Energy Transfer by Heat and Work

System: A system is a region containing energy and/or matter that is separated from its

surroundings by arbitrarily imposed walls or boundaries.

Surroundings: Everything that interacts with the system

Boundary: A boundary is a closed surface surrounding a system through which energy and mass

may enter or leave the system.

Open system: If the thermodynamic system has the capacity to exchange both matter and energy

with its surroundings, it is said to be an open system.

Example: Consider a beaker in the presence of reactants in an open beaker. Here the boundary is

an imaginary surface enclosing the beaker and reactants. A steam turbine, a pool filled with water,

where the water can enter or leave the pool.

Closed system: A system which has the ability to exchange only energy with its surroundings and

cannot exchange matter is known as a closed system.

Example: Reactants placed in a closed vessel made of materials like steel, copper, and silver are

an ideal example of a closed system since the material of the vessel is conducting in nature. A

cylinder in which the valve is closed is an example of a closed system. When the cylinder is heated

or cooled, it does not lose its mass.

Isolated System: A system which cannot exchange matter or energy with the surroundings is

known as an isolated system. The zeroth law of thermodynamics states that thermodynamic

processes do not affect the total energy of the system.

Example: Reactants are present in a thermos flask or an insulated vessel, where neither energy nor

matter is exchanged with the environment. If the piston and cylinder arrangement in which the

fluid like air or gas is being compressed or expanded is insulated, it becomes an isolated system.

Heat: Heat is defined as the flow of energy from a warm to a cooler object. The direction of flow

of the heat energy takes from the substance of higher temperature to the substance of lower

temperature.

Conduction: It is the method in which the transfer of heat takes place between atoms and

molecules in direct contact.

Convection: It is the method in which the transfer of heat happens by the movement of the heated

substance.

Radiation: It is the method in which the transfer of heat takes place by electromagnetic waves.

Adiabatic Process: The thermodynamic process in which there is no exchange of heat from the

system to its surrounding neither during expansion nor during compression.

The adiabatic process can be either reversible or irreversible. Following are the essential conditions

for the adiabatic process to take place:

• The system must be perfectly insulated from the surrounding.

• The process must be carried out quickly so that there is a sufficient amount of time for heat

transfer to take place.

Following is the adiabatic process equation:

𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Where,

P is the pressure of the system, V is the volume of the system, γ is the adiabatic index and is defined

as the ratio of heat capacity at constant pressure Cp to heat capacity at constant volume Cv.
Heat capacity: heat capacity of a substance is the quantity of the heat required to raise the

temperature of the whole substance by one degree. Its S.I unit is J K-1.

Specific heat (Csp): If the mass of the substance is unity then the heat capacity is called Specific

heat capacity or the specific heat. S.I unit of specific heat is J kg-1 K-1.

Heat capacity at constant pressure (Cp): In a system, Cp is the amount of heat energy released

or absorbed by a unit mass of the substance with the change in temperature at a constant pressure.

Heat capacity at constant volume (Cv): The heat energy transfer between a system and its

surroundings without any change in the volume of that system.

Isothermal process: An isothermal process is defined as one of the thermodynamic processes

which occur at a constant temperature.

Difference Between Isothermal and Adiabatic Process

Isothermal process Adiabatic process

1. An isothermal process is defined as one of An adiabatic process is defined as one of the

the thermodynamic processes which occur thermodynamic processes which occur
at a constant temperature without any heat transfer between the system
and the surrounding

2. Work done is due to the change in the net Work done is due to the change in its internal
heat content in the system energy

3. The temperature cannot be varied The temperature can be varied

4. There is a transfer of heat There is no transfer of heat

Positive Negative
Heat transferred to a system Heat transferred from a system

Work done by a system Work done on a system

Chapter 3

Work, heat and the first law of

thermodynamics

3.1 Mechanical work

Mechanical work is defined as an energy transfer to the system through the change of an
external parameter. Work is the only energy which is transferred to the system through
external macroscopic forces.
Example: consider the mechanical work performed on a gas
due to an infinitesimal volume change (reversible transfor-
mation)
dV = adx ,
where a is the active area of the piston. In equilibrium, the
external force F is related to pressure P as

F = −P a .

For an infinitesimal process, the change of the position of the wall by dx results in per-
forming work δW :

δW = F dx = −P dV, δW = −P adx . (3.1)

For a transformation of the system along a finite reversible path in the equation-of-state
space (viz for a process with finite change of volume), the total work performed is
� V2
ΔW = − P dV.
V1

Note:
• Mechanical work is positive when it is performed on the system.

