Numerical A

Techniques

Lake Michigan—unsalted and shark free.

A.1 Useful Integrals in Reactor Design

Also see www.integrals.com.

x dx 1
! 0
------------ " ln ------------
1!x 1!x
(A-1)

x2
dx 1 1
! x1
-----------------2- " -------------- ! --------------
(1 ! x) 1 ! x 2 1 ! x1
(A-2)

x dx x
! 0
-----------------2- " ------------
(1 ! x) 1!x
(A-3)

x dx 1
! 0
--------------- " --- ln ( 1 $ #x )
1 $ #x #
(A-4)

x
(------------------------
1 $ #x )dx- " ( 1 $ # ) ln -----------
1 -
! 0 1!x 1!x
! #x (A-5)

x
( 1 $ #x )dx " (-------------------
1 $ # ) x- 1
!0
------------------------
(1 ! x)
2
-
1!x
! # ln ------------
1!x
(A-6)

2
x ( 1 $ #x )2dx " 2#( 1 $ # ) ln ( 1 ! x ) $ #2x $ ( 1 $ # ) x
! 0
--------------------------
( 1 ! x )2
- ---------------------
1!x
(A-7)

715
716 Numerical Techniques Appendix A

x dx 1 &B ! x
! 0
------------------------------------- " ---------------- ln ------------------------
( 1 ! x ) ( &B ! x ) &B ! 1 &B ( 1 ! x )
&B ' 1 (A-8)

W
2
!
1)2 3)2
( 1 ! (W ) dW " ------ [ 1 ! ( 1 ! (W ) ] (A-9)
0 3(

x dx !2 2
! 0
--------------------------- " ----------------- $ ---
ax2 $ bx $ c 2ax $ b b
for b2 " 4ac (A-10)

x dx 1  q x ! p
! 0
--------------------------- " ------------------
ax2 $ bx $ c a ( p ! q )  p x ! q
- ln  -- * ----------- for b2 + 4ac (A-11)

where p and q are the roots of the equation.

! b , b2 ! 4ac
ax2 $ bx $ c " 0 i.e., p, q " --------------------------------------
2a

x a $ bx bx ag ! bc c $ gx
! 0
-------------- dx " ----- $ ---------------
c $ gx g g2
- ln -------------
c
(A-12)

A.2 Equal-Area Graphical Differentiation

There are many ways of differentiating numerical and graphical data (cf. Chapter 7). We shall confine
our discussions to the technique of equal-area differentiation. In the procedure delineated here, we
want to find the derivative of y with respect to x.
This method finds use in Chapter 5.

1. Tabulate the ( y i , xi ) observations as shown in Table A-1.

2. For each interval, calculate %xn " xn ! xn!1 and %yn " yn ! yn!1 .

TABLE A-1

%y dy-
xi yi %x %y ------ ----
%x dx

 dy
x1 y1  -----
 dx 1
 %y
x2 ! x1 y2 ! y1  ------
 %x 2
 dy
x2 y2  -----
 dx 2
 %y
x3 ! x2 y3 ! y2  ------
 %x 3
 dy
x3 y3  -----
 dx 3
x4 y4 etc.
Section A.2 Equal-Area Graphical Differentiation 717

3. Calculate %yn / %xn as an estimate of the average slope in an interval xn!1 to xn .

4. Plot these values as a histogram versus xi . The value between x2 and x3 , for example, is
( y3 ! y2 )/(x3 ! x2 ). Refer to Figure A-1.

Figure A-1 Equal-area differentiation.

5. Next, draw in the smooth curve that best approximates the area under the histogram. That is,
attempt in each interval to balance areas such as those labeled A and B, but when this
approximation is not possible, balance out over several intervals (as for the areas labeled C
and D). From our definitions of %x and %y, we know that

n
%y
yn ! y1 "
" -------
% xi i
%x (A-13)
i"2

The equal-area method attempts to estimate dy / dx so that

xn
dy
yn ! y1 "
! x1
----- dx
dx
(A-14)

that is, so that the area under %y / %x is the same as that under dy / dx, everywhere possible.
6. Read estimates of dy / dx from this curve at the data points x1 , x2 , … and complete the table.

