NSSCAS Chemistry

Theme 2

Physical chemistry
Theme 2 is comprised of FOUR topics

2.1 Chemical energetics

2.2 Electrochemistry
2.3 Equilibria
2.4 Reaction kinetics
 2.1 Chemical energetics

2.1.1 Enthalpy change (∆H)

2.1.2 Hess’ law
2.1.1 Enthalpy change (∆H)
• explain that chemical reactions are accompanied by energy changes,
principally in the form of heat energy; the energy changes can be
exothermic (ΔH is negative) or endothermic (ΔH is positive)
• explain and use the terms:
– enthalpy change of reaction and standard conditions, with particular reference to:
formation, combustion, hydration, solution, neutralisation, atomisation
– bond energy (ΔH positive, i.e. bond breaking)
• calculate enthalpy changes from appropriate experimental results, including
the use of the relationship enthalpy change, ΔH = –mcΔT
• outline chemical reactions in terms of energy transfers associated with the
breaking and making of chemical bonds
• calculate energy changes for simple reactions using bond energies
• explain why ΔH values from calculated bond energies differ from those
obtained from data booklet and experimentally determined values
 enthalpy, H and enthalpy change, ΔH
•• Enthalpy,
  H is an indication of the total energy of a substance and it
cannot be measured directly.
• When a chemical reaction occurs, there is normally a change in
energy.
• The enthalpy change of a reaction is the heat change in a reaction
at constant pressure.
• Enthalpy change H and has the unit kJmol-1. Notice that from this
unit, it can be deduced that H is the heat change (kJ) per mole
(mol-1).
• ‘delta’ () means ‘change in’, ‘H’ means enthalpy/heat.
• Chemical reactions are accompanied by energy (enthalpy) changes,
principally in the form of heat energy; and the energy changes can
be exothermic (ΔH is negative) or endothermic (ΔH is positive).
• Enthalpy change, ΔH is measurable.
 Exothermic and endothermic reactions

1. Most chemical reactions are accompanied by energy changes. Some

chemical reactions absorb energy while some release it.
2. An exothermic reaction is a reaction that releases energy to the
surroundings. Therefore the product contain less energy with respect
to the reactants. The energy is released as heat energy, so the
surroundings warm up.
3. An endothermic reaction is a reaction that absorbs energy from the
surroundings. Therefore the products contain more energy with
respect to the reactants. The energy is absorbed as heat energy, so
the surroundings cool down
• Examples of exothermic reactions are neutralisation, combustion,
dissolving anhydrous salts and the reaction between acids and metals,
reaction between acids and metal carbonates.
• Examples of endothermic reactions are atomisation, photosynthesis,
dissolving crystalline salts and thermal decomposition.
Exothermic and endothermic reactions
Exothermic reactions Endothermic reactions
releases heat to the absorbs heat from the
surroundings surroundings
has a negative ΔH by has a positive ΔH by convention
convention
enthalpy of the products is the enthalpy of the products is
lower than the enthalpy of the higher than the enthalpy of the
reactants reactants

The enthalpies of these The enthalpies of these

reactions are less than zero reactions are more than zero
(ΔH < 0, ΔH is negative) (ΔH > 0, ΔH is positive)
exothermic and endothermic reactions
– energy level diagrams
 measuring enthalpy changes
• Enthalpy changes can be
measured experimentally by
measuring the temperature
change as a reaction proceeds.
• Two common examples are
measuring the enthalpy change
of neutralisation and
combustion.
• Calorimetry is used to work out
the enthalpy changes of
reactions.
• Certain assumptions are made
when using calorimetry to
calculate enthalpy changes.
 q = mcT and ΔH = –mcΔT
•• It  is assumed that the reactions occur under completely constant
pressure, that no heat is lost to the surroundings and that the
specific heat capacity (4.18 kJ) and density (1 g ) of dilute solutions is
the same as that of water, Thus, numerically, it is assumed that 1 = 1
g.
• Enthalpy change form experimental results is calculated using the
equations q = mcT and ΔH = –mcΔT
• q = mcT where:
m = mass of substance or solution in grams (it is assumed
that 1 = 1 g)
c = specific heat capacity of solution (assumed to be 4.18 kJ)
T = change in temperature in Kelvin ( ) so if the reaction is
endothermic, T will be negative and if the reaction is
exothermic T will be positive.
 q = mcT and ΔH = –mcΔT
• Enthalpy
  change H and has the unit kJmol-1.
• Notice that from this unit, it can be deduced that
H is the heat change (kJ) per mole (mol-1).
Using ΔH = –mcΔT:
• for exothermic reactions (T ) it will be:
• ΔH = = = ΔH
• for endothermic reactions (T ) it will be:
• ΔH = = = ΔH
 An example

To calculate the enthalpy change of the reaction

(neutralisation reaction) between sodium hydroxide,
NaOH(aq) and hydrochloric acid, HCl(aq).

NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

 standard conditions
To make comparison of enthalpy changes a fair comparison, same conditions
must be used. These are called the standard conditions:
• A pressure of 100 kPa(approximately atmospheric pressure).
• A temperature of 298 K or 25 °C.
• Where solutions are involved, a concentration of 1.0 mol dm⁻³.
• Every substance involved must be in its normal (standard) physical state at
100 kPa and 298 K. The standard state of a substance depends on the state of
matter (i.e. solid, liquid or gas) in which the substance exists under standard
conditions. For solids, liquids and gases, the standard state is the state of
being a pure solid, liquid or gas at standard conditions. For example, chlorine
exists as gas, mercury exists as a liquid and sodium exists as a solid at
standard conditions. For a substance in solution (e.g. sodium hydroxide
aqueous), it is the state of being in solution of a concentration of 1 mol/dm 3
at standard conditions.
• If allotropes are involved, the allotrope which is more energetically stable is
used. For example, for carbon, graphite is chosen over diamond because
graphite is energetically more stable than diamond.
 Standard enthalpy changes ΔH°
• Standard enthalpy changes can be represented by the symbol ΔH°.
•  
• This refers that the reaction is carried out under standard conditions. For
example:
• (g) +2 (g) → (g) +2O(l); ΔH° = 890.3 kJ
• Standard enthalpy changes are described according to the type of reaction.

• Standard enthalpy change of reaction, ΔH°r is the enthalpy change when the
amount of reactants shown in the equation react to give products under
standard conditions.
• The reactants and products must be in their standard states.
• (g) + (g) → O(l) ; ΔH°r = -576 kJ

• The equation shows that 576 kJ of energy is released when two moles of
hydrogen react with one mole of oxygen to give two moles of water.
• This is a theoretical reaction, it does not happen in practice. The enthalpy
change can be found by applying Hess' law (section 2.1.2).
  
Standard enthalpy changes of reactions ()
• The
  standard enthalpy change of reaction () is the
enthalpy change of a reaction according to the molar
quantities in the reaction under standard conditions.
• There are six types of standard enthalpy changes ()
that you need to be familiar with for the purposes of
this syllabus.
– standard enthalpy change of formation (),
– standard enthalpy change of combustion (),
– standard enthalpy change of hydration (),
– standard enthalpy change of solution (),
– standard enthalpy change of neutralisation (),
– standard enthalpy change of atomisation ().
  
Standard enthalpy change of formation ()

•• This
  is the enthalpy change when one mole of a compound is formed
from its elements in their standard states under standard conditions.
• For example, to form one mole of water, the equation is H2 (g) + O2
(g) → H2O (l).
• For water, = 286 kJmol-1.
• Notice that the value for water is negative, meaning that this is an
exothermic reaction.
• For a pure element in its standard state, the = 0 kJmol-1 because
elements in their standard states are not formed, they just exist as
such.
• The standard enthalpy change of formation can be exothermic or
endothermic.
   of combustion ()
standard enthalpy change

• Standard
  enthalpy change of combustion is the
enthalpy change when one mole of a substance is
burnt in excess oxygen (completely burned,
complete combustion) under standard conditions.
• The reactants and products must be in their
standard states.
• (g) +2 (g) → (g) +2O(l);
• ΔH° = 890.3 kJ
• The standard enthalpy change of combustion is
always exothermic.
  
standard enthalpy change of hydration ()
•• Standard
  enthalpy change of hydration, is the enthalpy
change when one mole of gaseous ions dissolve in water to
form hydrated ions of infinite dilution under standard
conditions.
• Ca2+ (g) + (aq) Ca2+ (aq), = 1650 kJmol-1 and (g) + (aq)
• Water is a polar molecule, this means that it has a negative
end and a positive end. The negative end of the water
molecule will be attracted to the cations while the positive
end of the water molecule will be attracted to the anions.
• The attraction set up is called the ion-dipole forces.
• The standard enthalpy change of hydration is always
exothermic.
  
