1.

0 THERMOCHEMISTRY
Learning Outcomes
At the end of this topic, you should be able to:

1. Explain the concept of chemical energy, potential energy, work, heat, heat
capacity, specific heat capacity and Hess’s Law
2. Draw energy profiles diagram of exothermic and endothermic reactions.
3. Distinguish the differences between the reaction in a simple and bomb
calorimeter
4. Calculate the heat of reaction, enthalpy of combustion and enthalpy of
formation.
 Contents
1.1 Exothermic and endothermic reactions
1.1.1 Energy profile
1.1.2 Activation energy for reversible and non reversible reaction
1.2 Enthalpy and enthalpy change
1.2.1 Definitions of heats of reaction, enthalpy of combustion and enthalpy of formation
1.2.2 Calculation of heats of reaction using standard enthalpy of formation
1.3 Calorimetry
1.3.1 Heat capacity and specific heat
1.3.2 Simple calorimeter and bomb calorimeter
1.3.3 Calculation of enthalpy of combustion
1.4 Hess’s Law
1.4.1 Definition and calculation
 branch of thermodynamics

Study of the energy transferred as heat during the

THERMOCHEMISTRY course of chemical reactions

A reaction vessel and its contents form a system, and

chemical reactions result in the exchange of energy
between the system and the surroundings
 WORK
• the transfer of energy resulting from a process that
causes or utilize motion of atoms in the surroundings ENERGY
• done to achieve motion against an opposing force capacity of a system to do work
Work = force x distance

The process of raising a weight against the pull  When work is done on an isolated system
of gravity (for example by compressing a gas),
the capacity of the system to do work is
work is done on a system, when molecules in the
surroundings are used to transfer energy to it in increased; the energy of the system is
an organized way as the atoms in a weight are increased.
lowered.

A chemical reaction that drives an electric current  When the system does work
through a resistance (i.e. when the piston moves out)
the energy of the system is reduced and it can
work is done on a system, when molecules in the do less work than before.
surroundings are used to transfer energy to it in an
organized way as a current of electrons is passed.
• Kinetic energy
– energy of motion

• Potential energy
– energy due to condition/position/composition

• Chemical energy
– energy stored within the structural units of
chemical substances
HEAT
When the energy of a system changes as a result of a
temperature difference between the system and its
Boundaries that do permit the transfer of energy as
surroundings we say that energy has been transferred heat are called diathermic;
as heat.
Boundaries that do not permit the transfer of energy
those parts around the system as heat are called adiabatic.
that interact with the system

substances involved in a reaction

TYPES OF SYSTEM
Exchanging matter and Exchange energy Exchange neither
energy with its but not matter energy nor matter
surroundings

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1.1 Exothermic and endothermic reactions
1.1.1 Energy profile
Exothermic Reaction ENERGY LEVEL DIAGRAM
• Process that release energy to the surroundings in
the form of heat energy/thermal energy Reactants
H
• E.g.: combustion reactions and forming of chemical
bond
∆H = - x kJ
• Heat flow : System → Surroundings
∆H = negative sign (-)
due to lowering of potential energy of reaction system
PE Products < PE Reactants q<0 Products
• Causing the reaction mixture and its surroundings to
become hotter
• Reaction temperature increase Reaction pathway
Energy profile diagram (Exothermic reaction)

❑ The products have a lower energy than the

reactants, so energy is released when the
reaction happens.
❑ Molecules have to possess enough energy
(called activation energy) to get the products.
❑ T (system) decrease
❑ T (surrounding) increase

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A few examples of exothermic reactions are:

▪ Mixing of acids and alkalis (releases heat)

▪ Combustion of fuels (releases heat and light)

CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g) + heat

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 Endothermic Reaction
• Any reaction that absorbs energy from the ENERGY LEVEL DIAGRAM
surroundings in the form of heat.
Products
• Example - the vaporization of water, electrolysis and H

breaking chemical bond.

∆H = +x KJ
• Heat is supplied to the system by the surrounding
∆H = positive sign (+)
• Energy flow into the system as heat is used to
increase potential energy of system
Reactants
PE Products > PE Reactants q>0
• Reaction temperature decrease Reaction pathway

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Energy profile diagram (Endothermic reaction)

• The products have higher energy than the

reactants, and so energy absorb when the
reaction happens

• T (system) increase
• T (surrounding) decrease

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A few examples of endothermic reactions are:

▪ Dissolving ammonium nitrate (NH4NO3) in water (absorbs heat and cools the
surroundings)
▪ Photosynthesis of chlorophyll plus water plus sunlight to form
carbohydrates and oxygen (absorbs light)

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1.1.2 Activation energy for reversible and non reversible reaction
Energy Profile
➢ Activation energy, Ea : Is the minimum amount of energy of the reactant
molecules required in order to form products.

➢ On an energy profile, the activation energy is measured from the energy of the
reactants to the peak of the energy profile diagram.

➢ The lower the activation energy, the faster the reaction will proceed.

