Week 3

Energy changes in chemical reactions

Energy changes in chemical reactions
• All chemical reactions involve an energy change. Which is a
transfer of energy into or out of a reaction mixture.
• When petrol is burned energy is given off in a form of heat. And
when ammonium nitrate is dissolved in water heat is taken in.
• In a chemical reaction reactants are converted into products:
ReactantsProducts
• in any such reaction energy change will occur.
• The energy change are given the symbol ΔH.
• ΔH=Σtotal energy of products- Σtotal energy of reactants
Temperature change
• Some reactions cause the temperature of the reaction
mixture to increase. This type of reaction is called
exothermic. ΔH is -ve.
• Heat energy is given out by the reaction mixture hence the
surroundings increase in temperature.
• Some reactions cause the temperature of the reaction
mixture to decrease. This type of a reaction is called
endothermic. ΔH is +ve.
• Heat energy is taken in by the reaction mixture hence the
surroundings decrease in temperature
Energy diagrams
• The energy changes in a chemical reaction can be
represented using energy level diagrams.
• Energy diagrams make it easier for us to decide whether a
reaction is endothermic or exothermic.
• In an exothermic reaction, the products are at a lower
energy than the reactants. The difference between the
energy of the reactants and the energy of the products is
called the enthalpy change (ΔH) of the reaction.
• For an exothermic reaction, the enthalpy change is always
negative.
Exothermic reaction
• In an exothermic reaction,
the products are at a lower
energy than the reactants.
• The difference between the
energy of the reactants and
the energy of the products is
called the enthalpy change
(ΔH) of the reaction.
• For an exothermic reaction,
the enthalpy change is
always negative.
Endothermic reaction

• In an endothermic
reaction, the products are
at a higher energy than
the reactants.
• This means that the
enthalpy change of the
reaction (ΔH) is positive
Endothermic and exothermic reactions
H2(g) + Cl2(g) 2HCl(g) H =-185 kJ.mol-1 Exothermic

H2(g) + I2(g) 2HI(g) H =+ 53kJ.mol-1 Endothermic

Making and Breaking Bonds

• All chemical reactions involve bond

‘rearrangements’.
• Bonds are broken and new ones are formed.
• Making chemical bonds is always exothermic.
• Breaking chemical bonds is always endothermic.
The law of conservation of energy

• The law of conservation of energy states that energy cannot

be created or destroyed, but can be converted from one
form to another.
• Thus the energy given out by an exothermic reaction cannot
just disappear – it will be absorbed by the surroundings and
the temperature of the surroundings generally rises
• Conversely the energy absorbed by an endothermic reaction
is obtained from the surroundings and the temperature of
the surroundings will generally drop.
Enthalpy
• Enthalpy (denoted H) is an extensive property of a substance
that can be used to obtain the heat absorbed or evolved in a
chemical reaction.
• Most chemical reactions occur at constant pressure and so we
usually talk about ‘enthalpy changes’ rather than ‘energy
changes’.
• Enthalpy is a state function. A state function is a property of a
system that depends only on its present state, which is
determined by variables such as temperature and pressure, and
is independent of any previous history of the system.
• This means that a change in enthalpy does not depend on how
the change was made, but only on the initial state and final state
of the system.
Standard Enthalpy Changes, ΔHo
• It is important to realize that the actual enthalpy, H, (energy)
of a substance, element or compound cannot be measured.
• Only changes of enthalpy, H can be measured.
• The standard enthalpy change, ΔHo is the enthalpy change
that occurs when all the reactants and products are in their
standard states.
• The standard state of a substance is its normal, pure form at
a pressure of 1 atm.
• The standard states of water at -10 oC; 20 oC and 120 oC refer
to H2O(s); H2O(l) and H2O(g) respectively.
Reference States
• When elements occur with more than one allotrope(another
form) then the most stable form is usually taken as the
reference state.
• Most elements have only one allotrope at 1 atm and so it is
not necessary to identify a reference state.
• Four common elements with more than one allotrope are
listed below.
• Oxygen: dioxygen O2, and ozone, O3
• Carbon: graphite and diamond
• Sulphur: rhombic and monoclinic
• Phosphorus: white and red
Key points about Enthalpy changes
• 1. ΔH values change when the stoichiometry coefficients of
the reaction are changed. For this reason, when a value of
ΔH is stated, it is also necessary to write the relevant
equation.
H2(g) + I2(s)  2 HI(g) ΔH = +52 kJ.mol-1

