Bab 4 Termo

Chapter 4
Heat Effects
Heat effects refer to physical and chemical phenomena that are associated with heat transfer to
or from a system or that result in temperature changes within a system, or both. The simplest
example of a heat effect is the heating or cooling of a fluid by the purely physical direct transfer
of heat to or from the fluid. The temperature changes that occur are known as sensible heat
effects, because they may be detected by our sense perception of temperature. Phase changes,
physical processes occurring for a pure substance at constant temperature and pressure, are
accompanied by latent heats. Chemical reactions are characterized by heats of reaction, which
for combustion reactions evolve heat. Every chemical or biochemical process is associated with
one or more heat effects. The metabolism of the human body, for example, generates heat which
is either transferred to its surroundings or used to maintain or increase body temperature.
Chemical manufacturing processes may include a number of heat effects. Ethylene
glycol (a coolant and antifreeze) is made by catalytic partial oxidation of ethylene to form
ethylene oxide, followed by a hydration reaction:
C 2 H 4 +  _12  O2 → C 2 H 4O
   
C 2 H 4O + H 2O → C 2 H 4 (OH)
 2
The oxidation reaction is carried out near 250°C, and the reactants must be heated to
this temperature, a sensible heat effect. The oxidation reaction tends to raise the temperature,
and the heat of reaction is removed from the reactor to keep the temperature near 250°C. The
ethylene oxide is hydrated to glycol by absorption in water. Heat is evolved because of the
phase change and dissolution, and also because of the hydration reaction. Finally, the glycol
is purified by distillation, a process of vaporization and condensation, resulting in the sepa-
ration of glycol from solution. Virtually all of the important heat effects are included in this
process. Most of these are treated in the present chapter, although heat effects related to mix-
ing processes must be delayed until Chap. 11, after thermodynamics of solutions have been
introduced in Chap. 10. The following important heat effects are considered in this chapter:
∙ Sensible heat effects, characterized by temperature changes

∙ Heat capacities as a function of temperature and their use through defined functions
∙ Heats of phase transition, i.e., latent heats of pure substances
133
134 CHAPTER 4. Heat Effects
∙ Heats of reaction, combustion, and formation

∙ Heats of reaction as a function of temperature
∙ The calculation of heat effects for industrial reactions
4.1 SENSIBLE HEAT EFFECTS
Heat transfer to or from a system in which there are no phase transitions, no chemical reac-
tions, and no changes in composition causes a sensible heat effect, i.e., the temperature of the
system is caused to change. The need here is for a relation between the quantity of heat trans-
ferred and the resulting temperature change.
When the system is a homogeneous substance of constant composition, the phase rule
indicates that fixing the values of two intensive properties establishes its state. The molar or
specific internal energy of a substance may therefore be expressed as a function of two other
state variables. The key thermodynamic variable is temperature. With molar or specific vol-
ume chosen arbitrarily, we have U = U(T, V). Then
( ∂ T ) ( ∂ V )
∂ U ∂ U
dU = ___
        dT +  ___
        dV
V T
With the definition of CV provided by Eq. (2.15) this becomes:
( ∂ V )
∂ U
dU = CV  dT +  ___
        dV
T
The final term is zero in two circumstances:
∙ For any closed-system constant-volume process.

∙ Whenever the internal energy is independent of volume, as for the ideal-gas state and the
incompressible liquid.
In either case, dU = CV  dT
ΔU =     CV  dT 
T 2
∫ T 1
and (4.1)
Although real liquids are to some degree compressible, far below their critical temper-
ature they can often be treated as incompressible fluids. The ideal-gas state is also of inter-
est, because actual gases at low pressures approach ideality. The only possible mechanically
reversible constant-volume process is simple heating (stirring work is inherently irreversible),
for which Q = ΔU, and Eq. (2.18) written for a unit mass or a mole becomes:
T 2
∫T 1
Q = ΔU =      CV  dT
4.1. Sensible Heat Effects 135
The enthalpy may be treated similarly, with molar or specific enthalpy expressed most
conveniently as a function of temperature and pressure. Then H = H(T, P), and
( ∂ T ) ( ∂ P )
∂ H ∂ H
dH =   ___      dT +  ___
        dP
P T
With the definition of CP provided by Eq. (2.19),
( ∂ P )
∂ H
dH = CP  dT +  ___
        dP
T
Again, the final term is zero for two situations:
∙ For any constant-pressure process.

∙ When the enthalpy is independent of pressure, regardless of process. This is exactly true
for the ideal-gas state and approximately true for real gases at low pressure and high
temperature.
In either case, dH = CP  dT
ΔH =      CP  dT 

T 2
∫ T 1
and (4.2)
Moreover, Q = ΔH for mechanically reversible, constant-pressure, closed-system processes

[Eq. (2.22)] and for the transfer of heat in steady-flow processes where ΔEP and ΔEK are
negligible and Ws = 0 [Eq. (2.32)]. In either case,
T 2
∫T 1

Q = ΔH =       CP  dT (4.3)
This equation finds frequent application for flow processes designed for simple heating and
cooling of gases, liquids, and solids.
Temperature Dependence of the Heat Capacity

Evaluation of the integral in Eq. (4.3) requires knowledge of the temperature dependence of
the heat capacity. This is usually given by an empirical equation; the two simplest expressions
of practical value are:
CP  CP 
 ___   = α + βT + γT 2 and ___
     = a + bT + cT −2
R R
where α, β, and γ and a, b, and c are constants characteristic of the particular substance. With
the exception of the last term, these equations are of the same form. We therefore combine
them to provide a single expression:
CP 
___
     = A + BT + CT 2 + DT −2
(4.4)
R
where either C or D is usually zero, depending on the substance considered.1 Because the
ratio CP/R is dimensionless, the units of CP are governed by the choice of R. The parameters
are independent of temperature, but, at least in principle, depend on the value of the constant
pressure. However, for liquids and solids the effect of pressure is usually very small. Values
of the constants for selected solids and liquids are given in Tables C.2 and C.3 of App. C. The
heat capacities of solids and liquids are usually found by direct measurement. Correlations for
the heat capacities of many solids and liquids are given by Perry and Green and in the DIPPR
Project 801 collection.2
Heat Capacity in the Ideal-Gas State

We noted in Section 3.3 that as P → 0 a gas approaches the ideal-gas state, wherein molecular
volumes and intermolecular forces are negligible. If these conditions are imagined to persist
with increasing pressure, a hypothetical ideal-gas state continues to exist at finite pressures.
The gas still has properties reflective of its internal molecular configuration, just as does a
real gas, but without the influence of intermolecular interactions. Accordingly, ideal-gas-state
ig ig
heat capacities, designated by CP  and CV  , are functions of temperature, but independent of
pressure, providing for ease of correlation. Fig. 4.1 illustrates the temperature dependence of
ig
CP  for several representative substances.
Statistical mechanics provides a basic equation for the temperature dependence of the
ideal-gas-state internal energy:
3
U ig = __     RT + f (T)
2
Equation (3.10), for the ideal-gas state, H   = U ig + RT, becomes:
ig
5
H ig =  __  RT + f (T)
2
In view of Eq. (2.19),
( ∂ T ) 2 ( ∂ T )
∂ H ig 5 ∂ f (T)
CP   ≡  ____     = __
    R +  _____
ig
   
      
   
P P
The first term on the right represents translational kinetic energy of the molecule, whereas the
second combines all rotational and vibrational kinetic energies associated with the molecule.
Because the molecules of a monatomic gas have no energies of rotation or vibration, f (T) in the
ig
preceding equation is zero. Thus, in Fig. 4.1 the value of C P  / Rfor argon is constant at a value
of 5/2. For diatomic and polyatomic gases, f (T) contributes importantly at all temperatures of
practical importance. Diatomic molecules have a contribution equal to RT from their two
ig
rotational modes of motion. Thus, in Fig. 4.1, C
P  / Rfor N2 is about 7/2 R at moderate temper-
ature, and it increases at higher temperatures as intramolecular vibration begins to contribute.
Nonlinear polyatomic molecules have a contribution of 3/2 R from their three rotational modes
1The NIST Chemistry Webbook, http://webbook.nist.gov/ uses the Shomate equation for heat capacities, which
also includes a T3 term as well as all four terms of Eq. (4.4).

2R. H. Perry and D. Green, Perry’s Chemical Engineers’ Handbook, 8th ed., Sec. 2, McGraw-Hill, New York,
2008; Design Institute for Physical Properties, Project 801, http://www.aiche.org/dippr/projects/801.

of motion, and in addition usually have low-frequency vibrational modes that make an addi-
tional contribution at moderate temperature. The contribution becomes larger the more com-
plex the molecule and increases monotonically with temperature, as is evident from the curves
in Fig. 4.1 for H2O and CO2. The trend with molecular size and complexity is illustrated by the
ig
values of C
P  / Rat 298 K in Table C.1 of App. C.
7
CO 2
6
Figure 4.1: Ideal-gas-state heat
capacities of argon, nitrogen,
H 2O
water, and carbon dioxide.
Ideal-gas-state heat capacities 5
increase smoothly with increas- CPig
ing temperature toward an upper R
limit, which is reached when 4
N2
all translational, rotational, and
vibrational modes of molecular
motion are fully excited.
3
Ar
2
500 1000 1500 2000
T/K
ig ig
The temperature dependence of CP  or C
V  is determined by experiment, most often
from spectroscopic data and knowledge of molecular structure through calculations based on
statistical mechanics.3 Increasingly, quantum chemistry calculations, rather than spectroscopy
experiments, are used to provide the molecular structure, and they often permit the calculation
of heat capacities with precision comparable to experimental measurement. Where experi-
mental data are not available, and quantum chemistry calculations are not warranted, methods
of estimation are employed, as described by Prausnitz, Poling, and O’Connell.4
3D. A. McQuarrie, Statistical Mechanics, pp. 136–137, HarperCollins, New York, 1973.
4B. E. Poling, J. M. Prausnitz, and J. P. O’Connell, The Properties of Gases and Liquids, 5th ed., chap. 3, McGraw-
Hill, New York, 2001.

Temperature dependence is expressed analytically by equations such as Eq. (4.4), here written:
ig
CP 
 ___     = A + BT + CT 2 + DT −2 (4.5)
R
Values of the constants are given in Table C.1 of App. C for a number of common
organic and inorganic gases. More accurate but more complex equations are found in the liter-
ature.5 As a result of Eq. (3.12), the two ideal-gas-state heat capacities are related:
ig ig
CV  ___ C  
 ___     =   P    − 1 (4.6)
R R
ig ig
The temperature dependence of C V  / Rfollows from the temperature dependence of C P  / R.
Although ideal-gas-state heat capacities are exactly correct for real gases only at zero
pressure, the departure of real gases from the ideal-gas state is seldom significant at pressures
ig ig
below several bars, and here C P  and CV  are usually good approximations to their true heat
capacities. Reference to Fig. 3.14 indicates a vast range of conditions at Pr < 0.1 for which
assumption of the ideal-gas state is usually a suitable approximation. For most substances Pc
exceeds 30 bar, which means that ideal-gas state behavior is often closely approximated up to
a pressure of at least 3 bar.
Example 4.1
The parameters listed in Table C.1 of Appendix C require use of Kelvin temperatures
in Eq. (4.5). Equations of the same form may also be developed for use with tempera-
tures in °C, but the parameter values are different. The molar heat capacity of methane
in the ideal-gas state is given as a function of temperature in kelvins by:
ig
___C  
  P    = 1.702 + 9.081 × 10 −3 T − 2.164 × 10 −6 T 2
R
ig
where the parameter values are from Table C.1. Develop an equation for C
P  / Rfor use
with temperatures in °C.
Solution 4.1
The relation between the two temperature scales is: T
K = t° C + 273.15.
Therefore, as a function of t,
ig
___C  
  P    = 1.702 + 9.081 × 10 −3(t + 273.15) − 2.164 × 10 −6 (t + 273.15) 2
R
ig
CP 
or  ___     = 4.021 + 7.899 × 10 −3 t − 2.164 × 10 −6 t 2
R
5See F. A. Aly and L. L. Lee, Fluid Phase Equilibria, vol. 6, pp. 169–179, 1981, and its bibliography; see also
Design Institute for Physical Properties, Project 801, http://www.aiche.org/dippr/projects/801, and the Shomate equa-
tion employed by the NIST Chemistry Webbook, http://webbook.nist.gov.
Gas mixtures of constant composition behave exactly as do pure gases. In the ideal-gas
state, molecules in mixtures have no influence on one another, and each gas exists independent
of the others. The ideal-gas-state heat capacity of a mixture is therefore the mole-fraction-
weighted sum of the heat capacities of the individual gases. Thus, for gases A, B, and C, the
molar heat capacity of a mixture in the ideal-gas state is:
ig ig ig ig
CP m 
ixture  
= y ACP A    + y BCP B    + y CCP C    (4.7)
ig ig ig
where CP A ,  CP B ,  and CP C   are the molar heat capacities of pure A, B, and C in the ideal-gas state,
and yA, yB, and yC are mole fractions. Because the heat-capacity polynomial, Eq. (4.5), is lin-
ear in the coefficients, the coefficients A, B, C, and D for a gas mixture are similarly given by
mole-fraction weighted sums of the coefficients for the pure species.
Evaluation of the Sensible-Heat Integral

