MODULE IN THERMODYNAMICS

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I. INTRODUCTION

Thermodynamics is an exciting and fascinating subject that deals with energy,

and thermodynamics has long been an essential part of engineering curriculum all

over the world. It has broad application area arranging from microscopic organism to

common household appliances, transportation vehicles, power generation systems,

and even philosophy.

Thermodynamics is the science that deals with heat and work and these

properties of substances that bear a relation to heat and work. Like all sciences, the

basis of thermodynamics is experimental observation. In thermodynamics these

findings have been formalized into certain basic laws, which are known as the first,

second, and third law of thermodynamics. In addition to these laws, the zeroth law of

thermodynamics, which in the logical development of thermodynamics precedes the

first law, has been set forth.

In what follows, we will present the basic thermodynamics laws, and apply

them to a number of representative examples.

Refrigeration and air conditioning involves various processes such as

compression, expansion, cooling, heating, humidification, de-humidification, air

purification, air distribution etc. In all these processes, there is an exchange of mass,

momentum and energy. All these exchanges are subject to certain fundamental laws.

Hence to understand and analyze refrigeration and air conditioning systems, a basic

knowledge of the laws of thermodynamics, fluid mechanics and heat transfer that

govern these processes is essential. It is assumed that the reader has studied courses in

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engineering thermodynamics, fluid mechanics and heat transfer. This chapter reviews

some of the fundamental concepts of thermodynamics pertinent to refrigeration and

air-conditioning.

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II. BASIC CONCEPTS AND DEFINITIONS

2.1 THERMODYNAMICS

Thermodynamics is the study of energy and the ways in which it can be used

to improve the lives of people around the world. The efficient use of natural and

renewable energy sources is one of the most important technical, political, and

environmental issues of the 21st century.

Thermodynamics is the study of energy interactions between systems and the

effect of these interactions on the system properties. Energy transfer between systems

takes place in the form of heat and/or work. Thermodynamics deals with systems in

equilibrium.

2.2 THERMODYNAMIC SYSTEM

A thermodynamic system is defined as a quantity of matter of fixed mass and

identity upon which attention is focused for study. In simple terms, a system is

whatever we want to study. A system could be as simple as a gas in a cylinder or as

complex as a nuclear power plant. Everything external to the system is the

surroundings. The system is separated from the surroundings by the system

boundaries. Thermodynamic systems can be further classified into closed systems,

open systems and isolated systems.

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In the figure, the gas in the cylinder is considered to be the system. When the

cylinder is heated from below, the temperature of the gas will increase and the piston

will rise. As the piston rises, the boundary of the system moves. Heat and work cross

the boundary of the system during this thermodynamic process, but the matter that

comprises the system can always be identified.

SYSTEM – is a collection of matter within prescribed and identifiable

boundaries. A system maybe either an open one, or a closed one, referring to whether

mass transfer or does not take place across the boundary.

SURROUNDINGS – is usually restricted to those particles of matter

external to the system which may be affected by changes within the system., and the

surroundings themselves may form another system.

BOUNDARY – is a physical or imaginary surface, enveloping the

system and separating it from the surroundings.

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2.3CONTROL VOLUME

Mass, as well as heat and work (and momentum), can flow across the

control surface. Example is air compressor.

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2.4PROPERTIES AND STATE OF A SUBSTANCE

We define:

• Phase - a quantity of matter that is homogeneous throughout, and

• Phase Boundaries - interfaces between different phases.

An example of a single phase is ice. Another single phase is liquid water.

A glass of ice water is a two-phase mixture with the phase boundaries at the

edge of each ice cube.

We next define (circularly):

• State - condition described by observable macroscopic properties, and

• Property - quantity which only depends on the state of the system and is

independent of the history of the system.

Examples of properties include temperature and pressure. Two states are

equivalent if they have the same properties. So if state 1 is defined by

temperature T1 and pressure P1, and state 2 is defined is by temperature T2 and

P2, state 1 is equivalent to state 2 if (that is, if and only if) T1 = T2 and P1 = P2.

There are two important classes of properties we consider in

thermodynamics:

• Extensive Property - a property which depends on the mass (or the

extent) of the system, example extensive properties include mass, total

volume, total energy, and

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• Intensive Property - a property which is independent of the mass of the

system. Example intensive properties include temperature and pressure.

In general, if you cut a system in half and re-measure its properties,

intensive properties remain unchanged, while extensive properties are cut in

half. Properties are defined for systems which are in

• Equilibrium - state in which no spontaneous changes are observed with

respect to time.

We actually never totally achieve equilibrium, we only approximate it. It

takes infinite time to achieve final equilibrium. In this class we will mainly be

concerned with two types of equilibrium:

• Mechanical equilibrium - characterized by equal pressure, and

• Thermal equilibrium - characterized by equal temperature.

A third type of equilibrium is chemical equilibrium, which we will not

consider here, and is characterized by equal chemical potentials.

A difficult conceptual challenge of thermodynamics is to reckon with two

systems initially at their own equilibria, to bring them into contact so that they

find a new equilibria. How to do this without consideration of time can be

difficult. Another branch of thermodynamics, which we will consider only

briefly in this course is

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• Non-equilibrium thermodynamics - branch of thermodynamics which

considers systems often far from equilibrium and the time-dynamics of their

path to equilibrium.

We will go to great effort to construct a thermodynamics which is

generally not burdened with time. Occasionally we will bring time into our

problems. Unfortunately, ignoring time occasionally requires some mental

contortions, as seen in the next section.

2.5PROCESS AND CYCLE

Often systems undergo a:

• Change of State - implies one or more properties of the system has

changed.

How these properties would change outside of time is curiously outside

the framework of equilibrium thermodynamics! The best way to think of

them is that the changes are slow relative to the underlying molecular time

scales. Fortunately, this will allow us to do a wide variety of problems of

engineering relevance.

We also define a

• Process - a succession of changes of state.

We assume our processes are all sufficiently slow such that each stage

of the process is near equilibrium. Certain common processes are given

special names, based on the Greek , ι ′ σoς, isos, meaning “equal”:

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• isothermal - constant temperature,

• isobaric - constant pressure, and

• isochoric - constant volume.

An important notion in thermodynamics is that of a

• cycle - series of processes which returns to the original state. The

cycle is a thermodynamic “round trip.”

Whenever one or more of the properties of a system change, a Change in

State has occurred. For example, when one of the weights on the piston in the

figure is removed, the piston rises and a change in state occurs, for the

pressure decreases and the specific volume increases. The path of the

succession of states through which the system passes is called the process.

When a system in a given initial state goes through a number of different

changes of state or processes and finally returns to its initial state, the system

has undergone a Cycle. Therefore, at the conclusion of a cycle, all the

properties have the same value they had at the beginning. Steam (water) that

circulates through a steam power plant (like the conventional side of a nuclear

reactor) undergoes a cycle.

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2.6FUNDAMENTALS VARIABLES AND UNITS

We will mainly use the System International (SI) units in this course.

Occasionally, we will use the English Engineering system of units. As found

in US National Institute of Standards and Technology (NIST) documents, the

important fundamental base SI units, and corresponding English units are:

• MASS

– KILOGRAM (KG): a mass equal to the mass of the international

prototype of the kilogram (a platinum-iridium bar stored in Paris), roughly

equal to the mass of one liter of water at standard temperature and pressure

– POUND MASS: (lbm)

• LENGTH

– METER (m): the length of the path traveled by light in vacuum during a

time interval of 1/299792458 of a second

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– FOOT (f t)

• TIME

– SECOND: (s) the duration of 9192631770 periods of the radiation

corresponding to the transition between the two hyperfine levels of the ground

state of the cesium 133 atom

– SECOND: (s) English time units are identical to those of SI

• TEMPERATURE - an equilibrium property which roughly measures

how hot or cold an object is. Note our senses are poor judges of temperature.

Consider snow and air in thermal equilibrium at 20 ◦F. Usually, it is possible

to keep your bare hands warm for many hours at 20 ◦F if you are otherwise

dressed warmly. However, if you place your bare hand in a snow bank you for

a few minutes, you have a danger of frostbite. Yet both are at the same

temperature. Why the difference in sense? Our bodies actually have more

sensitivity to heat fluxes instead of temperature; heat leaves our body more

rapidly when in contact with high density objects like snow relative to that of

low density objects like air. More fundamental than common units such as ◦F

are so-called absolute temperature units:

– Kelvin: (K) the fraction 1/273.16 of the thermodynamic temperature

of the triple point of water

– Rankine: (◦R).

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2.7 ZEROTH LAW OF THERMODYNAMICS

The so-called zeroth law of thermodynamics is the axiom which is

probably most fundamental. It was formalized after the so-called first and

second laws, and so it is called the zeroth law.

• Zeroth law of thermodynamics - When two bodies have equality of

temperature with a third body, then they have equality of temperature.

The origins of the zeroth law are murky. Sommerfeld attributes the notion

to R. H. Fowler in a 1931 review of a thermodynamics book. Fowler and

Guggenheim explicitly introduce the term “zeroth law of thermodynamics”

later. The equivalent statement in mathematical logic is that if x = y and x = z,

then y = z; this is in fact equivalent to the first of Euclid’s common notions:

things that are equal to the same thing are also equal to each other.

Definition of the zeroth law enables the use of a thermometer as a

measurement device. A scale however needs to be defined. The old metric

temperature scale, Celsius (◦C), was defined so that

• 0 ◦C is the freezing point of water, and

• 100 ◦C is the boiling point of water.

These quantities varied with pressure however, so that different values

would be obtained on top of a mountain versus down in the valley, and so this

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is not a good standard. The modern Celsius scale is defined to be nearly the

same, but has

• 0.01 ◦C as the so-called triple point of water, and

• −273.15 ◦C as absolute zero in K.

The triple point of water is defined at the state where three phases of water

(solid, liquid, and gas) are observed to co-exist. The transformation between

the absolute Kelvin scale and the Celsius scale is given by

K = ◦C + 273.15

The English equivalents are degrees Fahrenheit (◦F) for relative

temperature and degrees Rankine (◦R) for absolute temperature. The

conversions are

T( ◦R) = 1.8T(K),

T( ◦F) = 1.8T( ◦C) + 32,

T( ◦F) = T( ◦R) − 459.67

2.8 SECONDARY VARIABLES AND UNITS

Many units can be derived from the base units. Some important units for

thermodynamics include

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• FORCE: This unit is defined from Newton’s second law, m d2 y/dt2 =

PF.

– Newton: (N), 1 N = 1 kg m s 2 , and

– pound force: (lbf).

Force is straightforward in SI units. It is more confusing in English units,

where the so-called gravitational constant gc is often introduced. In SI units, gc

= 1. However in English units, the law for force is better stated as:

Moreover, a gravitational body force is better stated as mg/gc in English

units. Now, 1 lbf is induced by a mass of 1 lbm in places where local

gravitational acceleration is g = 32.1740 ft/s2

• ENERGY: roughly speaking, the ability to do work, found from the

product of force and distance.

– Joule: (J), 1 J = 1 (N m), and

– foot-pound force: (f t lbf).

• Specific Volume: the volume per unit mass, known as v = V/m.

– (m3/kg)

– (ft3/lbm)

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• Density: the mass per unit volume, the inverse of specific volume ρ =

m/V.

– (kg/m3 )

– (lbm/ft3)

Note also that:

• PRESSURE: the limA→0 F/A where A is the cross-sectional area and F is

the component of force acting normal to that area. In thermodynamics, we are

almost always concerned with the absolute pressure as opposed to the gauge

pressure. Most common pressure gauges do not measure the absolute pressure;

instead they measure the difference between the absolute pressure and the

atmospheric pressure. The two are related via the formula

Pgauge = Pabsolute

We nearly always interpret P as an absolute pressure, so we could also say

Pgauge = P – Patm

– Pascal: (P a), 1 P a = 1 N/m2 ; note other common units are 1 bar =

105 Pa, 1 atm = 1.01325 × 105 Pa = 101.325 kPa = 0.101325 MPa, and

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– (psia): 1 psia = 1 lbf/in2. 1 atm = 14.696 psia. The a denotes the

“absolute” pressure as opposed to the “gauge” pressure. The units psig refer to

a gauge pressure.

The SI unit is named after Blaise Pascal, the French polymath who

conducted early scientific experiments with manometers, a common

measuring device for pressure, see Fig. 2.5. There are a variety of styles of

manometers. Here, a pipe containing fluid at pressure P and density ρ has a

small tube with cross sectional area A connecting it to the outside atmosphere

at a different pressure Patm. The length H is easily measured. The gravitational

acceleration is g and is in the negative y direction. Because P > Patm, the

manometer fluid is pushed up. However, it finds a mechanical equilibrium

where the weight of the manometer fluid balances the net force induced by the

pressure differential.

