CHEMICAL ENGINEERING

THERMODYNAMICS
(CHE 325)
Dr. Engr. O.D. ADENIYI
B.Eng, M.Eng, Ph.D (Sheffield,U.K.), COREN, MNSE, MNSChE, AMIChemE, SEG,
SPE, GradEI, CombInst

M O D U L E 3 : H E AT E F F E C T S

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 REFERENCES
Klotz I.M. and Rosenberg R.M. (2008), Chemical Thermodynamics, basic concepts and methods,
7th Edition, John Wiley and sons, Inc, New Jersey, USA, 563pp.
Moran M.J. and Shapiro H.N. (2008), Fundamentals of Engineering thermodynamics, John wiley
and Sons, USA.
Smith J.M., Van Ness H.C. and Abbott M.M. (2001), Introduction to Chemical engineering
thermodynamics, 6th edition, McGraw Hill International Edition, U.S.A. 731pp.
Sandler S.I. (1989) “Chemical and engineering thermodynamics” 2nd Edition, Wiley Series in
Chemical engineering, NY.
Warn J.R.W. and Peters A.P.H. (1996), Concise Chemical Thermodynamics, 2nd edition, Thomsen
Press, India.
Green D.W and Perry R.H. (2008), Perry’s Chemical Engineers’ Handbook, 8th edition, McGraw
Hill Companies Inc., USA.
Riley K.F. , Hobson M.P. and Bence S.J (2006), Mathematical methods for physics and
engineering, 3rd ed., Cambridge University Press, U.K., pp. 1333.

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 COURSE STRUCTURE

 Lectures & Note

 Quiz
 Assignment
 Examinations

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 HEAT EFFECTS

SENSITIVE HEAT EFFECTS

When heat is transferred to any system where there is no
phase transition, no change in composition and no
chemical reaction there will be a change in the system
temperature.

The sensible heat effects relate the quantity of heat

transferred and the resulting change in temperature.

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 HEAT EFFECTS
U = U(T,V) (3.1)
Where (3.2)

The constant volume heat capacity is given by Equation (3.3);

(3.3)
Substituting Equation (3.3) into (3.2) we have;

(3.4)

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 HEAT EFFECTS
Under two conditions the final terms of Equation (3.4) is equal to zero, that is;
• For any constant volume process, irrespective of the material.
• When the internal energy is independent of the volume, irrespective of the
process. This is true for ideal gases and incompressible fluids and also
approximately true for low pressure gases.
Under these conditions then Equation (3.4) become Equation (3.5).
(3.5)

(3.6)

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 HEAT EFFECTS
For mechanically reversible constant volume process,
Q=ΔU;
(3.7)

Likewise the molar or specific enthalpy is expressed as a

function of temperature and pressure as;
H = H(T,P) (3.8)

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 HEAT EFFECTS
H = H(T,P) (3.8)

(3.9)

(3.10)

Likewise under two conditions the final term of Equation (3.10)

becomes zero.
• For any constant pressure process, irrespective of the material.
• When the enthalpy is independent of the pressure, irrespective
of the process. This is true for ideal gases and also
approximately true for low pressure gases.
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 HEAT EFFECTS
.
(3.11)

(3.12)

(3.13)

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 HEAT CAPACITY AND TEMPERATURE
Temperature dependence of the heat capacity:

(3.14)

(3.15)

(3.16)

Where α, β and γ, a, b and c are constants features of a given material

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 HEAT CAPACITY AND TEMPERATURE
Equation (3.18) relates the two ideal gas heat capacities:

(3.17)

(3.18)

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 EXAMPLE 3.1
The specific heat capacity of methane in the ideal gas state is given
as a function of temperature in kelvin by Equation E1. Develop
an equation for this expression as a function of temperature in
oC.

(E1)

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 SOLUTION 3.1
The relation between the two temperature scales is:
T (K) = t (oC) + 273.15

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 GAS MIXTURE SPECIFIC HEAT CAPACITY
For gas mixture:

(3.19)

Where CPAig, CPBig and CPCig are the molar or specific heat capacities
of pure A,B, and C in the ideal gas state.

