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Chapter 2 Heat Effects

This document discusses heat effects that accompany physical and chemical reactions. It covers two main topics: 1. Sensible heat, which is the heat required to change a substance's temperature without changing its state. The specific heat capacity of a substance determines how much heat is required. 2. Latent heat, which is the heat required for a substance to change state, such as melting or boiling, without a change in temperature. The latent heat of vaporization is considered for various pure substances evaporating at constant pressure. Empirical equations are provided to estimate latent heat values.

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401 views

Chapter 2 Heat Effects

This document discusses heat effects that accompany physical and chemical reactions. It covers two main topics: 1. Sensible heat, which is the heat required to change a substance's temperature without changing its state. The specific heat capacity of a substance determines how much heat is required. 2. Latent heat, which is the heat required for a substance to change state, such as melting or boiling, without a change in temperature. The latent heat of vaporization is considered for various pure substances evaporating at constant pressure. Empirical equations are provided to estimate latent heat values.

Uploaded by

prakash_krishnan_2
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPT, PDF, TXT or read online on Scribd
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Chemical Engineering

Thermodynamics

Chapter 2
Heat Effects
Chapter Outline
2.1 Sensible Heat
2.2 Latent Heat of Pure Substances
Design of reactors requires knowledge
of the heat rate which depends on
the heat effects associated with the
chemical reactions.

Thermodynamics is applied to evaluate


most of heat effects that accompany
physical and chemical reactions.
2.1 Sensible Heat
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
volume, V;
 U  constant-
CV    = volume heat
 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
 V T Internal energy independent of
volume. True for ideal gases and
incompressible fluids.
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-
CP    = 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 independent of
 P T volume. 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 Q  U  C dT and
 V 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.
Heat capacity is given by 2 simplest
expressions;
CP CP
 α  T  T and
2
 a  bT  cT  2
R R
Where  , ,  , a, b and c are constants
characteristic of the particular substance.

They are combined to give:


CP 2
 A  BT  CT  DT
2

R
ig
C
Idea-gas-state heat capacities, P and V
C
ig

are dependence on temperature but


independent of pressure.
Temperature-dependence heat capacity
is expressed by:
ig
CP
 A  BT  CT 2  DT  2
R
Value of parameter are given in Table C.1
(pg. 684) for common organic and inorganic
gases.
Two ideal-gas heat capacities are related:
ig ig
CV CP
 1
R R
Table C.1
Try this…

Given the molar heat capacity of methane in


the ideal-gas-state as functions of
temperature
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.


Evaluation of the
Sensible Heat Integral
Now, we can calculate Q or H at given T0
and T by integrating C P .

C P dT is solved as a function of T followed


by integration
B 2 2

T0 CP dT  AT0   1  2 T0   1 
T
 T

D   1
C 3 3
3

T0   1  
T0   

T0
If Q or H were given and asked to
calculate T the equation is rearranged:

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

The quantity in square bracket   is identify


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

H  C P H  T  T0 

Solution for T if CP H is given,

H
T  T0
CP H
Try this…

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.
2.2 Latent Heat of Pure Substances
When a pure substance if
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.
Example: Water
There are coexistance of two phases.
Latent heat accompanying a phase
change is a function of temperature
and related to Clapeyron equation:
dP sat
H  TV
dT

For pure substance at T ,


H = latent heat
V = volume change accompanying
the phase change
sat
P = saturation pressure
In the vaporization of a pure liquid:
dP sat
dT
= the slope of the vapor pressure-vs-
temperature curve at the temperature of
interest.
V = the difference between molar volume
of saturated vapor and saturated liquid.

H = latent heat of vaporization


H can be calculated from vapor-pressure
and volumetric data.
Rough estimates of heat of vaporization for
pure liquids at their normal boling points are
given by Trounton’s rule;
H n
 10
RTn

where Tn is the absolute temperature of the


boiling point.
Ar: 8.0; N2:8.7; O2:9.1; HCl:10.4; C6H6:10.5;
H2S:10.6; H2O: 13.2
Estimation of heat of vaporization at normal
boiling point proposed by Riedel:
H n 1.092 ln Pc  1.013

RTn 0.930  Trn

where Pc is the critical pressure (bar),


Trn is the reduced temperature at Tn .
Estimation of heat of vaporization at any
temperature from the known value at single
temperature value proposed by Watson:
0.38
H 2  1  Tr2 


H1  1  Tr1 

Try this…

Given the latent heat of vaporization of


water at 100°C is 2,257 Jg-1, estimate the
latent heat at 300°C.
What have you learned…

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