Part 4

Heat Effects

Sensible Heat Effects

Sensible heat is heat transfer resulting in a temperature change in the system with no change in phase, no chemical reactions and no changes in composition Quantity of Heat Transferred = f(Tf Ti)

I. For a system of homogeneous substance of constant composition

U = U(T,V)

dU =
U Cv = T V

U T

dT +
V =c

U V

dV
T =c

dU = C v dT +

U V

dV
T =c

U dV = 0 V T

dU = C v dT

1. For any constant volume process, regardless of the substance. (true for ideal and T2 Q = U = C v dT low pressure gases, T1 incompressible fluids)

2. Whenever the internal energy is independent of volume, regardless of the process.

II. For a system of homogeneous substance of constant pressure. H = H (T , P )

,

dH =

H H dT + dP T P P T

dH = C P dT +

H dP P T

CP

H T

H dP = 0 P T
If : 1. constant P process, regardless of the substance. 2. the enthalpy of the substance is independent of pressure, regardless of the process (true for ideal gases and low pressure process) 3. transfer of heat occurs in steady flow system where KE, PE, and Ws = 0

Temperature Dependence of Heat Capacities of Gases

The temperature dependence of specific heats [Cp=f(T)] is given by an empirical equation, the two simplest expressions of practical value of which are:

Cp

= + T + T 2 R Cv = a + bT + cT 2 R
where , , , a, b, and c are constants characteristic of the particular gas.

Cp R
Where:

= A + BT + CT 2 + DT 2

C or D = 0 (depending on the gas considered) A, B, C, and D (from Table C.1, App. C, p. 684. Unit of Cp is governed by the unit of R.

Thermodynamic property evaluation is most conveniently accomplished in two steps:

calculation of values for a hypothetical ideal gas state wherein ideal gas heat capacities are used. correction of the ideal gas state values to the real gas values. (A real gas becomes ideal in the limit as P 0).

For Ar, N2, H2O and CO2, the influence of T on Cpig is illustrated in Fig. 4.1/p. 128. 7 CO2 H2 O N2

Cp

ig

6 5 4 3 2 500

Ar 1000 1500 Temperature [K] 2000

Ideal gas heat capacities of N2, H2O, Ar and CO2

ig Cp Cv = 1 R R

ig

Cv R

ig

or

Cp

ig : determined by experiment and

solved by methods of statistical mechanics (from spectroscopic data and molecular structure).

If experimental data are not available, methods of estimations are employed. (Refer to Liquids and Gases by Reid, Prausnitz and Poling). Note: Cpig are exactly correct for real gases only at P = 0.

Latent Heat of Pure Substances

At constant pressure:
(1) (2) Pure solid substance at T Pure solid substance at T

Hf Hv

Liquid state of substance at T Vapor state of substance at T

Hf = latent heat of fusion Hv = latent heat of vaporization

Latent heat is heat transfer resulting in the coexistence of two phases of the system of constant temperature and pressure.

sat Clapeyron Equation: H = TV dP dT

where: H = latent heat V = volume change accompanying the phase change Psat = vapor pressure For the vaporization of pure liquid:

dP sat dT
V H

slope of the vapor pressure vs. temperature curve at the temperature of interest. = difference between molar volumes of saturated vapor and saturated liquid. = latent heat of vaporization =

Approximate Methods for Evaluating H

1. Prediction of the heat of vaporization at the normal boiling point, i.e., at a pressure of 1 standard atmosphere, defined as 101,325 Pa.
Reidel Equation

H n (1.092)(ln Pc 1.013) = RTn 0.930 Trn

where:

Hn = molar latent heat of vaporization at Tn

Tn = normal boiling point

Trn

Pc

= critical pressure, bar = reduced temperature at Tn

2. Estimation of the heat of vaporization at any temperature from the known value at a single temperature. 0.38 H 2 1 Tr2 Watson Equation: = H1 1 Tr1
where: H1 = latent heat of vaporization at T1 H2 = latent heat of vaporization at T2

T= r1

reduced temperature at T1

Tr2 = reduced temperature at T2

Standard Heat of Reaction

Thermochemical Equation:
The heat associated with a given reaction depends on: a) the quantity that reacts; b) temperature of reaction; c) physical state of each reactant and product; and d) whether the reaction occurs at constant volume or at constant temperature

Hess Law of Heat Summation:

If a reaction proceeds in several steps, the heat involved in the overall reaction is the algebraic sum of the various steps, and this sum will be identical with the heat involved if the reaction proceeds in a single step.

Standard State particular state of a species at temperature T and at specified conditions of pressure, composition and physical condition as gas, liquid or solid. For gases: physical state is the ideal gas state at P = 1 bar. For liquids and solids: physical state is the real gas state at P = 1 bar. Cpo : standard state heat capacity For gases: Cpo = Cpig

Standard Heat of Formation

Heat of Formation of a Compound [Hf] heat involved in the formation of one mole of a compound from its constituent elements. C + O2 Obtained by: 1. direct measurement of the H of the reaction of the formation of the compound from its constituent elements 2. calculation from heats of reaction involving the compound. + 2 H2 CH3OH

Heat of Reaction from Heats of Formation of Reactants and Products

Hreaction = Hproducts Hreactants

Refer to Table C.4 / pp. 686-687

Standard Heat of Combustion

Heat of Combustion : the heat liberated in the
complete combustion of 1 mole of the substance with oxygen.

Heat of combustion is always negative since heat is always given off and it can directly be measured by the combustion reaction itself.

Higher Heat and Lower Heat of Combustion:

If water is a product of combustion, the higher heat of combustion is obtained when the water product is in the liquid state and the lower heat of combustion is obtained when the water product is in the vapor state.

Application of Heat of Combustion:

1. To determine the suitability of a substance as an industrial fuel with respect to heat evolved on combustion. 2. To calculate heats of formation of substances whole formation reactions cannot be carried out experimentally. 3. Heat of reaction in cases where the heats of formation of a reactant or product is not available. 4. Energy differences of allotropic forms of elements. 5. Energy associated with certain atomic groups in a molecule.

Heat of Reaction as a Function of Temperature

The heat of reaction obtained calorimetrically or by calculation corresponds to some one definite temperature. At other temperatures, the heat of reaction will not usually be the same. For standard reactions, products and reactants are always at the standard state pressure of 1 bar. Standard state enthalpies are functions of temperature only.

dH io = Cp io dT
i

Cp o = vi Cp io Cp o dT R
T T0

dH o = Cp o dT
o H = H 0 + R T To

where

H o =
o H 0 =

Heats of reaction at

Heat Effects of Industrial Reactions

In industrial reactions,
1) the reactants may not be present in stoichiometric proportions; 2) reaction may not go to completion; 3) final temperature may differ from the initial temperature; 4) inert species may be present; and 5) several reactions may occur simultaneously.