• δW is not an exact differential, i.e., W (P, V ) does not define any state property.

• ΔW depends on the path connecting A (V1 ) and B (V2 ).

21
22 CHAPTER 3. WORK, HEAT AND THE FIRST LAW OF THERMODYNAMICS

Cyclic process. During a cyclic process the path in

the equation-of-state space is a closed loop; the work
done is along a closed cycle on the equation-of-state
surface f (P, V, T ) = 0:
�
W = − P dV.

3.2 Heat
Energy is transferred in a system in the from of heat when no mechanical work is exerted,
viz when δW = −P dV vanishes. Compare (3.1). Other forms of energy (magnetic,
electric, gravitational, ...) are also considered to be constant.
Heat transfer is a thermodynamic process representing the transfer of energy in the form
of thermal agitation of the constituent particles. In practice one needs heating elements
to do the job, f.i. a flame.
As an example of a process where only heat is transferred, we consider two isolated systems
with temperatures TA and TB such that TA > TB . The two systems are brought together
without moving the wall between them. Due to the temperature difference, the energy is
transferred through the static wall without any change of the systems’ volume (no work
is done). Under such conditions, the transferred energy from A to B is heat.

Heat capacity. If a system absorbs an amount of heat ΔQ, its temperature rises pro-
portionally by an amount ΔT :
ΔQ = CΔT . (3.2)

The proportionality constant C is the heat capacity of the substance (Wärmekapazität).

It is an extensive quantity.
Specific heat. The intensive heat capacity c may take various forms:
per particle : C/N
per mole : C/n
per unit volume : C/V
The unit of heat is calorie or, equivalently, Joule

1 cal ≡ 4.184 J .
3.3. EXACT DIFFERENTIALS 23

Thermodynamic processes. Heat may be absorbed by a body retaining one of its

defining variables constant. The various possible processes are:

isothermal : T = const.
isobaric : P = const.
isochoric : V = const.
adiabatic : ΔQ = 0 (no heat is transferred)

A corresponding subscript is used to distinguish the various types of paths. For example,
CV – for the heat capacity at constant volume,
CP – for the heat capacity at constant pressure.

Thermodynamic response coefficients. Examples of other thermodynamic coeffi-

cients measuring the linear response of the system to an external source are
1 ΔV
compressibility : κ=−
V ΔP
1 ΔV
the coefficient of thermal expansion : α= .
V ΔT
Sign convention. We remind that the convention is that
δQ > 0
when heat is transferred to the system
δW > 0
when work is done on the system, with δW = −P dV .

3.3 Exact differentials

A function f = f (x, y) of two variables has the differential
∂f ∂f
df = Adx + Bdy, A= , B= .
∂x ∂y
Reversely one says that Adx + Bdy is an exact differential if

∂A ∂B ∂ 2f ∂ 2f
= , = .
∂y ∂x ∂x∂y ∂y∂x

An example from classical example is the potential energy Φ(x, y). For all exact differen-
tials dΦ the path of integration is irrelevant,
� (x2 ,y2 )
Φ(x2 , y2 ) = Φ(x1 , y1 ) + dΦ .
(x1 ,y1 )
24 CHAPTER 3. WORK, HEAT AND THE FIRST LAW OF THERMODYNAMICS

Any path connecting (x1 , y1 ) to (x2 , y2 ) results in the same Φ(x2 , y2 ).

Stirling cycle. Heat and work are both –not– exact differentials. This is an experimental
fact which can be illustrated by any reversible cyclic process. As an example we consider
here the Stirling cycle, which consist of four sub-processes.

(1) Isothermal expansion. The heat Q1 delivered to the gas makes it expand at constant
temperature.

(2) Isochoric cooling. The volume of the piston is kept constant while the gas cools
down. The transferred heat and work are Q2 and W2 .

(3) Isothermal compression. The heat Q3 removed makes the gas contract at constant
temperature.

(4) Isochoric heating. The volume of the piston is kept constant while is heated up.
The transferred heat and work are Q4 and W4 .

The experimental fact that the Stirling cycle can be used either as an engine (W2 + W4 <
0), or as an heat pump (W2 + W4 > 0), proves that work and heat cannot be exact
differentials, viz that �
δQ �= 0 .

