Thermo Heat Effects

CHAPTER 4
HEAT EFFECTS
2006/2007 II
BKF2413 Chemical Engineering Thermodynamics
4.1 SENSIBLE HEAT EFFECTS

Is defined as heat transfer to a system in which
there are no phase transition,
transition no chemical
reactions,
reactions and no changes in composition and
resulted in temperature changes.
changes
The molar or specific internal energy of substance
can be expressed as a function of two other state
variables. These may be arbitrarily selected as
temperature and molar or specific volume:
Whence,
U f T ,V
dU
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U
dV
V T
dT
V
U
dU CV dT
dV
V T
BKF2413 Chemical Engineering
dV 0
V T
under two circumstances:
For any constant-volume process, regardless of

substance.
Whenever the internal energy is independent of
volume, regardless of the process. This is exactly
true for ideal gases and incompressible fluids and
approximately true for low-pressure gases.
In these cases:
dU CV dT
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T2
U CV dT
T1
For a mechanically reversible constantvolume process, Q U T CvdT
T1
The molar or specific enthalpy may be

expressed as a function of temperature and
pressure: H f T , P
Whence,
H
H
dH
dT
dP
T P
P T
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and
H
dP
P T
dH C P dT
dP 0 under two circumstances:

P T
For any constant-pressure process, regardless of

substance.
Whenever the enthalpy is independent of
pressure, regardless of the process. This is exactly
true for ideal gases and approximately true for
low-pressure gases.
dH C P dT
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T2
H C P dT
T1
Moreover, Q = H for mechanically

reversible, constant-pressure, and for the
transfer of heat in steady-flow exchangers
where Ep and EK are negligible and
Ws = 0
T2
Q H C P dT
T1
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Temperature Dependence of The Heat

Capacity
.
Integral of equation in previous slide is given by an
empirical equation of the forms of either:
CP
T T 2
R
CP
a bT cT 2
R
where , & and a, b & c are constants characteristic of

the particular substance.
Combining both expressions, a generic equation produced:
CP
A BT CT 2 DT 2
R
where either C or D is zero, depending on the substance

considered.
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For ideal-gas heat capacity:

C Pig
A BT CT 2 DT 2
R
Values of parameters are given in Table C.1

for number of common organic and
inorganic gases.
Two ideal-gas heat capacities are related:
ig
V
ig
P
C
C
1
R
R
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Example 4.1
The parameters listed in Table C.1 require use of
Kelvin temperatures in Eq. (4.4). Equations of the
same form may also be developed for use with
temperatures in C, (R), and (F), 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 (K) by:
C Pig
1.702 9.081 10 3 T 2.164 10 6 T 2
R
where the parameter values are from Table C.1.

Develop an equation for C Pig
for T in C.
R
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Solution 4.1 :
The relation between the two temperature scales is:
T K = t0C + 273.15
Therefore, as a function of
C Pig
2
1.702 9.08110 3 t 273.15 2.164 10 6 t 273.15
R
or
C Pig
4.021 7.899 10 3 t 2.164 10 6 t 2
R
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Evaluation of the Sensible Heat

Integral
Evaluation of C dT is accomplished by
substitution for cp, followed by formal
integration.
T
T C
B 2 2
C 3 3
D 1 where
P
T R dT AT0 1 2 T0 1 3 T0 1 T0
T0
P
The above equation is to solve Q or H

given T and T.
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If given Q or H and you are asked to calculate T,

you need to iterate. Rearrange to get:
T
To
B
C 2 2
D
dT A To ( 1) To ( 1) 2 (T To )
R
2
3
To
Cp
Identify the quantity in square brackets as

