invented by the famous English chemist John Dalton (1766-1844).
Dalton reasoned that the low density and high compressibility of gases indicates that they consist
mostly of empty space; from this it follows that when two or more different gases occupy the same
volume, they behave entirely independently.
The contribution that each component of a gaseous mixture makes to the total pressure of the
gas is known as the partial pressure of that gas. Dalton himself stated this law in the simple way
shown:

Ptotal = P1 + P2 + P3 + ...... Dalton's Law of Partial Pressures

Remember, PV = nRT so P = nRT/V

However, a mixture of gases are all at the same temperature and are occupying the same container
(so same volume) so the individual Pressures depend only on the number of moles of each gas.

so P1 ∝ n1 and P2 ∝ n2 and P3 ∝ n3 etc

In other words, partial pressures will be detrmined by the mole ratios of the gases present in the
mixture. This is usually expressed as:
P1 = Ptotal x n1 / ntotal

or P1 = Ptotal x X1 X1 = mole fraction = n1 / ntotal

Again, there do not seem to be too many question requiring detailed calculation of Partial
Pressure - most questions simply require you to apply the idea of mole fractions.

However, the equations are in the AP Formula Sheet, so detailed calculations should not cause
too many difficulties.

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3.4 Practice Problems - Part 5
11. A gas mixture at 0°C and 1.0 atm contains 0.010 mol of H2, 0.015 mol of O2, and 0.025 mol
of N2. Assuming ideal behavior, what is the partial pressure of hydrogen gas (H2)
in the mixture?

A About 0.010 atm, because there is 0.010mol of H2 in the sample.

B About 0.050 atm, because there is 0.050mol of gases at 0°C and 1.0 atm.

O
C About 0.20 atm, because H2 comprises 20% of the total number of moles of gas.
D About 0.40 atm, because the mole ratio of H2 : O2 : N2 is 0.4 : 0.6 : 1.

12.

Diagram 1 above shows equimolar samples of two gases inside a container fitted with a
removable barrier placed so that each gas occupies the same volume.
The barrier is carefully removed as the temperature is held constant. Diagram 2 above
shows the gases soon after the barrier is removed. Which statement describes the
changes to the initial pressure of each gas and the final partial pressure of each gas in the
mixture and also indicates the final total pressure?

A The partial pressure of each gas in the mixture is double its initial pressure;
the final total pressure is half the sum of the initial pressures of the two gases.
B The partial pressure of each gas in the mixture is double its initial pressure;
the final total pressure is twice the sum of the initial pressures of the two gases.

O
C The partial pressure of each gas in the mixture is half its initial pressure;
the final total pressure is half the sum of the initial pressures of the two gases.
D The partial pressure of each gas in the mixture is half its initial pressure;
the final total pressure is the same as the sum of the initial pressures of the two gases.

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13. An equimolar mixture of N2(g) and Ar(g) is kept inside a rigid container at a constant
temperature of 300 K. The initial partial pressure of Ar in the mixture is 0.75atm.
An additional amount of Ar was added to the container, enough to double the number of
moles of Ar gas in the mixture. Assuming ideal behavior, what is the final pressure
of the gas mixture after the addition of the Ar gas?

A 0.75 atm, because increasing the partial pressure of Ar decreases the partial pressure
of N2.
B 1.13 atm, because 33% of the moles of gas are N2.
C 1.50 atm, because the number of moles of N2 did not change.

O
D 2.25 atm, because doubling the number of moles of Ar doubles its partial pressure.

14. A 2 L sample of N2(g) and a 1 L sample of Ar(g), each originally at 1 atm and 0°C, are
combined in a 1 L tank. If the temperature is held constant, what is the total pressure of the
gases in the tank?

A 1 atm B 2 atm O
C 3 atm D 4 atm E 5 atm

15. A flask contains 0.25 mole of SO2(g), 0.50 mole of CH4(g), and 0.50 mole of O2(g). The total
pressure of the gases in the flask is 800 mm Hg. What is the partial pressure of the SO2(g) in
the flask? (All pressures are mm Hg)

A 800 B 600 C 250 D 200 O

E 160

16. A sealed vessel contains 0.200 mol of oxygen gas, 0.100 mol of nitrogen gas, and 0.200 mol
of argon gas. The total pressure of the gas mixture is 5.00 atm. The partial pressure of the
argon is

A 0.200 atm B 0.500 atm C 1.000 atm O

D 2.000 atm E 5.000 atm

17. Equal masses of He and Ne are placed in a sealed container. What is the partial pressure of
He if the total pressure in the container is 6 atm?

A 1 atm B 2 atm C 3 atm D 4 atm O

E 5 atm

18. When 4.0 L of He(g), 6.0 L of N2(g), and 10. L of Ar(g), all at 0°C and 1.0 atm, are pumped into
an evacuated 8.0 L rigid container, the final pressure in the container at 0°C is

A 0.5 atm B 1.0 atm O

C 2.5 atm D 4.0 atm

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19. When 6.0 L of He(g) and 10. L of N2(g), both at 0°C and 1.0 atm, are pumped into an
evacuated 4.0 L rigid container, the final pressure in the container at 0°C is

A 2.0 atm O
B 4.0 atm C 6.4 atm D 8.8 atm D 16 atm

20. Equal masses of three different ideal gases, X, Y, and Z, are mixed in a sealed rigid
container. If the tem­perature of the system remains constant, which of the following
statements about the par­tial pres­sure of gas X is correct?
A It is equal to ⅓ the total pressure
B It depends on the intermolecular forces of at­trac­tion between molecules of X, Y,
and Z.

O
C It depends on the relative molecular masses of X, Y, and Z.
D It depends on the average distance traveled be­tween molecular collisions.
E It can be calculated with knowledge only of the volume of the container.

3.4 Quick Check - AP FRQ Questions 2

5. C(s) + CO2(g) ⇌ 2 CO(g)

Solid carbon and carbon dioxide gas at 1,160 K were

placed in a rigid 2.00 L container, and the reaction
represented above occurred.
As the reaction proceeded, the total pressure in the
container was monitored. When equilibrium was
reached, there was still some C(s) remaining in the
container. Results are recorded in the table opposite.
a) Calculate the number of moles of CO2(g) initially placed in the container.
(Assume that the volume of the solid carbon is negligible.)
1 point is earned for correct setup.
1 point is earned for the correct answer.

n = PV / RT

= (5.00 atm)(2.00 L) / (0.0821 [Link]-1.K-1)(1,160 K)

= 0.105 mol
b) For the reaction mixture at equilibrium at 1,160 K, the partial pressure of the
CO
2(g)
is 1.63 atm. Calculate the partial pressure of CO(g)

1 point is earned for correct answer supported by correct method.

PCO2 + PCO = Ptotal PCO = Ptotal - PCO2 = 8.37 -1.63 = 6.74 atm

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3.5 Kinetic Molecular Model

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Kinetic Molecular Model
The ideal-gas equation describes how gases behave but not
why they behave as they do.
Why does a gas expand when heated at constant pressure?
Or why does its pressure increase when the gas is compressed
at constant temperature?
To understand the physical properties of gases, we need a model
that helps us picture what happens to gas particles when conditions
such as pressure or temperature change.
Such a model, known as the kinetic-molecular theory of gases,
was developed over a period of about 100 years, culminating in
1857 when Rudolf Clausius (1822–1888) published a complete
and satisfactory form of the theory.

The kinetic-molecular theory (the theory of moving molecules) is summarized by the following
statements:
① Gases consist of large numbers of molecules (atoms for Noble Gases) that are
in continuous, random motion.
② The combined volume of all the molecules of the gas is negligible relative to the
total volume in which the gas is contained.
③ Attractive and repulsive forces between gas molecules are negligible.
④ Energy can be transferred between molecules during collisions but, as long as
temperature remains constant, the average kinetic energy of the molecules does not
change with time.
⑤ The average kinetic energy of the molecules is proportional to the absolute
temperature.
At any given temperature the molecules
of all gases have the same average
kinetic energy.

KE = ½mv2

However, since molecules of different

gases will have different masses
At same temperature the molecules
of different gases have different speeds.
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The dependence of molecular speed on mass has two consequences.

The first is effusion, which is the escape of gas molecules through a tiny hole (b). The second is
diffusion, (a) , which is the spread of one substance throughout a space or throughout a second
substance. For example, the molecules of a perfume diffuse throughout a room.
Rate of effusion and diffusion increases as the mass decreases

HCl NH3
36.5 amu 17 amu

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3.5 Quick Check - AP FRQ Questions
1.
A student is doing experiments with CO2(g). Originally, a sample of the gas is in a rigid
container at 299K and 0.70atm. The student increases the temperature of the CO2(g) in the

container to 425K. .
a) Describe the effect of raising the temperature on the motion of the CO2(g)

molecules.

The response indicates that the average speed of the molecules increases as
temperature increases

b) Calculate the pressure of the CO2(g) in the container at 425K.

The response shows a calculation similar to the following.

P
1
/ T1 = P2 / T2 0.70 atm / 425 K = P2 / 425 K P2 = 0.99 atm

c) In terms of kinetic molecular theory, briefly explain why the pressure of the CO2(g)
 
  in the container changes as it is heated to 425K
The response meets one or both of the following criteria.

The response indicates that faster-moving gas particles collide more


frequently with the walls of the container, thus increasing the pressure.
The response indicates that faster-moving gas particles collide more forcefully


with the walls of the container, thus increasing the pressure.

* d) The student measures the actual pressure of the CO2(g) in the container at 425K
and observes that it is less than the pressure predicted by the ideal gas law.
Explain this observation.

The response indicates that the attractive forces between CO2 molecules result in a


pressure that is lower than that predicted by the ideal gas law.

* This question might be best left until after next section on deviations fron Ideal Gas.

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3.5 Practice Problems
1. A 0.5 mol sample of He(g) and a 0.5 mol sample of Ne(g) are placed separately in two
10.0 L rigid containers at 25°C. Each container has a pinhole opening. Which of the gases,
He(g) or Ne(g), will escape faster through the pinhole and why?

O
A He(g) will escape faster because the He(g) atoms are moving at a higher average speed
than the Ne(g) atoms.
B Ne(g) will escape faster because its initial pressure in the container is higher.
C Ne(g) will escape faster because the Ne(g) atoms have a higher average kinetic energy
than the He(g) atoms.
D Both gases will escape at the same rate because the atoms of both gases have the
same average kinetic energy.