An example illustrating the technique is given on the CRE Web site, Appendix A.
Differentiation is, at best, less accurate than integration. This method also clearly indicates bad data
and allows for compensation of such data. Differentiation is only valid, however, when the data are
presumed to differentiate smoothly, as in rate-data analysis and the interpretation of transient diffusion
data.
718 Numerical Techniques Appendix A

A.3 Solutions to Differential Equations

A.3.A First-Order Ordinary Differential Equations

See the CRE Web site, Appendix A.3.

dy
----- $ f ( t )y " g( t ) (A-15)
dt

Using integrating factor = exp  f dt , the solution is

!
 

!
! f dt
! f dt
!
! f dt
y"e ! g(t) e dt $ K1e (A-16)

Example A–1 Integrating Factor for Series Reactions

dy $ k y " k e!k1t
----- 2 1
dt
Comparing the above equation with Equation (A-15) we note
f (t) = k2

and the integrating factor = exp ! k2 dt " e

k2 t

Integrating factor = exp ! k2 dt " e

k2 t

k2 t
d( ye ) k2 t !k1 t ( k2 ! k1 )t
---------------- " e k1 e " k1 e
dt
k2 t ( k2 ! k1 )t k1 (k2 ! k1)t
e y " k1 ! e dt " --------------
-e $ K1
k2 ! k1
k 1 !k1 t !k2 t
y " --------------
-e $ K1 e
k2 ! k1

t=0 y=0

k1 !k1 t !k2 t
y " --------------
- e !e
k2 ! k1

A.3.B Coupled Differential Equations

Techniques to solve coupled first-order linear ODEs such as

dx " ax $ by
-----
dt
Section A.4 Numerical Evaluation of Integrals 719

dy
----- " cx $ dy
dt

are given in Web Appendix A.3 on the CRE Web site (http://www.umich.edu/~elements/5e/appendix/
AppA.3_Web.pdf).

A.3.C Second-Order Ordinary Differential Equations

Methods of solving differential equations of the type

d2y
-------2 ! -y " 0 (A-17)
dx

can be found in such texts as Applied Differential Equations by M. R. Spiegel (Upper Saddle River,
NJ: Prentice Hall, 1958, Chapter 4; a great book even though it’s old) or in Differential Equations by
F. Ayres (New York: Schaum Outline Series, McGraw-Hill, 1952). Solutions of this type are required in
PDF Chapter 15. One method of solution is to determine the characteristic roots of

 d2 
 -------2 ! - y " (m2 ! -)y
 dx 

which are

m". -

The solution to the differential equation is

y " A1 e ! -x $ B
1e
$ -x (A-18)

where A1 and B1 are arbitrary constants of integration. It can be verified that Equation (A-18) can be
arranged in the form

y " A sinh -x $ B cosh -x (A-19)

Equation (A-19) is the more useful form of the solution when it comes to evaluating the constants A
and B because sinh(0) " 0 and cosh(0) " 1.0. Also see Appendix A.3.B.

A.4 Numerical Evaluation of Integrals

In this section, we discuss techniques for numerically evaluating integrals for solving first-order dif-
ferential equations.

1. Trapezoidal rule (two-point) (Figure A-2). This method is one of the simplest and most approx-
imate, as it uses the integrand evaluated at the limits of integration to evaluate the integral
X1
h
! X0
f ( X ) dX " --- [ f ( X0 ) $ f ( X1 ) ]
2
(A-20)

when h " X1 ! X0 .
720 Numerical Techniques Appendix A

2. Simpson’s one-third rule (three-point) (Figure A-3). A more accurate evaluation of the integral
can be found with the application of Simpson’s rule:
X2
h
! X0
f ( X ) dX " --- [ f ( X0 ) $ 4f ( X1 ) $ f ( X2 ) ]
3
(A-21)

where
X2 ! X0
h " -----------------
- X1 " X0 $ h
2

Methods to solve
X F
!0 --------
!rA
A0
- dX

in Chapters 2, 4, 12,
and
/
!0 X (t)E (t) dt
in PDF Chapter 17

Figure A-2 Trapezoidal rule illustration. Figure A-3 Simpson’s three-point rule
illustration.
3. Simpson’s three-eighths rule (four-point) (Figure A-4). An improved version of Simpson’s
one-third rule can be made by applying Simpson’s three-eighths rule:
X3

!X0
f ( X ) dX " 3--8- h [ f ( X0 ) $ 3f ( X1 ) $ 3f ( X2 ) $ f ( X3 ) ] (A-22)

where
X3 ! X0
h " -----------------
- X1 " X0 $ h X2 " X0 $ 2h
3

Figure A-4 Simpson’s four-point rule illustration.

