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SMJC 2243 Chemical Engineering

Thermodynamics
Semester 2
Session 2014/2015
16th March 2015
Room 4.37.01/02

Chapter 3:
HEAT EFFECTS

INTRODUCTION
Heat transfer is a common operation in the chemical
industry
Example;
Manufacture of ethylene glycol (an antifreeze agent)
Ethylene ethylene oxide ethylene glycol
Oxidation
Hydration

Catalytic oxidation reaction temp.: 250C


Reactant (ethylene + air) heated before enter the reactor
Preheater design depends on the Rate of Heat Transfer
Combustion reaction (ethylene + O2) raise temperature
Heat removed from the reactor, temp. doesnt rise much above
250 C
Higher temp.; produce CO2 (unwanted product)
Design the reactor requires knowledge heat transfer rate; depends
on the heat effects assoc. with chemical reaction
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Ethylene ethylene oxide ethylene glycol


Oxidation
Hydration
Ethylene oxide ; hydrated to glycol by
absorption in water
Heat evolved;
Phase change + dissolution process
Hydration reaction between dissolved ethylene
oxide + water

Glycol recovered from water distillation


(process of vaporization + condensation
Separate solution into its components

Simple chemical-manufacturing process


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Characteristic of Sensible Heat Effect


1. Temperature changes
2. Heat effects of chemical reaction
3. Phase transition
4. Formation of solution
5. Separation of solution
determined from experimental measurement at
constant temperature

SENSIBLE HEAT EFFECTS


When heat transfer to a system;
No phase transitions
No chemical reactions
No changes in composition
Cause the changes of temperature (system)

When the system is a homogeneous substance


(constant composition),
phase rule: fixing the values of 2 intensive properties
establishes its state
Molar @ specific internal energy of a substance:
expressed as a function of 2 other state variable
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Total internal Energy,


= ,

= +

where is constant-volume heat capacity


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The final term may be set = 0 in 2


circumstances;
=0

= +


1. For any constant-volume process, regardless of substance
2. Whenever the internal energy is independent of volume,
regardless of the process
this is exactly true for ideal gases & incompressible
fluids, approximately true for low-pressure gases
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In either case,
=
2

For a mechanically reversible constant-volume


process, =
2

= =

Similarly, the molar @ specific enthalpy may be expressed as a


function of temperature & pressure, then = ,

= +


where is constant-pressure heat capacity
Again, 2 circumstances allow the final term to be set = 0
1.
2.

For any constant-pressure process, regardless of substance


Whenever the internal energy is independent of volume,
regardless of the process
this is exactly true for ideal gases & incompressible fluids,
approximately true for low-pressure gases

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In either case,
=
2

Moreover, = for a mechanically reversible


constant-pressure, closed-system processes,
2

= =

The common engineering application of this


equation is to steady-flow heat transfer
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Temperature Dependence (Heat Capacity)


Evaluation of the integral in below equation requires knowledge of the
temperature dependence of the heat capacity
2

= =

Given by empirical equation

= + + 2 + 2

1.

= + + 2

2.

= + + 2

where either C @ D is zero, depending on the substance considered

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For gases,
Ideal-gas heat capacity ( actual heat capacity) is
used in the evaluation of such thermodynamic
properties as the enthalpy
Reason: thermodynamic-property evaluation is most
conveniently accomplish in 2 steps
1.

Calculation of values for hypothetical ideal gas state, ideal-gas


heat capacities are used;
2. Correction of ideal-gas-state values to the real-gas-values
A real gas becomes ideal in the limit as P 0,

Ideal-gas- state het capacities (designated by and


) are therefore different for different gases; although
functions of temperature, they are independent of
pressure

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The influence of temperature on


for Ar, N2, H2O and CO2 is illustrated in
Fig. 4.1
Temp. dependence is expressed
analytically by equation, such as:

2
2

= + + +

Values of parameters are given in Table


C.1 (Appendix C)
Two ideal-gas heat capacities are
related

Temp. dependence of

the temp. dependence of

follows from

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As with gases, the heat capacities of solids &


liquids are found by experiment
Parameters for the temperature dependence
of are given for a few solids & liquids in
Table C.3 & C.4 (Appendix 3)

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Sensible Heat-Integral
Evaluation of the integral is accomplished by
substituting for as a function of T, followed by normal
integration
For temp. limits of T0 and T, the result is expressed as;

0
2 2
3 3
= 0 1 + 0 1 + 0 1
2
3
1
+
0

Where

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Mean heat capacity;


2

= + 0 + 1 + 0 2 + + 1

2
3

+
0 2
=

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