The First Law of Thermodynamics

Conservation of Energy (1st law of thermodynamics)

 one of the most fundamental laws of nature is the conservation of energy principle. It
simply states that during an interaction, energy can change from one form to another
but the total amount of energy remains constant.
Effect of Heat on a System
 Suppose that a system gains heat Q and that is the only effect occurring.
 Consistent with the law of conservation of energy, the internal energy of the system
changes:
 Heat is positive when the system gains heat and negative when the system loses heat.
Effect of Work on a System
 If a system does work W on its surroundings and there is no heat flow, conservation of
energy indicates that the internal energy of the system will decrease:
 Work is positive when it is done on the system and negative when it is done by the
system.

Ideal Gas Equation

The macroscopic properties of matter (as stated in the introduction of thermodynamics in this
module) can be described by state variables. These are the physical quantities such as
pressure (p), volume (V), temperature (T), and amount of substance. For simple cases, the
relationship among them can be expressed in an equation called the equation of state.
pV= nRT
the proportionality constant R is called the ideal gas constant.
R= 8.314 J/mol = 0.0821 L

Microscopically, the behavior of an ideal gas can be explained by Kinetic Molecular Theory
which states that:
 Gas particles move in straight line and obey Newton’s laws.
 Gas particles have negligible volumes.
 The intermolecular forces between gas particles are negligible.
 The temperature of a gas is proportional to the average translational kinetic energy.
Example: What is the volume of 1 mol of an ideal gas at STP?
Solution: Big Idea
Given: Ideal gas does not exist. But it
STP stands for standard temperature and pressure conditions has been the basis to describe
T= 0 = 273.15 K how gases react to external
P = 1 atm = 1.013 x 105 N/m2 stimuli.

V= = = 22. 4 x 10-3 m3

What Have I Learned So Far?

Solve. Show your solution.
A sample of neon with a molar mass of 20.18 g/mol has a volume of 2.00 L under a pressure of
1.10 atm and at temperature of 39.0 . It is eventually warmed up to have its pressure and
volume double in value. Assuming that that it behaves like an ideal gas, what is the final
temperature of this particular sample of neon?

THERMODYNAMIC PROCESSES
Thermodynamic process is said to take place if some change occurs in the state of a
thermodynamic system, i.e. the thermodynamic variables of the system - pressure, volume,
temperature and entropy change with time.

In practice, the following types of thermodynamic processes can take place:

 Isothermal process: A thermodynamic process that takes place at constant temperature.
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 Isobaric process: A thermodynamic process that takes place at constant pressure.
 Isochoric process: A thermodynamic process that takes place at constant volume.
 Adiabatic process: A thermodynamic process in which no heat enters or leaves the system.
 Cyclic process: A thermodynamic process in which the system returns to its original state.

1. Isothermal Expansion or Compression of an Ideal Gas

Example: An ideal gas is compressed in an isothermal manner by removing 335 J of heat. What
amount of work was done in this case?

Solution: Because heat was released by the ideal gas, Q (heat) = -335 J. For an isothermal
process, Q=W. Thus, W = -335 J. (Negative sign means that work is done on the gas)

2. Isobaric Process


W   PV   P V f  Vi 
Work by the system is the area
under a PV graph.
Work is path dependent

Example: Isobaric Expansion of Water

One gram of water is placed in the cylinder
W  PV
and the pressure is maintained at 2.0x105Pa. W  2.0 105 Pa 1.0 108 m3 
The temperature of the water is raised by
31oC. The water is in the liquid phase and  0.0020J
expands by the small amount of 1.0x10-8m3. Negative means heat is released by
Find the work done. the gas
3. Isochoric Process

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 Example: An ideal gas undergoes
an isochoric process that changes
its temperature from 20 to 50 .
If 50 J of heat was added to the
gas during this process, by how
much did its internal energy
change?
Solution:
In this problem, Q= 50 J. For an
isochoric process, Q= Thus, =
= 50 J

The positive value for means that the internal energy and the temperature of the ideal gas
have increased.

4. Adiabatic Expansion/Compression of a
Monatomic Ideal Gas
Adiabatic: no heat transfer

Case 1: Adiabatic Expansion

 The work done by the
gas is positive
 Change in internal
energy is negative
Case 2: Adiabatic
Compression
 The work done by the
gas is negative
 Change in internal
energy is positive

Example: AN ideal gas expands adiabatically,

decreasing its temperature from 60°C to 30°C corresponding to a 50 J decrease in its internal
energy. How much work is done by th gas during this expansion?
Solution:
Because the internal energy has decreased, so W=50 J. A positive work means that work is
done by the gas on the surroundings. This means that the gas expanded.

Process Characteristics What the First Law of

Thermodynamics Predicts
Isothermal ,
Isobaric
Isochoric
Adiabatic

What have I Learned So Far?

Isothermal Expansion of an Ideal Gas
Two moles of the monatomic gas argon expand isothermally at 298K from an initial volume of
0.025m3 to a final volume of 0.050m3. Assuming that argon is an ideal gas, find (a) the work
done by the gas, (b) the change in internal energy of the gas, and (c) the heat supplied to the
gas.
Solution:
A. Use this formula:W= nRT In(
B. (Refer to Adiabatic Expansion in answering letter b and the table above in answering c.)

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 Second Law of Thermodynamics
Kelvin-Planck statement: It is impossible for an engine working between a cyclic process to
extract heat from a reservoir and convert completely into work. In other words, 100%
conversion of heat into work is impossible.

