SKF 2213 Chemical Engineering

Thermodynamics
Chapter 4: Heat Effects

Introduction to different types of heat effects

Sensible heat and heat capacity
oConstant-volume heat capacity
oConstant-pressure heat capacity
oThe temperature dependency of the heat capacity
Latent heat
oIntroduction to different types of latent heat
oLatent heat calculation and estimations.
Standard heat of reaction
oCalculation using standard heat of formations
Heat effects of industrial reactions
It is expected that students have the ability to:
Differentiate the different types of heat effects and their
importance in chemical engineering.
Calculate the enthalpy change for ideal fluids at given
conditions
Construct the hypothetical path for enthalpy change
calculation.
 Calculate the heat transfer to/from the system that involves
in the physical or chemical processes.
Apply the enthalpy calculation in the energy balance (open
and closed systems).
 Introduction

• Almost all chemical processes involve heat

transfer.

• Type of heat transfer.

– Sensible heat
– Latent heat
– Heat of reaction
– Heat of mixing/solution
  U   U 
• Let U=U(T,V) dU   dT   dV
 T  V  V  T
 U 
dU  Cv dT    dV
 V  T

• For isochoric process dU  Cv dT

U  U2  U1   Cv dT

• So this equation for U is valid for constant

volume (isochoric) process, or
• Whenever the U is independent of volume
– Ideal gases
– Incompressible liquid
– Approximately true for low pressure gases
• Let H=H(T,P)
 H   H 
dH    dT    dP
  T p   P T
 H 
dH  Cp dT   dP
  P  T

• For isobaric process dH  Cp dT

T2

H  H2  H1   Cp dT
T1

• So this equation for H is valid for isobaric

process, or
• Whenever the U is independent of pressure
– Ideal gases
– Approximately true for low pressure gases
 Heat Capacity

• A,B,C and D are constants for heat capacity and

values for ideal gas, solid and liquid are tabulated in
Table C1, C2, C3 respectively

• In this textbook, the tabulated constants are for Cp/R.

The units for CP depends on the unit for R.
Heat Capacity
• To simplify calculation, let us define mean
heat capacity
T

 C dT p


To
Cp
H T  To
T

R  (A  BT  CT 2  DT 2 )dT

To
Cp
H T  To
Cp B C D
H
 A To (  1)  To2 ( 2    1)  2  MCPH(T0,T;A,B,C,D)
R 2 3 To

• where


T
To
Hence, H  C p
H
T  T 
0
 Example 4.2

Solution for Q is straight forward as both T0 and T are known

 Latent Heat of Vaporization

• Information on process

– Pure substance
– Initial condition is saturated liquid at T1 and
P1
– Final condition is saturated vapor at T1 and
P1
– Phase change is taking place
• Energy Balance
Q  W  dU  dEK  dEP
Q  W  dU
Q  PdV  dU
Q  dU  PdV  dH
Q  H , this is delta H of vaporization at temperature T1
note,
Q  Hn , this is delta H of vaporization at normal boiling point

• Degree of freedom, F=2-π+N=2-2+1=1

– Once we specified one thermodynamic
properties, other properties will depends on this.
• For example, saturated H2O at 150oC
We can use Clapeyron equation to estimate
∆Hvap
dP sat
H vap  T V (4.11)
dT

• We need data for Psat, Tsat ,V sat liq and

V sat vap

• Or from steam table we get,

P sat ,H vsat ,H lsat
so
H vap  H vsat  H lsat
• At normal boiling point we could
estimate ∆Hvap by simple equation
known as Riedel equation
H vap,n 1.092(ln Pc  1.013)
 (4.12)
RTn 0.930  Tr
n

