SKF2213: CHEMICAL ENGINEERING THERMODYNAMICS

HEAT EFFECTS

Mohammad Fadil Abdul Wahab

• Almost all chemical processes involve heat
transfer.

• Heat is a path function and it is an energy in

transition (we do not store heat, we transfer it!).

• Type of heat transfer effects.

– Sensible heat
– Latent heat
– Heat of reaction
– Heat of mixing/solution
 Sensible Heat Effect
• Information on process,
Liq Liq
– Pure substance T 1 , P1 T 2 , P1
– Closed system
– Constant pressure
Gas
– Initial conditions: T 1 and P 1
– Final conditions: T2 and P1
Gas
– No reaction T 1 , P1 T 2 , P1
– No phase change
• Energy balance for closed system.
Q  W  dU  dEK dEP Q  W  dU Q  PdV  dU

• Also, H  U  PV
dH  dU  PdV  VdP

dH  dU  PdV
• For constant P
dU  dH  PdV

• Substitute and integrate Q  H

• So how do we determine ∆H?

 • F = 2-‐1+1 = 2
 H   H 
• Let H = H(T,P) dH    dT   dP
T  p  P T
 H 
dH  CpdT    dP
 T
P

dH  CpdT
• For isobaric process T2

H  H2  H1   CpdT
T1

• So this equation for ΔH is only valid for isobaric

process and no change of phase.

• If the process is not isobaric,

the equation is also valid for ideal gas

Also applicable for liquid and solid as H is

not highly dependent on pressure
• Similarly, let U = U(T,V) U  U 
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 ΔU is only valid for isochoric

process and single phase.

• If the process is not isochoric,

The equation is also valid for ideal gas
Also applicable for liquid and solid as U is
not highly dependent on specific volume
 Example
• Hot oil at To1 is supplied to a heater to heat air entering at
Ta1. The oil exits at To2 and the air heater is totally
insulated.

• Do the energy balance in order to determine the outlet air

temperature, Ta2.

Hot Oil in, o1 Hot oil out, o2

Air out, a2 Air in, a1

Steady state energy balance for open system:
    mH   E
Q  W   mH 2 1 K  EP
0  0   mH    mH   0  0
2 1

0  mo H o2  ma H a 2  mo Ho1  ma Ha1

mo (H o2  Ho1 )  ma (H a 2  Ha1 )  0
Assume air is an ideal gas:
T T
m o  C lpo dT  ma  Cigpa dT 0
To To

Assume constant CP:

m C l (T  T )  m C ig (T  T )  0
o po o2 o1 a pa a2 a1

m C (T  T )  m C ig (T  T )
l
o po o2 o1 a pa a2 a1

Solve for Ta2

 Heat Capacity
• A function of temperature

Cp
 A  BT  CT 2  DT 2 (4.4)
R

• 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.
 Mean Heat Capacity
• To simplify calculation, let us define mean heat capacity
as, T

C p dT

To
Cp
H T  To

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(T 0,T; A, B,C, D)
R 2 3  To

• Where MCPH is a subroutine function and T


To
• Since T

C p dT

To
Cp
H T  To

Hence,

H  C p
H
T T  0
• We could also write,

H  C p
H

T2  T1  
T2
T1

 B C 2 2 D 
H  R  A  T1 ( 1)  T1 (   1)  2 (T2 - T1)
 2 3 T1 

• Heat capacity for ideal mixture,

CPigmix   y iC pigi Ideal gas mixture

CPidmix   x iC pi Ideal solution
 • Example 4.2

Solution for Q is straight forward if T1 and T2 are

known

 B C 2 2 D 
Q  H  R  A  T1 ( 1)  T1 (   1)  2 (T2 - T)
 2 3  T1 
1
• Example 4.3

Solution for T2 is by iteration if T1 and Q (or ∆H)

are known

H
T 2  T1
 B C 2 2 D
R  A  T1 ( 1)  T1 (   1)  2 
 2 3 T1 
 Latent Heat of Vaporization
• Information on process
– Pure substance
– Initial condition is saturated liquid at T1 (or T1sat) andP 1
(or P1sat)
(first bubble appears)
– Final condition is saturated vapor at T1 and P1
(last drop of liquid (dew) is to disappear))
– Phase change is taking place

