Chapter 4

Heat Effects

Heat Effects:

• Sensible Heat: When the transfer of heat produces a change in temperature.

• Latent Heat: When a phase change takes place with out a change in
temperature.

• Other heat effects includes heat accompany chemical reactions, and heats
associated with formation or separation of solutions and heat effects of
mixing process.

4.1 Sensible Heat Effects

Molar or specific enthalpy, H,

H = H(T,P)

Then, dH= (δH/δT)P dT + (δH/δp)T dP

= =
Cp Eq’n(2.20) Zero, under the following conditions:
1- The change occurs @ constant pressure, dP = 0 Or
2- The enthalpy of substance is indep. of pressure.
(exactly for ideal gas, and approximately for low press. gases.)

Then, dH = Cp dT
T2

and ΔH = ∫
T1
Cp dT (4.2)

Since Q = ΔH Rev., Const. Press., nonflow process & st. st. process.
T2

Then Q= ΔH = ∫
T1
Cp dT (4.3)

Similarly, U = U(T,P)
T2

ΔU = ∫
T1
Cv dT (4.1)

Since Q = ΔU Rev., Const. Vol., nonflow process & st. st. process.
T2

Then Q= ΔU = ∫
T1
Cv dT

• Heat Capacities of Gases

 • For gases it’s the ideal gas heat capacity (rather than the actual) that is used in
evaluation of the thermodynamic properties such as U and H.

• Ideal gas properties are used because such properties can be evaluated by two
steps:
A. Calculation of ideal gas values from ideal heat capacities.
B. From PVT data of the difference between real gas and ideal gas values.

• The ideal gas heat capacities are different for different gases and function of
Temp. but indep. of Pressure.

• Can be given an experimental equations:

ig
C P = A + BT + C T2 + DT-2
Table C-1 gives values of these constants.
ig
• C P /R is dimensionless.
ig ig
• For ideal gas, C V /R = C P /R -1 (4.5)

• Heat Capacities of Gas mixtures

ig ig ig ig
C Pmixture =y C P +y C P +y C P (4.6)
A A B B C C
Where, y is mole fraction.

• Heat Capacities of solids & liquids

CP / R= A + BT + C T2 + DT-2 (4.4)
Table C-2, C-3and Perry’s hand book , gives values of these constants.
Read Ex. 4.1 and 4.2
• Iteration procedure is required to calculate T2 given T1 and Q or ΔH.

• Define a mean heat capacity, CP , as

H
T2

CP =
H
∫
T1
Cp dT / T2-T1

• Substitute to the above eq’n,

CP / R= A + BT + C T2 + DT-2
and integrate,

2 a
• CP / R= A + BTH + C/3 (4 TH - T1 T2) + D / T1 T2
H

Where TH = T1 + T2 / 2 The arithmetic mean temperature.

T2

• Then, ∫
T1
Cp dT = CP (T2-T1)
H

and, ΔH = CP (T2-T1) b
H

Consequently, T2 = ΔH/ CP + T1 c
H

Solve by iteration:
• Assume value of T2.
• Subs. in eq’n a, then find CP .
H
• Subs. in eq’n c, then find T2.
• Recalculate CP , repeat until convergence is achieved for T2.
H

OR, use the book solution using τ

4.2 Latent Heats of Pure Substances

• Latent heat of
Fusion S→ L
Vaporization L→G
Sublimation S→G

During this process, 2 phases exist.

• Latent heat is function of temp. and related to other system properties by exact
thermodynamic equations:

Clapeyron Equation ΔH = T ΔV dpsat/dT (4.11)

Where,
ΔH = Latent heat.
ΔV = Volume change accompanying the phase change.
psat = Vapor pressure.

When applied for vaporization,

dpsat/dT = Slope of vapor pressure vs. temp.
ΔV = Vsat - Vsat
Vap Liq

• Latent heats may also be measured calorimetrically. Experimental values are

available at selected temperatures for many substances.

• Correlations, like Calpeyron, are available but no enough data information at the
desired temperature are known.

• For this reasons, approximate methods have been developed to estimate latent
heat of vaporization. They are serve one of two purpose:
• To predict the heat of vaporization at the normal boiling point.
• To estimate the heat of vaporization at any temperature from that known at
another single temperature.
™ Trouton’s rule: Rough estimates of latent heat of vaporization for pure
liquids at their normal boiling point.

ΔHn / R Tn ~ 10

Experimental values for this ratio are: Ar, 8.0; N2, 8.7; O2, 9.1; HCl, 10.4; C6H6,
10.5; H2S, 10.6; and H2O, 13.1.

™ Riedel Equation:.

ΔHn / R Tn = 1.092 (ln Pc -1.013)/ 0.93 - Tr (4.12)

n

Where, Tn = normal boiling pt.

ΔHn = molar latent heat of vaporization @ Tn.
Pc = critical pressure, bar.
Tr = reduced temp. @ Tn.
n

Error < 5%

™ Watson Equation:

ΔH2 / ΔH1 = (1 - Tr / 1 - Tr )0.38 (4.13)

2 1

Simple and accurate.

Read Ex. 4.4

4.3 Standard Heat of Reaction

• Chemical reactions are accompanied by the transfer of heat, by temp. changes

or by both.

• Enthalpy changes during reaction

ΔH = ΔHp - ΔHR
Or the heat of reaction, when both reactant and products are under the same T, P.

