SPB 2305: Thermodynamics

1.0 Introduction

1.1 Thermodynamics is the basic science, which deals with heat and other forms of energy,
their transformations and their relationships with properties of substances

There are two classes of thermodynamics namely classical and statistical thermodynamics:
I. Classical thermodynamics: It is a science that is concerned only with the average
characteristics of large aggregates of molecules, not with the characteristics of
individual molecules i.e. classical thermodynamics takes macroscopic point of view
and deals with macroscopic phenomenon.
II. Statistical thermodynamics: It considers the microscopic structure of matter and
adopts the laws of mechanics on the statistical analysis of the individual particles.

1.2 Some Definitions

 System: A system is defined as a quantity of matter or a region in space chosen for study.
The mass or region outside the system is called the surroundings. The real or imaginary
surface that separates the system from its surroundings is called the boundary

Alternatively; This is a specific portion of matter with definite boundaries on which

attention is focussed. The boundaries are well prescribed and may be either movable
or fixed
 Surrounding (Environment): This refers to all space of matter external to the
system, which may or may not interact with the system
 Closed system: This is a system of fixed (constant) content (mass) i.e. one in which
no transfer of mass occurs.

 Open system: A system in which mass may be transferred between the system and the
surrounding

 Isolated Systems: Systems which can not exchange energy of any kind including
mass with their surroundings, i.e. isolated system is not allowed to exchange heat,
work or mass with its surroundings

 A process: Any transformation of a system from one equilibrium state to another over
an interval of time. Work and energy transfer may occur. When any property of a
system changes there is change in the state and the system is said to undergo a process

 Isothermal: Is the locus of all points representing states at which a system is in

thermal equilibrium with one state of another system

 Adiabatic wall: It does not allow heat to pass through (impervious to heat)

 Diathermic Wall: It allow heat to pass through

1
  State Zeroth law of thermodynamic

1.3 Zeroth law of thermodynamics

Imagine two systems A and B separated from each other by an adiabatic wall but each in
contact with a third system C through diathermic walls, the whole assembly being surrounded
by an adiabatic wall as shown in figure 1a. The two systems will come to thermal equilibrium
with the third and that no further change will occur if the adiabatic wall separating A and B is

then replaced by a diathermic wall figure 1b. This experimental fact can then be stated
concisely in the following form: Two systems in thermal equilibrium with a third are in
thermal equilibrium with each other. This is the Zeroth law of thermodynamics.

Figure 1. a). Systems A and B separated from each other by an adiabatic wall but each in
contact with a third system C through diathermic walls. b). Systems A and B after the
adiabatic wall separating them is replaced with diathermic wall but each in contact with a
third system C through adiabatic wall.

2
2.0 FIRST LAW OF THERMODYNAMICS

Objectives: By the end of this lesson, you should be able to

 State first law of thermodynamics both mathematically and qualitatively
 Show that the internal energy of a system is a point function and it is a property of
the system.
 Solve problems involving internal energy, heat and work done

2.1 Definition
The first law of thermodynamics is essentially the law of conservation of energy applied to
thermodynamic system. It states

Heat Work
Mathematically

dw 0 i.e. in a cyclic process the work done is not equal to zero.
This implies that

dq 0 heat is not equal to zero.

Thus dw dq  ( dq dw) 0

Let U be internal energy function (function of state)

dU dq dw dU 0

First law of thermodynamics states that; if heat is added to the system so as to

increase the internal energy by dU and also give rise to an amount of work dw,
then: dq = dU + dw

First law applies to any process; reversible or irreversible. Let consider a system that absorbs
heat Q and does work W and its internal energy change by U from U1 to U2 . From
conservation of energy Q =U +W, U = U2-U1.

Note
Sign convention
 Heat absorbed by system (positive)
 Heat rejected by system (negative)
 Work done by system (positive)
 Work done on the system (negative)

3
Consider a system which changes from state 1 to state 2 by the process A and returns to state
1 by process B or C (figure 2.1). For the cycle composed of A and B we have

Figure 2.1: A cyclic process

2 1
…………………………….(2.1)
(dQ dW )  (dQ dW ) 0
1A 2B

and for the cycle composed of process A and C.

2 1

(dQ dW )  (dQ dW ) 0 ………………………………..(2.2)

1A 2C
Comparing equations (2.1) and (2.2) we find that

1 1

(dQ dW )  (dQ dW )

2B 2C

Since B and C are arbitrary functions then

(dQ dW ) is equal for both processes and is independent of the path taken,
is a point function and it is a property of the system.