3.4 First law of thermodynamics – internal energy

The first law of thermodynamics expresses that energy is conserved, when all forms of
energy, including heat, are taken into account.
Definition 1. For a closed thermodynamic system, there exists a function of state, the
internal energy U , whose change ΔU in any thermodynamic transformation is given by

ΔU = ΔQ + ΔW + . . . , (3.3)

where ΔQ is heat transferred to the system and ΔW is mechanical work performed on

the system. If present, other forms of energy transfer processes need to taken into account
on the RHS of (3.3).
ΔU is independent of the path of transformation, although ΔQ and ΔW are path-
dependent. Correspondingly, in a reversible infinitesimal transformation, the infinitesimal
3.4. FIRST LAW OF THERMODYNAMICS – INTERNAL ENERGY 25

δQ and δW are not exact differentials (in the sense that they do not represent the changes
of definite functions of state), but

dU = δQ + δW , dU = CV dT − P dV (3.4)

is an exact differential. For the second part of (3.4) we have used (3.2) and (3.1), namely
that δQ = CV dT (when the volume V is constant) and that δW = −P dV .
Definition 2. Energy cannot be created out of nothing in a closed cycle process:
�
dU = 0 ⇒ ΔQ = −ΔW .

Statistical mechanics. The iternal energy U is a key quantity in statistical mechanics,

as it is given microscopically by the sum of kinetic and potential energy of the constituent
particles of the system
N N N
1 � 2 � 1�
U = E = p + φ(�ri ) + V (�ri − �rj ) ,
2m i=1 i i=1
2 i�=j

where φ(�ri ) is the external potential and V (�ri − �rj ) is the potential of the interaction
between particles (f.i. the Coulomb interaction potential between charged particles).

3.4.1 Internal energy of an ideal gas

We consider N molecules, i.e. n = N/NA moles, in a cubic
box of side L and volume V = L3 . A particle hitting a given
wall changes its momentum by y

Δpx = 2mvx , Δt = 2L/vx L

where m is the mass, vx the velocity in x−direction and Δt

the average time between collisions. The momentum hence
changes on the average as
Δpx 2mvx mvx2 mv2 2 x
= = = = Ekin ,
Δt 2L/vx L 3L 3L
z
where Ekin = mv2 /2 is the kinetic energy of the molecule
and v2 = vx2 + vy2 + vz2 .
Newton’s law. Newton’s law, dp/dt = F, tells us that the total force Ftot on the wall is
2N Ekin /(3L). We then obtain for the pressure
Ftot 2 N m 2
P = 2
= Ekin , Ekin = v .
L 3 L3 2
Assuming the ideal gas relation (1.3) we find consequently
N 2 N 3
P = kB T = Ekin , Ekin = kB T (3.5)
V 3 L3 2
26 CHAPTER 3. WORK, HEAT AND THE FIRST LAW OF THERMODYNAMICS

for the kinetic energy Ekin of a single molecule. The internal energy is then, with φ(�ri ) =
V (�ri − �rj ) = 0,
3 3 3
U = N kB T = nRT = P V , (3.6)
2 2 2

where R = 8.314 J/(mol K) is the gas constant.

3.5 Energy and heat capacity for various processes

In this section we shall analyze various heat transfer processes and derive the correspond-
ing heat capacities with the help of the first law of thermodynamics.

3.5.1 Isochoric process

An isochoric process is a constant volume pro-
cess. We have hence

dV = 0, δW = 0, dU |V = δQ|V ,

and
� � � �
δQ dU
= = CV (3.7)
dT V dT V

for the heat capacity at constant volume CV .

Ideal gas. An ideal gas containing n moles is defined by its equation of state,

P V = N kB T , N kB = nR . (3.8)

Using the internal energy (3.6),

3 3 3
U = N kB T = nRT, dU = nRdT ,
2 2 2
we obtain
3 3 PV
CV = nR = (3.9)
2 2 T

for the heat capacity of the ideal gas at constant volume.

3.5.2 Isobaric process

3.5. ENERGY AND HEAT CAPACITY FOR VARIOUS PROCESSES 27

An isobaric process is a constant pressure pro-

cess. In order to evaluate CP we consider

δQ|P = dU |P + P dV |P ,

which, under an infinitesimal increment of tem-

perature, is written as
� � � �
∂U ∂V
δQ|P = dT + P dT
∂T P ∂T P
≡ CP dT.

