CHAPTER 4

Heat Effects: Part 1

Mohd Asmadi Bin Mohammed Yussuf

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Topic Outcomes
Week Topic Topic Outcomes
3-5 Heat Effects It is expected that students are
able to:
• Introd. to different types of heat effects
• Differentiate the different types of
• Sensible heat & heat capacity heat effects & their importance in
• Constant–V heat capacity chemical engineering.
• Constant–P heat capacity
• The T dependency of the heat • Calculate the enthalpy change for
capacity ideal fluids at given conditions.

• Latent heat • Construct the hypothetical path for

• Introd. to different types of latent heat enthalpy change calculation.
• Latent heat calculation & estimations.
• Calculate the heat transfer to/from
• Standard heat of reaction the system that involves in the
• Calculation using standard heat of physical or chemical processes.
formations
• Apply the enthalpy calculation in
• Heat effects of industrial reactions the energy balance (open & closed
systems).

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 Scope of Lecture

Introduction to different types of heat

effects

Sensible heat and heat capacity

Latent heat for pure substances

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 Introduction
Almost all chemical processes involve heat transfer

Design of reactors

Knowledge of the HEAT RATE

Heat effects Associated Chemical reactions

THERMODYNAMICS is applied to evaluate most of heat effects

that accompany physical and chemical reactions

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Types of Heat Transfer Effects

HEAT
TRANSFER

Sensible Latent Heat of Heat of Heat of

Heat Heat Reaction Formation Combustion

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 Sensible Heat Effects

7
CO2

C Pig H2O
R 5

N2
4

3
Ar

2
500 1,000 1,500 2,000
T/K
Figure: Ideal-gas heat capacities of Ar, N2 H2O & CO2 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Heat Transfer

Sensible heat effects →characterized by temperature changes.

Heat transfer Cause the T of system

System
to a system to change

No phase transition
No chemical reactions
No changes in composition

OBJECTIVE: Develop relations between the quantity of heat

transferred and the resulting T-change.

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 Information on Process

• Pure substance Liq. Liq.

• Closed-system T1, P1 T2, P1
• Constant-pressure
• Initial condition: T1 and P1
Gas
• Final condition: T2 and P2
• No reaction Gas
T1, P1 T2, P1
• No phase change

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 Energy Balance
Closed system

Q  W  dU  dE k  dE p Q  W  dU Q  PdV  dU

Also
H  U  PV dH  dU PdV  VdP

Constant P

dH  dU PdV dU  dH PdV

How do we determine ∆H?

Substitute and integrate
Q  PdV  dH PdV Q  H

Note: +ve : work done on the system by the surrounding; -ve : work done by the system on its surrounding
 Specific Enthalpy

 H   H 
Let H  HT, P  dH    dT    dP
 T P  P  T

 H 
dH  C P dT    dP
 P  T
Conts. P

Valid for isobaric process & no dH  C P dT

change of phase

Whenever the H is independent of P T2

• True for ideal gas Q  ΔH   C P dT
• Approximately true for low P gases T1

H2  H1

Note: H, enthalpy; P, pressure Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Internal Energy

 U   U 
Let U  UT, V  dU    dT    dV
 T  V  P  T

 U 
dU  C V dT    dV
 V  T
Conts. V

Valid for isochoric process & single

phase dU  C V dT

Whenever the U is independent of V

T2
• True for ideal gas
• Incompressible liquid Q  ΔU   C V dT
• Approximately true for low P gases T1

U2  U1

Note: U, internal energy; V, volume Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Example 1

Hot oil ay 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 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

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 Solution 1

Steady state energy balance Assume air = ideal gas

for open system
T T
  mH  mH  E  E
 W
Q  2  1 k p  o  C lpodT  m
m  a  C igpa dT  0
To To

0  0   mH2   mH1  0  0 Assume Cp = constant

 oC lpo To2  To1   m

m  a C igpa Ta2  Ta1   0
0m
 oHo2  m
 aHa2  m
 oHo1  m
 aHa1
 oC lpo To2  To1   m
m  a C igpa Ta2  Ta1 

 o Ho2  Ho1   m
m  a Ha2  Ha1   0 Solve for Ta2

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 Heat Capacity
T2 T2
Since Q  ΔH   C P dT or Q  ΔU   C V dT We need C = f(T)
T1 T1

The Idea of heat capacity

Which one stays hot

longer after being
removed from heat
source?

The substance with the higher specific heat capacity stays hot
longer.
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 Heat Capacity
From empirical equation,

CP
 A  BT  CT 2  DT 2
R
Unit for Cp depends • Constant heat capacity
on the unit for R
• Values for Ideal gas, solid, liquid
→Table C1, C2, C3

C Pig
For ideal-gas heat capacity,  A  BT  CT 2  DT 2
R

C igV C Pig
2 ideal-gas heat capacities are related,  1
R R

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 Example 2
Given the molar heat capacity of CH4 in the ideal-gas-state as functions of
temperature
C Pig
 1.702  9.081 10 3 T  2.164  10 6 T 2
R
Calculate the value of heat capacity at 87 C.

