Placement Team, Chemical Engineering, IIT Madras 2012

THERMODYNAMICS

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 Placement Team, Chemical Engineering, IIT Madras 2012

REFERENCE TEXT BOOK: INTRODUCTION TO CHEMICAL ENGINEERING

THERMODYNAMICS (SMITH AND VAN NESS).

LAWS OF THERMODYNAMICS:

ZEROTH LAW: if a system A is in thermal equilibrium with system C and

a system B is also in thermal equilibrium with system C then the
systems A and B are also in thermal equilibrium.

FIRST LAW: energy can neither be created nor destroyed. It can only be
transformed from one form to another. It is impossible to create a
perpetual motion machine i.e. a machine which gives energy without
expenditure of energy.

(energy of system) + (energy of surroundings) =0.

Reference: page number18 to page number 52.

SECOND LAW:

Statement1: no apparatus can operate in such a way that its only

effect (in system and surroundings) is to convert heat absorbed by
a system completely into work done by the system.
Statement2: no process is possible which consists solely in the
transfer of heat from one temperature level to a higher one.

Reference: page number148 to page number 178.

HEAT ENGINES: essentially all heat engine cycles are absorption of heat
into the system at higher temperature, rejection of heat to the
surroundings at lower temperature and production of work.

Efficiency () = (net work output/heat absorbed).

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= 1- |QC/QH|

Where,

QC is the heat rejected at the cold reservoir.

QH is the heat absorbed at the hot reservoir.

CARNOT CYCLE: refer page number150 (smith and van ness).

CARNOT THEORM: for two given heat reservoirs no engine can have a
thermal efficiency higher than that of a carnot engine.

Corollary: the efficiency of carnot engine depends only on the

temperature levels and not upon the working substance of the engine.

Reference: page numbers149, 150, 151.

TYPES OF SYSTEMS:

ISOLATED SYSTEM: it is a system which doesnt interact at all with

the surroundings i.e. there is no heat transfer and mass transfer
between the system and surroundings.
OPEN SYSTEM: it is a type of system where there are both mass
transfer and heat transfer between the surroundings and the
system.
CLOSED SYSTEM: there is no mass transfer but heat transfer takes
place between the system and the surroundings. Closed systems
often undergo processes that cause no change in the system
other than its internal energy.
Ut = Q+W.

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PHASE RULE: it is applied to systems at equilibrium only.

F = 2- + N.

Where,

is the number of phases.

N is the number of chemical species.

F is the degrees of freedom of the system.

Reference: page number 26 and 27.

SIGN CONVENTION:

Work done by the system: W is -ve.

Work done on the system: W is +ve.
Heat flows into the system: Q is +ve.
Heat flows out of the system: Q is -ve.

H = U + nRT

Where,

H is internal heat content or enthalpy change.

U is internal energy change.

EXTENSIVE PROPERTIES: these are those properties which depend

upon the amount of substance present in the system. Ex: mass, energy,
volume, enthalpy, entropy, free energy etc.

INTENSIVE PROPERTIES: these are those properties independent of the

amount of substance. Ex: pressure, density, viscosity, temperature,
concentration, surface tension, refractive index etc.

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PROCESS: the operation by which a system changes from initial state to

final state is called a process.

DIFFERENT TYPES OF PROCESSES:

ISOTHERMAL PROCESS: the temperature of the system remains

constant throughout the process.
ADIABATIC PROCESS: no heat enters or leaves the system during
this process.
ISOBARIC PROCESS: the pressure of the system remains constant
throughout the process.
ISOCHORIC PROCESS: volume of the system remains constant
throughout the process.
reference page numbers: 34 and 35.
Reversible processes and irreversible processes.

Reference: page numbers 28,29,30,31.

ENTHALPY:

H = U + (PV).

Reference page numbers: 35 and 36.

HEAT CAPACITY: C = dQ/dT

This definition makes Q a process dependent quantity rather than a

state function.

Heat capacity at constant volume.

Heat capacity at constant pressure.
Reference page numbers:37, 38.

ENTROPY (S):
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The entropy of the universe always tends towards a maximum.

For a process to be spontaneous the entropy should increase i.e.

S > 0.

S mixing of gasses is always greater than zero.

S mixing of gas is ( ni *R* lnxi)

Where ni is the number of moles of

Reference page numbers: page 155 to page 164.

THERMODYNAMIC PROPERTIES OF FLUIDS:

H = U + PV.
A = U TS.
G = H TS.
dU = TdS PdV
dH = TdS + VdP
dA = -PdV SdT
dG = VdP - SdT

reference page numbers: 186, 187, 188.

MAXWELLS EQUATIONS: reference page : 189.

INTERNAL ENERGY (U):

It is a path independent function.

FREE ENERGY (G):

For a process to be spontaneous the free energy should decrease i.e.

G < 0.

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REFRIGRATION: vapor compression cycle.

Coefficient of performance () = heat absorbed at lower

temperature/net work.

Reference page numbers: 295, 296, 297.

FUGACITY (f):

f = p * exp (( - o) / RT).

Reference page numbers: page 368 to page 375.

ROULTS LAW:

Vapor phase is an ideal gas

Liquid phase is an ideal solution.

yiP = xiPisat

Reference page numbers: 326, 327.

HENRYS LAW:

yiP = xiHi

Reference page number: 333, 334.

VAPOR LIQUID EQUILIBRIUM (VLE):

CONDITION:

At equilibrium, the temperature (Tv = Tl), pressure (Pv = Pl) and

fugacity (fv =fl) of both the vapor phase and liquid phase are equal.

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WHEN A SUBCOOLED LIQUID IS HEATED:

BUBBLE POINT: the first bubble of vapor is formed.

DEW POINT: the last drop of liquid is about to vaporize. The vapor
would have same composition as that of feed.

T-x-y diagrams or P-x-y diagrams are used to represent the vapor-liquid

equilibrium.

Reference page numbers: page 314 to page 346.

CHEMICAL REACTION EQUILIBRIA:

o Extent of reaction.
o Equilibrium constant.
o Equilibrium conversion of reactants.
o Equilibrium concentration of all species.
Reference page numbers: page 450 to page 468.

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