The figure includes a cutaway with a free body diagram. The interior

fluid exerts a positive force of PA on the manometer fluid in the cutaway. The

atmosphere exerts another force of PatmA in the negative direction. The third

force is the weight of the fluid: mg. Thus, Newton’s second law tells us:

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Now, we are concerned with cases which are static, in which case the

acceleration d2y/dt2 = 0. Thus, we require a force balance, i.e. mechanical

equilibrium, which is achieved when

0 = P A − PatmA − mg

P A = PatmA + mg.

Now, mg = ρV g, where V is the volume of the fluid in the cutaway. Obviously from

the geometry, we have V = AH, so mg = ρAHg. Thus,

P A = PatmA + ρAHg

P = Patm + ρgH.

Or ∆P = P − Patm = Pgauge = ρgH

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*QUANTITATIVE ANALYSIS

1. A manometer gives a reading of H = 2ft in a region where local g = 32.2 ft/s2. The

working fluid has specific volume v = 0.0164 f t3/lbm. The atmospheric pressure is

Patm = 14.42 lbf /in2 = 14.42 psia. Find the fluid pressure.

We know that in the SI system

P = Patm + ρgH

In terms of specific volume, recalling that ρ = 1/v, we have

P = Patm + gH/v

The challenge here is really the English units. A fair way to approach English units is

to replace g by g/gc in every formula. Thus, in English units, we have

P = Patm + 1g/vgc (H)

So our fluid pressure is

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2. A piston weighs 4.3 kgs and has a cross sectional area of 450 mm2. Determine the

pressure that is exerted by this piston on the gas in the chamber, as shown in the

figure. Assume gravitational acceleration 'g' to be 9.81 m/sec2.

Solution: From Newton's Law

F = mg

Where: F = Force in Newtons (N)

m = Mass in kilograms (kg)

g = acceleration in m/sec2

So,
F = 4.3 × 9.81

= 42.18 N

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P = (Force / Area)

= [(42.18 / 4.5 × 10– 4) (N/m2)]

= 9.37 × 104 N/m2 = 9.37 × 104 Pa

Or P = 9.37 × 104 Pa × (1kPa / 1000Pa) = 93.7 kPa

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3. The temperature of a given gas is – 10°C. What are the equivalent Fahrenheit and

absolute Kelvin scale readings?

Solution:

The Fahrenheit and Celsius scales are related by the following equation:

TF = [32 + (9/5) Tc]

Where: TF = Temperature in degrees Fahrenheit

Tc = Temperature in degrees Celsius

Therefore, using Eq. (1) we can convert – 10°C to °F.

TF = [32 + {(9/5)(– 10)}]

= 32 + (– 18)

= 14°F

0°C is equivalent to 273°K

Where K = absolute Kelvin scale

To convert from °C to °K, the relationship

Tk = 273 + Tc is used.

The problem above indicates that Tc =– 10°.

Therefore: TK = 273 + (– 10)

= 273 – 10 = 263

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4.Calculate the temperature of a fluid when both a Fahrenheit and a Celsius

thermometer are immersed in it, under the following conditions: a) the numerical

reading is identical in both thermometers and b) the Fahrenheit reading is numerically

twice that of the Celsius reading. Express the values in °R and °K.

Solution: The Fahrenheit scale is related to the Celsius scale by the equation

TC = [(TF – 32) / (1.8)] eq. 1

Where: TC = temperature in the Celsius scale

TF = temperature in the Fahrenheit scale

a) TC = TF = T

Using Eq. (1) T = [(T – 32) / (1.8)]

Solving for T 1.8 T – T = – 32

T = (– 32 / 0.8) = – 40

Therefore, T = – 40°C or T = – 40°F

The relations between the absolute temperature scales and the conventional

scales are given by T(F)abs = TF + 460 eq. 2

The Fahrenheit absolute scale T(F)abs, is also called the Rankine scale (symbol

R) and the Centigrade absolute scale is called the Kelvin scale (symbol K), and TR =

1.8 TK eq. 3

Using Eq. (2) TR = TF + 460

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= – 40 + 460

TR = 420

From Eq. (3) TK = (TR / 1.8)

TK = (420 / 1.8)

= 233.33

b) Using Eq. (1) TC = [(2TC – 32) / (1.8)]

Solving for TC 1.8TC – 2TC = – 32

TC = (– 32 / – 0.2)

= 160

Given TF = 2TC TF = 2 × 160

TF = 320 F

Using Eqs. (2) and (3) TR = TF + 460

= 320 + 460

TR = 780 and,

TK = (TR / 1.8)

= (780 / 1.8)

TK = 433.33

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5. Find the mass of air in a closed chamber measuring 35 ft × 20 ft × 10 ft, when the

pressure is 17 lb/in2 and the temperature is 75°F. Assume air to be an ideal gas.

Solution: The pressure P = 17 (lb / in2) × 122 (in2 / ft2)

= 2448 (lb / ft2)

The volume V of the room = 35 × 20 × 10

= 7000 ft3

TR = TF + 460

= 75 + 460

TR = 535°

R = (R / M)

where R = universal gas constant

R = specific gas constant

M = molecular weight

R = [1545.3 {(ft–lb) / (lbm.mol–°R)}]

M for air = 28.97 lbm / lbm.mol

R = [(1545.3 ft–lb / lbm.mol–°R) / (28.97 lbm / lbm.mol)]

An ideal gas is a simple compressible substance and is defined as one whose thermal

equation of state is given by

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PV = mRT

where P = pressure

V = volume

m = mass

R = specific gas constant

T = temperature

So,

m = PV / RT

= [(2448 lb / ft2 × 7000 ft3) / (53.27 ft–lb / lbm–°R × 535°R)]

= 601 lbm

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6. The gauge pressure in an automobile tire when measured during winter at 32°F was

30 pounds per square inch (psi). The same tire was used during the summer, and its

temperature rose to 122°F. If we assume that the volume of the tire did not change,

and no air leaked out between winter and summer, what is the new pressure as

measured on the gauge?

Solution: From one season to another, the only properties of the gas that will

change are pressure and temperature. The mass (hence the number of moles) and the

volume will remain the same. If it is assumed that this gas is ideal, then

PV = nRT eq. 1

Where: P = Pressure of the gas

V = Volume of the gas

n = number of moles

R = gas constant

T = Temperature of the gas

Rearranging equation (1) to solve for P gives P = (n / V)RT eq. 2

Since n and V are constant, equation (2) shows that pressure is directly proportional

to temperature. That is, P/T = nR/V = constant. Therefore,

(P1 / T1) = (P2 / T2) = (n1R / V1) = (n2R / V2) eq. 3

Where: P1 = initial pressure

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T1 =initial temperature

P2 = final pressure

T2 = final temperature

n1 and n2 are initial and final moles respectively. V1 and V2 are initial and final

volume respectively.

The moles and volume are not changing; therefore, n1 = n2 and V1 = V2. Consequently,

equation (3) can be written as

(P1 / T1) = (P2 / T2) eq. 4

Before equation (4) can be used, the pressure and temperature must be in absolute

scales.

(TC / 5) = [(TF – 32) / 9] eq. 5 and,

P = 14.7 psia + psig eq. 6

Where: TC = temperature in degrees centigrade

TF = temperature in degrees Fahrenheit

Psia = absolute psi

Psig = gauge psi

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Using equations (5) and (6),

122°F = 50°C = (50 + 273)°K = 323°K and,

P = 14.7 + 30 = 44.7 psia

These can now be inserted into equation (4) to give,

(44.7 / 273) = (P2 / 323)

Therefore,

P2 = [(44.7)(323) / (273)] psia

= 52.9 psia

or from equation (6),

52.9 psia = 14.7 psia + x psig

P2 = (52.9 – 14.7) psig

= 38.2 psig

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7. a) Calculate the specific volume of water at 1.0 MPa with an internal energy of

3200 kJ/kg.

b) Determine the enthalpy of freon-12 at 1.0843 MPa and 30°C.

c) Determine the specific volume of freon-12 at 1.0 MPa with an entropy of

0.91 kJ/kg–°K.

In addition, show for each case whether it is a liquid, vapor, or a mixture. Is it

reasonable to assume ideal gas behavior in each case?

Solution: a) Using the given values, the internal energy ug for a saturated

vapor can be obtained from the steam tables.

ug = 2,583 kJ/kg.

Since the given value of the internal energy is greater than the one

obtained from the table ugiven = 3200 kJ/kg > ug = 2583.6 kJ/kg, the state is

superheated vapor.

From the superheated steam tables, the specific volume is

v = 0.2921 m3/kg (by interpolation)

To check for ideal gas behavior the temperature must be known, and is

obtained from the steam tables to be

T = 369.9°C = 643.1°K

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If Tgiven ≥ 2Tcr then ideal gas assumption is reasonable at relatively low pressures (P ≤

10 MPa). From the table of the critical constants, for water Tcr = 647.3°K

Thus, Tgiven ≤ 2Tcr (643.1 << 1,294.6).

Therefore it is not reasonable to assume ideal gas behavior.

b) From the Freon-12 tables at 30°C, the saturation pressure is given as

Psat = 0.7449 MPa.

Since the given value for the pressure is greater than the saturation pressure at

the given temperature, Pgiven = 1.0843 MPa < Psat = 0.7449 MPa, the state is

compressed liquid.

From the same freon-12 table, the enthalpy for the liquid phase is

h = hf = 64.539 kJ/kg.

This value is obtained by using the temperature and not the pressure, since the

enthalpy is a function of the temperature. In this case the substance does not lie in the

superheated region so ideal gas approximations are not reasonable.

c) From the saturated freon-12 tables at the given pressure, the entropies for the

liquid and vapor states are given as

Sf = 0.2767 kJ/kg–K; Sg = 0.6816 kJ/kg–°K (by interpolation)

Since the given value for the entropy is greater than the entropy for the

saturated vapor state: Sgiven = 0.91 kJ/kg–°K > Sg = 0.6816 kJ/kg–°K, the vapor is

superheated.

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From the superheated freon-12 tables, the specific volume is

v = 0.027667 m3/kg

To check for ideal gas behavior the temperature is required. This is obtained from the

freon-12 tables.

T = 154.9°C = 428°K

If Tgiven ≥ 2Tcr then ideal gas approximations are reasonable at relatively

low pressures. From the table of critical constants, for freon-12

Tcr = 384.7°K

Since Tgiven ≤ 2Tcr (428 < 769.4),

it is not reasonable to assume ideal gas behavior.

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8. A cylinder which contains 3 pounds of saturated liquid water at a constant pressure

of 30 psia is heated until the quality of the mixture is 70 per cent.

Calculate: a) the initial temperature,

b) the final pressure and temperature, and

c) the volume change of the mixture.

Solution: a) In a saturation state there is only one saturation temperature for a

given pressure. From the saturation pressure table (steam tables) for water, the

saturation temperature corresponding to 30 psia is 250.34°F.

b) Since the fluid is not completely vaporized, the pressure and

temperature remain equal to the initial values of 30 psia and 250.34°F.

c) The volume and enthalpy changes are computed from the basic

relations ∆V = m(v2 – v1) and ∆H = m(h2 – h1), where 1 and 2 represent the initial and

final states. The initial specific volume and specific enthalpy are read directly from

the steam tables in terms of vf and hf. These values are

v1 = vf = 0.017 ft3/lb and h1 = hf = 218.93 Btu/lb

The values of v2 and h2 must be calculated on a basis of a liquid-vapor mixture of 70

percent quality. Hence

V2 = vf + xvfg = 0.017 + 0.70(13.75 – 0.017) = 9.63 ft3/lb

h2 = hf + xhfg = 218.9 + 0.70(945.4) = 880.7 Btu/lb

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Consequently,

∆V = 3 lb × (9.63 – 0.02) ft3/lb = 28.8 ft3

∆H = 3 lb × (880.7 – 218.9) Btu/lb = 1985

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9. Assuming steam to be an ideal gas, obtain its specific volume and density at a

pressure of 90 lb/in2 and a temperature of 650°F.

Solution: Given P = 90 lb/in2

= [{90 (lb / in2)} × {122 (in2 / ft2)}]

= [{90 (lb / in2)} × {122 (in2 / ft2)}]

The specific gas constant R is related to the universal gas constant R through its

molecular weight M in the following manner.

R = (R / M) eq.1

From the table, M for steam = 18.016

R = (1545.3 / 18.016) [(ft–lb / lbm.mole °R) / (lbm / lbm.mole)]

= 85.77 ft–lb/lbm °R

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v = (RT / P) eq. 2

ρ =1/V eq. 3

Where: v = specific volume of steam

ρ = density of steam

From Eq. 2

v = {(85.77 ft–lb / lbm–°R × 1110°R) / (12960 lb / ft2)}

= 7.34 (ft3 / lbm)

From Eq. 3

ρ = [1 / (7.34 ft3 / lbm)]

= 0.136 (lbm / ft3)

By interpolation from the system tables, the values of v and ρ are 7.26 (ft3 / lbm) and

0.1355 (lbm / ft3) respectively.

