Thermochemistry: Chemical

Energy

Presented by:

T B Moekwa
Department of Chemistry

Chapter 9
 Introduction
• Thermodynamics: The science of energy and its
transformation
• Thermochemistry is defined as the branch of
thermodynamics that focuses on energy changes
occurring during chemical reactions.
• State function: Property whose value depends on the
initial and final state; independent of the path from the
initial to the final state.
• The system is the part of the world in which we have a
special interest e.g. a reaction vessel.
• Around the system is the surrounding.
• System + Surrounding = Universe
• Thermochemistry is defined as the branch of thermodynamics that
focuses on changes occurring during chemical reactions.
 Introduction cont.

• Thermodynamics is the science of the

relationship between heat and other forms of
energy.

• Thermochemistry is the study of the quantity

of heat absorbed or evolved by chemical
reactions.
 Energy and it’s conservation

• For a reaction to take place, the final product of

the reaction must be more stable than the
reactants
• The stability is determined by the Energy
• Less stable substance have higher energy and
are converted into more stable substance with
lower energy
• ENERGY is the capacity or ability to do work or
supply heat
 Energy

Types of Energy

1. Kinetic energy
2. Potential energy
3. Chemical energy
4. Heat energy
5. Electric energy
6. Radiant energy
 Energy
• There are three broad concepts of energy:

• Kinetic Energy is the energy associated with an

object by virtue of its motion.

• Potential Energy is the energy an object has by

virtue of its position in a field of force.

• Internal Energy is the sum of the kinetic and

potential energies of the particles making up a
substance.
 Energy
• Kinetic Energy: An object of mass m and
speed or velocity has kinetic energy Ek equal to

2
Ek  2 mv
1
This shows that the kinetic energy of an object
depends on both its mass and its speed.
 Energy
• Consider the kinetic energy of a person whose
mass is 59.0 kg traveling in a car at 26.8 m/s.

2
Ek  (59.0 kg ) (26.8 m / s )
1
2
4 2 2
2.12 10 kg m / s
4
2.12 10 J
• The SI unit of energy, kg.m2/s2, is given the name
Joule.
• Potential Energy: This energy depends on the
“position” (such as height) in a “field of force”
(such as gravity).

• For example, water of a given mass m at the top

of a dam is at a relatively high “position” h in the
“gravitational field” g of the earth.

E p mgh
 Energy
• Consider the potential energy of water 453.6
kg at the top of a dam 91.44 m.
2
E p (453.6 kg ) (9.80 m / s ) (91.44 m)
5 2 2
4.06 10 kg m / s
5
4.06 10 J
• The SI unit of energy, kg.m2/s2, is given the name
Joule.
 Other forms of Energy
• Thermal energy is the energy associated with
the random motion of atoms and molecules,
which can be measured by Temperature (T)
• Chemical energy is the energy stored within
the bonds of chemical substances, chemicals
releases it in the form of heat or light during rxn
• Nuclear energy is the energy stored within the
collection of neutrons and protons in the atom
• Electrical energy is the energy associated
with the flow of electrons
 Energy
• Internal Energy is the energy of the particles
making up a substance.
• The total energy of a system is the sum of its
kinetic energy, potential energy, and internal
energy, ( E ) or U (in other books).

Etot Ek  E p  E / U
 Energy
• The Law of Conservation of Energy: Energy
cannot be created nor destroyed, it can only be
converted from one form to another.
N.B Remember that the total quantities of
energy remain constant.

THIS LAW IS ALSO KNOWN AS

First Law of Thermodynamics
 Energy
• In chemical reactions, heat is often transferred from the
“system” to its “surroundings,” or vice versa.

• The substance or mixture of substances under study in

which a change occurs is called the thermodynamic
system (or simply system), i.e, substance we focus on
in an experiment - reactants and product (are
collectively called system)