Evaluation of the integral ∫ CPdT is accomplished by substitution for CP as a function of T
by Eq. (4.4), followed by formal integration. For temperature limits of T0 and T the result is:
( T T 0 )
T C  T − T 0
∫T 0 R
B C
     ___
     dT = A(T − T 0) + __
     (T 2 − T02  ) + __
     (T 3 − T03  )  + D _
P
       (4.8)
2 3
Given T0 and T, the calculation of Q or ΔH is straightforward. Less direct is the calcula-
tion of T, given T0 and Q or ΔH. Here, an iteration scheme may be useful. Factoring (T − T0)
from each term on the right side of Eq. (4.8) gives:
[ T T 0]
T C 
∫T 0 R
B C D
     ___
     dT =  A + _
       (T + T 0) + _
      (T 2 + T02   + T T 0) + _
P
      (T − T 0)
2 3
We identify the quantity in square brackets as 〈CP  〉 H / R, where 〈CP  〉 His defined as a mean heat
capacity for the temperature range from T0 to T:
〈CP  〉 H
________ B C D

        = A + __
     (T + T 0) + __
     (T 2 + T02   + T T 0) + ____
        (4.9)
R 2 3 T T 0
Equation (4.2) may therefore be written:
ΔH = 〈CP  〉 H(T − T 0)
(4.10)
The angular brackets enclosing CP identify it as a mean value; subscript H denotes a mean
value specific to enthalpy calculations and distinguishes this mean heat capacity from a simi-
lar quantity introduced in the next chapter.
Solution of Eq. (4.10) for T gives:
ΔH
T = ________
      
+ T  (4.11)
〈CP  〉 H 0
With a starting value for T, one can first evaluate ⟨CP  ⟩ Hby Eq. (4.9). Substitution into
Eq. (4.11) provides a new value of T from which to reevaluate ⟨CP  ⟩ H. Iteration continues to
convergence on a final value of T. Of course, such iteration is readily automated with built-in
functions in a spreadsheet or a numerical analysis software package.
Example 4.2
Calculate the heat required to raise the temperature of 1 mol of methane from 260 to
600°C in a steady-flow process at a pressure sufficiently low that the ideal-gas state is
a suitable approximation for methane.
Solution 4.2
Equations (4.3) and Eq. (4.8) together provide the required result. Parameters
ig
for C
P  / Rare from Table C.1; T0 = 533.15 K and T = 873.15 K.
Then 873.15 C   ig
∫533.15 R
Q = ΔH = R ___P
dT
          
[
9.081 × 10  −3 2
Q = (8.314) 1.702(T − T 0) +  ___________ (T   − T0  )
      2
2
]
2.164 × 10  −6 3
−  ___________
    (  T   − T03  ) = 19,778 J
3

Use of Defined Functions

The integral ∫ (CP/R)dT appears often in thermodynamic calculations. As a matter of con-
venience, we therefore define the right side of Eq. (4.8) as the function, ICPH(T0, T; A, B,
C, D), and presume the availability of a computer routine for its evaluation.6 Equation (4.8)
then becomes:
T C 
∫T 0 R
     ___
P
     dT ≡ ICPH(T 0, T; A, B, C, D)
The function name is ICPH (I indicates an integral), and the quantities in parentheses are the
variables T0 and T, followed by parameters A, B, C, and D. When these quantities are assigned
numerical values, the notation represents a value for the integral. Thus, for the evaluation of
Q in Ex. 4.2:
Q = 8.314 × ICPH(533.15, 873.15; 1.702, 9.081 × 10 −3, −2.164 × 10 −6, 0.0) = 19,778 J
Also useful is a defined function for the dimensionless mean value ⟨ CP  ⟩  H / Rgiven by
Eq. (4.9). The function name is MCPH (M indicates a mean). The right side defines the func-
tion, MCPH(T0, T; A, B, C, D). With this definition, Eq. (4.9) becomes:
〈CP  〉 H
________
        = MCPH(T 0, T; A, B, C, D)
R
6Examples of these defined functions implemented in Microsoft Excel, Matlab, Maple, Mathematica, and Mathcad
are provided in the online learning center at http://highered.mheducation.com:80/sites/1259696529.

4.2. Latent Heats of Pure Substances 141
A specific numerical value of this function is:

MCPH(533.15, 873.15; 1.702, 9.081×10 −3, −2.164 × 10 −6, 0.0) = 6.9965
representing ⟨ CP  ⟩ H / Rfor methane in the calculation of Ex. 4.2. By Eq. (4.10),
ΔH = (8.314)(6.9965)(873.15 − 533.15) = 19,778 J

Example 4.3
What is the final temperature when heat in the amount of 400 × 106 J is added to 11 × 103
mol of ammonia initially at 530 K in a steady-flow process at 1 bar?
Solution 4.3
If ΔH is the enthalpy change for 1 mol, Q = n ΔH, and
Q 400 × 10 6
ΔH = __
     = _________
     = 36,360 J·mol −1
  
n 11,000
Then for any value of T, with parameters from Table C.1 and R = 8.314 J·mol−1·K−1:
_ ⟨ CP  ⟩  H
        = MCPH(530, T; 3.578, 3.020 × 10 −3, 0.0, −0.186 × 10 5)
R
This equation and Eq. (4.11) together may be solved for T, yielding T = 1234 K.
A trial procedure is an alternative approach to solution of this problem. One
sets up an equation for Q by combining Eqs. (4.3) and (4.8), with T as an unknown
on the right. With Q known, one merely substitutes a rational succession of values
for T until the value of Q is reproduced. Microsoft Excel’s Goal Seek function is
an example of an automated version of this procedure.
4.2 LATENT HEATS OF PURE SUBSTANCES
When a pure substance is liquefied from the solid state or vaporized from the liquid or solid at
constant pressure, no change in temperature occurs; however, these processes require the transfer
of finite amounts of heat to the substance. These heat effects are called latent heats: of fusion, of
vaporization, and of sublimation. Similarly, there are heats of transition accompanying the change
of a substance from one allotropic solid state to another; for example, the heat absorbed when
rhombic crystalline sulfur changes to the monoclinic structure at 95°C and 1 bar is 11.3 J⋅g−1.
The characteristic feature of all these processes is the coexistence of two phases. Accord-
ing to the phase rule, the intensive state of a two-phase system consisting of a single species
is fixed by specification of just one intensive property. Thus the latent heat accompanying a
phase change is a function of temperature only, and is related to other system properties by an
exact thermodynamic equation:
dP sat
ΔH = TΔV _
       (4.12)
dT
where for a pure species at temperature T,

ΔH = latent heat = enthalpy change accompanying the phase change
ΔV = volume change accompanying the phase change
Psat = saturation pressure, i.e., the pressure at which the phase change occurs, which is
a function only of T
The derivation of this equation, known as the Clapeyron equation, is given in Section 6.5.
When Eq. (4.12) is applied to the vaporization of a pure liquid, dPsat/dT is the slope
of the vapor pressure-versus-temperature curve at the temperature of interest, ΔV is the dif-
ference between molar volumes of saturated vapor and saturated liquid, and ΔH is the latent
heat of vaporization. Thus, ΔH may be calculated from vapor-pressure and volumetric data,
yielding an energy value with units of pressure × volume.
Latent heats are also measured calorimetrically. Experimental values are reported at
selected temperatures for many substances.7 Empirical correlations for the latent heats of
many compounds as a function of temperature are given by Perry and Green and in the DIPPR
Project 801 collection.8 When required data are not available, approximate methods can pro-
vide estimates of the heat effect accompanying a phase change. Because heats of vaporization
are by far the most important in practice, they have received the most attention. Predictions are
most often made by group-contribution methods.9 Alternative empirical methods serve one of
two purposes:
∙ 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.
∙ Estimation of the heat of vaporization at any temperature from the known value at a
single temperature.
Rough estimates of latent heats of vaporization for pure liquids at their normal boiling
points (indicated by subscript n) are given by Trouton’s rule:
ΔHn 
____
    ~ 10
RTn 
where Tn is the absolute temperature of the normal boiling point. The units of ΔHn, R, and Tn
are chosen so that ΔHn/RTn is dimensionless. Dating from 1884, this empirical rule provides
a simple check on whether values calculated by other methods are reasonable. Representative
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. The high value for water reflects the existence of intermolecular hydro-
gen bonds that rupture during vaporization.
7V. Majer and V. Svoboda, IUPAC Chemical Data Series No. 32, Blackwell, Oxford, 1985; R. H. Perry and D.
Green, Perry’s Chemical Engineers’ Handbook, 8th ed., Sec. 2, McGraw-Hill, New York, 2008.
8R. H. Perry and D. Green, Perry’s Chemical Engineers’ Handbook, 8th ed., Sec. 2, McGraw-Hill, New York,
2008; Design Institute for Physical Properties, Project 801, http://www.aiche.org/dippr/projects/801.

9See, for example, M. Klüppel, S. Schulz, and P. Ulbig, Fluid Phase Equilibria, vol. 102, pp. 1–15, 1994.
4.2. Latent Heats of Pure Substances 143
Also for the normal boiling point, but not quite so simple, is the equation proposed by
Riedel:10
ΔHn  ________________
1.092(ln Pc   − 1.013)
 ____    =   
       (4.13)
RTn  0.930 − Tr  n
where Pc is the critical pressure in bars and T  r n is the reduced temperature at Tn. Equation

(4.13) is surprisingly accurate for an empirical expression; errors rarely exceed 5 percent.
Applied to water it gives:
ΔHn  ____________________
1.092(ln 220.55 − 1.013)
 ____   =           = 13.56
R Tn  0.930 − 0.577
from which ΔHn   = (13.56)(8.314)(373.15) = 42,065 J⋅mol −1
This corresponds to 2334 J⋅g−1; the steam-table value of 2257 J⋅g−1 is lower by 3.4 percent.
Estimates of the latent heat of vaporization of a pure liquid at any temperature from the
known value at a single temperature are given by the method of Watson.11 The basis may be a
known experimental value or a value estimated by Eq. (4.13):
0.38
ΔH 1 ( 1 − Tr  1)
ΔH 2
____
1 − Tr  2

   =  ______
       
  (4.14)
This empirical equation is simple and fairly accurate; its use is illustrated in the following
example.
Example 4.4
Given that the latent heat of vaporization of water at 100°C is 2257 J⋅g−1, estimate the
latent heat at 300°C.
Solution 4.4
Let ΔH 1 = latent heat at 100° C = 2257 J⋅g −1
ΔH 2 = latent heat at 300° C
  
    
         
Tr  1 = 373.15 / 647.1 = 0.577
Tr  2 = 573.15 / 647.1 = 0.886
Then by Eq. (4.14),
0.38
( 1 − 0.577 )
1 − 0.886
ΔH 2 = (2257) ________
    = (2257)( 0.270) 0.38 = 1371 J⋅g −1
  