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10. A cylinder contains 30 lbm of liquid water and water vapor mixture in equilibrium

at a pressure of 100 lbf/in2. If the volume of the cylinder is 10 ft3 calculate:

a) the volume and mass of liquid

b) the volume and mass of vapor

Solution: The specific volume is calculated first using the formula

v = V/m

= (10.0 / 3.0) = 3.333 ft3/lbm

The quality can now be calculated, using the following equation:

v = vg – (1 – x)vfg

Where: vg = specific volume of saturated vapor

Vf = specific volume of saturated liquid

vfg = vg – vf

Thus, from steam tables,

3.333 = 4.432 – (1 – x) 4.414

(1 – x) = (1.099 / 4.414) = 0.249

solving for x gives x = 0.751

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a) The mass of liquid is given by the formula

m1 = mT(1 – x)

Where: m1 = mass of liquid

mT = total mass

substituting the numerical values

m1 = 3 lbm(0.249) = 0.747 lbm.

The volume of liquid is Vliq = m1vf

The value of vf is obtained from the steam tables at the given states, as

vf = 0.01774 ft3/lbm

Therefore, Vliq = 0.747(0.01774) = 0.0133 ft3.

b) The mass of the vapor is

mv = mTx

Where: mv = mass of vapor

mT = total mass of water

x = quality

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substituting the numerical values

mv = 3 lbm(0.751) = 2.253 lbm.

The volume of the vapor is Vvap = mvap vg

Where vg is obtained from the steam tables at the given state as

Vg = 4.432 ft3/lbm

Therefore, Vvap = 2.253(4.432) = 9.99 ft3

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III. PROPERTIES OF A PURE SUBSTANCE

A pure substance is a material with a constant chemical composition throughout

its entire mass. A pure substance can exist in one or more physical phases such as a

solid, liquid or vapor. Each phase will have homogeneous physical characteristics, but

all three phases could be different physical forms of the same pure substance. The

temperature and pressure boundaries between phases are well defined and it usually

requires an input or extraction of thermal energy to change from one phase to another.

Most pure substances have a well defined Triple Point where all three phases exist in

equilibrium.

In general matter can be classified into two broad categories:

1. Pure-Substances.

2. Mixture.

Each of these categories can be described as:

1. Pure substance - A pure substance is defined as a substance having a constant

and uniform chemical composition. Typically, it can be divided in two groups as:

I. Elements—all the same type of atom.

II. Compounds—substances made from two or more different kinds of atoms.

2. Mixture - The thermodynamic properties of a mixture of substances can be

determined in the same way as for a single substance. The most common

example of this is dry air, which is a mixture of oxygen, nitrogen, a small

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percentage of argon, and traces of other gases. The properties of air are well

determined and it is often considered as a single substance. Mixtures can be

categorized as two general types:

I. Homogeneous—A substance that has uniform thermodynamic properties

throughout is said to be homogeneous. The characteristics of a homogeneous mixture

are;

(a) Mixtures, which are the same throughout with identical properties

everywhere in the mixture.

(b) Not easily separated.

(c) This type of mixture is called a solution. A good example would be sugar

dissolved in water or some type of metal alloy like the CROmium-

MOLYbdenum steel used in many bike frames.

II. Heterogeneous—A heterogeneous mixture is a type of mixture in which the

composition can easily be identified. Often there is two or more phases present. Each

substance retains its own identifying properties (e.g., granite) and it includes.

(a) Mixtures, which have different properties when sampled from different

areas. An example of this would be sand mixed with water.

(b) A mixture in which the individual components can be seen with the naked

eye.

(c) A mixture that can be easily separated.

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Air is a homogeneous mixture of the gases nitrogen, oxygen, and other minor

gases.

A pure substance normally requires only two independent properties to specify

its state. If pressure and specific volume, for example, are fixed, then all the other

properties become fixed. The equation relating pressure, volume, and temperature to

each other is called an Equation of State. However, a more fundamental equation is

required to specify all thermodynamic variables as a function of only two properties.

An example of a simple equation of state which is satisfactory for most dilute gases is

the Ideal Gas Law—pV = nRT.

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3.1 THE PURE SUBSTANCE

We define a

 Pure substance: a material with homogeneous and invariable composition. To

elaborate,

 Pure substances can have multiple phases: an ice-water mixture is still a pure

substance.

 An air-steam mixture is not a pure substance.

 Air, being composed of a mixture of N2, O2, and other gases, is formally not a

pure substance. However, experience shows that we can often treat air as a

pure substance with little error.

3.2 PHASES OF A PURE SUBSTANCE

There are three principle phases – solid, liquid and gas, but a substance can have

several other phases within the principle phase. Examples include solid carbon

(diamond and graphite) and iron (three solid phases). Nevertheless, thermodynamics

deals with the primary phases only. In general:

- Solids have strongest molecular bonds.

- Solids are closely packed three dimensional crystals.

- Their molecules do not move relative to each other

- Intermediate molecular bond strength

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- Liquid molecular spacing is comparable to solids but their molecules can

float about in groups.

- There is molecular order within the groups

- Weakest molecular bond strength.

- Molecules in the gas phases are far apart, they have no ordered structure

- The molecules move randomly and collide with each other.

- Their molecules are at higher energy levels, they must release large amounts

of energy to condense or freeze.

3.3 THERMAL EQUATIONS OF STATE

Here, we will describe some of the many different ways to capture the relation

between two independent properties and a third dependent property for a simple

compressible substance. We will focus on a so-called

 Thermal equation of state - an equation which gives the pressure as a function

of two independent state variables. An example is the general form:

P = P(T, v)

We will progress from simple thermal equations of state to more complex.

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3.3.1 IDEAL GAS LAW

For many gases, especially at low density and far from the critical point, it is

possible to write a simple thermal equation of state which accurately describes the

relation between pressure, volume, and temperature. Such equations were developed

in the 1600s and early 1800s based entirely on macroscopic empirical observation. In

the late 1800s, statistical mechanics provided a stronger theoretical foundation for

them, but we will not consider that here.

Let us start with the most important equation of state:

 Ideal gas law - This equation, which is a combination of Boyle’s law, Charles’

law, and Avogadro’s law, is most fundamentally stated as

P V = nRT

On the continent, Boyle’s law is sometimes known as Mariotte’s law after

Edme Mariotte (1620-1684), but Boyle published it fourteen years earlier. The data in

(V, 1/P) space is fit well by a straight line with intercept at the origin; that is 1/P =

KV, where K is a constant. Thus, P V = C, where C = 1/K is a constant.

It is critical that the temperature here be the absolute temperature. For the

original argument, see Thomson.8 Here, n is the number of moles. Recall there are N

= 6.02214179× 1023 molecules in a mole, where N is Avogadro’s number. Also R is

the universal gas constant, whose history is recounted by Jensen. From experiment,

many performed by by Regnault, depicted in Fig. 3.11, it is determined to be

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Intensive properties without over bars will be on a per mass basis. Recall the mass-

basis specific volume is v = V/m. Let us define the mole-based specific volume as

Thus, the ideal gas law can be represented in terms of intensive properties as

There are other ways to write the ideal gas law. Recall the molecular mass M is the

mass in g of a mole of substance. More common in engineering, it is the mass in kg of

a kmole of substance. These numbers are the same! From chemistry, for example, we

know the molecular mass of O2 is 32 g/mole = 32 kg/kmole. Symbolically, we can

say that

Now, take the ideal gas law and divide by m:

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Now, let us define

Let’s check the units:

We have actually just lost some universality. Recall R is independent of material. But

since each different gas has a different M, then each gas will have its own R.

With this definition, the ideal gas law becomes

This is the form we will use most often in this class. Note the useful fact that

Thus, if an ideal gas undergoes a process going from state 1 to state 2, we can safely

say

Similarly, the ideal gas equation P(v, T) = RT/v describes a surface in the P

− v − T volume. A surface for air is shown in Fig. 3.14. Often, it is easier to

understand the behavior of the thermodynamic surfaces by projection into various

thermodynamic planes and plotting various iso-contours. Let us do this for an ideal

gas.

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 isobars:

– Consider curves in the T − v plane on which P is constant. Thus, for the ideal

gas, we consider:

If we insist that P is constant, this gives the equation of an isobar in the T −

v plane. Moreover, for the ideal gas, we see that in the T − v plane isobars are straight

lines with slope P/R. The slope is always positive since P > 0 and R > 0. So if the

pressure is high, the slope is positive and steep. If the pressure is low, the slope is

positive and shallow.

– Consider curves in the P − v plane in which P is constant. Thus, we

consider P = constant, which are straight horizontal lines in the P − v plane.

– Consider curves in the P − T plane in which P is a constant. Thus, we

consider P = constant, which ar e straight horizontal lines in the P − v plane.

 isotherms

– Consider curves in the T − v plane on which T is constant. Thus, for the

ideal gas, we have T = constant. These are straight horizontal lines in the T − v

plane.

– Consider curves in the P − v plane on which T is a constant. Thus, for the

ideal gas, we have

These are hyperbolas in the P − v plane.

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– Consider curves in the P − T plane on which T is a constant. Thus, for the

ideal gas, we have T = constant. These are straight vertical lines in the P − T

plane.

 isochores

– Consider curves in the T − v plane on which v is constant. Thus, for the

ideal gas, we have v = constant. These are straight vertical lines in the T − v

plane.

– Consider curves in the P − v plane on which v is a constant. Thus, for the

ideal gas, we have v = constant. These are straight vertical lines in the P − v

plane.

– Consider curves in the P − T plane on which v is a constant. Thus, for the

ideal gas, we have

These are straight lines in the P − T plane with slope R/v. Since R > 0 and v

> 0, the slope is always positive. For large v, the slope is shallow. For small v, the

slope is steep.

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3.3.2 TABULAR THERMAL EQUATIONS OF STATE

Often equations are too inaccurate for engineering purposes. This is

generally because we may be interested in behavior under a vapor dome. In such

cases, one should use tables to find a third property, given two independent

properties. We can say that the thermal equation of state is actually embodied in the

tabular data.

We lay down some rules of thumb for this class:

• If steam, use the tables.

• If air or most other gas, use the ideal gas law, but check if the pressure is high

or the properties are near the vapor dome, in which case use compressibility

charts or non-ideal state equations.

3.3.2.1 SATURATED LIQUID-VAPOR WATER, TEMPERATURE

TABLES

For water, the most important table is the saturated steam table. One should

go to such tables first. If the water is a two-phase mixture, tables of this type must be

used as the equation of state. Recall, for two-phase mixtures, pressure and

temperature are not independent thermodynamic variables. Two properties still

determine the state, but quality x is now important. So for two-phase mixtures we

allow

• T = T(v, x),

• P = P(v, x), or

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• v = v(T, x)

Consider the structure of saturation tables, as shown in Table 3.2, extracted

from BS’s Table B.1.1. Data from the steam tables is sketched in Fig. 3.23. We have

the notation:

• f: saturated liquid,

• g: saturated vapor,

• vf : specific volume of saturated liquid, and

• vg: specific volume of saturated vapor.

Note for liquid-vapor mixtures, this table begins at the triple point temperature 0.01

◦C and ends at the critical temperature 374.1 ◦C. At P = Pc and T = Tc, we have vf =

vg. Note that

• vf ≃ constant

• vg decreases with increasing T

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We define vfg as vfg ≡ vg − vf

Recall the quality x is

Consider a mass of fluid m in total volume V. We must have

V = Vliq + Vvap,

m = mliq + mvap.

Now, use the definition of specific volume and analyze to get

We get the final important results:

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3.3.2.2 SATURATED LIQUID-VAPOR WATER, PRESSURE TABLES

Sometimes we are given the pressure of the mixture, and a saturation table

based on the pressure is more useful. An example of a portion of such a table is

shown in Table.

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*QUANTITATIVE ANALYSIS

1. Given air in a cylinder with stops and a frictionless piston with area A = 0.2 m2 ,

stop height of 1 m, and total height of 2 m, at initial state P1 = 200 kP a and T1 = 500

◦C with cooling, find

a) the temperature when the piston reaches the stops, and

b) the pressure if the cooling continues to T = 20 ◦C.

The initial state along with a free body diagram is sketched in Figure.

We have three distinct states:

• state 1: initial state

• state 2: piston reaches the stops

• state 3: final state, where T = 20◦C.

