Thermodynamics

LEARNING OBJECTIVES

 Define a thermodynamic system, its boundary, and its surroundings

 Explain the roles of all the components involved in thermodynamics
 Define thermal equilibrium and thermodynamic temperature
 Link an equation of state to a system
 INTRODUCTION

 Heat is the transfer of energy due to a temperature difference between two

systems.
 Heat describes the process of converting from one form of energy into another.
 A car engine, for example, burns gasoline. Heat is produced when the burned
fuel is chemically transformed into mostly 𝐶𝑂2 and 𝐻2 𝑂 , which are gases at
the combustion temperature.
 These gases exert a force on a piston through a displacement, doing work and
converting the piston’s kinetic energy into a variety of other forms of energy
 THERMODYNAMIC SYSTEMS

 A thermodynamic system includes anything whose thermodynamic properties are of

interest.
THERMODYNAMIC SYSTEMS

An isolated system cannot

exchange any heat, work, or
matter with the surroundings,
A closed system can
exchange energy (as heat or
work) but not matter, with its
surroundings.
while an open system can
exchange energy and matter.
 THERMODYNAMIC SYSTEMS CONT.
 The measurable properties of the system at least include its volume,
pressure, and temperature.
 The range of specific relevant variables depends upon the system.
 The relationship between these three basic properties of the system
is called the equation of state of the system and is written
symbolically for a closed system as
f ( p, V , T ) = 0
 where 𝑉 , 𝑝 , and 𝑇 are the volume, pressure, and temperature of
the system at a given condition.
 ZEROTH LAW OF THERMODYNAMICS

If object 1 is in thermal equilibrium with objects 2 and 3,

respectively, then objects 2 and 3 must also be in thermal
equilibrium.
This is the most fundamental way of defining temperature: Two
objects must be at the same temperature thermodynamically if
the net heat transfer between them is zero when they are put
in thermal contact and have reached a thermal equilibrium.
 THERMODYNAMIC SYSTEMS CON.

 We have so far introduced several physical properties that are relevant to the
thermodynamics of a thermodynamic system, such as its volume, pressure, and
temperature.
 We can separate these quantities into two generic categories
1. An extensive variable doubles its value if the amount of matter in the system
doubles, provided all the intensive variables remain the same. For example, the volume
or total energy of the system doubles if we double the amount of matter in the
system while holding the temperature and pressure of the system constant.
2. An intensive variable is one which does not depend on system size (like
temperature, pressure, or density).
Work, Heat, and Internal Energy
LEARNING OBJECTIVES

 Describe the work done by a system, heat transfer between objects,

and internal energy change of a system
 Calculate the work, heat transfer, and internal energy change in a
simple process
 WORK DONE BY A SYSTEM

 A force created from any source can do work by

moving an object through a displacement.
 Then how does a thermodynamic system do work?
The Figure shows a gas confined to a cylinder that
has a movable piston at one end. If the gas
expands against the piston, it exerts a force through
a distance and does work on the piston.
 If the piston compresses the gas as it is moved
inward, work is also done, on the gas.
 WORK, HEAT, AND INTERNAL ENERGY
 The work associated with such volume changes can be determined as
follows:
➢ . When the piston is pushed outward an infinitesimal distance 𝑑𝑥 , the
magnitude of the work done by the gas is
dW = Fdx = pAdx
➢ Since the change in volume of the gas is 𝑑𝑉 = 𝐴𝑑𝑥 , this becomes
dW = pdV
➢ For a finite change in volume from 𝑉1 to 𝑉2 , we can integrate this equation
from 𝑉1 to 𝑉2 to find the net work:
V2 V2  nRT 
W =  pdV =   dV
V1 V1
 V 
 WORK, HEAT, AND INTERNAL ENERGY

