PROCESS ENGINEERING

THERMODYNAMICS

Dr. Dharmendra Kumar Bal

Assistant Professor (Sr.)
SCALE
MODULE-2
First law of Thermodynamics

First law of thermodynamics while applied to a process for a closed system give
rise to a property called internal energy U.

If Q is the amount of heat transferred to the system and W is the amount of work
transferred from the system during the process the net energy transfer (Q - W) will
be stored in the system.

both the heat and work are energies in transit,

they can not be stored. Hence, the quantity (Q
- W) is not either heat or work, but it is entirely
a new form of energy, known as internal
energy or simply the energy of the system.

Q - W = ΔE
Q = W + ΔE

Q2 + Q3 - Q1 = ΔE + (W2 + W3 - W1 - W4)
 First Law of Thermodynamics

• This implies that the difference between the heat

and work interactions during a process is a
property of the system and a point function. This
property is called the energy of the system.
Energy of a system is an extensive property
E consists of
U -internal energy
KE -the kinetic energy Mathematically properties are called point
PE - Potential Energy functions or state functions
HEAT and WORK are not properties because
they depend on the path and end states.
Analogy
Balance in your bank account is a property. The deposits and withdrawals are not.
A given balance can be obtained by a series of deposits and withdrawals or a single
large credit or debit!
 First law

First Law gives a quantitative measure of energy

It can not distinguish the different types of energy
It fails to indicate the direction of flow of energy
It can not indicate whether the process is cyclic or not.
First law applied to a process gives rise to a property (internal
energy, U for a closed system and enthalpy, h for a open system)
First Law of Thermodynamics

for non Flow Process

H  Q  Ws
for Flow Process

1 2
H  gZ  u  Q  Ws
2
• The cyclic integral of any thermodynamic
property is zero (∫dE = 0)
Thermodynamic Processes
 Process : Any change that a system undergoes from one equilibrium state to
another is called a process.
The series of states through which a system passes during a process is called
the path of the process.
Properties like heat and work interactions are functions of path. Changes
in enthalpy and internal energy are functions of only state and not of the
path taken between the two states.
• Common Processes:
– Isothermal: Constant Temperature
– Isobaric: Constant Pressure
– Isometric: Constant Volume
– Adiabatic: No Heat Transfer
P = constant T = constant
(isobaric) (isothermal)

P T
v =constant v =constant
(isometric) (isometric)

v v
Sl Parameter Held Equation of state
Name of the process
No Constant for simple system

1 Constant pressure(Isobaric) p = constant v = (mR/P)T

Constant volume(isochoric)
2 V = constant p = (mR/V)T
process
Constant temperature
3 T = constant pV = constant
(isothermal) process
4 Polytropic process n pVn = constant
no heat flow
5 Adiabatic process across the system pvγ = constant
boundary
6 Isoenthalpic process h = constant h=c
Reversible Process:
When reversed the process the system
and surroundings will come back to
the same initial state.
Equilibrium at
all points along the path
Internally Reversible Process:
When reversed the process only the system
will come back to the same initial state

Irreversible Process:
Is the one in which only initial and final
states are known. Path is not known as
equilibrium is not maintained during the
process.
 Quasi-static Processes
A quasi-static process is one in which
 The deviation from thermodynamic equilibrium is infinitesimal.
 All states of the system passes through are equilibrium states.

 If we remove the weights slowly one by one the pressure of the gas will
displace the piston gradually. It is quasistatic.
 On the other hand if we remove all the weights at once the piston will be
kicked up by the gas pressure.(This is unrestrained expansion) but we don’t
consider that the work is done -because it is not in a sustained manner
 In both cases the systems have undergone a change of state.
 Another eg: if a person climbs down a ladder from roof to ground, it is a
quasistatic process. On the other hand if he jumps then it is not a
quasistatic process.

