Thermodynamics Theory + Questions

Basic Concepts
S K Mondals Chapter 1
1.
Basic Concepts
Theory at a Glance (For GATE, IES & PSUs) Intensive and Extensive Properties
Intensive property: Whose value is independent of the size or extent i.e. mass of the system. These are, e.g., pressure p and temperature T. Extensive property: Whose value depends on the size or extent i.e. mass of the system (upper case letters as the symbols). e.g., Volume, Mass (V, M). If mass is increased, the value of extensive property also increases. e.g., volume V, internal energy U, enthalpy H, entropy S, etc. Specific property: It is a special case of an intensive property. It is the value of an extensive property per unit mass of system. (Lower case letters as symbols) eg: specific volume, density (v, ).
Thermodynamic System and Control Volume

In our study of thermodynamics, we will choose a small part of the universe to which we will apply the laws of thermodynamics. We call this subset a SYSTEM. The thermodynamic system is analogous to the free body diagram to which we apply the laws of mechanics, (i.e. Newtons Laws of Motion). The system is a macroscopically identifiable collection of matter on which we focus our attention (e.g., the water kettle or the aircraft engine).
System
Definition
System: A quantity of matter in space which is analyzed during a problem. Surroundings: Everything external to the system. System Boundary: A separation present between system and surrounding. Classification of the system boundary: Real solid boundary Imaginary boundary
B Basic C Conce epts

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Th he system bou undary may be b further cla assified as: : rol Mass Syst tem. Contr Contr rol Volume Sy ystem. Th he choice of bo oundary depends on the problem p bei ing analyzed d.
Cha apter 1
Ty ypes of f Syste em
Closed System S (Contro ( ol Mass System m)

1. Its a system of fixed mass s with fixed identity. 2. This s type of system s is us sually referred d to as closed system. . 3. Ther re is no mas ss transfer across a the syst tem boundar ry. 4. Energy transfer r may take place into or out of the system. Fig. A Co ontrol Mass s System or Closed C Syst tem

S K Mondals Cha apter 1
O Open Sy ystem (Contr rol Vol lume System S )

1. 2. Its a system of fixed f volum me. Thi is type of system s is us sually refe erred to as "open system m or a "c control volu ume" Mass transfer can take place acro oss a control volume. Ene ergy transfer may also occur into o or out of the system. A control volum me can be seen n as a fixe ed region ac cross which mass and d energy tran nsfers are stu udied. Con ntrol Surfa ace Its the bou undary of a control vo olume Fig. A Co ontrol Volum me System acro oss which th he transfer of f both or r Open System mass and energ gy takes place e. The e mass of a co ontrol volum me (open syste em) may or may m not be fix xed. Wh hen the net in nflux of mass across the control surfa ace equals ze ero then the mass of the syst tem is fixed and a vice-vers sa. The e identity of mass in a control c volum me always ch hanges unlik ke the case for f a control mass system (cl losed system) ). Most of the engi ineering devi ices, in gener ral, represent an open sys stem or contr rol volume.
3. 4. 5.
6.
7. 8. 9. 10.
Ex xample:
Heat exchanger - Fluid enters an nd leaves the e system con ntinuously with w the transfer of heat across the sy ystem bound dary. Pump - A continuous c fl low of fluid takes place th hrough the system s with a transfer of f mechanical energy from m the surroun ndings to the system.

Is solated d Syste em
1. 2. It is a sys stem of fixed d mass with h same identity and fixed energy e . No intera action of mas ss or energy takes place be etween the system and d the surround dings. In more informal words w an iso olated system is s like a closed shop ami idst a busy mar rket.
3.
Fig. An n Isolated System S
Q Quasi-St tatic Pr rocess

Th he processe es un nrestrained can be e restrained d or We e need restra ained process ses in practice. Aq quasi static c process is one o in which The dev viation from m thermodyn namic equilibriu um is infinite esimal. All states s of the syste em passes th hrough are equil librium state es. If we rem move the weig ghts slowly one o by Fig. A quasi q static process one the pressure of the gas s will displace the piston gradually. It is quasista atic. On the other hand if we remove all a the weights at once th he piston will be kicked up p by the gas pressure. (This is un nrestrained expansion) but b we dont t consider th hat the work k is done because it i is not in a sustained manner. In both cases c the syst tems have un ndergone a ch hange of stat te. Another e.g., if a person climbs down d a ladder from roof to t ground, it is a quasista atic process. On the ot ther hand if he jumps the en it is not a quasistatic process. p

La aws of Thermodynam mics
h Law deals with ther rmal equilib brium and provides a means for measuring The Zeroth temperature es. L deals with w the cons servation of energy and introduces the concept of internal The First Law energy. modynamics provides wit th the guideli ines on the co onversion he eat energy of The Second Law of therm matter into work. It also o introduces the t concept of o entropy. L of therm modynamics defines the absolute zer ro of entropy y. The entrop py of a pure The Third Law crystalline substance s at absolute zero o temperatur re is zero.
Summat tion of 3 Laws s

Firstly, there isnt a meaningful m te emperature of the sourc ce from whi ich we can get g the full conversion of o heat to wo ork. Only at infinite tem mperature one e can dream of getting th he full 1 kW work output t. Secondly, more m interesti ingly, there isnt i enough work availab ble to produc ce 0 K. In oth her words, 0 K is unattai inable. This is i precisely th he Third law w. Because, we e dont know what 0 K lo ooks like, we havent got a starting po oint for the temperature t scale!! That is why all te emperature scales are at best b empirica al. Yo ou cant get something for nothing g: To get work k output you must m give som me thermal energy. e Yo ou cant get something for very litt tle: To get some e work output t there is a minimum m amount of therm mal energy th hat needs to be given. 5

S K Mondals
Yo ou cant get every thing g: However mu uch work you u are willing to give 0 K cant c be reach hed. Vio olation of all a 3 laws: Try to get ev verything for r nothing.
Cha apter 1
eroth Law L of Thermo T odynam mics Ze

If two syste ems (say A an nd B) are in thermal equ uilibrium wit th a third sy ystem (say C) ) separately
(that is A an nd C are in th hermal equil librium; B an nd C are in th hermal equil librium) then n they are in thermal equ uilibrium themselves (tha at is A and B will be in thermal equilib brium).
All tem mperature measuremen m nts are base ed on Zeroth h law of the ermodynam mics
In nternati ional Te empera ature Sc cale

To provide a standard s for r temperatur re measurem ment taking g into accoun nt both theo oretical and pra actical consid derations, th he Internation nal Tempera ature Scale (I ITS) was ado opted in 1927 7. This scale has been refin ned and exte ended in several revisio ons, most re ecently in 1990. The In nternational Temperature Scale S of 1990 (ITS-90) is defined in su uch a way th hat the temp perature mea asured on it con nforms with the thermod dynamic temp perature, the e unit of which is the kel lvin, to withi in the limits of accuracy of measuremen nt obtainabl le in 1990. The T ITS90 is based on the assigne ed values of tem mperature of f a number of o reproducib ble fixed poin nts (Table). In nterpolation between the e fixed-point tem mperatures is i accomplis shed by form mulas that give g the rela ation between readings of o standard ins struments an nd values of the ITS. In the t range fro om 0.65 to 5.0 K, ITS-90 is defined by b equations giv ving the temp perature as functions f of the t vapor pr ressures of pa articular helium isotopes s. The range fro om 3.0 to 24.5561 K is ba ased on meas surements us sing a helium m constant-vo olume gas th hermometer. In the range fr rom 13.8033 to 1234.93 K, K ITS-90 is defined by means m of cert tain platinum m resistance the ermometers. Above 1234 4.9 K the tem mperature is s defined usi ing Plancks equation for blackbody rad diation and measuremen m nts of the inte ensity of visib ble-spectrum m radiation th he absolute temperature t

ale. The abso olute temper rature scale is also know wn as Kelvin n temperatur re scale. In defining d the sca Ke elvin tempera ature scale also, the triple point of wa ater is taken as the stand dard referenc ce point. For aC Carnot engin ne operating between rese ervoirs at tem mperature and tp, tp being the tri iple point of wa ater arbitrari ily assigned the t value of 273.16 K. Tim me Constan nts: The time constant is s the amount t of time req quired for a thermocouple t e to indicate 63.2% of step change c in te emperature of o a surround ding media. Some of the e factors influ uencing the me easured time e constant are sheath wal ll thickness, degree of ins sulation com mpaction, and d distance of jun nction from the t welded ca an on an ung grounded the ermocouple. In I addition, the t velocity of o a gas past the e thermocoup ple probe gre eatly influenc ces the time constant c mea asurement. In general, tim me constants for f measurem ment of gas can c be estima ated to be ten times as lo ong as those for r measureme ent of liquid. The time con nstant also varies v inverse ely proportional to the sq quare root of the e velocity of the t media.

W Work a path p fun nction

Wo ork is one of the basic mo odes of energy y transfer. Th he work done e by a system m is a path fu unction, and not t a point fun nction. There efore, work is not a pr roperty of th he system, and it cann not be said tha at the work k is posses ssed by the system. It is an intera action across s the bounda ary. What is sto ored in the system is ene ergy, but not t work. A decrease in energy of the system s appea ars as work don ne. Therefore, work is energy in transit and d it can be identified i o only when the t system un ndergoes a process. p
Free Exp pansion n with Zero Z W Work Tra ansfer

Fr ree Expansio on Let us con nsider an insu ulated containe er (Figure) wh hich is divided d into two com mpartments A
and d B by a thin n diaphragm. Compartmen nt A contains a mass of ga as, while com mpartment B is i completely eva acuated. If the e diaphragm is punctured, the gas in A will expand into B until the t pressures in A and B bec come equal. This T is known n as free or unrestrained expansion.
T The process of free ex xpansion is
irr reversible. . Also work done is zero o during fre ee expansion n.
Free Expa ansion
pd dV-wor rk or Displacement Work W

Let the gas in the t cylinder (Figure show wn in below) be a system having initia ally the pressure p1 and vol lume V1. Th he system is in thermody ynamic equilibrium, the state of wh hich is described by the coo ordinates p1 , V1. The pist ton is the on nly boundary which moves due to gas pressure. Le et the piston mo ove out to a new final po osition 2, wh hich is also a thermodyn namic equilib brium state specified by pre essure p2 an nd volume V2. At any inte ermediate poi int in the tra avel of the pi iston, let the pressure be pa and the volu ume V. This must m also be e an equilibrium state, si ince macrosc copic propert ties p and V 8

S K Mondals
sig gnificant only.
Cha apter 1
r equilibrium m states. Whe en the piston n moves an in nfinitesimal distance dl, and if a' be e the area of for the e piston, the force F actin ng on the pist ton F = p.a. and a the infinitesimal amo ount of work done by the gas s on the pisto on.
dW W=
F dl d = pad dl = pdV V
wh here dV = ad dl = infinitesimal displa acement volu ume. The dif fferential sig gn in dW with the line dra awn at the to op of it will be explained later. l Wh hen the pisto on moves out from positio on 1 to positio on 2 with the e volume cha anging from V1 to V2, the am mount of work k W done by the t system will w be
W12 =
V2
V1
pd dV

S K Mondals
Th he magnitude e of the wor rk done is given g by the e area under r the path 1-2, as shown n in Fig. Sin nce p is at t all times a thermod dynamic coo ordinate, all the states pa assed through h by the sys stem as the volume cha anges from V1 to V2 mu ust be equili ibrium states s, and the path p 1-2 mu ust be qua asi-static. The T piston moves inf finitely slow wly so that every state passed thr rough is an equilibrium e state.
Th he integration n
Cha apter 1
pdV
can n be perform med only
on a quasi-sta atic path.
Fig. Quasi-Static pdV Work k
Heat Tra ansfer-A A Path Functio on

He eat transfer is i a path fu unction, that t is, the amo ount of heat transferred when a syst tem changes fro om state 1 to state 2 depe ends on the intermediate i e states throu ugh which th he system pa asses, i.e. its pat th. Therefore e dQ is an ine exact differen ntial, and we e write
Th he displaceme ent work is given g by
dQ Q = Q12 or
Q2 Q2 Q1
W12 =
dW =
pdV W2 W1
PR ROBLEM MS & SO OLUTION NS
Ex xample 1 In a closed syst tem, volume changes from m 1.5m3 to 4.5 m3 and hea at addition is s 2000 kJ. Ca alculate the cha ange in inter rnal energy given g the pres ssure volume e relation as 10 W Where p is in n kPa and V is in m3. p = V 2 + V So olution:
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Basic Concepts
S K Mondals
Work done =
V2 V1
Chapter 1
V1
p.dV =
V2
10 dV V
1 V = V23 V13 + 10ln 2 V1 3 4.5 1 = 4.53 1.53 + 10ln 1.5 3
1 = ( 91.125 3.375 ) + 10ln3 3 = [29.250 + 10.986] = 40.236 kJ
First Law of Thermodynamics:Q = W + U 2000 = 40.236 + U U = 2000 40.236 = 1959.764 kJ Example 2. A fluid is contained in a cylinder piston arrangement that has a paddle that imparts work to the fluid. The atmospheric pressure is 760 mm of Hg. The paddle makes 10,000 revolutions during which the piston moves out 0.8m. The fluid exerts a torque of 1.275 N-m one the paddle. What is net work transfer, if the diameter of the piston is 0.6m? Solution: Work done by the stirring device upon the system W1 = 2TN = 2 1.275 10000 N-m = 80kJ This is negative work for the system.
(Fig.) Work done by the system upon the surroundings. W2 = p.dV = p.(A L) (0.6)2 0.80 = 22.9kJ 4 This is positive work for the system. Hence the net work transfer for the system. W = W1 + W2 = - 80 + 22.9 = - 57.l kJ. = 101.325
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Basic Concepts
ASKED OBJECTIVE QUESTIONS (GATE, IES, IAS)

Previous 20-Years GATE Questions
GATE-1. List-I A. Heat to work B. Heat to lift weight C. Heat to strain energy D. Heat to electromagnetic energy 5. Thermal radiation 6. Bimetallic strips Codes: A B C D (a) 3 4 6 5 (c) 3 6 4 2 1. 2. 3. 4. List II [GATE-1998] Nozzle Endothermic chemical reaction Heat engine Hot air balloon/evaporation A 3 1 B 4 2 C 5 3 D 6 4
(b) (d)
Open and Closed systems

GATE-2. An isolated thermodynamic system executes a process, choose the correct statement(s) form the following [GATE-1999] (a) No heat is transferred (b) No work is done (c) No mass flows across the boundary of the system (d) No chemical reaction takes place within the system [GATE-2011]
GATE-2a. Heat and work are (a) intensive properties (c) point functions
(b) extensive properties (d) path functions
Quasi-Static Process
GATE-3. A frictionless piston-cylinder device contains a gas initially at 0.8 MPa and 0.015 m3. It expands quasi-statically at constant temperature to a final volume of 0.030 m3. The work output (in kJ/kg) during this process will be: [GATE-2009] (a) 8.32 (b) 12.00 (c) 554.67 (d) 8320.00
Free Expansion with Zero Work Transfer

GATE-4. A balloon containing an ideal gas is initially kept in an evacuated and insulated room. The balloon ruptures and the gas fills up the entire room. Which one of the following statements is TRUE at the end of above process? (a) The internal energy of the gas decreases from its initial value, but the enthalpy remains constant [GATE-2008] (b) The internal energy of the gas increases from its initial value, but the enthalpy remains constant (c) Both internal energy and enthalpy of the gas remain constant (d) Both internal energy and enthalpy of the gas increase
12
Basic Concepts
S K Mondals
GATE-5.
Chapter 1
Air is compressed adiabatically in a steady flow process with negligible change in potential and kinetic energy. The Work done in the process is given by: [GATE-1996, IAS-2000] (a) Pdv (b) +Pdv (c) vdp (d) +vdp
pdV-work or Displacement Work

GATE-6. In a steady state steady flow process taking place in a device with a single inlet and a single outlet, the work done per unit mass flow rate is given by
outlet
inlet
vdp , where v is the specific volume and p is the pressure. The

[GATE-2008]
expression for w given above: (a) Is valid only if the process is both reversible and adiabatic (b) Is valid only if the process is both reversible and isothermal (c) Is valid for any reversible process
(d) Is incorrect; it must be =

GATE-7.
outlet
inlet
vdp
A gas expands in a frictionless piston-cylinder arrangement. The expansion process is very slow, and is resisted by an ambient pressure of 100 kPa. During the expansion process, the pressure of the system (gas) remains constant at 300 kPa. The change in volume of the gas is 0.01 m3. The maximum amount of work that could be utilized from the above process is: [GATE-2008] (a) 0kJ (b) 1kJ (c) 2kJ (d) 3kJ For reversible adiabatic compression in a steady flow process, the work transfer per unit mass is: [GATE-1996]
GATE-8.
(a) pdv
(b) vdp
(c) Tds
(d ) sdT
Previous 20-Years IES Questions

IES-1. Which of the following are intensive properties? [IES-2005] 1. Kinetic Energy 2. Specific Enthalpy 3. Pressure 4. Entropy Select the correct answer using the code given below: (a) 1 and 3 (b) 2 and 3 (c) 1, 3 and 4 (d) 2 and 4 Consider the following properties: [IES-2009] 1. Temperature 2. Viscosity 3. Specific entropy 4. Thermal conductivity Which of the above properties of a system is/are intensive? (a) 1 only (b) 2 and 3 only (c) 2, 3 and 4 only (d) 1, 2, 3 and 4 Consider the following: 1. Kinetic energy 2. Entropy [IES-2007, 2010]
IES-2.
IES-2a.
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Basic Concepts
S K Mondals
3. Thermal conductivity 4. Pressure Which of these are intensive properties? (a) 1, 2 and 3 only (b) 2 and 4 only (c) 3 and 4 only (d) 1, 2, 3 and 4 IES-3. Which one of the following is the extensive property of a thermodynamic system? [IES-1999] (a) Volume (b) Pressure (c) Temperature (d) Density Consider the following properties: [IES-2009] 1. Entropy 2. Viscosity 3. Temperature 4. Specific heat at constant volume Which of the above properties of a system is/are extensive? (a) 1 only (b) 1 and 2 only (c) 2, 3 and 4 (d) 1, 2 and 4 Consider the following: 1. Temperature 2. Viscosity 3. Internal energy 4. Entropy Which of these are extensive properties? (a) 1, 2, 3 and 4 (b) 2 and 4 only (c) 2 and 3 only (d) 3 and 4 only. [IES-2010]
Chapter 1
IES-4.
IES-4a
Thermodynamic System and Control Volume

IES-5. Assertion (A): A thermodynamic system may be considered as a quantity of working substance with which interactions of heat and work are studied. Reason (R): Energy in the form of work and heat are mutually convertible. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false [IES-2000] (d) A is false but R is true A control volume is [IES-2010] (a) An isolated system (b) A closed system but heat and work can cross the boundary (c) A specific amount of mass in space (d) A fixed region in space where mass, heat and work can cross the boundary of that region
IES-5a
Open and Closed systems

IES-6. A closed thermodynamic system is one in which [IES-1999, 2010, 2011] (a) There is no energy or mass transfer across the boundary (b) There is no mass transfer, but energy transfer exists (c) There is no energy transfer, but mass transfer exists (d) Both energy and mass transfer take place across the boundary, but the mass transfer is controlled by valves Isothermal compression of air in a Stirling engine is an example of
IES-7
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Basic Concepts
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(a) (b) (c) (d)
IES-8.
Chapter 1
[IES-2010]
Open system Steady flow diabatic system Closed system with a movable boundary Closed system with fixed boundary
Which of the following is/are reversible process(es)? [IES-2005] 1. Isentropic expansion 2. Slow heating of water from a hot source 3. Constant pressure heating of an ideal gas from a constant temperature source 4. Evaporation of a liquid at constant temperature Select the correct answer using the code given below: (a) 1 only (b) 1 and 2 (c) 2 and 3 (d) 1 and 4 Assertion (A): In thermodynamic analysis, the concept of reversibility is that, a reversible process is the most efficient process. [IES-2001] Reason (R): The energy transfer as heat and work during the forward process as always identically equal to the energy transfer is heat and work during the reversal or the process. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true Which one of the following represents open thermodynamic system? (a) Manual ice cream freezer (b) Centrifugal pump (c) Pressure cooker (d) Bomb calorimeter [IES-2011]
IES-9.
IES-9a
IES-10.
Ice kept in a well insulated thermo flask is an example of which system? (a) Closed system (b) Isolated systems [IES-2009] (c) Open system (d) Non-flow adiabatic system Hot coffee stored in a well insulated thermos flask is an example of (a) Isolated system (b) Closed system (c) Open system (d) Non-flow diabatic system A thermodynamic system is considered to be an isolated one if (a) Mass transfer and entropy change are zero (b) Entropy change and energy transfer are zero (c) Energy transfer and mass transfer are zero (d) Mass transfer and volume change are zero
IES-10a
[IES-2010]
IES10b
[IES-2011]
IES-10c.
Match List I with List II and select the correct answer using the code given below the lists: [IES-2011] List I List II A. Interchange of matter is not possible in a 1. Open system B. Any processes in which the system returns to 2. System its original condition or state is called C. Interchange of matter is possible in a 15
Basic Concepts
S K Mondals
D. The quantity of matter under consideration in thermodynamics is called 4. Cycle
Chapter 1
3. Closed system
Code: (a) (c)
A 2 2
B 1 4
C 4 1
D 3 3
(b) (d)
A 3 3
B 1 4
C 4 1
D 2 2
Zeroth Law of Thermodynamics

IES-11. Measurement of temperature is based on which law of thermodynamics? [IES-2009] (a) Zeroth law of thermodynamics (b) First law of thermodynamics (c) Second law of thermodynamics (d) Third law of thermodynamics Consider the following statements: [IES-2003] 1. Zeroth law of thermodynamics is related to temperature 2. Entropy is related to first law of thermodynamics 3. Internal energy of an ideal gas is a function of temperature and pressure 4. Van der Waals' equation is related to an ideal gas Which of the above statements is/are correct? (a) 1 only (b) 2, 3 and 4 (c) 1 and 3 (d) 2 and 4 Zeroth Law of thermodynamics states that [IES-1996, 2010] (a) Two thermodynamic systems are always in thermal equilibrium with each other. (b) If two systems are in thermal equilibrium, then the third system will also be in thermal equilibrium with each other. (c) Two systems not in thermal equilibrium with a third system are also not in thermal equilibrium with each other. (d) When two systems are in thermal equilibrium with a third system, they are in thermal equilibrium with each other.
IES-12.
IES-13.
International Temperature Scale

IES-14. Which one of the following correctly defines 1 K, as per the internationally accepted definition of temperature scale? [IES-2004] (a) 1/100th of the difference between normal boiling point and normal freezing point of water (b) 1/273.15th of the normal freezing point of water (c) 100 times the difference between the triple point of water and the normal freezing point of water (d) 1/273.15th of the triple point of water In a new temperature scale say , the boiling and freezing points of water at one atmosphere are 100 and 300 respectively. Correlate this scale with the Centigrade scale. The reading of 0 on the Centigrade scale is: [IES-2001] (a) 0C (b) 50C (c) 100C (d) 150C
IES-15.
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Basic Concepts
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IES-16.
Chapter 1
Assertion (a): If an alcohol and a mercury thermometer read exactly 0C at the ice point and 100C at the steam point and the distance between the two points is divided into 100 equal parts in both thermometers, the two thermometers will give exactly the same reading at 50C. [IES-1995] Reason (R): Temperature scales are arbitrary. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true Match List-I (Type of Thermometer) with List-II (Thermometric select the correct answer using the code given below the List-I List-II 1. Pressure A. Mercury-in-glass B. Thermocouple 2. Electrical resistant C. Thermistor 3. Volume D. Constant volume gas 4. Induced electric voltage Codes: A B C D A B (a) 1 4 2 3 (b) 3 2 (c) 1 2 4 3 (d) 3 4 Pressure reaches a value of absolute zero (a) At a temperature of 273 K (b) Under vacuum condition (c) At the earth's centre (d) When molecular momentum of system becomes zero Property) and [IES 2007]
IES-17.
C 4 2
D 1 1 [IES-2002]
IES-18.
IES-19.
The time constant of a thermocouple is the time taken to attain: (a) The final value to he measured [IES-1997, 2010] (b) 50% of the value of the initial temperature difference (c) 63.2% of the value of the initial temperature difference (d) 98.8% of the value of the initial temperature difference
Work a Path Function

IES-20. Assertion (A): Thermodynamic work is path-dependent except for an adiabatic process. [IES-2005] Reason(R): It is always possible to take a system from a given initial state to any final state by performing adiabatic work only. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true Work transfer between the system and the surroundings (a) Is a point function (b) Is always given by pdv [IES-2011]
IES-20a
(c) Is a function of pressure only
(d) Depends on the path followed by the system 17
Basic Concepts

IES-21. Match items in List-I (Process) with those in List-II (Characteristic) and select the correct answer using the codes given below the lists: List-I List-II [IES-2001] A. Throttling process 1. No work done B. Isentropic process 2. No change in entropy C. Free expansion 3. Constant internal energy D. Isothermal process 4. Constant enthalpy Codes: A B C D A B C D (a) 4 2 1 3 (b) 1 2 4 3 (c) 4 3 1 2 (d) 1 3 4 2 The heat transfer, Q, the work done W and the change in internal energy U are all zero in the case of [IES-1996] (a) A rigid vessel containing steam at 150C left in the atmosphere which is at 25C. (b) 1 kg of gas contained in an insulated cylinder expanding as the piston moves slowly outwards. (c) A rigid vessel containing ammonia gas connected through a valve to an evacuated rigid vessel, the vessel, the valve and the connecting pipes being well insulated and the valve being opened and after a time, conditions through the two vessels becoming uniform. (d) 1 kg of air flowing adiabatically from the atmosphere into a previously evacuated bottle.
IES-22.

IES-23. One kg of ice at 0C is completely melted into water at 0C at 1 bar pressure. The latent heat of fusion of water is 333 kJ/kg and the densities of water and ice at 0C are 999.0 kg/m3 and 916.0 kg/m3, respectively. What are the approximate values of the work done and energy transferred as heat for the process, respectively? [IES-2007] (a) 9.4 J and 333.0 kJ (b) 9.4 J and 333.0 kJ (c) 333.0 kJ and 9.4 J (d) None of the above Which one of the following is the correct sequence of the three processes A, B and C in the increasing order of the amount of work done by a gas following idealgas expansions by these processes?
IES-24.
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IES-25.
Chapter 1
(c) A C B
[IES-2006] (d) C A B
(a) A B C (b) B A C An ideal gas undergoes an isothermal expansion from state R to state S in a turbine as shown in the diagram given below:
The area of shaded region is 1000 Nm. What is the amount is turbine work done during the process? (a) 14,000 Nm (b) 12,000 Nm (c) 11,000 Nm (d) 10,000 Nm
[IES-2004]
IES-26.
Assertion (A): The area 'under' curve on pv plane, reversible non-flow process. Reason (R): The area 'under' the curve Ts plane
pdv represents the work of

[IES-1992]
Tds represents heat of any
reversible process. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true IES-27. If
pdv
and vdp for a thermodynamic system of an Ideal gas on valuation
give same quantity (positive/negative) during a process, then the process undergone by the system is: [IES-2003]
(a) Isomeric
IES-28.
(b) Isentropic
(c) Isobaric
(d) Isothermal
Which one of the following expresses the reversible work done by the system (steady flow) between states 1 and 2? [IES-2008]
(a)
pdv
1
(b) vdp
1
(c) pdv
1
(d)
vdp
1
Heat Transfer-A Path Function

IES-29. Assertion (A): The change in heat and work cannot be expressed as difference between the end states. [IES-1999] Reason (R): Heat and work are both exact differentials. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
19
Basic Concepts
Previous 20-Years IAS Questions Thermodynamic System and Control Volume

IAS-1. The following are examples of some intensive and extensive properties: 1. Pressure 2. Temperature [IAS-1995] 3. Volume 4. Velocity 5. Electric charge 6. Magnetisation 7. Viscosity 8. Potential energy Which one of the following sets gives the correct combination of intensive and extensive properties? Intensive Extensive (a) 1, 2, 3, 4 5, 6, 7, 8 (b) 1, 3, 5, 7 2, 4, 6, 8 (c) 1, 2, 4, 7 3, 5, 6, 8 (d) 2, 3, 6, 8 1, 4, 5, 7
Zeroth Law of Thermodynamics

IAS-2. Match List-I with List-II and select the correct answer using the codes given below the lists: [IAS-2004] List-I List-II A. Reversible cycle 1. Measurement of temperature B. Mechanical work 2. Clapeyron equation C. Zeroth Law 3. Clausius Theorem D. Heat 4. High grade energy 5. 3rd law of thermodynamics 6. Inexact differential Codes: A B C D A B C D (a) 3 4 1 6 (b) 2 6 1 3 (c) 3 1 5 6 (d) 1 4 5 2 Match List-I with List-II and select the correct answer: [IAS-2000] List-I List-II A. The entropy of a pure crystalline 1. First law of thermodynamics substance is zero at absolute zero temperature B. Spontaneous processes occur 2. Second law of thermodynamics in a certain direction C. If two bodies are in thermal 3. Third law of thermodynamics equilibrium with a third body, then they are also in thermal equilibrium with each other D. The law of conservation of energy 4. Zeroth law of thermodynamics. Codes: A B C D A B C D (a) 2 3 4 1 (b) 3 2 1 4 20
IAS-3.
Basic Concepts
S K Mondals
(c) 3 2 4 1 (d) 2 3 1
Chapter 1
4
International Temperature Scale

IAS-4. A new temperature scale in degrees N is to be defined. The boiling and freezing on this scale are 400N and 100N respectively. What will be the reading on new scale corresponding to 60C? [IAS-1995] (c) 220N (d) 280N (a) 120N (b) 180N

IAS-5. In free expansion of a gas between two equilibrium states, the work transfer involved [IAS-2001] (a) Can be calculated by joining the two states on p-v coordinates by any path and estimating the area below (b) Can be calculated by joining the two states by a quasi-static path and then finding the area below (c) Is zero (d) Is equal to heat generated by friction during expansion. Work done in a free expansion process is: (a) Positive (b) Negative (c) Zero In the temperature-entropy diagram of a vapour shown in the given figure, the thermodynamic process shown by the dotted line AB represents (a) Hyperbolic expansion (b) Free expansion (c) Constant volume expansion (d) Polytropic expansion [IAS-1995] IAS-8. If [IAS-2002] (d) Maximum
IAS-6. IAS-7.
pdv
and vdp for a thermodynamic system of an Ideal gas on valuation
give same quantity (positive/negative) during a process, then the process undergone by the system is: [IAS-1997, IES-2003] (a) Isomeric (b) Isentropic (c) Isobaric (d) Isothermal IAS-9. For the expression
pdv
to represent the work, which of the following
conditions should apply? [IAS-2002] (a) The system is closed one and process takes place in non-flow system (b) The process is non-quasi static (c) The boundary of the system should not move in order that work may be transferred (d) If the system is open one, it should be non-reversible
21
Basic Concepts
S K Mondals
IAS-10.
Chapter 1
IAS-11.
Air is compressed adiabatically in a steady flow process with negligible change in potential and kinetic energy. The Work done in the process is given by: [IAS-2000, GATE-1996] (a) pdv (b) +pdv (c) vdp (d) +vdp Match List-I with List-II and select the correct answer using the codes given below the lists: [IAS-2004] List-I List-II A. Bottle filling of gas 1. Absolute Zero Temperature B. Nernst simon Statement 2. Variable flow C. Joule Thomson Effect 3. Quasi-Static Path D. pdv 4. Isentropic Process 5. Dissipative Effect 6. Low grade energy 7. Process and temperature during phase change. Codes: A B C D A B C D (a) 6 5 4 3 (b) 2 1 4 3 (c) 2 5 7 4 (d) 6 1 7 4

IAS-13. Thermodynamic work is the product of (a) Two intensive properties (b) Two extensive properties (c) An intensive property and change in an extensive property (d) An extensive property and change in an intensive property [IAS-1998]
Heat Transfer-A Path Function

IAS-14. Match List-I (Parameter) with List-II using the codes given below the lists: List-I A. Volume B. Density C. Pressure D. Work Codes: A B C D (a) 3 2 4 1 (c) 2 3 4 1 (Property) and select the correct answer List-II 1. Path function 2. Intensive property 3. Extensive property 4. Point function A B C (b) 3 2 1 (d) 2 3 1 [IAS-1999]
D 4 4
22
Basic Concepts
Answers with Explanation (Objective)

Previous 20-Years GATE Answers
GATE-1. Ans. (a) GATE-2. Ans. (a, b, c) For an isolated system no mass and energy transfer through the system.
dQ = 0,
GATE-2a. Ans. (d)
dW = 0,
dE = 0
or E = Constant
GATE-3. Ans. (a) Iso-thermal work done (W) = RT1 ln
V2 V1 V = P1V1 ln 2 V1
0.030 = 800 0.015 ln 0.015 = 8.32 kJ/kg
GATE-4. Ans. (c) It is free expansion. Since vacuum does not offer any resistance, there is no work transfer involved in free expansion.
Here,
= 0
1
and Q1-2=0 therefore Q1-2 = U + W1-2 so, U = 0
GATE-5. Ans. (c) For closed system W =
+ pdv , for steady flow W = vdp
GATE-6. (c) GATE-7. Ans. (b) W = Resistance pressure. V = 1 V = 100 0.1 kJ = 1kJ GATE-8. Ans. (b) W = vdp
Previous 20-Years IES Answers

IES-1. Ans. (b) IES-2. Ans. (d) Intensive property: Whose value is independent of the size or extent i.e. mass of the system. Specific property: It is a special case of an intensive property. It is the value of an extensive property per unit mass of system (Lower case letters as symbols) e.g., specific volume, density (v, ). IES-2a. Ans. (c) Kinetic energy
1 mv 2 depends on mass, Entropy kJ/k depends on mass so 2

23
Entropy is extensive property but specific entropy kJ/kg K is an intensive property.
Basic Concepts
IES-3. Ans. (a) Extensive property is dependent on mass of system. Thus volume is extensive property. IES-4. Ans. (a) Extensive property: Whose value depends on the size or extent i.e. mass of the system (upper case letters as the symbols) e.g., Volume, Mass (V, M). If mass is increased, the value of extensive property also increases. IES-4a Ans. (d) The properties like temperature, viscosity which are Independent of the MASS of the system are called Intensive property IES-5. Ans. (d) But remember 100% heat cant be convertible to work but 100% work can be converted to heat. It depends on second law of thermodynamics. A thermodynamic system is defined as a definite quantity of matter or a region in space upon which attention is focused in the analysis of a problem. The system is a macroscopically identifiable collection of matter on which we focus our attention IES-5a Ans. (d) IES-6. Ans. (b) In closed thermodynamic system, there is no mass transfer but energy transfer exists. IES-7. Ans. (c) IES-8. Ans. (d) Isentropic means reversible adiabatic. Heat transfer in any finite temp difference is irreversible. IES-9. Ans. (a) The energy transfer as heat and work during the forward process as always identically equal to the energy transfer is heat and work during the reversal or the process is the correct reason for maximum efficiency because it is conservative system. IES-9a. Ans. (b) IES-10. Ans. (b) Isolated System - in which there is no interaction between system and the surroundings. It is of fixed mass and energy, and hence there is no mass and energy transfer across the system boundary. IES-10a Ans. (a) IES-10b. Ans. (c) IES-10c. Ans. (d) IES-11. Ans. (a) All temperature measurements are based on Zeroth law of thermodynamics. IES-12. Ans. (a) Entropy - related to second law of thermodynamics. Internal Energy (u) = f (T) only (for an ideal gas) Van der Wall's equation related to => real gas. IES-13. Ans. (d) IES-14. Ans. (d) IES-15.Ans. (d)
C 0 0 300 = C = 150C 100 300 100 0
24
Basic Concepts
IES-16. Ans. (b) Both A and R are correct but R is not correct explanation for A. Temperature is independent of thermometric property of fluid. IES-17. Ans. (d) IES-18. Ans. (d) But it will occur at absolute zero temperature. IES-19. Ans. (c) Time Constants: The time constant is the amount of time required for a thermocouple to indicated 63.2% of step change in temperature of a surrounding media. Some of the factors influencing the measured time constant are sheath wall thickness, degree of insulation compaction, and distance of junction from the welded cap on an ungrounded thermocouple. In addition, the velocity of a gas past the thermocouple probe greatly influences the time constant measurement. In general, time constants for measurement of gas can be estimated to be ten times as long as those for measurement of liquid. The time constant also varies inversely proportional to the square root of the velocity of the media. IES-20. Ans. (c) IES-20a Ans. (d) IES-21. Ans. (a) IES-22. Ans. (c) In example of (c), it is a case of free expansion heat transfer, work done, and changes in internal energy are all zero. IES-23. Ans. (a) Work done (W) = P V = 100 (V2 V1) = 100
1 1 = 100 kPa = 9.1 J 999 916
m 2
m 1
IES-24. Ans. (d)
WA = pdV = 4 (2 1) = 4 kJ
1 WB = pdV = 3 (7 4) = 4.5 kJ 2 WC = pdV = 1 (12 9) = 3kJ

IES-25. Ans. (c) Turbine work = area under curve RS
= pdv = 1 bar ( 0.2 0.1) m3 + 1000 Nm
= 105 ( 0.2 0.1) Nm + 1000Nm = 11000 Nm

IES-26. Ans. (b) IES-27. Ans. (d) Isothermal work is minimum of any process.
pv = mRT
pdv + vdp = 0[ T is constant]
pdv = vdp
IES-28. Ans. (b) For steady flow process, reversible work given by vdp .
1
IES-29. Ans. (c) A is true because change in heat and work are path functions and thus can't be expressed simply as difference between the end states. R is false because both work and heat are inexact differentials.
25
Basic Concepts
Previous 20-Years IAS Answers

IAS-1. Ans. (c) Intensive properties, i.e. independent of mass are pressure, temperature, velocity and viscosity. Extensive properties, i.e. dependent on mass of system are volume, electric charge, magnetisation, and potential energy. Thus correct choice is (c). IAS-2. Ans. (a) IAS-3. Ans. (c) IAS-4. Ans. (d) The boiling and freezing points on new scale are 400 N and 100N i.e. range is 300N corresponding to 100C. Thus conversion equation is N = 100 + 3 C = 100+ 3 60 = 100 + 180 = 280 N IAS-5. Ans. (c) IAS-6. Ans. (c) Since vacuum does not offer any resistance, there is no work transfer involved in free expansion. IAS-7. Ans. (b) IAS-8. Ans. (d) Isothermal work is minimum of any process. IAS-9. Ans. (a) IAS-10. Ans. (c) For closed system W = IAS-12. Ans. (b) Start with D. PdV only valid for quasi-static path so choice (c) & (d) out. Automatically C-4 then eye on A and B. Bottle filling of gas is variable flow so A-2. IAS-13. Ans. (c) W = pdv where pressure (p) is an intensive property and volume (v) is an
+ pdv , for steady flow W = vdp
extensive property IAS-14. Ans. (a) Pressure is intensive property but such option is not there.
26
Fir rst Law w of Therm T odyna amics