• The surroundings are everything in the vicinity of the

thermodynamic system, i.e, reaction flask, solvents,
the room, building and so on
 Energy
• If the system could truly be isolated from its
surroundings so that no energy transfer occurs
between them, the total internal energy (E) of the
system would be conserved and remain constant
throughout the reaction. This assertion a restatement
of the first law of thermodynamics.
• First law of thermodynamics(restatement) – The
total internal energy E of an isolated system is
constant
• Practically impossible. What is important is to
accurately measure any energy that enters or leaves
the system from the surrounding. Measure changes in
internal energy
 Energy
• Practically impossible. What is important is to
accurately measure any energy that enters or leaves
the system from the surrounding.
• Measure changes in internal energy of the system
between the final state of the system after the reaction
and the initial state of the system before reaction;
E E(final)  E(initial )
• Energy that flows from the system to the surrounding
has a negative sign (the system has lost energy) and
that flowing from the surrounding to the system has a
positive sign (the system has gain the energy).
 Energy
• The internal energy of the system depends on many
things such as chemical identity, sample size, T , P,
physical state (g, l or s) and so forth, but not system’s
past history.
• All that matters is the present condition of the system.
Thus, internal energy is said to be state function, one
whose value depends only on the present state of the
system.
• State function – a function or property whose value
depends only on the present state, or, condition of the
system, not on the path used to arrive at that state.
 Heat of Reaction
• Heat is defined as the energy that flows into or
out of a system because of a difference in
temperature between the system and its
surroundings

• Heat flows from a region of higher temperature

to one of lower temperature; once the
temperatures become equal, heat flow stops.
 Heat of Reaction
• Heat is denoted by the symbol q.
• The sign of q is positive if heat is absorbed by the
system.

• The sign of q is negative if heat is evolved by the

system.

• Heat of Reaction is the value of q required to

return a system to the given temperature at the
completion of the reaction.
 Heat of Reaction
• An exothermic process is a chemical reaction
or physical change in which heat is evolved or
released (q is negative).

• An endothermic process is a chemical

reaction or physical change in which heat is
absorbed (q is positive).
 Enthalpy and Heat Change
• The heat absorbed or evolved by a reaction
depends on the conditions under which it
occurs

• Usually, a reaction takes place in an open vessel,

and therefore at the constant pressure of the
atmosphere.

• The heat of this type of reaction is denoted qp, the

heat at constant pressure.
 Enthalpy and Heat Change
• 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.
- An extensive property is one that depends on
the quantity of substance.

- Enthalpy is a state function, a property of a

system that depends only on its present state and
is independent of any previous history of the
system, or independent of path
 Enthalpy Change
• The change in enthalpy for a reaction at a
given temperature and pressure (called the
enthalpy of reaction) is obtained by
subtracting the enthalpy of the reactants from
the enthalpy of the products

H H (products)  H ( reactants)
 Enthalpy and Change
• The change in enthalpy is equal to the heat
of reaction at constant pressure. This
represents the entire change in internal energy
minus any expansion “work” done by the
system.

H q p
 Expansion work
• Like Energy, work comes in many forms
• Work is defined as the force (F) that produces
the movement of an object times the distance
travelled/ moved (d)
W=Fxd
• Work in chemical system, is the Expansion
work (also pressure –volume, PV work), which
is the work done as the result of a volume
change in the system
• If the reaction is in the container with a
movable piston, the volume of the gas in the
product will force the piston outward against
the pressure of the atmosphere (P) moving the
air aside doing work.
• From Physics,
F = -P x A (Area times pressure)
Since P is external it has negative (-) sign
W = F x d = -P x A x d, A is the area it occupies
and d is the distance moves which is change in
volume (DV)
• Therefore,
w  PV
Work done is pressure exerted times the
volume, hence the name PV work.
• Work energy is leaving the system (negative
sign)
Units for w = L.atm
1 atm = 101 x 103 kg/m.s2 ,thus 1L.atm = 101J

1 m3 = 1000 L
• When the reaction takes place with
contraction in volume rather than expansion

w PV
• i.e, change in volume is negative (-)
Enthalpy and Energy Change
• System can exchange energy or heat with its
surrounding by transferring heat or doing work
• Considering transfer of heat with symbol q and
work given by w  PV

• We can represent the total change in internal

energy of a system, DE, as
• DE = q + w = q – PDV
• Heat (q) is positive, when system gain heat
and negative, when system loses heat
Enthalpy and Energy Change
• Rearranging the equation, to solve for q,
q = DE + PDV
• For a system where the reaction is carried out in a
closed container at constant volume,i.e, DV = 0 then
DE = qV.
• For a system where the reaction is carried out in an
open flask, that keeps the pressure constant, and
allowing the volume to change freely
DE = qP – PDV or DE + PDV = qP
• Because open container reactions are common in
chemistry, the heat change qP is given special symbol
called heat of reaction or enthalpy change (DH)
Enthalpy and Energy Change
• Since the heat at constant pressure, q p,
represents DH, then