• Standard states:
ƒ Liquids and solids: The real pure liquid or solid at 1 bar.
ƒ Gases: The pure substance in the ideal-gas state at 1 bar (105 Pa).
(used to be 1 atm (101,325 Pa)).

• Property values at standard stae is denoted by (o). For example heat capacity at
standard state is: Cpo = Cpig

• The heat of reaction depends on how the reaction written:

½ N2 + 3/2 H2 → NH3 ΔHo298 = -46,11 J

Or
N2 + 3H2 → 2NH3 ΔHo298 = -92,22 J (Double)
4.4 Standard Heat of Formation

• A formation reaction is the reaction, which forms one mole of a single

compound from its constituent elements.

For example,
C + ½ O2 + 2H2 → CH3OH
The formation reaction of Methanol.
But,
H2O + SO3 → H2SO4
Not formation reaction.

• The standard heat of formation for compounds are tabulated at 298 K (the
o
standard reference temperature). (ΔH 298).
Given at table C.4.

• Heat of formation reactions at different temperatures can be calculated from

heat capacity data and the known value of the standard heat of formation at
298 K.

• Standard heat of formation for any elements = 0.

• Chemical equations and standard heat of reaction resulted may added or

subtracted to give the standard heat of the required reaction. (Hess’s law).

Consider,
CO2(g) + H2 (g)→ CO (g) + H2O (g) @ 25oC

The formation reactions related to this reaction are as follow:

CO2(g): C (s) + O2 (g) → CO2 ΔHoƒ 298 = -393,509 J

H2 (g) : is an element. ΔHoƒ 298 = 0
CO(g) : C (s) + ½ O2 (g) → CO (g) ΔHoƒ 298 = -110,526 J
H2O(g) : H2 (g) + ½ O2 (g) → H2O (g) ΔHoƒ 298 = -241,818 J

Rewrite these equations so that their sum gives the desired reaction

CO2 (g) → C (s) + O2 (g) ΔHoƒ 298 = +393,509 J

C (s) + ½ O2 (g) → CO (g) ΔHoƒ 298 = -110,526 J
H2 (g) + ½ O2 (g) → H2O (g) ΔHoƒ 298 = -241,818 J

CO2 (g) + H2 (g) → CO (g) + H2O (g) ΔHoƒ 298 = 41,166 J

 • Standard heat of formation depend on the compound state (g, L, …).

H2 (g) + ½ O2 (g) → H2O (g) ΔHoƒ 298 = -241,818 J

However, for

H2 (g) + ½ O2 (g) → H2O (L) ΔHoƒ 298 = -285,830 J

The difference (44,012 J) is approximately the heat of vaporization of H2O @ 25oC.

Read Example 4.5

4.5 Standard Heat of Combustion

• A combustion reaction is defined as a reaction between an element or

compound and oxygen to form specified combustion products.

• Many standard heat of formation cam be determined through combustion

reactions.

Consider the formation of n-butane

4C (s) + 5H2 (g) → C4H10 (g)

This reaction does not proceed as indicated above.
So, we can’t directly measure its heat of formation. However consider the
combustion reactions:

4C (s) + 4O2 (g) → 4CO2 (g) ΔHo 298 = (4)(-393,509) J

5H2 (g) + 5/2O2 (g) → 5H2O (L) ΔHo 298 = (5)(-285,830) J
4 CO2 (g) + 5H2O (L) → C4H10 (g) + 13/2O2 (g) ΔHo 298 = (4)(2,877,396) J

4C (s) + 5H2 (g) → C4H10 (g) ΔHo 298 = -125,790 J

The result is standard heat of formation of n-butane listed in table C.4.

4.6 Temperature Dependence of ΔHo

• Standard heat of reaction from standard heat of formation at 298 K can be

calculated directly:
ΔHo = ∑ νi ΔHoƒi (4.15)

For example, 4HCl (g) + O2 (g) → 2H2O (g) + 2 Cl2 (g)

ΔHo = 2 ΔHoƒH2O – 4 ΔHoƒHCl

@ 298 K from table C.4

ΔHo = 2(-241,818) – 4(-92,307)

= - 114,408 J

• If reaction occurs at temperature other than 298 K,

d ΔHo = ΔCpo dT (4.17)

Integrate between 298K and T

T

ΔHo = ΔHo298 + R ∫
298.15
ΔCpo / R dT (4.18)

Then, ΔHo = ΔHo298 + ΔCpoH (T- 298.15)

Where ΔCpoH can be evaluated similar to CpoH (mean heat capacity) as:
2
ΔCPoH / R= ΔA + ΔBTH + ΔC/3 (4 TH - T1 T2) + ΔD / T1 T2

Where ΔA = ∑ νI Αi and so on ………

Read Example 4.6.

4.7 Heat Effects Of Industrial Reactions

• Industrial reactions are rarely carried out under standard state conditions.

• Reactants may not present in stoichiometric ratios.

• Reaction may not go to completion.
• Final temperature may differ from the initial temperature.
• Inert species may be present.
• Several reactions may occur simultaneously.

• Calculations of the heat effects of actual reactions are based on theoretical

flame temperature (TFT) calculation.

• TFT: is useful to predict the highest achievable temperature, which is useful

to select the material type. Usually highest temperature occurs at adiabatic
process.

Example 4.7

Read Examples 4.8 and 4.9