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Chapt 4 Heat Effects - Lecture notes 4

Thermodynamics (Mangosuthu University of Technology)

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CHAP 4. HEAT EFFECTS

 Sensible heat effects (no phase transition, no reactions, no changes in composition).
 Latent heat (associated with phase change; no reaction)
 Heat of reaction (associated with a reaction; change of composition)

4.1. Sensible heat effects

- Molar or specific internal energy:

 U   U 
dU    dT    dV (4.1)
 T V  V  T
For a process at constant volume or such that internal energy is independent of volume,

dU  CV dT (4.2)

T2

U   CV dT (4.3)
T1
For a mechanically reversible constant-volume process,

Q  U (4.4)

T2

Q  U   CV dT (4.5)
T1

-Molar or specific enthalpy:

 H   H 
dH    dT    dP (4.6)
 T  P  P  T

Using the definition of Cp,

 H 
dH  C P dT    dP (4.7)
 P  T

For a process at constant pressure or such that the enthalpy is independent of pressure,

dH  C p dT (4.8)

T2

H   C P dT (4.9)
T1
For a mechanically reversible constant-pressure process,

Q  H (4.10)

T2

Q  H   C P dT (4.11)
T1

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- Temperature-dependence of the heat capacity

CP
In general:  A  BT  CT 2  DT 2 (4.12)
R

C Pig
For an ideal gas:  A  BT  CT 2  DT  2 (4.13)
R

C Pig C vig
Notes: For ideal gases:  1 (4.14)
R R

For mixtures, C P ,mix  y AC P , A  y B C P , B  yC C P ,C  ...

ig ig ig ig
(4.15)

where y A, y B , yC refer to mole fractions and A, B and C refer to ideal gases

The sensible heat integral can be evaluated as follows:

T2
CP
H  R  dT (4.16)
T1
R

4.2. Latent heats of pure substances

- Definition: Heat required for phase change or phase transition
-Some correlations to predict latent heats of pure substances

dP sat
 H  TV (4.17)
dT

where ΔH: latent heat; ΔV: volume change associated with the phase change; Psat: saturation pressure

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 Watson correlation

It is used to predict the latent heat of vapourisation of a pure liquid at any temperature from
the known value at a single temperature:

0.38
H 2  1  Tr 2 
  (4.18)
H 1  1  Tr1 

 Correlation by Riedel
It is valid for normal boiling point only (Tb).

H n 1.092ln PC  1.013
 (4.19)
RTn 0.930  Trn
,
Pc: critical pressure in bar
Trn: reduced temperature at Tn

4.3. Heat (Enthalpy) of reaction

1 A1   2 A2   3 A3   4 A4 (CE 4.1)

Heat of reaction is the enthalpy change when v1 moles of A1 and v2 moles of A2 react to form v3 moles
of A3 and v4 moles of A4, both reactants and products being at a given temperature T.

Enthalpies of reaction are tabulated under standard conditions.

A standard state is a particular state of a species corresponding to a certain temperature T, and

specified conditions of pressure, composition, and physical conditions e.g. gas, liquid and solid.

Generally,
 Standard state pressure: 1 bar;
 Gases: pure substance in the ideal gas state at 1 bar;
 Liquids and solids: the real pure liquid or solid at 1 bar

Properties for standard state are denoted by the degree symbol: C P ; H f , …

o o

H 298
o
Standard enthalpy change at 298 K

Standard-state properties are functions of temperature only.

When the heat of reaction is provided for a particular reaction, it applies for the stoichiometric
1 3
coefficients as written. Example: N 2  H 2  NH 3 .......... ...... H 298
o
 46110J (CE 4.2)
2 2

N 2  3H 2  2 NH 3 .......... ......H 298

o
 92220J (CE 4.3)

Standard heat of formation: Standard heat associated with the formation of a single compound from its
constituent elements.

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1
Example: Formation reaction of methanol. C  O2  2 H 2  CH 3 OH (CE 4.4)
2
From Tables: Standard heat of formation = ????
Formation reactions produce one mole of compound. Hence the heat of formation is based on 1 mol of
compound formed.

The heat of reaction can be calculated knowing heats of formation of reactants and products:

Considering equation (4.20):

  
H ro, 298   vi H of , 298  v3 H of ,3, 298  v4 H of , 4, 298  v1H of ,1, 298  v2 H of , 2, 298  (4.20)
i

If the reaction is combustion, then the heat of reaction is termed as heat of combustion.

Hess’ law allows for obtaining enthalpies of formation from enthalpies of combustion

Hess’ law: …………………………………………………………………………………………..

4.4. Temperature dependence of ΔHo (Van’t Hoff equation)

dH  C P dT (4.21)

T2

H  
T1
C P dT (4.22)

T
H r ,T  H r , 298   v C
298
k P ,k dT (4.23)

4.5. Heat effects of industrial reactions

Industrial reactions are not usually carried out at standard state conditions,
The reaction may not be present in stoichiometric proportions
The reaction may not go to completion
The final temperature may differ from initial temperature (Adiabatic flame temperature)
This can be calculated using the following equations
H  0 (4.24)
Tf Tf

H  H r , 298   v C
298
k P ,k dT   n'i C P ,i
T
(4.25a)

 Tf
 Tf
H  n H r , 298    v k C P ,k dT    n'i C P ,i (4.25b)
 298  T
--n; number of moles for the limiting reactant consumed
--n’: number of moles for the inerts and the reactant in excess

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Worked examples
1) What is the maximum temperature that can be reached by the combustion of methane with 20 %
excess air? Both the methane and the air enter the burner at 25 oC.
2) One method for the manufacture of synthesis gas (mixture of CO and H2) is the catalytic reforming
of CH4 with steam at high temperature and atmospheric pressure:

CH 4( g )  H 2 O( g )  CO( g )  3H 2( g )

The only other reaction to consider is the water-gas shift reaction:

CO( g )  H 2 O( g )  CO2( g )  H 2( g )

If the reactants are supplied in the ratio, 2 mol steam to 1 mol CH4, and If heat is supplied to the
reactor so that the products reach a temperature of 1300 K, the CH4 is completely converted and the
product stream contains 17.4 mol-% CO. Assuming the reactants to be heated to 600 K, calculate the
heat requirement for the reactor

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