½ H2(g) + ½ I2(s)  HI(g) ΔH = +26 kJ.mol-1

2H2(g) + 2 I2(s) 4 HI(g) ΔH = +104 kJ.mol-1

Key points about Enthalpy changes
• 2. Reversing a chemical equation reverses the sign of ΔH. That
is, if the forward reaction is exothermic, then the reverse
reaction must be endothermic.
H2(g) + I2(s)  2 HI(g) ΔH = +52 kJ.mol-1
• 2 HI(g) H2(g) + I2(s) ΔH = -52 kJ.mol-1
• 3. When giving ΔH values, the physical state of the reactants
and products must be stated.
H2(g) + I2(s)  2 HI(g) ΔH = +52 kJ.mol-1
H2(g) + I2(g)  2HI(g) ΔH = - 9 kJ.mol-1
Key points about Enthalpy changes
• 4. When a particular reaction can occur by more than one
route, then ΔH is the same whichever route is taken. This
statement is known as Hess’s Law.
• A. H2(g) + I2(s)  2 HI(g) ΔH = +52 kJ.mol-1
• B. H2(g) + I2(g)  2 HI(g) ΔH = -9kJ.mol-1
• C. I2(s) I2(g) ΔH = +61 kJ.mol-1
Hess law examples
Use Hess’s Law, to calculate ΔH for the following reaction:
HCl(g) + NH3(g)  NH4Cl(s) ΔH = ?
A. H2(g) + Cl2(g)  2 HCl(g) ΔH = - 184.6 kJ.mol-1
B. 2 NH3(g)  N2(g) + 3 H2(g) ΔH = + 92.2 kJ.mol-1
C. ½ N2(g) + 2 H2(g) + ½ Cl2(g)  NH4Cl(s) ΔH = - 314.4 kJ.mol-1
ΔH of D = - ½ A + ½ B + C HCl(g)  ½ H2(g) + ½ Cl2(g)
= - ½ (- 184.6) + ½ (92.2) + - (314.4) NH3(g) ½ N2(g) + 3/2 H2(g)
= - 176.0 kJ.mol-1 ½ N2(g) + 2 H2(g) + ½ Cl2(g)  NH4Cl(s)
HCl(g) + NH3(g)  NH4Cl(s)
 Calculate ΔH for the reaction
4 NH3 (g) + 5 O2 (g)  4 NO (g) + 6 H2O (g),
Given that :
(a) N2 (g) + O2 (g) 2 NO (g) ΔH = -180.5 kJ
(b) N2 (g) + 3 H2 (g) 2 NH3 (g) ΔH = -91.8 kJ
(c) 2 H2 (g) + O2 (g) 2 H2O (g) ΔH = -483.6 kJ
ΔH = 2(a) + -2 (b) + 3(c) 2 N2 (g) + 2O2 (g) 4 NO (g)
4 NH3(g) 2N2 (g) + 6 H2 (g)
= 2(-180.5) + -2 (-91.8) + 3(-483)
6 H2 (g) + 3O2 (g) 6 H2O (g)
=-1626.4 4 NH3(g) + 5O2 (g) 4 NO (g)+ 6 H2O (g)
 Find the Δ H for the reaction below, given the following reactions and
subsequent Δ H values:
HCl(g) + NaNO2(s) → HNO2(l) + NaCl(s)
A. 2 NaCl(s) + H2O(l) → 2 HCl(g) + Na2O(s) Δ H = 507 kJ
B. NO(g) + NO2(g) + Na2O(s) → 2 NaNO2(s) Δ H = –427 kJ
C. NO(g) + NO2(g) → N2O(g) + O2(g) Δ H = –43 kJ
D. 2 HNO2(l) → N2O(g) + O2(g) + H 2O(l) Δ H = 34 kJ
ΔH = -1/2 A + -1/2 B HCl(g) + ½ Na2O(s) → NaCl(s) + ½ H2O(l)
+ 1/2 C + -1/2 D NaNO (s)→ ½ NO(g) + ½ NO (g) + ½ Na O(s)
2 2 2
= -1/2(507) + -1/2 (-427) ½ N2O(g) + ½ O2(g) + ½ H 2O(l) → HNO2(l)
+ -1/2(34)+1/2(-43)
½ NO(g) + ½ NO2(g) → ½ N2O(g) + ½ O2(g)
=-78 kJ
HCl(g) + NaNO2(s) → HNO2(l) + NaCl(s)
Experimental determination of ΔH
• Several experimental techniques may be used to measure ΔH
for chemical reactions.
• These include calorimetry, spectroscopy and electrochemical
methods.
• The method used depends on the type of chemical reaction.
• For many reactions ΔH cannot be accurately measured
experimentally. In such cases Hess’s law may be used.
Standard enthalpy of reaction ΔrH o