2.
First t Law w of T herm modyn namic cs
Theo ory at a Glance (Fo or GAT TE, IES S & PS SUs) First Law w of Th hermody ynamic cs
St tatement:
When a closed syste em executes a complete cy ycle the sum of heat interact tions is equa al to the sum of work interact tions. Mathem matically
( Q)cycl le = ( W)cycle
The sum mmations be eing over the entire cycle.
Al lternate st tatement: :
Wh hen a closed system undergoes a cycl le the cyclic integral of heat h is equal to the cyclic c integral of wo ork. Ma athematical lly
Q
In other word ds for a two process cycle
Q A1 A 2 + QB2 1 = WA1 2 + WB 2 1
In nternal Energy y A Pr roperty y of Sys stem
W Which can be e written as s
28

Since A and B are arbitrarily a ch hosen, the con nclusion is, as a far as a pr rocess is conc cerned (A or B) the difference Q W rema ains a consta ant as long as a the initial and the fina al states are the sam me. The diffe erence depends only on th he end points of the proc cess. Note that Q and W themse elves depend on the path followed. f But t their differe ence does not t. This im mplies that th he difference between the e heat and wo ork interactio ons during a process is a propert ty of the system. This pr roperty is called the energ gy of the syst tem. It is des signated as E and is equa al to some of all the energies e at a given state.
We e enunciate the t FIRST LA AW for a proc cess as
Q W = dE
An isol lated system m which do oes not inter ract with th he surround dings Q = 0 and W = 0. Theref fore, E rema ains constan nt for such a system. Let us reconsider r th he cycle 1-2 along a path A and 2-1 alon ng path B as shown s in fig. Work done d during the path A = Area A under 1-A-2-3-4 1 Work done d during the path B = Area A under 1-B-2-3-4 1 Since these two are eas are not equal, e the ne et work inter raction is tha at shown by the shaded area.
29

S K Mondals

Cha apter 2
The net t area is 1A2B1. Therefo ore some wor rk is derived by the cycle. First la aw compels that this is s possible only o when there t is also o heat interaction betwe een the syst tem and the surrounding gs. In oth her words, if i you have e to get wo ork out, yo ou must give e heat in. Thus, the t first law can be const trued to be a statement of o conservatio on of energy - in a broad sense. In the example e show wn the area under u curve A < that und der B The cyc cle shown ha as negative work output t or it will receive work from the su urroundings. Obviously, the net heat h interact tion is also ne egative. This s implies that this cycle will w heat the nment. (as pe er the sign co onvention). environ For a process we can n have Q = 0 or W = 0 We can n extract wor rk without su upplying heat (during a process) bu ut sacrificing g the energy of the system. s We can n add heat to the system without doin ng work (in process) p wh hich will go to o increasing the ene ergy of the sy ystem. Energy y of a system m is an exte ensive prop perty
he internal en nergy depend ds only upon the initial an nd final state es of the syst tem. Internal l energy of a Th sub bstance does not include any energy that t it may possess p as a result r of its macroscopic m c position or mo ovement. Tha at so why in SFEE S (Stead dy flow energ gy equation) C2/2 and gz is s there. ecognize that h Re and similarly
= u + pv p from whic ch u2 + p2 v2 = h2
u1 + p1v1 = h1
Q QW = [(h2 + C22/2 + gZ2) - (h1+C C12/2 + gZ1)] = [(h2 - h1) + (C22/2 - C12/2) + g(Z2 - Z1)]
[W Where C = Vel locity (m/s), h = Specific enthalpy e (J/k kg), z = elevat tion (m)
or
Bu ut Reme ember:
Mi icroscopic vie ew of a gas is a collection of particles in random mo otion. Energy y of a particle consists of tra anslational energy, rot tational ene ergy, vibrat tional energ gy and speci ific electron nic energy. All l these energ gies summed d over all the e particles of f the gas, form m the specifi ic internal en nergy, e , of the e gas.
30

Perpetua al Motio on Mac chine of f the First Kind-PMM M1

Th he first law st tates the gen neral principl le of the cons servation of energy. e Energ gy is neither created nor des stroyed, but only gets tra ansformed fro om one form to t another. here can be no n machine which would d continuous sly supply mechanical m wo ork without some other Th for rm of energy disappearing g simultaneo ously (Fig. sh hown in below w). Such a fictitious mach hine is called ap perpetual mo otion machine e of the first kind, or in br rief, PMM1. A PMM1 is thus t impossible. he converse of the above statement t is also tru ue, i.e. there e can be no machine which w would Th con ntinuously co onsume work k without som me other form m of energy appearing a sim multaneously y (Fig.).
A PMM1 P
The e Converse of o PMM1
Enthalpy y
Th he enthalpy of a substance e H is defined d as
It i is an extens sive propert ty of a system m and its uni it is kJ.
H = U + PV P h = u + pv p
lpy Specific Enthal
is an intensi ive propert ty of a system m and its unit t is kJ/kg. It i Int ternal energy y change is equal to the heat transfe erred in a co onstant volum me process involving i no wo ork other tha an pdv work. It is possibl le to derive an a expression n for the hea at transfer in n a constant pre essure process involving no work oth her than pdv v work. In su uch a proces ss in a closed d stationary sys stem of unit mass m of a pure substance e. d Q = du + pdv At constan nt pressure pdv = d(pv) Therefo ore ( dQ ) = du + d ( pv ) or ( dQ ) or
P
( dQ ) P =
= d(u+pv) dh
W Where H = U + PV is the enthalpy, a property of system. s Specific enth halpy h = H/m m, kJ/kg and also h = u + pdv Where h = sp pecific enthalpy, kJ/kg 31
First Law of Thermodynamics

S K Mondals
u = specific internal energy, kJ/kg dv = change in specific volume, m3/kg.
Chapter 2
The specific heat of a substance at constant volume Cv is defined as the rate of change of specific internal energy with respect to temperature when the volume is held constant, i.e., u Cv = T v For a constant volume process
Specific heat at constant volume
( u )v =
T2
T1
C .dT
v
The first law may be written for a closed stationary system composed of a unit mass of a pure substance. Q = u + W or d Q = du + d W For a process in the absence of work other than pdv work d W = pdv Therefore d Q = du + pdv Therefore, when the volume is held constant (Q )v = ( u )v
(Q )v = Cv .dT
T1
T2
Since u, T and v are properties, Cv is a property of the system. The product m Cv is called the heat capacity at constant volume (J/K).
Specific heat at constant pressure

The specific heat at constant pressure Cp is defined as the rate of change of specific enthalpy with respect to temperature when the pressure is held constant. h CP = T P For a constant pressure process
( h )P
T2
T1
.dT
The first law for a closed stationary system of unit mass dQ = du + pdv Again, h = u + pv Therefore dh = du + pdv + vdp = d Q + vdp Therefore
dQ = dh vdp
Therefore ( dQ )P = dh
32

S K Mondals
or
Chapter 2
= ( h) p
T2
(Q ) p
( Q )P
Form abow equations

=
T1
.dT
Cp
is a property of the system, just like Cv. The heat capacity at constant pressure is equal to m C p (J/K).
Application of First Law to Steady Flow Process S.F.E.E

S.F.E.E. per unit mass basis
2 2 C1 C2 dQ dW + gz1 + = h2 + + gz2 + h1 + 2 dm 2 dm
(i)
[h, W, Q should be in J/Kg and C in m/s and g in m/s2]
(ii)
2 2 C1 dQ C2 dW gZ1 gZ 2 h1 + + + = h2 + + + 2000 1000 dm 2000 1000 dm
[h, W, Q should be in KJ/Kg and C in m/s and g in m/s2]
S.F.E.E. per unit time basis
dQ C12 w1 h1 + + z1 g + 2 d
2 dWx C2 = w2 h2 + + z2 g + d 2
Where, w = mass flow rate (kg/s)

Steady Flow Process Involving Two Fluid Streams at the Inlet and Exit of the Control Volume
33

Ma ass balance
w A 1C v1
1
+ w
2
= w A 3C v3
3 3
+ w +
4 4
A 2C v2
A 4C v4
here v = spec cific volume (m ( 3/kg) Wh En nergy balan nce

2 dQ C12 C2 w1 h1 + + Z1 g + w2 h2 + + Z2 g + 2 2 d
dWx C2 C2 = w3 h3 + 3 + Z3 g + w4 h4 + 4 + Z4 g + 2 2 d
ome exampl le of steady y flow proce esses:So Th he following examples e illu ustrate the applications of o the steady flow energy equation in some of the eng gineering sys stems. No ozzle and Di iffuser: An nozzle is a device d which increases th he velocity or o K.E. of a fluid at the e expense of its pressure dro op, whereas a diffuser in ncreases the pressure of a fluid at the e expense of its K.E. Figu ure show in bel low a nozzle which is insu ulated. The steady s flow en nergy equation of the con ntrol surface gives dWx C2 C2 dQ = h2 + 2 + Z 2 g + h1 + 1 + Z1 g + dm dm 2 2
F Fig. 34

S K Mondals
Here
Chapter 2
dWx dQ = 0; = 0, and the change in potential energy is zero. The equation reduces to dm dm C2 C2 h1 + 1 = h2 + 2 (a) 2 2 The continuity equation gives AC AC (b) w= 1 1 = 2 2 v1 v2 When the inlet velocity or the velocity of approach V1 is small compared to the exit velocity V2, Equation (a) becomes
2 C2 h1 = h2 + 2
or
C2 = 2(h1 h2 )m / s
where (h1 h2) is in J/kg. Equations (a) and (b) hold good for a diffuser as well.
Throttling Device: When a fluid flows through a constricted passage, like a partially opened value, an orifice, or a porous plug, there is an appreciable drop in pressure, and the flow is said to be throttled. Figure shown in below, the process of throttling by a prettily opened value on a fluid flowing in an insulated pipe. In the steady-flow energy equationdWx dQ = 0, =0 dm dm And the changes in P. E. are very small and ignored. Thus, the S.F.E.E. reduces to C2 C2 h1 + 1 = h2 + 2 2 2
(Fig.- Flow Through a Valve) Often the pipe velocities in throttling are so low that the K. E. terms are also negligible. So
h1 = h2
or the enthalpy of the fluid before throttling is equal to the enthalpy of the fluid after throttling.
Turbine and Compressor: Turbines and engines give positive power output, whereas compressors and pumps require power input. For a turbine (Fig. below) which is well insulated, the flow velocities are often small, and the K.E. terms can be neglected. The S.F.E.E. then becomes
35

(Fig.-. Flow through a Turbine)

h1 = h2 + or dWx dm
Wx = h1 h2 m The enthalpy of the fluid increase by the amount of work input.
Heat Exchanger: A heat exchanger is a device in which heat is transferred from one fluid to another, Figure shown in below a steam condenser where steam condense outside the tubes and cooling water flows through the tubes. The S.F.E.E for the C.S. gives wc h1 + ws h2 = w c h3 + ws h4
or , ws ( h2 h4 ) = w c (h3 h1 )
Here the K.E. and P.E. terms are considered small, there is no external work done, and energy exchange in the form of heat is confined only between the two fluids, i.e. there is no external heat interaction or heat loss.
Fig. Figure (shows in below) a steam desuperheater where the temperature of the superheated steam is reduced by spraying water. If w1, w2, and w3 are the mass flow rates of the injected water, of the steam entering, and of the steam leaving, respectively, and h1, h2, and h3 are the corresponding enthalpies, and if K.E. and P.E. terms are neglected as before, the S.F.E.E. becomes w1h1 + w2 h2 = w3 h3 and the mass balance gives w1 + w2 = w3
36

Th he above law w is also call led as stead dy flow ene ergy equati ion. This can n be applied d to various pra actical situat tions as work k developing system and work absorp ption system. Let the ma ass flow rate un nity. (1) ) Work deve eloping syst tems (a) Water turbines In this cas se Q = 0 and U = 0 and equation e becomes 2 C p1 v1 +z1g + 1 = z2g + p2 v2 +W 2 (b) Steam or gas turbin nes In this cas se generally Z can be assumed to be zero and the e equation becomes 2 C12 C2 W = ( h1 h2 ) + + Q 2 ) Work abso orbing syste ems (2) (a) Centrifug gal water pum mp The system m is shown in the Figure below b
Fig. stem Q = 0 and U = 0; th he energy equ uation now becomes, b In this sys 2 C2 p1 v1 +z1g + W = z2g + p2 v2 + 2 al compress sor In this system s z = 0 and the equ uation becom mes, (b) Centrifuga 2 2 C1 C + h1 + W Q = 2 + h2 2 2 (c) Blowers In this case we have z = 0, p1 v1 = p2 v 2 and Q = 0; now the e energy simp plifies to 37

C2 u1 +W = u2 s C2 C1 + 2 as 2 ) Fans In fans f the tem mperature rise is very small and heat loss is negle ected (i.e.) h = 0, q = 0 (d) and hence th he energy equ uation for fan ns becomes, C2 W= 2 2 ting compre essor In a reciprocating g compressor r KE and PE P are neglig gibly energy (e) Reciprocat equation app plied to a reciprocating co ompressor is h1 Q = h 2 W
or W = Q + ( h2 h1 )
) Non-work developing g and absorb bing system ms (3)

(a) Steam boi iler In this s system we neglect Z, KE and W (i.e.) Z = KE K = W = 0; ; the energy equation for a boiler beco omes Q = (h2 h1) (b) Steam con ndenser In n this system m the work do one is zero and a we can also a assume Z and KE are very sma all. Under ste eady conditio ons the chang ge in enthalp py is equal to o heat lost by y steam. Q = (h1 h2) and d this heat is also equal to the change e in enthalpy y of cooling water w circulat ted (i.e.) the heat lost by steam will be e equal to heat gained by the cooling water. w (c) Steam nozz zle:
In this syste em we can assume Z an nd W to be zero z and hea at transfer which w is nothing but any possible heat t loss also zero. The ene ergy equation n for this cas se becomes. 2 C C2 h1 + 1 = h2 + 2 2 2
or C2 = C12 + 2(h1 h2 )
(vi ii) Unsteady y Flow Anal lysis:Ma any flow proc cesses, such as a filling up and a evacuati ing gas cylind ders, are not steady, Such h processes can n be analyzed d by the cont trol volume te echnique. Co onsider a dev vice through which w a fluid d is flowing un nder non-stea ady state cond ditions (Figu ure-shown in below). The rate r at which h the mass of f fluid wit thin the cont trol volume is s accumulate ed is equal to o the net rate e of mass flow w across the control c sur rface, as give en below:
38

F Fig. dmv dm1 dm d 2 = w1 w2 = d d d

here mv is th he mass of flu uid within th he control volume at any instant. i Wh Over an ny finite peri iod of time mv = m1 m2 Th he rate of acc cumulation of f energy with hin the contr rol volume is s equal to the e net rate of energy flow acr ross the control surface. If I Ev is the en nergy of fluid d within the control c volum me at any instant, Ra ate of energy increase = Rate R of energy y inflow Ra ate of energy outflow. 2 2 dW dEv C C dQ w2 h 2 + 2 +Z2g = w1 h1 + 1 +Z Z1g + equati ion... A d 2 2 d d
mC2 Ev = U + + mgZ m 2 v Wh here m is the e mass of flui id in the cont trol volume at a any instant t 2 dE d mC C v = + mgZ = U + d d 2 v dm1 dQ dm 2 dW C12 C2 + h 2 + 2 +Z2g +Z1g h1 + 2 2 d d d d ation........B ) ( equa
Following Figu ure shows all these energy y flux quantit ties. For any y time interva al, equation (B) ( becomes 2 2 C C Ev = Q W + h1 + 1 +Z1g dm m1 h2 + 2 +Z2g dm2 2 2
Fig. Equatio on (A) is gene eral energy equation. e For r steady flow, dEv =0 d and the equatio on reduces For F a closed system s w1 = 0, 0 w2 = 0, the en from equat tion (A), dEv dQ dW = d d d Or r dEv = dQ d dW or dQ = dE + dW d
39

S K Mondals
ow Processes s Flo
Cha apter 2
Ex xample of a variable flo ow problem m: Va ariable flow processes p may y be analyzed d either by th he system tec chnique or th he control vol lume tec chnique, as il llustrated below. Conside er a process in i which a ga as bottle is filled from a pipeline p (Figu ure shown in below). In the e beginning the t bottle con ntains gas of mass m1 at state s p1, T1, v1, h1 and u1. The valve is s opened and gas flows in nto the bottle e till the mas ss of gas in th he bottle is m2 at state p2, T2, v2, h2 an nd u2. The sup pply to the pi ipeline is ver ry large so th hat the state of gas in the pipeline is constant at p p ,TP , v P , h P , u P and v P .
Sy ystem Techn nique: Assum me an envelo ope (which is extensible) of o gas in the pipeline p and the tube wh hich would ev ventually ent ter the bottle e, as shown in n Figure abov ve. Energy y of the gas be efore filling. C2 E1 = m1 u1 + ( m2 m1 ) P + uP 2 Wh here ( m2 m1 ) is the ma ass of gas in the t pipeline and a tube whi ich would enter the bottle e.
E2 = m2 u2 C2 E = E2 E1 = m2 u2 m1 u1 ( m1 u1 ) P + uP 2 The P.E. terms t are neglected. The gas in the bo ottle is not in n motion, and d so the K.E. terms have en omitted. bee Now, ther re is a chang ge in the volume of gas because of the t collapse of the envel lope to zero vol lume. Then the t work done W = p (V2 V1 )
p
= pp 0 ( m2 m1 ) v P = ( m2 m1 ) p p v P
Us sing the first t for the process Q = E + W
C2 = m2 u2 m1 u1 ( m2 m1 ) P + uP ( m2 m1 ) pP vP 2
40

S K Mondals
C2 = m2 u2 m1 u1 ( m2 m1 ) P + h P 2 hich gives the e energy bala ance for the process. p wh
Co ontrol Volum me Techniq que: Assume a control vol lume bounded by a contro ol surface as shown in Fig gure above, Applying A the energy equa ation in this case, the foll lowing energy y balance ma ay be wr ritten on a tim me rate basis sdEv dQ C 2 dm m = + hP + P d d 2 d
Sin nce hP and CP are constan nt, the equati ion is integra ated to give for f the Total process 2 C Ev = Q + h P + P ( m2 m1 ) 2 No ow Ev = U 2 U1 = m2 u2 m1 u1
Cha apter 2
C2 Q = m2 u2 m1 u1 h P + P ( m2 m1 ) 2
D Discharg ging an nd Char rging a Tank

Let us consider r a tank disc charging a flu uid into a su upply line (Fi igure). Since e dWx = 0 an nd dmin = 0, app plying first la aw to the con ntrol volume, ,
C2 + gz dmout dUV = dQ Q + h + 2 out

Assuming K.E. and P.E. of the t fluid to be b small and dQ = 0
d(mu) = hdm mdu+ udm = udm+ pv dm d
dm du = m pv onst. V = vm = co vdm + mdv = 0 dm dv = m v du dv = pv v d ( u + pv ) = 0 or dQ = 0
Ag gain or
wh hich shows that t the process is adiab batic and quasi-static. For cha arging the tan nk 41
Charging and Disc charging a Tank

S K Mondals
( hdm )
in
Chapter 2
= UV = m2u2 m1u1 mphp = m2u2 m1u1
where the subscript p refers to the constant state of the fluid in the pipeline. If the tank is initially empty, m1 = 0. m p h p = m2 u2 Since
mp = m2 hp = u2
If the fluid is an ideal gas, the temperature of the gas in the tank after it is charged is given by
c pTp = cvT2 or T2 = Tp
PROBLEMS & SOLUTIONS
Example 1 The work and heat transfer per degree of temperature change for a closed system is given by dW 1 dQ 1 = kJ / C; = kJ / C dT 30 dT 10 Calculate the change in internal energy as its temperature increases from 125C to 245C. Solution: dT dW = 30
W =
T2
dT 1 1 = (T2 T1 ) = ( 245 125 ) 30 30 T1 30
dQ = Q=
T2
dT 10 dT = 1 ( 245 125 ) = 12 kJ 10
T1
10
Applying First Law of Thermodynamics Q = W + U U = Q W = 12 4 = 8kJ.

Example 2 Air expands from 3 bar to 1 bar in a nozzle. The initial velocity is 90 m/s. the initial temperature is 150C. Calculate the velocity of air at the exit of the nozzle. Solution: The system in question is an open one. First Law of Thermodynamics for an open system gives C2 C2 w1 h1 + 1 + Z1 g + Q = w2 h2 + 2 + Z2 g + W 2 2 Since the flow is assumed to be steady. w1 = w2 Flow in a nozzle is adiabatic flow. 42

S K Mondals
Hence Q = 0 Also W = 0 The datum can be selected to pass through axis; then Z1 = Z2. Hence C2 C2 h1 + 1 = h2 + 2 2 2 2 C2 C2 ( or ) = ( h1 h2 ) + 1 2 2 and
p T2 = T1 2 p1 for air = 1.4
1
Chapter 2
T1 = 150 + 273 = 423 1 T2 = 423 = 309 K 3 For air Cp = 1.005 kJ/kgC Cv = 0.718 kJ/kgC. R = 287 J/kg K = 0.287 kJ/kg K S.F.E.E. : - We have (h1 h2) = Cp(T1 - T2) 2 C2 C2 902 = ( h1 h2 ) + 1 = 1.005 103 (423 309) + 2 2 2 or, C2 = 487 m / s.
0.4/1.4
Example 3 An evacuated cylinder fitted with a valve through which air from atmosphere at 760 mm Hg and 25C is allow to fill it slowly. If no heat interaction is involved, what will be the temperature of air in the bottle when the pressure reaches 760 mm Hg? Use the following: (1) Internal energy of air u = u0 + 0.718T kJ/kg where T is temperature in C. (2) R = 0.287 kJ/kg K. Solution: Applying first law, ignoring potential and kinetic energy terms, to the vessel as control volume.
43

S K Mondals
Q + m i h i = m e h e + m2 u2 m1 u1 + W m1 = 0 ( evacuated ) m2 = mi hi = ui + pv = u0 + 0.718Ti + 0.287 (Ti + 273 ) = u0 + 0.718 25 + 0.287 298 = u0 + 103.48kJ / kg = u2 or u2 u0 = 103.48kJ / kg u2 = u0 + 0.718T2 T2 = u2 u0 103.48 = = 144.2C 0.718 0.718 hi = u2 Here Q = 0, W = 0, m e = 0 ( no mass leaving from control vol.)
Chapter 2
Example 4 A system whose mass is 4.5 kg undergoes a process and the temperature changes from 50 C to 100C. Assume that the specific heat of the system is a function of temperature only. Calculate the heat transfer during the process for the following relation ship. 80 cn = 1.25 + kJ / kg C [t is in oC] t + 160 Solution: 100 100 80 = = Q mc dt 4.5 n 1 2 1.25 + t + 160 dt 50 50
100 100 dt = 4.5 1.25dt + + t 0.0125 2.0 50 50 100 100 1 = 4.5 [1.25t ]50 + ln ( 0.0125t + 2.0 ) 0.0125 50
1 = 4.5 [1.25 50] + (ln (1.25 + 2.0 ) ln (0.625 + 2 )) 0.0125 1 3.25 = 4.5 62.5 + ln = 358 kJ 0.0125 2.625
44

ASKED D OBJEC CTIVE QUESTIONS (G GATE, IES, IAS)

P Previou us 20-Y Years GATE E Ques stions
A Applicati ion of First F Law w to Ste eady Flo ow Proc cess S.F F.E.E
Co ommon Data for Qu uestions Q1 Q and Q2 2:
Th he inlet and d the outle et conditions of ste eam for an n adiabatic c steam tur rbine are as indic cated in the t figure. The otations are as usually followed. no
[GA ATE-2009]
ATE-1. GA
If mass m flow rate r of steam through the turbine is 20 kg/s s the power r output of the e turbine (in n MW) is: (a) 12.157
[GA ATE-2009]
(b) 12.941 (c c) 168.001 (d) 168.785
GA ATE-2.
Ass sume the ab bove turbin ne to be par rt of a simp ple Rankine e cycle. The density of water at the inlet to the e pump is 1000 kg/m3. Ignoring kinetic k and d potential ene ergy effects s, the specifi fic work (in kJ/kg) supp plied to the pump is: [G GATE-2009] (a) 0.293 (b) 0.35 1 (c) ) 2.930 (d) 3.510 3
GA ATE-3. The e following g four figures have been dra awn to re epresent a fictitious the ermodynam mic cycle, on n the p-v and d T-s planes s. [G GATE-2005]
Acc cording to the t first law w of thermodynamics, equal e areas are enclose ed by (a) Figures 1and d 2 (b) Fig gures 1and 3 (c) Figures s 1and 4 (d) Figures 2 and 3
45

Internal Energy A Property of System

GATE-4. A gas contained in a cylinder is compressed, the work required for compression being 5000 kJ. During the process, heat interaction of 2000 kJ causes the surroundings to the heated. The change in internal energy of the gas during the process is: [GATE-2004] (a) 7000 kJ (b) 3000 kJ (c) + 3000 kJ (d) + 7000 kJ
GATE-4a. The contents of a well-insulated tank are heated by a resistor of 23 in
which 10 A current is flowing. Consider the tank along with its contents as a thermodynamic system. The work done by the system and the heat transfer to the system are positive. The rates of heat (Q), work (W) and change in internal energy ( U) during the process in kW are [GATE-2011] (a) Q = 0, W = 2.3, U = +2.3 (b) Q = +2.3, W = 0, U = +2.3 (c) Q = 2.3, W = 0, U = 2.3 (d) Q = 0, W = +2.3, U = 2.3
Discharging and Charging a Tank

GATE-5. A rigid, insulated tank is initially evacuated. The tank is connected with a supply line through which air (assumed to be ideal gas with constant specific heats) passes at I MPa, 350C. A valve connected with the supply line is opened and the tank is charged with air until the final pressure inside the tank reaches I MPa. The final temperature inside the tank (A) Is greater than 350C (B) Is less than 350C (C) Is equal to 350C (D) May be greater than, less than, or equal to 350C, depending on the volume of the tank
Previous 20-Years IES Questions First Law of Thermodynamics

IES-1. Which one of the following sets of thermodynamic laws/relations is directly involved in determining the final properties during an adiabatic mixing process? [IES-2000] (a) The first and second laws of thermodynamics (b) The second law of thermodynamics and steady flow relations (c) Perfect gas relationship and steady flow relations (d) The first law of thermodynamics and perfect gas relationship
46

S K Mondals
IES-2.
Chapter 2
Two blocks which are at different states are brought into contact with each other and allowed to reach a final state of thermal equilibrium. The final temperature attained is specified by the [IES-1998] (a) Zeroth law of thermodynamics (b) First law of thermodynamics (c) Second law of thermodynamics (d) Third law of thermodynamics For a closed system, the difference between the heat added to the system and the work done by the system is equal to the change in [IES-1992] (a) Enthalpy (b) Entropy (c) Temperature (d) Internal energy An ideal cycle is shown in the figure. Its thermal efficiency is given by
IES-3.
IES-4.
v3 1 v (a)1 1 p2 1 p1
(c)1
( v3 v1 ) p1 ( p2 p1 ) v1
v3 1 1 v1 (b) 1 p2 1 p1
(b) 1
1 ( v3 v1 ) p1 ( p2 p1 ) v1
[IES-1998] [IES-2007]
IES-5.
Which one of the following is correct? The cyclic integral of (Q W ) for a process is:
(a) Positive
IES-6.
(b) Negative
(c) Zero
(d) Unpredictable
A closed system undergoes a process 1-2 for which the values of Q1-2 and W1-2 are +20 kJ and +50 kJ, respectively. If the system is returned to state, 1, and Q2-1 is [IES-2005] 10 kJ, what is the value of the work W2-1? (a) + 20 kJ (b) 40 kJ (c) 80 kJ (d) +40 kJ A gas is compressed in a cylinder by a movable piston to a volume one-half of its original volume. During the process, 300 kJ heat left the gas and the internal energy remained same. What is the work done on the gas? [IES-2005] (a) 100kNm (b) 150 kNm (c) 200 kNm (d) 300 kNm In a steady-flow adiabatic turbine, the changes in the internal energy, enthalpy, kinetic energy and potential energy of the working fluid, from inlet to exit, are -100 kJ/kg, -140 kJ/kg, -10 kJ/kg and 0 kJ/kg respectively. Which one of the following gives the amount of work developed by the turbine? [IES-2004] (a) 100 kJ/kg (b) 110 kJ/kg (c) 140 kJ/kg (d) 150 kJ/kg
IES-7.
IES-8.
47

S K Mondals
IES-9.
Chapter 2
Gas contained in a closed system consisting of piston cylinder arrangement is expanded. Work done by the gas during expansion is 50 kJ. Decrease in internal energy of the gas during expansion is 30 kJ. Heat transfer during the process is equal to: [IES-2003] (a) 20 kJ (b) +20 kJ (c) 80 kJ (d) +80 kJ A system while undergoing a cycle [IES-2001] A B C D A has the values of heat and work transfers as given in the Table: Process AB BC CD DA Q kJ/min +687 -269 -199 +75 W kJ/min +474 0 -180 0
IES-10.
The power developed in kW is, nearly, (a) 4.9 (b) 24.5 (c) 49 IES-11.
(d) 98
The values of heat transfer and work transfer for four processes of a thermodynamic cycle are given below: [IES-1994] Process 1 2 3 4 Heat Transfer (kJ) 300 Zero -100 Zero Work Transfer (kJ) 300 250 -100 -250
The thermal efficiency and work ratio for the cycle will be respectively. (a) 33% and 0.66 (b) 66% and 0.36. (c) 36% and 0.66 (d) 33% and 0.36. IES-12. A tank containing air is stirred by a paddle wheel. The work input to the paddle wheel is 9000 kJ and the heat transferred to the surroundings from the tank is 3000 kJ. The external work done by the system is: [IES-1999] (a) Zero (b) 3000 kJ (c) 6000 kJ (d) 9000 kJ

IES-13. For a simple closed system of constant composition, the difference between the net heat and work interactions is identifiable as the change in [IES-2003] (a) Enthalpy (b) Entropy (c) Flow energy (d) Internal energy Assertion (A): The internal energy depends on the internal state of a body, as determined by its temperature, pressure and composition. [IES-2006] Reason (R): Internal energy of a substance does not include any energy that it may possess as a result of its macroscopic position or movement. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
IES-14.
48

S K Mondals
IES-15.
Chapter 2
Change in internal energy in a reversible process occurring in a closed system is equal to the heat transferred if the process occurs at constant: [IES-2005] (a) Pressure (b) Volume (c) Temperature (d) Enthalpy 170 kJ of heat is supplied to a system at constant volume. Then the system rejects 180 kJ of heat at constant pressure and 40 kJ of work is done on it. The system is finally brought to its original state by adiabatic process. If the initial value of internal energy is 100 kJ, then which one of the following statements is correct? [IES-2004] (a) The highest value of internal energy occurs at the end of the constant volume process (b) The highest value of internal energy occurs at the end of constant pressure process. (c) The highest value of internal energy occurs after adiabatic expansion (d) Internal energy is equal at all points 85 kJ of heat is supplied to a closed system at constant volume. During the next process, the system rejects 90 kJ of heat at constant pressure while 20 kJ of work is done on it. The system is brought to the original state by an adiabatic process. The initial internal energy is 100 kJ. Then what is the quantity of work transfer during the process? [IES-2009] (a) 30 kJ (b) 25 kJ (c) 20 kJ (d) 15 kJ
IES-16.
IES-17.
IES-17a
A closed system receives 60 kJ heat but its internal energy decreases by 30 kJ. Then the [IES-2010] work done by the system is (a) 90 kJ (b) 30 kJ (c) 30 kJ (d) 90 kJ
A system undergoes a process during which the heat transfer to the system per degree increase in temperature is given by the equation: [IES-2004] dQ/dT = 2 kJ/C The work done by the system per degree increase in temperature is given by the equation dW/dT = 2 0.1 T, where T is in C. If during the process, the temperature of water varies from 100C to 150C, what will be the change in internal energy? (a) 125 kJ (b) 250 kJ (c) 625 kJ (d) 1250 kJ When a system is taken from state A to state B along the path A-C-B, 180 kJ of heat flows into the system and it does 130 kJ of work (see figure given): How much heat will flow into the system along the path A-D-B if the work done by it along the path is 40 kJ? (a) 40 kJ (b) 60 kJ (c) 90 kJ (d) 135 kJ
IES-18.
IES-19.
[IES-1997]
IES-20.
The internal energy of a certain system is a function of temperature alone and is given by the formula E = 25 + 0.25t kJ. If this system executes a process for which the work done by it per degree temperature increase is 0.75 kJ/K, then the heat interaction per degree temperature increase, in kJ, is: [IES-1995] (a) 1.00 (b) 0.50 (c) 0.50 (d ) 1.00
49

S K Mondals
IES-21.
Chapter 2
When a gas is heated at constant pressure, the percentage of the energy supplied, which goes as the internal energy of the gas is: [IES-1992] (a) More for a diatomic gas than for triatomic gas (b) Same for monatomic, diatomic and triatomic gases but less than 100% (c) 100% for all gases (d) Less for triatomic gas than for a diatomic gas
Perpetual Motion Machine of the First Kind-PMM1

IES-22. Consider the following statements: [IES-2000] 1. The first law of thermodynamics is a law of conservation of energy. 2. Perpetual motion machine of the first kind converts energy into equivalent work. 3. A closed system does not exchange work or energy with its surroundings. 4. The second law of thermodynamics stipulates the law of conservation of energy and entropy. Which of the statements are correct? (a) 1 and 2 (b) 2 and 4 (c) 2, 3 and 4 (d) 1, 2 and 3
Enthalpy
IES-23. Assertion (A): If the enthalpy of a closed system decreases by 25 kJ while the system receives 30 kJ of energy by heat transfer, the work done by the system is 55 kJ. [IES-2001] Reason (R): The first law energy balance for a closed system is (notations have their usual meaning) E = Q W
(a) (b) (c) (d)
Both A and R are individually true and R is the correct explanation of A Both A and R are individually true but R is NOT the correct explanation of A A is true but R is false A is false but R is true

IES-24. Which one of the following is the steady flow energy equation for a boiler?
(a) h1 + (c) h1 +
IES-25.
v12 v2 = h2 + 2 2 gJ 2 gJ v12 v2 + Q = h2 + 2 2 gJ 2 gJ
(b) Q = ( h2 h1 ) (d) Ws = ( h2 h1 ) + Q
[IES-2005]
A 4 kW, 20 litre water heater is switched on for 10 minutes. The heat capacity Cp for water is 4 kJ/kg K. Assuming all the electrical energy has gone into heating the water, what is the increase of the water temperature? [IES-2008] (a) 15C (b) 20C (c) 26C (d) 30C
Discharging and Charging a Tank

50

S K Mondals
IES-26.
Chapter 2
An insulated tank initially contains 0.25 kg of a gas with an internal energy of 200 kJ/kg .Additional gas with an internal energy of 300 kJ/kg and an enthalpy of 400 kJ/kg enters the tank until the total mass of gas contained is 1 kg. What is the final internal energy(in kJ/kg) of the gas in the tank? [IES-2007] (a) 250 (b) 275 (c) 350 (d) None of the above
Previous 20-Years IAS Questions

IAS-1. A system executes a cycle during which there are four heat transfers: Q12 = 220 kJ, Q23 = -25kJ, Q34 = -180 kJ, Q41 = 50 kJ. The work during three of the processes is W12 = 15kJ, W23 = -10 kJ, W34 = 60kJ. The work during the process 4 1 is: [IAS-2003] (a) - 230 kJ (b) 0 kJ (c) 230 kJ (d) 130 kJ Two ideal heat engine cycles are represented in the given figure. Assume VQ = QR, PQ = QS and UP =PR =RT. If the work interaction for the rectangular cycle (WVUR) is 48 Nm, then the work interaction for the other cycle PST is: (a) 12Nm (b) 18 Nm (c) 24 Nm (d) 36 Nm
IAS-2.
IAS-2001]
IAS-3.
A reversible heat engine operating between hot and cold reservoirs delivers a work output of 54 kJ while it rejects a heat of 66 kJ. The efficiency of this engine is: [IAS-1998] (a) 0.45 (b) 0.66 (c) 0.75 (d) 0.82 If a heat engine gives an output of 3 kW when the input is 10,000 J/s, then the thermal efficiency of the engine will be: [IAS-1995] (a) 20% (b) 30% (c) 70% (d) 76.7% In an adiabatic process, 5000J of work is performed on a system. The system returns to its original state while 1000J of heat is added. The work done during the non-adiabatic process is: [IAS-1997] (a) + 4000J (b) - 4000J (c) + 6000J (d) - 6000J In a thermodynamic cycle consisting of four processes, the heat and work are as follows: [IAS-1996] Q: + 30, - 10, -20, + 5 W: + 3, 10, - 8, 0 The thermal efficiency of the cycle will be: (a) Zero (b) 7.15% (c) 14.33% (d) 28.6%
IAS-4.
IAS-5.
IAS-6.
51

S K Mondals
IAS-7.
Chapter 2
Match List-I (Devices) with List-II (Thermodynamic equations) and select the correct answer using the codes below the lists: [IAS-1996] List-I List-II A. Turbine 1. W = h2 h1 B. Nozzle 2. h1 = h2 C. Valve 3. h1 = h2 + V2/2 D. Compressor 4. W = h1 h2 Codes: A B C D A B C D (a) 4 3 2 1 (b) 2 3 1 4 (c) 4 3 1 2 (d) 3 2 4 1 Given that the path 1-2-3, a system absorbs 100kJ as heat and does 60kJ work while along the path 14-3 it does 20kJ work (see figure given). The heat absorbed during the cycle 1-4-3 is: (a) - 140 Kj (b) - 80 kJ (c) - 40kJ (d) + 60 kJ The given figure shows the variation of force in an elementary system which undergoes a process during which the plunger position changes from 0 to 3 m. lf the internal energy of the system at the end of the process is 2.5 J higher, then the heat absorbed during the process is: (a) 15 J (b) 20 J The efficiency of a reversible cyclic process undergone by a substance as shown in the given diagram is: (a) 0.40 (b) 0.55 (c) 0.60 (d) 0.80 [IAS 1994]
IAS-8.
IAS-9.
(c) 25 J
[IAS-1994] (d) 30 J
IAS-10.
[IAS 1994]

IAS-11. Which one of the following is the correct expression for change in the internal energy for a small temperature change T for an ideal gas? [IAS-2007] (a) U = Cv T (b) U = C p T
52

