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Heat Effects
Heat transfer is a common operation in the chemical industry.
In this chapter we apply thermodynamics to the evaluation of most of the
heat effects that accompany physical and chemical operations
The phase rule implies that the state of homogeneous system of constant
composition is established by fixing two intensive properties
2
For example U = U(T, V)
U U U
dU dT dV dU CV dT dV
T V V T V T
T2
In either case, dU CV dT U CV dT
T1
T2
For mechanical rev const V process: Q U CV dT
3
T1
Similarly H = H(T, P)
H H H
dH dT dP dH CP dT dP
T P P T P T
CP
a bT gT 2
R CP
A BT CT 2 DT 2
CP R
a bT cT 2
R
a, b, c, a, b, g, A, B, C, D are conts characteristics for particular substance
Ideal gas heat capacity Cpig is used rather than Cp for evaluating
thermodynamic properties as enthalpy. Ideal gas heat capacities increase
smoothly with increasing T toward an upper limit.
5
Influence of T on Cpig for Ar, N2, H20 and CO2
ig
CP
A BT CT 2 DT 2
R
Parameters are given in App. C (Table C.1)
As a result of R CP CV
ig ig
CV CP
1
R R
With:
CP
R
H
A
B
2 3
T0 1 T02 2 1 2
C D
T
T
T0
7
Evaluation of the sensible heat integral
1. Evaluate <CP>H with a starting value of T (and hence )
H
2. Use this value of <CP>H to calculate T by T T0
CP H
3. With the new value, <CP>H is reevaluated
4. Iteration continues to convergence on a final value of T.
CP 2
T
C dT ICPHT0, T; A, B, C, D A BT CT DT
2
P
T0 R
CP
A T0 1
H B
CP R 2
H
MCPHT0, T; A, B, C, D D
R
C 2 2
T0 1 8 2
T
3
Latent heats of pure substances
When a pure substance occurs a change in its state, no change in
temperature occurs. However, the process requires a transfer of a finite
amount of heat to the substance.
This heat effect is called the latent heat accompanying a phase change
(Latent heat of fusion or latent heat of vaporization for example)
According to the phase rule, a such system is univariant (its intensive state
is described by the specification of just one intensive property (T only).
H n
Troutons rule 10
RTn
H n 1.092ln PC 1.013
Riedels equation
RTn 0.930 Trn
2. Estimation of the heat of vaporization at any T from just one known
value of DH at a given T (for example estimated by Riedels equation):
0.38
H 2 1 Tr 2
Watsons equation
H1 1 Tr1 Ex: 4.4 10
Standard heat of reaction (Chemical heat effect)
Tabulation of all possible heat effects for all possible reactions is impossible.
We therefore calculate the heat effects for reactions carried out in diverse
ways from data for reactions carried out in a standard way
For gases: the ST is the pure substance in the ideal gas state at 1 bar.
For liquids and solids: the ST is the real pure liquid or solid at 1 bar. 11
Standard heat of reaction (Chemical heat effect)
Property value at the standard state are denoted by the dergee symbol.
For example CP is the standard state heat capacity.
For gases CP is identical with CPig. (Table C.1 applies for CP)
12
Standard heat of formation (Chemical heat effect)
1 3
N 2 H 2 NH3 Formation reaction of NH3
2 2
SO 3 H 2O H 2SO 4 Not a formation reaction
The standard heat of any reaction can be calculated if the standard heats
of formation of the compounds taking part in the reaction are known.
Formation reactions are understood to produce 1 mol of product, the heat
of formation is therefore based on 1 mol of the compound formed.
Heats of reaction at any T can be calculated from Cp data if the value for
one T is known: the usual choice of this T is 25C (298,15K)
13
Standard heat of formation (Chemical heat effect)
Study the example of the reaction from the book page 137 -138:
Study the example of the reaction from the book page 139:
Standard heat of combustion are not given in the appendix of this book
but can be found in many handbooks. (For example the value used for
C4H10 in 4.5)
15
Temperature dependence of H (Chemical heat effect)
1 A1 2 A 2 3 A3 4 A 4
i Is the stoichiometric coefficient of component Ai
positive for products and negative for reactants
This sign convention allows to express the standard heat of this reaction by:
H i H io
i
Where Hi is the enthalpy of species i in its standard state and the
summation is all over products and reactants. 16
Temperature dependence of H (Chemical heat effect)
If the standard state enthalpies of all elements are arbitrarily set equal to
zero, then:
H H o
i
i fi
For standard reactions, products and reactants are at the same pressure
(1 bar), so Hi are function of temperature only dH o C o dT i Pi
i
i
Because i is constant:
d H o
i i i Pi dT
C o
d i H io i CPoi dT
i i i i
d i H dH C o T
i H H 0o R P
dT
C
i
i
o
Pi C o
P T0
R
17
Temperature dependence of H (Chemical heat effect)
CP
A BT CT 2 DT 2
R
Then:
CP B C 3 3 D 1
T
T 0 R dT AT0 1 2 T0 1 3 T0 1 T0
2
H H 0 CP
H
T T0
18
Temperature dependence of H (Chemical heat effect)
With:
CP B C 2 2 D
R
H
A
2
T0 1
3
T0 1 2
T0
Ex: 4.6
Use of defined functions
CP
T
Ex: 4.8
C
MDCPHT0, T; DA, DB, DC, DD
P H
Ex: 4.9
R
19