4. Five-point quadrature formula.

X4
h
! X0
f ( X ) dX " --- ( f0 $ 4f1 $ 2f2 $ 4f3 $ f4 )
3
(A-23)

X4 ! X0
where h " -----------------
-
4
Section A.6 Software Packages 721

5. For N $ 1 points, where (N /3) is an integer

XN

!X0
f ( X ) dX " 3--8- h [f0 $ 3f1 $ 3f2 $ 2f3

$ 3f4 $ 3f5 $ 2f6 $ *** $ 3fN!1 $ fN ] (A-24)

XN ! X0
where h " ------------------
-
N
6. For N $ 1 points, where N is even
XN
h
! X0
f ( X ) dX " --- ( f0 $ 4f1 $ 2f2 $ 4f3 $ 2f4 $ *** $ 4fN!1 $ fN )
3
(A-25)

XN ! X0
where h " ------------------
-
N
These formulas are useful in illustrating how the reaction engineering integrals and coupled
ODEs (ordinary differential equation(s)) can be solved and also when there is an ODE solver power
failure or some other malfunction.

A.5 Semilog Graphs

Review how to take slopes on semilog graphs on the Web. Also see www.physics.uoguelph.ca/tutorials/
GLP. Also see Web Appendix A.5, Using Semi-Log Plots for Data Analysis.

A.6 Software Packages

Instructions on how to use Polymath, COMSOL, and Aspen can be found on the CRE Web site.
For the ordinary differential equation solver (ODE solver), contact:
Polymath Software Aspen Technology, Inc.
P.O. Box 523 10 Canal Park
Willimantic, CT 06226-0523 Cambridge, MA 02141-2201
Web site: Email: info@aspentech.com
www.polymathsoftware.com/fogler www.aspentech.com

MATLAB COMSOL, Inc.

The Math Works, Inc. 1 New England Executive Park
20 North Main Street, Suite 250 Burlington, MA 01803
Sherborn, MA 01770 Tel: +1-781-273-3322
www.mathworks.com Fax: +1-781-273-6603
Email: info@comsol.com
Wolfram www.comsol.com
100 Trade Center Drive
Champaign, IL 61820-7237
Tel: +1-217-398-0700
+1-800-WOLFRAM (965-3726)
Fax: +1-217-398-0747
www.wolfram.com
This page intentionally left blank
 Ideal Gas Constant B
and Conversion
Factors

See www.onlineconversion.com.

Ideal Gas Constant

0.73 ft3 # atm 1.987 Btu
R ! ------------------------------ R ! -------------------------
lb mol # "R lb mol # "R
8.314 kPa # dm3 8.3144 J
R ! ------------------------------------- R ! -------------------
mol # K mol # K
dm3 # atm 0.082 m3 # atm 1.987cal
R ! 0.082 ----------------------- ! ---------------------------------- R ! --------------------
mol # K kmol # K mol # K
J
Boltzmann’s constant kB ! 1.381 × 10–23 ----------------------------
-
molecule # K
! 1.381 × 10–23 kg m2/s2/molecule/K

Volume of Ideal Gas

1 lb-mol of an ideal gas at 32"F and 1 atm occupies 359 ft3 (0.00279 lbmol/ft3).
1 mol of an ideal gas at 0"C and 1 atm occupies 22.4 dm3 (0.0446 mol/dm3).
PA yA P
CA ! ------ ! -------
-
RT RT
where CA ! concentration of A, mol/dm3 T ! temperature, K
P ! pressure, kPa yA ! mole fraction of A
R ! ideal gas constant, 8.314 kPa#dm3/mol#K

1M = 1 molar = 1 mol/liter = 1 mol/dm3 = 1 kmol/m3 = 0.062 lb mol/ft3

723
724 Ideal Gas Constant and Conversion Factors Appendix B

Volume Length
1 cm3 ! 0.001 dm3 1 Å ! 10$8 cm
1 in3 ! 0.0164 dm3 1 dm ! 10 cm
1 fluid oz ! 0.0296 dm3 1 %m ! 10$4 cm
1 ft3 ! 28.32 dm3 1 in. ! 2.54 cm
1 m3 ! 1000 dm3 1 ft ! 30.48 cm
1 U.S. gallon ! 3.785 dm3 1 m ! 100 cm
1 liter (L) ! 1 dm3
 1 gal 
 1 ft3 ! 28.32 dm3 & -------------------------3 ! 7.482 gal
 3.785 dm 