E H  PV
• So ΔH is essentially the heat obtained or
absorbed by a reaction in an open vessel
where the work portion of ΔE is unmeasured.
 Enthalpy and it’s Change
• The change in enthalpy for a reaction at a
given temperature and pressure (called the
enthalpy of reaction) is obtained by
subtracting the enthalpy of the reactants from
the enthalpy of the products
H H (products)  H ( reactants)
• The difference between DE and DH is usually
smaller, so the two quantities are nearly equal.
Chem and Physical Changes
• Every change in a system involves either gain
or loss of enthalpy
• Enthalpy change often called heat of
reaction because it is a measure of the heat
flow into or out of the system at constant P
• If enthalpy of products is greater than that of
reactants, then heat flowed into the system and
ΔH has (+) sign and RXNs are called
Endothermic (endo for “within” so heat flows in)
Chem and Physical Changes
• If enthalpy of products is less than that of
reactants, then heat flowed out of the system
to surrounding and ΔH has (-) sign and RXNs
are called Exothermic (exo for “out” so heat
flows out)

• Enthalpy of fusion/Heat of fusion is the

amount of heat necessary to melt a substance
without changing its temperature.
• i.e, solid to liquid (melting)
.
Chem and Physical Changes
• Enthalpy of vaporization/ Heat of
vaporization is the amount of heat necessary/
required to vaporize a substance without
changing its temperature.
• i.e, liquid to gas (boiling)
• Sublimation is the direct conversion of a solid
to a vapor without going through liquid phase
• Enthalpy of sublimation/Heat of sublimation is
equal to the sum of the heat of fusion and heat
of vaporization
.
Chem and Physical Changes
• In the case of sublimation and vaporisation, V f
>> Vi and the expression for work done on gas
becomes W = PVf = -RT for 1 mole of a gas.
 Examples
• Calculate the work done when25g of iron
reacts with hydrochloric acid in
a) a closed system
b) an open beaker at 25oC
 Answer
a) W = 0, since no work is being done.
b) Reaction equation is:
Fe(s) + 2HCl(aq) → FeCl2(aq) + H2(g)
The H2(g) drives the atmosphere back and therefore
work is done by the gas:
W = -P∆V = -PVf = -P x nRT/P = nRT
Since ∆V = Vf and molar mass of Fe is 55.85, then
W = -25g/ 55.85 gmol-1 x (8.314JK-1 mol-1) x (298K)
= -1.1 KJ
Thus the reaction mixture, which constitutes the
system, does 1.1KJ work against the atmosphere.
 Answer (cont.)
• In the case where the ideal gas expands
against the atmospheric pressure, then
W = P∆V = P(Vf – Vi)
For sublimation and vaporisation Vf >> Vi and
the expression for work done on gas becomes
W ≈ -PVf = -RT
For 1 mole of gas.
Calorimetry and Heat capacity
• The amount of heat transferred during a
reaction can be measured with a device called
a calorimeter.
• The reaction is carried out inside the vessel,
and the heat evolved/transferred or absorbed
is calculated from temperature change (DT).
• This temperature measurements makes it
possible to calculate the enthalpy change (DH)
during reaction, because pressure inside
calorimetry is constant.
Calorimetry and Heat capacity
• A “bomb” calorimeter is used to find heat of
combustion; the “bomb” contains oxygen and a
sample of the material to be burned.
• The reactants are ignited electrically, and the
heat evolved/transferred or absorbed is
calculated from temperature change (DT).
• This temperature measurements makes it
possible to calculate DE rather than DH
because reaction takes place at constant
volume.
Calorimetry and Heat capacity
• Heat evolved in a reaction is absorbed by the
calorimeter and its contents.
• In a calorimeter we measure the temperature
change of water or a solution to determine the
heat absorbed or evolved by a reaction, which
depends on the calorimeter’s heat capacity.
• The heat capacity (C) is the quantity of heat