S K Mondals
(c)
IAS-12.
Chapter 2
T
(d) U = C p Cv T
U =
Cp Cv
The heat transferred in a thermodynamic cycle of a system consisting of four processes is successively 0, 8, 6 and -4 units. The net change in the internal energy of the system will be: [IAS-1999] (a) 8 (b) Zero (c) 10 (d) 10 During a process with heat and work interactions, the internal energy of a system increases by 30 kJ. The amounts of heat and work interactions are respectively [IAS-1999] (a) - 50 kJ and - 80 kJ (b) -50 kJ and 80 kJ (c) 50 kJ and 80 kJ (d) 50 kJ and - 80 kJ A mixture of gases expands from 0.03 m3 to 0.06 m3 at a constant pressure of 1 MPa and absorbs 84 kJ of heat during the process. The change in internal energy of the mixture is: [IAS 1994] (a) 30 kJ (b) 54 kJ (c) 84 kJ (d) 114 kJ In an adiabatic process 6000 J of work is performed on a system. In the nonadiabatic process by which the system returns to its original state 1000J of heat is added to the system. What is the work done during non-adiabatic process? [IAS-2004] (a) + 7000 J (b) - 7000 J (c) + 5000 J (d) - 5000 J
IAS-13.
IAS-14.
IAS-15.
Enthalpy
IAS-16. The fundamental unit of enthalpy is: (a) MLT-2 (b) ML-2T-1 (c) ML2T-2 [IAS 1994]
(d) ML3T-2

IAS-17. In a test of a water-jacketed compressor, the shaft work required is 90 kN-m/kg of air compressed. During compression, increase in enthalpy of air is 30 kJ/kg of air and increase in enthalpy of circulating cooling water is 40 kJ/ kg of air. The change is velocity is negligible. The amount of heat lost to the atmosphere from the compressor per kg of air is: [IAS-2000] (a) 20kJ (b) 60kJ (c) 80 kJ (d) 120kJ When air is compressed, the enthalpy is increased from 100 to 200 kJ/kg. Heat lost during this compression is 50 kJ/kg. Neglecting kinetic and potential energies, the power required for a mass flow of 2 kg/s of air through the compressor will be: [IAS-1997] (a) 300 kW (b) 200 kW (c) 100 kW (d) 50 kW
IAS-18.
53

Variable Flow Processes

IAS-19. Match List-I with List-II and select the correct answer using the codes given below Lists: [IAS-2004] List-I List-II A. Bottle filling of gas 1. Absolute zero temperature B. Nernst Simon statement 2. Variable flow C. Joule Thomson effect 3. Quasistatic path D.
pdv
4. Isenthalpic process 5. Dissipative effect 6. Low grade energy 7. Process and temperature change A B C (b) 2 1 4 (d) 6 1 7
during phase
D 3 4
Codes: (a) (c) IAS-20.
A 6 2
B 5 5
C 4 7
D 3 4
A gas chamber is divided into two parts by means of a partition wall. On one side, nitrogen gas at 2 bar pressure and 20C is present. On the other side, nitrogen gas at 3.5 bar pressure and 35C is present. The chamber is rigid and thermally insulated from the surroundings. Now, if the partition is removed, (a) High pressure nitrogen will get throttled [IAS-1997] (b) Mechanical work, will be done at the expense of internal energy (c) Work will be done on low pressure nitrogen (d) Internal energy of nitrogen will be conserved
54


GATE-1. Ans. (a)
C12 C2 gZ1 gZ2 dQ dW + + = h2 + 1 + + 2000 1000 dm 2000 1000 dm 2 160 9.81 10 100 2 9.81 6 dW 3200 + + = 2600 + + + 2000 1000 2000 1000 dm dW 600 + 7.8 + 0.04 = + dm h1 +
W = (P2 P1 ) = 1 ( 3000 70 ) kJ/kg = 2.93 1000
GATE-2. Ans. (c)
GATE-3. Ans. (a) Fig-1 & 2 both are power cycle, so equal areas but fig-3 & 4 are reverse power cycle, so area is not meant something. GATE-4. Ans. (c) dQ = du + dw Q = u2 u1 + W or 2000 = u2 u1 5000 or u2 u1 = 3000kJ GATE-4a. Ans. (a) Q = 0, W = 2.3, U =
+2.3 Tank is well insulated so Q = 0 Work is given to the system in the form of electric current.
So, W = I2 R = 102 23 = 2300 W = 2.3 kW By 1st Law of Thermodynamics Q1 2 = U2 U1 + W1 2 0 = U 2 U1 2.3 U = 2.3 kW

GATE-5. Ans (a) The final Temp. (T2)=
T1

IES-1. Ans. (a) If we adiabatically mix two liquid then perfect gas law is not necessary. But entropy change in the universe must be calculated by Second law of thermodynamics. Final entropy of then system is also a property. That so why we need second law. IES-2. Ans. (b) Using conservation of energy law we may find final temperature. IES-3. Ans. (d) From First law of thermodynamics, for a closed system the net energy transferred as heat Q and as work W is equal to the change in internal energy, U, i.e. Q W = U
55

S K Mondals
Now w from equat tion of state
Cha apter 2
IES-4. Ans. (c) ) Total heat addition a is co onstant volum me heat addi ition, Q12 = cv (T2 T1 )
Tot tal heat rejection is consta ant pressure heat rejectio on, Q31 = c p (T3 T1)
P P1 P2 = ( v = const.) or T2 = 2 T1 P1 T1 T2 and d v v1 v 3 = ) or T3 = 3 T1 ( p = const.) v1 T1 T3
Effi iciency, = 1
c (T T ) Q31 (T T ) = 1 p 3 1 = 1 3 1 cv (T2 T1) Q12 (T2 T1)
v3 T1 T1 v = 1 (v 3 v1) p1 or = 1 1 ( p2 p1) v1 P2 T1 T1 P1
IES-5. Ans. (c c) It is du = Q W, as u is a thermo odynamic pro operty and it ts cyclic integ gral must be zero o. W or Q1 2 + Q2 1 = W1 2 + W2 1 IES-6. Ans. (b) dQ = dW
or 20 + ( 10 ) = 50 + W21
or W21 = 40kJ
IES-7. Ans. (d) dQ = du + dw as u = const. The erefore du = 0 or dQ = dw d = 300kNm IES-8. Ans. (d) V2 Q Wx = h + + gz 2
O Wx = 140 10 + 0 or Wx = 150 kJ / kg
Cha ange of internal energy = -100 kJ/kg is superfluous data. IES-9. Ans. (b) Q = E+ W E = 30 kJ (d decrease in in nternal energ gy) ( done by the system m) W = + 50 kJ (work Q = 30 + 50 = + 20 kJ IES-10. Ans. (a a) Net work = 74 180 kJ/m min = 294 kJ J/min = 294/6 60 kJ/s = 4.9 kW dW =47
IES-11. Ans. (b b)
th =
Work done 30 00 100 = 0. .66 = at added 300 hea
Wo ork ratio =
IES-12. Ans. (a) This is s a case of constant vo olume process or an n is isocho oric process. . By per rforming wor rk on the sys stem tempera ature can n be raised. In an irrev versible constant volu ume process, the system m doesn't per rform wor rk on the sur rrounding at the expense of its inte ernal energy. 56
( + w) ( w) = 550 350 = 0.36 6 5 550 ( + w)

IES-13. Ans. (d d) IES-14. Ans. (a) ( The inter rnal energy depends d only y upon the in nitial and fin nal states of the system. Inte ernal energy y of a substa ance does no ot include an ny energy th hat it may possess p as a resu ult of its ma acroscopic position or movement. m T That so why in SFEE v2/2 / and gz is there.
If in nternal energ gy include po osition or movement then n why this v2/2 / and gz term ms is there. Bur Remembe er: Mic croscopic view of a gas is a collectio on of particl les in rando om motion. Energy E of a par rticle consists of transla ational energy, rotatio onal energy y, vibration nal energy and d specific el lectronic en nergy. All th hese energies summed ove er all the par rticles of the gas s, form the sp pecific interna al energy, e , of the gas. IES-15. Ans. (b b) dQ = dU + pdV if V is con s tan t ( dQ )v = ( dU)v
IES-16. Ans. (a a)
Q2 = 180 0kJ = u + W = u + ( 40) )
U1 = 100kJ, U2 = 100 0 + 170 = 270 0 kJ, U3 = 270 180 + 40 = 130 kJ
IES-17. Ans. (d d)
For the process p 1-2 dQ = +85 , dW = 0 For the process p 2-3 dQ = -90 kJ, dW = -20kJ For the process p 3-1 dQ = 0, dW = ? For a cyc clic process dQ = dW 85-90+ +0 = 0-20+ dW W -5 = -20+ dW 5 = +15kJ dW = -20+5
IES-17a.
An ns. (a) dQ = dU + dW d or 60 = 30 + dW or dW = 90 KJ
57

S K Mondals
IES-18. Ans. (c) dQ = du + dw
Chapter 2
2.dt = du + ( 2 0.1T ) dT
150 0.1 0.1 1502 1002 T2 = = 625kJ 100 2 2 IES-19. Ans. (c) Change of internal energy from A to B along path ACB = 180 - 130 = 50 kJ. It will be same even along path ADB. Heat flow along ADB = 40 + 50 = 90 kJ.
or
du = 0.1TdT =
IES-20. Ans. (d) dQ = dE + dW
or
dQ dE dW = + dt dt dt
Given: E = 25 + 0.25t kJ and then
dW = 0.75 kJ / k dt
dE = 0.25 kJ / K dt dQ dE dW Therefore = + = 0.25 + 0.75 kJ / K = 1.00 kJ / K dt dt dt

IES-21. Ans. (a) IES-22. Ans. (a) A closed system does exchange work or energy with its surroundings. option 3 is wrong. 4. The law of conservation of entropy is imaginary so option 4 is also wrong. IES-23. Ans. (a) v2 v2 dQ dw IES-24. Ans. (b) h1 + 1 + gz1 + = h2 + 2 + gz 2 + =0 2 dm 2 dm dw =0 For boiler v1, v2 is negligible and z1 = z2 and dm dQ or = ( h2 h1 ) dm IES-25. Ans. (d) mCP T = ( 4 10 60 )
20 4 T = 2400 T = 30C IES-26. Ans. (c) Enthalpy of additional gas will be converted to internal energy. Uf= miui+(mf-mi)hp = 0.25x200+(1-0.25)x400 = 350 kJ As total mass = 1kg, uf=350 kJ/kg Note: You cannot simply use adiabatic mixing law here because it is not closed system. This is a problem of variable flow process. If you calculate in following way it will be wrong.
Final internal energy of gas(mixture) is m u + m2 u2 u= 1 1 m1 + m2
kJ kJ (0.25kg) 200 + (0.75kg) 300 kg kg u= (0.25 + 0.75)kG
u = 275
kJ kg
58

S K Mondals
It is valid for closed system only.
Chapter 2

IAS-1. Ans. (b)
dQ = dW
or 220 -25 -180 +50 = 15 -10 +60 +W4-1
IAS-2. Ans. (c) Area under p-v diagram is represent work.
Areas PTS=
IAS-3. Ans. (a) =
1 1 Area (WVUR) Work PTS= 48 =24 Nm 2 2
work output work out put 54 = = = 0.45 Heat input work output + heat rejection 54 + 66
IAS-4. Ans. (b) Thermal efficiency = IAS-5. Ans. (c)

Q1 2 = (U2 U1 ) + W12
W 3 103 watts = = 0.3 = 30% Q 10.000 J/s
or 0 = (U2 U1 ) + ( 5000 ) or (U2 U1 ) = 5000 J Q21 = (U1 U2 ) + W21 or W21 = Q21 (U1 U2 ) = Q21 + (U2 U1 ) = 1000 + 5000 = 6000 J
IAS-6. Ans. (c) Net work output = 3 + 10 8 = 5 unit
and Heat added = 30 + 5 = 35 unit
Therefore efficiency, =
5 100% = 14.33% 35
IAS-7. Ans. (a) IAS-8. Ans. (d) Q123 = U13 + W123 or, 100 = U13 + 60 or, U13 = 40 kJ And Q143 = U13 + W143 = 40+20 = 60 kJ IAS-9.Ans. (b) Total work = 5 3 + IAS-10. Ans. (c) Efficiency =
1 5 1 = 17.5 J or W = du + W = 2.5 + 17.5 = 20 J 2
Area under 500 and 1500 Area under 0 and 1500
=
IAS-11. Ans. (a)
1 {(5 1) + (4 2)} (1500 500) + (5 1) 500 2
1 {(5 1) + (4 2)} (1500 500) 2
3000 = 0.6 5000
IAS-12. Ans. (b) Internal energy is a property of a system so IAS-14. Ans. (b) W = du + W = du + pdV
du = 0
IAS-13. Ans. (a) dQ = du + dW if du = +30kJ then dQ = 50kJ and dW = 80kJ
or 84 103J = du + 1 106 (0.06 0.03) = du +30 kJ or du = 83 30 = 54 kJ 59

S K Mondals
IAS-15. Ans. (a) Q1-2 = U2 U1 +W1-2 Or 0 = U2 U1 - 6000 or U2 U1 = +6000 Q2-1 = U1-U2+W2-1 or W2-1 = Q2-1 - (U1-U2) =1000+6000=7000J
Chapter 2
IAS-16. Ans. (c) IAS-17. Ans. (a) Energy balance gives as dW dQ = ( h )air + ( h ) water + dm dm dQ or = 90 30 40 dm = 20kJ / kg of air compressed. IAS-18. Ans. (a)
m ( h1 ) + dQ dw = m ( h2 ) + dt dt dw dQ or = m ( h1 h2 ) + = 2 (100 200 ) 50 2 = 300kW dt dt i.e. 300kW work have to given to the system.
IAS-19. Ans. (b) IAS-20. Ans. (a)
60
Second Law of Thermodynamics

3.
Theory at a Glance (For GATE, IES & PSUs)

The first law of thermodynamics states that a certain energy balance will hold when a system undergoes a change of state or a thermodynamic process. But it does not give any information on whether that change of state or the process is at all feasible or not. The first law cannot indicate whether a metallic bar of uniform temperature can spontaneously become warmer at one end and cooler at the other. All that the law can state is that if this process did occur, the energy gained by one end would be exactly equal to that lost by the other. It is the second law of thermodynamics which provides the criterion as to the probability of various processes.
Regarding Heat Transfer and Work Transfer

(a) Heat transfer and work transfer are the energy interactions. A closed system and its surroundings can interact in two ways: by heat transfer and by work transfer. Thermodynamics studies how these interactions bring about property changes in a system. (b) The same effect in a closed system can be brought about either by heat transfer or by work transfer. Whether heat transfer or work transfer has taken place depends on what constitutes the system. (c) (d)
Both heat transfer and work transfer are boundary phenomena. Both are observed at
the boundaries of the system, and both represent energy crossing the boundaries of the system. It is wrong to say 'total heat' or 'heat content' of a closed system, because heat or work is not
a property of the system. Heat, like work, cannot be stored by the system. Both heat and
work are the energy is transit. (e) (f) Heat transfer is the energy interaction due to temperature difference only. All other energy interactions may be termed as work transfer.
Both heat and work are path functions and inexact differentials. The magnitude of
heat transfer or work transfer depends upon the path the system follows during the change of state. (g) Heat transfer takes place according to second law of thermodynamics as it tells about the direction and amount of heat flow that is possible between two reservoirs.
62
Seco ond La aw of Therm modyn namics s

S K Mondals
Cha apter 3
Q Qualitati ive Diff ference e between Hea at and Work W

Thermo odynamic def finition of wo ork: Positive e work is done by a system when the e sole effec ct external to t the system m could be reduced d to the rise of o a weight. Thermo odynamic def finition of he eat: It is th he energy in n transition n between th he system an nd the surrou undings by virtue v of the differen nce in temper rature.
Si ign Conv ventions s

Work done d BY the system s is +ve e Obviously work don ne ON the sys stem is ve Heat gi iven TO the system s is +v ve Obviously Heat reje ected by the system s is v ve
He eat and work are not comp pletely interc changeable forms f of energy. When wo ork is convert ted into hea at, we alway ys have
W =Q
but when heat is converted into work in n a complete closed c cycle process p
Q >W
Th he arrow indicates the direction of energy transform mation.
Wo ork is said to o be a high grade g energ gy and heat is i low grade e energy. Th he complete conversion c of low grade en nergy into high grade ene ergy in a cycle is impossib ble.
HEAT T and WORK K are NOT pr roperties be ecause they depend d on the e 63

S K Mondals
path and end states. HEAT and WORK are not properties because their net change in a cycle is not zero.
Chapter 3
Heat and work are inexact differentials. Their change cannot be written as differences between their end states.
Thus Similarly
differentials.
1 2
Q Q2 Q1 and is shown as 1 Q2 or Q12 W W2 W1 and is shown as 1W2 or W12
Note. The operator is used to denote inexact differentials and operator d is used to denote exact
Kelvin-Planck Statement of Second Law

There are two statements of the second law of thermodynamics, the Kelvin-Planck statement, and the Clausius statement. The Kelvin-Planck statement pertains to heat engines. The Clausius statement pertains to refrigerators/heat pumps .
Kelvin-Planck statement of second law

It is impossible to construct a device (engine) operating in a cycle that will produce no effect other than extraction of heat from a single reservoir and convert all of it into work.
Mathematically, Kelvin-Planck statement can be written as:
Wcycle 0 (for a single reservoir)

Clausius statement of second law
It is impossible to transfer heat in a cyclic process from low temperature to high temperature without work from external source.
Reversible and Irreversible Processes

A process is reversible with respect to the system and surroundings if the system and the surroundings can be restored to their respective initial states by reversing the direction of the process, that is, by reversing the heat transfer and work transfer. The process is irreversible if it cannot fulfill this criterion.
64

C Clausius s' Theo orem

Let a system be b taken from m an equilib brium state i to another equilibrium state f by fo ollowing the rev versible path h i-f(Figure). Let a revers sible adiabati ic i-a be draw wn through i and anothe er reversible adi iabatic b-f be e drawn thro ough f. Then a reversible e isothermal a-b is drawn n in such a way w that the are ea under i-a-b-f is equal to t the area under u i-f. App plying the firs st law for
Process si f Qi f = U f U i + Wif Process s i a b f Qiabf = U f U i + Wiabf i Since Wif = Wiabf Since Qi f = Qiabf = Qia + Qab + Qbf Qia = 0 and d Qbf = 0 Qif = Qab
Fig. Rev versible Pat th Substitut ted by Two o Reversible e Adiabatics and a Reversible e Isothermal l
He eat transferre ed in the process i-f is equ ual to the hea at transferre ed in the isoth hermal proce ess a-b. Th hus any reve ersible path may m be subs stituted by a reversible zigzag path, between th he same end sta ates, consisti ing of a rev versible adia abatic follow wed by a rev versible isot thermal and then by a rev versible adia abatic, such that t the hea at transferred during the e isothermal process is the t same as tha at transferred during the original proc cess. Let a smooth closed c curve representing g a reversible e cycle (Fig below.) b be considered. Le et the closed cyc cle be divided d into a larg ge number of f strips by means m of reversible adiaba atics. Each strip may be clo osed at the to op and bottom m by reversib ble isotherma als. The origi inal closed cy ycle is thus re eplaced by a zig gzag closed path p consisti ing of altern nate adiabati ic and isothe ermal proces sses, such th hat the heat tra ansferred dur ring all the isothermal pr rocesses is eq qual to the heat h transferr red in the or riginal cycle. Th hus the origin nal cycle is replaced by a large number of Carnot cycles. If th he adiabatics are close to one e another an nd the numbe er of Carnot cycles c is larg ge, the saw-to oothed zig-za ag line will co oincide with the e original cyc cle.
65

F Fig. A Revers sible Cycle Split S into a Large Num mber of Carn not Cycles
ental cycle abcd a dQ1 heat is absorb bed reversibl ly at T1, an nd dQ2 heat is rejected For the eleme versibly at T2 rev
dQ1 dQ2 = T1 T2
If h heat supplied d is taken as positive and d heat rejecte ed as negative

dQ1 dQ2 + =0 T2 T1
Sim milarly, for th he elemental l cycle efgh

dQ3 dQ4 + =0 T3 T4
If s similar equat tions are wri itten for all th he elemental l Carnot cycles, then for the t whole original cycle
dQ3 dQ4 d Q1 dQ2 + + + + ... = 0 T1 T2 T3 T4
or
dQ d =0 T
Th he cyclic int tegral of d Q/T for a re eversible cy ycle is equal l to zero. Th his is known as a Clausius'
the eorem. The le etter R emph hasizes the fa act that the equation is va alid only for a reversible cycle. c
66

S K Mondals
the original cycle.
Chapter 3
Thus the original cycle is replaced by a large number of Carnot cycles. If the adiabatics are close to one another and the number of Carnot cycles is large, the saw-toothed zig-zag line will coincide with
Refrigerator and Heat Pump [with RAC]

Equivalence of Kelvin-Planck and Clausius Statements
II Law basically a negative statement (like most laws in society). The two statements look distinct. We shall prove that violation of one makes the other statement violation too.
Let us suspect the Clausius statement-it may be possible to transfer heat from a body at colder
to a body at hotter temperature without supply of work
Let us have a heat engine operating between T1 as source and T2 as a sink. Let this heat engine reject exactly the same Q2 (as the pseudo-Clausius device) to the reservoir at T2. To do this an amount of Q1 needs to be drawn from the reservoir at T1. There will also be a W = Q1 Q2. Combine the two. The reservoir at T2 has not undergone any change (Q2 was taken out and by pseudo-Clausius device and put back by the engine). Reservoir 1 has given out a net Q1-Q2. We got work output of W. Q1-Q2 is converted to W with no net heat rejection. This is violation of KelvinPlanck statement.
67

S K Mondals
Chapter 3
Let us assume that Clausius statement is true and suspect Kelvin-Planck statement
Pseudo Kelvin Planck engine requires only Q1Q2 as the heat interaction to give out W (because it does not reject any heat) which drives the Clausius heat pump Combining the two yields: The reservoir at T1 receives Q1 but gives out Q1Q2 implying a net delivery of Q2 to it. Q2 has been transferred from T2 to T1 without the supply of any work!! A violation of Clausius statement
Moral: If an engine/refrigerator violates one version of II Law, it violates the other one too.
All reversible engine operating between the same two fixed temperatures will have the same and COP. If there exists a reversible engine/ or a refrigerator which can do better than that, it will violate the Clausius statement. Let us presume that the HP is super efficient!! For the same work given out by the engine E, it can pick up an extra Q from the low temperature source and deliver over to reservoir at T1 . The net effect is this extra has Q been transferred from T2 to T1 with no external work expenditure. Clearly, a violation of Clausius statement!!
SUM UP Heat supplied = Q1; Source temperature = T1 ; Sink temperature = T2 Maximum possible efficiency = W/Q1= (T1 T2)/T1 Work done = W = Q1(T1 T2)/T1
68

S K Mondals
Sin nce,
T1 Q1 = T2 Q2
Cha apter 3
Carnot Engine E with w sam me effic ciency or o same e work output o

T1 T2 Q1 Q2 = T2 Q2 T1 T2 = (Q1 Q2 ) T2 T3 = (Q2 Q3 )
For sam me work ou utput W1 = W2 Q1 Q 2 = Q2 Q3
T2 Q2 T3 T = (Q2 Q3 ) 2 Q2 Q3
T1 T2 = T2 T3
For sam me efficiency
1 = 2
or r 1 T T2 = 1 3 T1 T2
o T2 = T1 T3 or
Whic ch is the t mo ore effe ective way w to increase the efficiency of f a Carn not engi ine: to increase e T1 keeping T2 stant; or r to decr rease T2 keeping g T1 con nstant? cons
Th he efficiency of o a Carnot engine is give en by
= 1
If T2 is constan nt
T2 T1
T2 = 2 T1 T2 T1
AS S T1 increases s, increases s, and the slo ope d (Fi igure). If T1 is i constant, decreases T1 T2
69

S K Mondals
1 = T1 T2 T1 As T2 decreases s, increases s, but the slo ope r const tant (Figure) ). remains T2 T1
Cha apter 3
Also Since
T2 T1 = 2 = 2 and T1 T1 T2 T1 T2 T1 T1 > T2 , > T2 T1 T1 T2
So, the more effective e way y to increas se the efficie ency is to de ecrease T2. Alternatively A y, let T2 be dec creased by T with T1 rem maining the same s
1 = 1
T2 T T1
If T1 is increase ed by the sam me T, T2 rem maining the same s
2 = 1 The en 1 2 =
T2 T1 + T
T2 T T 2 T1 + T T1
1
(T =
Sin nce
T2 ) T + ( T ) T1 (T1 + T )
T1 > T2 , ( 1 2 ) > 0
Th he more e effectiv ve way to incre ease the e cycle efficiency e y is
to
d decrea ase T2.

70

S K Mondals
Example 1. An inventor claims that his petrol engine operating between temperatures of 2000C and 600C will produce 1 kWhr consuming 150g of petrol having 45000 kJ/kg calorific value. Check the validity of the claim. Solution: By Carnot's theorem, the thermal efficiency of a reversible cycle engine which cannot be exceeded is given by T T2 2273 873 max = 1 = = 0.616 or 61.6% 2273 T1 Actual thermal efficiency is given by 1 103 3600 = 0.53 or 53% t = 0.15 45000 103 Since actual efficiency is less than the maximum obtainable, the inventor's claim is feasible. Example 2. Two reversible engines takes 2400 kJ per minute from a reservoir at 750 K and develops 400 kJ of work per minute when executing complete cycles.The engines reject heat two reservoirs at 650 K and 550 K. Find the heat rejected to each sink. Solution: QA + QB = 2400 QA2 + QB2 = 2000
QA QA2 QA 750 650 = 0.1333 750
Chapter 3
QA = 1.1539QA 2
71

S K Mondals
Similarly QB = 1.3636QB 2 i.e. 1.1539Q A 2 + 1.3636QB 2 = 2400kJ Q A 2 = 2000 QB 2 i.e. 1.1539 2000 QB 2 + 1.3636QB 2 = 2400kJ . 0.2091QB 2 = 92 QB 2 = 440kJ and QA 2 = 1560kJ
Chapter 3
Example 3. A solar powerd heat pump receives heat from a solar collector at temperature Th, uses the entire energy for pumping heat from cold atmosphere at temperature Tc to a room at temperature Ta. The three heat transfer rates are Qh, Qa and Qc respectively. Derive an expression for the minimum ratio Qh/Qc, in terms of the three temperatures. If Th = 400 K, Ta = 300 K, Tc = 200 K, Qc = 12 kW, what is the minimum Qh? If the collector captures 0.2 kW/m2, what is the minimum collector area required? Solution: Let Qh, Qa and Qc be the quantity of heat transferred from solar collector, room and atmosphere respectively.
Qa = Qh + Qc or, Qa Qc = Qh Ta Qa Q + Qc = h and also Ta Tc Qa Qc Qh COPHP =
Qh + Qc Ta = Qh Ta Tc
Qc Ta T Ta + Tc Tc = 1 = a = Qh Ta Tc Ta Tc Ta Tc Qh = Qh (Ta Tc ) = Qc Tc Tc 6 = 30m2 0.2 =
Qc (Ta Tc )
12 ( 300 200 ) 200
= 6kW
Area =
72

Example 4. A reversible engine works between 3 thermal reservoirs A, B and C. The engine absorbs an equal amount of heat from the reservoirs A and B, maintained at temperatures of T1 and T2 respectively and rejects heat to the thermal reservoir C maintained at T3. The efficiency of this engine is times the efficiency of reversible engine operating between reservoirs A and C only. Show that T1 2T = ( 2 1) + 1 (1 ) T2 T3
Solution:
1 = 2 =
W1 2Q1 T1 T3 T1 T1 T3 T1
1 = 2 =
The cycle is reversible so S = 0 Q Q Q 1+ 1 = 2 T1 T2 T3 Also, 2Q1 = W1 + Q2 Combining above equations we have Q1 Q1 2Q1 W1 + = T1 T2 T3 T T3 W1 = 1 2Q1 T1
73

S K Mondals
T T3 W1 = 2Q1 1 T1 ( T1 T3 ) Q1 Q1 2Q1 1 + = T1 T2 T3 T1 1 1 2 2 2 + = + T1 T2 T3 T3 T1 T1 2T1 = (1 ) + ( 2 1) T2 T3
Chapter 3
Example 5. Ice is to be made from water supplied at 15C by the process shown in figure. The final temperature of the ice is -10C, and the final temperature of the water that is used as cooling water in the condenser is 30C.
Determine the minimum work required to produce 1000 kg of ice. Solution: Quantity of ice produced = 1000 kg. Specific heat of ice = 2070 J/kg K Specific heat of water = 4198 J/kgK Latent heat of ice = 335 kJ/kg 15 + ( 10 ) Mean temperature of ice bath = = 2.5 C 2 15 + 30 = 22.5 C Mean temperature of condenser bath = 2 Q2 = 1000 4198(15 - 2.5) + 1000 335 103 +1000 2070(2.5 + 10) = 413.35MJ For a reversible refrigerator system T Q T Q 1 L = 1 2 ; L = 2 ; TH Q1 TH Q1
Q1 = Q2 TH 22.5 + 273 = 413.35 106 = 443.36 MJ TL 2.5 + 273
Minimum work required = Q1 Q2 = 443.36 - 413.35 = 30.01 MJ.
74

75


IES-1. Which one of the following is correct on basis of the second law of thermodynamics? [IES 2007] (a) For any spontaneous process, the entropy of the universe increases (b) S =qrev/T at constant temperature (c) Efficiency of the Stirling cycle is more than that of a Carnot cycle (d) E=q+w (The symbols have their usual meaning) Assertion (A): Second law of thermodynamics is called the law of degradation of energy. [IES-1999] Reason (R): Energy does not degrade each time it flows through a finite temperature difference. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true Heat transfer takes place according to (a) Zeroth Law of Thermodynamics (c) Second Law of Thermodynamics [IES-1996] (b) First Law of Thermodynamics (d) Third Law of Thermodynamics.
IES-2.
IES-3.
IES-3a.
Consider the following statements: [IES-2010] 1. Slow heating of water from an electric heater. 2. Isentropic expansion of air. 3. Evaporation of a liquid from a heat source at the evaporation temperature. 4. Constant pressure heating of a gas by a constant temperature source. Which of these processes is/are reversible? (a) 3 only (b) 2 and 3 only (c) 2 and 4 only (d) 1, 2, 3 and 4 Consider the following statements: [IES-2010] 1. Boiling of water from a heat source at the same boiling temperature. 2. Theoretical isothermal compression of a gas. 3. Theoretical polytropic compression process with heat rejection to atmosphere. 4. Diffusion of two ideal gases into each other at constant pressure and temperature. Which of these processes are irreversible? (a) 1, 2, 3 and 4 (b) 1 and 4 only (c) 2, 3 and 4 only (d) 3 and 4 only
IES-3b.
76

[IES-1993]
Kelvin-Planck Statement of Second Law

IES-4. Consider the following statements: The definition of 1. Temperature is due to Zeroth Law of Thermodynamics. 2. Entropy is due to First Law of Thermodynamics. 3. Internal energy is due to Second Law of Thermodynamics. 4. Reversibility is due to Kelvin-Planck's statement. Of these statements (a) 1, 2 and 3 are correct (b) 1, 3 and 4 are correct (c) 1 alone is correct (d) 2 alone is correct
Clausius' Statement of the Second Law

IES-5. Assertion (A): Heat cannot spontaneously pass from a colder system to a hotter system without simultaneously producing other effects in the surroundings. Reason (R): External work must be put into heat pump so that heat can be transferred from a cold to a hot body. [IES-1999] (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
Clausius' Theorem
IES-6. A steam power plant is shown in figure,
(a) The
cycle
violates
first
and
second laws of thermodynamics. (b) The cycle does not satisfy the condition of Clausius inequality. (c) The cycle only violates the second laws of thermodynamics (d) The cycle satisfies the Clausius inequality
[IES-1992] IES-7. An inventor says that his new concept of an engine, while working between temperature limits of 27C and 327C rejects 45% of heat absorbed from the source. His engine is then equivalent to which one of the following engines? (a) Carnot engine (b) Diesel engine [IES-2009] (c) An impossible engine (d) Ericsson engine
77

S K Mondals
IES-7a
Chapter 3
An inventor states that his new engine rejects to the sink 40% of heat absorbed from the source while the source and sink temperatures are 327 C and 27 C respectively. His engine is therefore equivalent to [IES-2010] (a) Joule engine (b) Stirling engine (c) Impossible engine (d) Carnot engine

IES-8. Assertion (A): Efficiency of a reversible engine operating between temperature [IES-2002] limits T1 and T2 is maximum. Reason (R): Efficiency of a reversible engine is greater than that of an irreversible engine. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
Carnot Engine with same efficiency or same work output

IES-9. A reversible engine operates between temperatures T1, and T2, The energy rejected by this engine is received by a second reversible engine at temperature T2 and rejected to a reservoir at temperature T3. If the efficiencies of the engines are same then the relationship between T1, T2 and T3 is given by: [IES-2002]
(a) T2
IES-10.
(T1 + T3 )
2
(b) T2
(T
2 1
+ T32
(c) T2
= T1T3
(d)
T2 =
(T1 + 2T3 )
2
A reversible engine operates between temperatures 900 K & T2 (T2 < 900 K), & another reversible engine between T2 & 400 K (T2 > 400 K) in series. What is the value of T2 if work outputs of both the engines are equal? [IES-2005] (a) 600 K (b) 625 K (c) 650 K (d) 675 K An engine operates between temperature limits of 900 K and T2 and another between T2 and 400 K. For both to be equally efficient, the value of T2 will be (a) 700 K (b) 600 K (c) 750 K (d) 650 [IES-2010] Two reversible engine operate between thermal reservoirs at 1200 K, T2K and 300 K such that 1st engine receives heat from 1200 K reservoir and rejects heat to thermal reservoir at T2K, while the 2nd engine receives heat from thermal reservoir at T2K and rejects heat to the thermal reservoir at 300 K. The efficiency of both the engines is equal. [IES-2004] What is the value of temperature T2? (a) 400 K (b) 500 K
IES-10a.
IES-11.
(c) 600 K
(d) 700 K
IES-12.
A series combination of two Carnots engines operate between the temperatures of 180C and 20C. If the engines produce equal amount of work, then what is the intermediate temperature? [IES-2009]
78

S K Mondals
(a) 80C
IES-13.
Chapter 3
(b) 90C (c) 100C (d) 110C
An engine working on Carnot cycle rejects 40% of absorbed heat from the source, while the sink temperature is maintained at 27C, then what is the source temperature? [IES-2009] (a) 750C (b) 477C (c) 203C (d) 67.5C A Carnot engine rejects 30% of absorbed that to a sink at 30 C. The temperature of the heat source is [IES-2010] (a) 100 C (b) 433 C (c) 737 C (d) 1010 C A reversible heat engine rejects 50 percent of the heat supplied during a cycle of operation. If this engine is reversed and operates as a heat pump, then what is its coefficient of performance? [IES-2009] (a) 1.0 (b) 1.5 (c) 2.0 (d) 2.5
IES-13a
IES-14.
IES-15. A heat engine is supplied with 250 kJ/s of heat at a constant fixed temperature of 227C; the heat is rejected at 27C, the cycle is reversible, then what amount of heat is rejected? [IES-2009] (a) 250 kJ/s (b) 200 kJ/s (c) 180 kJ/s (d) 150 kJ/s IES-16. One reversible heat engine operates between 1600 K and T2 K, and another reversible heat engine operates between T2K and 400 K. If both the engines have the same heat input and output, then the temperature T2 must be equal to: [IES-1993] (a) 1000 (b) 1200 (c) 1400 (d) 800
Previous 20-Years IAS Questions Kelvin-Planck Statement of Second Law

IAS-1. Assertion (A): No machine would continuously supply work without expenditure of some other form of energy. [IAS-2001] Reason (R): Energy can be neither created nor destroyed, but it can only be transformed from one form into another. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true

IAS-2. A heat engine is supplied with 250 KJ/s of heat at a constant fixed temperature of 227C. The heat is rejected at 27C. The cycle is reversible, if the amount of heat rejected is: [IAS-1995] (a) 273 KJ/s (b) 200 KJ/s (c) 180 KJ/s (d) 150 KJ/s.
79

S K Mondals
IAS-3. A reversible engine En as shown in the given figure draws 300 kcal from 200 K reservoir and does 50 kcal of work during a cycle. The sum of heat interactions with the other two reservoir is given by: (a) Q1 + Q2 = + 250 kcal (b) Q1 + Q2 = 250 kcal (c) Q1 + Q2 = + 350 kcal (d) Q1 + Q2 = 350 kcal
Chapter 3
[IAS-1996]
Carnot Engine with same efficiency or same work output

IAS-4. Consider the following statements: [IAS-2007] 1. Amount of work from cascaded Carnot engines corresponding to fixed temperature difference falls as one goes to lower absolute level of temperature. 2. On the enthalpy-entropy diagram, constant pressure lines diverge as the entropy increases. Which of the statements given above is/are correct? (a) 1 only (b) 2 only (c) Both 1 and 2 (d) Neither 1 nor 2 In a cyclic heat engine operating between a source temperature of 600C and a sink temperature of 20C, the least rate of heat rejection per kW net output of the engine is: [IAS 1994] (a) 0.460 kW (b) 0.505 kW (c) 0.588 kW (d) 0.650 kW
IAS-5.