CP
where
capacity:
H
CP
CP
R
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is defined as a mean heat
B
C
D
T0 1 T02 2 1 2
2
3
T0
12
Then, H C P H T T0
Solution for T, T H T
CP
A starting value for T (and hence for = T/T0)

allows evaluation of C P H
Substitution of this value into equation above
.
provides
a new value of T from which to reCP H
evaluate
Iteration continue to convergence on a final value
of T.
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Example 4.2
Calculate the heat required to raise the temperature of 1 mol of
methane from 260 to 600C in a steady-flow process at a pressure
sufficiently low that methane may be considered an ideal gas.
Solution 4.2:
Equation (4.3) in combination with Eq. (4.7) provides the required
ig
C
P
result. Parameters for
R
come from Table C. 1; temperatures are:
T0 = 533.15 K
873.15
1.6377
533.15
T = 873.15 K
C Pig
Q R
dT
533.15 R
873.15
Whence,
9.081 10 3 2 2
2.164 10 6 3 3
Q 8.314 1.702T0 1
T0 1
T0 1 19,778 J
2
3
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Example 4.3
What is the final temperature when heat in the amount of 0.4 x 106
(Btu) is added to 25 (Ib mol) of ammonia initially at 500(F) in a
steady-flow process at 1 (atm)?
Solution 4.3
If H is the enthalpy change for 1(Ib mol), Q = n H. And
Q 0.4 10 6
1
H
16,000 Btu Ibmol
n
25
The heat-capacity equation requires temperatures in kelvins; therefore,

conversion of all units to the SI system is indicated. Since 1 J mo1-1 is
equivalent to 0.4299(Btu)(lb mol)-1, divide the preceding result by
0.4299:
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H =16,000/0.4299 = 37,218 J mol-1

With
500 459.67
T0
533.15 K
1.8
then for any value of T:
CP
R
MCPH 533.15, T ;3.578,3.020 E 3,0.0,0.186 E 5
Iteration between this eqn and Eq. (4.10) starts with a value T T0 ,
and converges on the final value:
T = 1,250 K
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or
1,790 ( F )
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4.2 LATENT HEATS OF PURE SUBSTANCES
Heat that is required when a pure substance

is liquefied from solid or vaporized from
liquid at constant pressure. In this process
no change in temperature occurs.
Clapeyron equation: H TV dP
sat
dT
where for a pure species at temperature T,

H = latent heat, V = volume change
accompanying the phase change, Psat =
vapor pressure.
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For vaporization of a pure liquid , dPsat/dT is

the slope of the vapor PT curve at the
temperature of interest.
V is the difference between molar
volumes of saturated liquid and saturated
vapor, and H is the latent heat of
vaporization.
H can calculated from vaporpressure and
volumetric data.
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Rough estimates of latent heats of

vaporization for pure liquids at their normal
boiling points are given by Troutons rule:
H n
10
RTn
where Tn = absolute temperature at the

normal boiling point.
As comparison ~~** [Ar,8.0; N2,8.7; O2,9.1;
HCl,10.4; C6H6,10.5; H2S,10.6 & H2O,13.1]
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Equation proposed by Riedel:
H n 1.092 ln Pc 1.013
RTn
0.930 Trn
where Pc = critical pressure, Trn = reduced

temperature at Tn .
Estimates of the latent heat of vaporization of pure
liquid at any temperature from the known value at
a single temperature may be based on a known
experiment value or on the value estimated by
equation above.
The method proposed by Watson has found wide
acceptance : H 1 T
0.38
H 1
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r2
1 Tr
1
20
Example 4.4
Given that the latent heat of vaporization of water at 1000C is
2,257 J g-1, estimate the latent heat at 300C.
Solution 4.4
Let H1 = latent heat at 1000C = 2.257 Jg -1
H2= latent heat at 3000C
Tr1 =373.15/647.1 =0.577
Tr2 =573.15/647.1 = 0.886
Then by Eq. (4.13),
1 0.886
H 2 2,257
0
.
577
0.38
2,257 0.270
0.38
1,371Jg 1
The value given in the steam tables is 1,406 Jg-1.