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At the initial state, the total volume is

V1 = A((1 m) + (1 m)) = (0.2 m2 )(2 m) = 0.4 m3

We also know that P1 = 200 kP a. For use of the ideal gas law, we must use absolute

temperature. So

T1 = 500 + 273.15 = 773.15 K

Now, use the ideal gas law to get v1:

Let us check the units:

As long as we employ kJ for energy and kP a for pressure, we will have few

problems with units. Now, the mass of the air, m, is constant in this problem. Since

we have V1 and v1, we can get m:

Now, as long as the piston does not touch the stops, it will be in a force

balance giving PatmA = PA. So our atmosphere must be at Patm = 200 kPa. As the air

cools, its temperature will go down. Since Pv = RT , as temperature goes down with

constant P, we expect the volume to decrease. Just when the piston hits the stops, the

stops still exert no force on the piston, so

P2 = P1 = 200 kPa

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Now, after the piston reaches the stops, the volume is constant. So the process from 2

to 3 is isochoric, and V3 = V2 = 0.2 m3

Thus v3 = v2 = 0.554735 m3 /kg

So,

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2. Given a vessel with V = 0.4 m3 filled with m = 2 kg of H2O at P = 600 kP a, find:

a) the volume and mass of liquid, and

b) the volume and mass of vapor.

First, calculate the specific volume of the water:

Next go to the saturated water tables with pressure entry to see if the water is a two-

phase mixture. We find at P = 600 kPa that

Now, for our mixture, we see that vf < v < vg, so we have a two-phase mixture. Now,

apply Eq. (3.61) to find the quality.

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Now, we have x = mvap/mtotal, so

Now, for the liquid mass we have

Most of the mass is vapor, but the fraction that is liquid is large. Now, let us calculate

the volumes

The volume is nearly entirely vapor.

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3. A tank has a volume of 0.5 m3 and contains 10 kg of an ideal gas having a

molecular weight of 24. The temperature is 25 °C. What is the pressure? The

gas constant is determined first:

We now solve for P:

= 2066kPa

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4. At what temperature will 0.654 moles of neon gas occupy 12.30 liters at 1.95

atmospheres?

Solution:

1) Rearrange PV = nRT to this:

T = PV / nR

2) Substitute:

T = [ (1.95 atm) (12.30 L) ] / [ (0.654 mol) (0.08206 L atm mol¯1 K¯1) ]

T = 447 K

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5. A 12.0 g sample of gas occupies 19.2 L at STP. What is the molecular weight

of this gas?

Solution:

1) Use PV = nRT:

(1.00atm) (19.2 L) = (n) (0.08206) (273 K)

n = 0.8570518 mol

2) Determine the molecular weight:

12.0 g / 0.8570518 mol = 14.0 g/mol

3) Since it is at STP, we can also use molar volume:

(19.2 L / 12.0 g) = (22.414 L / x)

19.2x = 268.968

x = 14.0 g/mol

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6. 1.00 mole of gas occupies 22.414 L at STP. Calculate the temperature and

pressure conditions needed to fit 2.00 moles of a gas into a volume of

22.414L.

Solution:

1) Notice that the problem asks for two conditions: one of temperature and one of

pressure. The answer we arrive at will not be a value of T and one of P, but a

ratio between the two. Start here:

PV = nRT

2) Insert our known values:

(P) (22.414 L) = (2.00 mol) (0.08206 L atm / mol K) (T)

3) Since the question mentions T first, let's determine a T/P ratio:

T/P = 22.414 L / [(2.00 mol) (0.08206 L atm / mol K)]

T/P = 136.57 K/atm

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7. A balloon has a mass of 0.5 g when completely deflated. When it is filled with

an unknown gas, the mass increases to 1.7 g. You notice on the canister of the

unknown gas that it occupies a volume of 0.4478 L at a temperature of 50 °C.

You note the temperature in the room is 25 °C. Identify the gas.

Solution:

1) Use Charles' Law to get volume at 25 °C:

0.4478 / 323 = x / 298

2) Assume balloon is at 1.00 atm. Use PV = nRT to get moles of gas:

(1.00) (0.41314) = (x) (0.08206) (298)

3) Divide grams of gas (1.7 g - 0.5 g = 1.2 g) by moles to get moles weight:

1.2 g / 0.01689466 mol = 71.0 g/mol

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8. A 10.20 g sample of a gas has a volume of 5.25 L at 23.0 °C and 751 mmHg.

If 2.30 g of the same gas is added to this constant 5.25 L volume and the

temperature raised to 67.0 degrees Celsius, what is the new gas pressure?

Solution:

1) Use PV = nRT to determine moles of 10.20 g sample:

(751 mmHg/760 mmHg atm-1) (5.25 L) = (n) (0.08206 L atm mol-1 K-1) (296 K)

n = 0.21358 mol

2) Determine molecular weight of gas:

10.20 g / 0.21358 mol = 47.757 g/mol

3) Determine moles of 2.30 g of gas:

2.30 g / 47.757 g/mol = 0.04816 mol

4) Determine new pressure with new amount of moles and at new temperature:

(P) (5.25 L) = (0.26174 mol) (0.08206 L atm mol-1 K-1) (340 K)

P = 1.39 atm

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9. A gas consisting of only carbon and hydrogen has an empirical formula of

CH2. The gas has a density of 1.65 g/L at 27.0 °C and 734.0 torr. Determine

the molar mass and molecular formula of the gas.

Solution:

1) Use PV = nRT to determine moles of the gas in 1.00 L:

(734.0 torr/760.0 torr atm-1) (1.00 L) = (n) (0.08206 L atm mol-1 K-1) (300. K)

n = 0.039231 mol

2) Determine molecular weight of gas:

1.65 g / 0.039231 mol = 42.06 g/mol

3) Determine the molecular formula:

The "empirical formula weight" of CH2 = 14.027

"Empirical formula weight" units of CH2 present:

42.06 / 14.027 = 2.998 = 3

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10. The vapor pressure of water at 25 °C is 23.76 torr. If 1.50 g of water is

enclosed in a 2.0 L container, will any liquid be present? If so, what mass of

liquid?

Solution:

1) Use the ideal gas law to find out how many moles of gas would have to be

vaporized to obtain a pressure of 23.76 torr.

PV = nRT

Where:

P = gas pressure in atm = 23.76 torr x (1 atm / 760 torr) = 0.0313 atm

V = gas volume in L = 2.0

n = moles of gas = ?

R = gas constant = 0.08206 L atm / K mole

T = Kelvin temperature = 25 °C + 273 = 298 K

n = PV / RT = (0.0313)(2.0) / (0.08206)(298) = 0.00255992 moles of H2O gas

2) Determine mass of the water vapor:

0.00255992 moles H2O gas x (18.015 g H2O / 1 mole H2O) = 0.046117 g H2O gas

3) Amount of H2O liquid in the container:

total g H2O - g H2O gas = 1.50 - 0.046117 = 1.45 g H2O liquid

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IV. WORK AND HEAT

It is essential to understand clearly the definitions of both work and heat,

because the correct analysis of many thermodynamic problems depends on

distinguishing between them.

4.1 WORK

Work is defined as a force F acting through a displacement x, the displacement

being in the direction of the force.

Thermodynamics defines work as follows: work is done by a system if the sole

effect on the surroundings (everything external to the system) could be the raising

of a weight. Work done by a system is considered positive and work done to a

system is considered negative.

In differential form, we have

In one-dimensional systems, we have

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Note that we have anticipated that the work differential is inexact. This is an

important point, as work integrals will be path-dependent, and work will not be a state

variable for a system. Here, F is a three-dimensional force vector, x is a three-

dimensional distance vector, and · is the dot product operator. Recall that the dot

product of two vectors yields a scalar. The terms F and x are scalar equivalents valid

for one-dimensional systems. The units of force are N, those of distance are m, so the

units of work are N m, which have been defined as Joules (J).

Work is done by a system if the sole effect on the surroundings (i.e. everything

external to the system) could be the raising of a weight. We take the following sign

convention:

o + work done by the system,

o − work done on the system

This sign convention is not universal. Many physicists use precisely the opposite

convention. Probably the reason for this convention is that thermodynamics is a

science that was invented by engineers in the nineteenth century. And those engineers

wanted to produce work from steam engines. Systems doing work were viewed

favorably and endowed with a positive sign. We associate energy with the ability to

do work. We define

• Power - the time rate of doing work = δW/dt.

• Specific work - the work per unit mass w = W/m. Because work is path-

dependent, the intensive quantity w is not a thermodynamic state variable.

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4.1.1 WORK FOR A SIMPLE COMPRESSIBLE SUBSTANCE

Consider the scenario sketched in Fig. 4.4. In state 1, we have a material at

pressure P confined in a cylinder of cross-sectional area A. The height of the piston in

the cylinder is x. The pressure force of the material on the piston is just balanced by

weights on top of the piston.

Now, remove one of the weights. We notice a motion of the piston to a new

height x+dx. We let a long time elapse so the system comes to rest at its new

equilibrium. We notice there is a new pressure in the chamber, P + dP sufficient to

balance the new weight force. Obviously work was done as a force acted through a

distance. Let us calculate how much work was done. The differential work is given

from equation above as:

Now, F varies during the process. At state 1, we have F = P A. At state 2, we

have F = (P + dP)A. Let us approximate F by its average value:

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So,

Let us only retain terms which are differential and neglect the square of

differential terms,

Now, since Adx = dV , the differential volume, we get the important formula:

We can integrate this and get the equally important,

• Polytropic process - a process which is described well by an equation of the

form P V n = constant = C.

Here, n is known as the polytropic exponent.

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4.1.2 OTHER FORMS OF WORK

We note that there are other forces besides pressure forces, and those forces

can also do work. Consider:

• a stretching wire stretched by tension force F through length change dL. The

differential work is

• a surface with surface tension S. The differential work is

• a system with electrical work where E is the electrical field strength, q is the

particle charge, and x is the distance:

In total, for materials which are more than simple compressible substances, we have

It can be shown that the more work modes we include the more independent

thermodynamic variables are necessary to specify the state of the system.

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4.2 HEAT

Heat is defined as the form of energy that is transferred across the boundary of

a system at a given temperature to another system (or the surroundings) at a lower

temperature by virtue of the temperature difference between the two systems. Another

aspect of this definition of heat is that a body never contains heat. Rather, heat can be

identified only as it crosses the boundary. Thus, heat is a transient phenomenon.

We adopt the notion that bodies do not contain heat, but that heat only has

relevance as a type of energy that crosses system boundaries. Note that work is in a

similar class; it is not contained within a system, but can be identified when it crosses

system boundaries. We will make a distinction between heat and work energy

transfers.

We also note that when two bodies are at the same temperature, there can be

no heat transferred between the two bodies. The subject of heat transfer considers the

details of the heat transfer process. There are three fundamental classes of heat

transfer:

• heat diffusion, also called conduction. Physically this is due to local effects.

Bacon is fried via conduction effects as a culinary example. This is characterized by

Fourier’s law.

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Where: q is the heat flux vector with unit J/s/m2 = W/m2

k is the thermal conductivity with unit J/s/m/K = W/m/K, and

∇T is the vector representing the gradient of temperature.

In one dimension, we get

If we multiply by the local cross-sectional area, we find Q˙ = qA, and

Here, Q˙ has unit J/s or W (Watts).

• convection. This is actually a version of conduction, albeit enhanced by fluid

flow. For some systems, convective effects are well modeled by Newton’s law of

cooling:

Here, h is a constant with units W/m2/K.

• thermal radiation. Physically this is due to remote effects. The earth is heated

by the sun via radiation effects, not conductive energy diffusion. For some systems,

the radiative heat transfer rate is well modeled by:

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Here, σ is the Stefan-Boltzmann constant, σ = 5.67 × 10−8 W/m2/K4.

We adopt the traditional engineering sign convention for heat:

• + heat enters the system,

• - heat leaves the system.

The sign convention again is motivated by nineteenth century steam engines.

Heat had to be added into a system to get work out of the system. Since engineers

were and are concerned with this problem, this convention is taken.

We define a special kind of process in which Q = 0 as

• Adiabatic - a type of process for which there is no heat transfer.

As is work, heat transfer is a path function characterized by inexact differentials. We

take:

Here, q is the specific thermal energy transfer. It has units J/kg. Note q 6= q,

where q is the heat flux with units W/m2 . In this thermodynamics course, we will

mainly be concerned with q. In a heat transfer course, q is more important.

We finish with some notes of comparison:

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• Q and W as well as q and w are affiliated with transient phenomena; both

cross boundaries when the system changes state.

• Q and W as well as q and w only exist at system boundaries.

• Q and W as well as q and w are both path-dependent, have inexact

differentials, and are not properties of the system.