IES-1. Ans. (a) IES-2. Ans. (c) A is true but R is false. IES-3. Ans. (c) Heat transfer takes place according to second law of thermodynamics as it tells about the direction and amount of heat flow that is possible between two reservoirs. IES-3a. Ans. (b) All spontaneous processes are irreversible. Statement-1 and statement-4 heat is transferred with a finite temperature difference they are irreversible. IES-3b. Ans. (d) Any natural process carried out with a finite temperature gradient is an irreversible process. All spontaneous processes are irreversible. Statement -4 is a spontaneous process. IES-4. Ans. (c) Out of 4 definitions given, only first definition is correct and balance three are wrong. IES-5. Ans. (b) A and R are true. A is the Clausius statement of second law of thermodynamics. Spontaneously means without change in surroundings. If question comes like following then answer will be (a).
80

Assertion (A): External work must be put into heat pump so that heat can be transferred from a cold to a hot body. Reason (R): Heat cannot spontaneously pass from a colder system to a hotter system without simultaneously producing other effects in the surroundings. IES-6. Ans. (d) 300 T = 0.5 IES-7. Ans. (c) Carnot efficiency of engine = = 1 2 = 1 600 T1 But according to the inventors Claim Efficiency of engine = 1-0.45 = 0.55 Efficiency of Actual Engine cannot be greater then Carnot efficiency. So this is an impossible engine. Ans. (c) We know Carnot efficiency
carnot = 1
IES-7a
T2 T1
300 1 = = 0.5 600 2
carnot = 50% But inventor claims 60% efficiency (means 40% heat rejection). It is then impossible. IES-8. Ans. (a) IES-9. Ans. (c) IES-10. Ans. (c) Figure from another question W1 = W2
or Q1 Q2 = Q2 Q3 or T1 T2 = T2 T3 or T2 =
IES-10a. Ans. (b) When equally efficiency
T1 + T3 900 + 400 = = 650K 2 2
T T2 = 1 3 T1 T2
or T2 = T1T3 = 900 400 = 600 K
IES-11. Ans. (c) 1 = 2
or 1
T2 300 = 1 1200 T2
or T2 = 1200 300 = 600K
81

S K Mondals
IES-12. Ans. (c c) Sou urce Tempera ature = T1,
Inte ermediate Temperature = T Sin nk Temperatu ure = T2
Cha apter 3
W1 = W2
T T Q1 1 = Q2 1 2 T T1
T1 T1 T2 T T2 1 = 1 1 = 1 T T1 T T T T1 + T2 T + T2 180 + 20 0 =2 = = 100C T = 1 2 2 T IES-13. Ans. (b b) Sink temp perature = 27 7C = 27 + 27 73 = 300K It is given that engine rejec cts 40% of ab bsorbed heat from the sou urce Q Q For r a carnot cyc cle engine 1 = 2 T2 T1
Q 0.4 4Q 30 00 = T= = 750K = 477C T 30 00 0. .4
IES-13a
Ans. (c) Q1 Q2 = T1 T2
or T1 = T2 Q1 Q = 30 03 1 = 1010 K = 737 o C Q2 0.3Q1
IES-14. Ans. (c c)
Q1 Q2 = T1 T2 Q 0.5 Q1 1 = T1 T2
T2 = 0.5 T1
If the engine is reversed an nd operated as a the Heat Pum mp. The en COP coeff ficient of perf formance
T1 = T1 T2
1 1 = =2 T2 5 1 0.5 1 T1
IES-15. Ans. (d d) Heat supp plied by the Heat H Engine = Q1 = 250 kJ/sec k
Sou urce tempera ature = 227C = 500 K Sin nk temperatu ure = 27C = 300K 3 82

S K Mondals
250 Q2 = Q2 = 250 0.6 = 150kJ / sec 500 300 IES-16. Ans. (d) Two reversible heat engines operate between limits of T2 and 400K 1600K and T2; Both have the same heat input and output,
Chapter 3
i.e.
T1 T2 1600 T2 T2 400 is same for both or = or T2 = 800 K T1 1600 T2

IAS-1. Ans. (a) IAS-2. Ans. (d) IAS-3. Ans. (b)
Q = W
Q1 Q2 = T1 T2
300 + Q1 + Q2 = 50 IAS-4. Ans. (b) For reversible cycle
T1 T2 T3 = = Q1 Q2 T3 or T1 T2 Q1 Q2 = T2 Q2 T2 Q2 T3 Q3
or T1 T2 = (Q1 Q2 ) Similarly
T2 T3 = ( Q2 Q3 )
If T1 T2 = T2 T3 then Q1 Q2 = Q2 Q3 or W1 = W2
IAS-5. Ans. (b) Reversible engine has maximum efficiency where
Q1 Q2 Q1 Q2 W = = = T1 T2 T1 T2 T1 T2
Therefore least heat rejection per kW net output, W 1 Q2 = T2 = 293 = 0.505 kW T1 T2 873 293
83
Ent tropy
4.
Entro opy
Theo ory at a Glance (Fo or GAT TE, IES S & PS SUs)

Tw wo Reve ersible Adiabati A c Paths cannot Intersec ct Each Other
Let it be assum med that two o reversible adiabatics a AC and BC in ntersect each h other at point C (Fig.). e isotherm AB A be drawn in such a wa ay that it inte ersects the re eversible adiabatics at A Let a reversible e processes AB, A BC, and CA C together constitute c a reversible cy ycle, and the and B. The three reversible ea included represents r th he net work output in a cycle. But such s a cycle is impossibl le, since net are wo ork is being produced p in a cycle by a heat h engine by b exchangin ng heat with a single rese ervoir in the pro ocess AB, which w violat tes the Kelv vin-Planck statement s o the secon of nd law. The erefore, the ass sumption of the intersection of the reversible r ad diabatics is Fig. F wrong. Through T one point, there can n pass only one o reversible e adiabatic. nce two cons stant propert ty lines can never intersect each ot ther, it is inf ferred that a reversible Sin adi iabatic path must represe ent some pro operty, which h is yet to be identified. i
83
Entropy
The Property of Entropy
dQ ds = T

Reversible
dS is an exact differential because S is a point function and a property. The subscript R in dQ indicates that heat dQ is transferred reversibly.
S s = J / kg K m
It is an extensive property, and has the unit J/K. The specific entropy is an intensive property and has unit J/kgK
The change of entropy may be regarded as a measure of the rate of availability of heat for transformation into work.
If the system is taken from an initial equilibrium state i to a final equilibrium state f by an irreversible path, since entropy is a point or state function, and the entropy change is independent of the path followed, the non-reversible path is to be replaced by a reversible path to integrate for the evaluation of entropy change in the irreversible process
Sf Si =
dQrev = ( S )irrev path T
Integration can be performed only on a reversible path.
84
Ent tropy
Te empera ature-Entropy Plot
The Ineq quality of Clau usius

Th hen for any cy ycle
dQ T
ds
Sin nce entropy is i a property and the cycli ic integral of f any property is zero
dQ T
Th his equation is i known as the t inequalit ty of Clausiu us. It provides s the criterion of the rever rsibility of a cyc cle.
If
dQ ble, = 0 , the cyclle is reversib T d dQ i irreversib ble and possible < 0, the cycle is T
85
Entropy
dQ > 0 , the cycle is impossible, since it violates the second law. T
Entropy Change in an Irreversible Process
Flow of current through a resistance when a battery discharges through a resistance heat is dissipated. You cant recharge the battery by supplying heat back to the resistance element!! Pickpocket !!!Marriage!!!!.............................................are irreversible Process.
Applications of Entropy Principle

(S1-S2)irreversible > (S1-S2)reversible An irreversible process generates more entropy than a reversible process. An irreversible engine cant produce more work than a reversible one.
An irreversible heat pump will always need more work than a reversible heat pump.
An irreversible expansion will produce less work than a reversible expansion

An irreversible compression will need more work than a reversible compression.
86
Ent tropy
Maximum Work W Obtainable fr rom two Finite F Bod dies at tem mperature es T1 and T2
Let us conside er two inden ntical finite bodies b of con nstant heat capacity at temperature e T1 and T2 res spectively, T1 being high her than T2. If the two bodies b are me erely brough ht together in nto thermal con ntact, deliver ring no work, , the final tem mperature Tf reached wou uld be the maximum T + T2 Tf = 1 2 ne is operated d between th he two bodies acting as thermal t ener rgy reservoir rs (shown in If a heat engin Fig g. below), par rt of the hea at withdrawn n from body 1 is converted to work W by the heat engine, and the e remainder is rejected to t body 2. Th he lowest att tainable fina al temperatur re Tf corresp ponds to the del livery of the largest possi ible amount of o work, and is associated d with a rever rsible process. A As work is de elivered by th he heat engin ne, the temp perature of body 1 will be e decreasing and that of bod dy 2 will be increasing. i When W both th he bodies atta ain the final temperature e Tf, the heat t engine will sto op operating. Let the bodi ies remain at t constant pressure and undergo u no ch hange of phase.
Fig. Total heat with hdrawn from body 1 Q1 = Cp ( T1 Tf )

Wh here Cp is the e heat capaci ity of the two o bodies at co onstant press sure. Total heat rejec cted to body 2 Q2 = Cp (Tf T2) A Amount of to otal work del livered by the e heat engine e W = Q1 Q2 = Cp (T1 + T2 - 2T Tf) For given value es of Cp, T1 and a T2, the magnitude m of f work W dep pends on Tf. Work obtain nable will be ma aximum when n Tf is minim mum. No ow, for body 1, 1 entropy ch hange S1 is given g by T Tf dT f S1 = C p = C pln T1 T1 T tropy change S2 would be For body 2, ent Tf Tf dT S2 = C p = C pln T2 T T2 nce the work king fluid ope erating in the e heat engine cycle does not undergo any entropy y change, S Sin of t the working fluid in heat engine = dS d = 0 . Applying the entr ropy principl le
87
Ent tropy
S K Mondals
Suniv 0 C pln Tf T1 + C pln Tf2 T1T2 Tf T2 0
Cha apter 4
C pln
e Eq. for Tf to be a min nimum From above C pln n or Tf2 T1 .T2 ln =0 Tf2 T1T2 = 0 = ln 1
Tf = T1 .T2
For W to be e a maximum m, Tf will be T1 .T2 . From m abow Equat tion Wmax = C p (T1 + T2 2 T1T2 ) = C p ( T1 T2 )2 Th he final temp peratures of the t two bodie es, initially at a T1 and T2, can range from f (T1 + T2)/2 with no del livery of work k to T1 .T2 with w maximu um delivery of o work.
Let one of the bodies consi idered in the e previous se ection be a thermal t ener rgy reservoir r. The finite bod dy has a ther rmal capacity y Cp and is at a temperatur re T and the TER is at te emperature T0, such that T > T0. Let (Q - W). Then
Maximu um Work Obtainable from a Finite Bo ody and a TER :-
F Fig.
Ma aximum Wor rk Obtainable e When One of the Bodies s is a TER.
88
Ent tropy
S K Mondals
SBody = C p
T T0
Cha apter 4
T dT = C pln n 0 T T s=0 ds Q W To
SHE = STER =
T0 Q W + T To By the entropy principle,. Suniv = C pln l
Suniv 0 C pln or or or or C pln T0 Q W 0 + T To T0 W Q To T
T W Q C pln l 0 T To W Q + T0C pln To T To T
Wmax = Q + T0C pln
T Wmax = C p (T T0 ) T0ln n To
Process ses Exhibi iting Exte ernal Mec chanical Ir rreversibility :l Dissipatio on of Work :: Let us con nsider the iso othermal diss sipation of work w through [i] Isothermal a s system into the internal l energy of a reservoir, as a in the flow of an elec ctric current through a res sistor in cont tact with a re eservoir (Fig.in below.) At A steady stat te, the intern nal energy of the resistor and hence its te emperature is i constant. So, S by first la aw: W=Q he flow of cur rrent represents work tr ransfer. At steady s state the work is dissipated isothermally Th int to heat trans sfer to the surroundings. Since the sur rroundings absorb a Q unit t of heat at temperature t T,
89
Ent tropy
S K Mondals
(Fig. .)
Cha apter 4
Q W = T T At stea ady state, Ssys = 0 Ssurr = W T he irreversible process is thus t accompa anied by an entropy e incre ease of the un niverse. Th Suni u v = Ssys + Ssurr =
[ii] ] Adiabatic c Dissipation of Work :: Let W be the t stirring work w supplied to a viscou us thermally ins sulated liquid, which is dissipated adiabatically a into interna al energy inc crease of the e liquid, the tem mperature of f which incre eases from Ti to Tf ( show wn in fig belo ow). Since th here is no flow w of heat to or from the sur rroundings.
( (Fig. ) To calculate th he entropy ch hange of the system, the e original irreversible pat th (dotted lin ne) must be rep placed by a reversible r on ne between the t same end d states, i an nd f. Let us replace the irreversible per rformance of f work by a reversible r iso obaric flow of f heat from a series of res servoirs rang ging from Ti to Tf to cause th he same chan nge in the sta ate of the sys stem. The entropy change e of the syste em will be C p dT Tf dQ Ssys = f =f = C p ln T Ti Ri T Ri here Cp is the e heat capac city of the liq quid. wh
Suniv = Ssys + Ssurr = C pln n Tf Ti
Entropy Genera ation

Irreversible Process ses increase the t entropy of o the univers se. Reversi ible Processe es do not effec ct the entrop py of the univ verse. Impossible Processe es decrease th he entropy of f the univers se.
Suniverse = 0
90
Entropy
S K Mondals
Entropy Generation in the universe is a measure of lost of work.
Chapter 4
S Universe = S System + S Surroundings

The losses will keep increasing. The sin keeps accumulating. Damage to environment keeps increasing. When the entropy of the universe goes so high, then some one has to come and set it right. HE
SAYS HE WILL COME. Every religion confirms this. Let us all wait. Cheer up, things are not that bad yet!!
Entropy and Direction: The Second Law a Directional law of Nature

The second law indicates the direction in which a process takes place. A process always occurs in such a direction as to cause an increase in the entropy of the universe.
91
Entropy
Summary
1. Clausius theorem:
dQ =0 T rev.
2.
S f Si =
dQ rev = ( s ) irrev . path . T
Integration can be performed only on a reversible path. 3. 4. 5. 6. 7. 8. Clausius Inequality:

dQ 0 T At the equilibrium state. The system is at the peak of the entropy hill. (isolated)
Tds = du + Pdv Tds = dh Vdp where K =Boltzmann constant W = thermodynamic probability General case of change of entropy of a Gas. Famous relation S = K lnW
P V S2 S1 = m Cv ln 2 + CP ln 2 P1 V1
Initial condition of gas P1, V1, T1, S1 and Final condition of gas P2, V2, T2, S2 9. Process and property change Table:
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Entropy

Example 1. 5 kg of air is compressed in a reversible polytrophic process from 1 bar and 40C to 10 bar with an index of compression 1.25. Calculate the entropy change during the process. Solution:T2 p2 = T1 p1
n 1 n
p n 10 1.25 = ( 273 + 40 ) T2 = T1 2 p 1 1 Therefore T2 = 496 K
n 1
0.25
2 1 = C p
dT vdp dT dp = Cp R T T T p 1 1 1 1
T p =1.005ln 2 R ln 2 T 1 p1 496 = 1.005ln 0.287 ln(10) 313 = 0.4627 0.6608 = 0.1981 kJ / kg K . Total change in entropy = 5 (-0.1981) = - 0.9905 kJ/K (Reduction). (Hence heat is rejected during the process).
Example 2.
Two compartments of an insulated vessel each of 3 m3 contain air at 0.7 MPa, 95C and 0.35 MPa, 205C. If the removed, find the change in entropy, if the two portions mix completely and adiabatically. Solution:
93
Entropy
S K Mondals
m1 = m2 = p1V1 0.7 106 3 = = 19.883 kg RT1 287 ( 273 + 95 ) p2V2 0.35 106 3 = = 7.654 kg RT2 287 ( 273 + 205 ) Cv (m1T1 + m2T2 ) Cv (m1 + m2 ) Tf T1
Chapter 4
Assuming specific heat to be constant Tf = = 398.6 K = 125.6C 398.6 = 1595J / K 368
S1 = m1Cv ln
= 19.883 1005 ln
398.6 = 1396.6J / K 478 S = 1595 1397 = 198J / K S2 = 7.654 1005 ln
94
Entropy

Previous 20-Years GATE Questions Applications of Entropy Principle
GATE-1. A 1500 W electrical heater is used to heat 20 kg of water (Cp = 4186 J/kg K) in an insulated bucket, from a temperature of 30C to 80C. If the heater temperature is only infinitesimally larger than the water temperature during the process, the change in entropy for heater is.. J/k and for water ............. J/K. [GATE-1994]
Entropy Generation in a Closed System

GATE-1A An ideal gas of mass m and temperature T1 undergoes a reversible isothermal process from an initial pressure P1 to final pressure P2. The heat loss during the process is Q. The entropy change S of the gas is P P P Q (a) mR ln 2 (b) mR ln 1 (c) mR ln 2 (d ) zero [GATE-2012] P P T1 1 1 2 P
Data for Q2 and Q3 are given below. Solve the problems and choose correct answers.
Nitrogen gas (molecular weight 28) is enclosed in a cylinder by a piston, at the initial condition of 2 bar, 298 K and 1 m3. In a particular process, the gas slowly expands under isothermal condition, until the volume becomes 2m3. Heat exchange occurs with the atmosphere at 298 K during this process. GATE-2. The work interaction for the Nitrogen gas is: (a) 200 kJ (b) 138.6 kJ (c) 2 kJ [GATE-2003] (d) 200 kJ
GATE-3.
The entropy change for the Universe during the process in kJ/K is: [GATE-2003] (a) 0.4652 (b) 0.0067 (c) 0 (d) 0.6711 If a closed system is undergoing an irreversible process, the entropy of the system [GATE-2009] (a) Must increase (b) Always remains constant (c) Must decrease (d) Can increase, decrease or remain constant
GATE-4.

GATE-5. One kilogram of water at room temperature is brought into contact with a high temperature thermal reservoir. The entropy change of the universe is: (a) Equal to entropy change of the reservoir [GATE-2010]
95
Entropy
S K Mondals
(b) Equal to entropy change of water (c) Equal to zero (d) Always positive
Chapter 4
Common Data for Questions GATE-6 and GATE-7:

In an experimental set-up, air flows between two stations P and Q adiabatically. The direction of flow depends on the pressure and temperature conditions maintained at P and Q. The conditions at station P are 150 kPa and 350 K. The temperature at station Q is 300 K. The following are the properties and relations pertaining to air: Specific heat at constant pressure, cp = 1.005 kJ/kg K; Specific heat at constant volume, cv = 0.718 kJ/kg K; Characteristic gas constant, R = 0.287 kJ/kg K. Enthalpy, h = cpT Internal energy, u = cvT GATE-6. If the pressure at station Q is 50 kPa, the change in entropy (sQ sP ) in kJ/kg K is (a) 0.155 GATE-7.
(b) 0
(c) 0.160
[GATE-2011] (d) 0.355
If the air has to flow from station P to station Q, the maximum possible value of pressure in kPa at station Q is close to [GATE-2011] (a) 50 (b) 87 (c) 128 (d) 150

Two Reversible Adiabatic Paths cannot Intersect Each Other
IES-1. The relation ds =
dQ , where s represents entropy, Q represents heat and T T
represents temperature (absolute), holds good in which one of the following processes? [IES-2009] (a) Reversible processes only (b) Irreversible processes only (c) Both reversible and irreversible processes (d) All real processes IES-2. Which of the following statement is correct? [IES-2008] (a) The increase in entropy is obtained from a given quantity of heat transfer at a low temperature. (b) The change in entropy may be regarded as a measure of the rate of the availability of heat for transformation into work. (c) The entropy represents the maximum amount of work obtainable per degree drop in temperature (d) All of the above A heat engine receives 1000 kW of heat at a constant temperature of 285C and rejects 492 kW of heat at 5C. Consider the following thermodynamic cycles in this regard: [IES-2000] 1. Carnot cycle 2. Reversible cycle 3. Irreversible cycle 96
IES-2a.
Entropy
Which of these cycles could possible be executed by the engine? (a) 1 alone (b) 3 alone (c) 1 and 2 (d) None of 1, 2 and 3
The Property of Entropy

IES-3. Assigning the basic dimensions to mass, length, time and temperature respectively as M, L, T and (Temperature), what are the dimensions of entropy? [IES-2007] (a) M LT-2 (b) M L2 T-1 -1 (c) M L2 T-2-1 (d) M L3T-2 -1 A Carnot engine operates between 327C and 27C. If the engine produces 300 kJ of work, what is the entropy change during heat addition? [IES-2008] (a) 0.5 kJ/K (b) 1.0 kJ/K (c) 1.5 kJ/K (d) 2.0 kJ/K
IES-4.
Temperature-Entropy Plot
IES-4a Isentropic flow is [IES-2011]
(a) Irreversible adiabatic flow (c) Ideal fluid flow
(b) Reversible adiabatic flow (d) Frictionless reversible flow
IES-5.
A system comprising of a pure substance executes reversibly a cycle 1 -2 -3 -4 -1 consisting of two isentropic and two isochoric processes as shown in the Fig. 1. Which one of the following is the correct representation of this cycle on the temperature entropy coordinates? [IES-2002]
97
Ent tropy
IES-6.
A cycle of pressure p volume dia agram is sh hown in th he given Fig g. I, Same S cyc cle on tem mperature-e entropy diagram wil ll be represe ented by:
[IES-1995]
IES-7.
An ideal air standard cycle c is given sho own in the tem mperature-e entropy diagram.
[IES-1997]
98
Ent tropy
The e same cyc cle, when re epresented on the pre essure-volum me coordin nates takes the e form
IES-8.
Ma atch figures s of Colum mn-I with th hose given in Column n-II and se elect given bel low the colu umns: [IES-1994] Col lumn-I (p-v diagram) Colum mn-II (T-s diagram)
Cod des: (a) (c) IES-9.
A 1 3
B 2 1
C 3 2
(b) (d)
A 2 3
B 3 2
C 1 1
A cyclic c proce ess ABCD shown s in the e V-T diagra am perform med with a constant c ma ass of an id deal gas. The e process of o p-V diagr ram will be as shown in n [IES-1992]
99
Ent tropy
IES-10.
Thr ree process ses are repr resented on n the p-v an nd T-s diagr rams in the e following figu ures. Match h processes s in the tw wo diagrams s and selec ct the corre ect answer usi ing the code es given bel low the diag grams: [IES-1994]
Cod des: (a) (c) IES-11.
A 1 3
B 2 2
C 3 1
(b) (d)
A 2 1
B 3 3
C 1 2
Tw wo polytropi ic processes undergon ne by a perf fect gas are e shown be elow in the pre essure-volum me co-ordin nates. [IES-2008]
Wh hich represe entation sho ows correct tly the abov ve processes s on the tem mperature ent tropy co-ord dinates?
100 0
Entropy
IES-12.
Assertion (A): If a graph is plotted for absolute temperature as a function of entropy, the area under the curve would give the amount of heat supplied. Reason (R): Entropy represents the maximum fraction of work obtainable from heat per degree drop in temperature. [IES-1998] (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
The Inequality of Clausius

IES-13. For real thermodynamic cycle: [IES-2005]
(a)
IES-14.
dQ > 0 but < T
(b)
dQ <0 T
(c)
dQ =0 T
(d)
dQ = T
For a thermodynamic cycle to be irreversible, it is necessary that
(a)
IES-15.
Q
T
=0
(b)
Q
T
<0
(c)
Q
T
>0
(d)
Q
T
[IES-1998]
For an irreversible cycle:
[IES-1994, 2011]
(a)
IES-16.
dQ 0 T
(b)
dQ >0 T
(c)
dQ <0 T
(d)
dQ 0 T
If a system undergoes an irreversible adiabatic process, then (symbols have usual meanings) [IES-1997]
dQ = 0 and S > 0 T dQ (c) > 0 and S = 0 T

(a)
(b)
dQ = 0 and S = 0 T dQ (d) < 0 and S < 0 T
101
Entropy
Entropy Change in an Irreversible Process

IES-17. Consider the following statements: [IES-1998] In an irreversible process 1. Entropy always increases. 2. The sum of the entropy of all the bodies taking part in a process always increases. 3. Once created, entropy cannot be destroyed. Of these statements (a) 1 and 2 are correct (b) 1 and 3 are correct (c) 2 and 3 are correct (d) 1, 2 and 3 are correct Consider the following statements: [IES-1997] When a perfect gas enclosed in a cylinder piston device executes a reversible adiabatic expansion process, 1. Its entropy will increase 2. Its entropy change will be zero 3. The entropy change of the surroundings will be zero Of these statements (a) 1 and 3 are correct (b) 2 alone is correct (c) 2 and 3 are correct (d) 1 alone is correct A system of 100 kg mass undergoes a process in which its specific entropy increases from 0.3 kJ/kg-K to 0.4 kJ/kg-K. At the same time, the entropy of the surroundings decreases from 80 kJ/K to 75 kJ/K. The process is: [IES-1997] (a) Reversible and isothermal (b) Irreversible (c) Reversible (d) Impossible Which one of the following temperature entropy diagrams of steam shows the reversible and irreversible processes correctly? [IES-1996]
IES-18.
IES-19.
IES-20.
Applications of Entropy Principle

IES-21. A Carnot engine operates between 27C and 327C. If the engine produces 300 kJ of Work, What is the entropy change during heat addition? [IES-2005] 102
Entropy
S K Mondals
(a) 0.5 kJ/K
IES-22.
Chapter 4
(b) 1.0 kJ/K (c) 1.5 kJ/K (d) 2.0 kJ/K
The entropy of a mixture of ideal gases is the sum of the entropies of constituents evaluated at: [IES-2005] (a) Temperature and pressure of the mixture (b) Temperature of the mixture and the partial pressure of the constituents (c) Temperature and volume of the mixture (d) Pressure and volume of the mixture The heat added to a closed system during a reversible process is given by Q = T + T 2 , where and are constants. The entropy change of the system as its temperature changes from T1 to T2 is equal to: [IES-2000]
IES-23.
(a) + (T2 T1 )
(b) (T2 T1 ) + T22 T12 / T1 2
(c) T22 T12 + T23 T13 / T12 2 2
( d ) ln
T2 + 2 (T2 T1 ) T1
IES-24.
One kg of air is subjected to the following processes: [IES-2004] 1. Air expands isothermally from 6 bar to 3 bar. 2. Air is compressed to half the volume at constant pressure 3. Heat is supplied to air at constant volume till the pressure becomes three fold In which of the above processes, the change in entropy will be positive? (a) 1 and 2 (b) 2 and 3 (c) 1 and 3 (d) 1, 2 and 3 A reversible heat engine receives 6 kJ of heat from thermal reservoir at temperature 800 K, and 8 kJ of heat from another thermal reservoir at temperature 600 K. If it rejects heat to a third thermal reservoir at temperature 100 K, then the thermal efficiency of the engine is approximately equal to: [IES-2002] (a) 65% (b) 75% (c) 80% (d) 85% A reversible engine exceeding 630 cycles per minute drawn heat from two constant temperature reservoirs at 1200 K and 800 K rejects heat to constant temperature at 400 K. The engine develops work 100kW and rejects 3200 KJ heat per minute. The ratio of heat drawn from two reservoirs
IES-25.
IES-26.
Q1200 is nearly. Q800

[IES-1992] (d) 10.5
(a) 1
IES-27.
(b) 1.5
(c) 3
In which one of the following situations the entropy change will be negative (a) Air expands isothermally from 6 bars to 3 bars [IES-2000] (b) Air is compressed to half the volume at constant pressure (c) Heat is supplied to air at constant volume till the pressure becomes three folds (d) Air expands isentropically from 6 bars to 3 bars
103
Ent tropy
Entropy and Direction n: The Second Law a Direc ctional aw of Nature la

IES-28. A mass m M of a fluid at tem mperature T1 is mixed d with an eq qual mass of o the same flui id at tempe erature T2. The T resultan nt change in n entropy of o the universe is: [IES-1992] (a) Zero (b) Negli igible (c) Always s negative (d) Always positive p Increase in n entropy of f a system represents r (a) Increase in availabili ity of energy (b) Increas se in tempera ature e in pressure (d) Degrad dation of energy (c) Decrease [IES-2011]
IES-29
Previo ous 20 0-Years s IAS Quest Q ions

Tw wo Reve ersible Adiabati A c Paths cannot Intersec ct Each Other
IA AS-1. Wh hich one of the t followin ng is the cor rrect statem ment? Tw wo adiabatic c will: (a) Intersect at absolute zer ro temperature (b) Never inters sect (c) Become orth hogonal at ab bsolute zero temperature t (d) Become parallel at absol lute zero tem mperature [IAS-2007]
The Prop perty of o Entro opy

IA AS-2. Heat flows be etween two o reservoirs s having te emperature es 1000 K and a 500 K, res spectively. If I the entrop py change of o the cold reservoir r is s 10 kJ/K, th hen what is the e entropy ch hange for th he hot reser rvoir? [IAS-2004] (a) 10 kJ/K (b) 5 kJ/K (c) ) 5 kJ/K (d) 10 kJ/K
Te empera ature-Entropy Plot

IA AS-3. An ideal cycl le is shown n in the giv ven pressure e-volume di iagram:
[IAS-1997]
104 4
Ent tropy
The e same cycl le on temperature-entr ropy diagram will be re epresented as:
IA AS-4.
The e therma al efficien ncy of t the hyp pothetical heat h engine e cycle show wn in the t given figure is: (a) 0.5 (b) 0.45 0 (c) 0.35 (d) 0.25
[IAS-2000] AS-5. IA Wh hich one of the followi ing pairs be est expresses a relatio onship similar to that exp pressed in the pair r pressure e-volume for a the ermodynam mic system und dergoing a process? [IAS-1995] (a) Enthalpy-en ntropy (b) Pressu ure-enthalpy P mperature (d) Tempe erature-entro opy (c) Pressure-tem An ideal gas contained c in n a rigid ta ank is cooled c such h that T2 < and P2 <P1 In the e given ure entro opy temperatu dia agram, th his proces ss path is rep presented by the line la abelled. (a) A (b) B (c) C (d) D [IAS-1999]
IA AS-6.
105 5
Ent tropy
S K Mondals
IA AS-7. In the T-S di iagram shown in the figu ure, which one of the e following is represented r d by the area a under the e curve? (a) Total work done d during the process (b) Total heat absorbed during the process t rejected during d the (c) Total heat process (d) Degree of irreversibility [IAS-2004]
Cha apter 4
The Ineq quality of Clau usius

IA AS-8. Cla ausius inequ uality is sta ated as
(a)
[IAS-2001]
) (c)
Q < 0

dQ t< > 0 but T
(b)
Q = 0
dQ <0 T
>0
(d)
IA AS-9.
For r real therm modynamic cycle:

(a) (b) (c) )
[IAS-2003]
dQ =0 T
(d)
dQ = T
IA AS-10(i). If a system undergoes an a irreversi ible adiabatic process s, then (sym mbols have usu ual meaning gs) [IAS-1999]
dQ = 0 an nd S > 0 T dQ (c) > 0 an nd S = 0 T

(a)
dQ = 0 and S = 0 T dQ (d) < 0 and S < 0 T

(b)
IA AS-10(ii). A cyclic c heat engine rece eives 600 kJ of heat fr rom a 1000 K source and a rejects 450 0 kJ to a 300 3 K sink. The quant tity res spectively (a) 2.1 kJ/K and d 70% nd 70% (c) + 0.9 kJ/K an
dQ a and efficien ncy of the engine e are T

(b) ) 0.9 kJ/K and a 25% (d) ) 2.1 kJ/K and a 25%
[IAS-2001]
A Applicat tions of f Entrop py Prin nciple

IA AS-11. Wh hich one of the t followin ng statemen nts is not co orrect? [IAS-2003] (a) Change in entropy e durin ng a reversibl le adiabatic process p is zer ro (b) Entropy increases with the t addition of heat ansion proces ss (c) Throttling is a constant entropy expa hen a gas is heated under u consta ant pressure given by (d) Change in entropy wh
s2 s1 = mC C p log e
IA AS-12.
T2 T1
Ass sertion (A): Entropy ch hange for a reversible adiabatic a pr rocess is zero. 106 6
Entropy
Reason (R): There is no heat transfer in an adiabatic process. [IAS 1994] (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
Entropy Generation in a Closed System

IAS-13. 1600 kJ of energy is transferred from a heat reservoir at 800 K to another heat reservoir at 400 K. The amount of entropy generated during the process would be: [IAS-2000] (a) 6 kJ/k (b) 4 kJ/k (c) 2kJ/k (d) Zero An electric motor of 5 kW is subjected to a braking test for 1 hour. The heat generated by the frictional forces in the process is transferred to the surroundings at 20C. The resulting entropy change will be: [IAS-1998] (a) 22.1 kJ/K (b) 30.2 kJ/K (c) 61.4 kJ/K (d) 82.1 kJ/K
IAS-14.

IAS-15. M1 kg of water at T1 is isobarically and adiabatically mixed with M2 kg of water at T2 (T1 > T2). The entropy change of the universe is: [IAS-2004] (a) Necessarily positive (b) Necessarily negative (c) Always zero (d) Negative or positive but not zero In which one of the following processes is there an increase in entropy with no degradation of energy? [IAS-1996] (a) Polytropic expansion (b) Isothermal expansion (c) Isochoric heat addition (d) Isobaric heat addition
IAS-16.
107
Entropy

GATE-1. Ans. 11858 J/K, 12787 J/K. GATE-1A Ans. (b) 2 GATE-2. Ans. (b) w1 2 = mRT In 2 = p In 2 = 200 1 In kJ = 138.6 kJ 1 1 1 GATE-3. Ans. (c) It is reversible process so ( S )universe = 0 GATE-4. Ans. (d) GATE-5. Ans. (d) It is a case of spontaneous process i.e. irrepressibility involved that so why entropy change of the universe is positive. GATE-6. Ans. (c)
TQ = 300 K, TP = 350 K,
PQ = 50 kPa
PP = 150 kPa T P SQ SP = c P ln Q R ln Q TP PP
300 50 SQ SP = 1.005 ln 0.287 ln 350 150 SQ SP = 0.160 kJ/kg-K
GATE-7. Ans. (b) If air has to flow from station P to station Q adiabatically means no entropy change in surroundings, then
SQ SP 0
c P ln
TQ TP
R ln
PQ PP
PQ 300 1.005 ln 0.287 ln 0 350 150 P 0.287 ln Q 0.15492 150 PQ 87.43
P 0.15492 0.287 ln Q 0 150 P ln Q 0.53979 150
So, Ans. is PQ = 87 kPa
108
Ent tropy
Previ ious 20-Year rs IES Answ wers

IES-1. Ans. (a) ) Remember ds =
dQ T R Re v
IES-2. Ans. (b b) The chang ge of entropy y may be regarded as a measure m of th he rate of av vailability of hea at for transformation into o work. IES-2a Ans. (b b)
S gen =
1000 492 + = 0.02233 kW k /K (285 ( + 273) (5 + 273)
IES-3. Ans. (c) ) IES-4. Ans. (b) Q1 Q1 Q1 Q2 W = = = T1 T1 T1 T2 T1 T2

Q1 = 600kJ
So cycle is im mpossible Cy ycle See in both the case Car rnot Cycle an nd Reversible e cycle entrop py change of the t ill be zero. Universe wi Irreversible cycle entrop py change wil ll be positive.
The e entropy ch hange durin ng heat add dition Q1 600 = = = 1 kJ k /K T1 600 IES-4a Ans. (b) IES-5. Ans. (c) ) IES-6. Ans. (b) IES-7. Ans. (b) IES-8. Ans. (c) ) IES-9. Ans. (d) AB constan nt pressure heat h addition. IES-10. Ans. (c) XA cons stant pressu ure heat reje ection. XB = const. temp p. heat rejec ction. XC = isen ntropic heat rejection. r IES-11. Ans. (b b)
IES-12. Ans. (b b) IES-13. Ans. (b b) b) IES-14. Ans. (b IES-15. Ans. (c c)

109 9
Ent tropy
S K Mondals
IES-16. Ans. (a a) IES-17.
Cha apter 4
Ans. (c) In irreversible i heat reje ection process tropy ent decreases. In an irrever rsible y of the univ verse process entropy ways increas ses i.e. sum m of alw syst tem + su urroundings will incr reases.
dQ cessarily mea ans reversibl le process. If dQ = 0 . = 0 does not nec T
Con nsider the pr rocess 34 if f it is irre eversible pr rocess then also entropy will dec crease. IES-18. Ans. (c) ( In reversi ible adiabatic c expansion, entropy chan nge is zero and no change e in entropy of surroundings s s. b) Entropy in ncrease in pr rocess = 100 (0.4 0.3) = 10 kJ/kg IES-19. Ans. (b Ent tropy change e of surround dings = 5 kJ/K K Thu us net entrop py increases and a the proce ess is irrever rsible. IES-20. Ans. (c) ( In reversi ible process entropy e chan nge is zero an nd in four figu ures it is rep presented by stra aight vertical line. Howev ver, in irreve ersible proces ss, entropy in ncreases in all a processes (exp pansion as well w as compression). IES-21. Ans. (b b)
( T1 T2 ) S = W
or S = 300 = 1 kJ / k 600 300
IES-22. Ans. (c c)
T dQ 1 + 2 T IES-23. Ans. (d d) dT = T = ln 2 + 2 (T2 T1 ) T T T1 T1 T1

T1 T
IES-24. Ans. (c c)
IES-25. Ans. (d d)
110 0
Entropy
S K Mondals
Q 6 = 2 800 100 Q 8 = 4 600 100 Q + Q4 = 1 2 Q1 + Q3
Chapter 4
3 4 + 4 3 = 0.85 = 1 6+8
IES-26. Ans. (d) Refer to given figure, as given Engine work developed = 100 kW = 100 1000 60 = 6 106 J/min. Qs = total heat supplied Thus,
= 6 106 +3.2 106 = 9.2 106 J/min. Let reservoir at 1200 K supply Qs1 J/min. Therefore reservoir at 800 o K will supply. Qs2 = 9.2 106 Qs1 Also, by data the engine is a reversible heat engine completing 600 cycles/min. and therefore entropy change after every complete cycle is zero. Thus, or
Qs1 Qs2 QR + =0 1200 800 400

Qs1 9.2 106 Q 6 3.2 106 + =0 1200 800 400
2Qs1 + 3(9.2 106 Qs1 ) 6 3.2 106 =0 2400
or
Qs1 = 3 9.3 106 6 3.2 106

= 8.4 106 J/min
Qs2 = 9.2 106 8.4 106
= 0.8 106 J/min 8.4 Hence ratio = =10.5 0.8 IES-27. Ans. (b) It is isobaric compression.
111
Ent tropy
IES-28. Ans. (d d)
IES-29
Ans. (d)
Previ ious 20 0-Year rs IAS Answ wers

IA AS-1. Ans. (b) IA AS-2. Ans. (b)
+Q = 10 0 500 or Q = 5000 kJ Q 5000 S1 = = = 5kJ / k 1000 1000 1 t thesystem m is +ive Heat added to Heat rejecte ed from the sy ystem is -ive S2 =
IA AS-3. Ans. (d)

1 ( 5 1) ( 800 40 00 ) Work done d area1 2 3 = = 2 = 0.25 IA AS-4. Ans. (d) = Heat ad dded areaunder curve 2 3 ( 5 1) 800
IA AS-5. Ans. (d) That so wh hy we are usin ng pv or T s diagram. IA AS-6. Ans. (a) ) IA AS-7. Ans. (b b) IA AS-8. Ans. (d) IA AS-9. Ans. (b)
112 2
Entropy
S K Mondals
IAS-10(i). Ans. (a)
Chapter 4
dQ = 0 does not necessarily means reversible process. If dQ = 0 . T Q Q2 Q 450 = 1 2 = 1 = 0.25 = 25% IAS-10(ii). Ans. (b) = 1 600 Q1 Q1
IAS-11. Ans. (c) Throttling is a constant enthalpy expansion process. IAS-12. Ans. (b) dQ dQ 1600 1600 = = 2kJ / K IAS-13. Ans. (c) Entropy generated = dsat 400K dsat 800K = 400 800 400 800 Q 5 3600 = kJ / K = 61.4kJ / K IAS-14. Ans. (c) S = T 293 IAS-15. Ans. (a) IAS-16. Ans. (b)
113
Availability, Irreversibility
5.