standard enthalpy change of solution ()
• Standard enthalpy change of solution, is the enthalpy
change when one mole of solute is dissolved in a solvent
to form an infinitely dilute solution under standard
conditions.
• NaCl (s) + aq → NaCl(aq) ; ΔH°sol = +6.0 kJ mol⁻1
• NaOH(s) + aq → NaOH(aq) ; ΔH°sol = -44.5 kJ mol⁻1
• An infinitely dilute solution is one which does not
produce any further enthalpy change when more
solvent is added.
• The standard enthalpy change of solution can be
exothermic or endothermic.
   of neutralisation ()
standard enthalpy change

•• Standard enthalpy change of neutralisation, is the enthalpy change when

 
one mole of water is formed by the reaction of an acid with an alkali under
standard conditions.
• HCl(aq) + NaOH(aq) → NaCl(aq) + O (l);
• ΔH = -57.1 kJ mol⁻1
• For any acid-alkali reaction, the ionic equation is:
• H⁺(aq) + OH⁻(aq) → O (l)
• The enthalpy change of neutralisation between strong acids and strong
bases is a constant(-57.1 kJ mol⁻1). This is because all strong acids and
strong bases dissociate completely in water to form aqueous ions.
• So, neutralisation between strong acids and strong bases involves the same
reaction, that is, H⁺ reacts with OH⁻ to form O (l) . The other ions present
are just simply spectator ions. They do not take part in the reaction. Hence,
the heat released is the same.
 standard enthalpy change of neutralisation
 
() ….
• The enthalpy change of neutralisation between sulfuric acid and sodium
• hydroxide
  is more exothermic(-66.8 kJ ) than expected.
• This is because the enthalpy change of dilution of sufuric acid is significant.
When sulfuric acid is added to sodium hydroxide, the acid is diluted in the
process and heat is released.
• The enthalpy change of neutralisation involving weak acids or weak bases is
less than 57.1 kJ mol⁻1.
• For example:
• COOH(aq) + NaOH(aq) → COONa(aq) + O (l);
• ΔH = -56.1 kJ
• NaOH(aq) + HCN(aq) → NaCN(aq) + O (l); ΔH = -11.7 kJ
• This is because weak acids and weak bases only partially dissociated in water.
• For example: COOH(aq) 􂾮 CH3COO⁻(aq) + H⁺(aq) ; ΔH = positive
 standard enthalpy change of neutralisation
 
() ….
• On
  addition of strong base such as NaOH, the OH⁻
ions react with H⁺ from the dissociation of COOH.
The removal of H⁺ ions causes the position of
equilibrium to shift to the right and more COOH
molecules dissociate.
• However the dissociation of COOH is an endothermic
process, hence, some energy is absorbed and the
enthalpy change overall is less negative.
• The standard enthalpy change of neutralisation is
always exothermic.
  
standard enthalpy change of atomisation ()

•• Standard
  enthalpy change of atomisation is the enthalpy change
when one mole of gases atoms is formed from its element under
standard conditions.
• (g) → H(g) ; ΔH [] = +218 kJ
• Na(s) → Na(g) ; ΔH°[Na] = +107 kJ kJ
• By definition, the standard enthalpy change of atomisation of the
noble gases is zero because all of them exist as monoatomic gases
at standard conditions.
• The standard enthalpy change of atomisation of diatomic gases
(example: , , and ) is equal to half the value of their bond energies.
• The standard enthalpy change of atomisation is always
endothermic.
 bond (enthalpy) energy

•• Every
  chemical bond has an energy value. This tells us the
energy required to break that bond.
• Bond energy, E is the energy needed to break one mole of
covalent bonds between two atoms in the gaseous state.
• For example Br-Br(g) → 2Br(g) ; E(Br-Br) = +193 kJ
• Bond energy is often called bond enthalpy or bond
dissociation energy.
• Bonds of the same type do not all have the same amount of
energy. For example, there are four C-H bonds in methane
(CH4) all with slightly different individual bond enthalpies.
• The energy needed to break the first C-H bond is different
from the energy needed to break the second C-H bond and so
on.
 average bond (enthalpy) energy
•• Bond energy is often affected by the presence of other atoms in the
 molecule.
• For example, the O-H bond in water has a different bond energy value
than the O-H bond in ethanol.
• Even in the same molecule, for example, , the energy needed to break all
the C-H bonds are not identical.
• We measure the enthalpy of breaking all the four bonds and divide by 4 to
get the mean bond enthalpy of a C-H bond.
• The average amount of energy needed to break 1 mole of a bond type in a
molecule in the gaseous state is known as the bond energy (enthalpy).
• Therefore, bond energies are taken from a number of bonds of the same
type from different environment and average out to get the average bond
energy.
• The values are not always accurate.
 bond breaking and bond making