A reversible state is a quasi-static process without any

dissipation.
 Isothermal process: T=constant
Energy balance U=Q-W, for ideal gas U=H=0
since both are functions of temperature only
mRT 2 dV
Q=W, W=  PdV   dV  mRT 
V 1 V

 V2   P1 
 mRT ln    mRT ln  
 V1   P2 
 Isobaric process: P=constant
2
U=Q-W, W=  PdV=P  dV=P(V2  V1 )
1

Q  U  P(V2  V1 )  (U 2  U1 )  P (V2  V1 )
 (U 2  PV2 )  (U1  PV1 )  H 2  H1  H
 Constant volume process: V=constant
Q-W=U, W=  PdV  0, no work done
Q=U=mu=m  c dT v

 Adiabatic process: Q=0

Q-W=U, -W=U
- W=dU (infinitesimal increment of work and energy)
 mRT 
dU+PdV=0, mc v dT    dV  0
 V 
 RT  cv dT dV
cv dT    dV  0,  , integrate and assume
 V  R T V
c v =constant
Rc k 1
cv  T2   V2  T2  V1  v  V1 
ln     ln   ,    
R  T1   V1  T1  V2   V2 
 k 1
T2  V1 
  , from ideal gas relation
T1  V2 
 V1   T1  P2
PV=RT,      , substitute
 V2   T2  P1
k 1 k 1
T2   T1  P2    T2 
      , multiply   from both sides
T1   T2  P1    T1 
( k 1) k
T2  P2  k  P2   V1 
  , and   
T1  P1   P1   V2 
k k
k  cons tan t
Also PV
1 1  PV
2 2 and pV
For an ideal gas undergoing adiabatic process
Polytropic Process: its P-V relation can be expressed as
PVn = constant, where n is a constant for a specific process
 Isothermal, T=constant, if the gas is an ideal gas then
PV=RT=constant, n=1
 Isobaric, P=constant, n=0 (for all substances)
 Constant-volume, V=constant, V=constant(P)(1/n), n= (for
all substances)
 Adiabatic process, n=k for an ideal gas

PV
1 1
n
 PV
2 2
n
 PV n

2 2
W   PdV   ( PV
1 1
n
)V n
dV
1 1

2 2  PV
2 n
( PV
1 1 ) PV
1 1 
n 1 n 1 n
 ( PV n
) V dV  (V  V )  1 1
1 n 1 n
2 1
1
 Problem

Sulphurdioxide is circulated as the refrigerant in a small refrigerator. SO2 gas at pressure

of 5 bar and temperature 340 K is to be cooled at constant volume of 0.142 m3, to 293 K
as part of refrigeration cycle. Calculate (a) the heat liberated (b) the work done by the
gas on cooling (c) the final pressure attained on cooling and (d) the change in enthalpy.
Sulphur dioxide may be treated as an ideal gas. The specific heat (J/mol K) is found to
vary with temperature (K) according to
Cp  25.736  5.796 102 T  3.8112 105 T 2  8.612 10 9 T 3
Solution
(a) The heat Liberated
P1 = 5 bar P2 = ?
V1 = 0.142 m3 V2 = 0.142 m3
T1 = 340 K T2 = 293 K
Cp= 25.736 + 5.796 x 10-2 T -3.8112 x 10-5 T2 +8.612 x 10-9 T3
Cp – Cv = R = 8.314
Cv = 17.422+ 5.796 x 10-2 T -3.8112 x 10-5 T2 +8.612 x 10-9 T3
 P1 = 5 bar P2 = ?
V1 = 0.142 m3 V2 = 0.142 m3
T1 = 340 K T2 = 293 K
(b) Final pressure attained on cooling

(c ) work done on cooling

(d) Change in enthalpy

 Number of moles of the gas = n =

The total heat liberated = -1514.16 x 25.1171

= 38.031 x 10 3 Joules
Heat out put is negative;

The change in enthalpy = - 1904.3 x 25.1171

= -47.817 x 10 3 joules
 SECOND LAW OF THERMODYNAMICS

KELVIN – PLANCK STATEMENT: It is impossible for a device that operates in a cycle to

receive heat from a single reservoir and produce a net amount of work.

CLAUSIUS STATEMENT: It is impossible to construct a device that operates in a cycle and

produces no effect other than the transfer of heat from lower temperature body to a
higher temperature body.