 This integral is only meaningful for a quasi-static

process, which means a process that takes place in
infinitesimally small steps, keeping the system at
thermal equilibrium.
V2 V2  nRT 
W =  pdV =   dV
V1 V1
 V 
 The integral is interpreted graphically as the area under
the 𝑝𝑉 curve (the shaded area of the Figure).
 Work done by the gas is positive for expansion and
negative for compression.
 TYPES OF THERMODYNAMIC PROCESS

isobaric,
isochoric,
isothermal,
adiabatic
 ISOTHERMAL
 an isothermal process is a type of
thermodynamic process in which the
temperature of the system remains constant:
Δ𝑇 = 0
 Temperature (T) remains constant over the
entire process. Since n and R are also constant,
the only variable in the integrand is V, so the
work done by an ideal gas in an isothermal
process is

V2 dV  V2 
W = nRT  = nRT ln  
V1 V  V1 
 ISOBARIC PROCESS

 An isobaric process is a type of

thermodynamic process in which the pressure
of the system stays constant: ΔP = 0.
 An isobaric process could be established by
allowing the piston to move freely.
 The work done on the gas in an isobaric
process is simply

W = p (V2 − V1 )
 ISOCHORIC

 The process that takes place at constant

volume is called an isovolumetric process.
Another name for this type of process is
isochoric.
 Because the volume of the gas does not
change in such a process, the work done is
equal to zero.
W =0
 ADIABATIC PROCESS

 An adiabatic process is one during which no

energy enters or leaves the system by heat.
 An adiabatic process can be achieved either by
thermally insulating the walls of the system or by
performing the process rapidly so that there is
negligible time for energy to transfer by heat.
 Unlike an isothermal process, an adiabatic process
transfers energy to the surroundings only as work
 INTERNAL ENERGY

 The internal energy 𝐸𝑖𝑛𝑡 of a thermodynamic system is, by definition, the

sum of the mechanical energies of all the molecules or entities in the system.
If the kinetic and potential energies of molecule 𝑛𝑖 are 𝐾𝑖 and 𝑈𝑖
respectively, then the internal energy of the system is the average of the total
mechanical energy of all the entities:

Eint =  (U i + K i )
i
 INTERNAL ENERGY CONT.
 In an ideal monatomic gas, each molecule is a single atom. Consequently,
there is no rotational or vibrational energy.
 Furthermore, there are no interatomic interactions), so 𝑈𝑖 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 , which
we set to zero.
 The internal energy is therefore due to translational kinetic energy only and

Eint =  K i
i

 The internal energy of an ideal monatomic gas is a function only of

temperature.
 FIRST LAW OF THERMODYNAMICS

 Suppose Q represents the heat exchanged between a system and the

surrounding , and W is the work done by or on the system.
 The first law states that the change in internal energy of that system is given
by Q−W.
 Since added heat increases the internal energy of a system, Q is positive
when it is added to the system and negative when it is removed from the
system.
 When a gas expands, it does work and its internal energy decreases. Thus, W
is positive when work is done by the system and negative when work is done
on the system.
 FIRST LAW OF THERMODYNAMICS

 Associated with every equilibrium state of a system is its internal energy 𝐸𝑖𝑛𝑡 .
The change in 𝐸𝑖𝑛𝑡 for any transition between two equilibrium states

Eint = Q − W
 Where 𝑄 and 𝑊 represent, respectively, the heat exchanged by the system
and the work done by the system.
 The first law is a statement of energy conservation that tells us that a system
can exchange energy with its surroundings by the transmission of heat and by
the performance of work.
 EXAMPLE

 Heat is added to 1 mol of an ideal monatomic gas confined to a cylinder with a

movable piston at one end. The gas expands quasi-statically at a constant
temperature of 300 K until its volume increases from V to 3V.

A. What is the change in internal energy of the gas?

B. How much work does the gas do?
C. How much heat is added to the gas?
 EXAMPLE CONT.

 strategy
➢ (a) Because the system is an ideal gas, the internal energy only changes when
the temperature changes.
➢ (b) The heat added to the system is therefore purely used to do work that has
been calculated in Work, Heat, and Internal Energy.
➢ (c) Lastly, the first law of thermodynamics can be used to calculate the heat
added to the gas.
 EXAMPLE CONT.