Pressure Energy (Work)

1 torr (1 mmHg) ! 0.13333 kPa 1 kg#m2/s2 ! 1 J
1 in. H2 O ! 0.24886 kPa 1 Btu ! 1055.06 J
1 in. Hg ! 3.3843 kPa 1 cal ! 4.1868 J
1 atm ! 101.33 kPa 1 L#atm ! 101.34 J
1 psia ! 6.8943 kPa 1 hp#h ! 2.6806 & 106 J
1 megadyne/cm2 ! 100 kPa 1 kWh ! 3.6 & 106 J

Temperature Mass
"F ! 1.8 & "C ' 32 1 lbm ! 454 g
"R ! "F ' 459.69 1 kg ! 1000 g
"K ! "C ' 273.16 1 grain ! 0.0648 g
"R ! 1.8 & K 1 oz (avoird.) ! 28.35 g
"Réamur ! 1.25 & "C 1 ton ! 908,000 g

Viscosity
1 poise ! 1 g/cm/s = 0.1 kg/m/s
1 centipoise = 1 cp = 0.01 poise = 0.1 micro Pascal ⋅ second

Force
1 dyne ! 1 g ⋅ cm/s2
1 Newton ! 1 kg ⋅ m/s2

Pressure
1 Pa ! 1 Newton/m2

Work
A. Work ! Force × Distance
1 Joule ! 1 Newton ⋅ meter ! 1 kg m2/s2 ! 1 Pa ⋅ m3
B. Pressure × Volume ! Work
(1 Newton/ m2) ⋅ m3 ! 1 Newton ⋅ m ! 1 Joule
Appendix B Ideal Gas Constant and Conversion Factors 725

Time Rate of Change of Energy with Time (Power)

1 Watt ! 1 J/s
1 hp ! 746 J/s

Gravitational Conversion Factor

Gravitational constant
g ! 32.2 ft/s2
American Engineering System
( ft )( lbm )
gc ! 32.174 --------------------
2
( s )( lbf )
SI/cgs System
gc ! 1 (Dimensionless)

TABLE B-1 TYPICAL PROPERTY VALUES

Liquid Gas
(water) (air, 77°C, 101 kPa) Solid
Density 1000 kg/m3 1.0 kg/m3 3000 kg/m3
Concentration 55.5 mol/dm3 0.04 mol/dm3 –
Diffusivity 10–8 m2/s 10–5 m2/s 10–11 m2/s
Viscosity 10–3 kg/m/s 1.82 × 10–5 kg/m/s –
Heat capacity 4.31 J/g/K 40 J/mol/K 0.45 J/g/K
Thermal conductivity 1.0 J/s/m/K 10–2 J/s/m/K 100 J/s/m/K
Kinematic viscosity 10–6 m2/s 1.8 × 10–5 m2/s –
Prandtl number 7 0.7 –
Schmidt number 200 2 –

TABLE B-2 TYPICAL TRANSPORT VALUES

Liquid Gas
Heat transfer coefficient, h 1000 W/m2/K 65 W/m2/K
Mass transfer coefficient, kc 10–2 m/s 3 m/s
This page intentionally left blank
 Thermodynamic C
Relationships
Involving
the Equilibrium
Constant 1

For the gas-phase reaction

b → c d
A $ -- B ← -- C $ -- D (2-2)
a a a
1. The true (dimensionless) equilibrium constant
RT lnK ! "#G

c%a d%a
aC aD
K ! ----------------
b%a
aA aB

where ai is the activity of species i

f
ai ! ---i
fi&
where f i ! fugacity of species i
f i& ! fugacity of species i at the standard state. For gases, the
standard state is 1 bar, which is in the noise level of
1 atm, so we will use atm.
f
ai ! ---i ! 'i Pi
f i&

1 For the limitations and for further explanation of these relationships, see, for example,
K. Denbigh, The Principles of Chemical Equilibrium, 3rd ed. (Cambridge: Cambridge Uni-
versity Press, 1971), p. 138.