ENTROPY : The entropy change of a system undergoing a reversible process is given by

dQ CP dT
dS  
T T
 Entropy calculation
PROBLEM

A 40 kg steel casting (CP=0.5 kJ/kg.K) at temperature of 450oC is

quenched In 150 kg of oil (CP=2.5 kJ /kg.K) at 25oC. If there is no
heat loss, what is the change in entropy of (a) steel casting, (b) oil
and (c) both considered together.
We need to know the final temperature.
Whatever heat is lost by the steal casting is the heat absorbed by the oil.

If T is the final temperature,

Heat transfer from steel = heat transfer to oil
dQ  mCP dT
40(0.5)(723  T )  150(2.5)(T  298) Integrating,

14460  20T  375T 111750

395T  126210 dS 
dQ CP dT

T  319.5K T T
 For steel casting,
T2
CP dT
ΔSsc   For the oil,
T1
T 319.5
CP dT
319.5
CP dT ΔSoil  
  298
T
723
T
319.5
 0.5 ln
319.5  2.5 ln
723 298
 0.408kJ / kg  0.174kJ / kg

Total entropy change of steel casting = - 16.32 kJ

Total entropy change of oil = 26.1 kJ
Total entropy change for oil and steel
casting together is ΔS  9.78kJ / K
T
 PROBLEM

A perfect gas is heated from 60 to 300oC at a constant pressure

of 4 bar. The gas is then cooled to 60oC at constant volume. The
mass of the gas is 5 kg. Determine total entropy change. CP and
CV are 1.0 and 0.72 kJ/kg.K

T2
dQ T2 CpdT

pressure

T1 2 ΔS12 
T1
T T
1 T2
T 1

573
3  ln  0.5427kJ / kg.K
333
volume
22
 T3 T3
dQ CV dT
ΔS2  3  
T2
T T
T 2

333
 0.72 ln  0.3907kJ / kg.K
pressure

T1 2 573
1 ΔS1 3  ΔS12  ΔS2  3
T2
3 S13  0.5427  0.3907
volume  0.152kJ / kg.K
Total entropy change = 5(0.152)=0.76 kJ / K
Heat Effects
Hess’s Law
 Heat Capacity
Heat Capacity : quantity of heat supplied to raise the temperature by one
degree (Extensive property)

Specific heat capacity: quantity of heat supplied to one kg mass to raise the
temperature by one degree ( intensive property)

the heat energy required to raise water’s temperature one kelvin (equal to one
degree Celsius) is 4186 Joules per kilogram, c = 4.186 kJ/(kg·K)
 HEAT EFFECTS – Sensible heat & Latent heat
Sensible heat: which involve heating that changes the temperature of the system.
no phase transitions, no chemical reactions, and no changes in the composition of
the system

Heat added is stored as internal energy or as enthalpy

the internal energy or enthalpy can be written as a function of two intensive
variables, like temperature, pressure, and molar volume. Thus, using T and V as the
independent variables for U, we write
for constant-volume processes, Q = ∆U
for constant-pressure processes, Q = ∆H

Heat capacities are often expressed in the form of polynomials in temperature

Heat of reaction: the change in enthalpy of the system for the
reaction proceeding at constant temperature

Standard Heat of reaction: the change in enthalpy of the system for

the reaction proceeding at 298K temperature and 1 atm pressure

Standard Heat of Combustion: the change in enthalpy of the system

for the combustion reaction ( a substance is oxidised with molecular
oxygen to form CO2 and Water) at 298K temperature and 1 atm
pressure. The standard heat of combustion of liquid acetaldehyde at
298K,

The negative of the heat of combustion of a fuel is refered as heating

value, which is positive.
Gross heating value – when water formed during combustion is in the
liquid state. ( more energy is liberated)
Net heating value – when water formed during combustion is in the vapor
state.
Enthalpy of Formation

When a compound is formed from its elements (e.g., CH4, from C and H2).

The enthalpy of the elements or their stable compounds is defined to be ZERO at

25oC (298 K) and 1 atm (or 0.1 MPa).