The value given in the steam tables is 1406 J⋅g−1.
10L. Riedel, Chem. Ing. Tech., vol. 26, pp. 679–683, 1954.
11K. M. Watson, Ind. Eng. Chem., vol. 35, pp. 398–406, 1943.
4.3 STANDARD HEAT OF REACTION
Heat effects of chemical processes are fully as important as those for physical processes. Chemical
reactions are accompanied by the transfer of heat, by temperature changes during reaction,
or by both. The ultimate cause lies in the difference between the molecular configurations of
products and reactants. For an adiabatic combustion reaction, reactants and products possess
the same energy, requiring an elevated temperature for the products. For the corresponding
isothermal reaction, heat is necessarily transferred to the surroundings. Between these two
extremes an infinite combination of effects is possible. Each reaction carried out in a particu-
lar way is accompanied by particular heat effects. Their complete tabulation is impossible. Our
object is therefore to devise methods of calculation of the heat effects for reactions carried out
in diverse ways from data for reactions carried out in an arbitrarily defined standard way, thus
leading to standard heats of reaction. This reduces the required data to a minimum.
Heats of reaction are based on experimental measurements. Most easily measured are
heats of combustion, because of the nature of such reactions. A simple procedure is provided
by a flow calorimeter. Fuel is mixed with air at a temperature T, and the mixture flows into a
combustion chamber where reaction occurs. The combustion products enter a water-jacketed
section in which they are cooled to temperature T. Because no shaft work is produced and the
calorimeter is designed to eliminate potential- and kinetic-energy changes, the overall energy
balance, Eq. (2.32), reduces to
ΔH = Q
Thus the enthalpy change caused by the combustion reaction is equal in magnitude to the heat
flowing from the reaction products to the water, and may be calculated from the temperature
rise and flow rate of the water. The enthalpy change of reaction ΔH is called the heat of
reaction. If the reactants and products are in their standard states, then the heat effect is the
standard heat of reaction.
The definition of a standard state is straightforward. For a given temperature,
A standard state is defined as the state of a substance at specified pres-
sure, composition, and physical condition as, e.g., gas, liquid, or solid.
The standard states in use throughout the world have been established by general agree-
ment. They are based on a standard-state pressure of 1 bar (105 Pa). With respect to composi-
tion, the standard states used in this chapter are states of pure species. For liquids and solids it
is the actual state of the pure species at the standard-state pressure. Nothing could be simpler.
However, for gases there is a small complication, as the chosen physical state is the ideal-gas
state, for which we have already established heat capacities. In summary, the standard states
used in this chapter are:
∙
Gases: The pure substance in the ideal-gas state at 1 bar.
∙
Liquids and solids: The real pure liquid or solid at 1 bar.
One must understand that standard states apply at any temperature.
There is no specification of temperature for any standard state. Refer-
ence temperatures, also in use with heats of reaction, are entirely inde-
pendent of standard states.
4.3. Standard Heat of Reaction 145
With respect to the chemical reaction, aA + bB → lL + mM, the standard heat of reac-
tion at temperature T is defined as the enthalpy change when a moles 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 temperature T. The mechanism of this change is immaterial to the
calculation of the enthalpy change. One may view the process shown in Fig. 4.2 as occurring
in a “box of tricks.” If the properties of reactants and products in their standard states are not
significantly different from the properties of actual reactants and products, the standard heat
of reaction is a reasonable approximation to the actual heat of reaction. If this is not the case,
then additional steps must be incorporated into the calculation scheme to account for any
differences. The most common difference is caused by pressures higher than appropriate to
the ideal-gas state (as for the ammonia-synthesis reaction). In this case, enthalpy changes for
transformation from real-gas states to ideal-gas states and the reverse are required. These are
readily made, as shown in Chapter 6.
nA = a mol·s-1 nL = l mol·s -1
“Box of Tricks”
nB = b mol·s-1 nM = m mol·s-1
In standard states, at T In standard states, at T
Q J·s-1 = ΔHT° J
Figure 4.2: Schematic representation of the standard heat of reaction at temperature T.
Property values in the standard state are denoted by the degree symbol. For exam-
C P° is the standard-state heat capacity. Because the standard state for gases is the
ple,
ig
ideal-gas state, C P°  is identical with CP  , and the data of Table C.1 apply to the standard state
for gases.
All conditions for a standard state are fixed except temperature, which
is always the temperature of the system. Standard-state properties are
therefore functions of temperature only.
The standard state chosen for gases is hypothetical or fictitious because at 1 bar actual
gases deviate from the ideal-gas state. However, they seldom deviate much, and for most pur-
poses enthalpies for the real-gas state at 1 bar and the ideal-gas state are negligibly different.
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. For example, two versions of the ammonia synthesis reaction are written:
_
2 2
°   = − 46,110 J
  1   N   +  _3   H   → NH   
ΔH 298 3
2 2   

°   = − 92,220 J
N 2 + 3 H 2 → 2 NH 3 ΔH 298
  

°   indicates that the heat of reaction is the standard value for a temperature of
The symbol ΔH 298
298.15 K (25°C) and for the reaction as written.
4.4 STANDARD HEAT OF FORMATION
Tabulation of data for just one temperature and for just the standard heats of reaction for all
of the vast number of possible reactions is impractical. Fortunately, the standard heat of any
reaction at temperature T can be calculated if the standard heats of formation at the same
temperature are known for the compounds taking part in the reaction. A formation reaction is
defined as a reaction that forms a single compound from its constituent elements. For example,
the reaction C + _ 12 O2 + 2 H 2 → CH 3OHis a formation reaction for methanol. The reaction
H 2O + SO 3 → H 2 SO 4 is not a formation reaction, because it forms sulfuric acid not from the
elements but from other compounds. 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 temperature can be calculated from heat-capacity data if the
value for one temperature is known; the tabulation of data can therefore be reduced to the
compilation of standard heats of formation at a single temperature. The usual choice for this
reference temperature is 298.15 K or 25°C. The standard heat of formation of a compound
at this temperature is represented by the symbol ΔH °f 2 98
.  The degree symbol denotes
the standard-state value, subscript f identifies a heat of formation, and the 298 is the
rounded absolute temperature in kelvins. Tables of these values for common substances
may be found in standard handbooks, but the most extensive compilations available are in
specialized reference works.12 An abridged list of values is given in Table C.4 of App. C, and
values for many additional compounds are given in publicly available online databases.13
When chemical reactions 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, and its changes for given initial and final states are independent of
path. In particular, formation reactions and standard heats of formation may be combined to
produce any desired reaction (not itself a formation reaction) and its accompanying standard
heat of reaction. Reactions written for this purpose often include an indication of the physical
state of each reactant and product—that is, the letter g, l, or s is placed in parentheses after the
chemical formula to show whether it is a gas, a liquid, or a solid. This might seem unnecessary
because a pure chemical species at a particular temperature and 1 bar can usually exist only in
one physical state. However, fictitious states (e.g., the ideal-gas state) are often employed for
convenience in such calculations.
12For example, see TRC Thermodynamic Tables—Hydrocarbons and TRC Thermodynamic Tables—Non-Hydrocarbons,
serial publications of the Thermodynamics Research Center, Texas A & M Univ. System, College Station, Texas;
“The NBS Tables of Chemical Thermodynamic Properties,” J. Physical and Chemical Reference Data, vol. 11,
supp. 2, 1982; and the DIPPR Project 801 Database, http://www.aiche.org/dippr/projects/801. Where data
are unavailable, estimates based only on molecular structure may be found by the methods of S. W. Benson,
Thermochemical Kinetics, 2nd ed., John Wiley & Sons, New York, 1976. An improved version of this method is
implemented online at http://webbook.nist.gov/chemistry/grp-add/.
13Values for more than 7000 compounds are available at http://webbook.nist.gov/.
4.4. Standard Heat of Formation 147
The water-gas-shift reaction, CO 2(g) + H 2(g)→ CO(g) + H 2O(g)at 25°C, is commonly

encountered in the chemical industry. Although it takes place only at temperatures well above
25°C, the data are for 25°C, and the initial step in any calculation of heat effects for this reac-
tion is evaluation of the standard heat of reaction at 25°C. The pertinent formation reactions
and the corresponding heats of formation from Table C.4 are:
CO 2(g) : C(s) + O 2(g) → CO 2(g) ΔH °f 2 98  = − 393,509 J
H 2( g)  : Because hydrogen is an element ΔH  f° 2    = 0
98
       
     
                
CO(g)  : C(s) +  _2   O 2 (g) → CO(g)
1
ΔH °f 2 98   = − 110,525 J
H 2 O(g) : H 2 (g) +  _12   O 2 (g) → H 2 O(g) ΔH °f 2 98  = − 241,818 J
Because the reaction is actually carried out entirely in the gas phase at high temperature, con-
venience dictates that the standard states of all products and reactants at 25°C be taken as the
ideal-gas state at 1 bar, even though water does not actually exist as a gas at these conditions.14
Writing the formation reactions so that their sum yields the desired reaction requires that
the formation reaction for CO2 be written in reverse; the heat of reaction is then of opposite
sign to its standard heat of formation:
CO 2(g) → C(s) + O 2(g)        ΔH °298
    = 393,509 J
C(s) +  _1   O  (g)   → CO(g)   
     
        2 2          ΔH °    = − 110,525 J
298
 2 (g) +  _12   O 2 (g) →
H  H 2 O(g)      ΔH  °298    = − 241,818 J
_____
CO 2( g)  + H 2( g)   → CO(g)  + H 2 O(g)     ΔH °298
    = 41,166 J
     
 
The meaning of this result is that the enthalpy of 1 mol of CO plus 1 mol of H2O is greater
than the enthalpy of 1 mol of CO2 plus 1 mol of H2 by 41,166 J when each product and reac-
tant is taken as the pure gas at 25°C in its ideal-gas state at 1 bar.
In this example the standard heat of formation of H2O is available for its hypothetical
ideal-gas state at 25°C. One might expect the value of the heat of formation of water to be
listed for its actual state as a liquid at 1 bar and 25°C. As a matter of fact, values for both states
are given in Table C.4 because they are both often used. This is true for many compounds that
normally exist as liquids at 25°C and 1 bar. Cases do arise, however, in which a value is given
only for the standard state as a liquid or for the ideal-gas state when what is needed is the other
value. Suppose this were the case for the preceding example, with only the standard heat of
formation of liquid H2O available. We would then include an equation for the physical change
that transforms water from its standard state as a liquid into its ideal-gas state. The enthalpy
change for this physical process is the difference between the heats of formation of water in its
two standard states:
− 241,818 − (−285,830) = 44,012 J
14One might wonder about the origin of data for such hypothetical states, as it would appear difficult to make
measurements for states that cannot exist. For the case of water vapor in the ideal gas state at 25˚C and 1 bar, obtaining
the enthalpy is straightforward. While water cannot exist as a gas at these conditions, it is a gas at 25˚C at sufficiently
low pressure. In the ideal gas state, enthalpy is independent of pressure, so the enthalpy measured in the limit of low
pressure is exactly the enthalpy in the desired hypothetical state.
This is approximately the latent heat of vaporization of water at 25°C. The sequence of steps
is now:
°    = 393,509 J
C O 2( g) → C(s)  + O 2( g)       ΔH 298
C(s) +  _12   O 2 (g) → CO(g) °    = − 110,525 J
      ΔH 298
     
                        

H 2 (g) +  _21   O 2 (g) → H 2 O(l) °    = − 285,830 J
      ΔH 298
H 2 O(l) → H 2 O(g)       ΔH 298 °    = 44,012 J
_____
°    = 41,166 J
C O 2( g)  + H 2( g)   → CO(g)  + H 2 O(g)   ΔH 298
     
 
This result is of course in agreement with the previous answer.
Example 4.5
Calculate the standard heat of reaction at 25°C for the following reaction:
4HCl(g) + O 2(g) → 2H 2O(g) + 2Cl 2(g)
Solution 4.5
Standard heats of formation at 298.15 K from Table C.4 are:
HCl(g) : − 92,307 J H 2O(g) : −241,818 J
The following combination gives the desired result:

°    = (4) (92,307)
4HCl(g)   → 2H 2( g)  + 2Cl 2( g)     ΔH 298
        
           
2H 2(g) + O 2(g)   → 2H 2O(g) °    = (2)(−241,818)
    ΔH 298
___________
4HCl(g)  + O 2( g)   → 2 H 2O( g)  + 2Cl 2( g)   ΔH 298°    = −114,408 J
      
 
4.5 STANDARD HEAT OF COMBUSTION
Only a few formation reactions can actually be carried out at the conditions of interest, and there-
fore data for these reactions are determined indirectly. One kind of reaction that readily lends
itself to experiment is the combustion reaction, and many standard heats of formation come from
standard heats of combustion, measured calorimetrically. A combustion reaction is defined as
a reaction of an element or compound with oxygen to form specified combustion products. For
organic compounds consisting only of carbon, hydrogen, and oxygen, the products are carbon
dioxide and water, but the state of the water may be either vapor or liquid. The value for liquid
water product is called the higher heat of combustion, while that with water vapor as product is
the lower heat of combustion. Data are always based on 1 mol of the substance burned.
A reaction such as the formation of n-butane:
4C(s) +5H 2(g) → C 4H 10(g)
4.6. Temperature Dependence of ΔH° 149
is not feasible in practice. However, this equation results from combination of the following
combustion reactions:
4C(s) + 4 O 2(g) → 4 CO 2(g) °    =  4 −393,509
ΔH 298 ( )( )
5 H 2 (g) + 2  _2   O 2 (g)   → 5 H 2 O(l) 
      
         1 °    =  5 −285,830
  ΔH 298   ( )( )
4CO 2(g) + 5 H 2 O(l) → C 4 H 10 (g) + 6  _2   O 2 (g) ΔH 298
1 °    = 2,877,396
_______
   4C(s)  + 5 H 2( g)   → C 4 H 10( g)     °    = − 125,790 J
ΔH 298
      