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 SENSIBLE HEAT INTEGRAL
To evaluate the integral ∫CpdT for the temperature limits of To and T
(3.20)

Where

When we are given T and To, the calculation of Q or ΔH becomes

easy .

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 SENSIBLE HEAT INTEGRAL
Factoring (τ -1) from each term on the right- hand side of Equation
(3.20) gives (3.21):

(3.21)

Where

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 EXAMPLE 3.2
Calculate the heat required to raise the temperature of 1
mol of methane from 533.15 K to 873.15 K (260 to
600oC) in a steady flow process at a pressure
sufficiently low that methane may be considered as
ideal gas.
Given that;
A= 1.702, B=9.081 x 10-3, and C= -2.164 x 10-6

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 SOLUTION 3.2
Given that To= 533.15 K, T=873.15 K τ = T/To=873.15/533.15 = 1.6377
Applying Equations 3.13 and 3.20 :
(3.13)

(3.20)

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 PURE SUBSTANCES LATENT HEAT
A given substance when liquefied from the solid state to the liquid state or when
vaporized from the liquid at constant pressure, no change in temperature
occurs but the process requires the transfer of a determinate amount of heat
to the substance. The heat effects are known as the latent heat of fusion and
the latent heat of vaporization.
The latent heat accompanying a phase change is a function of temperature only
and is related to the system properties by Clapeyron Thermodynamic Equation
(3.26).

(3.26)

For pure species at temperature T, ΔH= latent heat, ΔV = volume change

accompanying phase change, Psat = vapour pressure.

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 WATSON’S CORRELATION
The estimation of the latent heat of vaporization of a pure liquid at
a given temperature from the known value of a single
temperature is done experimentally and also through the use of
Watson’s correlation:

(3.27)

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 EXAMPLE 3.4
The latent heat of vaporization of water at 373.15
K (100oC) is 2257 kJ kg-1, estimate the latent
heat at 573.15 K (300oC).

Given that Tc= 647.1 K.

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 SOLUTION 3.4
ΔH1 = latent heat at 373.15 K (100oC) = 2257 kJ/kg
ΔH2 = latent heat at 573.15 K (300oC) = ?
Tr1 = T/Tc = 373.15/647.1 = 0.577
Tr2 = T/Tc = 573.15/647.1 = 0.886

= 2257 x (0.270)0.38 = 1371 kJ/kg

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 STANDARD HEAT OF REACTION
Most chemical reactions are complemented by the transfer of heat
or by temperature changes during the reaction or by the two.
These are as a result of the molecular structure differences and
also differences in energy of the products and reactants.
Consider the following reaction:
aA + bB  cC + dD
The standard heat of reaction of the above reaction is defined as
the enthalpy change when a mole of A and b moles of B in their
standard states at temperature T react to form c moles of C and
d moles of D in their standard states at the same temperature T.

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 STANDARD HEAT OF REACTION
The standard state pressure is 1 bar (105 pa) and the property
values in the standard state are denoted by the degree symbol
(o). Cpo is the standard state heat capacity, and because the
standard state for gases is the ideal gas state, Cpo is equal to
Cpig. All conditions for the standard state are constant with the
exception of temperature, defined as the operating temperature
of the system. The standard state properties are functions of
temperature only.
The symbol ΔHo298 represent the standard heat of reaction at the
standard state temperature of 298.15 K (25oC).

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 STANDARD HEAT OF FORMATION
When all the compounds taking place in any given
reaction is known then the standard heat of formation
can be used to calculate the standard heat of reaction.
A formation reaction itself is a reaction which forms a
single compound from its constituent elements.

As an example the reaction C + ½O2 + 2H2  CH3OH is

the formation reaction for methanol.