That part of the low grade energy which is available for conversion is referred to as available energy, while the part which, according to the second law, must be rejected, is known as unavailable energy.
Availability
The availability of a given system is defined as the maximum useful work that can be obtained in a process in which the system comes to equilibrium with the surroundings or attains a dead state. Clearly, the availability of a system depends on the condition of the system as well as those of the surroundings.
Availability:
Yields the maximum work producing potential or the minimum work requirement of a process Allows evaluation and quantitative comparison of options in a sustainability context Availability = Maximum possible work-Irreversibility
W useful = W rev I Irreversibility

The actual work done by a system is always less than the idealized reversible work, and the difference between the two is called the irreversibility of the process.
I = Wmax W
This is also sometimes referred to as 'degradation' or 'dissipation'.
Availability and Irreversibility

1. Available Energy (A. E.)
T T0 T = Wmax = Q1 1 = mcp 1 0 dT T1 T T0 = (T1 T0 ) S
Where To is surroundings temperature. 112
S K Mondals
1 2
= u u T (S S
0 1
) )
Chapter 5
(For closed system), it is NOT ( 1 2) because
change of volume is present there.

1 2 0 1
= h h T (S S
(For steady flow system), it is (A1-A2) as in steady state
no change in volume in C.V. (i.e. change in availability in steady flow)

2. Decrease in Available Energy
= T0 [ S S ]
3.
Take S and S both positive quantity.
Availability function
C A = h T0S + + gz 2 = u T0S + P0V

Availability = maximum useful work. For steady flow
For open system
For closed system
C12 Availability = A1 A0 = ( h1 h0 ) T0 ( S1 S0 ) + + gz 2
For closed system
Availability = 1 0 = u1 u0 T0 ( S1 S0 ) + P0 ( V1 V0 )
4.
Unavailable Energy (U.E.)
= T0 ( S1 S2 )
5.
Increase in unavailable Energy = Loss in availability
= T0 ( S )Univ
6.
Irreversibility
113
I = Wmax Wactual = T0 ( S )univ

S gen = mds
1 2
7.
Irreversibility rate = I = rate of energy degradation
= rate of energy loss (Wlost) =
T0
Sgen for all processes
8.
Wactual dQ = du + dWact this for closed system dWact C12 C22 dQ + gz1 + = h2 + + gz2 + this for steady flow h1 + 2 2 dm dm
9.
Helmholtz function
F = U TS
10. Gibbs function
G = H TS
11. Entropy generation number (Ns)
Ns =
12.
s mC
gen
To calculate dS
114
S K Mondals
( i ) Use S
P V S1 = m CV ln 2 + CP ln 2 P1 V1 For closed system
2
Chapter 5
or
Tds = du + PdV dT P + dV ds = m CV T T dT dV = m CV + mR T V 2 2 2 dT dV + mR ds = m CV T 1 1 1 V Tds = dh VdP
For steady flow system or dT V dP T T 2 2 2 dT dP = ds m C mR P T 1 1 1 P ds = m CP PV = mRT V mR = T P
But note that and Tds = du + PdV Both valid for closed system only. Tds = dh VdP
13.
In Pipe flow Entropy generation rate
S =S
gen sys
Q T
0
= m (S S )
2 1
mC (T T )
P 2 1
1 in Kg/s P,T1
Due to lack of insulation it may be T1 > T2 for hot fluid or T1 < T2 for cold fluid
P,T2
rate of irreversibility ( I ) = T0 Sgen

14. Flow with friction
Decrease in availability = m RT0
P P1
115
15. Second Law efficiency

Min n . exergy intake to perform the given tast (X min ) II = = I / carnot Actual exergy intake to perform the given tast (X) X min = W if work is involved T = Q 1 0 if Heat is involved. T
A common measure on energy use efficiency is the first law efficiency, 1 . The first law efficiency is defined as the ratio of the output energy of a device to the input energy of the device. The first law is concerned only with the quantities of energy, and disregards the forms in which the energy exists. It does not also discriminate between the energies available at different temperatures. It is the second law of thermodynamics which provides a means of assigning a quality index to energy. The concept of available energy or energy provides a useful measure of energy quality. With this concept it is possible to analyze means of minimizing the consumption of available energy to perform a given process, thereby ensuring the most efficient possible conversion of energy for the required task. The second law efficiency, 11 , of a process is defined as the ratio of the minimum available energy (or energy) which must be consumed to do a task divided by the actual amount of available energy (or energy) consumed in performing the task.
or
minimum exergy intake to perform the given task actual exergy intake to perform the same task A II = min A
II =
where A is the availability or energy. A power plant converts a fraction of available energy A or Wmax to useful work W. For the desired output of W, Amin = W and A = Wmax, Here,
116
Availab A bility, Irreversibi ility

S K Mondals
I = Wmax W and II = Now W Wmax W Wmax W = m QI Wmax Q1
Cha apter 5
I =
= II Carnot
II =
Ca arnot
Since Wmax = Q1 (l l-
T0 ), can n also be obt tained dire ectly as follows T I W = II = T Carnot Q1 1 0 T
T If w work is invol lved, Amin = W (desired) an nd if heat is involved, i Amin = Q 1 0 . T
Th he general de efinition of second s law ef fficiency of a process can n be obtained in terms of o change in ava ailability dur ring the process: Sec cond Law Eff fficiency = II = I Law
Produc ction of availability . Destru uction of avai ilability
A Available e Energ gy Refe erred to o a Cyc cle

Decrease e in Avail lable Ener rgy when Heat is Transferred T d through a Finite Tempera ature Defere ence :Wh henever heat is transfer rred through h finite temp perature def ference, ther re is a decrease in the ava ailability of energy e so tra ansferred. Let us consider r a reversible e heat engine e operating be etween T1 an nd T0 (Fig. sh hown in below w) Then
and
Q1 = T1 S, Q2 = T0 S, W = A.E. = (T1 T0) s
h Q1 is tr ransferred th hrough a fini ite temperat ture difference from the Let us now assume that heat servoir or sou urce at T1 to o the engine e absorbing, heat h at T1, lower l turn T1 (Fig.shown n in below). res 117 7

he availability y of Q1 as rec ceived by the e engine at T T 1 can be found by allowin ng the engin ne to operate Th rev versible in a cycle between T1 and T0, receiving Q1 and rejectin ng Q2.
No ow Sin nce Q2 = T0 s Q '2 = T0 s ' Sin nce an nd
Q1 = T1 s = T1' s ' T1 > T1' , s ' > s
s ' > s
Q '2 > Q2
W' = Q1 - Q'2 = T'1 s ' T0 s ' W = Q1 Q2 = T1 s T0 s
ecause Q2 W < W, be > Q2 Av vailable energ gy lost due to o irreversible e heat transf fer through fi inite tempera ature deferen nce between the e source and the working fluid during g the heat add dition proces ss is given by W - W = Q2 Q2 s = T0(s - s) n A.E. = T0(s - s) or decrease in
he decrease in n available energy e or exe ergy is thus the t product of o the lowest t feasible tem mperature of Th hea at rejection and the add ditional entro opy change in i the system m while rece eiving heat irreversibly, i com mpared to the t case of reversible heat h transfe er from the same sourc ce. The greater is the tem mperature di ifference (T1 - T1), the greater g is the heat reject tion Q2 and the greater will be the un navailable pa art of the ene ergy supplied d or energy (Fig. ( above). Energy is sa aid to be deg graded each tim me, it flows th hrough a fini ite temperatu ure difference e.
PR ROBLEMS & SOLUT TIONS

Ex xample 1 Wh hat is the ma aximum usef ful work whi ich can be ob btained when n 100 kJ are e abstracted from a heat res servoir at 675 K in an environmen ntal at 288 K? What is s the loss of o useful work if, (a) a tem mperature dr rop of 50C is introduced d between th he heat sour rce and the heat h engine, on the one hand and the heat h engine and a the heat sink, on the other. (b) th he source tem mperature drops by 50C
118 8

emperature rises r by 50C C during the heat transfer r process acc cording to the linear law and the sink te dQ Q = constan nt ? dT T So olution: Av vailability= To 288 8 Wm 33kJ 100 = 57.3 Q1 = 1 max = 1 T1 5 675
S =
W = S (T 1 T o ) = 0.16 ( 625 338 ) = 45.92 2kJ n availability y = 57.33-45.92 = 11.41 kJ J. Loss in
Q1 100 = = 0.16kJ / K T1 625
Av verage temperature of sou urce
119 9
S K Mondals
T1a = T1 + T "1 = 650 K 2 T0 + T "1 = 313 K 2 Average temperature of sink (T0 a ) = S" = Q1 100 = = 0.1538 kJ / K T1a 650
Chapter 5
W " = S " ( 650 313 ) = 51.83 kJ / K Loss in availability = 57.33 51.83 = 5.5 kJ . Example 2. A lead storage battery used in an automobile is able to deliver 5.2 MJ of electrical energy. This energy is available for starting the car. Let compressed air be considered for doing an equivalent amount of work in starting the car. The compressed air is to be stored at 7 MPa, 25C, what is the volume of the tank that would be required to let the compressed air having an availability of 5.2 MJ? For air pv = 0.287 T, where T is in K, p in kPa, and v in m3/kg. Solution: Availability is given by a = ( u uo ) To ( s so ) + po (v vo )
0.287 298 = 0.012218m3 / kg 7000 0.287 298 = 0.85526m3 / kg vo = 100 7000 7000 0.287ln + 100 ( 0.012218 0.85526 ) a = 0 298 0.287ln 7000 100 v= = 279 kJ / kg 5200 =18.635kg 279 V = m.v =18.635 0.012218 = 0.2277m3 For availability of 5.2 MJ, m =
Example 3. Air enters a compressor in steady flow at 140 kPa, 17C and 70 m/s and leaves it at 350 kPa, 127C and 110 m/s. The environment is at 100 kPa, 7C. Calculate per kg of air (a) the actual amount of work required, (b) the minimum work required, and (c) the irreversibility of the process. Solution: This is the case of a steady flow system in which the maximum useful work is given by 2 C 2 C2 Wmax useful = 1 2 + 1 2 2 C 2 C2 = ( H1 To S1 ) ( H 2 To S2 ) + 1 2 As air is to be considered as a perfect gas, h = CpT Hence 2 C 2 C2 Wmax useful = Cp (T1 T2 ) To ( S1 S2 ) + 1 2 In the above, expression (S1 - S2) is the entropy change. For a perfect gas, when pressure and temperature very, the entropy change is given by the relation
120
S K Mondals
S1 S2 = C p ln Hence
2 T P C 2 C2 Wmax useful = C p (T1 T2 ) To C p ln 1 R ln 1 + 1 T2 P2 2 Various parameters given are: T1 = 290 K; T2 = 400 K; Cp = 1.005 kJ/kg K P1 = 140 kPa; P2 = 350 kPa C1 = 70m / s; C2 = 110 m/s; To = 280 K (a) Actual work done in case of a steady flow process is given by C 2 1102 Wactual = ( H1 H 2 ) + 1 2 702 1102 = 1.005 ( 290 400 ) + = 114.1kJ 2 103 The negative sign obviously indicates that work is done on the air in compression. 290 140 702 1102 (b) Minimum work = 1.005(290 - 400) - 280 1.005 ln 0.287 ln + 400 350 2 103 = -97.3 kJ (c) Irreversibility= 114.1 - 97.3 = 16.8 kJ.
Chapter 5
T1 P R ln 1 T2 P2
Example 4. By how much is the available energy of 5 kg of air increased by heating reversibly at a constant pressure of 1.5 atm. from 27C to 227C with the lowest available temperature of 20C? (Cp for air = 1005 J/kgC). Solution: T Change in entropy = mC p ln 2 T1
500 = 2.567kJ / K 300 Availability = T0 S = 293 2.567 = 752kJ. = 5 1.005 ln
121

Previous 20-Years GATE Questions
GATE-1. A steel billet of 2000 kg mass is to be cooled from 1250 K to 450 K. The heat released during this process is to be used as a source of energy. The ambient temperature is 303 K and specific heat of steel is 0.5 kJ/kg K. The available energy of this billet is: [GATE-2004] (a) 490.44 MJ (b) 30.95 MJ (c) 10.35 MJ (d) 0.10 MJ
Availability
GATE-2. Availability of a system at any given state is: [GATE-2000] (a) A property of the system (b) The maximum work obtainable as the system goes to dead state (c) The total energy of the system (d) The maximum useful work obtainable as the system goes to dead state A heat reservoir at 900 K is brought into contact with the ambient at 300 K for a short time. During this period 9000 kJ of heat is lost by the heat reservoir. The total loss in availability due to this process is: [GATE-1995] (a) 18000 kJ (b) 9000 kJ (c) 6000 kJ (d) None of the above
GATE-3.
Irreversibility
GATE-4. Consider the following two processes: a. A heat source at 1200 K loses 2500 kJ of heat to sink at 800 K b. A heat source at 800 K loses 2000 kJ of heat to sink at 500 K Which of the following statements is TRUE? (a) Process I is more irreversible than Process II (b) Process II is more irreversible than Process I (c) Irreversibility associated in both the processes is equal (d) Both the processes are reversible [GATE-2010]
Previous 20-Years IES Questions Available Energy

IES-1. What will be the loss of available energy associated with the transfer of 1000 kJ of heat from constant temperature system at 600 K to another at 400 K when the environment temperature is 300 K? [IES-2004] (a) 150 kJ (b) 250 kJ (c) 500 kJ (d) 700 kJ What is the loss of available energy associated with the transfer of 1000 kJ of heat from a constant temperature system at 600 K to another at 400 K when the environmental temperature is 300 K? [IES-2008]
IES-2.
122
S K Mondals
(a) 150 kJ (b) 250 kJ (c) 16667 kJ
Chapter 5
(d) 180kJ
Available Energy Referred to a Cycle

IES-3. A heat source H1 can supply 6000kJ/min. at 300C and another heat source H2 can supply 60000 kJ/min. at 100C. Which one of the following statements is correct if the surroundings are at 27C? [IES-2006] (a) Both the heat sources have the same efficiency (b) The first heat source has lower efficiency (c) The second heat source has lower efficiency (d) The first heat source produces higher power
Availability
IES-4. Assertion (A): The change in availability of a system is equal to the change in the Gibbs function of the system at constant temperature and pressure. Reason (R): The Gibbs function is useful when evaluating the availability of systems in which chemical reactions occur. [IES-2006] (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true For a steady flow process from state 1 to 2, enthalpy changes from h1 = 400 kJ/kg to h2 = 100 kJ/kg and entropy changes from s1 = 1.1 kJ/kg-K to s2 = 0.7 kJ/kg-K. Surrounding environmental temperature is 300 K. Neglect changes in kinetic and potential energy. The change in availability of the system is: [IES-2003] (a) 420 kJ/kg (b) 300 kJ/kg (c) 180 kJ/kg (d) 90 kJ/kg Availability function for a closed system is expressed as: (a) = u + po v To S (b) = du + po dv To ds [IES-2002]
IES-5.
IES-6.
(c)
IES-7.
= du + po dv + To ds
(d)
= u + po v + To S
[IES-2001] is given by
Consider the following statements: 1. Availability is the maximum theoretical work obtainable. 2. Clapeyron's equation for dry saturated steam
(V
Vf =
dTs hg hf dQ Ts
s p h
3. A gas can have any temperature at a given pressure unlike a vapour which has a fixed temperature at a given pressure. 4. Joule Thomson coefficient is expressed as = Of these statements (a) 1, 2 and 3 are correct (c) 2 and 3 are correct
(b) 1, 3 and 4 are correct (d) 1, 2 and 4 are correct 123
S K Mondals
IES-8.
Chapter 5
10kg of water is heated from 300 K to 350 K in an insulated tank due to churning action by a stirrer. The ambient temperature is 300 K. In this context, match List-I and List-II and select the correct answer using the codes given below the Lists: [IES-2000] List-I List-II A. Enthalpy change 1. 12.2 kJ/kg B. Entropy change/kg 2. 1968 kJ C. Availability/kg 3. 2090 kJ D. Loss of availability 4. 656 J/kg-k Codes: A B C D A B C D (a) 3 1 4 2 (b) 2 4 1 3 (c) 3 4 1 2 (d) 2 1 4 3 Neglecting changes in kinetic energy and potential energy, for unit mass the availability in a non-flow process becomes a = - o, where is the availability function of the [IES-1998] (a) Open system (b) Closed system (c) Isolated system (d) Steady flow process
IES-9.
IES-10.
Consider the following statements: 1. Availability is generally conserved 2. Availability can either be negative or positive 3. Availability is the maximum theoretical work obtainable 4. Availability can be destroyed in irreversibility Of these correct statements are: (a) 3 and 4 (b) 1 and 2 (c) 1 and 3
[IES-1996]
(d) 2 and 4
Irreversibility
IES-11. The irreversibility is defined as the difference of the maximum useful work and actual work: I = Wmax,useful- Wactual. How can this be alternatively expressed?
(a) I = To ( S system + S surrounding ) (c)

IES-12.
(b) I = To ( S system S surrounding ) (d)
[IES-2005]
I = To ( Ssystem + Ssurrounding )
I = To ( Ssystem Ssurrounding )
Assertion (A): All constant entropy processes are adiabatic, but all adiabatic processes are not isentropic. [IES-2006] Reason (R): An adiabatic process which resists the exchange of energy to the surroundings may have irreversibility due to friction and heat conduction. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true Which of the following statement is incorrect? [IES-1992] (a) The greater the pressure difference in throttling the lesser the irreversibility (b) The primary source of internal irreversibility in power is fluid friction in rotary machines. (c) The greater the irreversibility, the greater the increase in adiabatic process 124
IES-13.
S K Mondals
(d) The entropy of the universe is continually on the increase.
Chapter 5
Previous 20-Years IAS Questions Available Energy

IAS-1. What will be the loss of available energy associated with the transfer of 1000 kJ of heat from constant temperature system at 600 K to another at 400 K when the environment temperature is 300 K? [IAS-1995] (a) 150 kJ (b) 250 kJ (c) 500 kJ (d) 700 kJ An inventor claims that heat engine has the following specifications: [IAS-2002] Power developed = 50 kW; Fuel burned per hour = 3 kg Heating value of fuel =75,000 kJ per kg; Temperature limits = 627C and 27C Cost of fuel = Rs. 30/kg; Value of power = Rs. 5/kWh (a) Possible (b) Not possible (c) Economical (d) Uneconomical For a reversible power cycle, the operating temperature limits are 800 K and 300 K. It takes 400 kJ of heat. The unavailable work will be: [IAS-1997] (a) 250 kJ (b) 150 kJ (c) 120 kJ (d) 100 kJ
IAS-2.
IAS-3.
Quality of Energy
IAS-4. Increase in entropy of a system represents (a) Increase in availability of energy (b) Increase in temperature (c) Decrease in pressure (d) Degradation of energy [IAS-1994]
Availability
IAS-5. If u, T, v, s, hand p refer to internal energy, temperature, volume, entropy, enthalpy and pressure respectively; and subscript 0 refers to environmental conditions, availability function for a closed system is given by: [IAS-2003] (a) u + Po v To s (b) u Po v+ To s (c) h + Po v Tos (d) h Po v + To s Match List-I with List-II and below the lists: List-I A. Irreversibility B. Joule Thomson experiment C. Joule's experiment D. Reversible engines Codes: A B C (a) 1 2 3 (c) 4 3 2 select the correct answer using the codes given List-II Mechanical equivalent Thermodynamic temperature scale Throttling process Loss of availability A B C D (b) 1 2 4 3 (d) 4 3 1 2 1. 2. 3. 4.
IAS-6.
D 4 1
125
Irreversibility
IAS-7. The loss due to irreversibility in the expansion valve of a refrigeration cycle shown in the given figure is represented by the area under the line. (a) GB (b) AG (c) AH (d) BH [IAS-1999] IAS-8. Assertion (A): When a gas is forced steadily through an insulated pipe containing a porous plug, the enthalpy of gas is the same on both sides of the plug. [IAS-1997] Reason (R): The gas undergoes an isentropic expansion through the porous plug. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
Second Law efficiency

IAS-9. Assertion (A): The first-law efficiency evaluates the energy quantity utilization, whereas the second-law efficiency evaluates the energy quality utilization. Reason (R): The second-law efficiency for a process is defined as the ratio of change of available energy of the source to the change of available energy of the system. [IAS-1998] (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
126

GATE-1. Ans. (a) A.E =
T2
T mc p 1 o T T1
T2 T = dT mc p ( T2 T1 ) To ln 2 T1 T1
1250 = 2000 0.5 (1250 450 ) 303ln = 490MJ 450 GATE-2. Ans. (d) Maximum useful work, i.e. total work minus pdv work. Not maximum work. GATE-3. Ans. (d) The availability of a thermal reservoir is equivalent to the work output of a Carnot heat engine operating between the reservoir and the environment. Here as there is no change in the temperatures of source (reservoir) or the sink (atmosphere), the initial and final availabilities are same. Hence, there is no loss in availability. GATE-4. Ans. (b)

1000 1000 IES-1. Ans. (b) Loss of available energy = To ( S )univ. = 300 kJ = 250kJ 600 400 IES-2. Ans. (b) Loss of Availability = T0 S T0 = 300K
S =
Q Q T1 T2
1000 1000 Loss of Availability = 300 = 250 kJ 600 400
IES-3. Ans. (c)
= 1
Tource Tsurroundings
1 >2
IES-4. Ans. (b) IES-5. Ans. (c) U.E. = To (s1 s 2 ) = 300 (1.1 0.7) = 120 kJ/kg
Change in availability = (h1 h 2 ) (U.E.) = (400 100) 120 = 180 kJ/kg

IES-6. Ans. (a) IES-7. Ans. (c) The availability of a given system is defined as the maximum useful work that can be obtained in a process in which the system comes to equilibrium with the surroundings or attains a dead state. Clearly, the availability of a system depends on the condition of the system as well as those of the surroundings.
127
IES-8. Ans. (c) IES-9. Ans. (a) IES-10. Ans. (a) Availability is the maximum theoretical work obtainable and it can be destroyed in irreversibility. IES-11. Ans. (a) I = To ( S )universe = To Ssystem + Ssurrounding IES-12. Ans. (d) A is false, For a process due to irreversibility entropy will increase and actual process may be 12' but due to heat loss to the surroundings, may 2' coincide with 2 but the process not adiabatic. So, all isentropic process is not adiabatic. IES-13. Ans. (a)

1000 1000 IAS-1. Ans. (b) Loss of available energy = To ( S )univ. = 300 kJ = 250kJ 600 400
IAS-2. Ans. (b) Maximum possible efficiency (max) = 1
T2 300 2 = 1 = 900 3 T1
Maximum possible Power output with this machine (Wmax) = Q max =
So above demand is impossible.
3 75000 2 kW 41. 67 KW 3600 3
T 300 IAS-3. Ans. (b) Available part of the heat (WE) = Q 1 2 = 400 1 = 250 kJ T 800 1 Unavailable work (Wu) = 400 250 = 150 kJ 1250 = 2000 0.5 (1250 450 ) 303ln = 490MJ s 450 IAS-4. Ans. (d) IAS-5. Ans. (a) IAS-6. Ans. (d) 128
IAS-7. Ans. (d) Entropy will increase in the process AH is BH. Therefore Irreversibility (I) = To S i.e. area under the line BH. IAS-8. Ans. (c) Expansion through the porous plug is adiabatic as no heat added or rejected to the system. It is not reversible, due to large irreversibility entropy increases so it is not an isentropic process. mimimum energy int ake to perform the given task IAS-9. Ans. (c) II = actual energy int ake to perform the same task
129
Thermodynamic Relations
6.
2 N

Adiabatic index () =1+ where N is degrees of freedom of molecules N=3 for monatomic gas N=5 for diatomic gas N=6 for try atomic gas.
Some Mathematical Theorem

Theorem 1. If a relation exists among the variables x, y and z, then z may be expressed as a function of x and y, or z z dz = dx + dy x y y x
then dz = M dx + N dy. where z, M and N are functions of x and y. Differentiating M partially with respect to y, and N with respect to x.
2z M y = x.y x 2 z N x = y.x y M N y = x y x This is the condition of exact (or perfect) differential.
Theorem 2. If a quantity f is a function of x, y and z, and a relation exists among x, y and z, then f is a function of any two of x, y and z. Similarly any one of x, y and z may be regarded to be a function of f and any one of x, y and z. Thus, if x = x (f, y) x x dx = df + dy f y y f
Similarly, if
y = y (f, z) y y dy = df + dz z f f z Substituting the expression of dy in the preceding equation
130
S K Mondals
x x dx = df + f y y f y y df + dz z f f z x x y x y = + df + dz y f z f f y y f f z Again x x dx = df + dz z f f z x y x z = y z f f f x y z y z x = 1 f f f
Chapter 6
Theorem 3. Among the variables x, y, and z any one variable may be considered as a function of the other two. Thus x = x(y, z) x x dx = dy + dz z y y z
Similarly, z z dz = dx + dy x y y x x z x z dx = dy + dx + dy z y y z y x x y x x z x z = + dy + dx y z y z y x y z y x x x z = + dy + dx y z z y y x x z x + = 0 y z y x z y x z y y x z = 1 z y x Among the thermodynamic variables p, V and T. The following relation holds good p V T V T p = 1 T p v
Maxwells Equations:131
A pure substance existing in a single phase has only two independent variables. Of the eight quantities p, V, T, S, U, H, F (Helmholtz function), and G (Gibbs function) any one may be expressed as a function of any two others. For a pure substance undergoing an infinitesimal reversible process (a) dU = TdS - pdV (b) dH = dU + pdV + VdP = TdS + Vdp (c) dF = dU - TdS - SdT = - pdT - SdT (d) dG = dH - TdS - SdT = Vdp - SdT Since U, H, F and G are thermodynamic properties and exact differentials of the type dz = M dx + N dy, then M N = y x x y Applying this to the four equations T p V = S s v
T V P = S s p p S T = V V T S V T = p P T These four equations are known as Maxwells equations.
(i) Derive:
dS = Cv
dT p + dV T T v
[IAS - 1986]
Let entropy S be imagined as a function of T and V.
132
S K Mondals
Then S = S ( T, V ) S S or dS = dT + dV T V V T multiplying both side by T S S TdS = T dT + T dV T V V T S T = CV , heat capacity at constant volume T V p S V = T by Maxwell 's equation V T p TdS = CV dT + T dV T V dT p + dV proved T T V
Chapter 6
Since and
dividing both side by T dS = C V
(ii) Derive:
V TdS = CpdT T dp T p
Let entropy S be imagined as a function of T and p.
[IES-1998]
Then S = S ( T, p) S S or dS = dT + dp T p p T multiplying both side by T S S TdS = T dT + T dp T p p T Since and S T = Cp , heat capacity at constant pressure T p S V p = T by Maxwell 's equation p T V TdS = CpdT T dp T p proved.
(iii) Derive:
133
k Cp dp CV TdS = CV dT + T dV = CpdT TV dp = dV + k V
[IES-2001]
We know that volume expansivity () = and
1 V V T p
1 V V p T
isothermal compressibility (k) =
From first TdS equation

p TdS = C V dT + T dV T V V T p V p = = k V T p V T p T
As or
V T p T p V = 1 p T V V p p = T p V T T V p = k T V TdS = CV dT + T dV k proved
From second TdS relation
V TdS = CpdT T dp T p as = 1 V V T p
V T = V p TdS = CpdT TV dp
proved
Let S is a function of p, V S = S(p, V)

S S dS = dp + dV p V V p
134
S K Mondals
Multiply both side by T
S S TdS = T dp + T dV p V p V or or S T S T TdS = T dp + T dV T V p T p V S T S T TdS = T dp + T dV T V p V T p V p S Cp = T T p
and
Chapter 6
S CV = T T V
T T TdS = Cp dp + C V V dV p p V p = k T V
or k T = p V
From first
TdS = Cp
k T dp + CV dV V p
1 V V T p
1 T V = V p C k dp C V TdS = p dV + V
proved.
(iv) Prove that
V p Cp Cv = T T p V T
We know that
[IAS-1998]
135
S K Mondals
V p TdS = CpdT T dp = CV dT + T dV T p T V or V p T dp + T dV T p T V (i )
Chapter 6
(C
Cv ) dT =
or
V p T dp T dV T T p V + dT = Cp C V Cp CV T = T ( p, V )
sin ce T is a function of p, V T T dT = dp + dV V p p V ( ii )
or
comparing ( i ) & ( ii ) we get V T T p T = Cp CV p V both these give p T T T V = and Cp CV V p
V p Cp CV = T T p T V
Here p T V p V p T V p = 1 or T = T V V p V p T T V p Cp CV = T T p V T
2
2
proved.
...............Equation(A)
This is a very important equation in thermodynamics. It indicates the following important facts.
V p (a) Since is always positive, and V for any substance is negative. (Cp Cv) is always T p T positive. Therefore, Cp is always greater than Cv. (b) As T 0 K ,C p Cv or at absolute zero, Cp = Cv.
V (c) When = 0 (e.g for water at 4C, when density is maximum. Or specific volume minimum). T p C p = C v.
(d) For an ideal gas, pV = mRT
136
S K Mondals
mR V V T = P = T p
and
Chapter 6
mRT p V = V2 T C p Cv = mR
or c p cv = R
Equation (A) may also be expressed in terms of volume expansively () defined as 1 V = V T p and isothermal compressibility (kT) defined as 1 V kT = V p T
1 V TV V T p C p Cv = 1 V V p T C p Cv = TV 2 kT
Ratio of heat capacities
At constant S, the two TdS equations become V C p dTs = T dps T p

p Cv dTs = T dVs T v p Cp V T p V = = Cv T p p v V s p V since > 1, p p V > V s T Therefore, the slope of an isentropic is greater than that of an isotherm on p-v diagram (figure below). For reversible and adiabatic compression, the work done is S = T
Ws = h2 s h1 = vdp
1
2s
= Area 1- 2 s - 3 - 4 - 1
137
Therm T modyna amic Relatio R ons

(Fig. Co ompression Work in Dif fferent Rev versible Pro ocess) a isotherm mal compress sion, the wor rk done would d be For reversible and
2T
WT = h2T h1 = WT < Ws
dp vdp
1
= Area A 1-2T - 3 - 4 - 1
For polytropic compression n with 1 < n < . the work done wi ill be betwee en these two o values. So iso othermal com mpression min nimum work. Th he adiabatic compressibili c ity (ks) is defi ined as 1 V or ks = V p s
1 V p Cp V T = = Cv 1 V V p s
k ks
En nergy Equ uation

For a system undergoing u an a infinitesimal reversib ble process between b two equilibrium m states, the ange of inter rnal energy is s cha dU = TdS - pdV p ubstituting th he first TdS equation e Su p dU = Cv dT + T dV pdV T V
p p dV = Cv dT + T T V if U = (T ,V ) U U dT + dU = dV V T T V p U V = T T p V T Th his is known as a energy equ uation. Two application a o the equatio of on are given belowb 138 8
S K Mondals
(a) For an ideal gas, p =
nRT V
Chapter 6
nR p p = V =T T V p U = T. p = 0 T V T U does not change when V changes at T = C. U p V =1 p T V T U T

U p U = =0 p T V T V T U p since 0, p = 0 V T T U does not change either when p changes at T = C. So the internal energy of an ideal gas is a function of temperature only. Another important point to note is that for an ideal gas p pV = nRT and T p=0 T v Therefore dU = Cv dT holds good for an ideal gas in any process (even when the volume changes). But for any other substance dU = Cv dT is true only when the volume is constant and dV = 0 Similarly
dH = TdS + Vdp
and
V TdS = Cp dT T dp T p V dH = C p dT + V T dp T p H V = V T p T p T
As shown for internal energy, it can be similarly proved from Eq. shown in above that the enthalpy of an ideal gas is not a function of either volume or pressure. H H = 0 i.e = 0 and V T p T but a function of temperature alone. Since for an ideal gas, pV = nRT V and V T =0 T p the relation dH = Cp dT is true for any process (even when the pressure changes.) 139
However, for any other substance the relation dH = Cp dT holds good only when the pressure remains constant or dp = 0. (b) Thermal radiation in equilibrium with the enclosing walls processes an energy that depends only on the volume and temperature. The energy density (u), defined as the ratio of energy to volume, is a function of temperature only, or U u = = f (T )only. V The electromagnetic theory of radiation states that radiation is equivalent to a photon gas and it exerts a pressure, and that the pressure exerted by the black body radiation in an enclosure is given by u p= 3 Black body radiation is thus specified by the pressure, volume and temperature of the radiation. since. u U = uV and p = 3 1 du U p V = u and T = 3 dT T V By substituting in the energy Eq. T du u u= 3 dT 3 du dT =4 u T or ln u = ln T4 + lnb or u = bT4 where b is a constant. This is known as the Stefan - Boltzmann Law. Since U = uV = VbT 4 U 3 T = Cv = 4VbT V 1 du 4 p 3 T = 3 dT = 3 bT V
and
From the first TdS equation p TdS = Cv dT + T dV T v

4 = 4VbT 3 dT + bT 4 .dV 3 For a reversible isothermal change of volume, the heat to be supplied reversibly to keep temperature constant. 4 Q = bT 4 V 3 For a reversible adiabatic change of volume
140
4 bT 4 dV = 4VbT 3 dT 3 dV dT or = 3 V T or VT3 = const If the temperature is one-half the original temperature. The volume of black body radiation is to be increased adiabatically eight times its original volume so that the radiation remains in equilibrium with matter at that temperature.
(v) Prove that
p = k T V
Hence show that Cp Cv = 2 TV k
and
U V Cp CV = p + V T T p
[IES - 2003]
Here =
1 V V T p 1 V V p T
k=
V T p V p = = k V T p V T p T V T p T p V = 1 p T V V p p = T p V T T V proved.
we know that or
p = k T V
From Tds relations
141
S K Mondals
V p TdS = CpdT T dP = C V dT + T T dV T p V
Chapter 6
(C
V p C v ) dT = T dP + T T dV T p v
or
V p T T T T p V dV i dT = dP + () Cp C V Cp CV T = T ( p, V )
S in ce T is a function of ( p, V ) T T dT = dp + V dV p p V ( ii )
Compairing ( i ) & ( ii ) we get V T T p T = Cp C V p V as

or or
and
p T T V = T Cp CV V p
V p Cp CV = T T p T V dU = dQ pdV
dU = TdS pdV U S V = T V p T T U S V + p = T V T T
From Maxwell 's Third relations p S T = V V T V p U V Cp CV = T = p + T p T V V T T p
(vi) Prove that

Joule Thomson co-efficient
T2 V T = = C T T p p h p
[IES-2002]
The numerical value of the slope of an isenthalpic on a T p diagram at any point is called the Joule Kelvin coefficient.
142
S K Mondals
Here as if so T = p h dH = TdS + Vdp V TdS = CpdT T dp T p V V dH = CpdT T dp + Vdp = CpdT T V dp T p T p H = cos t. dH = 0 V Cp ( dT )h T V ( dp)h = 0 T p T 2 1 V V T2 V 1 V T T V = = T 2 = C T T p C T T T p p h Cp p p p
Chapter 6
(vii) Derive clausius clapeyron equation

hfg dp = dT T ( vg v f )
p S T = V V T
and
h dp = fg2 dT p RT
[IES-2000]
Maxwells equation
When saturated liquid convert to saturated vapour at constant temperature. During the evaporation, the pr. & T is independent of volume.
sg s f dp dT = v v sat g f sg sf = sfg = h fg T
or
h fg dp = dT sat T ( v g v f )
It is useful to estimate properties like h from other measurable properties. At a change of phage we may find h fg i.e. latent heat.
143
S K Mondals
At very low pressure v g v f g as v f very small pv g = RT or vg = RT p
Chapter 6
h fg h fg h p dp = = = fg 2 RT dT T v g T RT p
or or
dp h fg dT = p R T2 p h fg 1 1 ln 2 = R T1 T2 p1
Knowing vapour pressure p1 at temperature T1, we may find out p2 at temperature T2.
Joule-Kelvin Effect or Joule-Thomson coefficient

The value of the specific heat cp can be determined from pvT data and the JouleThomson coefficient. The JouleThomson coefficient J is defined as
J = p h
Like other partial differential coefficients introduced in this section, the JouleThomson coefficient is defined in terms of thermodynamic properties only and thus is itself a property. The units of J are those of temperature divided by pressure. A relationship between the specific heat cp and the JouleThomson coefficient J can be established to write
T p h p h T = 1 p h T
The first factor in this expression is the JouleThomson coefficient and the third is cp. Thus 144

S K Mondals
cp =
Wi ith ( h / p )T = 1 / ( p / h )T
Cha apter 6
1 J ( p / h )T
1 h J p T
t this can be written as
cp =
Th he partial der rivative ( h / p )T , called the constan nt-temperat ture coeffici ient, can be eliminated. Th he following expression e re esults:
cp =
1 v v T J T p
allows the valu ue of cp at a state to be e determined d using pvT T data and the value of f the Joule Th homson coeffi icient at tha at state. Let us consider next how th he JouleTho omson coeffic cient can be fou und experime entally. Th he numerical value of the slope of an isenthalpic i on a T-p diagram at any point p is called the JouleKelvin coefficie ent and is denoted d by J . Thus the locus of all l points at which w J is zero is the version curve e. The regio on inside the e inversion curve c where J is positive is called the cooling inv reg gion and the region outsid de where J is negative is i called the heating h regio on. So,
J = p h
G Gibbs Phase Rule R

Gibbs Ph hase Rule determines wha at is expected d to define th he state of a system s
F=CP+2
145 5
S K Mondals
F = Number of degrees of freedom (i.e.., no. of properties required) C = Number of components P = Number of phases e.g., Nitrogen gas C = 1; P = 1. Therefore, F = 2 To determine the state of the nitrogen gas in a cylinder two properties are adequate. A closed vessel containing water and steam in equilibrium: P = 2, C = 1 Therefore, F = 1. If any one property is specified it is sufficient. A vessel containing water, ice and steam in equilibrium P = 3, C = 1 therefore F = 0. The triple point is uniquely defined.
Chapter 6
146
ASKED OBJECTIVE QUESTIONS (GATE, IES, IAS) Previous 20-Years GATE Questions Maxwell's Equations
GATE-1. Which of the following relationships is valid only for reversible processes undergone by a closed system of simple compressible substance (neglect changes in kinetic and potential energy? [GATE-2007] (a) Q = dU + W (b) TdS = dU + pdV (c) TdS = dU + W (d) Q = dU + pdV Considering the relationship TdS = dU + pdV between the entropy (S), internal energy (U), pressure (p), temperature (T) and volume (V), which of the following statements is correct? [GATE-2003] (a) It is applicable only for a reversible process (b) For an irreversible process, TdS > dU + pdV (c) It is valid only for an ideal gas (d) It is equivalent to 1 law, for a reversible process
GATE-2.
Difference in Heat Capacities and Ratio of Heat Capacities