Solution 2:

T K   87 C  273.15  360.15 K

C Pig
 1.702  9.081 10 3 360.15   2.164  10 6 360.15 
2

C Pig  41.5J mol1 K 1

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Evaluation of the Sensible-Heat Integral

Evaluation of the ∫ Cp dT is accomplished by substitution for Cp,

followed by integration,

CP B 2 2 C 3 3 D    1
T
T0 R dT  AT0   1 
2
T0 
  1 
3
T0 
  1 
T0



 
T
 
T0

Case 1

Given: T0 and T
Calculation is straightforward
Calculate: Q or H

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 Mean Heat Capacity

Case 2

Given: T0 and Q or H
Iteration
Calculate: T

Factoring ( –1) T  T0
 1 
T0

 B 2 C 3 2 D 
T
T0 P
C dT  AT
 0 
2
T0   1 
3
T0    1 
T0 

  1


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Mean Value Specific Enthalpy
 B C 2 2 D 
T
T0 P
C dT   A 
2
T0   1 
3
T0  
   1  2
T0 

T  T0 


CP H Mean heat capacity

R
Then

H  C P H
T  T0 
T2
Previous
Q  ΔH   C P dT
slide
T1

ΔH
T  T0
CP H

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 Iteration

Start =T (>T0)   T/T0

CP B C 2 D
<Cp>H H
A T0   1  T0  2    1  2
R 2 3 T0

ΔH
Substitute → T T  T0
CP H

New T Converges Final T

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 Example 3: Case 1
Calculate the heat required to raise the temperature of 1 mol of
methane from 260 to 600 °C in a steady-flow process at a pressure
sufficiently low that methane may be considered an ideal gas.

Solution 3:

T0  533.15K 873.15
T  873.15K   1.6377
533.15

C Pig
873.15
Q  ΔΗ  R  dT
533.15 R

 9.08110 3 2 2 2.164 10 6 3 3 

Q  8.314 1.702T0   1 
2

T0   1   3
T0   1   
 

Q  19,778J
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 Example 4: Case 2
What is the final temperature when heat in the amount of 0.4 x 106
(Btu) is added to 25 (Ib mol) of ammonia initially at 500 (°F) in a steady-
flow process at 1 (atm)?

Solution 4:

If ΔH is the enthalpy change for 1(Ib mol), Q = n ΔH.

Q 0.4  106
 16,000 BtuIbmol
1
H  
n 25

ΔH =16,000/0.4299 = 37,218 J mol-1

Note: 1 J mo1-1 = 0.4299(Btu)(lb mol)-1 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Solution 4 (Cont.)
500  459.67
T0   533.15K
1.8

Then for any value of T:

CP
 MCPH 533.15, T;3.578,3. 020E  3,0.0, 0.186E  5
R

Iteration, starts with a value T ≥ T0

T = 1,250 K or 1,790 (°F)

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 Tutorial 1

For steady flow in a heat exchanger at approximately atmospheric

pressure, what is the heat transferred:s
a) When 10 mol of SO2 is heated from 200 C to 1,100 C.
b) When 12 mol of propane is heated from 200 C to 1,200 C.

Tutorial 2:

How much heat is required when 10,000 kg of CaCO3 is heated at

atmospheric pressure from 50 C to 880 C. (MW CaCO3: 100.1 g/mol)

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Latent Heats of Pure
Substances

Latent Heat

Clayperon Trouton’s Riedel Watson

Equation Rule Equation Equation

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 Latent Heats

Pure substance

At constant P, no change in T occurs

Liquefied Vaporized
Solid Liquid Vapor

Process requires the transfer of finite

amount of heat to the substance.

These heat effects are called latent heat of fusion and latent heat of
vaporization.

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 Example: Water

140

Water & steam Steam

100
Temperature (C)

60
Ice &
Water
water
20

Ice
–20
Time

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 Information on Process

Pure substance
Initial condition
• Saturated liquid at T1 (or T1sat) and P1 (P1sat)
→ 1st bubble appears
Final condition
• Saturated vapor at T2 and P2
→ Last drop of liquid (dew) is to disappear
Phase change
No work

1st bubble appears Last drop of liq. Is

about to disappear

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 Equations

Latent Heat

Clayperon Trouton’s Riedel Watson

Equation Rule Equation Equation

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 Energy Balance

Closed system

Q  W  dU  dE k  dE p H of vaporization at temperature T1

Q  H
Q  W  dU
Q  Hn
Q  PdV  dU
H of vaporization at normal boiling point
Q  dU PdV  dH

DOF, F = 2 –  + N = 2 – 2 + 1 = 1
Specified 1 thermodynamic properties, other will depend on this
 Clapeyron Equation

There are coexistance of 2 phases

Latent heat accompanying a phase change is a function

of T & related to Clapeyron equation:

Vapor pressure
Latent heat
dP sat
H  T V
dT

Volume change accompanying

the phase change

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 Vaporization of a Pure Liquid

When Clapeyron equation applied to the vaporization of a

pure liquid,

Slope of the vapor pressure vs.