(dQ dW ) dU

By definition dU = Cv T
Therefore, while working with first law of thermodynamics we are concerned with U, W and
Q or

Q = U + W…………….......................................(2.3)

3.0 ADIABATIC PROCESSES

Objectives: By the end of this lesson, you should be able to:

 Explain adiabatic and isothermal process

 Show the importance of the ratio Cp/Cv in adiabatic processes
 Calculate work done in adiabatic and isothermal processes
4
 1 1  
 Show that for adiabatic process T V T V and PV P V 
1 1 2 2 1 1 2 2

Adiabatic processes
An adiabatic process is one in which no heat transfer takes place between the system and
its surrounding. The zero heat transfer is an ideal case but a system can approximate so
if it is well insulated. It can also approximate so if the process takes place so fast that
there is no enough time for heat flow to occur. In this process

dQ =0 dU = -dW

As the gas expands from V1 to V2 its temperature drops from T+dT to T. The drop in
temperature causes a decrease in internal energy due to work done by the gas. The change
in internal energy is given by dU= nCvdT while the work done by the gas during the
process is given by dW=PdV. But dU =-dW therefore
nCvdT=-PdV. (3.2)

From the ideal gas equation PV = nRT P = nRT/V, equation 2 becomes

𝑛𝑅𝑇
𝑛𝐶𝑣 𝑑𝑇 = − 𝑑𝑉 (3.3)
𝑉

𝑑𝑇 𝑅 𝑑𝑉
+ =0 𝑠𝑖𝑛𝑐𝑒 𝑅 = 𝐶𝑝 − 𝐶𝑣
𝑇 𝐶𝑣 𝑉
𝑅 𝐶𝑝 − 𝐶𝑣 𝐶𝑝
= = −1=𝛾−1 (3.4)
𝐶𝑣 𝐶𝑣 𝐶𝑣

Since >1 then (-1) is positive. From equation (3.4) we obtain that dV and dT are always
opposite in signs. Therefore we

Note:
 An adiabatic expansion of an ideal gas (dV>0) always occurs with a drop in
temperature (dT<0), and an adiabatic compression (dV<0) always occurs with
rise in temperature (dT>0).

For finite changes in temperature and volume, we can integrate equation (3.4) to get

5
 𝑑𝑇 𝑑𝑉
∫ + (𝛾 − 1) ∫ =0
𝑇 𝑉 (3.5)
ln T ( 1) lnV cons tan t
(3.6)
ln(TV 1 ) cons tan t
or

TV 1 cons tan t (3.7)

Thus for an initial state (T1V1) and final state (T2V2)

𝛾−1 𝛾−1
𝑇1 𝑉1 = 𝑇2 𝑉2 (5.8)

Similarly, from PV =nRT T = PV/nR

Therefore
PV
V 1 cons tan t
nR
PV  cons tan t
nR

or since nR is a constant

PV  cons tan t (3.9)

6
For initial state (P1V1) and final state (P2V2)
 
PV  P V  (3.10)
1 1 2 2

Work done in adiabatic process

W = -U.

For an ideal gas

U= nCv(T2-T1)

W=nCv(T1-T2) But from PV =nRT we get T1=P1V1/nR and

T2=P2V2/nR,
therefore,

W n C v P1V 1 P2 V 2  (3.11)

nR
W  1 P1V 1  P2V 2 
 1

7
4.0 IDEAL GAS LAWS

4.1 Equations of state

When a gas is compressed at constant temperature then.

1. Volume (V) decreases
2. Pressure (P) increases

Also when the gas is expanded at constant temperature,

1. Volume (V) increases
2. Pressure (P) decreases

That is to say,

PV = constant (constant temperature)

This equation holds approximately for all gases at low densities. At low densities PV is nearly
proportional to temperature T so that

PV =CT where C is a constant. ……….(4.1)

Suppose there are two identical containers each holding the same amount of the same kind of
the gas at the same temperature. Each has a volume V described be equation 4.1. If the two
containers are combined, the result is twice the volume of the gas at the same pressure P and
temperature T. It follows then that C in equation 4.1 must have increased by a factor 2.
Therefore C is proportional to the amount of the gas

C=kN……………………………………………….…(4.2) Where
N is the number of molecules of the gas and k is a constant.
Therefore equation 4.1 becomes

PV = kNT……………………………………………..…(4.3)
Where k is the Boltzmann’s constant.

The amount of the gas is conveniently written in moles

If there are n moles of a substance, the number of molecules is

N=nNA……………………………………………….(4.4) Where
NA is the Avogradros number (number of molecules in a mole).
Therefore equation (4.3) becomes

PV= nNAkT=nRT………………………………………………(4.5)
Where R = universal gas constant.

8
We define an ideal gas as one for which PV/nT is a constant for all pressures. For
ideal gas
PV = nRT……………………………………………(4.6)

9
10