➢ ∆H is the amount of energy absorbed or released by the reaction. On the energy

profile diagram, ∆H is measured between the energy of the reactant to the energy of
the products.
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1.1.2 Activation energy for reversible and non reversible reaction
Reversible reaction
chemical reaction that occurs in both direction (forward and reverse)

2 SO2(g) + O2(g) 2 SO3(g)

COCl2(g) CO(g) + Cl2(g)
N2(g) + O2(g) 2 NO(g)
Non reversible reaction
chemical reaction that occurs in forward reaction only

neutralization: NaOH + HCl → NaCl + H2O

double decomposition: Na2SO4 + BaCl2 → 2 NaCl + BaSO4

Activation energy for non reversible reaction

Activation energy: minimum energy required for chemical reaction to occur

Activation energy for reversible reaction

transition state
transition state

•the activation energy for the forward reaction: the difference in •the activation energy for the forward reaction: the difference in
energy between the reactant(s) (left) and the transition state (hill) energy between the reactant(s) (left) and the transition state (hill)
•the enthalpy of reaction is the difference in energy between the •the enthalpy of reaction is the difference in energy between the
product(s) (right) and reactant(s) (left) product(s) (right) and reactant(s) (left)

The activation energy of the reverse reaction: the difference in The activation energy of the reverse reaction: the difference in
energy between the product(s) (right) and the transition state (hill). energy between the product(s) (right) and the transition state (hill).
Thus, for this endothermic reaction, Ea,rev = Ea,fwd − ΔHrxn. Thus, for this exothermic reaction, Ea,rev = Ea,fwd + ΔHrxn.
 Describing the condition of the system by giving the values of a sufficient
STATE OF SYSTEM set of numerical variables

a property of a system that depends only on the current state (condition) of the
system, not on the way in which the system acquired that state (independent of path).

State Function
(State Variable) describes the equilibrium state of a system.

Example: internal energy (U), enthalpy (H) and entropy (S) are state quantities
because they describe quantitatively an equilibrium state of a thermodynamic system,
irrespective of how the system arrived in that state.
 Internal Energy (U)
• total energy of a system
• extensive property (directly proportional to the amount of material in the system - mass and
volume) of a system and is measured in joules (1 J = 1 kg m2 s−2).
• ∆U is the change in internal energy when a system changes from an initial state i with internal
energy Ui to a final state f of internal energy Uf
ΔU = Uf – Ui
• Um,(molar internal energy) is the internal energy divided by the amount of substance in a system,

Um = U/n

• intensive property (does not depend on the system size or the amount of material in the system -
temperature, refractive index, density) and commonly reported in kilojoules per mole (kJ mol−1).
 First Law of Thermodynamics
• internal energy of a system may be changed by doing work on the system or by heating
(i.e transfer of energy by doing work or transfer of energy by heating)

• if a system is isolated from its surroundings, then no change in internal energy takes
place
U=q+w

(w = work done, q = heat transferred)

q = + (heat flows into the system from the surrounding) internal energy is constant
q = - (heat flows from the system to the surroundings) in an isolated system (for
w = + (work is done on the system by the surrounding) which q = 0 and w = 0)
w = - ( system does work on the surroundings)
 Example:
1. If an electric motor produced 15 kJ of energy each second as mechanical work and lost 2 kJ
as heat to the surroundings, what is the change in the internal energy of the motor each
second?
∆U = q + w
∆U = −2 kJ −15 kJ = −17 kJ

2. Suppose that, when a spring was wound, 100 J of work was done on it but 15 J escaped to the
surroundings as heat. What is the change in internal energy of the spring ?
∆U = q + w
∆U = − 15 J + 100 J = +85 J

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3. Calculate ΔU for a system undergoing an endothermic process in which 15.6 kJ of heat flows
and where 1.4 kJ of work is done on the system.

Using, ∆U = q + w
given q = +15.6 w = + 1.4 kJ
∆U = (15.6 + 1.4) kJ = 17.0 kJ

The system has gained 17.0 kJ of energy

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 Expansion work
• Proportional to the external pressure.
• Free expansion (against zero pressure) does
no work.
• The work of expansion against constant
pressure is proportional to that pressure
and to the change in volume.
• To achieve reversible expansion, the external
pressure is matched at every stage to the
pressure of the system.
• The work of reversible, isothermal expansion
of a perfect gas is a logarithmic function of When a piston of area A moves out through a distance dz, it
the volume. sweeps out a volume dV =Adz. The external pressure pex is
equivalent to a weight pressing on the piston, and the force
opposing expansion is F = pexA.
F=PxA
dw = -Fdz (note: W = F x d)
Since F = pextA
dw = −pexAdz dV = Adz
= −pex dV

To obtain the total work done when the volume changes from an initial value Vi to a final value Vf we integrate
this expression between the initial and final volumes:

∆V = Vf − Vi,  w = - pexΔV

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w = - pexΔV
(If the system is compressed Vf < Vi)
 Expansion – work is done by the system to the surroundings, w = -
Compression – work is done to the system by the surroundings, w = +

For expansion of a gas,

w = - PΔV
Since ∆U = q + w
= q + (-pexΔV) If ∆V = 0 (adiabatic bomb calorimeter)
∆U = qv
(The heat change of a reaction at constant volume)
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