 Solution
A. The internal energy of an ideal monatomic gas is a function only of
temperature. Since Δ𝑇 = 0 , for this process, 𝐸𝑖𝑛𝑡 = 0 .
B. isothermal expansion of an ideal gas was considered in the preceding section
and was found to be

V2 3V
W = nRT ln = nRT ln = (1m ol )(8.314 J / K  mol )(300 K ) ln(3) = 2.74  103 J
V1 V
EXAMPLE CONT.

C. How much heat is added to the gas

Eint = Q − W = 0
Q = W = 2.74  10 J 3
 EXAMPLE 2

 When 1.00 g of water at 100°𝐶 changes from the liquid to the gas phase at
atmospheric pressure, its change in volume is 1.67 × 10−3 .
(a) How much heat must be added to vaporize the water?
(b) How much work is done by the water against the atmosphere in its
expansion?
(c) What is the change in the internal energy of the water?
 EXAMPLE 2 CONT.
 Solution
a) With 𝐿𝑣 representing the latent heat of vaporization, the heat required to
vaporize the water is
Q = mLv = (1.00 g )(2.26  103 J / g ) = 2.26  103 J
b) Since the pressure on the system is constant at 1𝑎𝑡𝑚 = 1.01 × 105 𝑁/𝑚2 the
work done by the water as it is vaporized is
W = p V = (1.01  105 N / m 2 )(1.67  10−3 m3 ) = 169 J
c) From the first law, the thermal energy of the water during its vaporization
changes by Eint = Q − W
Eint = 2.26  103 J − 169 J = 2.09  103 J
 CYCLIC PROCESSES AND ISOLATED SYSTEMS
 Two special cases of the first law of
thermodynamics are worth mentioning.
 A process that eventually returns a system to its
initial state is called a cyclic process.
 For such a process, the final state is the same as
the initial state, and so the total internal energy
change must be zero. Then

Eint = 0; Hence Eint = Q − W = 0 Q =W

CYCLIC PROCESSES AND ISOLATED SYSTEMS CONT.

 Another special case occurs in an isolated system, one that does no work on its
surroundings and has no heat flow to or from its surroundings. For any process
taking place in an isolated system,

W =Q=0 Hence Eint = 0

 In other words, the internal energy of an isolated system is constant
 QUASI-STATIC AND NON-QUASI-STATIC PROCESSES

 A quasi-static process refers to an

idealized or imagined process where the
change in state is made infinitesimally
slowly so that at each instant, the
system can be assumed to be at a
thermodynamic equilibrium with itself
and with the environment.
 Since quasi-static processes cannot
be completely realized for any finite
change of the system, all processes in
nature are non-quasi-static.
 HEAT CAPACITIES OF AN IDEAL GAS

 Molar heat capacity at constant volume of the gas

dQ = Cv ndT
 Molar heat capacity at constant pressure of the gas.

dQ = C p ndT
 The molar heat capacity of an ideal gas at constant pressure is greater than the
molar heat capacity at constant volume; the difference is the gas constant R.

C p = Cv + R
MOLAR HEAT CAPACITIES OF DILUTE IDEAL GASES AT ROOM TEMPERATURE
 ADIABATIC PROCESSES FOR AN IDEAL GAS
 When an ideal gas is compressed adiabatically (Q=0), work is done on it and
its temperature increases; in an adiabatic expansion, the gas does work and its
temperature drops.
 Adiabatic compressions actually occur in the cylinders of a car, where the
compressions of the gas-air mixture take place so quickly that there is no time
for the mixture to exchange heat with its environment.
 In the figure below the gas in the left chamber expands freely into the right
chamber when the membrane is punctured
End of Lecture 4 part 1