HEAT ENGINES
Heat engine is a device which converts heat energy into work. A heat engine, in general,
consists of three parts:
 A source or high temperature reservoir at temperature T1
 A working substance.
 A Sink or low temperature reservoir at temperature T2
Heat is supplied to the engine at a relatively high temperature from a place called the hot
reservoir.
Part of the input heat is used to perform work by the working substance of the engine.
The remainder of the input heat is rejected to a place called the cold reservoir
The efficiency of internal combustion engine is approximately 40% to 60%.

Thermal Efficiency is a dimensionless number that can have values between 0 and 1.
However, because the complete conversions of heat into work are forbidden by the second law
of thermodynamics, a thermal efficiency of unity or 100% is highly improbable.

Example: An automobile engine takes in 20 000 J of heat by burning fuel and delivers 5 000 J
of mechanical work per cycle. (a) What is the efficiency of the engine? (b) How much heat is
expelled to the environment per cycle?
Solution: a. in this problem, = 20 000 J and W= 5 000 J. The efficiency of the engine is
= = 0.25 or 25%
b. Note that . Thus,
= - = - = - 15 000 J
The negative sign means that heat is released by the engine.

Refrigerators and Heat Pumps

A refrigerator is the
reverse of a heat
engine. A heat pump is
the same as a
refrigerator.
Refrigerators, air
conditioners, and heat
pumps are devices that
make heat flow from
cold to hot. This is
called the
refrigeration
process.

Heat Pumps
The heat pump uses work to make heat from the wintry outdoors flow into the house or to hot
summer weather outside.

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Carnot Theorem
No irreversible engine (I) can have efficiency greater than Carnot reversible engine (R) working
between same hot and cold reservoirs.

CARNOT’S PRINCIPLE: AN ALTERNATIVE STATEMENT OF

THE SECOND
LAW OF THERMODYNAMICS
No irreversible engine operating between two reservoirs at
constant temperatures can have a greater efficiency than a
reversible engine operating between the same temperatures.
Furthermore, all reversible engines operating between the same
temperatures have the same efficiency.
The basic requirement for a Carnot cycle is to avoid all
irreversible processes. Because the flow of heat between bodies
that have different temperatures is irreversible, the following
requirements must be satisfied.
1. Processes that involve heat transfer must be isothermal.
2. Processes that involve a change in the temperature of the
working substance must be adiabatic.
The Carnot Cycle has two isothermal processes and two reversible
adiabatic processes.

 The Carnot engine is useful as an idealized model.

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  All of the heat input originates from a single temperature, and all the rejected heat goes
into a cold reservoir at a single temperature.
 Since the efficiency can only depend on the reservoir temperatures, the ratio of heats
can only depend on those temperatures

TC
ec  1 
TH

Example: The Ocean Thermal Energy Conversion (OTEC) takes advantage of the warm surface
temperature of the ocean and its cold underwater temperature. Calculate the ideal thermal
efficiency of OTEC that operates between temperatures 27°C and 4.0°C.
Solution:
e= 1- = 1-
The efficiency may look very low, but it is already the maximum possible efficiency for this
temperature difference that is consistent with the second law of Thermodynamics.
What Have I Learned So Far?
Water near the surface of a tropical ocean has a temperature of 298.2 K, whereas the water
700 meters beneath the surface has a temperature of 280.2 K. It has been proposed that the
warm water be used as the hot reservoir and the cool water as the cold reservoir of a heat
engine. Find the maximum possible efficiency for such and engine.
Solution:

Entropy
In general, irreversible processes cause us to lose some, but not necessarily all, of the ability to
do work. This partial loss can be expressed in terms of a concept called entropy. Entropy, like
internal energy, is a function of the state of the system. Q
S   
Restating the Second Law  T R
Any irreversible process increases the entropy of the universe.

THE SECOND LAW OF THERMODYNAMICS STATED IN TERMS OF ENTROPY

The total entropy of the universe does not change when a reversible process occurs and
increases when an irreversible process occurs.
Example: What is the change in entropy in converting 1.0 kg of ice at 0.0 to 1.0 kg of water at
0.0 ?
Solution: This is an irreversible isothermal process. However, as previously noted, because
entropy is path – independent, you can still use the equation for a reversible isothermal
process. Thus,

The 3rd Law of Thermodynamics

It is not possible to lower the temperature of any system to absolute zero in a finite number of
steps.

What Have I Learned So Far?

How much is the change in the entropy of 0.5 kg of water at freezing point when it is heated to
its boiling point?

Solution:

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Summary:
 An ideal gas can be described macroscopically by the equation of state pV= nRT
 Meanwhile, this equation is based microscopically on the kinetic molecular theory that
neglects the volume of the gas and the intermolecular forces, and it assumes that the
collision between gas particles as elastic.
 Thermodynamic processes can be described graphically using pV diagrams.
 Some examples of thermodynamic processes are the following: isothermal (constant
temperature), isobaric (constant pressure), isochoric (no work due to constant volume), and
adiabatic (no heat) processes.
 The first law of thermodynamics is a restatement of the law of conservation of energy. It
holds in systems where conservation of energy is true.
 The second law of thermodynamics gives limitation to the first law by stating the preferred
direction of natural processes. Here, natural processes proceed spontaneously in the
direction of greater disorder or entropy.
 In terms of heat flow, this direction toward increasing disorderliness corresponds to heat
flowing spontaneously from hot to cold objects (Clausius statement). Similarly, heat cannot
be spontaneously and completely converted into work (Kelvin-Planck statement).
 All natural processes are irreversible processes.
 A heat engine is a device that can be used to convert heat partially into work. Meanwhile,
the Carnot engine is an idealized engine that can give the highest possible efficiency that is
consistent with the second law of thermodynamics. A Carnot cycle is composed of reversible
processes consisting of two isothermal and two adiabatic processes.