First bubble appears Last drop of liquid is

about to disappear
• Energy Balance Closed System

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=2-2+1=1

– Once we specified one thermodynamic properties,
other properties will depends on this.
• For example, saturated H2O at a specified T=150oC.
a) We can use Clapeyron equation to estimate ∆Hvap

dPsat
Hvap  T V (4.11)
dT

To used eqn 4.11, we need data for Psat, Tsat ,Vsat liq
and Vsat vap

b) or from steam table we get,

Psat , H vsat , H lsat
so
H vap  H vsat  H lsat
• At normal boiling point (Tn) 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  RT n
0.930  T rn
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
g
Now, compare with the value from steam table
• Also Trouton’s Rule and Chen’s Equation (see
Felder’s Textbook)
• If we know ∆Hvap1 at T1, we could estimate ∆Hvap2 at T2
using Watson equation,

1 T  T  T 
0.38 0.38
Hvap
 r  = c  (4.13)
Hvap1 1 Tr1  Tc  T1

• So we could combine Riedel and Watson equations

to solve for ∆Hvap2, whereby ∆Hvap1 is ∆Hn and Tr1 is
Trn.
 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

 Stoichiometric reaction,

1 A1  2 A2  3 A3  4 A4

Where |vi| is stoichiometric coefficient

• Where the value of vi is positive for products

and negative for reactants.

e.g. CH 4  2O2  CO2  2H 2 O

1 CH 4  2 O2  1 CO2  2 H 2 O
|v1|, | v2|
|v3|, | v4|

Energy balance for steady-state open system

with stoichiometric reaction,

Q  H
 3 H 3  4 H 4  2 H 2  1 H1
 i H i
 Standard Heat of Reaction ∆HoT
• Defined as the enthalpy change from a
stoichiometric reaction where the reactants
entering at standard state (T=T and P=1 bar,
specified phase (g, l, s)) and the products are also
at specified phases and the same standard state.

• Rewrite energy balance as,

Q  H oT    iH io
• There are many references for tabulated data for
∆Ho for commonly found reactions.
298

|v1|, | v2|
|v3|, | v4|

T=25oC, P=1bar T=25oC, P=1bar

Ex. of Standard Heat of Reaction at T=298.15K, ∆Ho298
Note: The value of standard heat of reaction
depends on stoichiometric coefficients as written

1
N (g)  3 H (g)  NH (g)
2 2 2 2 3

J J
H298
o
 46110
H o
298
 46110 3
mol H2 reacted
mol NH3 produced 2

J
H298
o
 46110 1
mol N reacted
2 2

N2 (g)  3H2 (g)  2NH3 (g)

J
J H298
o
 92220
H o
298
 92220 3mol H2 reacted
2mol NH3 produced
J
H298
o
 92220
mol N2 reacted
• However, tabulation of all possible reactions are
not practical.

• Furthermore, not all reactions can take place at

298K

• So, how to calculate standard heat of reaction?

Standard Heat of Formation ∆Ho of species i
f,i

• For formation of 1 mol of compound Ai from its

elements (E),

1 E1  2 E 2  Ai

H o
f 298,i  H   | ve | H  H
i
o o
e i
o

• Here Hoi is calculated with reference to its elements’

enthalpy (Ho e) to be zero at standard state
(T=298.15K)
• So we can calculate standard
heat of reaction from standard heat of
formation of the reactants and products

H 298
o
   i H io

H 29
o
=  iH o
f 298,i
8
• Example of formation reaction,

Cs  12 O2 g  2H 2 g  CH3OHl

where
C,O2,H2 are elements

• Heat of formations are usually tabulated

at 298.15K, such as in Table C4. H of 298
Example:
Calculation of std heat of rxn using std heat of formation,

CO2 (g)  H 2 (g)  CO(g)  H2O(g)

H o
298   i H i
o

H o
29 =   H i
o
f 298,i
8

H 298
o
  co2 H o
f 298,co2   H 2 H of 298, H 2   co H oof 298,co   H 2O H f 298,H 2O

 1393509  10  1110525  1241818

H 298
o
 41166 mol CO2J reacted
• Note:

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

This is hypothetical state of H2O as an 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).
 Standard Heat of Combustion
• Type of heat of reaction that is commonly encountered.

• A reaction between fuel and oxygen to produce water and

carbon dioxide

• Reactants has higher chemical energy than the products,

therefore the heat of combustion is negative.