GATE-3. The specific heats of an ideal gas depend on its [GATE-1996] (a) Temperature (b) Pressure (c) Volume (d) Molecular weight and structure The specific heats of an ideal gas depends on its [GATE-1996] (a) Temperature (b) Pressure (c) Volume (d) Molecular weight and structure For an ideal gas the expression T
GATE-4.
GATE-5.
s s T is always equal to: T T v p

[GATE-1997]
(a ) zero
GATE-6.
(b)
cp cv
(c ) R
(d ) RT
A 2 kW, 40 litre water heater is switched on for 20 minutes. The heat capacity Cp for water is 4.2 kJ/kg K. Assuming all the electrical energy has gone into heating the water, increase of the water temperature in degree centigrade is: [GATE-2003] (a) 2.7 (b) 4.0 (c) 14.3 (d) 25.25

GATE-7. Which combination of the following statements is correct? [GATE-2007]
147
P: A gas cools upon expansion only when its Joule-Thomson coefficient is positive in the temperature range of expansion. Q: For a system undergoing a process, its entropy remains constant only when the process is reversible. R: The work done by a closed system in an adiabatic process is a point function. S: A liquid expands upon freezing when the slop of its fusion curve on Pressure Temperature diagram is negative. (a) R and S (b) P and Q (c) Q, R and S (d) P, Q and R GATE-8. A positive value to Joule-Thomson coefficient of a fluid means (a) Temperature drops during throttling (b) Temperature remains constant during throttling (c) Temperature rises during throttling (d) None of these [GATE-2002]
GATE-9.
A gas having a negative Joule-Thompson coefficient ( < 0), when throttled, will: [GATE-2001] (a) Become cooler (b) Become warmer (c) Remain at the same temperature (d) Either be cooler or warmer depending on the type of gas [GATE-1994]
GATE-10. Match 4 correct pairs between List-I and List-II for the questions For a perfect gas: List-I List-II (a) Isobaric thermal expansion coefficient 1. 0 (b) Isothermal compressibility 2. (c) Isentropic compressibility 3. 1/v (d) Joule Thomson coefficient 4. 1/T 5. 1/p 6. 1/ p
Previous 20-Years IES Questions Some Mathematical Theorems

IES-1. Given: [IES-1993] p = pressure, T = Temperature, v = specific volume Which one of the following can be considered as property of a system?
(a ) pdv
(b) vdp
dT p.dv (c ) + v T
dT v.dp (d ) T T
Maxwell's Equations
IES-2. Which thermodynamic property is evaluated with the help of Maxwell equations from the data of other measurable properties of a system? [IES 2007] (a) Enthalpy (b) Entropy (c) Latent heat (d) Specific heat 148
S K Mondals
IES-3.
Chapter 6
Consider the following statements pertaining to the Clapeyron equation: 1. It is useful to estimate properties like enthalpy from other measurable properties. [IES-2006] 2. At a change of phase, it can be used to find the latent heat at a given pressure. 3. It is derived from the relationship
p s = v T T V
(d) Only 2 and 3
[IES-2011]
Which of the statements given above are correct? (a) 1,2 and 3 (b) Only 1 and 2 (c) Only 1 and 3 IES-3a Clapeyrons equation is used for finding out the (a) Dryness fraction of steam only (b) Entropy of superheater vapour only (c) Specific volume at any temperature and pressure (d) Total heat of superheated steam only
TdS Equations
IES-4. T ds equation can be expressed as:
T dv k Tk dv (c) Tds = Cv dT +
(a) Tds = Cv dT +
[IES-2002]
Tdv k T (d) Tds = Cv dT + dp k

(b) Tds = Cv dT +
IES-5.
Which one of the following statements applicable to a perfect gas will also be true for an irreversible process? (Symbols have the usual meanings). [IES-1996] (a) dQ = du + pdV (b) dQ = Tds (c) Tds = du + pdV (d) None of the above Consider the following thermodynamic relations:
IES-6.
1.Tds = du + pdv 3.Tds = dh + vdp
2.Tds = du pdv 4.Tds = dh vdp
[IES-2000]
Which of these thermodynamic relations are correct? (a) 1 and 3 (b) 1 and 4 (c) 2 and 3
(d) 2 and 4

IES-7. Match List-l (Terms) with List-II (Relations) and select the correct answer using the codes given below the Lists: [IES-2003] List-I (Terms) List-II (Relations) A. Specific heat at constant volume, Cv 1 v 1. B. Isothermal compressibility kT 2.
v T p p v T T v T p
149
S K Mondals
C. Volume expansivity D. Difference between specific heats at constant pressure and at constant Cp Cv Codes: (a) (c) IES-8. A 3 3 B 4 4 C 2 1 D 1 2 3. 4.
Chapter 6
s T T v 1 v v p T
B 1 1 C 3 2 D 2 3
(b) (d)
A 4 4
Assertion (A): Specific heat at constant pressure for an ideal gas is always greater than the specific heat at constant volume. [IES-2002] Reason (R): Heat added at constant volume is not utilized for doing any external work. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true An insulated box containing 0.5 kg of a gas having Cv = 0.98 kJ/kgK falls from a balloon 4 km above the earths surface. What will be the temperature rise of the gas when the box hits the ground? [IES-2004] (a) 0 K (b) 20 K (c) 40 K (d) 60 K As compared to air standard cycle, in actual working, the effect of variations in specific heats is to: [IES-1994] (a) Increase maximum pressure and maximum temperature (b) Reduce maximum pressure and maximum temperature (c) Increase maximum pressure and decrease maximum temperature (d) Decrease maximum pressure and increase maximum temperature The number of degrees of freedom for a diatomic molecule (a) 2 (b) 3 (c) 4 The ratio [IES-1992] (d) 5 [IES-1992]
IES-9.
IES-10.
IES-11. IES-12.
Cp Cv
for a gas with n degrees of freedom is equal to:
(a) n + I
IES-13.
(b) n I
(c)
Molal specific heats of an ideal gas depend on [IES-2010] (a) Its pressure (b) Its temperature (c) Both its pressure and temperature (d) The number of atoms in a molecule
Assertion (A): Ratio of specific heats
Cp Cv
2 1 n
(d) 1 +
2 n
IES-14.
decreases with increase
in
temperature. [IES-1996] Reason (R): With increase in temperature, C p decreases at a higher rate than C v. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A
150
S K Mondals
(c) A is true but R is false (d) A is false but R is true
IES-15. It can be shown that for a simple compressible substance, the relationship
Chapter 6
V P Cp Cv = T exists. T p v T
2
[IES-1998]
Where C p and C v are specific heats at constant pressure and constant volume respectively. T is the temperature V is volume and P is pressure. Which one of the following statements is NOT true? (a) C p is always greater than C v. (b) The right side of the equation reduces to R for ideal gas.
(c) Since
V P must be positive, T can be either positive or negative, and v T T p P must have a sign that is opposite to that of v T
2
(d) Is very nearly equal to for liquid water.

IES-16. Joule-Thomson coefficient is defined as: [IES-1995]
T (a) p h
IES-17.
h (b) p T
h (c) T p
(d)
p T h
The throttling of certain gasses may be used for getting the refrigeration effect. What is the value of Joule Thomson coefficient () for such a throttling process? [IES-2007] (a) = 0 (b) = 1 (c) < 1 (d) > 1 Which one of the following is correct? [IES 2007] When a real gas undergoes Joule-Thomson expansion, the temperature (a) May remain constant (b) Always increases (c) May increase or decrease (d) Always decreases Assertion (A): Throttling process for real gases at initial temperature higher than maximum inversion temperature is accompanied by decrease in temperature of the gas. [IES-2003] Reason (R): Joule-Kelvin coefficient j is given ( T / p ) h and should have a positive value for decrease in temperature during throttling process. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
IES-18.
IES-19.
IES-20.
Match List-I (Name of entity) with List-II (Definition) and select the correct answer using the codes given below the lists: [IES-2001] List-I (Name of entity) List-II (Definition) 151
S K Mondals
A. Compressibility factor B. Joule Thomson coefficient C. Constant pressure specific heat D. Isothermal compressibility Codes: (a) (c) IES-21. A 2 2 B 1 3 C 4 4 D 3 1
Chapter 6
1 v v p T h 2. T p
1. 3. 4.
T p h
pv RT
A 4 4 B 3 1 C 2 2 D 1 3
(b) (d)
Joule Thomson coefficient is the ratio of [IES-1999] (a) Pressure change to temperature change occurring when a gas undergoes the process of adiabatic throttling (b) Temperature change to pressure change occurring when a gas undergoes the process of adiabatic throttling (c) Temperature change to pressure change occurring when a gas undergoes the process of adiabatic compression (d) Pressure change to temperature change occurring when a gas undergoes the process of adiabatic compression The Joule Thomson coefficient is the [IES-1996]
IES-22.
(a)
T of pressure-temperature curve of real gases p h T of temperature-entropy curve of real gases p v
(b) (c)
h of enthalpy-entropy curve of real gases s T V (d) of pressure-volume curve of real gases T p

IES-23. Match the following: List-I A. Work B. Heat C. Internal energy D. Joule Thomson Coefficient Code: A B C D List-II 1. Point function 2. [IES-1992]
Tds
u T h
3. 4.
pdv
152
S K Mondals
(a) (c) 4 4 2 1 1 2 3 3 (b) (d) 1 2 2 1 4 4
Chapter 6
3 3
Clausius-Clapeyron Equation
IES-24. Consider the following statements in respect of the Clausius Clapeyron equation: [IES-2007] 1. It points to one possible way of measuring thermodynamic temperature. 2. It permits latent heat of vaporization to be estimated from measurements of specific volumes of saturated liquid, saturated vapour and the saturation temperatures at two nearby pressures. 3. It does not apply to changes from solid to the liquid phase and from solid to the Vapour phase. Which of the statements given above are correct? (a) 1, 2 and 3 (b) 1 and 2 only (c) 2 and 3 only (d) 1 and 3 only The equation relating the following measurable properties: [IES-2005] (i) The slope of saturation pressure temperature line (ii) The latent heat, and (iii) The change in volume during phase transformation; is known as: (a) Maxwell relation (b) Joules equation (c) Clapeyron equation (d) None of the above The variation of saturation pressure with saturation temperature for a liquid is 0.1 bar/K at 400 K. The specific volume of saturated liquid and dry saturated vapour at 400 K are 0.251 and 0.001 m3/kg What will be the value of latent heat of vaporization using Clausius Clapeyron equation? [IES-2004] (a) 16000 kJ/kg (b) 1600 kJ/kg (c) 1000 kJ/kg (d) 160 kJ/kg If h, p, T and v refer to enthalpy, pressure, temperature and specific volume respectively and subscripts g and f refer to saturation conditions of vapour and liquid respectively then Clausius-Clapeyron equation applied to change of phase from liquid to vapour states is: [IES-1996, 2006]
IES-25.
IES-26.
IES-27.
(a)
dp (hg h f ) = dt (vg v f )
(b)
dp (hg h f ) = dt T (vg v f )
dp (vg v f )T = dt (hg h f )
(c)
dp (hg h f ) = dt T
(d)
IES-28.
Which one of the following functions represents the Clapeyron equation pertaining to the change of phase of a pure substance? [IES-2002] (a) f (T, p, hfg) (b) f (T, p, hfg, vfg) (c) f (T, p, hfg, sfg) (d) f (T, p, hfg, sfg, vfg) The Clapeyron equation with usual notations is given by: [IES-2000]
IES-29.
dT (a) = dP sat Tv fg h fg
IES-30.
dP (b) = dT sat Tv fg h fg
dT (c) = dP sat v fg
Th fg
Th fg dP (d ) = dT sat v fg
Clausius-Clapeyron equation gives the 'slope' of a curve in [IES-1999] (a) pv diagram (b) ph diagram (c) pT diagram (d) TS diagram
153
S K Mondals
IES-31.
Chapter 6
The thermodynamic parameters are: [IES-1997] I. Temperature II. Specific Volume III. Pressure IV. Enthalpy V. Entropy The Clapeyron Equation of state provides relationship between: (a) I and II (b) II, III and V (c) III, IV and V (d) I, II, III and IV
Gibbs Phase Rule

IES-32. Number of components (C), phase (P) and degrees of freedom (F) are related by Gibbs-phase rule as: [IES-2001] (a) C P F = 2 (b) F C P = 2 (c) C + F P = 2 (d) P + F C = 2 As per Gibb's phase rule, if number of components is equal to 2 then the number of phases will be: [IES-2002] (a) 2 (b) 3 (c) 4 (d) 5 Gibb's phase rule is given by: [IES-1999] (F = number of degrees of freedom; C = number of components; P = number of phases) (a) F = C + P (b) F = C + P 2 (c) F = C P 2 (d) F = C P + 2 Gibb's free energy 'c' is defined as: (a) G = H TS (b) G = U TS
IES-33.
IES-34.
IES-35.
(c) G = U + pV
[IES-1999] (d) G = H + TS
IES-36.
Which one of the following relationships defines the Helmholtz function F? [IES-2007] (a) F = H + TS (b) F = H TS (c) F = U TS (d) F = U +TS Assertion (A): For a mixture of solid, liquid and vapour phases of a pure substance in equilibrium, the number of independent intrinsic properties needed is equal to one. [IES-2005] Reason(R): The Three phases can coexist only at one particular pressure. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true Consider the following statements: [IES-2000] 1. Azeotropes are the mixtures of refrigerants and behave like pure substances. 2. Isomers refrigerants are compounds with the same chemical formula but have different molecular structures. 3. The formula n + p + q = 2m is used for unsaturated chlorofluorocarbon compounds (m, n, p and q are the numbers atoms of carbon, hydrogen, fluorine and chlorine respectively). Which of these statements are correct? (a) 1 and 3 (b) 2 and 3 (c) 1 and 2 (d) 1, 2 and 3
IES-37.
IES-38.
154
Previous 20-Years IAS Questions Maxwell's Equations

IAS-1. According to the Maxwell relation, which of the following is/are correct?
v s = T p P T P s (c) = T v v T
(a)
(b)
s P = v T T v
[IAS-2007]
(d) All of the above
TdS Equations
IAS-2. Which one of the following expressions for T ds is true for a simple compressible substance? (Notations have the usual meaning) [IAS-1998] (a) dh vdp (b) dh + vdp (c) dh pdv (d) dh + pdv

IAS-3. The specific heat Cp is given by: [IAS-2000]
v (a) T T p
IAS-4.
T (b) T s p
s (c) T T p
(d)
T T v p
For an ideal gas the expression T
s s T is always equal to: T v T p
(a ) zero
IAS-5.
(b)
cp cv
(c ) R
(d ) RT
[IAS-2003]
Assertion (A): Specific heat at constant pressure for an ideal gas is always greater than the specific heat at constant volume. [IAS-2000] Reason (R): Heat added at constant volume is not utilized for doing any external work. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true Match List-I with List-II and select the correct answers using the codes given below the lists. [IAS-2002] List-I List-II A. Joule Thomson co-efficient 1.
IAS-6.
5 R 2
B. Cp for monatomic gas

155
2. Cv
S K Mondals
C. Cp Cv for diatomic gas D. 3. R
T 4. P h
Chapter 6
U T v
A 3
3
Codes: (a)
(c)
B 2
1
C 4
4
D 1
2
(b) (d)
A 4
4
B 1
2
C 3
3
D 2
1
IAS-7.
Ratio of specific heats for an ideal gas is given by (symbols have the usual meanings) [IAS-1999]
(a)
1 1 R Cp
(b)
1 C 1 p R
(c)
1 C 1+ p R
(d)
1 1+ R Cp

IAS-8. Which one of the following properties remains unchanged for a real gas during Joule-Thomson process? [IAS-2000] (a) Temperature (b) Enthalpy (c) Entropy (d) Pressure
Clausius-Clapeyron Equation
IAS-9. If h, p, T and v refer to enthalpy, pressure, temperature and specific volume respectively and subscripts g and f refer to saturation conditions of vapour and liquid respectively then Clausius-Clapeyron equation applied to change of phase from liquid to vapour states is: [IAS-2003]
(a)
dp (hg h f ) = dt (vg v f )
(b)
dp (hg h f ) = dt T (vg v f ) dp (vg v f )T = dt (hg h f )
(c)
dp (hg h f ) = dt T
(d)
IAS-10.
Which one of the following is the correct statement? [IAS-2007] Clapeyron equation is used for: (a) Finding specific volume of vapour (b) Finding specific volume of liquid (c) Finding latent heat of vaporization (c) Finding sensible heat Assertion (A): Water will freeze at a higher temperature if the pressure is increased. [IAS-2003] Reason (R): Water expands on freezing which by Clapeyron's equation gives negative slope for the melting curve. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
156
IAS-11.
S K Mondals
IAS-12.
Chapter 6
Match List-I with List-II and select the correct answer using the codes given below the lists [IAS-1994] List-I List-II A. Mechanical work 1. Clausius-Clapeyron equation B.
C. Zeroth Law D. HTS Codes: A (a) 1 (c)
dQ 0 T
2. Gibb's equation 3. High grade energy 4. Concept of temperature A B C (b) 3 2 (d) 3 4
B 3 2
C 2 3
D 4 1
D 4 2
Gibbs Phase Rule

IAS-13. Which one of the following relationships defines Gibb's free energy G? [IAS-2007] (a) G = H + TS (b) G = H TS (c) G = U + TS (d) G = U TS The Gibbs free-energy function is a property comprising [IAS-1998] (a) Pressure, volume and temperature (b) Ethalpy, temperature and entropy (c) Temperature, pressure and enthalpy (d) Volume, ethalpy and entropy
IAS-14.
157

GATE-1. Ans. (d) GATE-2. Ans. (d) GATE-3. Ans. (a) GATE-4. Ans. (d)
S TS dQ GATE-5. Ans. (c) T = = = CP T P T P T P S TS dQ T = T = T = C V T V V V
S S T T = CP CV = R T P T V GATE-6. Ans. (c) Heat absorbed by water = Heat supplied by heater. m w c pw ( T ) w = P t or 40 4.2 ( T ) w = 2 20 60 or ( T ) w = 14.3o C
GATE-7. Ans. (b)

T GATE-8. Ans. (a) = i,e. > o, P is ( ive ) so T must be ive. P h T T GATE-9. Ans. (b) Joule-Thomson co-efficient . Here, p, ive and P , -ive so T must be P h h +ive so gas will be warmer. GATE-10. Ans. (a) 4, (b) 5, (c) 6, (d) 1

IES-1. Ans. (d) P is a function of v and both are connected by a line path on p and v coordinates.
Thus If X and Y are two properties of a system, then dx and dy are exact differentials. If the differential is of the form Mdx + Ndy, then the test for exactness is Now applying above test for
2 R dT p.dv (1/ T ) ( p / v) ( RT / v ) + , or 0 = 2 = = v v T T v v T T v
pdv and vdp are not exact differentials and thus not properties.
M N = y x x y
This differential is not exact and hence is not a point function and hence
dT
p.dv is not a point function and hence not a property. v

158
S K Mondals
And for
Chapter 6
v.dp (1/ T ) ( v / T ) ( R / P ) or 0 = 0 = = T p T T P T P dT v.dp Thus is exact and may be written as ds, where s is a point function and T T
dT
hence a property IES-2. Ans. (a) From Maxwell relation Clapeyron equation comes.
IES-3. Ans. (b) 3 is false. It is derived from the Maxwells 3rd relationship
p s = T v v T
IES-3a Ans. (c) IES-4. Ans. (a) IES-5. Ans. (c) The relations in (a) and (b) are applicable for a reversible processes and (c) Tds = du + pdV is a relation among properties which are independent of the path. IES-6. Ans. (b) IES-7. Ans. (c) IES-8. Ans. (a) IES-9. Ans. (c) Potential energy will converted to heat energy. gh 980 4000 = = 40K mgh = mc v T or T = cv 980 IES-10. Ans. (b) IES-11. Ans. (d) A diatomic gas (such as that of oxygen) has six degrees of freedom in all-three corresponding to translator motion, two corresponding to rotatory motion and one corresponding to vibratory motion. Experiments have shown that at ordinary temperatures, the vibratory motion does not occur. Hence, at 27C, an oxygen molecule has just five degrees of freedom. IES-12. Ans. (d)
IES-13. Ans. (b) For ideal gas CP and CV are constant but mole is depends on the number of atoms in a molecule. IES-14. Ans. (c). A is correct but R is false. We know that C p = a+KT+K1T2+K2T3 C v = b+ KT+K1T2+K2T3 See Cp and C v both increase with temperature and by same amount. As Cp > C v then C percentage increase of Cp is less than C v. So p decreases with temperature. Cv IES-15. Ans. (c) Sign of T must be positive
P is always negative. v T
IES-16. Ans. (a) IES-17. Ans. (d) Actually Joule Thomson coefficient will be positive. IES-18. Ans. (c) For ideal gas = 0 and for real gas may be positive (N2, O2, CO2 etc.) or negative (H2).
159

S K Mondals
IES-19. Ans. (d) When a real gas whi ich is initia ally at a tem mperature lower than the maximum inversion tem mperature is throttled, tem its mperature decreases.
Cha apter 6
IES-20. Ans. (b b) IES-21. Ans. (b) ( Joule Th homson coeffi icient is the ratio of temperature cha ange to press sure change whe en a gas und dergoes adiab batic throttlin ng. IES-22. Ans. (a) The slope of the is senthalpic cu urve at any point is kn nown as Jou ule-Thomson
coef fficient and is i expressed as, a
T p h
IES-23. Ans. (a a) IES-24. Ans. (b b) IES-25. Ans. (c c)

hfg dP IES-26. Ans. (c = c) dT sat T ( Vg Vf )
dP 5 or hfg = T ( Vg Vf ) = 400 ( 0251 0.001) 0.1 10 J / kg = 1000kJ / kg dT sat IES-27. Ans. (b b) b) IES-28. Ans. (b b) IES-29. Ans. (b c) IES-30. Ans. (c ron equation n state provi ides relation nship betwee en temperatu ure, specific IES-31. Ans. (d) Clapeyr volu ume, pressur re and enthal lpy. d) IES-32. Ans. (d c) IES-33. Ans. (c d) F = C P + 2 IES-34. Ans. (d ( Gibb's fre ee energy 'G' is defined as s G = H TS. . IES-35. Ans. (a) c) IES-36. Ans. (c d) F = C P + 2 IES-37. Ans. (d C = 1, P = 3 or F = 1 3 + 2 = 0 IES-38. Ans. (d) Isomers: Compounds with the same s chemic cal formula but differen nt molecular stru ucture.
160 0

IAS-1. Ans. (c)
P S = to memorize Maxwells relation remember T V P S, ive and S S V T V V T
P see highlights. IAS-2. Ans. (a) dQ = dh Vdp or Tds = dh Vdp dQp s IAS-3. Ans. (c) Cp = = T [ dQ = TdS] T T p IAS-4. Ans. (c) S TS dQ T = = = CP T P T P T P S TS dQ T = = = CV T V T V T V
S S T T T = CP CV = R T P V IAS-5. Ans. (a) Both A and R correct and R is the correct explanation of A IAS-6. Ans. (b) Cp Cv for all ideal gas is R, So C-3, (a) & (c) out. A automatically match 4, and
Cp =
5 5 R for monatomic gas = . So, = R . 3 2 1
IAS-7. Ans. (a) Cp Cv = R and = IAS-8. Ans. (b) IAS-9. Ans. (b) IAS-10. Ans. (c) IAS-11. Ans. (a) IAS-12. Ans. (d) IAS-13. Ans. (b) IAS-14. Ans. (b)
Cp Cv
Cp Cp R
1 R 1 Cp
161
Pu ure Su ubstan nces

7.
Pure e Subs stanc ces

A pure substan nce is define ed as one th hat is homog geneous and invariable in i chemical composition thr roughout its mass. The relative r prop portions of th he chemical elements e con nstituting the substance are e also consta ant. Atmosph heric air, ste eam water mixture and d combustion n products of o a fuel are reg garded as pu ure substance es. But the mixture m of air r and liquid air a is not a pure substanc ce, since the rel lative proportions of oxyg gen and nitrogen differ in the gas and liquid phases in equilibri ium. Mi ixtures are not pure subst tances. (e.g., Humid air) Ex xception!! Air A is treated d as a pure substance though t it is a mixture of o gases. In a majority of o cases a min nimum of tw wo properties are required d to define th he state of a system. s The bes st choice is an extensive property p and d an intensive e property. Th he state of a pure substa ance of given n mass can be b fixed by sp pecifying two o independen nt intensive pro operties, provided the sy ystem is in equilibrium. e T This is know wn as the 'tw wo-property y rule'. The sta ate can thus s be represented as a point p on ther rmodynamic property di iagrams. On nce any two pro operties of a pure substa ance are kno own, other properties p can n be determ mined from th he available the ermodynamic c relations.
p-v Diag gram for a Pure Subs stance
163 3

Tr riple po oint
Tri iple point is a point wher re all the thre ee phases exi ist in equilibr rium. u = 0 for water at triple poin nt. (You can assign any number n you li ike instead of o 0). Sin nce, p and v for f water at triple t point are a known yo ou can calcula ate h for water at triple point p (it will not t be zero).
The entropy of sa aturated water r is also chosen n to be zero at the t triple point.
Gibbs Pha ase Rule e at Tripl le Point

If C = 1, = 3, then t f = 0. Th he state is th hus unique fo or a substanc ce; and refers s to the triple e point wh here all the th hree phases exist e in equil librium. ln p = A + B/T valid d only near th he triple poin nt.(Called An ntoines equ uation)
164 4

p-T Diag gram fo or a Pur re Subs stance
165 5

p-v-T Su urface
TT-s Diagram for a Pure e Substance
C Critical Point P
A state at whi ich a phase change begin ns or ends is called a sa aturation state. s The do ome shaped reg gion compose ed of the two-phase liquid dvapor state es is called th he vapor do ome. The line es bordering the e vapor dome e are called saturated s liq quid and satu urated vapor lines. At the e top of the dome, d where the e saturated liquid l and sa aturated vapo or lines meet t, is the critical point. The critical temperature Tc of a pure su ubstance is th he maximum temperature e at which liq quid and vap por phases ca an coexist in equ uilibrium. Th he pressure at a the critica al point is cal lled the critical pressure, pc. The specific volume at this state is the critical specific sp volum me.
166 6

S K Mondals
Th he isotherm passing p through the crit tical point is called the e critical isotherm, and the rresponding temperatur re is known n as the cor cri itical tempe erature (tc). The press sure and vol lume at the critical poin nt are know wn as the cri itical pressur re (Pc) and th he critical vo olume (vc) res spectively. Fo or water
Cha apter 7
Pc = 221.2 bar tc = 374 4.15C vc = 0.0 00317 m3/kg
Fig. F Critical l Point on Pv, P TS, hs s diagram
Ch haracter ristics of f the crit tical poi int:

1. 2. 3. 4. It is the highest h temp perature at which w the liqu uid and vapou ur phases can n coexist. At the cri itical point hfg, ufg and vfg are zero. Liquid va apour menisc cus will disap ppear. Specific heat h at consta ant pressure is infinite. A ma ajority of eng gineering app plications (e.g g., steam bas sed power ge eneration; Re efrigeration, gas li iquefaction) involve i therm modynamic processes clos se to saturati ion. For saturated pha ase often it en nthalpy is an n important property. p alpy-pressur re charts are used for refr rigeration cyc cle analysis. Entha Entha alpy-entropy y charts for water w are used for steam cycle c analysis s. Note: : Unlike pres ssure, volume and tempe erature which h have specif fied numbers associated with it, in the cas se of interna al energy, en nthalpy (and entropy) onl ly changes ar re required. Conse equently, a base b (or datum m) is defined d - as you hav ve seen in the e case of water. For example e for NIST N steam tables u = 0 for water at a triple poin nt. (You can n assign any numb ber you like instead i of 0). [Dont be su urprised if tw wo different sets s of steam m tables give differ rent values fo or internal en nergy and en nthalpy].
167 7

S K Mondals
Cha apter 7
Since e, p and v for r water at tr riple point ar re known you u can calcula ate h for wat ter at triple point (it will not be b zero).
h-s Diagr ram or Mollier M Diagram m for a Pure Su ubstanc ce

Fro om the first and a second la aws of therm modynamics, the t following g property rel lation was ob btained.
Tds s = dh - vdp
or
h s = T p
Th his equation forms the basis b of the h-s diagram m of a pure substance, also a called the t Mollier dia agram. The e slope of an a isobar on n the h-s co oordinates is s equal to the t absolute e saturation tem mperature (tsat re. If the tem mperature rem mains consta ant the slope will remain s + 273) at that pressur con nstant. If the e temperature increases, the t slope of the t isobar wil ll increase.
Q Quality or o Dryn ness Fraction

The zon ne between th he saturated d liquid and the saturated d vapour region is called the t two phase region r - wher re the liquid and a vapour can c co-exist in n equilibrium m. Drynes ss fraction: It is the mass fraction of va apour in the mixture. Normal lly designate ed by x. On the saturated liquid l line x = 0 On the saturated vapour v line x = 1 x can have a value only o between n 0 and 1 Data ta ables will list t properties at a the two ends of saturat tion. To calcu ulate propert ties in the tw wo-phase regi ion: p, T wil ll be the sam me as for saturated liquid or saturated vapour.
168 8
Pure Substances
S K Mondals
v = x v + (1 x ) v
g g
Chapter 7
f
h = x h + (1 x ) h u = x u + (1 x ) u
g
AND
v = vf + xvfg u = uf + xufg h = hf + xhfg s = sf + xsfg

Saturation States
When a liquid and its vapour are in equilibrium at a certain pressure and temperature, only the pressure or the temperature is sufficient to identify the saturation state. If the pressure is given, the temperature of the mixture gets fixed, which is known as the saturation temperature, or if the temperature is given, the saturation pressure gets fixed. Saturated liquid or the saturated vapour has only one independent variable, i.e, only one property is required to be known to fix up the state. a Steam Table(saturated state) give the properties of sutured liquid and saturated vapour. In steam table the independent variable is temperature. At a particular temperature, the values of saturation pressure p, and states, Vg ,h g and S g refer to the saturated vapour state; and v fg ,h fg , and s fg refer to the changes in the property values during evaporation (or condensation) at the temperature. where v fg = v g v f and s fg = s g s f . If steam Table the independent variable is pressure. At a particular pressure, the values of v f , v g , h f , h fg , s f , and s g are given. whether the pressure or the saturation temperature t, and temperature is given, either steam Table can be conveniently used for computing the properties of saturation states. 169

If data a are required for inter rmediate tem mperature or r pressures, linear inter rpolation is nor rmally accur rate. The reas son for the tw wo tables is to t reduce the amount of in nterpolation required.
Liq quid vapou ur Mixtures: : Let us consider r a mixture of o saturated liquid water r and water vapour in eq quilibrium at t pressure p and temperatu ure t. The com mposition of the mixture by mass wil ll be within the t vapour dome d figure. Th he properties of the mixtu ure are as giv ven in Article. i.e
Fig. wh here v , v , h , s and d s fg are the saturation properties at the t given pre essure and te emperature.
f fg fg f
If p or t and th he quality of the t mixture are given, th he properties of the mixtu ure (v, u, h an nd s) can be eva aluated from m the above equations. e So ometimes instead of qua ality, one of the t above eq quations say spe ecific volume e v and press sure or temp perature are given. In tha at case, the quality of th he mixture x has to be calcu ulated from the given v and p or t and then x being know wn, other pro operties are aluated. eva If p or t and th he quality of the t mixture are given, th he properties of the mixtu ure (v, u, h an nd s) can be eva aluated from m the above equations. So ometimes, ins stead of qual lity, one of th he above prop perties, say, spe ecific volume e v and press sure or temp perature are given in tha at case, the quality q of th he mixture x has to be calcu ulated from the given v and p or t and then x being know wn, other pro operties are aluated. eva
Su uperheated Vapour: Wh hen the temp perature of the t vapour is greater tha an the satur ration tempe erature corresponding to the e given press sure, the vap pour is said to t be superheated (state 1 in figure). The differen nce between the e temperatur re of the superheated va apour and th he saturatio on temperatu ure at that pressure is cal lled the supe erheat or the degree of su uperheat. As shown in fig gure below, the t difference e (t1 - tsat) is the e superheat.
(Fig. - Superheat an nd Sub-cool ling.)

170 0
Pure Substances
In a superheated vapour at a given pressure, the temperature may have different values greater than the saturation temperature. Steam Table gives the values of the properties (volume, enthalpy, and entropy) of superheated vapour for each tabulated pair of values of pressure and temperature, both of which are now independent. Interpolation or extrapolation is to be used for pairs of values of pressure and temperature not given.
Compressed Liquid: When the temperature of a liquid is less than the saturation temperature at the given pressure, the liquid is called compressed liquid (state 2 in figure above). The pressure and temperature of compressed liquid may vary independently, and a table of properties like the superheated vapour table could be arranged, to give the properties at any p and t. However, the properties of liquids vary little with pressure. Hence the properties are taken from the saturation tables at the temperature of the compressed liquid. When a liquid is cooled below its saturation temperature at a certain pressure it is said to be sub-cool. The difference in saturation temperature and the actual liquid temperature is known as the degree of Sub-cooling, or simply, Sub-cooling.
Charts of Thermodynamic Properties

One of the important properties is the change in enthalpy of phase transition hfg also called the latent heat of vaporisation or latent heat of boiling. It is equal to hg - hf. Similarly ufg - internal energy change due to evaporation and v fg - volume change due to evaporation can be defined (but used seldom). The saturation phase depicts some very interesting properties: The following saturation properties depict a maximum:
1. T f 5. p ( Tc T ) 2. T ( f g) 6. p ( v g v f ) 3. T h fg 7. T ( c f g )
2
4. Tc ( pc p) 8. hg
The equation relating the pressure and temperature along the saturation is called the vapour pressure curve. Saturated liquid phase can exist only between the triple point and the critical point.
Measurement of Steam Quality

Throttling calorimeter: Throttling calorimeter is a device for determining the quality of a twophase liquidvapor mixture.
171

Int termediate states are non n-equilibrium m states not describable by thermody ynamic coord dinates. The ini itial state (we et) is given by b p1 and x1 , and a the final l state by p2 and a t2 (super rheated). Now w
since
h1 = h 2 H fp1 + x 1 h fg p1 = h 2 h 2 h fp 1 h fg gp 1
or
x1 =
Wi ith p2 and t2 being known n, h2 can be found out fro om the super rheated steam m table. The values of hf and hfg are ta aken from th he saturated d steam tabl le correspond ding to pres ssure p1 . Therefore, the w steam x1 can be calcu ulated. quality of the wet
T The Thrott T tling g Calo orime eter

Example e
A suppl ly line carrie es a two-phas se liquidvap por mixture of o steam at 20 2 bars. A sm mall fraction of the flow in the line is diver rted through h a throttling g calorimeter and exhau usted to the phere at 1 bar. b The te emperature of o the exha aust steam is i measured d as 120C. atmosp Determ mine the quality of the ste eam in the su upply line.
Solution n
Kn nown: Steam m is diverted from a supply line throu ugh a throttli ing calorimet ter and exhau usted to the atm mosphere. Fin nd: Determin ne the qualit ty of the steam in the sup pply line.
Sc chematic c and Gi iven Dat ta:
172 2

As ssumptio ons:
1. 2.
The contr rol volume sh hown on the accompanyin a ng figure is at steady stat te. The diver rted steam un ndergoes a th hrottling process.
An nalysis: For a throttling process, the energy and mass m balances reduce to give h2 = h1, Thus, with sta ate 2 fixed, the t specific enthalpy e in the t supply li ine is known n, and state 1 is fixed by y the known val lues of p1 an nd h1.
As shown on the t accompan nying pv di iagram, state e 1 is in the e two-phase liquidvapor l r region and sta ate 2 is in the e superheated vapor regio on. Thus
h2 = h1 = hf1 + x1 ( hg1 _ hf1 ) Solving for x1 x1 = h2 hf 1 hg1 hf 1
Fro om steam ta able at 20 ba ars, hf1 = 908 8.79 kJ/kg an nd hg1 = 279 99.5 kJ/kg. At A 1 bar and 120C, h2 = 276 66.6 kJ/kg fr rom steam table into the above a expres ssion, the qua ality in the line is x1 = 0.9 956 (95.6%). For throttling calorimeters s exhausting to the atmo osphere, the quality in th he line must t be greater tha an about 94% % to ensure th hat the steam m leaving the e calorimeter r is superhea ated.
Throttlin ng
Wh hen a fluid flows f throug gh a constric cted passage e, like a part tially opened d valve, an orifice, o or a por rous plug, th here is an ap ppreciable dr rop in pressu ure, and the flow is said d to be thrott tled. Figure sho ows the process of throttl ling by a par rtially opened d valve on a fluid f flowing g in an insula ated pipe. In the e steady-flow w energy equa ation.
173 3

dQ d = 0, 0 dm d
dW Wx =0 dm m
es in P.E. are e very small and a ignored. Thus, the S.F.E.E. reduc ces to and the change
C12 C22 h1 + = h2 + 2 2
Oft ften the pipe velocities in throttling ar re so low that t the K.E. ter rms are also negligible. So
h1 = h2
or the enthalpy y of the fluid before thrott tling is equal l to the entha alpy of the flu uid after thro ottling.
Co onsider a throttling proc cess (also ref ferred to as wire w drawing g process)
1 2
here is no wor rk done (risin ng a weight) Th If t there is no he eat transfer Co onservation of mass requires that Sin nce 1 and 2 are a at the sam me level
W=0 Q=0 C1 = C2 Z1 = Z2 174 4
Pure Substances
S K Mondals
From SFEE it follows that h1 = h2
Chapter 7
Conclusion: Throttling is a constant enthalpy process (isenthalpic process)
175
Pure Substances
Properties of Pure Substances

