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Chapter 4

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

Sensible heat effects


Latent heats of pure substances
Standard heat of reaction / formation / combustion
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Sensible heat effects

Sensible heat effects are characterized by temperature changes

Heat transfer to a system in which there are:


no phase transition,
no chemical reactions
and no changes in composition
causes the T of the system to change

We develop here relations between the quantity of heat transferred and


the resulting temperature change

The phase rule implies that the state of homogeneous system of constant
composition is established by fixing two intensive properties
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For example U = U(T, V)

U U U
dU dT dV dU CV dT dV
T V V T V T

Isochoric process for any substance


U
dV 0 When U is independent of V which is true for:
V T
Ideal gases
Incompressible fluids
Low pressure gases

T2
In either case, dU CV dT U CV dT
T1

T2
For mechanical rev const V process: Q U CV dT
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T1
Similarly H = H(T, P)

H H H
dH dT dP dH CP dT dP
T P P T P T

Isobaric process for any substance


H
dP 0 When H is independent of P which is true for:
P T
Ideal gases
Low pressure gases
T2
In either case, dH CP dT H CP dT
T1

Q = H for mechanical rev const P closed system T2


Q H CP dT
processes and for the transfer of heat in steady
T1
flow exchangers where Ep = Ek = Ws = 0: 4
T2
The evaluation of the integral
C
T1
P dT requires Cp variation with T

Two simplest expressions exist and can be combined in a unique one:

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

The unit of Cp is governed by the choice of R

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.
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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

The T dependence of Cvig/R follows from the T dependence of CPig/R

Gas mixtures of constant composition behave exactly as do pure gases


because in an ideal gas, molecules have no influence in one another

CPigmixture y ACPigA yBCPigB yC CPigC 6


Heat capacities of solids and liquids
As with gases, Cp of solids and liquids are found by experiment.
Parameters of Cp(T) for few solids and liquids are also given in App. C .

Evaluation of the sensible heat integral


When T0 and T are given, the calculation of Q or H is straightforward
But an iteration scheme must be used to calculate T for given T0 and Q
T
H CP dT CP H
T T0
T0

With:
CP
R
H
A
B
2 3

T0 1 T02 2 1 2
C D
T
T

T0
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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.

Use of defined functions

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
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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).

The latent heat accompanying a phase dP sat


H TV
change is given by Clapeyron equation dT
H: Latent heat Psat: saturation pressure
V: volume change accompanying the phase change 9
Latent heats of vaporization
Because their importance from a practical point of view, latent heats of
vaporization have received most attention. Some methods allow:

1. Prediction of the heat of vaporization at the normal boiling point (at a


pressure of 1 atm = 101325 Pa:

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 aA+bB lL+mM

The standard heat of reaction is defined as the enthalpy change when a


mole of A and b moles of B in their standard states at temperature T react to
form l moles of L and m moles of M in their standard states at the same T.

A Standard State (ST) is a particular state of a species at temperature T


and specified conditions of pressure, composition and physical condition

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)

When a heat of reaction is given for a particular reaction, it applies for


the stoichiometric coefficients as written. If each stoichiometric
coefficient is doubled, the heat of reaction is doubled.
1 3
N 2 H 2 NH3 H 298 46,110 J
2 2
N 2 3 H 2 2NH3 H 298 92,220 J

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Standard heat of formation (Chemical heat effect)

A formation reaction is defined as a reaction which forms a single


compound from its constituents elements

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)
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Standard heat of formation (Chemical heat effect)

Standard heat of formation of a compound at 25C is represented by H f 298


A list of values for some chemical compounds is available in Table C.4

When chemical equations are combined by addition, the standard heats of


reaction may also be added to give the standard heat of the resulting
reaction, This is possible because enthalpy is a state function.

Study the example of the reaction from the book page 137 -138:

CO2 g H2 g COg H2Og


Formation reaction of CO2 must be written in reverse

Formation reaction of H2 is equal to zero because hydrogen is an element


How to use formation reaction of HO2 in either liquid or gas state?
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Ex: 4.5
Standard heat of combustion (Chemical heat effect)

Many standard heats of formation come from standard heats of


combustion, measured calorimetrically.

Combustion reaction is defined as a reaction between an element or


compound and oxygen to form specified combustion product. Data are
based on one mole of the substance burned.

Study the example of the reaction from the book page 139:

4Cs 5H2 g C4 H10 g

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)
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Temperature dependence of H (Chemical heat effect)

In this section we treat the calculation of standard heats of reaction at


other temperatures from knowledge of the value at the reference T.
The general chemical reaction may be written as:

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

i Is the stoichiometric number for component Ai

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

Multiplying by i and summing over all


products and reactants gives: i i i P dT
dH
i
o
C o

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

As defined in the previous slide: i i H


i
H o

d i H dH C o T
i H H 0o R P
dT
C
i
i
o
Pi C o
P T0
R
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Temperature dependence of H (Chemical heat effect)

H and H0 are heats of reaction at T and at ref T (T0) respectively.


If the temperature dependence of Cp for each component is given by:

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

where A i Ai (with analogous definitions for B, C and D)


i

If the mean heat capacity change of reaction is defined, an alternative


formulation gives:

H H 0 CP
H
T T0
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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

T 0 R dT IDCPHT0, T; DA,DB, DC, DD


Ex: 4.7

Ex: 4.8
C
MDCPHT0, T; DA, DB, DC, DD
P H
Ex: 4.9
R
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