• Data for heat of combustion at standard state are widely

available
 • We could calculate standard heat of reaction from
standard heat of combustion as follows,
Heat of
298 
H o    H o i 298,i
combustion

• For example, for the following reaction,

4C(s)  5H 2 (g)  C4 H10 (g)

H298
o
       
 1 2877.4  5 285.83  4 393.51 
   
H o  125.79 kJ
298 mol C4 H10 produced

• Note, coincidentally this is also standard heat of

formation of n-Butane.
 Measurement of Heat of Combustion

• Bomb Calorimeter for liquid and

solid fuel

• Boys Calorimeter for gas fuel

 Temperature Dependence of ΔHo
T

• Most reactions in the industry occur at 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 473.15
o
 Convenient path is through standard state at 298.15K,

Rxts(473) Prds(473)

H rxts
H prds

Rxts(298)  Prds(298)
H o
298

H o  H  H o  H
473 rxts 298 prds

H473
o
 Sensible Heat + Std Heat of Rxn at 298 + Sensible Heat
dH o
473
  n C dT  dH o 
i p 298  niC p dT
rxts473298 prd 298473

dH o
473
  n C dT  dH o 
i p 298  niC p dT
rxt298473 prd 298473

o
dH 473  dH 298
o
  niC p dT   niC p dT
prd 298473 rxt298473
For stoichiometric reaction, ni =|vi|

dH o  dH o 
473 298  viC p dT   viC p dT
prd 298473 rxt298473

dH o  dH o
473 298K
 C dTi p

dH o  dH o  C op dT
473 298K

Where,
 C o   Mean Heat Capacity for Reaction
p H

and
 B C 2 2 D 
 C  H  R A 
o
T0 (  1)  T0 (    1)  2  (4.20)
p
 2 3  T0 
and M    i Mi , and A, B,C, D are constants for heat capacity.
 So,
H o
473
 H o
298
  C o 
p H
T  T o

H473
o

 Ho298   C op  H 473.15  298.15 

In general, standard heat of reaction at temperature T,

H o  H o   C o 
T To p H
T  T  o
(4.21)

H o  Ho   C o  T  298
T 298 p H  
 Heat Effects of Industrial Reactions
• Most reaction in industry rarely occur at 25 oC, 1bar and
also not 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

For example,

What is the maximum temperature that can be reached

by the combustion of 1 mol of methane with 20% excess
air? Both the methane and the air enter the burner at
25oC.
79 79
 CO  2H O   N
CH 4  2O2  2
 21 2 
N
 2 2 2
21 2

With 20% excess air,

 79   79 
CH 4  1.22O2  1.22 N2  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  EK  EP

Q  H
• Maximum temperature is when Q=0, so
H  0
 Prd Tout 
• Path
H prd
H o
298

Rxt(25o C)  Prd(25o C)

• Energy balance becomes,

H  H o  H 0
298 prd

where
H298
o
   i H 298,
o
f

H298
o
    
 1 393509  2 241818  1 74520  2 0       
J
H298
o
 802625
Mol
and

T  T 
T2

H prd   ni  C pdT   C o 
p H 2 1
T1
 T2

H prd   ni  C pdT  
 C op  H T2  T1 
T1

 B C 2 2 D 
H prd  R A  T1 (  1)  T1 (   1)  2
 T1 

T2  T1 
 2 3

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) 
 (298) 
T  298
2  2  
 Substitute into energy balance H  H298
o

H prd
0

H  802625
J
Mol

  C op  H T2  298  0 

J  9.502x103 0.645x105 
802625
J
Mol
 8.314 43.471 
MolK 
 2
(298)(  1) 
 (298)2 

 
T2  298 0

802625
T2   298
 9.502x103
0.645x10 
5
8.314 43.471  (298)(  1) 
 2  (298)2 


96539
T2   298
 0.7263 
43.471
  1.416(  1) 
   
 96539
T2   298
 0.7263 
43.471  1.416(  1) 

   

96539
T2  298 
 
 T2 0.7263
43.471  1.416(  1)  
 298 T2 
 298 

96539
T2  298 
 216.437 

44.887  0.00475T 
 T2  
2

• Solve by iteration (Use Excel or Casio fx-570)

Answer: T2 = 2066K = 1793oC
• What will happen to the outlet temperature (T2) if no
excess air is used?
 Reference
Smith J.M., Van Ness H.C. , and Abbott M. M. ,
Introduction to Chemical Engineering
Thermodynamics, 7th Edition, McGraw Hill,
New York, 2001.