• Example for water

1.092(ln Pc 1.013)
H n  RTn
0.930  Trn
J 1.092(ln 220.5 1.013) 1mol
H n  8.314 373.15K
mol.K 373.15 18g
0.930 
647.5
J
H n  2328 Now, compare with the value from steam table
g
• If we know ∆Hvap1 at T1, we could estimate ∆Hvap2
at T2 using Watson equation,
0.38 0.38
H vap2  1  Tr2   Tc  T2 
  =  (4.13)
H vap1  1  Tr1 

 c 1
T T
• So we could combine Riedel and Watson
equations to solve for ∆Hvap2, whereby ∆Hvap1 is
∆Hn and Tr1 is Trn.
Example 4.4
 Heat of Reaction
• Information on process

– Feeds (e.g. A1, A2) are reactants

– Outlets are products (e.g. A3, A4) of the reaction
– Heat is released or absorbed during the process
– Exothermic reaction: ∆H is negative
– Endothermic reaction: ∆H is positive

1 A1   2 A2   3 A3   4 A4
Where |vi| is stoichiometric coefficient
 Heat of Reaction
Energy balance,
Q  H   3 H 3   4 H 4   2 H 2  1 H1    i H i

• Where the value of vi is positive for products

and negative for reactants.
• There many references for tabulated data for
∆Ho298 for commonly found reactions.
• However, to tabulate all possible reactions
are not practical.
• Furthermore, not all reactions can take place
at 298K
• We can calculate standard heat of reaction from
standard heat of formation of the reactants and
products

H 298
o
=  i f 298,i
 H o
Heat of formations are usually tabulated at 298.15K, similar to Table C4.
 For example,
CO2 ( g )  H 2 ( g )  CO ( g )  H 2O( g )
H 298
o
  1 393509    10   1 110525  1 241818
H 298
o
 41166 mol COJ2 reacted

• Note:
H2O does not actually exist as gas at 25oC and 1 bar.

This is hypothetical state of H2O as ideal gas at 25oC

and 1 bar is used for convenience in calculation.

Notice also the standard heat of formation of H2O is

tabulated for liquid as well as gas at the standard
state (1bar, 25oC).
• We could calculate standard heat of
reaction from standard heat of
combustion as follows,
Heat of
combustion
H 298
o
    i H 298,i
o

• For example, for the following reaction,

4C(s)  5H 2 (g)  C4 H10 (g)
H 298
o
        
   1 2877.4  5 285.83  4 393.51 
H 298
o
 125.79 mol C H kJ produced
4 10

• Note, coincidentally this is also standard

heat of formation of n-Butane.
 Temperature Dependence of
Standard Heat of Reaction (cont’)
• Most reactions in industry occur temperature
other than standard state
• For example, reactants enter a reactor at
200oC and the products exit 200oC, so
std heat of reaction is H o
473.15
• Since H is state function, we can use
hypothetical path to determine H o
473.15

• Convenient path is through standard state at

298.15K
Rxts(473) Prds(473)
H rxts H prds
H o

Rxts(298)  Prds(298)
298
H 473
o
 Sensible Heat + Std Heat of Rxn + Sensible Heat
H 473
o
 H rxts  H 298
o
 H prds
o
dH 473   niC p dT  dH 298
o
  niC p dT
rxts473298 prd 298473
o
dH 473   niC p dT  dH 298
o
  niC p d
rxt 298473 prd 298473
o
dH 473  dH 298
o
  niC p d   niC p dT
prd 298473 rxt 298473

For stoichiometric reaction, ni =|vi|

o
dH 473  dH 298
o
  vi C p d   viC p dT
prd 298473 rxt 298473
o
dH 473  dH 298
o
K
   iC p dT
o
dH 473  dH 298
o
K
 C o
p
dT
 Lets us define,
 C po  H  Mean Heat Capacity for Reaction
where
 B C 2 2 D 
 C  H  R  A 
o
T0 (  1)  T0 (    1)  2  (4.20)
p
 2 3  T0 
and M    i M i

So,
H 473
o
 H 298
o
 
  C po  H T  To
H 473
o
 H 298
o
  C po  H 473.15  298.15
In general, standard heat of reaction at temperature T,
 
H o  H 0o   C po  H T  To (4.21)
H o  H 298
o
  C po  T  298
H
 Heat Effects of Industrial Reactions

