Chemical Engineering Thermodynamics

(CHPE3102)
Chapter 4

Dr Khashayar Nasrifar
Department of Petroleum and Chemical Engineering
Sultan Qaboos University, Muscat, Oman
Spring 2023

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Objective: Calculating Heat effects

 Heat effects: Sensible heat, Latent heat, Heat of
Reaction
 Sensible heat: Heat transfer due to temperature
difference
 Latent heat: Heat transfer due to phase change
 Heat of reaction: Heat release or absorption due to
reaction

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Sensible heat effects: Heat transfer

due to temperature difference
u  u( T , v )
 u   u 
du    dT    dv
 T  v  v T
 u 
 cv   
 T  v
If Volume is
constant
du  cv dT

T2 cv  const
Q  U  mu  m  cv dT  mcv T
T1
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Sensible heat effects

h  h( T , p )
 h   h 
dh    dT    dp
 T  p  p T
 h 
 cp   
 T  p
If pressure is
constant
dh  c p dT

c p  const
T2
Q  H  mh  m  c p dT  mc p T
T1
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Temperature dependence of heat

capacity at low pressures
cp
   T  T 2
R

OR

cp
 a  bT  cT  2
R

Sometimes a combination of them are used

cp
 A  BT  CT 2  DT  2
R
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Temperature dependence of heat

capacity for gases in ideal gas state
At Ideal gas state, gases behave like ideal gases at 1 bar.

c igp
 A  BT  CT 2  DT  2
R
See Table C.1, APP. C for values of A, B, C, and D for various gases

c c R
ig
v
ig
p

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Ideal gas heat capacity of gas

mixtures

c ig
p ,mix y c y c
ig
A pA
ig
B pB y c ig
C pC

The above equation is only valid for ideal gas mixtures. For real gas mixtures
An equation of state need to be used.

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Evaluation of sensible heat integral

T2
Q  n  c p dT  nR 
T1
T2

T1
A  BT  CT 2

 DT  2 dT

nR   1 1 
Q
T2  T1  
 2
 
C 3 3

 AT2  T1   T2  T1  T2  T1  D   T2  T1 
B 2
2 3  T2 T1 

  1 1 

cp

1
T2  T1  
B 2
 2 C 3
 
3

 AT2  T1   T2  T1  T2  T1  D  
R 2 3  T2 T1 

Q  n c p T2  T1 

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Mean Value Theorem

cp
cp

T1 T2
T

1 T2
cp  
T2  T1  T1
c p dT

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Example
What is the final temperature when heat in the amount
of 422 MJ is added to 11.3 kmol of ammonia initially at
260°C (533.15 K) in a steady-flow process at
approximately 1 atm?

Solution: Q  nh
First law: Q 422 103
h    37345 kJ / kmol
n 11.3
h 37345
h  c p T2  T1   T2  T1   T2  533.15 
cp cp

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Example (continued)
 For ammonia (see APP. C)

cp
 3.578  3.020 10 3 T  0.186 105 T  2
R

R  8.314 kJ / kmol .K

cp 
R 

T2  533.15 
3.578T2
 533.15   T
3.02  103 2
2
 533.15 2
 
0.186  10 5
T2
1
 533.15 1 

2 

By trial and error T2=1250 K.

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Latent heats of pure substances

Vapor
Vapor

Heat is absorbed

Heat is produced
Liqui
d
Liquid

Condensation Evaporation

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Latent heat of evaporation

Clapeyron equation

dp sat
H vap  Tv
dT
psat

Slope = dpsat/dT

v  v v  v l
H vap  H v  H l
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Classius-Clapeyron equation
Assumption: Volume of vapor is larger than volume of liquid

v  v v  v l  v v
Ideal gas law is held
RT
v  sat
p
RT dp sat
H vap
 T sat
p dT
The latter can be rearranged to

dT H vap dp sat
2
 sat
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T R p
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Classius-Clapeyron equation
Rearranging the latter gives

H vap  1 
d ln p sat
 d   dy  mdx ( y  mx  b )
R T 
y  ln p sat lnpsat
Slope=-Hvap/R
1
x
T
H vap
m
R
1/T

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Heat of evaporation at normal boiling point (p = 1 atm)

Trouton’s rule
H n
 10
RTn

Riedel’s correlation

H n 1.092ln pC  1.013 pC is in bar


RTn 0.930  Trn

Watson’s formula
0.38
H 2  1  Tr 2 
  
H1  1  Tr1 
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Example
Calculate latent heat of vaporization of water at normal boiling point.