2. A rigid metal tank contains oxygen gas. Which of the following applies to the gas in the
tank when additional oxygen is added at constant temperature?

A The volume of the gas increases.

B The pressure of the gas decreases.

O
C The average speed of the gas molecules remains the same.
D The total number of gas molecules remains the same.
E The average distance between the gas molecules increases.

3. A sample of an ideal gas is cooled from 50.0°C to 25.0°C in a sealed container of constant
volume. Which of the following values for the gas will decrease?
I. The average molecular mass of the gas
II. The average distance between the molecules
III. The average speed of the molecules

A I only
B II only

O
C III only
D I and III
E II and III
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4. At standard temperature and pressure, a 0.50 mol sample of H2 gas and a separate 1.0 mol
sample of O2 gas have the same

O
A average molecular kinetic energy
B average molecular speed
C volume
D effusion rate
E density

5. The diagram below shows the distribution of speeds for a sample of N2(g) at 25°C.

Which of the following graphs shows the distribution of speeds for a sample of O2(g)
at 25°C (dashed line) ?

O
A B

C D

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6. Equal numbers of moles of He(g), Ar(g), and Ne(g) are placed in a glass vessel at room
temperature. If the vessel has a pinhole-sized leak, which of the following will be true
regarding the relative values of the partial pressures of the gases remaining in the vessel
after some of the gas mixture has effused?

O
A PHe < PNe < PAr
B PHe < PAr < PNe
C PNe < PAr < PHe
D PAr < PHe < PNe
E PHe = PAr = PNe

7. The following question refers to the 1 L flasks shown below.

In which flask do the molecules have the greatest average speed?

A A O
B B C C D D E E

8. A 1L sample of helium gas at 25°C and 1atm is combined with a 1L sample of neon gas at
25°C and 1atm. The temperature is kept constant. Which of the following statements
about combining the gases is correct?

A The average speed of the helium atoms increases when the gases are combined.
B The average speed of the neon atoms increases when the gases are combined.
C The average kinetic energy of the helium atoms increases when the gases are
combined.

O
D The average kinetic energy of the helium atoms and neon atoms do not change
when the gases are combined.

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9.

The graph above shows the distribution of molecular speeds for four different gases at the
same temperature. What property of the different gases can be correctly ranked
using information from the graph, and why?

A The densities of the gases, because as the density of a gas increases,

the average speed of its molecules decreases.
B The pressures of the gases, because the pressure exerted by a gas depends on the
average speed with which its molecules are moving
C The volumes of the gases, because at a fixed temperature the volume of a gas can be
calculated using the equation PV=nRT .

O
D The molecular masses of the gases, because the gas molecules have the same average
kinetic energy and mass can be calculated using the equation KEavg=½mv2 .

10.

The average kinetic energy of the gas molecules is?

A greatest in A B greatest in B

C greatest in C D the same in all three containers O

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11.

The experimental apparatus represented above is used to demonstrate the rates at which
gases diffuse. When the cotton balls are placed in the ends of a tube at the same time,
the gases diffuse from each end and meet somewhere in between, where they react to
form a white solid. Which of the following combinations will produce a solid closest to
the center of the tube?

O
A HCl and CH3NH2
B HCl and NH3
C HBr and CH3NH2
D HBr and NH3

12.

The volume of a sample of air in a cylinder with a movable piston is 2.0 L at a pressure P1,
as shown in the diagram above. The volume is increased to 5.0 L as the temperature is
held constant. The pressure of the air in the cylinder is now P2. What effect do the volume
and pressure changes have on the average kinetic energy of the molecules in the sample?
A The average kinetic energy increases.
B The average kinetic energy decreases.

O
C The average kinetic energy stays the same.
D It cannot be determined how the kinetic energy is affected without knowing P1
and P2.
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13.

The distribution of speeds of H2(g) molecules at 273 K and 1 atm is shown in the diagram
above. Which of the following best shows the speed distribution of He(g) atoms under the
same conditions of temperature and pressure?

A B

C D

14. The table below contains information about samples of four different gases at 273 K. The
samples are in four identical rigid containers numbered 1 through 4.

Under the conditions given, consider containers 1, 2, and 4 only. The average speed of the
gas particles is

O
A greatest in container 1 B greatest in container 2
C greatest in container 4 D the same in containers 1, 2, and 4
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15. Two flexible containers for gases are at the same tem­perature and pressure. One holds 0.50
gram of hy­drogen and the other holds 8.0 grams of oxy­gen. Which of the following
statements re­garding these gas samples is FALSE?

O
A The volume of the hydrogen container is the same as the volume of the oxygen
container.
B The number of molecules in the hydrogen con­tainer is the same as the number of
molecules in the oxygen container.
C The density of the hydrogen sample is less than that of the oxygen sample.
D The average kinetic energy of the hydrogen molecules is the same as the average
kinetic en­ergy of the oxygen molecules.
E The average speed of the hydrogen molecules is the same as the average speed of the
oxygen molecules.

16. At 27°C, a rigid 2.0 L vessel is filled with N2(g) and sealed. The initial pressure of N2(g) is
720 mm Hg. The vessels is heated to 127°C and allowed to reach a constant pressure.

The gas particles in the vessel at 27°C are represented in the diagram above. The lengths of
the arrows represent the speeds of the particles. Which of the following diagrams best
represents the particles when the vessel is heated to 127°C?

O
A B

C D

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17.

The graph above shows the speed distribution of molecules in a sample of a gas at a certain
temperature. Which of the following graphs shows the speed distribution of the same
molecules at a lower temperature (as a dashed curve) ?

A B

C D

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3.6 Deviation from Ideal Gas Law

Deviations From Ideal Gas Law

The basic assumptions of the kinetic-molecular theory
of gases give us insight into why real gases deviate
from ideal behavior.
The molecules of an ideal gas are assumed to occupy
no space and have no attraction for one another.
Real molecules, however, do have finite volumes and
do attract one another.
One effect of these attractions is that molecules will be slowed down as the pass close to other
molecules and attract each other. As a result, collisions with the container wall will be less
energetic and pressure will be reduced.

① The stronger the intermolecular forces, the greater the deviation from Ideal Gas Law -
pressure will be less than predicted.

Differences in masses of molecules are normally only significant when comparing molecules
where the intermolecular forces are London Dispersion Forces.
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'Measuring' Deviations From Ideal Gas Law
We know that for an Ideal Gas,

PV = nRT so n = PV / RT
If we have 1 mole of a gas, e.g. N2 , then PV/RT
should equal exactly 1 for all combinations of
Temperature and Pressure.
Deviations from this value can be used to illustrate
deviations from the Ideal Gas Law.

Effect of Temperature
Temperature determines how effective attractive forces between gas molecules are in causing
deviations from ideal behavior at lower pressures.
The graph above and (selection) opposite shows that, at
pressures below about 400 atm, cooling increases the extent
to which a gas deviates from ideal behavior. 1000 K

As the gas cools, the average kinetic energy of the molecules

decreases. 500 K

This drop in kinetic energy means the molecules do not have 200 K
the energy needed to overcome intermolecular attraction,
and the molecules will be more likely to stick to each
other than bounce off each other.

② The lower the temperature, the greater the deviation from Ideal Gas Law -
pressure will be less than predicted.

Effect of Pressure
At low pressures, (< 10 atm) the
deviation from ideal behavior is
small, and we can use the
ideal-gas equation without
generating serious error.

At high pressures (> 10 atm) the deviation from ideal

behavior is large but different for each gas.

③ Real gases do not behave ideally at high pressure.

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3.6 Practice Problems

1. Which of the following behaves most like an ideal gas at the conditions indicated?

O
A H2(g) molecules at 10-3 atm and 200°C
B O2(g) molecules at 20 atm and 200°C
C SO2(g) molecules at 20 atm and 200°C
D NH3(g) molecules at 20 atm and 200°C
E NH3(g) molecules at 20 atm and 300°C

2. Ar(g) deviates more from ideal behavior at extremely high pressures than Ne(g) does.
Which of the following is one reason for this difference?

O
A The particle volume of Ar is greater than that of Ne
B Ar atoms have more valence electrons than Ne atoms have,
so Ar atoms have greater interparticle forces.
C The intermolecular forces between Ne atoms are greater than
those between Ar atoms.
D Ar atoms are more attracted to the walls of the container than Ne atoms are.
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3. Which of the following gases deviates most from ideal behavior?

O
A SO B2
Ne C CH4 D N2 E H2

4. When the actual gas volume is greater than the volume predicted by the ideal gas law, the
explanation lies in the fact that the ideal gas law does NOT include a factor for molecular

O
A volume
B mass
C velocity
D attractions
E shape

5. A vessel contains Ar(g) at a high pressure. Which of the following statements best helps to
explain why the measured pressure is significantly greater than the pressure calculated
using the ideal gas law?

A The molar mass of Ar is relatively large.

B A significant number of Ar2 molecules form.
C The attractive forces among Ar atoms cause them to collide with the walls of the
container with less force.

O
D The combined volume of the Ar atoms is too large to be negligible compared with
the total volume of the container.

6. At constant temperature, the behavior of a sample of a real gas more closely approximates
that of an ideal gas as its volume is increased because the

A collisions with the walls of the container become less frequent

B average molecular speed decreases
C molecules have expanded

O
D average distance between molecules becomes greater.
E average molecular kinetic energy decreases.

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7. The diagrams opposite represent two samples of Xe
gas in containers of equal volume at 280K.
Which of the following correctly compares the two
samples in terms of their deviation from ideal gas
behavior and explains why?

A The gas in sample 1 would deviate more from ideal behavior because the average
distance an Xe atom travels before colliding with another Xe atom is greater.

O
B The gas in sample 2 would deviate more from ideal behavior because the Xe atoms
are closer together, leading to an increase in intermolecular attractions.
C The gas in sample 2 would deviate more from ideal behavior because the average
speed of the Xe atoms is less, leading to an increase in intermolecular attractions.
D The gases in both sample 1 and sample 2 would show the same deviation from ideal
behavior.

8. Which of the following best helps explain why the pressure of a sample of CH4(g) (molar
mass 16g/mol) is closer to the pressure predicted by the ideal gas law than a
sample of NH3(g) (molar mass 17g/mol) ?

O
A NH3 molecules are polar while CH4 molecules are not, and the greater attractions
between NH3 molecules cause the molecules to collide with the walls of the
container with less force.
B NH3 molecules have a greater molar mass than CH4 molecules, so the NH3
molecules collide with the walls of the container with more force.
C CH4 molecules have more hydrogen atoms than NH3 molecules, so CH4 molecules
have more hydrogen bonding and greater intermolecular forces.
D CH4 molecules are larger than NH3 molecules, so the actual CH4 molecules take
up a significant portion of the volume of the gas.