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*QUANTITATIVE ANALYSIS

1. Consider as a system the gas in the cylinder in Fig. 4.2; the cylinder is fitted with a

piston on which a number of small weights are placed. The initial pressure is 200 kPa

and the initial volume of the gas is 0.04 m3.

1. Let a Bunsen burner be placed under the cylinder, and let the volume of the

gas increase to 0.1 m3 while the pressure remains constant. Calculate the

work done by the system during the process.

Since the pressure is constant,

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2. Consider the same system and initial conditions, but at the same time the

Bunsen burner is under the cylinder and the piston is rising, let weights be

removed from the piston at such a rate that, during the process, the temperature of

the gas remains constant. If we assume that the ideal-gas model is valid, and that

is a polytropic process with exponent n = 1. Therefore,

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3 The figure shows a chamber containing 0.04 m3 of a gas. The initial pressure

which is supplied by weights on the piston is 200 kPa. Keeping this pressure

constant the chamber is heated until the volume of the gas is 0.1 m3. Considering

the gas in the chamber as a system, a) calculate the work done by the system.

While heating is going on, weights are removed from the piston in such a way that

the relation between pressure and volume is given by the expression. b) PV =

constant = P1V1 = P2V2, c) PV1.3 = constant. Calculate the work done in both cases

if the initial conditions are the same and the final volume is 0.1 m3. d) Let the

piston be fixed so that the volume remains constant. For the same initial

conditions calculate the work done if heat is removed from the system and the

pressure drops to 100 kPa.

Solution: a) Since the pressure is constant,

1W2 = 2∫1 δW = 2∫1 PdV

= P(V2 – V1)

1W2 = 200 kPa × (0.1 – 0.04)m3

= 12.0 kJ

b) Determine the final pressure first.

P2 = [(P1V1) / V2]

= [200 × {(0.04) / (0.10)}]

= 80 kPa

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1W2 = 2∫1 PdV

Substitute P = constant / V = [(P1V1) / V] into this equation,

1W2 = P1V1 2∫1 (dV / V) = P1V1 In (V2 / V1)

= [200 kPa × 0.04 m3 × ln {(0.10) / (0.04)}]

= 7.33 kJ

c) First solve for the general case of PVn = constant

PVn = constant = P1V1n = P2V2n

P = (constant / Vn) = [(P1V1n) / Vn]

= [(P2V2n) / Vn]

1W2 = 2∫1 PdV = constant 2∫1 (dv / Vn)

= constant [(V–n+1) / (– n+1)]21

= [{(constant) / (1 – n)} {V21 – n – V11 – n}]

= [(P2V2nV21 – n) – (P1V1nV11 – n) / (1 – n)]

= [(P2V2 – P1V1) / (1 – n)]

In this case

P2 = 200 (0.04 / 0.10)1.3

= 60.77 kPa

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1W2 = [(P2V2 – P1V1) / (1 – 1.3)]

= [(60.77 × 0.1 – 200 × 0.04) / (1 – 1.3)]

= 6.41 kJ

d) Since δW = PdV

For a quasiequilibrium process, the work is zero, because in this case there is

no change in volume.

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4 Air inside a chamber is heated from an initial volume and pressure of 1.0 ft3 and

1500 psia respectively to a final volume of 8.0 ft3. Calculate the total work done

by the gas if the expansion process is quasi-static and given by the relation PV1.4 =

constant.

Solution: Since the process is quasi static the work done by the gas is

W12 = 2∫1 p dV eq. 1

Since pV1.4 = constant,

p = (constant / V1.4)

= [(p1V11.4) / V1.4]

= [(p2V21.4) / V1.4]

Substituting into Eq. 1, gives

W12 = constant 2∫1 (dV / V1.4)

= [{constant / (1 – 1.4)} (V21 – 1.4 – V11 – 1.4)]

= [{(p2V21.4) / (1 – 1.4)} (V21 – 1.4 – V11 – 1.4)]

= [{(1500 × 144) (1.0)1.4} / (1 – 1.4)] (81 –1.4 – 1.01 – 1.4)

= 305,000 ft-lbf.

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5 A vessel with a piston contains one pound mole of an ideal gas. The gas is

expanded at a constant temperature of 100°F from 20atm pressure to 5 atm.

Assuming losses to be negligible, calculate the work done for the following cases:

a) The expansion rate is large against a pressure of 1 atm.

b) The expansion rate is negligible.

c) The expansion rate is so large that it approaches infinity.

Solution: a) The resisting pressure is 1 atm.

W = (V)2∫(V)1 PrdV

= Pr (V2 – V1)

= PrRT(1/P2 – 1/P1)

= [(14.7) (144)] (0.73) (460 + 100) [1/5 – (1 / 20)]

= 166.7 Btu/lb mole

b) Since there is hardly any rate of expansion, i.e. the resisting pressure is equal to

that of the system, therefore

W = (V)2∫(V)1 (RT / V) dV

= RT In (V2 / V1)

= – RT

In (P2 / P1)

= – (1.987) (460 + 100) In (5 / 20)

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= 1546 Btu/lb mole.

c) Since the resisting pressure is equal to zero

W = 0.

6 How many joules are equivalent to one lit-atm of work?

Solution: For 76.00–cm column of mercury (density = 13.596 gm/cm3)

supported by the atmosphere,

M/A = (76 cm) (13.6 gm/cm3) = 1033 gm/cm2 = 1.033 kgm/cm2.

Hence,

PX = Mg/A = (1.033 kgm/cm2) (9.81 meter/sec2)

= 10.13 kgm–meter/sec2–cm2 = 10.13 newton/cm2; and one lit-atm will

represent

PXΔV = (10.13 newton/cm2) (1000 cm3) = 10130 newton–cm

= 101.3 newton–meter = 101.3 joule.

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7 During a process the volume of a unit weight system changes from 5 cu. ft to 3 cu.

ft. (a) Calculate the work done for this process if P = (500 / V) + 0.060 V3, where

P is the pressure and v is the specific volume. (b) Also calculate the work done for

the process if frictional losses are neglected.

Solution: (a) When losses are taken into account the work done for a process

which involves a unit weight system is

W + J = ∫ PdV

= (V)B=5∫(V)A=5 [(500 / V) + 0.060 V3)dV

= [500(In 3 – In 5) + {(0.060) / 4} (34 – 54)] × (0.1850)

= – 48.8 Btu/lb

∴ W = (– 48.8 – J) Btu/lb.

(b) If frictional losses are neglected, J = 0

W = ∫ PdV = – 48.8 Btu/lb.

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8 Calculate the heat transferred when 100J of work is done on a system consisting

of 1 mole of an ideal gas. At constant temperature, ΔE = 0 for the expansion of an

ideal gas.

Solution: A statement of the first law of thermodynamics is expressed as

ΔE = q – w

Where: ΔE = change in internal energy of the system

q = quantity of heat

w = work done

In this problem, work is done on the system and so w is negative. (Note

that we are adopting the convention that work done on the system is negative.) Since

ΔE = 0 for an isothermal expansion of an ideal gas,

ΔE = 0 = q – w

∴ q = w or,

q = – 100J

As a result, 100J of heat must be transferred from the system to maintain

isothermal conditions.

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9 What can you say about the following statements if one has an adiabatic process

in which there is no heat transfer between the system and the surroundings, either

because the system is well insulated or because the process occurs very rapidly?

1. q = + w

2. q = 0

3. ΔE = q

4. ΔE = w

5. PΔV = 0

Solution: In an adiabatic system there is no heat flow into or out of the system, thus

q=0

1. This statement gives q to be +w but this can only happen when ΔE = 0

since for instance ΔE = q – w for isothermal expansion of an ideal gas.

2. Statement (2) is correct since q = 0 for the process.

3. This statement indicates ΔE = q, but this can only happen, as in the case when

one expands a gas into a vacuum, when w = 0.

4. Since ΔE = q – w, ΔE will be equal to w only when q = 2w so that ΔE = 2w –

w=w

5. ΔE = q – w

= q – PΔV

Thus for PΔV to be zero, ΔE must be equal to q such that ΔE = ΔE – PΔV

∴ PΔV = 0

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10 An air compressor compresses air from 15psia to 75psia according to the relation

PV1.3 = constant along the path of compression.

a) Calculate the work done during the compression process if the entrance and

exit velocities are assumed to be the same.

b) Also calculate the shaft work of the compressor. Take specific volume of air to

be 13.1 cu ft/lb.

Solution: a) The work done w = (V)2∫(V)1 pdv.

Given: pv1.3 = C = p1v1 = p2v2 eq. 1

∴ p = (C / v1.3) = Cv–1.3 eq. 2

But, p1v11.3 = p2v21.3

∴ v21.3 = (p1 / p2) v11.3

v2 = (p1 / p2)1/1.3 v1 eq. 3

= (15 / 75)1/1.3 × 13.1 cu. Ft

= 3.8 cu. ft.

From Eq. 2 1W2 = (V)2∫(V)1 Cv–1.3 dv

= [C(v)2–0.3 / –0.3](V)2 (V)1 eq. 4

From Eq. 1 and 4 W = {(p2v21.3 × v2–0.3) – (p1v11.3 × v1–0.3) / (–0.3)}

= [(p2v2 – p1v1) / –0.3]

= (122 / 0.3) (15 × 13.1 – 75 × 3.8)

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= [(– 144 × 88.5) / 0.3]

= – 42,480 ft lb per lb.

b) In this case the work done by the shaft (Ws), i.e. the power required to drive the

shaft is to be determined.

WS = – (P)2∫(P)1 vdp + {(V12 – V22) / 2β}0 + g/β (Z1 – Z2)0

= – (P)2∫(P)1 vdp

p1/1.3 v = C1/1.3

v = (C)1/1.3 (p)–1/1.3

∴ WS = – C1/1.3 (P)2∫(P)1 p–1/1.3 dp

= – C1/1.3 [(p2(–1/1.3)+1 – p1(–1/1.3)+1) / {– (1 / 1.3) + 1}]

= [(– p2v2 – p1v1) / {– (1 / 1.3) + 1}]

= – 1.3 {(p2v2 – p1v1) / (1.3 – 1)}

= – 4.34 (p2v2 – p1v1)

= 122 × (– 4.34)(75 × 3.8 – 15 × 13.1)

= 55224 ft lb per lb.

Due to losses, the work done in each case is not the same.

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V. THE FIRST LAW OF THERMODYNAMICS

In this chapter, we will expand our notion of energy and in so doing recover a new

conservation principle. This new principle, not known to Newton, is the first law of

thermodynamics. It takes many equivalent forms, and relies at a minimum on the

introduction of a new type of energy, thermal energy, which is necessary to conserve

the total energy.

Thermal energy is actually a macro-scale representation of micro-scale

mechanical energy. Recall that at the micro-scale, molecules are in random motion.

This random motion has kinetic energy associated with it. But we cannot hope to keep

track of it all for each individual particle. So we surrender knowledge of the micro-

scale motions, and allow the temperature to be a measure of the average micro-scale

kinetic energy. We can also take the historical approach and develop the principle of

energy conservation without further appeal to micro-scale arguments. Let us begin

that approach here.

5.1 REPRESENTATION OF THE FIRST LAW

There are a variety of ways to represent the first law of thermodynamics, also

known as the principle of conservation of energy. Some of them are not obvious, but

have withstood the scrutiny of detailed experiment. Perhaps the simplest, but also the

most obtuse, is the following.

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5.1.1 CYCLE

• First law of thermodynamics - During any cycle, the cyclic integral of heat

added to a system is proportional to the cyclic integral of work done by the

system.

Here J is a proportionality constant, sometimes known as the mechanical

equivalent of heat. Now, during the development of thermodynamics, Q was

measured in cal, where 1 cal represented the energy necessary to raise 1 g of water 1

◦C, and W was measured in J which represented the work done in moving a 1 kg mass

against a gravitational field of strength g = 1 m/s2 through a distance of 1 m.

Now, in this class, we will not bother much with the mechanical equivalent of

heat, and simply insist that Q be measured in units of work. When Q has units of J,

then J = 1, and we recover our preferred form of the first law:

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5.1.2 PROCESS

We arrive at an alternate representation of the first law by the following analysis.

Consider the sketch of Fig. 5.6. Now, consider two cycles, each passing through

points 1 and 2, albeit via different paths:

• Cycle I: 1 to 2 on Path A followed by 2 to 1 on Path B,

• Cycle II: 1 to 2 on Path A followed by 2 to 1 on Path C.

The only difference between Cycles I and II is they take different return paths.