•• Bonds
  are broken and made during a reaction. For bond breaking,
energy needs to be absorbed from the surroundings. Therefore,
bond breaking is an endothermic process.
• Bonds are broken in the reactants, and this is an endothermic
process so H is positive.
• When bonds are made, energy is released to the surroundings.
Bonds are made when products are being produced and this is an
exothermic process so H is negative.
• If the energy needed to break bonds is less than the energy released
when new bonds are formed, then the reaction will be exothermic
• If the energy needed to break bonds is more than the energy
released when new bonds are formed, then the reaction will be
endothermic.
• In most chemical reactions, bonds have to be broken first and then
reformed into a new compound.
bond breaking and bond making
bond energies in homonuclear diatomic molecules (these are exact values)

Bond Energy (kJmol−1)

H−H 436
D−D 442
N≡N 944
O=O 496
P≡P 485
S=S 425
F−F 158
Cl−Cl 242
Br−Br 193
I−I 151
bond energies in heteronuclear diatomic
molecules (these are exact values)
Bond Energy (kJmol−1)
H−F 562
H−Cl 431
H−Br 366
H−I 299
C≡O 1077
bond energies in homonuclear polyatomic molecules (these are average
values)

Bond Energy (kJmol−1)

C−C 350
C=C 610
C≡C 840
benzene 520
N−N 160
N=N 410
O−O 150
Si−Si 222
P−P 200
S−S 264
bond energies in heteronuclear polyatomic
molecules (these are average values)
Bond Energy (kJmol−1)
C−H 410
C−Cl 340
C−Br 280
C−I 240
C−N 305
C=N 610
C≡N 890
C−O 360
C=O 740
C=O in CO2 805
N−H 390
N−Cl 310
O−H 460
Si−Cl 359
Si−H 320
Si−O in SiO2 (s) 460
Si=O in SiO2 (g) 640
P−H 320
P−Cl 330
P−O 340
P=O 540
S−H 347
S−Cl 250
S−O 360
S=O 500
 calculating enthalpy change using mean bond energies

• The
  enthalpy change of reaction () = total energy
needed to break bonds total energy released
forming bonds.
Example
• Calculate energy change for combustion of
methane CH4 (g) + 2O2 (g) 2H2O (g) + CO2 (g)

