Module 5:
Thermochemistry
Thermochemistry – is the study of
energy changes during a chemical
reaction and/or change in phase.
- is the
study of the quantity of heat absorbed or
evolved by chemical reactions.
Energy – refers to the capacity to do work
or supply heat.
Types of Energy
1. Kinetic energy
2. Potential energy
3. Chemical energy
4. Heat energy
5. Electric energy
6. Radiant energy
Kinetic energy – is the energy in motion.
- is the energy associated
with an object by virtue of
its motion.
- It is dependent on the
mass and velocity of an object.
FORMULA:
where:
m = mass of the object
v = velocity
Consider the kinetic energy of a person whose mass
is 59.0 kg traveling in a car at 26.8 m/s.
NOTE: The SI unit of energy, , is given the
name Joule.
Potential energy – is the energy at rest.
-This energy depends
on the “position”
(such as height) in a “field of force”
(such as gravity).
- is due to the position
or composition of an
object.
FORMULA:
where:
m = mass of the object
g = gravity (field of
force)
Consider
. the potential energy of 453.6 kg
of water at the top of a 91.44 m
System – could be a reactant, a product, or a
reaction vessel including its components.
Surroundings – refers to the system’s immediate
environment or the things found outside in the
system.
A system and its surrounding make up the universe.
Heat – is defined as the energy that is either release
or absorbed due differences in temperature
conditions.
Exothermic process – a process or reaction
involving the release of heat.
Endothermic process – those that involve the
absorption of heat.
- favors an increase in temperature .
Exothermic Reaction – favors a decrease in
3 Types of Systems
1. Open System: e.g. water in an open
container. Can exchange mass and
heat with surroundings(in the form of
heat).
2. Closed System: e.g. water in a closed
containers. Only transfer of energy,
not mass.
3. Isolated System: e.g. water in a
insulted container. No transfer of mass
or energy
The calorie (cal) is the unit used to express energy.
It is defined as the amount of heat needed to
increase the temperature of 1 gram of pure water by
274 K (1Its equivalent SI unit is joule or . One gram
of pure water requires 1 joule (J) of heat to increase
the temperature by 273.38 K (0.2390 )
1 J = 0.2390 cal
To convert J to liter-atmosphere (L-atm) or liter-
pascal (L-Pa), the R value can be 0.08205
L-atm/mol-K (8314 L-Pa/mol-K) or 8.314 J/mol-K.
The First Law of Thermodynamics
Thermodynamics – is the study of energy and its transformations.
- is the science of the relationship between heat and other
forms of energy.
First law of thermodynamics states that the energy of the universe is
constant. It is also referred to as the Law of conservation of energy, which
states that energy is neither created nor destroyed.
-Energy may be converted from one form to another, but the total quantities of
energy remain constant.
Internal energy – the total energy summation of potential and kinetic energies
(E).
- is the sum of the kinetic and potential energies of
the particles making up a substance.
Heat is represented by (q).
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
Thermodynamic System
The substance under study
in which a change occurs is
called the thermodynamic
system (or just system).
Thermodynamic
Surroundings
Everything else in the
vicinity is called the
thermodynamic
surroundings (or just the
surroundings).
NOTE: If q is positive (q = +), then the energy of the system is
increased. If the q is negative (q = -) then the energy flows from the
system to the surrounding, indicating a decrease in the energy of the
system.
(q = +); Endothermic;
(q = -); Exothermic;
Where P is the pressure of the gas, A is the area of cylinder, F is then
force applied .
Substituting this equation, you now have
Pressure–Volume Work
PV work is work that is the result of a volume
change against an external pressure.
When gases expand, DV is +, but the system is
doing work on the surroundings, so wgas is –.
As long as the external pressure is kept constant,
–work = external pressure × change in volume
w = –PDV
To convert the units to joules, use 101.3 J = 1 atm∙L.
Ex. 1
Calculate the change in the internal energy of a piston
expanding against a pressure of 0.75 atm from 10.3 L to 22.4
L. In the process, 1030 J of heat is absorbed.
Given:
P= 0.75 atm
q = 1030 J
Ex. 2
Calculate the change in the
internal energy of a piston
expanding against a pressure
of 0.55 atm from 15.7 L to
33.3 L. In the process, 2468 J
of heat is absorbed.
Enthalpy or Heat of a Chemical Reaction:
Thermochemical Equations
• 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.
• If a process takes place at constant
pressure (as the majority of processes
we study do) and the only work done is
this pressure–volume work, we can
account for heat flow during the
process by measuring the enthalpy of
the system.
• Enthalpy is the internal energy plus
the product of pressure and volume:
H = E + PV
• When the system changes at constant
pressure, the change in enthalpy, H, is
H = (E + PV)
• This can be written
H = E + PV
• Since E = q + w and w = −PV, we can
substitute these into the enthalpy expression:
H = E + PV
H = (q + w) − w
H = q
• So, at constant pressure, the change in
enthalpy is the heat gained or lost.
The change in enthalpy, H, is the
enthalpy of the products minus the
enthalpy of the reactants:
H = Hproducts − Hreactants
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
Calorimetry
Calorimetry is a scientific way of
determining the quantity of heat by measuring
the changes in the temperature of a system.
Calorimeter is used for such purpose; it is
used to measure the amount of heat involve in a
chemical reaction or other processes.
A calorimeter is a device used to measure
the heat absorbed or evolved during a physical
or chemical change.
A substance possesses the property of heat
capacity, C, which is mathematically represented
as:
𝒉𝒆𝒂𝒕 𝒂𝒃𝒔𝒐𝒓𝒃𝒆𝒅 (𝒊𝒏 𝑱𝒐𝒖𝒍𝒆𝒔 )
𝑪=
𝒄𝒉𝒂𝒏𝒈𝒆 𝒊𝒏𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 ( ∆ 𝑻 , 𝒊𝒏 𝑲𝒆𝒍𝒗𝒊𝒏)
• The specific heat capacity is the
amount of heat energy required to
raise the temperature of one gram
of a substance 1 °C.
• The molar heat capacity is the
amount of heat energy required to
raise the temperature of one mole
of a substance 1 °C.
• A thermochemical equation is
the chemical equation for a
reaction (including phase labels)
in which the equation is given a
molar interpretation, and the
enthalpy of reaction for these
molar amounts is written directly
after the equation.
• Chemical reaction with an
indicated change in enthalpy is
called thermochemical
Bomb Calorimetry
• Reactions can be carried out in a sealed “bomb” such as this
one.
The heat absorbed (or released) by the water is a very good
approximation of the enthalpy change for the reaction.
• Because the volume in the bomb calorimeter is constant,
what is measured is really the change in internal energy, E,
not H.
For most reactions, the difference is very small.