Chemical Engineering

Thermodynamics

Chapter 2
Heat Effects
 Chapter Outline
HEAT EFFECTS

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PHYSICAL HEAT CHEMICAL HEAT

4.1 Sensible Heat of Pure Substance 4.3 Standard Heat of Reaction (DHrxn),
Formation (DHf) and Combustion (DHc)
4.2 Latent Heat of Pure Substance
4.4 Temperature Dependence of DHrxn
Topic Outcomes

• Evaluate sensible heat integral

• Determine latent heat of substances by
application of Riedel and Watson equations
• Determine heat effect of industrial reactions
by the devising of actual and theoretical
path.
 Motivations
Thermodynamics is applied to evaluate most of heat
effects that accompany physical and chemical
reactions.
For example: Chemical industry
Design of reactors requires knowledge of the heat
transfer rate which depends on the heat effects
associated with the chemical reactions.
 4.1 Sensible Heat
• Heat transfer to a system in which there are
no phase change, chemical rxtn and composition
changes causes the temp of the system to change.
• The molar or specific internal energy, U
of a substances may be expressed as
a function of 2 state variables.
• As the variables randomly selected as
temperature., T and molar or specific
constant-
volume, V; 
  = volume heat
U
C 
V  
 T V capacity

 U   U 
dU    dT    dV
 T V  V T
  U 
dU  CV dT    dV
 V T
0 For any constant-volume
process, regardless of substance.
 U 
dU  CV dT    dV Internal energy independent of
 V T volume. True for ideal gases,
incompressible fluids and
low press gases.
T2
Integrate
dU  CV dT U  C
T1
V dT

For mechanically reversible

constant-volume process,
Q  U
T2

Q  U  C
T1
V dT
The molar or specific enthalpy, H
of a substances may be expressed as a
function of temperature, T and pressure, P;
 H  constant-
C P    = pressure heat
 T  P capacity

 H   H 
dH    dT    dP
 T  P  P T
  H 
dH  C P dT    dP
 P T
0 For any constant-pressure
process, regardless of substance.
 H 
dH  C P dT    dP Enthalpy is independent of
 P T pressure; this is true for ideal
gases and approximately
true for low pressure gases
Integrate T2

dH  C P dT H  C
T1
P dT

For mechanically reversible constant-pressure,

closed-system process, Q  H
T2

Q  H  C
T1
P dT
 Temperature Dependence of
the Heat Capacity
T2
To integrate and
Q  U   CV dT
T1

T2

Q  H  C
T1
P dT required knowledge of

the temperature dependence of the heat

capacity.
 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.
Temperature Dependence of the Heat Capacity
 
Heat capacity is given by 2 simplest expressions
and
where α, β, γ, a, b and c are constants, characteristic of
the particular substance

Both equations are combined to give:

(4.4)
 ig
C
Idea-gas-state heat capacities, P and CV
ig

are dependence on temperature but

independent of pressure.
 𝐶 𝑖𝑔
𝑃 2 −2
= 𝐴+ 𝐵𝑇 +𝐶 𝑇 + 𝐷 𝑇
𝑅
 𝐶 𝑖𝑔 𝐶 𝑖𝑔
𝑉 𝑃
= −1
𝑅 𝑅
 Try this…
Given the molar heat capacity of methane in
the ideal-gas-state as functions of
temperature. The molar heat capacity of
methane in the ideal gas state is given as a
function of temperature in kelvins by:
ig
CP
 1.702  9.08110 3 T  2.164  10 6 T 2
R
Calculate the value of heat capacity at 87°C.
(Ans:14.15 J/mol.K)
 Evaluation of the Sensible Heat Integral
 
Q and ΔH can be calculated at given T and T0 by
integrating CP
The integral can be evaluated as

where
If To, Q or H were given and asked to
calculate T the equation is rearranged:
 B 
 AT 0  T0   1  
CP 2
  T  T0 
T
T0 R
dT  
 C T 2  2    1  D 
3 0 2 
T0 


The quantity in square bracket   is identify

as C P H where CP H is mean heat capacity.
R
Hence, H can be calculated using mean
heat capacity, CP H

H  C P H
 T  T0 
Solution for T if CP H is given,

H
T  T0 Iterative solution
CP H
 Example 2
By using Table C.1, calculate the heat
required to raise the temperature of 1 mol
methane from 260 to 600°C in a steady-flow
process. Methane is considered in ideal-gas
state.
Example 3

What is the final temperature when 37, 218 J heat is

added to 25 moles of ammonia initially at 500K in a
steady-flow process at 1 atm?
4.2 Latent Heat of Pure Substances
When a pure substance is
liquefied from solid state or
vaporized from liquid at constant
pressure, no change in temperature
occurs.
However, the 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.
• Latent heat of
fusion: heat
required to liquefied
a pure substance
from solid state
• Latent heat of
vaporization: heat
required to vaporize
a pure substance
from liquid state
 4.2 Latent Heat of Pure Substances
 
During phase change, two phases co-exist
Latent heat accompanying a phase change is a
function of temperature and related to Clapeyron
equation:

where for a pure substance at temperature T

ΔH is latent heat, ΔV is volume change
accompanying the phase change, and is the
saturation pressure
 4.2 Latent Heat of Pure Substances
 

= the slope of the vapor pressure-vs-temperature

curve at the temperature of interest.
ΔV is the difference between molar volume of
saturated vapor and saturated liquid
ΔH can be calculated from vapor pressure and
volumetric data
 
Rough estimates of heat of vaporization for pure
liquids at their normal boiling points are given by
Trounton’s rule;

where ΔHn is the heat of vaporization at Tn, the

normal boiling point (absolute). Normal boiling point
is the boiling point at P = 1 atm.

Ar: 8.0; N2:8.7; O2:9.1; HCl:10.4; C6H6:10.5;

H2S:10.6; H2O: 13.1
 4.2 Latent Heat of Pure Substances
 
Estimation of heat of vaporization at normal
boiling point proposed by Riedel:

where Pc is the critical pressure (bar), is the

reduced temperature at Tn
 4.2 Latent Heat of Pure Substances
 
Estimation of heat of vaporization at any
temperature from the known value at single
temperature value proposed by Watson:
 Example 3 (page 134)
Given the latent heat of vaporization of water
at 100°C is 2,257 J.g-1, estimate the latent heat
at 300°C.
 Tutorial
Refer text book “Introduction to Chemical
Engineering Thermodynamics, Smith et al.,
2005, 7th ed.”
 4.1 (a)
 4.2 (b)
 4.11 (a) Chloroform
 4.14 (a)