• Most reaction in industry rarely occur at 25oC,

1bar and at stoichiometric proportion.
• Reactants always contains excess
component.
• The reaction is not always go to completion
(not 100% conversion)
• Outlet temperature is not the same as the
inlet.
• Presence of inert materials
• More than one reactions may took place
simultaneously
Example 4.7
What is the maximum temperature that
can be reached by the combustion of
methane with 20% excess air? Both the
methane and the air enter the burner at
25oC.
79 79
CH 4  2O2  2 N 2  CO2  2H 2O  2  N 2
21 21
With 20% excess air,
 79   79 
CH 4  1.22O2  1.22  N 2   CO2  2H 2O  1.22  N 2   0.22O2
 21   21 
  79   79 
CH 4  1.22O2  1.22  N 2   CO2  2H 2O  1.22  N 2   0.22O2
 21   21 

• Basis of calculation: 1 mol CH4

Inlet Outlet
1 mol CH4 1 mol CO2
2.4 mol O2 0.4 mol O2
9.03 mol N2 9.03 mol N2
2 mol H2O

• Energy balance Q  W s  H  E K  E P
Q  H
• Maximum temperature is when Q=0, so
H  0
 PRDTout 
• Path H prd
H o
298
RXT(25 C)  PRD(25 o C)
o

• Energy balance becomes,

H  H 298
o
 H prd  0
where
H 298
o
   i H 298,
o
f

H 298
o
    
 1 393509  2 241818  1 74520  1
-2 0      
J
H 298
o
 802625
Mol
and
T2


H prd   ni  C p dT  C po  H T2  T1 
T1
 T2


H prd   ni  C p dT  C po  H T2  T1 
T1

 B C 2 2 D 
H prd  R  A 
 2
T1 (  1) 
3
T1 (    1)  2  T2  T1
 T1 
 

M   ni M i
Outlet
n i is mol of each component in products. 1 mol CO2
0.4 mol O2
9.03 mol N2
A  1(5.457)  0.4(3.639)  9.03(3.28)  2(3.47)  43.471 2 mol H2O

B  [1(1.045)  0.4(0.506)  9.03(0.593)  2(1.45)]x103  9.502x103

D  [1(1.157)  0.4(0.227)  9.03(0.04)  2(0.121)]x105  0.645x105

For T1=298K,

 9.502x103 0.645x105 
H prd  R  43.471 
 2
(298)(  1)  2 
 (298) 

T2  298 
• Substitute into energy balance
H  802625
J
Mol

  C po  H T2  298  0 
J  9.502x103 0.645x105 
802625
J
Mol
 8.314
MolK 
43.471 
2
(298)(  1)   
T  298  0
 (298)2  2
802625
T2   298
 9.502x103 0.645x105 
8.314  43.471  (298)(  1) 
 2  (298)2 
96539
T2   298
 0.7263 
 43.471  1.416(  1) 
 

• Solve by iteration (Application of Excel spreadsheet

will help) Answer: T2 = 2066K = 1793oC
• What will happen to the outlet temperature (T2) if no
excess air is used?
Iteration T2 T2cal % changes
1 298.15 2416.234
2 2416.234 2013.56 20.00
3 2013.56 2074.511 2.94
4 2074.511 2064.994 0.46
5 2064.994 2066.472 0.07
6 2066.472 2066.242 0.01
7 2066.242 2066.278 0.00
8 2066.278 2066.273 0.00
9 2066.273 2066.274 0.00
10 2066.274 2066.273 0.00
 Problem 4.5 (pg 150)

If the heat capacity of a substance is correctly represented by an

equation of the form:

CP = A + BT + CT2

Show that the error resulting when <CP>H is assumed equal to CP

evaluated at the arithmetic mean of the initial and final temperature
is C(T2-T1)2/12

Hint: evaluate <CP>H – CP (at Tam)

 Assignment

-Summary for Chapter 4

-Example 4.7 (no excess air)

-Problems: 4.1(a), 4.6, 4.11 (for chloroform),

4.21(f), 4.27(b), 4.38

(due 9/2, Wednesday)