Solution:

App. B, Table B1
pC= 220.55 bar H n 1.092(ln( 220.55 )  1.013 )
  13.56
TC=647.1 K RTn 0.930  0.577
Tn= (373.15 K)?

H n  ( 13.56 )( 8.314 )( 373.15 )  42065 J .mol 1

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Example
Given the latent heat of vaporization of water at 100°C (373.15 K) is 2257 J.g-1. Estimate
the latent heat of water at 300°C (573.15 K).

Solution:

Tr1 = 373.15 / 647.1 = 0.577

Tr2 = 573.15 / 647.1 = 0.886
H1 = 2257 J.g-1
H2 = ?

 1  0.886 
0.38

H 2  ( 2257 )   ( 2257 )( 0.270 )0.38  1371 J .g 1

 1  0.577 

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Heat of reaction
aA  bB  cC  dD
T T
Reactor

Q  H
Standard heat of reaction: Enthalpy change when a moles A and b moles of B in their standard
states at temperature T react to form c moles of C and d moles of D in their standard states at
the same temperature

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Standard state

A standard state is a particular state of a species at

temperature T and at specified conditions of pressure,
composition, and physical condition as, e.g., gas, liquid
or solid.

Standard pressure = 1 atm (101325 Pa)

Standard temperature = 25°C (298.15 K)

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Standard heat of formation

A formation reaction is defined as a reaction which
forms a single compound from its constituent elements.
For example

1
C  O2  2 H 2  CH 3OH A FORMATION REACTION
2

H 2O  SO3  H 2 SO4 THIS IS NOT A FORMATION REACTION

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Some examples for standard heat of formation

CO2 : C( s )  O2 ( g )  CO2 ( g ) H f 298  393 509 J

H2 : Because hydrogen is an element H f 298  0
1
CO( g ) : C( s )  O2 ( g )  CO( g ) H f 298  110 525 J
2
1
H 2O( g ) : H 2 ( g )  O 2 ( g )  H 2O( g ) H  f 298  242 818 J
2

See appendix C, Table C.4 for values of heat of formation.

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Standard heat of formation and
combustion (App. C)

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Standard heat of combustion

A combustion reaction is defined as a reaction between
one mole of an element or compound and oxygen to
form specified combustion products.

For example
1
5 H 2 ( g )  2 O2 ( g )  5 H 2O( l ) H 298

 ( 5 )( 285 830 )
2
4C( s )  4O2 ( g )  4CO2 ( g ) H 298
 ( 4 )( 393509 )

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How to calculate the standard heat

of reaction at 298 K
Examples
N 2  3H 2  2 NH 3
H 
298  2H 
f NH 3  H 
f N2  3H 
f H2

H 298

 2H f NH 3  2( 46110 )  92220 J

4 HCl( g )  O2 ( g )  2 H 2O( g )  2Cl2 ( g )

H  298  2H f H 2O  4H f HCl  2( 241818 )  ( 4 )( 92307 )   114 408 J

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How to calculate heat of reaction at
any temperature (T)
T
aA  bB  cC  dD
T T
Reactor

a moles of A T c moles of C
b moles of B aA  bB  cC  dD d moles of D
At T At T

H  R H  P

a moles of A 298 K c moles of C

b moles of B aA  bB  cC  dD d moles of D
At T0= 298 K At T0= 298 K
H  298

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How to calculate heat of reaction
at any temperature (T)

H R  a c pA 298  T   b c pB 298  T 

H P  c c pC T  298  d c pD T  298

H 298

 cH f C  dH f D  aH f A  bH f B

H T  H R  H 298

 H P

H T   c p rn T  298  H 298



where
 c p rn  c c p C  d c p D  a c p A  b c p B
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Example: Adiabatic flame temperature

What is the maximum temperature that can be reached
by the combustion of methane with 20% excess air?
Both the methane and air enter the burner at 25°C
(298.15 K).

298 K T
Reactor

Q=0 because the maximum temperature at the outlet happens when there is no
heat loss from the reactor. This temperature often called adiabatic flame temperature.

H   H 298

 H P  0
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Solution

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Heat of reaction is calculated from

Energy balance reads

(A)

(B)

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Combining Eq. (A) and Eq. (B) yields:

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Conclusions
1. You have learnt different types of heat effects
2. You can calculate sensible heat for gases
3. You have learnt to calculate latent heat of fluids
4. You have learnt to calculate heat of reaction at any temperature

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