 
This result is the standard heat of formation of n-butane listed in Table C.4 of App. C.
4.6 TEMPERATURE DEPENDENCE OF ΔH°
In the foregoing sections, standard heats of reaction were discussed for an arbitrary reference
temperature of 298.15 K. In this section we treat the calculation of standard heats of reaction
at other temperatures from knowledge of the value at the reference temperature.
A general chemical reaction may be written:
| ν 1| A 1 + | ν 2| A 2 + . . . → | ν 3| A 3 + | ν 4| A 4 + . . .
where νi is a stoichiometric coefficient and Ai stands for a chemical formula. The species on
the left are reactants; those on the right, products. The sign convention for νi is as follows:
positive (+) for products  and   negative (− ) for reactants
For example, when the ammonia synthesis reaction is written:
N 2 + 3 H 2 → 2NH 3
ν N 2  = − 1  ν H 2  = − 3  ν NH 3  = 2

then
This sign convention allows the definition of a standard heat of reaction to be expressed
mathematically by the simple equation:
ΔH° ≡ ∑   ν iH i°  (4.15)
i
where H i° is the enthalpy of species i in its standard state and the summation is over all prod-
ucts and reactants. The standard-state enthalpy of a chemical compound is equal to its heat of
formation plus the standard-state enthalpies of its constituent elements. If the standard-state
enthalpies of all elements are arbitrarily set equal to zero as the basis of calculation, then
the standard-state enthalpy of each compound is simply its heat of formation. In this event,
H i°  = ΔH f°i  and Eq. (4.15) becomes:
ΔH° = ∑   ν iΔH fi°  (4.16)

i
where the summation is over all products and reactants. This formalizes the procedure
described in the preceding section for calculation of standard heats of other reactions from
standard heats of formation. Applied to the reaction,
4HCl(g) + O 2(g) → 2H 2O(g) + 2Cl 2(g)

Eq. (4.16) is written:

ΔH° = 2ΔH f° H  2O  − 4ΔH f° H Cl 
With data from Table C.4 of App. C. for 298.15 K, this becomes:
°    = (2)(−241,818) − (4)(−92,307) = −114,408 J
ΔH 298
in agreement with the result of Ex. 4.5. Note that for pure elemental gases that normally exist
as dimers (e.g., O2, N2, H2), it is the dimer form that is arbitrarily assigned a standard-state
enthalpy of zero.
For standard reactions, products and reactants are always at the standard-state pressure
of 1 bar. Standard-state enthalpies are therefore functions of temperature only, and by Eq. (2.20),
dH i°  = C P° i    dT
where subscript i identifies a particular product or reactant. Multiplying by νi and summing
over all products and reactants gives:
∑   ν i dH i°  = ∑   ν i C P° i    dT
i i
Because νi is a constant, it may be placed inside the differential:
∑   d(ν i H i° ) = ∑   ν i C P° i    dT  or   d∑   ν i H i°  = ∑   ν i C P° i    dT

i i i i
The term ∑ i ν i H i° is the standard heat of reaction, defined by Eq. (4.15) as ΔH°. The standard
heat-capacity change of reaction is defined similarly:
ΔC P°  ≡ ∑   ν i C P° i    (4.17)
i
From these definitions,
dΔH° = ΔC P°  dT (4.18)
This is the fundamental equation relating heats of reaction to temperature.
Integration of Eq. (4.18) yields:
T
∫T 0
ΔH° − ΔH 0°  =       ΔC P°  dT
where ΔH°and ΔH 0° are the standard heats of reaction at temperature T and at reference tem-
perature T0 respectively. This equation is more conveniently expressed as:
T ΔC ° 
∫T 0 R
P
ΔH° = ΔH 0°  + R       _____     dT (4.19)
The reference temperature T0 must be a temperature for which the heat of reaction is
known or can be calculated as described in the two preceding sections, most often 298.15 K.
What Eq. (4.19) provides is the means for calculation of a heat of reaction at temperature T
from a known value at temperature T0.
If the temperature dependence of the heat capacity of each product and reactant is given
by Eq. (4.5), then the integral is given by the analog of Eq. (4.8):
T ΔC ° 
( T T 0 )
ΔB ΔC T − T 0
∫T 0 R
P
     _____
       dT = ΔA(T − T 0) + ___
      (T 2 − T02  )  + ___
       (T 3 − T03  )  +ΔD _
      (4.20)
2 3
4.6. Temperature Dependence of ΔH° 151
where by definition, ΔA ≡ ∑   ν i Ai 

i
with analogous definitions for ΔB, ΔC, and ΔD.

An alternative formulation results when a mean heat capacity change of reaction is
defined in analogy to Eq. (4.9):
〈ΔC P° 〉  H ΔB ΔC ΔD
 _______      = ΔA + ___
      (T + T 0) + ___
       (T 2 + T02   + T T 0) +____
       (4.21)
R 2 3 T T 0
Equation (4.19) then becomes:

ΔH° = ΔH 0°  + 〈ΔC P° 〉  H(T − T 0) (4.22)
The integral of Eq. (4.20) is of the same form as that of Eq. (4.8), and in analogous fash-
ion may be set equal to a defined function:15
T ΔC  ° 
∫T 0 R
     ____
P
     
 dT = IDCPH (T0, T; DA, DB, DC, DD)
where “D” denotes “Δ.” The analogy requires simple replacement of CP by ΔC P°  and of A, B,
etc. by ΔA, ΔB, etc. The same computer routine serves for evaluation of either integral. The
only difference is in the function name.
Just as function MCPH is defined to represent ⟨CP⟩H/R, so function MDCPH by analogy
is defined to represent ⟨ΔC P° ⟩H/R; thus,
° 〈ΔC P 〉  H
_______
       = MDCPH (T0, T; DA, DB, DC, DD)
R
The calculation represented by both Eqs. (4.19) and (4.22) is represented schematically
in Fig. 4.3.
∆ H o = ∆ H0o +∫ ∆Cpo dT
T0
Reactants at T Products at T
Figure 4.3: Path
representing the pro-
cedure for calculating
T
a standard heat of
reaction at tempera-
∫ ∆ C dT
o
p
ture T from the value
T0 at reference tempera-
ture T0.
Reactants at T0 Products at T0
∆ H 0o
15Again, templates for these defined functions are available in the online learning center at http://highered.mheducation
.com:80/sites/1259696529.
Example 4.6
Calculate the standard heat of the following methanol-synthesis reaction at 800°C:
CO(g) + 2H 2(g) → CH 3OH(g)
Solution 4.6
Apply Eq. (4.16) to this reaction for reference temperature T0= 298.15 K and with
heat-of-formation data from Table C.4:
ΔH 0°  =  ΔH 298
°    = − 200,660 − (−110,525) = − 90,135 J
Evaluation of the parameters in Eq. (4.20) is based on data taken from Table C.1:
   
i 
_______ ν i    A  10 3 B  
  10 6 C  10 −5 D
CH 3OH 1 2.211 12.216 − 3.450 0.000
     
CO     − 1  
3.376  
0.557  
0.000  
− 0.031
H  
−
____________
2 2 3.249 0.422 0.000 0.083
     
 
From its definition,
ΔA = (1)(2.211) + (−1)(3.376) + (− 2)(3.249) = − 7.663
Similarly,
ΔB = 10.815 × 10 −3  ΔC = − 3.450 × 10 −6  ΔD = − 0.135 × 10 5
The value of the integral of Eq. (4.20) for T = 1,073.15 K is represented by:
IDCPH(298.15, 1073.15; − 7.663, 10.815 × 10 −3, − 3.450 × 10 −6, − 0.135 × 10 5)
The value of this integral is −1615.5 K, and by Eq. (4.19),
ΔH° = − 90,135 + 8.314(−1615.5) = −103,566 J
4.7 HEAT EFFECTS OF INDUSTRIAL REACTIONS
The preceding sections have dealt with the standard heat of reaction. Industrial reactions are
rarely carried out under standard-state conditions. Furthermore, in actual reactions the reac-
tants may not be present in stoichiometric proportions, the reaction may not go to completion,
and the final temperature may differ from the initial temperature. Moreover, inert species may
be present, and several reactions may occur simultaneously. Nevertheless, calculations of the
heat effects of actual reactions are based on the principles already considered and are illus-
trated by the following examples, wherein the ideal-gas state is assumed for all gases.
Example 4.7
What is the maximum temperature that can be reached by the combustion of methane
with 20% excess air? Both the methane and the air enter the burner at 25°C.
4.7. Heat Effects of Industrial Reactions 153
Solution 4.7
The reaction is CH4 + 2O2 → CO2 + 2H2O(g) for which,
°    = −393,509 + (2) (−241,818) − (−74,520) = −802,625 J
H 298
Δ
Because the maximum attainable temperature (called the theoretical flame
temperature) is sought, assume that the combustion reaction goes to completion
adiabatically (Q = 0). If the kinetic- and potential-energy changes are negligible
and if Ws = 0, the overall energy balance for the process reduces to ΔH = 0.
For purposes of calculation of the final temperature, any convenient path
between the initial and final states may be used. The path chosen is indicated in
the diagram.
Products at 1 bar
and T K
1 mol CO2
2 mol H2O
0.4 mol O2
0
H HP 9.03 mol N2
Reactants at 1 bar
and 25 C H 298
1 mol CH4
2.4 mol O2
9.03 mol N2
When one mole of methane burned is the basis for all calculations, the follow-
ing quantities of oxygen and nitrogen are supplied by the entering air:
Moles O 2 required = 2.0
Moles excess O 2 = (0.2)(2.0) = 0.4
   
  
Moles N 2 entering = (2.4)(79/21) = 9.03
The mole numbers ni of the gases in the product stream leaving the burner are
1 mol CO2, 2 mol H2O(g), 0.4 mol O2, and 9.03 mol N2. Because the enthalpy
change must be independent of path,
°    + ΔH P°  = ΔH = 0
ΔH 298 (A)
where all enthalpies are on the basis of 1 mol CH4 burned. The enthalpy change of
the products as they are heated from 298.15 K to T is:
ΔH P°  = ⟨C P° ⟩H
(T − 298.15) (B)
where we define ⟨C P° ⟩Has the mean heat capacity for the total product stream:
⟨C P° ⟩H  ≡ ∑   n i ⟨C P°i ⟩  H

i
The simplest procedure here is to sum the mean-heat-capacity equations for the
products, each multiplied by its appropriate mole number. Because C = 0 for each
product gas (Table C.1), Eq. (4.9) yields:
[i T T 0 ]
∑ i n i B i ∑ i n i D i
  = ∑   n i ⟨C P°i ⟩  H  = R ∑   n i Ai  + _
⟨C P° ⟩H         (T − T 0) + _
       
i 2
Data from Table C.1 are combined as follows:
A = ∑   n i Ai  = (1)(5.457) + (2)(3.470) + (0.4)(3.639) + (9.03)(3.280) = 43.471
i
Similarly, B = ∑   n i B i = 9.502 × 10 −3and D

 = ∑   n i D i = − 0.645 × 10 5.
i i
For the product stream ⟨C P° ⟩H

/ Ris therefore represented by:
MCPH(298.15, T; 43.471, 9.502 × 10 −3, 0.0, − 0.645 × 10 5)
Equations (A) and (B) are combined and solved for T:

ΔH 298°   
T = 298.15 −  ___________  
⟨C P° ⟩H
Because the mean heat capacities depend on T, one first evaluates ⟨ C P° ⟩H
for an
assumed value of T > 298.15, then substitutes the result in the preceding equation.
This yields a new value of T for which ⟨C P° ⟩H
is reevaluated. The procedure con-
tinues to convergence on the final value,
T = 2066 K or 1793° C
Again, solution can be easily automated with the Goal Seek or Solver function
in a spreadsheet or similar solve routines in other software packages.
Example 4.8
One method for the manufacture of “synthesis gas” (a mixture of CO and H2) is the
catalytic reforming of CH4 with steam at high temperature and atmospheric pressure:
CH 4(g) + H 2O(g) → CO(g) + 3H 2(g)
The only other reaction considered here is the water-gas-shift reaction:
CO(g) + H 2O(g) → CO 2(g) + H 2(g)
Reactants are supplied in the ratio 2 mol steam to 1 mol CH4, and heat is added to the
reactor to bring the products to a temperature of 1300 K. The CH4 is completely con-
verted, and the product stream contains 17.4 mol-% CO. Assuming the reactants to be
preheated to 600 K, calculate the heat requirement for the reactor.
Solution 4.8
The standard heats of reaction at 25°C for the two reactions are calculated from
the data of Table C.4:
°    = 205,813 J
CH 4(g) + H 2O(g) → CO(g) + 3H 2(g) ΔH 298
°    = −41,166 J
CO(g) + H 2O(g) → CO 2(g) + H 2(g) ΔH 298
These two reactions may be added to give a third reaction:

°    = 164,647 J
CH 4(g) + 2H 2O(g) → CO 2(g) + 4H 2(g) ΔH 298
Any pair of the three reactions constitutes an independent set. The third reaction
is not independent; it is obtained by combination of the other two. The reactions
most convenient to work with here are the first and third:
°    = 205,813 J
CH 4(g) + H 2O(g) → CO(g) + 3H 2(g) ΔH 298 (A)
°    = 164,647 J
CH 4(g) + 2H 2O(g) →  CO 2(g) + 4H 2(g) H 298 (B)
First one must determine the fraction of CH4 converted by each of these reactions.
As a basis for calculations, let 1 mol CH4 and 2 mol steam be fed to the reactor.
If x mol CH4 reacts by Eq. (A), then 1 − x mol reacts by Eq. (B). On this basis the
products of the reaction are:
CO: x
H2: 3x + 4(1 − x) = 4 − x
CO2: 1 − x
H2O: 2 − x − 2(1 − x) = x
Total: 5 mol products
The mole fraction of CO in the product stream is x/5 = 0.174; whence x = 0.870.
Thus, on the basis chosen, 0.870 mol CH4 reacts by Eq. (A) and 0.130 mol reacts
by Eq. (B). Furthermore, the amounts of the species in the product stream are:
Moles CO = x = 0.87
Moles H 2  = 4 − x = 3.13
  