9. Under which of the following conditions of temperature and pressure would 1.0 mol of the
real gas CO2(g) behave most like an ideal gas?

Temperature (K) Pressure (atm)

A 100 0.1
B 100 100

O
C 800 0.1
D 800 100
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10. The table below contains information about samples of four different gases at 273 K. The
samples are in four identical rigid containers numbered 1 through 4.

The best explanation for the lower pressure in container 4 is that SO2 molecules
A have a larger average speed than the other three gases
B occupy a larger portion of the container volume than the other three gases

O
C have stronger intermolecular attractions than the other three gases
D contain π bonds, while the other gases contain only σ bonds

11. The ideal gas law best describes the properties of which of the following gases at 0°C and
1 atm?

A PH3 B HBr C SO2 D N2 O

12. Under which of the following conditions of temperature and pressure will H2 gas be
expected to behave most like an ideal gas?

A 50 K and 0.10 atm B 50 K and 5.0 atm

O
C 500 K and 0.10 atm
D 500 K and 50 atm

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3.6 Quick Check - AP FRQ Questions
1. At 400K CH4(g) and CCl4(g)are gases. At this temperature, which compound, CH4(g) or
CCl4(g), behaves more like an ideal gas? Justify your answer, including reasoning about both
molecules. .
The response meets both of the criteria below:
The response indicates that both compounds have London dispersion forces.


(If the response indicates that either of the compounds has any other type of

intermolecular force, the criterion is not met.)
The response indicates that CCl4has the higher boiling point and that it has greater

intermolecular forces.

2.
* d) The student measures the actual pressure of the CO2(g) in the container at 425K
and observes that it is less than the pressure predicted by the ideal gas law.

Explain this observation.

The response indicates that the attractive forces between CO2 molecules result in a


pressure that is lower than that predicted by the ideal gas law.

*
. Last part of question asked in previous section.

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3.7 Solutions & Mixtures

Solutions & Mixtures

Pure substances are either elements or compounds. You can write
a chemical formula for a pure substance.
A mixture contains two or more components mixed in a variety
of proportions.
The components can be separated by physical means. There are
many types of mixtures but we will concentrate on solutions.
We consider something to be a solution when we have a
homogeneous mixture of two or more substances.
homogeneous mixture - any sample of the
solution should be identical
two or more substances - definition does not
specify solid, liquid or gas.
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Interactions
Whichever component has the larger quantity would be considered the solvent and the other
component would be the solute.
The intermolecular attractions that hold molecules together in liquids and solids also play a
central role in the formation of solutions.

When one substance (the solute) dissolves in another (the solvent), particles of the solute disperse
throughout the solvent.
The solute particles occupy positions that are normally taken by solvent [Link] ease with
which a solute particle replaces a solvent molecule depends on the relative strengths of three
types of interactions:
solute–solute interactions between solute particles must be overcome in order to
disperse the solute particles through the solvent.
solvent–solvent interactions between solvent particles must be overcome to make
room for the solute particles in the solvent.
solvent–solute interactions between solvent and solute particles occur as the particles
mix. to be continued ......
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Standard Solutions
A standard solution is one whose concentration is known very accurately.
Normally this requires an accurate mass
(2 or 3 dp minimum) of a pure and stable solid
(AR - Analytical Reagent grade) being carefully
dissolved in a volumetric flask.

Primary standard

'Weighing by difference' - removing the

required mass from a weighing bottle
containing excess chemical - will result Distilled water

in a smaller % error.
Distilled water

Concentration
(molarity, M)
can then be
calculated:

M = n /L
mol l-1

This primary standard can then be reacted with other solutions (typically by titration) to
calculate their concentrations accurately. These solutions would be accurate enough to be
considered as secondary standards.
Most acids and bases cannot be directly prepared from pure solids - most absorb water or react
with gases in the air - so would be standardised by reacting with a primary standard.
potassium hydrogen pthalate and oxalic acid can be used to standardise bases
anhydrous sodium carbonate can be used to standardise acids
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Dilution
A standard solution can also be
considered as a stock solution and
used to make other accurate solutions
by dilution.

Since,
nstock solution removed by pipette
=
nnew solution made in flask

Mstock x Lstock = Mnew x Lnew

For example, if 25 ml of a 0.25 M solution is pipetted into a 500 ml volumetric flask, what would be
the concentration of the new solution?
Mstock x Lstock = Mnew x Lnew

Mnew = (Mstock x Lstock ) / Lnew
(notice that since volumes can be used
in any unit as long as they are the same) Mnew = (0.25 x 25 ) / 500 = 0.0125 mol l-1
For techniques such as a spectrophotometric analysis, several solutions of known concentration
can be prepared using 20, 10 and 5 ml pipettes. These solutions can then be used to produce a
calibration curve plotting absorbance versus concentration. As a result, these solutions can be
referred to as calibration solutions.

Though less accurate, another method is to

do serial dilutions, where each new solution
is used to make the next one.
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3.7 Quick Check - AP FRQ Questions
1.
A student has 100. mL of 0.400 M CuSO4(aq) and is asked to make 100. mL of 0.150 M
CuSO4(aq) for a spectrophotometry experiment.

The following laboratory equipment is available for preparing the solution: centigram
balance, weighing paper, funnel, 10 mL beaker, 150 mL beaker, 50 mL graduated cylinder,
100 mL volumetric flask, 50 mL buret, and distilled water.

a) Calculate the volume of 0.400 M CuSO4(aq) required for the preparation.
1 point is earned for the correct volume.

M1V1 = M2V2 V2 = (0.150M)(0.100L) / 0.400M

V2 = 0.0375 L x (1000 mL/1L) = 37.5 mL

b) Briefly describe the essential steps to most accurately prepare the 0.150 M

CuSO 4(aq)
from the 0.400 M CuSO4(aq) using the equipment listed above.
1 point is earned for using the buret to measure 37.5 mL of 0.400 M CuSO4 solution.

1 point is earned for adding the CuSO4 solution to the volumetric flask and filling to


the mark with distilled water.

The student plans to conduct a

spectrophotometric analysis to
determine the concentration of
Cu2+(aq) in a solution.
The solution has a small amount
of Co(NO3)2(aq) present as a
contaminant. The student is given
the diagram opposite, which shows
the absorbance curves for aqueous
solutions of Co2+(aq) and Cu2+(aq).

c) The spectrophotometer available to the student has a wavelength range of 400 nm

to 700 nm.
What wavelength should the student use to minimize the interference from the

presence of the Co2+(aq) ions?

1 point is earned for a correct wavelength.
700 nm
(Any wavelength from 650 to 700 nm is acceptable.)
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2. A student is given a sample of CuSO4(s)
that contains a solid impurity that is
soluble and colorless.
The student wants to determine the

amount of CuSO4 in the sample and
decides to use a spectrophotometer.
First, the student prepares a calibration
graphby measuring the absorbances of
CuSO4(aq) solutions of known
concentrations. The graph is shown.

a) The student dissolves the entire impure sample of CuSO4(s) in enough distilled water

to make [Link] of solution. Then the student measures the absorbance of the
solution and observes that it is 0.30.

Determine the concentration of CuSO4(aq) in the solution.

The response indicates that the absorbance is 0.15 M.


(Unit not required. Any value from 0.14 M to 0.16 M is acceptable.)

b) Calculate the number of moles of CuSO4 that were in the impure sample of CuSO4(s)

The response gives the following calculation (or an equivalent): Unit not required.

0.15 mol / 1000 mL x 100. ml = 0.015 mol

c) In addition to the number of moles of CuSO4 calculated in part b), what other
quantity must be measured in order to calculate the mass percentage of CuSO4

in the impure sample of CuSO4(s) ?

The response indicates that the mass of the sample must be measured.

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3.
(s) + 2 H+(aq) → Mg2+(aq) + H2(g)
Mg
A student performs an experiment to determine the volume of hydrogen gas produced

when a given mass of magnesium reacts with excess HCl(aq) , as represented by the net
ionic equation above.
The student begins with a 0.0360 g sample of pure magnesium and a solution of
2.0 M HCl(aq).
a) Calculate the number of moles of magnesium in the 0.0360 g sample.
1 point is earned for the correct number of moles of Mg.


1 mol Mg / 24.30 g Mg x 0.0360 g = 0.00148 mol Mg
b) Calculate the number of moles of HCl(aq) needed to react completely with the sample
of
magnesium.
1 point is earned for the correct number of moles of HCl.


0.00148 mol Mg x 2 mol H+ / 1 mol Mg = 0.00296 mol HCl
As the magnesium reacts, the hydrogen gas produced is collected by water displacement at
23.0°C. The pressure of the gas in the collection tube is measured to be 749 torr.
c) Given that the equilibrium vapor pressure of water is 21 torr at 23.0°C, calculate the

pressure that the H2(g) produced in the reaction would have if it were dry.
1 point is earned for the correct pressure.


P = 749 torr − 21 torr = 728 torr
d) Calculate the volume, in liters measured at the conditions in the laboratory, that the
H
2(g) produced in the reaction would have if it were dry.
PV = nRT
V = nRT/ P
P = 728 torr x 1 atm / 760 torr = 0.958 atm
V = (0.00148 mol H2) (0.0821 L atm mol-1 K-1)(296 K) / 0.958 atm = 0.0375 L
1 point is earned for the correct moles of H2(g).
1 point is earned for agreement of units of P (from part c)) and R.
1 point is earned for the correct temperature substitution and calculated volume.

Note: For errors in significant figures or mathematics, there is a 1 point deduction;

For the entire question, only 1 point total can be deducted for each type of error.