Now, write the first law H δQ = H δW for Cycle I:

For Cycle II, we have similarly

Now, subtract first equation to second equation to get:

Rearrange the new equation to get:

Now, B and C are arbitrary paths, asserts that the integral of δQ − δW from 2 to 1 is

path-independent. This is in spite of the fact that both W and, as we will see later, Q

are path-dependent quantities. Therefore, we can deduce that this defines

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• energy - a thermodynamic property which is a theoretical construct suggested

by the first law of thermodynamics as something to account for the difference

between heat transfer and work in any process between the same start and end

states.

Energy is a new extensive property of the system denoted by E. While we like

to think we have intuition for what constitutes energy, it really is an elusive quantity.

Viewed at another way, the Newtonian mechanical energy is easily visualized in

terms of kinetic and potential energy, but it is not always conserved! Our new energy

includes thermal energy, which we think we can easily feel, so we still have a good

intuition for it. So we have generalized energy so that it is always conserved, at the

expense of losing the ability to easily visualize it.

Recall that properties depend only on the state and not the path taken to arrive

at the state. Let us then take the following definition for the differential of E:

If we integrate from 1 to 2, we get

Yielding

The equation above is the alternate representation of the:

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• First law of thermodynamics - For a system undergoing a process, the change

in energy is equal to the heat added to the system minus the work done by the

system.

Now, we consider E to represent the total energy of the system. It has units of J. It

includes energy which is

• potential,

• kinetic,

• thermal,

• chemical,

• electrical,

• magnetic,

• etc.

We will find it useful to lump all of the types of energy which are not potential or

kinetic into a single term U, which we call

• internal energy - that portion of total energy E which is not kinetic or

potential energy. It includes thermal, chemical, electric, magnetic, and other

forms of energy.

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We take U to have units of J. We call the kinetic energy KE and the potential

energy P E. So we take:

In this course we shall mainly be concerned with changes of U which are associated

with changes of the thermal energy of the system. A useful way to think of thermal

energy is

• Thermal energy - kinetic energy associated with random motions of

molecules at the microscale

We can only observe this microscale kinetic energy with great difficulty. We

usually have no hope of having any detailed knowledge of it, and so only consider it

in the average. In fact, the temperature is a measure of the average microscale kinetic

energy. We distinguish the thermal energy from KE, which we take to exist at the

observable macroscale.

Each form of energy is an extensive property of the system. Taking differentials of

equation above we get:

So the first law, dE = δQ − δW, can be written as

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5.2 SPECIFIC INTERNAL ENERGY FOR GENERAL MATERIAL

Just as P, v, and T are thermodynamic properties, so is u. In fact, it can be

considered to be one of the necessary two properties necessary to define a third. So,

for example, if we are given P and u, we could find v = v(P, u) or T = T(P, u).

More importantly, let us consider the most general form for u; a form where u is a

function of at most two independent thermodynamic variables, say T and v,

u = u(T, v)

For materials such as water, u(T, v) is tabulated. Note that the tables must presume

a reference value for energy so as to give it an absolute nature. However, as long as

we confine our thermodynamics to a single substance, differences in energy will be

the only quantities that have relevance in determining physical quantities of interest.

That is to say, the reference state will not be important for single material problems.

This is not true for multiple material problems such as when chemical reactions are

present.

Similar to vf and vg, the tables have:

• uf - the specific internal energy of a saturated liquid, and

• ug - the specific internal energy of a saturated vapor

Also similar to v, we have

ufg = ug − uf

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We also get a similar analysis for quality x as for volume. For a two-phase

mixture, the total energy of the mixture is the sum of the energies of the components:

We can solve for x by inverting the last equation above to get

Let us consider the heat transfer for an isochoric process in which we also

have ∆KE = ∆P E = 0. Because the process is isochoric . So the first

law, Eq. (5.36), reduces to

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5.3 SPECIFIC ENTHALPY FOR GENERAL MATERIALS

thermodynamic properties. The extensive total enthalpy H, and intensive specific

enthalpy h are defined as

Thus,

The equation above is valid for general materials. It will be seen to be useful

for many problems, though in principle, we could get by with u alone just as well.

Now, since u, P, and v are thermodynamic properties, so then is h:

h = h(T, P).

Sometimes tables give h and we need to find u; thus,

u = h − P v.

Similar to u, we can easily show

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The enthalpy is especially valuable for analyzing isobaric processes. Consider a

special isobaric process in which P1 = P2 = P, ∆KE = ∆P E = 0. Then the first law

equation reduces to:

U2 − U1 = 1Q2 − 1W2.

Since for the isobaric process, the first law reduces to

The change in H gives the heat transfer for isobaric processes.

5.4 SPECIFIC HEAT CAPACITY

We loosely define the

• Specific heat capacity - the amount of heat needed to raise the temperature of

a unit mass of material by one degree.

The word is a relic of the discredited caloric theory of heat in which heat was

thought to be a fluid which could somehow fill its container. We often simply call it

the “specific heat.” We give the specific heat the symbol c. It has units kJ/kg/K. Its

loose mathematical definition is

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We also define the extensive heat capacity as C = δQ/δT, where C has units

kJ/K. We will not use C explicitly from here on.

It turns out that since δQ is path-dependent, so is c. So let us specify two

common paths:

• specific heat at constant volume - cv. We determine this on a path which is

isochoric. On such a path, the first law holds that δQ = dU, since δW = 0. So

we take

Since u = U/m, and we take m to be constant, we get

Now, for general materials u = u(T, v), so we see that

cv = cv(T, v)

that is to say, cv(T, v) is itself a thermodynamic property for general materials.

It can vary with two independent variables. We shall see later for some

materials it varies only with T, and for other materials, it is actually a constant.

• specific heat at constant pressure - cP . We determine this on a path which is

isobaric. On such a path, the first law holds that δQ = dH. So we take

Since h = H/m, and we take m to be constant, we get

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Now, for general materials h = h(T, P), so we see that

cP = cP (T, P),

that is to say, cP (T, P) is itself a thermodynamic property for general

materials. It can vary with two independent variables. We shall see later for

some materials it varies only with T, and for other materials, it is actually a

constant.

• specific heat for incompressible materials - c. Most liquids and solids under

moderate to low pressure conditions (P < 1 GP a) are well modeled as

incompressible. Thus, in any heating process, there will be little if any

associated work of compression. For such a material, there is no need to

distinguish cv and cP , so we simply use c for the specific heat. We thus take

Often, especially if the temperature changes are small, we can ignore the

temperature variation of c for incompressible materials and simply take

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*QUANTITATIVE ANALYSIS

1. A group of twenty executives attend a board meeting in a room which measures 20

ft by 20 ft and has a 10 ft ceiling. Assume that each person occupies 2.5 ft3 and gives

out about 375 Btu of heat per hour. Calculate the air temperature rise occurring within

15 min of the start of the conference if the room is completely sealed and insulated.

Take cv for air as 0.1715 Btu/lbm°F.

Solution: Take the air in the room as a thermodynamic system and assume

that the people are adding heat to the air in a constant-volume process. The room

volume is

Vroom = 20 × 20 × 10 = 4000 ft3

The volume of air is obtained by subtracting the volume occupied by the people:

Vair = 4000 – (20)(2.5) = 3950 ft3

Assuming that the constant-volume heat-addition process starts at

standard atmospheric conditions of 14.7 psia and 70°F, the mass of air is

m = (pV / RT)

= [{(14.7)(144)(3950)} / (53.35)(530)]

= 295 lbm

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For the constant-volume process,

cv ≈ (Δu / ΔT)v and

ΔUv = mcvΔTv

The change in internal energy of the air is equal to the heat added by the people, since

Q + W = ΔU

and there is presumably no work done on the air. Thus

ΔU = (20)(375) = 7500 Btu/hr eq. 1

or, for a 15-min period,

ΔU = (15 / 60)(7500) = 1875 Btu eq. 2

The temperature increase is now calculated from Eq. 1 as

ΔT = (ΔU / mcv)[(1875) / {(295)(0.1715)}] = 37°F

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2. A container which has a volume of 0.1 m3 is fitted with a plunger enclosing

0.5 kg of steam at 0.4 MPa. Calculate the amount of heat transferred and the

work done when the steam is heated to 300°C at constant pressure.

Solution: For this system changes in kinetic and potential energy are not

significant. Therefore

Q = m(u2 – u1) + W

W = 2∫1 P dV = P 2∫1 dV = P(V2 – V1) = m(P2v2 – P1v1)

Therefore

Q = m(u2 – u1) + m(P2v2 – P1v1) = m(h2 – h1)

v1 = (V1 / m) = (0.1 / 0.5) = 0.2 = 0.001084 + x1(0.4614)

x1 = (0.1989 / 0.4614) = 0.4321

Then

h1 = hf + x1hfg = 604.74 + 0.4311 × 2133.8 = 1524.6

h2 = 3066.8

Q = 0.5 (3066.8 – 1524.6) = 771.1 kJ

W = mP (v2 – v1) = 0.5 × 400 (0.6548 – 0.2) = 91.0 kJ

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Therefore

U2 – U1 = Q – W = 771.1 – 91.0 = 680.1 kJ

The heat transfer can be calculated from u1 and u2 by using

Q = m(u2 – u1) + W

u1 = uf + x1ufg = 604.31 + 0.4311 × 1949.3 = 1444.6

u2 = 2804.8

and

Q = 0.5 (2804.8 – 1444.6) + 91.0 = 771.1 kJ

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3. To vaporise 1 mole of water at 1 atm pressure and 100°C, 9.71 kcal of heat is

required. a) Calculate the change in enthalpy and total energy for this

vaporisation process. b) If one mole of steam condenses at 100°C and 1 atm

pressure then what is the change in enthalpy and total energy for the process?

Solution: a) Given that the pressure is maintained at 1 atm.

∴ ΔH = 9.71 kcal/mole

The volume of the liquid vaporized, V1 ≅ 18 ml.

The volume of 1 mole of the gas produced, Vg ≅ 25,000 ml.

Since Vg is much larger than V1,

PΔV = P(Vg – V1) ≅ PVg = RT

= (2)(373)

= 746 cal/mole

≅ 0.75 kcal/mole

ΔH = ΔE + PΔV

The change in total energy = ΔH – PΔV

= 9.71 – 0.75

= 8.96 kcal/mole.

(b) When we consider condensation there will be an output of heat, ∴ ΔH = – 9.71

kcal/mole. Condensation will have a decrease in volume, so that

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PΔV ≅ P(– VG) = – RT = – 0.75 kcal/mole

Then ΔE = ΔH – PΔV

= – 9.71 – (– 0.75)

= – 8.96 kcal/mole.

4. Water is continuously spilling over a water tank at a height of 100 m from

ground level. a) Calculate the potential energy of the water at the top of the

tank with respect to its base. b) Calculate the kinetic energy of the water just

before it strikes the floor. c) After the water enters the flow below, what

change has occurred to its state? Calculate for 1 kg of water in all three cases,

assuming that there is no energy exchange with the surroundings.

Solution: Since there is no energy exchange Q and W = 0

ΔU + ΔEK + ΔEP = 0 eq. 1

EK = kinetic energy

EP = potential energy

U = internal energy.

Equation (1) can be applied to any point of the fall.

EP = (mzg / gc)

= [{1(kg) × 100(m) × 9.8066(m)/(s)2} / {1(kg)(m)/(N)(s)2}]

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where g has been taken as the standard value. This gives

EP = 980.66(N ∙ m) or 980.66(J)

b) During the free fall of the water no mechanism exists for conversion of potential or

kinetic energy into internal energy. Thus ΔU must be zero, and

ΔEK + ΔEP = E(K)2 – E(K)1 + E(P)2 – E(P)1 = 0

For practical purposes take E(K)1 = 0 and E(P)2 = 0. Then

E(K)2 = E(P)1 = 980.66(J)

c) As the 1(kg) of water strikes the bottom and joins with other masses of water to

form a flow, there is much turbulence, which has the effect of converting kinetic

energy into internal energy. During this process ΔEP is essentially zero. Therefore

ΔU + ΔEK = 0 or ΔU = E(K)2 – E(K)3

However, the velocity is assumed to be small, and therefore E(K)3 is negligible.

Thus

ΔU = E(K)2 = 980.66(J)

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5. Calculate the heat added when one mole of carbon dioxide is heated at

constant volume from 540 to 3540 F.