727
728 Thermodynamic Relationships Involving the Equilibrium Constant Appendix C

where 'i is the activity coefficient

K = True equilibrium
constant c/a d/a c/a d/a
K' = Activity
'C 'D PC PD
K ! -----------------
b/a
- ) -----------------
b/a
- ! K' Kp
equilibrium constant 'A 'B PA PB
Kp = Pressure








equilibrium constant K' Kp
Kc = Concentration
equilibrium constant b
" d / a $ c / a " -- " 1
 
K' has units of [ atm ] a
! [ atm ]"(
 d / a $ c / a " b-- " 1
 
Kp has units of [ atm ] ! [ atm ]( a

For ideal gases K' ! 1.0 atm – δ

2. For the generic reaction (2-2), the pressure equilibrium constant KP is

c/a d/a
PC PD
Kp ! ----------------
b/a
-
PA PB
(C-1)
Pi ! partial pressure of species i, atm, kPa.
Pi ! Ci RT
3. For the generic reaction (2-2), the concentration equilibrium constant
KC is
It is important to be CCc / aCDd / a
able to relate Kc ! ----------------- (C-2)
K, K', Kc , and Kp. CACBb / a
4. For ideal gases, Kc and Kp are related by
Kp !Kc (RT )( (C-3)
Where for the generic reaction (2-2),
c d b
( ! -- $ -- " -- " 1 (C-4)
a a a
5. KP is a function of temperature only, and the temperature dependence
of KP is given by van’t Hoff’s equation:

Van’t Hoff’s d ln Kp #HRx( T )

equation --------------- ! -------------------- (C-5)
dT RT2

d ln K #H&Rx ( TR ) $ #Cp ( T " TR )

---------------p ! -----------------------------------------------------------
- (C-6)
dT RT2
(http://www.umich.edu/~elements/5e/11chap/summary-biovan.html).
6. Integrating, we have

Kp ( T ) #H&Rx ( TR ) " TR #Cp 1 1 # C p T

ln --------------- ! --------------------------------------------
-  ----- " --- $ --------- ln ----- (C-7)
Kp ( T1 ) R  T1 T R T1

Kp and Kc are related by

Kp
Kc ! ------------(- (C-8)
( RT )
Appendix C Thermodynamic Relationships Involving the Equilibrium Constant 729

when
d c b 
( !  -- $ -- " -- " 1 ! 0
a a a 
then
KP ! KC
7. KP neglecting ∆CP. Given the equilibrium constant at one temperature,
T1, KP (T1), and the heat of reaction, #H &Rx , the partial pressure equilib-
rium constant at any temperature T is
#H Rx & ( T R )  1 1
KP(T) = KP(T1)exp ------------------------
- ----- " --- (C-9)
R  T1 T

8. From Le Châtelier’s principle we know that for exothermic reactions,

the equilibrium shifts to the left (i.e., K and Xe decrease) as the temper-
ature increases. Figures C-1 and C-2 show how the equilibrium con-
stant varies with temperature for an exothermic reaction and for an
endothermic reaction, respectively.

Variation of
equilibrium
constant with
temperature

Figure C-1 Exothermic reaction. Figure C-2 Endothermic reaction.

9. The equilibrium constant for the reaction (2-2) at temperature T can

be calculated from the change in the Gibbs free energy using
"RT ln[K (T )] ! # G&Rx (T ) (C-10)

c d b
#G&Rx ! - GC& $ -- GD& " -- GB& " GA& (C-11)
a a a
10. Tables that list the standard Gibbs free energy of formation of a given
species G&i are available in the literature (webbook.nist.gov).
11. The relationship between the change in Gibbs free energy and
enthalpy, H, and entropy, S, is
#G ! #H " T #S (C-12)
See bilbo.chm.uri.edu/CHM112/lectures/lecture31.htm. An example on how to calculate
the equivalent conversion for ∆G is given on the Web site.
730 Thermodynamic Relationships Involving the Equilibrium Constant Appendix C

Example C–1 Water-Gas Shift Reaction

The water-gas shift reaction to produce hydrogen

→ CO2 $ H2
H2 O $ CO ←
is to be carried out at 1000 K and 10 atm. For an equimolar mixture of water and
carbon monoxide, calculate the equilibrium conversion and concentration of each
species.
Data: At 1000 K and 10 atm, the Gibbs free energies of formation are G&CO ! "47,860
cal/mol; G&CO2 ! "94,630 cal/mol; G&H2O ! "46,040 cal/mol; and G&H2 ! 0.