  
     
Moles CO 2  = 1 − x = 0.13
Moles H 2O = x = 0.87
We now devise a path, for purposes of calculation, to proceed from reactants at

600 K to products at 1300 K. Because data are available for the standard heats of
reaction at 25°C, the most convenient path is the one which includes the reactions
at 25°C (298.15 K). This is shown schematically in the accompanying diagram.
The dashed line represents the actual path for which the enthalpy change is ΔH.
Because this enthalpy change is independent of path,
ΔH = ΔH R°  + ΔH 298
°    + ΔH P° 
Products at 1 bar
and 1300 K
0.87 mol CO
3.13 mol H2
∆H 0.13 mol CO2
0.87 mol H2O
∆H Po
Reactants at 1 bar
and 600 K ∆H Ro
1 mol CH4
2 mol H2O
o
∆H 298
°  ,  reactions (A) and (B) must both be taken into

For the calculation of ΔH 298
account. Because 0.87 mol CH4 reacts by (A) and 0.13 mol reacts by (B),
°    = (0.87)(205,813) + (0.13)(164,647) = 200,460 J
ΔH 298
The enthalpy change of the reactants cooled from 600 K to 298.15 K is:
ΔH R°  = (∑   n i ⟨C P°i ⟩  H
) (298.15 − 600)
i
where subscript i denotes reactants. The values of ⟨C P°i ⟩  H / R are:
H 4 : MCPH(298.15, 600; 1.702, 9.081 × 10 −3, − 2.164 × 10 −6, 0.0) = 5.3272
C
H −3 5
 2O : MCPH(298.15, 600; 3.470, 1.450 × 10  , 0.0, 0.121 × 10  ) = 4.1888 
       
and
ΔH R° = (8.314)[(1)(5.3272)+(2)(4.1888)](298.15 − 600) = − 34,390 J
The enthalpy change of the products as they are heated from 298.15 to 1300 K is
calculated similarly:
ΔH P°  = ( ∑   n i ⟨C P°i ⟩  H
) (1300 − 298 . 15)
i
where subscript i here denotes products. The ⟨C P°i ⟩  H

/ Rvalues are:
CO : MCPH(298.15, 1300; 3.376, 0.557 × 10 −3, 0.0, − 0.031 × 10 5) = 3.8131
H 2 : MCPH(298.15, 1300; 3.249, 0.422 × 10 −3, 0.0, − 0.083 × 10 5) = 3.6076
       
      
CO 2 : MCPH(298.15, 1300; 5.457, 1.045 × 10 −3, 0.0, − 1.157 × 10 5) = 5.9935
H 2O : MCPH(298.15, 1300; 3.470, 1.450 × 10 −3, 0.0, 0.121 × 10 5) = 4.6599
Whence,
ΔH P°   = (8.314)[(0.87)(3.8131) + (3.13)(3.6076) 
+ (0.13)( 5.9935) + (0.87)( 4.6599)]  × (1300 − 298.15) 
= 161, 940 J
Therefore,
ΔH = −34,390 + 200,460 + 161,940 = 328,010 J
The process is one of steady flow for which Ws, Δz, and Δu2/2 are presumed
negligible. Thus,
Q = ΔH = 328, 010 J
This result is on the basis of 1 mol CH4 fed to the reactor.
Example 4.9
Solar-grade silicon can be manufactured by thermal decomposition of silane at moder-
ate pressure in a fluidized-bed reactor, in which the overall reaction is:
SiH 4(g) → Si(s) + 2H 2(g)
When pure silane is preheated to 300°C, and heat is added to the reactor to promote
a reasonable reaction rate, 80% of the silane is converted to silicon and the products
leave the reactor at 750°C. How much heat must be added to the reactor for each
kilogram of silicon produced?
Solution 4.9
For a continuous-flow process with no shaft work and negligible changes in kinetic
and potential energy, the energy balance is simply Q = ΔH, and the heat added is
the enthalpy change from reactant at 300°C to products at 750°C. A convenient
path for calculation of the enthalpy change is to (1) cool the reactant to 298.15 K,
(2) carry out the reaction at 298.15 K, and (3) heat the products to 750°C.
On the basis of 1 mol SiH4, the products consist of 0.2 mol SiH4, 0.8 mol Si,
and 1.6 mol H2. Thus, for the three steps we have:
298.15K
∫573.15K P
ΔH 1 =       C ° (SiH 4) dT
   
   °   
ΔH 2 = 0.8 × ΔH 298

1023.15K
∫298.15K [
ΔH 3 =        0.2 × C P° (SiH 4) + 0.8 × C P° (Si) + 1.6 × C P° (H 2)]dT
Data needed for this example are not included in App. C, but are readily
obtained from the NIST Chemistry Webbook (http://webbook.nist.gov). The
reaction here is the reverse of the formation reaction for silane, and its standard
°    = − 34,310 J. Thus, the reaction is mildly
heat of reaction at 298.15 K is ΔH 298
exothermic.
Rev. Confirming Pages
Heat capacity in the NIST Chemistry Workbook is expressed by the Shomate

equation, a polynomial of different form from that used in this text. It includes a T3
term, and is written in terms of T/1000, with T in K:
( 1000 )
2 3 −2
( 1000 ) ( 1000 ) ( 1000 )

T T T T
C P°  = A + B _
        + C _____
          + D _____
          + E _____
        
Formal integration of this equation gives the enthalpy change:

T
∫T 0
ΔH =       C P°  dT
2 3 4 −1 T
[ ( 1000 ) 2 ( 1000 ) 3 ( 1000 ) 4 ( 1000 ) ( 1000 ) ] T 

T B T C T D T T
ΔH = 1000 A _____
        +  __     _____
         +  __     _____
         +  __     _____
         − E _____
             
0
The first three rows in the accompanying table give parameters, on a molar
basis, for SiH4, crystalline silicon, and hydrogen. The final entry is for the collec-
tive products, represented for example by:
A(products) = (0.2) (6.060) + (0.8)(22.817) + (1.6)(33.066) = 72.3712
with corresponding equations for B, C, D, and E.
Species A B C D E
SiH4(g) 6.060 139.96 −77.88 16.241 0.1355
Si(s) 22.817 3.8995 −0.08289 0.04211 −0.3541
H2(g) 33.066 −11.363 11.433 −2.773 −0.1586
Products 72.3712 12.9308 2.6505 −1.1549 −0.5099
For these parameters, and with T in Kelvins, the equation for ΔH yields values
in joules. For the three steps making up the solution to this problem, the following
results are obtained:
1. Substitution of the parameters for 1 mol of SiH4 into the equation for ΔH leads upon
evaluation to: ΔH1 = −14,860 J
2. Here, ΔH 2 = (0.8)(− 34,310) = − 27,450 J
3. Substitution of the parameters for the total product stream into the equation for ΔH
leads upon evaluation to: ΔH3 = 58,060 J
For the three steps the sum is:
ΔH = − 14,860 − 27,450 + 58,060 = 15,750 J
This enthalpy change equals the heat input per mole of SiH4 fed to the reactor. A kilo-
gram of silicon, with a molar mass of 28.09, is 35.60 mol. Producing a kilogram of
silicon therefore requires a feed of 35.60/0.8 or 44.50 mol of SiH4. The heat require-
ment per kilogram of silicon produced is therefore (15,750)(44.5) = 700,900 J.
smi96529_ch04_133-172.indd 158 06/19/17 12:12 PM

Example 4.10
A boiler is fired with a high-grade fuel oil (consisting only of hydrocarbons) having a
standard heat of combustion of −43,515 J·g−1 at 25°C with CO2(g) and H2O(l) as prod-
ucts. The temperature of the fuel and air entering the combustion chamber is 25°C.
The air is assumed dry. The flue gases leave at 300°C, and their average analysis (on a
dry basis) is 11.2% CO2, 0.4% CO, 6.2% O2, and 82.2% N2. Calculate the fraction of the
heat of combustion of the oil that is transferred as heat to the boiler.
Solution 4.10
Take as a basis 100 mol dry flue gases, consisting of:
CO2 11.2 mol
CO 0.4 mol
O2 6.2 mol
N2 82.2 mol
Total 100.0 mol
This analysis, on a dry basis, does not take into account the H2O vapor present in
the flue gases. The amount of H2O formed by the combustion reaction is found
from an oxygen balance. The O2 supplied in the air represents 21 mol-% of the
air stream. The remaining 79% is N2, which goes through the combustion process
unchanged. Thus the 82.2 mol N2 appearing in 100 mol dry flue gases is supplied
with the air, and the O2 accompanying this N2 is:
Moles O2 entering in air = (82.2)(21 / 79) = 21.85
and
Total moles O 2 in the dry flue gases  =  11.2 + 0.4 / 2 + 6.2 = 17.60
The difference between these figures is the moles of O2 that react to form H2O.
Therefore on the basis of 100 mol dry flue gases,
Moles H 2O formed = (21.85 − 17.60) (2) = 8.50
Moles H 2 in the fuel = moles of water formed = 8.50
The amount of C in the fuel is given by a carbon balance:

Moles C in flue gases = moles C in fuel = 11.2 + 0.4 = 11.60
These amounts of C and H2 together give:
Mass of fuel burned = (8.50)(2) + (11.6)(12) = 156.2 g
If this amount of fuel is burned completely to CO2(g) and H2O(l) at 25°C, the
heat of combustion is:
°    = (− 43,515) (156.2) = − 6,797,040 J
ΔH 298
However, the reaction actually occurring does not represent complete combustion,
and the H2O is formed as vapor rather than as liquid. The 156.2 g of fuel, consist-
ing of 11.6 mol of C and 8.5 mol of H2, is represented by the empirical formula
C11.6H17. Omit the 6.2 mol O2 and 82.2 mol N2 which enter and leave the reactor
unchanged, and write the reaction:
C 11.6 H 17(l) + 15.65 O 2(g) → 11.2 CO 2(g) + 0.4 CO(g) + 8.5 H 2 O(g)
This result is obtained by addition of the following reactions, for each of which the
standard heat of reaction at 25°C is known:
C 11.6 H 17(l) + 15.85 O 2 (g) → 11.6 CO 2(g) + 8.5 H 2 O(l)
8.5
  
     H 2 O(l)   → 8.5 H 2O(g)  
0.4 CO 2(g) → 0.4CO(g) + 0.2 O 2(g)
°   
The sum of these reactions yields the actual reaction, and the sum of the ΔH 298
values gives the standard heat of the reaction occurring at 25°C:
°    = −6,797,040 + (44,012) (8.5) + (282,984) (0.4) = − 6,309,740 J
ΔH 298
The actual process leading from reactants at 25°C to products at 300°C is rep-
resented by the dashed line in the accompanying diagram. For purposes of calcu-
lating ΔH for this process, we may use any convenient path. The one drawn with
solid lines is a logical one: Δ °   has already been calculated and Δ
H 298 H P°  is easily
evaluated.
Products at 1 bar
and 300 C
11.2 mol CO2
0.4 mol CO
H 8.5 mol H2O
HP
6.2 mol O2
82.2 mol N2
Reactants at 1 bar
and 25 C H298
156.2 g fuel
21.85 mol O2
82.2 mol N2
The enthalpy change caused by heating the products of reaction from 25 to

300°C is:
ΔH P°  = (∑   n i ⟨C P°i ⟩  H)(573.15 − 298.15)

i
where subscript i denotes products. The ⟨C P°i ⟩  H

/ Rvalues are:
O 2: MCPH(298.15, 573.15; 5.457, 1.045 × 10 −3, 0.0, −1.157 × 10 5) = 5.2352
C
CO: MCPH(298.15, 573.15; 3.376, 0.557 × 10 −3, 0.0, −0.031 × 10 5) = 3.6005
 2O  :  MCPH(298.15, 573.15; 3.470, 1.450 × 10 −3, 0.0, 0.121 × 10 5) = 4.1725 
       
       
H
 2:
O MCPH(298.15, 573.15; 3.639, 0.506 × 10 −3, 0.0, − 0.227 × 10 5) = 3.7267
N 2: MCPH(298.15, 573.15; 3.280, 0.593 × 10 −3, 0.0, 0.040 × 10 5) = 3.5618
Therefore,
ΔH P°  = (8.314)[(11.2)(5.2352) + (0.4)(3.6005) + (8.5)(4.1725) + (6.2)(3.7267) +
(82.2)(3.5618)](573.15 − 298.15) = 940,660 J
and
°    + ΔH P°  = − 6, 309,740 + 940,660 = − 5,369,080 J
ΔH = ΔH 298
Because the process is one of steady flow for which the shaft work and kinetic-
and potential-energy terms in the energy balance [Eq. (2.32)] are zero or negligi-
ble, ΔH = Q. Thus, Q = −5369 kJ, and this amount of heat is transferred to the
boiler for every 100 mol dry flue gases formed. This represents
5,369,080
_________
    
(100) = 79.0%
6,797,040
of the higher heat of combustion of the fuel.
In the foregoing examples of reactions that occur at approximately 1 bar, we have tacitly
assumed that the heat effects of reaction are the same whether gases are mixed or pure, an
acceptable procedure for low pressures. For reactions at elevated pressures, this may not be the
case, and it may be necessary to account for the effects of pressure and of mixing on the heat of
reaction. However, these effects are usually small. For reactions occurring in the liquid phase,
the effects of mixing are generally more important. They are treated in detail in Chapter 11.
For biological reactions, occurring in aqueous solution, the effects of mixing are par-
ticularly important. The enthalpies and other properties of biomolecules in solution usually
depend not only on temperature and pressure, but also on the pH, ionic strength, and concen-
trations of specific ions in solution. Table C.5 in App. C provides enthalpies of formation of
a variety of molecules in dilute aqueous solution at zero ionic strength. These can be used to
estimate heat effects of enzymatic or biological reactions involving such species. However,
corrections for effects of pH, ionic strength, and finite concentration may be significant.16
Heat capacities are often unknown for such species, but in dilute aqueous solution the over-
all specific heat is usually well approximated by the specific heat of water. Moreover, the
temperature range of interest for biological reactions is quite narrow. The following example
illustrates estimation of heat effects for a biological reaction.
16For analysis of these effects, see Robert A. Alberty, Thermodynamics of Biochemical Reactions, John Wiley &
Sons, Hoboken, NJ, 2003.