The specific heat at constant pressure,

� � � �
∂U ∂V
CP = +P , (3.10)
∂T P ∂T P

reduces then for an ideal gas, for which U = 3nRT /2 and P V = nRT , to

3 5
CP = nR + nR = nR = CV + N kB . (3.11)
2 2

Mayer’s relation between CP and CV . In order to evaluate the partial derivative

(∂U/∂T )P entering the definition (3.10) of the specific heat at constant pressure we note
that the equation of state f (P, V, T ) = 0 determines the interrelation between P , V and
T . A constant pressure P defines hence a functional dependence between V and T . We
therefore have � � � � � � � � � �
∂U ∂U ∂T ∂U ∂V
= +
∂T P ∂T V ∂T P ∂V T ∂T P
� �� � � �� �
= CV =1
and hence with � � � �� �
∂U ∂V
CP = CV + P + (3.12)
∂V T ∂T P

the Mayer relation. In Sect. 4.5 we will connect the partial derivatives entering (3.12)
with measurable quantities.

3.5.3 Isothermal processes for the ideal gas

An isothermal process takes place at constant temper-
ature. The work performed
� V2
ΔW = − dV P
V1
28 CHAPTER 3. WORK, HEAT AND THE FIRST LAW OF THERMODYNAMICS

is hence given by the area below P = P (T, V )|T . Using

the equation-of-state relation P V = nRT of the ideal
gas we obtain
� V2
dV V2
ΔW = −nRT = −nRT ln
V1 V V1
= −ΔQ ,

where the last relation follow from the first law, ΔU = ΔQ + ΔW , and from the fact that
the internal energy U = 3nRT /2 of the ideal gas remains constant during the isothermal
process. ΔW > 0 for V1 > V2 , viz when the gas is compressed.

Note. Heat cannot be transformed in work forever, as we will discuss in the next chapter.

3.5.4 Free expansion of an ideal gas

A classical experiment, as performed first by Joule, consist of allowing a thermally isolated
ideal gas to expand freely into an isolated chamber, which had been initially empty. After
a new equilibrium state was established, in which the gas fills both compartments, the
final temperature of the gas is found to be identical to the initial temperature.

The expansion process is overall isolated. Neither heat nor work is transferred into the
system,
ΔW = 0, ΔQ = 0, ΔU = 0 ,

and internal energy U stay constant

Ideal gas. The internal energy

3
U = nRT,
2
of the ideal gas with a contant number n of mols depends only on the temperature T , and
not on the volume V . The kinetic energy Ekin = 3kB T /2 of the constitutent particles is
not contingent on the enclosing volume. We hence have
� �
∂T
= 0, T2 = T 1 .
∂V U

Which means that for the ideal gas the free expansion is an isothermal expansion, in
agreement with Joule’s findings.
3.6. ENTHALPY 29

3.5.5 Adiabatic processes for the ideal gas

An adiabatic process happens without heat transfer:
δQ = 0, dU = −P dV ,
where the second relation follows from the first law of thermodynamics, dU = δQ + δW .
For the ideal gas we have P V = nRT , U = 3nRT /2 = 3P V /2 and hence

3� � 5 dV 3 dP
dU = P dV + V dP = −P dV, = − ,
2 2 V 2 P
which can be solved as
� � � �
V P0
γ log = log , P V γ = const. , γ = 5/3 .
V0 P

Using the ideal gas equation of state, P V =

nRT , we may write equivalently

T V γ−1 = const. .
Since γ > 1, an adiabatic path has a steeper
slope than an isotherm in a P − V diagram.

3.6 Enthalpy
The internal energy is a continuous differentiable state function for which the relations
� �
∂U
dU = δQ − P dV, δQ = CV dT, CV =
∂T V
hold. One can define equivalently with
H ≡ U + PV , (3.13)
a state function H, denote the enthalpy, which obeys
� �
∂H
dH = δQ + V dP, δQ = CP dT, CP = . (3.14)
∂T P
Note that P , V and T determine each others in pairs via the equation-of-state function
f (P, V, T ) = 0.
Derivation. We have
dH = dU + P dV + V dP = δQ − P dV + P dV + V dP
= δQ + V dP ,
in accordance with and (3.14), and
� � � � � � � �
∂H ∂(U + P V ) ∂U ∂V
= = +P = CP
∂T P ∂T P ∂T P ∂T P
in agreement with the definition (3.10) of the specific heat CP at constant pressure.