Solution
We first calculate the equilibrium constant. The first step in calculating K is to calculate
the change in Gibbs free energy for the reaction. Applying Equation (C-10) gives us
Calculate #G&Rx #G&Rx ! G&H2 $ G&CO2 " G&CO " G&H2O (EC-1.1)

! 0 $ ("94,630) " ("47,860) " ("46,040)

! "730 cal/mol
"RT ln K ! #G&Rx (T ) (C-10)

#G&Rx ( T ) "( "730 cal % mol ) -

- ! ----------------------------------------------------------------
ln K ! " -------------------- (EC-1.2)
RT 1.987 cal % mol ) K ( 1000 K )
! 0.367
then
Calculate K K ! 1.44
Expressing the equilibrium constant first in terms of activities and then finally in
terms of concentration, we have
aCO2aH2 fCO2 fH2 'CO2 PCO2'H2 PH2
K ! ------------------- ! ------------------
- ! -------------------------------------------
- (EC-1.3)
aCO aH2O fCO fH2O 'CO PCO 'H2O PH2O

where ai is the activity, f i is the fugacity, 'i is the activity coefficient (which we shall
take to be 1.0 owing to high temperature and low pressure), and yi is the mole frac-
tion of species i.2 Substituting for the mole fractions in terms of partial pressures
gives
PCO2PH2
K ! --------------------
- (EC-1.4)
PCO PH2O

Pi ! Ci RT (EC-1.5)

CCO2CH2O
K ! ----------------------
- (EC-1.6)
CCO CH2O

2 See Chapter 17 in J. R. Elliott and C. T. Lira, Introductory Chemical Engineering Thermody-

namics, 2nd ed. (Upper Saddle River, NJ: Prentice Hall, 2012), and Chapter 16 in J. W.
Tester and M. Modell, Thermodynamics and Its Applications, 3rd ed. (Upper Saddle River,
NJ: Prentice Hall, 1997).
Appendix C Thermodynamic Relationships Involving the Equilibrium Constant 731

In terms of conversion for an equimolar feed, we have

CCO, 0 Xe CCO, 0 Xe
K ! --------------------------------------------------------------------- (EC-1.7)
CCO, 0 ( 1 " Xe ) CCO, 0 ( 1 " Xe )
Relate K and Xe
Xe2
! ---------------------- ! 1.44 (EC-1.8)
( 1 " Xe )2

Figure EC-1.1 Modell, Michael, and Reid, Robert, Thermodynamics and Its
Applications, 2nd ed., © 1983. Reprinted and electronically reproduced by
permission of Pearson Education, Inc., Upper Saddle River, NJ.
732 Thermodynamic Relationships Involving the Equilibrium Constant Appendix C

From Figure EC-1.1 we read at 1000 K that log KP ! 0.15; therefore, KP ! 1.41, which
is close to the calculated value. We note that there is no net change in the number of
moles for this reaction (i.e., ( ! 0); therefore,

K ! Kp ! Kc (dimensionless)

Taking the square root of Equation (EC-1.8) yields

Calculate Xe, the Xe
equilibrium --------------- ! (1.44)1/2 ! 1.2 (EC-1.9)
conversion 1 " Xe

Solving for Xe , we obtain

1.2
Xe ! ------- ! 0.55
2.2
Then
yCO, 0 P0
CCO,0 ! -----------------
-
RT0

( 0.5 )( 10 atm )
! ----------------------------------------------------------------------------------------
( 0.082 dm ) atm / mol ) K )( 1000 K )
3

! 0.061 mol/dm3
Calculate CCO,e,
the equilibrium CCO,e ! CCO,0 (1 " Xe ) ! (0.061)(1 " 0.55) ! 0.0275 mol/dm3
conversion of CO
CH2O, e ! 0.0275 mol/dm3

CCO2,e ! CH2, e ! CCO,0 Xe ! 0.0335 mol/dm3

Figure EC-1.1 gives the equilibrium constant as a function of temperature for a

number of reactions. Reactions in which the lines increase from left to right are
exothermic.
The following links give thermochemical data. (Heats of Formation, CP, etc.)
1) www.uic.edu/~mansoori/Thermodynamic.Data.and.Property_html
2) webbook.nist.gov
Also see Chem. Tech., 28 (3) (March), 19 (1998).