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4.3 STANDARD HEAT OF REACTION

A standard state is a particular state of a
species at temperature T and at specified
conditions of pressure, composition and
physical condition as eg. gas, liquid or solid.
A standard state pressure of 1 standard
atmosphere (101,325 Pa) was in use for many
years. The standard is now 1 bar (105 Pa)
For composition, the standard states are pure
species.
Gases: The pure substance in the ideal-gas
state at 1 bar
Liquids and solids: The real pure liquid and solid
at 1 bar .
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4.4 STANDARD HEAT OF FORMATION

A formation reaction is defined as a reaction
which forms a single compound from its
constituent elements, e.g. C 1 O 2 H CH OH
2
Formation reactions are understood to result in

the formation of 1 mol of compound; the heat
of formation is therefore based on 1 mol of the
compound formed.
Hf298 = Standard heat of formation of a
compound at 298.15 K or 25C.
An abridged list of values is given in Table C.4 of
App. C.
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Example 4.5
Calculate the standard heat at 25C for the following reaction :
4HCl(g) + O2(g) 2H2O(g) + 2Cl2(g)
Solution 4.5
Standard heats of formation at 298.15 K from Table C.4 are :
HCl (g) :-92,307 J
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H2O (g) :-24,818J
24
The following combination gives the desired result :

4HCl (g) 2H2 (g) + 2Cl2 (g) H298=(4)(92,307)
2H2 (g) + O2 (g) 2H2O (g)
H298=(2)(-241,818)
4HCl (g) + O2 (g) 2H2O (g) + 2Cl2 (g)

H298 = -114,408 J
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4.5 STANDARD HEAT OF COMBUSTION

Only a few formation reactions can actually be
carried out , and therefore data for these
reactions must usually be determined indirectly.
Combustion reaction is defined as a reaction
between an element of compound and oxygen
to form specified combustion products .
A reaction such as the formation of n-butane:
4C s 5H 2 g C 4 H10 g
cannot
be carried out in practice.
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However , this equation results from

combination of the following combustion
reactions:
4C s 4O 2 g
4CO 2 g
0
H 298
4 393509
1
5H 2 g 2 O 2 g
2
5H 2 O l
0
H 298
5 285830
4CO 2 g 5H 2 O l
1
C 4 H10 g 6 O 2 g
2
4C s 5H 2 g
C 4 H10 g
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0
H 298
2877396
0
H 298
125790 J
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4.6 TEMPERATURE DEPENDENCE OF H

The general chemical reaction may be written:
1 A1 2 A2 ... 3 A3 4 A4 ...
where |vi| is a stoichiometric coefficient and Ai
stands for chemical formula.
If we assign the following sign convention for vi:
(+) for products; (-) for reactants: e.g.
H 2 1 O2 H 2O
2
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H 2 1;O2 1 ; H 2O 1
2
28
The vi with their accompanying signs are called

stoichiometric numbers.
This sign convention allows the definition of a
standard heat of reaction to be expressed
mathematically by the equation:
H i H i
i
where Hio is the enthalpy of species i in its

standard state and the summation is over all
products and reactants.
The standard-state enthalpy Hio of chemical
compound is equal to its heat of formation plus the
standard-state enthalpies of its constituent
elements.
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At standard-state enthalpies of all elements are

arbitrarily set equal zero as
the basis
of calculation.
H i H f
As such:
i
i
where the summation is over all products &

reactants.
This is the fundamental equation relating standard
heats of reaction to temperature. Integration gives:
T
H H R C P dT
T0
where Ho and H0o are heat of reaction at

temperature T and at reference temperature T0
respectively. Standard here refers to P = 1 bar.
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C P
B 2 2
C 3 3
D 1
dT
AT
0
0
0
T0 R
2
3
T0
o
A i Ai
where by definition
and so on
Mean heat capacity change of reaction is
defined in analogy:
C
B
C
D
A
T 1
T 1
R
2
3
T
i
2
0
2
0
Equation then become:

H H 0 C P
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T T0
H
31
Example 4.6
Calculate the standard heat of the methanol-synthesis reaction at 800 oC:
CO (g) + 2H2 (g) CH3OH (g)
Solution 4.6:
Apply Eq. (4.15) to this reaction for reference temperature
T0 = 298.15 K and with heat-of-formation data from Table C.4:
H 0 H 298
200,660 110,525 90,135 J
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Evaluation of the parameters in Eq. (4.19) is based on data taken

from Table C.1:
i
10 3 B
CH3OH
2.211
12.216
-3.450
0.000
CO
-1
3.376
0.557
0.000
-0.03 1
H2
-2
3.249
0.422
0.000
0.083
106C
10-5D
From its definition,