During the formation of methane from the elements at 298 K, 0.1 MPa, heat is given off (an
exothermic reaction) such that

kJ
 74,850
kmolCH 4
 Hess’s law
• Hess’s Law states that the net heat evolved or absorbed in a chemical reaction is
the same whether the reaction takes place in a single step or in a series of steps.
• For example: C + O2  CO2
The book tells us that this can occur as 2 steps
C + ½O2  CO H = – 110.5 kJ
CO + ½O2  CO2 H = – 283.0 kJ

C + CO + O2  CO + CO2 H = – 393.5 kJ

I.e. C + O2  CO2 H = – 393.5 kJ

• Hess’s law allows us to add equations.
• We add all reactants, products, & H values.
• We can also show how these steps add together via an “enthalpy diagram” …
The standard heat of reaction :
It is defined as the enthalpy change accompanying a
reaction when both reactants and products are at their
standard states at 298 K and is denoted by
ΔH 0 298 K .
2C( s )  O2 ( g )  2CO( g ) ΔH 0 298  221.2 kJ
Remember if the stoichiometry is represented as
1
C( s )  O2 ( g )  CO( g )
2
 221.2 kJ
Then ΔH 298 
0
 110.6 kJ
2
Standard heat of combustion:
Heat of reaction of any combustion reaction is called
standard heat of combustion. Only requirement is that
we must have one mol of species undergoing the
combustion reaction.
The standard heat of combustion of a substance is
defined as the enthalpy change accompanying the
reaction when one mol of the substance undergoes
combustion when both reactants and products are at
298K.
2CH3CHO( l )  5O2 ( g )  4CO2 ( g )  4 H2O;
ΔH 0 298  2336.24kJ

Standard heat of combustion of acetaldehyde is

 -1168.12 kJ
0
ΔHc 298
Standard heat of formation:
Standard heat of formation of a substance is defined
as the change in enthalpy accompanying the
formation of 1 mol of the substance from the
constituent elements when the reactants and
products are at 298K.
2C( s )  O2 ( g )  2CO( g ) ΔH 0 298  221.2 kJ
Standard heat of formation of carbon monoxide?
It is not –221.2kJ but Δ f  110.6 kJ
0
H
To determine the standard heat
of formation of sulfuric acid, we
should have a reaction
H2  S  2O2  H2SO4
Standard heat of reaction for the above reaction is the
required heat of formation of sulfuric acid.
Can we carry out this reaction?
This brings up what is known as Hess’s law of
constant heat summation.
Hess’s Law:
The net enthalpy involved in a reaction is the same
whether the reaction takes place in a single step or
in a series of steps.

A B C ΔH
A  B  AB ΔH1
AB  C ΔH2
A  B  C H1  H2  H
This permits the use of all
reactions along with their heat of
reaction as algebraic equations.

H2  S  2O2  H2SO4

S  O2  SO2 ΔH1
2SO2  O2  2SO3 ΔH2
SO3  H2O  H2 SO4 ΔH 3
S  O2  SO2 ΔH1

2SO2  O2  2SO3 ΔH2

SO3  H2O  H2 SO4 ΔH 3

1 ΔH4
H2  O2  H2O
2
 2S  2O2  2SO2 2 ΔH1
2SO2  O2  2SO3 ΔH2

2SO3  2 H2O  2 H2 SO4 2 ΔH3

2H2  O2  2H2O 2 ΔH4

2H2  2S  4O2  2H2SO4

2( ΔH1  ΔH3  ΔH 4 )  ΔH2

2H2  2S  4O2  2H2SO4
2( ΔH1  ΔH3  ΔH 4 )  ΔH2

H2  S  2O2  H2SO4
ΔH2
ΔH O
f  ΔH1  ΔH3  ΔH4 
2
 Problem
The standard heat of combustion of benzene at 298 K is – 3269.5 kJ/mol
when burnt completely to CO2 and liquid water. The standard heat of
combustion of hydrogen to liquid water -286.04 kJ/mol and that of carbon
dioxide is -393.78 kJ/mol. Calculate the standard heat of formation of
benzene.
We need to get heat of reaction for
6C  3H 2  C6 H 6 H  ?
The standard heat of combustion of benzene at 298 K
is – 3269.5 kJ/mol when burnt completely to CO2 and
liquid water.
2C6 H6  15O2  12CO2  6 H2O
15
C6 H6  O2  6CO2  3H2O – 3269.5 kJ
2
The standard heat of combustion of hydrogen to liquid
water -286.04 kJ/mol
1 - 286.04 kJ
H2  O2  H2O
2
42
and that of carbon dioxide is
- 393.78 kJ/mol.
(1) C  O2  CO2 - 393.78 kJ