Highlights
1. Triple Point On P T diagram it is a Point. On P V diagram it is a Line. Also in T S diagram it is a Line. On U V diagram it is a Triangle. Triple point of water T = 273.16 K P = 0.00612 bar
= 0.01C = 4.587 mm of Hg
2.
Entropy (s) = 0 Internal energy (u) =0 Enthalpy = u + PV = slightly positive.
3.
Triple point of CO2 P 5 atm and T = 216.55 K = 56.45C that so why sublimation occurred.
4.
Critical point For water pc = 221.2 bar 225.5 kgf/cm2 tc = 374.15C 647.15 K vc = 0.00317 m3/kg At critical point
hfg = 0 ; v fg = 0 ; sfg = 0
5. Mollier Diagram
Basis of the h s diagram is
h s = T P
Tds = dh vdp h = T s P
6.
The slope of an isobar on the hs co-ordinates is equal to the absolute saturation temperature at that pressure. And for that isobars on Mollier diagram diverges from one another. Dryness fraction
176
Pure Substances
m x= m +m
v v
7.
v = (1 x) vf + xvg u = (1 x) uf + xug h = (1 x) hf + xhg s = (1 x) sf + xsg
and
v = vf + xvfg u = uf + xufg h = hf + xhfg s = sf + xsfg
8.
Super heated vapour: When the temperature of the vapour is greater than the saturation temperature corresponding to the given pressure. Compressed liquid: When the temperature of the liquid is less than the Saturation temperature at the given pressure, the liquid is called compressed liquid. In combined calorimeter x = x1 x 2 x1 = from throttle calorimeter.
x 2 = from separation calorimeter.
9.
10.
177
Pure Substances
ASKED OBJECTIVE QUESTIONS (GATE, IES, IAS) Previous 20-Years GATE Questions
Common data for Question Q1 Q3
In the figure shown, the system is a pure substance kept in a piston-cylinder arrangement. The system is initially a two-phase mixture containing 1 kg of liquid and 0.03 kg of vapour at a pressure of 100 kPa. Initially, the piston rests on a set of stops, as shown in the figure. A pressure of 200 kPa is required to exactly balance the weight of the piston and the outside atmospheric pressure. Heat transfer takes place into the system until its volume increases by 50%. Heat transfer to the system occurs in such a manner that the piston, when allowed to move, does so in a very slow (quasi-static I quasi-equilibrium) process. The thermal reservoir from which heat is transferred to the system has a temperature of 400C. Average temperature of the system boundary can be taken as 17C. The heat transfer to the system is I kJ, during which its entropy increases by 10 J/K. Atmospheric pressure. Specific volumes of liquid (vf) and vapour (vg) phases, as well as values of saturation temperatures, are given in the table below.
Pressure (kPa)
100 200 GATE-1.
Saturation temperature, Tsat (C)

100 200
vf(m3/kg)
0.001 0.0015
vg(m3/kg)
0.1 0.002
At the end of the process, which one of the following situations will be true? (a) Superheated vapour will be left in the system [GATE-2008] (b) No vapour will be left in the system (c) A liquid + vapour mixture will be left in the system (d) The mixture will exist at a dry saturated vapour state The work done by the system during the process is: (a) 0.1 kJ (b) 0.2 kJ (c) 0.3 kJ [GATE-2008] (d) 0.4kJ
GATE-2. GATE-3.
The net entropy generation (considering the system and the thermal reservoir together) during the process is closest to: [GATE-2008] (a) 7.5 J/K (b) 7.7 J/K (c) 8.5 J/K (d) 10 J/K
178

TT-s Diagram for a Pure e Substance

Co ommon Data for Qu uestions GATE-4 G - GA ATE-5
At thermodyna amic cycle with w an ideal gas as wo orking fluid d is shown below. b
GA ATE-4.
The e above cyc cle is repres sented on T-S plane by
[GA ATE-2007]
GA ATE-5.
If the t specific heats of th he working fluid are co onstant and d the value of specific hea at ratio is 1.4, the the ermal efficie ency (%) of the cycle is s: [G GATE-2007] (a) 21 (b) 40.9 (c) 42.6 (d) 59.7
GA ATE-6. The slopes of constant c vo olume and constant c pr ressure line es in the T-s diagram are e.. and.. respectivel ly. [G GATE-1994]
179 9
Pure Substances
h-s Diagram or Mollier Diagram for a Pure Substance

GATE-7. Constant pressure lines in the superheated region of the Mollier diagram have what type of slope? [GATE-1995] (a) A positive slope (b) A negative slope (c) Zero slope (d) May have either positive or negative slopes
Quality or Dryness Fraction

GATE-8. Consider a Rankine cycle with superheat. If the maximum pressure in tile cycle is increased without changing the maximum temperature and the minimum pressure, the dryness fraction of steam after the isentropic expansion will increase. [GATE-1995]
Throttling
Statement for Linked Answer Questions Q9 & Q10:
The following table of properties was printed out for saturated liquid and saturated vapour of ammonia. The titles for only the first two columns are available. All that we know is that the other columns (columns 3 to 8) contain data on specific properties, namely, internal energy (kJ/kg), enthalpy (kJ/kg) and entropy (kJ/kgK) [GATE-2005]
GATE-9.
The specific enthalpy data are in columns (a) 3 and 7 (b) 3 and 8 (c) 5 and 7
[GATE-2005] (d) 5 and 8
GATE-10. When saturated liquid at 40C is throttled to -20C, the quality at exit will be [GATE-2005] (a) 0.189 (b) 0.212 (c) 0.231 (d) 0.788 GATE-11. When wet steam flows through a throttle valve and remains wet at exit (a) its temperature and quality increases [GATE-1996] (b) its temperature decreases but quality increases (c) its temperature increases but quality decreases (d) its temperature and quality decreases GATE-12. When an ideal gas with constant specific heats is throttled adiabatically, with negligible changes in kinetic and potential energies [GATE-2000]
( a ) h = 0, T = 0
( b ) h > 0, T = 0 ( c ) h > 0, S > 0
( d ) h = 0, S > 0
Where h, T and S represent respectively, enthalpy, temperature and entropy, temperature and entropy
GATE-13. One kilomole of an ideal gas is throttled from an initial pressure of 0.5 MPa to 0.1 MPa. The initial temperature is 300 K. The entropy change of the universe is: [GATE-1995] 180

S K Mondals
(a) 13.38 kJ/K (b)401.3 kJ/K K (c) ) 0.0446 kJ/K K
Cha apter 7
(d) -0.044 46 kJ/K
Previo ous 20 0-Years s IES Questi Q ions

IES-1. Ass sertion (A): Water is no ot a pure su ubstance. [IES-1999] Rea ason (R): The term pure subs stance des signates a substance which is hom mogeneous and has the e same chem mical composition in all a phases. (a) Both A and R are individ dually true and a R is the correct c explan nation of A dually true but b R is NOT T the correct explanation e o A of (b) Both A and R are individ (c) A is true bu ut R is false (d) A is false bu ut R is true The e given diag gram shows s an isomet tric coo oling proc cess 12 of a pu ure sub bstance. Th he ordinate and abscis ssa are e respective ely (a) Pressure an nd volume (b) Enthalpy an nd entropy (c) Temperatur re and entrop py (d) Pressure an nd enthalpy [IES-1998] IES-3. The e ordinate and absc cissa in the giv ven figure showing s th he saturated d liqu uid and vap pour region ns of a pur re sub bstance represent: (a) Temperatur re and pressu ure (b) Enthalpy an nd entropy (c) Pressure an nd volume (d) Pressure an nd enthalpy [IES-1997] IES-4. The e given dia agram show ws the thro ottling pro ocess of a pu ure substan nce. abscissa The e ordina ate and are res spectively (a) Pressure an nd volume (b) Enthalpy an nd entropy (c) Temperatur re and entrop py (d) Pressure an nd enthalpy
IES-2.
[IES-1995]
IES-5.
Wh hich one of the following systems can be con nsidered to be contain ning a pure sub bstance? [IES-1993]
181 1

IES-6.
[IES-2009] Con nsider the following: f 3. Steam 1. Air A 2. Gaseo ous combus stion produc cts Wh hich of these e are pure substances, s assuming there t is no phase p chang ge? (a) 1 and 2 only (b) 1 and d 3 only (c) 2 and 3 only (d) 1, 2 and 3 Ass sertion (A): At a given n temperatu ure, the enthalpy of super-heate s d steam is the e same as th hat of satura ated steam. [IES-1998] Rea ason (R): The T enthal lpy of vapour at low wer pressur res is depe endent on tem mperature alone. a (a) Both A and R are individ dually true and a R is the correct c explan nation of A (b) Both A and R are individ dually true but b R is NOT T the correct explanation e o A of (c) A is true bu ut R is false (d) A is false bu ut R is true Con nsiders the following properties p o vapour: of [IES-2009] 1. Pressure P 2. Tempe erature 3. Dryness D fraction 4. Specifi ic volume Wh hich of these two prope erties alone e are not su ufficient to specify the e condition of a vapour? (a) 1 and 2 (b) 1 and 3 (c) ) 2 and 3 (d) 3 and 4 Wh hich one of the t followin ng is correct? [IES-2008] The e specific vo olume of wa ater when heated h from m 0C (a) First increas ses and then decreases (b) First decreases d and d then increa ases (c) Increases I ste eadily (d) Decrea ases steadily
IES-7.
IES-8.
IES-9.
p v Diag gram fo or a Pur re Subs stance

IES-10. Wh hich pv di iagram for steam illu ustrates co orrectly the e isothermal process [IES 1995, 2007] und dergone by wet steam till it becom mes superhe eated?
182 2

p T Diag gram fo or a Pur re Subs stance

IES-11. Con nsider the e phase diagram of f a cer rtain subst tance as shown in the t giv ven figure. Match List-I (Proce ess) wit th List-II (Curves/line es) and select the e correct answer a usin ng the cod des giv ven below th he lists: Lis st-I (Pr rocess) A. Vaporization n B. Fusion n C. Sublimation Cod des: (a) (c) A 1 3 B 3 2 List-II (Cur rves/lines) 1. EF F 2. EG G 3. ED D C 2 1
(b) (d)
A 1 3
B 2 1
C 3 2
[ [IES-2001]
183 3
Pure Substances
p-v-T Surface
IES-12. The p-v-T surface of a pure substance is shown in the given p figure. The two-phase regions are labelled as: (a) R, T and X (b) S, U and W (c) S, W and V (d) R, T and V
[IES-1999]
T-s Diagram for a Pure Substance

IES-13. The conversion of water from 40C to steam at 200C pressure of 1 bar is best [IES-1994] represented as
184

S K Mondals
IES-14. The e followin ng figure shows th he T-s dia agram for steam. s With h respect to t this figu ure, match List I with List II and select the e correct an nswer using g the codes s given bel low the List ts: List-II Lis st-I A. Curve C I 1. Satu urated liquid line B. Curve C II 2. Satu urated vapour r line C. Curve C III 3. Cons stant pressur re line D. Curve C IV 4. Cons stant volume line Cod des: A B C D (a) 2 1 4 3 (b) (c) 1 2 3 4 (d)
Cha apter 7
[IES-1994] A 2 1 B 1 2 C 3 4 D 4 3
C Critical Point P
IES-15. Wh hich one of the t followin ng is correct? At critical point the enthalpy of vapo orization is s (a) dependent on n temperatur re only (b) ) maximum m (d) ) zero (c) minimum Con nsider the following f st tatements about a critica al point of water: w 1. The T latent heat h is zero. . 2. The T liquid is denser tha an its vapou ur. 3. Steam S gener rators can operate o abo ove this poin nt. Of these statem ments (a) 1, 2 and 3 ar re correct (b) 1 and a 2 are cor rrect c (d) 1 and a 3 are cor rrect (c) 2 and 3 are correct [ [IES-2008]
IES-16.
[ [IES-1993]
IES-17.
Wh hich one of the t followin ng statemen nts is correc ct when sat turation pre essure of a vap pour increa ases? [IES 2007] (a) Saturation temperature decreases d (b) Enthalpy of evaporation decreases E of evaporation e i increases (c) Enthalpy (d) Specific volu ume change of o phase incre eases Ma atch List I with w List II I and selec ct the corre ect answer using the code c given bel low the List ts: [IES-2005] List-I List-II I A. Critical poin nt 1. All the e three pha ases - solid, liquid and vapour r co-exists in equilibrium B. Sublimation n 2. Phase change c form solid to liqui id C. Triple point t 3. Properties of saturated liquid and saturat ted vapour are identical D. Melting 4. Heatin ng process where w solid gets g directly transfo ormed to gase eous phase des: A B C D A B C D Cod (a) 2 1 4 3 (b) 3 4 1 2 4 1 3 (d) 3 1 (c) 2 4 2
185 5
IES-18.
Pure Substances
S K Mondals
IES-19.
Chapter 7
With increase of pressure, the latent heat of steam [IES-2002] (a) Remains same (b) Increases (c) Decreases (d) Behaves unpredictably List-I gives some processes of steam whereas List-II gives the effects due to the processes. Match List I with List II, and select the correct answer using the codes given below the lists: [IES-1995] List-I List-II A. As saturation pressure increases 1. Entropy increases. B. As saturation temperature increases 2. Specific volume increases. C. As saturation pressure decreases 3. Enthalpy of evaporation decreases. D. As dryness fraction increases 4. Saturation temperature increases. Code: A B C D A B C D (a) 1 3 2 4 (b) 4 3 2 1 (c) 4 3 1 2 (d) 2 4 3 1
IES-20.

IES-21. Which one of the following represents the condensation of a mixture of saturated liquid and saturated vapour on the enthalpy-entropy diagram? [IES-2004] (a) A horizontal line (b) An inclined line of constant slope (c) A vertical line (d) A curved line
Measurement of Steam Quality

IES-22. Saturated liquid at a high pressure P1 having enthalpy of saturated liquid 1000 kJ/kg is throttled to a lower pressure P2. At pressure p2 enthalpy of saturated liquid and that of the saturated vapour are 800 and 2800 kJ/kg respectively. The dryness fraction of vapour after throttling process is: [IES-2003] (a) 0.1 (b) 0.5 (c) 18/28 (d) 0.8 Consider the following statements regarding the throttling process of wet steam: [IES-2002] 1. The steam pressure and temperature decrease but enthalpy remains constant. 2. The steam pressure decreases, the temperature increases but enthalpy remains constant. 3. The entropy, specific volume, and dryness fraction increase. 4. The entropy increases but the volume and dryness fraction decrease. Which of the above statements are correct? (a) 1 and 4 (b) 2 and 3 (c) 1 and 3 (d) 2 and 4 Match List-I (Apparatus) with List-II (Thermodynamic process) and select the correct answer using the code given below the Lists: [IES-2006] List-I List-II 1. Adiabatic process A. Separating calorimeter B. Throttling calorimeter 2. Isobaric process C. Sling psychrometer 3. Isochoric process
186
IES-23.
IES-24.

S K Mondals
D. Gas thermometer Cod des: A B (a) 1 3 4 (c) 1 IES-25. C 2 2 D 4 3 4. Isentha alpic process A B C (b) 2 4 1 (d) 2 3 1
Cha apter 7
D 3 4 [IES-1998]
Sel lect the corr rect answer r using the codes given n below the Lists: List-I List-II I A. Bomb calori imeter 1. Pressure B. Exhaust gas s calorimeter r 2. Enthal lpy C. Junker gas calorimeter 3. Volume e D. Throttling calorimeter c 4. Specific heats Cod de: A B C D A B C (a) 3 4 1 2 (b) 2 4 1 (c) 3 2 1 4 2 (d) 4 3
D 3 1
Throttlin ng
IES-26. In a throttlin ng process s, which on ne of the following parameter rs remains con nstant? [IES-2009] (a) Temperature e (b) Pressure (c) ) Enthalpy (d) Entropy E Con nsider the following f st tatements: [IES-2000] Wh hen dry sat turated ste eam is thro ottled from m a higher pressure to t a lower pre essure, the 1. Pressure decreases d an nd the volum me increase es 2. Temperatu ure decreases and the steam s becom mes superh heated 3. Temperatu ure and the dryness fra action incre ease 4. Entropy in ncreases wit thout any change in en nthalpy Wh hich of these e statement ts are correct? (a) 1and 4 (b) 1, 2 and a 4 (c) 1 and 3 (d) 2 and 4 The e process 1-2 for steam m shown in the t giv ven figure is s (a) Isobaric (b) Isentrop pic (c) Is senthalpic (d) Isotherm mal
IES-27.
IES-28.
[I IES-2000] IES-29. A fluid fl flowing g along a pi ipe line und dergoes a th hrottling process from 10 bar to 1 Bar r in passing through a partially open valve e. Before th hrottling, th he specific vol lume of the fluid is 0.5 m3 /kg and after thrott tling is 2.0 m3 /kg. What t is the Change in spe ecific intern nal energy during d the throttling t process? [IES 2007] (a) Zero (b) 100 0 kJ/kg (c) 200 kJ/ /kg (d) 300 kJ/k kg
187 7
Pure Substances
S K Mondals
IES-30. The throttling process undergone by a gas across an orifice is shown by its states in the following figure:
Chapter 7
[IES-1996] IES-31. In the figure shown, throttling process is represented by (a) a e (b) a d (c) a c (d) a b
[IES-1992] IES-32. Match List-l with List-Il and select the correct answer using the code given below the lists: [IES-2009] List-lI List-l 1. Energy is always constant A. Isolated system B. Nozzle 2. Increase in velocity at the expense of its C. Throttling device pressure drop D. Centrifugal compressor 3. Appreciable drop in pressure without any change in energy 4. Enthalpy of the fluid increases by the amount of work input Codes: (a) (c) A 4 4 B 3 2 C 2 3 D 1 1
(b) (d)
A 1 1
B 3 2
C 2 3
D 4 4
188

Previo ous 20 0-Years s IAS Quest Q ions

IA AS-1. Wh hich one of the following systems can be con nsidered to be contain ning a pure sub bstance? [IAS 1998]
IA AS-2.
Ass sertion (A): On the enthalpy-en e ntropy diag gram of a pure subs stance the con nstant dryn ness fraction n lines start t from the critical c poin nt. [IAS-2001] Rea ason (R): Al ll the three phases co-e exist at the critical point. (a) Both A and R are individ dually true and a R is the correct c explan nation of A dually true but b R is NOT T the correct explanation e o A of (b) Both A and R are individ (c) A is true bu ut R is false (d) A is false bu ut R is true Ass sertion (A): Air, a mixtu ure of O2 an nd N2, is a pure substan nce. [IAS-2000] Rea ason(R): Air is homo ogeneous in composition and uniform u in n chemical agg gregation. (a) Both A and R are individ dually true and a R is the correct c explan nation of A dually true but b R is NOT T the correct explanation e o A of (b) Both A and R are individ (c) A is true bu ut R is false (d) A is false bu ut R is true If a pure substance conta ained in a rigid r vessel passes thro ough the critical state on heating, its s initial stat te should be e: [IAS-1998] (a) Subcooled water (b) Saturated d water (c) ) Wet steam (d) Saturate ed steam Ass sertion (A): Air is a pu ure substan nce but a mixture m of air a and liqu uid air in a cylinder is not t a pure sub bstance. [IAS-1996] Rea ason (R): Ai ir is homog geneous in composition c n but a mix xture of air and liquid air is heteroge eneous. (a) Both A and R are individ dually true and a R is the correct c explan nation of A (b) Both A and R are individ dually true but b R is NOT T the correct explanation e o A of (c) A is true bu ut R is false (d) A is false bu ut R is true
IA AS-3.
IA AS-4.
IA AS-5.
189 9

S K Mondals
IA AS-6.
Cha apter 7
Ass sertion (A): Temperatu ure and pressure are sufficient to o fix the stat te of a two pha ase system. [IAS-1995] Rea ason(R): Tw wo indepen ndent and intensive properties are requi ired to be kno own to defin ne the state e of a pure substance. s (a) Both A and R are individ dually true and a R is the correct c explan nation of A (b) Both A and R are individ dually true but b R is NOT T the correct explanation e o A of (c) A is true bu ut R is false (d) A is false bu ut R is true
p v Diag gram fo or a Pur re Subs stance

IA AS-7. Tw wo-phase regions r in n the given g pre essure-volum me diagra am of a pure sub bstance are represente ed by (a) A, A E and F (b) B, C and D (c) B, B D and F (d) A, C and E [IAS-1999] IA AS-8. A cyclic c proce ess ABC is shown s on a VT dia agram in fig gure. The e same proc cess on a P V diagram m will be represent as: a
[ [IAS-1996]
190 0
Pure Substances
S K Mondals
IAS-9. The network done for the closed shown in the given pressure-volume diagram, is (a) 600kN-m (b) 700kN-m (c) 900kN-m (d) 1000kN-m
Chapter 7
[IAS-1995]
Triple point
IAS-10. Triple point temperature of water is: (a) 273 K (b) 273.14 K (c) 273.15K [IAS-2000] (d) 273.16 K
pT Diagram for a Pure Substance

IAS-11. In the following P-T diagram of water showing phase equilibrium lines, the sublimation line is: (a) p (b) q (c) r (d) S
[IAS-1998]
T-s Diagram for a Pure Substance

IAS-12. Entropy of a saturated liquid at 227C is 2.6 kJ/kgK. Its latent heat of vaporization is 1800 kJ/kg; then the entropy of saturated vapour at 227C would be: [IAS-2001] (a) 2.88 kJ/kg K (b) 6.2 kJ/kg K (c) 7.93 kJ/kg K (d) 10.53 kJ/kg K
191
Pure Substances
S K Mondals
IAS-13. Two heat engine cycles (l - 2 3 - 1 and l' - 2' - 3' - l) are shown on T-s co-ordinates in
Chapter 7
[IAS-1999]
IAS-14.
The mean effective pressure of the thermodynamic cycle shown in the given pressurevolume diagram is: (a) 3.0 bar (b) 3.5 bar (c) 4.0 bar (d) 4.5 bar
[IAS-1999]
192
Pure Substances
S K Mondals
IAS-15. The given figure shows a thermodynamic cycle on T-s diagram. All the processes are straight times. The efficiency of the cycle is given by (a) (0.5 Th Te)/ Th (b) 0.5 (Th Te)/ Th (c) (Th Te)/ 0.5 Th (d) (Th 0.5 Te)/ Th
Chapter 7
[IAS-1996]

IAS-16. Constant pressure lines in the superheated region of the Mollier diagram have what type of slope? [IAS-2007] (a) A positive slope (b) A negative slope (c) Zero slope (d) May have either positive or negative slopes Assertion (A): In Mollier chart for steam, the constant pressure lines are straight lines in wet region. Reason (R): The slope of constant pressure lines in wet region is equal to T. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is not the correct explanation of A (c) A is true but R is false [IAS-1995] (d) A is false but R is true
IAS-17.
Quality or Dryness Fraction

IAS-18. Dryness fraction of steam means the mass ratio of [IAS-2001] (a) Wet steam, to dry steam (b) Dry steam to water particles in steam (c) Water particles to total steam (d) Dry steam to total steam
Throttling
IAS-19. Assertion (A): Throttle governing is thermodynamically more efficient than nozzle control governing for steam turbines. [IAS-2000] Reason (R): Throttling process conserves the total enthalpy. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
193

Answ wers with Expla anatio on (Ob bjectiv ve)

Previo ous 20-Years s GATE E Answ wers
GA ATE-1. Ans. (a) Initial Volume V (V1) = 0.001 + 0.03 3 0.1 m3 = 0.004 0 m3 Let t dryness frac ction = x The erefore 0.004 4 1.5 = (1 x) 0.0015 1.03 + x 0.002 1.0 03 Tha at gives an absurd value of x = 8.65 (I It must be le ess than equa al to unity). So S vapour is sup perheated. GA ATE-2. Ans. (d) Work do one = first con nstant volum me heating +
= 0 + P (V2-V1) = 200 (0.006-0.004) = 0.4 kJ
pdv
GA ATE-3. Ans. (c) ( S = (S ) syatem + ( S ) surroundings = 10 GA ATE-4. Ans. (c) GA ATE-5. Ans. (b) GA ATE-6. Ans. . Higher, Low wer GA ATE-7. Ans. (a) Mollier diagram d is a h-s plot.
Tds s= dh - dp
00 100 = 8.51 J/K (273 + 400)
h = T = slope or r s P
T is s always + ive so slope al lways +ive. Not N only this if T then sl lope GA ATE-8. Ans. False
GA ATE-9. Ans. (d) ATE-10. Ans s. (b) GA h 40 = h20 = (1 x ) hf 20 + xhg
or 371.43 = (1 x ) 89.05 + x 1418.0 or x = 0.212 3

194 4
Pure Substances
S K Mondals
GATE-11. Ans. (b) GATE-12. Ans. (d) h = o
Chapter 7
s > 0 T < 0
GATE-13. Ans. (a) S2 S1 = C pav ln
T2 P Ru ln 2 T1 P1
P2 P1
Change in entropy of the universe = Ru ln
0.1 kJ = 13.38 0.5 K For an ideal gas change in enthalpy is a function of temperature alone and change in enthalpy of a throttling process is zero. = 8.314 ln

IES-1. Ans. (d) Water for all practical purpose can be considered as pure substance because it is homogeneous and has same chemical composition under all phases. IES-2. Ans. (d) IES-3. Ans. (d) The ordinate and abscissa in given figure are pressure and enthalpy. Such diagram is common in vapour compression refrigeration systems. IES-4. Ans. (d) The throttling process given in figure is on pressure-enthalpy diagram. IES-5. Ans. (d) IES-6. Ans. (b) A pure substance is one whose chemical composition does not change during thermodynamic processes. Pure Substance is one with uniform and invariant chemical composition. Eg: Elements and chemical compounds are pure substances. (water, stainless steel) Mixtures are not pure substances. (eg: Humid air) Exception!! Air is treated as a pure substance though it is a mixture of gases. Gaseous combustion products are a mixture of gases and not a pure substance. IES-7. Ans. (d) IES-8. Ans. (a) IES-9. Ans. (b) The largest density of water near atmospheric pressure is at 4c. IES-10. Ans. (c) Up to saturation point pressure must be constant. After saturation its slope will be dp p = ive, as pv = RT or pv = const. or vdp + pdv = 0 or dv v 195
Pure Substances
IES-11. Ans. (c) IES-12. Ans. (c) IES-13. Ans. (a) IES-14. Ans. (c) IES-15.Ans.(d) Characteristics of the critical point 1. It is the highest temperature at which the liquid and vapour phases can coexist. 2. At the critical point hfg, ufg and vfg are zero. 3. Liquid vapour meniscus will disappear. 4. Specific heat at constant pressure is infinite. IES-16. Ans. (d) At critical point, the latent heat in zero and steam generators can operate above this point as in the case of once through boilers. The density of liquid and its vapour is however same and thus statement 2 is wrong. IES-17. Ans. (b) IES-18. Ans. (b) IES-19. Ans. (c) IES-20. Ans. (c) IES-21. Ans. (b) h Tds = dh Vdp or s = T P
The slope of the isobar on the hs diagram is equal to the absolute temp, for condensation T is cost so slope is const, but not zero so it is inclined line.
IES-22. Ans. (a) For throttling process (1 2), h1 = h2
h1 = hf = 1000 kJ/kg at pressure P1 h2 = hf + x (hg hf ) at pressure P2 1000 = 800 + x (2800 800) or x = 0.1
IES-23. Ans. (c) IES-24. Ans. (c) IES-25. Ans. (a) IES-26. Ans. (c) Consider a throttling process (also referred to as wire drawing process)
There is no work done (rising a weight) If there is no heat transfer Conservation of mass requires that Since 1 and 2 are at the same level 196
W=0 Q=0
C1 = C 2 Z1 = Z 2
Pure Substances
From SFEE it follows that h1 = h2 Conclusion: Throttling is a constant enthalpy process (isenthalpic process) IES-27. Ans. (b) Temperature decreases and the steam becomes superheated.
IES-28. Ans. (d) IES-29. Ans. (d) Throttling is a isenthalpic process h1 = h2 or u1 + p1v1 = u2 + p2v2 or u2 u1 = p1v1 p2v2 = 1000 0.5 100 2 = 300 kJ/kg IES-30. Ans. (d) The throttling process takes places with enthalpy remaining constant. This process on TS diagram is represented by a line starting diagonally from top to bottom. IES-31. Ans. (b) IES-32. Ans. (d)

IAS-1. Ans. (d) IAS-2. Ans. (c) Only two phase liquid-vapour is co-exists at the critical point, but at triple point-all three phase are co-exists. IAS-3. Ans. (a) A pure substance is a substance of constant chemical composition throughout its mass. IAS-4. Ans. (c)
IAS-5. Ans. (a) IAS-6. Ans. (d) A is false but R is true. IAS-7. Ans. (c) IAS-8. Ans. (d) IAS-9. Ans. (d) Network done is area of closed loop ABCD = Area of trapezium AB32 + Area BC63 Area CD56 Area AD52 4+6 6+4 1 + 4 1 + 4 = (3 2) + 2 ( 6 3) 2 ( 6 5) + 2 (5 2) 2
= 5 1 + 5 3 2.5 1 2.5 3 = 10 bar m3 N m3 = 106 Nm = 1000 kNm m2 IAS-10. Ans. (d) Remember: Triple point temperature of water = 273.16 K = 0.01C = 10 105
197
Pure Substances
S K Mondals
IAS-11. Ans. (a) IAS-12. Ans.
Chapter 7
h fg Tsat = 2.6 +
Sg = S f +
1800 = 6.2 kJ / kgK 500

1 ( 600 400 ) ( 0.03 0.01) = 6kJ 2
IAS-13. Ans. (d) IAS-14. Ans. (a) Work (W) = ( 0.03 0.01) ( 400 200 ) +
W = pm V or pm =
W 6 = kPa = 3bar V ( 0.03 0.01)
IAS-15. Ans. (b) Work output = Area 123 =
1 ( Th Tc ) ( S2 S1 ) 2 Heat added = Area under 1 2 = Th ( S2 S1 )
1 ( Th Tc )( S2 S1 ) = 2 = 0.5 ( Th Tc ) / Th Th ( S2 S1 ) IAS-16. Ans. (a) Mollier diagram is a h-s plot.
Tds= dh dp
or
h = T = slope s P
T is always + ive so slope always +ive. Not only this if T then slope IAS-17. Ans. (a) Both A and R are true and R is the correct explanation of A IAS-18. Ans. (d) IAS-19. Ans. (d) If throttle governing is done at low loads, the turbine efficiency is considerably reduced. The nozzle control may then be a better method of governing.
198
Prop pertie es of Gasses G s & Ga as Mix.

8.
Prop pertie es of Gass G es an nd Ga as Mixtu ure

1. 2.
The fun nctional relat tionship amo ong the indep pendent prop perties, press sure P, mola ar or specific volume e v, and temp perature T, is s known as Equation E of st tate i.e. PV = RT for gas ses. A hypothetical gas which obeys the law PV = RT at all temperatures t s and pressures is called an idea al gas as has no forc ces of interm molecular attr raction. An ideal ga The specific heat capacit ties are const tant.
3. 4.
Real gas g does not t conform to equation of state with co omplete accu uracy. As P0 or T , the real gas approac ches the idea al gas behaviour. Joules s law state es that the specific int ternal energ gy of a gas s depends only o on the temperature of the gas and is in ndependent of f both pressu ure and volum me.
PR ROCESS Constant Vo olume Proce ess: The pr rocess is repr resented on a pv diagram as shown in Figure. C
F Fig.
Here or Therefore or work tr ransfer v1 = v2 dv = 0 pdv = 0 W=0 200 0

S K Mondals
Therefore d Q = dE = du = Cv (T2 T1) or Q1-2 = Cv (T2 T1) (i.e.,) duri ing constant volume proc cess, the heat t transfer is the change in internal en nergy. From gas s equation pv p1v1 = 2 2 T2 T1 We get, p1 T2 = p2 T1 Constant Pressure P Pr rocess: This s process is represented r o a pv diagram as shown on n in Figure. In this process. . p1 = p2 Fro om gas equat tion we get p1v1 pv = 2 2 T1 T2
Cha apter 8
Fig.v1 T2 = v2 T1 d W = pdv = p(v2 v1) d Q = dE + d W = du + d W = d(u + pv) = d (h) ) = CP (T T2 T1) (i.e.,) heat t transfer is the t change in n enthalpy in n the case of a constant pr ressure proce ess.
(or)
Constant tem mperature (or) Isother rmal proces ss:C The process is represented in figur re(below). Here T1 = T2 d W = pdv
W = p dv v = C dv ; V 1
2
since pv = C
201 1

F Fig.
v W = p1v1 l n 2 = p1v1 ln ( r ) v1 v r= 2 where v1 Since du =
(u2 u1 ) =
= T2 and dT T1 T = 0.
Cv ( T2 T1 ) = 0.
Therefore, by the First t Law of Thermodynamic cs Q = W = p1v1 ln (r)
Adiabatic pr rocess: A Th his is also ca alled isentro opic process as entropy y in this pro ocess will rem main constan nt and heat tra ansfer in this s process is al lso zero. The process is re epresented in n pv diagram m shown in Fi igure below.
F Fig.The equat tion for this process p becom mes, p1v1 = p2v2
where = ratio of spec cific heats CP (i.e.,) = Cv For this process Q = 0 Hence 0 = d E + d W = du + d W or d W = du = mCv dT d W = pdv or pdv = du = mCv dT d or pdv + mCvdT = 0 But pv = mRT differentia ating; pdv + vdp v = mR dT T From the above equati ion, pdv + vdp dT = mR R 202 2
quation.....1) ( eq
Properties of Gasses & Gas Mix.

S K Mondals
In equation-1, value of dT is substituted.
pdv + vdp pdv + mC v = 0 mR R.pdv + Cv (pdv + vdp) = 0 But R = (CP Cv) Therefore (CP Cv) pdv + Cv (pdv + vdp) = 0 or Cv vdp + CP pdv = 0 Dividing by (Cv p v) we get dp CP dv . + =0 p Cv V
Chapter 8
But Therefore
CP = Cv
dp dv + = 0 p V Integration and rearranging we get, ln p + ln v = C Or pv = C p1v1 = p2v2 (i.e.) From the gas equation pv = mRT, we can obtain the relationships between pressure and temperature and volume and temperature as given below.
v p T1 = 2 = 1 T2 v1 p2 Work transfer d W = pdv
1 1
W = pdv
1
pv = C p= C v
Therefore
W = C dv 1V
2
But
v +1 v1 +1 = C 2 - +1 C = p1v1 = p2v2
p v p1v1 W = 2 2 + 1 p v p2v2 W = 1 1 1 Also first law becomes W = E = U
203

General process or polytropic process: In the adiabatic process the index for V is . In a most general case this can be replaced by n. The values of n for different processes are indicated below : if n = 0 the process is constant pressure if n = 1 the process is isothermal if n = the process is constant volume if n = the process is adiabatic. and for any process other than the above, n becomes a general value n. All the equations of adiabatic process can be assumed for this process with replaced by n.
p T1 v2 = = 1 T2 v1 p2 p v p2v2 W = 1 1 n 1
But
n 1
n 1 n
W = is not true as Q is not zero. Q = pdv + ( u2 u1 )
By the first law of Thermodynamics,
p1v1 p2v2 + mCv (T2 T1 ) n 1 But by gas equation p1v1 = mRT1 and p2v2 = mRT2 =
so, Q = mCv ( T2 T1 ) + mR(T2 T1 ) 1n R = m(T2 T1 ) Cv + 1 n C Cv Q = m ( T2 T1 ) Cv + P 1n C Cv = m Cv + P ( T2 T1 ) 1n C nCv Q= P ( T2 T1 ) 1n Substituting CP = Cv n Q= Cv ( T2 T1 ) 1n Hence the specific heat for a polytropic process is Cn = Cv
n = Cn 1n
But,
( T2 T1 )
4.
For minimum work in multistage compression P2 = P1P3 a. Equal pressure ratio i.e. P2 = P3 P1 P2
204

S K Mondals
b. c. 5. Equal discha E arge temper rature i.e. T2 =T3 E Equal work required fo or both the stages. s Equati ion of states s for real ga as a.
V der waals Van s equation (p p+
Cha apter 8
a )(v-b) ) = RT v2
b.
The coefficien T nt a is intr roduced to account a for the t existenc ce of mutual attraction 2 between the molecules. m Th he term a/v is i called the force of coh hesion. The coefficient b is s introduced to account fo or the volume es of the mole ecules, and is s known as co-volume c . B Beattie Brid dgeman equation p=
A RT (1 e)( ) v + B) v2 v2
Where A = A0 (1-
a ) v2 b B = B0 (1- ) v c e= vT 3
T This equation n does not giv ve satisfactory results in the t critical po oint region.
6.
The rat tio
PV RT
is called c the com mpressibilit ty factor.
7.
Value of o compressib bility factor (Z Z) at critical point is 0.37 75 for Van der waals gas. For ide eal gas z = 1 Critica al Propertie es:
a =3PcVc2,
b=
8 PcVc Vc , and R= = 3 Tc 3
Where Pc, Vc and Tc are critica al point pres ssure, volume e and tempera ature respect tively. At Critical Po oint (i) Three rea al roots of Va ander Waal equation coincide. (ii) )
p am is zero. = 0 i.e. Slope of p-v diagra v Tc
(iii i)
2 p nge of slope also a zero. 2 = 0 i.e. Chan v Tc 3 p egative, and equal e to -9pc 3 < 0 i.e. ne v Tc
Boyles s Temperatu ure (TB) =
Fig.
Critical properties diagram
on
pv
(iv v)
8.
a b bR
205 5

S K Mondals
9.
Chapter 8
Boyles Law is obeyed fairly accurately up to a moderate pressure and the corresponding temperature is called the Boyles Temperature. Daltons Law a. The pressure of a mixture of gases is equal to the sum of the partial pressures of the constituents. b. The partial pressure of each constituent is that pressure which the gas would exert if it occupied alone that volume occupied by the mixture at the same temperature. Gibbs-Dalton Law a. The internal energy, enthalpy and entropy of a gaseous mixture are respectively equal to the sum of the internal energies, enthalpies, entropies of the constituents. b. Each Constituent has that internal energy, enthalpy and entropy, which it would have if it occupied alone that volume occupied by the mixture at the same temperature. Equivalent molecular weight (Me) = x1M1+x2M2+------------+ xnMn Equivalent gas constant (Re) = x1R1+x2R2+-------------+xnRn Equivalent constant volume specific heat (Cve) = x1Cv1+x2Cv2+------------+xnCnv Equivalent constant pressure specific heat (Cpe) = x1Cp1+x2Cp2+------------+xnCpn xi =
10.
11.
mi = mass fraction of a constituent m
12.
The value of Universal Gas constant R = 8.3143 KJ/Kg mole K.