Solution: Since the temperature is much higher than the critical temperature,

the compressibility factor can be taken as 1. The specific heat can be calculated from

the relationship

Cv = Cp – (Ro / J)Btu/lb/°F and

d'Q = NCvdT

Then d'Q = N(Cp – 1.985) dT

d'Q = 1[16.2 – {(6.53 × 103) / T} + {(1.41 × 106) / T2} – 1.985] dT

Hence,

d'Q = 1[16.2 – {(6.53 × 103) / T} + {(1.41 × 106) / T2} – 1.985] dT– 1.41 × 106[(1 /

4000) – (1 / 1000)]

= 42,645 – 9053 + 1058

= 34,650 Btu

Alternate Solution: At the mean temperature of 2500 R,

Cv = (16.2 – 1.985) – [(6.53 × 103) / 2500] + [(1.41 × 106) / 25002]

= 14.215 – 2.612 + 0.226

= 11.829 Btu/lbm–°F

Then, Q = NCv(T2 – T1) = 1 × 11.829 × 3000 = 35,487 Btu

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6. A container with an air tight piston is at a pressure of 100 psia and a

temperature of 70°F. The piston moves up when 100 Btu of heat is transferred

and the volume changes from 0.5 ft3 to 2.0 ft3. Assuming perfect gas behavior,

calculate

a) the change in internal energy,

b) the final temperature and

c) the heat capacity of the process.

Solution: (a) For a simple system ΔU = Q – W

Assuming the system behaves ideally: ΔU = Q – p (v)2∫(v)1 dV

where p is a constant. Then

ΔU = 100 – [(100 × 144) / 778] 2.0∫0.5 dV

1 BTU ≅ 778 ft lbf, and so

ΔU = 100 – 18.5(2.0 – 0.5) = 72.2 Btu

From the perfect gas laws:

(b) (p1V1 / T1) = (p2V2 / T2)

Hence, T2 = (T1V2 / V1) = [{(70 + 460)(2.0)} / 0.5] = 2120°R

t2 = 1660°F

Since the process is at constant pressure then Cp is the heat capacity desired.

Cp = (ΔQ / ΔT) = [100 / (2120 – 530)] = 0.0629 Btu/°R

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(c) dQ = Cpdt = dh

1Q2 = h2 – h1 = 66 Btu per lbm.

7. An air compressor takes in 2 ft3/lb of air at 15 psia and compresses it to a

pressure of 110 psia. The specific volume at discharge is 0.5 ft3/lb. Calculate

the amount of heat transferred if the increase in internal energy is 40 Btu/lb

and the work done is 70 Btu/lb.

Solution: The different forms of energy to be considered in this case are the

flow energy, internal energy, work and heat. For unit mass (1 lb) of a substance.

W1 = (p1v1 / J)

= [(15 × 122 × 2) / 778]

= 5.55 Btu/lb.

W2 = (p2v2 / J)

= [{(110) × 122 × 0.5} / 778]

= 10.18 Btu/lb.

∴ ΔWf = W2 – W1 = 10.18 – 5.55 = 4.63 Btu/lb

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In any case of compression, work must be done on the air to compress it and work

therefore is negative in this case.

W = – 70 Btu/lb

The change in internal energy is

Δu = u2 – u1 = 40 Btu/lb

The total heat transfer Q can be given by

Q = Δu + ΔWf + W

= 40 + 4.63 + (– 70)

= – 25.37 Btu/lb

The negative sign shows that heat is given out during the process, and air

compressors usually have water jackets for the purpose of cooling the air during

compression.

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8. A steam pipe containing saturated steam at 100 psia is connected to an empty

cylinder. What will be the final state of the steam if the cylinder is filled with

steam at the same pressure as the pipe?

Solution: Since the cylinder is empty at time zero, m1 = 0 and u1 = 0, while ef = h,

the enthalpy of the fluid in the reservoir. Then the equation

Qcv + ∑mihi = ∑mehe + (m2u2 – m1u1) + W12

reduces to m2u2 = m2ef

From the steam tables for 100 psia saturated steam,

h = 1187.2 Btu/lbm T = 328°F

The final conditions in the tank are

P2 = 100 psia u2 = ef = 1187.2 Btu/lbm

Interpolating in the steam tables for these values,

T2 ≈ 540°F (P2 = 100 psia)

The temperature rise from compression of the steam in the container is

540° – 328° = 212°F

Thus, the steam in the container is highly superheated although the steam in the

reservoir is not.

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9. Calculate the mass rate of flow of air through a pipeline with an inside

diameter of 3.5 in. if the average velocity of air at 80°F and 20 psia is 110

ft/min.

Solution: Using the ideal gas equation

Pv = RT eq. 1

And from the conservation of mass

ṁ = ρAV eq. 2

Where: V = velocity of air = 110 ft/min

A = area of cross section of the pipe

ρ = density of air

From eq. 2 ṁ = (1/v) AV eq. 3

Where: v = specific volume of air

From eq. 3 v = (AV / ṁ)

Combining eq. 3 and eq. 1, gives

(PAV / ṁ) = RT

ṁ = (P / RT) ∙ AV

ṁ = [(20 × 144) / {(1545 / 29)(80 + 460)}] ∙ [{π(3.5 / 12)2} / 4] × 110

= [(20 × 144 × π) / {(53.41)(540)}] × (0.085 / 4) × 110

ṁ = 0.733 lbm/min.

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10. Calculate the total work transfer that takes place for a process as shown in the

figure.

T1 = – 50°F T2 = + 70°F

P1 = 650 psia P2 = 25 psia

H1 = 300 Btu/lbm H2 = 410 Btu/lbm

S1 = 1.0 Btu/lbm°R S2 = 1.65 Btu/lbm°R

Z1 = 100 ft Z2 = 100 ft

V1 = 450 ft/sec V2 = 150 ft/sec

Solution: Taking into consideration the different forms of energy

Qact – (W)act = ΔH + ΔKE + ΔPE

= H2 – H1 + [(V22 – V12) / 2gc] + (Z2 – Z1)(g / gc)

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220(Btu / lbm) – (W)act

= (410 – 300)(Btu / lbm)

+ [{(1502 – 4502)(ft2 / sec2)} / {2 × (32.2 ft lbm / sec2 lbf)}]

× [(1 Btu) / (778 ft–lbf)]

+ [{(100 – 100)(32.2 ft / sec2)} / {(32.2 ft–lbm) / (sec2lbf)}]

220 – Wact = 110 + (– 3.6) + 0

∴ – Wact = – 113.6 Btu/lbm

Wact = 113.6 Btu/lbm

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VI. SECOND AND THIRD LAWS OF THERMODYNAMICS

The Second Law acknowledges that processes proceed in a certain direction but

not in the opposite direction. A hot cup of coffee cools by virtue of heat transfer to

the surroundings, but heat will not flow from the cooler surroundings to the hotter cup

of coffee.

Conservation of mass and energy are fine concepts that allow us to quantify and

predict well many phenomena which are observed in nature. And if a phenomenon

can be repeated, it becomes subject to prediction, and can be thought of as a science.

However, conservation of mass and energy, by themselves, admit as possibilities

phenomena which are not observed in nature! For instance consider an isolated

system composed of two equal masses of liquid water. See Fig. 7.1. The first is at TA

= 310 K, the second is at TB = 290 K. A long time elapses. Because the combined

system is isolated, there are no external heat or work exchanges with the environment.

But we will allow heat exchanges between mass A and mass B. Consider two

possibilities, both admitted by mass and energy conservation, as t → ∞:

• TA → 320 K, TB → 280 K. The thermal energy that is gained by A is lost by B,

such that the net energy is conserved and the first law is satisfied. This is never

observed in nature.

• TA → 300 K, TB → 300 K. The thermal energy that is lost by A is gained by B,

so once again the first law is satisfied. This is always observed in nature.

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So mass conservation and the first law of thermodynamics, both of which speak to

this gedanken experiment, are insufficient to guarantee that we will predict what is

observed in nature. We need another axiom!

In a similar way, there are a variety of phenomena which may satisfy mass and

energy conservation, but are not observed in nature. Some include

• water running uphill without an external assist,

• CO2 and H2O reacting spontaneously to form CH4 and O2, and

• air separating into its constituents spontaneously.

6.1 STATEMENTS OF THE SECOND LAW

The second law of thermodynamics is an attempt to provide a single all-

encompassing statement which expands our thermodynamic theory so as to predict

the just-described behavior. Though our statement of the second law will be simple

enough, it will be obtuse and sometimes difficult to reconcile with nature. It is also a

profound concept which has wide ranging ramifications. Its origins are firmly rooted

in the engineering sciences, as it was motivated by optimization of steam engines.

However, it has found applications in many realms of physics, chemistry, ecology,

economics, computer science, and other fields.

Let us summarize some more reasons for studying the second law:

• It predicts the direction in time of processes.

• It aids in determining equilibrium conditions.

• It allows one to determine peak performance of practical devices.

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• It enables one to frame analysis of the factors which inhibit the realization of

peak performance.

• It allows a rational definition of the absolute temperature scale.

• It has implications beyond engineering in physics, philosophy, economics,

computer science, etc.

6.2 INTRODUCTION OF ENTROPY

In our consideration of the first law, we initially stated the law in terms of a

cycle, but then defined a property, the internal energy, which enabled us to use the

first law quantitatively for processes. Similarly, we have stated the second law for a

cycle, and we now find that the second law leads to a property, entropy, which

enables us to treat the second law quantitatively for processes.

6.2.1 ENTROPY-BASED STATEMENT

There are many ways to state the second law of thermodynamics. One

statement is as follows:

• Second law of thermodynamics - The entropy of an isolated system can never

decrease with time.

This definition begs the question, what is entropy? A formal definition will be

deferred to the next chapter. Let us loosely define it here as a measure of the so-called

randomness (or disorder) of a system, with high randomness corresponding to high

entropy. Low randomness or low disorder often corresponds to low entropy.

Interpreted in another way, structure or order requires energy input to be

realized, while over time, without continued maintenance, structure and order decay.

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The formulation of the second law we adopt will be robust enough to prevent us from

predicting water to run uphill, methane to spontaneously form from carbon dioxide

and water, or air to separate into its constituents. It will also be seen to be an

important principle for predicting the optimal behavior of a wide variety of

engineering devices.

All that said, it should be noted that the equivalence of entropy with disorder,

while useful and common, is likely not universal.

6.3 HEAT ENGINES AND THERMAL EFFICIENCIES

A Heat Engine may be defined as a device that operates in a thermodynamics

cycle and does a certain amount of net positive work through the transfer of heat from

a high-temperature and to a low-temperature body. A simple steam power plant is an

example of a heat engine (Fig. 6.1).

An amount of heat, QH, is transferred from a high-temperature body. In Fig.

6.1 the turbine is shown as driving the pump. What is significant, however, is the

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network that is delivered during the cycle. The quantity of heat QL is rejected to a

low-temperature body. Thus, the simple steam power plant is a heat engine, for it has

a working fluid, to which and from which heat is transferred, and which does a certain

amount of work as it undergoes a cycle.

At this point it is appropriate to introduce the concept of Thermal Efficiency of

a heat engine. Thermal efficiency is the ratio of output, the energy sought, to input,

the energy that costs. Thermal efficiency is defined as

6.4 THE THIRD LAW OF THERMODYNAMICS

The entropy of all pure substances can be assigned the value of zero at the

absolute zero of temperature.

6.5 ENTROPY CHANGE OF A SYSTEM DURING AN

IRREVERSIBLE PROCESS

Consider a system that

undergoes the cycles shown in

Fig. 6.3. The cycle made up of the

reversible processes A and B is a

reversible cycle.

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Therefore, we can write

The cycle made up of the reversible process A and the irreversible process C is an

irreversible cycle. Therefore, for this cycle the inequality of Clausius may be applied,

giving the result

Since path B is reversible, and since entropy is a property,

Therefore,

For the general case we can write

In these equation the equality holds for a reversible process and the inequality

for an irreversible process.

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*QUANTITATIVE ANALYSIS

1. Three kilograms of air are at an initial state of 100 kPa, 300°K. The air is then

compressed polytropically with n = 2.56, to a final pressure of 500 kPa. Assuming

constant specific heats, calculate the change in entropy using the three ideal gas

equations.

Solution: The three different equation which give the change in entropy for an

ideal gas are

ΔS = mCv In (T2 / T1) + mR In (V2 / V1) eq. 1

ΔS = mCp In (T2 / T1) − mR In (P2 / P1) eq. 2 and

ΔS = m Cn In (T2 / T1) eq. 3

where Cn is the polytropic specific heat defined as

Cn = [(Cp – nCv) / (1 – n)] eq. 4

In all three equations the temperatures at both states is involved. To find

the temperature at state 2 the following expression is used.

T2 = T1 (P2 / P1)[(n – 1) / n]

Substituting the numerical values

T2 = 300 [(500) / (100)](2.56 – 1) / 2. 56

= 300 (5)0.6094

= 800°K

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Using the ideal gas equation of state

PV = mRT

the volumes at the two states are then calculated as

v1 = [(mRT1) / P1]

= [{3 (0.287) (300)} / (100)]

= 2.583 m3 and

v2 = [(mRT2) / P2]

= [{3 (0.287) (300)} / (500)]

= 1.378 m3.