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3.7 Practice Problems
1. A 0.20 mol sample of MgCl2(s)and a 0.10 mol sample of KCl(s)are dissolved in water and
diluted to 500 mL. What is the concentration of Cl- in the solution?
A 0.15 M B 0.30 M C 0.50 M D 0.60 M O
E 1.00 M

2. A 360 mg sample of aspirin, C9H8O4, (molar mass 180 g), is dissolved in enough water to
produce 200 mL of solution. What is the molarity of aspirin in a 50 mL sample
of this solution?
A 0.080 M B 0.040 M C 0.020 M O
D 0.010 M E 0.0025 M

3. A 40.0 mL sample of 0.25 M KOH is added to 60.0 mL of 0.15 M Ba(OH)2. What is the
molar concentration of OH-(aq) in the resulting solution? (Assume that the volumes are
additive.)
A 0.10 M B 0.19 M O
C 0.28 M D 0.40 M E 0.55 M

4. A student prepares a solution by dissolving 60.00 g of glucose (molar mass 180.2 g mol-1)
in enough distilled water to make 250.0 mL of solution. The molarity of the solution
should be reported as
A 12.01 M B 12.0 M O
C 1.332 M D 1.33 M E 1.3 M

5. A student wishes to prepare 2.00 liters of 0.100 mo­lar KIO3 (molecular weight 214).
The proper proce­dure is to weigh out
A 42.8 grams of KIO3 and add 2.00 kilograms of H2O

O

B 42.8 grams of KIO3 and add H2O until the fi­nal homogeneous solution has a
volume of 2.00 liters
C 21.4 grams of KIO3 and add H2O until the fi­nal homogeneous solution has a
volume of 2.00 liters
D 42.8 grams of KIO3 and add 2.00 liters of H2O
E 21.4 grams of KIO3 and add 2.00 liters of H2O

6. Approximately what mass of CuSO4 • 5H2O (250 g mol-1) is required to prepare 250 mL
of 0.10 M copper(II) sulfate solution?
A 4.0 g O
B 6.2 g C 34 g D 85 g E 140 g

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7. A student uses visible spectrophotometry to determine the concentration of CoCl2(aq) in a
sample solution. First the student prepares a set of CoCl2(aq) solutions of known
concentration.
Then the student uses a spectrophotometer to determine the absorbance of each of the
standard solutions at a wavelength of 510nm and constructs a standard curve. Finally, the
student determines the absorbance of the sample of unknown concentration.
The original solution used to make the solutions for the standard curve was prepared by
dissolving 2.60g of CoCl2 (molar mass 130 g/mol) in enough water to make 100 mL
of solution. What is the molar concentration of the solution?

O
A 0.200 M B 0.500 M C 1.00 M D 5.00 M

8. For an experiment, a student needs 100.0 mL of 0.4220 M NaCl. If the student starts with
NaCl(s) and distilled water, which of the following pieces of laboratory glassware should
the student use to prepare the solution with the greatest accuracy?
A 25 mL volumetric pipet
B 100 mL Erlenmeyer flask
C 100 mL graduated cylinder

O
D 100 mL volumetric flask
E 1 L beaker

9. How many mL of 10.0 M HCl are needed to prepare 500 mL of 2.00 M HCl ?
A 1.00 mL B 10.0 mL C 20.0 mL O
D 100 mL E 200 mL

10. If 200. mL of 0.60 M MgCl2(aq) is added to 400. mL of distilled water, what is the
concentration of Mg2+(aq) in the resulting solution? (Assume volumes are additive).

O
A 0.20 M B 0.30 M C 0.40 M D 0.60 M E 1.2 M

11. If 50. mL of 1.0 M NaOH is diluted with distilled water to a volume of 2.0 L,
the concentration of the resulting solution is

O
A 0.025 M B 0.050 M C 0.10 M D 0.50 M E 1.0 M

12. How many moles of Na+ ions are in [Link] of 0.100M Na3PO4(aq) ?
A 0.300 mol B 0.100 mol O
C 0.0300 mol D 0.0100 mol

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13. How many grams of CaCl2 (molar mass =111g/mol) are needed to prepare 100 mL of
0.100MCl−(aq) ions?

O
A 0.555 g B 1.11 g C 2.22 g D 5.55 g

14. Solid Al(NO3)3 is added to distilled water to produce a solution in which the concentration
of nitrate, [NO3-], is 0.10 M. What is the concentration of aluminum ion, [Al3+], in this
solution?
A 0.010 M O
B 0.033 M C 0.066 M D 0.10 M E 0.30 M

15. The volume of distilled water that should be added to 10.0 mL of 6.00 M HCl(aq) in order to
prepare a 0.500 M HCl(aq) solution is approximately
A 50.0 mL B 60.0 mL C 100 mL O
D 110 mL E 120 mL

16. The volume of water that must be added in order to dilute 40 mL of 9.0 M HCl to a
concentration of 6.0 M is closest to
A 10 mL O
B 20 mL C 30 mL D 40 mL E 60 mL

17. What is the molarity of I-(aq) in a solution that contains 34 g of SrI2 (molar mass 341 g) in
1.0 L of the solution?
A 0.034 M B 0.068 M C 0.10 M O
D 0.20 M E 0.68 M

18. When 70 milliliter of 3.0 molar Na2CO3 is added to 30 milliliters of 1.0-molar NaHCO3
the result­ing concentration of Na+ is
A 2.0 M B 2.4 M C 4.0 M O
D 4.5 M E 7.0 M

19. Which of the following is the best piece of laboratory glassware for preparing 500.0 mL of
an aqueous solution of a solid?

O
A Volumetric Falsk
B Erlenmeyer flask
C Test tube
D Graduated beaker
E Graduated cylinder

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3.8 Representations of Solutions

3.10 Solubility

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Solubility
In general, if the solvent–solute interactions are not at least similar, or possibly stronger, than
either of the solute–solute or solvent–solvent interactions, then the solute will not be able to
dissolve.

Hydrocarbons of similar chain lengths will have very similar strengths of London
Dispersion Forces so we would expect them to dissolve readily in each other.

Short chained alcohols will have very similar strengths of Hydrogen Bonding to those
existing between water molecules, so we would expect them to dissolve readily in each
other. Solubility decreases for the larger alcohols as the LDF carbon chain dominates.

Polar molecules (dipole-dipole) are harder to predict and we sometimes 'work backwards'
- since chloroform and acetone dissolve in each other, we deduce that the strengths
of attraction are similar.
However, acetone is soluble in water, wheras chloroform
has limited solubility in water. Acetone has the ability to
form hydrogen bonds with water wheras chloroform
cannot.
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Solvent Miscibility Table
Strictly speaking miscibility is the ability of two liquids to mix with each other, but it is very
similar to solubility. The difference, perhaps, is that a liquid that will not mix with water -
immiscible, will remain as separate layers - if mixed in equal quantities, might still be able to
dissolve if quantities are very low.
The table below is for a selection of liquids that are often used as solvents. Notice the almost
uniquely high Polarity Index of water. Not surprisingly, liquids with much lower polarities will
struggle to mix with water - unless they can get involved with hydrogen bonding.

9.0 Water
6.2 Acetic (Ethanoic) acid 100

5.2 Ethanol 100

5.1 Methanol 100

5.1 Acetone (propanone) 100

4.7 Butan-2-one (MEK) 24

4.4 Ethyl Acetate 8.7 Water Miscible

4.1 Chloroform 0.8 Miscible Liquids
4.0 Propan-1-ol 100 Immiscible Liquids
4.0 Butan-1-ol 100 24 Solubility in Water % w/w
3.9 Propan-2-ol 100

3.9 Butyl Acetate 7.8

3.1 Dichloromethane 1.6

2.8 Diethylether 6.9

2.4 Toluene neg

1.6 Carbon tetrachloride neg

0.2 Cyclohexane neg

0.0 Hexane neg

0.0 Pentane neg

Polarity Index →

Polarity Index →
9.0
6.2
5.2
5.1
5.1
4.7
4.4
4.1
4.0
4.0
3.9
3.9
3.1
2.8
2.4
1.6
0.2
0.0
0.0
Acetic (Ethanoic) acid

Acetone (propanone)

Carbon tetrachloride
Butan-2-one (MEK)

Dichloromethane
Butyl Acetate
Ethyl Acetate

Cyclohexane
Diethylether
Propan-1-ol

Propan-2-ol
Chloroform

Butan-1-ol
Methanol

Pentane
Ethanol

Toluene

Hexane
Water

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The most striking feature of the Solvent Miscibility Table is the range of liquids that will mix with
each other - ethanol (5.2 - hydrogen bonding & LDF's) mixes with pentane (0.0 - LDF's).

By themself, the pentane-pentane LDF's cannot compete with the hydrogen bonds in
ethanol. However, in a mixture, presumably, the combination of permanent dipole-induced
dipole and LDF's must be enough to allow the liquids to mix/dissolve.

As said earlier, predicting polar molecules is not 'easy' and there is no substitute for actually
putting liquids together and seeing what happens.
We have a 'like dissoves like' rule but it refers to attractions rather than labels such as polar and
non-polar which is how it is often described. However, in the absence of any other data it is
acceptable to assume that a polar solvent is best for disssolving polar substances while a non-polar
solvent is best for dissolving non-polar substances.

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Solubility of Ionic Compounds
With a polarity index of 9.0, water is about the only covalent molecule capable of dissolving ionic
substances.

Dissolving an ionic substance is a bit like a 'tug-of-war' - the combined force of several
ion-dipole attractions against the combined force of several ionic attractions.

Even once dissolved, the 'tug-of-war' is not over. We often represent dissolving as a
reversible reaction that reaches an
equilibrium with a certain proportion of the
solid dissolved while the rest remains solid.
⇌
This position can be described by an
equilibrium constant, Ksp , called the
solubility product.
In the case of NaCl, the equilibrium lies far to the right (Ksp = 37) and we would normally
consider that it dissolves 'completely'.
Lead (II) iodide, PbI2, on the other hand,
has a Ksp of 1.4 x 10-8 so a negligible amount
would dissolve in water.
However, we often make use of very low Ksp
values as an analytical tool.
Gravimetric analysis can involve the
formation of a solid precipitate which, once
filtered and dried, can be weighed to
determine the mass of precipitate formed.
We could use this to, for example, determine
the amount of lead in a water sample or the
amount of iodide ions in table salt.
1 mol of PbI2 ≡ 1 mole of Pb ≡ 2 mol of I
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Other Factors
Intermolecular attractions, alone, will never be able to fully explain or predict solubility.
For example , there are Thermodynamic
considerations (both Enthalpy and
Entropy) that need to be factored in.
Solute-solute attractions need to be
broken (endothermic), solvent-solvent
attractions need to be broken
(endothermic) and then solute-solvent
attractions formed (exothermic).
In a later Topic you will learn how to
factor in changes in disorder (Entropy).