Example 1. Ten moles of ethane were confined in a vessel of volume 4.86 litres at 300K. Predict the pressure of gaseous ethane under these conditions with the use of equation of state of Van der Waals when a = 5.44 litre2 atm mol-2; b = 64.3 millititre mol-1; R = 0.08205 atm mol-1 deg-1 Solution: Using van der Waals equation, (for total volume V = nv) nRT an2 10.00 0.08205 300 5.44 10.02 p= 2 = V nb V 4.86 10.0 0.0643 4.862 = 58.4 23 = 35.4 atm. Example 2. A rigid vessel of 0.3 m3 volume contains a perfect gas at a pressure of 1 bar. In order to reduce the pressure, it is connected to an extraction pump. The volume flow rate though the pump is 0.014 m3/min. Assuming the gas temperature remains constant, calculate the time taken to reduce the pressure to 0.35 bar. Solution: Vdp m = pV / RT ; dm = RT p. (Ve dt ) Mass of gas removed = RT Where Ve is the rate of extraction and dt is the time interval. Equating and simplifying
206

S K Mondals
dp V = e dt p V
p2
Chapter 8
dp Ve dt = p V p1 0 P2 V = e t P1 V
ln
V P t = ln 1 Ve P2 0.3 1.0 = ln 0.35 = 22.5min. 0.014
Example 3. The value of characteristic constant for a gas is 4.1 kJ/kgK and specific heat at constant pressure is 14.28 kJ/kg K. 5 cubic meters of this gas at a pressure of 100 kPa and 20C are compressed adiabatically to 500 kPa. The compressed gas is then expanded isothermally to original volume. Calculate: (a) The final pressure of the gas after expansion, (b) The quantity of heat added from the beginning of compression to the end of expansion. Solution: pV 100 103 5 m= = = 0.4162kg RT 4.1 103 293 C p = 14.28 kJ / kg K
Cv = C p R = 10.18
= 1.4028
p 1 1.4028 V2 = V1 1 = 5 = 1.5874m3 p 5 2 V 5 105 1.5874 p3 = 2 p2 = = 158.74 kPa V1 5 p T2 = T1 2 p1 V Q = p2V2 ln 1 V2 = 910.6 kJ .
1
1 1
= 465 K 5 5 = 5 10 1.5874 ln 1.5874
207

ASKED OBJECTIVE QUESTIONS (GATE, IES, IAS) Previous 20-Years GATE Questions Equation of State of a Gas
GATE-1. Nitrogen at an initial stage of 10 bar, 1 m3 and 300K is expanded isothermally a v = RT , where a > 0. to a final volume of 2 m3. The P-V-T relation is P + 2 v The final pressure will be: [GATE-2005] (a) Slightly less than 5 bar (b) Slightly more than 5 bar (c) Exactly 5 bar (d) Cannot be ascertained.
Adiabatic Process
GATE-2. A mono-atomic ideal l gas ( = 1.67, molecular weight = 40) is compressed adiabatically from 0.1 MPa, 300 K to 0.2 MPa. The universal gas constant is 8.314 kJ kmol-1K-1. The work of compression of the gas (in kJ kg-1) is: [GATE-2010] (a) 29.7 (b) 19.9 (c) 13.3 (d) 0
Statement for Linked Answer Questions Q3 & Q4:

A football was inflated to a gauge pressure of 1 bar when the ambient temperature was 15C. When the game started next day, the air temperature at the stadium was 5C. Assume that the volume of the football remains constant at 2500 cm3. GATE-3. The amount of heat lost by the air in the football and the gauge pressure of air in the football at the stadium respectively equal [GATE-2006] (a) 30.6 J, 1.94 bar (b) 21.8 J, 0.93 bar (c) 61.1 J, 1.94 bar (d) 43.7 J, 0.93 bar Gauge pressure of air to which the ball must have been originally inflated so that it would equal 1 bar gauge at the stadium is: [GATE-2006] (a) 2.23 bar (b) 1.94 bar (c) 1.07 bar (d) 1.00 bar A 100 W electric bulb was switched on in a 2.5 m 3 m 3 m size thermally insulated room having a temperature of 20C. The room temperature at the end of 24 hours will be [GATE-2006] (a) 321C (b) 341C (c) 450C (d) 470C
GATE-4.
GATE-5.
208

Isothermal Process
GATE-6. A frictionless piston-cylinder device contains a gas initially at 0.8 MPa and 0.015 m3. It expands quasi-statically at constant temperature to a final volume [GATE-2009] of 0.030 m3. The work output (in id) during this process will be: (a) 8.32 (b) 12.00 (c) 554.67 (d) 8320.00
Properties of Mixtures of Gases

GATE-7. 2 moles of oxygen are mixed adiabatically with another 2 moles of oxygen in a mixing chamber, so that the final total pressure and temperature of the mixture become same as those of the individual constituents at their initial states. The universal gas constant is given as R. The change in entropy due to mixing, per mole of oxygen, is given by [GATE-2008] (A) Rln2 (B) 0 (C) Rln2 (D) Rln4
Previous 20-Years IES Questions Avogadro's Law

IES-1. Assertion (A): The mass flow rate through a compressor for various refrigerants at same temperature and pressure, is proportional to their molecular weights. [IES-2002] Reason (R): According to Avogardos Law all gases have same number of moles in a given volume of same pressure and temperature. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is NOT the correct explanation of A (c) A is true but R is false (d) A is false but R is true
Ideal Gas
IES-2. Assertion (A): A perfect gas is one that satisfies the equation of state and whose specific heats are constant. [IES-1993] Reason (R): The enthalpy and internal energy of a perfect gas are functions of temperature only. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is not the correct explanation of A (c) A is true but R is false (d) A is false but R is true In a reversible isothermal expansion process, the fluid expands from 10 bar and 2 m3 to 2 bar and 10m3, during the process the heat supplied is 100 kW. What is the work done during the process? [IES-2009] (a) 33.3 kW (b) 100 kW (c) 80 kW (d) 20 kW Consider an ideal gas contained in vessel. If intermolecular interaction suddenly begins to act, which of the following happens? [IES-1992]
IES-3.
IES-4.
209

S K Mondals
(a) The pressure increase (c) The pressure increase
IES-5.
Chapter 8
(b) The pressure remains unchanged (d) The gas collapses
Which of the following statement is correct? [IES-1992] (a) Boilers are occasionally scrubbed by rapidly and artificially circulating water inside them to remove any thin water film may have formed on their inside (b) A sphere, a cube and a thin circular plate of the same mass are made of the same material. If all of them are heated to the same high temperature, the rate of cooling is maximum for the plate and minimum for the sphere. (c) One mole of a monoatomic ideal gas is mixed with one mole of diatomic ideal gas. The molar specific heat of the mixture a constant volume is 2R, where R is the molar gas constant. (d) The average kinetic energy of 1 kg of all ideal gases, at the same temperature, is the same. Consider the following statements: A real gas obeys perfect gas law at a very 1. High temperature 2. High-pressure Which of the following statements is/are correct? (a) 1 alone (b) 1 and 3 (c) 2 alone [IES-2000] 3. Low pressure
IES-6.
(d) 3 alone
Equation of State of a Gas

IES-7. The correct sequence of the decreasing order of the value of characteristic gas constants of the given gases is: [IES-1995] (a) Hydrogen, nitrogen, air, carbon dioxide (b) Carbon dioxide, hydrogen, nitrogen, air (c) Air, nitrogen, carbon dioxide, hydrogen (d) Nitrogen, air, hydrogen, carbon dioxide If a real gas obeys the Clausius equation of state p(v b) = RT then, [IES-1992]
IES-8.
(a)
u 0 v T
(b)
u =0 v T
(c)
1 u u = 1 (d) = v T p v T
[IES-2002]
IES-9.
Pressure reaches a value of absolute zero (a) At a temperature of -273K (b) Under vacuum condition (c) At the earths centre (d) When molecular momentum of system becomes zero Reduced pressure is (a) Always less than atmospheric pressure (c) An index of molecular position of a gas
IES-9a.
[IES-2011]
(b) Always unity (d) Dimensionless
210

Van der Waals equation

IES-10. Which one of the following is the characteristic equation of a real gas? [IES-2006]
(a) p +
a ( v b ) = RT v2 (c) pv = RT
(b) p
a ( v + b ) = RT v2 (d) pv = nRT
IES-11.
Which of the following statement about Van der waal's equation i valid? (a) It is valid for all pressure and temperatures [IES-1992] (b) It represents a straight line on pv versus v plot (c) It has three roots of identical value at the critical point (d) The equation is valid for diatomic gases only. The internal energy of a gas obeying Van der Waals equation [IES-2000]
IES-12.
a P + 2 ( v b ) = RT , depends on v
(a) Temperature (c) Temperature and specific volume

IES-13.
(b) Temperature and pressure (d) Pressure and specific volume
a Van der Waals equation of state is given by P + 2 ( v b ) = RT . The constant v
b in the equation in terms of specific volume at critical point Vc is equal to: [IES-2003]
(a) Vc/3
(b) 2 Vc
(c) 3 Vc
(d)
8a 27VcR
Compressibility
IES-14. Consider the following statements: [IES-2007] 1. A gas with a compressibility factor more than 1 is more compressible than a perfect gas. 2. The x and y axes of the compressibility chart are compressibility factor on y-axis and reduced pressure on x-axis. 3. The first and second derivatives of the pressure with respect to volume at critical points are zero. Which of the statements given above is/are correct? (a) 2 and 3 only (b) 1 and 3 only (c) 1 and 2 only (d) 1, 2 and 3 Which one of the following statements is correct? (a) Compressibility factor is unity for ideal gases (b) Compressibility factor is zero for ideal gases (c) Compressibility factor is lesser than unity for ideal gases 211 [IES-2007]
IES-15.

S K Mondals
(d) Compressibility factor is more than unity for ideal gases
IES-16. Assertion (A): At very high densities, compressibility of a real gas is less than one. [IES-2006] Reason (R): As the temperature is considerably reduced, the molecules are brought closer together and thermonuclear attractive forces become greater at pressures around 4 MPa. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is not the correct explanation of A (c) A is true but R is false (d) A is false but R is true The value of compressibility factor for an ideal gas may be: [IES-2002] 1. less or more than one 2. equal to one 3. zero 4. less than zero The correct value(s) is/are given by: (a) 1 and 2 (b) 1 and 4 (c) 2 only (d) 1 only Assertion (A): The value of compressibility factor, Z approaches zero of all isotherms as pressure p approaches zero. [IES-1992] Reason (R): The value of Z at the critical points is about 0.29. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is not the correct explanation of A (c) A is true but R is false (d) A is false but R is true
Chapter 8
IES-17.
IES-18.
Adiabatic Process
IES-19. Assertion (A): An adiabatic process is always a constant entropy process. Reason(R): In an adiabatic process there is no heat transfer. [IES-2005] (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is not the correct explanation of A (c) A is true but R is false (d) A is false but R is true A control mass undergoes a process from state 1 to state 2 as shown in the given figure. During this process, the heat transfer to the system is 200 KJ. IF the control mass returned adiabatically. From state 2 to state 1 by another process, then the work interaction during the return process (in kNm) would be: (a) 400 (b) 200 (c) 200 (d) 400
IES-20.
[IES-1998]
IES-21.
A gas expands from pressure P1 to pressure P2 (P2 = p1/10). If the process of expansion is isothermal, the volume at the end of expansion is 0.55 m3. If the process of expansion is adiabatic, the volume at the end of expansion will be closer to: [IES-1997]
212

S K Mondals
(a) 0.45 m3
IES-22.
Chapter 8
(b) 0.55 m3 (c) 0.65 m3 (d) 0.75 m3
A balloon which is initially collapsed and flat is slowly filled with a gas at 100 kPa so as to form it into a sphere of 1 m radius. What is the work done by the gas in the balloon during the filling process? [IES-2008] (a) 4289 kJ (b) 4189 kJ (c) 4209 kJ (d) 4169 kJ
Isothermal Process
IES-23. An ideal gas undergoes an isothermal expansion from state R to state S in a turbine as shown in the diagram given below: The area of shaded region is 1000 Nm. What is the amount is turbine work done during the process? (a) 14,000 Nm (b) 12,000 Nm
(c) 11,000Nm
[IES-2004] (d) 10,000Nm [IES-1997]
IES-24.
The work done in compressing a gas isothermally is given by

1 p2 (a) p1v1 1 p1 1
p (b) mRT1 log e 2 p1 T (d ) mRT1 1 2 kJ T1
(c) mc p (T2 T1 ) kJ
IES-25.
The slope of log P-log V graph for a gas for isothermal change is m1 and for [IES-1992] adiabatic changes is m2. If the gas is diatomic gas, then (a) m1<m2 (b) m1>m2 (c) m1 + m2 = 1.0 (d) m1 = m2 The work done during expansion of a gas is independent of pressure if the expansion takes place [IES-1992] (a) Isothermally (b) Adiabatically (c) In both the above cases (d) In none of the above cases Air is being forced by the bicycle pump into a tyre against a pressure of 4-5 bars. A slow downward movement of the piston can be approximated as (a) Isobaric process (b) Adiabatic process (c) Throttling process (d) Isothermal process [IES-2011] Three moles of an ideal gas are compressed to half the initial volume at a constant temperature of 300k. The work done in the process is [IES-1992] (a) 5188 J (b) 2500 J (c) 2500 J (d) 5188 J
IES-26.
IES-26a
IES-27.
213

S K Mondals
IES-28.
Chapter 8
The change in specific entropy of a system undergoing a reversible process is given by s2 s1 = c p cv ln ( v2 / v1 ) . This is valid for which one of the following?
(a) (b) (c) (d)
Adiabatic process undergone by an ideal gas Isothermal process undergone by an ideal gas Polytropic process undergone by a real gas Isobaric phase change from liquid to vapour
[IES-2008]
Polytropic Process
IES-29. Assertion (A): Though head is added during a polytropic expansion process for which > n> 1, the temperature of the gas decreases during the process. Reason (R): The work done by the system exceeds the heat added to the system. (a) Both A and R are individually true and R is the correct explanation of A [IES 2007] (b) Both A and R are individually true but R is not the correct explanation of A (c) A is true but R is false (d) A is false but R is true n p1v1 p2 v2 In a polytropic process, the term [IES-2005] is equal to: 1 (n 1)
IES-30.
(a) Heat absorbed or rejected (c) Ratio of T1/T2

IES-31.
(b) Change in internal energy (d) Work done during polytropic expansion
The heat absorbed or rejected during a polytropic process is equal to:
n (a) 1
1/2
x work done
n (b) x work done n 1

n (d ) x work done 1
2
[IES-2002]
n (c) x work done 1
Constant Pressure or Isobaric Process

IES-32. Change in enthalpy in a closed system is equal to the heat transferred, if the reversible process takes place at [IES-2005] (a) Temperature (b) Internal energy (c) Pressure (d) Entropy Which one of the following phenomena occurs when gas in a piston-in-cylinder assembly expands reversibly at constant pressure? [IES-2003] (a) Heat is added to the gas (b) Heat is removed from the gas (c) Gas does work from its own stored energy (d) Gas undergoes adiabatic expansion A saturated vapour is compressed to half its volume without changing its temperature. The result is that: [IES-1997] (a) All the vapour condenses to liquid (b) Some of the liquid evaporates and the pressure does not change (c) The pressure is double its initial value (d) Some of the vapour condenses and the pressure does not change
IES-33.
IES-34.
214

S K Mondals
IES-35.
Chapter 8
An ideal gas at 27C is heated at constant pressure till its volume becomes three times. [IES-2008] What would be then the temperature of gas? (a) 81 C (b) 627 C (c) 543 C (d) 327 C
Constant Volume or Isochoric Process

IES-36. In which one of the following processes, in a closed system the thermal energy transferred to a gas is completely converted to internal energy resulting in an increase in gas temperature? [IES-2008] (a) Isochoric process (b) Adiabatic process (c) Isothermal process (d) Free expansion Which one of the following thermodynamic processes approximates the steaming of food in a pressure cooker? [IES-2007] (a) Isenthalpic (b) Isobaric (c) Isochoric (d) Isothermal Assertion (A): The constant pressure lines are steeper than the constant volume lines for a perfect gas on the T-S plane. [IES-2010] Reason (R): The specific heat at constant pressure is more than the specific heat at constant volume for a perfect gas. (a) Both A and R are individually true and R is the correct explanation of A (b) Both A and R are individually true but R is not the correct explanation of A (c) A is true but R is false (d) A is false but R is true Consider the four processes A, B, C and D shown in the graph given above: Match List-I (Processes shown in the graph) with List-II (Index n in the equation pvn = Const) and select the correct answer using the code given below the lists: [IES-2007, 2011] List-I A. A B. B C. C D. D Codes: (a) (c) IES-38a List-II 1. 0 2. 1 3. 1.4 4. A 4 1 B 2 3 C 3 2 D 1 4
IES-37.
IES-37a
IES-38.
(b) (d)
A 1 4
B 2 3
C 3 2
D 4 1
Match List I with List II and select the correct answer using the code given below the lists: List I List II (Process index n) (T-s traces) A. 0 215

S K Mondals
Code :
B. 1.0 C. 1.4 D.
Chapter 8
1 2 3 T 4
(a) (b) (c) (d)
A 3 2 3 2
B 1 1 4 4
C 4 4 1 1
D 2 3 2 3
IES-39.
[IES-2010] Match List-I (process) with List-II (index n in PVn = constant) and select the correct answers using the codes given below the lists. [IES-1999] List-I List-II 1. n = infinity A. Adiabatic B. Isothermal 2. n = C p
Cv
C. Constant pressure D. Constant volume Codes: (a) (c) IES-40. A 2 2 B 3 3 C 5 5 D 4 1
3. n = 1 4. n = C p -1
Cv
5. n = zero A (b) 3 (d) 2
B 2 5
C 1 3
D 5 1
A system at a given state undergoes change through the following expansion processes to reach the same final volume [IES-1994] 1. Isothermal 2. Isobaric 4. Polytropic(n =1.3) 3. Adiabatic ( = 1.4) The correct ascending order of the work output in these four processes is (a) 3, 4, 1, 2 (b) 1, 4, 3, 2 (c) 4, 1, 3, 2 (d) 4, 1, 2, 3 Match the curves in Diagram-I with the curves in Diagram-II and select the correct answer. [IES-1996] Diagram-I (Process on p-V plane) Diagram-II (Process on T-s plane)
IES-41.
Code: (a)
A 3
B 2
C 4
D 5
(b) 216
A 2
B 3
C 4
D 5

S K Mondals
(c)
IES-42.
Chapter 8
2 3 4 1 (d) 1 4 2 3
Four processes of a thermodynamic cycle are shown above in Fig.I on the T-s plane in the sequence 1-2-3-4. The corresponding correct sequence of these processes in the p- V plane as shown above in Fig. II will be [IES-1998] (a) CDAB (b) DABC (c) ABCD (d) BCDA IES-43. Match List-I with List-II and select the correct answer List-I List-II A. Work done in a polytropic process B. Work done in a steady flow process C. Heat transfer in a reversible adiabatic process D. Work done in an isentropic process Codes: (a) (c) IES-44. A 4 4 B 1 1 C 3 2 D 2 3 1. 2. Zero 3. 4. [IES-1996]
vdp
p1V1 p2V2 1 p1V1 p2V2 n 1
C 2 3
(b) (d)
A 1 1
B 4 2
D 3 4
A perfect gas at 27C was heated until its volume was doubled using the following three different processes separately [IES-2004] 1. Constant pressure process 2 Isothermal process 3. Isentropic process Which one of the following is the correct sequence in the order of increasing value of the final temperature of the gas reached by using the above three different processes? (a) 1 2 3 (b) 2 3 1 (c) 3 2 1 (d) 3 1 2
Previous 20-Years IAS Questions Ideal Gas

IAS-1. Variation of pressure and volume at constant temperature are correlated through [IAS-2002] (a) Charles law (b) Boyles law (c) Joules Law (d) Gay Lussacs Law
217

S K Mondals
IAS-2. Reason (R): For a perfect gas,
Chapter 8
Pv = constant. T
Assertion (A): For a perfect gas, hyperbolic expansion is an isothermal expansion. [IAS-2007]
(a) (b) (c) (d)

IAS-3.
Both A and R are individually true and R is the correct explanation of A Both A and R are individually true but R is not the correct explanation of A A is true but R is false A is false but R is true
Variation of pressure and volume at constant temperature are correlated through [IAS-2002] (a) Charles law (b) Boyles law (c) Joules law (d)Gay Lussacs law An ideal gas with initial volume, pressure and temperature of 0.1 m3, 1bar and 27C respectively is compressed in a cylinder by a piston such that its final volume and pressure are 0.04 m3 and 5 bars respectively, then its final temperature will be: [IAS-2001] (a) 123C (b) 54C (c) 327C (d) 600C
IAS-4.
Equation of State of a Gas

IAS-5. The volumetric air content of a tyre at 27C and at 2 bars is 30 litres. If one morning, the temperature dips to -3C then the air pressure in the tyre would be: [IAS-2000] (a) 1.8 bars (b) 1.1 bars (c) 0.8 bars (d) The same as at 27C An Ideal gas with initial volume, pressure and temperature of 0.1m3, 1 bar and 27C respectively is compressed in a cylinder by piston such that its final volume and pressure 0.04 m3 and 5 bar respectively, then its final temperature will be: [IAS-2001] (a) 123C (b) 54C (c) 327C (d)600C Which one of the following PV-T diagrams correctly represents the properties of an ideal gas? [IAS-1995]
IAS-6.
IAS-7.
218

RTc is equal pc vc
Van der Waals Equation

IAS-8. If a gas obeys van der Waals' equation at the critical point, then to which one of the following (a) 0 (b) 1 [IAS-2004; 2007] (c) 15 (d) 267 a In Van der Waals gas equation P + 2 ( v b ) = RT (R = Universal gas v constant) the unit of b is: [IAS-1997]
IAS-9.
(a) Liter/moleC
IAS-10.
(b) m3/mole
(c) kg-liter/mole
(d) Dimensionless
A higher value of Van der waals constant for a gas indicates that the [IAS-2003] (a) Molecules of the gas have smaller diameter (b) Gas can be easily liquefied (c) Gas has higher molecular weight (d) Gas has lower molecular weight
Critical Properties
IAS-11. The mathematical conditions at the critical point for a pure substance are represented by: [IAS-1999]
(a) (c)
IAS-12.
p 2p 3p < 0, 2 = 0 and 3 = 0 v v v 2 p p 3p = 0, 2 = 0 and 3 < 0 v v v
(b) (d)
p 2p 3p = 0, 2 < 0 and 3 = 0 v v v 2 p p 3p = 0, 2 = 0 and 3 = 0 v v v
In the above figure, yc corresponds to the critical point of a pure substance under study. Which of the following mathematical conditions applies/apply at the critical point?
(a)
P =0 v Tc
2 P =0 (b) 2 v Tc
(c)
[IAS-2007]
P 3 <0 v T
3
c
(d) All of the above
Adiabatic Process
IAS-13. Consider the following statements: [IAS-2007]
219

1. During a reversible non-flow process, for the same expansion ratio, work done by a gas diminishes as the value of n in pvn = C increases. 2. Adiabatic mixing process is a reversible process. Which of the statements given above is/are correct? (a) 1 only (b) 2 only (c) Both 1 and 2 (d) Neither 1 nor 2
Isothermal Process
IAS-14. Identify the process of change of a close system in which the work transfer is maximum. [IAS-2003] (a) Isothermal (b) Isochoric (c) Isentropic (d) Polytrop In a reversible isothermal expansion process, the fluid expands from 10 bar and 2 m3 to 2 bar and 10 m3. During the process the heat supplied is at the rate of 100 kW. What is the rate of work done during the process? [IAS-2007] (a) 20 kW (b) 35 kW (c) 80 kW (d) 100 kW In respect of a closed system, when an ideal gas undergoes a reversible isothermal process, the [IAS-2000] (a) Heat transfer is zero (b) Change in internal energy is equal to work transfer (c) Work transfer is zero (d) Heat transfer is equal to work transfer IAS-15.
IAS-16.
Constant Pressure or Isobaric Process

IAS-17. For a non-flow constant pressure process the heat exchange is equal to: (a) Zero (b) The work done [IAS-2003] (c) The change in internal energy (d) The change in enthalpy
Constant Volume or Isochoric Process

IAS-18. An ideal gas is heated (i) at constant volume and (ii) at constant pressure from the initial state 1. Which one of the following diagrams shows the two processes correctly? [IAS-1996]
IAS-19.
One kg of a perfect gas is compressed from pressure P1 to pressure P2 by 1. Isothermal process 2. Adiabatic process 3. The law pv1.4 = constant The correct sequence of these processes in increasing order of their work requirement is: [IAS-2000] (a) 1, 2, 3 (b) 1, 3, 2 (c) 2, 3, 1 (d) 3, 1, 2 Match List-I with List-II and select the correct answer using the codes given below the Lists: [IAS-1997]
IAS-20.
220

S K Mondals
List-I A. Constant volume process B. Constant pressure process C. Constant temperature process D. Constant entropy process Codes: (a) (c) A 3 3 B 2 4 C 1 1 D 4 2 List- II dP P = 1. dV V dP P = 2. dV V dT T 3. = ds Cv 4.
dT T = ds CP A (b) 2 (d) 1
Chapter 8
B 4 3
C 3 4
D 1 2
Properties of Mixtures of Gases

IAS-21. If M1, M2, M3, be molecular weight of constituent gases and m1, m2, m3 their corresponding mass fractions, then what is the molecular weight M of the mixture equal to? [IAS-2007]
(a) m1M 1 + m2 M 2 + m3 M 3 + ........... (c)
1 1 1 + + + ........... m1M 1 m2 M 2 m3 M 3
1 m1M 1 + m2 M 2 + m3 M 3 + ........... 1 (d) m1 m2 m3 + ............... + + M1 M 2 M 3

(b)
IAS-22.
The entropy of a mixture of pure gases is the sum of the entropies of constituents evaluated at [IAS-1998] (a) Temperature and pressure for the mixture (b) Temperature of the mixture and the partical pressure of the constituents (c) Temperature and volume of the mixture (d) Pressure and volume of the mixture
221


GATE-1. (b). Let no of mole = n
Initial
P1 = 10 bar V1 = (
Final
P2 =? V2 = (
1 ) m3/mole n
2 ) m3/mole n
T1 = 300K
(P1+a/v12) v1 =(P2+a/v22) v2 (10 + an2) x (1/n)= (P2 + an2/4) x (2/n) 2P2 = 10 + an2-an2/2 = 10 + an2/2
T2 = 300K = T1=T (say)
P2 = 5 + an2/4
As a>0 P2 is slightly more than 5 bar.

GATE-2. Ans. (a) w.d =
W .K .T PV = mRT PV 1 1 = R T1 R = 8.314kJ kmol 1 K 1 m 8.314 0.1 103 V1 = 300 40 V1 = 0.623 m3
1
( p2 v2 p1v1 )
P V2 1 V2 = 0.41m3 = V1 P2 (.2 0.41 0.1 0.623) 103 W .d = = 29.7 0.67 GATE-3. Ans. (d) Heat lost = n Cv d T GATE-4. Ans. (c) GATE-5. Ans. (c) Heat produced by electric bulb in 24 hr. = 100 24 60 60 J = 8640kJ
Volume of air = 2.5 3 3 = 22.5 m 3 Density () = 1.24 kg/m3 Q 8640 Q = mCv t or t = = = 430 o C t = 430 + 20 = 450 o C mCv 22.5 1.24 0.716
GATE-6. Ans. (a) Iso-thermal work done (W) = RT1 ln
V2 V1
222

S K Mondals
V2 = PV 1 1 ln V1 0.030 = 800 0.015 ln = 8.32kJ/Kg 0.015
GATE-7. Ans. (b) Remember if we mix 2 mole of oxygen with another 2 mole of other gas the
Chapter 8
volume will be doubled for first and second constituents S = nR ln
Vtotal = 2 R ln 2 Vinitial
Total Entropy change = 4Rln2 So, Entropy change per mole=Rln2. And it is due to diffusion of one gas into another.

IES-1. Ans. (a) Both A and R correct and R is the correct explanation of A IES-2. Ans. (b) For perfect gas, both the assertion A and reason R are true. However R is not the explanation for A. A provides definition of perfect gas. R provides further relationship for enthalpy and internal energy but can't be reason for definition of perfect gas. IES-3. Ans. (b) As internal energy is a function of temperature only. In isothermal expansion process no temperature change therefore no internal energy change. A Reversible isothermal expansion process is constant internal energy process i.e. dU = 0 dQ = dU + dW
dQ = dW ( dU = 0 )
Work done during the process = 100kW IES-4. Ans. (a) IES-5. Ans. (d) (a) True. A water film, if formed, will act as a very poor conductor of heat and will not easily let the heat of the furnace pass into the boiler. An oil film if present, is even worse than water film and the formation of such films inside the boiler must be avoided. (b) Since the mass and material are the same, the volumes must also be the same. For the same volume, the surface area of the plate is the greatest and that of the sphere is the least. The rate of loss of heat by radiation being proportional to the surface area, the plate cools the fastest and the sphere the slowest. 3 5 (c) True, for a monoatomic gas, C1 = R and for a diatomic gas, C1 = R. 2 2 13 5 Since the mixture has two moles, the value of C1 for the mixture = R + R = 2 R 22 2 3 RT (d) False, The average kinetic energy of 1 g of an ideal gas = 2 M Where M is the molecular weight of the gas and it is different gases, as the value of M will be different. IES-6. Ans (b) In Perfect gas intermolecular attraction is zero. It will be only possible when intermolecular distance will be too high. High temperature or low pressure or both cause high intermolecular distance so choice 1 and 3. IES-7. Ans. (a) The correct sequence for decreasing order of the value of characteristic gas constants is hydrogen, nitrogen, air and carbon dioxide. IES-8. Ans. (b)
223

S K Mondals
IES-9. Ans. (d) we know that P =
Chapter 8
1 C 2 If momentum is zero then C must be zero. Hence P 3
would be zero. That will occur at absolute zero temperature. But note here choice (a) has in defined temp. 273K which is imaginary temp. IES-9a. Ans. (d) IES-10. Ans. (a) IES-11. Ans. (c) IES-12. Ans. (b) Joules law states that for an Ideal gas internal energy is a function of temperature only. u = (T). But this is not Ideal gas it is real gas. IES-13. Ans. (a) We know that at critical point a = 3PcVc2 ; b = Vc/3 and R =
8 PcVc 3Tc
IES-14. Ans. (a) 1 is false. At very low pressure, all the gases shown have z 1 and behave nearly perfectly. At high pressure all the gases have z > 1, signifying that they are more difficult to compress than a perfect gas (for a given molar volume, the product pv is greater than RT). Repulsive forces are now dominant. At intermediate pressure, must gasses have Z < 1, including that the attractive forces are dominant and favour compression. IES-15. Ans. (a) IES-16. Ans. (d) IES-17. Ans. (c) IES-18. Ans. (d) IES-19. Ans. (d) IES-20. Ans. (b) During adiabatic process, work done = change in internal energy. Since control man (so case of closed system). Intercept of path on X-axis is the work done by the process. W = area of A12 + area of A2CB 1 (3 - 1) 200 + 100 (3 - 1) W= 2 = 200 + 200 = 400 kJ
W=
1 (300 - 100) 2 + 100 2 2 = 200 + 200 = 400 kJ From 1 2. U1 + Q = U2 + W. U1 U2 = W Q = 400 200 = 200 kJ. From 2 1 Work done will be same Since adiabatic So Q = 0 U2 + Q = U1 + W W = U2 U1 = ( U1 U2 ) = 200 kJ.
IES-21. Ans. (a) For isothermal process, p1v1 = p2 v2 , or p1v1 =
For adiabatic process 224
p1 0.55, v1 = 0.055 m3 10

S K Mondals
1.4 p1v1 = p2 v1.4 2 , or p1 ( 0.055 ) 1.4
Chapter 8
= p1 1.4 v2 or v2 = 0.0551.4 10 = 0.45 m3 10
= 4 13 (100 ) = 418.9 kJ 3
IES-22. Ans. (b) Work done by the gas during filling process = vdp
IES-23. Ans. (c) Turbine work = area under curve RS = P dv
= 1 bar ( 0.2 0.1) m3 + 1000 Nm
= 105 ( 0.2 0.1) Nm + 1000Nm = 11000Nm

IES-24. Ans. (b) IES-25. Ans. (a) PV = constant, C log P + log V = log C m1 = -1
Pv 4 = C log P + q log V = log C m2 = -q = - 1.4 m2 > m1 IES-26. Ans. (d) IES-26a Ans. (d) IES-27. Ans. (d) Since the temperature remains constant, the process is isothemal. V Work-done in the process, W = 2.303 nRT log 2 V1 1 = 2.303 3 8.315 8.315 300 log 2 = 5188 J. The negative sign indicates that work is done on the gas. IES-28. Ans. (b) Tds = du + pdv
ds = C V dT + pdv
dT P + dv T T dT R ds = C V + dv T V
ds = C V
Integrating the above expression
S2 S1 = C V In
T2 V + RIn 2 T1 V1 V2 V1
For isothermal process undergone by ideal gas.
S2 S1 = ( CP C V ) In
IES-29. Ans. (a) IES-30. Ans. (a) IES-31. Ans. (c) IES-32. Ans. (c) dQ = du + pd + pd dp = d ( u + p ) dp = dh dp
225

S K Mondals
if dp = 0 or p = const. these for ( dQ )p = ( dh )p
Chapter 8
IES-33. Ans. (a)
IES-34. Ans. (d) By compressing a saturated vapour, its vapours condense and pressure remains unchanged. Remember it is not gas. V V V1 3V1 IES-35. Ans. (b) 1 = 2 = T1 T2 ( 273 + 27 ) T2
T2 = 300 3 = 900 K = 627C IES-36. Ans. (a) Constant volume (isochoric) process: An example of this process is the heating or cooling of a gas stored in a rigid cylinder. Since the volume of the gas does not change, no external work is done, and work transferred W is zero. Therefore from 1st law of thermodynamics for a constant volume process:
1
W2 = 0
2
1Q 2 = dU = U2 U1 1
IES-37. (c) In a pressure cooker, the volume of the cooker is fixed so constant volume process but for safety some of steam goes out to maintain a maximum pressure. But it occurs after proper steaming. IES-37a Ans. (d) IES-38. Ans. (b) IES-38a Ans. (c) IES-39. Ans. (c) IES-40. Ans. (a) IES-41. Ans. (b) IES-42. Ans. (d) IES-43. Ans. (c) IES-44. Ans. (c) Perfect gas T1 = 27 + 273 = 300 k V1 = initial volume V2 = final volume, V2 = 2V1 T2 = ?
226

S K Mondals
(i) Constant Pressure Process V T
V1 V2 = T1 T2 V1 2V1 = T1 T2
Chapter 8
T2 = 2T1 = 600 k (ii) Isothermal Process T = Constant T1 = T2 = 300 k (iii) Isentropic Process T1 V1r 1 = T2 V2r 1
V V T2 = T1 1 = T1 1 V2 2V2 T2 = 0.757 T1 = 227.35K
r 1 1.4 1

IAS-1. Ans. (b) Boyles law: It states that volume of a given mass of a perfect gas varies inversely as the absolute pressure when temperature is constant. IAS-2. Ans. (a) IAS-3. Ans. (b) IAS-4. Ans. (c)
PV PV 1 1 = 2 2 T1 T2
or T2 =
PV 5 0.04 2 2 T1 = (300) = 600 K = 327C 1 0.1 PV 1 1
IAS-5. Ans. (a) Apply equation of states ( 273 3 ) P1V1 P2 V2 T [V1 = V2 ] or P2 = P1 2 = 2 = = 1.8bar T1 T2 T1 ( 273 + 27 ) IAS-6. Ans. (c ) Apply equation of states
P1V1 P2V2 PV = or T2 = 2 2 xT1 T1 T2 P1V1
T2 = (
IAS-7. Ans. (c) For an ideal gas PV = MRT i.e. P and T follow direct straight line relationship, which is depicted in figure (c). IAS-8. Ans. (d) a = 3 pc Vc2, b =
5 0.04 )( ) (273 + 27) = 600K = 327C 1 0 .1
Vc 8 PV c c , R= 3 3 Tc
IAS-9. Ans. (b) According to dimensional homogeneity law unit of molar-volume and b must be
same. i.e. m3/mole

IAS-10. Ans. (b) IAS-11. Ans. (c) IAS-12. Ans. (d) Van der Waals equation
227

S K Mondals
RT a 2 b V 8 PV c c At critical point a= 3pcVc2, b= c , R = 3 3 Tc RTc 2a P = + 3 =0 2 V T =Tc (Vc b ) Vc or P = a P + 2 ( b ) = RT
Chapter 8
2 P 2.RTc 6a = 4 =0 2 3 V T =Tc (Vc b ) Vc 3 P 6 RTc 24a = 5 = 9 pc i.e.-ive And 3 ( vc b ) vc V T =Tc

IAS-13. Ans. (a) In adiabatic mixing there is always increase in entropy so large amount of irreversibility is these.
IAS-14. Ans. (c) IAS-15. Ans. (d) For reversible isothermal expansion heat supplied is equal to work done during the
process and equal to Q = W = mRT1 ln
v2 v1
Temperature constant so no change in internal energy dQ = dU + dW; dU = 0 Therefore dQ = dW. IAS-16. Ans. (d) In reversible isothermal process temperature constant. No change in internal energy. So internal energy constant dQ = u + W as u = 0 , dQ = dW IAS-17. Ans. (d) IAS-18. Ans. (d)
228

S K Mondals
IAS-19. Ans. (b) Work requirement 1. Isothermal area under 121B1A 2. Adiabatic area under 122B2A 3. pv1.1 = c area under 123B3A
Chapter 8
IAS-20. Ans. (c) IAS-21. Ans. (a) IAS-22. Ans. (b)
229

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Basic Concepts

Thermodynamic System and Control Volume

B Basic C Conce epts

Closed System S (Contro ( ol Mass System m)

B Basic C Conce epts

O Open Sy ystem (Contr rol Vol lume System S )

B Basic C Conce epts

Fig. An n Isolated System S

Q Quasi-St tatic Pr rocess

B Basic C Conce epts

La aws of Thermodynam mics

Summat tion of 3 Laws s

B Basic C Conce epts

eroth Law L of Thermo T odynam mics Ze

In nternati ional Te empera ature Sc cale

B Basic C Conce epts

B Basic C Conce epts

W Work a path p fun nction

Free Exp pansion n with Zero Z W Work Tra ansfer

T The process of free ex xpansion is

irr reversible. . Also work done is zero o during fre ee expansion n.

Free Expa ansion

pd dV-wor rk or Displacement Work W

B Basic C Conce epts

B Basic C Conce epts

can n be perform med only

on a quasi-sta atic path.

Fig. Quasi-Static pdV Work k

Heat Tra ansfer-A A Path Functio on

Th he displaceme ent work is given g by

PR ROBLEM MS & SO OLUTION NS

1 V = V23 V13 + 10ln 2 V1 3 4.5 1 = 4.53 1.53 + 10ln 1.5 3

1 = ( 91.125 3.375 ) + 10ln3 3 = [29.250 + 10.986] = 40.236 kJ

ASKED OBJECTIVE QUESTIONS (GATE, IES, IAS)

Open and Closed systems

(b) extensive properties (d) path functions

Free Expansion with Zero Work Transfer

pdV-work or Displacement Work

vdp , where v is the specific volume and p is the pressure. The

(d) Is incorrect; it must be =

Previous 20-Years IES Questions

Thermodynamic System and Control Volume

Open and Closed systems

Code: (a) (c)

Zeroth Law of Thermodynamics

International Temperature Scale

Work a Path Function

(c) Is a function of pressure only

(d) Depends on the path followed by the system 17

Free Expansion with Zero Work Transfer

pdV-work or Displacement Work

pdv represents the work of

Tds represents heat of any

and vdp for a thermodynamic system of an Ideal gas on valuation

Heat Transfer-A Path Function

Previous 20-Years IAS Questions Thermodynamic System and Control Volume

Zeroth Law of Thermodynamics

International Temperature Scale

Free Expansion with Zero Work Transfer

and vdp for a thermodynamic system of an Ideal gas on valuation

to represent the work, which of the following

pdV-work or Displacement Work

Heat Transfer-A Path Function

Answers with Explanation (Objective)