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 WATER GAS SHIFT REACTION
CO2(g) + H2(g)  CO(g) + H2O (g) (25oC). The formation reactions could be spilted
CO2 (g): C(s) + O2 (g)  CO2 (g) ΔHof298 = -393.509 kJ
H2 (g): Since hydrogen is an element ΔHof298 = 0
CO (g): C(s) + ½O2 (g)  CO (g) ΔHof298 = -110.525 kJ
H2O (g): H2(g) + ½O2 (g)  H2O (g) ΔHof298 = -241.818 kJ
In order to get the desired result, writing the formation reaction again so that the products
and the reactants are properly placed.
CO2 (g)  C(s) + O2 (g) ΔHo298 = +393.509 kJ
C(s) + ½O2 (g)  CO (g) ΔHo298 = -110.525 kJ
H2(g) + ½O2 (g)  H2O (g) ΔHo298 = -241.818 kJ
================================================================
CO2 (g) + H2(g)  CO(g) + H2O (g) ΔHo298 = 41.166 kJ

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 EXAMPLE 3.5
Consider the following reaction :
4HCl (g) + O2 (g)  2H2O (g) + 2Cl2 (g),

it is expected that you evaluate the standard heat

of formation. Given that the standard heat of
formation at 298.15 K of its constituent
composition are HCl (g) is -92.307 kJ; H2O(g) is -
241.818 kJ.

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 SOLUTION 3.5
Solution: the reaction combination that gives the required formation
are;

4HCl (g)  2H2 (g) + 2Cl2 (g) ΔHo298 = (4)( 92.307) kJ

2H2(g) + O2 (g)  2H2O (g) ΔHo298 = (2)(-241.818) kJ
----------------------------------------------------------------------------------------------------------------
4HCl(g) + O2(g)  2H2O(g) + 2Cl2(g) ΔHo298 = -114.408 kJ

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 STANDARD HEAT OF COMBUSTION
A combustion reaction is a reaction between any
given element or compound and oxygen to form
definite combustion products. Organic
compounds consists of carbon, hydrogen and
oxygen only and their combustion products are
water and carbon dioxide with the state of the
water either being vapour or liquid.

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 STANDARD HEAT OF COMBUSTION
As an example the formation reaction of n-butane cannot be carried out
practically.
4C(s) + 5H2(g)  C4H10(g)
The breakdown of the combustion reactions are:
4C(s) + 4O2(g)  4CO2(g) ΔHo298 = (4)(-393.509) kJ
5H2(g) + 2½O2(g)  5H2O(l) ΔHo298 = (5)(-285.830) kJ
4CO2(g) + 5H2O(l)  C4H10(g) + 6½O2(g) ΔHo298 = 2,877.396 kJ
-------------------------------------------------------------------------------------------------------------------------------------
4C(s) + 5H2(g)  C4H10(g) ΔHo298 = -125.790 kJ

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 TEMPERATURE EFFECTS ON STANDARD HEAT OF
REACTION
Consider the general chemical reaction;
|v1|A1 + |v2|A2 + .....  |v3|A3 + |v4|A4 + …….

Where |vi| is a stoichiometric coefficient and Ai is the chemical formula. The

components on the right are the product while the reactants are on the left. The
sign notations for |vi| is positive (+) for the products and negative (-) for the
reactants.
The |vi| with their signs are usually referred to as the stoichiometric numbers. Let
us consider the synthesis of ammonia reactions.
N2 + 3H2  2NH3
Thus the |vN2| = -1, |vH2| = -3, |vNH3| = 2

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 EXAMPLE 3.6
Consider the following methanol synthesis reaction
at 1073.15 K (800oC). Evaluate the standard
heat of reaction.

CO(g) + 2H2(g)  CH3OH(g)

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 SOLUTION 3.6
Applying Equation (3.29) to this reaction at the reference temperature To- 298.15 K and
with the heat of formation data from Table C.4 (Smith et al., 2001).

ΔHoo = ΔHo298= -200.660 – (-110.525) = - 90.135 kJ mol-1

The parameter evaluation of Equation 3.34 and data from Table C.1 (Smith et al., 2001)

i vi A 103B 106 C 10-5 D

CH3OH 1 2.211 12.216 -3.450 0.000
CO -1 3.376 0.557 0.000 -0.031
H2 -2 3.249 0.422 0.000 0.0830

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 SOLUTION 3.6
By definition
ΔA = (1)(2.211) + (-1)(3.376) + (-2)(3.249) = -7.663 and likewise
ΔB = 10.815 x 10-3
ΔC = -3.450 x 10-6
ΔD = -0.135 x 105

By Equation (3.33 )
ΔHoo = - 90.135 + 8.314[(-1615.5)/(103)]= -103.566 kJ mol-1

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