Not surprisingly, temperature, can have a big effect but not always as expected:
Most ionic solids become more soluble
as temperature increases - but not all:
solubility of NaCl remains
virtually constant.
Some will even become less soluble as
temperature increases.
Our equilibrium studies tell us that
increasing temperature normally
favours the endothermic direction and
vice versa - but not always in solutions!
Most gases are not that soluble in
water (notice scale) and their solubility
decreases as temperature increases.
One consequence of climate change is
that oxygen levels are dropping as sea
temperatures rise.
Certain species of shark, for example,
are being forced to move to shallower
waters to get their oxygen, leading to
increased competition with man.
Ocean CO2 is involved in a whole chain of reversible reactions but increasing sea temperatures
could see CO2 released back into the atmosphere leading to even more Climate Change.
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3.8 & 3.10 Practice Problems
1.

Based on concepts of polarity and hydrogen bonding, which of the following sequences
correctly lists the compounds above in the order of their increasing solubility in water?
A Z<Y<X B Y<Z<X C Y<X<Z D X<Z<Y O
E X<Y<Z

2.

Benzene, C6H6 , has the structure shown above. Considering the observation that benzene
is only sparingly soluble in water, which of the following best describes the intermolecular
forces of attraction between water and benzene?
A Benzene is nonpolar, therefore there are no forces between water and benzene.
B The H atoms in benzene form hydrogen bonds with the O atoms in water.
C Benzene is hydrophobic, therefore there is a net repulsion between water and
benzene.

O
D There are dipole-induced dipole and London dispersion interactions between water
and benzene.

3. On the basis of molecular structure and bond polarity, which of the following compounds
is most likely to have the greatest solubility in water?
A CH4 B CCl4 C NH3 D PH3 O
4. Sodium chloride is LEAST soluble in which of the following liquids?
A H2O B CCl4 C HF O D CH3OH E CH3COOH

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5.

Gases generated in a chemical reaction are sometimes collected by the displacement of

water, as shown above. Which of the following gases can be quantitatively collected by this
method?

O
A H 2
B CO2 C HCl D SO3OH E CH3COOH

6. M+ is an unknown metal cation with a +1 charge.

A student dissolves the chloride of the unknown metal, MCl, in enough water to make
100.0 mL of solution. The student then mixes the solution with excess AgNO3 solution,
causing AgCl to precipitate. The student collects the precipitate by filtration, dries it,
and records the data shown below. (The molar mass ofAgCl is 143 g/mol.)
Mass of unknown chloride MCl = 0.74 g
Mass of filter paper = 0.80 g
Mass of filter paper plus AgCl precipitate = 2.23 g

Which of the following diagrams best represents the AgNO3 solution before the reaction
occurs? Note: water molecules are represented by the symbol

A B

C D

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7. The survival of aquatic organisms depends on the small amount of O2 that dissolves in
H2O. The diagrams below represent possible models to explain this phenomenon.

Which diagram provides the better particle representation for the solubility of O2 in H2O,
and why?

A Diagram 1, because O2 molecules can form hydrogen bonds with the H2O
molecules.
B Diagram 1, because O2 and H2O are polar molecules that can interact through
dipole-dipole forces.

O
C Diagram 2, because the polar H2O molecules can induce temporary dipoles on the
electron clouds of O2 molecules.
D Diagram 2, because the nonpolar O2 molecules can induce temporary dipoles on
the electron clouds of H2O molecules.

8. Of the following organic compounds, which is LEAST soluble in water at 298 K?

A CH3OH, methanol
B CH3CH2CH2OH, l-propanol

O
C C6H14, hexane
D C6H12O6, glucose
E CH3COOH, ethanoic (acetic) acid

9. Which of the following molecules is least soluble in water?

A B C D

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10. Based on their Lewis diagrams, which of the following pairs of liquids are most soluble in
each other?

O
A

11. Which of the following substances has the greatest solubility in C H

5 12(l)
at 1 atm?

A SiO2(s)
B NaCl(s)
C H2O(l)

O
D CCl4(l)
E NH3(g)

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12. A student places a piece of I2(s) in 50.0    mL of H2O(l), another piece of I2(s) of the same mass
in 50.0    mL of C6H14(l), and shakes the mixtures. The results are shown below.
What do the results indicate about the intermolecular interactions of the substances?

A I2 and H2O have similar intermolecular interactions, and I2 and C6H14 do not.

O
B I2 and C6H14 have similar intermolecular interactions, and I2 and H2O do not.
C I2 , H2O , and C6H14 all have similar intermolecular interactions.
D I2 , H2O , and C6H14 have three completely different types of intermolecular
interactions.

13. Ag+(aq) + Cl—(aq) ⇄ AgCl(s)

A student mixes dilute AgNO3(aq) with excess NaCl(aq) to form AgCl(s), as represented
by the net ionic equation above. Which of the diagrams below best represents the
ions that are present in significant concentrations in the solution?
(Ksp for AgCl is 1.8 x 10−10.)

A B C O D

14. Which of the following compounds the LEAST soluble in water

O
A CH CH CH CH B
3 2 2 3
CH3CH2CH2OH C CH3COCH3

D CH3COOH E CH3CH2CH2NH2
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3.8 & 3.10 Quick Check - AP FRQ Questions
1. A student is given 50.0mL of a solution of Na2CO3 of unknown concentration.
To determine the concentration of the solution, the student mixes the solution with excess
1.0MCa(NO3)2(aq), causing a precipitate to form. The balanced equation for the reaction is
shown below.
Na2CO3(aq) + Ca(NO3)2(aq) → 2NaNO3(aq) + CaCO3(s)

a) Write the net ionic equation for the reaction that occurs when the solutions of
Na2CO3 and Ca(NO3)2 are mixed.

Ca2+(aq) + CO32-(aq) → CaCO3 (s)

phase designations not required

b) The diagram below is incomplete. Draw in the species needed to accurately

represent the major ionic species remaining in the solution after the reaction

has been completed.

The diagram shows one Ca 2+ ion (or more than one Ca2+ ion and the correct


number of additional NO3- ions to balance charge).
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2. A student prepares a calibration graph by measuring the absorbances of CuSO4(aq) solutions
of known concentrations.
A particulate drawing of a single Cu2+ ion is shown in the following box. Draw two H2O
molecules in the box to show the most likely orientation of H2O(l) molecules around the
Cu2+ ion.

The drawing shows two water molecules generally oriented so the large circle


(indicating oxygen) is closer to the ion than the two small circles.

3. The structures of a water molecule and a crystal of LiCl(s) are

represented opposite. A student prepares a 1.0 M solution
by dissolving 4.2 g of LiCl(s) in enough water to make
100 mL of solution.
In the space provided below, show the interactions
of the components of LiCl(aq) by making a drawing
that represents the different particles present in the
solution. Base the particles in your drawing on the particles shown in the representations
above. Include only one formula unit of LiCl and no more than ten molecules of water.
Your drawing must include the following details.
• identity of ions (symbol and charge)
• the arrangement and proper orientation
of the particles in the solution

The sketch should clearly show:

1. a clear representation of at least one Li+ ion
and one Cl– ion separated from each other,
labeled, and charged;
(answer continues on next page)
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The sketch should clearly show:

2. each ion surrounded by at least two H2O molecules; and

3. H2O molecules with the proper orientation around each ion (i.e., the oxygen end of
the watermolecules closer to the lithium ion and the hydrogen end of the water
molecules closer to the chloride ion).

4.

The compound urea, H2NCONH2 , is widely used in chemical fertilizers. The complete
Lewis electron-dot diagram for the urea molecule is shown above.
Urea has a high solubility in water, due in part to its ability to form hydrogen bonds. A
urea molecule and four water molecules are represented in the box below.
Draw ONE dashed line (----) to indicate a possible location of a hydrogen bond between a
water molecule and the urea molecule.

There is a dashed line connecting a hydrogen atom in water to a nitrogen or oxygen atom
in urea or a dashed line connecting an oxygen atom in water to a hydrogen atom in urea.

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3.9 Separation of Solutions & Mixtures

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Filtration
In general, filtration cannot be used to separate a substance
from a solution unless:-

① another chemical is added to precipitate

out the target substance, or
there is a large difference in solubility at
②
different temperatures allowing for
recrystallisation
Method ①, however, would change the substance
e.g. KI(aq) → PbI2 (s)
and method ② is unlikely to recover all of the substance.

Recrystallisation can be much more effective with organic molecules, which can have very large
differences in solubility at different temperatures in an optimum solvent.

Distillation

Evaporation (if solvent not needed) or distillation will be more effective at separating, for
example salt from water.
As a raw material for the chemical industry, salt can be collected from sea water with the water
allowed to escape into the atmosphere.
Elsewhere in the world, desalination plants are busy extracting drinking water from sea water
while the unwanted salt is dumped back into the sea.
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Fractional Distillation
Where a solution contains a
mixture of miscible liquids,
a tall column can be
added to the apparatus.
This technique relies on
the liquids having
different strengths of
intermolecular attraction.
As a result, the liquids will
vaporise to different extents.
Liquids with weak
attractions will vaporise
more easily and have higher
vapour pressures.

The liquids with higher vapour pressures will make it to the top of the column first where they will
enter the condenser to be cooled back to liquid and will be collected first.
Over time, the other liquids will vaporise, be condensed and collected.

Solvent Extraction
Solvent extraction is a method for
separating a soluble substance from a mixture
by using a different solvent.
It relies on variations in the solubilities of
different compounds in different substances.
It involves the use of two immiscible solvents
that will form separate layers.
If chosen carefully, the desired substance will be much more soluble in one solvent while the
other components of the mixture will remain dissolved in the original solvent (often water).
When a mixture is shaken in a separating funnel containing two immiacible solvents, the
chemicals will partition themselves according to their relative solubilities in each solvent.
This will generally be determined by how similar their intermolecular forces are. One solvent is
then removed through the tap while the other is poured out the top.
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Since the substance has solubility in both solvents, it will be impossible to obtain 100% with a
single extraction. For example, a substance may be only slightly more soluble in ether than water
so partitions itself 58%-ether and 42%- water.
However, the 42% left behind in the water can be put through a second and third extraction
which will significantly improve the yield.

Normally, 3 extractions are enough. In this case, 0.46 g

from the original 0.5 g represents a yield of:-
(0.46 / 0.50) x 100 = 92%

Chromatography
Similar to solvent extraction, chromatography utilises two immiscible phases. A mobile phase - a
solvent or solvent mixture - as well as a stationary phase - often paper - which will be polar.

The presence of a polar solvent will normally help

ensure that polar chemicals remain dissolved and
will aid interactions with the paper, thus slowing
those chemicals down.