Also from eq. 4 Cn = [{1.0035 − 2.56(0.717)} / (1 − 2.56)]

= 0.534 kJ/kg − °K.

Eq. 1 gives ΔS = 3(0.717) ln [(800) / (300)] + 3(0.287) In [(1.378) / (2.583)]

= 1.57 kJ/°K.

Eq. 2 gives ΔS = 3(1.0035) In [(800) / (300)] − 3(0.287) In [(500) / (100)]

= 1.57 kJ/°K.

Eq. 3 gives ΔS = 3(0.534) In [(800) / (300)]

= 1.57 kJ/°K

All three equations give the same result, as should be expected.

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2. Calculate the change in specific entropy of 1 lbm of air when it is compressed from

14 psia, 60°F to 84 psia and 460°F.

Solution: Assume a reversible process between the two state points. Thus

(T2 / T1) = (P2 / P1)[(n – 1) / n]

[(920) / (520)] = (84 / 14)[(n – 1) / n]

1.769 = (6)[(n – 1) / n]

Hence [(n – 1) / n] = 0.3185

n = 1.467

For a polytropic process

Cn = Cv + [R / {J (1 – n)}]

= 0.1715 + [(53.35) / {(1 – 1.467) 778}]

= 0.1715 – 0.1467

= 0.0248 Btu/lbm – °R

Then S2 – S1 = mCn ln (T2 / T1)

= 1 × 0.0248 ln [(920) / (520)]

= 0.01416 Btu/°R

The change in entropy is

ΔS = 0.01416 Btu/°R

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3. Helium is heated reversibly at constant pressure from 18psia, 80F to 200F in a

steady flow system. Calculate the change in entropy per pound of helium for this

process.

Solution: The first law for a steady flow system in differential form is

δq = dh + dKE + dPE + δw eq. 1

For a reversible steady-flow process

δw = – vdp – dKE – dPE eq. 2

From eq. 1 and eq. 2

δq = dh + dKE + dPE – vdp – dKE – dPE

For a constant pressure process dp = 0

∴ δq = dh

For a steady flow system dS = 0 and δm1 = δm2

The expression for dS of an open system is

dS = (δQ / T)rev + S1δm1 – S2δm2

dS = 0 = (δQ / T)rev + (S1 – S2) δm

S2 – S1 = 2∫1 (δQ / T) = 2∫1 (dh / T) = 2∫1 [(CP dT) / T]

for helium, Cp = 1.25 Btu/lb°F

= 1.25 Btu/lb°R

ΔS = CP In (T2 / T1)

= 1.25 ln [(660) / (540)]

= 0.251 Btu/lb – °R.

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4. A gas having a constant volume specific heat equal to (4.52 + 0.00737T) Btu/lbm –

°F is initially at 175°F. Heat is then added to the gas in a constant volume process

until its temperature rises to 200°F. Calculate the change in entropy associated with

this process.

Solution: In this case, Cv, for the gas is in the form

Cv = a + bT

Where: a = 4.52

b = 0.00737

The entropy change per unit mass is given as

ΔS = b∫a Cp (dT / T) = b∫a [(a + bT) / T} dT

= b∫a a (dT / T) + b∫a (bT / T) dT

Integration yields

ΔS = a In (Tb / Ta) + b (Tb – Ta)

= 4.52 In [(660) / (635)] + 0.00737(200 – 175)

= 0.1745 + 0.1843

= 0.3588 Btu/lbm.

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5. An ideal gas at an initial state of 4.1 atm, 38°C is expanded irreversibly to a final

state of 2 atm, 4.4°C. Assuming the specific heats of the gas to be Cp = 0.5150

and Cv = 0.3098 kJ/kg – °K calculate the change in entropy.

Solution: The change in entropy for a reversible or irreversible process is

given by the relation

dS = (1 / T) du + (P / T) dv eq. 1

However, for an ideal gas

du = Cv dT eq. 2 and

(P / T) = (R / v) = [(Cp – Cv) / v] eq. 3

Substituting Eqs. 2 and 3 into Eq. 1,

Integrating gives

ΔS1→2 = Cv In (T2 / T1) + (Cp – Cv) In (v2 / v1) eq. 4

The specific volumes at the initial and final states are then calculated as follows.

From Eq. 3

v = [{(Cp – Cv) T} / P] or

v1 = [{(0.5150 – 0.3098) × 311} / (4.1 × 101)]

= 0.5141 m3/kg and

v2 = [{(0.5150 – 0.3098) × 277.4} / (2 × 101)]

= 0.2818 m3/kg

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Substituting all the numerical values into Eq. 4,

ΔS1→2 = 0.3098 ln [(277.4) / (311)] + (0.5150 – 0.3098) ln [(0.2818) /

(0.1541)]

= – 0.0354 + 0.1239

= 0.0885 kJ/kg – °K

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6. Ten grams of argon gas at an initial pressure and temperature of 608 kPa, 300°K

respectively undergo a change of state at constant internal energy until the final

volume is three times the initial occupied volume. Assuming ideal gas behavior

determine the final state (pressure and temperature), and the entropy change of the gas

due to the change of state.

Solution: For a perfect gas, the internal energy is a function of the

temperature only.

u = f(T)

Assuming constant internal energy, follows that the temperature must also be a

constant. Therefore, for a change of state at constant internal energy.

T2 = T1 = 300°K

Since we have assumed ideal gas behavior

P1V1 = mRT1 eq. 1

P2V2 = mRT2 eq. 2

However, T2 = T1, V2 = 3V1, and m = constant. Combining Eqs. 2 and 1 and solving

for P2,

P2 = (P1 / 3) = [(608) / 3] = 202.7kPa

The change in entropy is given by the equation

s2 – s1 = Cp In (T2 / T1) – R In (P2 / P1) eq. 3

Since T2 = T1 Eq. 3 reduces to

s2 – s1 = – R ln (P2 / P1) eq. 4

where for argon gas R = 0.20813 kJ/kg – °K.

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Substituting the numerical values into Eq. 4

s2 – s1 = – (0.20813) In [(202.7) / (608)]

= + 0.2286 kJ/kg – °K

= + 228.6 J/kg – °K

For 10 g of argon gas

ΔS = S2 – S1 = m(s2 – s1)

= [{10 (228.6)} / (1000)]

= + 2.286 J/°K

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7. An insulated chamber containing oxygen, is divided equally into two by a partition,

as shown in Fig. 1. Part A of the chamber contains 1 lb-mole at 1 atm, 984°R while

part B contains 1 lb-mole at 1 atm, 492°R. The partition is then removed allowing the

oxygen in A and B to mix and attain the same temperature. Draw the T-S diagram for

this process, and calculate the change in entropy of the universe.

Solution: This system is a closed system and involves unbalanced temperature

forces. When the partition is removed the oxygen in A will cool to a final temperature

T2 and heat the oxygen in B to T2. For this process W1→2 = 0 and since the chamber is

insulated Q1→2 = 0. From the first law then

(Δu)syst = 0 or

(Δu)syst. = mAΔuA→2 + mBΔuB→2 eq. 1

Assuming ideal gas behavior with constant specific heats, and using the relation

Δu = CvΔT

Eq. 1 becomes

mA CvΔTA→1 + mBCvΔTB→1 = 0 eq. 2

However, because both gases are 02

(ΔS)max = 0

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Also since points A, B, and 2 all lie on the same isobar, an isobaric reversible path

can be used to evaluate (mΔS)A and (mΔS)B.

Therefore ΔSA = ∫(dQ / T) = ∫Cp (dT / T)

= Cp In (T2 / TA)

= 7 in [(738) / (984)]

= – 2.01 Btu/lb-mole – °R and

ΔSB = ∫(dQ / T) = ∫Cp (dT / T)

= Cp In (T2 / TB)

= 7 in [(738) / (492)]

= + 2.84 Btu/lb-mole – °R

or since mA = mB and the Cv is the same since there is only oxygen involved,

Eq. 2 becomes

ΔTA→2 + ΔTB→2 = 0 or

(T2 / TA) + (T2 / TB) = 0

Solving for T2

T2 = [(TA + TB) / 2]

= [(984 + 492) / 2]

= 738°R

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The T–S diagram can then be sketched as shown in Fig. 2.

The change in entropy of the universe for this process is

(mΔS)u – (mΔS)A + (mΔS)B + (mΔS)mix eq. 3

Substituting into Eq. 3

(mΔS)u = (1) (– 2.01) + (1) (2.84) + 0

= + 0.83 Btu/°R

The entropy increase of the universe shows that as a result of the unbalanced

temperature forces the system lost the ability to do work.

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8. Water at 15 kPa, 40°C enters a pump and leaves after the pressure has been raised

to 5 MPa. Assuming the process to be reversible and adiabatic determine the

temperature of the water at the exit of the pump.

Solution: Consider as the system, the pump with a steady flow in and out.

From the first law

q + hi + [(Vi2) / 2] + gZi = he + [(Ve2) / 2] + gZe + w

Neglecting potential and kinetic energies

q + h i = he + w eq. 1

The process is reversible and adiabatic, hence

q=0 and

se = si

Eq. 1 then becomes

he – hi = – w eq. 2

Using the relation

Tds = dh – vdP

Eq. 2 becomes

he – hi = – ∫vdP eq. 3

Assuming constant specific volume and substituting Eq. 3 into Eq. 2 and integrating

wp = – v1 (P2 – P1) eq. 4

where the subscripts 1 and 2, stand for the inlet and exit states. From the steam tables,

at T1 = 40°C

v1 = 0.001008 m3/kg

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Substituting into Eq. 4

wp = – 0.001008 (5000 – 15)

= – 5.02 kJ/kg

Also from the steam tables at T = 40°C

h1 = hf = 167.57 kJ/kg

From Eq. 2

h2 = h1 – wp

= 167.57 + 5.02

= 172.59 kJ/kg.

From the compressed liquid table at P2 = 5MPa and h2, by interpolation

T2 = 40.15°C

Note that the temperature does not change very much, and in many cases

constant temperature is assumed.

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9. Steam at 500°F and 100 lbf/ir2 enters a steam turbine with a velocity of 200 ft/sec.

The outlet steam has a velocity of 600 ft/sec and a pressure of 20 lbf/in2. If the

process is reversible and adiabatic, calculate the work per pound of steam.

Solution: The steady flow energy equation for this process can be written as

hi = [(Vi2) / (2gc)] = he + [(Ve2) / (2gc)] + w

The example is one of steady-flow, reversible, adiabatic process, se = si and

entropy and pressure for the final state are known.

From the steam tables

hi = 1279.1 Btu/lbm

si = 1.7085 Btu/lbm R

For the final state

Pe = 20 lbf/in2

Se = si = 1.7085 Btu/lbm R.

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From these values the quality and enthalpy leaving the turbine can be

determined, as follows:

se = 1.7085

= sg – (1 – x)e sfg

= 1.7319 – (1 – x)e 1.3962 or

(1 – x)e = [(0.0234) / (1.3962)]

= 0.01676

Then,

he = hg –(1 – x)e hfg

= 1156.3 – 0.01676 (960.1)

= 1140.2 Btu/lbm

Using the- steady flow energy equation, the work per pound of steam for this

process can be calculated, as

w = 1279.1 – 1140.2 + [{(200)2 – (600)2} / (2 × 32.17 × 778)]

= 132.5 Btu/lbm.

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10. An ideal gas undergoes an isothermal expansion in which its volume doubles. For

one mole of this gas calculate the change in entropy for the surroundings if the

process is assumed to be reversible.

Solution: For any reversible isothermal process, the surrounding temperature

and the system temperature must be the same

∴ (ΔS)surr = [{(qrev) surr} / T]

The surroundings absorb the heat that is given up by the system

∴ (ΔS)surr = – [{(qrev) sys} / T]

(qrev)sys = T(ΔS)sys

∴ (ΔS)surr = – T [(ΔS)sys / T}

= – (ΔS)sys

(S2 – S1)sys = C(v)0 In (T2 / T1) + R In (V2 / V1)

= R In (2)

(ΔS)surr = – 1.38 cal/mole – °K

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VII. REFERENCE:

https://www.chemteam.info/GasLaw/Gas-Ideal-Prob1-10.html

https://www3.nd.edu/~powers/ame.20231/notes.pdf?fbclid=IwAR1hEkmW7mmZe5

T2s6NqFQhTVBHKbI8xnwwsJCwEGD0gyXHT8EhDcCPu8Tc

https://stemez.com/subjects/technology_engineering/1DThermodynamics/1DThermo

dynamics/1DThermodynamics/1D00-Ch00.htm?fbclid=IwAR37L9pr8qL1-

tbL2hT3D6D0TtiJZeRpawHX5GiOLztSkRK4rl0qQmEO9k8

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