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BS MME 2024 Lec#4
BS MME 2024 Lec#4
Thermochemistry
Part-II
By
Sheeraz Mehboob, PhD
E-mail: sheeraz_ravian@hotmail.com
Department of Chemistry
Pakistan Institute of Engineering and Applied
Sciences
1
Thermodynamics
The release of energy can be used:
To provide heat when a fuel burns in a furnace,
To produce mechanical work when a fuel burns in an engine
To generate electrical work when a chemical reaction pumps
electrons through a circuit.
In chemistry, we encounter reactions that:
can be harnessed to provide heat and work,
liberate energy which is squandered (often to the detriment of
the environment) but which give products we require,
constitute the processes of life.
For the purposes of physical chemistry, the universe is divided into two parts, the system and its
surroundings.
The system is the part of the world in which we have a special interest. It may be a reaction vessel, an
engine, an electrochemical cell, a biological cell, and so on.
The surroundings comprise the region outside the system and are where we make our measurements.
The type of system depends on the characteristics of the boundary that divides it from the surroundings.
If matter can be transferred through the boundary between the system and its surroundings the system is
classified as open.
If matter cannot pass through the boundary the system is classified as closed.
Both open and closed systems can exchange energy with their surroundings.
2
The Basic Concepts
• Work: Motion against an opposing force.
• Energy: Capacity to do work
• Heat: Transfer of energy between system and
surroundings due to the difference in temperatures
• Exothermic Process: That releases energy as heat into its
surroundings.
• Endothermic Process: In which energy is acquired from its
surroundings as heat.
3
The internal energy and First Law of Thermodynamics
• In thermodynamics, the total energy of a • It has been found experimentally that the
system is called its internal energy, U.
internal energy of a system may be changed
• The internal energy is the total kinetic and
potential energy of the molecules in the either by doing work on the system or by
system heating it.
• We denote by ΔU the change in internal • Whereas we may know how the energy
energy when a system changes from an
initial state i with internal energy U i to a final
transfer has occurred (because we can see if a
state f of internal energy Uf : weight has been raised or lowered in the
surroundings, indicating transfer of energy by
doing work, or if ice has melted in the
surroundings, indicating transfer of energy as
• The internal energy is a state function in the heat), the system is blind to the mode
sense that its value depends only on the
current state of the system and is employed.
independent of how that state has been • Heat and work are equivalent ways of
prepared. changing a system’s internal energy.
• In other words, it is a function of the • It is also found experimentally that, if a
properties that determine the current state of
the system. Changing any one of the state system is isolated from its surroundings, then
variables, such as the pressure, results in a no change in internal energy takes place.
change in internal energy.
• This summary of observations is now known
• The internal energy is an extensive property.
as the First Law of thermodynamics and
• Internal energy, heat, and work are all
measured in the same units, the joule (J).
expressed as follows:
The internal energy of an isolated system is4
constant.
The internal energy and First Law of Thermodynamics
• If w is for the work done on a system, q for the energy transferred as heat to a
system, and ΔU for the resulting change in internal energy, then it follows
that
ΔU = q + w
• Equation is the mathematical statement of the First Law, for it summarizes
the equivalence of heat and work and the fact that the internal energy is
constant in an isolated system (for which q = 0 and w = 0).
• The equation states that the change in internal energy of a closed system is
equal to the energy that passes through its boundary as heat or work.
• It employs the ‘acquisitive convention’, in which w > 0 or q > 0 if energy is
transferred to the system as work or heat and w < 0 or q < 0 if energy is lost
from the system as work or heat. In other words, we view the flow of energy
as work or heat from the system’s perspective.
5
The Expansion Work
Considering infinitesimal changes, if the work done
on a system is dw and the energy supplied to it as
heat is dq, we have
dU = dq + dw.
To use this expression we must be able to relate dq
and dw to events taking place in the surroundings.
Expansion Work The work arising from a change
in volume.
This type of work includes the work done by a gas as
it expands and drives back the atmosphere.
The term ‘expansion work’ also includes work
associated with negative changes of volume, that is,
compression.
(i) General Expression for Work
The work required to move an object a distance dz
against an opposing force of magnitude F is
dw = -Fdz
Negative sign indicates the decrease in internal Total work done in expanding from
energy. volume Vi to Vf is given by:
6
The Expansion Work
(ii) Free Expansion
By free expansion we mean expansion against zero
opposing force. It occurs when pex = 0. According to eqn ,
dw = 0 for each stage of the expansion. Hence, overall:
Free expansion: w = 0
9
Heat Transactions
10
Heat Transactions
11
Enthalpy
The enthalpy, H, is defined as
H = U + pV
where p is the pressure of the system and V is its volume.
Because U, p, and V are all state functions, the enthalpy is
a state function too.
As is true of any state function, the change in enthalpy,
ΔH, between any pair of initial and final states is
independent of the path between them.
The change in enthalpy is equal to the energy supplied as
heat at constant pressure (provided the system does no
additional work):
dH = dq (at constant pressure, no additional work)
For a measurable change,
H = qp
Eqn states that, when a system is subjected to a constant
pressure, and only expansion work can occur, the change
in enthalpy is equal to the energy supplied as heat.
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Variation of Enthalpy with Temperature
The enthalpy of a substance increases as its temperature is
raised. The relation between the increase in enthalpy and
the increase in temperature depends on the conditions (for
example, constant pressure or constant volume). The most
important condition is constant pressure, and the slope of
the tangent to a plot of enthalpy against temperature at
constant pressure is called the heat capacity at constant
pressure,Cp, at a given temperature.
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