Bond C=O C-H O=O OH

Mean bond 805 410 496 460
enthalpy / kJ/mol
 calculating enthalpy change using
mean bond energies …
••Bond
  breaking - reactants (endothermic)
• 4 C-H = 410 4 = 1640
• 2 O=O = 496 2 = 992
• Total = 2632
• Bond making - products (exothermic)
• 4 O-H = 4 460 = 1840
• 2 C=O = 2 805 = 1610
• Total = 3450
• Enthalpy change = total energy needed to break bonds total
energy released forming bonds
• = 2632 3450
• = 818
• The overall enthalpy change of reaction is exothermic.
 Why ΔH values from calculated bond energies
differ from those obtained from data booklet and
experimentally determined values
• It may be that in the experiment, the heat
transferred to the calorimeter and its contents is
not enough, possibly because heat was lost to the
gauze, tripod and surrounding air.
• It may also be that combustion was incomplete,
some ethanol was lost by evaporation, the
reactants and products were not measured under
standard temperature and pressure conditions.
• These are some of the limitations.
 2.1.2 Hess’ law
• apply Hess’ law to construct simple energy
cycles, and carry out calculations involving such
cycles and relevant energy terms
• apply Hess’ law to determine enthalpy changes
that cannot be found by direct experiment, e.g.
an enthalpy change of formation from enthalpy
changes of combustion
• construct and interpret a reaction pathway
diagram, in terms of the enthalpy change of the
reaction and of the activation energy
Hess’ law
•• Enthalpy
  is a state function, in other words, it depends on the
current state of the system.
• The enthalpy change (H) for a reaction depends only on the initial
and final conditions (difference between enthalpy of the products
and the enthalpy of the reactants) and not the path taken (it does
not depend on how the reaction took place).
• Whether a given reaction occurs in one step or many steps, the
enthalpy change remains the same.
• Germain Hess, a chemist and doctor, proposed Hess’ Law.
• Hess’ Law states that the enthalpy change of a reaction is
independent of the route taken.
• In other words, the enthalpy change associated with a reaction
carried out in multiple steps is equal to the sum of the enthalpy
changes for each individual step.
 Hess’ law
•• Hess'
  law states that the total
enthalpy change in a chemical
reaction is independent of the
route which the reaction takes
place as long as the initial and
final conditions are the same.
• For example, the enthalpy change
of reaction from A to B is the
same whether the reaction takes
place in one stage(A to B) or two
stages(A to C then to B).
• = +
• =
 application of Hess’ law
• The enthalpy change of a reaction cannot always be
directly measured.
• Hess' law is useful to calculate enthalpy changes that
cannot be measured directly from experiments(theoretical
reactions that will not occur under standard conditions).
• Steps to construct a Hess' cycle:
Write down the equation for the enthalpy change that you are
asked to find and write ΔH on top of the arrow.
Use the information that you have been given to complete a
cycle.
Find the direct route and indirect route. The routes should not go
against any arrows. (Equations may be reversed when necessary,
but do not forget to reverse the sign as well.)
Apply Hess' law and form an equation to solve for ΔH.
 Hess’ law cycles
•• Enthalpy
  cycles can be used to help indirectly calculate enthalpy
changes.
• An enthalpy cycle is a pictorial representation showing the
alternative routes of a reaction between reactants and products.
• Enthalpy cycles are triangular. In each corner, there should be the
same number of atoms because, like energy, matter is also
conserved.
• The sides of the rectangle are arrows which show the direction of
the reaction.
• There are two main cycles about Hess’ law you need to be familiar
with namely the formation and combustion cycles.
• The cycle you draw depends on the data you are given. If you are
given enthalpy change of formation () data, you draw a formation
cycle. If you are given enthalpy change of combustion () data, you
draw a combustion cycle.
Hess’ formation
cycle

•• The formation cycle has reactants to form products like a normal reaction.
 
• The arrow of reactants products represents the enthalpy change of
combustion () or the enthalpy change of reaction () depending on what
you are asked in the equation.
• The elements in their standard states are always at the bottom of the
formation cycle.
• The arrows point upwards to the reactants and products and they
represent the enthalpy changes of formation () of the reactants and
products form their constituent elements respectively.
• When you go with the arrow, you keep the sign the same. When you go
against the arrow, you change the sign.
Hess’ formation cycle ….
 Hess’
combustion
cycle
• If you are given combustion data, draw a combustion cycle.
• Combustion cycles always have the products of combustion
carbon dioxide and water at the bottom of the cycle.
• Both arrows pointing downwards always point towards to
combustion products.
• The reactants / elements are placed on the far left top
corner and the products are placed on the far right top
corner.
Hess’ combustion cycle
Reaction pathway diagrams
 Reaction pathway diagrams

• The reaction pathway diagram is a plot of the energy of a substance versus its place in the progress
•  
of the reaction.
• When a reaction is going on, typically it starts with reactants and ends with products.
• At the beginning of the reaction, we have the energy of the reactants and at the end of the reaction
we have the energy of the products.
• For an exothermic reaction, the energy of the reactants is higher than the energy of the products
because the reactants give off energy to the surroundings during the course of the reaction.
• What happens in-between the reactants and the products is that reactants need a certain amount
of activation energy to start them off.
• Some reactions need a small amount of activation energy and others need more activation energy.
• The difference in the potential energy of the reactants and the potential energy of the products
(products reactants) is the enthalpy change of the reaction ().
• If the energy of the products is lower than the energy of the reactants, is negative and the reaction
is exothermic.
• If the energy of the reactants is lower than the energy of the products, is positive and the reaction
is endothermic.
• The energy difference between the transition state and the reactants is the activation energy.
• If a catalyst is added, the activation energy is reduced.
• You should be able to construct and interpret a reaction pathway diagram, in terms of the enthalpy
change of the reaction and of the activation energy.
End of topic activity