Example 4.11
A dilute solution of glucose enters a continuous fermentation process, where yeast
cells convert it to ethanol and carbon dioxide. The aqueous stream entering the reac-
tor is at 25°C and contains 5 wt% glucose. Assuming this glucose is fully converted to
ethanol and carbon dioxide, and that the product stream leaves the reactor at 35°C,
estimate the amount of heat added or removed per kg of ethanol produced. Assume
that the carbon dioxide remains dissolved in the product stream.
Solution 4.11
For this constant pressure process with no shaft work, the heat effect is simply
equal to the enthalpy change from the feed stream to the product stream. The fer-
mentation reaction is:
C 6 H 12 O 6(aq) → 2 C 2 H 5 OH(aq) + 2 CO 2(aq)
The standard enthalpy of reaction at 298 K obtained using the heats of forma-
tion in dilute aqueous solution from Table C.5 is:
°    = (2)(−288.3) + (2)(−413.8) − (−1262.2) = −142.0 kJ·mol −1
ΔH 298
One kg of ethanol is 1/(0.046069 kg·mol−1) = 21.71 mol ethanol. Each mole

of glucose produces two moles of ethanol, so 10.85 mol of reaction must occur to
produce 1 kg of ethanol. The standard enthalpy of reaction per kg ethanol is then
(10.85)(−142.0) = −1541 kJ·kg−1. The mass of glucose required to produce 1 kg
ethanol is 10.85 mol × 0.18016 kg·mol−1 = 1.955 kg glucose. If the feed stream
is 5 wt% glucose, then the total mass of solution fed to the reactor per kg ethanol
produced is 1.955/0.05 = 39.11 kg. Assuming that the product stream has the
specific heat of water, about 4.184 kJ·kg−1·K−1, then the enthalpy change per kg
ethanol for heating the product stream from 25°C to 35°C is:
4.184 kJ·kg  −1 ·K −1 × 10 K × 39.11 kg = 1636 kJ.
Adding this to the heat of reaction per kg ethanol gives the total enthalpy
change from feed to product, which is also the total heat effect:
Q = ΔH = − 1541 + 1636 = 95 kJ·(kg ethanol) −1
This estimate leads to the conclusion that a small amount of heat must be added to
the reactor because the reaction exothermicity is not quite sufficient to heat the feed
stream to the product temperature. In an actual process, the glucose would not be fully
converted to ethanol. Some fraction of the glucose must be directed to other products
of cellular metabolism. This means that somewhat more than 1.955 kg glucose will be
needed per kg of ethanol produced. The heat release from other reactions may be some-
what higher or lower than that for the production of ethanol, which would change the
estimate. If some of the CO2 leaves the reactor as a gas, then the heat requirement will
be slightly higher because the enthalpy of CO2(g) is higher than that of aqueous CO2.
4.9. Problems
4.9 163
4.8 SYNOPSIS
After studying this chapter, including the end-of-chapter problems, one should be able to:
∙ Define sensible heat effects, latent heat, heat of reaction, heat of formation, and heat of
combustion
∙ Formulate a heat-capacity integral, decide whether to use CP or CV in it, and evaluate it
with the heat capacity expressed as a polynomial in temperature
∙ Use a heat-capacity integral in an energy balance to determine the energy input required
to achieve a given temperature change or to determine the temperature change that will
result from a given energy input
∙ Look up or estimate latent heats of phase change and apply them in energy balances
∙ Apply the Clayperon equation
∙ Compute a standard heat of reaction at arbitrary temperature from heats of formation
and heat capacities
∙ Compute standard heats of reaction from standard heats of combustion
∙ Compute heat requirements for a process with specified chemical reactions and speci-
fied inlet and outlet temperatures
4.9 PROBLEMS
For steady flow in a heat exchanger at approximately atmospheric pressure, what is

4.1.
the heat transferred:
(a) When 10 mol of SO2 is heated from 200 to 1100°C?

(b) When 12 mol of propane is heated from 250 to 1200°C?
(c) When 20 kg of methane is heated from 100 to 800°C?
(d) When 10 mol of n-butane is heated from 150 to 1150°C?
(e) When 1000 kg of air is heated from 25 to 1000°C?
(f) When 20 mol of ammonia is heated from 100 to 800°C?
(g) When 10 mol of water is heated from 150 to 300°C?
(h) When 5 mol of chlorine is heated from 200 to 500°C?
(i) When 10 kg of ethylbenzene is heated from 300 to 700°C?
For steady flow through a heat exchanger at approximately atmospheric pressure,

4.2.
what is the final temperature,
(a) When heat in the amount of 800 kJ is added to 10 mol of ethylene initially at 200°C?
(b) When heat in the amount of 2500 kJ is added to 15 mol of 1-butene initially at 260°C?
(c) When heat in the amount of 106(Btu) is added to 40(lb mol) of ethylene initially at
500(°F)?
For a steady-flow heat exchanger with a feed temperature of 100°C, compute the out-
4.3.
let stream temperature when heat in the amount of 12 kJ·mol−1 is added to the follow-
ing substances.
(a) methane, (b) ethane, (c) propane, (d) n-butane, (e) n-hexane, (f) n-octane, (g) pro-
pylene, (h) 1-pentene, (i) 1-heptene, (j) 1-octene, (k) acetylene, (l) benzene, (m) eth-
anol, (n) styrene, (o) formaldehyde, (p) ammonia, (q) carbon monoxide, (r) carbon
dioxide, (s) sulfur dioxide, (t) water, (u) nitrogen, (ν) hydrogen cyanide
4.4. If 250(ft)3(s)−1 of air at 122(°F) and approximately atmospheric pressure is preheated

for a combustion process to 932(°F), what rate of heat transfer is required?
How much heat is required when 10,000 kg of CaCO3 is heated at atmospheric pres-
4.5.
sure from 50°C to 880°C?
If the heat capacity of a substance is correctly represented by an equation of the form,

4.6.
CP   = A + BT + CT  2
show that the error resulting when ⟨CP⟩H is assumed equal to CP evaluated at the
arithmetic mean of the initial and final temperatures is C(T2 − T1)2/12.
If the heat capacity of a substance is correctly represented by an equation of the form,

4.7.
CP   = A + BT + D T −2
show that the error resulting when ⟨CP⟩H is assumed equal to CP evaluated at the
arithmetic mean of the initial and final temperatures is:
2
T 1 T 2( T 2 + T 1)
D T 2 − T 1
_____ _______
            
 
Calculate the heat capacity of a gas sample from the following information: The sam-
4.8.
ple comes to equilibrium in a flask at 25°C and 121.3 kPa. A stopcock is opened
briefly, allowing the pressure to drop to 101.3 kPa. With the stopcock closed, the flask
warms, returning to 25°C, and the pressure is measured as 104.0 kPa. Determine CP
in J·mol−1·K−1 assuming the gas to be ideal and the expansion of the gas remaining in
the flask to be reversible and adiabatic.
A process stream is heated as a gas from 25°C to 250°C at constant P. A quick esti-
4.9.
mate of the energy requirement is obtained from Eq. (4.3), with CP taken as constant
and equal to its value at 25°C. Is the estimate of Q likely to be low or high? Why?
4.10. (a) For one of the compounds listed in Table B.2 of App. B, evaluate the latent heat
of vaporization ΔHn by Eq. (4.13). How does this result compare with the value
listed in Table B.2?
(b) Handbook values for the latent heats of vaporization at 25°C of four compounds
are given in the table. For one of these, calculate ΔHn using Eq. (4.14), and com-
pare the result with the value given in Table B.2.
4.9. Problems
4.9 165
Latent heats of vaporization at 25°C in J·g−1

n-Pentane 366.3 Benzene 433.3
n-Hexane 366.1 Cyclohexane 392.5
4.11. Table 9.1 lists the thermodynamic properties of saturated liquid and vapor tetrafluo-
roethane. Making use of the vapor pressures as a function of temperature and of the
saturated-liquid and saturated-vapor volumes, calculate the latent heat of vaporization
by Eq. (4.12) at one of the following temperatures and compare the result with the
latent heat of vaporization calculated from the enthalpy values given in the table.
(a) −16°C, (b) 0°C, (c) 12°C, (d) 26°C, (e) 40°C.
4.12. Handbook values for the latent heats of vaporization in J·g−1 are given in the table for
three pure liquids at 0°C.
ΔHlv at 0° C
Chloroform 270.9
Methanol 1189.5
Tetrachloromethane 217.8
For one of these substances, calculate:
(a) The value of the latent heat at Tn by Eq. (4.14), given the value at 0°C.
(b) The value of the latent heat at Tn by Eq. (4.13).
By what percentages do these results differ from the value listed in Table B.2 of App. B?
4.13. Table B.2 of App. B provides parameters for an equation that gives Psat as a function of
T for a number of pure compounds. For one of them, determine the heat of vaporization
at its normal boiling point by application of Eq. (4.12), the Clapeyron equation. Evaluate
dPsat/dT from the given vapor-pressure equation, and use generalized correlations from
Chapter 3 to estimate ΔV. Compare the computed value with the value of ΔHn listed in
Table B.2. Note that normal boiling points are listed in the last column of Table B.2.
4.14. A method for determination of the second virial coefficient of a pure gas is based on
the Clapeyron equation and measurements of the latent heat of vaporization ΔHlv,
the molar volume of saturated liquid Vl, and the vapor pressure Psat. Determine B in
cm3·mol−1 for methyl ethyl ketone at 75°C from the following data at this temperature:
ΔH lν = 31,600 J·mol −1 V l = 96.49 cm 3 ·mol −1
ln P sat / kPa = 48.158 − 5623 / T − 4.705 ln T [T = K]
4.15. One hundred kmol per hour of subcooled liquid at 300 K and 3 bar is superheated to
500 K in a steady-flow heat exchanger. Estimate the exchanger duty (in kW) for one of
the following:
(a) Methanol, for which T sat = 368.0 K at 3 bar.

(b) Benzene, for which T sat = 392.3 K at 3 bar.
(c) Toluene, for which T sat = 426.9 K at 3 bar.
4.16. For each of the following substances, compute the final temperature when heat in
the amount of 60 kJ·mol−1 is added to the subcooled liquid at 25°C at atmospheric
pressure.
(a) methanol
(b) ethanol
(c) benzene
(d) toluene
(e) water
4.17. Saturated-liquid benzene at pressure P1 = 10 bar ( T1sat     = 451.7K)is throttled in a

steady-flow process to a pressure P2 = 1.2 bar ( T2sat
    = 358.7K), where it is a liquid/
vapor mixture. Estimate the molar fraction of the exit stream that is vapor. For liquid
benzene, CP = 162 J·mol−1·K−1. Ignore the effect of pressure on the enthalpy of liquid
benzene.
4.18. Estimate ΔH f° 2 98 for one of the following compounds as a liquid at 25°C.
(a) Acetylene, (b) 1,3-Butadiene, (c) Ethylbenzene, (d) n-Hexane, (e) Styrene.
4.19. Reversible compression of 1 mol of an ideal gas in a piston/cylinder device results in

a pressure increase from 1 bar to P2 and a temperature increase from 400 K to 950 K.
The path followed by the gas during compression is given by PV1.55 = const, and the
molar heat capacity of the gas is given by:
C P / R = 3.85 + 0.57 × 10 −3 T [ T = K ]
Determine the heat transferred during the process and the final pressure.
4.20. Hydrocarbon fuels can be produced from methanol by reactions such as the following,
which yields 1-hexene:
6CH 3OH(g) → C 6H 12(g) + 6H 2O(g)
Compare the standard heat of combustion at 25°C of 6 CH3OH(g) with the standard
heat of combustion at 25°C of C6H12(g) for reaction products CO2(g) and H2O(g).
4.21. Calculate the theoretical flame temperature when ethylene at 25°C is burned with:
(a) The theoretical amount of air at 25°C.