Any non-polar solvent will normally help

ensure that non-polar chemicals remain dissolved.

The chemicals being separated will partition

themselves between the stationary phase and
mobile phase to different extents and thus
travel at different speeds.
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Once a chromatogram has been run it can be useful to record the distances
travelled by the different chemical relative to the distance travelled by the
solvent. This is called the Retention Factor, Rf

There are a wide variety of different types of chromatograph but they all involve the same
principles of a stationary phase, mobile phase and the partitioning of the mixture components.
In Thin Layer Chromatography (TLC) the stationary phase is thin sheets of plastic with a coating
of silica. The mobile phase will be, again, a solvent or mixture of solvents.
Column Chromatography utilises a glass tube filled with a resin - ionic, polar or non-polar.
It can have all solvents added at same time or at different times to wash out each component
separately.
Gas Layer Chromatography uses a long metal
column packed with powder and coiled to save space.
The mobile phase is a carrier gas. The speed at which
components travel is determined by interactions with
the stationary phase - polar or non-polar as needed.

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3.9 Practice Problems
1. Which of the following techniques is most appropriate for the recovery of solid KNO3 from
an aqueous solution of KNO3?

A Paper chromatography B Filtration C Titration

D Electrolysis OE Evaporation to dryness

2.

On the basis of the solubility curves shown above, the greatest percentage of which
compound can be recovered by cooling a saturated solution of that compound from 90°C
to 30°C?
A NaCl B KNO3 O C K2Cr2O7 D K2SO4 E Ce2(SO4)3

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3.

The diagram above shows a thin-layer chromatogram of a mixture of products from a

chemical reaction. The separation was performed using 50% ethyl acetate in hexane as the
solvent (mobile phase) and silica gel as the polar stationary phase.

On the basis of the chromatogram and the information about solvents in the table above,
which of the following would be the best way to decrease the distance that the products
travel up the plate?

A Use pentane instead of hexane in the solvent.

O
B Decrease the percentage of ethyl acetate in the solvent.
C Increase the percentage of ethyl acetate in the solvent.
D Add up to 5% methanol to the solvent.

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4. A student obtains a liquid sample of green food coloring that is known to contain a
mixture of two solid pigments, one blue and one yellow, dissolved in an aqueous solution
of ethanol.
Which of the following laboratory setups is most appropriate for the student to use in
order to separate and collect a substantial sample of each of the two pigments?
A B

C D

O

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5.

A student performed a fractional distillation of a mixture of two straight-chain

hydrocarbons, C7H16 and C8H18.
Using four clean, dry flasks, the student collected the distillate over the volume ranges
(A, B, C, and D) shown in the graph above.
Over what volume range should the student collect the distillate of the compound with the
stronger intermolecular forces?
A A B B C C O
D D

6. A mixture containing equal numbers of moles of

ethyl acetate and butyl acetate was separated using
distillation.
Based on the diagrams shown above, which of the
following identifies the substance that would be
initially present in higher concentration in the
distillate and correctly explains why that occurs?

A Ethyl acetate, because it has fewer C-C bonds to break

O
B Ethyl acetate, because it has a shorter carbon chain and weaker London dispersion
forces
C Butyl acetate, because it has more C-C bonds to break
D Butyl acetate, because it has a longer carbon chain and weaker dipole-dipole
attractions
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7.

In a paper chromatography experiment, a sample of a pigment is separated into two

components, X and Y, as shown in the figure above.
The surface of the paper is moderately polar. What can be concluded about X and Y based
on the experimental results?
A X has a larger molar mass than Y does.
B Y has a larger molar mass than X does.
C X is more polar than Y.

O
D Y is more polar than X.

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3.11 Spectroscopy & Electromagnetic Spectrum

Spectroscopy - The Interaction of Matter and Electromagnetic Radiation

In an earlier Unit, the absorption or emmission of

light gave us crucial information about how electrons
were arranged in atoms.
Energy is absorbed when atoms are excited and electrons
are temporarily boosted to higher energy levels.
Energy is emitted when electrons return to their normal
'ground' state.

For electron transitions, the energy absorbed or energy emitted is sometimes in the region of
visible light or (more usually) in the ultraviolet region.
Max Planck was able to determine the relationship between the energy changes and the frequency
of light being absorbed or emitted.
where ν is frequency ΔE = hν
and h is Planck’s constant, 6.626 x 10–34 Js
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Electromagnetic Spectrum

Visible and Ultraviolet light are just parts of a range of energies that behave as waves and make up
the Electromagnetic Spectrum.
As waves, they all have a wavelength, λ in metres and travel (in a vacuum) at the speed of light,
c = 3 x 108 ms-1, and
c = λν where ν is frequency with unit of per second, s-1 or Hz
Due to the wide range of energies found in the Electromagnetic Spectrum, wavelengths are often
given in nanometres (nm - x 10-9m so visible light is about 400 - 800 nm).

Various regions of the electromagnetic spectrum may be used to help us probe matter with the
assistance of a variety of different instruments in a process called spectroscopy:
• radio waves - nmr spectroscopy - identifies positions of atoms within a molecule

Can be used to tell the difference between butan-1-ol (on the left) and butan-2-ol
(on the right) by detecting slight changes in the spin of the proton in the nuclei of
the hydrogen atoms depending on neighbouring atoms and proximity to
electronegative groups.

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• microwaves - identifies molecular rotations
Much of current understanding of the nature of weak molecular
interactions such as London Dispersion forces, dipole-dipole and
hydrogen bonding has been established through rotational spectroscopy.

• infrared waves - IR spectroscopy - identifies molecular vibrations (functional groups)

IR Spectroscopy detects changes that take place in the vibrational

energies of a molecule when exposed to IR radiation.
Bonds such as C—H, C—O and C = O all vibrate with a particular
frequency and will absorb that frequency of radiation.
This allows the specific bonds present in a molecule to be identified -
including functional groups which will allow molecule to be assigned
to a particular family - alcohol, aldehyde, ketone, ester, amine etc.

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• ultraviolet and visible-light spectroscopy - identifies electronic transitions by
promoting electrons to higher energy levels.

Sometimes we provide energy in the form of heat from a flame or electrical energy
to excite the atoms and promote electrons to higher energy levels. We measure the
light energy released when the electrons return to their ground state.

Sometimes we provide energy in the form of light to excite the atoms and promote
electrons to higher energy levels. We measure the light energy absorbed. When the
electrons return to their ground state, they release the excess energy in the form of
heat.
Chemicals that have colours at room temperature (eg. chlorophyll) will be absorbing
certain frequencies from visible light (eg. corresponding to red and blue) and we will
observe the colours that remain (eg. green).
The characteristic yellow light in many street lights is due to the presence of sodium
atoms which become excited and emit yellow light when the street light heats up.

• X-rays - photoelectron spectroscopy - identifies electron configurations by removing

electrons from their ground states.

This was covered in an earlier Unit and

is covered again in the next lesson.
Main thing is to appreciate that PES
actually removes electrons from
the atoms.
This allows the electron configuration
of the atom to be determined.

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3.11 Practice Problems
1. Infrared spectroscopy is a useful tool for scientists who want to investigate the structure of
certain molecules. Which of the following best explains what can occur as the result of a
molecule absorbing a photon of infrared radiation?
A The energies of infrared photons are in the same range as the energies associated
with changes between different electronic energy states in atoms and molecules.
Molecules can absorb infrared photons of characteristic wavelengths, thus revealing
the energies of electronic transitions within the molecules.

O
B The energies of infrared photons are in the same range as the energies associated
with different vibrational states of chemical bonds. Molecules can absorb infrared
photons of characteristic wavelengths, thus revealing the types and strengths
of different bonds in the molecules.
C The energies of infrared photons are in the same range as the energies associated
with different rotational states of molecules. Molecules can absorb infrared photons
of characteristic wavelengths, thus revealing the energies of transition between
different rotational energy states of the molecules.
D The energies of infrared photons are in the same range as the total bond energies of
bonds within molecules. Chemical bonds can be completely broken as they absorb
infrared photons of characteristic wavelengths, thus revealing the energies of the
bonds within the molecules.

2. Which statement correctly compares what occurs when molecules absorb photons in the
microwave region with what occurs when molecules absorb photons in the infrared
region?

O
A
Microwave photons cause the molecules to increase their rotational energy states,
whereas infrared photons cause the molecules to increase their vibrational energy
states.

B Microwave photons cause electrons in the molecules to increase their electronic

energy states, whereas infrared photons cause the molecules to increase their
rotational energy states.

C Microwave photons cause the molecules to increase their vibrational energy states,
whereas infrared photons cause electrons in the molecules to increase their
electronic energy states.

D Microwave photons cause the molecules to increase their rotational energy states,
whereas infrared photons cause electrons in the molecules to increase their
electronic energy states.
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3. N2 molecules absorb ultraviolet light but not visible light. I2 molecules absorb both visible
and ultraviolet light. Which of the following statements explains the observations?
A More energy is required to make N2 molecules vibrate than is required to make I2
molecules vibrate.
B More energy is required to remove an electron from an I2 molecule than is required
to remove an electron from a N2 molecule.

O
C Visible light does not produce transitions between electronic energy levels in the N2
molecule but does produce transitions in the I2 molecule..
D The molecular mass of I2 is greater than the molecular mass of N2.

4.

Beta-carotene is an organic compound with an orange color. The diagram above shows
the ultraviolet spectrum of beta-carotene. Which of the following statements is true about
the absorption bands in the spectrum?
A The absorption band between 250 and 320 nm is due to transitions in electronic
energy levels, and the absorption band between 380 and 520 nm is due to
transitions in molecular vibrational levels.

B The absorption band between 250 and 320 nm is due to transitions in molecular
vibrational levels, and the absorption band between 380 and 520 nm is due to
transitions in molecular rotational levels.

O
C The two main absorption bands are associated with transitions in electronic energy
levels. The band in the region corresponding to shorter wavelengths shows a lower
absorbance than the band in the region corresponding to longer wavelengths.

D The two main absorption bands are associated with transitions in molecular
vibrational levels. The band in the region corresponding to shorter wavelengths
shows a lower absorbance than the band in the region corresponding to longer
wavelengths.
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5.

The diagram above represents the absorption spectrum for a pure molecular substance.
Which of the following correctly indicates the type of transition observed for the substance
in each of the regions of the absorption spectrum?