required to change the temperature of the
system by 1 °C or amount of heat required to
raise the temperature of an object or substance
by a given amount. Expressed by Equation
C = q/DT (units are J/°C)
Calorimetry and Heat capacity
• The greater the heat capacity, the greater the
amount of heat needed to produce a given
temperature change.
• Heat capacity (C) is an extensive property, so
its value depends on both the size of an object
and its composition.
• To compare different substances, we use
specific heat capacity or simply specific heat
(c).
Calorimetry and Heat capacity
• The specific heat (c) is the heat capacity of
one gram of a pure substance or the amount of
heat necessary to raise the temperature of 1 g
of a substance by 1 °C.
Specific heat (c) = heat capacity (C )/m =
q/(mDT)
q = specific heat (c ) x mass of substance (m) x
DT
• Molar heat capacity (Cm) is the amount of
heat needed to raise the T of 1 mol of a
substance by 1 °C, given by
• q = Cm x moles of substance x DT
 Calorimetry
• Exercises
• How many milliliters of water at 23 °C with a density of
1.00 g/mL must be mixed with 180 mL of coffee at 95
°C so that the resulting combination will have a
temperature of 60 °C? Assume that coffee and water
have the same density and the same specific heat
(4.184 J/g °C).
• How much will the temperature of a cup (180 g) of
coffee at 95 °C be reduced when a 45 g silver spoon
(specific heat 0.24 J/g °C) at 25 °C is placed in the
coffee and the two are allowed to reach the same
temperature? Assume that the coffee has the same
density and specific heat as water.
 Hess’s Law
• Hess’s law states that for a chemical equation
that can be written as the sum of two or more
steps, the enthalpy change for the overall
equation is the sum of the enthalpy changes
for the individual steps.
• So, you can calculate the enthalpy as the sum
of several small steps.
• There are a few rules that you must follow
when manipulating an equation.
 Hess’s Law
• The rules are as follows;
1. You can reverse the equation. This will
change the sign of ΔH.
2. You can multiply the equation by a constant.
You must then multiply the value of ΔH by the
same constant.
3. You can use any combination of the first two
rules.
• Let’s consider the following
 Hess’s Law
• What is ΔHo (heat of combustion), of the
following reaction?
• CS2(l)+3O2(g)→CO2(g)+2SO2(g) given:
• 1.C(s)+O2(g)→CO2(g) ΔHo=-393.5 kJ
2.S(s)+O2(g)→SO2(g) ΔHo=-296.8 kJ
3.C(s)+2S(s)→CS2(l) ΔHo= 87.9 kJ
• Solution:
• Write down the target equation.
• CS2(l)+3O2(g)→CO2(g)+2SO2(g)
• And organize the given equations so that they
add up to give the target equation.
 Hess’s Law
• Find one of the equations that contains the first
compound in the target equation (CS2),which
would be eq 3, but we must reverse it and
its ΔH to get the CS2 on the left
• CS2(l) →C(s)+2S(s) ΔHo= -87.9 kJ
• Find an equation that contains C(s), that would
be eq 1.
• CS2(l) →C(s)+2S(s) ΔHo= -87.9 kJ
• C(s)+O2(g)→CO2(g) ΔHo=-393.5 kJ
• Now we work on the S(s), but we have to
double it and its ΔH. We then get
 Hess’s Law
• We then get
• CS2(l) →C(s)+2S(s) ΔHo= -87.9 kJ
• C(s)+O2(g)→CO2(g) ΔHo=-393.5 kJ
• 2[S(s)+O2(g)→SO2(g)] ΔHo=-296.8 kJ x 2
• CS2(l)+3O2(g)→CO2(g)+2SO2(g) ΔHo=-1075.0
kJ
• Therefore, heat of combustion for the reaction
is -1075.0 kJ
 Hess’s Law
• Exercise
• Calculate ∆H0 for the reaction CH4 (g) + 3O2 (g)
→ CO2 (g) + 2H2O(l) given the following
information:
• CH4 (g) + 2 O2 (g) →CH2O (g) + H2O (g)
∆H0 = -200 kJ
• CH2O (g) + O2 (g) → CO2 (g) + H2O (g)
∆H0 = -443 kJ
• H2O (g) → H2O (l) ∆H0 = 24 kJ
 Hess’s Law
• Exercise
• Calculate ∆H0 for the reaction NO (g) + O (g)
→ NO2 (g) given the following information:

• NO (g) + O3 (g) →NO2 (g) + O2 (g)

∆H0 = -200 kJ O 3 (g)
→ 3/2O2 (g) ∆H0 = -143 kJ O2 (g)
→ 2O (g) ∆H0 = 498 kJ