(b) 25% excess air at 25°C.
(c) 50% excess air at 25°C.
(d) 100% excess air at 25°C.
(e) 50% excess air preheated to 500°C.
(f) The theoretical amount of pure oxygen.
4.22. What is the standard heat of combustion of each of the following gases at 25°C if the
combustion products are H2O(l) and CO2(g)? Compute both the molar and specific
heat of combustion in each case.
4.9. Problems
4.9 167
(a) methane, (b) ethane, (c) ethylene, (d) propane, (e) propylene, (f) n-butane,
(g) 1-butene, (h) ethylene oxide, (i) acetaldehyde, (j) methanol, (k) ethanol.
4.23. Determine the standard heat of each of the following reactions at 25°C:
(a) N2(g) + 3H2(g) → 2NH3(g)

(b) 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
(c) 3NO2(g) + H2O(l) → 2HNO3(l) + NO(g)
(d) CaC2(s) + H2O(l) → C2H2(g) + CaO(s)
(e) 2Na(s) + 2H2O(g) → 2NaOH(s) + H2(g)
(f) 6NO2(g) + 8NH3(g) → 7N2(g) + 12H2O(g)
(g) C2H4(g) + _ 12 O2(g) → ⟨(CH2)2⟩O(g)
(h) C2H2(g) + H2O(g) → ⟨(CH2)2⟩O(g)
(i) CH4(g) + 2H2O(g) → CO2(g) + 4H2(g)
(j) CO2(g) + 3H2(g) → CH3OH(g) + H2O(g)
(k) CH3OH(g) + _ 12 O2(g) → HCHO(g) + H2O(g)
(l) 2H2S(g) + 3O2(g) → 2H2O(g) + 2SO2(g)
(m) H2S(g) + 2H2O(g) → 3H2(g) + SO2(g)
(n) N2(g) + O2(g) → 2NO(g)
(o) CaCO3(s) → CaO(s) + CO2(g)
(p) SO3(g) + H2O(l) → H2SO4(l)
(q) C2H4(g) + H2O(l) → C2H5OH(l)
(r) CH3CHO(g) + H2(g) → C2H5OH(g)
(s) C2H5OH(l) + O2(g) → CH3COOH(l) + H2O(l)
(t) C2H5CH:CH2(g) → CH2:CHCH:CH2(g) + H2(g)
(u) C4H10(g) → CH2:CHCH:CH2(g) + 2H2(g)
(ν) C2H5CH:CH2(g) + _ 12 O2(g) → CH2:CHCH:CH2(g) + H2O(g)
(w) 4NH3(g) + 6NO(g) → 6H2O(g) + 5N2(g)
(x) N2(g) + C2H2(g) → 2HCN(g)
(y) C6H5C2H5(g) → C6H5CH:CH2(g) + H2(g)
(z) C(s) + H2O(l) → H2(g) + CO(g)
4.24. Determine the standard heat for one of the reactions of Prob. 4.23: part (a) at 600°C,
part (b) at 50°C, part (f) at 650°C, part (i) at 700°C, part (j) at 590(°F), part (l) at
770(°F), part (m) at 850 K, part (n) at 1300 K, part (o) at 800°C, part (r) at 450°C, part
(t) at 860(°F), part (u) at 750 K, part (v) at 900 K, part (w) at 400°C, part (x) at 375°C,
part (y) at 1490(°F).
4.25. Develop a general equation for the standard heat of reaction as a function of tempera-
ture for one of the reactions given in parts (a), (b), (e), (f), (g), (h), (j), (k), (l), (m), (n),
(o), (r), (t), (u), (v), (w), (x), (y), and (z) of Prob. 4.23.
4.26. Compute the standard heat of reaction for each of the following reactions taking place
at 298.15 K in dilute aqueous solution at zero ionic strength.
(a) D-Glucose + ATP2− → D-Glucose 6-phosphate− + ADP−

(b) D-Glucose 6-phosphate− → D-Fructose 6-phosphate−
(c) D-Fructose 6-phosphate− + ATP2− → D-Fructose 1,6-biphosphate2− + ADP−

(d) D-Glucose + 2 ADP− + 2H 2 PO− + −
4  + 2 NAD → 2 Pyruvate + 2 ATP
2− +
2 NADH + 4H+ + 2H2O

(e) D-Glucose + 2 ADP− + 2H 2 PO− − 2− +
4  → 2 Lactate + 2 ATP + 2H + 2H2O
(f) D-Glucose + 2 ADP− + 2H 2 PO−  4 → 2CO2 + 2 Ethanol + 2 ATP2− + 2 H2O
(g) 2 NADH + O2 + 2H+ → 2 NAD+ + 2H2O
(h) ADP− + H 2 PO− 4  →ATP
2− + H O
2
(i) 2 NADH + 2 ADP−+ 2H 2 PO− +
4  + O2 + 2H → 2 NAD + 2 ATP
+ 2− + 4H O
2
(j) D-Fructose + 2 ADP− + 2H 2 PO−  4 → 2CO2 + 2 Ethanol +2 ATP2− + 2H2O
(k) D-Galactose + 2 ADP− + 2H 2 PO− 4  → 2CO2 + 2
(l) Ethanol + 2 ATP2− + 2H2O
NH+ − 2− → L-asparagine + ADP− + H  PO− 
4  + L-aspartate + ATP 2 4
4.27. The first step in the metabolism of ethanol is dehydrogenation by reaction with
nicotinamide-adenine dinucleotide (NAD):
C  2H  5OH + NAD + → C  2H  4O + NADH
What is the heat effect of this reaction upon metabolizing 10 g of ethanol from a typical
cocktail? What is the total heat effect for complete metabolism of the 10 g of ethanol
to CO2 and water? How, if at all, is the perception of warmth that accompanies eth-
anol consumption related to these heat effects? For computing heat effects, you may
neglect the temperature, pH, and ionic strength dependence of the enthalpy of reaction
(i.e. apply the enthalpies of formation from Table C.5 of App. C at physiological conditions).
4.28. Natural gas (assume pure methane) is delivered to a city via pipeline at a volumetric
rate of 150 million standard cubic feet per day. If the selling price of the gas is
$5.00 per GJ of higher heating value, what is the expected revenue in dollars per day?
Standard conditions are 60(°F) and 1(atm).
4.29. Natural gases are rarely pure methane; they usually also contain other light
hydrocarbons and nitrogen. Determine an expression for the standard higher heat of
combustion as a function of composition for a natural gas containing methane, ethane,
propane, and nitrogen. Assume liquid water as a product of combustion. Which of the
following natural gases has the highest heat of combustion?
(a)
y  CH 4 = 0.95, y C 2H 6 = 0.02, y C 3H 8 = 0.02, y N 2 = 0.01.
(b)
y CH 4 = 0.90, y C 2H 6 = 0.05, y C 3H 8 = 0.03, y N 2 = 0.02.
(c)
y CH 4 = 0.85, y C 2H 6 = 0.07, y C 3H 8 = 0.03, y N 2 = 0.05.
4.30. If the heat of combustion of urea, (NH2)2CO(s), at 25°C is 631,660 J·mol−1 when the
products are CO2(g), H2O(l), and N2(g), what is ΔH f° 2 98  for urea?
4.31. The higher heating value (HHV) of a fuel is its standard heat of combustion at 25°C with
liquid water as a product; the lower heating value (LHV) is for water vapor as product.
(a) Explain the origins of these terms.

(b) Determine the HHV and the LHV for natural gas, modeled as pure methane.
4.9. Problems
4.9 169
(c) Determine the HHV and the LHV for a home-heating oil, modeled as pure liquid
n-decane. For n-decane as a liquid
ΔH f° 2 98   = − 249,700 J·mol −1.
4.32. A light fuel oil with an average chemical composition of C10H18 is burned with oxy-
gen in a bomb calorimeter. The heat evolved is measured as 43,960 J·g−1 for the reac-
tion at 25°C. Calculate the standard heat of combustion of the fuel oil at 25°C with
H2O(g) and CO2(g) as products. Note that the reaction in the bomb occurs at constant
volume, produces liquid water as a product, and goes to completion.
4.33. Methane gas is burned completely with 30% excess air at approximately atmos-
pheric pressure. Both the methane and the air enter the furnace at 30°C saturated
with water vapor, and the flue gases leave the furnace at 1500°C. The flue gases then
pass through a heat exchanger from which they emerge at 50°C. Per mole of methane,
how much heat is lost from the furnace, and how much heat is transferred in the heat
exchanger?
4.34. Ammonia gas enters the reactor of a nitric acid plant mixed with 30% more dry air
than is required for the complete conversion of the ammonia to nitric oxide and water
vapor. If the gases enter the reactor at 75°C, if conversion is 80%, if no side reactions
occur, and if the reactor operates adiabatically, what is the temperature of the gases
leaving the reactor? Assume ideal gases.
4.35. Ethylene gas and steam at 320°C and atmospheric pressure are fed to a reaction pro-
cess as an equimolar mixture. The process produces ethanol by the reaction:
C 2H 4(g) + H 2O(g) → C 2H 5OH(l)
The liquid ethanol exits the process at 25°C. What is the heat transfer associated with
this overall process per mole of ethanol produced?
4.36. A gas mixture of methane and steam at atmospheric pressure and 500°C is fed to a
reactor, where the following reactions occur:
CH 4 + H 2O → CO + 3 H 2  and   CO + H 2O → CO 2 + H 2
The product stream leaves the reactor at 850°C. Its composition (mole fractions) is:
y CO 2 = 0.0275  y CO = 0.1725  y H 2O = 0.1725  y H 2 = 0.6275
Determine the quantity of heat added to the reactor per mole of product gas.
4.37. A fuel consisting of 75 mol-% methane and 25 mol-% ethane enters a furnace with
80% excess air at 30°C. If 8 × 105 kJ·kmol−1 fuel is transferred as heat to boiler tubes,
at what temperature does the flue gas leave the furnace? Assume complete combus-
tion of the fuel.
4.38. The gas stream from a sulfur burner consists of 15 mol-% SO2, 20 mol-% O2, and
65 mol-% N2. The gas stream at atmospheric pressure and 400°C enters a catalytic
converter where 86% of the SO2 is further oxidized to SO3. On the basis of 1 mol of
gas entering, how much heat must be added to or removed from the converter so that
the product gases leave at 500°C?
4.39. Hydrogen is produced by the reaction: C O(g) + H 2O(g) → CO 2(g) + H 2(g).

The feed stream to the reactor is an equimolar mixture of carbon monoxide and steam,
and it enters the reactor at 125°C and atmospheric pressure. If 60% of the H2O is
converted to H2 and if the product stream leaves the reactor at 425°C, how much heat
must be transferred to or from the reactor?
4.40. A direct-fired dryer burns a fuel oil with a lower heating value of 19,000(Btu)
(lbm)−1. [Products of combustion are CO2(g) and H2O(g).] The composition of
the oil is 85% carbon, 12% hydrogen, 2% nitrogen, and 1% water by weight. The
flue gases leave the dryer at 400(°F), and a partial analysis shows that they contain
3 mol-% CO2 and 11.8 mol-% CO on a dry basis. The fuel, air, and material being
dried enter the dryer at 77(°F). If the entering air is saturated with water and if
30% of the net heating value of the oil is allowed for heat losses (including the sen-
sible heat carried out with the dried product), how much water is evaporated in the
dryer per (lbm) of oil burned?
4.41. An equimolar mixture of nitrogen and acetylene enters a steady-flow reactor at 25°C
and atmospheric pressure. The only reaction occurring is: N 2(g) + C 2 H 2(g) → 2HCN
(g) . The product gases leave the reactor at 600°C and contain 24.2 mol-% HCN. How
much heat is supplied to the reactor per mole of product gas?
4.42. Chlorine is produced by the reaction: 4HCl(g) + O 2(g) → 2 H 2O(g) + 2 Cl 2(g). The

feed stream to the reactor consists of 60 mol-% HCl, 36 mol-% O2, and 4 mol-% N2,
and it enters the reactor at 550°C. If the conversion of HCl is 75% and if the process is
isothermal, how much heat must be transferred to or from the reactor per mole of the
entering gas mixture?
4.43. A gas consisting only of CO and N2 is made by passing a mixture of flue gas and
air through a bed of incandescent coke (assume pure carbon). The two reactions that
occur both go to completion:
CO 2 + C → 2CO  and   2C + O 2 → 2CO