A = (1)(2.21 1) + (-1)(3.376) + (-2)(3.249) = -7.663
Similarly, B = 10.8 15 x l0-3
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C = -3.450 x l0-6 D = -0.135 x l05
33
The value of the integral of Eq. (4.19) for T = 1,073.15 K is

represented by:
IDCPH(298.15,1073.15;-7.663, 10.815E-3,-3.450E-6,-0.135E+5)
= -1,615.5 K
Then by Eq. (4.18),
H = -90,135 + 8.314(-l,615.5) = -l03,566J
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4.7 HEAT EFFECTS OF INDUSTRIAL

REACTIONS
Industrial reactions are rarely carried out

under standard-state conditions.
In actual reactions the reactants may not
be present in stoichiometric proportions,
the reaction may not go to completion,
and the final temperature may differ from
the initial temperature.
Inert species may be present and several
reactions may occur simultaneously.
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Calculations of the heat effects of actual

reactions are based on the principles
already considered and are best
illustrated by example.
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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 25C.
Solution
The reaction is CH4 + 2O2 CO2 + 2H2O(g)
for which
H298=-393,509 + (2)(-241,818) - (-74,520) 802.625 J
Since 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 H = 0. For purposes of calculation of the final
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Since 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 H = 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.
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When one mole of methane burned is the

basis for all calculations, the following
quantities of oxygen and nitrogen are
supplied by the entering air:
Moles 02 required = 2.0
Moles excess 02 = (0.2)(2.0) = 0.4
Moles N2 entering = (2.4)(79/21) = 9.03
The gases leaving the burner contain 1 mol
CO2 , 2 mol H2O(g) , 0.4 mol O2 and 9.03 mol
N2. Since the enthalpy change must be
independent of path.
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H 298
H P H 0
(A)
T 298.15
H
(B)
H P C P
C P
where we define
as the mean heat
capacity for the total product stream:
The simplest procedure here is to sum the
mean-heat-capacity equations for the
products, each multiplied by its appropriate
mole number. Since C = 0 for each product
gas (Table C.1), Eq. (4.8) yields:
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C
i
ni Ai
nB
nD
T 1
T02
Data from Table C.1 are combined as follows:

A ni Ai 1 5.457 2 3.470 0.4 3.639 9.03 3.280 43.471
i
Similarly,
B ni Bi 9.502 x10 3
D ni Di 0.645x105
i
C P
For the product stream

/R is therefore
represented by:
MCPH(298. 15,T; 43.471,9.502E-3,0.0,-0.645
E+5)
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Equations (A) and (B) may be combined
H
and solved for TT: 298.15 298
C P
Because the mean heat capacities depend

on T, first evaluate C
for an assumed
value of T>298.15, and substitute the result
in the preceding equation. This yields a new
value of T for which C is reevaluated.
The procedure continues to convergence on
the final value, T = 2,066 K or 1,793C
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Example 4.8
One method for the manufacture of synthesis gas (primarily a mixture of CO and H2) is the
catalytic reforming of CH4 with steam at high temperature and atmospheric pressure:
CH4(g) H2O(g) CO(g) 3H2(g)
The only other reaction which occurs to an appreciable extent is the water-gas-shift reaction:
CO(g) + H2O(g) CO2(g) + H2(g)
If the reactants are supplied in the ratio, 2 mol steam to 1 mol CH4, and if heat is supplied to the
reactor so that the products reach a temperature of 1,300 K, the CH4 is completely converted
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.
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Solution 4.8
The standard heats of reaction at 25C for the two reactions are calculated from the data of
Table C.4:
CH4 (g) + H2O (g) CO (g) + 3H2(g) H298= 205,813 J
CO (g) +H2O (g) CO2 (g) +H2 (g) H298= -41,166 J
These two reactions may be added to give a third reaction:
CH4(g) + 2H2O(g) CO2(g) + 4H2(g) H298= 164,647 J
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Any pair of the three reactions constitutes an independent set. The third reaction is not
independent, since it is obtained by combination of the other two. The reactions most
convenient to work with here are:
CH4(g) + H2O(g) CO(g) +3H2(g)
H298= 205,813 J
(A)
CH4(g) +2H2O(g) CO2(g) +4H2(g)
H298= 164,647J
(B)
First 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).
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On this basis the products of the reaction are:

CO:
x
H2:
3x + 4(1 - x) = 4 - x
CO2:
1- x
H2O:
2x2(1x)=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).
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Furthermore, the amounts of the species in the product stream are:

Moles CO = x = 0.87
Moles H2 = 4 - x = 3.13
Moles CO2 = 1 - x = 0.13
Moles H2O = x =0 87
We now devise a path, for purposes of calculation, to proceed from reactants at 600 K to
products at 1.300 K. Since data are available for the standard heats of reaction at 25 0C. the most
convenient path is the one which includes the reactions at 25C (298.15 K). This is shown
schematically in the accompanying diagram. The dashed line represents the actual path for
which the enthalpy change is z\H. Since this enthalpy change is independent of path,
H H R H 298
H P
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For the calculation of H298 , reactions (A) and (B) must both be taken into account.
Since 0.87 mol CH4 reacts by (A) and 0.13 mol reacts by (B).
H298 =(0.87)(205,8l3) + (0.l3)(164,647) = 200.460J
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The enthalpy change of the reactants for cooling from 600 K to 298. 15 K is:
H R
where the values of

CH4:
H2O:
C Pi
n
i
C Pi
298.15 600
are:
MCPH(298.l5,600;l .702,9.081 E-3,-2.1 64E-6,0.0) = 5.3272

MCPH(298.15,600;3.470,1.450E-3,0.0,0.121E+5) = 4.1888
Whence.
H R 8.314 1 5.3272 2 4.1888 298.15 600 34,390 J
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The enthalpy change of the products as they are heated from 298.15 to 1300 K is calculated
similarly:
H P
where
Pi
n
i
C Pi
1,300 298.15
values are:
CO: MCPH(298.15,1300;3.376,0.557E-3,0.0,-0.031E+5) = 3.8131

H2: MCPH(298.15,1300;3.249,0.422E-3,0.0,0.083E+5) = 3.6076
CO2: MCPH(298.15,1300;5.457,1.045E-3,0.0,-1.157E+5) = 5.9935
H20: MCPH(298.15,1300;3.470,1.450E-3,0.0,0.1 21 E+5) = 4.6599
Whence,
HP =(8.314)[(0.87)(3.8131) + (3.13)(3.6076)+(0.13)(5.9935) + (0.87)(4.6599)] x (1,300298.15) = 161,940J
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Therefore,
HP=
-34,390 + 200,460 + 161,940 = 328,010J
The process is one of steady flow for which Ws, z , and u2/2 are presumed negligible.
Thus.
Q = H = 328,010J
This result is on the basis of 1 mol CH4 fed to the reactor.
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Example 4.9
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 25C with CO2(g) and H2O(l) as products. The temperature
of the fuel and air entering the combustion chamber is 25C. The air is assumed dry. The flue gases
leave at 300C, and their average analysis (on a dry basis) is 11.2% CO 2 , 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.
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Solution 4.9
Take as a basis 100 mol dry flue gases, consisting of:
CO2
CO
O2
N2
Total
ll.2mol
0.4 mol
6.2 mol
82.2 mol
100.0 mol
This analysis, on a dry basis, does not take into account the H20 vapor present in the flue
gases. The amount of H20 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.
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Thus the 82.2 mol N2 appearing in 100 mol dry flue gases is supplied with the air, and the 02
accompanying this N2 is:
Moles O2 entering in air = (82.2)(21/79) = 21.85
However,
Moles O2 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 H2O formed = (21.85 - 17.60)(2) = 8.50
Moles H2 in the fuel = moles of water formed = 8.50
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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 25C, the heat of
combustion is:
H298 = (-43,515)(156.2) = -6,797,040J
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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, consisting 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:
C11.6H17(l) + 15.65O2 (g) 11.2 CO2(g) + 0.4 CO(g) + 8.5 H2O(g)
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This result is obtained by addition of the following reactions, for each of which the
standard heat of reaction at 25C is known:
C11.6H17(l) + 15.85O2(g) 11.6CO2(g) + 8.5H20(l)
8.5H20(l) 8.5H2O(g)
0.4CO2(g) 0.4CO(g) + 0.2O2(g)
The sum of these reactions yields the actual reaction. and the sum of the H298 values
gives the standard heat of the reaction occurring at 25 C:
H298 = -6,797,040 + (44,012)(8.5) + (282,984)(0.4) = -6,309,740 J
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The actual process leading from reactants at 25C to products at 300C is represented by
the dashed line in the accompanying diagram. For purposes of calculating H for this
process, we may use any convenient path. The one drawn with solid lines is a logical one:
H298 has already been calculated and HP is easily evaluated.
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59
The enthalpy change caused by heating the products of reaction from 25 to 300C is:
H P
where the
CO2:
CO:
H2O:
O2:
N2:
2006/200
C Pi
n
i
C Pi
573.15 298.15
values are:
MCPH(298.15,573.15;5.457,1.045E-3,0.0,-1.157E+5) = 5.2352
MCPH(298.15,573.15;3.376,0.557E-3,0.0,-0.031 E+5) = 3.6005
MCPH(298.15,573.15;3.470,1.450E-3,0.0,0.121 E+5) = 4.1725
MCPH(298.15,573.15;3.639,0.506E-3,0.0,-0.227E+5) = 3.7267
MCPH(298.15,573.15;3.280,0.593E-3,0.0,0.040E+5) = 3.5618
60
Whence.
HP =(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) = 940,660J
and
H H 298
H P 6,309,740 940,660 5,369,080 J
Since 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 negligible, H = Q. Thus.
Q =5,369.08 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 heat of combustion of the fuel.
2006/200
61