Region X Region Y Region Z

A molecular vibration molecular rotation electronic transition

B electronic transition molecular rotation molecular vibration

C molecular rotation molecular vibration electronic transition

O
D electronic transition molecular vibration molecular rotation

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3.12 Properties of Photons

In general, when matter interacts with radiation from the Electromagnetic Spectrum, energy is
absorbed or emitted. In these circumstances, we consider the radiation to consist of photons and
the energy of the photon is proportional to the frequency of the radiation:
where ν is frequency ΔE = hν
and h is Planck’s constant, 6.626 x 10–34 Js
In Chemistry, we prefer to work in wavelengths (λ), so we may use the Wave Equation (c = λν) to
convert λ → ν, or we combine the two equations:

ΔE = hν and c = λν rearranges to become ν=c/λ

ΔE = hc / λ
where λ is wavelength in metres, m
and h is Planck’s constant, 6.626 x 10–34 Js
and c is Speed of Light, 3.00 x 108 ms-1
so E is Energy in joules, J
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Example 1: In the Balmer Series of Hydrogen, the transitions represent excited electrons
dropping back to the n = 2 energy level. Calculate the energy of the n=6 → n=2
transition.
From the diagram, λ = 410 nm for n=6 → n=2
This must be converted to metres: 1 nm = 10-9 m
So 410 nm = 410 x 10-9 m ( or 4.10 x 10-7 m in true scientific notation)

ΔE = hc / λ = (6.626 x 10–34 Js) (3.00 x 108 ms-1)

(410 x 10-9 m)
= 4.85 x 10-19 J (answer to 3 sig figs to reflect the least
accurate sig figs of data used)

This is the energy of a single photon of light released when one electron transitions
from n=6 → n=2. We normally prefer to scale up to one mole using Avogadros
constant, L = 6.023 x 1023 mol-1
So, ΔE = 4.85 x 10-19 J x 6.023 x 1023 mol-1

= 292115.5 J mol-1 (round to 3 sig figs and convert to kJ)

= 292 kJ mol-1

All '3 steps' can be combined: ΔE = Lhc / λ

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Example 2:

The diagram above shows the Photoelectron Spectrum (PES) for Hydrogen. Use this
to calculate the wavelength of the radiation needed to remove an electron from
Hydrogen.
From the diagram, ΔE = 1.31 MJ mol-1 = 1.31 x 106 J mol-1
As we have been given a molar quantity of energy and are required to
calculate a wavelength, the combined equation is most appropriate.

ΔE = Lhc / λ rearranges to λ = Lhc /ΔE

λ = Lhc /ΔE = (6.023 x 1023 mol-1) (6.626 x 10–34 Js) (3.00 x 108 ms-1)
(1.31 x 106 J mol-1)
= 0.000000091393278 m
or (in scientific notation) = 9.1393278 x 10-8 m
to 3 sig figs = 9.14 x 10-8 m
in nanometres = 91.4 x 10-9 m = 91.4 nm

Prior to PES, we relied on data from

UV spectroscopy. The Lyman Series on
the previous page only shows
transition values up to n=6.
If taken 'to the limit', the energy
needed to remove the electron from
hydrogen was equivalent to a
wavelength of 91.2 nm.
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3.12 Practice Problems
The first two questions are based on the information given below.

The diagram above represents the photoelectric effect for a metal. When the metal surface
is exposed to light with increasing frequency and energy of photons, electrons first begin to
be ejected from the metal when the energy of the photons is 3.3×10−19 J

1. Which of the following is closest to the frequency of the light with photon energy of
3.3 × 10−19 J ?
A 5.0 × 10−53 s−1 B 5.0 × 10−16 s−1 O
C 5.0 × 10 s
14 −1
D 5.0 × 1052 s−1

2. Using the wavelength information provided above, what is the color of the light?
A Red O
B Orange C Yellow D Blue

3. A student uses visible spectrophotometry to determine the concentration of CoCl2(aq) in a

sample solution. First the student prepares a set of CoCl2(aq) solutions of known
concentration.
Then the student uses a spectrophotometer to determine the absorbance of each of the
standard solutions at a wavelength of 510nm and constructs a standard curve. Finally, the
student determines the absorbance of the sample of unknown concentration.
A wavelength of 510nm corresponds to an approximate frequency of 6 × 1014 s−1. What is
the approximate energy of one photon of this light?

A 9 × 1047 J B 3 × 1017 J C 5 × 10−7 J O

D 4 × 10 −19
J

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3.13 Beer-Lambert Law

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Colorimetry - Origin of Colour
Colorimetry is a widely used analytical tool. Electron transitions within atoms, ions & molecules
are often within the visible region of the Electromagnetic Spectrum. Energy will be absorbed to
temporarily boost electrons to higher energy levels - they will then release heat energy as they
return to ground state.
For example, Indigo carmine dye:

absorbs light from the visible and

ultra-violet parts of the
electromagnetic spectrum.
It absorbs mainly in the red-orange-
yellow part of the visible spectrum
but transmits the blue-purple light
which accounts for the indigo colour
observed.

Best practice is to take all measurements at the wavelength

corresponding to the strongest absorbance - about 285 nm
in this case. However, this is likely to be outwith the range of most UV-Visible spectrometers, so
measurements are more likely to be taken at about 615 nm.
Spectrophotometers use prisms and will be able to select any wavelength required. Colorimeters
rely on coloured filters that are placed in front of the light source - in this case a red filter would
be selected which may not match exactly with the maximum absorbance.

Issue: Use of a filter (eg 650 nm) will require solution to be of a higher concentration to
get 'decent' absorption values.
Result: Linear relationships 'tail off' at higher concentrations (see later).

Before taking measurements, a cuvette filled with colourless solvent (often water) is used and the
Intensity of light transmitted (It) can be measured and this value can be assumed to be the same
as the Intensity of the Incident light ( Ii or Io ).

The use of a 'blank' cuvette will calibrate the

appartaus so that any absorption due to the solvent
or the glass/plastic cuvette is subtracted from any
measurements of subsequent solutions.
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Issue: Failure to calibrate using same cuvette filled with same solvent mixture.
Result: Subsequent measurements may include some absorbtion due to cuvette and/or
solvent which will lead to higher concentrations being calculated.

Preparation of Solutions
Before analysing a sample to determine the amount of a coloured substance that is present, it will
be necessary to prepare solutions of known concentration to help determine the linear
relationship between concentration and absorption.
A Standard Stock solution will be prepared accurately (Lesson 3.7) and then diluted (Lesson 3.7)
to produce a series of solutions of accurately known concentrations.

Issue: Failure to weigh accurately / transfer completely to standard flask / make up to

exactly the mark on the standard flask
Result: Subsequent calculations will be based on inaccurate concentrations.

Determination of Linear Relationship

Once the calibration solutions have been prepared, they can each have their absorbance
measured and plotted against their
calculated concentrations.
It is quite common for a 'first attempt'
to fail to produce a satisfactory straight
line.
One of the main problems is that, at
higher concentrations, intermolecular
interactions can have an effect and will
reduce absorption.
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Issue: Using too high concentrations

Result: Absorbances will 'tail off' resulting in a curve rather than a straight line.

Poor technique can also be an issue. Ideally, the same cuvette should be used for every
measurement (though expensive 'matched' cuvettes can be available) but that will require the
cuvette to be flushed between solutions.

Issue: Flushing cuvettes with water

Result: Some water remains in the cuvette (sticking to sides) which slightly dilutes next
solution.

This can be avoided by using the 'new solution' to flush out the 'previous solution'. The first flush
may have its concentration altered but by the third flush changes should be minimal.
Using lower concentrations and
working carefully should result in a
straight-line relationship between
concentration and absorbance.
A ∝ c
The size of the cuvette (usually 1 cm)
determines the path length for the light
travelling through the solution.
A ∝ b (or l)
Issue: Changing cuvette
Result: A smaller cuvette will result in a reduced absorbance while a larger cuvette will
result in an increased absorbance.

Mixtures / Impurities
Wavelengths must be chosen to avoid detecting other chemicals present.

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Beer-Lambert Law
Firstly, Spectrophotometers and colorimeters
measure the intensity of light hitting their
detector - often a light dependent resistor.

The Absorbance is then calculated using the

following relationship:

Absorbance is proportional to concentration (c): A ∝ c

Absorbance is proportional to path length (b): A ∝ b (or l)

The constant of proportionality is referred to as the Molar Absortivity ( ε - epsilon) and is

a measure of how strongly a chemical species or substance absorbs light at a particular wavelength.
It is an intrinsic property of chemical species that is dependent upon their chemical composition
and structure.
It is normally determined by
experiment and can be calculated from
the gradient of a plot of absorbance
against concentration.
It will only be valid for the particular
wavelength, cuvette, species, solvent,
temperature etc. that were used when
taking measurements.
Gathering all our terms together
produces the Beer-Lambert Law:
AA = ε b c where = absorbance and has no units due to Io / It

b = path length (in cm)
c = concentration (in mol l-1 or M)
ε = molar absortivity ( in M-1 cm-1 )
Unit for molar absortivity is largely meaningless - chosen to ensure all units cancel out to leave
Absorbance with no unit.
Most of the time, the species being measured (eg Cu2+ ), the cuvette, the wavelength chosen, the
temperature etc. are not changing so Absorbance ∝ c

Issue: Not controlling variables

Result: Absorbances will not be trustworthy.
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3.13 Practice Problems
1.

The diagrams above show the ultraviolet absorption spectra for two compounds.
Diagram 1 is the absorption spectrum of pure acetone, a solvent used when preparing
solutions for an experiment. Diagram 2 is the absorption spectrum of the solute for which
the absorbance needs to be measured to determine its concentration.
When the student reads the absorbance of the solution at 280nm, the result is too high.

Which of the following is most likely responsible for the error in the measured absorbance?

A The student added too little solute to the acetone before measuring its absorbance.

B The student rinsed the cuvette with the solution before filling the cuvette with the
solution.

O
C The student forgot to calibrate the spectrophotometer first by using a cuvette
containing only acetone.

D The wavelength setting was accidentally changed from 280nm to 300nm before the
student made the measurement.

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2. A student uses visible spectrophotometry to determine the concentration of CoCl2(aq)
in a sample solution. First the student prepares a set of CoCl2(aq) solutions of known
concentration.
Then the student uses a spectrophotometer to determine the absorbance of each of the
standard solutions at a wavelength of 510nm and constructs a standard curve. Finally, the
student determines the absorbance of the sample of unknown concentration.

The student made the standard curve above. Which of the following most likely caused
the error in the point the student plotted at 0.050 M Co2+(aq) ?