Latent heat of vaporization T curve at the T of interest.
dP sat
H  T V
dT

Different between molar

volumes of sat. liq. & sat. vap.

Thus, ΔH can be calculated from vapor–pressure &

volumetric data.

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Example: Saturated H2O at 150 C
Use Clapeyron equation to estimate Hvap

dP sat
Hvap  T V
dT

Need data for Psat, Tsat, Vsat. liq. & Vsat. vap.

Or
From steam table we get,

P sat , Hsat
v , Hl
sat

Hvap  Hsat
v  Hsat
l

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 Example 5
Table B.2 of App. B provides parameters for an equation that gives Psat as a
function of T for a number of pure compounds. Determine the heat of
vaporization of ACETONE at its boiling point by application of Clapeyron
equation. Evaluate dPsat/dT from the given vapor-pressure equation, and use
generalize correlations from Chap. 3 to estimate V. Compare the computed
value with the value of Hn listed in Table B.2

Additional Information
Clapeyron equation: Hvap  T VdP sat / dT
Pr P (1  Tr )0.2857
Generalize correlations from Chap. 3: Z  1 B 0  ωB1 r V sat
V Z
B
Tr Tr c c

Antoine equation: lnP sat /kPa  A 

T/K  C

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 Approximate Methods
Data are always not available at the T of interest.

Approximate methods are used to estimate the heat effects

accompanying a phase change.

1. Prediction of heat of vaporization at 2. Estimation of heat of vaporization at any

normal boiling point (at 1 atm.) T from the known value at a single T.

Trouton’s
Rule
Watson
Equation
Riedel
Equation

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 Trouton’s Rule

Rough estimates of latent heats of vaporization for pure liquids

at their normal boiling points.

Hn
 10
RT n

Absolute T of the bp

Exp. values for this ratio: Ar: 8.0; N2: 8.7; O2: 9.1; HCl: 10.4;
C6H6: 10.5; H2S: 10.6; H2O: 13.2

Note: T, temperature; bp, boiling point. Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Riedel Equation

Estimation of heat of vaporization at normal boiling point

Critical pressure

ΔHn 1.092lnPc  1.013 

 Accurate! Error rarely exceed 5%
RT n 0.930  Trn

Reduced T at Tn

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 Example for Water

1.092 lnPc  1.013 

Hn  RT n
0.930  Trn

 J  1.092 ln220.5  1.013   1mol

Hn   8.314 373.15K   
 mol.K   373.15   18g 
0.930   
 647.5 

J Compare with the value

Hn  2328
g from steam table

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 Watson Equation
Estimates of the latent heat of vaporization of pure liquid at any T
from the known value at a single T

0.38
H2  1 Tr2 


H1  1 Tr1 


0.38
Hvap2  Tc  T2  Know Hvap1 at T1, we
   could estimate Hvap2
Hvap1  Tc  T2 

We could combine Riedel and Watson equations to solve Hvap2,

whereby Hvap1 is Hn and Tr1 is Trn

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 Example 6
Given the latent heat of vaporization of water at 100 °C is 2,257 J.g-1,
estimate the latent heat at 300°C.

Solution 6:

0.38
 1 0.886 
Let, ΔH2  2,257  
 1  0.577 
H1 = latent heat at 100 C = 2.257 Jg -1
ΔH2  2,257 0.270 
0.38
Tr1 =373.15/647.1 =0.577
Tr2 =573.15/647.1 = 0.886
ΔH2  1,371Jg 1

H2= latent heat at 300 C = ?

The value given in the steam tables
is 1,406 Jg-1.
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 Tutorial 3
Saturated-liquid benzene at pressure P1 = 10 bar (T1sat = 451.7 K) is
throttled in a steady-flow process to a pressure P2 = 1.2 bar (T2sat = 358.7
K), where it is a liquid/vapor mixture. Estimate the molar fraction of the
exit stream that is vapor. For liquid benzene, Cp = 162 J mol-1 K-1.
Ignore the effect of pressure on the enthalpy of liquid benzene.

Additional information:
Throttling process is adiabatic and isenthalpic.
Hint: Given Cp (T1sat – T2sat) = x.Hv, Find x

Tutorial 4:

Estimate H298 for acetylene as a liquid at 25 C

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