Thermo Heat Effects

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Thermo Heat Effects

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CHAPTER 4

BKF2413 Chemical Engineering Thermodynamics

4.1 SENSIBLE HEAT EFFECTS

BKF2413 Chemical Engineering

under two circumstances:

For any constant-volume process, regardless of

BKF2413 Chemical Engineering

For a mechanically reversible constantvolume process, Q U T CvdT

The molar or specific enthalpy may be

BKF2413 Chemical Engineering

dP 0 under two circumstances:

For any constant-pressure process, regardless of

BKF2413 Chemical Engineering

Moreover, Q = H for mechanically

BKF2413 Chemical Engineering

Temperature Dependence of The Heat

where , & and a, b & c are constants characteristic of

where either C or D is zero, depending on the substance

BKF2413 Chemical Engineering

For ideal-gas heat capacity:

Values of parameters are given in Table C.1

BKF2413 Chemical Engineering

where the parameter values are from Table C.1.

BKF2413 Chemical Engineering

BKF2413 Chemical Engineering

Evaluation of the Sensible Heat

The above equation is to solve Q or H

BKF2413 Chemical Engineering

If given Q or H and you are asked to calculate T,

Identify the quantity in square brackets as

is defined as a mean heat

BKF2413 Chemical Engineering

A starting value for T (and hence for = T/T0)

BKF2413 Chemical Engineering

BKF2413 Chemical Engineering

The heat-capacity equation requires temperatures in kelvins; therefore,

BKF2413 Chemical Engineering

H =16,000/0.4299 = 37,218 J mol-1

MCPH 533.15, T ;3.578,3.020 E 3,0.0,0.186 E 5

BKF2413 Chemical Engineering

4.2 LATENT HEATS OF PURE SUBSTANCES

Heat that is required when a pure substance

where for a pure species at temperature T,

BKF2413 Chemical Engineering

For vaporization of a pure liquid , dPsat/dT is

BKF2413 Chemical Engineering

Rough estimates of latent heats of

where Tn = absolute temperature at the

BKF2413 Chemical Engineering

Equation proposed by Riedel:

where Pc = critical pressure, Trn = reduced

BKF2413 Chemical Engineering

The value given in the steam tables is 1,406 Jg-1.

BKF2413 Chemical Engineering

4.3 STANDARD HEAT OF REACTION

BKF2413 Chemical Engineering

4.4 STANDARD HEAT OF FORMATION

Formation reactions are understood to result in

BKF2413 Chemical Engineering

H2O (g) :-24,818J

BKF2413 Chemical Engineering

The following combination gives the desired result :

4HCl (g) + O2 (g) 2H2O (g) + 2Cl2 (g)

BKF2413 Chemical Engineering