O
A There was distilled water in the cuvette when the student put the standard solution
in it.

B There were a few drops of the 0.100 M Co2+(aq) standard solution in the cuvette when
the student put the 0.050  M standard solution in it.

C The student used a cuvette with a longer path length than the cuvette used for the
other standard solutions.

D The student did not run a blank between the 0.050 M Co2+(aq) solution and the one
before it.

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3. Fe3+(aq) + KSCN(s) → FeSCN2+(aq) + K+(aq)

To determine the moles of Fe3+(aq) in a 100. mL sample of an unknown solution, excess

KSCN(s) is added to convert all the Fe3+(aq) into the dark red species FeSCN2+(aq), as
represented by the equation above.
The absorbance of FeSCN2+(aq) at different concentrations is shown in the graph below.

If the absorbance of the mixture is 0.20 at 453 nm, how many moles of Fe3+(aq) were present
in the 100. mL sample? (Assume that any volume change due to adding the KSCN(s) is
negligible.)
A 4 x 10-4 mol B 3 x 10-4 mol O
C 4 x 10 -6
mol D 3 x 10-6 mol

4. Using a spectrophotometer, a student

measures the absorbance of four solutions
of CuSO4 at a given wavelength.
The collected data is given in the table
opposite.

Which of the following is the most likely explanation for the discrepant data in trial 4 ?
A The solution was at a lower temperature than the solutions in the other trials.

B The measurement was made using a different spectrophotometer that uses a cell
with a longer path length.

C The solution was saturated and the flow of light through the solution was restricted.

O
D The concentration of the solution was actually lower than 0.150M .
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5. A student prepared five solutions of CuSO4 with different concentrations, and then filled
five cuvettes, each containing one of the solutions.
The cuvettes were placed in a spectrophotometer set to the appropriate wavelength for
maximum absorbance. The absorbance of each solution was measured and recorded.

The student plotted absorbance versus concentration, as shown in the figure above.
Which of the following is the most likely explanation for the variance of the data point for
the 0.600 M CuSO4 solution?

A The cuvette into which the 0.600 M solution was placed had some water droplets
inside.

B The cuvette into which the 0.600 M solution was placed was filled slightly more than
the other cuvettes.

C The wavelength setting was accidentally moved away from that of maximum
absorbance.

O
D The cuvette used for the 0.600 M solution had not been wiped clean before being put
in the spectrophotometer.

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6. Cu(s) + 4 HNO3(aq) → Cu(NO3)2(aq) + 2 NO2(g) + 2 H2O(l)

Each student in a class placed a 2.00 g sample of a mixture of Cu and Al in a beaker and
placed the beaker in a fume hood.
The students slowly poured 15.0 mL of 15.8 M HNO3(aq) into their beakers. The reaction
between the copper in the mixture and the HNO3(aq) is represented by the equation above.
The students observed that a brown gas was released from the beakers and that the
solutions turned blue, indicating the formation of Cu2+(aq). The solutions were then diluted
with distilled water to known volumes
To determine the number of moles of Cu in the sample
of the mixture, the students measured the absorbance
of known concentrations of Cu(NO3)2(aq) using a
spectrophotometer.
A cuvette filled with some of the solution produced from
the sample of the mixture was also tested. The data
recorded by one student are shown in the table opposite.
On the basis of the data provided, which of the following is a possible error that the
student made?

A The Cu(NO3)2(aq) from the sample of the mixture was not diluted properly.

B The spectrophotometer was calibrated with tap water instead of distilled water.

O
C The student labeled the cuvettes incorrectly, reversing the labels on two of the
solutions of known concentration.

D The spectrophotometer was originally set to an inappropriate wavelength, causing

the absorbance to vary unpredictably

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3.9 & 3.11 - 3.13 Quick Check - AP FRQ Questions
1.
A student investigates the reaction between Ag(s) and HNO3(aq) represented by the equation
below.
3 Ag(s) + 4 HNO3(aq) → 3 AgNO3(aq) + NO(g) + 2 H2O(l)
The student runs the reaction using a 3 to 4 mole ratio of Ag(s) to HNO3(aq) . Suggest a
method the student can use to isolate solid AgNO3 from the other products of the
reaction.
The student can evaporate the water, leaving behind solid silver nitrate.

2. To spectrophotometrically determine the mass percent of cobalt in an ore containing

cobalt and some inert materials, solutions with known [Co2+] are prepared and the
absorbance of each of the solutions is measured at the wavelength of optimum absorbance.
The data are used to create a calibration plot,
shown opposite.
A 0.630 g sample of the ore is completely
dissolved in concentrated HNO3(aq).

The mixture is diluted with water to a

final volume of 50.00 mL. Assume that all
the cobalt in the ore sample is converted
to Co2+(aq) .

a) What is the [Co2+] in the solution if the

absorbance of a sample of the solution is 0.74?

An absorbance of 0.74 corresponds to a concentration of 0.0130 M (0.0125 M to

0.0135 M).

b) Calculate the number of moles of Co2+(aq) in the 50.00 mL solution.

1 point is earned for the correct calculation of the number of moles.

0.05000 L x (0.0130 mol Co2+/ 1.00 L) = 6.50 x 10-4 mol Co2+
c) Calculate the mass percent of Co in the 0.630 g sample of the ore.
1 point is earned for a correct calculation of the number of grams of Co that is
consistent with the number of moles of Co2+ in part b). (may be implicit)
1 point is earned for a correct calculation of the mass percent that is consistent
with the number of grams of Co.
6.50 x 10-4 mol x 58.93 g Co / 1.00 mol = 0.0383g Co
0.0383g Co / 0.630g ore x 100 % = 6.08 %
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3. A student has 100. mL of 0.400 M CuSO4(aq) and is asked to make 100. mL of 0.150 M
CuSO4(aq) for a spectrophotometry experiment.
The following laboratory equipment is available for preparing the solution: centigram
balance, weighing paper, funnel, 10 mL beaker, 150 mL beaker, 50 mL graduated cylinder,
100 mL volumetric flask, 50 mL buret, and distilled water.

a) Calculate the volume of 0.400 M CuSO4(aq) required for the preparation.

1 point is earned for the correct volume.
M1V1 = M2V2

V2 = (0.150M)(0.100L) / 0.400M V2 = 0.0375 L x (1000 mL/1L) = 37.5 mL

b) Briefly describe the essential steps to most accurately prepare the 0.150 M
CuSO4(aq) from the 0.400 M CuSO4(aq) using the equipment listed above.

1 point is earned for using the buret to measure 37.5 mL of 0.400 M CuSO4 solution.

1 point is earned for adding the CuSO4 solution to the volumetric flask and filling to
the mark with distilled water.

The student plans to conduct a spectrophotometric analysis to determine the

concentration of Cu2+(aq) in a solution. The solution has a small amount of Co(NO3)2(aq)
present as a contaminant.
The student is given the diagram below, which shows the absorbance curves for aqueous
solutions of Co2+(aq) and Cu2+(aq).

c) The spectrophotometer available to the student has a wavelength range of 400 nm

to 700 nm. What wavelength should the student use to minimize the interference
from the presence of the Co2+(aq) ions?
1 point is earned for a correct wavelength. 700 nm
(Any wavelength from 650 to 700 nm is acceptable.)
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4. A student is given a sample of CuSO4(s) that contains a solid impurity that is soluble and
colorless. The student wants to determine the amount of CuSO4 in the sample and
decides to use a spectrophotometer.
First, the student prepares a calibration graph by measuring the absorbances of CuSO4(aq)
solutions of known concentrations. The graph is shown below

a) The student dissolves the entire impure sample of CuSO4(s) in enough distilled water
to make [Link] of solution. Then the student measures the absorbance of the
solution and observes that it is 0.30. Determine the concentration of CuSO4(aq) in the
solution.

The response indicates that the absorbance is 0.15M .

(Unit not required. Any value from 0.14M to 0.16M is acceptable.)

b) Calculate the number of moles of CuSO4 that were in the impure sample of CuSO4(s).

The response gives the following calculation (or an equivalent): Unit not required.
0.15 mol /1000 mL x 100. moL = 0.015 mol

c) In addition to the number of moles of CuSO4 calculated in part b) , what other

quantity must be measured in order to calculate the mass percentage of CuSO4
in the impure sample of CuSO4(s) ?

The response indicates that the mass of the sample must be measured.

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5. The complete photoelectron spectrum of an element in its ground state is represented
below.

a) Based on the spectrum,

i) write the ground-state electron configuration of the element, and
The response gives one of the following two answers.

1s2 2s2 2p6 3s2 3p6 4s2 or
[Ar] 4s2

ii) identify the element.

The response indicates Ca

b) Calculate the wavelength, in meters, of electromagnetic radiation needed to remove

an electron from the valence shell of an atom of the element.

The response meets both of the following criteria.
The response indicates that the energy required is 0.980 x 10-18 J .
The response shows a calculation similar to the following.

E = h𝛎 = h c /λ so λ = hc / E

λ = (6.626 x 10-34 J)(2.998 x 108 ms-1) / (0.980 x 10-18 J)

λ = 2.03 x 10-7 m

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6. A student is given a solution of phenol red of unknown concentration. Solutions of phenol
red are bright pink under basic conditions. The student analyzes a sample of the solution
using a spectrophotometer set at a wavelength of 559 nm, the wavelength of
maximum absorbance for phenol red.
The measured absorbance of the phenol red solution at 559 nm is 0.35.

a) Based on the calibration curve shown below, what is the concentration of the
solution in micromoles per liter (μM) ?

The response gives a value between 5.2 μM and 5.6 μM.
b) If the student mixed 10mL of distilled water with 10mL of the sample, would this

diluted solution have an absorbance greater than, less than, or equal to the

absorbance of the original solution? Justify your answer.

The response meets both of the following criteria.

The response indicates that the diluted solution would have an absorbance less than
that of the original solution.


The response indicates that the diluted solution would have a lower concentration

and therefore a lower absorbance, in accordance with Beer’s law.
c) If the student measured the absorbance of the solution at a wavelength of 650nm,

would the absorbance be greater than, less than, or equal to the absorbance of

the solution at 559nm? Justify your answer.

The response meets both of the following criteria.
The response indicates that the absorbance at 650 nm would be less than the
absorbance at 559 nm .
The response indicates that 599 nm is the wavelength of maximum absorbance so
the absorbance at any other wavelength will be lower.
ISPS Chemistry Oct 2025 page 148 Intermolecular Forces