15
(2) C6 H6  O2  6CO2  3H2O – 3269.5 kJ
2
1 - 286.04 kJ
(3) H2  O2  H2O
2
6C  3H2  C6 H6
6(1) + 3(3) gives,

43
6(1) 6C  6O2  6CO2 6(- 393.78 kJ)

3 3(- 286.04 kJ)

3(3) 3H2  O2  3H2O
2

15
6C  3H2  O2  6CO2  3H2O - 3220.8 kJ
2

44
 15
6C  3H2  O2  6CO2  3H2O - 3220.8 kJ
2
15
C6 H6  O2  6CO2  3H2O – 3269.5 kJ
2
15
6CO2  3H2O  C6 H6  O2 +3269.5 kJ
2

45
 15
6C  3H2  O2  6CO2  3H2O - 3220.8 kJ
2
15
6CO2  3H2O  C6 H6  O2 +3269.5 kJ
2
6C  3H2  C6 H6 48.7 kJ

The standard heat of formation of benzene is

48.7 kJ / mol.

46
Determine the standard enthalpy change, entropy change and standard Gibbs free
energy change of reaction at 400 K for the reaction
CO( g )  2 H 2  CH 3OH ( g )
at 298.15 K ,
H of ,CO ( g )  26.4157 kcal / mol , H of ,CH3OH ( g )  48.08 kcal / mol ,
G of ,CO ( g )  32.8079 kcal / mol , G of ,CH 3OH ( g )  38.69 kcal / mol ,

The standard heat capacity of various components is given by

C po  a  bT  cT 2  dT 3 , where C po is in cal/mol-K and T is in K

Component a b x 102 c x 10 5 d x 109

CH3OH 4.55 2.186 -0.291 -1.92

CO 6.726 0.04001 0.1283 -0.5307

H2 6.952 -0.04576 0.09563 -0.2079

Solution: per mol basis

The standard enthalpy change of the reaction at 298.15 K is

( product – reactant) =-48.08-(-26.4157)=-21.6643 kcal =21664.3 cal.

The standard enthalpy change of reaction at 400K is given by

400
H  H   dT

o o o
rxn , 400 rxn , 298.15 C p
298.15

a  16.08, b  2.2375 x10 2 , c  0.6106 x10 5 , d  0.9735 x10 9

2.2375 x102
H o
rxn ,400  21664.3  16.08(400  298.15)  (4002  298.152 )
2
0.6106 x105 0.9735 x109
 (400  298.15 ) 
3 3
(4004  298.154 )
3 4

H rxn
o
, 400  22587 .17 cal
The standard Gibbs free energy change of the reaction at 298.15 K is
( product – reactant)
= -38.69-(-32.8079) = - 5.8821 kcal = 5882.1 cal

The standard entropy change of reaction at 298.15K is

H rxn
o
 G o

S rxn
o
, 298.15 
, 298.15 rxn , 298.15
 52.93 cal / K
298 .15
The standard entropy change of the reaction at 400 K is

400
C po
S rxn , 400  S rxn , 298.15  
o o
dT
298.15
T
 400
S rxn
o
, 400  52.93  16.08 ln  2.2375 x10 2 (400  298 .15)
298 .15
0.6106 x10 5 0.9735 x10 9
 (400  298 .15 ) 
2 2
(400 3  298 .15 3 )
2 3

Srxn
o
,400  55.61 cal / K

Grxn
o
,4000  H rxn ,4000  400 x S rxn ,400  22587.17  400 x (55.61)
o o

 343.17 cal