• The term standard state refers to the standard thermodynamic

conditions chosen for substances when listing or comparing
thermodynamic data: 1 atm pressure and the specified
temperature (usually 25oC).
• The enthalpy change for a reaction in which reactants in their
standard states yield products in their standard states is denoted
ΔH.
• All the ΔH’s we have used up until now are standard reaction
enthalpies, ΔrHo.
• This symbol(ΔrHo) has no meaning unless the actual reaction
(equation) it refers to is written down.
Some Special cases of the Standard Reaction
Enthalpies
1. The standard formation enthalpy, ΔfHo
• It is defined as the enthalpy change for the formation of one mole
of the substance in its standard state from its elements in their
reference form and in their standard states.
• Example: ΔfHo (H2O, l) = - 285.83 kJ.mol-1 refers to this equation:
H2(g) +O2(g)H2O(l) ΔfHo = - 285.83 kJ.mol-1
N2(g) + H2(g) NH3(g) ΔfHo = - 46 kJ.mol-1
• Note that ΔfHo for elements is always zero
Some Special cases of the Standard Reaction
Enthalpies
• 2. The standard combustion enthalpy, ΔcHo
• This is defined as the energy released when one mole of a
combustible substance reacts with excess oxygen to form
products. ΔcHo is always exothermic.
• Example: ΔcHo (CH4, g) = -890 kJ.mol -1 refers to the process
• CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(l)
• Note that all organic compounds that contain C, H and O only will
burn with excess oxygen to produce CO2 and H2O only.
Some Special cases of the Standard Reaction
Enthalpies
• 3. The standard vaporization enthalpy, ΔvapHo
• This is defined as the energy required to convert one mole of a
liquid to a vapour at the same temperature. (phase change from
liquid to gas)
• Example: ΔvapHo (H2O) = + 44 kJ.mol-1 refers to the process
H2O(l)  H2O(g) ΔvapHo = + 44 kJ.mol-1
H2O(g)  H2O(l) ΔconHo = - 44 kJ.mol-1
H2O(s)  H2O(l) ΔfusHo = + 6 kJ.mol-1
Some Special cases of the Standard
Reaction Enthalpies
• 4. Please note that the values of ΔrHo are meaningless
without the relevant chemical equations.
• However, ΔfHo, ΔcHo, and ΔvapHo are defined in terms of
specific reactions and it is not necessary to write their
corresponding chemical reactions.
Calculations of ΔrHo from ΔfHovalues
rHo = Σ n. ΔfHo(products) - Σ n. ΔfHo(reactants)

Given that ΔfHo(CO2(g))=-393 kJ.mol-1, what is ΔrHo for the

following reaction?
C (graphite) + O2(g)  CO2(g)

rHo = Σ n. ΔfHo(products) - Σ n. ΔfHo(reactants)

=1(-393kJ.mol-1)-(1(0)+1(0)
=-393 kJ.mol-1
Example: Using the ΔfHo values, calculate ΔrHo for the
following reaction:

4NH3(g) + 5 O2(g)  4 NO(g) + 6 H2O(l)

ΔfH (NH3(g))= -46 kJ
o
ΔfH (H2O)= -286 kJ
o
fHo
(NO(g))= -90 kJ

ΔrHo = Σ n. Δ fHo (products) - Σ n. ΔfHo (reactants)

=[4(NO)+6(H2O)]-[4(NH3) +5(O2)]
=[4(90)+6(-286)]-[4(-46)+5(0)]
=-1172 kJ.mol-1
 Consider the equation
CH4(g) + 4Cl2(g)  CCl4(l ) + 4HCl(g); what is ΔHo?

ΔfHo(CH4(g))= -74.9 kJ, ΔfHo (HCl(g))= -92.3 kJ , ΔfHo (CCl4)= -135.4 kJ

ΔrHo = Σ n. Δ fHo (products) - Σ n. ΔfHo (reactants)

=[4(HCl)+1(CCl4)]-[4(Cl2) +1(CH4)]

=[4(-92.3)+(-135.4)]-[4(0)+1(-74.9)]
=-429 kJ.mol-1