The flue gas composition is 12.8 mol-% CO, 3.7 mol-% CO2, 5.4 mol-% O2, and
78.1 mol-% N2. The flue gas/air mixture is so proportioned that the heats of the two
reactions cancel, and the temperature of the coke bed is therefore constant. If this
temperature is 875°C, if the feed stream is preheated to 875°C, and if the process is
adiabatic, what ratio of moles of flue gas to moles of air is required, and what is the
composition of the gas produced?
4.9. Problems
4.9 171
4.44. A fuel gas consisting of 94 mol-% methane and 6 mol-% nitrogen is burned with
35% excess air in a continuous water heater. Both fuel gas and air enter dry at 77(°F).
Water is heated at a rate of 75(lbm)(s)−1 from 77(°F) to 203(°F). The flue gases leave
the heater at 410(°F). Of the entering methane, 70% burns to carbon dioxide and 30%
burns to carbon monoxide. What volumetric flow rate of fuel gas is required if there
are no heat losses to the surroundings?
4.45. A process for the production of 1,3-butadiene results from the catalytic dehydrogena-
tion at atmospheric pressure of 1-butene according to the reaction:
C 4 H 8(g) → C 4 H 6(g) + H 2(g)
To suppress side reactions, the 1-butene feed stream is diluted with steam in the ratio
of 10 moles of steam per mole of 1-butene. The reaction is carried out i sothermally
at 525°C, and at this temperature 33% of the 1-butene is converted to 1,3-butadiene.
How much heat is transferred to or from the reactor per mole of entering 1-butene?
n air-cooled condenser transfers heat at a rate of 12(Btu)·s−1 to ambient air at

4.46. (a) A
70(°F). If the air temperature is raised 20(°F), what is the required volumetric
flow rate of the air?
(b) Rework part (a) for a heat-transfer rate of 12 kJ·s−1, ambient air at 24°C, and a
temperature rise of 13°C.
n air-conditioning unit cools 50(ft)3·s−1 of air at 94(°F) to 68(°F). What is the

4.47. (a) A
required heat-transfer rate in (Btu)·s−1?
(b) Rework part (a) for a flow rate of 1.5 m3·s−1, a temperature change from 35°C to
25°C, and units of kJ·s−1.
4.48. A propane-fired water heater delivers 80% of the standard heat of combustion of the
propane [at 25°C with CO2(g) and H2O(g) as products] to the water. If the price of
propane is $2.20 per gallon as measured at 25°C, what is the heating cost in $ per
million (Btu)? In $ per MJ?
4.49. Determine the heat transfer (J·mol−1) when one of the gases identified below is heated
in a steady-flow process from 25°C to 500°C at atmospheric pressure.
(a) Acetylene; (b) Ammonia; (c) n-Butane; (d) Carbon dioxide; (e) Carbon monoxide;
(f) Ethane; (g) Hydrogen; (h) Hydrogen chloride; (i) Methane; (j) Nitric oxide;
(k) Nitrogen; (l) Nitrogen dioxide; (m) Nitrous oxide; (n) Oxygen; (o) Propylene
4.50. Determine the final temperature for one of the gases of the preceding problem if heat
in the amount of 30,000 J·mol−1 is transferred to the gas, initially at 25°C, in a steady-
flow process at atmospheric pressure.
4.51. Quantitative thermal analysis has been suggested as a technique for monitoring the
composition of a binary gas stream. To illustrate the principle, do one of the following
problems.
(a) A methane/ethane gas mixture is heated from 25°C to 250°C at 1(atm) in a steady-
flow process. If Q = 11,500 J·mol−1, what is the composition of the mixture?
(b) A benzene/cyclohexane gas mixture is heated from 100°C to 400°C at 1(atm)
in a steady-flow process. If Q = 54,000 J·mol−1, what is the composition of the
mixture?
(c) A toluene/ethylbenzene gas mixture is heated from 150°C to 250°C at 1(atm) in a
steady-flow process. If Q = 17,500 J·mol−1, what is the composition of the mixture?
4.52. Saturated steam at 1(atm) and 100°C is continuously generated from liquid water at
1(atm) and 25°C by thermal contact with hot air in a counterflow heat exchanger. The
˙  (steam)/n˙ (  air) for two cases:
air flows steadily at 1(atm). Determine values for m
(a) Air enters the exchanger at 1000°C.

(b) Air enters the exchanger at 500°C.
For both cases, assume a minimum approach ΔT for heat exchange of 10°C.
4.53. Saturated water vapor, i.e., steam, is commonly used as a heat source in heat-
exchanger applications. Why saturated vapor? Why saturated water vapor? In a plant
of any reasonable size, several varieties of saturated steam are commonly available;
for example, saturated steam at 4.5, 9, 17, and 33 bar. But the higher the pressure the
lower the useful energy content (why?), and the greater the unit cost. Why then is
higher-pressure steam used?
4.54. The oxidation of glucose provides the principal source of energy for animal cells.
Assume the reactants are glucose [C6H12O6(s)] and oxygen [O2(g)]. The products are
CO2(g) and H2O(l).
(a) Write a balanced equation for glucose oxidation, and determine the standard heat
of reaction at 298 K.
(b) During a day an average person consumes about 150 kJ of energy per kg of body
mass. Assuming glucose the sole source of energy, estimate the mass (grams) of
glucose required daily to sustain a person of 57 kg.
(c) For a population of 275 million persons, what mass of CO2 (a greenhouse gas) is
produced daily by mere respiration. Data: For glucose, ΔH f° 2 98  = − 1274.4 kJ·mol −1.
Ignore the effect of temperature on the heat of reaction.
4.55. A natural-gas fuel contains 85 mol-% methane, 10 mol-% ethane, and 5 mol-% nitrogen.
(a) What is the standard heat of combustion (kJ·mol−1) of the fuel at 25°C with
H2O(g) as a product?
(b) The fuel is supplied to a furnace with 50% excess air, both entering at 25°C. The
products leave at 600°C. If combustion is complete and if no side reactions occur,
how much heat (kJ per mol of fuel) is transferred in the furnace?

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Chapter 4

∙ Sensible heat effects, characterized by temperature changes

∙ Heats of reaction, combustion, and formation

4.1 SENSIBLE HEAT EFFECTS

With the definition of CV provided by Eq. (2.15) this becomes:

The final term is zero in two circumstances:

∙ For any closed-system constant-volume process.

In either case, ​dU = ​CV​ ​​ dT​

With the definition of CP provided by Eq. (2.19),

Again, the final term is zero for two situations:

∙ For any constant-pressure process.

In either case, ​dH = ​CP​ ​​ dT​

ΔH = ​ ​ ​​CP​ ​​ dT ​​

Moreover, Q = ΔH for mechanically reversible, constant-pressure, closed-system processes

Temperature Dependence of the Heat Capacity

Heat Capacity in the Ideal-Gas State

also includes a T3 term as well as all four terms of Eq. (4.4).

2008; Design Institute for Physical Properties, Project 801, http://www.aiche.org/dippr/projects/801.

Hill, New York, 2001.

Evaluation of the Sensible-Heat Integral

Then 873.15 ​C​ ​ ​ ig

Use of Defined Functions

are provided in the online learning center at http://highered.mheducation.com:80/sites/1259696529.

A specific numerical value of this function is:

4.2 LATENT HEATS OF PURE SUBSTANCES

where for a pure species at temperature T,

2008; Design Institute for Physical Properties, Project 801, http://www.aiche.org/dippr/projects/801.

The value given in the steam tables is 1406 J⋅g−1.

4.3 STANDARD HEAT OF REACTION

Figure 4.2: Schematic representation of the standard heat of reaction at temperature T.

4.4 STANDARD HEAT OF FORMATION

The water-gas-shift reaction, ​CO​ 2​(g) + ​H​ 2​(g)→ CO(g) +​ H​ 2​O(g)​at 25°C, is commonly

​4HCl(g) + ​O​ 2​(g) → 2​H​ 2​O(g) + 2​Cl​ 2​(g)​

The following combination gives the desired result:

4.5 STANDARD HEAT OF COMBUSTION

4.6 TEMPERATURE DEPENDENCE OF ΔH°

​ν​ ​N​ 2​ ​ = − 1​ ​ν​ ​H​ 2​ ​ = − 3​ ​ν​ ​NH​ 3​ ​ = 2​​

​ΔH° = ​∑​ ​ ​ν​ i​Δ​H​ fi°​ ​ (4.16)

​4HCl(g) + ​O​ 2​(g) → 2​H​ 2​O(g) + 2​Cl​ 2​(g)​

Eq. (4.16) is written:

​​∑​ ​ d(​ν​ i​ ​H​ i°​ ​) = ​∑​ ​ ​ν​ i​ ​C​ ​P°​ i ​ ​​ dT​ or ​ d​∑​ ​ ​ν​ i​ ​H​ i°​ ​ = ​∑​ ​ ​ν​ i​ ​C​ ​P°​ i ​ ​​ dT​

where by definition, ​ΔA ≡ ​∑​ ​ ​ν​ i​ ​Ai​ ​​

with analogous definitions for ΔB, ΔC, and ΔD.

Equation (4.19) then becomes:

4.7 HEAT EFFECTS OF INDUSTRIAL REACTIONS

Similarly, ​B = ​∑​ ​ ​n​ i​ ​B​ i​ = 9.502 × ​10​​ −3​and D

For the product stream ​​⟨​C​ P°​ ⟩H

​MCPH(298.15, T; 43.471, 9.502 × ​10​​ −3​, 0.0, − 0.645 × ​10​​ 5​)​

Equations (A) and (B) are combined and solved for T:

​T = 2066 K or 1793° C​

​CH​ 4​(g) + ​H​ 2​O(g) → CO(g) + ​3H​ 2​(g)​

The only other reaction considered here is the water-gas-shift reaction:

​CO(g) + ​H​ 2​O(g) → ​CO​ 2​(g) + ​H​ 2​(g)​

These two reactions may be added to give a third reaction:

We now devise a path, for purposes of calculation, to proceed from reactants at

° ​​, reactions (A) and (B) must both be taken into

where subscript i here denotes products. The ​​⟨​C​ P°i ​⟩​ H

This result is on the basis of 1 mol CH4 fed to the reactor.

158 CHAPTER 4. Heat Effects

In either case, dU = CV  dT

In either case, dH = CP  dT

ΔH =      CP  dT 

Then 873.15 C   ig

The water-gas-shift reaction, CO 2(g) + H 2(g)→ CO(g) + H 2O(g)at 25°C, is commonly

4HCl(g) + O 2(g) → 2H 2O(g) + 2Cl 2(g)

ν N 2  = − 1  ν H 2  = − 3  ν NH 3  = 2

ΔH° = ∑   ν iΔH fi°  (4.16)

4HCl(g) + O 2(g) → 2H 2O(g) + 2Cl 2(g)

∑   d(ν i H i° ) = ∑   ν i C P° i    dT  or   d∑   ν i H i°  = ∑   ν i C P° i    dT

where by definition, ΔA ≡ ∑   ν i Ai 

Similarly, B = ∑   n i B i = 9.502 × 10 −3and D

For the product stream ⟨C P° ⟩H

MCPH(298.15, T; 43.471, 9.502 × 10 −3, 0.0, − 0.645 × 10 5)

T = 2066 K or 1793° C

CH 4(g) + H 2O(g) → CO(g) + 3H 2(g)

CO(g) + H 2O(g) → CO 2(g) + H 2(g)

°  ,  reactions (A) and (B) must both be taken into

where subscript i here denotes products. The ⟨C P°i ⟩  H

[ ( 1000 ) 2 ( 1000 ) 3 ( 1000 ) 4 ( 1000 ) ( 1000 ) ] T 

smi96529_ch04_133-172.indd 158 06/19/17 12:12 PM

Moles O2 entering in air = (82.2)(21 / 79) = 21.85

C 11.6 H 17(l) + 15.65 O 2(g) → 11.2 CO 2(g) + 0.4 CO(g) + 8.5 H 2 O(g)

ΔH P°  = (∑   n i ⟨C P°i ⟩  H)(573.15 − 298.15)

where subscript i denotes products. The ⟨C P°i ⟩  H

4.17. Saturated-liquid benzene at pressure P1 = 10 bar ( T1sat     = 451.7K)is throttled in a

4.18. Estimate ΔH f° 2 98 for one of the following compounds as a liquid at 25°C.

C 2H 4(g) + H 2O(g) → C 2H 5OH(l)

CH 4 + H 2O → CO + 3 H 2  and   CO + H 2O → CO 2 + H 2

y CO 2 = 0.0275  y CO = 0.1725  y H 2O = 0.1725  y H 2 = 0.6275

4.39. Hydrogen is produced by the reaction: C O(g) + H 2O(g) → CO 2(g) + H 2(g).

4.42. Chlorine is produced by the reaction: 4HCl(g) + O 2(g) → 2 H 2O(g) + 2 Cl 2(g). The

CO 2 + C → 2CO  and   2C + O 2 → 2CO

n air-cooled condenser transfers heat at a rate of 12(Btu)·s−1 to ambient air at

n air-conditioning unit cools 50(ft)3·s−1 of air at 94(°F) to 68(°F). What is the