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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

Latent heats of pure substances

Standard heat of reaction / formation / combustion

1

Sensible heat effects

no phase transition,

no chemical reactions

and no changes in composition

causes the T of the system to change

the resulting temperature change

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

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

3

T1

Similarly H = H(T, P)

H H H

dH dT dP dH CP dT dP

T P P T P T

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 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

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

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

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 .

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

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 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:

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

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.

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)

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

12

Standard heat of formation (Chemical heat effect)

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)

13

Standard heat of formation (Chemical heat effect)

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

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:

Formation reaction of CO2 must be written in reverse

How to use formation reaction of HO2 in either liquid or gas state?

14

Ex: 4.5

Standard heat of combustion (Chemical heat effect)

combustion, measured calorimetrically.

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:

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)

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

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

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

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

17

Temperature dependence of H (Chemical heat effect)

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

i

formulation gives:

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: 4.7

Ex: 4.8

C

MDCPHT0, T; DA, DB, DC, DD

P H

Ex: 4.9

R

19

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