Chemical Engineering

Thermodynamics – I
ChE–301
Aqeel Ahmad TAIMOOR
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
 Sensible Heat
 Layman Definition: Heat that is detected by the
thermometer

 Sensible heat is the heat transfer when there is

 No Phase change
 No chemical reaction
 No change in the composition
 Sensible Heat
 For Ideal gas
 Closed system (Constant volume)
T2
Q = DU = ò CV dT
T1
 Open system (No work)
T2
Q = DH = ò CP dT
T1
 Cv & Cp are not constant as considered previously, rather
they are the function of temperature
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
 Real gas as an Ideal gas
 The ideal gas postulates suggests that the gas molecules
do not interact with each other (collision – elastic)

 Ideal gas molecules does not have volume (PV = RT)

 At very low pressure, the distance between the gas

molecules becomes very large compared to the gas
molecule size. So gas molecules size becomes negligible

 Similarly the interaction between molecules fades away

with increasing distance between them

 So, at very low pressure a gas may be assumed as an

ideal gas
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
 Ideal gas heat capacity for
real gas

 Ideal gas heat capacity for a real gas is the heat capacity
of that gas when P 0

 At low pressures, it is a good supposition that the heat

capacity is the function of temperature only even for
non-ideal/real gas
 Heat capacity as a
function of temperature
 Regression of the curves
gives the heat capacity
equation:

C pig
= A + BT + CT 2 + DT -2
R

 Values of A, B, C & D are

provided in Table C.1
 Problem
The parameters listed in Table C.1 require use of Kelvin
temperatures in heat capacity equation. Equation of the
same form may also be developed for use with temperatures
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. Determine the values of
constants to use the equation with temperature values in oC.
 Problem
Calculate the heat required to raise the temperature of 1 mol
of methane from 260 to 600°C (533.15 K to 873.15 K) in a
steady-flow process at a pressure sufficiently low that
methane may be considered an ideal gas.
 Problem
What is the final temperature when heat in the amount of
422 MJ is added to 11.3 kmol of ammonia initially at 260
oC (533.15 K) in a steady-flow process at approximately 1

atm?
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
Pure Substance Phase
Diagram

Fusion Curve

Vaporization Curve

Sublimation Curve
 Latent Heat
 When a substance is liquified, vaporised or solidified no
temperature change is observed but heat transfer (removal
or addition) is there
 This heat is not detected by the thermometer
 So this heat is insensible to the thermometer
 This is termed as Latent heat
 Specifically latent heat of Fusion or Vaporization
 Similarly some times heat is also involved when substance
changes from one solid state to another (Latent heat of
Transition), rhombic Sulphur to Monoclinic Sulphur
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
 Clapeyron equation
 At vapor liquid equilibrium
 dGL = dGV
 VLdP – SLdT = VVdP – SVdT
 dP/dT = ΔSLV/ΔVLV
 ΔS = Q/T
 ΔSLV = ΔHLV/T
 dP/dT = ΔHLV/TΔVLV
 Volume of vapors very high (ΔVLV= Vv)compared to liquid
(Clausis – Clapeyron equation) For an ideal gas
 d(lnP)/dT = ΔH/RT2
 Antoine Equation
 d(lnP)/dT = ΔHLV/RT2

 If ΔH is independent of T then

 lnPsat = –ΔHLV/RT + IC

 The above equation can be written as

 lnPsat = A –B/T

 More accurately, lnPsat = A –B/(T+C) (Antoine Equation)

 Appendix B.2 tabulates the values of the constants

Other forms of Liquid/Gas
Equilibrium line

 Riedel Equation, lnPsat = A + B/T + ClnT + DT6

 Wagnor equation lnPrsat = (Aτ + Bτ1.5 + Cτ3 + Dτ6)/(1-
τ)

τ = 1 – Tr
 Problem
Estimate the latent heat of vaporization at 300°C for water
by using Antoine and Clausis Claperyon Equation
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
Standard Heat of Reaction
 When ever a chemical reaction occurs it involves energy
depending upon the chemical structure of the reactants
and products

 The energy thus evolved or absorbed is termed as Heat

of Reaction

 Heat of reaction is a function of temperature

 Also it is not possible to tabulate the heat of reactions of

almost infinite number of chemical reactions

 So a standard way is devised to calculate the heat of

reactions
 Standard Heat of
Formation
 Standard heat of formation is the heat involved when a
chemical substance is formed from its constituents at 25°C

 For elements heat of formation is 0

 Consider the reaction

 CO2 + H2  CO + H2O

 What is the heat of reaction at 25°C? (Values in Table C.4)

Standard Heat of Reaction
 In Table C.4 check the standard heat of formation for
the components
 CO2 : ΔH°f298 = -393509J
 C + O2  CO2 ΔH°f298 = -393509J
 H2 : ΔH°f298 = 0J
 CO : ΔH°f298 = -110525J
 C + 1/2O2  CO ΔH°f298 = -110525J
 H2O : ΔH°f298 = -241818J
 H2 + 1/2O2  H2O ΔH°f298 = -241818J
 Hess’s Law
 CO2  C + O2 ΔH°f298 = 393509J

 C + 1/2O2  CO ΔH°f298 = -110525J

 H2 + 1/2O2  H2O ΔH°f298 = -241818J

 CO2 + H2  CO + H2O ΔH°f298 = 41166J

 So heat of reaction is just:

 Sum of heat of formation of Products – Sum of heat of

formation of Reactants
Standard Heat of Reaction
 All the components in the reaction were in gaseous
phase

 CO2(g) + H2(g)  CO(g) + H2O(g) ΔH°f298 = 41166J

 What happens if the any one component is in liquid

phase

 CO2(g) + H2(g)  CO(g) + H2O(l)

Standard Heat of Reaction
 CO2(g)  C(g) + O2(g) ΔH°f298 = 393509J

 C(g) + 1/2O2(g)  CO(g) ΔH°f298 = -110525J

 H2(g) + 1/2O2(g)  H2O(g) ΔH°f298 = -241818J

 H2O(g)  H2O(l) ΔH°f298 = -44012J

 CO2(g) + H2(g)  CO(g) + H2O(l) ΔH°298 = -2846J

 Problem
Calculate the standard heat at 25°C (298.15 K) for the
following reaction:

4HCl(g) +O2(g)  2H2O(g)+2Cl2(g)

 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
 Standard Heat of
Combustion
 Similarly to heat of formation, heat of combustion data
has also been tabulated.

 Heat of combustion is the heat evolved when 1 mole of

the substance is completely burned or oxygenated.

 E.g. find the heat of reaction for the following reaction

 4C(s) + 5H2(g)  C4H10(g)

 Standard Heat of Reaction
 4C(s) + 4O2  4CO2(g) ΔH°298 = 4 x -393509J

 5H2(g) + 2.5O2(g)  5H2O(l) ΔH°298 = 5 x -285830J

 CO2(g) + 5H2O(l)  C4H10(g) + 6.5O2 ΔH°298 = 2877396

 4C(s) + 5H2(g)  C4H10(g) ΔH°298 = -125790

 So heat of reaction is just:
 Sum of heat of Combustion of Reactants – Sum of heat of
combustion of Products
 Relation between heat of
formation with heat of
Combustion
 A direct relation between heat of combustion and heat
of formation as

H of  393.78 N C  121 N H  N X   271.81N F

 92.37 N Cl  36.26 N Br  24.81N I  297.26 N S  H comb
o
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard
 Heat of Reaction
 Heat of reaction is a function of temperature

 At any other temperature the reactants and the products

must be raised to the temperature of the reaction
 Problem
Calculate the standard heat of the methanol-synthesis
reaction at 800°C (1073.15 K):

CO(g) + 2H2(g)  CH3OH(g)

 Problem
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 (298.15 K).
 Problem
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:
CH4(g) + H2O(g)  CO(g) + 3H2(g)
The only other reaction to be considered 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 1300 K, the CH4 is completely converted
and the product stream contains 17.4 mole % CO. Assuming the
reactants to be preheated to 600 K, calculate the heat requirement
for the reactor.
 Problem
A boiler is fired with a high-grade fuel oil (consisting only of
hydrocarbons) having a standard heat of combustion of -
43515 J/g at 25°C (298.15 K) with CO(g)and H20(l) as
products. The temperature of the fuel and air entering the
combustion chamber is 25°C (298.15 K). The air is assumed
dry. The flue gases leave at 300°C (573.15 K), and their
average analysis (on a dry basis) is 11.2% CO2, 0.4% CO,
6.2% O2, and 82.2% N2 on volume basis. Calculate the
fraction of the heat of combustion of the oil that is
transferred as heat to the boiler.
 Class Objectives
 Understand the difference between sensible and insensible
heat
 Understand, when any gas is considered as an Ideal gas
 Understand, why heat capacity for an ideal gas is function of
temperature only and how the experimental values are
regressed to obtain the equation
 Understand the concept of Latent Heat
 Understand the regression of phase equilibrium lines, Clausis
Clapeyron Equation and Antoine equation
 Understand the standard heat of reaction, Hess’s Law
 Understand the standard heat of combustion
 Be able to calculate Heat of reaction at temperatures other
than standard